TW201200555A - Inorganic particle dispersion, energy-ray curing resin composition and film - Google Patents

Inorganic particle dispersion, energy-ray curing resin composition and film Download PDF

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Publication number
TW201200555A
TW201200555A TW100109915A TW100109915A TW201200555A TW 201200555 A TW201200555 A TW 201200555A TW 100109915 A TW100109915 A TW 100109915A TW 100109915 A TW100109915 A TW 100109915A TW 201200555 A TW201200555 A TW 201200555A
Authority
TW
Taiwan
Prior art keywords
meth
group
dispersion
film
resin
Prior art date
Application number
TW100109915A
Other languages
Chinese (zh)
Other versions
TWI500679B (en
Inventor
Ryou Minakuchi
Masao Yamada
Hisayoshi Arai
Youichi Tanimoto
Hideyuki Ishida
Hiroyuki Tereda
Original Assignee
Dainippon Ink & Chemicals
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Application filed by Dainippon Ink & Chemicals filed Critical Dainippon Ink & Chemicals
Publication of TW201200555A publication Critical patent/TW201200555A/en
Application granted granted Critical
Publication of TWI500679B publication Critical patent/TWI500679B/en

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Classifications

    • 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
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • 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
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • 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
    • C08J2300/00—Characterised by the use of unspecified polymers
    • 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
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2433/14—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Dispersion Chemistry (AREA)
  • Materials Engineering (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Paints Or Removers (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Epoxy Resins (AREA)

Abstract

This application provides an inorganic particle dispersion, an energy-ray curing resin composition and a film of the cured composition. The dispersion with high hardness and superior dispersion stability is characterized in that, in a dispersion formed by dispersing inorganic particles (A) which have been subject to a surface treatment into a reactive dispersing agent, (1) the surface-treated inorganic particles (A) are obtained by performing the surface treatment to inorganic particles (C) via using compound (B) having a (meth)acryloyl group; (2) the reactive dispersing agent is a reaction product formed either by performing an addition reaction of a monomer having a (meth)acryloyl group and a corboxyl group with a (meth)acrylic polymer having an epoxy group, or by performing an addition reaction of a monomer having a (meth)acryloyl group and an epoxy group with a (meth)acrylic polymer having a carboxyl group, wherein the reaction product has a (meth)acryloyl group equivalent of 200-600 and a hydroxyl value of 90-280 mg/KOH.

