TWI675742B - Method for producing roll-shaped acrylic resin film and method for producing polarizing plate - Google Patents

Abstract

關於本發明的輥狀丙烯酸系樹脂薄膜之製造方法，其係將丙烯酸系樹脂進行熔融混練，由T型模頭(10)擠出薄膜狀物(1)，將該薄膜狀物(1)挾持於第一冷卻輥(11)與第二冷卻輥(12)之間而作為薄膜狀成形體(2)，將該薄膜狀成形體(2)之寬度方向側端部以切割器(14)切斷，將所得的薄膜(3)纏繞於捲取核心(19)而捲取為輥狀，在纏繞於捲取核心(19)時之捲取張力設為50~250N/m，在捲取核心(19)側配置按壓輥(18)，該按壓輥(18)之線壓設為0.01~0.6N/mm，將上述之側端部被切斷的丙烯酸系樹脂薄膜(3)捲取為輥狀。 Regarding the method for producing a roll-shaped acrylic resin film of the present invention, the acrylic resin is melt-kneaded, a film-shaped object (1) is extruded from a T-die (10), and the film-shaped object (1) is held. Between the first cooling roll (11) and the second cooling roll (12) as a film-like formed body (2), the width-direction side end portion of the film-like formed body (2) is cut with a cutter (14) The winding film (3) is wound around the winding core (19) and wound into a roll shape. The winding tension when winding around the winding core (19) is set to 50 to 250 N / m. (19) A pressing roller (18) is arranged on the side, and the linear pressure of the pressing roller (18) is set to 0.01 to 0.6 N / mm, and the acrylic resin film (3) whose side end portion is cut is taken up as a roller. shape.

Description

輥狀丙烯酸系樹脂薄膜之製造方法及偏光板之製造方法 Manufacturing method of roll-shaped acrylic resin film and manufacturing method of polarizing plate

本發明係關於將可利用作為使用於液晶顯示裝置(LCD)等的偏光板之保護薄膜的丙烯酸系樹脂薄膜，捲取為輥狀，製造該樹脂薄膜的方法。本發明係另外關於，以藉由此方法而製造的輥狀丙烯酸系樹脂薄膜所製造的偏光板的方法。 The present invention relates to a method for manufacturing an acrylic resin film which can be used as a protective film for a polarizing plate of a liquid crystal display device (LCD) or the like by rolling it into a roll shape. The present invention further relates to a method of a polarizing plate produced by a roll-shaped acrylic resin film produced by this method.

近年來，液晶顯示裝置或電漿顯示器等之平板顯示器(FPD)之需要擴大，需要使用於此的高機能的光學薄膜。例如，在液晶顯示裝置中，由該圖像形成方法必需在形成液晶面板的玻璃基板之兩面配置偏光板。此偏光板在一般而言，其係成為在由聚乙烯醇系薄膜和碘等之二色性材料所構成的偏光子之兩面，將三乙醯基纖維素等之透明樹脂所構成的偏光子保護薄膜，使用接著劑而黏合的構造。 In recent years, the demand for flat panel displays (FPDs) such as liquid crystal display devices and plasma displays has expanded, and high-performance optical films used therefor have been required. For example, in a liquid crystal display device, it is necessary for this image forming method to arrange polarizing plates on both sides of a glass substrate on which a liquid crystal panel is formed. This polarizer is generally a polarizer made of a transparent resin such as triethylfluoride on both sides of a polarizer made of a dichroic material such as a polyvinyl alcohol film and iodine. A structure that protects a film and is bonded using an adhesive.

但是，三乙醯基纖維素係在耐濕熱性並不充分，將三乙醯基纖維素薄膜作為保護薄膜而使用的偏光板，其係在高溫條件下及高濕熱條件下，有偏光度或色相 等之性能低下的狀況。因此，作為相較於三乙醯基纖維素薄膜而透濕度低的偏光子保護薄膜，已知有使用丙烯酸系樹脂薄膜。 However, triethyl cellulose is not sufficient in moisture and heat resistance. A polarizing plate using a triethyl cellulose film as a protective film is polarized under high temperature and high humidity and heat conditions. Hue And other poor performance. Therefore, it is known to use an acrylic resin film as a polarizer protective film having a lower moisture permeability than a triethylfluorene-based cellulose film.

在製造丙烯酸系樹脂薄膜時，於使用溶液流延製膜法的情況中，其係將樹脂溶解於溶劑的溶液，流延於金屬支持體上，以乾燥步驟除去溶劑而捲取薄膜的方式來製造。另外，在使用熔融擠出製膜法的情況，其係將樹脂以熱熔融，將成為高溫的熔融樹脂從T型模頭熔融擠出於冷卻輥上而製膜，經由用以降低薄膜之溫度之搬送步驟，捲取薄膜的方式來製造。 When an acrylic resin film is produced, when a solution casting film method is used, it is a solution in which a resin is dissolved in a solvent, cast on a metal support, and the solvent is removed by a drying step to roll the film. Manufacturing. In addition, when a melt extrusion film-forming method is used, the resin is melted by heat, and a molten resin that becomes a high temperature is melt-extruded from a T-die onto a cooling roll to form a film. In the conveying step, the film is rolled.

在將此製膜後之薄膜捲取為輥狀時，若在薄膜間捲入空氣，則會有在捲取之後、更進一步隨時間經過，會從薄膜輥漏出空氣而在輥產生變形，而發生被稱為破裂(knick)的點狀缺陷的問題。另外，在輥之保管時，因薄膜之自體重量而在捲取核心上部與捲取核心下部產生半徑不同的向下鬆弛，有薄膜變形而變得有缺陷的問題。特別是，在丙烯酸系樹脂薄膜的情況，相較於三乙醯基纖維素而透濕度更低，更難以吸收水分。因此，在偏光板製造時之薄膜之洗淨或乾燥步驟，難以修正起因於破裂(knick)等之薄膜變形的缺陷，因為輥之變形或薄膜之變形的缺陷產生而有產率大幅下降的問題。 When this film is rolled into a roll shape, if air is drawn in between the films, air will leak out from the film roll and cause deformation in the roll after winding, and further elapsed with time. A problem of point defects called knicks occurs. In addition, during storage of the roll, due to the film's own weight, downward sags with different radii occur in the upper part of the winding core and the lower part of the winding core, and there is a problem that the film deforms and becomes defective. In particular, in the case of an acrylic resin film, the moisture permeability is lower than that of triethylfluorenyl cellulose, and it is more difficult to absorb moisture. Therefore, in the process of cleaning or drying the film during the manufacture of the polarizing plate, it is difficult to correct the defects caused by the deformation of the film such as cracks, and there is a problem that the yield is greatly reduced due to the deformation of the roller or the deformation of the film .

作為用以解決如此的問題之對策，於日本特開2002-220143號公報，開示有捲取時使用按壓輥(在此文獻中，表記為「壓帶輪(lay-on roller)」而抑制進入 薄膜間的空氣層的方法。在此文獻中，以溶液製膜法製作的薄膜作為中心來說明，表示有適用於三乙醯基纖維素薄膜的例子。另外，在日本特開2007-91784號公報，開示有在丙烯酸系樹脂薄膜之寬度方向側端部施加滾邊加工，抑制捲取於輥時之空氣層的方法。若藉由此方法，則因為滾邊之高度不同而有在加工中產生薄膜之斷裂的情事。而且，在加熱薄膜而藉由壓印加工而施加滾邊的情況，有薄膜自身之物性變化之疑慮。 As a countermeasure to solve such a problem, in Japanese Patent Application Laid-Open No. 2002-220143, it is disclosed that the use of a pressing roller is used when winding up (in this document, it is denoted as "lay-on roller" to prevent entry) Method of air layer between films. In this document, a film produced by a solution film-forming method is mainly described, and an example in which it is applied to a triethylfluorene-based cellulose film is shown. In addition, Japanese Patent Application Laid-Open No. 2007-91784 discloses a method of applying a hemming process to an end portion in the width direction of an acrylic resin film to suppress an air layer when being wound around a roll. According to this method, the film may be broken during processing due to the difference in the height of the piping. In addition, when the film is heated and piping is applied by embossing, there is a concern that the physical properties of the film itself change.

另一方面，從以前就知道有在丙烯酸系樹脂調配橡膠彈性體粒子而提高耐衝擊性之情事。作為開示此技術的文獻之例，可舉出日本特公昭55-27576號公報。如此的調配有橡膠彈性體粒子的丙烯酸系樹脂，在薄膜之製膜性亦變得良好。 On the other hand, it has been known that rubber elastomer particles are blended with acrylic resin to improve impact resistance. As an example of a document which discloses this technology, Japanese Patent Publication No. 55-27576 can be cited. The acrylic resin blended with the rubber elastomer particles in this manner also has good film-forming properties.

本發明之目的係提供一種方法，該方法係可抑制在捲取為輥狀的丙烯酸系樹脂薄膜中，起因於隨著歷時變化的輥之變形或薄膜之變形而容易產生的缺陷。本發明係特別是作為用以解決上述問題之對策，其目的在提供一種丙烯酸系樹脂薄膜的製造方法，該方法係藉由在捲取丙烯酸系樹脂薄膜時使用按壓輥而控制進入薄膜間的空氣層，不會產生因輥之變形或薄膜之變形所造成的缺陷。本發明之另一個目的係在提供一種方法，將藉由該方法而製 造的輥狀丙烯酸系樹脂薄膜作為偏光子保護薄膜而使用，製造偏光板。 An object of the present invention is to provide a method capable of suppressing defects easily caused in a roll-shaped acrylic resin film caused by deformation of a roll or deformation of a film over time. The present invention is particularly a countermeasure for solving the above-mentioned problems, and an object thereof is to provide a method for manufacturing an acrylic resin film by controlling the air entering into the film by using a pressing roller when winding the acrylic resin film. Layer, no defects caused by the deformation of the roller or the deformation of the film. Another object of the present invention is to provide a method by which The produced roll-shaped acrylic resin film was used as a polarizer protective film to manufacture a polarizing plate.

關於本發明的輥狀丙烯酸系樹脂薄膜之製造方法，其係將丙烯酸系樹脂進行熔融混練，由T型模頭擠出薄膜狀物，將該薄膜狀物挾持於第一冷卻輥與第二冷卻輥之間而作為薄膜狀成形體，切斷該薄膜狀成形體之寬度方向側端部，將所得的薄膜纏繞於捲取核心而捲取為輥狀，在將薄膜纏繞於捲取核心時之捲取張力設為50~250N/m，在捲取核心側配置按壓輥，該按壓輥之線壓設為0.01~0.6N/mm，將上述側端部被切斷的薄膜捲取為輥狀的方法。 Regarding the method for producing a roll-shaped acrylic resin film of the present invention, the acrylic resin is melt-kneaded, a film-like object is extruded from a T-die, and the film-like object is held by a first cooling roller and a second cooling. As a film-shaped formed body between the rolls, the width-direction side end of the film-shaped formed body is cut, and the obtained film is wound around a winding core and wound into a roll shape. When the film is wound around the winding core, The winding tension is set to 50 to 250 N / m. A pressing roller is arranged on the winding core side, and the linear pressure of the pressing roller is set to 0.01 to 0.6 N / mm. The film with the side ends cut off is wound into a roll shape. Methods.

另外，關於本發明的偏光板之製造方法，其係將藉由上述方法而製造的輥狀丙烯酸系樹脂薄膜捲出，黏合於由聚乙烯醇系樹脂所構成的偏光子的方法。 Moreover, the manufacturing method of the polarizing plate of this invention is a method of rolling out the roll-shaped acrylic resin film manufactured by the said method, and adhering to the polarizer which consists of a polyvinyl alcohol resin.

藉由本發明之方法，可製造一種丙烯酸系樹脂薄膜，其係不易產生因為歷時變化所造成的輥之變形或薄膜之變形所致的缺陷。而且，在製造將丙烯酸系樹脂薄膜作為保護薄膜的偏光板時，其生產性可提高。 By the method of the present invention, an acrylic resin film can be manufactured, which is less prone to defects due to roll deformation or film deformation caused by diachronic changes. In addition, when manufacturing a polarizing plate using an acrylic resin film as a protective film, the productivity can be improved.

1‧‧‧薄膜狀物 1‧‧‧ film

2‧‧‧薄膜狀成形體 2‧‧‧ thin film shaped body

3‧‧‧丙烯酸系樹脂薄膜 3‧‧‧ acrylic resin film

5‧‧‧輥狀丙烯酸系樹脂薄膜 5‧‧‧ roll-shaped acrylic resin film

10‧‧‧T型模頭 10‧‧‧T-type die

11‧‧‧第一冷卻輥 11‧‧‧The first cooling roller

12‧‧‧第二冷卻輥 12‧‧‧second cooling roller

13‧‧‧第三冷卻輥 13‧‧‧third cooling roller

14‧‧‧切割器 14‧‧‧ Cutter

15‧‧‧累積器 15‧‧‧ Accumulator

16‧‧‧夾輥 16‧‧‧ pinch roller

17‧‧‧跳動輥 17‧‧‧beating roller

18‧‧‧按壓輥 18‧‧‧Press roller

19‧‧‧捲取核心 19‧‧‧ take-up core

20‧‧‧搬送輥 20‧‧‧ transport roller

θ‧‧‧進入角度 θ‧‧‧ entry angle

A‧‧‧捲取方向 A‧‧‧ Take-up direction

B‧‧‧進行方向 B‧‧‧ Direction

第1圖係概略地表示有關本發明的方法之一實施形態全體之側面的說明圖。 FIG. 1 is an explanatory diagram schematically showing the entire side of one embodiment of the method of the present invention.

第2圖係放大表示在本發明的捲取步驟之側面的說明圖。 Fig. 2 is an explanatory view showing the side of the winding step of the present invention in an enlarged manner.

第3圖係用以說明在捲取步驟的薄膜之進入角度之圖。 Fig. 3 is a diagram for explaining the entrance angle of the film in the winding step.

[丙烯酸系樹脂] [Acrylic resin]

在本發明所使用的丙烯酸系樹脂係例如可舉出甲基丙烯酸樹脂(甲基丙烯酸酯之均聚物、或將其作為主成分之共聚物)。由賦予薄膜耐衝擊性的觀點來看，丙烯酸系樹脂係調配有橡膠粒子之物，特別是在甲基丙烯酸樹脂調配有橡膠粒子之物為理想。甲基丙烯酸樹脂係甲基丙烯酸酯之均聚物、或將其作為主成分之共聚物。作為甲基丙烯酸酯，其係通常使用甲基丙烯酸之烷基酯，該烷基之碳數為1~4左右。作為共聚物的情況，已知作為甲基丙烯酸樹脂之共聚成分而為有利的丙烯酸酯、或對於甲基丙烯酸烷基酯以及/或是丙烯酸酯可以共聚的其他聚合性單體。 Examples of the acrylic resin used in the present invention include a methacrylic resin (a homopolymer of a methacrylic acid ester or a copolymer containing this as a main component). From the viewpoint of imparting impact resistance to a film, an acrylic resin is preferably prepared by blending rubber particles with a methacrylic resin. A methacrylic resin is a homopolymer of a methacrylic acid ester, or a copolymer containing this as a main component. As the methacrylate, an alkyl ester of methacrylic acid is generally used, and the carbon number of the alkyl group is about 1 to 4. In the case of copolymers, acrylates which are advantageous as copolymerization components of methacrylic resins, or other polymerizable monomers which are copolymerizable with alkyl methacrylates and / or acrylates are known.

