201035214 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種於硬化後具有遮光性與黏著性之光 硬化性樹脂組成物。本發明之光硬化性樹脂組成物係就光 學機器尤其液晶顯示器的密封劑而言，可適宜使用於液晶 面板等之光學材料零件的固定或背光之防止漏光、防止外 光進入用。 Ο 【先前技術】 近年，伴隨液晶顯示器等之顯示器或光學透鏡、光拾 取器、感測器等之電子光學機器的高性能化，爲實現並維 持高感度，使來自通過構件或固定樹脂層之外部的透過光 或來自內部之漏光、來自間隙之漏光所造成的損失降低乃 不可或缺。於圖1中，顯示習知之液晶顯示器的模式圖。 尤其，如固定樹脂層，可尋求接著性或黏著性、強度、耐 〇 久性、耐濕性等各種特性的部分中，係必須在同一樹脂使 此等之特性與遮光倂存。 爲達成上述的要求，已報告一種光硬化性樹脂組成物 ，其係藉由利用基材樹脂之光硬化性樹脂的硬化物與添加 於其之化合物之間的折射率差，俾藉光而有效地硬化，因 此，即使爲厚的膜厚之樹脂亦可硬化，所得到之硬化樹脂 的光透過率低（專利文獻〇 。 又，目前，一般已使用未硬化之黏著性薄膜沖擊加工 成框狀，貼合於玻璃基板後，使薄膜硬化之方法。 -5- 201035214 [先前技術文獻] [專利文獻] [專利文獻1]特開20〇7_ 1 1 9684號公報 【發明內容】 [發明欲解決之問題] 使用光硬化性樹脂組成物作爲液晶顯示器之密#齊1時 ，係實施於基板等之上呈框狀形成光硬化性樹脂組成物後 ，使光硬化性樹脂硬化，使被黏物（液晶面板）以光硬化 性樹脂組成物接著之步驟。此處，爲使用專利文獻1記載 之光硬化性樹脂組成物作爲液晶顯示器之密封劑等，係可 尋求一種於光硬化性樹脂組成物調配熱硬化性樹脂，對光 硬化後之光硬化性樹脂組成物賦予黏著性。因此，除了光 硬化之步驟，尙必須熱硬化之步驟，此熱硬化之步驟中係 需要長時間。又，液晶顯示器之零件係有時含有在約7 〇 °C變形者，此時，在光硬化性樹脂組成物之熱硬化步驟中 ，液晶顯示器之零件會變形之問題仍存在。 又’使用加工成框狀之黏著性薄膜的方法，薄膜之沖 擊幅寬以約〇.5mm爲限，於高密度封裝化上有限度，又 ’產生於沖擊後不使用之薄膜部分，故有材料良率低之問 題。 又’在使用加工成框狀之薄膜的方法中，加工後之薄 膜的處理性很麻煩’進一步’薄膜之貼合步驟係很難機械 -6- 201035214 化，故在目前，人員以手作業進行薄膜之貼合，生產線很 難自動化等的問題仍存在。 [用以解決課題之方法] 本發明人等經專心硏究之結果，發現藉由使光硬化性 樹脂組成物形成爲光硬化後具有黏著性者，俾使用來作爲 液晶顯示器之密封劑等時，可達成上述課題，終完成本發 Ο 明。 亦即，本發明之目的在於提供一種光硬化性樹脂組成 物，其係藉光而有效地硬化，因此即使厚的膜厚亦可硬化 ，硬化後，光透過率低，具有黏著性，且強度、耐久性、 耐濕性等各種之特性亦均優。 第1之本發明係關於光硬化性樹脂組成物，其係含有 :(A )光硬化性樹脂、（B )黏著性賦予劑、（C )具有 與該（A)成分及（B)成分之硬化物的折射率之差爲 Ο 0.01以上之折射率，對該（A)成分及（B)成分爲非相 溶性且具有分散性之化合物，以及（D )黑色顏料。 第2之本發明係關於光硬化性樹脂組成物，其中（C )成分爲選自由氧化鋁粉末及氧化鈦粉末所構成之群。 第3之本發明係關於光硬化性樹脂組成物，其中（D )成分爲碳粉末。 第4之本發明係關於光硬化性樹脂組成物，其中（B )成分爲丙烯酸系、聚矽氧系、馬來醯亞胺系、松香酯系 、萜烯系、橡膠系、或芳香族氫化石油系黏著賦予劑。 -7- 201035214 第5之本發明係關於光硬化性樹脂組成物，其中（A )成分爲丙烯酸改性樹脂或環氧樹脂。 第6之本發明係關於光硬化性樹脂組成物，其中相對 於（A)成分100重量份，（B)成分爲20〜170重量份’ (C)成分爲0.2〜80重量份及（D)成分爲0.1〜3 5重量份 〇 第7之本發明係關於光硬化性樹脂組成物，其係進一* 步含有光聚合起始劑。 第8之本發明係關於上述之光硬化性樹脂組成物的$ 化物。 第9之本發明係關於光學機器構件，其係含有上述= 硬化物。 第10之本發明係關於光學機器，其係含有上述之光 學機器構件。 本發明之電子光學機器構件的槪念表示於圖2。 [發明之效果] 本發明之光硬化性樹脂組成物係可以光有效率地硬化 ，故可厚膜硬化，所得到之硬化物係來自內外之光透過性 低，亦即，遮光性高，黏著性優，且強度、耐久性、耐濕 性等各種特性亦優異。又，光硬化性樹脂組成物係可印刷 或點膠等，故光硬化性樹脂組成物之使用率高外，尙容易 形成微細線，進一步，生產線可自動化，故可充分提高生 產性。 -8- 201035214 因此，本發明之光硬化性樹脂組成物係可適宜作爲光 學機器尤其液晶顯示器之密封劑。 [用以實施發明之形態] 以下詳細說明本發明。 本發明之光硬化性樹脂組成物，其特徵在於含有：（ A )光硬化性樹脂、（B )黏著性賦予劑、（C )具有與該 Ο (A)成分及（B)成分之硬化物的折射率之差爲0.01以 上之折射率，對該（A )成分及（B )成分爲非相溶性且 具有分散性之化合物，以及（D)黑色顏料。在本發明中 係組合（C )成分與（D )成分，利用（C )成分之光反射 性而實現厚膜硬化與遮光、以（D )成分所產生之光吸收 實現遮光之點爲特徵。 本發明中之（A)成分係與（B)成分一起形成所謂 基材樹脂’即使在使光硬化性樹脂組成物硬化之硬化物中 〇 亦可形成連續相。 本發明之光硬化性樹脂係只要爲藉可見光、紫外線等 之光進行硬化之樹脂即可，並無特別限定，而可舉例如（ 甲基）丙烯酸樹脂、胺基甲酸酯丙烯酸酯樹脂及聚酯丙烯 酸酯樹脂等之丙烯酸改性樹脂；環氧樹脂；氧雜環丁烷樹 脂。光硬化性樹脂宜可舉例如丙烯酸改性樹脂及環氧樹脂 〇 丙嫌酸改性樹脂係定義爲具有丙烯醯基或甲基丙烯醯 基之單官能性及多官能性之（甲基）丙烯酸酯化合物，可 ~ 9 - 201035214 例示如甲基丙烯酸酯、乙基丙烯酸酯、正丙基丙烯酸酯、 正丁基丙烯酸酯、第三丁基丙烯酸酯、異丁基丙烯酸酯、 乙基己基丙烯酸酯、異癸基丙烯酸酯、正己基丙烯酸酯、 硬脂基丙烯酸酯、月桂基丙烯酸酯、十三碳基丙烯酸酯、 乙氧基乙基丙烯酸酯、甲氧基乙基丙烯酸酯、縮水甘油基 丙烯酸酯、丁氧基乙基丙烯酸酯、2-羥基乙基丙烯酸酯、 2-羥基丙基丙烯酸酯、2-甲氧基乙基丙烯酸酯、2-乙氧基 乙氧基乙基丙烯酸酯、甲氧基二乙二醇丙烯酸酯、乙氧基 二乙二醇丙烯酸酯、甲氧基二丙二醇丙烯酸酯、八氟戊基 丙烯酸酯' N，N-二甲基胺基乙基丙烯酸酯、N，N-二乙基胺 基乙基丙烯酸酯、烯丙基丙烯酸酯、1，3-丁二醇丙烯酸酯 、1，4-丁二醇丙烯酸酯、丙烯醯基嗎啉、1，6-己二醇丙烯 酸酯、聚乙二醇二丙烯酸酯、二乙二醇二丙烯酸酯、新戊 二醇二丙烯酸酯、三乙二醇二丙烯酸酯、三丙二醇二丙烯 酸酯、羥基三甲基乙酸酯、新戊二醇二丙烯酸酯、三羥甲 基丙烷二丙烯酸、1,3-雙（羥乙基）-5,5-二甲基乙內醯脲 、3 -甲基戊二醇丙烯酸酯、α，ω-二丙烯酸基雙二乙二醇 酞酸酯、三羥甲基丙烷三丙烯酸酯、季戊四醇丙烯酸酯、 季戊四醇六丙烯酸酯、二季戊四醇單羥基五丙烯酸酯、五 季戊四醇三丙烯酸酯、季戊四醇四丙烯酸酯、三羥乙基三 聚異氰酸酯之三（甲基）丙烯酸酯、二季戊四醇六丙烯酸 酯、及此等之ΕΟ及/或Ρ◦加成物、α,ω -四烯丙基雙 三羥甲基丙烷四氫酞酸酯、2-羥乙基丙烯醯基磷酸酯、三 羥甲基丙烷三甲基丙烯酸酯、乙二醇二（甲基）丙烯酸酯 -10- 201035214 、四乙二醇二（甲基）丙烯酸酯、聚乙二醇二（甲基）丙 燃酸酯、1，4 -丁二醇二（甲基）丙烯酸酯、丨，6-己二醇二 (甲基）丙烯酸酯、新戊二醇二甲基丙烯酸酯、二丙烯醯 氧乙基憐酸醋、N-乙烯基吡咯烷酮及具有此等之光反應性 官能基之寡聚物。寡聚物係可舉例如具有聚醚骨架、聚碳 酸酯骨架或聚酯骨架之（甲基）丙烯酸酯化合物。所市售 之製品係可舉例如根上工業股份公司製之聚碳酸酯系丙烯 Ο 酸酯（製品名·· UN5 500 )、聚酯系丙烯酸酯（製品名： UN7700 )、日本合成化學工業股份公司製之聚醚系丙烯 酸酯（製品名：UV3 700B )等。上述之丙烯酸改性樹脂之 中，（A)成分尤佳者係聚碳酸酯系丙烯酸酯。 環氧樹脂係定義爲具有含1個以上環氧基之分子構造 的化合物’可舉例如雙酚、雙酚A、氫化雙酚A、雙酚F 、雙酚AD、雙酚S、四甲基雙酚A、四甲基雙酚F、四氯 雙酚A、四溴雙酚A等之雙酚類之二縮水甘油基醚類、酚 〇 酚醛清漆、甲酧酚醛清漆、溴化酚酚醛清漆、鄰甲酚酚酸 清漆等之酚醛清漆樹脂的聚縮水甘油基醚類、乙二醇、聚 乙二醇、聚丙二醇、丁二醇、1，6 -己二醇、新戊二醇、三 羥甲基丙烷、1，4-環己烷二甲醇、雙酚A之環氧乙烷加成 物、雙酚A之環氧丙烷加成物等之伸烷基甘醇類的二縮 水甘油基醚類、六氫酞酸之縮水甘油基酯或偶體酸之二縮 水甘油基酯等之縮水甘油基酯類、3，4-環氧基環己基甲基_ 3’，4’_環氧基環己烷羧酸酯、3,4-環氧基環己基乙基-3’，4，_ 環氧基環己烷羧酸酯、3，4·環氧基-6-甲基環己基-3，，4’-環 -11 - 201035214 氧基-6’-甲基環己烷羧酸酯、乙烯基環己嫌〜 农u钸〜氧化物、 3.4- 環氧基-4-甲基環己基-2_環氧丙烷、2_ ( 3，t環氧基環 己基-5,5-螺-3,4_環氧基）環己烷-間-二噁烷、雙（3 ‘環 氧基環己基）己二酸酯、雙（3,4-環氧基環ρ ^基甲基）己 二酸酯、內酯改性3,4-環氧基環己基甲基_v 密十盎3，4，_環氧基環 己烷羧酸酯、亞甲基雙（3,4-環氧基環己檢、 兀）、亞甲基雙 (3,4-環氧基環己院竣酸醋）、二環己二烯二環氧化物、 雙（3,4-環氧基環己基）醚、·雙（3,4_環氧基環己基甲基 )醚、四（3,4-環氧基環己基甲基）丁烷四羧酸醋、雙（ 3.4- 環氧基環己基甲基）-4,5-環氧基四氫酞酸醋、雙（ 3.4- 環氧基環己基）二乙基砂氧烷等之脂環式環氧化合物 及具有此等之光反應性官能基的寡聚物。上述之環氧樹脂 中，（A )成分尤佳者係雙酚A。環氧樹脂係可與丙嫌酸 改性樹脂倂用。 在本發明中之（A )成分係依硬化後之折射率而定， 無特別限定，可使用賦予具有任意折射率之硬化物的光硬 化性樹脂。在本發明中，（A )成分係可從上述之樹脂， 考量在使用之部位中所求出的性能而形成1種或2種以上 之混合物而選擇。 在本發明中之（B)成分係與（A)成分一起形成基 材樹脂。（B )成分爲黏著性賦予劑’對硬化後之光硬化 性樹脂組成物賦予黏著性。（B )成分可舉例如丙嫌酸系 、聚矽氧系、馬來醯亞胺系、松香酯系、萜稀系、橡膠系 、芳香族石油系等的黏著性賦予劑’從耐熱性 '相溶性之 -12- 201035214 觀點’宜爲丙嫌酸系、松香酯系、萜烧系、芳香族氫化石 油系。所市售之製品係可舉例如以式（1 ):[Technical Field] The present invention relates to a photocurable resin composition having light blocking properties and adhesion after curing. The photocurable resin composition of the present invention can be suitably used for fixing an optical material such as a liquid crystal panel or preventing light leakage of a backlight or preventing external light from entering the sealing agent of an optical device, particularly a liquid crystal display.先前 [Prior Art] In recent years, with the high performance of displays such as liquid crystal displays, optical lenses such as optical lenses, optical pickups, and sensors, in order to achieve and maintain high sensitivity, it is possible to obtain a high-sensitivity from a passing member or a fixing resin layer. The loss of external transmitted light or light leakage from the inside and leakage from the gap is indispensable. In Fig. 1, a schematic diagram of a conventional liquid crystal display is shown. In particular, in the case where the resin layer is fixed, various properties such as adhesion, adhesion, strength, durability, and moisture resistance can be sought, and it is necessary to make such characteristics and light-shielding in the same resin. In order to achieve the above-mentioned requirements, a photocurable resin composition which is effective by utilizing a difference in refractive index between a cured product of a photocurable resin of a base resin and a compound added thereto has been reported. Since the resin is hardened, the resin having a thick film thickness can be hardened, and the obtained cured resin has a low light transmittance (Patent Document 又. Further, at present, it has been generally processed into a frame shape by using an uncured adhesive film. A method of hardening a film after being bonded to a glass substrate. -5 - 201035214 [Prior Art Document] [Patent Document] [Patent Document 1] JP-A-207-17-1684 [Invention] [Invention When the photocurable resin composition is used as a liquid crystal display, the photocurable resin composition is formed in a frame shape on a substrate or the like, and then the photocurable resin is cured to form an adherend. (Liquid crystal panel) The step of using a photocurable resin composition is followed by a photocurable resin composition described in Patent Document 1 as a sealing agent for a liquid crystal display. The photocurable resin composition is blended with a thermosetting resin to impart adhesiveness to the photocurable resin composition after photocuring. Therefore, in addition to the step of photocuring, the step of thermally hardening is required, and the step of thermal hardening is performed. Further, the parts of the liquid crystal display sometimes contain a deformation at about 7 〇 ° C. At this time, in the thermal hardening step of the photocurable resin composition, the problem that the parts of the liquid crystal display are deformed still exists. In addition, the method of processing the adhesive film into a frame shape has a thickness width of about 〇5. 