TW202030209A - Actinic ray curable composition and film using same - Google Patents
Actinic ray curable composition and film using same Download PDFInfo
- Publication number
- TW202030209A TW202030209A TW108132181A TW108132181A TW202030209A TW 202030209 A TW202030209 A TW 202030209A TW 108132181 A TW108132181 A TW 108132181A TW 108132181 A TW108132181 A TW 108132181A TW 202030209 A TW202030209 A TW 202030209A
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- Prior art keywords
- meth
- acrylate
- active energy
- ray curable
- energy ray
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
- C08F220/343—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate in the form of urethane links
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
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- C—CHEMISTRY; METALLURGY
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Abstract
Description
本發明係關於一種可形成硬塗層之活性能量線硬化性組成物及使用其之薄膜。The present invention relates to an active energy ray curable composition capable of forming a hard coating layer and a film using the same.
樹脂薄膜係使用於液晶顯示器(LCD)、有機EL顯示器(OLED)、電漿顯示器(PDP)等平板顯示器(FPD)表面之防傷痕用薄膜、汽車之內外裝用加飾薄膜(薄片)、適合窗戶的低反射薄膜或隔絕熱射線薄膜等各種用途。然而，樹脂薄膜表面，由於柔軟且耐擦傷性低，故以補足其為目的，一般係進行將包含活性能量線硬化性組成物等之硬塗劑塗布於薄膜表面，並進行硬化，將硬塗層設置於薄膜表面。Resin film is used for anti-scratch film on the surface of flat panel display (FPD) such as liquid crystal display (LCD), organic EL display (OLED), plasma display (PDP), and decorative film (sheet) for interior and exterior of automobiles. Various applications such as low-reflection film for windows or heat-ray insulation film. However, since the surface of the resin film is soft and has low scratch resistance, it is generally used to apply a hard coating agent containing active energy ray curable composition on the surface of the film, and then harden the hard coating. The layer is arranged on the surface of the film.
又，該等之用途中，近年來低成本與高精細之需求高漲，但若高速塗布硬塗劑，則容易剝離帶電，且吸附空氣中的浮游異物，而導致塗膜缺陷，造成招致良率降低的問題。因此，作為抑制該良率降低的對策，已廣泛利用賦予帶電防止性的方法，且常使用特別便宜且透明性高的四級銨鹽系的帶電防止劑(參考例如專利文獻1及2)。In addition, in these applications, the demand for low cost and high precision has been increasing in recent years. However, if the hard coating agent is applied at a high speed, it is easy to peel off and charge and adsorb floating foreign matter in the air, resulting in coating film defects, resulting in yield Reduce the problem. Therefore, as a countermeasure to suppress the decrease in yield, a method of imparting antistatic properties has been widely used, and quaternary ammonium salt-based antistatic agents that are particularly inexpensive and highly transparent are often used (see, for example, Patent Documents 1 and 2).
另一方面，作為在FPD之製造中使用的樹脂薄膜，至今為止，主流為三乙醯纖維素(TAC)薄膜或環烯烴聚合物(COP)薄膜，但由於低成本化之趨勢，故將相較便宜而且具有低透濕性及高尺寸安定性的聚甲基丙烯酸甲酯基材作為支撐基材而成之附有硬塗層的薄膜的使用率增加。On the other hand, as the resin film used in the manufacture of FPD, the mainstream has so far been triacetyl cellulose (TAC) film or cyclic olefin polymer (COP) film. The use rate of films with hard coats, which are relatively inexpensive, have low moisture permeability and high dimensional stability, are used as support substrates and have hard coat films.
偏光板係使用防眩硬塗，但近年來伴隨聚甲基丙烯酸甲酯基材使用之增加，而更要求賦予帶電防止性。但是，在硬塗組成物之塗膜乾燥時粒子凝聚過程與帶電防止展現過程會混雜，所以防眩性之展現所需要的低霧度化與帶電防止性之兼具非常困難。 [先前技術文獻] [專利文獻]The polarizing plate uses an anti-glare hard coat, but in recent years, with the increase in the use of polymethyl methacrylate substrates, it is required to provide anti-static properties. However, when the coating film of the hard coating composition is dried, the particle aggregation process and the charging prevention process are mixed, so it is very difficult to combine the low haze required for the antiglare performance and the charging prevention property. [Prior Technical Literature] [Patent Literature]
專利文獻1：日本特開2004-143303號公報 專利文獻2：日本特開2004-123924號公報Patent Document 1: Japanese Patent Application Publication No. 2004-143303 Patent Document 2: JP 2004-123924 A
[發明欲解決之課題][The problem to be solved by the invention]
本發明欲解決的課題為提供一種可形成具有優異的防眩性及帶電防止性的硬塗層之活性能量線硬化性組成物及使用其之薄膜。 [用以解決課題之手段]The problem to be solved by the present invention is to provide an active energy ray curable composition capable of forming a hard coat layer having excellent anti-glare and anti-static properties and a film using the same. [Means to solve the problem]
本發明提供一種活性能量線硬化性組成物，其係含有活性能量線硬化性化合物(A)、及帶電防止劑(B)之活性能量線硬化性組成物，特徵為前述帶電防止劑(B)為具有下述式(1)所示之陽離子部者；及使用其之薄膜。The present invention provides an active energy ray curable composition, which is an active energy ray curable composition containing an active energy ray curable compound (A) and an antistatic agent (B), characterized by the aforementioned antistatic agent (B) It has a cationic part represented by the following formula (1); and a film using it.
本發明的活性能量線硬化性組成物，係在包含聚甲基丙烯酸甲酯基材之各式各樣的基材之上，可形成塗布安定性、塗膜外觀、防眩性及帶電防止性優異的硬塗層者。The active energy ray-curable composition of the present invention is formed on various substrates including polymethyl methacrylate substrates, and can form coating stability, coating appearance, anti-glare and anti-static properties Excellent hard coater.
因此，具有包含本發明活性能量線硬化性組成物之硬化塗膜的硬塗層之薄膜，可適當使用作為使用於液晶顯示器(LCD)、有機EL顯示器(OLED)、電漿顯示器(PDP)等平板顯示器(FPD)的光學薄膜。Therefore, a thin film having a hard coat layer containing a hardened coating film of the active energy ray curable composition of the present invention can be suitably used as a liquid crystal display (LCD), organic EL display (OLED), plasma display (PDP), etc. Optical film for flat panel displays (FPD).
本發明的活性能量線硬化性組成物係為含有活性能量線硬化性化合物(A)及帶電防止劑(B)作為必須成分者。The active energy ray curable composition system of the present invention contains the active energy ray curable compound (A) and the antistatic agent (B) as essential components.
作為前述活性能量線硬化性化合物(A)，可使用例如，胺基甲酸酯(甲基)丙烯酸酯(A1)、環氧(甲基)丙烯酸酯(A2)、前述胺基甲酸酯(甲基)丙烯酸酯(A1)及前述環氧(甲基)丙烯酸酯(A2)以外的多官能(甲基)丙烯酸酯(以下簡稱為「其它多官能(甲基)丙烯酸酯(A3)」)、聚酯(甲基)丙烯酸酯、聚醚(甲基)丙烯酸酯、苯乙烯等。該等之活性能量線硬化性化合物(A)，可單獨使用，亦可併用2種以上。又，從得到更優異的硬塗性之觀點而言，該等之中，較佳為使用選自包含胺基甲酸酯(甲基)丙烯酸酯(A1)、環氧(甲基)丙烯酸酯(A2)、及其它多官能(甲基)丙烯酸酯(A3)的群組之1種以上的化合物。As the active energy ray curable compound (A), for example, urethane (meth)acrylate (A1), epoxy (meth)acrylate (A2), and the aforementioned urethane (A1) can be used. Multifunctional (meth)acrylates other than meth)acrylate (A1) and the aforementioned epoxy (meth)acrylate (A2) (hereinafter referred to as "other multifunctional (meth)acrylates (A3)") , Polyester (meth)acrylate, polyether (meth)acrylate, styrene, etc. These active energy ray-curable compounds (A) may be used alone or in combination of two or more kinds. In addition, from the viewpoint of obtaining more excellent hard coat properties, among these, it is preferable to use selected from the group consisting of urethane (meth)acrylate (A1) and epoxy (meth)acrylate. (A2) and one or more compounds of the group of other multifunctional (meth)acrylates (A3).
再者，在本發明中，「(甲基)丙烯酸酯」係指丙烯酸酯與甲基丙烯酸酯之一方或雙方，「(甲基)丙烯醯基」係指丙烯醯基與甲基丙烯醯基之一方或雙方，「(甲基)丙烯酸」係指丙烯酸與甲基丙烯酸之一方或雙方。Furthermore, in the present invention, "(meth)acrylate" means one or both of acrylate and methacrylate, and "(meth)acryloyl" means acryloyl and methacryloyl One or both, "(meth)acrylic acid" refers to one or both of acrylic acid and methacrylic acid.
