TWI692518B - Hardened adhesive for polarizing film, polarizing film, optical film and image display device - Google Patents
Hardened adhesive for polarizing film, polarizing film, optical film and image display device Download PDFInfo
- Publication number
- TWI692518B TWI692518B TW103130064A TW103130064A TWI692518B TW I692518 B TWI692518 B TW I692518B TW 103130064 A TW103130064 A TW 103130064A TW 103130064 A TW103130064 A TW 103130064A TW I692518 B TWI692518 B TW I692518B
- Authority
- TW
- Taiwan
- Prior art keywords
- adhesive
- meth
- hardening
- polarizing film
- film
- Prior art date
Links
- 0 CC(*)C1(C)C(C2)C=CCC2C(C)C1 Chemical compound CC(*)C1(C)C(C2)C=CCC2C(C)C1 0.000 description 6
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
-
- 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
-
- 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
- C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/24—Homopolymers or copolymers of amides or imides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/24—Homopolymers or copolymers of amides or imides
- C09J133/26—Homopolymers or copolymers of acrylamide or methacrylamide
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J201/00—Adhesives based on unspecified macromolecular compounds
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
- G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
- G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
-
- 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
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Polarising Elements (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
- Liquid Crystal (AREA)
Abstract
本發明之含有硬化性成分之偏光薄膜用硬化型接著劑在將該偏光薄膜用硬化型接著劑之硬化物浸漬於23℃之純水中24小時的情況下,以下述式表示之整體吸水率為10重量%以下,即:整體吸水率(%)=式:{(M2-M1)/M1}×100(%) The curable adhesive for polarizing film containing a curable component of the present invention, when the cured product of the polarizing film curable adhesive is immersed in pure water at 23° C. for 24 hours, the overall water absorption rate is expressed by the following formula 10% by weight or less, namely: overall water absorption rate (%) = formula: {(M2-M1)/M1}×100(%)
{惟,前述式中,M1表示浸漬前之硬化物重量,M2表示浸漬後之硬化物重量}。該偏光薄膜用硬化型接著劑在偏光件與透明保護薄膜之接著性上甚是良好,且可滿足高溫高濕下之嚴苛環境下的光學耐久性,同時即使是長時間浸漬於水中時,亦具有充分之接著力。 {However, in the above formula, M1 represents the weight of the hardened material before dipping, and M2 represents the weight of the hardened material after dipping}. The hardening adhesive for polarizing film is very good in the adhesion between the polarizer and the transparent protective film, and can meet the optical durability under the harsh environment of high temperature and high humidity, and even when immersed in water for a long time, It also has sufficient adhesion.
Description
本發明是有關於一種偏光薄膜用硬化型接著劑,其係用以於隔著接著劑層積層有偏光件與透明保護薄膜之偏光薄膜中形成前述接著劑層者。又,本發明並有關於一種使用前述接著劑層之偏光薄膜。該偏光薄膜可以其單獨或作成積層有該偏光薄膜之光學薄膜來形成液晶顯示裝置(LCD)、有機EL顯示裝置、CRT、PDP等影像顯示裝置。 The present invention relates to a hardening adhesive for polarizing films, which is used to form the adhesive layer in a polarizing film in which a polarizer and a transparent protective film are laminated via an adhesive layer. In addition, the present invention relates to a polarizing film using the adhesive layer. The polarizing film can be used alone or as an optical film laminated with the polarizing film to form an image display device such as a liquid crystal display device (LCD), an organic EL display device, a CRT, and a PDP.
於鐘錶、行動電話、PDA、筆記型個人電腦、個人電腦用監視器、DVD播放機、TV等中,液晶顯示裝置急速地在市場上擴展。液晶顯示裝置是將利用液晶之切換之偏光狀態視覺化,並根據其顯示原理使用偏光件。特別是在TV等用途中,越發要求高亮度、高對比、廣視野角,且於偏光薄膜中,亦越發要求高透射率、高偏光度、高色彩再現性等。 In watches, mobile phones, PDAs, notebook personal computers, personal computer monitors, DVD players, TVs, etc., liquid crystal display devices are rapidly expanding in the market. The liquid crystal display device visualizes the polarization state using the switching of liquid crystal, and uses a polarizer according to its display principle. Especially in applications such as TV, high brightness, high contrast, and wide viewing angle are increasingly required, and in polarizing films, high transmittance, high polarization, and high color reproducibility are also required.
由於具有高透射率、高偏光度,因此,舉例言之,使碘吸附於聚乙烯醇(以下,亦僅稱作「PVA」)並延伸之結 構之碘系偏光件一般最廣為使用作為偏光件。一般而言,偏光薄膜是使用以下偏光薄膜,即:藉由將聚乙烯醇系之材料溶解於水中之所謂水系接著劑,將透明保護薄膜黏合於偏光件之兩面(下述專利文獻1及專利文獻2)。透明保護薄膜是使用透濕度高之三乙醯纖維素等。使用前述水系接著劑時(所謂濕式層合),在黏合偏光件與透明保護薄膜後,必須進行乾燥步驟。 Due to its high transmittance and high degree of polarization, for example, iodine is adsorbed on polyvinyl alcohol (hereinafter, also simply referred to as "PVA") and extended. Iodine-based polarizers are generally the most widely used as polarizers. In general, the polarizing film uses the following polarizing film, that is, a transparent protective film is bonded to both sides of the polarizer by a so-called water-based adhesive dissolving a polyvinyl alcohol-based material in water (Patent Document 1 and Patent below Literature 2). The transparent protective film is made of triacetyl cellulose with high moisture permeability. When using the aforementioned water-based adhesive (so-called wet lamination), after the polarizer and the transparent protective film are bonded, a drying step must be performed.
另一方面,目前揭示有活性能量線硬化型接著 劑,以取代前述水系接著劑。使用活性能量線硬化型接著劑而製造偏光薄膜時,由於毋須進行乾燥步驟,因此,可提升偏光薄膜之生產性。舉例言之,目前揭示有使用N-取代醯胺系單體作為硬化性成分之自由基聚合型活性能量線硬化型接著劑(下述專利文獻3及專利文獻4)。前述接著劑於高濕度下及高溫下之嚴苛環境下可發揮優異之耐久性,然而,實情是市場上仍要求可提升更進一步之接著性及/或耐水性之接著劑。 On the other hand, it is currently revealed that there is an active energy ray hardening type Agent to replace the aforementioned water-based adhesive. When a polarizing film is manufactured using an active energy ray-curable adhesive, since a drying step is not necessary, the productivity of the polarizing film can be improved. For example, there is currently disclosed a radical polymerization type active energy ray-curable adhesive using N-substituted amide-based monomer as a curable component (Patent Document 3 and Patent Document 4 below). The aforementioned adhesive agent can exhibit excellent durability under severe environments under high humidity and high temperature, however, the fact is that an adhesive agent that can improve further adhesiveness and/or water resistance is still required on the market.
又,著眼於硬化性成分之SP值(溶解度參數),目 前揭示有一種活性能量線硬化型接著劑,其藉由預定之組成比率使用至少3種SP值不同之自由基聚合性化合物,藉此,可形成提升耐久性及耐水性之接著劑層(下述專利文獻5)。 Also, focusing on the SP value (solubility parameter) of the hardening component, the It was previously disclosed that there is an active energy ray hardening type adhesive, which uses at least three kinds of radically polymerizable compounds with different SP values by a predetermined composition ratio, whereby an adhesive layer with improved durability and water resistance can be formed (below Refer to Patent Document 5).
專利文獻1:日本專利特開2006-220732號公報 Patent Document 1: Japanese Patent Laid-Open No. 2006-220732
專利文獻2:日本專利特開2001-296427號公報 Patent Document 2: Japanese Patent Laid-Open No. 2001-296427
專利文獻3:日本專利特開2008-287207號公報 Patent Document 3: Japanese Patent Laid-Open No. 2008-287207
專利文獻4:日本專利特開2010-078700號公報 Patent Document 4: Japanese Patent Laid-Open No. 2010-078700
專利文獻5:日本專利特開2012-144690號公報 Patent Literature 5: Japanese Patent Laid-Open No. 2012-144690
若藉由前述專利文獻5所揭示之活性能量線硬化型接著劑,則可對偏光薄膜之製造時使用的各種透明保護薄膜滿足耐久性及耐水性。然而,使用專利文獻5所揭示之活性能量線硬化型接著劑而製得之偏光薄膜雖然可滿足浸漬於60℃之溫水中6小時下的耐水性(溫水浸漬試驗),然而,市場上卻要求更進一步之高溫高濕下之嚴苛環境下的光學耐久性。再者,前述偏光薄膜會要求即使是長時間浸漬於水中時,亦具有充分之接著力。 The active energy ray-curable adhesive disclosed in the aforementioned Patent Document 5 can satisfy the durability and water resistance of various transparent protective films used in the manufacture of polarizing films. However, although the polarized film prepared using the active energy ray-curable adhesive disclosed in Patent Document 5 can satisfy the water resistance (warm water immersion test) immersed in 60°C warm water for 6 hours, however, It requires further optical durability under severe environments under high temperature and high humidity. Furthermore, the polarizing film requires sufficient adhesion even when immersed in water for a long time.
本發明之目的在提供一種偏光薄膜用硬化型接著劑,其於偏光件與透明保護薄膜之接著性上甚是良好,且可滿足高溫高濕下之嚴苛環境下的光學耐久性,同時即使是長時間浸漬於水中時,亦具有充分之接著力。 The object of the present invention is to provide a hardening adhesive for polarizing film, which is very good in the adhesion between the polarizer and the transparent protective film, and can meet the optical durability under the harsh environment of high temperature and high humidity, while It has sufficient adhesion when immersed in water for a long time.
又,本發明之目的在提供一種偏光薄膜,其係藉由使用偏光薄膜用硬化型接著劑所形成的接著劑層,於偏光件設置透明保護薄膜者,再者,提供一種使用有前述偏光薄膜之光學薄膜,更提供一種使用有前述偏光薄膜或光學薄膜之影像顯示裝置。 In addition, an object of the present invention is to provide a polarizing film which is formed by using an adhesive layer formed of a hardening adhesive for polarizing film, a transparent protective film is provided on a polarizer, and further, a polarizing film is used The optical film further provides an image display device using the aforementioned polarizing film or optical film.
發明人等為了解決上述課題反覆鑽研之結果,發現藉由下述偏光薄膜用硬化型接著劑可達成前述目的,以致解決本發明。 In order to solve the above-mentioned problems, the inventors have repeatedly studied and found that the above-mentioned object can be achieved by the following hardening adhesive for polarizing film, so as to solve the present invention.
即,本發明係有關於一種偏光薄膜用硬化型接著劑,其含有硬化性成分,且該偏光薄膜用硬化型接著劑在將使該硬化型接著劑硬化而得之硬化物浸漬於23℃之純水中24小時的情況下,以下述式表示之整體吸水率為10重量%以下,即:整體吸水率(%)={(M2-M1)/M1}×100 That is, the present invention relates to a hardening adhesive for polarizing films, which contains a curable component, and the hardening adhesive for polarizing films is immersed in a cured product obtained by hardening the hardening adhesive at 23°C. In the case of pure water for 24 hours, the overall water absorption rate expressed by the following formula is 10% by weight or less, that is, the overall water absorption rate (%)={(M2-M1)/M1}×100
{惟,前述式中,M1表示浸漬前之硬化物重量,M2表示浸漬後之硬化物重量}。 {However, in the above formula, M1 represents the weight of the hardened material before dipping, and M2 represents the weight of the hardened material after dipping}.
前述偏光薄膜用硬化型接著劑之辛醇/水分配係數(logPow值)宜為1以上。 The octanol/water partition coefficient (logPow value) of the hardening adhesive for polarizing film is preferably 1 or more.
前述偏光薄膜用硬化型接著劑在前述硬化性成分為活性能量線硬化性成分時,可作成活性能量線硬化型接著劑來使用。前述硬化性成分可含有自由基聚合性化合物。前述自由基聚合性化合物宜含有(甲基)丙烯醯胺衍生物。又,前述自由基聚合性化合物宜含有多官能性化合物,且該多官能性化合物具有至少2個具自由基聚合性之官能基。又,前述活性能量線硬化型接著劑更可含有光聚合引發劑。 The curable adhesive for polarizing film can be used as an active energy ray-curable adhesive when the curable component is an active energy ray-curable component. The curable component may contain a radical polymerizable compound. The aforementioned radical polymerizable compound preferably contains a (meth)acrylamide derivative. Furthermore, the radical polymerizable compound preferably contains a polyfunctional compound, and the polyfunctional compound has at least two radically polymerizable functional groups. Furthermore, the active energy ray-curable adhesive may further contain a photopolymerization initiator.
前述偏光薄膜用硬化型接著劑更可含有丙烯酸系低聚物(A)。 The hardening adhesive for polarizing film may further contain an acrylic oligomer (A).
前述偏光薄膜用硬化型接著劑更可含有光酸產生劑(B)。 The hardening type adhesive for polarizing films may further contain a photoacid generator (B).
前述偏光薄膜用硬化型接著劑更可含有包含烷氧基、環氧基中任一者之化合物(C)。前述包含烷氧基、環氧基中任一者之化合物(C)宜為包含烷氧基之化合物(C1)。再者,前述包含烷氧基之化合物(C1)宜為包含烷氧基之三聚氰胺化合物。 The hardening-type adhesive for polarizing films may further contain a compound (C) containing any of alkoxy groups and epoxy groups. The compound (C) containing any of the aforementioned alkoxy and epoxy groups is preferably an alkoxy-containing compound (C1). Furthermore, the aforementioned alkoxy-containing compound (C1) is preferably an alkoxy-containing melamine compound.
又,前述偏光薄膜用硬化型接著劑更可含有異氰酸酯化合物(D)。 In addition, the hardening adhesive for polarizing film may further contain an isocyanate compound (D).
前述偏光薄膜用硬化型接著劑在前述硬化性成分為熱硬化性成分時更含有熱聚合引發劑,藉此,可作成熱硬化型接著劑來使用。 The hardening type adhesive for polarizing film further contains a thermal polymerization initiator when the hardening component is a thermosetting component, and thus can be used as a thermosetting adhesive.
又,本發明是有關於一種偏光薄膜,係於偏光件之至少其中一面隔著接著劑層設有透明保護薄膜者,且前述接著劑層是藉由前述偏光薄膜用硬化型接著劑之硬化物層形成。 In addition, the present invention relates to a polarizing film in which at least one side of a polarizer is provided with a transparent protective film via an adhesive layer, and the adhesive layer is a cured product of the hardening adhesive for polarizing film Layer formation.
於前述偏光薄膜中,前述接著劑硬化物層之厚度宜為0.1~3μm。 In the polarizing film, the thickness of the adhesive hardened layer is preferably 0.1 to 3 μm.
再者,本發明是有關於一種光學薄膜,其積層至少一片前述偏光薄膜。 Furthermore, the present invention relates to an optical film in which at least one polarizing film is laminated.
再者,本發明是有關於一種影像顯示裝置,其使用有前述偏光薄膜或前述光學薄膜。 Furthermore, the present invention relates to an image display device using the polarizing film or the optical film.
本發明之偏光薄膜用硬化型接著劑之使該硬化 型接著劑硬化而得之硬化物的整體吸水率為10重量%以下。該整體吸水率顯示出藉由自本發明之偏光薄膜用硬化型接著劑所得之硬化物層形成接著劑層時的吸水性非常低。故,於偏光件上隔著前述硬化物層所構成的接著劑層設有透明保護薄膜之偏光薄膜,其於偏光件與透明保護薄膜層之接著性上甚是良好,且可滿足高溫高濕下之嚴苛環境下的光學耐久性。 The hardening type adhesive for polarizing film of the present invention makes the hardening The overall water absorption of the cured product obtained by curing the type adhesive is 10% by weight or less. This overall water absorption rate shows that the water absorption when the adhesive layer is formed from the hardened layer obtained from the hardening adhesive for polarizing film of the present invention is very low. Therefore, a polarizing film provided with a transparent protective film on the polarizer through the adhesive layer formed by the hardened layer is very good in adhesion between the polarizer and the transparent protective film layer, and can meet high temperature and high humidity The optical durability under the harsh environment.
舉例言之,具有使用本發明之偏光薄膜用硬化型接著劑所形成的硬化物層(接著劑層)的偏光薄膜即使於嚴苛之加濕環境下(85℃×85%RH),光學耐久性(加濕耐久性試驗)亦良好。故,本發明之偏光薄膜即使於放置在前述嚴苛之加濕環境下時,亦可壓低偏光薄膜之透射率、偏光度之降低(變化)。又,本發明之偏光薄膜即使於像是浸漬於水中之嚴苛環境下,亦可抑制接著力之降低,且可提供即使是長時間浸漬於水中時亦具有充分接著力之偏光薄膜。 For example, a polarizing film having a hardened layer (adhesive layer) formed using the hardening type adhesive for polarizing film of the present invention is optically durable even under severe humidified environment (85°C×85%RH) The performance (humidification durability test) is also good. Therefore, even when the polarizing film of the present invention is placed under the severe humidification environment described above, it can suppress the decrease (change) in the transmittance and polarization degree of the polarizing film. In addition, the polarizing film of the present invention can suppress the decrease in adhesion even under severe environments such as being immersed in water, and can provide a polarizing film having sufficient adhesion even when immersed in water for a long time.
<整體吸水率> <overall water absorption rate>
本發明之偏光薄膜用硬化型接著劑在將使該硬化型接著劑硬化而得之硬化物浸漬於23℃之純水中24小時下所測定的前述揭示之整體吸水率為10重量%以下。將偏光薄膜放置於嚴苛之高溫高濕(85℃/85%RH等)環境下時,業已透 過透明保護薄膜與接著劑層之水分會朝偏光件滲入,且交聯結構水解,藉此,二色性色素之定向紊亂,並引起透射率上升、偏光度降低等光學耐久性之惡化。藉由將接著劑層之整體吸水率作成10重量%以下,可抑制將偏光薄膜放置於嚴苛之高溫高濕環境下時水朝偏光件之移動,且可抑制偏光件之透射率上升、偏光度降低。針對偏光薄膜之接著劑層,若由將高溫下之嚴苛環境下的光學耐久性作成更加良好之觀點來看,則前述整體吸水率宜為5重量%以下,且更宜為3重量%以下,進而宜為1.5重量%以下,最為理想的是1重量%以下。另一方面,黏合偏光件與透明保護薄膜時,偏光件會保持一定量之水分,且該硬化型接著劑與包含於偏光件之水分接觸時,會有產生塌凹、氣泡等外觀不良之情形。為了抑制外觀不良,該硬化型接著劑宜可吸收一定量之水分。更具體而言,整體吸水率宜為0.01重量%以上,且更宜為0.05重量%以上。具體而言,前述整體吸水率是藉由JIS K 7209所揭示之吸水率試驗方法來測定。 The hardening-type adhesive for polarizing films of the present invention has an overall water absorption of 10% by weight or less as measured by immersing the hardened product obtained by hardening the hardening-type adhesive in pure water at 23° C. for 24 hours. When the polarizing film is placed in the harsh environment of high temperature and high humidity (85℃/85%RH, etc.), it has been transparent The moisture of the over-transparent protective film and the adhesive layer penetrates into the polarizer, and the cross-linked structure is hydrolyzed, whereby the orientation of the dichroic pigment is disordered, and the optical durability such as increased transmittance and decreased polarization degree is deteriorated. By setting the overall water absorption of the adhesive layer to 10% by weight or less, the movement of water toward the polarizer can be suppressed when the polarizing film is placed in a severe high temperature and high humidity environment, and the transmittance of the polarizer can be suppressed from rising and polarizing Degrees decrease. For the adhesive layer of the polarizing film, from the viewpoint of making the optical durability in a severe environment under high temperature more favorable, the overall water absorption rate is preferably 5% by weight or less, and more preferably 3% by weight or less Furthermore, it is preferably 1.5% by weight or less, and most preferably 1% by weight or less. On the other hand, when the polarizer and the transparent protective film are bonded, the polarizer will maintain a certain amount of moisture, and when the hardening adhesive contacts the moisture contained in the polarizer, it may cause appearance defects such as collapse and bubbles. . In order to suppress poor appearance, the hardening type adhesive should preferably absorb a certain amount of moisture. More specifically, the overall water absorption rate is preferably 0.01% by weight or more, and more preferably 0.05% by weight or more. Specifically, the aforementioned overall water absorption rate is measured by the water absorption rate test method disclosed in JIS K 7209.
本發明之偏光薄膜用硬化型接著劑宜為辛醇/水 分配係數(以下稱作logPow值)高。所謂logPow值是表示物質之親油性之指標,並意味著辛醇/水之分配係數之對數值。logPow高是意味著屬於親油性,即,意味著吸水率低。 logPow值可進行測定(JIS-Z-7260所揭示之燒瓶震盪法),然而,亦可根據屬於偏光薄膜用硬化型接著劑之構成成分(硬化性成分等)的各化合物之結構,藉由計算來算出。於本說明書中,使用藉由劍橋軟體(CambridgeSoft)公司製Chem Draw Ultra所計算之logPow值。 The hardening adhesive for polarizing film of the present invention is preferably octanol/water The partition coefficient (hereinafter referred to as logPow value) is high. The so-called logPow value is an index indicating the lipophilicity of the substance, and means the logarithmic value of the partition coefficient of octanol/water. A high logPow means it is lipophilic, that is, it means low water absorption. The logPow value can be measured (the flask shaking method disclosed in JIS-Z-7260), however, it can also be calculated by calculation according to the structure of each compound that is a constituent component (hardening component, etc.) of the hardening adhesive for polarizing film To figure it out. In this manual, Chem manufactured by CambridgeSoft is used The logPow value calculated by Draw Ultra.
根據前述計算值,本發明中的偏光薄膜用硬化型接著劑之logPow值可藉由下述式來計算。 Based on the aforementioned calculation value, the logPow value of the hardening type adhesive for polarizing film in the present invention can be calculated by the following formula.
硬化型接著劑之logPow=Σ(logPowi×Wi) LogPow=Σ(logPowi×Wi) of hardening adhesive
logPowi:硬化型接著劑之各成分之logPow值 logPowi: the logPow value of each component of the hardening adhesive
Wi:(i成分之莫耳數)/(硬化型接著劑之各成分之總莫耳數) Wi: (mole number of component i)/(total moles of each component of hardening adhesive)
在前述計算時,於硬化型接著劑之各成分中,聚合引發劑或光酸產生劑等不會形成硬化物(接著劑層)之骨架之成分會自前述計算中之成分扣除。本發明之偏光薄膜用硬化型接著劑之logPow值宜為1以上,且更宜為1.5以上,最宜為2以上。藉此,可提高接著耐水性或加濕耐久性。另一方面,本發明之偏光薄膜用硬化型接著劑之logPow值通常為8以下,且宜為5以下,更宜為4以下。若該logPow值過高,則如前述,由於容易產生塌凹或氣泡等外觀不良,因此較不理想。 In the foregoing calculation, among the components of the hardening adhesive, components such as a polymerization initiator or a photoacid generator that do not form a skeleton of the cured product (adhesive layer) are deducted from the components in the foregoing calculation. The logPow value of the hardening adhesive for polarizing film of the present invention is preferably 1 or more, more preferably 1.5 or more, and most preferably 2 or more. With this, the subsequent water resistance or humidification durability can be improved. On the other hand, the logPow value of the hardening adhesive for polarizing film of the present invention is usually 8 or less, and preferably 5 or less, and more preferably 4 or less. If the logPow value is too high, as described above, since appearance such as collapse or bubbles is likely to occur, it is less desirable.
又,將本發明中的前述整體吸水率作成10重量%以下之方法並無特殊之限制,然而,當偏光薄膜用硬化型接著劑是含有複數種成分之組成物時,藉由選擇各成分,可將整體吸水率控制在前述範圍。舉例言之,當偏光薄膜用硬化型接著劑是含有複數種成分之接著劑組成物時,藉由調製成減少該接著劑組成物中logPow值構成1以下之成分之比例等方法,可將整體吸水率控制在前述範圍。欲將本發明中的前述整體吸水率調整為10重量%以下時,舉例 言之,可藉由將偏光薄膜用硬化型接著劑之logPow值控制為1以上來進行。 In addition, there is no particular limitation on the method of making the overall water absorption rate of 10% by weight or less in the present invention. However, when the hardening adhesive for polarizing film is a composition containing a plurality of components, by selecting each component, The overall water absorption rate can be controlled within the aforementioned range. For example, when the hardening adhesive for polarizing film is an adhesive composition containing a plurality of components, by adjusting to reduce the ratio of components with a logPow value of 1 or less in the adhesive composition, the whole The water absorption rate is controlled within the aforementioned range. To adjust the overall water absorption in the present invention to 10% by weight or less, for example In other words, it can be performed by controlling the logPow value of the hardening adhesive for polarizing film to 1 or more.
<硬化收縮率> <hardening shrinkage>
又,由於本發明之偏光薄膜用硬化型接著劑具有硬化性成分,因此,使該硬化型接著劑硬化時,通常會產生硬化收縮。硬化收縮率是顯示自偏光薄膜用硬化型接著劑形成接著劑層時的硬化收縮比例之指標。若接著劑層之硬化收縮率增大,則在使偏光薄膜用硬化型接著劑硬化而形成接著劑層時會產生界面應變,在抑制產生接著不良上較為理想。若由前述觀點來看,則有關使本發明之偏光薄膜用硬化型接著劑硬化而得之硬化物之前述硬化收縮率宜為10%以下。較為理想的是前述硬化收縮率小,且前述硬化收縮率宜為8%以下,更宜為5%以下。前述硬化收縮率是藉由特開2013-104869號所揭示之方法來測定,具體而言,藉由實施例所揭示利用聖鐵克(SENTEC)公司製硬化收縮感測器之方法來測定。 In addition, since the curable adhesive for polarizing film of the present invention has a curable component, when the curable adhesive is cured, curing shrinkage usually occurs. The curing shrinkage rate is an index showing the curing shrinkage ratio when the adhesive layer is formed from the hardening adhesive for polarizing film. If the curing shrinkage of the adhesive layer increases, interface strain will occur when the adhesive layer is formed by hardening the polarizing film hardening adhesive, and it is desirable to suppress the occurrence of adhesive defects. From the aforementioned viewpoint, the curing shrinkage rate of the cured product obtained by curing the curing adhesive for polarizing film of the present invention is preferably 10% or less. Preferably, the hardening shrinkage rate is small, and the hardening shrinkage rate is preferably 8% or less, and more preferably 5% or less. The aforementioned hardening shrinkage rate is measured by the method disclosed in JP-A-2013-104869. Specifically, it is measured by a method using a hardening shrinkage sensor manufactured by SENTEC Corporation as disclosed in the examples.
<硬化性成分> <hardening ingredient>
本發明之偏光薄膜用硬化型接著劑含有硬化性成分。該硬化性成分可適當地選擇,使硬化物滿足前述整體吸水率。 The curable adhesive for polarizing film of the present invention contains a curable component. The curable component can be appropriately selected so that the cured product satisfies the aforementioned overall water absorption rate.
硬化性成分可大致區別為電子射線硬化型、紫外線硬化型、可見光線硬化型等活性能量線硬化型與熱硬化型。再者,紫外線硬化型、可見光線硬化型接著劑可區分為自由基聚合硬化型接著劑與陽離子聚合型接著劑。於本 發明中,將波長範圍10nm~小於380nm之活性能量線標示為紫外線,將波長範圍380nm~800nm之活性能量線標示為可見光線。前述自由基聚合硬化型接著劑之硬化性成分可作成熱硬化型接著劑之硬化性成分來使用。 Curable components can be roughly divided into active energy ray curing type and thermosetting type such as electron beam curing type, ultraviolet curing type and visible light curing type. Furthermore, ultraviolet curing type and visible light curing type adhesives can be divided into radical polymerization curing type adhesives and cationic polymerization type adhesives. Yu Ben In the invention, the active energy line with a wavelength range of 10 nm to less than 380 nm is marked as ultraviolet rays, and the active energy line with a wavelength range of 380 nm to 800 nm is marked as visible light. The curable component of the radical polymerization hardening type adhesive can be used as the curable component of the thermosetting type adhesive.
<1:自由基聚合硬化型接著劑> <1: Radical polymerization hardening type adhesive>
舉例言之,前述硬化性成分可列舉如:使用於自由基聚合硬化型接著劑之自由基聚合性化合物。自由基聚合性化合物可列舉如:具有(甲基)丙烯醯基、乙烯基等碳-碳雙鍵之自由基聚合性官能基之化合物。該等硬化性成分可使用單官能自由基聚合性化合物或雙官能以上之多官能自由基聚合性化合物中任一者。又,該等自由基聚合性化合物可單獨1種或組合2種以上來使用。舉例言之,該等自由基聚合性化合物適合為具有(甲基)丙烯醯基之化合物。另,於本發明中,所謂(甲基)丙烯醯基是意味著丙烯醯基及/或甲基丙烯醯基,且「(甲基)」是以下相同之意思。 For example, the aforementioned curable component can be exemplified by radical polymerizable compounds used in radical polymerization hardening type adhesives. Examples of the radically polymerizable compound include compounds having a radically polymerizable functional group having a carbon-carbon double bond such as (meth)acryloyl group and vinyl group. As these hardening components, any of a monofunctional radical polymerizable compound or a bifunctional or higher polyfunctional radical polymerizable compound can be used. Moreover, these radically polymerizable compounds can be used individually by 1 type or in combination of 2 or more types. For example, these radically polymerizable compounds are suitably compounds having a (meth)acryloyl group. In the present invention, the term "(meth)acryloyl" means propenyl and/or methacryl, and "(meth)" has the same meaning as below.
《單官能自由基聚合性化合物》 "Monofunctional Radical Polymerizable Compound"
舉例言之,單官能自由基聚合性化合物可列舉如:具有(甲基)丙烯醯胺基之(甲基)丙烯醯胺衍生物。在確保與偏光件或各種透明保護薄膜之接著性上,又,在聚合速度快且生產性優異方面,(甲基)丙烯醯胺衍生物是較為理想的。舉例言之,(甲基)丙烯醯胺衍生物之具體例可列舉如:N-甲基(甲基)丙烯醯胺、N,N-二甲基(甲基)丙烯醯胺、N,N-二乙基(甲基)丙烯醯胺、N-異丙基(甲基)丙烯醯胺、N-丁基(甲基)丙烯醯胺、N-己基(甲基)丙烯醯胺等含有N-烷基之 (甲基)丙烯醯胺衍生物;N-羥甲基(甲基)丙烯醯胺、N-羥乙基(甲基)丙烯醯胺、N-羥甲基-N-丙烷(甲基)丙烯醯胺等含有N-羥烷基之(甲基)丙烯醯胺衍生物;胺甲基(甲基)丙烯醯胺、胺乙基(甲基)丙烯醯胺等含有N-胺烷基之(甲基)丙烯醯胺衍生物;N-甲氧基甲基丙烯醯胺、N-乙氧基甲基丙烯醯胺等含有N-烷氧基之(甲基)丙烯醯胺衍生物;巰甲基(甲基)丙烯醯胺、巰乙基(甲基)丙烯醯胺等含有N-巰烷基之(甲基)丙烯醯胺衍生物等。又,舉例言之,(甲基)丙烯醯胺基之氮原子形成雜環之含有雜環之(甲基)丙烯醯胺衍生物可列舉如:N-丙烯醯基嗎啉、N-丙烯醯基哌啶、N-甲基丙烯醯基哌啶、N-丙烯醯基吡咯啶等。 For example, examples of the monofunctional radical polymerizable compound include (meth)acrylamide derivatives having a (meth)acrylamide group. The (meth)acrylamide derivative is preferable in terms of securing the adhesion to the polarizer or various transparent protective films, and in terms of fast polymerization speed and excellent productivity. For example, specific examples of (meth)acrylamide derivatives include N-methyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N -Diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N-butyl(meth)acrylamide, N-hexyl(meth)acrylamide, etc. contain N -Alkyl (Meth) acrylamide derivatives; N-hydroxymethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N-hydroxymethyl-N-propane (meth) acryl N-hydroxyalkyl-containing (meth)acrylamide derivatives such as amides; aminemethyl (meth)acrylamide, amine ethyl (meth)acrylamides containing N-aminoalkyl ( (Meth)acrylamide derivatives; N-methoxymethacrylamide, N-ethoxymethacrylamide and other (meth)acrylamide derivatives containing N-alkoxy; mercaptomethyl N-mercaptoalkyl-containing (meth)acrylamide derivatives and the like, such as (meth)acrylamide and mercaptoethyl (meth)acrylamide. In addition, for example, the heterocyclic ring-containing (meth)acrylamide derivatives in which the nitrogen atom of the (meth)acrylamide group forms a heterocyclic ring include N-propenyl morpholine, N-acryl amide Piperidine, N-methacryloyl piperidine, N-propenyl pyrrolidine, etc.
於前述(甲基)丙烯醯胺衍生物中,若由與偏光件 或各種透明保護薄膜之接著性之觀點來看,則亦宜為含有N-羥烷基之(甲基)丙烯醯胺衍生物,特別是宜為N-羥乙基(甲基)丙烯醯胺。 Among the aforementioned (meth)acrylamide derivatives, if the polarizer is used Or from the viewpoint of the adhesion of various transparent protective films, it is also preferably a (meth)acrylamide derivative containing N-hydroxyalkyl, especially N-hydroxyethyl (meth)acrylamide .
