200906867 九、發明說明： 【發明所屬之技術領域】 本發明係有關一種光學透鏡片用之能量線硬化型樹脂組 合物及其硬化物，尤指一種特別適於菲涅爾透鏡、雙凸透 鏡、稜鏡、微透鏡等之透鏡類的樹脂組合物及其硬化物。 【先前技術】 迄今為止，上述透鏡係由慶製法、洗禱法（注模成形法） 等方法成形。前者之壓製法，係以加熱、加壓、冷卻循環 製造，生產性不佳。又，後者之㈣法，係在模具中流入 f體並聚合之，製作時間長且需多個模具，故製造成本 高’是為其問題。為解決此等問題，針對使用紫外線硬化 性樹脂組合物已有各種提案（專利文獻ι、專利文獻2)。 另，專利文獻3中，曾記載一種含（甲基）丙稀酸鄰-苯基酚 (聚）乙氧醋之透過型營幕等所用的樹脂組合物。此外，在 專利文獻4中，曾記載一種含9,9-二（4-甲基丙稀疏氧苯基 苟之眼鏡透鏡用樹脂組合物。 使用此等紫外線硬化性樹脂組合物，t造用於透過型螢 幕等之光學透鏡片之方法’在某種成度上算是成功 '然 而，此等先前之樹脂組合物之硬化物，在對於基板之密接 !·生土自模具之脫模性等方面卻不一定令人滿意。密接性若 不仫則脫杈時樹脂會殘留於模具内，以致模具變得無法 此夠k供岔接性佳的硬化物之樹脂組合物，因 對於模具的密接亦轉佳之故，則脫模性易於轉劣，另-方 面脫換性佳之樹脂組合物，則密接性易於趨劣，此均亦 128948.doc 200906867 為其課題者。是以，業界期 及自模具之脫模性兩種性能约2供—種與基板之密接性 皇,…… 犯均旎令人滿意之樹脂組合物。 專利文獻2及專利文獻3中，均未曾提到密接性。 用於光學透鏡片等之透鏡類用組合物，伴隨著近年之圖 像之高精細化等，為了被加 帽者近年之圖 攻更為倣細之形狀、或為了 被加工成更薄，或為了將其 、違續加工成捲狀之片體或薄 Π必要具有低黏度。專利文獻4中所記载之樹脂組合 物，其主成分之9,二(4_甲基丙締醯氧苯基常溫下為 固體物質’因此黏度高，不適於製造具有微細構造之光學 透鏡片。X ’專利文獻4中所記载之樹脂組合物，係妖硬 化性樹脂組合物’因此不適於利用紫外線硬化所製造之光 學透鏡片。 再者’在將透鏡片捲取時等等之情況下，有必要使微細 構造不容易壓潰’此一情形下，被要求的是玻璃轉移溫度 (Tg)高。 又，作為硬化物之物性也是，為了能使即便是透過型螢 幕使用時之高溫環境下物性變化不大，則應傾向於儘量要 求硬化物之玻璃轉移溫度（Tg)高。針對上述要求，迄今為 止，此界並未獲得一種具有高折射率，且為高丁§點、高脫 模性、高密接性、低黏度，同時適於具有微細構造之光學 透鏡片的製造之樹脂組合物’是為其問題。 [專利文獻1 ] 曰本特開昭63-167301號公報 [專利文獻2] 128948.doc 200906867 曰本特開昭63-199302號公報 [專利文獻3] 曰本特許第3209554號 [專利文獻4 ] 曰本特許第3 130555號 【發明内容】 [發明之解決課題] r \200906867 IX. Description of the Invention: The present invention relates to an energy ray-curable resin composition for an optical lens sheet and a cured product thereof, and more particularly to a Fresnel lens, a lenticular lens, and an edge. A resin composition of a lens such as a mirror or a microlens and a cured product thereof. [Prior Art] Heretofore, the lens has been formed by a method such as a celebration method or a washing method (injection molding method). The former's pressing method is manufactured by heating, pressurizing, and cooling cycles, and the productivity is poor. Further, the latter method (4) is a problem in which the f body is poured into a mold and polymerized, and the production time is long and a plurality of molds are required, so that the manufacturing cost is high. In order to solve such problems, various proposals have been made for the use of an ultraviolet curable resin composition (Patent Document 1 and Patent Document 2). Further, Patent Document 3 describes a resin composition for use in a transmissive curtain or the like containing (meth)acrylic acid o-phenylphenol (poly) ethoxy vinegar. Further, Patent Document 4 describes a resin composition for a spectacle lens containing 9,9-bis(4-methylpropenoxy phenyl hydrazine). Using these ultraviolet curable resin compositions, t is used for The method of transmitting an optical lens sheet such as a screen is 'successful in a certain degree of success'. However, the cured product of the prior resin composition is in close contact with the substrate, the release property of the raw soil from the mold, and the like. However, it is not necessarily satisfactory. If the adhesion is not good, the resin will remain in the mold during the dislocation, so that the mold becomes unable to provide a resin composition of the cured product having good splicability, because of the adhesion to the mold. For better reasons, the mold release property is easy to be deteriorated, and the resin composition with good exchangeability is easy to be inferior, and this is also the subject of 128948.doc 200906867. The two properties of the release property are about two, and the adhesion between the substrate and the substrate is excellent, and the resin composition is satisfactory. In Patent Document 2 and Patent Document 3, the adhesion is not mentioned. Lens type composition such as optical lens sheet With the high-definition of images in recent years, in order to be more like a shape of a hater in recent years, or to be processed into a thinner, or to process it into a roll In addition, it is necessary to have a low viscosity. The resin composition described in Patent Document 4 has a main component of 9, 2 (4-methyl-propyl sulfonyloxyphenyl is a solid substance at normal temperature), so the viscosity is high, and it is not suitable. An optical lens sheet having a fine structure is produced. The resin composition described in Patent Document 4 is a softening resin composition which is not suitable for optical lens sheets produced by ultraviolet curing. In the case of film winding, etc., it is necessary to make the fine structure less likely to be crushed. In this case, it is required that the glass transition temperature (Tg) is high. Moreover, the physical properties of the cured product are also When the physical properties of the transmissive screen are not changed in a high temperature environment, the glass transition temperature (Tg) of the hardened material should be as high as possible. To meet the above requirements, no high refractive index has been obtained in this field. The resin composition which is suitable for the manufacture of an optical lens sheet having a fine structure is a problem of high hardness, high mold release property, high adhesion, low viscosity, and the like. [Patent Document 1] 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 SUMMARY OF THE INVENTION [Solutions of the Invention] r \