前述胺基甲酸酯(甲基)丙烯酸酯(A1)為以調整耐擦傷性及彎曲性為目的而使用之物，例如為：聚異氰酸酯(a1-1)與具有羥基的(甲基)丙烯酸酯(a1-2)之反應物(A1X)；聚異氰酸酯(a1-1)、具有羥基的(甲基)丙烯酸酯(a1-2)及多元醇(a1-3)之反應物(A1Y)，且可使用具有(甲基)丙烯醯基1個以上者，較佳為具有(甲基)丙烯醯基2～6個者。The aforementioned urethane (meth)acrylate (A1) is used for the purpose of adjusting scratch resistance and flexibility, such as polyisocyanate (a1-1) and (meth)acrylic acid having a hydroxyl group The reactant (A1X) of ester (a1-2); the reactant (A1Y) of polyisocyanate (a1-1), (meth)acrylate (a1-2) with hydroxyl group and polyol (a1-3), In addition, those having one or more (meth)acryloyl groups can be used, and those having 2 to 6 (meth)acryloyl groups are preferred.
作為前述聚異氰酸酯(a1-1)，可使用例如：六亞甲基二異氰酸酯、離胺酸二異氰酸酯、離胺酸三異氰酸酯等脂肪族聚異氰酸酯；降莰烷二異氰酸酯、異佛爾酮二異氰酸酯、亞甲基雙(4-環己基異氰酸酯)、1,3-雙(異氰酸基甲基)環己烷、2-甲基-1,3-二異氰酸基環己烷、2-甲基-1,5-二異氰酸基環己烷等脂環式聚異氰酸酯；甲苯二異氰酸酯、二甲苯二異氰酸酯、二苯甲烷二異氰酸酯等芳香族聚異氰酸酯等。該等之聚異氰酸酯，可單獨使用，亦可併用2種以上。As the aforementioned polyisocyanate (a1-1), for example, aliphatic polyisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, and lysine triisocyanate; norbornane diisocyanate, isophorone diisocyanate, etc. can be used , Methylenebis(4-cyclohexylisocyanate), 1,3-bis(isocyanatomethyl)cyclohexane, 2-methyl-1,3-diisocyanatocyclohexane, 2- Alicyclic polyisocyanates such as methyl-1,5-diisocyanatocyclohexane; aromatic polyisocyanates such as toluene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, etc. These polyisocyanates may be used alone or in combination of two or more kinds.
作為前述聚異氰酸酯(a1-1)，從可減低活性能量線硬化性組成物的硬化塗膜之著色的觀點而言，前述者之中，較佳為使用脂肪族聚異氰酸酯及/或脂環式聚異氰酸酯，更佳為選自包含六亞甲基二異氰酸酯、異佛爾酮二異氰酸酯、及二環己基甲烷二異氰酸酯的群組之1種以上的聚異氰酸酯，進一步更佳為六亞甲基二異氰酸酯及/或異佛爾酮二異氰酸酯。As the aforementioned polyisocyanate (a1-1), from the viewpoint of reducing the coloration of the cured coating film of the active energy ray curable composition, among the aforementioned, it is preferable to use aliphatic polyisocyanate and/or alicyclic The polyisocyanate is more preferably one or more polyisocyanates selected from the group consisting of hexamethylene diisocyanate, isophorone diisocyanate, and dicyclohexylmethane diisocyanate, and still more preferably hexamethylene diisocyanate Isocyanate and/or isophorone diisocyanate.
前述(甲基)丙烯酸酯(a1-2)為具有羥基與(甲基)丙烯醯基者，可舉出例如：(甲基)丙烯酸2-羥乙酯、(甲基)丙烯酸2-羥丙酯、(甲基)丙烯酸2-羥丁酯、(甲基)丙烯酸4-羥丁酯、1,5-戊二醇單(甲基)丙烯酸酯、1,6-己二醇單(甲基)丙烯酸酯、新戊二醇單(甲基)丙烯酸酯、羥基三甲基乙酸新戊二醇單(甲基)丙烯酸酯等二元醇的單(甲基)丙烯酸酯；三羥甲基丙烷二(甲基)丙烯酸酯、環氧乙烷(EO)改質三羥甲基丙烷(甲基)丙烯酸酯、環氧丙烷(PO)改質三羥甲基丙烷二(甲基)丙烯酸酯、丙三醇二(甲基)丙烯酸酯、雙(2-(甲基)丙烯醯氧乙基)羥乙基異三聚氰酸酯等之3元醇的單或二(甲基)丙烯酸酯、或將該等之醇性羥基的一部分以ε-己內酯改質之具有羥基的單及二(甲基)丙烯酸酯；季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二三羥甲基丙烷三(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯等具有1官能的羥基與3官能以上的(甲基)丙烯醯基之化合物、或將該化合物進一步以ε-己內酯改質之具有羥基的多官能(甲基)丙烯酸酯；二丙二醇單(甲基)丙烯酸酯、二乙二醇單(甲基)丙烯酸酯、聚丙二醇單(甲基)丙烯酸酯、聚乙二醇單(甲基)丙烯酸酯等具有氧化烯鏈的(甲基)丙烯酸酯；聚乙二醇-聚丙二醇單(甲基)丙烯酸酯、聚氧丁烯-聚氧丙烯單(甲基)丙烯酸酯等具有嵌段結構之氧化烯鏈的(甲基)丙烯酸酯；聚(乙二醇-伸丁二醇)單(甲基)丙烯酸酯、聚(丙二醇-伸丁二醇)單(甲基)丙烯酸酯等具有隨機結構之氧化烯鏈的(甲基)丙烯酸酯等。該等之(甲基)丙烯酸酯(a1-2)，可單獨使用，亦可併用2種以上。該等之中，在將未使用多元醇(a1-3)的類型(A1X)作為前述胺基甲酸酯(甲基)丙烯酸酯(A2)使用之情況，從得到更優異的耐擦傷性之觀點而言，較佳為使用選自包含季戊四醇三(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、及三季戊四醇七(甲基)丙烯酸酯的群組之1種類以上的化合物。又，在將使用多元醇(a1-3)的類型(A1Y)作為胺基甲酸酯(甲基)丙烯酸酯(A2)使用之情況，從得到更優異的彎曲性之觀點而言，較佳為使用(甲基)丙烯酸2-羥乙酯。The (meth)acrylate (a1-2) has a hydroxyl group and a (meth)acrylic acid group, and examples include 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate Ester, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 1,5-pentanediol mono(meth)acrylate, 1,6-hexanediol mono(methyl) ) Mono(meth)acrylate of diols such as acrylate, neopentyl glycol mono(meth)acrylate, hydroxytrimethylacetate neopentyl glycol mono(meth)acrylate, etc.; trimethylolpropane Di(meth)acrylate, ethylene oxide (EO) modified trimethylolpropane (meth)acrylate, propylene oxide (PO) modified trimethylolpropane di(meth)acrylate, Glycerol di(meth)acrylate, bis(2-(meth)acryloyloxyethyl)hydroxyethyl isocyanurate and other trivalent alcohol mono- or di(meth)acrylates, Or a part of these alcoholic hydroxyl groups is modified with ε-caprolactone and has hydroxyl mono- and di(meth)acrylates; pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, Ditrimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, and other compounds having monofunctional hydroxyl group and trifunctional or more (meth)acryloyl group, or the compound further ε-caprolactone modified polyfunctional (meth)acrylate with hydroxyl group; dipropylene glycol mono(meth)acrylate, diethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylic acid (Meth)acrylates with alkylene oxide chains such as polyethylene glycol mono(meth)acrylate; polyethylene glycol-polypropylene glycol mono(meth)acrylate, polyoxybutylene-polyoxypropylene mono (Meth)acrylates with block structure of alkylene oxide chains such as (meth)acrylates; poly(ethylene glycol-butylene glycol) mono(meth)acrylate, poly(propylene glycol-butylene glycol) ) Mono(meth)acrylates and other (meth)acrylates with random structure of alkylene oxide chains. These (meth)acrylates (a1-2) may be used alone, or two or more of them may be used in combination. Among these, when the type (A1X) not using the polyol (a1-3) is used as the aforementioned urethane (meth)acrylate (A2), a more excellent scratch resistance is obtained. From a viewpoint, it is preferable to use one or more compounds selected from the group consisting of pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, and tripentaerythritol hepta(meth)acrylate. In addition, in the case of using the type (A1Y) using the polyol (a1-3) as the urethane (meth)acrylate (A2), it is preferable from the viewpoint of obtaining more excellent flexibility To use 2-hydroxyethyl (meth)acrylate.
作為前述多元醇(a1-3)，可使用例如：聚乙二醇、聚丙二醇、聚四乙二醇等聚醚多元醇；聚酯多元醇、聚碳酸酯多元醇等。該等之多元醇，可單獨使用，亦可併用2種以上。從得到更優異的彎曲性之觀點而言，該等之中，較佳為使用聚醚多元醇，更佳為聚四乙二醇。As the aforementioned polyol (a1-3), for example, polyether polyols such as polyethylene glycol, polypropylene glycol, and polyethylene tetraethylene glycol; polyester polyols, polycarbonate polyols, and the like can be used. These polyhydric alcohols may be used alone, or two or more of them may be used in combination. From the viewpoint of obtaining more excellent flexibility, among these, polyether polyol is preferably used, and polyethylene tetraethylene glycol is more preferably used.
