TW201605955A - Methacrylic resin composition - Google Patents

Methacrylic resin composition Download PDF

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TW201605955A
TW201605955A TW104117589A TW104117589A TW201605955A TW 201605955 A TW201605955 A TW 201605955A TW 104117589 A TW104117589 A TW 104117589A TW 104117589 A TW104117589 A TW 104117589A TW 201605955 A TW201605955 A TW 201605955A
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methacrylic resin
mass
acrylate
film
resin composition
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TW104117589A
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TWI662074B (en
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Toru Abe
Atsuhiro Nakahara
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Kuraray Co
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/04—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • C08L33/12—Homopolymers or copolymers of methyl methacrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state

Abstract

A methacrylic resin composition comprising a methacrylic resin (A) comprising not less than 90 % by mass of a structural unit derived from methyl methacrylate in which the methacrylic resin (A) has a triad syndiotacticity (rr) of not less than 58 % and a block copolymer (B) comprising 10 to 80 % by mass of a polymer block (b1) of a methacrylic acid ester and 90 to 20 % by mass of a polymer block (b2) of an acrylic acid ester, in which a mass ratio of the block copolymer (B) to the methacrylic resin (A) is from 1/99 to 90/10.

Description

甲基丙烯酸樹脂組成物 Methacrylic resin composition

本發明關於甲基丙烯酸樹脂組成物。更詳細地，本發明關於成形加工性優異且玻璃轉移溫度高之甲基丙烯酸樹脂組成物，其可得到透明性高，在寬廣的溫度範圍中霧度之變化小，厚度方向的相位差小，熱收縮率小且強度大之成形體。 The present invention relates to a methacrylic resin composition. More specifically, the present invention relates to a methacrylic resin composition which is excellent in moldability and has a high glass transition temperature, and has high transparency, a small change in haze in a wide temperature range, and a small phase difference in the thickness direction. A molded body having a small heat shrinkage rate and high strength.

作為玻璃轉移溫度高的甲基丙烯酸樹脂，已知高間規性(syndiotacticity)的甲基丙烯酸樹脂(參照專利文獻1、2)。然而，高間規性的甲基丙烯酸樹脂係成形加工性差，難以得到表面平滑的成形體。又，高間規性的甲基丙烯酸樹脂係耐溶劑性及耐熱性優異，但有力學強度低、脆弱、容易破裂之傾向。 As a methacrylic resin having a high glass transition temperature, a syndiotactic methacrylic resin is known (see Patent Documents 1 and 2). However, the high syndiotactic methacrylic resin has poor moldability, and it is difficult to obtain a molded body having a smooth surface. Further, the highly syndiotactic methacrylic resin is excellent in solvent resistance and heat resistance, but has a tendency to be low in mechanical strength, fragile, and easily broken.

另一方面，為了提高具有戊二醯亞胺結構的高玻璃轉移溫度之甲基丙烯酸樹脂的機械強度，尤其薄膜的折彎強度，有提案摻合含有玻璃轉移溫度0℃以下的橡膠狀聚合物之芯殼結構的接枝共聚物(例如，參照專利文獻3)。 On the other hand, in order to improve the mechanical strength of the methacrylic resin having a high glass transition temperature of a pentamethylene imine structure, especially the bending strength of the film, it is proposed to blend a rubbery polymer containing a glass transition temperature of 0 ° C or less. A graft copolymer of a core-shell structure (for example, refer to Patent Document 3).

[先前技術文獻] [Previous Technical Literature] [專利文獻] [Patent Literature]

[專利文獻1]日本特開平3-263412號公報 [Patent Document 1] Japanese Patent Laid-Open No. Hei 3-263412

[專利文獻2]日本特開2002-327012號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2002-327012

[專利文獻3]日本特許5408885號公報 [Patent Document 3] Japanese Patent No. 5,408,885

然而，若將上述專利文獻記載的接枝共聚物摻合於甲基丙烯酸樹脂中，則有透明性的降低、表面平滑性的降低、變形時或加熱時發生白色化等之現象。 However, when the graft copolymer described in the above patent document is blended in a methacrylic resin, there is a phenomenon in which transparency is lowered, surface smoothness is lowered, whitening occurs during deformation, or heating.

本發明之目的在於提供一種成形加工性優異且玻璃轉移溫度高之甲基丙烯酸樹脂組成物，其可得到透明性高，在寬廣的溫度範圍中霧度之變化小，厚度方向的相位差小，熱收縮率小且強度大之成形體。 An object of the present invention is to provide a methacrylic resin composition which is excellent in moldability and has a high glass transition temperature, and has high transparency, a small change in haze in a wide temperature range, and a small phase difference in a thickness direction. A molded body having a small heat shrinkage rate and high strength.

為了達成前述目的而進行探討，結果終於完成包含以下的實施形態之本發明。 In order to achieve the above object, the present invention finally completed the present invention including the following embodiments.

[1]一種甲基丙烯酸樹脂組成物，其包含：三元組表示之間規性(rr)為58%以上，且來自甲基丙烯酸甲酯的結構單元之含量為90質量%以上之甲基丙烯酸樹脂(A)，及具有10~80質量%的甲基丙烯酸酯聚合物嵌段(b1)與90~20質量%的丙烯酸酯聚合物嵌段(b2)之嵌段共聚物(B)，且嵌段共聚物(B)相對於甲基丙烯酸樹脂(A)之質量比為1/99~90/10。 [1] A methacrylic resin composition comprising: a triad indicating a degree of (rr) of 58% or more, and a content of a structural unit derived from methyl methacrylate of 90% by mass or more Acrylic resin (A), and block copolymer (B) having 10 to 80% by mass of methacrylate polymer block (b1) and 90 to 20% by mass of acrylate polymer block (b2), Further, the mass ratio of the block copolymer (B) to the methacrylic resin (A) is from 1/99 to 90/10.

[2]如[1]記載之甲基丙烯酸樹脂組成物，其中前述丙烯酸酯聚合物嵌段(b2)包含50~90質量的來自丙烯酸烷酯的結構單元%與50~10質量的來自(甲基)丙烯酸芳香族酯的結構單元%。 [2] The methacrylic resin composition according to [1], wherein the acrylate polymer block (b2) comprises 50 to 90% by mass of a structural unit derived from an alkyl acrylate and 50 to 10% by mass (a) %) structural unit % of an aromatic acrylate.

[3]如[1]或[2]記載之甲基丙烯酸樹脂組成物，其中嵌段共聚物(B)相對於甲基丙烯酸樹脂(A)之質量比為5/95~25/75。 [3] The methacrylic resin composition according to [1] or [2], wherein the mass ratio of the block copolymer (B) to the methacrylic resin (A) is from 5/95 to 25/75.

[4]如[1]~[3]中任一項記載之甲基丙烯酸樹脂組成物，其中甲基丙烯酸樹脂(A)係來自甲基丙烯酸甲酯的結構單元之總含量為99質量%以上，且在波長587.6nm(D線)及23℃的折射率n23D為1.488~1.490，嵌段共聚物(B)係在波長587.6nm(D線)及23℃的折射率n23D為1.485~1.495。 [4] The methacrylic resin composition according to any one of [1] to [3] wherein the methacrylic resin (A) is a total content of structural units derived from methyl methacrylate of 99% by mass or more The refractive index n 23D at a wavelength of 587.6 nm (D line) and 23 ° C is 1.488 to 1.490, and the block copolymer (B) has a refractive index n 23D at a wavelength of 587.6 nm (D line) and 23 ° C of 1.485~. 1.495.

[5]如[1]~[4]中任一項記載之甲基丙烯酸樹脂組成物，其中甲基丙烯酸樹脂(A)係重量平均分子量為50000~150000，分子量200000以上的成分之含量為0.1~10%，且分子量小於15000的成分之含量為0.2~5%。 [5] The methacrylic resin composition according to any one of [1] to [4] wherein the methacrylic resin (A) has a weight average molecular weight of 50,000 to 150,000, and a component having a molecular weight of 200,000 or more is 0.1. ~10%, and the content of the component having a molecular weight of less than 15,000 is 0.2 to 5%.

[6]如[1]~[5]中任一項記載之甲基丙烯酸樹脂組成物，其中甲基丙烯酸樹脂(A)係以甲基丙烯酸樹脂(a1)/甲基丙烯酸樹脂(a2)之質量比40/60~70/30，含有三元組表示之間規性(rr)為65%以上的甲基丙烯酸樹脂(a1)與三元組表示之間規性(rr)為45~58%的甲基丙烯酸樹脂(a2)。 [6] The methacrylic resin composition according to any one of [1] to [5] wherein the methacrylic resin (A) is a methacrylic resin (a1) / methacrylic resin (a2) The mass ratio is 40/60~70/30, and the ternary group has a regularity (rr) of 65% or more. The methacrylic resin (a1) and the triad have a regularity (rr) of 45 to 58. % methacrylic resin (a2).

[7]如[6]記載之甲基丙烯酸樹脂組成物，其中甲基丙烯酸樹脂(a2)係重量平均分子量為80000~150000。 [7] The methacrylic resin composition according to [6], wherein the methacrylic resin (a2) has a weight average molecular weight of 80,000 to 150,000.

[8]如[1]~[7]中任一項記載之甲基丙烯酸樹脂組成物，其進一步含有紫外線吸收劑。 [8] The methacrylic resin composition according to any one of [1] to [7] further comprising an ultraviolet absorber.

[9]如[1]~[8]中任一項記載之甲基丙烯酸樹脂組成物，其中相對於甲基丙烯酸樹脂(A)及嵌段共聚物(B)之合計量100質量份，進一步含有1~10質量份的聚碳酸酯樹脂。 [10] The methacrylic resin composition according to any one of [1] to [8], wherein the total amount of the methacrylic resin (A) and the block copolymer (B) is 100 parts by mass, further It contains 1 to 10 parts by mass of a polycarbonate resin.

[10]如請求項1~8中任一項記載之甲基丙烯酸樹脂組成物，其中相對於甲基丙烯酸樹脂(A)及嵌段共聚物(B)之合計量100質量份，進一步含有1~10質量份的苯氧樹脂。 [10] The methacrylic resin composition according to any one of claims 1 to 8, which further contains 1 part by mass based on 100 parts by mass of the total of the methacrylic resin (A) and the block copolymer (B). ~10 parts by mass of phenoxy resin.

[11]一種成形體，其係由如前述[1]~[10]中任一項記載之甲基丙烯酸樹脂組成物所構成。 [11] A molded article comprising the methacrylic resin composition according to any one of the above [1] to [10].

[12]一種薄膜，其係由如前述[1]~[10]中任一項記載之甲基丙烯酸樹脂組成物所構成。 [12] A film comprising the methacrylic resin composition according to any one of the above [1] to [10].

[13]如[12]記載之薄膜，其係以面積比在至少一方向中經延伸至1.5~8倍。 [13] The film according to [12], which is extended to 1.5 to 8 times in an area ratio in at least one direction.

[14]一種偏光鏡保護膜，其包含如前述[12]或[13]記載之薄膜。 [14] A polarizer protective film comprising the film according to the above [12] or [13].

本發明之甲基丙烯酸樹脂組成物係成形加工性優異且玻璃轉移溫度高。藉由使用本發明之甲基丙烯酸樹脂組成物，可得到透明性高，在寬廣的溫度範圍中霧度之變化小，厚度方向的相位差小，熱收縮率小且強度大之成形體。該成形體係適合於偏光鏡保護膜、液晶保護板、攜帶型資訊終端之表面材料、攜帶型資訊 終端的顯示窗保護膜、導光膜、各種顯示器之前面板用途等。 The methacrylic resin composition of the present invention is excellent in moldability and high in glass transition temperature. By using the methacrylic resin composition of the present invention, a molded article having high transparency, small change in haze in a wide temperature range, small phase difference in the thickness direction, small heat shrinkage ratio, and high strength can be obtained. The forming system is suitable for polarizing mirror protective film, liquid crystal protective board, surface material of portable information terminal, and portable information Display window protective film, light guide film, front panel use of various displays, etc.

11‧‧‧偏光鏡 11‧‧‧ polarizer

12‧‧‧接著劑層 12‧‧‧ adhesive layer

13‧‧‧易接著層 13‧‧‧Easy layer

14‧‧‧偏光鏡保護膜 14‧‧‧ polarizer protective film

15‧‧‧接著劑層 15‧‧‧ adhesive layer

16‧‧‧光學薄膜 16‧‧‧Optical film

第1圖係顯示本發明之一實施形態的偏光板之構成的圖。 Fig. 1 is a view showing the configuration of a polarizing plate according to an embodiment of the present invention.

[實施發明之形態] [Formation of the Invention]

本發明之甲基丙烯酸樹脂組成物含有甲基丙烯酸樹脂(A)與嵌段共聚物(B)。 The methacrylic resin composition of the present invention contains a methacrylic resin (A) and a block copolymer (B).

本發明所用的甲基丙烯酸樹脂(A)，係三元組表示之間規性(rr)為58%以上，較佳為59%以上，更佳為60%以上。甲基丙烯酸樹脂(A)的三元組表示之間規性(rr)之上限係沒有特別的限制，但從成形加工性之觀點來看，較佳為99%，更佳為85%，尤佳為77%，尤較佳為70%，尤更佳為65%，最佳為64%。 The methacrylic resin (A) used in the present invention has a regularity (rr) of 58% or more, preferably 59% or more, more preferably 60% or more. The ternary group of the methacrylic resin (A) means that the upper limit of the regularity (rr) is not particularly limited, but from the viewpoint of moldability, it is preferably 99%, more preferably 85%. Preferably, the ratio is 77%, particularly preferably 70%, especially preferably 65%, and most preferably 64%.

三元組表示之間規性(rr)(以下亦僅稱「間規性(rr)」)係連續3個結構單元之鏈(三元組，triad)中存在的2個鏈(二元組，diad)皆為外消旋(記載為rr)之比例。再者，於聚合物分子中的結構單元之鏈(二元組，diad)中，將立體構型相同者稱為內消旋(meso)，將相反者稱為外消旋(racemo)，各自記載為m、r。 The triad indicates the regularity (rr) (hereinafter also referred to as "syndiotactic (rr)") is the two chains existing in the chain of three consecutive structural units (triad) (dual group) , diad) are all ratios of racemic (denoted as rr). Furthermore, in the chain of structural units (diads) in a polymer molecule, the same stereo configuration is referred to as meso (meso), and the opposite is referred to as racem, each It is described as m and r.

三元組表示之間規性(rr)(%)係在重氫化氯仿中，於30℃測定1H-NMR光譜，自該光譜來計算TMS為0ppm時的0.6~0.95ppm之區域的面積(X)與0.6~ 1.35ppm之區域的面積(Y)，用式：(X/Y)×100算出。 The triad indicates that the regularity (rr) (%) is in the hydrogenated chloroform, and the 1 H-NMR spectrum is measured at 30 ° C, and the area of the region of 0.6 to 0.95 ppm when the TMS is 0 ppm is calculated from the spectrum ( The area (Y) of X) and the region of 0.6 to 1.35 ppm is calculated by the formula: (X/Y) × 100.

本發明所用的甲基丙烯酸樹脂(A)係重量平均分子量MwA較佳為5萬~15萬，更佳為6萬~14萬，尤佳為7萬~12萬。由於MwA為5萬以上且間規性(rr)為58%以上，所得之薄膜係強度大，難以破裂，容易延伸。因此，可將薄膜更減薄。又，由於MwA為15萬以下，甲基丙烯酸樹脂係成形加工性升高，故有所得之薄膜的厚度均勻且表面平滑性優異之傾向。 The methacrylic resin (A) used in the present invention has a weight average molecular weight Mw A of preferably 50,000 to 150,000, more preferably 60,000 to 140,000, and particularly preferably 70,000 to 120,000. Since Mw A is 50,000 or more and the syndiotacticity (rr) is 58% or more, the obtained film has high strength, is difficult to be broken, and is easily stretched. Therefore, the film can be made thinner. In addition, since the Mw A is 150,000 or less, the moldability of the methacrylic resin is increased, so that the obtained film has a uniform thickness and excellent surface smoothness.

本發明所用的甲基丙烯酸樹脂(A)係MwA與數量平均分子量MnA之比(MwA/MnA)較佳為1.2~5.0，更佳為1.3~3.5。由於MwA/MnA為1.2以上，甲基丙烯酸樹脂之流動性升高，所得之薄膜係有表面平滑性優異之傾向。由於MwA/MnA為5.0以下，所得之薄膜係有耐衝擊性及韌性優異之傾向。再者，MwA及MnA係將以凝膠滲透層析術(GPC)所測定的層析圖換算成標準聚苯乙烯的分子量而得之值。 The ratio (Mw A /Mn A ) of the methacrylic resin (A) to Mw A and the number average molecular weight Mn A used in the present invention is preferably from 1.2 to 5.0, more preferably from 1.3 to 3.5. When Mw A /Mn A is 1.2 or more, the fluidity of the methacrylic resin is increased, and the obtained film tends to have excellent surface smoothness. When Mw A /Mn A is 5.0 or less, the obtained film tends to have excellent impact resistance and toughness. Further, Mw A and Mn A are obtained by converting a chromatogram measured by gel permeation chromatography (GPC) into a molecular weight of standard polystyrene.

本發明所用的甲基丙烯酸樹脂(A)係分子量200000以上的成分(高分子量成分)之含量較佳為0.1~10%，更佳為0.5~5%。又，本發明所用的甲基丙烯酸樹脂(A)係分子量小於15000的成分(低分子量成分)之含量較佳為0.2~5%，更佳為1~4.5%。由於甲基丙烯酸樹脂(A)以該範圍含有高分子量成分及低分子量成分，製膜性升高，容易得到均勻的膜厚之薄膜。 The content of the component (high molecular weight component) having a molecular weight of 200,000 or more in the methacrylic resin (A) used in the present invention is preferably from 0.1 to 10%, more preferably from 0.5 to 5%. Further, the content of the component (low molecular weight component) having a molecular weight of less than 15,000 in the methacrylic resin (A) used in the present invention is preferably 0.2 to 5%, more preferably 1 to 4.5%. Since the methacrylic resin (A) contains a high molecular weight component and a low molecular weight component in this range, the film formability is improved, and a film having a uniform film thickness can be easily obtained.

分子量200000以上的成分之含量，係在GPC測定的層析圖與基線所包圍的部分之面積中，作為在分子量 200000的標準聚苯乙烯之保持時間之前檢測出的層析圖與基線所包圍的部分之面積的比例算出。分子量小於15000的成分之含量，係在GPC所得之層析圖與基線所包圍的部分之面積中，作為分子量15000的標準聚苯乙烯之保持時間之後檢測出的層析圖與基線所包圍的部分之面積的比例算出。 The content of the component having a molecular weight of 200,000 or more is in the area of the portion surrounded by the chromatogram and the baseline measured by GPC, as the molecular weight in the molecular weight The ratio of the chromatogram detected before the retention time of the standard polystyrene of 200000 to the area of the portion surrounded by the baseline was calculated. The content of the component having a molecular weight of less than 15,000 is in the area of the portion surrounded by the chromatogram obtained by GPC and the baseline, and the portion surrounded by the chromatogram and the baseline detected after the retention time of the standard polystyrene having a molecular weight of 15,000. The ratio of the area is calculated.

再者，GPC測定係如以下地進行。使用四氫呋喃作為洗提液，使用串聯連接有東曹股份有限公司製的TSKgel SuperMultipore HZM-M兩支與SuperHZ4000者作為管柱。使用具備差示折射率檢測器(RI檢測器)的東曹股份有限公司製之HLC-8320(型號)作為檢測裝置。試料係使用在5ml的四氫呋喃中溶解有4mg的甲基丙烯酸樹脂之溶液。將管柱烘箱之溫度設定在40℃，以0.35ml/分鐘的洗提液流量，注入20μl的試料溶液，測定層析圖。 Further, the GPC measurement was carried out as follows. Tetrahydrofuran was used as the eluent, and two TSKgel SuperMultipore HZM-M and SuperHZ4000 manufactured by Tosoh Corporation were connected in series as a column. A HLC-8320 (model) manufactured by Tosoh Corporation, which has a differential refractive index detector (RI detector), was used as a detecting device. The sample used was a solution in which 4 mg of methacrylic resin was dissolved in 5 ml of tetrahydrofuran. The temperature of the column oven was set at 40 ° C, and 20 μl of the sample solution was injected at a flow rate of the elution solution of 0.35 ml/min, and the chromatogram was measured.

測定分子量為400~5000000之範圍的標準聚苯乙烯，作成表示保持時間與分子量之關係的校正曲線。將連接層析圖的高分子量側之斜率自零變成正之點與低分子量側的波峰之斜率自負變成零之點的線作為基線。當層析圖顯示複數的波峰時，將連接最高分子量側的波峰之斜率自零變成正之點與最低分子量側的波峰之斜率自負變成零之點的線作為基線。 A standard polystyrene having a molecular weight of 400 to 5,000,000 was measured, and a calibration curve indicating the relationship between the retention time and the molecular weight was prepared. A line connecting the slope of the high molecular weight side of the chromatogram from zero to a positive point and the slope of the peak of the low molecular weight side from a negative to zero is taken as a baseline. When the chromatogram shows a complex peak, a line connecting the slope of the peak on the highest molecular weight side from zero to a positive point and the slope of the peak on the lowest molecular weight side from a negative to zero is taken as a baseline.

本發明所用的甲基丙烯酸樹脂(A)係依據JIS K7210，在230℃、3.8kg荷重之條件下測定的熔體流速較佳為0.1~20g/10分鐘，更佳為0.5~15g/10分鐘，最 佳為1.0~10g/10分鐘。 The methacrylic resin (A) used in the present invention is preferably a melt flow rate of 0.1 to 20 g/10 min, more preferably 0.5 to 15 g/10 min, measured under conditions of 230 ° C and a load of 3.8 kg in accordance with JIS K7210. ,most Good for 1.0~10g/10 minutes.

本發明所用的甲基丙烯酸樹脂(A)，從耐熱性提高之觀點來看，以甲基丙烯酸樹脂(A)之質量作為基準，來自甲基丙烯酸甲酯的結構單元之含量為90質量%以上，較佳為93質量%以上，更佳為95質量%以上，特佳為98質量%以上，最佳為100質量%。 The methacrylic resin (A) used in the present invention has a content of a structural unit derived from methyl methacrylate of 90% by mass or more based on the mass of the methacrylic resin (A) from the viewpoint of improvement in heat resistance. It is preferably 93% by mass or more, more preferably 95% by mass or more, particularly preferably 98% by mass or more, and most preferably 100% by mass.

本發明所用的甲基丙烯酸樹脂(A)亦可含有來自甲基丙烯酸甲酯的結構單元以外之結構單元，例如可舉出甲基丙烯酸乙酯、甲基丙烯酸環己酯、甲基丙烯酸第三丁酯、甲基丙烯酸異酯、甲基丙烯酸8-三環[5.2.1.02,6]癸酯、甲基丙烯酸4-第三丁基環己酯等之甲基丙烯酸甲酯以外的甲基丙烯酸烷酯，丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸丁酯、丙烯酸2-乙基己酯等之丙烯酸烷酯，丙烯酸苯酯等之丙烯酸芳酯，丙烯酸環己酯、丙烯酸降烯酯等之丙烯酸環烷酯，丙烯醯胺，甲基丙烯醯胺，丙烯腈，甲基丙烯腈等之在一分子中僅具有一個聚合性碳-碳雙鍵之來自乙烯系單體的結構單元。 The methacrylic resin (A) used in the present invention may further contain a structural unit other than the structural unit derived from methyl methacrylate, and examples thereof include ethyl methacrylate, cyclohexyl methacrylate, and methacrylic acid. Butyl ester, methacrylic acid Esters, alkyl methacrylates other than methyl methacrylate such as 8-tricyclo[5.2.1.0 2,6 ]decyl methacrylate or 4-t-butylcyclohexyl methacrylate, methyl acrylate , alkyl acrylate such as ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, aryl acrylate such as phenyl acrylate, cyclohexyl acrylate, acrylic acid A structure derived from a vinyl monomer such as a cycloalkyl acrylate such as an enester, a acrylamide, a methacrylamide, an acrylonitrile or a methacrylonitrile having only one polymerizable carbon-carbon double bond in one molecule. unit.

本發明所用的甲基丙烯酸樹脂(A)之玻璃轉移溫度較佳為120℃以上，更佳為123℃以上，尤佳為124℃以上。該甲基丙烯酸樹脂之玻璃轉移溫度的上限較佳為135℃，更佳為130℃。玻璃轉移溫度係可藉由調節分子量或間規性(rr)而控制。玻璃轉移溫度若在此範圍，則所得之薄膜的熱收縮等之變形係難以發生。再者，玻璃轉移溫度係依據JIS K7121所測定之中間點玻璃轉移 溫度。具體而言，係將試料升溫至230℃為止，其次冷卻至室溫為止，然後於自室溫至230℃為止以10℃/分鐘使其升溫之條件下測定DSC曲線。決定自第2次的升溫時所測定之DSC曲線所求得的中間點玻璃轉移溫度。 The glass transition temperature of the methacrylic resin (A) used in the present invention is preferably 120 ° C or higher, more preferably 123 ° C or higher, and particularly preferably 124 ° C or higher. The upper limit of the glass transition temperature of the methacrylic resin is preferably 135 ° C, more preferably 130 ° C. The glass transition temperature can be controlled by adjusting the molecular weight or the syndiotacticity (rr). When the glass transition temperature is within this range, the deformation of the resulting film such as heat shrinkage is less likely to occur. Furthermore, the glass transition temperature is based on the intermediate point glass transfer measured according to JIS K7121. temperature. Specifically, the sample was heated to 230 ° C, and then cooled to room temperature, and then the DSC curve was measured under the conditions of raising the temperature from room temperature to 230 ° C at 10 ° C /min. The intermediate point glass transition temperature determined from the DSC curve measured at the second temperature rise was determined.

本發明所用的甲基丙烯酸樹脂(A)在23℃、50%RH下測定的在波長587.6nm(D線)的折射率n23D，從所得之甲基丙烯酸樹脂組成物的透明性之觀點來看，較佳為1.488~1.490，更佳為1.4885~1.4897。 The methacrylic resin (A) used in the present invention has a refractive index n 23D at a wavelength of 587.6 nm (D line) measured at 23 ° C and 50% RH from the viewpoint of transparency of the obtained methacrylic resin composition. Look, it is preferably 1.488~1.490, more preferably 1.4885~1.4897.

本發明所用的甲基丙烯酸樹脂(A)係可藉由1種的甲基丙烯酸樹脂滿足前述特性，也可藉由複數種的甲基丙烯酸樹脂之混合物滿足前述特性。 The methacrylic resin (A) used in the present invention can satisfy the above characteristics by one type of methacrylic resin, and can satisfy the above characteristics by a mixture of a plurality of kinds of methacrylic resins.

構成本發明所用之甲基丙烯酸樹脂(A)的1種或2種以上之甲基丙烯酸樹脂，係可藉由眾所周知的聚合方法來製造。前述甲基丙烯酸樹脂(A)的各特性係可藉由調整聚合溫度、聚合時間、鏈轉移劑之種類或量、聚合起始劑之種類或量等之聚合條件而實現。 One or two or more kinds of methacrylic resins constituting the methacrylic resin (A) used in the present invention can be produced by a known polymerization method. The respective characteristics of the methacrylic resin (A) can be achieved by adjusting the polymerization conditions such as the polymerization temperature, the polymerization time, the kind or amount of the chain transfer agent, and the kind or amount of the polymerization initiator.

作為甲基丙烯酸樹脂之製造時所用的聚合反應形態，例如可舉出自由基聚合法、陰離子聚合法等。 Examples of the polymerization reaction form used in the production of the methacrylic resin include a radical polymerization method and an anionic polymerization method.

於自由基聚合法中，可採用懸浮聚合法、塊狀聚合法、溶液聚合法、乳化聚合法等之聚合手法。於此等之中，從生產性及耐熱分解性之觀點來看，較佳為懸浮聚合法、塊狀聚合法。 In the radical polymerization method, a polymerization method such as a suspension polymerization method, a bulk polymerization method, a solution polymerization method, or an emulsion polymerization method can be employed. Among these, from the viewpoint of productivity and thermal decomposition resistance, a suspension polymerization method or a bulk polymerization method is preferred.

於陰離子聚合法中，可採用塊狀聚合法、溶液聚合法等之聚合手法。 In the anionic polymerization method, a polymerization method such as a bulk polymerization method or a solution polymerization method can be employed.

聚合反應係因聚合起始劑而開始。自由基聚合中所用的聚合起始劑，只要是產生反應性自由基者，則沒有特別的限定。該聚合起始劑係1小時半衰期溫度較佳為60~140℃，更佳為80~120℃。 The polymerization reaction starts with a polymerization initiator. The polymerization initiator used in the radical polymerization is not particularly limited as long as it generates reactive radicals. The polymerization initiator has a one-hour half-life temperature of preferably from 60 to 140 ° C, more preferably from 80 to 120 ° C.

作為自由基聚合中所用的聚合起始劑，例如可舉出第三己基過氧異丙基單碳酸酯、第三己基過氧2-乙基己酸酯、1,1,3,3-四甲基丁基過氧2-乙基己酸酯、第三丁基過氧三甲基乙酸酯、第三己基過氧三甲基乙酸酯、第三丁基過氧新癸酸酯、第三己基過氧新癸酸酯、1,1,3,3-四甲基丁基過氧新癸酸酯、1,1-雙(第三己基過氧)環己烷、苯甲醯基過氧化物、3,5,5-三甲基己醯基過氧化物、月桂醯基過氧化物、2,2’-偶氮雙(2-甲基丙腈)、2,2’-偶氮雙(2-甲基丁腈)、二甲基2,2’-偶氮雙(2-甲基丙酸酯)等。其中，較佳為第三己基過氧2-乙基己酸酯、1,1-雙(第三己基過氧)環己烷、二甲基2,2’-偶氮雙(2-甲基丙酸酯)。此等聚合起始劑係可單獨1種或組合2種以上使用。聚合起始劑之添加量或添加方法等，只要是按照目的來適宜設定即可，並沒有特別的限定。例如，懸浮聚合法所用的聚合起始劑之量，相對於供聚合反應的全部單體100質量份，較佳為0.0001~0.1質量份，更佳為0.001~0.07質量份。 Examples of the polymerization initiator used in the radical polymerization include, for example, a third hexylperoxyisopropylmonocarbonate, a third hexylperoxy-2-ethylhexanoate, and 1,1,3,3-tetra Methyl butyl peroxy 2-ethylhexanoate, t-butyl peroxytrimethyl acetate, third hexyl peroxytrimethyl acetate, tert-butyl peroxy neodecanoate, Third hexyl peroxy neodecanoate, 1,1,3,3-tetramethylbutyl peroxy neodecanoate, 1,1-bis(trihexylperoxy)cyclohexane, benzamidine Peroxide, 3,5,5-trimethylhexyl peroxide, lauryl peroxide, 2,2'-azobis(2-methylpropionitrile), 2,2'-couple Nitrogen bis(2-methylbutyronitrile), dimethyl 2,2'-azobis(2-methylpropionate), and the like. Among them, preferred is third hexylperoxy 2-ethylhexanoate, 1,1-bis(trihexylperoxy)cyclohexane, dimethyl 2,2'-azobis(2-methyl Propionate). These polymerization initiators may be used alone or in combination of two or more. The amount of the polymerization initiator to be added, the method of addition, and the like are not particularly limited as long as they are appropriately set according to the purpose. For example, the amount of the polymerization initiator used in the suspension polymerization method is preferably 0.0001 to 0.1 parts by mass, more preferably 0.001 to 0.07 parts by mass, per 100 parts by mass of the total monomers for the polymerization reaction.

陰離子聚合中所用的聚合起始劑，只要是產生反應性陰離子者，則沒有特別的限定。作為該聚合起始劑，可舉出有機鹼金屬化合物、鹼金屬或鹼土類金屬的礦酸鹽、由有機鹼金屬化合物與有機鋁化合物之組合所成者、有機稀土類金屬錯合物等。 The polymerization initiator used in the anionic polymerization is not particularly limited as long as it is a reactive anion. Examples of the polymerization initiator include an organic alkali metal compound, a mineral acid salt of an alkali metal or an alkaline earth metal, a combination of an organic alkali metal compound and an organoaluminum compound, and an organic rare earth metal complex.

作為陰離子聚合法中所用的聚合起始劑之具體例，可舉出正丁基鋰、第二丁基鋰、異丁基鋰、第三丁基鋰等之烷基鋰等。 Specific examples of the polymerization initiator used in the anionic polymerization method include alkyllithium such as n-butyllithium, second butyllithium, isobutyllithium, and t-butyllithium.

又，作為有機鋁化合物，可舉出AlR1R2R3所示的化合物。 Further, examples of the organoaluminum compound include compounds represented by AlR 1 R 2 R 3 .

而且，式中R1、R2及R3各自獨立地表示可具有取代基的烷基、可具有取代基的環烷基、可具有取代基的芳基、可具有取代基的芳烷基、可具有取代基的烷氧基、可具有取代基的芳氧基或N,N-二取代胺基。再者，R2及R3亦可為彼等鍵結而成之可具有取代基的伸芳二氧基。 Further, in the formula, R 1 , R 2 and R 3 each independently represent an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent, an aralkyl group which may have a substituent, An alkoxy group which may have a substituent, an aryloxy group which may have a substituent, or an N,N-disubstituted amine group. Further, R 2 and R 3 may also be a arylene dioxy group which may be bonded thereto and which may have a substituent.

作為有機鋁化合物之具體例，可舉出異丁基雙(2,6-二第三丁基-4-甲基苯氧基)鋁、異丁基雙(2,6-二第三丁基苯氧基)鋁、異丁基[2,2’-亞甲基雙(4-甲基-6-第三丁基苯氧基)]鋁等。 Specific examples of the organoaluminum compound include isobutylbis(2,6-di-t-butyl-4-methylphenoxy)aluminum and isobutylbis(2,6-di-t-butylene). Phenoxy)aluminum, isobutyl [2,2'-methylenebis(4-methyl-6-t-butylphenoxy)]aluminum, and the like.

作為用以調節所得之甲基丙烯酸樹脂的重量平均分子量、數量平均分子量、分子量分布之手法，可於自由基聚合中添加鏈轉移劑至反應系統，於陰離子聚合中添加聚合抑制劑至反應系統。 As a method for adjusting the weight average molecular weight, the number average molecular weight, and the molecular weight distribution of the obtained methacrylic resin, a chain transfer agent may be added to the reaction system in the radical polymerization, and a polymerization inhibitor may be added to the reaction system in the anionic polymerization.

