TWI679262B - UV-curable resin composition - Google Patents

UV-curable resin composition Download PDF

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Publication number
TWI679262B
TWI679262B TW106123152A TW106123152A TWI679262B TW I679262 B TWI679262 B TW I679262B TW 106123152 A TW106123152 A TW 106123152A TW 106123152 A TW106123152 A TW 106123152A TW I679262 B TWI679262 B TW I679262B
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Taiwan
Prior art keywords
resin composition
curable resin
meth
component
mass
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TW106123152A
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Chinese (zh)
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TW201811946A (en
Inventor
佐藤信之
Nobuyuki Sato
福田裕美
Hiromi Fukuda
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有澤製作所股份有限公司
Arisawa Mfg. Co., Ltd.
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Publication of TWI679262B publication Critical patent/TWI679262B/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/067—Polyurethanes; Polyureas
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    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
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    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
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    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
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    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
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    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
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    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
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    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
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Abstract

本發明提供一種即便於常溫下亦能夠容易地將LCD自被接著體剝離而可二次加工且能夠賦予良好之接著性之UV硬化型樹脂組合物、及包含其之接著片。 本發明之UV硬化型樹脂組合物含有(A)UV硬化型預聚物、(B)UV硬化型多官能單體、(C)光聚合起始劑、及(D)矽烷偶合劑； 上述(A)成分為(甲基)丙烯酸胺基甲酸酯；且 相對於上述(A)成分100質量份，上述(B)成分之含量為15～60質量份，上述(C)成分之含量為0.5質量份以上，上述(D)成分之含量為0.1～5質量份。The present invention provides a UV-curable resin composition capable of easily peeling an LCD from an adherend even at ordinary temperature, allowing secondary processing, and providing good adhesiveness, and an adhesive sheet including the same. The UV-curable resin composition of the present invention contains (A) a UV-curable prepolymer, (B) a UV-curable polyfunctional monomer, (C) a photopolymerization initiator, and (D) a silane coupling agent; A) The component is urethane (meth) acrylate; and the content of the component (B) is 15 to 60 parts by mass with respect to 100 parts by mass of the component (A), and the content of the component (C) is 0.5 The content of the component (D) is 0.1 to 5 parts by mass.

Description

UV硬化型樹脂組合物UV-curable resin composition

本發明係關於一種可用於液晶顯示器顯示部之UV(Ultraviolet，紫外線)硬化型樹脂組合物及包含其之接著片。The present invention relates to a UV (Ultraviolet) curable resin composition that can be used in a display portion of a liquid crystal display and an adhesive sheet containing the same.

當前，隨著數位化之電子機器之普及，液晶顯示器(LCD)成為極其普遍之顯示裝置，用作液晶電視或PC(Personal Computer，個人電腦)顯示器、行動電話終端、攜帶型遊戲機、計算器、時鐘等各種機器之顯示部。尤其是近年來為了賦予3D功能，存在將LCD與包含玻璃之圖案化相位差板接著者。 此處，接著有相位差板之LCD有於使用後被回收而僅再利用LCD之情形。例如，要求將相位差板自LCD剝離而對LCD進行二次加工。此時，於先前方法中，採用將LCD整體冷卻(換言之，將接著劑冷卻)而將相位差板自LCD剝離之方法。但是於該方法中，需要用於冷卻之設備，作業性亦不可謂良好。進而，由於相位差板與LCD均具有剛性，故存在於剝離時某一者發生破損之問題。即，先前之接著片難以於將LCD與相位差板接著之後容易地將其等剝離而對LCD進行二次加工。 為了解決此種問題點，而研究即便於常溫下且被接著體為如玻璃般堅硬者，亦能夠容易地剝離之接著片。例如，於專利文獻1中提出有一種透明接著膜，其含有接著劑成分、及藉由照射紫外線而產生氣體之氣體產生劑。又，於專利文獻2中提出有一種熱及光化射線硬化型(光硬化型)接著劑組合物。 [先前技術文獻] [專利文獻] [專利文獻1]日本專利特開2016-56244號公報 [專利文獻2]日本專利特表2011-508814號公報At present, with the popularization of digital electronic devices, liquid crystal displays (LCDs) have become extremely popular display devices used as liquid crystal television or PC (Personal Computer) displays, mobile phone terminals, portable game consoles, and calculators. , Clock, and other display units. In particular, in recent years, in order to provide a 3D function, there are those who connect an LCD with a patterned retardation plate including glass. Here, the LCD with the phase difference plate is recovered after use and only the LCD is reused. For example, it is required to separate the retardation plate from the LCD and perform secondary processing on the LCD. At this time, in the previous method, the entire LCD is cooled (in other words, the adhesive is cooled), and the retardation plate is peeled from the LCD. However, in this method, equipment for cooling is required, and workability is not good. Furthermore, since both the retardation plate and the LCD have rigidity, there is a problem that one of them is broken during peeling. In other words, it is difficult for the previous bonding sheet to easily separate the LCD and the retardation plate and to perform secondary processing on the LCD. In order to solve such a problem, it has been studied that the adhesive sheet that can be easily peeled off even at room temperature and the adherend is as hard as glass. For example, Patent Document 1 proposes a transparent adhesive film containing an adhesive agent component and a gas generating agent that generates a gas by irradiating ultraviolet rays. In addition, Patent Document 2 proposes a heat and actinic ray-curable (photocurable) adhesive composition. [Prior Art Literature] [Patent Literature] [Patent Literature 1] Japanese Patent Laid-Open No. 2016-56244 [Patent Literature 2] Japanese Patent Laid-Open No. 2011-508814

[發明所欲解決之問題] 然而，專利文獻1所記載之透明接著膜於二次加工時需要曝光，又，專利文獻2所記載之光化射線硬化型(光硬化型)接著劑組合物係藉由於二次加工時進行加熱並使用金屬線切進接著劑而去除接著劑。即，現狀為至今為止，尚未獲得既確保良好之接著性又能夠於常溫下容易地將LCD自被接著體剝離之接著片。 鑒於上述情況，本發明之目的在於提供一種即便於常溫下亦能夠容易地將LCD自被接著體剝離且能夠賦予良好之接著性的UV硬化型樹脂組合物、及包含其之接著片。 [解決問題之技術手段] 本發明人等為解決上述問題，經過努力研究，結果發現如下UV硬化型樹脂組合物能夠解決上述問題，從而完成本發明，上述UV硬化型樹脂組合物含有(A)UV硬化型預聚物、(B)UV硬化型多官能單體、(C)光聚合起始劑、及(D)矽烷偶合劑；上述(A)成分為(甲基)丙烯酸胺基甲酸酯；且相對於上述(A)成分100質量份，上述(B)成分之含量為15～60質量份，上述(C)成分之含量為0.5質量份以上，上述(D)成分之含量為0.1～5質量份。 即，本發明如下所述。 [1] 一種UV硬化型樹脂組合物，其含有(A)UV硬化型預聚物、(B)UV硬化型多官能單體、(C)光聚合起始劑、及(D)矽烷偶合劑； 上述(A)成分為(甲基)丙烯酸胺基甲酸酯；且 相對於上述(A)成分100質量份，上述(B)成分之含量為15～60質量份，上述(C)成分之含量為0.5質量份以上，上述(D)成分之含量為0.1～5質量份。 [2] 如上述[1]所記載之UV硬化型樹脂組合物，其中上述(甲基)丙烯酸胺基甲酸酯係選自由具有聚碳酸酯骨架之(甲基)丙烯酸胺基甲酸酯、具有聚醚骨架之(甲基)丙烯酸胺基甲酸酯、及具有聚酯骨架之(甲基)丙烯酸胺基甲酸酯所組成之群中之1種以上。 [3] 如上述[1]或[2]所記載之UV硬化型樹脂組合物，其中上述(甲基)丙烯酸胺基甲酸酯之重量平均分子量為10,000～100,000，雙鍵當量為1,000～5,000 g/eq。 [4] 如上述[1]至[3]中任一項所記載之UV硬化型樹脂組合物，其中上述(B)UV硬化型多官能單體為具有2個以上之官能基之(甲基)丙烯酸系單體。 [5] 如上述[1]至[4]中任一項所記載之UV硬化型樹脂組合物，其中上述(C)光聚合起始劑為醯基氧化膦系光聚合起始劑。 [6] 如上述[5]所記載之UV硬化型樹脂組合物，其中上述醯基氧化膦系光聚合起始劑為2,4,6-三甲基苯甲醯基二苯基氧化膦。 [7] 如上述[1]至[6]中任一項所記載之UV硬化型樹脂組合物，其中上述(D)矽烷偶合劑為具有(甲基)丙烯醯基之矽烷偶合劑。 [8] 一種接著片，其包含如上述[1]至[7]中任一項所記載之UV硬化型樹脂組合物。 [9] 如上述[8]所記載之接著片，其乾燥後之膜厚為10～250 μm。 [10] 一種3D液晶面板，其係將LCD與圖案化相位差板積層而成者；且 上述LCD與上述相位差板係藉由如上述[8]或[9]所記載之接著片而接著。 [11] 如上述[10]所記載之3D液晶面板，其中上述圖案化相位差板為形成有圖案之玻璃板。 [發明之效果] 本發明之包含UV硬化型樹脂組合物之接著片即便於常溫下亦能夠容易地將LCD自被接著體剝離而進行二次加工，且能夠賦予良好之接著性。[Problems to be Solved by the Invention] However, the transparent adhesive film described in Patent Document 1 requires exposure during secondary processing, and the actinic ray-curable (photocurable) adhesive composition described in Patent Document 2 The adhesive is removed by heating during the secondary processing and cutting into the adhesive using a wire. That is, the present state of the art is that there has not yet been obtained a bonding sheet that can ensure good adhesion and can easily peel the LCD from the adherend at room temperature. In view of the foregoing, an object of the present invention is to provide a UV-curable resin composition capable of easily peeling an LCD from an adherend even at normal temperature and providing good adhesiveness, and an adhesive sheet including the same. [Technical Means for Solving the Problem] The present inventors have made diligent research in order to solve the above problems, and found that the following UV-curable resin composition can solve the above problems, and thus completed the present invention. The UV-curable resin composition contains (A) UV-curable prepolymer, (B) UV-curable polyfunctional monomer, (C) photopolymerization initiator, and (D) silane coupling agent; the component (A) is (meth) acrylic acid urethane With respect to 100 parts by mass of the component (A), the content of the component (B) is 15 to 60 parts by mass, the content of the component (C) is 0.5 part by mass or more, and the content of the component (D) is 0.1 ~ 5 parts by mass. That is, the present invention is as follows. [1] A UV-curable resin composition containing (A) a UV-curable prepolymer, (B) a UV-curable polyfunctional monomer, (C) a photopolymerization initiator, and (D) a silane coupling agent The component (A) is a (meth) acrylic acid urethane; and the content of the component (B) is 15 to 60 parts by mass relative to 100 parts by mass of the component (A), and the component (C) is The content is 0.5 parts by mass or more, and the content of the component (D) is 0.1 to 5 parts by mass. [2] The UV-curable resin composition according to the above [1], wherein the (meth) acrylic acid urethane is selected from a (meth) acrylic acid urethane having a polycarbonate skeleton, One or more of the group consisting of a (meth) acrylic acid urethane having a polyether skeleton and a (meth) acrylic acid urethane having a polyester skeleton. [3] The UV-curable resin composition according to the above [1] or [2], wherein the weight average molecular weight of the (meth) acrylic acid urethane is 10,000 to 100,000, and the double bond equivalent is 1,000 to 5,000 g / eq. [4] The UV-curable resin composition according to any one of the above [1] to [3], wherein the (B) UV-curable polyfunctional monomer is a (methyl group having 2 or more functional groups) ) Acrylic monomer. [5] The UV-curable resin composition according to any one of the above [1] to [4], wherein the (C) photopolymerization initiator is a fluorenyl phosphine oxide-based photopolymerization initiator. [6] The UV-curable resin composition according to the above [5], wherein the fluorenylphosphine oxide-based photopolymerization initiator is 2,4,6-trimethylbenzylidenediphenylphosphine oxide. [7] The UV-curable resin composition according to any one of the above [1] to [6], wherein the (D) silane coupling agent is a silane coupling agent having a (meth) acrylfluorenyl group. [8] An adhesive sheet comprising the UV-curable resin composition according to any one of the above [1] to [7]. [9] The adhesive sheet according to the above [8], wherein the film thickness after drying is 10 to 250 μm. [10] A 3D liquid crystal panel, which is formed by laminating an LCD and a patterned retardation plate; and the LCD and the retardation plate are adhered by a bonding sheet as described in [8] or [9] above . [11] The 3D liquid crystal panel according to the above [10], wherein the patterned retardation plate is a patterned glass plate. [Effects of the Invention] The adhesive sheet containing the UV-curable resin composition of the present invention can easily peel the LCD from the adherend and perform secondary processing even at normal temperature, and can provide good adhesiveness.

以下，對用於實施本發明之形態(以下，稱為「本實施形態」)詳細地加以記載。再者，本發明並不限定於以下之實施形態，可於其主旨之範圍內實施各種變化。 本實施形態中之UV硬化型樹脂組合物含有(A)UV硬化型預聚物、(B)UV硬化型多官能單體、(C)光聚合起始劑、及(D)矽烷偶合劑； 上述(A)成分為(甲基)丙烯酸胺基甲酸酯；且 相對於上述(A)成分100質量份，上述(B)成分之含量為15～60質量份，上述(C)成分之含量為0.5質量份以上，上述(D)成分之含量為0.1～5質量份。 [(A)UV硬化型預聚物] 本實施形態中之UV硬化型樹脂組合物包含(A)UV硬化型預聚物(以下，亦稱為「(A)成分」)。UV硬化型預聚物只要為主鏈包含胺基甲酸酯結構、側鏈包含(甲基)丙烯醯基之(甲基)丙烯酸胺基甲酸酯，則並無特別限定。作為(甲基)丙烯酸胺基甲酸酯，並無特別限定，例如可列舉：具有聚碳酸酯骨架之(甲基)丙烯酸胺基甲酸酯、具有聚醚骨架之(甲基)丙烯酸胺基甲酸酯、具有聚酯骨架之(甲基)丙烯酸胺基甲酸酯等，其中，就硬化接著片之無黃變性之觀點而言，較佳為具有聚碳酸酯骨架之(甲基)丙烯酸胺基甲酸酯。 所謂具有聚碳酸酯骨架之(甲基)丙烯酸胺基甲酸酯，係指主鏈具有聚碳酸酯結構及胺基甲酸酯結構、側鏈具有(甲基)丙烯醯基之預聚物。具有聚碳酸酯骨架之(甲基)丙烯酸胺基甲酸酯例如可藉由使聚碳酸酯二醇、二異氰酸酯及羧酸二醇發生反應後，使(甲基)丙烯酸縮水甘油酯發生反應而獲得。 聚碳酸酯二醇之重量平均分子量較佳為170～1,000，更佳為300～700，進而較佳為400～600。若聚碳酸酯二醇之重量平均分子量為上述範圍，則有向胺基甲酸酯預聚物主鏈賦予二次加工所需之膜性之傾向。 作為二異氰酸酯，並無特別限定，例如可列舉：2,4-甲苯二異氰酸酯(2,4-TDI)、2,6-甲苯二異氰酸酯(2,6-TDI)、4,4'-二苯基甲烷二異氰酸酯(4,4'-MDI)、2,4'-二苯基甲烷二異氰酸酯(2,4'-MDI)、1,4-伸苯基二異氰酸酯、苯二甲基二異氰酸酯(XDI)、四甲基苯二甲基二異氰酸酯(TMXDI)、聯甲苯胺二異氰酸酯(TODI)、1,5-萘二異氰酸酯(NDI)等芳香族異氰酸酯；六亞甲基異氰酸酯(HDI)、三甲基六亞甲基二異氰酸酯(TMHDI)、離胺酸二異氰酸酯、降𦯉烷二異氰酸甲酯(NBDI)等脂肪族多異氰酸酯；反式環己烷-1,4-二異氰酸酯、異佛爾酮二異氰酸酯(IPDI)、H6XDI(氫化XDI)等脂環式多異氰酸酯等；其中，就光學特性(黃變難易度)之觀點而言，較佳為六亞甲基二異氰酸酯。 作為羧酸二醇並無特別限定，例如可列舉：二羥甲基丁酸、二羥甲基丙酸等。 所謂具有聚醚骨架之(甲基)丙烯酸胺基甲酸酯係指主鏈具有聚醚結構及胺基甲酸酯結構、側鏈具有(甲基)丙烯醯基之預聚物，具有聚酯骨架之(甲基)丙烯酸胺基甲酸酯係指主鏈具有聚酯結構及胺基甲酸酯結構、側鏈具有(甲基)丙烯醯基之預聚物。該等預聚物除分別使用聚醚二醇、聚酯二醇代替聚碳酸酯二醇以外，可藉由與上述具有聚碳酸酯骨架之(甲基)丙烯酸胺基甲酸酯相同之方法而獲得。此時，聚醚二醇、聚酯二醇之較佳之重量平均分子量與上述聚碳酸酯二醇之較佳之重量平均分子量相同。 (A)成分之重量平均分子量較佳為10,000～100,000，更佳為30,000～70,000，進而較佳為40,000～60,000。若重量平均分子量為上述範圍，則有製膜性、硬化性變得良好，且長期可靠性變得良好之傾向。 此處，重量平均分子量係指使用平均分子量為約500～約100萬之標準聚苯乙烯，且藉由凝膠滲透層析法(GPC)而測定之值。 (A)成分之雙鍵當量較佳為1,000～5,000 g/eq，更佳為1,500～2,500 g/eq，進而較佳為1,800～2,200 g/eq。若雙鍵當量為上述範圍，則有硬化收縮之影響較少，長期可靠性優異，又，變得容易硬化，且亦變得容易進行二次加工之傾向。 此處，雙鍵當量係指藉由含羧基之(甲基)丙烯酸酯之固形物成分質量(g)/具有環氧乙烷環及乙烯性不飽和鍵之化合物之莫耳數(g/mol)而算出之值。 (A)成分之玻璃轉移溫度(Tg)較佳為-10～20℃，更佳為-5～15℃，進而較佳為0～10℃。若玻璃轉移溫度為上述範圍，則有長期可靠性與二次加工性之平衡變得良好之傾向。 此處，玻璃轉移溫度係指藉由動態黏彈性測定(DMA)而測定之值。 [(B)UV硬化型多官能單體] 本實施形態中之UV硬化型樹脂組合物包含(B)UV硬化型多官能單體(以下，亦稱為「(B)成分」)。為了能夠進行LCD之二次加工，需要提高常溫下之黏彈性，於本實施形態中，藉由對UV硬化型預聚物添加UV硬化型多官能單體，而提高硬化後之交聯密度，從而提高常溫下之黏彈性。此處，UV硬化型樹脂組合物之黏彈性可藉由動態黏彈性測定(DMA)而測定，較佳為硬化後於常溫(25℃)下之儲存模數為1.0×108 ～1.0×1010 Pa，更佳為4.0×108 ～5.0×109 Pa，進而較佳為6.0×108 ～3.0×109 Pa。 作為(B)成分，並無特別限定，例如可列舉(甲基)丙烯酸系單體，其中，就提高交聯密度，提高二次加工性之觀點而言，較佳為具有2個以上之官能基之(甲基)丙烯酸系單體。 作為(B)成分，具體而言，作為官能基為2個者，可列舉：1,4-丁二醇二(甲基)丙烯酸酯、乙二醇二(甲基)丙烯酸酯、甘油二(甲基)丙烯酸酯、三環癸烷二甲醇二丙烯酸酯，作為官能基為3個者，可列舉：三羥甲基丙烷三丙烯酸酯、三羥甲基甲烷三(甲基)丙烯酸酯、三羥甲基丙烷環氧丙烷改性三(甲基)丙烯酸酯，作為官能基為4個以上者，可列舉：二季戊四醇四(甲基)丙烯酸酯、季戊四醇環氧乙烷改性四(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、季戊四醇環氧乙烷改性四(甲基)丙烯酸酯、二-三羥甲基丙烷四(甲基)丙烯酸酯、二季戊四醇六丙烯酸酯等，其中，就二次加工性之觀點而言，較佳為具有4個以上之官能基之(甲基)丙烯酸系單體，更佳為具有6個官能基之二季戊四醇六丙烯酸酯。 (B)成分相對於(A)成分100質量份之含量為15～60質量份，較佳為18～40質量份，更佳為20～30質量份。(B)成分之含量若未達15質量份，則硬化後之接著性較高，常溫下之二次加工性較差，若超過60質量份，則接著性不充分，長期可靠性較差。又，於將(B)成分相對於(A)成分100質量份之含量調整為上述範圍之情形時，因將樹脂組合物之熔融黏度保持於一定範圍內，故而有不易產生貼合不均或影像紊亂之優點。 [(C)光聚合起始劑] 本實施形態中之UV硬化型樹脂組合物包含(C)光聚合起始劑(以下，亦稱為「(C)成分」)。作為光聚合起始劑，並無特別限定，例如亦可使用醯基氧化膦系光聚合起始劑、苯烷酮系光聚合起始劑、分子內奪氫型光聚合起始劑等任一光聚合起始劑，其中，就反應性、硬化之均勻性之觀點而言，較佳為醯基氧化膦系光聚合起始劑。具體而言，可列舉：2,4,6-三甲基苯甲醯基苯基氧化膦、2,2-二甲氧基-1,2-二苯基乙烷-1-酮、苯基乙醛酸甲酯等，其中，就自由基產生效率較高及深部硬化性之觀點而言，較佳為2,4,6-三甲基苯甲醯基苯基氧化膦。 (C)成分相對於(A)成分100質量份之含量為0.5質量份以上，較佳為1.0質量份以上，更佳為1.5質量份以上。(C)光聚合起始劑之含量若為上述，則有硬化反應性變得良好，二次加工性、長期可靠性提高之傾向。作為(C)成分之含量之上限，並無特別限定，但由於有若過多則光學特性降低之傾向，故較佳為7.0質量份以下。 [(D)矽烷偶合劑] 本實施形態中之UV硬化型樹脂組合物除上述(A)～(C)成分以外，進而包含(D)矽烷偶合劑(以下，亦稱為「(D)成分」)。如上所述，本實施形態之UV硬化型樹脂組合物藉由包含UV硬化型多官能單體，能夠提高常溫下之黏彈性而進行LCP之二次加工。另一方面，於黏彈性較高之情形時，有與被接著體之接著性降低之傾向。於本實施形態中，藉由使UV硬化型樹脂組合物中含有矽烷偶合劑而維持接著力，尤其是提高被接著體為玻璃板之情形時之長期可靠性。 作為(D)成分，並無特別限定，例如亦可使用單體型矽烷偶合劑、烷氧基低聚物型矽烷偶合劑、多官能型矽烷偶合劑等任一矽烷偶合劑。其中，就提高被接著體為玻璃之情形時之接著性、及保持長期可靠性之觀點而言，較佳為具有(甲基)丙烯醯基之矽烷偶合劑，更佳為3-丙烯醯氧基丙基三甲氧基矽烷。 (D)成分相對於(A)成分100質量份之含量為0.1～5質量份，較佳為0.5～3.0質量份，更佳為0.5～1.5質量份。(D)成分之含量若為上述範圍，則有長期可靠性與二次加工性之平衡變得良好之傾向。 [其他成分] 本實施形態中之UV硬化型樹脂組合物除上述(A)～(D)成分以外，亦可包含二氧化矽、氧化鋁、水合氧化鋁等各種填料、及抗氧化劑、紫外線吸收劑、光穩定劑、抗靜電劑、調平劑、消泡劑、著色顏料、有機溶劑等通常有添加於接著劑之情況之添加劑。 [接著片] 本實施形態中之接著片包含上述UV硬化型樹脂組合物。具體而言，例如可藉由在PET(Polyethylene Terephthalate，聚對苯二甲酸乙二酯)等之保護膜上塗佈樹脂組合物並使其乾燥後，亦在相反面設置保護膜，從而獲得於雙面設置有保護膜之接著片。尤其是較佳為使用有機溶劑將UV硬化型樹脂組合物製成清漆之後，塗佈於保護膜上並進行乾燥。作為此時所使用之有機溶劑，並無特別限定，例如可列舉：甲苯、甲基乙基酮、環己酮、丙二醇單甲醚、二甲基乙醯胺等。其中，就溶解性之觀點而言，較佳為甲基乙基酮。又，清漆中之有機溶劑之含量相對於(A)成分100質量份，較佳為30～90質量份，更佳為40～70質量份。 作為保護膜，並無特別限定，例如，可列舉包含選自由聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯、及聚對苯二甲酸丁二酯所組成之群中之1種以上之樹脂的膜，其中，就減少製造成本之觀點而言，較佳為包含聚對苯二甲酸乙二酯樹脂之膜。 亦可對保護膜於供樹脂組合物塗佈之面實施脫模處理。由於藉由對保護膜實施脫模處理，而能夠於使用時容易地剝離保護膜，故而操作性提高。作為脫模處理，並無特別限定，例如可使用藉由矽酮系脫模劑、氟系脫模劑、長鏈烷基接枝聚合物系脫模劑等脫模劑或電漿處理而進行表面處理之方法等。 作為對保護膜塗佈UV硬化型樹脂組合物之方法，可根據塗佈厚度，適當地採用缺角輪塗佈機、模嘴塗佈機、凹版塗佈機等。 UV硬化型樹脂組合物之乾燥可利用線內乾燥器等而實施，彼時之乾燥條件可根據各成分之種類及量等而適當地進行調整。乾燥後之接著片之厚度較佳為10～250 μm，更佳為25～125 μm，進而較佳為30～75 μm。接著片之厚度若為上述範圍，則接著性變得良好，長期可靠性提高。於本實施形態中所謂長期可靠性，具體而言，包括因LCD與圖案化相位差板之接著性良好，故難以產生偏移，結果，觀察者能夠觀察到良好之3D影像。進而，接著片之厚度若為上述範圍，則LCD與圖案化相位差板之距離變得適當，於觀看3D影像時，能夠確保適度之視角。 [3D液晶面板] 本實施形態中之3D液晶面板為將LCD與圖案化相位差板積層而成者，且上述LCD與上述相位差板係藉由本實施形態中之接著片而接著。3D液晶面板例如係藉由在將接著片貼合於相位差板之後，自其上貼合LCD，進而利用UV之照射使接著片UV硬化而獲得。 作為圖案化相位差板，可使用形成有圖案之玻璃板。 再者，本實施形態中之UV硬化型樹脂組合物不僅可用於3D液晶面板之用途，亦可用於預想對LCD、有機EL(Electro-Luminescence，電致發光)等顯示裝置進行二次加工之全部用途。作為此種用途，例如可列舉觸控感測器面板、數位標牌等。 [實施例] 以下，藉由實施例及比較例對本發明進一步具體地進行說明，但本發明並不僅限定於該等實施例。 於實施例及比較例中所使用之各成分、材料如下所述。 [(A)成分：UV硬化型預聚物] 依據以下之合成例1～3及比較合成例1，製作UV硬化型預聚物(a)～(d)。 [(B)成分：UV硬化型多官能單體] (1)UV硬化型多官能單體(a) 二季戊四醇六丙烯酸酯 DAICEL ALLNEX公司製造，製品名「DPHA」 (2)UV硬化型多官能單體(b) 三環癸烷二甲醇二丙烯酸酯 DAICEL ALLNEX公司製造，製品名「IRR214-K」 (3)UV硬化型多官能單體(c) 三羥甲基丙烷三丙烯酸酯 DAICEL ALLNEX公司製造，製品名「TMPTA」 (4)UV硬化型多官能單體(d) 丙烯酸乙氧化苯酯(一官能) DAICEL ALLNEX公司製造，製品名「EBECRYL110」 [(C)成分：光聚合起始劑] (1)光聚合起始劑(a) 2,4,6-三甲基苯甲醯基苯基氧化膦 BASF公司製造，商品名「Irgacure TPO」，醯基氧化膦系光聚合起始劑 (2)光聚合起始劑(b) 2,2-二甲氧基-1,2-二苯基乙烷-1-酮 BASF公司製造，商品名「Irgacure 651」，苯烷酮系光聚合起始劑 (3)光聚合起始劑(c) 苯基乙醛酸甲酯 BASF公司製造，商品名「Irgacure MBF」，分子內奪氫型光聚合起始劑 [(D)成分：矽烷偶合劑] (1)矽烷偶合劑(a) 單體型矽烷偶合劑 信越化學工業公司製造，商品名「KBM-5103」，3-丙烯醯氧基丙基三甲氧基矽烷 (2)矽烷偶合劑(b) 烷氧基低聚物型矽烷偶合劑 信越化學工業公司製造，商品名「KR-513」 (3)矽烷偶合劑(c) 多官能型矽烷偶合劑 信越化學工業公司製造，商品名「X-12-1050」 各評價方法及測定方法如下所述。 [二次加工性] (1)樣品製作程序 將接著片之單側PET膜剝離，且藉由層壓而貼合於玻璃(0.7 t，19英吋)，並進行高壓釜處理。層壓係使用輥式層壓，於層壓輥溫度25～40℃、層壓輥線壓1.0～2.0 kgf/cm、層壓輥速度0.3～2.0 m/min下實施，高壓釜係於溫度60℃、壓力0.6 MPa、時間10 min下實施。將另一側之PET膜剝離，藉由真空層壓與LCD貼合，再次進行高壓釜處理之後進行UV曝光，藉此獲得試驗樣品。真空層壓係於溫度25～50℃、壓力0.01～0.05 MPa、抽真空60 s、加壓30 s下實施。高壓釜係於溫度60℃、壓力0.6 MPa、時間1 hr下實施。UV曝光係使用超高壓水銀燈光源，以累計光量成為3000 mJ/cm2 之方式實施。 (2)測定方法 將試驗樣品於常溫下放置24 hr以上之後，觀察剝離玻璃後之被接著體(玻璃、LCD)之破損，並依據下述進行評價。 ◎：未使被接著體破損，可容易地進行二次加工 ○：未使被接著體破損，可進行二次加工 ×：難以進行二次加工 [接著性] (1)樣品製作程序 藉由與二次加工性同樣之程序製作試驗樣品。 (2)測定方法 將試驗樣品以立於濕熱器之狀態放置。條件係設為溫度50℃、濕度80%、時間240 hr。其後，於常溫下放置24 hr。對與開始放置於濕熱器時相比較之情形的玻璃貼合位置之偏移或***、發泡之有無進行觀察，並依據下述進行評價。 ○：未產生玻璃之位置偏移、***、發泡 ×：產生玻璃之位置偏移、***、發泡 [貼合性] (1)樣品製作程序 藉由與二次加工性同樣之程序製作試驗樣品。 (2)測定方法 點亮試驗樣品之顯示器，並依據下述進行評價。 ○：顯示圖像未產生貼合不均、3D偏移(無重影之產生) ×：顯示圖像產生貼合不均、3D偏移(有重影之產生) [光學特性] (1)樣品製作程序 將接著片之單側PET膜剝離，且藉由真空層壓而貼合於光學玻璃(40 mm見方)。真空層壓係於溫度25～50℃、壓力0.01～0.05 MPa、抽真空10 s、加壓10 s下實施。將另一側之PET膜剝離，於與上述真空層壓之條件相同之條件下貼合於光學玻璃後，進行高壓釜處理，繼而進行UV曝光，藉此獲得試驗樣品。高壓釜係於溫度60℃、壓力0.6 MPa、時間1 hr下實施。UV曝光係使用超高壓水銀燈光源，以累計光量成為3000 mJ/cm2 之方式實施。 使用分光光度計(Hitachi High-Technologies Corporation製造之U-4100)測定試驗樣品之黃色指數(YI，Yellow Index)。測定條件係設為C光源、透過、波長λ＝380～760 nm。 ◎：YI值未達1.5 ○：YI值為1.5以上且未達2 ×：YI值為2以上 (合成例1)UV硬化型預聚物(a) 於具備溫度計、冷凝管、攪拌裝置之4口燒瓶中，將六亞甲基二異氰酸酯(Tosoh股份有限公司製造，商品名：HDI，簡稱：HDI)33.3質量份、重量平均分子量400之聚碳酸酯二醇59.4質量份、二羥甲基丁酸7.3質量份、作為觸媒之月桂酸二丁基錫等有機錫化合物1質量份、作為有機溶劑之甲基乙基酮100質量份添加至反應容器，於70℃下反應24小時。 為了確認所獲得之合成物之反應狀況，使用IR(Infrared Radiation，紅外線)測定機器進行分析。於IR圖中，確認該合成物之NCO特性吸收(2270 cm-1 )消失，而確認合成物為具有羧基之丙烯酸胺基甲酸酯。 繼而，將所獲得之具有羧基之丙烯酸胺基甲酸酯100質量份、甲基丙烯酸縮水甘油酯7.1質量份、作為觸媒之三乙胺0.7質量份、作為聚合抑制劑之對苯二酚0.05重合份添加至反應容器，於75℃下進行反應12小時而進行加成反應，藉此獲得UV硬化型預聚物(a)。 再者，加成反應於依據以下方法而測定之酸值成為5 mgKOH/g以下之時間點結束。又，關於所獲得之UV硬化型預聚物(a)，重量平均分子量為50,000，固形物成分濃度為50質量%，雙鍵當量為2,000 g/eq，Tg為5℃。 (酸值測定方法) 稱量1 g之樹脂之固形物成分，添加混合溶劑(質量比：甲苯/甲醇＝50/50)，且適量地添加酚酞溶液作為溶解後指示劑，利用0.1 N之氫氧化鉀水溶液進行滴定，並根據下述式(α)測定酸值： x＝10×Vf×56.1/(Wp×I) (α) (式(α)中，x表示酸值(mgKOH/g)，Vf表示0.1 N之KOH水溶液之滴定量(mL)，Wp表示所測定之樹脂溶液之質量(g)，I係以(質量%)表示所測定之樹脂溶液中之不揮發分之比率)。 (合成例2)UV硬化型預聚物(b) 除使用聚醚二醇代替聚碳酸酯二醇以外，藉由與合成例1同樣之方法獲得UV硬化型預聚物(b)。 (合成例3)UV硬化型預聚物(c) 除使用聚酯二醇代替聚碳酸酯二醇以外，藉由與合成例1同樣之方法獲得UV硬化型預聚物(c)。 (比較合成例1)UV硬化型預聚物(d) 向具備攪拌機、溫度計、滴液漏斗、及氮氣導入管之反應容器中添加作為聚合溶劑之甲氧基丙醇丙二醇單甲醚(PGM)100.0 g，一面於氮氣氣流下攪拌，一面升溫至80度。在保溫於80℃之狀態下，耗時3小時自滴液漏斗向其中滴加於室溫下預先混合之苯乙烯13.5質量份、丙烯酸乙酯67質量份、丙烯酸11.5質量份、作為自由基聚合起始劑之偶氮雙異丁腈0.5 g。滴加結束後，一面攪拌反應溶液，一面升溫至90℃，使反應溶液之溫度保持於90度，並且進而攪拌2小時，而獲得共聚物。 繼而，將所獲得之共聚物100質量份、甲基丙烯酸縮水甘油酯7.8質量份、作為觸媒之三乙胺0.8質量份、作為聚合抑制劑之對苯二酚0.05重合份添加至反應容器，於100℃下進行反應12小時而進行加成反應，藉此獲得UV硬化型預聚物(d)。 再者，加成反應於酸值成為5 mgKOH/g以下之時間點結束。又，關於所獲得之UV硬化型預聚物(d)，重量平均分子量為45,000，固形物成分濃度為47質量%，Tg為3℃。 (實施例1) (1)UV硬化型樹脂組合物之製備 向反應容器中添加UV硬化型預聚物(a)100質量份，進而，添加UV硬化型多官能單體(a)25質量份、光聚合起始劑(a)1.5質量份、矽烷偶合劑(a)1質量份、及作為溶劑之甲基乙基酮140質量份進行攪拌，獲得樹脂組合物。 (2)接著片之製作 將上述(1)所獲得之樹脂組合物以乾燥後之厚度成為30 μm以上之方式塗佈於38 μm之PET膜上，以130℃乾燥5分鐘之後，亦在相反面設置PET膜，從而獲得雙面具備PET膜之接著片。 使用所獲得之接著片，進行二次加工性、接著性、貼合性、光學特性之評價。 (實施例2～20)、(比較例1～7) 除如表1～3所記載般變更各成分之種類及含量以外，藉由與實施例1同樣之方法，獲得UV硬化型樹脂組合物及接著片。 使用所獲得之接著片，進行二次加工性、接著性、貼合性、光學特性之評價。 [表1] [表2] [表3] [產業上之可利用性] 本發明之包含UV硬化型樹脂組合物之接著片具有作為液晶表示顯示器等之接著劑的產業上之可利用性。