TW201132657A - Active energy line cured-type composition for optical component - Google Patents
Active energy line cured-type composition for optical component Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
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201132657 六、發明說明： 【發明所屬之技術領域】 本發明係關於活性能量線硬化型光學構件用組成物。本 發明更詳言之，係關於活性能量線硬化型透鏡片用組成物， 其屬於使用於投影電視等螢幕的夫瑞乃（fresnel)透鏡或使用 於雙凸透鏡等透鏡部、或液晶顯示裝置之背光的稜鏡透鏡片 之技術領域。 【先前技術】 先前，夫瑞乃透鏡及雙凸透鏡等之透鏡片，係藉由壓製 法及鑄製法等方法予以成形來製造。 但是，前者之壓製法因係以加熱、加壓及冷卻之循環 製造，故會有生產性惡化等的問題。又，後者之鑄製法，因 係將單體傾注於鑄模而聚合，故製作時間耗時，同時因鑄模 需要多數個，故會有製造成本上升等的問題。 爲了解決此種問題，關於使用活性能量線硬化型組成 物則有各種提案（例如專利文獻1至6)。 但是，先前之活性能量線硬化型組成物，由折射率及 透明性之觀點觀之並不充分，再者爲要改良該觀點，吾人硏 討倂用雙酚型二（甲基）丙烯酸酯與具有芳香族環的單（甲基） 丙烯酸酯之組成物（例如專利文獻7及8)。 又，亦有揭示其他活性能量線硬化型光學材料用組成 物（專利文獻9至1 1)。 201132657 [先前技術文獻] [專利文獻] [專利文獻1]日本特開昭61-177215號公報 [專利文獻2]日本特開昭61—248707號公報 [專利文獻3]曰本特開昭61-248708號公報 [專利文獻4]日本特開昭63-163330號公報 [專利文獻5]日本特開昭63-167301號公報 [專利文獻6]日本特開昭63-199302號公報 [專利文獻7 ]日本特開平9 - 8 7 3 3 6號公報 [專利文獻8]日本專利第3397448公報 [專利文獻9]國際公開第2〇〇5/〇44882號要約 [專利文獻10]國際公開第2〇〇5/〇77997號要約 [專利文獻11]日本特開2006-307049號公報 【發明內容】 [發明所欲解決之課題] 但是’在前述活性能量線硬化型組成物，伴隨液晶顯示 裝置或投影電視等之薄型化，進一步被要求高度折射率及透 明性。又’爲了獲得更高折射率之組成物，在製成組合有更 高折射率的（甲基）丙烯酸酯的組成物時來自具有透鏡形狀的 壓模之脫模性，或轉印薄膜之密合性大幅降低了，而有生產 性的問題。 本發明人，首先發現一種活性能量線硬化型光學構件用 201132657 組成物，其所獲得硬化物，從壓模之脫模性或對轉印薄膜之 密合性優異，且可使高折射率並存，所獲得硬化物因熱所致 著色少，以此作爲本發明之課題並戮力硏討。 [解決課題之手段] 本發明人等，爲解決前述課題，進行各種檢討，結果首 先發現得以下述手段（1)解決，因而完成本發明。茲與適當實 施態樣（2)至（13)及關連的發明（14)及（15)—起列記。 < 1 >一種活性能量線硬化型光學構件用組成物，其含有：（ 甲基）丙烯酸環氧酯（成分A);下述式（1)所示單（甲基）丙烯 酸酯（成分B-1)及/或下述式（2)所示單（甲基）丙烯酸酯（成 分B-2)(成分B):成分A及成分B以外之乙烯性不飽和化合 物（成分C);光聚合引發劑（成分D);在苯基中有至少一個 -(：((：113)2115基（115表示碳數1至6之烷基或苯基）取代的酚 化合物（成分E);及在組成物中具有溶解性的亞磷酸酯化 合物（成分F); 在由成分A、B及C所構成之硬化性成分中各含有5至70 重量％成分A、10至90重量％成分B、0.1至60重量％成分C; 相對於硬化性成分之合計100重量份，各含有〇.〇1至20 重量份成分D、0.01至5重量份成分E、及〇.〇1至5重量份成分 F ； 201132657[Technical Field] The present invention relates to a composition for an active energy ray-curable optical member. More specifically, the present invention relates to a composition for an active energy ray-curable lens sheet, which belongs to a fresnel lens used for a screen such as a projection television, a lens portion used for a lenticular lens, or a liquid crystal display device. The technical field of backlighting lenticular lenses. [Prior Art] Conventionally, a lens sheet such as a Fresnel lens or a lenticular lens is produced by a method such as a pressing method or a casting method. However, since the former is produced by a cycle of heating, pressurization, and cooling, there is a problem that productivity is deteriorated. Further, in the casting method of the latter, since the monomer is poured into the mold to be polymerized, the production time is time consuming, and since a large number of molds are required, there is a problem that the manufacturing cost increases. In order to solve such a problem, various proposals have been made regarding the use of an active energy ray-curable composition (for example, Patent Documents 1 to 6). However, the previous active energy ray-curable composition is not sufficient from the viewpoints of refractive index and transparency, and in order to improve this viewpoint, we have pleaded with bisphenol-type di(meth)acrylate and A composition of a mono(meth) acrylate having an aromatic ring (for example, Patent Documents 7 and 8). Further, other active energy ray-curable optical material compositions are disclosed (Patent Documents 9 to 11). [Patent Document 1] Japanese Patent Laid-Open Publication No. SHO 61-248707 (Patent Document 3) 曰本特开昭61- [Patent Document 5] Japanese Laid-Open Patent Publication No. JP-A-63-169301 (Patent Document No. 6) [Patent Document 8] Japanese Patent No. 3397448 (Patent Document 9) International Publication No. 2/5/44882 (Offer) [Patent Document 10] International Publication No. 2 [Patent Document 11] Japanese Laid-Open Patent Publication No. 2006-307049 [Draft of the Invention] [Problems to be Solved by the Invention] However, the active energy ray-curable composition is accompanied by a liquid crystal display device or a projection television. Such as thinning, further required high refractive index and transparency. Further, in order to obtain a composition having a higher refractive index, the release property of a stamper having a lens shape or the density of a transfer film is obtained when a composition of a (meth) acrylate having a higher refractive index is formed. The compatibility is greatly reduced, and there is a problem of productivity. The present inventors first discovered a composition of 201132657 for an active energy ray-curable optical member, which obtained a cured product excellent in mold release property from a stamper or adhesion to a transfer film, and which can coexist with a high refractive index. The obtained cured product is less colored by heat, and this is a subject of the present invention. [Means for Solving the Problem] The inventors of the present invention have made various reviews in order to solve the above problems, and as a result, have found that the present invention has been solved by the following means (1). It is to be noted from the appropriate implementations (2) to (13) and related inventions (14) and (15). < 1 > A composition for an active energy ray-curable optical member, comprising: (meth)acrylic acid epoxy ester (component A); and a mono(meth)acrylate (component) represented by the following formula (1) B-1) and/or a mono(meth)acrylate (component B-2) (component B) represented by the following formula (2): an ethylenically unsaturated compound (component C) other than the component A and the component B; a photopolymerization initiator (ingredient D); a phenol compound (ingredient E) having at least one -(:((:113) 2115 group (115 represents an alkyl group having 1 to 6 carbon atoms or a phenyl group) substituted in the phenyl group; And a phosphite compound (component F) having solubility in the composition; and 5 to 70% by weight of the component A and 10 to 90% by weight of the component B in each of the curable components composed of the components A, B and C 0.1 to 60% by weight of the component C; each of 100 parts by weight of the curable component, each containing 1 to 20 parts by weight of the component D, 0.01 to 5 parts by weight of the component E, and 1 to 5 parts by weight of the component. Ingredient F; 201132657
Rt Ο H2C=C-C 〇4h-CH5Rt Ο H2C=C-C 〇4h-CH5
〔式（1)中’ 1^及112係各自獨立表示氫原子或甲基；1表 示0至4之數〕[In the formula (1), '1^ and 112 each independently represent a hydrogen atom or a methyl group; 1 represents a number from 0 to 4]
〔式（2)中> R3及R4係各自獨立地表示氫原子或甲基；m 表示〇至4之數〕。 <2>如< 1 >項之活性能量線硬化型光學構件用組成物，其中成 分A係雙酚型環氧樹脂之（甲基）丙烯酸加成物。 <3>如<1>或<2>項之活性能量線硬化型光學構件用組成物， 其中在該硬化性成分中含有〇·5至3〇重量％具有3個以上（ 甲基）丙烯醯基的化合物作爲成分C。 <4>如<1>至<3>項中任一項之活性能量線硬化型光學構件用 組成物，其中在該硬化性成分中含有〇·5至40重量％心乙 烯咔唑作爲成分C。 <5>如<1>至<4>項中任一項之活性能量線硬化型光學構件用 組成物，其中在該硬化性成分中含有合計〇 . 5至3 0重量％ 具有3個以上（甲基）丙烯醯基的化合物及N-乙烯咔唑作爲[In the formula (2) > R3 and R4 each independently represent a hydrogen atom or a methyl group; m represents a number of 〇 to 4]. <2> The composition for an active energy ray-curable optical member according to the item <1>, wherein the component A is a (meth)acrylic acid addition product of a bisphenol type epoxy resin. <3> The composition for an active energy ray-curable optical member according to the item <1> or <2>, wherein the curable component contains 〇·5 to 3 〇% by weight and has three or more (methyl) A compound of an acrylonitrile group as component C. The composition for an active energy ray-curable optical member according to any one of the above-mentioned items, wherein the curable component contains 至·5 to 40% by weight of a cardiac vinyl carbazole. As component C. The composition for an active energy ray-curable optical member according to any one of the above-mentioned items, wherein the sclerosing component contains a total of 〇. 5 to 30% by weight. More than one (meth) propylene fluorenyl compound and N-vinyl carbazole
成分C <6>如< 1 >至<5>項中任一項之活性能量線硬化型光學構件用 組成物，其含有下述式（3)所示之化合物作爲成分E, 201132657The composition for an active energy ray-curable optical member according to any one of the above-mentioned items (3), which contains a compound represented by the following formula (3) as a component E, 201132657
〔式（3)中，115表示碳數1至5之烷基或苯基；R6表示 氫原子、碳數1至5之烷基或苯基；R7及Rs表示氫原子或 甲基；X表示η價之基；η表示1至4之整數〕。 <7>如<6>項之活性能量線硬化型光學構件用組成物，其係含 有上述式（3)中X具有一個以上羧酸酯鍵的化合物（成分Ε1 )作爲成分Ε。 < 8 >如< 7 >項之活性能量線硬化型光學構件用組成物， 其中成分Ε1係下述式（4)所示之化合物，[In the formula (3), 115 represents an alkyl group having 1 to 5 carbon atoms or a phenyl group; R6 represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a phenyl group; and R7 and Rs represent a hydrogen atom or a methyl group; X represents The base of the η valence; η represents an integer from 1 to 4. <7> The composition for an active energy ray-curable optical member according to the above item (3), which comprises a compound (component Ε1) having one or more carboxylic acid ester bonds in the above formula (3) as a component Ε. The composition for an active energy ray-curable optical member according to the item <7>, wherein the component Ε1 is a compound represented by the following formula (4),
HuC m H3( HO h3c h3c八ch3 〔式（4)中，R9表示碳數1至20之烷基〕。 < 9 >如< 7 >項之活性能量線硬化型光學構件用組成物’ 其中成分Ε1係下述式（5)所示之化合物’ -10 - 201132657HuC m H3 ( HO h3c h3c 八 ch3 [in the formula (4), R9 represents an alkyl group having 1 to 20 carbon atoms]. < 9 > The composition of the active energy ray-curable optical member of the item < 7 > ''Ingredient Ε1 is a compound represented by the following formula (5)' -10 - 201132657
CH2-CH2.^0-CH2|^°2)^^fcH2-〇XcH2-CH2CH2-CH2.^0-CH2|^°2)^^fcH2-〇XcH2-CH2