又,舉例言之,單官能自由基聚合性化合物可列舉如:具有(甲基)丙烯醯氧基之各種(甲基)丙烯酸衍生物。具體而言,舉例言之,可列舉如:甲基(甲基)丙烯酸酯、乙基(甲基)丙烯酸酯、n-丙基(甲基)丙烯酸酯、異丙基(甲基)丙烯酸酯、2-甲基-2-硝基丙基(甲基)丙烯酸酯、n-丁基(甲基)丙烯酸酯、異丁基(甲基)丙烯酸酯、s-丁基(甲基)丙烯酸酯、t-丁基(甲基)丙烯酸酯、n-戊基(甲基)丙烯酸酯、t-戊基(甲基)丙烯酸酯、3-戊基(甲基)丙烯酸酯、2,2-二甲基丁基(甲基)丙烯酸酯、n-己基(甲基)丙烯酸酯、十六基(甲基)丙烯酸 酯、n-辛基(甲基)丙烯酸酯、2-乙基己基(甲基)丙烯酸酯、4-甲基-2-丙基戊基(甲基)丙烯酸酯、n-十八基(甲基)丙烯酸酯等(甲基)丙烯酸(碳數1-20)烷基酯類。 In addition, for example, the monofunctional radical polymerizable compound may include various (meth)acrylic acid derivatives having (meth)acryloyloxy groups. Specifically, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate , 2-methyl-2-nitropropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, s-butyl (meth)acrylate , T-butyl (meth)acrylate, n-pentyl (meth)acrylate, t-pentyl (meth)acrylate, 3-pentyl (meth)acrylate, 2,2-di Methylbutyl (meth)acrylate, n-hexyl (meth)acrylate, hexadecyl (meth)acrylic acid Ester, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 4-methyl-2-propylpentyl (meth)acrylate, n-octadecyl (meth) (Meth)acrylic acid (C 1-20) alkyl esters such as acrylate.
又,舉例言之,前述(甲基)丙烯酸衍生物可列舉 如:環己基(甲基)丙烯酸酯、環戊基(甲基)丙烯酸酯等環烷基(甲基)丙烯酸酯;苄基(甲基)丙烯酸酯等芳烷基(甲基)丙烯酸酯;2-異莰基(甲基)丙烯酸酯、2-降莰基甲基(甲基)丙烯酸酯、5-降莰烯-2-基-甲基(甲基)丙烯酸酯、3-甲基-2-降莰基甲基(甲基)丙烯酸酯、二環戊烯基(甲基)丙烯酸酯、二環戊烯基氧基乙基(甲基)丙烯酸酯、二環戊烷基(甲基)丙烯酸酯等多環式(甲基)丙烯酸酯;2-甲氧基乙基(甲基)丙烯酸酯、2-乙氧基乙基(甲基)丙烯酸酯、2-甲氧基甲氧基乙基(甲基)丙烯酸酯、3-甲氧基丁基(甲基)丙烯酸酯、乙基卡必醇(甲基)丙烯酸酯、苯氧基乙基(甲基)丙烯酸酯、烷基苯氧基聚乙二醇(甲基)丙烯酸酯等含有烷氧基或苯氧基之(甲基)丙烯酸酯等。 Also, for example, the aforementioned (meth)acrylic acid derivative can be exemplified Such as: cyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate and other cycloalkyl (meth) acrylate; benzyl (meth) acrylate and other aralkyl (meth) acrylate; 2-isobornyl (meth)acrylate, 2-norbornyl methyl (meth)acrylate, 5-norbornen-2-yl-methyl (meth)acrylate, 3-methyl- 2-norbornyl methyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentyl (meth) ) Polycyclic (meth)acrylates such as acrylate; 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-methoxymethoxy Ethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, ethyl carbitol (meth)acrylate, phenoxyethyl (meth)acrylate, alkylbenzene Oxypolyethylene glycol (meth)acrylates and the like (meth)acrylates containing alkoxy or phenoxy groups.
又,前述(甲基)丙烯酸衍生物可列舉如:2-羥乙 基(甲基)丙烯酸酯、2-羥丙基(甲基)丙烯酸酯、3-羥丙基(甲基)丙烯酸酯、2-羥丁基(甲基)丙烯酸酯、4-羥丁基(甲基)丙烯酸酯、6-羥己基(甲基)丙烯酸酯、8-羥辛基(甲基)丙烯酸酯、10-羥癸基(甲基)丙烯酸酯、12-羥月桂基(甲基)丙烯酸酯等羥烷基(甲基)丙烯酸酯或[4-(羥甲基)環己基]甲基丙烯酸酯、環己烷二甲醇單(甲基)丙烯酸酯、2-羥基-3-苯氧基丙基(甲基)丙烯酸酯等含有羥基之(甲基)丙烯酸酯;環氧丙 基(甲基)丙烯酸酯、4-羥丁基(甲基)丙烯酸酯環氧丙基醚等含有環氧基之(甲基)丙烯酸酯;2,2,2-三氟乙基(甲基)丙烯酸酯、2,2,2-三氟乙基乙基(甲基)丙烯酸酯、四氟丙基(甲基)丙烯酸酯、六氟丙基(甲基)丙烯酸酯、八氟戊基(甲基)丙烯酸酯、十七氟癸基(甲基)丙烯酸酯、3-氯-2-羥丙基(甲基)丙烯酸酯等含有鹵素之(甲基)丙烯酸酯;二甲基胺基乙基(甲基)丙烯酸酯等烷基胺基烷基(甲基)丙烯酸酯;3-氧雜環丁烷基甲基(甲基)丙烯酸酯、3-甲基-氧雜環丁烷基甲基(甲基)丙烯酸酯、3-乙基-氧雜環丁烷基甲基(甲基)丙烯酸酯、3-丁基-氧雜環丁烷基甲基(甲基)丙烯酸酯、3-己基-氧雜環丁烷基甲基(甲基)丙烯酸酯等含有氧雜環丁烷基之(甲基)丙烯酸酯;四氫糠基(甲基)丙烯酸酯、丁內酯(甲基)丙烯酸酯等具有雜環之(甲基)丙烯酸酯或羥基三甲基乙酸新戊二醇(甲基)丙烯酸加成物、p-苯基苯酚(甲基)丙烯酸酯等。 In addition, the (meth)acrylic acid derivatives include, for example, 2-hydroxyethyl (Meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl ( Methacrylates, 6-hydroxyhexyl (meth)acrylates, 8-hydroxyoctyl (meth)acrylates, 10-hydroxydecyl (meth)acrylates, 12-hydroxylauryl (meth) Hydroxyalkyl (meth)acrylates such as acrylates or [4-(hydroxymethyl)cyclohexyl]methacrylate, cyclohexanedimethanol mono (meth)acrylate, 2-hydroxy-3-phenoxy Hydroxy-containing (meth)acrylates such as propyl (meth)acrylate; glycidyl oxide (Meth)acrylates containing epoxy groups such as (meth)acrylate, 4-hydroxybutyl (meth)acrylate epoxypropyl ether; 2,2,2-trifluoroethyl (methyl ) Acrylate, 2,2,2-trifluoroethylethyl (meth)acrylate, tetrafluoropropyl (meth)acrylate, hexafluoropropyl (meth)acrylate, octafluoropentyl ( (Meth) acrylate, heptafluorodecyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate and other halogen-containing (meth) acrylate; dimethylamino ethyl Alkyl (meth) acrylate and other alkylamino alkyl (meth) acrylate; 3-oxetanyl methyl (meth) acrylate, 3-methyl-oxetanyl methyl (Meth)acrylate, 3-ethyl-oxetanyl methyl (meth)acrylate, 3-butyl-oxetanyl methyl (meth)acrylate, 3- Hexyl-oxetanyl methyl (meth)acrylates and other (meth)acrylates containing oxetane groups; tetrahydrofurfuryl (meth)acrylates, butyrolactone (methyl) Acrylates and the like (meth)acrylates having heterocycles, hydroxytrimethylacetic acid neopentyl glycol (meth)acrylic acid adducts, p-phenylphenol (meth)acrylates and the like.
又,單官能自由基聚合性化合物可列舉如:(甲 基)丙烯酸、羧乙基丙烯酸酯、羧戊基丙烯酸酯、伊康酸、馬來酸、延胡索酸、巴豆酸、異巴豆酸等含有羧基之單體。 In addition, the monofunctional radical polymerizable compound may be exemplified by: (A Base) acrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, isocrotonic acid and other monomers containing carboxyl groups.
又,舉例言之,單官能自由基聚合性化合物可列 舉如:N-乙烯基吡咯啶酮、N-乙烯基-ε-己內醯胺、甲基乙烯基吡咯啶酮等內醯胺系乙烯基單體;乙烯基吡啶、乙烯基哌啶酮、乙烯基嘧啶、乙烯基哌嗪、乙烯基吡嗪、乙烯基吡咯、乙烯基咪唑、乙烯基噁唑、乙烯基嗎啉等具有含氮雜環之乙烯基系單體等。 Also, for example, monofunctional radical polymerizable compounds can be listed Examples include: N-vinylpyrrolidone, N-vinyl-ε-caprolactam, methylvinylpyrrolidone, and other vinylamide vinyl monomers; vinylpyridine, vinylpiperidone, Nitrogen-containing heterocyclic vinyl monomers such as vinylpyrimidine, vinylpiperazine, vinylpyrazine, vinylpyrrole, vinylimidazole, vinyloxazole, vinylmorpholine, etc.
又,單官能自由基聚合性化合物可使用具有活性 亞甲基之自由基聚合性化合物。具有活性亞甲基之自由基聚合性化合物是末端或分子中具有(甲基)丙烯醯基等活性雙鍵基且具有活性亞甲基之化合物。舉例言之,活性亞甲基可列舉如:乙醯乙醯基、烷氧基丙二醯基或氰基乙醯基等。前述活性亞甲基宜為乙醯乙醯基。舉例言之,具有活性亞甲基之自由基聚合性化合物之具體例可列舉如:2-乙醯乙醯氧基乙基(甲基)丙烯酸酯、2-乙醯乙醯氧基丙基(甲基)丙烯酸酯、2-乙醯乙醯氧基-1-甲基乙基(甲基)丙烯酸酯等乙醯乙醯氧基烷基(甲基)丙烯酸酯;2-乙氧基丙二醯基氧基乙基(甲基)丙烯酸酯、2-氰基乙醯氧基乙基(甲基)丙烯酸酯、N-(2-氰基乙醯氧基乙基)丙烯醯胺、N-(2-丙醯基乙醯氧基丁基)丙烯醯胺、N-(4-乙醯乙醯氧基甲基苄基)丙烯醯胺、N-(2-乙醯乙醯基胺基乙基)丙烯醯胺等。具有活性亞甲基之自由基聚合性化合物宜為乙醯乙醯氧基烷基(甲基)丙烯酸酯。 In addition, monofunctional radical polymerizable compounds can be used with activity Radical polymerizable compounds of methylene. A radical polymerizable compound having an active methylene group is a compound having an active double bond group such as a (meth)acryloyl group at the terminal or molecule and having an active methylene group. For example, the active methylene group can be exemplified by: acetoacetoxy, alkoxypropanedioxy, cyanoacetoxy, etc. The aforesaid active methylene group is preferably acetyl acetyl group. For example, specific examples of the radically polymerizable compound having an active methylene group include: 2-acetoacetoxyethyl (meth)acrylate, 2-acetoxyacetoxypropyl ( Methacrylic acid ester, 2-acetoxyethyloxy-1-methylethyl (meth)acrylate, etc. Acetylacetoxyalkyl (meth)acrylate; 2-ethoxypropanedi Acetyloxyethyl (meth)acrylate, 2-cyanoacetoxyethyl (meth)acrylate, N-(2-cyanoacetoxyethyl)acrylamide, N- (2-Propionylacetoxybutyl)acrylamide, N-(4-acetylacetoxymethylbenzyl)acrylamide, N-(2-acetylacetoacetamide) Radicals) acrylamide etc. The free-radical polymerizable compound having an active methylene group is preferably acetyl acetyl oxyalkyl (meth) acrylate.
《多官能自由基聚合性化合物》 "Multifunctional Radical Polymerizable Compound"
又,舉例言之,雙官能以上之多官能自由基聚合性化合物可列舉如:三丙二醇二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、1,9-壬二醇二(甲基)丙烯酸酯、1,10-癸二醇二丙烯酸酯、2-乙基-2-丁基丙二醇二(甲基)丙烯酸酯、雙酚A二(甲基)丙烯酸酯、雙酚A環氧乙烷加成物二(甲基)丙烯酸酯、雙酚A環氧丙烷加成物二(甲基)丙烯酸酯、雙酚A二環氧丙基醚二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、三環癸烷二甲醇二(甲基) 丙烯酸酯、環狀三羥甲基丙烷縮甲醛(甲基)丙烯酸酯、二氧六環二醇二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、新戊四醇三(甲基)丙烯酸酯、新戊四醇四(甲基)丙烯酸酯、二新戊四醇五(甲基)丙烯酸酯、二新戊四醇六(甲基)丙烯酸酯、EO變性二甘油四(甲基)丙烯酸酯等(甲基)丙烯酸與多元醇之酯化物、9,9-雙[4-(2-(甲基)丙烯醯氧基乙氧基)苯基]茀。具體例可列舉如:ARONIX M-220、M-306(東亞合成公司製)、LIGHT ACRYLATE1,9ND-A(共榮社化學公司製)、LIGHT ACRYLATE DGE-4A(共榮社化學公司製)、LIGHT ACRYLATE DCP-A(共榮社化學公司製)、SR-531(沙多瑪(Sartomer)公司製)、CD-536(沙多瑪公司製)等。又,依需要可列舉如:各種環氧(甲基)丙烯酸酯、胺基甲酸酯(甲基)丙烯酸酯、聚酯(甲基)丙烯酸酯或各種(甲基)丙烯酸酯系單體等。 In addition, for example, the bifunctional or higher polyfunctional radical polymerizable compound may include tripropylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, 1,6-hexanediol Di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol diacrylate, 2-ethyl-2-butylpropanediol di(meth)acrylic acid Ester, bisphenol A di(meth)acrylate, bisphenol A ethylene oxide adduct di(meth)acrylate, bisphenol A propylene oxide adduct di(meth)acrylate, bisphenol A Diglycidyl ether di(meth)acrylate, neopentyl glycol di(meth)acrylate, tricyclodecane dimethanol di(methyl) Acrylate, cyclic trimethylolpropane formal (meth)acrylate, dioxanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, neopentyl alcohol Tri (meth) acrylate, neopentaerythritol tetra (meth) acrylate, di neopentaerythritol penta (meth) acrylate, di neopentaerythritol hexa (meth) acrylate, EO modified diglycerol Ester of (meth)acrylic acid and polyol, such as tetra(meth)acrylate, 9,9-bis[4-(2-(meth)acryloyloxyethoxy)phenyl] stilbene. Specific examples include: ARONIX M-220, M-306 (manufactured by East Asia Synthesizer), LIGHT ACRYLATE 1, 9ND-A (manufactured by Kyoeisha Chemical Company), LIGHT ACRYLATE DGE-4A (manufactured by Kyoeisha Chemical Company), LIGHT ACRYLATE DCP-A (manufactured by Kyoeisha Chemical Co., Ltd.), SR-531 (manufactured by Sadoomer), CD-536 (manufactured by Sadoomer), etc. Moreover, various epoxy (meth)acrylates, urethane (meth)acrylates, polyester (meth)acrylates, various (meth)acrylate monomers, etc. are mentioned as needed. .
在控制前述硬化物之吸水率上,又,在滿足偏光 薄膜於嚴苛加濕環境下的光學耐久性上,自由基聚合性化合物含有前述多官能自由基聚合性化合物是較為理想的。 於前述多官能自由基聚合性化合物中,亦宜為logPow值高者。自由基聚合性化合物之logPow值宜為2以上,且更宜為3以上,最宜為4以上。 In controlling the water absorption rate of the aforementioned hardened material, in addition, in meeting the polarized light In terms of optical durability of the film under severe humidified environments, it is desirable that the radically polymerizable compound contains the aforementioned multifunctional radically polymerizable compound. Among the aforementioned multifunctional radical polymerizable compounds, those with a high logPow value are also preferred. The logPow value of the radical polymerizable compound is preferably 2 or more, more preferably 3 or more, and most preferably 4 or more.
舉例言之,logPow值高之自由基聚合性化合物可 列舉如:三環癸烷二甲醇二(甲基)丙烯酸酯(logPow=3.05)、異莰基(甲基)丙烯酸酯(logPow=3.27)等脂環(甲基)丙烯酸酯;1,9-壬二醇二(甲基)丙烯酸酯 (logPow=3.68)、1,10-癸二醇二丙烯酸酯(logPow=4.10)等長鏈脂肪族(甲基)丙烯酸酯;羥基三甲基乙酸新戊二醇(甲基)丙烯酸加成物(logPow=3.35)、2-乙基-2-丁基丙二醇二(甲基)丙烯酸酯(logPow=3.92)等多支鏈(甲基)丙烯酸酯;雙酚A二(甲基)丙烯酸酯(logPow=5.46)、雙酚A環氧乙烷4莫耳加成物二(甲基)丙烯酸酯(logPow=5.15)、雙酚A環氧丙烷2莫耳加成物二(甲基)丙烯酸酯(logPow=6.10)、雙酚A環氧丙烷4莫耳加成物二(甲基)丙烯酸酯(logPow=6.43)、9,9-雙[4-(2-(甲基)丙烯醯氧基乙氧基)苯基]茀(logPow=7.48)、p-苯基苯酚(甲基)丙烯酸酯(logPow=3.98)等含有芳香環之(甲基)丙烯酸酯等。 For example, a radical polymerizable compound with a high logPow value can Examples include: alicyclic (meth)acrylates such as tricyclodecane dimethanol di(meth)acrylate (logPow=3.05), isobornyl (meth)acrylate (logPow=3.27); 1,9- Nonanediol di(meth)acrylate (logPow=3.68), 1,10-decanediol diacrylate (logPow=4.10) and other long-chain aliphatic (meth)acrylate; hydroxytrimethylacetic acid neopentyl glycol (meth)acrylic acid adduct (logPow=3.35), 2-ethyl-2-butylpropanediol di(meth)acrylate (logPow=3.92) and other multi-branched (meth)acrylates; bisphenol A di(meth)acrylate ( logPow=5.46), bisphenol A ethylene oxide 4 mole adduct di(meth)acrylate (logPow=5.15), bisphenol A propylene oxide 2 mole adduct di(meth)acrylate (logPow=6.10), bisphenol A propylene oxide 4 mole adduct di(meth)acrylate (logPow=6.43), 9,9-bis[4-(2-(meth)acryloyloxy) (Ethoxy) phenyl] stilbene (logPow = 7.48), p-phenylphenol (meth) acrylate (logPow = 3.98) and other aromatic ring-containing (meth) acrylate.
若由兼顧與偏光件或各種透明保護薄膜之接著 性與嚴苛環境下的光學耐久性之觀點來看,則自由基聚合性化合物宜併用單官能自由基聚合性化合物與多官能自由基聚合性化合物。通常而言,相對於自由基聚合性化合物100重量%,以單官能自由基聚合性化合物3~80重量%與多官能自由基聚合性化合物20~97重量%之比例併用是較為理想的。 If it is combined with polarizers or various transparent protective films From the viewpoint of the optical durability in the harsh environment and the harsh environment, it is preferable to use a monofunctional radically polymerizable compound and a polyfunctional radically polymerizable compound in combination with the radically polymerizable compound. Generally speaking, it is preferable to use a monofunctional radical polymerizable compound at a ratio of 3 to 80% by weight and a polyfunctional radical polymerizable compound at 20 to 97% by weight relative to 100% by weight of the radical polymerizable compound.
<自由基聚合硬化型接著劑之態樣> <Appearance of free radical polymerization hardening type adhesive>
本發明之偏光薄膜用硬化型接著劑在將硬化性成分作成活性能量線硬化性成分而使用時,可作成活性能量線硬化型接著劑來使用,又,在將硬化性成分作成熱硬化性成分而使用時,可作成熱硬化型接著劑來使用。前述活性能量線硬化型接著劑在活性能量線使用電子射線等時,該活 性能量線硬化型接著劑毋須含有光聚合引發劑,然而,在活性能量線使用紫外線或可見光線時,宜含有光聚合引發劑。另一方面,在將前述接著劑之硬化性成分作成熱硬化性成分而使用時,該接著劑宜含有熱聚合引發劑。 When the curable adhesive for polarizing film of the present invention is used as a curable component as an active energy ray curable component, it can be used as an active energy ray curable adhesive, and when the curable component is a thermosetting component When used, it can be used as a thermosetting adhesive. When the active energy ray-curable adhesive described above uses electron beams or the like for active energy rays, the active The energy curable adhesive does not need to contain a photopolymerization initiator. However, when using ultraviolet rays or visible rays for the active energy ray, it is preferable to contain a photopolymerization initiator. On the other hand, when the curable component of the adhesive is used as a thermosetting component, the adhesive preferably contains a thermal polymerization initiator.
《光聚合引發劑》 "Photopolymerization Initiator"
使用自由基聚合性化合物時之光聚合引發劑可依照活性能量線適當地選擇。在藉由紫外線或可見光線硬化時,使用紫外線或可見光線分裂之光聚合引發劑。舉例言之,前述光聚合引發劑可列舉如:二苯乙二酮、二苯基酮、苯甲醯苯甲酸、3,3’-二甲基-4-甲氧基二苯基酮等二苯基酮系化合物;4-(2-羥乙氧基)苯基(2-羥基-2-丙基)酮、α-羥基-α,α’-二甲基苯乙酮、2-甲基-2-羥基苯丙酮、α-羥環己基苯基酮等芳香族酮化合物;甲氧基苯乙酮、2,2-二甲氧基-2-苯基苯乙酮、2,2-二乙氧基苯乙酮、2-甲基-1-[4-(甲硫基)-苯基]-2-嗎啉丙烷-1等苯乙酮系化合物;苯偶姻甲醚、苯偶姻乙醚、苯偶姻異丙醚、苯偶姻丁醚、大茴香偶姻甲醚等苯偶姻醚系化合物;二苯乙二酮二甲基縮酮等芳香族縮酮系化合物;2-萘磺醯氯等芳香族磺醯氯系化合物;1-苯酮-1,1-丙二酮-2-(o-乙氧羰基)肟等光活性肟系化合物;9-氧硫(thioxanthone)、2-氯9-氧硫、2-甲基9-氧硫、2,4-二甲基9-氧硫、異丙基9-氧硫、2,4-二氯9-氧硫、2,4-二乙基9-氧硫、2,4-二異丙基9-氧硫、十二基9-氧硫等9-氧硫系化合物;樟腦醌;鹵化酮;醯基氧化膦;醯基膦酸酯等。於光聚合引發劑中,亦宜為 logPow值高者。光聚合引發劑並未包含於偏光薄膜用硬化型接著劑之logPow值之計算中之成分,然而,光聚合引發劑之logPow值宜為1以上,且更宜為2以上,最宜為3以上。 When a radically polymerizable compound is used, the photopolymerization initiator can be appropriately selected according to the active energy ray. When curing by ultraviolet rays or visible rays, a photopolymerization initiator that splits ultraviolet rays or visible rays is used. For example, the aforementioned photopolymerization initiator may include diphenyl ethyl ketone, diphenyl ketone, benzoyl benzoic acid, 3,3'-dimethyl-4-methoxydiphenyl ketone, etc. Phenyl ketone compounds; 4-(2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone, α-hydroxy-α, α'-dimethylacetophenone, 2-methyl Aromatic ketone compounds such as -2-hydroxyphenylacetone and α-hydroxycyclohexyl phenyl ketone; methoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-bis Acetophenone compounds such as ethoxyacetophenone, 2-methyl-1-[4-(methylthio)-phenyl]-2-morpholinepropane-1; benzoin methyl ether, benzoin Benzoin ether compounds such as diethyl ether, benzoin isopropyl ether, benzoin butyl ether, anisein methyl ether, etc.; aromatic ketal compounds such as diphenyl ethyl ketone dimethyl ketal; 2-naphthalene Aromatic sulfonyl chloride compounds such as sulfonyl chloride; photoactive oxime compounds such as 1-benzophenone-1,1-propanedione-2-(o-ethoxycarbonyl)oxime; 9-oxosulfur (thioxanthone), 2-chloro 9-oxysulfur , 2-methyl 9-oxysulfur , 2,4-Dimethyl 9-oxysulfur , Isopropyl 9-oxysulfur , 2,4-Dichloro 9-oxysulfur , 2,4-Diethyl 9-oxysulfur , 2,4-Diisopropyl 9-oxysulfur , Dodecyl 9-oxysulfur 9-oxygen sulfur Compounds; camphorquinone; halogenated ketones; acylphosphine oxide; acylphosphonate, etc. Among photopolymerization initiators, those with a high logPow value are also preferred. The photopolymerization initiator is not included in the calculation of the logPow value of the hardening adhesive for polarizing film, however, the logPow value of the photopolymerization initiator is preferably 1 or more, more preferably 2 or more, and most preferably 3 or more .
相對於硬化性成分(自由基聚合性化合物)之全 量100重量份,前述光聚合引發劑之摻合量為20重量份以下。光聚合引發劑之摻合量宜為0.01~20重量份,且更宜為0.05~10重量份,進而是0.1~5重量份。 Relative to the total content of hardening components (radical polymerizable compounds) The amount is 100 parts by weight, and the blending amount of the aforementioned photopolymerization initiator is 20 parts by weight or less. The blending amount of the photopolymerization initiator is preferably 0.01 to 20 parts by weight, and more preferably 0.05 to 10 parts by weight, and further 0.1 to 5 parts by weight.
又,以含有自由基聚合性化合物作為硬化性成分 之可見光線硬化型使用本發明之偏光薄膜用硬化型接著劑時,特別是宜使用對380nm以上之光為高感度之光聚合引發劑。對380nm以上之光為高感度之光聚合引發劑如後述。 In addition, it contains a radically polymerizable compound as a hardening component Visible light curing type When using the curing type adhesive for polarizing film of the present invention, it is particularly preferable to use a photopolymerization initiator with high sensitivity to light of 380 nm or more. The photopolymerization initiator having high sensitivity to light of 380 nm or more will be described later.
前述光聚合引發劑宜單獨使用藉由下述一般式(1)所表示之化合物:
又,依需要,宜添加聚合引發助劑。聚合引發助 劑可列舉如:三乙胺、二乙胺、N-甲基二乙醇胺、乙醇胺、4-二甲胺苯甲酸、4-二甲胺苯甲酸甲酯、4-二甲胺苯甲酸乙酯、4-二甲胺苯甲酸異戊酯等,特別是宜為4-二甲胺苯甲酸乙酯。使用聚合引發助劑時,相對於硬化性成分之全量100重量份,其添加量通常為0~5重量份,且宜為0~4重量份,最宜為0~3重量份。 Moreover, if necessary, it is preferable to add a polymerization initiation aid. Polymerization initiator Examples of the agent include: triethylamine, diethylamine, N-methyldiethanolamine, ethanolamine, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, Isoamyl 4-dimethylaminobenzoate, etc., particularly preferably ethyl 4-dimethylaminobenzoate. When using a polymerization initiation aid, the addition amount is usually 0 to 5 parts by weight, preferably 0 to 4 parts by weight, and most preferably 0 to 3 parts by weight relative to 100 parts by weight of the total amount of the hardening component.
又,依需要,可併用公知之光聚合引發劑。由於 具有UV吸收能力之透明保護薄膜不會透射380nm以下之光,因此,光聚合引發劑宜使用對380nm以上之光為高感度之光聚合引發劑。具體而言,可列舉如:2-甲基-1-(4-甲硫基苯基)-2-嗎啉丙烷-1-酮、2-苄基-2-二甲胺基-1-(4-嗎啉苯基)-丁酮-1、2-(二甲胺基)-2-[(4-甲基苯基)甲基]-1-[4-(4-嗎啉基)苯基]-1-丁酮、2,4,6-三甲基苯甲醯基-二苯基-膦氧化物、雙(2,4,6-三甲基苯甲醯基)-苯基膦氧化物、雙(η 5-2,4-環戊二烯-1-基)-雙(2,6-二氟-3-(1H-吡咯-1-基)-苯基)鈦等。 In addition, if necessary, a known photopolymerization initiator may be used in combination. due to The transparent protective film with UV absorption ability will not transmit light below 380nm. Therefore, the photopolymerization initiator should be a photopolymerization initiator with high sensitivity to light above 380nm. Specific examples include 2-methyl-1-(4-methylthiophenyl)-2-morpholinepropane-1-one and 2-benzyl-2-dimethylamino-1-( 4-morpholinylphenyl)-butanone-1, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)benzene Group]-1-butanone, 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzyl)-phenylphosphine Oxides, bis(η 5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl) titanium, etc.
特別是除了一般式(1)之光聚合引發劑外,光聚合引發劑更宜使用藉由下述一般式(2)所表示之化合物:
<具有活性亞甲基之自由基聚合性化合物(a1)與具有奪氫作用之自由基聚合引發劑(a2)> <Free radical polymerizable compound (a1) with active methylene group and free radical polymerization initiator (a2) with hydrogen abstraction function>
於前述活性能量線硬化型接著劑中,當自由基聚合性化合物使用具有活性亞甲基之自由基聚合性化合物(a1)時,宜與具有奪氫作用之自由基聚合引發劑(a2)組合而使用。若藉由前述構造,則即使是特別是剛自高濕度環境或水中取出後(非乾燥狀態),亦可明顯地提升偏光薄膜所具有的接著劑層之接著性。該理由並不明確,然而,一般認為是以下原因。即,具有活性亞甲基之自由基聚合性化合物(a1)是與構成接著劑層之其他自由基聚合性化合物一同聚合,並取入接著劑層中的基礎聚合物之主鏈及/或側鏈,且形成接著劑層。於前述聚合過程中,若存在具有奪氫作用之自由基聚合引發劑(a2),則會自形成構成接著劑層之基礎聚合物並具有活性亞甲基之自由基聚合性化合物(a2)奪氫,且於亞甲基產生自由基。又,業已產生自由基之亞甲 基與PVA等偏光件之羥基反應,並於接著劑層與偏光件間形成共價鍵。其結果,一般推測即使是特別是非乾燥狀態,亦可明顯地提升偏光薄膜所具有的接著劑層之接著性。 Among the aforementioned active energy ray-curable adhesives, when the radical polymerizable compound uses a radical polymerizable compound (a1) having an active methylene group, it should be combined with a radical polymerization initiator (a2) having a hydrogen abstraction effect And use. With the aforementioned structure, even after taking out from a high-humidity environment or water (non-dry state), the adhesion of the adhesive layer of the polarizing film can be significantly improved. This reason is not clear, however, the following reasons are generally considered. That is, the radically polymerizable compound (a1) having an active methylene group is polymerized together with other radically polymerizable compounds constituting the adhesive layer and taken into the main chain and/or side of the base polymer in the adhesive layer Chain and form an adhesive layer. In the aforementioned polymerization process, if a radical polymerization initiator (a2) having a hydrogen abstraction function is present, a radical polymerizable compound (a2) having an active methylene group that forms the base polymer of the adhesive layer will be formed. Hydrogen, and generate free radicals in the methylene group. Moreover, the free radical methylene The base reacts with the hydroxyl group of the polarizer such as PVA and forms a covalent bond between the adhesive layer and the polarizer. As a result, it is generally speculated that even in a non-dry state, the adhesion of the adhesive layer of the polarizing film can be significantly improved.
於本發明中,舉例言之,具有奪氫作用之自由基 聚合引發劑(a2)可列舉如:9-氧硫系自由基聚合引發劑、二苯基酮系自由基聚合引發劑等。前述自由基聚合引發劑(a2)宜為9-氧硫系自由基聚合引發劑。舉例言之,9-氧硫系自由基聚合引發劑可列舉如:藉由前述一般式(1)所表示之化合物。舉例言之,藉由一般式(1)所表示之化合物之具體例可列舉如:9-氧硫、二甲基9-氧硫、二乙基9-氧硫、異丙基9-氧硫、氯9-氧硫等。 於藉由一般式(1)所表示之化合物中,亦特別宜為R1及R2為-CH2CH3之二乙基9-氧硫。 In the present invention, for example, the radical polymerization initiator (a2) having a hydrogen abstraction effect can be exemplified by: 9-oxysulfur Radical polymerization initiators, diphenyl ketone radical polymerization initiators, etc. The aforementioned radical polymerization initiator (a2) is preferably 9-oxysulfur It is a radical polymerization initiator. For example, 9-oxosulfur Examples of the radical polymerization initiator include compounds represented by the general formula (1). For example, specific examples of the compound represented by the general formula (1) include: 9-oxysulfur Dimethyl 9-oxysulfur , Diethyl 9-oxysulfur , Isopropyl 9-oxysulfur , Chlorine 9-oxygen sulfur Wait. Among the compounds represented by the general formula (1), diethyl 9-oxysulfur wherein R 1 and R 2 are -CH 2 CH 3 is also particularly preferred .
於前述活性能量線硬化型接著劑中,當含有具有 活性亞甲基之自由基聚合性化合物(a1)與具有奪氫作用之自由基聚合引發劑(a2)時,在將硬化性成分之全量作成100重量%時,宜含有前述具有活性亞甲基之自由基聚合性化合物(a1)1~50重量%,以及相對於硬化性成分之全量100重量份,含有自由基聚合引發劑(a2)0.1~10重量份。 In the aforementioned active energy ray hardening type adhesive, when containing When the radically polymerizable compound (a1) of the active methylene group and the radical polymerization initiator (a2) having a hydrogen abstraction function, when the total amount of the curable component is 100% by weight, it is preferable to contain the aforementioned active methylene group The radical polymerizable compound (a1) is 1 to 50% by weight, and the total amount of the curable component is 100 parts by weight, and contains 0.1 to 10 parts by weight of the radical polymerization initiator (a2).