本發明之目的，係在提供—種適於製造菲沒爾透鏡、雙 凸透鏡、稜鏡、微透鏡、片狀透鏡類之低黏度樹脂組合 物’或該樹脂組合物之脫模性、模具形狀再現性、密接性 優異且為高折射率之硬化物。 發明人等為解決上述課題，銳意研究的結果發現一種具 有定組成之紫外線硬化性樹脂組合物及其硬化物可解決前 述課題，終而完成本發明。 具體言之，本發明係 (1)種以（甲基）丙烯酸鄰-苯基酚（聚）乙氧酯（Α)為主 成刀3 3有！t式⑴所示之化合物⑻及光聚合起始劑（c) 之光學透鏡片用之能 篁線硬化型樹脂組合物：The object of the present invention is to provide a low-viscosity resin composition suitable for the manufacture of a phenanthrene lens, a lenticular lens, a ruthenium, a microlens, a sheet lens, or a mold release property or a mold shape of the resin composition. A cured product having excellent reproducibility and adhesion and having a high refractive index. In order to solve the above problems, the inventors of the present invention have found that an ultraviolet curable resin composition having a predetermined composition and a cured product thereof can solve the aforementioned problems, and the present invention has been completed. Specifically, the present invention is characterized in that (1) is mainly composed of o-phenylphenol (poly)ethoxylate (meth)acrylate. The fluorene-curable resin composition for the optical lens sheet of the compound (8) represented by the formula (1) and the photopolymerization initiator (c):
128948.doc 200906867 (Ri、R2分別獨立表氫原子或甲基，a、b分別表i以上之 正數，a+b為2〜4)。 (2) 如（1)之樹脂組合物，其中該（甲基）丙烯酸鄰_苯基 酚（聚）乙氧醋（A)與通式（1)所示之化合物（B)之合計量設為 100質量份時，（曱基）丙烯酸鄰-苯基酚（聚）乙氧酯（A)之含 量為其中之60質量份至95質量份； (3) 如（1)或（2)之樹脂組合物，其中又含有除（甲基）丙 稀酸鄰-苯基酚（聚）乙氧雖（A)與通式〇)所示之化合物（b)以 外的（曱基）丙烯酸酯化合物（D); (4) 如（3)之樹脂組合物，其中該樹脂組合物中之（曱 基）丙烯酸酯（A)、（B)、（D)之合計量設為1〇〇質量份時， (甲基）丙烯酸鄰-苯基酚（聚）乙氧酯（A)與通式（丨）所示之化 合物（B)之合計的含量為其中之7〇〜99質量份； (5) 如（1)至（4)中任一項之樹脂組合物，其中該（甲基） 丙烯酸鄰-苯基酚（聚）乙氧酯（A)與通式（1)所示之化合物（B) 之合計量設為1〇〇質量份時，（甲基）丙烯酸鄰_苯基酚（聚） 乙氧酯（A)之含量為其中之60質量份至98質量份； (6) 如（1)至（5)中任一項之樹脂組合物，其中以E型黏 度計測定之25°C下之黏度為1500 mPa.s以下； ⑺-種硬化物’其係將⑴至（6)中任—項之樹脂組合 物硬化而獲得，25T：下之折射率為丨58以上； (8) 一種光學片狀透鏡，其係使用之硬化物。 [發明之效果] 本發明之樹脂組合物為低黏度，其硬化物之脫模性、模 Ϊ 28948.doc 200906867 具形狀再現性、與基板之密接性均屬優異且為高折射率。 因此，特別適於製造菲涅爾透鏡、雙凸透鏡、稜鏡、微透 鏡專之光學透鏡片。 【實施方式】 本發明之樹脂組合物，含有（甲基）丙烯酸鄰_苯基酚(聚） 乙軋酯（A)、通式（1)所示之化合物（8)及光聚合起始劑 (C)。 絲就本發明中所使用之（曱基）丙烯酸鄰-苯基酚（聚）乙氧 酯（A)進行說明。作為丙烯酸鄰_苯基酚聚乙氧酯，宜為 乙氧基構造部分之重複數為數平均1〜3之正數之化合物， α藉由7邠苯基酚與環氧乙烷之反應物與（甲基）丙烯酸反 應而獲得。鄰.苯基酚與環氧乙烧之反應物可以公知之方 法獲得，其次，藉#在對-甲苯績酸或硫酸等之酿化觸 媒、氫職、吩料等之聚合禁止劑之存在下，宜在溶劑類 (例如曱本、環己貌、正己烧、正庚烧等）之存在下，並宜 在70〜150。〇之溫度下，與（曱基）丙烯酸反應，而獲得丙烯 酸鄰-苯基紛聚乙氧醋⑷。（甲基）丙稀酸之使用比例，相 對對-苯絲與環氧乙燒之反應物1莫耳為卜5莫耳，宜為 2莫耳自曰化觸媒，相對使用之（曱基）丙烯酸為 〇 ·1〜1 5莫耳％，宜為1〜6莫耳％。 、下兹就本發明樹脂組合物中所使用之通式（1)所示之 化合物（Β)說明。 128948.doc 10 200906867128948.doc 200906867 (Ri and R2 are each independently represented by a hydrogen atom or a methyl group, and a and b are respectively positive numbers above i, and a+b is 2 to 4). (2) The resin composition of (1), wherein the total amount of the (meth)acrylic acid o-phenylphenol (poly) ethoxy vinegar (A) and the compound (B) represented by the formula (1) is When it is 100 parts by mass, the content of (mercapto)acrylic acid o-phenylphenol (poly)ethoxylate (A) is 60 parts by mass to 95 parts by mass; (3) as in (1) or (2) a resin composition further containing a (fluorenyl) acrylate compound other than the compound (b) represented by (A) and the formula (b) in addition to (meth)acrylic acid o-phenylphenol (poly)ethoxy (4) The resin composition of (3), wherein the total amount of (mercapto) acrylates (A), (B), and (D) in the resin composition is set to 1 part by mass. When the content of the o-phenylphenol (poly)ethoxylate (A) (meth) acrylate (A) and the compound (B) represented by the formula (丨) is 7 〇 to 99 parts by mass; The resin composition according to any one of (1) to (4), wherein the (meth)acrylic acid o-phenylphenol (poly)ethoxylate (A) is a compound represented by the formula (1) ( B) When the total amount is set to 1 part by mass, (meth) propylene The content of the acid o-phenylphenol (poly) ethoxylate (A) is from 60 parts by mass to 98 parts by mass; (6) The resin composition according to any one of (1) to (5), wherein The viscosity at 25 ° C measured by an E-type viscometer is 1500 mPa·s or less; (7) - The hardened material is obtained by hardening the resin composition of any of (1) to (6), and the refractive index of 25T: It is 58 or more; (8) An optical sheet lens which is a cured product to be used. [Effects of the Invention] The resin composition of the present invention has a low viscosity, and the mold release property of the cured product, the shape reproducibility of the mold, and the adhesion to the substrate are both excellent and high