<1〇>如<1>至<9>項中任—項之活性能量線硬化型光學構件 用組成物’其中成分F係下述式（6)所示之化合物， p(or10)3 ...(6) 〔但在式（6)中’ RiQ表示烷基或芳香族基〕。 <1 1>如<1>至<1〇>項中任—項之活性能量線硬化型光學構件 用組成物’其進一步含有紫外線吸收劑（成分G)。 < 1 2>如< 1 >至< 1 1 >項中任一項之活性能量線硬化型光學構件 用組成物，其中硬化後2 5 °C，鈉D線中折射率爲1 . 5 7 0以 上。 <13>如<1>至<12>項中任一項之活性能量線硬化型光學構件 用組成物，其係透鏡片製造用。 <14>—種光學構件之製造方法，其特徵爲包含準備硬化性組 成物之步驟，及照射活性能量線於上述組成物之步驟， 其中該硬化性組成物係含有（甲基）丙烯酸環氧酯（成分 A);下述式（1)所示單（甲基）丙烯酸酯（成分B-1)及/或下 述式（2)所示單（甲基）丙烯酸酯（成分B-2)(成分B);成分a 及成分B以外之乙烯性不飽和化合物（成分C);光聚合引 發劑（成分D);在苯基中有至少一個_C(CH3)2R5基（r5表示 201132657 碳數1至6之烷基或苯基）取代的酚化合物（成分E);及在 組成物中具有溶解性的亞磷酸酯化合物（成分F);在由成 分A、B及C所構成之硬化性成分中，各自含有5至70重量 %成分A、10至90重量％成分B、0.1至60重量％成分C ;相 對於硬化性成分之合計100重量份，各自含有0.01至20重 量份成分D、0.01至5重量份成分E、及0.01至5重量份成 分F ;<1〇> The composition for active energy ray-curable optical member of any one of <1> to <9>, wherein component F is a compound represented by the following formula (6), p( Or10) 3 (6) [However, in the formula (6), ' RiQ represents an alkyl group or an aromatic group]. <1 1> The composition for active energy ray-curable optical member according to any one of <1> to <1>> further contains an ultraviolet absorber (component G). The composition for an active energy ray-curable optical member according to any one of the above items, wherein the refractive index in the sodium D line is 25 ° C after hardening. 1. 5 7 0 or more. The composition for an active energy ray-curable optical member according to any one of <1> to <12>, which is used for the production of a lens sheet. <14> - A method for producing an optical member, comprising the steps of preparing a curable composition, and irradiating an active energy ray to the composition, wherein the curable composition contains a (meth)acrylic acid ring Oxy ester (component A); mono (meth) acrylate (component B-1) represented by the following formula (1) and/or mono (meth) acrylate represented by the following formula (2) (component B- 2) (Component B); an ethylenically unsaturated compound other than the component a and the component B (component C); a photopolymerization initiator (component D); and at least one _C(CH3)2R5 group in the phenyl group (r5 represents 201132657 Alkyl or phenyl substituted phenolic compound having a carbon number of 1 to 6 (ingredient E); and a phosphite compound (ingredient F) having solubility in the composition; composed of components A, B and C Each of the curable components contains 5 to 70% by weight of the component A, 10 to 90% by weight of the component B, and 0.1 to 60% by weight of the component C, and each of the curing component is contained in an amount of 0.01 to 20 parts by weight per 100 parts by weight of the total of the curable component. Component D, 0.01 to 5 parts by weight of component E, and 0.01 to 5 parts by weight of component F;
〔式（1)中，1^及112係各自獨立地表示氫原子或甲 基；1表示〇至4之數〕[In the formula (1), 1 and 112 each independently represent a hydrogen atom or a methyl group; 1 represents a number of 〇 to 4]
(2)(2)
H2C-C-CTO-CH—CH 〔式（2)中，R3&R4係各自獨立地表示氫原子或甲基 ;m表示0至4之數〕。 此外，在本說明書中，丙烯酸酯及/或甲基丙烯酸酯係表 示（甲基）丙烯酸酯。 茲詳細說明本發明如下。 [發明效果] 本發明之組成物，在室溫之作業性優異，所獲得硬化物 ，透明性優異高折射率且透光率良好，可適當使用於要求透 明性、高折射率及高透光率的透鏡片及塑膠透鏡等之光學構 -12 - 201132657 件。 【實施方式】 本發明之活性能量線硬化型光學構件用組成物，含有：（ 甲基）丙烯酸環氧酯（成分A);下述式（1)所示之單（甲基）丙烯 酸酯（成分B-1)及/或下述式（2)所示之單（甲基）丙烯酸酯（成分 B-2)(成分B);(成分A)及（成分B)以外之乙烯性不飽和化合物（ 成分C);光聚合引發劑（成分D); 在苯基中有至少一個_C(CH3)2r5基（115表示碳數1至6之 烷基或苯基）取代的酚化合物（成分E);以及在組成物中具有 溶解性的亞磷酸酯化合物（成分F);在由成分A、B及C所構成 之硬化性成分中各含有5至70重量％成分A，10至90重量％成分 B，0.1至60重量％成分C，相對於成分A、B及C之合計100重 量份，各含有0.01至20重量份成分D, 0.01至5重量份成分E， 及0.01至5重量份成分F。 以下，就（A)至（F)成分加以說明。H2C-C-CTO-CH-CH [In the formula (2), R3 & R4 each independently represents a hydrogen atom or a methyl group; m represents a number of 0 to 4]. Further, in the present specification, the acrylate and/or methacrylate means (meth) acrylate. The invention is described in detail below. [Effect of the Invention] The composition of the present invention is excellent in workability at room temperature, and the obtained cured product has excellent transparency, high refractive index, and good light transmittance, and can be suitably used for transparency, high refractive index, and high light transmittance. The optical structure of the lens sheet and the plastic lens is -12 - 201132657 pieces. [Embodiment] The composition for an active energy ray-curable optical member of the present invention contains (meth)acrylic acid epoxy ester (component A); and a mono(meth)acrylate represented by the following formula (1) ( Component B-1) and/or mono(meth)acrylate (component B-2) (component B) represented by the following formula (2); ethylenic unsaturation other than (component A) and (component B) a compound (component C); a photopolymerization initiator (ingredient D); a phenol compound having at least one _C(CH3)2r5 group (115 represents an alkyl group having 1 to 6 carbon atoms or a phenyl group) in a phenyl group (ingredient) E); and a phosphite compound (component F) having solubility in the composition; and 5 to 70% by weight of the component A, 10 to 90 by weight in each of the curable components composed of the components A, B and C % Component B, 0.1 to 60% by weight of Component C, each of 100 parts by weight of the components A, B and C, each containing 0.01 to 20 parts by weight of the component D, 0.01 to 5 parts by weight of the component E, and 0.01 to 5 parts by weight. Ingredient F. Hereinafter, the components (A) to (F) will be described.
1 .成分A 成分A係（甲基）丙烯酸環氧酯。 (甲基）丙烯酸環氧酯係在環氧樹脂進行（甲基）丙烯酸加 成反應之化合物。 在此，環氧樹脂係指分子中具有平均2個以上之環氧基， 以反應硬化的低分子化合物或聚合物（高分子）之謂。依照在 本領域之慣例，在本說明書中，只要是分子內具有2個以上硬 -13 - 201132657 化性之環氧基之物，則除了分子量爲ι000以上之聚合物之外 ，即使分子量低於1，〇〇〇之低分子化合物亦稱爲環氧樹脂。 在環氧樹脂方面，可例舉芳香族環氧樹脂及脂肪族環氧 樹脂等。 芳香族環氧樹脂方面’具體言之’可例舉間苯二酚二環 氧丙醚；雙酚A、雙酚F、雙酚S、雙酚苐或其氧化烯加成物 之二或聚環氧丙醚；酚式酚醛清漆型環氧樹脂及甲酚式酚醛 清漆型環氧樹脂等之酚醛清漆型環氧樹脂；環氧丙基鄰苯二 甲醯亞胺；鄰酞酸二環氧丙基酯等。 脂肪族環氧樹脂方面，具體言之，可例舉乙二醇、丙二 醇、1,4-丁二醇及1，6-己二醇等之伸烷二醇之二環氧丙醚；聚 乙二醇及聚丙二醇之二環氧丙醚等之聚伸烷二醇之二環氧丙 醚；新戊二醇、二溴新戊二醇及其氧化烯加成物之二環氧丙 醚；三羥甲基乙烷、三羥甲基丙烷、甘油及其氧化烯加成物 之二或三環氧丙醚、以及新戊四醇及其氧化烯加成物之二、 三或四環氧丙醚等多價醇之聚環氧丙醚；氫化雙酚A及其環 氧烷加成物之二或聚環氧丙醚：四氫酞酸二環氧丙醚；氫醌 二環氧丙醚等。 該等中’（A)成分方面，較佳爲將雙酚a型環氧樹脂及雙 S&F環氧樹脂等之雙酚型環氧樹脂與（甲基）丙烯酸反應所獲 得化合物。 雙酣A型環氧樹脂方面，可例舉日本環氧樹脂股份有限公 -14 - 201132657 司之jER-827(環氧當量：180至190g/eq)，jER-828(環氧當量： 184 至 194g/eq)，jER-834(環氧當量：230 至 270g/eq)等之例。 雙酚F型環氧樹脂方面，可例舉日本環氧樹脂股份有限公 司之jER-806(環氧當量：160至170g/eq)，jER-807(環氧當量：1 60至 175g/eq)等。 環氧樹脂方面，不必限定於該等，即可使用各種結構之環 氧樹脂，或各種環氧當量之環氧樹脂。 在（甲基）丙烯酸環氧酯之合成中，相對於環氧基1當量， (甲基）丙烯酸較佳爲0..7至1.5當量，再佳爲0.9至1.1當量之比 率予以反應。本發明之（甲基）丙烯酸環氧酯方面，以雙酚A型 (甲基）丙烯酸環氧酯，硬化性高，因可提高所獲得硬化物之 耐熱性故較適當。 成分A之含有比率，在成分A、B及C所構成之硬化性成分 中爲5至70重量％，較佳爲8至40重量％。成分A之比率低於5 重量％之情形，造成硬化所致收縮或變形發生，無法獲得形 狀良好的硬化物薄片，一方面，在超過70重量％時，則造成 黏度上升，變的難以處理，或因氣泡而使薄片發生缺陷。1. Component A Component A is an epoxy (meth)acrylate. The (meth)acrylic acid epoxy ester is a compound in which an epoxy resin is subjected to a (meth)acrylic acid addition reaction. Here, the epoxy resin refers to a low molecular compound or a polymer (polymer) having an average of two or more epoxy groups in the molecule and being reactively hardened. According to the conventional practice in the art, in the present specification, as long as it is an epoxy group having two or more hard-13 - 201132 657 in the molecule, the molecular weight is lower than the polymer having a molecular weight of 1,000,000 or more. 1, 低 low molecular compound is also known as epoxy resin. The epoxy resin may, for example, be an aromatic epoxy resin or an aliphatic epoxy resin. The term "specifically" for the aromatic epoxy resin may, for example, be resorcinol diglycidyl ether; bisphenol A, bisphenol F, bisphenol S, bisphenol oxime or an alkylene oxide adduct thereof Glycidyl ether; phenol novolak type epoxy resin and phenol novolak type epoxy resin, such as novolak type epoxy resin; epoxy propyl phthalimide; o-nonanoic acid epoxide Propyl ester and the like. In terms of the aliphatic epoxy resin, specifically, a diglycidyl ether of an alkylene glycol such as ethylene glycol, propylene glycol, 1,4-butanediol or 1,6-hexanediol; a diglycidyl ether of a polyalkylene glycol such as a diol or a polypropylene glycol diglycidyl ether; a diglycidyl ether of neopentyl glycol, dibromo neopentyl glycol, and an alkylene oxide adduct thereof; Tris or trimethylolpropane ether of trimethylolethane, trimethylolpropane, glycerol and its alkylene oxide adducts, and di-, tri- or tetraepoxy of pentaerythritol and its alkylene oxide adducts Polyglycidyl ether of polyvalent alcohol such as propyl ether; hydrogenated bisphenol A and its alkylene oxide adducts or polyglycidyl ether: tetrahydrofurfuryl diglycidyl ether; hydroquinone diepoxypropyl Ether, etc. In the case of the '(A) component, a compound obtained by reacting a bisphenol type epoxy resin such as a bisphenol a type epoxy resin and a double S&F epoxy resin with (meth)acrylic acid is preferred. For the double bismuth A type epoxy resin, the jen-827 (epoxy equivalent: 180 to 190 g/eq) and jER-828 (epoxy equivalent: 184 to 5% of the epoxy resin company limited edition -14-201132657) can be exemplified. 194 g/eq), jER-834 (epoxy equivalent: 230 to 270 g/eq), and the like. The bisphenol F type epoxy resin may, for example, be JER-806 (epoxy equivalent: 160 to 170 g/eq), jER-807 (epoxy equivalent: 1 60 to 175 g/eq) of Japan Epoxy Resin Co., Ltd. Wait. As the epoxy resin, it is not necessary to be limited to these, and various types of epoxy resins or epoxy equivalent epoxy resins can be used. In the synthesis of the (meth)acrylic acid epoxy ester, the (meth)acrylic acid is preferably reacted in a ratio of from 0.7 to 1.5 equivalents, more preferably from 0.9 to 1.1 equivalents, per equivalent of the epoxy group. In the case of the (meth)acrylic acid epoxy ester of the present invention, bisphenol A type (meth)acrylic acid epoxy ester has high hardenability and is suitable for improving the heat resistance of the obtained cured product. The content ratio of the component A is 5 to 70% by weight, preferably 8 to 40% by weight, based on the curable component composed of the components A, B and C. When the ratio of the component A is less than 5% by weight, shrinkage or deformation due to hardening occurs, and a cured sheet having a good shape cannot be obtained. On the other hand, when it exceeds 70% by weight, the viscosity is increased and it becomes difficult to handle. Or the sheet is defective due to bubbles.