Hereinafter, the form for implementing this invention (henceforth "this embodiment") is described in detail. The present invention is not limited to the following embodiments, and various changes can be made within the scope of the gist thereof. The UV-curable resin composition in this embodiment contains (A) a UV-curable prepolymer, (B) a UV-curable polyfunctional monomer, (C) a photopolymerization initiator, and (D) a silane coupling agent; The component (A) is (meth) acrylic acid urethane; and the content of the component (B) is 15 to 60 parts by mass with respect to 100 parts by mass of the component (A), and the content of the component (C) It is 0.5 parts by mass or more, and the content of the component (D) is 0.1 to 5 parts by mass. [(A) UV-curable prepolymer] The UV-curable resin composition in this embodiment includes (A) a UV-curable prepolymer (hereinafter, also referred to as "(A) component"). The UV-curable prepolymer is not particularly limited as long as it is a (meth) acrylic acid urethane having a urethane structure in its main chain and a (meth) acrylfluorenyl group in its side chain. The (meth) acrylic acid urethane is not particularly limited, and examples thereof include (meth) acrylic acid urethane having a polycarbonate skeleton, and (meth) acrylic acid amine having a polyether skeleton. Formic acid esters, (meth) acrylic acid urethanes having a polyester skeleton, and the like, from the viewpoint of non-yellowing of the cured adhesive sheet, (meth) acrylic acid having a polycarbonate skeleton is preferred. Carbamate. The (meth) acrylic acid urethane having a polycarbonate skeleton refers to a prepolymer having a polycarbonate structure and a urethane structure in a main chain and a (meth) acrylfluorene group in a side chain. The (meth) acrylic acid urethane having a polycarbonate skeleton can be obtained, for example, by reacting a polycarbonate diol, a diisocyanate, and a carboxylic acid diol, and then reacting a glycidyl (meth) acrylate. obtain. The weight average molecular weight of the polycarbonate diol is preferably 170 to 1,000, more preferably 300 to 700, and still more preferably 400 to 600. When the weight average molecular weight of the polycarbonate diol is within the above range, the film properties required for secondary processing tend to be imparted to the urethane prepolymer main chain. The diisocyanate is not particularly limited, and examples thereof include 2,4-toluene diisocyanate (2,4-TDI), 2,6-toluene diisocyanate (2,6-TDI), and 4,4'-diphenyl Methane diisocyanate (4,4'-MDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI), 1,4-phenylene diisocyanate, xylylene diisocyanate ( XDI), tetramethylxylylene diisocyanate (TMXDI), p-toluidine diisocyanate (TODI), 1,5-naphthalene diisocyanate (NDI) and other aromatic isocyanates; hexamethylene isocyanate (HDI), three Aliphatic polyisocyanates such as methyl hexamethylene diisocyanate (TMHDI), lysine diisocyanate, alkane diisocyanate (NBDI); transcyclohexane-1,4-di Alicyclic polyisocyanates, such as isocyanate, isophorone diisocyanate (IPDI), and H6XDI (hydrogenated XDI). Among them, hexamethylene diisocyanate is preferred from the viewpoint of optical characteristics (easiness of yellowing). . The carboxylic acid diol is not particularly limited, and examples thereof include dimethylolbutanoic acid and dimethylolpropionic acid. The so-called (meth) acrylic acid urethane having a polyether skeleton refers to a prepolymer having a polyether structure and a urethane structure in a main chain and a (meth) acrylfluorene group in a side chain, and having a polyester The (meth) acrylic acid urethane of the skeleton refers to a prepolymer having a polyester structure and a urethane structure in the main chain and a (meth) acrylfluorene group in the side chain. These prepolymers can be prepared by the same method as the above-mentioned (meth) acrylic acid urethane having a polycarbonate skeleton, except that the polyether diol and polyester diol are used instead of the polycarbonate diol. obtain. At this time, the preferred weight average molecular weight of the polyether diol and polyester diol is the same as the preferred weight average molecular weight of the polycarbonate diol described above. The weight average molecular weight of the component (A) is preferably 10,000 to 100,000, more preferably 30,000 to 70,000, and still more preferably 40,000 to 60,000. When the weight average molecular weight is in the above-mentioned range, the film-forming properties and hardenability tend to be good, and the long-term reliability tends to be good. Here, the weight average molecular weight refers to a value measured by gel permeation chromatography (GPC) using standard polystyrene having an average molecular weight of about 5 to about 1 million. The double bond equivalent of the component (A) is preferably 1,000 to 5,000 g / eq, more preferably 1,500 to 2,500 g / eq, and even more preferably 1,800 to 2,200 g / eq. When the double bond equivalent is within the above range, there is less effect of hardening shrinkage, excellent long-term reliability, easy hardening, and easy secondary processing. Here, the double bond equivalent means the solid content of the carboxyl group-containing (meth) acrylate (g) / mole number of the compound having an ethylene oxide ring and an ethylenically unsaturated bond (g / mol ). The glass transition temperature (Tg) of the component (A) is preferably -10 to 20 ° C, more preferably -5 to 15 ° C, and even more preferably 0 to 10 ° C. When the glass transition temperature is in the above range, the balance between long-term reliability and secondary processability tends to be good. Here, the glass transition temperature refers to a value measured by a dynamic viscoelasticity measurement (DMA). [(B) UV-curable polyfunctional monomer] The UV-curable resin composition in this embodiment includes (B) a UV-curable polyfunctional monomer (hereinafter, also referred to as "(B) component"). In order to enable the secondary processing of LCD, it is necessary to increase the viscoelasticity at room temperature. In this embodiment, by adding a UV-curable polyfunctional monomer to the UV-curable prepolymer, the cross-linking density after curing is increased. So as to improve the viscoelasticity at room temperature. Here, the viscoelasticity of the UV-curable resin composition can be measured by dynamic viscoelasticity measurement (DMA), and it is preferable that the storage modulus at room temperature (25 ° C) after curing is 1.0 × 10 8 to 1.0 × 10 10 Pa, more preferably 4.0 × 10 8 to 5.0 × 10 9 Pa, and even more preferably 6.0 × 10 8 to 3.0 × 10 9 Pa. The component (B) is not particularly limited, and examples thereof include (meth) acrylic monomers. Among them, from the viewpoint of increasing the crosslinking density and improving the secondary processability, it is preferable to have two or more functions. (Meth) acrylic monomer. As the component (B), specifically, as two functional groups, 1,4-butanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, and glycerol bis ( Meth) acrylate, tricyclodecane dimethanol diacrylate, and three functional groups include trimethylolpropane triacrylate, trimethylolmethane tri (meth) acrylate, and trimethylmethacrylate. Methylolpropane propylene oxide modified tri (meth) acrylates, which have four or more functional groups, include