TW201229158A - Method for forming hard-coated layer - Google Patents

Method for forming hard-coated layer Download PDF

Info

Publication number
TW201229158A
TW201229158A TW100141810A TW100141810A TW201229158A TW 201229158 A TW201229158 A TW 201229158A TW 100141810 A TW100141810 A TW 100141810A TW 100141810 A TW100141810 A TW 100141810A TW 201229158 A TW201229158 A TW 201229158A
Authority
TW
Taiwan
Prior art keywords
component
weight
meth
parts
curable composition
Prior art date
Application number
TW100141810A
Other languages
Chinese (zh)
Other versions
TWI506100B (en
Inventor
Hideyuki Matsumoto
Masanobu Sugimoto
Jun Morita
Katsutoshi Sawada
Tarou Kanamori
Original Assignee
Jsr Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jsr Corp filed Critical Jsr Corp
Publication of TW201229158A publication Critical patent/TW201229158A/en
Application granted granted Critical
Publication of TWI506100B publication Critical patent/TWI506100B/en

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
    • B05D3/061—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation using U.V.
    • B05D3/065—After-treatment
    • B05D3/067—Curing or cross-linking the coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions 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; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Plasma & Fusion (AREA)
  • Physics & Mathematics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Paints Or Removers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

The present invention relates to a curable composition capable of obtaining a cured film with excellent fingerprint recognition and wiping properties and high transparency. The present invention provides a method for forming a hard-coated layer, comprising a step of spray-coating on a substrate a curable composition containing ingredients (A) to (D) to form a coating, and a step of irradiating radiation to the coating to form a hard-coated layer: (A) the polyfunctional (meth)acrylic acid monomer, (B) the photopolymerization initiator, (C) the nonionic surfactant formed of fatty acid ester with HLB of 2-7, and (D) the organic solvent.