2·成分B 成分B係下述式（1)所示之單（甲基）丙烯酸酯（成分8_1}及 /或下述式（2)所示之單（甲基）丙烯酸酯（成分B — 2)。 -15 - 2011326572. Component B Component B is a mono(meth)acrylate (component 8_1} represented by the following formula (1) and/or a mono(meth)acrylate represented by the following formula (2) (component B - 2) -15 - 201132657
〔式（1)中’心及艮2係各自獨立地表示氫原子或甲基； 1表示0至4之數〕[In the formula (1), the heart and the oxime 2 each independently represent a hydrogen atom or a methyl group; 1 represents a number from 0 to 4]
⑵ 〔式（2)中’ R3及R4係各自獨立地表示氫原子或甲基；m 表示0至4之數〕。 該式（1)及式（2)中1及m表示氧化烯之加成數，其意指每1 分子之平均加成數之意。 成分B係使組成物低黏度化’又可防止組成物之結晶化 ，再加上爲提供硬化物折射率等光學特性之成分。 成分B-1之具體例方面，可例舉例如（甲基）丙烯酸對枯烯 基（(：1111161171)苯酯及（甲基）丙烯酸對枯烯基苯氧基乙酯等。 成分B - 1方面，由於是可獲得良好的硬化性，故R i以氫原 子爲佳。又，由於所獲得硬化物之折射率更高，加上可抑制 組成物之黏度爲低，故1以〇至2爲佳。 該等中，就室溫且爲液狀易於處理、折射率高、易於取 得的觀點觀之，較佳爲丙烯酸對枯烯基苯酯及丙烯酸對枯烯 -16 - 201132657 基苯氧基乙酯。 成分B - 2之具體例方面，可例舉例如（甲基）丙烯酸鄰苯基 苯酯、（甲基）丙烯酸間苯基苯酯、（甲基）丙烯酸對苯基苯酯、 (甲基）丙烯酸鄰苯基苯氧基乙酯、（甲基）丙烯酸間苯基苯氧基 乙酯及（甲基）丙烯酸對苯基苯氧基乙酯等° 該等中，由室溫且爲液狀易於處理、易於取得之觀點觀 之，較佳爲（甲基）丙烯酸鄰苯基苯酯及（甲基）丙烯酸鄰苯基苯 氧基乙酯。再者在該等中，由於可抑制組成物之黏度爲低’ 故特佳爲m = 0的鄰（甲基）丙烯酸苯基苯酯。 (B)成分之含有比率，在成分A、B及C所構成之硬化性 成分中爲10至90重量％、較佳爲50至85重量％。（B)成分之比 率低於1 〇重量％之情形，造成硬化物之折射率降低，並造成 後述（E)及（F)成分之互溶性降低，一方面，超過90重量％時’ 則會降低硬化物之耐熱性或機械強度。(2) [In the formula (2), R3 and R4 each independently represent a hydrogen atom or a methyl group; m represents a number from 0 to 4. In the formulae (1) and (2), 1 and m represent the number of additions of alkylene oxide, which means the average number of additions per molecule. Component B is a composition which makes the composition low in viscosity, and prevents the crystallization of the composition, and is a component which provides optical properties such as a refractive index of the cured product. Specific examples of the component B-1 include, for example, (meth)acrylic acid p-cumenyl ((1111161171) phenyl ester, (meth)acrylic acid p-cumenylphenoxyethyl ester, etc. Component B-1 On the other hand, since good hardenability is obtained, R i is preferably a hydrogen atom. Further, since the refractive index of the obtained cured product is higher, and the viscosity of the composition is suppressed to be low, 1 to 2 Preferably, in the case of room temperature and liquid, easy to handle, high refractive index, and easy to obtain, it is preferably p-cumenyl acrylate and p-cumene-16 - 201132657 phenoxy acrylate. Specific examples of the component B-2 include, for example, o-phenylphenyl (meth)acrylate, m-phenylphenyl (meth)acrylate, p-phenylphenyl (meth)acrylate, O-phenylphenoxyethyl (meth)acrylate, m-phenylphenoxyethyl (meth)acrylate, p-phenylphenoxyethyl (meth)acrylate, etc. In view of the fact that it is easy to handle in a liquid form and is easy to obtain, it is preferably o-phenylphenyl (meth)acrylate and ( O-phenylphenoxyethyl acrylate. Further, in the above, phenylphenyl (meth) acrylate is particularly preferable as m = 0 because it can suppress the viscosity of the composition to be low. The content ratio of the component is 10 to 90% by weight, preferably 50 to 85% by weight in the curable component composed of the components A, B and C. The ratio of the component (B) is less than 1% by weight. The refractive index of the cured product is lowered, and the mutual solubility of the components (E) and (F) described later is lowered. On the other hand, when it exceeds 90% by weight, the heat resistance or mechanical strength of the cured product is lowered.
3 .成分C 本發明之組成物含有成分A及成分B以外之乙烯性不飽 和化合物。 成分C方面，可使用各種化合物，可例舉乙烯化合物及（ 甲基）丙烯酸酯等、較佳爲（甲基）丙烯酸酯。 (甲基）丙烯酸酯之具體例方面，可例舉具有1個（甲基）丙 烯醯基的（甲基）丙烯酸酯（以下稱爲單官能（甲基）丙烯酸酯） 及具有2個以上（甲基）丙烯醯基的（甲基）丙烯酸酯（以下稱爲 -17 - 201132657 多官能（甲基）丙烯酸酯）。 單官能（甲基）丙烯酸酯方面，可例舉（甲基）丙烯酸苯氧基 乙酯、（甲基）丙烯酸四氫糠酯、（甲基）丙烯酸苄酯、（甲基） 丙烯酸卡必醇酯、（甲基）丙烯醯基嗎福啉、（甲基）丙烯酸環氧 丙酯、（甲基）丙烯酸2_羥基乙酯、（甲基）丙烯酸2 -羥基丙酯、 具有順丁烯二醯亞胺基的（甲基）丙烯酸酯及（甲基）丙烯酸1,4 -丁二醇單酯等。 在多官能（甲基）丙烯酸酯中，2官能（甲基）丙烯酸酯方面 ，可例舉二（甲基）丙烯酸1，6-己二醇酯，二（甲基）丙烯酸壬二 醇酯’聚乙二醇二（甲基）丙烯酸酯，二（甲基）丙烯酸乙二醇酯 ，（甲基）丙烯酸三溴苯氧基乙酯等。3官能以上之（甲基）丙烯 酸酯方面，可例舉三（甲基）丙烯酸三羥甲基丙酯，三（甲基） 丙烯酸新戊四醇酯，四（甲基）丙烯酸新戊四醇酯，五（甲基） 丙烯酸二新戊四醇酯，六（甲基）丙烯酸二新戊四醇酯及參（2-(甲基）丙烯醯氧基乙基）異三聚氰酸酯等。 、多官能（甲基）丙烯酸酯方面，亦可使用寡聚物，可例舉 聚胺基甲酸酯聚（甲基）丙烯酸酯及聚酯聚（甲基）丙烯酸酯等 。寡聚物之適當分子量範圍，係重量平均分子量在500至 40,000 ° 乙烯化合物方面，可例舉N -乙烯己內酯，N -乙烯吡咯啶 酮及N -乙烯咔唑等。該等中，因可提高所獲得組成物之折射 率，故以N-乙烯咔唑爲適當。 -18 - 201132657 成分C可單獨使用或組合2種以上組合使用。 成分C之含有比率，係在成分A、B及C所構成之硬化性成 分之合計量中爲0.1至60重量％。成分C之比率低於0.1重量％ 時，則硬化性降低，或使組成物之密合性降低，在超過6〇重 量％時，則造成所獲得光學構件之折射率降低。 在成分C方面，3官能以上之（甲基）丙烯酸酯，係爲了獲 得來自壓模之良好的脫模性而具效果故較適當。 在3官能以上（甲基）丙烯酸酯之含有比率方面，以硬化性 成分之合計中調配0.5至30重量％爲佳，更佳爲5至2 0重量％。 藉由設爲〇.5重量％以上，而可製成對轉印薄膜之密合性 優異，加上因硬化物柔軟性爲優異，故可防止變脆而使透鏡 形狀產生缺陷。一方面，藉由設爲3 0重量％以下則可獲得充 分的脫模性。 市售有3官能以上之（甲基）丙烯酸酯，可例舉東亞合成股 份有限公司製，Aronics Μ-305(以下省略「Aronics」之記載 )、M- 309、M-3 1 0、M-3 1 5、M-320、M-3 50、M-3 60 ' M-402、M-404、M-408 及 M-45 0 等 ° 在進一步提高對組成物之硬化物的折射率之情形，成分C 較佳爲使用N-乙烯咔唑。 在N-乙烯咔唑之含有比率方面，在硬化性成分之合計中 以0.5至40重量％爲佳，更佳爲5至30重量％。 -19 - 201132657 再者，因進一步提高對組成物之硬化物的折射率，並具 有來自壓模之良好的脫模性’故較佳爲倂用3官能以上之（甲 基）丙烯酸酯與N·乙烯咔唑來使用。 在3官能以上之（甲基）丙烯酸酯及N -乙烯咔唑之含有比 率方面，該等合計量較佳爲在硬化性成分之合計中調配0.5至 40重量％，更佳爲5至30重量％。 成分A、B及C之含有率之合計爲100重量％。3. Component C The composition of the present invention contains an ethylenically unsaturated compound other than the component A and the component B. As the component C, various compounds can be used, and examples thereof include a vinyl compound and a (meth)acrylate, and a (meth)acrylate is preferable. Specific examples of the (meth) acrylate include (meth) acrylate having one (meth) acryl fluorenyl group (hereinafter referred to as monofunctional (meth) acrylate) and having two or more ( Methyl) acrylonitrile-based (meth) acrylate (hereinafter referred to as -17 - 201132657 polyfunctional (meth) acrylate). The monofunctional (meth) acrylate may, for example, be phenoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, benzyl (meth)acrylate or carbitol (meth)acrylate. Ester, (meth) propylene decyl porphyrin, glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, with maleic acid (I) imine group (meth) acrylate and (meth) acrylate 1,4 - butanediol monoester. In the polyfunctional (meth) acrylate, the bifunctional (meth) acrylate may, for example, be 1,6-hexanediol di(meth)acrylate or decyl glycol di(meth)acrylate. Polyethylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, tribromophenoxyethyl (meth)acrylate, and the like. The trifunctional or higher (meth) acrylate may, for example, be trimethylolpropyl tri(meth)acrylate, neopentyl glycol tri(meth)acrylate, and neopentyltetrakis(meth)acrylate. Ester, pentaerythritol penta(meth)acrylate, dineopentaerythritol hexa(meth)acrylate and bis(2-(methyl)propenyloxyethyl)isocyanate . As the polyfunctional (meth) acrylate, an oligomer may be used, and examples thereof include polyurethane poly(meth)acrylate and polyester poly(meth)acrylate. The appropriate molecular weight range of the oligomer, and the weight average molecular weight is from 500 to 40,000 °, and the vinyl compound may, for example, be N-vinylcaprolactone, N-vinylpyrrolidone or N-vinylcarbazole. Among these, N-vinylcarbazole is suitable because the refractive index of the obtained composition can be improved. -18 - 201132657 The component C may be used singly or in combination of two or more. The content ratio of the component C is 0.1 to 60% by weight in the total amount of the curable components composed of the components A, B and C. When the ratio of the component C is less than 0.1% by weight, the curability is lowered or the adhesion of the composition is lowered. When the ratio is more than 6% by weight, the refractive index of the obtained optical member is lowered. In the case of the component C, a trifunctional or higher functional (meth) acrylate is preferable in order to obtain a good release property from a stamper. In terms of the content ratio of the trifunctional or higher (meth) acrylate, it is preferably 0.5 to 30% by weight, more preferably 5 to 20% by weight, based on the total of the curable components. When the content is 5% by weight or more, the adhesion to the transfer film is excellent, and since the cured product is excellent in flexibility, it is possible to prevent brittleness and cause defects in the shape of the lens. On the other hand, sufficient mold release property can be obtained by setting it to 30% by weight or less. A commercially available trifunctional or higher (meth) acrylate is exemplified by East Asia Synthetic Co., Ltd., Aronics Μ-305 (hereinafter, "Aronics" is omitted), M-309, M-3 10, M- 3 1 5, M-320, M-3 50, M-3 60 'M-402, M-404, M-408 and M-45 0 etc. In the case of further increasing the refractive index of the cured product of the composition Preferably, component C is N-vinylcarbazole. The content ratio of the N-vinylcarbazole is preferably from 0.5 to 40% by weight, more preferably from 5 to 30% by weight, based on the total of the curable components. -19 - 201132657 Further, since the refractive index of the cured product of the composition is further improved and the mold release property is good from the stamper, it is preferred to use a trifunctional or higher (meth)acrylate and N. · Vinyl carbazole for use. In terms of the content ratio of the trifunctional or higher (meth) acrylate and the N-vinyl carbazole, the total amount is preferably 0.5 to 40% by weight, more preferably 5 to 30% by weight based on the total of the hardening components. %. The total content of the components A, B and C was 100% by weight.
