200904634 九、發明說明： 【發明所屬之技術領域】 本發明係有關一種可以在廣泛 的製造方法，且俨而…/ 使用的層疊薄膜 脂系黏接劑從而 腹有關一種使用光固化型環氧樹 而貼3賴而成的層疊薄膜的製造方法。 L无刖技術】 泛=薄Γ被用於包括汽車、飛機、電氣.電子儀器的廣 來越多樣是近年來，電氣.電子儀器中的層疊薄膜越 於層疊薄膜的f造方高度化，關 的衣k方法，也需要在維持製造的層疊薄膜的 簡略化、自動4革的“、成品率的提高、震置的 常在光學構件或液晶顯示裝置中制的偏光板通 $壤胺/醇（PVA)系偏光片薄膜的兩面以黏接劑貼合保 ΐί斑ί光學補償薄膜來製達。作為該黏接劑，使用的是 、、4或有機溶劑系黏接劑，但近年來取而代之開始 ^用作為非u、非有機溶劑系的非溶m接劑，特 疋光固化型環氧樹脂系黏接劑。 认，=，在使用光固化型環氧樹脂系黏接劑作為黏接劑 系膜的製造中’為了充分地固化光固化型環氧樹脂 遠3知’必須照射強照度的光從而用照射熱或反應熱加 、、固化反應、或者在照射光後利用烤料加熱從錢固化 反應^束（後固化（After cure))。如果光固化型環氧樹脂系 減劑被照射到光，則其中内含的光聚合起始劑（催化劑） 320119 5 200904634 會活化，而產生酸。該酸會與光固化型環氧樹脂的環氧基 反應，使裱氧基開環，而產生碳陽離子（carb〇cati〇n)。該 碳陽離子不斷地與環氧樹脂的環氧基反應，使環氧樹脂系 黏，劑發生固化。不過’碳陽離子與環氧基的反應是難以 在吊1下發生的反應，所以必須照射強照度的光或者在照 射光之後利用烤箱等加熱，從而加速或結束碳陽離子與環 氧基的反應。 如果照射强照度的光，光會變成熱，例如在為偏光片 薄膜的情况下’會造成魏被蛾等染色的聚乙烯醇薄膜(偏 光^薄膜）脫出，或者使偏光片薄膜或保護薄膜或者光學補 佔薄膜發生變形，因而使品質變差。 另卜在光照射之後用烤箱等加熱的情況下，需要^ 熱烤箱等加熱裝置，尤其在生產線速度（nn e ^ =多加熱烤㈣㈣常長’運轉㈣上升，設備投資^ 【發明内容】 ㈣ίΓ月的目的在於提供一種使用光固化型環氧樹脂: 黏接劑來貼合薄膜而成的層疊薄膜的製: 了使光固化型環氧樹赌系黏接劑充分地固化而昭射 的紫外線或者在照射光之後進行加熱（後固化）f j 發現了解決上述課題而進行精心研究， 至特定的溫度，可以實現^㈣糸黏接劑加滿 成本發明。 核題’基於料見解以至完 320119 6 200904634 利用本發明，提俾 捉仏以下1至4的發明。 (1)一種層疊薄膜的製造 3 Μ月曰糸黏接劑來貼合薄膜 i衣乳 特徵在於包括：將存納專膜的製造方法，其 接劑加溫至4(ΤΓ、4 光固化型環氧樹脂系黏 η 以的溫度，並對前述黏結劑進行光照射 使其固化從而黏接薄膜。 …、 (2) —種薄膜黏接方法 θ 设乃次其疋使用光固化 黏接劑來貼合偏光片薄膜和保㈣^ 树曰系 寻膜#保濩溥膜及/或光學補償薄膜 而形成的薄膜的黏接方法，1牯 、 r, „ ΑΑ ^ π 套其特被在於包括：將存在於薄 、曰、“ *化型裱氧樹脂系黏接劑加溫至仂。◦以上且所 述薄膜的耐熱溫度以下的溫度’並對前述黏 射使其固化從而黏接薄膜。 仃尤'、、、 (3) 如⑴或（2)中記载的方法，其中，前述加溫溫 40 至120°(：〇 (4)如（1)至（3)中任意一項記載的方法，其中，光為波 長在400nm以下的光中的至少一部分被截止的紫外線。 利用本發明的黏接裝置，不必為了使光固化型環氧樹 脂系黏接劑充分地固化而照射強照度的光或者在照射光之 後進行加熱（後固化），所以可以簡便而且有效地製造品質 良好的如偏光板之類的層疊薄膜。 【實施方式】 以下時細說明本發明。 在本發明中使用的光固化型環氧樹脂系黏接劑含有光 固化型環氧樹脂和光聚合起始劑，此外也可以含有慣用的 7 320119 200904634 添加成分。 光固化型環氧樹脂只要是 脂，特別限定，例如包括芳香族= 固，:環氧樹 氣樹脂、赌環式環 氧樹腊等。、展氣樹脂、脂肪族環 作為芳香族環氧樹月旨，可 雙紛F型環氧樹腊、雙“型環氧樹腊、二!!】樹赌、 酚酚醛清漆型環氧樹脂等。 π月木％氧樹脂、 作為脂肪族環氧樹脂，可以使肽乂 > 氧化物加成物的聚縮水甘油 曰、：：醇或其環 子，可以舉出乙-萨广曰肪麵裱氧樹脂的例 醚、丙二醇二縮水甘乙-醇-縮水甘油 二醇二縮水甘油：二縮水甘㈣、新戊 基丙燒二縮水甘油趟基水甘㈣、三經甲 還可以❹了n / 醇—縮水甘朗#。另外， 飽和糸環氧樹脂、異戊二烯系環氧樹脂等不 甲美二錢乳樹脂。三羥甲基丙烷三縮水甘油醚、三羥 二上縮水甘油趟係因黏度低而為較佳。脂肪族環氧 (三^甲其。品例如包括共榮社化學（股）製Ep〇nght i〇〇mf200904634 IX. Description of the Invention: [Technical Field] The present invention relates to a laminated film fat-based adhesive which can be used in a wide range of manufacturing methods, and is used in a belly-related use of a photocurable epoxy tree. A method of manufacturing a laminated film obtained by laminating three layers. L flawless technology] Pan = thin enamel is used to include automobiles, airplanes, electrical and electronic equipment. In recent years, the laminated film in electrical and electronic equipment has become more advanced than the laminated film. In the method of the k-coating, it is also required to maintain the simplification of the produced laminated film, the "improvement of the yield, the improvement of the yield, and the polarizing plate which is often formed in an optical member or a liquid crystal display device. (PVA) is a two-sided polarizer film which is made of an adhesive to adhere to an optical compensation film. As the adhesive, 4, or an organic solvent-based adhesive is used, but in recent years it has been replaced. Starting with non-u, non-organic solvent-based non-solvent m-bonding agent, special-curing epoxy resin-based adhesive. Recognition, =, using a photocurable epoxy resin adhesive as a bonding In the manufacture of the agent film, in order to sufficiently cure the photocurable epoxy resin, it is necessary to irradiate light of strong illuminance to be applied by irradiation heat or reaction heat, curing reaction, or heating with baking material after irradiation of light. Money curing reaction bundle (post-cure (After cu Re)) If the photocurable epoxy resin reducing agent is irradiated with light, the photopolymerization initiator (catalyst) 320119 5 200904634 contained therein is activated to generate an acid. The acid and the photocurable ring are activated. The epoxy group reacts to open the ring to form a carbocation (carb〇cati〇n). The carbocation continuously reacts with the epoxy group of the epoxy resin to make the epoxy resin adhesive. Curing occurs. However, the reaction of the carbon cation with the epoxy group is a reaction that is difficult to occur under the suspension, so it is necessary to irradiate light of strong illuminance or to heat with an oven or the like after the light is irradiated, thereby accelerating or ending the carbocation and the epoxy group. If the light of strong illuminance is irradiated, the light will become hot, for example, in the case of a polarizer film, a polyvinyl alcohol film (polarized film) which causes dyeing of the moth or the like, or a film of the polarizer Or the protective film or the optical compensating film is deformed, so that the quality is deteriorated. In addition, in the case of heating with an oven or the like after light irradiation, a heating device such as a hot oven is required, especially at a line speed (n Ne ^ = multi-heating roasting (four) (four) constant length 'running (four) rising, equipment investment ^ [invention content] (d) The purpose of the month is to provide a laminated