TW200810922A - Active energy ray curable composition, transparent film made of the composition, and optical disk using the film - Google Patents
Active energy ray curable composition, transparent film made of the composition, and optical disk using the film Download PDFInfo
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- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
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- G11B7/252—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
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- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
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Abstract
Description
200810922 九、發明說明： 【發明所屬之技術領域】 本發明係關於活性能量射線硬化性組成物、由該組成物 所構成之透明薄膜、及將該薄膜用作構成構件之光碟，上 述活性能量射線硬化性組成物適合用作透明且光學畸鐵 小之薄膜或經光學功能調整之窗、顯示器·光碟等摄 構件等光學用途。 成 尤其是，上述薄膜能以高厚度精度實現厚度薄至丨“厕 者到2000 左右者，且透明度高而光學畸變小，因此， 適於形成次世代型碟片之高密度記錄媒體，例如藍光光 碟、UDO (超密度光碟 Ultra Density 〇pticai)等光 至少1層。 ' ' 【先前技術】 習知，於液晶顯示器、電漿顯示器等之用於調整光學功 能的薄膜之基底或間隔片、光碟之記錄層上之間隔片上， 形成.應用有光學畸變小之塑膠薄膜，但因該薄膜利用流 每法或塗佈法等而成形，故材料受到限^，耐執變形性、 耐熱分解性、薄膜化加工性、成本等無法達成一致，從而 令使用用途·條件受到制約。 例如專利文獻i中揭示有含有（甲基）丙稀酸胺基甲 酉旨化合物等寡聚物成分、特定（甲基）丙稀酸醋化合物之 性能量射線硬化性組成物，其顯示出作為5G幻00 u 之活性能量射線硬化性組成物之加卫方法的塗佈法（尤 是旋轉塗佈法）之優缝，但藉由旋轉㈣法使具有專· 312XP/發明說明書(補件)/96-10/96123707 6 200810922 ::，1二所揭示之組成的活性能量射線硬化性組成物成 並二：:人將其加工為50至100 之厚度則厚度精度 77進而，所使用之活性能量射線硬化性組成物之 加工乂驟中的飛散等之損失較大，難說其具有實用性。200810922 IX. The present invention relates to an active energy ray-curable composition, a transparent film composed of the composition, and a disc for using the film as a constituent member, the active energy ray The curable composition is suitably used for optical applications such as a film which is transparent and optically distorted, or a member such as an optically-adjustable window, a display, or a disc. In particular, the above-mentioned film can achieve a thin thickness to a high thickness precision of "the toilet is up to about 2000, and the transparency is high and the optical distortion is small. Therefore, it is suitable for forming a high-density recording medium of a next-generation type disc, such as blue light. Optical disc, UDO (Ultra Density 〇pticai), etc., at least one layer of light. '' [Prior Art] Conventionally, a substrate or spacer for optical films for adjusting optical functions, such as a liquid crystal display or a plasma display, or a disc A plastic film having a small optical distortion is formed on the spacer on the recording layer. However, since the film is formed by a flow method or a coating method, the material is limited, resistant to deformation, thermal decomposition resistance, The filming processability, cost, and the like cannot be agreed, and the use and conditions are restricted. For example, Patent Document i discloses an oligomer component such as a (meth)acrylic acid amine-based compound, and a specific component (A) A sexual energy ray-curable composition of an acrylic acid vinegar compound which exhibits a coating method as a curing method of an active energy ray hardening composition of 5G magic 00 u The superiority of the method (especially the spin coating method), but by the rotation (four) method, the activity of the composition disclosed in the special 312XP/invention specification (supplement)/96-10/96123707 6 200810922::,1 The energy ray-curable composition is formed into two: a person who processes the thickness to a thickness of 50 to 100 and has a thickness accuracy of 77. Further, the loss of scattering or the like in the processing step of the active energy ray-curable composition used is large. It is difficult to say that it is practical.
六另外、，紫外線⑽硬化之環氧樹脂、丙烯酸樹脂薄膜雖 谷易製造，但與上述樹脂同樣容易破碎，進而，將該等樹 脂可用於用以獲得厚度為數"以下之膜的塗佈法或洗 鑄法等中但加工為厚度為數十#m〜數百#^之薄膜之 例則不得而知。 另外’作為光學畸變小且耐熱變形性高 所周知有改質聚酿亞胺、聚㈣等各種卫程塑膠^; 價格高且成形溫度高，故料受到限定。料f利用流= 法製造聚碳酸醋薄膜則費工夫且價格高而難以使用，熱硬 化之紛樹脂、環氧樹脂、丙烯酸樹脂薄膜容易破碎且製造 費工夫’該等樹脂並不適合用作薄膜用素材。 _ 例如專利文獻2中記載了如下樹脂組成物，其作為解決 變形後無法恢復為原來形狀之現象（放置痕跡），且透明 性、折射率、表面硬度等優良，生產性亦優良之光學物品 用電離放射線硬化型樹脂組成物，係由雙 脂、雙紛F型環氧樹脂等具有環狀構造且具有兩 丙烯酸酯基的丙烯酸環氧酯（a)，及具有環狀構造之單官 能丙烯酸酯（b)所構成，且包含特定量之丙烯酸酯官能基。 然而，專利文獻2中所記載之光學物品用電離放射線硬 化型樹脂組成物於韌性、耐熱性及二次加工性方面並不充 312XP/發明說明書(補件)/96-10/96123707 7 200810922 , 分，光學用途之適用性差。 因此’業者期望開發出光學 Λ 尤予岬、交小，靭性、耐熱性等物 性及二次加工性更優良，日：t ®, ^ 炎艮且主要適於光學用途之樹脂組成 : 物〇 (專利文獻1)曰本專利特開2003_231725號公報 (專利文獻2)曰本專利特開平9_616〇1號公報 【發明内容】 (發明所欲解決之問題） 籲本發明之目的在於提供活性能量射線硬化性組成物、由 該組成物所構成之透明薄膜及包含將該透㈣膜層作為 構成構件之-部分且艎曲小的光碟，上述活性能量射線硬 化性組成物透明且光學畸變小，勃性、耐熱性、及二次加 工丨生優良，且可容易地成形為連續之輥狀薄膜。 (解決問題之手段） 本發明者針對可吸收光、電子束等活性能量射線而硬化 馨之各種材料，研究使該等組合反應時所獲得之反應生成物 之物性’其結果發現，以特定調配比調配特定組成之丙稀 酸鹽，並使該丙烯酸鹽於活性能量射線之照射下反應，藉 此可獲得可實現上述目的之樹脂組成物、透明薄膜及 碟。 、 即，本發明係採用下述（1)〜（18)之構成者。 ‘ β(υ—種透明薄膜，其由以下（Α)〜（(:）中任一種活性能 量射線硬化性組成物所構成·· U)含有（甲基）丙烯酸胺基甲酸酯3〇〜6〇重量份、（甲 312ΧΡ/發明說明書(補件)/96-10/96123707 8 200810922 基）丙烯酸苯氧酯20〜50重量份、（曱基）丙烯酸環^ > 〜30重量份的活性能量射線硬化性組成物；衣虱酯0 (B) 含有（甲基）丙烯酸胺基曱酸酯4〇〜6〇重量份、 基）丙烯酸環氧酯10〜40重量份、（甲基）丙烯酸脂環^甲〇 〜30重量份的活性能量射線硬化性組成物； f曰 (C) 含有（曱基）丙烯酸胺基曱酸酯2〇〜7〇重量份、具有 環氧烷基之2官能以上之（甲基）丙烯酸酯1〇〜6〇重量 份、（甲基）丙烯酸環氧酯〇〜3〇重量份、（甲基）丙烯酸= 氧酯10〜50重量份的活性能量射線硬化性組成物。 (2) 如上述（〇之透明薄膜，其中，25它之儲存彈性模數 (E )為2000 MPa以上，且l〇(Tc之儲存彈性模數（E，） 未滿 100 MPa。 (3) 如上述（1)或（2)之透明薄膜，其中，上述（甲基）丙 烯酸胺基甲酸酯由下述通式[丨]或[2]表示， [化1] [化2]In addition, although the ultraviolet (10) hardened epoxy resin or the acrylic resin film is easy to manufacture, it is easily broken as with the above resin, and further, these resins can be used for coating methods for obtaining a film having a thickness of " It is not known that the film is processed into a film having a thickness of several tens #m to several hundred #^ in a washing method or the like. In addition, as a small optical distortion and high heat deformation resistance, various modified plastics such as polyacrylamide and poly(tetra) are known. The price is high and the molding temperature is high, so the material is limited. The production of polycarbonate film by the flow method is laborious and expensive, and it is difficult to use. The heat-hardened resin, epoxy resin, and acrylic resin film are easily broken and the manufacturing time is difficult. These resins are not suitable for use as a film. material. For example, Patent Document 2 describes a resin composition which is excellent in transparency, refractive index, surface hardness, and the like, and which is excellent in productivity, and which is excellent in transparency, refractive index, surface hardness, and the like. The ionizing radiation-curable resin composition is an epoxy acrylate (a) having a cyclic structure and having two acrylate groups, such as a bi-fat or a double-type F-type epoxy resin, and a monofunctional acrylate having a cyclic structure. (b) is constructed and contains a specific amount of acrylate functional groups. However, the ionizing radiation-curable resin composition for an optical article described in Patent Document 2 does not charge 311 XP/invention specification (supplement)/96-10/96123707 7 200810922 in terms of toughness, heat resistance, and secondary workability. The applicability of optical applications is poor. Therefore, the industry expects to develop optical properties such as 岬 岬, cross-linking, toughness, heat resistance and other secondary properties. Day: t ® , ^ Inflammable and mainly suitable for optical use of resin composition: [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei 9-616 No. 1 (Invention) The object of the present invention is to provide active energy ray hardening. The transparent composition comprising the composition, the optical film comprising the transmissive (four) film layer as a constituent member and having a small distortion, the active energy ray-curable composition is transparent and optically distorted, and the bo It is excellent in heat resistance and secondary processing, and can be easily formed into a continuous roll-shaped film. (Means for Solving the Problem) The present inventors have studied the physical properties of the reaction product obtained by the combination of the active energy rays such as light and electron beams, and studied the physical properties of the reaction product obtained by the combination reaction. A resin composition, a transparent film, and a dish which can achieve the above object can be obtained by blending a specific acid salt of a specific composition and allowing the acrylate to react under irradiation with an active energy ray. That is, the present invention employs the following components (1) to (18). 'β(υ-transparent film, which consists of any of the following active energy ray-curable compositions (·: U) contains (meth)acrylic acid urethane 3〇~ 6 parts by weight, (A 312 ΧΡ / invention manual (supplement) / 96-10/96123707 8 200810922) phenoxy acrylate 20~50 parts by weight, (fluorenyl) acrylate ring > ~ 30 parts by weight of activity Energy ray hardening composition; clothing ester 0 (B) containing (meth)acrylic acid amide phthalate 4 〇 ~ 6 〇 parts by weight, methacrylate epoxy ester 10 to 40 parts by weight, (meth) acrylic acid Alicyclic ring oxime ~ 30 parts by weight of active energy ray hardening composition; f 曰 (C) containing (mercapto) acrylamide phthalic acid ester 2 〇 ~ 7 〇 parts by weight, having an epoxy alkyl group The above (meth) acrylate is used in an amount of from 1 to 6 parts by weight, (meth)acrylic acid epoxy ester 〇 to 3 parts by weight, and (meth)acrylic acid = oxyester is 10 to 50 parts by weight of active energy ray hardening property. Composition. (2) As described above (a transparent film of which 2525 has a storage elastic modulus (E) of 2000 MPa or more, and l〇 (the storage elastic modulus (E) of Tc is less than 100 MPa. (3) The transparent film of the above (1) or (2), wherein the above (meth)acrylic acid urethane is represented by the following formula [丨] or [2], [Chemical Formula 1] [Chemical 2]
(其中，上述通式[1]中，1表示含有羥基之（曱基）丙烯酸 312XP/發明說明書(補件)/96-10/96123707 9 200810922 ,曰之㈣部分’ R2表示異氰酸酯殘基，&表示醇殘基 4醚二醇、聚酯二醇及聚碳酸酯二醇中選擇之 醇殘基，r4表示氫或甲基，n表示2〜2〇之整數 y 上述通式[2]中，n表示4以上之整數）。 (4) 如上述（1)至（3)中任一項之透明薄膜， 7基)丙稀酸苯氧醋於分子内具有至少丨、異苯2 一、表氣醇縮合二 (5) 如上述（丨）至（3)中任一項之透明薄膜，盆 (甲基）丙烯酸苯氧酯於分子内具有至少^美^ =碳以上之一及表氯醇= 次者乙一醇細合組成。 (6) 如上述（1)至（5)中任一項之透明薄膜，i (甲基）丙烯酸環氧酯由下述通式[3]表示，' 八，处 [化 3] '(In the above formula [1], 1 represents a hydroxy group-containing (mercapto)acrylic acid 312XP/invention specification (supplement)/96-10/96123707 9 200810922, and a part (R) represents an isocyanate residue, & And represents an alcohol residue selected from the group consisting of an alcohol residue 4 ether diol, a polyester diol, and a polycarbonate diol, r4 represents hydrogen or a methyl group, and n represents an integer y of 2 to 2 上述 in the above formula [2] , n represents an integer of 4 or more). (4) The transparent film according to any one of (1) to (3) above, wherein the 7-base acrylic acid phenoxy acetonate has at least fluorene, isophthalene 2, and epigas alcohol condensation in the molecule (5) The transparent film according to any one of the above (A) to (3), wherein the phenoxy (phenoxy) phenoxylate has at least one of the above-mentioned ^=carbon and the epichlorohydrin=the second ethyl alcohol is combined in the molecule. . (6) The transparent film of any one of the above (1) to (5), wherein the (meth)acrylic acid epoxy ester is represented by the following general formula [3], 'eight, at [chemical 3]'
[3】 (其中’R1、R2表示氩或曱基，η表示 (7)如上述（1)至（5)中任一項之透 12之整數） 甲基）丙稀酸環氧酯係雙紛Α環氧 酯 明薄膜，其中，上述 丙基醚（甲基）丙烯酸 ⑻如上述⑴至⑺中任一項之透明薄膜，其中，具有 312XP/發明說明書(補件)/96-10/96123707 10 200810922 上述環氧烷基之式[4 ]表示，[化4] B月b以上之（甲基）丙烯酸酯由下述通[3] (wherein 'R1, R2 represents an argon or a fluorenyl group, and η represents (7) an integer of 12 according to any one of the above (1) to (5)) methyl) acrylate epoxy ester double A transparent film of any one of the above (1) to (7), which has a 312XP/invention specification (supplement)/96-10/96123707, which is a transparent film of the above-mentioned propyl ether (meth)acrylic acid (8). 10 200810922 The above formula (4) of the alkylene oxide group indicates that the (meth) acrylate of the above B b or more is passed through
C4]C4]
(其中’ R表示氫或甲基，n、m表示 (9)一種光碟用保護薄膜，其由如 項之透明薄膜所構成。 1〜4之整數）。 上述（1)至（8)中任一 (10) —種光碟，其至少積層一層 護薄膜而形成。 如上述（9)之光碟用保(wherein 'R represents hydrogen or methyl, and n and m represent (9) a protective film for a disc, which is composed of a transparent film of the above. An integer of 1 to 4). The optical disc of any one of the above (1) to (8), which is formed by laminating at least one protective film. As in the above (9)