如前述,於本發明中,在具有奪氫作用之自由基 聚合引發劑(a2)之存在下,使具有活性亞甲基之自由基聚合性化合物(a1)之亞甲基產生自由基,且前述亞甲基與PVA等偏光件之羥基反應,並形成共價鍵。故,為了使具有活性亞甲基之自由基聚合性化合物(a1)之亞甲基產生自由基,並 充分地形成前述共價鍵,在將硬化性成分之全量作成100重量%時,宜含有具有活性亞甲基之自由基聚合性化合物(a1)1~50重量%,再者,更宜含有3~30重量%。欲充分地提升耐水性而提升非乾燥狀態下之接著性時,具有活性亞甲基之自由基聚合性化合物(a1)宜作成1重量%以上。另一方面,若大於50重量%,則會有產生接著劑層之硬化不良之情形。又,相對於硬化性成分之全量100重量份,具有奪氫作用之自由基聚合引發劑(a2)宜含有0.1~10重量份,再者,更宜含有0.3~9重量份。欲充分地進行奪氫反應時,宜使用自由基聚合引發劑(a2)0.1重量份以上。另一方面,若大於10重量份,則會有並未於接著劑中完全溶解之情形。 As mentioned above, in the present invention, the free radicals with hydrogen abstraction function In the presence of the polymerization initiator (a2), the methylene group of the radically polymerizable compound (a1) having an active methylene group generates radicals, and the aforementioned methylene group reacts with the hydroxyl group of the polarizer such as PVA to form a Price key. Therefore, in order to generate free radicals for the methylene group of the radical polymerizable compound (a1) having an active methylene group, and When the aforementioned covalent bond is sufficiently formed, when the total amount of the hardenable component is 100% by weight, it is preferable to contain 1 to 50% by weight of the radically polymerizable compound (a1) having an active methylene group, and more preferably 3 ~30% by weight. In order to sufficiently improve the water resistance and the adhesion in the non-dry state, the radical polymerizable compound (a1) having an active methylene group is preferably made 1% by weight or more. On the other hand, if it exceeds 50% by weight, the hardening of the adhesive layer may occur. Furthermore, the radical polymerization initiator (a2) having a hydrogen abstraction effect preferably contains 0.1 to 10 parts by weight relative to 100 parts by weight of the total amount of the hardenable component, and further preferably contains 0.3 to 9 parts by weight. In order to sufficiently perform the hydrogen abstraction reaction, it is preferable to use 0.1 parts by weight or more of the radical polymerization initiator (a2). On the other hand, if it exceeds 10 parts by weight, it may not be completely dissolved in the adhesive.
《熱聚合引發劑》 "Thermal Polymerization Initiator"
熱聚合引發劑宜為在接著劑層之形成時未藉由熱分裂而開始聚合者。舉例言之,熱聚合引發劑宜為10小時半衰期溫度為65℃以上,進而是75~90℃者。另,所謂半衰期是表示聚合引發劑之分解速度之指標,並指直到聚合引發劑之殘存量構成一半為止之時間。有關用以於任意時間獲得半衰期之分解溫度或於任意溫度下之半衰期時間是揭示於製造者目錄等,舉例言之,揭示於日本油脂股份有限公司之「有機過氧化物目錄第9版(2003年5月)」等。 The thermal polymerization initiator is preferably one that does not start polymerization by thermal cracking when the adhesive layer is formed. For example, the thermal polymerization initiator is preferably a 10-hour half-life temperature of 65 ℃ or more, and further 75 ~ 90 ℃. In addition, the half-life is an index indicating the decomposition rate of the polymerization initiator and refers to the time until the remaining amount of the polymerization initiator constitutes half. The decomposition temperature used to obtain the half-life at any time or the half-life time at any temperature is disclosed in the manufacturer's catalog, etc., for example, in the "Organic Peroxide Catalog 9th Edition (2003 May)) etc.
舉例言之,熱聚合引發劑可列舉如:過氧化月桂 醯基(10小時半衰期溫度:64℃)、過氧化苯甲醯基(10小時半衰期溫度:73℃)、1,1-雙(t-丁過氧)-3,3,5-三甲基環己烷(10小時半衰期溫度:90℃)、二(2-乙基己基)過氧二碳酸酯 (10小時半衰期溫度:49℃)、二(4-t-丁基環己基)過氧二碳酸酯、二-sec-丁過氧二碳酸酯(10小時半衰期溫度:51℃)、t-丁過氧新癸酸酯(10小時半衰期溫度:48℃)、t-己過氧三甲基乙酸酯、t-丁過氧三甲基乙酸酯、二月桂醯基過氧化物(10小時半衰期溫度:64℃)、二-n-辛醯基過氧化物、1,1,3,3-四甲基丁過氧-2-乙基己酸酯(10小時半衰期溫度:66℃)、二(4-甲基苯甲醯基)過氧化物、二苯甲醯基過氧化物(10小時半衰期溫度:73℃)、t-丁過氧異丁酸酯(10小時半衰期溫度:81℃)、1,1-二(t-己過氧)環己烷等有機系過氧化物。 For example, the thermal polymerization initiator can be exemplified by: Laurel peroxide Acyl (10-hour half-life temperature: 64°C), Benzoyl peroxide (10-hour half-life temperature: 73°C), 1,1-bis(t-butoxyperoxy)-3,3,5-trimethyl Cyclohexane (10-hour half-life temperature: 90°C), bis(2-ethylhexyl) peroxydicarbonate (10-hour half-life temperature: 49°C), bis(4-t-butylcyclohexyl) peroxydicarbonate, di-sec-butylperoxydicarbonate (10-hour half-life temperature: 51°C), t-butane Peroxyneodecanoate (10-hour half-life temperature: 48°C), t-hexaperoxytrimethyl acetate, t-butylperoxytrimethyl acetate, dilauryl peroxide (10 hours Half-life temperature: 64°C), di-n-octyl peroxide, 1,1,3,3-tetramethylbutoxyperoxy-2-ethylhexanoate (10-hour half-life temperature: 66°C), di( 4-methylbenzyl peroxide), dibenzoyl peroxide (10-hour half-life temperature: 73°C), t-butyl peroxyisobutyrate (10-hour half-life temperature: 81°C), Organic peroxides such as 1,1-di(t-hexaperoxy)cyclohexane.
又,舉例言之,熱聚合引發劑可列舉如:2,2’-偶氮雙異丁腈(10小時半衰期溫度:67℃)、2,2’-偶氮雙(2-甲基丁腈)(10小時半衰期溫度:67℃)、1,1-偶氮雙-環己烷-1-腈(10小時半衰期溫度:87℃)等偶氮系化合物。 In addition, for example, the thermal polymerization initiator may include: 2,2'-azobisisobutyronitrile (10 hour half-life temperature: 67°C), 2,2'-azobis(2-methylbutyronitrile ) (10 hour half-life temperature: 67°C), 1,1-azobis-cyclohexane-1-carbonitrile (10 hour half-life temperature: 87°C) and other azo compounds.
相對於硬化性成分(自由基聚合性化合物)之全量100重量份,熱聚合引發劑之摻合量為0.01~20重量份。熱聚合引發劑之摻合量更宜為0.05~10重量份,進而是0.1~3重量份。 The blending amount of the thermal polymerization initiator is 0.01 to 20 parts by weight with respect to 100 parts by weight of the total amount of the curable component (radical polymerizable compound). The blending amount of the thermal polymerization initiator is more preferably 0.05 to 10 parts by weight, and further 0.1 to 3 parts by weight.
<2:陽離子聚合硬化型接著劑> <2: Cationic polymerization hardening type adhesive>
陽離子聚合硬化型接著劑之硬化性成分可列舉如:具有環氧基或氧雜環丁烷基之化合物。具有環氧基之化合物只要是分子內具有至少2個環氧基,則無特殊之限制,可使用一般已知的各種硬化性環氧化合物。作為理想之環氧化合物,可列舉為例的是:分子內具有至少2個環氧基與至少1個芳香環之化合物(芳香族系環氧化合物),或分子內具有 至少2個環氧基且其中至少1個於構成脂環式環之相鄰之2個碳原子間形成之化合物(脂環式環氧化合物)等。 Examples of the hardening component of the cationic polymerization hardening type adhesive include compounds having epoxy groups or oxetanyl groups. The compound having an epoxy group is not particularly limited as long as it has at least two epoxy groups in the molecule, and various generally known hardenable epoxy compounds can be used. Examples of the ideal epoxy compound include compounds having at least two epoxy groups and at least one aromatic ring in the molecule (aromatic epoxy compounds), or having A compound having at least two epoxy groups and at least one of which is formed between two adjacent carbon atoms constituting an alicyclic ring (alicyclic epoxy compound), etc.
<光陽離子聚合引發劑> <Photo cationic polymerization initiator>
由於陽離子聚合硬化型接著劑含有以上所說明的環氧化合物及氧雜環丁烷化合物作為硬化性成分,且該等皆藉由陽離子聚合而硬化,因此,摻合光陽離子聚合引發劑。該光陽離子聚合引發劑是藉由可見光線、紫外線、X射線、電子射線等活性能量線之照射,產生陽離子種或路易斯酸,並開始環氧基或氧雜環丁烷基之聚合反應。 Since the cationic polymerization hardening type adhesive contains the epoxy compound and the oxetane compound described above as hardening components, and these are hardened by cationic polymerization, a photo-cationic polymerization initiator is blended. The photo-cationic polymerization initiator generates cationic species or Lewis acid by irradiation of active energy rays such as visible rays, ultraviolet rays, X-rays, and electron rays, and starts the polymerization reaction of epoxy groups or oxetanyl groups.
<其他成分> <other ingredients>
有關本發明之硬化型接著劑宜含有下述成分。 The hardening type adhesive of the present invention preferably contains the following components.
<丙烯酸系低聚物(A)> <Acrylic oligomer (A)>
除了有關前述自由基聚合性化合物之硬化性成分外,有關本發明之活性能量線硬化型接著劑可含有聚合(甲基)丙烯酸單體所構成的丙烯酸系低聚物(A)。藉由於活性能量線硬化型接著劑中含有丙烯酸系低聚物(A),可減低使活性能量線照射至該接著劑並硬化時的硬化收縮,並減低接著劑與偏光件及透明保護薄膜等被接著體之界面應力。其結果,可抑制接著劑層與被接著體之接著性之降低。為了充分地抑制硬化物層(接著劑層)之硬化收縮,相對於硬化性成分之全量100重量份,丙烯酸系低聚物(A)之含量宜為20重量份以下,且更宜為15重量份以下。若接著劑中的丙烯酸系低聚物(A)之含量過多,則將活性能量線照射至該接著劑時的反應速度之降低劇烈,並有構成硬化不良之情形。另 一方面,相對於硬化性成分之全量100重量份,宜含有丙烯酸系低聚物(A)3重量份以上,更宜含有5重量份以上。 In addition to the curable component of the radical polymerizable compound, the active energy ray-curable adhesive of the present invention may contain an acrylic oligomer (A) composed of polymerized (meth)acrylic monomers. Since the active energy ray-curable adhesive contains an acrylic oligomer (A), the curing shrinkage when the active energy ray is irradiated to the adhesive and hardens can be reduced, and the adhesive, polarizer, transparent protective film, etc. can be reduced The interface stress of the attached body. As a result, a decrease in the adhesion between the adhesive layer and the adherend can be suppressed. In order to sufficiently suppress the curing shrinkage of the cured product layer (adhesive layer), the content of the acrylic oligomer (A) is preferably 20 parts by weight or less and more preferably 15 parts by weight with respect to 100 parts by weight of the total amount of the curable component. Below. If the content of the acrylic oligomer (A) in the adhesive is too large, the reaction rate when the active energy ray is irradiated to the adhesive is drastically reduced, and it may constitute a curing failure. another On the one hand, the acrylic oligomer (A) is preferably contained in an amount of 3 parts by weight or more relative to 100 parts by weight of the total amount of the hardenable component, more preferably 5 parts by weight or more.
在考慮塗覆時之作業性或均一性時,活性能量線 硬化型接著劑宜為低黏度,因此,聚合(甲基)丙烯酸單體所構成的丙烯酸系低聚物(A)亦宜為低黏度。屬於低黏度且可防止接著劑層之硬化收縮之丙烯酸系低聚物宜為重量平均分子量(Mw)為15000以下,且更宜為10000以下,特別是宜為5000以下。另一方面,為了充分地抑制硬化物層(接著劑層)之硬化收縮,丙烯酸系低聚物(A)之重量平均分子量(Mw)宜為500以上,且更宜為1000以上,特別是宜為1500以上。 具體而言,舉例言之,構成丙烯酸系低聚物(A)之(甲基)丙烯酸單體可列舉如:甲基(甲基)丙烯酸酯、乙基(甲基)丙烯酸酯、n-丙基(甲基)丙烯酸酯、異丙基(甲基)丙烯酸酯、2-甲基-2-硝基丙基(甲基)丙烯酸酯、n-丁基(甲基)丙烯酸酯、異丁基(甲基)丙烯酸酯、S-丁基(甲基)丙烯酸酯、t-丁基(甲基)丙烯酸酯、n-戊基(甲基)丙烯酸酯、t-戊基(甲基)丙烯酸酯、3-戊基(甲基)丙烯酸酯、2,2-二甲基丁基(甲基)丙烯酸酯、n-己基(甲基)丙烯酸酯、十六基(甲基)丙烯酸酯、n-辛基(甲基)丙烯酸酯、2-乙基己基(甲基)丙烯酸酯、4-甲基-2-丙基戊基(甲基)丙烯酸酯、N-十八基(甲基)丙烯酸酯等(甲基)丙烯酸(碳數1-20)烷基酯類,再者,舉例言之,環烷基(甲基)丙烯酸酯(例如環己基(甲基)丙烯酸酯、環戊基(甲基)丙烯酸酯等)、芳烷基(甲基)丙烯酸酯(例如苄基(甲基)丙烯酸酯等)、多環式(甲基)丙烯酸酯(例如2-異莰基(甲基)丙烯酸 酯、2-降莰基甲基(甲基)丙烯酸酯、5-降莰烯-2-基-甲基(甲基)丙烯酸酯、3-甲基-2-降莰基甲基(甲基)丙烯酸酯等)、含有羥基之(甲基)丙烯酸酯類(例如羥乙基(甲基)丙烯酸酯、2-羥丙基(甲基)丙烯酸酯、2,3-二羥丙基甲基-丁基(甲基)甲基丙烯酸酯等)、含有烷氧基或苯氧基之(甲基)丙烯酸酯類(2-甲氧基乙基(甲基)丙烯酸酯、2-乙氧基乙基(甲基)丙烯酸酯、2-甲氧基甲氧基乙基(甲基)丙烯酸酯、3-甲氧基丁基(甲基)丙烯酸酯、乙基卡必醇(甲基)丙烯酸酯、苯氧基乙基(甲基)丙烯酸酯等)、含有環氧基之(甲基)丙烯酸酯類(例如環氧丙基(甲基)丙烯酸酯等)、含有鹵素之(甲基)丙烯酸酯類(例如2,2,2-三氟乙基(甲基)丙烯酸酯、2,2,2-三氟乙基乙基(甲基)丙烯酸酯、四氟丙基(甲基)丙烯酸酯、六氟丙基(甲基)丙烯酸酯、八氟戊基(甲基)丙烯酸酯、十七氟癸基(甲基)丙烯酸酯等)、烷基胺基烷基(甲基)丙烯酸酯(例如二甲基胺基乙基(甲基)丙烯酸酯等)等。該等(甲基)丙烯酸酯可單獨使用或併用2種以上。丙烯酸系低聚物(A)之具體例可列舉如:東亞合成公司製「ARUFON」、綜研化學公司製「ACTFLOW」、日本BASF公司製「JONCRYL」等。於聚合(甲基)丙烯酸單體所構成的丙烯酸系低聚物(A)中,亦宜為logPow值高者。丙烯酸系低聚物(A)包含於偏光薄膜用硬化型接著劑之logPow值之計算中之成分。於logPow值之計算中,有關丙烯酸系低聚物(A)之成分之莫耳數是採用業已換算成構成丙烯酸系低聚物(A)之(甲基)丙烯酸單體之莫耳數。聚合(甲基)丙烯酸單體所構成的丙烯酸系低聚物(A)之 logPow值宜為2以上,且更宜為3以上,最宜為4以上。 When considering the workability or uniformity of coating, the active energy ray The hardening adhesive is preferably of low viscosity. Therefore, the acrylic oligomer (A) composed of polymerized (meth)acrylic monomers is also preferably of low viscosity. The acrylic oligomer which belongs to low viscosity and can prevent hardening and shrinkage of the adhesive layer preferably has a weight average molecular weight (Mw) of 15,000 or less, and more preferably 10,000 or less, and particularly preferably 5000 or less. On the other hand, in order to sufficiently suppress the curing shrinkage of the cured product layer (adhesive layer), the weight average molecular weight (Mw) of the acrylic oligomer (A) is preferably 500 or more, and more preferably 1000 or more, and particularly preferably It is more than 1500. Specifically, for example, examples of the (meth)acrylic monomer constituting the acrylic oligomer (A) include: methyl (meth)acrylate, ethyl (meth)acrylate, n-propylene (Meth)acrylate, isopropyl (meth)acrylate, 2-methyl-2-nitropropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (Meth)acrylate, S-butyl (meth)acrylate, t-butyl (meth)acrylate, n-pentyl (meth)acrylate, t-pentyl (meth)acrylate , 3-pentyl (meth)acrylate, 2,2-dimethylbutyl (meth)acrylate, n-hexyl (meth)acrylate, hexadecyl (meth)acrylate, n- Octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 4-methyl-2-propylpentyl (meth)acrylate, N-octadecyl (meth)acrylate (Meth)acrylic acid (C 1-20) alkyl esters, and, for example, cycloalkyl (meth) acrylates (such as cyclohexyl (meth) acrylate, cyclopentyl (meth Group) acrylate, etc.), aralkyl (meth)acrylate (such as benzyl (meth)acrylate, etc.), polycyclic (meth)acrylate (such as 2-isobornyl (meth)acrylic acid Ester, 2-nor camphenyl methyl (meth) acrylate, 5-nor camphen-2-yl-methyl (meth) acrylate, 3-methyl-2-nor camphenyl methyl (meth ) Acrylates, etc.), (meth)acrylates containing hydroxyl groups (eg hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2,3-dihydroxypropylmethyl -Butyl(meth)methacrylate, etc.), (meth)acrylates containing alkoxy or phenoxy groups (2-methoxyethyl(meth)acrylate, 2-ethoxy Ethyl (meth)acrylate, 2-methoxymethoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, ethyl carbitol (meth)acrylic acid Esters, phenoxyethyl (meth)acrylates, etc.), epoxy-containing (meth)acrylates (such as epoxypropyl (meth)acrylates, etc.), halogen-containing (meth) Acrylic esters (e.g. 2,2,2-trifluoroethyl (meth)acrylate, 2,2,2-trifluoroethyl ethyl (meth)acrylate, tetrafluoropropyl (meth)acrylic acid Ester, hexafluoropropyl (meth)acrylate, octafluoropentyl (meth)acrylate, heptafluorodecyl (meth)acrylate, etc.), alkylaminoalkyl (meth)acrylate (For example, dimethylaminoethyl (meth)acrylate, etc.) and the like. These (meth)acrylates can be used alone or in combination of two or more. Specific examples of the acrylic oligomer (A) include: "ARUFON" manufactured by Toya Synthetic Corporation, "ACTFLOW" manufactured by Kken Chemical Co., Ltd., and "JONCRYL" manufactured by BASF Corporation of Japan. Among acrylic oligomers (A) composed of polymerized (meth)acrylic monomers, those with a high logPow value are also preferred. The acrylic oligomer (A) is included in the calculation of the logPow value of the hardening adhesive for polarizing film. In the calculation of the logPow value, the molar number of the component of the acrylic oligomer (A) is the molar number of the (meth)acrylic monomer that has been converted into the acrylic oligomer (A). The acrylic oligomer (A) composed of polymerized (meth)acrylic monomers The logPow value should be 2 or more, more preferably 3 or more, and most preferably 4 or more.
<光酸產生劑(B)> <Photoacid generator (B)>
於前述活性能量線硬化型接著劑中,可含有光酸產生劑(B)。於前述活性能量線硬化型接著劑中含有光酸產生劑時,相較於未含有光酸產生劑時,可躍進地提升接著劑層之耐水性及耐久性。光酸產生劑(B)可藉由下述一般式(3)來表示。 The aforementioned active energy ray-curable adhesive may contain a photoacid generator (B). When the active energy ray-curable adhesive contains a photoacid generator, the water resistance and durability of the adhesive layer can be improved dramatically compared to when no photoacid generator is included. The photoacid generator (B) can be represented by the following general formula (3).
一般式(3)[化學式3]L + X - [Chemical Formula 3] L in general formula (3) + X -
(然而,L+表示任意之鎓陽離子。又,X-表示選自於由PF66 -、SbF6 -、AsF6 -、SbCl6 -、BiCl5 -、SnCl6 -、ClO4 -、二硫胺基甲酸酯陰離子、SCN-所構成群中之相對陰離子。) (However, L + represents a cation and any of, X -. Selected from the group consisting represents PF6 6 -, SbF 6 -, AsF 6 -, SbCl 6 -, BiCl 5 -, SnCl 6 -, ClO 4 -, disulfide Carbamate anions, relative anions in the SCN-group.)
宜作為構成一般式(3)之鎓陽離子L+之鎓陽離子之結構可列舉如:選自於下述一般式(4)~一般式(12)之鎓陽離子。 Suitable onium cations constituting the onium cation L + of the general formula (3) include, for example, the onium cations selected from the following general formula (4) to general formula (12).
一般式(4)
一般式(5)[化學式5]
一般式(6)
一般式(7)
一般式(8)
一般式(9)[化學式9]
一般式(10)
一般式(11)
一般式(12)
(然而,前述一般式(4)-(12)中,R1、R2及R3分別獨立地表示選自於氫原子、取代或未取代之烷基、取代或未取代 之烯基、取代或未取代之芳基、取代或未取代之雜環基、取代或未取代之烷氧基、取代或未取代之芳氧基、取代或未取代之雜環氧基、取代或未取代之醯基、取代或未取代之羰氧基、取代或未取代之氧羰基或鹵素原子之基。R4表示與R1、R2及R3所揭示之基相同之基。R5表示取代或未取代之烷基、取代或未取代之烷硫基。R6及R7分別獨立地表示取代或未取代之烷基、取代或未取代之烷氧基。R表示鹵素原子、羥基、羧基、巰基、氰基、硝基、取代或未取代之胺甲醯基、取代或未取代之烷基、取代或未取代之烯基、取代或未取代之芳基、取代或未取代之雜環基、取代或未取代之烷氧基、取代或未取代之芳氧基、取代或未取代之雜環氧基、取代或未取代之烷硫基、取代或未取代之芳硫基、取代或未取代之雜環硫基、取代或未取代之醯基、取代或未取代之羰氧基、取代或未取代之氧羰基中之任一者。Ar4、Ar5表示取代或未取代之芳基、取代或未取代之雜環基中之任一者。X表示氧或硫原子。i表示0~5之整數。j表示0~4之整數。k表示0~3之整數。又,鄰接之R彼此、Ar4與Ar5、R2與R3、R2與R4、R3與R4、R1與R2、R1與R3、R1與R4、R1與R或R1與R5亦可為相互鍵結之環狀結構。) (However, in the aforementioned general formulas (4)-(12), R 1 , R 2 and R 3 each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substitution Or unsubstituted aryl, substituted or unsubstituted heterocyclic group, substituted or unsubstituted alkoxy, substituted or unsubstituted aryloxy, substituted or unsubstituted heterocyclic oxy, substituted or unsubstituted acryl Group, substituted or unsubstituted carbonyloxy group, substituted or unsubstituted oxycarbonyl group or halogen atom group. R 4 represents the same group as disclosed by R 1 , R 2 and R 3. R 5 represents substituted or unsubstituted Substituted alkyl, substituted or unsubstituted alkylthio. R 6 and R 7 independently represent substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy. R represents halogen atom, hydroxyl, carboxyl, mercapto , Cyano, nitro, substituted or unsubstituted amine formyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocyclic, Substituted or unsubstituted alkoxy, substituted or unsubstituted aryloxy, substituted or unsubstituted heterocyclic oxy, substituted or unsubstituted alkylthio, substituted or unsubstituted arylthio, substituted or unsubstituted Any one of heterocyclic thio group, substituted or unsubstituted acetyl group, substituted or unsubstituted carbonyloxy group, substituted or unsubstituted oxycarbonyl group. Ar 4 and Ar 5 represent substituted or unsubstituted aryl group, Either a substituted or unsubstituted heterocyclic group. X represents an oxygen or sulfur atom. i represents an integer from 0 to 5. j represents an integer from 0 to 4. k represents an integer from 0 to 3. In addition, adjacent R Each other, Ar 4 and Ar 5 , R 2 and R 3 , R 2 and R 4 , R 3 and R 4 , R 1 and R 2 , R 1 and R 3 , R 1 and R 4 , R 1 and R or R 1 and R 5 may also be a ring structure bonded to each other.)
相當於一般式(4)之鎓陽離子(鋶陽離子):可列舉如:二甲基苯基鋶、二甲基(o-氟苯基)鋶、二甲基(m-氯苯基)鋶、二甲基(p-溴苯基)鋶、二甲基(p-氰基苯基)鋶、二甲基(m-硝基苯基)鋶、二甲基(2,4,6-三溴苯基)鋶、二甲基(五氟苯基)鋶、二甲基(p-(三氟甲基)苯基)鋶、二甲 基(p-羥苯基)鋶、二甲基(p-巰苯基)鋶、二甲基(p-甲亞磺醯基苯基)鋶、二甲基(p-甲磺醯基苯基)鋶、二甲基(o-乙醯基苯基)鋶、二甲基(o-苯甲醯基苯基)鋶、二甲基(p-甲基苯基)鋶、二甲基(p-異丙基苯基)鋶、二甲基(p-十八基苯基)鋶、二甲基(p-環己基苯基)鋶、二甲基(p-甲氧基苯基)鋶、二甲基(o-甲氧羰基苯基)鋶、二甲基(p-苯基磺醯基苯基)鋶、(7-甲氧基-2-側氧-2H-色烯-4-基)二甲基鋶、(4-甲氧基萘-1-基)二甲基鋶、二甲基(p-異丙氧羰基苯基)鋶、二甲基(2-萘基)鋶、二甲基(9-蒽基)鋶、二乙基苯基鋶、甲基乙基苯基鋶、甲基二苯基鋶、三苯基鋶、二異丙基苯基鋶、二苯基(4-苯基磺醯基-苯基)-鋶、4,4’-雙(二苯基鋶)二苯基硫醚、4,4’-雙[二[(4-(2-羥基-乙氧基)-苯基)]鋶]]二苯基硫醚、4,4’-雙(二苯基鋶)伸聯苯、二苯基(o-氟苯基)鋶、二苯基(m-氯苯基)鋶、二苯基(p-溴苯基)鋶、二苯基(p-氰基苯基)鋶、二苯基(m-硝基苯基)鋶、二苯基(2,4,6-三溴苯基)鋶、二苯基(五氟苯基)鋶、二苯基(p-(三氟甲基)苯基)鋶、二苯基(p-羥苯基)鋶、二苯基(p-巰苯基)鋶、二苯基(p-甲亞磺醯基苯基)鋶、二苯基(p-甲磺醯基苯基)鋶、二苯基(o-乙醯基苯基)鋶、二苯基(o-苯甲醯基苯基)鋶、二苯基(p-甲基苯基)鋶、二苯基(p-異丙基苯基)鋶、二苯基(p-十八基苯基)鋶、二苯基(p-環己基苯基)鋶、二苯基(p-甲氧基苯基)鋶、二苯基(o-甲氧羰基苯基)鋶、二苯基(p-苯基磺醯基苯基)鋶、(7-甲氧基-2-側氧-2H-色烯-4-基)二苯基鋶、(4-甲氧基萘-1-基)二苯基鋶、二苯基(p-異丙氧羰基苯基)鋶、二苯基(2-萘基)鋶、二苯基 (9-蒽基)鋶、乙基二苯基鋶、甲基乙基(o-甲苯基)鋶、甲基二(p-甲苯基)鋶、三(p-甲苯基)鋶、二異丙基(4-苯基磺醯基苯基)鋶、二苯基(2-噻吩基)鋶、二苯基(2-呋喃基)鋶、二苯基(9-乙基-9H咔唑-3-基)鋶等,然而,並不限於該等。 Equivalent to the onium cation (cerium cation) of general formula (4): examples include: dimethylphenyl cerium, dimethyl (o-fluorophenyl) cerium, dimethyl (m-chlorophenyl) cerium, Dimethyl (p-bromophenyl) alkene, dimethyl (p-cyanophenyl) agar, dimethyl (m-nitrophenyl) agar, dimethyl (2,4,6-tribromo Phenyl) cerium, dimethyl (pentafluorophenyl) cerium, dimethyl (p-(trifluoromethyl) phenyl) cerium, dimethyl (P-hydroxyphenyl)ammonium, dimethyl (p-mercaptophenyl)ammonium, dimethyl (p-methylsulfinylphenyl)ammonium, dimethyl (p-methylsulfonylphenyl) ) 鋶, dimethyl (o-ethoxyphenyl) 鋶, dimethyl (o-benzoylphenyl) 鋶, dimethyl (p-methylphenyl) 鋶, dimethyl (p -Isopropylphenyl) agar, dimethyl (p-octadecylphenyl) agar, dimethyl (p-cyclohexylphenyl) agar, dimethyl (p-methoxyphenyl) agar, Dimethyl (o-methoxycarbonylphenyl) amide, dimethyl (p-phenylsulfonylphenyl) amide, (7-methoxy-2-oxo-2H-chromen-4-yl ) Dimethyl alkane, (4-methoxynaphthalene-1-yl) dimethyl alkane, dimethyl (p-isopropoxycarbonylphenyl) agar, dimethyl (2-naphthyl) agar, di Methyl (9-anthracenyl) alkane, diethylphenyl alkane, methyl ethyl phenyl alkane, methyl diphenyl alkane, triphenyl alkane, diisopropylphenyl alkane, diphenyl (4 -Phenylsulfonyl-phenyl)-ammonium, 4,4'-bis(diphenylammonium) diphenyl sulfide, 4,4'-bis[di[(4-(2-hydroxy-ethoxy Yl)-phenyl)] 鋶]] diphenyl sulfide, 4,4'-bis (diphenyl carbamide) biphenylene, diphenyl (o-fluorophenyl) carbamide, diphenyl (m- Chlorophenyl) alkene, diphenyl (p-bromophenyl) agar, diphenyl (p-cyanophenyl) agar, diphenyl (m-nitrophenyl) agar, diphenyl (2, 4,6-tribromophenyl) agaric, diphenyl (pentafluorophenyl) agaric, diphenyl (p-(trifluoromethyl)phenyl) agaric, diphenyl (p-hydroxyphenyl) agaric , Diphenyl (p-mercaptophenyl) alkene, diphenyl (p-methylsulfinylphenyl) alkene, diphenyl (p-methylsulfonylphenyl) alkane, diphenyl (o- Acetylphenyl) amide, diphenyl (o-benzylphenyl) amide, diphenyl (p-methylphenyl) amide, diphenyl (p-isopropylphenyl) amide, Diphenyl (p-octadecylphenyl) alkene, diphenyl (p-cyclohexylphenyl) alkane, diphenyl (p-methoxyphenyl) alkane, diphenyl (o-methoxycarbonyl) Phenyl) alkene, diphenyl (p-phenylsulfonylphenyl) alkene, (7-methoxy-2-oxo-2H-chromen-4-yl) diphenyl alkane, (4- Methoxynaphthalene-1-yl) diphenyl alkene, diphenyl (p-isopropoxycarbonylphenyl) alkene, diphenyl (2-naphthyl) alkane, diphenyl (9-anthracenyl) agar, ethyl diphenyl agar, methyl ethyl (o-tolyl) agar, methyl di (p-tolyl) agar, tri (p-tolyl) agar, diisopropyl (4-phenylsulfonylphenyl) alkane, diphenyl (2-thienyl) alkane, diphenyl (2-furyl) alkane, diphenyl (9-ethyl-9Hcarbazole-3 -Base) Kaku, etc. However, it is not limited to these.