refractive index. Therefore, it is particularly suitable for manufacturing optical lens sheets for Fresnel lenses, lenticular lenses, cymbals, and microlenses. [Embodiment] The resin composition of the present invention contains o-phenylphenol (poly) acetonitrile (meth)acrylate (A), a compound (8) represented by the formula (1), and a photopolymerization initiator. (C). The silk is described as (mercapto)acrylic acid o-phenylphenol (poly)ethoxylate (A) used in the present invention. As the o-phenylphenol polyethoxylate of acrylic acid, it is preferred that the repeating number of the ethoxy moiety is a compound having a number average of 1 to 3, and the α is reacted with 7 phenylphenol and ethylene oxide ( Obtained by the reaction of methyl)acrylic acid. The reaction product of o-phenylphenol and ethylene bromide can be obtained by a known method, and secondly, the presence of a polymerization inhibiting agent such as a catalyst for hydrogenation, hydrogen, and the like in p-toluene acid or sulfuric acid Next, it should be in the presence of a solvent (for example, sputum, ring, hexam, gamma, etc.), and preferably in the range of 70 to 150. At a temperature of hydrazine, it is reacted with (hydrazino)acrylic acid to obtain an o-phenyl ethoxy acrylate (4). The proportion of (methyl)acrylic acid used is relative to the reaction of p-benzene and ethylene bromide. The molar amount of the catalyst is 5 moles, preferably 2 moles of self-decomposing catalyst. Acrylic acid is 〇·1~1 5 mol%, preferably 1 to 6 mol%. The following is a description of the compound (Β) represented by the formula (1) used in the resin composition of the present invention. 128948.doc 10 200906867
b分別表1以上之 (Ri、R·2分別獨立表氫原子或曱基 正數，a+b為2〜4)，b are respectively above Table 1 (Ri, R·2 are each independently a hydrogen atom or a sulfhydryl group, and a+b is 2 to 4),
可藉由將通式（2): --By using the general formula (2): --
CH2CH〇 )γη (2) (式中，R1、a、b之定義與通式⑴相同） \ 所不之化合物與（甲基）丙烯酸，在溶劑（例如曱苯、苯、環 己烷正己烷、正庚烷等）中行脫水反應而獲得。為促進 反應，且使用酸觸媒（例如硫酸、對甲苯磺酸、甲烷磺 鲛）。反應中，為防止聚合，宜使用聚合禁止劑（例如氫 醌、對-甲氧基酚、甲基氫醌等）。 通式（2)所示化合物與（甲基）丙烯酸之使用比例，相對通 f (2)所示化合物之羥基1當量’（甲基）丙烯酸宜使用1〜2當 里反應溫度宜為70〜1 50°C，反應時間宜為3〜20小時。 通式（2)所示化合物，可藉9,9-二（4-羥基苯基）芴與伸烷 128948.doc 200906867 氧化丁烯等）反應而製 氧化物（例如環氧乙烷、氧化丙烯 得。 再者，除早先所舉之（曱基）丙烯酸鄰-苯基紛（聚）乙氧酿 (± )匕通式⑴所不之化合物⑻以外，考慮所獲得之本發明 树月曰、.且口物之黏度、密接性或玻璃轉移溫度(U)、硬化物 之硬度等等’可混合成分⑷、成分（B)以外之（甲基）丙晞 ❼旨化合物⑼單獨—種或兩種以上。作為該（曱基）丙稀酸 酉曰化σ物⑴），可舉的是（甲基）丙烯酸酯（d)單體或（甲基） 丙烯酸酯寡聚合物。 作為（曱基）丙稀酸酯單體’可舉的是單官能（甲基）丙烯 酸酉旨單體、2官能（甲基）丙烯酸醋㈣、3官能以上之多官 能（甲基）丙稀酸酯單體等等。 作為單官能（甲基）丙烯酸酯單體，可舉的實例包括：丙 稀自&馬琳、（曱基）丙烯酸2_羥基丙酯、（曱基）丙烯酸4_羥基 丁酯、環己烷-1，4-二曱醇一（曱基）丙烯酸酯 ' (曱基）丙烯 酸四氫糠酯、（曱基）丙烯酸苯氧基乙酯、（曱基）丙烯酸苯 基聚乙氧酯、（曱基）丙烯酸2_羥基_3_苯基氧基丙酯、（甲 基）丙烯酸對-枯基苯氧基乙酯、（甲基）丙烯酸異冰片酯、 (曱基）丙烯酸三溴苯基氧基乙酯、（甲基）丙烯酸二環戊 酯、（甲基）丙烯酸二環戊烯酯、（曱基）丙烯酸二環戊烯氧 乙酯等等。 作為2官能（甲基）丙烯酸酯單體，可舉的實例包括：二 (甲基）丙烯酸1，4-丁烷二醇酯 '二（曱基）丙烯酸丨，6_己烷二 醇酯、二（曱基）丙烯酸1,9-壬院二醇酯、（曱基）丙浠酸三環 128948.doc 12 200906867 癸烷二甲醇酯、二（曱基）丙烯酸雙酚A聚乙氧酯、二（曱基） 丙烯酸雙酚A聚丙氧酯 '二（甲基）丙烯酸雙酚F聚乙氧酯、 二（曱基）丙烯酸乙二醇酯、二（甲基）丙烯酸聚乙二醇酯等 等。 作為3官能（曱基）丙烯酸酯單體，可舉的實例包括··異 氰脲酸三（丙烯醯氧乙酯）、四（曱基）丙烯酸季戊四醇酯、 六（曱基）丙烯酸二季戊四醇酯、五（甲基）丙烯酸二季戊四 酵酯、六（甲基）丙烯酸三季戊四醇酯、五（曱基）丙烯酸三 季戊四醇酯、羥基特戊酸新戊二醇酯之心己内酯加成物之 一（曱基）丙烯酸酯（例如日本化藥股份有限公司製之 KAYARAD HX-220、HX-620等等）、三（甲基）丙稀酸三經 甲基丙烷酯、三（曱基）丙烯酸三羥甲基丙烷聚乙氧酯、四 (甲基）丙烯酸二（三羥曱基丙烷）酯等等。 作為（甲基）丙稀酸醋募聚合物，可舉的實例包括：氨酯 (甲基）丙烯酸酯、環氧（曱基）丙烯酸酯、聚酯（甲基）丙烯酸 酯等等。 作為氨酯（甲基）丙稀酸酯，其可舉實例為例如二醇化合 物（如乙二醇、二甘醇、三乙二醇、丙二醇、二丙二醇、 三丙二醇' 1，4· 丁二醇、新戊二醇、；!，6_己二醇、丨，8_辛二 醇、1,9-壬二醇、2-甲基_1，8_辛二醇、3_甲基戍二 醇、2,4-二曱基-1，5-戊二醇、2-丁基_2-乙基-:^弘丙二醇、 環己烷-M-二甲醇、聚乙二醇、聚丙二醇、雙酚a聚乙氧 基二醇、雙酚A聚丙氧基二醇等）或此等二醇化合物與二元 酸或其酐（如琥珀酸、己二酸、壬二酸、二聚酸、異酞 128948.doc -13- 200906867 酸、對酞酸、酞酸或其等之酐）之反應物聚酯二醇，與有 機多異氰酸酯（如二異氰酸四亞甲酯、二異氰酸六亞甲 酯、二異氰酸2,2,4-三曱基六亞甲酯、二異氰酸2,4,4-三曱 基六亞甲酯等之鏈狀飽和烴異氰酸酯，二異氰酸異佛爾酮 醋、二異氰酸原冰片烷酯、二異氰酸二環己基曱烷酯、亞 曱基一（異氰酸4 -環己g旨）、二異氰酸加氫二苯甲烧g旨、二 異氰酸加氫二甲苯酯、二異氰酸加氫甲苯酯等之環狀飽和 烴異氰酸酯’二異氰酸2,4-甲代苯撐酯、二異氰酸〗，3_苯 二甲酯、二異氰酸對-苯撐酯、二異氰酸3,3，_二甲基_4,4，_ 酯、二異氰酸6-異丙基-1,3-苯酯、二異氰酸ι,5-萘酯等之 芳香族多異氰酸酯）反應’而後再加成含羥基（曱基）丙烯酸 酯所得之反應物等等。 作為環氧（甲基）丙烯酸酯，其可舉實例為雙酚A型環氧 樹脂、雙酚F型環氧樹脂、酚醛型環氧樹脂、雙酚a之氡化 丙烯加成物之末端縮水甘油醚、苟環氧樹脂等之環氧樹脂 類與（甲基）丙烯酸之反應物等等。 作為聚醋（甲基）丙烯酸酯，例如可為上述二醇化合物與 上述二元酸或其酐之反應物聚酯二醇與（甲基）丙烯酸之反 應物等等。 其中，作為本發明樹脂組合物中可使用之（曱基）丙烯酸 酯化合物（D) ’適合的是黏度低、硬化物之密接性良好的 單官能或2官能（甲基）丙烯酸酿單體。其中較適宜的是丙烯 酿嗎啉、（甲基）丙烯酸四氫糠醋、（甲基）丙烯酸苯氧基乙 面曰、一（甲基）丙烯酸1，4-丁烷二醇酯、（曱基）丙烯酸酯、二 128948.doc •14- 200906867 (曱基）丙烯酸1，6-己烷二醇酯、（曱基）丙烯酸異冰片酯、 (曱基）丙烯酸二環戊酯、（甲基）丙烯酸二環戊烯酯、（甲基） 丙烯酸二環戊烯氧乙酯等等之單官能或2官能（甲基）丙烯酸 酯單體。CH2CH〇)γη (2) (wherein, R1, a, b are the same as defined in the formula (1)) \ Compounds and (meth)acrylic acid in a solvent (for example, toluene, benzene, cyclohexane-n-hexane , n-heptane, etc.) obtained by a dehydration reaction. To promote the reaction, an acid catalyst (e.g., sulfuric acid, p-toluenesulfonic acid, methanesulfonate) is used. In the reaction, in order to prevent polymerization, a polymerization inhibiting agent (e.g., hydroquinone, p-methoxyphenol, methylhydroquinone, etc.) is preferably used. The ratio of the compound represented by the formula (2) to (meth)acrylic acid is 1 equivalent to the hydroxyl group of the compound represented by the formula (2). The (meth)acrylic acid is preferably used in an amount of 1 to 2, and the reaction temperature is preferably 70 to 70. 