(11) 如上述10之光碟’其中’至少按照基板、記錄層、 保護膜之順序積層而成之光碟中，上述保護膜包含如上述 (9)之光碟用保護薄膜，且該保護膜之厚度為〇 2咖以下1 (12) —種活性能量射線硬化性組成物，其含 〜（C)之任一種： 下以） (A)(曱基）丙烯酸胺基曱酸酯3〇〜6〇 丙烯酸苯氧酯20〜50重量份、（曱基）丙 30重量份； 重量份、（曱基） 埽酸環氧酯〇〜 (B)(曱基）丙烯酸胺基曱酸酯 丙烯酸環氧酯10〜40重量份、 30重量份； 4〇〜60重量份、（甲基) (曱基)丙烯酸脂環酉"〜 議基)丙烯酸胺基甲酸醋20〜70重量份、具有環氧 312XP/發明說明書(補件)/96-10/96123707 11 200810922 烧基之1 2官能以上之（曱基）丙烯酸酯10〜60重量份、（曱 基）丙稀酸環氧酯〇〜30重量份、（曱基）丙烯酸苯氧酯10 ' 〜50重量份。 ' (13)如上述（12)之活性能量射線硬化性組成物，其中， 上述（甲基）丙烯酸胺基甲酸酯由下述通式[i ]或[2 ]表 示， [化1] [化2](11) The optical disc according to the above-mentioned (9), wherein the protective film comprises the protective film for the optical disk as described in (9) above, and the thickness of the protective film is as described above. 1 (12) is an active energy ray hardening composition containing any of ~(C): Bottom to) (A) (fluorenyl) acrylamide phthalate 3〇~6〇 20 to 50 parts by weight of phenoxy acrylate, 30 parts by weight of (mercapto) propylene; parts by weight, (fluorenyl) phthalic acid epoxy ester 〇 ~ (B) (fluorenyl) acrylamide phthalate acrylate acrylate 10 to 40 parts by weight, 30 parts by weight; 4 〇 to 60 parts by weight, (methyl) (fluorenyl) acrylate ring 酉 〜 〜 〜 议 ) 丙烯酸 20 20 20 20 20 20 具有 具有 312 312 312 /Invention Manual (Supplement)/96-10/96123707 11 200810922 A base of 2 (functional) or higher (fluorenyl) acrylate 10 to 60 parts by weight, (mercapto) acrylate epoxy ester 〇 30 parts by weight , (fluorenyl) phenoxy acrylate 10' to 50 parts by weight. (13) The active energy ray-curable composition according to the above (12), wherein the (meth)acrylic acid urethane is represented by the following general formula [i] or [2], [Chemical Formula 1] [ 2]
312XP/發明說明書(補件)/96-10/96123707 12 1 2 二中、’上述通式[1]中，^表示含有羥基之（曱基）丙烯酸 酯之殘鏈部分，r2表示異氰酸_基，1表示醇殘基或自 聚醚二醇、聚酯二醇及聚碳酸酯二醇中選擇之至少1種二 醇殘基，R3表示氳或甲基，n表示2〜2〇之整數；另外， 上述通式[2]中，η表示4以上之整數）。 3 U4)如上述（12)或⑽之活性能量射線硬化性組成 物，其中，上述（甲基）丙烯酸苯氧酯於分子内呈有至少工 個異丙苯基組成、碳原子數為8以上之燒基組成、表氯醇 200810922 縮合組成及乙二醇縮合組成中之任一種。 舊(15)如上述（12)或（13)之活性能量射線硬化性組成 •物，其中，上述（T基）丙烯酸苯氧酯於分子内具有至少1 :個異丙苯基組成或者碳原子數為8以上之炫基組成、及表 氯醇縮合組成或者乙二醇縮合組成。 (16)如上述（12)至（15)中任一項之活性能量射線硬化 11組成物，其中，上述（甲基）丙烯酸環氧酯由下述通式[3 ] 表示， _ [化 3]312XP/Invention Manual (Supplement)/96-10/96123707 12 1 2 In the above formula [1], ^ represents a residual moiety of a (hydroxyl) acrylate containing a hydroxyl group, and r2 represents isocyanic acid. _ group, 1 represents an alcohol residue or at least one diol residue selected from the group consisting of polyether diol, polyester diol and polycarbonate diol, R 3 represents hydrazine or methyl group, and n represents 2 〜 2 〇 In the above formula [2], η represents an integer of 4 or more). (3) The active energy ray-curable composition according to the above (12) or (10), wherein the phenoxy (meth) acrylate has at least one cumene group in the molecule and has a carbon number of 8 or more. Any of the base composition, epichlorohydrin 200810922 condensation composition and ethylene glycol condensation composition. The active energy ray-curable composition of (12) or (13) above, wherein the above (T-based) phenoxy acrylate has at least 1: cumene composition or carbon atom in the molecule. The number is 8 or more of the stimuli composition, and the epichlorohydrin condensation composition or the ethylene glycol condensation composition. (16) The active energy ray hardening 11 composition according to any one of the above (12), wherein the (meth)acrylic acid epoxy ester is represented by the following general formula [3], _ [Chemical 3 ]
[3] (其中’ Rl、R2表示氳或甲基，η表示1〜;[2之整數）。 • (17)如上述（12)至（15)中任一項之活性能量射線硬化 性組成物，其中’上述（甲基）丙烯酸環氧酯係雙酚Α環氧 丙基醚（曱基）丙烯酸酯。 (18)如上述（12)至（17)中任一項之活性能量射線硬化 性組成物，其中，具有上述環氧烷基之2官能以上之（甲 基）丙烯酸酯由下述通式[4]表示， .[化 4] 312ΧΡ/發明說明書(補件)/96-10/96123707 13 200810922[3] (wherein 'Rl, R2 represents 氲 or methyl, and η represents 1~; [an integer of 2). (17) The active energy ray-curable composition according to any one of the above (12) to (15), wherein the above (meth)acrylic acid epoxy ester is bisphenolphthalein epoxypropyl ether (fluorenyl) Acrylate. The active energy ray-curable composition of any one of the above-mentioned (12) to (17), wherein the (meth) acrylate having a bifunctional or higher functional group of the above epoxyalkyl group is represented by the following formula [ 4] indicates, .[化4] 312ΧΡ/invention specification (supplement)/96-10/96123707 13 200810922
(其中，R表示氫或甲基，n、m表示1〜4之整數）。 (發明效果） 本發明之活性能量射線硬化性組成物係透明且光學畸 變小’具有韌性、耐熱性，且二次加工性優良，並具有高 厚度精度，可使1〜2000 // m左右之自極薄至極厚的薄膜 ®容易地連續成形。 另外’由本發明之活性能量射線硬化性組成物所構成之 透明薄膜，不僅光學畸變小，具有優良之韌性、耐熱性， 且積層之簡便性、厚度精度、成本方面亦優良。 積層該薄膜所得之光碟除了具有上述優良之光學·物理 特性之外，亦具有可進一步改善碟片之翹曲的效果，可極 為有效地用作次世代型碟片之高密度記錄媒體， 鲁光碟、UD0等光碟。 【實施方式】 本發明之活性能量射線硬化性組成物係以特定比例含 有（曱基）丙烯酸胺基甲酸酯、（曱基）丙婦酸笨氧酉匕 基）丙烯酸環氧酿、（曱基）丙烯酸脂環_、 曰 之2官能以上的（甲基）丙烯酸酉旨之任一種而成的^兀土 〜（C)樹脂組成物， （ (A)(甲基）丙烯酸胺基曱酸酯3〇〜⑽重旦八 丙烯酸苯氧酯20〜50重量份、n 里知（曱基） (甲基)丙烯酸環氧酯〇〜 312XP/發明說明書(補件)/96-10/96123707 14 200810922 30重量份； (B) (曱基）丙烯酸胺基甲酸酯40〜60重量份、（曱美） 丙烯酸環氧酯1〇〜4〇重量份、（曱基）丙烯酸脂環醋〇〜 30重量份； (C) (甲基）丙烯酸胺基甲酸酯20〜70重量份、具有環氧 烧基之2官能以上之（甲基）丙烯酸酯10〜6〇重量份、（甲 基）丙烯酸環氧酯〇〜30重量份、（甲基）丙烯酸苯氧酯1〇 〜5 0重量份。 作為本發明之活性能量射線硬化性組成物之構成成分 之一的（甲基）丙烯酸胺基甲酸酯，為至少二官能以上之 (甲基）丙烯酸胺基曱酸酯寡聚物，由下述通式[丨]表示， [化1] 蜷料仏魴㈣⑽❹咖盼❹崎綱㈣疒酿【1 ] (其中，上述通式[1]中，1表示含有羥基之（甲基）丙烯酸 酯之殘鏈部分，R2表示異氰酸酯殘基，Rs表示醇殘基或自 聚醚二醇、聚酯二醇及聚碳酸酯二醇中選擇之至少1種二 醇殘基，R4表示氫或者甲基，n表示2至2〇之整數）。 對（甲基）丙烯酸胺基甲酸酯之合成方法並未加以特別 限定，例如，可藉由於如下化合物中加成含有羥基之（甲 基）丙烯酸酯而合成，上述化合物係將脂肪族多元醇或者 脂肪族多元醇環氧丙基醚與脂環式二異氰酸酯進行胺基 甲酸酯縮合而成之化合物。 1 3 UXP/發明說明書(補件)/%-i0/96123707 15 200810922 上述通式[1]中之R!係於分子内具有至少1個（曱基）丙 烯醯基與至少1個羥基之含有羥基之（甲基）丙烯酸酯殘 :鏈。 :作為含有羥基之（甲基）丙烯酸酯成分之具體例，例如可 舉出（曱基）丙烯酸2-經乙g旨、（曱基）丙烯酸2-經丙酯、 (甲基）丙烯酸4-羥丁酯、（甲基）丙烯酸6-羥己酯、環己 烧二曱醇單（曱基）丙烯酸酯、（曱基）丙烯酸2-羥乙酯與 己内酯之加成物、（甲基）丙烯酸4-羥丁酯與己内酯之加 肇成物、二經甲基丙烧二丙稀酸酯、季戊四醇三丙烯酸酯、 雙季戊四醇五丙烯酸酯等。該等可單獨使用一種，或併用 兩種以上。彼等之中，較佳為（甲基）丙烯酸2-羥乙酯、（曱 基）丙烯酸2-羥丙酯、（曱基）丙烯酸4 —羥丁酯。 上述通式[1 ]中之R2係二異氰酸酯殘基，作為具體例， 除了曱苯二異氰酸酯、4, 4-二苯基曱烷二異氰酸酯等芳香 族系之二異氰酸酯之外，亦可舉出二異氰酸己二酯、異佛 馨f酮二異氰酸酯、雙（4 —異氰酸基環己基）曱烷、1，2-氫化 苯二甲基二異氰酸酯、丨，4-氫化苯二甲基二異氰酸酯、氫 =四甲基苯二甲基二異氰酸酯、降稍烷二異氰酸酯等脂肪 族系”異氰酸酯。該等可單獨使用一種，或併用兩種以 上°亥等之中，較佳為異佛爾酮二異氰酸酯、雙（4—異氰 ’酸基環己基)甲烷等脂環式二異氰酸酯，其中因異佛爾： -一異氰酸酯於光線透過率、耐熱變形性、耐熱分解性方面 優良，故更佳。 上述通式[1 ]中之係2官能醇殘基，作為具體例，除 312XP/發明說明書(補件)/96-10/96123707 ^ 200810922 了乙二醇、丙二醇、丁二醇、己二醇等烷基多元醇之外， 亦可舉出聚乙二醇、聚丙二醇、聚丁二醇等聚越多元醇等 二醇系化合物；聚乙二醇、聚丙二醇、聚丁二醇、卜甲基 ：丁二醇等聚醚二醇類；新戊二醇、乙二醇、二乙二醇、丙 二醇、1，6-己二醇、i，4-丁 二醇、—壬二醇、11〇 癸 -醇、3-甲基戊二醇、2’4-二乙基戍二醇、三環癸烧二甲 醇、1，4-環己烷二甲醇、；!，2_環己烷二甲醇、u —環己烷 二曱醇、環己烷二醇、氫化雙酚A、雙酚A等二醇類；於 上述二醇類中加成環氧乙烧、環氧丙燒、環氧丁院等環氧 烧而成之聚謎改質二醇類；藉由上述二醇類與號玉白酸、鄰 苯二甲酸、六氫鄰苯二甲酸、對苯二甲酸、己二酸、壬二 酸、四氫鄰苯二甲酸等多元酸類或該等多元酸之酸肝類的 反應而獲得之聚酯二醇，或藉由上述二醇類與己内 酉旨、r-丁㈣、[戊内酯、r戊内酿#内酯類之反應 而獲得的聚己内酯二醇等聚酯二醇類；藉由上述二醇類及 上述多元酸類與卜己内酯、厂丁内醋、厂戊内醋、 戊内醋等内醋類的反應而獲得之己内醋改質聚醋二醇 類.；芳香族聚碳酸㈣朗族聚碳酸㈣聚碳酸醋二醇 類；聚丁二稀二醇類等。該等可單獨使用一種，或併用兩 種以亡彼等之中，較佳為丁二醇骨架或聚鍵二醇類、聚 酯二醇類、聚碳酸酯二醇類。 >於賦予硬化物fe；性之情況下’較佳為脂肪族聚碳酸醋二 醇另外於亦重視組成物之塗敷性之情況下較佳為具 有丁二醇骨架者。 312XP/發明說明書(補件)/96-1 〇/96123707 17 200810922 將使異佛爾酮二異氰酸醋與四乙二醇進行胺基曱酸醋 縮合之末端進行（甲基）丙烯酸化而獲得之（甲基）丙烯酸 -胺基曱酸酯之中，較理想的是如下構造，即，數量平均分 :子量為6〇〇〜10000，進而較佳為10〇〇〜4〇〇〇，使分子= 存在10〜18個胺基甲酸醋鍵之構造的末端與丙稀酸4_經 丁酯反應而獲得之構造，其係由下述構造式[2 ]表示。 [化 2] ^(wherein R represents hydrogen or a methyl group, and n and m represent an integer of 1 to 4). (Effect of the Invention) The active energy ray-curable composition of the present invention is transparent and has small optical distortion. It has toughness and heat resistance, is excellent in secondary workability, and has high thickness precision, and can be about 1 to 2000 // m. The film® from very thin to very thick is easily formed continuously. Further, the transparent film composed of the active energy ray-curable composition of the present invention has excellent optical toughness, excellent toughness and heat resistance, and is excellent in ease of lamination, thickness accuracy, and cost. In addition to the above-mentioned excellent optical and physical properties, the optical disc obtained by laminating the film has an effect of further improving the warpage of the disc, and can be extremely effectively used as a high-density recording medium for the next-generation disc, Luguang disc. , UD0 and other CDs. [Embodiment] The active energy ray-curable composition of the present invention contains (mercapto) urethane amide, (mercapto) acetophenoxy phenoxy acrylate) in a specific ratio, (曱(a) acrylate _, 曰 2 2 2 任 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 Ester 3 〇 ~ (10) heavy octadecyl phenoxy acrylate 20 to 50 parts by weight, n ri (methylene) (meth) acrylate epoxy ester 〇 ~ 312XP / invention manual (supplement) / 96-10/96123707 14 200810922 30 parts by weight; (B) 40 parts by weight of (mercapto) acrylate urethane, (comparable) epoxide acrylate 1 〇 ~ 4 〇 parts by weight, (fluorenyl) acrylate ring vinegar 〇 ~ 30 parts by weight; (C) 20 to 70 parts by weight of (meth)acrylic acid urethane, (meth)acrylate having 2 or more functional groups having an epoxy group, 10 to 6 parts by weight, (meth) Acrylic epoxy oxime 30 30 parts by weight, phenoxy (meth) acrylate 1 〇 to 50 parts by weight. As the active energy ray of the present invention The (meth)acrylic acid urethane which is one of the constituent components of the chemical composition is an at least difunctional or higher (meth)acrylic acid amino phthalate oligomer, which is represented by the following formula [丨] (1) 蜷 仏鲂 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四Isocyanate residue, Rs represents an alcohol residue or at least one diol residue selected from the group consisting of polyether diol, polyester diol and polycarbonate diol, R4 represents hydrogen or methyl, and n represents 2 to 2 〇. The method for synthesizing the (meth)acrylic acid urethane is not particularly limited, and for example, it can be synthesized by adding a hydroxyl group-containing (meth) acrylate to the following compound, and the above compound will be A compound obtained by condensing an aliphatic polyol or an aliphatic polyol glycidyl ether with an alicyclic diisocyanate. 1 3 UXP/Invention Manual (supplement)/%-i0/96123707 15 200810922 The R! in the above formula [1] has at least one (indenyl) C in the molecule. The (meth) acrylate residue having a hydroxyl group and at least one hydroxyl group is a chain: As a specific example of the hydroxyl group-containing (meth) acrylate component, for example, (mercapto)acrylic acid 2-乙克,(曱基)acrylic acid 2-propyl acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, cyclohexanol di(mercapto) acrylate , an adduct of 2-hydroxyethyl acrylate and caprolactone, a ruthenium of 4-hydroxybutyl (meth) acrylate and caprolactone, and a dimethyl propylene diacetate Ester, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and the like. These may be used alone or in combination of two or more. Among them, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate are preferred. In addition to the aromatic diisocyanate such as toluene diisocyanate or 4, 4-diphenyldecane diisocyanate, an R 2 -based diisocyanate residue in the above formula [1] may be mentioned. Hexyl diisocyanate, isophora ketone diisocyanate, bis(4-isocyanatocyclohexyl)decane, 1,2-hydrogenated dimethyl diisocyanate, hydrazine, 4-hydrogenated phthalic acid An aliphatic "isocyanate" such as bis-isocyanate, hydrogen = tetramethyl dimethyl dimethyl diisocyanate or decane diisocyanate. These may be used singly or in combination of two or more kinds, preferably different. An alicyclic diisocyanate such as phorone diisocyanate or bis(4-isocyano-cyclohexyl)methane, wherein isophor:-isocyanate is excellent in light transmittance, heat deformation resistance, and heat decomposition resistance. More preferably. The above-mentioned bifunctional alcohol residue in the above formula [1], as a specific example, in addition to 312XP / invention specification (supplement) / 96-10/96123707 ^ 200810922 ethylene glycol, propylene glycol, butanediol In addition to alkyl polyols such as hexanediol, polyethylene glycol is also mentioned. a glycol compound such as a polyhydric alcohol such as an alcohol, a polypropylene glycol or a polybutylene glycol; a polyether glycol such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol or polymethylene glycol; and neopentyl glycol; Ethylene glycol, diethylene glycol, propylene glycol, 1,6-hexanediol, i,4-butanediol, decanediol, 11-anol, 3-methylpentanediol, 2'4- Diethyl decanediol, tricycloanthracene dimethanol, 1,4-cyclohexanedimethanol, ;, 2_cyclohexanedimethanol, u-cyclohexanedimethanol, cyclohexanediol, Hydrogenated diols such as bisphenol A and bisphenol A; and polygly-modified diols obtained by epoxy burning such as epoxy bake, propylene bromide, and epoxy butyl so as to be added to the diol; By the above-mentioned diols and polybasic acids such as leucovorin, phthalic acid, hexahydrophthalic acid, terephthalic acid, adipic acid, sebacic acid, tetrahydrophthalic acid or the like The polyester diol obtained by the reaction of acid acid liver, or obtained by the reaction of the above diol with hexanol, r-butyl (tetra), [valerolactone, r-pentane # lactone Polyester diol such as polycaprolactone diol; The diol and the above-mentioned polybasic acid and the internal vinegar of the caprolactone, the vinegar, the vinegar, the vinegar, the vinegar, etc. Polycarbonate (4) Longan polycarbonate (IV) Polycarbonate glycols; polybutylene dilute glycols, etc. These may be used alone or in combination with two, preferably a butanediol skeleton or Polyglycol diols, polyester diols, and polycarbonate diols. > In the case of imparting a cured product, it is preferred that the aliphatic polycarbonate diol is additionally coated with the composition. In the case of compressibility, it is preferred to have a butanediol skeleton. 312XP/Invention Manual (Supplement)/96-1 〇/96123707 17 200810922 Will make isophorone diisocyanate and tetraethylene glycol amine Among the (meth)acrylic acid-amino phthalic acid ester obtained by (meth) acylation of the end of the acid vinegar condensation, it is desirable to have the following structure, that is, the number average score: the sub-amount is 6〇〇 ~10000, and further preferably 10〇〇~4〇〇〇, so that the molecule = the end of the structure of 10~18 amino citrate bonds 4_ configured by dilute acid ester obtained by the reaction, which is based [2] represented by the following structure formula. [化2] ^