相當於一般式(5)之鎓陽離子(氧化鋶陽離子): 可列舉如:二甲基苯基氧化鋶、二甲基(o-氟苯基)氧化鋶、二甲基(m-氯苯基)氧化鋶、二甲基(p-溴苯基)氧化鋶、二甲基(p-氰基苯基)氧化鋶、二甲基(m-硝基苯基)氧化鋶、二甲基(2,4,6-三溴苯基)氧化鋶、二甲基(五氟苯基)氧化鋶、二甲基(p-(三氟甲基)苯基)氧化鋶、二甲基(p-羥苯基)氧化鋶、二甲基(p-巰苯基)氧化鋶、二甲基(p-甲亞磺醯基苯基)氧化鋶、二甲基(p-甲磺醯基苯基)氧化鋶、二甲基(o-乙醯基苯基)氧化鋶、二甲基(o-苯甲醯基苯基)氧化鋶、二甲基(p-甲基苯基)氧化鋶、二甲基(p-異丙基苯基)氧化鋶、二甲基(p-十八基苯基)氧化鋶、二甲基(p-環己基苯基)氧化鋶、二甲基(p-甲氧基苯基)氧化鋶、二甲基(o-甲氧羰基苯基)氧化鋶、二甲基(p-苯基磺醯基苯基)氧化鋶、(7-甲氧基-2-側氧-2H-色烯-4-基)二甲基氧化鋶、(4-甲氧基萘-1-基)二甲基氧化鋶、二甲基(p-異丙氧羰基苯基)氧化鋶、二甲基(2-萘基)氧化鋶、二甲基(9-蒽基)氧化鋶、二乙基苯基氧化鋶、甲基乙基苯基氧化鋶、甲基二苯基氧化鋶、三苯基氧化鋶、二異丙基苯基氧化鋶、二苯基(4-苯基磺醯基-苯基)-氧化鋶、4,4’-雙(二苯基氧化鋶)二苯基硫醚、4,4’-雙[二[(4-(2-羥基-乙氧基)-苯基)]氧化鋶]二苯基硫醚、4,4’-雙(二苯基氧 化鋶)伸聯苯、二苯基(o-氟苯基)氧化鋶、二苯基(m-氯苯基)氧化鋶、二苯基(p-溴苯基)氧化鋶、二苯基(p-氰基苯基)氧化鋶、二苯基(m-硝基苯基)氧化鋶、二苯基(2,4,6-三溴苯基)氧化鋶、二苯基(五氟苯基)氧化鋶、二苯基(p-(三氟甲基)苯基)氧化鋶、二苯基(p-羥苯基)氧化鋶、二苯基(p-巰苯基)氧化鋶、二苯基(p-甲亞磺醯基苯基)氧化鋶、二苯基(p-甲磺醯基苯基)氧化鋶、二苯基(o-乙醯基苯基)氧化鋶、二苯基(o-苯甲醯基苯基)氧化鋶、二苯基(p-甲基苯基)氧化鋶、二苯基(p-異丙基苯基)氧化鋶、二苯基(p-十八基苯基)氧化鋶、二苯基(p-環己基苯基)氧化鋶、二苯基(p-甲氧基苯基)氧化鋶、二苯基(o-甲氧羰基苯基)氧化鋶、二苯基(p-苯基磺醯基苯基)氧化鋶、(7-甲氧基-2-側氧-2H-色烯-4-基)二苯基氧化鋶、(4-甲氧基萘-1-基)二苯基氧化鋶、二苯基(p-異丙氧羰基苯基)氧化鋶、二苯基(2-萘基)氧化鋶、二苯基(9-蒽基)氧化鋶、乙基二苯基氧化鋶、甲基乙基(o-甲苯基)氧化鋶、甲基二(p-甲苯基)氧化鋶、三(p-甲苯基)氧化鋶、二異丙基(4-苯基磺醯基苯基)氧化鋶、二苯基(2-噻吩基)氧化鋶、二苯基(2-呋喃基)氧化鋶、二苯基(9-乙基-9H咔唑-3-基)氧化鋶等,然而,並不限於該等。 Equivalent to the onium cation of the general formula (5) (oxide cation): Examples include: dimethylphenyl oxide oxide, dimethyl (o-fluorophenyl) oxide oxide, dimethyl (m-chlorophenyl) oxide oxide, dimethyl (p-bromophenyl) oxide oxide , Dimethyl (p-cyanophenyl) oxide, dimethyl (m-nitrophenyl) oxide, dimethyl (2,4,6-tribromophenyl) oxide, dimethyl (Pentafluorophenyl) alkoxide, dimethyl (p-(trifluoromethyl)phenyl) alkoxide, dimethyl (p-hydroxyphenyl) alkoxide, dimethyl (p-mercaptophenyl) Oxygen oxide, dimethyl (p-methylsulfinylphenyl) oxymethylene, dimethyl (p-methylsulfonylphenyl) oxymethylene, dimethyl (o-ethoxyphenyl) oxymethylene , Dimethyl (o-benzylphenyl) oxide, dimethyl (p-methylphenyl) oxide, dimethyl (p-isopropylphenyl) oxide, dimethyl ( p-octadecylphenyl) alkoxide, dimethyl (p-cyclohexylphenyl) alkoxide, dimethyl (p-methoxyphenyl) alkoxide, dimethyl (o-methoxycarbonylbenzene Group) oxidized cerium oxide, dimethyl (p-phenylsulfonylphenyl) oxidized cerium oxide, (7-methoxy-2-oxo-2H-chromen-4-yl) dimethyl oxidized cerium oxide, ( 4-Methoxynaphthalene-1-yl) dimethyl alkoxide, dimethyl (p-isopropoxycarbonylphenyl) alkoxide, dimethyl (2-naphthyl) alkoxide, dimethyl (9 -Anthracenyl) oxide, diethylphenyl oxide, methylethylphenyl oxide, methyldiphenyl oxide, triphenyl oxide, diisopropylphenyl oxide, diphenyl oxide (4-Phenylsulfonyl-phenyl)-oxane, 4,4'-bis(diphenyloxane)diphenyl sulfide, 4,4'-bis[di[(4-(2- Hydroxy-ethoxy)-phenyl)] oxybenzone]diphenyl sulfide, 4,4'-bis(diphenyloxy Carbamazepine) biphenylene, diphenyl (o-fluorophenyl) oxide, diphenyl (m-chlorophenyl) oxide, diphenyl (p-bromophenyl) oxide, diphenyl ( p-cyanophenyl) oxide, diphenyl (m-nitrophenyl) oxide, diphenyl (2,4,6-tribromophenyl) oxide, diphenyl (pentafluorophenyl) )Cerbium oxide, diphenyl (p-(trifluoromethyl)phenyl) cerium oxide, diphenyl (p-hydroxyphenyl) cerium oxide, diphenyl (p-mercaptophenyl) cerium oxide, diphenyl (P-methylsulfinylphenyl) oxide, diphenyl (p-methylsulfonylphenyl) oxide, diphenyl (o-ethoxyphenyl) oxide, diphenyl ( o-benzylphenylphenyl) oxide, diphenyl (p-methylphenyl) oxide, diphenyl (p-isopropylphenyl) oxide, diphenyl (p-octadecyl Phenyl) alkoxide, diphenyl (p-cyclohexylphenyl) alkoxide, diphenyl (p-methoxyphenyl) alkoxide, diphenyl (o-methoxycarbonylphenyl) alkoxide, Diphenyl (p-phenylsulfonylphenyl) oxide, (7-methoxy-2-oxo-2H-chromen-4-yl) diphenyl oxide, (4-methoxy Naphthalene-1-yl)diphenyl oxide, diphenyl (p-isopropoxycarbonylphenyl) oxide, diphenyl (2-naphthyl) oxide, diphenyl (9-anthryl) oxidation Cerium oxide, ethyl diphenyl cerium oxide, methyl ethyl (o-tolyl) cerium oxide, methyl bis (p-tolyl) cerium oxide, tri (p-tolyl) cerium oxide, diisopropyl ( 4-Phenylsulfonylphenyl) oxide, diphenyl (2-thienyl) oxide, diphenyl (2-furyl) oxide, diphenyl (9-ethyl-9Hcarbazole- 3-yl) oxirane etc., however, it is not limited to these.
相當於一般式(6)之鎓陽離子(鏻陽離子):鏻陽離子之例子:可列舉如:三甲基苯基鏻、三乙基苯基鏻、四苯基鏻、三苯基(p-氟苯基)鏻、三苯基(o-氯苯基)鏻、三苯基(m-溴苯基)鏻、三苯基(p-氰基苯基)鏻、三苯基(m-硝基苯基)鏻、三 苯基(p-苯基磺醯基苯基)鏻、(7-甲氧基-2-側氧-2H-色烯-4-基)三苯基鏻、三苯基(o-羥苯基)鏻、三苯基(o-乙醯基苯基)鏻、三苯基(m-苯甲醯基苯基)鏻、三苯基(p-甲基苯基)鏻、三苯基(p-異丙氧基苯基)鏻、三苯基(o-甲氧羰基苯基)鏻、三苯基(1-萘基)鏻、三苯基(9-蒽基)鏻、三苯基(2-噻吩基)鏻、三苯基(2-呋喃基)鏻、三苯基(9-乙基-9H咔唑-3-基)鏻等,然而,並不限於該等。 Equivalent to the onium cation (phosphonium cation) of the general formula (6): Examples of phosphonium cations: for example: trimethylphenylphosphonium, triethylphenylphosphonium, tetraphenylphosphonium, triphenyl (p-fluoro Phenyl)phosphonium, triphenyl(o-chlorophenyl)phosphonium, triphenyl(m-bromophenyl)phosphonium, triphenyl(p-cyanophenyl)phosphonium, triphenyl(m-nitro Phenyl)phosphonium, three Phenyl (p-phenylsulfonylphenyl) phosphonium, (7-methoxy-2-oxo-2H-chromen-4-yl) triphenylphosphonium, triphenyl (o-hydroxyphenyl ) Phosphonium, triphenyl (o-acetyl phenyl) phosphonium, triphenyl (m-benzyl phenyl) phosphonium, triphenyl (p-methylphenyl) phosphonium, triphenyl (p -Isopropoxyphenyl)phosphonium, triphenyl(o-methoxycarbonylphenyl)phosphonium, triphenyl(1-naphthyl)phosphonium, triphenyl(9-anthryl)phosphonium, triphenyl( 2-thienyl)phosphonium, triphenyl(2-furyl)phosphonium, triphenyl(9-ethyl-9Hcarbazol-3-yl)phosphonium, etc., however, it is not limited to these.
相當於一般式(7)之鎓陽離子(吡啶鎓陽離子):吡啶鎓陽離子之例子:可列舉如:N-苯基吡啶鎓、N-(o-氯苯基)吡啶鎓、N-(m-氯苯基)吡啶鎓、N-(p-氰基苯基)吡啶鎓、N-(o-硝基苯基)吡啶鎓、N-(p-乙醯基苯基)吡啶鎓、N-(p-異丙基苯基)吡啶鎓、N-(p-十八烷氧基苯基)吡啶鎓、N-(p-甲氧羰基苯基)吡啶鎓、N-(9-蒽基)吡啶鎓、2-氯-1-苯基吡啶鎓、2-氰基-1-苯基吡啶鎓、2-甲基-1-苯基吡啶鎓、2-乙烯基-1-苯基吡啶鎓、2-苯基-1-苯基吡啶鎓、1,2-二苯基吡啶鎓、2-甲氧基-1-苯基吡啶鎓、2-苯氧基-1-苯基吡啶鎓、2-乙醯基-1-(p-甲苯基)吡啶鎓、2-甲氧羰基-1-(p-甲苯基)吡啶鎓、3-氟-1-萘基吡啶鎓、4-甲基-1-(2-呋喃基)吡啶鎓、N-甲基吡啶鎓、N-乙基吡啶鎓等,然而,並不限於該等。 Equivalent to the onium cation of the general formula (7) (pyridinium cation): Examples of pyridinium cations: N-phenylpyridinium, N-(o-chlorophenyl)pyridinium, N-(m- Chlorophenyl)pyridinium, N-(p-cyanophenyl)pyridinium, N-(o-nitrophenyl)pyridinium, N-(p-acetylphenyl)pyridinium, N-( p-isopropylphenyl)pyridinium, N-(p-octadecyloxyphenyl)pyridinium, N-(p-methoxycarbonylphenyl)pyridinium, N-(9-anthryl)pyridine Onium, 2-chloro-1-phenylpyridinium, 2-cyano-1-phenylpyridinium, 2-methyl-1-phenylpyridinium, 2-vinyl-1-phenylpyridinium, 2 -Phenyl-1-phenylpyridinium, 1,2-diphenylpyridinium, 2-methoxy-1-phenylpyridinium, 2-phenoxy-1-phenylpyridinium, 2-ethyl Acyl-1-(p-tolyl)pyridinium, 2-methoxycarbonyl-1-(p-tolyl)pyridinium, 3-fluoro-1-naphthylpyridinium, 4-methyl-1-( 2-furyl)pyridinium, N-methylpyridinium, N-ethylpyridinium, etc., however, it is not limited to these.
相當於一般式(8)之鎓陽離子(喹啉鎓陽離子):喹啉鎓陽離子之例子:可列舉如:N-甲基喹啉鎓、N-乙基喹啉鎓、N-苯基喹啉鎓、N-萘基喹啉鎓、N-(o-氯苯基)喹啉鎓、N-(m-氯苯基) 喹啉鎓、N-(p-氰基苯基)喹啉鎓、N-(o-硝基苯基)喹啉鎓、N-(p-乙醯基苯基)喹啉鎓、N-(p-異丙基苯基)喹啉鎓、N-(p-十八烷氧基苯基)喹啉鎓、N-(p-甲氧羰基苯基)喹啉鎓、N-(9-蒽基)喹啉鎓、2-氯-1-苯基喹啉鎓、2-氰基-1-苯基喹啉鎓、2-甲基-1-苯基喹啉鎓、2-乙烯基-1-苯基喹啉鎓、2-苯基-1-苯基喹啉鎓、1,2-二苯基喹啉鎓、2-甲氧基-1-苯基喹啉鎓、2-苯氧基-1-苯基喹啉鎓、2-乙醯基-1-苯基喹啉鎓、2-甲氧羰基-1-苯基喹啉鎓、3-氟-1-苯基喹啉鎓、4-甲基-1-苯基喹啉鎓、2-甲氧基-1-(p-甲苯基)喹啉鎓、2-苯氧基-1-(2-呋喃基)喹啉鎓、2-乙醯基-1-(2-噻吩基)喹啉鎓、2-甲氧羰基-1-甲基喹啉鎓、3-氟-1-乙基喹啉鎓、4-甲基-1-異丙基喹啉鎓等,然而,並不限於該等。 Equivalent to the onium cation of the general formula (8) (quinolinium cation): Examples of quinolinium cations: N-methylquinolinium, N-ethylquinolinium, N-phenylquinoline Onium, N-naphthylquinolinium, N-(o-chlorophenyl) quinolinium, N-(m-chlorophenyl) Quinolinium, N-(p-cyanophenyl)quinolinium, N-(o-nitrophenyl)quinolinium, N-(p-acetylphenyl)quinolinium, N-( p-isopropylphenyl) quinolinium, N-(p-octadecyloxyphenyl) quinolinium, N-(p-methoxycarbonylphenyl) quinolinium, N-(9-anthracene Group) quinolinium, 2-chloro-1-phenylquinolinium, 2-cyano-1-phenylquinolinium, 2-methyl-1-phenylquinolinium, 2-vinyl-1 -Phenylquinolinium, 2-phenyl-1-phenylquinolinium, 1,2-diphenylquinolinium, 2-methoxy-1-phenylquinolinium, 2-phenoxy -1-phenylquinolinium, 2-acetoxy-1-phenylquinolinium, 2-methoxycarbonyl-1-phenylquinolinium, 3-fluoro-1-phenylquinolinium, 4 -Methyl-1-phenylquinolinium, 2-methoxy-1-(p-tolyl)quinolinium, 2-phenoxy-1-(2-furyl)quinolinium, 2- Acetyl-1-(2-thienyl)quinolinium, 2-methoxycarbonyl-1-methylquinolinium, 3-fluoro-1-ethylquinolinium, 4-methyl-1-iso Propylquinolinium and the like, however, are not limited to these.
相當於一般式(9)之鎓陽離子(異喹啉鎓陽離子):異喹啉鎓陽離子之例子:可列舉如:N-苯基異喹啉鎓、N-甲基異喹啉鎓、N-乙基異喹啉鎓、N-(o-氯苯基)異喹啉鎓、N-(m-氯苯基)異喹啉鎓、N-(p-氰基苯基)異喹啉鎓、N-(o-硝基苯基)異喹啉鎓、N-(p-乙醯基苯基)異喹啉鎓、N-(p-異丙基苯基)異喹啉鎓、N-(p-十八烷氧基苯基)異喹啉鎓、N-(p-甲氧羰基苯基)異喹啉鎓、N-(9-蒽基)異喹啉鎓、1,2-二苯基異喹啉鎓、N-(2-呋喃基)異喹啉鎓、N-(2-噻吩基)異喹啉鎓、N-萘基異喹啉鎓等,然而,並不限於該等。 Equivalent to the onium cation of the general formula (9) (isoquinolinium cation): Examples of the isoquinolinium cation: N-phenylisoquinolinium, N-methylisoquinolinium, N- Ethyl isoquinolinium, N-(o-chlorophenyl) isoquinolinium, N-(m-chlorophenyl) isoquinolinium, N-(p-cyanophenyl) isoquinolinium, N-(o-nitrophenyl) isoquinolinium, N-(p-acetylphenyl) isoquinolinium, N-(p-isopropylphenyl) isoquinolinium, N-( p-octadecyloxyphenyl) isoquinolinium, N-(p-methoxycarbonylphenyl) isoquinolinium, N-(9-anthryl) isoquinolinium, 1,2-diphenyl Isoquinolinium, N-(2-furyl)isoquinolinium, N-(2-thienyl)isoquinolinium, N-naphthylisoquinolinium, etc., however, it is not limited to these.
相當於一般式(10)之鎓陽離子(苯并噁唑鎓陽離子、苯并噻唑鎓陽離子): 苯并噁唑鎓陽離子之例子:可列舉如:N-甲基苯并噁唑鎓、N-乙基苯并噁唑鎓、N-萘基苯并噁唑鎓、N-苯基苯并噁唑鎓、N-(p-氟苯基)苯并噁唑鎓、N-(p-氯苯基)苯并噁唑鎓、N-(p-氰基苯基)苯并噁唑鎓、N-(o-甲氧羰基苯基)苯并噁唑鎓、N-(2-呋喃基)苯并噁唑鎓、N-(o-氟苯基)苯并噁唑鎓、N-(p-氰基苯基)苯并噁唑鎓、N-(m-硝基苯基)苯并噁唑鎓、N-(p-異丙氧羰基苯基)苯并噁唑鎓、N-(2-噻吩基)苯并噁唑鎓、N-(m-羧苯基)苯并噁唑鎓、2-巰基-3-苯基苯并噁唑鎓、2-甲基-3-苯基苯并噁唑鎓、2-甲硫基-3-(4-苯基磺醯基苯基)苯并噁唑鎓、6-羥基-3-(p-甲苯基)苯并噁唑鎓、7-巰基-3-苯基苯并噁唑鎓、4,5-二氟-3-乙基苯并噁唑鎓等,然而,並不限於該等。 Equivalent to the onium cation of general formula (10) (benzoxazolium cation, benzothiazolium cation): Examples of benzoxazolium cations: N-methylbenzoxazolium, N-ethylbenzoxazolium, N-naphthylbenzoxazolium, N-phenylbenzoxazolium Oxazolium, N-(p-fluorophenyl)benzoxazolium, N-(p-chlorophenyl)benzoxazolium, N-(p-cyanophenyl)benzoxazolium, N -(o-methoxycarbonylphenyl)benzoxazolium, N-(2-furyl)benzoxazolium, N-(o-fluorophenyl)benzoxazolium, N-(p- Cyanophenyl)benzoxazolium, N-(m-nitrophenyl)benzoxazolium, N-(p-isopropoxycarbonylphenyl)benzoxazolium, N-(2- Thienyl)benzoxazolium, N-(m-carboxyphenyl)benzoxazolium, 2-mercapto-3-phenylbenzoxazolium, 2-methyl-3-phenylbenzoxazol Oxazolium, 2-methylthio-3-(4-phenylsulfonylphenyl)benzoxazolium, 6-hydroxy-3-(p-tolyl)benzoxazolium, 7-mercapto- 3-phenylbenzoxazolium, 4,5-difluoro-3-ethylbenzoxazolium, etc., however, it is not limited to these.
苯并噻唑鎓陽離子之例子:可列舉如:N-甲基苯并噻唑鎓、N-乙基苯并噻唑鎓、N-苯基苯并噻唑鎓、N-(1-萘基)苯并噻唑鎓、N-(p-氟苯基)苯并噻唑鎓、N-(p-氯苯基)苯并噻唑鎓、N-(p-氰基苯基)苯并噻唑鎓、N-(o-甲氧羰基苯基)苯并噻唑鎓、N-(p-甲苯基)苯并噻唑鎓、N-(o-氟苯基)苯并噻唑鎓、N-(m-硝基苯基)苯并噻唑鎓、N-(p-異丙氧羰基苯基)苯并噻唑鎓、N-(2-呋喃基)苯并噻唑鎓、N-(4-甲硫基苯基)苯并噻唑鎓、N-(4-苯基磺醯基苯基)苯并噻唑鎓、N-(2-萘基)苯并噻唑鎓、N-(m-羧苯基)苯并噻唑鎓、2-巰基-3-苯基苯并噻唑鎓、2-甲基-3-苯基苯并噻唑鎓、2-甲硫基-3-苯基苯并噻唑鎓、6-羥基-3-苯基苯并噻唑鎓、7-巰基-3-苯基苯并噻唑鎓、4,5-二氟-3- 苯基苯并噻唑鎓等,然而,並不限於該等。 Examples of benzothiazolium cations: N-methylbenzothiazolium, N-ethylbenzothiazolium, N-phenylbenzothiazolium, N-(1-naphthyl)benzothiazole Onium, N-(p-fluorophenyl)benzothiazolium, N-(p-chlorophenyl)benzothiazolium, N-(p-cyanophenyl)benzothiazolium, N-(o- Methoxycarbonylphenyl)benzothiazolium, N-(p-tolyl)benzothiazolium, N-(o-fluorophenyl)benzothiazolium, N-(m-nitrophenyl)benzo Thiazolium, N-(p-isopropoxycarbonylphenyl) benzothiazolium, N-(2-furyl)benzothiazolium, N-(4-methylthiophenyl) benzothiazolium, N -(4-phenylsulfonylphenyl)benzothiazolium, N-(2-naphthyl)benzothiazolium, N-(m-carboxyphenyl)benzothiazolium, 2-mercapto-3- Phenylbenzothiazolium, 2-methyl-3-phenylbenzothiazolium, 2-methylthio-3-phenylbenzothiazolium, 6-hydroxy-3-phenylbenzothiazolium, 7 -Mercapto-3-phenylbenzothiazolium, 4,5-difluoro-3- Phenylbenzothiazolium and the like, however, are not limited to these.
相當於一般式(11)之鎓陽離子(呋喃基或噻吩基錪鎓陽離子):可列舉如:二呋喃基錪鎓、二噻吩基錪鎓、雙(4,5-二甲基-2-呋喃基)錪鎓、雙(5-氯-2-噻吩基)錪鎓、雙(5-氰基-2-呋喃基)錪鎓、雙(5-硝基-2-噻吩基)錪鎓、雙(5-乙醯基-2-呋喃基)錪鎓、雙(5-羧基-2-噻吩基)錪鎓、雙(5-甲氧羰基-2-呋喃基)錪鎓、雙(5-苯基-2-呋喃基)錪鎓、雙(5-(p-甲氧基苯基)-2-噻吩基)錪鎓、雙(5-乙烯基-2-呋喃基)錪鎓、雙(5-乙炔基-2-噻吩基)錪鎓、雙(5-環己基-2-呋喃基)錪鎓、雙(5-羥基-2-噻吩基)錪鎓、雙(5-苯氧基-2-呋喃基)錪鎓、雙(5-巰基-2-噻吩基)錪鎓、雙(5-丁硫基-2-噻吩基)錪鎓、雙(5-苯硫基-2-噻吩基)錪鎓等,然而,並不限於該等。 Equivalent to the onium cation of the general formula (11) (furanyl or thienylphosphonium cation): examples include difuranylphosphonium, dithienylphosphonium, and bis(4,5-dimethyl-2-furan Group) phosphonium, bis(5-chloro-2-thienyl) sulfonium, bis(5-cyano-2-furanyl) sulfonium, bis(5-nitro-2-thienyl) sulfonium, bis (5-Acetyl-2-furanyl) sulfonium, bis(5-carboxy-2-thienyl) sulfonium, bis(5-methoxycarbonyl-2-furanyl) sulfonium, bis(5-benzene Yl-2-furyl)phosphonium, bis(5-(p-methoxyphenyl)-2-thienyl)phosphonium, bis(5-vinyl-2-furyl)phosphonium, bis(5 -Ethynyl-2-thienyl) sulfonium, bis(5-cyclohexyl-2-furyl) sulfonium, bis(5-hydroxy-2-thienyl) sulfonium, bis(5-phenoxy-2 -Furanyl) sulfonium, bis(5-mercapto-2-thienyl) sulfonium, bis(5-butylthio-2-thienyl) sulfonium, bis(5-phenylthio-2-thienyl) Phonium, etc., however, are not limited to these.
相當於一般式(12)之鎓陽離子(二芳基錪鎓陽離子):可列舉如:二苯基錪鎓、雙(p-甲苯基)錪鎓、雙(p-辛基苯基)錪鎓、雙(p-十八基苯基)錪鎓、雙(p-辛氧基苯基)錪鎓、雙(p-十八烷氧基苯基)錪鎓、苯基(p-十八烷氧基苯基)錪鎓、4-異丙基-4’-甲基二苯基錪鎓、(4-異丁基苯基)-p-甲苯基錪鎓、雙(1-萘基)錪鎓、雙(4-苯基磺醯基苯基)錪鎓、苯基(6-苯甲醯基-9-乙基-9H-咔唑-3-基)錪鎓、(7-甲氧基-2-側氧-2H-色烯-3-基)-4’-異丙基苯基錪鎓等,然而,並不限於該等。 Equivalent to the onium cation of the general formula (12) (diarylionium cation): examples include: diphenyl sulfonium, bis(p-tolyl) sulfonium, bis(p-octylphenyl) sulfonium , Bis(p-octadecylphenyl) sulfonium, bis(p-octyloxyphenyl) sulfonium, bis(p-octadecyloxyphenyl) sulfonium, phenyl (p-octadecane Oxyphenyl) konium, 4-isopropyl-4'-methyldiphenyl konium, (4-isobutylphenyl)-p-tolyl konium, bis(1-naphthyl) konium Onium, bis(4-phenylsulfonylphenyl) sulfonium, phenyl (6-benzyl-9-ethyl-9H-carbazol-3-yl) sulfonium, (7-methoxy -2-oxo-2H-chromen-3-yl)-4'-isopropylphenylphosphonium, etc., however, it is not limited to these.
其次,說明一般式(3)中的相對陰離子X-。 Next, the relative anion X - in the general formula (3) will be explained.
一般式(3)中的相對陰離子X-原則上並無特殊之限制,然而,宜為非親核性陰離子。當相對陰離子X-為非親核性陰離子時,由於不易引起共存於分子內之陽離子或併用之各種材料中的親核反應,因此,結果可提升藉由一般式(2)所標示之光酸產生劑本身或使用其之接著劑之經時安定性。在此所謂之非親核性陰離子是指引起親核反應之能力低之陰離子。此種陰離子可列舉如:PF6 -、SbF6 -、AsF6 -、SbCl6 -、BiCl5 -、SnCl6 -、ClO4 -、二硫胺基甲酸酯陰離子、SCN-等。 The relative anion X - in the general formula (3) is not particularly limited in principle, however, it is preferably a non-nucleophilic anion. When the relative anion X -is a non-nucleophilic anion, since it is not easy to cause nucleophilic reactions in the cations coexisting in the molecule or various materials used in combination, the result can be improved by the photoacid generation indicated by the general formula (2) The stability over time of the agent itself or its adhesive. The non-nucleophilic anions referred to herein refer to anions with low ability to cause nucleophilic reactions. Such anions include such as: PF 6 -, SbF 6 - , AsF 6 -, SbCl 6 -, BiCl 5 -, SnCl 6 -, ClO 4 -, urethane disulfide anion, SCN - and the like.
於前述例示之陰離子中,特別宜作為一般式(3)中的相對陰離子X-者可列舉如:PF6 -、SbF6 -及AsF6 -,特別理想的可列舉如:PF6 -、SbF6 -。 In the illustrated embodiment of the anion, particularly suitable as a general formula opposing anions (3) X - as exemplified by: PF 6 -, SbF 6 - and AsF 6 -, particularly preferably include such as: PF 6 -, SbF 6 -.
故,構成光酸產生劑(B)之理想鎓鹽之具體例是由以下所構成的鎓鹽,即:藉由前述例示之一般式(3)~一般式(12)所表示之鎓陽離子之結構之具體例與選自於PF6 -、SbF6 -、AsF6 -、SbCl6 -、BiCl5 -、SnCl6 -、ClO4 -、二硫胺基甲酸酯陰離子、SCN-之陰離子。 Therefore, a specific example of an ideal onium salt constituting the photoacid generator (B) is an onium salt composed of the following, namely: the onium cation represented by the general formula (3) to the general formula (12) exemplified above specific examples of the structures selected from PF 6 -, SbF 6 -, AsF 6 -, SbCl 6 -, BiCl 5 -, SnCl 6 -, ClO 4 -, urethane disulfide anion, SCN - anion of.
具體而言,可列舉為光酸產生劑(B)之理想具體例的是:「CYRACURE UVI-6992」、「CYRACURE UVI-6974」(以上為日本陶氏化學(Dow Chemical)股份有限公司製)、「ADEKA OPTOMER SP150」、「ADEKA OPTOMER SP152」、「ADEKA OPTOMER SP170」、「ADEKA OPTOMER SP172」(以上為艾迪科(ADEKA)股份有限公司製)、「IRGACURE250」(汽巴精化(Ciba Specialty Chemicals)公 司製)、「CI-5102」、「CI-2855」(以上為日本曹達公司製)、「SAN-AID SI-60L」、「SAN-AID SI-80L」、「SAN-AID SI-100L」、「SAN-AID SI-110L」、「SAN-AID SI-180L」(以上為三新化學公司製)、「CPI-100P」、「CPI-100A」(以上為三亞普羅(SAN-APRO)股份有限公司製)、「WPI-069」、「WPI-113」、「WPI-116」、「WPI-041」、「WPI-044」、「WPI-054」、「WPI-055」、「WPAG-281」、「WPAG-567」、「WPAG-596」(以上為和光純藥公司製)。 Specifically, examples of ideal specific examples of the photoacid generator (B) include: "CYRACURE UVI-6992" and "CYRACURE UVI-6974" (above are manufactured by Japan Dow Chemical Co., Ltd.) , ``ADEKA OPTOMER SP150'', ``ADEKA OPTOMER SP152'', ``ADEKA OPTOMER SP170'', ``ADEKA OPTOMER SP172'' (above manufactured by ADEKA Co., Ltd.), ``IRGACURE250'' (Ciba Specialty Chemicals) Company), ``CI-5102'', ``CI-2855'' (the above is manufactured by Soda Japan), ``SAN-AID SI-60L'', ``SAN-AID SI-80L'', ``SAN-AID SI-100L'' , "SAN-AID SI-110L", "SAN-AID SI-180L" (above manufactured by Sanxin Chemical Co., Ltd.), "CPI-100P", "CPI-100A" (above are SAN-APRO) shares Co., Ltd.), ``WPI-069'', ``WPI-113'', ``WPI-116'', ``WPI-041'', ``WPI-044'', ``WPI-054'', ``WPI-055'', ``WPAG- "281", "WPAG-567", "WPAG-596" (above manufactured by Wako Pure Chemical Industries, Ltd.).
相對於硬化性成分之全量100重量份,光酸產生劑(B)之含量為10重量份以下,且宜為0.01~10重量份,更宜為0.05~5重量份,特別是宜為0.1~3重量份。 The content of the photoacid generator (B) is less than 10 parts by weight relative to the total amount of the hardening component of 100 parts by weight, and is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, and particularly preferably 0.1 to 3 parts by weight.
<包含烷氧基、環氧基中任一者之化合物(C)> <Compound (C) containing any of alkoxy group and epoxy group>
於前述活性能量線硬化型接著劑中,可含有包含烷氧基、環氧基中任一者之化合物(C)。舉例言之,在與PVA系偏光件之羥基之關係中,包含烷氧基之化合物(C1)會進行烷氧基與羥基之縮合反應,包含環氧基之化合物(C2)會進行環氧基與羥基之加成反應,且可賦予活性能量線硬化型接著劑更堅固之接著性。使用包含環氧基之化合物(C2)時,藉由環氧基與羥基之加成反應,於反應後生成二級羥基,且可能會使本發明之整體吸水率上升,因此,更宜使用具有烷氧基之化合物(C1)。即,隔著含有光酸產生劑(B)與具有烷氧基之化合物(C1)的活性能量線硬化型接著劑,積層偏光件與透明保護薄膜,並在活性能量線照射下,藉由產生自光酸產生劑(B)之酸,具有烷氧基之化合物(C1)之 烷氧基與偏光件之羥基會進行縮合反應,並顯現偏光件與透明保護薄膜良好之接著性。又,藉由具有烷氧基之化合物(C1)彼此之縮合反應,形成吸水率更低之接著劑層,且可滿足高溫高濕下之嚴苛環境下的光學耐久性。 The active energy ray-curable adhesive described above may contain a compound (C) containing any one of an alkoxy group and an epoxy group. For example, in the relationship with the hydroxyl group of the PVA polarizer, the compound (C1) containing an alkoxy group will undergo a condensation reaction of an alkoxy group and a hydroxyl group, and the compound (C2) containing an epoxy group will undergo an epoxy group Addition reaction with hydroxyl groups, and can give the active energy ray hardening adhesive more firm adhesion. When using an epoxy group-containing compound (C2), by the addition reaction of an epoxy group and a hydroxyl group, a secondary hydroxyl group is formed after the reaction, and the overall water absorption rate of the present invention may be increased. Therefore, it is more suitable to use Alkoxy compound (C1). That is, through the active energy ray-curable adhesive containing the photoacid generator (B) and the compound having an alkoxy group (C1), the polarizer and the transparent protective film are laminated, and under the irradiation of the active energy ray, by generating Acids from photoacid generators (B), compounds with alkoxy groups (C1) The alkoxy group and the hydroxyl group of the polarizer will undergo a condensation reaction, and show good adhesion between the polarizer and the transparent protective film. In addition, by the condensation reaction of the compounds (C1) having alkoxy groups, an adhesive layer with a lower water absorption rate is formed, and the optical durability in a severe environment under high temperature and high humidity can be satisfied.
