TWI363764B

TWI363764B -

Info

Publication number: TWI363764B
Application number: TW97105039A
Authority: TW
Inventors: Hitoshi Miyao; Yasunobu Suzuki; Shuichi Sugawara; Noriyasu Shinohara
Original assignee: Jsr Corp
Priority date: 2007-02-16
Filing date: 2008-02-13
Publication date: 2012-05-11
Also published as: JP5092440B2; JP2008201818A; TW200844127A

Description

1363764 九、發明說明【發明所屬之技術領域】本發明係關於硬化性組成物、其硬化膜及層合體。更詳細地說，本發明係關於一種可獲得具有優異的防靜電性 (防污染性）之硬化膜的硬化性組成物、其硬化膜及層合體。【先前技術】近年來，防止塑膠（聚碳酸酯、聚甲基甲基丙烯酸酯、聚苯乙烯、聚酯、聚烯烴、環氧樹脂、三聚氰酸樹脂、三乙酸纖維素樹脂、ABS樹脂、AS樹脂、降冰片烯系樹脂等）、金屬、木材、紙、玻璃、石板等之各種基材表面之損傷（擦傷）或防污染用作爲保護塗佈材料及防反射膜用被覆材料之硬化性組成物，係要求具有優異的塗佈性 ’且可形成對各種基材之表面不管是硬度、耐擦傷性、耐磨耗性、表面光滑性、低捲曲性、密著性、透明性、耐藥品性及塗膜面的外觀之任一項均優異的硬化膜。各種.基材之表面賦予了防污染性，故一般而言，硬化膜具有防靜電性。賦予硬化膜防靜電性之方法之1，係於組成物中搭配鋰化合物。例如，在專利文獻1中，揭示有由聚二（甲基）丙烯酸乙二醇酯、分子中不具有聚乙二醇單位而至少有2個 (甲基）丙烯醯氧基之聚合性化合物 '雙全氟鏈烷烴硫醯亞胺鋰、及光起始劑所成之光硬化性樹脂組成物。 -6- 1363764 此專利中，並無使用含聚醚之聚二甲基矽氧烷或含聚醚之全氟烷基寡聚物。此外，因使用較多量的二丙烯酸酯，硬度可能低。專利文獻2中，係揭示有含有選自電離輻射線硬化型樹脂組成物、及全氟烷基磺酸鋰、雙全氟烷基硫醯亞胺鋰及過氯酸鋰之1或2種以上之鋰鹽的光學元件用樹脂組成物。未使用含聚醚之聚二甲基矽氧烷或含聚醚之全氟烷基寡聚物。又，光硬化性單體係使用單官能或二官能之單體，作爲硬塗層有硬度低的可能性。專利文獻3中，係揭示有將矽酸膠微粒子及有機矽烷化合物之水解生成物進行縮合反應所得之含有二氧化矽（ A )、乙烯性不飽和化合物（B)、及特定的鋰化合物之硬化性組成物。雖使用以矽烷偶合劑修飾之二氧化矽粒子，實施例中係使用含有甲基丙烯醯基之矽烷偶合劑，以反應性之觀點來看，可能無法獲得充分的硬度或耐擦傷性。再者，用爲DVD等之記錄用光碟用的硬塗層或、防反射薄膜之情況時，係要求具有指紋拭去性等之防污性。又，例如，用於車輛搭載用之電子機器之記錄用光碟等之情況時，使用中會因爲硬化膜成分流出，或光碟的讀取有障礙，再者可能起火之故，必須要耐濕熱性。 [專利文獻1] 特開2004-331909號公報 1363764 [專利文獻2] 特開2005-3 1 282號公報 [專利文獻3] 特開2005- 146 1 1 0號公報【發明內容】 [發明所欲解決之課題] φ 本發明係以提供可獲得具有優異的防靜電性、防污性、耐濕熱性之硬化膜的硬化性組成物爲其目的。 [解決課題的方法] ' 本發明者等爲達到上述目的而不斷專致於硏究之結果發現，具有聚合性不飽和基，且搭配具聚醚鏈與聚二甲基矽氧烷基之化合物、特定的鋰化合物所成之硬化性組成物係可解決上述課題，本發明遂得以完成。 # 根據本發明，可提供以下的硬化性組成物、其硬化膜及層合體。 1 · 一種硬化性組成物’其係含有下述成分（A)〜 (D ): (A) 含有聚合性不飽和基、以下述式（la)所示之重複單位及以下述式（lb)所示之重複單位之聚合物、 (B) 以下述式（3a)或（3b)所示之化合物、 (c)則述成分（A)以外之分子內具有2個以上之聚合性不飽和基的化合物、 -8- 1363764 (D )光聚合起始劑； [化1] *— -CpH2p〇——* (1a) Γ ch3 ί (1b)1363764 IX. Description of the Invention [Technical Field] The present invention relates to a curable composition, a cured film thereof, and a laminate. More specifically, the present invention relates to a curable composition capable of obtaining a cured film having excellent antistatic properties (anti-contamination property), a cured film thereof, and a laminate. [Prior Art] In recent years, prevention of plastics (polycarbonate, polymethyl methacrylate, polystyrene, polyester, polyolefin, epoxy resin, cyanuric resin, cellulose triacetate resin, ABS resin) , AS resin, norbornene resin, etc., metal, wood, paper, glass, slate, etc., damage (scratch) or anti-pollution on the surface of various substrates, as a protective coating material and hardening of the coating material for anti-reflection film The composition is required to have excellent coating properties' and can form surfaces for various substrates regardless of hardness, scratch resistance, abrasion resistance, surface smoothness, low curling property, adhesion, transparency, A cured film excellent in any of chemical resistance and appearance of a coating film surface. Various surfaces of the substrate impart antifouling properties, and therefore, the cured film generally has antistatic properties. In the method of imparting antistatic property to a cured film, a lithium compound is blended in the composition. For example, Patent Document 1 discloses a polymerizable compound having polyethylene (di)(meth)acrylate and having at least two (meth)acryloxy groups in a molecule without polyethylene glycol units. A photocurable resin composition composed of lithium perfluoroalkane sulfonium imide and a photoinitiator. -6- 1363764 In this patent, polyether-containing polydimethyloxane or polyether-containing perfluoroalkyl oligomers are not used. In addition, the hardness may be low due to the use of a larger amount of diacrylate. Patent Document 2 discloses that one or more selected from the group consisting of an ionizing radiation curable resin composition, lithium perfluoroalkyl sulfonate, lithium diperfluoroalkyl sulfoximine, and lithium perchlorate are contained. A resin composition for an optical element of a lithium salt. Polyether-containing polydimethyl siloxane or polyether-containing perfluoroalkyl oligo is not used. Further, the photocurable single system uses a monofunctional or difunctional monomer, and has a low hardness as a hard coat layer. Patent Document 3 discloses the hardening of cerium oxide (A), an ethylenically unsaturated compound (B), and a specific lithium compound obtained by subjecting a hydric acid colloid fine particle and a hydrolyzate of an organic decane compound to a condensation reaction. Sexual composition. Although cerium oxide particles modified with a decane coupling agent were used, in the examples, a decane coupling agent containing a methacryl oxime group was used, and from the viewpoint of reactivity, sufficient hardness or scratch resistance may not be obtained. In the case of a hard coat layer or an antireflection film for a recording disc such as a DVD, it is required to have antifouling properties such as fingerprint wiping property. In addition, for example, when it is used for a recording disc or the like of an electronic device for mounting a vehicle, the cured film component may flow out during use, or the reading of the optical disk may be impeded, and further heat may occur, and heat and humidity resistance must be maintained. . [Patent Document 1] Japanese Laid-Open Patent Publication No. 2005-331909 (Patent Document 2) Japanese Laid-Open Patent Publication No. Hei No. 2005-3 129 (Patent Document 3) JP-A-2005-146 Problem to be Solved φ The present invention has an object of providing a curable composition capable of obtaining a cured film having excellent antistatic properties, antifouling properties, and moist heat resistance. [Means for Solving the Problem] The inventors of the present invention have found that they have a polymerizable unsaturated group and are compounded with a polyether chain and a polydimethylphosphonium group in order to achieve the above object. The curable composition formed by a specific lithium compound can solve the above problems, and the present invention can be completed. According to the present invention, the following curable composition, cured film, and laminate can be provided. 1 . A curable composition comprising the following components (A) to (D): (A) a repeating unit having a polymerizable unsaturated group represented by the following formula (la) and having the following formula (lb) The polymer of the repeating unit shown, (B) having a compound represented by the following formula (3a) or (3b), and (c) having two or more polymerizable unsaturated groups in a molecule other than the component (A) Compound, -8-1363764 (D) photopolymerization initiator; [Chemical 1] *- -CpH2p〇——* (1a) Γ ch3 ί (1b)

I *βίο ι L CH3」I *βίο ι L CH3"

[式（la)及（lb)中，p 爲 1〜10。][In the formulas (la) and (lb), p is 1 to 10. ]

LiCn，F2n’ + lX (3a) Li(Cn，F2n，+1 Y)2N (3b) [式（3a)及（3b)中，X表示C02或S03、Y表示CO或 S02、n’ 表示1〜9之整數。] 2. 如上述第1項之硬化性組成物，其中，前述成分 (A)所具有之聚合性不飽和基係（甲基）丙烯醯基。 3. 如上述第1或.2項之硬化性組成物，其中，前述成分（A)更含有胺基甲酸酯基。 4. 如上述第1〜3項中任1項之硬化性組成物，其係進一步含有下述成分（E): (E)具有聚合性不飽和基，且以選自矽、鋁、鉻、鈦、鋅、鍺、銦、錫、銻及铈所成群之至少一個元素之氧化物爲主成分之粒子。 5. 如上述第4項之硬化性組成物，其中，前述成分 (E)所具有之聚合性不飽和基係含有以下述式（4)所示 -9- 1363764 構造之基； [化2] —u—c—N— ⑷LiCn, F2n' + lX (3a) Li(Cn, F2n, +1 Y)2N (3b) [In the formulas (3a) and (3b), X represents CO 2 or S03, Y represents CO or S02, and n' represents 1 An integer of ~9. 2. The curable composition according to the above item 1, wherein the component (A) has a polymerizable unsaturated group (meth) acrylonitrile group. 3. The curable composition according to item 1 or 2 above, wherein the component (A) further contains a urethane group. 4. The curable composition according to any one of the above items 1 to 3, further comprising the following component (E): (E) having a polymerizable unsaturated group and selected from the group consisting of ruthenium, aluminum, chromium, A particle containing at least one element of a group of titanium, zinc, bismuth, indium, tin, antimony, and bismuth as a main component. 5. The curable composition according to the above item 4, wherein the polymerizable unsaturated group of the component (E) contains a group having a structure of -9 to 1363764 represented by the following formula (4); —u—c—N— (4)