film using a photocurable epoxy resin: adhesive to laminate the film : The ultraviolet curing of the photocurable epoxy gambling-based adhesive is fully cured, and the ultraviolet light is irradiated or heated (post-curing) after the irradiation of light. It has been found that solving the above problems and carefully studying it to a specific temperature. The invention is based on the material discovery and the completion of the invention. The invention is based on the following claims 1 to 4. (1) The manufacture of a laminated film 3 Μ月曰糸Adhesive bonding film I is characterized by: a method for manufacturing a film to be deposited, and the bonding agent is heated to a temperature of 4 (ΤΓ, 4 photocurable epoxy resin η, and The binder is cured by light irradiation to adhere the film. ..., (2) - a film bonding method θ is set to use a photocurable adhesive to bond the polarizer film and protect the film and/or the optical compensation film. The bonding method of the formed film, 1 牯, r, „ ΑΑ ^ π sets is specifically included: the addition of the thin, 曰, “*-type oxime resin-based adhesive to the 仂. The film is adhered to the film at a temperature lower than the heat-resistant temperature of the film and adhered to the film. The method according to (1) or (2), wherein the heating temperature is 40 to 120° (: 〇 (4) is as described in any one of (1) to (3). A method in which light is ultraviolet light whose at least a part of light having a wavelength of 400 nm or less is cut off. With the bonding apparatus of the present invention, it is not necessary to irradiate a strong illuminance in order to sufficiently cure the photocurable epoxy resin-based adhesive. The light is heated (post-cured) after the light is irradiated, so that a laminated film such as a polarizing plate having good quality can be easily and efficiently produced. [Embodiment] Hereinafter, the present invention will be described in detail. The photocurable epoxy resin-based adhesive contains a photocurable epoxy resin and a photopolymerization initiator, and may also contain a conventional addition component of 7 320119 200904634. The photocurable epoxy resin is particularly limited as long as it is a fat, and includes, for example, Aromatic = solid, epoxy resin, gambling ring epoxy wax, etc., gas-enhancing resin, aliphatic ring as an aromatic epoxy tree, can be double F-type epoxy tree wax, double " Epoxy wax, two!! Tree gambling, phenol novolac type epoxy resin, etc. π 月木% oxygen resin, as an aliphatic epoxy resin, can make peptide 乂> oxide polyaddition polyglycidyl hydrazine, :: alcohol or its ring , can be exemplified by the ether of B-Saiguang fat-faced enamel resin, propylene glycol diglycidyl-alcohol-glycidyl glycol diglycidyl: diglycidyl (tetra), neopentyl propylene diglycidyl hydrazide Gan (4), Sanjing A can also lick n / alcohol - shrinking Gan Lang #. In addition, saturated 糸 epoxy resin, isoprene epoxy resin, etc. Glycidyl ether and trishydroxydihydroglycidyl fluorene are preferred because of low viscosity. Aliphatic epoxy (such as Ep〇nght i〇〇mf manufactured by Kyoeisha Chemical Co., Ltd.)
“ 土丙烷—缩水甘油醚）、Nagase ChemteX(股）製EX —321L(三羥曱基丙烷二缩水甘油醚）。 彳班月曰？％氧樹脂是在分子内具有1個以上結合於脂環 二氧基的化合物’作為該例’可以舉出乙稀基環己 烯^^化物、1,2-環氧基-4 -乙烯基環己烷、1，2 : 8,9 衣氧基#檬烯、3,4 —環氧基環己烤基甲基—3’，4’ —環氧 8 320119 200904634 基環己烯羧酸酯等。該等係由DAICEL化學工業（股）以 CEL2000、CEL3000、CEL2021P 市售。 作為本發明中的光固化型環氧樹脂，可以單獨使用上 述的環氧樹脂，也可以以任意配合比例混合使用多種環氧 樹脂。 本發明中的光聚合引發劑只要是利用可見光線、紫外 線、X射線、電子射線等活化能線的照射而產生陽離子或 路易斯酸，並起始環氧基的聚合的光聚合引發劑即可，沒 有特別限定。作為光聚合引發劑的例子，可以舉出銃鹽、 錤鹽、重氮鹽（diazonium)。 作為疏系的例子，可列舉例如： 六氟磷酸三苯基銃、 六氟銻酸三苯基鏟、 四（五氟苯基）硼酸三苯基銃、 4,4’一雙[二苯基銃基]二苯基硫化物雙六氟磷酸鹽、 4,4’_雙[二（β_羥基乙氧基）苯基銃基]二苯基硫化物雙 六亂録酸鹽、 4,4’一雙[二—羥基乙氧基）苯基銃基]二苯基硫化物雙 六氟麟酸鹽、 7_ [二（對曱苯曱醯基）锍基]—2 —異丙基噻噸酮六氟銻酸 鹽、 7 —[二（對甲苯曱醯基）銕基]—2 —異丙基噻噸酮四（五氟 苯基）硼酸鹽、 4 —苯基幾基一4’ 一二苯基疏基一二苯基_硫化物六敦鱗酸 9 320119 200904634 苯基銃基一二苯基硫 4 —(對·第三丁基苯基羰基）—4, 一 化物六氟銻酸鹽、 41·第三丁基苯絲基卜4，—二（對甲苯甲醯基）銃基 —一苯基硫化物四（五氟苯基）硼酸鹽等。 作為銷鹽的例子，例如可以舉出. 四（五氟苯基）棚酸二苯基鎭、 六氟磷酸二苯基錤、 六氟銻酸二苯基鎭、 六氟磷酸二（4—壬基苯基）鎭等。 作為重氮鹽的例子，例如可以舉出： 六氟銻酸苯重氮鹽 六氟磷酸苯重氮鹽等。 作為光聚合起始劑的市售品，可以舉出旭電化工業 (股）製的 ADEKA Optomer SP- 150 及 SP— 17〇、rh〇dia (如）衣的PI2074、日本化藥（股）的Kayara(j pci_ 220等。 沒些光聚合起始劑相對於光固化型環氧樹脂1〇〇質量 份，係使用0.5至20質量份、較佳為1至1〇質量份。光 聚合起始劑可以分別單獨使用’也可以使用兩種以上。 人^發明中的光固化型環氧樹脂系黏接劑根據需要可以 二有氧雜環丁烷（oxetane)化合物。氧雜環丁烷化合物是在 刀子内具有4員環醚（亦即氧雜環丁烷環）的化合物。作為 氧雜％ 丁烷化合物的例子，可以舉出3 _乙基_ 3 —羥基甲 基氧雜環丁院、i，4-雙[{(3—乙基—3_氧雜環丁烧基）甲 320119 10 200904634 氧基}甲基]苯、3—r其 〇 尸 雙（3—乙Α —3一# (本氣基Τ基）氧雜環丁烷、 土 乳雜環丁烷基甲基）醚、"Minepropane-glycidyl ether", Nagase ChemteX (stock) EX-321L (trihydroxydecylpropane diglycidyl ether). 彳班月曰?