於前述活性能量線硬化型接著劑中,包含烷氧 基、環氧基中任一者之化合物(C)可單獨使用1種,亦可組合使用複數種。又,包含烷氧基、環氧基中任一者之化合物(C)亦可併用包含烷氧基之化合物(C1)與包含環氧基之化合物(C2)來使用。又,包含烷氧基、環氧基中任一者之化合物(C)可與光酸產生劑(B)併用或未併用而使用,然而,若由促進PVA系偏光件之羥基與烷氧基、環氧基之反應之觀點來看,則包含烷氧基、環氧基中任一者之化合物(C)宜與光酸產生劑(B)併用。 The aforementioned active energy ray-curable adhesive contains alkoxy The compound (C) of any one of the group and the epoxy group may be used alone or in combination. Moreover, the compound (C) containing either an alkoxy group or an epoxy group can also be used together with the compound (C1) containing an alkoxy group and the compound (C2) containing an epoxy group. In addition, the compound (C) containing any of the alkoxy group and the epoxy group may be used with or without the photoacid generator (B). However, if the hydroxyl and alkoxy groups of the PVA polarizer are promoted From the viewpoint of the reaction of epoxy groups, the compound (C) containing any of alkoxy groups and epoxy groups is preferably used in combination with the photoacid generator (B).
(具有烷氧基之化合物(C1)) (Compound with alkoxy group (C1))
分子內具有烷氧基之化合物(C1)只要是分子內具有1個以上之烷氧基,則無特殊之限制,可使用公知者。舉例言之,可列舉如:具有藉由一般式:-(CH2)n-O-R(式中,n為1~3之整數,R表示碳數1~4之烷基或H。前述式中的R宜為甲基。)所表示之烷氧基作為取代基之化合物。具體而言,舉例言之,可列舉如:烷氧基烷基(甲基)丙烯酸酯、烷氧基烷基(甲基)丙烯醯胺等含有烷氧基之自由基聚合性化合物、羥甲基三聚氰胺、烷氧基甲基化三聚氰胺等三聚氰胺化合物、胺基樹脂及矽烷耦合劑。含有烷氧基之自由基聚合性化合物之具體例可列舉如:笠野興產公司製之 WASMER 2MA、WASMER 3MA、WASMER IBM、N-異丁氧基甲基丙烯醯胺、WASMER EMA、N-MAM-PC、MM90、WASMER A等。三聚氰胺化合物之具體例可例示:住友化學公司製之SUMITEX RESIN系列之M-3、MK、M-6、M-100、MC等或三和化學股份有限公司製之NIKALAC MW-30、MW-100LM、MX-750LM、MX-280、MX-270等。 於該等中,若由反應性之觀點來看,則宜使用WASMER 2MA、N-MAM-PC、MX-750LM等。另,在計算接著劑層之玻璃轉移溫度Tg時,作成未將具有烷氧基之化合物及高分子(C1)納入計算。 The compound (C1) having an alkoxy group in the molecule is not particularly limited as long as it has one or more alkoxy groups in the molecule, and known ones can be used. For example, it can be exemplified by the following general formula: -(CH 2 ) n -OR (where n is an integer of 1 to 3, and R represents an alkyl group of 1 to 4 carbon or H. In the foregoing formula R is preferably a methyl group.) The compound represented by an alkoxy group as a substituent. Specifically, for example, an alkoxy-containing radical polymerizable compound such as alkoxyalkyl (meth)acrylate, alkoxyalkyl (meth)acrylamide, hydroxymethyl Based melamine, alkoxymethylated melamine and other melamine compounds, amine-based resin and silane coupling agent. Specific examples of the radical polymerizable compound containing an alkoxy group include: WASMER 2MA, WASMER 3MA, WASMER IBM, N-isobutoxymethacrylamide, WASMER EMA, N-MAM manufactured by Kasano Kosei Corporation -PC, MM90, WASMER A, etc. Specific examples of melamine compounds can be exemplified: M-3, MK, M-6, M-100, MC, etc. of SUMITEX RESIN series manufactured by Sumitomo Chemical Co., Ltd. or NIKALAC MW-30, MW-100LM manufactured by Sanwa Chemical Co., Ltd. , MX-750LM, MX-280, MX-270, etc. Among these, from the viewpoint of reactivity, WASMER 2MA, N-MAM-PC, MX-750LM, etc. are preferably used. In addition, when calculating the glass transition temperature Tg of the adhesive layer, the compound having an alkoxy group and the polymer (C1) were not included in the calculation.
(具有環氧基之化合物(C2)) (Compound with epoxy group (C2))
具有環氧基之化合物(C2)可使用分子內具有1個以上之環氧基之化合物或分子內具有2個以上之環氧基之高分子(環氧樹脂)。使用高分子(環氧樹脂)時,亦可併用分子內具有二個以上具有與環氧基之反應性之官能基之化合物。在此,舉例言之,所謂具有與環氧基之反應性之官能基可列舉如:羧基、酚性羥基、巰基、一級或二級之芳香族胺基等。考慮三維硬化性,該等官能基特別宜為一分子中具有2個以上者。 As the compound (C2) having an epoxy group, a compound having more than one epoxy group in the molecule or a polymer (epoxy resin) having more than two epoxy groups in the molecule can be used. When a polymer (epoxy resin) is used, a compound having two or more functional groups having reactivity with epoxy groups in the molecule may be used in combination. Here, for example, the functional group having reactivity with an epoxy group may include a carboxyl group, a phenolic hydroxyl group, a mercapto group, a primary or secondary aromatic amine group, and the like. Considering the three-dimensional hardenability, these functional groups are particularly preferably those having two or more in one molecule.
舉例言之,分子內具有1個以上之環氧基之高分子可列舉如:環氧樹脂,並包括:衍生自雙酚A與環氧氯丙烷之雙酚A型環氧樹脂、衍生自雙酚F與環氧氯丙烷之雙酚F型環氧樹脂、雙酚S型環氧樹脂、苯酚酚醛型環氧樹脂、甲酚酚醛型環氧樹脂、雙酚A酚醛型環氧樹脂、雙酚F酚醛 型環氧樹脂、脂環式環氧樹脂、二苯基醚型環氧樹脂、氫醌型環氧樹脂、萘型環氧樹脂、聯苯型環氧樹脂、茀型環氧樹脂、三官能型環氧樹脂或四官能型環氧樹脂等多官能型環氧樹脂、縮水甘油酯型環氧樹脂、縮水甘油胺型環氧樹脂、尿囊素型環氧樹脂、三聚異氰酸酯型環氧樹脂、脂肪族鏈狀環氧樹脂等,且該等環氧樹脂亦可鹵素化,亦可氫化。舉例言之,市售之環氧樹脂製品可列舉如:日本環氧樹脂股份有限公司製之JER塗料828、1001、801N、806、807、152、604、630、871、YX8000、YX8034、YX4000、DIC股份有限公司製之EPICLON830、EXA835LV、HP4032D、HP820、艾迪科股份有限公司製之EP4100系列、EP4000系列、EPU系列、大賽璐(DAICEL)化學股份有限公司製之CELLOXIDE系列(2021、2021P、2083、2085、3000等)、EPOLEAD系列、EHPE系列、新日鐵化學公司製之YD系列、YDF系列、YDCN系列、YDB系列、苯氧基樹脂(由雙酚類與環氧氯丙烷合成之多羥基聚醚且兩末端具有環氧基;YP系列等)、長瀨化成(Nagase Chemtex)公司製之DENACOL系列、共榮社化學公司製之EPOLIGHT系列等,然而,並不限於該等。該等環氧樹脂亦可併用2種以上。另,在計算接著劑層之玻璃轉移溫度Tg時,作成未將具有環氧基之化合物(C2)納入計算。 For example, polymers with more than one epoxy group in the molecule can be exemplified by epoxy resins, and include: bisphenol A epoxy resins derived from bisphenol A and epichlorohydrin, derived from bisphenol Bisphenol F epoxy resin, bisphenol S epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, bisphenol A novolac epoxy resin, bisphenol F phenolic Epoxy resin, alicyclic epoxy resin, diphenyl ether epoxy resin, hydroquinone epoxy resin, naphthalene epoxy resin, biphenyl epoxy resin, fuze epoxy resin, trifunctional epoxy resin Multifunctional epoxy resin such as epoxy resin or tetrafunctional epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, allantoin epoxy resin, triisocyanate epoxy resin, Aliphatic chain epoxy resin, etc., and these epoxy resins can also be halogenated or hydrogenated. For example, commercially available epoxy resin products include: JER coatings 828, 1001, 801N, 806, 807, 152, 604, 630, 871, YX8000, YX8034, YX4000, manufactured by Japan Epoxy Resin Co., Ltd. EPICLON830, EXA835LV, HP4032D, HP820 manufactured by DIC Co., Ltd., EP4100 series, EP4000 series, EPU series, and DAICEL Chemical Co., Ltd.-made CELLOXIDE series (2021, 2021P, 2083) , 2085, 3000, etc.), EPOLEAD series, EHPE series, YD series, YDF series, YDCN series, YDB series, phenoxy resin (polyhydroxyl synthesized from bisphenols and epichlorohydrin) Polyether with epoxy groups at both ends; YP series, etc.), DENACOL series manufactured by Nagase Chemtex, EPOLIGHT series manufactured by Kyoeisha Chemical Co., etc. However, it is not limited to these. Two or more of these epoxy resins may be used in combination. In addition, when calculating the glass transition temperature Tg of the adhesive layer, the compound (C2) having an epoxy group was not included in the calculation.
相對於硬化性成分之全量100重量份,包含烷氧 基、環氧基中任一者之化合物(C)之摻合量通常為30重量份以下,若活性能量線硬化型接著劑中的前述化合物(C)之含 量過多,則接著性會降低,並有對掉落試驗之耐衝擊性惡化之情形。活性能量線硬化型接著劑中的前述化合物(C)之含量更宜為20重量份以下。另一方面,若由耐水性之觀點來看,則活性能量線硬化型接著劑中,宜含有前述化合物(C)2重量份以上,更宜含有5重量份以上。 Contains 100 parts by weight of the total amount of hardenable components, including alkoxy The compounding amount of the compound (C) of any one of the group and the epoxy group is usually 30 parts by weight or less, if the content of the compound (C) in the active energy ray-curable adhesive is If the amount is too large, the adhesiveness will decrease, and the impact resistance to the drop test may deteriorate. The content of the aforementioned compound (C) in the active energy ray-curable adhesive is more preferably 20 parts by weight or less. On the other hand, from the viewpoint of water resistance, the active energy ray-curable adhesive preferably contains 2 parts by weight or more of the compound (C), more preferably 5 parts by weight or more.
<異氰酸酯化合物(D)> <isocyanate compound (D)>
本發明之活性能量線硬化型接著劑可含有異氰酸酯化合物(D)。異氰酸酯化合物(D)是分子中具有至少1個異氰酸酯基之化合物。當活性能量線硬化型接著劑含有異氰酸酯化合物(D)時,藉由偏光件表面之羥基與異氰酸酯基相互作用,可賦予偏光薄膜更堅固之接著性、耐水性。又,當活性能量線硬化型接著劑包含有含N-羥烷基之(甲基)丙烯醯胺衍生物作為自由基聚合性化合物時,若含N-羥烷基之(甲基)丙烯醯胺衍生物之含量變多,則由於羥基包含於接著劑層中,因此,會有整體吸水率提高之傾向,結果,會有嚴苛之加濕環境下的光學耐久性降低之傾向。藉由併用含有N-羥烷基之(甲基)丙烯醯胺衍生物與具有異氰酸酯基之化合物,無助於與偏光件之接著之羥基與異氰酸酯基會形成胺基甲酸酯鍵結,且可一面保持接著性,一面降低整體吸水率。 The active energy ray-curable adhesive of the present invention may contain an isocyanate compound (D). The isocyanate compound (D) is a compound having at least one isocyanate group in the molecule. When the active energy ray-curable adhesive contains an isocyanate compound (D), the hydroxyl group on the surface of the polarizer interacts with the isocyanate group, thereby giving the polarizing film stronger adhesion and water resistance. In addition, when the active energy ray-curable adhesive contains an N-hydroxyalkyl group-containing (meth)acrylamide derivative as a radical polymerizable compound, if the N-hydroxyalkyl group-containing (meth)acrylamide As the content of the amine derivative increases, the hydroxyl group is contained in the adhesive layer, so the overall water absorption tends to increase, and as a result, the optical durability under severe humidified environments tends to decrease. By combining the (meth)acrylamide derivative containing N-hydroxyalkyl and the compound having an isocyanate group, it is not helpful to form a carbamate bond with the hydroxyl group and the isocyanate group of the polarizer, and It can maintain the adhesion while reducing the overall water absorption rate.
異氰酸酯化合物(D)可列舉如:多官能異氰酸酯 化合物、活性能量線硬化型異氰酸酯化合物等。舉例言之,多官能異氰酸酯化合物可列舉如:1,2-伸乙基二異氰酸酯、1,4-伸丁基二異氰酸酯、1,6-六亞甲基二異氰酸酯等低級脂 肪族聚異氰酸酯類;伸環戊基二異氰酸酯、伸環己基二異氰酸酯、異佛酮二異氰酸酯、加氫甲伸苯基二異氰酸酯、加氫二甲苯二異氰酸酯等脂環族聚異氰酸酯類;2,4-甲伸苯基二異氰酸酯、2,6-甲伸苯基二異氰酸酯、4,4’-二苯甲烷二異氰酸酯、伸茬基二異氰酸酯等芳香族聚異氰酸酯類等。 舉例言之,前述異氰酸酯化合物(D)亦可列舉如:三羥甲基丙烷/甲伸苯基二異氰酸酯加成物[日本聚胺基甲酸酯工業股份有限公司製,商品名「CORONATE L」]、三羥甲基丙烷/六亞甲基二異氰酸酯加成物[日本聚胺基甲酸酯工業股份有限公司製,商品名「CORONATE HL」]、商品名「CORONATE HX」(日本聚胺基甲酸酯工業股份有限公司)、三羥甲基丙烷/伸茬基二異氰酸酯加成物[三井化學股份有限公司製,商品名「TAKENATE110N」]等市售品。活性能量線硬化型異氰酸酯化合物(D)可列舉如:具有(甲基)丙烯醯基之異氰酸酯類,舉例言之,可列舉如:KARENZ AOI(昭和電工股份有限公司製)、KARENZ BEI(昭和電工股份有限公司製)、Laromer LR9000(BASF公司製)等市售品。 Examples of the isocyanate compound (D) include: polyfunctional isocyanate Compounds, active energy ray-curable isocyanate compounds, etc. For example, the multifunctional isocyanate compound can be exemplified by: 1,2-ethylidene diisocyanate, 1,4-butylene diisocyanate, 1,6-hexamethylene diisocyanate, etc. Aliphatic polyisocyanates; cyclopentyl diisocyanate, cyclohexyl diisocyanate, isophorone diisocyanate, hydrogenated methylenediphenyl diisocyanate, hydrogenated xylene diisocyanate and other alicyclic polyisocyanates; 2, Aromatic polyisocyanates such as 4-toluene diisocyanate, 2,6-tolyl diisocyanate, 4,4'-diphenylmethane diisocyanate, and stubble diisocyanate. For example, the aforementioned isocyanate compound (D) can also be exemplified by: trimethylolpropane/toluene diisocyanate adduct [manufactured by Japan Polyurethane Industry Co., Ltd., trade name "CORONATE L" ], trimethylolpropane/hexamethylene diisocyanate adduct [manufactured by Japan Polyurethane Industry Co., Ltd., trade name "CORONATE HL"], trade name "CORONATE HX" (Japanese polyamine group Formate Industrial Co., Ltd.), trimethylolpropane/stubble diisocyanate adduct [Mitsui Chemical Co., Ltd., trade name "TAKENATE110N"] and other commercially available products. Examples of the active energy ray-curable isocyanate compound (D) include isocyanates having a (meth)acryloyl group. For example, KARENZ AOI (manufactured by Showa Denko Co., Ltd.), KARENZ BEI (Showa Denko) Co., Ltd.), Laromer LR9000 (manufactured by BASF) and other commercially available products.
相對於硬化性成分之全量100重量份,異氰酸酯 化合物(D)之摻合量通常為30重量份以下,若活性能量線硬化型接著劑中的前述化合物(D)之含量過多,則接著性會降低,並有對掉落試驗之耐衝擊性惡化之情形。活性能量線硬化型接著劑中的前述化合物(D)之含量更宜為20重量份以下。另一方面,若由耐水性之觀點來看,則活性能量線硬化型接著劑中,宜含有前述化合物(D)0.1重量份以上,更 宜含有1重量份以上。 Relative to 100 parts by weight of the total amount of the hardenable component, isocyanate The compounding amount of the compound (D) is usually 30 parts by weight or less. If the content of the aforementioned compound (D) in the active energy ray-curable adhesive is too large, the adhesion will be lowered and it will have impact resistance to the drop test. Worsening situation. The content of the aforementioned compound (D) in the active energy ray-curable adhesive is more preferably 20 parts by weight or less. On the other hand, from the viewpoint of water resistance, the active energy ray-curable adhesive preferably contains 0.1 parts by weight or more of the compound (D), more It should preferably contain more than 1 part by weight.
<矽烷耦合劑(E)> <Silane Coupling Agent (E)>
本發明之偏光薄膜用硬化型接著劑為活性能量線硬化性硬化型時,矽烷耦合劑(E)宜使用活性能量線硬化性化合物,然而,即使並非活性能量線硬化性,亦可賦予相同之耐水性。 When the curing adhesive for polarizing film of the present invention is an active energy ray-curable curing type, the silane coupling agent (E) is preferably an active energy ray-curable compound. However, even if it is not active energy ray-curable, the same Water resistance.
作為矽烷耦合劑(E)之具體例,活性能量線硬化 性化合物可列舉如:乙烯基三氯矽烷、乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、2-(3,4環氧環己基)乙基三甲氧基矽烷、3-環氧丙氧基丙基三甲氧基矽烷、3-環氧丙氧基丙基甲基二乙氧基矽烷、3-環氧丙氧基丙基三乙氧基矽烷、p-苯乙烯基三甲氧基矽烷、3-甲基丙烯醯氧基丙基甲基二甲氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基甲基二乙氧基矽烷、3-甲基丙烯醯氧基丙基三乙氧基矽烷、3-丙烯醯氧基丙基三甲氧基矽烷等。 As a specific example of the silane coupling agent (E), active energy ray hardening Examples of the sexual compounds are: vinyl trichlorosilane, vinyl trimethoxy silane, vinyl triethoxy silane, 2-(3,4 epoxycyclohexyl) ethyl trimethoxy silane, 3-epoxypropyl Oxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane , 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxy Silane, 3-methacryloxypropyltriethoxysilane, 3-propenyloxypropyltrimethoxysilane, etc.
較為理想的是3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-丙烯醯氧基丙基三甲氧基矽烷。 More preferably, 3-methacryloxypropyltrimethoxysilane and 3-propenyloxypropyltrimethoxysilane.
並非活性能量線硬化性之矽烷耦合劑之具體例宜為具有胺基之矽烷耦合劑(E1)。具有胺基之矽烷耦合劑(E1)之具體例可列舉如:γ-胺丙基三甲氧基矽烷、γ-胺丙基三乙氧基矽烷、γ-胺丙基三異丙氧基矽烷、γ-胺丙基甲基二甲氧基矽烷、γ-胺丙基甲基二乙氧基矽烷、γ-(2-胺乙基)胺丙基三甲氧基矽烷、γ-(2-胺乙基)胺丙基甲基二甲氧基矽烷、γ-(2-胺乙基)胺丙基三乙氧基矽烷、γ-(2-胺乙 基)胺丙基甲基二乙氧基矽烷、γ-(2-胺乙基)胺丙基三異丙氧基矽烷、γ-(2-(2-胺乙基)胺乙基)胺丙基三甲氧基矽烷、γ-(6-胺己基)胺丙基三甲氧基矽烷、3-(N-乙胺基)-2-甲基丙基三甲氧基矽烷、γ-脲丙基三甲氧基矽烷、γ-脲丙基三乙氧基矽烷、N-苯基-γ-胺丙基三甲氧基矽烷、N-苄基-γ-胺丙基三甲氧基矽烷、N-乙烯基苄基-γ-胺丙基三乙氧基矽烷、N-環己基胺基甲基三乙氧基矽烷、N-環己基胺基甲基二乙氧基甲基矽烷、N-苯基胺基甲基三甲氧基矽烷、(2-胺乙基)胺甲基三甲氧基矽烷、N,N’-雙[3-(三甲氧基矽基)丙基]乙二胺等含有胺基之矽烷類;N-(1,3-二甲基亞丁基)-3-(三乙氧基矽基)-1-丙胺等酮亞胺型矽烷類。 A specific example of the silane coupling agent that is not active energy ray-curable is preferably a silane coupling agent (E1) having an amine group. Specific examples of the silane coupling agent (E1) having an amine group include: γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-(2-aminoethyl)aminopropyltrimethoxysilane, γ-(2-amineethyl Group) aminopropylmethyldimethoxysilane, γ-(2-aminoethyl)aminopropyltriethoxysilane, γ-(2-aminoethyl Group) aminopropylmethyl diethoxysilane, γ-(2-aminoethyl)aminopropyltriisopropoxysilane, γ-(2-(2-aminoethyl)aminoethyl)aminopropyl Trimethoxysilane, γ-(6-aminohexyl)aminopropyltrimethoxysilane, 3-(N-ethylamino)-2-methylpropyltrimethoxysilane, γ-ureapropyltrimethoxysilane Silane, γ-ureapropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-benzyl-γ-aminopropyltrimethoxysilane, N-vinylbenzyl -γ-aminopropyltriethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexylaminomethyl diethoxymethylsilane, N-phenylaminomethyl Amino group-containing silanes such as trimethoxysilane, (2-aminoethyl)aminemethyltrimethoxysilane, N,N'-bis[3-(trimethoxysilyl)propyl]ethylenediamine; N-(1,3-dimethylbutylene)-3-(triethoxysilyl)-1-propanamine and other ketimine type silanes.
具有胺基之矽烷耦合劑(E1)亦可僅使用1種,且 亦可組合使用複數種。於該等中,為了確保良好之接著性,宜為γ-胺丙基三甲氧基矽烷、γ-(2-胺乙基)胺丙基三甲氧基矽烷、γ-(2-胺乙基)胺丙基甲基二甲氧基矽烷、γ-(2-胺乙基)胺丙基三乙氧基矽烷、γ-(2-胺乙基)胺丙基甲基二乙氧基矽烷、N-(1,3-二甲基亞丁基)-3-(三乙氧基矽基)-1-丙胺。 Only one type of silane coupling agent (E1) with an amine group may be used, and You can also use a combination of multiple species. Among these, in order to ensure good adhesion, γ-aminopropyltrimethoxysilane, γ-(2-aminoethyl)aminopropyltrimethoxysilane, γ-(2-aminoethyl) Aminopropylmethyldimethoxysilane, γ-(2-aminoethyl)aminopropyltriethoxysilane, γ-(2-aminoethyl)aminopropylmethyldiethoxysilane, N -(1,3-dimethylbutylene)-3-(triethoxysilyl)-1-propanamine.
相對於硬化性成分之全量100重量份,矽烷耦合 劑(E)之摻合量宜為0.01~20重量份之範圍,且宜為0.05~15重量份,更宜為0.1~10重量份。這是因為當大於20重量份之摻合量時,接著劑之保存安定性惡化,又,當小於0.1重量份時,無法充分地發揮耐水接著性之效果之故。另,在計算接著劑層之玻璃轉移溫度Tg時,作成未將矽烷耦合劑 (E)納入計算。 Silane coupling relative to 100 parts by weight of total hardenable component The blending amount of the agent (E) is preferably in the range of 0.01 to 20 parts by weight, and is preferably 0.05 to 15 parts by weight, more preferably 0.1 to 10 parts by weight. This is because when the blending amount is more than 20 parts by weight, the storage stability of the adhesive deteriorates, and when it is less than 0.1 parts by weight, the effect of water resistance adhesion cannot be sufficiently exhibited. In addition, when calculating the glass transition temperature Tg of the adhesive layer, the silane coupling agent was not used. (E) included in the calculation.
前述以外並非活性能量線硬化性之矽烷耦合劑 之具體例可列舉如:3-脲丙基三乙氧基矽烷、3-氯丙基三甲氧基矽烷、3-巰丙基甲基二甲氧基矽烷、3-巰丙基三甲氧基矽烷、四硫化雙(三乙氧基矽基丙基)、3-異氰酸丙基三乙氧基矽烷、咪唑矽烷等。 Silane coupling agent other than the aforementioned, which is not active energy ray curable Specific examples include: 3-ureapropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane , Bis(triethoxysilylpropyl) tetrasulfide, 3-isocyanatopropyltriethoxysilane, imidazole silane, etc.
針對前述光酸產生劑(B)、包含烷氧基、環氧基 中任一者之化合物(C)、異氰酸酯化合物(D)、矽烷耦合劑(E),各成分之logPow值亦宜為1以上,且更宜為2以上。另,光酸產生劑(B)、矽烷耦合劑(E)並未包含於偏光薄膜用硬化型接著劑之logPow值之計算中之成分。另一方面,包含烷氧基、環氧基中任一者之化合物(C)、異氰酸酯化合物(D)包含於偏光薄膜用硬化型接著劑之logPow值之計算中之成分。 For the aforementioned photoacid generator (B), including alkoxy groups and epoxy groups For any of the compound (C), isocyanate compound (D), and silane coupling agent (E), the logPow value of each component should also be 1 or more, and more preferably 2 or more. In addition, the photoacid generator (B) and the silane coupling agent (E) are not included in the calculation of the logPow value of the hardening adhesive for polarizing films. On the other hand, the compound (C) and the isocyanate compound (D) containing any of the alkoxy group and the epoxy group are included in the calculation of the logPow value of the hardening adhesive for polarizing film.
<前述以外之添加劑> <Additives other than the aforementioned>
又,於本發明之偏光薄膜用硬化型接著劑中,在無損本發明之目的、效果之範圍,可摻合各種添加劑作為其他任意成分。前述添加劑可列舉如:聚醯胺、聚醯胺醯亞胺、聚胺基甲酸酯、聚丁二烯、聚氯丁二烯、聚醚、聚酯、苯乙烯-丁二烯嵌段共聚物、石油樹脂、二甲苯樹脂、酮樹脂、纖維素樹脂、氟系低聚物、聚矽氧系低聚物、聚硫系低聚物等聚合物或低聚物;吩噻嗪、2,6-二-t-丁基-4-甲苯酚等聚合抑制劑;聚合引發助劑;調平劑;潤濕性改良劑;界面活性劑;可塑劑;紫外線吸收劑;無機填充劑;顏料; 染料等。於各種添加劑中,亦宜為logPow值高者。各種添加劑之logPow值宜為2以上,且更宜為3以上,最宜為4以上。另,該等添加劑並未包含於偏光薄膜用硬化型接著劑之logPow值之計算中之成分。 In addition, in the hardening type adhesive for polarizing films of the present invention, various additives may be blended as other arbitrary components within a range that does not impair the object and effect of the present invention. Examples of the aforementioned additives include: polyamidoamine, polyamidoamide imine, polyurethane, polybutadiene, polychloroprene, polyether, polyester, styrene-butadiene block copolymerization Polymers, petroleum resins, xylene resins, ketone resins, cellulose resins, fluorine-based oligomers, polysiloxane-based oligomers, polysulfide-based oligomers and other polymers or oligomers; phenothiazine, 2, 6-di-t-butyl-4-cresol and other polymerization inhibitors; polymerization initiation aids; leveling agents; wettability modifiers; surfactants; plasticizers; ultraviolet absorbers; inorganic fillers; pigments; Dyes, etc. Among various additives, the one with the highest logPow value is also suitable. The logPow value of various additives should be 2 or more, more preferably 3 or more, and most preferably 4 or more. In addition, these additives are not included in the calculation of the logPow value of the hardening adhesive for polarizing films.
相對於硬化性成分之全量100重量份,前述添加 劑通常為0~10重量份,且宜為0~5重量份,最宜為0~3重量份。 The aforementioned addition is relative to 100 parts by weight of the total amount of the hardenable component The agent is usually 0 to 10 parts by weight, and preferably 0 to 5 parts by weight, most preferably 0 to 3 parts by weight.
<接著劑之黏度> <viscosity of adhesive>
本發明之偏光薄膜用硬化型接著劑含有前述硬化性成分,然而,若由塗覆性之觀點來看,則該接著劑之黏度於25℃中宜為100cp以下。另一方面,當本發明之偏光薄膜用硬化型接著劑於25℃中大為100cp時,亦可於塗覆時控制接著劑之溫度而調整為100cp以下來使用。黏度之更為理想之範圍為1~80cp,最為理想的是10~50cp。黏度可使用東機產業公司製之E型黏度計TVE22LT來測定。 The curable adhesive for polarizing films of the present invention contains the aforementioned curable components. However, from the viewpoint of coatability, the viscosity of the adhesive is preferably 100 cp or less at 25°C. On the other hand, when the hardening adhesive for polarizing film of the present invention is 100 cp at 25° C., the temperature of the adhesive may be controlled to be 100 cp or less during coating. The more ideal range of viscosity is 1~80cp, the most ideal is 10~50cp. Viscosity can be measured using TVE22LT, an E-type viscometer manufactured by Toki Industry Corporation.
又,若由安全性之觀點來看,則本發明之偏光薄 膜用硬化型接著劑宜使用皮膚刺激低之材料作為前述硬化性成分。皮膚刺激性可藉由所謂P.I.I之指標來判斷。P.I.I是顯示皮膚障礙之程度而廣泛地運用,並藉由崔氏法來測定。測定值是以0~8之範圍來表示,值越小,判斷為刺激性越低,然而,由於測定值之誤差大,因此,可作為參考值來掌握。P.I.I宜為4以下,且更宜為3以下,最宜為2以下。 In addition, from the viewpoint of safety, the polarized light of the present invention is thin For the film-curing adhesive, a material with low skin irritation is preferably used as the aforementioned curable component. Skin irritation can be judged by the so-called P.I.I index. P.I.I is widely used to show the degree of skin disorders, and is measured by the Choi method. The measured value is expressed in the range of 0 to 8. The smaller the value, the lower the irritation. However, because the error of the measured value is large, it can be grasped as a reference value. P.I.I is preferably 4 or less, and more preferably 3 or less, and most preferably 2 or less.
<偏光薄膜> <polarizing film>
本發明之偏光薄膜是在偏光件之至少單面隔著前述偏 光薄膜用硬化型接著劑之硬化物層所形成的接著劑層黏合有透明保護薄膜。屬於前述硬化物層的接著劑層如前述,整體吸水率為10重量%以下。 The polarizing film of the present invention has at least one side of the polarizer interposed by the aforementioned polarizer A transparent protective film is bonded to the adhesive layer formed by the hardened layer of the hardening adhesive for the optical film. As described above, the adhesive layer belonging to the hardened material layer has an overall water absorption rate of 10% by weight or less.
<接著劑層> <adhesive layer>
藉由前述硬化型接著劑所形成的接著劑層之厚度宜控制為0.1~3μm。接著劑層之厚度更宜為0.3~2μm,進而宜為0.5~1.5μm。在藉由接著劑層之凝聚力抑制接著不良之產生或層合時產生外觀不良(氣泡)上,將接著劑層之厚度作成0.1μm以上是較為理想的。另一方面,若接著劑層比3μm厚,則會有偏光薄膜無法滿足耐久性之虞。 The thickness of the adhesive layer formed by the aforementioned hardening adhesive should be controlled to 0.1 to 3 μm. The thickness of the adhesive layer is more preferably 0.3 to 2 μm, and further preferably 0.5 to 1.5 μm. In order to suppress the occurrence of adhesion defects by the cohesive force of the adhesive layer or the appearance defects (bubbles) during lamination, it is preferable to make the thickness of the adhesive layer 0.1 μm or more. On the other hand, if the adhesive layer is thicker than 3 μm, there is a possibility that the polarizing film cannot satisfy the durability.
又,硬化型接著劑宜選擇為藉此所形成的接著劑 層之Tg會構成60℃以上,且更宜為70℃以上,再者,宜為75℃以上,進而是100℃以上,甚至是120℃以上。另一方面,若接著劑層之Tg過高,則偏光薄膜之彎曲性會降低,因此,接著劑層之Tg宜作成300℃以下,進而是240℃以下,甚至是180℃以下。Tg<玻璃轉移溫度>是使用TA儀器製動態黏彈性測定裝置RSAIII,並藉由以下測定條件來測定。 Moreover, the hardening type adhesive should be selected as the adhesive formed by this The Tg of the layer will constitute above 60°C, and more preferably above 70°C. Furthermore, it is preferably above 75°C, further above 100°C, or even above 120°C. On the other hand, if the Tg of the adhesive layer is too high, the bendability of the polarizing film will decrease. Therefore, the Tg of the adhesive layer should preferably be 300°C or lower, further 240°C or lower, or even 180°C or lower. Tg <glass transition temperature> is measured using the following measuring conditions using a dynamic viscoelasticity measuring device RSAIII made by TA Instruments.