IIII

VV

[式（4)中，U表示NH、0(氧原子）或s(硫原子 )，V表示0或S。] $ 6.—種硬化膜，其係使如上述第1〜5項中任1項之硬化性組成物硬化而成。 7. —種層合體，其係於基材上具有如上述第6項之硬化膜。 - [發明的效果] 根據本發明，可提供能獲得具有優異的防靜電性、指紋拭去性及耐濕熱性之硬化膜的硬化性組成物。 [實施發明之最佳形態] 1 ·硬化性組成物本發明之硬化性組成物係以含有下述之成分（A )〜 (D)爲特徵。藉由組合成分（A)與（B)進行搭配，即使成分（B )的搭配量少亦可發揮防靜電性。此係推論爲，使此組成物硬化之際，因成分（A )偏向於塗膜之空氣側或基材側界面附近存在，或因成分（A)之聚醚鏈，使成分（B) -10- 1363764 也偏向在界面附近移動存在之故。本發明之硬化性組成物中，以再含有下述成分（E) 爲佳。 (E)具有聚合性不飽和基，且以選自矽、鋁、锆、鈦、鋅、鍺、銦、錫、銻及鈽所成群之至少一個元素之氧化物爲主成分之粒子（以下稱爲反應性粒子）。藉由搭配如此之反應性粒子，可進一步提升硬化膜的 ^ 耐擦傷性。以下，就各成分進行說明。成分（A):含有聚合性不飽和基、式（la)所示之 m複單位及式（lb)所示之重複單位的聚合物用於本發明之成分（A)，係含有聚合性不飽和基 ' '以下述式（la)所示重複單位之聚醚鏈及以下述式（lb )戶斤示重複單位之聚二甲基矽氧烷鏈的聚合物。 [化3] φ *—-CpH2p〇4-* (1a) ch3 ί (1b)[In the formula (4), U represents NH, 0 (oxygen atom) or s (sulfur atom), and V represents 0 or S. A sclerosing film obtained by curing the curable composition according to any one of items 1 to 5 above. 7. A laminate comprising a cured film as in item 6 above, on a substrate. [Effects of the Invention] According to the present invention, it is possible to provide a curable composition capable of obtaining a cured film having excellent antistatic properties, fingerprint wiping property, and moist heat resistance. [Best Mode for Carrying Out the Invention] 1 - Curable Composition The curable composition of the present invention is characterized by containing the following components (A) to (D). By combining the components (A) and (B), the antistatic property can be exhibited even if the amount of the component (B) is small. It is inferred that when the composition is hardened, the component (B) is biased toward the air side of the coating film or near the interface of the substrate side, or the component (B) is caused by the polyether chain of the component (A). 10- 1363764 also tends to move around the interface. The curable composition of the present invention preferably contains the following component (E). (E) particles having a polymerizable unsaturated group and having an oxide of at least one element selected from the group consisting of ruthenium, aluminum, zirconium, titanium, zinc, bismuth, indium, tin, antimony, and bismuth as a main component (hereinafter Known as reactive particles). By combining such reactive particles, the scratch resistance of the cured film can be further improved. Hereinafter, each component will be described. Component (A): a polymer containing a polymerizable unsaturated group, a m complex unit represented by the formula (1), and a repeating unit represented by the formula (lb), which is used in the component (A) of the present invention, and contains a polymerizable property. The saturated group '' repeats a unit of a polyether chain represented by the following formula (la) and a polymer of a polydimethylsiloxane chain having a repeating unit of the following formula (lb). [Chemical 3] φ *—-CpH2p〇4-* (1a) ch3 ί (1b)

I -βίο ι L CH3」 [式（la)中，p 爲 1〜10。；| 成分（A)係藉由與下述成分（B)倂用，即使成分 (B)的添加量少，亦可賦予優異的防靜電性。又，成分 (A)因具有聚合性不飽和基，而以聚合與其他成分鍵結 -11 - 1363764 ，故即使在濕熱條件下，也不會發生凝出粉化。以上述式（la)所示重複單位之聚醚鏈（次烴基氧構造）可爲直鏈狀亦可分支。聚合性不飽和基可具有1個以上，但具有2個以上更好。聚合性不飽和基可舉例如（甲基）丙烯醯基、乙烯基，其中以（甲基）丙烯醯基爲佳。再者，聚合性不飽和基之外，亦可具有胺基甲酸酯。成分（A)以具有下述式（5)〜（8)所示之構造的化合物爲佳。本發明中所用之成分（A)，可藉由在具有下述式（5)〜（8)所示之構造的化合物中導入聚合性不飽和基而製造。I -βίο ι L CH3" [In the formula (la), p is 1 to 10. The component (A) is used in combination with the component (B) described below, and even if the amount of the component (B) added is small, excellent antistatic properties can be imparted. Further, since the component (A) has a polymerizable unsaturated group and is polymerized to bond with other components -11 - 1363764, the clotting does not occur even under moist heat conditions. The polyether chain (sub-hydrocarbyloxy structure) of the repeating unit represented by the above formula (la) may be linear or branched. The polymerizable unsaturated group may have one or more, but more preferably two or more. The polymerizable unsaturated group may, for example, be a (meth)acryl fluorenyl group or a vinyl group, and among them, a (meth) acrylonitrile group is preferred. Further, in addition to the polymerizable unsaturated group, a urethane may also be present. The component (A) is preferably a compound having a structure represented by the following formulas (5) to (8). The component (A) used in the present invention can be produced by introducing a polymerizable unsaturated group into a compound having a structure represented by the following formulas (5) to (8).

-12- 1363764 [化4]-12- 1363764 [化4]

ch3 I O^CkH2k〇)^si〇|^-(-CkH2k〇)-- (5)Ch3 I O^CkH2k〇)^si〇|^-(-CkH2k〇)-- (5)

CH 3 CH, (6) CH34-|i〇|^fckH2k〇)— CH, ch3 ch3 ch3 (7) CH3^SiO-)^Si〇4^SiO^—Si(CH3)3 CH, CH3 R~{ckH2ko 七 ch3 CH3—^SiO CH, CH3 ~)vfs 丨〇+ •Si(CH3)3 (8) R—^CkH2k〇- nCH 3 CH, (6) CH34-|i〇|^fckH2k〇)— CH, ch3 ch3 ch3 (7) CH3^SiO-)^Si〇4^SiO^—Si(CH3)3 CH, CH3 R~{ ckH2ko Seven ch3 CH3—^SiO CH, CH3 ~)vfs 丨〇+ •Si(CH3)3 (8) R—^CkH2k〇- n

[式（5)〜（8)中，p爲1〜l〇; R表示可含有子、硫原子、或雜原子之碳數丨〜2〇的2價有機基； η分別獨立地爲5〜1，〇〇〇; q爲1〜100。] 具有式（5)所示之構造的化合物，其市售品可 SF8427、BY16-201、SF8428、SZ-2162、SH3 773 M ( Corning Toray 製）、KF-8010、KF-1 002、X-22-4952 22-4272、X-22-6266 (信越 Silicone 製）等。成分（A)之聚合物，係可藉由例如’使具有上 (5)〜（8)所示之任一構造的聚合物、2,4 一甲苯 -13- 氧原 m、舉出 Dow 、X- 述式二異 1363764 氰酸酯、二異氰酸異佛爾酮等之異氰酸酯，在二丁基月酸錫存在下進行混合，例如使其於室溫〜40°C反應數小後，添加季戊四醇三丙烯酸酯、丙烯酸羥基乙酯等之含基（甲基）丙烯酸酯，再以例如60 °C〜70 °C使其反應小時程度而製造。本發明之組成物中的成分（A)，當除去（F)有溶劑之組成物全量爲100質量％時，其搭配量以0.01〜質量％爲佳’ 0.1〜25質量％更佳，而0.5〜15質量％更佳。成分（A )之搭配量若低於〇 · 〇 1質量％，恐怕無獲得充分的防靜電性，若超過40質量％則恐怕作爲硬物時的硬度不足。成分（B):式（3a)或（3b)所示之化合物用於本發明之組成物的成分（B)係以下述式（3a 或（3b)所示之含鋰化合物》[In the formulae (5) to (8), p is 1 to l?; R represents a divalent organic group having a carbon number of 丨~2〇 which may contain a sub, a sulfur atom or a hetero atom; η is independently 5~ 1, 〇〇〇; q is 1 to 100. A compound having a structure represented by the formula (5), which is commercially available as SF8427, BY16-201, SF8428, SZ-2162, SH3 773 M (manufactured by Corning Toray), KF-8010, KF-1 002, X- 22-4952 22-4272, X-22-6266 (Shin-Etsu Silicone system), etc. The polymer of the component (A) can be, for example, 'a polymer having any of the structures shown in the above (5) to (8), 2,4-toluene-13-oxygen m, and Dow, X- the above-mentioned diiso 1363764 isocyanate such as cyanate ester or isophorone diisocyanate, and mixed in the presence of tin dibutyl phthalate, for example, after reacting at room temperature to 40 ° C for a small amount, A base (meth) acrylate such as pentaerythritol triacrylate or hydroxyethyl acrylate is added, and the reaction is carried out, for example, at a temperature of from 60 ° C to 70 ° C. In the component (A) in the composition of the present invention, when the total amount of the (F) solvent-containing composition is 100% by mass, the blending amount is preferably 0.01 to 5% by mass, preferably 0.1 to 25% by mass, and 0.5. ~15% by mass is better. If the amount of the component (A) is less than 〇 · 〇 1% by mass, the antistatic property may not be sufficiently obtained. If it exceeds 40% by mass, the hardness may be insufficient as a hard material. Component (B): a compound represented by the formula (3a) or (3b) The component (B) used in the composition of the present invention is a lithium-containing compound represented by the following formula (3a or (3b)"

LiCn’F2n，+ iX (3 a)LiCn’F2n, + iX (3 a)