自由基聚合中所用的鏈轉移劑係沒有特別的限定。例如，可舉出正辛基硫醇、正十二基硫醇、三級十二基硫醇、1,4-丁二硫醇、1,6-己二硫醇、乙二醇雙硫代丙酸酯、丁二醇雙硫代乙醇酸酯、丁二醇雙硫代丙酸酯、己二醇雙硫代乙醇酸酯、己二醇雙硫代丙酸酯、三羥甲基丙烷參(β-硫代丙酸酯)、季戊四醇肆硫代丙酸酯等之烷基硫醇類；α-甲基苯乙烯二聚物；萜品二烯等 。於此等之中，較佳為正辛基硫醇、季戊四醇肆硫代丙酸酯等之烷基硫醇。此等鏈轉移劑係可單獨1種或組合2種以上使用。 The chain transfer agent used in the radical polymerization is not particularly limited. For example, n-octyl mercaptan, n-dodecyl mercaptan, tridecyl mercaptan, 1,4-butanedithiol, 1,6-hexanedithiol, ethylene glycol dithio Propionate, butanediol dithioglycolate, butanediol dithiopropionate, hexanediol dithioglycolate, hexanediol dithiopropionate, trimethylolpropane (β-thiopropionate), alkyl mercaptans such as pentaerythritol thiopropionate; α-methylstyrene dimer; . Among these, an alkyl mercaptan such as n-octyl mercaptan or pentaerythritol thiopropionate is preferred. These chain transfer agents may be used alone or in combination of two or more.

相對於供聚合反應的全部單體100質量份，該鏈轉移劑之使用量較佳為0.1~1質量份，更佳為0.15~0.8質量份，尤佳為0.2~0.6質量份，最佳為0.2~0.5質量份。又，相對於聚合起始劑100質量份，該鏈轉移劑之使用量較佳為2500~10000質量份，更佳為3000~9000質量份，尤佳為3500~6000質量份。鏈轉移劑之使用量若在上述範圍，則由於可控制所得之甲基丙烯酸樹脂的分子量，而可具有良好的成形加工性與高的力學強度。 The amount of the chain transfer agent used is preferably 0.1 to 1 part by mass, more preferably 0.15 to 0.8 part by mass, even more preferably 0.2 to 0.6 part by mass, based on 100 parts by mass of all monomers of the polymerization reaction. 0.2 to 0.5 parts by mass. Further, the amount of the chain transfer agent used is preferably from 2,500 to 10,000 parts by mass, more preferably from 3,000 to 9,000 parts by mass, even more preferably from 3,500 to 6,000 parts by mass, per 100 parts by mass of the polymerization initiator. When the amount of the chain transfer agent used is in the above range, since the molecular weight of the obtained methacrylic resin can be controlled, it is possible to have good moldability and high mechanical strength.

作為陰離子聚合法中所用的聚合抑制劑，可舉出醇或水等。聚合抑制劑的使用量係沒有特別的限定，但比聚合反應的途中聚合起始劑之量較少之量，具體而言，相對於聚合起始劑之量，較佳為1莫耳%~50莫耳%，更佳為2莫耳%~20莫耳%，尤佳為5莫耳%~10莫耳%。 The polymerization inhibitor used in the anionic polymerization method may, for example, be an alcohol or water. The amount of the polymerization inhibitor to be used is not particularly limited, but is preferably a smaller amount than the amount of the polymerization initiator in the middle of the polymerization reaction, and specifically, preferably 1 mol% based on the amount of the polymerization initiator. 50% by mole, more preferably 2% by mole to 20% by mole, and particularly preferably 5% by mole to 10% by mole.

於陰離子聚合中，為了調節所得之甲基丙烯酸樹脂的重量平均分子量、數量平均分子量、分子量分布，可在聚合反應之途中追加添加聚合起始劑。於聚合反應之途中所追加添加的聚合起始劑之量，相對於在聚合開始時已添加的聚合起始劑之量，較佳為1莫耳%~50莫耳%，更佳為2莫耳%~20莫耳%，尤佳為5莫耳%~10莫耳%。 In the anionic polymerization, in order to adjust the weight average molecular weight, the number average molecular weight, and the molecular weight distribution of the obtained methacrylic resin, a polymerization initiator may be additionally added in the middle of the polymerization reaction. The amount of the polymerization initiator added in the middle of the polymerization is preferably from 1 mol% to 50 mol%, more preferably 2 mol, based on the amount of the polymerization initiator added at the start of the polymerization. Ear %~20% by mole, especially preferably 5% by mole to 10% by mole.

甲基丙烯酸樹脂之製造所用的各單體、聚合起始劑、鏈轉移劑係可將彼等全部整批地供給至反應 槽，也可將彼等分別地供給至反應槽。 Each monomer, polymerization initiator, and chain transfer agent used in the production of the methacrylic resin can be supplied to the reaction in whole batches. The tanks may also be supplied separately to the reaction tank.

溶液聚合法中所用的溶劑，只要可溶解單體及甲基丙烯酸樹脂，不使自由基或陰離子失去活性者，則沒有特別的限制。作為該溶劑，較佳為苯、甲苯、乙苯等之芳香族烴。此等之溶劑係可單獨1種或組合2種以上使用。溶劑的使用量係可根據反應液的黏度與生產性之觀點來適宜設定。溶劑的使用量例如相對於聚合反應原料100質量份，較佳為100質量份以下，更佳為90質量份以下。 The solvent used in the solution polymerization method is not particularly limited as long as it can dissolve the monomer and the methacrylic resin without deactivating the radical or anion. The solvent is preferably an aromatic hydrocarbon such as benzene, toluene or ethylbenzene. These solvents may be used alone or in combination of two or more. The amount of the solvent to be used can be appropriately set depending on the viewpoint of the viscosity and productivity of the reaction liquid. The amount of the solvent used is, for example, 100 parts by mass or less, more preferably 90 parts by mass or less, based on 100 parts by mass of the polymerization raw material.

聚合反應時之溫度係可按照反應形態，或根據聚合反應速度、聚合反應液之黏度、副生成物之生成抑制等之觀點來適宜設定。於自由基聚合中，進行懸浮聚合時，聚合反應時之溫度較佳為50~180℃，更佳為60~140℃。於自由基聚合中，進行塊狀聚合時，聚合反應時之溫度較佳為100~200℃，更佳為110~180℃。 The temperature at the time of the polymerization reaction can be appropriately set depending on the reaction form or the polymerization reaction rate, the viscosity of the polymerization reaction liquid, and the suppression of formation of by-products. In the radical polymerization, when the suspension polymerization is carried out, the temperature during the polymerization is preferably from 50 to 180 ° C, more preferably from 60 to 140 ° C. In the radical polymerization, when the bulk polymerization is carried out, the temperature during the polymerization is preferably from 100 to 200 ° C, more preferably from 110 to 180 ° C.

甲基丙烯酸樹脂製造用的聚合反應，係可以分批式反應或連續流通式反應進行。於分批式反應中，例如在氮氣環境下等調製聚合反應原料(包含單體、聚合起始劑、鏈轉移劑等之混合液)，將其全部加入反應器內，進行指定時間的反應，取出反應物。另一方面，於連續流通式反應中，例如在氮氣環境下等調製聚合反應原料(包含單體、聚合起始劑、鏈轉移劑等之混合液)，將其以一定流量供給至反應器，以對應於該供給量的流量，抽出反應器內的液體。於本發明中，從生產性及安定性之觀點來看，較佳為連續流通式。作為連續流通式 反應器，可使用能接近栓流之狀態的管型反應器及/或能接近完全混合之狀態的槽型反應器。又，可以一座反應器進行連續流通式之聚合，也可連接二座以上的反應器進行連續流通式之聚合。於本發明中，較佳為至少一座採用連續流通式的槽型反應器。聚合反應時的槽型反應器內之液量，相對於槽型反應器的容積，較佳為1/4~3/4，更佳為1/3~2/3。於反應器中通常安裝有攪拌裝置。作為攪拌裝置，可舉出靜態攪拌裝置、動態攪拌裝置。作為動態攪拌裝置，可舉出高效率(maxblend)式攪拌裝置、具有配置於中央的縱型旋轉軸之在周圍旋轉的格子狀之翼的攪拌裝置、槳葉式攪拌裝置、螺桿式攪拌裝置等。於此等之中，從均勻混合性之點來看，較宜使用高效率式攪拌裝置。 The polymerization reaction for producing a methacrylic resin can be carried out in a batch reaction or a continuous flow reaction. In a batch reaction, for example, a polymerization reaction raw material (a mixed solution containing a monomer, a polymerization initiator, a chain transfer agent, etc.) is prepared in a nitrogen atmosphere, and the like, and all of them are fed into a reactor for a reaction for a predetermined period of time. The reaction was taken out. On the other hand, in the continuous flow reaction, for example, a polymerization raw material (a mixed liquid containing a monomer, a polymerization initiator, a chain transfer agent, etc.) is prepared in a nitrogen atmosphere, and the like, and is supplied to the reactor at a constant flow rate. The liquid in the reactor is withdrawn at a flow rate corresponding to the supply amount. In the present invention, from the viewpoint of productivity and stability, a continuous flow type is preferred. Continuous circulation As the reactor, a tubular reactor which is close to the state of the plug flow and/or a tank reactor which can be brought close to the state of complete mixing can be used. Further, it is possible to carry out continuous flow polymerization in one reactor, or to carry out continuous flow polymerization by connecting two or more reactors. In the present invention, it is preferred that at least one of the continuous flow type tank reactors is used. The amount of the liquid in the tank type reactor during the polymerization reaction is preferably 1/4 to 3/4, more preferably 1/3 to 2/3, based on the volume of the tank type reactor. A stirring device is usually installed in the reactor. Examples of the stirring device include a static stirring device and a dynamic stirring device. Examples of the dynamic stirring device include a high-efficiency (maxblend) stirring device, a stirring device having a lattice-like wing that rotates around the center of the vertical rotating shaft, a paddle stirring device, a screw stirring device, and the like. . Among these, from the viewpoint of uniform mixing, it is preferred to use a high-efficiency stirring device.

於聚合結束後，視需要去除未反應單體等的揮發分。去除方法係沒有特別的限制。於懸浮聚合、溶液聚合、乳化聚合中，在聚合反應結束後，藉由眾所周知的操作，去除懸浮介質、溶劑或乳化介質，視需要可將剩餘的樹脂成分予以洗淨、乾燥。於塊狀聚合法中，去除未反應的單體，視需要可將剩餘的樹脂成分予以乾燥。 After the completion of the polymerization, volatiles such as unreacted monomers are removed as needed. The removal method is not particularly limited. In the suspension polymerization, solution polymerization, and emulsion polymerization, after the completion of the polymerization reaction, the suspension medium, the solvent or the emulsion medium is removed by a well-known operation, and the remaining resin component can be washed and dried as needed. In the bulk polymerization method, unreacted monomers are removed, and the remaining resin components can be dried as needed.

為了懸浮介質、溶劑、乳化介質或未反應單體等之去除，可採用眾所周知的脫揮發分法。作為脫揮發分法，可舉出平衡閃蒸方式或絕熱閃蒸方式。絕熱閃蒸方式的脫揮發分溫度較佳為200~280℃，更佳為220~260℃。以絕熱閃蒸方式加熱樹脂的時間較佳為0.3~5分鐘， 更佳為0.4~3分鐘，尤佳為0.5~2分鐘。若以如此的溫度範圍及加熱時間使其脫揮發分，則容易得到著色少的甲基丙烯酸樹脂。所去除的未反應單體係可回收，再度使用於聚合反應。所回收的單體之黃色指數會因在回收操作時等所加的熱而變高。所回收的單體較佳為用適當的方法精製，減小黃色指數。 For the removal of suspension medium, solvent, emulsifying medium or unreacted monomer, etc., a well-known devolatilization method can be employed. As the devolatilization method, a balanced flash method or an adiabatic flash method can be mentioned. The devolatilization temperature of the adiabatic flash mode is preferably from 200 to 280 ° C, more preferably from 220 to 260 ° C. The time for heating the resin by adiabatic flashing is preferably 0.3 to 5 minutes. More preferably 0.4 to 3 minutes, especially preferably 0.5 to 2 minutes. When devolatilization is carried out in such a temperature range and heating time, it is easy to obtain a methacrylic resin which is less colored. The unreacted single system removed can be recovered and reused in the polymerization. The yellowness index of the recovered monomer becomes high due to the heat added during the recovery operation. The recovered monomer is preferably purified by an appropriate method to reduce the yellow index.

為了得到構成本發明所用的甲基丙烯酸樹脂(A)之複數種的甲基丙烯酸樹脂之混合物，可採用眾所周知的混煉方法，例如使用捏合機、擠壓機、混合輥、班百里混合機等的熔融混煉裝置之方法。混煉時之溫度係可按照所使用的甲基丙烯酸樹脂之熔融溫度來適宜調節，通常為150℃~300℃。 In order to obtain a mixture of a plurality of methacrylic resins constituting the methacrylic resin (A) used in the present invention, a well-known kneading method such as a kneader, an extruder, a mixing roll, a Banbury mixer can be employed. A method of a melt-kneading device. The temperature at the time of kneading can be suitably adjusted according to the melting temperature of the methacrylic resin to be used, and is usually 150 ° C to 300 ° C.

又，為了得到複數種的甲基丙烯酸樹脂之混合物，可採用在某一種的甲基丙烯酸樹脂之存在下，將能得到另一種的甲基丙烯酸樹脂之單體予以聚合之方法。該聚合係可藉由前述自由基聚合法或陰離子聚合法進行。此方法由於施加於甲基丙烯酸樹脂的熱歷程係比混煉之方法還短，而抑制甲基丙烯酸樹脂之熱分解，容易得到著色或異物少之薄膜。 Further, in order to obtain a mixture of a plurality of methacrylic resins, a method of polymerizing a monomer capable of obtaining another methacrylic resin in the presence of a methacrylic resin may be employed. The polymerization can be carried out by the aforementioned radical polymerization method or anionic polymerization method. In this method, since the thermal history applied to the methacrylic resin is shorter than that of the kneading method, the thermal decomposition of the methacrylic resin is suppressed, and a film having less coloration or foreign matter is easily obtained.

作為甲基丙烯酸樹脂(A)之複數種的甲基丙烯酸樹脂之混合物，較佳為含有甲基丙烯酸樹脂(a1)與甲基丙烯酸樹脂(a2)。 The mixture of a plurality of methacrylic resins as the methacrylic resin (A) preferably contains a methacrylic resin (a1) and a methacrylic resin (a2).

甲基丙烯酸樹脂(a1)係含有來自甲基丙烯酸甲酯的結構單元者。從耐熱性之觀點來看，以甲基丙烯酸樹脂(a1)之質量作為基準，來自甲基丙烯酸甲酯的 結構單元之含量較佳為92質量%以上，更佳為95質量%以上，尤佳為98質量%以上，特佳為99質量%以上，最佳為100質量%。 The methacrylic resin (a1) contains a structural unit derived from methyl methacrylate. From the viewpoint of heat resistance, based on the mass of the methacrylic resin (a1), from methyl methacrylate The content of the structural unit is preferably 92% by mass or more, more preferably 95% by mass or more, still more preferably 98% by mass or more, particularly preferably 99% by mass or more, and most preferably 100% by mass.

甲基丙烯酸樹脂(a1)亦可包含來自甲基丙烯酸甲酯以外的單體之結構單元。作為甲基丙烯酸甲酯以外之單體，例如可舉出甲基丙烯酸乙酯、甲基丙烯酸環己酯、甲基丙烯酸第三丁酯、甲基丙烯酸異酯、甲基丙烯酸8-三環[5.2.1.02,6]癸酯、甲基丙烯酸4-第三丁基環己酯等之甲基丙烯酸甲酯以外的甲基丙烯酸烷酯；丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸丁酯、丙烯酸2-乙基己酯等之丙烯酸烷酯；丙烯酸苯酯等之丙烯酸芳酯；丙烯酸環己酯、丙烯酸降烯酯等之丙烯酸環烷酯，丙烯醯胺，甲基丙烯醯胺，丙烯腈，甲基丙烯腈等之在一分子中僅具有一個聚合性碳-碳雙鍵之乙烯系單體。 The methacrylic resin (a1) may also contain a structural unit derived from a monomer other than methyl methacrylate. Examples of the monomer other than methyl methacrylate include ethyl methacrylate, cyclohexyl methacrylate, butyl methacrylate, and methacrylic acid. An alkyl methacrylate other than methyl methacrylate such as 8-tricyclo[5.2.1.0 2,6 ]decyl methacrylate or 4-tert-butylcyclohexyl methacrylate; methyl acrylate , an alkyl acrylate such as ethyl acrylate, propyl acrylate, butyl acrylate or 2-ethylhexyl acrylate; an aryl acrylate such as phenyl acrylate; cyclohexyl acrylate or acrylic acid A vinyl monomer such as a cycloalkyl acrylate such as an enester, a acrylamide, a methacrylamide, an acrylonitrile or a methacrylonitrile having only one polymerizable carbon-carbon double bond in one molecule.

甲基丙烯酸樹脂(a1)係三元組表示之間規性(rr)較佳為65%以上，更佳為70~90%，尤佳為72~85%。該間規性(rr)係65%以上。 The methacrylic resin (a1) is a triad indicating that the regularity (rr) is preferably 65% or more, more preferably 70 to 90%, and particularly preferably 72 to 85%. The regularity (rr) is 65% or more.

甲基丙烯酸樹脂(a1)之重量平均分子量Mwa1較佳為4萬~15萬，更佳為4萬~12萬，尤佳為5萬~10萬。Mwa1若為4萬以上，則有耐衝擊性或韌性提高之傾向。Mwa1若為15萬以下，則有成形加工性提高之傾向。 The weight average molecular weight Mw a1 of the methacrylic resin (a1) is preferably from 40,000 to 150,000, more preferably from 40,000 to 120,000, and particularly preferably from 50,000 to 100,000. When the Mw a1 is 40,000 or more, the impact resistance or the toughness tends to be improved. When the Mw a1 is 150,000 or less, the formability tends to be improved.

甲基丙烯酸樹脂(a1)係Mwa1與數量平均分子量Mna1之比(Mwa1/Mna1)較佳為1.01~3.0，更佳為1.05~2.0，尤佳為1.05~1.5。若使用具有在如此的範圍 內之Mwa1/Mna1的甲基丙烯酸樹脂(a1)，則容易得到力學強度優異之成形體。Mwa1及Mna1係可藉由調整甲基丙烯酸樹脂(a1)之製造時所使用的聚合起始劑之種類或量來控制。Mwa1及Mna1係將以凝膠滲透層析術(GPC)所測定的層析圖換算成標準聚苯乙烯的分子量而得之值。 The ratio (Mw a1 /Mn a1 ) of the methacrylic resin (a1) to Mw a1 and the number average molecular weight Mn a1 is preferably from 1.01 to 3.0, more preferably from 1.05 to 2.0, still more preferably from 1.05 to 1.5. When the methacrylic resin (a1) having Mw a1 /Mn a1 in such a range is used, a molded body excellent in mechanical strength can be easily obtained. Mw a1 and Mn a1 can be controlled by adjusting the kind or amount of the polymerization initiator used in the production of the methacrylic resin (a1). Mw a1 and Mn a1 are values obtained by converting a chromatogram measured by gel permeation chromatography (GPC) into a molecular weight of standard polystyrene.

甲基丙烯酸樹脂(a1)之玻璃轉移溫度較佳為125℃以上，更佳為128℃以上，尤佳為130℃以上。甲基丙烯酸樹脂(a1)之玻璃轉移溫度的上限較佳為140℃。玻璃轉移溫度係可藉由調節分子量或間規性(rr)等來控制。隨著甲基丙烯酸樹脂(a1)之玻璃轉移溫度變高，所得的甲基丙烯酸樹脂組成物之玻璃轉移溫度變高，由該甲基丙烯酸樹脂組成物所構成的成形體係難以發生熱收縮等的變形。 The glass transition temperature of the methacrylic resin (a1) is preferably 125 ° C or higher, more preferably 128 ° C or higher, and particularly preferably 130 ° C or higher. The upper limit of the glass transition temperature of the methacrylic resin (a1) is preferably 140 °C. The glass transition temperature can be controlled by adjusting the molecular weight or the syndiotacticity (rr) or the like. As the glass transition temperature of the methacrylic resin (a1) becomes high, the glass transition temperature of the obtained methacrylic resin composition becomes high, and the molding system composed of the methacrylic resin composition is less likely to undergo heat shrinkage or the like. Deformation.

甲基丙烯酸樹脂(a2)係含有來自甲基丙烯酸酯的結構單元者。甲基丙烯酸樹脂(a2)中所含有之來自甲基丙烯酸酯的結構單元之量，較佳為90質量%以上，更佳為95質量%以上，尤佳為98質量%以上，尤更佳為99質量%以上，最佳為100質量%。作為該甲基丙烯酸酯，可舉出甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丁酯等之甲基丙烯酸烷酯，甲基丙烯酸苯酯等之甲基丙烯酸芳酯；甲基丙烯酸環己酯、甲基丙烯酸降烯酯等之甲基丙烯酸環烷酯，較佳為甲基丙烯酸烷酯，最佳為甲基丙烯酸甲酯。 The methacrylic resin (a2) contains a structural unit derived from methacrylate. The amount of the structural unit derived from the methacrylate contained in the methacrylic resin (a2) is preferably 90% by mass or more, more preferably 95% by mass or more, still more preferably 98% by mass or more, and even more preferably 99% by mass or more, preferably 100% by mass. Examples of the methacrylate include alkyl methacrylate such as methyl methacrylate, ethyl methacrylate and butyl methacrylate, and aryl methacrylate such as phenyl methacrylate; methyl group; Cyclohexyl acrylate, methacrylic acid A cycloalkyl methacrylate such as an ester or the like is preferably an alkyl methacrylate, and most preferably methyl methacrylate.

甲基丙烯酸樹脂(a2)係在來自甲基丙烯酸酯的結構單元之中，來自甲基丙烯酸甲酯的結構單元之 含量較佳為90質量%以上，更佳為95質量%以上，尤佳為98質量%以上，尤更佳為99質量%以上，最佳為100質量%。 The methacrylic resin (a2) is a structural unit derived from methacrylic acid ester from a structural unit derived from methacrylic acid ester. The content is preferably 90% by mass or more, more preferably 95% by mass or more, still more preferably 98% by mass or more, still more preferably 99% by mass or more, and most preferably 100% by mass.

甲基丙烯酸樹脂(a2)亦可含有來自甲基丙烯酸酯以外的單體之結構單元。作為甲基丙烯酸酯以外的單體，例如可舉出丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸丁酯、丙烯酸2-乙基己酯等之丙烯酸烷酯，丙烯酸苯酯等之丙烯酸芳酯；丙烯酸環己酯、丙烯酸降烯酯等之丙烯酸環烷酯；苯乙烯、α-甲基苯乙烯等之芳香族乙烯基化合物，丙烯醯胺，甲基丙烯醯胺，丙烯腈，甲基丙烯腈等之在一分子中僅具有一個聚合性碳-碳雙鍵之乙烯系單體。 The methacrylic resin (a2) may also contain a structural unit derived from a monomer other than methacrylate. Examples of the monomer other than the methacrylate include an alkyl acrylate such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate or 2-ethylhexyl acrylate, and an acrylic acid such as phenyl acrylate. Ester; cyclohexyl acrylate, acrylic acid drop a cycloalkyl acrylate such as an ester; an aromatic vinyl compound such as styrene or α-methyl styrene; acrylamide, methacrylamide, acrylonitrile, methacrylonitrile or the like in one molecule only A vinyl monomer having a polymerizable carbon-carbon double bond.

甲基丙烯酸樹脂(a2)係三元組表示之間規性(rr)較佳為45~58%，更佳為49~55%。 The methacrylic resin (a2) is a triad indicating that the regularity (rr) is preferably from 45 to 58%, more preferably from 49 to 55%.

甲基丙烯酸樹脂(a2)之重量平均分子量Mwa2較佳為8萬~15萬，更佳為8萬~14萬，尤佳為8萬~13萬。Mwa2若為8萬以上，則有耐衝擊性或韌性提高之傾向。Mwa2若為15萬以下，則有成形加工性提高之傾向。 The weight average molecular weight Mw a2 of the methacrylic resin (a2) is preferably from 80,000 to 150,000, more preferably from 80,000 to 140,000, and particularly preferably from 80,000 to 130,000. When the Mw a2 is 80,000 or more, the impact resistance or the toughness tends to be improved. When the Mw a2 is 150,000 or less, the formability tends to be improved.

甲基丙烯酸樹脂(a2)係Mwa2與數量平均分子量Mna2之比(Mwa2/Mna2)較佳為1.7~2.6，更佳為1.7~2.3，尤佳為1.7~2.0。若使用具有在如此的範圍內之Mwa2/Mna2的甲基丙烯酸樹脂(a2)，則容易得到力學強度優異之成形體。Mwa2及Mna2係可藉由甲基丙烯酸樹脂(a2)之製造時所使用的聚合起始劑之種類或量來控制。Mwa2及Mna2係將以凝膠滲透層析術(GPC)所測定的層析 圖換算成標準聚苯乙烯的分子量而得之值。 The ratio (Mw a2 /Mn a2 ) of the methacrylic resin (a2) to Mw a2 and the number average molecular weight Mn a2 is preferably from 1.7 to 2.6, more preferably from 1.7 to 2.3, still more preferably from 1.7 to 2.0. When the methacrylic resin (a2) having Mw a2 /Mn a2 in such a range is used, a molded body excellent in mechanical strength can be easily obtained. Mw a2 and Mn a2 can be controlled by the kind or amount of the polymerization initiator used in the production of the methacrylic resin (a2). Mw a2 and Mn a2 are values obtained by converting a chromatogram measured by gel permeation chromatography (GPC) into a molecular weight of standard polystyrene.

甲基丙烯酸樹脂(a2)係玻璃轉移溫度較佳為100℃以上，更佳為110℃以上，尤佳為115℃以上，最佳為117℃以上。甲基丙烯酸樹脂(a2)之玻璃轉移溫度的上限較佳為125℃。玻璃轉移溫度係可藉由調節分子量或間規性(rr)等來控制。甲基丙烯酸樹脂(a2)之玻璃轉移溫度若在此範圍，則耐熱性變高，容易得到熱收縮等的變形難以發生之成形體。 The methacrylic resin (a2)-based glass transition temperature is preferably 100 ° C or higher, more preferably 110 ° C or higher, and particularly preferably 115 ° C or higher, and most preferably 117 ° C or higher. The upper limit of the glass transition temperature of the methacrylic resin (a2) is preferably 125 °C. The glass transition temperature can be controlled by adjusting the molecular weight or the syndiotacticity (rr) or the like. When the glass transition temperature of the methacrylic resin (a2) is within this range, heat resistance is increased, and a molded body in which deformation such as heat shrinkage is unlikely to occur is easily obtained.

甲基丙烯酸樹脂(a1)及甲基丙烯酸樹脂(a2)之製造方法係沒有特別的限制。作為甲基丙烯酸樹脂(a1)及甲基丙烯酸樹脂(a2)之製造方法，可採用前述的自由基聚合法、陰離子聚合法等。作為甲基丙烯酸樹脂(a1)之製造方法，從高的間規性(rr)與高的玻璃轉移溫度之觀點來看，較佳為陰離子聚合法或低溫的懸浮聚合法。 The method for producing the methacrylic resin (a1) and the methacrylic resin (a2) is not particularly limited. As a method for producing the methacrylic resin (a1) and the methacrylic resin (a2), the above-described radical polymerization method, anionic polymerization method, or the like can be employed. As a method for producing the methacrylic resin (a1), from the viewpoint of high syndiotacticity (rr) and high glass transition temperature, an anionic polymerization method or a low-temperature suspension polymerization method is preferred.

於自甲基丙烯酸樹脂(a1)與甲基丙烯酸樹脂(a2)所得之甲基丙烯酸樹脂(A)中，從使高的玻璃轉移溫度及良好的成形加工性並存之觀點來看，甲基丙烯酸樹脂(a1)之含量較佳為40~95%，更佳為40~70質量%，尤佳為45~65質量%，最佳為50~60質量%，甲基丙烯酸樹脂(a2)之含量較佳為5~60%，更佳為30~60質量%,尤佳為35~55質量%，最佳為40~50質量%。再者，甲基丙烯酸樹脂(a1)/甲基丙烯酸樹脂(a2)之質量比較佳為40/60~95/5，更佳為40/60~70/30，尤佳為45/55~65/35，最佳為50/50~60/40。 In the methacrylic resin (A) obtained from the methacrylic resin (a1) and the methacrylic resin (a2), methacrylic acid is obtained from the viewpoint of coexisting high glass transition temperature and good moldability. The content of the resin (a1) is preferably 40 to 95%, more preferably 40 to 70% by mass, particularly preferably 45 to 65% by mass, most preferably 50 to 60% by mass, and the content of the methacrylic resin (a2). It is preferably 5 to 60%, more preferably 30 to 60% by mass, particularly preferably 35 to 55% by mass, most preferably 40 to 50% by mass. Furthermore, the quality of the methacrylic resin (a1)/methacrylic resin (a2) is preferably 40/60 to 95/5, more preferably 40/60 to 70/30, and particularly preferably 45/55 to 65. /35, the best is 50/50~60/40.

本發明之甲基丙烯酸樹脂組成物係含有 甲基丙烯酸樹脂(A)與嵌段共聚物(B)者。藉由含有嵌段共聚物(B)，可得到透明性高，在寬廣的溫度範圍中霧度之變化小，玻璃轉移溫度高且機械強度大，低分子化合物(紫外線吸收劑)的滲出經抑制之甲基丙烯酸樹脂組成物。 The methacrylic resin composition of the present invention contains The methacrylic resin (A) and the block copolymer (B). By containing the block copolymer (B), transparency can be obtained, the change in haze is small in a wide temperature range, the glass transition temperature is high, and the mechanical strength is high, and the bleeding of the low molecular compound (ultraviolet absorber) is suppressed. A methacrylic resin composition.

本發明所用的嵌段共聚物(B)係具有甲基丙烯酸酯聚合物嵌段(b1)與丙烯酸酯聚合物嵌段(b2)。嵌段共聚物(B)所具有的甲基丙烯酸酯聚合物嵌段(b1)係可僅為一者，也可為兩者以上。當甲基丙烯酸酯聚合物嵌段(b1)為兩者以上時，各自之構成甲基丙烯酸酯聚合物嵌段(b1)之結構單元的比率或分子量係可互相相同或相異。又，嵌段共聚物(B)所具有的丙烯酸酯聚合物嵌段(b2)係可僅為一者，也可為兩者以上。當丙烯酸酯聚合物嵌段(b2)為兩者以上時，各自之構成丙烯酸酯聚合物嵌段(b2)之結構單元的比率或分子量係可互相相同或相異。 The block copolymer (B) used in the present invention has a methacrylate polymer block (b1) and an acrylate polymer block (b2). The methacrylate polymer block (b1) which the block copolymer (B) has may be one or more. When the methacrylate polymer block (b1) is two or more, the ratio or molecular weight of each of the structural units constituting the methacrylate polymer block (b1) may be the same or different from each other. Further, the acrylate polymer block (b2) which the block copolymer (B) has may be one or more. When the acrylate polymer block (b2) is two or more, the ratio or molecular weight of the structural units constituting the acrylate polymer block (b2) may be the same or different from each other.

甲基丙烯酸酯聚合物嵌段(b1)係以來自甲基丙烯酸酯的結構單元作為主要構成單元。甲基丙烯酸酯聚合物嵌段(b1)中之來自甲基丙烯酸酯的結構單元之比例較佳為80質量%以上，更佳為90質量%以上，尤佳為95質量%以上，特佳為98質量%以上。 The methacrylate polymer block (b1) is a structural unit derived from a methacrylate as a main constituent unit. The proportion of the structural unit derived from the methacrylate in the methacrylate polymer block (b1) is preferably 80% by mass or more, more preferably 90% by mass or more, and particularly preferably 95% by mass or more, particularly preferably 98% by mass or more.

作為甲基丙烯酸酯，可舉出甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸正丙酯、甲基丙烯酸異丙酯、甲基丙烯酸正丁酯、甲基丙烯酸異丁酯、甲基丙烯酸第二丁酯、甲基丙烯酸第三丁酯、甲基丙烯酸戊酯、甲基丙烯酸異戊酯、甲基丙烯酸正己酯、甲基丙烯 酸環己酯、甲基丙烯酸2-乙基己酯、甲基丙烯酸十五酯、甲基丙烯酸十二酯、甲基丙烯酸異酯、甲基丙烯酸苯酯、甲基丙烯酸苄酯、甲基丙烯酸苯氧基乙酯、甲基丙烯酸2-羥基乙酯、甲基丙烯酸2-甲氧基乙酯、甲基丙烯酸環氧丙酯、甲基丙烯酸烯丙酯等。於此等之中，從提高透明性、耐熱性之觀點來看，較佳為甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸異丙酯、甲基丙烯酸正丁酯、甲基丙烯酸第三丁酯、甲基丙烯酸環己酯、甲基丙烯酸異酯等之甲基丙烯酸烷酯，更佳為甲基丙烯酸甲酯。此等甲基丙烯酸酯係可單獨1種或組合2種以上使用。 Examples of the methacrylate include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, and A. Dibutyl acrylate, butyl methacrylate, amyl methacrylate, isoamyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate , pentadecyl methacrylate, dodecyl methacrylate, methacrylic acid Ester, phenyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, 2-hydroxyethyl methacrylate, 2-methoxyethyl methacrylate, glycidyl methacrylate , allyl methacrylate and the like. Among these, from the viewpoint of improving transparency and heat resistance, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, and methacrylic acid are preferred. Third butyl ester, cyclohexyl methacrylate, methacrylic acid An alkyl methacrylate such as an ester, more preferably methyl methacrylate. These methacrylates may be used alone or in combination of two or more.

於不妨礙本發明之目的及效果之範圍內，甲基丙烯酸酯聚合物嵌段(b1)亦可包含來自甲基丙烯酸酯以外之單體的結構單元。甲基丙烯酸酯聚合物嵌段(b1)中所包含之來自甲基丙烯酸酯以外之單體的結構單元之比例，較佳為20質量%以下，更佳為10質量%以下，尤佳為5質量%以下，特佳為2質量%以下。 The methacrylate polymer block (b1) may also contain a structural unit derived from a monomer other than methacrylate, within a range not inhibiting the object and effect of the present invention. The proportion of the structural unit derived from the monomer other than the methacrylate contained in the methacrylate polymer block (b1) is preferably 20% by mass or less, more preferably 10% by mass or less, and particularly preferably 5 The mass% or less is particularly preferably 2% by mass or less.

作為甲基丙烯酸酯以外之單體，可舉出丙烯酸酯、不飽和羧酸、芳香族乙烯基化合物、烯烴、共軛二烯、丙烯腈、甲基丙烯腈、丙烯醯胺、甲基丙烯醯胺、乙酸乙烯酯、乙烯基吡啶、乙烯基酮、氯乙烯、偏二氯乙烯、偏二氟乙烯等。此等甲基丙烯酸酯以外之單體係可單獨1種或組合2種以上使用。 Examples of the monomer other than the methacrylate include an acrylate, an unsaturated carboxylic acid, an aromatic vinyl compound, an olefin, a conjugated diene, acrylonitrile, methacrylonitrile, acrylamide, and methacryl Amine, vinyl acetate, vinyl pyridine, vinyl ketone, vinyl chloride, vinylidene chloride, vinylidene fluoride, and the like. These single systems other than the methacrylate may be used alone or in combination of two or more.