1 50 ° C, the reaction time is preferably 3 to 20 hours. The compound of the formula (2) can be prepared by reacting 9,9-bis(4-hydroxyphenyl)anthracene with an alkylene oxide (128948.doc 200906867 butylene oxide, etc.) to produce an oxide (for example, ethylene oxide, propylene oxide). Furthermore, in addition to the compound (8) which is not mentioned in the above formula (8), which is not described in the above formula (1), in consideration of the obtained invention, And the viscosity, adhesion or glass transition temperature (U) of the mouth material, hardness of the hardened material, etc. 'mixable component (4), component (B) other than the component (B) (9) alone - or two The (meth) acrylate (d) monomer or the (meth) acrylate oligomer may be mentioned as the (indenyl) acrylate yttrium (1). The (fluorenyl) acrylate monomer may be a monofunctional (meth)acrylic acid monomer, a bifunctional (meth)acrylic acid vinegar (tetra), or a trifunctional or higher polyfunctional (meth) propylene. Acid ester monomers and the like. As the monofunctional (meth) acrylate monomer, exemplified by: propylene from & Marlene, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, cyclohexane -1,4-dioxanol (mercapto) acrylate 'tetrahydrofurfuryl acrylate, phenoxyethyl (meth) acrylate, phenyl polyethoxylate (mercapto) acrylate, ( Mercapto) 2_hydroxy_3_phenyloxypropyl acrylate, p-cumylphenoxyethyl (meth)acrylate, isobornyl (meth)acrylate, tribromophenyl (meth) acrylate Ethyloxyethyl ester, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopenteneoxyethyl (meth)acrylate, and the like. As the bifunctional (meth) acrylate monomer, there may be mentioned, for example, 1,4-butanediol di(meth)acrylate, bis(indenyl) acrylate, 6-hexanediol ester, Di-(indenyl)acrylic acid 1,9-anthracene glycol ester, (mercapto)propionic acid tricyclic 128948.doc 12 200906867 decane dimethanol ester, bis(indenyl)acrylic acid bisphenol A polyethoxylate, Bis(fluorenyl) bisphenol A acrylate polypropyl acrylate di(meth)acrylic acid bisphenol F polyethoxylate, ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, etc. Wait. As the trifunctional (fluorenyl) acrylate monomer, there may be mentioned, for example, isocyanuric acid tris(propylene oxy oxyethyl ester), tetrakis(mercapto)acrylic acid pentaerythritol ester, and hexakis(yl)acrylic acid dipentaerythritol ester. , dipentaerythritol penta(meth)acrylate, tripentaerythritol hexa(meth)acrylate, tripentaerythritol penta(indenyl)acrylate, caprolactone adduct of neopentyl glycol hydroxypivalate One (mercapto) acrylate (such as KAYARAD HX-220, HX-620, etc. manufactured by Nippon Kayaku Co., Ltd.), tris(methyl)propionic acid trimethyl propyl ester, tris(sulfonate) Trimethylolpropane acrylate polyethoxylate, bis(trihydroxydecylpropane) tetra(meth)acrylate, and the like. As the (meth)acrylic acid vinegar polymer, examples may be mentioned: urethane (meth) acrylate, epoxy (fluorenyl) acrylate, polyester (meth) acrylate, and the like. As the urethane (meth) acrylate, for example, a diol compound (e.g., ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol '1, 4 · butyl) Alcohol, neopentyl glycol, ;!,6-hexanediol, hydrazine, 8-octyl glycol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 3-methylhydrazine Glycol, 2,4-dimercapto-1,5-pentanediol, 2-butyl-2-ethyl-: propylene glycol, cyclohexane-M-dimethanol, polyethylene glycol, polypropylene glycol , bisphenol a polyethoxy diol, bisphenol A polypropoxy diol, etc.) or such diol compounds and dibasic acids or anhydrides thereof (such as succinic acid, adipic acid, sebacic acid, dimer acid) , isophthalide 128948.doc -13- 200906867 The reaction of polyester, phthalic acid, citric acid or its anhydride, polyester diol, with organic polyisocyanate (such as tetramethylene diisocyanate, diisocyanate) a chain-like saturated hydrocarbon isocyanate such as hexamethylene acid methyl ester, 2,2,4-trimethyl hexamethylene diisocyanate or 2,4,4-trimethyl hexamethylene diisocyanate, Isophorone isocyanate, borneol diisocyanatoate, dicyclohexyldecyl diisocyanate, Aa a cyclic saturated hydrocarbon such as (isocyanate 4-cyclohexan), diisocyanate hydrogenation of diphenylmethane, diisocyanato hydrogenated xylyl ester, diisocyanate hydrogenated toluene Isocyanate '2,4-methylphenylene diisocyanate, diisocyanate, 3-phenylene dicarboxylate, p-phenylene diisocyanate, diisocyanate 3,3,_dimethyl Aromatic polyisocyanate such as ketone, 4,4, _ ester, 6-isopropyl-1,3-phenyl diisocyanate, diisocyanate ι, 5-naphthyl ester, etc. The