Description

201229158 六、發明說明： 【發明所屬之技術領域】 本發明係關於硬塗層之形成方法。更詳言之，係關於 使用適於噴霧塗佈之硬化性組成物之硬塗層形成方法。 【先前技術】 用以防止塑膠（聚碳酸酯'聚甲基丙烯酸甲酯、聚苯 0 乙烯、聚酯、聚烯烴、環氧樹脂、三聚氰胺樹脂、三乙醯 基纖維素樹脂、ABS樹脂、AS樹脂、降冰片烯系樹脂等） 、金屬、木材、紙、玻璃、石板等各種基材表面之損傷（ 擦傷）或防止污染之保護塗覆材要求具有優異之塗佈性， 且可在各種基材表面形成硬度、耐擦傷性、防污性、耐磨 耗性、表面平滑性、低捲曲性、密著性、透明性、耐藥品 性及塗膜面之外觀均優異之硬化膜之硬化性組成物。 近年來，於表面施予硬塗處理之行動電話或資訊終端 Q 等已上市。藉由進行硬塗處理成爲有光澤之表面使設計性 提高，但由於有光澤，使指紋之附著變得明顯。爲此，以 往之硬塗除要求耐刮傷性、透明性以外，對於防污性，尤 其是指紋擦拭性之要求亦高，但全部滿足該等特性之材料 於現況並不存在。另一方面，該等之塗佈時，基於可對曲 面進行塗佈而要求進行噴霧塗佈。 於專利文獻1中揭示於電離輻射線硬化型樹脂中添加 由脂肪酸酯組成之HLB2-15之非離子界面活性劑之觸控面 板或顯示器用之硬塗覆薄膜。該薄膜之指紋辨識性或指紋 -5- 201229158 擦拭性良好，但耐刮傷性差，且透明性亦差。此係由於脂 肪酸酯系界面活性劑爲了展現指紋辨識性、指紋擦拭性， 而於硬化膜表面滲出，因此使硬化膜之耐刮傷性或透明性 降低。即使噴霧塗佈該組成物，仍無法獲得足夠之指紋辨 識性、指紋擦拭性。 專利文獻2揭示包含具有特定構造且含有所有末端具 有聚合性不飽和基之聚環氧烷鏈之聚合物（具體而言爲脂 肪酸酯系界面活性劑）、具有兩個以上（甲基）丙烯醯基 之化合物及表面具有聚合性不飽和基之無機微粒子，且該 等成分可相互反應之硬塗層用硬化性樹脂組成物。使該硬 化性樹脂組成物硬化獲得之硬化膜藉由使上述含有聚環氧 烷鏈之聚合物、具有（甲基）丙烯醯基之化合物、及表面 具有聚合性官能基之無機粒子相互反應，而使含有聚環氧 烷鏈之聚合物不會滲出於硬化膜表面，且由於各成分彼此 交聯，故提高耐刮傷性。專利文獻2之硬化膜之耐刮傷性 雖亦優異，但無法獲得足夠之指紋辨識性或指紋擦拭性。 [先前技術文獻] [專利文獻] [專利文獻1 ]特開2 0 0 4 - 1 1 4 3 5 5號公報 [專利文獻2 ]特開2 0 0 8 - 1 6 5 0 4 0號公報 【發明內容】 [發明欲解決之課題] -6- 201229158 本發明係鑑於上述問題而完成者，其目的係提供一種 可使用作爲所得硬化膜具有優異之指紋辨識性、指紋擦拭 性之硬塗覆材之噴霧塗佈用之硬化性組成物。 [用以解決課題之手段] 爲達成上述目的，本發明人等進行積極硏究之結果， 發現藉由使用調配一定量之羥基濃度於一定量以下之脂肪 0 酸酯系界面活性劑之組成物，可對藉由噴霧塗佈形成之硬 塗層賦予優異之防污性與高的透明性，因而完成本發明。 亦即，本發明提供下述層膜薄膜及硬化性組成物。 1. 一種硬塗層之形成方法，其包含： 於基材上噴霧塗佈含有下述成分（a)~(d)，且下 述成分（C)之HLB爲2〜7之硬化性組成物而形成塗膜之步 驟，以及 對前述塗膜照射輻射線之步驟： 〇 (A)多官能（甲基）丙烯酸單體 (B )光聚合起始劑 (C )由脂肪酸酯所成之非離子性界面活性劑 (D)有機溶劑。 2. 如上述1所記載之硬塗層之形成方法，其中前述成 分（C)之調配量相對於前述（A)成分及前述（B)成分 之合計100重量份，爲超過1〇重量份且100重量份以下。 3. 如上述1或2所記載之硬塗層之形成方法，其中前 述成分（C)之HLB爲2~4之範圍。 201229158 4. 一種噴霧塗佈用硬化性組成物，其含有下述成分 (A)〜（D)，且下述成分（C)之HLB爲2〜7: (A)多官能（甲基）丙烯酸單體， (B )光聚合起始劑， (C) 由脂肪酸酯所成之非離子性界面活性劑， (D) 有機溶劑。 5 ·如上述4所記載之噴霧塗佈用硬化性組成物，其中 前述成分（C)之調配量相對於前述（A)成分及前述（B )成分之合計100重量份，爲超過10重量份且100重量份以 下 6 .如上述4或5所記載之噴霧塗佈用硬化性組成物， 其中前述成分（C)爲分子內具有直鏈狀或分支狀之碳數 6〜3 0之一價或二價烴基之界面活性劑。 7 ·如上述4〜6中任一項所記載之噴霧塗佈用硬化性組 成物，其中前述成分（C)爲具有（甲基）丙烯醯基之界 面活性劑。 8 ·如上述4〜7中任一項所記載之噴霧塗佈用硬化性組 成物，其中前述成分（C)之HLB爲2~4之範圍。 9 .如上述4〜8中任一項所記載之噴霧塗佈用硬化性組 成物，其係進而含有（E)數平均粒徑1〜200 nm之無機氧 化物粒子。 10.如上述9所記載之噴霧塗佈用硬化性組成物，其 中前述成分（E)爲表面具有聚合性不飽和基之無機氧化 物粒子。 -8 - 201229158 [發明之效果] 依據本發明，可提供指紋辨識性、指紋擦拭性優異， 同時具有高透明性之硬塗層。 依據本發明，可進一步提供透明性優異之層合薄膜。 依據本發明，可提供獲得指紋辨識性、指紋擦拭性優 異，耐刮傷性亦優異，同時具有耐濕熱性或耐乾熱性等耐 0 久性，且透明性優異之硬化膜之硬化性組成物。 【實施方式】 以下詳細說明本發明。 1.硬化性組成物 本發明之硬化性組成物（以下稱爲本發明之組成物） 可含有下述成分（A)〜（F)。其中成分（A) ~(D)爲 Q 必要成分，成分（E)〜（F)爲視需要添加之任意成分。 (A) 多官能（甲基）丙烯酸單體 (B) 光聚合起始劑 (C) 由脂肪酸酯所成之非離子性界面活性劑 (D )有機溶劑 (E)數平均粒徑l~200nm之無機氧化物粒子 (F )其他添加劑。 本發明之組成物藉由使上述成分（C)爲由具有脂肪 酸酯基與（甲基）丙烯醯基之HLB値（親水性-疏水性平衡 201229158 )2〜7之脂肪酸酯所成之非離子界面活性劑，即使大量調 配成分（C)，仍可防止硬化膜（塗膜）之白化，獲得具 有高透明性之硬化膜。 且，藉由具有直鏈狀或分支鏈狀之碳數6〜3 0之一價或 二價烴基，而使指紋擦拭性優異。 以下，針對本發明之組成物之各成分加以說明。 (A)多官能（甲基）丙烯酸單體 本發明中使用之成分（A)多官能（甲基）丙烯酸單 體爲具有兩個以上（甲基）丙烯醯基之（甲基）丙烯酸單 體。成分（A )爲用以提高組成物之成膜性之所謂黏合劑 成分。 又’雖有後述之成分（E )爲反應性粒子（Ec )之情 況及後述之成分（C)亦具有複數個（甲基）丙烯醯基之 情況’但本發明中之多官能（甲基）丙烯酸單體（A )爲 不包含反應性粒子（Ec )及成分（C )者。 多官能（甲基）丙烯酸單體之具體例可列舉爲三羥甲 基丙烷（甲基）丙烯酸酯、二-三羥甲基丙烷四（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-羥基乙基）三聚異氰酸酯三（甲基）丙烯酸酯等 具有三個以上（甲基）丙烯醯基之多官能（甲基）丙烯酸 單體；乙二醇二（甲基）丙烯酸酯、1,3· 丁二醇二（甲基 -10- 201229158 )丙烯酸酯、1,4-丁二醇二（甲基）丙烯酸酯、i，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）丙烯酸酯、三乙二醇二（甲基）丙烯 酸酯、二丙二醇二（甲基）丙烯酸酯等具有兩個（甲基） 丙烯醯基之多官能（甲基）丙烯酸單體，雙（2-羥基乙基 )三聚異氰酸酯二（甲基）丙烯酸酯等含有羥基之多官能 (甲基）丙烯酸酯類，及於該等之羥基加成環氧乙烷或環 0 氧丙烷之加成物之聚（甲基）丙烯酸酯類；具有兩個以上 之（甲基）丙烯醯基之寡聚酯（甲基）丙烯酸酯類、寡聚 醚（甲基）丙烯酸酯類及寡聚環氧（甲基）丙烯酸酯類等 。以上列舉之多官能（甲基）丙烯酸單體可單獨使用一種 ，亦可倂用兩種以上。 其中，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、 季戊四醇三（甲基）丙烯酸酯、二-三羥甲基丙烷四（甲 〇 基）丙烯酸酯等較佳。 該等多官能（甲基）丙烯酸單體（A)之市售品可列 舉爲例如東亞合成（股）製造之ARONIX M-400、M-404、 M-408、M-45 0、M-3 05、M-3 09、M-310、M-315、M-320 、M-3 50、M-360、M-208、M-210、M-215、M-220、M-225 ' M-23 3、M-240、M-245、M-260、M-270、M-1100、 Μ- 1 200、Μ-1 2 1 0、Μ-1 3 1 0、Μ- 1 600、M-22 1、M-203、 TO-924、TO- 1 270 > TO-1 23 1 ' TO-5 95、TO-7 5 6、TO-1 343 、TO-902 ' TO-904、TO-905、TO-1330，日本化藥（股） -11 - 201229158 製造之 KAYARAD D-3 1 0、D-3 3 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-368 、SR-415、SR-444、SR-454、SR-492、SR-499、SR-502、 SR-9020、SR-9035、SR-111 ' SR-212、SR-213、SR-230、 SR-259 ' SR-268、SR-272、SR-344、SR-349、SR-601、 SR-602、SR-610、SR-9003、PET-30 ' T-1 420、GPO-303 、TC-120S 、HDDA、NPGDA、TPGDA、PEG400DA、 MANDA、HX-220、HX-620、R-551、R-721、R-167、R-5 26、R-551、R-712、R-604、R-684、TMPTA、THE-330 、TPA-3 20 、 TPA-3 3 0 、 KS-HDD A 、 KS-TPGD A 、 KS-TMPTA，共榮社化學（股） 4A、DPE-6A、DTMP-4A，新中村化學（股）製造之NK ESTER A-TMM-3LM-N等。 成分（A )以其總量作爲1 〇 0重量％，較好含有5 0重量 %以上之具有三個以上（甲基）丙烯醯基之多官能（甲基 )丙烯酸單體，更好爲70重量％以上，又更好爲100重量％ 〇 本發明之組成物中之成分（A)之調配量以成分（D )以外之合計作爲100重量份時，較好在40~95重量份之範 圍內，更好爲45〜90重量份之範圍內，又更好爲50〜90重量 份之範圍內。藉由以上述範圍調配成分（A )，可獲得高 硬度之硬化膜。 -12- 201229158 (B )光聚合起始劑 本發明中之成分（B)爲光聚合起始劑。光聚合起始 劑（B )爲藉由輻射線（光）照射產生活性自由基種之化 合物（輻射線（光）聚合起始劑），可列舉爲慣用者。 至於光聚合起始劑只要是藉由光照射而分解產生自由 基而起始聚合者即無特別限制，可列舉爲例如苯乙酮、苯 乙酮苄基縮酮、1-羥基環己基苯基酮、2，2-二甲氧基-1,2-0 二苯基乙烷-1-酮、咕噸酮、蕗酮、苯甲醛、弗、蒽醌、三 苯基胺、咔唑、3-甲基苯乙酮、4-氯二苯甲酮、4，4’-二甲 氧基二苯甲酮、4，4’-二胺基二苯甲酮、苯偶因丙基醚、苯 偶因乙基醚、苄基二甲基縮醛、卜（4-異丙基苯基）-2-羥 基-2-甲基丙-1-酮、2-羥基-2-甲基-1-苯基丙-1-酮、噻噸酮 、二乙基噻噸酮、.2-異丙基噻噸酮、2-氯噻噸酮、2-甲基-1-[4-(甲硫基）苯基]-2-嗎啉基-丙-1-酮、2-苄基-2-二甲 胺基-1-(4-嗎啉基苯基）-丁酮-1,4-(2-羥基乙氧基）苯 Q 基-(2-羥基-2-丙基）酮、2,4,6-三甲基苯甲醯基二苯基氧 化膦、雙-(2,6-二甲氧基苯甲醯基）-2,4,4-三甲基戊基氧 化膦、寡聚（2-羥基-2-甲基-1-(4-(1-甲基乙烯基）苯基 )丙酮）等。 光聚合起始劑之市售品可列舉爲例如BASF公司製造 之 IRGACURE 184、369、65 1、500、819、907、784、 2959 、 CGI 1 700 、 CGI 1 75 0 、 CGI 1 8 50 、 CG24-61 、201229158 VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a method of forming a hard coat layer. More specifically, it relates to a method of forming a hard coat layer using a hardenable composition suitable for spray coating. [Prior Art] Used to prevent plastics (polycarbonate 'polymethyl methacrylate, polystyrene, polyester, polyolefin, epoxy resin, melamine resin, triethylene glycol cellulose resin, ABS resin, AS Resin, norbornene-based resin, etc., metal, wood, paper, glass, slate, etc. Surface damage (scratch) or contamination-preventing protective coating material is required to have excellent coating properties and can be used in various bases. The surface of the material forms the hardenability of the cured film which is excellent in hardness, scratch resistance, antifouling property, abrasion resistance, surface smoothness, low curling property, adhesion, transparency, chemical resistance and appearance of the coating film surface. Composition. In recent years, mobile phones or information terminals Q that have been subjected to hard coating on the surface have been put on the market. The design is improved by the hard coating treatment to form a glossy surface, but the adhesion of the fingerprint becomes conspicuous due to the gloss. For this reason, in addition to the scratch resistance and transparency required for hard coating, the antifouling property, especially the fingerprint wiping property, is also high, but all materials satisfying these characteristics do not exist in the present state. On the other hand, in the case of such coating, spray coating is required based on the application of the curved surface. Patent Document 1 discloses a touch panel or a hard coat film for a display in which a nonionic surfactant of HLB 2-15 composed of a fatty acid ester is added to an ionizing radiation curable resin. Fingerprint identification or fingerprint of the film -5- 201229158 Good wiping property, but poor scratch resistance and poor transparency. In this case, since the fatty acid ester surfactant exhibits fingerprint recognition and fingerprint wiping, it bleeds out on the surface of the cured film, so that the scratch resistance or transparency of the cured film is lowered. Even if the composition is spray-coated, sufficient fingerprint recognition and fingerprint wiping property cannot be obtained. Patent Document 2 discloses a polymer (specifically, a fatty acid ester-based surfactant) having a specific structure and containing a polyalkylene oxide chain having a polymerizable unsaturated group at all terminals, and having two or more (meth) propylene groups. A compound of a mercapto group and an inorganic fine particle having a polymerizable unsaturated group on the surface thereof, and a curable resin composition for a hard coat layer in which the components can react with each other. The cured film obtained by curing the curable resin composition reacts with the above-mentioned polymer containing a polyalkylene oxide chain, a compound having a (meth)acryl fluorenyl group, and inorganic particles having a polymerizable functional group on the surface. On the other hand, the polymer containing the polyalkylene oxide chain does not penetrate the surface of the cured film, and since the components are crosslinked with each other, the scratch resistance is improved. Although the scratch resistance of the cured film of Patent Document 2 is excellent, it is not possible to obtain sufficient fingerprint visibility or fingerprint wiping property. [Prior Art Document] [Patent Document 1] [Patent Document 1] Japanese Patent Publication No. 2 0 0 4 - 1 1 4 3 5 5 [Patent Document 2] Japanese Patent Publication No. 2 0 0 8 - 1 6 5 0 4 0 Disclosure of the Invention [Problems to be Solved by the Invention] -6-201229158 The present invention has been made in view of the above problems, and an object thereof is to provide a hard coating material which can be used as a obtained cured film and which has excellent fingerprint visibility and fingerprint wiping property. A curable composition for spray coating. [Means for Solving the Problem] In order to achieve the above object, the inventors of the present invention conducted active research and found that a composition of a fatty acid ester-based surfactant which is formulated with a certain amount of a hydroxyl group concentration to a certain amount or less is used. The present invention can be completed by imparting excellent antifouling properties and high transparency to a hard coat layer formed by spray coating. That is, the present invention provides the following film film and curable composition. A method for forming a hard coat layer, comprising: spray-coating a curable composition containing the following components (a) to (d), and having an HLB of 2 to 7 in the following component (C); The step of forming a coating film, and the step of irradiating the coating film with radiation: 〇(A) polyfunctional (meth)acrylic monomer (B) photopolymerization initiator (C) is formed by a fatty acid ester Ionic surfactant (D) organic solvent. 2. The method for forming a hard coat layer according to the above, wherein the amount of the component (C) is more than 1 part by weight based on 100 parts by weight of the total of the component (A) and the component (B). 100 parts by weight or less. 3. The method of forming a hard coat layer according to the above 1 or 2, wherein the HLB of the component (C) is in the range of 2 to 4. 201229158 4. A curable composition for spray coating comprising the following components (A) to (D), and the HLB of the following component (C) is 2 to 7: (A) Polyfunctional (meth)acrylic acid Monomer, (B) photopolymerization initiator, (C) a nonionic surfactant composed of a fatty acid ester, (D) an organic solvent. The curable composition for spray coating according to the above-mentioned item 4, wherein the amount of the component (C) is more than 10 parts by weight based on 100 parts by weight of the total of the components (A) and (B). The curable composition for spray coating according to the above 4 or 5, wherein the component (C) is a linear or branched carbon number of 6 to 3 in the molecule. Or a divalent hydrocarbon-based surfactant. The curable composition for spray coating according to any of the above 4 to 6, wherein the component (C) is an interface having a (meth)acryl oxime group. The curable composition for spray coating according to any one of the above 4 to 7, wherein the component (C) has an HLB of from 2 to 4. The curable composition for spray coating according to any one of the above 4 to 8, which further comprises (E) inorganic oxide particles having a number average particle diameter of from 1 to 200 nm. 10. The curable composition for spray coating according to the above-mentioned item 9, wherein the component (E) is an inorganic oxide particle having a polymerizable unsaturated group on its surface. -8 - 201229158 [Effects of the Invention] According to the present invention, it is possible to provide a hard coat layer which is excellent in fingerprint visibility and fingerprint wiping property and which has high transparency. According to the present invention, a laminated film excellent in transparency can be further provided. According to the present invention, it is possible to provide a curable composition of a cured film which is excellent in fingerprint visibility, excellent in fingerprint wiping property, and excellent in scratch resistance, and which has durability against moisture and heat resistance and dry heat resistance, and which is excellent in transparency. [Embodiment] Hereinafter, the present invention will be described in detail. 1. Curable composition The curable composition of the present invention (hereinafter referred to as the composition of the present invention) may contain the following components (A) to (F). Among them, the components (A) to (D) are essential components of Q, and the components (E) to (F) are optional components added as needed. (A) Polyfunctional (meth)acrylic monomer (B) Photopolymerization initiator (C) Nonionic surfactant (D) organic solvent (E) number average particle size l~ 200 nm of inorganic oxide particles (F) other additives. The composition of the present invention is obtained by making the above component (C) a fatty acid ester having a fatty acid ester group and a (meth) acrylonitrile group HLB hydrazine (hydrophilic-hydrophobic balance 201229158) 2 to 7. The nonionic surfactant can prevent whitening of the cured film (coating film) even when the component (C) is compounded in a large amount, and a cured film having high transparency can be obtained. Further, the fingerprint wiping property is excellent by having a linear or branched chain carbon number of 6 to 30 or a divalent hydrocarbon group. Hereinafter, each component of the composition of the present invention will be described. (A) Polyfunctional (meth)acrylic monomer The component (A) used in the present invention is a (meth)acrylic monomer having two or more (meth)acrylonitrile groups. . The component (A) is a so-called binder component for improving the film formability of the composition. Further, although the component (E) to be described later is a reactive particle (Ec) and the component (C) described later also has a plurality of (meth)acryl fluorenyl groups, the polyfunctional (methyl group) in the present invention The acrylic monomer (A) is one which does not contain the reactive particles (Ec) and the component (C). Specific examples of the polyfunctional (meth)acrylic monomer include trimethylolpropane (meth) acrylate, di-trimethylolpropane tetra(meth) acrylate, and pentaerythritol tri(meth) acrylate. , pentaerythritol tetrakis (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerol tri (meth) acrylate, ginseng (2-hydroxyethyl) three a polyfunctional (meth)acrylic monomer having three or more (meth)acrylonitrile groups such as polyisocyanate tri(meth)acrylate; ethylene glycol di(meth)acrylate, 1,3-butanediol Di(methyl-10-201229158) acrylate, 1,4-butanediol di(meth)acrylate, i,6-hexanediol di(meth)acrylate, neopentyl glycol di(methyl) Acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, etc. having two (meth) acrylonitrile groups Functional (meth)acrylic monomer, bis(2-hydroxyethyl) trimeric a polyfunctional (meth) acrylate containing a hydroxyl group such as an acid ester di(meth)acrylate, and a poly(methyl) group of such an hydroxy group-added ethylene oxide or cyclooxypropane adduct. Acrylates; oligoester (meth) acrylates having two or more (meth) acrylonitrile groups, oligoether (meth) acrylates, and oligo-epoxy (meth) acrylates Wait. The above-mentioned polyfunctional (meth)acrylic monomers may be used singly or in combination of two or more. Among them, dipentaerythritol hexa(meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, di-trimethylolpropane tetra ( Mercapto) acrylate or the like is preferred. Commercial products of these polyfunctional (meth)acrylic monomers (A) can be exemplified by ARONIX M-400, M-404, M-408, M-45 0, M-3 manufactured by, for example, East Asia Synthetic Co., Ltd. 05, M-3 09, M-310, M-315, M-320, M-3 50, M-360, M-208, M-210, M-215, M-220, M-225 'M- 23 3. M-240, M-245, M-260, M-270, M-1100, Μ-1 200, Μ-1 2 1 0, Μ-1 3 1 0, Μ-1 600, M-22 1. M-203, TO-924, TO-1 270 > TO-1 23 1 'TO-5 95, TO-7 5 6, TO-1 343, TO-902 'TO-904, TO-905, TO-1330, Nippon Kayaku Co., Ltd. -11 - 201229158 KAYARAD D-3 1 0, D-3 3 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-368, SR-415, SR-444, SR-454, SR-492, SR- 499, SR-502, SR-9020, SR-9035, SR-111 'SR-212, SR-213, SR-230, SR-259' SR-268, SR-272, SR-344, SR-349, SR-601, SR-602, SR-610, SR-9003, PET-30 'T-1 420, GPO-303, TC-120S, HDDA, NPGDA, TPGDA, PEG400DA, MANDA, HX-220, HX-620 , R-551, R-721, R-167 R-5 26, R-551, R-712, R-604, R-684, TMPTA, THE-330, TPA-3 20, TPA-3 3 0, KS-HDD A, KS-TPGD A, KS- TMPTA, Kyoeisha Chemical Co., Ltd. 4A, DPE-6A, DTMP-4A, NK ESTER A-TMM-3LM-N manufactured by Shin-Nakamura Chemical Co., Ltd. The component (A) is used in an amount of 1 〇 0% by weight, preferably 50% by weight or more, of a polyfunctional (meth)acrylic monomer having three or more (meth) acrylonitrile groups, more preferably 70% by weight. When the amount of the component (A) in the composition of the present invention is 100 parts by weight or less, preferably in the range of 40 to 95 parts by weight, based on the total amount of the component (A). The inner portion is preferably in the range of 45 to 90 parts by weight, more preferably in the range of 50 to 90 parts by weight. By compounding the component (A) in the above range, a cured film having a high hardness can be obtained. -12- 201229158 (B) Photopolymerization initiator The component (B) in the present invention is a photopolymerization initiator. The photopolymerization initiator (B) is a compound (radiation (light) polymerization initiator) which generates an active radical species by irradiation with radiation (light), and can be exemplified. The photopolymerization initiator is not particularly limited as long as it is decomposed by light irradiation to generate a radical, and examples thereof include, for example, acetophenone, acetophenone ketal, and 1-hydroxycyclohexylphenyl. Ketone, 2,2-dimethoxy-1,2-0 diphenylethane-1-one, xanthone, anthrone, benzaldehyde, fluorene, anthracene, triphenylamine, carbazole, 3 -methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, benzoin propyl ether, benzene Equivalent ethyl ether, benzyl dimethyl acetal, di(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1- Phenylpropan-1-one, thioxanthone, diethylthioxanthone, .2-isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1-[4-(methylthio) Phenyl]-2-morpholinyl-propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1,4-(2) -hydroxyethoxy)benzene Q-(2-hydroxy-2-propyl)one, 2,4,6-trimethylbenzimidyldiphenylphosphine oxide, bis-(2,6-dimethyl Oxylbenzylidene)-2,4,4-trimethylpentylphosphine oxide, oligo(2-hydroxy-2-methyl-1-(4-(1-A) Vinyl)phenyl)acetone). Commercial products of the photopolymerization initiator are exemplified by, for example, IRGACURE 184, 369, 65 1 , 500, 819, 907, 784, 2959, CGI 1 700, CGI 1 75 0 , CGI 1 8 50 , CG24 manufactured by BASF Corporation. -61,

