200940588 九、發明說明 【發明所屬之技術領域】 本發明係有關硬化性組成物，特別是有關適用於筆記 型電腦、電視、手機等之裝置之密封劑、黏著劑之硬化性 組成物。更詳細者，本發明係有關藉由滴入方式（ODF ) 所製造之適於液晶顯示裝置之密封的硬化性組成物。 〇 【先前技術】 近年來，筆記型電腦、電視等之裝置中使用液晶顯示 裝置，朝液晶顯示裝置之大型化發展。作爲此等液晶顯示 裝置之製造方法者，被揭示有生產性高、且高價之液晶材 料的利用效率極高之滴入方式（ODF) (JP63- 1 79323A、 JP 1 0-239694A)。具體而言，於單面基板上藉由稱爲主密 封之液晶密封用之密封劑進行塗佈成形成堤防狀框，使該 密封劑於未硬化狀態下，於框內側滴入液晶組成物後，貼 © 合另一面之基板，藉由硬化密封劑，製造液晶顯示裝置之 方式。 ，惟，滴入方式中，其未硬化之主密封與液晶組成物進 行接觸。因此，使用先行技術之熱硬化型密封劑，則硬化 所需時間較長，故密封劑成份溶出於液晶組成物中等，而 使液晶材料、周邊構件之定向膜等被污染，顯示裝置之顯 示品質明顯降低，故不太實用化。 因此，爲儘可能使未硬化之主密封與液晶組成物之接 觸時間儘量縮短，故揭示一種光硬化型之主密封（JP1- -5- 200940588 243029A)。惟，滴入方式中，因爲液晶顯示裝置之TFT 基板之金屬配線部份、彩色濾光片基板之黑色矩陣部份的 存在，故未照到光的遮光部份其密封劑成未硬化而以未硬 化部之殘留，因此，仍存在劣化液晶顯示裝置之顯示品質 之問題點。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a curable composition, and particularly to a sealant for an apparatus for use in a notebook computer, a television, a mobile phone, or the like, and a hardenable composition of an adhesive. More specifically, the present invention relates to a curable composition suitable for sealing of a liquid crystal display device manufactured by a dropping method (ODF).先前 [Prior Art] In recent years, liquid crystal display devices have been used in devices such as notebook computers and televisions, and the size of liquid crystal display devices has increased. As a method of manufacturing such a liquid crystal display device, an instillation method (ODF) (JP 63- 1 79323 A, JP 1 0-239694 A) in which the productivity of the liquid crystal material having high productivity and high cost is extremely high is disclosed. Specifically, the single-sided substrate is coated with a sealant for liquid crystal sealing called a main seal to form a bank frame, and the sealant is dropped into the liquid crystal composition on the inside of the frame in an uncured state. , a method of manufacturing a liquid crystal display device by hardening a sealant. However, in the dropping mode, the unhardened main seal is in contact with the liquid crystal composition. Therefore, the use of the thermosetting sealant of the prior art requires a long period of hardening, so that the sealant component is dissolved in the liquid crystal composition, and the alignment film of the liquid crystal material and the peripheral member is contaminated, and the display quality of the display device is exhibited. Significantly reduced, so it is not practical. Therefore, in order to minimize the contact time between the uncured main seal and the liquid crystal composition as much as possible, a photocurable main seal (JP1- -5-200940588 243029A) is disclosed. However, in the dropping method, since the metal wiring portion of the TFT substrate of the liquid crystal display device and the black matrix portion of the color filter substrate exist, the sealing agent is not hardened due to the light-shielding portion not irradiated with light. Since the uncured portion remains, there is still a problem that the display quality of the liquid crystal display device is deteriorated.
熱硬化法、光硬化法各自有其問題點，因此作爲該解 決對策者，提出許多關於倂用光硬化與熱硬化之二階段硬 _ 化型之主密封（JP58-105124A 、 JP1-266510A 、 JP7· Q 13175A、JP8-328026A、JP9-5759A)。使用經由該光與熱 之二階段硬化型之主密封之方法，其特徵爲首先，對挾夾 於二片玻璃基板之密封劑照射光後，進行第1階段之硬化 後，加熱之後進行第2階段的熱硬化。 惟，載於JP8-328026A之主密封其主成份爲丙烯酸酯 或甲基丙烯酸酯，以自由基聚合機序進行聚合，故對於玻 璃之黏著強度，特別是於高溫高濕之雰圍下，大幅降低黏 著強度，相較於熱硬化型，有信賴性之問題點。因此，經 © 由光與熱之二階段硬化型爲直接倂用作爲主成份之（甲基 )丙烯酸酯與環氧樹脂之密封劑，經由JP2001-133794A、 JP2004-37937A、 JP2004-61925A、 JP5-295087A 等被揭示 〇 惟’如上述之主密封係於光硬化後所進行之熱硬化製 程中，會有因爲密封劑黏度的降低而造成密封爆裂或密封 劑成份溶出於液晶中等問題。因此，用於環氧樹脂之熱硬 化劑，被要求低溫硬化性、速硬化性之特性。 -6- 200940588 滿足上述要求特性之硬化劑中，有某種聚胺系硬化劑 、某種咪唑系硬化劑等。惟，使用聚胺系硬化劑之硬化物 ，因爲其玻璃轉移點皆低至loot以下，因此無法保持實 用強度。又，一般咪唑系硬化劑中，經由陰部其密封劑之 光硬化性樹脂之未反應個處中，出現液晶污染之問題點。 爲了改良此陰部硬化性，考慮添加（甲基）丙烯酸酯之熱 ' 啓始劑，但使熱啓始劑與液晶組成物接觸則污損液晶組成 Φ 物，且降低硬化性樹脂組成物之保存穩定性。 【發明內容】 本發明之目的係爲解決上述之先行技術問題，提供一 種特別具有良好的保存穩定性、塗佈作業性，於短時間內 可製成高品質之硬化物，適用於藉由滴入方式所製造之液 晶顯示裝置之封閉用密封劑之二階段硬化型之硬化性樹脂 組成物。 〇 爲解決該課題，本發明第1形態係含有（A)l分子 中至少具有1個（甲基）丙烯基之（甲基）丙烯酸化合物 、（B)光啓始劑、（C) 1分子中至少具有1個縮水甘油 基之環氧樹脂、及（D)由胺烷基咪唑化合物所成之硬化 劑爲必須成份之硬化性樹脂組成物。 本發明之第2形態係其（D )成份之胺烷基咪唑化合 物爲一般式（1)所示之胺烷基咪唑化合物之該第1形態 之硬化性樹脂組成物。 -7- (1) 200940588Since each of the thermal curing method and the photo-curing method has its problems, many main seals for the two-stage hardening type of the photohardening and the thermal curing have been proposed as the countermeasure (JP58-105124A, JP1-266510A, JP7). · Q 13175A, JP8-328026A, JP9-5759A). A method of using a two-stage hardening type main seal by the light and heat is characterized in that first, after the sealing agent which is sandwiched between the two glass substrates is irradiated with light, the first stage is hardened, and then heated and then subjected to the second step. Thermal hardening of the stage. However, the main seal of JP8-328026A has a main component of acrylate or methacrylate, which is polymerized by a free radical polymerization sequence, so that the adhesion strength of the glass, especially in a high-temperature and high-humidity atmosphere, is greatly reduced. Adhesive strength is a problem of reliability compared to the thermosetting type. Therefore, the sealant of (meth) acrylate and epoxy resin which is used as a main component by the two-stage hardening type of light and heat is passed through JP2001-133794A, JP2004-37937A, JP2004-61925A, JP5- 295087A et al. have revealed that the above-mentioned main seal is a heat-hardening process performed after photohardening, and there is a problem that the seal bursts or the sealant component dissolves out of