% oxygen resin has more than one molecule bound to the alicyclic ring The dioxy compound 'as this example' can be exemplified by ethylene cyclohexene compound, 1,2-epoxy-4-vinylcyclohexane, 1,2:8,9 ketoxy# Cumene, 3,4-epoxycyclohexyloxymethyl-3',4'-epoxy 8 320119 200904634 Cyclohexene carboxylic acid ester, etc. These are made by DAICEL Chemical Industry Co., Ltd. as CEL2000, CEL3000 and CEL2021P are commercially available. The above-mentioned epoxy resin may be used singly as the photocurable epoxy resin in the present invention, or a plurality of epoxy resins may be used in combination at any mixing ratio. The photopolymerization initiator in the present invention is only The photopolymerization initiator which generates a cation or a Lewis acid by irradiation with an activation energy line such as a visible light, an ultraviolet ray, an X-ray or an electron beam, and initiates polymerization of an epoxy group is not particularly limited. As a photopolymerization initiator Examples include bismuth salts, strontium salts, and diazonium salts (d Iazonium. As an example of a sparse system, for example, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrakis(pentafluorophenyl)borate, 4,4'-double [ Diphenylindenyl]diphenyl sulfide bishexafluorophosphate, 4,4'-bis[bis(β-hydroxyethoxy)phenylindenyl]diphenyl sulfide bis-ranching salt, 4,4'-[2-hydroxyethoxy)phenylindenyl]diphenyl sulfide dihexaflurane, 7_[di(p-quinone)indolyl]-2-isopropyl Thiophenone hexafluoroantimonate, 7-[bis(p-tolylhydrazyl)fluorenyl]-2-isopropylthioxanthone tetrakis(pentafluorophenyl)borate, 4-phenylphenyl group 4'-diphenylsulfonyl-diphenyl-sulfide hexazone sulphate 9 320119 200904634 phenyl fluorenyl-diphenylsulfan 4-(p-t-butylphenylcarbonyl)-4, a compound of six Fluoride, 41. tert-butylbenzene, 4, di(p-tolylmethyl) fluorenyl-monophenyl sulfide tetrakis(pentafluorophenyl)borate, etc. As an example of a pin salt For example, tetrakis(pentafluorophenyl) linonic acid diphenyl hydrazine And diphenylphosphonium hexafluorophosphate, diphenylphosphonium hexafluoroantimonate, bis(4-nonylphenyl)phosphonium hexafluorophosphate, etc. Examples of the diazonium salt include benzene hexafluoroantimonate. A diazonium salt, a benzene diazonium salt of hexafluorophosphate, etc. As a commercial product of a photopolymerization initiator, ADEKA Optomer SP-150 and SP-17, manufactured by Asahi Kasei Co., Ltd., and rhrdia (e.g. ) PI 2 074 of clothing, Kayara of Japanese chemical (stock), j pci_ 220, etc. No photopolymerization initiator is used in an amount of 0.5 to 20 parts by mass, preferably 0.5 to 20 parts by mass, based on the amount of the photocurable epoxy resin. It is 1 to 1 part by mass. The photopolymerization initiators may be used singly or in combination of two or more. The photocurable epoxy resin-based adhesive in the invention can be an oxetane compound as needed. The oxetane compound is a compound having a 4-membered cyclic ether (i.e., an oxetane ring) in a knife. Examples of the oxab% butane compound include 3-ethyl-3-hydroxymethyl oxetane, i,4-bis[{(3-ethyl-3-oxetanyl) ) A 320119 10 200904634 oxy}methyl]benzene, 3-r- 〇 双 双 (3 - Α Α - 3 a # (this gas based fluorenyl) oxetane, earth-heterocyclic polyalkylene Ether,
-乙基己氧基甲基)氧雜環丁烷、3—乙基 二J 基甲石夕烧基丙氧基）甲基}氧雜環丁院]、氧雜環丁 :氧烧、盼崎漆氧雜環丁燒等。在這些氧雜二化 :=,佳為3—乙基—3_經基甲基氧雜環丁院、雙(3 —乙基―3—氧雜環丁烷基曱基）醚、3—乙基—(2_乙 基己氧基甲基）氧雜環丁燒。氧雜環丁烧化合物的市售品例 如包括東亞合成（股）市售的商品名〇χτ — 1〇ι(3 —乙美—3 —經基甲基氧雜環丁燒）、ΟΧΤ_211(3—[基—3 —(土苯氧 基甲基）氧雜環丁烧）、ΟΧΤ—221(二[卜乙基（3—氧雜環丁 烷基）]甲基醚）、〇ΧΤ—212(3—乙基_3 —(2—乙基己氧基 甲基）氧雜環丁烷）。 ^ 在本發明中，氧雜環丁烷化合物相對於光固化型環氧 樹脂100質量份，以50質量份以下的量使用。氧雜環丁烷 化合物可以分別單獨使用’也可以使用兩種以上。 本發明中的光固化型環氧樹脂系黏接劑可以再根據需 要而倂用光敏劑。藉由使用光敏劑，使反應性能提高，可 以提高固化物的機械強度或黏接強度。作為光敏劑，可以 舉出羰基化合物、有機硫化合物、過硫化物、氧化還原系 化合物、偶氮及重氮化合物、鹵素化合物、光還原性色素 等。作為光敏劑的例子，可以舉出苯偶因曱醚、苯偶因異 丙謎、α，α —二曱氧基一苯基乙醯苯之類的苯偶因衍 生物，一本曱嗣、2,4 — 一 ^ ,一本曱嗣、鄰笨曱酸笨曱酸曱 320119 11 200904634 醋、4,4，一雙（二乙胺基）二苯甲酮之類的二苯甲鲖 (benZ_en〇ne)衍生物；2〜氯嗟侧、2 —異丙基噻噸g同、 2,4:二乙基。㈣酮之類的^㈣酮邮_她嶋清生物；2 -氯蒽酿、2-甲基f、藏之類的蒽酿衍生物；N—甲基w 酮、N一丁基°丫啶酮之類的，定嗣(acridone)衍生物；9:〇 -二丁氧基X之類的蒽衍生物；此外，α，α —二乙氧基 醯苯、苯偶醯(benzil)、苟酮、氧雜—二 __化合物、鹵素化合物、光還原性色素等，但不被= =:Γ卜這些光敏劑可以單獨使用，也可以使用兩 smp敏，劑的市售品例如可以舉出Kay贿e DETX〜 樂（股）製）等。光敏劑的量相對於光固化型環氧樹 脂系黏接劑100質量份，Α Λλι I衣氣樹 至5質量份。 為〇.01至20質量份，較佳為叫 發明=不破壞本發明的效果的範圍内，可以進而在本 加劑，例如填充劑=;黏接劑中配合上述以外的添 抗氧化劑、矽烷偶合劑。 等二=:?例子，可以舉出滑石、二氧化石夕、雲母 作从丙稀、聚乙烯等樹脂填充劑。 邗為抗氧劑’例如 _，咖 x 1G3=V*T_基甲苯_)、 作為石夕烧偶合劑，可Γ二 65等。 烯基三乙氧基石夕燒、舉出乙婦基三甲氧基石夕烧、乙 基矽烷、3—環氧# 3,4~·環氧基環己基）乙基三甲氧 基丙基甲基二乙:，基两基三甲氧基石夕烧、3-環氧丙氧 羊土矽烷、3—環氧丙氧基丙基三乙氧基矽 320119 12 200904634 烷、對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—曱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 —甲基丙烯醯氧基丙基三甲氧 基石夕烧、3 —二乙氧基石夕烧基_n—(ι，3 —二甲基—亞丁基） 丙基胺等。 ^ 矽烷偶合劑的市售品例如可以舉出環氧系（例如 KBM403、KBM303)、乙烯基系（KBM1〇〇3)、丙烯酸系矽 烷偶合劑（KBM503)、3—乙基（三乙氧基矽烷基丙氧基甲基） 氧雜環丁烷（TESOX(東亞合成（股）製））等。 本發明中的光固化型環氧樹脂系黏接劑較佳為黏度 2〇〇mPa.s(25t)以下、更佳為 15〇mPa.s(25t)以下。黏度 越低越容易進行塗敷’另外，可以使黏接劑層的塗敷厚度 1，例如用於將保護薄膜或光學補償薄膜貼附於偏光板ς ί·月況下，偏光板的外觀也變得良好。也可以使用高黏度的 黏接劑’但在該情況下要減少塗敷量。 本發明中使用的薄膜必須至少丨個薄膜為透過光的薄 膜作為這樣的光透過性薄膜，可以舉出聚醋系薄膜、聚 碳酸醋系薄膜、丙烯酸系薄膜、聚醯胺系薄膜、聚醯亞胺 $薄膜、非結晶性聚烯烴系薄膜、環烯烴系薄膜、pVA系 薄膜、纖維素系薄膜等。 ’' 、非結晶性聚烯烴系樹脂通常為具有降冰片烯或多環降 冰片：系單體之類的環狀聚烯烴的聚合單元的樹脂，也可 以為％狀烯烴和鏈狀環狀烯烴的共聚物。作為市售的非結 320119 13 200904634 晶性聚烯烴系樹脂，包括册(股）的商品名art〇n;日本 ΖΕΟΝ(股）的 ΖΕ0ΝΕχ、ZE〇N〇R ;三井化學的 、 APEL 等。 在本發明中，可以與不透過光的薄膜組合，不透過光 的薄_如也可_作層疊薄膜的基材薄膜。作為這樣的 :透過光的薄膜，例如可以舉出為了著色或遮光而内含有 著色顏料著色木料、碳黑、無機粒子或高分子微粒的樹 月旨、或在45Gnm以下的波長區域沒有光透過性的聚酿亞胺 •對本發财的各薄膜的厚度沒有❹i限定，可以根據 需要使用各種厚度的薄膜。 在層疊薄膜為偏光板的情況下，可以使用pvA系偏光 或三乙醯纖維素等纖維素㈣膜、環_系薄膜等 保瘦薄膜或光學補償薄膜。 ^本發明中，對於基材薄膜錄光固化型環氧樹脂系 的方法，没有特别限I例如包括❹❹、_ (―M、模具式塗敷機、逗號式刮刀塗敷機（⑶脑 _er)、凹板印刷塗敷機等的方法。另外，本發明中 膜的層壓可以使用金屬輥、 ' 力可以為0至5_ 等進灯，此時的層㈣ 本發明中的層疊薄膜可以具有由2層、3層、4層、5 曰6層或其以上的薄膜構成的層疊結構。 