reactant obtained from the hydroxy(indenyl) acrylate and the like. Examples of the epoxy (meth) acrylate include bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolac type epoxy resin, and bisphenol a decane propylene adduct end shrinkage. A reaction of an epoxy resin such as glycerin ether or an anthracene epoxy resin with (meth)acrylic acid or the like. The polyester (meth) acrylate may, for example, be a reaction of the above diol compound with the above dibasic acid or an anhydride thereof, a reaction of a polyester diol with a (meth)acrylic acid or the like. Among them, the (fluorenyl) acrylate compound (D) which can be used in the resin composition of the present invention is preferably a monofunctional or bifunctional (meth)acrylic monomer having a low viscosity and a good adhesion of a cured product. Among them, propylene morpholine, tetrahydroanthracene (meth) acrylate, phenoxy bismuth (meth) acrylate, 1,4-butanediol (meth) acrylate, (曱) Acrylate, II 128948.doc • 14- 200906867 (fluorenyl) 1,6-hexanediol, (isoyl)isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, (methyl) A monofunctional or bifunctional (meth) acrylate monomer such as dicyclopentenyl acrylate, dicyclopentene oxyethyl (meth) acrylate or the like.
本發明樹脂組合物中所含之光聚合起始劑，可舉的 實例是苯偶姻、苯偶姻甲基醚、苯偶姻乙基醚、苯偶姻丙 基醚、苯偶姻丁基醚等之苯偶姻類；苯乙酮、2,2-二乙氧 基-2-苯基苯乙酮、2,2-二乙氧基苯基苯乙酮、丨，丨-二氣 苯乙酮、2-羥基-2-甲基-笨基丙烷-丨_酮、二乙氧基笨乙 酮、1-羥基環己基苯基酮、2-甲基-1_[4-(甲硫基）苯基卜2 嗎啉代丙烷-1-酮等之笨乙酮類；2-乙基蒽醌、2-第三丁基 恩酿、2-氯蒽酿、2-戊基蒽酿等之蒽親類；2,4_二乙基硫 雜蒽酮、2-異丙基硫雜蒽酮、2_氯硫雜蒽酮等之硫雜蒽酮 類；苯乙酮二曱基縮酮、苄基二曱基縮酮等之縮酮類；二 苯曱酮、4-苯醯-4，-甲基二苯基硫醚、4,4，_二曱胺基二苯 曱酮等之二苯曱酮類；2,4,6_三甲基苯醯二苯基膦氧化 物、二（2,4,6-三甲基苯醯）_苯基膦氧化物等之氧化鱗類等 等。其中較佳的是苯乙酮類，更好可舉的是2_羥基_2_曱基 苯基丙烷-1-酮、1-羥基環己基苯基酮 又’本發明樹脂組 合物中，光聚合起始劑可單獨使用或混合複數種使用。 本發明樹脂組合物之各成分的使用比例雖係考慮所期望 之折射率或玻璃轉移溫度或黏度或密接性而決定7在成分 ⑷十成分（B)+成分⑼設為剛質量份時，若不含成分⑼: 則成分成分（B)之含量為70〜丨〇〇質量份，特別好的是 128948.doc 15 200906867 75〜100質量份。若含成分（D)時，成分（D)之含量為丨〜3〇質 量份’特別好的是1〜25質量份。又’成分（A)+成分（B)+成 分（D)之合計量設為100質量份時’成分（A)之含量，無關 成分（D)之有無，為其中之60〜98質量份，特別好的是 70〜95質量份。成分（c)相對成分（A)+成分（b)+成分（D)之總 量100質量份，宜使用〇.1〜10質量份，特別好的是〇 3〜5質 量份。 本發明樹脂組合物之各成分的使用比例雖係考慮所期望 之折射率或玻璃轉移溫度或黏度或密接性而決定，在成分 (A)+成分（B)+成分（D)設為1〇〇質量份時，（A) : :⑴）= 42〜98 : 2〜38 : 30〜0，宜為（A): (B) : (D) = 42〜95 : 5〜38 : 3 〇〜〇 〇 因成分（B)為固體，故藉由止於上述使用量或使用比 例，可獲得適於製造光學透鏡片類之黏度的本發明樹脂組 合物。 本發明樹脂組合物中，為改善處理時之便利性等，除了 上述成分以外’可依狀況併用含有脫模劑、消泡劑、平整 劑、光安定劑、抗氧化劑、聚合禁止劑、帶電防止劑等 等再者，因應必要，還可添加丙稀酸系聚合物、聚酿彈 性體、氨酯聚合物、及腈橡膠等之聚合物類。也可添加溶 劑，但且不添加溶劑。 本發明樹脂組合物，可將各成分依—般方法混合溶解而 調製。例如，可將各成分饋人时㈣裝置、溫度計之圓 底燒瓶，在40〜8(TC下攪拌〇,5〜6小時而獲得。 128948.doc 16 200906867 本發明樹脂組合物之減，作為適於光學透鏡片類製造 之黏度，宜為以E型黏度計（TV_2〇〇:東機產業社製）測定 之黏度在25C下為10〜1 50 mPa.s以下者。 依一般方法，對本發明樹脂組合物照射紫外線等之能量 線而硬化之硬化物亦包含於本發明内。該硬化物可藉:將 本發明之樹脂組合物塗布於例如具有菲淫爾透鏡、^凸透 鏡、稜鏡等形狀之印模上而設置該樹脂組合物之層，再於 該層上黏著硬質透明基板之背板（例如聚甲基丙_醋樹 脂、聚碳酸酿樹脂、聚苯乙稀樹脂、聚g旨樹脂、或此等聚 合物之混合品等所構成之基板或薄膜），而後自該硬質透 明基板側以高廢水銀燈等照射紫外線而將該樹脂組合物硬 化後，自該印模將硬化物剝離而獲得。又，作為此等過程 之應用’可採用連續式加工。 王 依此-方式，可獲得折射率（25。〇在158以上之脫模 性、模具形狀再現性、密接性、耐光性優異之形成菲淫爾 透鏡、雙凸透鏡、稜鏡、微透鏡等的光學透鏡部分之光學 透鏡片，此亦包含於本發明之中。又，折射率係由阿貝= 射率計（DR-M2 :阿塔勾公司製）等測定。 本發明樹脂組合物可供光學透鏡片有效使用。作為光取 透鏡片’可舉的有菲㈣透鏡、雙凸透鏡、稜鏡、微透= 等。又，本發明樹脂組合物還可用於光學透鏡^外之兄 途此荨用途包括各種被覆劑、接著劑等等。 [實施例] 以下，兹以實施例將本發明更詳細說明。又，本發明不 128948.doc 200906867 受以下實施例之任何限制。 合成例1.化合物（B)之合成 在乾燥容器中饋入於通式（2)中1^ =氫、、b=l之化人 物400份、曱苯500份、丙烯酸158份、對_甲苯磺酸5〇份及 氫醌5份，予以加熱之，進行脫水反應，令反應進行到餾 出水至33份為止。反應溫度為n〇〜112^。其次，將反應 液冷卻，將曱苯1 500份及20%苛性鈉水溶液2〇〇份饋入反 應系予以中和之，其次再使用20%氯化鈉水溶液2〇〇份洗 淨，再除去甲苯，獲得淡黃色之固體。折射率為丨.62。 以下述實施例中所示之組成（數值表質量份），獲得本發 明之紫外線硬化型樹脂組合物及硬化物。又，樹脂組合物 及硬化膜之評估方法及評價基準係如下所述。 (1) 黏度：使用E型黏度計（TV-200 :東機產業社製）在 25°C下測定。 (2) 脫模性：表硬化之樹脂自模具脫模時之難易度。 〇.…自模具之脫模良好 △…·脫模稍有困難或脫模時有剝離聲 X ····脫模困難或模具殘留 (3) 模具形狀再現性： 〇····再現性良好 x····再現性不良 ⑷密接性：在基材上塗布膜厚約5〇卿程度之樹脂組 合物’其次再以高Μ水銀燈⑽w/cm、無臭氧）照射硬化 而製成測試件’依JISK560〇-5-6進行密接性評價。 128948.doc -18- 200906867 (5) 折射率（25°C):以阿貝折射率計（DR-M2 :阿塔勾 公司製）進行測定。 (6) 玻璃轉移溫度（Tg) ·以黏彈性測定系統（dmS· 6000 :精工電子工業股份有限公司製），利用拉伸模式， 在頻率1Hz下測定硬化之紫外線硬化型樹脂層之丁匕點 實施例1 作為成分（A)使用丙烯酸鄰-苯基酚一乙氧酯（日本化藥股 份有限公司製之KAYARAD ΟΡΡ-1)85份、作為成分（B)使 用合成例1所得之化合物5份、作為成分（C)使用2_羥基_2_ 甲基-1-苯基丙烷_1_酮3份、作為成分（D)使用丙烯醯嗎啉 1 〇份，在6(TC下加溫混合之，獲得本發明樹脂組合物。此 樹脂組合物之黏度為120mPa.s〇又，將此樹脂組合物硬化 所得薄臈之折射率（25。〇為1.604，玻璃轉移溫度（1^)為 50〇C。 將此樹脂組合物以膜厚50 μΓη之方式塗布於稜鏡透鏡模 具上，在其上黏著聚碳酸酯薄膜5〇〇 μηι厚作為基材，再自 其上方以高壓水銀燈照射1〇〇〇 mJ/cm2照射量之紫外線， 硬化後予以剝離，獲得稜鏡透鏡片。 評價結果 脫模性：〇，模具形狀再現性：〇，密接性··〇。 實施例2 作為成分（A)使用丙烯酸鄰_苯基酚—乙氧酯（日本化藥股 份有限公5]製之KAYARAD贈_1)75份、作為成分⑻使 用口成例1所4^•之化合物25份、作為成分（c)使用經基冬 I28948.doc -19- 200906867 甲基-卜苯基丙烷-1 -酮3份，在60。〇下加溫混合之，獲得本 發明樹脂組合物。此樹脂組合物之黏度為71 〇 mPa.s。又， 將此樹脂組合物硬化所得薄膜之折射率（25。〇)為丨.616，玻 璃轉移溫度（Tg)為59°C。 將此樹脂組合物以膜厚50μηι之方式塗布於稜鏡透鏡模 具上’在其上黏著聚碳酸酯薄膜5〇〇 μηΊ厚作為基材，再自 其上方以南壓水銀燈照射丨〇〇〇 mJ/cm2照射量之紫外線， 硬化後予以剝離，獲得稜鏡透鏡片。 評價結果 脫模性：〇’模具形狀再現性：〇，密接性：〇。 實施例3 將κ施例1所得之樹脂組合物以膜厚2〇〇 之方式塗布 於菲淫爾透鏡模具上，在其上黏著聚碳酸酯基材丨mm厚， 再自其上方以高壓水銀燈照射丨〇〇〇 mJ/cm2照射量之紫外 線’硬化後予以剝離，獲得菲涅爾透鏡。 評價結果 脫模性.〇 ’模具形狀再現性：〇，密接性：〇。 比較例1 據專利文獻丨（特開昭63-167301)之實施例1 ,將阿羅尼 克沂M315(異氰脲酸三（2_丙烯醯氧乙酯））7〇份、丙烯酸四 氫糠酯3 〇份、竹么土 &人丄 作為先聚合起始劑之1-(4-異丙基苯基）-2-羥 土士甲基丙烷-1-酮3份，在6〇。〇下加溫混合之，獲得比較 用樹月曰、，且合物。此樹脂組合物之黏度為134 mPa.s。