前述聚異氰酸酯(a1-1)與前述(甲基)丙烯酸酯(a1-2)之反應、及前述聚異氰酸酯(a1-1)與前述(甲基)丙烯酸酯(a1-2)與前述多元醇(a1-3)之反應，可使用常法的胺基甲酸酯化反應。又，在進行胺基甲酸酯化反應之際，視需要也可使用胺基甲酸酯化觸媒。作為前述胺基甲酸酯化觸媒，可使用例如：吡啶、吡咯、三乙胺、二乙胺、二丁胺等胺化合物；三苯基膦、三乙基膦等磷化合物；二丁基錫二月桂酸酯、辛基錫三月桂酸酯、辛基錫二乙酸酯、二丁基錫二乙酸酯、辛酸錫等有機錫化合物、辛酸鋅等有機鋅化合物等。The reaction of the aforementioned polyisocyanate (a1-1) and the aforementioned (meth)acrylate (a1-2), and the aforementioned polyisocyanate (a1-1) and the aforementioned (meth)acrylate (a1-2) and the aforementioned polyol For the reaction of (a1-3), a conventional carbamate reaction can be used. In addition, when the urethane reaction is performed, a urethane catalyst may be used as necessary. As the aforementioned carbamate catalyst, for example, amine compounds such as pyridine, pyrrole, triethylamine, diethylamine, and dibutylamine; phosphorus compounds such as triphenylphosphine and triethylphosphine; dibutyltin Organic tin compounds such as laurate, octyl tin trilaurate, octyl tin diacetate, dibutyl tin diacetate, tin octoate, and organic zinc compounds such as zinc octoate.
從得到更優異的彎曲性與耐擦傷性之觀點而言，在將使用多元醇(a1-3)的類型(A1Y)作為前述胺基甲酸酯(甲基)丙烯酸酯(A2)使用之情況中的胺基甲酸酯(甲基)丙烯酸酯之數量平均分子量，較佳為800～6,000的範圍，更佳為1,000～4,000的範圍。再者，前述胺基甲酸酯(甲基)丙烯酸酯的數量平均分子量係表示利用凝膠滲透管柱層析(GPC)法(溶離液；四氫呋喃、聚苯乙烯換算)測定到的數值。From the viewpoint of obtaining more excellent flexibility and scratch resistance, when using the type (A1Y) using polyol (a1-3) as the aforementioned urethane (meth)acrylate (A2) The number-average molecular weight of the urethane (meth)acrylate in in is preferably in the range of 800 to 6,000, and more preferably in the range of 1,000 to 4,000. In addition, the number average molecular weight of the aforementioned urethane (meth)acrylate represents a value measured by a gel permeation column chromatography (GPC) method (eluent; tetrahydrofuran, polystyrene conversion).
在併用前述(A1X)及(A1Y)作為前述胺基甲酸酯(甲基)丙烯酸酯(A1)之情況，從得到更優異的彎曲性及耐擦傷性之觀點而言，其質量比[(A1X)/(A1Y)]，較佳為10/90～90/10的範圍，更佳為30/70～70/30的範圍。When the aforementioned (A1X) and (A1Y) are used in combination as the aforementioned urethane (meth)acrylate (A1), from the viewpoint of obtaining more excellent flexibility and scratch resistance, the mass ratio [( A1X)/(A1Y)], preferably in the range of 10/90 to 90/10, more preferably in the range of 30/70 to 70/30.
前述環氧(甲基)丙烯酸酯(A2)為以提升帶電防止性及防眩性為目的而使用之物，可使用例如：不飽和單羧酸與環氧化合物之加成反應物。The aforementioned epoxy (meth)acrylate (A2) is used for the purpose of improving anti-static properties and anti-glare properties. For example, an addition reaction product of an unsaturated monocarboxylic acid and an epoxy compound can be used.
作為前述不飽和單羧酸，可使用例如：(甲基)丙烯酸、巴豆酸、肉桂酸等。該等之化合物，可單獨使用，亦可併用2種以上。從耐擦傷性及帶電防止性之觀點而言，該等之中，較佳為使用(甲基)丙烯酸。As the aforementioned unsaturated monocarboxylic acid, for example, (meth)acrylic acid, crotonic acid, cinnamic acid and the like can be used. These compounds may be used alone or in combination of two or more kinds. From the viewpoint of scratch resistance and anti-static property, among these, (meth)acrylic acid is preferably used.
作為前述環氧化合物，可使用例如：雙酚A二環氧丙醚、氫化雙酚A二環氧丙醚、溴化雙酚A二環氧丙醚等具有雙酚A骨架的環氧化合物；雙酚F二環氧丙醚等具有雙酚F骨架的環氧化合物；具有氫化鄰苯二甲酸骨架的環氧化合物；(甲基)丙烯酸環氧丙酯、丙烯酸4-羥丁酯環氧丙醚、(甲基)丙烯酸3,4-環氧環己基甲酯等具有環氧基及(甲基)丙烯醯基的化合物等。該等之化合物，可單獨使用，亦可併用2種以上，也可使用該等之聚合物。該等之中，從耐擦傷性及帶電防止性之觀點而言，較佳為使用環氧基及(甲基)丙烯酸化合物，更佳為使用(甲基)丙烯酸環氧丙酯的聚合物。As the aforementioned epoxy compound, for example, epoxy compounds having a bisphenol A skeleton such as bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, and brominated bisphenol A diglycidyl ether can be used; Epoxy compounds with bisphenol F skeleton such as bisphenol F diglycidyl ether; epoxy compounds with hydrogenated phthalic acid skeleton; (meth) glycidyl acrylate, 4-hydroxybutyl acrylate glycidyl Compounds having epoxy groups and (meth)acrylic groups, such as ether and 3,4-epoxycyclohexyl methyl (meth)acrylate. These compounds may be used alone or in combination of two or more, and these polymers may also be used. Among them, from the viewpoint of scratch resistance and anti-static property, it is preferable to use an epoxy group and a (meth)acrylic compound, and it is more preferable to use a polymer of glycidyl (meth)acrylate.
使用前述環氧化合物的聚合物作為前述環氧(甲基)丙烯酸酯(A2)的原料時，從黏度調整之觀點而言，也可併用溶劑。作為前述溶劑，可使用例如：甲基乙基酮、甲基異丁基酮、乙酸乙酯、乙酸丁酯等。該等溶劑，可單獨使用，亦可併用2種以上。作為使用前述溶劑時的含量，相對於環氧(甲基)丙烯酸酯(A2)100質量份，較佳為50～150質量份的範圍。When using the polymer of the epoxy compound as the raw material of the epoxy (meth)acrylate (A2), a solvent may be used in combination from the viewpoint of viscosity adjustment. As the aforementioned solvent, for example, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, and the like can be used. These solvents may be used alone or in combination of two or more kinds. As content when using the said solvent, the range of 50-150 mass parts is preferable with respect to 100 mass parts of epoxy (meth)acrylate (A2).
在使用前述環氧化合物的聚合物作為前述環氧(甲基)丙烯酸酯(A2)的原料之情況，包含溶劑之前述環氧(甲基)丙烯酸酯(A2)的黏度，從可更進一步提升形成硬塗層之際的塗布安定性之觀點而言，較佳為100～3,000mPa・s的範圍，更佳為150～2,000mPa・s的範圍。再者，前述黏度係表示使用B型黏度計進行測定的值。When the polymer of the aforementioned epoxy compound is used as the raw material of the aforementioned epoxy (meth)acrylate (A2), the viscosity of the aforementioned epoxy (meth)acrylate (A2) containing a solvent can be further improved From the viewpoint of coating stability when forming the hard coat layer, the range is preferably 100 to 3,000 mPa·s, and more preferably 150 to 2,000 mPa·s. In addition, the aforementioned viscosity represents a value measured using a B-type viscometer.