試樣尺寸:寬度10mm、長度30mm,夾具距離20mm,測定模式:拉伸,頻率:1Hz,升溫速度:5℃/分 Sample size: width 10mm, length 30mm, fixture distance 20mm, measurement mode: stretching, frequency: 1Hz, heating rate: 5°C/min
進行動態黏彈性之測定,並作成tan δ之峰頂之溫度Tg而採用。 The dynamic viscoelasticity is measured and used as the temperature Tg at the peak top of tan δ.
又,硬化型接著劑宜為藉此所形成的接著劑層之儲存模數於70℃以下之領域為1.0×106Pa以上。再者,更宜 為1.0×107Pa以上。接著劑層之儲存模數會影響於偏光薄膜施加熱循環(-40℃至80℃等)時的偏光件裂紋,當儲存模數低時,容易產生偏光件裂紋之問題。具有高儲存模數之溫度領域更宜為80℃以下,最宜為90℃以下。儲存模數是與Tg<玻璃轉移溫度>同時地使用TA儀器製動態黏彈性測定裝置RSAIII,並藉由相同之測定條件來測定。進行動態黏彈性之測定,並採用儲存模數(Eˊ’)之值。 In addition, the hardening type adhesive preferably has a storage modulus of 1.0×10 6 Pa or higher in a field where the storage modulus of the adhesive layer formed by this is 70° C. or lower. Furthermore, it is more preferably 1.0×10 7 Pa or more. The storage modulus of the adhesive layer will affect the polarizer cracking when the polarizing film is subjected to a thermal cycle (-40°C to 80°C, etc.). When the storage modulus is low, the polarizer cracking problem is likely to occur. The temperature range with a high storage modulus is more preferably below 80°C and most preferably below 90°C. The storage modulus was measured with the same measurement conditions using the dynamic viscoelasticity measuring device RSAIII made by TA Instruments at the same time as Tg<glass transition temperature>. The dynamic viscoelasticity is measured and the value of the storage modulus (Eˊ') is used.
有關本發明之偏光薄膜具有:於業已於偏光件形成接著劑層之面及/或透明保護薄膜形成接著劑層之面塗覆硬化型接著劑後,黏合偏光件與透明保護薄膜之步驟;接著,將硬化型接著劑硬化而形成接著劑層之步驟。 The polarizing film of the present invention includes the steps of bonding the polarizing member and the transparent protective film after applying a hardening adhesive on the surface of the polarizing member where the adhesive layer is formed and/or the transparent protective film forming the adhesive layer; The step of curing the hardening adhesive to form an adhesive layer.
偏光件、透明保護薄膜亦可於塗覆前述硬化型接著劑前進行表面改質處理。具體之處理可列舉如:利用電暈處理、電漿處理、皂化處理之處理等。 The polarizer and the transparent protective film may be surface-modified before applying the hardening adhesive. Specific treatments include, for example, treatment using corona treatment, plasma treatment, and saponification treatment.
硬化型接著劑之塗覆方式可依照該硬化型接著劑之黏度或作為目標之厚度適當地選擇。舉例言之,塗覆方式之例子可列舉如:反向塗佈機、凹版塗佈機(直接、反向或間接)、棒式反向塗佈機、輥式塗佈機、壓鑄模塗佈機、棒式塗佈機、桿式塗佈機等。除此之外,塗覆可適當地使用浸漬方式等方式。 The application method of the hardening adhesive can be appropriately selected according to the viscosity of the hardening adhesive or the target thickness. For example, examples of coating methods include: reverse coater, gravure coater (direct, reverse or indirect), rod reverse coater, roll coater, die casting die coating Machine, bar coater, rod coater, etc. In addition, for the coating, a dipping method or the like can be used as appropriate.
隔著業已如前述般塗覆的硬化型接著劑,黏合偏光件與透明保護薄膜。偏光件與透明保護薄膜之黏合可藉由輥式層合機等來進行。 The polarizer and the transparent protective film are bonded through the hardening adhesive that has been applied as described above. The bonding of the polarizer and the transparent protective film can be performed by a roll laminator or the like.
<接著劑之硬化> <hardening of adhesive>
有關本發明之偏光薄膜用硬化型接著劑可作成活性能量線硬化型接著劑或熱硬化型接著劑來使用。於活性能量線硬化型接著劑中,可於電子射線硬化型、紫外線硬化型、可見光線硬化型之態樣下使用。若由生產性之觀點來看,則前述硬化型接著劑之態樣為活性能量線硬化型接著劑優於熱硬化型接著劑,再者,若由生產性之觀點來看,則活性能量線硬化型接著劑宜為可見光線硬化型接著劑。 The hardening type adhesive for polarizing films of the present invention can be used as an active energy ray hardening type adhesive or a thermosetting type adhesive. It can be used in the form of electron beam curing type, ultraviolet curing type, visible light curing type in active energy ray curing type adhesive. From the viewpoint of productivity, the form of the aforementioned hardening adhesive is that the active energy ray curing adhesive is superior to the thermosetting adhesive. Furthermore, from the viewpoint of productivity, the active energy ray The hardening type adhesive is preferably a visible light hardening type adhesive.
《活性能量線硬化型》 "Active Energy Ray Hardening Type"
於活性能量線硬化型接著劑中,在黏合偏光件與透明保護薄膜後,照射活性能量線(電子射線、紫外線、可見光線等),並將活性能量線硬化型接著劑硬化而形成接著劑層。活性能量線(電子射線、紫外線、可見光線等)之照射方向可自任意適切之方向照射。較為理想的是自透明保護薄膜側照射。若自偏光件側照射,則會有偏光件因活性能量線(電子射線、紫外線、可見光線等)而劣化之虞。 In the active energy ray-curable adhesive, after bonding the polarizer and the transparent protective film, the active energy ray (electron rays, ultraviolet rays, visible light, etc.) is irradiated, and the active energy ray-curable adhesive is hardened to form an adhesive layer . The irradiation direction of active energy rays (electron rays, ultraviolet rays, visible rays, etc.) can be irradiated from any suitable direction. It is more desirable to irradiate from the side of the transparent protective film. If irradiated from the polarizer side, the polarizer may deteriorate due to active energy rays (electron rays, ultraviolet rays, visible rays, etc.).
《電子射線硬化型》 "Electronic beam hardening type"
於電子射線硬化型中,電子射線之照射條件只要是可將前述活性能量線硬化型接著劑硬化之條件,則可採用任意適切之條件。舉例言之,電子射線照射是加速電壓宜為5kV~300kV,且更宜為10kV~250kV。當加速電壓小於5kV時,電子射線無法抵達接著劑而有硬化不足之虞,若加速電壓大於300kV,則通過試料之滲透力過強而有對透明保護薄膜或偏光件造成損害之虞。照射線量為5~100kGy,且更宜為10~75kGy。當照射線量小於5kGy時,接著劑會硬化不 足,若大於100kGy,則會對透明保護薄膜或偏光件造成損害,並產生機械強度之降低或黃變,且無法獲得預定之光學特性。 In the electron beam curing type, as long as the irradiation condition of the electron beam is a condition that can cure the aforementioned active energy ray curing type adhesive, any appropriate conditions can be adopted. For example, for electron beam irradiation, the acceleration voltage should be 5 kV to 300 kV, and more preferably 10 kV to 250 kV. When the acceleration voltage is less than 5kV, the electron beam cannot reach the adhesive and there is a risk of insufficient hardening. If the acceleration voltage is greater than 300kV, the penetration force of the sample is too strong, which may damage the transparent protective film or the polarizer. The irradiation dose is 5~100kGy, and more preferably 10~75kGy. When the irradiation dose is less than 5kGy, the adhesive will not harden If it is more than 100kGy, it will cause damage to the transparent protective film or polarizer, and reduce the mechanical strength or yellowing, and the predetermined optical characteristics cannot be obtained.
電子射線照射通常於惰性氣體中進行照射,然 而,若為必要,則亦可於大氣中或導入少量氧之條件下進行。雖然依照透明保護薄膜之材料而有所不同,然而,藉由適當地導入氧,使電子射線最初照射的透明保護薄膜面特意產生氧抑制,且可防止對透明保護薄膜之損害,並可有效地使電子射線僅照射至接著劑。 Electron beam irradiation is usually carried out in an inert gas, but However, if necessary, it can also be carried out in the atmosphere or under the condition of introducing a small amount of oxygen. Although it differs according to the material of the transparent protective film, by introducing oxygen appropriately, the surface of the transparent protective film initially irradiated with electron beams intentionally produces oxygen suppression, and can prevent damage to the transparent protective film and can effectively The electron beam is irradiated only to the adhesive.
《紫外線硬化型、可見光線硬化型》 "Ultraviolet curing type, visible light curing type"
於有關本發明之偏光薄膜之製造方法中,活性能量線宜使用包含有波長範圍380nm~450nm之可見光線者,特別是波長範圍380nm~450nm之可見光線之照射量最多之活性能量線。於紫外線硬化型、可見光線硬化型中,使用業已賦予紫外線吸收能力之透明保護薄膜(紫外線不透射型透明保護薄膜)時,由於大致吸收波長短於380nm之光,因此,波長短於380nm之光不會到達活性能量線硬化型接著劑而無助於其聚合反應。再者,藉由透明保護薄膜所吸收波長短於380nm之光會轉換成熱,且透明保護薄膜本身會發熱,並成為偏光薄膜之捲邊、皺摺等不良之原因。故,於本發明中採用紫外線硬化型、可見光線硬化型時,活性能量線產生裝置宜使用不會發出波長短於380nm之光之裝置,更具體而言,波長範圍380~440nm之累計照度與波長範圍250~370nm之累計照度之比宜為100:0~100:50,且更宜 為100:0~100:40。有關本發明之活性能量線宜為封入鎵之金屬鹵素燈、發光波長範圍380~440nm之LED光源。或,可使用低壓水銀燈、中壓水銀燈、高壓水銀燈、超高壓水銀燈、白熾燈、氙燈、鹵素燈、碳弧燈、金屬鹵素燈、螢光燈、鎢絲燈、鎵燈、準分子雷射或太陽光等包含有紫外線與可見光線之光源,且亦可使用帶通濾波器而阻斷波長短於380nm之紫外線而使用。為了提高偏光件與透明保護薄膜間之接著劑層之接著性能,並防止偏光薄膜之捲邊,宜使用以下活性能量線,即:使用封入鎵之金屬鹵素燈並透過可阻斷波長短於380nm之光之帶通濾波器而得之活性能量線,或使用LED光源而得之波長405nm之活性能量線。 In the manufacturing method of the polarizing film of the present invention, the active energy ray preferably includes visible light with a wavelength range of 380 nm to 450 nm, especially the active energy line with the largest exposure to visible light with a wavelength range of 380 nm to 450 nm. In the ultraviolet curing type and the visible light curing type, when using a transparent protective film (ultraviolet-transmissive transparent protective film) that has been provided with ultraviolet absorption capacity, the light with a wavelength shorter than 380nm is generally absorbed, so the light with a wavelength shorter than 380nm It will not reach the active energy ray hardening type adhesive without helping its polymerization reaction. Furthermore, the light with a wavelength shorter than 380 nm absorbed by the transparent protective film will be converted into heat, and the transparent protective film itself will generate heat, and cause the curling, wrinkling and other defects of the polarizing film. Therefore, when the ultraviolet curing type and the visible light curing type are used in the present invention, the active energy ray generating device should preferably use a device that does not emit light with a wavelength shorter than 380 nm. More specifically, the cumulative illuminance of the wavelength range 380 to 440 nm and The ratio of the cumulative illuminance in the wavelength range 250~370nm should be 100:0~100:50, and more preferably It is 100:0~100:40. The active energy ray of the present invention is preferably a metal halide lamp enclosed with gallium and an LED light source with a light emitting wavelength range of 380-440 nm. Or, low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, incandescent lamps, xenon lamps, halogen lamps, carbon arc lamps, metal halogen lamps, fluorescent lamps, tungsten filament lamps, gallium lamps, excimer lasers or Sunlight and other light sources including ultraviolet rays and visible rays can also be used with a band-pass filter to block ultraviolet rays with a wavelength shorter than 380nm. In order to improve the adhesion performance of the adhesive layer between the polarizer and the transparent protective film, and to prevent the curling of the polarizing film, it is advisable to use the following active energy ray, that is: use a metal halide lamp enclosed in gallium and pass through to block wavelengths shorter than 380nm The active energy line obtained by the bandpass filter of light, or the active energy line with a wavelength of 405 nm obtained by using an LED light source.
於紫外線硬化型或可見光線硬化型中,宜於照射 紫外線或可見光線前將活性能量線硬化型接著劑加溫(照射前加溫),此時,宜加溫為40℃以上,且更宜加溫為50℃以上。又,亦宜於照射紫外線或可見光線後將活性能量線硬化型接著劑加溫(照射後加溫),此時,宜加溫為40℃以上,且更宜加溫為50℃以上。 Suitable for irradiation in ultraviolet curing type or visible light curing type The active energy ray-curable adhesive is heated before ultraviolet or visible light (heating before irradiation). At this time, the heating is preferably 40°C or higher, and more preferably 50°C or higher. In addition, it is also suitable to heat the active energy ray-curable adhesive after irradiating ultraviolet rays or visible rays (heating after irradiation). In this case, the temperature is preferably 40°C or higher, and more preferably 50°C or higher.
有關本發明之活性能量線硬化型接著劑特別是可適當地使用於以下情形,即:形成接著偏光件與波長365nm之光線透射率小於5%之透明保護薄膜之接著劑層。在此,有關本發明之活性能量線硬化型接著劑是含有前述一般式(1)之光聚合引發劑,藉此,可隔著具有UV吸收能力之透明保護薄膜照射紫外線而硬化形成接著劑層。依此,即使於業已將具有UV吸收能力之透明保護薄膜積層於偏 光件之兩面之偏光薄膜中,亦可使接著劑層硬化。然而,理所當然,於業已積層未具有UV吸收能力之透明保護薄膜之偏光薄膜中,亦可使接著劑層硬化。另,所謂具有UV吸收能力之透明保護薄膜是意味著對380nm之光之透射率小於10%之透明保護薄膜。 In particular, the active energy ray-curable adhesive of the present invention can be suitably used in the case of forming an adhesive layer for adhering a polarizer and a transparent protective film having a light transmittance of less than 5% at a wavelength of 365 nm. Here, the active energy ray-curable adhesive of the present invention contains the photopolymerization initiator of the general formula (1), whereby the transparent protective film with UV absorption ability can be irradiated with ultraviolet rays to harden to form an adhesive layer . Accordingly, even though Yu has already laminated transparent protective films with UV absorption In the polarizing films on both sides of the optical member, the adhesive layer can also be hardened. However, as a matter of course, the adhesive layer can also be hardened in a polarizing film that has been laminated with a transparent protective film that does not have UV absorption capability. In addition, the so-called transparent protective film with UV absorption capability means a transparent protective film whose transmittance to light at 380 nm is less than 10%.
對透明保護薄膜賦予UV吸收能力之方法可列舉如:使透明保護薄膜中含有紫外線吸收劑之方法,或使含有紫外線吸收劑之表面處理層積層於透明保護薄膜表面之方法。 The method of imparting UV absorption ability to the transparent protective film may include, for example, a method of containing an ultraviolet absorber in the transparent protective film, or a method of laminating a surface treatment layer containing an ultraviolet absorber on the surface of the transparent protective film.
舉例言之,紫外線吸收劑之具體例可列舉如:以 往公知之氧二苯基酮系化合物、苯并三唑系化合物、水楊酸酯系化合物、二苯基酮系化合物、氰基丙烯酸酯系化合物、鎳錯鹽系化合物、三嗪系化合物等。 For example, specific examples of ultraviolet absorbers can be cited as: Conventionally known oxygen diphenyl ketone compounds, benzotriazole compounds, salicylate compounds, diphenyl ketone compounds, cyanoacrylate compounds, nickel complex compounds, triazine compounds, etc. .
在黏合偏光件與透明保護薄膜後,照射活性能量線(電子射線、紫外線、可見光線等),並將活性能量線硬化型接著劑硬化而形成接著劑層。活性能量線(電子射線、紫外線、可見光線等)之照射方向可自任意適切之方向照射。較為理想的是自透明保護薄膜側照射。若自偏光件側照射,則會有偏光件因活性能量線(電子射線、紫外線、可見光線等)而劣化之虞。 After the polarizer and the transparent protective film are bonded, active energy rays (electron rays, ultraviolet rays, visible rays, etc.) are irradiated, and the active energy ray hardening type adhesive is hardened to form an adhesive layer. The irradiation direction of active energy rays (electron rays, ultraviolet rays, visible rays, etc.) can be irradiated from any suitable direction. It is more desirable to irradiate from the side of the transparent protective film. If irradiated from the polarizer side, the polarizer may deteriorate due to active energy rays (electron rays, ultraviolet rays, visible rays, etc.).
《熱硬化型》 "Thermosetting"
另一方面,於熱硬化型接著劑中,在黏合偏光件與透明保護薄膜後,藉由進行加熱,藉由熱聚合引發劑開始聚合,並形成硬化物層。加熱溫度可按照熱聚合引發劑來設 定,但為60~200℃,且宜為80~150℃。 On the other hand, in the thermosetting adhesive, after the polarizer and the transparent protective film are bonded, by heating, the polymerization is started by the thermal polymerization initiator, and a hardened layer is formed. The heating temperature can be set according to the thermal polymerization initiator It is fixed, but it is 60~200℃, and preferably 80~150℃.
在藉由連續線製造有關本發明之偏光薄膜時,線 速度雖然依照接著劑之硬化時間而有所不同,然而,宜為1~500m/min,且更宜為5~300m/min,進而宜為10~100m/min。當線速度過小時,缺乏生產性,或者對透明保護薄膜之損害過大而無法製作可承受耐久性試驗等之偏光薄膜。當線速度過大時,接著劑之硬化不足,並有無法獲得作為目標之接著性之情形。 When manufacturing the polarizing film of the present invention by a continuous wire, the wire Although the speed varies according to the curing time of the adhesive, it is preferably 1 to 500 m/min, and more preferably 5 to 300 m/min, and further preferably 10 to 100 m/min. When the linear speed is too small, it lacks productivity, or the damage to the transparent protective film is too great to make a polarizing film that can withstand durability tests. When the linear velocity is too high, the curing of the adhesive is insufficient, and the target adhesiveness may not be obtained.
另,本發明之偏光薄膜是隔著前述活性能量線硬 化型接著劑之硬化物層所形成的接著劑層,黏合偏光件與透明保護薄膜,然而,於透明保護薄膜與接著劑層間可設置易接著層。舉例言之,易接著層可藉由具有聚酯骨架、聚醚骨架、聚碳酸酯骨架、聚胺基甲酸酯骨架、聚矽氧系、聚醯胺骨架、聚醯亞胺骨架、聚乙烯醇骨架等之各種樹脂來形成。該等聚合物樹脂可單獨1種或組合2種以上來使用。又,易接著層之形成亦可添加其他添加劑。具體而言,亦可進一步地使用黏著賦予劑、紫外線吸收劑、抗氧化劑、耐熱安定劑等安定劑等。 In addition, the polarizing film of the present invention is hard through the aforementioned active energy rays The adhesive layer formed by the hardened layer of the chemical adhesive bonds the polarizer and the transparent protective film. However, an easy adhesive layer may be provided between the transparent protective film and the adhesive layer. For example, the easy-adhesion layer can be formed by having a polyester skeleton, a polyether skeleton, a polycarbonate skeleton, a polyurethane skeleton, a polysiloxane system, a polyamide skeleton, a polyimide skeleton, polyethylene It is formed by various resins such as alcohol skeleton. These polymer resins can be used alone or in combination of two or more. In addition, other additives may be added to the formation of the easy-adhesion layer. Specifically, stabilizers such as adhesion-imparting agents, ultraviolet absorbers, antioxidants, and heat-resistant stabilizers can also be used.
易接著層通常預先設置於透明保護薄膜,並藉由接著劑層,黏合該透明保護薄膜之易接著層側與偏光件。易接著層之形成是藉由於透明保護薄膜上,藉由公知之技術將易接著層之形成材塗覆、乾燥而進行。易接著層之形成材通常調整為業已考慮乾燥後之厚度、塗覆之圓滑性等而稀釋為適當濃度之溶液。易接著層乾燥後之厚度宜為 0.01~5μm,且更宜為0.02~2μm,進而宜為0.05~1μm。另,易接著層可設置複數層,然而,此時,易接著層之總厚度亦宜作成前述範圍。 The easy-adhesive layer is usually provided in advance on the transparent protective film, and the easy-adhesive layer side of the transparent protective film and the polarizer are bonded by an adhesive layer. The formation of the easy-adhesion layer is performed by coating and drying the forming material of the easy-adhesion layer on the transparent protective film by a known technique. The forming material of the easy-adhesion layer is usually adjusted to a solution having an appropriate concentration after taking into consideration the thickness after drying, the smoothness of coating, etc. The thickness of the easy-adhesion layer after drying should be 0.01~5μm, and more preferably 0.02~2μm, further preferably 0.05~1μm. In addition, the easy-adhesion layer may be provided with a plurality of layers, however, at this time, the total thickness of the easy-adhesion layer is also preferably within the aforementioned range.
<偏光件> <polarizer>
偏光件並無特殊之限制,可使用各種偏光件。舉例言之,偏光件可列舉如:使碘或二色性染料等二色性材料吸附於聚乙烯醇系薄膜、局部縮甲醛化聚乙烯醇系薄膜、乙烯.醋酸乙烯酯共聚物系局部皂化薄膜等親水性高分子薄膜而單軸延伸者、聚乙烯醇之脫水處理物或聚氯乙烯之脫鹽酸處理物等多烯系定向薄膜等。於該等中,亦適合為由聚乙烯醇系薄膜與碘等二色性物質所構成的偏光件。該等偏光件之厚度並無特殊之限制,然而,一般為80μm以下。 There are no special restrictions on polarizers, and various polarizers can be used. For example, the polarizer may include, for example, adsorbing a dichroic material such as iodine or a dichroic dye to a polyvinyl alcohol-based film, a partially formalized polyvinyl alcohol-based film, and ethylene. Vinyl acetate copolymers are hydrophilic polymer films such as partially saponified films and uniaxially stretched, polyene oriented films such as dehydration treatment of polyvinyl alcohol or dehydrochlorination treatment of polyvinyl chloride. Among these, a polarizer composed of a polyvinyl alcohol-based film and a dichroic substance such as iodine is also suitable. The thickness of these polarizers is not particularly limited, however, it is generally below 80 μm.
舉例言之,藉由碘將聚乙烯醇系薄膜染色並單軸延伸之偏光件可依下述來製作,即:藉由將聚乙烯醇浸漬於碘之水溶液中而染色,並延伸成原長度之3~7倍。依需要,亦可浸漬於硼酸或碘化鉀等之水溶液中。再者,依需要,亦可於染色前將聚乙烯醇系薄膜浸漬於水中並水洗。藉由將聚乙烯醇系薄膜水洗,可洗淨聚乙烯醇系薄膜表面之髒污或抗結塊劑,除此之外,藉由使聚乙烯醇系薄膜膨潤,亦具有防止染色不均等不均一之效果。延伸可於藉由碘染色後進行,亦可一面染色一面延伸,又,亦可於延伸後再藉由碘來染色。於硼酸或碘化鉀等之水溶液中或水浴中亦可延伸。 For example, a polarizing member in which a polyvinyl alcohol-based film is dyed by iodine and uniaxially extended can be produced as follows: that is, dyed by dipping polyvinyl alcohol in an aqueous solution of iodine and extended to the original length 3~7 times. If necessary, it can also be immersed in an aqueous solution of boric acid or potassium iodide. Furthermore, if necessary, the polyvinyl alcohol-based film may be immersed in water and washed before being dyed. By washing the polyvinyl alcohol-based film with water, the dirt or anti-caking agent on the surface of the polyvinyl alcohol-based film can be washed. In addition, by swelling the polyvinyl alcohol-based film, it also prevents uneven dyeing. Uniform effect. The extension can be carried out after dyeing with iodine, or it can be dyed on one side and extended on the other side, or it can be dyed with iodine after the extension. It can also be extended in aqueous solutions such as boric acid or potassium iodide or in a water bath.
又,本發明之硬化型接著劑在使用厚度為10μm 以下之薄型偏光件作為偏光件時,可明顯地顯現其效果(滿足高溫高濕下之嚴苛環境下的光學耐久性)。相較於厚度大於10μm之偏光件,前述厚度為10μm以下之偏光件相對而言水分之影響大,且於高溫高濕下之環境下光學耐久性不足,並容易引起透射率上升或偏光度降低。即,在藉由本發明之整體吸水率為10重量%以下之接著劑層積層前述10μm以下之偏光件時,藉由抑制於嚴苛之高溫高濕下之環境下水朝偏光件之移動,可明顯地抑制偏光薄膜之透射率上升、偏光度降低等光學耐久性之惡化。若由薄型化之觀點而言,則偏光件之厚度宜為1~7μm。此種薄型偏光件之厚度不均少,且辨識性優異,又,尺寸變化少,再者,作為偏光薄膜之厚度在達成薄型化方面亦是理想的。 In addition, the hardening type adhesive of the present invention has a thickness of 10 μm When the following thin polarizer is used as a polarizer, its effect can be clearly exhibited (satisfying the optical durability under severe environments under high temperature and high humidity). Compared with polarizers with a thickness greater than 10 μm, the polarizers with a thickness of 10 μm or less have a relatively large influence on moisture, and have insufficient optical durability under high-temperature and high-humidity environments, and are likely to cause an increase in transmittance or a decrease in polarization. . That is, when the polarizer with the overall water absorption rate of 10% by weight or less according to the present invention is laminated to the polarizer with a thickness of 10 μm or less, by suppressing the movement of water toward the polarizer in an environment under severe high temperature and high humidity, it is obvious To suppress deterioration of optical durability such as increase in transmittance of polarizing film and decrease in polarization degree. From the viewpoint of thinning, the thickness of the polarizer is preferably 1 to 7 μm. Such a thin polarizer has less unevenness in thickness and excellent recognizability, and has less dimensional change. Furthermore, the thickness of the polarizing film is also ideal for achieving thinness.
代表而言,薄型偏光件可列舉如:揭示於日本特 開昭51-069644號公報或特開2000-338329號公報,或是WO2010/100917號說明書、PCT/JP2010/001460之說明書,或是日本特願2010-269002號說明書或特願2010-263692號說明書之薄型偏光膜。該等薄型偏光膜可利用包含有以下步驟之製法而得,即:在積層體之狀態下將聚乙烯醇系樹脂(以下亦稱作PVA系樹脂)層與延伸用樹脂基材延伸之步驟;及染色之步驟。若為該製法,則即使PVA系樹脂層薄,藉由支持於延伸用樹脂基材,亦不會有因延伸所造成的破裂等問題而可延伸。 Representatives, the thin polarizers can be listed as follows: Kazakhstan 51-069644 or JP 2000-338329, WO2010/100917, PCT/JP2010/001460, Japanese Patent Application No. 2010-269002 or Japanese Patent Application No. 2010-263692 Thin polarizing film. Such thin polarizing films can be obtained by a manufacturing method including the following steps: a step of extending a layer of a polyvinyl alcohol-based resin (hereinafter also referred to as PVA-based resin) and a resin substrate for extension in a state of a laminate; And dyeing steps. According to this manufacturing method, even if the PVA-based resin layer is thin, by supporting the resin substrate for stretching, there is no problem such as cracking due to stretching and the like, and it can be stretched.
於包含有在積層體之狀態下延伸之步驟及染色之步驟之製法中,若由可延伸成高倍率而提升偏光性能之 觀點來看,則前述薄型偏光膜亦宜藉由如WO2010/100917號說明書、PCT/JP2010/001460之說明書或是特願2010-269002號說明書或特願2010-263692號說明書中所揭示包含有於硼酸水溶液中延伸之步驟之製法而得,特別是宜藉由如特願2010-269002號說明書或特願2010-263692號說明書中所揭示包含有於硼酸水溶液中延伸前輔助性地空中延伸之步驟之製法而得。 In the manufacturing method including the step of extending in the state of the laminate and the step of dyeing, if it can be extended to a high magnification to improve the polarization performance From a viewpoint, the aforementioned thin polarizing film should also be included in the specification disclosed in WO2010/100917, PCT/JP2010/001460, Japanese Patent Application No. 2010-269002, or Japanese Patent Application No. 2010-263692. The preparation method of the step of extending in the aqueous solution of boric acid, in particular, it is preferable to include the step of auxiliary air extension before extension in the aqueous solution of boric acid as disclosed in the specification of Japanese Patent Application No. 2010-269002 or the specification of Japanese Patent Application No. 2010-263692 Derived from the system.
前述PCT/JP2010/001460之說明書中所揭示之薄 型高機能偏光膜是一體地成膜於樹脂基材,並由業已使二色性物質定向之PVA系樹脂所構成,且厚度為7μm以下,並具有單體透射率為42.0%以上及偏光度為99.95%以上之光學特性。 The thinness disclosed in the aforementioned PCT/JP2010/001460 specification Type high-performance polarizing film is integrally formed on the resin substrate, and is composed of PVA-based resin that has already oriented the dichroic substance, and has a thickness of 7 μm or less, and has a single transmittance of 42.0% or more and a degree of polarization The optical characteristics are above 99.95%.
前述薄型高機能偏光膜可依下述來製造,即:藉 由PVA系樹脂之塗佈及乾燥,於具有至少20μm之厚度之樹脂基材生成PVA系樹脂層,且將所生成的PVA系樹脂層浸漬於二色性物質之染色液中,並使二色性物質吸附於PVA系樹脂層,且於硼酸水溶液中,將業已吸附二色性物質之PVA系樹脂層與樹脂基材一體地延伸成總延伸倍率構成原長度之5倍以上。 The aforementioned thin high-performance polarizing film can be manufactured as follows, namely: By coating and drying the PVA-based resin, a PVA-based resin layer is formed on a resin substrate having a thickness of at least 20 μm, and the generated PVA-based resin layer is immersed in the dyeing solution of the dichroic substance, and the dichroic The sexual substance is adsorbed on the PVA-based resin layer, and in the boric acid aqueous solution, the PVA-based resin layer on which the dichroic substance has been adsorbed and the resin base material are integrally extended to a total extension ratio of more than 5 times the original length.
又,一種製造包含有業已使二色性物質定向之薄 型高機能偏光膜之積層體薄膜之方法,其包含有以下步驟,即:生成積層體薄膜之步驟,該積層體薄膜包含有樹脂基材及PVA系樹脂層,且前述樹脂基材具有至少20μm之厚度,前述PVA系樹脂層是藉由於樹脂基材之單面將含PVA 系樹脂之水溶液塗佈及乾燥而形成;吸附步驟,係藉由將包含有樹脂基材及形成於樹脂基材單面之PVA系樹脂層的前述積層體薄膜浸漬於含二色性物質之染色液中,使積層體薄膜所含之PVA系樹脂層吸附二色性物質;延伸步驟,係於硼酸水溶液中,使包含有業已吸附二色性物質之PVA系樹脂層的前述積層體薄膜以總延伸倍率為原長度5倍以上之方式進行延伸;及製造積層體薄膜之步驟,該積層體薄膜係藉由使業已吸附二色性物質之PVA系樹脂層與樹脂基材一體延伸而於樹脂基材單面形成有薄型高機能偏光膜者,且該薄型高機能偏光膜是由業已使二色性物質定向之PVA系樹脂層所構成,厚度為7μm以下,並具有單體透射率為42.0%以上且偏光度為99.95%以上之光學特性;藉此,可製造前述薄型高機能偏光膜。 Also, a manufacturing method that contains already oriented dichroic substances A laminated film of a high-performance polarizing film, which includes the following steps, that is, a step of forming a laminated film including a resin base material and a PVA-based resin layer, and the resin base material has at least 20 μm The thickness of the PVA-based resin layer is due to the fact that one side of the resin substrate will contain PVA It is formed by coating and drying an aqueous solution of a resin; the adsorption step is performed by immersing the laminate film including the resin base material and the PVA-based resin layer formed on one side of the resin base material into a dye containing a dichroic substance In the solution, the PVA-based resin layer contained in the laminate film adsorbs the dichroic substance; the extension step is in a boric acid aqueous solution to allow the aforementioned laminate film containing the PVA-based resin layer that has adsorbed the dichroic substance to The stretching ratio is stretched by 5 times or more of the original length; and a step of manufacturing a laminate film, which is formed on the resin base by integrally extending the PVA-based resin layer that has adsorbed the dichroic substance and the resin substrate The thin high-function polarizing film is formed on one side of the material, and the thin high-function polarizing film is composed of a PVA-based resin layer that has oriented a dichroic substance, has a thickness of 7 μm or less, and has a monomer transmittance of 42.0% The above and the optical property of the polarization degree is 99.95% or more; thereby, the aforementioned thin high-performance polarizing film can be manufactured.