又，將 于曰、且〇物硬化所得薄膜之折射率（25。(：）為1.52。 128948.doc -20· 200906867 由此結果可知，比較例1之組合物較本發明組合物之折 射率為低，不適於製造本發明之透鏡類。 比較例2 依據專利文獻3(曰本特許第3209554)之實施例，合成該 文獻之合成例1的氨酯丙烯酸酯（新戊二醇與己二酸之聚酯 一醇’乙二醇、二異氰酸甲代苯樓酯及丙婦酸2_經基乙酯 之反應物）、以及該文獻合成例3之化合物（丙烯酸鄰-苯基 酚—乙氧酯）’將上述氨酯丙烯酸酯30份、上述丙烯酸鄰_ 苯基酚二乙氧酯15份、KAYARAD R-551(二丙烯酸雙酚A 四乙氧酯）45份、丙烯酸三溴苯酯10份、及Irgcure_184(1 — 經基環己基苯基酮）3份，在6(rc下加溫混合之，獲得比較 用樹脂組合物。此樹脂組合物之黏度為442〇 mpa.s。又， 將此树月曰組合物硬化所得薄膜之折射率（25 ο。）為1 $ μ。 由此結果可知’比較例丨之組合物較本發明組合物之黏 又為问不適於微細加工或捲狀片體或薄膜之連續加工。 度，脫模性、模具形 且其硬化物為高折射 由實施例卜2、3及比較例i、2之評價、结果可知，具有 特定組成之本發明樹脂組合物為低黏度，脫模性、 因此， 適於製造具有The photopolymerization initiator contained in the resin composition of the present invention may, for example, be benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether or benzoin butyl. Benzoin such as ether; acetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxyphenylacetophenone, hydrazine, hydrazine-dibenzene Ethyl ketone, 2-hydroxy-2-methyl-p-mentylpropane-nonanone, diethoxy acetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1_[4-(methylthio) Phenyl ketones such as phenyl phenyl 2 morpholinopropan-1-one; 2-ethyl oxime, 2-t-butyl ketone, 2-chloro oxime, 2-pentyl broth, etc. Anthraquinone; a thioxanthone such as 2,4-diethylthianone, 2-isopropylthioxanthone or 2-chlorothiazinone; acetophenone didecyl ketal, benzyl a ketal such as a bis- fluorenyl ketone; a diphenyl benzophenone, a 4-benzoquinone-4, a methyl diphenyl sulfide, a diphenyl benzoate such as a 4,4, dioxin benzophenone Anthrones; oxidized scales such as 2,4,6-trimethylphenylhydrazine diphenylphosphine oxide, bis(2,4,6-trimethylphenylhydrazine)-phenylphosphine oxide, and the like. Among them, preferred are acetophenones, more preferably 2-hydroxy-2-nonylphenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, and the resin composition of the present invention. The polymerization initiators may be used singly or in combination of plural kinds. The ratio of use of each component of the resin composition of the present invention is determined in consideration of a desired refractive index, glass transition temperature, viscosity, or adhesion. 7 When the component (4) ten component (B) + component (9) is a mass component, Including the component (9): The content of the component (B) is 70 to 丨〇〇 by mass, particularly preferably 128,948.doc 15 200906867 75 to 100 parts by mass. When the component (D) is contained, the content of the component (D) is 丨 〜 3 〇 mass parts ' particularly preferably 1 to 25 parts by mass. In addition, when the total amount of the component (A) + the component (B) + the component (D) is 100 parts by mass, the content of the component (A) and the presence or absence of the component (D) are 60 to 98 parts by mass. Particularly preferably, it is 70 to 95 parts by mass. The total amount of the component (c) relative component (A) + component (b) + component (D) is preferably 0.1 to 10 parts by mass, particularly preferably 〇 3 to 5 parts by mass. The ratio of use of each component of the resin composition of the present invention is determined in consideration of a desired refractive index, glass transition temperature, viscosity or adhesion, and the component (A) + component (B) + component (D) is set to 1 〇. 〇 mass parts, (A) : :(1)) = 42~98 : 2~38 : 30~0, should be (A): (B) : (D) = 42~95 : 5~38 : 3 〇~ Since the component (B) is a solid, the resin composition of the present invention which is suitable for producing the viscosity of an optical lens sheet can be obtained by the above-mentioned use amount or use ratio. In the resin composition of the present invention, in order to improve the convenience in handling, etc., in addition to the above-mentioned components, a mold release agent, an antifoaming agent, a leveling agent, a photostabilizer, an antioxidant, a polymerization inhibiting agent, and a charge prevention can be used in combination. Further, if necessary, a polymer such as an acrylic polymer, a polystyrene elastomer, a urethane polymer, or a nitrile rubber may be added. A solvent may also be added, but no solvent is added. The resin composition of the present invention can be prepared by mixing and dissolving each component in a usual manner. For example, when the components are fed, the device (4) and the round bottom flask of the thermometer are obtained by stirring at 40 to 8 (TC for 5 to 6 hours). 