DAROCURE 1116、1173、LUCIRIN TPO、8893 ' UCB公司 製造之 UBEACRYL P36、LAMBERTI公司製造之 EZACURE -13- 201229158 KIP150、KIP65LT、KIP100F、KT37、KT55、KT046、 KIP75/B等。 本發明之組成物中之成分（B )含量以成分（D )以外 之合計作爲100重量份時，較好爲0.1〜10重量份之範圍內 ，更好爲0.3〜5重量份之範圍內，又更好爲0.5〜5重量份之 範圍內。又，成分（B)之含量亦可基於成分（A)之含量 在上述範圍內決定。例如，成分（A)之含量爲100重量份 時，成分（B)之含量較好爲0.25〜20重量份，更好爲 〇·5〜15重量份。藉由使成分（B)之含量在上述範圍內可 獲得高硬度之硬化膜。 (C )由脂肪酸酯所成之非離子界面活性劑（以下有時稱 成分（C )爲「（ C )脂肪酸酯系界面活性劑」） 成分（C)調配之目的係爲了不易看見附著於本發明 中獲得之硬塗層之指紋，同時使指紋之擦拭性良好。本發 明之硬化性組成物較好以噴霧塗佈使用。噴霧塗佈時，由 於界面活性劑不易局部偏在於塗膜表面，故相較於以其他 塗佈方法塗佈時，而產生調配大量界面活性劑之必要，但 藉由使用HLB爲2〜7範圍之非離子界面活性劑，可抑制硬 化膜之白化。且基於相同理由，成分（C)之HLB較好爲 2 ~4。另外，藉由對成分（C)賦予（甲基）丙烯醯基，可 與本發明組成物中之黏合劑成分鍵結而固定化，故可防止 (C )脂肪酸酯系界面活性劑滲出於硬化膜表面。據此， 提高所得硬化膜之耐久性。再者，成分（C)較好爲具有 -14- 201229158 直鏈狀或分支鏈狀之碳數6~30之一價或二價之烴基。藉由 具有碳數6〜3 0之烴基，可對所得硬化膜賦予指紋辨識性或 指紋擦拭性。此處所謂「指紋辨識性」意指薄膜表面附著 指紋時以肉眼難以看見。 此處，所謂HLB (親水性-疏水性平衡）値爲顯示界面 活性劑特性之重要指數，顯示親水性或親油性大小之程度 。HLB値可以下述計算式求得。 ◎ HLB = 7 + 1 1.7Log(Mw/M〇) 此處Mw爲親水基之分子量，Μ。爲親油基之分子量。 Mw + M〇 = M (界面活性劑之分子量）。本發明中使用之（C )脂肪酸酯系界面活性劑之HLB値須在2〜7之範圍內，較 好爲2〜4之範圍內。藉由使HLB値在上述範圍內，即使調 配大量之界面活性劑仍不會白化，可獲得適合噴霧塗佈之 組成物。 對成分（C)賦予（甲基）丙烯醯基之方法可藉由例 Q 如將具有羥基之脂肪酸酯系界面活性劑之羥基轉換成（甲 基）丙烯醯基而獲得。具體而言，成分（C)可藉由使脂 肪酸酯系界面活性劑所具有之羥基與具有（甲基）丙烯醯 基之化合物反應獲得。 具有（甲基）丙烯醯基之化合物可使用例如具有異氰 酸酯基及（甲基）丙烯醯基之化合物。藉由使用該種化合 物，可使脂肪酸酯系界面活性劑之羥基與異氰酸酯基反應 形成胺基甲酸酯鍵而導入（甲基）丙烯醯基。 具有異氰酸酯基及（甲基）丙烯醯基之化合物之具體 -15- 201229158 例可使用異氰酸2-(甲基）丙烯醯氧基乙基酯、異氰酸2-(甲基）丙烯醯氧基丙基酯、異氰酸1,1-雙[(甲基）丙烯 醯氧基甲基]乙基酯等。又，亦可使二異氰酸酯化合物與 含有羥基與（甲基）丙烯醯基之化合物反應獲得。至於該 種二異氰酸酯化合物列舉爲異佛爾酮二異氰酸酯、甲苯二 異氰酸酯、六亞甲基二異氰酸酯等。 具有羥基之脂肪酸酯系界面活性劑之具體例列舉爲例 如聚氧伸烷基硬化蓖麻油、聚氧伸烷基脂肪酸酯等。較好 爲聚氧伸乙基硬化蓖麻油、聚氧伸乙基脂肪酸酯。 聚氧伸乙基硬化蓖麻油之市售品列舉爲例如EM A LEX HC系歹ij (日本Emulsion公司製造）、NOIGEN HC系列（ 第一工業製藥公司製造）等。 聚氧伸乙基脂肪酸酯之市售品列舉爲例如EMALEX GWIS-100EX (異硬脂酸甘油酯，日本Emulsion公司製造 )、NOIGEN GIS系列（第一工業製藥公司製造）等。 具有羥基之脂肪酸酯系界面活性劑與具有異氰酸酯基 及（甲基）丙烯醯基之化合物之反應可如下列般進行。 亦即’異氰酸酯化合物與含有羥基之化合物之反應較 好使用相對於反應物之總量1 〇 〇重量份爲〇 . 〇 1〜1重量份之 一般環烷酸銅、環烷酸鈷、環烷酸鋅、二丁基錫二月桂酸 酯、三乙基胺、1,4 -二氮雜雙環[2.2.2]辛烷、2,6，7 -三甲 基-1,4-二氮雜雙環[2.2.2]辛烷等胺基甲酸酯化觸媒。且， 該等化合物之反應亦可在無觸媒下進行。反應溫度通常爲 〇〜9 0 °C ’較好在40〜80 °C進行。反應可在無溶劑下進行， -16- 201229158 亦可溶解於溶劑中進行。 成分（C)可具有例如以下述式（1)表示之構造。 【化1】DAROCURE 1116, 1173, LUCIRIN TPO, 8893 ' UBEACRYL P36 manufactured by UCB, EZACURE -13- 201229158 manufactured by LAMBERTI, KIP150, KIP65LT, KIP100F, KT37, KT55, KT046, KIP75/B, etc. The content of the component (B) in the composition of the present invention is preferably in the range of 0.1 to 10 parts by weight, more preferably 0.3 to 5 parts by weight, based on 100 parts by weight of the total of the components (D). It is more preferably in the range of 0.5 to 5 parts by weight. Further, the content of the component (B) may be determined within the above range based on the content of the component (A). For example, when the content of the component (A) is 100 parts by weight, the content of the component (B) is preferably 0.25 to 20 parts by weight, more preferably 5 to 15 parts by weight. A cured film of high hardness can be obtained by setting the content of the component (B) within the above range. (C) a nonionic surfactant composed of a fatty acid ester (hereinafter referred to as a component (C) is a "(C) fatty acid ester-based surfactant"). The component (C) is formulated for the purpose of not easily attaching. The fingerprint of the hard coat layer obtained in the present invention at the same time makes the fingerprint wiping property good. The curable composition of the present invention is preferably used by spray coating. At the time of spray coating, since the surfactant is not locally biased on the surface of the coating film, it is necessary to prepare a large amount of surfactant when coated by other coating methods, but by using HLB in the range of 2 to 7. The nonionic surfactant can inhibit the whitening of the cured film. For the same reason, the HLB of the component (C) is preferably from 2 to 4. Further, by imparting a (meth)acrylonyl group to the component (C), it can be bonded and immobilized to the binder component in the composition of the present invention, so that the (C) fatty acid ester-based surfactant can be prevented from permeating. Hardened film surface. According to this, the durability of the obtained cured film is improved. Further, the component (C) is preferably a hydrocarbon group having a linear or branched chain having a carbon number of 6 to 30 or a divalent hydrocarbon group of -14 to 201229158. By having a hydrocarbon group having a carbon number of 6 to 30, the obtained cured film can be imparted with fingerprint visibility or fingerprint wiping property. Here, "fingerprinting" means that it is difficult to see with the naked eye when the fingerprint is attached to the surface of the film. Here, the HLB (hydrophilic-hydrophobic balance) 値 is an important index showing the characteristics of the surfactant, and shows the degree of hydrophilicity or lipophilicity. HLB値 can be obtained by the following calculation formula. ◎ HLB = 7 + 1 1.7Log(Mw/M〇) where Mw is the molecular weight of the hydrophilic group, Μ. It is the molecular weight of the lipophilic group. Mw + M〇 = M (molecular weight of the surfactant). The HLB of the (C) fatty acid ester-based surfactant used in the present invention is not in the range of 2 to 7, more preferably in the range of 2 to 4. By setting the HLB within the above range, even if a large amount of the surfactant is formulated, it is not whitened, and a composition suitable for spray coating can be obtained. The method of imparting a (meth)acrylonitrile group to the component (C) can be obtained by, for example, converting a hydroxyl group of a fatty acid ester-based surfactant having a hydroxyl group into a (meth)acrylonitrile group. Specifically, the component (C) can be obtained by reacting a hydroxyl group of a fatty acid ester surfactant with a compound having a (meth) propylene group. As the compound having a (meth) acrylonitrile group, for example, a compound having an isocyanate group and a (meth) acrylonitrile group can be used. By using such a compound, a hydroxyl group of a fatty acid ester type surfactant can be reacted with an isocyanate group to form a urethane bond, and a (meth) acrylonitrile group can be introduced. Specific -15-201229158 of a compound having an isocyanate group and a (meth) acrylonitrile group can be used as 2-(meth) propylene methoxyethyl isocyanate or 2-(meth) propylene hydride isocyanate. Oxypropyl propyl ester, 1,1-bis[(meth)acryloxymethyl]ethyl isocyanate, and the like. Further, a diisocyanate compound can be obtained by reacting a compound having a hydroxyl group with a (meth) acrylonitrile group. The diisocyanate compound is exemplified by isophorone diisocyanate, toluene diisocyanate, hexamethylene diisocyanate or the like. Specific examples of the fatty acid ester-based surfactant having a hydroxyl group are exemplified by polyoxyalkylene hardened castor oil, polyoxyalkylene alkyl fatty acid ester and the like. It is preferably polyoxyethylene ethyl hardened castor oil or polyoxyethylene ethyl ester. Commercially available products of polyoxyethylene hardened castor oil are exemplified by, for example, EM A LEX HC system 歹 ij (manufactured by Japan Emulsion Co., Ltd.), NOIGEN HC series (manufactured by Daiichi Kogyo Co., Ltd.), and the like. Commercially available products of the polyoxyethylene fatty acid ester are exemplified by, for example, EMALEX GWIS-100EX (glyceryl isostearate, manufactured by Japan Emulsion Co., Ltd.), NOIGEN GIS series (manufactured by Daiichi Kogyo Co., Ltd.), and the like. The reaction of a fatty acid ester-based surfactant having a hydroxyl group with a compound having an isocyanate group and a (meth) acrylonitrile group can be carried out as follows. That is, the reaction of the 'isocyanate compound and the hydroxyl group-containing compound is preferably 1 part by weight relative to the total amount of the reactants. 〇 1 to 1 part by weight of the general copper naphthenate, cobalt naphthenate, naphthenic Zinc acid, dibutyltin dilaurate, triethylamine, 1,4-diazabicyclo[2.2.2]octane, 2,6,7-trimethyl-1,4-diazabicyclo[ 2.2.2] A urethane catalyst such as octane. Moreover, the reaction of the compounds can also be carried out without a catalyst. The reaction temperature is usually 〇~90 °C ', preferably 40 to 80 °C. The reaction can be carried out in the absence of a solvent, and -16-201229158 can also be dissolved in a solvent. The component (C) may have a structure represented by, for example, the following formula (1). 【化1】