理、用在薄臈的貼合面實施電暈處 處理準刀子處理、UV處理等的薄膜。 320119 14 200904634 /本發明中的光固化型環氧樹脂系黏接劑的加溫溫度必 、為 c X上加μ溫度的上限是黏附物薄膜的耐熱溫 度依存於霉占附物薄膜的对熱性，所以不能一概限定，例 如為120 C。在此，薄膜的耐熱溫度是指將薄膜放置於某 温度下6〇秒時，與加熱前相比，在實際上沒有出現薄膜的 變形（翹曲、變形）而且薄膜的光學特性（透過率、偏光度） 不發生劣士化的溫度中最高的溫度。黏接劑的加溫溫度為 =乂下％利用光照射的光固化型環氧樹脂的固化不充 刀不月匕達到本發明的效果。黏接劑的加溫溫度較佳為％ 至loot： ’更佳為60至80。(：。 、本發明中的光固化型環氧樹脂系黏接劑的加溫例如可 以舉出近紅外線齒素燈、遠紅外線加熱器、熱風、加熱板、 加熱輥等，但不被這些所限定。 本發明中的光是指可見光線、紫外線、χ射線、電子 射線等活化能線，較佳為紫外線。光照射可以使用金屬齒 =燈、高壓汞燈、氣燈、自素燈等進行。在使用紫外線 的情況下，為了使薄膜的劣化最少，宜為不含有波長在 〇咖以下(較宜為39Gnm以下）的光的至少—部分的 線，另外更宜為不含有波長在400nm以下（特宜為39〇咖 以下）的光的全部的紫外線。這樣的紫外線例如可以藉 =線燈赫附物薄膜之間使料紅外線截止㈣遽波器 =截^皮長在3m9〇nm以下的光的光學遽波器而得 唐為這種光學遽波器，可以舉出石英破璃 '熱線截止 4波益（贿）、··以下截止遽波器、32〇nm截止遽波 320119 15 200904634 态、340nm戴止濾波器、39〇nm截止濾波器、鈉鈣玻璃 (soda-lime glass)、400 至 45〇nm 帶通濾波器（bandpass fme 等。 本發明中的光的照射係在光固化型環氧樹脂系黏接劑 的溫度具有40t以上時進行。本發明中的光的照射強度根 據目的黏接劑或樹脂薄膜而不同，沒有限定，對光聚合引 發劑的活化有效的波長區域的照射強度較佳為至 500mW/cm。光的照射時間根據使用的光固化性環氧樹脂 ==薄膜的材質而不同，沒有限定，設定成使作為照 射強度與照射時間的乘積而表示的累計光量成^ _至 =二㈣.）’ _彻至2⑼q (波 [實施例] 以下利用貫施例顯示本發明 例所限定。 料3但树料被這些實苑 製造例A至F光固仆开』王夢备 ^ 1衣氧树月曰糸黏接劑的調製 在♦乙烯製容器中計量並加入以下原材料田 混合、授拌’得到均一的光固化型環氧樹"用㈣機 度· ISOniPa/spSt ))。 、曰系勘接劑（黎 320119 16 200904634 [表i]-ethylhexyloxymethyl)oxetane, 3-ethyldiJ-methylmethylsulfanylpropoxy)methyl}oxetan],oxeane:oxygen, expectant Saki oxycycline and so on. In these oxazepines: =, preferably 3-ethyl-3-yl-based methyl oxetan, bis(3-ethyl-3-oxetanyl decyl) ether, 3- Ethyl-(2-ethylhexyloxymethyl)oxetane. Commercial products of the oxetane compound include, for example, the commercially available product name 〇χτ - 1 〇ι(3 - 乙美-3, methoxymethyl oxetane), ΟΧΤ 211 (3) —[基—(—(phenphenoxymethyl)oxetane), ΟΧΤ—221 (bis[iethyl(3-oxetanyl)methyl ether), 〇ΧΤ—212 (3) —Ethyl-3-(2-ethylhexyloxymethyl)oxetane). In the present invention, the oxetane compound is used in an amount of 50 parts by mass or less based on 100 parts by mass of the photocurable epoxy resin. The oxetane compounds may be used singly or in combination of two or more. The photocurable epoxy resin-based adhesive of the present invention can be further used as a photosensitizer as needed. By using a photosensitizer, the reaction performance is improved, and the mechanical strength or the bonding strength of the cured product can be improved. The photosensitizer may, for example, be a carbonyl compound, an organic sulfur compound, a persulfide compound, a redox system compound, an azo or diazo compound, a halogen compound or a photoreductive dye. Examples of the photosensitizer include a benzoin derivative such as benzoin oxime ether, benzoin isopropyl mystery, α,α-dimethoxyoxyphenylene benzene, and a bismuth, 2,4 — a ^ , a 曱嗣 , 邻 曱 曱 119 119 119 320119 11 200904634 vinegar, 4, 4, a pair of (diethylamino) benzophenone and other benzamidine (benZ_en 〇ne) derivative; 2~chloroguanidine side, 2-isopropyl thioxanthene, 2,4: diethyl. (4) ketones and the like (4) ketone mail _ her cockroach biological; 2 - chlorohydrin, 2-methyl f, Tibetan and other brewing derivatives; N-methyl w ketone, N-butyl ketone An acridine derivative such as a ketone; 9: an anthracene derivative such as anthracene-dibutoxy X; in addition, α,α-diethoxyanthracene, benzil, anthrone , an oxa-di-compound, a halogen compound, a photoreducible dye, etc., but not by ==: 这些 These photosensitizers may be used singly or in combination with two smp-sensitive agents, for example, Kay may be mentioned. Bribe e DETX ~ music (shares) system and so on. The amount of the photosensitizer is from 5 parts by mass to 5% by mass based on 100 parts by mass of the photocurable epoxy resin-based adhesive. In the range of from 0.01 to 20 parts by mass, preferably in the form of an invention = not detrimental to the effects of the present invention, it may be further blended with the above-mentioned additive antioxidant, decane in the present additive such as a filler =; Coupling agent. For example, talc, silica dioxide, and mica can be used as a resin filler such as propylene or polyethylene.邗 is an antioxidant ', for example, _, coffee x 1G3 = V * T_ based toluene _), as a Shi Xi siu coupling agent, Γ 65 65, and the like. Alkenyl triethoxy zebra, exemplified by ethoxylated trimethoxy sulphur, ethyl decane, 3-epoxy # 3,4~·epoxycyclohexyl)ethyltrimethoxypropylmethyldi B: bis-yltrimethoxy zephyr, 3-glycidoxypropoxide, 3-glycidoxypropyltriethoxy ruthenium 320119 12 200904634 alkane, p-styryltrimethoxy decane, 3-methacryloxypropylmethyldimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-mercaptopropenyloxypropylmethyldiethoxydecane , 3-methyl propylene methoxy propyl triethoxy decane, 3- methacryloxypropyl trimethoxy sulphur, 3 - diethoxy sulphide _ n - (ι, 3 - Dimethyl-butylene) propylamine and the like. ^ Commercial examples of the decane coupling agent include epoxy (for example, KBM403, KBM303), vinyl (KBM1〇〇3), acrylic decane coupling agent (KBM503), and 3-ethyl (triethoxy).