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201200555 六、發明說明： 【發明所屬之技術領域】 本發明關於一種將經表面處理的無機粒子（A)分散在反應性 分散劑中所形成的分散體，並進一步關於該分散體的製造方法、 含有該分散體的硬化性樹脂組合物，以及使該組合物硬化所得的 膜。 、【先前技術】 為了使活性能量射線硬化性樹脂組合物硬化所得之硬化塗膜 的硬度提升，有將二氧化矽微粒分散在活性能量射線硬化性樹脂 組合物中的方法。二氧化石夕微粒中有以濕式法所製造的膠體二氧 化石夕、以^式法所製造的氣相二氧切。在二氧化雜粒的表面 上具有石夕醇基，且一氧化石夕微粒是親水性的。因此，盥作為活性 線硬化型賴、絲轉組合齡之絲分^機相的親 ^差。此外’二氧化石夕微粒的比重比有機相大。因此，使二氧 量射線硬化性樹脂組合物巾長 合Ϊ，甚ΐ二:Ϊ二^化石夕微粒的活性能量射線硬化性樹脂組 貯存穩’貞—氧切微粒會發生凝集和沉降等，其 子(pri^ / ϋ之外’二氧化石夕微粒通常會因作用於初級粒 =^^partlde)間的分子間力和靜電 這對於貯存穩定性也產生了不良影響。 強U的凝集 的方法所得的二氣化欲與物户π π寻利又獻1甲所記載 油性染料擦紐的各項 二ϋ财、^紋擦除性、 先前技術文獻 貝仁疋/又有明確的硬化物硬度。 的方法㈣文獻）。然而，利用專利文獻ί中所記載 專利文獻 201200555 專利文獻1 :日本特開2006—348196號公報 【發明内容】 [發明所欲解決的問題] 本發明有鑑於上述背景技術而提供—種硬化 分散穩定性優異的分散體。此外，本發_課題還=== 該特性之分散體的製造方法。 〜、有 [解決問題之方式] 體 本案發明人為解決上述問題努力研究的結果發 對於解決上述問題極為有效，並由此完成本發明， 刀欢 劑者m係經表面處理的無機粒子（/)分散在反應性分散 1)經表面處理的無機粒子（A)是藉由以具有（甲其） 的化合物⑻對無機粒子（⑷進行表面處有理；^)，丙婦酿基 ϋ應性f散劑是使具有（曱基）丙烯酸基和雜的單體與呈有 丙烯酸聚合物進行加成反應而得之反應生成物 或使具有（曱基）Θ烯醯基和環氧基的單體與具有錄的 合物進行加成反應而得之反應生成物，i (甲基）丙土) 酿基备I為200〜600，羥基值為90〜280mg/K〇H。 八與J7 d發供種分散體’係將經表面處理的無機粒子（A) 刀政在反應性分散劑中之分散體中，其特徵為 理1 無機粒子（A)，是藉由以具有（曱基）丙稀醯基 的化合物⑻對無機粒子（bl)進行表面處理而得者， 有Λ應是使具有（甲基〕丙烯醯基和絲的單體與具 物，或二右r 丙湘1^聚合物進行加成反應而得之反應生成 或使八有（甲基）丙烯絲和環氧基的單體與具有絲的（甲 =丙烯酸聚合物進行加成反應而得之反應生成物，且（曱基） 稀酿基當莖為200〜6〇〇 ’羥基值為9〇〜28〇mg/K〇H。 此外’、本發明提供—種分散體的製造方法，其特徵在於在由 下所構成的濕式攪拌球研磨機中：圓筒型定子、設置於定子一 201200555 端的漿料供給口、設置於定子另— 子内填充的介質和由供給的出σ、f拌混合定 Ϊ離ii轉，或與轉子各自獨立且旋轉，並藉 離哭.將刀矣離田、毁料’將漿料從排出口排出的葉輪型分 t = 八Μ =的域奸（Α)和反舰分侧的漿料， ====== 分錢錢性分散劑 会且人ϊ外佳if提供含有上述分散體的能量射線硬化性樹脂 [;;=^_硬_ _硬條，以及膜。 於該===編魏她細，錢可以用 【實施方式】 (實施發明的形態） 即，本發明關於 1.-種分散體’係絲面處理的域粒子⑷分散在反應性 劑者，其特徵為： 1)經表面處理的無機粒子（A)是藉由以具有（甲基）丙婦酿基 的化合物（B)對無機粒子（bi)進行表面處理而得者， 反應性分散劑是使具有（曱基）丙烯醯基和羧基的單體與具有 裱氧基的（甲基）丙烯酸聚合物進行加成反應而得之反應生成物， 或使具有（甲基）丙烯醯基和環氧基的單體與具有羧基的（甲基） 丙烯酸聚合物進行加成反應而得之反應生成物，且（甲基）丙烯 酿基當量為200〜600，羥基值為90〜280mg/KOH。 2·如1之分散體，其中，該反應性分散劑的（甲基）丙烯醯基當量 為200〜400 ’經基值為140〜280mg/KOH。 3.如1或2之分散體’其中’該反應性分散劑是使（甲基）丙烯酸， 201200555 與使（甲基）丙烯酸縮水甘油g旨聚合所得的 丙烯酸聚合物進行加成反應而得。 *樣暴的（甲基） 4.如1〜3中任-項之分散體，其中，該反應性 分子量為5娜〜1〇()，_。 均 分散體，其中’該無機粒子（bl)的初級粒 =Γ。5中任一項之分散體，其中，該無機粒子⑻為二氧化 7.如卜6性—項之分散體，其中，該具 化合是以通式⑴所表示的有機石夕^^ ORi R2〇—Si—(CH2)n—O 〇R3 (CH3) (1) 〜6 &l)Rl、R2、R3各自獨立’為碳數為1〜4的烧基，n為1 物。冑巾任㉟之分散體的能量射線硬化性樹脂組合 機⑶製 =二於定子另」=出 以及與排出口連接，並與轉給，料的轉子、 輪§=?力作用分離介質與;; 其特徵為：將含有如1〜7 了介質的定子’並在該定子内進行漿料中 201200555 及分散至分散劑後，從該漿料中分離介質。 10.如9之分散體的製造方法’其中該介質是粒徑為15〜1〇〇μιη的 氧化錯微粒。 U·—種能量射線硬化性樹脂組合物’其特徵在於含有以9的製造 方法而得的分散體。 12.種膜’其特徵在於在膜狀基材上具有使如8或η之該能量射 線硬化性樹脂組合物硬化而得的硬化層。 如12的膜，其中，該膜狀基材是選自聚對苯二甲酸乙二醇酯樹 月曰的膜狀基材、聚碳旨樹脂賴狀紐和乙醯化_ 膜狀基材中的一種以上的膜狀基材。 H^1。3的膜’其中該硬化層的膜厚相對於膜狀基材的膜厚 散在賊為：將經表面處理的無機粒子（A)分 的化具有藉由含有（甲基）丙稀酿基 化合i%) 口要’且這種具有（甲基）丙稀酿基的 二;:的表面上導入具有(，丙稀酿基的== 子從與無機粒 的有機魏化合物。 号應例如·具有（甲基）丙稀醯基 gjt來說’紐為狀⑴卿之化合物， 广 R2〇 一 φ—~(CH2)r 〇R3 —〇V (CH3) 0) 1〜6的整數。） 各自獨立地為碳數為1〜4的烧基，η為 在無機粒子（bl)的砉；u 表面上’必須具有和含有（甲基）丙烯 201200555 醯基的化合物（B)形成化學鍵的基團，例如，在使 粒作為無機粒子⑻日夺，石夕醇基可以用作形成化= =成化學鍵的反應條件’可岐慣關反應條件，而為了促 應，也可以使用觸媒。所使用的觸媒並無限制，例如：磷酸酷。 無機粒子（bl)沒有特別限定，可以是二氧化石夕微粒 ，微粒、氧化織粒、氧化雜粒、氧化鈦錄、姐酸鎖微粒 等能夠藉由有機矽烧化合物進行表面處理的無機粒子，尤其二 化矽微粒為佳。這些微粒的較佳初級粒徑，例如1〇〜3〇〇nm的範 圍。若為10nm以下，則分散體中的無機粒子的分散度不充分，= 若為300nm以上，則無法保持硬化膜的足夠強度，並不理想。 、本發明的反應性分散劑所具有的（甲基）丙烯醯基當^較佳 為200〜400。且’經基當量較佳為140〜280。 在本發明中，反應性分散劑是指在活性能量射線下進行聚合 反應的反應性分散劑。（甲基）丙烯醯基當量是指相當於每丨莫^ (甲基）丙烯醯基（丙烯醯基或甲基丙稀醯基）之反應性分散 的固體成分重量（g/eq)。 為了方便起見， 說明。 如下該對本發明的反應性分散劑進行簡述且 反應性分散劑，例如：使具有（曱基）丙烯醯基和羧基的單 體（M)與具有環氧基的（甲基）丙烯酸聚合物（al)進行加成 反應而得之反應性分散劑（A1)，或使具有（甲基）丙烯醯基和環 ，基的單體（b2)與具有羧基的（曱基）丙烯酸聚合物（u)進 行加成反應而得之反應性分散劑（A2)，本發明的反應性分散劑， 可以是（A1)和（A2)的任一種。 用於調製該反應性分散劑（A1)的（曱基）丙烯酸系聚合物 jal )’例如，可以藉由具有（甲基）丙烯醯基和環氧基的聚合性 單體，及視需要與其他聚合性單體的共聚反應而得。 該具有（甲基）丙烯醯基和環氧基的聚合性單體，例如：（甲 基）丙烯酸縮水甘油酯、α—乙基（甲基）丙烯酸縮水甘油酯、α —正丙基（甲基）丙烯酸縮水甘油醋、α—正丁基（甲基）丙烯酸 201200555 縮：?'”旨、（曱基）丙稀酸―3,4—環氧基丁酉旨、.（甲基）丙烯酸 (甲S|、（甲基）丙婦酸—6,7 —環氧基戊酷、α-乙基 (:=氧3=二—/Λ缩水甘油基（甲基) 用4—I袁氧基環己醋、乙稀基環氧環己燒等。這ϋ 以早獨使用，也可以將2種以上並用。 在調整（甲基）丙稀酸聚合物（al)時，且 ⑽合性單_制量通㈣“二。 ?為為二=他=r成分，其使用二 據需要的其鱗合性單_共肢應而得到Γ㈣β早體與根 具有（甲基）丙烯醯基和羧基的聚合性單體 仁 稀醯氧基乙基鄰本一甲酸酉旨、2—丙稀·酿惫其7 | Ϊίί鄰酯以及此等的内酯改質物等具有酯鍵的ΐ飽ΐ ，馬來W。這些_可以單獨使用，也可以將2種以1 在調整（甲基）丙烯酸聚合物（a2)時，具 絲和縣的聚合性單體的朗量通常為25〜⑽ ^ 僖 Ϊί二，重❶4量份。，其他聚合財體為任意成分，其二量^ 节马υ 75重量份，且較佳為〇〜60重量份。 里、 在调製（甲基）丙烯酸聚合物（al)和（甲 物㈤時根據需要進行共聚的其他聚合2烯酉夂“ 以下的聚合性單體等。不飽和早體，例如： 心」1匕甲基）丙烯酸曱醋、（甲基）丙烯酸乙醋、（甲美、而 ϋϊ 1(甲基）丙稀酸正丁醋、（甲基）丙烯酸第三丁醋土、（甲 基）丙湘_旨、（甲基）丙烯酸癸醋、（甲基）丙烯酸辛十知二2 201200555 @曰、（曱基）丙烯酸十四院基醋、（甲基）丙烯酸十六院基自旨、 基）丙烯酸硬脂酯、（甲基）丙烯酸十八烷基酯、（曱基"）丙 一十一烷基酯等具有碳原子數為1〜22的烷基的（甲基）丙嫌萨 酯類； π < (2) (曱基）丙烯酸環己g旨、（甲基）丙烯酸異范酯、（甲基 丙烯酸二環戊酯、（曱基）丙烯酸二環戊烯基氧乙酯等具有脂 烷基的（甲基）丙烯酸酯類； 、 u (3) (甲基）丙烯酸苯曱醯氧乙酯、（甲基）丙烯酸苄酯、（甲 基）丙烯酸苯乙酯、（甲基）丙烯酸苯氧乙酯、（甲基）丙烯酸苯 氧基二乙二醇酯、（甲基）丙烯酸2 —羥基_3_苯氧基丙酯等具有 芳香環的（曱基）丙烯酸酯類； 〃 (4) (甲基）丙稀酸每乙酯，（甲基）丙婦酸經丙g旨、（甲基） 丙烯酸羥丁酯、（曱基）丙烯酸甘油酯；内酯改質（甲基）丙烯酸 ，乙醋、（甲基）丙烯酸聚乙二醇g旨、（曱基）丙烯酸聚丙二醇醋 等具有聚烯烴基二醇基(Polyalkyienegiycoi)的（曱基）丙烯酸酯之 具有羥烷基的丙烯酸酯類； (5) 苜馬酸二曱酯、富馬酸二乙酯、富馬酸二丁酯、衣康酸 一曱酯、衣康酸二丁酯、富馬酸甲乙酯、富馬酸甲丁酯、衣康酸 曱乙酯等不飽和二敌酸酯類； (6) 苯乙烯、α—甲基苯乙烯、氯苯乙烯等苯乙烯衍生物類； (7) 丁二烯、異戊二烯、戊二烯、二曱基丁二烯等二烯系化 合物類； (8) 氣乙烯、溴乙烯等鹵化乙烯和偏鹵化乙烯類； (9) 甲基乙婦基g同、丁基乙稀基g同等不飽和酮類； (10) 乙酸乙烯醋、丁酸乙烯醋等乙稀基醋類； (11) 甲基乙烯基醚、丁基乙烯基醚等乙烯基醚類； (12) 丙烯腈、甲基丙烯腈、偏氰乙烯等氮化乙烯類； (13) 丙烯醯胺及其醇酸取代醯胺類； (14) N—苯基馬來醯亞胺、N一環己基馬來醯亞胺等]^—取 代馬來醯亞胺類； 11 201200555 (15)氟化乙烯、偏氟乙烯、三氟乙 氟乙浠、五氟丙烯或六敦丙烯等含忿 ，細、五氣乙基三a乙稀細或七氟丙基三 二八氟戊基(甲基)丙馳旨，，“Η) 酸醋等（全）氟烧基的破原子數為i至18的（ ^ = 丙烯酸酯類等含氟乙烯性不飽和單體類. J鼠沉暴C曱基） 的(⑵二=醒氧丙㈣氧基魏等含有魏㈣ (17) NN—二甲基胺基乙基（曱基）丙稀酸醋、NN— 基=基乙基（曱基）丙烯酸醋或N，N—二乙基胺基丙芙 丙烯酸醋等^ί-二烧基胺基炫基（甲基）丙稀酸|等' 土） 在調製這些（曱基）丙稀酸聚合物（al) ，物⑷時所用的其他聚合性不飽和單體，可 也可以將2種以上並用。 早倒便用 該（曱基）丙烯酸聚合物⑷和（a2)， 的方法進行聚合(共聚)即可，其共聚合 聚合方法可以使賴體聚合法、溶液聚合法、 ^外^ 聚合法等公知的聚合方法。 〜來CT法礼化 此處，溶液聚合等中可以使用的溶劑，若 例如：确、曱基乙細、甲基正丙基酮、甲基显m ϊ:基酮、甲基異丁基酮、曱基正戊基_、甲i:己i酮、二： 基酮、乙基正丁基酮、二正丙基ϋ!、二異丁基_ 酮等酮系溶劑； 衣已钔佛爾 乙越、異丙細、正丁基趟、二異戊基鱗、乙二醇 乙一醇二乙基醚、二乙二醇二甲基醚、二乙二醇、二氧六二四 12 201200555 氫咳喃等醚系溶劑； ^酸^旨、甲酸觸、甲酸正丁，、乙酸乙，、乙酸正丙醋、 『:以旨η丁酯、乙酸正戊酯、乙二醇單曱基醚乙酸酯、 乙一醇早乙基鱗乙㈣、二乙二醇單曱基醚乙酸自旨、二乙 、丙二醇單曱基喊乙酸醋、乙基—3_乙氧基義 曱醇、^醇、異丙醇、正丁醇、異丁醇、二丙明醇、3 基―1 —丙醇、3—甲氧基―1-丁醇、3-甲基-3-曱氧基丁醇等 醇系溶劑； Τ^Ί 甲笨、一曱笨、S〇lvesso 1〇〇、s〇lvess〇 15〇、8·ζ〇1 工細、 'IS〇Par E'Is0par G'Exxon NaPhtha 5 ^' Exxon Naphtha 说雜系溶劑。這些溶劑可以單獨使用，也可以將2種以上並 用，而為了有效進行作為第二階段反應的具有環氧基的（甲基） 聚，（al)和具有羧基的單體（Μ)的反應，或具有羧 土的（了土）丙烯酸系單體（公）和具有環氧基的單體的 f應二較，為在l〇〇〜150°c的高溫下進行反應，因此從馳點考 f 佳為，用溶劑沸點為置。以上的溶劑，且更佳為使用沸點 為100〜150 C的溶劑。 此外，上述觸媒，可以使用作為自由基聚合起始劑而公知者， 例如.2，^—偶氮二異丁腈、2,2，—偶氮二_ (2,4 —二甲基戊腈）、 氮二—（4—甲氧基―2,4 —二甲基戊腈）等偶氮化合物； if化，甲醯、過氧化月桂酿、第三丁基過氧化·_旨、第三 =亡=化乙基己酸g旨、u’ —二—（第三丁基過氧化）環己烧、 第二戍基過氧化-2-乙基己酸醋、第三己基過氧化—2—乙基己 酸酯等有機過氧化物以及過氧化氫等。 在使用過氧化物作為觸媒時，也可以將過氧化物與還原劑一 起使用，作為氧化還原型起始劑。 性分散劑（A1) ’是使如前述之具有環氧基的（曱基）丙 稀^聚。物⑷與具有（甲基）丙雜基和雜的單體（bl) 進订反應而得。具有（甲基）丙烯醯基和麟的單體（bl)，例如： 13 201200555 (曱基）丙烯酸；β-缓基乙基（甲基）丙稀酸§旨、2 基乙基_酸醋、2—丙烯醯氧基乙基鄰苯二曱酸g旨、2—兩 氧基乙基六氫化鄰苯二甲酸酯以及它們的㈣改質 鍵 的不餘和單紐；馬練等。 具有酉曰鍵 ^，單體（bl)也可以使用：使_酸酐或馬來酸針等酸 季戊四醇二丙烯_旨等含抛基的多官能（甲基 單體反應後’製成含有幾基的多官能（甲基）丙稀酸醋單體的者。 這些具有（甲基）丙烯和羧基的單體⑽可 用，也可以將2種以上並用。 曰早侧便 -八聚與賴（Μ)的反應，通常是藉由將兩種成分 的使用量，只要是使所得的（A1)的（甲基）丙稀酿基當（施) ，駿有制岐，通常祕為使單體（Μ)中^ 莫耳數，相對1莫耳的環氧基，為0.4〜u莫耳。 反應性分散劑（A2)，可以藉由使如前述的具有羧基的 (32)與具有(甲基)丙烯醯基和環氧基的單體(G) ^丁反應i而仔。具有（甲基）丙烯醯基和環氧基的單體㈤），例 甲基）丙烯酸縮水甘油g旨、α—乙美（曱基）丙職缩水甘 油西曰、《 —正丙基（甲基）丙烯酸縮水甘油酯、α—正丁基 縮f甘油Λ旨、（甲基）丙職—3,4 —環氧基丁酯、（^)) 其^Vt環氧基戊醋、（甲基）丙烯酸—6,7—環氧基戊醋、α )丙婦酸—6,7_環氧基戊酯、卜甲基縮水甘油基（甲 ί、石陡^日、（甲基）丙烯酸―3,4—環氧基環己酯、内酯改質（甲 田4—環氧基環己醋、乙稀基環氧環己烧等。這些單 體了以早獨使用，也可以將2種以上並用。 、、曰人聚*合Λ(&2)與單體（bl)的反應，通常是藉由將兩種成分 =田旦口…至80〜12〇°C左右而進行的。聚合物（al )和單體（bl ) /置，只要是使所得的（A1)的（甲基）丙烯醯基當量為200 I曾’就沒有特別限定，通常較佳為使單體（bl)中的環氧 土莫耳數，相對1莫耳的羧基，為〇 4〜U莫耳。 201200555 丙稀當聚合物(ai)與具有(甲基) 酸聚與具有（㈤丙的 的反應，也可以藉由例如下述方法進行魏基的早體（b2) 並在H1二用溶液聚合法聚合（甲基）丙埽酸聚合物⑷， 具有（甲基）丙烯醯基和麟的單體⑻以 ^ ίίΓ/吏用溶液聚合法聚合（甲基）丙稀酸聚合物⑽， 的方口法:有（甲基）丙烯縣和環氧基的單體⑽以進行反應 此外，本發明的反應性分散劑較佳為：以每i分子中且右一 2聚=不飽和雙鍵的單體聚合所得的結構作為主骨架的 Ί 以上合，不會產生凝膠化的範圍内，也可以並用具有兩個 以上4合性不餘和雙鍵的單體。 =述’本發明的反應性分散劑（A1)[藉由使具有環氧基的 丙稀酸聚合物⑷與具有（甲基）丙烯醯基和致基的 =體（M)進行反應所得的聚合物]，較佳為使含有（甲基）丙 =水甘油_聚合性單體聚合所得之含有環氧基的丙烯酸系 5物與（曱基）丙烯酸反應所得的丙烯酸系聚合物。 、作為該含有環氧基的丙烯酸聚合物（al)的環氧當量，較佳 J 140〜500g/eq，且更佳為140〜300g/eq。此外，作為含有環 基的丙婦酸聚合物（al)的玻璃轉移溫度，較佳為如它以〈 更佳為30〜l〇〇°C。 另外’在本發明中，環氧當量是以JIS — K—7236所定義的值。 本發明中的重直平均分子里和數量平均分子量的測定是使用 膠過濾管柱層析（GPC)，並根據下述條件而求出的。 測定裝置；東曹股份有限公司製HLC—8220 柱 ;東曹股份有限公司製保護柱Hxl—Η +東曹股份有限公司製TSKgel G5000Hxl +東曹股份有限公司製TSKgel G4000H& 15 201200555 +東曹股份有限公司製TSKgel G3000Hxl +東曹股份有限公司製TSKgel G2000Hja 檢測器；RI (差示折射計）201200555 6. OBJECTS OF THE INVENTION: TECHNICAL FIELD The present invention relates to a dispersion formed by dispersing surface-treated inorganic particles (A) in a reactive dispersant, and further relates to a method for producing the dispersion, A curable resin composition containing the dispersion, and a film obtained by curing the composition. [Prior Art] In order to increase the hardness of the cured coating film obtained by curing the active energy ray-curable resin composition, there is a method of dispersing cerium oxide fine particles in the active energy ray-curable resin composition. Among the silica dioxide particles, there are colloidal silica produced by a wet method, and gas phase dioxotomy produced by the method. There is an anthraquinone group on the surface of the oxidized particles, and the cerium oxide particles are hydrophilic. Therefore, 盥 is used as the affinity of the active-line-hardening type, the silk-to-wire combination age. In addition, the specific gravity of the dioxide dioxide particles is larger than that of the organic phase. Therefore, the dioxi-ray ray-curable resin composition is long and sturdy, and the active energy ray-curable resin group of the bismuth bismuth oxide particles is stably stored, and the argon-oxygen-cutting particles are agglomerated and settled. The intermolecular force and static electricity between the pri^ / ' 'the dioxide dioxide particles usually act on the primary particles = ^^partlde) also have an adverse effect on the storage stability. The method of agglomeration of strong U is obtained by the method of agglomeration of the two gases, and the π π 寻 寻 又 又 又 又 油 油 油 油 油 油 油 油 油 油 油 油 油 油 油 油 油 油 油 油 油 油 油 油 油 油 油 油 油 油Has a clear hardened hardness. Method (4) literature). However, the patent document 201200555 is disclosed in the patent document: Patent Document 1: JP-A-2006-348196 SUMMARY OF INVENTION [Problems to be Solved by the Invention] The present invention provides a hardening and dispersion stabilization in view of the above background art. Excellent dispersion. Further, the present invention has a method of producing a dispersion of the characteristics. ~, there is [the way to solve the problem] The inventor of the present invention has worked hard to solve the above problems, and the result of the research has been extremely effective in solving the above problems, and thereby completing the present invention, the knife-inducing agent m is a surface-treated inorganic particle (/) Dispersed in Reactive Dispersion 1) Surface-treated inorganic particles (A) are obtained by reacting the inorganic particles ((4) with a compound (8) having ((a)); a reaction product obtained by subjecting a monomer having a (fluorenyl)acrylic group and a hetero group to an addition reaction with an acrylic polymer or having a monomer having a (fluorenyl) terpene group and an epoxy group The reaction product obtained by the addition reaction of the recorded compound, i (methyl) propyl territate, has a hydroxyl group value of 200 to 600 and a hydroxyl value of 90 to 280 mg/K 〇H. Eight and J7 d hair seed dispersions are the surface treated inorganic particles (A) in the dispersion of the reactive dispersant, characterized by the rational inorganic particles (A), by The (mercapto) acrylonitrile-based compound (8) is obtained by subjecting the inorganic particles (bl) to a surface treatment, and the ruthenium should be a monomer having a (meth)acryl fluorenyl group and a silk, or a second right r The reaction of the addition reaction of the propylene hydride polymer to form or react the monomer having octa(meth) propylene filament and epoxy group with the addition reaction of the silk (meth) polymer The product, and the (indenyl) thinning base is 200 to 6 〇〇 'hydroxyl value of 9 〇 to 28 〇 mg / K 〇 H. Further, the present invention provides a method for producing a dispersion, which is characterized In the wet agitating ball mill composed of the following: a cylindrical stator, a slurry supply port provided at the end of the stator 1201200, a medium filled in the stator, and a mixture of the supplied σ and f. Mixing the Ϊ turn away from the ii, or rotating independently from the rotor, and borrowing to cry. 'The impeller type that discharges the slurry from the discharge port is t = eight Μ = the traitor (Α) and the anti-ship side of the slurry, ====== The money dispersant will be good If the energy ray-curable resin containing the above dispersion is provided [;; = ^ _ hard _ _ hard strip, and the film. In this = = = edited fine, money can be used [embodiment] (implementation of the form of the invention) That is, the present invention relates to a domain-dispersed domain particle (4) dispersed in a reactive agent, which is characterized in that: 1) the surface-treated inorganic particle (A) is obtained by having (methyl) The compound (B) of the propylene-based base is obtained by subjecting the inorganic particles (bi) to a surface treatment, and the reactive dispersant is a monomer having a (fluorenyl) acryloyl group and a carboxyl group (a) a reaction product obtained by an addition reaction of an acrylic polymer, or an addition reaction of a monomer having a (meth)acryl fluorenyl group and an epoxy group with a (meth)acrylic polymer having a carboxyl group; The reaction product has a (meth)acrylic base equivalent of 200 to 600 and a hydroxyl value of 90 to 280 mg/KOH. a liquid, wherein the reactive dispersant has a (meth) acrylonitrile equivalent of from 200 to 400 Å and a base value of from 140 to 280 mg/KOH. 3. A dispersion such as 1 or 2 wherein 'the reactive dispersant It is obtained by addition reaction of (meth)acrylic acid, 201200555 with an acrylic acid polymer obtained by polymerizing glycidol (meth)acrylate. *Mixed (methyl) 4. As in 1 to 3 - The dispersion of the item, wherein the reactive molecular weight is 5 Na~1〇(), a uniform dispersion, wherein the primary particle of the inorganic particle (bl) is a dispersion of any one of the following, wherein The inorganic particle (8) is a dispersion of the same. The compound is a compound represented by the formula (1): ORO R2〇—Si—(CH 2 ) n—O 〇R3 (CH3) (1) 〜6 &l) Rl, R2, and R3 are each independently 'a burning group having a carbon number of 1 to 4, and n is 1 substance. The energy ray-curable resin combination machine (3) of the dispersion of 35 is made up of the second stator and is connected to the discharge port, and is separated from the rotor and the wheel of the material; It is characterized in that a stator containing a medium such as 1 to 7 is placed in the slurry and 201200555 is dispersed in the stator and dispersed to a dispersing agent, and then the medium is separated from the slurry. 10. The method for producing a dispersion according to 9, wherein the medium is an oxidized particle having a particle diameter of 15 to 1 μm. The U-type energy ray curable resin composition' is characterized by containing a dispersion obtained by the production method of 9. 