the liquid crystal due to a decrease in the viscosity of the sealant. Therefore, the thermosetting agent for epoxy resins is required to have properties of low-temperature hardening property and quick-curing property. -6- 200940588 Among the hardeners that satisfy the above requirements, there are some polyamine-based curing agents and some imidazole-based curing agents. However, the hardened material of the polyamine-based hardener is used because the glass transition point is as low as below the loot, so that the practical strength cannot be maintained. Further, in the general imidazole-based curing agent, the problem of liquid crystal contamination occurs in the unreacted portion of the photocurable resin which is a sealant of the genital portion. In order to improve the sclerosing degree of the genital area, it is considered to add a heat initiator of (meth) acrylate, but the contact of the heat starter with the liquid crystal composition contaminates the liquid crystal composition Φ and lowers the preservation of the curable resin composition. stability. SUMMARY OF THE INVENTION The object of the present invention is to solve the above-mentioned prior art problems and to provide a cured product which has good storage stability and coating workability and can be made into a high quality in a short time, and is suitable for use in dripping. A two-stage curing type curable resin composition of a sealing agent for sealing a liquid crystal display device manufactured by the method. In order to solve this problem, the first aspect of the present invention includes (A) a (meth)acrylic compound having at least one (meth)acryl group in the molecule, (B) a photoinitiator, and (C) 1 molecule. An epoxy resin having at least one glycidyl group and (D) a curing agent composed of an amine alkyl imidazole compound is an essential component of a curable resin composition. According to a second aspect of the invention, the aminoalkylimidazole compound of the component (D) is a curable resin composition of the first aspect of the amine alkylimidazole compound represented by the general formula (1). -7- (1) 200940588
(其中，R爲氫原子或一價烴基、1〜113各自獨立地 -爲氫原子或具有取代基亦可之烴基，η爲2或3) 。 〇 本發明之第3形態係其（D)成份以使胺烷基咪唑化 合物（dl)，預先與具有環狀構造之二胺化合物（d2)、 尿素（d3)、及分子內具有平均2個縮水甘油基之環氧樹 脂（d4)共同進行加熱處理之處理物之形態存在之第1或 第2形態之硬化性樹脂組成物。 本發明第4形態係其（D )成份爲每（A )成份〜（C )成份之合計100重量份存在1〜20重量份之任意第1〜(wherein R is a hydrogen atom or a monovalent hydrocarbon group, and 1 to 113 are each independently - a hydrogen atom or a hydrocarbon group which may have a substituent, and η is 2 or 3). The third aspect of the present invention is the component (D), wherein the amine alkyl imidazole compound (dl) has an average of two diamine compounds (d2), urea (d3), and intramolecular groups having a cyclic structure. The curable resin composition of the first or second aspect in which the glycidyl group-containing epoxy resin (d4) is subjected to a heat treatment together. According to a fourth aspect of the present invention, the component (D) is any 1 to 20 parts by weight per 100 parts by weight of each of the components (A) to (C).
第3形態之硬化性樹脂組成物。 Q 本發明第5形態係其（A )成份係使1分子中至少具 有2個縮水甘油基之環氧樹脂與（甲基）丙烯酸進行部份 酯化反應後取得部份酯化環氧基（甲基）丙烯酸化合物之 該第1〜第4形態之硬化性樹脂組成物。 本發明第6形態係由第1〜第5之任一形態之硬化性 樹脂組成物所成之用於貼合經由滴入方式之液晶顯示裝置 之密封劑。 本發明中，「（甲基）丙烯酸」係代表如公知之「丙 -8 - 200940588 烯酸及/或甲基丙烯酸」之意。「（甲基）丙烯酸化合物 」、「（甲基）丙烯酸酯」等亦代表與「（甲基）」之意 義內容爲相同。 本發明硬化性樹脂組成物係使用由胺烷基咪唑化合物 所成之熱硬化劑後，保持咪唑類特有的低溫速硬化性與耐 熱性，同時藉由經與胺烷基之活化氫部位之反應的（甲基 ' )丙烯基之硬化，可取得陰部硬化性良好之光•熱硬化性 φ 樹脂組成物。又，使用本發明硬化性樹脂組成物作爲貼合 液晶顯示裝置之密封劑後，具有液晶污染性低、對於基板 之塗佈作業性良好，理想的保存穩定性之特徵，更作成具 有高度黏著力之密封劑。將該密封劑適用於滴入方式，可 製造提昇顯示品質、收率、生產性之液晶顯示裝置。 本發明之（D)成份係藉由與（A)成份、（C)成份 之組合後，並非僅作爲（C )成份之環氧硬化劑之作用， 其存在於其構造中之烷基胺基，藉由與經由光照射未硬化 〇 之陰部所具有之（A)成份進行反應，將此硬化，其結果 未硬化之（A)成份未溶出於液晶中溶解析出，因此可製 造高品質之液晶顯示裝置。 【實施方式】 [發明實施之最佳形態] 本發明所使用之（A) 1分子中至少具有1個（甲基 )丙烯基之丙烯酸化合物，只要於分子末端或側鏈具有（ 甲基）丙烯基之自由基聚合性單體、低聚物即可，並未特 -9- 200940588 別限定’如：聚酯（甲基）丙烯酸酯系、環氧基（甲基） 丙烯酸酯系、胺基甲酸乙酯（甲基）丙烯酸酯系、聚醚（ 甲基）丙烯酸酯系、聚丁二烯（甲基）丙烯酸酯系、聚矽 氧（甲基）丙烯酸酯系等之各種聚合性單體、低聚物等化 合物之例。 其中，作爲聚酯（甲基）丙烯酸酯系低聚物者，如： 將多價羧酸與多價醇經縮合取得之兩末端具有羥基之聚酯 ^ 低聚物之羥基以（甲基）丙烯酸藉由酯化，或將於多價羧 0 酸加成烯化氧後取得之低聚物之末端羥基以（甲基）丙烯 酸藉由酯化後可取得。環氧基（甲基）丙烯酸酯系低聚物 係如：使較低分子量之雙酚型環氧樹脂或漆用酚醛型環氧 樹脂之環氧乙烷環，與（甲基）丙烯酸進行反應後，藉由 酯鍵可取得（甲基）丙烯酸改性之化合物。 另外，亦可使用使該環氧基（甲基）丙烯酸酯系低聚 物之一部份經由二鹼性羧酸酐進行改性的羧基改性型環氧 基（甲基）丙烯酸酯低聚物。胺基甲酸乙酯（甲基）丙烯 © 酸酯系低聚物，係如：可將藉由聚醚聚醇或聚酯聚醇與聚 異氰酸酯之反應取得之聚胺基甲酸乙酯低聚物，以（甲基 )丙烯酸經由酯化後取得，聚醇（甲基）丙烯酸酯系低聚 物，可使聚醚聚醇之羥基以（甲基）丙烯酸經由酯化後取 得。 此等低聚物係因應光硬化性材料之用途進行適當選擇 。如：被要求光硬化性、硬度、耐熱性、電氣特性等之領 域中，主要使用環氧基（甲基）丙烯酸化合物，被要求柔 -10- 200940588 軟性、強韌性、耐磨損性、耐藥性等之領域中，主要使用 胺基甲酸乙酯（甲基）丙烯酸化合物。又，被要求低黏度 、掌控性、低價格等之領域中，主要使用聚酯（甲基）丙 烯酸化合物、聚醚（甲基）丙烯酸化合物，被要求鹼顯像 性、硬度、耐熱性等之阻焊劑等領域中，主要使用羧基改 性型之環氧基（甲基）丙烯酸酯系化合物。 作爲光聚合性低聚物者，其他有：於聚丁二烯低聚物 ❹ 之側鏈中，具有（甲基）丙烯基之疏水性高之聚丁二烯（ 甲基）丙烯酸酯系低聚物，於主鏈具有聚矽氧烷鍵之聚矽 氧（甲基）丙烯酸酯系低聚物，使於小分子內具有大量反 應性基之胺基塑料樹脂進行改性之胺基塑料樹脂（甲基） 丙烯酸酯系低聚物等，分別之特性被利用於可發揮領域中 。該光聚合性低聚物可單獨使用1種，亦可組合2種以上 使用。該光聚合性低聚物其黏度均較高，且伴隨分子量之 增加，其黏度亦提昇。因此，單獨使該光聚合性低聚物進 〇 行光硬化後，未充分促進交聯反應時，反而使交聯密度變 高，使硬化物變脆之情況產生。因此，本發明中，爲調整 黏度、促進光交聯反應、調整硬化物之交聯密度等，可倂 用單官能性、多官能性之光聚合性單體。 本發明中，作爲（A)成份者，使用於1分子中至少 具有2個縮水甘油基之環氧樹脂之一部份縮水甘油基與使 (甲基）丙烯酸進行反應取得之部份酯化環氧基（甲基） 丙烯酸化合物爲有效者。此乃，例如使用本發明硬化性組 成物作爲液晶密封劑使用時，由於極力縮小無法光硬化之 -11 - 200940588 陰部未反應之（甲基）丙烯酸樹脂，故亦爲有效者。 作爲該酯化反應所使用之環氧樹脂者，只要至少具有 2個縮水甘油基之環氧樹脂即可，並未特別限定，此等中 又以使用雙酚A型、F型、或漆用酚醛型環氧樹脂者宜。 考量反應時之使用、容易性等，又以室溫下液狀者爲更佳 使用者。此等環氧樹脂可單獨使用，亦可倂用2種以上。 部份酯化環氧基（甲基）丙烯樹脂係可於該分子中至 少具有2個環氧基之環氧樹脂中，對於其環氧樹脂之縮水 甘油基之當量而言，任意選擇（甲基）丙烯酸之當量比， 進行酯化反應後取得。本發明中使該酯化率爲20〜80當 量％者宜。