甲基丙烯酸樹脂係理想為藉由具有碳數1~4之烷基的甲基丙烯酸烷基酯50~100重量%、與丙烯酸酯0~50重量%、與可共聚於這些成分的其他之聚合性單體 之至少1種0~49重量%所構成的單體之聚合而得。理想上係玻璃轉移溫度為40℃以上之熱塑性聚合物。在此，丙烯酸酯係較理想為在0.1~50重量%之範圍來使用，甲基丙烯酸烷基酯之較理想的共聚比例係50~99.9重量%之範圍。另外，此甲基丙烯酸樹脂之玻璃轉移溫度，較理想為60℃以上。尚，在本說明書中單獨稱「單體」時，其不僅為由某單體1種所構成的情況，亦包含混合複數之單體的狀態。 The methacrylic resin is preferably polymerized by 50 to 100% by weight of an alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms, 0 to 50% by weight with an acrylate, and other polymers copolymerizable with these components. Sex monomer It is obtained by polymerizing at least one monomer composed of 0 to 49% by weight. Ideally, it is a thermoplastic polymer with a glass transition temperature of 40 ° C or higher. Here, the acrylate is preferably used in the range of 0.1 to 50% by weight, and the more preferable copolymerization ratio of the alkyl methacrylate is in the range of 50 to 99.9% by weight. The glass transition temperature of the methacrylic resin is preferably 60 ° C or higher. In addition, in this specification, when a "monomer" is called individually, it is not only the case which consists of 1 type of certain monomer, but also the state which mixed plural monomers.

在此熱可塑性聚合物，作為甲基丙烯酸烷基酯，例如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、甲基丙烯酸第三丁酯、甲基丙烯酸2-乙基己酯、甲基丙烯酸環己酯、甲基丙烯酸2-羥基乙基酯等之烷基之碳數為1~8的甲基丙烯酸烷基酯。烷基之碳數，理想為1~4。在這些成分中由耐久性之觀點而言，特別是甲基丙烯酸甲酯可為理想地使用。甲基丙烯酸烷基酯係可僅使用1種，亦可併用2種以上。 As the thermoplastic polymer, examples of the alkyl methacrylate include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, and n-butyl methacrylate. Carbon number of alkyl groups such as esters, isobutyl methacrylate, third butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, 2-hydroxyethyl methacrylate, etc. 1 to 8 alkyl methacrylates. The carbon number of the alkyl group is preferably 1 to 4. Among these components, methyl methacrylate is particularly preferably used from the viewpoint of durability. The alkyl methacrylate system may be used alone or in combination of two or more.

作為丙烯酸酯，通常可使用丙烯酸烷基酯。作為丙烯酸烷基酯，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、丙烯酸第三丁酯、丙烯酸2-乙基己酯、丙烯酸環己酯、丙烯酸2-羥基乙基酯等之烷基之碳數為1~8的丙烯酸烷基酯。烷基之碳數，理想為1~4。丙烯酸烷基酯係可僅使用1種，亦可併用2種以上。 As the acrylate, an alkyl acrylate is usually used. Examples of the alkyl acrylate include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, third butyl acrylate, and 2-ethylhexyl acrylate. Alkyl acrylates having 1 to 8 carbon atoms in alkyl groups such as esters, cyclohexyl acrylate, and 2-hydroxyethyl acrylate. The carbon number of the alkyl group is preferably 1 to 4. The alkyl acrylate may be used alone or in combination of two or more.

作為可聚合在甲基丙烯酸烷基酯以及/或是丙烯酸酯的其他之聚合性單體，可舉出先前在此領域已知的各種單體。作為如此的單體，例如可舉出在分子內有1個聚合性的碳-碳雙鍵的單官能單體、在分子內至少具有2個聚合性之碳-碳雙鍵的多官能單體等，單官能單體係可理想地使用。作為單官能單體，具體而言，可舉出如苯乙烯、α-甲基苯乙烯、乙烯基甲苯、鹵化苯乙烯、羥基苯乙烯的苯乙烯系單體；丙烯腈、甲基丙烯腈等的氰化乙烯；丙烯酸、甲基丙烯酸、無水順丁烯二酸、衣康酸酐等之不飽和酸；N-甲基馬來醯亞胺、N-環己基馬來醯亞胺、N-苯基馬來醯亞胺等的馬來醯亞胺；甲基烯丙醇、烯丙醇等的不飽和醇；醋酸乙烯酯、氯乙烯、乙烯、丙烯、4-甲基-1-戊烯、2-羥甲基-1-丁烯、甲基乙烯基酮、N-乙烯基吡咯啶酮、N-乙烯基咔唑等其他之單體。 Examples of other polymerizable monomers that can be polymerized in alkyl methacrylate and / or acrylate include various monomers known in the art. Examples of such a monomer include a monofunctional monomer having one polymerizable carbon-carbon double bond in the molecule, and a polyfunctional monomer having at least two polymerizable carbon-carbon double bonds in the molecule. Etc. Monofunctional single systems can be ideally used. Specific examples of the monofunctional monomer include styrene-based monomers such as styrene, α-methylstyrene, vinyl toluene, halogenated styrene, and hydroxystyrene; acrylonitrile, methacrylonitrile, and the like Ethylene cyanide; unsaturated acids such as acrylic acid, methacrylic acid, anhydrous maleic acid, itaconic anhydride; N-methylmaleimide, N-cyclohexylmaleimide, N-benzene Maleimide, such as methylmaleimide; unsaturated alcohols, such as methallyl alcohol, allyl alcohol; vinyl acetate, vinyl chloride, ethylene, propylene, 4-methyl-1-pentene, Other monomers such as 2-hydroxymethyl-1-butene, methyl vinyl ketone, N-vinyl pyrrolidone, and N-vinyl carbazole.

作為多官能單體，具體而言係可舉出乙二醇二甲基丙烯酸酯、丁二醇二甲基丙烯酸酯、三羥甲基丙烷三丙烯酸酯般的多元醇之聚不飽和羧酸酯；丙烯酸烯丙酯、甲基丙烯酸烯丙酯、桂皮酸烯丙酯般的不飽和羧酸之烯基酯；酞酸二烯丙酯、馬來酸二烯丙酯、三烯丙基三聚異氰酸酯、三烯丙基異三聚異氰酸酯般的多元酸之聚烯基酯；二乙烯基苯般的芳香族聚烯基化合物等。 Examples of the polyfunctional monomer include polyunsaturated carboxylic acid esters of polyhydric alcohols such as ethylene glycol dimethacrylate, butanediol dimethacrylate, and trimethylolpropane triacrylate. ; Allyl acrylate, allyl methacrylate, allyl esters of unsaturated carboxylic acids like allyl cinnamate; diallyl phthalate, diallyl maleate, triallyl trimer Isocyanates, polyallyl esters of polyallylic acids such as triallyl isotrimeric isocyanates; aromatic polyalkenyl compounds such as divinylbenzene.

如以上成分，可共聚於甲基丙烯酸烷基酯以及/或是丙烯酸酯的其他之聚合性單體，可使用僅1種，亦可併用2種以上。 As described above, other polymerizable monomers which can be copolymerized with alkyl methacrylate and / or acrylate can be used alone or in combination of two or more.

作為甲基丙烯酸樹脂，依照之前所述，將理想為由具有碳數1~4之烷基的甲基丙烯酸烷基酯50~100重量%，較理想為50~99.9重量%、與丙烯酸酯0~50重量%，較理想為0.1~50重量%、與可共聚於這些成分的其他之聚合性單體之至少1種0~49重量%所構成的單體加以聚合而得到的熱可塑性聚合物為合適，可將在此範圍內的聚合物，作為單獨或是2種以上之聚合物之混合物而使用。此熱可塑性聚合物係玻璃轉移溫度為40℃以上即可，理想為具有60℃以上之玻璃轉移溫度。如熱可塑性聚合物之玻璃轉移溫度為40℃以上，則所得到的薄膜之耐熱性會更提高。玻璃轉移溫度，其係藉由變化甲基丙烯酸烷基酯與共聚的其他之單體之種類與量，可適宜地設定。 As the methacrylic resin, 50 to 100% by weight of an alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms, more preferably 50 to 99.9% by weight, and 0 ~ 50% by weight, preferably 0.1 ~ 50% by weight, and a thermoplastic polymer obtained by polymerizing at least one type of 0 ~ 49% by weight of other polymerizable monomers copolymerizable with these components If appropriate, the polymers in this range can be used alone or as a mixture of two or more polymers. The thermoplastic polymer-based glass transition temperature may be 40 ° C or higher, and preferably has a glass transition temperature of 60 ° C or higher. If the glass transition temperature of the thermoplastic polymer is 40 ° C or higher, the heat resistance of the obtained film will be further improved. The glass transition temperature can be appropriately set by changing the kinds and amounts of the alkyl methacrylate and other monomers to be copolymerized.

甲基丙烯酸樹脂係可提高薄膜之耐久性，所以亦可於高分子主鏈具有環狀構造。環構造係環狀酸酐構造、環狀醯亞胺構造、內酯環構造等之雜環構造為理想。具體而言，可舉出如戊二酸酐構造、琥珀酸酐構造般的環狀酸酐構造；如戊二醯亞胺構造、琥珀醯亞胺構造般的環狀醯亞胺構造；如丁內酯、戊內酯般的內酯環構造等。主鏈中之環構造含有量越大，甲基丙烯酸樹脂之玻璃轉移溫度就可變得越高。環狀酸酐構造或環狀醯亞胺構造，其係藉由使具有無水順丁烯二酸或馬來醯亞胺等之環狀構造的單體共聚而導入的方法、藉由在聚合後脫水‧脫甲醇縮合反應而導入環狀酸酐構造的方法、使胺基化合物反應而導 入環狀醯亞胺構造的方法等，可導入至主鏈中。 Methacrylic resin can improve the durability of the film, so it can also have a ring structure in the polymer main chain. The ring structure is preferably a heterocyclic structure such as a cyclic acid anhydride structure, a cyclic amidine structure, and a lactone ring structure. Specific examples include cyclic acid anhydride structures such as glutaric anhydride structure and succinic anhydride structure; cyclic fluorene imine structures such as glutaric acid imine structure and succinic acid imine structure; such as butyrolactone, Valerolactone-like lactone ring structures and the like. The larger the content of the ring structure in the main chain, the higher the glass transition temperature of the methacrylic resin. The cyclic acid anhydride structure or the cyclic amidine structure is a method of introducing a monomer having a cyclic structure such as anhydrous maleic acid, maleimide, or the like, and dehydrating it after polymerization. ‧A method for introducing a cyclic anhydride structure by a de-methanol condensation reaction, The method of introducing a cyclic fluorene imine structure, etc., can be introduced into the main chain.

具有內酯環構造的樹脂(聚合物)係可依以下方式而可得。首先，調製於高分子鏈具有羥基與酯基的聚合物。之後，將在所得到的聚合物的羥基與酯基，藉由加熱，在按照必要而有機磷酸化合物般的觸媒存在下使其進行環化縮合而形成內酯環構造。在高分子鏈中具有羥基與酯基的聚合物，其係例如藉由將如2-(羥甲基)丙烯酸甲酯、2-(羥甲基)丙烯酸乙酯、2-(羥甲基)丙烯酸異丙酯、2-(羥甲基)丙烯酸正丁酯、2-(羥甲基)丙烯酸第三丁酯般的具有羥基與酯基的丙烯酸酯或甲基丙烯酸酯，作為單體之一部分使用而可得到。具有內酯環構造的聚合物之更具體的調製方法，例如記載於日本特開2007-254726號公報。 A resin (polymer) having a lactone ring structure can be obtained in the following manner. First, a polymer having a hydroxyl group and an ester group in a polymer chain is prepared. Thereafter, the hydroxy group and the ester group of the obtained polymer are subjected to cyclization and condensation to form a lactone ring structure by heating in the presence of an organic phosphate compound-like catalyst as necessary. A polymer having a hydroxyl group and an ester group in a polymer chain is, for example, a compound such as methyl 2- (hydroxymethyl) acrylate, ethyl 2- (hydroxymethyl) acrylate, 2- (hydroxymethyl) Isopropyl acrylate, n-butyl 2- (hydroxymethyl) acrylate, tertiary butyl 2- (hydroxymethyl) acrylate, acrylate or methacrylate with hydroxyl and ester groups, as part of the monomer Available. A more specific method for preparing a polymer having a lactone ring structure is described in, for example, Japanese Patent Application Laid-Open No. 2007-254726.

上述熱可塑性聚合物之聚合方法係不特別限定，但可以通常之懸浮聚合、乳化聚合、塊狀聚合等之方法進行。另外，為了得到合適的玻璃轉移溫度，或是為了得到表現出向合適的薄膜之成形性的黏度，在聚合時使用鏈轉移劑為理想。鏈轉移劑之量係由單體之種類及組成而適宜地決定即可。 The polymerization method of the above-mentioned thermoplastic polymer is not particularly limited, but it can be performed by methods such as ordinary suspension polymerization, emulsion polymerization, and block polymerization. In addition, in order to obtain a suitable glass transition temperature or to obtain a viscosity exhibiting moldability to a suitable film, it is desirable to use a chain transfer agent during polymerization. The amount of the chain transfer agent may be appropriately determined depending on the type and composition of the monomer.

在如此的甲基丙烯酸樹脂，如上所述，由賦予薄膜耐衝擊性的觀點而言，亦可調配橡膠粒子。所使用的橡膠粒子，平均粒徑在0.05~0.4μm，更進一步在0.06~0.3μm，特別是0.1~0.25μm之範圍者為理想。如橡膠粒子之平均粒徑為如此的範圍，則不易損及薄膜之透明 性，可賦予更良好的耐衝擊性。橡膠粒子，其係在丙烯酸系樹脂(例如甲基丙烯酸樹脂)與橡膠粒子之合計100重量份中，理想為含有3~60重量份，較理想為含有5~50重量份，更理想為含有10~40重量份之比例。 In such a methacrylic resin, as described above, from the viewpoint of imparting impact resistance to a film, rubber particles can also be blended. The rubber particles used preferably have an average particle diameter of 0.05 to 0.4 μm, more preferably 0.06 to 0.3 μm, and particularly a range of 0.1 to 0.25 μm. If the average particle diameter of the rubber particles is in this range, the transparency of the film will not be easily damaged. It can provide better impact resistance. The rubber particles are preferably contained in an amount of 3 to 60 parts by weight, more preferably 5 to 50 parts by weight, and more preferably 10% by weight based on 100 parts by weight of the acrylic resin (for example, methacrylic resin) and the rubber particles. ~ 40 parts by weight.

