TW201237557A - Actinic radiation curable resin composition containing polyfunctional acrylate compound - Google Patents

Abstract

The present invention provides a resin composition which serves as an adhesive for accurately fixing a component made of a material such as metal or plastic. This resin composition exhibits high initial adhesion to the material. In the durability tests including high-temperature and high-humidity test, the resin composition exhibits high holding power, and is rarely deformed even when heated under loading as well as when heated, thus inhibiting the movement of the part. An actinic radiation curable resin composition characterized by comprising (A) a polyfunctional acrylate compound having four or more (meth)acryloyl groups in the molecule, (B) a photocurable prepolymer, (C) a mono- or bi-functional (meth)acryloyl -containing monomer and (D) a photopolymerization initiator, said polyfunctional acrylate compound (A) being selected from the group consisting of (a1) glycerol derivatives, and linear or branched polymers thereof which each comprise ether skeletons as the connecting functional groups, (a2) trimethylolpropane derivatives, and linear or branched polymers thereof which each comprise ether skeletons as the connecting functional groups, (a3) monomeric pentaerythritol derivatives, and linear or branched polymers thereof which each comprise ether skeletons as the connecting functional groups, and (a4); dendrimers which contain ether or ester bonds and in which (meth)acryloyl groups are present at four or more terminals.

Description

.201237557 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種含有多官能丙烯酸酯化合物的活性 能量線硬化性樹脂組成物，特別係關於一種活性能量線硬 化性樹脂組成物，其係對於金屬或塑膠構件具有黏著性， 同時並以耐熱試驗爲首之耐久性試驗，呈現高的保持力與 熱時之尺寸安定性，可藉UV或可見光等之活性能量線之 照射進行硬化。 【先前技術】 在CD或DVD、或在近年，可使用於藍光爲首之記錄 材料的記錄、再生之機材領域中，隨機器之小型化、各構 件係積極尋求耐熱性、耐衝擊性，於可高精度成形之液晶 聚合物（LCP)、環烯烴聚合物（COP)、環烯烴共聚物（COC) 、聚苯硫醚（PPS)、聚苯氧（PPO)、或於上述塑膠材中混練 有玻璃纖維或碳纖維之複合塑膠材料等已常被用。爲使由 此等之材料所構成的零件黏合、固定，對於此等之材料， 尋求具有高黏著性且高耐久性，硬化後之樹脂部的熱時變 形少之高固定精度的黏著劑。進一步，從作業性之觀點， 要求藉可見光、紫外光等之活性能量線之照射更迅速地硬 化之黏著劑。 所謂固定精度係將發光元件或光檢測器固定於由上述 構件所構成的基材構件之殼體時，顯示光檢測器不會從特 定之位置移動的精度。若固定精度低，光拾取裝置之製造 -5- 201237557 時或耐久試驗後，發光元件或光檢測器會從特定之位置移 動，無法檢測出光。因此，要求高的固定精度。 若考量固定精度，就光硬化型黏著劑，陽離子硬化性 環氧樹脂優於光硬化性丙烯酸系樹脂黏著劑，又，陽離子 硬化性環氧樹脂組成物係無受如丙烯酸系樹脂黏著劑之氧 所造成的硬化阻礙（非專利文獻1)»但，陽離子硬化性環 氧樹脂係對於丙烯酸樹脂系，有速硬化性差之問題。 於專利文獻1中係揭示一種可使用來作爲液晶聚合物 、環烯烴聚合物、聚芳酸酯、聚碳酸酯等對被黏體之黏著 劑的硬化性組成物。近年，在丙烯酸系之黏著劑中係於固 定構件之後，尤其熱時隨樹脂之熱應力或外部應力之樹脂 變形的構件移動成爲問題。丙烯酸系之黏著劑係較環氧樹 脂’更具有硬化性佳之優點，反之，被賦予熱時之彈性率 變化大，故黏著劑變形，容許構件之移動。 於專利文獻2中係記載含有偏光器、黏著劑層與硬化 樹脂層之偏光板。於專利文獻2中記載由含多官能丙燃酸 單體及多官能甲基丙烯酸單體之至少一者及光硬化性預聚 物的無溶劑型光硬化性組成物所形成之硬化樹脂層係可使 用來作爲硬塗（高硬度）層。但，於專利文獻2所記載之無 溶劑型光硬化性組成物係使用來作爲黏著劑時，有硬化收 縮大，且易引起翹曲或剝離之問題。 [專利文獻] [專利文獻] [專利文獻1]特開2008-101106號公報 201237557 [專利文獻2]特開2008-2089 1號公報 [非專利文獻] [非專利文獻1 ]「光應用技術、材料辭典 2006年4月26日發行 【發明內容】 [發明欲解決之課題] 本發明之課題在於提供一種樹脂組成物，其係對於聚 苯硫醚（PPS)等塑膠材、或金屬構件，具有高的初期黏著 性’以闻溫高濕試驗爲首之耐久性試驗，呈現高的保持力 ’可抑制其熱時之變形、及對於熱時與荷重之變形性至極 少，藉此，可抑制零件之移動。 [用以解決課題之手段] 本發明人係爲解決前述之課題，累積專心硏究之結果 ’發現以含有下述（A)成分〜（D)成分爲特徵之活性能量線 硬化性樹脂組成物可達成前述之目的，終達成本發明。 亦即’本發明係關於一種活性能量線硬化性樹脂組成 物，其特徵係含有下述（A)成分〜（D)成分： (A)由（al)以甘油衍生物及醚骨架作爲鍵結官能基之直線狀 或分枝狀之其多量體、 (a2)以三羥甲基丙烷衍生物及.酸骨架作爲鍵結官能基之直 線狀或分枝狀之其多量體、 (a3)以季戊四醇衍生物之單體及醚骨架作爲鍵結官能基之 201237557 直線狀或分枝狀之其多量體、以及 (a4)含有醚鍵或酯鍵，且於4以上之末端配置（甲基）丙烯 醯基之樹木狀分子化合物 所構成之群中選出的於分子中含有4個以上之（甲基）丙烯 醯基的多官能丙烯酸酯化合物、 (B) 光硬化性預聚物、 (C) 單官能或2官能之含（甲基）丙烯醯基單體、及 (D) 光聚合起始劑。 本發明係關於前述記載之活性能量線硬化性樹脂組成 物，其中相對於（A)成分〜（D)成分之重量，（A)成分爲 0.0 1 〜2 5 重量 °/〇。 本發明係關於前述記載之活性能量線硬化性樹脂組成 物，其係用以貼合光學零件之黏著劑。 本發明係關於前述記載之活性能量線硬化性樹脂組成 物，其係光拾取裝置組裝用之黏著劑。 本發明係關於一種黏著構造體，其係以前述記載之活 性能量線硬化性樹脂組成物貼合。 本發明係關於一種光學零件，其係使用前述記載之活 性能量線硬化性樹脂組成物而貼合。 本發明係關於一種光拾取裝置，其係使用前述記載之 活性能量線硬化性樹脂組成物而組裝。 [發明之效果] 若依本發明，可得到一種樹脂組成物，其係對於聚苯 -8- 201237557 硫醚（PPS)等塑膠材、或金屬構件，具有高的初期黏著性 ，以高溫高濕試驗爲首之耐久性試驗，呈現高的保持力， 可抑制其熱時之變形、及對於熱時與荷重之變形性至極少 ，藉此，可抑制零件之移動。 依本發明，可提供一種啷筒塗佈性等之作業性佳，照 射紫外光時，可以短時間硬化之活性能量線硬化性樹脂組 成物。 [用以實施發明之最佳形態] 在本發明中，（A)成分係由（a 1)以甘油衍生物及醚骨架 作爲鍵結官能基之直線狀或分枝狀之其多量體、（a2)以三 羥甲基丙烷衍生物及醚骨架作爲鍵結官能基之直線狀或分 枝狀之其多量體、（a3)以季戊四醇衍生物之單體及醚骨架 作爲鍵結官能基之直線狀或分枝狀之其多量體、以及（a4) 含有醚鍵或酯鍵，且於4以上之末端配置（甲基）丙烯醯基 之樹木狀分子化合物所構成之群中選出的於分子中含有4 個以上之（甲基）丙烯醯基的多官能丙烯酸酯化合物。（A)成 分係可分別單獨使用，亦可組合二種以上而使用。又，在 本說明書中，（甲基）丙烯酸酯係含有丙烯酸酯及甲基丙烯 酸酯之兩者，（甲基）丙烯醯氧基係包含丙烯醯氧基及甲基 丙烯醯氧基之兩者。 在本發明中，甘油衍生物、三羥甲基丙烷衍生物、季 戊四醇衍生物、及以醚骨架作爲連結官能基之直線狀或分 枝狀之其等多量體係於分子中含有甘油單元、三羥甲基丙 201237557 烷單元及季戊四醇單元，於分子中含有4個以上之（甲基） 丙烯醯氧基。此處，甘油單元係意指從甘油除去3個羥基 之構造’三羥甲基丙烷單元係意指從三羥甲基丙烷除去3 個羥基之構造，季戊四醇單元係意指從季戊四醇單元除去 4個羥基之構造。 在本發明中，甘油衍生物、三羥甲基丙烷衍生物、及 季戊四醇衍生物係甘油、三羥甲基丙烷、及季戊四醇爲被 4個以上之（甲基）丙烯醯氧基取代的化合物。 在本發明中，鍵結官能基之醚骨架係在甘油、三羥甲 基丙烷、及季戊四醇之分子間中的藉2個羥基的縮合所形 成之醚鍵，或藉甘油、三羥甲基丙烷或季戊四醇、與乙二 醇等之二醇化合物的縮合所形成之聚醚骨架。在本發明中 ，鍵結官能基之醚骨架係以下述通式（1): -0-(Χ-0)ηΐ- (1) (式中， X爲碳原子數1〜4之伸烷基， nl爲0或1〜3之整數） 所示。 碳原子數1〜4之伸烷基係可舉例如亞甲基、亞乙基 、三亞甲基、及四亞甲基，宜爲亞乙基。 在通式（1)中，nl宜爲0。亦即，在本發明中之醚骨架 宜爲醚鍵（-〇-)。 在本發明中，以醚骨架作爲鍵結官能基之直線狀甘油 衍生物的多量體係宜以下述通式（2): -10- 201237557 【化1】 (式中， n2爲2〜1 0， R1爲氫、丙烯醯氧基、或甲基丙烯醯氧基， R2爲氫或甲基， 其中’丙烯醯氧基及甲基丙烯醯氧基之合計爲4以上） 所示之化合物。 在本發明中，以醚骨架作爲鍵結官能基之直線狀三羥 甲基丙烷衍生物的多量體係宜以下述通式（3): 【化2】BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an active energy ray-curable resin composition containing a polyfunctional acrylate compound, and more particularly to an active energy ray-curable resin composition. It has adhesiveness to metal or plastic members and durability test including heat resistance test. It exhibits high retention and dimensional stability during heat, and can be hardened by irradiation with active energy rays such as UV or visible light. [Prior Art] In the field of recording or reproducing a recording material for blue light, in the field of CD or DVD, or in recent years, the size of the randomizer is reduced, and each member is actively seeking heat resistance and impact resistance. High-precision liquid crystal polymer (LCP), cycloolefin polymer (COP), cyclic olefin copolymer (COC), polyphenylene sulfide (PPS), polyphenylene oxide (PPO), or kneading in the above plastic materials Composite plastic materials such as glass fiber or carbon fiber have been frequently used. In order to bond and fix the components made of these materials, an adhesive having high adhesion and high durability with high adhesiveness and low heat-time deformation of the resin portion after curing is sought for these materials. Further, from the viewpoint of workability, an adhesive which is hardened more rapidly by irradiation with an active energy ray such as visible light or ultraviolet light is required. The fixing accuracy is such that when the light-emitting element or the photodetector is fixed to the casing of the base member constituted by the above member, the accuracy of the photodetector not moving from a specific position is displayed. If the fixing accuracy is low, the light-emitting device is manufactured from -5 to 201237557 or after the endurance test, the light-emitting element or photodetector moves from a specific position, and light cannot be detected. Therefore, high fixing accuracy is required. When considering the fixed precision, the photocurable adhesive, the cationic hardening epoxy resin is superior to the photocurable acrylic resin adhesive, and the cationic hardening epoxy resin composition is not affected by the oxygen such as the acrylic resin adhesive. The hardening barrier caused by the non-patent document (Non-Patent Document 1)» However, the cation-curable epoxy resin has a problem that the speed-hardenability is poor in the acrylic resin system. Patent Document 1 discloses a curable composition which can be used as an adhesive for a liquid crystal polymer, a cycloolefin polymer, a polyarylate, a polycarbonate, or the like to an adherend. In recent years, after the fixing member is attached to the acrylic adhesive, the movement of the member which is deformed with the thermal stress of the resin or the external stress is particularly problematic. The acrylic adhesive has an advantage of being more curable than the epoxy resin. On the contrary, the elastic modulus changes when heat is applied, so that the adhesive is deformed and the movement of the member is allowed. Patent Document 2 describes a polarizing plate including a polarizer, an adhesive layer, and a cured resin layer. Patent Document 2 describes a cured resin layer formed of a solventless photocurable composition containing at least one of a polyfunctional fluorinated acid monomer and a polyfunctional methacrylic monomer and a photocurable prepolymer. It can be used as a hard coat (high hardness) layer. However, when the solvent-free photocurable composition described in Patent Document 2 is used as an adhesive, there is a problem that the hardening shrinkage is large and warping or peeling is likely to occur. [Patent Document] [Patent Document 1] JP-A-2008-101106, JP-A No. 200837557 [Patent Document 2] JP-A-2008-2089 No. 1 [Non-Patent Document] [Non-Patent Document 1] [Technical Problem] The object of the present invention is to provide a resin composition having a resin material such as polyphenylene sulfide (PPS) or a metal member. High initial adhesion 'durability test based on temperature and high humidity test, showing high retention force' can suppress deformation during heat and deformation to heat and load to a minimum, thereby suppressing [Means for Solving the Problem] In order to solve the above-mentioned problems, the present inventors have accumulated the results of intensive research and found that active energy ray hardening characterized by containing the following components (A) to (D) The present invention relates to an active energy ray-curable resin composition characterized by containing the following components (A) to (D): (A) ) by (al) to Gan The oil derivative and the ether skeleton are linear or branched as a bonding functional group, and (a2) are linear or branched as a bonding functional group with a trimethylolpropane derivative and an acid skeleton. a multi-volume, (a3) a monomer having a pentaerythritol derivative and an ether skeleton as a bonding functional group, 201237557, a linear or branched multi-volume, and (a4) an ether bond or an ester bond, and 4 a polyfunctional acrylate compound containing four or more (meth) acryloyl fluorenyl groups in the molecule selected from the group consisting of a (meth)acryloyl group-based molecular compound at the end, and (B) photohardening The prepolymer, (C) a monofunctional or bifunctional (meth)acrylonitrile-containing monomer, and (D) a photopolymerization initiator. The present invention relates to the active energy ray-curable resin composition described above. In the above, the component (A) has a weight ratio of (A) to (D) of from 0.01 to 25% by weight. The present invention relates to the active energy ray-curable resin composition described above. An adhesive for bonding optical parts. The present invention relates to the foregoing The present invention relates to an active energy ray-curable resin composition which is an adhesive for assembling an optical pickup device. The present invention relates to an adhesive structure which is bonded together with the active energy ray-curable resin composition described above. The optical component is bonded together using the active energy ray-curable resin composition described above. The present invention relates to an optical pickup device which is assembled by using the active energy ray-curable resin composition described above. [Effect of the Invention] According to the present invention, a resin composition having high initial adhesion to a plastic material such as polyphenyl-8-201237557 thioether (PPS) or a metal member, and high temperature and high humidity can be obtained. The endurance test, which is the first test, exhibits a high holding force, suppresses deformation during heat, and has little deformation to heat and load, thereby suppressing movement of parts. According to the present invention, it is possible to provide an active energy ray-curable resin composition which is excellent in workability such as coating properties and can be cured in a short time when irradiated with ultraviolet light. [Best Mode for Carrying Out the Invention] In the present invention, the component (A) is a linear or branched multi-component of (a1) a glycerin derivative and an ether skeleton as a bonding functional group, ( A2) a linear or branched multi-component of a trimethylolpropane derivative and an ether skeleton as a bonding functional group, (a3) a straight line of a functional group of a pentaerythritol derivative and an ether skeleton as a bonding functional group a multi-component in the form of a branch or a branch, and (a4) a group selected from a group consisting of a tree-like molecular compound having an ether bond or an ester bond and having a (meth)acryloyl group at the end of 4 or more A polyfunctional acrylate compound containing 4 or more (meth) acrylonitrile groups. (A) The components may be used singly or in combination of two or more. Further, in the present specification, the (meth) acrylate type contains both an acrylate and a methacrylate, and the (meth) acryloxy group includes both an acryloxy group and a methacryloxy group. . In the present invention, a glycerin derivative, a trimethylolpropane derivative, a pentaerythritol derivative, and a linear or branched system having an ether skeleton as a linking functional group have a glycerin unit and a trihydroxyl group in the molecule. The methyl propyl 201237557 alkane unit and the pentaerythritol unit contain four or more (meth) acryloxy groups in the molecule. Here, the glycerin unit means a structure in which three hydroxyl groups are removed from glycerol. The 'trimethylolpropane unit system means a structure in which three hydroxyl groups are removed from trimethylolpropane, and the pentaerythritol unit means four from the pentaerythritol unit. The structure of the hydroxyl group. In the present invention, the glycerin derivative, the trimethylolpropane derivative, and the pentaerythritol derivative glycerin, trimethylolpropane, and pentaerythritol are compounds substituted with four or more (meth) acryloxy groups. In the present invention, the ether skeleton of the bonding functional group is an ether bond formed by condensation of two hydroxyl groups in the molecules of glycerin, trimethylolpropane, and pentaerythritol, or by glycerol or trimethylolpropane. Or a polyether skeleton formed by the condensation of pentaerythritol and a glycol compound such as ethylene glycol. In the present invention, the ether skeleton of the bonding functional group is represented by the following formula (1): -0-(Χ-0)ηΐ- (1) (wherein X is an alkylene group having 1 to 4 carbon atoms , nl is 0 or an integer from 1 to 3). The alkylene group having 1 to 4 carbon atoms may, for example, be a methylene group, an ethylene group, a trimethylene group or a tetramethylene group, and is preferably an ethylene group. In the formula (1), nl is preferably 0. Namely, the ether skeleton in the present invention is preferably an ether bond (-〇-). In the present invention, a multi-component system of a linear glycerin derivative having an ether skeleton as a bonding functional group is preferably represented by the following formula (2): -10- 201237557 (wherein n2 is 2 to 1 0, R1 is a compound represented by hydrogen, an acryloxy group, or a methacryloxy group, and R2 is hydrogen or a methyl group, and the total of the 'acryloxy group and the methacryloxy group is 4 or more. In the present invention, a plurality of systems of linear trimethylolpropane derivatives having an ether skeleton as a bonding functional group are preferably represented by the following formula (3):