(其中，上述構造式[2]中，n表示4以上之整數 對於作為本發蚊㈣能㈣㈣化性組絲之構成 成分之-的（甲基)丙烯酸苯氧醋，並未加以特別限制，詳 細而言，由於具有兩個以下（甲基）丙烯酿基之（甲基）丙稀 φ酸苯氧醋單體分子量相對較低、黏度低、且單獨之聚合物 之延伸率大，因此，容易降低組成物之黏度且容易改良物 性之，造較為優良。尤其較佳為，於分子内至少具有工個 2丙本基組成、碳原子數為8以上之燒基組成、表氯醇縮 &組成及乙二醇縮合組成中之任—種者，或者，於分子内 至少具有1個異丙苯基組成或者碳原子數為8以上之烧基 組成、及表氯醇縮合組成或者乙二醇縮合組成者。 ㈣而言，例如可舉出（甲基）㈣酸苯氧基乙酯、苯氧 土聚乙二酵（甲基）丙稀酸酯、（甲基）丙烯酸苯氧基丙醋、 312ΧΡ/發明說明書(補件)/96•膽61237〇7 18 200810922 苯氧基聚丙二醇（曱基）丙烯酸酯、壬基苯氧基乙二醇（甲 基）丙烯酸酯、壬基苯氧基聚乙二醇（曱基）丙稀酸酯、壬 基笨氧基丙二醇（曱基）丙烯酸酯、 1 (曱基）丙烯酸酯、對異丙苯基苯氧基乙二醇（曱基）丙烯酸 酯、對異丙苯基苯氧基聚乙二醇（曱基）丙烯酸酯、對異丙 苯基苯氧基丙二醇（曱基）丙烯酸酯、對異丙苯基苯氧基聚 丙一醇（曱基）丙烯酸酯、2-經基-3-苯氧基-丙基（甲基） 丙烯酸酯、雙酚A環氧乙烷加成二（曱基）丙烯酸酯、雙酚 A聚環氧乙烷加成二（曱基）丙烯酸酯、雙酚A環氧丙烷加 成二（曱基）丙烯酸酯、雙酚A聚環氧丙烷加成二（甲基） 丙烯酸酯等。尤其是，更佳為壬基苯氧基乙二醇（曱基） 丙烯1¾、壬基笨氧基丙二醇（曱基）丙烯酸酯、對異丙苯 基苯氧基乙二醇（甲基）丙烯酸酯、2_羥基_3_苯氧基—丙基 (曱基）丙烯酸醋（=表氯醇改質（曱基）丙稀酸苯氧醋）。土 對於作為本發明之活性能量射線硬化性組成物之構成 土：之-的(甲基)丙烯酸環氧醋，並未加以特別限 ;有兩個以上”基）丙稀酿基之（曱基）丙稀酸環氧醋实 構或Γ性高’於丙烯酿基之反應中物性易於提 醚、聚丙二醇二環—U己二醇二丙基 丙三醇二環氧丙基_ 4丙基醚、 雔酪Α τ丞丙烷二核氧丙基醚、筒化 環氧丙基醚 又齡氧丙基醚、2,2_二漠新戊 k虱化 312X17 發明說明書(補件)/96-10/96123707 19 200810922 三經甲基乙烧三環氧丙基趟、脂肪族多元醇聚環氧丙基 ϋ、二環氧化聚乙二醇、蓖麻油聚環氧丙基鱗、環己烧二 曱醇二環氧丙基醚、間苯二酚二環氧丙基醚、雙酚Α二環 氧丙基醚、雙酚F二環氧丙基醚、雙酚s二環氧丙基醚: 雙紛A環氧乙烧加成二環氧丙基醚、雙紛A環氧丙烧加成 二環氧丙基醚、藉由鄰苯二曱酸及二氫鄰苯二甲酸等二元 酸與表鹵醇之反應而獲得之二環氧丙基g旨化合物；藉由胺 基苯盼及雙（4-胺基苯基）曱烧等芳香族胺與表_醇之反 應而獲得之環氧化合物；六氟 ^普^一-環氧基丙氧幻苯幻丙烧’盼類紛酸清漆 型環氧樹脂及Μ㈣清漆型環氧_等多官能環氧化 合物之（甲基）丙烯酸加成體。(In the above structural formula [2], n represents an integer of 4 or more, and is not particularly limited as the (meth)acrylic acid phenoxy vinegar which is a constituent component of the (four) (four) chemical group of the present mosquito (4). In detail, since the (meth) propylene oxy phenoxy phenate having two or less (meth) acryl groups has a relatively low molecular weight, a low viscosity, and a large elongation of a single polymer, It is easy to reduce the viscosity of the composition and to improve the physical properties, and is preferably excellent. Particularly preferably, it has at least a composition of 2 propyl groups in the molecule, a composition of a carbon atom of 8 or more, and epichlorohydrin & Any one of the composition and the ethylene glycol condensation composition, or a composition having at least one cumene group or a carbon number of 8 or more in the molecule, and epichlorohydrin condensation composition or ethylene (4) Examples thereof include phenoxyethyl (meth)(tetra) acid, phenoxylate poly(ethylene) acrylate, and phenoxypropyl (meth)acrylate. Vinegar, 312 ΧΡ / invention manual (supplement) / 96 • biliary 61237 〇 7 18 200810 922 phenoxy polypropylene glycol (mercapto) acrylate, nonylphenoxy ethylene glycol (meth) acrylate, nonyl phenoxy polyethylene glycol (fluorenyl) acrylate, sulfhydryl Propylene glycol (mercapto) acrylate, 1 (fluorenyl) acrylate, p-cumylphenoxyethylene (decyl) acrylate, p-cumyl phenoxy polyethylene glycol (fluorenyl) Acrylate, p-cumylphenoxypropanediol (fluorenyl) acrylate, p-cumylphenoxypolypropanol (mercapto) acrylate, 2-carbyl-3-phenoxy-propene Base (meth) acrylate, bisphenol A ethylene oxide addition bis(indenyl) acrylate, bisphenol A polyethylene oxide addition bis(indenyl) acrylate, bisphenol A propylene oxide plus Into bis(indenyl) acrylate, bisphenol A polypropylene oxide addition di(meth) acrylate, etc. In particular, more preferably decyl phenoxy glycol (fluorenyl) propylene 13⁄4, fluorenyl Phenoxypropanediol (mercapto) acrylate, p-cumylphenoxyethylene glycol (meth) acrylate, 2-hydroxy-3-phenoxy-propyl (fluorenyl) propyl Sour vinegar (= epichlorohydrin modified (mercapto) acrylic acid phenoxy vinegar). As the constituent material of the active energy ray hardening composition of the present invention: (meth)acrylic epoxy vinegar, It is not particularly limited; there are two or more "base" acrylonitrile-based (mercapto) acrylic acid acetal vinegars with high or high enthalpy. In the reaction of propylene, the physical properties are easy to extract ether, polypropylene glycol Cyclo-U-hexanediol dipropyl glycerol diepoxypropyl _ 4 propyl ether, 雔 Α Α 丞 丞 丞 dihydro propyl propyl ether, tubular epoxypropyl ether and oxypropyl ether 2,2_二漠新戊k虱化312X17 invention manual (supplement)/96-10/96123707 19 200810922 trimethyl sulfonate triepoxypropyl hydrazine, aliphatic polyol polyepoxypropyl hydrazine, Dicycloepoxidized polyethylene glycol, castor oil polyepoxypropyl scale, cyclohexane terpineol diepoxypropyl ether, resorcinol diepoxypropyl ether, bisphenol quinone diepoxypropyl ether , bisphenol F diglycidyl ether, bisphenol s diglycidyl ether: double bis, A epoxy Ethylene sulphide addition diepoxy propyl ether, double argon A epoxidized propylene, addition of diepoxy propylene Phthalic acid a diepoxypropyl g-derived compound obtained by the reaction of a dibasic acid such as dihydrophthalic acid with an epihalohydrin; an aromatic amine such as an aminobenzene and a bis(4-aminophenyl) oxime Epoxy compound obtained by reaction with the table-alcohol; hexafluoro-p-mono-epoxypropoxy pheno- phenanthrene- sulphur-like varnish-type epoxy resin and bismuth (four) varnish-type epoxy _ and other polyfunctional (meth)acrylic acid addition of an epoxy compound.
進而’使雙酚Α型環氧樹脂、雙酚F型環氧樹脂、雙酚 型環氧樹脂、四漠雙紛A型環氧樹脂、_贿清漆型 環氧樹脂、甲酚酚醛清漆型環氧樹脂、雙苯氧基弟二環氧 丙基輕、雙苯氧基ϋ乙醇二環氧丙基驗、 氧樹脂、氫化雙紛F型環氧樹脂、環己燒二甲醇二環氧丙 基醚、三環癸烧二甲醇二環氧丙基醚等環氧樹脂，與（甲 基）丙烯酸、（甲基）丙烯酸二聚物、己内醋改質（甲基）丙 烯酸等不飽和-元酸類反應而獲得之（甲基） 酯類等。 該等（f基）丙烯酸環氧醋之中，因可提高所獲得之組成 物之硬化後之耐熱性，故較佳為作為㈣A二環氧丙基 驗、雙朌F二環A丙基ϋ、雙紛纟環氧乙燒加成二環氧丙 312XP/發明說明書(補件)/96-10/96123707 20 200810922 基鱗、雙酚A環氧丙炫加成— 合物之Γ审苴、 成一衣虱丙基醚等多官能環氧化 土）丙烯酸加成體的雙酚型（ 酯化合物類、雙酚Α tμ IT基）丙烯酸環氧 基)丙婦酸環：：、=?丙烯酸環氧酿、雙㈣型(甲 雙龄A型（甲其、曰又甲基）兩婦酸環氧醋、四溴 二=):r= (甲基)丙烯西…又 丙烯酸環氧酯等雙酚型 烯酉文裱巩酯類，其中，因黏度與 =更:她㈣(甲基)丙稀酸環_:= ㈣環氧酿，特佳為雙紛A環氧丙基㈣甲基）丙^ 基)另外，特佳為由下述通式[3]所表示之雙紛型環氧（甲 [化3]Further, 'making bisphenol fluorene type epoxy resin, bisphenol F type epoxy resin, bisphenol type epoxy resin, Si Mo Shuang A type epoxy resin, _ brie lacquer type epoxy resin, cresol novolak type ring Oxygen resin, bisphenoxy diepoxypropyl light, bisphenoxy oxime ethanol diepoxypropyl test, oxygen resin, hydrogenated double F type epoxy resin, cyclohexane dimethanol diepoxypropyl Epoxy resin such as ether, tricycloanthracene dimethanol diglycidyl ether, and unsaturated (meth)acrylic acid, (meth)acrylic acid dimer, caprolactone modified (meth)acrylic acid, etc. A (meth) ester obtained by an acid reaction or the like. Among these (f-based) acrylic epoxies, since the heat resistance after curing of the obtained composition can be improved, it is preferably used as (iv) A-diepoxypropyl group, biguanide F-bicyclic A propyl group. , double bismuth epoxy Ethylene Ethylene addition diethylene propylene 312XP / invention manual (supplement) / 96-10/96123707 20 200810922 squama, bisphenol A epoxy propylene shuang addition - a polyfunctional epoxidized earth such as a propyl propyl ether) bisphenol type (ester compound, bisphenol Α tμ IT based) acrylate epoxy group acrylic acid ring::, =? acrylic epoxy Stuffed, double (four) type (A double age A type (Kaki, 曰 and methyl) two women's acid vinegar, tetrabromo two =): r = (meth) propylene West ... and acrylate epoxide Type of olefinic sulfonamide, in which, due to viscosity and = more: she (tetra) (methyl) acrylate ring _: = (four) epoxy brewing, especially good for double bis-epoxypropyl (tetra) methyl) ^基) In addition, it is a double-type epoxy represented by the following general formula [3] (A)
(其中，上述通式[3]中，R1、R2表示氫或者曱基，n表示 1至12之整數）。 另外，於Ik著所獲得之組成物之聚合而降低體積收縮率 之方面而言，較佳為處於重量平均分子量700〜4000之範 圍’上述通式[3]中較佳為n = 2〜12之範圍。 若上述雙酚型（甲基）丙烯酸環氧酯之重量平均分子量 312XP/發明說明書(補件)/96-10/96123707 21 200810922 :於700，貝仏著所獲得之組成物之聚合而體 大:當使用所獲得之活性能量射線硬化性組 二 之保護膜或透光層時，存在光碟之輕曲增大之傾向另 外’若雙驗型（甲基）丙烯酸環氧酯之重量平均分子量 侧’载成物之黏度會變得非f高，U存在加工性降 此’本發明中，當使用雙紛型(甲基)丙埽酸 衣虱-曰日守’較佳為使用重量平均分子量為7〇〇〜4_者。 種Π(甲基)丙烯酸環氧，可視需要混合使用i種或者2 裡Μ上。 =於作為本發明之活性能量射線硬化性組成物之構成 —刀上之6Κ曱基)丙稀酸脂環酷成分，並未加以特別限 =細而言為具有至少i官能以上之(甲基)_基之 甲基)㈣酸脂環轉㈣，職構造為賦料化物 二硬度t構，：較佳例可舉出：降稻基環、金剛院基 二一?:5烷％、三環癸烷環、四環十二烷環、稍烯環、 力虱化不' %、來氫化恩環、三環烯、膽固醇環等類固醇骨 =，、毛地黃⑷咐師衰、樟腦環、異樟腦環、 :帖％ η塞’壤、二祐環、三結環、類固料素環等， /、，因所獲得之活性能量射線硬化組成物之表面硬度優 又二較佳為具有三環癸烷骨架之(甲基)丙烯酸酯。 或Π種:基上)丙稀酸脂環醋成分可視需要滿合使用丨種 ^ ;乍為本么明之，舌性能量射線硬化性組成物之構成 勿之一的具有環氧烷之2官能以上之（甲基）丙烯酸 3_發明說明書(補件)/96·10/9612遍 22 200810922 酯，並未加以特別限定，為了提高塗敷性，較佳為硬化前 ，度杈減表面張力較高者。其原因在於，於彻模余法 等一般製膜方法將組成物進行製彻去、主 厚度精度獲得塗膜，且表面張τ;:;易者易於以高 了“表面之平滑性。為了於硬化後具有塗膜之尺寸穩定 為料適#之硬度的構造，較佳為#由2官能以 上之（甲基）丙細酸s旨官能基賦予塗膜以交聯構造，且主鍵 為適度剛直之骨架，可由下述構造式[4]表示。 [化4](In the above formula [3], R1 and R2 represent hydrogen or a fluorenyl group, and n represents an integer of 1 to 12). Further, in terms of reducing the volume shrinkage ratio of the composition obtained by Ik, it is preferably in the range of a weight average molecular weight of 700 to 4000. In the above formula [3], preferably n = 2 to 12 The scope. If the weight average molecular weight of the above bisphenol type (meth)acrylic acid epoxy ester is 312XP/invention specification (supplement)/96-10/96123707 21 200810922: at 700, the polymerization of the obtained composition is large. : When using the protective film or light-transmitting layer of the active energy ray-curable group 2 obtained, there is a tendency that the light curve of the optical disk is increased. In addition, the weight average molecular weight side of the double-type (meth)acrylic acid epoxy ester is used. 'The viscosity of the carrier will become non-f high, and U has a decrease in workability.' In the present invention, it is preferred to use a weight average molecular weight when using a double-type (methyl)propionic acid 虱-曰日守' For 7〇〇~4_. A kind of bismuth (meth) acrylate epoxy can be mixed with i or 2 Μ as needed. = as a constituent of the active energy ray-curable composition of the present invention - a 6-mercapto-acrylic acid ring-cooling component on a knife, which is not particularly limited to have at least an i-functional or higher (methyl group) (4) methyl group) (4) acid ester ring (4), the structure is the material of the two hardness t structure, the preferred examples can be mentioned: the rice base ring, the King Kong base two?: 5 alkane%, three Cyclodecane ring, tetracyclododecane ring, slightly olefinic ring, hydrazine not %%, hydrazine ring, tricycloolefin, cholesterol ring and other steroid bones =, foxglove (4) 咐 衰 樟, camphor ring , 樟 樟 、 , : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : A (meth) acrylate having a tricyclodecane skeleton. Or Π : 基 丙 丙 丙 丙 丙 丙 丙 丙 丙 丙 丙 丙 丙 丙 丙 丙 丙 丙 丙 丙 丙 丙 丙 丙 丙 丙 丙 丙 丙 丙 丙 丙 丙 丙 丙 丙 丙 丙 丙 丙 丙 丙 丙 丙 丙The above (meth)acrylic acid 3_invention specification (supplement)/96·10/9612 times 22 200810922 ester is not particularly limited, and in order to improve coating properties, it is preferred to reduce the surface tension before curing. The taller. The reason is that the composition is formed by a general film forming method such as a die-molding method, and the film thickness is obtained by the main thickness precision, and the surface tension τ is easy to increase the smoothness of the surface. After the hardening, the coating film has a structure in which the size of the coating film is stable to the hardness of the material. It is preferable that the functional group based on the bifunctional or higher (meth)propionic acid s imparts a crosslinked structure to the coating film, and the primary bond is moderately rigid. The skeleton can be expressed by the following structural formula [4].