從提高本發明之甲基丙烯酸樹脂組成物的透明性之觀點來看，甲基丙烯酸酯聚合物嵌段(b1)係 在23℃、50%RH下測定的在波長587.6nm(D線)之折射率較佳為1.485~1.495。 From the viewpoint of improving the transparency of the methacrylic resin composition of the present invention, the methacrylate polymer block (b1) is The refractive index at a wavelength of 587.6 nm (D line) measured at 23 ° C and 50% RH is preferably 1.485 to 1.495.

甲基丙烯酸酯聚合物嵌段(b1)之重量平均分子量Mwb1係下限較佳為5千，更佳為8千，尤佳為1萬2千，尤更佳為1萬5千，最佳為2萬，上限較佳為15萬，更佳為12萬，尤佳為10萬。再者，於嵌段共聚物(B)中含有複數的甲基丙烯酸酯聚合物嵌段(b1)時，上述之重量平均分子量Mwb1係定義為對於全部的甲基丙烯酸酯聚合物嵌段(b1)，算出各自的重量平均分子量，將數值予以合計者。 The lower limit of the weight average molecular weight Mw b1 of the methacrylate polymer block (b1) is preferably 5,000, more preferably 8,000, particularly preferably 12,000, and more preferably 15,000. For 20,000, the upper limit is preferably 150,000, more preferably 120,000, and especially 100,000. Further, when the block copolymer (B) contains a plurality of methacrylate polymer blocks (b1), the above weight average molecular weight Mw b1 is defined as a block for all the methacrylate polymers ( B1), calculate the respective weight average molecular weights, and add the values to the total.

又，MwA/Mwb1較佳為0.5以上6以下，更佳為0.5以上3.5以下，尤佳為0.6以上2.7以下，最佳為0.7以上2.5以下。MwA/Mwb1若過小，則由甲基丙烯酸樹脂組成物所製作的成形品之耐衝擊性有降低之傾向。另一方面，MwA/Mwb1若過大，則由甲基丙烯酸樹脂組成物所製作的成形品之表面平滑性及霧度之溫度依賴性有變差之傾向。MwA/Mwb1在上述範圍時，不論溫度變化為何，也維持低的霧度，在寬廣的溫度範圍中霧度之變化係變小。此係因為嵌段共聚物(B)以小的粒徑均勻分散在甲基丙烯酸樹脂(A)中。 Further, Mw A / Mw b1 is preferably 0.5 or more and 6 or less, more preferably 0.5 or more and 3.5 or less, still more preferably 0.6 or more and 2.7 or less, and most preferably 0.7 or more and 2.5 or less. When Mw A /Mw b1 is too small, the impact resistance of the molded article produced from the methacrylic resin composition tends to be lowered. On the other hand, when Mw A /Mw b1 is too large, the surface smoothness of the molded article produced from the methacrylic resin composition tends to deteriorate the temperature dependency of the haze. When Mw A /Mw b1 is in the above range, the haze is maintained regardless of the temperature change, and the change in haze is small in a wide temperature range. This is because the block copolymer (B) is uniformly dispersed in the methacrylic resin (A) with a small particle diameter.

嵌段共聚物(B)中的甲基丙烯酸酯聚合物嵌段(b1)之比例，從透明性、柔軟性、成形加工性、表面平滑性之觀點來看，較佳為10質量%以上80質量%以下，更佳為20質量%以上70質量%以下，尤佳為40質量%以上60質量%以下。嵌段共聚物(B)中的甲基丙烯酸酯聚合 物嵌段(b1)之比例若在上述範圍內，則本發明之甲基丙烯酸樹脂組成物或由其所成的成形品之透明性、可撓性、耐彎曲性、耐衝擊性、柔軟性等優異。於嵌段共聚物(B)含有複數的甲基丙烯酸酯聚合物嵌段(b1)時，上述之比例係以全部的甲基丙烯酸酯聚合物嵌段(b1)之合計質量為基礎而算出。 The ratio of the methacrylate polymer block (b1) in the block copolymer (B) is preferably 10% by mass or more from the viewpoints of transparency, flexibility, moldability, and surface smoothness. The mass% or less is more preferably 20% by mass or more and 70% by mass or less, and particularly preferably 40% by mass or more and 60% by mass or less. Polymerization of methacrylate in block copolymer (B) When the ratio of the block (b1) is within the above range, the methacrylic resin composition of the present invention or the molded article formed therefrom has transparency, flexibility, bending resistance, impact resistance, and flexibility. Excellent. When the block copolymer (B) contains a plurality of methacrylate polymer blocks (b1), the above ratio is calculated based on the total mass of all the methacrylate polymer blocks (b1).

丙烯酸酯聚合物嵌段(b2)係以來自丙烯酸酯的結構單元作為主要構成單元。丙烯酸酯聚合物嵌段(b2)中之來自丙烯酸酯的結構單元之比例較佳為45質量%以上，更佳為50質量%以上，尤佳為60質量%以上，特佳為90質量%以上。作為丙烯酸酯，例如可舉出丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丙酯、丙烯酸異丙酯、丙烯酸正丁酯、丙烯酸異丁酯、丙烯酸第二丁酯、丙烯酸第三丁酯、丙烯酸戊酯、丙烯酸異戊酯、丙烯酸正己酯、丙烯酸環己酯、丙烯酸2-乙基己酯、丙烯酸十五酯、丙烯酸十二酯、丙烯酸異酯、丙烯酸苯酯、丙烯酸苄酯、丙烯酸苯氧基乙酯、丙烯酸2-羥基乙酯、丙烯酸2-甲氧基乙酯、丙烯酸環氧丙酯、丙烯酸烯丙酯等。此等丙烯酸酯係可單獨1種或組合2種以上使用。 The acrylate polymer block (b2) is mainly composed of a structural unit derived from an acrylate. The proportion of the structural unit derived from the acrylate in the acrylate polymer block (b2) is preferably 45 mass% or more, more preferably 50 mass% or more, particularly preferably 60 mass% or more, and particularly preferably 90 mass% or more. . Examples of the acrylate include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, second butyl acrylate, tert-butyl acrylate, and butyl acrylate. Ester, isoamyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, pentadecyl acrylate, dodecyl acrylate, acrylic acid Ester, phenyl acrylate, benzyl acrylate, phenoxyethyl acrylate, 2-hydroxyethyl acrylate, 2-methoxyethyl acrylate, glycidyl acrylate, allyl acrylate, and the like. These acrylates may be used alone or in combination of two or more.

於不妨礙本發明之目的及效果之範圍內，丙烯酸酯聚合物嵌段(b2)亦可包含來自丙烯酸酯以外之單體的結構單元。丙烯酸酯聚合物嵌段(b2)中所包含之來自丙烯酸酯以外之單體的結構單元之量，較佳為55質量%以下，更佳為50質量%以下，尤佳為40質量%以下，特佳為10質量%以下。作為丙烯酸酯以外之單體，可 舉出甲基丙烯酸酯、不飽和羧酸、芳香族乙烯基化合物、烯烴、共軛二烯、丙烯腈、甲基丙烯腈、丙烯醯胺、甲基丙烯醯胺、乙酸乙烯酯、乙烯基吡啶、乙烯基酮、氯乙烯、偏二氯乙烯、偏二氟乙烯等。此等丙烯酸酯以外之單體可單獨1種或組合2種以上使用。 The acrylate polymer block (b2) may also contain a structural unit derived from a monomer other than the acrylate, within a range not inhibiting the object and effect of the present invention. The amount of the structural unit derived from the monomer other than the acrylate contained in the acrylate polymer block (b2) is preferably 55 mass% or less, more preferably 50 mass% or less, still more preferably 40 mass% or less. It is particularly preferably 10% by mass or less. As a monomer other than acrylate, Examples of methacrylate, unsaturated carboxylic acid, aromatic vinyl compound, olefin, conjugated diene, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, vinyl acetate, vinyl pyridine , vinyl ketone, vinyl chloride, vinylidene chloride, vinylidene fluoride and the like. The monomers other than the acrylates may be used alone or in combination of two or more.

從提高本發明之甲基丙烯酸樹脂組成物的透明性之觀點等來看，丙烯酸酯聚合物嵌段(b2)較佳為由丙烯酸烷酯與(甲基)丙烯酸芳香族烴酯所構成。 The acrylate polymer block (b2) is preferably composed of an alkyl acrylate and an (meth)acrylic aromatic hydrocarbon ester from the viewpoint of improving the transparency of the methacrylic resin composition of the present invention.

作為丙烯酸烷酯，可舉出丙烯酸甲酯、丙烯酸乙酯、丙烯酸異丙酯、丙烯酸正丁酯、丙烯酸2-乙基己酯、丙烯酸十二酯等。於此等之中，較佳為丙烯酸正丁酯、丙烯酸2-乙基己酯。 Examples of the alkyl acrylate include methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, and dodecyl acrylate. Among these, n-butyl acrylate and 2-ethylhexyl acrylate are preferred.

(甲基)丙烯酸芳香族烴酯係意指丙烯酸芳香族烴酯或甲基丙烯酸芳香族烴酯。作為(甲基)丙烯酸芳香族烴酯，例如可舉出丙烯酸苯酯、丙烯酸苄酯、丙烯酸苯氧基乙酯、丙烯酸苯乙烯酯、甲基丙烯酸苯酯、甲基丙烯酸苄酯、甲基丙烯酸苯氧基乙酯、甲基丙烯酸苯乙烯酯等。其中，較佳為甲基丙烯酸苯酯、甲基丙烯酸苄酯、甲基丙烯酸苯氧基乙酯、丙烯酸苄酯。 The (meth)acrylic aromatic hydrocarbon ester system means an aromatic hydrocarbon ester of acrylic acid or an aromatic hydrocarbon ester of methacrylic acid. Examples of the (meth)acrylic aromatic hydrocarbon ester include phenyl acrylate, benzyl acrylate, phenoxyethyl acrylate, styrene acrylate, phenyl methacrylate, benzyl methacrylate, and methacrylic acid. Phenoxyethyl ester, styrene methacrylate, and the like. Among them, preferred are phenyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, and benzyl acrylate.

由丙烯酸烷酯與(甲基)丙烯酸芳香族烴酯所成的丙烯酸酯聚合物嵌段(b2)，較佳含有50~90質量%，更佳含有60~80質量%之來自丙烯酸烷酯的結構單元，且較佳含有50~10質量%。更佳含有40~20質量%之來自(甲基)丙烯酸芳香族酯的結構單元。 The acrylate polymer block (b2) composed of an alkyl acrylate and an aromatic hydrocarbon (meth) acrylate preferably contains 50 to 90% by mass, more preferably 60 to 80% by mass, of an alkyl acrylate. The structural unit is preferably 50 to 10% by mass. More preferably, it contains 40 to 20% by mass of a structural unit derived from an aromatic (meth)acrylic acid ester.

從提高甲基丙烯酸樹脂組成物的透明性 之觀點來看，丙烯酸酯聚合物嵌段(b2)係在23℃ 50%RH下測定的在波長587.6nm(D線)之折射率較佳為1.485~1.495。 From improving the transparency of the methacrylic resin composition From the viewpoint of the acrylate polymer block (b2), the refractive index at a wavelength of 587.6 nm (D line) measured at 23 ° C and 50% RH is preferably 1.485 to 1.495.

丙烯酸酯聚合物嵌段(b2)之重量平均分子量Mwb2係下限較佳為5千，更佳為1萬5千，尤佳為2萬，尤更佳為3萬，最佳為4萬，上限較佳為12萬，更佳為11萬，尤佳為10萬。Mwb2若小，則由甲基丙烯酸樹脂組成物所製作的成形品之耐衝擊性有降低之傾向。另一方面，Mwb2若大，則由甲基丙烯酸樹脂組成物所製作的成形品之表面平滑性有降低之傾向。再者，於嵌段共聚物(B)中含有複數的丙烯酸酯聚合物嵌段(b2)時，上述之重量平均分子量Mwb2係定義為對於全部的丙烯酸酯聚合物嵌段(b2)，算出各自的重量平均分子量，將數值予以合計者。 The lower limit of the weight average molecular weight Mw b2 of the acrylate polymer block (b2) is preferably 5,000, more preferably 15,000, particularly preferably 20,000, particularly preferably 30,000, and most preferably 40,000. The upper limit is preferably 120,000, more preferably 110,000, and especially 100,000. When Mw b2 is small, the impact resistance of the molded article produced from the methacrylic resin composition tends to be lowered. On the other hand, when Mw b2 is large, the surface smoothness of the molded article produced from the methacrylic resin composition tends to be lowered. Further, when the block copolymer (B) contains a plurality of acrylate polymer blocks (b2), the above-mentioned weight average molecular weight Mw b2 is defined as calculated for all the acrylate polymer blocks (b2). The weight average molecular weight of each will be added to the value.

再者，Mwb1及Mwb2係於嵌段共聚物(B)之製造的各階段，具體而言係用以製造甲基丙烯酸酯聚合物嵌段(b1)的聚合之結束時及用以製造丙烯酸酯聚合物嵌段(b2)的聚合之結束時，分別測定重量平均分子量，將該聚合開始前之重量平均分子量的測定值與該聚合結束時之重量平均分子量的測定值之差視為由該聚合所得的聚合物嵌段之重量平均分子量而求得之值。各重量平均分子量係以GPC(凝膠滲透層析術)所測定的標準聚苯乙烯換算值。 Further, Mw b1 and Mw b2 are in various stages of the production of the block copolymer (B), specifically, at the end of the polymerization for producing the methacrylate polymer block (b1) and for production. At the end of the polymerization of the acrylate polymer block (b2), the weight average molecular weight is measured, and the difference between the measured value of the weight average molecular weight before the start of polymerization and the measured value of the weight average molecular weight at the end of the polymerization is regarded as The weight average molecular weight of the polymer block obtained by the polymerization is determined. Each weight average molecular weight is a standard polystyrene equivalent value measured by GPC (gel permeation chromatography).

嵌段共聚物(B)中的丙烯酸酯聚合物嵌段(b2)之比例，從透明性、柔軟性、成形加工性、表面平 滑性之觀點來看，較佳為20質量%以上90質量%以下，更佳為30質量%以上80質量%以下。嵌段共聚物(B)中的丙烯酸酯聚合物嵌段(b2)之比例若在上述範圍內，則本發明之甲基丙烯酸樹脂組成物或由其所成的成形品之耐衝擊性、柔軟性等優異。於嵌段共聚物(B)中含有複數的丙烯酸酯聚合物嵌段(b2)時，上述之比例係以全部的丙烯酸酯聚合物嵌段(b2)之合計質量為基礎而算出。 The ratio of the acrylate polymer block (b2) in the block copolymer (B) is from transparency, flexibility, formability, and surface flatness. From the viewpoint of slipperiness, it is preferably 20% by mass or more and 90% by mass or less, and more preferably 30% by mass or more and 80% by mass or less. When the ratio of the acrylate polymer block (b2) in the block copolymer (B) is within the above range, the methacrylic resin composition of the present invention or the molded article formed therefrom is impact-resistant and soft. Excellent in sex. When the block copolymer (B) contains a plurality of acrylate polymer blocks (b2), the above ratio is calculated based on the total mass of all the acrylate polymer blocks (b2).

嵌段共聚物(B)係不被甲基丙烯酸酯聚合物嵌段(b1)與丙烯酸酯聚合物嵌段(b2)之結合形態所特別限定。例如，可舉出在甲基丙烯酸酯聚合物嵌段(b1)的一末端連接有丙烯酸酯聚合物嵌段(b2)的一末端者((b1)-(b2)結構的二嵌段共聚物)；在甲基丙烯酸酯聚合物嵌段(b1)的兩末端各自連接有丙烯酸酯聚合物嵌段(b2)的一末端者((b2)-(b1)-(b2)結構的三嵌段共聚物)；在丙烯酸酯聚合物嵌段(b2)的兩末端各自連接有甲基丙烯酸酯聚合物嵌段(b1)的一末端者((b1)-(b2)-(b1)結構的三嵌段共聚物)等之串聯連接有甲基丙烯酸酯聚合物嵌段(b1)與丙烯酸酯聚合物嵌段(b2)的結構之嵌段共聚物。 The block copolymer (B) is not particularly limited by the form of bonding of the methacrylate polymer block (b1) and the acrylate polymer block (b2). For example, a diblock copolymer of (b1)-(b2) structure in which one end of the acrylate polymer block (b2) is bonded to one end of the methacrylate polymer block (b1) At the both ends of the methacrylate polymer block (b1), one end of the acrylate polymer block (b2) is bonded to each other (the (b2)-(b1)-(b2) structure of the triblock Copolymer); at the both ends of the acrylate polymer block (b2), one end of the methacrylate polymer block (b1) is attached (the (b1)-(b2)-(b1) structure of the three A block copolymer having a structure of a methacrylate polymer block (b1) and an acrylate polymer block (b2) is connected in series to a block copolymer or the like.

又，可舉出連接複數的(b1)-(b2)結構之臂狀(arm)嵌段共聚物的一末端而形成放射狀結構的嵌段共聚物([(b1)-(b2)-]mX結構星型嵌段共聚物)；連接複數的(b2)-(b1)結構之臂狀嵌段共聚物的一末端而形成放射狀結構的嵌段共聚物([(b2)-(b1)-]mX結構星型嵌段共聚物)；連接複數的(b1)-(b2)-(b1)結構之臂狀嵌段共聚物的一末端而形成放射狀結構的嵌段共聚物([(b1)-(b2)-(b1)- ]mX結構星型嵌段共聚物)；連接複數的(b2)-(b1)-(b2)結構之臂狀嵌段共聚物的一末端而形成放射狀結構的嵌段共聚物([(b2)-(b1)-(b2)-]mX結構星型嵌段共聚物)等之星型嵌段共聚物，或具有分支結構的嵌段共聚物等。再者，此處X表示偶合劑殘基。於此等之中，較佳為二嵌段共聚物、三嵌段共聚物、星型嵌段共聚物，更佳為(b1)-(b2)結構的二嵌段共聚物、(b1)-(b2)-(b1)結構的三嵌段共聚物、[(b1)-(b2)-]mX結構的星形嵌段共聚物、[(b1)-(b2)-(b1)-]mX結構的星形嵌段共聚物。m各自獨立地表示臂狀嵌段共聚物之數。 Further, a block copolymer ([(b1)-(b2)-]) which forms one end of a plurality of arm block copolymers of the (b1)-(b2) structure to form a radial structure may be mentioned. m X structure star block copolymer); a block copolymer ([(b2)-(b1)) which forms a radial structure by connecting one end of a plurality of (b2)-(b1) arm block copolymers )]] m X structure star block copolymer); a block copolymer which forms a radial structure by connecting one end of a plurality of (b1)-(b2)-(b1) arm block copolymers ( [(b1)-(b2)-(b1)-] m X-structured star-shaped block copolymer); one end of an arm-shaped block copolymer connecting a plurality of (b2)-(b1)-(b2) structures And forming a star-shaped block copolymer such as a radial structure block copolymer ([(b2)-(b1)-(b2)-] m X structure star block copolymer), or having a branched structure Segment copolymers, etc. Further, here, X represents a coupling agent residue. Among these, a diblock copolymer, a triblock copolymer, a star block copolymer, a diblock copolymer of a (b1)-(b2) structure, and (b1)- are preferred. a triblock copolymer of (b2)-(b1) structure, a star block copolymer of [(b1)-(b2)-] m X structure, [(b1)-(b2)-(b1)-] A star block copolymer of m X structure. m each independently represents the number of arm-shaped block copolymers.

又，嵌段共聚物(B)亦可具有甲基丙烯酸酯聚合物嵌段(b1)及丙烯酸酯聚合物嵌段(b2)以外之聚合物嵌段(b3)。 Further, the block copolymer (B) may have a polymer block (b3) other than the methacrylate polymer block (b1) and the acrylate polymer block (b2).

構成聚合物嵌段(b3)的主要結構單元係來自甲基丙烯酸酯及丙烯酸酯以外之單體的結構單元。作為該單體，例如可舉出乙烯、丙烯、1-丁烯、異丁烯、1-辛烯等之烯烴；丁二烯、異戊二烯、香葉烯等之共軛二烯；苯乙烯、α-甲基苯乙烯、p-甲基苯乙烯、m-甲基苯乙烯等之芳香族乙烯基化合物；乙酸乙烯酯、乙烯基吡啶、丙烯腈、甲基丙烯腈、乙烯基酮、氯乙烯、偏二氯乙烯、偏二氟乙烯、丙烯醯胺、甲基丙烯醯胺、ε-己內酯、戊內酯等。 The main structural unit constituting the polymer block (b3) is a structural unit derived from a monomer other than methacrylate and acrylate. Examples of the monomer include olefins such as ethylene, propylene, 1-butene, isobutylene, and 1-octene; and conjugated dienes such as butadiene, isoprene, and geranene; and styrene. An aromatic vinyl compound such as α-methylstyrene, p-methylstyrene or m-methylstyrene; vinyl acetate, vinyl pyridine, acrylonitrile, methacrylonitrile, vinyl ketone, vinyl chloride , vinylidene chloride, vinylidene fluoride, acrylamide, methacrylamide, ε-caprolactone, valerolactone, and the like.

該嵌段共聚物(B)中的甲基丙烯酸酯聚合物嵌段(b1)、丙烯酸酯聚合物嵌段(b2)及聚合物嵌段(b3)之結合形態係沒有特別的限定。作為由甲基丙烯酸酯聚 合物嵌段(b1)、丙烯酸酯聚合物嵌段(b2)及聚合物嵌段(b3)所構成的嵌段共聚物(B)之結合形態，例如可舉出(b1)-(b2)-(b1)-(b3)結構的嵌段共聚物、(b3)-(b1)-(b2)-(b1)-(b3)結構的嵌段共聚物等。於嵌段共聚物(B)中聚合物嵌段(b3)為複數時，構成各自的聚合物嵌段(b3)之結構單元的組成比或分子量，係可互相相同或相異。 The bonding form of the methacrylate polymer block (b1), the acrylate polymer block (b2), and the polymer block (b3) in the block copolymer (B) is not particularly limited. As a methacrylate poly The bonding form of the block copolymer (B) composed of the conjugate block (b1), the acrylate polymer block (b2) and the polymer block (b3) is, for example, (b1)-(b2) a block copolymer of (b1)-(b3) structure, a block copolymer of (b3)-(b1)-(b2)-(b1)-(b3) structure, and the like. When the polymer block (b3) in the block copolymer (B) is plural, the composition ratio or molecular weight of the structural units constituting the respective polymer blocks (b3) may be the same or different from each other.

嵌段共聚物(B)係視需要在分子鏈中或分子鏈末端亦可具有羥基、羧基、酸酐、胺基等之官能基。 The block copolymer (B) may have a functional group such as a hydroxyl group, a carboxyl group, an acid anhydride, an amine group or the like in the molecular chain or at the end of the molecular chain as needed.

嵌段共聚物(B)係重量平均分子量MwB較佳為3萬2千以上30萬以下，更佳為4萬5千以上23萬以下。MwB若小，則於熔融擠壓成形中無法保持充分的熔融張力，難以得到良好的板狀成形體，而且所得之板狀成形體的斷裂強度等之力學物性有降低之傾向。另一方面，MwB若大，則熔融樹脂之黏度變高，則在以熔融擠壓成形所得之板狀成形體的表面上發生微細的花紋狀之凹凸或未熔融物(高分子量體)所造成的麻點，有難以得到良好的板狀成形體之傾向。 The weight average molecular weight Mw B of the block copolymer (B) is preferably from 32,000 to 300,000, more preferably from 45,000 to 230,000. When the Mw B is small, sufficient melt tension cannot be maintained in the melt extrusion molding, and it is difficult to obtain a favorable plate-like molded body, and the mechanical properties of the obtained plate-shaped formed body such as breaking strength tend to be lowered. On the other hand, when the Mw B is large, the viscosity of the molten resin is increased, and fine irregularities or unmelted substances (high molecular weight bodies) are formed on the surface of the plate-shaped formed body obtained by melt extrusion molding. The resulting pitting has a tendency to be difficult to obtain a good plate-shaped formed body.

又，嵌段共聚物(B)係MwB與數量平均分子量MnB之比(MwB/MnB)較佳為1.0以上2.0以下，更佳為1.0以上1.6以下。藉由MwB/MnB在如此的範圍內，可使未熔融物之含量成為極少量，該未熔融物係造成由本發明之甲基丙烯酸樹脂組成物所構成的成形品中之麻點的發生原因。再者，MwB及MnB係以GPC(凝膠滲透層析術)所測定的標準聚苯乙烯換算之分子量。 Further, the ratio (Mw B /Mn B ) of the block copolymer (B) based on Mw B to the number average molecular weight Mn B is preferably 1.0 or more and 2.0 or less, more preferably 1.0 or more and 1.6 or less. When Mw B /Mn B is in such a range, the content of the unmelted substance can be made extremely small, and the unmelted substance causes the occurrence of pitting in the molded article composed of the methacrylic resin composition of the present invention. the reason. Further, Mw B and Mn B are molecular weights in terms of standard polystyrene measured by GPC (gel permeation chromatography).

嵌段共聚物(B)係折射率較佳為1.485~ 1.495，更佳為1.487~1.493。折射率若為此範圍內，則本發明之甲基丙烯酸樹脂組成物的透明性變高。再者，本說明書中所謂的「折射率」，就是如後述之實施例，意指以波長587.6nm(D線)所測定之值。 The block copolymer (B) has a refractive index of preferably 1.485~ 1.495, better 1.487~1.493. When the refractive index is within this range, the transparency of the methacrylic resin composition of the present invention becomes high. In addition, the "refractive index" as used in the present specification means an example measured at a wavelength of 587.6 nm (line D) as will be described later.

嵌段共聚物(B)之製造方法係沒有特別的限定，可採用依據眾所周知的手法之方法。例如，一般使用將構成各聚合物嵌段的單體予以活性聚合之方法。作為如此的活性聚合之手法，例如可舉出使用有機鹼金屬化合物作為聚合起始劑，於鹼金屬或鹼土類金屬鹽等的礦酸鹽之存在下進行陰離子聚合之方法；使用有機鹼金屬化合物作為聚合起始劑，於有機鋁化合物之存在下進行陰離子聚合之方法；使用有機稀土類金屬錯合物作為聚合起始劑而聚合之方法；使用α-鹵化酯化合物作為起始劑，於銅化合物之存在下進行自由基聚合之方法等。又，亦可舉出使用多價自由基聚合起始劑或多價自由基鏈轉移劑，使構成各嵌段的單體聚合，製造本發明所用之含有嵌段共聚物(B)的混合物之方法等。於此等方法之中，特別地從以高純度得到嵌段共聚物(B)，且分子量或組成比之控制為容易，且經濟的來看，使用有機鹼金屬化合物作為聚合起始劑，於有機鋁化合物之存在下進行陰離子聚合之方法為較佳。 The method for producing the block copolymer (B) is not particularly limited, and a method according to a well-known method can be employed. For example, a method of livingly polymerizing a monomer constituting each polymer block is generally used. As such a method of living polymerization, for example, a method of performing anionic polymerization in the presence of a mineral acid such as an alkali metal or an alkaline earth metal salt using an organic alkali metal compound as a polymerization initiator; and an organic alkali metal compound are used. As a polymerization initiator, a method of performing anionic polymerization in the presence of an organoaluminum compound; a method of polymerizing using an organic rare earth metal complex as a polymerization initiator; using an α-halogenated ester compound as a starter in copper A method of performing radical polymerization in the presence of a compound or the like. Further, a polyvalent radical polymerization initiator or a polyvalent radical chain transfer agent may be used to polymerize the monomers constituting each block to produce a mixture containing the block copolymer (B) used in the present invention. Method, etc. Among these methods, in particular, the block copolymer (B) is obtained in a high purity, and the control of the molecular weight or composition ratio is easy, and economically, an organic alkali metal compound is used as a polymerization initiator. A method of performing anionic polymerization in the presence of an organoaluminum compound is preferred.

本發明之甲基丙烯酸樹脂組成物，係嵌段共聚物(B)相對於甲基丙烯酸樹脂(A)之質量比(B/A)較佳為1/99~90/10，更佳為5/95~85/15，尤佳為5/95~25/75。嵌段共聚物(B)相對於甲基丙烯酸樹脂(A)之質量 比若大，則在藉由使用T模頭的熔融擠壓成形所得之板狀成形體的表面上，發生微細的條狀凹凸，有難以得到表面平滑性良好的板狀成形體之傾向。相反地，嵌段共聚物(B)相對於甲基丙烯酸樹脂(A)之質量比若小，則甲基丙烯酸樹脂組成物及由其所成的板狀成形體之拉伸彈性模數增加，柔軟性有降低之傾向。 The methacrylic resin composition of the present invention preferably has a mass ratio (B/A) of the block copolymer (B) to the methacrylic resin (A) of from 1/99 to 90/10, more preferably 5 /95~85/15, especially good for 5/95~25/75. The mass of the block copolymer (B) relative to the methacrylic resin (A) When the ratio is large, fine strip-like irregularities are formed on the surface of the plate-shaped formed body obtained by melt extrusion molding using a T die, and it is difficult to obtain a plate-shaped formed body having excellent surface smoothness. On the other hand, when the mass ratio of the block copolymer (B) to the methacrylic resin (A) is small, the tensile modulus of elasticity of the methacrylic resin composition and the plate-like formed body formed therefrom increases. The softness tends to decrease.

本發明之較佳實施形態的甲基丙烯酸樹脂組成物，係含有甲基丙烯酸樹脂(A)與嵌段共聚物(B)和聚碳酸酯樹脂。藉由含有聚碳酸酯樹脂，可得到相位差之調整為容易的甲基丙烯酸樹脂組成物。相對於甲基丙烯酸樹脂(A)與甲基丙烯酸樹脂嵌段共聚物(B)之合計量100質量份，聚碳酸酯樹脂之量較佳為1~10質量份，更佳為2~7質量份，尤佳為3~6質量份。 The methacrylic resin composition of the preferred embodiment of the present invention contains a methacrylic resin (A), a block copolymer (B) and a polycarbonate resin. By containing a polycarbonate resin, a methacrylic resin composition which is easy to adjust the phase difference can be obtained. The amount of the polycarbonate resin is preferably from 1 to 10 parts by mass, more preferably from 2 to 7 parts by mass, based on 100 parts by mass of the total of the methacrylic resin (A) and the methacrylic resin block copolymer (B). It is especially suitable for 3 to 6 parts by mass.

本發明中所用的聚碳酸酯樹脂，從與甲基丙烯酸樹脂的相溶性，以及所得之薄膜的透明性及面內均勻性之觀點來看，在300℃、1.2Kg的MVR值較佳為130~250cm3/10分鐘，更佳為150~230cm3/10分鐘，尤佳為180~220cm3/10分鐘。MVR值係依據JIS K7210，在300℃、1.2kg荷重、10分鐘之條件下所測定之值。 The polycarbonate resin used in the present invention has an MVR value of preferably 130 at 300 ° C and 1.2 Kg from the viewpoint of compatibility with the methacrylic resin and transparency and in-plane uniformity of the obtained film. ~250cm 3 /10 minutes, more preferably 150~230cm 3 /10 minutes, especially preferably 180~220cm 3 /10 minutes. The MVR value is a value measured under conditions of 300 ° C, 1.2 kg load, and 10 minutes in accordance with JIS K7210.

又，本發明中所用的聚碳酸酯樹脂係重量平均分子量Mwp較佳為15000~28000，更佳為18000~27000，尤佳為20000~24000。再者，聚碳酸酯樹脂的MVR值或重量平均分子量之調節係可藉由調整末端終止劑或分歧劑之量而進行。再者，Mwp係以GPC(凝膠滲透層析術)所測定的標準聚苯乙烯換算之分子量。 Further, the polycarbonate resin used in the present invention has a weight average molecular weight Mw p of preferably from 15,000 to 28,000, more preferably from 18,000 to 27,000, still more preferably from 20,000 to 24,000. Further, the adjustment of the MVR value or the weight average molecular weight of the polycarbonate resin can be carried out by adjusting the amount of the terminal terminator or the diverging agent. Further, Mw p is a molecular weight in terms of standard polystyrene measured by GPC (gel permeation chromatography).

本發明中所用的聚碳酸酯樹脂之玻璃轉移溫度，較佳為130℃以上，更佳為135℃以上，尤佳為140℃以上。該聚碳酸酯樹脂之玻璃轉移溫度的上限較佳為180℃。 The glass transition temperature of the polycarbonate resin used in the present invention is preferably 130 ° C or higher, more preferably 135 ° C or higher, and particularly preferably 140 ° C or higher. The upper limit of the glass transition temperature of the polycarbonate resin is preferably 180 °C.

本發明中所用的聚碳酸酯樹脂，係不受其製造方法所特別限定。例如，可舉出光氣法(界面聚合法)、熔融聚合法(酯交換法)等。又，本發明中所較佳使用的芳香族聚碳酸酯樹脂，係可對經熔融聚合法所製造的聚碳酸酯樹脂，施予用以調整末端羥基量之後處理者。 The polycarbonate resin used in the present invention is not particularly limited as long as it is produced. For example, a phosgene method (interfacial polymerization method), a melt polymerization method (transesterification method), and the like can be given. Further, the aromatic polycarbonate resin preferably used in the present invention can be applied to a polycarbonate resin produced by a melt polymerization method to adjust the amount of terminal hydroxyl groups.

作為用以製造聚碳酸酯樹脂之原料的多官能羥基化合物，可舉出可具有取代基的4,4’-二羥基聯苯類；可具有取代基的雙(羥基苯基)烷類；可具有取代基的雙(4-羥基苯基)醚類；可具有取代基的雙(4-羥基苯基)硫化物類；可具有取代基的雙(4-羥基苯基)亞碸類；可具有取代基的雙(4-羥基苯基)碸類；可具有取代基的雙(4-羥基苯基)酮類；可具有取代基的雙(羥基苯基)茀類；可具有取代基的二羥基-p-聯三苯類；可具有取代基的二羥基-p-聯四苯類；可具有取代基的雙(羥基苯基)吡類；可具有取代基的雙(羥基苯基)烷類；可具有取代基的雙[2-(4-羥基苯基)-2-丙基]苯類；可具有取代基的二羥基萘類；可具有取代基的二羥基苯類；可具有取代基的聚矽氧烷類；可具有取代基的二氫全氟烷類等。 The polyfunctional hydroxy compound used as a raw material for producing a polycarbonate resin may, for example, be a 4,4'-dihydroxybiphenyl group which may have a substituent; a bis(hydroxyphenyl)alkane which may have a substituent; a bis(4-hydroxyphenyl)ether having a substituent; a bis(4-hydroxyphenyl) sulfide which may have a substituent; a bis(4-hydroxyphenyl)anthracene which may have a substituent; a bis(4-hydroxyphenyl)anthracene having a substituent; a bis(4-hydroxyphenyl)ketone which may have a substituent; a bis(hydroxyphenyl)anthracene which may have a substituent; a substituent which may have a substituent Dihydroxy-p-biphenyls; dihydroxy-p-biphenyls which may have a substituent; bis(hydroxyphenyl)pyrene which may have a substituent a bis(hydroxyphenyl) group which may have a substituent Alkane; a bis[2-(4-hydroxyphenyl)-2-propyl]benzene which may have a substituent; a dihydroxynaphthalene which may have a substituent; a dihydroxybenzene which may have a substituent; A polyoxyalkylene of a substituent; a dihydroperfluoroalkane which may have a substituent, and the like.