橡膠粒子，其係理想為在具有由丙烯酸烷基酯50~99.9重量%、與可共聚於此的其他之乙烯基單體之至少1種0~49.9重量%、與共聚性之交聯性單體0.1~10重量%所構成的單體加以聚合而得的層的彈性共聚物100重量份之存在下，藉由聚合以甲基丙烯酸酯50~100重量%、與丙烯酸酯0~50重量%、與可共聚於此的其他之乙烯基單體之至少1種0~49重量%所構成的單體10~400重量份，將來自後者之單體之聚合層至少1層結合於前述彈性共聚物之表面而形成的含有橡膠的聚合物。橡膠粒子係藉由聚合條件之變更，可製造平均粒徑不同之物。 The rubber particles are preferably a crosslinkable monomer having 50 to 99.9% by weight of an alkyl acrylate and at least one type of 0 to 49.9% by weight with other vinyl monomers copolymerizable therewith. In the presence of 100 parts by weight of an elastic copolymer of a layer obtained by polymerizing a monomer composed of 0.1 to 10% by weight of a monomer, 50 to 100% by weight of methacrylate and 0 to 50% by weight of acrylate are polymerized by polymerization. 10 to 400 parts by weight of a monomer composed of at least one kind of 0 to 49% by weight of other vinyl monomers copolymerizable here, and at least one layer of a polymer layer derived from the latter monomer is combined with the aforementioned elastic copolymerization A polymer containing rubber formed on the surface of an object. By changing the polymerization conditions, rubber particles can be produced with different average particle diameters.

此含有橡膠的聚合物，例如可藉由以下之方法而得到。將彈性共聚物用之上述成分藉由乳化聚合法等，以至少單段之反應而使其聚合而得到彈性共聚物。在所得到的此彈性共聚物之存在下，將含有上述的甲基丙烯酸酯的單體，藉由乳化聚合法等，以至少單段之反應而使其聚合。藉由如此的多段之聚合，在後段使用的含有甲基丙烯酸酯的單體係接枝共聚於彈性共聚物，生成具有接枝鏈的交聯彈性共聚物。也就是，此含有橡膠的聚合物，其係成為具有將丙烯酸烷基酯作為橡膠之主成分而包含的多層構造的接枝共聚物。尚，在將彈性共聚物之聚合以二段 以上進行的情況，或是在之後將甲基丙烯酸酯作為主成分的單體之聚合，以二段以上進行的情況中，均非各段之單體組成，而是作為全體之單體組成係在上述範圍內即可。 This rubber-containing polymer can be obtained, for example, by the following method. An elastic copolymer can be obtained by polymerizing the above-mentioned components for the elastic copolymer by at least a single-stage reaction by an emulsion polymerization method or the like. In the presence of the obtained elastic copolymer, a monomer containing the methacrylate described above is polymerized by at least a single-stage reaction by an emulsion polymerization method or the like. By such a multi-stage polymerization, a single system containing a methacrylate used in the subsequent stage is graft-copolymerized to the elastic copolymer to produce a crosslinked elastic copolymer having a graft chain. That is, the rubber-containing polymer is a graft copolymer having a multilayer structure including an alkyl acrylate as a main component of the rubber. Still, in the polymerization of elastic copolymers in two stages In the case of the above, or the polymerization of monomers with methacrylate as the main component in the following, in the case of two or more stages, the monomer composition of each stage is not the entire monomer composition system. It is sufficient to be within the above range.

在上述之含有橡膠的聚合物，作為為了構成彈性共聚物所使用的丙烯酸烷基酯，例如可舉出烷基之碳數為1~8者。其中，如丙烯酸丁酯或丙烯酸2-乙基己基酯般的，烷基之碳數為4~8者為理想。 Among the above-mentioned rubber-containing polymers, examples of the alkyl acrylate used for constituting the elastic copolymer include those having 1 to 8 carbon atoms in the alkyl group. Among them, like butyl acrylate or 2-ethylhexyl acrylate, the number of carbon atoms of the alkyl group is preferably 4 to 8.

在含有橡膠的聚合物中，為了構成彈性共聚物而依期望所使用，作為可共聚於丙烯酸烷基酯的其他之乙烯基單體，例如像甲基丙烯酸甲酯、甲基丙烯酸丁酯、甲基丙烯酸環己酯般的甲基丙烯酸烷基酯、苯乙烯、丙烯腈等為理想。 Among rubber-containing polymers, it is used as desired in order to constitute an elastic copolymer. As other vinyl monomers that can be copolymerized with alkyl acrylate, for example, methyl methacrylate, butyl methacrylate, and formic acid Cyclohexyl methacrylate-like alkyl methacrylate, styrene, acrylonitrile, and the like are preferred.

在含有橡膠的聚合物，為了構成彈性共聚物所使用的共聚性之交聯性單體，其係在1分子內至少具有2個聚合性碳-碳雙鍵者即可。作為如此的交聯性單體，例如可舉出乙二醇二甲基丙烯酸酯、丁二醇二甲基丙烯酸酯般的乙二醇類之不飽和羧酸二酯；丙烯酸烯丙酯、甲基丙烯酸烯丙酯、桂皮酸烯丙酯般的不飽和羧酸之烯基酯；酞酸二烯丙酯、馬來酸二烯丙酯、三烯丙基三聚異氰酸酯、三烯丙基異三聚異氰酸酯般的多元羧酸之聚烯基酯；三羥甲基丙烷三丙烯酸酯般的多元醇之不飽和羧酸酯；二乙烯基苯等。在此之中，不飽和羧酸之烯基酯或多元羧酸之聚烯基酯為理想。這些交聯性單體，其係可各自單獨，或是按照必要而組合2種以上而使用。 In the polymer containing a rubber, in order to constitute a copolymerizable crosslinkable monomer used for the elastic copolymer, it may be one having at least two polymerizable carbon-carbon double bonds in one molecule. Examples of such a crosslinkable monomer include ethylene glycol dimethacrylate and unsaturated glycol carboxylic acid diesters such as butanediol dimethacrylate; allyl acrylate and methyl acrylate Allyl acrylate, allyl ester of unsaturated carboxylic acid like allyl cinnamate; diallyl phthalate, diallyl maleate, triallyl trimer isocyanate, triallyl isocyanate Polyalkenyl esters of polycarboxylic acids such as trimeric isocyanates; unsaturated carboxylic acid esters of polyhydric alcohols such as trimethylolpropane triacrylate; divinylbenzene and the like. Among these, an alkenyl ester of an unsaturated carboxylic acid or a polyalkenyl ester of a polycarboxylic acid is preferable. These crosslinkable monomers can be used individually or in combination of 2 or more types as needed.

如以上般的，在藉由將丙烯酸烷基酯作為主體的單體之聚合而得到的彈性共聚物中，將由甲基丙烯酸酯50~100重量%、與丙烯酸酯0~50重量%、可共聚於這些成分的其他之乙烯基單體之至少1種0~49重量%所構成的單體，使其進行接枝。接枝於彈性共聚物的甲基丙烯酸酯，其係甲基丙烯酸烷基酯為理想，例如可舉出甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丁酯、甲基丙烯酸2-乙基己酯、甲基丙烯酸環己酯等。作為對這些甲基丙烯酸酯而藉由期望而共聚的丙烯酸酯，例如可舉出丙烯酸甲酯、丙烯酸丁酯、丙烯酸環己酯般的丙烯酸烷基酯。另外，作為可共聚於甲基丙烯酸酯以及/或是丙烯酸酯的其他之乙烯基單體，例如可舉出苯乙烯、丙烯腈等。 As described above, in the elastic copolymer obtained by polymerizing a monomer having an alkyl acrylate as a main component, 50 to 100% by weight of methacrylate, 0 to 50% by weight and acrylate can be copolymerized. Grafting is performed on at least one kind of a monomer composed of 0 to 49% by weight of other vinyl monomers in these components. The methacrylate grafted to the elastic copolymer is preferably an alkyl methacrylate, and examples thereof include methyl methacrylate, ethyl methacrylate, butyl methacrylate, and methacrylic acid 2- Ethylhexyl, cyclohexyl methacrylate and the like. Examples of the acrylate copolymerized with these methacrylates as desired include alkyl acrylates such as methyl acrylate, butyl acrylate, and cyclohexyl acrylate. Examples of other vinyl monomers copolymerizable with methacrylate and / or acrylate include styrene and acrylonitrile.

使其進行接枝的單體，其係可相對於彈性共聚物100重量份，理想為使用10~400重量份，較理想為20~200重量份，至少以單段以上之反應來聚合。在此使其進行接枝的單體之使用量若設為10重量份以上，則難以產生彈性共聚物之凝聚，透明性變良好。 The monomer to be grafted can be polymerized in a reaction of at least a single stage based on 100 parts by weight of the elastic copolymer, preferably 10 to 400 parts by weight, more preferably 20 to 200 parts by weight. When the amount of the monomer to be grafted is 10 parts by weight or more, aggregation of the elastic copolymer is difficult to occur, and transparency becomes good.

另外，在上述之彈性共聚物層之內側，其係可設置以甲基丙烯酸酯作為主體的硬質層。在此情況中，將構成最內層的硬質層之單體，首先使其聚合即可。接著，在所得的硬質聚合物之存在下，使構成上述彈性共聚物的單體聚合。更進一步，在所得的彈性共聚物之存在下，將上述之甲基丙烯酸酯作為主體，讓進行接枝的單體聚合即可。在此，成為最內層的硬質層，其係將由甲基丙 烯酸酯70~100重量%、與可共聚於該成分的其他之乙烯基單體0~30重量%所構成的單體進行聚合為理想。此時，作為其他乙烯基單體之一，使用共聚性之交聯性單體亦為有效。作為甲基丙烯酸酯，係甲基丙烯酸烷基酯，特別是甲基丙烯酸甲酯為有效。如此的3層構造之含有橡膠的聚合物，例如開示於上述日本特公昭55-27576號公報(專利文獻3)。特別是記載於專利文獻3之實施例3者，其係理想的組成之一。 In addition, a hard layer mainly composed of methacrylate may be provided inside the elastic copolymer layer. In this case, the monomers constituting the innermost hard layer may be polymerized first. Next, the monomer which comprises the said elastic copolymer is polymerized in the presence of the obtained hard polymer. Furthermore, in the presence of the obtained elastic copolymer, the above-mentioned methacrylate may be used as a main component, and the monomer to be grafted may be polymerized. Here, it becomes the innermost hard layer, which will be made of methyl propylene It is preferable to polymerize a monomer composed of 70 to 100% by weight of an acrylate and 0 to 30% by weight of another vinyl monomer copolymerizable with the component. In this case, it is also effective to use a copolymerizable crosslinkable monomer as one of the other vinyl monomers. As the methacrylate, an alkyl methacrylate, particularly methyl methacrylate is effective. Such a rubber-containing polymer having a three-layer structure is disclosed, for example, in the aforementioned Japanese Patent Publication No. 55-27576 (Patent Document 3). In particular, it is described in Example 3 of Patent Document 3, which is one of the ideal compositions.

尚，橡膠粒子之平均粒徑係可以電子顯微鏡觀察而求出。例如，將各自之橡膠粒子單獨與甲基丙烯酸樹脂混合而薄膜化，在該剖面，使用氧化釕而將橡膠成分染色。在染色後，以電子顯微鏡觀察，可由被染色的粒子外層部之直徑來求出。因此，在此所謂的粒子直徑是數平均粒徑。 The average particle diameter of the rubber particles can be determined by observation with an electron microscope. For example, each of the rubber particles is mixed with a methacrylic resin to form a thin film. In this cross section, the rubber component is dyed using ruthenium oxide. After dyeing, observation with an electron microscope can be obtained from the diameter of the outer layer portion of the dyed particles. Therefore, the so-called particle diameter is a number average particle diameter.

上述丙烯酸系樹脂中，亦可含有通常之添加劑，例如紫外線吸收劑、有機系染料、無機系染料、顏料、防氧化劑、防帶電劑、界面活性劑等。其中尤其是紫外線吸收劑，在提供更長時間之耐候性優異的薄膜之觀點上，可理想的使用。作為紫外線吸收劑，例如可舉出一般所使用的苯并***系紫外線吸收劑、2-羥基二苯甲酮系紫外線吸收劑、水楊酸苯基酯系紫外線吸收劑等。作為苯并***系紫外線吸收劑，具體而言，可例示2,2’-亞甲基鏈雙〔4-(1,1,3,3-四甲基丁基)-6-(2H-苯并***-2-基)酚〕、2-(5-甲基-2-羥苯基)苯并***、2-〔2-羥基-3,5- 雙(α,α-二甲基苄基)苯基〕-2H-苯并***、2-(3,5-二-tert-丁基-2-羥苯基)苯并***、2-(3-tert-丁基-5-甲基-2-羥苯基)-5-氯苯并***、2-(3,5-二-tert-丁基-2-羥苯基)-5-氯苯并***、2-(3,5-二-tert-戊基-2-羥苯基)苯并***、2-(2’-羥基-5’-tert-辛基苯基)苯并***等。 The acrylic resin may contain ordinary additives such as an ultraviolet absorber, an organic dye, an inorganic dye, a pigment, an antioxidant, an antistatic agent, and a surfactant. Among them, an ultraviolet absorber is preferably used from the viewpoint of providing a film having excellent weather resistance for a longer period of time. Examples of the ultraviolet absorber include benzotriazole-based ultraviolet absorbers, 2-hydroxybenzophenone-based ultraviolet absorbers, and phenylsalicylate-based ultraviolet absorbers, which are generally used. As a benzotriazole-based ultraviolet absorber, specifically, 2,2'-methylene chain bis [4- (1,1,3,3-tetramethylbutyl) -6- (2H- Benzotriazol-2-yl) phenol], 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5- Bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (3,5-di-tert-butyl-2-hydroxyphenyl) benzotriazole, 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-tert-butyl-2-hydroxyphenyl) -5 -Chlorobenzotriazole, 2- (3,5-di-tert-pentyl-2-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5'-tert-octylphenyl) Benzotriazole and so on.

作為2-羥基二苯甲酮系紫外線吸收劑，具體而言係可例示2-羥基-4-甲氧基二苯基酮、2-羥基-4-辛氧基二苯基酮、2,4-二羥基二苯基酮、2-羥基-4-甲氧基-4’-氯二苯基酮、2,2’-二羥基-4-甲氧基二苯基酮、2,2’-二羥基-4,4’-二甲氧基二苯基酮等。 Specific examples of the 2-hydroxybenzophenone-based ultraviolet absorber include 2-hydroxy-4-methoxydiphenyl ketone, 2-hydroxy-4-octyloxydiphenyl ketone, and 2,4 -Dihydroxydiphenyl ketone, 2-hydroxy-4-methoxy-4'-chlorodiphenyl ketone, 2,2'-dihydroxy-4-methoxydiphenyl ketone, 2,2'- Dihydroxy-4,4'-dimethoxydiphenyl ketone and the like.

另外，作為水楊酸苯基酯系紫外線吸收劑，具體而言可例示，p-tert-丁基苯基水楊酸酯、p-辛基苯基水楊酸酯等。 Specific examples of the phenylsalicylate-based ultraviolet absorber include p-tert-butylphenylsalicylate, p-octylphenylsalicylate, and the like.