4.成分D 成分D之光聚合引發劑，係爲了以紫外線或可視光線之照 射而使前述成分A至C硬化而調配之物。 成分D之具體例方面，可例舉安息香、安息香甲醚及安息 香丙醚等之安息香；乙醯苯、2,2-二甲氧基-2-苯基乙醯苯、2 ,2-二乙氧基-2-苯基乙醯苯、1,1-二氯乙醯苯、1·羥基環己基 苯酮、2-甲基-1-[4-(甲基硫）苯基]-2-嗎啉代-丙烷-1-酮及N，N -二甲基胺基乙醯苯等之乙醯苯；2·甲基蒽醌、1-氯蒽醌及2-戊基蒽醌等之蒽醌：2,4 -二甲基9 -氧硫卩山唱、2,4 -二乙基9 -氧 硫灿喔、2-氯9-氧硫mil唱及2,4-二異丙基9_氧硫灿卩星等之9-氧硫 D山噃；乙醯苯二甲基縮酮及苄基二甲基縮酮等之縮酮；二苯 酮、甲基二苯酮、4，4’-二氯二苯酮、4,4，·雙二乙基胺基二苯 酮、米蚩酮及4-苯甲醯基-4’-甲基二苯基硫化物等之二苯酮； 以及氧化2,4，6-三甲基苯甲醯基二苯膦等。 成分D可單獨使用亦可併用2種以上。 -20 - 201132657 相對於成分A、B及C之合計100重量份，成分D之含有比 率爲〇.〇1至2〇重量份，較佳爲1至10重量份。成分D之比率低 於0.0 1重量份時，則多量之能量之活性能量線照射爲必要’ 造成生產性降低，一方面，超過20重量份時，則因成分D之 分解物而致光學構件著色。4. Component D The photopolymerization initiator of component D is a compound which is prepared by curing the components A to C by irradiation with ultraviolet rays or visible light. Specific examples of the component D include benzoin, benzoin methyl ether and benzoin propyl ether; acetophenone, 2,2-dimethoxy-2-phenylethyl benzene, 2,2-diethyl Oxy-2-phenylethyl benzene, 1,1-dichloroethyl benzene, 1 hydroxycyclohexyl benzophenone, 2-methyl-1-[4-(methylthio)phenyl]-2- Morpholine-propan-1-one and N,N-dimethylaminoethyl benzene and the like acetophenone; 2·methyl hydrazine, 1-chloroindole and 2-pentyl hydrazine醌: 2,4-dimethyl 9-oxosulfonyl sing, 2,4-diethyl 9-oxosulfanthine, 2-chloro 9-oxothio sing and 2,4-diisopropyl 9 _ oxysulfuric acid such as 9-oxo-sulfur D-Hawthorn; ketal such as acetophenone ketal and benzyl dimethyl ketal; benzophenone, methyl benzophenone, 4, 4 a benzophenone such as '-dichlorobenzophenone, 4,4, bisdiethylamino benzophenone, Michler's ketone, and 4-benzylidene-4'-methyldiphenyl sulfide; And oxidation of 2,4,6-trimethylbenzhydryldiphenylphosphine, and the like. The component D may be used alone or in combination of two or more. -20 - 201132657 The content ratio of the component D is from 〇1 to 2 parts by weight, preferably from 1 to 10 parts by weight, based on 100 parts by weight of the total of the components A, B and C. When the ratio of the component D is less than 0.01 part by weight, the active energy ray irradiation of a large amount of energy is necessary to cause a decrease in productivity. On the other hand, when it exceeds 20 parts by weight, the optical member is colored by the decomposition product of the component D. .
5.成分E及成分F 在本發明中，在目的係顯著抑制硬化物經時間變化之著 色爲低，則在組成物中配合有在苯基中取代有至少一個 -C(CH3)2R基（R表示碳數1至6之烷基或苯基）的酚化合物（成 分E)及亞磷酸酯化合物（但是，在組成物中具有溶解性之物）（ 成分F)。 以下，就成分E及成分F加以說明。5. Ingredient E and Component F In the present invention, in the case where the purpose is to significantly suppress the color change of the cured product over time, the composition is compounded with at least one -C(CH3)2R group substituted in the phenyl group ( R represents a phenol compound (component E) having a carbon number of 1 to 6 or a phenyl group) and a phosphite compound (however, it has a solubility in the composition) (component F). Hereinafter, the component E and the component F will be described.
5-1.成分E 成分E，係苯基中取代有至少一個-C(CH3)2R5基（R5表示 碳數1至6之烷基或苯基）的酚化合物。 成分E之R所示之烷基方面’以碳數1至4之烷基爲佳’以 甲基更適當。 苯基之-C(CH3)2R基的取代數方面，以1個或2個爲適當。 又，取代位置較佳爲酚性羥基之近鄰’更佳爲3,5-二取代-4-酚之所謂受阻酚類。 成分E方面，以含有下述式（3)所示之化合物爲佳，以僅1 種或2種以上式（3)所示之化合物更佳。 -21 - 2011326575-1. Component E Component E is a phenol compound in which at least one -C(CH3)2R5 group (R5 represents an alkyl group having 1 to 6 carbon atoms or a phenyl group) is substituted with a phenyl group. The alkyl group represented by R of the component E is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group. The number of substitutions of the phenyl-C(CH3)2R group is preferably one or two. Further, the substitution position is preferably a phenolic hydroxyl group, which is more preferably a so-called hindered phenol of 3,5-disubstituted-4-phenol. In the case of the component E, a compound represented by the following formula (3) is preferred, and only one or two or more compounds represented by the formula (3) are more preferable. -21 - 201132657
〔式（3)中，R5表示碳數1至6之烷基或苯基；r6表示氫 原子，碳數1至6之烷基或苯基；R7及Rs表示氫原子或甲基； X表示η價之基；n表示1至4之整數〕。 式（3)中，X爲1價或2價之基，η較佳爲1或2之整數。 式（3)之化合物方面，以下述式（3 Α)或/及式（3 Β)所示之化 合物較佳。[In the formula (3), R5 represents an alkyl group having 1 to 6 carbon atoms or a phenyl group; r6 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a phenyl group; and R7 and Rs represent a hydrogen atom or a methyl group; X represents The base of the η valence; n represents an integer from 1 to 4. In the formula (3), X is a monovalent or divalent group, and η is preferably an integer of 1 or 2. In the case of the compound of the formula (3), a compound represented by the following formula (3 Α) or / and formula (3 Β) is preferred.
式（3)中，X之具體例方面，可例舉以下所示1價至4價之 基。 1價之基方面，可例舉烷基、具有一個以上酯鍵（-c〇〇-及/或-OCO-)的脂肪族基、含有苯并***基及受阻胺基骨架之 基等。 烷基方面，以碳數2以上20以下之烷基’由硬化物之防止 著色爲優異之觀點觀之較適當。 在具有一個以上酯鍵的基方面，可例示烷氧羰烷基’較 佳爲- RnCOORs所示之基。在此，Rn係伸乙基等碳數1至12 -22 - 201132657 之伸烷基，R9表示碳數1至20之烷基；Rn方面，較佳爲碳數2 至6之伸烷基。 2價基方面，可例舉碳數2以上20以下之伸烷基及碳數2 以上20以下之具有一個以上酯鍵的基等。在具有一個以上酯 鍵的基方面，可例示連結2個以上選自由1價至4價之烷基、酯 鍵，及醚鍵所構成群組之結構，且一個以上之較佳爲具有1 至4個醒鍵的2價基，較佳爲具有螺原醚（spiro-orthoether)環 及一個以上酯鍵的2價基。 在3價基方面，可例舉異三聚氰酸基（1,3,5-三阱-2,4,6(1H ，3H，5H)-三酮-1，3,5-三基）等》 4價基方面，可例舉具有一個以上酯鍵的基等，較佳可例 舉連結2個以上選自1價至4價烷基、酯鍵 '及醚鍵所構成之群 組之結構’且一個以上之較佳爲具有1至4個酯鍵的4價基。更 具體言之，可例舉C^dOCORu-h等。RM與前述相同，表示 碳數1至12之伸烷基；較佳爲與前述相同之物。 又’該式（3)所示之化合物方面，較佳爲X具有一個以上 酯鍵的基之化合物（E1)〔以下稱爲「成分E1」〕。 成分E1中’單酚化合物之適當例方面，可例舉下述式（4) 所不之化合物等。 -23 - 201132657In the formula (3), specific examples of X include the following monovalent to tetravalent groups. The monovalent group may, for example, be an alkyl group, an aliphatic group having one or more ester bonds (-c〇〇- and/or -OCO-), a group containing a benzotriazolyl group and a hindered amine group skeleton, and the like. In the case of the alkyl group, it is preferred that the alkyl group having a carbon number of 2 or more and 20 or less is excellent in preventing coloration of the cured product. In the case of a group having one or more ester bonds, an alkoxycarbonylalkyl group is preferably exemplified as a group represented by -RnCOORs. Here, Rn is an alkyl group having a carbon number of 1 to 12 -22 to 201132657, and R9 represents an alkyl group having 1 to 20 carbon atoms; and in terms of Rn, a alkylene group having 2 to 6 carbon atoms is preferred. The divalent group may, for example, be an alkylene group having 2 or more and 20 or less carbon atoms and a group having one or more ester bonds having 2 or more and 20 or less carbon atoms. In the case of a group having one or more ester bonds, a structure in which two or more groups selected from the group consisting of a monovalent to tetravalent alkyl group, an ester bond, and an ether bond are bonded is exemplified, and one or more preferably have 1 to The divalent group of the four awake bonds is preferably a divalent group having a spiro-orthoether ring and one or more ester bonds. In terms of a trivalent group, an iso-trisocyanate group (1,3,5-tri-trap-2,4,6(1H,3H,5H)-trione-1,3,5-triyl) can be exemplified. In the case of the tetravalent group, a group having one or more ester bonds or the like may be mentioned, and a group of two or more selected from the group consisting of a monovalent to a tetravalent alkyl group, an ester bond 'and an ether bond is preferably exemplified. The structure 'and more than one is preferably a tetravalent group having 1 to 4 ester bonds. More specifically, C^dOCORu-h and the like can be exemplified. The RM is the same as the above, and represents an alkylene group having 1 to 12 carbon atoms; preferably the same as the above. Further, in the case of the compound represented by the formula (3), the compound (E1) wherein X has one or more ester bond groups (hereinafter referred to as "component E1") is preferred. A suitable example of the 'monophenol compound' in the component E1 may, for example, be a compound of the following formula (4). -23 - 201132657
式（4)中’ 之碳數爲1以上時，相對於組成物之溶解性 爲充分，又，碳數爲20以下時，則少量即可獲得所期望之效 果，並可獲得均一的組成物。 在單酚化合物之具體例方面，119爲-C18H372化合物，由 於是旭電化工業股份有限公司以製品名AO-50販售，故取得 較容易。 在（E)成分中，在二酚化合物之適當例方面，可例舉下述 式（5)所示之化合物等。When the carbon number in the formula (4) is 1 or more, the solubility with respect to the composition is sufficient, and when the carbon number is 20 or less, a desired effect can be obtained in a small amount, and a uniform composition can be obtained. . In the specific example of the monophenol compound, 119 is a compound of -C18H372, which is sold by Asahi Denki Kogyo Co., Ltd. under the product name AO-50, so that it is easy to obtain. In the component (E), a compound represented by the following formula (5), and the like are exemplified as a suitable example of the diphenol compound.