作爲部份酯化環氧基（甲基）丙烯酸樹脂之合 成方法者，於特定當量比下混合環氧基樹脂與（甲基）丙 烯酸，添加酯化觸媒（如：苄基二甲胺、三乙胺、苄基三 甲銨氯化物、三苯膦、三苯睇等）與聚合防止劑（如：甲 匯、氫醌、甲基氫醌、吩噻嗪、二丁基羥甲苯等），進行 反應》 另外，如··以當量比1 : 1使2官能之環氧樹脂與（ 甲基）丙烯酸進行酯化反應後，一般生成50當量％之部份 酯化環氧基（甲基）丙烯酸樹脂與25當量％未反應之2官 能環氧樹脂、25當量％之2官能（甲基）丙烯酸樹脂（完 全酯化物）。本發明中區分上述之三種成份，顯示其配合 比例。 本發明如上述，合成部份酯化環氧基（甲基）丙烯酸 樹脂時’於其製程中，含有任意量之完全酯化物，而此生 -12- 200940588 成物之量被加算於（A)成份中。此部份酯化環氧基（甲 基）丙烯酸樹脂之配合量，於（A)成份中配合50重量％ 以上，較佳者爲65重量％以上，可有效發揮其效果。又， 選擇與環氧樹脂反應之（甲基）丙烯酸之當量比、觸媒等 後，亦可控制所合成之該3種生成物之生成比例。 本發明所使用之（B)光啓始劑可使用先行技術公知 之自由基產生型之光聚合啓始劑。具體而言，可使用二苯 Q 甲酮、2，2-二乙氧基苯乙酮、苄基、苯甲醯異丙醚、苯甲 醯二甲基縮酮、1-羥基環己基苯酮、噻噸酮苄基二甲基縮 酮、1-羥基環己基苯酮、二乙基噻噸酮、2-二乙基蒽、2-羥基-2-甲基苯丙酮、2-甲基-[4-(甲基硫代）苯基]-2-嗎 啉-1-丙烷、2,4,6-三甲基苯甲醯二苯膦氧化物等。特別適 用下述一般式（3)所示之含羥基之苯甲醯化合物與異氰 酸酯化合物藉由胺基甲酸乙酯化反應所得之自由基產生型 光聚合啓始劑。此等光硬化時之外氣產生量少，對於液晶 〇 材料之污染性極低，因此極適用於本發明。A curable resin composition of the third aspect. In the fifth aspect of the present invention, the component (A) is obtained by partially esterifying an epoxy resin having at least two glycidyl groups in one molecule with (meth)acrylic acid to obtain a partially esterified epoxy group ( The curable resin composition of the first to fourth aspects of the methyl methacrylate compound. According to a sixth aspect of the present invention, there is provided a sealant for bonding a liquid crystal display device via a dropping method, comprising a curable resin composition according to any one of the first to fifth aspects. In the present invention, "(meth)acrylic acid" means a known "C-8-200940588 enoic acid and/or methacrylic acid". "(Meth)acrylic acid compound", "(meth)acrylate", etc. are also the same as the meaning of "(meth)". The curable resin composition of the present invention retains the low-temperature fast-curing property and heat resistance peculiar to the imidazole by using a thermosetting agent composed of an amine alkylimidazole compound, and at the same time, reacts with an activated hydrogen moiety of the amine alkyl group. The (methyl') propylene group is cured to obtain a light having a good sclerosing property and a thermosetting φ resin composition. Further, when the curable resin composition of the present invention is used as a sealing agent for a liquid crystal display device, it has low liquid crystal contamination, good coating workability for a substrate, and excellent storage stability characteristics, and is highly adhesive. Sealant. The sealant is applied to a dropping method, and a liquid crystal display device which improves display quality, yield, and productivity can be manufactured. The component (D) of the present invention is an alkylamine group present in the structure thereof by the combination of the component (A) and the component (C), not only as an epoxy hardener of the component (C). This is hardened by reacting with the component (A) which is contained in the genital portion of the unhardened enamel by light irradiation, and as a result, the component (A) which is not hardened is dissolved in the liquid crystal and is dissolved, so that high-quality liquid crystal can be produced. Display device. [Embodiment] [Best Mode for Carrying Out the Invention] (A) An acrylic compound having at least one (meth)acryl group in one molecule of the present invention, as long as it has (meth) propylene at a molecular terminal or a side chain. The radical polymerizable monomer or oligomer can be used, and it is not limited to -9 to 200940588, such as polyester (meth) acrylate, epoxy (meth) acrylate, or amine. Various polymerizable monomers such as ethyl formate (meth) acrylate, polyether (meth) acrylate, polybutadiene (meth) acrylate, or polyoxyl (meth) acrylate Examples of compounds such as oligomers. Among them, as a polyester (meth) acrylate type oligomer, for example, a hydroxy group of a polyester having an hydroxy group at both ends thereof obtained by condensing a polyvalent carboxylic acid and a polyvalent alcohol is (meth) Acrylic acid can be obtained by esterification or esterification of a terminal hydroxyl group of an oligomer obtained by adding an alkylene oxide to a polyvalent carboxylic acid to (meth)acrylic acid. The epoxy group (meth) acrylate type oligomer is, for example, a reaction of a lower molecular weight bisphenol type epoxy resin or a phenolic epoxy resin epoxide ring with (meth)acrylic acid. Thereafter, a (meth)acrylic modified compound can be obtained by an ester bond. Further, a carboxyl group-modified epoxy (meth) acrylate oligomer in which a part of the epoxy (meth) acrylate oligomer is modified via a dibasic carboxylic anhydride can also be used. . An urethane (meth) propylene acrylate oligomer, such as a polyurethane oligomer which can be obtained by reacting a polyether polyol or a polyester polyol with a polyisocyanate The (meth)acrylic acid oligomer is obtained by esterification of (meth)acrylic acid, and the hydroxyl group of the polyether polyol can be obtained by esterification of (meth)acrylic acid. These oligomers are appropriately selected depending on the use of the photocurable material. For example, in the field where photohardenability, hardness, heat resistance, electrical properties, etc. are required, epoxy-based (meth)acrylic compounds are mainly used, and softness is required. -10-200940588 Softness, toughness, abrasion resistance, and resistance In the field of medicinal properties and the like, an ethyl urethane (meth) acrylate compound is mainly used. Further, in the fields where low viscosity, controllability, and low price are required, polyester (meth)acrylic compounds and polyether (meth)acrylic compounds