dipentaerythritol tetra (meth) acrylate, pentaerythritol ethylene oxide modified tetra (methyl) ) Acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol ethylene oxide modified tetra (meth) acrylate, di-trimethylolpropane tetra (meth) acrylate, dipentaerythritol hexaacrylate, etc., Among these, from the viewpoint of secondary processability, a (meth) acrylic monomer having 4 or more functional groups is preferred, and dipentaerythritol hexaacrylate having 6 functional groups is more preferred. The content of the component (B) with respect to 100 parts by mass of the component (A) is 15 to 60 parts by mass, preferably 18 to 40 parts by mass, and more preferably 20 to 30 parts by mass. (B) If the content of the component is less than 15 parts by mass, the adhesiveness after hardening is high, and the secondary processability at room temperature is poor. If it exceeds 60 parts by mass, the adhesiveness is insufficient and the long-term reliability is poor. When the content of the component (B) with respect to 100 parts by mass of the component (A) is adjusted to the above-mentioned range, the melt viscosity of the resin composition is kept within a certain range, so that uneven bonding is unlikely to occur or The advantages of image disorder. [(C) Photopolymerization Initiator] The UV-curable resin composition in this embodiment includes (C) a photopolymerization initiator (hereinafter, also referred to as "(C) component"). The photopolymerization initiator is not particularly limited. For example, any photopolymerization such as a fluorenylphosphine oxide-based photopolymerization initiator, an benzonone-based photopolymerization initiator, or an intramolecular hydrogen abstraction type photopolymerization initiator may be used. Among the initiators, a fluorenylphosphine oxide-based photopolymerization initiator is preferred from the viewpoints of reactivity and uniformity of curing. Specific examples include 2,4,6-trimethylbenzylidenephenylphosphine oxide, 2,2-dimethoxy-1,2-diphenylethane-1-one, and phenyl Among them, methyl glyoxylate and the like are more preferably 2,4,6-trimethylbenzylphenylphenylphosphine oxide from the viewpoints of high radical generation efficiency and deep sclerosis. The content of the component (C) with respect to 100 parts by mass of the component (A) is 0.5 parts by mass or more, preferably 1.0 part by mass or more, and more preferably 1.5 parts by mass or more. (C) When content of a photoinitiator is the said thing, hardening reactivity will become favorable, and secondary workability and long-term reliability will improve. The upper limit of the content of the component (C) is not particularly limited, but if it is too large, the optical characteristics tend to decrease, and therefore it is preferably 7.0 parts by mass or less. [(D) Silane Coupling Agent] The UV-curable resin composition in this embodiment contains, in addition to the components (A) to (C), (D) a silane coupling agent (hereinafter, also referred to as "(D) component "). As described above, the UV-curable resin composition of this embodiment can improve the viscoelasticity at room temperature by including a UV-curable polyfunctional monomer, and perform secondary processing of LCP. On the other hand, when the viscoelasticity is high, the adhesion to the adherend tends to decrease. In this embodiment, the adhesive force is maintained by including a silane coupling agent in the UV-curable resin composition, and the long-term reliability is particularly improved when the adherend is a glass plate. The component (D) is not particularly limited, and for example, any silane coupling agent such as a monomer-type silane coupling agent, an alkoxy oligomer-type silane coupling agent, or a polyfunctional silane coupling agent may be used. Among these, from the viewpoints of improving adhesion when the adherend is glass, and maintaining long-term reliability, a silane coupling agent having a (meth) acrylfluorenyl group is preferred, and 3-propylenefluorene is more preferred. Propyltrimethoxysilane. The content of the component (D) with respect to 100 parts by mass of the component (A) is 0.1 to 5 parts by mass, preferably 0.5 to 3.0 parts by mass, and more preferably 0.5 to 1.5 parts by mass. (D) If content of a component is the said range, there exists a tendency for the balance of long-term reliability and secondary processability to become favorable. [Other components] In addition to the components (A) to (D) described above, the UV-curable resin composition in this embodiment may contain various fillers such as silica, alumina, and hydrated alumina, as well as antioxidants and ultraviolet absorption. Agents, light stabilizers, antistatic agents, leveling agents, antifoaming agents, coloring pigments, organic solvents, and the like are usually added to the case of the adhesive. [Adhesive sheet] The adhesive sheet in this embodiment contains the above-mentioned UV-curable resin composition. Specifically, for example, by coating and drying a resin composition on a protective film such as PET (Polyethylene Terephthalate), a protective film can also be provided on the opposite side, thereby obtaining Adhesive sheets are provided on both sides with a protective film. In particular, the UV-curable resin composition is preferably made into a varnish using an organic solvent, and then coated on a protective film and dried. The organic solvent used at this time is not particularly limited, and examples thereof include toluene, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether, and dimethylacetamide. Among these, methyl ethyl ketone is preferred from the viewpoint of solubility. The content of the organic solvent in the varnish is preferably 30 to 90 parts by mass, and more preferably 40 to 70 parts by mass with respect to 100 parts by mass of the component (A). The protective film is not particularly limited, and examples thereof include one selected from the group consisting of polyethylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate. Among the above-mentioned resin films, a film containing a polyethylene terephthalate resin is preferred from the viewpoint of reducing manufacturing costs. The protective film may be subjected to a release treatment on the surface to which the resin composition is applied. Since the protective film can be easily peeled during use by applying a release treatment to the protective film, operability is improved. The release treatment is not particularly limited. For example, the release treatment can be performed using a release agent such as a silicone release agent, a fluorine release agent, a long-chain alkyl graft polymer release agent, or a plasma treatment. Surface treatment methods. As a method of applying the UV-curable resin composition to the protective