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TW201127480A - Method for producing silica dispersing element, energy-ray curable resin composition, and film - Google Patents

Method for producing silica dispersing element, energy-ray curable resin composition, and film Download PDF

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Publication number
TW201127480A
TW201127480A TW099120036A TW99120036A TW201127480A TW 201127480 A TW201127480 A TW 201127480A TW 099120036 A TW099120036 A TW 099120036A TW 99120036 A TW99120036 A TW 99120036A TW 201127480 A TW201127480 A TW 201127480A
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Taiwan
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meth
group
acrylic polymer
acrylate
fluorenyl
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TW099120036A
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Chinese (zh)
Inventor
Youichi Tanimoto
Yasuyuki Watanabe
Masao Yamada
Hisayoshi Arai
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Dainippon Ink & Chemicals
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    • 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
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F27/00—Mixers with rotary stirring devices in fixed receptacles; Kneaders
    • B01F27/80—Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a substantially vertical axis
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • 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
    • 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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Mixers Of The Rotary Stirring Type (AREA)

Abstract

To provide a method for easily and simply producing a silica dispersing element which is excellent in storage stability and is obtained by dispersing silica microparticulates in an active energy-ray curable resin composition. The silica dispersing element is produced by dispersing silica microparticulates (F) in a (meth)acrylic polymer (B) having (meth)acryloyl groups and hydroxy groups in the molecular structure, the (meth)acryloyl equivalent being in the range of 200-600 g/eq and the hydroxyl value being in the range of 90-280 mg-KOH/g. In the method for producing the silica dispersing element, a wet ball mill 3 having an impeller-type separator 4 is used; media and slurry are agitated and mixed in the inside of the wet ball mill; the silica microparticulates (F) in the slurry are crushed and dispersed into the (meth)acrylic polymer (B); and the slurry and the media are separated by the action of centrifugal force in an impeller-type separator section.

Description

201127480 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種將二氧化矽微粒子分散在活性能量 線硬化型組合物中而形成的貯存穩定性優異的分散體的製 造方法、含有藉由該製造方法得到的分散體的能量線硬化 型樹脂組成物、具有使該組合物硬化而得之硬化層之膜、 二氧化石夕微粒用反應性分散媒介、以及二氧化矽^粒用反 應性分散劑。 【先前技術】 為了提高硬化塗膜(使活性能量線硬化型樹脂組成物硬 化而得到）的硬度’有將二氧切微粒分散在活性能量線硬 化型樹脂組成物中的方法。二氧化輕粒有利用渴式法製 造的膠態二氧切，或㈣乾式法製造的煙氣二氧化石夕。 二氧化石夕微粒表面有石夕醇基，二氧化石夕微粒是親水性的。 因此，與作為活性能量線硬化型單體、寡聚物等的組成物 中之主成分的有機相的親和性差。另夕卜二氧化錢粒的 匕重比有機相A。因此’使二氧化矽微粒在活性能量線硬 化型樹脂組成物中達到長時間穩定分散通常是固難的，含 有二氧切微粒的活性能量線硬化型樹脂組成物如果進行 長時間放置，：氧切微粒會發生㈣與沉降等貯存穩 定性差。另外’二氧切微粒通常會因作用於—次粒子間、 的分子間力及靜電力等發生強烈地凝集，這也對貯存穩定 性產生不良影響。 “ 作為使二氧化石夕微粒穩定地分散在活性能量線硬化型 4 201127480 树脂組成物中的方法，例如已記載有利用具有疏水性基團 的反應性㈣偶聯劑對二氧化輕粒進行表面處理，將二 氧化石夕微粒表面疏水化的方法（例如，參見專利文獻！），但 是，即便藉由專利文獻1中記載的方法得到的：氧化㈣ 粒，在活性能量線硬化型樹脂組成物中的分散穩定性仍献 不足，如果在室溫下保存―肖，就會產生二氧切微粒的 沉降物。另外，還需要除去使时㈣聯劑進行表面處理 後的副產物、詩賦予料散性而進行的溶劑濃縮及溶 劑置換等煩雜的製造步驟，在經濟上亦不佳。 