這些紫外線吸收劑，可各自單獨或2種以上混合使用。紫外線吸收劑之含有量係由所期望之丙烯酸系樹脂擠出成形薄膜之厚度而適宜地設定，但相對於丙烯酸系樹脂100重量份而言，通常為0.1重量份以上，理想為0.3重量份以上，另外通常為5重量份以下。具有所期望之厚度的丙烯酸系樹脂擠出成形薄膜之在波長380nm的透過率，可在理想為25%以下，較理想為15%以下，更理想為5%以下的範圍加以選擇。例如在具有80μm之厚度的薄膜之情況，為了顯現與作為光學薄膜而使用的三乙醯基纖維素薄膜相同之紫外線吸收能，其係將甲基丙烯酸樹脂及橡膠粒子之合計100重量份設為基準，將紫外線吸收 劑之量設為2.0重量份左右為合適。以這些紫外線吸收劑為首的添加劑，為了防止在將丙烯酸系樹脂由模頭吐出時成為揮發成分而蒸散，污染輥等情事，所以具有180℃以上之融點者為理想。 These ultraviolet absorbers can be used individually or in mixture of 2 or more types. The content of the ultraviolet absorber is appropriately set based on the thickness of the desired acrylic resin extruded film, but it is usually 0.1 parts by weight or more, and preferably 0.3 parts by weight or more, based on 100 parts by weight of the acrylic resin. In addition, it is usually 5 parts by weight or less. The transmittance of the acrylic resin extruded film having a desired thickness at a wavelength of 380 nm can be selected within a range of preferably 25% or less, more preferably 15% or less, and even more preferably 5% or less. For example, in the case of a film having a thickness of 80 μm, 100 parts by weight of the total of methacrylic resin and rubber particles is set in order to show the same ultraviolet absorption energy as the triethyl cellulose film used as an optical film. Benchmark, absorbs ultraviolet light The amount of the agent is preferably set to about 2.0 parts by weight. The additives including these ultraviolet absorbers are preferably those having a melting point of 180 ° C. or higher in order to prevent volatile components from evaporating when the acrylic resin is ejected from the die and contamination of the roller.

[丙烯酸系樹脂薄膜之製造方法] [Manufacturing method of acrylic resin film]

接著，將本發明之丙烯酸系樹脂薄膜之製造方法之一實施形態，參照圖面而進行說明。第1圖係概略地表示有關本發明的製造方法之一實施形態全體的說明圖。在此圖中，以熔融狀態擠出的薄膜狀物1，以及此物冷卻固化後之物的薄膜狀成形體2以及丙烯酸系樹脂薄膜3，以虛線表示。然後，由T型模頭10所擠出的薄膜狀物1，係被挾持在第一冷卻輥11與第二冷卻輥12而成為薄膜狀成形體2，經由按照必要所配置的第三冷卻輥13之後，以搬送輥20、20搬送。在搬送中，由切割器14而切斷薄膜狀成形體2之寬度方向側端部，成為具有目的之寬度的丙烯酸系樹脂薄膜3。之後，以通過累積器15、夾輥16、跳動輥17，由搬送輥20而被引導向捲取核心19的方式進行。在捲取核心19側係配置有按壓輥18。藉由此按壓輥18而薄膜3被按壓在捲取核心19側而捲取，可得輥狀丙烯酸系樹脂薄膜5(被捲成輥狀的丙烯酸系樹脂薄膜)。在將薄膜捲取之前的期間，亦可包含延伸、或含有塗佈的表面處理等加工製程。 Next, an embodiment of a method for producing an acrylic resin film of the present invention will be described with reference to the drawings. FIG. 1 is an explanatory diagram schematically showing the entirety of an embodiment of a manufacturing method of the present invention. In this figure, the film-like object 1 extruded in a molten state, and the film-like formed body 2 and the acrylic resin film 3 after the object is cooled and solidified are shown by dotted lines. Then, the film-like object 1 extruded from the T-die 10 is held by the first cooling roll 11 and the second cooling roll 12 to form a film-like formed body 2, and the third cooling roll is arranged as necessary. After 13, it is conveyed by the conveying rollers 20 and 20. During conveyance, the width-direction side end portion of the film-shaped molded body 2 is cut by the cutter 14 to become the acrylic resin film 3 having a desired width. Thereafter, it is performed so that it may be guided to the winding core 19 by the conveying roller 20 through the accumulator 15, the nip roller 16, and the jump roller 17. A pressing roller 18 is arranged on the winding core 19 side. As a result, the roller 3 is pressed and the film 3 is pressed against the winding core 19 and rolled up, and a roll-shaped acrylic resin film 5 (acrylic resin film rolled into a roll shape) can be obtained. The period before the film is wound up may include processing processes such as stretching or surface treatment including coating.

丙烯酸系樹脂薄膜之製造方法係有將丙烯酸 系樹脂由T型模頭10作為薄膜狀物1而擠出的擠出步驟。擠出機係藉由投入於其中的樹脂之形態，使用具有1支或2支的螺桿之物，熔融混練丙烯酸系樹脂。在由T型模頭10擠出薄膜狀物1之前，亦可適宜地設置用以過濾樹脂中較大的異物等而除去之網板篩、用以過濾樹脂中較小的異物或膠體等而除去之聚合物過濾器、用以將擠出樹脂量加以安定定量化之齒輪泵等。 Acrylic resin film The extrusion step of extruding the resin from the T-die 10 as the film-like material 1. The extruder is based on the form of the resin to be used, and the acrylic resin is melt-kneaded using a screw having one or two screws. Before the film-like object 1 is extruded from the T-die 10, a screen sieve for removing large foreign matters in the resin and a small foreign matter or colloid in the resin may also be appropriately provided. Removed polymer filters, gear pumps to stabilize and quantify the amount of resin extruded.

T型模頭10係具有狹縫狀之唇口的模頭，可適宜地選擇使用歧管模頭、魚尾模頭、衣架模頭、螺紋模頭等。在製造多層之樹脂薄膜的情況中，亦可使用多歧管模頭等。另外，T型模頭10之唇口寬度係對應於由擠出而製造的薄膜狀成形體2之薄膜寬度，在不使生產效率低落的範圍內適宜地設定。通常，具有相對於所製造的薄膜狀成形體2之寬度而言，1.2~1.5倍左右之唇口寬度者係可理想地使用。 The T-die 10 is a die having a slit-shaped lip, and a manifold die, a fish tail die, a hanger die, a thread die, and the like can be appropriately selected and used. In the case of manufacturing a multilayer resin film, a multi-manifold die or the like may be used. The lip width of the T-die 10 corresponds to the film width of the film-like formed body 2 produced by extrusion, and is appropriately set within a range that does not reduce production efficiency. Generally, those having a lip width of about 1.2 to 1.5 times the width of the manufactured film-like molded body 2 are preferably used.

具有可將狹縫狀之唇口之開度，以排列於T型模頭10之寬度方向的螺栓而調整的可撓性唇口者係可理想地使用，但不特別限定於此。另外唇口開度係由所期望的薄膜之厚度而適宜地調整。一般而言，相對於設為目的的薄膜之厚度，在1.01~10倍左右，理想為在1.1~5倍左右之範圍調整。唇口開度係在寬度方向並不均勻，為了將所得的薄膜之厚度作為均勻，一般而言在寬度方向上有分布。 Those having a flexible lip that can adjust the opening of the slit-shaped lip with bolts arranged in the width direction of the T-die 10 are ideally used, but are not particularly limited thereto. The lip opening degree is appropriately adjusted by the thickness of the desired film. Generally, the thickness of the intended film is adjusted from about 1.01 to 10 times, and preferably from about 1.1 to 5 times. The lip opening is not uniform in the width direction. In order to make the thickness of the obtained film uniform, it is generally distributed in the width direction.

丙烯酸系樹脂薄膜之製造方法係更進一步， 將由上述之擠出步驟而擠出的薄膜狀物1，至少接觸到1支輥，成形為薄膜狀成形體2的成形步驟。輥支數，如至少有1支，則可作為薄膜狀成形體2。在本發明中，將以熔融狀態擠出的薄膜狀物1，挾持於第一冷卻輥11與第二冷卻輥12之間，成形為薄膜狀成形體2。此時，在第一冷卻輥11與第二冷卻輥12之間的間隙(輥縫)係依所期望的薄膜厚度而適宜地調整。以薄膜狀物1之兩表面係同時確實地接於2支冷卻輥11、12之表面之方式，來設定輥縫為理想。 The manufacturing method of acrylic resin film is further, The step of forming the film-like article 1 extruded from the above-mentioned extrusion step into at least one roll to form a film-like formed body 2. If the number of rolls is at least one, it can be used as the film-shaped formed body 2. In the present invention, the film-like object 1 extruded in a molten state is held between the first cooling roll 11 and the second cooling roll 12 to form a film-like formed body 2. At this time, the gap (roll gap) between the first cooling roll 11 and the second cooling roll 12 is appropriately adjusted depending on the desired film thickness. The roll gap is ideally set such that both surfaces of the film-like object 1 are reliably connected to the surfaces of the two cooling rolls 11 and 12 at the same time.

冷卻輥11、12係可以金屬構成，亦可以橡膠構成。例如，第一冷卻輥11與第二冷卻輥12係雙方都可為金屬輥，亦可一方為橡膠輥，另一方為金屬輥。而且，亦可雙方都是橡膠輥。但是，為了將所得到的薄膜狀成形體2之表面修整為光澤面，則使用金屬輥為理想。特別是，研磨金屬輥表面，施以電鍍加工，在可得更高的光澤面之觀點上為理想。此時，金屬輥係在圓筒形之金屬內部配置熱媒，圓筒形金屬係因內部熱媒之壓力而可變形，即所謂的金屬彈性輥為理想。特別是，將第一冷卻輥11以如此的金屬彈性輥構成為理想。 The cooling rollers 11 and 12 may be made of metal or rubber. For example, both the first cooling roll 11 and the second cooling roll 12 may be metal rolls, one may be a rubber roll, and the other may be a metal roll. Moreover, both sides may be rubber rollers. However, in order to trim the surface of the obtained film-like formed body 2 to a glossy surface, it is preferable to use a metal roller. In particular, it is preferable from the viewpoint of obtaining a higher gloss surface that the surface of the metal roll is polished and electroplated. At this time, the metal roller is arranged with a heat medium inside the cylindrical metal, and the cylindrical metal system is deformable by the pressure of the internal heat medium, which is a so-called metal elastic roller. In particular, it is desirable that the first cooling roller 11 is configured by such a metal elastic roller.

另外，在另一方之第二冷卻輥12，理想上可使用金屬剛體。由金屬剛體所構成的輥，也就是金屬剛體輥，其係高剛性而可調節溫度者為理想，例如可舉出鑽孔型輥或螺旋形輥。 In addition, a metal rigid body can be preferably used for the other second cooling roller 12. A roll made of a metal rigid body, that is, a metal rigid body roll, is preferably one having high rigidity and adjustable temperature, and examples thereof include drill-type rolls and spiral rolls.

理想為以金屬剛體構成的第二冷卻輥12之表 面，其係於丙烯酸系樹脂薄膜之表面轉印該形狀。因為，為了抑制薄膜之外部霧度，得到透明的薄膜，所以該平均表面粗糙度Ra係0.04以下為理想。平均表面粗糙度Ra係依照JIS B0601-1982之「表面粗糙度之定義與表示」而測定的值。 Ideally a table of the second cooling roller 12 made of a metal rigid body This shape is transferred to the surface of the acrylic resin film. Since a transparent film is obtained in order to suppress the external haze of the film, the average surface roughness Ra is preferably 0.04 or less. The average surface roughness Ra is a value measured in accordance with "Definition and Expression of Surface Roughness" in JIS B0601-1982.

第二冷卻輥12係將該表面溫度調整至理想為60~130℃，較理想為80~115℃之範圍為佳。藉由調整至如此的溫度範圍，變得更容易由第二冷卻輥12剝離薄膜狀成形體2。而且在冷卻固化時難以收縮，可得均勻的薄膜。另外，因為由第一冷卻輥11剝離薄膜狀物1變得容易，所以第二冷卻輥12之表面溫度係調整為比第一冷卻輥11之表面溫度高1℃以上為理想。 The second cooling roll 12 adjusts the surface temperature to a range of preferably 60 to 130 ° C, and more preferably a range of 80 to 115 ° C. By adjusting to such a temperature range, it becomes easier to peel the film-like molded body 2 from the second cooling roll 12. In addition, it is difficult to shrink during cooling and solidification, and a uniform film can be obtained. In addition, since it is easy to peel off the film-like object 1 from the first cooling roll 11, it is desirable that the surface temperature of the second cooling roll 12 is adjusted to be 1 ° C. or higher than the surface temperature of the first cooling roll 11.

經由以上之擠出步驟及成形步驟而得到的丙烯酸系樹脂所構成的薄膜狀成形體2，其係在之後接觸1支或複數支的輥，同時徐徐地冷卻。在第1圖所示的例子中，挾持於第一冷卻輥11與第二冷卻輥12而冷卻的薄膜狀物1，之後，其以接觸在第二冷卻輥12之與第一冷卻輥11相反側設置的第三冷卻輥13之方式而冷卻。如此進行冷卻，成為固體的薄膜狀成形體2，其係被支持在搬送輥20、20，同時被連續地送到接下來的步驟。 The film-like formed body 2 made of the acrylic resin obtained through the above-mentioned extrusion step and forming step is slowly cooled while contacting one or more rolls. In the example shown in FIG. 1, the film-like object 1 that is cooled by being held by the first cooling roll 11 and the second cooling roll 12 is then opposed to the first cooling roll 11 in contact with the second cooling roll 12. It is cooled by the third cooling roller 13 provided on the side. After cooling in this manner, the solid film-like formed body 2 is supported by the conveying rollers 20 and 20 and is continuously conveyed to the next step.

在本發明中，設有將薄膜狀成形體2之寬度方向側端部藉由切割器14而切斷，得到具有設為目的的寬度的丙烯酸系樹脂薄膜3的縱切步驟。由T型模頭10擠出，由冷卻輥11、12、13而冷卻的薄膜狀成形體2， 其係在寬度方向兩端部之厚度變動大。因而，若依照原樣態捲取則輥狀樹脂薄膜之外觀變差。另外丙烯酸系樹脂薄膜係一般而言容易破裂，如上述般的擠出而得到的薄膜狀成形體2，其係寬度方向兩端部變得比中心部厚。因此，因為若依照原樣態捲取則會成為在搬送中發生斷裂的原因，所以設有此縱切步驟。 In the present invention, there is provided a slitting step of cutting the widthwise side end portion of the film-like formed body 2 by a cutter 14 to obtain an acrylic resin film 3 having a desired width. Film-shaped formed body 2 extruded from T-die 10 and cooled by cooling rolls 11, 12, 13 It has a large variation in thickness at both ends in the width direction. Therefore, if it is wound up as it is, the appearance of the roll-shaped resin film is deteriorated. In addition, the acrylic resin film is generally easy to crack, and the film-shaped molded body 2 obtained by extrusion as described above has thicker end portions in the width direction than the central portion. Therefore, this rewinding step is provided because it can cause breakage during transportation if it is wound up as it is.

以先前之成形步驟所得到的薄膜狀成形體2，其係以此縱切步驟而在寬度方向之兩側端部按照所期之製品寬度而切斷，成為製品(丙烯酸系樹脂薄膜3)。因此而使用的切割器14，其係將薄膜狀成形體2沿著進行方向，也就是與進行方向平行，可進行切斷者即可。例如，由薄膜狀成形體2之上面或下面壓住圓刃之切割器而裁切的旋轉切斷機，係由防止薄膜之斷裂的觀點而言，可合適地使用。另外，亦可使用以雷射而切斷薄膜狀成形體2之兩端部的雷射切割機。 The film-shaped molded body 2 obtained in the previous molding step is cut into the product (acrylic resin film 3) by cutting in the slitting step at both end portions in the width direction according to the desired product width. The cutter 14 used for this purpose is only required to cut the film-shaped formed body 2 along the direction of progress, that is, parallel to the direction of progress. For example, a rotary cutter that cuts a cutter with a round blade pressed from above or below the film-shaped formed body 2 can be suitably used from the viewpoint of preventing film breakage. In addition, a laser cutter that cuts both end portions of the film-shaped formed body 2 with a laser may be used.