5-2.成分F 成分F係亞磷酸酯化合物，在組成物中具有溶解性。在本 發明中「具有溶解性」，係指將組成物於-1 0 °C靜置7天，而 無觀察到析出之意》 在本發明，藉由含有成分F而可達成尤其是同時加諸光與 熱於硬化有組成物的積層物之情形之抑制著色的效果，除此 -24 - 201132657 之外在寒冷地區卻無在組成物中產生析出物等的問題。 成分F方面，可使用各種化合物。 成分F方面’可例舉下述式（6)至（8)所示之化合物等。 p(〇Rio)3 …⑷ 〔式（6)中’ R1()表示碳數1至2〇之烷基或芳香族基；複數 個Rio可各自相同或相異〕 (〇Rl2)2P-〇-Ri3-〇-P(〇Rl2)2 ...(7) 〔式（7)中’ 1112表示碳數1至2〇之烷基；R13表示具有碳數 6至10之芳香環的2價基；複數個R12可各自相同或相異〕 oh2c ch2o5-2. Component F Component F is a phosphite compound and has solubility in a composition. In the present invention, "having solubility" means that the composition is allowed to stand at -10 ° C for 7 days without any precipitation being observed. In the present invention, by containing the component F, it is possible to achieve, in particular, simultaneous addition. In the case where the light and the heat are hardened to laminate the laminate having the composition, the effect of suppressing the coloring is not caused by the occurrence of precipitates or the like in the composition in the cold region except for the period of -24-201132657. As the component F, various compounds can be used. The component F can be exemplified by the following formulas (6) to (8). p(〇Rio)3 (4) [In the formula (6), 'R1() represents an alkyl group or an aromatic group having 1 to 2 carbon atoms; and a plurality of Rios may be the same or different each other) (〇Rl2)2P-〇 -Ri3-〇-P(〇Rl2) 2 (7) [1112] represents an alkyl group having 1 to 2 carbon atoms; and R13 represents a 2 valent group having an aromatic ring having 6 to 10 carbon atoms. Base; plural R12 can be the same or different] oh2c ch2o
Rl4-Ο—P\ 〉：〔 〕Ρ-Ο—R14 ...(8) 'OH2C, 'CH2。/ 〔式（8)中，R14表示碳數1至20之烷基或芳香族基；複數 個Rm可各自相同或相異〕 R1〇、R12、及r14之烷基方面，可爲直鏈狀或分支狀。碳 數方面’因相對於組成物之溶解性優異，故碳數方面較佳爲6 至1 4之物。 R1〇及Rm之芳香族基方面，可例舉苯基、烷基取代苯基 等。在烷基取代苯基中，烷基方面，可爲直鏈狀亦可爲分支 狀。碳數方面可例舉1至18之物，因相對於組成物之溶解性優 異，故碳數方面較佳爲6至15之物。 R13之具有芳香環之2價基方面，可例舉例如下述所示之 基等 -25 - 201132657Rl4-Ο-P\ 〉: [ ] Ρ-Ο-R14 (8) 'OH2C, 'CH2. In the formula (8), R14 represents an alkyl group or an aromatic group having 1 to 20 carbon atoms; a plurality of Rm may be the same or different each other; and the alkyl group of R1〇, R12, and r14 may be a linear chain. Or branching. Since the carbon number is excellent in solubility with respect to the composition, it is preferably from 6 to 14 in terms of carbon number. The aromatic group of R1〇 and Rm may, for example, be a phenyl group or an alkyl-substituted phenyl group. In the alkyl-substituted phenyl group, the alkyl group may be linear or branched. The number of carbon atoms may be 1 to 18, and since it is excellent in solubility with respect to the composition, it is preferably 6 to 15 in terms of carbon number. The R2 having a divalent group of an aromatic ring may, for example, be a group shown below. -25 - 201132657
成分F方面，相較於具有螺旋雙環骨架式（8)之化合物， 式（6)及式（7)之化合物，因對組成物之溶解性優異，且因長期 著色抑制效果優異故適當。再者，式（6)之化合物由於少量之 添加，而相對於熱或光之著色抑制效果優異更適當。 式（6)之化合物方面，相對應於R爲烷基之情形（以Ral表示 )與R爲芳香族基之情形（以Rar表示），則有下述式（6-1)至（6-4 )所示之化合物。 P(〇Ral)3 • ·· ( 6 -1 ) Rar〇P(〇Ral)2 …（6_2) (Rar〇)2P(〇Ral) • · . (6 - 3 ) (RarO)jP • · · ( 6 - 4) 在該（6-1)至（6-4)所示之化合物中，由相對於組成物之溶 解性與長期著色抑制效果均爲優異之觀點觀之，以下述順序 較適當。 (6-2)>(6-1)>(6-3)>(6-4) 該（6-1)至（6-4)所示化合物之具體例方面，可例舉例如下 述化合物等。 (6-1):亞磷酸三辛酯、亞磷酸三癸酯、亞磷酸三月桂酯 (6-2):亞磷酸苯基二烷酯（烷基方面有碳數8至12之物） (6-3):亞磷酸二苯基烷酯（烷基方面有碳數8至12之物） -26 - 201132657 (6-4):亞磷酸三苯酯、亞磷酸參（4-壬基苯基）酯，亞磷酸 參（2,4-二-三級丁基）酯 在成分E及成分F成分之調配比率方面，相對於硬化性成 分（成分A、B及C)之合計量100重量份，較佳是調配0.01至5 重量份成分E，調配0.01至5重量份成分F，更佳爲調配0.05至 3重量份成分E，調配0.05至1重量份成分F » 成分E及成分F各自低於0.01重量份時，則在硬化組成物 的硬化物中，造成熱或光所致著色發生，在超過5重量份時， 則析出而無法獲得均一的組成物，又，會使硬化性降低。 6.其他成分 本發明之組成物雖然該成分A至F爲必須，不過可依目的 調配各種任意成分。 以下，就各自之成分加以說明。 本發明之組成物，在目的係進一步進行硬化，可調配熱 聚合引發劑於組成物中，並在活性能量線照射後可予以加熱 〇 熱聚合引發劑方面，可使用各種化合物，較佳爲有機過 氧化物及偶氮系引發劑。 有機過氧化物之具體例方面，可例舉1，1-雙（三級丁基過 氧基）2-甲基環己烷、1,1-雙（三級己基過氧基）-3,3，5-三甲基 環己烷、1，1-雙（三級己基過氧基）環己烷、1，1-雙（三級丁基過 氧基）-3,3,5-三甲基環己烷、1，1-雙（三級丁基過氧基）環己烷 -27 - 201132657 、2,2-雙（4,4-二-丁基過氧環己基）丙烷、1，1-雙（三級丁基過 氧基）環十二烷、過氧異丙基單碳酸三級己酯、過氧順丁烯二 酸三級丁酯、過氧-3,5,5-三甲基己酸三級丁酯、過氧月桂酸 三級丁酯、2,5-二甲基-2,5-二（間甲苯醯基過氧基）己烷、過氧 異丙基單碳酸三級丁酯、過氧2 -乙基己基單碳酸三級丁酯、 過氧苯甲酸三級己酯、2,5-二-甲基-2,5-二（苯甲醯基過氧基） 己烷、過氧乙酸三級丁酯、2,2-雙（三級丁基過氧基）丁烷、過 氧苯甲酸三級丁酯、正丁基-4，4-雙（三級丁基過氧基）戊酸酯 、過氧異鄰苯二甲酸二-三級丁酯、α、α‘-雙（三級丁基過氧基 )二異丙苯、二枯烯基過氧化物、2,5-二甲基-2，5-二（三級丁基 過氧基）己烷、三級丁基枯烯基過氧化物、二-三級丁基過氧 化物、對薄荷烷氫過氧化物、2,5-二甲基-2，5·二（三級丁基過 氧基）己炔-3、二異丙苯氫過氧化物、三級丁基三甲基矽烷基 過氧化物、1，1,3,3-四甲基丁基氫過氧化物、二異丙苯（cumyl )氫過氧化物、三級己基氫過氧化物及三級丁基氫過氧化物等 〇 偶氮系化合物之具體例方面、可例舉1，1 偶氮雙（環己烷 -1-腈（carbonitrile))、2-(胺甲醯基偶氮）異丁腈、2 -苯基偶氮-4-甲氧基-2,4-二甲基戊腈、偶氮二-三級辛烷及偶氮二-三級 丁烷等。 該等可單獨使用、亦可倂用2種以上。又，有機過氧化物 係藉由與還原劑之組合而可進行氧化還原反應。 -28 - 201132657 在本發明中，藉由在硬化步驟照射於組成物之低波長活 性能量線之影響，而可防止所獲得光學構件著色，或在使用 所獲得光學構件的環境中，例如從以液晶顯示裝置使用作爲 光源之冷陰極管所照射之紫外線區域之活性能量線所致著色 ，在目的爲防止此等著色’較佳爲調配紫外線吸收劑。 紫外線吸收劑方面，雖可使用各種化合物，不過較佳爲 溶解於組成物之物。 紫外線吸收劑之具體例方面，可例舉2-[4-[(2 -羥基-3-十 二矽烷氧丙基）氧]-2-羥苯基]-4,6-雙（2,4-二甲基苯基）-1，3,5-三畊' 2-[4-[(2-羥基-3-十三矽烷氧丙基）氧]-2-羥苯基]-4,6-雙（2,4-二甲基苯基）-l，3,5-三阱、2-[4-[(2-羥基- 3-(2-乙基六 矽烷氧）丙基）氧]-2 -羥苯基]-4,6 -雙（2,4 -二甲基苯基）-1,3，5-三畊、2，4-雙（2-羥基_4 -丁氧基苯基）-6-(2，4 -雙-丁氧基苯基）· 1，3,5-三阱、2-(2-羥基- 4-[l-辛氧基羰乙氧基]苯基）_4,6_雙（4· 苯基苯基）-1,3,5-三阱等之三畊系紫外線吸收劑； 2-(2H-苯并***-2-基）-4,6-雙（1-甲基-丨_苯基乙基）酚、2 -(2-經基-5-三級丁基苯基）-2H -苯并三哩、2-[2-羥基- 5- (2-( 甲基）丙烯醯氧乙基）苯基]-2H-苯并***等之苯并***系紫外 線吸收劑； 2,4-二羥基二苯酮、2-羥基-4-甲氧基二苯酮等之二苯酮 系紫外線吸收劑；丙稀酸乙基-2-氰-3,3 -二苯醋、丙燃酸辛基 -2-氰基-3,3-二苯酯等之氰丙烯酸酯系紫外線吸收劑等。 -29 - 201132657In the case of the component F, the compound of the formula (6) and the formula (7) is excellent in solubility in the composition and is excellent in long-term coloring suppressing effect, as compared with the compound having the helical bicyclic skeleton formula (8). Further, since the compound of the formula (6) is added in a small amount, it is more preferable because it is excellent in the coloring suppressing effect against heat or light. In the case of the compound of the formula (6), in the case where R is an alkyl group (indicated by Ral) and R is an aromatic group (indicated by Rar), there are the following formulas (6-1) to (6-). 4) The compound shown. P(〇Ral)3 • ·· ( 6 -1 ) Rar〇P(〇Ral)2 ...(6_2) (Rar〇)2P(〇Ral) • · . (6 - 3 ) (RarO)jP • · · (6 - 4) Among the compounds represented by the above (6-1) to (6-4), the solubility in the composition and the long-term coloring inhibitory effect are excellent, and the following order is appropriate. . (6-2)>(6-1)>(6-3)>(6-4) Specific examples of the compounds represented by the above (6-1) to (6-4) can be exemplified as follows Said compounds and the like. (6-1): Trioctyl phosphite, tridecyl phosphite, trilauryl phosphite (6-2): phenyl dialkyl phosphite (having an alkyl group of 8 to 12) 6-3): Diphenylalkyl phosphite (having a carbon number of 8 to 12 in the alkyl group) -26 - 201132657 (6-4): Triphenyl phosphite, phosphite (4-mercaptobenzene) The base of the ester, the bisphosphonium phosphite (2,4-di-tert-butyl) ester, the total ratio of the component E and the component F, relative to the curable component (components A, B and C) 100 weight For the portion, preferably 0.01 to 5 parts by weight of the component E, 0.01 to 5 parts by weight of the component F, more preferably 0.05 to 3 parts by weight of the component E, and 0.05 to 1 part by weight of the component F » component E and component F, respectively. When the amount is less than 0.01 part by weight, coloring occurs due to heat or light in the cured product of the cured composition, and when it exceeds 5 parts by weight, precipitation is performed to obtain a uniform composition, and the hardenability is lowered. . 6. Other components Although the components A to F are essential to the composition of the present invention, various optional components may be formulated depending on the purpose. Hereinafter, the respective components will be described. The composition of the present invention may be further cured, and a thermal polymerization initiator may be added to the composition, and after heating the active energy ray to heat the thermal polymerization initiator, various compounds may be used, preferably organic. Peroxide and azo initiators. Specific examples of the organic peroxide include 1,1-bis(tertiarybutylperoxy)2-methylcyclohexane and 1,1-bis(tri-hexylperoxy)-3. 