專利文獻η日本特開2006— 348196號公報（第12頁） 【發明内容】 本發明要解決之課題，係在於提供一種製造方法：即 可容易且簡便地製造貯存安定性優異之分散體，該分散體 係將一氧化石夕微粒分散在活性能量線硬化型组成物中而 成。又在於提供-種含有藉由此製造方法得到之分散體且 二氧化石夕微粒能夠長時間保持穩定之分散狀態的能量線硬 化型樹月曰組成物、&以具有該&量線硬化型樹脂組成物的 硬化層作為硬塗層之膜。 為了解決上述問題’本發明人等進行了深入研究，結 果發現’作為將^氧化石夕微粒⑺分散於（甲基）丙稀酸系聚 。物（B)(分子結構中具有（曱基）丙烯醯基與羥基且（曱基） 丙烯醯基當1在2〇〇〜6〇〇g/eq的範圍、羥基值在9〇〜 280mgKOH/g的範圍）的分散體之製造方法，使用具有葉輪 型分離器的濕式球磨機’將介質與漿料在該濕式球磨機内 201127480 部授拌混合，錢❹的：氧切録（F)粉碎並分散在（甲 基)丙稀酸系聚合物(B)中，且在葉輪型分離器部藉由離心力 作用使漿料與介質分離，從而得到 J忖則刀散體，藉由使用此方 法可以容易且簡便地製造貯存稃 于德疋性優異的二氧化矽分散 體等，從而完成了本發明。 即’本發明關於-種分散體的製造方法，其特徵在於， 將含有（甲基）丙稀it系聚合物（B)(分子結構中且有（甲基）丙 稀醯基與經基，且（甲基）丙烯酿基當量在扇〜的 範圍、經基值在90〜·mgK〇H/g的範圍）與二氧化石夕微粒 (F)的衆料，從包含以下構件的濕式球磨機之毅料供給口供 給到定子内： 1) 内部填充有介質的圓筒形定子、 2) 設置於該定子下端的聚料供給口、 3) 位於該定子的軸心’且其上部設置有中空狀液體排放 通道之進行旋轉驅動的旋轉軸、 4) 與該旋轉軸進行同軸旋轉驅動的轉子、與 5) 以同軸Μ置於該旋轉軸上部i以與該/中空狀液體 排放通道連通而排出分離液之方式所構成之進行旋轉驅動 的葉輪型分離器； 在定子内旋轉驅動該轉子以攪拌混合介質與漿料，使 得漿料中的二氧化矽微粒（F)粉碎並分散至（甲基）丙烯酸系 聚合物（Β)，且在旋轉驅動的分離器部藉由離心力作用使漿 料與介質分離’將被誘導到分離器轴心部的毁料從該旋轉 軸内的中空狀排放通道排出。 進而，本發明係關於一種能量線硬化型樹脂組成物， 6 201127480 其特徵在於，含有藉由上述製造方法得到之分散體。 進而，本發明係關於一種膜，其特徵在於，在膜狀基 材上具有使上述能量線硬化型樹脂組成物硬化而得到之硬 化層。 進而，本發明係關於一種二氧化矽微粒用反應性分散 媒介，其特徵在於，含有（甲基）丙烯酸系聚合物⑺），該（甲 基）丙烯酸系聚合物（B)分子結構中具有（甲基）丙烯醯基與羥 基且（甲基）丙烯醯基當量在200〜600g/eq的範圍、羥基 值在90〜280mgKOH/g的範圍。 進而，本發明係關於一種二氧化矽微粒用反應性分散 劑，其特徵在於，含有（曱基）丙烯酸系聚合物（B)，該（甲基） 丙烯酸系聚合物（B)分子結構中具有（甲基）丙烯醯基與羥 基，且（曱基）丙烯醯基當量在2〇〇〜6〇〇g/eq的範圍、羥基 值在90〜2 80mgKOH/g的範圍。 根據本發明，可以容易且簡便地製造貯存安定性優異 之为政體（係將一氧化石夕微粒分散在活性能量線硬化型組成 物中而成）。又，可提供一種二氧化矽微粒能長時間穩定保 持刀散狀態的能篁線硬化型樹脂組成物。又’本發明可提 供一種具有高硬度硬化層之膜。並且，本發明可提供一種 能適用於分散二氧化矽微粒的反應性分散劑。 【實施方式】 本發明中使用的（曱基）丙烯酸系聚合物係用作為： 用於使一氧化石夕微粒（F)分散的反應性分散媒介、或用於使 二氧化石夕微粒（F)分散在後述之（曱基）丙烯酸系聚合物（B)以 201127480 外的具有（曱基）丙烯醯基之化合物中的分散劑，其特徵在 於’分子結構中具有（曱基）丙烯醯基與羥基，且（甲基）丙稀 醢基當量在200〜600g/eq的範圍、羥基值在9〇〜 280mgKOH/g的範圍。此處，（曱基）丙烯醯基當量是指每1 莫耳（甲基）丙烯醯基（指丙烯醯基及/或曱基丙烯醯基）的（甲 基）丙烯醢酸系聚合物（B)的固體成分重量（g/eq)。藉由使（甲 基）丙烯醯基當量處於200〜600g/eq範圍内，可以達成高交 聯密度，該結果可達到高硬度。另外，本發明的（曱基）丙烯 酸系聚合.物（B)具有羥基，該羥基與二氧化矽微粒表面上存 在的矽醇基形成氫鍵。藉由使羥基值處於9〇〜28〇mgK〇H/g 的範圍内，可以（甲基）丙烯酸系聚合物（B)密集地覆蓋二氧 化矽表面，可實現高分散性。藉此可以使分散於（甲基）丙烯 酸系聚合物（B)中的二氧化矽微粒長時間地穩定存在於活性 能量線硬化型樹脂組成物中。 本發明的（甲基）丙烯酸系聚合物（B)具有的（甲基）丙烯 醯基當量較佳在200〜400g/eq的範圍。另外，羥基值較佳 在140〜280mgKOH/g的範圍。藉由使（甲基）丙烯醯基與羥 基值處於此等範圍内，可使得到的分散體的分散穩定性優 異，且可使使用有該分散體之活性能量線硬化型樹脂組成 物的硬化塗膜成為高硬度塗膜。 上述（甲基）丙稀酸系聚合物（B)，例如可舉出使具有（甲 基）丙烯醯基及羧基的單體（(〇與具有環氧基的（甲基）丙烯酸 系聚合物（al)進行加成反應而形成的反應生成物（bl)、使具 有（甲基）丙烯醯基及環氧基的單體（d)與具有羧基的單體（甲 基）丙烯酸系聚合物（a2)進行加成反應而形成的反應生成物 201127480 (b2)、以及使具有一個異氰酸酯基及（甲基）丙烯醯基的單體 (e)與具有羥基的（甲基）丙烯酸系單體（a3)進行加成反應而 形成的反應生成物（b3)等。 在製備上述反應生成物（bi)中使用的具有環氧基的（曱 基）丙烯酸系聚合物（al)，例如可以利用具有（甲基）丙烯醯基 及環氧基的聚合性單體的均聚反應或與其他聚合性單體的 共聚反應而得到。 上述具有（甲基）丙烯醯基及環氧基的聚合性單體，例如 可舉出（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）丙烯酸縮水甘油酯、〇 _正丁 基（曱基）丙烯酸縮水甘油酯、（甲基）丙烯酸一 3,4一環氧基丁 酯、（甲基）丙烯酸一4,5 —環氧基戊酯、（甲基）丙烯酸一 6,7 一裱氧基戊酯、α —乙基（曱基）丙烯酸_ 6,7 —環氧基戊 酯、/5 —甲基縮水甘油基（甲基）丙烯酸酯、（甲基）丙烯酸— 3,4一環氧基環己酯、内酯改質（曱基）丙烯酸一 一環氧基 %己酯、乙烯基環氧己烷等。這些單體可以單獨使用，也 可以同時使用2種以上。 (曱基）丙烯酸系聚合物（al)可以是具有（曱基）丙烯醯基 及環氧基的聚合性單體的均聚物，也可以是與其他聚合性 單體的共聚物。為與其他聚合性不飽和單體的共聚物時， 使用上較佳為〔具有（曱基）丙烯醢基及環氧基的聚合性單 體〕：〔其他聚合性單體〕為25〜1〇〇質量份：75〜〇質量 伤之範圍，更佳為40〜100質量份：6〇〜〇質量份之範圍。 在製備上述反應生成物（b2}中使用的具有羧基的（甲基） 丙烯I系聚合物（a2)，例如可以藉由具有（甲基）丙烯醯基及 201127480 羧基的聚合性單體的均聚反應 '或與其他聚合性單體的丑 聚反應而得到。 ^ 具有（曱基）丙稀醯基及叛基的聚合性單體，例如可I (甲基）丙稀酸；召一缓基乙基（曱基）丙埽酸醋、2 —丙歸酉盘& 基乙基破ί6酸S旨、2—丙稀酿氧基乙基鄰苯二甲酸自t 2 丙烯醯氧基乙基六氫鄰苯二曱酸酯及該等之内 _曰P又買物等 具有酯鍵的不飽和單羧酸；馬來酸等。這些單體可 。 A平獨 使用，也可以同時使用2種以上。 (甲基）丙稀酸系聚合物（a2)亦可為具有（曱基）丙稀醯基 及叛基的聚合性單體的均聚物，亦可為與其他聚合性單^ 的共聚物。為與其他聚合性單體的共聚物時，使用上較& 為〔具有（甲基）丙烯醯基及羧基的聚合性單體〕：〔其他聚^ 合性單體〕為25〜100質量份：75〜〇質量份之範圍，更佳 為40〜100質量份：60〜0質量份之範圍。 