薄膜狀成形體2，再加上將該寬度方向兩端部切斷除去而得的丙烯酸系樹脂薄膜3之厚度，按照用途而選擇即可。例如，在10~500μm之範圍者為理想，較理想為20~100μm之範圍。特別是，若丙烯酸系樹脂薄膜3之厚度為100μm以下，則薄膜之剛性低，由其本身重量，在捲取的狀態容易產生多角形，所以更期待本發明之效果。在此所謂的多角形，意味著已捲取為輥狀的輥狀丙烯酸系樹脂薄膜5之剖面，在本來應該成為圓形處(圓柱剖面)，變為多角形的現象。 The thickness of the film-like molded body 2 and the acrylic resin film 3 obtained by cutting and removing both ends in the width direction may be selected according to the application. For example, a range of 10 to 500 μm is desirable, and a range of 20 to 100 μm is more desirable. In particular, if the thickness of the acrylic resin film 3 is 100 μm or less, the rigidity of the film is low, and a polygon is liable to be generated in a rolled state due to its own weight. Therefore, the effect of the present invention is more expected. The term “polygonal” here means a phenomenon in which the cross-section of the roll-shaped acrylic resin film 5 which has been wound into a roll shape should have a circular shape (cylindrical cross-section) and become a polygon.

在切斷側端部後所得到的丙烯酸系樹脂薄膜3之寬度，亦按照用途而選擇即可。例如，在250~3000mm之範圍者為理想，較理想為500~2000mm之範圍。特別是，若薄膜之寬度為500mm以上，則還是因其本身重量，在捲取的狀態容易產生多角形，所以更期待本發明之效果。 The width of the acrylic resin film 3 obtained after cutting the side end portion may be selected according to the application. For example, a range of 250 to 3000 mm is desirable, and a range of 500 to 2000 mm is more desirable. In particular, if the width of the film is 500 mm or more, it is easy to generate a polygon in the rolled state due to its own weight, so the effect of the present invention is more expected.

[丙烯酸系樹脂薄膜之捲取方法] [Winding method of acrylic resin film]

在縱切步驟已切斷除去寬度方向兩端部的丙烯酸系樹脂薄膜3，其係依序經過累積器15、夾輥16、以及跳動輥17，於捲取核心19捲取，得到輥狀丙烯酸系樹脂薄膜5。然後，於捲取核心19側係配置按壓輥18，以此按壓輥18將丙烯酸系樹脂薄膜3緊壓於捲取核心19側之方式來捲取。累積器15及夾輥16，亦可配置於縱切步驟之前，也就是切割器14之前。 In the slitting step, the acrylic resin film 3 at both ends in the width direction has been cut and removed. The acrylic resin film 3 passes through the accumulator 15, the nip roller 16, and the jump roller 17 in order, and is wound on the winding core 19 to obtain roll-shaped acrylic.系 Before a resin film 5. Then, a pressing roller 18 is arranged on the side of the winding core 19, and the acrylic resin film 3 is tightly pressed against the side of the winding core 19 by the pressing roller 18 to be wound. The accumulator 15 and the nip roller 16 may be disposed before the slitting step, that is, before the cutter 14.

在輥狀樹脂薄膜5之捲取進行至特定長度或特定直徑而結束時，停止捲取核心19之旋轉，交換為其他之捲取核心19。即使伴隨著此交換作業，薄膜之搬送係暫時性停止的狀態，以可不停止T型模頭10及冷卻輥11、12、13之生產之方式，也就是以在捲取核心19交換時先儲存薄膜為目的，設置有累積器15。另外夾輥16，其係在隨著上述的捲取核心19之交換而暫時停止薄膜之搬送時，擔任賦予生產線全體與平穩時間相同的搬送張力，換言之就是在成為沒有來自捲取核心19的捲取張力 時，賦與代替其的張力等之角色。跳動輥17，其係用以調節被捲取在捲取核心19的丙烯酸系樹脂薄膜3之張力(捲取張力)而設置。在第1圖中，藉由使3支輥之中，位於中央的輥上下移動而控制被捲取的薄膜3之張力。因而，丙烯酸系樹脂薄膜3之捲取張力係經由跳動輥17而測定。 When the winding of the roll-shaped resin film 5 is completed to a specific length or a specific diameter, the rotation of the winding core 19 is stopped and exchanged for other winding cores 19. Even with this exchange operation, the film conveyance is temporarily stopped, and the production of the T-die 10 and the cooling rollers 11, 12, and 13 can be stopped, that is, the film is stored before the winding core 19 is exchanged. For the purpose of the film, an accumulator 15 is provided. In addition, the nip roller 16 is used to give the entire production line the same conveying tension as the smooth time when the film conveyance is temporarily stopped as the winding core 19 is exchanged. In other words, it becomes a coil without the winding core 19 Take tension At the same time, it is given the role of replacing the tension. The jump roller 17 is provided to adjust the tension (winding tension) of the acrylic resin film 3 wound on the winding core 19. In FIG. 1, the tension of the film 3 to be wound is controlled by moving the roller located at the center among the three rollers up and down. Therefore, the take-up tension of the acrylic resin film 3 is measured via the jumping roller 17.

按壓輥18，其係配置在與被捲取的丙烯酸系樹脂薄膜3接觸的位置即可。理想為丙烯酸系樹脂薄膜3捲取，成為輥狀丙烯酸系樹脂薄膜5的位置或配置於該處稍前。一般而言是如第1圖，成為在輥狀丙烯酸系樹脂薄膜5之最表面，按壓輥18所接觸的位置。但是，例如若由輥狀丙烯酸系樹脂薄膜5之最表面至10mm左右，則按壓輥18係不接觸輥狀丙烯酸系樹脂薄膜5之最表面的部位，也就是，設置於成為輥狀丙烯酸系樹脂薄膜5的部位之稍前處亦可。 The pressing roller 18 may be disposed at a position in contact with the acrylic resin film 3 being wound up. It is desirable that the acrylic resin film 3 is wound up, and the position to be the roll-shaped acrylic resin film 5 is placed or placed slightly in front of it. Generally, as shown in FIG. 1, it is a position which the pressing roller 18 contacts on the outermost surface of the roll-shaped acrylic resin film 5. However, for example, from the top surface of the roll-shaped acrylic resin film 5 to about 10 mm, the pressing roller 18 is not in contact with the top surface of the roll-shaped acrylic resin film 5, that is, it is provided at the position of the roll-shaped acrylic resin. The film 5 may be slightly forward.

若輥狀丙烯酸系樹脂薄膜5之匝徑達到特定之長度，則暫時中斷捲取作業，切斷丙烯酸系樹脂薄膜3。接著，將輥狀丙烯酸系樹脂薄膜5與捲取核心19一起卸下，將新的其他捲取核心19裝於架台，將切斷後之丙烯酸系樹脂薄膜3固定於新的捲取核心19，恢復捲取作業。 When the roll diameter of the roll-shaped acrylic resin film 5 reaches a specific length, the winding operation is temporarily suspended, and the acrylic resin film 3 is cut. Next, the roll-shaped acrylic resin film 5 is unloaded together with the winding core 19, and another new winding core 19 is mounted on a stand. The cut acrylic resin film 3 is fixed to the new winding core 19 and restored. Take-up job.

將丙烯酸系樹脂薄膜3捲取為輥狀時之捲取張力，其係設為50~250N/m之範圍。此捲取張力係60~200N/m之範圍為理想，70~170N/m之範圍為較理想。若 捲取張力低於50N/m，則於輥狀丙烯酸系樹脂薄膜5產生捲繞偏移的可能性變大。另一方面，若捲取張力超過250N/m，則於輥狀丙烯酸系樹脂薄膜5顯著產生暴筋(gauge band)。在此所謂的暴筋(gauge band)，其係沿著捲取為輥狀的丙烯酸系樹脂薄膜5之表面之圓周方向，可觀察到突起狀的瘤狀物或捲瘤狀物。 The winding tension when the acrylic resin film 3 is rolled into a roll shape is set in a range of 50 to 250 N / m. The winding tension is ideally in the range of 60 to 200 N / m, and more preferably in the range of 70 to 170 N / m. If When the take-up tension is less than 50 N / m, there is a high possibility that a roll offset may occur in the roll-shaped acrylic resin film 5. On the other hand, if the take-up tension exceeds 250 N / m, a significant band is generated in the roll-shaped acrylic resin film 5. Here, a so-called “gauge band” is a protrusion-shaped nodule or a rolled nodule observed along the circumferential direction of the surface of the acrylic resin film 5 wound into a roll shape.

捲取張力係亦可不管輥狀丙烯酸系樹脂薄膜5之匝徑，以成為一定的方式進行，但按照匝徑而使其變化較佳。在後者的情況中，可按照匝徑而捲取張力以直線性變化，且亦可按照匝徑而捲取張力以曲線或某函數而變化。此時之變化率，被稱為尖削率(taper rate)。尖削率係初期捲取張力F1與變化後之捲取張力F2之比例，也就是，以下式(1)定義。 The winding tension system may be performed regardless of the turn diameter of the roll-shaped acrylic resin film 5, but it is preferable to change it according to the turn diameter. In the latter case, the winding tension can be changed linearly in accordance with the turn diameter, and the winding tension can also be changed in a curve or a function according to the turn diameter. The rate of change at this time is called the taper rate. The sharpening rate is a ratio of the initial winding tension F1 to the changed winding tension F2, that is, defined by the following formula (1).

[1-(F2/F1)]×100[%] (1) [1- (F2 / F1)] × 100 [%] (1)

捲取張力係隨著匝徑變大，可變得比初期值大，且亦可變得比初期值小。以初期值之捲取張力開始捲取，只有在之後立即暫時變得比初期值大，之後徐徐地下降而變得比初期值小之方式進行，則來自捲取核心19的向輥狀丙烯酸系樹脂薄膜5所造成的影響變小，輥外觀變好。即使在將捲取張力按照匝徑而變化的情況，在本發明中，由捲取初期至捲取結束，亦以成為上述的50~250N/m之範圍的方式來進行。 The winding tension may become larger than the initial value as the turn diameter becomes larger, and may also be smaller than the initial value. The winding is started with the winding tension of the initial value, and only after it becomes temporarily larger than the initial value, and then gradually decreases and becomes smaller than the initial value. Then, the roll-shaped acrylic from the winding core 19 is performed. The influence caused by the resin film 5 is reduced, and the roll appearance is improved. Even in the case where the winding tension is changed according to the turn diameter, in the present invention, it is performed so as to fall within the above-mentioned range of 50 to 250 N / m from the beginning of winding to the end of winding.

按壓輥18係例如為金屬輥或橡膠輥、碳輥等。在按壓輥18之寬度方向中央部與端部亦可為輥徑不 同的凸面連續變化輥。在使用凸面連續變化輥的情況，該凸面連續變化量，也就是，輥徑最大之部位(通常表現在寬度方向中央部)與輥徑最小之部位(通常表現在寬度方向端部)之間之直徑之差，為1~100μm之範圍為理想。 The pressing roller 18 is, for example, a metal roller, a rubber roller, a carbon roller, or the like. The center and end portions of the pressing roller 18 in the width direction may also have different roller diameters. The same convex surface continuously changes the roller. In the case of using a continuously changing roller with a convex surface, the amount of continuous change of the convex surface, that is, between the portion with the largest roll diameter (usually shown in the center in the width direction) and the portion with the smallest roll diameter (usually in the width direction at the end) The difference in diameter is preferably in the range of 1 to 100 μm.

在使用橡膠輥的情況，該硬度係以JIS K6233-3：2012「加硫橡膠及熱可塑性橡膠-硬度之求得方法-第3部：硬度計硬度」的type A，在A10~A90之範圍為理想。硬度計硬度之type A係一般而言亦被稱為邵氏硬度A」。如使用具有此程度之硬度的橡膠輥，則因為可用面接觸於薄膜，所以輥外觀變良好。另外，在使用金屬輥的情況，以在該表面纏繞緩衝材料，可得到輥外觀為更良好的輥狀丙烯酸系樹脂薄膜5。 When using a rubber roller, the hardness is based on JIS K6233-3: 2012 "Vulcanized rubber and thermoplastic rubber-Method for determining hardness-Part 3: Hardness hardness" Type A, in the range of A10 ~ A90 As ideal. The type A of durometer hardness is also generally called the Shore A hardness. " If a rubber roller having such a degree of hardness is used, the usable surface contacts the film, so the appearance of the roller becomes good. When a metal roll is used, a roll-shaped acrylic resin film 5 having a better roll appearance can be obtained by winding a buffer material on the surface.

在將丙烯酸系樹脂薄膜3捲取於捲取核心19，作為輥狀丙烯酸系樹脂薄膜5時，控制捲取張力，使用按壓輥18而朝向捲取核心19而壓緊，同時按照已捲取的輥狀丙烯酸系樹脂薄膜5之直徑而控制按壓輥18之線壓。按壓輥18之線壓係設為0.01~0.6N/mm之範圍。此線壓係0.05~0.5N/mm之範圍為理想，0.1~0.4N/mm之範圍為較理想。若此線壓超過0.6N/mm，則輥狀丙烯酸系樹脂薄膜5之表面可顯著觀察到暴筋(gauge band)的狀況會有很多，所以不理想。另外，為了按壓到丙烯酸系樹脂薄膜3，其係需要至少0.01N/mm左右之線壓。 When the acrylic resin film 3 is wound around the winding core 19 as the roll-shaped acrylic resin film 5, the winding tension is controlled, and the pressing roller 18 is used to press the winding core 19 toward the winding core 19. The diameter of the roll-shaped acrylic resin film 5 controls the linear pressure of the pressing roller 18. The linear pressure of the pressing roller 18 is set in the range of 0.01 to 0.6 N / mm. The line pressure is preferably in the range of 0.05 to 0.5 N / mm, and more preferably in the range of 0.1 to 0.4 N / mm. If the linear pressure exceeds 0.6 N / mm, a large number of gauge bands can be noticeably observed on the surface of the roll-shaped acrylic resin film 5, which is not desirable. In addition, in order to press the acrylic resin film 3, a linear pressure of at least about 0.01 N / mm is required.

按壓輥18之線壓，其係按照輥狀丙烯酸系樹脂薄膜5之匝徑，可為一定，亦可使其變化。線壓之變 化，可按照匝徑成為直線性，亦可隨著曲線或某函數之方式來進行。線壓係特別是以隨著匝徑變大而減弱(小)之方式來進行為理想。另外，向薄膜之兩端部之線壓亦可獨立地控制。 The linear pressure of the pressing roller 18 may be constant or changed according to the turn diameter of the roll-shaped acrylic resin film 5. Changes in line pressure The change can be made linear according to the turn diameter, or it can be performed with a curve or a function. The line pressure system is preferably performed in such a manner that the line pressure becomes weaker (smaller) as the turn diameter becomes larger. In addition, the linear pressure to both ends of the film can also be controlled independently.