前述其它多官能(甲基)丙烯酸酯(A3)為用以得到硬塗性者，表示前述(A1)及(A2)以外之在1分子中具有較佳為2～8個，更佳為3～6個(甲基)丙烯醯基的化合物。作為前述其它多官能(甲基)丙烯酸酯(A3)，可使用例如：1,4-丁二醇二(甲基)丙烯酸酯、3-甲基-1,5-戊二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、2-甲基-1,8-辛二醇二(甲基)丙烯酸酯、2-丁基-2-乙基-1,3-丙二醇二(甲基)丙烯酸酯、三環癸烷二甲醇二(甲基)丙烯酸酯、乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、三乙二醇二(甲基)丙烯酸酯、二丙二醇二(甲基)丙烯酸酯、三丙二醇二(甲基)丙烯酸酯等二元醇的二(甲基)丙烯酸酯；聚乙二醇二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、參(2-羥乙基)異三聚氰酸酯的二(甲基)丙烯酸酯、對1莫耳新戊二醇加成4莫耳以上的環氧乙烷或環氧丙烷而得到之二醇的二(甲基)丙烯酸酯；對1莫耳雙酚A加成2莫耳的環氧乙烷或環氧丙烷而得到之二醇的二(甲基)丙烯酸酯；三羥甲基丙烷三(甲基)丙烯酸酯、環氧乙烷改質三羥甲基丙烷三(甲基)丙烯酸酯、環氧丙烷改質三羥甲基丙烷三(甲基)丙烯酸酯、二三羥甲基丙烷三(甲基)丙烯酸酯、二三羥甲基丙烷四(甲基)丙烯酸酯、參(2-(甲基)丙烯醯基氧乙基)異三聚氰酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇三(甲基)丙烯酸酯、二季戊四醇四(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、三季戊四醇六(甲基)丙烯酸酯、三季戊四醇七(甲基)丙烯酸酯、三季戊四醇八(甲基)丙烯酸酯等。該等之化合物，可單獨使用，亦可併用2種以上。The aforementioned other polyfunctional (meth)acrylates (A3) are those used to obtain hard coat properties, and it means that those other than the aforementioned (A1) and (A2) have preferably 2 to 8 per molecule, more preferably 3 ~ 6 (meth)acrylic compounds. As the aforementioned other polyfunctional (meth)acrylate (A3), for example, 1,4-butanediol di(meth)acrylate, 3-methyl-1,5-pentanediol bis(methyl) )Acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 2-methyl-1,8-octanediol di(meth)acrylate , 2-Butyl-2-ethyl-1,3-propanediol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, ethylene glycol di(meth)acrylate, two Ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate and other dihydric alcohols Base) acrylate; polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, di(meth)acrylate of (2-hydroxyethyl) isocyanurate, Di(meth)acrylate of diol obtained by adding more than 4 moles of ethylene oxide or propylene oxide to 1 mole of neopentyl glycol; adding 2 moles of bisphenol A to 1 mole Di(meth)acrylate of glycol derived from ethylene oxide or propylene oxide; trimethylolpropane tri(meth)acrylate, ethylene oxide modified trimethylolpropane tri(methyl) ) Acrylate, propylene oxide modified trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, Ginseng (2-(meth)acryloyloxyethyl) isocyanurate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tri(meth)acrylate, Dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol hexa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, Tripentaerythritol octa(meth)acrylate and the like. These compounds may be used alone or in combination of two or more kinds.
從得到更優異的耐擦傷性之觀點而言，作為前述其它多官能(甲基)丙烯酸酯(A3)，前述之中，更佳為使用選自包含三季戊四醇八(甲基)丙烯酸酯、三季戊四醇七(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、及季戊四醇三(甲基)丙烯酸酯的群組之1種以上的化合物，進一步更佳為季戊四醇四(甲基)丙烯酸酯、及季戊四醇三(甲基)丙烯酸酯。From the standpoint of obtaining more excellent scratch resistance, as the aforementioned other polyfunctional (meth)acrylate (A3), among the aforementioned, it is more preferable to use a compound selected from tripentaerythritol octa(meth)acrylate, tripentaerythritol Groups of pentaerythritol hepta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, pentaerythritol tetra(meth)acrylate, and pentaerythritol tri(meth)acrylate One or more of the compounds are more preferably pentaerythritol tetra(meth)acrylate and pentaerythritol tri(meth)acrylate.
從得到更優異的帶電防止性、防眩性、及耐擦傷性之觀點而言，作為前述活性能量線硬化性化合物(A)，較佳為胺基甲酸酯(甲基)丙烯酸酯(A1)與環氧(甲基)丙烯酸酯(A2)與其它多官能(甲基)丙烯酸酯(A3)之組合、或是環氧(甲基)丙烯酸酯(A2)與其它多官能(甲基)丙烯酸酯(A3)之組合。From the viewpoint of obtaining more excellent anti-static properties, anti-glare properties, and scratch resistance, the active energy ray-curable compound (A) is preferably urethane (meth)acrylate (A1) ) And epoxy (meth)acrylate (A2) and other multifunctional (meth)acrylate (A3), or epoxy (meth)acrylate (A2) and other multifunctional (meth) Combination of acrylate (A3).
在使用(A1)～(A3)全部作為前述活性能量線硬化性化合物(A)之情況，前述胺基甲酸酯(甲基)丙烯酸酯(A1)的使用量，從得到更優異的耐擦傷性、帶電防止性及防眩性之觀點而言，較佳為活性能量線硬化性化合物(A)中1～50質量%的範圍，更佳為5～30質量%的範圍。又，從得到更優異的耐擦傷性、帶電防止性及防眩性之觀點而言，前述環氧(甲基)丙烯酸酯(A2)的使用量，較佳為活性能量線硬化性化合物(A)中10～80質量%的範圍，更佳為20～60質量%的範圍。In the case of using all (A1) to (A3) as the active energy ray-curable compound (A), the amount of the urethane (meth)acrylate (A1) used will provide more excellent scratch resistance From the viewpoints of performance, anti-static properties, and anti-glare properties, the range of 1 to 50% by mass in the active energy ray curable compound (A) is preferable, and the range of 5 to 30% by mass is more preferable. In addition, from the viewpoint of obtaining more excellent scratch resistance, anti-static properties, and anti-glare properties, the amount of the epoxy (meth)acrylate (A2) used is preferably an active energy ray curable compound (A ) Is in the range of 10 to 80% by mass, more preferably in the range of 20 to 60% by mass.
在使用環氧(甲基)丙烯酸酯(A2)與其它多官能(甲基)丙烯酸酯(A3)之組合作為前述活性能量線硬化性化合物(A)之情況，作為前述多官能(甲基)丙烯酸酯(A1)與前述環氧(甲基)丙烯酸酯(A3)之質量比[(A2)/(A3)]，從得到更優異的耐擦傷性及帶電防止性之觀點而言，較佳為20/80～90/10的範圍，更佳為40/60～80/20的範圍。When a combination of epoxy (meth)acrylate (A2) and other polyfunctional (meth)acrylate (A3) is used as the active energy ray curable compound (A), it is used as the polyfunctional (meth) The mass ratio [(A2)/(A3)] of the acrylate (A1) and the aforementioned epoxy (meth)acrylate (A3) is preferable from the viewpoint of obtaining more excellent scratch resistance and anti-static properties It is the range of 20/80-90/10, More preferably, it is the range of 40/60-80/20.
作為前述活性能量線硬化性化合物(A)，除前述(A1)～(A3)以外，視需要也可使用聚酯(甲基)丙烯酸酯、聚醚(甲基)丙烯酸酯、苯乙烯等。該等之化合物，可單獨使用，亦可併用2種以上。作為前述活性能量線硬化性化合物(A)中之前述(A1)～(A3)的合計質量，較佳為50質量%以上，更佳為80質量%以上，進一步更佳為90質量%以上。As the active energy ray-curable compound (A), in addition to the above (A1) to (A3), polyester (meth)acrylate, polyether (meth)acrylate, styrene, etc. may be used as needed. These compounds may be used alone or in combination of two or more kinds. The total mass of (A1) to (A3) in the active energy ray curable compound (A) is preferably 50% by mass or more, more preferably 80% by mass or more, and still more preferably 90% by mass or more.
作為前述帶電防止性(B)，為了兼具優異的防眩性與帶電防止性，必須使用具有下述式(1)所示之陽離子部的離子性液體。As the aforementioned anti-static property (B), in order to have both excellent anti-glare properties and anti-static properties, it is necessary to use an ionic liquid having a cationic portion represented by the following formula (1).
前述帶電防止劑(B)，推測因為在陽離子部具有長鏈的烴，所以與以往使用的帶電防止劑相比，立體結構大，且疏水性高，因此可兼具優異的防眩性與帶電防止性。The aforementioned anti-static agent (B) is presumed to have long-chain hydrocarbons in the cation part, so compared with conventional anti-static agents, it has a larger three-dimensional structure and high hydrophobicity, so it can have both excellent anti-glare properties and electrification. Preventive.
作為前述帶電防止劑(B)，可使用例如：前述式(1)中之X為磷原子或氮原子，R1 ～R4 各別獨立地為碳原子數1～20的烷基或烯基，碳原子數之合計為10以上且小於30的離子性液體(B1)；或前述式(1)中之X為磷原子或氮原子，R1 ～R4 各別獨立地為碳原子數3～20的烷基或烯基，碳原子數之合計為30以上的離子性液體(B2)等。As the aforementioned antistatic agent (B), for example, X in the aforementioned formula (1) is a phosphorus atom or a nitrogen atom, and R 1 to R 4 are each independently an alkyl or alkenyl group having 1 to 20 carbon atoms. , An ionic liquid (B1) with a total number of carbon atoms of 10 or more and less than 30; or X in the aforementioned formula (1) is a phosphorus atom or a nitrogen atom, and R 1 to R 4 are each independently a carbon atom number of 3 -20 alkyl or alkenyl, ionic liquid (B2) with a total of 30 or more carbon atoms, etc.