式（1 )中，各符號意義如下。X表示可經取代之碳數 〇 3~10之（n^+m2)價之烴基。複數個Y1及Y2各獨立爲含有 醚鍵、酯鍵、或胺基甲酸酯鍵之二價基或單鍵’且γ1及γ2 之至少一個具有源自脂肪酸之構造。Ζ表示具有一個以上 之（甲基）丙烯醯基之基。複數個R11及R12各獨立表示碳 數1~4之直鏈或分支之烴基。m1及m2分別爲〇~1〇之整數， η1及n2各獨立爲0~2 0之整數。但，m1及m2不同時爲〇。 成分（C )之化合物可如下列般合成。 對於具有羥基之界面活性劑，以使反應後之HLB成爲 Ο 2~7之比率’使具有（甲基）丙烯醯基之異氰酸酯化合物 或（甲基）丙烯酸反應而獲得。例如，使用具有三個羥基 之界面活性劑作爲原料時，原料之界面活性劑之HLB爲5 時’亦可僅使羥基之1/3莫耳當量之具有（甲基）丙烯醯 基之異氰酸酯化合物或（甲基）丙烯酸反應。原料之界面 活性劑之HLB爲9時’較好使羥基等莫耳當量之具有（甲 基）丙烯醯基之異氰酸酯化合物或（甲基）丙烯酸反應。 本發明之組成物中之成分（C)之含量相對於成分（a )及（B )之合計1〇〇重量份爲1〇〜1〇〇重量份之範圍內，較 -17- 201229158 好爲10〜80重量份之範圍內，更好爲ίο〜50重量份之範圍內 。藉由使成分（C)之含量落在上述範圍，即使噴霧塗佈 亦可獲得充分之指紋辨識性故較佳。又，成分（c )不具 有（甲基）丙烯醯基時，有硬化膜硬度下降之虞，故成分 (C)之調配量相對於成分（A)及（B)之合計100重量 份較好爲1 0〜5 0重量份。 (E )無機氧化物粒子 本發明之組成物亦可含有無機氧化物粒子作爲成分（ E )。成分（E)只要爲以無機氧化物作爲主成分之粒子即 無特別限制。成分（E)期待可提高層合薄膜之硬度、縮 小捲曲之效果。 成分（E )可依據所得硬化性組成物之硬化膜透明性 、色調之觀點選擇使用。 成分（E )之較佳例示可列舉爲以由矽、鋁、锆、鈦 、鋅、鍺、銦、錫、銻及姉所組成群組選出之至少一種元 素之無機氧化物作爲主成分之粒子。具體而言可列舉爲二 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 粒子。其中，就高硬度之觀點而言，較好爲二氧化矽、氧 化鋁、氧化锆及氧化銻之粒子。該等可單獨使用或組合兩 種以上使用。另外，成分（E )較好以粉體狀或溶劑分散 溶膠使用。以溶劑分散溶膠使用時，作爲分散介質並不特 別限於水或有機溶劑等，但就與其他成分之相溶性 '分散 -18- 201229158 性之觀點而言，分散介質較好爲有機溶劑。該種有機溶劑 可列舉爲例如甲醇、乙醇、異丙醇、丁醇、辛醇等醇類； 丙酮、甲基乙基酮、甲基異丁基酮、環己酮等酮類；乙酸 乙酯、乙酸丁酯、乳酸乙酯、γ-丁內酯、丙二醇單甲基醚 乙酸酯、丙二醇單乙基醚乙酸酯等酯類；乙二醇單甲基醚 、二乙二醇單丁基醚等醚類；苯、甲苯、二甲苯等芳香族 烴類；二甲基亞颯、二甲基乙醯胺、Ν-甲基吡咯烷酮等醯 Q 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、二甲苯較佳。 成分（Ε)之數平均粒徑較好在l~200nm之範圍內， 更好在5〜150nm之範圍內，又更好在10~100nm之範圍內。 數平均粒徑爲上述範圍時，可同時具有作爲硬化物時之透 明性與硬度。無機氧化物粒子（E )之數平均粒徑意指以 透射型電子顯微鏡觀察測定20個粒徑之平均値。另外，亦 可添加各種界面活性劑或胺類以改良粒子之分散性。 Q 作爲矽氧化物粒子（例如，二氧化矽粒子）之市售商 品可列舉爲例如作爲膠體二氧化矽之日產化學工業（股） 製造之甲醇二氧化矽溶膠、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，作爲粉體二 氧化砂可列舉爲日本Aerosil (股）製造之Aerosil 130、 Aerosil 3 00、Aerosil 3 80、Aerosil 600、Aerosil 0X50、 旭硝子（股）製造之 SILDEX H31、H32、H51、H52、 H121、H122、日本 Silica 工業（股）製造之 E220A、E220 -19- 201229158 、富士 SYLYSIA (股）製造之SYLYSIA 470、日本板硝子 (股）製造之SG薄片等。 另外，作爲氧化鋁之水分散品可列舉爲日產化學工業 (股）製造之氧化鋁溶膠-100、-2 00、-520;作爲氧化鋁 之異丙醇分散品可列舉爲住友大阪Cement (股）製造之 A S-l 5 01 ;作爲氧化鋁之甲苯分散品可列舉爲住友大阪 Cement (股）製造之AS-15 0T ;作爲氧化銷之甲苯分散品 可列舉爲住友大阪Cement (股）製造之HXU-1 10JC ;作爲 銻酸鋅粉末之水分散品可列舉爲日產化學工業（股）製造 之CENACCS ;作爲氧化鋁、氧化鈦、氧化錫、氧化銦、氧 化鋅等粉末及溶劑分散品可列舉爲CIK化成（股）製造之 Nanotech ;作爲摻雜銻之氧化錫之水分散溶膠可列舉爲石 原產業（股）製造之SN-100D ;作爲ITO粉末可列舉爲三 菱材料（股）製造之製品；作爲氧化铈水分散液可列舉爲 多木化學（股）製造之NEEDRAL等。 成分（E)之形狀爲球狀、中空狀、多孔質狀、棒狀 、板狀、纖維狀、或無定形狀，較好爲球狀。成分（E ) 之比表面積（使用氮氣以B E T比表面積測定法測得）較好 爲 10〜1000m2/g，更好爲 100~500m2/g。 成分（E)亦較好爲以分子內具有聚合性不飽和基及 水解性矽烷基之有機化合物（Eb )(以下稱爲「粒子改質 劑（Eb )」）表面處理之無機氧化物粒子（以下稱爲「反 應性粒子（Ec )」）。對於反應性粒子（Ec ),未以粒子 改質劑（Eb)表面處理之成分（E)稱爲「氧化物粒子（ -20- 201229158In the formula (1), the meaning of each symbol is as follows. X represents a hydrocarbon group which may be substituted with a carbon number of ~ 3 to 10 (n^+m2). The plurality of Y1 and Y2 are each independently a divalent group or a single bond' containing an ether bond, an ester bond, or a urethane bond, and at least one of γ1 and γ2 has a structure derived from a fatty acid. Ζ represents a group having one or more (meth) acrylonitrile groups. A plurality of R11 and R12 each independently represent a linear or branched hydrocarbon group having 1 to 4 carbon atoms. M1 and m2 are integers of 〇~1〇, and η1 and n2 are each an integer of 0~20. However, m1 and m2 are different at the same time. The compound of the component (C) can be synthesized as follows. The surfactant having a hydroxyl group is obtained by reacting an isocyanate compound having a (meth)acrylonitrile group or (meth)acrylic acid in such a ratio that HLB after the reaction becomes Ο 2 to 7. For example, when a surfactant having three hydroxyl groups is used as a raw material, when the HLB of the surfactant of the raw material is 5, an isocyanate compound having a (meth)acrylonitrile group of only 1/3 molar equivalent of the hydroxyl group may be used. Or (meth)acrylic acid reaction. The interface of the raw materials When the HLB of the active agent is 9, it is preferred to react a (meth)acrylonitrile-based isocyanate compound or (meth)acrylic acid having a molar equivalent such as a hydroxyl group. The content of the component (C) in the composition of the present invention is in the range of 1 〇 to 1 〇〇 by weight based on 1 part by weight of the total of the components (a) and (B), which is better than -17 to 201229158. It is preferably in the range of 10 to 80 parts by weight, more preferably in the range of ίο 50 parts by weight. By setting the content of the component (C) within the above range, it is preferable to obtain sufficient fingerprint recognition even by spray coating. Further, when the component (c) does not have a (meth) acrylonitrile group, the hardness of the cured film is lowered. Therefore, the compounding amount of the component (C) is preferably 100 parts by weight based on the total of the components (A) and (B). It is 1 0 to 50 parts by weight. (E) Inorganic oxide particles The composition of the present invention may contain inorganic oxide particles as a component (E). The component (E) is not particularly limited as long as it is a particle having an inorganic oxide as a main component. The component (E) is expected to have an effect of improving the hardness and shrinking the curl of the laminated film. The component (E) can be selected and used depending on the transparency of the cured film of the curable composition and the color tone. A preferred example of the component (E) is a particle having an inorganic 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. . Specific examples thereof include particles of cerium oxide, aluminum oxide, zirconium oxide, titanium oxide, zinc oxide, cerium oxide, indium oxide, tin oxide, indium tin oxide (ITO), cerium oxide, and cerium oxide. Among them, from the viewpoint of high hardness, particles of cerium oxide, aluminum oxide, zirconium oxide and cerium oxide are preferred. These may be used alone or in combination of two or more. Further, the component (E) is preferably used in the form of a powder or a solvent-dispersed sol. When it is used as a solvent-dispersing sol, the dispersion medium is not particularly limited to water or an organic solvent, but the dispersion medium is preferably an organic solvent from the viewpoint of compatibility with other components. 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; and ethyl acetate; , butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and other esters; ethylene glycol monomethyl ether, diethylene glycol monobutyl An ether such as an ether; an aromatic hydrocarbon such as benzene, toluene or xylene; or a quinone Q amine such as dimethyl hydrazine, dimethyl acetamide or hydrazine-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 component (Ε) is preferably in the range of from 1 to 200 nm, more preferably in the range of from 5 to 150 nm, and still more preferably in the range of from 10 to 100 nm. When the number average particle diameter is in the above range, it is possible to have both transparency and hardness as a cured product. The number average particle diameter of the inorganic oxide particles (E) means an average enthalpy of 20 particle diameters as measured by transmission electron microscopy. Further, various surfactants or amines may be added to improve the dispersibility of the particles. Q, as a commercially available product of cerium oxide particles (for example, cerium oxide particles), for example, a methanol cerium oxide sol, IPA-ST, MEK-ST manufactured by Nissan Chemical Industries Co., Ltd. as a colloidal cerium oxide, NBA-ST, 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 silica sand include Aerosil 130 manufactured by Japan Aerosil Co., Ltd., Aerosil 3 00, Aerosil 3 80, Aerosil 600, Aerosil 0X50, and SILDEX H31, H32, H51, and H52 manufactured by Asahi Glass Co., Ltd. H121, H122, E220A, E220 -19- 201229158 manufactured by Japan Silica Industrial Co., Ltd., SYLYSIA 470 manufactured by Fuji SYLYSIA Co., Ltd., SG sheet manufactured by Nippon Sheet Glass Co., Ltd., etc. Further, as the water-dispersible product of alumina, alumina sol-100, -200, -520 manufactured by Nissan Chemical Industries Co., Ltd.; and isopropyl alcohol dispersion as alumina can be cited as Sumitomo Osaka Cement. A Sl 5 01 manufactured; A toluene dispersion of alumina is exemplified by AS-15 0T manufactured by Sumitomo Osaka Cement Co., Ltd.; and as a toluene dispersion of oxidation powder, HXU manufactured by Sumitomo Osaka Cement Co., Ltd. -1 10JC ; As a water dispersion of zinc phthalate powder, CENACCS manufactured by Nissan Chemical Industries Co., Ltd.; and powders and solvent dispersions such as alumina, titania, tin oxide, indium oxide, and zinc oxide can be cited as Nanotech manufactured by CIK Chemicals Co., Ltd.; SN-100D manufactured by Ishihara Sangyo Co., Ltd. as a water-dispersible sol of antimony-doped tin oxide; and ITO powder as a product manufactured by Mitsubishi Materials Co., Ltd.; The aqueous cerium oxide dispersion can be exemplified by NEEDRAL manufactured by Doki Chemical Co., Ltd. The component (E) has a spherical shape, a hollow shape, a porous shape, a rod shape, a plate shape, a fibrous shape, or an amorphous shape, and is preferably spherical. The specific surface area of the component (E) (measured by B E T specific surface area measurement using nitrogen gas) is preferably from 10 to 1,000 m 2 /g, more preferably from 100 to 500 m 2 /g. The component (E) is also preferably an inorganic oxide particle surface-treated with an organic compound (Eb) having a polymerizable unsaturated group and a hydrolyzable decyl group in the molecule (hereinafter referred to as "particle modifier (Eb)") ( Hereinafter, it is referred to as "reactive particle (Ec)"). For the reactive particles (Ec), the component (E) which is not surface-treated with the particle modifier (Eb) is called "oxide particles" (-20- 201229158)