在製備上述反應生成物（b3)中使用的具有羥基的（曱基） 丙烯酸系聚合物（a3) ’例如可以藉由具有（甲基）丙烯醯基及 羥基的聚合性單體的均聚反應、或與其他聚合性單體的共 聚反應而得到。 具有（甲基）丙稀酿基及輕基的聚合性單體，例如可舉出 丙烯酸2 _羥基乙酯、丙烯酸2 —羥基丙酯、丙烯酸4 —經 基丁酯、丙稀酸2，3—二經基丙酯、曱基丙稀酸2 —經基乙 酯、曱基丙烯酸2 —羥基丙酯、甲基丙烯酸4 —羥基丁醋、 曱基丙烯酸2,3 —二羥基丙酯等。這些單體可以單獨使用， 也可以同時使用2種以上。 (甲基）丙烯酸系聚合物（a3)亦可為具有（甲基）丙烯醯基 201127480 及經基的聚合性單體的均聚物，亦可為與其他聚合性單體 的共聚物。為與其他聚合性單體的共聚物時，使用上較佳 為〔具有（曱基）丙烯醯基及羥基的聚合性單體〕：〔其他聚 合性單體〕為25〜100質量份：75〜〇質量份之範圍更佳 為40〜100質量份：6〇〜〇質量份之範圍。 製備（甲基）丙烯酸系聚合物（al)、（a2)及（a3)時進行共聚 的上述其他聚合性單體，例如可舉出以下的聚合性單體。 (!)(曱基）丙烯酸曱酯、（甲基）丙烯酸乙酯、（甲基）丙烯 酸丙酯、（曱基）丙烯酸正丁酯、（曱基）丙烯酸三級丁酯、（甲 基）丙烯酸己酯、（曱基）丙烯酸庚酯、（甲基）丙烯酸辛酯、（曱 基）丙烯酸壬酯、（曱基）丙烯酸癸酯、（曱基）丙烯酸十二烷基 酯、（曱基）丙烯酸十四烷基酯、（甲基）丙烯酸十六烷基酯、（曱 基）丙烯酸硬脂酯、（甲基）丙烯酸十八烷基酯、（甲基）丙烯酸 二十二烷基酯等具有碳原子數為1〜22的烷基的（曱基）丙 烯酸酯類； (2) (甲基）丙烯酸環己酯、（曱基）丙烯酸異冰片酯、（甲 基）丙烯酸雙環戊酯、（曱基）丙烯酸雙環戊烯基氧乙酯等具 有脂環式烷基的（甲基）丙烯酸酯類； (3) (曱基）丙烯酸苯甲醯氧乙酯、（甲基）丙烯酸苄酯、（甲 基）丙稀酸苯乙酯、（曱基）丙烯酸苯氧乙酯、（曱基）丙烯酸笨 氧基二乙二醇酯、（甲基）丙烯酸2 —羥基一 3 —苯氧基丙酯 等具有芳香環的（甲基）丙烯酸酯類； (4) (甲基）丙烯酸羥乙酯；（曱基）丙烯酸羥丙酯、（甲基） 丙稀酸經丁酯、（曱基）丙烯酸甘油酯；内酯改質（曱基）丙稀 酸經乙酿、（甲基）丙烯酸聚乙二醇酯、（甲基）丙烯酸聚丙二 201127480 醇酯等具有聚烷撐二醇基的（甲基）丙烯酸酯等具有經燒基 的丙烯酸酯類； (5 )反丁稀—酸二曱S旨、反丁稀—酸二乙S旨、反丁稀二 酸二丁酯、伊康酸二甲酯、伊康酸二丁酯、反丁稀二酸甲 基乙酯、反丁烯二酸甲基丁酯、伊康酸甲基乙酯等不飽和 二羧酸酯類； (6) 苯乙烯、α —甲基苯乙烯、氣笨乙烯等苯乙烯衍生 物類； (7) 丁二烯、異戊二烯、戊間二烯、二曱基丁二稀等二 稀系化合物； (8) 氣乙烯、演乙稀等鹵乙稀及偏鹵乙稀類； (9) 曱基乙稀基酮、丁基乙稀基嗣等不飽和酮類； (10) 醋酸乙稀δ旨、丁酸乙稀醋等乙稀基自旨類； (Π)甲基乙烯基鍵、丁基乙烯基醚等乙稀基醚類； (12)丙烯腈、甲基丙烯腈、偏氰乙烯等氰化乙稀類； (1 3)丙烯醯胺及其醇酸取代醯胺類； (14) Ν —笨基馬來醢亞胺、ν —環己基馬來醯亞胺等Ν 一取代馬來醯亞胺類； (15) 氟乙烯、偏氟乙烯、三氟乙烯、氣三氟乙烯、溴三 氟乙烯、五氟丙烯或六氟丙烯之類的含氟α—烯烴類；或 二氟甲基二氟乙烯基醚、五氟乙基三氟乙烯基醚或七氟丙 基三氟乙烯基醚之類的（全）氟烷基的碳原子數為丨至18的 (全）氟烷基.全氟乙烯基醚類；2,2,2—三氟乙基（甲基）丙烯 酸醋、2,2,3,3 —四氟丙基（曱基）丙烯酸酯、1Η，1Η,5Η—八氟 戍基（甲基）丙稀酸醋、1Η，1Η，2Η,2Η~十七氟癸基（曱基）丙 12 201127480 稀酸s旨或全氟乙基氧乙基（甲基）丙烯酸酯之類的（全）氟烷基 的碳原子數為1至18的（全）氟烷基（甲基）丙烯酸酯類等含氟 乙稀性不飽和單體類； (16) T —曱基丙烯醢氧丙基三曱氧基矽烷等含有矽基 的（甲基）丙稀酸酯類； (17) Ν，Ν—二甲基氨基乙基（甲基）丙烯酸酯、ν，ν —二乙 基氨基乙基（甲基）丙烯酸酯或Ν，Ν—二乙基氨基丙基（甲基） 丙烯酸酯等Ν，Ν —二烷基氨基烷基（甲基）丙烯酸酯等。 製備此等（曱基）丙烯酸系聚合物（al)、（a2)及（a3)時所使 用的其他I 5性不飽和單 '體，可以單獨使用，也可以併用2 種以上。 上述（甲基）丙烯酸系聚合物（al)、（a2)&(a3)，若使用公 知慣用的方法進行聚合（共聚）即可得到，其共聚方式沒有特 别地限制。可以在催化劑（聚合起始劑）的存在下，藉由加成 聚合進行製造，可以是隨機共聚物、嵌段共聚物、接枝共 聚物等中的任-種。另外，聚合方法也可以使用本體聚合、 溶液聚合、懸浮聚合、乳化聚合中等公知的聚合方法。 此處，作為溶液聚合等中可以使用溶劑，若列舉 性：劑，如可舉出丙酮、甲基乙基酮、甲基正丙基嗣、 甲基異丙基酮、甲基正丁基酮、甲基 正丙基 基酮、甲其並Τ &正戊 土】甲基正己基酮、二乙酮、乙基正丁基酮 酮、二異丁基酮、環己酮 '佛爾鲖等酮系溶劑 乙 乙 乙趟、異丙基越、正丁基鱗、二異戊基醚 醇 甲基驗、乙二醇二乙驗、二乙二醇二甲基峻、 二氧六環、四氫呋喃等醚系溶劑； 201127480 曱酸乙酯、甲酸丙酯、甲酸正丁酯、醋酸乙酯、醋酸 正丙S旨、醋酸異丙醋、 單曱基醚醋酸酯、乙二 、醋酸正丁酯、醋酸正戊酯、乙二醇 二醇單乙醚醋酸酯、二乙二醇單曱基 醚醋酸酯'二乙二醇單乙醚醋酸酯'丙二醇單甲基醚醋酸 酯、乙基一3 —乙氧基丙酸酯等酯系溶劑； 、正丁醇、異丁醇、二丙酮醇、2 甲氧基一1 — 丁醇、3 —曱基一3 — 甲苯、SOLVESSO 1〇〇、SOLVESSO 150、[Technical Field] The present invention relates to a method for producing a dispersion excellent in storage stability by dispersing cerium oxide fine particles in an active energy ray-curable composition, and The energy ray-curable resin composition of the dispersion obtained by the production method, the film having the hardened layer obtained by curing the composition, the reactive dispersion medium for the silica dioxide particles, and the reactivity of the cerium oxide particles Dispersant. [Prior Art] In order to increase the hardness of the cured coating film (obtained by hardening the active energy ray-curable resin composition), there is a method of dispersing the oxidized particles in the active energy ray-hardening resin composition. The dioxide light particles have a colloidal dioxygen cut produced by a thirst method, or a (four) dry method of flue gas dioxide. The surface of the dioxide dioxide particles has a stone base, and the particles of the dioxide are hydrophilic. Therefore, the affinity to the organic phase which is a main