從得到更優異的防眩性及帶電防止性之觀點而言，作為前述離子性液體(B1)，較佳為使用：前述式(1)中之R1 ～R4 各別獨立且較佳表示碳原子數1～16(更佳為1～14)的烷基、碳原子數之合計較佳為15～28的範圍(更佳為20～26的範圍)者。From the viewpoint of obtaining more excellent anti-glare properties and anti-static properties, as the aforementioned ionic liquid (B1), it is preferable to use: R 1 to R 4 in the aforementioned formula (1) are independently and preferably represented The alkyl group having 1 to 16 carbon atoms (more preferably 1 to 14) and the total number of carbon atoms are preferably those in the range of 15 to 28 (more preferably the range of 20 to 26).
從得到更優異的防眩性及帶電防止性之觀點而言，作為前述離子性液體(B2)，較佳為使用：前述式(1)中之X較佳表示磷原子、R1 ～R4 各別獨立且較佳表示碳原子數4～18(更佳為5～16)的烷基、碳原子數之合計較佳為30～40的範圍(更佳為31～36的範圍)者。From the viewpoint of obtaining more excellent anti-glare properties and anti-static properties, as the ionic liquid (B2), it is preferable to use: X in the aforementioned formula (1) preferably represents a phosphorus atom, R 1 to R 4 Each independently and preferably represents an alkyl group having 4 to 18 carbon atoms (more preferably 5 to 16), and the total number of carbon atoms is preferably in the range of 30 to 40 (more preferably, the range of 31 to 36).
作為前述帶電防止劑(B)之陰離子部，可使用例如：Br- 、Cl- 、I- 、BF4 - 、PF6 - 、FeCl4 - 、AlCl4 - 、Al2 Cl7 - 、NO3 - 、ClO4 - 、HSO4 - 、CH3 SO4 - 、CH3 SO3 - 、CF3 SO3 - 、C6 H4 CH3 SO3 - 、C4 F7 SO3 - 、CH3 CH2 OSO3 - 、CH3 COO- 、CF3 COO- 、C3 F7 COO- 、(NC)2 N- 、(CF3 SO2 )2 N- 、(C2 F5 SO2 )2 N- 、(CF3 SO2 )(CF3 CO)N- 、Tf2 N- 、SCN- 、(CF3 SO2 )3 C- 、AsF6 - 、SbF6 - 、NbF6 - 、TaF6 - 、C(CN)3 - 等。Examples of the antistatic agent (B) of the anionic portion, may be used, for example: Br -, Cl -, I -, BF 4 -, PF 6 -, FeCl 4 -, AlCl 4 -, Al 2 Cl 7 -, NO 3 - , ClO 4 -, HSO 4 - , CH 3 SO 4 -, CH 3 SO 3 -, CF 3 SO 3 -, C 6 H 4 CH 3 SO 3 -, C 4 F 7 SO 3 -, CH 3 CH 2 OSO 3 -, CH 3 COO -, CF 3 COO -, C 3 F 7 COO -, (NC) 2 N -, (CF 3 SO 2) 2 N -, (C 2 F 5 SO 2) 2 N -, ( CF 3 SO 2) (CF 3 CO) N -, Tf 2 N -, SCN -, (CF 3 SO 2) 3 C -, AsF 6 -, SbF 6 -, NbF 6 -, TaF 6 -, C (CN ) 3 - Wait.
從得到更優異的防眩性及帶電防止性之觀點而言，前述帶電防止劑(B)的含量，較佳為活性能量線硬化性組成物中0.01～20質量%的範圍，更佳為0.05～5質量%的範圍。From the viewpoint of obtaining more excellent anti-glare properties and anti-static properties, the content of the anti-static agent (B) is preferably in the range of 0.01 to 20% by mass in the active energy ray curable composition, more preferably 0.05 ～5% by mass range.
作為本發明的活性能量線硬化性組成物，為了提升塗布性，較佳為含有溶劑(C)。As the active energy ray-curable composition of the present invention, in order to improve coatability, it is preferable to contain a solvent (C).
作為前述溶劑(C)，可使用例如：甲醇、乙醇、丙醇、丁醇、二丙酮醇、雙丙酮醇、二甲基卡必醇、乙酸甲酯、乙酸乙酯、甲基乙基酮、甲基異丁基酮、乙醯丙酮、乙醯丙酮、丙二醇單甲醚乙酸酯、乙二醇單甲醚等。該等之溶劑，可單獨使用，亦可併用2種以上。從得到更優異的帶電防止性之觀點而言，該等之中，較佳為使用乙醇。As the aforementioned solvent (C), for example, methanol, ethanol, propanol, butanol, diacetone alcohol, diacetone alcohol, dimethyl carbitol, methyl acetate, ethyl acetate, methyl ethyl ketone, Methyl isobutyl ketone, acetone, acetone, propylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether, etc. These solvents can be used alone or in combination of two or more kinds. From the viewpoint of obtaining more excellent antistatic properties, among these, ethanol is preferably used.
從塗布性等之觀點而言，作為使用前述溶劑(C)時的使用量，較佳為活性能量線硬化性組成物中40～80質量%的範圍。From the viewpoint of coatability, etc., the amount used when the solvent (C) is used is preferably in the range of 40 to 80% by mass in the active energy ray curable composition.
本發明的活性能量線硬化性組成物，塗布於基材後，藉由照射活性能量線，可形成硬化塗膜。該活性能量線係指紫外線、電子束、α射線、β射線、γ線等游離輻射。在照射紫外線作為活性能量線成為硬化塗膜時，較佳為在本發明的活性能量線硬化性組成物中添加光聚合起始劑(D)，提升硬化性。又，若有需要，則進一步添加光增感劑(E)，也可提升硬化性。另一方面，在使用電子束、α射線、β射線、γ線等游離輻射時，因為就算不使用光聚合起始劑(D)或光增感劑(E)，也會迅速地硬化，所以不需要特別添加光聚合起始劑(D)或光增感劑(E)。The active energy ray curable composition of the present invention can form a hardened coating film by irradiating the active energy ray after coating on a substrate. The active energy rays refer to ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. When irradiating ultraviolet rays as active energy rays to form a cured coating film, it is preferable to add a photopolymerization initiator (D) to the active energy ray curable composition of the present invention to improve curability. Moreover, if necessary, a photosensitizer (E) can be further added to improve the curability. On the other hand, when ionizing radiation such as electron beam, α-ray, β-ray, and γ-ray is used, it hardens quickly even if the photopolymerization initiator (D) or photosensitizer (E) is not used. It is not necessary to particularly add a photopolymerization initiator (D) or photosensitizer (E).