Ea )」°反應性粒子（Ec )由於可與黏合劑成分形成共價 鍵’故可獲得耐刮傷性 '耐熱性及透明性均優異之硬化膜 粒子改質劑（Eb) 本發明中使用之粒子改質劑（Eb )只要具有聚合性不 飽和基及水解性矽烷基之有機化合物即無特別限制。至於 0 聚合性不飽和基列舉爲乙烯基、（甲基）丙烯醯基等乙烯 性不飽和基。又’所謂水解性矽烷基爲與水反應生成矽烷 醇（Si-OH)基者，列舉爲例如矽上鍵結1個以上之甲氧基 、乙氧基、正丙氧基、異丙氧基、正丁氧基等烷氧基、芳 氧基、乙醯氧基、胺基、鹵素原子者。 本發明中使用之粒子改質劑（Eb)亦可使用γ-甲基丙 烯醯氧基丙基三甲氧基矽烷等市售品，例如可使用國際公 開公報W097/12942號公報中所記載之化合物。 ❹ 反應性粒子（Ec)之調製 反應性粒子（Ec )係藉由使粒子改質劑（Eb )與氧化 物粒子（Ea )混合，並經水解，使二者結合獲得。所得反 應性粒子（Ec )中之有機聚合物成分即水解性矽烷之水解 物及縮合物之比例，通常可藉由使反應性粒子（Ec )之乾 燥粉體在空氣中完全燃燒時之重量減少％作爲恆量値，例 如在空氣中自室溫至通常爲8〇〇 °C之熱重量分析求得。 粒子改質劑（E b )對氧化物粒子（E a )之結合量以反 -21 - 201229158 應性粒子（Ec )(氧化物粒子（Ea )及粒子改質劑（Eb ) 之合計）作爲1〇〇重量％，較好爲0.01〜40重量％，更好爲 0.1〜30重量％，最好爲1〜2〇重量％。藉由使與氧化物粒子 (Ea )反應之粒子改質劑（Eb )之量落在上述範圍，可提 高組成物中之反應性粒子（Ec )之分散性，可期待提高所 得硬化物之透明性、耐刮傷性之效果。 本發明之組成物中之成分（E )爲任意成分，但添加 時之含量於係氧化物粒子（Ea )之情況或係反應性粒子（ Ec )之情況均同樣，以成分（D )以外之合計作爲1 00重量 份時，較好爲1〜30重量份，更好爲2〜20重量份之範圍內。 成分（E)之含量未達1重量％時’有無法表現調配效果之 虞，超過3 0重量份時會有塗佈性降低之虞。 又，無機氧化物粒子（E)之含量意指固體成分，以 溶劑分散溶膠之狀態使用無機氧化物粒子（E )時，其含 量不包含溶劑之量。 (D )有機溶劑 本發明之組成物可以有機溶劑稀釋使用以提高噴霧之 塗佈性。例如，作爲硬塗覆材使用時之黏度通常爲 0.1-100 mPa·秒/ 25°c，較好爲 0.5 〜50mPa·秒/25°C。 有機溶劑（D )列舉爲例如甲醇、乙醇、異丙醇、丁 醇、辛醇等醇類；丙酮、甲基乙基酮、甲基異丁基酮、環 己酮等酮類；乙酸乙酯、乙酸丁酯、乳酸乙酯、γ-丁內酯 、丙二醇單甲基醚乙酸酯、丙二醇單乙基醚乙酸酯等酯類 -22- 201229158 :乙二醇單甲基醚、二乙二醇單丁基醚等醚類；苯、甲苯 、二甲苯等芳香族烴類；二甲基甲醯胺、二甲基乙醯胺、 N-甲基吡咯烷酮等醯胺類等。 本發明之組成物中視需要使用之有機溶劑（D )之調 配量以除溶劑外之成分之合計作爲1 00重量份時，較好在 5 0〜10, 〇〇〇重量份之範圍內。溶劑之調配量可考慮塗佈膜 厚、組成物黏度、噴霧噴嘴之形狀、噴嘴直徑等適當決定 (F )其他添加劑 本發明之組成物中除上述成分外，亦可視需要添加（ A) 、 （C)及（Ec)成分以外之自由基聚合性化合物、 抗氧化劑、紫外線吸收劑、平流劑等。 本發明之組成物可藉由分別添加上述（A ) ~ ( D )成 分及視需要由（E)〜（G)成分任意選擇之成分，在室溫 〇或加熱條件下混合而調製。具體而言，可使用混練機、捏 合機、球磨機等習知之混合機調製。但，在加熱條件下混 合時，較好在聚合起始劑或聚合性不飽和基之分解起始溫 度以下進行。 如上述獲得之本發明之組成物可藉由輻射線（光）硬 化。 硬化膜 本發明之硬化膜可藉由將前述本發明之組成物塗覆於 -23- 201229158 各種基材上並經硬化獲得。具體而言，可藉由塗佈組成物 ’且視需要在0〜200°C使（D)有機溶劑等揮發成分揮發去 除後’以輻射線進行硬化處理而獲得。 塗覆基材之方法除噴霧塗佈以外，可列舉爲一般之塗 覆方法，例如浸漬塗佈、流動塗佈、淋流塗佈、輥塗佈、 旋轉塗佈、刷毛塗佈等。該等塗佈中之塗膜厚度以乾燥、 硬化後之膜厚計，較好爲0.1〜4 0 0 μιη，更好爲0.5-2 0 0 μηι。 至於輻射線只要是可在塗佈後短時間使組成物硬化者 即無特別限制，但就照射裝置取容易等之理由而言，較好 爲紫外線、電子束。作爲紫外線之線源可使用水銀燈、鹵 素燈、雷射等，且作爲電子束之線源可使用利用市售之自 鎢絲產生熱電子之方式等。使用紫外線或電子束作爲輻射 線時，較好紫外線之照射光量爲0.01〜l〇J/cm2，更好爲 0.1〜2J/cm2。且，較佳之電子束照射條件爲加速電壓爲 10〜3 00kV，電子密度爲0.02〜0.30mA/cm2，電子束照射量 爲 1 〜lOMrad。 III.基材 至於成爲被覆對象之基材並無特別限制’列舉爲例如 聚碳酸酯、聚甲基丙烯酸酯、聚苯乙烯、聚酯、聚烯烴、 環氧樹脂、三聚氰胺、三乙醯基纖維素、ABS、AS、降冰 片烯系樹脂等塑膠、玻璃、木材、金屬等。直接塗佈時， 基材與硬塗層之密著性差時，亦可預先對基材進行底層處 理。 -24 - 201229158 IV.應用例 本發明之硬塗層由於具有優異之指紋辨識性及指紋擦 拭性，故特別適用作爲人類會直接接觸般之行動電話、資 訊終端等各種攜帶式機器之表面保護層。 [實施例] 以下，利用實施例更具體說明本發明，但本發明並不 受該等實施例之任何限制。又，只要沒有特別指明，則^ %」表不重量％，「份」表不重量份。 合成例1 :化合物（C-1 )之製造 【化2】 (OCH2CH2)a〇R1 CH2〇CO(CH2)i〇CH(CH2)5CH3 (OCH2CH2)b 〇r1 CHOCO(CH2)10CH(CH2)5CH3 (OCH2CH2)c 〇r1Ea)" The reactive particles (Ec) can form a covalent bond with the binder component, so that scratch-resistant "curing film particle modifier (Eb) excellent in heat resistance and transparency can be obtained. The particle modifier (Eb) is not particularly limited as long as it has a polymerizable unsaturated group and a hydrolyzable alkylene group. The 0 polymerizable unsaturated group is exemplified by an ethylenically unsaturated group such as a vinyl group or a (meth) acrylonitrile group. Further, the term "hydrolyzable alkylene group" is a group which reacts with water to form a stanol (Si-OH) group, and is exemplified by, for example, a methoxy group, an ethoxy group, a n-propoxy group or an isopropoxy group bonded to the oxime. An alkoxy group such as n-butoxy group, an aryloxy group, an ethoxylated group, an amine group or a halogen atom. The particle modifier (Eb) used in the present invention may be a commercially available product such as γ-methacryloxypropyltrimethoxydecane, and for example, a compound described in International Publication No. WO97/12942 may be used. .调制 Preparation of Reactive Particles (Ec) The reactive particles (Ec) are obtained by mixing a particle modifier (Eb) with an oxide particle (Ea) and hydrolyzing the two. The ratio of the hydrolyzate and the condensate of the organic polymer component in the obtained reactive particles (Ec), that is, the hydrolyzable decane, can usually be reduced by the weight of the dry powder of the reactive particles (Ec) when completely burned in the air. % is obtained as a constant enthalpy, for example, in a thermogravimetric analysis in air from room temperature to usually 8 °C. The amount of the particle modifier (E b ) bound to the oxide particles (E a ) is determined by the anti-21 - 201229158 particles (Ec ) (the total of the oxide particles (Ea) and the particle modifier (Eb)). 1% by weight, preferably 0.01 to 40% by weight, more preferably 0.1 to 30% by weight, most preferably 1 to 2% by weight. When the amount of the particle modifier (Eb) reacted with the oxide particles (Ea) falls within the above range, the dispersibility of the reactive particles (Ec) in the composition can be improved, and the transparency of the obtained cured product can be expected to be improved. Sexual and scratch resistant effects. The component (E) in the composition of the present invention is an optional component, but the content at the time of addition is the same as that of the oxide particles (Ea) or the reactive particles (Ec), and is different from the component (D). When the total amount is 100 parts by weight, it is preferably from 1 to 30 parts by weight, more preferably from 2 to 20 parts by weight. When the content of the component (E) is less than 1% by weight, the amount of the coating may not be exhibited, and when it exceeds 30 parts by weight, the coating property may be lowered. Further, the content of the inorganic oxide particles (E) means a solid component, and when the inorganic oxide particles (E) are used in a state in which the solvent-dispersed sol is used, the content thereof does not include the amount of the solvent. (D) Organic solvent The composition of the present invention can be used in an organic solvent to improve the coating property of the spray. For example, the viscosity when used as a hard coating material is usually from 0.1 to 100 mPa·s / 25 ° C, preferably from 0.5 to 50 mPa·s / 25 ° C. The organic solvent (D) is exemplified by alcohols such as methanol, ethanol, isopropanol, butanol, and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; , butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and other esters-22- 201229158 : ethylene glycol monomethyl ether, two An ether such as diol monobutyl ether; an aromatic hydrocarbon such as benzene, toluene or xylene; or a guanamine such as dimethylformamide, dimethylacetamide or N-methylpyrrolidone. The amount of the organic solvent (D) to be used in the composition of the present invention is preferably in the range of from 50 to 10 parts by weight based on 100 parts by weight of the total of the components other than the solvent. The amount of the solvent to be formulated may be appropriately determined in consideration of the coating film thickness, the viscosity of the composition, the shape of the spray nozzle, the diameter of the nozzle, etc. (F) Other additives In addition to the above components, the composition of the present invention may be added as needed (A), ( A radical polymerizable compound other than the components C) and (Ec), an antioxidant, an ultraviolet absorber, a leveling agent, and the like. The composition of the present invention can be prepared by mixing the components (A) to (D) and optionally arbitrarily selected from the components (E) to (G), and mixing them under room temperature or heating. Specifically, it can be prepared by a conventional mixer such as a kneader, a kneader or a ball mill. However, when it is mixed under heating, it is preferably carried out below the decomposition initiation temperature of the polymerization initiator or the polymerizable unsaturated group. The composition of the present invention obtained as described above can be hardened by radiation (light). Cured Film The cured film of the present invention can be obtained by applying the aforementioned composition of the present invention to various substrates of -23 to 201229158 and hardening it. Specifically, it can be obtained by applying a composition ' and optionally removing a volatile component such as an organic solvent (D) at 0 to 200 ° C to remove it by radiation. The method of coating the substrate may be, for example, a general coating method such as dip coating, flow coating, trickle coating, roll coating, spin coating, brush coating or the like, in addition to spray coating. The thickness of the coating film in the coating is preferably from 0.1 to 4,000 μm, more preferably from 0.5 to 200 μm, based on the film thickness after drying and hardening. The radiation is not particularly limited as long as it can cure the composition for a short period of time after application. However, it is preferably an ultraviolet ray or an electron beam because the irradiation device is easy to handle. A mercury lamp, a halogen lamp, a laser or the like can be used as the source of the ultraviolet rays, and as a line source of the electron beam, a commercially available method of generating hot electrons from a tungsten wire can be used. When ultraviolet rays or electron beams are used as the radiation, the amount of ultraviolet light to be irradiated is preferably 0.01 to 1 〇 J/cm 2 , more preferably 0.1 to 2 J/cm 2 . Further, preferred electron beam irradiation conditions are an acceleration voltage of 10 to 300 kV, an electron density of 0.02 to 0.30 mA/cm2, and an electron beam irradiation amount of 1 to 1 OMrad. III. Substrate As the substrate to be coated, there is no particular limitation 'exemplified as polycarbonate, polymethacrylate, polystyrene, polyester, polyolefin, epoxy resin, melamine, triethylene fluorene fiber, for example. Plastics, glass, wood, metal, etc., such as ABS, AS, norbornene resin. In the case of direct coating, when the adhesion between the substrate and the hard coat layer is poor, the substrate may be subjected to the underlayer treatment in advance. -24 - 201229158 IV. Application Example The hard coat layer of the present invention is particularly suitable as a surface protective layer for various portable machines such as mobile phones and information terminals which are directly in contact with human beings because of excellent fingerprint recognition and fingerprint wiping. . [Examples] Hereinafter, the present invention will be specifically described by examples, but the present invention is not limited by the examples. Further, unless otherwise specified, the "%" table is not a weight%, and the "part" table is not a part by weight. Synthesis Example 1: Production of Compound (C-1) [Chem. 2] (OCH2CH2) a〇R1 CH2〇CO(CH2)i〇CH(CH2)5CH3 (OCH2CH2)b 〇r1 CHOCO(CH2)10CH(CH2)5CH3 (OCH2CH2)c 〇r1

I CH2OCO(CH2)10CH(CH2)5CH3 ⑵ 式（2)中，R1爲以下述式（3)表示之基。a + b + c = 7 -25 - 201229158 【化3】I CH2OCO(CH2)10CH(CH2)5CH3 (2) In the formula (2), R1 is a group represented by the following formula (3). a + b + c = 7 -25 - 201229158 【化3】

NHCOOCH2 Ο ΗNHCOOCH2 Ο Η

II III I

—C-N—C-N

X (3) ch2oc〇ch=ch2 ch2ococh=ch2 CH2OCOCH=CH2 將2,6-二第三丁基-對-甲酚（吉富精密化學公司製造 ，YOSHINOX BHT) 0.03 0g、季戊四醇三丙烯酸酯（新中X (3) ch2oc〇ch=ch2 ch2ococh=ch2 CH2OCOCH=CH2 2,6-di-t-butyl-p-cresol (manufactured by Jifu Precision Chemical Co., Ltd., YOSHINOX BHT) 0.03 0g, pentaerythritol triacrylate (Xinzhong

村化學製造，NK ESTER A-TMM-3LM-N) 21.05g、異氰酸Village Chemical Manufacturing, NK ESTER A-TMM-3LM-N) 21.05g, isocyanic acid

3-異氰酸酯甲基-3,5,5-三甲基環己基酯（住化拜耳胺基甲 酸酯公司製造，Desmodur I) 9.10g、及甲基異丁基酮（三 菱化學公司製造）50_00g饋入安裝有攪拌機之三頸燒瓶中 ，於其中添加二月桂酸二辛基錫（共同藥品公司製造， KS- 1 200-A) 0.031g後，在室溫攪拌2小時。接著，添加聚 氧伸乙基硬化蓖麻油（日本Emulsion公司製造，EMALAX HC-7; HLB値6) 19.52g。使反應液升溫至60°C且攪拌2小 時’獲得化合物（C-1 )。又’由於丙烯酸化反應幾乎定 量進行，故由饋入量求得化合物（C-1)之HLB爲3。 合成例2〜6:化合物（C-2)〜（C-6)之製造 除以表1所示之比例使用表1所示之化合物以外，餘與 合成例1同樣獲得化合物（C-2 )〜（c_6 )。該等之Hlb — 起記載於表1。 化合物（C - 2 ) -26- 201229158 【化4】 (0CH2CH2)a0R23-Isocyanate methyl-3,5,5-trimethylcyclohexyl ester (Desmodur I, manufactured by Bayer Ammonium Co., Ltd.) 9.10 g, and methyl isobutyl ketone (manufactured by Mitsubishi Chemical Corporation) 50_00 g The mixture was fed to a three-necked flask equipped with a stirrer, and 0.031 g of dioctyltin dilaurate (manufactured by Kyocera Corporation, KS-1200-A) was added thereto, followed by stirring at room temperature for 2 hours. Next, 19.52 g of polyoxyethylene hardened castor oil (manufactured by Japan Emulsion Co., Ltd., EMALAX HC-7; HLB®6) was added. The reaction solution was warmed to 60 ° C and stirred for 2 hours to obtain a compound (C-1). Further, since the acrylation reaction proceeds almost quantitatively, the HLB of the compound (C-1) was found to be 3 from the amount of the feed. Synthesis Example 2 to 6: Production of Compounds (C-2) to (C-6) The compound (C-2) was obtained in the same manner as in Synthesis Example 1 except that the compound shown in Table 1 was used in the ratio shown in Table 1. ~(c_6). These Hlbs are described in Table 1. Compound (C - 2 ) -26- 201229158 [Chemical 4] (0CH2CH2) a0R2

I CH2OCO(CH2)10CH(CH2)5CH3 (OCH2CH2)b〇R2 CHOCO(CH2)10CH(CH2)5CH3 (OCH2CH2)c 〇r2I CH2OCO(CH2)10CH(CH2)5CH3(OCH2CH2)b〇R2 CHOCO(CH2)10CH(CH2)5CH3 (OCH2CH2)c 〇r2

I (4) CH2OCO(CH2)10CH(CH2)5CH3I (4) CH2OCO(CH2)10CH(CH2)5CH3

式（4 )中，R2分別爲以下述式 表币之基。 a+b+c=7 0 【化5】 0 H ch2〇coch=ch2 —c—N—-NHCOOCH2--CH2〇COCH=CH2 CH2OCOCH=CH2 (5) 化合物（C-3 ) 、（ C-4 )及（C-5 ) O【化6】 (OCH2CH2)aOR3In the formula (4), R2 is each based on the following formula. a+b+c=7 0 【化5】 0 H ch2〇coch=ch2 —c—N—-NHCOOCH2--CH2〇COCH=CH2 CH2OCOCH=CH2 (5) Compound (C-3), (C-4 ) and (C-5 ) O [Chemical 6] (OCH2CH2) aOR3

I CH2OCO(CH2)10CH(CH2)5CH3 (OCH2CH2)b〇R3 / CHOCO(CH2)10CH(CH2)5CH3 (OCH2CH2)cOR3I CH2OCO(CH2)10CH(CH2)5CH3 (OCH2CH2)b〇R3 / CHOCO(CH2)10CH(CH2)5CH3 (OCH2CH2)cOR3

I CH2OCO<CH2)10CH(CH2)5CH3 (6) 式（6)中，R3各獨立爲氫原子或以下述式表示之基 。但，式（6 )爲（C-3 )時，R3爲以下述式（5 )表示之 -27- 201229158 基 ° a+b+c=5 【化7】 Ο Η II I •C-N- CH2〇COCH=CH2 —-NHCOOCH2—j—CH2OCOCH=CH2 CH2OCOCH=CH2 (5) 化合物（C-6) 【化8】 (OCH2CH2)a〇R4 9H2OCO(CH2)104h(CH2)5CH3 (OCH2CH2)bOR4 CHOCO(CH2)i〇CH(CH2)5CH3 (OCH2CH2)c or4I CH2OCO <CH2)10CH(CH2)5CH3 (6) In the formula (6), each of R3 is independently a hydrogen atom or a group represented by the following formula. However, when the formula (6) is (C-3), R3 is represented by the following formula (5): -27-201229158 base ° a+b+c=5 [chemical 7] Ο Η II I • CN-CH2〇 COCH=CH2 —-NHCOOCH2—j—CH2OCOCH=CH2 CH2OCOCH=CH2 (5) Compound (C-6) (Chem. 8) (OCH2CH2) a〇R4 9H2OCO(CH2)104h(CH2)5CH3 (OCH2CH2)bOR4 CHOCO(CH2 )i〇CH(CH2)5CH3 (OCH2CH2)c or4