5 mm, limited in high-density encapsulation, and 'produces a film portion which is not used after the impact, so The problem of low material yield. In addition, in the method of processing a film formed into a frame shape, the handling property of the processed film is troublesome. Further, the film bonding step is difficult to mechanically -6-201035214, so At present, the problem that the production of the film is difficult to be automated by the hand work is still in place. [The method for solving the problem] The inventors have concentrated on the results of the research. When the photocurable resin composition is formed into a light-curable resin and is used as a sealant for a liquid crystal display, the above-mentioned problems can be attained, and the present invention has been completed. Provided is a photocurable resin composition which is effectively cured by light, so that it can be cured even with a thick film thickness, has low light transmittance after curing, has adhesiveness, and has strength, durability, and moisture resistance. The first aspect of the invention relates to a photocurable resin composition comprising: (A) a photocurable resin, (B) an adhesion imparting agent, and (C) having (A) The difference in refractive index between the component and the cured product of the component (B) is a refractive index of Ο 0.01 or more, a compound which is incompatible and dispersible to the component (A) and the component (B), and (D) black pigment. According to a second aspect of the invention, there is provided a photocurable resin composition, wherein the component (C) is selected from the group consisting of alumina powder and titanium oxide powder. The third aspect of the invention relates to a photocurable resin composition, wherein the component (D) is a carbon powder. According to a fourth aspect of the invention, there is provided a photocurable resin composition, wherein the component (B) is an acrylic, a polyoxygen, a maleimine, a rosin ester, a terpene, a rubber, or an aromatic hydrogenation. Petroleum system adhesion imparting agent. -7- 201035214 The fifth invention relates to a photocurable resin composition in which the component (A) is an acrylic modified resin or an epoxy resin. The present invention relates to a photocurable resin composition, wherein the component (B) is 20 to 170 parts by weight with respect to 100 parts by weight of the component (A), and the component (C) is 0.2 to 80 parts by weight and (D) The present invention relates to a photocurable resin composition which contains a photopolymerization initiator in a step of 0.1 to 35 parts by weight. The invention of the eighth aspect relates to the above-mentioned photocurable resin composition. The ninth aspect of the invention relates to an optical machine component comprising the above-mentioned = hardened material. The invention of claim 10 relates to an optical machine comprising the above-described optical machine member. The commemoration of the electro-optical machine component of the present invention is shown in Fig. 2. [Effects of the Invention] The photocurable resin composition of the present invention can be efficiently cured by light, so that it can be cured by a thick film, and the obtained cured product has low light transmittance from inside and outside, that is, high light-shielding property and adhesion. It is excellent in properties and excellent in various properties such as strength, durability, and moisture resistance. Further, since the photocurable resin composition can be printed or dispensed, the use ratio of the photocurable resin composition is high, and fine lines are easily formed, and the production line can be automated, so that the productivity can be sufficiently improved. -8- 201035214 Therefore, the photocurable resin composition of the present invention can be suitably used as a sealant for optical machines, particularly liquid crystal displays. [Mode for Carrying Out the Invention] The present invention will be described in detail below. The photocurable resin composition of the present invention comprises: (A) a photocurable resin, (B) an adhesion imparting agent, and (C) a cured product of the bismuth (A) component and the (B) component. The difference in refractive index is 0.01 or more, the compound (A) and the component (B) are incompatible and dispersible, and (D) a black pigment. In the present invention, the components (C) and (D) are combined, and the light reflectance of the component (C) is used to achieve thick film hardening and light shielding, and the light absorption by the component (D) is used to achieve light-shielding. In the present invention, the component (A) forms a so-called base resin together with the component (B), and a continuous phase can be formed even in the cured product obtained by curing the photocurable resin composition. The photocurable resin of the present invention is not particularly limited as long as it is a resin which is cured by light such as visible light or ultraviolet light, and examples thereof include (meth)acrylic resin, urethane acrylate resin, and poly Acrylic modified resin such as ester acrylate resin; epoxy resin; oxetane resin. The photocurable resin is preferably, for example, an acrylic modified resin or an epoxy resin, which is defined as a monofunctional and polyfunctional (meth)acrylic acid having an acrylonitrile group or a methacrylonitrile group. Ester compound, can be ~ 9 - 201035214 exemplified as methacrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, third butyl acrylate, isobutyl acrylate, ethyl hexyl acrylate , isodecyl acrylate, n-hexyl acrylate, stearyl acrylate, lauryl acrylate, tridecyl acrylate, ethoxyethyl acrylate, methoxy ethyl acrylate, glycidyl acrylate Ester, butoxyethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-methoxyethyl acrylate, 2-ethoxyethoxyethyl acrylate, A Oxydiethylene glycol acrylate, ethoxy diethylene glycol acrylate, methoxydipropylene glycol acrylate, octafluoropentyl acrylate 'N,N-dimethylaminoethyl acrylate, N, N-diethylaminoethyl Acrylate, allyl acrylate, 1,3-butylene glycol acrylate, 1,4-butanediol acrylate, propylene decylmorpholine, 1,6-hexanediol acrylate, polyethylene glycol II Acrylate, diethylene glycol diacrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate, tripropylene glycol diacrylate, hydroxytrimethyl acetate, neopentyl glycol diacrylate, three Hydroxymethylpropane diacrylic acid, 1,3-bis(hydroxyethyl)-5,5-dimethylhydantoin, 3-methylpentanediol acrylate, α,ω-diacrylic acid di-diethyl Terephthalate, trimethylolpropane triacrylate, pentaerythritol acrylate, pentaerythritol hexaacrylate, dipentaerythritol monohydroxypentaacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, trishydroxyethyl trimer isocyanate Tris(meth)acrylate, dipentaerythritol hexaacrylate, and/or ruthenium adducts thereof, α,ω-tetraallylbistrimethylolpropane tetrahydrofurfurate, 2 -hydroxyethyl propylene decyl phosphate, trimethylolpropane trimethacrylic acid Ester, ethylene glycol di(meth)acrylate-10-201035214, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)propionate, 1,4-butanediol Di(meth)acrylate, anthracene, 6-hexanediol di(meth)acrylate, neopentyl glycol dimethacrylate, dipropylene oxirane ethyl vinegar, N-vinylpyrrolidone and An oligomer of such photoreactive functional groups. The oligomer may, for example, be a (meth) acrylate compound having a polyether skeleton, a polycarbonate skeleton or a polyester skeleton. The product which is commercially available is, for example, a polycarbonate-based acrylic acid ester (product name: UN5 500) manufactured by Kokusai Industrial Co., Ltd., a polyester acrylate (product name: UN7700), and a synthetic chemical industry company. A polyether acrylate (product name: UV3 700B) or the like. Among the above acrylic modified resins, the component (A) is preferably a polycarbonate acrylate. The epoxy resin is defined as a compound having a molecular structure