[其中，R表示氫或者曱基，n、m表示}〜4之整數]。 作為具有環氧烷之2官能以上之（甲基）丙烯酸酯化合 _物組成，可舉出如下之例：乙二醇改質雙酚A二丙烯酸 酯、乙二醇改質雙酚F二丙烯酸酯、（聚）乙二醇二丙烯酸 醋、（聚）丙二醇改質雙酚A二丙烯酸酯、（聚）丙二醇改質 雙紛F二丙烯酸酯、（聚）乙丙二醇改質雙酚a二丙烯酸 酯、（聚）乙丙二醇改質雙酚F二丙烯酸酯、（聚）丙二醇二 丙烯酸酯、甘油環氧丙基醚二丙烯酸酯、三丙二醇環氧丙 -基醚二丙烯酸酯、丁二醇二丙烯酸酯、己二醇二丙稀酸 酯、E0改質新戊二醇二丙烯酸酯、P0改質新戊二醇二丙 烯酸酯、E0改質三羥甲基丙烷三丙烯酸酯、P0改質三_ 312XP/發明說明書(補件)/96-10/96123707 23 200810922 甲基丙烧三丙烯酸酯、E0 ?文質季戍四醇三汚稀酸醋、p〇 改質季戊四醇三丙烯酸酯、E0改質季戊四醇四丙㈣酉旨、 P0改質季戊四醇四丙烯酸酯、E0改質雙季戊四 及六 丙烯酸S旨、PG改質雙季戊四醇戊及六丙稀酸@旨等。其中 因黏度低且硬化前之表面張力幸交高’可賦予硬化後之塗膜 以適度之硬度，故較佳為即改質雙紛A:丙烯酸醋。' 於衣備本發明之活性能量射線硬化性組成物時，上述各 構—成成分按照以下（A)〜（c)之比例調配，於適度之黏^ (薄膜化加工性）、韌性、耐熱變形性、耐熱分解性、二$ 加工=成本之方面較佳，《其於可獲得用⑨次世代型碟 片之高密度記錄媒體（藍光光碟或UD〇等）之薄膜方較 佳。 议 [本發明之第一硬化性組成物（A)] (A)(甲基）丙烯酸胺基甲酸酯3〇〜6〇重量份、（甲美 酸酯20〜50重量份、及(曱基)丙烯酸環氧酯〇〜3〇 此時，若（甲基）丙烯酸胺基甲酸酯未滿30重量份則五 =差，若超過60重量份則耐熱分解性方面差，故不理邦軔 二（甲基）丙烯目文笨氧酯未滿2 〇重量份，則組成物之 冋且非常薄為1㈣，故以高厚度精度獲得非常厚為2〇〇^η //m之薄膜時之薄臈化加工性差，若 ^ 過於軟質而強度、二次加工性方面較差。再者重里，則 丙烯酸環氧i旨係視需要調配者，若調配，則可獲得接含 熱變形性、耐熱分解牲、二次加工性、成本之效果，：： 312XP/發明說明書(補件)/96·10/96123707 24 200810922 過30重量份，則因樹脂組成物變為高黏度，故不利於薄 膜形成’且亦會降低硬化物之光線透過率，尤其於獲得用 :於次世代型碟片之高密度記錄媒體（例如藍光光碟或_ : 荨）的薄膜方面不理想。 [本發明之第二硬化性組成物（B)] (B)(甲基)丙烯酸胺基甲酸酯4〇〜6〇重量份、（甲基)丙烯 酸玉衣氧酉旨1 〇〜4 〇曹晉/f合、；^ γ|I ^ 里里切及（甲基）丙烯酸脂環酯〇〜3〇 重量份[wherein R represents hydrogen or a fluorenyl group, and n and m represent an integer of 〜4]. Examples of the (meth) acrylate compound composition having a difunctional or higher functional group of an alkylene oxide include ethylene glycol modified bisphenol A diacrylate and ethylene glycol modified bisphenol F diacrylic acid. Ester, (poly) ethylene glycol diacrylate vinegar, (poly) propylene glycol modified bisphenol A diacrylate, (poly) propylene glycol modified double F acrylate, (poly) ethylene propylene glycol modified bisphenol a diacrylic acid Ester, (poly)ethylene propylene glycol modified bisphenol F diacrylate, (poly) propylene glycol diacrylate, glycerol epoxy propyl ether diacrylate, tripropylene glycol propylene propylene ether diacrylate, butanediol II Acrylate, hexanediol diacrylate, E0 modified neopentyl glycol diacrylate, P0 modified neopentyl glycol diacrylate, E0 modified trimethylolpropane triacrylate, P0 modified three _ 312XP / invention manual (supplement) /96-10/96123707 23 200810922 methyl propyl triacrylate, E0 文 戍 戍 戍 tetraol three dirty acid vinegar, p 〇 modified pentaerythritol triacrylate, E0 change Pentylenetetraol tetrapropyl (IV), P0 modified pentaerythritol tetraacrylate, E0 modified double And S pentylenetetrazol purpose hexaacrylate, PG modified dipentaerythritol ACID @ pentyl and six other purpose. Among them, because the viscosity is low and the surface tension before hardening is high, the coating film after hardening can be imparted with moderate hardness, so it is preferable to modify the double A: acrylic vinegar. In the case of the active energy ray-curable composition of the present invention, the above-mentioned constituent components are formulated in the following ratios (A) to (c), and are moderately bonded (thinning processability), toughness, and heat resistance. Deformability, thermal decomposition resistance, and processing cost are preferable. "It is preferable to obtain a film of a high-density recording medium (Blu-ray disc, UD, etc.) using a 9-generation type disc. [The first curable composition (A) of the present invention] (A) (meth)acrylic acid urethane 3 〇 to 6 〇 parts by weight, (methyl methacrylate 20 to 50 parts by weight, and (曱Acrylic epoxy oxime 〇3 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若When the bis(meth)propene phenoxy ester is less than 2 parts by weight, the composition is very thin and is 1 (four), so when a film having a thickness of 2 〇〇^η //m is obtained with high thickness precision The thinning processability is poor, and if it is too soft, the strength and secondary workability are inferior. In addition, the acrylic epoxy i is intended to be blended as needed, and if it is blended, it can be thermally deformed and heat resistant. Decomposition, secondary processing, and cost effects:: 312XP/Invention Manual (Supplement)/96·10/96123707 24 200810922 After 30 parts by weight, the resin composition becomes highly viscous, which is not conducive to film formation. 'It also reduces the light transmission rate of the hardened material, especially for obtaining high density recording media for the next generation disc. (for example, a Blu-ray disc or a _: 荨) film is not preferable. [The second curable composition (B) of the present invention] (B) (meth)acrylic acid urethane 4 〇 to 6 〇 by weight, (Meth)acrylic acid jade oxime 1 〇 4 4 4 4 〇 〇 ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ;
此時，若（甲基）丙烯酸胺基曱酸酯未滿40重量份則韌 性差，若超過60重量份則耐熱分解性方面較差。若（甲基） 丙烯酸環氧醋未滿10重量份，則組成物之耐熱變形： 、,若超過40重里伤則組成物之黏度高而薄膜化加工性 硬化物t光線透過率降低。（甲基）丙烯酸月旨環醋係視 需要調配者，若調配’料獲得提高組成物之薄膜化加工 性i耐熱變形性、耐熱分解牲、成本之效果，若超過㈣ 重1份，則樹脂組成物之硬化收縮增大，且硬化物容易破 碎，因此難以成形為輥狀薄膜，二次加工性亦較差。 [本發明之第三硬化性組成物（C )] («(甲基）丙烯酸胺基甲酸酯20〜70重量份、具有環氧烷 基之2官能以上之（甲基）丙烯酸酯1〇〜6〇重量份、（甲美） 丙婦酸環氧_ 0〜30重量份、及（甲基）丙稀酸苯氧醋土1〇 〜50重量份 此時，若（甲基）丙烯酸胺基甲酸酯未滿2〇重量份則韌 性差，若超過70重量份則耐熱分解性之方面較差。朝 312XP/發明說明書(補件)/96-10/96123707 25 200810922 具有環氧烷之2官能以上之（曱基）丙烯酸酯，若超過 60重I份則硬化物容易破碎且韌性差，若未滿1〇重量 •知，則組成物之塗敷性、硬化物之線膨脹係數增大，即薄 :膜之寸法穩定性差，故不理想。 若（甲基）丙烯酸苯氧酯未滿1 〇重量份，則組成物之黏 度咼而薄膜化加工性差，若超過5〇重量份，則過於軟質 且強度、二次加工性方面較差。 (曱基）丙烯酸環氧酯係視需要調配者，若調配，則可獲 •得提高耐熱變形性、耐熱分解牲、二次加工性、成本之^ 果，若超過30重量份，則因樹脂組成物變為高黏度故不 利於薄膜形成，且硬化物之光線透過率亦降低，故不理想。 ，另外，對於上述第三硬化組成物（c)而言，較佳為硬化 刖之黏度為1 0000 MPa.s以下，且組成物之表面張力為 35 45 mN/m。若為黏度超過iQooo Mpa . s者，則製膜時 之給液變得困難，且難以獲得塗敷精度。表面張力係對塗 ⑩敷面造成影響之因素，若表面張力過低，則將該組成物供 給至工程用薄膜時液易變得不穩定，且容易產生塗佈缺 陷。另外，若表面張力過高，則於工程用薄膜上組成物容 易彈起，會損害塗敷面之平滑性。 “另外，使用本發明之第三硬化性組成物（c)而形成之薄 膜較仏為兼具柔軟性、強韌性，耐熱牲，根據該觀點， '較佳為玻璃轉移溫度處於60〜loot:之範圍内。玻璃轉移 /里度過尚，則容易破碎，而難以成形為輥狀薄膜，將該薄 膜應用於光碟之透光層則易於產生翹曲，尤其於高溫·高 312XP/發明說明書(補件)/96-10/96123707 26 200810922 濕等惡劣條件下保存時，會產生較大翹曲。另一方面，薄 膜之玻璃轉移溫度過低，則無法獲得室溫下自立之薄膜， :作為光碟之透光層而應用時之強度不充分，保護資訊記錄 :層之效果不充分，即使於其上設置強度高之表面層，亦無 法獲得充分之保護效果。 …、 另卜β /#膜於5 C〜55 C之溫度範圍内’線膨服係數 較佳為170 _以下。若膨脹係數過高，則將該薄膜應用 於光碟之透光層時，會大於一般光碟之線膨服係數，使用 籲溫度範圍内碟片上易產生翹曲。 作為組成物’上述以外之成分，其他光硬化性募聚物. 單體或光起始劑、增感劑、交聯劑、紫外線吸收劑、聚合 抑制劑、填充料、熱可塑性樹脂.染料.顏料等著色劑等， 可在對硬化或透明性、耐熱性等物性有效而不會妨礙1之 範圍内進行調配。尤其是於應用紫外線照射作為活性能量 射線時，必需光起始劑，並未限制使用安息香系、苯乙酮 籲系、噻噸酮系、氧化膦系及過氧化物系等。 作為光起始劑，例如，可例示：苯曱酮、4,4—雙（二乙 基胺基）二苯曱酮、2,4,6_三曱基二苯甲酮、甲基鄰苯甲 =基苯甲酸醋、4-苯基二苯甲酮、第三丁基蒽醌、2_乙基 恩醌、一乙氧基苯乙酮、2_羥基_2_甲基―丨―苯基丙烷一丄一 •酮、2-羥基-ΐ-[4-[4-(2-羥基_2 一甲基_丙醯基）苄基]苯 "基]2甲基_丙烷酮、苄基二曱基縮酮、卜羥基環己基 苯基酮、安息香曱轉、安息香乙鍵、安息香丙謎、安息香 異丁鍵、2-曱基-[[(曱硫基）苯基]_2_咮啉基+丙酮、 312ΧΡ/發明說明書(補件)/96-1〇/96123707 27 200810922 2-节基-2-二曱基胺基-丨气扣味啉基苯基）_丁目同_丨、二乙 基噻噸酮、異丙基噻噸酮、2, 4,6_三曱基苯甲醯基二= :氧化膦、雙(2,6-二曱氧基苯曱醯基)—2,4,4一三甲基： :膦氧，物、雙(2,4,6-三甲基苯曱酸基)_苯基麟氧化物： 甲基苯甲酸基甲酸西旨等。該等可單獨使用i種或併用2種 以上。 其中’安息香系、具體而言2_羥基+[4_[4—(2,美 2-甲基—丙醯基）¥基]苯基卜2_甲基等於^ 響性、耐久性方面優良。 可根據組成物之硬化性等對光起始劑之量進行適當調 整’較為常見的是相對於本發明之活性能量射線硬化:組 成物100重量份，為1〜10重量份。 、對於本發明之活性能量射線硬化性組成物（本發明之組 成物）之薄膜化（本發明之透明薄膜之製造方法）而言，並 未對既存之塗佈法之應用等加以特別制約，但較佳為利用 _以下方法。 於連續地以固定速度進行驅動之工程用脫模薄膜.帶. 軏上，疋里供給充分混合分散之該組成物，並藉由表面張 力或加熱、加廢效果而賦予其薄膜形狀，照射活性能量射 線使之硬化，浦職薄膜.帶._成形為薄膜。 作，工程用脫模薄膜，可利用聚乙稀薄膜、雙轴延伸聚 丙稀薄膜、t 4-甲基戊烯―丨薄膜、雙軸延伸聚對苯二甲 :巧二酯薄膜、雙軸延伸聚萘二甲酸乙二酯薄膜、氟樹脂 涛膜等脫模性、尺寸穩定性、平滑性優良的薄膜，較佳為 312xp/發明說明書(補件)/96-10/96123707 28 200810922 =予用之平滑性優良之雙軸延伸聚對苯二甲酸乙二醋薄 膜，更佳為進一步利用矽酮塗佈進行脫模處理之光學用之 平滑性優良的雙軸延伸聚對苯二甲酸乙二酯薄膜。 對於脫模性之程度而言，除了使組成物硬化後之脫模性 方面之外’亦於塗佈時之薄膜形態之潤濕穩定性、密接性 之平衡方面進行。In this case, if the (meth)acrylic acid amide phthalate is less than 40 parts by weight, the toughness is inferior, and if it exceeds 60 parts by weight, the heat decomposition resistance is inferior. When the (meth)acrylic epoxy vinegar is less than 10 parts by weight, the composition is heat-resistant and deformed: if it exceeds 40 weights, the viscosity of the composition is high, and the thin film-forming workable cured product t light transmittance is lowered. The (meth)acrylic acid vinegar system is required to be blended. If the material is blended, the effect of improving the film forming processability, heat deformation resistance, heat decomposition and cost of the composition is obtained. If the weight exceeds (4), the resin is required. Since the hardening shrinkage of the composition is increased and the cured product is easily broken, it is difficult to form into a roll-shaped film, and secondary workability is also inferior. [The third curable composition (C) of the present invention] ({(meth)acrylic acid urethane 20 to 70 parts by weight, and an epoxy group-containing bifunctional or higher (meth) acrylate 1 〇 ～6〇 parts by weight, (甲美) propyl ethyl epoxide _ 0~30 parts by weight, and (meth) acrylic acid phenoxy acetonate 1〇~50 parts by weight at this time, if (meth) acrylate If the amount of the urethane is less than 2 parts by weight, the toughness is poor, and if it exceeds 70 parts by weight, the heat decomposition resistance is inferior. The 312XP/invention specification (supplement)/96-10/96123707 25 200810922 has an alkylene oxide 2 If the functional group is more than 60 parts by weight, the hardened material is easily broken and the toughness is poor. If the weight is less than 1 •, the coating property of the composition and the linear expansion coefficient of the cured product are increased. , that is, thin: the stability of the film is poor, so it is not ideal. If the phenoxy (meth) acrylate is less than 1 part by weight, the viscosity of the composition is poor and the filming processability is poor. If it exceeds 5 parts by weight, Too soft and inferior in strength and secondary processing. (Mercapto) acrylate epoxy ester is required to be blended if When blending, it is possible to obtain heat resistance, heat decomposition, secondary workability, and cost. If it exceeds 30 parts by weight, the resin composition becomes highly viscous, which is disadvantageous for film formation and hardening. Further, it is not preferable that the light transmittance of the third hardening composition (c) is not less than 1,000,000 MPa.s, and the surface tension of the composition is 35. 45 mN/m. If the viscosity exceeds iQooo Mpa. s, the liquid supply during film formation becomes difficult and the coating accuracy is difficult to obtain. The surface tension is a factor affecting the application of the coating surface, if the surface tension is excessive When the composition is supplied to the film for engineering, the liquid tends to be unstable, and coating defects are likely to occur. When the surface tension is too high, the composition on the engineering film tends to bounce and damage the coating. The smoothness of the surface to be coated. "In addition, the film formed by using the third curable composition (c) of the present invention has softness, toughness, and heat resistance. According to this viewpoint, 'preferably glass transfer. The temperature is at 60~loot: the van In the circumference, if the glass is transferred or immersed, it is easy to be broken, and it is difficult to form into a roll-shaped film. When the film is applied to the light-transmitting layer of the optical disk, warpage is liable to occur, especially at high temperature and high 312XP/invention manual (complement) ())/96-10/96123707 26 200810922 When stored under severe conditions such as humidity, large warpage will occur. On the other hand, if the glass transition temperature of the film is too low, a film that is self-standing at room temperature cannot be obtained: as a disc The light-transmissive layer is not sufficiently strong in application, and the protection information is recorded: the effect of the layer is insufficient, and even if a surface layer having a high strength is provided thereon, sufficient protective effect cannot be obtained. ..., another β /# film is In the temperature range of 5 C to 55 C, the 'line expansion coefficient is preferably 170 _ or less. If the expansion coefficient is too high, the film will be applied to the light transmissive layer of the optical disc, which is larger than the linear expansion coefficient of the conventional optical disc, and the warpage is likely to occur on the disc in the temperature range. As a composition other than the above components, other photocurable polymer. Monomer or photoinitiator, sensitizer, crosslinker, UV absorber, polymerization inhibitor, filler, thermoplastic resin. Dye. A coloring agent such as a pigment can be formulated in a range that is effective for physical properties such as curing, transparency, and heat resistance without interfering with one. In particular, when ultraviolet irradiation is used as the active energy ray, a photoinitiator is required, and the use of benzoin, acetophenone, thioxanthone, phosphine oxide, and peroxide is not limited. As the photoinitiator, for example, benzophenone, 4,4-bis(diethylamino)benzophenone, 2,4,6-tridecylbenzophenone, methyl ortho benzene can be exemplified. A = benzoic acid vinegar, 4-phenyl benzophenone, tert-butyl hydrazine, 2 - ethyl hydrazine, monoethoxy acetophenone, 2 - hydroxy 2 - methyl - hydrazine - benzene Propane-one-ketone, 2-hydroxy-indole-[4-[4-(2-hydroxy-2-methyl-propionyl)benzyl]benzene "yl]2 methyl-propanone, benzyl Di-decyl ketal, hydroxycyclohexyl phenyl ketone, benzoin, benzoin, benzoin, benzoin, butyl, 2-mercapto-[[(indolyl)phenyl]_2_咮啉 + 丙酮 丙酮 丙酮 丙酮 丙酮 丙酮 丙酮 丙酮 96 96 961 961 961 961 961 961 961 961 961 961 961 961 961 961 961 961 961 961 961 961 961 961 961 961 961 961 961 961 961 961 961 961 961 961 961 961 961 961 961 961 961 Diethyl thioxanthone, isopropyl thioxanthone, 2, 4,6-trimethyl benzhydryl bis- =: phosphine oxide, bis(2,6-didecyloxyphenyl)- 2 , 4,4-trimethyl:: phosphine oxide, bis(2,4,6-trimethylphenylnonanoate)-phenyl lining: methyl benzoic acid. These may be used alone or in combination of two or more. Among them, the benzoin system, specifically 2_hydroxyl + [4_[4-(2,-2-methyl-propenyl)-yl]phenyl-2-yl-methyl group, is excellent in sound resistance and durability. The amount of the photoinitiator can be appropriately adjusted depending on the hardenability of the composition or the like. It is more usually 1 to 10 parts by weight based on 100 parts by weight of the active energy ray hardening of the composition. The film formation of the active energy ray-curable composition (the composition of the present invention) of the present invention (the method for producing a transparent film of the present invention) does not particularly restrict the application of the existing coating method, and the like. However, it is preferable to use the following method. A release film for engineering which is continuously driven at a fixed speed. The crucible is supplied with a composition which is sufficiently mixed and dispersed, and is imparted to the film shape by surface tension or heating or addition effect, and is irradiated. The energy ray hardens it, and the film is formed into a film. For the engineering release film, it can use polyethylene film, biaxially stretched polypropylene film, t 4-methylpentene-ruthenium film, biaxially extended polyparaphenylene: a diester film, biaxial extension A film excellent in mold release property, dimensional stability, and smoothness, such as a polyethylene naphthalate film or a fluororesin film, is preferably 312xp/invention specification (supplement)/96-10/96123707 28 200810922=approved The biaxially-oriented polyethylene terephthalate film excellent in smoothness is more preferably a biaxially-oriented polyethylene terephthalate excellent in smoothness for optical use for further release treatment by an anthrone coating. film. The degree of mold release property was carried out in addition to the mold release property after hardening the composition, and also in terms of the balance of wettability and adhesion of the film form at the time of coating.