component in the composition of the active energy ray-curable monomer or oligomer is inferior. In addition, the weight of the dihydrated particles is higher than that of the organic phase A. Therefore, it is usually difficult to achieve stable dispersion of the cerium oxide microparticles in the active energy ray-curable resin composition for a long period of time, and if the active energy ray-curable resin composition containing the oxidized particles is placed for a long time, oxygen is used. The cut particles will occur (4) and the storage stability such as sedimentation is poor. Further, the diced particles are strongly agglomerated by the intermolecular force and electrostatic force acting between the secondary particles, which also adversely affects storage stability. "As a method of stably dispersing the silica fine particles in the active energy ray-curable type 4 201127480 resin composition, for example, surface of the oxidized light granules using a reactive (tetra) coupling agent having a hydrophobic group has been described. The method of hydrophobizing the surface of the cerium oxide particles (for example, see the patent document!), but the oxidized (tetra) granule obtained by the method described in Patent Document 1, the active energy ray-curable resin composition The dispersion stability in the medium is still insufficient. If the "Sha" is stored at room temperature, the sediment of the dioxo particles will be produced. In addition, it is necessary to remove the by-products and poetry materials after the surface treatment of the (4) crosslinking agent. The troublesome manufacturing steps, such as solvent concentration and solvent replacement, which are carried out in a dispersive manner, are not economically advantageous. Patent Document η-JP-A-2006-348196 (page 12) [Disclosure] The problem to be solved by the present invention is It is to provide a manufacturing method in which a dispersion excellent in storage stability can be easily and easily produced, and the dispersion disperses the cerium oxide particles It is formed in an active energy ray-curable composition, and further provides an energy ray-curable tree sputum composition containing a dispersion obtained by the production method and a dispersed state in which the cerium oxide particles can be stably maintained for a long period of time. And a hardened layer having the & wire-curing resin composition as a film of a hard coat layer. In order to solve the above problem, the present inventors conducted intensive studies and found that 'as a oxidized stone particle (7) Dispersed in (meth)acrylic acid-based polymer (B) (having (fluorenyl) acrylonitrile group and hydroxyl group in the molecular structure and (mercapto) acryl fluorenyl group when 1 in 2〇〇~6〇〇g a method for producing a dispersion having a range of /eq and a hydroxyl value in the range of 9 〇 to 280 mgKOH/g, using a wet ball mill having an impeller type separator to mix the medium and the slurry in the wet ball mill 201127480 Mixing, money :: oxygen cutting (F) is pulverized and dispersed in the (meth) acrylic acid polymer (B), and the slurry is separated from the medium by centrifugal force in the impeller type separator portion, thereby Get the J忖 knife, by using this The present invention can be easily and easily produced by dissolving a cerium oxide dispersion or the like which is excellent in Germanium, etc., which