are mainly used, and alkali developability, hardness, heat resistance, and the like are required. In the field of solder resists and the like, a carboxyl group-modified epoxy group (meth) acrylate compound is mainly used. Other examples of the photopolymerizable oligomer include a polybutadiene (meth)acrylate having a high hydrophobicity of a (meth)acryl group in a side chain of the polybutadiene oligomer oxime. Polymer, a polyoxymethylene (meth) acrylate oligomer having a polyoxyalkylene bond in a main chain, and an amine-based plastic resin modified with an amine-based plastic resin having a large number of reactive groups in a small molecule (Methyl) acrylate-based oligomers and the like are used in various fields. These photopolymerizable oligomers may be used alone or in combination of two or more. The photopolymerizable oligomer has a high viscosity and an increase in viscosity with an increase in molecular weight. Therefore, when the photopolymerizable oligomer is directly photocured, when the crosslinking reaction is not sufficiently promoted, the crosslinking density is increased to cause the cured product to become brittle. Therefore, in the present invention, a monofunctional or polyfunctional photopolymerizable monomer can be used for adjusting the viscosity, promoting the photocrosslinking reaction, adjusting the crosslinking density of the cured product, and the like. In the present invention, as the component (A), a partial glycidyl group which is a part of an epoxy resin having at least two glycidyl groups in one molecule and a partial esterification ring obtained by reacting (meth)acrylic acid are used. An oxy (meth) acrylate compound is effective. For example, when the curable composition of the present invention is used as a liquid crystal sealing agent, it is also effective because it is possible to reduce the unreacted (meth)acrylic resin which cannot be photohardened by the -11 - 200940588. The epoxy resin used in the esterification reaction is not particularly limited as long as it has at least two glycidyl group-containing epoxy resins, and in this case, bisphenol A type, F type, or paint is used. Phenolic epoxy resin is preferred. Considering the use, ease, etc. in the reaction, it is better to use liquid at room temperature. These epoxy resins may be used singly or in combination of two or more. The partially esterified epoxy (meth) propylene resin may be arbitrarily selected from the epoxy resin having at least two epoxy groups in the molecule, and is arbitrarily selected for the equivalent of the glycidyl group of the epoxy resin. The equivalent ratio of acrylic acid is obtained after the esterification reaction. In the present invention, the esterification ratio is preferably from 20 to 80% by weight. As a method for synthesizing a partially esterified epoxy (meth)acrylic resin, an epoxy resin and (meth)acrylic acid are mixed at a specific equivalent ratio, and an esterification catalyst (for example, benzyldimethylamine, Triethylamine, benzyltrimethylammonium chloride, triphenylphosphine, triphenylsulfonium, etc.) and a polymerization inhibitor (eg, methyl hydrazine, hydroquinone, methylhydroquinone, phenothiazine, dibutylhydroxytoluene, etc.), Further, if an esterification reaction of a bifunctional epoxy resin with (meth)acrylic acid is carried out at an equivalent ratio of 1:1, 50% by weight of a partially esterified epoxy group (methyl) is generally formed. Acrylic resin with 25 equivalent % of unreacted bifunctional epoxy resin and 25 equivalent % of bifunctional (meth)acrylic resin (completely esterified). In the present invention, the above three components are distinguished, and the blending ratio thereof is shown. The present invention, as described above, synthesizes a partially esterified epoxy (meth)acrylic resin in a process which contains any amount of a complete esterified product, and the amount of this raw -12-200940588 is added to (A) Ingredients. The blending amount of the partially esterified epoxy group (meth)acrylic resin is 50% by weight or more, preferably 65% by weight or more, based on the component (A), and the effect can be effectively exhibited. Further, after the equivalent ratio of (meth)acrylic acid reacted with the epoxy resin, the catalyst, and the like are selected, the ratio of formation of the three kinds of products synthesized can be controlled. The (B) photoinitiator used in the present invention may be a radical polymerization type photopolymerization initiator known in the prior art. Specifically, diphenyl Q ketone, 2,2-diethoxyacetophenone, benzyl, benzamidine isopropyl ether, benzamidine dimethyl ketal, 1-hydroxycyclohexyl benzophenone can be used. , thioxanthone benzyl dimethyl ketal, 1-hydroxycyclohexyl ketone, diethyl thioxanthone, 2-diethyl hydrazine, 2-hydroxy-2-methylpropiophenone, 2-methyl- [4-(Methylthio)phenyl]-2-morpholin-1-propane, 2,4,6-trimethylbenzimidium diphenylphosphine oxide, and the like. Particularly, a radical-generating photopolymerization initiator obtained by subjecting a hydroxyl group-containing benzamidine compound and an isocyanate compound represented by the following general formula (3) to an ethyl carbamate reaction can be suitably used. Such light hardening is less suitable for the present invention because the amount of external gas generated is small and the contamination of the liquid crystal ruthenium material is extremely low.