於此等的多官能羥基化合物之中，較佳為2,2-雙(4-羥基苯基)丙烷、1,1-雙(4-羥基苯基)環己烷、雙(4-羥基苯基)二苯基甲烷、1,1-雙(4-羥基苯基)-1-苯基乙 烷、2,2-雙(4-羥基-3-甲基苯基)丙烷、2,2-雙(4-羥基-3-苯基苯基)丙烷、4,4’-二羥基聯苯、雙(4-羥基苯基)碸、2,2-雙(3,5-二溴-4-羥基苯基)丙烷、3,3-雙(4-羥基苯基)戊烷、9,9-雙(4-羥基-3-甲基苯基)茀、雙(4-羥基苯基)醚、4,4’-二羥基二苯基酮、2,2-雙(4-羥基-3-甲氧基苯基)1,1,1,3,3,3-六氟丙烷、α,ω-雙[3-(2-羥基苯基)丙基]聚二甲基矽氧烷、間苯二酚、2,7-二羥基萘，特佳為2,2-雙(4-羥基苯基)丙烷。 Among these polyfunctional hydroxy compounds, 2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, bis(4-hydroxybenzene) are preferred. Diphenylmethane, 1,1-bis(4-hydroxyphenyl)-1-phenyl Alkane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxy-3-phenylphenyl)propane, 4,4'-dihydroxybiphenyl, Bis(4-hydroxyphenyl)indole, 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane, 3,3-bis(4-hydroxyphenyl)pentane, 9,9- Bis(4-hydroxy-3-methylphenyl)indole, bis(4-hydroxyphenyl)ether, 4,4'-dihydroxydiphenyl ketone, 2,2-bis(4-hydroxy-3-methyl Oxyphenyl) 1,1,1,3,3,3-hexafluoropropane, α,ω-bis[3-(2-hydroxyphenyl)propyl]polydimethyloxane, isophthalic acid Phenol, 2,7-dihydroxynaphthalene, particularly preferably 2,2-bis(4-hydroxyphenyl)propane.

作為碳酸酯形成性化合物，可舉出光氣等之各種二鹵化羰基、或氯甲酸酯等之鹵甲酸酯、雙芳基碳酸酯等之碳酸酯化合物。此碳酸酯形成性化合物之量，只要考慮與多官能羥基化合物的反應之化學計量比而適宜調整即可。 Examples of the carbonate-forming compound include various dihalogenated carbonyl groups such as phosgene, and carbonate compounds such as a haloformate such as chloroformate or a bisaryl carbonate. The amount of the carbonate-forming compound may be appropriately adjusted in consideration of the stoichiometric ratio of the reaction with the polyfunctional hydroxy compound.

聚合反應通常係在酸結合劑之存在下於溶劑中進行。作為酸結合劑，可舉出氫氧化鈉、氫氧化鉀、氫氧化鋰、氫氧化銫等之鹼金屬氫氧化物；碳酸鈉、碳酸鉀等之鹼金屬碳酸鹽；三甲胺、三乙胺、三丁胺、N,N-二甲基環己胺、吡啶、二甲基苯胺等之三級胺；氯化三甲基苄基銨、氯化三乙基苄基銨、氯化三丁基苄基銨、氯化三辛基甲基銨、氯化四丁基銨、溴化四丁基銨等之四級銨鹽；氯化四丁基鏻、溴化四丁基鏻等之四級鏻鹽等。再者，按照所欲，亦可在此反應系統中添加少量的亞硫酸鈉或氫硫化物等之抗氧化劑。酸結合劑之量只要考慮反應之化學計量比而適宜調整即可。具體而言，相對於原料之多官能羥基化合物的羥基1莫耳，酸結 合劑較佳為使用1克當量或比其過剩之量，較佳為使用1~5克當量。 The polymerization is usually carried out in a solvent in the presence of an acid binder. Examples of the acid binder include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and barium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; trimethylamine and triethylamine; a tertiary amine such as tributylamine, N,N-dimethylcyclohexylamine, pyridine or dimethylaniline; trimethylbenzylammonium chloride, triethylbenzylammonium chloride, tributyl chloride a quaternary ammonium salt of benzylammonium chloride, trioctylmethylammonium chloride, tetrabutylammonium chloride, tetrabutylammonium bromide, etc.; four grades of tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, etc.鏻 salt and so on. Further, a small amount of an antioxidant such as sodium sulfite or hydrosulfide may be added to the reaction system as desired. The amount of the acid binder may be appropriately adjusted in consideration of the stoichiometric ratio of the reaction. Specifically, the hydroxyl group 1 mol of the polyfunctional hydroxy compound relative to the raw material Preferably, the mixture is used in an amount of 1 gram equivalent or more, preferably 1 to 5 gram equivalents.

又，於反應中，可使用眾所周知的末端終止劑或分岐劑。作為末端終止劑，可舉出對第三丁基苯酚、對苯基苯酚、對異丙苯基苯酚、對全氟壬基苯酚、對(全氟壬基苯基)苯酚、對(全氟己基苯基)苯酚、對三級全氟丁基苯酚、1-(對羥基苄基)全氟癸烷、對[2-(1H,1H-全氟參十二氧基)-1,1,1,3,3,3-六氟丙基]苯酚、3,5-雙(全氟己氧羰基)苯酚、對羥基苯甲酸全氟十二酯、對(1H,1H-全氟辛氧基)苯酚、2H,2H,9H-全氟壬酸、1,1,1,3,3,3-四氟-2-丙醇等。 Further, in the reaction, a well-known terminal terminator or a branching agent can be used. Examples of the terminal terminator include p-tert-butylphenol, p-phenylphenol, p-cumylphenol, p-perfluorononylphenol, p-(perfluorodecylphenyl)phenol, and p-perfluorohexyl. Phenyl)phenol, p-tertiary perfluorobutylphenol, 1-(p-hydroxybenzyl)perfluorodecane, p-[2-(1H,1H-perfluoro-dodedodecyloxy)-1,1,1 ,3,3,3-hexafluoropropyl]phenol, 3,5-bis(perfluorohexyloxycarbonyl)phenol, perfluorododecyl p-hydroxybenzoate, p-(1H,1H-perfluorooctyloxy) Phenol, 2H, 2H, 9H-perfluorodecanoic acid, 1,1,1,3,3,3-tetrafluoro-2-propanol and the like.

作為分岐劑，可舉出間苯三酚、焦棓酚、4,6-二甲基-2,4,6-參(4-羥基苯基)-2-庚烯、2,6-二甲基-2,4,6-參(4-羥基苯基)-3-庚烯、2,4-二甲基-2,4,6-參(4-羥基苯基)庚烷、1,3,5-參(2-羥基苯基)苯、1,3,5-參(4-羥基苯基)苯、1,1,1-參(4-羥基苯基)乙烷、參(4-羥基苯基)苯基甲烷、2,2-雙[4,4-雙(4-羥基苯基)環己基]丙烷、2,4-雙[2-雙(4-羥基苯基)-2-丙基]苯酚、2,6-雙(2-羥基-5-甲基苄基)-4-甲基苯酚、2-(4-羥基苯基)-2-(2,4-二羥基苯基)丙烷、肆(4-羥基苯基)甲烷、肆[4-(4-羥基苯基異丙基)苯氧基]甲烷、2,4-二羥基苯甲酸、均苯三酸、三聚氰酸、3,3-雙(3-甲基-4-羥基苯基)-2-氧代-2,3-二氫吲哚、3,3-雙(4-羥基芳基)氧基吲哚、5-氯靛紅、5,7-二氯靛紅、5-溴靛紅等。 Examples of the branching agent include phloroglucinol, pyrogallol, 4,6-dimethyl-2,4,6-cis (4-hydroxyphenyl)-2-heptene, 2,6-dimethyl Base-2,4,6-gin (4-hydroxyphenyl)-3-heptene, 2,4-dimethyl-2,4,6-gin (4-hydroxyphenyl)heptane, 1,3 , 5-paraxyl (2-hydroxyphenyl)benzene, 1,3,5-gin (4-hydroxyphenyl)benzene, 1,1,1-paraxyl (4-hydroxyphenyl)ethane, ginseng (4- Hydroxyphenyl)phenylmethane, 2,2-bis[4,4-bis(4-hydroxyphenyl)cyclohexyl]propane, 2,4-bis[2-bis(4-hydroxyphenyl)-2- Propyl]phenol, 2,6-bis(2-hydroxy-5-methylbenzyl)-4-methylphenol, 2-(4-hydroxyphenyl)-2-(2,4-dihydroxyphenyl) Propane, hydrazine (4-hydroxyphenyl)methane, hydrazine [4-(4-hydroxyphenylisopropyl)phenoxy]methane, 2,4-dihydroxybenzoic acid, trimesic acid, melamine Acid, 3,3-bis(3-methyl-4-hydroxyphenyl)-2-oxo-2,3-dihydroanthracene, 3,3-bis(4-hydroxyaryl)oxyanthracene , 5-chloroindole, 5,7-dichloropurine, 5-bromine ruthenium, and the like.

聚碳酸酯樹脂係除了聚碳酸酯單元，還可 含有具有聚酯結構、聚胺基甲酸酯結構、聚醚結構或聚矽氧烷結構等的單元。 Polycarbonate resin is available in addition to polycarbonate units. It contains a unit having a polyester structure, a polyurethane structure, a polyether structure, or a polyoxyalkylene structure.

本發明的較佳實施形態之甲基丙烯酸樹脂組成物，係含有甲基丙烯酸樹脂(A)與嵌段共聚物(B)和苯氧樹脂，藉由含有苯氧樹脂，可得到相位差之調整為容易的甲基丙烯酸樹脂組成物。相對於甲基丙烯酸樹脂(A)與甲基丙烯酸樹脂嵌段共聚物(B)之合計量100質量份，苯氧樹脂之量較佳為1~10質量份，更佳為2~7質量份，尤佳為3~6質量份。 The methacrylic resin composition of the preferred embodiment of the present invention contains a methacrylic resin (A), a block copolymer (B) and a phenoxy resin, and the phase difference can be adjusted by containing a phenoxy resin. It is an easy methacrylic resin composition. The amount of the phenoxy resin is preferably from 1 to 10 parts by mass, more preferably from 2 to 7 parts by mass, per 100 parts by mass of the total of the methacrylic resin (A) and the methacrylic resin block copolymer (B). , especially good for 3 to 6 parts by mass.

苯氧樹脂係熱塑性聚羥基聚醚樹脂。苯氧樹脂例如包含1種以上之式(1)所示的結構單元，且包含50質量%之式(1)所示的結構單元。 A phenoxy resin is a thermoplastic polyhydroxy polyether resin. The phenoxy resin contains, for example, one or more structural units represented by the formula (1), and contains 50% by mass of the structural unit represented by the formula (1).

式(1)中，X係包含至少一個苯環的2價基，R係碳數1~6之直鏈或支鏈的伸烷基。式(1)所示的結構單元係可以無規、交替或嵌段之任一形態連接。 In the formula (1), X is a divalent group containing at least one benzene ring, and R is a linear or branched alkyl group having 1 to 6 carbon atoms. The structural unit represented by the formula (1) may be bonded in any form of random, alternating or block.

苯氧樹脂較佳為包含10~1000個式(1)所示的結構單元，更佳為包含15~500個，尤佳為包含30~300個。 The phenoxy resin preferably contains 10 to 1000 structural units represented by the formula (1), more preferably 15 to 500, and particularly preferably 30 to 300.

苯氧樹脂較佳為在末端沒有環氧基者。若使用末端沒有環氧基的苯氧樹脂，則容易得到凝膠缺點少之薄膜。 The phenoxy resin is preferably one having no epoxy group at the terminal. When a phenoxy resin having no epoxy group at its end is used, it is easy to obtain a film having less gel defects.

苯氧樹脂之數量平均分子量較佳為3000~2000000，更佳為5000~100000，最佳為10000~50000。由於數量平均分子量在此範圍，可得到耐熱性高、強 度高之甲基丙烯酸樹脂組成物。 The number average molecular weight of the phenoxy resin is preferably from 3,000 to 2,000,000, more preferably from 5,000 to 100,000, most preferably from 10,000 to 50,000. Since the number average molecular weight is in this range, heat resistance is high and strong. A highly methacrylic resin composition.

苯氧樹脂之玻璃轉移溫度較佳為80℃以上，更佳為90℃以上，最佳為95℃以上。苯氧樹脂之玻璃轉移溫度若低，則所得之甲基丙烯酸樹脂組成物的耐熱性會變低。苯氧樹脂之玻璃轉移溫度的上限係沒有特別的規定，但一般為150℃。苯氧樹脂之玻璃轉移溫度若過高，則由所得之甲基丙烯酸樹脂組成物所構成的成形體會變脆。 The glass transition temperature of the phenoxy resin is preferably 80 ° C or higher, more preferably 90 ° C or higher, and most preferably 95 ° C or higher. If the glass transition temperature of the phenoxy resin is low, the heat resistance of the obtained methacrylic resin composition becomes low. The upper limit of the glass transition temperature of the phenoxy resin is not particularly specified, but is generally 150 °C. If the glass transition temperature of the phenoxy resin is too high, the molded body composed of the obtained methacrylic resin composition becomes brittle.

苯氧樹脂係可自2價苯酚化合物與環氧鹵丙烷之縮合反應、或2價苯酚化合物與2官能環氧樹脂之聚加成反應而得。該反應係可在溶液中或無溶劑下進行。 The phenoxy resin can be obtained by a condensation reaction of a divalent phenol compound with an epihalohydrin or a polyaddition reaction of a divalent phenol compound with a bifunctional epoxy resin. The reaction can be carried out in solution or without solvent.

作為苯氧樹脂之製造時所用的2價苯酚化合物，例如可舉出氫醌、間苯二酚、4,4-二羥基聯苯、4,4’-二羥基二苯基酮、2,2-雙(4-羥基苯基)丙烷、1,1-雙(4-羥基苯基)環己烷、1,1-雙(4-羥基苯基)-3,3,5-三甲基環己烷、雙(4-羥基苯基)甲烷、1,1-雙(4-羥基苯基)乙烷、2,2-雙(4-羥基苯基)丁烷、1,1-雙(4-羥基苯基)-1-苯基乙烷、雙(4-羥基苯基)二苯基甲烷、2,2-雙(4-羥基-3-甲基苯基)丙烷、2,2-雙(3-苯基-4-羥基苯基)丙烷、2,2-雙(4-羥基-3-第三丁基苯基)丙烷、1,3-雙(2-(4-羥基苯基)丙基)苯、1,4-雙(2-(4-羥基苯基)丙基)苯、2,2-雙(4-羥基苯基)-1,1,1,3,3,3-六氟丙烷、9,9’-雙(4-羥基苯基)茀等。於此等之中，從物性、成本方面來看，特佳為4,4-二羥基聯苯、4,4’-二羥基二苯基酮、2,2-雙(4-羥基苯基)丙烷、或9,9’-雙(4-羥基苯基)茀。 Examples of the divalent phenol compound used in the production of the phenoxy resin include hydroquinone, resorcin, 4,4-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl ketone, and 2,2. - bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclo Hexane, bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)butane, 1,1-double (4 -hydroxyphenyl)-1-phenylethane, bis(4-hydroxyphenyl)diphenylmethane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-double (3-phenyl-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-tert-butylphenyl)propane, 1,3-bis(2-(4-hydroxyphenyl) Propyl)benzene, 1,4-bis(2-(4-hydroxyphenyl)propyl)benzene, 2,2-bis(4-hydroxyphenyl)-1,1,1,3,3,3- Hexafluoropropane, 9,9'-bis(4-hydroxyphenyl)anthracene, and the like. Among these, in terms of physical properties and cost, it is particularly preferred to be 4,4-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl ketone, 2,2-bis(4-hydroxyphenyl). Propane, or 9,9'-bis(4-hydroxyphenyl)anthracene.

作為苯氧樹脂之製造時所用的2官能環氧樹脂類，可舉出由上述的2價苯酚化合物與環氧鹵丙烷之縮合反應所得的環氧寡聚物，例如氫醌二環氧丙基醚、間苯二酚二環氧丙基醚、雙酚S型環氧樹脂、雙酚A型環氧樹脂、雙酚F型環氧樹脂、甲基氫醌二環氧丙基醚、氯氫醌二環氧丙基醚、4,4’-二羥基二苯基氧化物二環氧丙基醚、2,6-二羥基萘二環氧丙基醚、二氯雙酚A二環氧丙基醚、四溴雙酚A型環氧樹脂、9,9’-雙(4)-羥基苯基)茀二環氧丙基醚等。於此等之中，從物性、成本方面來看，特佳為雙酚A型環氧樹脂、雙酚S型環氧樹脂、氫醌二環氧丙基醚、雙酚F型環氧樹脂、四溴雙酚A型環氧樹脂、或9,9’-雙(4)-羥基苯基)茀二環氧丙基醚。 Examples of the bifunctional epoxy resin used in the production of the phenoxy resin include an epoxy oligomer obtained by the condensation reaction of the above divalent phenol compound with an epihalohydrin, for example, hydroquinone diepoxypropyl group. Ether, resorcinol diepoxypropyl ether, bisphenol S epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, methylhydroquinone diepoxypropyl ether, chlorohydrogen Diethylene oxide propyl ether, 4,4'-dihydroxydiphenyl oxide diepoxypropyl ether, 2,6-dihydroxynaphthalene diepoxypropyl ether, dichlorobisphenol A diepoxypropyl Ethyl ether, tetrabromobisphenol A type epoxy resin, 9,9'-bis(4)-hydroxyphenyl) quinone diepoxypropyl ether, and the like. Among these, in terms of physical properties and cost, it is particularly preferred to be a bisphenol A epoxy resin, a bisphenol S epoxy resin, a hydroquinone diepoxypropyl ether, a bisphenol F epoxy resin, Tetrabromobisphenol A type epoxy resin or 9,9'-bis(4)-hydroxyphenyl)phosphonium diepoxypropyl ether.

作為苯氧樹脂之製造時所用的反應溶劑，可適宜使用非質子性有機溶劑，例如甲基乙基酮、二烷、四氫呋喃、苯乙酮、N-甲基吡咯啶酮、二甲亞碸、N,N-二甲基乙醯胺、環丁碸等。 As the reaction solvent used in the production of the phenoxy resin, an aprotic organic solvent such as methyl ethyl ketone or the like can be suitably used. Alkane, tetrahydrofuran, acetophenone, N-methylpyrrolidone, dimethyl hydrazine, N,N-dimethylacetamide, cyclobutyl hydrazine, and the like.

作為苯氧樹脂之製造時可用的反應觸媒，於習知的聚合觸媒中，可適宜使用鹼金屬氫氧化物、三級胺化合物、四級銨化合物、三級膦化合物及四級鏻化合物。 As a reaction catalyst usable in the production of a phenoxy resin, an alkali metal hydroxide, a tertiary amine compound, a quaternary ammonium compound, a tertiary phosphine compound, and a quaternary phosphonium compound can be suitably used in a conventional polymerization catalyst. .

本發明中所較佳使用的苯氧樹脂，係式(1)中的X較佳為來自式(2)~(8)所示的化合物之2價基。 In the phenoxy resin which is preferably used in the present invention, X in the formula (1) is preferably a divalent group derived from the compound represented by the formulae (2) to (8).

再者，構成2價基的2個結合鍵之位置只要是化學可能的位置，則沒有特別的限定。式(1)中之X較佳為自式(2)~(8)所示的化合物中之苯環上能拔掉2個氫原子的具有結合鍵之二價基。特佳為自式(3)~(8)所示的化合物中 之任二個苯環上能各自拔掉1個氫原子的具有結合鍵之二價基。 Further, the position of the two bonding bonds constituting the divalent group is not particularly limited as long as it is a chemically possible position. X in the formula (1) is preferably a divalent group having a bonding bond capable of extracting two hydrogen atoms from the benzene ring in the compound represented by the formula (2) to (8). Particularly preferred among the compounds represented by formulas (3) to (8) A divalent group having a bonding bond capable of unplugging one hydrogen atom on each of two benzene rings.

式(2)中，R4係氫原子、碳數1~6之直鏈或支鏈的烷基、或碳數2~6之直鏈或支鏈的烯基，p係1~4的任一整數。 In the formula (2), R 4 is a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, or a linear or branched alkenyl group having 2 to 6 carbon atoms, and p is 1 to 4 An integer.

式(3)中，R1係單鍵、碳數1~6之直鏈或支鏈的伸烷基、碳數3~20的伸環烷基、或碳數3~20的亞環烷基。 In the formula (3), R 1 is a single bond, a linear or branched alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or a cycloalkylene group having 3 to 20 carbon atoms. .

式(3)及(4)中，R2及R3各自獨立地係氫原子、碳數1~6之直鏈或支鏈的烷基、或碳數2~6之直鏈或支鏈的烯基，n及m各自獨立地係1~4之任一整數。 In the formulae (3) and (4), R 2 and R 3 each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, or a linear or branched carbon number of 2 to 6. The alkenyl group, n and m are each independently an integer of from 1 to 4.

式(5)及(6)中，R6及R7各自獨立地係單鍵、碳數1~6之直鏈或支鏈的伸烷基、碳數3~20的伸環烷基、或碳數3~20的亞環烷基。 In the formulae (5) and (6), R 6 and R 7 are each independently a single bond, a linear or branched alkyl group having 1 to 6 carbon atoms, a stretched alkyl group having 3 to 20 carbon atoms, or A cycloalkylene group having 3 to 20 carbon atoms.

式(5)、(6)、(7)及(8)中，R5及R8各自獨立地係氫原子、碳數1~6之直鏈或支鏈的烷基、或碳數2~6之直鏈或支鏈的烯基，q及r各自獨立地係1~4之任一整數。 In the formulae (5), (6), (7) and (8), R 5 and R 8 each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, or a carbon number of 2 to 6; A straight or branched alkenyl group of 6 wherein q and r are each independently an integer of from 1 to 4.

式(1)中，X亦可為來自複數的苯環與脂環或雜環所縮合成的化合物之2價基。例如，可舉出來自具有茀結構或咔唑結構的化合物之2價基。 In the formula (1), X may be a divalent group derived from a compound in which a benzene ring is condensed with an alicyclic or heterocyclic ring. For example, a divalent group derived from a compound having an anthracene structure or a carbazole structure can be mentioned.

作為來自上述式(2)至(9)所示的化合物之2價基之例，可舉出如以下者。再者，此例示並不意味本 案發明中的X受此等所限定。 Examples of the divalent group derived from the compounds represented by the above formulas (2) to (9) include the following. Furthermore, this illustration does not mean this. The X in the invention is limited by these.

式(1)所示的結構單元較佳為式(9)或(10)所示的結構單元，更佳為式(11)所示的結構單元。較佳態樣之苯氧樹脂宜包含10~1000個該結構單元。 The structural unit represented by the formula (1) is preferably a structural unit represented by the formula (9) or (10), and more preferably a structural unit represented by the formula (11). The preferred aspect of the phenoxy resin preferably comprises from 10 to 1000 such structural units.

式(9)中，R9係單鍵、碳數1~6之直鏈或支鏈的伸烷基、碳數3~20的伸環烷基、或碳數3~20的亞環烷基。 In the formula (9), R 9 is a single bond, a linear or branched alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or a cycloalkylene group having 3 to 20 carbon atoms. .

式(9)或(10)中，R10係碳數1~6之直鏈或支鏈的伸烷基。 In the formula (9) or (10), R 10 is a linear or branched alkylene group having 1 to 6 carbon atoms.

作為此等苯氧樹脂，可使用新日鐵住金化學的YP-50或YP-50S、三菱化學的jER系列、InChem公司的苯氧樹脂之PKFE或PKHJ等。 As such a phenoxy resin, YP-50 or YP-50S of Nippon Steel & Sumitomo Chemical Co., Ltd., jER series of Mitsubishi Chemical, PKFE or PKHJ of phenoxy resin of InChem Co., Ltd., etc. can be used.

於本發明之甲基丙烯酸樹脂組成物中，除了甲基丙烯酸樹脂(A)、嵌段共聚物(B)及聚碳酸酯樹脂或苯氧樹脂，還可含有其它的聚合物。 The methacrylic resin composition of the present invention may contain other polymers in addition to the methacrylic resin (A), the block copolymer (B), and the polycarbonate resin or the phenoxy resin.

作為其它的聚合物，可舉出聚乙烯、聚丙烯、聚丁烯-1、聚-4-甲基戊烯-1、聚降烯等之聚烯烴樹脂；乙烯系離子聚合物；聚苯乙烯、苯乙烯-馬來酸酐共聚物、高衝擊聚苯乙烯、AS樹脂、ABS樹脂、AES樹脂、AAS樹脂、ACS樹脂、MBS樹脂等之苯乙烯系樹脂；甲基丙烯酸甲酯系聚合物、甲基丙烯酸甲酯-苯乙烯共聚物；聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯等之聚酯樹脂；尼龍6、尼龍66、聚醯胺彈性體等之聚醯胺；聚氯乙烯、聚偏二氯乙烯、聚乙烯醇、乙烯-乙烯醇共聚物、聚縮醛、聚偏二氟乙烯、聚胺基甲酸酯、改性聚苯醚、聚苯硫、聚矽氧改性樹脂；丙烯酸橡膠、聚矽氧橡膠；SEPS、SEBS、SIS等之苯乙烯系熱塑性彈性體；IR、EPR、EPDM等之烯烴系橡膠等。本發明之甲基丙烯酸樹脂組成物中可含有之其它的聚合物之量較佳為10質量%以下，更佳為5質量%以下，最佳為0質量%。 Examples of other polymers include polyethylene, polypropylene, polybutene-1, poly-4-methylpentene-1, and polycondensation. Polyolefin resin such as olefin; ethylene ionomer; polystyrene, styrene-maleic anhydride copolymer, high impact polystyrene, AS resin, ABS resin, AES resin, AAS resin, ACS resin, MBS resin, etc. Styrene resin; methyl methacrylate polymer, methyl methacrylate-styrene copolymer; polyester resin such as polyethylene terephthalate or polybutylene terephthalate; nylon 6. Polyamides such as nylon 66 and polyamide elastomer; polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyacetal, polyvinylidene fluoride, polyamine Formate, modified polyphenylene ether, polyphenylene sulfide, polyfluorene modified resin; acrylic rubber, polyoxyethylene rubber; styrene thermoplastic elastomers such as SEPS, SEBS, SIS, etc.; IR, EPR, EPDM, etc. Olefin-based rubber and the like. The amount of the other polymer which may be contained in the methacrylic resin composition of the present invention is preferably 10% by mass or less, more preferably 5% by mass or less, and most preferably 0% by mass.

於本發明的甲基丙烯酸樹脂組成物中，亦可包含填料、抗氧化劑、熱降解防止劑、紫外線吸收劑、光安定劑、滑劑、脫模劑、高分子加工助劑、抗靜電劑、難燃劑、染料顏料、光擴散劑、有機色素、消光劑 、螢光體等之摻合在通常的樹脂中之添加劑。此等係可在製造甲基丙烯酸樹脂(A)或嵌段共聚物(B)時的聚合反應液之任一者或兩者中添加，亦可在經由聚合反應所製造的甲基丙烯酸樹脂(A)或嵌段共聚物(B)之任一者或兩者中添加。 The methacrylic resin composition of the present invention may further comprise a filler, an antioxidant, a thermal degradation inhibitor, an ultraviolet absorber, a light stabilizer, a slip agent, a mold release agent, a polymer processing aid, an antistatic agent, Flame retardant, dye pigment, light diffusing agent, organic pigment, matting agent An additive such as a phosphor or the like which is blended in a usual resin. These may be added to either or both of the polymerization reaction liquids in the production of the methacrylic resin (A) or the block copolymer (B), or may be a methacrylic resin produced by a polymerization reaction ( Add either A) or block copolymer (B) or both.

作為填料，可舉出碳酸鈣、滑石、碳黑、氧化鈦、矽石、黏土、硫酸鋇、碳酸鎂等。本發明之甲基丙烯酸樹脂組成物中可含有的填料之量，較佳為3質量%以下，更佳為1.5質量%以下。 Examples of the filler include calcium carbonate, talc, carbon black, titanium oxide, vermiculite, clay, barium sulfate, and magnesium carbonate. The amount of the filler which can be contained in the methacrylic resin composition of the present invention is preferably 3% by mass or less, more preferably 1.5% by mass or less.

抗氧化劑係在氧存在下具有以其單質防止樹脂之氧化降解的效果者。例如，可舉出磷系抗氧化劑、受阻酚系抗氧化劑、硫醚系抗氧化劑等。此等的抗氧化劑係可單獨使用1種，也可併用2種以上。其中，從著色所致的光學特性之劣化防止效果的觀點來看，較佳為磷系抗氧化劑或受阻酚系抗氧化劑，更佳為磷系抗氧化劑與受阻酚系抗氧化劑之併用。 The antioxidant has an effect of preventing oxidative degradation of the resin by its elemental substance in the presence of oxygen. For example, a phosphorus-based antioxidant, a hindered phenol-based antioxidant, a thioether-based antioxidant, or the like can be given. These antioxidants may be used alone or in combination of two or more. In particular, a phosphorus-based antioxidant or a hindered phenol-based antioxidant is preferable from the viewpoint of the effect of preventing deterioration of optical properties due to coloring, and it is more preferably used in combination with a phosphorus-based antioxidant and a hindered phenol-based antioxidant.

併用磷系抗氧化劑與受阻酚系抗氧化劑時，磷系抗氧化劑的使用量：受阻酚系抗氧化劑的使用量係質量比較佳為1：5~2：1，更佳為1：2~1：1。 When a phosphorus-based antioxidant and a hindered phenol-based antioxidant are used together, the amount of the phosphorus-based antioxidant used: the amount of the hindered phenol-based antioxidant is preferably 1:5 to 2:1, more preferably 1:2 to 1 :1.

作為磷系抗氧化劑，較佳為2,2-亞甲基雙(4,6-二第三丁基苯基)辛基亞磷酸酯(ADEKA公司製；商品名：Adkstab HP-10)、參(2,4-二第三丁基苯基)亞磷酸酯(BASF公司製；商品名：IRGAFOS 168)、3,9-雙(2,6-二第三丁基-4-甲基苯氧基)-2,4,8,10-四氧雜-3,9-二磷雙螺[5.5]十一烷(ADEKA公司製；商品名：Adkstab PEP-36) 等。 As the phosphorus-based antioxidant, 2,2-methylenebis(4,6-di-t-butylphenyl)octylphosphite (manufactured by Adeka Co., Ltd.; trade name: Adkstab HP-10), ginseng is preferred. (2,4-di-t-butylphenyl)phosphite (manufactured by BASF Corporation; trade name: IRGAFOS 168), 3,9-bis(2,6-di-t-butyl-4-methylphenoxyl) Base)-2,4,8,10-tetraoxa-3,9-diphosphocyrro[5.5]undecane (made by Adeka; trade name: Adkstab PEP-36) Wait.

作為受阻酚系抗氧化劑，較佳為季戊四醇基-肆[3-(3,5-二第三丁基-4-羥基苯基)丙酸酯](BASF公司製；商品名IRGANO 01010)、十八基-3-(3,5-二第三丁基-4-羥基苯基)丙酸酯(BASF公司製；商品名IRGANO 01076)等。 As the hindered phenol-based antioxidant, pentaerythritol-indole [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] (manufactured by BASF Corporation; trade name IRGANO 01010), ten Octyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate (manufactured by BASF Corporation; trade name IRGANO 01076).

熱降解防止劑係藉由在實質上無氧之狀態下捕捉暴露於高熱時所產生的聚合物自由基，而可防止樹脂的熱降解者。 The thermal degradation preventing agent prevents thermal degradation of the resin by capturing polymer radicals generated when exposed to high heat in a substantially oxygen-free state.

作為該熱降解防止劑，較佳為2-第三丁基-6-(3’-第三丁基-5’-甲基-羥基苄基)-4-甲基苯基丙烯酸酯(住友化學公司製；商品名Sumilizer GM)、2,4-二第三戊基-6-(3’,5’-二第三戊基-2’-羥基-α-甲基苄基)苯基丙烯酸酯(住友化學公司製；商品名Sumilizer GS)等。 As the thermal degradation preventing agent, 2-t-butyl-6-(3'-tert-butyl-5'-methyl-hydroxybenzyl)-4-methylphenyl acrylate is preferred (Sumitomo Chemical Co., Ltd. Company name; trade name Sumilizer GM), 2,4-di-p-pentyl-6-(3',5'-di-p-tripentyl-2'-hydroxy-α-methylbenzyl)phenyl acrylate (made by Sumitomo Chemical Co., Ltd.; trade name Sumilizer GS).

紫外線吸收劑係具有吸收紫外線之能力的化合物。紫外線吸收劑主要是認為具有將光能轉換成熱能之機能的化合物。 The ultraviolet absorber is a compound having an ability to absorb ultraviolet rays. Ultraviolet absorbers are mainly considered to have a function of converting light energy into heat energy.

作為紫外線吸收劑，可舉出二苯基酮類、苯并***類、三類、苯甲酸酯類、水楊酸酯類、氰基丙烯酸酯類、草醯替苯胺類、丙二酸酯類、甲脒類等。於此等之中，較佳為苯并***類、三類或在波長380~450nm的莫耳吸光係數之最大值εmax為1200dm3．mol-1cm-1以下之紫外線吸收劑。 Examples of the ultraviolet absorber include diphenyl ketones, benzotriazoles, and trisole. Classes, benzoates, salicylates, cyanoacrylates, oxalic anilides, malonic esters, formazan, and the like. Among them, preferred are benzotriazoles, three The maximum value ε max of the class or the molar absorption coefficient at a wavelength of 380-450 nm is 1200 dm 3 . Ultraviolet absorber of mol -1 cm -1 or less.

苯并***類由於抑制因紫外線照射所造成的著色等之光學特性降低之效果高，作為將本發明之 甲基丙烯酸樹脂組成物應用於要求該特性的用途之情況中所用的紫外線吸收劑較佳。作為苯并***類，較佳為2-(2H-苯并***-2-基)-4-(1,1,3,3-四甲基丁基)苯酚(BASF公司製；商品名TINUVIN 329)、2-(2H-苯并***-2-基)-4,6-雙(1-甲基-1-苯基乙基)苯酚(BASF公司製；商品名TINUVIN 234)、2,2’-亞甲基雙[6-(2H-苯并***-2-基)-4-第三辛基苯酚](ADEKA公司製；LA-31)、2-(5-辛硫基-2H-苯并***-2-基)-6-第三丁基-4-甲基苯酚等。 The benzotriazole has a high effect of suppressing a decrease in optical characteristics such as coloring due to ultraviolet irradiation, and is a method of the present invention. The ultraviolet absorber used in the case where the methacrylic resin composition is used for the application requiring this property is preferable. As the benzotriazole, 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol (manufactured by BASF Corporation; trade name) is preferred. TINUVIN 329), 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol (manufactured by BASF Corporation; trade name TINUVIN 234), 2 , 2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-trioctylphenol] (made by ADEKA); LA-31, 2-(5-octylthio -2H-benzotriazol-2-yl)-6-tert-butyl-4-methylphenol.