containing one or more epoxy groups, and examples thereof include bisphenol, bisphenol A, hydrogenated bisphenol A, bisphenol F, bisphenol AD, bisphenol S, and tetramethyl group. Bisphenol A, tetramethyl bisphenol F, tetrachlorobisphenol A, tetrabromobisphenol A, etc. bisphenolic diglycidyl ethers, phenolphthalein novolacs, formazan novolacs, brominated phenol novolacs Polyglycidyl ethers of novolac resins such as o-cresol novolac varnish, ethylene glycol, polyethylene glycol, polypropylene glycol, butylene glycol, 1,6-hexanediol, neopentyl glycol, and three A diglycidyl group of an alkylene glycol such as methylolpropane, 1,4-cyclohexanedimethanol, an ethylene oxide adduct of bisphenol A, or a propylene oxide adduct of bisphenol A a glycidyl ester such as an ether, a glycidyl hexahydrophthalic acid or a diglycidyl ester of a dibasic acid, or a 3,4-epoxycyclohexylmethyl-3',4'-epoxy Cyclohexane carboxylate, 3,4-epoxycyclohexylethyl-3',4,-epoxycyclohexanecarboxylate, 3,4·epoxy-6-methylcyclohexyl -3,,4'-ring-11 - 201035214 oxy-6 -Methylcyclohexanecarboxylate, vinyl ring susceptibility ~ agricultural 钸~ oxide, 3.4-epoxy-4-methylcyclohexyl-2 propylene oxide, 2_(3,t epoxy Cyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-m-dioxane, bis(3'epoxycyclohexyl) adipate, bis(3,4-epoxy) Base ring ρ ^ ylmethyl) adipate, lactone modified 3,4-epoxycyclohexylmethyl _v miloxime 3,4, _epoxycyclohexane carboxylate, methylene Bis (3,4-epoxycyclohexane, hydrazine), methylene bis(3,4-epoxycyclohexanyl citrate), dicyclohexadiene diepoxide, double (3) , 4-epoxycyclohexyl)ether, bis(3,4-epoxycyclohexylmethyl)ether, tetrakis(3,4-epoxycyclohexylmethyl)butanetetracarboxylic acid vinegar, double An alicyclic epoxy compound such as (3.4-epoxycyclohexylmethyl)-4,5-epoxytetrahydrophthalic acid vinegar or bis(3.4-epoxycyclohexyl)diethylsiloxane An oligomer having such photoreactive functional groups. Among the above epoxy resins, the component (A) is particularly preferred as bisphenol A. Epoxy resin can be used with acrylic acid modified resin. The component (A) in the present invention is not particularly limited as long as it depends on the refractive index after curing, and a photohardenable resin which imparts a cured product having an arbitrary refractive index can be used. In the present invention, the component (A) can be selected from the above-mentioned resins, and one or a mixture of two or more kinds can be selected in consideration of the properties obtained in the site to be used. The component (B) in the present invention forms a base resin together with the component (A). The component (B) is an adhesiveness imparting agent', and the adhesiveness is imparted to the photocurable resin composition after curing. The component (B) may, for example, be an acidity-imparting agent such as an acrylic acid-based, polyfluorene-based, maleic imine-based, rosin-ester, sulfonium-based, rubber-based or aromatic petroleum-based heat-resistant member. Compatibility -12- 201035214 The viewpoint 'should be a C-acid, a rosin ester, an anthraquinone, or an aromatic hydrogenated petroleum system. The commercially available product can be, for example, given by formula (1):
CHjOHCHjOH
HsOCHj-e-CHjCHa ⑴ CHzOH 所示之Fudow股份公司製多元醇型二甲苯樹脂（改性品 )(K140 )等。 〇 本發明之光硬化性樹脂組成物係可含有（B )成分之 1個或此等之2以上的組合。 (A )成分及（B )成分的硬化物之折射率係使（A ) 成分及（B )成分的混合物硬化，對於此混合物使用Abbe 折射率（At ago股份公司製），藉D線進行測定。 在本發明中之（C)成分係具有與該（A)成分及（B )成分之硬化物的折射率之差爲〇.〇1以上之折射率，對 該（A )成分及（B )成分爲非相溶性且具有分散性之化 Ο 合物，可依（A )成分及（B )成分之硬化物的折射率、 及對（A )成分及（B )成分之非相溶性、分散性而選擇 。（C)成分係可大致區分成：具有折射率較（A)成分 及（B )成分之硬化物的折射率還大〇 · 〇 1以上之化合物（ 高折射率化合物）以及具有折射率較（A )成分及（B ) 成分之硬化物的折射率還小〇.〇丨以上之化合物（低折射 率化合物）。（C)成分爲有機化合物與無機化合物。 在本發明可使用之（A)成分及（B)成分的硬化物 (亦稱爲基材樹脂）與折射率爲0 ·0 1以上相異的（C )成 -13- 201035214 分之無機化合物，例如包含ZnO、Ti02 (氧 、Sb205、Sn02、ITO、Y203、La203、Zr02 鋁）、二氧化矽、橄欖石、玻璃、白碳，較 折射率爲1.60以上之A1203、Ti02、Zr02。 係可舉例如股份公司Admatechs製氧化鋁塡 :AO-902H)等。此處，Al2〇3、Ti02 係光 故尤佳。無機化合物係亦可藉各種之無機、 覆其表面。又，無機化合物之形狀亦可爲球 狀等之任意形狀，其粒徑亦無限定，但粒徑 徑宜爲〇.l~l〇〇Aim，更宜爲0.1〜10"m，尤 // m。 本發明可使用之基材樹脂與折射率爲（ 之（C )成分的有機化合物係可爲液狀或固 聚物、或聚合物化合物的任一者均可，又， 熱硬化性樹脂、光硬化性樹脂之任一者均無 於基材樹脂之光硬化性樹脂，必須爲非相溶 好者。可舉例如包含（甲基）丙烯酸樹脂、 脂、聚酯丙烯酸酯樹脂、環氧樹脂、氧雜環 苯乙烯等之苯乙烯系樹脂、聚對苯二甲酸乙 基咔唑、雙酚A的聚碳酸酯、聚氯化乙烯、 縮水甘油基醚、聚雙酚S縮水甘油基醚、聚 硫胺基甲酸酯樹脂、硫環氧樹脂、含氟的（ 酯類' 氟化伸烷基醚、寡聚物類（平均分5 下）的一官能及二官能以上之多官能（甲基 化鈦）、Ce〇2 、Al2〇3 (氧化 佳係可舉例如 所市售之製品 充劑（製品名 反射性優異， 有機化合物被 狀、針狀、板 愈小愈佳。粒 宜爲〇.1~1 ),〇 1以上相異 體之單體 '寡 熱塑性樹脂、 問題，但相對 性且分散性良 胺基甲酸酯樹 丁烷樹脂、聚 二酯、聚乙烯 聚四溴雙酚A 乙烯基吡啶、 甲基）丙烯酸 F·量：4000 以 )丙烯酸酯類 -14- 201035214 、含有矽之（甲基）丙烯酸酯類、聚乙烯或聚四氟乙烯之 結晶性高分子。又，有機化合物爲固形時，其形狀亦可爲 球狀、針狀、板狀等之任意形狀’其粒徑亦無限定，但粒 徑愈小愈佳。其粒徑宜爲更宜爲0.1~10/zm ，尤宜爲0.1 ~1 β m。有機化合物爲液狀時，該化合物係 分散於光硬化性樹脂。分散粒子之粒徑宜爲0.1-100// m ，更宜爲 尤宜爲 0·1~1μιη。 〇 在本發明中有關一些可使用來作爲（c)成分之化合 物，其折射率例示於以下。 ΖηΟ (折射率 1.90 ) 、Ti02 (折射率 2.3 〜2.7 )、HsOCHj-e-CHjCHa (1) Polyol type xylene resin (modified product) (K140) manufactured by Fudow Co., Ltd. as shown in CHzOH. The photocurable resin composition of the present invention may contain one or a combination of two or more of the components (B). The refractive index of the cured product of the component (A) and the component (B) is a mixture of the component (A) and the component (B), and the Abbe refractive index (manufactured by At ago Co., Ltd.) is used for the mixture, and the measurement is performed by the D line. . In the present invention, the component (C) has a refractive index difference from the cured product of the component (A) and the component (B) of not less than 〇1〇, and the component (A) and (B) The composition is an incompatible and dispersible chemical composition, and the refractive index of the cured product of the component (A) and the component (B) and the incompatibility and dispersion of the component (A) and the component (B) are dispersed. Choose sex. The component (C) can be roughly classified into a compound having a refractive index higher than that of the cured component of the component (A) and the component (B), and a compound having a refractive index greater than or equal to 1 (high refractive index compound) and having a refractive index ( The cured component of the component A and the component (B) has a refractive index of less than 〇丨. The above compound (low refractive index compound). The component (C) is an organic compound and an inorganic compound. In the present invention, the hardened material of the component (A) and the component (B) (also referred to as a base resin) and the inorganic compound having a refractive index of 0·0 1 or more and (C) of -13 to 201035214 For example, it includes ZnO, TiO 2 (oxygen, Sb205, Sn02, ITO, Y203, La203, Zr02 aluminum), cerium oxide, olivine, glass, white carbon, and A1203, Ti02, and Zr02 having a refractive index of 1.60 or more. For example, an alumina 塡: AO-902H manufactured by the company Admatechs, etc. may be mentioned. Here, Al2〇3 and Ti02 are particularly preferred. Inorganic compounds can also be coated with various inorganic and surface materials. Further, the shape of the inorganic compound may be any shape such as a spherical shape, and the particle diameter thereof is not limited, but the particle diameter is preferably 〇.l~l〇〇Aim, more preferably 0.1 to 10"m, especially // m. The base resin which can be used in the present invention and the organic compound having a refractive index (the component (C) can be either a liquid or a solid polymer or a polymer compound, and a thermosetting resin or light. Any of the curable resins is not photocurable resin of the base resin, and must be incompatible. For example, (meth)acrylic resin, fat, polyester acrylate resin, epoxy resin, Styrene resin such as oxostyrene, polyethylene terephthalate, polycarbonate of bisphenol A, polyvinyl chloride, glycidyl ether, polybisphenol S glycidyl ether, poly Thiamate resin, sulfur epoxy resin, fluorine-containing (ester 'fluorinated alkyl ether, oligomer (average of 5) monofunctional and