(式中，R、爲羥基、羥基甲氧基、羥基乙氧基、羥基丙基 等之羥基烷氧基、R2及R3爲甲基、乙基、丙基等之烷基 -13- 200940588 。烷基之碳數並未特別限定，一般爲6以下者宜。Ri爲鍵 結於鄰位、間位、對位任一位置。 對於用於本發明（A)成份之（B)光聚合啓始劑配合 比，係對於100重量份（A )成份爲1〜1 〇重量份者宜， 特別爲1.5〜5重量份最佳。當光啓始劑之配合量少於1 重量份則光硬化反應不足，反之多於1 〇重量份則啓始劑 之量太多，導致對於液晶之啓始劑污染問題。 作爲用於本發明之（C )環氧樹脂者，如：以相同於 (A)成份一種之部份醋化環氧基（甲基）丙儲酸樹脂進 行合成時所使用之環氧樹脂爲首，其他如：雙酚A型環氧 樹脂、雙酚F型環氧樹脂、漆用酚醛型環氧樹脂、環式脂 肪族環氧樹脂等由先前技術之公知的環氧樹脂例。此等（ C)成份之環氧樹脂對於（A)成份100重量份而言，使用 80〜250重量份，較佳者爲90〜200重量份之範圍。 另外，作爲（A)成份所選擇之部分酯化環氧基（甲 基）丙烯酸樹脂之合成時，於生成混合物中除部份酯化物 之外，通常含有未反應之環氧樹脂與完全酯化物，該殘留 未反應環氧樹脂存在時，其量作成加計（C)成份環氧樹 脂之量。當（C )成份環氧樹脂量少於90重量份則將無法 取得充足的黏著強度，反之，多於25 0重量份則於UV暫 時硬化後之熱硬化過程中，未硬化之環氧樹脂於液晶材料 中溶解析出，導致產生顯示不良等問題。 構成由本發明所使用之（D)胺烷基咪唑化合物所成 之硬化物之胺烷基係具有構成咪哇環之氮原子上鍵結具有 -14- 200940588 於本 進行 1級或2級胺基之烷基的基本構造之化合物，主要g 發明組成物中之環氧基及（甲基）丙烯基作爲硬化； 作用。作爲胺烷基咪唑化合物者，特別以下述一般 )所示之構造之化合物爲最佳。 【化3】 r3. r2.(In the formula, R is a hydroxyalkoxy group such as a hydroxyl group, a hydroxymethoxy group, a hydroxyethoxy group or a hydroxypropyl group, and R2 and R3 are an alkyl group of a methyl group, an ethyl group, a propyl group or the like-13-200940588. The carbon number of the alkyl group is not particularly limited, and is generally preferably 6 or less. Ri is bonded to any of the ortho, meta or para positions. (B) Photopolymerization for the component (A) of the present invention The initial mixture ratio is preferably 1 to 1 part by weight for 100 parts by weight of the component (A), particularly preferably 1.5 to 5 parts by weight. When the amount of the light initiator is less than 1 part by weight, the photohardening is carried out. The reaction is insufficient, and if more than 1 part by weight, the amount of the initiator is too large, resulting in a problem of the initiator contamination of the liquid crystal. As the (C) epoxy resin used in the present invention, for example, the same as (A) The epoxy resin used in the synthesis of a part of the acetated epoxy (meth) propylene storage acid resin, such as: bisphenol A epoxy resin, bisphenol F epoxy resin, Examples of epoxy resins known in the prior art, such as phenolic epoxy resins and cyclic aliphatic epoxy resins, are lacquers of such (C) components. The fat is used in an amount of 80 to 250 parts by weight, preferably 90 to 200 parts by weight, based on 100 parts by weight of the component (A). Further, a partially esterified epoxy group (methyl group) selected as the component (A) When the acrylic resin is synthesized, in addition to a part of the esterified product, it usually contains an unreacted epoxy resin and a completely esterified product. When the residual unreacted epoxy resin is present, the amount is added as an additive (C) component. The amount of epoxy resin. When the amount of (C) component epoxy resin is less than 90 parts by weight, sufficient adhesive strength will not be obtained. Conversely, more than 25 parts by weight is in the thermal hardening process after UV temporary hardening. The hardened epoxy resin is dissolved and precipitated in the liquid crystal material, causing problems such as poor display. The amine alkyl group constituting the hardened product of the (D) amine alkyl imidazole compound used in the present invention has nitrogen constituting the imiline ring. The atomically bonded compound has a basic structure of the alkyl group of the first or second amino group of the present invention, and the epoxy group and the (meth)acryl group in the composition of the invention are hardened; Amine The compound of the structure of the imidazole compound, particularly the structure shown by the following general formula) is preferred. [chemical 3] r3. r2.
RiRi
(其中，R爲氫原子或1價烴基（較佳者爲碳數1 -烷基）各自獨立地爲氫原子或具有取代基功 烴基（較佳者爲碳數1〜3之烷基）、11爲2或3)。 本發明中（D)成份之添加量對於合計100重邏 (A)成份與（C)成份之添加量，爲1〜20重量份考 特別爲5〜1 5重量份最佳。當少於1重量份時，則东 時無法取得（A)成份之硬化性，反之多於20重量任 使硬化物之玻璃轉移溫度降低。 (D)成份亦可使胺烷基咪唑化合物與其他成任 使用。特別以與具有環狀構造物之二胺化合物（d2 ) 素（d3)、及分子內具有平均2個縮水甘油基之環# (d4)共同進行加熱處理之處理物（參照特開 206447A )之形態使用者宜。該處理物係由富士化场 '3之 :可之 :份之 ，宜’ ，加熱 >則將 •組合 、尿 i樹脂 2005- :工業 -15- 200940588 (股份）以FXR-l 1 1 0之名被市售之。 本發明之硬化性組成物中，在不損及其特性之範圍下 ’亦可適量配合其他添加劑。作爲其他添加劑之例者如： 增敏劑、顏料、染料等之著色劑、保存穩定劑、聚合停止 劑、顏劑、消泡劑、偶合劑、有機、無機塡充劑等例。如 :作爲塡充劑者有：熔融二氧化矽、結晶二氧化矽、碳化 ― 矽、氮化矽、氮化砸、碳酸鈣、碳酸鎂、硫酸鋇、硫酸鈣 、雲母、滑石、黏土、氧化鋁、氧化鎂、氧化锆、氫氧化 0 鋁、氫氧化鎂、矽酸鈣、矽酸鋁、矽酸鋰鋁、矽酸锆、鈦 酸鋇、玻璃纖維、碳纖維、二硫化鉬等例，較佳者爲熔融 二氧化矽、結晶二氧化矽、氮化矽、氮化硼、碳酸鈣、碳 酸鋇、硫酸鈣、雲母、滑石、黏土、氧化鋁、氫氧化鋁、 矽酸鈣、矽酸鋁、更佳者爲熔融二氧化矽、結晶二氧化矽 、滑石。此等塡充劑之有效平均粒徑爲5μηι以下者宜。如 :液晶顯示裝置之玻璃基板間隙，爲實現其高速應答性， 務必進一步縮小，具體而言，被期待爲5μιη以下。當平均 〇 粒徑大於5μιη時，則無法製造目前所期待之液晶顯示裝置 〇 本發明硬化性組成物除上述各成份之外，更可添加爲 改良黏著性之偶合劑，爲確保特定間隙之調距劑，更可添 加保存穩定劑等。作爲矽烷偶合劑例者如：3-環氧丙氧基 丙基三甲氧基矽烷、3-環氧丙氧基丙基甲基二甲氧基矽烷 、3-環氧丙氧基丙基甲基二甲氧基矽烷2- (3,4-環氧基環 己基）乙基三甲氧基矽烷、Ν-苯基-r-胺基丙基甲基二甲 -16- 200940588 氧基矽烷、N- (2-胺基乙基）-3-胺基丙基甲基三甲氧基矽 烷、3 -胺基丙基三乙氧基矽烷、3 -氫硫基丙基三甲氧基矽 烷、乙烯基三甲氧基矽烷、N-(2-(乙烯基苄基胺基）乙 基）3 -胺基丙基三甲氧基砂院鹽酸鹽、3 -甲基丙嫌釀氧基 丙基三甲氧基矽烷、3-氯丙基甲基二甲氧基矽烷、3-氯丙 基三甲氧基矽烷等之矽烷偶合劑例。此等矽烷偶合劑亦可 混合2種以上使用之。藉由使用矽烷偶合劑，可提昇黏著 φ 強度，取得耐濕信賴性良好之液晶密封劑。 又，作爲保存穩定劑者，如：三壬基苯基亞磷酸酯、 三苯基亞磷酸酯、二異辛基辛基苯基亞磷酸酯、二苯基異 辛基亞磷酸酯、二苯基異癸基亞磷酸酯、苯基二異癸基亞 磷酸酯、三異癸基亞磷酸酯、三異辛基亞磷酸酯、三月桂 基亞磷酸酯、烷基烯丙基亞磷酸酯、三烷基亞磷酸酯、烯 丙基亞磷酸酯、二異癸基季戊四醇二亞磷酸酯、雙（2,4-二-第3 丁基苯基）季戊四醇二亞磷酸酯、二硬脂醯季戊 〇 四醇二亞磷酸酯、二硬脂醯季戊四醇二亞磷酸酯等之磷酸 酯衍生物、三苯撐雙硼酸鹽、雙苯撐焦硼酸鹽、雙_ 2,3-二甲基乙烯焦硼酸鹽、雙-2,2-二甲基三甲撐焦硼酸鹽 、2,2-氧基雙（5,5-二甲基-1，3,2-二氧化硼氫烷）等之硼 酸酯衍生物例。此等與苯酚系化合物共同使用後，可大幅 提昇保存穩定性。 取得液晶密封劑時’首先，於（A)成份中使（B )成 份與（C)成份進行溶解混合，接著於此混合物中，以特 定量添加熱硬化劑之（D )成份及必要時之該偶合劑、塡 -17- 200940588 充劑、保存穩定劑等，藉由公知之混合裝置，如：滾輥硏 磨機、混砂機、球磨機等進行均勻混合者宜。經由此方法 可製造本發明之液晶密封劑。 [實施例] 以下，利用實施例進行本發明之詳細說明。 <部份酯化環氧基（甲基）丙烯酸樹脂之合成> (合成例1 ) 反應器中，置入312g(2.0等量）之雙酚F型環氧樹 脂（大日本油墨化學工業（股份）製EPICLON83 0-LVP ) 、與72g(1.0等量）之丙烯酸、與0.2g之氫醌、以及 1.5g之苄基二甲胺，吹入空氣同時於110°C〜120 °C下反 應8小時，取得目的之反應生成物。（雙酚F型環氧樹脂 與丙烯酸以莫耳比計爲等量）。 [反應生成物之評定] 將取得之反應生成物溶於氯仿，於分取型HPLC裝置 中注入〇.45μπι膜濾器過濾者，針對所確定之波峰進行分 取。接著，分取物含雙酚F型二縮水甘油醚單丙烯酸酯（ 部份酯化環氧基丙烯酸酯樹脂）、與雙酚F型二縮水甘油 醚二丙烯酸酯（環氧丙烯酸酯）、以及雙酚F型二縮水甘 油醚（環氧樹脂）被確定以莫耳比計，約爲2 ： 1 -18- 200940588 (合成例2) 反應容器中，置入35 0g (2.0等量）之苯酚漆用酚醛 型環氧樹脂（曰本環氧樹脂（股份）製epikote 1 52 )、與 7 2g(1.0等量）之丙烯酸、以及〇.2g氫醌、1.5g苄基二 甲基胺，與合成例1同法進行反應，取得目的之反應生成 物。