(式中， π2、R1、R2爲以通式（2)所定義般， 其中，丙烯醯氧基及甲基丙烯醯氧基之合計爲4以上） 所示之化合物。 在本發明中，以醚骨架作爲鍵結官能基之直線狀季戊 四醇衍生物的多量體係宜以下述通式（4): -11 - 201237557 【化3】 OR1(wherein π2, R1 and R2 are compounds represented by the formula (2), wherein the total of the acryloxy group and the methacryloxy group is 4 or more). In the present invention, a multivalent system of a linear pentaerythritol derivative having an ether skeleton as a bonding functional group is preferably represented by the following formula (4): -11 - 201237557 [Chemical 3] OR1

(式中， η 3爲1〜1 〇， R1爲以通式（2)所定義般， 其中，丙烯醯氧基及甲基丙烯醯氧基之合計爲4以上） 所示之化合物。 在本發明中，以醚骨架作爲鍵結官能基之直線狀或分 枝狀的多量體係尤宜以通式（5): 【化4】(wherein η 3 is 1 to 1 Torr, and R1 is a compound represented by the formula (2), wherein the total of the acryloxy group and the methacryloxy group is 4 or more). In the present invention, a linear or branched multi-volume system having an ether skeleton as a bonding functional group is preferably a compound of the formula (5):

(式中， R3爲氫或甲基， η4爲1〜5， 其中，丙烯醯氧基及甲基丙烯醯氧基之合計爲4以上） 所示之化合物。 -12- 201237557 在以通式（5)所示之化合物中，η4更宜爲3〜4。藉由 使用如此之化合物’可得到一種使對於熱時之變形、及熱 時與加重之變形性抑制至極少之樹脂組成物。 在以通式（5)所示之化合物係市售品可舉例如V#802( 在通式（5)中n4 = 3_45)(大阪有機化學公司製）、DPE-6A(二 季戊四醇六丙烯酸酯）、及PE-4A(共榮社化學公司製）。 在本發明中，藉鍵結官能基存在分枝狀構造之分枝狀 多量體化的多官能丙烯酸酯化合物係甘油衍生物、三羥甲 基丙烷衍生物及季戊四醇衍生物爲以醚骨架作爲鍵結官能 基之呈分枝狀多量體化的化合物。如此之多量體係從甘油 、三羥甲基丙烷及季戊四醇除去羥基之構造間介由醚骨架 之鍵結官能基而多量體化的化合物，爲具有（甲基）丙烯醯 氧基4以上之化合物。例如於季戊四醇衍生物介由鍵結官 能基而呈分枝狀多量體化的多官能丙烯酸酯化合物所含有 之季戊四醇的構造係以下述式（6a)〜（6d): 201237557 【化5】 \ OR1 ch2(In the formula, R3 is hydrogen or a methyl group, and η4 is a compound represented by 1 to 5, wherein the total of the acryloxy group and the methacryloxy group is 4 or more). -12- 201237557 In the compound represented by the formula (5), η4 is more preferably from 3 to 4. By using such a compound, a resin composition which suppresses deformation at the time of heat and deformation at the time of heat and weight can be obtained. The commercially available product represented by the formula (5) is, for example, V#802 (n4 = 3_45 in the formula (5)) (manufactured by Osaka Organic Chemical Co., Ltd.), DPE-6A (dipentaerythritol hexaacrylate) ), and PE-4A (manufactured by Kyoeisha Chemical Co., Ltd.). In the present invention, a branched polyfunctional acrylate compound having a branched structure by a bonding functional group is a glycerol derivative, a trimethylolpropane derivative, and a pentaerythritol derivative having an ether skeleton as a bond. A branched, multi-quantitative compound having a functional group. The compound having such a large amount of a system in which a hydroxyl group is removed from glycerin, trimethylolpropane or pentaerythritol by a bonding functional group of an ether skeleton is a compound having a (meth)acryloyloxy group of 4 or more. For example, the structure of the pentaerythritol contained in the polyfunctional acrylate compound which is branched and multi-quantified by the bonding functional group in the pentaerythritol derivative is represented by the following formula (6a) to (6d): 201237557 [Chemical 5] \ OR1 Ch2

or1 (6a) OR1 \ ch2Or1 (6a) OR1 \ ch2

(6b) OR1(6b) OR1

(6c)及 (6 d ) (式中，R1係如上述定義） -14- .201237557 所示。 在本發明中，季戊四醇衍生物的分枝狀多量體之化合 物係以式（6a)〜（6 d)所示之構造間爲介由醚骨架而隨機鍵 結之構造（其中，只以式（6b)所示之構造呈直線狀鍵結，於 末端以式（6a)所示之構造鍵結之直線狀分枝的多量體係除 外）。在本發明中，隨機鍵結之季戊四醇衍生物的分枝狀 多量體之化合物係可爲任一構造，例如可爲環狀，亦可爲 網目狀構造。 就季戊四醇衍生物的分枝狀多量體而言，可舉例如， 以通式（7): 【化6】(6c) and (6 d ) (wherein R1 is as defined above) -14- .201237557. In the present invention, the branched polyvalent compound of the pentaerythritol derivative is a structure in which the structures represented by the formulae (6a) to (6d) are randomly bonded via an ether skeleton (wherein only the formula ( The structure shown in Fig. 6b) is a linear bond, except for a large number of systems in which linear branches are bonded at the end with the structure shown by the formula (6a). In the present invention, the branched multi-component compound of the randomly-bonded pentaerythritol derivative may have any structure, and may be, for example, a ring shape or a mesh-like structure. The branched multi-quantity of the pentaerythritol derivative may, for example, be represented by the formula (7):