I 表示 CH2OCO(CH2)10CH(CH2)5CH3 ⑺ 式（7 )中，R4各獨立爲氫原子或以下& 之基。a + b + c = 5。 【化9】I represents CH2OCO(CH2)10CH(CH2)5CH3 (7) In the formula (7), R4 is each independently a hydrogen atom or a group of the following & a + b + c = 5. 【化9】

Ο Η II I 一C-N NHCOOCH2CH2〇COCH-CM2 合成例7 :化合物（C-7)之製造 -28- (8) 201229158 【化1 0】 (0CH2CH2)a0R5 ch2oco(ch2)100h(ch2)5ch3 (OCH2CH2)b〇R5 CHOC〇(CH2)10CH(CH2)5CH3 (OCH2CH2)c〇R5Ο Η II I -CN NHCOOCH2CH2〇COCH-CM2 Synthesis Example 7: Production of Compound (C-7) -28- (8) 201229158 [Chemical 1 0] (0CH2CH2) a0R5 ch2oco(ch2)100h(ch2)5ch3 (OCH2CH2 )b〇R5 CHOC〇(CH2)10CH(CH2)5CH3 (OCH2CH2)c〇R5

I CH2OCO(CH2)10CH(CH2)5CH3 ⑼ O 式（9)中，R5各獨立爲氫原子或以下述式（1〇)表 示之基。a + b + c = 5 〇 【化11】 Ο H CH3 II I I ' —C—N—CH2〇H2〇C〇~C—CH2 (10) 將2,6-二第三丁基-對-甲酚（吉富精密化學公司製造 ，YOSHINOX BHT) 0.005g、異氰酸2-甲基丙烯醯氧基乙 〇 基酯（昭和電工公司製造’ KAREN Z MOI) 1.79 g饋入安裝 攪拌機之三頸燒瓶中，於其中添加二月桂酸二辛基錫（共 同藥品公司製造，KS- 1 200-A) 0.040g後，在室溫攪拌2小 時。接著，添加聚氧伸乙基硬化蓖麻油（日本Emulsion公 司製造，EMALAX HC-5; HLB値5) 48.17g。使反應液升 溫至60°C且攪拌2小時，獲得化合物（C-7 )。 -29- 201229158 [表1] 成分(重量％) 合成例1 合成例2 合成例3 合成例4 合成例5 合成例6 合成例7 (C-1) (C-2) (C-3) (C-4) (C-5) (C-6) (C-7) HC-5 - - 18.61 23.54 31.88 36.42 48.169 HC-7 19.52 20.03 - - — - - TDI — 8.05 8.43 7.11 4.82 8.25 - 1PDI 9.10 - - - — 一 — KARENZ M0I 一 一 - 一 - - 1.786 PETA 21.05 21.60 22.62 19.07 12.92 - — HEA - 一 - — 一 5.00 - DPHA 一 - - - - 一 - BHT 0.030 0.030 0.036 0.030 0.041 0.035 0.005 KS-1200-A 0.310 0.292 0.306 0.258 0.349 0.299 0.040 MIBK 50 50 50 50 50. 50 50 HLB 3 3 2 2 3 4 4I CH2OCO(CH2)10CH(CH2)5CH3 (9) O In the formula (9), each of R5 is independently a hydrogen atom or a group represented by the following formula (1). a + b + c = 5 〇 [化11] Ο H CH3 II II '-C-N-CH2〇H2〇C〇~C—CH2 (10) 2,6-di-tert-butyl-p-- Phenol (manufactured by Jifu Precision Chemical Co., Ltd., YOSHINOX BHT) 0.005g, 2-methylpropenyl ethoxyethyl methacrylate (Manufactured by Showa Denko's KAREN Z MOI) 1.79 g fed into a three-necked flask equipped with a mixer After adding 0.040 g of dioctyltin dilaurate (manufactured by Co-Pharmaceutical Co., Ltd., KS-1200-A), it was stirred at room temperature for 2 hours. Next, polyoxyethylene ethyl hardened castor oil (manufactured by Japan Emulsion Co., Ltd., EMALAX HC-5; HLB® 5) was added in an amount of 48.17 g. The reaction solution was warmed to 60 ° C and stirred for 2 hours to give Compound (C-7). -29-201229158 [Table 1] Ingredient (% by weight) Synthesis Example 1 Synthesis Example 2 Synthesis Example 3 Synthesis Example 4 Synthesis Example 5 Synthesis Example 6 Synthesis Example 7 (C-1) (C-2) (C-3) ( (4) - (1) - - - one - KARENZ M0I one - one - - 1.786 PETA 21.05 21.60 22.62 19.07 12.92 - — HEA - one - one 5.00 - DPHA one - - - - one - BHT 0.030 0.030 0.036 0.030 0.041 0.035 0.005 KS-1200- A 0.310 0.292 0.306 0.258 0.349 0.299 0.040 MIBK 50 50 50 50 50. 50 50 HLB 3 3 2 2 3 4 4

合成例8 :化合物（C-8 )之製造 【化1 2】Synthesis Example 8: Production of Compound (C-8) [Chemical Formula 1 2]

OH OH h2c-oco(ch2)70h(ch2)20h(ch2)5ch3OH OH h2c-oco(ch2)70h(ch2)20h(ch2)5ch3

OH OHOH OH

CHOCO(CH2)70H(CH2)20H(CH2)5CH3 OH OH H2C-〇CO(CH2)7iH(CH2)20H(CH2)5CH3 於安裝攪拌機之三頸燒瓶中混合蓖麻油（和光純藥製 造）0.93 3 g、0.03 6g之0.05ml/l硫酸，在60°C加熱攪拌，藉 此獲得羥基濃度6.1mmol/g之化合物（C-8 ) 。（C-8)之 HLB爲 2。 表1中所記載之化合物如下。 HC-7 ： EMALAX HC-7，具有以下述式表示之構造之 聚氧伸乙基硬化蓖麻油，日本Emulsion公司製造。 -30- 201229158 【化1 3】CHOCO(CH2)70H(CH2)20H(CH2)5CH3 OH OH H2C-〇CO(CH2)7iH(CH2)20H(CH2)5CH3 Mixed with castor oil (manufactured by Wako Pure Chemical Industries, Ltd.) in a three-necked flask equipped with a mixer 0.93 3 g, 0.03 6 g of 0.05 ml/l of sulfuric acid, and heating and stirring at 60 ° C, thereby obtaining a compound (C-8 ) having a hydroxyl group concentration of 6.1 mmol/g. The HLB of (C-8) is 2. The compounds described in Table 1 are as follows. HC-7: EMALAX HC-7, a polyoxyethylene hardened castor oil having a structure represented by the following formula, manufactured by Japan Emulsion Co., Ltd. -30- 201229158 【化1 3】