Li (Cn，F2η ’ + 1 Y)2N (3 b) [式（3a)及（3b)中，X表示c〇2或S03、Y表示CO SO2、n’表示1〜9之整數。] 成分（B)的具體例可舉出全氟乙酸鋰、全氟丙酸、全氟丁酸鋰、全氟戊酸鋰、全氟己酸鋰、全氟庚酸鋰全氟辛酸鋰、全氟壬酸鋰、全氟癸酸鋰、三氟甲磺酸鋰全氟乙磺酸鋰、全氟丙磺酸鋰、全氟丁磺酸鋰、全氟戊酸鋰、全氟己磺酸鋰、全氟庚酸鋰、全氟辛酸鋰、全氟桂時羥數機 40 又法化或鋰 X % 擴壬 -14· 1363764 酸鋰、鋰雙三氟甲硫醯亞胺、鋰雙全氟甲硫醯亞胺、鋰全氟乙硫醯亞胺、鋰雙全氟丙硫醯亞胺、鋰雙全氟丁硫亞胺、鋰雙全氟戊硫醯亞胺、鋰雙全氟己硫醯亞胺、鋰 '全氟庚硫醯亞胺、鋰雙全氟辛硫醯亞胺、鋰雙全氟壬硫亞胺、鋰雙三氟甲碳化亞胺、鋰雙全氟乙酸醯亞胺、鋰全氟丙酸醯亞胺、鋰雙全氟丁酸醯亞胺、鋰雙全氟戊酸亞胺、鋰雙全氟己酸醯亞胺、鋰雙全氟庚酸醯亞胺、鋰全氟辛酸醯亞胺、鋰雙全氟壬酸醯亞胺、鋰雙全氟癸酸 .亞胺等。又，市售亦有成分（B)與具聚合性不飽和基之化物的混合物，可舉例如 SankonolA600-30R、A600-20R PETA-30R、PETA-20R、A4 00-20R (三光化學工業（股 )等。本發明之組成物中的成分（B)，當除去（F)有溶劑之組成物全量爲1 0 0質量％時，其搭配量以0.0 1〜質量％爲佳，更佳爲0.05〜15質量％，而0.1〜10質 %又更佳。成分（B)之搭配量若低於〇.〇1質量％，恐無法獲得充分的靜電衰減性，若超過20質量％，則恐作爲硬化物時之硬度不足。又，作爲硬化物時擔心硬化法到達下部（內部）。 (C)前述成分（A)之外的分子內具有2個以上合性不飽和基之化合物（多官能聚合性有機化合物）本發明所用之多官能聚合性有機化合物（C)，適用於提高組成物之成膜性。硬化時，成分（A)之聚合雙醯雙醯雙醯雙醯合 ) 機 20 量怕怕姐 y»\> 聚合性 -15- 1363764 不飽和基也一起反應形成聚合物。多官能聚合性有機化合物（C)只要爲分子內含有2個以上聚合性不飽和基者則無特別限制’可舉例如（甲基）丙烯酸酯類、乙烯基化合物類。此等之中，以（甲基）丙烯酸酯類爲佳。 (甲基）丙烯酸酯類可舉出三羥甲基丙三（甲基）丙烯酸酯、二三羥甲基丙四（甲基）丙烯酸酯、季戊四醇三 (甲基）丙烯酸酯、季戊四醇四（甲基）丙烯酸酯、二季戊四醇五（甲基）丙烯酸酯、二季戊四醇六（甲基）丙烯酸酯、丙三醇三（甲基）丙烯酸酯、參（2—羥乙基）異氰尿酸酯三（甲基）丙烯酸酯、乙二醇二（甲基）丙烯酸酯、丨，3 — 丁二醇二（甲基）丙烯酸酯、1,4 — 丁二醇二（甲基）丙烯酸酯、1，6—己二醇二（甲基）丙烯酸酯、新戊二醇二（甲基）丙烯酸酯、二乙二醇二（甲基）丙烯酸醋、三乙二醇二（甲基）丙烯酸酯、二丙二醇二（甲基）丙烯酸酯、雙（2—羥乙基）異氰尿酸酯二（甲基）丙烯酸酯等羥基含有（甲基）丙烯酸酯類、及對此等羥基之氧化乙烯或氧化丙烯加成物之聚（甲基）丙烯酸酯類、分子內具有2個以上（甲基）丙烯醯基之寡聚酯（甲基）丙烯酸酯類、寡聚醚（甲基）丙烯酸酯類、寡聚胺基甲酸酯（甲基）丙烯酸酯類 '及寡聚環氧（甲基）丙烯酸酯類、下述式（4) 、（5)所示之化合物等。此等之中，係以二季戊四醇六（甲基）丙烯酸酯、二季戊四醇五（甲基）丙烯酸酯、季戊四醇四（甲基）丙烯酸酯、二三羥甲基丙四（甲基）丙烯酸酯' 下述式（9) 、（10)所示之化合物等 -16- 1363764Li (Cn, F2η ' + 1 Y) 2N (3 b) [In the formulae (3a) and (3b), X represents c〇2 or S03, and Y represents CO SO2 and n' represents an integer of 1 to 9. Specific examples of the component (B) include perfluoroacetic acid lithium, perfluoropropionic acid, perfluorobutyric acid lithium, perfluoropentanoic acid lithium, perfluorohexanoic acid lithium, lithium perfluoroheptanoate perfluorooctanoic acid, and perfluoroanthracene. Lithium acid, lithium perfluoroantimonate, lithium trifluoromethanesulfonate, lithium perfluoropropane sulfonate, lithium perfluoropropane sulfonate, lithium perfluoropentanoic acid, lithium perfluoropentanoic acid, lithium Lithium fluoroheptanoate, lithium perfluorooctanoate, perfluoro-cold-counting machine 40 or normalized or lithium X% 壬-14· 1363764 Lithium acid, lithium bistrifluoromethyl sulfoximine, lithium bis-perfluoromethyl thioimine , lithium perfluoroethyl sulfinimide, lithium bis-perfluoropropanthine, lithium bis-perfluorobutyl sulfilimine, lithium bis-perfluoropentathioimine, lithium bis perfluoro hexamethylene sulfoxide, lithium 'perfluoroglycol Thioinimide, lithium bis-perfluorooctyl sulfinimide, lithium bisperfluoro sulfinimide, lithium bistrifluoromethaneimide, lithium bis-perfluoroacetate yttrium, lithium perfluoropropionate yttrium, lithium bis Bismuth fluorobutyrate, lithium diperfluorovaleric acid imide, lithium bis-perfluorohexanoate yttrium imide, lithium bis-perfluoroheptanoate yttrium imide, lithium perfluorooctanoate ylide, lithium bis-perfluoroantimonate yttrium, lithium double Fluoro decanoic acid. Imine. Further, a mixture of the component (B) and a compound having a polymerizable unsaturated group is commercially available, and examples thereof include Sankonol A600-30R, A600-20R PETA-30R, PETA-20R, and A4 00-20R (Sanguang Chemical Industry Co., Ltd. When the component (B) in the composition of the present invention is removed, the total amount of the solvent-containing composition is 100% by mass, and the amount thereof is preferably 0.01 to 3% by mass, more preferably 0.05. ~15% by mass, and 0.1 to 10% by mass is more preferable. If the amount of the component (B) is less than 〇.〇1% by mass, sufficient electrostatic attenuation may not be obtained, and if it exceeds 20% by mass, it may be When the cured product is insufficient in hardness, it is feared that the hardening method reaches the lower portion (inside). (C) Compound having two or more unsaturated unsaturated groups in the molecule other than the above component (A) (polyfunctional polymerization) Organic compound (C) The polyfunctional polymerizable organic compound (C) used in the present invention is suitable for improving the film formability of the composition. When hardened, the amount of the polymerized bismuth-biguanide compound of the component (A) is 20 Fear of sister y»\> Polymerity -15- 1363764 Unsaturation is also anti- To form a polymer. The polyfunctional polymerizable organic compound (C) is not particularly limited as long as it contains two or more polymerizable unsaturated groups in the molecule, and examples thereof include (meth)acrylates and vinyl compounds. Among these, (meth) acrylates are preferred. Examples of the (meth) acrylate include trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, and pentaerythritol tetra(a). Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa(meth) acrylate, glycerol tri(meth) acrylate, ginseng (2-hydroxyethyl) isocyanurate (meth) acrylate, ethylene glycol di(meth) acrylate, hydrazine, 3-butanediol di(meth) acrylate, 1,4-butanediol di(meth) acrylate, 1, 6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, diethylene glycol di(meth)acrylate vinegar, triethylene glycol di(meth)acrylate, two Hydroxy groups such as propylene glycol di(meth) acrylate and bis(2-hydroxyethyl)isocyanurate di(meth)acrylate contain (meth) acrylates, and ethylene oxide or oxidation of such hydroxyl groups Poly(meth)acrylates of propylene adducts having two or more molecules (in the molecule) Methyl) acrylonitrile-based oligoester (meth) acrylates, oligoether (meth) acrylates, oligomeric urethane (meth) acrylates, and oligomeric epoxies ( Methyl) acrylates, compounds represented by the following formulas (4) and (5), and the like. Among these, dipentaerythritol hexa(meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylol propyl tetra (meth) acrylate Compounds represented by the following formulas (9) and (10), etc. - 16 - 1363764

爲佳。 [化5]It is better. [Chemical 5]

OAcryl (9)OAcryl (9)

OAcryl OAcryl (10) [式（9)及式（10)中，「Acryl」表示丙烯醯基。] 乙烯基化合物類可舉出二乙烯基苯、乙二醇二乙烯基醚、二乙二醇二乙烯基醚、三乙二醇二乙烯基醚等。OAcryl OAcryl (10) [In the formulas (9) and (10), "Acryl" means an acrylonitrile group. The vinyl compound may, for example, be divinylbenzene, ethylene glycol divinyl ether, diethylene glycol divinyl ether or triethylene glycol divinyl ether.