is a method for producing a dispersion of the present invention, which is characterized in that it contains (methyl ) propylene-based polymer (B) (molecular structure and (meth) propyl sulfhydryl group and warp group, and (meth) propylene base equivalent in the range of fan ~, the base value is 90~ The range of mgK〇H/g) and the mass of the silica dioxide particles (F) are supplied to the stator from the supply port of the wet ball mill containing the following components: 1) Cylindrical stator filled with medium inside 2) a collecting supply port provided at the lower end of the stator, 3) a rotating shaft located at the axial center of the stator and having a hollow liquid discharge passage on the upper portion thereof, 4) rotating coaxially with the rotating shaft a driven rotor and 5) an impeller-type separator that is coaxially disposed on the upper portion of the rotating shaft and that communicates with the hollow liquid discharge passage to discharge the separation liquid, and is rotationally driven in the stator; The rotor is stirred and mixed And the slurry, so that the cerium oxide particles (F) in the slurry are pulverized and dispersed to the (meth)acrylic polymer (Β), and the slurry and the medium are caused by centrifugal force in the rotary driven separator portion. The separation 'disintegration that is induced into the core of the separator is discharged from the hollow discharge passage in the rotating shaft. Further, the present invention relates to an energy ray-curable resin composition, and 6, 201127480, which comprises a dispersion obtained by the above production method. Furthermore, the present invention relates to a film comprising a hardened layer obtained by curing the energy ray-curable resin composition on a film-form substrate. Further, the present invention relates to a reactive dispersion medium for cerium oxide microparticles, which comprises a (meth)acrylic polymer (7)) having a molecular structure (B) The methyl group has a fluorenyl group and a hydroxyl group, and the (meth) acrylonitrile group has an equivalent weight in the range of 200 to 600 g/eq and a hydroxyl value in the range of 90 to 280 mg KOH/g. Further, the present invention relates to a reactive dispersant for cerium oxide microparticles, comprising a (fluorenyl)acrylic polymer (B) having a molecular structure in the (meth)acrylic polymer (B) The (meth) acrylonitrile group and the hydroxy group have a (fluorenyl) acrylonitrile group equivalent weight in the range of 2 〇〇 6 6 g/eq, and a hydroxyl value in the range of 90 〜 2 80 mg KOH / g. According to the present invention, it is possible to easily and easily produce a government body having excellent storage stability (which is obtained by dispersing fine particles of monoxide in an active energy ray-curable composition). Further, it is possible to provide a krypton-curable resin composition in which the cerium oxide fine particles can stably maintain the state of the knives for a long period of time. Further, the present invention can provide a film having a hardened layer of high hardness. Further, the present invention can provide a reactive dispersant which can be suitably used for dispersing cerium oxide microparticles. [Embodiment] The (fluorenyl) acrylic polymer used in the present invention is used as: a reactive dispersion medium for dispersing monolithic particles (F), or for making silica dioxide