Rr1 OR1Rr1 OR1

R1 (7) (式中， η 5爲1〜1 〇， η6爲0〜1 〇， R1爲以通式（2)所定義般， R2爲以通式（8)或通式（9): 201237557 【化7】R1 (7) (wherein η 5 is 1 to 1 〇, η 6 is 0 to 1 〇, R1 is as defined by the general formula (2), and R2 is represented by the general formula (8) or the general formula (9): 201237557 【化7】

(8 (式中， n7爲1〜1 〇， R1爲以通式（2)所定義般） 【化8】(8 (where n7 is 1~1 〇, R1 is defined by the general formula (2))

(式中， R1爲以通式（2)所定義般’ n8爲1〜1 0 ’ η9爲1〜1 0， R4爲以通式（8)所定義般）’ 其中，1分子中，丙烯醯氧基及甲基丙烯醯氧基之合 §十爲4以上） 所示之化合物。如此之以酸骨架作爲鍵結官能基的季戊四 醇的分枝狀多量體係可舉例如V#Star-501(大阪有機化學 公司製）。 在本發明中，含有醚鍵或酯鍵，且於4以上末端配置（ -16- 201237557 甲基）丙烯醯氧基的樹木狀分子化合物’即於分子中含有4 個以上之（甲基）丙烯醯氧基的多官能丙烯酸酯化合物係具 有由核體、含分枝單元的樹枝構造所構成之化學構造的化 合物。如此之化合物係可舉例如樹枝狀高分子（Dendrimer) 型丙烯酸酯化合物。在本發明之樹木狀分子化合物中，使 由核體至最初之樹枝構造及其末端部分定義爲第1世代。 於第1世代之樹枝構造的外側具有其次之樹枝構造時，從 該其次之樹枝構造至其末端定義爲第2世代。第3世代以 後亦同樣地從其次之樹枝構造至其末端定義爲次世代。在 本發明之樹枝狀高分子中較佳的世代數爲1〜5之範圍， 更宜爲1〜3。 在本發明中，樹木狀分子化合物之核體係可舉例如三 羥甲基丙院、季戊四醇及二季戊四醇。 在本發明中，含有樹木狀分子化合物之分枝單元的樹 枝構造可舉例如以下述式（丨〇):(wherein R1 is as defined by the formula (2): n8 is 1 to 1 0 'n9 is 1 to 1 0, and R4 is as defined by the formula (8)) wherein 1 molecule is propylene The compound represented by the decyloxy group and the methacryloxy group is more than 4 or more. For example, V# Star-501 (manufactured by Osaka Organic Chemical Co., Ltd.), which is a branched system of pentaerythritol having an acid skeleton as a bonding functional group, may be mentioned. In the present invention, a dendrimer compound having an ether bond or an ester bond and having 4 or more terminal positions (-16-201237557 methyl) propylene oxy group contains 4 or more (meth) propylene in the molecule. The polyfunctional acrylate compound having a decyloxy group is a compound having a chemical structure composed of a core structure and a branch structure including branching units. Such a compound may, for example, be a dendrimer type acrylate compound. In the dendrimer compound of the present invention, the nucleus to the initial dendritic structure and its terminal portion are defined as the first generation. When the outer side of the branch structure of the first generation has the next branch structure, the second branch is defined from the next branch structure to the end thereof. The third generation is also defined as the next generation from the second branch to the end. The preferred number of generations in the dendrimer of the present invention is in the range of 1 to 5, more preferably 1 to 3. In the present invention, the core system of the dendrimer compound may, for example, be trimethylol propylate, pentaerythritol or dipentaerythritol. In the present invention, the branch structure of the branching unit containing the dendrimer compound may be, for example, the following formula (丨〇):

(式中， R1爲以通式（2)所定義般， s爲1〜5之整數） 所示之構造。此處，在通式（1〇)中之R1係相當於本發明之 樹木狀化合物的末端。 -17- 201237557 在通式（10)中之重複數s係相當於樹枝狀高分子 (Dendrimer)化合物之世代數。例如通式（1〇)中之重複數s 爲2時，以下述（10a):(wherein, R1 is a structure represented by the formula (2), and s is an integer of 1 to 5). Here, R1 in the general formula (1〇) corresponds to the terminal of the dendritic compound of the present invention. -17- 201237557 The number of repetitions in the general formula (10) corresponds to the number of generations of dendrimer compounds. For example, when the number of repetitions s in the formula (1〇) is 2, the following (10a) is used:

(式中， R1爲以通式（2)所定義般） 所示。 在本發明中，含有醚鍵或酯鍵且於末端配置（甲基）丙 烯醯氧基之樹木狀分子化合物係宜以下述式（11): 【化1 1】(wherein R1 is as defined by the formula (2)). In the present invention, a dendrimer compound having an ether bond or an ester bond and having a (meth) propyleneoxy group at the terminal is preferably a formula (11):

(11) {式中， nlO互相獨立爲1〜3之整數， R4係互相獨立爲氫、丙烯醯氧基、甲基丙烦醯氧基、 -18- 201237557 或通式（ίο): 【化1 2】(11) In the formula, nlO is independently an integer of 1 to 3, and R4 is independently hydrogen, acryloxy, methyl propyl oxy, -18-201237557 or formula (ίο): 1 2]

(式中， R1及s係如以上述定義）， 其中’丙烯醯氧基及甲基丙烯醯氧基之合計爲4以上} 所示之化合物。 在本發明中’含有醚鍵或酯鍵且於末端配置（甲基）丙 嫌醯氧基之樹木狀分子化合物即於分子中含有4個以上之 (甲基）丙烯醯氧基的多官能丙烯酸酯化合物係就市售品可 舉例如V# 1 000(分子量爲28 00之通式（1 1)的化合物、大阪 有機化學公司製）。又，在本發明中分子量係藉凝膠滲透 色層分析（GPC)以聚苯乙烯換算所算出之數目平均分子量 〇 在本案發明中，具有樹枝狀高分子（Dendrimer)構造之 樹木狀化合物的合成方法，可舉例如從中心之核體朝向外 側而進行合成的發散法、與從外側朝向核體而進行合成之 收斂法，此等之合成方法係熟悉此技藝者公知’例如記載 於特開平11-60540號公報中。具體上’藉由使二季戊四 醇與2,2-二羥甲基丙酸反應所得到之聚酯多元醇化合物與 (甲基）丙烯酸反應來製造第1世代的樹木狀化合物。又’ 使前述聚_多元醇化合物進一步與2,2_—經甲基丙酸反應 -19- 201237557 ，繼而與（甲基）丙烯酸反應來製造第2世代的樹木狀化合 物。 在本發明中，相對於（A)成分〜（D)成分之重量，（A)成 分係宜爲〇.〇1〜25重量％，宜爲0.5〜10重量％。 在本發明中，（B)成分之光硬化性預聚物係黏著組成 物之基材樹脂（基材寡聚物），藉紫外線等之活性能量線的 照射，反應基之（甲基）丙烯醯氧基進行聚合的感光性樹脂 。（B)成分係透明之低吸濕性樹脂，具有極低之極性及分 子構造，故爲阻隔欲從黏合面外周侵入之油或水之成分。 就本發明之（B)光硬化性預聚物而言，具有1個以上 之（甲基）丙烯醯氧基，具有由聚丁二烯、聚異戊二烯、聚 丁二烯或聚異戊二烯之氫化物、聚丁二烯或聚異戊二烯之 羧基改性的改性物、介由胺基甲酸酯鍵之聚酯骨架所構成 之群中選出的1種以上之主鏈骨架，於前述主鏈骨架之末 端或側鏈具有1個以上之（甲基）丙烯醯氧基即含（甲基）丙 烯醯氧基之寡聚物。在本發明中，（B)光硬化性預聚物係 宜由聚丁二烯、或聚丁二烯之氫化物所構成之群中選出的 主鏈骨架，尤宜具有聚丁二烯之氫化物作爲主鏈骨架。又 ，在本發明中，（B)光硬化性預聚物係宜具有2個以上之（ 甲基）丙烯醯氧基者，尤宜於主鏈骨架之兩末端具有（甲基） 丙烯醯氧基者。在本發明中，（B)成分係可分別單獨使用 ’亦可組合二種以上而使用。 在本發明中，（B)成分之光硬化性預聚物的分子量一 般爲400〜200,000，宜爲800〜1 00,000，尤宜爲1,000〜 -20- 201237557 3 0,000。若爲如此之分子量，成爲黏度適當的範圍，啷筒 的塗佈性良好，黏著後之活性能量線硬化性樹脂組成物的 硬化物之硬化收縮不變大。 (B) 成分之光硬化性預聚物係就市售品而言，可舉例 如日本曹達公司製「NISSO-PB TEAI-1000」（兩末端丙烯酸 酯改性氫化丁二烯系寡聚物）、日本曹達公司製「NISSO-PB TE-2000」（兩末端甲基丙烯酸酯改性丁二烯系寡聚物）、 Kuraray公司製「UC-203」（異戊二烯聚合物之馬來酸酐加 成物與2-羥乙基甲基丙烯酸酯之酯化物寡聚物）、香川化 學公司製「UA-1」（末端胺基甲酸酯丙烯酸酯改性聚丁二 烯氫化物）等。 在本發明中，相對於（A)成分〜（D)成分之重量，（B)成 分係宜爲25〜60重量％，宜爲30〜50重量％。 在本發明中，（C)成分之含單官能或2官能的（甲基）丙 烯醯氧基之單體（（甲基）丙烯酸酯單體）係反應性稀釋劑， 硬化時使基材樹脂固化，發揮與被黏體優異之黏著性的成 分。 (C) 成分係可舉例如具有極性基之（甲基）丙烯酸酯、例 如含有羥基之（甲基）丙烯酸酯、含有羧基之（甲基）丙烯酸 酯、及含有胺基之丙烯酸酯；具有低極性之分子構造的（ 甲基）丙烯酸酯單體、例如脂肪族（甲基）丙烯酸酯單體、脂 環式（甲基）丙烯酸酯單體、及芳香族（甲基）丙烯酸酯單體 〇 如此之（甲基）丙烯酸醋單體係可爲單官能之（甲基）丙 -21 - 201237557 烯酸酯單體，亦可爲2官能性之（甲基）丙烯酸酯單體，可 分別單獨使用，或亦可組合二種以上而使用。 含有羥基之（甲基）丙烯酸酯單體係可舉例如2·羥乙基 (甲基）丙烯酸酯、2_羥丙基（甲基）丙烯酸酯、2-羥丁基（甲 基）丙烯酸酯、2-羥基-3-苯氧基丙基（甲基）丙烯酸酯、2-( 甲基）丙烯醯氧基氧乙基-2-羥基丙基酞酸酯、甘油單（甲基 )丙烯酸酯。 含有羧基之（甲基）丙烯酸酯單體係可舉例如2-(甲基） 丙烯醯氧基乙基琥珀酸、2-(甲基）丙烯醯氧基乙基酞酸、 2-(甲基）丙烯醯氧基乙基六氫酞酸。 含有胺基之（甲基）丙烯酸酯單體係可舉例如二乙基胺 乙基（甲基）丙烯酸酯、二甲基胺基甲基（甲基）丙烯酸酯。 脂肪族（甲基）丙烯酸酯係可舉例如月桂基（甲基）丙烯 酸酯、2-乙基己基（甲基）丙烯酸酯、異癸基（甲基）丙烯酸 酯、硬脂基（甲基）丙烯酸酯、1,6-己二醇（甲基）丙烯酸酯。 芳香族（甲基）丙烯酸酯係可舉例如苯甲基（甲基）丙烯 酸酯。 脂環式（甲基）丙烯酸酯係具有碳數_3〜20的單環或多 環的脂環式烴基的（甲基）丙烯酸酯，可舉例如環己基（甲基 )丙烯酸酯、異冰片基（甲基）丙烯酸酯、二環戊烯氧基乙基 (甲基）丙烯酸酯、二環戊二烯基（甲基）丙烯酸酯' 三環癸 烯基（甲基）丙烯酸酯、降茨烯基（甲基）丙烯酸酯等。 此等之單官能或2官能的含（甲基）丙烯醯氧基單體， 就市售品係可舉例如「SA-1 002」（三菱化學公司製）、「 -22- 201237557(wherein R1 and s are as defined above), wherein the total of the "acryloxy group and the methacryloxy group is 4 or more". In the present invention, a dendrimer compound having an ether bond or an ester bond and having a (methyl)-propyl oxime-oxy group at the terminal is a polyfunctional acrylic acid having 4 or more (meth) acryloxy groups in the molecule. The ester compound is, for example, V# 1 000 (a compound of the formula (1 1) having a molecular weight of 28 00, manufactured by Osaka Organic Chemical Co., Ltd.). Further, in the present invention, the molecular weight is a number average molecular weight calculated by gel permeation chromatography (GPC) in terms of polystyrene. In the present invention, the synthesis of a dendrimer having a dendrimer structure The method may be, for example, a divergence method in which synthesis is performed from the center of the core body toward the outside, and a convergence method in which synthesis is performed from the outside toward the core body. These synthesis methods are well known to those skilled in the art, for example, as described in JP-A-11 -60540. Specifically, the first generation of the dendrimer compound is produced by reacting a polyester polyol compound obtained by reacting dipentaerythritol with 2,2-dimethylolpropionic acid with (meth)acrylic acid. Further, the poly-polyol compound is further reacted with 2,2--methylpropionic acid -19-201237557, followed by reaction with (meth)acrylic acid to produce a second-generation tree-like compound. In the present invention, the component (A) is preferably from 1 to 25% by weight, preferably from 0.5 to 10% by weight, based on the weight of the component (A) to the component (D). In the present invention, the photocurable prepolymer of the component (B) is a base resin (substrate oligomer) of the adhesive composition, and is irradiated with an active energy ray such as ultraviolet rays, and the (meth) propylene of the reactive group. A photosensitive resin obtained by polymerizing a decyloxy group. (B) The component is a transparent, low-absorbency resin having a very low polarity and a molecular structure, and is therefore intended to block oil or water components which are intended to invade from the periphery of the adhesive surface. The (B) photocurable prepolymer of the present invention has one or more (meth) acryloxy groups having polybutadiene, polyisoprene, polybutadiene or polyiso One or more selected from the group consisting of a hydride of pentadiene, a modified group of a carboxyl group modified with polybutadiene or polyisoprene, and a polyester skeleton having a urethane bond The chain skeleton has one or more (meth)acryloxycarbonyl groups, that is, oligomers containing a (meth)acryloxy group, at the terminal or side chain of the main chain skeleton. In the present invention, the (B) photocurable prepolymer is preferably a main chain skeleton selected from the group consisting of polybutadiene or a hydride of polybutadiene, and particularly preferably hydrogenated with polybutadiene. The object acts as the backbone of the main chain. Further, in the present invention, the (B) photocurable prepolymer preferably has two or more (meth) acryloxy groups, and it is particularly preferable to have (meth) propylene oxide at both ends of the main chain skeleton. Base. In the present invention, the component (B) may be used singly or in combination of two or more. In the present invention, the photocurable prepolymer of the component (B) has a molecular weight of usually from 400 to 200,000, preferably from 800 to 1,000,000, particularly preferably from 1,000 to -20 to 201237557 3 0,000. If the molecular weight is such a range, the coating property is good, and the coating property of the cylinder is good, and the hardening shrinkage of the cured product of the active energy ray-curable resin composition after adhesion does not become large. (B) The photocurable prepolymer of the component is, for example, "NISSO-PB TEAI-1000" (two-terminal acrylate-modified hydrogenated butadiene-based oligomer) manufactured by Nippon Soda Co., Ltd. "NISSO-PB TE-2000" (two-terminal methacrylate-modified butadiene-based oligomer) manufactured by Japan Soda Co., Ltd., "UC-203" manufactured by Kuraray Co., Ltd. (maleic anhydride maleic anhydride) An adduct and an esterified oligomer of 2-hydroxyethyl methacrylate), "UA-1" (terminal urethane acrylate-modified polybutadiene hydride) manufactured by Kagawa Chemical Co., Ltd., and the like. In the present invention, the component (B) is preferably 25 to 60% by weight, preferably 30 to 50% by weight, based on the weight of the component (A) to the component (D). In the present invention, the monofunctional or bifunctional (meth) acryloxy group-containing monomer ((meth) acrylate monomer) which is a component (C) is a reactive diluent, and the base resin is cured. It cures and exerts excellent adhesion to the adherend. The component (C) may, for example, be a (meth) acrylate having a polar group, for example, a hydroxyl group-containing (meth) acrylate, a carboxyl group-containing (meth) acrylate, and an amine group-containing acrylate; A (meth) acrylate monomer having a polar molecular structure, such as an aliphatic (meth) acrylate monomer, an alicyclic (meth) acrylate monomer, and an aromatic (meth) acrylate monomer 〇 Such a (meth)acrylic acid vinegar single system may be a monofunctional (meth) propyl-21 - 201237557 enoate monomer, or a bifunctional (meth) acrylate monomer, which may be separately They may be used or combined in combination of two or more. The hydroxyl group-containing (meth) acrylate single system may, for example, be hydroxyethyl (meth) acrylate, 2- hydroxypropyl (meth) acrylate or 2-hydroxybutyl (meth) acrylate. , 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-(methyl) propylene oxyoxyethyl 2-hydroxypropyl phthalate, glycerol mono (meth) acrylate . The mono-system of the (meth) acrylate having a carboxyl group may, for example, be 2-(meth) propylene methoxyethyl succinic acid, 2-(methyl) propylene methoxyethyl decanoic acid, 2-(methyl ) propylene methoxyethyl hexahydrophthalic acid. The mono-system of the (meth) acrylate containing an amine group may, for example, be diethylamine ethyl (meth) acrylate or dimethylaminomethyl (meth) acrylate. Examples of the aliphatic (meth) acrylate include lauryl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, and stearyl (methyl). Acrylate, 1,6-hexanediol (meth) acrylate. The aromatic (meth) acrylate may, for example, be benzyl (meth) acrylate. The alicyclic (meth) acrylate is a (meth) acrylate having a monocyclic or polycyclic alicyclic hydrocarbon group having a carbon number of _3 to 20, and examples thereof include cyclohexyl (meth) acrylate and isobornyl. (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentadienyl (meth) acrylate 'tricyclodecenyl (meth) acrylate, dec Alkenyl (meth) acrylate and the like. Such a monofunctional or bifunctional (meth) propylene oxime-containing monomer may be, for example, "SA-1 002" (manufactured by Mitsubishi Chemical Corporation), "-22-201237557".