作為前述光聚合起始劑(D)，可使用例如：二乙氧基苯乙酮、2-羥基-2-甲基-1-苯基丙烷-1-酮、寡{2-羥基-2-甲基-1-[4-(1-甲基乙烯基)苯基]丙酮}、苯甲基二甲基縮酮、1-(4-異丙基苯基)-2-羥基-2-甲基丙烷-1-酮、4-(2-羥基乙氧基)苯基-(2-羥基-2-丙基)酮、1-羥基環己基苯酮、2-甲基-2-[口+末]啉基(4-硫代甲基苯基)丙烷-1-酮、2-苯甲基-2-二甲胺基-1-(4-[口+末]啉基苯基)-丁酮等苯乙酮系化合物；苯偶姻、苯偶姻甲醚、苯偶姻異丙醚等苯偶姻系化合物；2,4,6-三甲基苯偶姻二苯基氧化膦、雙(2,4,6-三甲基苯甲醯基)-苯基氧化膦等醯基氧化膦系化合物；苯甲基(二苯甲醯基)、甲基苯基乙醛酸酯、氧基苯乙酸2-(2-羥基乙氧基)乙酯、氧基苯乙酸2-(2-側氧基-2-苯基乙醯氧基乙氧基)乙酯等苯甲基系化合物；二苯甲酮、o-苯甲醯基苯甲酸甲酯-4-苯基二苯甲酮、4,4’-二氯二苯甲酮、羥基二苯甲酮、4-苯甲醯基-4’-甲基-二苯硫醚、丙烯酸化二苯甲酮、3,3’,4,4’-四(三級丁基過氧化羰基)二苯甲酮、3,3’-二甲基-4-甲氧基二苯甲酮、2,4,6-三甲基二苯甲酮、4-甲基二苯甲酮等二苯甲酮系化合物；2-異丙基噻噸酮、2,4-二甲基噻噸酮、2,4-二乙基噻噸酮、2,4-二氯噻噸酮等噻噸酮系化合物；米氏酮、4,4’-二乙胺基二苯甲酮等胺基二苯甲酮系化合物；10-丁基-2-氯基吖啶酮、2-乙基蒽醌、9,10-菲醌、樟腦醌、1-[4-(4-苯甲醯基苯基氫硫基)苯基]-2-甲基-2-(4-甲苯基磺醯基)丙烷-1-酮等。該等之光聚合起始劑(D)，可單獨使用，亦可併用2種以上。As the aforementioned photopolymerization initiator (D), for example, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, oligo{2-hydroxy-2- Methyl-1-[4-(1-methylvinyl)phenyl]acetone}, benzyl dimethyl ketal, 1-(4-isopropylphenyl)-2-hydroxy-2-methyl Propane-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexylphenone, 2-methyl-2-[口+ Terminal] linyl (4-thiomethylphenyl) propane-1-one, 2-benzyl-2-dimethylamino-1-(4-[口+ terminal] linyl phenyl)-butanol Acetophenone compounds such as ketones; benzoin compounds such as benzoin, benzoin methyl ether, and benzoin isopropyl ether; 2,4,6-trimethylbenzoin diphenyl phosphine oxide, double (2,4,6-Trimethylbenzyl)-phenylphosphine oxide and other phosphine oxide compounds; benzyl (dibenzyl), methyl phenyl glyoxylate, oxy Benzyl compounds such as 2-(2-hydroxyethoxy)ethyl phenylacetate and 2-(2-oxo-2-phenylacetoxyethoxy)ethyl oxyphenylacetate; two Benzophenone, o-benzylmethyl benzoate-4-phenylbenzophenone, 4,4'-dichlorobenzophenone, hydroxybenzophenone, 4-benzyl-4 '-Methyl-diphenyl sulfide, acrylated benzophenone, 3,3',4,4'-tetra(tertiary butylperoxycarbonyl)benzophenone, 3,3'-dimethyl Benzophenone compounds such as -4-methoxybenzophenone, 2,4,6-trimethylbenzophenone, 4-methylbenzophenone; 2-isopropylthioxanthone, 2,4-Dimethylthioxanthone, 2,4-Diethylthioxanthone, 2,4-Dichlorothioxanthone and other thioxanthone compounds; Michler's ketone, 4,4'-diethylamine Amino benzophenone compounds such as benzophenone; 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, camphorquinone, 1-[4- (4-Benzylphenylsulfanyl)phenyl]-2-methyl-2-(4-tolylsulfonyl)propan-1-one and the like. These photopolymerization initiators (D) may be used alone or in combination of two or more kinds.
又，作為前述光增感劑(E)，可使用例如：二乙醇胺、N-甲基二乙醇胺、三丁胺等三級胺化合物、o-甲苯基硫脲等脲化合物、二乙基鈉二硫代磷酸鹽、s-苯甲基異脲鎓-p-甲苯磺酸鹽等硫化合物等。In addition, as the aforementioned photosensitizer (E), for example, tertiary amine compounds such as diethanolamine, N-methyldiethanolamine, and tributylamine, urea compounds such as o-tolylthiourea, and sodium diethyl Sulfur compounds such as thiophosphate and s-benzylisouronium-p-toluenesulfonate.
使用上述之光聚合起始劑(D)及光增感劑(E)時的使用量，相對於前述活性能量線硬化性化合物(A)100質量份，各別較佳為0.05～20質量份的範圍，更佳為0.5～10質量份的範圍。The usage amount when using the above-mentioned photopolymerization initiator (D) and photosensitizer (E) is preferably 0.05 to 20 parts by mass relative to 100 parts by mass of the active energy ray curable compound (A) The range of is more preferably the range of 0.5-10 parts by mass.
本發明的活性能量線硬化性組成物，含有前述活性能量線硬化性化合物(A)及前述帶電防止劑(B)作為必要成分，但視需要亦可含有其它添加劑。The active energy ray curable composition of the present invention contains the active energy ray curable compound (A) and the antistatic agent (B) as essential components, but may also contain other additives as necessary.
作為前述其它添加劑，可使用例如：聚合抑制劑、表面調整劑、前述(B)以外的帶電防止劑、消泡劑、黏度調整劑、耐光安定劑、耐候安定劑、耐熱安定劑、紫外線吸收劑、抗氧化劑、調平劑、有機顏料、無機顏料、顏料分散劑、微粒等添加劑；二氧化矽、氧化鋁、氧化鈦、氧化鋯、五氧化銻等無機填充劑等。該等之添加劑，可單獨使用，亦可併用2種以上。As the aforementioned other additives, for example, polymerization inhibitors, surface modifiers, antistatic agents other than (B) above, defoamers, viscosity modifiers, light stabilizers, weather stabilizers, heat stabilizers, ultraviolet absorbers can be used , Antioxidants, leveling agents, organic pigments, inorganic pigments, pigment dispersants, particles and other additives; silica, alumina, titanium oxide, zirconium oxide, antimony pentoxide and other inorganic fillers. These additives may be used alone or in combination of two or more kinds.
作為前述微粒，可使用無機系微粒、有機系微粒，較佳為使用透明性者。作為前述有機系微粒，可使用塑膠聚合物珠粒，可使用例如：苯乙烯系珠粒(折射率1.60)、三聚氰胺系珠粒(折射率1.57)、丙烯酸系珠粒(折射率1.49～1.535)、丙烯酸-苯乙烯系珠粒(折射率1.54～1.58)、苯并胍胺-甲醛珠粒、聚碳酸酯珠粒、聚乙烯珠粒等。作為前述無機系微粒，可使用例如，球狀二氧化矽、不定形二氧化矽等。該等之中，較佳為使用有機微粒，從凝聚力高且與前述帶電防止劑(B)之相溶性為良好，並且得到更優異的帶電防止性及防眩性之觀點而言，較佳為使用丙烯酸系珠粒、及/或丙烯酸-苯乙烯系珠粒，更佳為丙烯酸系珠粒。As the above-mentioned fine particles, inorganic fine particles and organic fine particles can be used, and transparent ones are preferred. As the aforementioned organic particles, plastic polymer beads can be used. For example, styrene beads (refractive index 1.60), melamine beads (refractive index 1.57), acrylic beads (refractive index 1.49 to 1.535) can be used. , Acrylic-styrene beads (refractive index 1.54-1.58), benzoguanamine-formaldehyde beads, polycarbonate beads, polyethylene beads, etc. As the aforementioned inorganic fine particles, for example, spherical silica, amorphous silica, etc. can be used. Among them, organic fine particles are preferably used. From the viewpoint of high cohesive force and good compatibility with the aforementioned anti-static agent (B), and obtaining more excellent anti-static properties and anti-glare properties, it is more preferable to Acrylic beads and/or acrylic-styrene beads are used, more preferably acrylic beads.
從得到凝聚力高且更優異的帶電防止性及防眩性之觀點而言，前述微粒的粒徑，較佳為0.5～5.0μm的範圍，更佳為0.8～3.5μm的範圍，進一步更佳為1.0～2.5μm的範圍。再者，前述有機微粒的粒徑表示在粒度分布中之粒度分布測定結果的累計粒子量曲線中，其累計量佔50%時的粒徑。From the viewpoint of obtaining high cohesive force and more excellent anti-static properties and anti-glare properties, the particle size of the aforementioned fine particles is preferably in the range of 0.5 to 5.0 μm, more preferably in the range of 0.8 to 3.5 μm, and still more preferably The range of 1.0～2.5μm. In addition, the particle size of the aforementioned organic fine particles represents the particle size when the cumulative amount is 50% in the cumulative particle amount curve of the particle size distribution measurement result in the particle size distribution.
從得到更優異的帶電防止性及防眩性之觀點而言，使用前述微粒時的使用量，較佳為活性能量線硬化性組成物中0.5～15質量%的範圍，更佳為1～7質量%的範圍。From the viewpoint of obtaining more excellent anti-static properties and anti-glare properties, the amount used when using the aforementioned fine particles is preferably in the range of 0.5 to 15% by mass in the active energy ray curable composition, more preferably 1 to 7 The range of mass %.
本發明的薄膜為：在薄膜基材之至少1面，塗布本發明的活性能量線硬化性組成物之後，照射活性能量線成為硬化塗膜而藉此得到者。The film of the present invention is obtained by coating the active energy ray curable composition of the present invention on at least one side of a film substrate, and then irradiating the active energy ray to form a cured coating film.