film, a notch wheel coater, a die coater, a gravure coater, etc. may be appropriately used depending on the coating thickness. The drying of the UV-curable resin composition can be performed using an in-line dryer or the like, and the drying conditions at that time can be appropriately adjusted according to the type and amount of each component and the like. The thickness of the adhesive sheet after drying is preferably 10 to 250 μm, more preferably 25 to 125 μm, and even more preferably 30 to 75 μm. When the thickness of the adhesive sheet is within the above range, the adhesiveness is improved and the long-term reliability is improved. The so-called long-term reliability in this embodiment specifically includes that since the adhesion between the LCD and the patterned retardation plate is good, it is difficult to cause offset, and as a result, the observer can observe a good 3D image. Furthermore, if the thickness of the adhesive sheet is within the above range, the distance between the LCD and the patterned retardation plate becomes appropriate, and a proper viewing angle can be ensured when viewing a 3D image. [3D Liquid Crystal Panel] The 3D liquid crystal panel in this embodiment is a laminate of an LCD and a patterned retardation plate, and the LCD and the retardation plate are connected by a bonding sheet in this embodiment. The 3D liquid crystal panel is obtained by, for example, bonding a bonding sheet to a retardation plate, bonding a LCD thereon, and further curing the bonding sheet by UV irradiation. As the patterned retardation plate, a patterned glass plate can be used. In addition, the UV-curable resin composition in this embodiment can be used not only for the application of a 3D liquid crystal panel, but also for all the secondary processing of display devices such as LCD and organic EL (Electro-Luminescence). use. Examples of such applications include touch sensor panels and digital signage. [Examples] Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to these examples. Each component and material used in an Example and a comparative example are as follows. [(A) Component: UV-curable prepolymer] UV-curable prepolymers (a) to (d) were prepared according to the following Synthesis Examples 1 to 3 and Comparative Synthesis Example 1. [(B) Ingredient: UV-curable polyfunctional monomer] (1) UV-curable polyfunctional monomer (a) Dipentaerythritol hexaacrylate manufactured by DAICEL ALLNEX, product name "DPHA" (2) UV-curable polyfunctional Monomer (b) Tricyclodecane dimethanol diacrylate manufactured by DAICEL ALLNEX Corporation, product name "IRR214-K" (3) UV-curable polyfunctional monomer (c) Trimethylolpropane triacrylate DAICEL ALLNEX Corporation Manufactured under the product name "TMPTA" (4) UV-curable polyfunctional monomer (d) Phenyl ethoxylate (monofunctional) manufactured by DAICEL ALLNEX Corporation, with the product name "EBECRYL110" [(C) Ingredient: Photopolymerization initiator (1) Photopolymerization initiator (a) 2,4,6-trimethylbenzylidenephenylphosphine oxide manufactured by BASF, trade name "Irgacure TPO", fluorenylphosphine oxide-based photopolymerization initiator (2) Photopolymerization initiator (b) 2,2-dimethoxy-1,2-diphenylethane-1-one Manufactured by BASF Corporation under the trade name "Irgacure 651", benzonone-based photopolymerization Initiator (3) Photopolymerization initiator (c) Methyl phenylglyoxylate manufactured by BASF, trade name "Irgacure MBF", intramolecular hydrogen abstraction type photopolymerization initiator [(D) component: silane coupling ] (1) Silane coupling agent (a) Monomer type silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd., trade name "KBM-5103", 3-propenyloxypropyltrimethoxysilane (2) Silane coupling agent (b ) Alkoxy oligomeric silane coupling agent manufactured by Shin-Etsu Chemical Industry Co., Ltd. under the trade name "KR-513" (3) Silane coupling agent (c) Multifunctional silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd. under the trade name "X- 12-1050 "Each evaluation method and measurement method are described below. [Secondary processability] (1) Sample preparation procedure The one-sided PET film of the adhesive sheet was peeled off, laminated to glass (0.7 t, 19 inches) by lamination, and subjected to an autoclave treatment. The lamination system uses roll lamination, and is carried out at a lamination roll temperature of 25 to 40 ° C, a lamination roll pressure of 1.0 to 2.0 kgf / cm, and a lamination roll speed of 0.3 to 2.0 m / min. The autoclave is at a temperature of 60 It was carried out at a temperature of 0.6 ° C, a pressure of 0.6 MPa, and a time of 10 minutes. The PET film on the other side was peeled off and bonded to the LCD by vacuum lamination. After autoclave treatment was performed again, UV exposure was performed to obtain a test sample. The vacuum lamination is performed at a temperature of 25 to 50 ° C, a pressure of 0.01 to 0.05 MPa, a vacuum for 60 s, and a pressure of 30 s. The autoclave was implemented at a temperature of 60 ° C, a pressure of 0.6 MPa, and a time of 1 hr. The UV exposure is performed using an ultra-high pressure mercury lamp light source so that the accumulated light amount becomes 3000 mJ / cm 2 . (2) Measurement method After the test sample was left at room temperature for more than 24 hr, the adherend (glass, LCD) after the glass was peeled off was observed for damage, and evaluated according to the following. ◎: The bonded body is not damaged, and secondary processing can be easily performed. ○: The bonded body is not damaged, and secondary processing can be performed. ×: Secondary processing is difficult. [Adhesiveness] (1) Sample preparation procedure A test sample was made with the same secondary processability. (2) Measurement method Place the test sample on a humidifier. The conditions were set to a temperature of 50 ° C, a humidity of 80%, and a time of 240 hr. Thereafter, it was left at room temperature for 24 hr. The presence or absence of deviation, bulging, or foaming of the glass bonding position compared to the case when it was initially placed in a humidifier was observed and evaluated based on the following. ○: No positional deviation, bulging, or foaming of the glass was generated ×: No positional deviation, bulging, or foaming of the glass occurred [adhesiveness] (1) Sample preparation procedure The test was made using the same procedure as the secondary processability sample. (2) Measurement method The display of the test sample is lighted, and evaluation is performed according to the following. ○: Display image does not have uneven bonding and 3D shift (no ghosting) ×: Display image shows uneven bonding and 3D shift (with ghosting) [Optical characteristics] (1) The sample preparation procedure peeled off the one-sided PET film of the