Kayarad R-684」（日本化藥）、「Light Ester BZ」、「Light Ester ΙΒ·Χ」、「Light Ester HO」、「Light Ester HO-MS」（ 「Light Ester」係任一者均爲共榮社化學公司製）等。 在本發明中’相對於（A)成分〜（D)成分之重量，（C)成 分係宜爲25〜70重量％，宜爲40〜60重量％。 在本發明中’（D)成分爲光聚合起始劑。光聚合起始 劑係可舉例如紫外線聚合起始劑或可見光聚合起始劑等， 但任一者均可無限制使用。紫外線聚合起始劑係可舉例如 苯偶因系、二苯甲酮系、及乙醯苯系等，於可見光聚合起 始劑中可舉例如醯基氧化磷系、硫雜蔥酮系、二茂鐵系、 及醌系等。 紫外線聚合起始劑具體上可舉例如二苯甲酮、4_苯基 二苯甲酮、苯甲醯基安息香酸、及雙二乙基胺基二苯甲酮 等之二苯甲酮系聚合起始劑；2,2_二乙氧基乙醯苯等之乙 醯苯系聚合起始劑；苯甲基、苯偶因、及苯偶因異丙基醚 等之苯偶因系聚合起始劑；苯甲基二甲基縮酮等之烷基酚 系聚合起始劑；硫雜蔥酮等之硫雜蔥酮系聚合起始劑；^ 羥基環己基苯基酮、1-(4 -異丙基苯基）2 -羥基_2_甲基丙烷_ 1-酮、1-(4-(2-羥基乙氧基）_苯基）_2_羥基_2_甲基_丨_丙烷- 1-酮、及2-羥基-2-甲基苯基丙烷酮等之羥基烷基酚 系聚合起始劑。 可見光聚合起始劑係可舉例如2，4,6_三甲基苯甲醯基 —苯基氧化磷、雙（2，4,6-三甲基苯甲醯基）_苯基氧化磷、 及雙（2,6-二甲氧基苯甲醯基）_2,4,4_三甲基_戊基氧化磷等 -23- 201237557 之醯基氧化磷系光起始劑；樟腦酮、2 -甲基-1_(4 -甲基硫） 苯基）-2-嗎啉基丙烷-1-酮、及2 -苯甲基-2 -二甲基胺基-i_ (4-嗎啉基苯基）-1-丁酮-1等的酮系聚合起始劑等。 在本發明中，就（D)光聚合起始劑而言，較佳係丨_羥基 環己基苯基嗣（IRGACURE 184、Ciba Specialty Chemicals 公 司製）及雙（2,4,6-三甲基苯甲醯基）-苯基氧化磷（iRGACURE 819、Ciba Specialty Chemicals 公司製）。 在本發明中，相對於（A)成分〜（D)成分之重量，（D)成 分係宜爲0.1〜1重量％，宜爲0.5〜5重量％。 本發明之活性能量線硬化性樹脂組成物係在無損本發 明之目的的範圍，可使用無機塡充劑、抗氧化劑、聚合抑 制劑、可塑劑、有機塡充劑、丙烯酸橡膠、胺基甲酸酯橡 膠等之各種彈性體、甲基丙烯酸甲酯-丁二烯-苯乙烯系接 枝共聚物或丙烯腈-丁二烯-苯乙烯系接枝共聚物等之接枝 共聚物、溶劑、增量材、補強材、增黏劑、染料、顔料、 耐燃劑及界面活性劑以及熱聚合起始劑等的添加劑。 本發明之硬化性組成物係目的在於進一步賦予高硬度 、樹脂剛性及低硬化收縮性，就（E)成分而言，可進一步 含有無機塡充劑。 無機塡充劑可舉例如石英、石英玻璃、熔融二氧化矽 、球狀二氧化矽等之二氧化矽粉末等或球狀氧化鋁、破碎 氧化鋁、氧化鎂、氧化鈹、氧化鈦等之氧化物類、氮化硼 、氮化矽、氮化鋁等之氮化物類、碳化矽等之碳化物類、 氫氧化鋁、氫氧化鎂等之氫氧化物類、銅、銀、鐵、鋁、 -24- 201237557 鎳、鈦等之金屬類或合金類、鑽石、碳等之碳系塡充劑、 複合氧化物所構成之玻璃塡充劑等。此等無機塡充劑係可 使用1種或2種以上。無機塡充劑係可容易取得，就市售 品而言可舉例如玻璃塡充劑（日本Frit公司製「CF0023-05C 」）、非晶質二氧化矽（日本觸媒公司製「SEAHOSTAR KE-P250」）、發煙質二氧化矽（搖變賦予劑）（Cabot Specialty Chemicals公司製「TG3 08 F」）、球狀二氧化矽（日本Frit 公司製「CF0018-WB15C」）。在本發明中，若考量對丙烯 酸樹脂之塡充性，宜爲由已調整折射率之複合氧化物所構 成的調光玻璃纖維，其時，爲免過度提昇黏度，宜爲球狀 形狀。 在本發明中，相對於（A)成分〜（D)成分之合計100重 量份，（E)成分係宜爲70〜3 00重量份，更宜爲100〜250 重量份。 本發明之硬化性組成物係目的在於組成物之安定性， 就（F)成分而言，可進一步含有抗氧化劑。 就抗氧化劑而言可舉例如酚系抗氧化劑、氫醌系抗氧 化劑、及其他之抗氧化劑，較佳係酚系抗氧化劑。 酚系抗氧化劑係可舉例如2,2-亞甲基-雙（4-甲基-6-第 三丁基酚）、兒茶酚、苦味酸、第三丁基兒茶酚、2,6-第三 丁基-對甲酚、及4,4’-硫雙[亞乙基（氧）（羰基）（乙烯）]雙 [2,6-雙（1，1-二甲基乙基）酚]。 氫醌系抗氧化劑係可舉例如々-萘醌、2-甲氧基-1，4-萘醌、甲基氫醌、氫醌、氫醌單甲基醚、單第三丁基氫醌 -25- 201237557 、2,5-二第三丁基氫醌、對苯醌、2,5-二苯基-對苯醌、及 2,5-二第三丁基-對苯醌。 其他之抗氧化劑係可例示檸檬酸 '酚嗪、及2 - 丁基-4-羥基茴香醚等。 抗氧化劑就市售品而言，可舉例如IRGANOX 1〇1〇、 及 IRGANOX 1 03 5FF(任一者均爲 Ciba Specailty Chemicals 公司製）。 在本發明中，相對於（A)成分〜（D)成分之合計1〇〇重 量份，（F)成分係宜爲0.01〜5重量份，更宜爲0.1〜2重 量份。 本發明之硬化性組成物係就（G)成分而言，可進一步 含有聚合抑制劑。 聚合抑制劑係可舉例如酚系聚合抑制劑及酚嗪系聚合 抑制劑。 酚系聚合抑制劑係可舉例如2,2-亞甲基-雙（4·甲基- 6-第三丁基酚）（BHT)、兒茶酚、苦味酸、第三丁基兒茶酚、 2，6 -第三丁基-對甲酚、及4,4，-硫雙[亞乙基（氧）（羰基）（乙 烯）]雙[2,6-雙（1，1-二甲基乙基）酚]。 酚嗪系聚合抑制劑係可舉例如酚嗪、雙甲基苯甲 基酚嗪）、3,7-二辛基酚曝及雙（α，α-二甲基苯甲基）酚嗪 〇 又’ ΒΗΤ等之酚系聚合抑制劑係亦可使用來作爲抗氧 化劑。 在本發明中’相對於（Α)成分〜（D)成分之合計100重 -26- 201237557 量份’（G)成分係宜爲0.01〜3重量份，更宜爲0.05〜1重 量份。 本發明之硬化性組成物係以更進一步提昇黏著性 '黏 著耐久性以及提昇硬化體之耐熱性爲目的，可含有（H)可 塑劑。如此之可塑劑宜爲使聚丁二烯之不飽和鍵進行環氧 基化所得到之寡聚物，就市售品而言，可舉例如BF-1 000 (ADEKA公司製）或PB-3600(Daicel工業化學公司製）。 在本發明之硬化性組成物中，相對於（A)成分〜（D)成 分之合計100重量份，（H)成分係宜爲〇.〇1〜20重量份， 更宜爲0.1〜10重量份。 本發明之活性能量線硬化性樹脂組成物係以進一步降 低硬化收縮率作爲目的，可含有（I)有機塡充劑。有機塡充 劑係可舉例如丙烯酸系塡充劑、苯乙烯系塡充劑、丙烯酸/ 苯乙烯共聚合系塡充劑、氟系樹脂塡充劑、聚乙烯系塡充 劑及聚丙烯系塡充劑，就市售品而言，可舉例如「PPW-5」 (聚丙烯塡充劑、SEISHIN企業公司製）、及「PROPYLPAD 31」（聚丙烯塡充劑、MICROPOWDERS INC.公司製）。可 分別單獨使用，亦可組合2種以上而使用。更佳之有機塡 充劑係膨潤少之聚丙烯塡充劑。 在本發明之硬化性組成物中，相對於（A)成分〜（D)成 分之合計1〇〇重量份，（I)成分係宜爲〇.〇1〜20重量份， 更宜爲0.1〜10重量份。 本發明之硬化性組成物係以更進一步提昇對玻璃面之 密著性爲目的，可進一步含有矽烷偶合劑。 -27- 201237557 矽烷偶合劑可舉例如r-氯丙基三甲氧基矽烷、 基三甲氧基矽烷、乙烯基三氯矽烷、乙烯基三乙氧基 、乙烯基-参甲氧基乙氧基）矽烷' r-甲基丙烯醯 基三甲氧基矽烷、r-丙烯醯氧丙基三甲氧基矽烷’ (3,4-環氧基環己基）乙基三甲氧基矽烷、r-環氧丙氧 基三甲氧基矽烷、r-氫硫基丙基三甲氧基矽烷、r-丙基三乙氧基矽烷、n-沒-(胺基乙基）-r -胺基丙基三 基矽烷、ν·α-(胺基乙基）-r-胺基丙基甲基二甲氧基 及脲基丙基三乙氧基矽烷等，較佳係r-環氧丙氧 基三甲氧基矽烷、r-環氧丙烷基丙基三乙氧基矽烷 (3,4-環氧基環己基）乙基三甲氧基矽烷、環氧丙氧 基甲基二乙氧基矽烷。此等之矽烷偶合劑係可單獨亦 合2種以上而使用。 在本發明之硬化性組成物中，矽烷偶合劑之含量 對於（A)成分〜（D)成分之合計1〇〇重量份，宜爲〇〜1 量份。但，矽烷偶合劑係在硬化性組成物之硬化後的 試驗時易釋出成爲釋氣成分，故相對於不含有矽烷偶 之硬化性組成物，亦即（A)成分〜（D)成分的總重量， 烷偶合劑之含量爲〇重量份。 在本發明中’活性能量線硬化性樹脂組成物之硬 係可藉由使本發明之活性能量線硬化性樹脂組成物硬 得到。使本發明之活性能量線硬化性樹脂組成物硬化 法係包含對本發明之活性能量線硬化性樹脂組成物照 線能量線之步驟。 乙烯 矽烷 氧丙 • β -基丙 胺基 甲氧 矽烷 基丙 、2- 基丙 可組 係相 0重 耐熱 合劑 宜矽 化物 化所 之方 射活 -28- 201237557 在本發明中，活性能量線之波長係只要爲本發明之活 性能量線硬化性樹脂組成物硬化的波長即可，無特別限定 ，而爲100〜420nm，更宜爲300〜420nm。 本發明之活性能量線硬化性樹脂組成物係黏著性組成 物，可用來作爲黏著劑、尤其光學構件黏著用之黏著劑。 使用本發明之黏著劑而貼合的構件可舉例如由金屬、 或金屬被鍍金之構件或塑膠等所構成的小零件。構成小零 件之金屬可舉例如Mg、Zn、Ni、及A1等，塑膠可舉例如 液晶聚合物（LCP)、環烯烴聚合物（COP)、環烯烴共聚物 (COC)、聚苯硫醚（PPS)、聚苯氧（PPO)、或於上述塑膠材 中混練有玻璃纖維或碳纖維之複合塑膠材料等。塑膠材料 係可取自市售品，PPS係可舉例如出光社製「出光PPS」 、及Toray公司製「Torelina」，液晶聚合物可舉例如Toray 公司製「Siveras」、Polyplastic 公司製「Vectora」，聚 芳酸酯可舉例如Unitika公司製「U Polymer」，環烯烴聚 合物可舉例如日本Zeon公司製「Zeonex」、三井化學公 司製「Apel」、及 JSR公司製「Arton」，聚碳酸醋可舉 例如帝人公司製「Panlite」等，但不限定於此等。 又，使用本發明之黏著劑而貼合的光學零件，可舉例 如在記錄材料之記錄再生所使用的機器領域中所使用的機 器之構件例如光檢測器（PD)、雷射二極體（LD)、透鏡、稜 鏡等之光學零件或透鏡等之光學零件搭載的光學模組。又 ，光學拾取零件係依零件所求取之固定精度的要求相異， 具體上係可舉例如光檢測器（PD)、雷射二極體（LD)、集光 -29- 201237557 鏡（NAL)等之高精度要求高的零件、半鏡片（光束分離器 )(HM(PBS))、斜度等之高精度要求略高的零件、反射鏡 (RM)等的高精度要求爲中程度之零件，、對物透鏡（OBL)、 光準直器透鏡等之高精度要求略低之零件。 本發明之硬化性組成物係具有多官能丙烯酸酯化合物 、二烯系或氫化之二烯系的（甲基）丙烯酸酯的光硬化性預 聚物、具有各種官能基之反應稀釋性的（甲基）丙烯酸酯、 及含有光聚合起始劑的特定組成，故具有特徵係：可藉照 射活性能量線，以短時間硬化，對於聚苯硫醚（PPS)等塑 膠構件、或金屬構件，具有高的初期黏著性，以高溫高濕 試驗爲首之耐久性試驗，呈現高的保持力。可抑制其熱時 之變形、及對於熱時與荷重之變形性至極少。因此可抑制 被本發明之活性能量線硬化性樹脂組成物所黏著之硬化後 的零件之移動至最大限。 1J 式 方 施 實 [實施例] 以下，舉出實施例及比較例，更詳細地說明本發明， 但本發明係不限定於此等。又，於實施例及比較例記載之 慘合組成物中之各成分係選擇以下之化合物。 (A)多官能丙烯酸酯化合物 (A-1)V#802(大阪有機化學公司製） (A-2)二季戊四醇六丙烯酸酯（共榮社化學公司製「DPE-6A」） (A-3 )V #1000(大阪有機化學公司製） -30- 201237557 (A_4)V#Star-5 0 1(大阪有機化學公司製） (B) 光硬化性預聚物 (B-1)末端胺基甲酸酯丙烯酸酯改性聚丁二烯（曰本曹達公 司製「TE-2000」） (B-2)末端胺基甲酸酯丙烯酸酯改性聚丁二烯氫化物（香川 化學公司製「UA-24」） (C) 單官能或2官能之含（甲基）丙烯醯氧基單體（丙烯酸酯 單體） (C-1)三環癸烷二甲醇丙烯酸酯（三菱化學公司製「SA-1002」） (C-2)苯甲基甲基丙烯酸酯（共榮社化學公司製「Light Ester BZ」） (C-3)異冰片基甲基丙烯酸酯（共榮社化學公司製「Light Ester IB-X j ) (C-4)2-羥基乙基甲基丙嫌.酸酯（共榮社化學公司製「Light Ester HO」） (C-5)2-甲基丙烯醯氧乙基琥珀酸（共榮社化學公司製「 Light Ester HO-MS」） (D) 光聚合起始劑 (D-l)l-羥基環己基苯基酮（Ciba Specialty Chemicals公司 製「IRGACURE 184」） (D-2)雙（2,4,6-三甲基苯甲醯基）-苯基氧化磷（Ciba Specialty Chemicals 公司製「IRGACURE 819」） (E) 無機塡充劑 (E-1)玻璃塡充劑（日本Frit公司製「CF0023-05C」） -31 - 201237557 (E_2)發煙質二氧化砂（Cabot Specialty Chemicals 公司製「 TG308F」） (F) 抗氧化劑 (F-l)(Ciba Specialty Chemicals 公司製「IRGANOX1010」） (F-2)(Ciba Specialty Chemicals 公司製「IRGANOX1 035」） (G) 聚合抑制劑 (G-l )2，2-亞甲基-雙（4-甲基-6-第三丁基酚）（關東化學公司 製「BHT」） (H) 可塑劑 (H-1)使聚丁二烯之不飽和鍵環氧基化所得到的寡聚物 (ADEKA 公司製「BF-1000」）. ⑴成分：有機塡充劑 (1-1)聚丙嫌塡充劑（Seishin企業公司製「ppw-5」） 活性能量線硬化性樹脂組成物之硬化物的各種物性係 如以下般測定。 [光硬化條件] 就活性能量線源而言’使用點照相機（浜松ph〇t〇nix 公司製「LC-8」），使用USHI〇公司製紫外線照度計「UIT_ 1〇1」，以照射強度250mW/cm2的條件照射12秒，使之硬 化。 [角度變化測定] (1)角度變化測定用試料之製作 -32- 201237557 如圖1所示般，使鋁板2垂直固定’隔開3 ΟΟμιη之間 隙，使 10(固定邊）xl.0(厚）χ20(長）mm 之 SUS 板 4(SUS 304 、1.5 g)，對於鋁板而大槪成爲90度載置於座台5之上而 配置。爲使鋁板與SUS板固定，使用點膠機調整器（武藏 Engineering製ML-606)而於固定邊之中央部塗佈本發明之 活性能量線硬化性樹脂組成物1(0.002 5 cc)。塗佈後立即， 從斜45度、20mm之距離使用UV照射器3，照射250mW/cm2 之UV光12秒而固定。然後，卸下座台5而作爲評估用 試料。 (2)角度變化之測定 使用傾斜感測器（NISSHO ELECTRONICS公司製MTS-T20)而從角度變化監視熱時之黏著劑部分的變形。如圖2 所示般’使前述記載之角度變化測定用試料固定於恆溫槽 (E S P E C公司製M C - 7 1 1 T)內’使傾斜感測器之光束反射至 SU S板，爲可監視般’調整傾斜感測器之位置。恆溫槽內 之溫度係以2 5 °C保持3 0分鐘來調溫。測定調溫後之角度 變化量而爲〇。溫度循環係以2 5。(：保持1小時，然後，以 30分從25C使溫度上昇至60C，達到60°C後以60°C保持 1小時’進一步’以30分從60°C使溫度上昇至80〇c，達 到8 0 C後以8 0 C保持1小時’以3 0分從8 0 °C使溫度降至 2 5 C，作爲1循環。以此溫度循環使恆溫槽內之溫度改變 爲25°C、60°C、80°C。在初次之循環中，求取以6〇它及 8 0 °C保持1小時後，以及以1循環後的2 5它保持丨小時後 33 · 201237557 之角度變化量。又，表中之角度變化量依分鐘而定。 [黏著性試驗] 黏著性試驗係藉押脫黏著強度來測定。如圖3所示般 ，於PPS (聚苯硫醚、出光PPS NT7790(出光公司製）），經 端面硏磨之銘粒（Engineering test Service公司製、A5052P 、縱 lOmmx橫lOmmx高2mm)，使用點膠機調整器（武藏 Engineering製ML-606)而使用唧筒塗佈0.002 5cc之活性 能量線硬化性樹脂組成物，然後，離20mm之距離使用 UV照射器（浜松Photonix公司製、LC6)，使用UV照度計 (Ushiro電機公司製、UIT-101)而照射 2 5 0mW/cm2之 UV 光1 2秒來固定。如此做法而製作黏著性試驗片。使用押 脫試驗機（島津製作所製AGS-500D)，從不固定晶粒之側 ，對於直徑4mm的區域，以押脫速度10mm/分測定押脫 強度。以40N以上之強度顯示無浮離的狀態者爲〇。使同 樣之試驗以PPS塑粒（縱lOmmx橫lOmmx高2mm)與PPS 板，及以經端面硏磨之銘晶片與銘板（Engineering test Service 公司製、A505 2P)進行。 (實施例1〜7及比較例1〜2) 以表1及表2所示之組成混合表1及表2所示之種類 的原材料而調製樹脂組成物。對於所得到之組成物，進行 黏著強度之測定及耐濕性、耐熱性、耐熱沖擊評估試驗。 將其等之結果表示於表1及表2中。又，含有量爲重量份 -34- 201237557 耐濕性試驗係使用LH21-21M(Nagano Science )，以65°C /95%RH-3 3 6小時之條件進行。未觀察到 或龜裂、端部之龜裂，黏著強度爲40N以上者爲〇 耐熱性係使用LC-1 12(Espec公司製），以80°C 時之條件進行。未觀察到浮離、或龜裂、端部之龜 著強度爲40N以上者爲〇。 耐熱沖擊評估試驗係使用TSA-41L(Espec公ΐ 以-40°C (3 0分）/85°C (30分）之1〇〇循環的條件進行 察到浮離、或龜裂、端部之龜裂，黏著強度爲40N 爲〇。 公司製 浮離、 〇 -3 3 6 小 裂，黏 製）， 。未觀 以上者 -35- 201237557 [表1] 實施例 1 實施例 2 實施例 3 實施例 4 實施例 5 實施例 6 實施例 7 (A)多官能丙烯 酸酯化合物 A-1 6.25 7.5 20 7.5 A-2 7.5 A-3 20 A-4 20 (B)光硬化性 預聚物 B-1 100 100 100 B-2 100 100 100 100 (C)丙烯酸酯單體 C-1 7.5 25 25 23.3 7.5 23.3 23.3 C-2 25 25 25 83.3 25 83.3 83.3 C-3 25 25 25 33.3 25 33.3 33.3 C-4 25 25 25 6.67 25 6.67 6.67 C-5 12.5 12.5 12.5 16.7 12.5 16.7 16.7 (D)聚合起始劑 D-1 4.5 4.5 4.5 9.33 4.5 9.33 9.33 D-2 0.5 0.5 0.5 0.5 (E憮機塡充劑 E-1 225 380 380 487 380 487 487 E-2 2.5 2.5 2.5 6.7 2.5 6.7 6.7 (F)抗氧化劑 F-1 1 1 1 F-2 1.25 1.25 1.25 1.25 (G)聚合抑制劑 G-1 0.25 0.25 0.25 0.67 0.25 0.67 0.67 (H河塑劑 H-1 66.7 66.7 66.7 (I)有機塡充劑 1-1 26.7 26.7 26.7 黏著性(PPS/AI) Ο Ο Ο 〇 〇 Ο 〇 黏著性(PPS/PPS) ο 〇 Ο Ο Ο Ο 〇 黏著性(AI/AI) ο Ο Ο Ο Ο Ο 〇 耐濕性 ο 〇 ο Ο 〇 〇 Ο 耐熱性 ο 〇 〇 Ο Ο 〇 Ο 耐熱沖擊性 ο 0 Ο 〇 Ο 〇 Ο 角度變化量 (初次） 25°C 0 0 0 0 0 0 0 60°C 〜20， 5, …0' -20, 5, 〜20, 〜20, 80°C 〜30, 〜15， 〜15# 〜30, 〜15， 〜30, 〜30, 角度變化量 25°C 〜15， 〜5' 〜5， 〜15# 〜 〜15， 〜15， -36- 201237557 [表2] 比較例1 比較例2 (A)多官能丙烯 酸酯化合物 A-1 A-2 A — 3 A-4 (B)光硬化性 預聚物 B— 1 100 B-2 100 (C)丙烯酸 酯單體 C-1 7.5 23 C-2 25 83 C-3 25 33 C-4 25 6.7 C-5 12.5 16.7 (D)聚合起始劑 D-1 4.5 9.3 D-2 0.5 (E)無機塡充劑 E-1 225 487 E-2 2.5 6.7 (F)抗氧化劑 F-1 1 F-2 1.25 (G)聚合抑制劑 G-1 0.25 0.67 (H河塑劑 H-1 66.7 (I)有機塡充劑 1-1 26.7 黏著性(PPS/AI) 〇 〇 黏著性(PPS/PPS) 〇 〇 黏著性(AI/AI) 〇 〇 耐濕性 〇 〇 耐熱性 〇 〇 耐熱沖擊性 〇 〇 角度變化量 (初次） 25°C 0 0 60°C 超過3(Τ 超過30' 80°C 超過30' 超過30' 角度變化量 25°C 超過30' 超過30' 本發明之硬化性組成物係可使例如LD、光檢測器、 透鏡、稜鏡等之光學零件、或透鏡等之光學零件搭載的光 學模組等以高的固定精度固定，故可用來作爲光學裝置組 -37- 201237557 裝用之黏著劑。 