12. Seed film' is characterized in that it has a hardened layer obtained by curing the energy ray curable resin composition such as 8 or η on a film-form substrate. The film of 12, wherein the film-form substrate is a film-form substrate selected from the group consisting of polyethylene terephthalate, and a carbon-based resin-like resin and a film-like substrate. More than one type of film-like substrate. a film of H^1.3, wherein the film thickness of the hardened layer is dispersed relative to the film thickness of the film-form substrate: the surface-treated inorganic particles (A) are classified by having (meth)acrylic acid Brewing base i%) mouth and 'this kind of (meth) acrylic acid-based two;: the surface of the introduction of (, propylene-based == sub- and inorganic particles of organic Wei compound. For example, a compound having a (meth) propyl sulfhydryl group, gjt, is a compound of the formula (1), a broad R2〇-φ-~(CH2)r 〇R3 —〇V (CH3) 0) an integer of 1 to 6 . Each of them is independently a burning group having a carbon number of 1 to 4, and η is a ruthenium of the inorganic particles (bl); the surface of the u must have a chemical bond with the compound (B) containing a (meth) propylene 201200555 fluorenyl group. The group, for example, can be used as the inorganic particle (8), and the alkaloid can be used as a reaction condition for forming a == chemical bond, which can be used as a reaction condition, and a catalyst can also be used for the purpose of promoting the reaction. There is no limit to the catalyst used, for example: phosphoric acid is cool. The inorganic particles (bl) are not particularly limited, and may be inorganic particles which can be surface-treated by an organic calcining compound, such as silica fine particles, fine particles, oxidized woven particles, oxidized particles, titania, and sulphur-locking fine particles. In particular, the bismuth oxide particles are preferred. The preferred primary particle size of these particles is, for example, in the range of 1 〇 to 3 〇〇 nm. When it is 10 nm or less, the dispersion degree of the inorganic particles in the dispersion is insufficient, and if it is 300 nm or more, sufficient strength of the cured film cannot be maintained, which is not preferable. The (meth)acrylonitrile group of the reactive dispersant of the present invention is preferably 200 to 400. Further, the base equivalent is preferably from 140 to 280. In the present invention, the reactive dispersant means a reactive dispersant which undergoes polymerization under an active energy ray. The (meth)acryl oxime equivalent means a weight (g/eq) of a solid component corresponding to the reactive dispersion of each (meth) acrylonitrile group (propylene fluorenyl group or methyl propyl sulfhydryl group). For the sake of convenience, explain. The reactive dispersant of the present invention will be briefly described below and a reactive dispersant such as a monomer (M) having a (fluorenyl) acrylonitrile group and a carboxyl group and a (meth)acrylic polymer having an epoxy group. (al) a reactive dispersant (A1) obtained by an addition reaction, or a monomer (b2) having a (meth) acrylonitrile group and a ring group, and a (fluorenyl) acrylic acid polymer having a carboxyl group ( u) The reactive dispersant (A2) obtained by the addition reaction, and the reactive dispersant of the present invention may be either (A1) or (A2). The (fluorenyl)acrylic polymer jal) for preparing the reactive dispersant (A1) can be, for example, a polymerizable monomer having a (meth)acryl fluorenyl group and an epoxy group, and optionally Copolymerization of other polymerizable monomers. The polymerizable monomer having a (meth) acrylonitrile group and an epoxy group, for example, glycidyl (meth)acrylate, glycidyl α-ethyl (meth)acrylate, α-n-propyl (A) Acrylic glycidol vinegar, α-n-butyl (meth) acrylate 201200555 condensed: ?'", (mercapto) acrylic acid - 3,4-epoxy butyl hydrazine, (meth)acrylic acid ( A S|, (methyl)-propionic acid-6,7-epoxy valerate, α-ethyl (:=oxy 3=di-/ Λglycidyl (methyl) with 4-I alkoxy Cyclohexan vinegar, ethylene epoxicyclohexene, etc. This ϋ can be used alone or in combination of two or more. When adjusting (meth)acrylic acid polymer (al), and (10) commensurate _ Quantitative pass (four) "two. ? For the two = he = r component, which uses the sigmoidal single _ common limb required for the sputum to obtain Γ (4) β early body and root with (meth) propylene sulfhydryl and carboxyl Polymerizable monomer, linoleyloxyethyl ortho-formic acid, 2-propene, yoghurt 7 | Ϊίί o-ester and such lactone modified substances, etc. Come to W. These _ can When used alone, when the (meth)acrylic polymer (a2) is adjusted, the amount of the polymerizable monomer of the silk and county is usually 25 to 10 (10) ^ 僖Ϊ ί 2, and the weight is 4 parts. The other aggregated financial body is an arbitrary component, and the amount thereof is 75 parts by weight, and preferably 〇60 parts by weight. In the preparation of the (meth)acrylic polymer (al) and (a) (5) Other polymerization 2 olefins which are copolymerized as needed "The following polymerizable monomers, etc. Unsaturated precursors, for example: heart" 1 匕 methyl) acrylic vinegar, (meth) acrylate vinegar, (A US, and ϋϊ 1 (methyl) acrylic acid n-butyl vinegar, (meth)acrylic acid terpene vinegar, (methyl) propylene xiang, (meth) acrylate vinegar, (meth) acrylate xin十知二2 201200555 @曰,(曱基)Acrylic 14-yard vinegar, (meth)acrylic acid hexadecane, stearyl acrylate, octadecyl (meth) acrylate, (meth)propensate having an alkyl group having 1 to 22 carbon atoms such as a propylene group; π < (2) (fluorenyl) acrylate ring, (meth) acrylate, (dicyclopentyl methacrylate, dicyclopentenyloxyethyl (meth) acrylate, etc. (meth) acrylates; , u (3) phenyl oxime ethyl (meth) acrylate, benzyl (meth) acrylate, phenethyl (meth) acrylate, phenoxy (meth) acrylate (mercapto) acrylates having an aromatic ring such as ester, phenoxy diethylene glycol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate; 〃 (4) ( Methyl)acrylic acid per ethyl ester, (methyl)propionic acid, hydroxybutyl (meth) acrylate, glyceryl (meth) acrylate; lactone modified (meth) acrylate, B An acrylate having a hydroxyalkyl group of a (meth) acrylate having a polyolefin-based diol group, such as vinegar, (meth)acrylic acid polyethylene glycol g, (mercapto)acrylic polypropylene glycol vinegar; (5) Diterpene fumarate, diethyl fumarate, dibutyl fumarate, monoterpenic acid, dibutyl itaconate, rich Unsaturated dicarboxylic acid esters such as methyl ethyl acrylate, methyl butyl fumarate and lanthanum itaconate; (6) styrene derivatives such as styrene, α-methyl styrene and chlorostyrene; (7) Diene compounds such as butadiene, isoprene, pentadiene and dimercaptobutadiene; (8) halogenated ethylene and vinylidene halides such as ethylene oxide and vinyl bromide; (9) Ethyl ethyl ketone g, butyl vinyl group g equivalent unsaturated ketone; (10) vinyl acetate vinegar, butyric acid vinyl vinegar and other ethylene vinegar; (11) methyl vinyl ether, butyl vinyl Vinyl ethers such as ethers; (12) vinyl nitrides such as acrylonitrile, methacrylonitrile, and vinylidene; (13) acrylamide and its alkyd substituted amides; (14) N-phenyl horses醯iimine, N-cyclohexylmaleimide, etc.]--substituted maleic imines; 11 201200555 (15) fluorinated ethylene, vinylidene fluoride, trifluoroethyl fluoride, pentafluoropropylene or six丙烯, such as propylene, fine, five-gas ethyl tri-ethyl or hexafluoropropyl tri-octafluoropentyl (methyl) propyl, "Η" vinegar, etc. (all) fluoroalkyl The number of broken atoms is i to 18 ( ^ = C Fluorinated ethylenically unsaturated monomers such as acid esters. J (suppressed C thiol) ((2) s = azeoxy propyl (tetra) oxy wei, etc. contains Wei (tetra) (17) NN-dimethylaminoethyl (Mercapto) acrylic acid vinegar, NN-based = ethyl ethyl (fluorenyl) acrylate vinegar or N, N-diethyl propyl acrylate acrylate vinegar, etc. ^ί-dialkylamino thiol (methyl (Acrylic acid), etc. The other polymerizable unsaturated monomers used in the preparation of these (mercapto)acrylic acid polymers (al) and (4) may be used in combination of two or more kinds. The (co-based) acrylic polymer (4) and (a2) may be polymerized (copolymerized) in advance, and the copolymerization polymerization method may be a solution polymerization method, a solution polymerization method, an external polymerization method, or the like. A known polymerization method. ~ Come to CT method, solvent, etc., which can be used in solution polymerization, etc., for example: Exact, mercapto, methyl n-propyl ketone, methyl ketone: methyl ketone, methyl isobutyl ketone , fluorenyl-n-pentyl _, ai: hexanone, ketone, ethyl n-butyl ketone, di-n-propyl hydrazine!, diisobutyl ketone and other ketone solvents; Ethyl, isopropyl, n-butyl fluorene, diisoamyl squam, ethylene glycol ethyl alcohol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol, dioxygen hexafluoride 12 201200555 hydrogen Ether solvent such as cough; ^ acid, formic acid, n-butyl formate, acetic acid, acetic acid, propylene glycol, 『: η butyl ester, n-amyl acetate, ethylene glycol monodecyl ether Acid ester, ethyl alcohol, early ethyl scale ethyl (tetra), diethylene glycol monodecyl ether acetic acid, diethyl, propylene glycol monodecyl acetate, ethyl 3-methoxy ethoxylated alcohol, alcohol, different Alcohols such as propanol, n-butanol, isobutanol, dipropanol, 3-yl-1-propanol, 3-methoxy-1-butanol, 3-methyl-3-decyloxybutanol Solvent; Τ^Ί A stupid, a stupid, S〇lvesso 1〇〇, s〇lvess 15〇, 8. ζ〇1 works fine, 'IS〇Par E'Is0par G'Exxon NaPhtha 5 ^' Exxon Naphtha said heteroaryl solvents. These solvents may be used singly or in combination of two or more kinds, and in order to efficiently carry out the reaction of (meth) poly(ep) having an epoxy group as a second-stage reaction, and (a) having a carboxyl group, Or a monomer having a carboxylate (earth) acrylic monomer (male) and a monomer having an epoxy group are reacted at a high temperature of from 1 150 to 150 ° C, so f is preferred, using the boiling point of the solvent. The above solvent, and more preferably a solvent having a boiling point of 100 to 150 C. Further, the above catalyst can be used as a radical polymerization initiator, for example, 2,^-azobisisobutyronitrile, 2,2,-azobis(2,4-dimethylpenta Azo compound such as nitrile), nitrogen di-(4-methoxy-2,4-dimethylvaleronitrile); if, formazan, peroxidized laurel, tert-butyl peroxide, _ Three = death = ethylhexanoic acid g, u' - di - (t-butyl peroxy) cyclohexene, second mercapto peroxy-2-ethylhexanoic acid vinegar, third hexyl peroxidation - An organic peroxide such as 2-ethylhexanoate or hydrogen peroxide. When a peroxide is used as a catalyst, a peroxide can also be used together with a reducing agent as a redox type initiator. The dispersing agent (A1) ' is a (mercapto) propylene group having an epoxy group as described above. The compound (4) is obtained by a sequential reaction with a (meth)propenyl group and a heterogeneous monomer (bl). Monomer (bl) having (meth) acrylonitrile and lin, for example: 13 201200555 (mercapto) acrylic acid; β-futylethyl (meth) acrylic acid §, 2 base ethyl vinegar 2, propylene methoxyethyl phthalic acid g, 2-dioxyethyl hexahydrophthalate and their (iv) modified bonds and single-joint; Ma Lian and so on. It has a hydrazone bond, and the monomer (bl) can also be used: an acid such as an acid anhydride or a maleic acid needle, pentaerythritol dipropylene, and the like. The monomer having a (meth) propylene and a carboxyl group (10) may be used alone or in combination of two or more kinds. The reaction is usually carried out by using the amount of the two components as long as the obtained (meth) propylene (A1) (meth) propylene base is used as a sputum. ^) Mo content, relative to 1 mol of epoxy group, is 0.4 to u mole. Reactive dispersant (A2) can be obtained by (32) having a carboxyl group as described above and having (methyl) a monomer (G) of an acryloyl group and an epoxy group, and a monomer (5) having a (meth)acryl fluorenyl group and an epoxy group, and a glycidyl group of methyl methacrylate —Beimei (曱基), C, glycerin, —, n-propyl (meth) acrylate, glycidyl, α-n-butyl glycerol, (methyl) propyl -3,4 - butyl butyl acrylate, (^)) ^Vt epoxy pentyl vinegar, (meth)acrylic acid - 6,7 - epoxy pentyl vinegar, α) propyl benzoic acid - 6,7 - epoxy pentane Ester, methyl glycidyl group (methyl, stone steep, Japanese, (meth)acrylic acid - 3,4-epoxycyclohexyl ester, lactone modification (Ada 4-epoxycyclohexanol, ethylene base Epoxy cyclohexane or the like. These monomers may be used alone or in combination of two or more kinds. The reaction between the poly(poly) and the monomer (bl) is usually carried out by The two components = Tiandan mouth ... to 80 ~ 12 ° ° C. Polymer (al) and monomer (bl) / set, as long as the resulting (A1) (meth) propylene oxime The base equivalent is 200 I, which is not particularly limited, and it is usually preferred to make the number of molybdenum molars in the monomer (bl) to be 〇4 to U molar with respect to 1 mol of the carboxyl group. 201200555 Acetylene The polymer (ai) is polymerized with (meth) acid and reacted with ((f)C, and can also be polymerized by H1 dimerization (b2) by, for example, the following method (A) Propionate polymer (4) with (methyl A monomeric method for polymerizing a (meth)acrylic acid polymer (10) by a solution polymerization method using a monomer of acrylonitrile and lanthanum (8): a monomer having (meth)acrylic acid and an epoxy group (10) In addition, the reactive dispersant of the present invention preferably has a structure obtained by polymerizing a monomer having a right-only di-unsaturated double bond per molecule and having a structure as a main skeleton, and does not cause coagulation. In the range of gelation, a monomer having two or more 4-mercapto and double bonds may also be used in combination. The reactive dispersant (A1) of the present invention [by making an acrylic acid having an epoxy group] The polymer obtained by reacting the polymer (4) with the (meth)acrylanyl group and the radical (M) is preferably obtained by polymerizing a (meth)propane=hydrogen glycerol-polymerizable monomer. An acrylic polymer obtained by reacting an epoxy group-containing acrylic material with (mercapto)acrylic acid. The epoxy equivalent of the epoxy group-containing acrylic polymer (al) is preferably J 140 to 500 g/eq, and more preferably 140 to 300 g/eq. Further, as the glass transition temperature of the bupropionic acid polymer (al) having a cyclic group, it is preferably such that it is more preferably 30 to 10 °C. Further, in the present invention, the epoxy equivalent is a value defined by JIS - K-7236. The measurement of the weight average molecular weight and the number average molecular weight in the present invention was carried out by using gel filtration column chromatography (GPC) under the following conditions. Measuring device; HLC-8220 column manufactured by Tosoh Corporation; Txgel G5000Hxl manufactured by Tosoh Corporation + TSKgel G4000Hxl manufactured by Tosoh Corporation TSKgel G3000Hxl from Tosoh Co., Ltd. + TSKgel G2000Hja detector manufactured by Tosoh Corporation; RI (Differential Refractometer)