如此之聚合性有機化合物（C )的市售品，可舉例如東亞合成（股）製 ARONIXM-400、M-404、M-408、M-450、M-3 05、M-3 09、M-3 10、M-3 1 5、M-3 20、M-3 5 0、 M-3 60、M-208、M-210、M-215、M-220、M-225、M-233 、M-240 ' M-245、M-260、M-270、M-1100、M- 1 200、M-1210、M-1310、M- 1 600、M-221、M-203、TO-924、T0-1 270 ' TO-1231、TO-5 9 5、TO-756、TO- 1 3 43、TO-902 ' TO-904、TO-905 、TO- 1 3 3 0、日本化藥（股）製 KAYARAD D-310' D-33 0、DPHA、DPCA-20、DPCA-30、 DPCA-60、DPCA-120、DN-0075、DN-2475 ' SR-295、 SR-3 5 5、SR-399E、SR-494、SR-904 1、SR-3 68、SR-415 、SR-444 、 SR-454 、 SR-492 、 SR-499 、 SR-502 、 SR-9020 -17- 1363764 、SR-9035 ' SR-1 1 1、SR-212、SR-213、SR-23 0、SR-259 、SR-268、SR-272、SR-344、SR-3 49、SR-601、SR-602 、SR-610、SR-9003、PET-30、T- 1 420、GPO-3 03、TC-120S、HDDA、NPGDA、TPGDA、PEG400DA、MANDA、 HX-220、HX-620、R-551、R-712 ' R-167、R-526、R-551 、R-712、R-604、R-684、TMPTA、THE-3 30、TPA-320、 TPA-330 ' KS-HDDA、KS-TPGDA、KS-TMPTA、共榮社 • 化學（股）製 LIGHT-ACRYLATE PE-4A、DPE-6A、 DTMP-4A 等。本發明之組成物中的成分（C)，當除去（F)有機溶劑之組成物全量爲100質量％時，其搭配量爲5〜80質 ' 量％。較佳爲1〇〜80質量％，更佳爲15〜80質量％。若 - 低於5質量％或超過80質量％時，作爲硬化物時恐無法獲得高硬度者。又，作爲層合體時，硬化膜與基材間的密著性可能會降低。 φ 此外’若是含有後述之成分（E)之組成物的情況，成分（C)的搭配量中，不含成分（e)。 (D)光聚合起始劑聚合起始劑（D )可舉出，藉由輻射線（光）照射而使其產生活性自由基種之化合物（輻射線（光）聚合起始劑）。幅射線（光）聚合起始劑，若爲藉由光照射而分解產生自由基後開始聚合者並無特別限制，可舉例如苯乙酮 -18- 1363764 、苯乙酮苄基縮酮、1 一羥基環己基苯基酮、2,2 —二甲氧基一 1，2 —二苯基乙一1—酮、氧雜蒽酮、芴酮、苯甲醛、芴、蒽醌、三苯基胺、咔唑、3 —甲基苯乙酮、4_氯二苯甲酮、4,4’一二甲氧基二苯甲酮、4,4’一二胺基二苯甲酮、苯偶因丙基酸、苯偶因乙基醚、苄基二甲基縮酮、1-(4_異丙基苯基）一2 —羥基一2 —甲基丙一1 一酮、2 — 經基—2—甲基-1 一苯基丙一 1-酮、硫代氧雜恵酮、二乙基硫代氧雜蒽酮、2—異丙基硫代氧雜蒽酮、2 -氯硫代氧雜蒽酮、2 -甲基_1_ [4 一（甲基硫代）苯基]_2_嗎啉代—丙一 1-酮、2_苄基一 2 —二甲基胺基—1— (4 一嗎啉代苯基）一丁酮一 1，4_ (2 -羥基乙氧基）苯基—（ 2_羥基一 2 —丙基）酮、2,4,6 —三甲基苯醯二苯基氧化膦、雙一（2,6—二甲氧基苯醯）一2,4,4 —三甲基戊基氧化膦、寡聚（2 -羥基_2_甲基一 1一（4- (1—甲基乙烯基）苯基）丙酮）等。輻射線（光）聚合起始劑之市售品可舉例如Ciba Specialty Chemicals (股）製 IRUGACUR 184、3 69、651 、5 00、819、907、784、2959、CGI 1 700、CGI 1 75 0 > CGI1850、CG2 4-61、DAROCUR 1116、1173、BASF 社製 LUCIRIN TPO、8 8 93 、UCB 社製 UBECRYL P36、 LANBELTY CORPORATION 社製 EZACUR - KIP150、 KIP65LT、KIP100F、KT37、KT55、KT046、KIP75/B 等 o 聚合起始劑（D)之搭配量，當除去（F)有機溶劑 -19- 1363764 之組成物全量爲100質量％時，係以搭配0.01〜20質量 %爲佳，〇_1〜10質量％更佳，0.5〜10質量％又更佳。若低於0.0 1質量％，作爲硬化物時之硬度會不足，若超過20質量％，則作爲硬化物時硬化無法到達內部（下層 )° 此外’本發明中，視其必要可使光聚合起始劑與熱聚合起始劑倂用。較佳的熱聚合起始劑可舉例如過氧化物、偶氮化合物 ’具體例可舉出苯醯過氧化物、t-丁基-過氧化苯甲酸酯、偶氮雙異丁腈等。 (E)具有聚合性不飽和基，且以選自矽、鋁、錆、鈦、鋅、鍺、銦、錫、銻及铈所成群之至少一個元素之氧化物爲主成分之粒子本發明中，視其必要可搭配之成分（E )(以下亦稱爲「反應性粒子」）係藉由使選自矽、鋁、锆'鈦、鋅、鍺、銦、錫、銻及鈽所成群之至少一個元素之氧化物爲主成分之粒子（Ea)，與分子內具有聚合性不飽和基及水解性甲矽烷基之有機化合物（Eb )反應而得。若搭配成分（E)，可與成分（A)及（C)所具有之聚合性不飽和基反應’且藉由聚合，可更加提高所得硬化膜之硬度，而且，因可減少硬化收縮（彎曲）而較佳。 (1)以氧化物爲主成分之粒子（Ea) 用於製造反應性粒子（E)之氧化物粒子（Ea)，由 -20- 1363764 所得硬化性組成物之硬化膜的無色性觀點來看，其係以選自矽、鋁、鉻、鈦、鋅、鍺、銦、錫、銻及铈所成群之至少一個元素之氧化物爲主成分之粒子》此等之氧化物粒子（Ea )可舉例如二氧化矽、氧化鋁、氧化锆、氧化鈦、氧化鋅、氧化鍺、氧化銦、氧化錫、銦錫氧化物（ITO)、氧化銻、氧化鈽等之粒子。其中，從高硬度之觀點來看，以二氧化矽、氧化鋁、氧化鉻及氧化銻之粒子爲佳。此等可單獨使用或組合2種以上使用。尙且，氧化物粒子（Ea)較佳係用爲粉體狀或溶劑分散溶膠。用爲溶劑分散溶膠時，從與其他成分之相溶性、分散性的觀點來看，其分散媒介以有機溶劑爲佳。如此之有機溶劑可舉例如甲醇、乙醇、異丙醇、丁醇、辛醇等之醇類 :丙酮、甲基乙基酮、甲基異丁基酮、環己酮等之酮類；乙酸乙酯、乙酸丁酯、乳酸乙酯、r — 丁內酯、丙二醇單甲基醚乙酸酯、丙二醇單乙基醚乙酸酯等之酯類；乙二醇單甲基醚、二乙二醇單丁基醚等之醚類；苯、甲苯、二甲苯等之芳香族烴類；二甲基甲醯胺、二甲基乙醯胺、N-甲基吡咯烷酮等之醯胺類。其中，以甲醇、異丙醇、丁醇、甲基乙基酮、甲基異丁基酮、乙酸乙酯、乙酸丁酯、甲苯、二甲苯爲佳。氧化物粒子（Ea)之數平均粒子徑，以0.001 // m〜2 較佳，更佳爲 0.003/zm〜1/zm，而 0_005/zm 〜0.5 /zm特別佳。數平均粒子徑若超過2/zm，作爲硬化物時之透明性會降低，且作爲硬化膜時的表面狀態有惡化之傾 -21 - 1363764 向。又，爲了改善粒子的分散性’可添加各種界面活性劑或胺類。氧化物粒子之數平均粒子徑係以動態散亂進行測定。矽氧化物粒子（例如二氧化矽粒子）之市售商品，可舉例如矽酸膠，可舉出日產化學工業（股）製甲醇二氧化矽溶膠、IPA-ST、MEK-ST、NBA-ST、XBA-ST、DMAC-ST ' ST-UP ' ST-OUP ' ST-20、ST-40、ST-C、ST-N ' ST-0、ST-50、ST-OL等。又，粉體二氧化矽方面可舉出日本 AER0SIL (股）製 AER0SIL 130、AEROSIL 3 00、 AEROSIL 380、 AEROSIL TT600、 AEROSIL 0X50、旭硝子（股）製 SILDEX H31、H32、H51、H52、H121、H122 、曰本二氧化矽工業（股）製E220A、E220、富士 Fuji Silysia (股）製SYLYSIA4 70、日本板硝子（股）製SG 薄片等。又，氧化鋁之水分散品可舉出有日產化學工業（股）製氧化鋁溶膠-100、-200、-520 ;氧化鋁之異丙醇分散品可舉出有住友大阪CEMENT (股）製AS-150I;氧化鋁之甲苯分散品可舉出有住友大阪CEMENT (股）製AS-150T :氧化锆之甲苯分散品可舉出有住友大阪CEMENT (股）製HXU-1 10JC ;銻酸鋅粉末之水分散品可舉出有日產化學工業（股）製CELNAX ;氧化鋁、氧化鈦、氧化錫、氧化銦、氧化鋅等之粉末及溶劑分散品可舉出有C.I.化成（股）製NAN0TEK;摻雜銻之氧化錫的水分散溶膠可舉出有石原產業（股）製 SN-100D; ITO粉末可舉出有三菱 -22- 1363764Such a commercially available product of the polymerizable organic compound (C) may, for example, be ARONIXM-400, M-404, M-408, M-450, M-3 05, M-3 09, M manufactured by East Asia Synthetic Co., Ltd. -3 10, M-3 1 5, M-3 20, M-3 5 0, M-3 60, M-208, M-210, M-215, M-220, M-225, M-233, M-240 'M-245, M-260, M-270, M-1100, M-1 200, M-1210, M-1310, M-1 600, M-221, M-203, TO-924, T0-1 270 'TO-1231, TO-5 9 5, TO-756, TO- 1 3 43, TO-902 'TO-904, TO-905, TO- 1 3 3 0, Nippon Chemical Co., Ltd. KAYARAD D-310' D-33 0, DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA-120, DN-0075, DN-2475 'SR-295, SR-3 5 5, SR-399E , SR-494, SR-904 1, SR-3 68, SR-415, SR-444, SR-454, SR-492, SR-499, SR-502, SR-9020 -17- 1363764, SR-9035 'SR-1 1 1, SR-212, SR-213, SR-23 0, SR-259, SR-268, SR-272, SR-344, SR-3 49, SR-601, SR-602, SR -610, SR-9003, PET-30, T-1 420, GPO-3 03, TC-120S, HDDA, NPGDA, TPGDA, PEG400DA, MANDA, HX-220, HX-620, R-551, R-712 'R-167, R-526, R-551, R-712, R-604, R-684, TMPTA, THE-3 30, TPA-320, TPA-330 'KS-HDDA, KS-TPGDA, KS-TMPTA, Kyoeisha Chemical Co., Ltd. LIGHT-ACRYLATE PE-4A , DPE-6A, DTMP-4A, etc. In the component (C) in the composition of the present invention, when the total amount of the composition of the (F) organic solvent is 100% by mass, the amount of the component is 5 to 80% by mass. It is preferably from 1 to 80% by mass, more preferably from 15 to 80% by mass. If it is less than 5% by mass or more than 80% by mass, it may not be possible to obtain a high hardness as a cured product. Further, when it is a laminate, the adhesion between the cured film and the substrate may be lowered. φ In addition, in the case of a composition containing the component (E) to be described later, the component (C) does not contain the component (e). (D) Photopolymerization initiator The polymerization initiator (D) is a compound (radiation (light) polymerization initiator) which generates an active radical species by irradiation with radiation (light). The ray (light) polymerization initiator is not particularly limited as long as it is decomposed by light irradiation to generate a radical, and is, for example, acetophenone-18-1638764 or acetophenone benzyl ketal. 1 monohydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenyleth-1-one, xanthone, anthrone, benzaldehyde, hydrazine, hydrazine, triphenylamine , carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, benzoin Propyl acid, benzoin ethyl ether, benzyl dimethyl ketal, 1-(4-isopropylphenyl)-2-hydroxyl-2-methylpropan-1-one, 2- — 2-methyl-1-phenylpropan-1-one, thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioox Xanthone, 2-methyl_1_[4-(methylthio)phenyl]_2-morpholino-propan-1-one, 2-benzyl- 2-dimethylamino-1—( 4 monomorpholinophenyl)-butanone-1,4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-oxa)one, 2,4,6 — Methylphenylphosphonium diphenylphosphine oxide, bis(2,6-dimethoxybenzoquinone)-2,4,4-trimethylpentylphosphine oxide, oligomeric (2-hydroxy-2-methyl) 1-1-1 (4-(1-methylvinyl)phenyl)acetone) and the like. Commercial products of the radiation (photo) polymerization initiator may, for example, be IRUGACUR 184, 3 69, 651, 5 00, 819, 907, 784, 2959, CGI 1 700, CGI 1 75 0 manufactured by Ciba Specialty Chemicals Co., Ltd. > CGI1850, CG2 4-61, DAROCUR 1116, 1173, LUCIRIN TPO, 8 8 93 by BASF, UBECRYL P36 by UCB, EZACUR - KIP150, KIP65LT, KIP100F, KT37, KT55, KT046, KIP75/ B, etc. o The amount of the polymerization initiator (D), when the total amount of the composition of the organic solvent -19-1363764 is removed to 100% by mass, preferably 0.01 to 20% by mass, 〇_1~ 10% by mass is more preferable, and 0.5 to 10% by mass is more preferably. When it is less than 0.01% by mass, the hardness as a cured product may be insufficient. When it exceeds 20% by mass, the hardened material may not be cured to the inside (lower layer). Further, in the present invention, photopolymerization may be carried out as necessary. The initiator is used in combination with a thermal polymerization initiator. The preferred thermal polymerization initiator may, for example, be a peroxide or an azo compound. Specific examples thereof include benzoquinone peroxide, t-butyl-peroxybenzoate, azobisisobutyronitrile, and the like. (E) particles having a polymerizable unsaturated group and having an oxide of at least one element selected from the group consisting of ruthenium, aluminum, iridium, titanium, zinc, ruthenium, indium, tin, antimony and bismuth as a main component of the present invention Among them, the component (E) (hereinafter also referred to as "reactive particle") which is compatible with it is formed by selecting yttrium, aluminum, zirconium, titanium, zinc, antimony, indium, tin, antimony and bismuth. The particles (Ea) having an oxide of at least one element of the group as a main component are reacted with an organic compound (Eb) having a polymerizable unsaturated group and a hydrolyzable formyl group in the molecule. When the component (E) is blended, it can react with the polymerizable unsaturated groups of the components (A) and (C) and the hardness of the obtained cured film can be further improved by polymerization, and the hardening shrinkage can be reduced (bending) ) and better. (1) Particles containing oxide as a main component (Ea) For producing oxide particles (Ea) of reactive particles (E), from the viewpoint of colorlessness of a cured film of a curable composition obtained in -20 to 1363764 It is a particle mainly composed of an oxide of at least one element selected from the group consisting of ruthenium, aluminum, chromium, titanium, zinc, bismuth, indium, tin, antimony and bismuth. These oxide particles (Ea) For example, particles such as cerium oxide, aluminum oxide, zirconium oxide, titanium oxide, zinc oxide, cerium oxide, indium oxide, tin oxide, indium tin oxide (ITO), cerium oxide, or cerium oxide may be mentioned. Among them, from the viewpoint of high hardness, particles of cerium oxide, aluminum oxide, chromium oxide and cerium oxide are preferred. These may be used alone or in combination of two or more. Further, the oxide particles (Ea) are preferably used in the form of a powder or a solvent dispersion sol. When it is used as a solvent-dispersed sol, the dispersion medium is preferably an organic solvent from the viewpoint of compatibility with other components and dispersibility. Examples of such an organic solvent include alcohols such as methanol, ethanol, isopropanol, butanol, and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; Ester, butyl acetate, ethyl lactate, r-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, etc.; ethylene glycol monomethyl ether, diethylene glycol An ether such as monobutyl ether; an aromatic hydrocarbon such as benzene, toluene or xylene; or a guanamine such as dimethylformamide, dimethylacetamide or N-methylpyrrolidone. Among them, methanol, isopropanol, butanol, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, toluene, and xylene are preferred. The number average particle diameter of the oxide particles (Ea) is preferably 0.001 // m 2 or more, more preferably 0.003 / zm 1 / 1 / zm, and 0 - 005 / zm - 0.5 / zm is particularly preferable. When the number average particle diameter exceeds 2/zm, the transparency as a cured product is lowered, and the surface state as a cured film is deteriorated to a gradient of -21 - 1363764. Further, various surfactants or amines may be added in order to improve the dispersibility of the particles. The number average particle diameter of the oxide particles was measured by dynamic dispersion. The commercially available product of the cerium oxide particles (for example, cerium oxide particles) may, for example, be a ceric acid gel, and may be a methanol dioxide cerium oxide sol, IPA-ST, MEK-ST or NBA-ST manufactured by Nissan Chemical Industries Co., Ltd. , XBA-ST, DMAC-ST 'ST-UP 'ST-OUP 'ST-20, ST-40, ST-C, ST-N 'ST-0, ST-50, ST-OL, etc. Further, examples of the powdered cerium oxide include AER0SIL 130, AEROSIL 3 00, AEROSIL 380, AEROSIL TT600, AEROSIL 0X50, and Asahi Glass Co., Ltd. manufactured by AER0SIL Co., Ltd., H32, H51, H52, H121, H122. E220A, E220, SYLYSIA4 70 made by Fuji Fuji Silysia Co., Ltd., SG sheet made by Nippon Sheet Glass Co., Ltd., etc. Further, the water-dispersion of alumina may be exemplified by Nissan Chemical Industry Co., Ltd. alumina sol-100, -200, -520; and the isopropyl alcohol dispersion of alumina may be Sumitomo Osaka CEMENT (share) AS-150I; Alumina toluene dispersibles include Sumitomo Osaka CEMENT (stock) AS-150T: zirconia toluene dispersions can be found in Sumitomo Osaka CEMENT (shares) HXU-1 10JC; zinc citrate Examples of the water-dispersible powder include CELNAX manufactured by Nissan Chemical Industries Co., Ltd.; powders and solvent dispersions of alumina, titania, tin oxide, indium oxide, zinc oxide, and the like, and NAN0TEK manufactured by CI Chemical Co., Ltd. The water-dispersible sol of cerium-doped tin oxide may be SN-100D manufactured by Ishihara Sangyo Co., Ltd.; ITO powder may be exemplified by Mitsubishi-22-1363764