【圖式簡單說明】 圖1係用以從角度變化測定本發明之硬化性組成物的 熱時黏著劑部分之變形的裝置。 圖2係使本發明之硬化性組成物光硬化後，卸下治具 ，用以藉傾斜感測器測定角度變化之圖。 圖3係以本發明之活性能量線硬化性樹脂組成物貼t 的黏著構造體之押脫強度試驗之模式圖。 【主要元件符號說明】 1 :活性能量線硬化性樹脂組成物 2 :鋁板 3 : UV照射器 4 : SUS 板 5 :座台 6 :傾斜感測器 7 :活性能量線硬化性樹脂組成物 8 :銘板 9 : PPS 板 -38-Kayarad R-684", "Light Ester BZ", "Light Ester ΙΒ Χ", "Light Ester HO", "Light Ester HO-MS" ("Light Ester") are all Rongshe Chemical Co., Ltd.). In the present invention, the component (C) is preferably from 25 to 70% by weight, preferably from 40 to 60% by weight, based on the weight of the component (A) to the component (D). In the present invention, the component (D) is a photopolymerization initiator. The photopolymerization initiator may, for example, be an ultraviolet polymerization initiator or a visible light polymerization initiator, but any of them may be used without limitation. Examples of the ultraviolet polymerization initiator include a benzoin-based system, a benzophenone-based system, and an acetophenone-based system. Examples of the visible-light polymerization initiator include a sulfhydryl phosphorus oxide system, a thioxanthene system, and Ferrocene, and lanthanide. Specific examples of the ultraviolet polymerization initiator include benzophenone polymerization such as benzophenone, 4-phenylbenzophenone, benzamidine benzoic acid, and bis diethylaminobenzophenone. Starting agent; acetophenone polymerization initiator such as 2,2-diethoxyethyl benzene; polymerization of benzoin such as benzyl, benzoin, and benzoin isopropyl ether a starting agent; an alkylphenol-based polymerization initiator such as benzyl dimethyl ketal; a thioglycan-based polymerization initiator such as thioidone; hydroxycyclohexyl phenyl ketone, 1-(4) -isopropylphenyl)2-hydroxy-2-methylpropan-1-one, 1-(4-(2-hydroxyethoxy)-phenyl)_2-hydroxy-2-methyl-oxime-propane a hydroxyalkylphenol-based polymerization initiator such as 1-ketone or 2-hydroxy-2-methylphenylpropanone. The visible light polymerization initiator may, for example, be 2,4,6-trimethylbenzimidyl-phenylphosphine oxide, bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide, And bis(2,6-dimethoxybenzylidene)_2,4,4-trimethyl-pentylphosphine oxide, etc. -23- 201237557 sulfhydryl phosphide-based photoinitiator; camphorone, 2 -methyl-1_(4-methylsulfanyl)phenyl)-2-morpholinylpropan-1-one, and 2-benzyl-2-aminomethyl-i-(4-morpholinylbenzene A ketone-based polymerization initiator such as 1-butanone-1. In the present invention, as the (D) photopolymerization initiator, hydrazine-hydroxycyclohexylphenyl hydrazine (IRGACURE 184, manufactured by Ciba Specialty Chemicals) and bis(2,4,6-trimethylbenzene) are preferred. Mercapto)-phenylphosphine oxide (iRGACURE 819, manufactured by Ciba Specialty Chemicals). In the present invention, the component (D) is preferably 0.1 to 1% by weight, preferably 0.5 to 5% by weight based on the weight of the component (A) to the component (D). The active energy ray-curable resin composition of the present invention can be used in the range which does not impair the object of the present invention, and an inorganic chelating agent, an antioxidant, a polymerization inhibitor, a plasticizer, an organic chelating agent, an acrylic rubber, an aminocarboxylic acid can be used. a graft copolymer, solvent, or the like of various elastomers such as ester rubber, methyl methacrylate-butadiene-styrene graft copolymer or acrylonitrile-butadiene-styrene graft copolymer Additives for materials, reinforcing materials, tackifiers, dyes, pigments, flame retardants and surfactants, and thermal polymerization initiators. The curable composition of the present invention is intended to further impart high hardness, resin rigidity, and low hardenability and shrinkage, and the (E) component may further contain an inorganic chelating agent. Examples of the inorganic chelating agent include oxidized cerium oxide powder such as quartz, quartz glass, molten cerium oxide, or spherical cerium oxide, or spherical alumina, crushed alumina, magnesia, cerium oxide, titanium oxide, or the like. Nitrides such as boron nitride, tantalum nitride, aluminum nitride, carbides such as tantalum carbide, hydroxides such as aluminum hydroxide and magnesium hydroxide, copper, silver, iron, aluminum, -24- 201237557 A metal or alloy such as nickel or titanium, a carbon-based chelating agent such as diamond or carbon, or a glass enthalpy composed of a composite oxide. These inorganic chelating agents can be used alone or in combination of two or more. In the case of a commercially available product, for example, a glass ruthenium ("CF0023-05C" manufactured by Frit Corporation of Japan) and an amorphous cerium oxide ("SEAHOSTAR KE-" manufactured by Nippon Shokubai Co., Ltd.) may be mentioned. P250"), fuming cerium oxide (shake imparting agent) ("TG3 08 F" manufactured by Cabot Specialty Chemicals Co., Ltd.), and spherical cerium oxide ("CF0018-WB15C" manufactured by Frit Corporation, Japan). In the present invention, in consideration of the compatibility with the acrylic resin, it is preferred that the light-adjusting glass fiber is composed of a composite oxide having a refractive index adjusted, and in order to avoid excessively increasing the viscosity, it is preferably a spherical shape. In the present invention, the component (E) is preferably 70 to 300 parts by weight, more preferably 100 to 250 parts by weight, based on 100 parts by weight of the total of the components (A) to (D). The curable composition of the present invention is intended to have stability of the composition, and may further contain an antioxidant in the component (F). The antioxidant may, for example, be a phenol-based antioxidant, a hydroquinone-based antioxidant, or another antioxidant, and is preferably a phenol-based antioxidant. Examples of the phenolic antioxidant include 2,2-methylene-bis(4-methyl-6-tert-butylphenol), catechol, picric acid, t-butylcatechol, and 2,6. - tert-butyl-p-cresol, and 4,4'-thiobis[ethylene (oxy)(carbonyl)(ethylene)]bis[2,6-bis(1,1-dimethylethyl) phenol]. Examples of the hydroquinone-based antioxidants include anthraquinone-naphthoquinone, 2-methoxy-1,4-naphthoquinone, methylhydroquinone, hydroquinone, hydroquinone monomethyl ether, and mono-tert-butylhydroquinone- 25- 201237557, 2,5-di-t-butylhydroquinone, p-benzoquinone, 2,5-diphenyl-p-benzoquinone, and 2,5-di-t-butyl-p-benzoquinone. Other antioxidants include citric acid 'phenol azine, and 2-butyl-4-hydroxyanisole. Examples of the antioxidants include, for example, IRGANOX 1〇1〇 and IRGANOX 1 03 5FF (all of which are manufactured by Ciba Specailty Chemicals Co., Ltd.). In the present invention, the component (F) is preferably 0.01 to 5 parts by weight, more preferably 0.1 to 2 parts by weight, based on 1 part by weight of the total of the components (A) to (D). The curable composition of the present invention may further contain a polymerization inhibitor as the component (G). The polymerization inhibitor may, for example, be a phenol-based polymerization inhibitor or a phenolazine-based polymerization inhibitor. Examples of the phenolic polymerization inhibitor include 2,2-methylene-bis(4·methyl-6-t-butylphenol) (BHT), catechol, picric acid, and tert-butylcatechol. , 2,6-t-butyl-p-cresol, and 4,4,-thiobis[ethylene(oxy)(carbonyl)(ethylene)]bis[2,6-bis(1,1-dimethyl) Base ethyl) phenol]. The phenolphthalein polymerization inhibitor may, for example, be a phenolphthalein or bismethylbenzylphenol oxazine, a 3,7-dioctylphenol, or a bis(α,α-dimethylbenzyl)phenol azine. A phenolic polymerization inhibitor such as hydrazine can also be used as an antioxidant. In the present invention, the total amount of the component (g) is preferably from 0.01 to 3 parts by weight, more preferably from 0.05 to 1 part by weight, per 100 parts by weight of the component (e) to the component (D). The curable composition of the present invention may contain (H) a plasticizer for the purpose of further improving the adhesiveness of the adhesive durability and the heat resistance of the cured body. Such a