3,5-trimethylcyclohexane, 1,1-bis(tri-hexylperoxy)cyclohexane, 1,1-bis(tri-butylperoxy)-3,3,5-three Methylcyclohexane, 1,1-bis(tertiary butylperoxy)cyclohexane-27 - 201132657, 2,2-bis(4,4-di-butylperoxycyclohexyl)propane, 1 , 1-bis(tertiary butylperoxy)cyclododecane, peroxyisopropyl monocarbonate, ternary butyl peroxy maleate, peroxy-3,5,5 -trimethyl butyl trimethyl hexanoate, butyl laurate laurate, 2,5-dimethyl-2,5-di(m-tolylperyloxy)hexane, peroxyisopropyl Tert-butyl butyl carbonate, tertiary butyl 2-ethylhexyl monocarbonate, tertiary hexyl peroxybenzoate, 2,5-di-methyl-2,5-di(benzhydryl) Oxy) hexane, butyl peroxyacetate, 2,2-bis(tertiary butylperoxy)butane, tert-butyl peroxybenzoate, n-butyl-4,4-dual Tert-butyl butyl peroxy) valerate Di-tertiary butyl isophthalate, α,α'-bis(tertiary butylperoxy)diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2, 5-bis(tertiary butylperoxy)hexane, tertiary butyl cumyl peroxide, di-tertiary butyl peroxide, p-menthane hydroperoxide, 2,5-dimethyl Base-2,5.di(tris-butylperoxy)hexyne-3, diisopropylbenzene hydroperoxide, tertiary butyltrimethyldecyl peroxide, 1,1,3,3 Specific examples of a quinone azo compound such as tetramethylbutyl hydroperoxide, cumyl hydroperoxide, tertiary hexyl hydroperoxide, and tertiary butyl hydroperoxide, 1,1 azobis(carbonitrile), 2-(aminomethylmercaptoazo)isobutyronitrile, 2-phenylazo-4-methoxy-2 can be exemplified. , 4-dimethylvaleronitrile, azobis-tertiary octane, azobis-tertiary butane, and the like. These may be used alone or in combination of two or more. Further, the organic peroxide can be subjected to a redox reaction by a combination with a reducing agent. -28 - 201132657 In the present invention, the coloring of the obtained optical member can be prevented from being colored by the influence of the low-wavelength active energy ray irradiated on the composition in the hardening step, or in the environment in which the obtained optical member is used, for example, from The liquid crystal display device is colored by the active energy ray of the ultraviolet ray region irradiated by the cold cathode tube as a light source, and it is preferable to dispose the ultraviolet ray absorbing agent in order to prevent such coloring. In the case of the ultraviolet absorber, various compounds can be used, but it is preferably dissolved in the composition. Specific examples of the ultraviolet absorber include 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis (2,4) -Dimethylphenyl)-1,3,5-three tillage '2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6 - bis(2,4-dimethylphenyl)-l,3,5-tripper, 2-[4-[(2-hydroxy-3-(2-ethylhexacyloxy)propyl)oxy] -2 -hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-three tillage, 2,4-bis(2-hydroxy-4-isobutoxybenzene -6-(2,4-bis-butoxyphenyl)· 1,3,5-tritrap, 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl _4,6_bis(4.phenylphenyl)-1,3,5-tri-trap, etc., three-till ultraviolet absorber; 2-(2H-benzotriazol-2-yl)-4,6 - bis(1-methyl-indole-phenylethyl)phenol, 2-(2-carb-5-tributylphenyl)-2H-benzotriazine, 2-[2-hydroxy-5 - a benzotriazole-based ultraviolet absorber such as (2-(methyl)acryloxyethyl)phenyl]-2H-benzotriazole; 2,4-dihydroxybenzophenone, 2-hydroxy-4 a benzophenone-based ultraviolet absorber such as methoxybenzophenone; ethyl-2-cyano-3,3-diphenylacetate or propyl acrylate 2-cyano-3,3-diphenyl octyl acrylate and the like of the cyanoacrylate-based ultraviolet absorber. -29 - 201132657
紫外線吸收劑係市售品，可例舉日本BASF製TINUVIN P S ' TINUVIN 99-2、TINUVIN 109 ' TINUVIN 3 84-2 ' TINU VIN 900 ' TINUVIN 928等之苯并***系紫外線吸收劑、 或TINUVIN 479、TINUVIN 460等之羥苯基三阱系紫外線吸 收劑。 該等中’則以揮發性低，再者在光學構件之使用環境中 多有問題之長波長紫外線區域中紫外線吸收能力高，苯并三 唑系紫外線吸收劑爲佳，具體言之，以τ IN U V IN 9 0 0、T IN U VIN 92 8等爲適當。 紫外線吸收劑之比率方面，相對於硬化性成分之合計量1 〇〇重量份，以0.01至5重量份爲佳，更佳爲〇.1至3重量份。 紫外線吸收劑爲0 · 0 1重量份以上時，在光學構件之使用 環境中可抑制著色’若爲5重量份以下時，則可保持相對於組 成物之充分的溶解性，與良好的活性能量線硬化性。. 即使該成分以外’可依照需要，調配消泡劑、均平劑、 無機充塡劑、有機充塡劑、光穩定劑及本發明之必須成分以 外之抗氧化劑等。 7 .活性能量線硬化型光學構件用組成物 本發明之組成物係以即述成分A至F爲必須成分，可以前 述之調配比率含有該等。 在組成物之製造方法方面，較佳是依照通常方法，可例 舉將（A)至（F)成分，依照需要之其他成分予以攪拌.混合之方 -30 - 201132657 法等。 (A)成分因在常溫黏度高，或固體之物多，故組成物 溫不能爲液狀之情形，在將組成物攪拌·混合後亦可予以 。加熱溫度方面，較佳爲50至100 °C。 本發明之組成物可提供較佳爲折射率（25°C ) 1.5 70以 更佳爲1.590以上，特佳爲1.570至1.650高折射率之硬化 再者，該硬化物從壓模之脫模性及對轉印薄膜之密合性 優異。再者，藉由含有成分E及成分F，而可獲得因熱或 致著色或劣化少耐久性良好的光學構件。 如此，本發明之組成物之硬化物，因具有高折射率 生產性，故可使用於夫瑞乃透鏡及雙凸透鏡、液晶顯示 之背光用稜鏡薄片等之透鏡片以及塑膠透鏡等各種光學 〇 在透鏡片方面，更詳言之，可例舉視訊投影機，投 視及液晶顯不器等用途。 8.使用方法 本發明之組成物之使用方法方面，可依照通常方法 具體而言，可例舉將組成物塗布於具有透鏡形狀的 ，在以薄膜或薄片基材（以下該等歸納稱爲「薄膜基材」 合後，照射活性能量線予以硬化之方法等。 本發明可使用之薄膜基材方面，較佳爲聚甲基丙烯 酯、聚甲基丙烯酸甲酯-苯乙烯共聚物薄膜、聚對酞酸乙 在室 加熱 上， 物。 亦爲 光所 且高 裝置 材料 影電 壓模 )貼 酸甲 二酯 -31 - 201132657 、聚萘二甲酸乙烯酯、聚芳基化物、聚丙烯酸腈、聚碳酸酯 、聚楓、聚醚碾、聚醚醯亞胺、聚醚酮、聚醯亞胺、聚甲基 戊烯等之塑膠·薄膜’若有必要則可使用玻璃系基材》 基材以透明或者半透明（例如乳白色）之物爲適當。薄膜 基材之厚度方面較佳爲20至200μιη。 本發明之組成物係以活性能量線照射予以硬化，不過以 簡便且廉價之觀點觀之，以紫外線較適當。 在紫外線照射中，一般是使用在紫外線硬化型組成物之 硬化所使用之超高壓汞燈、高壓汞燈、低壓汞燈、金屬鹵素 燈、碳弧及氙燈、LED等較佳。較佳爲使用以波長3 6 5nm作爲 中心之紫外線比較多的高壓汞燈或金屬鹵素燈。紫外線之照 射量若爲200mJ/cm2以上則可使之硬化，較佳爲300至2,000mJ /cm2 ° 茲就使用本發明之組成物，製造透鏡片之例加以說明。 在製造膜厚比較薄的透鏡片之情形，係將本發明之組成 物’塗布於目的之具有透鏡之形狀的被稱爲壓模的鑄模，設 置該組成物之層，並在該層之上將轉印透鏡片的透明基板予 以密合。 接著，自透明基板側照射活性能量線，使組成物硬化， 其後，自鑄模予以剝離。 一方面，在製造膜厚比較厚的透鏡片之情形，在目的之 具有透鏡形狀的鑄模與透明基板之間，傾注本發明之組成物 -32 - 201132657 接著，自透明基板側照射活性能量線，使組成物硬化， 其後，自鑄模脫模（form removal)。 該鑄模方面，其材質並無特別限定，可例舉例如黃銅及 鎳等金屬，以及環氧樹脂等之樹脂。由鑄模之壽命長之觀點 觀之，以金屬製爲佳。 [實施例] 茲例舉實施例（E)及比較例（C)，更具體說明本發明如下 。另外，在以下「份」係指重量份之意。 〇實施例1至5(E1至E5)及比較例1至10(C1至C10) 使用下述表1所示（成分A)至（成分F)，依照通常方法予以 攪拌·混合，來製造活性能量線硬化型光學構件用組成物。 -33 - 201132657 其他 CL ϋ 1 1 1 1 1 1 1 1 1 1 1 LO ο ι ι 1 eg 1 1 1 1 1 1 ι 1 1 1 ο 1 1 1 1 σ X 1 1 1 1 1 1 1 1 1 ιη ο 1 1 1 1 1 Τ-900 1 1 1 1 τ-Η 1 1 1 1 1 1 1 1 1 1 Τ-928 1 1 1 τ-Η 1 1 ί 1 1 1 1 1 1 1 1 成分F 3010 Ο 1 »-Η ο CO ο τ-Η ο 1 1 1 ι—Η ο 1 1 1 1 1 CO ο 135Α t ο 1 1 1 1 1 1 1 I 1 1 1 1 1 成分E Α0*080 CO ο 1 CO ο »-Η CO ο 1 1 1 1 1 1 1 1 1 ΑΟ-050 I CO ο 1 1 1 1 1 1 ΓΟ ο 1 CO ο 1 1 1 1 成分D ΤΡΟ r-H ?—Η τ-Η »-Η 1 1 1 1 1 1 1 ) 1 τ—Η Irgl84 ΙΟ m m LO ΙΟ LO m LO LO LO LD LO LO LO ΙΟ 成分C NVC 1 I 1 艺 1 1 1 1 1 t 1 \ 1 1 ο »-Η Μ-1600 1 I 1 1 1 1 1 ο ο ο ο ο 1 ) 1 ΡΟΑ 1 1 1 1 1 1 1 ο ο ο ο ο 1 1 1 Μ-211Β 1 1 1 1 1 1 1 ο ο ο ο ο 1 I 1 Μ-305 ο ο LO ο ο 1 1 1 ι 1 I 1 1 1 1 成分B ΤΟ-2344 1 § § 1 1 1 1 t 1 1 ' I 1 1 § 1 ΤΟ-1463 § ι 1 g ο ο ι-Η 1 ο ο ο ο ο § 1 1 成分A ΟΤ-2501 ο ο LO § 1 ο f-^ t 1 1 1 1 宕 1 CM ω CO m 寸 ω LO ω (Μ υ CO ο S ΰ δ 卜 g ο C10 201132657 使用於實施例（E)的化合物之簡稱，係下述之意。 •〇T-2501:A型丙烯酸環氧酯[東亞合成（股）製]Aronics OT-250 1 ) •TO-1463:丙烯酸鄰苯基苯氧基乙酯[東亞合成（股）製] AronicsTO-1 463) • ΤΟ-23 44··ο-丙烯酸鄰苯基苯酯[東亞合成（股）製]Aronics TO -2344) •M-3〇5:三丙烯酸新戊四醇酯與四丙烯酸新戊四醇酯 混合物[東亞合成（股）製]Aronics M-305〕 •NVC:N-乙烯咔唑[和光純藥（股）製N-乙烯咔唑] •Irgl84:l-羥基環己基苯酮（BASF公司製Irgacure 184 ) •TPO:2,4,6-三甲基苯甲醯基二苯膦氧化物（BASF公司 製 Lucirin TPO) .AO-50··十八基- 3-(3,5-二-三級丁基-4-羥苯基）丙酸酯 [Adeca(股）製AO-50，式（3)中R1爲十八基之化合物] •AO-80:3,9-雙[2-{3-(3-三級丁基-4-羥基-5-甲基苯基） 丙醯氧基}-1，1-二甲基乙基]-2,4,8,10 -四氧雜螺旋[5.5]十 一烷[Adeca(股）製AO-80，式（5)之化合物] .135A:亞憐酸二苯基異癸醋[Adeca(股）_Adeca stab 135A] .3010:亞磷酸三異癸酯[Adeca(股）製Adeca stab 3010 ] •T-928:苯并***系紫外線吸收劑，日本BASF公司製τ -35 - 201132657 INUVIN 928 •T-900:苯并***系紫外線吸收劑，曰本BASF公司製τ INUVIN 900 使用於比較例（C)的化合物之簡稱，係下述之意。 •M-211B:雙酚A EO加成物之二丙烯酸酯[東亞合成（ 股）製 Aronics M-2 1 1 B] •POA:丙烯酸苯氧基乙酯[東亞合成（股）製AronicsM- 100] •M-1600:聚醚系胺基甲酸酯丙烯酸酯[東亞合成（股）製 AronicsM-1600] •HQ:氫醌 .412:新戊四醇-肆- (β-月桂基-硫代丙酸酯）〔Adeca(股） 製 AO-4 1 2S〕 •GP:6-[3-(3-三級丁基-4-羥基-5-甲基）丙氧基]-2,4,8，1 0-四-三級丁基二苯并[(1彳][1，3,2]二氧雜二噁磷品（？11〇8?116 pin)[住友化學（股）製 Sumilizer GP] 〇評價 使用前述所獲得之組成物，依照下述之方法評價。 該等結果如表2所示。 1) 黏度 使用E型黏度計，於25 °C測定黏度。 另外，比較例2之組成物，黏度過高而無法測定。 2) 折射率 -36 - 201132657 使用所獲得之組成物，並使用具備傳送裝置（conveyor )的高壓汞燈，在365nm附近之照射量成爲500mJ/cm2之條件 下使用經硬化之物。 關於所獲得之硬化物，在鈉D線中，以Atago(股）製阿 倍折射計DR-M2來測定折射率（25°C )。 3) 密合性 相對於轉印薄膜之密合性，係以棋盤眼試驗予以評價 〇 基材薄膜，係使用聚對苯二甲酸乙二酯（以下稱爲PET) 薄膜[東洋紡績（股）製Cosmo shine A4300]，使用棒塗布機 以膜厚30μιη塗布，以與折射率試驗相同之條件下進行紫外 線照射。 使用所獲得之硬化物，依照JIS Κ5 400記載之方法，測 定硬化物層之脆性或對薄膜基材之附著性，以下述之三階 段評價。 〇：棋盤眼殘留數90以上，△:棋盤眼殘留數70以上，X:棋 盤眼殘留數69以下 4) 剝離試驗 在具有透鏡形狀之鎳製壓模中，塗布以膜厚50μιη所獲 得之組成物，並以膜厚ΙΟΟμιη之PET薄膜貼合》 接著，以與折射率試驗相同之條件下進行紫外線照射 來製作硬化物。 將在鎳壓模與PET薄膜之間保持於90°之剝離試驗，以 -37 - 201132657 試樣寬度50mm，拉伸速度lm/miη進行，測定剝離強度。剝 離強度爲200g/5 0mm以下且全部之樹脂硬化物密合於轉印 薄膜之物，被判斷爲來自壓模之脫模性爲良好。 5) 透鏡形狀之外觀 以顯微鏡觀察前述..剝離試驗之結果所獲得之透鏡 > 確 認透鏡形狀並無缺陷。 顯微鏡方面，係使用Keyence(股）製數位顯微鏡VH-6 30 〇 ’以倍率1 5 00倍觀察透鏡形狀。無缺陷者爲〇，確認有缺 陷者爲X。 6) 低溫穩定性 將組成物在-1 〇 °C之冷凍庫靜置7天，以目視確認有無 析出，並以下述基準判定。 〇：7日後亦無見到析出。X:在1至2日後見到析出。 7) 著色之測定 使用以與轉印薄膜密合性評價相同之方法製作的試驗 片’評價80°C X 500小時後之著色。使用積分球式光譜反射 率測定儀（村上色材技術硏究所公司製D Ο T - 3 C )，測定試驗 前試樣（test specimen)之YI値，以及，耐熱試驗後試樣之γ 1値。另外，在後述表中’關於試驗後之著色，係以△ Y I ( 各試驗後之試樣B之YI値與各試驗前試樣B之YI値之差）表 示。 -38 - 201132657 [表2] 黏度 (mPa · s) 折射率 密合性 剝離試驗 (g/50mm) 透鏡形狀的外觀 低溫穩 定性 耐熱試驗 後的」YI E1 270 1.598 〇 145 〇 〇 0.2 E2 240 1.603 〇 163 〇 〇 0.4 E3 200 1.596 〇 140 〇 〇 0.2 E4 553 1.616 〇 160 〇 〇 0.3 E5 270 1.598 〇 145 〇 〇 0.1 C1 160 1.610 X 30 X 〇 0.8 C2 - 1.576 Δ 308 X 〇 1.5 C3 250 1.566 〇 190 〇 〇 0.8 C4 250 1.566 〇 190 〇 〇 0.5 C5 250 1.566 〇 190 〇 〇 3.2 C6 250 1.566 〇 190 〇 X 0.4 C7 250 1.566 〇 190 〇 〇 1.0 C8 450 1.602 〇 185 〇 〇 0.6 C9 370 1.575 〇 181 〇 〇 0.6 C10 - - - - - X - 由實施例之結果明顯可知，本發明之組成物，其硬化 物係高折射率，又，對轉印薄膜之密合性高，由於具有透 鏡形狀之壓模亦使脫模性爲良好，作爲透鏡片生產性非常 高，故可獲得耐久性優異、熱所致著色少的硬化物。含有N VC之實施例4之組成物，進一步折射率極爲優異。 一方面，不含成分A之比較例1之組成物，雖然折射率 變高，不過對轉印薄膜之密合性低，並無法獲得良好的透 鏡形狀。又，硬化性成分係僅成分A的比較例2之組成物， 黏度過高，在室溫之處理有問題，加上會有密合性或透鏡 形狀的問題。再者，在成分A並非必須的組成物中，如比較 例3至7所顯而可知，並無法獲得充分高的折射率。含有成 分E以外之酚系抗氧化劑的比較例5之組成物則熱所致著色 -39 - 201132657 變大。又，含有成分F以外之硫系抗氧化劑的比較例6之組 成物，雖可防止熱所致著色，不過因低溫且易於析出，故 會有組成物穩定性上的問題。又，使用到抗氧化劑的比較 例7之組成物，該抗氧化劑係在同一分子中具有酚性羥基與 磷者，則可見到熱所致著色變大的傾向。雖含有成分A至C 成分，不過在不含成分E及成分F的比較例8及同9之組成物 ，雖然折射率、密合性及脫模性優異，不過熱所致著色則 因而變大。含有NVC的實施例4之組成物，進一步折射率極 爲優異。不含成分A及成分B，僅含有作爲成分C之NVC的 組成物（比較例1 0)，熔點高，即使調配成分D，因在室溫進 行結晶化，故無法進行低溫穩定性試驗以外之評價。 [產業上可利用性] 本發明之組成物，可使用於各種光學材料製造，更 具體言之’在使用於投影電視等螢幕的夫瑞乃透鏡或雙凸 透鏡等之透鏡部，或使用於液晶顯示裝置之背光的稜鏡透 鏡片特別有用。 【圖式簡單說明】 無。 【主要元件符號說明】 dnt 無0 • 40 -The ultraviolet absorber is a commercially available product, and may be a benzotriazole-based ultraviolet absorber such as TINUVIN PS ' TINUVIN 99-2, TINUVIN 109 ' TINUVIN 3 84-2 ' TINU VIN 900 ' TINUVIN 928, or TINUVIN, manufactured by BASF, Japan. 479, hydroxyphenyl tri-trap UV absorbers such as TINUVIN 460. In these cases, the volatility is low, and in the long-wavelength ultraviolet region where there is a problem in the use environment of the optical member, the ultraviolet absorbing ability is high, and the benzotriazole-based ultraviolet absorbing agent is preferable, specifically, τ IN UV IN 9 0 0, T IN U VIN 92 8 and the like are appropriate. The ratio of the ultraviolet absorber is preferably from 0.01 to 5 parts by weight, more preferably from 0.1 to 3 parts by weight, based on 1 part by weight of the total amount of the curable component. When the amount of the ultraviolet absorber is 0. 