矽alkylpropoxymethyl) oxetane (TESOX (manufactured by Toago)). The photocurable epoxy resin-based adhesive of the present invention preferably has a viscosity of 2 〇〇 mPa.s (25 t) or less, more preferably 15 〇 mPa.s (25 t) or less. The lower the viscosity, the easier it is to apply. In addition, the thickness of the adhesive layer can be applied, for example, to attach a protective film or an optical compensation film to a polarizing plate. The appearance of the polarizing plate is also Becomes good. It is also possible to use a high-viscosity adhesive agent', but in this case, the amount of application is reduced. The film used in the present invention is required to have at least one film which is a light-transmissive film as such a light-transmitting film, and examples thereof include a polyester film, a polycarbonate film, an acrylic film, a polyamide film, and a polyfluorene film. An imide $ film, a non-crystalline polyolefin film, a cycloolefin film, a pVA film, a cellulose film, or the like. '', the amorphous polyolefin-based resin is usually a resin having a polymerization unit of a norbornene or a polycyclic norborne: a cyclic polyolefin such as a monomer, and may also be a % olefin and a chain cyclic olefin Copolymer. As a commercially available non-junction 320119 13 200904634 crystalline polyolefin-based resin, including the trade name of the book (stock), art〇n; ΖΕΟΝ0ΝΕχ, ZE〇N〇R of Japan ΖΕΟΝ(股); Mitsui Chemicals, APEL, etc. In the present invention, it is possible to combine with a film which does not transmit light, and a thin film which does not transmit light can also be used as a base film of a laminated film. As a film which transmits light, for example, a coloring pigment colored wood, carbon black, inorganic particles or polymer fine particles are contained therein for coloring or light shielding, or no light is transmitted in a wavelength region of 45 Gnm or less. Sexual Polyimine • The thickness of each film of the present invention is not limited, and films of various thicknesses can be used as needed. When the laminated film is a polarizing plate, a thin film or an optical compensation film such as a cellulose (tetra) film such as pvA-based polarized film or triethylene fluorene cellulose or a ring-based film can be used. In the present invention, there is no particular limitation on the method of the base film recording and curing epoxy resin system, for example, including ❹❹, _ ("M, mold coating machine, comma knife coating machine ((3) brain _er The method of the gravure printing coater, etc. Further, in the present invention, the lamination of the film may be carried out using a metal roll, and the force may be 0 to 5 or the like, and the layer (4) at this time may have the laminated film of the present invention. A laminated structure composed of a film of two layers, three layers, four layers, and five layers of six or more layers. The film is subjected to corona treatment at the corrugated surface, and a film such as a quasi-knife treatment or a UV treatment is used. 14 200904634 / The heating temperature of the photocurable epoxy resin adhesive of the present invention is such that the upper limit of the temperature of the addition of μ to c X is that the heat resistance temperature of the adhesive film depends on the heat resistance of the film of the mold. Therefore, it cannot be limited, for example, 120 C. Here, the heat-resistant temperature of the film means that when the film is placed at a certain temperature for 6 sec seconds, there is practically no deformation of the film (warpage and deformation) compared with before heating. And the optical properties of the film (transmittance, polarization) The highest temperature in the temperature at which the inferiority does not occur. The heating temperature of the adhesive is = 乂% The curing of the photocurable epoxy resin irradiated with light does not fill the knives to achieve the effect of the present invention. The heating temperature of the bonding agent is preferably from % to loot: 'more preferably from 60 to 80. (In addition, the heating of the photocurable epoxy resin-based adhesive in the present invention is, for example, a near-infrared acne The lamp, the far-infrared heater, the hot air, the heating plate, the heating roller, and the like are not limited thereto. The light in the present invention means an active energy line such as visible light, ultraviolet rays, xenon rays, or electron beams, and is preferably ultraviolet light. The light irradiation can be carried out using a metal tooth = a lamp, a high pressure mercury lamp, a gas lamp, a self-priming lamp, etc. In the case of using ultraviolet rays, in order to minimize the deterioration of the film, it is preferable to have no wavelength below the enamel (more preferably 39 Gnm). The light of at least a part of the light of the following) is more preferably an ultraviolet ray which does not contain light having a wavelength of 400 nm or less (particularly 39 Å or less). Such an ultraviolet ray can be, for example, a film of a light-emitting device. Infrared Cut-off (4) Chopper = optical chopper with a length of light below 3m9〇nm and get the optical chopper of