士另夕^對於脫模薄膜之厚度主要於塗佈本發明之組成物 才之％疋性、對硬化後之硬化收縮所引起的翹曲之抑制、 有關硬化之活性能量射線透過性、脫膜成本之平衡方 面進行調整，實用性的是50〜250 #m。 工程用脫模帶係將不銹鋼或表面電鑛加工鋼等平滑 :生、尺寸穩定性優良之板材無縫地連接，並將該板材搭在 、、上之輮上，藉由親之驅動而用於連續定速加工。亦 可進而利用氟樹脂或陶变等塗佈表面並進行高脫模化。進 =用_脂或陶£等塗佈表面電錢加工鋼後，使工程用 =親脫模。該等步驟既可於每次進行薄膜化時，於僅接 態下對組成物賦形，而另-個面於大氣接觸 = =::，亦可利用各種組合使兩面工程用脫模材 線日i n仃、°卫°其中’當應用紫外線作為活性能量射 或二：’、低透過性之制約，而必須使至少-個面為大氣 _卜8塑膠）薄膜，照射亦限定於大氣或者（透明塑膠） 疋量供給本發明之組成物時 法、棒式塗佈法、氣刀塗佈法、 ’可使用凹版塗佈法、輥塗 刮刀塗佈法、網版塗佈法、 312ΧΡ/發明說明書(補件)/96-10/96123707 29 200810922 模塗法、淋幕式平面塗佈法等 溥膜化時之該薄膜之厚度等， 合之方式。 可根據使本發明之組成物 该等塗佈方法中選擇出適 2二發明之目的在於獲得厚度1〜2_ 較多為5〜 透明:m更夕為1〇〜500㈣、更多為20〜200 之 該等厚度作為塗佈加工所獲得之薄膜之厚度而 區域，若考慮厚度精度、加工之工夫、外觀等，On the other hand, the thickness of the release film is mainly based on the % composition of the composition of the present invention, the suppression of the warpage caused by the hardening shrinkage after hardening, the active energy ray permeability of the hardening, and the release film. The cost balance is adjusted, and the practicality is 50~250 #m. The mold release belt for engineering smoothes stainless steel or surface electric ore processing steel, etc.: the plates with excellent raw and dimensional stability are seamlessly connected, and the plate is placed on the top and bottom, and driven by the pro-driver. Continuous continuous speed processing. Further, the surface may be coated with a fluororesin or a ceramic or the like to perform high release. Into = use _ fat or Tao, etc. coated surface electric money processing steel, so that engineering = pro-release. These steps can be used to shape the composition in the joint state only when the film is formed, and the other surface is in contact with the atmosphere ==::, and the combination can be used to make the mold release line for the double-sided engineering. In in, ° ° ° ° "When applying UV as active energy shot or two: ', low permeability, and must make at least - a surface of the atmosphere _ _ 8 plastic) film, the exposure is also limited to the atmosphere or ( Transparent plastic) Method for supplying the composition of the present invention, bar coating method, air knife coating method, 'gravure coating method, roll coating blade coating method, screen coating method, 312 ΧΡ/invention Instruction manual (supplement)/96-10/96123707 29 200810922 The thickness of the film, such as the die coating method and the curtain coating method, is the same as the thickness of the film. According to the composition of the present invention, the coating method is selected to obtain the thickness of 1 to 2 _ more than 5 to transparent: m is 1 〇 to 500 (four), more is 20 to 200 The thickness is the area of the thickness of the film obtained by the coating process, and considering the thickness precision, the processing time, the appearance, and the like,
於模塗方式中’較佳為將組成物製成硬化成分實 貝上為100%之無溶劑系之組合。 趣if :實質i 100%表示：組成物處方中未使用溶劑或 止又刀《者以既定條件去除之内容中，目溶劑殘留或 =始劑殘留對實際性能之不良影響低而可以忽略。可藉 ^成物中之材料選擇或加熱，對伴隨組成物之無溶劑化 而¥致之黏度上升的塗佈加工性之影響進行調整。 旦1用以“、、射並使各化合物原料之混合物硬化之活性能 里射線亚未加以特別制約，可應用可用於工業者，列舉紫 卜Λ电子束7射線、X射線等，當綜合判斷對透過厚 能量、設備成本、光起始劑或增感劑等添加劑之成本· 品質之負荷等時，則利用紫外線則尤為容易。 产對於紫外線而言，以低壓水銀燈、高壓水銀燈、氤氣燈 等紫外線燈為代表，可無特別限制地利用各種發光特性 者，可根據薄膜厚度或硬化狀況等加以適當調整。另外， 同樣對能量亦可進行調整，照度大約為〇1〜5 J/cm2。 進而’為了提高照射效率，可-面將照射環境設為氮氣 312XP/發明說明書(補件)/96-10/96123707 30 200810922 等惰性氣體環境，或者— 而-面進行照射。 面對所成形之組成物進行加溫， 未使用工㈣脫模_時，因僅獲得_ 狀捲取並切割而單片化 、、支直接呈輥 用薄膜化等具體料中形“用於光學功能調整 膜時，因獲得|脫模薄膜^方面’於使用工程用脫模薄 剝離工程用脫模薄膜而盘：層之溥膜’故除了可於硬化後 •離而直接積層之形態下用於具體用途，將工程剝 、體用途中之工程用脫模薄膜，$肉& 亦處於本主旨之範圍内。 物5亥内谷 =明之活性能量硬化性組成物，硬化收縮率較佳為 ::更佳4 5%以下。若硬化收縮率為7%以上，則薄 、形成¥之捲曲增大’將該薄膜應用於光碟之透光層，合 2伴隨硬化收縮之薄膜之殘留應力而容易產生趣㈣ 使用本發明之組成物所形成之薄膜，拉伸破裂延伸率較 ^為5〜70%，更佳為15〜5〇%。拉伸破裂延伸率過小，則 谷易破碎且難以成形為輕狀薄膜，將該薄膜應用於光碟之 =光層％，谷易產生翹曲，尤其是於高溫高濕等惡劣條 件下保存時會產生較大之翹曲。 另一方面，若薄膜之拉伸破裂延伸率過大，則過於柔軟 …、法U彳于自立之薄膜，應用為光碟之透光層時強度不充 刀保°蒦貧成S己錄層之效果不充分，即使於其上設置強度 高之表面層，亦無法獲得充分之保護效果。 Π2ΧΡ/發明說明書(補件)/96·Ι0/96 123707 31 200810922 。。之二::二:之，成物所形成之薄膜’較佳為25 :存彈性模數(E，、）未满，2〇〇〇MPa以上，且議之儲 :之本發明之薄 ’ 〇，。如此調節了黏彈性行為 箄門9 、 冒產生容易破碎、沒有韌性難以處理 纪肺’可加工為薄膜狀，例如，可應用於保護光碟等之 记錄層之保護薄膜等。 坑本ΓΠ光Γ例如係如下光碟’該光碟於表面形成有訊 置蚕你圖案絲作為錢記錄面之碟丨基板上設 二 /、&膜之透光層，自該透光層侧照射雷射光進行資 ^記錄、再生；且❹由上述本發明之活性能量射線硬 組成物所構成之薄膜作為該透光層。 為了於碟片基板上形成透光層，例如，可於形成於 ^板上之記錄膜（信號記錄面）之表面，塗佈本發明之組成 形成塗膜後，對該塗膜照射活性能量射線，而使之硬 化。另外，為了形成多層記錄型光碟之接著劑兼透光層， 例如，可於光碟基板之一侧或者兩侧塗佈本發明之組成 物，介隔該組成物貼附數塊碟片基板後，透過基板照射活 性能量射線，使組成物硬化。 / 此時，為了防止光信號之劣化，則該薄膜之透光率越高 越好，由本發明之活性能量硬化性組成物所構成之硬化薄 膜，380〜800 nm之範圍之波長區域的光之透過率為88% 以上，尤其是400〜410 nm之範圍之波長區域的光之透過 率為90%以上。 對於應用於本發明之光碟的光信號之波長並未加以特 312XP/發明說明書(補件)/96-10/96123707 32 200810922 別限定，-般較佳為用於光碟之讀取或寫入的波長為· 〜_ nm之範圍之雷射光’尤其是若為可實現光碟之記 錄容量的高密度化之400 nm左右之藍紫色雷射光，如上 所述該波長區域之透過率為90%以上，故極佳。 士再者’將本發明之透明薄膜作為光碟之保護膜而積層 日=使用^外準備之接著劑、黏著劑或者其薄膜材料等。 =時^於溥膜或者光碟基板面上對接著劑或黏著劑進行塗 敷.乾燥.軟化（接著劑之情況下）.硬化（黏著劑 後，積層各光碟基板與薄冑，使彼等硬化或者冷卻固化 =之情況下）。若為該薄膜材料，則將該薄膜材料於光 ί基板面/積層·軟化(接著劑之情況下)·硬化(黏著劑之 月况下纟，積層光碟基板與薄膜，使彼 固化（接著劑之情況下）。 飞者/7部 對接著劑、黏著劑或者其薄膜材料並未加以特別 除了耐熱性、透明性、成本卜， 、 較佳為丙婦酸系。 自接者性之硯點考慮， 本發明之柄之透光層之總厚度 ：：M：5r ㈣之乾圍。由構成透光層 :、 硬化性組成物所構成的薄膜之厚度，為〗〜二= 致的劣化之觀點考慮，較佳為L=劣 侍之先碟之翹曲量之觀點考慮， ”又 佳為100…下。 &仫為200“以下，更 mm發明說明書(補件)/96-10/961237〇7 33 200810922 (實施例） [實施例1] : [1 ]硬化性組成物（A)之製備 ； 混合溶解作為丙烯酸胺基曱酸酯成分之下述構造式[2] 所示之丙烯酸胺基曱酸醋50重量份、作為丙稀酸^氧醋 成分之壬基苯酚E0改質丙烯酸酯30重量份、从& ^ ^ 作為丙焊酸 環氧酯成分之雙酚A環氧丙基醚型丙烯酸環氧酿重量 份、作為聚合起始劑之2-羥基[4-(2〜經基2—曱基一 _丙醯基）苄基]苯基]-2-曱基-丙烷—1 —酮2質量份，彳雈得實 施例1之硬化性組成物。 又 、 [化2]In the die coating method, it is preferred that the composition be made into a combination of a solvent-free system having a hardening component of 100%. Interesting if: Substance i 100% means: In the composition prescription, no solvent is used or the knife is removed. The content of the solvent residue or the initiator residue has a low adverse effect on the actual performance and can be ignored. It is possible to adjust the influence of the coating processability which increases the viscosity of the composition due to the unsolvation of the composition by material selection or heating. Once the energy is used to ",, and to harden the mixture of the raw materials of each compound, the ray is not particularly restricted. It can be used in industrial applications, and the electron beam 7-ray, X-ray, etc. It is especially easy to use ultraviolet rays when it is required to pass the cost and quality of additives such as thick energy, equipment cost, photoinitiator or sensitizer. It is easy to use ultraviolet light, high pressure mercury lamp, xenon lamp for ultraviolet light. The ultraviolet light is used as a representative, and various light-emitting characteristics can be used without particular limitation, and can be appropriately adjusted depending on the thickness of the film, the curing condition, etc. In addition, the energy can be adjusted as well, and the illuminance is approximately 〜1 to 5 J/cm2. Furthermore, in order to improve the irradiation efficiency, the irradiation environment can be set to an inert gas atmosphere such as nitrogen 312XP/invention specification (supplement)/96-10/96123707 30 200810922, or the surface can be irradiated. The composition is heated, and when it is not used (4) demoulding_, it is obtained by simply obtaining a _-like winding and cutting, and singulating, and directly forming a thin film for rolling. When it is used for the optical function adjustment film, it is obtained by using the release film of the mold release thinning process and the film of the layer: the film of the layer is removed. It is also used in the form of a release film for engineering peeling and body application, and the meat & is also within the scope of the present invention.物5海内谷 = Ming active energy hardening composition, the hardening shrinkage ratio is preferably :: more preferably 4 5% or less. When the curing shrinkage ratio is 7% or more, the thickness of the film is increased, and the curl is increased. The film is applied to the light-transmitting layer of the optical disk, and the residual stress of the film which is accompanied by the hardening shrinkage is easily generated. (IV) Composition using the present invention The film formed by the object has a tensile elongation at break of from 5 to 70%, more preferably from 15 to 5 %. If the tensile elongation at break is too small, the valley is easily broken and difficult to form into a light film. The film is applied to the optical layer of the optical layer, and the valley is prone to warpage, especially when stored under severe conditions such as high temperature and high humidity. Produces a large warp. On the other hand, if the tensile elongation at break of the film is too large, it is too soft... The method is applied to the film of self-standing, and the effect is not sufficient when the light-transmissive layer of the optical disk is used. Insufficient, even if a surface layer having a high strength is provided thereon, sufficient protection effect cannot be obtained. Π 2ΧΡ / invention manual (supplement) / 96 · Ι 0 / 96 123707 31 200810922 . . The second:: two:, the film formed by the product 'preferably 25: the storage modulus (E,,) is not full, 2 〇〇〇 MPa or more, and the storage: the thin of the invention' Oh, The viscoelastic behavior is adjusted in this way. The cardia 9 is easy to be broken, and the toughness is difficult to handle. The lungs can be processed into a film shape, for example, a protective film which can be applied to a recording layer for protecting a disc or the like. The 坑 ΓΠ ΓΠ Γ Γ Γ Γ ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' The laser light is recorded and reproduced, and a film composed of the above-described active energy ray hard composition of the present invention is used as the light-transmitting layer. In order to form a light-transmitting layer on the disc substrate, for example, a coating film can be formed on the surface of the recording film (signal recording surface) formed on the board, and the coating film is irradiated with an active energy ray. And make it harden. In addition, in order to form an adhesive and a light-transmitting layer of a multi-layer recording type optical disc, for example, the composition of the present invention may be applied to one side or both sides of the optical disc substrate, and after attaching a plurality of disc substrates to the composition, The active energy ray is irradiated through the substrate to harden the composition. / In this case, in order to prevent deterioration of the optical signal, the light transmittance of the film is preferably as high as possible, and the cured film composed of the active energy curable composition of the present invention has a light region in a wavelength range of 380 to 800 nm. The transmittance of light in a wavelength region of 88% or more, particularly in the range of 400 to 410 nm, is 90% or more. The wavelength of the optical signal applied to the optical disc of the present invention is not limited to the special 312XP/invention specification (supplement)/96-10/96123707 32 200810922, and is generally preferably used for reading or writing of the optical disc. The laser light having a wavelength in the range of ~ _ nm is particularly a blue-violet laser light having a density of about 400 nm which can achieve a high recording density of the optical disk, and the transmittance of the wavelength region is 90% or more as described above. It is excellent. Further, the transparent film of the present invention is laminated as a protective film for an optical disk. The following is an adhesive used for external use, an adhesive, or a film material thereof. When the film is applied to the film or the substrate of the film, the adhesive or the adhesive is applied. Drying and softening (in the case of an adhesive). Hardening (after the adhesive, the layers of the optical disk substrate and the thin film are laminated to make them harden) Or in case of cooling and curing =). In the case of the film material, the film material is cured on the surface of the substrate, laminated, softened (in the case of an adhesive), and cured (the adhesive substrate is laminated, and the optical disk substrate and the film are laminated to cure the film (adhesive agent). In the case of the flyer/7 parts, the adhesive, the adhesive or the film material thereof are not particularly heat-resistant, transparent, and cost-effective, and it is preferably a glycerol acid system. It is considered that the total thickness of the light transmissive layer of the handle of the present invention is: M: 5r (d) dry circumference. The thickness of the film formed by the light transmissive layer: the hardenable composition is 〖~2 = deterioration From the point of view of consideration, it is better to consider the amount of warpage of the first dish of L=wort service, "good for 100... under. & 仫 is 200" or less, more mm invention manual (supplement) / 96-10/ 961237〇7 33 200810922 (Example) [Example 1]: [1] Preparation of curable composition (A); Acrylic acid represented by the following structural formula [2] which is dissolved as an amino phthalate component 50 parts by weight of amino phthalic acid vinegar, decyl phenol E0 modified acrylate 30 as acrylic acid vinegar component Quantities, from & ^ ^ as a propylene oxide epoxy ester component of bisphenol A epoxidized propyl ether type acrylic emulsified parts by weight, 2-hydroxyl as a polymerization initiator [4-(2~ 2 parts by mass of 2-fluorenyl-propionyl)benzyl]phenyl]-2-indenyl-propane-1-one, and the hardening composition of Example 1 was obtained.