又，在波長380~450nm的莫耳吸光係數之最大值εmax為1200dm3．mol-1cm-1以下之紫外線吸收劑，係可抑制所得之成形體的黃色調。作為如此的紫外線吸收劑，可舉出2-乙基-2’-乙氧基-草醯替苯胺(CLARIANT日本公司製；商品名Sundupore VSU)等。 Further, the maximum value ε max of the molar absorption coefficient at a wavelength of 380 to 450 nm is 1200 dm 3 . The ultraviolet absorber of mol -1 cm -1 or less can suppress the yellow tone of the obtained molded body. Examples of such an ultraviolet absorber include 2-ethyl-2'-ethoxy-oxabenzidine (manufactured by CLARIANT Japan Co., Ltd.; trade name Sundupore VSU).

於此等紫外線吸收劑之中，從抑制因紫外線照射所致的樹脂劣化之觀點來看，較宜使用苯并***類。 Among these ultraviolet absorbers, benzotriazoles are preferably used from the viewpoint of suppressing deterioration of the resin due to ultraviolet irradiation.

又，欲有效率地吸收波長380nm附近之波長時，較宜使用三類的紫外線吸收劑。作為如此的紫外線吸收劑，可舉出2,4,6-參(2-羥基-4-己氧基-3-甲基苯基)-1,3,5-三(ADEKA公司製；LA-F70)、或其類似物之羥基苯基三系紫外線吸收劑(BASF公司製；CGL777MPA-D或TINUVIN 460)、2,4-二苯基-6-(2-羥基-4-己氧基苯基)-1,3,5-三等。 Moreover, in order to efficiently absorb the wavelength near the wavelength of 380 nm, it is preferable to use three a class of UV absorbers. As such an ultraviolet absorber, 2,4,6-gin(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-three can be mentioned. (ADEKA company; LA-F70), or its analog hydroxyphenyl three UV absorber (BASF company; CGL777MPA-D or TINUVIN 460), 2,4-diphenyl-6-(2-hydroxy-4-hexyloxyphenyl)-1,3,5-three Wait.

尚且，紫外線吸收劑的莫耳吸光係數之最大值εmax係如以下測定。於1L的環己烷中添加10.00mg紫外線吸收劑，使其溶解直到目視觀察沒有未溶解物。將 此溶液注入1cm×1cm×3cm之石英玻璃槽中，使用日立製作所公司製U-3410型分光光度計，測定在波長380~450nm的吸光度。自紫外線吸收劑之分子量(MUV)與所測定的吸光度之最大值(Amax)，藉由下式計算，算出莫耳吸光係數之最大值εmax。 Further, the maximum value ε max of the molar absorption coefficient of the ultraviolet absorber is measured as follows. To 1 L of cyclohexane, 10.00 mg of an ultraviolet absorber was added and dissolved until no undissolved matter was visually observed. This solution was poured into a quartz glass tank of 1 cm × 1 cm × 3 cm, and the absorbance at a wavelength of 380 to 450 nm was measured using a U-3410 spectrophotometer manufactured by Hitachi, Ltd. From the molecular weight (M UV ) of the ultraviolet absorber and the maximum value (A max ) of the measured absorbance, the maximum value ε max of the Mohr absorbance coefficient was calculated by the following formula.

εmax=[Amax/(10×10-3)]×MUV ε max =[A max /(10×10 -3 )]×M UV

再者，欲特別有效果地收380nm~400nm的波長之光時，較宜使用WO2011/089794A1、WO2012/124395A1、日本特開2012-012476號公報、日本特開2013-023461號公報、日本特開2013-112790號公報、日本特開2013-194037號公報、日本特開2014-62228號公報、日本特開2014-88542號公報、日本特開2014-88543號公報等中揭示之具有雜環結構的配位子之金屬錯合物(例如，式(A)所示的結構之化合物等)作為紫外線吸收劑。 In addition, when it is desired to receive light of a wavelength of 380 nm to 400 nm, it is preferable to use WO2011/089794A1, WO2012/124395A1, JP-A-2012-012476, JP-A-2013-023461, and JP-A. The heterocyclic structure disclosed in Japanese Laid-Open Patent Publication No. Hei. No. 2014-88543, Japanese Patent Application Laid-Open No. Hei No. Hei. A metal complex of a ligand (for example, a compound of a structure represented by the formula (A)) is used as an ultraviolet absorber.

[式(A)中，M係金屬原子。 [In the formula (A), M is a metal atom.

Y1、Y2、Y3及Y4各自獨立地係碳原子以外的二價基(氧原子、硫原子、NH、NR5等)。R5各自獨立地係烷基、 芳基、雜芳基、雜芳烷基、芳烷基等之取代基。該取代基係可在該取代基上更具有取代基。 Y 1 , Y 2 , Y 3 and Y 4 are each independently a divalent group other than a carbon atom (oxygen atom, sulfur atom, NH, NR 5 or the like). R 5 is each independently a substituent of an alkyl group, an aryl group, a heteroaryl group, a heteroarylalkyl group, an aralkyl group or the like. The substituent may have a more substituent on the substituent.

Z1及Z2各自獨立地係三價基(氮原子、CH、CR6等)。R6各自獨立地係烷基、芳基、雜芳基、雜芳烷基、芳烷基等之取代基。該取代基係可在該取代基上更具有取代基。 Z 1 and Z 2 are each independently a trivalent group (nitrogen atom, CH, CR 6 or the like). R 6 is each independently a substituent of an alkyl group, an aryl group, a heteroaryl group, a heteroarylalkyl group, an aralkyl group or the like. The substituent may have a more substituent on the substituent.

R1、R2、R3及R4各自獨立地係氫原子、烷基、羥基、羧基、烷氧基、鹵基、烷基磺醯基、嗎啉代磺醯基、哌啶基磺醯基、硫嗎啉代磺醯基、哌基磺醯基等之取代基。該取代基可在該取代基上更具有取代基。a、b、c及d各自表示R1、R2、R3及R4之數且為1~4之任一整數]。 R 1 , R 2 , R 3 and R 4 are each independently a hydrogen atom, an alkyl group, a hydroxyl group, a carboxyl group, an alkoxy group, a halogen group, an alkylsulfonyl group, a morpholinosulfonyl group or a piperidinylsulfonium group. Thiomorpholsulfonyl, piperazine Substituents such as sulfonyl groups. The substituent may have a more substituent on the substituent. a, b, c and d each represent the number of R 1 , R 2 , R 3 and R 4 and are any integer of 1 to 4].

作為該雜環結構之配位子，可舉出2,2’-亞胺基雙苯并噻唑、2-(2-苯并噻唑基胺基)苯并唑、2-(2-苯并噻唑基胺基)苯并咪唑、(2-苯并噻唑基)(2-苯并咪唑基)甲烷、雙(2-苯并唑基)甲烷、雙(2-苯并噻唑基)甲烷、雙[2-(N-取代)苯并咪唑基]甲烷等及彼等之衍生物。作為如此的金屬錯合物之中心金屬，較宜使用銅、鎳、鈷、鋅。又，為了將此等金屬錯合物作為紫外線吸收劑使用，較佳為使金屬錯合物分散於低分子化合物或聚合物等之介質中。相對於本發明的薄膜100質量份，該金屬錯合物之添加量較佳為0.01質量份~5質量份，更佳為0.1~2質量份。由於前述金屬錯合物在380nm~400nm的波長之莫耳吸光係數大，用以得到充分的紫外線吸收效果所添加之量少即足夠。添加量若少，則可抑制因滲出等所致的樹脂薄膜外觀之惡化。又，前述金屬錯合物 由於耐熱性高，成形加工時的劣化或分解少。再者，前述金屬錯合物由於耐光性高，可長期間保持紫外線吸收性能。 Examples of the ligand of the heterocyclic structure include 2,2'-iminobisbenzothiazole and 2-(2-benzothiazolylamino)benzo Oxazole, 2-(2-benzothiazolylamino)benzimidazole, (2-benzothiazolyl)(2-benzimidazolyl)methane, bis(2-benzoxyl) Azolyl)methane, bis(2-benzothiazolyl)methane, bis[2-(N-substituted) benzimidazolyl]methane, and the like, and derivatives thereof. As the central metal of such a metal complex, copper, nickel, cobalt, and zinc are preferably used. Further, in order to use these metal complexes as ultraviolet absorbers, it is preferred to disperse the metal complex in a medium such as a low molecular compound or a polymer. The amount of the metal complex added is preferably from 0.01 part by mass to 5 parts by mass, more preferably from 0.1 to 2 parts by mass, per 100 parts by mass of the film of the present invention. Since the metal complex has a large molar absorption coefficient at a wavelength of 380 nm to 400 nm, it is sufficient to obtain a sufficient ultraviolet absorbing effect. When the amount of addition is small, deterioration of the appearance of the resin film due to bleeding or the like can be suppressed. Further, the metal complex has high heat resistance and is less deteriorated or decomposed during molding. Further, the metal complex compound has high light resistance and can maintain ultraviolet absorbing performance for a long period of time.

光安定劑主要是認為具有捕捉因光所致的氧化而生成的自由基之機能的化合物。作為合適的光安定劑，可舉出具有2,2,6,6-四烷基哌啶骨架的化合物等之受阻胺類。 The light stabilizer is mainly a compound having a function of capturing radicals generated by oxidation due to light. As a suitable light stabilizer, a hindered amine such as a compound having a 2,2,6,6-tetraalkylpiperidine skeleton may be mentioned.

作為滑劑，例如可舉出硬脂酸、二十二酸、硬脂醯胺酸、亞甲基雙硬脂醯胺、羥基硬脂酸三甘油酯、石蠟、酮蠟、辛醇、硬化油等。 Examples of the slip agent include stearic acid, behenic acid, stearic acid, methylenebisstearylamine, hydroxystearic acid triglyceride, paraffin wax, ketone wax, octanol, and hardened oil. Wait.

作為脫模劑，可舉出鯨蠟醇、硬脂醇等之高級醇類，硬脂酸單甘油酯、硬脂酸二甘油酯等之甘油高級脂肪酸酯等。於本發明中，作為脫模劑，較佳為併用高級醇類與甘油脂肪酸單酯。併用高級醇類與甘油脂肪酸單酯時，其比例係沒有特別的限制，但高級醇類的使用量：甘油脂肪酸單酯的使用量係質量比較佳為2.5：1~3.5：1，更佳為2.8：1~3.2：1。 Examples of the release agent include higher alcohols such as cetyl alcohol and stearyl alcohol, and glycerin higher fatty acid esters such as stearic acid monoglyceride and stearic acid diglyceride. In the present invention, as the release agent, it is preferred to use a higher alcohol and a glycerin fatty acid monoester in combination. When a higher alcohol and a glycerin fatty acid monoester are used together, the ratio is not particularly limited, but the amount of the higher alcohol used is preferably from 2.5:1 to 3.5:1, more preferably 2.8:1~3.2:1.

作為高分子加工助劑，通常使用藉由乳化聚合法可製造之具有0.05~0.5μm的粒徑之聚合物粒子。該聚合物粒子係可為由單一組成比及單一極限黏度的聚合物所構成之單層粒子，而且也可為由組成比或極限黏度不同的2種以上之聚合物所構成之多層粒子。其中，可舉出具有在內層具有低極限黏度的聚合物層，且在外層具有5dl/g以上的高極限黏度之聚合物層的2層結構之粒子作為較佳者。高分子加工助劑係極限黏度較佳為3 ~6dl/g。極限黏度若過小，則有成形性的改善效果低之傾向。極限黏度若過大，則有招致甲基丙烯酸樹脂組成物的成形加工性降低之傾向。具體而言，可舉出三菱麗陽公司製Metablen-P系列或Rohm & Hass公司製Paraloid系列等。 As the polymer processing aid, polymer particles having a particle diameter of 0.05 to 0.5 μm which can be produced by an emulsion polymerization method are usually used. The polymer particles may be a single layer particle composed of a polymer having a single composition ratio and a single ultimate viscosity, or may be a multilayer particle composed of two or more polymers having different composition ratios or ultimate viscosity. Among them, a particle having a two-layer structure having a polymer layer having a low ultimate viscosity in the inner layer and a polymer layer having a high ultimate viscosity of 5 dl/g or more in the outer layer is preferable. The ultimate viscosity of the polymer processing aid is preferably 3 ~6dl/g. If the ultimate viscosity is too small, the effect of improving the formability tends to be low. If the ultimate viscosity is too large, the formability of the methacrylic resin composition tends to be lowered. Specifically, a Metablen-P series manufactured by Mitsubishi Rayon Co., Ltd. or a Paraloid series manufactured by Rohm & Hass Co., Ltd., and the like can be given.

作為有機色素，較宜使用具有將紫外線轉換成可見光線之機能的化合物。 As the organic dye, a compound having a function of converting ultraviolet rays into visible light is preferably used.

作為光擴散劑或消光劑，可舉出玻璃微粒子、聚矽氧烷系交聯微粒子、交聯聚合物微粒子、滑石、碳酸鈣、硫酸鋇等。 Examples of the light diffusing agent or the matting agent include glass fine particles, polyoxyalkylene-based crosslinked fine particles, crosslinked polymer fine particles, talc, calcium carbonate, barium sulfate, and the like.

作為螢光體，可舉出螢光顏料、螢光染料、螢光白色染料、螢光增白劑、螢光漂白劑等。 Examples of the phosphor include a fluorescent pigment, a fluorescent dye, a fluorescent white dye, a fluorescent whitening agent, and a fluorescent bleaching agent.

本發明之甲基丙烯酸樹脂組成物中可含有的抗氧化劑、熱降解防止劑、紫外線吸收劑、光安定劑、滑劑、脫模劑、高分子加工助劑、抗靜電劑、難燃劑、染料顏料、光擴散劑、有機色素、消光劑及螢光體之合計量，較佳為7質量%以下，更佳為5質量%以下，尤佳為4質量%以下。 The antioxidant, thermal degradation inhibitor, ultraviolet absorber, light stabilizer, slip agent, mold release agent, polymer processing aid, antistatic agent, flame retardant, etc. which may be contained in the methacrylic resin composition of the present invention. The total amount of the dye pigment, the light diffusing agent, the organic dye, the matting agent, and the phosphor is preferably 7% by mass or less, more preferably 5% by mass or less, and particularly preferably 4% by mass or less.

本發明之甲基丙烯酸樹脂組成物係可藉由眾所周知之方法製造。本發明之甲基丙烯酸樹脂組成物，例如可藉由將甲基丙烯酸樹脂(A)及嵌段共聚物(B)與其它的聚合物等予以熔融混煉，而製造甲基丙烯酸樹脂組成物。熔融混煉例如可使用捏合機、擠壓機、混合輥、班百里混合機等之熔融混煉裝置進行。混煉時之溫度係可按照甲基丙烯酸樹脂(A)、嵌段共聚物(B)及其它 的聚合物之軟化溫度來適宜設定，較佳為150℃~300℃。 The methacrylic resin composition of the present invention can be produced by a well-known method. The methacrylic resin composition of the present invention can be produced by, for example, melting and kneading a methacrylic resin (A) and a block copolymer (B) with another polymer or the like to produce a methacrylic resin composition. The melt kneading can be carried out, for example, by a melt kneading device such as a kneader, an extruder, a mixing roll, or a Banbury mixer. The temperature at the time of mixing can be methacrylic resin (A), block copolymer (B) and others. The softening temperature of the polymer is suitably set, preferably from 150 ° C to 300 ° C.

甲基丙烯酸樹脂組成物，亦可藉由在嵌段共聚物(B)之存在下，將甲基丙烯酸樹脂(A)之原料的單體予以聚合而製造。該聚合係可與甲基丙烯酸樹脂(A)之製造用的聚合方法同樣地進行。於嵌段共聚物(B)之存在下，將甲基丙烯酸樹脂(A)之原料的單體予以聚合的製造方法，係與藉由將甲基丙烯酸樹脂(A)與嵌段共聚物(B)予以熔融混煉而製造之方法比較下，由於施加於甲基丙烯酸樹脂的熱歷程變短，而抑制甲基丙烯酸樹脂之熱分解，容易得到著色或異物少的成形體。 The methacrylic resin composition can also be produced by polymerizing a monomer of a raw material of the methacrylic resin (A) in the presence of the block copolymer (B). This polymerization can be carried out in the same manner as the polymerization method for producing methacrylic resin (A). A method for polymerizing a monomer of a raw material of a methacrylic resin (A) in the presence of a block copolymer (B) by using a methacrylic resin (A) and a block copolymer (B) In the method of melt-kneading and manufacturing, the thermal history of the methacrylic resin is shortened, and the thermal decomposition of the methacrylic resin is suppressed, whereby a molded article having less coloration or foreign matter is easily obtained.

本發明之甲基丙烯酸樹脂組成物係重量平均分子量Mwc較佳為3萬2千~30萬，更佳為4萬5千~23萬，尤佳為6萬~20萬。本發明之甲基丙烯酸樹脂組成物係Mwc與數量平均分子量Mnc之比Mwc/Mnc較佳為1.2~2.5，更佳為1.3~2.0。Mwc或Mwc/Mnc若在此範圍，則甲基丙烯酸樹脂組成物的成形加工性變良好，容易得到耐衝擊性或韌性優異的成形體。再者，Mwc及Mnc係以GPC(凝膠滲透層析術)所測定的標準聚苯乙烯換算之分子量。 The weight average molecular weight Mw c of the methacrylic resin composition of the present invention is preferably from 30,000 to 300,000, more preferably from 45,000 to 230,000, and particularly preferably from 60,000 to 200,000. The ratio Mw c /Mn c of the methacrylic resin composition system Mw c of the present invention to the number average molecular weight Mn c is preferably from 1.2 to 2.5, more preferably from 1.3 to 2.0. When Mw c or Mw c /Mn c is in this range, the moldability of the methacrylic resin composition is improved, and a molded article excellent in impact resistance and toughness is easily obtained. Further, Mw c and Mn c are molecular weights in terms of standard polystyrene measured by GPC (gel permeation chromatography).

本發明之甲基丙烯酸樹脂組成物係在230℃及3.8kg荷重之條件下測定而決定的熔體流速，較佳為0.1g/10分鐘以上，更佳為0.2~30g/10分鐘，尤佳為0.5~20g/10分鐘，最佳為1.0~10g/10分鐘。 The melt flow rate determined by measuring the methacrylic resin composition of the present invention at 230 ° C and a load of 3.8 kg is preferably 0.1 g/10 min or more, more preferably 0.2 to 30 g/10 min. It is 0.5 to 20 g/10 minutes, preferably 1.0 to 10 g/10 minutes.

又，本發明之甲基丙烯酸樹脂組成物係玻璃轉移溫度較佳為120℃以上，更佳為123℃以上，尤佳 為124℃以上。甲基丙烯酸樹脂組成物之玻璃轉移溫度的上限係沒有特別的限制，但較佳為130℃。 Further, the methacrylic resin composition of the present invention has a glass transition temperature of preferably 120 ° C or higher, more preferably 123 ° C or higher, and particularly preferably It is above 124 °C. The upper limit of the glass transition temperature of the methacrylic resin composition is not particularly limited, but is preferably 130 °C.

本發明之甲基丙烯酸樹脂組成物係為了提高保存、搬運或成形時的便利性，可成為丸粒(pellet)等之形態。 The methacrylic resin composition of the present invention can be in the form of a pellet or the like in order to improve convenience in storage, transportation, or molding.

本發明之成形體係由本發明的甲基丙烯酸樹脂組成物所構成。本發明之成形體的製造方法係沒有特別的限定。例如，可舉出T模頭法(積層法、共擠出法等)、吹脹法(共擠出法等)、壓縮成形法、吹塑成形法、壓延成形法、真空成形法、射出成形法(***法、二色法、加壓法、芯後退法、夾芯法等)等之熔融成形法以及溶液澆鑄法等。於此等之中，從生產性高、成本等之點來看，較佳為T模頭法、吹脹法或射出成形法。 The molding system of the present invention is composed of the methacrylic resin composition of the present invention. The method for producing the molded body of the present invention is not particularly limited. For example, a T-die method (such as a laminate method or a co-extrusion method), an inflation method (such as a co-extrusion method), a compression molding method, a blow molding method, a calender molding method, a vacuum molding method, and an injection molding method are mentioned. A melt molding method such as a method (insertion method, two-color method, pressurization method, core back-off method, sandwich method, etc.), a solution casting method, and the like. Among these, from the viewpoint of high productivity, cost, and the like, a T die method, an inflation method, or an injection molding method is preferred.

作為本發明之成形體的用途，例如可舉出廣告塔、立式招牌、袖形招牌、欄間招牌、屋頂招牌等之招牌零件；櫥窗、隔板、店舗展示等的展示器零件；螢光燈罩、氣氛照明罩、燈罩、光頂棚、光牆、吊燈等之照明零件；垂飾、鏡子等之室內裝飾零件；門、圓頂、安全窗玻璃、隔板、樓梯裙板，陽台裙板、休閒用建築物之屋頂等之建築用零件；航空機擋風、飛行員用遮陽帽、摩托車、汽艇擋風、巴士用遮光板、汽車用遮陽板、後遮陽板、頭翼、頭燈罩等之輸送機相關零件；音響映像用銘牌、立體音響外罩(stereo cover)、電視防護罩、自動販賣機用顯示器外罩等之電子機器零件；保育器、X光零件等之醫療機器零件；機械外罩、儀器外罩、 實驗裝置、尺、錶盤、觀察窗等之機器相關零件；顯示裝置之前燈用導光板及薄膜、背光用導光板及薄膜、液晶保護板、菲涅耳透鏡、雙凸透鏡、各種顯示器之前面板、擴散板、反射材料等之光學相關零件；道路標識、導引板、曲面鏡、隔音牆等之交通相關零件；汽車內裝用表面材料、行動電話之表面材料、標記薄膜等之薄膜構件；洗衣機篷材料或控制面板、電鍋的頂板等之家電製品用構件；以及，溫室、大型水槽、水槽箱、時鐘面板、浴缸、衛生設備(sanitary)、桌墊、遊戲零件、玩具、熔接時的臉部保護用面具等。 Examples of the use of the molded article of the present invention include signboard parts such as an advertising tower, a vertical signboard, a sleeve signboard, an inter-column signboard, and a roof signboard; display parts such as a window, a partition, and a shop display; and a fluorescent lamp cover. Lighting parts such as atmosphere lighting, lampshade, light ceiling, light wall, chandelier; interior decoration parts such as pendants and mirrors; doors, domes, safety window glass, partitions, stair skirts, balcony skirts, leisure Building parts such as roofs of buildings; aircraft windshield, pilot sun hat, motorcycle, motorboat windshield, bus visor, automotive sun visor, rear sun visor, head wing, headlight cover, etc. Related parts; electronic parts for sound image with nameplate, stereo cover, TV shield, monitor cover for vending machines; medical machine parts for incubators, X-ray parts, etc.; mechanical cover, instrument cover, Machine-related parts such as experimental devices, rulers, dials, observation windows, etc.; light guide plates and films for lamps before the display device, light guide plates and films for backlights, liquid crystal protection plates, Fresnel lenses, lenticular lenses, front panels for various displays, diffusion Optical related parts such as plates and reflective materials; traffic-related parts such as road signs, guide plates, curved mirrors, and soundproof walls; film materials for surface materials for automotive interiors, surface materials for mobile phones, and marking films; Components for home appliances such as materials or control panels, top plates of electric cookers; and, greenhouses, large sinks, sink boxes, clock panels, bathtubs, sanitary equipment, table mats, game parts, toys, and faces when welding Protective masks, etc.

本發明之成形體係透明性高，在寬廣的溫度範圍中霧度之變化小，玻璃轉移溫度高，厚度方向的相位差小，熱收縮率小，強度大且成形加工性優異。本發明之成形體例如可特別適宜使用於各種罩蓋、各種端子板、印刷配線板、揚聲器、顯微鏡、雙筒望遠鏡、照相機、時鐘等為代表的光學機器，且作為映像．光記錄．光通信．資訊機器關聯零件，照相機、VTR、投影TV等之取景器、濾光片、稜鏡、菲涅耳透鏡、各種光碟(VD、CD、DVD、MD、LD等)基板之保護膜、光開關、光連接器、液晶顯示器、液晶顯示器用導光膜．薄片、平面顯示器、平面顯示器用導光膜．薄片、電漿顯示器、電漿顯示器用導光膜．薄片、電子紙用導光膜．薄片、相位差薄膜．薄片、偏光薄膜．薄片、偏光板保護膜．薄片、偏光鏡保護膜．薄片、波長板、光擴散薄膜．薄片、稜鏡薄膜．薄片、反射薄膜．薄片、抗反射薄膜．薄 片、視角擴大薄膜．薄片、防眩薄膜．薄片、亮度提升薄膜．薄片、液晶或電致發光用途之顯示元件基板、觸控面板、觸控面板用導光膜．薄片、各種前面板與各種模組間之間隔物等各種的光學用途。再者，本發明之成形體例如可用於行動電話、數位資訊終端、呼叫器、導航、車載用液晶顯示器、液晶螢幕、調光面板、OA機器用顯示器、AV機器用顯示器等之各種液晶顯示元件或電致發光顯示元件或觸控面板等。又，從耐候性、柔軟性等優異之點來看，本發明之成形體例如亦可特別適宜使用於建築用內．外裝用構件、簾牆(curtain wall)、屋頂用構件、屋頂材、窗用構件、雨水溝、外部材類、牆壁材料、地板材料、修建材料、道路建設用構件、再度返回反射薄膜．薄片、農業用薄膜．薄片、照明罩、招牌、透光性隔音壁等眾所周知的建材用途。 The molding system of the present invention has high transparency, a small change in haze in a wide temperature range, a high glass transition temperature, a small phase difference in the thickness direction, a small heat shrinkage ratio, a large strength, and excellent moldability. The molded article of the present invention can be suitably used, for example, as an optical device represented by various covers, various terminal plates, printed wiring boards, speakers, microscopes, binoculars, cameras, clocks, etc., and as an image. Light recording. Optical Communication. Information machine related parts, camera, VTR, projection TV and other viewfinders, filters, cymbals, Fresnel lenses, various optical discs (VD, CD, DVD, MD, LD, etc.) substrate protective film, optical switch, Light guides for optical connectors, liquid crystal displays, and liquid crystal displays. Thin film, flat panel display, light guide film for flat panel display. Thin film, plasma display, light guide film for plasma display. Thin film, light guide film for electronic paper. Sheet, phase difference film. Sheet, polarized film. Sheet, polarizer protective film. Sheet, polarizer protective film. Sheet, wave plate, light diffusing film. Thin film, tantalum film. Sheet, reflective film. Sheet, anti-reflective film. thin Film, viewing angle expansion film. Sheet, anti-glare film. Thin film, brightness enhancement film. Display element substrate for sheet, liquid crystal or electroluminescence, touch panel, light guide film for touch panel. Various optical applications such as thin sheets, various front panels, and spacers between various modules. Further, the molded article of the present invention can be used, for example, in various liquid crystal display elements such as mobile phones, digital information terminals, pagers, navigation, vehicle-mounted liquid crystal displays, liquid crystal screens, dimming panels, OA machine displays, and AV machine displays. Or an electroluminescent display element or a touch panel or the like. Moreover, the molded article of the present invention can be suitably used, for example, in construction, from the viewpoint of excellent weather resistance, flexibility, and the like. Exterior components, curtain wall, roofing members, roofing materials, window members, rain gutters, exterior materials, wall materials, flooring materials, construction materials, road construction components, re-reflective film. Thin film, agricultural film. Well-known building materials such as sheets, lighting covers, signboards, and translucent soundproof walls.

本發明之薄膜係由本發明的甲基丙烯酸樹脂組成物所構成。從減小厚度方向的相位差的觀點來看，本發明之薄膜較佳為由含有1~9質量%、更佳2~7質量%、尤佳3~6質量%之聚碳酸酯樹脂的本發明之甲基丙烯酸樹脂組成物所構成。 The film of the present invention is composed of the methacrylic resin composition of the present invention. The film of the present invention is preferably a polycarbonate resin containing 1 to 9% by mass, more preferably 2 to 7% by mass, and particularly preferably 3 to 6% by mass, from the viewpoint of reducing the phase difference in the thickness direction. The composition of the methacrylic resin composition of the invention.

本發明之薄膜係可藉由溶液澆鑄法、熔融流延法、擠壓成形法、吹脹成形法、吹塑成形法等來製造。於此等之中，從能得到透明性優異、具有經改善的韌性、操作性優異、韌性與表面硬度及剛性的平衡優異之薄膜的觀點來看，較佳為擠壓成形法。自擠壓機所吐出的甲基丙烯酸樹脂組成物之溫度較佳為設定在160~270℃，更 佳為在220~260℃。 The film of the present invention can be produced by a solution casting method, a melt casting method, an extrusion molding method, an inflation molding method, a blow molding method, or the like. Among these, from the viewpoint of obtaining a film excellent in transparency, improved toughness, excellent workability, and excellent balance between toughness and surface hardness and rigidity, an extrusion molding method is preferred. The temperature of the methacrylic resin composition discharged from the extruder is preferably set at 160 to 270 ° C, Jia is at 220~260°C.

於擠壓成形法之中，從得到良好的表面平滑性、良好的鏡面光澤、低霧度之薄膜的觀點來看，較佳為包含將甲基丙烯酸樹脂組成物以熔融狀態自T模頭擠出，其次以二個以上的鏡面輥或鏡面帶夾持以進行成形之方法。鏡面輥或鏡面帶較佳為金屬製。一對的鏡面輥或鏡面帶之間的線壓較佳為10N/mm以上，更佳為30N/mm以上。 Among the extrusion molding methods, from the viewpoint of obtaining a film having good surface smoothness, good specular gloss, and low haze, it is preferred to contain the methacrylic resin composition in a molten state from the T die. Next, a method of sandwiching two or more mirror rolls or mirror belts for forming. The mirror roll or mirror belt is preferably made of metal. The line pressure between the pair of mirror rollers or mirror belts is preferably 10 N/mm or more, more preferably 30 N/mm or more.

又，鏡面輥或鏡面帶之表面溫度較佳為皆130℃以下。又，一對的鏡面輥或鏡面帶較佳為至少一者之表面溫度係60℃以上。若設定在如此的表面溫度，則可將自擠壓機所吐出的甲基丙烯酸樹脂組成物以比自然放置冷卻更快的速度冷卻，容易製造表面平滑性優異且霧度低的薄膜。由擠壓成形所得之未延伸薄膜的厚度較佳為10~300μm。薄膜之霧度係在100μm的厚度時較佳為0.5%以下，更佳為0.3%以下。 Further, the surface temperature of the mirror roll or the mirror strip is preferably 130 ° C or less. Further, it is preferable that at least one of the pair of mirror rollers or the mirror belt has a surface temperature of 60 ° C or higher. When such a surface temperature is set, the methacrylic resin composition discharged from the extruder can be cooled at a faster rate than natural place cooling, and a film having excellent surface smoothness and low haze can be easily produced. The thickness of the unstretched film obtained by extrusion molding is preferably from 10 to 300 μm. The haze of the film is preferably 0.5% or less, more preferably 0.3% or less, in the case of a thickness of 100 μm.

本發明之薄膜亦可為施有延伸處理者。施有延伸處理的薄膜，係具有高的機械強度，且難以龜裂。延伸處理之方法係沒有特別的限定，可舉出單軸延伸法、同時雙軸延伸法、逐次雙軸延伸法、管形延伸法等。從可均勻地延伸，得到高強度的薄膜之觀點來看，延伸時之溫度較佳為100~200℃，更佳為120℃~160℃。延伸通常係以長度基準，用100~5000%/分鐘進行。於延伸之後，藉由進行熱固定，可得到熱收縮少之薄膜。 The film of the present invention may also be applied to an extension processor. The film subjected to the elongation treatment has high mechanical strength and is difficult to crack. The method of the stretching treatment is not particularly limited, and examples thereof include a uniaxial stretching method, a simultaneous biaxial stretching method, a sequential biaxial stretching method, and a tubular stretching method. From the viewpoint of being uniformly stretchable and obtaining a high-strength film, the temperature at the time of stretching is preferably from 100 to 200 ° C, more preferably from 120 ° C to 160 ° C. The extension is usually carried out on a length basis of 100 to 5000%/min. After the stretching, a film having less heat shrinkage can be obtained by heat setting.

本發明之薄膜係其厚度沒有特別的限制 ，但作為光學薄膜使用時之厚度，較佳為1~300μm，更佳為10~50μm，尤佳為15~40μm。 The film of the present invention has no particular limitation on its thickness. However, the thickness when used as an optical film is preferably from 1 to 300 μm, more preferably from 10 to 50 μm, still more preferably from 15 to 40 μm.

本發明之薄膜係厚度50μm時之霧度較佳為0.2%以下，更佳為0.1%以下。藉此，表面光澤或透明性優異。又，於液晶保護膜或導光膜等之光學用途中，光源之利用效率高而較佳。再者，由於在進行表面賦形之際的賦形精度優異而較佳。 The haze of the film of the present invention at a thickness of 50 μm is preferably 0.2% or less, more preferably 0.1% or less. Thereby, surface gloss or transparency is excellent. Further, in optical applications such as a liquid crystal protective film or a light guiding film, the use efficiency of the light source is high, and it is preferable. Further, it is preferable because the forming accuracy is excellent at the time of surface forming.

亦可於本發明之薄膜的表面上設置機能層。作為機能層，可舉出硬塗層、防耀眼層、抗反射層、沾黏(sticking)防止層、擴散層、防眩層、抗靜電層、防污層、微粒子等之易滑性層等。 A functional layer may also be provided on the surface of the film of the present invention. Examples of the functional layer include a hard coat layer, an antiglare layer, an antireflection layer, a sticking preventing layer, a diffusion layer, an antiglare layer, an antistatic layer, an antifouling layer, and a slippery layer such as fine particles. .