前述特願2010-269002號說明書或特願 2010-263692號說明書之薄型偏光膜是由業已使二色性物質定向之PVA系樹脂所構成的連續基料之偏光膜,且包含有業已成膜於非晶性酯系熱可塑性樹脂基材之PVA系樹脂層之積層體是藉由2段延伸步驟來延伸,藉此,作成10μm以下之厚度,而該2段延伸步驟是由空中輔助延伸與硼酸水中延伸所構成。在將單體透射率作成T,並將偏光度作成P時,前述薄型偏光膜宜作成具有滿足P>-(100.929T-42.4-1)×100(然而,T<42.3)及P≧99.9(然而,T≧42.3)之條件之光學特性。 The thin polarizing film of the aforementioned Japanese Patent Application No. 2010-269002 or Japanese Patent Application No. 2010-263692 is a continuous base polarizing film composed of PVA-based resins which have orientated dichroic substances, and contains the film formed in The laminated body of the PVA-based resin layer of the amorphous ester-based thermoplastic resin substrate is extended by two-step stretching step, thereby making the thickness less than 10 μm, and the two-step extension step is assisted by air-assisted extension and boric acid Consists of extension in water. When the transmittance of the monomer is T and the polarization degree is P, the thin polarizing film is preferably made to satisfy P>-(10 0.929T-42.4-1 )×100 (however, T<42.3) and P≧99.9 (However, the optical characteristics of the condition T≧42.3).
具體而言,前述薄型偏光膜可藉由包含有以下步 驟之薄型偏光膜之製造方法來製造,即:一步驟,其藉由對業已成膜於連續基料之非晶性酯系熱可塑性樹脂基材之PVA系樹脂層之空中高溫延伸,生成由業已定向之PVA系樹脂層所構成的延伸中間生成物;一步驟,其藉由對延伸中間生成物之二色性物質之吸附,生成由業已使二色性物質(宜為碘或碘與有機染料之混合物)定向之PVA系樹脂層所構成的著色中間生成物;及一步驟,其藉由對著色中間生成物之硼酸水中延伸,生成由業已使二色性物質定向之PVA系樹脂層所構成且厚度為10μm以下之偏光膜。 Specifically, the thin polarizing film may include the following steps It is manufactured by a method of manufacturing a thin polarizing film in one step, that is, in one step, it is formed by stretching the PVA-based resin layer of an amorphous ester-based thermoplastic resin substrate that has been deposited on a continuous base material at high temperature in the air to generate The extended intermediate product composed of the oriented PVA-based resin layer; a step of generating a dichromatic substance (preferably iodine or iodine and organic) by adsorbing the dichroic substance of the extended intermediate product A mixture of dyes) a colored intermediate product composed of an oriented PVA-based resin layer; and a step of generating a PVA-based resin layer by orienting a dichroic substance by extending the colored intermediate product in boric acid water A polarizing film with a thickness of 10 μm or less.
於該製造方法中,利用空中高溫延伸與硼酸水中 延伸之業已成膜於非晶性酯系熱可塑性樹脂基材之PVA系樹脂層之總延伸倍率宜作成5倍以上。硼酸水中延伸用之硼酸水溶液之液溫可作成60℃以上。於硼酸水溶液中延伸著色中間生成物前,宜對著色中間生成物施行不溶化處理,此時,宜藉由將前述著色中間生成物浸漬於液溫未大於40℃之硼酸水溶液中來進行。前述非晶性酯系熱可塑性樹脂基材可作成包含有使異酞酸共聚合之共聚合聚對酞酸乙二酯、使環己烷二甲醇共聚合之共聚合聚對酞酸乙二酯或其他共聚合聚對酞酸乙二酯之非晶性聚對酞酸乙二酯,且宜為由透明樹脂所構成,其厚度可作成所成膜的PVA系樹脂層之厚度之7倍以上。又,空中高溫延伸之延伸倍率宜為3.5倍以下,且空中高溫延伸之延伸溫度宜為PVA系樹脂之玻璃轉移溫度以上,具體而言為95℃~150℃之範圍。在藉由自由端單軸延伸進行空中高溫延伸時,業已成膜於非晶性 酯系熱可塑性樹脂基材之PVA系樹脂層之總延伸倍率宜為5倍以上、7.5倍以下。又,在藉由固定端單軸延伸進行空中高溫延伸時,業已成膜於非晶性酯系熱可塑性樹脂基材之PVA系樹脂層之總延伸倍率宜為5倍以上、8.5倍以下。 In this manufacturing method, high temperature extension in the air and boric acid water are used The total stretching ratio of the PVA-based resin layer that has been filmed on the amorphous ester-based thermoplastic resin substrate for stretching is preferably 5 times or more. The liquid temperature of the boric acid aqueous solution for extension in boric acid water can be made to be above 60°C. Before extending the colored intermediate product in the aqueous solution of boric acid, the colored intermediate product is preferably subjected to an insolubilization treatment. In this case, it is preferably performed by immersing the aforementioned colored intermediate product in an aqueous solution of boric acid having a liquid temperature not higher than 40°C. The aforementioned amorphous ester-based thermoplastic resin substrate can be made of copolymerized polyethylene terephthalate copolymerized with isophthalic acid and copolymerized polyethylene terephthalate copolymerized with cyclohexane dimethanol Or other copolymerized polyethylene terephthalate, amorphous polyethylene terephthalate, and preferably made of transparent resin, the thickness of which can be made up to 7 times the thickness of the film-formed PVA-based resin layer . In addition, the stretching ratio of the high-temperature stretching in the air is preferably 3.5 times or less, and the stretching temperature of the high-temperature stretching in the air is preferably higher than the glass transition temperature of the PVA-based resin, specifically in the range of 95°C to 150°C. When the high-temperature stretching in the air is carried out by uniaxial stretching at the free end, the film has been formed in the amorphous The total stretching ratio of the PVA-based resin layer of the ester-based thermoplastic resin substrate is preferably 5 times or more and 7.5 times or less. In addition, when performing high-temperature stretching in the air by uniaxial stretching at the fixed end, the total stretching ratio of the PVA-based resin layer that has been formed on the amorphous ester-based thermoplastic resin substrate is preferably 5 times or more and 8.5 times or less.
更具體而言,藉由如下述方法,可製造薄型偏光膜。 More specifically, a thin polarizing film can be manufactured by the following method.
製作業已使異酞酸6mol%共聚合之異酞酸共聚合聚對酞酸乙二酯(非晶性PET)之連續基料之基材。非晶性PET之玻璃轉移溫度為75℃。如下述般製作由連續基料之非晶性PET基材與聚乙烯醇(PVA)層所構成的積層體。附帶一提,PVA之玻璃轉移溫度為80℃。 The manufacturing operation has made the isophthalic acid 6mol% copolymerized isophthalic acid copolymerized polyethylene terephthalate (non-crystalline PET) continuous base material of the base material. The glass transition temperature of amorphous PET is 75℃. A laminate composed of an amorphous PET substrate of a continuous base material and a polyvinyl alcohol (PVA) layer was prepared as follows. Incidentally, the glass transition temperature of PVA is 80°C.
準備200μm厚之非晶性PET基材,與業已將聚合度1000以上、皂化度99%以上之PVA粉末溶解於水中的4~5%濃度之PVA水溶液。其次,將PVA水溶液塗佈於200μm厚之非晶性PET基材,且藉由50~60℃之溫度乾燥,並製得業已於非晶性PET基材成膜7μm厚之PVA層之積層體。 Prepare an amorphous PET substrate with a thickness of 200 μm, and a PVA aqueous solution with a concentration of 4 to 5% that has dissolved PVA powder with a polymerization degree of 1000 or more and a saponification degree of 99% or more in water. Next, the PVA aqueous solution was applied to a 200 μm thick amorphous PET substrate, and dried at a temperature of 50 to 60° C., and a laminate having a 7 μm thick PVA layer formed on the amorphous PET substrate was prepared.
使包含有7μm厚之PVA層之積層體歷經包含有空中輔助延伸及硼酸水中延伸之2段延伸步驟之以下步驟,並製造3μm厚之薄型高機能偏光膜。藉由第1段之空中輔助延伸步驟,將包含有7μm厚之PVA層之積層體與非晶性PET基材一體地延伸,並生成包含有5μm厚之PVA層之延伸積層體。具體而言,該延伸積層體是將包含有7μm厚之PVA層之積層體置於烘箱中所配備的延伸裝置,並於自由端單軸延伸成延伸倍率構成1.8倍,而該烘箱設定為130℃之延伸溫度環境。藉由該延伸處理,使包含於延伸積層體之PVA 層變化成PVA分子業已定向之5μm厚之PVA層。 The laminate including the PVA layer with a thickness of 7 μm was subjected to the following steps including the two-step extension step of air-assisted extension and boric acid water extension, and a thin high-function polarizing film with a thickness of 3 μm was manufactured. By the air-assisted extension step of the first stage, the laminate including the 7 μm thick PVA layer and the amorphous PET substrate are extended integrally, and an extended laminate including the 5 μm thick PVA layer is produced. Specifically, the extension laminate is an extension device equipped with a laminate including a 7 μm thick PVA layer placed in an oven, and uniaxially extended at a free end to an extension ratio of 1.8 times, and the oven is set to 130 ℃ extended temperature environment. By this extension process, the PVA included in the extension laminate The layer changes to a 5 μm thick PVA layer with PVA molecules already oriented.
其次,藉由染色步驟,生成業已使碘吸附於PVA 分子業已定向之5μm厚之PVA層之著色積層體。具體而言,該著色積層體是將延伸積層體浸漬於液溫30℃包含有碘及碘化鉀之染色液中任意時間,以使構成最終所生成的高機能偏光膜之PVA層之單體透射率構成40~44%,藉此,使碘吸附於包含於延伸積層體之PVA層。於本步驟中,染色液是將水作為溶劑,並將碘濃度作成0.12~0.30重量%之範圍內,且將碘化鉀濃度作成0.7~2.1重量%之範圍內。碘與碘化鉀之濃度比為1比7。附帶一提,欲將碘溶解於水中時,必須要碘化鉀。更詳而言之,藉由將延伸積層體浸漬於碘濃度0.30重量%、碘化鉀濃度2.1重量%之染色液中60秒鐘,生成業已使碘吸附於PVA分子業已定向之5μm厚之PVA層之著色積層體。 Second, through the dyeing step, the production has already adsorbed iodine to PVA The colored layered body of PVA layer with 5μm thickness oriented by molecules. Specifically, the colored laminate is to immerse the stretch laminate in a dyeing solution containing iodine and potassium iodide at a liquid temperature of 30°C for an arbitrary period of time, so as to make the single-component transmittance of the PVA layer constituting the high-functional polarizing film finally generated The composition is 40% to 44%, thereby allowing iodine to be adsorbed on the PVA layer included in the elongated laminate. In this step, the dyeing solution uses water as a solvent, and the iodine concentration is in the range of 0.12 to 0.30% by weight, and the potassium iodide concentration is in the range of 0.7 to 2.1% by weight. The concentration ratio of iodine to potassium iodide is 1 to 7. By the way, when iodine is to be dissolved in water, potassium iodide must be used. More specifically, by immersing the extended laminate in a dyeing solution having an iodine concentration of 0.30% by weight and a potassium iodide concentration of 2.1% by weight for 60 seconds, a 5 μm-thick PVA layer having iodine adsorbed to PVA molecules has been formed. Colored laminate.
再者,藉由第2段之硼酸水中延伸步驟,將著色 積層體與非晶性PET基材一體地進一步延伸,並生成包含有構成3μm厚之高機能偏光膜之PVA層之光學薄膜積層體。具體而言,該光學薄膜積層體是將著色積層體置於處理裝置中所配備的延伸裝置,並於自由端單軸延伸成延伸倍率構成3.3倍,而該處理裝置設定為包含有硼酸及碘化鉀之液溫範圍60~85℃之硼酸水溶液。更詳而言之,硼酸水溶液之液溫為65℃。又,將硼酸含量相對於水100重量份而作成4重量份,並將碘化鉀含量相對於水100重量份而作成5重量份。於本步驟中,將業已調整碘吸附量之著色積層體先浸 漬於硼酸水溶液中5~10秒鐘。然後,使該著色積層體直接通過屬於處理裝置中所配備的延伸裝置之複數組周速不同之輥間,並花費30~90秒,於自由端單軸延伸成延伸倍率構成3.3倍。藉由該延伸處理,使包含於著色積層體之PVA層變化成所吸附之碘作成多碘離子複合物而多次定向於一方向之3μm厚之PVA層。該PVA層構成光學薄膜積層體之高機能偏光膜。 Furthermore, through the boric acid water extension step of the second paragraph, the coloring The laminate is further extended integrally with the amorphous PET substrate, and an optical thin-film laminate including a PVA layer constituting a high-functional polarizing film having a thickness of 3 μm is produced. Specifically, the optical film laminate is an extension device equipped with a colored laminate placed in a processing device, and is uniaxially extended at a free end to an extension magnification of 3.3 times, and the processing device is set to include boric acid and potassium iodide Boric acid aqueous solution with a liquid temperature range of 60~85℃. More specifically, the liquid temperature of the aqueous solution of boric acid is 65°C. The boric acid content was 4 parts by weight with respect to 100 parts by weight of water, and the potassium iodide content was 5 parts by weight with respect to 100 parts by weight of water. In this step, the color lamination body with adjusted iodine adsorption capacity is first dipped Stain in boric acid aqueous solution for 5~10 seconds. Then, the colored layered product is directly passed between rollers with different peripheral speeds of the complex device belonging to the stretching device provided in the processing device, and it takes 30 to 90 seconds to uniaxially stretch to a stretch magnification of 3.3 times at the free end. By this extension treatment, the PVA layer included in the colored laminate was changed to adsorbed iodine as a polyiodide ion complex and oriented multiple times in a direction of a 3 μm thick PVA layer. The PVA layer constitutes a high-performance polarizing film of an optical thin film laminate.
雖然並非光學薄膜積層體之製造所必須之步 驟,然而,宜藉由洗淨步驟,自硼酸水溶液取出光學薄膜積層體,並藉由碘化鉀水溶液,洗淨附著於業已成膜於非晶性PET基材之3μm厚之PVA層表面之硼酸。然後,藉由利用60℃之溫風之乾燥步驟,將業已洗淨之光學薄膜積層體乾燥。另,洗淨步驟是用以解決硼酸析出等外觀不良之步驟。 Although it is not a necessary step for the manufacture of optical film laminates However, it is advisable to take out the optical film laminate from the aqueous solution of boric acid by the washing step, and wash the boric acid attached to the surface of the 3 μm thick PVA layer that has been formed on the amorphous PET substrate by the aqueous potassium iodide solution. Then, the dried optical film laminate is dried by a drying step using warm air at 60°C. In addition, the washing step is a step to solve the appearance defects such as boric acid precipitation.
雖然同樣地並非光學薄膜積層體之製造所必須 之步驟,然而,亦可藉由黏合及/或轉印步驟,一面於業已成膜於非晶性PET基材之3μm厚之PVA層之表面塗佈接著劑,一面黏合80μm厚之三乙醯纖維素薄膜後,剝離非晶性PET基材,並將3μm厚之PVA層轉印於80μm厚之三乙醯纖維素薄膜。 Although it is also not necessary for the manufacture of optical film laminates However, it is also possible to apply a bonding agent on the surface of the 3 μm thick PVA layer of the amorphous PET substrate that has been film-formed by bonding and/or transfer steps, while bonding 80 μm thick triethyl acetylene on the one side After the cellulose film, the amorphous PET substrate was peeled off, and the 3 μm thick PVA layer was transferred to an 80 μm thick triacetyl cellulose film.
[其他步驟] [Other steps]
除了前述步驟外,前述薄型偏光膜之製造方法可包含有其他步驟。舉例言之,其他步驟可列舉如:不溶化步驟、交聯步驟、乾燥(含水量之調節)步驟等。其他步驟可於任意 適切之時間點進行。 In addition to the aforementioned steps, the aforementioned method of manufacturing the thin polarizing film may include other steps. For example, other steps may include, for example, an insolubilization step, a cross-linking step, and a drying (adjustment of water content) step. Other steps can be arbitrary At the right time.
代表而言,前述不溶化步驟是藉由使PVA系樹脂層浸漬於硼酸水溶液中來進行。藉由施行不溶化處理,可賦予PVA系樹脂層耐水性。相對於水100重量份,該硼酸水溶液之濃度宜為1重量份~4重量份。不溶化浴(硼酸水溶液)之液溫宜為20℃~50℃。較為理想的是不溶化步驟於積層體製作後在染色步驟或水中延伸步驟前進行。 Representatively, the aforementioned insolubilization step is performed by immersing the PVA-based resin layer in an aqueous solution of boric acid. By performing insolubilization treatment, water resistance can be imparted to the PVA-based resin layer. The concentration of the boric acid aqueous solution is preferably 1 part by weight to 4 parts by weight relative to 100 parts by weight of water. The liquid temperature of the insolubilization bath (boric acid aqueous solution) is preferably 20°C to 50°C. It is preferable that the insolubilization step is performed after the layered body is produced and before the dyeing step or the water extension step.
代表而言,前述交聯步驟是藉由使PVA系樹脂層浸漬於硼酸水溶液中來進行。藉由施行交聯處理,可賦予PVA系樹脂層耐水性。相對於水100重量份,該硼酸水溶液之濃度宜為1重量份~4重量份。又,於前述染色步驟後進行交聯步驟時,更宜摻合碘化物。藉由摻合碘化物,可抑制業已吸附於PVA系樹脂層之碘之溶出。相對於水100重量份,碘化物之摻合量宜為1重量份~5重量份。碘化物之具體例是如前述。交聯浴(硼酸水溶液)之液溫宜為20℃~50℃。較為理想的是交聯步驟於前述第2硼酸水中延伸步驟前進行。於理想之實施形態中,將染色步驟、交聯步驟及第2硼酸水中延伸步驟依該順序進行。 Representatively, the aforementioned cross-linking step is performed by immersing the PVA-based resin layer in an aqueous solution of boric acid. By performing the cross-linking treatment, the PVA-based resin layer can be given water resistance. The concentration of the boric acid aqueous solution is preferably 1 part by weight to 4 parts by weight relative to 100 parts by weight of water. In addition, when the cross-linking step is performed after the aforementioned dyeing step, it is more preferable to blend the iodide. By blending iodide, the elution of iodine that has been adsorbed to the PVA-based resin layer can be suppressed. The blending amount of iodide is preferably 1 part by weight to 5 parts by weight relative to 100 parts by weight of water. Specific examples of iodide are as described above. The liquid temperature of the cross-linking bath (boric acid aqueous solution) is preferably 20°C to 50°C. Preferably, the cross-linking step is performed before the second boric acid water extension step. In an ideal embodiment, the dyeing step, the cross-linking step, and the second boric acid water extension step are performed in this order.
<透明保護薄膜> <transparent protective film>
形成設於前述偏光件之單面或兩面之透明保護薄膜之材料宜為透明性、機械強度、熱安定性、水分阻斷性、等向性等優異之材料。舉例言之,可列舉如:聚對酞酸乙二酯或聚萘二甲酸乙二酯等聚酯系聚合物、二乙醯纖維素或三乙醯纖維素等纖維素系聚合物、聚甲基甲基丙烯酸酯等 丙烯酸系聚合物、聚苯乙烯或丙烯腈.苯乙烯共聚物(AS樹脂)等苯乙烯系聚合物、聚碳酸酯系聚合物等。又,亦可列舉為形成前述透明保護薄膜之聚合物之例子的是:如聚乙烯、聚丙烯、具有環系或降莰烯結構之聚烯烴、乙烯.丙烯共聚物之聚烯烴系聚合物、氯乙烯系聚合物、耐綸或芳香族聚醯胺等醯胺系聚合物、醯亞胺系聚合物、碸系聚合物、聚醚碸系聚合物、聚醚醚酮系聚合物、聚苯硫系聚合物、乙烯醇系聚合物、二氯亞乙烯系聚合物、乙烯丁醛系聚合物、芳酯系聚合物、聚甲醛系聚合物、環氧系聚合物或前述聚合物之摻合物等。於透明保護薄膜中亦可含有1種以上任意適切之添加劑。舉例言之,添加劑可列舉如:紫外線吸收劑、抗氧化劑、潤滑劑、可塑劑、脫模劑、防著色劑、難燃劑、成核劑、防帶電劑、顏料、著色劑等。 透明保護薄膜中的前述熱可塑性樹脂之含量宜為50~100重量%,且更宜為50~99重量%,進而宜為60~98重量%,特別是宜為70~97重量%。當透明保護薄膜中的前述熱可塑性樹脂之含量為50重量%以下時,會有熱可塑性樹脂原本所具有的高透明性等無法充分地顯現之虞。 The material forming the transparent protective film provided on one or both sides of the polarizer is preferably a material excellent in transparency, mechanical strength, thermal stability, moisture blocking property, isotropy and the like. Examples include polyester-based polymers such as polyethylene terephthalate or polyethylene naphthalate, cellulose-based polymers such as diethyl cellulose or triethylene cellulose, and polymethine Methacrylate Acrylic polymer, polystyrene or acrylonitrile. Styrene-based polymers such as styrene copolymers (AS resins) and polycarbonate-based polymers. Also, examples of the polymer forming the transparent protective film are: polyethylene, polypropylene, polyolefin having a ring system or norbornene structure, ethylene. Propylene copolymers such as polyolefin-based polymers, vinyl chloride-based polymers, nylon or aromatic polyamide-based amide-based polymers, amide-imide-based polymers, lanyard-based polymers, polyether lanyard-based polymers, Polyetheretherketone polymer, polyphenylene sulfide polymer, vinyl alcohol polymer, dichlorovinylidene polymer, ethylene butyraldehyde polymer, aryl ester polymer, polyoxymethylene polymer, epoxy It is a polymer or a blend of the aforementioned polymers. The transparent protective film may also contain more than one kind of any suitable additives. For example, the additives may include, for example, ultraviolet absorbers, antioxidants, lubricants, plasticizers, mold release agents, anti-coloring agents, flame retardants, nucleating agents, anti-static agents, pigments, coloring agents, and the like. The content of the aforementioned thermoplastic resin in the transparent protective film is preferably 50 to 100% by weight, and more preferably 50 to 99% by weight, further preferably 60 to 98% by weight, and particularly preferably 70 to 97% by weight. When the content of the thermoplastic resin in the transparent protective film is 50% by weight or less, there is a possibility that the high transparency originally possessed by the thermoplastic resin and the like may not be sufficiently exhibited.
又,透明保護薄膜可列舉如:日本特開 2001-343529號公報(WO01/37007)中所揭示之聚合物薄膜,例如含有(A)側鏈具有取代及/或非取代亞胺基之熱可塑性樹脂及(B)側鏈具有取代及/或非取代苯基及腈基之熱可塑性樹脂之樹脂組成物。具體例可列舉如:含有由異丁烯與N-甲基馬來醯亞胺所構成的交替共聚物及丙烯腈.苯乙 烯共聚物之樹脂組成物之薄膜。薄膜可使用由樹脂組成物之混合押出品等所構成的薄膜。該等薄膜之相位差小,且光彈性係數小,因此,可解決偏光薄膜之應變所造成的不均等問題,又,由於透濕度小,因此,加濕耐久性優異。 In addition, the transparent protective film may be exemplified by Japanese Patent Application The polymer film disclosed in Gazette No. 2001-343529 (WO01/37007), for example, a thermoplastic resin containing (A) a substituted and/or unsubstituted imide group in the side chain and (B) a substituted and/or side chain Resin composition of unsubstituted phenyl and nitrile based thermoplastic resin. Specific examples include, for example, containing alternating copolymers consisting of isobutylene and N-methylmaleimide and acrylonitrile. Styrene Film of resin composition of olefin copolymer. As the film, a film composed of a mixed extruded product of a resin composition or the like can be used. The phase difference of these films is small, and the photoelastic coefficient is small. Therefore, the unevenness caused by the strain of the polarizing film can be solved. Also, because the moisture permeability is small, the humidification durability is excellent.
於前述偏光薄膜中,前述透明保護薄膜之透濕度 宜為150g/m2/24h以下。若藉由前述構造,則空氣中的水分難以進入偏光薄膜中,且可抑制偏光薄膜本身之含水量變化。其結果,可抑制因保存環境所產生的偏光薄膜之捲邊或尺寸變化。 In the polarizing film, the transparent protective film preferably has a moisture permeability of 150 g/m 2 /24h or less. With the aforementioned structure, it is difficult for moisture in the air to enter the polarizing film, and the change in the water content of the polarizing film itself can be suppressed. As a result, the curling or dimensional change of the polarizing film due to the storage environment can be suppressed.
形成設於前述偏光件之單面或兩面之透明保護 薄膜之材料宜為透明性、機械強度、熱安定性、水分阻斷性、等向性等優異之材料,特別是更宜為透濕度為150g/m2/24h以下者,且特別理想的是140g/m2/24h以下,更為理想的是120g/m2/24h以下。透濕度可藉由實施例所揭示之方法來求取。 The material forming the transparent protective film provided on one or both sides of the polarizer is preferably a material with excellent transparency, mechanical strength, thermal stability, moisture blocking property, isotropy, etc. 150 g/m 2 /24h or less, and particularly preferably 140 g/m 2 /24h or less, and more preferably 120 g/m 2 /24h or less. The water vapor permeability can be obtained by the method disclosed in the embodiment.
舉例言之,滿足前述低透濕度之透明保護薄膜之 形成材料可使用:聚對酞酸乙二酯或聚萘二甲酸乙二酯等聚酯樹脂;聚碳酸酯樹脂;芳酯系樹脂;耐綸或芳香族聚醯胺等醯胺系樹脂;如聚乙烯、聚丙烯、乙烯.丙烯共聚物之聚烯烴系聚合物、具有環系或降莰烯結構之環狀烯烴系樹脂、(甲基)丙烯酸系樹脂或該等之混合體。於前述樹脂中,亦宜為聚碳酸酯系樹脂、環狀聚烯烴系樹脂、(甲基)丙烯酸系樹脂,特別是宜為環狀聚烯烴系樹脂、(甲基)丙烯酸系樹脂。 For example, a transparent protective film that satisfies the aforementioned low moisture permeability The forming material can be used: polyester resins such as polyethylene terephthalate or polyethylene naphthalate; polycarbonate resins; aryl ester resins; nylon or aromatic polyamide resins such as polyamide resins; such as Polyethylene, polypropylene, ethylene. A polyolefin polymer of a propylene copolymer, a cyclic olefin resin having a ring system or norbornene structure, a (meth)acrylic resin, or a mixture of these. Among the aforementioned resins, polycarbonate resins, cyclic polyolefin resins, and (meth)acrylic resins are also preferred, and cyclic polyolefin resins and (meth)acrylic resins are particularly preferred.
透明保護薄膜之厚度可適當地決定,一般而言, 若由強度或處理性等作業性、薄層性等觀點來看,則為1~100μm。特別是宜為1~80μm,且更宜為3~60μm。 The thickness of the transparent protective film can be appropriately determined. Generally speaking, From the viewpoint of workability such as strength and handleability, and thin layer properties, it is 1 to 100 μm. In particular, it is preferably 1 to 80 μm, and more preferably 3 to 60 μm.
另,於偏光件之兩面設置透明保護薄膜時,可使用由其表裡相同之聚合物材料所構成的透明保護薄膜,亦可使用由不同之聚合物材料等所構成的透明保護薄膜。 In addition, when the transparent protective films are provided on both sides of the polarizer, a transparent protective film composed of the same polymer material on the surface and a transparent protective film composed of different polymer materials can also be used.
於前述透明保護薄膜未接著偏光件之面可設置硬塗層、防反射層、防黏層、擴散層或防眩光層等機能層。另,前述硬塗層、防反射層、防黏層、擴散層或防眩光層等機能層除了可設置於透明保護薄膜本身之外,亦可另外設置成有別於透明保護薄膜。 A functional layer such as a hard coat layer, an anti-reflection layer, an anti-adhesive layer, a diffusion layer, or an anti-glare layer may be provided on the surface of the transparent protective film that is not attached to the polarizer. In addition, the functional layer such as the hard coat layer, the anti-reflection layer, the anti-sticking layer, the diffusion layer, or the anti-glare layer can be provided not only on the transparent protective film itself, but also on a transparent protective film.
<光學薄膜> <optical film>
本發明之偏光薄膜可作成實用上與其他光學層積層之光學薄膜來使用。該光學層並無特殊之限制,舉例言之,可使用1層或2層以上之反射板、半透射板、相位差板(包含有1/2或1/4等之波長板)或視角補償薄膜等使用於液晶顯示裝置等之形成的光學層。特別理想的是構成為於本發明之偏光薄膜更積層反射板或半透射反射板之反射型偏光薄膜或半透射型偏光薄膜、構成為於偏光薄膜更積層相位差板之橢圓偏光薄膜或圓偏光薄膜、構成為於偏光薄膜更積層視角補償薄膜之廣視野角偏光薄膜或構成為於偏光薄膜更積層亮度提昇薄膜之偏光薄膜。 The polarizing film of the present invention can be used as an optical film laminated with other optical layers in practical use. The optical layer is not particularly limited. For example, one or more reflective plates, semi-transmissive plates, retardation plates (including 1/2 or 1/4 wavelength plates) or viewing angle compensation can be used Thin films and the like are used for optical layers formed in liquid crystal display devices and the like. It is particularly desirable to construct a reflective polarizing film or a semi-transmissive polarizing film configured as a laminated polarizer film or a semi-transmissive reflective plate of the present invention, an elliptical polarizing film or a circularly polarized light configured as a polarizing film further laminated as a retardation plate The film, the wide viewing angle polarizing film configured to layer a viewing angle compensation film on the polarizing film, or the polarizing film configured to layer a brightness enhancement film on the polarizing film.
業已於偏光薄膜積層前述光學層之光學薄膜亦可藉由於液晶顯示裝置等之製造過程中依序個別地積層之 方式來形成,然而,預先積層而作成光學薄膜者具有品質安定性或組裝作業等優異而可提昇液晶顯示裝置等之製造步驟之優點。積層可使用黏著層等適當之接著機構。於前述偏光薄膜或其他光學薄膜之接著時,該等之光學軸可按照作為目標之相位差特性等而作成適當之配置角度。 The optical films that have been laminated on the polarizing film can also be individually laminated in sequence due to the manufacturing process of liquid crystal display devices, etc. However, the optical film that is laminated in advance to produce an optical film has the advantages of excellent quality stability, assembly work, and the like, and can improve the manufacturing steps of the liquid crystal display device and the like. For the lamination, an appropriate bonding mechanism such as an adhesive layer can be used. When attaching the aforementioned polarizing film or other optical film, the optical axes of these can be arranged at an appropriate angle according to the target phase difference characteristics and the like.
於前述偏光薄膜或積層至少1層偏光薄膜之光學薄膜亦可設置用以與液晶晶胞等其他構件接著之黏著層。形成黏著層之黏著劑並無特殊之限制,舉例言之,可適當地選擇、使用將丙烯酸系聚合物、聚矽氧系聚合物、聚酯、聚胺基甲酸酯、聚醯胺、聚醚、氟系或橡膠系等之聚合物作為基礎聚合物之黏著劑。特別是宜使用如丙烯酸系黏著劑般光學透明性優異並顯示適度之潤濕性、凝聚性與接著性之黏著特性而耐氣候性或耐熱性等優異之黏著劑。 The polarizing film or the optical film laminated with at least one polarizing film may also be provided with an adhesive layer for adhering to other members such as liquid crystal cells. The adhesive that forms the adhesive layer is not particularly limited. For example, acrylic polymers, polysiloxane polymers, polyesters, polyurethanes, polyamides, Polymers such as ether, fluorine or rubber are used as adhesives for basic polymers. In particular, adhesives that are excellent in optical transparency like acrylic adhesives, exhibit moderate wettability, cohesiveness, and adhesive properties, and have excellent weather resistance, heat resistance, etc. are preferably used.
黏著層亦可作成不同組成或種類等者之重疊層而設於偏光薄膜或光學薄膜之單面或兩面。又,設於兩面時,亦可於偏光薄膜或光學薄膜之表裡作成不同組成、種類或厚度等之黏著層。黏著層之厚度可按照使用目的或接著力等適當地決定,然而,一般為1~500μm,且宜為1~200μm,特別是宜為1~100μm。 The adhesive layer can also be made as an overlapping layer of different composition or type, etc. and provided on one side or both sides of the polarizing film or the optical film. In addition, when it is provided on both sides, adhesive layers of different compositions, types, or thicknesses may be formed on the surface of the polarizing film or the optical film. The thickness of the adhesive layer can be appropriately determined according to the purpose of use or adhesion, etc. However, it is generally 1 to 500 μm, and preferably 1 to 200 μm, especially 1 to 100 μm.
在直到供實用為止之期間,以防止其污染等為目的,對黏著層之露出面暫時黏著、覆蓋分隔件。藉此,可防止於慣例之處理狀態下與黏著層接觸。除了前述厚度條件外,分隔件可使用例如依需要藉由聚矽氧系或長鏈烷基系、氟系或硫化鉬等適當之剝離劑,將塑膠薄膜、橡膠片、 紙、布、不織布、網狀物、發泡片或金屬箔、該等之層合體等適當之薄片體進行塗佈處理等遵照以往標準之適當者。 During the period until it is put into practical use, for the purpose of preventing contamination, etc., the exposed surface of the adhesive layer is temporarily adhered to cover the partition. This prevents contact with the adhesive layer under conventional processing conditions. In addition to the aforementioned thickness conditions, the separator can be used, for example, by a suitable release agent such as polysiloxane-based or long-chain alkyl-based, fluorine-based or molybdenum sulfide, to separate the plastic film, rubber sheet, Appropriate sheet materials such as paper, cloth, non-woven fabric, mesh, foamed sheet or metal foil, laminates of these, etc. are subjected to coating treatment, etc., which are in conformity with conventional standards.