資料處理；東曹股份有限公司製SC —8010 測定條件；柱溫40°C 溶劑四氫呋喃 流速1.0ml/分鐘 標準 ；聚苯乙烯 試樣；用微濾器對以樹脂固體成分換算為〇·4重量％的 四氫呋喃溶液進行過濾所得的試樣（1〇〇μ1) 本發明的反舰分散_重量平均分子量，從硬化收縮效果 和水平度(leveling)觀點考慮，較佳為5,〇⑻〜1〇 ， 5,000〜50,000。 钩Data processing; SC-8010 measurement conditions prepared by Tosoh Corporation; column temperature 40 ° C solvent tetrahydrofuran flow rate 1.0 ml / min standard; polystyrene sample; using microfilter to convert resin solid content to 〇 · 4 wt% The sample obtained by filtering the tetrahydrofuran solution (1 μμ1) The anti-ship dispersion_weight average molecular weight of the present invention is preferably 5, 〇(8) 〜1 〇 from the viewpoint of hardening shrinkage effect and leveling. 5,000~50,000. hook

[化3][Chemical 3]

通式（1)中， 的伸炫基。η表示1In the general formula (1), the swellable base. η means 1

的整數。具體來說， ° R2為碳原子數為2至4 兒’例如’可以舉例Karenz 201200555 —ΑΟΙ、Karenz—MOI、Karenz—ΒΕΙ (商品名，昭和電工（股） 製），此外還可以舉例如二異氰酸酯化合物與羥基丙烯酸酯的反應 加成物等。在此，二異氰酸酯化合物，可以沒有特別限制地使用 公知物質，例如：曱苯二異氰酸酯、六亞曱基二異氰酸酯、異佛 爾酮二異氰酸酯等。羥基丙烯酸酯，只要是具有羥基和（曱基） 丙烯醯基的化合物，就沒有特別限定，可以使用公知物質，例如： 丙烯酸2 —羥基乙酯、丙烯酸2 —羥基丙酯、丙烯酸4—羥基丁酯、 甘油一丙烯酸g曰、二經曱基丙烧二丙烯酸醋、季戍四醇三丙烯酸 酯、二季戊四醇五丙烯酸酯等。其中，從可以提高交聯密度這方 面考慮，較佳為如Karenz—βει這樣的在一個分子中具有2個以 上（曱基）丙稀酿基的物質。 使具有一個異氰酸酯基和（曱基）丙烯醯基的單體與本發明 的反應性分散劑進行反應的方法沒有特別限定，可以採用公知的 $法。具，來說’例可以在本發明的反應性分散劑中滴加具 有二個異氰_旨基和（曱基）丙烯醯基的單體，並加熱至5〇〜 ;2〇C」更佳為60〜90。。進行反應。另外，反應性分散劑和具有一 個，氰酸喊和（甲基）丙烯醯基的單體的使用量沒有特別限定， 分散躺絲（莫朴具有-個躲_旨基和（曱 ^丙烯醯基的單體的異旨基（莫耳）=1 : α 佳為 1 : 0.1〜1 : 0.7。 性分適當地用作各種無機粒子的反應 iiii。r 列舉乾式二氧化石夕微粒、濕式二氧化 焰中燃燒而“ 藉t四氣化抑氧或氫 =酸:和“t:氧=微r=:反 穩定,。此外’在將該分散體加入到r甲散 酸;化型低聚“活性“ 求凋1活性此I射線硬化性樹脂組合物時， 17 201200555 無機粒子在該活性能量射線硬化性樹脂組合物中也可以長時間地 穩疋分散。由於本發明的反應性分散劑的無機粒子分散性高，因 此杈佳為用作將在組合物中分散性穩定性差的無機粒子進行分散 時的反應性分散劑。此外，本發明的反應性分散劑，較佳為用作 在將無機粒子分散在具有（曱基）丙烯醯基的化合物中時所使用 的反應性分散劑。 本發明的反應性分散劑較佳為作為平均初級粒徑為1〇nm〜 =0nm的無機粒子的反應性分散劑使用，更佳為作為平均初級粒 徑為10nm〜200nm的無機粒子的反應性分散劑使用。 使用本發明的反應性分散劑，可以調製將無機粒子分散所形 成的反應性分散體。反應性分散體中各成分的含量沒有特別限 制，但較佳為以[(反應性分散劑）：（無機粒子）]為1〇〜9〇重量 份：90〜1〇重量份，且更佳為30〜9〇重量份：7〇〜1〇重量份的 比例含有本發明的反應性分散劑和二氧化矽微粒。此外，本發明 的分散體中的反應性分散劑和二氧化矽微粒的合計含有率，^固 體成分換算較佳為1〜50重量％，更佳為1〜3〇重量％。 在製造反應性分散體時，藉由含有本發明的反應性分散劑、 無機粒子和該反應性分散劑以外之具有（甲基）丙烯醯基的化合 物，可以製成能量射線硬化性樹脂組合物。該反應性分散劑以外 之具有（甲基）丙烯醯基的化合物，例如：活性能量射線硬化型 單體或活性能量射線硬化型低聚物等。各成分的含量沒有特別限 制，但較佳為以[(反應性分散劑）：（活性能量射線硬化型單體或 活性能量射線硬化型低聚物）]為10〜90重量份：9〇〜10重量份' 更佳為30〜90重量份：70〜10重量份的比例含有本發明的^性 分散劑和活性能量射線硬化型單體或活性能量射線硬化型^聚 物。 一 該活性能量射線硬化型單體，例如，除了在本發明的反應性 分散劑的調製中可以使用的該聚合性單體等之外，例如：乙:醇 二（曱基）丙烯酸酯、丙二醇二（曱基）丙烯酸酯；二乙二醇二 (曱基）丙烯酸酉旨、二乙一醇二（甲基）丙烯酸酉旨、四乙二醇二 18 201200555 (甲基）丙婦酸酯、聚乙二醇二（甲基）丙烯酸酯、 二丙二醇二（曱基）丙烯酸醋、三丙二醇二 Ϊ: Γ3丙ί醇ί (t 烯酸醋、聚丙二醇二（甲基)丙二 -，丁一醇一（甲基）丙烯酸酯、1，4—丁二醇二（甲美）雨 „旨、1>6—六亞甲基二醇二（甲基）丙烯酸酯、…壬：醇二 新作亡薛丙旨、、新ΐ二醇二（曱基）㈣酸醋、絲新戊酸 新戍一κ甲基）丙烯酸g旨、在祕新戊酸新戊二醇上加成己 „的化合物的二（甲基）丙烯酸酯、新戊二醇己二酸酯 一 C T基）丙稀酸酯、 一三經曱基秘、雙三m曱基诚、季細醇、二季戊四醇、 四輕曱基及在這些化合物上加成卜如莫耳的環氧烧炉 (alkylene oxide)所形成的含羥基化合物等具有3個以上經基的化^ 物與3分子以上（甲基）丙烯酸形成酯鍵所得到的化合物等。 該活性能量射線硬化型低聚物，例如：選自本發^的反應性 分散劑以外之丙烯醯基（曱基）丙烯酸酯、胺基曱酸酯（甲基)丙烯 酸酯、酯（曱基）丙烯酸酯、環氧（曱基）丙烯酸醋等中的一種 以上的（曱基）丙烯酸酯化合物。 胺基甲酸酯（甲基)丙烯酸酯，例如：使異氰酸酯化合物與含有 羥基的（曱基）丙烯酸酯化合物反應所形成的多官能胺基曱酸醋（甲 基)丙稀酸S曰。此處所用的異氮酸g旨化合物，例如：六亞甲基二異 亂酸醋、異佛爾S同二異氰酸醋、二曱苯二異氰酸醋、氫化二曱笨 一異氰》酸s曰、一$衣己基曱烧二異亂酸醋、降伯藤二異氮酸醋等脂 肪族或脂環式二異氰酸醋化合物；曱苯二異氰酸g旨、4,4，一二苯基 曱烷二異氰酸酯等芳香族二異氰酸酯；作為二異氰酸醋化合物^ 聚物的異氰脲緩醋型異氰酸S旨預聚合物等。此外，在製造該多官 能胺基曱酸酯（曱基)丙烯酸酯時，也可以用2元〜4元醇或多元醇 化合物對與異氰酸酯化合物反應的含經基的（曱基）丙烯酸酿化 合物的一部分進行置換而進行聚合。 此外，酯丙烯酸酯，可以列舉使選自乙二醇、丙二醇、二乙 二醇、新戊二醇、雙酚A、氫化雙酚A、乙氧基化雙酚a、乙氧 201200555 基化氫化物A、丙祕化鑛a、丙化故 — =上的多7G醇中的—種以上’與選自以鄰 $ ，、對苯二甲_、己二酸、四氫化鄰苯二?二、=: 代表的多元酸中的一種以上I;醋四酸酐等為 元醇，並進-步對細旨多元基的酉旨多 多官能酯（甲基）丙烯酸酯等。 ^曰化所形成的 聚丙二醇、新戊二醇、經基新戊酸新戊二醇四、、 物上，加成(甲Α基等Γ丙以環氧基化合 了基丙烧、甘油等三元醇進行環氧化 t「 (甲基）丙烯酸所得的具有平均3個以上自力^ 甲基）丙_旨化合物；在使縮水甘 個方香_多元紛或其環氧燒煙（alkylene敗 ，所得的環氧化合物上加成（甲基） g 脂等多官能芳香族環氧丙稀酸自旨==ΐϊί -的氫化型的多官能脂環式環氧丙烯_旨；在進 步用分子中存在的2級羥基和二显教酸酯介人 =進行胺基曱酸g旨化後，使殘留的單個末“_ :口曱基)丙賴進行反應所得的胺基‘ 中別具有平均3姐X上自由基聚合性不餘和雙鍵之、 Ϊ 胺基曱酸㈣烯㈣，其硬化塗膜的耐磨損性良 h反應性分散體的製造方法沒有_限定，例如用分散介質（有 物1G〜9G重量份與減粒子9g〜ig重量份進 丁稀釋，使反應性》散劑和二氧化錢粒的合計濃度為U重 20 201200555 量％’並使關械裝置進行分散的方法，其巾，該反應The integer. Specifically, ° R2 is a carbon number of 2 to 4 'for example', such as Karenz 201200555 - ΑΟΙ, Karenz-MOI, Karenz-ΒΕΙ (trade name, Showa Denko), and A reaction adduct of an isocyanate compound and a hydroxy acrylate. Here, as the diisocyanate compound, a known one can be used without particular limitation, and examples thereof include indane diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate. The hydroxy acrylate is not particularly limited as long as it has a hydroxy group and a (fluorenyl) acryl fluorenyl group, and a known substance such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate or 4-hydroxy butyl acrylate can be used. Ester, glycerol monoacrylic acid g hydrazine, dipyridyl propyl acrylate acrylate, quaternary tetraol triacrylate, dipentaerythritol pentaacrylate, and the like. Among them, from the viewpoint of improving the crosslinking density, a substance having two or more (mercapto) acrylonitrile groups in one molecule such as Karenz-βει is preferable. The method of reacting a monomer having one isocyanate group and (fluorenyl)propenyl group with the reactive dispersant of the present invention is not particularly limited, and a known method can be employed. Having, for example, a monomer having two isocyanate groups and a (fluorenyl) acrylonitrile group may be added dropwise to the reactive dispersant of the present invention and heated to 5 〇 〜 2 〇 C" Good for 60~90. . Carry out the reaction. Further, the amount of the reactive dispersant and the monomer having one, cyanate and (meth)acryl fluorenyl group is not particularly limited, and the dispersing lying wire (Mo Pup has a hiding point and (曱 醯 醯 醯) The radical of the monomer of the radical (mole) = 1: α is preferably 1: 0.1 to 1: 0.7. The fraction is suitably used as the reaction of various inorganic particles iiii. r Lists dry silica dioxide particles, wet type Combustion in a oxidizing flame and "by t four gasification to suppress oxygen or hydrogen = acid: and "t: oxygen = micro r =: anti-stable, in addition to 'add this dispersion to r-distributed acid; low formation When the "active" is used to obtain the activity of the I-ray curable resin composition, 17 201200555 inorganic particles can be stably dispersed in the active energy ray-curable resin composition for a long period of time. Due to the reactive dispersant of the present invention Since the inorganic particles have high dispersibility, they are preferably used as a reactive dispersant when the inorganic particles having poor dispersibility stability in the composition are dispersed. Further, the reactive dispersant of the present invention is preferably used as Dispersing inorganic particles in a compound having a (fluorenyl) acrylonitrile group The reactive dispersant used in the present invention is preferably used as a reactive dispersant of inorganic particles having an average primary particle diameter of from 1 nm to =0 nm, more preferably as an average primary particle diameter. A reactive dispersant of inorganic particles of 10 nm to 200 nm is used. The reactive dispersion formed by dispersing inorganic particles can be prepared by using the reactive dispersant of the present invention. The content of each component in the reactive dispersion is not particularly limited, It is preferably [(reactive dispersant): (inorganic particles)] of 1 〇 to 9 〇 by weight: 90 to 1 〇 by weight, and more preferably 30 to 9 〇 by weight: 7 〇 to 1 〇 by weight The ratio of the content of the reactive dispersant and the cerium oxide microparticles in the dispersion of the present invention is preferably 1 to 50 in terms of the total content of the reactive dispersant and the cerium oxide microparticles in the dispersion of the present invention. More preferably, the weight % is more preferably 1 to 3 % by weight. When the reactive dispersion is produced, it has a (meth)acrylonitrile group other than the reactive dispersant, the inorganic particles and the reactive dispersant of the present invention. compound of The energy ray curable resin composition may be used. The compound having a (meth) acrylonitrile group other than the reactive dispersant may be, for example, an active energy ray-curable monomer or an active energy ray-curable oligomer. The content of the component is not particularly limited, but is preferably [(reactive dispersant): (active energy ray-curable monomer or active energy ray-curable oligomer)] 10 to 90 parts by weight: 9 〇 10 More preferably, the amount of the component is more preferably 30 to 90 parts by weight: 70 to 10 parts by weight, and the active dispersing agent of the present invention and the active energy ray-curable monomer or the active energy ray-curable polymer are contained. The hardening type monomer, for example, in addition to the polymerizable monomer or the like which can be used in the preparation of the reactive dispersant of the present invention, for example: B: alcohol bis(indenyl) acrylate, propylene glycol bis(indenyl) Acrylate; diethylene glycol di(indenyl)acrylic acid, diethylene glycol di(meth)acrylic acid, tetraethylene glycol 2 18 201200555 (methyl) propionate, polyethylene glycol II ( Methyl acrylate , dipropylene glycol di(indenyl)acrylic acid vinegar, tripropylene glycol diterpene: Γ3 propanol ί (t oleic acid vinegar, polypropylene glycol di(methyl) propylene di-, butanol mono(meth) acrylate, 1 , 4-butanediol II (K.) rain „ 、, 1 > 6 hexamethylene glycol di (meth) acrylate, ... 壬: alcohol two new works Xue Xue, red diol (曱) (4) Acidic vinegar, silk pivalic acid, neodymium-kappamethyl)acrylic acid, di(meth) acrylate, neopentyl compound, which is added to pironic acid neopentyl glycol Glycol adipate-CT base) acrylate, triterpene sulfhydryl, bis-trimethyl sulfhydryl, quaternary fine alcohol, dipentaerythritol, tetrasodium fluorenyl and the addition of these compounds to A compound obtained by forming an ester bond between three or more molecules of a hydroxyl group-containing compound such as a hydroxyl group-containing compound formed by an alkylene oxide in an ear and three or more molecules of (meth)acrylic acid. The active energy ray-curable oligomer is, for example, an acryloyl (mercapto) acrylate, an amino phthalate (meth) acrylate, or an ester selected from the reactive dispersants of the present invention. One or more (mercapto) acrylate compounds of acrylate, epoxy (fluorenyl) acrylate vinegar, and the like. The urethane (meth) acrylate is, for example, a polyfunctional amine bismuth citrate (meth) acrylate S 形成 formed by reacting an isocyanate compound with a hydroxy group-containing (fluorenyl) acrylate compound. As used herein, a compound of isochloric acid g, for example, hexamethylene diisophoric acid vinegar, isophor S homo-isocyanuric acid vinegar, diterpene benzene diisocyanate vinegar, hydrogenated diterpene, an isocyanate 》Acid 曰 曰, one 衣 曱 曱 曱 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二An aromatic diisocyanate such as tetraphenylnonane diisocyanate; a prepolymer of isocyanuric slow vinegar type isocyanate as a diisocyanate compound; Further, in the production of the polyfunctional amino decanoate (mercapto) acrylate, a transbasic (fluorenyl) styrene compound which reacts with an isocyanate compound can also be used with a 2 to 4 membered alcohol or a polyol compound. A part of the replacement is carried out for polymerization. Further, the ester acrylate may be exemplified by a hydrogenation selected from the group consisting of ethylene glycol, propylene glycol, diethylene glycol, neopentyl glycol, bisphenol A, hydrogenated bisphenol A, ethoxylated bisphenol a, and ethoxy 201200555. A, a secreted mineral a, a propylation - = more than 7G in the above - and above selected from the neighboring $,, terephthalic acid, adipic acid, tetrahydrophthalic acid? And =: one or more of the polybasic acids represented by the formula I; the tetraacetic anhydride or the like is a diol, and the polyfunctional ester (meth) acrylate or the like which is a polybasic group is further advanced. ^Polypropylene glycol, neopentyl glycol, neopentyl glycol neopentyl glycol formed by deuteration, addition, on-site, addition (methyl indenyl group, etc., epoxide group, propyl group, glycerol, etc.) The triol is subjected to epoxidation of t "(meth)acrylic acid, which has an average of 3 or more self-supporting methyl groups). The compound is used in the reduction of the water. The obtained epoxy compound is added with a polyfunctional aromatic epoxidic acid such as (meth) g-ester, and a hydrogenated polyfunctional alicyclic epoxy propylene having a meaning of ==ΐϊί - in the molecule for progress The presence of the second-order hydroxyl group and the di-scientific acid ester intermediator = after the amino group is subjected to the reaction, the residual amino group obtained by reacting the residual single "-:-mercapto-based" propylene has an average of 3 The radical polymerization property of the sister X and the double bond, Ϊ 胺 曱 曱 四 四 四 四 四 四 , , 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的The weight of 1G~9G of the material is diluted with the 9g~ig parts of the reduced particles to make the total concentration of the reactive powder and the dioxide particles. Method U% by weight 20201200555 'and off mechanically dispersing apparatus, the towel, the reaction