<硬塗層> <hard coating>

硬塗層係具有將本發明之薄膜的表面予以高硬度化而保護之機能的層。硬塗層係可自習知者之中適宜選擇而使用。作為硬塗層，較佳為由硬化性樹脂組成物之硬化物所構成的層。作為可適用作為硬塗層的硬化性樹脂，只要是電離放射線硬化性樹脂、其它眾所周知的硬化性樹脂等符合所要求的性能等，則可適宜採用。作為電離放射線硬化性樹脂，可舉出丙烯酸酯系、氧雜環丁烷系、聚矽氧系等。例如，丙烯酸酯系的電離放射線硬化性樹脂係由單官能(甲基)丙烯酸酯單體、2官能(甲基)丙烯酸酯單體單體、3官能以上的(甲基)丙烯酸酯單體等之(甲基)丙烯酸酯單體、胺基甲酸酯(甲基)丙烯酸酯、環氧(甲基)丙烯酸酯、聚酯(甲基)丙烯酸酯等之(甲基)丙烯酸酯寡聚物或(甲基)丙烯酸酯預聚物等所構成。再者，作 為3官能以上的(甲基)丙烯酸酯單體，例如可舉出三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯等。硬塗層係藉由將含有上述硬化性樹脂的硬塗層用樹脂組成物直接塗布於本發明之薄膜上，或塗布於已塗布有底漆層的本發明之薄膜的底漆層面上，進行硬化而。 The hard coat layer has a function of imparting high hardness to the surface of the film of the present invention to protect it. The hard coat layer can be suitably selected from the conventional ones. The hard coat layer is preferably a layer composed of a cured product of a curable resin composition. The curable resin to be used as the hard coat layer can be suitably used as long as it is an ionizing radiation curable resin or other well-known curable resin and the like. Examples of the ionizing radiation curable resin include an acrylate type, an oxetane type, and a polyfluorene type. For example, the acrylate-based ionizing radiation curable resin is a monofunctional (meth) acrylate monomer, a bifunctional (meth) acrylate monomer monomer, a trifunctional or higher (meth) acrylate monomer, or the like. (meth) acrylate oligomers such as (meth) acrylate monomers, urethane (meth) acrylates, epoxy (meth) acrylates, polyester (meth) acrylates Or a (meth) acrylate prepolymer or the like. Again, Examples of the trifunctional or higher (meth) acrylate monomer include trimethylolpropane tri(meth) acrylate, pentaerythritol tetra(meth) acrylate, dipentaerythritol hexa(meth) acrylate, and the like. . The hard coat layer is applied by directly applying the resin composition for a hard coat layer containing the curable resin to the film of the present invention or to the primer layer of the film of the present invention to which the primer layer has been applied. Hardened.

<抗反射層> <anti-reflection layer>

抗反射層係防止外來光之因鏡面反射而映入背景之層。於本發明之薄膜的表面上所積層的抗反射層，係可自習知的抗反射層之中適宜選擇而使用。作為抗反射層，例如可舉出交替地積層高折射率層與低折射率層，以最表面成為低折射率層之方式所多層化(多道塗布)之樹脂層，或形成微細凹凸形狀等之奈米結構的抗反射層等。作為上述高折射率層，可舉出含有鈦、鉭、鋯、銦等的金屬氧化物微粒子之高折射率層形成用樹脂組成物及其硬化物等。又，作為上述低折射率層，可舉出氟系的樹脂、或含有中空矽石微粒子等的低折射率層形成用樹脂組成物及其硬化物等。藉由使用此等之抗反射層，因干涉而抵消在層界面的反射光，抑制表面之反射，可成為得到良好的抗反射效果之抗反射層等。又，藉由使前述硬塗層成為比經該硬塗層所保護的薄膜之折射率更低的折射率者，可對於硬塗層賦予抗反射機能。 The anti-reflective layer prevents the external light from being reflected into the background layer due to specular reflection. The antireflection layer laminated on the surface of the film of the present invention can be suitably selected and used among conventional antireflection layers. Examples of the antireflection layer include a resin layer in which a high refractive index layer and a low refractive index layer are alternately laminated, and a multilayered (multi-coated) layer is formed so that the outermost surface is a low refractive index layer, or a fine uneven shape is formed. Anti-reflective layer of nano structure. The high refractive index layer may be a resin composition for forming a high refractive index layer containing fine particles of metal oxide such as titanium, tantalum, zirconium or indium, a cured product thereof, or the like. In addition, examples of the low refractive index layer include a fluorine-based resin or a resin composition for forming a low refractive index layer such as hollow vermiculite fine particles, a cured product thereof, and the like. By using such an anti-reflection layer, the reflected light at the layer interface is cancelled by the interference, and the reflection of the surface is suppressed, so that an antireflection layer or the like which has a good antireflection effect can be obtained. Further, by making the hard coat layer have a lower refractive index than that of the film protected by the hard coat layer, an antireflection function can be imparted to the hard coat layer.

<防眩層> <anti-glare layer>

防眩層係使外來光散射或擴散之層。例如，藉由將光的入射面予以粗面化，可擴散外來光。於此粗面化處 理中，可舉出如噴砂法或壓花法等等之在基體表面本身形成微細凹凸而粗面化之方法，在基體表面上塗布含有矽石等的無機填料或/及樹脂粒子等的有機填料之放射線硬化性或熱硬化性的樹脂組成物以形成微細凹凸塗膜而粗面化之方法，塗布能形成海島結構的樹脂組成物以形成多孔質膜而粗面化之方法等。作為所塗布的樹脂組成物中使用之樹脂，從提高表面層的強度之觀點來看，較宜使用硬化性丙烯酸樹脂或在上述硬塗層中能使用的電離放射線硬化性樹脂等。 The anti-glare layer is a layer that scatters or diffuses extraneous light. For example, external light can be diffused by roughening the incident surface of light. Here In the case of a sandblasting method, an embossing method, or the like, a method of forming fine irregularities on the surface of the substrate itself to roughen the surface, and applying an inorganic filler such as vermiculite or the like and organic particles to the surface of the substrate may be mentioned. A method of forming a resin composition capable of forming a sea-island structure to form a porous film and roughening it by coating a resin composition having a radiation-curable or thermosetting property of a filler to form a fine uneven coating film. As the resin to be used in the resin composition to be applied, from the viewpoint of improving the strength of the surface layer, a curable acrylic resin or an ionizing radiation curable resin which can be used in the above hard coat layer is preferably used.

<抗靜電層> <antistatic layer>

為了抑制本發明之薄膜的靜電，亦可設置抗靜電層。抗靜電層係可自習知者中適宜選擇而使用。例如，藉由於上述硬塗層用的樹脂組成物中，混合眾所周知的抗靜電劑而使用，可成為抗靜電層。作為抗靜電劑之具體例，可舉出四級銨鹽、吡啶鎓鹽、具有一級~三級胺基等之陽離子性基的各種陽離子性化合物、具有磺酸鹽基、硫酸酯鹽基、磷酸酯鹽基、膦酸鹽基等之陰離子性基的陰離子性化合物、胺基酸系、胺基硫酸酯系等之兩性化合物、胺基醇系、甘油系、聚乙二醇系等之非離子性化合物、如錫及鈦之烷氧化物的有機金屬化合物及如彼等之乙醯丙酮酸鹽的金屬螯合化合物等，更且可舉出上述列舉的化合物經高分子量化之化合物。又，可使用具有三級胺基、四級銨基或金屬螯合部且藉由電離放射線可聚合之單體或寡聚物、或具有藉由電離放射線可聚合的官能基且如偶合劑之有機金屬化合物等的聚合性化合 物作為抗靜電劑。又，作為抗靜電劑，亦可使用導電性聚合物或奈米管、銀奈米線等。 In order to suppress the static electricity of the film of the present invention, an antistatic layer may also be provided. The antistatic layer can be suitably selected from the conventional ones. For example, the resin composition for a hard coat layer can be used as an antistatic layer by mixing a well-known antistatic agent. Specific examples of the antistatic agent include various cationic compounds having a quaternary ammonium salt, a pyridinium salt, and a cationic group having a primary to tertiary amino group, and a sulfonate group, a sulfate group, and a phosphoric acid. An anionic compound such as an ester group or a phosphonate group; an amphoteric compound such as an amino acid or an amine sulfate; or a nonionic such as an amino alcohol, a glycerin or a polyethylene glycol; Examples of the compound, an organometallic compound such as an alkoxide of tin and titanium, and a metal chelate compound such as acetoacetate of the same, and the compound of the above-exemplified compound are polymerized. Further, a monomer or oligomer having a tertiary amino group, a quaternary ammonium group or a metal chelate portion and polymerizable by ionizing radiation, or a functional group polymerizable by ionizing radiation and using a coupling agent may be used. Polymerization of organometallic compounds, etc. As an antistatic agent. Further, as the antistatic agent, a conductive polymer, a nanotube tube, a silver nanowire or the like can also be used.

於本發明之薄膜的表面上亦可設置接著劑層。作為構成接著劑層的接著劑，例如可使用水系接著劑、溶劑系接著劑、熱熔系接著劑、活性能量線硬化型接著劑等。於此等之中，水系接著劑及活性能量線硬化型接著劑係較宜。 An adhesive layer may also be provided on the surface of the film of the present invention. As the adhesive agent constituting the adhesive layer, for example, a water-based adhesive, a solvent-based adhesive, a hot-melt adhesive, an active energy ray-curable adhesive, or the like can be used. Among these, a water-based adhesive and an active energy ray-curable adhesive are preferred.

本發明之甲基丙烯酸樹脂組成物由於雙折射性小，容易得到面內方向相位差或厚度方向相位差小的薄膜。當薄膜的厚度為40μm時，本發明之薄膜係對於波長590nm的光之面內方向相位差Re較佳為5nm以下，更佳為4nm以下，尤佳為3nm以下，特佳為2nm以下，最佳為1nm以下。又，當薄膜的厚度為40μm時，本發明之薄膜係對於波長590nm的光之厚度方向相位差Rth較佳為-5nm以上5nm以下，更佳為-4nm以上4nm以下，尤佳為-3nm以上3nm以下，特佳為-2nm以上2nm以下，最佳為-1nm以上1nm以下。 Since the methacrylic resin composition of the present invention has a small birefringence, it is easy to obtain a film having a phase difference in the in-plane direction or a phase difference in the thickness direction. When the thickness of the film is 40 μm, the phase difference Re of the film in the in-plane direction of light having a wavelength of 590 nm is preferably 5 nm or less, more preferably 4 nm or less, still more preferably 3 nm or less, and particularly preferably 2 nm or less. Preferably, it is 1 nm or less. Further, when the thickness of the film is 40 μm, the film of the present invention has a phase difference Rth in the thickness direction of light having a wavelength of 590 nm of preferably -5 nm or more and 5 nm or less, more preferably -4 nm or more and 4 nm or less, and particularly preferably -3 nm or more. 3 nm or less is particularly preferably -2 nm or more and 2 nm or less, and most preferably -1 nm or more and 1 nm or less.

面內方向相位差及厚度方向相位差若在如此的範圍內，則可顯著地抑制因相位差所造成的對於圖像顯示裝置之顯示特性的影響。更具體而言，可顯著地抑制干涉不均或用於3D顯示器用液晶顯示裝置時的3D影像之歪斜。再者，面內方向相位差Re及厚度方向相位差Rth各自係由下式所定義之值。 When the in-plane direction phase difference and the thickness direction phase difference are within such a range, the influence on the display characteristics of the image display device due to the phase difference can be remarkably suppressed. More specifically, the skew of the 3D image when the interference unevenness or the liquid crystal display device for a 3D display is used can be remarkably suppressed. Further, the in-plane direction phase difference Re and the thickness direction phase difference Rth are each a value defined by the following formula.

Re=(nx-ny)×d Re=(n x -n y )×d

Rth=((nx+ny)/2-nz)×d Rth=((n x +n y )/2-n z )×d

此處，nx係薄膜的遲相軸方向之折射率，ny係薄膜的進相軸方向之折射率，nz係薄膜的厚度方向之折射率，d(nm)係薄膜之厚度。遲相軸係指薄膜面內的折射率成為最大之方向，進相軸係指在面內垂直於遲相軸之方向。 Here, the refractive index of the n x based film in the slow axis direction, the refractive index of the n y type film in the direction of the phase axis, the refractive index of the thickness direction of the n z type film, and the thickness of the d (nm) film. The retardation axis refers to the direction in which the refractive index in the plane of the film becomes maximum, and the phase axis refers to the direction perpendicular to the slow axis in the plane.

本發明之甲基丙烯酸樹脂組成物係可成形為具有高透明性與高耐熱性且薄之薄膜。本發明之薄膜係適合偏光鏡保護膜、相位差薄膜、液晶保護板、攜帶型資訊終端之表面材料、攜帶型資訊終端之顯示窗保護膜、導光膜、在表面上塗布有銀奈米線或奈米管的透明導電薄膜、各種顯示器之前面板等。尤其，由本發明所得之相位差小的薄膜係適合偏光鏡保護膜。又，本發明之薄膜係可使用於IR截止薄膜、防止犯罪薄膜、防飛散薄膜、裝飾薄膜、金屬裝飾薄膜、太陽電池的背板、可撓性太陽電池用前板、收縮薄膜、模內標籤用薄膜、窗膜、阻氣薄膜之基礎薄膜等。 The methacrylic resin composition of the present invention can be formed into a thin film having high transparency and high heat resistance. The film of the invention is suitable for a polarizer protective film, a retardation film, a liquid crystal protection board, a surface material of a portable information terminal, a display window protection film of a portable information terminal, a light guiding film, and a silver nanowire coated on the surface thereof. Or a transparent conductive film of a nanotube, a front panel of various displays, and the like. In particular, the film having a small phase difference obtained by the present invention is suitable for a polarizer protective film. Further, the film of the present invention can be used for an IR cut film, a crime prevention film, a scattering prevention film, a decorative film, a metal decorative film, a back sheet for a solar cell, a front plate for a flexible solar cell, a shrink film, an in-mold label A film, a window film, a base film of a gas barrier film, or the like.

使用本發明之薄膜作為偏光鏡保護膜或相位差薄膜時，可僅在偏光鏡薄膜的單面上積層，也可在兩面上積層。與偏光鏡薄膜積層時，可隔著接著層或黏著層進行積層。作為偏光鏡薄膜，可使用由聚乙烯醇系樹脂與碘所成之延伸薄膜，其膜厚為1μm~100μm。 When the film of the present invention is used as a polarizer protective film or a retardation film, it may be laminated only on one surface of the polarizing film or may be laminated on both surfaces. When laminating with the polarizing film, it can be laminated via an adhesive layer or an adhesive layer. As the polarizing film, a stretched film made of a polyvinyl alcohol-based resin and iodine can be used, and the film thickness thereof is from 1 μm to 100 μm.

使用本發明之偏光鏡保護膜的偏光板，係包含至少1片的本發明之偏光鏡保護膜。較佳為由聚乙烯醇系樹脂所形成的偏光鏡與本發明之偏光鏡保護膜隔著接著劑層積層而成。 The polarizing plate using the polarizer protective film of the present invention contains at least one of the polarizer protective films of the present invention. Preferably, the polarizer formed of a polyvinyl alcohol-based resin and the polarizer protective film of the present invention are laminated with an adhesive layer interposed therebetween.

本發明之較佳的一實施形態的偏光板係 如第1圖所示，於偏光鏡11的一側之面，依順序積層接著劑層12及本發明之偏光鏡保護膜14，於偏光鏡11的另一側之面，依順序積層接著劑層15及光學薄膜16而成。於與接著劑層12接觸的本發明之偏光鏡保護膜14的表面，亦可設置易接著層13(參照第2圖)，於本發明的偏光鏡保護膜14之情況，即使不設置易接著層13，也可適宜地保持接著性。設置易接著層13時，於接著劑層12與偏光鏡保護膜14之接著性成為更良好之點較佳，但於生產性與成本之點差。 A preferred embodiment of the polarizing plate of the present invention As shown in FIG. 1, the adhesive layer 12 and the polarizer protective film 14 of the present invention are laminated on the surface of one side of the polarizer 11, and the adhesive is laminated on the other side of the polarizer 11 in this order. The layer 15 and the optical film 16 are formed. The surface of the polarizer protective film 14 of the present invention which is in contact with the adhesive layer 12 may be provided with an easy-adhesion layer 13 (see FIG. 2). In the case of the polarizer protective film 14 of the present invention, even if it is not provided, it is easy to follow. The layer 13 can also suitably maintain the adhesion. When the easy-adhesion layer 13 is provided, it is preferable that the adhesion between the adhesive layer 12 and the polarizer protective film 14 is better, but the difference between productivity and cost.

由上述聚乙烯醇系樹脂所形成的偏光鏡，例如係藉由以二色性物質(代表為碘、二色性染料)來染色聚乙烯醇系樹脂薄膜，進行單軸延伸而得。聚乙烯醇系樹脂薄膜係可藉由將聚乙烯醇系樹脂以任意適當的方法(例如將在水或有機溶劑中溶解有樹脂的溶液予以流延成膜之流延法、澆鑄法、擠壓法)製膜而得。 The polarizer formed of the above polyvinyl alcohol-based resin is obtained by, for example, dyeing a polyvinyl alcohol-based resin film with a dichroic substance (represented as iodine or a dichroic dye) and performing uniaxial stretching. The polyvinyl alcohol-based resin film can be cast by a suitable method (for example, a casting method in which a solution in which a resin is dissolved in water or an organic solvent is cast into a film, casting method, extrusion) Method) obtained by film formation.

該聚乙烯醇系樹脂係聚合度較佳為100~8000，更佳為1400~6000。又，用於偏光鏡的聚乙烯醇系樹脂薄膜之厚度，係可按照使用偏光板的LCD之目的或用途來適宜設定，代表性為1~80μm。 The degree of polymerization of the polyvinyl alcohol-based resin is preferably from 100 to 8,000, more preferably from 1400 to 6,000. Moreover, the thickness of the polyvinyl alcohol-based resin film used for the polarizer can be appropriately set according to the purpose or use of the LCD using a polarizing plate, and is typically 1 to 80 μm.

使用本發明之偏光鏡保護膜的偏光板中可設置之接著劑層，只要是光學透明則沒有特別的限制。作為構成接著劑層的接著劑，例如可使用水系接著劑、溶劑系接著劑、熱熔系接著劑、UV硬化型接著劑等。於此等之中，水系接著劑及UV硬化型接著劑較宜。 The adhesive layer which can be provided in the polarizing plate using the polarizer protective film of the present invention is not particularly limited as long as it is optically transparent. As the adhesive constituting the adhesive layer, for example, a water-based adhesive, a solvent-based adhesive, a hot-melt adhesive, a UV-curable adhesive, or the like can be used. Among these, a water-based adhesive and a UV-curable adhesive are preferred.

作為水系接著劑，並沒有特別的限定，例 如可例示乙烯基聚合物系、明膠系、乙烯系乳膠系、聚胺基甲酸酯系、異氰酸酯系、聚酯系、環氧系等。於如此的水系接著劑中，視需要亦可摻合交聯劑或其它的添加劑、酸等之觸媒。作為前述水系接著劑，較佳為使用含有乙烯基聚合物的接著劑等，作為乙烯基聚合物，較佳為聚乙烯醇系樹脂。又，於聚乙烯醇系樹脂中，可含有硼酸或硼砂、戊二醛或三聚氰胺、草酸等之水溶***聯劑。尤其，使用聚乙烯醇系的聚合物薄膜作為偏光鏡時，從接著性之點來看，較佳為使用含有聚乙烯醇系樹脂的接著劑。再者，從提高耐久性之點來看，更佳為包含具有乙醯乙醯基的聚乙烯醇系樹脂之接著劑。前述水系接著劑通常係作為由水溶液所成的接著劑使用，通常含有0.5~60重量%的固體成分而成。 The water-based adhesive is not particularly limited, and examples thereof are not particularly limited. For example, a vinyl polymer type, a gelatin type, a vinyl type latex type, a polyurethane type, an isocyanate type, a polyester type, an epoxy type, etc. are illustrated. In such a water-based adhesive, a crosslinking agent or other additives, an acid or the like may be blended as needed. As the water-based adhesive, an adhesive containing a vinyl polymer or the like is preferably used, and as the vinyl polymer, a polyvinyl alcohol-based resin is preferable. Further, the polyvinyl alcohol-based resin may contain a water-soluble crosslinking agent such as boric acid or borax, glutaraldehyde or melamine or oxalic acid. In particular, when a polyvinyl alcohol-based polymer film is used as the polarizer, it is preferable to use an adhesive containing a polyvinyl alcohol-based resin from the viewpoint of adhesion. Further, from the viewpoint of improving durability, an adhesive containing a polyvinyl alcohol-based resin having an ethyl acetate group is more preferable. The water-based adhesive is usually used as an adhesive agent formed from an aqueous solution, and usually contains 0.5 to 60% by weight of a solid component.

又，於前述接著劑中，可含有金屬化合物填料。藉由金屬化合物填料，可控制接著劑層之流動性，將膜厚安定化，具有良好的外觀，得到面內均勻且接著性無偏差之偏光板。 Further, a metal compound filler may be contained in the above-mentioned adhesive. By the metal compound filler, the fluidity of the adhesive layer can be controlled, the film thickness can be stabilized, and a good appearance can be obtained, and a polarizing plate having uniform in-plane and no deviation in adhesion can be obtained.

接著劑層之形成方法係沒有特別的限制。例如，可藉由將上述接著劑塗布於對象物，其次加熱或乾燥而形成。接著劑之塗布係可對於本發明的偏光鏡保護膜或光學薄膜進行，也可對於偏光鏡進行。形成接著劑層後，藉由壓合偏光鏡保護膜或光學薄膜與偏光鏡，可積層兩者。於積層中，可使用輥壓機或平板壓機等。加熱乾燥溫度、乾燥時間係按照接著劑的種類來適宜決定。 The method of forming the subsequent layer is not particularly limited. For example, it can be formed by applying the above-mentioned adhesive agent to an object, followed by heating or drying. The coating of the subsequent agent may be performed on the polarizer protective film or the optical film of the present invention, or may be performed on a polarizing mirror. After the formation of the adhesive layer, both of them can be laminated by laminating a polarizer protective film or an optical film and a polarizing mirror. In the laminate, a roll press or a plate press or the like can be used. The heating and drying temperature and the drying time are appropriately determined depending on the type of the adhesive.

接著劑層之厚度係在乾燥狀態下較佳為0.01~10μm，更佳為0.03~5μm。 The thickness of the subsequent layer is preferably from 0.01 to 10 μm, more preferably from 0.03 to 5 μm in the dry state.

對於使用本發明之偏光鏡保護膜的偏光板可施予的易接著處理，係提高偏光鏡保護膜與偏光鏡接觸面之接著性。作為易接著處理，可舉出電暈處理、電漿處理、低壓UV處理等之表面處理。 The easy-to-handle treatment which can be applied to the polarizing plate using the polarizer protective film of the present invention improves the adhesion between the polarizer protective film and the polarizing mirror contact surface. As the easy-to-handle treatment, surface treatment such as corona treatment, plasma treatment, and low-pressure UV treatment may be mentioned.

又，亦可設置易接著層。作為易接著層，例如可舉出具有反應性官能基的聚矽氧層。具有反應性官能基的聚矽氧層之材料，係沒有特別的限制，但例如可舉出含有異氰酸酯基的烷氧基矽烷醇類、含有胺基的烷氧基矽烷醇類、含有巰基的烷氧基矽烷醇類、含有羧基的烷氧基矽烷醇類、含有環氧基的烷氧基矽烷醇類、含有乙烯基型不飽和基的烷氧基矽烷醇類、含有鹵基的烷氧基矽烷醇類、含有異氰酸酯基的烷氧基矽烷醇類。於此等之中，較佳為胺基系矽烷醇。藉由將用以使矽烷醇高效率地反應的鈦系觸媒或錫系觸媒加到上述矽烷醇中，可使接著力成為強固。又，於上述具有反應性官能基的聚矽氧中，亦可添加其它的添加劑。作為其它的添加劑，可舉出萜烯樹脂、酚樹脂、萜烯-酚樹脂、松香樹脂、二甲苯樹脂等之增黏劑，紫外線吸收劑、抗氧化劑、耐熱安定劑等之安定劑等。另外，作為易接著層，亦可舉出由纖維素乙酸丁酸酯樹脂經皂化者所構成的層。 Also, an easy-to-back layer can be provided. As the easy-adhesion layer, for example, a polyfluorene oxide layer having a reactive functional group can be mentioned. The material of the polyfluorene oxide layer having a reactive functional group is not particularly limited, and examples thereof include alkoxystanols containing an isocyanate group, alkoxystanols containing an amine group, and alkane-containing alkane. Oxol stanols, carboxyl group-containing alkoxystanols, epoxy group-containing alkoxystanols, vinyl group-containing unsaturated alkoxystanols, halogen group-containing alkoxy groups A stanol or an alkoxystanol containing an isocyanate group. Among these, an amino group stanol is preferred. By adding a titanium-based catalyst or a tin-based catalyst for efficiently reacting stanol in the above stanol, the bonding force can be made strong. Further, other additives may be added to the above-mentioned polyfluorene oxide having a reactive functional group. Examples of other additives include a tackifier such as a terpene resin, a phenol resin, a terpene-phenol resin, a rosin resin, and a xylene resin, and a stabilizer such as an ultraviolet absorber, an antioxidant, and a heat stabilizer. Further, as the easy-adhesion layer, a layer composed of a cellulose acetate butyrate resin by saponification may also be mentioned.

上述易接著層係藉由眾所周知的技術，塗布、乾燥而形成。易接著層之厚度係在乾燥狀態下較佳為1~100nm，更佳為10~50nm。塗布時，亦可用溶劑稀 釋易接著層形成用藥液。稀釋溶劑係沒有特別的限制，但可舉出醇類。稀釋濃度係沒有特別的限制，但較佳為1~5質量%，更佳為1~3質量%。 The above-mentioned easy-to-adhere layer is formed by coating and drying by a well-known technique. The thickness of the easy-adhesion layer is preferably from 1 to 100 nm, more preferably from 10 to 50 nm in a dry state. When coating, it can also be diluted with solvent The release layer forms a drug solution. The diluent solvent is not particularly limited, and examples thereof include alcohols. The dilution concentration is not particularly limited, but is preferably from 1 to 5% by mass, more preferably from 1 to 3% by mass.

光學薄膜16係可為本發明之偏光鏡保護膜，也可為其它任意適當的光學薄膜。光學薄膜係可發揮偏光鏡保護機能、亮度提升機能、視角調節機能、光擴散機能等之機能。光學薄膜係不受其材料所特別限制，例如可舉出由纖維素樹脂、聚碳酸酯樹脂、環狀聚烯烴樹脂、甲基丙烯酸樹脂、聚對苯二甲酸乙二酯樹脂等所構成的薄膜。 The optical film 16 may be the polarizer protective film of the present invention, or may be any other suitable optical film. The optical film system can function as a polarizer protection function, a brightness enhancement function, a viewing angle adjustment function, a light diffusion function, and the like. The optical film is not particularly limited as long as it is a material, and examples thereof include a film composed of a cellulose resin, a polycarbonate resin, a cyclic polyolefin resin, a methacrylic resin, a polyethylene terephthalate resin, or the like. .

纖維素樹脂係纖維素與脂肪酸之酯。作為如此的纖維素酯系樹脂之具體例，可舉出纖維素三乙酸酯、纖維素二乙酸酯、纖維素三丙酸酯、纖維素二丙酸酯等。於此等之中，特佳為纖維素三乙酸酯。纖維素三乙酸酯係市售有許多製品，於取得容易性或成本之點亦有利。作為纖維素三乙酸酯的市售品之例，可舉出富士軟片公司製的商品名「UV-50」、「UV-80」、「SH-80」、「TD-80U」、「TD-TAC」、「UZ-TAC」、或Konica-Minolta公司製的「KC系列」等。 The cellulose resin is an ester of cellulose and a fatty acid. Specific examples of such a cellulose ester-based resin include cellulose triacetate, cellulose diacetate, cellulose tripropionate, and cellulose dipropionate. Among them, cellulose triacetate is particularly preferred. Cellulose triacetate is commercially available in many products and is advantageous in terms of ease of availability or cost. Examples of commercially available products of cellulose triacetate include "UV-50", "UV-80", "SH-80", "TD-80U", and "TD" manufactured by Fujifilm Co., Ltd. -TAC", "UZ-TAC", or "KC Series" made by Konica-Minolta.

環狀聚烯烴樹脂係以環狀烯烴作為聚合單元而聚合的樹脂之總稱，例如可舉出日本特開平1-240517號公報、日本特開平3-14882號公報、日本特開平3-122137號公報等中記載的樹脂。作為具體例，可舉出環狀烯烴的開環(共)聚合物、環狀烯烴的加成聚合物、環狀烯烴與乙烯、丙烯等之α-烯烴的共聚物(代表為無 規共聚物)、及此等經不飽和羧酸或其衍生物所改性的接枝聚合物、以及彼等之氫化物等。作為環狀烯烴之具體例，可舉出降烯系單體。 The cyclic polyolefin resin is a general term for a resin which is polymerized by using a cyclic olefin as a polymerization unit, and is disclosed in Japanese Unexamined Patent Application Publication No. Hei No. Hei No. Hei. The resin described in the above. Specific examples thereof include a ring-opened (co)polymer of a cyclic olefin, an addition polymer of a cyclic olefin, and a copolymer of a cyclic olefin and an α-olefin such as ethylene or propylene (represented as a random copolymer). And graft polymers modified with unsaturated carboxylic acids or derivatives thereof, and their hydrides and the like. Specific examples of the cyclic olefin include a drop An olefinic monomer.

作為環狀聚烯烴樹脂，市售有各種的製品。作為具體例，可舉出日本ZEON股份有限公司製之商品名「Zeonex」、「Zeonor」、JSR股份有限公司製之商品名「Arton」、POLYPLASTICS股份有限公司製之商品名「Topas」、三井化學股份有限公司製之商品名「APEL」。 As the cyclic polyolefin resin, various products are commercially available. Specific examples include the product name "Zeonex" manufactured by Japan ZEON Co., Ltd., "Zeonor", the product name "Arton" manufactured by JSR Co., Ltd., the product name "Topas" manufactured by POLYPLASTICS Co., Ltd., and Mitsui Chemicals Co., Ltd. The product name "APEL" manufactured by the company limited by shares.

作為構成光學薄膜16的甲基丙烯酸樹脂，在不損害本發明的效果之範圍內，可採用任意適當的甲基丙烯酸樹脂。例如，可舉出聚甲基丙烯酸甲酯等之聚甲基丙烯酸酯、甲基丙烯酸甲酯-(甲基)丙烯酸共聚、甲基丙烯酸甲酯-(甲基)丙烯酸酯共聚物、甲基丙烯酸甲酯-丙烯酸酯-(甲基)丙烯酸共聚物、(甲基)丙烯酸甲酯-苯乙烯共聚物(MS樹脂等)、具有脂環族烴基的聚合物(例如，甲基丙烯酸甲酯-甲基丙烯酸環己酯共聚物、甲基丙烯酸甲酯-(甲基)丙烯酸降酯共聚物等)。 As the methacrylic resin constituting the optical film 16, any appropriate methacrylic resin can be employed as long as the effects of the present invention are not impaired. For example, polymethacrylate such as polymethyl methacrylate, methyl methacrylate-(meth)acrylic copolymer, methyl methacrylate-(meth) acrylate copolymer, methacrylic acid Methyl ester-acrylate-(meth)acrylic acid copolymer, methyl (meth)acrylate-styrene copolymer (MS resin, etc.), polymer having an alicyclic hydrocarbon group (for example, methyl methacrylate-A) Cyclohexyl acrylate copolymer, methyl methacrylate-(meth) acrylate Ester copolymers, etc.).

作為構成光學薄膜16的甲基丙烯酸樹脂之具體例，例如可舉出三菱麗陽股份有限公司製之Acrypet VH或Acrypet VRL20A、日本特開2013-033237或WO2013/005634號公報中記載之共聚合有甲基丙烯酸甲酯與馬來醯亞胺系單體的丙烯酸樹脂、WO2005/108438號公報中記載之在分子內具有環結構的丙烯酸樹脂、日本特開2009-197151號公報中記載之在分 子內具有環結構的甲基丙烯酸樹脂、藉由分子內交聯或分子內環化反應而得之高玻璃轉移溫度(Tg)甲基丙烯酸樹脂。 Specific examples of the methacrylic resin constituting the optical film 16 include, for example, a copolymer of Acrypet VH or Acrypet VRL 20A manufactured by Mitsubishi Rayon Co., Ltd., and JP-A-2013-033237 or WO 2013/005634. An acrylic resin of a methyl methacrylate and a maleic imine monomer, an acrylic resin having a ring structure in a molecule described in WO2005/108438, and a Japanese Patent Application Publication No. 2009-197151 A methacrylic resin having a ring structure, a high glass transition temperature (Tg) methacrylic resin obtained by intramolecular crosslinking or intramolecular cyclization.

作為構成光學薄膜16的甲基丙烯酸樹脂，亦可使用具有內酯環結構的甲基丙烯酸樹脂。此係因為高耐熱性、高透明性、藉由雙軸延伸而具有高機械強度。 As the methacrylic resin constituting the optical film 16, a methacrylic resin having a lactone ring structure can also be used. This is because of high heat resistance, high transparency, and high mechanical strength by biaxial stretching.

作為具有內酯環結構的甲基丙烯酸樹脂，可舉出日本特開2000-230016號公報、日本特開2001-151814號公報、日本特開2002-120326號公報、日本特開2002-254544號公報、日本特開2005-146084號公報等中記載之具有內酯環結構的甲基丙烯酸樹脂。 Japanese Patent Publication No. 2000-230016 A methacrylic resin having a lactone ring structure described in JP-A-2005-146084 or the like.

作為構成光學薄膜16的聚對苯二甲酸乙二酯樹脂，可舉出WO2011-162198號公報、WO2015-037527號公報、WO2007-020909號公報、日本特開2010-204630號公報等中記載之聚對苯二甲酸乙二酯樹脂。 The polyethylene terephthalate resin constituting the optical film 16 is exemplified in WO2011-162198, WO2015-037527, WO2007-020909, and JP-A-2010-204630. Ethylene terephthalate resin.

使用本發明之偏光鏡保護膜的偏光板，係可使用於圖像顯示裝置。作為圖像顯示裝置之具體例，可舉出如電致發光(EL)顯示器、電漿顯示器(PD)、電場發射顯示器(FED：Field Emission Display)之自發光型顯示裝置、液晶顯示裝置。液晶顯示裝置具有液晶胞與在該液晶胞的至少一側上配置之上述偏光板。 A polarizing plate using the polarizer protective film of the present invention can be used for an image display device. Specific examples of the image display device include a self-luminous display device such as an electroluminescence (EL) display, a plasma display (PD), and an electric field emission display (FED: Field Emission Display), and a liquid crystal display device. The liquid crystal display device has a liquid crystal cell and the above-described polarizing plate disposed on at least one side of the liquid crystal cell.

以下，藉由實施例及比較例來具體說明本發明，惟本發明不受下述實施例所限定。 Hereinafter, the present invention will be specifically described by way of examples and comparative examples, but the present invention is not limited by the following examples.

(聚合轉化率) (polymerization conversion rate)

於島津製作所公司製氣相層析儀GC-14A中，連結GL Sciences Inc.製Inert CAP 1(df=0.4μm、I.D.=0.25mm、長度=60m)作為管柱，注射溫度為180℃，檢測器溫度為180℃，將管柱溫度在60℃保持5分鐘，自60℃起以10℃/分鐘的升溫速度升溫至200℃為止，在200℃保持10分鐘之條件下測定，根據其結果，算出聚合轉化率。 In the gas chromatograph GC-14A manufactured by Shimadzu Corporation, Inert CAP 1 (df = 0.4 μm, ID = 0.25 mm, length = 60 m) manufactured by GL Sciences Inc. was used as a column, and the injection temperature was 180 ° C. The temperature of the tube was 180 ° C, the column temperature was maintained at 60 ° C for 5 minutes, the temperature was raised from 200 ° C to 200 ° C at a temperature increase rate of 10 ° C / minute, and the temperature was measured at 200 ° C for 10 minutes. Calculate the polymerization conversion rate.