(OCH2CH2)a〇H(OCH2CH2)a〇H

I CH2OCO(CH2)10CH(CH2)5CH3I CH2OCO(CH2)10CH(CH2)5CH3

(OCH2CH2)b〇H(OCH2CH2)b〇H

I CHOCO(CH2)10CH(CH2)5CH3I CHOCO(CH2)10CH(CH2)5CH3

(OCH2CH2)c〇H(OCH2CH2)c〇H

I CH2OCO(CH2)10CH(CH2)5CH3 EMALAX HC-7 ( a + b + c = 7) ，HLB値：6 〇 TDI:二井化學 Polyurethane 公司製造，tolDY-100, 甲苯二異氰酸酯，分子量：174.16 IPDI: Desmodur I，住化拜耳胺基甲酸酯公司製造， 異佛爾酮二異氰酸酯，分子量：222.29 KARENZ MOI:昭和電工公司製造，異氰酸2 -甲基丙 烯醯氧基乙基酯，分子量：155.15 PET A ： NK ESTER A-TMM-3LM-N，新中村化學公司 製造，季戊四醇三丙烯酸酯，分子量：298.3 ◎ HEA:大阪有機化學公司製造，丙燃酸徑基乙醋，分 子量：1 1 6 . 1 1 BHT : YOSHINOX BHT，吉富精密化學公司製造， 2,6-二第三丁基-對-甲酚，分子量：220 KS- 1 20 0-A :共同藥品公司製造，二月桂酸二辛基錫 MIBK :甲基異丁基酮 製造例1 粒子改質劑（Eb)之合成 -31 - 201229158 在乾燥空氣中，對由锍基丙基三甲氧基矽烷221份、 二丁基錫二月桂酸酯1份所組成之溶液，邊攪拌邊在50°C 於1小時內滴加異佛爾酮二異氰酸酯222份後，在70°C加熱 攪拌3小時。在3 0 °C於1小時內將新中村化學製造之NK ESTER A-TMM-3LM-N (由季戊四醇三丙烯酸酯60重量％ 與季戊四醇四丙烯酸酯40重量％組成。其中，與反應有關 僅爲具有羥基之季戊四醇三丙烯酸酯）5 49份後，在60°C 加熱攪拌1 〇小時，藉此獲得含聚和性不飽和基之粒子改質 劑（Eb )。以FT-IR分析產物中殘留之異氰酸酯量爲0.1% 以下，顯示反應以幾乎定量地完成。產物之紅外線吸收光 譜中，原料中之巯基特徵之25 5 OcnT1之吸收峰及原料異氰 酸酯化合物特徵之2260CHT1之吸收峰消失，且觀察到新的 胺基甲酸酯鍵及S(C = 〇)NH-基特徵之ISSOcmd之峰及丙烯 醯基特徵之172 OcnT1之峰，顯示生成同時具有作爲聚合性 不飽和基之丙烯醯基及- S(C = 0)NH-、胺基甲酸酯鍵之丙烯 醯基修飾之烷氧基矽烷。依據上述，獲得粒子改質劑（Eb )合計773份與季戊四醇四丙烯酸酯220份。 製造例2 (Ec)之反應性粒子1 ( I)之製造 製造例1中製造之組成物2.9 8份（含2.3 2份粒子改質劑 (Eb))、二氧化砂粒子分散液（Ea)(固體成分：35重 量％，MEK-ST-L，數平均粒徑0.08μπι，日產化學工業（股 )製造）89.90份，離子交換水〇·12份、及對-羥基苯基單 -32- 201229158 甲基醚0.01份之混合液在60°C攪拌4小時後’添加原甲酸甲 酯1.3 6份，接著在同一溫度下加熱攪拌1小時’獲得反應 性粒子分散液。將該分散液秤量2g於銘盤上後’在175°C 之加熱板上乾燥1小時’經秤量求得固體成分含量後’爲 36.5重量％。且，將分散液秤量2g於磁性缽中之後，在 80 °C之加熱板上預乾燥30分鐘’且由在75〇 °C之回熱爐中燒 成1小時後之無機殘留物求得固體成分中之無機含量，爲 0 95重量％。濃縮至固體成分量爲70重量％，作爲二氧化矽 粒子（I )之分散液。所得二氧化矽粒子（I )以透射型顯 微鏡法測定之數平均粒徑爲8〇nm。 製造例3 (Ec )之反應性粒子2 ( S )之製造 使γ-甲基丙烯醯氧基丙基三甲氧基矽烷（ Toray-Dowconing· Silicon公司製造 SZ6030 ) 3.14 份、 Q 二氧化矽粒子分散液（Da)(固體成分：35重量％，MEK-ST-L，數平均粒徑〇.〇8μπι，日產化學工業（股）製造） 8 9.90份、離子交換水0.12份、及對-羥基苯基單甲基醚 〇.〇1份之混合液在60°C攪拌4小時後，添加原甲酸甲酯1.36 份’接著在相同溫度下加熱攪拌1小時，獲得反應性粒子 分散液。將該分散液秤量2g於鋁盤上後，在175 °C之加熱 板上乾燥1小時，經秤量求得固體成分含量爲36.5重量％。 另外’將分散液秤量2 g於磁性缽中之後，在8 0。(：之加熱板 上預乾燥30分鐘，且由在75 (TC之回熱爐中燒成1小時後之 -33- 201229158 無機殘留物求得固體成分中之無機含量爲93重量。/°。所得 二氧化矽粒子（I )以透射型顯微鏡法測定之數平均粒徑 爲 5 0 nm。 實施例1 添加二季戊四醇六丙烯酸酯（日本化藥股份有限公司 製造：KAYARAD DPHA) 21.6重量份、光聚合起始劑（ BASF製造：IRGACURE 184) 0.6重量份、光聚合起始劑（ BASF製造：IRGACURE 907 ) 〇. 4重量份及4 8重量份（固 體成分爲2.4重量份）之合成例1中製造之化合物（C-1 ) ，接著添加22.6份之甲基異丁基酮、丙二醇單甲基醚乙酸 酯5 0重量份，經攪拌獲得硬化性組成物1。 實施例2 ~ 1 8及比較例1 ~ 3 除以表2及表3所示之調配量使用各成份以外，餘與實 施例1同樣製造各硬化性組成物。又，表2及表3中所記載 之（D)成分以外之調配量係表示固體成分之量。 〈硬化膜之製造〉 以噴霧塗佈法將上述實施例及比較例中獲得之各硬化 性組成物塗佈（膜厚6 μιη )於厚度1 8 8 μηι之PET薄膜上。在 8 0 °C乾燥3分鐘後，使用高壓水銀燈在空氣下以照射量3 〇 〇 m J / c m2照射紫外線，經光硬化製作各硬化膜。 -34- 201229158 〈硬化膜之物性評價〉 評價如上述作成之硬化膜之下列特性，所得結果示於 表2。 (1 )濁度（％ )之測定 使用彩色濁度計（Suga試驗機（股）製造），依據 JIS K7 1 05測定硬化膜之濁度（％ )。 〇 (2 )全光線透射率（Tt ; % )之測定 使用彩色濁度計（Suga試驗機（股）製造），依據 JI S K 7 1 0 5測定硬化膜之全光線透射率（％)。 (3 )指紋辨識性 將薄膜之內面打黑，且使指紋附著於薄膜表面。隨後 ，自薄膜表面之垂直上方目視觀察’依據下列評價基準進 〇 ㈣° 〇：難看見指紋 △:雖有指紋但看不清楚 X :清楚看見指紋 (4 )指紋擦拭性試驗 將薄膜之內面打黑，使指紋附著於薄膜表面。隨後’ 以衛生紙擦拭指紋’依據下列評價基準進行評價。 〇：已擦拭掉 -35- 201229158 △:不易擦拭掉 X :無法擦拭掉 (5 )接觸角（◦)之測定 使用協和界面化學股份有限公司製造之接觸角計Drop Master 5 00，依據JIS 6 768測定硬化膜對水及十六烷之接 觸角。 -36- 201229158 二雲恤 - •31 s 09 0=1 •s oI CH2OCO(CH2)10CH(CH2)5CH3 EMALAX HC-7 ( a + b + c = 7) , HLB値: 6 〇TDI: manufactured by Mitsui Chemicals Polyurethane, tolDY-100, toluene diisocyanate, molecular weight: 174.16 IPDI: Desmodur I, manufactured by Sussex Bayer Amino Acid Co., Ltd., Isophorone diisocyanate, molecular weight: 222.29 KARENZ MOI: manufactured by Showa Denko, 2-methoxypropenyl isocyanate, molecular weight: 155.15 PET A : NK ESTER A-TMM-3LM-N, manufactured by Shin-Nakamura Chemical Co., Ltd., pentaerythritol triacrylate, molecular weight: 298.3 ◎ HEA: manufactured by Osaka Organic Chemical Co., Ltd., propylene sulphate-based vinegar, molecular weight: 1 16 . 1 1 BHT : YOSHINOX BHT, manufactured by Jifu Precision Chemical Co., Ltd., 2,6-di-t-butyl-p-cresol, molecular weight: 220 KS- 1 20 0-A: manufactured by Co-Pharma, Dioctyl Dilaurate Tin MIBK: methyl isobutyl ketone production example 1 synthesis of particle modifier (Eb) -31 - 201229158 221 parts of mercaptopropyltrimethoxydecane, dibutyltin dilaurate 1 in dry air a solution consisting of parts and dropping at 50 ° C for 1 hour while stirring After isophorone diisocyanate, 222 parts, was heated with stirring at 70 ° C for 3 hours. NK ESTER A-TMM-3LM-N (manufactured by Xinzhongcun Chemical Co., Ltd., 60% by weight of pentaerythritol triacrylate and 40% by weight of pentaerythritol tetraacrylate) at 30 ° C for 1 hour. After 5 49 parts of pentaerythritol triacrylate having a hydroxyl group, the mixture was heated and stirred at 60 ° C for 1 hour to obtain a particle-modified agent (Eb ) containing a polyunsaturated unsaturated group. The amount of isocyanate remaining in the product by FT-IR analysis was 0.1% or less, indicating that the reaction was almost quantitatively completed. In the infrared absorption spectrum of the product, the absorption peak of 25 5 OcnT1 of the thiol characteristic in the raw material and the absorption peak of 2260 CHT1 characteristic of the raw material isocyanate compound disappeared, and a new urethane bond and S(C = 〇) NH were observed. The peak of the ISSOcmd of the base feature and the peak of the 172 OcnT1 characteristic of the acrylonitrile group, which shows that the propylene sulfhydryl group and the -S(C=0)NH-, urethane bond are simultaneously formed as a polymerizable unsaturated group. Acryl fluorenyl modified alkoxy decane. According to the above, a total of 773 parts of the particle modifier (Eb) and 220 parts of pentaerythritol tetraacrylate were obtained. Production Example 2 (Ec) Reactive Particle 1 (I) Production Manufactured in Production Example 1 2.9 8 parts (containing 2.3 2 parts of particle modifier (Eb)), silica sand particle dispersion (Ea) (solid content: 35% by weight, MEK-ST-L, number average particle diameter 0.08 μm, manufactured by Nissan Chemical Industries Co., Ltd.) 89.90 parts, ion exchanged water hydrazine · 12 parts, and p-hydroxyphenyl mono-32- 201229158 A mixture of 0.01 parts of methyl ether was stirred at 60 ° C for 4 hours, and then "1.6 parts of methyl orthoformate was added, followed by heating and stirring at the same temperature for 1 hour" to obtain a reactive particle dispersion. After weighing 2 g of the dispersion on a dial, it was dried on a hot plate at 175 ° C for 1 hour, and the solid content was determined to be 36.5 wt%. Further, after weighing 2 g of the dispersion in a magnetic crucible, pre-drying on a hot plate at 80 ° C for 30 minutes' and obtaining a solid by inorganic residue after firing in a reheating furnace at 75 ° C for 1 hour The inorganic content of the ingredients was 0.995% by weight. The mixture was concentrated to a solid content of 70% by weight as a dispersion of the cerium oxide particles (I). The number average particle diameter of the obtained cerium oxide particles (I) measured by a transmission type microscopic method was 8 Å. Production of Reactive Particle 2 (S) of Production Example 3 (Ec) γ-Methyl propylene methoxypropyltrimethoxy decane (SZ6030, manufactured by Toray-Dowconing Silicon Co., Ltd.) 3.14 parts, Q cerium oxide particles dispersed Liquid (Da) (solid content: 35% by weight, MEK-ST-L, number average particle diameter 〇.〇8μπι, manufactured by Nissan Chemical Industries Co., Ltd.) 8 9.90 parts, 0.12 parts of ion-exchanged water, and p-hydroxybenzene After the mixture of the monomethyl ether oxime and the hydrazine was stirred at 60 ° C for 4 hours, 1.36 parts of methyl orthoformate was added, followed by heating and stirring at the same temperature for 1 hour to obtain a reactive particle dispersion. The dispersion was weighed to 2 g on an aluminum pan, and then dried on a hot plate at 175 °C for 1 hour, and the solid content was found to be 36.5 wt%. In addition, after weighing 2 g of the dispersion into the magnetic crucible, it was at 80. (The hot plate was pre-dried for 30 minutes, and the inorganic content in the solid content was found to be 93% by weight from -33 to 201229158 inorganic residue after firing for 1 hour in a TC reheating furnace. The number average particle diameter of the obtained cerium oxide particles (I) measured by transmission microscopy was 50 nm. Example 1 Addition of dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.: KAYARAD DPHA) 21.6 parts by weight, light Polymerization initiator (manufactured by BASF: IRGACURE 184) 0.6 parts by weight, photopolymerization initiator (manufactured by BASF: IRGACURE 907) 4. 4 parts by weight and 48 parts by weight (solid content: 2.4 parts by weight) in Synthesis Example 1 The compound (C-1) produced was then added with 22.6 parts of methyl isobutyl ketone and 50 parts by weight of propylene glycol monomethyl ether acetate, and the hardened composition 1 was obtained by stirring. Examples 2 to 18 and Comparative Examples 1 to 3 Each of the curable compositions was produced in the same manner as in Example 1 except that the components shown in Tables 2 and 3 were used, and the components (D) described in Tables 2 and 3 were produced. The amount other than the compounding amount indicates the amount of the solid component. 〉 Each of the curable compositions obtained in the above examples and comparative examples was applied by a spray coating method (film thickness: 6 μm) onto a PET film having a thickness of 18 8 μm. After drying at 80 ° C for 3 minutes, The high-performance mercury lamp was irradiated with ultraviolet rays at an irradiation dose of 3 〇〇m J / c m2 in the air, and each of the cured films was formed by photohardening. -34- 201229158 <Evaluation of physical properties of the cured film> The following characteristics of the cured film prepared as described above were evaluated. The results obtained are shown in Table 2. (1) Measurement of turbidity (%) The haze (%) of the cured film was measured in accordance with JIS K7 05 using a color haze meter (manufactured by Suga Tester Co., Ltd.) 〇 (2) The measurement of the total light transmittance (Tt; %) was measured using a color turbidimeter (manufactured by Suga Tester Co., Ltd.), and the total light transmittance (%) of the cured film was measured in accordance with JIS K 7 105. (3) Fingerprint The inner surface of the film is blackened and the fingerprint is attached to the surface of the film. Then, it is visually observed from the vertical upper side of the film surface. 'According to the following evaluation criteria (4) ° 〇: Unsightly fingerprint △: Although there is fingerprint, it is not clear X: Clearly see the fingerprint (4) fingerprint The wipe test blackened the inner surface of the film to make the fingerprint adhere to the surface of the film. Then 'wipe the fingerprint with the toilet paper' according to the following evaluation criteria. 〇: wiped off -35- 201229158 △: not easy to wipe off X: can not be wiped off (5) Measurement of contact angle (◦) The contact angle of water and hexadecane of the cured film was measured in accordance with JIS 6768 using a contact angle meter Drop Master 5 00 manufactured by Kyowa Interface Chemical Co., Ltd. -36- 201229158 二云恤 - •31 s 09 0=1 •s o

•D•D

IB οIB ο

O &quot; 9&gt; 01囊权 CT雲w 卜荽港m 9震取 i 的麗m 3麗» iw iel Ϊ3 ·0 2 - sO &quot;9&gt; 01 权 right CT cloud w 荽 荽 m m 9 shock i 丽 m 3 Li » iw iel Ϊ 3 · 0 2 - s

GDI •01 - o ·0 s οGDI •01 - o ·0 s ο

O - &quot; •u - ·- u mu - •u 91 •u 豳齷我胜ae^:: ·0O - &quot; •u - ·- u mu - •u 91 •u 豳龌I win ae^:: ·0

•G •3 s s• G • 3 s s

I •Ql - o ·0 s οI • Ql - o · 0 s ο

O sO s

G ·0 s 09 001 s - o ·0 18 οG ·0 s 09 001 s - o ·0 18 ο

O s 0 •α •3 - 09 =01 •Ql - oO s 0 •α •3 - 09 =01 •Ql - o

G t6 ο o s •3 £ 05 GQl •Ql - o 16 ο o s c ·0 •~ sG t6 ο o s •3 £ 05 GQl •Ql - o 16 ο o s c ·0 •~ s

0QI •Ξ - o 1°5 ο o - 5&gt; ·0 •3 s 09 G°l a o 16 ο o 98 ·0 •3 2 ,u Q2 •01 s o t6 ο o s &quot; 0 ·0 S-M- ·0 ·00QI •Ξ - o 1°5 ο o - 5&gt; ·0 •3 s 09 G°lao 16 ο o 98 ·0 •3 2 ,u Q2 •01 so t6 ο os &quot; 0 ·0 SM- ·0 · 0

S-2I •2 s s OQl 9·2 - o ·0 - ο o s 的&gt; •ζ — υ 7υ 了 υ τυ olo L· —° w —o τυΗ sgsds X3VW3 ooi— s 09 §一 匾蝴h蛾蝴&amp;S-2I •2 ss OQl 9·2 - o ·0 - ο os > ζ υ υ 7υ υ τυ olo L· —° w —o τυΗ sgsds X3VW3 ooi— s 09 §One hh h moth &amp;

磘趣Μ趙职啤胜HK 85¾¾11 雔卜掛趣Me 暖«2蝴 $ •01 - o ·0 18 ο o s &quot;&gt; s + v) /ϋ 鼷陌 (sw® 呶饑¥娜馨 ri镟 % i rt υ (κ&lt;磘 Μ Μ 职 职 职 • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • % i rt υ (κ&lt;

Q -37- 201229158 比較例3 €0 CO 士 ο 1 1 1 1 I 1 1 I 1 1 t *&gt;r CM 1 ur&gt; C-Λ s 1 1 I 1 ο ο CD C3 ! iS9 〇 〇» X κ iA oo tS&gt; V 比較例2 09 I a CO C3 1 1 1 ( 1 1 1 1 l 1 1 C«1 19.S s 1 1 \ ιΛ ο a Q ： ! lX&gt; a&gt; X X oo U9 SX 比較例1 03 1 tn cs CO C3 CO 1 l 1 1 1 1 1 1 l l CA 1 oo 〇» s 1 1 I Ο-Λ ιΛ ο o o 〇 〇 ca X X 却 oo tS9 V 實施例18 22.0 \ CD Ο •«Γ G 1 1 二 1 J i 1 1 1 1 1 1 I lA Cs) a lA 1 1 1 » ο CO ur&gt; C〇J o tn o 09 &lt; &lt;1 un CO V 實施例1? 22.9 1 «0 CD Ο 1 1 1 1 ) J 1 t 1 1 二 1 1 U9 Cs* C3 t t 1 1 ο CO rr Irt 0 ιΛ 〇 σ» &lt;i &lt; ^r oo i/» 實施例16 σ» 1 χΛ Ο CO ο CQ 1 1 1 Cvl i 1 1 1 1 1 1 1 19.8 ! 1 1 1 s 0*4 lA ο 10.6 07 Csl o o o 0 iS9 OO iA V 實施例15 1 α&gt; ο ο &lt;n 1 1 ί 1 1 1 1 1 1 1 1 oo 09 1 I s 1 Cs) Ll? α ◦ CO o ° »s&gt; C3 o ο u» oo tS7 V 寅施例14 ( ιΑ C3 CO CD i 1 1 οό ( ί ) 1 1 ί 1 J 19.8 1 s ) f csl ο CO CD kA 04 0 \£9 C3 a? 〇 ο kO oo xS&gt; V mmmn 19.4 ' CO Ο 1 &lt;s&gt; eg 1 1 Cs» Cs) 1 1 1 1 1 ( 1 1 20.4 〇 1 1 1 eo ο α 10.9 ： ! Q ai o ο lA OO L» V» 實施例12 σ» 1 4Α Ο CO C3 1 1 1 C&lt;4 1 1 1 1 1 1 1 1 19.S 1 s 1 1 t α ο 10.6 ： ! bA 〇 03 o ο \S3 OO V 1 組成(重置份） 二季戊四醇六丙嫌酸酯 季戊四醇三丙烯酸酯 Ir«.184 Irg.m 反應性粒子1 (80n») 反應性粒子2(50rm) ♦Η 1 ο Οϊ 1 υ CQ 1 υ 寸 I υ in I υ to 1 υ 1 o CO 1 υ HC- 7 EMALEX SPE-100S EMELEX SPO-lOO 甲基異丁基酮 丙二醇單甲醚乙酸酯 丙二酵單甲醚 二異丁基酮 ! 乙二醇單丁醚 甲基乙基爾 合計 C/ (A+ B) 固體成分濃度U) 面觀 濁度（％&gt; 全光線透射率（Tt ; %) 指紋看見難易 指紋擦式性 接觸角(水)Γ ) 接觸角(環己烷)Γ ) π 表2及表3中所記載之化合物如下述。 反應性粒子1 :製造例2中合成之反應性粒子1 ( E c ) 反應性粒子2 :製造例3中合成之反應性粒子2 ( E c ) 二季戊四醇六丙烯酸酯：日本化藥股份有限公司製造Q -37- 201229158 Comparative Example 3 €0 CO 士ο 1 1 1 1 I 1 1 I 1 1 t *&gt;r CM 1 ur&gt; C-Λ s 1 1 I 1 ο ο CD C3 ! iS9 〇〇» X κ iA oo tS&gt; V Comparative Example 2 09 I a CO C3 1 1 1 ( 1 1 1 1 l 1 1 C«1 19.S s 1 1 \ ιΛ ο a Q : ! lX&gt;a&gt; XX oo U9 SX Comparison Example 1 0 1 1 1 1 1 1 1 1 1 1 Γ G 1 1 2 1 J i 1 1 1 1 1 1 I lA Cs) a lA 1 1 1 » ο CO ur> C〇J o tn o 09 &lt;1 un CO V Example 1? 22.9 1 « 0 CD Ο 1 1 1 1 ) J 1 t 1 1 2 1 1 U9 Cs* C3 tt 1 1 ο CO rr Irt 0 ιΛ 〇σ» &lt;i &lt; ^r oo i/» Example 16 σ» 1 χΛ Ο CO ο CQ 1 1 1 Cvl i 1 1 1 1 1 1 1 19.8 ! 1 1 1 s 0*4 lA ο 10.6 07 Csl ooo 0 iS9 OO iA V Example 15 1 α&gt; ο ο &lt;n 1 1 ί 1 1 1 1 1 1 1 1 oo 09 1 I s 1 Cs) Ll? α ◦ CO o ° »s&gt; C3 o ο u» oo tS7 V 寅 Example 14 ( ιΑ C3 CO CD i 1 1 οό ( ί ) 1 1 ί 1 J 19.8 1 s ) f csl ο CO CD kA 04 0 \£9 C3 a? 〇ο kO oo xS&gt; V mmmn 19.4 'CO Ο 1 &lt;s&gt; eg 1 1 Cs» Cs) 1 1 1 1 1 ( 1 1 20.4 〇1 1 1 eo ο α 10.9 : ! Q ai o ο lA OO L» V » Example 12 σ» 1 4Α Ο CO C3 1 1 1 C&lt;4 1 1 1 1 1 1 1 1 19.S 1 s 1 1 t α ο 10.6 : ! bA 〇03 o ο \S3 OO V 1 Composition ( Reset parts) Dipentaerythritol hexa-propyl decanoate pentaerythritol triacrylate Ir«.184 Irg.m Reactive particle 1 (80n») Reactive particle 2 (50rm) ♦Η 1 ο Οϊ 1 υ CQ 1 υ inch I υ In I υ to 1 υ 1 o CO 1 υ HC- 7 EMALEX SPE-100S EMELEX SPO-lOO Methyl isobutyl ketone propylene glycol monomethyl ether acetate propylene glycol monomethyl ether diisobutyl ketone! Monobutyl ether methyl ethyl group total C / (A + B) Solid content concentration U) Apparent turbidity (% > total light transmittance (Tt; %) Fingerprint seeing difficult fingerprint rubbing contact angle (water)Γ Contact angle (cyclohexane) Γ) π The compounds described in Table 2 and Table 3 are as follows. Reactive particle 1 : Reactive particle 1 ( E c ) synthesized in Production Example 2 Reactive particle 2 : Reactive particle 2 ( E c ) synthesized in Production Example 3 Dipentaerythritol hexaacrylate: Nippon Kayaku Co., Ltd. Manufacturing