(其中’上述構造式[2]中η表示4〜8之整數）。 所獲得之組成物之黏度於25°C為l〇〇〇〇MPa.s，為淡黃 色透明且黏稠之液體。 於28 C之溫度條件下，利用250 mm寬度之模塗機，將 該實施例1之硬化性組成物於自卷軸卷開之厚度為25〇 # m的光學用之平滑性優良的雙軸延伸聚對苯二曱酸乙二 酉曰薄膜面上塗佈為80 # m之厚度，利用金屬鹵素燈以置 J/cm之照度，照射紫外線並使之硬化後進行捲取，獲得 312XP/發明說明書(補件)/96·1〇/961237〇7 34 200810922 :層雙轴延伸聚對苯二甲酸乙二醋薄膜作為工程用脫模 ’專膜之貫施例1之透明薄膜。 ‘對4過程中硬化以後之薄膜之硬化收縮所伴隨的所積 :=之薄膜之延伸率、捲曲情況、厚度精度、二次加工性: =線透過率進行如下所示之評估，將所獲得之結果表示於 表1中。 、 〈溥膜之延伸率〉 ^用截切刀將該樣品（實施例丨之透明賴）切下平面 :?〇補_之矩形作為測試片，使用該 ， =康m nm- 1989藉由Int⑽公司製造之IM—2〇 1測试機測定拉伸破裂延伸率。 〈捲曲情況> /捲取輥之張力使硬化錢㈣直至捲取為止 潯膜保持平面狀，藉由硬 * + 貝运 力寇 更化收'、、倍而使潯胰收縮，根據其應 力私度或工程用脫模薄膜之勤性 : 臈側捲曲。藉由此蚌力“ 5 — 専膜之兩鸲於溥 作用會導致===賴之張力而欲恢復至平面的 曰¥致賴產生龜裂·裂痕、捲取位置之 $或起鈹彎曲，根據該狀況進行如下判定。 折 〇··未發現捲曲。 △ ··發現因捲曲而導致一部 薄膜產生龜裂.裂痕或兩端部之折疊級成者丐曲，但未發現 X::現因捲曲而導致起皺或者彎、 裂痕或兩端部之折疊α ^之龜裂· 〈厚度精度〉彳且之任種，無法獲得部分薄膜。 312XP/發明說明書(補件)/96-10/96123707 35 200810922 自所獲得之經積層之實施例i之透明薄膜剝離去除工 程用脫模薄膜，於薄臈250 mm寬度方向上以均等寬度並 根據JIS K713GA-1法，利用2〇點測微計來】“ 如下判定。 j 〇：測定值之範圍未滿G. GG5 _且標準偏差未滿〇剛 mm U疋值之耗圍未滿0·005 _或者標準偏差未滿 U.ϋϋζϋ mm 為 0. 0020 x ·測疋值之範圍為〇 · 〇 〇 5 mm以上且標準偏差 mm以上 〈二次加工性> 將所獲得之經積層之薄膜之薄膜面作為移動刀側，於 20C下對片薄膜進行沖切刀（Th〇_biade)之切割加 工，根據薄膜之剖面之狀況進行如下判定。 Ο·所有均被徹底地毫無問題地切斷 • △•發現未滿3片之於剖面出現細微龜裂者 X ·叙現3片以上之於剖面出現細微龜裂者 〈光線透過率〉 自所獲侍之積層薄膜剝離去除工程用脫模薄膜，測定初 期之波長為400 nm時之光線透過率。其次，將其硬化物 於80C、85%RH之環境條件下放置5〇〇小時後，以與初期 .之光線透過率相同之方式，再次測定環境測試後之波長為 時之⑽透過率。再者，基於下述基準對初期及 環境測忒後之光線透過率進行評估。 犯辦發明說明書(補件)/96-10/96123707 36 200810922 〇·· 90%以上 △ : 88%以上 : X ··未滿 8 8 % • [ 2 ]具有硬化物層之光碟之製作及評估 (評估用光碟基材之製作） 使用20 _厚度之黏著劑，將由上述⑴所獲得之硬化 性組成物所構成之實施例1之透明薄膜，以平膜 之方式，貼合於具有光碟形狀之聚碳酸醋樹脂製 ❿透明圓盤狀鏡面基板（直徑12 cm，板厚hl咖，翹曲角 〇度，以下簡稱為基材）之一個面上，製作具有由實施例1 之硬化性組成物所構成之硬化物層的實施例丨之光碟，並 進行以下評估，將所獲得之結果表示於表丨中。 〈鉛筆硬度〉 對所獲得之實施例1之光碟，根據JISK_54〇〇測定透 光層之鉛筆硬度，進行以下判定，(wherein η in the above structural formula [2] represents an integer of 4 to 8). The viscosity of the obtained composition was 10 MPa.s at 25 ° C, which was a yellowish transparent and viscous liquid. The curable composition of Example 1 was subjected to a biaxial stretching excellent in smoothness for optical use of a thickness of 25 Å #m wound from a reel under a temperature condition of 28 C using a die coater of 250 mm width. The surface of the polyethylene terephthalate film is coated to a thickness of 80 #m, and the metal halide lamp is used to set the illuminance of J/cm, and the ultraviolet ray is irradiated and hardened, and then coiled, and 312XP/invention specification is obtained. (Repair)/96·1〇/961237〇7 34 200810922: A layer of biaxially stretched polyethylene terephthalate film is used as a transparent film for the application of the demolding of the film. 'Production accompanying the hardening shrinkage of the film after hardening in 4: = elongation of the film, curl, thickness accuracy, secondary workability: = line transmittance is evaluated as shown below, and obtained The results are shown in Table 1. [Elongation of the enamel film] ^ The sample (transparent lye of the example )) was cut into a plane with a cutting knife: the rectangle of the 〇 _ _ was used as a test piece, and the =m nm- 1989 was used by Int(10) The tensile elongation at break was measured by an IM-2〇1 tester manufactured by the company. <Curling condition> /The tension of the take-up roll makes the hardening money (4) until the film is kept flat until the winding, and the sputum and pancreas shrinks by the hard ** Mobility of the release film for degree or engineering: Curl on the side. By this force "5 - the two 鸲 溥 溥 会 会 会 会 = = = = = = = 赖 赖 赖 赖 赖 赖 致 致 致 致 致 致 致 致 致 致 致 致 致 致 致 致 致 致 致 致 致 致 致 致 致 致 致 致According to this situation, the following determination was made. Folding··No curl was found. △ ·· It was found that a film was cracked due to curling. Cracks or folding stages at both ends were distorted, but X:: A part of the film cannot be obtained due to wrinkles or wrinkles, cracks, cracks at the ends, or cracks at both ends of the crack of the α ^ thickness accuracy. 312XP / invention manual (supplement) / 96-10 / 96123707 35 200810922 The release film for the transparent film peeling removal process of the obtained example i obtained in the laminated layer is uniformly width-width in the width direction of 250 mm and according to the JIS K713GA-1 method, using a 2-point micrometer Come] "Determined as follows. j 〇: The range of measured value is less than G. GG5 _ and the standard deviation is not full 〇 mm mm 疋 value of the circumference is less than 0·005 _ or the standard deviation is less than U.ϋϋζϋ mm is 0. 0020 x · 疋The value range is 〇· 〇〇 5 mm or more and the standard deviation is mm or more. <Second workability> The film surface of the obtained laminated film is used as a moving blade side, and the film is punched at 20 C ( The cutting process of Th〇_biade) is determined as follows according to the condition of the profile of the film. Ο·All are completely cut off without problems. △•Discover 3 pieces of micro-cracks in the profile. X·Summary of 3 or more pieces with slight cracks in the section <Light transmittance> The obtained release film for the film peeling removal process was used to measure the light transmittance at an initial wavelength of 400 nm. Next, after the cured product was allowed to stand under an environmental condition of 80 C and 85% RH for 5 hours, the transmittance of the wavelength after the environmental test was measured again (10) in the same manner as the initial light transmittance. Furthermore, the light transmittance after initial and environmental measurements was evaluated based on the following criteria. Infringement invention manual (supplement) /96-10/96123707 36 200810922 〇·· 90% or more △ : 88% or more: X ·· under 8 8 % • [ 2 ] Production and evaluation of CD with hardened layer (Production of Optical Disk Substrate for Evaluation) The transparent film of Example 1 composed of the curable composition obtained in the above (1) was bonded to a disk-shaped shape by a flat film using a 20 _ thick adhesive. A curable composition of Example 1 was produced on one side of a transparent disc-shaped mirror substrate (diameter 12 cm, thickness hl coffee, warp angle twist, hereinafter referred to as a substrate) made of polycarbonate resin. The optical disk of the embodiment of the cured layer formed was subjected to the following evaluation, and the obtained result was shown in the form. <Pencil Hardness> With respect to the obtained optical disk of Example 1, the pencil hardness of the light-transmitting layer was measured in accordance with JIS K_54, and the following determination was made.
_ 〇：鉛筆硬度5B以上 X :鉛筆硬度未滿5B 〈勉曲〉 對將所獲得之實施例1之光碟於8〇°c、85%之相對濕度 下放置5 0 0小時後之麵曲進行如下判定。 〇：初期翹曲角與80°C 85%相對濕度下500小時後之翹 . 曲角之差未滿〇. 3。。 X :初期翹曲角與80°C 85%相對濕度下500小時後之翹 曲角之差為0. 3。以上。 312XP/發明說明書(補件)/96·10/96123707 37 200810922 [實施例2〜4、比較例1〜5 ] 除了利用表1之實施例2〜4及比較例1〜5之硬化性組 -成物之欄所示之化合物及以其調配比進行製備以外，以與 :實施例1相同之方式，獲得於基材上形成分別由實施例2 〜4及比較例1〜5之硬化組成物所構成之層的實施例2 〜4及比較例1〜5之光碟。 另外，對所獲得之實施例2〜4及比較例1〜5之透明薄 膜及光碟與實施例1同樣進行評估的結果分別表示於表j _之評估結果攔中。 再者，表1中之原料如下所示。 (* 1 )·丙烯酸胺基曱酸酯[1 ]:於使異佛爾酮二異氰酸 酯與丁二醇進行胺基甲酸酯縮合之末端加成丙烯酸4一羥 丁酯所獲得的丙烯酸胺基甲酸酯（重量平均分子；1〇〇〇〜 4000)。_ 〇: pencil hardness 5B or more X: pencil hardness less than 5B <勉曲> The surface of the obtained optical disk of Example 1 was placed at 80 ° C and 85% relative humidity for 500 hours. Determine as follows. 〇: The initial warpage angle is 500 hrs after 80 hours at 80 ° C 85% relative humidity. The difference between the corners is not full. . 5。 The difference between the initial warp angle and the warp angle after 500 hours at 80 ° C 85% relative humidity is 0.3. the above. 312XP/Invention Manual (Supplement)/96·10/96123707 37 200810922 [Examples 2 to 4, Comparative Examples 1 to 5] In addition to the use of the sclerosing group of Examples 2 to 4 and Comparative Examples 1 to 5 of Table 1 - The hardened compositions of Examples 2 to 4 and Comparative Examples 1 to 5 were respectively formed on the substrate in the same manner as in Example 1 except that the compound shown in the column of the product was prepared at the blending ratio. The optical disks of Examples 2 to 4 and Comparative Examples 1 to 5 of the layer formed. Further, the results of evaluation of the obtained transparent films and optical disks of Examples 2 to 4 and Comparative Examples 1 to 5 in the same manner as in Example 1 are shown in the evaluation results of Table j_, respectively. Further, the raw materials in Table 1 are as follows. (* 1 )·Amino phthalic acid acrylate [1 ]: an amide group obtained by adding 4-hydroxybutyl acrylate to the terminal of urethane condensation of isophorone diisocyanate with butane diol Formate (weight average molecule; 1〇〇〇~4000).
所獲彳寸的丙烯酸胺基曱酸酯（重量平均分子；1 〇〇〇 5000)。 (*3) ·丙稀酸苯氧酯： (* 4):丙烯酸環氧酯： :壬基苯氧基乙二醇丙烯酸酯。 :雙酚Α環氧丙基醚丙烯酸環氧 (* 5 ) 1聚合起始劑· 2 -經基_ 1 - [ 4 - [ 4 -(經基2 丙醯基）τ基]苯基]- 2-曱基-丙烧一 1-剛j。 312XP/發明說明書(補件)/96-10/96123707 38 200810922 [表1]The obtained acrylamide decanoate (weight average molecule; 1 〇〇〇 5000). (*3) · Phenyl acrylate: (* 4): Epoxy acrylate: decyl phenoxy glycol acrylate. : bisphenol oxime epoxy propyl ether acrylate epoxy (* 5 ) 1 polymerization initiator · 2 - thiol_ 1 - [ 4 - [ 4 -(transyl 2 propyl fluorenyl) yl ) phenyl] - 2-mercapto-propyl-one-n-j. 312XP/Invention Manual (supplement)/96-10/96123707 38 200810922 [Table 1]
自表1可知，活性能 胺基甲酸醋為3G〜6G重量份範圍内、（甲基）丙烯酸苯氧 酯為20〜50重量份範圍内、且（曱基）丙烯酸環氧酯為〇 3 0重里伤範圍内的組成物（實施例1〜*之組成物），與 如下組成物（比較例1〜5之組成物）相比較，於綜合地觀 察所有上述各評估項目的綜合判斷中為優良，上述組成物 (比較例1〜5之組成物）雖係與上述各實施例之組成物同 樣由（曱基）丙烯酸胺基甲酸酯、（甲基）丙烯酸苯氧酯、及 (曱基）丙烯酸環氧酯所構成之組成物，但該等3種成分中 之任一種成分處於與上述各實施例之組成物不同的含量 範圍中。 (實施例5) [3 ]硬化性組成物（Β)之製備 混合溶解作為（曱基）丙烯酸胺基曱酸酯成分之上述通 式[1]所示之丙烯酸胺基曱酸酯50重量份、作為（甲基） 312ΧΡ/發明說明書(補件)/96-10/96123707 39 200810922 丙烯酸環氧酯成分之上述通式[2 ]所示之雙酚A環氧丙基 醚型丙烯酸環氧酯（重量平均分子量2〇〇〇)2〇重量份、作 :為（曱基）丙烯酸脂環酯成分之三環癸烷二丙烯酸酯3〇重 • 置份、作為聚合起始劑之2-羥基— i-[4—[4-(2-羥基2-甲 基-丙醯基）苄基]苯基]-2-甲基-丙烷一丨—酮2質量份，獲 得貫施例1之硬化性組成物。該硬化性組成物之黏度於 60 C為9000 MPa.s，為淡黃色透明且黏稠之液體。 於60 C之溫度條件下，利用250 mm寬度之模塗機，將 •實施例5之硬化性組成物於自卷軸卷開之厚度為25〇 之平滑性優良的光學用之雙軸延伸聚對苯二甲酸乙二酯 薄膜面上塗佈未80 之厚度，利用金屬鹵素燈以i J/cm2 之照度進行照射，利用自該金屬鹵素燈射出之紫外線使之 硬化後進行捲取，獲得將雙軸延伸聚對苯二甲酸乙二酯薄 膜積層為工程用脫模薄膜的實施例丨之薄膜。對該過程中 實施例1之硬化性組成物之硬化收縮、薄膜之硬化收縮所 φ伴隨的積層之薄膜之捲曲情況、厚度精度、二次加工性、 及透光率進行如下所示之評估，並將結果表示於表2中。 [評估項目及評估方法] 〈硬化收縮〉 精密地秤量20 ml紫外線照射前之組成物原料混合物並 測定重量，求出該組成物之密度（dl)。自所積層之實施例 1之溥膜剝離去除工程用脫模薄膜，根據JIS K7ii2求 硬化物之密度（d2)，並依據下述式計算出硬化收縮率。 硬化收縮率（％)= [(d2)- (dl)/(d2)]xl 〇〇 312XP/發明說明書(補件)/96-10/96123707 40 200810922 〈捲曲情況〉 與實施例1之<捲曲情況〉同 判定。 订測试，亚進行相同之 〈厚度精度〉 與實施例1之〈厚度精度〉 判定。 灰進仃測試，並進行相同之 〈二次加工性〉 與實施例1之<二次加工性〉 之判定。 進行測試，並進行相同 〈光線透過率〉 之=施例1之〈光線透過率〉同樣進行測試叫^ [4]具有硬化物層之光碟之製作及評估 (評估用光碟基材之製作） 使用20 /zm厚度之黏著劑 ^ r 4ιί μ ^ ^ 寻上述[3 ]所獲得之硬化薄 M C剝離去除工程用脫模薄 尋 之方式，貼合於、开:：：以平均膜厚為 透明圓盤狀鏡面基板(直；t業讀厂之聚⑽ n ^ 土极、直^ 12 cm，板厚1. 1 mm，翹曲角 0度，以下簡稱為基材）一 芦之来蹀、、们之個面上，製作具有透明薄膜 層之先碟’亚切以下評估，將結果表示於表2中。 〈翹曲〉 /、貝施例1之〈想曲〉同樣進行測試，並進行相同之判 定。 [實施例6〜8、比較例6〜1〇] 312XP/翻說囑(細^抓聰⑽斯 200810922 除了使用下述表2之實施例6〜8及比較 所示之硬化性組成物以外’以與實施例 〜10之攔 得於基材上形成有硬化薄膜層之 式，獲 成物、由該組成物㈣得之硬化賴及積料=2之組 之光碟，與實施例5同樣進行評 二=獲得 表2之評估結果攔中。 將、-果分別表示於 再者’表2中之原料如下所示。 (*1)·於使雙（4 -異氰酸其王班p甘、 ^ 鼠文基％己基）甲烷與脂肪族聚碳 酸3日·一醇進行胺基甲酸@旨縮人夕古a山 ^ 輔口之末舄加成丙烯酸4—羥丁 酯所獲得的丙稀酸胺基甲醅萨「舌曰丁 土 T齔酉日（重®平均分子；5000)。 (*2)·聚（雙盼A環氣丙其辦a 乳内暴秘）丙烯酸環氧酯（重量平均 分子；1 000)。 量平均分子；484)。 2〜甲基-丙醯基）苄基] (* 3):雙酚A丙烯酸環氧酯（重 (* 4 )·二環癸燒二丙烯酸醋。 (* 5) : 2-羥基-1-[4-[4-(羥基It can be seen from Table 1 that the active energy amino carboxylic acid vinegar is in the range of 3G to 6G parts by weight, the phenoxy (meth) acrylate is in the range of 20 to 50 parts by weight, and the (mercapto) acrylate epoxy ester is 〇3 0 The composition in the range of the heavy injury (the composition of the examples 1 to *) was superior to the following composition (composition of the comparative examples 1 to 5) in comprehensively observing the comprehensive judgment of all the above evaluation items. The composition (comparatives of Comparative Examples 1 to 5) is the same as the composition of each of the above examples, and is composed of (mercapto)acrylic acid urethane, phenoxy (meth)acrylate, and (fluorenyl). A composition comprising an epoxy acrylate, but any one of the three components is in a different content range from the composition of each of the above embodiments. (Example 5) [3] Preparation of curable composition (Β) 50 parts by weight of an amino phthalic acid acrylate represented by the above formula [1] which is a (mercapto) acrylamide phthalate component As a (meth) 312 ΧΡ / invention specification (supplement) / 96-10/96123707 39 200810922 bisphenol A epoxidized propyl ether type acrylate acrylate represented by the above formula [2] (weight average molecular weight: 2 〇〇〇) 2 parts by weight, as: (decyl) acrylate alicyclic ester component of tricyclodecane diacrylate 3 〇 weight • fraction, 2-hydroxyl as a polymerization initiator — i-[4-[4-(2-hydroxy-2-methyl-propenyl)benzyl]phenyl]-2-methyl-propane-indolyl ketone 2 parts by mass, obtained the hardening of Example 1 Sexual composition. The curable composition has a viscosity of 9000 MPa.s at 60 C and is a pale yellow transparent and viscous liquid. The thermosetting composition of Example 5 was coated with a 250 mm-width mold at a temperature of 60 C, and the thickness of the hardened composition of Example 5 was 25 Å. The surface of the phthalic acid phthalate film is coated with a thickness of not 80, and is irradiated with a illuminance of i J/cm 2 by a metal halide lamp, and is hardened by ultraviolet rays emitted from the metal halide lamp, and then wound up to obtain a double The axially stretched polyethylene terephthalate film laminate is a film of the embodiment of the release film for engineering. The film thickness, thickness accuracy, secondary workability, and light transmittance of the laminated film accompanying the curing shrinkage of the curable composition of Example 1 and the hardening shrinkage of the film φ in the process were evaluated as follows. The results are shown in Table 2. [Evaluation item and evaluation method] <Curing hardening shrinkage> 20 ml of the composition raw material mixture before ultraviolet irradiation was accurately weighed, and the weight was measured, and the density (dl) of the composition was determined. The release film for the detachment of the enamel film of Example 1 was laminated, and the density (d2) of the cured product was determined in accordance with JIS K7ii2, and the curing shrinkage ratio was calculated according to the following formula. Hardening shrinkage ratio (%) = [(d2) - (dl) / (d2)] xl 〇〇 312XP / invention specification (supplement) / 96-10 / 96123707 40 200810922 <curl condition> < Curl condition> Same judgment. In the test, the same <thickness accuracy> and the <thickness accuracy> of the first embodiment are determined. The ash was tested and the same <secondary workability> and the <secondary workability> of the first embodiment were determined. Test and perform the same <light transmittance> = the light transmittance of the example 1 is also tested. [4] Production and evaluation of the optical disk with the cured layer (production of the optical substrate for evaluation) Adhesive of 20 /zm thickness ^ r 4ιί μ ^ ^ The hardened thin MC stripping removal obtained by the above [3] is obtained by stripping and thinning, and is bonded to and opened::: the average film thickness is transparent Disc-shaped mirror substrate (straight; t industry read the poly (10) n ^ soil pole, straight ^ 12 cm, plate thickness 1. 