當量為200〜600，經基值為9〇 下，稱為反應性分散劑）。 該有機溶劑，例如：丙酮、甲基乙基酮（MgK)、甲基異丁美 酮（MBK)軸類，四氫α夫喃（THF)、二氧戊環等環狀^類, 乙酸甲醋:乙酸乙_、乙酸丁 g旨等g旨類，甲苯、二f苯等芳香族 類，卡必醇(carbitol)、赛路蘇(cen〇s〇lve)、曱醇、異丙醇、丁醇、 丙二醇單曱基醚等醇類，這些溶劑可以單獨使用或並用，其中， 從塗佈時的揮發性和溶劑回收方面考慮，較佳為作為反應,/生分散 劑的合成溶劑之甲基乙基酮。 機械裝置’例如：分散器、具有渦輪葉片等攪拌葉的分散機、 塗料攪拌器、輥研磨機、球研磨機、磨碎機、砂研磨機、珠粒研 磨機等。在製造反應性分散體時，在將得到的分散體用於塗佈劑 專的情況下，從塗佈性、塗料穩定性和硬化塗膜的透明性等方面 考慮，較佳為利用使用玻璃珠粒、氧化鍅珠粒等分散介質的珠粒 研磨機進行分散。 該珠粒研磨機，例如：Ashizawa.Finetech (股）製造的STAR MILL ;三井礦山（股）製造的 MSC—MILL、SC—MILL、Attritor MA01 SC ;淺田鐵工（股）的 Nano Grain MiU、Pico Grain MiU、 Pure Grain Mill' Mechagaper Grain Mill > Cerapower Grain Mill ' Dual Grain Mill' AD Mill' Twin AD Mill' Basket Mill > Twin Basket Mill，哥工業（股）製造的 Apex Mill、Ultra Apex Mill、 Super Apex Mill 等。 上述Ultra Apex Mill是一種濕式櫈拌球研磨機，其特徵在於 由以下所構成：圓筒型定子、設置於定子一端的漿料（本發明的 21 201200555 反應性分散劑和二氧化^夕微粒的混合物，下同。）供給口、設置 ί定^一端的藥料排出口、攪拌混合定子内填充的介質和二 、，，《二i、、、，。的漿料的轉子、以及與排出口連接，並與轉子形成一體 ’或與轉子各自獨立且旋轉，並藉由離心力侧分離介質 ίΓίϊ中’明動分離11旋轉__心作為與上述排出口 ii 道；a ’使用該濕讀拌球研磨機的分散體的製造 smr供給至填充了介質的定子，並在 後，從該漿料中分離介質的方法。 刀散 行詳ίί明根據關，對使用上述辆磨機的本發贿造方法進 圖1是具備本發明的分散體製造方法中使 =時的供給口的縱剖：使; 式攪拌球研磨機的分離器橫截面的圖。’ °中所不的濕 在圖1中’利用原料泵2從儲在將祖 23中和介質—起擾拌❿粉碎，崎藉二離器?分=^研 ^通過軸5 _順，並沿著細球1的通路，進粉 在漿料中，可以根據需要適當添加右 在漿料巾宜含有錢關。 ’、械_、各錄加劑等。 該有機溶劑的使用量，相對於太恭 化石夕微粒的合計·重量份，較佳性分散劑和二氧 ⑽為150〜500重量份，其中從在 22 201200555 作時_與介⑽分離良好，戏料 .過紅可f在短時間内完成的觀點考慮，較佳為20。〜3。〇重量t 调衣漿料時，較佳為在本發明的反應性分散劑中加入 劑得到反舰分制的有機關溶液後，加人二氧切微粒。’ 片六2種5加劑，例如交聯劑。交聯劑，例如：乙烯基系的石夕 ’元父聯別、ί魏系的石規交聯劑、苯乙烯系时敍聯劑美 丙稀酿氧基系的魏交聯劑、丙烯酿氧基系的魏交聯劑、胺二 糸，魏交聯劑、醯脲系的石夕烧交聯劑、氯丙基系的石夕貌交聯劑土、 疏f系的⑪敍聯劑、硫化物系㈣敍聯劑、異氰酸醋系 烧交聯劑、鋁系的矽烧交聯劑等。 乙烯基系的矽烷交聯劑，例如：乙烯基三氯矽烷、乙烯基三 T氧基石夕烧、乙婦基三乙氧基石規、2— (3,4_環氧環己基）乙基 二甲氧基矽烷、3 —縮水甘油氧基丙基三曱氧基石夕烷、3 —縮水甘 油氧基丙基曱基二乙氧基石夕烷、3 —縮水甘油氧基丙基三乙氧基石夕 烧、對苯乙烯基二甲氧基石夕烧、3—曱基丙烯醯氧丙基甲基二甲氧 基石夕烷、3—曱基丙烯醯氧丙基三曱氧基石夕烷、3_曱基丙烯醯氧 丙基曱基一乙氧基矽烧、3—曱基丙烯醯氧丙基三乙氧基矽烧、3 一丙烯醯氧丙基三甲氧基矽烷、N_2—(胺基乙基）一3_胺基丙 基曱基二甲氧基石夕烧、N—2—(胺基乙基）—3 —胺基丙基三甲氧 基石夕烧、N—2—(胺基乙基）—3 —胺基丙基三乙氧基石夕烷、3_ 胺基丙基三甲氧基矽烷、3 —胺基丙基三乙氧基矽烷、3一三乙氧 基曱矽烷基一N— (1，3 —二曱基.亞丁基）丙基胺、N_苯基—3_ 胺基丙基三曱氧基矽烷、N_ (乙烯基苄基）—2一胺基乙基—3 —胺基丙基三甲氧基石夕烷的鹽酸鹽、特殊胺基矽烷、3_醯脲丙基 二乙氧基石夕烧、3 —氯丙基三曱氧基石夕烧、3 —魏基丙基曱基二甲 氧基石夕燒、3 —巯基丙基三甲氧基石夕烧、二（三乙氧基甲矽烧基丙 基）四硫化物、3 —異氰酸酯基丙基三乙氧基石夕烧、稀丙基三氯石夕 烧、稀丙基三乙氧基石夕烧、婦丙基三甲氧基石夕烧、二乙氧基甲基 乙婦基砍炫、三氯乙嫦基秒烧、乙烯基三氯梦燒、乙稀基三甲氧 基石夕烷、乙烯基三乙氧基矽烷、乙烯基三（2—甲氧基乙氧基）石夕 23 201200555 烷。 環氧系雜交聯劑，例如：..二乙氧基（縮水甘油氧基丙基） 甲基石夕烧、2- (3,4-環氧環己基）乙基三曱氧基石夕烧、3 甘油氧基丙基三甲氧基魏、3-縮水甘吨絲基甲基二乙氧基 石夕烧、3 —縮水甘油氧基丙基三乙氧基石夕燒等。 苯乙烯系石夕烧交聯劑’例如：對苯乙烯基三甲氧基石夕烧等。 曱基丙烯酿氧基系矽烷交聯劑，例如可以舉 氧丙基甲基二甲氧基魏、3—甲基丙烯醯氧丙基!三甲匕=1 3-曱基丙_氧丙基曱基二乙氧基石夕烧、3—甲基丙烯醯氧丙基 二乙氧基矽烧。 石夕^烯醯氧基系械交聯劑，例如：3—丙烯輒丙基三甲氧基 胺基系石夕燒交聯劑，例如：N—2—(胺基乙基）一3_胺美 氧基石夕r烧、N—2—(胺基乙基）—3 —胺基丙基三ΐ氧 ^m、N-2「（胺基乙基）—3—胺基丙基三乙氧基魏、3— 絲丙基三甲氧基魏、3-胺絲基三乙氧基魏 基甲繼—N—二甲基—亞丁基)丙基;-乙二 —胺基丙基三曱氧基矽烷等。 女以本基3 ，腺系碎敍彳n 3—财基三乙氧絲 。 氯丙基系石夕烧交聯劑，例如：3 —氯丙基三甲氧 絲系魏交聯劑’例如：3 —疏基丙基 3-疏基丙基三甲氧基魏等。 T氧基魏 四硫ίΐΐ系魏交聯劑，例如：二（三乙氧基甲魏基丙基） 雜ί氰_系魏交聯劑，例如：3 —異氰_旨基丙基三乙氧基 鋁系交聯劑，例如：乙酿烧氧基紹二異丙醇化物等。 該研磨機3，如圖2詳細所示，以縱向的圓筒 f :具有可通過肋冷卻研磨機的冷卻水之絲6的定子 疋子7的軸心且在定子上部形成能夠旋轉的軸承，同時在轴承 24 201200555 二車由丄t以亡側部的轴心作為中空溢流道9的軸5、 5上iHf向上犬出設置的針狀或圓盤狀轉子n、固定在 ==所二的馬達12的滑輪13以及帶有傳動帶的』 並固定_ 口端_子連接頭15、接近定子内的上部， 、1在軸5上用於介質分離的分離器4、在定子底部盥 端相對設置的原料喈料的徂办σΜ ^隹疋于履冲興軸5的軸 的制4 在設置於定子底部偏心位置 ，二ίίΪ出口 19上所設置的格子狀_支撐物17上所安裝 的，分離介質的篩網18。 m文衣 連接在軸5上存在—定間隔而固定的—對圓盤21和 旋轉而ί的葉片22形成而構成葉輪，且藉由與轴5 一起 到圓盤間的介質和漿料賦予離心力，利用兩者= 排出。使;1質沿技向向外飛出’並使毁料通過軸5軸心的溢流道9 原料漿料的供給口 16，如圖3詳細所示，由在定子底部上带 24、能夠升降地嵌合於閥座24的倒梯形形狀的閥體/ 4疋氐邛向下犬出並形成有原料漿料的導入口 27的有底圓筒體 =及從糊斷迦驗版口 29 28、月:夠升降地喪合於圓筒體％的活塞3卜連接活塞si和;體 25的;f干32、女裝在圓筒體％内的活塞上且在壓下活塞31時 =閥體25賦予向下作用力的彈簧33、和從難體28突出並轉入 桿端部之錄置可機的方式钱的螺帽34#成，若_料製料 的供給而將曝25推上，則在與_ 24之間形成環狀縫隙，由 此原料漿料被供給至研磨機内，但壯述縫義寬度可藉由螺帽 34的轉f、放鬆進行調整，從而可以將該寬度設定為以下寬度： 即使在供給原料時螺帽34碰到圓筒體28而形成最大寬度，介質 .仍不能通過。供給原料時的閥體25，由於送入圓筒體26内的原料 漿料的供給壓，抵抗了研磨機内的壓力及彈簧33的作用而上升， 與閥座24之間形成縫隙，但是原,料漿料的供給壓因原料供給而形 成的縫隙寬度，稍微小於螺帽34所規定的最大缝隙寬度，因此在 螺帽34與圓筒體28之間還有一迪空間。 25 201200555 ，過閥座24和閥體25之間形成的缝隙而被供給至研磨機内 的原料漿料中含有粗粒子，因此可以預料其會夾入閥座和閥體之 間而產生堵塞，且在因夾入而產生堵塞時，通過提高供給壓使閥 體25上升到極限，縫隙寬度達到最大。因此，夾入的粗粒子流出， 堵塞消除。若堵塞消除，則供給壓下降，閥體25落下。 為了消除縫隙處的堵塞，在圖示的例子中，進一步使來自於 圖不中省略的壓縮空氣源的壓縮空氣通過調節器23，經過電磁切 換閥30,由導入口 29供給至圓筒體28内，藉由在較短週期内使 ，磁=換閥30反復進行on—OFF切換，從而斷續地供給壓縮空 氣’藉此，閥體25在較短週期内反復進行上升到上限位置的上下 動作，從而可以消除夾入問題。 田該閥體25的振動可以通常進行，或者可以在原料漿料中含有 大量粗粒子時進行，且在因堵塞而使原料漿料的供給壓上升時， 也可以與其連動進行。 粉碎結束後，將攪拌後的介質與製品漿料一起取出，或在抽 出製。〇漿料後取出時，如圖所示降低螺帽34的安裝位置。將電磁 =閥30切換至0Ν。藉此，以從導入口 29導入的壓縮空氣使閥 體25上升到閥座24的邊緣上。 a在上，實施方式中，轉子η和分離器4均固定在軸5上，但 是在其他實施方式中固定於同軸配置的不同軸上，並分別進行^ 轉驅動。 1丁疋 在轉子和分離器安裝於同軸的上述圖示實施方式中，由於驅 ，裝置有一套即可，因此結構簡單，相對於此，在轉子和分離器 ，震於不_上，用刊的驅動裝置進行旋轉鋪驗—實施^ 式中’可以使轉子和分離器分別以最適合的旋轉數進行旋轉驅動。 圖5所示的球研磨機，其軸43為帶肩軸(shoulder shaft)，且從 接著交替地嵌人隔板45和關狀或針狀的 46然後在軸下端用螺釘48固定塞子47，藉由軸43的肩43a ίί"!47夾住分離器44、隔板45以及轉子46，使其連接固定， ~離5 44㈣6崎’縣汹谢目制表社分卿成葉片嵌 26 201200555 • 合溝51的一對圓盤52、介於兩個圓盤之 合的葉片53、以及使兩個β 嵌合溝51嵌 54連通的孔55的環狀板56組成並有與溢流道 5: ^ ^ ^ ΛΙΓ"Γ；Ϊ： fo^ 面，ϊϊίίίίίΓ务因二氧化石夕微粒破損而產成新的活性表 人ϊΐΐ集的現象。若過分散，則分散液變為膠狀。 由使的填充率’例如為定子内容積的8〇〜_。藉 8〇^9〇〇/°j 所而要的動力最少。即，可以最有效地進行粉碎。 μ 磨機3的定子7内填充介質後，在關閉閥門％％和 ^打^間門61和62的狀態下，首先驅動馬達12，接著驅動 另、=2。藉由驅動前者馬達12的來旋轉驅動轉子η矛口分離器4， f二方面’藉由驅動後者原料泵2以每次-定的量’將原料槽1 ^原料漿料送至供給口 的導入口 π，由此通過在閥座％的 邊緣和閥體25之間形成的狹缝而供給至研磨機内。 驅動馬達12，使轉子U和分離器4旋轉時，旋轉數越大、圓 周^度越大，則所受離心力越大，且介質和二氧化矽微粒撞擊時 的衝擊也越大。使用粒徑為15μιη的介質作為介質時的圓周速度較 另藉由轉子.11的旋轉，攪拌混合研磨機内的漿料和介質，進行 漿料的粉碎，且藉由分離器4的旋轉，利用比重差分離進入分離 27 201200555 器内的介質和漿料，比重較重的 輕的漿料通過在軸5軸心中 的益°1=，出，而比重較 料槽卜 乃训/益机道9排出，並返回至原 返回至原料槽1的m重複進 研磨機的循環，進行粉碎。在進行了一定^^料泵2供給至 當測定漿料的粒度，並在達到所希=度^碎的階段中’適 接著停止馬達12，從而停止研磨^ 3 H夺停止膽泵， 打開閥門58和59，同時關_&和， 馬達12，然後打開閥門6〇。於是，原 $啟動原料泵和 料栗2而抽出，並送至製品槽原的料通過原 的旋轉來授拌研磨機内的製品裝料，一另藉由轉子7 9，或利用由機上部供給至 ^ =和溢流道 和研磨機3中的製品裝料被回收至製品槽幻中十斤于的原枓槽1 —二氧化梦微粒的分散所需的時間，&分散良好 研磨機的循環心 分鐘。 1㈣钱為5〜6G分鐘’且更佳為1〇〜40 時。此外’該循環流量較佳為5〜15L/小時，且更佳為8〜肌/小 另外’在製品回收時，使轉子7旋轉’是藉由混合使 研磨機内^會沉降而不均勻地存在於研磨機下層部位，以防止 網18的師孔堵塞，且為了消除筛孔堵塞，可以由取出卩H 適當的壓縮线或n2氣，從㈣_ 18進行反向沖洗。 .此外·在本發明的製造方法中，可以較佳使用 Ashizawa*Finetech股份有限公司製造的STAR⑽江。該 MILL、，:種介質祕型粉碎裝置，其具備在—端具有漿料入口 的筒狀容H、在該容H内在長度方向上延伸配置之可自由旋轉的 授拌軸、和位於上述容H料並與賴雜連_,轉 述授拌軸具錢拌構件，在上賴拌姉上述容糾表面之間的 28 201200555 用上述驅動裝=上漿料，-邊 授拌轴和上述容3!㈣A述獅軸上軸了將該中空部分與上述 的移動到達的上述空間連通的縫隙，隨著聚料 上述授拌軸和，進行從上述縫隙返回至 内部在上述軸的上述中空部分 出口的筛網，且該筛網被旋部分内部設置有包圍上述漿料 沾*，上述;|質擾拌型粉碎裂置巾，由於用以從漿料中分離介皙 趙=被婦，動，因此到達_断的祕和介質也被誘發旋 因此旋轉運騎產生的離*力對於介質來說高於漿料， 漿料中分離的偏離力。因此，介f不接近_ 而進仃循裱。因而可以有效地從漿料中除去介質。 利用本發明的製造方法所得的分散體，可以藉由與其他化合 物混合而製成活性能量射線硬錄樹脂組合物。這些化&物，; 以列舉上述活性能量射線硬化型單體、活性能量射&硬&型低聚 物、紫外線吸收劑、抗氧劑、矽系添加劑、氟系添加劑、流變性 控製劑、消泡劑、脫模劑、矽烷交聯劑、抗靜電劑、防霧劑、著 色劑等。 該紫外線吸收劑，例如：2 —[4—{ (2—羥基—3 —十二烷基氧 丙基）氧卜2—羥基苯基]—4,6-二（2,4-二甲基苯基）―；^) —二氮雜苯、2 —[4—{ (2 —羥基一3—十三烧基氧丙基）氧} — 2 -羥基苯基]—4,6-二（2,4—二曱基苯基）一1，3,5 —三氮雜苯等三 氮雜苯衍生物、2— (2’一卩山卩星缓基一5’一甲基笨基）苯並三唾、2 —(2’一鄰罐基苄氧基— 5’一曱基苯基）苯並三π坐、2 —卩山卩星缓基 ―4一十二烧氧基二苯甲酮、2—鄰硝基苄氧基—4 —十二烧氧基二 苯曱酮等。 29 201200555 该抗氧劑，例如：受阻酚系抗氧化 有機硫系抗氧化劑 '磷_旨系抗氧化解。 认氧化劑、 ㈣該’例⑹：二曱基聚魏烧、曱基苯基聚石夕氧燒、 狀-m魏院、曱基氫聚魏貌 : 烧共聚物、聚酷改質二甲基聚魏烧縣物、氟 乳烧共聚物、胺級質二曱基料魏共 ^ 的聚有機魏絲。 ⑽n絲或本基 且 如上述的各種添加劑的使用量，考慮觀分發揮i效 在不妨礙紫外線硬化的範圍内，較佳為相對於議重量份 活性能量射線硬化性樹脂組合物，分別為αοι〜ίο ^量份 在本發明的分散體中可以添加的光聚合起始劑，例如：二笨 :ΐη，二甲基—4 ~~甲氧基二苯曱綱、4,4,—雙二甲基胺基二 本曱酮、4,4 -雙二乙基胺基二苯曱酮、4,4，_二氯二苯甲酮、米 氏酮(Michlefsketone)、3,3，，4,4，一四（第三丁基過氧羰基）二笨 酮等二苯曱酮類； 咖星(xanthene)、9_氧硫咖星、2-甲基9-氧硫_星、2—9_氧 硫咖星、2,4—二乙基9-氧硫咖星等卩山卩星（xanthene)、9-氧硫卩山口星 類；安息香(Benzoin)、安息香(Benzoin)甲基醚、安息香(Benz〇in) 乙基鱗、女息香(Benzoin)異丙基驗等偶姻峻類(aCyi〇in ether); 聯苯甲醯(benzil)、雙乙醯等α—二酮類；二硫化四甲基秋蘭 姆(tetramethylthiuram disulfide)、對甲苯二硫化物等硫化物類；4_ 二甲基胺基苯甲酸、4 —二甲基胺基苯甲酸乙酯等苯曱酸類； 3,3’一羰基一雙（7—二乙基胺基）香豆素、〗_羥基環己基苯 基酮、2,2’一二甲氧基一1，2 —二苯基乙燒一 1_酮、2—〒基—1 — [4—(甲硫基）苯基]—2 —味琳代丙烧一i — g同、2—苄基—2 —二 甲基胺基一1— (4 —味琳代苯基）一丁烧—1 —酮、2 —經基—2 — 甲基一1 一苯基丙烷一1 —酮、2,4,6 —三甲基苯曱醯基二苯基氧化 膦、雙（2,4,6 —三甲基苯甲醯基）苯基氧化膦、1 —[4— (2 —羥基 乙氧基）苯基]—2 —經基一2—甲基一1 —丙貌—1 —銅、1_ (4— 201200555The equivalent weight is 200 to 600, and the base value is 9 〇, which is called a reactive dispersant). The organic solvent, for example, acetone, methyl ethyl ketone (MgK), methyl isobutyl ketone (MBK) axis, tetrahydro alpha pentane (THF), dioxolane, etc. Vinegar: acetic acid B, acetic acid butyl g, etc., aromatics such as toluene, di-f-benzene, carbitol, cen〇s〇lve, sterol, isopropanol, An alcohol such as butanol or propylene glycol monodecyl ether. These solvents may be used singly or in combination. Among them, from the viewpoint of volatility at the time of coating and solvent recovery, it is preferably a reaction solvent as a reaction or a dispersant. Ketoethyl ketone. The mechanical device 'for example: a disperser, a disperser having a stirring blade such as a turbine blade, a paint agitator, a roll grinder, a ball grinder, an attritor, a sand grinder, a bead grinder, or the like. In the case of producing a reactive dispersion, when the obtained dispersion is used for a coating agent, it is preferred to use glass beads from the viewpoints of coatability, coating stability, transparency of the cured coating film, and the like. Dispersion is carried out by a bead mill of a dispersion medium such as granules or cerium oxide beads. The bead mill, for example, STAR MILL manufactured by Ashizawa. Finetech Co., Ltd.; MSC-MILL, SC-MILL, Attritor MA01 SC manufactured by Mitsui Mining Co., Ltd.; Nano Grain MiU, Pico of Asada Iron Works Co., Ltd. Grain MiU, Pure Grain Mill' Mechagaper Grain Mill > Cerapower Grain Mill ' Dual Grain Mill' AD Mill' Twin AD Mill' Basket Mill > Twin Basket Mill, Apex Mill, Ultra Apex Mill, Super Apex Mill et al. The above Ultra Apex Mill is a wet bench ball mill characterized by consisting of a cylindrical stator and a slurry disposed at one end of the stator (21 201200555 reactive dispersant of the present invention and oxidized particles) The mixture, the same as below.) Supply port, set the drug discharge port at one end, stir the medium filled in the stator and the second, ", i,,,,. The rotor of the slurry is connected to the discharge port and is integrally formed with the rotor or rotates independently of the rotor, and is separated from the rotor by the centrifugal force side. A method of manufacturing a dispersion using the wet-read ball mill to supply a smr to a stator filled with a medium, and thereafter, separating the medium from the slurry. Fig. 1 is a vertical cross-sectional view of a supply port in a method for producing a dispersion of the present invention, in which the stirring nozzle is used; A diagram of the cross section of the separator of the machine. The humidity in '° is not shown in Fig. 1 'Using the raw material pump 2 to smash from the storage of the ancestors 23 and the medium - the smashing of the smashing, the smashing of the shovel Along the path of the fine ball 1, the powder is poured into the slurry, and it may be appropriately added as needed. ', machinery _, each recording agent, and so on. The amount of the organic solvent to be used is preferably from 150 to 500 parts by weight, based on the total weight of the chlorinated particles, and the amount of the dispersant and the dioxane (10) is from 150 to 100 parts by weight. In the case of a play that is too red to be completed in a short period of time, it is preferably 20. ~3. When the weight of the coating slurry is t, it is preferred to add the oxidant particles after the agent solution of the anti-ship system is added to the reactive dispersant of the present invention. 'Six six kinds of 5 additives, such as cross-linking agent. Cross-linking agent, for example, vinyl-based Shi Xi's parent-child joint, wei-wei stone-based cross-linking agent, styrene-based anti-linking agent, propylene-based oxy-based Wei cross-linking agent, propylene brewing Oxygen-based Wei cross-linking agent, amine dioxime, Wei cross-linking agent, bismuth-urea-based Shishi-burning cross-linking agent, chloropropyl-based Shixi cross-linking agent soil, and s-f-type 11-synthesis agent The sulfide system (4) is a cross-linking agent, an isocyanate-based cross-linking agent, and an aluminum-based antimony-crosslinking agent. Vinyl-based decane cross-linking agent, for example: vinyl trichloromethane, vinyl tri-T-oxide, ethidium triethoxy stone, 2-(3,4-epoxycyclohexyl)ethyl Methoxy decane, 3-glycidoxypropyl trimethoxy oxetane, 3-glycidoxypropyl decyl diethoxy oxane, 3-glycidoxy propyl triethoxy sulphur Burning, p-styryl dimethoxy zephyr, 3-mercapto propylene methoxypropyl methyl dimethoxy oxane, 3-mercapto propylene methoxy propyl trimethoxy oxetane, 3 曱Propylene oxypropyl fluorenyl monoethoxy oxime, 3-mercapto propylene oxypropyl triethoxy oxime, 3- propylene methoxypropyl trimethoxy decane, N 2 - (aminoethyl) a 3-aminopropylmercaptodimethoxycarbazone, N-2-(aminoethyl)-3-aminopropyltrimethoxycarbazide, N-2-(aminoethyl) —3 —Aminopropyltriethoxy oxalate, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3—triethoxydecyl-N—(1 , 3 —dimercapto.butylene) a hydrochloride of N, phenyl-3-ylaminopropyltrimethoxy decane, N-(vinylbenzyl)-2-aminoethyl 3-aminopropyltrimethoxy oxalate, Special amino decane, 3_ guanidinyl propyl diethoxy sulphur, 3 - chloropropyl tributary oxime, 3 - Weipropyl propyl decyl dimethoxy sulphur, 3 - decyl propyl Trimethoxy zephyr, bis(triethoxymethyl sulfonylpropyl) tetrasulfide, 3-isocyanate propyl triethoxy sulphur, propyl trichloride, propyl triethyl Oxygen stone simmering, propyl propyl trimethoxy sulphur, diethoxymethyl ethoxylate, sulphur, sulphur trichloromethane, vinyl trichloromethane, ethylene trimethoxy oxalate, Vinyl triethoxy decane, vinyl tris(2-methoxyethoxy) zea 23 201200555 alkane. An epoxy-based hetero cross-linking agent, for example: diethoxy (glycidoxypropyl) methyl sulphur, 2-(3,4-epoxycyclohexyl)ethyltrimethoxy oxylate, 3 glyceryloxypropyltrimethoxywei, 3-glycidylmethyldiethoxyxanthine, 3-glycidoxypropyltriethoxysulfate, etc. The styrene-based sulfonated cross-linking agent ’, for example, p-styryltrimethoxy zebra or the like. The mercapto propylene-based oxy-decane crosslinking agent may, for example, be oxypropylmethyldimethoxy-wei, 3-methylpropenyloxypropyl!trimethylhydrazine=13-mercaptopropene-oxypropyl hydrazine Bis-ethoxylated sulphur, 3-methylpropenyloxypropyldiethoxy oxime. Shixi ^ ene oxy group mechanical crosslinking agent, for example: 3-propenyl propyl propyl methoxy amine based sulphur cross-linking agent, for example: N-2-(aminoethyl)- 3 -amine Methoxylate shi r, N-2-(aminoethyl)-3-aminopropyltrioxane^m, N-2 "(aminoethyl)-3-aminopropyltriethoxy Kewei, 3-propylpropyltrimethoxywei, 3-aminofilyltriethoxyweiylmethyl-N-dimethyl-butylene)propyl;-ethylenedi-aminopropyltrimethoxyoxydecane Etc. Female base 3, glandular sputum n 3 - hydroxy-triethoxylate. Chloropropyl ketone burn cross-linking agent, for example: 3-chloropropyl trimethicone-based cross-linker For example: 3 - thiopropyl 3- benzyl propyl trimethoxy wei, etc. T oxy Wei tetra thio ruthenium is a cross-linking agent, for example: bis(triethoxymethyl-propyl propyl) _ is a Wei cross-linking agent, for example: 3 - isocyanide - propyl propyl triethoxy aluminum cross-linking agent, for example: E-brewed alkoxy diisopropanolate, etc. The grinder 3, as shown 2 shown in detail, in the longitudinal cylinder f: having the cooling water wire 6 which can cool the grinder by the rib The axis of the sub-tweezer 7 forms a rotatable bearing on the upper part of the stator, and at the same time, the bearing 24 201200555 is driven by the 轴t with the axis of the dead side as the axis 5, 5 of the hollow overflow channel 9 a needle-shaped or disk-shaped rotor n, a pulley 13 fixed to the motor 12 of the == and a belt with a belt and a fixed-head _ sub-connector 15, close to the upper part of the stator, 1 on the shaft 5, the separator 4 for separating the medium, the raw material 相对 相对 相对 相对 相对 在 在 在 在 履 履 履 履 履 履 履 履 履 履 履 履 履 履 履 履 履 履 履 履 履 履 履 履 履 履 履 履 履 履 履 履 履 履 履 履a mesh 18 for separating the medium mounted on the grid-like support 17 provided on the outlet 19. The m-shirt is attached to the shaft 5 and is fixed at intervals - the disc 21 and the rotating blades 22 is formed to form the impeller, and the centrifugal force is imparted by the medium and the slurry together with the shaft 5 to the disc, and both are discharged; the mass is flung out along the technical direction and the debris is passed through the shaft 5 Axial overflow passage 9 The feed port 16 of the raw material slurry, as shown in detail in Fig. 3, is at the bottom of the stator The belt 24, the inverted trapezoidal valve body that can be lifted and fitted to the valve seat 24, the bottomed cylindrical body that is downwardly pulled out and formed with the inlet port 27 of the raw material slurry = and Verification port 29 28, month: enough to fall and fall in the cylinder% of the piston 3 connected to the piston si and; body 25; f dry 32, women on the piston within the cylinder% and under pressure At the time of the piston 31, the spring 33 which gives the downward force to the valve body 25, and the nut 34# which protrudes from the difficult body 28 and is transferred to the end of the rod, can be supplied as a nut material. When the exposure 25 is pushed up, an annular gap is formed between the and the _ 24, whereby the raw material slurry is supplied into the grinder, but the width of the seam can be adjusted by the rotation and relaxation of the nut 34. Thereby, the width can be set to the following width: Even if the nut 34 hits the cylindrical body 28 to form the maximum width when the raw material is supplied, the medium cannot pass. In the valve body 25 when the raw material is supplied, the supply pressure of the raw material slurry fed into the cylindrical body 26 rises against the pressure in the grinder and the action of the spring 33, and a gap is formed between the valve seat 24 and the valve seat 24, but the original The gap width of the supply pressure of the slurry is slightly smaller than the maximum slit width defined by the nut 34, so that there is a space between the nut 34 and the cylindrical body 28. 25 201200555, the raw material slurry supplied to the grinder through the gap formed between the valve seat 24 and the valve body 25 contains coarse particles, so that it is expected to be caught between the valve seat and the valve body to cause clogging, and When clogging occurs due to the pinching, the valve body 25 is raised to the limit by increasing the supply pressure, and the slit width is maximized. Therefore, the coarse particles that are trapped flow out, and the clogging is eliminated. When the clogging is eliminated, the supply pressure is lowered and the valve body 25 is dropped. In order to eliminate the clogging at the slit, in the illustrated example, the compressed air from the compressed air source omitted from the drawing is further passed through the regulator 23, passed through the electromagnetic switching valve 30, and supplied to the cylindrical body 28 through the introduction port 29. By repeating the on-off switching of the magnetic/valve valve 30 in a short period, the compressed air is intermittently supplied, whereby the valve body 25 is repeatedly raised to the upper limit position in a short period. Actions that eliminate the pinch problem. The vibration of the valve body 25 may be carried out normally, or may be carried out when a large amount of coarse particles are contained in the raw material slurry, and may be carried out in conjunction with the increase in the supply pressure of the raw material slurry due to clogging. After the pulverization is completed, the stirred medium is taken out together with the product slurry, or is extracted. When the slurry is taken out, the mounting position of the nut 34 is lowered as shown. Switch the solenoid = valve 30 to 0 Ν. Thereby, the valve body 25 is raised to the edge of the valve seat 24 by the compressed air introduced from the introduction port 29. In the above embodiment, the rotor η and the separator 4 are both fixed to the shaft 5, but in other embodiments, they are fixed to different shafts of the coaxial arrangement and are respectively driven by the rotation. In the above-described illustrated embodiment in which the rotor and the separator are mounted coaxially, since the drive and the device have one set, the structure is simple, and in contrast, the rotor and the separator are not affected. The drive unit performs a rotary test—in the middle of the equation, the rotor and the splitter can be rotationally driven at the most suitable number of revolutions. The ball grinder shown in FIG. 5 has a shaft 43 which is a shoulder shaft, and is then alternately embedded with a partition 45 and a closed or needle-shaped 46 and then the plug 47 is fixed at the lower end of the shaft with a screw 48, The separator 44, the partition plate 45 and the rotor 46 are clamped by the shoulder 43a ίί"! 47 of the shaft 43 to be fixedly connected, and are separated from the 5 44 (four) 6 崎 崎 县 县 县 目 目 目 目 目The pair of discs 52 of the grooving 51, the vanes 53 interposed between the two discs, and the annular plate 56 of the holes 55 that connect the two β-fit grooves 51 to each other 54 and have the overflow passage 5 : ^ ^ ^ ΛΙΓ"Γ;Ϊ: fo^面,ϊϊίίίίΓ The phenomenon of new active episodes due to the breakage of the dioxide particles. If it is excessively dispersed, the dispersion becomes a gel. The filling rate by the ' is, for example, 8 〇 to _ of the inner volume of the stator. The motivation required by 8〇^9〇〇/°j is the least. That is, the pulverization can be performed most efficiently. After the medium 7 of the μ mill 3 is filled with the medium, the motor 12 is first driven in the state where the valves %% and the gates 61 and 62 are closed, and then the other is driven to =2. By driving the former motor 12 to rotationally drive the rotor η spear separator 4, f is 'by driving the latter material pump 2 to send the raw material slurry 1 ^ raw material slurry to the supply port by driving the raw material pump 2 The inlet π is thereby supplied into the grinder through a slit formed between the edge of the valve seat % and the valve body 25. When the motor 12 is driven to rotate the rotor U and the separator 4, the larger the number of revolutions and the larger the circumference, the larger the centrifugal force and the greater the impact when the medium and the ceria particles collide. When the medium having a particle size of 15 μm is used as the medium, the slurry and the medium in the grinding machine are stirred and stirred by the rotation of the rotor 11. The slurry is pulverized, and the specific gravity is utilized by the rotation of the separator 4. The difference is separated into the medium and the slurry in the separation unit 201200555. The lighter weight of the light slurry passes through the shaft in the axis of the shaft 5, and the specific gravity is discharged from the trough, and the specific gravity is discharged. The m returned to the raw material tank 1 is returned to the cycle of the grinder and pulverized. When a certain amount of pump 2 is supplied to measure the particle size of the slurry, and in the stage of reaching the peak degree, the motor 12 is stopped appropriately, thereby stopping the grinding, stopping the bile pump, and opening the valve. 58 and 59, while closing _& and, motor 12, then opening valve 6〇. Then, the original $ start material pump and the chestnut 2 are extracted, and the raw material sent to the product tank is fed by the original rotation to feed the product charge in the grinding machine, and is further supplied by the rotor 7 9 or by the upper part of the machine. The product charge to the ^ = and the overflow channel and the grinder 3 is recovered to the time required for the dispersion of the original gutter 1 - dioxide dioxide particles in the product tank, & Cycle the heart minutes. 1 (four) money is 5 to 6G minutes' and more preferably 1 to 40 minutes. In addition, the circulation flow rate is preferably 5 to 15 L/hour, and more preferably 8 to 8 muscle/small. In addition, when the product is recovered, the rotation of the rotor 7 is caused by mixing so that the inside of the grinding machine will settle unevenly. In the lower part of the grinder, to prevent blockage of the mesh hole of the net 18, and in order to eliminate the clogging of the mesh hole, the reverse rinsing can be performed from (4) _ 18 by taking out a suitable compression line or n2 gas of 卩H. Further, in the production method of the present invention, STAR (10) River manufactured by Ashizawa* Finetech Co., Ltd. can be preferably used. The MILL, a media-type secret pulverizing apparatus, comprising: a cylindrical capacity H having a slurry inlet at the end, a freely rotatable mixing shaft extending in the longitudinal direction of the volume H, and the above-mentioned capacity H material is mixed with Lai _, and the nutrient mixing member is transferred to the mixing shaft. The above-mentioned driving and pressing surface is used in the above-mentioned squeezing and squeezing surface. (4) A gap in the upper shaft of the lion shaft that communicates the hollow portion with the space reached by the above movement, and returns from the slit to the inner hollow portion outlet of the shaft along with the mixing shaft a screen, and the screen is disposed inside the rotating portion to surround the slurry, and the above-mentioned;|mass disturbing type crushing and splitting towel, because it is used to separate the medium from the slurry; The secret and medium of the arrival_break are also induced to rotate. Therefore, the force generated by the rotary ride is higher than the deviation of the slurry and the separation in the slurry for the medium. Therefore, the f is not close to _ and is circulated. It is thus possible to effectively remove the medium from the slurry. The dispersion obtained by the production method of the present invention can be prepared by mixing with other compounds to prepare an active energy ray hard recording resin composition. These chemical & substances, to enumerate the above active energy ray hardening type monomer, active energy radiation & hard & type oligomer, ultraviolet absorber, antioxidant, lanthanide additive, fluorine additive, rheology control Formulations, antifoaming agents, mold release agents, decane crosslinkers, antistatic agents, antifogging agents, colorants, and the like. The ultraviolet absorber is, for example, 2—[4-{(2-hydroxy-3-cyclododecyloxypropyl)oxy-2-hydroxyphenyl]-4,6-di(2,4-dimethyl Phenyl)-;^)-diazabenzene, 2-[4-{(2-hydroxy-3-tridecyloxypropyl)oxy}-2-hydroxyphenyl]-4,6-di a diazabenzene derivative such as 2,4-dimercaptophenyl)-1,3,5-triazabenzene, 2—(2' 卩山卩星缓基基-5'-methylphenyl) Benzotri-salt, 2-(2'-ortho-benzyloxy-5'-mercaptophenyl)benzotriazine, 2-卩山卩星---4-12 alkoxybenzene Methyl ketone, 2-o-nitrobenzyloxy-4-pyroxybenzenedibenzophenone and the like. 29 201200555 The antioxidant, for example, a hindered phenolic antioxidant, an organic sulfur-based antioxidant, 'phosphorus' is an antioxidant solution. The oxidizing agent, (4) the 'Example (6): Diterpene-based poly-Wei-burn, nonylphenyl poly-stone oxy-fire, shape-m Weiyuan, sulfhydryl hydrogen poly-wei: burnt copolymer, poly-modified dimethyl Polyweiweixian, fluorinated emulsion copolymer, amine-grade diterpene base Wei-communication of poly-organic Weisi. (10) The amount of the n-ray or the base and the various additives as described above, in consideration of the fact that the effect is not inhibited by the ultraviolet curing, preferably the active energy ray-curable resin composition is αοι - ίο ^ The photopolymerization initiator which can be added to the dispersion of the present invention, for example: dipheno: ΐη, dimethyl-4~~methoxydibenzoquinone, 4,4,-bis Methylaminodibenzionone, 4,4-diethylaminodibenzophenone, 4,4,-dichlorobenzophenone, Michlefsketone, 3,3,,4, 4, tetraphenyl ketones such as tetrakis (tertiary butylperoxycarbonyl) dimercapone; xanthene, 9-oxythiocarb, 2-methyl 9-oxo-s-star, 2-9 _Oxythiocarbazone, 2,4-diethyl 9-oxothiocaine, etc. xanthene, 9-oxosulfanyl sulphate; Benzoin, Benzoin methyl ether, Benzinin, Benzoin, Benzoin, etc. (aCyi〇in ether); benzil, benzidine, etc. Tetramethylthiuram disu Sulfide such as lfide), p-toluene disulfide, benzoic acid such as 4-dimethylaminobenzoic acid or ethyl 4-dimethylaminobenzoate; 3,3'-carbonyl-double (7-two) Ethylamino) coumarin, _hydroxycyclohexyl phenyl ketone, 2,2'-dimethoxy- 1,2-diphenylethene-1-one, 2-indenyl- 1 - [ 4-(Methylthio)phenyl]-2(-------------- 2-, 2-benzyl- 2-dimethylamino- 1 - (4----- - 1 - ketone, 2 - thiol - 2 - methyl - 1 - phenylpropan-1-one, 2,4,6 -trimethylphenylnonyldiphenylphosphine oxide, double (2,4 ,6-trimethyl benzhydryl)phenylphosphine oxide, 1-[4-(2-hydroxyethoxy)phenyl]-2-trans-yl-2-methyl-1-pyrene-1 Copper, 1_ (4—201200555