plasticizer is preferably an oligomer obtained by epoxidizing an unsaturated bond of a polybutadiene, and a commercial product may, for example, be BF-1 000 (made by Adeka) or PB-3600. (made by Daicel Industrial Chemical Co., Ltd.). In the curable composition of the present invention, the component (H) is preferably from 1 to 20 parts by weight, more preferably from 0.1 to 10 parts by weight, per 100 parts by weight of the total of the components (A) to (D). Share. The active energy ray-curable resin composition of the present invention may contain (I) an organic chelating agent for the purpose of further reducing the curing shrinkage ratio. The organic chelating agent may, for example, be an acrylic ruthenium, a styrene ruthenium, an acrylic/styrene copolymerization oxime, a fluororesin oxime, a polyethylene ruthenium, and a polypropylene ruthenium. In the case of the commercial product, for example, "PPW-5" (polypropylene sputum, manufactured by SEISHIN Co., Ltd.), and "PROPYLPAD 31" (polypropylene sputum, manufactured by MICROBODERERS INC.) can be mentioned. They may be used alone or in combination of two or more. A better organic hydrazine is a polypropylene sputum agent with less swelling. In the curable composition of the present invention, the component (I) is preferably 1 to 20 parts by weight, more preferably 0.1 to 1 part by weight based on 1 part by weight of the total of the components (A) to (D). 10 parts by weight. The curable composition of the present invention may further contain a decane coupling agent for the purpose of further improving the adhesion to the glass surface. -27- 201237557 The decane coupling agent may, for example, be r-chloropropyltrimethoxydecane, lutylmethoxydecane, vinyltrichlorodecane, vinyltriethoxy, vinyl-methoxymethoxyethoxy) Decane 'r-methacryl fluorenyltrimethoxydecane, r-propylene oxypropyltrimethoxydecane' (3,4-epoxycyclohexyl)ethyltrimethoxydecane, r-glycidoxy Trimethoxy decane, r-hydrothiopropyltrimethoxy decane, r-propyltriethoxy decane, n-dis-(aminoethyl)-r-aminopropyltriyl decane, ν Α-(Aminoethyl)-r-aminopropylmethyldimethoxy and ureidopropyltriethoxydecane, etc., preferably r-glycidoxytrimethoxydecane, r - propylene oxide propyl triethoxy decane (3,4-epoxycyclohexyl)ethyl trimethoxy decane, glycidoxymethyl diethoxy decane. These decane coupling agents may be used alone or in combination of two or more. In the curable composition of the present invention, the content of the decane coupling agent is preferably 〇1 to 1 part by weight based on 1 part by weight of the total of the components (A) to (D). However, since the decane coupling agent is easily released as an outgassing component after the curing of the curable composition, it is a component of the (A) component to the (D) component with respect to the curable composition not containing the decane couple. The total weight, the amount of the alkane coupling agent is 〇 by weight. In the present invention, the hardening of the active energy ray-curable resin composition can be obtained by hardening the active energy ray-curable resin composition of the present invention. The active energy ray-curable resin composition curing method of the present invention comprises the step of illuminating the energy ray of the active energy ray-curable resin composition of the present invention.矽 矽 氧 β β β β β β β β -28 -28 -28 -28 -28 - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - The wavelength of the active energy ray-curable resin composition of the present invention is not particularly limited, and is preferably from 100 to 420 nm, more preferably from 300 to 420 nm. The active energy ray-curable resin composition of the present invention is an adhesive composition which can be used as an adhesive for an adhesive, particularly an optical member. The member to be bonded by using the adhesive of the present invention may be, for example, a small component made of a metal or a metal-plated member or a plastic. The metal constituting the small part may, for example, be Mg, Zn, Ni, or A1, and the plastic may, for example, be a liquid crystal polymer (LCP), a cycloolefin polymer (COP), a cyclic olefin copolymer (COC), or a polyphenylene sulfide ( PPS), polyphenylene oxide (PPO), or a composite plastic material of glass fiber or carbon fiber mixed in the above plastic material. The plastic material is commercially available, and the PPS system is, for example, "Lighting PPS" manufactured by Idemitsu Co., Ltd., and "Torelina" manufactured by Toray Co., Ltd., and the liquid crystal polymer is, for example, "Siveras" manufactured by Toray Co., Ltd. and "Vectora" manufactured by Polyplastic Co., Ltd. Examples of the polyarylate include "U Polymer" manufactured by Unitika Co., Ltd., and examples of the cycloolefin polymer include "Zeonex" manufactured by Zeon Corporation of Japan, "Apel" manufactured by Mitsui Chemicals Co., Ltd., and "Arton" manufactured by JSR Corporation, and polycarbonate. For example, "Panlite" manufactured by Teijin Co., Ltd., etc., is not limited thereto. Moreover, the optical component to be bonded by using the adhesive of the present invention may be, for example, a member of a machine used in the field of equipment used for recording and reproducing a recording material such as a photodetector (PD) or a laser diode ( An optical module mounted on an optical component such as an optical component such as an LD), a lens, or a lens. Moreover, the optical pickup components differ depending on the requirements for the fixed accuracy of the components, and specifically, for example, a photodetector (PD), a laser diode (LD), and a collection -29-201237557 mirror (NAL) High-precision requirements such as high-precision parts, half-lens (beam splitter) (HM (PBS)), high-precision parts such as pitch, and high-precision requirements such as mirrors (RM) are moderate. Parts with low precision requirements for parts, objective lenses (OBL), and light collimator lenses. The curable composition of the present invention is a photocurable prepolymer having a polyfunctional acrylate compound, a diene-based or hydrogenated diene-based (meth) acrylate, and a reaction dilution having various functional groups (A) a acrylate, and a specific composition containing a photopolymerization initiator, so that it has a characteristic system: it can be hardened in a short time by irradiation with an active energy ray, and has a plastic member such as polyphenylene sulfide (PPS) or a metal member. High initial adhesion, durability test led by high temperature and high humidity test, showing high retention. It can suppress deformation during heat and deformation to heat and load to a minimum. Therefore, the movement of the hardened component adhered to the active energy ray-curable resin composition of the present invention to the maximum limit can be suppressed. The present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited thereto. Further, the following compounds were selected for each component in the composition of the tragic composition described in the examples and the comparative examples. (A) Polyfunctional acrylate compound (A-1) V#802 (manufactured by Osaka Organic Chemical Co., Ltd.) (A-2) Dipentaerythritol hexaacrylate ("DPE-6A" manufactured by Kyoeisha Chemical Co., Ltd.) (A-3) ) V #1000 (made by Osaka Organic Chemical Co., Ltd.) -30- 201237557 (A_4) V#Star-5 0 1 (made by Osaka Organic Chemical Co., Ltd.) (B) Photocurable prepolymer (B-1) terminal amine group A Acid ester acrylate modified polybutadiene ("TE-2000" manufactured by Sakamoto Soda Co., Ltd.) (B-2) Terminal urethane acrylate modified polybutadiene hydride ("Kawakawa Chemical Co., Ltd." -24") (C) Monofunctional or bifunctional (meth)acryloyloxyl monomer (acrylate monomer) (C-1) Tricyclodecane dimethanol acrylate ("Sanitary Chemical Co., Ltd." -1002") (C-2) Benzyl methacrylate ("Light Ester BZ" manufactured by Kyoeisha Chemical Co., Ltd.) (C-3) Isobornyl methacrylate ("Light from Kogyo Chemical Co., Ltd." Ester IB-X j ) (C-4) 2-Hydroxyethyl methacrylate. (Light Ester HO, manufactured by Kyoeisha Chemical Co., Ltd.) (C-5) 2-Methyl propylene oxirane Succinic acid (Light Ester, manufactured by Kyoeisha Chemical Co., Ltd.) HO-MS") (D) Photopolymerization initiator (Dl) 1-hydroxycyclohexyl phenyl ketone ("IRGACURE 184" manufactured by Ciba Specialty Chemicals Co., Ltd.) (D-2) bis (2,4,6-trimethyl) Benzobenzyl)-phenylphosphine oxide ("IRGACURE 819" manufactured by Ciba Specialty Chemicals Co., Ltd.) (E) Inorganic chelating agent (E-1) glass enamel ("CF0023-05C", manufactured by Frit Corporation, Japan) - 31 - 201237557 (E_2) Nicotinated silica sand ("TG308F" manufactured by Cabot Specialty Chemicals Co., Ltd.) (F) Antioxidant (Fl) ("IRGANOX1010" manufactured by Ciba Specialty Chemicals Co., Ltd.) (F-2) (Ciba Specialty Chemicals "IRGANOX1 035") (G) Polymerization inhibitor (Gl) 2,2-methylene-bis(4-methyl-6-tert-butylphenol) ("BHT" manufactured by Kanto Chemical Co., Ltd.) (H) Plasticizer (H-1) An oligomer obtained by epoxidizing an unsaturated bond of polybutadiene ("BF-1000" manufactured by Adeka Co., Ltd.). (1) Component: organic chelating agent (1-1) polyacrylic acid The sputum sputum ("ppw-5" manufactured by Seishin Co., Ltd.) The various physical properties of the cured product of the active energy ray-curable resin composition were measured as follows. [Photohardening conditions] For the active energy source, 'Using a point camera ("LC-8" manufactured by Hamamatsu ph〇t〇nix Co., Ltd.), using an ultraviolet illuminometer "UIT_1〇1" manufactured by USHI Co., Ltd. The condition of 250 mW/cm2 was irradiated for 12 seconds to harden it. [Measurement of angle change] (1) Preparation of sample for measuring angle change -32- 201237557 As shown in Fig. 1, the aluminum plate 2 is vertically fixed by a gap of 3 ΟΟμιη, so that 10 (fixed side) xl.0 (thick SUS 20 (length) mm of SUS plate 4 (SUS 304, 1.5 g) is placed on the table 5 at a 90-degree angle for the aluminum plate. In order to fix the aluminum plate and the SUS plate, the active energy ray-curable resin composition 1 (0.002 5 cc) of the present invention was applied to the central portion of the fixed side using a dispenser adjuster (ML-606, manufactured by Musashi Engineering Co., Ltd.). Immediately after the application, the UV irradiator 3 was used from a distance of 45 degrees and 20 mm, and UV light of 250 mW/cm 2 was irradiated for 12 seconds to be fixed. Then, the table 5 was removed and used as an evaluation sample. (2) Measurement of the angle change The deformation of the adhesive portion at the time of heat was monitored from the angle change using a tilt sensor (MTS-T20 manufactured by NISSHO ELECTRONICS). As shown in Fig. 2, the angle change measurement sample described above was fixed in a thermostatic chamber (MC-7 1 1 T manufactured by ESPEC). The beam of the tilt sensor was reflected to the SU S plate, which was monitorable. 'Adjust the position of the tilt sensor. The temperature in the bath was maintained at 25 ° C for 30 minutes to adjust the temperature. The amount of change in angle after the temperature adjustment was measured and it was 〇. The temperature cycle is 2 5 . (: Hold for 1 hour, then raise the temperature from 25C to 60C at 30 minutes, 60 °C and hold at 60 °C for 1 hour 'further' to increase the temperature from 60 °C to 80 °C by 30 minutes. After 8 0 C, hold at 80 ° C for 1 hour. Reduce the temperature to 2 5 C from 80 ° C at 30 ° C. Take 1 cycle. Change the temperature in the bath to 25 ° C, 60 by this temperature cycle. °C, 80 ° C. In the first cycle, the amount of change in the angle of 33 · 201237557 after 6 〇 and 80 ° C for 1 hour, and 2 5 after 1 cycle. In addition, the amount of change in the angle in the table depends on the minute. [Adhesion test] The adhesion test is measured by the debonding strength. As shown in Fig. 3, in PPS (polyphenylene sulfide, light-emitting PPS NT7790 (lighting) Company system)), the honing of the end face honing (Engineering test Service company, A5052P, vertical lOmmx horizontal lOmmx height 2mm), using the dispenser adjuster (Mu Zha Engineering ML-606) and using the cylinder coating 0.002 5cc The active energy ray-curable resin composition was then used, and a UV illuminator (manufactured by Hamamatsu Photonix Co., Ltd., LC6) was used at a distance of 20 mm. A UV illuminometer (Ushiro Electric Co., Ltd., UIT-101) was used to irradiate UV light of 250 mW/cm2 for 12 seconds to fix it. In this way, an adhesive test piece was produced. An detachment tester (AGS manufactured by Shimadzu Corporation) was used. -500D), from the side where the crystal grain is not fixed, for the area of 4 mm in diameter, the detachment strength is measured at an detaching speed of 10 mm/min. The intensity of the non-floating state is indicated by the intensity of 40 N or more. PPS plastic pellets (longitudinal lOmmx horizontal lOmmx height 2 mm) and PPS plates, and wafers and nameplates (manufactured by Engineering Test Service, A505 2P) were used for the end face grinding. (Examples 1 to 7 and Comparative Examples 1 to 2) The resin composition was prepared by mixing the materials shown in Tables 1 and 2 to the materials shown in Tables 1 and 2. The obtained composition was measured for adhesion strength, moisture resistance, heat resistance, and heat resistance. Impact evaluation test. The results are shown in Tables 1 and 2. In addition, the content is in parts by weight -34 - 201237557. The moisture resistance test is performed using LH21-21M (Nagano Science) at 65 ° C / 95%. RH-3 3 was carried out under 6 hours. No cracks or cracks at the ends were observed. When the adhesive strength was 40 N or more, the heat resistance was carried out using LC-1 12 (manufactured by Espec Co., Ltd.) at 80 ° C. No floating or cracking was observed, and the tortoise strength at the end was 40 N or more. It is awkward. The thermal shock evaluation test was carried out using TSA-41L (Espec) at -40 ° C (30 ° C) / 85 ° C (30 min) for 1 〇〇 cycle to observe floatation, or cracking, end The crack is cracked and the adhesive strength is 40N. The company is made of float, 〇-3 3 6 small crack, sticky). None of the above - 35 - 201237557 [Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 (A) Polyfunctional acrylate compound A-1 6.25 7.5 20 7.5 A- 2 7.5 A-3 20 A-4 20 (B) Photocurable prepolymer B-1 100 100 100 B-2 100 100 100 100 (C) Acrylate monomer C-1 7.5 25 25 23.3 7.5 23.3 23.3 C -2 25 25 25 83.3 25 83.3 83.3 C-3 25 25 25 33.3 25 33.3 33.3 C-4 25 25 25 6.67 25 6.67 6.67 C-5 12.5 12.5 12.5 16.7 12.5 16.7 16.7 (D) Polymerization initiator D-1 4.5 4.5 4.5 9.33 4.5 9.33 9.33 D-2 0.5 0.5 0.5 0.5 (E 怃 塡 E E-1 225 380 380 487 380 487 487 E-2 2.5 2.5 2.5 6.7 2.5 6.7 6.7 (F) Antioxidant F-1 1 1 1 F-2 1.25 1.25 1.25 1.25 (G) Polymerization inhibitor G-1 0.25 0.25 0.25 0.67 0.25 0.67 0.67 (H-plasticizer H-1 66.7 66.7 66.7 (I) Organic chelating agent 1-1 26.7 26.7 26.7 Adhesion (PPS/AI) Ο Ο Ο 〇〇Ο 〇 Adhesiveness (PPS/PPS) ο 〇Ο Ο Ο Ο 〇 Adhesiveness (AI/AI) ο Ο Ο Ο Ο Ο 〇 Moisture resistance ο 〇ο耐热 Heat resistance ο 〇〇Ο Ο 耐热 Thermal shock resistance ο 0 Ο 〇Ο 〇Ο Angle change amount (first time) 25°C 0 0 0 0 0 0 0 60°C ~20, 5, ...0' - 20, 5, ~20, ~20, 80 °C ~30, ~15, ~15#~30, ~15, ~30, ~30, angle change amount 25 °C ~15, ~5' ~5, ~ 15#~15, -15, -36- 201237557 [Table 2] Comparative Example 1 Comparative Example 2 (A) Polyfunctional acrylate compound A-1 A-2 A-3 A-4 (B) Photocurability pre- Polymer B-1 100 B-2 100 (C) Acrylate monomer C-1 7.5 23 C-2 25 83 C-3 25 33 C-4 25 6.7 C-5 12.5 16.7 (D) Polymerization initiator D -1 4.5 9.3 D-2 0.5 (E) Inorganic chelating agent E-1 225 487 E-2 2.5 6.7 (F) Antioxidant F-1 1 F-2 1.25 (G) Polymerization inhibitor G-1 0.25 0.67 ( H River Plastic Agent H-1 66.7 (I) Organic Tanning Agent 1-1 26.7 Adhesion (PPS/AI) Adhesiveness (PPS/PPS) Adhesiveness (AI/AI) 〇〇 Moisture Resistance 〇 〇 heat resistance 〇〇 thermal shock resistance 〇〇 angle change (initial) 25 ° C 0 0 60 ° C more than 3 (Τ more than 30 ' 80 ° C more than 30 ' super 30°C. Angle change amount 25°C, more than 30′, more than 30′ The curable composition of the present invention is an optical device such as an optical component such as an LD, a photodetector, a lens or a lens, or an optical component such as a lens. The module and the like are fixed with a high fixed precision, so that it can be used as an adhesive for the optical device group -37-201237557. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing a device for measuring deformation of a heat-sensitive adhesive portion of a curable composition of the present invention from an angle change. Fig. 2 is a view showing the change of the angle of the fixture by the tilt sensor after photohardening the curable composition of the present invention. Fig. 3 is a schematic view showing an detachment strength test of an adhesive structure in which the active energy ray-curable resin composition of the present invention is applied. [Explanation of main component symbols] 1 : Active energy ray-curable resin composition 2 : Aluminum plate 3 : UV illuminator 4 : SUS plate 5 : Seat 6 : Tilt sensor 7 : Active energy ray-curable resin composition 8 : Nameplate 9 : PPS board -38-