，KAYARAD DPHA -38- 201229158,KAYARAD DPHA -38- 201229158

季戊四醇三丙烯酸酯：新中村化學股分有限公司製， NK ESTER A-TMM-3LM-NPentaerythritol triacrylate: manufactured by Xinzhongcun Chemical Co., Ltd., NK ESTER A-TMM-3LM-N

Irg. 184 : BASF公司製造，光聚合起始劑 Irg. 907: BASF公司製造，光聚合起始劑 成分（C)之各化合物係以合成例1〜7合成 EMALEX SPE-100S ：日本Emulsion公司製造，椰子脂 肪酸山梨糖醇酐酯，HLB9 EMALEX SPO-100:日本Emulsion公司製造，單油酸 〇 山梨糖醇酐酯，HLB9 由表2及表3之結果，了解實施例之硬化膜之透明性、 指紋辨識性、指紋擦拭性之任一種均優異。 相對於此，HLB爲9之比較例1〜3之指紋辨識性、指紋 擦拭性均不良。 [產業上之可能利用性] 本發明之組成物可提供指紋辨識性、指紋擦拭性優異 ^ ，同時具有高透明性之硬化膜。 本發明之組成物可使用作爲適合噴霧塗佈之硬塗形成 用硬化性組成物。 使本發明之組成物硬化而成之硬化膜之指紋辨識性或 指紋擦拭性優異，耐刮傷性、耐乾熱性、耐濕熱性優異， 進而具有高的透明性，故作爲觸控面板、薄膜型液晶元件 、塑膠容器、建築內裝材之地板材、壁材、人工大理石、 玻璃板等防止損傷（刮傷）或防止污染用之保護塗覆材尤 其有用。 -39-Irg. 184: Photopolymerization initiator Irg. 907: manufactured by BASF Corporation, each compound of photopolymerization initiator component (C), synthesized by Synthetic Examples 1 to 7 EMALEX SPE-100S: manufactured by Japan Emulsion Co., Ltd. , coconut fatty acid sorbitan ester, HLB9 EMALEX SPO-100: manufactured by Japan Emulsion Co., Ltd., sorbitan monooleate, HLB9 The results of Table 2 and Table 3, to understand the transparency of the cured film of the example, Both fingerprint recognition and fingerprint wiping are excellent. On the other hand, in Comparative Examples 1 to 3 in which the HLB was 9, the fingerprint visibility and the fingerprint wiping property were both poor. [Industrial Applicability] The composition of the present invention can provide a cured film having high fingerprint visibility and excellent fingerprint wiping property and high transparency. The composition of the present invention can be used as a curable composition for hard coating formation suitable for spray coating. The cured film obtained by curing the composition of the present invention is excellent in fingerprint visibility or fingerprint wiping property, and is excellent in scratch resistance, dry heat resistance, and moist heat resistance, and further has high transparency, so that it is used as a touch panel or a film type. Protective coating materials for preventing damage (scratching) or preventing contamination, such as liquid crystal elements, plastic containers, flooring materials for building interior materials, wall materials, artificial marble, and glass plates, are particularly useful. -39-

Claims (1)

201229158 七、申請專利範圍： 1. 一種硬塗層之形成方法，其包含： 於基材上噴霧塗佈含有下述成分（A) ~(D)之硬化 性組成物而形成塗膜之步驟，以及 對前述塗膜照射輻射線而形成硬塗層之步驟： (A) 多官能（甲基）丙烯酸單體， (B) 光聚合起始劑， (C) 由脂肪酸酯所成之HLB爲2~15之具有聚合性反 應性基之非離子性界面活性劑， (D) 有機溶劑。 2. 如申請專利範圍第1項之硬塗層之形成方法，其中 前述成分（C)具有直鏈狀或分支狀之碳數6~3〇之一價或 二價烴基。 3. 如申請專利範圍第1或2項之硬塗層之形成方法，其 中前述成分（C)之調配量相對於前述（A)成分及前述（ B )成分之合計100重量份，爲超過10重量份且1〇〇重量份 以下。 4 ·如申請專利範圍第1或2項之硬塗層之形成方法’其 中前述成分（C)之HLB爲2〜4。 5 . —種噴霧塗佈用硬化性組成物，其係含有下述成分 (A )〜（D )： (A) 多官能（甲基）丙烯酸單體， (B) 光聚合起始劑， (C) 由脂肪酸酯所成之HLB爲2〜15之具有聚合性反 -40- 201229158 應性基之非離子性界面活性劑， (D)有機溶劑。 6. 如申請專利範圍第5項之噴霧塗佈用硬化性組成物 ，其中前述成分（C)具有直鏈狀或分支狀之碳數6~3 0之 一價或二價烴基。 7. 如申請專利範圍第5或6項之噴霧塗佈用硬化性組成 物，其中前述成分（C)之調配量相對於前述（A)成分及 0 前述（B)成分之合計100重量份，爲超過10重量份且100 重量份以下。 8. 如申請專利範圍第5或6項之噴霧塗佈用硬化性組成 物，其中前述成分（C)之HLB爲2〜4。 9 ·如申請專利範圍第5或6項之噴霧塗佈用硬化性組成 物，其係進而含有（E )數平均粒徑1〜200nm之無機氧化 物粒子。 1 0.如申請專利範圍第9項之噴霧塗佈用硬化性組成物 Q ，其中前述成分（E)具有聚合性不飽和基。 -41 - 201229158 四、指定代表圖： (一） 本案指定代表圖為：無 (二） 本代表圖之元件符號簡單說明：無 201229158 五、本案若有化學式時，請揭示最能顯示發明特徵的化學 式：無201229158 VII. Patent Application Range: 1. A method for forming a hard coat layer, comprising: a step of spray-coating a curable composition containing the following components (A) to (D) on a substrate to form a coating film, And a step of irradiating the coating film with radiation to form a hard coat layer: (A) a polyfunctional (meth)acrylic monomer, (B) a photopolymerization initiator, (C) an HLB of a fatty acid ester 2 to 15 nonionic surfactant having a polymerizable reactive group, (D) an organic solvent. 2. The method for forming a hard coat layer according to the first aspect of the invention, wherein the component (C) has a linear or branched carbon number of 6 to 3 Å or a divalent hydrocarbon group. 3. The method for forming a hard coat layer according to the first or second aspect of the invention, wherein the amount of the component (C) is more than 10 based on 100 parts by weight of the total of the component (A) and the component (B). Parts by weight and 1 part by weight or less. 4. The method of forming a hard coat layer according to claim 1 or 2 wherein the component (C) has an HLB of 2 to 4. A curable composition for spray coating comprising the following components (A) to (D): (A) a polyfunctional (meth)acrylic monomer, and (B) a photopolymerization initiator; C) A nonionic surfactant having a polymerizable anti-40-201229158-based HLB of 2 to 15 and a (D) organic solvent. 6. The curable composition for spray coating according to claim 5, wherein the component (C) has a linear or branched carbon number of 6 to 30 or a divalent hydrocarbon group. 7. The curable composition for spray coating according to claim 5, wherein the amount of the component (C) is 100 parts by weight based on the total of the component (A) and the component (B). It is more than 10 parts by weight and 100 parts by weight or less. 8. The curable composition for spray coating according to claim 5 or 6, wherein the component (C) has an HLB of 2 to 4. 9. The curable composition for spray coating according to claim 5 or 6, further comprising (E) inorganic oxide particles having an average number of particles of from 1 to 200 nm. The curable composition Q for spray coating according to claim 9, wherein the component (E) has a polymerizable unsaturated group. -41 - 201229158 IV. Designated representative map: (1) The representative representative of the case is: No (2) The symbol of the representative figure is simple: No 201229158 V. If there is a chemical formula in this case, please reveal the best indication of the characteristics of the invention. Chemical formula: none
TW100141810A 2010-11-17 2011-11-16 The formation of hard coatings TWI506100B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2010257341A JP5589791B2 (en) 2010-11-17 2010-11-17 Method for forming hard coat layer

Publications (2)

Publication Number Publication Date
TW201229158A true TW201229158A (en) 2012-07-16
TWI506100B TWI506100B (en) 2015-11-01

Family

ID=46269660

Family Applications (1)

Application Number Title Priority Date Filing Date
TW100141810A TWI506100B (en) 2010-11-17 2011-11-16 The formation of hard coatings

Country Status (4)

Country Link
JP (1) JP5589791B2 (en)
KR (1) KR101804761B1 (en)
CN (1) CN102555387B (en)
TW (1) TWI506100B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI572485B (en) * 2016-01-05 2017-03-01 shu-lin Zhao A Method for Making Contact Coating of Fingerprint Identification Module

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5850631B2 (en) * 2011-04-05 2016-02-03 大阪有機化学工業株式会社 Fingerprint disappearance material
CN104755562B (en) * 2012-06-19 2017-05-17 3M创新有限公司 Additive comprising low surface energy group and hydroxyl groups and coating compositions
EP2861678B1 (en) 2012-06-19 2017-10-11 3M Innovative Properties Company Coating compositions comprising polymerizable non-ionic surfactant exhibiting reduced fingerprint visibility
CN107207639A (en) * 2015-09-24 2017-09-26 Jsr株式会社 Emulsion compositions and its manufacture method and layered product and its manufacture method
EP3432070A4 (en) * 2016-03-16 2019-09-25 Toyobo Co., Ltd. Water-developable photosensitive resin composition for flexographic printing, and photosensitive resin original plate for flexographic printing obtained from same
CN106957599A (en) * 2017-04-01 2017-07-18 江苏俊视光学有限公司 A kind of resin lens coating formula and preparation method

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4216031B2 (en) 2002-09-24 2009-01-28 リンテック株式会社 Hard coat film for touch panel or display
JP4508635B2 (en) * 2003-12-26 2010-07-21 リンテック株式会社 Hard coat film for image display device
JP5136224B2 (en) * 2008-06-03 2013-02-06 Ｊｓｒ株式会社 Coating composition for spray coating
JP5020913B2 (en) * 2008-09-19 2012-09-05 リンテック株式会社 Hard coat film for touch panel or display
JP5316092B2 (en) * 2008-09-26 2013-10-16 東洋インキＳｃホールディングス株式会社 Active energy ray-curable composition

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI572485B (en) * 2016-01-05 2017-03-01 shu-lin Zhao A Method for Making Contact Coating of Fingerprint Identification Module

Also Published As

Publication number Publication date
CN102555387B (en) 2015-06-24
CN102555387A (en) 2012-07-11
KR20120053470A (en) 2012-05-25
JP2012106186A (en) 2012-06-07
KR101804761B1 (en) 2017-12-05
JP5589791B2 (en) 2014-09-17
TWI506100B (en) 2015-11-01

Similar Documents

Publication Publication Date Title
TWI457372B (en) Polydialkylsiloxanes having alkyl poly silicon oxide, perfluoropolyether group, a urethane group and a (meth) Bing Xixi the group containing the curable composition and its cured film
JP4273362B1 (en) Hard coat film
TWI506100B (en) The formation of hard coatings
JP5218127B2 (en) Curable composition, cured film and laminate
TWI266773B (en) Resin composition comprising particles
JP2001200023A (en) Curable composition, its cured product and laminate
JP4872248B2 (en) Curable composition and cured film thereof
JP5098741B2 (en) Hard coat forming curable composition, cured film and laminate
TWI424020B (en) Hardened composition and laminated film
JP5594476B2 (en) Laminated body, touch panel and composition
TWI363764B (en)
JP2001302943A (en) Reactive particle, curable composition containing the same, and cured item obtained therefrom
TWI389991B (en) Curable composition, cured layer, and laminate
JP2000281863A (en) Resin composition and its cured material
TWI306885B (en) Curable composition and cured film thereof
CN102463723B (en) Laminated film
JP2008081575A (en) Curable composition, cured film and laminated form
JP5136224B2 (en) Coating composition for spray coating
JP2013237772A (en) Curable composition for spray coating and forming method of cured film
JP2012197331A (en) Curable composition, laminate and method for producing cured film