異丙基苯基）—2—經盖__ 9田I 基苯基）.經基12基甲2丙f—卜g同、1- (4—十二烧 基二甲基硫化物、22，— 嗣、4—苯甲酿基—4，-甲Isopropyl phenyl)—2—cleared __ 9 field I phenyl). 12-based methyl 2, propyl, propyl, 1-(4-didecyl dimethyl sulfide, 22 , — 嗣, 4—Benyl-based—4,-A

Dim_Ketal)、苯曱美―只氧田基^乙酉同、二甲鮮細(Be_ 甲阶二 L甲基—P—f氧基乙基乙縮經、鄰苯，基苯 α二-H 二甲基胺基苯基）酉同、對三甲基胺基苯乙_、 苯乙酮、戊基—4 —二甲基胺基苯曱酸醋、2 6- 苯練坐琳二聚物、2,4 —雙三氯甲基— t i C乙乳基祕曱基）胺基]笨基—s—三氮雜苯、2,4—雙三 7土，6、（4—乙氧基）苯基_S—三氮雜苯、2,4—雙三氯曱基 μ— (3 —漠—4—乙氧基）苯基—S —三氮雜苯蒽酿*、2—第三丁 基蒽酿；、2—戊基蒽酿、β—氯蒽醒等。 該光聚合起始劑，可以單獨使用，也可以將2種以上组合使 用。其使用量沒有特別限制，但為了保持良好的感度，防止結晶 析出、塗膜物性變差等，較佳為相對於丨⑻重量份活性能量射線 硬化性樹脂組合物使用〇.05〜20重量份，並尤佳為使用〇1〜1〇 重量份。 該光聚合起始劑，選自1 —羥基環己基苯基酮、2 —羥基_2 —甲基一1 一苯基丙烷一1 —酮、1 —[4— (2 —羥基乙氧基）苯基] —2 —羥基一2—甲基一1 —丙烷—1 —酮、9_氧硫咖星及9-氧硫咄 口星衍生物、2,2’_二曱氧基一1，2 —二苯基乙烧—1 —酮、2,4,6—三 曱基苯曱醯基二苯基氧化膦、雙（2,4,6 —三曱基苯曱醯基）苯基 氧化膦、2—曱基一1 —[4—(曱硫基）苯基]一2 —味琳代—1 —丙 酮'2—苄基一2—二曱基胺基_1— (4 —B末琳代苯基）—丁烷—1 —酮中的1種或2種以上的混合系，因為可得到硬化性高之塗佈 用活性能量射線硬化型樹脂組合物，尤佳。 該光聚合起始劑的市售品，例如：Irgacure—184、Irgacure— 149、Irgacure—261、Irg 贫 cure—369、Irgacure—500、Irgacure—651、 Irgacure —754、Irgacure —784、Irgacure—819、Irgacure —907、 Irgacure —1116、Irgacure —1664、Irgacure —1700、Irgacure —1800、 Irgacure—1850、Irgacure—2959、Irgacure—4043、Darocur—1173 31 201200555 (汽巴精化公司製）、Lucirin TPO (BASF公司製）、KAYACURE -DETX > KAYACURE - MBP' KAYACURE - DMBI' KAYACURE —EPA、KAYACURE —OA[日本化藥（股）製]、VICURE—10、 VICURE— 55 ( STAUPFER—有限公司製）、TRIGONALP1 ( AKZO 有限公司製）、SANDORY 1000 ( SANDOZ有限公司製）、DEAP (APJOHN 有限公司製）、QUANTACURE — PDO、 QUANTACURE - ITX > QUANTACURE - EPD ( WARD BLEKINSOP有限公司製）等。 進一步’在活性能量射線硬化性樹脂組合物中，還可以將各 種光敏劑與上述光聚合起始劑並用。光敏劑，例如：胺類、脲類、 含硫化合物、含磷化合物、含氣化合物或腈類或其他含氮化合物 等。 此外，為了改善對膜基材的黏接性等，活性能量射線硬化性 樹脂組合物還可以並用其他樹脂。 /該其他樹脂，例如：甲基丙烯酸曱酯樹脂、曱基丙烯酸甲酯 f共聚物等丙烯酸樹脂；聚苯乙婦、曱基㈣酸曱g旨—苯乙稀系 蓉樹聚胺醋樹脂；聚丁二烯或丁二烯-丙烯腈系 化性繼獅能量射線硬 基材進行塗佈，即，在對膜基材等薄膜塑膠 曲（捲曲）較小。且，因’且硬化時為低收縮，膜的翹 在哕可以適用於膜基材的塗佈。 基材上，塗i使乾^臭塗^夺曰的=量，例如2’較佳為在各種膜 2蛛2。此外為0•卜30-2,且較佳為1〜 臈，由於容易達到作^硬塗膜= 基材的膜厚為3%以上的 硬化，更佳為 硬化層的獏厚相對於膜 為3〜100%的膜’又更佳為 為硬化層的膜厚相對於膜臈厚為5〜腦的膜，並特別佳 、、狀基材的膜厚為5〜50%的膜。 32 201200555Dim_Ketal), benzoquinone-oxygen-only base^Ethyl phthalate, dimethyl fresh (Be_ A-order L-methyl-P-f oxyethyl condensate, o-benzene, phenyl benzene α-H dimethyl Aminophenyl phenyl) bis, p-trimethylaminophenyl benzene, acetophenone, pentyl-4-dimethylamino benzoic acid vinegar, 2 6- benzoparin dimer, 2 ,4-bis-trichloromethyl-ti C-ethyl thiol-based amide group; amino group] stupid-s-triazabenzene, 2,4-bis-3, 6-(4-ethoxy)benzene _S-triazabenzene, 2,4-bistrichloroindolyl-(3-moly-4-ethoxy)phenyl-S-triazabenzene styrene*, 2-t-butyl Brewing; 2 - pentyl brewing, β-chlorine awake and so on. These photopolymerization initiators may be used singly or in combination of two or more kinds. The amount of use is not particularly limited, but it is preferably used in an amount of 〇.05 to 20 parts by weight based on the active energy ray-curable resin composition of bismuth (8) by weight, in order to maintain good sensitivity and prevent crystallization and deterioration of physical properties of the coating film. And especially good for using 〇1~1〇 parts by weight. The photopolymerization initiator is selected from the group consisting of 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy) Phenyl]-2-hydroxy- 2-methyl-1-propan-1-one, 9-oxythiocarban and 9-oxothiopurine derivative, 2,2'-dimethoxy-1, 2-diphenylethene-1-ketone, 2,4,6-trimercaptophenylphosphonium diphenylphosphine oxide, bis(2,4,6-trimercaptophenyl)phenyl oxide Phosphine, 2-indenyl- 1 -[4-(indolyl)phenyl]- 2-------Acetone '2-Benzyl- 2 -didecylamino-1—(4-B The mixed active energy ray-curable resin composition for coating having high curability is particularly preferable because one or a mixture of two or more of the linalyl-phenylene-butanone-ketones can be obtained. Commercial products of the photopolymerization initiator are, for example, Irgacure-184, Irgacure-149, Irgacure-261, Irg-lean cure-369, Irgacure-500, Irgacure-651, Irgacure-754, Irgacure-784, Irgacure-819. Irgacure - 907, Irgacure - 1116, Irgacure - 1664, Irgacure - 1700, Irgacure - 1800, Irgacure - 1850, Irgacure - 2959, Irgacure - 4043, Darocur - 1173 31 201200555 (made by Ciba Specialty Chemicals), Lucirin TPO ( BASF Corporation), KAYACURE -DETX > KAYACURE - MBP' KAYACURE - DMBI' KAYACURE - EPA, KAYACURE - OA [Nippon Chemical Co., Ltd.], VICURE-10, VICURE-55 (made by STAUPFER - Co., Ltd.), TRIGONALP1 (manufactured by AKZO Co., Ltd.), SANDORY 1000 (manufactured by SANDOZ Co., Ltd.), DEAP (manufactured by APJOHN Co., Ltd.), QUANTACURE - PDO, QUANTACURE - ITX > QUANTACURE - EPD (manufactured by WARD BLEKINSOP Co., Ltd.). Further, in the active energy ray-curable resin composition, various photosensitizers may be used in combination with the above photopolymerization initiator. A photosensitizer such as an amine, a urea, a sulfur-containing compound, a phosphorus-containing compound, a gas-containing compound or a nitrile or other nitrogen-containing compound. Further, in order to improve the adhesion to the film substrate or the like, the active energy ray-curable resin composition may be used in combination with other resins. / the other resin, such as: methacrylate methacrylate resin, methacrylate methacrylate f copolymer and other acrylic resin; polystyrene, thiol (tetra) ruthenium g - styrene-based polyurethane resin; The polybutadiene or butadiene-acrylonitrile-based lion energy ray hard substrate is coated, that is, the film plastic (curl) is less on the film substrate or the like. Further, because of the low shrinkage at the time of hardening, the film can be applied to the coating of the film substrate. On the substrate, i is applied to make the amount of dryness, such as 2', preferably in various films. Further, it is 0•b 30-2, and preferably 1 to 臈, since it is easy to achieve hardening of the film = the film thickness of the substrate is 3% or more, and more preferably the thickness of the hardened layer is 3 with respect to the film. Further, the film having a thickness of the hardened layer is a film having a film thickness of 5 to 1 with respect to the film thickness of the hardened layer, and is preferably a film having a film thickness of 5 to 50%. 32 201200555

聚烯煙、環氧樹脂、三聚氰胺樹脂、三乙釀 基材，例如：聚碳酸酯、聚曱基丙烯酸甲酯 膠膜狀基材等。塑膠膜狀 甲酯、聚苯乙烯、聚酯、 樹脂、As樹脂、降猫烯系、樹脂、環狀烯烴、 材等。 三乙醯基纖維素樹脂、ABS :烯烴、聚醯亞胺樹脂等膜基 射線硬化性細旨組合物的塗佈方法’沒有特別限定 凹方法，例如：棒塗法、邁耶棒式塗佈法、氣刀塗佈法、 佈法、反轉凹版塗佈法、膠印法、柔版印刷法、絲網印刷 ，射的活性能量射線，例如：紫外線或電子射線。利用紫外 時’使用具梳燈、高壓水紐、金屬自化物燈作為 ίί，紫外線照射裝置’並根據需要卿衫、光源配置等，在 壓水紐的情況下’通雜佳為械於具有8G〜16權咖 ，量的一個燈，以5〜50m/分鐘的輸送速度進行硬化。另一方面， 士，電子射線進行硬化時，通_佳為用具* 1G〜施v加速 电堊的電子射線加速裝置，以5〜5〇m/分鐘的輸送速度進行硬化。 如上述，，活性能量射線硬化性樹脂組合物在硬化時的收縮 *生土，且硬度高。因此，藉由使用該組合物，可以提供在膜基材 上，置該組合物的硬化層的膜。這種膜可以適用於例如以偏光板 保護臈、觸摸屏等光學物品用硬塗層膜為代表的各種保 反射膜、擴散膜或棱鏡片的背面塗層等。 ❹隻膜防 ^ 此外，上述活性能量射線硬化性樹脂組合物不僅適合用作保 述偏光板、觸摸屏等平面狀物品的保護膜，而且也適合用於 保5蒦上述平面狀物品以外的塑膠物品，例如行動電話等家電製品 或汽車保險桿等成型品的表面。 對於使用活性能量射線硬化性樹脂組合物形成保護成型品表 面的保護層的方法，可以列舉塗裝法、轉印法、片材黏接法等。 ^塗裝法是將由活性能量射線硬化性樹脂組合物所形成的塗佈 劑進行喷塗，或使用簾塗機、輥塗機、凹版塗佈機等印刷機將其 33 201200555 塗佈在成型品上形成外塗層後，照射活性能量射線使外塗層交聯 的方法。 轉印法是將在具有脫膜性的基體片材上塗佈了活性能量射 硬化性樹脂組合物的轉印材料黏接於成型品表面，然後藉由離 基體片材而將外塗層轉印職型品表社，接著照射活^能量 線製作交聯塗膜，或者將該轉印材料黏接於成型品表面，妙 射活性能量麟製作交聯塗膜，接麵由_基體片材而將；； 層轉印到成型品表面上的方法。 i 此外’片材黏接法^:將在基體片材上具有保護層以及根 要的修飾層的保護片黏接於塑膠成型品，從而在成型品表面上形 成保護層的方法。其巾，本發明的塗佈用活佩量轉硬化性1 月j組合物可以較佳用於轉印法或片材黏接法的用途。以下， 藉由轉印法、片材黏接法形成保護層的方法進行詳細說明。 為了使用活性能量射線硬化性樹脂組合物並藉由 保護層’首先製作轉印材料。轉印材料，例如，可以藉由將活 能量射線硬錄齡組合物單獨、或衫官能異驗自旨配合，#A polyene olefin, an epoxy resin, a melamine resin, or a triethyl styrene substrate, for example, a polycarbonate, a polymethyl methacrylate film-like substrate, or the like. Plastic film methyl ester, polystyrene, polyester, resin, As resin, catene, resin, cyclic olefin, and the like. The method of applying a film-based ray-curable composition such as a triethylenesulfonyl cellulose resin or an ABS: olefin or a polyimide resin is not particularly limited, and for example, a bar coating method or a Meyer bar coating method Method, air knife coating method, cloth method, reverse gravure coating method, offset printing method, flexographic printing method, screen printing, active energy ray, such as ultraviolet light or electron ray. When using ultraviolet light, 'use a comb lamp, high-pressure water button, metal self-organized lamp as ίί, ultraviolet irradiation device' and according to the needs of the shirt, light source configuration, etc., in the case of pressure water button, 'passive good for the machine with 8G ~16 right coffee, the amount of one lamp, hardened at a conveying speed of 5~50m/min. On the other hand, when the electron beam is hardened, it is hardened by an electron beam accelerating device of an electric device*1G to a v-acceleration electric motor at a conveying speed of 5 to 5 〇m/min. As described above, the active energy ray-curable resin composition shrinks at the time of curing * soil and has high hardness. Therefore, by using the composition, it is possible to provide a film on which a hardened layer of the composition is placed on a film substrate. Such a film can be applied to, for example, various antireflection films such as a polarizing plate protective film, a hard coat film for optical articles such as a touch panel, a back coat layer of a diffusion film or a prism sheet, and the like. In addition, the active energy ray curable resin composition is not only suitable for use as a protective film for a flat article such as a polarizing plate or a touch panel, but also suitable for use in protecting plastic articles other than the above planar articles. For example, the surface of a molded article such as a mobile phone such as a mobile phone or a car bumper. The method of forming the protective layer for protecting the surface of the molded article using the active energy ray-curable resin composition may, for example, be a coating method, a transfer method, a sheet bonding method, or the like. The coating method is a method in which a coating agent formed of an active energy ray curable resin composition is sprayed, or a coating machine such as a curtain coater, a roll coater, or a gravure coater is used to apply the film 33 201200555 to a molded article. After the overcoat layer is formed, the active energy ray is irradiated to crosslink the overcoat layer. In the transfer method, a transfer material coated with an active energy sclerosing resin composition on a base sheet having a release property is adhered to a surface of a molded article, and then the overcoat layer is transferred from the base sheet. Ink-type products, then irradiate the active energy line to make a cross-linked coating film, or bond the transfer material to the surface of the molded product, and make a cross-linked coating film by using the active energy energy. The joint surface is made of _ base sheet. And the method of transferring the layer onto the surface of the molded article. i In addition, the sheet bonding method is a method of bonding a protective sheet having a protective layer and a desired decorative layer on a base sheet to a plastic molded article to form a protective layer on the surface of the molded article. As the towel, the composition for coating of the present invention can be preferably used for a transfer method or a sheet bonding method. Hereinafter, a method of forming a protective layer by a transfer method or a sheet bonding method will be described in detail. The transfer material is first produced by using the active energy ray-curable resin composition and by the protective layer'. The transfer material can be, for example, a combination of a live energy ray hard ageing composition alone or a shirt functional sensation, #

佈在基材片上’並藉*加熱使硬化性樹脂 ；J 化（Β —階化）而製造。 〜疋们·干硬 、力有Si=量”性細旨組合物並㈣多官能異氰酸醋， '又ίΐΐί 吏用公知的各種多官能異氰咖旨。例如，可 以使用異佛義二異紐g旨、二？苯二異氰酸_、氫化 異、甲苯二異、二苯基甲燒二異氰咖旨、^—己& ===質的三聚物、多元醇和上述二異氰酸酯反應 二，的預物4。即’藉由使聚合物中所含_基與多官能 異氰旨的異氰酸酯基反應而進行B —階化。 、 柄硬化蝴脂組合物和多官能異氣_旨的使用比 “二組合物的祕和多官能異氰酸_ 異氛^基的比例宜為·w/卜且較佳為1/〇.〇5〜则。 姆乃城V白、纖維素片、這些片材的複合物等。 34 201200555 上述，膠片’例如：上述塑膠狀膜等。 加1金^箔，例如：鋁箔、銅箔等。此外，作為上述纖維素片， 倒如.玻璃紙、塗佈紙、赛璐玢等。 ’、 ’較佳㈣膠片’其中更佳為聚醋片。 渺ίΐίΐ印材料時，首先在基材片上塗佈活性能量射線硬化性 |曰二σ物。該樹脂組合物在後述的保護層形成方法中，形成成 二外層’且該層是用於保_型品或成型品上的圖案 二或摩擦損害的層。塗佈轉印材料用硬化性樹脂組合^勿The cloth is placed on the substrate sheet and manufactured by heating the hardening resin to a certain degree. ~ We have a dry and hard, force Si=quantity composition and (4) polyfunctional isocyanuric acid, 'also ΐΐ ΐΐ 吏 公 公 公 公 公 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 Iso-g, bis-benzene diisocyanate _, hydrogenated iso-, toluene diiso, diphenyl-methyl diisocyanate, ^-hex & === terpolymer, polyol and the above two Precipitate 4 of the isocyanate reaction 2, that is, 'B-staged by reacting the _ group contained in the polymer with the isocyanate group of the polyfunctional isocyanate. The stalk hardening butterfly composition and the polyfunctional gas The ratio of the use of the two compositions is more than /w and preferably 1/〇.〇5~. Mnacheng V white, cellulose sheets, composites of these sheets, and the like. 34 201200555 The above film is, for example, the above-mentioned plastic film or the like. Add 1 gold foil, for example: aluminum foil, copper foil, etc. Further, as the above cellulose sheet, it is, for example, cellophane, coated paper, cellophane or the like. ', 'Best (four) film' is more preferably a vinegar piece.渺ίΐί In the case of a printing material, first, an active energy ray hardening property is applied to a substrate sheet. This resin composition is formed into a second outer layer in a protective layer forming method to be described later, and this layer is a layer for protecting the pattern or the pattern on the molded article or the frictional damage. Curing resin combination for coating transfer material

Si蓉tti凹版塗佈法、輥塗法、喷'塗法、唇塗法、逗點式 佈法，凹版印刷法、絲網印刷法等印刷法等。塗佈時， 劑性良好的觀點考慮，較佳為以保護層厚度為 的方式=于 = '塗佈’其中更佳為以保護層厚度為卜― 當上述保護層由基體片材的剝 層的方式塗佈轉印材料用硬丄^ 仁^為I改善保護層由基體片材的剝離性，也可以在基體片材上 ί ’在整面上形成脫臈層。脫模層，在後述=型 W的保€層械方法中，將轉印材料 σ 獅時’與基體 石《脫模劑、 法、槪、喷塗法、唇塗::法=凹版塗佈 刷法、絲網印刷法等印刷法。 、、等塗佈法，凹版印 在基材片上塗佈轉印材料用硬 燥。乾燥例如可以利用加熱來進行y曰”使其乾 能量射線硬化型樹脂組合物含有有丁機^，加:當塗佈用活性 加熱溫度通常為.靴 常為30秒〜30分鐘，較佳為1叫〇分鐘’且更佳為通 35 201200555 刷塗印=^的B—階化樹脂層’從容易在該樹脂層上 量射線前料方面考慮’希望其在照射活性能 h, 也可以形成圖案層。圖案層是在B—階化樹脂層 嫌二5 ίΐ刷，而形成的。印刷層的材質’可以使用以聚乙 樹脂、聚g旨系樹脂、聚丙烯酸系樹脂、聚胺 ΐί=Η、产 縮醛系樹脂、聚§旨胺基甲酸_脂、纖維 旨?樹脂作為黏結劑，並含有適當顏色的顏 、/者色_#色油墨°圖案層的形成方法，例如可以 凹版印刷法、絲網印刷法等常用印刷法等。特別是 調表現’適合使用膠印法和凹版印刷法。此外， 辰i法二μ 用凹版塗佈法、輥塗法、逗點式塗佈法、 ϊ設置的情況。此外，圖案層可以由金屬蒸鑛層$ 成或由印刷層和金屬蒸鍵層組合形成。 不層或圖案層對成型品有足夠的黏接性時，可以 也可以根據需要形成黏接層。黏接層是在成型 】行黏接的部分。心想==ί 面的’則在整面上形成黏接層。若想要黏接的部分是 在局部上形成勒接層。黏接層，適宜使用適合於成型。:斜咸 熱性或感壓性樹脂。例如’當成型品的材質 ^樹^ /乙烯系樹知、聚碳酸酯系樹脂、苯乙稀共聚物系樹脂 =合樹脂時，使用與這些樹脂具有親合性的聚丙稀=烯 聚苯乙烯系樹脂、聚醯胺系樹脂等即可。進一半，杏_开、，月曰、 質為聚丙稀樹脂時，可以使用氯化聚烯烴樹脂( ' 里品的材 烯醋共聚物樹脂、環化橡膠、古馬隆節樹脂為乙酸乙 方法，_版_、缝法、逗“成 凹版印刷法、絲網印刷法等印刷法。 主佈法， 36 201200555 用成型品的定於亡述形式」例如在使用利 轉印材料時，可以進行表面保護處理為目的之 和黏接層字並=#===依次形成-階化樹脂層 也可以置層上具有圖案層或黏接層時， 學試劑料、倾賴品簡簡不受化 三聚可以使用雙液型硬化性聚胺醋樹脂、 等熱塑性樹脂:加;氯乙婦共聚物樹脂 點式塗佈法等塗=層凹版塗佈法、法、逗 盔m伸 版印刷法和絲網印刷法等印刷法。 轉印;^上述轉印材料形成成型品的保護層，例如，將上过、 化後_旨層鱼成』L3i說：例如：將轉印材料的Β-階 材剝離，將轉印材 材料的基體片 的交聯硬化的方法f線硬化’從而進行樹脂層 内，在模腔内注射充滿樹脂，成型模具 面黏接，並剝離基體片材從而 交聯硬化的方法（同時成化’細進行樹脂層的 土糾另!!姑樹脂層的交聯硬化和轉印操作過程’較佳為如卜、十、古 法所不將轉印材料與成型品表面黏接，然後夢由Stiff 而將其轉印到成型品表面上錢 ^材剝離 ，操作過程，但也可以是將轉射的順 從基體片材-側照射活性能量射線^ +接’然後 體片材而進行轉印的順序的操作過程。…€ ’接著剝離基 〇 ^成型品，材質並沒有限定，例如：樹脂成型口 口口、此專的複合製品等。這些成型品可以是透明、‘月木= 37 201200555 =的任*7種。此外’成型品可以是著色的，也可以是未著色的。 似:丄可以列舉聚苯乙稀系樹脂、聚烯烴系樹脂、樹脂、AS 石山樹脂。此外，也可以使用聚苯醚·聚苯乙稀系樹脂、聚 =_曰1繼、聚縮㈣樹脂、丙烯酸系樹脂、聚碳_改質聚 二：5對Ϊ二曱酸乙二醇醋樹脂、聚對苯二甲酸丁二醇醋 取为子1聚乙烯樹脂等通用工程樹脂，以及聚砜樹脂、 樹脂、聚苯醚系樹脂、I丙烯酸酯樹脂、聚醚醯亞胺 工^t亞胺樹脂、液晶雜樹脂、聚芳基㈣熱樹脂等超級 嶋了_綱錢填料等增 1本ί明成型品賴層的形成方法巾所使用的活性能量射線， hi *、轉ρ材料用硬化性樹脂組合物的組成而決定，通常 量撕珊，聰_累積光 ，使用，耐熱橡膠狀彈性體’例如矽橡膠的輥式轉印機、 )轉印機等轉印機，並介㈣定為溫度80〜 料的mso〜2〇〇kg/m2的條件的耐熱橡膠狀彈性體，從轉印材 ΐϊ 加ί和/或壓力。由此將黏接層與成型品表= m μ I右在、㈠卩後剝離基體片材，則在基體片材和樹脂層 ϊΐΐίί產生剝離。此外’在基體片材上設置脫模層時，若將 ，則在脫模層和樹脂層的交界面上產生剝2最後， ί 量ίί，使轉印到成型品上的樹脂層完全交聯硬 隹層外’也可以在娜基體片材操作過程之前， 進仃照射活性能量射線的操作過程。 τι杈之月jSi Rong tti gravure coating method, roll coating method, spray coating method, lip coating method, comma method, gravure printing method, screen printing method, etc. At the time of coating, from the viewpoint of good agent properties, it is preferable to use a thickness of the protective layer === "coating", more preferably, the thickness of the protective layer is - when the protective layer is peeled off from the base sheet The coating material is coated with a hard material to improve the peelability of the protective layer from the base sheet, and a release layer may be formed on the entire surface of the base sheet. The release layer, in the protective method of the type of W described later, the transfer material σ lion's and the base stone "release agent, method, enamel, spray method, lip coating:: method = gravure coating Printing methods such as brushing and screen printing. , and the like, the gravure printing is applied to the substrate sheet to apply a transfer material for hard drying. Drying can be carried out, for example, by heating, so that the dry energy ray-curable resin composition contains a dicing agent, and the active heating temperature for coating is usually 30 seconds to 30 minutes, preferably 30 seconds to 30 minutes. 1 〇 minute ' and more preferably pass 35 201200555 brush printing = ^ B-staged resin layer 'from the easy to measure the amount of ray on the resin layer, 'hope that it can be formed in the irradiation activity h, can also form Pattern layer: The pattern layer is formed by brushing a B-staged resin layer. The material of the printed layer can be used as a polyethylene resin, a polyg resin, a polyacryl resin, or a polyamine. A method for forming a pattern layer of a color, a color, or a color ink of a suitable color, such as a acetal resin, a polyacetal carboxylic acid, a resin, or a resin, as a binder, for example, gravure printing Common printing methods such as printing methods, screen printing methods, etc. In particular, the adjustment performance is suitable for the offset printing method and the gravure printing method. In addition, the g-method method is a gravure coating method, a roll coating method, a comma coating method, ϊSettings. In addition, the pattern layer can be made of metal The mineral layer is formed by a combination of a printed layer and a metal vapor-bonding layer. When the layer or the pattern layer has sufficient adhesion to the molded article, the bonding layer may be formed as needed. The bonding layer is formed in the line. The part that is bonded. The thought of == ί 面 ' 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成A salty heat-sensitive or pressure-sensitive resin. For example, when the material of the molded article is ^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^ Polypropylene = olefinic polystyrene resin, polyamidamide resin, etc.. In half, apricot _ open, moon 曰, quality is polypropylene resin, chlorinated polyolefin resin can be used ( ' 里The olefinic vinegar copolymer resin, the cyclized rubber, the coumarone resin is the acetic acid B method, the _ version _, the stitching method, the simplification printing method, the gravure printing method, the screen printing method, etc. Main cloth method, 36 201200555 The shape of the molded article is determined in the form of a description, for example, when using a transfer material, For the purpose of surface protection treatment and adhesion layer words and = # = = = sequentially formed - the graded resin layer can also be layered with a pattern layer or adhesive layer, the study reagents, lean products are not simplified For the polymerization, it is possible to use a two-liquid type curable polyurethane resin, a thermoplastic resin such as a compounding agent, a coating method such as a chloroethylene copolymer resin, a coating method, a coating method, a method, a masking method, and a silk coating method. Printing method such as screen printing method. Transfer; ^ The above-mentioned transfer material forms a protective layer of the molded article, for example, after the above-mentioned transfer, the layered fish is formed into a "L3i": for example, a transfer material of Β-staging The method of peeling and hardening the cross-linking and hardening of the base sheet of the transfer material is performed in the resin layer, and the resin is filled in the cavity, and the surface of the molding die is bonded, and the base sheet is peeled off to crosslink and harden. (At the same time, the process of 'finishing the resin layer is fine!! The cross-linking hardening and transfer operation process of the resin layer' is preferably such that the transfer material and the surface of the molded product are not bonded to each other. , then dream by Stiff and transfer it to the surface of the molded product The operation process, but may also be a sequence of operations in which the transferred substrate is irradiated with the active material ray and then transferred to the body sheet. ...€ ‘and then peeling the base 〇 ^ molded product, the material is not limited, for example: resin molding mouth, this special composite products. These molded articles may be transparent, ‘moon wood = 37 201200555 = any of the 7 types. Further, the molded article may be colored or uncolored. Like: 聚 can be listed as a polystyrene resin, a polyolefin resin, a resin, and an AS stone resin. In addition, polyphenylene ether polystyrene resin, poly = _ 曰 1 followed by polycondensation (tetra) resin, acrylic resin, poly carbon _ modified poly 2: 5 pairs of decyl phthalate Resin, polybutylene terephthalate vinegar is used as general engineering resin such as sub-1 polyethylene resin, and polysulfone resin, resin, polyphenylene ether resin, I acrylate resin, polyether oxime Amine resin, liquid crystal resin, polyaryl (four) thermal resin, etc. are super 嶋 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The composition of the resin composition is determined, usually the amount of tearing, Cong_cumulative light, use, heat-resistant rubber-like elastomers such as roll transfer machines such as enamel rubber, transfer machines, etc., and (4) It is a heat-resistant rubber-like elastomer of a condition of mso to 2 〇〇 kg/m2 of a temperature of 80 Å, and ί and/or pressure is applied from the transfer material. Thus, the adhesive layer and the molded article table = m μ I are right, and after (1) the base sheet is peeled off, and the base sheet and the resin layer are peeled off. In addition, when the release layer is provided on the base sheet, if it is, the peeling is caused at the interface between the release layer and the resin layer, and finally, the resin layer transferred onto the molded article is completely crosslinked. The outer layer of the hard layer can also be used to irradiate the active energy ray before the operation of the substrate. Τι杈之月j