第2圖，其係將由搬送輥20開始，於捲取核心19捲取丙烯酸系樹脂薄膜3，直到得到輥狀丙烯酸系樹脂薄膜5之捲取步驟，予以放大表示的說明圖。在第2圖中，配置在按壓輥18之前的搬送輥20之數量、或切斷兩端部後之丙烯酸系樹脂薄膜，以按壓輥18按壓，同時進入捲取核心19側時之角度等，以不同於第1圖的形態表示。在第2圖中，經由表示於第1圖的跳動輥17之後之丙烯酸系樹脂薄膜3，沿著3支搬送輥20而搬送。之後，以按壓輥18按壓，同時捲取於捲取核心19，成為可得到輥狀丙烯酸系樹脂薄膜5。 FIG. 2 is an explanatory diagram showing a step of winding up the acrylic resin film 3 starting from the conveying roller 20 and winding the acrylic resin film 3 at the winding core 19 until the roll-shaped acrylic resin film 5 is obtained. In the second figure, the number of the conveying rollers 20 arranged before the pressing roller 18, or the angle of the acrylic resin film after cutting off both ends, and pressing the pressing roller 18 while entering the winding core 19 side, etc. It is shown in a different form from the first figure. In FIG. 2, the acrylic resin film 3 after the jump roller 17 shown in FIG. 1 is conveyed along three conveying rollers 20. Thereafter, while being pressed by the pressing roller 18, it is wound around the winding core 19 to obtain a roll-shaped acrylic resin film 5.

在第1圖及第2圖，按壓輥18係將切斷為特定寬度的丙烯酸系樹脂薄膜3，相對於纏繞於捲取核心19上的輥狀丙烯酸系樹脂薄膜5之捲取方向，以任意之角度進入而按壓捲取。第3圖係用以說明丙烯酸系樹脂薄膜3朝向捲取核心19上之輥狀丙烯酸系樹脂薄膜5側進入時之角度(在本說明書中亦有稱為「進入角度」)之圖，相當於在第2圖加入了此進入角度θ的狀態。亦即，將在丙烯酸系樹脂薄膜3接觸於輥狀丙烯酸系樹脂薄膜5的點(在三維上係大略直線部分)的輥狀丙烯酸系樹脂薄膜5之切線方向(也就是捲取方向)A、與丙烯酸系樹脂薄膜 3直到接觸於按壓輥18之進行方向B所形成的角度，設為進入角度θ。在按壓輥18係以將丙烯酸系樹脂薄膜3壓緊於輥狀丙烯酸系樹脂薄膜5之方式配置的情況中，切線方向(捲取方向)A係成為正交於相連按壓輥18之中心軸與捲取核心19之中心軸的線段(在三維上為平面)的方向。然後，在即使沒有按壓輥18而由捲取方向進入丙烯酸系樹脂薄膜3的情況，也就是由第3圖之A方向有丙烯酸系樹脂薄膜3進入的情況之進入角度設為0度。如此地定義的進入角度θ係在由0度至120度左右之範圍，可取適宜的值。 In FIGS. 1 and 2, the pressing roller 18 is an acrylic resin film 3 cut to a specific width, and the winding direction of the roll-shaped acrylic resin film 5 wound around the winding core 19 is optional. Enter at an angle and press the coil. FIG. 3 is a diagram for explaining the angle when the acrylic resin film 3 enters toward the roll-shaped acrylic resin film 5 on the winding core 19 (also referred to as “entrance angle” in this specification), which is equivalent to The state of this entering angle θ is added to FIG. 2. That is, the tangential direction (that is, the winding direction) A of the roll-shaped acrylic resin film 5 at a point where the acrylic resin film 3 contacts the roll-shaped acrylic resin film 5 (a substantially straight portion in three dimensions) A, With acrylic resin film 3 The angle formed by the proceeding direction B until it contacts the pressing roller 18 is set as the entering angle θ. In the case where the pressing roller 18 is arranged so that the acrylic resin film 3 is pressed against the roll-shaped acrylic resin film 5, the tangential direction (winding direction) A is orthogonal to the central axis of the continuous pressing roller 18 and Take up the direction of the line segment (plane in three dimensions) of the central axis of the core 19. Then, in the case where the acrylic resin film 3 enters from the winding direction without pressing the roller 18, that is, when the acrylic resin film 3 enters from the direction A in FIG. 3, the entry angle is set to 0 degrees. The entering angle θ defined in this way is in a range from about 0 degrees to about 120 degrees, and can take an appropriate value.

丙烯酸系樹脂薄膜3之捲取量係1m以上9000m以下之範圍為理想，更進一步係設為10m以上6000m以下之範圍為理想。若該捲取量低於1m，則因為捲取量少，本發明之效果變成無特別的必要。另一方面，若捲取量超過9000m，則輥狀丙烯酸系樹脂薄膜5之重量變大，變得難以搬運。 The winding amount of the acrylic resin film 3 is preferably in a range of 1 m to 9000 m, and more preferably in a range of 10 m to 6000 m. If the winding amount is less than 1 m, the effect of the present invention is not particularly necessary because the winding amount is small. On the other hand, when the winding amount exceeds 9000 m, the weight of the roll-shaped acrylic resin film 5 becomes large, and it becomes difficult to carry it.

作為為了捲取丙烯酸系樹脂薄膜3而使用的捲取核心19之材質，例如可舉出如聚乙烯或聚丙烯般的聚烯烴系樹脂、氯乙烯系樹脂、聚苯乙烯系樹脂、ABS(丙烯腈‧丁二烯‧苯乙烯共聚)樹脂、聚醯胺系樹脂、聚酯系樹脂、纖維強化塑膠(Fiber Reinforced Plastics)等作為代表例的塑膠或紙。在將丙烯酸系樹脂薄膜3作為光學薄膜而使用的情況，為了不帶入灰塵，其係作為捲取核心19而理想為使用塑膠製者。 Examples of the material of the winding core 19 used for winding the acrylic resin film 3 include polyolefin resins such as polyethylene or polypropylene, vinyl chloride resins, polystyrene resins, and ABS (propylene Nitrile, butadiene, styrene copolymer) resins, polyamide resins, polyester resins, fiber-reinforced plastics, and other plastics or paper are typical examples. When the acrylic resin film 3 is used as an optical film, it is preferable to use a plastic material as the winding core 19 so as not to bring in dust.

[偏光板及該製造方法] [Polarizing Plate and Manufacturing Method]

如以上方式進行而以輥狀製造的丙烯酸系樹脂薄膜，其係作為偏光板之保護薄膜(偏光子保護薄膜)，可合適地使用。因此，接著說明有關使用此丙烯酸系樹脂薄膜的偏光板及該製造方法。 The acrylic resin film produced in a roll shape as described above can be suitably used as a protective film (a polarizer protective film) of a polarizing plate. Therefore, the polarizing plate using this acrylic resin film and the manufacturing method are demonstrated next.

在將捲取為輥狀的丙烯酸系樹脂薄膜適用於偏光板之製造的情況，在工業上，例如將此輥狀丙烯酸系樹脂薄膜捲出，貼合於用其他方法以長尺狀搬送的由聚乙烯醇系樹脂所構成的偏光子。在此情況，丙烯酸系樹脂薄膜係作為保護薄膜而可僅貼合於偏光子之單面，亦可貼合於偏光子之兩面。在偏光子之單面貼合丙烯酸系樹脂薄膜的情況，於偏光子之另一面，亦可貼合其他的樹脂薄膜，而且亦可將用以把該偏光板適用於液晶晶胞等之黏著劑層，加以直接設置。在偏光子之單面貼合丙烯酸系樹脂薄膜，在偏光子之另一面貼合其他的樹脂薄膜的情況，該其他之樹脂薄膜，亦通常為一邊以長尺狀連續地搬送，同時貼合偏光子。在偏光子與丙烯酸系樹脂薄膜之貼合，另外在偏光子與其他的樹脂薄膜之貼合，通常係使用接著劑。 When the acrylic resin film wound into a roll shape is suitable for manufacturing a polarizing plate, in industry, for example, this roll-shaped acrylic resin film is rolled out, and it is bonded to a long-distance conveyed by another method. A polarizer made of a polyvinyl alcohol resin. In this case, as the protective film, the acrylic resin film may be bonded only to one side of the polarizer, or may be bonded to both sides of the polarizer. When the acrylic resin film is bonded on one side of the polarizer, other resin films can be bonded on the other side of the polarizer, and the polarizer can be used as an adhesive for liquid crystal cells. Layer and set it directly. In the case where an acrylic resin film is bonded to one side of the polarizer and another resin film is bonded to the other side of the polarizer, the other resin film is usually continuously conveyed in a long shape on one side, and polarized light is also bonded at the same time. child. Generally, an adhesive is used for bonding a polarizer to an acrylic resin film, and for bonding a polarizer to another resin film.

<偏光子> <Polarized photon>

作為偏光子，可使用在聚乙烯醇系樹脂薄膜使二色性色素吸附配向，賦與特定之偏光特性者。作為二色性色素，可使用碘或二色性有機染料。亦即，作為偏光子，具 體而言，可使用在聚乙烯醇系樹脂薄膜使碘吸附配向的碘系偏光子薄膜、或在聚乙烯醇系樹脂薄膜使二色性有機染料吸附配向的染料系偏光子薄膜等。 As the polarizer, a polyvinyl alcohol-based resin film can be used to adsorb and align a dichroic dye and impart specific polarization characteristics. As the dichroic dye, iodine or a dichroic organic dye can be used. That is, as a polarized photon, with Specifically, an iodine-based polarizer film in which a iodine is adsorbed and aligned on a polyvinyl alcohol-based resin film, and a dye-based polarizer film in which a dichroic organic dye is aligned on a polyvinyl alcohol-based resin film can be used.

構成偏光子的聚乙烯醇系樹脂係可藉由將聚醋酸乙烯酯系樹脂皂化而製造。作為聚醋酸乙烯酯系樹脂，除了醋酸乙烯酯之均聚物的聚醋酸乙烯酯以外，還可使用醋酸乙烯酯、與可共聚於此成分的其他之單體之共聚物等。作為可共聚於醋酸乙烯酯的其他單體，例如可舉出不飽和羧酸類、烯烴類、乙烯基醚類、不飽和磺酸類等。聚乙烯醇系樹脂亦可被改質，例如亦可使用以醛類改質的聚乙烯甲醛、聚乙烯縮醛、聚乙烯丁醛等。 The polyvinyl alcohol-based resin constituting the polarizer can be produced by saponifying a polyvinyl acetate-based resin. As the polyvinyl acetate-based resin, in addition to polyvinyl acetate, which is a homopolymer of vinyl acetate, copolymers of vinyl acetate and other monomers that can be copolymerized with this component can also be used. Examples of other monomers copolymerizable with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, and unsaturated sulfonic acids. The polyvinyl alcohol-based resin may be modified, and for example, polyvinyl aldehyde, polyvinyl acetal, and polyvinyl butyral modified with aldehydes may be used.

偏光子係通常以下述之(i)~(v)之步驟而製造。 A polarized system is usually manufactured by the following steps (i) to (v).

(i)調整聚乙烯醇系樹脂薄膜之水分的調濕步驟。 (i) A humidity adjustment step for adjusting the moisture content of the polyvinyl alcohol-based resin film.

(ii)將聚乙烯醇系樹脂薄膜單軸延伸的步驟。 (ii) A step of uniaxially stretching the polyvinyl alcohol-based resin film.

(iii)將聚乙烯醇系樹脂薄膜以二色性色素染色，使二色性色素吸附配向的步驟。 (iii) A step of dyeing a polyvinyl alcohol-based resin film with a dichroic dye to adsorb and align the dichroic dye.

(iv)將已吸附配向二色性色素的聚乙烯醇系樹脂薄膜，以硼酸水溶液處理的步驟。 (iv) A step of treating a polyvinyl alcohol-based resin film having adsorbed and aligned dichroic dye with a boric acid aqueous solution.

(v)清洗硼酸水溶液的洗淨步驟。 (v) A washing step of washing the boric acid aqueous solution.

單軸延伸係可在染色前進行，亦可在染色中進行，且亦可在染色後之硼酸處理中進行。另外，亦可在這些複數之段階進行單軸延伸。單軸延伸之方法，其係可以是在周速度不同的輥間於單軸延伸的方法，亦可以是使用加熱輥 而於單軸延伸的方法。另外，可以是在大氣中進行延伸的乾式延伸，亦可以是在用溶劑使其膨潤的狀態進行延伸的濕式延伸。延伸倍率係通常為4~8倍左右。最終可得到的偏光子薄膜之厚度，例如可設為1~50μm左右。 Uniaxial stretching can be performed before or during dyeing, and can also be performed in boric acid treatment after dyeing. In addition, uniaxial extension may be performed at these plural steps. The method of uniaxial stretching can be a method of uniaxial stretching between rollers with different peripheral speeds, or a heating roller can be used. And the method of uniaxial extension. In addition, it may be dry stretching performed in the air, or wet stretching may be performed in a state of being swollen with a solvent. The stretching ratio is usually about 4 to 8 times. The thickness of the polarizer film finally obtained can be set to, for example, about 1 to 50 μm.

<其他之樹脂薄膜> <Other resin films>

在偏光子之單面貼合丙烯酸系樹脂薄膜，在偏光子之另一面貼合其他之樹脂薄膜，作為該其他之樹脂薄膜，可使用由如聚丙烯系樹脂般的鏈狀聚烯烴系樹脂、環狀聚烯烴系樹脂、纖維素系樹脂(例如三乙酸纖維素或二乙酸纖維素所代表的纖維素乙酸酯系樹脂)、聚碳酸酯系樹脂、聚對苯二甲酸乙二醇酯系樹脂、聚對苯二甲酸丁二酯系樹脂、聚苯乙烯系樹脂、丙烯腈‧丁二烯‧苯乙烯系共聚樹脂、丙烯腈‧苯乙烯系共聚樹脂、聚醋酸乙烯酯系樹脂、聚氯乙烯系樹脂、聚偏二氯乙烯系樹脂、聚醯胺系樹脂、聚縮醛系樹脂、改質聚苯醚系樹脂、聚碸系樹脂、聚醚碸系樹脂、聚芳酯系樹脂、聚醯胺醯亞胺系樹脂、聚醯亞胺系樹脂等所構成的薄膜。這些其他之樹脂薄膜之厚度係通常為5~200μm，理想為10~170μm。在偏光子之單面貼合以本發明之方法而製造的丙烯酸系樹脂薄膜，於偏光子之另外一面係貼合以與本發明之方法不同的方法而製造的丙烯酸系樹脂薄膜的形態，當然亦包含於本發明。 An acrylic resin film is bonded to one side of the polarizer, and another resin film is bonded to the other side of the polarizer. As the other resin film, a chain-like polyolefin resin such as a polypropylene resin, Cyclic polyolefin resin, cellulose resin (e.g. cellulose acetate resin represented by cellulose triacetate or cellulose diacetate), polycarbonate resin, polyethylene terephthalate resin Resin, polybutylene terephthalate resin, polystyrene resin, acrylonitrile, butadiene, styrene copolymer resin, acrylonitrile, styrene copolymer resin, polyvinyl acetate resin, polyvinyl chloride Ethylene resin, polyvinylidene chloride resin, polyamide resin, polyacetal resin, modified polyphenylene ether resin, polyfluorene resin, polyether resin, polyarylate resin, polymer A thin film made of fluorene amine imine-based resin, polyimide-based resin, and the like. The thickness of these other resin films is usually 5 to 200 μm, and preferably 10 to 170 μm. The form of laminating an acrylic resin film manufactured by the method of the present invention on one side of a polarizer, and the form of laminating an acrylic resin film manufactured by a method different from the method of the present invention on the other side of a polarizer, of course. Also included in the present invention.