0.001 parts by weight or more, the coloring can be suppressed in the use environment of the optical member. When the amount is 5 parts by weight or less, sufficient solubility with respect to the composition can be maintained, and good active energy can be maintained. Line hardenability. In addition to the components, an antifoaming agent, a leveling agent, an inorganic filling agent, an organic filling agent, a light stabilizer, and an antioxidant other than the essential components of the present invention may be formulated as needed. 7. Composition for active energy ray-curable optical member The composition of the present invention contains the components A to F as essential components, and may be contained in the above-mentioned blending ratio. In terms of the method for producing the composition, it is preferred to carry out the mixing of the components (A) to (F) and other components as necessary in accordance with a usual method. The mixing method is -30 - 201132657. Since the component (A) has a high viscosity at room temperature or a large amount of solid matter, the temperature of the composition may not be liquid, and the composition may be stirred and mixed. In terms of heating temperature, it is preferably from 50 to 100 °C. The composition of the present invention can provide a refractive index (25 ° C) of 1.5 70 or more, more preferably 1.590 or more, particularly preferably a high refractive index of 1.570 to 1.650, and the release property of the cured product from the stamper. And excellent in adhesion to the transfer film. Further, by containing the component E and the component F, an optical member excellent in durability due to heat or coloration or deterioration can be obtained. As described above, since the cured product of the composition of the present invention has high refractive index productivity, it can be used for various optical ray such as lens sheets and plastic lenses for Fresnel lenses and lenticular lenses, liquid crystal display backlight sheets, and the like. In terms of the lens sheet, more specifically, it can be exemplified by a video projector, a projector, and a liquid crystal display. 8. Method of Use In terms of the method of using the composition of the present invention, it is possible to specifically apply the composition to a film having a lens shape in a film or a sheet substrate (hereinafter referred to as " After the film substrate is combined, it is cured by irradiation with an active energy ray. The film substrate which can be used in the present invention is preferably a polymethacrylic ester, a polymethyl methacrylate-styrene copolymer film, or a poly For the heating of bismuth citrate in the chamber, it is also a light and high device material photovoltage mode) acid methyl ester-31 - 201132657, polyethylene naphthalate, polyarylate, polyacrylonitrile, poly Plastics/films such as carbonate, poly maple, polyether mill, polyether oxime, polyether ketone, polyimide, polymethylpentene, etc. If necessary, a glass substrate can be used. Transparent or translucent (eg milky white) is appropriate. The thickness of the film substrate is preferably from 20 to 200 μm. The composition of the present invention is hardened by irradiation with an active energy ray, but it is suitable for ultraviolet rays from the viewpoint of simplicity and low cost. In the ultraviolet irradiation, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, a carbon arc lamp, a xenon lamp, or the like which is used for curing the ultraviolet curable composition is generally used. It is preferred to use a high-pressure mercury lamp or a metal halide lamp having a relatively high ultraviolet ray having a wavelength of 365 nm as a center. When the amount of ultraviolet rays is 200 mJ/cm2 or more, it can be cured, and it is preferably 300 to 2,000 mJ/cm2. The composition of the present invention is used to produce a lens sheet. In the case of producing a lens sheet having a relatively thin film thickness, a composition of the present invention is applied to a mold having a shape of a lens called a stamper, and a layer of the composition is disposed on and above the layer. The transparent substrate of the transfer lens sheet is brought into close contact. Next, the active energy ray is irradiated from the transparent substrate side to cure the composition, and thereafter, it is peeled off from the mold. On the one hand, in the case of producing a lens sheet having a relatively thick film thickness, a composition of the present invention is poured between a target mold having a lens shape and a transparent substrate -32 - 201132657, and then the active energy ray is irradiated from the transparent substrate side. The composition is allowed to harden, and thereafter, form removal is performed from the mold. The material of the mold is not particularly limited, and examples thereof include metals such as brass and nickel, and resins such as epoxy resins. From the standpoint of the long life of the mold, it is preferable to use metal. [Examples] Examples (E) and Comparative Examples (C) are exemplified, and the present invention will be more specifically described below. In addition, the following "parts" means the parts by weight. Examples 1 to 5 (E1 to E5) and Comparative Examples 1 to 10 (C1 to C10) Using the components (component A) to (component F) shown in the following Table 1, stirring and mixing were carried out in accordance with a usual method to produce an activity. A composition for an energy ray-curable optical member. -33 - 201132657 Other CL ϋ 1 1 1 1 1 1 1 1 1 1 1 LO ο ι ι 1 eg 1 1 1 1 1 1 ι 1 1 1 ο 1 1 1 1 σ X 1 1 1 1 1 1 1 1 1 Ιη ο 1 1 1 1 1 Τ-900 1 1 1 1 τ-Η 1 1 1 1 1 1 1 1 1 1 Τ-928 1 1 1 τ-Η 1 1 ί 1 1 1 1 1 1 1 1 Component F 3010 Ο 1 »-Η ο CO ο τ-Η ο 1 1 1 ι—Η ο 1 1 1 1 1 CO ο 135Α t ο 1 1 1 1 1 1 1 I 1 1 1 1 1 Component E Α0*080 CO ο 1 CO ο »-Η CO ο 1 1 1 1 1 1 1 1 1 ΑΟ-050 I CO ο 1 1 1 1 1 1 ΓΟ ο 1 CO ο 1 1 1 1 Composition D ΤΡΟ rH ?—Η τ-Η »-Η 1 1 1 1 1 1 1 ) 1 τ—Η Irgl84 ΙΟ mm LO ΙΟ LO m LO LO LO LD LO LO ΙΟ Component C NVC 1 I 1 Art 1 1 1 1 1 t 1 \ 1 1 ο »-Η Μ- 1600 1 I 1 1 1 1 1 ο ο ο ο ο 1 ) 1 ΡΟΑ 1 1 1 1 1 1 1 ο ο ο ο ο 1 1 1 Μ-211Β 1 1 1 1 1 1 1 ο ο ο ο ο 1 I 1 Μ-305 ο ο LO ο ο 1 1 1 ι 1 I 1 1 1 1 Component B ΤΟ-2344 1 § § 1 1 1 1 t 1 1 ' I 1 1 § 1 ΤΟ-1463 § ι 1 g ο ο ι- Η 1 ο ο ο ο ο § 1 1 Ingredient A ΟΤ-2501 ο ο LO § 1 ο f-^ t 1 1 1 1 宕1 CM ω CO m inch ω LO ω (Μ υ CO ο S ΰ δ 卜 g ο C10 201132657 The abbreviation for the compound used in the embodiment (E) is as follows: • 〇T-2501: A type acrylate epoxy ester [East Asia Synthetic Co., Ltd.) Aronics OT-250 1) • TO-1463: o-phenylphenoxyethyl acrylate [manufactured by Toagos Corporation] AronicsTO-1 463) • ΤΟ-23 44··ο-o-phenylphenyl acrylate [East Asia Synthetic (Share) System] Aronics TO -2344) • M-3〇5: a mixture of neopentyl glycol triacrylate and pentaerythritol tetraacrylate [Aritas M-305] NVC: N-vinylcarbazole [N-vinylcarbazole manufactured by Wako Pure Chemical Co., Ltd.] • Irgl 84: 1-hydroxycyclohexyl benzophenone (Irgacure 184 manufactured by BASF Corporation) • TPO: 2,4,6-trimethyl Benzomidine diphenylphosphine oxide (Lucirin TPO manufactured by BASF Corporation) .AO-50··octadecyl-3-(3,5-di-tri-tert-butyl-4-hydroxyphenyl)propionate [ Adeca (stock) system AO-50, formula (3) where R1 is a compound of octadecyl group] • AO-80: 3,9-bis[2-{3-(3-tertiary butyl-4-hydroxy- 5-methylphenyl)propenyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane [AO-made by Adeca) 80, Compound of formula (5)] .135A: diphenylisophthalic acid vinegar [Adeca (share)_Adeca stab 135A] .3010: triisodecyl phosphite [Adeca stab 3010 made by Adeca] • T- 928: benzotriazole-based ultraviolet absorber, manufactured by BASF Corporation, Japan τ -35 - 201132657 INUVIN 928 • T-900: benzotriazole-based ultraviolet absorber, τ INUVIN 900 manufactured by BASF Corporation Used in Comparative Example (C The abbreviation of the compound is as follows. • M-211B: Diacrylate of bisphenol A EO adduct [Aronics M-2 1 1 B made from East Asia Synthetic (Shares)] • POA: Phenyloxyethyl acrylate [Aronics M-100 manufactured by East Asia Synthetic Co., Ltd. • M-1600: Polyether urethane acrylate [Aronics M-1600 manufactured by East Asia Synthetic Co., Ltd.] • HQ: Hydroquinone. 412: Neopentyl alcohol-肆- (β-lauryl-thio Propionate) [Adeca (stock) AO-4 1 2S] • GP: 6-[3-(3-tert-butyl-4-hydroxy-5-methyl)propoxy]-2,4, 8,1 0-tetra-tertiary butyldibenzo[(1彳][1,3,2]dioxadioxaphos (?11〇8?116 pin)[Sumitomo Chemical Co., Ltd. Sumilizer GP] 〇 Evaluation Using the composition obtained above, it was evaluated according to the following method. The results are shown in Table 2. 1) Viscosity The viscosity was measured at 25 ° C using an E-type viscometer. Further, in the composition of Comparative Example 2, the viscosity was too high to be measured. 