128948.doc 16 200906867 The resin composition of the present invention is reduced as appropriate. The viscosity of the optical lens sheet is preferably 10 to 150 mPa.s or less at 25 C as measured by an E-type viscometer (TV_2: manufactured by Toki Sangyo Co., Ltd.). A cured product obtained by irradiating an energy ray of an ultraviolet ray or the like with a resin composition is also included in the present invention. The cured resin can be applied to a resin composition of the present invention, for example, having a shape such as a phenanthrene lens, a convex lens, or a crucible. a layer of the resin composition is disposed on the stamp, and a back sheet of the hard transparent substrate is adhered to the layer (for example, polymethyl acrylate resin, polycarbonate resin, polystyrene resin, poly phenol resin) Or a substrate or a film formed of a mixture of such polymers, and then irradiating the resin composition with ultraviolet rays from a high-purity silver lamp or the like from the side of the hard transparent substrate, and then peeling off the cured product from the stamp. Acquire The application of these processes can be carried out in a continuous process. In this way, Wang can obtain a refractive index (25. The release property of 158 or more, the reproducibility of mold shape, the adhesion, and the light resistance are excellent. An optical lens sheet of an optical lens portion of a lens, a lenticular lens, a cymbal, a microlens or the like is also included in the present invention. Further, the refractive index is determined by an Abbe = luminometer (DR-M2: Attaco) The resin composition of the present invention can be effectively used for an optical lens sheet. As the light-receiving lens sheet, there are phenanthrene (tetra) lenses, lenticular lenses, enamel, micro-transparent =, etc. Further, the resin composition of the present invention It is also possible to use it in the optical lens, including various coating agents, adhesives, etc. [Embodiment] Hereinafter, the present invention will be described in more detail by way of examples. Further, the present invention is not limited to 128948.doc 200906867 Any of the following examples. Synthesis Example 1. Synthesis of Compound (B) In a dry container, 1 ^ = hydrogen in the formula (2), 400 parts of the b = l, 500 parts of toluene, 158 parts of acrylic acid, 5 parts of p-toluenesulfonic acid and hydroquinone 5 parts, heated, and subjected to a dehydration reaction, and the reaction was carried out until the distilled water reached 33 parts. The reaction temperature was n〇~112^. Next, the reaction liquid was cooled, and 500 parts of toluene and 20% aqueous solution of caustic soda were added. 2 parts of the feed reaction system was neutralized, and then washed with 2% aqueous solution of 20% sodium chloride, and then toluene was removed to obtain a pale yellow solid. The refractive index was 丨.62. The composition shown in the above (quantity of the numerical value) is obtained by obtaining the ultraviolet curable resin composition and the cured product of the present invention. Further, the evaluation methods and evaluation criteria of the resin composition and the cured film are as follows: (1) Viscosity: The measurement was carried out at 25 ° C using an E-type viscometer (TV-200: manufactured by Toki Sangyo Co., Ltd.). (2) Mold release property: The ease with which the hardened resin is released from the mold. 〇 ... ... 自 模具 模具 模具 模具 自 自 自 自 自 自 自 自 自 自 自 自 自 ...... ...... ...... ...... ...... ...... ...... ...... ...... ...... ...... ...... ...... ...... ...... ...... ...... ...... ...... ...... ...... ...... ...... ...... ...... ...... ...... ...... ...... ...... Good x····Reproducibility is poor (4) Adhesiveness: A resin composition having a film thickness of about 5 〇 is applied to a substrate, and then a sorghum mercury lamp (10) w/cm, no ozone is irradiated and hardened to prepare a test piece. 'Adhesion evaluation according to JISK560〇-5-6. 128948.doc -18- 200906867 (5) Refractive index (25 ° C): It was measured by an Abbe refractometer (DR-M2: manufactured by Atta Co., Ltd.). (6) Glass transition temperature (Tg) - The viscoelasticity measurement system (dmS·6000: manufactured by Seiko Instruments Inc.) was used to measure the hardness of the cured UV-curable resin layer at a frequency of 1 Hz using a tensile mode. Example 1 As component (A), 85 parts of o-phenylphenol monoethoxylate (KAYARAD®-1 manufactured by Nippon Kayaku Co., Ltd.) was used, and as a component (B), 5 parts of the compound obtained in Synthesis Example 1 was used. As component (C), 3 parts of 2-hydroxy-2-methyl-1-phenylpropan-1-one was used, and as component (D), 1 part of propylene morpholine was used, and it was heated at 6 (TC). The resin composition of the present invention is obtained. The viscosity of the resin composition is 120 mPa·s, and the refractive index of the thin enamel obtained by hardening the resin composition (25. 〇 is 1.604, glass transition temperature (1^) is 50 〇). C. The resin composition was applied to a ruthenium lens mold at a film thickness of 50 μΓ, and a polycarbonate film of 5 μm thick was applied as a substrate thereon, and then irradiated with a high-pressure mercury lamp from above.