另外，作為貼合於與偏光子之丙烯酸系樹脂薄膜係相反側的面的樹脂薄膜，亦可使用1/4波長板或 1/2波長板、視角補償薄膜等的相位差薄膜。藉由作為層積如此的相位差薄膜的構成，可減少薄膜之層積數。因此，變為可謀求適用此薄膜的液晶顯示裝置之輕量化、薄型化。作為包含波長板或視角補償薄膜的相位差薄膜，係可使用先前周知者。例如，可將如聚碳酸酯系樹脂、聚乙烯醇系樹脂、聚苯乙烯系樹脂、甲基丙烯酸酯系樹脂、聚丙烯般的聚烯烴系樹脂、環狀聚烯烴系樹脂、聚芳酯系樹脂、聚醯亞胺系樹脂、聚醯胺系樹脂等所構成的薄膜，以一軸或二軸等之適宜的方式延伸而得到相位差薄膜。相位差薄膜，其係亦可為在與熱收縮性薄膜之接著下施加收縮力以及/或是延伸力而控制薄膜之厚度方向之折射率的雙折射性薄膜。 In addition, as the resin film bonded to the surface opposite to the acrylic resin film of the polarizer, a 1/4 wavelength plate or A retardation film such as a 1/2 wavelength plate and a viewing angle compensation film. With such a configuration that the retardation film is laminated, the number of laminated films can be reduced. Therefore, it is possible to reduce the weight and thickness of the liquid crystal display device to which the film is applied. As the retardation film including a wavelength plate or a viewing angle compensation film, a conventionally known one can be used. For example, polycarbonate-based resin, polyvinyl alcohol-based resin, polystyrene-based resin, methacrylate-based resin, polypropylene-based polyolefin-based resin, cyclic polyolefin-based resin, and polyarylate-based resin can be used. A film made of a resin, a polyimide-based resin, a polyamidine-based resin, or the like is stretched in a suitable manner such as one or two axes to obtain a retardation film. The retardation film may be a birefringent film that controls the refractive index in the thickness direction of the film by applying a shrinkage force and / or an extension force to the heat shrinkable film.

<偏光子與樹脂薄膜(保護薄膜)之接著> <Adhesion between polarizer and resin film (protective film)>

在對於偏光子之，丙烯酸系樹脂薄膜之貼合，另外其他的樹脂薄膜之貼合，其係依照上述通常使用接著劑。在貼合之前，在各自之薄膜之貼合面之至少一方，理想為先施加電暈放電處理、電漿照射處理、電子束照射處理、或是其他之表面活性化處理。接著劑係相對於各自之構件而顯現接著力者，所以可任意選擇使用。典型上可舉出含有藉由活性能量射線之照射而硬化的成分的活性能量射線硬化性接著劑。 In the case of polarizers, the bonding of acrylic resin films and the bonding of other resin films are generally performed using an adhesive in accordance with the above. Prior to lamination, it is desirable to apply corona discharge treatment, plasma irradiation treatment, electron beam irradiation treatment, or other surface activation treatment to at least one of the lamination surfaces of the respective films. Since the adhesive agent exhibits adhesiveness with respect to each member, it can be arbitrarily selected and used. Typical examples include active energy ray-curable adhesives containing a component that is hardened by irradiation with active energy rays.

在使用活性能量射線硬化性接著劑的情況，構成該劑的藉由活性能量射線之照射而硬化的成分(以 下，有單獨稱為「硬化性成分」者)，其係可能有環氧化合物、氧雜環丁烷化合物、丙烯酸系化合物等。在使用如環氧化合物或氧雜環丁烷化合物般的陽離子聚合性之化合物的情況中，調配陽離子聚合起始劑。另外，在使用如丙烯酸系化合物般的自由基聚合性化合物的情況中，調配自由基聚合起始劑。在其中，將環氧化合物作為硬化性成分之一的接著劑為理想，尤其是，將在飽和烴環上直接鍵結有環氧基的脂環式環氧化合物作為硬化性成分之一的接著劑為理想。另外，於該劑併用氧雜環丁烷化合物者亦為有效。 In the case of using an active energy ray-curable adhesive, the constituents of the agent that are hardened by irradiation with active energy rays (by Hereinafter, there are those which are called "hardening component" alone), and the system may include epoxy compounds, oxetane compounds, acrylic compounds, and the like. When a cationically polymerizable compound such as an epoxy compound or an oxetane compound is used, a cationic polymerization initiator is blended. When a radical polymerizable compound such as an acrylic compound is used, a radical polymerization initiator is blended. Among them, an adhesive agent using an epoxy compound as one of the hardening components is preferable, and in particular, an alicyclic epoxy compound having an epoxy group directly bonded to a saturated hydrocarbon ring as one of the hardening components. Agent is ideal. It is also effective to use an oxetane compound in combination with this agent.

環氧化合物係可容易地取得市售品。例如，有各自商品名，日本環氧樹脂公司所販賣的"EPIKOTE"系列、DIC公司所販賣的"EPICLON"系列、東都化成公司所販賣的"Epotohto"系列、ADEKA公司所販賣的"Adeka Resin"系列、Nagase ChemteX公司所販賣的"Denacol"系列、陶氏化學公司所販賣的"DOW Epoxy"系列、日產化學工業公司所販賣的"TEPIC"系列等。 Epoxy compounds are easily available in the market. For example, there are respective brand names, "EPIKOTE" series sold by Japanese epoxy resin company, "EPICLON" series sold by DIC company, "Epotohto" series sold by Totsuka Kasei, and "Adeka Resin" sold by ADEKA company. Series, "Denacol" series sold by Nagase ChemteX, "DOW Epoxy" series sold by The Dow Chemical Company, "TEPIC" series sold by Nissan Chemical Industries, and so on.

在飽和烴環上直接鍵結有環氧基的脂環式環氧化合物，亦可容易地取得市售品。例如，在各自的商品名，有daicel化學工業公司販賣的"CELLOXIDE"系列及"CYCLOMER"系列、陶氏化學公司販賣的"CYRACURE"系列等。 An alicyclic epoxy compound having an epoxy group directly bonded to a saturated hydrocarbon ring can also easily obtain a commercially available product. For example, the respective brand names include the "CELLOXIDE" series and "CYCLOMER" series sold by Daicel Chemical Industries, and the "CYRACURE" series sold by Dow Chemical.

氧雜環丁烷化合物，亦可容易地取得市售品。例如，以各自商品名，有東亞合成公司販賣的"ARON OXETANE"系列、宇部興產公司販賣的"ETERNACOLL"系列等。 Commercially available oxetane compounds can also be easily obtained. For example, "ARON" sold by Toa Kasei Corporation under their respective trade names "OXETANE" series, "ETERNACOLL" series sold by Ube Kosan.

陽離子聚合起始劑，亦可容易地取得市售品。例如，在各自的商品名，有日本化藥公司販賣的"KAYARAD"系列、Union Carbide公司販賣的"CYRACURE"系列、San-Apro公司販賣的光酸產生劑"CPI"系列、Midori化學公司販賣的光酸產生劑"TAZ"、"BBI"及"DTS"、ADEKA公司販賣的"ADEKA OPTOMER"系列、Rhodia公司販賣的"RHODORSIL"系列等。 Cationic polymerization initiators can also easily obtain commercially available products. For example, there are "KAYARAD" series sold by Nippon Kayakusho, "CYRACURE" series sold by Union Carbide, photoacid generator "CPI" series sold by San-Apro, and Midori Chemical Co., Ltd. Photoacid generators "TAZ", "BBI" and "DTS", "ADEKA OPTOMER" series sold by ADEKA, and "RHODORSIL" series sold by Rhodia.

活性能量射線硬化性接著劑係可按照必要而含有光增感劑。以使用光增感劑，可使反應性提高，使硬化物層之機械強度或接著強度更提高。作為光增感劑，例如可舉出羰基化合物、有機硫化合物、過硫化物、氧化還原系化合物、偶氮及重氮化合物、蒽系化合物、鹵素化合物、光還原性色素等。 The active-energy-ray-curable adhesive system may contain a photosensitizer as needed. By using a photosensitizer, the reactivity can be improved, and the mechanical strength or adhesion strength of the hardened layer can be further improved. Examples of the photosensitizer include carbonyl compounds, organic sulfur compounds, persulfides, redox compounds, azo and diazo compounds, anthracene compounds, halogen compounds, and photoreducing pigments.

另外，在活性能量射線硬化性接著劑，可在不損及該接著性的範圍中，調配各種添加劑。作為添加劑，例如可舉出離子捕捉劑、防氧化劑、鏈轉移劑、增黏劑、熱可塑性樹脂、填充劑、流動調整劑、可塑劑、消泡劑等。而且，在不損及該接著性的範圍，亦可調配以與陽離子聚合以外不同之反應機構來硬化的硬化性成分。 Moreover, various additives can be mix | blended in the range which does not impair this adhesiveness with an active-energy-ray-curable adhesive agent. Examples of the additives include ion trapping agents, antioxidants, chain transfer agents, tackifiers, thermoplastic resins, fillers, flow regulators, plasticizers, and defoamers. Moreover, in the range which does not impair this adhesiveness, you may mix | blend a hardening component hardened | cured by the reaction mechanism different from cation polymerization.

以上說明的活性能量射線硬化性接著劑係塗布於保護薄膜或樹脂薄膜之貼合面或是偏光子之貼合面。經由該塗布層而貼合兩薄膜後，於該處照射活性能量射線 而硬化，成為接合偏光子與保護薄膜以及/或是樹脂薄膜的接著劑層。於偏光子之兩面貼合保護薄膜或樹脂薄膜的情況，向偏光子之一方之面與另一方之面貼合係可逐次進行，亦可同時進行。同時進行係在生產性之方面為較有利。另外，適用於偏光子之兩面的接著劑，係可為相同的組成亦可為不同的組成。用以使兩者硬化的活性能量射線之照射，其係同時進行而在生產性的方面上為較理想。 The active energy ray-curable adhesive agent described above is applied to a bonding surface of a protective film or a resin film or a bonding surface of a polarizer. After the two films are bonded through the coating layer, active energy rays are irradiated there. And it hardens and becomes the adhesive layer which joins a polarizer, a protective film, and / or a resin film. In the case where a protective film or a resin film is bonded to both sides of the polarizer, the bonding to one side of the polarizer and the other side may be performed sequentially or simultaneously. Simultaneous execution is advantageous in terms of productivity. In addition, the adhesive suitable for both sides of the polarizer may have the same composition or different compositions. Irradiation of active energy rays to harden both is performed simultaneously, and it is preferable in terms of productivity.

被使用在活性能量射線硬化性接著劑之硬化的活性能量射線，例如可能是波長為1~10nm之X光、波長為10~400nm之紫外線、波長為400~800nm之可見光線等。在此之中，就利用之容易度、以及活性能量射線硬化性接著劑之調製之容易度、安定性及硬化性能之觀點，紫外線係可理想地使用。在紫外線之光源中，例如可使用在波長400nm以下具有發光分布的低壓水銀燈、中壓水銀燈、高壓水銀燈、超高壓水銀燈、化學燈、黑光燈、微波激發水銀燈、金屬鹵素燈等。 The active energy rays used for curing of the active energy ray-curable adhesive may be, for example, X-rays having a wavelength of 1 to 10 nm, ultraviolet rays having a wavelength of 10 to 400 nm, and visible rays having a wavelength of 400 to 800 nm. Among these, from the viewpoints of ease of use and ease of preparation of active energy ray-curable adhesive, stability, and curing performance, ultraviolet rays are preferably used. As the ultraviolet light source, for example, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a chemical lamp, a black light lamp, a microwave-excited mercury lamp, a metal halide lamp, and the like having a light emission distribution below a wavelength of 400 nm can be used.

使用活性能量射線硬化性接著劑而得的接著劑層之厚度，通常可取0.1~50μm左右之範圍。在可得充分的接著力的範圍中，以設為10μm以下，更進一步以設為5μm以下之方式為較理想。 The thickness of the adhesive layer obtained by using an active energy ray-curable adhesive is usually in the range of about 0.1 to 50 μm. In a range where a sufficient adhesive force can be obtained, it is preferable to set it as 10 μm or less, and further set it as 5 μm or less.

<黏著劑層> <Adhesive layer>

於偏光板係通常設置有用以貼合於液晶晶胞等之黏著劑層。在偏光子之單面，將依本發明之方法而製造的丙烯 酸系樹脂薄膜作為保護薄膜而貼合。於偏光子之另一面貼合了其他樹脂薄膜或相位差薄膜的構造之偏光板，通常，在與作為該保護薄膜之丙烯酸系樹脂薄膜係相反側之面，設有黏著劑層。亦可在偏光子之單面，將依本發明之方法而製造的丙烯酸系樹脂薄膜作為保護薄膜而貼合，在偏光子之另一面直接設有黏著劑層。在黏著劑層之形成中，使用將丙烯酸酯作為主要的構成單體的樹脂。具體而言，在如丙烯酸或丙烯酸2-羥乙基酯般的含有極性官能基的單體係被少量共聚的丙烯酸系樹脂所構成的黏著性樹脂中，調配了交聯劑等的丙烯酸系黏著劑係由透明性或適度之黏著力等之觀點而言，可合適地使用。 An adhesive layer is usually provided on the polarizing plate to adhere to a liquid crystal cell or the like. Acrylic on one side of a polarizer to be produced by the method of the present invention The acid-based resin film is bonded as a protective film. A polarizing plate having a structure in which another resin film or a retardation film is laminated on the other side of the polarizer is generally provided with an adhesive layer on the side opposite to the acrylic resin film serving as the protective film. The acrylic resin film produced by the method of the present invention may be laminated on one side of the polarizer as a protective film, and an adhesive layer may be directly provided on the other side of the polarizer. In the formation of the adhesive layer, a resin having acrylate as a main constituent monomer is used. Specifically, in an adhesive resin composed of a small amount of an acrylic resin copolymerized with a single system containing a polar functional group such as acrylic acid or 2-hydroxyethyl acrylate, a crosslinking agent or the like is blended. The agent is suitably used from the viewpoints of transparency and moderate adhesion.

[實施例] [Example]

以下，舉出實施例及比較例而更具體地說明本發明，但本發明係不因這些實施例而被限定。在例中，表示含有量或使用量的%及份係只要無特別記述，就是重量基準。 Hereinafter, the present invention will be described more specifically with examples and comparative examples, but the present invention is not limited by these examples. In the examples,% and parts indicating the content or amount used are based on weight unless otherwise specified.