Tang. This can be exemplified by quartz broken glass 'hot line cutoff 4 wave benefit (bribery), · ·The following cut-off chopper, 32〇nm cut-off chopper 320119 15 200904634 state, 340nm wear stop filter, 39〇nm cut-off filter, soda-lime glass, 400 to 45〇nm bandpass filter (Bandpass fme, etc. The irradiation of light in the present invention is carried out when the temperature of the photocurable epoxy resin-based adhesive has a temperature of 40 t or more. The irradiation intensity of light in the present invention varies depending on the intended adhesive or resin film. It is not limited, and the irradiation intensity in the wavelength region effective for activation of the photopolymerization initiator is preferably 500 mW/cm. The irradiation time of the light differs depending on the material of the photocurable epoxy resin used = the film, and is not limited, and is set such that the integrated light amount expressed as the product of the irradiation intensity and the irradiation time is ^ _ to = two (four). _Essence to 2 (9) q (waves [Examples] The following examples are used to illustrate the examples of the present invention. Material 3, but the tree material is opened by these solid manufacturing examples A to F. Wang Mengbei ^ 1 Yixing Shuyue The preparation of the adhesive is measured in a ♦ ethylene container and added to the following raw material fields for mixing and mixing to obtain a uniform photocurable epoxy tree "(4) machine degree ISOniPa/spSt). , 曰 system survey agent (Li 320119 16 200904634 [Table i]
原材料 調配量（質量份） 100MF 100 100 CEL2000 100 100 CEL3000 100 100 N740 10 10 10 10 850S 10 10 CEL2021P 10 10 10 10 10 10 KBM403 1 1 1 1 1 1 SP- 172 3 3 3 CPI- 101A 3 3 3 DBA 0.5 0.5 0.5 0.5 0.5 0.5 符號 A B C D E F 100MF:三羥曱基丙烷三縮水甘油醚，共榮社公司化學（股）Raw material dosage (parts by mass) 100MF 100 100 CEL2000 100 100 CEL3000 100 100 N740 10 10 10 10 850S 10 10 CEL2021P 10 10 10 10 10 10 KBM403 1 1 1 1 1 1 SP- 172 3 3 3 CPI- 101A 3 3 3 DBA 0.5 0.5 0.5 0.5 0.5 0.5 Symbol ABCDEF 100MF: Trihydrodecylpropane triglycidyl ether, Kyoritsu Corporation Chemicals Co., Ltd.
Epiclon EXA— 850S : 4,4’一二缩水甘油氧基一 2,2’一二苯 基丙烧’大曰本油墨化學（股）Epiclon EXA-850S: 4,4'-diglycidyloxy-2,2'-diphenylpropanol- 曰大曰本墨化学(股)
Epiclon N740 :紛盼醒·清漆型環氧寡聚物，大日本油墨化 學（股） CEL2000 : 1，2 —環氧基_ 4 一乙烯基環己烧，DAICEL化學 工業（股） CEL3000 : 1，2: 8,9二環氧基檸檬烯，DAICEL化學工業（股) CEL2021P : 3,4一環氧基環己烯基甲基一3’,4’一環氧基環 己烯羧酸酯，DAICEL化學工業（股） CPI—101A:光聚合催化劑，SAN-APR0(股）Epiclon N740: Awakening varnish-type epoxy oligomer, Dainippon Ink Chemicals Co., Ltd. CEL2000: 1,2-epoxy _ 4 vinylcyclohexene, DAICEL Chemical Industry Co., Ltd. CEL3000: 1, 2: 8,9-diethoxylated limonene, DAICEL Chemical Industry Co., Ltd. CEL2021P: 3,4-epoxycyclohexenylmethyl- 3',4'-epoxycyclohexenecarboxylate, DAICEL Chemical Industry (shares) CPI-101A: Photopolymerization Catalyst, SAN-APR0 (shares)
SP—172 :光聚合催化劑，（股）ADEKA KBM403 : 3—環氧丙氧基丙基三曱氧基矽烷，信越化學工 業（股) DBA : 9,10—二丁氧基蒽，川崎化成工業（股) 17 320119 200904634 實施例1至6及比較例1至3層疊薄膜（偏光板）的製造 經，在製造例中所配製的光固化性環氧樹脂系黏接劑 (符號：A) ’在經單向拉伸並用碘染色的聚乙烯醇偏光片薄 膜的單面黏合三乙醯纖維素薄膜’並在另一單面黏合非結 晶性聚烯烴系樹脂薄膜（日本ΖΕΟΝ(股）製的ZEONOR薄 膜），而得到3層結構的薄膜。使用红外線燈，將所得到的 3層結構薄膜加溫至室溫（25。〇、30。(：、4(TC、50°C、60°C、 70°C、80°C、100°C、120°C及140°C，然後立即使用金屬鹵 化物燈（Eyegraphic公司製），以照射强度2〇〇mW/cm2 (405nm)、累計光量1000mJ/cm2(405nm)，進行光照射，得 到層疊薄膜。層疊薄膜之間的黏接劑層為1至3μπι左右的 厚度’為均一者。利用電子顯微鏡確認這些結果。 表2表示材料溫度、UV照射後的黏接劑的狀態、υν 照射後的層疊薄膜的變形、層疊薄膜的耐久特性、耐濕試 驗後的光學特性。 [表2] 實施例或 比較例 材料溫度 (°C) UV照射後的黏接劑 的狀態 UV照射後的 薄膜的變形 耐濕試驗後 的耐久特性 耐濕 比較例1 25 為液態，固化不充分 無 X 比較例2 30 為液態，固化不充分 無 X 二 實施例1 40 Δ 無 X 實施例2 50 〇 無 X — 實施例3 60 "1 ◎ 無 Δ 有 — 實施例4 70 ◎ 無 Δ 沒 實施例5 80 〇 略微翹曲 △ 實施例6 100 〇 極大地麵曲 X ---—-- 比較例3 140 1 剝脫 極大地變形 X ------ 材料溫度：即將照射UV前的黏接劑的溫度（加溫溫度) UV照射後的黏接劑的狀態： 18 320119 200904634 按照以下標準進行評價。 為液態，固化不充分：為液體狀態而固化不充分，沒 有黏接 剝脫：薄膜被剝脫 △:黏接，但強度有些弱（〜l〇〇g/25mm) 〇：黏接，強度為中程度（100至200g/25mm) ◎:黏接，強度充分(200g/25mm〜） UV照射後的薄膜的變形：用肉眼觀察。 耐濕試驗後的耐久特性： 按照以下標準’評價將層疊薄膜放置於60。(：至90%的 條件的耐濕試驗槽中5〇〇小時之後的外觀（脫染或薄膜變 性）。 X ··嚴重地發生剝脫或變形、偏光片部分的脫染。 △.發生剝脫或變形、偏光片部分的脫染。 〇.極少地發生偏光片部分的脫染，但不發生剥脫或 變形。 ◎.不發生剝脫或變形、偏光片部分的脫染。 耐濕試驗後的光學特性： 率，對耐濕試驗前以及後的層疊薄膜，測定偏光度和透過 :以。亥等的劣化（從耐濕試驗前的層疊薄膜的值的降低） 進行評價。 二對於黏附物材料的變性(變形、耐久特性、光學特性)而 ° \不僅會因熱而發生劣化，在紫外線下也會發生劣化。 "表2可知，如果在加濃到4〇至7〇它之後，進行光 320119 19 200904634 照射，固化，則光固化型環氧樹脂系黏接劑充分地固化， 顯不出良好的黏接性，同時也幾乎沒有薄膜的變形。另— 方面’在加溫溫度為25 巧5 C、30 c的情況下，儘管沒有薄臈 的變形，但光固化型瑗ΛΛ 、 i衣氧树月曰糸黏接劑固化不充分或者未 口化黏接f生極為不良。另外，材料溫度為至湖。c以 二的If況下A固化型¥氧樹脂系黏接劑充分地固化，顯 。示出良好的黏接性’但薄膜略微地翹曲。另外，超過100 _勺ί♦況下％固化型知氧樹脂系黏接劑充分地固化，顯 不出良好的黏接性，但薄臈極大地變性。 、對光固化性樹脂Β至F進行相同的研究，儘管黏接性 或多或少存在差異，但均可以得到同樣的結果。 此外，代替紅外線燈而用加熱板進行加溫時或用熱風 進行的情況下，可以得到與上述同樣的性能的層疊薄膜。 貫施例7至13以及比較例4至6層疊薄膜的製造 在實施例1至6及比較例1至3的層疊薄膜的製造中， 在金屬齒化物燈與黏附物薄膜之間，酉己置截止波長在 39〇咖以下的光的光學濾'波器（咖抑昭 射光。與實施例1至6及比較例1至3門接丄衣）… 千乂列i主3问樣地進行，分別 得到實施例⑴3以及比較例4至6的層疊薄膜。 