紫外线mJ/cm2 exposure to ultraviolet light, peel off after hardening, obtain Mirror lens sheet. Evaluation results Release property: 〇, mold shape reproducibility: 〇, adhesion··〇. Example 2 As component (A), o-phenylphenol-ethoxylate acrylate was used (Nippon Chemical Co., Ltd. limited) KAYARAD of the public company 5), 75 parts, as a component (8), 25 parts of the compound of the example 1 of the mouth, used as the component (c) by the base of the winter I28948.doc -19-200906867 methyl-b 3 parts of phenylpropan-1-one, which was mixed under heating at 60 ° C to obtain a resin composition of the present invention. The viscosity of the resin composition was 71 〇 mPa·s. Further, the film obtained by hardening the resin composition was obtained. The refractive index (25. 〇) was 丨.616, and the glass transition temperature (Tg) was 59 ° C. The resin composition was applied to a ruthenium lens mold at a film thickness of 50 μm, and the polycarbonate was adhered thereto. The film was 〇〇μηΊ thick as a substrate, and ultraviolet rays irradiated with 丨〇〇〇mJ/cm2 were irradiated from a mercury lamp at a south pressure thereon, and after being hardened, it was peeled off to obtain a ruthenium lens sheet. Evaluation results Release property: 〇' Mold shape reproducibility: 〇, adhesion: 〇. Example 3 κ Example 1 The resin composition was applied to a Philippine lens mold with a film thickness of 2 Å, and a polycarbonate substrate was adhered thereto to a thickness of 丨mm, and then irradiated with 高压mJ/cm2 from a high-pressure mercury lamp thereon. The amount of ultraviolet rays was peeled off after hardening to obtain a Fresnel lens. Evaluation results of mold release. 〇 'Mold shape reproducibility: 〇, adhesion: 〇. Comparative Example 1 According to the patent document 特 (Japanese Unexamined Patent Publication No. 63-167301) Example 1 , aronenic oxime M315 (three (2- propylene oxirane) isocyanurate), 7 parts of tetrahydrofurfuryl acrylate, bamboo mulch & The starting agent 1-(4-isopropylphenyl)-2-hydroxyindolizan-1-one 3 parts, at 6 Torr. The underarms are warmed and mixed, and the comparison is made with the tree sap, and the compound. The viscosity of this resin composition was 134 mPa.s. Further, the refractive index of the film obtained by hardening the ruthenium and the ruthenium (25: (:) is 1.52. 128948.doc -20· 200906867. From the results, it is understood that the composition of Comparative Example 1 has a refractive index higher than that of the composition of the present invention. It is not suitable for the production of the lens of the present invention. Comparative Example 2 According to the example of Patent Document 3 (Japanese Patent No. 3209554), the urethane acrylate of the synthesis example 1 of the document (neopentylene glycol and hexamethylene) was synthesized. Acid polyester monool 'ethylene glycol, methicillary diisocyanate and propylene glycol 2 - thioethyl ester reactant), and the compound of the synthesis example 3 of the literature (o-phenylphenol acrylate) - ethoxylate) '30 parts of the above urethane acrylate, 15 parts of the above o-phenylphenol diethoxylate, 45 parts of KAYARAD R-551 (bisphenol A tetraethoxy acrylate), tribromo acrylate 10 parts of phenyl ester and 3 parts of Irgcure_184 (1 - cyclohexyl phenyl ketone) were mixed and mixed at 6 (rc) to obtain a comparative resin composition. The viscosity of the resin composition was 442 〇mpa.s. Further, the refractive index (25 ο.) of the film obtained by hardening the tree enamel composition is 1 $ μ. It is known that the composition of the comparative example is less suitable for the continuous processing of microfabrication or rolled sheet or film than the composition of the present invention. Degree, mold release, mold shape and hardening of the cured product are carried out by high refractive The results of the evaluations of Examples 2 and 3 and Comparative Examples i and 2 show that the resin composition of the present invention having a specific composition has a low viscosity and a mold release property, and therefore, is suitable for production.
狀再現性、對於基材之密接性優異， 率’玻璃轉移溫度（Tg)為5〇t：以上。 微細構造之光學透鏡片 鏡、稜鏡、微透鏡等。 連續加工為必要步驟之製造。 [產業上之可利用性] 本發明之紫外線硬化型樹脂組合物 及其硬化物， 主要特 I28948.doc 200906867 別適用於菲涅爾透鏡、雙凸透鏡、稜鏡、微透鏡等之光學 透鏡片。 f 128948.doc -22-The form reproducibility is excellent in adhesion to a substrate, and the rate 'glass transition temperature (Tg) is 5 〇 t: or more. Microlens optical lens, mirror, microlens, etc. Continuous processing is the manufacture of the necessary steps. [Industrial Applicability] The ultraviolet curable resin composition of the present invention and the cured product thereof are mainly applied to an optical lens sheet such as a Fresnel lens, a lenticular lens, a crucible, or a microlens. f 128948.doc -22-