Materials (股）製之製品；氧化鈽之水分散液可舉出有多木化學（股）製NEEDRAL等。氧化物粒子（Ea)之形狀爲球狀、中空狀、多孔質狀、棒狀、板狀、纖維狀、或不固定形狀，較佳爲球狀。氧化物粒子（Ea)之比表面積（使用氮氣之BET比表面積測定法）較佳爲 10〜1 000m2/g，更佳爲100〜5 00m2/g。此等氧化物粒子（Ea )的使用形態係可使用以乾燥狀態之粉末、或水或是有機溶劑經分散之狀態。例如，上述氧化物的溶劑分散溶膠係可直接使用該當業界習知之微粒子狀氧化物粒子的分散液。特別是在硬化物上要求具優異的透明性之用途中，以氧化物之有機溶劑分散溶膠的利用爲佳 (2)有機化合物（Eb) 本發明中所用之有機化合物（Eb )係具有聚合性不飽和基之化合物，較佳爲含有以下述式（4)所示之基之有機化合物。 [化6] Η … —U-C-N—— (4)Products made of Materials; the water dispersion of cerium oxide can be exemplified by NEEDRAL. The oxide particles (Ea) have a spherical shape, a hollow shape, a porous shape, a rod shape, a plate shape, a fibrous shape, or an unfixed shape, and are preferably spherical. The specific surface area of the oxide particles (Ea) (the BET specific surface area measurement using nitrogen) is preferably from 10 to 1 000 m 2 /g, more preferably from 100 to 500 m 2 /g. The use form of these oxide particles (Ea) can be used in a state in which a powder in a dry state or water or an organic solvent is dispersed. For example, as the solvent-dispersing sol of the above oxide, a dispersion of fine particle-like oxide particles as known in the art can be used as it is. In particular, in the use of an excellent transparency in a cured product, it is preferred to use an organic solvent-dispersed sol of an oxide. (2) Organic compound (Eb) The organic compound (Eb) used in the present invention is polymerizable. The compound of the unsaturated group is preferably an organic compound containing a group represented by the following formula (4). [6] Η ... —U-C-N—— (4)

IIII

VV

[式（4)中，U表示ΝΗ、0(氧原子）或S(硫原子 )，乂表不0或8。] 其中，又以含有[-0-C( = 0)-NH-]基，且更含有 -23- 1363764 [-〇-C( = S)-NH-]基及[-S-C( = 0)-NH-]基之至少其1者爲佳。又，此有機化合物（Eb)係以分子內具有矽氫氧基之化合物或藉由水解而生成矽氫氧基之化合物爲佳。 (i) 聚合性不飽和基有機化合物（Eb)中所含之聚合性不飽和基並無特別限制，可舉例如丙烯醯基、甲基丙烯醯基、乙烯基、丙烯基、丁二烯基、苯乙烯基、乙炔基、肉桂醯基、順丁烯二酸酯基、丙烯醯胺基爲較適之例。此聚合性不飽和基係藉由活性自由基種進行加成聚合之構成單位。 (ii) 前述式（4)所示之基有機化合物中所含之以前述式（4)所示之基[-U-C( = V)-NH-]具體而言有[-0-C( = 0)-NH-]、[-0-C( = S)-NH-] 、[-S-C( = 0)-NH-]、[-NH-C( = 0)-NH-]、[-NH-C( = S)-NH-] 、及[-S-C( = S)-NH-]之6種。此等之基係可單獨使用1種或組合2種以上使用。其中，從熱安定性之觀點來看，以與[-0-C( = 0)-NH-]基、[-0-C( = S)-NH-]基及[-S-C( = 0)-NH-]基之至少一個併用爲佳。前述式（4)所示之基[-U-C( = V)-NH-]，若於分子間使其產生氫鍵所致之適度的凝聚力而爲硬化物的情況時，會賦予優異的機械性強度、基材或高折射率層等之與鄰接層的密著性及耐熱性等之特性。 -24- 1363764 (in)藉由矽氫氧基或水解生成矽氫氧基之基有機化合物（Eb)係以分子內具有矽氫氧基之化合物或藉由水解生成矽氫氧基之化合物爲佳。如此生成矽氫氧基之化合物，可舉出於矽原子上鍵結烷氧基、芳氧基、乙醯氧基、胺基、齒素原子等化合物，其中較佳爲矽原子上鍵結烷氧基或芳氧基之化合物，意即，含烷氧基甲矽烷基之化合物或含芳氧基甲矽烷基之化合物。矽氫氧基或生成矽氫氧基之化合物的矽氫氧基生成部位，係藉由縮合反應或水解後發生之縮合反應而與氧化物粒子（Ea)鍵結之構成單位。 (iv)較佳樣態有機化合物（Eb )的較佳具體例，可舉例如下述式（ 1 1 )所示之化合物。 [化7] (〇R6)j | |_| R73.j—SiH-R8—S-C-N-R9—N-C-O-R10—(Z)k 〇 Ο 式（1 1 )中’ R6、R7係可相同或相異之氫原子或碳數1〜8之烷基或芳基，可舉例如甲基、乙基、丙基、丁基、辛基、苯基、二甲苯基等。在此，j係1〜3之整數。 [(R60)jR73.jSi-]所示之基，可舉例如三甲氧基甲矽烷基、三乙氧基甲矽烷基、三苯氧基甲矽烷基、甲基二甲氧 -25- 1363764 基甲矽烷基、二甲基甲氧基甲矽烷基等。此等基之中，以三甲氧基甲矽烷基或三乙氧基甲矽烷基等爲佳。 R8係碳數1〜12之脂肪族或具有芳香族構造之2價有機基，亦可含鏈狀、分支狀或環狀之構造。具體例可舉出甲撐、乙撐、丙撐、丁撐、六甲撐、環己撐、苯撐、苯撐二甲基、十二甲撐等。 R9係2價有機基，通常分子量爲14至1萬；較佳爲由分子量76至5 00之2價有機基中選出。具體例可舉出六甲撐、八甲撐、十二甲撐等之鏈狀聚烷撐基；環己撐、伸降冰片烷基等之脂環式或多環式的2價有機基；苯撐、萘撐、雙苯撐、聚苯撐等之2價芳香族基；及此等之烷基取代物、芳基取代物。又，此等2價有機基可具有含碳及氫原子以外之元素的原子團，亦可含有聚醚鍵、聚酯鍵、聚醯胺鍵、聚碳酸酯鍵。 R1()爲（k+Ι)價之有機基，較佳係由鏈狀、分支狀或環狀之飽和烴基、不飽和烴基之中所選出。 Z表示在活性自由基種的存在下，於分子中具有進行分子間交聯反應之聚合性不飽和基之1價有機基。又，k 較佳爲1〜20之整數，更佳爲1〜10之整數，其中特別佳爲1〜5之整數。式（11)所示之化合物的具體例，係可舉出下述式（ 1 2 )及（1 3 )所示之化合物。 -26- 1363764[In the formula (4), U represents ΝΗ, 0 (oxygen atom) or S (sulfur atom), and 乂 is not 0 or 8. Wherein, it contains [-0-C(=0)-NH-], and further contains -23- 1363764 [-〇-C(=S)-NH-] and [-SC( = 0) At least one of the -NH-] groups is preferred. Further, the organic compound (Eb) is preferably a compound having a hydrazine hydroxyl group in the molecule or a compound which forms a hydrazine hydroxy group by hydrolysis. (i) The polymerizable unsaturated group contained in the polymerizable unsaturated organic compound (Eb) is not particularly limited, and examples thereof include an acryl fluorenyl group, a methacryl fluorenyl group, a vinyl group, a propenyl group, and a butadienyl group. A styryl group, an ethynyl group, a cinnamyl group, a maleate group, and an acrylamide group are preferred examples. The polymerizable unsaturated group is a constituent unit of addition polymerization by an active radical species. (ii) The group [-UC(=V)-NH-] represented by the above formula (4) contained in the base organic compound represented by the above formula (4) specifically has [-0-C (= 0) -NH-], [-0-C( = S)-NH-] , [-SC( = 0)-NH-], [-NH-C( = 0)-NH-], [-NH 6 kinds of -C( = S)-NH-] and [-SC( = S)-NH-]. These bases may be used alone or in combination of two or more. Among them, from the viewpoint of thermal stability, with [-0-C(=0)-NH-], [-0-C(=S)-NH-], and [-SC( = 0) It is preferred to use at least one of the -NH-] groups. The group [-UC(=V)-NH-] represented by the above formula (4) imparts excellent mechanical properties when it is a hardened material due to an appropriate cohesive force due to hydrogen bonding between molecules. Characteristics such as strength, adhesion to the adjacent layer, and heat resistance of the substrate, the high refractive index layer, and the like. -24- 1363764 (in) The organic compound (Eb) based on a hydronium oxy group or hydrolyzed to form a hydrazine hydroxy group is a compound having a hydrazine hydroxyl group in the molecule or a compound forming a hydrazine hydroxy group by hydrolysis. good. The compound in which the hydrazine hydroxy group is formed may be a compound in which an alkoxy group, an aryloxy group, an ethoxylated group, an amine group, a dentate atom or the like is bonded to a ruthenium atom, and preferably a ruthenium atom-bonded alkane. A compound of an oxy or aryloxy group, that is, a compound containing an alkoxycarbenyl group or a compound containing an aryloxycarboxyalkyl group. The oxime hydroxyl group forming moiety of the hydrazine hydroxyl group or the hydrazine hydroxy group-forming compound is a constituent unit bonded to the oxide particles (Ea) by a condensation reaction or a condensation reaction which occurs after hydrolysis. (iv) Preferred embodiment A preferred embodiment of the organic compound (Eb) is, for example, a compound represented by the following formula (1 1 ). [〇7] (〇R6)j | |_| R73.j—SiH-R8—SCN-R9—NCO-R10—(Z)k 〇Ο In the formula (1 1 ), the R6 and R7 systems can be the same or phase. Examples of the hydrogen atom or the alkyl group or the aryl group having 1 to 8 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group, a phenyl group, and a xylyl group. Here, j is an integer of 1 to 3. The group represented by [(R60)jR73.jSi-] may, for example, be a trimethoxycarbenyl group, a triethoxycarbenyl group, a triphenyloxycarbenyl group or a methyldimethoxy-25-1363764 group. Formyl, dimethylmethoxymethyl, and the like. Among these groups, a trimethoxycarbenyl group or a triethoxycarbenyl group is preferred. R8 is an aliphatic group having 1 to 12 carbon atoms or a divalent organic group having an aromatic structure, and may have a chain, a branched or a cyclic structure. Specific examples thereof include methyl, ethylene, propylene, butyl, hexamethylene, cyclohexene, phenylene, benzodimethyl, and dodecyl. R9 is a divalent organic group, usually having a molecular weight of from 14 to 10,000; preferably selected from a divalent organic group having a molecular weight of from 76 to 500. Specific examples thereof include a chain polyalkylene group such as hexamethylene, octamethylidene, and dodecylylene; an alicyclic or polycyclic divalent organic group such as cyclohexene or bornereyl; and benzene; a divalent aromatic group such as a phthalocyanine, a bisphenylene or a polyphenylene; and an alkyl substituent or an aryl substituent. Further, these divalent organic groups may have an atomic group containing an element other than carbon and a hydrogen atom, and may also contain a polyether bond, a polyester bond, a polyamine bond, or a polycarbonate bond. R1() is an organic group of (k + Ι) valence, and is preferably selected from a chain hydrocarbon, a branched or cyclic saturated hydrocarbon group, and an unsaturated hydrocarbon group. Z represents a monovalent organic group having a polymerizable unsaturated group which undergoes an intermolecular crosslinking reaction in the molecule in the presence of a living radical species. Further, k is preferably an integer of from 1 to 20, more preferably an integer of from 1 to 10, and particularly preferably an integer of from 1 to 5. Specific examples of the compound represented by the formula (11) include compounds represented by the following formulas (1 2 ) and (13). -26- 1363764

[化8][化8]

'sw/Svv<>>/\^Si(OCH3)3 τ (12)'sw/Svv<>>/\^Si(OCH3)3 τ (12)