(重量平均分子量Mw、重量平均分子量Mw/數量平均分子量Mn、高分子量成分含量及低分子量成分含量) (weight average molecular weight Mw, weight average molecular weight Mw / number average molecular weight Mn, high molecular weight component content, and low molecular weight component content)

藉由凝膠滲透層析術(GPC)，於下述條件下測定層析圖，算出經換算成標準聚苯乙烯的分子量之值。基線係連接GPC圖的高分子量側之波峰的斜率自保持時間快者來看由零變成正之點、與低分子量側之波峰的斜率自保持時間快者來看由負變成零之點的線。自使用校正曲線所算出的積分分子量分布，算出分子量小於15000的成分(低分子量成分)之比例與分子量200000以上的成分(高分子量成分)之比例。 The chromatogram was measured by gel permeation chromatography (GPC) under the following conditions, and the value of the molecular weight converted into standard polystyrene was calculated. The slope of the peak on the high molecular weight side of the GPC map connected to the baseline is a line from zero to a positive point, and a slope from a negative to zero point in the slope of the peak on the low molecular weight side from the fast hold time. From the integrated molecular weight distribution calculated using the calibration curve, the ratio of the ratio of the component having a molecular weight of less than 15,000 (low molecular weight component) to the component having a molecular weight of 200,000 or more (high molecular weight component) was calculated.

GPC裝置：東曹股份有限公司製HLC-8320 GPC device: HTC-8320 manufactured by Tosoh Corporation

檢測器：差示折射率檢測器 Detector: Differential Index Detector

管柱：使用串聯連接有東曹股份有限公司製的TSKgel SuperMultipore HZM-M2兩支與SuperHZ4000者。 Pipe column: Two TSKgel SuperMultipore HZM-M2 manufactured by Tosoh Corporation and SuperHZ4000 are connected in series.

洗提劑：四氫呋喃 Eluent: tetrahydrofuran

洗提劑流量：0.35ml/分鐘 Stripping agent flow rate: 0.35ml/min

管柱溫度：40℃ Column temperature: 40 ° C

校正曲線：使用標準聚苯乙烯10點的數據來作成 Calibration curve: using standard polystyrene 10 points data to create

(三元組表示之間規性(rr)) (Triple indicates the regularity (rr))

使用核磁共振裝置(Bruker公司製ULTRA SHIELD 400 PLUS)，使用重氫化氯仿作為溶劑，在室溫、累計次數64次之條件下，測定1H-NMR光譜。自該光譜，計測TMS成為0ppm時的0.6~0.95ppm之區域的面積A0與0.6~1.35ppm之區域的面積AY，其次，以式：(A0/AY)×100算出三元組表示之間規性(rr)。 The 1 H-NMR spectrum was measured using a nuclear magnetic resonance apparatus (ULTRA SHIELD 400 PLUS manufactured by Bruker) and using hydrogenated chloroform as a solvent at room temperature and a cumulative number of 64 times. From the spectrum, the area A 0 of the region of 0.6 to 0.95 ppm and the area A Y of the region of 0.6 to 1.35 ppm when TMS was 0 ppm were measured, and then, the triad was calculated by the formula: (A 0 /A Y )×100. Indicates the regularity (rr).

(玻璃轉移溫度Tg) (glass transition temperature Tg)

依據JIS K7121，使用差示掃描熱量測定裝置(島津製作所製DSC-50(型號))，一次升溫至230℃為止，其次冷卻至室溫為止，然後於自室溫起至230℃為止以10℃/分鐘使其升溫之條件下，測定DSC曲線。將自第2次的升溫時測定之DSC曲線所求得的中間點玻璃轉移溫度作為本發明中的玻璃轉移溫度。 According to JIS K7121, a differential scanning calorimeter (DSC-50 (model) manufactured by Shimadzu Corporation) was used, and the temperature was raised to 230 ° C once, and then cooled to room temperature, and then 10 ° C from room temperature to 230 ° C. The DSC curve was measured under the conditions that the temperature was raised in minutes. The intermediate point glass transition temperature obtained from the DSC curve measured at the second temperature rise is taken as the glass transition temperature in the present invention.

(甲基丙烯酸樹脂(A)、嵌段共聚物(B)之折射率n23D) (Metal acid resin (A), block copolymer (B) refractive index n 23D )

藉由加壓成形來製作3cm×3cm、厚度3mm的薄片，使用KALNEW光學工業股份有限公司「KPR-200」，在23℃、50%RH下以波長587.6nm(D線)測定折射率n23D。 A sheet of 3 cm × 3 cm and a thickness of 3 mm was produced by press molding, and the refractive index n 23D was measured at a wavelength of 587.6 nm (D line) at 23 ° C and 50% RH using KALNEW Optical Industries Co., Ltd. "KPR-200". .

(熔體質量流速(MFR)) (melt mass flow rate (MFR))

依據JIS K7210，在230℃、3.8kg荷重、10分鐘之條件下測定。 According to JIS K7210, it was measured at 230 ° C under a load of 3.8 kg for 10 minutes.

製造例1(甲基丙烯酸樹脂[A-1]之製造) Production Example 1 (Manufacture of methacrylic resin [A-1])

以氮氣置換安裝有攪拌翼與三通旋塞之5L的玻璃製反應容器內。於其中，在室溫下加入1600g甲苯、 2.49g(10.8mmol)1,1,4,7,10,10-六甲基三伸乙四胺、53.5g(30.9mmol)濃度0.45M的異丁基雙(2,6-二第三丁基-4-甲基苯氧基)鋁之甲苯溶液及6.17g(10.3mmol)濃度1.3M的第二丁基鋰之溶液(溶劑：環己烷95%、正己烷5%)。一邊攪拌，一邊於其中在20℃費30分鐘滴下550g經蒸餾精製的甲基丙烯酸甲酯。滴下結束後，在25℃攪拌90分鐘。溶液之顏色係自黃色變成無色。此時間點的甲基丙烯酸甲酯之聚合轉化率為100%。於所得之溶液中加入1500g甲苯而稀釋。其次，將該稀釋液注入100kg甲醇中，得到沉澱物。將所得之沉澱物在80℃、140Pa下乾燥24小時，得到MwA 79400、MwA/MnA 1.08、間規性(rr)70%、玻璃轉移溫度130℃低分子量成分含量0.19質量%、高分子量成分含量0.02質量%、MFR0.9g/10分鐘、n23D1.489及來自甲基丙烯酸甲酯的結構單元之含量100質量%的甲基丙烯酸樹脂[A-1]。 A 5 L glass reaction vessel equipped with a stirring blade and a three-way cock was replaced with nitrogen. Among them, 1600 g of toluene, 2.49 g (10.8 mmol) of 1,1,4,7,10,10-hexamethyltrimethylenetetramine, 53.5 g (30.9 mmol) of 0.45 M of isobutylene were added at room temperature. a solution of bis(2,6-di-t-butyl-4-methylphenoxy)aluminum in toluene and 6.17 g (10.3 mmol) of a 1.3 M solution of a second butyllithium (solvent: cyclohexane 95) %, n-hexane 5%). While stirring, 550 g of distilled purified methyl methacrylate was added dropwise thereto at 20 ° C for 30 minutes. After the completion of the dropwise addition, the mixture was stirred at 25 ° C for 90 minutes. The color of the solution changed from yellow to colorless. The polymerization conversion ratio of methyl methacrylate at this time point was 100%. The obtained solution was diluted by adding 1500 g of toluene. Next, the diluted solution was poured into 100 kg of methanol to obtain a precipitate. The obtained precipitate was dried at 80 ° C and 140 Pa for 24 hours to obtain Mw A 79400, Mw A /Mn A 1.08, syndiotacticity (rr) 70%, glass transition temperature of 130 ° C, low molecular weight component content of 0.19% by mass, and high. The methacrylic resin [A-1] having a molecular weight component content of 0.02% by mass, MFR of 0.9 g/10 min, n 23D 1.489, and a content of 100% by mass of a structural unit derived from methyl methacrylate.

製造例2(甲基丙烯酸樹脂[A-2]之製造) Production Example 2 (Manufacture of methacrylic resin [A-2])

以氮氣置換安裝有攪拌機及採集管的高壓釜內。於其中加入100質量份的經精製之甲基丙烯酸甲酯、0.0052質量份的2,2’-偶氮雙(2-甲基丙腈(奪氫能力：1%，1小時半衰期溫度：83℃)及0.23質量份的正辛基硫醇，攪拌而得到原料液。將氮氣送入該原料液中，去除原料液中的溶存氧。 The autoclave in which the mixer and the collection tube were installed was replaced with nitrogen. 100 parts by mass of purified methyl methacrylate and 0.0052 parts by mass of 2,2'-azobis(2-methylpropionitrile) (hydrogen-capturing capacity: 1%, 1 hour half-life temperature: 83 ° C) And 0.23 parts by mass of n-octyl mercaptan was stirred to obtain a raw material liquid, and nitrogen gas was fed into the raw material liquid to remove dissolved oxygen in the raw material liquid.

於與高壓釜經配管所連接的槽型反應器中，置入原料液直到容量的2/3為止。將溫度維持在140℃，首先以分批方式開始聚合反應。於聚合轉化率成為55質量%時 ，以成為平均滯留時間150分鐘之流量，自高壓釜將原料液供給至槽型反應器，且以相當於原料液的供給流量之流量，自槽型反應器中抽出反應液，將反應器內的反應液溫度維持在溫度140℃，切換成連續流通方式的聚合反應。切換後，穩定狀態的聚合轉化率為55質量%。 In the tank reactor connected to the autoclave via piping, the raw material liquid was placed until 2/3 of the capacity. The temperature was maintained at 140 ° C, and the polymerization was first started in a batch mode. When the polymerization conversion ratio is 55 mass% The raw material liquid is supplied from the autoclave to the tank reactor at a flow rate of an average residence time of 150 minutes, and the reaction liquid is withdrawn from the tank type reactor at a flow rate corresponding to the supply flow rate of the raw material liquid, and the inside of the reactor is taken. The temperature of the reaction solution was maintained at a temperature of 140 ° C, and was switched to a polymerization reaction in a continuous flow mode. After the switching, the polymerization conversion rate in the steady state was 55 mass%.

將自成為穩定狀態的槽型反應器所抽出的反應液，以成為平均滯留時間2分鐘之流量，供給至內溫230℃的多管式熱交換器而加溫。其次，將經加溫的反應液導入閃蒸器中，去除以未反應單體作為主成分的揮發分，得到熔融樹脂。將揮發分經去除的熔融樹脂供給至內溫260℃的雙軸擠壓機，吐出股條狀，用造粒機切割，得到MwA 101000、MwA/MnA 1.87、間規性(rr)52%、玻璃轉移溫度120℃、低分子量成分含量2.54質量%、高分子量成分含量0.73質量%、MFR 1.6g/10分鐘、n23D1.491及來自甲基丙烯酸甲酯的結構單元含量100質量%之丸粒狀甲基丙烯酸樹脂[A-2]。 The reaction liquid extracted from the tank reactor in a stable state was supplied to a multi-tube heat exchanger having an internal temperature of 230 ° C to be heated at a flow rate of 2 minutes in an average residence time. Next, the heated reaction liquid is introduced into a flasher, and volatile matter containing unreacted monomers as a main component is removed to obtain a molten resin. The molten resin obtained by removing the volatile matter was supplied to a biaxial extruder having an internal temperature of 260 ° C, spun out, and cut by a granulator to obtain Mw A 101000, Mw A /Mn A 1.87, and syndiotacticity (rr). 52%, glass transition temperature 120 ° C, low molecular weight component content 2.54% by mass, high molecular weight component content 0.73 mass%, MFR 1.6 g/10 min, n 23D 1.491, and structural unit content from methyl methacrylate 100% by mass Pellet methacrylic resin [A-2].

製造例3(甲基丙烯酸樹脂[A-3]之製造) Production Example 3 (Manufacture of methacrylic resin [A-3])

混合57質量份的甲基丙烯酸樹脂[A-1]及43質量份的甲基丙烯酸樹脂[A-2]，以雙軸擠壓機(TECHNOVEL(股)製，商品名：KZW20TW-45MG-NH-600)在250℃混煉擠出，得到MwA 88600、MwA/MnA 1.32、間規性(rr)62%、玻璃轉移溫度126℃、低分子量成分含量1.20質量%、高分子量成分含量0.33質量%、MFR 1.3g/10分鐘、n23D1.489及來自甲基丙烯酸甲酯的結構單元含量100質量%之丸粒狀甲基丙烯酸樹脂[A-3]。 57 parts by mass of methacrylic resin [A-1] and 43 parts by mass of methacrylic resin [A-2] were mixed in a twin-screw extruder (TECHNOVEL, trade name: KZW20TW-45MG-NH) -600) kneading at 250 ° C to obtain Mw A 88600, Mw A /Mn A 1.32, syndiotacticity (rr) 62%, glass transition temperature 126 ° C, low molecular weight component content 1.20 mass%, high molecular weight component content 0.33 mass%, MFR 1.3 g/10 min, n 23D 1.489, and pelletized methacrylic resin [A-3] having a structural unit content of 100% by mass from methyl methacrylate.

製造例4(甲基丙烯酸樹脂[A-4]之製造) Production Example 4 (Manufacture of methacrylic resin [A-4])

於100質量份的甲基丙烯酸甲酯中，加入0.07質量份的聚合起始劑(2,2’-偶氮雙(2,4-二甲基戊腈)、奪氫能力：1%，10小時半衰期溫度：51℃)及0.26質量份的鏈轉移劑(正辛基硫醇)，使其溶解而得到原料液。 0.07 parts by mass of a polymerization initiator (2,2'-azobis(2,4-dimethylvaleronitrile), hydrogen abstracting ability: 1%, 10 in 100 parts by mass of methyl methacrylate The hourly half-life temperature: 51 ° C) and 0.26 parts by mass of a chain transfer agent (n-octyl mercaptan) were dissolved to obtain a raw material liquid.

於100質量份的離子交換水中混合0.03質量份的硫酸鈉及0.46質量份的懸浮分散劑而得到混合液。 0.03 parts by mass of sodium sulfate and 0.46 parts by mass of a suspension dispersant were mixed in 100 parts by mass of ion-exchanged water to obtain a mixed solution.

於耐壓聚合槽中，加入420質量份的前述混合液與210質量份的前述原料液。在氮氣環境下邊攪拌，邊使溫度成為60℃而開始聚合反應。於自聚合反應開始起4小時經過時，將溫度提高至70℃，在70℃繼續進行攪拌1小時，得到分散有珠狀微粒子的分散液。自該分散液濾取微粒子，以離子交換水洗淨該微粒子，其次在80℃、100Pa下減壓乾燥4小時，得到MwA 89700、MwA/MnA 1.91、間規性(rr)60%、玻璃轉移溫度124℃、MFR 1.3g/10分鐘、n23D1.489、低分子量成分含量2.91質量%、高分子量成分含量0.38質量%及來自甲基丙烯酸甲酯的結構單元含量100質量%之珠狀的甲基丙烯酸樹脂[A-4]。 To the pressure-resistant polymerization tank, 420 parts by mass of the above mixed liquid and 210 parts by mass of the above raw material liquid were added. The polymerization was started while stirring at a temperature of 60 ° C under a nitrogen atmosphere. When the temperature was 4 hours from the start of the polymerization, the temperature was raised to 70 ° C, and stirring was continued at 70 ° C for 1 hour to obtain a dispersion in which bead fine particles were dispersed. The fine particles were collected from the dispersion, and the fine particles were washed with ion-exchanged water, and then dried under reduced pressure at 80 ° C and 100 Pa for 4 hours to obtain Mw A 89700, Mw A /Mn A 1.91, and syndiotacticity (rr) 60%. , glass transition temperature of 124 ° C, MFR 1.3 g / 10 min, n 23D 1.489, low molecular weight component content of 2.91% by mass, high molecular weight component content of 0.38% by mass, and 100% by mass of structural unit content of methyl methacrylate Methacrylic resin [A-4].

製造例5(甲基丙烯酸樹脂[A-5]之製造) Production Example 5 (Manufacture of methacrylic resin [A-5])

於85質量份的甲基丙烯酸甲酯及15質量份的丙烯酸甲酯中，加入0.10質量份的聚合起始劑(2,2’-偶氮雙(2-甲基丙腈)，奪氫能力：1%，1小時半衰期溫度：83℃)及0.2質量份的鏈轉移劑(正辛基硫醇)，使其溶解而得到原料液。 0.10 parts by mass of a polymerization initiator (2,2'-azobis(2-methylpropionitrile) was added to 85 parts by mass of methyl methacrylate and 15 parts by mass of methyl acrylate to obtain hydrogen. : 1%, 1 hour half-life temperature: 83 ° C) and 0.2 parts by mass of a chain transfer agent (n-octyl mercaptan) were dissolved to obtain a raw material liquid.

於100質量份的離子交換水中混合0.03質量份的硫 酸鈉及0.46質量份的懸浮分散劑而得到混合液。 Mixing 0.03 parts by mass of sulfur in 100 parts by mass of ion-exchanged water Sodium acetate and 0.46 parts by mass of a suspension dispersant were used to obtain a mixed solution.

於耐壓聚合槽中，加入420質量份的前述混合液與210質量份的前述原料液。在氮氣環境下邊攪拌，邊使溫度成為70℃而開始聚合反應。於自聚合反應開始起3小時經過時，將溫度提高至90℃，在90℃繼續進行攪拌1小時，得到分散有珠狀微粒子的分散液。自該分散液濾取微粒子，以離子交換水洗淨該微粒子，其次在80℃、100Pa下減壓乾燥4小時，得到MwA 107000、MwA/MnA 1.91、間規性(rr)58%、玻璃轉移溫度100℃、低分子量成分含量2.23質量%、高分子量成分含量0.63質量%、MFR 1.2g/10分鐘、n23D1.490及來自甲基丙烯酸甲酯的結構單元含量85質量%之珠狀的甲基丙烯酸樹脂[A-5]。 To the pressure-resistant polymerization tank, 420 parts by mass of the above mixed liquid and 210 parts by mass of the above raw material liquid were added. The polymerization was started while stirring at a temperature of 70 ° C under a nitrogen atmosphere. When the temperature was 3 hours from the start of the polymerization, the temperature was raised to 90 ° C, and stirring was continued at 90 ° C for 1 hour to obtain a dispersion in which bead fine particles were dispersed. The fine particles were collected from the dispersion, and the fine particles were washed with ion-exchanged water, and then dried under reduced pressure at 80 ° C and 100 Pa for 4 hours to obtain Mw A 107000, Mw A /Mn A 1.91, and syndiotacticity (rr) 58%. , glass transition temperature of 100 ° C, low molecular weight component content of 2.23 mass%, high molecular weight component content of 0.63 mass%, MFR of 1.2 g/10 min, n 23D 1.490 and the content of structural unit derived from methyl methacrylate of 85 mass% Methacrylic resin [A-5].

製造例6(甲基丙烯酸樹脂[A-6]之製造) Production Example 6 (Manufacture of methacrylic resin [A-6])

以氮氣置換安裝有攪拌翼與三通旋塞之5L的玻璃製反應容器內。於其中，在室溫下加入1600g甲苯、3.19g(13.9mmol)1,1,4,7,10,10-六甲基三伸乙四胺、68.6g(39.6mmol)濃度0.45M的異丁基雙(2,6-二第三丁基-4-甲基苯氧基)鋁之甲苯溶液及7.91g(13.2mmol)濃度1.3M的第二丁基鋰之溶液(溶劑：環己烷95質量%、正己烷5質量%)。一邊攪拌，一邊於其中在20℃費30分鐘滴下550g經蒸餾精製的甲基丙烯酸甲酯。滴下結束後，在20℃攪拌90分鐘。溶液之顏色係自黃色變成無色。此時間點的甲基丙烯酸甲酯之聚合轉化率為100%。 A 5 L glass reaction vessel equipped with a stirring blade and a three-way cock was replaced with nitrogen. Among them, 1600 g of toluene, 3.19 g (13.9 mmol) of 1,1,4,7,10,10-hexamethyltrimethylenetetramine, 68.6 g (39.6 mmol) of 0.45 M of isobutylene were added at room temperature. a solution of bis(2,6-di-t-butyl-4-methylphenoxy)aluminum in toluene and a solution of 7.91 g (13.2 mmol) of a 1.3 M solution of second butyllithium (solvent: cyclohexane 95) Mass%, n-hexane 5 mass%). While stirring, 550 g of distilled purified methyl methacrylate was added dropwise thereto at 20 ° C for 30 minutes. After the completion of the dropwise addition, the mixture was stirred at 20 ° C for 90 minutes. The color of the solution changed from yellow to colorless. The polymerization conversion ratio of methyl methacrylate at this time point was 100%.

於所得之溶液中加入1500g甲苯而稀釋。其次，將該稀釋液注入100kg甲醇中，得到沉澱物。將所得之沉澱物 在80℃、140Pa下乾燥24小時，得到MwA 58900、MwA/MnA 1.06、間規性(rr)74%、玻璃轉移溫度130℃、低分子量成分含量0.02質量%、高分子量成分含量0.01質量%、MFR 2.1g/10分鐘、n23D1.489及來自甲基丙烯酸甲酯的結構單元含量100質量%之甲基丙烯酸樹脂[A-6]。 The obtained solution was diluted by adding 1500 g of toluene. Next, the diluted solution was poured into 100 kg of methanol to obtain a precipitate. The obtained precipitate was dried at 80 ° C and 140 Pa for 24 hours to obtain Mw A 58900, Mw A /Mn A 1.06, syndiotacticity (rr) of 74%, glass transition temperature of 130 ° C, and low molecular weight component content of 0.02% by mass. The methacrylic resin [A-6] having a high molecular weight component content of 0.01% by mass, MFR of 2.1 g/10 min, n 23D 1.489, and a structural unit content of methyl methacrylate of 100% by mass.

製造例7(甲基丙烯酸樹脂[A-7]之製造) Production Example 7 (Manufacture of methacrylic resin [A-7])

事先調製將馬來酸酐以成為20質量%濃度之方式在甲基異丁基酮中溶解之20%馬來酸酐溶液，與將第三丁基過氧-2-乙基己酸酯以成為2質量%之方式在甲基異丁基酮中稀釋之2%第三丁基過氧-2-乙基己酸酯溶液，使用於聚合。 A 20% maleic anhydride solution in which maleic anhydride is dissolved in methyl isobutyl ketone in a concentration of 20% by mass is prepared in advance, and the third butyl peroxy-2-ethylhexanoate is used as 2 A 2% by weight solution of 2% t-butylperoxy-2-ethylhexanoate diluted in methyl isobutyl ketone for polymerization.

於具備攪拌機的10L高壓釜中，加入28g 20%馬來酸酐溶液、224g苯乙烯、130g甲基丙烯酸甲酯、0.4g三級十二基硫醇，以氮氣置換氣相部後，邊攪拌邊費40分鐘升溫至88℃為止。升溫後邊保持88℃，邊各連續地費8小時，以21g/小時之速度繼續添加20%馬來酸酐溶液，及以3.75g/小時之速度繼續添加2%第三丁基過氧-2-乙基己酸酯溶液。然後，停止2%第三丁基過氧-2-乙基己酸酯溶液之添加，添加0.4g第三丁基過氧異丙基單碳酸酯。20%馬來酸酐溶液係一邊照樣維持21g/小時之添加，一邊以8℃/小時的升溫速度費4小時升溫至120℃為止。20%馬來酸酐溶液之添加係在添加量累計成為252g之時間點停止。升溫後，1小時保持120℃，於結束聚合的聚合液中加入3000g甲苯而稀釋。其次，將該稀釋液注入200kg甲醇內，得到沉澱物。將所得之沉澱物在80℃、140Pa下乾燥 24小時，得到甲基丙烯酸樹脂[A-7]。實施13C-NMR分析，結果所得之樹脂的組成係來自甲基丙烯酸甲酯的結構單元為26質量%，具有環狀結構的來自馬來酸酐的結構單元為18質量%，來自苯乙烯的結構單元為56質量%。 In a 10 L autoclave equipped with a stirrer, 28 g of a 20% maleic anhydride solution, 224 g of styrene, 130 g of methyl methacrylate, and 0.4 g of a tertiary dodecyl mercaptan were added, and the gas phase portion was replaced with nitrogen, followed by stirring. The temperature was raised to 88 ° C for 40 minutes. After heating up, the temperature was maintained at 88 ° C, and each was continuously charged for 8 hours. The 20% maleic anhydride solution was continuously added at a rate of 21 g / hour, and the 2% tert-butylperoxy-2- was continuously added at a rate of 3.75 g / hour. Ethyl hexanoate solution. Then, the addition of a 2% solution of t-butylperoxy-2-ethylhexanoate was stopped, and 0.4 g of t-butyl peroxyisopropyl monocarbonate was added. The 20% maleic anhydride solution was heated to 120 ° C for 4 hours at a temperature increase rate of 8 ° C / hour while maintaining the addition of 21 g / hour. The addition of the 20% maleic anhydride solution was stopped at the time when the added amount was 252 g cumulatively. After the temperature was raised, the temperature was maintained at 120 ° C for 1 hour, and 3000 g of toluene was added to the polymerization liquid in which the polymerization was completed, and the mixture was diluted. Next, the diluted solution was poured into 200 kg of methanol to obtain a precipitate. The obtained precipitate was dried at 80 ° C and 140 Pa for 24 hours to obtain a methacrylic resin [A-7]. 13 C-NMR analysis was carried out, and the obtained resin was obtained from a structural unit of methyl methacrylate of 26% by mass, and a structural unit derived from maleic anhydride having a cyclic structure of 18% by mass. Structure derived from styrene. The unit was 56% by mass.

所得之樹脂為Mw：169000、Mw/Mn：2.47、Tg：137℃。 The obtained resin was Mw: 169000, Mw/Mn: 2.47, Tg: 137 °C.

表1中顯示甲基丙烯酸樹脂(A-1)~(A-7)之物性。 Table 1 shows the physical properties of the methacrylic resins (A-1) to (A-7).

於以下所示的製造例8~13中，化合物係使用藉由常見方法進行乾燥精製，經氮氣脫氣者。又，化合物的移送及供給係在氮氣環境下進行。 In Production Examples 8 to 13 shown below, the compound was subjected to dry purification by a usual method and degassed by nitrogen. Further, the transfer and supply of the compound were carried out under a nitrogen atmosphere.

製造例8(二嵌段共聚物[B-1]之製造) Production Example 8 (manufacture of diblock copolymer [B-1])

於內部脫氣，經氮氣置換的三口燒瓶中，在室溫下置入735g乾燥甲苯、0.4g六甲基三伸乙四胺及39.4g含有 異丁基雙(2,6-二第三丁基-4-甲基苯氧基)鋁20mmol的甲苯溶液。於其中加入1.17mmol的第二丁基鋰。再者，於其中加入39.0g甲基丙烯酸甲酯，在室溫下反應1小時而得到甲基丙烯酸甲酯聚合物(b11)。反應液中所含有的甲基丙烯酸甲酯聚合物(b11)之重量平均分子量Mwb11為45800。 After degassing internally, a nitrogen-replaced three-necked flask was charged with 735 g of dry toluene, 0.4 g of hexamethyltrimethylenetetramine, and 39.4 g of isobutyl bis(2,6-di-third butyl) at room temperature. A solution of 20 mmol of toluene in 4-methylphenoxy)aluminum. 1.17 mmol of the second butyllithium was added thereto. Further, 39.0 g of methyl methacrylate was added thereto, and the mixture was reacted at room temperature for 1 hour to obtain a methyl methacrylate polymer (b1 1 ). The weight average molecular weight Mw b11 of the methyl methacrylate polymer (b1 1 ) contained in the reaction liquid was 45,800.

其次，使反應液成為-25℃，費0.5小時滴下29.0g丙烯酸正丁酯及10.0g丙烯酸苄酯的混合液，自甲基丙烯酸甲酯聚合物(b11)之末端起，繼續聚合反應，得到自甲基丙烯酸甲酯聚合物嵌段(b11)與由丙烯酸正丁酯及丙烯酸苄酯所成的丙烯酸酯聚合物嵌段(b2)所構成之二嵌段共聚物[B-1]。反應液中所含有的嵌段共聚物[B-1]係重量平均分子量MwB為92000，重量平均分子量MwB/數量平均分子量MnB為1.06。由於甲基丙烯酸甲酯聚合物(b11)之重量平均分子量為45800，將由丙烯酸正丁酯及丙烯酸苄酯所成的丙烯酸酯聚合物(b2)之重量平均分子量斷定為46200。丙烯酸酯聚合物(b2)中所含有的丙烯酸苄酯之比例為25.6質量%。 Next, the reaction liquid was brought to -25 ° C, and a mixture of 29.0 g of n-butyl acrylate and 10.0 g of benzyl acrylate was added dropwise over 0.5 hours, and the polymerization was continued from the end of the methyl methacrylate polymer (b1 1 ). a diblock copolymer obtained from a methyl methacrylate polymer block (b1 1 ) and an acrylate polymer block (b2) composed of n-butyl acrylate and benzyl acrylate [B-1] . The block copolymer [B-1] contained in the reaction liquid had a weight average molecular weight Mw B of 92,000, and a weight average molecular weight Mw B / number average molecular weight Mn B of 1.06. Since the weight average molecular weight of the methyl methacrylate polymer (b1 1 ) was 45,800, the weight average molecular weight of the acrylate polymer (b2) composed of n-butyl acrylate and benzyl acrylate was determined to be 46,200. The ratio of the benzyl acrylate contained in the acrylate polymer (b2) was 25.6% by mass.

繼續，於反應液中添加4g甲醇而使聚合停止。然後，將反應液注入大量的甲醇中而使二嵌段共聚物[B-1]析出，濾取該析出物，在80℃、1torr(約133Pa)下乾燥12小時。所得之二嵌段共聚物[B-1]的n23D為1.490。甲基丙烯酸酯聚合物嵌段(b11)的質量相對於丙烯酸酯聚合物嵌段(b2)的質量之比為50/50。 Further, 4 g of methanol was added to the reaction liquid to stop the polymerization. Then, the reaction solution was poured into a large amount of methanol to precipitate a diblock copolymer [B-1], and the precipitate was collected by filtration, and dried at 80 ° C and 1 torr (about 133 Pa) for 12 hours. The n 23D of the obtained diblock copolymer [B-1] was 1.490. The ratio of the mass of the methacrylate polymer block (b1 1 ) to the mass of the acrylate polymer block (b2) was 50/50.

製造例9(二嵌段共聚物[B-2]之製造) Production Example 9 (Production of Diblock Copolymer [B-2])

除了將甲基丙烯酸甲酯之量改變為78g，將丙烯酸正丁酯之量改變為58g，將丙烯酸苄酯之量改變為20g以外，以與製造例7相同之方法得到自甲基丙烯酸甲酯聚合物嵌段(b11)與由丙烯酸正丁酯及丙烯酸苄酯所成的丙烯酸酯聚合物(b2)所構成之二嵌段共聚物[B-2]。 Methyl methacrylate was obtained in the same manner as in Production Example 7, except that the amount of methyl methacrylate was changed to 78 g, the amount of n-butyl acrylate was changed to 58 g, and the amount of benzyl acrylate was changed to 20 g. A diblock copolymer [B-2] composed of a polymer block (b1 1 ) and an acrylate polymer (b2) composed of n-butyl acrylate and benzyl acrylate.

甲基丙烯酸甲酯聚合物嵌段(b11)係Mwb11為74300。丙烯酸酯聚合物(b2)係Mwb2為81700，丙烯酸苄酯之比例為25.6質量%。二嵌段共聚物[B-2]係MwB為156000，MwB/MnB為1.08，n23D為1.490。甲基丙烯酸酯聚合物嵌段(b11)的質量相對於丙烯酸酯聚合物嵌段(b2)的質量之比為48/52。 The methyl methacrylate polymer block (b1 1 ) was Mw b11 of 74,300. The acrylate polymer (b2) had a Mw b2 of 81,700 and a ratio of benzyl acrylate of 25.6% by mass. The diblock copolymer [B-2] had a Mw B of 156,000, a Mw B /Mn B of 1.08 and an n 23D of 1.490. The ratio of the mass of the methacrylate polymer block (b1 1 ) to the mass of the acrylate polymer block (b2) was 48/52.

製造例10(三嵌段共聚物[B-3]之製造) Production Example 10 (Manufacture of Triblock Copolymer [B-3])

於內部脫氣，經氮氣置換的三口燒瓶中，在室溫下置入2003g乾燥甲苯、2.1g六甲基三伸乙四胺及51.5g含有異丁基雙(2,6-二第三丁基-4-甲基苯氧基)鋁20mmol的甲苯溶液。於其中加入1.13mmol的第二丁基鋰。再者，於其中加入108.5g甲基丙烯酸甲酯，在室溫下反應1小時而得到甲基丙烯酸甲酯聚合物(b11)。反應液中所含有的甲基丙烯酸甲酯聚合物(b11)之重量平均分子量Mwb11為19000。 Internally degassed, placed in a three-necked flask purged with nitrogen, placed at room temperature with 2003 g of dry toluene, 2.1 g of hexamethyltrimethylenetetramine, and 51.5 g of isobutyl bis (2,6-di-third) A solution of 20 mmol of toluene in 4-methylphenoxy)aluminum. To this was added 1.13 mmol of second butyllithium. Further, 108.5 g of methyl methacrylate was added thereto, and the mixture was reacted at room temperature for 1 hour to obtain a methyl methacrylate polymer (b1 1 ). The weight average molecular weight Mw b11 of the methyl methacrylate polymer (b1 1 ) contained in the reaction liquid was 19,000.

其次，使反應液成為-30℃，費0.5小時滴下219.6g丙烯酸正丁酯及77.1g丙烯酸苄酯的混合液，自甲基丙烯酸甲酯聚合物(b11)之末端起，繼續聚合反應，得到自甲基丙烯酸甲酯聚合物嵌段(b11)與由丙烯酸正丁酯及丙烯酸苄酯所成的丙烯酸酯聚合物嵌段(b2)所構成 之二嵌段共聚物。反應液中所含有的二嵌段聚合物之重量平均分子量為57800。由於甲基丙烯酸甲酯聚合物嵌段(b11)之重量平均分子量為19000，將由丙烯酸正丁酯及丙烯酸苄酯所成的丙烯酸酯聚合物嵌段(b2)之重量平均分子量斷定為38800。丙烯酸酯聚合物(b2)中所含有的丙烯酸苄酯之比例為25.6質量%。 Next, the reaction liquid was brought to -30 ° C, and a mixture of 219.6 g of n-butyl acrylate and 77.1 g of benzyl acrylate was added dropwise over 0.5 hours, and the polymerization was continued from the end of the methyl methacrylate polymer (b1 1 ). A diblock copolymer composed of a methyl methacrylate polymer block (b1 1 ) and an acrylate polymer block (b2) composed of n-butyl acrylate and benzyl acrylate was obtained. The weight average molecular weight of the diblock polymer contained in the reaction liquid was 57,800. Since the weight average molecular weight of the methyl methacrylate polymer block (b1 1 ) was 19,000, the weight average molecular weight of the acrylate polymer block (b2) composed of n-butyl acrylate and benzyl acrylate was determined to be 38,800. The ratio of the benzyl acrylate contained in the acrylate polymer (b2) was 25.6% by mass.