adhesive sheet, and bonded it to the optical glass (40 mm square) by vacuum lamination. Vacuum lamination is performed at a temperature of 25 to 50 ° C, a pressure of 0.01 to 0.05 MPa, a vacuum for 10 s, and a pressure of 10 s. The PET film on the other side was peeled off and bonded to optical glass under the same conditions as the conditions for the vacuum lamination described above, and then subjected to an autoclave treatment followed by UV exposure to obtain a test sample. The autoclave was implemented at a temperature of 60 ° C, a pressure of 0.6 MPa, and a time of 1 hr. The UV exposure is performed using an ultra-high pressure mercury lamp light source so that the accumulated light amount becomes 3000 mJ / cm 2 . The yellow index (YI, Yellow Index) of the test sample was measured using a spectrophotometer (U-4100 manufactured by Hitachi High-Technologies Corporation). The measurement conditions were a C light source, transmission, and a wavelength λ = 380 to 760 nm. ◎: YI value is less than 1.5 ○: YI value is 1.5 or more and less than 2 ×: YI value is 2 or more (synthesis example 1) UV-curable prepolymer (a) 4 is equipped with a thermometer, a condenser tube, and a stirring device In a beaker, 33.3 parts by mass of hexamethylene diisocyanate (manufactured by Tosoh Co., Ltd., trade name: HDI, abbreviation: HDI), 59.4 parts by mass of polycarbonate diol with a weight average molecular weight of 400, and dimethylolbutane 7.3 parts by mass of an acid, 1 part by mass of an organic tin compound such as dibutyltin laurate as a catalyst, and 100 parts by mass of methyl ethyl ketone as an organic solvent were added to a reaction vessel, and reacted at 70 ° C. for 24 hours. In order to confirm the reaction status of the obtained composition, an IR (Infrared Radiation) measurement device was used for analysis. In the IR chart, it was confirmed that the NCO characteristic absorption (2270 cm -1 ) of the composition disappeared, and it was confirmed that the composition was an acrylic urethane having a carboxyl group. Next, 100 parts by mass of the acrylic urethane having a carboxyl group, 7.1 parts by mass of glycidyl methacrylate, 0.7 parts by mass of triethylamine as a catalyst, and hydroquinone as a polymerization inhibitor 0.05 were obtained. The weight fraction was added to a reaction container, and a reaction was performed at 75 ° C. for 12 hours to perform an addition reaction, thereby obtaining a UV-curable prepolymer (a). In addition, the addition reaction was completed at the time point when the acid value measured by the following method became 5 mgKOH / g or less. The obtained UV-curable prepolymer (a) had a weight average molecular weight of 50,000, a solid content concentration of 50% by mass, a double bond equivalent of 2,000 g / eq, and a Tg of 5 ° C. (Acid value measurement method) Weigh 1 g of the solid content of the resin, add a mixed solvent (mass ratio: toluene / methanol = 50/50), and appropriately add a phenolphthalein solution as an indicator after dissolution, using 0.1 N hydrogen The potassium oxide aqueous solution was titrated, and the acid value was measured according to the following formula (α): x = 10 × Vf × 56.1 / (Wp × I) (α) (In the formula (α), x represents an acid value (mgKOH / g) Vf represents the titer (mL) of a 0.1 N KOH aqueous solution, Wp represents the mass (g) of the measured resin solution, and I represents the ratio of the nonvolatile content in the measured resin solution by (mass%). (Synthesis Example 2) A UV-curable prepolymer (b) was obtained in the same manner as in Synthesis Example 1 except that a polyether diol was used instead of the polycarbonate diol. (Synthesis Example 3) A UV-curable prepolymer (c) was obtained in the same manner as in Synthesis Example 1 except that a polyester diol was used instead of the polycarbonate diol. (Comparative Synthesis Example 1) UV-curable prepolymer (d) To a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a nitrogen introduction tube, methoxypropanol propylene glycol monomethyl ether (PGM) was added as a polymerization solvent. 100.0 g, while stirring under a stream of nitrogen, the temperature was raised to 80 degrees. With a temperature of 80 ° C, 13.5 parts by mass of styrene, 67 parts by mass of ethyl acrylate, and 11.5 parts by mass of acrylic acid were added dropwise from the dropping funnel to the dropping funnel. Azobisisobutyronitrile 0.5 g as the starter. After the dropwise addition was completed, the reaction solution was heated to 90 ° C. while the reaction solution was stirred, and the temperature of the reaction solution was maintained at 90 ° C., and further stirred for 2 hours to obtain a copolymer. Then, 100 parts by mass of the obtained copolymer, 7.8 parts by mass of glycidyl methacrylate, 0.8 parts by mass of triethylamine as a catalyst, and 0.05 parts by weight of hydroquinone as a polymerization inhibitor were added to the reaction container, The reaction was performed at 100 ° C for 12 hours to perform an addition reaction, thereby obtaining a UV-curable prepolymer (d). The addition reaction was completed at a time point when the acid value became 5 mgKOH / g or less. The obtained UV-curable prepolymer (d) had a weight-average molecular weight of 45,000, a solid content concentration of 47% by mass, and a Tg of 3 ° C. (Example 1) (1) Preparation of UV-curable resin composition 100 parts by mass of a UV-curable prepolymer (a) was added to a reaction vessel, and 25 parts by mass of a UV-curable polyfunctional monomer (a) was added. 1.5 parts by mass of the photopolymerization initiator (a), 1 part by mass of the silane coupling agent (a), and 140 parts by mass of methyl ethyl ketone as a solvent were stirred to obtain a resin composition. (2) Preparation of the next sheet The resin composition obtained in the above (1) was coated on a PET film of 38 μm so that the thickness after drying became 30 μm or more, and after drying at 130 ° C. for 5 minutes, it was also reversed. A PET film is provided on one side to obtain an adhesive sheet having a PET film on both sides. The obtained adhesive sheet was used to evaluate secondary workability, adhesiveness, adhesion, and optical characteristics. (Examples 2 to 20) and (Comparative Examples 1 to 7) A UV-curable resin composition was obtained in the same manner as in Example 1 except that the types and contents of the components were changed as described in Tables 1 to 3. And then the film. The obtained adhesive sheet was used to evaluate secondary workability, adhesiveness, adhesion, and optical characteristics. [Table 1] [Table 2] [table 3] [Industrial Applicability] The adhesive sheet containing the UV-curable resin composition of the present invention has industrial applicability as an adhesive for liquid crystal display and the like.