Si(OCH3)3 (13) [式（12)及式（13)中，「Aery 1」表示丙烯醯基。] 本發明中所用之有機化合物（Eb )的合成，係可使用例如特開平9- 1 00 11 1號公報中所記載之方法。較佳爲藉由使氫硫基丙基三甲氧基矽烷與二異氰酸異佛爾酮於二丁基錫二月桂酸酯存在下混合，在60〜7〇t使其反應數小時程度之後，添加季戊四醇三丙烯酸酯，再於60〜70 t 使其反應數小時程度所製造。 (3)反應性粒子（E)之調製使具有矽氫氧基或藉由水解而生成矽氫氧基之基的有機化合物（Eb)與金屬氧化物粒子（Ea)混合，使其水解並使兩者鍵結。所得之反應性粒子（E)中的有機聚合物成分即水解性矽烷的水解物及縮合物之比例，通常，使乾燥粉體於空氣中完全燃燒時的質量減少％之恆量値，係可藉由例如於空氣中由室溫至通常800 °C爲止的熱質量分析 -27- 1363764 而求得。朝氧化物粒子（Ea)鍵結之有機化合物（Eb)的鍵結量’當反應性粒子（E)(金屬氧化物粒子（Ea)及有機化合物（Eb)之合計）爲1〇〇質量％，較佳爲〇.〇!質量 %以上，而更佳爲0.1質量％以上，其中以1質量％以上特別好。鍵結於金屬氧化物粒子（Ea)之有機化合物（Eb )的鍵結量若低於0.01質量％，組成物中之反應性粒子 (E)的分散性不足，所得硬化物的透明性、耐擦傷性會變得不夠充分。又，反應性粒子（E)製造時，原料中的金屬氧化物粒子（Ea)之搭配比例較佳爲5〜99質量％，更佳爲10〜98質量％。構成反應性粒子（E)之氧化物粒子（Ea)的含量，較佳爲反應性粒子（E)的65〜95質量 %。反應性粒子（E)於硬化性組成物中之含量，當除去 (F )有機溶劑使組成物全體爲1 00質量.％，係以5〜8 5 質量％爲佳。更佳爲10〜80質量％，而10〜75質量％特別佳。若低於5質量％，作爲硬化物時，將無法得到高硬度的硬化物，而超過85質量％時，則成膜性不足。此外，反應性粒子（E)之含量意指固形成分，當反應性粒子（E )以溶劑分散溶膠之形態被使用時，其含量不包含溶劑的量。本發明之硬化性組成物中，亦可視需要添加（F )有機溶劑。有機溶劑可舉例如甲醇、乙醇、異丙醇、丁醇、辛醇 -28- 1363764 等之醇類；丙酮、甲基乙基酮、甲基異丁基酮、環己酮等之酮類；乙酸乙酯、乙酸丁酯、乳酸乙酯、r_T內醋、丙二醇單甲基醚乙酸酯、丙二醇單乙基醚乙酸醋等之酯類 :乙二醇單甲基醚、二乙二醇單丁基醚等之醚類；苯、甲苯、二甲苯等之芳香族烴類；二甲基甲醯胺、二甲基乙醯胺、N—甲基吡咯烷酮等之醯胺類等。 (F )有機溶劑本發明之硬化性樹脂組成物中，以進一步添加有機溶劑爲佳。藉由添加如此之有機溶劑，係可均—地形成硬化膜。如此之有機溶劑係可舉出丙酮、甲基異丁基酮、甲基乙基酮、環己酮、甲基戊基酮等之酮類、乙酸乙酯、乙酸丁酯、丙二醇單甲基醚乙酸酯等之酯類、丙二醇單甲基醚、甲醇、乙醇、sec — 丁醇、t - 丁醇、2 —丙醇、異丙醇等之醇類、苯、甲苯、氯苯等之芳香族類、己烷、環己烷等之脂肪族類等，其單獨一種或或組合二種以上。此等之中，以丙酮、甲基異丁基酮、甲基乙基酮、環己酮、甲基戊基酮等之酮類、乙酸乙酯、乙酸丁酯、丙二醇單甲基醚乙酸酯等之酯類、丙二醇單甲基醚、甲醇、乙醇、sec-丁醇、t 一丁醇、2—丙醇、異丙醇等之醇類爲佳，而更佳爲甲醇、丙二醇單甲基醚、甲基乙基酮、甲基異丁基酮之單獨一種或組合二種以上。關於（F )有機溶劑的添加量並無特別限制，相對於去除有機溶劑之組成物全量100質量份而言，較佳爲100 -29- 1363764 〜100,000質量份。此理由在於，添加量若低於100質量份，有硬化性組成物的黏度調整困難之情形，另外，添加量若超過1 00,000質量份，則硬化性組成物的保存安定性將會降低、或有黏度過低而難以操作的情形》 ' (G)氟系添加劑本發明之硬化性組成物中因添加氟系之添加劑，而可 φ 賦予防污性、指紋拭去性。成分（G)的市售品有]^0?-35 0SF、F-470、F4 77大日本油墨化學工業（股）社製等。氟系添加劑（G)之搭配量，當去除（F)有機溶劑之組成物全量爲100質量％時，以搭配0.01〜10質量％爲 ' 佳，0·05〜5質量％更佳，0.1〜3質量％又更佳。若低於 - 〇.01質量％ ’無法獲得充分的效果，若超過ίο質量％，則作爲硬化物時無法得到足夠的硬度，或硬化達不到內部 (下層）。 (Η )其他的添加劑本發明之硬化性組成物中，在無損本發明之效果下，可視必要適當地搭配光增感劑、聚合禁止劑、聚合起始助劑、勻塗劑、潤濕性改良劑、界面活性劑、可塑劑、紫外線吸收劑、抗氧化劑、防靜電劑 '無機塡充劑、顔料、染料等。 2 ·硬化膜•層合體 -30- 本發明的硬化膜或層合體係藉由使本發明之硬化性組成物於基材上硬化而得。基材可舉例如塑膠（聚碳酸酯、聚甲基丙烯酸酯、聚苯乙烯、聚酯、聚烯烴、環氧、三聚氰酸、三乙酸纖維素、ABS、AS、降冰片烯系樹脂等）、金屬、木材、紙、玻璃、石板等。此等基材之形狀可爲板狀、薄膜狀或3次元成形體。此外，可視需要於基材與硬化膜之間形成介在層。組成物的塗佈方法係可舉出一般的塗佈方法，例如浸漬塗佈、噴墨塗佈、流液塗佈、淋液塗佈、輥筒塗佈、旋轉塗佈、刷毛塗佈等。此等塗佈中之塗膜的厚度，經乾燥、硬化後通常爲0.1〜400#m，較佳爲1〜200ym。爲了調節塗膜的厚度，本發明之組成物係可以上述之有機溶劑（F)稀釋後使用。例如，用爲防反射膜或被覆材料時之黏度，通常爲 0.1〜5 0,000mPa·秒/25t，較佳爲 0.5 〜1 0,000mPa·秒/25。。° 塗佈之後，較佳係於〇〜20(TC使其揮發成分乾燥後，可藉由熱及/或輻射線進行硬化處理得到層合體。藉由熱硬化時，較佳的硬化條件係於20〜150 °C、10 秒〜24小時之範圍內施行。藉由輻射線硬化時，係以使用紫外線或電子線爲佳，而在該情況下，較佳的紫外線照射光量係0.01〜10J/cm2，較佳爲0.1〜2J/cm2。又，較佳的電子線照射條件係加速電壓1 〇〜300kV、電子密度〇.〇2 〜0.30mA/cm2、電子線照射量爲1〜lOMrad。 1363764 硬化時的熱源可使用例如電熱器、紅外線燈、熱風等〇又，光或電子線的線源，若是可使組成物在塗佈後短時間內硬化者，並無特別限制。例如，紅外線的線源可舉出照射燈、電阻加熱板、雷射等，可視光線的線源可舉出曰光、照射燈、螢光燈、雷射等，紫外線的線源可舉出水銀照射燈、鹵素燈、雷射等。又，電子線的線源則可舉出有市售之利用由鎢燈絲產生之熱電子的方式，或利用於金屬上透過高電壓脈衝產生之冷陰極方式及利用藉由經離子化之氣態分子與金屬電極之衝突產生之2次電子之2次電子方式。又，α射線、yS射線及r射線之線源可舉例如 Co等之核分裂物質’而r射線可利用使加速電子對陽極衝突之真空管等。此等輻射線係可以單獨1種或2種以上同時地或間隔固定期間進行照射。本發明之層合體用爲防反射膜時，使本發明之組成物硬化所得之硬化膜通常可爲具有防靜電性之硬塗層之層的功能。作爲防反射膜時，端視其必要而形成高折射率層、中折射率層、低折射率層等》【實施方式】 [實施例] 以下’本發明藉由實施例更具體地進行說明，但本發明並不受限於此等之實施例。此外，以下所述之「份」、「％」若無特別記載’則分別表示質量份、質量％。 -32- 1363764 製造例1:具有聚合性不飽和基之有機化合物（Eb)的製造乾燥空氣中，對氫硫基丙基三甲氧基矽烷221份、二丁基錫二月桂酸酯1份所成之溶液，以1小時於50°C將二異氰酸異佛爾酮222份一邊攪拌邊滴下後，於701加熱攪拌3小時。於上述溶液中，於30 °C下花1小時將新中村化學製NK酯 A-TMM-3LM-N (由季戊四醇三丙烯酸酯60質量％與季戊四醇四丙烯酸酯40質量％所組成。當中，參與反應的只爲具有羥基之季戊四醇三丙烯酸酯） 5 49份滴下後，於60 °C經過10小時的加熱攪拌而獲得含聚合性不飽和基之有機化合物（Ab )。以FT-IR分析生成物中的殘存異氰酸酯量，若爲0.1%以下，則表示反應幾乎爲定量性地終了。生成物之紅外線吸收光譜，係原料中氫硫基上特徵之25 5 0CITT1的吸收波峰及原料異氰酸酯化合物上特徵之2260(:1^1的吸收波峰消失，而新觀察到胺基甲酸酯鍵結及S(C = 0)NH-基上特徵之1 660cm·1的波峰及丙烯醯氧基上特徵之 mOcrrT1的波峰，其係表示生成作爲聚合性不飽和基且同時具有丙烯醯氧基與-S(C = 0)NH-、胺基甲酸酯鍵結之經丙烯醯氧基修飾之烷氧基矽烷。依上述，除了獲得773份前述式（12)或（13) 所示之化合物（Eb)之外，有220份與反應無關之季戊四醇四丙烯酸酯混在其中。 -33- 1363764 製造例2:反應性粒子分散液的調製使製造例1中製造之組成物9.35份（含有具聚合性不飽和基之有機化合物（Eb) 7.28份）、二氧化矽粒子分散液（Ea)(二氧化矽濃度32%、平均粒徑10nm、日產化學工業（股）製甲醇二氧化矽溶膠）89.90份、離子交換水0.12份、及p -羥基苯基單甲基醚0.01份之混合液，於60°C攪拌4小時後，添加原甲酸甲基酯1.36份，再於同一溫度加熱攪拌1小時而得反應性粒子之分散液。將此分散液於鋁製秤量盤秤2 g後，於175 °C之加熱板上乾燥1小時進行秤量，求得固形成分含量37.8%。又，將分散液於磁性鍋爐秤量2g後，在80 °C的加熱板上預備乾燥30分，於750°C之隔焰爐中經1小時燒成後，從其無機殘渣求得固形成分中之無機含量爲75.5%。製造例3:成分（A)之化合物的製造對由甲苯二異氰酸酯59份及二丁基錫二月桂酸酯1 份所成之溶液，以數個小時滴入含聚醚之聚二甲基矽氧烷 (DOWCORNING TORAY (股）社製 S F 8427 ) 360 份，在室溫攪拌3小時。於上述溶液中，25t下以1小時將新中村化學製NK酯 A-TMM-3LM-N(由季戊四醇三丙烯酸酯60質量％與季戊四醇四丙烯酸酯40質量％所組成。當中，參與反應的只爲具有羥基之季戊四醇三丙烯酸酯） 1 7 3份滴下後，於6 0 °C經過1 0小時的加熱攪拌獲得目的之含聚合性不飽和基的有機化合物（A)。以FT-IR分析 -34- 1363764 生成物中的殘存異氰酸酯量，若爲0.1%以下，則應幾乎爲定量性地終了。生成物之紅外線吸收光譜料異氰酸酯化合物上特徵之2260cm·1的吸收波峰而新觀察到胺基甲酸酯鍵結及 C = ONH -基上； 1 660CJTT1的波峰及丙烯醯氧基上特徵之1 720cm·1 ，其係表示生成同時具有作爲聚合性不飽和基的丙基與-C = ONH-、胺基甲酸酯鍵結之含聚醚之聚二甲烷。依上述，除了獲得522份賦予成分（A)聚合和基之含聚醚之聚二甲基矽氧烷之外，有69份與關之季戊四醇四丙烯酸酯混在其中。實施例1 (1)硬化性組成物的調製於遮蔽紫外線之附有攪拌機的容器中，以表1 比例加入各成分，於室溫下攪拌1小時後得到均一物。 (2 )層合體的製作使以上述（1)所作成之組成物，於基材之聚上藉由旋轉塗佈進行塗佈。之後，室溫下乾燥1分塗膜。接著，在大氣中使用高壓水銀照射’J 500mJ/cm2之光照射條件使塗膜經紫外線硬化，製 l〇/zm之硬化膜，而得層合體。表不反，係原消失，寺徵之的波峰烯醯氧基矽氧性不飽反應無所示之的組成碳酸酯鐘形成 I，以作膜厚 -35- 1363764 實施例2〜3、參考例1〜2及比較例1〜4 其他表1中記載之搭配，係與實施例1同樣實施以調製組成物，並獲得層合體。評價例就上述實施例、參考例及比較例所得之層合體，評價下述特性，其結果列示於表1。 (1)靜電衰減率半衰期（分）就上述實施例、參考例及比較例所作成之層合體，使用 Static Honest Meter 、 Honest Meter Analyzer ( ' SHISHID〇靜電氣（股）社製）施加3kV之電壓，測定所 • 施加電壓變成一半之i.5kV時的時間（靜電衰減率半衰期 (分））。 (2)水及油酸接觸角（°) 水及油酸的接觸角，係使用固液界面解析裝置 DROP MASTER500 (協和界面科學（股）社製）之自動接觸角接觸角計’於層合體表面作成液滴，就作成5秒後，分別測定水與層合體、油酸與層合體之界面的角度。水及油酸的接觸角係與指紋拭去性有密切的關係，水、油酸接觸角之値愈高，指紋拭去性愈好。 (3 )指紋拭去性 -36- 1363764 實際上將指紋附著於層合體上，以柔軟的布拭去後’ 目測觀察指紋的痕跡。沒有痕跡爲〇、殘留若干痕跡爲^ '無法拭去爲X。 (4)濕熱試驗下析出物的有無將層合體置於80 °C、80% RH的恆溫恆濕下，經過 1 00小時後，目測以確認油狀析出物的有無。Si(OCH3)3 (13) [In the formulas (12) and (13), "Aery 1" represents an acrylonitrile group. For the synthesis of the organic compound (Eb) used in the present invention, for example, the method described in JP-A-9-10011 1 can be used. Preferably, the mixture is prepared by mixing thiopropylpropyltrimethoxydecane with isophorone diisocyanate in the presence of dibutyltin dilaurate, reacting at 60 to 7 Torr for several hours, and then adding Pentaerythritol triacrylate is produced by reacting it at 60 to 70 t for several hours. (3) Preparation of Reactive Particles (E) An organic compound (Eb) having a hydrazine hydroxyl group or a group which forms a hydrazine hydroxy group by hydrolysis is mixed with metal oxide particles (Ea) to be hydrolyzed and The two keys. The ratio of the hydrolyzate and the condensate of the hydrolyzable decane to the organic polymer component in the obtained reactive particle (E) is usually a constant amount of % reduction in mass when the dry powder is completely burned in the air. It is determined by, for example, thermal mass analysis -27- 1363764 in air from room temperature to usually 800 °C. The amount of bonding of the organic compound (Eb) bonded to the oxide particles (Ea) is 1% by mass of the reactive particles (E) (the total of the metal oxide particles (Ea) and the organic compound (Eb)) It is preferably 〇.〇!% by mass or more, and more preferably 0.1% by mass or more, and particularly preferably 1% by mass or more. When the amount of bonding of the organic compound (Eb) bonded to the metal oxide particles (Ea) is less than 0.01% by mass, the dispersibility of the reactive particles (E) in the composition is insufficient, and the cured product is transparent and resistant. The scratching will become insufficient. Further, in the production of the reactive particles (E), the proportion of the metal oxide particles (Ea) in the raw material is preferably from 5 to 99% by mass, more preferably from 10 to 98% by mass. The content of the oxide particles (Ea) constituting the reactive particles (E) is preferably 65 to 95% by mass based on the reactive particles (E). The content of the reactive particles (E) in the curable composition is preferably from 5 to 85% by mass, based on the total amount of the organic solvent to be removed (F). More preferably, it is 10 to 80% by mass, and 10 to 75% by mass is particularly preferable. When the amount is less than 5% by mass, a cured product having a high hardness cannot be obtained as a cured product, and when it is more than 85% by mass, the film formability is insufficient. Further, the content of the reactive particles (E) means a solid component, and when the reactive particles (E) are used in the form of a solvent-dispersed sol, the content thereof does not include the amount of the solvent. In the curable composition of the present invention, (F) an organic solvent may be added as needed. The organic solvent may, for example, be an alcohol such as methanol, ethanol, isopropanol, butanol or octanol-28-1363764; a ketone such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone; Esters of ethyl acetate, butyl acetate, ethyl lactate, r_T internal vinegar, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate vinegar, etc.: ethylene glycol monomethyl ether, diethylene glycol single An ether such as butyl ether; an aromatic hydrocarbon such as benzene, toluene or xylene; or a guanamine such as dimethylformamide, dimethylacetamide or N-methylpyrrolidone. (F) Organic solvent In the curable resin composition of the present invention, it is preferred to further add an organic solvent. By adding such an organic solvent, a hardened film can be formed uniformly. Examples of such an organic solvent include ketones such as acetone, methyl isobutyl ketone, methyl ethyl ketone, cyclohexanone, and methyl amyl ketone, ethyl acetate, butyl acetate, and propylene glycol monomethyl ether. An ester such as acetate, propylene glycol monomethyl ether, methanol, ethanol, sec-butanol, t-butanol, 2-propanol, isopropanol, alcohol, benzene, toluene, chlorobenzene, etc. An aliphatic group such as a steroid, a hexane or a cyclohexane may be used alone or in combination of two or more. Among these, ketones such as acetone, methyl isobutyl ketone, methyl ethyl ketone, cyclohexanone, methyl amyl ketone, ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate An ester such as an ester, propylene glycol monomethyl ether, methanol, ethanol, sec-butanol, t-butanol, 2-propanol, isopropanol or the like is preferred, and more preferably methanol or propylene glycol monomethyl The ether, methyl ethyl ketone, and methyl isobutyl ketone may be used alone or in combination of two or more. The amount of the (F) organic solvent to be added is not particularly limited, and is preferably from 100 -29 to 1363764 to 100,000 parts by mass based on 100 parts by mass of the total amount of the organic solvent-removing composition. The reason for this is that if the amount is less than 100 parts by mass, the viscosity of the curable composition is difficult to adjust, and if the amount is more than 100,000 parts by mass, the storage stability of the curable composition is lowered, or In the case where the viscosity is too low, it is difficult to handle. '(G) Fluorine-based additive The fluorine-based additive is added to the curable composition of the present invention to impart antifouling properties and fingerprint wiping properties. Commercially available products of the component (G) include ^0?-35 0SF, F-470, F4 77, and the Japan Ink Chemical Industry Co., Ltd. system. When the total amount of the fluorine-based additive (G) is 100% by mass, the composition of the organic solvent is preferably 0.01 to 10% by mass, preferably 0.05 to 5% by mass, and 0.1 to 0.1%. 3% by mass is better. If it is less than - 〇.01% by mass, a sufficient effect cannot be obtained. If it exceeds ί% by mass, sufficient hardness cannot be obtained as a cured product, or hardening does not reach the inside (lower layer). (Η) Other Additives In the curable composition of the present invention, the photosensitizer, the polymerization inhibiting agent, the polymerization starting aid, the leveling agent, and the wettability may be appropriately blended as necessary, without impairing the effects of the present invention. Improver, surfactant, plasticizer, UV absorber, antioxidant, antistatic agent 'inorganic chelating agent, pigment, dye, etc. 2. Cured film/laminate -30- The cured film or laminate system of the present invention is obtained by hardening the curable composition of the present invention on a substrate. Examples of the substrate include plastics (polycarbonate, polymethacrylate, polystyrene, polyester, polyolefin, epoxy, cyanuric acid, cellulose triacetate, ABS, AS, norbornene-based resin, etc.). ), metal, wood, paper, glass, slate, etc. The shape of these substrates may be a plate shape, a film shape or a ternary molded body. Further, a meso layer may be formed between the substrate and the cured film as needed. The coating method of the composition may be a general coating method such as dipping coating, inkjet coating, flow coating, drip coating, roll coating, spin coating, brush coating, or the like. The thickness of the coating film in such coating is usually from 0.1 to 400 #m, preferably from 1 to 200 μm, after drying and hardening. In order to adjust the thickness of the coating film, the composition of the present invention can be used after being diluted with the above organic solvent (F). For example, when used as an antireflection film or a covering material, the viscosity is usually 0.1 to 50,000 mPa·s / 25 t, preferably 0.5 to 1 0,000 mPa · sec / 25. . ° After coating, it is preferably after 〇~20 (TC has its volatile component dried, and can be cured by heat and/or radiation to obtain a laminate. By thermal hardening, the preferred hardening condition is It is carried out in the range of 20 to 150 ° C for 10 seconds to 24 hours. It is preferable to use ultraviolet rays or electron beams when it is hardened by radiation, and in this case, the preferred amount of ultraviolet light is 0.01 to 10 J/ The cm2 is preferably 0.1 to 2 J/cm 2 . Further, the preferred electron beam irradiation conditions are an acceleration voltage of 1 〇 to 300 kV, an electron density of 〇. 〇 2 to 0.30 mA/cm 2 , and an electron beam irradiation amount of 1 to 1 OMrad. The heat source at the time of hardening can be, for example, an electric heater, an infrared lamp, a hot air or the like, and a line source of light or an electron wire, and if the composition can be hardened in a short time after coating, it is not particularly limited. For example, infrared rays Examples of the line source include an illuminating lamp, a resistance heating plate, and a laser. The line source of visible light includes a neon, an illuminating lamp, a fluorescent lamp, and a laser. The source of the ultraviolet ray is a mercury illuminating lamp or a halogen. Lights, lasers, etc. Also, the line source of the electronic line can be cited There are commercially available methods of utilizing hot electrons generated by tungsten filaments, or cold cathode methods produced by high voltage pulses on metal and secondary electrons generated by collision of ionized gaseous molecules with metal electrodes. In addition, the line source of the α-ray, the y-ray, and the r-ray may be, for example, a nuclear cleavage substance such as Co, and the r-ray may be a vacuum tube that accelerates the collision of electrons with the anode, etc. These radiation systems may be individually 1 When the laminate of the present invention is used as an antireflection film, the cured film obtained by hardening the composition of the present invention may generally be a layer of an antistatic hard coat layer. When the antireflection film is used as an antireflection film, a high refractive index layer, a medium refractive index layer, a low refractive index layer, and the like are formed as necessary. [Embodiment] [Embodiment] Hereinafter, the present invention more specifically by way of example In addition, the present invention is not limited to the examples, and the "parts" and "%" described below indicate the parts by mass and mass% unless otherwise specified. -32- 13637 64 Production Example 1: Production of Organic Compound (Eb) Having Polymerizable Unsaturated Group In a dry air, a solution of 221 parts of thiopropylpropyltrimethoxydecane and 1 part of dibutyltin dilaurate was used. 222 parts of isophorone diisocyanate was added dropwise at 50 ° C for 1 hour while stirring, and then stirred and heated at 701 for 3 hours. In the above solution, NK ester of Xinzhongcun Chemical was prepared at 30 ° C for 1 hour. A-TMM-3LM-N (composed of 60% by mass of pentaerythritol triacrylate and 40% by mass of pentaerythritol tetraacrylate. Among them, only pentaerythritol triacrylate having a hydroxyl group) 5 49 parts after dropping, at 60 The organic compound (Ab ) containing a polymerizable unsaturated group was obtained by heating and stirring for 10 hours. When the amount of residual isocyanate in the FT-IR analysis product was 0.1% or less, the reaction was almost quantitatively terminated. The infrared absorption spectrum of the product is the absorption peak of the 25 25 COTT1 characteristic on the hydrogen-sulfur group in the raw material and the 2260 characteristic of the raw isocyanate compound (the absorption peak of 1^1 disappears, and the urethane bond is newly observed). a peak of 1 660 cm·1 and a peak of mOcrrT1 characterized by an acryloxy group on the S(C = 0)NH- group, which is formed as a polymerizable unsaturated group and has both a propylene oxy group and -S(C = 0) NH-, a urethane-bonded acryloxy-modified alkoxy decane. In addition to the above, 773 parts of the compound of the above formula (12) or (13) are obtained. In addition to (Eb), there were 220 parts of pentaerythritol tetraacrylate which were not related to the reaction. -33 - 1363764 Production Example 2: Preparation of Reactive Particle Dispersion 9.35 parts of the composition produced in Production Example 1 (containing polymerization) Unsaturated organic compound (Eb) 7.28 parts), cerium oxide particle dispersion (Ea) (cerium dioxide concentration 32%, average particle diameter 10 nm, Nissan Chemical Industry Co., Ltd. methanol cerium oxide sol) 89.90 Parts, 0.12 parts of ion-exchanged water, and p-hydroxyphenyl monomethyl A mixture of 0.01 parts of ether was stirred at 60 ° C for 4 hours, then 1.36 parts of methyl orthoformate was added, and the mixture was heated and stirred at the same temperature for 1 hour to obtain a dispersion of reactive particles. The dispersion was weighed in aluminum. After weighing 2 g, the plate was dried on a hot plate at 175 °C for 1 hour, and the solid content was determined to be 37.8%. Further, the dispersion was weighed 2 g in a magnetic boiler and then dried on a hot plate at 80 °C. After 30 minutes of firing in a muffle furnace at 750 ° C for 1 hour, the inorganic content in the solid component was determined to be 75.5% from the inorganic residue. Production Example 3: Preparation of the compound of the component (A) by toluene A solution of 59 parts of diisocyanate and 1 part of dibutyltin dilaurate was added dropwise 360 parts of polyether-containing polydimethyl siloxane (SF 8427 manufactured by DOWCORNING TORAY Co., Ltd.) over several hours. The mixture was stirred at room temperature for 3 hours, and NK ester A-TMM-3LM-N (manufactured by Xinzhongcun Chemical Co., Ltd., 60% by mass of pentaerythritol triacrylate and 40% by mass of pentaerythritol tetraacrylate) was added in one hour at 25 Torr. Among them, only the pentaerythritol tripropyl group having a hydroxyl group is involved in the reaction. After the dropwise addition, the desired polymerizable unsaturated group-containing organic compound (A) is obtained by heating and stirring at 60 ° C for 10 hours. The product is analyzed by FT-IR -34 - 1363764. When the amount of the residual isocyanate is 0.1% or less, it should be almost quantitatively finished. The infrared absorption spectrum of the product is an absorption peak of 2260 cm·1 characteristic on the isocyanate compound, and a urethane bond is newly observed. And C = ONH - on the base; 1 660CJTT1 peak and propylene oxy group on the characteristic 1 720cm · 1 , which means the formation of a propyl group as a polymerizable unsaturated group and -C = ONH-, amine A Acid-bonded polyether-containing polydimethylene. According to the above, in addition to 522 parts of the polyether-containing polydimethyl methoxy oxane which imparts the polymerization of the component (A) and the base, 69 parts of the pentaerythritol tetraacrylate is mixed therein. Example 1 (1) Preparation of curable composition In a container equipped with a stirrer to shield ultraviolet rays, each component was added in the proportions shown in Table 1, and the mixture was stirred at room temperature for 1 hour to obtain a uniform. (2) Preparation of the laminate The composition obtained in the above (1) was applied by spin coating on the polymerization of the substrate. Thereafter, the film was dried for 1 minute at room temperature. Next, the coating film was cured by ultraviolet light using high-pressure mercury irradiation under the conditions of light irradiation of 'J 500 mJ/cm 2 in the atmosphere to obtain a cured film of 〇/zm to obtain a laminate. The table is not reversed, and the original disappears. The peak olefinic oxime oxime-free reaction of the temple is not formed. The composition of the carbonate ring is formed to form a film thickness of -35-1363764. Examples 2 to 3, reference Examples 1 to 2 and Comparative Examples 1 to 4 The combination shown in the other Table 1 was carried out in the same manner as in Example 1 to prepare a composition, and a laminate was obtained. Evaluation Example The following properties were evaluated for the laminates obtained in the above examples, reference examples and comparative examples, and the results are shown in Table 1. (1) Electrostatic decay rate half-life (minutes) A laminate of the above-described examples, reference examples, and comparative examples was applied with a voltage of 3 kV using a Static Honest Meter and an Honest Meter Analyzer ('SHISHID® Electrostatic Gas Co., Ltd.). , the time when the applied voltage becomes half of i.5kV (the electrostatic decay rate half-life (minutes)). (2) Contact angle of water and oleic acid (°) The contact angle of water and oleic acid is the automatic contact angle contact angle meter of the solid-liquid interface analysis device DROP MASTER500 (made by Kyowa Interface Science Co., Ltd.) After the surface was formed into droplets, the angle between the water and the laminate, and the interface between the oleic acid and the laminate was measured for 5 seconds. The contact angle of water and oleic acid is closely related to fingerprint wiping. The higher the water and oleic acid contact angle, the better the fingerprint wiping. (3) Fingerprint wiping off -36- 1363764 In fact, the fingerprint is attached to the laminate, and the fingerprint is traced after being wiped off with a soft cloth. There are no traces of defects, and some traces remain as ^ 'cannot be wiped out as X. (4) Presence of precipitates under the damp heat test The laminate was placed under constant temperature and humidity of 80 ° C and 80% RH, and after 100 hours, visual inspection was performed to confirm the presence or absence of oily precipitates.