繼續，添加125.6g甲基丙烯酸甲酯，使反應液回到室溫，藉由8小時攪拌，而自丙烯酸酯聚合物嵌段(b2)的末端起繼續聚合反應，得到自甲基丙烯酸甲酯聚合物嵌段(b11)、由丙烯酸正丁酯及丙烯酸苄酯所成的丙烯酸酯聚合物嵌段(b2)與甲基丙烯酸甲酯聚合物嵌段(b12)所構成之三嵌段共聚物[B-3]。 Continuing, 125.6 g of methyl methacrylate was added, the reaction solution was returned to room temperature, and the polymerization was continued from the end of the acrylate polymer block (b2) by stirring for 8 hours to obtain methyl methacrylate. a polymer block (b1 1 ), an acrylate polymer block (b2) composed of n-butyl acrylate and benzyl acrylate, and a triblock composed of a methyl methacrylate polymer block (b1 2 ) Copolymer [B-3].

然後，於反應液添加4g甲醇而使聚合停止。然後，將反應液注入大量的甲醇中而使三嵌段共聚物[B-3]析出，濾取該析出物，在80℃、1torr(約133Pa)下乾燥12小時。所得之三嵌段共聚物[B-3]係重量平均分子量MwB為75800，MwB/MnB為1.10，n23D為1.490。由於二嵌段共聚物之重量平均分子量為57800，將甲基丙烯酸甲酯聚合物嵌段(b12)之重量平均分子量斷定為18000。甲基丙烯酸酯聚合物嵌段(b11)與(b12)的合計質量相對於丙烯酸酯聚合物嵌段(b2)的質量之比為49/51。 Then, 4 g of methanol was added to the reaction liquid to stop the polymerization. Then, the reaction liquid was poured into a large amount of methanol to precipitate a triblock copolymer [B-3], and the precipitate was collected by filtration, and dried at 80 ° C and 1 torr (about 133 Pa) for 12 hours. The obtained triblock copolymer [B-3] had a weight average molecular weight Mw B of 75,800, Mw B /Mn B of 1.10, and n 23D of 1.490. Since the weight average molecular weight of the diblock copolymer was 57,800, the weight average molecular weight of the methyl methacrylate polymer block (b1 2 ) was determined to be 18,000. The ratio of the total mass of the methacrylate polymer blocks (b1 1 ) to (b1 2 ) to the mass of the acrylate polymer block (b2) was 49/51.

由於甲基丙烯酸甲酯聚合物嵌段(b11)之重量平均分子量為19000，甲基丙烯酸甲酯聚合物嵌段(b12)之重量平均分子量為18000，甲基丙烯酸甲酯聚合物嵌段(b1)之重量平均分子量Mwb1為37000。 Since the weight average molecular weight of the methyl methacrylate polymer block (b1 1 ) is 19,000, the weight average molecular weight of the methyl methacrylate polymer block (b1 2 ) is 18,000, and the methyl methacrylate polymer block The weight average molecular weight Mw b1 of (b1) was 37,000.

製造例11(二嵌段共聚物[B-4]之製造) Production Example 11 (Production of Diblock Copolymer [B-4])

除了將甲基丙烯酸甲酯之量改變為90g，將丙烯酸正丁酯之量改變為4g，將丙烯酸苄酯之量改變為14g以外，以與製造例7相同之方法得到自甲基丙烯酸甲酯聚合物嵌段(b11)與由丙烯酸正丁酯及丙烯酸苄酯所成的丙烯酸酯聚合物(b2)所構成之二嵌段共聚物[B-4]。甲基丙烯酸甲酯聚合物嵌段(b11)係Mwb11為88900。丙烯酸酯聚合物(b2)係Mwb2為5200，丙烯酸苄酯之比例為26.0質量%。二嵌段共聚物[B-4]係MwB為94100，MwB/MnB為1.08，n23D為1.490。甲基丙烯酸酯聚合物嵌段(b11)的質量相對於丙烯酸酯聚合物嵌段(b2)的質量之比為94/6。 Methyl methacrylate was obtained in the same manner as in Production Example 7, except that the amount of methyl methacrylate was changed to 90 g, the amount of n-butyl acrylate was changed to 4 g, and the amount of benzyl acrylate was changed to 14 g. A diblock copolymer [B-4] composed of a polymer block (b1 1 ) and an acrylate polymer (b2) composed of n-butyl acrylate and benzyl acrylate. The methyl methacrylate polymer block (b1 1 ) has a Mw b11 of 88,900. The acrylate polymer (b2) had a Mw b2 of 5,200 and a ratio of benzyl acrylate of 26.0% by mass. The diblock copolymer [B-4] had a Mw B of 94,100, Mw B /Mn B of 1.08, and n 23D of 1.490. The ratio of the mass of the methacrylate polymer block (b1 1 ) to the mass of the acrylate polymer block (b2) was 94/6.

製造例12(二嵌段共聚物[B-5]之製造) Production Example 12 (Production of Diblock Copolymer [B-5])

除了將甲基丙烯酸甲酯之量改變為5g，將丙烯酸正丁酯之量改變為63g，將丙烯酸苄酯之量改變為22g以外，以與製造例7相同之方法得到自甲基丙烯酸甲酯聚合物嵌段(b11)與由丙烯酸正丁酯及丙烯酸苄酯所成的丙烯酸酯聚合物(b2)所構成之二嵌段共聚物[B-5]。 Methyl methacrylate was obtained in the same manner as in Production Example 7, except that the amount of methyl methacrylate was changed to 5 g, the amount of n-butyl acrylate was changed to 63 g, and the amount of benzyl acrylate was changed to 22 g. A diblock copolymer [B-5] composed of a polymer block (b1 1 ) and an acrylate polymer (b2) composed of n-butyl acrylate and benzyl acrylate.

甲基丙烯酸甲酯聚合物嵌段(b11)係Mwb11為4500。丙烯酸酯聚合物(b2)係Mwb2為88300，丙烯酸苄酯之比例為26.0質量%。二嵌段共聚物[B-5]係MwB為92800，MwB/MnB為1.10，n23D為1.489。甲基丙烯酸酯聚合物嵌段(b11)的質量相對於丙烯酸酯聚合物嵌段(b2)的質量之比為5/95。 The methyl methacrylate polymer block (b1 1 ) was Mw b11 of 4500. The acrylate polymer (b2) had a Mw b2 of 88,300 and a ratio of benzyl acrylate of 26.0% by mass. The diblock copolymer [B-5] had Mw B of 92800, Mw B /Mn B of 1.10, and n 23D of 1.489. The ratio of the mass of the methacrylate polymer block (b1 1 ) to the mass of the acrylate polymer block (b2) was 5/95.

製造例13(二嵌段共聚物[B-6]之製造) Production Example 13 (Production of Diblock Copolymer [B-6])

除了將甲基丙烯酸甲酯之量改變為50g，將丙烯酸正 丁酯之量改變為50g，將丙烯酸苄酯之量改變為0g以外，以與製造例7相同之方法得到自甲基丙烯酸甲酯聚合物嵌段(b11)與由丙烯酸正丁酯所成的丙烯酸酯聚合物(b2)所構成之二嵌段共聚物[B-6]。 Methyl methacrylate was obtained in the same manner as in Production Example 7, except that the amount of methyl methacrylate was changed to 50 g, the amount of n-butyl acrylate was changed to 50 g, and the amount of benzyl acrylate was changed to 0 g. A diblock copolymer [B-6] composed of a polymer block (b1 1 ) and an acrylate polymer (b2) made of n-butyl acrylate.

甲基丙烯酸甲酯聚合物嵌段(b11)係Mwb11為45000。丙烯酸酯聚合物(b2)係Mwb2為45000，丙烯酸苄酯之比例為0質量%。二嵌段共聚物[B-6]係MwB為90000，MwB/MnB為1.08，n23D為1.476。甲基丙烯酸酯聚合物嵌段(b11)的質量相對於丙烯酸酯聚合物嵌段(b2)的質量之比為50/50。 The methyl methacrylate polymer block (b1 1 ) was Mw b11 of 45,000. The acrylate polymer (b2) had a Mw b2 of 45,000 and a ratio of benzyl acrylate of 0% by mass. The diblock copolymer [B-6] had a Mw B of 90,000, Mw B /Mn B of 1.08, and n 23D of 1.476. The ratio of the mass of the methacrylate polymer block (b1 1 ) to the mass of the acrylate polymer block (b2) was 50/50.

表2中顯示嵌段共聚物(B-1)~(B-6)之物性。 Table 2 shows the physical properties of the block copolymers (B-1) to (B-6).

製造例14(含有多層結構聚合物粒子(A)的乳液之製造) Production Example 14 (Manufacture of emulsion containing multilayer structure polymer particles (A))

於具備冷凝器、溫度計及攪拌機之施有玻璃襯裏的反應槽(100升)中，投入48kg離子交換水，其次投入416g硬脂酸鈉、128g月桂基肌胺酸鈉及16g碳酸鈉並使其溶解。隨後，投入11.2kg甲基丙烯酸甲酯及110g甲基丙烯酸 烯丙酯，邊攪拌邊升溫至70℃。然後，添加560g 2%過硫酸鉀水溶液而使其開始聚合。因聚合的放熱，內部溫度上升，然後於開始下降後，歷經30分鐘保持在70℃而得到乳液。 48 kg of ion-exchanged water was placed in a glass-lined reaction vessel (100 liter) equipped with a condenser, a thermometer, and a stirrer, and 416 g of sodium stearate, 128 g of sodium lauryl sarcosinate, and 16 g of sodium carbonate were added thereto. Dissolved. Subsequently, 11.2 kg of methyl methacrylate and 110 g of methacrylic acid were charged. The allyl ester was heated to 70 ° C with stirring. Then, 560 g of a 2% potassium persulfate aqueous solution was added to initiate polymerization. The internal temperature rose due to the exothermic heat of the polymerization, and then, after starting to fall, it was maintained at 70 ° C for 30 minutes to obtain an emulsion.

於所得之乳液中，添加720g 2%過硫酸鈉水溶液。然後，費60分鐘滴下由12.4kg的丙烯酸丁酯、1.76kg苯乙烯及280g甲基丙烯酸烯丙酯所構成之單體混合物，更且在經過60分鐘之前，使其接枝聚合。 To the resulting emulsion, 720 g of a 2% aqueous solution of sodium persulfate was added. Then, a monomer mixture composed of 12.4 kg of butyl acrylate, 1.76 kg of styrene, and 280 g of allyl methacrylate was dropped for 60 minutes, and graft polymerization was further carried out before 60 minutes passed.

於接枝聚合後的乳液中，添加320g 2%過硫酸鉀水溶液，更且費30分鐘添加由6.2kg甲基丙烯酸甲酯、0.2kg丙烯酸甲酯及200g正辛基硫醇所構成之單體混合物。然後繼續60分鐘攪拌而完成聚合。得到含有40%的平均粒徑0.23μm之多層結構聚合物粒子(A)的乳液(A)。 To the emulsion after the graft polymerization, 320 g of a 2% potassium persulfate aqueous solution was added, and a monomer composed of 6.2 kg of methyl methacrylate, 0.2 kg of methyl acrylate, and 200 g of n-octyl mercaptan was added for 30 minutes. mixture. The polymerization was then completed by stirring for 60 minutes. An emulsion (A) containing 40% of the multilayer structure polymer particles (A) having an average particle diameter of 0.23 μm was obtained.

製造例15(含有(甲基)丙烯酸酯系聚合物粒子(B)的乳液之製造) Production Example 15 (Production of Emulsion Containing (Meth) Acrylate Polymer Particles (B))

於具備冷凝器、溫度計及攪拌機之施有玻璃襯裏的反應槽(100升)中，投入48kg離子交換水，其次投入252g界面活性劑(花王股份有限公司製「Pelex SS-H」)而使其溶解。將此升溫至70℃。於其中添加160g 2%過硫酸鉀水溶液，其次添加由3.04kg甲基丙烯酸甲酯、0.16kg丙烯酸甲酯及15.2g正辛基硫醇所構成之混合物，使其開始聚合。於自聚合的放熱結束時起30分鐘經過時，添加160g 2%過硫酸鉀水溶液，其次費2小時滴下由27.4kg甲基丙烯酸甲酯、1.44kg丙烯酸甲酯及98g正辛基硫醇所構成之混合物，進行聚合。自滴下結束時起60分鐘經過後，冷卻反 應液，得到含有40%的平均粒徑0.12μm且極限黏度0.44g/dl之(甲基)丙烯酸酯系聚合物粒子(B)的乳液(B)。 48 kg of ion-exchanged water was placed in a glass-lined reaction vessel (100 liter) equipped with a condenser, a thermometer, and a stirrer, and 252 g of a surfactant ("Pelex SS-H" manufactured by Kao Co., Ltd.) was placed in the reactor. Dissolved. This was warmed to 70 °C. 160 g of a 2% potassium persulfate aqueous solution was added thereto, and a mixture of 3.04 kg of methyl methacrylate, 0.16 kg of methyl acrylate, and 15.2 g of n-octyl mercaptan was added thereto to start polymerization. At the end of 30 minutes from the end of the exothermic heat of polymerization, 160 g of 2% potassium persulfate aqueous solution was added, followed by 2 hours of dropwise addition of 27.4 kg of methyl methacrylate, 1.44 kg of methyl acrylate and 98 g of n-octyl mercaptan. The mixture is polymerized. Cooling back after 60 minutes from the end of the drop In the liquid solution, an emulsion (B) containing 40% of (meth)acrylate polymer particles (B) having an average particle diameter of 0.12 μm and an ultimate viscosity of 0.44 g/dl was obtained.

製造例16[耐衝擊性改良劑[C]之製造] Production Example 16 [Manufacture of Impact Resistance Improver [C]]

以多層結構聚合物粒子(A)：(甲基)丙烯酸酯系聚合物粒子(B)之重量比成為2：1之方式，混合乳液(A)與乳液(B)。在-20℃費2小時使其冷凍。將所得之凍結物投入其質量之2倍量的80℃溫水中而使其溶解，得到漿體。將該漿體在80℃保持20分鐘。其次，脫水，使固體成分在70℃乾燥，得到粉末狀的耐衝擊性改良劑[C]。 The emulsion (A) and the emulsion (B) were mixed so that the weight ratio of the multilayered polymer particles (A): (meth)acrylate polymer particles (B) was 2:1. It was allowed to freeze at -20 ° C for 2 hours. The obtained frozen product was poured into warm water of 80 ° C twice the mass and dissolved to obtain a slurry. The slurry was held at 80 ° C for 20 minutes. Next, dehydration was carried out, and the solid component was dried at 70 ° C to obtain a powdery impact resistance improver [C].

準備以下的聚碳酸酯樹脂。 The following polycarbonate resin was prepared.

PC1：住化STYRON聚碳酸酯公司製，SD POLYCATR-2201(型號)，MVR(300℃、1.2Kg、10分鐘；依據JIS K7210)=210cm3/10分鐘 PC1: STYRON polycarbonate company, SD POLYCATR-2201 (model), MVR (300 ° C, 1.2 Kg, 10 minutes; according to JIS K7210) = 210 cm 3 /10 minutes

PC2：三菱工程塑膠公司製，Lupilon HL-8000(型號)，MVR(300℃、1.2Kg、10分鐘；依據JIS K7210準拠)=136cm3/10分鐘 PC2: manufactured by Mitsubishi Engineering Plastics Co., Ltd., Lupilon HL-8000 (model), MVR (300 ° C, 1.2 Kg, 10 minutes; according to JIS K7210) = 136 cm 3 /10 minutes

準備以下的苯氧樹脂。 Prepare the following phenoxy resin.

Phenoxy1：(新日鐵住金化學公司製，YP-50S(型號)，MFR(230℃、3.8Kg、10分鐘；依據JIS K7210)=22g/10分鐘，Mw=55000，Mw/Mn=2.5) Phenoxy1: (made by Nippon Steel & Sumitomo Chemical Co., Ltd., YP-50S (model), MFR (230 ° C, 3.8 Kg, 10 min; according to JIS K7210) = 22 g/10 min, Mw = 55000, Mw / Mn = 2.5)

準備以下的紫外線吸收劑。 Prepare the following UV absorbers.

UVA1：2,4,6-參(2-羥基-4-己氧基-3-甲基苯基)-1,3,5-三(ADEKA公司製；LA-F70) UVA1: 2,4,6-gin (2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-three (ADEKA company; LA-F70)

UVA2：2,2’-亞甲基雙[6-(2H-苯并***-2-基)-4-(1,1,3,3-四甲基丁基)苯酚](ADEKA公司製；LA-31) UVA2: 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol] (made by ADEKA) ;LA-31)

除了製造例1~7所得之甲基丙烯酸樹脂，還準備以下的甲基丙烯酸樹脂。 In addition to the methacrylic resins obtained in Production Examples 1 to 7, the following methacrylic resins were prepared.

A-8：Parapet HR-1000S(KURARAY公司製) A-8: Parapet HR-1000S (KURARAY company)

A-9：含有耐衝擊性改良劑的Acrypet VRL40(三菱麗陽公司製) A-9: Acrypet VRL40 (manufactured by Mitsubishi Rayon Co., Ltd.) containing impact modifier

<實施例1> <Example 1>

混合90質量份的甲基丙烯酸樹脂[A-3]、10質量份的嵌段共聚物[B-1]、4質量份的聚碳酸酯樹脂[PC1]及2質量份的加工助劑((Paraloid K125-P(KUREHA公司製))，用雙軸擠壓機(TECHNOVEL(股)製，商品名：KZW20TW-45MG-NH-600)在250℃混煉擠出，製造甲基丙烯酸樹脂組成物[C-1]。 90 parts by mass of methacrylic resin [A-3], 10 parts by mass of block copolymer [B-1], 4 parts by mass of polycarbonate resin [PC1], and 2 parts by mass of processing aid (( Paraloid K125-P (manufactured by KUREHA Co., Ltd.), which was kneaded and extruded at 250 ° C by a biaxial extruder (manufactured by TECHNOVEL Co., Ltd., trade name: KZW20TW-45MG-NH-600) to produce a methacrylic resin composition. [C-1].

(全光線透過率) (total light transmittance)

將甲基丙烯酸樹脂組成物[C-1]予以熱壓成形而得到130mm×50mm×3.2mm的板狀成形體。依據JIS K7361-1，使用霧度計(村上色彩研究所製HM-150)，測定3.2mm厚的全光線透過率。 The methacrylic resin composition [C-1] was subjected to hot press molding to obtain a plate-shaped formed body of 130 mm × 50 mm × 3.2 mm. According to JIS K7361-1, a haze meter (HM-150 manufactured by Murakami Color Research Laboratory) was used, and a total light transmittance of 3.2 mm was measured.

(霧度(23℃)) (Haze (23 ° C))

將甲基丙烯酸樹脂組成物[C-1]予以熱壓成形而得到130mm×50mm×3.2mm的板狀成形體。依據JIS K7136，使用霧度計(村上色彩研究所製HM-150)，在23℃測定3.2mm厚部之霧度。 The methacrylic resin composition [C-1] was subjected to hot press molding to obtain a plate-shaped formed body of 130 mm × 50 mm × 3.2 mm. The haze of a 3.2 mm thick portion was measured at 23 ° C using a haze meter (HM-150, manufactured by Murakami Color Research Laboratory) in accordance with JIS K7136.

(霧度(70℃)) (Haze (70 ° C))

將甲基丙烯酸樹脂組成物[C-1]予以熱壓成形而得到130mm×50mm×3.2mm的板狀成形體。於70℃的恒溫器 內放置30分鐘。自恒溫器取出板狀成形體，立刻依據JIS K7136，使用霧度計(村上色彩研究所製HM-150)測定3.2mm厚部之霧度。 The methacrylic resin composition [C-1] was subjected to hot press molding to obtain a plate-shaped formed body of 130 mm × 50 mm × 3.2 mm. Thermostat at 70 ° C Leave it inside for 30 minutes. The plate-shaped molded body was taken out from the thermostat, and the haze of the 3.2 mm thick portion was measured by a haze meter (HM-150, manufactured by Murakami Color Research Laboratory) in accordance with JIS K7136.

(附缺口的彎曲強度) (with bending strength of the notch)

將甲基丙烯酸樹脂組成物[C-1]在230℃射出成形，得到80mm×10mm×厚度4.0mm的試驗片。除了使用該試驗片，使缺口角度僅成為45°以外，依據ASTM E399-83，使用Autograph(島津製作所股份有限公司製)，實施在23℃的3點彎曲。將當時的最大點應力作為附缺口的彎曲強度。 The methacrylic resin composition [C-1] was injection-molded at 230 ° C to obtain a test piece of 80 mm × 10 mm × 4.0 mm in thickness. In addition to the use of the test piece, the notch angle was only 45°, and a three-point bending at 23° C. was carried out in accordance with ASTM E399-83 using Autograph (manufactured by Shimadzu Corporation). The maximum point stress at that time was taken as the bending strength with a notch.

表3中顯示甲基丙烯酸樹脂組成物[C-1]之物性。 The physical properties of the methacrylic resin composition [C-1] are shown in Table 3.

<實施例2~17、比較例1~9> <Examples 2 to 17 and Comparative Examples 1 to 9>

除了成為表3、4或5所示的摻合以外，以與實施例1相同之方法製造甲基丙烯酸樹脂組成物[C-2]~[C-26]。表3、4或5中顯示甲基丙烯酸樹脂組成物[C-2]~[C-26]之物性。 The methacrylic resin compositions [C-2] to [C-26] were produced in the same manner as in Example 1 except that the blending shown in Tables 3, 4 or 5 was carried out. The physical properties of the methacrylic resin compositions [C-2] to [C-26] are shown in Tables 3, 4 or 5.

如表3、4或5所示，本發明之甲基丙烯酸樹脂組成物(實施例)係透明性高，在寬廣的溫度範圍中霧度之變化小，玻璃轉移溫度高且機械強度大。 As shown in Tables 3, 4 or 5, the methacrylic resin composition (Example) of the present invention has high transparency, a small change in haze in a wide temperature range, a high glass transition temperature, and a large mechanical strength.

<實驗例A> <Experimental Example A>

使甲基丙烯酸樹脂組成物[C-6]在80℃乾燥12小時。使用20mmΦ單軸擠壓機(OCS公司製)，在樹脂溫度260℃，自150mm寬的T模頭擠出甲基丙烯酸樹脂組成物[C-6]，以表面溫度85℃的輥牽引其，得到寬度110mm、厚度160μm之未延伸薄膜。 The methacrylic resin composition [C-6] was dried at 80 ° C for 12 hours. The methacrylic resin composition [C-6] was extruded from a 150 mm wide T die at a resin temperature of 260 ° C using a 20 mm Φ single-axis extruder (manufactured by OCS), and pulled at a surface temperature of 85 ° C. An unstretched film having a width of 110 mm and a thickness of 160 μm was obtained.

(表面平滑性) (surface smoothness)

藉由目視觀察未延伸薄膜之表面，用以下之基準來評價表面平滑性。 The surface smoothness was evaluated by the following basis by visually observing the surface of the unstretched film.

A：表面平滑。 A: The surface is smooth.

B：在表面有凹凸。 B: There are irregularities on the surface.

自未延伸薄膜切出100mm×100mm之尺寸的切片。將該切片固定於集電弓式雙軸延伸試驗機(東洋精機(股)製)上，以玻璃轉移溫度+20℃的延伸溫度、1000%/分鐘的延伸速度、2倍的延伸倍率在縱向延伸，其次以玻璃轉移溫度+20℃的延伸溫度、1000%/分鐘的延伸速度、2倍的延伸倍率在橫向延伸。將如此地經逐次雙軸延伸4倍的面積比之薄膜予以徐冷，得到厚度40μm的雙軸延伸薄膜。 A slice of a size of 100 mm x 100 mm was cut out from the unstretched film. The slice was fixed on a pantograph type double-axis extension tester (manufactured by Toyo Seiki Co., Ltd.) at a glass transition temperature of +20 ° C extension temperature, an extension speed of 1000% / min, and a stretching ratio of 2 times in the longitudinal direction. The elongation was followed by a glass transition temperature of +20 ° C extension temperature, an extension speed of 1000% / minute, and a stretching ratio of 2 times in the transverse direction. The film was thus quenched by sequentially biaxially stretching four times the area to obtain a biaxially stretched film having a thickness of 40 μm.

(延伸性) (extensibility)

對於10片的切片，進行上述的逐次雙軸延伸，將能取得無破裂或裂紋的薄膜5片以上之情況評價為「A」，將僅能取得無破裂或裂紋的薄膜4片以下之情況評價「B」。 The above-described sequential biaxial stretching was performed on 10 slices, and it was evaluated as "A" in the case where five or more films having no cracks or cracks were obtained, and only four films having no cracks or cracks were obtained. "B".

(全光線透過率) (total light transmittance)

依據JIS K7361-1，使用霧度計(村上色彩研究所製HM-150)測定薄膜的全光線透過率。 The total light transmittance of the film was measured using a haze meter (HM-150, manufactured by Murakami Color Research Laboratory) in accordance with JIS K7361-1.

(霧度(23℃)) (Haze (23 ° C))

依據JIS K7136，使用霧度計(村上色彩研究所製HM-150)，在23℃測定薄膜的霧度。 The haze of the film was measured at 23 ° C using a haze meter (HM-150 manufactured by Murakami Color Research Laboratory) in accordance with JIS K7136.

(膜厚方向之相位差(Rth)) (phase difference (Rth) in the film thickness direction)

將40mm×40mm的試驗片固定於自動雙折射計(王子計測股份有限公司製KOBRA-WR)上，在溫度23±2℃、濕度50±5%下，測定波長590nm、40°傾斜方向之相位差，自其值與平均折射率n來算出射率nx、ny及nz，更且算出厚度方向相位差Rth(=((nx+ny)/2-nz)×d)。nx係面內遲相軸方向的折射率，ny係相對於遲相軸在面內為直角方向之折射率，nz係厚度方向之折射率。 The test piece of 40 mm × 40 mm was fixed on an automatic birefringence meter (KOBRA-WR manufactured by Oji Scientific Co., Ltd.), and the phase of the wavelength of 590 nm and 40° was measured at a temperature of 23 ± 2 ° C and a humidity of 50 ± 5%. The difference is calculated from the value and the average refractive index n to calculate the illuminances n x , n y and n z , and the thickness direction phase difference Rth (=((n x + n y )/2 - n z ) × d)) . The refractive index of the n x- plane in the direction of the slow axis, n y is the refractive index in the plane perpendicular to the slow axis, and n z is the refractive index in the thickness direction.

試驗片的厚度d[nm]係使用Digimatic Indicator(MI TUTOYO股份有限公司製)進行測定。折射率nx、ny及nz之算出所需要的平均折射率n，係使用數位精密折射計(KALNEW光學工業股份有限公司KPR-200)所測定之在波長587.6nm(D線)的平均折射率之值。 The thickness d [nm] of the test piece was measured using a Digimatic Indicator (manufactured by MI TUTOYO Co., Ltd.). The average refractive index n required for the calculation of the refractive indices n x , n y , and n z is an average of 587.6 nm (D line) measured by a digital precision refractometer (KALNEW Optical Industries, Ltd. KPR-200). The value of the refractive index.

<實驗例B~I> <Experimental Example B~I>

除了使用表6所示的甲基丙烯酸樹脂組成物以外，以與實驗例A相同之方法得到厚度40μm的雙軸延伸薄膜。表6中顯示所得之雙軸延伸薄膜的延伸性、全光線透過率、霧度及厚度方向相位差(Rth)之測定結果。再者，實驗例G及H所得之薄膜由於霧度值高，而未測定Rth。又，觀察實驗例E之製膜後的輥，儘管樹脂組成物含有紫外線吸收劑，卻無因滲出所致的輥污染。 A biaxially stretched film having a thickness of 40 μm was obtained in the same manner as in Experimental Example A except that the methacrylic resin composition shown in Table 6 was used. Table 6 shows the results of measurement of the elongation, total light transmittance, haze, and thickness direction phase difference (Rth) of the obtained biaxially stretched film. Further, the films obtained in Experimental Examples G and H had high haze values, and Rth was not measured. Further, the roll after the film formation of Experimental Example E was observed, and although the resin composition contained the ultraviolet absorber, there was no roll contamination due to bleeding.

如表6所示，使用本發明之甲基丙烯酸樹脂組成物所得之雙軸延伸薄膜，係透明性高、延伸性良好，可減小厚度方向相位差。又，本發明之薄膜由於延伸性良好，而能以如此方式得到薄的延伸薄膜。 As shown in Table 6, the biaxially stretched film obtained by using the methacrylic resin composition of the present invention has high transparency and good elongation, and can reduce the phase difference in the thickness direction. Further, since the film of the present invention is excellent in stretchability, a thin stretched film can be obtained in this manner.

Claims (14)

一種甲基丙烯酸樹脂組成物，其包含：三元組表示之間規性(rr)為58%以上，且來自甲基丙烯酸甲酯的結構單元之含量為90質量%以上之甲基丙烯酸樹脂(A)，及具有10~80質量%的甲基丙烯酸酯聚合物嵌段(b1)與90~20質量%的丙烯酸酯聚合物嵌段(b2)之嵌段共聚物(B)，且嵌段共聚物(B)相對於甲基丙烯酸樹脂(A)之質量比為1/99~90/10。 A methacrylic resin composition comprising: a trimethacrylate resin having a conformity (rr) of 58% or more and a content of a structural unit derived from methyl methacrylate of 90% by mass or more ( A), and a block copolymer (B) having 10 to 80% by mass of a methacrylate polymer block (b1) and 90 to 20% by mass of an acrylate polymer block (b2), and a block The mass ratio of the copolymer (B) to the methacrylic resin (A) is from 1/99 to 90/10. 如請求項1之甲基丙烯酸樹脂組成物，其中該丙烯酸酯聚合物嵌段(b2)包含50~90質量的來自丙烯酸烷酯的結構單元%與50~10質量的來自(甲基)丙烯酸芳香族酯的結構單元%。 The methacrylic resin composition of claim 1, wherein the acrylate polymer block (b2) comprises 50 to 90% by mass of structural unit derived from alkyl acrylate and 50 to 10% by mass of (meth)acrylic acid % of structural units of the family ester. 如請求項1或2之甲基丙烯酸樹脂組成物，其中嵌段共聚物(B)相對於甲基丙烯酸樹脂(A)之質量比為5/95~25/75。 The methacrylic resin composition of claim 1 or 2, wherein the mass ratio of the block copolymer (B) to the methacrylic resin (A) is from 5/95 to 25/75. 如請求項1至3中任一項之甲基丙烯酸樹脂組成物，其中甲基丙烯酸樹脂(A)係來自甲基丙烯酸甲酯的結構單元之總含量為99質量%以上，且在波長587.6nm(D線)、23℃的折射率為1.488~1.490，嵌段共聚物(B)係在波長587.6nm(D線)、23℃的折射率為1.485~1.495。 The methacrylic resin composition according to any one of claims 1 to 3, wherein the methacrylic resin (A) is a total content of structural units derived from methyl methacrylate of 99% by mass or more and at a wavelength of 587.6 nm. (D line), the refractive index at 23 ° C is 1.488 to 1.490, the block copolymer (B) is at a wavelength of 587.6 nm (D line), and the refractive index at 23 ° C is 1.485 to 1.495. 如請求項1至4中任一項之甲基丙烯酸樹脂組成物，其中甲基丙烯酸樹脂(A)係重量平均分子量為50000~ 150000，分子量200000以上的成分之含量為0.1~10%，且分子量小於15000的成分之含量為0.2~5%。 The methacrylic resin composition according to any one of claims 1 to 4, wherein the methacrylic resin (A) has a weight average molecular weight of 50,000~ 150000, the content of the component having a molecular weight of 200,000 or more is 0.1 to 10%, and the content of the component having a molecular weight of less than 15,000 is 0.2 to 5%. 如請求項1至5中任一項之甲基丙烯酸樹脂組成物，其中甲基丙烯酸樹脂(A)係以甲基丙烯酸樹脂(a1)/甲基丙烯酸樹脂(a2)之質量比40/60~70/30，含有三元組表示之間規性(rr)為65%以上的甲基丙烯酸樹脂(a1)與三元組表示之間規性(rr)為45~58%的甲基丙烯酸樹脂(a2)。 The methacrylic resin composition according to any one of claims 1 to 5, wherein the methacrylic resin (A) is a mass ratio of methacrylic resin (a1)/methacrylic resin (a2) of 40/60~ 70/30, a ternary group containing a methacrylic resin (a1) and a triad having a regularity (rr) of 65% or more and a methacrylic resin having a regularity (rr) of 45 to 58% (a2). 如請求項6之甲基丙烯酸樹脂組成物，其中甲基丙烯酸樹脂(a2)係重量平均分子量為80000~150000。 The methacrylic resin composition of claim 6, wherein the methacrylic resin (a2) has a weight average molecular weight of 80,000 to 150,000. 如請求項1至7中任一項之甲基丙烯酸樹脂組成物，其進一步含有紫外線吸收劑。 The methacrylic resin composition according to any one of claims 1 to 7, which further contains an ultraviolet absorber. 如請求項1至8中任一項之甲基丙烯酸樹脂組成物，其中相對於甲基丙烯酸樹脂(A)及嵌段共聚物(B)之合計量100質量份，進一步含有1~10質量份的聚碳酸酯樹脂。 The methacrylic resin composition according to any one of claims 1 to 8, which further contains 1 to 10 parts by mass based on 100 parts by mass of the total of the methacrylic resin (A) and the block copolymer (B). Polycarbonate resin. 如請求項1至8中任一項之甲基丙烯酸樹脂組成物，其中相對於甲基丙烯酸樹脂(A)及嵌段共聚物(B)之合計量100質量份，進一步含有1~10質量份的苯氧樹脂。 The methacrylic resin composition according to any one of claims 1 to 8, which further contains 1 to 10 parts by mass based on 100 parts by mass of the total of the methacrylic resin (A) and the block copolymer (B). Phenoxy resin. 一種成形體，其係由如請求項1至10中任一項之甲基丙烯酸樹脂組成物所構成。 A molded body comprising the methacrylic resin composition according to any one of claims 1 to 10. 一種薄膜，其係由如請求項1至11中任一項之甲基丙烯酸樹脂組成物所構成。 A film comprising the methacrylic resin composition according to any one of claims 1 to 11. 如請求項12之薄膜，其係以面積比在至少一方向中經延伸至1.5~8倍。 The film of claim 12, which is extended to 1.5 to 8 times in at least one direction by an area ratio. 一種偏光鏡保護膜，其包含如請求項12或13之薄膜。 A polarizer protective film comprising the film of claim 12 or 13.
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