另外，與合成例1同法進行評定反應生成物後，可確 定以莫耳比計含有苯酚漆用酚醛型縮水甘油醚半丙烯酸酯 〇 (部份酯化環氧基丙烯酸酯樹脂）與苯酚漆用酚醛型縮水 甘油醚丙烯酸酯（環氧基丙烯酸酯）、以及苯酚漆用酚醛 型二縮水甘油醚（環氧樹脂）爲約2 ： 1 :1。 <硬化性組成物之調整> 以表1所示之配合比例、混合各成份，調整各試料（ 實施例1、2及比較例1〜3)。適用於（D)成份之胺化 合物等之添加量對於（C)成份中之反應性基而言，其（D ©)成份中之反應性基之和分別添加幾乎相同之比例。另外 ，表中之添加量未特別限定下爲重量基準。又，用於實施 例、比較例之各成份爲如下。 •部份酯化環氧基（甲基）丙烯酸樹脂：使用合成例 1、2之化合物。 •環氧樹脂：漆用酣酵型環氧樹脂（商品名epikote 152、日本環氧樹脂公司製） 雙酚A/F型環氧混合樹脂（商品名epici〇ne EXA-835 LV、大日本油墨化學工業公司製） -19- 200940588 •自由基產生型光聚合啓始劑 PI-1 : 1-[4- ( 2-羥基乙氧基）-苯基]-2-羥基-2-甲基-1-丙烷-1-酮與異氟爾酮二異氰酸酯之胺基甲酸乙酯化反應 所取得之光聚合啓始劑 •磷酸酯衍生物（保存穩定劑）：JPP-13R (城北化 學工業公司製品） •苯酚樹脂（保存穩定劑）：HF -1 Μ (明和化成公司 製品） © • ( D )成份：由胺基烷基咪唑化合物所成之硬化劑 (1-(2-胺基乙基）·2-甲基咪唑於異氟爾酮二胺、雙酚F 型環氧化物及尿素之存在下進行加熱處理之處理物）： FXR-1 1 10 (富士化成工業公司製品） •脂肪族聚胺化合物：EH-43 42S (旭電化工業公司製 品） •含有芳香族系胺基之咪唑衍生物：2MA-OKPW (四 國化成公司製品） 〇 •無機塡充劑：滑石（日本滑石公司製 商品名 microaceL-1 ) 針對所得各試料，進行以下評定，合倂其結果示於表 1 ° [黏度]:利用EHD型黏度計（東機產業（股份）製， 測定25°C之黏度。（JIS-K-5600-2-3爲基準） [黏度穩定性試驗]:於25 °C恆溫槽中放置所得之各液 晶密封劑，以該黏度計進行初期黏度與24小時後黏度之 -20- 200940588 測定比較，評定樹脂之保存穩定性。 [黏著強度試驗]:(試驗片作成方法）於玻璃板（ 100mm x25mm x5mm)中，依 JIS-K-6850 所規定之方法， 塗佈表1所示組成之硬化性樹脂組成物，貼合另一面玻璃 板，利用燈高度15cm之高壓水銀燈80W/cm，照射合計光 量3 0kJ/m2之紫外線後，使用120°C xl小時加熱之試驗片 進行評定。 0 (評定方法）將試驗片兩端固定於吸盤，以拉伸速度 50mm/min，加入拉伸剪切載重，測定破損試驗片爲止之最 大載重，由下式算出拉伸剪切黏著強度。 (剪切黏著強度算出方法）Ts = Fs/A Ts :拉伸剪切黏著強度 Pa{kgf/cm2}(wherein R is a hydrogen atom or a monovalent hydrocarbon group (preferably, a C 1 -alkyl group) each independently a hydrogen atom or a substituted hydrocarbon group (preferably an alkyl group having 1 to 3 carbon atoms), 11 is 2 or 3). In the present invention, the amount of the component (D) added is preferably from 1 to 20 parts by weight, particularly preferably from 5 to 15 parts by weight, based on the total amount of the 100 weight (A) component and the (C) component. When it is less than 1 part by weight, the hardenability of the component (A) cannot be obtained in the east, and if it is more than 20, the glass transition temperature of the cured product is lowered. The component (D) can also be used in combination with other amine alkyl imidazole compounds. In particular, it is treated with a heat treatment together with a diamine compound (d2) having a cyclic structure (d3) and a ring # (d4) having an average of two glycidyl groups in the molecule (see JP-A 206447A). The shape is suitable for the user. The treatment is from Fuji Chemical Field '3: can be: part, Yi', heating> will be combined, urine i resin 2005-: industry-15- 200940588 (shares) to FXR-l 1 1 0 The name is commercially available. In the curable composition of the present invention, other additives may be blended in an appropriate amount without impairing the properties thereof. Examples of other additives include coloring agents such as sensitizers, pigments, and dyes, storage stabilizers, polymerization stoppers, pigments, antifoaming agents, coupling agents, organic and inorganic chelating agents, and the like. Such as: as a sputum agent: molten cerium oxide, crystalline cerium oxide, carbonized - cerium, tantalum nitride, tantalum nitride, calcium carbonate, magnesium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, oxidation Aluminum, magnesium oxide, zirconium oxide, aluminum hydroxide, magnesium hydroxide, calcium citrate, aluminum silicate, lithium aluminum niobate, zirconium silicate, barium titanate, glass fiber, carbon fiber, molybdenum disulfide, etc. The best is molten cerium oxide, crystalline cerium oxide, cerium nitride, boron nitride, calcium carbonate, barium carbonate, calcium sulfate, mica, talc, clay, alumina, aluminum hydroxide, calcium citrate, aluminum citrate More preferably, it is molten cerium oxide, crystalline cerium oxide, and talc. The effective average particle diameter of these chelating agents is preferably 5 μηι or less. For example, the glass substrate gap of the liquid crystal display device must be further reduced in order to achieve high-speed response, and specifically, it is expected to be 5 μm or less. When the average cerium particle diameter is more than 5 μm, the liquid crystal display device which is currently expected cannot be produced. In addition to the above components, the curable composition of the present invention can be added as a coupling agent for improving adhesion, in order to ensure a specific gap. For the agent, a storage stabilizer or the like can be added. As a decane coupling agent, for example, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, 3-glycidoxypropylmethyl Dimethoxydecane 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, fluorenyl-phenyl-r-aminopropylmethyldimethyl-16- 200940588 oxydecane, N- (2-Aminoethyl)-3-aminopropylmethyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-hydrothiopropyltrimethoxydecane, vinyltrimethoxy Hydrazin, N-(2-(vinylbenzylamino)ethyl)3-aminopropyltrimethoxylate hydrochloride, 3-methylpropionoxypropyltrimethoxydecane, Examples of decane coupling agents such as 3-chloropropylmethyldimethoxydecane and 3-chloropropyltrimethoxydecane. These decane coupling agents may be used in combination of two or more kinds. By using a decane coupling agent, the adhesion φ strength can be improved, and a liquid crystal sealing agent having good moisture resistance can be obtained. Further, as a storage stabilizer, for example, tridecylphenylphosphite, triphenylphosphite, diisooctyloctylphenylphosphite, diphenylisooctylphosphite, diphenyl Isodecyl phosphite, phenyl diisodecyl phosphite, triisodecyl phosphite, triisooctyl phosphite, trilauryl phosphite, alkyl allylic phosphite, Trialkyl phosphite, allyl phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-butyl butyl) pentaerythritol diphosphite, distearin season Phosphate derivatives such as pentamidine tetraol diphosphite, distearyl pentaerythritol