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參考例3 1 1 1 0.30 26.06 0.69 0.94 0.56 70.95 0.50 100.00 10.00 90.00 (N Ό 60分鐘以上〇〇薜參考例2 5.95 1 1 1 18.85 1 0.96 0.57 1 73.16 0.51 100.00 10.00 | 90.00 CS VO 60分鏑以上 On 00 〇 m 比較例1 1 1 1 1 21.67 1 ο 0.60 76.72 1 100.00 10.00 90.00 (N Ό 60分鐘以上卜 < 鹿參考例2 1 1 8.77 1 18.28 « , 0.94 0.56 70.95 0.50 100.00 10.00 90.00 CN VO 60分鐘以上 CN 00 〇 W- 參考例1 1 8.69 1 0.30 18.10 0.69 0.93 0.55 70.25 0.49 100.00 10.00 90.00 CS m Μ 〇實施例4 5.83 1 1 0.23 20.24 0.52 0.95 0.56 71.67 1 100.00 10.00 90.00 (N VO (Ν 〇壊實施例3 5.80 1 1 1 0.30 19.89 0.70 ! 0.94 0.56 71.31 0.50 100.00 10.00 90.00 CS VO m 〇〇摧實施例2 5.80 • 1 0.23 20.14 0.52 0.94 0.56 71.31 0.50 100.00 10.00 90.00 (N v〇寸 § 〇 m 實施例1 1.00 1 1 0.23 24.94 0.52 0.94 1 0.56 71.31 0.50 100.00 10.00 90.00 (N (N 2 〇璀組成(質量部） SF8427-TP(SF8427 的丙烯酸酯改性物） ADDID130 SF8427 PETA-30R中的Li化合物 DPHA PETA-30中的(C)成分 s 卜 gb 反應性粒子(YSX-91S) MCF-350SF 固形成分合計甲醇丙二醇單甲醚固形成分濃度(質量％) 靜電衰減率半衰期(分鐘）水接觸角(。）油酸接觸角0 指紋拭去性 tidi ν •Κ Φ % 8 § 33 3：戶I Η- ^ 鏍00 Μ 0 m ss 成分 1 β g 〇 g -38- 1363764 反射膜用被覆材料。本發明之硬化膜或層合體，因具有高硬度及耐有 ’同時依其組成可形成表面光滑性優異的塗膜（被拒特徵’特別適用於：CD、DVD、M0、高密度DVD density-DVD;HD-DVD)、藍光光碟（Blu-ray disc) 二代DVD等之記錄用光碟；塑膠光學部品、觸控居薄膜型液晶元件、塑膠容器、建築內裝材料之地板本壁面材料、人工大理石等之防損傷（擦傷）或防污努保護材料：或者作爲薄膜型液晶元件、觸控面版、習學部品等之防反射膜等。傷性 )之 high 等之版、料、用的膠光Reference Example 3 1 1 1 0.30 26.06 0.69 0.94 0.56 70.95 0.50 100.00 10.00 90.00 (N Ό 60 minutes or more 〇〇薜 Reference Example 2. 5.95 1 1 1 18.85 1 0.96 0.57 1 73.16 0.51 100.00 10.00 | 90.00 CS VO 60 minutes or more On 00 〇m Comparative Example 1 1 1 1 1 21.67 1 ο 0.60 76.72 1 100.00 10.00 90.00 (N Ό 60 minutes or more) < Deer Reference Example 2 1 1 8.77 1 18.28 « , 0.94 0.56 70.95 0.50 100.00 10.00 90.00 CN VO 60 minutes Above CN 00 〇W- Reference Example 1 1 8.69 1 0.30 18.10 0.69 0.93 0.55 70.25 0.49 100.00 10.00 90.00 CS m Μ 〇 Example 4 5.83 1 1 0.23 20.24 0.52 0.95 0.56 71.67 1 100.00 10.00 90.00 (N VO (Ν 〇壊 implementation Example 3 5.80 1 1 1 0.30 19.89 0.70 ! 0.94 0.56 71.31 0.50 100.00 10.00 90.00 CS VO m 实施实施 Example 2 5.80 • 1 0.23 20.14 0.52 0.94 0.56 71.31 0.50 100.00 10.00 90.00 (N v 〇 § 〇m Example 1 1.00 1 1 0.23 24.94 0.52 0.94 1 0.56 71.31 0.50 100.00 10.00 90.00 (N (N 2 〇璀 composition (mass part) SF8427-TP (acrylate modification of SF8427) ADDID130 SF8427 PETA-30R (C) component of the Li compound DPHA PETA-30 卜 gb reactive particles (YSX-91S) MCF-350SF solid component total methanol propylene glycol monomethyl ether solid component concentration (% by mass) electrostatic decay rate half-life (minutes) water Contact angle (.) Oleic acid contact angle 0 Fingerprint wipeability tidi ν • Κ Φ % 8 § 33 3: Household I Η- ^ 镙00 Μ 0 m ss Component 1 β g 〇g -38- 1363764 Reflex film coating material. The cured film or laminate of the present invention has a high hardness and resistance to a coating film which is excellent in surface smoothness according to its composition (rejected characteristics are particularly suitable for: CD, DVD, M0, high density DVD density- DVD; HD-DVD), Blu-ray disc, recording disc for second-generation DVD, plastic optical parts, touch-film type liquid crystal elements, plastic containers, floor materials for building interior materials, artificial Anti-damage (scratch) or anti-fouling protective material for marble, etc.: or an anti-reflection film such as a film type liquid crystal element, a touch panel, or a part of a school. Injury, high, etc.