<影像顯示裝置> <Image display device>
本發明之偏光薄膜或光學薄膜可理想地使用於液晶顯示裝置等各種裝置之形成等。液晶顯示裝置之形成可遵照以往標準來進行。即,一般而言,液晶顯示裝置是藉由適當地組裝液晶晶胞與偏光薄膜或光學薄膜及依需要之照明系統等構成零件而裝入驅動電路等來形成,然而,於本發明中,除了使用依據本發明之偏光薄膜或光學薄膜方面外,並無特殊之限制,可遵照以往標準。舉例言之,液晶晶胞亦可使用TN型、STN型或π型等任意型式者。 The polarizing film or optical film of the present invention can be preferably used for forming various devices such as liquid crystal display devices. The formation of the liquid crystal display device can be carried out in accordance with previous standards. That is, in general, a liquid crystal display device is formed by appropriately assembling a liquid crystal cell and a polarizing film or an optical film, and as necessary a lighting system and other components, and incorporating a driving circuit, etc. However, in the present invention, except There is no special restriction on the use of the polarizing film or optical film according to the present invention, and it can follow the previous standards. For example, the liquid crystal cell may use any type such as TN type, STN type, or π type.
可形成業已於液晶晶胞之單側或兩側配置偏光薄膜或光學薄膜之液晶顯示裝置,或於照明系統中使用背光源或反射板者等適當之液晶顯示裝置。此時,依據本發明之偏光薄膜或光學薄膜可設置於液晶晶胞之單側或兩側。將偏光薄膜或光學薄膜設於兩側時,該等可為相同,亦可為不同。再者,於液晶顯示裝置之形成時,舉例言之,可將擴散板、防眩光層、防反射膜、保護板、稜鏡陣列、透鏡陣列片、光擴散板、背光源等適當之零件於適當之位置配置1層或2層以上。 Appropriate liquid crystal display devices such as a liquid crystal display device in which a polarizing film or an optical film is arranged on one or both sides of a liquid crystal cell, or a backlight or a reflective plate used in an illumination system can be formed. At this time, the polarizing film or the optical film according to the present invention can be disposed on one side or both sides of the liquid crystal cell. When polarizing films or optical films are provided on both sides, these may be the same or different. Furthermore, in the formation of the liquid crystal display device, for example, appropriate parts such as a diffusion plate, an anti-glare layer, an anti-reflection film, a protection plate, a prism array, a lens array sheet, a light diffusion plate, a backlight, etc. can be used Arrange one layer or more than two layers in appropriate locations.
以下揭示本發明之實施例,然而,本發明之實施形態並不限於該等。 The embodiments of the present invention are disclosed below, however, the embodiments of the present invention are not limited to these.
<偏光件之製作> <Production of polarizers>
將平均聚合度2400、皂化度99.9莫耳%之厚度75μm之聚乙烯醇薄膜浸漬於30℃之溫水中60秒鐘,並使其膨潤。接著,浸漬於碘/碘化鉀(重量比=0.5/8)之濃度0.3%之水溶液中,且一面延伸至3.5倍,一面將薄膜染色。然後,於65℃之硼酸酯水溶液中進行延伸,以使總延伸倍率構成6倍。延伸後,藉由40℃之烘箱進行乾燥3分鐘,並製得PVA系偏光件X(厚度23μm)。 A 75 μm thick polyvinyl alcohol film with an average degree of polymerization of 2400 and a degree of saponification of 99.9 mol% was immersed in warm water at 30° C. for 60 seconds and swelled. Next, it was immersed in an aqueous solution of 0.3% concentration of iodine/potassium iodide (weight ratio=0.5/8), and the film was dyed while being extended to 3.5 times. Then, stretching is carried out in an aqueous solution of boric acid ester at 65° C., so that the total stretching ratio becomes 6 times. After the extension, drying was carried out in an oven at 40° C. for 3 minutes, and a PVA-based polarizer X (thickness 23 μm) was prepared.
<透明保護薄膜> <transparent protective film>
透明保護薄膜1:未進行皂化、電暈處理等而使用厚度60μm之三乙醯纖維素薄膜(透濕度530g/m2/24h)(表1中標示為TAC)。 Transparent protective film 1: without saponification, corona treatment, etc., a triacetyl cellulose film with a thickness of 60 μm (moisture permeability 530 g/m 2 /24h) (marked as TAC in Table 1) was used.
透明保護薄膜2:於厚度40μm之具有內酯環結構之(甲基)丙烯酸樹脂(透濕度96g/m2/24h)施行電暈處理而使用(表1中標示為丙烯酸)。 Transparent protective film 2: (meth)acrylic resin having a lactone ring structure with a thickness of 40 μm (moisture permeability 96 g/m 2 /24h) is used after corona treatment (marked as acrylic in Table 1).
透明保護薄膜3:於厚度55μm之環狀聚烯烴薄膜(日本瑞翁(ZEON)公司製:ZEONOR,透濕度11g/m2/24h)施行電暈處理而使用(於表1中標示為COP)。 Transparent protective film 3: cyclic polyolefin film with a thickness of 55 μm (manufactured by Zeon Corporation: ZEONOR, moisture permeability 11 g/m 2 /24h) and used for corona treatment (marked as COP in Table 1) .
<透明保護薄膜之透濕度> <Moisture permeability of transparent protective film>
透濕度之測定是遵照JIS Z0208之透濕度試驗(透濕杯法)來測定。將業已切斷成直徑60mm之試樣安置於業已放入約15g之氯化鈣之透濕杯,並放入溫度40℃、濕度90%R.H.之恆溫機中,且測定放置24小時前後之氯化鈣之重量增加,藉此,求取透濕度(g/m2/24h)。 The moisture permeability is measured in accordance with the moisture permeability test (moisture permeability cup method) of JIS Z0208. Place the sample that has been cut into a diameter of 60mm in a moisture-permeable cup that has been placed with about 15g of calcium chloride, and put it into a thermostat with a temperature of 40°C and a humidity of 90%RH, and measure the chlorine before and after 24 hours. By increasing the weight of calcium chloride, the moisture permeability (g/m 2 /24h) was determined.
<活性能量線> <active energy line>
活性能量線是使用可見光線(封入鎵之金屬鹵素燈),照射裝置:Fusion UV Systems,Inc公司製Light HAMMER10,閥:V閥,峰值照度:1600mW/cm2,累計照射量1000mJ/cm2(波長380~440nm)。另,可見光線之照度是使用Solatell公司製Sola-Check系統來測定。 The active energy ray uses visible light (metal halide lamp enclosed in gallium), irradiation device: Fusion UV Systems, Inc. Light HAMMER10, valve: V valve, peak illuminance: 1600mW/cm 2 , cumulative exposure 1000mJ/cm 2 ( (Wavelength 380~440nm). In addition, the illuminance of visible light is measured using the Sola-Check system manufactured by Solatell.
實施例1~4及比較例1~5 Examples 1 to 4 and Comparative Examples 1 to 5
(活性能量線硬化型接著劑之調製) (Preparation of active energy ray hardening adhesive)
依據表1所揭示之摻合表,混合各成分而藉由50℃攪拌1小時,並製得有關實施例1及比較例1之活性能量線硬化型接著劑。另,有關實施例1之活性能量線硬化型接著劑之黏度為95cp(25℃),有關比較例1之活性能量線硬化型接著劑之黏度為45cp(25℃)。 According to the blending table disclosed in Table 1, the components were mixed and stirred at 50° C. for 1 hour, and the active energy ray-curable adhesives related to Example 1 and Comparative Example 1 were prepared. In addition, the viscosity of the active energy ray-curable adhesive in Example 1 is 95 cp (25°C), and the viscosity of the active energy ray-curable adhesive in Comparative Example 1 is 45 cp (25°C).
(偏光薄膜之製作) (Production of polarizing film)
使用MCD塗佈機(富士機械公司製)(單胞形狀:蜂巢狀,凹版輥線數:1000支/inch,旋轉速度140%/成對線速),於前述透明保護薄膜上將有關前述實施例或比較例之活性能量線硬化型接著劑塗覆成厚度0.7μm,並藉由輥機黏合於前述偏光件X之兩面。然後,使用IR加熱器,自業已黏合之透明保護薄膜側(兩側)加溫成50℃,並將前述可見光線照射至兩面而使有關前述實施例或比較例之活性能量線硬化型接著劑硬化後,藉由70℃熱風乾燥3分鐘,並製得於偏光件之兩側具有透明保護薄膜之偏光薄膜。黏合之線速度是藉由25m/min來進行。 Using the MCD coater (manufactured by Fuji Machinery Co., Ltd.) (single cell shape: honeycomb shape, gravure roll line number: 1000 pcs/inch, rotation speed 140%/pair line speed), the above-mentioned implementation of the above-mentioned transparent protective film The active energy ray hardening type adhesive of the example or the comparative example is coated to a thickness of 0.7 μm, and is bonded to both sides of the polarizer X by a roller machine. Then, using an IR heater, the self-adhesive transparent protective film side (both sides) is heated to 50° C., and the aforementioned visible light is irradiated to both sides to make the active energy ray-curable adhesive agent related to the aforementioned example or comparative example. After curing, it is dried by hot air at 70°C for 3 minutes, and a polarizing film having transparent protective films on both sides of the polarizing member is prepared. The linear speed of bonding is carried out by 25m/min.
偏光薄膜之製作是針對前述透明保護薄膜1至3三種分別進行。 The polarizing film is produced for the three types of transparent protective films 1 to 3 mentioned above.
針對藉由前述實施例及比較例所製得之偏光薄膜進行以下評價。表1顯示評價結果。另,於加濕耐久性及接著耐水性之評價時,另外分別製作相同之偏光薄膜。 The following evaluation was performed on the polarizing film produced by the foregoing examples and comparative examples. Table 1 shows the evaluation results. In addition, in the evaluation of the humidification durability and the subsequent water resistance, the same polarizing film was separately prepared.
<整體吸水率> <overall water absorption rate>
使用各例中所使用的偏光薄膜用硬化型接著劑,並藉由設置有100μm之分隔件之2片玻璃來夾持,且藉由與實施例相同之活性能量條件硬化而調製厚度100μm之接著劑層(硬化物)。將此作為試樣。將試樣之重量作成M1g。將試樣M1g浸漬於23℃之純水中24小時。然後,自純水取出而藉由乾布擦拭後,於1分鐘以內再度測定試樣之重量(M2g)。藉由下述式,自該等結果算出整體吸水率,即:式:{(M2-M1)/M1}×100(%)。 The hardening adhesive for polarizing film used in each example was used, sandwiched by two pieces of glass provided with a 100 μm separator, and cured with the same active energy conditions as in the example to modulate a thickness of 100 μm. Agent layer (hardened). Use this as a sample. Make the weight of the sample M1g. The sample M1g was immersed in pure water at 23°C for 24 hours. Then, after taking out from pure water and wiping with a dry cloth, the weight (M2g) of the sample was measured again within 1 minute. The overall water absorption rate is calculated from these results by the following formula, namely: Formula: {(M2-M1)/M1}×100(%).
<硬化收縮率> <hardening shrinkage>
藉由聖鐵克公司製硬化收縮感測器「樹脂硬化收縮應力測定裝置EU201C」來測定。具體而言,藉由特開2013-104869所揭示之方法,算出硬化收縮率。另,自有關實施例1之活性能量線硬化型接著劑所形成的硬化物之硬化收縮率為8.9%,自有關比較例1之活性能量線硬化型接著劑所形成的硬化物之硬化收縮率為11.9%。 It is measured by the hardening shrinkage sensor "resin hardening shrinkage stress measuring device EU201C" manufactured by Shengtieke. Specifically, by the method disclosed in JP-A 2013-104869, the hardening shrinkage ratio is calculated. In addition, the curing shrinkage rate of the cured product formed from the active energy ray hardening type adhesive of Example 1 is 8.9%, and the curing shrinkage rate of the cured product formed from the active energy ray hardening type adhesive of Related Example 1 is 11.9%.
<接著力> <adhesion>
將各例中所製得之偏光薄膜切出與偏光件之延伸方向平行為200mm、直行方向為20mm之大小,並藉由截切刀, 於透明保護薄膜與偏光件間加入切口,並將偏光薄膜黏合於玻璃板。藉由萬能試驗機(TENSILON),於90度方向將透明保護薄膜與偏光件以剝離速度500mm/min進行剝離,並測定其剝離強度。又,藉由ATR法,測定剝離後之剝離面之紅外線吸收光譜,並根據下述基準評價剝離界面。 The polarizing film prepared in each example was cut out to a size parallel to the extending direction of the polarizing member of 200 mm and a straight direction of 20 mm, and by a cutting knife, A cut is added between the transparent protective film and the polarizer, and the polarizing film is adhered to the glass plate. With a universal testing machine (TENSILON), the transparent protective film and the polarizer were peeled at a peeling speed of 500 mm/min in the direction of 90 degrees, and the peel strength was measured. In addition, the infrared absorption spectrum of the peeled surface after peeling was measured by the ATR method, and the peeling interface was evaluated according to the following criteria.
A:透明保護薄膜之凝聚破壞 A: Cohesive destruction of transparent protective film
B:透明保護薄膜/接著劑層間之界面剝離 B: Interface peeling between transparent protective film/adhesive layer
C:接著劑層/偏光件間之界面剝離 C: Interface peeling between adhesive layer/polarizer
D:偏光件之凝聚破壞 D: Cohesive destruction of polarizer
於前述基準中,A及D是意味著接著力為薄膜之凝聚力以上,因此,接著力非常優異。另一方面,B及C是意味著透明保護薄膜/接著劑層(接著劑層/偏光件)界面之接著力不足(接著力差)。考慮該等而將屬於A或D時之接著力作成○,將屬於A.B(同時產生「透明保護薄膜之凝聚破壞」與「透明保護薄膜/接著劑層間之界面剝離」)或A.C(同時產生「透明保護薄膜之凝聚破壞」與「接著劑層/偏光件間之界面剝離」)時之接著力作成△,將屬於B或C時之接著力作成×。 In the aforementioned criteria, A and D mean that the adhesive force is more than the cohesive force of the film, and therefore, the adhesive force is very excellent. On the other hand, B and C mean that the adhesive force at the interface of the transparent protective film/adhesive layer (adhesive layer/polarizer) is insufficient (adhesive force is poor). Considering these and making the adhesive force when it belongs to A or D ○, it will belong to A. B (simultaneously produces "agglomeration destruction of transparent protective film" and "interfacial peeling between transparent protective film/adhesive layer") or A. C (At the same time, the "cohesive failure of the transparent protective film" and "the peeling of the interface between the adhesive layer and the polarizer") are made into △, and the adhesion force of B or C is made into ×.
<加濕耐久性:單體透射率、偏光度變化之測定> <Humidity Durability: Measurement of Changes in Transmittance and Polarization of Monomers>
藉由與實施例及比較例相同之方法,將業已於偏光件之兩面分別積層各一片透明保護薄膜2與3作為透明保護薄膜之偏光薄膜製作成試樣。將該偏光薄膜(試樣)投入85℃/85%RH之恆溫恆濕機中500小時。使用具積分球之分光透射率測定器(村上色彩技術研究所之Dot-3c),測定投入前與 投入後之偏光薄膜之單體透射率與偏光度,並求取:單體透射率之變化量(△T:%)=(投入後之單體透射率(%))-(投入前之單體透射率(%));偏光度之變化量(△P:%)=(投入後之偏光度(%))-(投入前之偏光度(%))。 By the same method as in the examples and comparative examples, a polarizing film having transparent protective films 2 and 3 as transparent protective films laminated on each side of the polarizer was prepared as a sample. This polarizing film (sample) was put into a constant temperature and humidity machine at 85°C/85%RH for 500 hours. Use a spectrophotometer with an integrating sphere (Dot-3c from Murakami Color Technology Research Institute) to measure the Monomer transmittance and polarization degree of the polarizing film after input, and calculate: the amount of change in monomer transmittance (△T:%) = (monomer transmittance after input (%))-(single before input Volume transmittance (%)); the amount of change in polarization (△P:%) = (polarization after input (%))-(polarization before input (%)).
另,偏光度P是藉由將業已將2片相同之偏光薄膜疊合成兩者之透射軸構成平行時之透射率(平行透射率:Tp)及疊合成兩者之透射軸呈正交時之透射率(正交透射率:Tc)應用於以下式中而求取。 In addition, the polarization degree P is obtained by stacking two identical polarizing films into a parallel transmission axis (parallel transmittance: Tp) and when the transmission axes of the two are orthogonal. The transmittance (orthogonal transmittance: Tc) is obtained by applying the following formula.
偏光度P(%)={(Tp-Tc)/(Tp+Tc)}1/2×100 Polarization P(%)={(Tp-Tc)/(Tp+Tc)} 1/2 ×100
各透射率是將通過格蘭泰勒稜鏡偏光件而得之完全偏光作成100%而藉由業已藉由JIS Z8701之2度視野(C光源)進行視感度校正之Y值來表示。 Each transmittance is expressed by the Y value of the visual acuity correction which has been performed by the 2 degree field of view (C light source) of JIS Z8701 by making 100% of the fully polarized light obtained by the polarizer of Gran Taylor.
<接著耐水性(溫水浸漬試驗)> <Next water resistance (warm water immersion test)>
藉由與實施例及比較例相同之方法,將業已於偏光件之兩面分別積層各一片透明保護薄膜1與3作為透明保護薄膜之偏光薄膜製作成試樣。將該偏光薄膜(試樣)切割成偏光件之延伸方向為50mm、垂直方向為25mm之長方形。將前述偏光薄膜浸漬於60℃之溫水中6小時後,藉由放大鏡以目視測定業已剝離之長度。測定是作成起自引起剝離之部分之截面之垂直距離之最大值(mm)。 By the same method as the examples and the comparative examples, polarizing films which have been respectively laminated with transparent protective films 1 and 3 as transparent protective films on both sides of the polarizer were prepared as samples. The polarizing film (sample) was cut into a rectangular shape in which the polarizer had an extension direction of 50 mm and a vertical direction of 25 mm. After immersing the polarizing film in warm water at 60°C for 6 hours, the length after peeling was visually measured with a magnifying glass. The measurement is the maximum value (mm) of the vertical distance of the cross-section from the part causing peeling.
<接著耐水性(耐水剝離力)> <Next Water Resistance (Water Peeling Resistance)>
藉由與實施例及比較例相同之方法,將業已於偏光件之兩面分別積層各一片透明保護薄膜1與3作為透明保護薄 膜之偏光薄膜製作成試樣。將該偏光薄膜(試樣)切出與偏光件之延伸方向平行為200mm、直行方向為20mm之大小。將該偏光薄膜浸漬於23℃之純水中24小時後,自純水中取出,並藉由乾布擦拭後,藉由截切刀,於透明保護薄膜與偏光件間加入切口,並將偏光薄膜黏合於玻璃板。自純水中取出後至評價為止是在1分鐘以內進行。以後,進行與前述<接著力>相同之評價。 By the same method as the examples and comparative examples, a transparent protective film 1 and 3 have been laminated on both sides of the polarizer as a transparent protective thin film The polarized film of the film is made into a sample. The polarizing film (sample) was cut out to a size parallel to the extending direction of the polarizer of 200 mm and the straight direction of 20 mm. After immersing the polarizing film in pure water at 23°C for 24 hours, remove it from the pure water and wipe it off with a dry cloth, add a cut between the transparent protective film and the polarizer with a cutting knife, and apply the polarizing film Bonded to the glass plate. It takes less than 1 minute from taking out pure water to evaluation. Thereafter, the same evaluation as the aforementioned <adhesive force> is performed.
<logPow之計算> <Calculation of logPow>
使用藉由Chem Draw Ultra(劍橋軟體公司製)而得之各個化合物之logPow值,並藉由下述式進行計算。另,聚合引發劑及光酸產生劑會自計算中扣除。 The logPow value of each compound obtained by Chem Draw Ultra (manufactured by Cambridge Software Corporation) was used, and calculation was performed by the following formula. In addition, the polymerization initiator and photoacid generator will be deducted from the calculation.
硬化型接著劑之logPow=Σ(logPowi×Wi) LogPow=Σ(logPowi×Wi) of hardening adhesive
logPowi:硬化型接著劑之各成分之logPow值 logPowi: the logPow value of each component of the hardening adhesive
Wi:(i成分之莫耳數)/(硬化型接著劑之各成分之總莫耳數) Wi: (mole number of component i)/(total moles of each component of hardening adhesive)
表1中,自由基聚合性化合物是顯示:HEAA:羥乙基丙烯醯胺,logPow=-0.56,均聚物之Tg=123℃,興人公司製;ACMO:丙烯醯基嗎啉,logPow=-0.20,均聚物之Tg=150℃,興人公司製;FA-THFM:四氫糠基(甲基)丙烯酸酯,logPow=1.13,均聚物之Tg=45℃,日立化成公司製;LIGHT ACRYLATE DCP-A:三環癸烷二甲醇二丙烯酸酯,logPow=3.05,均聚物之Tg=134℃,共榮社化學公司製;LIGHT ACRYLATE1,9ND-A:1,9-壬二醇二丙烯酸酯,logPow=3.68,均聚物之Tg=68℃,共榮社化學公司製; ARONIX M-220:三丙二醇二丙烯酸酯,logPow=1.68,均聚物之Tg69℃,東亞合成公司製;ARONIX M-306:新戊四醇三/四丙烯酸酯,logPow=1.04,均聚物之Tg=250℃以上,東亞合成公司製。丙烯酸系低聚物:ARUFON UP-1190,logPow=1.95是顯示東亞合成公司製;包含烷氧基之化合物:NIKALAC MX-750LM,logPow=0.8是顯示日本碳化物工業公司製;包含環氧基之化合物:JER828,logPow=4.76是顯示日本環氧樹脂股份有限公司製;異氰酸酯化合物:KARENZ AOI,logPow=1.6是顯示昭和電工股份有限公司製。光聚合引發劑是顯示:IRGACURE907(2-甲基-1-(4-甲硫基苯基)-2-嗎啉丙烷-1-酮),logPow=2.09,BASF公司製;KAYACURE DETX-s(二乙基9-氧硫),logPow=5.12,日本化藥公司製。 In Table 1, the radically polymerizable compounds are shown as follows: HEAA: hydroxyethyl acrylamide, logPow=-0.56, homopolymer Tg=123°C, manufactured by Xingren Company; ACMO: acryloyl morpholine, logPow= -0.20, Tg of homopolymer=150℃, manufactured by Xingren Company; FA-THFM: tetrahydrofurfuryl (meth)acrylate, logPow=1.13, Tg of homopolymer=45℃, manufactured by Hitachi Chemical; LIGHT ACRYLATE DCP-A: Tricyclodecane dimethanol diacrylate, logPow=3.05, homopolymer Tg=134℃, manufactured by Kyoeisha Chemical Company; LIGHT ACRYLATE1,9ND-A: 1,9-nonanediol Diacrylate, logPow=3.68, homopolymer Tg=68℃, manufactured by Kyoeisha Chemical Company; ARONIX M-220: tripropylene glycol diacrylate, logPow=1.68, homopolymer Tg69℃, manufactured by East Asia Synthesis ; ARONIX M-306: neopentaerythritol tri/tetraacrylate, logPow=1.04, homopolymer Tg=250℃ or more, manufactured by East Asia Synthetic Corporation. Acrylic oligomer: ARUFON UP-1190, logPow=1.95 is made by East Asia Synthetic Corporation; compound containing alkoxy groups: NIKALAC MX-750LM, logPow=0.8 is made by Japan Carbide Industry Corporation; contains epoxy group Compound: JER828, logPow=4.76 is manufactured by Japan Epoxy Resin Co., Ltd.; isocyanate compound: KARENZ AOI, logPow=1.6 is manufactured by Showa Denko Corporation. The photopolymerization initiator shows: IRGACURE907 (2-methyl-1-(4-methylthiophenyl)-2-morpholinepropane-1-one), logPow=2.09, manufactured by BASF; KAYACURE DETX-s( Diethyl 9-oxosulfur ), logPow=5.12, manufactured by Nippon Kayaku.
光酸產生劑是顯示CPI-100P(將六氟化磷酸三芳基鋶作為主成分之有效成分50%之碳酸丙烯酯溶液),三亞普羅公司製。 The photoacid generator is CPI-100P (a 50% propylene carbonate solution containing triaryl hexafluoride phosphate as the main component), manufactured by Sanya Pro Company.
Claims (17)
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2013180478 | 2013-08-30 | ||
JP2013-180478 | 2013-08-30 | ||
JP2014175328A JP2015064575A (en) | 2013-08-30 | 2014-08-29 | Curable adhesive for polarization film, polarization film, optical film and image display device |
JP2014-175328 | 2014-08-29 |
Publications (2)
Publication Number | Publication Date |
---|---|
TW201514269A TW201514269A (en) | 2015-04-16 |
TWI692518B true TWI692518B (en) | 2020-05-01 |
Family
ID=52586749
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
TW103130064A TWI692518B (en) | 2013-08-30 | 2014-08-29 | Hardened adhesive for polarizing film, polarizing film, optical film and image display device |
TW108136691A TWI702270B (en) | 2013-08-30 | 2014-08-29 | Hardening adhesive for polarizing film, polarizing film, optical film and image display device |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
TW108136691A TWI702270B (en) | 2013-08-30 | 2014-08-29 | Hardening adhesive for polarizing film, polarizing film, optical film and image display device |
Country Status (4)
Country | Link |
---|---|
JP (1) | JP2015064575A (en) |
KR (2) | KR102278125B1 (en) |
TW (2) | TWI692518B (en) |
WO (1) | WO2015030203A1 (en) |
Families Citing this family (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2016010031A1 (en) * | 2014-07-16 | 2016-01-21 | 日東電工株式会社 | Polarizing film and method for producing same |
US20160033699A1 (en) | 2014-08-04 | 2016-02-04 | Nitto Denko Corporation | Polarizing plate |
JP5871408B1 (en) | 2014-09-19 | 2016-03-01 | 日東電工株式会社 | Polarizing plate and optical laminate |
JP6712846B2 (en) * | 2015-03-25 | 2020-06-24 | 日東電工株式会社 | Curable adhesive composition for polarizing film, polarizing film and method for producing the same, optical film and image display device |
WO2016152564A1 (en) * | 2015-03-25 | 2016-09-29 | 日東電工株式会社 | Curable adhesive composition for polarizing films, polarizing film and method for producing same, optical film, and image display device |
KR102457858B1 (en) * | 2015-06-23 | 2022-10-21 | 주식회사 쿠라레 | Bonding agent, bonded body, and method for manufacturing bonded body |
JP2017021239A (en) * | 2015-07-13 | 2017-01-26 | 日東電工株式会社 | Curable adhesive composition for polarization film, polarization film and manufacturing method thereof, optical film and image display device |
WO2017134753A1 (en) * | 2016-02-02 | 2017-08-10 | 日東電工株式会社 | Polarizing plate |
WO2017134754A1 (en) * | 2016-02-02 | 2017-08-10 | 日東電工株式会社 | Polarizing plate and optical laminate |
JP6868343B2 (en) * | 2016-04-20 | 2021-05-12 | 日東電工株式会社 | Polarizing film and its manufacturing method, optical film and image display device |
JP6904666B2 (en) * | 2016-05-17 | 2021-07-21 | 日東電工株式会社 | Optical laminate |
JP6811549B2 (en) * | 2016-05-23 | 2021-01-13 | 日東電工株式会社 | Laminated film and image display device |
WO2017204271A1 (en) * | 2016-05-27 | 2017-11-30 | 日本合成化学工業株式会社 | Polyvinyl alcohol-based film, production method therefor, and polarization film using polyvinyl alcohol-based film |
JP2018025765A (en) * | 2016-07-29 | 2018-02-15 | 住友化学株式会社 | Optical laminate |
JP2018025764A (en) * | 2016-07-29 | 2018-02-15 | 住友化学株式会社 | Optical laminate |
JP6993979B2 (en) * | 2016-09-30 | 2022-01-14 | 日東電工株式会社 | Liquid crystal panel and image display device |
JP7195041B2 (en) * | 2017-02-08 | 2022-12-23 | 住友化学株式会社 | Polarizing film, circularly polarizing plate and display device |
CN115657192A (en) * | 2018-11-12 | 2023-01-31 | 日东电工株式会社 | Polarizing film, laminated polarizing film, image display panel, and image display device |
JP7342579B2 (en) * | 2019-09-30 | 2023-09-12 | 日本ゼオン株式会社 | Laminate and its manufacturing method |
JP7176829B2 (en) * | 2020-07-13 | 2022-11-22 | 日東電工株式会社 | Polarizing film, optical film, and image display device |
JP7179802B2 (en) * | 2020-07-13 | 2022-11-29 | 日東電工株式会社 | Polarizing film, optical film, and image display device |
KR102338420B1 (en) * | 2020-12-23 | 2021-12-10 | 삼성에스디아이 주식회사 | Adhesive film, optical member comprising the same and optical display apparatus comprising the same |
CN114736627A (en) * | 2022-05-17 | 2022-07-12 | 新纶电子材料(常州)有限公司 | Semi-solidified pressure-sensitive polymer film, foldable glass cover plate and preparation methods of semi-solidified pressure-sensitive polymer film and foldable glass cover plate |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TW201109405A (en) * | 2009-07-28 | 2011-03-16 | Toagosei Co Ltd | Actinic-energy-ray-curable adhesive composition for plastic film or sheet |
JP2013112715A (en) * | 2011-11-28 | 2013-06-10 | Toagosei Co Ltd | Active energy ray-curing type adhesive composition |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001296427A (en) | 2000-04-17 | 2001-10-26 | Nitto Denko Corp | Method for manufacturing polarizing plate and liquid crystal display device |
JP2006220732A (en) | 2005-02-08 | 2006-08-24 | Nitto Denko Corp | Polarizer protective film and manufacturing method thereof, polarizing plate and manufacturing method thereof, and image display device |
JP4744496B2 (en) | 2007-04-16 | 2011-08-10 | 日東電工株式会社 | Polarizing plate, optical film and image display device |
JP5124406B2 (en) | 2008-09-24 | 2013-01-23 | 日東電工株式会社 | Adhesive for polarizing plate, polarizing plate, method for producing the same, optical film, and image display device |
JP5296575B2 (en) * | 2009-03-06 | 2013-09-25 | 住友化学株式会社 | Photocurable adhesive composition, polarizing plate and method for producing the same, optical member and liquid crystal display device |
JP5959799B2 (en) * | 2010-02-25 | 2016-08-02 | 住友化学株式会社 | Manufacturing method of polarizing plate |
WO2012064142A2 (en) * | 2010-11-10 | 2012-05-18 | 주식회사 엘지화학 | Optical element |
KR101204135B1 (en) * | 2010-11-10 | 2012-11-22 | 주식회사 엘지화학 | Optical elemet |
TWI537356B (en) * | 2010-12-17 | 2016-06-11 | Toagosei Co Ltd | Photo-curable adhesive composition, polarizing adhesive and manufacturing method thereof, optical member and liquid crystal display device (1) |
JP5313297B2 (en) | 2010-12-24 | 2013-10-09 | 日東電工株式会社 | Active energy ray-curable adhesive composition, polarizing plate, optical film, and image display device |
JP5652380B2 (en) * | 2011-11-25 | 2015-01-14 | 東亞合成株式会社 | Curable adhesive composition |
-
2014
- 2014-08-29 KR KR1020207035422A patent/KR102278125B1/en active IP Right Grant
- 2014-08-29 JP JP2014175328A patent/JP2015064575A/en active Pending
- 2014-08-29 WO PCT/JP2014/072816 patent/WO2015030203A1/en active Application Filing
- 2014-08-29 KR KR1020167006693A patent/KR20160048105A/en not_active IP Right Cessation
- 2014-08-29 TW TW103130064A patent/TWI692518B/en active
- 2014-08-29 TW TW108136691A patent/TWI702270B/en active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TW201109405A (en) * | 2009-07-28 | 2011-03-16 | Toagosei Co Ltd | Actinic-energy-ray-curable adhesive composition for plastic film or sheet |
JP2013112715A (en) * | 2011-11-28 | 2013-06-10 | Toagosei Co Ltd | Active energy ray-curing type adhesive composition |
Also Published As
Publication number | Publication date |
---|---|
KR20160048105A (en) | 2016-05-03 |
TW201514269A (en) | 2015-04-16 |
KR20200141535A (en) | 2020-12-18 |
KR102278125B1 (en) | 2021-07-15 |
TW202003733A (en) | 2020-01-16 |
TWI702270B (en) | 2020-08-21 |
WO2015030203A1 (en) | 2015-03-05 |
JP2015064575A (en) | 2015-04-09 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
TWI692518B (en) | Hardened adhesive for polarizing film, polarizing film, optical film and image display device | |
TWI723010B (en) | Polarizing film and manufacturing method thereof, optical film and image display device | |
TWI655461B (en) | Laminated polarizing film, manufacturing method thereof, laminated optical film and image display device | |
TWI708682B (en) | Manufacturing method of laminated optical film | |
JP6308721B2 (en) | Polarizing film, optical film, and image display device | |
TWI592457B (en) | Active energy ray-curable adhesive composition, polarizing adhesive film, method of manufacturing the same, optical film and image display device (1) | |
TWI794418B (en) | Active energy ray-curable adhesive composition, polarizing film and manufacturing method thereof, optical film, and image display device | |
TWI593771B (en) | Active energy ray-curable adhesive composition, polarizing adhesive film, method of manufacturing the same, optical film and image display device (2) | |
CN109073810B (en) | Polarizing film, method for producing same, optical film, and image display device | |
JP7214397B2 (en) | Polarizers, polarizing films, optical films, and image display devices | |
CN109536046B (en) | Curing adhesive for polarizing film, optical film, and image display device | |
JP6931629B2 (en) | Manufacturing method of laminated optical film | |
JP7213037B2 (en) | Polarizers, polarizing films, optical films, and image display devices |