1 mm, warp angle 0 degrees, hereinafter referred to as the substrate) On one of the faces, the following dish with a transparent film layer was prepared and the following results were evaluated. The results are shown in Table 2. <warp> /, and the "thinking" of the example 1 of Beishi apply the same test and make the same judgment. [Examples 6 to 8 and Comparative Examples 6 to 1 〇] 312XP/Flip 嘱 (fine ^ Cong Cong (10) s 200810922 except for the use of the sclerosing compositions shown in the following Tables 2 to 8 and the comparison] In the same manner as in Example 5, the optical disk in which the hardened film layer was formed on the substrate and the obtained product and the hardened material of the composition (4) were formed in the same manner as in Example 5 was obtained. Comment 2 = Obtain the results of the evaluation of Table 2. The results are shown in Table 2 below. (*1)·To make bis (4-isocyanate its king class p Gan , ^鼠文基%己基)Methane and aliphatic polycarbonate 3 ·········································· Acid-amine-based methadone "tongue glutinous soil T-day (heavy averaging numerator; 5000). (*2)·poly (double-awaiting A ring gas, its a creamy secret) acrylic epoxy ester ( Weight average molecule; 1 000). Amount average molecule; 484). 2~Methyl-propionyl)benzyl] (*3): bisphenol A acrylate epoxy ester (heavy (* 4 )·bicyclopyrene Diacrylate vinegar. (* 5) : 2-hydroxy-1 -[4-[4-(hydroxyl)
苯基} -2 -曱基-丙烧-1 —酮。 312XP/發明說明書(補件)/96-10/96123707 42 200810922 [表2]Phenyl} -2 -fluorenyl-propan-1-one. 312XP/Invention Manual (supplement)/96-10/96123707 42 200810922 [Table 2]
自表2可知，活性能量硬化性組成物中之 胺基曱酸酯為40〜60重量之範圍内、（甲基）丙烯酸環^ 酯為10〜40重量％之範圍内、且（甲基）丙烯酸脂環酯為〇 3 0重里％之範圍内的組成物（實施例5〜8之組成物j， 與如下組成物（比較例6〜1 〇之組成物）相比較，於綜合地 觀察所有上述各評估項目的综合判斷中為優良，上述組成 物（比較例6〜10之組成物）雖係由（曱基）丙烯酸胺基甲 酸酯、（甲基）丙烯酸環氧酯、及（曱基）丙烯酸脂環酯所構 成之組成物，但該等3種成分中之任一種成分處於與各實 施例之組成物不同的含量範圍、或為不同成分。 (實施例9) [5]硬化性組成物（c)之製備 混合溶解作為（曱基）丙烯酸胺基甲酸酯成分之上述[2 ] 所示之丙烯酸胺基曱酸酯30質量份、作為含有環氧烷之 (甲基）丙烯酸酯成分之雙酚A環氧乙烷2 mol改質二丙烯 312XP/發明說明書(補件)/96-10/96123707 43 200810922 酸醋20質量份、作為丙烯酸苯氧酯成分之丙烯酸2-經基 - 3-苯氧基丙酯30質量份、作為（甲基）丙烯酸環氧酯成分 '之雙酚A環氧丙基醚型丙烯酸環氧酯20質量份、作為聚 :合起始劑之2一羥基-1 一[4-[4-（2-羥基2-甲基一丙醯基\; 基]苯基]-2-曱基-丙烷—〗—酮2質量份，獲得硬化性組成 物。 所獲得之組成物之黏度於“乞為6〇〇〇 MPa.s，為淡黃 色透明且黏稠的之液體。 _ 於25。0之溫度條件下，利用250 mm寬度之模塗機，將 該硬化性組成物於自卷軸卷開之厚度為188 “mi光學用 之平滑性優良的雙軸延伸聚對苯二甲酸乙二酯薄膜面上 塗佈75 /zm之厚度，利用金屬鹵素燈以} J/cm2之照度， 射紫外線並使之硬化後進行捲取，獲得將雙軸延伸聚對 笨二甲酸乙二酯薄膜積層為工程用脫模薄膜之薄膜。對經 調整之硬化性組成物、使組成物硬化所獲得之薄膜進行如 肇下所示之評估。 [評估項目及評估方法] 〈組成物之黏度〉 使用東機產業公司製造之「黏度測定裝置」m — 10 ，測定25°c之活性能量射線硬化性組成物之黏度。 〈組成物之表面張力〉 ‘使用協和界面科學公司製造之「接觸角測定裝置」 Drop master DM5 00” ，並利用懸滴法測定表面張力。 〈捲曲情況〉 312XP/發明說明書(補件)/96·1〇/961237〇7 44 200810922 與實施例i之〈捲曲情況〉同樣進行測試，並進行相 判定。 α之 :〈硬化物之玻璃轉移溫度〉 ： 使用ίΤ測量控制公司製造之“ΜΑ— 200” ，以1〇 Ηζ 3C/分鐘之速度，使其自—5(rc升溫至15(rc，將t帥占之 最大值作為玻璃轉移溫度。 〈薄膜之線膨脹係數〉 使用Seiko電子（股）製造之“ TMA/ssl2〇(：型，，熱應 ❿畸變測定裝置，於存在氮氣之條件下，以每i分鐘‘、2ς之 比例’使荷重為5 g拉伸模式下所獲得之薄膜的溫度自 上升為60 C，保持1〇分鐘後，以每丨分鐘2它之比例 溫度冷卻至ot，測定並求出5t:〜55t時之值，將線膨 脹係數小於170卿者判定為〇，將大於17{) ppm = 為x。 弋 ◊薄膜平滑性〉 ⑩對於所製作之積層薄膜，使用表面粗度測定器（小阪 究所（股）製造，Siirfacecorder ET4000AK)，來測定硬化 性組成物之空氣侧之表面形狀，且使用三維表面粗度形狀 解析軟體（TDA-22)進行解析。表面形狀之測定條件為， 觸針之遞达速度設為0.5 mm/s，遞送間距設為1〇以瓜， *線數設為1〇卜2倍率設為50000倍。此時，將測定面之 •中心點平均粗糙度Ra為1〇 nm以下者判定為〇，將1〇⑽ 以上者判定為Χ 〇 〈光線透過率〉 312XP/發明說明書(補件)/96-i〇/96123707 45 200810922 〇：90%以上 X :未滿90% 〈二次加工性〉 剝離所獲得之穑局續腊β ^ > 、3 /專膜之工程用基材，對10片薄膜進 丁，切刀之切剔加工，根據切割時之狀況進行以下評估。 〇：所有均被徹底地毫無問題地切斷 X ·發現剖面出現細小龜裂者 - [6][具有硬化物層之光碟之製作及評估] (評估用光碟基材之製作） 使用25 //m厚度之黏著劑，將實施例中所獲得之硬化 2、、且成物’貼合於具有光碟形狀之聚碳酸酯樹脂製透明圓 i狀鏡面基板（直徑12 cin，板厚1· i麗，翹曲角〇°c， 以下簡稱為基材）之一個面上，製作具有硬化物層之光 碟’並進行以下評估。 <耐環境測試〉 對將所獲得之光碟於80°C 85%相對濕度下放置500小時 後之龜曲進行如下判定。 〇 :初期翹曲角與80。〇 85%相對濕度下500小時後之翹 曲角之差未滿〇. 4。。 X ··初期翹曲角與80°C 85%相對濕度下500小時後之翹 曲角之差為〇· 4。以上。 312聊發明說明書(補件)/96•聽61237〇7 46 200810922 〈熱衝擊測試> 對使所獲传之柄於肌至抓之溫度環境下驟變時 :之翹曲變化量進行如下判定。 ~ 5 C /里度環)兄下之翹曲角與環境驟變為55。匸時之魅 曲角之差未滿0.4。 X· 25C溫度環境下之翹曲角肖環境驟變4 55°C時之翹 曲角之差為〇· 4。以下 [實施例10〜丨3、比較例Π〜15] •一除了使用表3之實施例1()〜13及比較例u〜i5之棚所 不之硬化性組成物以外，以與實施例9相同之方式，獲得 於基材上形成有硬化物層之光碟。另外，將與實施例9同 樣對所獲之組成物及光碟進行評估的結果分別表示於 表3之评估結果棚中。 藉由以上所示之方法，組成物之耐熱性、加工性優良， 結果由該組成物所成形之薄膜的韌性、耐熱性、二次加工 •性優良，且積層該薄膜所獲得之光碟的積層之簡便性、厚 度精度、成本優良，^附加價值於工業上較為有用。 312XP/發明說明書(補件)/96-10/96123707 47 200810922It can be seen from Table 2 that the amino phthalic acid ester in the active energy curing composition is in the range of 40 to 60% by weight, and the (meth)acrylic acid ester is in the range of 10 to 40% by weight, and (meth) The acrylate cyclic ester was a composition in the range of 3% by weight (the composition j of Examples 5 to 8 was compared with the following composition (composition of Comparative Example 6 to 1 〇), and all of them were observed comprehensively. It is excellent in the comprehensive judgment of each of the above-mentioned evaluation items, and the above-mentioned composition (composition of Comparative Examples 6 to 10) is made of (meth)acrylic acid urethane, (meth)acrylic acid epoxy ester, and (曱a composition composed of a acrylate cyclic ester, but any one of the three components is in a different content range or a different component from the composition of each example. (Example 9) [5] Hardening Preparation of the composition (c): 30 parts by mass of the amino phthalic acid acrylate represented by the above [2] as a (mercapto) urethane urethane component, as a (meth) group containing an alkylene oxide Acrylate component bisphenol A ethylene oxide 2 mol modified dipropylene 312XP / hair Instruction manual (supplement)/96-10/96123707 43 200810922 20 parts by mass of sour vinegar, 30 parts by mass of 2-cyano-3-phenoxypropyl acrylate as a phenoxy acrylate component, as a (meth)acrylic acid ring 20 parts by mass of bisphenol A epoxidized propyl ether acrylate epoxy ester of oxyester component, 2-hydroxy-1 -[4-[4-(2-hydroxy 2-methyl) as a poly-starter 2 parts by mass of a propyl group; phenyl]-2-mercapto-propane- ketone, a hardening composition is obtained. The viscosity of the obtained composition is "乞 〇〇〇 6 〇〇〇 MPa. It is a light yellow transparent and viscous liquid. _ Under the temperature condition of 25.0, the thickness of the hardening composition is 188" from the reel by a die coater with a width of 250 mm. The biaxially-oriented polyethylene terephthalate film having excellent smoothness is coated on the surface of a film having a thickness of 75 /zm, and is irradiated with ultraviolet light by a metal halide lamp at an illuminance of J/cm2, and is obtained by coiling. The biaxially stretched poly(p-ethylene dicarboxylate) film is a film of a release film for engineering. The cured composition is hardened and the composition is hardened. The obtained film was evaluated as shown in the following section. [Evaluation Project and Evaluation Method] <Viscosity of Composition> Using the "viscosity measuring device" m-10 manufactured by Toki Sangyo Co., Ltd., the active energy ray of 25 °c was measured. Viscosity of the curable composition. <Surface tension of the composition> 'Using the "contact angle measuring device" manufactured by Kyowa Interface Science Co., Ltd., Drop master DM5 00", and measuring the surface tension by the hanging drop method. <Curling condition> 312XP/Invention Instruction manual (supplement)/96·1〇/961237〇7 44 200810922 The test was carried out in the same manner as the <curl condition> of the example i, and the phase determination was performed. α: <glass transition temperature of hardened material>: Use “Τ-200” manufactured by Τ Τ 控制 , , , , , , 200 200 200 200 升温 升温 升温 升温 升温 升温 升温 升温 rc rc rc rc rc rc rc 升温 升温 升温 rc 升温 升温 升温 升温 升温 升温 升温 升温The maximum value of the handsome is taken as the glass transition temperature. <The linear expansion coefficient of the film> The "TMA/ssl2" (: type, heat-induced distortion measurement device manufactured by Seiko Electronics Co., Ltd.) is used in the presence of nitrogen. The ratio of ', 2ς per i minute' makes the temperature of the film obtained in the 5 g tensile mode rise to 60 C. After 1 minute, it is cooled to ot at a rate of 2 per minute. And find the value of 5t: ~ 55t, the coefficient of linear expansion is less than 170, it is judged as 〇, will be greater than 17{) ppm = x. 弋◊ film smoothness> 10 for the fabricated laminated film, the use of thick surface The surface measuring device (Siirfacecorder ET4000AK) was used to measure the surface shape of the air-side of the curable composition, and was analyzed using a three-dimensional surface roughness shape analysis software (TDA-22). Condition, stylus delivery The speed is set to 0.5 mm/s, the delivery pitch is set to 1 〇 melon, * the number of lines is set to 1 〇, and the 2 times ratio is set to 50,000 times. At this time, the average roughness Ra of the center point of the measurement surface is 1〇. Those below nm are judged as 〇, and those below 1〇(10) are judged as Χ 〇 <Light transmittance> 312XP/Invention manual (supplement)/96-i〇/96123707 45 200810922 〇: 90% or more X: Less than 90% <Secondary workability> The substrate obtained for the separation of the wax obtained from the peeling of the β ^ > 3 / film, the cutting of 10 pieces of film, the cutting process of the cutting knife, according to the condition at the time of cutting Evaluation: 〇: All were completely cut off without any problems. X. Found a small crack in the profile - [6] [Production and evaluation of CD with hardened layer] (Production of evaluation disc substrate) 25 / m thick adhesive, the hardened 2 obtained in the example, and the product 'applied to a transparent circular i-shaped mirror substrate made of polycarbonate resin with a disc shape (diameter 12 cin, thickness 1 · i ray, warp angle 〇 ° c, hereinafter referred to as the substrate), on the surface of the substrate, and make a disc with a hardened layer' The following evaluation was carried out. <Environmental resistance test> The tortuosity of the obtained optical disk after being placed at 80 ° C and 85% relative humidity for 500 hours was determined as follows: 〇: initial warpage angle and 80. 〇 85% relative humidity The difference between the warp angles after the next 500 hours is less than 〇. 4. X ·· The initial warpage angle and the warp angle after 500 hours at 80 ° C 85% relative humidity are 〇·4 or more. 312 Talk about the invention (supplement) / 96 • Listen to 61,237 〇 7 46 200810922 <Thermal impact test> When the stalk of the obtained stalk is suddenly changed in the temperature environment of the muscle to the grip: the amount of warpage change is determined as follows. ~ 5 C / 里度环) The warping angle of the brother and the environment suddenly become 55. The charm of the time is less than 0.4. The warpage angle of the X·25C temperature environment suddenly changes. The sharpness of the bend angle at 55 °C is 〇·4. The following [Examples 10 to 3, Comparative Example 15 15] • In addition to the curable composition of Examples 1 () to 13 of Table 3 and Comparative Examples u to i5, In the same manner, a disc having a cured layer formed on the substrate was obtained. Further, the results of evaluation of the obtained composition and optical disk in the same manner as in Example 9 are shown in the evaluation result shed of Table 3, respectively. According to the method shown above, the heat resistance and workability of the composition are excellent, and as a result, the film formed from the composition is excellent in toughness, heat resistance, secondary processing property, and lamination of the optical disk obtained by laminating the film. The simplicity, thickness accuracy, and cost are excellent, and the added value is useful in the industry. 312XP/Invention Manual (supplement)/96-10/96123707 47 200810922