-40--40-

Claims

1363764 Announcement ^13⁄4° Patent Application No. 097105039 Patent Application Revision of the Chinese Patent Application Revision of the People's Republic of China on January 4, 101. Patent Application No. 1, a curable composition containing the following components (A)~( E): (A) a polymer containing a polymerizable unsaturated group, a repeating unit represented by the following formula (la), and a repeating unit represented by the following formula (lb), (B) having the following formula (3a) Or a compound represented by (3b), (C) a compound having two or more polymerizable unsaturated groups in a molecule other than the component (A), (D) a photopolymerization initiator, and (E) a polymerizable property a particle having a saturated group and having an oxide of at least one element selected from the group consisting of ruthenium, aluminum, zirconium, titanium, zinc, bismuth, indium, tin, antimony and bismuth as a main component; [Chemical Formula 1] * CpH2pO--* (1a) Formula rL CS——C » I » a H3QH31 and medium \)/ is CX Li(Cn,F2n,+ 1 Y)2N (3b) [In equations (3a) and (3b), X represents CO 2 or S03, Y represents CO or S02, and n' represents an integer of 1 to 9]. 1363764 2. The sulfhydryl group of the aforementioned component (A) as claimed in the patent scope f. 3. In the scope of patent application f, the aforementioned component (A) is further included. 4. As claimed in the patent scope | The above component (E) has: (4) the basis of the structure shown; [Chemical 2] Η ... -U —C—N — (4) II V [in the formula (4), U represents), and V represents a hardening composition of 0 or S], wherein: a condensed unsaturated group (meth) propylene A curable composition of 1 or 2, which has a urethane group. A hardening composition of the item 1, wherein the hydrophilic unsaturated group contains a formula of ΝΗ, 0 (oxygen atom) or S (sulfur atom)