diphosphite, triphenylene diborate, bisphenylpyroborate, bis-2,3-dimethylethylene coke Boric acid such as borate, bis-2,2-dimethyltrimethylpyroborate, 2,2-oxybis(5,5-dimethyl-1,3,2-borane hydroalkane) Examples of ester derivatives. When these are used together with a phenolic compound, storage stability can be greatly improved. When the liquid crystal sealing agent is obtained, 'Firstly, the component (B) and the component (C) are dissolved and mixed in the component (A), and then the component (D) of the thermosetting agent is added to the mixture in a specific amount and, if necessary, The coupling agent, 塡-17-200940588 charge, storage stabilizer, and the like are preferably uniformly mixed by a known mixing device such as a roll honing machine, a sand mixer, a ball mill, or the like. The liquid crystal sealing agent of the present invention can be produced by this method. [Examples] Hereinafter, the present invention will be described in detail by way of examples. <Synthesis of Partially Esterified Epoxy (Meth) Acrylic Resin> (Synthesis Example 1) 312 g (2.0 equivalent) of bisphenol F type epoxy resin was placed in the reactor (Daily Ink Chemical Industry) (Stock) EPICLON83 0-LVP), with 72g (1.0 equivalent) of acrylic acid, with 0.2g of hydroquinone, and 1.5g of benzyldimethylamine, blown in air at 110 ° C ~ 120 ° C The reaction was carried out for 8 hours to obtain a desired reaction product. (Bisphenol F type epoxy resin and acrylic acid are equivalent in molar ratio). [Evaluation of Reaction Product] The obtained reaction product was dissolved in chloroform, and injected into a 〇.45 μπι membrane filter in a fractionation type HPLC apparatus, and the peak was determined for the peak. Next, the fraction contains bisphenol F type diglycidyl ether monoacrylate (partially esterified epoxy acrylate resin), and bisphenol F type diglycidyl ether diacrylate (epoxy acrylate), and Bisphenol F type diglycidyl ether (epoxy resin) was determined to be in the molar ratio of about 2: 1 -18 to 200940588 (Synthesis Example 2) In a reaction vessel, 35 0 g (2.0 equivalent) of phenol was placed. The paint is a phenolic epoxy resin (epikote 1 52 manufactured by Epoxy Epoxy Co., Ltd.), and 72 g (1.0 equivalent) of acrylic acid, and 2 g of hydroquinone, 1.5 g of benzyldimethylamine, and Synthesis Example 1 was reacted in the same manner to obtain a desired reaction product. Further, after the reaction product was evaluated in the same manner as in Synthesis Example 1, it was confirmed that the phenolic type glycidyl ether semi-acrylate phenol (partially esterified epoxy acrylate resin) and the phenol paint for the phenol paint were contained in the molar ratio. The phenolic type glycidyl ether acrylate (epoxy acrylate) and the phenol paint phenolic diglycidyl ether (epoxy resin) were about 2:1:1. <Adjustment of Curable Composition> Each sample was mixed at the mixing ratio shown in Table 1 (Examples 1, 2 and Comparative Examples 1 to 3). The amount of the amine compound or the like which is suitable for the component (D) is added to the reactive group in the component (C), and the sum of the reactive groups in the component (D) is added in almost the same ratio. Further, the amount of addition in the table is not particularly limited to the weight basis. Further, the components used in the examples and comparative examples are as follows. • Partially esterified epoxy (meth)acrylic resin: The compounds of Synthesis Examples 1 and 2 were used. • Epoxy resin: lacquer type epoxy resin (trade name epikote 152, manufactured by Nippon Epoxy Co., Ltd.) Bisphenol A/F epoxy mixed resin (trade name epici〇ne EXA-835 LV, Dainippon ink) Chemical Industry Co., Ltd.) -19- 200940588 • Free radical generating photopolymerization initiator PI-1 : 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl- Photopolymerization initiator/phosphate derivative (preservation stabilizer) obtained by ethylation of 1-propan-1-one with isophorone diisocyanate: JPP-13R (product of Chengbei Chemical Industry Co., Ltd.) • Phenol resin (preservation stabilizer): HF -1 Μ (Products of Minghe Chemical Co., Ltd.) © • (D) Ingredients: Hardener (1-(2-Aminoethyl)) formed from an aminoalkyl imidazole compound · Treatment of 2-methylimidazole in the presence of isophorone diamine, bisphenol F-epoxide and urea): FXR-1 1 10 (product of Fuji Chemical Industry Co., Ltd.) • Aliphatic aggregation Amine compound: EH-43 42S (product of Asahi Kasei Kogyo Co., Ltd.) • Imidazole derivative containing aromatic amine group: 2MA-OKPW制品•Inorganic 塡 :: talc (trade name microaceL-1 manufactured by Japan Talc Co., Ltd.) The following evaluations were made for each sample obtained, and the results are shown in Table 1 ° [Viscosity]: Using EHD type viscometer ( Toki Industrial Co., Ltd., measuring the viscosity at 25 ° C. (JIS-K-5600-2-3 is the basis) [Visco Stability Test]: Place the obtained liquid crystal sealant in a 25 ° C thermostat, The initial viscosity was measured by the viscosity meter and compared with the viscosity after 24 hours, and the storage stability of the resin was evaluated. [Adhesive strength test]: (Test piece preparation method) In a glass plate (100 mm x 25 mm x 5 mm), According to the method specified in JIS-K-6850, the curable resin composition of the composition shown in Table 1 is applied, and the other side glass plate is bonded, and the total light amount is 30 kJ/m2 by using a high-pressure mercury lamp of 80 W/cm having a lamp height of 15 cm. After the ultraviolet ray, the test piece was heated at 120 ° C for 1 hour. 0 (Evaluation method) Both ends of the test piece were fixed to a suction cup at a tensile speed of 50 mm/min, and a tensile shear load was added to measure the damaged test piece. Maximum load, by The tensile shear adhesion strength is calculated by the formula (cutting adhesion strength calculation method) Ts = Fs/A Ts : tensile shear adhesion strength Pa{kgf/cm2}