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0CN οε 0§ 9Γη 〇 89 〇 〇 〇 〇 sslg 肅 rf^lasls 裝l^gl ®^^^δ4 a 1 齋慕蹇 |»裝接 Ι^Ι 姓、 SS3 <|敖 導一邊肊-讀旷-<>|-«^«^曾8肊·讀s--(N-w敏di-寸Η,讀部z :瘃紫案鉍 s$,np ^0s3d^2$ - ?T000- 5w$i^^s§.Mh^ss^is#5i - 8寸 卜 0卜 s96/0I-96/ff}«)_&^^a^Aixn e 200810922 自表3可知如下情況。 如實施例9〜13所示，經硬化之蒲π .^ ^ ^ τ 、更化之溥馭於捲曲狀況、薄膜 - 十滑性、光線透過率、-呤知丁从 耐環境測試、熱衝擊 :內】=為良好，對於此種物性而言，於本發明之調配範圍 二正丙烯酸胺基甲酸酯、含有環氧烷之烷化物、丙烯酸 …旨、及根據情況調配之丙烯酸環氧醋的調配量，藉 ^混合物黏土為謂GMPa.s以下，且組成物之表面張0CN οε 0§ 9Γη 〇89 〇〇〇〇sslg Su rf^lasls 装 l^gl ®^^^δ4 a 1 斋慕蹇|»装ΙΙ^Ι Surname, SS3 <|敖导肊肊-读旷-<>|-«^«^ 曾8肊·read s--(Nw敏di-inchΗ, reading z:瘃紫铋铋s$,np ^0s3d^2$ - ?T000- 5w$ i^^s§.Mh^ss^is#5i - 8 inch Bu 0 Bu s96/0I-96/ff}«)_&^^a^Aixn e 200810922 From Table 3, the following is known. As shown in Examples 9 to 13, the hardened Pu π .^ ^ ^ τ , the entanglement of the curling condition, the film - the ten-slip property, the light transmittance, the 呤 丁 从 from the environmental resistance test, the thermal shock :内]= is good, for such physical properties, in the formulation range of the present invention, di-n-acrylic acid urethane, alkylene oxide-containing alkylate, acrylic acid, and acrylic acrylate vinegar formulated according to circumstances The amount of blending, by the mixture of clay is GMPa.s below, and the surface of the composition
Lt:5:45mN/m之範圍内，進而該薄膜之硬化後之玻璃 i二=60〜1〇Q°c之範圍’且於5ΐ〜55°c之範圍内 脹係數可調整為17〇娜化以下，上述測試中，可 滿足所要求之特性且作為本發明之目的的透明而光 :^小之薄膜，或形成經光學功能調整後之窗顯示器. 光碟等之至少一部分之層時的薄膜。 然而，上述混合樹脂中，當超出調配範圍時，如比較例 11〜15所示，無法製造滿足所有要求特性的薄膜。 其次，對由上述硬化性組成物（A)〜（c)m構成之透明薄 膜（上述實施例卜4、5、7、9、1G、12)，進行如下所; 之關於儲存彈性模數測定、厚度精度、抗結塊性、二次加 工性的評估，並將儲存彈性模數及關於薄臈之加工性的 性之评估結果表示於表4中。 、 [評估項目及評估方法] 〈儲存彈性模數測定〉 自上述各實施例之透明薄膜剝離去除工程用脫模薄 膜’使用IT測量控制公司製造之j)VA— 200，以3cc/分鐘 312XP/發明說明書(補件)/96-10/96123707 49 200810922 之升溫速度，使該透明薄膜自—5〇ΐ升溫至15代，測定 25°C與100°C之拉伸彈性率，並進行以下評估。 :室溫彈性# 25°C之儲存彈性模數為2〇〇〇 _以上〇Lt: in the range of 5:45 mN/m, and then the glass after hardening of the film i=60~1〇Q°c range' and the expansion coefficient in the range of 5ΐ~55°c can be adjusted to 17〇娜In the above test, a film which satisfies the required characteristics and which is a transparent film for the purpose of the present invention, or a film which forms an optically-adjusted window display, at least a part of an optical disk or the like . However, in the above mixed resin, when the blending range was exceeded, as shown in Comparative Examples 11 to 15, it was impossible to produce a film satisfying all the required characteristics. Next, the transparent film (the above-described examples 4, 5, 7, 9, 1G, and 12) composed of the curable compositions (A) to (c) m is subjected to the following; The evaluation of the thickness precision, the anti-caking property, and the secondary workability, and the evaluation results of the storage elastic modulus and the workability of the thin enamel are shown in Table 4. [Evaluation Project and Evaluation Method] <Storage Elastic Modulus Measurement> The release film for the transparent film peeling removal engineering of each of the above examples was manufactured using IT Measurement Control Co., Ltd., j) VA-200, at 3 cc/min 312XP/ The temperature rise rate of the invention specification (supplement)/96-10/96123707 49 200810922 is such that the transparent film is heated from -5 Torr to 15 generations, and the tensile modulus at 25 ° C and 100 ° C is measured, and the following evaluation is performed. . : room temperature elasticity # 25 ° C storage elastic modulus is 2 〇〇〇 _ above 〇
: ^ 25 C之儲存彈性模數未滿2000 MPa X 冋/皿彈性率1〇〇c之儲存彈性模數未滿100 MPa〇: ^ 25 C storage elastic modulus less than 2000 MPa X 冋 / dish elastic rate 1〇〇c storage elastic modulus less than 100 MPa〇
looc之儲存彈性模數為100 MPa以上X 〈厚度精度〉 自所積層之各實施例之透明薄膜剝離去除工程用脫模 •薄膜，於該透明薄膜250 _寬度方向上以均等寬度，依 據JIS K7130A—1法並藉由20點測微計來測定，進行如 下判定。 〇·測定值之範圍未滿〇j05mm且標準偏差未滿〇〇〇2〇 mm X ·測定值之範圍未滿〇· 〇05 mm或者標準偏差未滿 0.0020 mmThe storage elastic modulus of the looc is 100 MPa or more. X <Thickness Accuracy> The release film for the transparent film peeling removal process of each of the laminated layers is uniform width in the width direction of the transparent film 250 _ according to JIS K7130A The -1 method was measured by a 20-point micrometer, and the following determination was made. 〇·The range of measured values is less than 05j05mm and the standard deviation is less than 〇2〇 mm X ·The range of measured values is less than 〇· 〇05 mm or the standard deviation is less than 0.0020 mm
〈抗結塊性〉 自所積層之透明薄膜剝離去除 吋之丙烯腈-丁二烯<Anti-caking property> Peeling away from the laminated transparent film Acrylonitrile-butadiene
工程用脫模薄膜，於6 -苯乙烯（ABS 英 acrylonitrile-butadiene-styrene)轴心上捲繞 1〇 m， 將其放置1週之後，進行以下判定。 〇：並未產生結塊，可無問題地進行捲出 X :薄膜之間密接，捲出時發現剝離痕跡 〈二次加工性〉 將所積層之薄膜之薄膜面作為移動刃侧，於2 〇 下對 312XP/發明說明書(補件)/96-10/96123707 50 200810922 根據薄膜之剖面之狀 10片薄膜進行沖切刀之切割加工 況進行如下判定。 所有均被徹底地亳無問題地切斷 X·觀察到剖面出現細小龜裂 另外 、上述比較例 1、2、5、7、9、1{)、n _所構成之薄膜，亦以與上述相同之方丄;估15? 將結果表示於表4中。 万式進仃砰估，並The release film for engineering was wound on a 6-styrene (ABS acrylonitrile-butadiene-styrene) core by 1 〇 m, and after standing for 1 week, the following determination was made. 〇: No agglomeration occurred, and it can be unwound without any problems. X: The film is in close contact with each other, and the peeling marks are found when unwinding. [Secondary workability] The film surface of the film of the laminated layer is used as the moving edge side, at 2 〇 Next, 312XP/Invention Manual (Supplement)/96-10/96123707 50 200810922 The cutting process of the punching blade is performed on the basis of 10 sections of the film. All of them were completely and completely cut off without problems. X. The cracks in the cross section were observed. In addition, the films of Comparative Examples 1, 2, 5, 7, 9, 1{), and n _ were also The same formula; estimate 15? The results are shown in Table 4. 10,000-style estimator, and
再者，表4中之原料如下所示。 丁醋納旱的二=甲酸醋縮合之末端加成丙烯酸4, 4000) 胺基甲酸醋（重量平均分子；觸〜 細酸胺基甲酸醋2:於使甲苯二異氰卿 丁一酵進仃胺基曱酸I缩合之末端加成丙烯酸 : =寻的丙烯酸胺基甲酸醋(重量平均分子；1_: (* 3).丙烯酸胺基f酸§旨3 :於使雙（4_異氰酸基 ，)曱烷與脂肪族聚碳酸酯二醇進行胺基曱酸酯縮合之末 而加成丙烯酉夂4-羥丁酯所獲得的丙烯酸胺基甲酸人 平均分子量5000) α (*4):丙烯酸環氧酯1 :雙酚Α環氧丙基ϋ丙稀酸環 氧酯（分子量484) (*5)丙烯&環氧酯2:聚（雙紛a環氧丙基醚）丙烯 酸環氧酯（重量平均分子量1 Q 〇 〇 ) 312XP/發明說明書(補件)/96-10/96123707 51 200810922 (* 6):含有環氧烷之丙烯酸酯：雙酚a環氧乙烷4 m〇1 改質二丙烯酸酯 (氺7):丙烯酸笨氧酯1:壬基苯氧基乙二醇丙浠酸酯。 (* 8) ··丙烯酸苯氧酯2:丙烯酸2-羥基-3-苯氧基丙酯 (* 9):丙烯酸脂環酯：三環癸烷二丙烯酸酯 (* 10):丙烯酸烷基酯：丙烯酸異癸酯 (* 11):光聚合起始劑：2 -羥基-1 - [ 4 - [ 4 - (經基- 2 -甲 基-丙醯基）苄基]苯基]—2-甲基-丙烷-1-酮。Further, the materials in Table 4 are as follows. Dibutyl vinegar dry 2 = formic acid condensate end addition acrylic acid 4, 4000) Amino carboxylic acid vinegar (weight average molecule; touch ~ fine acid amino carboxylic acid vinegar 2: in the toluene diisocyanine Acryl phthalic acid I condensation end-added acrylic acid: = osmolar acid urethane carboxylic acid (weight average molecule; 1_: (* 3). Amino acid f acid § 3: to make bis (4-isocyanate) Base,) decane and aliphatic polycarbonate diol are condensed with an amino phthalate, and the acryl carboxylic acid obtained by adding 4-hydroxybutyl acrylate has an average molecular weight of 5000) α (*4) : acrylate epoxy ester 1: bisphenol oxime epoxy propyl acrylate acrylic acid ester (molecular weight 484) (*5) propylene & epoxy ester 2: poly (double a epoxidized propyl ether) acrylic ring Oxygen ester (weight average molecular weight 1 Q 〇〇) 312XP / invention specification (supplement) / 96-10/96123707 51 200810922 (* 6): acrylate containing alkylene oxide: bisphenol a ethylene oxide 4 m 〇 1 modified diacrylate (氺7): oxyalkyl acrylate 1: mercaptophenoxy glycol propionate. (* 8) ··Phenyl acrylate 2: 2-hydroxy-3-benzene acrylate Oxypropyl propyl ester (* 9): acrylic acid Cyclic ester: tricyclodecane diacrylate (* 10): alkyl acrylate: isodecyl acrylate (* 11): photopolymerization initiator: 2 -hydroxy-1 - [ 4 - [ 4 - (base group) - 2 -Methyl-propenyl)benzyl]phenyl]-2-methyl-propan-1-one.
312XP/發明說明書(補件)/96-10/96123707 52 200810922-312XP/Invention Manual (supplement)/96-10/96123707 52 200810922-
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0(N os τ 〇 〇 9·9Ι 8061 〇 〇 〇 0。§ (aosl) $s ρ*)ΐ 餵tfIM毽裝lyg 貨 JMlpqwsssf £薦 卜 0Asl96/0I-96/ff}3i)_s?iK^/dx<NIrn 200810922 自表4可知’因以室溫域（25。〇之 _胸以上、高溫域⑽。。)之_ == M:a以下之方式對由本發明之硬化性組 = =薄膜進行調整，故即使加工為薄膜狀，亦不二冓 二沒有黏力而難以處理等問題’各評估項目中 比較例之透明薄膜之儲存彈性模數並未處於 上述靶圍内，因此並不滿足所有各評估項目。 _ (產業上之可利用性） 本發明之活性能量硬化性組成物，近紫外〜近紅外之波 長區域之光之透過率高’透明且光學畸變小，且具有韋刃 性、财熱性，二次加卫性優良，將該活性能量硬化性组成 物薄膜化後，可用作CD等切之光碟之保護層或_等 多層記錄型光碟之接著劑兼透光層。0(N os τ 〇〇9·9Ι 8061 〇〇〇0.§ (aosl) $s ρ*)ΐ Feed tfIM armored lyg goods JMlpqwsssf £ recommended Bu 0Asl96/0I-96/ff}3i)_s?iK^ /dx<NIrn 200810922 It can be seen from Table 4 that the sclerosing group of the present invention = = film due to the _ == M: a or less in the room temperature domain (25 〇 _ _ _ _ _ _ _ _ _ _ _ _ _ Since the adjustment is made, even if it is processed into a film shape, there is no problem that it is difficult to handle without adhesion. The storage elastic modulus of the transparent film of the comparative example in each evaluation item is not in the above-mentioned target circumference, and thus is not satisfied. All evaluation items. _ (Industrial Applicability) The active energy-curable composition of the present invention has a high transmittance of light in a wavelength range from near ultraviolet to near-infrared, which is transparent and has small optical distortion, and has a sharp edge and a richness. It is excellent in secondary addition property, and after thinning the active energy hardening composition, it can be used as a protective layer of a CD or the like, or as an adhesive and a light-transmitting layer of a multilayer recording type optical disc.
^其是’由本發明之活性能量硬化性組成物所構成之透 明薄膜中，400〜410 nm之波長區域之光線透過率高，可 有效地用作利用該波長區域之光信號的次世代型光碟（例 如藍光光碟，UD0等）之構成構件。 312XP/發明說明書(補件 y96-10/96123707 54^ It is a transparent film composed of the active energy-hardening composition of the present invention, and has a high light transmittance in a wavelength region of 400 to 410 nm, and can be effectively used as a next-generation optical disk using an optical signal of the wavelength region. The constituent members of (for example, Blu-ray Disc, UD0, etc.). 312XP / invention manual (supplement y96-10/96123707 54
Claims (1)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006182805 | 2006-06-30 | ||
| JP2006184871 | 2006-07-04 | ||
| JP2007111363 | 2007-04-20 |
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| Publication Number | Publication Date |
|---|---|
| TW200810922A true TW200810922A (en) | 2008-03-01 |
Family
ID=38845619
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW096123707A TW200810922A (en) | 2006-06-30 | 2007-06-29 | Active energy ray curable composition, transparent film made of the composition, and optical disk using the film |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JPWO2008001855A1 (en) |
| TW (1) | TW200810922A (en) |
| WO (1) | WO2008001855A1 (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008176901A (en) * | 2006-12-19 | 2008-07-31 | Mitsubishi Chemicals Corp | Radiation curing composition for optical recording medium and optical recording medium |
| KR20090076754A (en) | 2008-01-08 | 2009-07-13 | 주식회사 엘지화학 | Optical films, retardation films, protective films, and liquid crystal display comprising the sames |
| KR20090076753A (en) | 2008-01-08 | 2009-07-13 | 주식회사 엘지화학 | Transparent resin composition |
| JP5846709B2 (en) * | 2008-03-31 | 2016-01-20 | 太陽ホールディングス株式会社 | Active energy ray-curable resin composition, and its cured product and transparent molded product |
| US8613986B2 (en) | 2008-04-30 | 2013-12-24 | Lg Chem, Ltd. | Optical film and information technology apparatus comprising the same |
| KR101105424B1 (en) | 2008-04-30 | 2012-01-17 | 주식회사 엘지화학 | Resin compositions and optical films formed by using the same |
| JP5504412B2 (en) * | 2008-05-09 | 2014-05-28 | 株式会社ディスコ | Wafer manufacturing method and manufacturing apparatus, and curable resin composition |
| JP5384963B2 (en) * | 2009-02-05 | 2014-01-08 | 株式会社イノアックコーポレーション | Light guide sheet and flexible light guide composition |
| JP5772022B2 (en) * | 2011-02-03 | 2015-09-02 | ソニー株式会社 | Optical information recording medium |
| JP7226324B2 (en) * | 2018-08-23 | 2023-02-21 | 東レ株式会社 | Resin film, laminate, and method for producing laminate |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3176430B2 (en) * | 1992-03-30 | 2001-06-18 | ジェイエスアール株式会社 | Optical three-dimensional molding resin composition |
| JPH0689462A (en) * | 1992-09-07 | 1994-03-29 | Three Bond Co Ltd | Optical disk |
| JPH10182779A (en) * | 1996-12-24 | 1998-07-07 | Dainippon Ink & Chem Inc | Ultraviolet light curable type composition |
| JP2891257B2 (en) * | 1997-07-03 | 1999-05-17 | 住友化学工業株式会社 | Resin composition for protective coating and bonding of DVD |
| JP2001163937A (en) * | 1999-12-07 | 2001-06-19 | Nippon Kayaku Co Ltd | Resin composition for lens and lens sheet |
| JP3897583B2 (en) * | 2000-11-30 | 2007-03-28 | 三菱レイヨン株式会社 | optical disk |
| JP4549657B2 (en) * | 2003-11-25 | 2010-09-22 | 株式会社三共 | Game machine |
| JP2006257342A (en) * | 2005-03-18 | 2006-09-28 | Dainippon Ink & Chem Inc | Ultraviolet-curable composition for optical disc and optical disc using the same |
| JP2007169450A (en) * | 2005-12-21 | 2007-07-05 | Mitsubishi Plastics Ind Ltd | Active energy ray-curable composition, cured film using the composition and optical disk |
-
2007
- 2007-06-28 WO PCT/JP2007/063020 patent/WO2008001855A1/en active Application Filing
- 2007-06-28 JP JP2008522626A patent/JPWO2008001855A1/en active Pending
- 2007-06-29 TW TW096123707A patent/TW200810922A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2008001855A1 (en) | 2009-11-26 |
| WO2008001855A1 (en) | 2008-01-03 |
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