difunctional or higher polyfunctional (methyl Titanium), Ce〇2, and Al2〇3 (for example, a commercially available product charge is preferred. (The product name is excellent in reflectivity, and the organic compound is in the form of a needle or a needle, and the smaller the plate, the better. .1~1), 〇1 above the monomer of the monomer 'oligo-thermoplastic resin, problem, but relative And disperse good urethane-based butane resin, polydiester, polyethylene polytetrabromobisphenol A vinyl pyridine, methyl acrylate F · amount: 4000 acrylate class-14- 201035214, containing a crystalline polymer of (meth) acrylate, polyethylene or polytetrafluoroethylene. When the organic compound is solid, the shape may be any shape such as a spherical shape, a needle shape, or a plate shape. The particle size is also not limited, but the smaller the particle size, the better the particle size is preferably 0.1 to 10/zm, and more preferably 0.1 to 1 β m. When the organic compound is in a liquid state, the compound is dispersed in the light. The curable resin. The particle diameter of the dispersed particles is preferably from 0.1 to 100 / m, more preferably from 0.1 to 1 μm. In the present invention, some of the compounds which can be used as the component (c) are refracted. The rate is exemplified below. ΖηΟ (refractive index 1.90), Ti02 (refractive index 2.3 to 2.7),
Ce02(折射率 1.95) 、Sb205 (折射率 1.71) 、Sn02、 ITO(折射率 1，95) 、Y203 (折射率 1.87) 、La203 (折 射率 1.95 ) 、Zr02 (折射率 2.05 ) 、Al2〇3 (折射率 1.6〜1.8)、三聚氰胺樹脂（1.6)、尼龍（1.53)、聚苯 乙烯（1.6)、聚乙烯（1_53)、聚四氟乙烯（1,35)、甲 Ο 基丙烯酸甲酯樹脂（1.. 4 9 )、氯化乙烯樹脂（1 · 5 4 )、聚 石夕氧油（1 · 4 )。 在本發明中，（C)成分之折射率與（A)成分及（B )成分之硬化物的折射率之差宜爲0.05以上，更宜爲0.1 以上，尤宜爲〇 . 1 5以上。 本發明之光硬化性樹脂組成物係就（C )成分而言可 含有有機及無機之高折射率化合物及有機及無機之低折射 率化合物的一個或此等2以上之組合。 若相對於（A )成分及（B )成分爲「非相溶性」係 -15- 201035214 意指（c)成分不與（A)成分及（B)成分之混合物均一 地混合’對於（A)成分及（B)成分爲「分散性」意指 (C)成分與（a)成分及（B)成分之混合物擾拌後不分 離成二層。 在本發明中之（D )成分爲黑色顏料，對光硬化性樹 脂組成物賦予遮光性。（D )成分爲維持光硬化性樹脂組 成物之加工性，宜以少量之添加賦予遮光性。（d )成分 可舉例如無機或有機顏料。無機顏料可舉例如含有碳粉末 ^ 、象牙（ivory )黑、火星（Mars )黑、瀝青黑、燈黑' 銅、鐵、鉻、錳 '鈷等之無機系黑、鈦黑等。宜爲碳粉末 ，更宜爲碳黑、乙诀黑、科琴黑（Ketjen black)、奈米 碳管、天然石墨粉末、人造石墨粉末等，從以少量添加對 硬化後之光硬化性樹脂組成物賦予遮光性的觀點，尤宜爲 碳黑、乙炔黑、科琴黑。有機顏料可舉例如苯胺黑、茈黑 ，宜爲茈黑。所市售之製品係可舉例如日弘BICS股份公 司製黑色顏料（製品名：NBD-0744 )等。（有關黑顏料 0 之粒徑，若有可例示之範圍或較佳之範圍，請記載） 本發明之光硬化性樹脂組成物係可含有（D )成分之 一個或此等之2以上的組合。 本發明之光硬化性樹脂組成物係相對於（A )成分 100重量份，（B )成分可爲20〜170重量份，（c )成分 可爲0.2~80重量份以及（D)成分爲0.1~35重量份。 本發明之光硬化性樹脂組成物係相對於（A )成分 100重量份，（B)成分宜爲30〜150重量份’更宜爲 -16- 201035214 5 0〜1 2 0重量份。 本發明之光硬化性樹脂組成物係相對於（A )成分 1〇〇重量份’ （C)成分宜爲1~50重量份，更宜爲5〜4〇 重量份，尤宜爲8~30重量份。 本發明之光硬化性樹脂組成物係相對於（A )成分 100重量份，（D)成分宜爲0.1〜20重量份，更宜爲 0.1〜10重量份，尤宜爲0.14〜0.7重量份。 〇 本發明之光硬化性樹脂組成物係從印刷性、點膠性之 觀點，宜爲 5,000~200,000mPa. S 的黏度，更宜爲 1 0,000〜8 0,00011^.3之黏度。此處光硬化性樹脂組成物 之黏度係使用東機產業製RE-10U型黏度計，以Cone Plate型旋轉子，在室溫之條件下測定。 本發明之光硬化性樹脂組成物係進一步可含有光聚合 起始劑。光聚合起始劑可包含一般所市售之自由基或陽離 子系起始劑，可例示如羰基系：二苯甲酮、二乙醯基、苯 〇 甲基、苯偶因、ω-溴乙醯苯、氯丙酮、乙醯苯、2，2-二乙 氧基乙醯苯、2，2_二甲氧基-2-苯基丙酮、ρ-二甲基胺基乙 醯苯、ρ-二甲基胺基丙醯苯、2_氯二苯甲酮、ρ,ρ’-雙二乙 基胺基二苯甲酮、米希勒酮、苯偶因甲基醚、苯偶因異丁 基醚 '苯偶因-正丁基醚、苯甲基二甲基縮酮、卜羥基環 己基苯基酮、2 -經基-2-甲基-1-酮、1-(4 -異丙基本基）· 2 -羥基-2 -甲基丙烷-1-酮、甲基苯甲醯基甲酸酯、2,2·二 乙氧基乙醯苯、4-Ν，Ν，-二甲基乙醯苯類；硫醚系：二苯 基二硫醚、二苯甲基二硫醚；醌系：苯醌、蔥醌：偶氮系 -17- 201035214 :偶氮雙異丁腈、2,2’-偶氮雙丙烷。所市售之製品可舉例 如Ciba Japan股份公司製1-羥基環己基苯基酮（製品名 :IRGACURE 184) 、1-羥基環己基苯基酮50份與二苯甲 酮50份之共融混合物（製品名：IRGACURE 500)等。光 聚合起始劑係可以一般所使用之量例如相對於（A )成分 之光硬化性樹脂100重量份爲1~1〇重量份之量使用。照 射光係可爲可見光線、紫外線、輻射線、電子束之任一者 ’但從硬化後之黏著性的觀點宜爲紫外線。 又’本發明之光硬化性樹脂組成物係爲提昇硬化後之 黏著性’在無損本發明之效果的範圍，可含有氣泡。 本發明之光硬化性樹脂組成物係就印刷性之改善等目 的可含有溶劑’但從對環境之考量、及光硬化性樹脂組成 物的使用率之觀點，亦宜以無溶劑使用。 本發明之光硬化性樹脂組成物係依據目的而進一步可 添加其他公知之添加劑，例如抗氧化劑、紫外線吸收劑、 光安定劑、矽烷偶合劑、熱聚合抑制劑、流平劑、界面活 性劑、著色劑、保存安定劑、可塑劑、滑劑、塡充劑、抗 老化劑、潤濕性改良劑、離型劑等。 本發明之光硬化性樹脂組成物係可使前述各成分藉常 用方法進行混合而製造。各成分之添加順序無特別限制。 高折射率或低折射率化合物爲液狀時係宜使該化合物於光 硬化性樹脂以細的粒徑分散。 本發明之光硬化性樹脂組成物係於網版印刷機或點膠 機等熟悉此技藝者可以公知的方法進行印刷、點膠，可容 -18- 201035214 易地形成微細線。微細線之線寬宜爲1 000 " m以下，更 宜爲700 // m以下，尤宜爲600 // m以下。又，從遮光性 、黏著性、密封性之觀點，微細線之線寬宜爲500 # m以 上，更宜爲600/zm以上。 本發明之光硬化性樹脂組成物係可藉由可見光、紫外 線等之光有效地硬化，可在廣範圍之膜厚例如0.5〆m以 上範圍的膜厚硬化。光硬化之條件係可依樹脂組成物之組 Ο 成或膜厚等而改變，但例如成分（A ):丙烯酸樹脂、成 分（B ):丙烯酸系黏著賦予劑、成分（C ):氧化鋁、 成分（D):碳黑 '膜厚100/im時，紫外線照射量爲 1 000mJ/cm2 以上 ° 本發明係含有光硬化性樹脂組成物之硬化物。此硬化 物爲具有遮光性與黏著性者，且強度' 耐久性、耐濕性等 各種特性優異，故同時滿足固定（密封）用樹脂與遮光用 樹脂的特性。本發明之硬化物在30/zm〜150/zm之範圍的 〇 Μ 膜厚中，可使300〜800nm中之光透過率爲1%以下，例如 〇·5%以下，宜爲0.1%以下，尤宜爲0.05%以下，最宜爲 〇 · 〇 1 %以下。 在本發明中，所謂「具有黏著性」意指被黏體與硬化 後之光硬化性樹脂組成物接觸時，可對被黏體潤濕的黏性 、及貼黏後，具有很難從被黏體剝離之彈性兩者的狀態。 本發明係亦含有具上述硬化物之光學機器構件。光學 機器構件係可舉例如液晶面板、感測器、光拾取器、光學 透鏡、LED。本發明係尤其適用於液晶面板。 -19 - 201035214 本發明係進一步亦有關含有上述光學機器構件的光學 機器。光學機器可舉例如各種顯示器、數位照相機、各種 記錄媒體播放機等’尤其適於液晶顯不器。 【實施方式】 [實施例] 以下，藉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實施例。在以下中，「份」爲重量基 準。 (實施例1~6及比較例1 ) 首先，硏究成分（D )之添加量對光硬化性樹脂組成 物之深度硬化性的影響，故進行實施例1〜6。 (光硬化性樹脂組成物之調製） 使作爲（A)成分之根上工業股份公司製聚碳酸酯系 胺基甲酸酯丙烯酸酯（製品名：UN- 5 5 00，重量平均分子 量：約50,000 ) 84份、共榮社化學股份公司製2-羥基乙 基甲基丙烯酸酯（製品名：HO) 14份、及共榮社化學股 份公司月桂基丙烯酸酯（製品名：LA ) 2份、作爲（B ) 成分之Fudow股份公司製多元醇型二甲苯樹脂（改性品 )(K140) 84份、作爲（C)成分之Admatechs股份公司 製氧化鋁塡充劑（製品名：AO-902H、平均粒徑： 、折射率1.76 ) 14份、作爲（D )成分之日弘Vies股份 -20- 201035214 公司製黑色顏料（製品名：NBD-0744 ) 0.1 4〜7.0份（參 照表1 )、作爲光聚合起始劑之Ciba Japan股份公司製1 _ 羥基環己基苯基酮50份與二苯甲酮50份之化合物（製品 名：IRGACURE 500 ) 4.2份進行混合，調製光硬化性樹 脂組成物。就比較例1而言，只（D )成分爲0份其他係 調製與實施例1〜6同樣地進行混合之光硬化性樹脂組成物 。又，成分（A)及（B)成分之硬化物的折射率爲1>52 ❹ (光硬化性樹脂組成物於管體的塡充） 如圖3所示般，於鋁板上貼黏5mm徑的紫外線透過 性之黑色聚乙烯管。於鋁板上成爲管體高1〜2mm般，塡 充所調製之光硬化性樹脂組成物至黑色管體的前端後，密 封黑色管體，製作試樣。 〇 (光照射） 於所製作之試樣，Eyegraphics股份公司製Metal係 使用1^§1^17?6 1；¥燈（型號：1^03-1^31)，以股份公司 OAK製作所製UV感測器（型號：UV_3 5 )所測得的測定 値成爲3，000mJ/cm2般，照射UV。又，照射係只對UV 燈平行（相對於樹脂爲深度方向）之UV光進行。 (光硬化性樹脂組成物之硬化部分的測定） 從U V照射後之黑色管體取出已硬化的部分之光硬化 -21 - 201035214 性樹脂組成物，使所硬化的部分之厚度以毫米計（ m i c r 〇 m e t e r )測定。測定爲 η = 5。 (結果） 結果表示於表1中。 [表1] 黑色顔料之添加量 所硬化之部分的厚度 (份） (β m) 比較例1 0.0 1014 實施例1 0.14 320 實施例2 0.28 265 實施例3 0.7 220 實施例4 1.4 140 實施例5 4.2 110 實施例6 7.0 64 如表1般，若黑色顏料之添加量爲4.2份以下，證實 可使厚1 1 0 Αί m以上之光硬化性樹脂組成物硬化。從可得 到200〜3 0〇em之硬化厚的點，更佳之黑色顏料的添加量 爲 0.14~0.7 份。 (實施例7 ) 其次，爲硏究已硬化之光硬化性樹脂組成物之膜厚與 遮光性之關係，故進行實施例7。 (光硬化性樹脂組成物之調製） -22- 201035214 使作爲（A)成分之根上工業股份公司製聚碳酸酯系 胺基甲酸酯丙烯酸酯（製品名：UN-5500，重量平均分子 量：約50,000 ) 84份、共榮社化學股份公司製2-羥基乙 基甲基丙烯酸酯（製品名：HO ) 14份、及共榮社化學股 份公司月桂基丙烯酸酯（製品名：LA ) 2.0份、作爲（B )成分之Fudow股份公司製多元醇型二甲苯樹脂（改性 品）（K140) 84份、作爲（C)成分之Admatechs股份公 〇 司製氧化鋁塡充劑（製品名：AO-902H、平均粒徑：0.7 /zm、折射率1.76) 21份、作爲（D)成分之日弘Vies股 份公司製黑色顏料（製品名：NBD-0744) 0.42份、作爲 光聚合起始劑之Ciba Japan股份公司製卜羥基環己基苯 基酮50份與二苯甲酮5〇份之混合物（製品名： IRGACURE 500 ) 4.2份進行混合，調製光硬化性樹脂組 成物。又’成分（A)及（B)成分之硬化物的折射率爲 1.52。 〇 (光硬化性組成物之塗佈） 其次’使用點膠機’於厚1 . 〇mm之冕牌玻璃基板上 ，以寬：1mm、長：50mm、厚 5(^m* ，塗佈所 調製之光硬化性樹脂組成物，製作試胃。 (光照射） 與貫施例1〜6同樣地，對所製作之試樣照射uv。 -23- 201035214 (厚度200、3 00、5 00 # m硬化之光硬化性樹脂組成物的 試樣製作） 膜厚200、3 00、500 // m硬化之光硬化性樹脂組成物 的試樣係藉由反覆厚1 〇〇 m之上述光硬化性樹脂組成物 的塗佈、上述光照射來製作。 (光之透過率的測定） 如以上般所製作之膜厚爲50、100、200、3 00、500 am的試樣，使用日本分光股份公司製紫外可見光分光光 度計（型號：U-best V-5 70 )，而測定波長爲3 00nm (紫 外線區域）、400nm (紫外線/可見光區域）、500nm (可 見光區域）、600nm (可見光區域）、700nm (可見光區 域）、8 OOnm (可見光區域/紅外線區域）之光的透過率。 (結果） 有關光硬化性樹脂組成物之膜厚與透過率的關係，所 得到之結果表示於表2中。 [表2] 膜厚 波長 50 /z m 100" m 200 β m 300 /z m 500 β m 300nm 1.60 0.00 0.00 0.00 0.00 400nm 8.50 0.16 0.00 0.00 0.00 500nm 16.60 0.51 0.00 0.04 0.00 600nm 25.20 1.44 0.10 0.07 0.00 700nm 33.20 3.10 0.73 0.16 0.00 800nm 40.30 5.20 1.60 0.40 0.05 -24- 201035214 從表2之結果’可證實若硬化後之光硬化性樹脂組成 物的厚度爲以下’透過紫外線或可見光，即使厚 度爲200 # m亦透過可見光區域/紅外線區域光。此結果， 認爲對於硬化前之光硬化性樹脂組成物亦同樣。另外，在 厚度爲1〇〇"111以上時紫外線不會透過，若厚度爲2〇0 "m以上’較佳係300 // m以上，可證實紫外線/可見光區 〇 域〜可見光區域/紅外線區域不會透過，或幾乎不透過。 (實施例8 ) 其次’硏究成分（D )之添加對已硬化的光硬化性樹 脂組成物之遮光性的影響，故進行實施例8。 (光硬化性樹脂組成物之調製） 使作爲（A )成分之根上工業股份公司製聚碳酸酯系 G 胺基甲酸酯丙烯酸酯（製品名：UN-5500，重量平均分子 量：約50,000 ) 84份、共榮社化學股份公司製2-羥基乙 基甲基丙烯酸酯（製品名：HO) 10份、及共榮社化學股 份公司月桂基丙稀酸酯（製品名：LA) 2.0份 '作爲（B )成分之Fudow股份公司製多元醇型二甲苯樹脂（改性 品）（K140) 84份、作爲（C)成分之Admateehs股份公 司製氧化鋁塡充劑（製品名：A 0 - 9 0 2 Η、平均粒徑：〇 . 7 # m、折射率1.76 ) 14份、作爲（D )成分之曰弘Vies股 份公司製黑色顏料（製品名：NBD-0744 ) 0.28份、作爲 -25- 201035214 光聚合起始劑之Ciba Japan股份公司製1-羥基環己基苯 基酮 50份與二苯甲酮 50份之混合物（製品名： IRGACURE 500 ) 4.2份進行混合，調製光硬化性樹脂組 成物。就比較例2而言，只（D )成分爲〇份其他係調製 與實施例8同樣地進行混合之光硬化性樹脂組成物。又’ 成分（A)及（B )成分之硬化物的折射率爲1.52。 (光硬化性組成物之塗佈） 其次，使用點膠機，於厚1.0mm之冕牌玻璃基板上 ，以寬：1mm、長：50mm、厚100"m’塗佈所調製之光 硬化性樹脂組成物，製作試樣。 (光照射） 與實施例1 同樣地，對所製作之試樣照射UV。 (厚度5 00 /2 m硬化之光硬化性樹脂組成物的試樣製作） 膜厚5 Ο Ο μ m硬化之光硬化性樹脂組成物的試樣係藉 由進一步反覆4次厚1 0 〇 # m之上述光硬化性樹脂組成物 的塗佈、及光照射來製作。 (光之透過率的測定） 與實施例2同樣做法’而測定透過率’進一步測定反 射率。又，反射率係使用日本分光股份公司製紫外可見光 分光光度計（型號：U-best V-570 )，藉90°C絕對反射法 -26- 201035214 進行測定。 (結果） 將光硬化性樹脂組成物之膜厚與透過率的關係之結果 表示於圖4中，光硬化性樹脂組成物之膜厚與反射率的關 係之結果表示於圖5中。 如圖4所示般，添加成分（D)之實施例8、與未添 〇 加成分（D )之比較例2的透過率存在差。如圖5所示般 ，可證實實施例8之反射率若與比較例2之反射率比較， 在3 00nm之波長中降低至約1/2，在3 50nm以上之波長係 降低至比較例2之反射率的約1 /5以下。 (實施例9〜16 ) 其次，爲硏究成分（A )的添加對已硬化之光硬化性 樹脂組成物的黏著強度之影響，進行實施例9〜1 6。Ce02 (refractive index 1.95), Sb205 (refractive index 1.71), Sn02, ITO (refractive index 1, 95), Y203 (refractive index 1.87), La203 (refractive index 1.95), Zr02 (refractive index 2.05), Al2〇3 ( Refractive index 1.6 to 1.8), melamine resin (1.6), nylon (1.53), polystyrene (1.6), polyethylene (1_53), polytetrafluoroethylene (1, 35), methyl methacrylate resin (1) .. 4 9 ), chlorinated vinyl resin (1 · 5 4 ), polysulfuric acid (1 · 4). In the present invention, the difference between the refractive index of the component (C) and the refractive index of the cured product of the component (A) and the component (B) is preferably 0.05 or more, more preferably 0.1 or more, and particularly preferably 〇1.5 or more. The photocurable resin composition of the present invention may contain one or more of a combination of an organic and inorganic high refractive index compound and an organic and inorganic low refractive index compound as the component (C). If it is "incompatible" with respect to (A) and (B), -15- 201035214 means that component (c) is not uniformly mixed with the mixture of (A) and (B) 'for (A) The component and the component (B) are "dispersible" means that the mixture of the component (C) and the component (a) and the component (B) is not separated into two layers after being scrambled. In the present invention, the component (D) is a black pigment, and the light-curable resin composition is provided with a light-shielding property. The component (D) is a process for maintaining the workability of the photocurable resin composition, and it is preferred to impart a light-shielding property with a small amount of addition. The component (d) may, for example, be an inorganic or organic pigment. The inorganic pigment may, for example, be inorganic black or titanium black containing carbon powder ^, ivory black, Mars black, pitch black, lamp black 'copper, iron, chromium, manganese 'cobalt or the like. It should be carbon powder, more preferably carbon black, acetonitrile black, Ketjen black, carbon nanotubes, natural graphite powder, artificial graphite powder, etc., from a small amount of added hardened photocurable resin From the viewpoint of imparting light-shielding properties to the composition, carbon black, acetylene black, and ketjen black are particularly preferable. The organic pigment may, for example, be aniline black or ruthenium black, and is preferably ruthenium. The commercially available product may, for example, be a black pigment (product name: NBD-0744) manufactured by Rihong BICS Co., Ltd., or the like. (The photocurable resin composition of the present invention may contain one or a combination of two or more of the components (D), if the particle size of the black pigment 0 is in the range of the exemplified or the preferred range. The photocurable resin composition of the present invention may be 20 to 170 parts by weight based on 100 parts by weight of the component (A), 0.2 to 80 parts by weight of the component (c) and 0.1 to (D). ~35 parts by weight. The photocurable resin composition of the present invention is preferably 30 to 150 parts by weight, more preferably -16 to 201035214 5 0 to 1 2 parts by weight, based on 100 parts by weight of the component (A). The photocurable resin composition of the present invention is preferably 1 to 50 parts by weight, more preferably 5 to 4 parts by weight, even more preferably 8 to 30 parts by weight per part by weight of the component (A). Parts by weight. The photocurable resin composition of the present invention is preferably used in an amount of 0.1 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, even more preferably 0.14 to 0.7 part by weight, per 100 parts by weight of the component (A). The photocurable resin composition of the present invention preferably has a viscosity of 5,000 to 200,000 mPa·s from the viewpoint of printability and dispensing property, and more preferably a viscosity of from 10,000 to 80,00011. Here, the viscosity of the photocurable resin composition was measured using a RE-10U viscometer manufactured by Toki Sangyo Co., Ltd. using a Cone Plate type rotor at room temperature. The photocurable resin composition of the present invention may further contain a photopolymerization initiator. The photopolymerization initiator may comprise a commercially available radical or cationic initiator, such as a carbonyl system: benzophenone, diethyl hydrazino, benzoquinone methyl, benzoin, ω-bromine B. Benzene, chloroacetone, acetophenone, 2,2-diethoxyethyl benzene, 2,2-dimethoxy-2-phenylacetone, ρ-dimethylaminoethyl benzene, ρ- Dimethylaminobenzidine, 2-chlorobenzophenone, ρ,ρ'-bisdiethylaminobenzophenone, michelone, benzoin methyl ether, benzoin isobutylene Ether Benzene-n-butyl ether, benzyl dimethyl ketal, hydroxycyclohexyl phenyl ketone, 2-cyano-2-methyl-1-one, 1-(4-isopropyl Base) · 2-hydroxy-2-methylpropan-1-one, methyl benzhydrazide, 2,2·diethoxyethyl benzene, 4-anthracene, fluorene, -dimethyl Acetylbenzene; thioether system: diphenyl disulfide, diphenylmethyl disulfide; lanthanide: benzoquinone, onion 醌: azo -17- 201035214: azobisisobutyronitrile, 2, 2'-azobispropane. The commercially available product may, for example, be 1-hydroxycyclohexyl phenyl ketone (product name: IRGACURE 184) manufactured by Ciba Japan Co., Ltd., a mixture of 50 parts of 1-hydroxycyclohexyl phenyl ketone and 50 parts of benzophenone. (product name: IRGACURE 500) and so on. The photopolymerization initiator can be used in an amount of usually 1 to 1 part by weight based on 100 parts by weight of the photocurable resin of the component (A). The illuminating light system may be any one of visible light, ultraviolet ray, radiation, and electron beam, but is preferably ultraviolet ray from the viewpoint of adhesion after curing. Further, the photocurable resin composition of the present invention has an adhesive property after the hardening is cured, and does not detract from the effects of the present invention, and may contain bubbles. The photocurable resin composition of the present invention may contain a solvent for the purpose of improving the printability, etc., but it is also preferably used without a solvent from the viewpoint of environmental considerations and the use ratio of the photocurable resin composition. The photocurable resin composition of the present invention may further contain other known additives depending on the purpose, such as an antioxidant, an ultraviolet absorber, a light stabilizer, a decane coupling agent, a thermal polymerization inhibitor, a leveling agent, a surfactant, A coloring agent, a storage stabilizer, a plasticizer, a slip agent, a chelating agent, an anti-aging agent, a wettability improver, a release agent, and the like. The photocurable resin composition of the present invention can be produced by mixing the above components by a usual method. The order of addition of each component is not particularly limited. When the high refractive index or low refractive index compound is in the form of a liquid, the compound is preferably dispersed in a fine particle diameter in the photocurable resin. The photocurable resin composition of the present invention is printed or dispensed by a method known to those skilled in the art such as a screen printing machine or a dispenser, and can