作為本發明的薄膜所使用之前述薄膜基材的材質，較佳為透明性高的樹脂，且可舉出例如：聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯、聚萘二甲酸乙二酯等聚酯系樹脂；聚丙烯、聚乙烯、聚甲基戊烯-1等聚烯烴系樹脂；纖維素乙酸酯(二乙醯纖維素、三乙醯纖維素等)、纖維素乙酸酯丙酸酯、纖維素乙酸酯丁酸酯、纖維素乙酸酯丙酸酯丁酸酯、纖維素乙酸酯苯二甲酸酯、硝酸纖維素等纖維素系樹脂；聚甲基丙烯酸甲酯等丙烯酸系樹脂；聚氯乙烯、聚二氯亞乙烯等氯乙烯系樹脂；聚乙烯醇；乙烯-乙酸乙烯酯共聚物；聚苯乙烯；聚醯胺；聚碳酸酯；聚碸；聚醚碸；聚醚醚酮；聚醯亞胺、聚醚醯亞胺等聚醯亞胺系樹脂；降莰烯系樹脂(例如Zeon Corporation製「ZEONOR」)、改質降莰烯系樹脂(例如JSR股份有限公司製「ARTON」)、環狀烯烴共聚物(例如三井化學股份有限公司製「APEL」)等。再者，也可使用貼合2種以上之包含該等之樹脂的基材者。The material of the aforementioned film substrate used in the film of the present invention is preferably a resin with high transparency, and examples thereof include polyethylene terephthalate, polybutylene terephthalate, and polynaphthalene Polyester resins such as ethylene dicarboxylate; polyolefin resins such as polypropylene, polyethylene, and polymethylpentene-1; cellulose acetate (diacetyl cellulose, triacetyl cellulose, etc.), Cellulosic resins such as cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate propionate butyrate, cellulose acetate phthalate, and nitrocellulose; Acrylic resins such as polymethyl methacrylate; vinyl chloride resins such as polyvinyl chloride and polyvinylidene chloride; polyvinyl alcohol; ethylene-vinyl acetate copolymer; polystyrene; polyamide; polycarbonate; Polyether; Polyether; Polyetheretherketone; Polyimine resins such as polyimine and polyetherimine; Norbornene resin (such as "ZEONOR" manufactured by Zeon Corporation), modified norbornene Resin (for example, "ARTON" manufactured by JSR Co., Ltd.), cyclic olefin copolymer (for example, "APEL" manufactured by Mitsui Chemicals Co., Ltd.), etc. In addition, a substrate in which two or more types of resins are bonded together can also be used.
再者，在本發明中，藉由使用前述活性能量線硬化性組成物，即使為使用聚甲基丙烯酸甲酯作為前述薄膜基材的情況，也可形成防眩性及帶電防止性優異的硬塗層。Furthermore, in the present invention, by using the active energy ray curable composition, even in the case of using polymethyl methacrylate as the film substrate, it is possible to form a rigid material with excellent anti-glare properties and anti-static properties. coating.
前述聚甲基丙烯酸甲酯基材(以下簡稱為「PMMA」)為以聚甲基丙烯酸甲酯作為主成分(較佳為100質量%)之聚合物所形成的基材，作為市售品，可取自例如：住友化學股份有限公司製「Technolloy S014G」、「Technolloy S001G」、「Technolloy S000」；三菱化學股份有限公司製「ACRYPLEN HBS006」、「ACRYPLEN HBXN47」、「ACRYPLEN HBS010」；帝人化成股份有限公司製「Panlite Flim PC-2151」等。The aforementioned polymethyl methacrylate substrate (hereinafter referred to as "PMMA") is a substrate formed of a polymer with polymethyl methacrylate as the main component (preferably 100% by mass), as a commercially available product, Can be taken from, for example: "Technolloy S014G", "Technolloy S001G", "Technolloy S000" made by Sumitomo Chemical Co., Ltd.; "ACRYPLEN HBS006", "ACRYPLEN HBXN47", "ACRYPLEN HBS010" made by Mitsubishi Chemical Corporation; and Teijin Chemical Co., Ltd. Limited company "Panlite Flim PC-2151", etc.
前述薄膜基材，可為薄膜狀，也可為薄片狀，其厚度，例如為20～500μm的範圍。又，在使用薄膜狀的基材薄膜時，其厚度，較佳為20～200μm的範圍，更佳為30～150μm的範圍，進一步更佳為40～130μm的範圍。藉由將薄膜基材的厚度定為該範圍，即使在薄膜的單面藉由本發明的活性能量線硬化性組成物設置硬塗層時，也變得容易抑制捲曲。The aforementioned film substrate may be in the form of a film or a sheet, and its thickness is, for example, in the range of 20 to 500 μm. Moreover, when a film-like base film is used, its thickness is preferably in the range of 20 to 200 μm, more preferably in the range of 30 to 150 μm, and still more preferably in the range of 40 to 130 μm. By setting the thickness of the film base material within this range, even when a hard coat layer is provided on one side of the film with the active energy ray curable composition of the present invention, it becomes easy to suppress curling.
作為在前述薄膜基材塗布本發明之活性能量線硬化性組成物的方法，可舉出例如，模塗布、微凹版塗布、凹版塗布、輥塗布、缺角輪塗布、氣刀塗布、吻合塗布、噴灑塗布、浸漬塗布、旋轉器塗布、刷塗、利用絲網的無光澤塗布、線棒塗布、覆墨(flow coat)等。As a method of coating the active energy ray curable composition of the present invention on the aforementioned film substrate, for example, die coating, micro-gravure coating, gravure coating, roll coating, chamfered wheel coating, air knife coating, kiss coating, Spray coating, dip coating, spinner coating, brush coating, matte coating with a screen, wire bar coating, flow coating, etc.
在將前述活性能量線硬化性組成物，對基材薄膜進行塗布之後，在照射活性能量線之前，為了揮發溶媒(C)，較佳為進行加熱或室溫乾燥。作為加熱乾燥的條件，可舉出例如，在溫度50～100℃的範圍，且時間為0.5～10分鐘的範圍進行加熱乾燥。After the active energy ray curable composition is applied to the base film and before the active energy ray is irradiated, in order to volatilize the solvent (C), it is preferably heated or dried at room temperature. As the conditions for the heating and drying, for example, heating and drying are performed at a temperature in the range of 50 to 100°C and a time in the range of 0.5 to 10 minutes.
作為使本發明之活性能量線硬化性組成物硬化的活性能量線，如上述為紫外線、電子束、α射線、β射線、γ線等游離輻射。在此，使用紫外線作為活性能量線時，作為照射其紫外線的裝置，可舉出例如，低壓汞燈、高壓汞燈、超高壓汞燈、金屬鹵素燈、無電極燈(fusion lamp)、化學燈、黑光燈、汞-氙氣燈、短弧燈、氦・鎘雷射、氬雷射、太陽光、LED燈等。The active energy rays for curing the active energy ray curable composition of the present invention include ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays as described above. Here, when ultraviolet rays are used as the active energy rays, as a device that irradiates the ultraviolet rays, for example, low pressure mercury lamps, high pressure mercury lamps, ultra high pressure mercury lamps, metal halide lamps, fusion lamps, chemical lamps , Black light lamp, mercury-xenon lamp, short arc lamp, helium and cadmium laser, argon laser, sunlight, LED lamp, etc.
從使硬化塗膜的硬度變足夠，且可抑制塗膜之硬化收縮所致的薄膜之捲曲的觀點而言，在前述薄膜基材上形成本發明之活性能量線硬化性組成物的硬化塗膜之際的硬化塗膜之膜厚，較佳為1～30μm的範圍，更佳為3～15μm的範圍，進一步更佳為4～10μm的範圍。From the viewpoint of making the hardness of the cured coating film sufficient and suppressing the curling of the film caused by the curing shrinkage of the coating film, the cured coating film of the active energy ray curable composition of the present invention is formed on the aforementioned film substrate The thickness of the cured coating film at this time is preferably in the range of 1 to 30 μm, more preferably in the range of 3 to 15 μm, and still more preferably in the range of 4 to 10 μm.
以上本發明的活性能量線硬化性組成物，以包含聚甲基丙烯酸甲酯基材之各式各樣的基材為前提，可形成塗布安定性、塗膜外觀、防眩性及帶電防止性優異的硬塗層。The active energy ray curable composition of the present invention is based on various substrates including polymethyl methacrylate substrates, and can provide coating stability, coating appearance, anti-glare properties, and anti-static properties. Excellent hard coating.
因此，具有包含本發明的活性能量線硬化性組成物之硬化塗膜的硬塗層之薄膜，可適當使用作為使用於液晶顯示器(LCD)、有機EL顯示器(OLED)、電漿顯示器(PDP)等平板顯示器(FPD)的光學薄膜。 [實施例]Therefore, a thin film having a hard coat layer containing a hardened coating film of the active energy ray curable composition of the present invention can be suitably used as a liquid crystal display (LCD), organic EL display (OLED), and plasma display (PDP) Such as flat panel display (FPD) optical film. [Example]
以下根據實施例更具體地說明本發明。Hereinafter, the present invention will be explained more specifically based on examples.