保護射成型的同時成型轉印法形成成型品 iff 如具體制。首先，在由活纏和©定模所W 、成錢模具内，使黏接層作為内側，也就是說，送入轉印材料 38 201200555 f基^材與si定模接觸。此時，可以—片—片地送入轉 ί可以性地送人長條轉印材料的必要部分。在使用# 的成型用模具的方位達到—致即可。此外，在間歇= 時’用感測器檢測轉印材料的位置後，若用活動模 置，不材=雜通常可以將轉印材料固定在相同的位 位置不會偏離’因此相當方便。在關閉成型用模且 ㈣在活動模上的如向模具中注射充滿溶融樹脂，形成 料與成型品表面黏接。將樹月旨成型品i 量細細旨層完全交聯硬化，形成保護 曰匕外，也可以在照射活性能量射線後，剝離基體片材。 為轉，性樹脂組合物，不僅可以作 逗點還可以_上述凹版塗佈法、輥塗法、 舍塗佈法，凹版印刷法和絲網印刷法等印刷法，噴 塗法專塗佈在膜、片材、成型物等細品上。 $ _黏接法進行說明。片材黏接法，例如：將預先 ί二埶ί广材的基則材與成型*歸，然後利用加 忑接法r n，從而進行b—階化的樹脂層的交聯硬化的方法（後 ^注上，保ff形成用片材插人成型模具内，在模腔 成用η奸办拉曰’、ί导到樹脂成型品，並同時使其表面與保護層形 咖介二ϊ:然後利用加熱使其熱硬化，從而進行樹脂層的交 聯硬化的方法（同時成型黏接法）等。 方、、共iii賴形成用片材’例如可以藉由製造上述轉印材料的 其雜η t。鱗’在紐片材上塗佈硬化性樹驗合物時，在 性樹脂組合物的黏接力不足的情況下，也可以h 上ί佈硬t生ίίίίίΓΓ 2合物的面上塗佈底漆，並在其 #&、'^^@+/月曰、〇物2.猎由利用電暈放電等使基體片材的 录面^化等方法，可提高基體片材和硬化性樹脂組合物的黏接性。 述1·中使用的底漆’例如可以使用雙液型硬化性聚胺醋樹 39 201200555 脂、三聚氰胺系樹脂、環氧系樹脂等熱硬化性樹脂，氯乙稀丘聚 物樹脂、由丙烯酸樹脂所構成的水性乳膠等熱可塑性樹脂。^佈 黏接劑的方法’例如：凹版塗佈法、減法、逗點式塗佈法等塗 佈法，凹版印刷法、絲網印刷法等印刷法。 在上述製造轉印材料的方法巾，在基體諸上塗佈活性能量 ^硬化性職組合物後’照射活性能量躲。該活性能量 化0 性樹脂組合物中的（甲基）丙顧基藉由自由基 ^反應而鍵、纟。’並職三維㈣’從而使魏性細旨組合物硬 性倉化性樹脂組合物，在使用含有有機溶劑的活 ίΪΪΪ谷ί有機溶劑時:例如可以在照射活性能量射線 以直接放詈蚀&照射活性能置射線之前進行。去除方法，可 右撼，ίΐ使其揮發，也可以使用乾燥機等進行乾燥，作是去除 =洛劑時的溫度通常較佳為在7G〜13(rc下進行iq秒^ 另外，保護層形成用片材的構成並不限 的樹脂層成硬化 樹脂、環氧她f，胺㈣脂、三聚氰胺系 性樹脂开等Γίί 稀共聚物樹脂等熱可塑 佈法:J佈法，凹版印刷法和絲網印‘法ί印:f法、逗點式塗 所舉例法中所用的成型品，例如可以使用上述轉印法中 ，後黏接法中黏接成型品和保護層 如.在保護層形成用片材的基體片材或成 201200555 .表峰接的方法、 成月材的基體>1材和成型品表_接的方法 =At the same time as the protective injection molding, the molding transfer method forms a molded article iff as a specific system. First, in the mold and the mold, the adhesive layer is made inside, that is, the transfer material is fed into the mold. At this time, it is possible to feed the sheet to the sheet and transfer the necessary portion of the strip transfer material. The orientation of the molding die using # can be achieved. Further, after the position of the transfer material is detected by the sensor at the interval = ', if the movable mold is used, it is usually convenient to fix the transfer material at the same position without deviating from the use of the material. When the molding die is closed and (4) the molten mold is injected into the mold on the movable mold, the formed material is bonded to the surface of the molded article. The substrate may be completely cross-linked and hardened to form a protective layer, and the base sheet may be peeled off after the active energy ray is irradiated. In order to rotate, the resin composition can be used not only as a comma but also as a gravure coating method, a roll coating method, a coating method, a gravure printing method, a screen printing method, or the like, and a spray coating method is applied to the film. , sheets, molded products and other fine products. $ _ bonding method for explanation. The sheet bonding method, for example, a method of pre-bonding a base material and a molding*, and then performing a cross-linking hardening method of the b-staged resin layer by using a twisting method rn (after ^ Note that the ff formation sheet is inserted into the mold, and the mold cavity is made into a resin molded product, and the surface is protected with a protective layer. A method of performing cross-linking and hardening of a resin layer by heating (simultaneous molding bonding method), etc., and a sheet for forming a film, for example, by using the above-mentioned transfer material t. Scale 'When applying a curable tree test on a sheet, if the adhesive strength of the resin composition is insufficient, it is also possible to apply a surface on the surface of the lyophilized material. Primer, and in its #&, '^^@+/月曰, 〇物2. Hunting by using corona discharge to make the recording surface of the base sheet, etc., can improve the base sheet and hardenability Adhesiveness of the resin composition. The primer used in the above-mentioned 'for example, a two-liquid type curable polyurethane tree 39 201200555 grease can be used. A thermosetting resin such as a melamine resin or an epoxy resin, a vinyl chloride polymer resin, or a thermoplastic resin such as an aqueous latex composed of an acrylic resin. A method of bonding an adhesive agent, for example, gravure coating method a coating method such as a subtractive method or a comma coating method, a printing method such as a gravure printing method or a screen printing method. In the above method for producing a transfer material, an active energy/curing composition is applied to the substrate. After the 'irradiation activity energy hiding, the (meth) propyl group in the active energy-enhancing resin composition is bonded and enthalpy by a radical reaction. 'Part-time three-dimensional (four)' thus making the composition of the fine-grained composition hard The chemical resin composition is used in the case of using an organic solvent containing an organic solvent: for example, it can be carried out before the irradiation of the active energy ray to directly eclipse & illuminate the active energy. The removal method can be performed right, ΐ The volatilization may be carried out by using a dryer or the like, and the temperature at which the agent is removed is usually preferably 7 g to 13 (iq seconds at rc). Further, the composition of the protective layer forming sheet is not The limited resin layer is made of a hardening resin, an epoxy resin, an amine (tetra) grease, a melamine-based resin, etc., and a thermoplastic cloth method such as a J-method, a gravure printing method, and a screen printing method. For the molded article used in the method of the f-method or the comma-coating method, for example, in the above transfer method, a post-bonding method in which a molded article and a protective layer, such as a base sheet of a sheet for forming a protective layer, can be used. Or into 201200555. Table peak connection method, the base of the moon material > 1 material and molded product table _ connection method =

ZtilZZT^TtT' 基體ΐ材溶融:用:;#利用模内成型時的熱使 «此黏接保護層為一趙，並 用的黏接劑，例如:胺基甲酸酯系黏接劑处環氧法t所 黏接劑、丙稀酸系黏接劑和熱熔型黏接劑等糸黏細卜酉曰系 具體說:。S利的方法進行 形成用片材。接著，使用具備耐方式配置保護層 輥式轉印機、升降轉印機等轉^機，夕 ^如石^橡，的 形成用片材的保護層一侧施加執和/ 二體從保濩層 品表面雜。最後，利用加執成n字黏接層與成型 交聯硬化，形成保護層。Μ 成上所形成的樹脂層完全 保護層的方法進法形成成型品 的成型用模具内，使黏接層作㈡和固定飾^ 裝置，使保護層形成用片材的圖案===機構的輸送 致即可。此外，在間歇性地送人保^ 方位達到- 檢測保護層形成用片材的位置後IdU日:，用感測器 層形成_，通常可以將保護層形成 201200555 置，圖案層的位置不會偏離，因此相當方便。在關閉成型用模具 後，從設置在活動模上的澆口向模具中注射充滿熔融樹脂，形成 成型品’並同時將保護層形成用片材與成型品表面黏接。將樹脂 成型品冷卻後，打開成型用模具取出樹脂成型品。最後，使用熱 風式烘箱等進行加熱，使樹脂層完全交聯硬化，形成保護層。 [實施例] a 以下列舉實施例和比較例，對本發明作更具體的說明。實例 中的份和％，只要沒有特別描述，都是為質量基準。 (製造例1) 在具備授拌裝置、冷卻管、滴液漏斗和氮氣導入管的反應裝 置中’力口入250g曱基丙彿酸縮水甘油g旨（以下，稱為GMA)、i〇〇〇g 曱基異丁基酮（以下，稱為MIBK)以及l〇g第三丁基過氧化乙 基己酸醋（以下’稱為P — 0)後’在1氣流下用約1小時使反應 系内的溫度升溫到約9(TC，保溫1小時。接著，從預先加入有由 750g GMA、30g P —〇所形成的混合液的滴液漏斗，在氮氣流下 用約2小時向反應系内滴加混合液，在相同溫度下保溫3小時。 然後’升溫到120°C ’保溫2小時。冷却到60。(：後，將氮氣導入 管替換為空氣導入管’加入507g丙烯酸（以下，稱為AA)、2.3g 對曱氧基苯酚和9.3g三苯膦進行混合後，在空氣鼓入（Air Bubbling)下，升溫到ll〇°c。在相同的溫度下保溫8小時後，加 入1.6g對曱氧基苯酴，冷卻，並添加MIBK使不揮發成分為50%， 得到反應性分散劑（A—1)的溶液。該反應性分散劑（A—1)的 丙烯醯基當量約為214g/eq，羥基值約為262mgKOH/g、重量平均 分子量約為30,000。 (製造例2) 使用與製造例1相同的反應裝置，加入125g GMA、125g曱 基丙烯酸甲酯（以下，稱為MMA)、lOOOgMIBK以及10gP—Ο 後，在氮氣流下用約1小時使反應系内的溫度升溫到約90°C，保 溫1小時。接著，從預先加入有由375gGMA、375gMMA、30gP — Ο所形成的混合液的滴液漏斗，在氮氣流下用約2小時向反應 42 201200555 系内滴加混合液，在相同溫度下保溫3小時。然後，升溫到120°C， 保溫2小時。冷卻到6〇°C後，將氮氣導入管替換為空氣導入管，. 加入254g AA、2.3g對曱氧基苯酚和9.3g三苯膦進行混合後，在 空氣鼓入下’升溫到11(TC。在相同的溫度下保溫8小時後，加入 1.6g對甲氧基苯酚，冷卻，並添加MIBK使不揮發成分為50%， 得到反應性分散劑（A—2)的溶液。該反應性分散劑（A—2)的 丙烯醯基當量約為356g/eq，羥基值約為158mgKOH/g，重量平均 分子量約為40,000。 (製造例3) 使用與製造例1相同的反應裝置，加入75g GMA、175g MMA、1000g MIBK以及8g P —0後，在氮氣流下用約1小時使 反應系内的溫度升溫到約90。(：，保溫1小時。接著，從預先加入 有由300g GMA、700g MMA、23g P —0所形成的混合液的滴液 漏斗’在氮氣流下用約2小時向反應系内滴加混合液，在相同溫 度下保溫3小時。然後，升溫到12〇。〇，保溫2小時。冷卻到60°C 後，將氮氣導入管替換為空氣導入管，加入152g AA、2.3g對曱 氧基苯酚和5.6g三苯膦進行混合後，在空氣鼓入下，升溫到 110°C。在相同的溫度下保溫8小時後’加入16g對甲氧基苯酚， 冷卻，並添加MBK使不揮發成分為50%，得到反應性分散劑（A —3)的溶液。該反應性分散劑（A — 3)的丙烯醯基當量約為 545g/eq’羥基值約為103mgK〇H/g，重量平均分子量約為7〇,〇〇〇。 (實施例1) 在具備攪拌裝置、冷卻管、滴液漏斗和空氣導入管的反應裝 置中，添加50g二氧化矽微粒（Aerosil—50，曰本AEROSIL製’ 平均初級粒徑為30nm)、500gMIBK以及4g曱基丙烯醯氧基丙基 三甲氧基石夕烷（KBM503，信越化學製）、.磷酸酯（ph〇slexA—3， sc。有機化學製）的5%水溶液088g後，在空氣氣流下升溫至 l〇〇°C。保溫6小時後’得到經表面處理的無機粒子的漿料。 曰在所得的經表面處理的無機粒子的漿料（固體成分為50g的 量）中，加入25g製造例1中所得的反應性分散劑（A—u和5〇g 43 201200555 二季戊四醇六丙烯酸酯，得到調配物。 使用壽工業（股）製的UltraApexMill—UAM015進行該調配 物中二氧化矽微粒的分散。此處所用的Ultra Apex Mill — UAM015，具有在圖！中具有定子7的内徑為5〇mm(p，内容積為 0.Π公升，分離器4的直徑為4〇mm(p，分離器4的圓盤21間的 間隔為5mm的研磨機3，且在製造分散體時，向研磨機3中填充 相對於研磨機3的容積為50%之粒徑為30μιη的氧化鍅珠粒作為 介質。 ” 由圖1的原料槽1並通過供給口 16供給該調配物。然後，在 轉子的旋轉速度為恆定（轉子前端的圓周速度為8m/sec)的情況 下運轉研磨機3 ’独每分鐘L5公升的流量進行娜物的循環粉 碎。進行30分鐘循環粉碎的二氧化矽微粒係指分散在反應性分散 劑（A—1)、DPHA和MIBK的混合物中的分散體。從Ultra A Mdl-UAMOI5的取出口取出所得的分散體，並使用蒸發 MIBK，得到不揮發成分濃度為5〇%的分散體。 ’、 (實施例2) 除了使用由甲基丙烯酿基修部的二氧化石夕 AEROSIL製，平均初級粒捏為3ten)，代替實施例\之經表= 飾，一氧化梦微粒外，和實施例丨同樣的方式得到分 二 能量射線硬化性樹脂組合物即使在室溫（25。〇 _曰 $ίί ίΓ物，保存穩定性良好。·的方_雜筆硬ί的 (實施例3 ) 除了使用由甲基丙烯輯修飾的二氧 ΛΒ廳IL製，平均初級粒徑為12nm)，代替實‘二= tZtilZZT^TtT' base coffin melting: use:; #Using the heat in the in-mold molding to make «this bonding protective layer is a Zhao, and the adhesive used, for example: urethane-based adhesive ring Oxygen method t adhesive, acrylic acid adhesive and hot-melt adhesive, etc. The method of S is carried out to form a sheet. Next, using a transfer type roll-type transfer machine or a lift transfer machine equipped with a resisting type, the protective layer side of the forming sheet is applied to the side of the protective layer, and the two-body protection is applied. The surface of the layer is mixed. Finally, a protective layer is formed by bonding and bonding the n-type adhesive layer to the molding cross-linking. Μ A method of completely protecting the resin layer formed thereon is carried out to form a mold for molding a molded article, and the adhesive layer is used as a (2) and fixing device to form a pattern of the protective layer forming sheet === mechanism It can be delivered. In addition, after intermittently delivering the position of the protective sheet to the position of the sheet for detecting the protective layer formation, the IdU day: forming a layer with the sensor layer, the protective layer can be formed into 201200555, and the position of the pattern layer does not deviate. So it is quite convenient. After the molding die is closed, the molten resin is injected into the mold from the gate provided on the movable mold to form a molded article', and the protective layer forming sheet is bonded to the surface of the molded article. After the resin molded article is cooled, the molding die is opened to take out the resin molded article. Finally, heating is carried out using a hot air oven or the like to completely crosslink and harden the resin layer to form a protective layer. [Examples] a Hereinafter, the present invention will be more specifically described by way of examples and comparative examples. The parts and % in the examples are based on quality unless otherwise specified. (Production Example 1) In a reaction apparatus including a mixing device, a cooling tube, a dropping funnel, and a nitrogen introduction tube, 250 g of thioglycolic acid glycidol was used (hereinafter referred to as GMA), i〇〇 〇g decyl isobutyl ketone (hereinafter referred to as MIBK) and l〇g of tert-butylperoxyethylhexanoic acid vinegar (hereinafter referred to as P-0) are treated with a gas stream for about 1 hour. The temperature in the reaction system was raised to about 9 (TC, and kept for 1 hour. Then, a dropping funnel having a mixed solution of 750 g of GMA and 30 g of P-? was added in advance, and the reaction system was applied to the reaction system under a nitrogen stream for about 2 hours. The mixture was added dropwise and kept at the same temperature for 3 hours. Then, the temperature was raised to 120 ° C for 2 hours. Cooled to 60. (: After that, the nitrogen introduction tube was replaced with an air introduction tube to add 507 g of acrylic acid (hereinafter, It is called AA), 2.3g, and the mixture of decyloxyphenol and 9.3g of triphenylphosphine is heated to ll〇°c under air bubbling. After being kept at the same temperature for 8 hours, it is added. 1.6g of p-nonoxyphenyl hydrazine, cooled, and added MIBK to make the non-volatile component 50%, to obtain a reactive dispersant (A A solution of the reactive dispersant (A-1) having an acrylonitrile equivalent of about 214 g/eq, a hydroxyl value of about 262 mgKOH/g, and a weight average molecular weight of about 30,000. (Production Example 2) Use and manufacture In the same reaction apparatus of Example 1, after adding 125 g of GMA, 125 g of methyl methacrylate (hereinafter referred to as MMA), 100 g of MIBK, and 10 g of P-ruthenium, the temperature in the reaction system was raised to about 90 ° in about 1 hour under a nitrogen stream. C, kept for 1 hour. Then, from the dropping funnel previously added with a mixture of 375 g of GMA, 375 g of MMA, and 30 g of P?, the mixture was added dropwise to the reaction 42 201200555 under a nitrogen stream for about 2 hours. The temperature was maintained for 3 hours. Then, the temperature was raised to 120 ° C and kept for 2 hours. After cooling to 6 ° C, the nitrogen inlet tube was replaced with an air introduction tube. 254 g of AA, 2.3 g of p-methoxyphenol and 9.3 were added. After g triphenylphosphine is mixed, the temperature is raised to 11 (TC after air bubbling. After 8 hours of incubation at the same temperature, 1.6 g of p-methoxyphenol is added, cooled, and MIBK is added to make the non-volatile component 50. %, a solution of the reactive dispersant (A-2) is obtained. The reactive dispersant (A-2) had an acrylonitrile equivalent of about 356 g/eq, a hydroxyl value of about 158 mgKOH/g, and a weight average molecular weight of about 40,000. (Production Example 3) The same reaction apparatus as in Production Example 1 was used. After adding 75 g of GMA, 175 g of MMA, 1000 g of MIBK and 8 g of P-0, the temperature in the reaction system was raised to about 90 with a flow of nitrogen for about 1 hour. (:, holding for 1 hour. Then, a dropping funnel of a mixture of 300 g of GMA, 700 g of MMA, and 23 g of P-0 was added to the reaction system for about 2 hours under a nitrogen stream, and the mixture was added dropwise. The temperature was kept at the same temperature for 3 hours. Then, the temperature was raised to 12 Torr. 〇, kept for 2 hours. After cooling to 60 ° C, the nitrogen inlet tube was replaced with an air introduction tube, and 152 g of AA, 2.3 g of p-methoxyphenol and After mixing 5.6 g of triphenylphosphine, the temperature was raised to 110 ° C under air blasting. After holding at the same temperature for 8 hours, '16 g of p-methoxyphenol was added, cooled, and MBK was added to make the nonvolatile content 50. %, a solution of the reactive dispersant (A-3) is obtained. The reactive dispersant (A-3) has an acrylonitrile equivalent of about 545 g/eq' hydroxyl value of about 103 mg K〇H/g, and a weight average molecular weight of about 7 〇, 〇〇〇. (Example 1) In a reaction apparatus equipped with a stirring device, a cooling tube, a dropping funnel, and an air introduction tube, 50 g of cerium oxide microparticles (Aerosil-50, manufactured by AE AEROSIL) was added. Primary particle size 30nm), 500g MIBK and 4g mercapto propylene methoxypropyl A 5% aqueous solution of methoxy oxalate (KBM503, manufactured by Shin-Etsu Chemical Co., Ltd.) and a phosphate ester (ph〇slex A-3, sc. manufactured by Organic Chemical Co., Ltd.) was heated to 1 ° C in an air stream. After the hour, a slurry of the surface-treated inorganic particles was obtained. 曰 In the obtained slurry of the surface-treated inorganic particles (amount of solid content of 50 g), 25 g of the reactive dispersant obtained in Production Example 1 was added ( A-u and 5〇g 43 201200555 Dipentaerythritol hexaacrylate, a formulation was obtained. The dispersion of cerium oxide microparticles in the formulation was carried out using UltraApexMill-UAM015 manufactured by Shou Industrial Co., Ltd. The Ultra Apex Mill used herein was used. UAM015 has the inner diameter of the stator 7 in the figure! 5 〇mm (p, the inner volume is 0. Π liter, the diameter of the separator 4 is 4 〇 mm (p, the interval between the discs 21 of the separator 4) In the case of a 5 mm grinder 3, and in the production of the dispersion, the grinder 3 is filled with cerium oxide beads having a volume of 50% with respect to the volume of the grinder 3 of 30 μm as a medium. 1 and supply the formulation through the supply port 16. Then, at the turn When the rotation speed is constant (the circumferential speed of the rotor tip is 8 m/sec), the grinding machine 3' is operated at a flow rate of L5 liters per minute to carry out the cycle pulverization of the Nas. The cerium oxide particles which are cyclically pulverized for 30 minutes are referred to. Dispersion dispersed in a mixture of reactive dispersant (A-1), DPHA and MIBK. The obtained dispersion was taken out from the outlet of Ultra A Mdl-UAMOI5, and the concentration of the nonvolatile matter was obtained by evaporating MIBK. % dispersion. ', (Example 2) In addition to the use of the methacrylic acid-based base of the oxidizer AEROSIL, the average primary granules are 3ten), instead of the embodiment of the table = decoration, oxidized dream particles, and EXAMPLES In the same manner, a two-component energy ray-curable resin composition was obtained at room temperature (25 〇 曰 ί ί , , , , 保存 保存 保存 保存 保存 保存 保存 保存 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( 实施 实施 实施 实施In addition to the use of dioxin-modified dioxin halls, the average primary particle size is 12 nm) instead of real 'two = t