320119 20 200904634 [表3]SP-172 : Photopolymerization catalyst, (stock) ADEKA KBM403 : 3-glycidoxypropyl trimethoxy decane, Shin-Etsu Chemical Co., Ltd. DBA: 9,10-dibutoxy oxime, Kawasaki Chemical Industry (Shares) 17 320119 200904634 Production of laminated films (polarizing plates) of Examples 1 to 6 and Comparative Examples 1 to 3, Photocurable epoxy resin-based adhesives prepared in Production Examples (symbol: A) A single-sided bonded triacetone cellulose film of a polyvinyl alcohol polarizer film which is uniaxially stretched and dyed with iodine, and a non-crystalline polyolefin resin film bonded to the other side (manufactured by Nippon Kasei Co., Ltd.) ZEONOR film), and a film having a three-layer structure was obtained. The obtained 3-layer structure film was heated to room temperature using an infrared lamp (25. 〇, 30. (:, 4 (TC, 50 ° C, 60 ° C, 70 ° C, 80 ° C, 100 ° C) At 120 ° C and 140 ° C, a metal halide lamp (manufactured by Eyegraphic Co., Ltd.) was used, and light irradiation was performed at an irradiation intensity of 2 〇〇 mW/cm 2 (405 nm) and an integrated light amount of 1000 mJ/cm 2 (405 nm) to obtain a laminate. The thickness of the adhesive layer between the laminated films was about 1 to 3 μm. The results were confirmed by an electron microscope. Table 2 shows the material temperature, the state of the adhesive after UV irradiation, and the υν irradiation. The deformation of the laminated film, the durability characteristics of the laminated film, and the optical properties after the moisture resistance test. [Table 2] Example or Comparative Example Material Temperature (°C) The state of the adhesive after UV irradiation The deformation of the film after UV irradiation Durability after moisture resistance test Wet resistance Comparative Example 1 25 is liquid, insufficient curing is not X Comparative Example 2 30 is liquid, insufficient curing is not X. 2 Example 1 40 Δ No X Example 2 50 〇 No X - Implementation Example 3 60 "1 ◎ No Δ Yes - Example 4 70 ◎ None Δ No Example 5 80 〇 slightly warped △ Example 6 100 〇 maximal ground curvature X --- --- -- Comparative Example 3 140 1 Stripping greatly deformed X ------ Material temperature: UV irradiation Pre-adhesive temperature (heating temperature) Adhesive state after UV irradiation: 18 320119 200904634 Evaluated according to the following criteria. In liquid state, curing is insufficient: curing is insufficient in liquid state, no bonding Stripping: The film is peeled off △: Bonded, but the strength is somewhat weak (~l〇〇g/25mm) 〇: Bonding, medium strength (100 to 200g/25mm) ◎: Bonding, sufficient strength (200g/ 25mm~) Deformation of film after UV irradiation: Observed with the naked eye. Durability after moisture resistance test: The laminated film was placed at 60 according to the following criteria. (: 5 to 90% moisture resistance test tank) Appearance after 〇 hours (de-staining or film denaturation) X ·· Severe peeling or deformation, partial decolorization of the polarizer. △. Stripping or deformation, partial depolarization of the polarizer. 极. Decolorization of the polarizer portion occurs, but no peeling or deformation occurs. No peeling or deformation, and partial dyeing of the polarizer. Optical properties after moisture resistance test: Rate, measurement of the degree of polarization and transmission of the laminated film before and after the moisture resistance test: The evaluation of the value of the laminated film before the moisture resistance test was carried out. 2. The deterioration (deformation, durability characteristics, and optical characteristics) of the adhesive material was not deteriorated by heat, but also deteriorated under ultraviolet light. " Table 2 shows that if it is irradiated and cured by light 320119 19 200904634 after enriching it to 4〇 to 7〇, the photocurable epoxy resin adhesive is fully cured, showing no good adhesion. Sex, and there is almost no deformation of the film. On the other hand, in the case where the heating temperature is 25, 5 C, and 30 c, although there is no deformation of the thin crucible, the photocurable type i, i ene oxide moon 曰糸 adhesive is not sufficiently cured or not The bonding is extremely bad. In addition, the material temperature is to the lake. c is sufficiently cured by the A-curing type epoxy resin-based adhesive under the condition of two. Good adhesion was shown' but the film was slightly warped. Further, in the case of more than 100 scoops, the % curable oxygen-based adhesive is sufficiently cured to exhibit good adhesion, but the haf is greatly denatured. The same study was conducted on the photocurable resin Β to F, and although the adhesion was more or less different, the same result was obtained. Further, when heating is performed by a hot plate instead of an infrared lamp or by hot air, a laminated film having the same performance as described above can be obtained. Production of the laminated films of Examples 7 to 13 and Comparative Examples 4 to 6 In the production of the laminated films of Examples 1 to 6 and Comparative Examples 1 to 3, between the metal toothed lamp and the adhesive film, The optical filter of the light having a cut-off wavelength of 39 〇 or less (the smear of the light is suppressed. It is connected to the first to third and the first to third comparative examples 1 to 3). The laminated films of Example (1) 3 and Comparative Examples 4 to 6 were obtained, respectively. 320119 20 200904634 [Table 3]