2) Refractive index -36 - 201132657 Using the obtained composition, a hardened material was used under the condition that the irradiation amount near 365 nm became 500 mJ/cm 2 using a high-pressure mercury lamp equipped with a conveyor. Regarding the obtained cured product, the refractive index (25 ° C) was measured by an Ato refractometer DR-M2 manufactured by Atago (manufactured). 3) The adhesion of the adhesiveness to the transfer film is evaluated by a checkerboard test using a polyethylene terephthalate (hereinafter referred to as PET) film [Toyobo Co., Ltd.) Cosmo shine A4300] was applied at a film thickness of 30 μm using a bar coater, and ultraviolet irradiation was performed under the same conditions as the refractive index test. Using the obtained cured product, the brittleness of the cured layer or the adhesion to the film substrate was measured in accordance with the method described in JIS Κ 5 400, and evaluated in the following three stages. 〇: the number of the checkerboard eyes is 90 or more, △: the number of the checkerboard eyes is 70 or more, and X: the number of the checkerboard eyes is 69 or less. 4) Peeling test The composition obtained by coating the film thickness of 50 μm in a nickel stamper having a lens shape The film was bonded to a PET film having a film thickness of ιμηη. Next, ultraviolet rays were irradiated under the same conditions as those of the refractive index test to prepare a cured product. A peeling test was carried out at a temperature of 90° between the nickel stamper and the PET film, and the peeling strength was measured by a sample width of 50 mm and a tensile speed of lm/miη at -37 - 201132657. When the peeling strength was 200 g/5 0 mm or less and all the resin cured products were adhered to the transfer film, it was judged that the mold release property from the stamper was good. 5) Appearance of lens shape The lens obtained by observing the result of the above peeling test by a microscope > confirms that the lens shape is not defective. For the microscope, the shape of the lens was observed at a magnification of 1 500 times using a digital microscope VH-6 30 〇 ' by a Keyence. If there is no defect, it is confirmed that the defect is X. 6) Low-temperature stability The composition was allowed to stand in a freezer at -1 〇 °C for 7 days, and it was visually confirmed whether or not precipitation occurred, and it was judged by the following criteria. 〇: Nothing has been seen since 7 days. X: Precipitation was seen after 1 to 2 days. 7) Measurement of coloring A test piece prepared by the same method as the evaluation of the adhesion of the transfer film was used to evaluate the color after 80 hours at 80 °C. The YI値 of the test specimen was measured using an integrating sphere spectral reflectance meter (D Ο T - 3 C manufactured by Murakami Materials Research Institute Co., Ltd.), and the γ 1 of the specimen after the heat resistance test. value. Further, in the following table, the color after the test is expressed by Δ Y I (the difference between the YI 试样 of the sample B after each test and the YI 试样 of the sample B before each test). -38 - 201132657 [Table 2] Viscosity (mPa · s) Refractive index adhesion peel test (g/50mm) Appearance of lens shape Low temperature stability After heat resistance test "YI E1 270 1.598 〇145 〇〇0.2 E2 240 1.603 〇163 〇〇0.4 E3 200 1.596 〇140 〇〇0.2 E4 553 1.616 〇160 〇〇0.3 E5 270 1.598 〇145 〇〇0.1 C1 160 1.610 X 30 X 〇0.8 C2 - 1.576 Δ 308 X 〇1.5 C3 250 1.566 〇190 〇〇0.8 C4 250 1.566 〇190 〇〇0.5 C5 250 1.566 〇190 〇〇3.2 C6 250 1.566 〇190 〇X 0.4 C7 250 1.566 〇190 〇〇1.0 C8 450 1.602 〇185 〇〇0.6 C9 370 1.575 〇181 〇〇 0.6 C10 - - - - - X - It is apparent from the results of the examples that the composition of the present invention has a cured product having a high refractive index and a high adhesion to a transfer film due to a lens-shaped stamper. Further, since the mold release property is good and the productivity of the lens sheet is extremely high, a cured product having excellent durability and less coloration due to heat can be obtained. The composition of Example 4 containing N VC was extremely excellent in refractive index. On the other hand, the composition of Comparative Example 1 containing no component A had a high refractive index, but the adhesion to the transfer film was low, and a good lens shape could not be obtained. Further, the curable component is a composition of Comparative Example 2 containing only component A, and the viscosity is too high, and there is a problem in handling at room temperature, and there is a problem of adhesion or lens shape. Further, in the composition in which the component A is not essential, as is apparent from Comparative Examples 3 to 7, a sufficiently high refractive index cannot be obtained. The composition of Comparative Example 5 containing a phenolic antioxidant other than the component E was thermally colored - 39 - 201132657. Further, the composition of Comparative Example 6 containing a sulfur-based antioxidant other than the component F can prevent coloring due to heat, but is liable to precipitate at a low temperature, which causes a problem in stability of the composition. Further, the composition of Comparative Example 7 in which an antioxidant is used, which has a phenolic hydroxyl group and phosphorus in the same molecule, tends to cause a large coloration due to heat. Although the components A to C are contained, the composition of Comparative Example 8 and the same composition which does not contain the component E and the component F is excellent in refractive index, adhesion, and mold release property, but the coloration due to heat is increased. . The composition of Example 4 containing NVC was extremely excellent in refractive index. The component A and the component B were not contained, and only the composition of the NVC as the component C (Comparative Example 10) was contained, and the melting point was high. Even if the component D was prepared, it was crystallized at room temperature, and thus the low-temperature stability test could not be performed. Evaluation. [Industrial Applicability] The composition of the present invention can be used for the production of various optical materials, and more specifically, a lens portion such as a Fresnel lens or a lenticular lens used for a screen such as a projection television, or a liquid crystal. A 稜鏡 lens sheet that is backlit by the display device is particularly useful. [Simple description of the diagram] None. [Main component symbol description] dnt no 0 • 40 -
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| US9957376B2 (en) | 2015-03-31 | 2018-05-01 | Eternal Materials Co., Ltd. | Optical material composition and use thereof |
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| JP6381318B2 (en) * | 2014-06-30 | 2018-08-29 | 新日鉄住金化学株式会社 | Active energy ray-curable resin composition for optical lenses |
| CN105802238B (en) * | 2014-12-31 | 2019-06-25 | 埃肯有机硅（上海）有限公司 | Curable polysiloxane composition |
| JP6554987B2 (en) * | 2015-08-10 | 2019-08-07 | 東洋インキＳｃホールディングス株式会社 | Active energy ray-polymerizable resin composition for optical three-dimensional modeling, and three-dimensional modeling |
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| JPH0593121A (en) * | 1991-07-08 | 1993-04-16 | Hitachi Chem Co Ltd | Production of thermoplastic resin for lens |
| JP3209554B2 (en) * | 1991-12-19 | 2001-09-17 | 日本化薬株式会社 | Resin composition, ultraviolet curable resin composition for transmission screen and cured product thereof |
| JPH07238119A (en) * | 1994-03-01 | 1995-09-12 | Tokuyama Corp | Polymerizable composition |
| JPH0881527A (en) * | 1994-09-13 | 1996-03-26 | Nippon Kayaku Co Ltd | Resin composition and its cured item |
| JP3202884B2 (en) * | 1995-02-13 | 2001-08-27 | 三菱レイヨン株式会社 | Optical element |
| JP3670747B2 (en) * | 1996-02-27 | 2005-07-13 | Ｊｓｒ株式会社 | Liquid curable resin composition for optical member preparation |
| JP3788858B2 (en) * | 1997-09-19 | 2006-06-21 | 日本化薬株式会社 | Lens resin composition and cured product thereof |
| JPH11171941A (en) * | 1997-12-12 | 1999-06-29 | Mitsubishi Rayon Co Ltd | Active energy ray-setting composition and optical sheet |
| JP2002356524A (en) * | 2001-05-30 | 2002-12-13 | Dainippon Ink & Chem Inc | Active energy ray-hardenable resin composition for cast polymerization |
| JP2003261645A (en) * | 2002-03-11 | 2003-09-19 | Jsr Corp | Photocurable resin composition and optical member |
| JP4520124B2 (en) * | 2002-09-27 | 2010-08-04 | 帝人化成株式会社 | Polycarbonate resin composition and molded product thereof |
| WO2005044882A1 (en) * | 2003-11-07 | 2005-05-19 | Toagosei Co., Ltd. | Actinic-energy-ray-curable composition for optical material |
| JP4644429B2 (en) * | 2004-02-02 | 2011-03-02 | 三菱瓦斯化学株式会社 | Photochromic lens and manufacturing method thereof |
| JP4457960B2 (en) * | 2005-04-28 | 2010-04-28 | 東亞合成株式会社 | Active energy ray-curable composition for optical members |
| JP2010060890A (en) * | 2008-09-04 | 2010-03-18 | Dic Corp | Active energy ray-curable resin composition for optical article and cured product |
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2010
- 2010-12-17 WO PCT/JP2010/072765 patent/WO2011074666A1/en active Application Filing
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