Claims (10)

一種UV硬化型樹脂組合物，其含有(A)UV硬化型預聚物、(B)UV硬化型多官能單體、(C)光聚合起始劑、及(D)矽烷偶合劑；上述(A)成分為(甲基)丙烯酸胺基甲酸酯；且相對於上述(A)成分100質量份，上述(B)成分之含量為15~60質量份，上述(C)成分之含量為0.5質量份以上，上述(D)成分之含量為0.1~5質量份；上述(C)光聚合起始劑為醯基氧化膦系光聚合起始劑；上述UV硬化型樹脂組合物之硬化後於常溫(25℃)下之儲存模數為6.0×108~1.0×1010Pa；將上述UV硬化型樹脂組合物以下述方法製為接著片，將所製作之接著片以下述測定方法測定黃色指數(YI)時之YI值未達2；(接著片之製作方法)將上述UV硬化型樹脂組合物以乾燥後之厚度成為30μm以上之方式塗佈於38μm之PET膜上，以130℃乾燥5分鐘之後，亦在相反面設置PET膜，從而獲得雙面具備PET膜之接著片；(YI值之測定方法)將上述接著片之單側PET膜剝離，藉由真空層壓而貼合於光學玻璃(40mm見方)，真空層壓係於溫度25~50℃、壓力0.01~0.05MPa、抽真空10s、加壓10s下實施，將另一側之PET膜剝離，於與上述真空層壓之條件相同之條件下貼合於光學玻璃後，進行高壓釜處理，繼而藉由UV曝光而獲得試驗樣品，高壓釜係於溫度60℃、壓力0.6MPa、時間1hr下實施，UV曝光係使用超高壓水銀燈光源，以累計光量成為3000mJ/cm2之方式實施，使用分光光度計(Hitachi High-Technologies Corporation製造之U-4100)測定試驗樣品之黃色指數(YI)，測定條件係設為C光源、透過、波長λ=380~760nm。A UV-curable resin composition comprising (A) a UV-curable prepolymer, (B) a UV-curable polyfunctional monomer, (C) a photopolymerization initiator, and (D) a silane coupling agent; the above ( A) The component is urethane (meth) acrylate; and the content of the component (B) is 15 to 60 parts by mass with respect to 100 parts by mass of the component (A), and the content of the component (C) is 0.5 The content of the (D) component is 0.1 to 5 parts by mass; the (C) photopolymerization initiator is a fluorenylphosphine oxide-based photopolymerization initiator; the UV-curable resin composition is cured at The storage modulus at normal temperature (25 ° C) is 6.0 × 10 8 to 1.0 × 10 10 Pa. The UV-curable resin composition is prepared as a bonding sheet by the following method, and the prepared bonding sheet is used to measure the yellow color by the following measurement method. The YI value at the time of the index (YI) is less than 2; (the production method of the subsequent sheet) The above UV-curable resin composition is applied to a 38 μm PET film so that the thickness after drying becomes 30 μm or more, and dried at 130 ° C. After 5 minutes, a PET film was also set on the opposite side to obtain a bonding sheet with PET film on both sides; (method of measuring the YI value) The PET film on one side is peeled off and bonded to the optical glass (40mm square) by vacuum lamination. The vacuum lamination is performed at a temperature of 25 to 50 ° C, a pressure of 0.01 to 0.05MPa, a vacuum for 10s, and a pressure of 10s. The PET film on the other side was peeled off, bonded to the optical glass under the same conditions as the vacuum lamination, and then subjected to an autoclave treatment, followed by UV exposure to obtain a test sample. The autoclave was at a temperature of 60 ° C, The test was performed at a pressure of 0.6 MPa and a time of 1 hr. The UV exposure was performed using an ultra-high pressure mercury lamp light source with a cumulative light amount of 3000 mJ / cm 2. The spectrophotometer (U-4100 manufactured by Hitachi High-Technologies Corporation) was used to measure the Yellow index (YI). The measurement conditions are set as C light source, transmission, and wavelength λ = 380 ~ 760nm. 如請求項1之UV硬化型樹脂組合物，其中上述(甲基)丙烯酸胺基甲酸酯係選自由具有聚碳酸酯骨架之(甲基)丙烯酸胺基甲酸酯、具有聚醚骨架之(甲基)丙烯酸胺基甲酸酯、及具有聚酯骨架之(甲基)丙烯酸胺基甲酸酯所組成之群中之1種以上。The UV-curable resin composition according to claim 1, wherein the (meth) acrylic acid urethane is selected from the group consisting of (meth) acrylic acid urethane having a polycarbonate skeleton, and ( One or more of the group consisting of a meth) acrylic acid urethane and a (meth) acrylic acid urethane having a polyester skeleton. 如請求項1或2之UV硬化型樹脂組合物，其中上述(甲基)丙烯酸胺基甲酸酯之重量平均分子量為10,000~100,000，雙鍵當量為1,000~5,000g/eq。The UV-curable resin composition according to claim 1 or 2, wherein the weight average molecular weight of the (meth) acrylic acid urethane is 10,000 to 100,000, and the double bond equivalent is 1,000 to 5,000 g / eq. 如請求項1或2之UV硬化型樹脂組合物，其中上述(B)UV硬化型多官能單體為具有2個以上之官能基之(甲基)丙烯酸系單體。The UV-curable resin composition according to claim 1 or 2, wherein the (B) UV-curable polyfunctional monomer is a (meth) acrylic monomer having two or more functional groups. 如請求項1之UV硬化型樹脂組合物，其中上述醯基氧化膦系光聚合起始劑為2,4,6-三甲基苯甲醯基二苯基氧化膦。The UV-curable resin composition according to claim 1, wherein the fluorenylphosphine oxide-based photopolymerization initiator is 2,4,6-trimethylbenzylidenediphenylphosphine oxide. 如請求項1或2之UV硬化型樹脂組合物，其中上述(D)矽烷偶合劑為具有(甲基)丙烯醯基之矽烷偶合劑。The UV-curable resin composition according to claim 1 or 2, wherein the (D) silane coupling agent is a silane coupling agent having a (meth) acrylfluorenyl group. 一種接著片，其包含如請求項1至6中任一項之UV硬化型樹脂組合物。An adhesive sheet comprising the UV-curable resin composition according to any one of claims 1 to 6. 如請求項7之接著片，其乾燥後之膜厚為10~250μm。For example, the adhesive sheet of claim 7 has a film thickness of 10 to 250 μm after drying. 一種3D液晶面板，其係將LCD與圖案化相位差板積層而成者；且上述LCD與上述相位差板係藉由如請求項7或8之接著片而接著。A 3D liquid crystal panel is formed by laminating an LCD and a patterned retardation plate; and the LCD and the retardation plate are connected by a bonding sheet according to claim 7 or 8. 如請求項9之3D液晶面板，其中上述圖案化相位差板為形成有圖案之玻璃板。The 3D liquid crystal panel according to claim 9, wherein the patterned retardation plate is a glass plate with a pattern formed.
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