實施例或 比較例 材料溫度 (°C) ]-_ —· 照射後的黏接劑 的狀態 UV照射後的 薄膜的變形 耐濕試驗後 的耐久特性 耐濕試驗後 的光學牿,w： 比較例4 25 為液態，固化不充分 無 X 比較例5 30 為液態，固化不充分 無 X — 實施例7 40 Δ 無 Δ 實施例各 50 〇 〇 實施例9 60 ◎ 無 無變化 賞地例10 70 ◎ 無 ◎ 無變化 賞施例π 80 ◎ 無 ◎ 無變化 貧施例i2 100 --_©_ 無 △ Γ有些變差 實施例13 120 〇 略微翹曲 Δ 有4b轡j ~ 比較例6 140 〇 變形 X 從表3可知，如果在金屬鹵化物燈與黏附物之間配置 截止波長在390nm以下的光的光學濾波器，則與不配置的 情況相比’偏光片以及薄膜的變性少，可以得到具有良好 的黏接性和耐久特性的層疊薄膜。即使代替截止波長在 390nm以下的渡波器，而使用截止波長在32〇nm以下的濾 波器、截止波長在34〇nm以下的濾波器或截止波長在 370nm以下的濾波器，也可以得到同樣的結果，但以使用 裁止波長在39〇nm以下的濾波器時對構成薄膜的影響最 少。藉由使用光學濾波器，可以抑制加溫至12〇。〇時的薄 膜的變形’而不能抑制加溫至140°C時的薄膜的變形。 比較例7至12層疊薄膜的製造 與實施例1同樣地進行’得到3層結構的薄膜。不加 溫得到的3層結構的薄膜，而使用金屬鹵化物燈 (Eyegraphics 公司製），以照射强度 5〇〇mW/cm2(4〇5nm)、 累計光篁 500、1〇〇〇、2〇〇〇 以及 3〇〇〇mJ/cm2(4〇5nm)，進 21 320119 200904634 行光照射，得到層疊薄膜。進而，在累計光量為2000以及 3000mJ/cm2(405nm)的情况下，使用配置於金屬鹵化物燈與 黏附物薄膜之間的截止波長在390nm以下的光的光學濾波 器（Eyegraphics公司製），進行光照射，得到層疊薄膜。 [表4] 實施例或 比較例 光學濾 波器 UV的累計光量 (mJ/cm2(405nm)) UV照射後的黏接劑 的狀態 UV照射後的薄 膜的變形 比較例7 無 500 為液態，固化不充分 無 比較例8 無 1000 為液態，固化不充分 無 比較例9 無 2000 〇 變形 比較例10 有 2000 ' 〇 變形 比較例11 無 3000 ◎ 變形 比較例12 有 3000 ◎ 變形 從表4可知，在光照射之前不進行加溫的情況下，即 使增減光的照射光量，也不能得到黏接性優異而且沒有薄 膜的變形的層疊薄膜。 (產業上岛可利用性） 本發明可以用於在包括汽車、飛機、電氣·電子儀器的 廣泛產業領域中使用的層疊薄膜的製造。另外，由於為具 有快速固化性、快速黏接性的步驟，所以極有助於製造速 度的提高或加熱步驟的削減。 【圖式簡單說明】 無 【主要元件符號說明】 無 22 320119Example or Comparative Example Material Temperature (°C) ]-_—· The state of the adhesive after irradiation The deformation of the film after UV irradiation The durability after the moisture resistance test The optical 后 after the moisture resistance test, w: Comparative Example 4 25 is liquid, insufficient curing, no X. Comparative Example 5 30 is liquid, insufficient curing, no X - Example 7 40 Δ No Δ Example 50 〇〇 Example 9 60 ◎ No change without appreciation Example 10 70 ◎ No ◎ No change Appreciation π 80 ◎ No ◎ No change in poor example i2 100 --_© _ No △ Γ Some variation Example 13 120 〇 slightly warped Δ 4b辔j ~ Comparative example 6 140 〇 deformation X. As can be seen from Table 3, when an optical filter having a light having a cutoff wavelength of 390 nm or less is disposed between the metal halide lamp and the adherend, the polarizer and the film have less denaturation than the case where they are not disposed, and it is possible to obtain A laminated film with good adhesion and durability properties. The same result can be obtained even if a filter having a cutoff wavelength of 32 〇 nm or less, a filter having a cutoff wavelength of 34 〇 nm or less, or a filter having a cutoff wavelength of 370 nm or less is used instead of a ferrator having a cutoff wavelength of 390 nm or less. However, the effect of constituting the film is minimized when a filter having a cutoff wavelength of 39 Å or less is used. By using an optical filter, it is possible to suppress the heating to 12 〇. The deformation of the film at the time of ’ does not suppress the deformation of the film when heated to 140 °C. Production of Comparative Films of Comparative Examples 7 to 12 In the same manner as in Example 1, a film having a three-layer structure was obtained. A film of a three-layer structure obtained without heating was used, and a metal halide lamp (manufactured by Eyegraphics Co., Ltd.) was used, and the irradiation intensity was 5 〇〇mW/cm 2 (4 〇 5 nm), and the cumulative pupil was 500, 1 〇〇〇, 2 〇. 〇〇 and 3〇〇〇mJ/cm2 (4〇5nm) were irradiated with light at 21 320119 200904634 to obtain a laminated film. Further, when the integrated light amount is 2,000 and 3,000 mJ/cm 2 (405 nm), an optical filter (manufactured by Eyegraphics Co., Ltd.) which is disposed between the metal halide lamp and the adhesive film and has a cutoff wavelength of 390 nm or less is used. Light irradiation was performed to obtain a laminated film. [Table 4] The cumulative light amount of the optical filter UV of the example or the comparative example (mJ/cm2 (405 nm)) The state of the adhesive after the UV irradiation The deformation of the film after the UV irradiation Comparative Example 7 No 500 is a liquid, and the curing is not Full No Comparative Example 8 No 1000 is liquid, insufficient curing No Comparative Example 9 No 2000 〇 Deformation Comparative Example 10 Having 2000 '〇 Deformation Comparative Example 11 No 3000 ◎ Deformation Comparative Example 12 3,000 ◎ Deformation As shown in Table 4, in the light In the case where heating is not performed before the irradiation, even if the amount of light to be irradiated is increased or decreased, a laminated film which is excellent in adhesion and which is free from deformation of the film cannot be obtained. (Industrial Island Usability) The present invention can be applied to the production of a laminated film used in a wide range of industrial fields including automobiles, airplanes, electric and electronic instruments. In addition, since it is a step having rapid curability and fast adhesiveness, it contributes greatly to the improvement of the manufacturing speed or the reduction of the heating step. [Simple diagram description] None [Main component symbol description] None 22 320119