particles (F) a dispersing agent dispersed in a compound having a (fluorenyl) acrylonitrile group other than 201127480, which is a (mercapto) acryl fluorenyl group in a molecular structure. With a hydroxyl group, the (meth) acrylonitrile group equivalent is in the range of 200 to 600 g/eq, and the hydroxyl value is in the range of 9 Å to 280 mg KOH/g. Here, the (mercapto) acrylonitrile-based equivalent means a (meth)acrylic acid-based polymer per 1 mole of (meth)acrylonitrile group (referred to as an acrylonitrile group and/or a mercapto propylene group) ( B) solid component weight (g/eq). By setting the (meth)acrylonitrile equivalent in the range of 200 to 600 g/eq, a high crosslinking density can be achieved, and as a result, high hardness can be attained. Further, the (mercapto)acrylic acid-based polymer (B) of the present invention has a hydroxyl group which forms a hydrogen bond with a sterol group present on the surface of the ceria particle. By setting the hydroxyl value in the range of 9 Torr to 28 〇 mg K 〇 H / g, the (meth)acrylic polymer (B) can be densely covered with the surface of the ruthenium dioxide, and high dispersibility can be achieved. Thereby, the cerium oxide fine particles dispersed in the (meth)acrylic polymer (B) can be stably present in the active energy ray-curable resin composition for a long period of time. The (meth)acrylic polymer (B) of the present invention preferably has a (meth)acryl oxime equivalent weight in the range of 200 to 400 g/eq. Further, the hydroxyl value is preferably in the range of from 140 to 280 mgKOH/g. By setting the (meth) acrylonitrile group and the hydroxyl value in the above range, the dispersion stability of the obtained dispersion can be excellent, and the hardening of the active energy ray-curable resin composition using the dispersion can be obtained. The coating film becomes a high hardness coating film. The (meth)acrylic acid-based polymer (B) may, for example, be a monomer having a (meth)acryl fluorenyl group and a carboxyl group ((anthracene and (meth)acrylic polymer having an epoxy group) (al) a reaction product (bl) formed by an addition reaction, a monomer (d) having a (meth)acryl fluorenyl group and an epoxy group, and a monomer (meth)acrylic polymer having a carboxyl group (a2) a reaction product 201127480 (b2) formed by an addition reaction, and a monomer (e) having one isocyanate group and (meth)acryl fluorenyl group and a (meth)acrylic monomer having a hydroxyl group (a3) The reaction product (b3) or the like which is formed by the addition reaction. The (fluorenyl) acrylic polymer (al) having an epoxy group used in the preparation of the above reaction product (bi) can be used, for example. A homopolymerization reaction of a polymerizable monomer having a (meth) acrylonitrile group and an epoxy group or a copolymerization reaction with another polymerizable monomer. The above polymerizable property having a (meth) acrylonitrile group and an epoxy group Examples of the monomer include glycidyl (meth)acrylate and α. Glycidyl ethyl (meth)acrylate, glycidyl α-n-propyl (meth)acrylate, glycidyl hydrazide-n-butyl(meth)acrylate, a 3,4-ring of (meth)acrylic acid Oxybutyl butyl ester, 4,5-epoxypentyl (meth)acrylate, 6,7-decyloxypentyl (meth)acrylate, α-ethyl(fluorenyl)acrylic acid _ 6,7 - epoxy pentanyl ester, /5-methyl glycidyl (meth) acrylate, (meth)acrylic acid - 3,4-epoxycyclohexyl