[實施例1] [Example 1] (1)原料樹脂之製作 (1) Production of raw resin

作為甲基丙烯酸樹脂，使用甲基丙烯酸甲酯97重量%與丙烯酸甲酯3重量%之共聚物的熱可塑性聚合物(玻璃轉移溫度104℃)之顆粒。作為丙烯酸橡膠粒子，以上述日本特公昭55-27576號公報(專利文獻3)之實施例3 相同之方法來製造，其係由在最內層為在甲基丙烯酸甲酯中共聚有少量之甲基丙烯酸烯丙酯的硬質聚合物，中間層為以丙烯酸丁酯作為主成分，而且共聚有苯乙烯及少量之甲基丙烯酸烯丙酯的彈性聚合物，最外層為在甲基丙烯酸甲酯中共聚有少量之丙烯酸甲酯的硬質聚合物所構的球形3層構造，使用平均粒徑為0.22μm者。 As the methacrylic resin, pellets of a thermoplastic polymer (glass transition temperature: 104 ° C.) of a copolymer of 97% by weight of methyl methacrylate and 3% by weight of methyl acrylate were used. As the acrylic rubber particles, Example 3 of the aforementioned Japanese Patent Publication No. 55-27576 (Patent Document 3) was used. It is produced by the same method. It is a hard polymer in which a small amount of allyl methacrylate is copolymerized in methyl methacrylate in the innermost layer, and butyl acrylate is used as the main component in the middle layer. An elastic polymer of styrene and a small amount of allyl methacrylate. The outermost layer is a spherical three-layer structure composed of a hard polymer copolymerized with a small amount of methyl acrylate in methyl methacrylate. The average particle size is 0.22μm.

將甲基丙烯酸樹脂之顆粒70份與丙烯酸橡膠粒子30份，以超級混合機進行混合。接著，以二軸擠出機進行熔融混練而作為樹脂組成物之顆粒，將此作為丙烯酸系樹脂而使用。 70 parts of methacrylic resin particles and 30 parts of acrylic rubber particles were mixed with a super mixer. Next, melt-kneading was performed with a biaxial extruder to obtain pellets of a resin composition, and this was used as an acrylic resin.

(2)丙烯酸系樹脂薄膜之製作 (2) Production of acrylic resin film

將所得的顆粒以130mm

一軸擠出機而熔融，以T型模頭擠出，參照第1圖而說明的金屬彈性輥(表面為由不銹鋼所構成的彈性輥)的第一冷卻輥11與不銹鋼之剛性輥的第二冷卻輥12(表面溫度102℃)而挾持冷卻。而且使其通過第三冷卻輥13，以厚度成為80μm的方式適宜地調整吐出量和線速度，得到丙烯酸系樹脂薄膜。將所得到的薄膜縱切為寬度1330mm之後，纏繞在直徑6吋(15.2mm)之捲取核心上捲取長度2000m。 The obtained particles were

It is melted by a one-axis extruder and extruded with a T-die. The first cooling roll 11 of the metal elastic roll (the surface is an elastic roll made of stainless steel) and the second of the rigid roll of stainless steel described with reference to FIG. The cooling roll 12 (surface temperature: 102 ° C.) was held and cooled. Then, it was made to pass through the 3rd cooling roll 13, and the discharge amount and linear velocity were adjusted suitably so that thickness might be 80 micrometers, and the acrylic resin film was obtained. The obtained film was slit into a width of 1330 mm, and then wound around a winding core with a diameter of 6 inches (15.2 mm) and a winding length of 2000 m.

此時之捲取條件，係將捲取張力設為135N/m，使用按壓輥而捲取，得到輥狀丙烯酸系樹脂薄膜。在按壓輥係使用橡膠輥。藉由按壓輥而在輥狀丙烯酸系樹脂薄膜施加0.36N/mm之線壓。將所得到的輥狀丙烯 酸系樹脂薄膜之外觀評估，用以下之(A)~(D)的方式來進行。 The winding conditions at this time were set to a winding tension of 135 N / m, and the winding was performed using a pressing roller to obtain a roll-shaped acrylic resin film. A rubber roller is used for the pressing roller system. A linear pressure of 0.36 N / mm was applied to the roll-shaped acrylic resin film by pressing the roll. Roll the obtained propylene The appearance evaluation of the acid-based resin film was performed by the following methods (A) to (D).

(A)多角形之有無評估 (A) Evaluation of the presence of polygons

所謂的「多角形」，意味著已捲取為輥狀的丙烯酸系樹脂薄膜之剖面，在本來應該成為圓形處(圓柱剖面)變為多角形狀的現象。在此，觸診已捲取為輥狀的丙烯酸系樹脂薄膜之表面(相當於圓柱側面的薄膜之最表面)，評估薄膜變形之有無。評估係在捲取之後立即及該10日後之2次進行。然而，將不感到凹凸，可確認剖面為圓者的等級設為「+」，將感到凹凸，可確認剖面非圓形者的等級設為「-」，將結果表示於表1。 The so-called "polygon" means a phenomenon in which the cross section of the acrylic resin film that has been wound into a roll shape turns into a polygonal shape at a place where it is supposed to be circular (cylindrical cross section). Here, the surface of the acrylic resin film rolled up into a roll shape (corresponding to the outermost surface of the film on the side of the cylinder) was palpated, and the presence or absence of film deformation was evaluated. The evaluation was performed immediately after the take-up and twice after the 10th day. However, the level of those who did not feel unevenness and confirmed that the cross-section was round was set to "+", and the level of those who felt unevenness and confirmed that the cross-section was not rounded to "-", and the results are shown in Table 1.

(B)薄膜之向下鬆弛之評估 (B) Evaluation of downward relaxation of the film

所謂「薄膜之向下鬆弛」，其係已捲取為輥狀的丙烯酸系樹脂薄膜是因為該重量而垂向下方的現向。在此，將丙烯酸系樹脂薄膜捲取為輥狀時，先在捲取核心附近設置壓力感測器，在已捲取的狀態使輥旋轉時，評估壓力感測器所偵測的值有無變化。然後，即使讓輥旋轉而壓力亦無變化，判斷為並無向下鬆弛的情況設為「+」，使輥旋轉時偵測到壓力變化，判斷為有向下鬆弛的情況設為「-」，將結果表示於表1。 The so-called "downward slackening of the film" refers to the current direction of the acrylic resin film that has been wound into a roll shape because of the weight. Here, when the acrylic resin film is rolled into a roll shape, a pressure sensor is installed near the winding core. When the roll is rotated in the rolled state, it is evaluated whether the value detected by the pressure sensor changes. . Then, even if the roller is rotated, the pressure does not change. If it is determined that there is no downward slack, it is set to "+". When the roller is rotated, a pressure change is detected, and if it is determined that there is a downward slack, it is set to "-". The results are shown in Table 1.

(C)高邊緣之評估 (C) Evaluation of high margins

所謂「高邊緣」，其係已捲取為輥狀的丙烯酸系樹脂薄膜之寬度方向端部係變得高於寬度方向中央部的現象。在此，將已捲取為輥狀的丙烯酸系樹脂薄膜以目視觀察而評估。然後，將未觀察到高邊緣的情況設為「+」，將觀察到高邊緣的情況設為「-」，將將結果表示於表1。 The "high edge" is a phenomenon in which the widthwise end portion of the acrylic resin film which has been wound into a roll shape becomes higher than the widthwise center portion. Here, the acrylic resin film wound up into a roll shape was evaluated by visual observation. Then, the case where no high edge was observed was set to "+", the case where high edge was observed was set to "-", and the results are shown in Table 1.

(D)暴筋(gauge band)之評估 (D) Evaluation of gauge band

所謂的暴筋(gauge band)，其係沿著已捲取為輥狀的丙烯酸系樹脂薄膜之表面之圓周方向，可觀察到瘤狀物或捲瘤狀物。在此，由已捲取為輥狀的丙烯酸系樹脂薄膜之一方側之端面(相當於圓柱之底面的面)，以HID燈(高強度氣體放電燈High Intensity Discharged Lump)照射，由薄膜表面(相當於圓柱之側面的面)加以觀察，評估暴筋之有無。然後，將未觀察到暴筋的情況設為「+」，將觀察到暴筋的情況設為「-」，將結果表示於表1。 The so-called "gauge band" is a bulge or bulge that can be observed along the circumference of the surface of the acrylic resin film that has been rolled into a roll. Here, one end surface (a surface corresponding to the bottom surface of a cylinder) of one side of the acrylic resin film wound into a roll shape was irradiated with a HID lamp (High Intensity Discharged Lump), and the film surface ( The surface corresponding to the side of a cylinder) was observed to evaluate the presence or absence of violent tendons. Then, the case where no glutton was observed was set to "+", and the case where glutton was observed was set to "-". The results are shown in Table 1.

[實施例2] [Example 2]

除了藉由實施例1之按壓輥而對輥狀丙烯酸系樹脂薄膜施加0.18N/mm之線壓以外，以相同條件捲取。 Except that a linear pressure of 0.18 N / mm was applied to the roll-shaped acrylic resin film by the pressing roll of Example 1, it was wound up under the same conditions.

[實施例3] [Example 3]

除了將在實施例2，所得到的丙烯酸系樹脂薄膜之厚度變更為60μm以外，以相同條件捲取。 Except that the thickness of the obtained acrylic resin film in Example 2 was changed to 60 μm, it was wound under the same conditions.

[實施例4] [Example 4]

除了將在實施例2，所得到的丙烯酸系樹脂薄膜之厚度變更為40μm以外，以相同條件捲取。 Except that the thickness of the obtained acrylic resin film in Example 2 was changed to 40 μm, it was wound up under the same conditions.

[比較例1] [Comparative Example 1]

除了將實施例1之捲取張力設為75N/m，不使用按壓輥以外，以相同條件捲取。 Except that the winding tension of Example 1 was set to 75 N / m, and a pressing roller was not used, the winding was performed under the same conditions.

[比較例2] [Comparative Example 2]

除了將實施例1之捲取張力設為190N/m，不使用按壓輥以外，以相同條件捲取。 Except that the take-up tension of Example 1 was set to 190 N / m, and no pressing roller was used, the take-up was performed under the same conditions.

[比較例3] [Comparative Example 3]

除了將實施例1之捲取張力設為260N/m，不使用按壓輥以外，以相同條件捲取。 Except that the take-up tension of Example 1 was set to 260 N / m and the pressing roller was not used, the take-up was performed under the same conditions.

[比較例4] [Comparative Example 4]

除了藉由實施例1之按壓輥而對輥狀丙烯酸系樹脂薄膜施加0.72N/mm之線壓之壓力以外，以相同條件捲取。 The roll was wound under the same conditions except that a linear pressure of 0.72 N / mm was applied to the roll-shaped acrylic resin film by the pressing roll of Example 1.

如表1所示，將捲取張力設為在本發明所規定的範圍，但不配置按壓輥而捲取的比較例1及2，其雖然在製造之後立即顯現出良好的外觀，但是若就如此保管則會產生多角形。另外，亦產生有薄膜之向下鬆弛。將捲取張力變大的比較例3，其雖然在將所得的輥狀樹脂薄膜依原樣進行保管的情況之外觀不產生變化，但會產生薄膜之向下鬆弛、高邊緣及暴筋。在此狀態使按壓輥作用的情況，雖然薄膜之向下鬆弛係有被解除的可能性，但被認為難以解除高邊緣及暴筋。配置按壓輥，但加大該線壓的比較例4，其係產生高邊緣及暴筋。 As shown in Table 1, Comparative Examples 1 and 2 in which the take-up tension was set within the range specified in the present invention, but was not rolled with a pressing roller, exhibited a good appearance immediately after production. Polygons will result if stored in this way. In addition, downward slack of the film is also produced. In Comparative Example 3 in which the take-up tension was increased, the appearance of the obtained roll-shaped resin film was not changed when stored, but the film was loosened downward, high edges, and tendons were generated. When the pressing roller acts in this state, although the downward slackness of the film may be released, it is considered difficult to release the high edge and the ribs. In Comparative Example 4 in which the pressing roller was arranged but the line pressure was increased, it caused high edges and tendons.

相對於此，將捲取張力設為在本發明所規定的範圍，而且配置按壓輥而將其線壓設為本發明所規定的 範圍的實施例1~4，其係以無上述般缺陷的外觀良好的狀態捲取，在保管10日後，其狀態亦不變。 In contrast, the take-up tension is set to the range specified in the present invention, and the pressing roller is arranged to set the linear pressure to the range specified in the present invention. Examples 1 to 4 in the range are wound up in a state of good appearance without the above-mentioned defects, and the state remains unchanged after storage for 10 days.

Claims (7)

一種輥狀丙烯酸系樹脂薄膜之製造方法，其係將丙烯酸系樹脂熔融混練而由T型模頭擠出薄膜狀物，將該薄膜狀物挾持於第一冷卻輥與第二冷卻輥之間而作為薄膜狀成形體，將該薄膜狀成形體之寬度方向側端部切斷，將得到的薄膜纏繞於捲取核心而捲取為輥狀，製造丙烯酸系樹脂薄膜的方法，其特徵為：將前述薄膜纏繞於前述捲取核心時之捲取張力設為50~250N/m，於前述捲取核心側配置按壓輥，將該按壓輥之線壓設為0.01~0.6N/mm，將已切斷前述側端部的薄膜捲取為輥狀。A method for manufacturing a roll-shaped acrylic resin film, comprising melting and kneading an acrylic resin, extruding a film-like object from a T-die, and holding the film-like object between a first cooling roll and a second cooling roll. As a film-shaped molded body, the width-direction side end portion of the film-shaped molded body is cut, and the obtained film is wound around a winding core and wound into a roll shape to produce an acrylic resin film. The winding tension when the film is wound around the winding core is set to 50 to 250 N / m. A pressing roller is arranged on the winding core side, and the linear pressure of the pressing roller is set to 0.01 to 0.6 N / mm. The film which cut | disconnected the said side edge part was taken up in roll shape. 如請求項1之輥狀丙烯酸系樹脂薄膜之製造方法，其中，前述丙烯酸系樹脂薄膜之厚度為20μm以上100μm以下。The method for producing a roll-shaped acrylic resin film according to claim 1, wherein the thickness of the acrylic resin film is 20 μm or more and 100 μm or less. 如請求項1之輥狀丙烯酸系樹脂薄膜之製造方法，其中，前述丙烯酸系樹脂薄膜之寬度為500mm以上2000mm以下。The method for manufacturing a roll-shaped acrylic resin film according to claim 1, wherein the width of the acrylic resin film is 500 mm or more and 2000 mm or less. 如請求項1之輥狀丙烯酸系樹脂薄膜之製造方法，其中，前述第二冷卻輥之表面溫度為60℃以上130℃以下。The method for manufacturing a roll-shaped acrylic resin film according to claim 1, wherein the surface temperature of the second cooling roll is 60 ° C or higher and 130 ° C or lower. 如請求項1之輥狀丙烯酸系樹脂薄膜之製造方法，其中，前述丙烯酸系樹脂薄膜之捲取量係1m以上9000m以下。The method for producing a roll-shaped acrylic resin film according to claim 1, wherein the winding amount of the acrylic resin film is 1 m to 9000 m. 如請求項1之輥狀丙烯酸系樹脂薄膜之製造方法，其中，前述丙烯酸系樹脂調配有橡膠粒子。The method for producing a roll-shaped acrylic resin film according to claim 1, wherein the acrylic resin is blended with rubber particles. 一種偏光板之製造方法，其特徵為：捲出藉由如請求項1~6中任一項之方法所製造的輥狀丙烯酸系樹脂薄膜，貼合於由聚乙烯醇系樹脂所構成的偏光子。A method for manufacturing a polarizing plate, characterized in that: a roll-shaped acrylic resin film manufactured by the method according to any one of claims 1 to 6 is rolled out, and the polarized light composed of a polyvinyl alcohol resin is bonded to the roll-shaped acrylic resin film. child.