easily form fine lines by -18-201035214. The line width of the fine line should be 1 000 " m or less, more preferably 700 // m or less, and particularly preferably 600 // m or less. Further, from the viewpoint of light-shielding property, adhesiveness, and sealing property, the line width of the fine wire should preferably be 500 # m or more, and more preferably 600/zm or more. The photocurable resin composition of the present invention can be effectively cured by light such as visible light or ultraviolet light, and can be cured in a wide range of film thicknesses, for example, a film thickness of 0.5 〆m or more. The photohardening conditions may vary depending on the composition of the resin composition, the film thickness, and the like, but for example, the component (A): an acrylic resin, the component (B): an acrylic adhesion imparting agent, and the component (C): alumina, Component (D): When the film thickness of carbon black is 100/im, the amount of ultraviolet irradiation is 1 000 mJ/cm 2 or more. The present invention contains a cured product of a photocurable resin composition. Since the cured product is excellent in various properties such as light resistance and adhesion, and has properties such as durability and durability, it satisfies the properties of the resin for sealing (sealing) and the resin for light shielding. The cured product of the present invention may have a light transmittance of from 1 to 300% in the range of from 300 to 800 nm in the thickness of the ruthenium in the range of from 30 to zm to 150/zm, for example, 〇·5% or less, preferably 0.1% or less. It is particularly preferably 0.05% or less, and most preferably 〇·〇1% or less. In the present invention, the term "adhesive" means that when the adherend is in contact with the cured photocurable resin composition, it is hard to be wetted by the adherend, and after sticking, it is difficult to be The state of both elasticity of the body peeling. The present invention also encompasses an optical machine component having the above cured product. The optical machine member may be, for example, a liquid crystal panel, a sensor, an optical pickup, an optical lens, or an LED. The invention is particularly applicable to liquid crystal panels. -19 - 201035214 The invention further relates to an optical machine comprising the above optical machine component. The optical device can be, for example, various displays, digital cameras, various recording media players, etc., which are particularly suitable for liquid crystal displays. [Embodiment] [Examples] Hereinafter, the present invention will be described in more detail by way of examples and comparative examples, but the invention is not limited to the examples. In the following, "parts" are weight basis. (Examples 1 to 6 and Comparative Example 1) First, the effects of the addition amount of the component (D) on the deep curing property of the photocurable resin composition were examined, and Examples 1 to 6 were carried out. (Preparation of a photocurable resin composition) A polycarbonate-based urethane acrylate (product name: UN-5500, weight average molecular weight: about 50,000) manufactured by Kokusai Kogyo Co., Ltd. as the component (A) 84 parts, 14 parts of 2-hydroxyethyl methacrylate (product name: HO) manufactured by Kyoeisha Chemical Co., Ltd., and 2 parts of lauryl acrylate (product name: LA) of Kyoeisha Chemical Co., Ltd. B) A total of 84 parts of polyol type xylene resin (modified product) (K140) made by Fudow Co., Ltd., and an alumina chelating agent made by Admatechs Co., Ltd. as a component (C) (product name: AO-902H, average grain) Diameter: refractive index 1.76) 14 parts, as a component (D), Nikko Vies shares -20- 201035214 Company black pigment (product name: NBD-0744) 0.1 4 to 7.0 parts (refer to Table 1), as photopolymerization 50 parts of 1 - hydroxycyclohexyl phenyl ketone prepared by Ciba Japan Co., Ltd. and 50 parts of benzophenone (product name: IRGACURE 500) were mixed with 4.2 parts to prepare a photocurable resin composition. In Comparative Example 1, only the (D) component was 0 parts, and the photocurable resin composition which was mixed in the same manner as in Examples 1 to 6 was prepared. Further, the cured product of the components (A) and (B) has a refractive index of 1 > 52 ❹ (the photocurable resin composition is filled in the tube). As shown in Fig. 3, the 5 mm diameter is adhered to the aluminum plate. UV-transparent black polyethylene tube. On the aluminum plate, the tube body was made 1 to 2 mm high, and the prepared photocurable resin composition was applied to the front end of the black tube body, and then the black tube body was sealed to prepare a sample. 〇 (light irradiation) The sample produced by Eyegraphics Co., Ltd. uses 1^§1^17?6 1; ¥ lamp (model: 1^03-1^31), manufactured by the company OAK. The measured enthalpy measured by the sensor (model: UV_3 5 ) was 3,000 mJ/cm 2 and was irradiated with UV. Further, the irradiation is performed only on the UV light in which the UV lamps are parallel (in the depth direction with respect to the resin). (Measurement of Hardened Portion of Photocurable Resin Composition) The hardened portion of the hardened portion was taken out from the black tube after UV irradiation to measure the thickness of the hardened portion in millimeters (micr) 〇meter ). The measurement was η = 5. (Results) The results are shown in Table 1. [Table 1] Thickness (parts) of the portion to which the black pigment was added (β m) Comparative Example 1 0.0 1014 Example 1 0.14 320 Example 2 0.28 265 Example 3 0.7 220 Example 4 1.4 140 Example 5 4.2 110 Example 6 7.0 64 As shown in Table 1, when the amount of the black pigment added was 4.2 or less, it was confirmed that the photocurable resin composition having a thickness of 1 10 Å or more was hardened. From the point where the hardening thickness of 200 to 30 〇em is obtained, the addition amount of the black pigment is preferably 0.14 to 0.7 parts. (Example 7) Next, in order to investigate the relationship between the film thickness of the cured photocurable resin composition and the light-shielding property, Example 7 was carried out. (Preparation of a photocurable resin composition) -22- 201035214 A polycarbonate-based urethane acrylate manufactured by Kokusai Kogyo Co., Ltd. as a component (A) (product name: UN-5500, weight average molecular weight: about 50,000) 84 parts, 14 parts of 2-hydroxyethyl methacrylate (product name: HO) manufactured by Kyoeisha Chemical Co., Ltd., and 2.0 parts of lauryl acrylate (product name: LA) of Kyoeisha Chemical Co., Ltd. 84 parts of polyol type xylene resin (modified product) (K140) manufactured by Fudow Co., Ltd. as component (B), and Admatechs Co., Ltd. as a component (C), alumina filler (product name: AO- 902H, average particle diameter: 0.7 / zm, refractive index 1.76) 21 parts, as a component (D), a black pigment (product name: NBD-0744) made by Nippon Vies Co., Ltd. 0.42 parts, Ciba as a photopolymerization initiator A mixture of 50 parts of hydroxycyclohexyl phenyl ketone and 5 parts of benzophenone (product name: IRGACURE 500) of Japan Corporation was mixed to prepare a photocurable resin composition. Further, the cured product of the components (A) and (B) had a refractive index of 1.52. 