[實施例1] 將季戊四醇四丙烯酸酯(以下簡稱為「PETTA」)與季戊四醇三丙烯酸酯(以下簡稱為「PETA」)之等量混合物40質量份、胺基甲酸酯丙烯酸酯(1)(二季戊四醇五丙烯酸酯與異佛爾酮二異氰酸酯之反應物、固體成分100質量%、以下簡稱為「UA(1)」)20質量份、胺基甲酸酯丙烯酸酯(2)(聚四乙二醇與異佛爾酮二異氰酸酯及丙烯酸2-羥乙酯之反應物、數量平均分子量；1,600、固體成分100質量%、以下簡稱為「UA(2)」)、環氧丙烯酸酯(1)(聚甲基丙烯酸環氧丙酯與丙烯酸之反應物的甲基異丁基酮溶液、固體成分50質量%、黏度1,000mPa・s、以下簡稱為「EA(1)」)40質量份、乙醇144質量份、及1-羥基環己基苯酮5質量份充分混合後，混合帶電防止劑(B)(式(1)中，X表示磷原子，R1 ～R3 表示碳原子數6的烷基，R4 表示碳原子數14的烷基，碳原子數之合計為32者，陰離子部為(CF3 SO2 )2 N- 。)3質量份、及有機珠粒(積水化成品工業股份有限公司製的交聯丙烯酸微粒、粒徑1.5μm、折射率1.495)3.5質量份，且將混合物以分散攪拌機攪拌30分鐘，藉以調製活性能量線硬化性組成物。[Example 1] 40 parts by mass of an equivalent mixture of pentaerythritol tetraacrylate (hereinafter referred to as "PETTA") and pentaerythritol triacrylate (hereinafter referred to as "PETA"), urethane acrylate (1) ( The reactant of dipentaerythritol pentaacrylate and isophorone diisocyanate, solid content 100% by mass, hereinafter referred to as "UA(1)") 20 parts by mass, urethane acrylate (2) (polytetraethylene The reaction product of diol, isophorone diisocyanate and 2-hydroxyethyl acrylate, number average molecular weight; 1,600, solid content 100% by mass, hereinafter referred to as "UA(2)"), epoxy acrylate (1) (Methyl isobutyl ketone solution of the reactant of polyglycidyl methacrylate and acrylic acid, solid content 50% by mass, viscosity 1,000mPa·s, hereinafter referred to as "EA(1)") 40 parts by mass, ethanol After 144 parts by mass and 5 parts by mass of 1-hydroxycyclohexylphenone are thoroughly mixed, the antistatic agent (B) is mixed (in formula (1), X represents a phosphorus atom, and R 1 to R 3 represent an alkane with 6 carbon atoms. group, R 4 represents an alkyl carbon atoms, the total number of carbon atoms of 14 to 32 persons, the anion portion of (CF 3 SO 2) 2 N -.) 3 parts by mass, and organic beads (SEKISUI shares The crosslinked acrylic particles manufactured by Co., Ltd. have a particle size of 1.5 μm and a refractive index of 1.495) 3.5 parts by mass, and the mixture is stirred with a dispersion mixer for 30 minutes to prepare an active energy ray curable composition.
[實施例2～16、比較例1～6] 將使用之活性能量線硬化性化合物(A)及帶電防止劑(B)的種類與使用量如表1～4所示而變更，除此以外係與實施例1同樣進行，調製活性能量線硬化性組成物。[Examples 2 to 16, Comparative Examples 1 to 6] The types and amounts of active energy ray curable compound (A) and antistatic agent (B) used were changed as shown in Tables 1 to 4, except that the same procedure as in Example 1 was carried out to prepare active energy ray hardening Sexual composition.
[評價用樣本之製作] 將實施例及比較例所得之活性能量線硬化性組成物，在厚度60μm之聚甲基丙烯酸甲酯薄膜上，使用棒塗機進行塗布成為膜厚5μm，於60℃乾燥1分鐘後，在氮氣環境下使用紫外線照射裝置(EYE GRAPHICS股份有限公司製、高壓汞燈)，以照射光量75mJ/m2 照射2次，得到具有硬化塗膜的聚甲基丙烯酸甲酯薄膜作為評價用樣本。[Preparation of evaluation sample] The active energy ray curable composition obtained in the examples and comparative examples was applied to a polymethyl methacrylate film with a thickness of 60 μm using a bar coater to have a film thickness of 5 μm at 60°C After drying for 1 minute, use an ultraviolet irradiation device (manufactured by EYE GRAPHICS Co., Ltd., a high-pressure mercury lamp) in a nitrogen atmosphere, and irradiate twice with an irradiation light amount of 75 mJ/m 2 to obtain a polymethyl methacrylate film with a cured coating film As a sample for evaluation.
[防眩性之評價方法] (1)霧度之評價 將得到的評價用樣本，依據JISK7136：2000，使用霧度計(日本電飾股份有限公司製「NDH4000」)測定霧度。 (2)穿透鮮明度之評價 將得到的評價用樣本，依據JISK7374：2007，使用清晰度測定器(Suga Test Instruments股份有限公司製「ICM-IT」)，在光梳寬：0.125、0.5、1.0、2.0mm之4點進行測定。評價係使用測定的4點之合計值。 根據以上，霧度為4以下、穿透鮮明度為375%以下者，判斷為防眩性優異。[Evaluation method of anti-glare property] (1) Evaluation of haze The obtained sample for evaluation was measured for haze using a haze meter ("NDH4000" manufactured by Nippon Denshi Co., Ltd.) in accordance with JISK7136:2000. (2) Evaluation of the sharpness of penetration The obtained evaluation sample was measured at 4 points of comb width: 0.125, 0.5, 1.0, 2.0 mm using a sharpness measuring device ("ICM-IT" manufactured by Suga Test Instruments Co., Ltd.) in accordance with JISK7374: 2007 . The evaluation uses the total value of 4 points measured. From the above, it is judged that the haze is 4 or less and the penetration sharpness is 375% or less, which is judged to be excellent in antiglare properties.
[帶電防止性之評價方法] 針對得到的評價用樣本之硬化塗膜的表面，依據JIS試驗方法C2139：2008，使用高電阻率計(Mitsubishi Chemical Analytech股份有限公司製「高阻抗率計UP MCP-HT450」)，以施加電壓：500V、測定時間：10秒鐘，測定表面電阻值。將表面電阻值(Ω/□)為10-13 台以下者判斷為帶電防止性優異。[Evaluation method of anti-static property] For the surface of the cured coating film of the obtained evaluation sample, a high resistivity meter (Mitsubishi Chemical Analytech Co., Ltd. "High resistivity meter UP MCP-" was used in accordance with JIS test method C2139: 2008 HT450”), the surface resistance value is measured with the applied voltage: 500V and the measurement time: 10 seconds. A surface resistance value (Ω/□) of 10-13 units or less was judged to be excellent in antistatic property.
[表1]
[表2]
[表3]
[表4]
表4中之縮寫為以下者 ・「吡啶系帶電防止劑」：東京化成工業股份有限公司製「1-丁基-4-甲基吡啶鎓雙(三氟甲烷磺醯基)醯亞胺」 ・「咪唑系帶電防止劑」：東京化成工業股份有限公司製「1-乙基-3-甲基咪唑鎓雙(三氟甲烷磺醯基)醯亞胺」The abbreviations in Table 4 are as follows ・"Pyridine series antistatic agent": "1-Butyl-4-methylpyridinium bis(trifluoromethanesulfonyl)imidine" manufactured by Tokyo Chemical Industry Co., Ltd. ・"Imidazole-based antistatic agent": "1-Ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide" manufactured by Tokyo Chemical Industry Co., Ltd.
由表1～4所示的評價結果，可知：實施例1～16之本發明的活性能量線硬化性組成物之硬化塗膜具有優異的帶電防止性及防眩性。又，越增加帶電防止劑(B)，穿透鮮明度越降低，並得到防眩性，且帶電防止性也提升。From the evaluation results shown in Tables 1 to 4, it can be seen that the cured coating film of the active energy ray curable composition of the present invention of Examples 1 to 16 has excellent anti-static properties and anti-glare properties. In addition, the more the anti-static agent (B) is added, the sharper the penetration decreases, the anti-glare property is obtained, and the anti-static property is also improved.
表4所示的比較例1～2為未含有帶電防止劑(B)的態樣，且穿透鮮明度上升，帶電防止性也不良。比較例3～5為使用其它帶電防止劑代替本案所使用之帶電防止劑(B)的態樣，但帶電防止性為不良。Comparative Examples 1 to 2 shown in Table 4 are aspects that do not contain the antistatic agent (B), and the penetration sharpness is increased, and antistatic properties are also poor. Comparative Examples 3 to 5 are aspects in which other anti-static agents are used instead of the anti-static agents (B) used in this case, but the anti-static properties are poor.
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| JP3963447B2 (en) | 2002-10-03 | 2007-08-22 | 竹本油脂株式会社 | Antistatic agent for polyester film and antistatic method for polyester film |
| JP4229228B2 (en) | 2002-10-25 | 2009-02-25 | 日本合成化学工業株式会社 | Urethane (meth) acrylate compound and active energy ray-curable resin composition using the same |
| JP5206294B2 (en) * | 2008-10-02 | 2013-06-12 | 大日本印刷株式会社 | Method for producing hard coat film and method for producing optical functional member |
| JP5549279B2 (en) * | 2010-03-05 | 2014-07-16 | 東洋インキＳｃホールディングス株式会社 | Antistatic agent and its use |
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