Fs :最大載重 N{kgf} A :黏著面積 m2{cm2} [信賴性試驗]:針對於PCT ( 121°C、2atm)雰圍下， Φ 將前述方法所作成之試驗片放置12小時者，進行相同測 定。 [液晶污染性試驗]:作爲本發明之液晶污染性評定方 法者，經由液晶組成物之相轉移溫度測定進行之。作爲試 驗方法者，於樣品瓶中置入〇. 1 5g之本發明硬化性樹脂組 成物，調製未作成照射合計光量30kJ/m2之紫外線者。分 別使此等進行120 °C XI小時加熱硬化後，加入1.5g之液 晶組成物（merck製 ZLI-4792 )。將此等投入l〇(TC烤箱 中1小時，促進硬化性樹脂組成物之溶出。之後於室溫放 -21 - 200940588 涼1小時，由處理過之樣品瓶中取出上澄液之液晶組成物 ’利用DSC 220 ( seiko Instruments製），測定液晶之相 轉移溫度。其中，本發明硬化性樹脂組成物所接觸處理之 液晶組成物（以下簡稱接觸液晶）之相轉移溫度與未接觸 下’同樣處理之液晶組成物（以下簡稱非接觸液晶）之相 轉移溫度進行比較之結果’該接觸液晶之相轉移溫度之値 爲〇 . 5 °C以上未降低者代表合格以〇示之，〇 . 6 °C以上降低 者代表不合格以X示之。 I^i]Fs : Maximum load N{kgf} A : Adhesion area m2{cm2} [Reliability test]: For PCT (121 ° C, 2 atm) atmosphere, Φ The test piece made by the above method is placed for 12 hours. The same measurement. [Liquid crystal contamination test]: The liquid crystal contamination evaluation method of the present invention was carried out by measuring the phase transition temperature of the liquid crystal composition. As a test method, 1.55 g of the curable resin composition of the present invention was placed in a sample bottle, and ultraviolet rays which were not irradiated with a total light amount of 30 kJ/m 2 were prepared. After heating and hardening at 120 ° C for XI hours, 1.5 g of a liquid crystal composition (ZLI-4792 manufactured by Merck) was added. This was put into the 〇 oven for 1 hour to promote the dissolution of the curable resin composition. After cooling at room temperature for 21 hours at -200940588, the liquid crystal composition of the supernatant liquid was taken out from the treated sample bottle. 'The phase transition temperature of the liquid crystal is measured by DSC 220 (manufactured by Seiko Instruments). The phase transition temperature of the liquid crystal composition (hereinafter referred to as contact liquid crystal) which is treated by the curable resin composition of the present invention is the same as that of the untouched The phase transition temperature of the liquid crystal composition (hereinafter referred to as non-contact liquid crystal) is compared as a result of 'the phase transition temperature of the contact liquid crystal is 〇. 5 °C or more is not reduced, the representative is qualified, 〇. 6 ° Those who are lower than C are not qualified to show X. I^i]
— 實施例1 實施例2 比較例1 比較例2 比較例3 (A)成份 合成樣品1 30 20 60 20 60 合成樣品2 30 50 40 (C诚份 epikotel52 40 40 40 EPICLON EXA-835LV 30 40 诚份 PI-1 2 2 2 2 2 安定劑 '— JPP-13R 1 1 1 1 1 HF-1M 1 1 1 1 1 ①诚份 --- FXR-1110 15 10 EH-4342S 40 20 2MA-OKPW 5 3 _^充劑 microaceL-1 10 10 10 10 10 --- 評價結果 實施例1 實施例2 比較例1 比較例2 比較例3 黏度安定性 試驗 初期黏度[Pa · s] 300 310 320 300 330 (25°C x24 小時） 300 310 320 300 330 〜 黏著爾試驗[MPa] 7.5 7.2 7.3 7.5 7.3 〜 信賴性試驗[MPa】 7.1 7.2 4.2 7.1 5.5 玻璃體點[〇C ] 125 120 82 135 94 液晶 污染性 UV+加麵化 〇 〇 〇 X X 加熱硬化 〇 〇 〇 X X 200940588 由表1顯示，實施例1〜2證明無作業上問題之黏度 變化，黏著強度高。又，均使用胺基烷基咪唑類爲熱硬化 劑，因此液晶污染性低、玻璃轉移點、信賴性試驗後之黏 著強度高。反觀比較例1係使用聚胺系化合物爲熱硬化劑 ，因此與丙烯基反應後液晶污染性雖低，卻降低玻璃轉移 點，降低信賴性試驗後之黏著強度。比較例2係使用未具 胺基烷基之咪唑衍生物爲熱硬化劑。該咪唑衍生物中存在 1級胺基，惟此係芳香族性胺基，不與丙烯基反應，因此 於熱硬化時，其未硬化部位未交聯硬化，故液晶污染性高 。使用混合咪唑類、及脂肪族聚胺化合物爲熱硬化劑之比 較例3藉由混合脂肪族聚胺化合物之影響而無法取得充足 的玻璃轉移溫度，其結果顯示信賴性試驗後之黏著強度降 低。 [產業上可利用性] 〇 本發明可提供一種黏度穩定性高，且具有高度黏著強 度，具有信賴性之光硬化性樹脂組成物。又，將本發明之 光硬化性樹脂組成物適用於液晶面板之主密封劑、CCD相 機組件之黏著構件後，可提昇製品之信賴性、收率。 -23-- Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 (A) Composition Synthesis Sample 1 30 20 60 20 60 Synthesis Sample 2 30 50 40 (C Chengfen epikotel 52 40 40 40 EPICLON EXA-835LV 30 40 PI-1 2 2 2 2 2 Stabilizer' — JPP-13R 1 1 1 1 1 HF-1M 1 1 1 1 1 1 诚份--- FXR-1110 15 10 EH-4342S 40 20 2MA-OKPW 5 3 _ ^ Charge microaceL-1 10 10 10 10 10 --- Evaluation results Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Viscosity stability test Initial viscosity [Pa · s] 300 310 320 300 330 (25° C x24 hours) 300 310 320 300 330 ~ Adhesion test [MPa] 7.5 7.2 7.3 7.5 7.3 ~ Reliability test [MPa] 7.1 7.2 4.2 7.1 5.5 Vitreous point [〇C ] 125 120 82 135 94 Liquid crystal contamination UV+ 〇〇〇 XX heat hardening 〇〇〇 200940588 It is shown in Table 1 that Examples 1 to 2 demonstrate that there is no problem of viscosity change on the job, and the adhesive strength is high. Further, all of the aminoalkyl imidazoles are used as a heat hardener. Therefore, the liquid crystal contamination is low, the glass transition point, and the adhesion strength after the reliability test are high. In Comparative Example 1, since the polyamine compound was used as the thermal curing agent, the liquid crystal contamination was low after the reaction with the propylene group, but the glass transition point was lowered, and the adhesion strength after the reliability test was lowered. Comparative Example 2 used without an amine. The imidazole derivative of the alkyl group is a thermosetting agent. The imidazole derivative has a primary amine group, but is an aromatic amine group, and does not react with the propylene group, so when it is thermally hardened, the unhardened portion is not paid. Since the hardening is high, the liquid crystal is highly polluted. In Comparative Example 3 using a mixed imidazole and an aliphatic polyamine compound as a thermal curing agent, sufficient glass transition temperature cannot be obtained by mixing the effects of the aliphatic polyamine compound, and the result is shown. The adhesive strength after the reliability test is lowered. [Industrial Applicability] The present invention provides a photocurable resin composition having high viscosity stability and high adhesion strength and reliability. The photocurable resin composition is suitable for the main sealant of the liquid crystal panel and the adhesive member of the CCD camera module, and can improve the reliability and yield of the product.