Claims (1)

201237557 七、申請專利範圍： 1 · 一種活性能量線硬化性樹脂組成物，其特徵係含有 下述（A)成分〜（D)成分： (A) 由（a 1)以甘油衍生物及醚骨架作爲鍵結官能基之直線狀 或分枝狀之其多量體、 (a2)以三羥甲基丙烷衍生物及醚骨架作爲鍵結官能基之直 線狀或分枝狀之其多量體、 (a3)以季戊四醇衍生物之單體及醚骨架作爲鍵結官能基之 直線狀或分枝狀之其多量體、以及 (a4)含有醚鍵或酯鍵，且於4以上之末端配置（甲基）丙烯 醯基之樹木狀分子化合物 所構成之群中選出的於分子中含有4個以上之（甲基）丙烯 醯基的多官能丙烯酸酯化合物、 (B) 光硬化性預聚物、 (C) 單官能或2官能之含（甲基）丙烯醯基單體、及 (D) 光聚合起始劑。 2.如申請專利範圍第1項之活性能量線硬化性樹脂組 成物’其中相對於（A)成分〜（D)成分之重量，（A)成分爲 0 · 0 1〜2 5重量％。 3 .如申請專利範圍第1或2項之活性能量線硬化性樹 脂組成物，其係用以貼合光學零件之黏著劑。 4.如申請專利範圍第1或2項之活性能量線硬化性樹 脂組成物，其係光拾取裝置組裝用之黏著劑。 5 . —種黏著構造體’其係以如申請專利範圍第1或2 -39- 201237557 項之活性能量線硬化性樹脂組成物貼合。 6 . —種光學零件，其係使用如申請專利範圍第3項之 活性能量線硬化性樹脂組成物而貼合。 7. —種光拾取裝置，其係使用如申請專利範圍第4項 之活性能量線硬化性樹脂組成物而組裝。 -40-201237557 VII. Patent application scope: 1 · An active energy ray-curable resin composition characterized by containing the following components (A) to (D): (A) glycerin derivative and ether skeleton from (a1) a linear or branched multi-component of a bonding functional group, (a2) a linear or branched multi-component with a trimethylolpropane derivative and an ether skeleton as a bonding functional group, (a3) a monomer or an ether skeleton of a pentaerythritol derivative as a linear or branched multi-component of a bonding functional group, and (a4) an ether bond or an ester bond, and is disposed at a terminal of 4 or more (methyl) a polyfunctional acrylate compound containing four or more (meth) acrylonitrile groups in a molecule selected from the group consisting of a arsenic-based dendrimer compound, (B) a photocurable prepolymer, and (C) A monofunctional or bifunctional (meth)acrylonitrile-containing monomer, and (D) a photopolymerization initiator. 2. The active energy ray-curable resin composition of the first aspect of the invention, wherein the component (A) is from 0. 0 1 to 25% by weight based on the weight of the components (A) to (D). 3. The active energy ray-curable resin composition according to claim 1 or 2, which is an adhesive for bonding optical parts. 4. The active energy ray-curable resin composition according to claim 1 or 2, which is an adhesive for assembling an optical pickup device. An adhesive structure is bonded to an active energy ray-curable resin composition as disclosed in claim 1 or 2 to 39 to 201237557. An optical component which is bonded using an active energy ray-curable resin composition as in claim 3 of the patent application. 7. An optical pickup device assembled by using an active energy ray-curable resin composition as disclosed in claim 4 of the patent application. -40-