〇 (application of photo-curable composition) Next, 'use a dispenser' on a 1 冕 冕 冕 brand glass substrate, width: 1 mm, length: 50 mm, thickness 5 (^m*, coating station The photocurable resin composition was prepared to prepare a stomach test. (Light Irradiation) The prepared sample was irradiated with uv in the same manner as in Examples 1 to 6. -23- 201035214 (thickness 200, 300, 5 00 # Sample preparation of m-cured photocurable resin composition) The sample of the photocurable resin composition having a thickness of 200, 300, and 500 m was cured by the reverse photohardness of 1 μm thick. The coating of the resin composition and the above-mentioned light irradiation were carried out. (Measurement of transmittance of light) Samples having a film thickness of 50, 100, 200, 300, and 500 am produced as described above were used. UV-visible spectrophotometer (model: U-best V-5 70), and measuring wavelengths of 300 nm (ultraviolet region), 400 nm (ultraviolet/visible region), 500 nm (visible region), 600 nm (visible region), 700 nm (visible light region), transmittance of light of 800 nm (visible region/infrared region) (Result) The relationship between the film thickness of the photocurable resin composition and the transmittance was shown in Table 2. [Table 2] Film thickness wavelength 50 /zm 100" m 200 β m 300 /zm 500 β m 300nm 1.60 0.00 0.00 0.00 0.00 400nm 8.50 0.16 0.00 0.00 0.00 500nm 16.60 0.51 0.00 0.04 0.00 600nm 25.20 1.44 0.10 0.07 0.00 700nm 33.20 3.10 0.73 0.16 0.00 800nm 40.30 5.20 1.60 0.40 0.05 -24- 201035214 The results from Table 2 can be confirmed The thickness of the photocurable resin composition after curing is as follows: 'transmits ultraviolet rays or visible light, and transmits light in the visible light region/infrared region even if the thickness is 200 # m. As a result, it is considered that the photocurable resin composition before curing is also Similarly, when the thickness is 1〇〇"111 or more, the ultraviolet rays will not pass through. If the thickness is 2〇0 "m or more, and the thickness is preferably more than 300 // m, it can be confirmed that the ultraviolet/visible region is visible to the visible light. The region/infrared region is not transmitted or hardly permeated. (Example 8) Next, the addition of the component (D) to the hardened photocurable resin composition Light-shielding effect, it is carried out in Example 8. (Preparation of a photocurable resin composition) A polycarbonate-based G urethane acrylate (product name: UN-5500, weight average molecular weight: about 50,000) manufactured by Kokusai Kogyo Co., Ltd. as the component (A) 84 Co., Ltd., Co., Ltd., 2-hydroxyethyl methacrylate (product name: HO), 10 parts, and Kyungworgan Chemical Co., Ltd., lauryl acrylate (product name: LA) 2.0 parts (B) component of the polyol type xylene resin (modified product) (K140) manufactured by Fudow Co., Ltd., 84 parts, and alumina filler (made by Admateehs Co., Ltd.) as component (C) (product name: A 0 - 9 0 2 Η, average particle size: 〇. 7 # m, refractive index 1.76) 14 parts, as a component (D), 黑色Hong Vies Co., Ltd. made black pigment (product name: NBD-0744) 0.28 parts, as -25- 201035214 A mixture of 50 parts of 1-hydroxycyclohexyl phenyl ketone prepared by Ciba Japan Co., Ltd. and 50 parts of benzophenone (product name: IRGACURE 500) of a photopolymerization initiator was mixed to prepare a photocurable resin composition. In Comparative Example 2, only the component (D) was a component of the photocurable resin which was mixed in the same manner as in Example 8 except for the other components. Further, the cured product of the components (A) and (B) had a refractive index of 1.52. (Coating of Photocurable Composition) Next, using a dispenser, the light hardening property was adjusted by a width of 1 mm, a length of 50 mm, and a thickness of 100 Å on a 玻璃 brand glass substrate having a thickness of 1.0 mm. A resin composition was used to prepare a sample. (Light Irradiation) In the same manner as in Example 1, the produced sample was irradiated with UV. (Preparation of a sample of a photocurable resin composition having a thickness of 5 00 /2 m) Film thickness 5 Ο Ο μ m The sample of the photocurable resin composition which is hardened by further reversing the thickness of 4 times 10 〇# It is produced by coating and photoirradiation of the photocurable resin composition of m described above. (Measurement of light transmittance) The transmittance was measured in the same manner as in Example 2, and the reflectance was further measured. Further, the reflectance was measured by an ultraviolet-visible spectrophotometer (Model: U-best V-570) manufactured by JASCO Corporation, by the 90 °C absolute reflection method -26-201035214. (Result) The result of the relationship between the film thickness of the photocurable resin composition and the transmittance is shown in Fig. 4, and the results of the relationship between the film thickness of the photocurable resin composition and the reflectance are shown in Fig. 5 . As shown in Fig. 4, the transmittance of Example 8 in which the component (D) was added and Comparative Example 2 in which the component (D) was not added was inferior. As shown in FIG. 5, it was confirmed that the reflectance of Example 8 was lowered to about 1/2 in the wavelength of 300 nm as compared with the reflectance of Comparative Example 2, and the wavelength was lowered to Comparative Example 2 at a wavelength of 3 50 nm or more. The reflectance is about 1 /5 or less. (Examples 9 to 16) Next, in order to investigate the influence of the addition of the component (A) on the adhesion strength of the cured photocurable resin composition, Examples 9 to 16 were carried out.
G (光硬化性樹脂組成物之調製） 以表3所示之量，使作爲（A)成分之根上工業股份 公司製聚碳酸酯系胺基甲酸酯丙烯酸酯（製品名：UN-5500，重量平均分子量：約50,000 )、共榮社化學股份公 司製2-羥基乙基甲基丙烯酸酯（製品名：HO )、及共榮 社化學股份公司苯甲基甲基丙烯酸酯（製品名：BZ )、 作爲（B )成分之Fudow股份公司製多元醇型二甲苯樹脂 (改性品）（K140 )、作爲（C )成分之Admatechs股份 -27- 201035214 公司製氧化鋁塡充劑（製品名：AO-902H、平均粒徑： 0.7 // m、折射率1.76)、作爲（D )成分之日弘Vies股 份公司製黑色顏料（製品名：NBD-0744 )、作爲光聚合 起始劑之Ciba Japan股份公司製1-羥基環己基苯基酮5〇 份與二苯甲酮50份之混合物（製品名：IRGA CURE 5 00 ) 進行混合，調製光硬化性樹脂組成物。又，成分（A )及 (B)成分之硬化物的折射率爲1.53。 (黏著強度試驗試樣的製作） 使用所調製之光硬化性樹脂組成物，如圖6所示般， 於長度：75mm、寬·· 25mm、厚：2.5mm的玻璃板上以 1 00 # m厚的2片間隔物所區隔的寬1 · 5 cm溝塗佈光硬化 性樹脂組成物（塗佈長：75mm、塗佈寬：1 5mm、塗佈厚 :100 β ra)。除去2片間隔物後，使塗佈於玻璃板上之 光硬化性樹脂組成物藉UV照射進行硬化。貼合厚度： 5 0 0 /z m之聚碳酸酯（P C )板，製作剝離強度試驗的試樣 。光硬化性樹脂組成物之硬化係與實施例1〜6同樣地進行 ，但UV光係從玻璃側照射。 (黏著強度試驗） 對所製作之試樣安裝治具，使用島津製作所公司製抗 拉試驗機，剝離試驗係以3 00mm/分進行試驗，剪切試驗 係以5mm /分進行試驗。結果表示於表3中。 -28- 201035214 (結果） 剝離試驗、剪切試驗之結果表示於表3中。 [表3] 實施例9 實施例10 實施例11 實施例12 實施例13 實施例14 實施例15 實施例16 UN-5500 51.3 61.2 67.8 72.5 75.9 78.7 80.8 82.6 HO 25.6 20.4 16.9 14.5 12. 7 11.2 10.1 9.2 BZ 23.1 18.4 15.3 13 11.4 10. 1 9.1 8.3 A0-902H 25.5 20.4 16.9 14.5 12.7 11.2 10.1 9.2 NBD-0744 0.51 0,41 0. 34 0.29 0.25 0. 22 0.2 0.18 K140 128.2 102 84.7 72.5 63.3 56.2 50.5 45.9 IRGACURE 500 7.7 6.1 5.1 4.3 3.8 3.4 3 2.8 合計 262.1 229 207.1 191.6 180 171 163.8 158 剝離強度 (N/25mm) 0.3 0.5 1.2 1.7 1,4 1.0 0.6 0.4 剪切強度 (Mpa) 1.3 2.1 2.9 4.3 3.3 2.2 1.3 0.8 從表3可知，證實在成分（A)之添加量爲1〇〇重量 份，成分（B )爲55〜85重量份中，可得到1 .ON/25mm以 ❹ 上之剝離強度、2.2MPa以上之剪切強度，在成分（A)之 添加量爲1〇〇重量份，成分（B)爲60〜85重量份中，可 得到1.2N/25mm以上之剝離強度、2.9MPa以上之剪切強 度。 (實施例17〜23 ) 其次，爲硏究成分（B )的添加對已硬化之光硬化性 樹脂組成物的黏著強度之影響，進行實施例1 7〜23。 (光硬化性樹脂組成物之調製） -29 - 201035214 以表4所示之量，使作爲（A)成分之根上工業股份 公司製聚碳酸酯系胺基甲酸酯丙烯酸酯（製品名：UN-5500， 重量平 均分子 量：約 50,000) 、 共榮 社化學 股份公 司製2-羥基乙基甲基丙烯酸酯（製品名：HO )、及共榮 社化學股份公司苯甲基甲基丙烯酸酯（製品名：BZ )、 作爲（B )成分之Fudow股份公司製多元醇型二甲苯樹脂 (改性品）（K140 )、作爲（C )成分之Admatechs股份 公司製氧化鋁塡充劑（製品名：AO-902H、平均粒徑： 0.7// m、折射率1.76)、作爲（D)成分之日弘 Vies股 份公司製黑色顏料（製品名：NBD-0744 )、作爲光聚合 起始劑之Ciba Japan股份公司製1-羥基環己基苯基酮50 份與二苯甲酮50份之混合物（製品名：IRGACURE 500 ) 進行混合，調製光硬化性樹脂組成物。又，成分（A )及 (B)成分之硬化物的折射率爲1.53。 (黏著強度試驗試樣的製作、黏著強度試驗） 使用所調製之光硬化性樹脂組成物，與實施例9〜1 6 同樣地，製作試樣，測定剝離強度、剪切強度。 (結果） 剝離試驗、剪切試驗之結果表示於表4中。 -30 - 201035214 [表4] 實施例17 實施例18 實施例19 實施例20 實施例21 實施例22 UN-5500 72.5 72.5 72.5 72.5 72.5 72.5 HO 14.5 14.5 14.5 14.5 14.5 14.5 BZ 13 13 13 13 13 13 AO-902H 14.5 14.5 14.5 14.5 14.5 14.5 NBD-0744 0.29 0.29 0.29 0.29 0.29 0.29 K140 43.5 58 72.5 87 101.4 115.9 IRGACURE 500 4.3 4.3 4.3 4.3 4.3 4.3 合計 162.6 177.1 191.6 206.1 220.6 235.1 剝離強度 (N/25mm) 0.3 0.5 1.7 2.2 1.6 1.0 剪切強度 (MPa) 0.8 1.3 4.3 5.8 4.6 3.7 從表4可知，證實在成分（A)之添加量爲100重量 份，成分（B )之添加量爲7 0 ~ 1 16份中’可得到 1.0N/25mm以上之剝離強度、3.7MPa以上之剪切強度， 在成分（B)之添加量爲70〜101份中’可得到l.6N/25mm 以上之剝離強度、4.3 MP a以上之剪切強度。 (產業上之利用可能性） 本發明之光硬化性樹脂組成物係可厚膜硬化，硬化後 ，光透過性低，具有黏著性’且強度、耐久性、耐濕性等 各種的特性優異。生產性充分提高，適用來作爲必須遮光 性之各種光學機器構件或成形樹脂等之製造用樹脂。 -31 - 201035214 【圖式簡單說明】 圖1係表示習知之光學機器構件的圖。 圖2係表示本發明之光學機器構件的槪念圖。 圖3係實施例1之試樣的模式圖。 圖4係表示光硬化性樹脂組成物之膜厚與透過率的關 係之圖。 圖5係表示光硬化性樹脂組成物之膜厚與反射率的關 係之圖。 圖6係剝離強度試驗用試樣之模式圖。 圖7係剝離強度試驗法之模式圖。 【主要元件符號說明】 1 : LCD面板 2 :固定（密封）樹脂層 3 :基板 4 :背光 5 :具有遮光性與黏著性之硬化後的光硬化性樹脂組 成物 6 :硬化前之光硬化性樹脂組成物 7 :黑色管體 8 :鋁板 9 :玻璃板 10 : PC 板 A:來自外部之透過光 -32- 201035214 B :來自內部的漏光（損失光） C :紫外線 ❹ 〇 -33-G (Preparation of a photocurable resin composition) In the amount shown in Table 3, a polycarbonate-based urethane acrylate (product name: UN-5500, manufactured by Kokusai Industrial Co., Ltd.) as the component (A) was used. Weight average molecular weight: about 50,000), 2-hydroxyethyl methacrylate (product name: HO) manufactured by Kyoeisha Chemical Co., Ltd., and benzyl methacrylate of Kyoeisha Chemical Co., Ltd. (product name: BZ) ), a polyol type xylene resin (modified product) (K140) manufactured by Fudow Co., Ltd. as component (B), and Admatechs shares as a component (C) -27- 201035214 Alumina sputum made by the company (product name: AO-902H, average particle size: 0.7 // m, refractive index: 1.76), black pigment (product name: NBD-0744) made by Nippon Vies Co., Ltd. as component (D), Ciba Japan as photopolymerization initiator A mixture of 5-hydroxycyclohexyl phenyl ketone prepared by the company and 50 parts of benzophenone (product name: IRGA CURE 5 00) was mixed to prepare a photocurable resin composition. Further, the cured product of the components (A) and (B) had a refractive index of 1.53. (Production of Adhesive Strength Test Specimen) Using the prepared photocurable resin composition, as shown in Fig. 6, on a glass plate having a length of 75 mm, a width of 25 mm, and a thickness of 2.5 mm, 1 00 # m A light-curable resin composition (coating length: 75 mm, coating width: 15 mm, coating thickness: 100 β ra) was applied to a wide 1 · 5 cm groove partitioned by two thick spacers. After removing the two spacers, the photocurable resin composition applied to the glass plate was cured by UV irradiation. A polycarbonate (P C ) plate having a thickness of 5 0 0 /z m was prepared for the peel strength test. The curing of the photocurable resin composition was carried out in the same manner as in Examples 1 to 6, but the UV light was irradiated from the glass side. (Adhesive strength test) For the sample to be produced, a tensile tester manufactured by Shimadzu Corporation was used, and the peeling test was carried out at 300 mm/min, and the shear test was carried out at 5 mm/min. The results are shown in Table 3. -28- 201035214 (Results) The results of the peel test and the shear test are shown in Table 3. [Table 3] Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 Example 16 UN-5500 51.3 61.2 67.8 72.5 75.9 78.7 80.8 82.6 HO 25.6 20.4 16.9 14.5 12. 7 11.2 10.1 9.2 BZ 23.1 18.4 15.3 13 11.4 10. 1 9.1 8.3 A0-902H 25.5 20.4 16.9 14.5 12.7 11.2 10.1 9.2 NBD-0744 0.51 0,41 0. 34 0.29 0.25 0. 22 0.2 0.18 K140 128.2 102 84.7 72.5 63.3 56.2 50.5 45.9 IRGACURE 500 7.7 6.1 5.1 4.3 3.8 3.4 3 2.8 Total 262.1 229 207.1 191.6 180 171 163.8 158 Peel strength (N/25mm) 0.3 0.5 1.2 1.7 1,4 1.0 0.6 0.4 Shear strength (Mpa) 1.3 2.1 2.9 4.3 3.3 2.2 1.3 0.8 From the table 3, it was confirmed that the amount of the component (A) added was 1 part by weight, and the component (B) was 55 to 85 parts by weight, and a peel strength of 1. ON/25 mm and a shear of 2.2 MPa or more were obtained. The cutting strength is 1 part by weight of the component (A) and 60 to 85 parts by weight of the component (B), and a peel strength of 1.2 N/25 mm or more and a shear strength of 2.9 MPa or more are obtained. (Examples 17 to 23) Next, in order to investigate the influence of the addition of the component (B) on the adhesion strength of the cured photocurable resin composition, Examples 17 to 23 were carried out. (Preparation of Photocurable Resin Composition) -29 - 201035214 In the amount shown in Table 4, a polycarbonate urethane acrylate manufactured by Kokusai Kogyo Co., Ltd. as a component (A) (product name: UN) -5500, Weight average molecular weight: about 50,000), 2-hydroxyethyl methacrylate (product name: HO) manufactured by Kyoeisha Chemical Co., Ltd., and benzyl methacrylate (product) of Kyoeisha Chemical Co., Ltd. Name: BZ), polyol type xylene resin (modified product) (K140) manufactured by Fudow Co., Ltd. as component (B), and alumina enamel filler manufactured by Admatechs Co., Ltd. as component (C) (product name: AO -902H, average particle diameter: 0.7//m, refractive index: 1.76), as a component (D), a black pigment (product name: NBD-0744) manufactured by Rihung Vies Co., Ltd., and a Ciba Japan company as a photopolymerization initiator A mixture of 50 parts of 1-hydroxycyclohexyl phenyl ketone and 50 parts of benzophenone (product name: IRGACURE 500) was mixed to prepare a photocurable resin composition. Further, the cured product of the components (A) and (B) had a refractive index of 1.53. (Preparation of Adhesive Strength Test Specimen and Adhesive Strength Test) Using the prepared photocurable resin composition, samples were prepared in the same manner as in Examples 9 to 16 to measure peel strength and shear strength. (Results) The results of the peeling test and the shear test are shown in Table 4. -30 - 201035214 [Table 4] Example 17 Example 18 Example 19 Example 20 Example 21 Example 22 UN-5500 72.5 72.5 72.5 72.5 72.5 72.5 HO 14.5 14.5 14.5 14.5 14.5 14.5 BZ 13 13 13 13 13 13 AO -902H 14.5 14.5 14.5 14.5 14.5 14.5 NBD-0744 0.29 0.29 0.29 0.29 0.29 0.29 K140 43.5 58 72.5 87 101.4 115.9 IRGACURE 500 4.3 4.3 4.3 4.3 4.3 4.3 Total 162.6 177.1 191.6 206.1 220.6 235.1 Peel strength (N/25mm) 0.3 0.5 1.7 2.2 1.6 1.0 Shear strength (MPa) 0.8 1.3 4.3 5.8 4.6 3.7 From Table 4, it is confirmed that the amount of the component (A) is 100 parts by weight, and the amount of the component (B) is 70 to 16 parts. A peel strength of 1.0 N/25 mm or more and a shear strength of 3.7 MPa or more are obtained, and in the case where the amount of the component (B) is 70 to 101 parts, a peel strength of 1.6 N/25 mm or more and a peel strength of 4.3 MP a or more are obtained. Shear strength. (Industrial Applicability) The photocurable resin composition of the present invention can be cured by a thick film, has low light transmittance after curing, and has adhesiveness and is excellent in various properties such as strength, durability, and moisture resistance. The production property is sufficiently improved, and it is applied as a resin for manufacturing various optical device members or molding resins which are required to be light-shielding. -31 - 201035214 BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing a conventional optical machine component. Fig. 2 is a view showing the concept of the optical machine component of the present invention. Figure 3 is a schematic view of a sample of Example 1. Fig. 4 is a view showing the relationship between the film thickness of the photocurable resin composition and the transmittance. Fig. 5 is a graph showing the relationship between the film thickness of the photocurable resin composition and the reflectance. Fig. 6 is a schematic view showing a sample for peel strength test. Figure 7 is a schematic view of the peel strength test method. [Explanation of main component symbols] 1 : LCD panel 2 : Fixed (sealed) resin layer 3 : Substrate 4 : Backlight 5 : Photocurable resin composition after curing with light blocking property and adhesiveness 6 : Photocurability before curing Resin composition 7 : Black tube 8 : Aluminum plate 9 : Glass plate 10 : PC plate A : Transmitted light from outside - 32 - 201035214 B : Light leakage from inside (loss of light) C : Ultraviolet ❹ 〇-33-