I 在1〇〇份該分散體中加入2份Irgacure 184 (光起始劑） 活性能量射線硬化性樹脂組合物。活性能量射 室溫（25°C)下保存2個月，也未產生職物 ίίίΪτ。糾，在下述條件下製作硬化塗臈，測定錯筆硬度了 結呆馬4Η。 44 201200555 飾的二氧化矽微粒外，和實施例丨同樣的方 能量射線硬錄樹驗合物較在技(Ig l2 7。活性 也未產生沉澱物，保存穩定性良好。同個月’ 結果為4H。 7的方式測疋銘筆硬度的 (實施例4) 除了使用二氧化矽微粒（R72〇〇，日制 級粒徑為12rnn)，代替實施例！之經表 =微=初 合物即使在室溫（25。〇絲2細， \ 定性良r同樣的方式測定錯筆硬度的結果為411。’物保存穩 (實施例5) r8g甲基丙稀醯氧基丙基三甲氧基魏（kbm503， ϊϊϋ 施例1 w4g f基⑽醯氧基丙基三曱氧基 =(趣棚，信越化學製）夕卜，和實施例i同樣的方式得到分 J體。活性能量射線硬化性樹脂組合物即使在室溫（25。〇下保 =1月，也未產生沉殿物，保存敎性良好。同樣的方式測定 鉛筆硬度的結果為5H。 <錯筆硬度的測定方法〉 1. 硬化塗膜的製作方法 使用棒塗機在三乙醯基纖維素（TAC)膜（膜厚40μιη)上塗 佈^性能量射線硬化性樹脂组合物（膜厚10μιη)，在7(rc下乾燥 ^分鐘，再在氮氣下使用高壓水銀燈，並使其在250mJ/cm2的照射 i下通過，進行硬化，從而得到具有硬化塗膜的試驗片。 2. 硬化塗膜的評價方法 、^根據JIS K5400，並利用載重為5〇〇g的鉛筆畫線試驗評價上 述試驗片的硬化塗膜。 (實施例6) ^除了使用25g製造例2中所得的反應性分散劑（a-2)，代替 貫，例1的25g反應性分散劑（A—丨）外，和實施例丨同樣的方 式得到分散體。活性能量射線硬化性樹脂組合物即使在室溫 45 201200555 c)保存2個月，也未產生沉澱物，保存穩定性良好。同樣 的方式測定鉛筆硬度的結果為5H。. (實施例7) 一除了使用25g製造例3中得到的反應性分散劑（a一3)，代替 例1的25g反應性分散劑（a—1)外，和實施例1同樣的方 $得。到分散體。活性能量射線硬化性樹脂組合物即使在室溫 C)保存2個月，也未產生沉殿物，保存穩定性良好。同樣 的方式測定鉛筆硬度的結果為5H。 (比較例1) —以固體成分叶為；25g之製造例1中所得的反應性分散劑（a 25g —季戊四醇六丙稀酸酯（DPHA)、50g二氧化石夕微粒（曰 f AEROSIL (股）製AER0SIL_5()，平均初級粒徑約為12nm) 細'調配’制調配物。活性能量射線硬化性樹脂 使在至溫（25C)下保存2個月，也未產生沉澱物，保 =1=樣的方式進行該調配物的分散， 表作硬化塗膜，並測定鉛筆硬度，結果為2H。 (比較例2) 除了使用5〇g以曱基丙烯醯基修姊的二氧切微粒（腺5〇， 日本AEROSIL製’平均初級粒徑為3〇nm) =⑽⑻製侧C V—550。)和2〇g二二= 樣的方式得财揮發成减度為5()%_較對照用反 在100份該比較對照用反應性分散體中加人2份I e 184 ’得較對照用活性能量射線硬化性樹脂組合物。比較對照 用活性旎量射線硬化性樹脂組合物在室溫（25。〇保 (比較例3 ) 除了使用5=份以甲基丙棘基修飾的 日本AE歷L製，平均初級粒徑為12nm)、5〇 46 201200555 份MIBK外，和實施例丨同樣的方式得到不揮發成分濃度為5〇% 的比較對照用反應性分散體。 在胃1〇〇份該比較對照用反應性分散體中加入2份Irgacure 184，得到比权對照用活性能量射線硬化性樹脂組合物。比較對照 用活丨生月b里射線硬化性樹脂組合物在室溫（Μ。。）保存1周時， 物。此外，和實補4同樣的方式製作硬化塗膜，測 疋鉛筆硬度，結果為3H。 【圖式簡單說明】 備本㈣之分紐的製造綠帽之上述濕 式攪拌球研磨機之原料漿料粉碎處理回路的概略圖。 採找細本發明之分紐的製造方法巾所使用之上述濕式擾 拌球研磨機之縱剖面圖。 拌球紐的製造方种所使狀上述濕式攪 衣研磨捣:在t、、、Ό J:料時的供給口的縱剖面圖。 [圖4]顯示介質排出時之供給口的縱剖面圖。 拌球樹細社述臟 圖。[圖6]顯示圖5中所示之濕式餅球研磨機之分離器的橫剖面 【主要元件符號說明】 1原料槽； 2原料泵； 3磨碎型濕式攪拌球研磨機； 4分離器； 5軸； 6夾套； 7定子； 9 溢流道(spillway); 201200555 11轉子； 12馬達； 13滑輪； 14滑輪； 15轉子連接頭； 16供給口； 17篩網支撐物； 18篩網； 19取出口； 21圓盤； 22葉片； 23調節器； 24閥座； 25閥體； 26 .圓筒體； 27導入口； 28圓筒體； 29氣體導入口； 30電磁切換閥； 31活塞； 32桿； 33彈簧； 34螺帽； 43軸； 43a 軸 43 的肩(shoulder) 44分離器； 45隔板， 45轉子； 47塞子； 48螺釘； 201200555 51葉片嵌合溝； 52圓盤； 53葉片； 54溢流道； 55孔； 56 ί哀狀隔板， 58閥門； 59閥門； 60閥門； 61閥門； 62閥門； 63製品槽。I Two parts of Irgacure 184 (photoinitiator) active energy ray curable resin composition were added to 1 part of this dispersion. The active energy was stored at room temperature (25 ° C) for 2 months, and no ίίίΪτ was produced. Correction, the hardening coating was made under the following conditions, and the hardness of the wrong pen was measured. 44 201200555 decorated with cerium oxide particles, the same as the energy ray hard-recorded tree test of the same example ( (Ig l27. The activity also did not produce precipitates, good storage stability. same month' results The hardness of the pen is 4H. 7 (Example 4) In addition to the use of ceria particles (R72〇〇, the daily particle size is 12rnn), instead of the example! Even at room temperature (25. Filament 2 fine, \ qualitatively good r the same way to determine the wrong pen hardness is 411. 'Storage stability (Example 5) r8g methyl propyl methoxypropyl trimethoxy Wei (kbm503, ϊϊϋ Example 1 w4g f-based (10) methoxypropyltrimethoxy group = (Fun, Shin-Etsu Chemical Co., Ltd.), obtained in the same manner as in Example i. Active energy ray hardening The resin composition did not produce a sinking material even at room temperature (25. 〇 =1 =1), and the storage stability was good. The result of measuring the pencil hardness in the same manner was 5H. <Measurement method of wrong pen hardness> 1 . The method of making the hardened coating film is to use a bar coater in a triethylenesulfonated cellulose (TAC) film (film thickness 40 μm). Applying an energy ray curable resin composition (film thickness: 10 μm), drying at 7 (rc) for 2 minutes, using a high-pressure mercury lamp under nitrogen, and passing it under irradiation i of 250 mJ/cm 2 The test piece having a cured coating film was obtained by hardening. 2. Evaluation method of the cured coating film, and the cured coating film of the test piece was evaluated by a pencil line test using a load of 5 〇〇g according to JIS K5400. 6) ^ A dispersion was obtained in the same manner as in Example 除了 except that 25 g of the reactive dispersant (a-2) obtained in Production Example 2 was used instead of 25 g of the reactive dispersant (A-丨) of Example 1. The active energy ray curable resin composition did not precipitate even when stored at room temperature for 45 201200555 c) for 2 months, and the storage stability was good. The pencil hardness was measured in the same manner and the result was 5H. (Example 7) In the same manner as in Example 1, except that 25 g of the reactive dispersant (a-3) obtained in Production Example 3 was used instead of 25 g of the reactive dispersant (a-1) of Example 1, the dispersion was obtained. Active energy ray curable resin composition even in the room C) After 2 months of storage, the sediment was not produced, and the storage stability was good. The result of measuring the pencil hardness in the same manner was 5H. (Comparative Example 1) - obtained as a solid component leaf; 25 g of Production Example 1 Reactive dispersant (a 25g - pentaerythritol hexaacrylate (DPHA), 50g of dioxide dioxide particles (AER0SIL_5 (made by 曰f AEROSIL), average primary particle size of about 12nm) fine 'mixed' system The active energy ray-curable resin was stored at a temperature of (25 C) for 2 months, and no precipitate was produced. The dispersion of the formulation was carried out in a manner of 1 = 1 to form a hardened coating film, and the pencil was measured. Hardness, the result is 2H. (Comparative Example 2) In addition to the use of 5 〇g of bismuth propylene fluorene-modified dioxoparticles (gland 5 〇, Japan AEROSIL made by 'average primary particle diameter of 3 〇 nm) = (10) (8) side C V-550. And 2〇g二二= The way to get the volatilization into a reduction of 5 ()% _ compared to the control in the 100 copies of the comparative control with a reactive dispersion of 2 parts I e 184 'Compared An active energy ray curable resin composition is used. Comparative control active ray amount curable resin composition at room temperature (25. ( (Comparative Example 3) except that 5 parts by weight of Japanese AE L-modified with methyl propyl thorn group was used, the average primary particle diameter was 12 nm. A comparative control reactive dispersion having a nonvolatile content of 5% by weight was obtained in the same manner as in Example 〇 except for MIBK. Two parts of Irgacure 184 were added to the comparative control reactive dispersion in one part of the stomach to obtain a comparative active energy ray-curable resin composition. Comparative control The material was stored at room temperature (Μ 。) for 1 week at the room temperature (b). Further, a hardened coating film was produced in the same manner as in the case of the solid addition 4, and the pencil hardness was measured. As a result, it was 3H. [Simplified Schematic Description] A schematic diagram of the raw material slurry pulverization processing circuit of the above-described wet agitating ball mill for manufacturing a green hat of the present invention. A longitudinal sectional view of the above-described wet spoiler ball mill used for the manufacturing method of the present invention. In the manufacturing method of the mixing ball, the above-mentioned wet squeegee polishing 捣: a longitudinal sectional view of the supply port at the time of t, Ό, J:. Fig. 4 is a longitudinal sectional view showing a supply port when a medium is discharged. Mix the ball tree to discuss the dirty picture. [Fig. 6] A cross section showing a separator of the wet cake ball mill shown in Fig. 5 [Major component symbol description] 1 material tank; 2 material pump; 3 grinding type wet stirring ball mill; 4 separation 5 axis; 6 jacket; 7 stator; 9 spillway; 201200555 11 rotor; 12 motor; 13 pulley; 14 pulley; 15 rotor connector; 16 supply port; Net; 19 take-out; 21 disc; 22 blades; 23 regulator; 24 valve seat; 25 valve body; 26; cylinder; 27 inlet; 28 cylinder; 29 gas inlet; 30 electromagnetic switching valve; 31 piston; 32 rod; 33 spring; 34 nut; 43 shaft; 43a shoulder 43 shoulder 44 splitter; 45 partition, 45 rotor; 47 plug; 48 screw; 201200555 51 blade fitting groove; 52 round 53; blade; 54 overflow channel; 55 holes; 56 ί 状 隔板, 58 valves; 59 valves; 60 valves; 61 valves; 62 valves; 63 product slots.

Claims (1)

201200555 七、申請專利範圍： 1.一種分散體，係經表面處理的無機粒子（A)分 反應 分散劑者，其特徵為： ~ 1) 經表面處理的無機粒子（A)是藉由以具有（甲基）丙稀 醯基的化合物⑻對無機粒子⑻進行表面處理而得者， 2) 反應性分散劑是使具有（甲基）丙烯醯基和羧基的單體(Μ) 與具J環氧基的（甲基）_酸聚合物⑷進行加成反應而得 之反應生成物，或使具有（曱基）丙烯醯基和環氧基的單體（b2 =她基的（甲基）丙烯酸聚合物⑽進行加成反應而得之 1生成/^且（甲基）丙稀酿基當量為2〇〇〜6〇〇，經基值為9〇 〜280mg/KOH。 r田^申ΐ專利範關1項之分散體，其中，該反應性分散劑的 (甲基）丙烯醯基當量為200〜400，經基值為14〇〜28〇mg/K〇H。 3. 如申請專利範圍第i或2項之分散體，射，該反秦 ，是使（甲基）丙稀酸，與使（甲基）丙烯酸縮水甘油醋^合所 付的具有環氧基的（甲基）丙烯酸聚合物進行加成反應而得。 4. 如申請專利範圍第1〜3項中任一項之分 1 應性分散劑的重量平均分子量為5,〇〇〇〜10〇,〇〇〇。八 。 5·如申請專利範圍第丨〜4項中任一項之分 立 機粒子（c)的初級粒徑為10nm〜300nm。 ’、 έ、、、、 機也？利範圍第1〜5項中任—項之分散體，其中，該益 機粒子（C)為二氧化石夕微粒。 … 有/甲利範Μ1〜6項中任—項之分散體，其中，該罝 触基的化合物(Β)是以通式⑴所表示的有機 Ο OR- (1) R2〇—Si—(CH2)n·—Ο V L3 (ch3) (式中，R!、R2、R3各自獨立，為碳數為i〜4的絲，n為 50 201200555 4 〜6的整數）。 量射線硬化性樹脂組3利賴第1〜7項中任一項之分散體的能 與排出口連接,S么开ϊ=、=γ的•料的轉子、以及 旋轉’並藉峰^力作用2 ’或與轉子各自獨立且 的葉輪型分離器； 77 料’將漿料從排出口排出 機粒項中任一項的該無 流㈣== 賴nr及，分散劑後二子料内中進：：。二氧化 疋粒徑為15二ΙΟΟμιη 介質 11.一種能量射線硬化性樹脂組合，^ ^ 專利範圍9該的製造方法而得的分散^。，、特徵在於含有以申請 第8二，篇射£更在=^^ 明專利範圍第12項的膜，其中，該 a 對苯二甲酸乙二醇醋樹脂的膜狀基材、 和， 相對於膜狀基材賴厚為3〜職項的膜’其中該硬化層的膜厚 八、圖式： 51201200555 VII. Patent application scope: 1. A dispersion, which is a surface-treated inorganic particle (A), which is characterized by the following: ~ 1) The surface-treated inorganic particles (A) are The (meth) acrylonitrile-based compound (8) is obtained by surface-treating the inorganic particles (8), 2) the reactive dispersant is a monomer having a (meth) acrylonitrile group and a carboxyl group (Μ) and a ring J a reaction product obtained by an addition reaction of an oxy (meth)-acid polymer (4), or a monomer having a (fluorenyl) acrylonitrile group and an epoxy group (b2 = her group (meth) The acrylic polymer (10) is subjected to an addition reaction to obtain a product of 1 Å and a (meth) propylene equivalent weight of 2 〇〇 to 6 〇〇, and a base value of 9 〇 to 280 mg / KOH. The dispersion of Patent No. 1, wherein the reactive dispersant has a (meth) acrylonitrile equivalent of 200 to 400 and a base value of 14 〇 28 〇 mg / K 〇 H. The dispersion of the range i or 2, shot, the anti-Qin, is made of (meth)acrylic acid, and the (meth)acrylic acid glycidol vinegar The epoxy group-containing (meth)acrylic acid polymer is subjected to an addition reaction. 4. The weight average molecular weight of the one-component dispersant according to any one of claims 1 to 3 is 5 , 〇〇〇 〇 〇 〇 〇 〇 〇 〇 〇 5 5 5 5 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 分 分 分 分 分And the machine is also a dispersion of any of the items 1 to 5 in the range of interest, wherein the probiotic particles (C) are particles of the cerium dioxide. a dispersion in which the compound (Β) of the oxime group is an organic oxime OR-(1) R2〇—Si—(CH 2 ) n·—Ο V L3 (ch3) represented by the formula (1) (wherein R!, R2, and R3 are each independently, and are carbons having a carbon number of i to 4, and n is an integer of 50 201200555 4 to 6.) The ray-curable resin group 3 is dispersed in any one of the first to seventh items. The body can be connected to the discharge port, the rotor of the material, the rotor of the material, and the impeller type separator that rotates and is independent of the rotor; 77 The slurry is discharged from the discharge port to the no-flow of any one of the machine particles (4) == 赖nr and the second sub-material of the dispersant is:: the particle size of the cerium oxide is 15 ΙΟΟμιη medium 11. An energy ray The curable resin combination, the dispersion obtained by the manufacturing method of the ninth patent, is characterized in that it contains a film which is applied in the eighth item of the application, and is in the 12th item of the patent range of the invention. The film-form substrate of the a-terephthalic acid glycol vinegar resin, and the film having a thickness of 3 to the film-like substrate, wherein the film thickness of the hardened layer is eight, and the pattern: 51
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