ester, lactone modified (mercapto) acrylic acid - one by one Epoxy group hexyl ester, vinyl hexylene hexane, etc. These monomers may be used singly or in combination of two or more kinds. The (fluorenyl) acryl-based polymer (al) may have (fluorenyl) acrylonitrile. The homopolymer of the polymerizable monomer of the epoxy group and the epoxy group may be a copolymer with another polymerizable monomer. When it is a copolymer with another polymerizable unsaturated monomer, it is preferably used [with ( Mercapto group) polymerizable monomer of acrylonitrile group and epoxy group]: [other polymerizable monomer] is 25 to 1 part by mass: 75 The range of the mass damage of the 〇 , is more preferably 40 to 100 parts by mass: the range of 6 〇 to 〇 by mass. The (meth) propylene I-based polymer having a carboxyl group used in the preparation of the above reaction product (b2) ( A2) can be obtained, for example, by a homopolymerization reaction of a polymerizable monomer having a (meth)acrylinyl group and a 201127480 carboxyl group or an oligopolymerization reaction with another polymerizable monomer. ^ (曱) propylene A thiol-based and a thiol-containing polymerizable monomer, for example, I (meth)acrylic acid; a sulfoethyl (mercapto) propionate vinegar, a 2-propyl hydrazine platter & Acid S, 2-propylene oxyethyl phthalic acid from t 2 propylene oxiranyl ethyl hexahydrophthalic acid ester and these have no ester bond Saturated monocarboxylic acid; maleic acid, and the like. These monomers are available. A can be used alone or in combination of two or more types. The (meth)acrylic acid polymer (a2) may also be a homopolymer of a polymerizable monomer having a (fluorenyl) acrylonitrile group and a thiol group, or a copolymer with other polymerizable monomers. . In the case of a copolymer with another polymerizable monomer, the above-mentioned & is [polymerizable monomer having a (meth) acrylonitrile group and a carboxyl group]: [other polymerizable monomer] is 25 to 100 mass. Parts: 75 to 〇 parts by mass, more preferably 40 to 100 parts by mass: 60 to 0 parts by mass. The (fluorenyl) acrylic polymer (a3) having a hydroxyl group used in the preparation of the above reaction product (b3) can be, for example, homopolymerized by a polymerizable monomer having a (meth) acrylonitrile group and a hydroxyl group. Or obtained by copolymerization with other polymerizable monomers. Examples of the polymerizable monomer having a (meth) acrylonitrile group and a light group include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-butyl butyl acrylate, and acrylic acid 2, 3. - Di-propyl propyl ester, mercapto acrylic acid 2 - trans-ethyl ester, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl methacrylate, and the like. These monomers may be used singly or in combination of two or more kinds. The (meth)acrylic polymer (a3) may be a homopolymer of a polymerizable monomer having a (meth)acrylonitrile group 201127480 and a warp group, or may be a copolymer with another polymerizable monomer. In the case of copolymerization with another polymerizable monomer, it is preferably [polymerizable monomer having a (fluorenyl) acrylonitrile group and a hydroxyl group]: [other polymerizable monomer] is 25 to 100 parts by mass: 75 The range of the mass fraction of 〇 更 is preferably 40 to 100 parts by mass: 6 〇 〇 〇 〇 。. The above other polymerizable monomer which is copolymerized when the (meth)acrylic polymer (al), (a2) and (a3) are prepared, for example, may be the following polymerizable monomer. (!) (fluorenyl) decyl acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, tert-butyl (meth) acrylate, (methyl) Hexyl acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, decyl acrylate, decyl acrylate, lauryl (decyl) acrylate, fluorenyl Tetradecyl acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, octadecyl (meth) acrylate, behenyl (meth) acrylate a (fluorenyl) acrylate having an alkyl group having 1 to 22 carbon atoms; (2) cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate (meth)acrylates having an alicyclic alkyl group such as (fluorenyl) biscyclopentenyloxyethyl acrylate; (3) benzhydryloxyethyl (meth) acrylate, benzyl (meth) acrylate Ester, phenethyl (meth) acrylate, phenoxyethyl (meth) acrylate, stupid a (meth) acrylate having an aromatic ring such as a diethylene glycol ester or a 2-hydroxy-3-phenoxypropyl (meth) acrylate; (4) hydroxyethyl (meth) acrylate; Hydroxypropyl acrylate, (meth) acrylate butyl acrylate, glyceryl (meth) acrylate; lactone modified (mercapto) acrylic acid, ethylene (meth) acrylate polyethylene glycol a methacrylate having a polyalkylene glycol group (meth) acrylate such as an ester or a (meth)acrylic acid polyacrylic acid 201127480 alcohol ester; and (5) a reverse butyl-acid diterpene Anti-butadiene-acid diacetate, dibutyl butyl succinate, dimethyl iconate, dibutyl itaconate, methyl ethyl bromide, methyl fumarate Unsaturated dicarboxylic acid esters such as butyl ester and methyl ethyl itaconate; (6) styrene derivatives such as styrene, α-methylstyrene, and stupid ethylene; (7) butadiene and isobutylene Diluted compounds such as pentadiene, piperylene, and dimercaptobutylene; (8) vinylidene and vinylidene such as vinylidene and vinylidene; (9) mercapto ketone Butyl Unsaturated ketones such as dilute hydrazine; (10) Ethyl acetate such as ethyl acetate, ethylene succinate, etc.; (Π) ethyl vinyl ether, butyl vinyl ether and other ethyl ethers (12) Ethyl cyanide such as acrylonitrile, methacrylonitrile or vinylidene; (1) acrylamide and its alkyd substituted amide; (14) Ν-stupyl maleimide , ν —cyclohexylmaleimide, etc. Ν a substituted maleimide; (15) vinyl fluoride, vinylidene fluoride, trifluoroethylene, trifluoroethylene, bromotrifluoroethylene, pentafluoropropylene or six Fluorine-containing α-olefins such as fluoropropene; or (per)fluoroalkanes such as difluoromethyldifluorovinyl ether, pentafluoroethyl trifluorovinyl ether or heptafluoropropyl trifluorovinyl ether a (per)fluoroalkyl group of perylene having a carbon number of from 18 to 18 perfluorovinyl ether; 2,2,2-trifluoroethyl(meth)acrylate vinegar, 2,2,3,3 - four Fluoropropyl (decyl) acrylate, 1 Η, 1 Η, 5 Η octafluoro fluorenyl (meth) acrylate vinegar, 1 Η, 1 Η, 2 Η, 2 Η ~ heptafluoro fluorenyl (fluorenyl) propyl 12 201127480 Acid s or perfluoroethyl oxyethyl (meth) acrylate a fluorine-containing ethylenically unsaturated monomer such as a (per)fluoroalkyl (meth) acrylate having a (per)fluoroalkyl group of 1 to 18; (16) T-mercaptopropene a fluorenyl-containing (meth) acrylate such as decyloxypropyltrioxane; (17) hydrazine, hydrazine-dimethylaminoethyl (meth) acrylate, ν, ν - diethyl Alkylaminoethyl (meth) acrylate or hydrazine, hydrazine-diethylaminopropyl (meth) acrylate or the like, hydrazine-dialkylaminoalkyl (meth) acrylate, and the like. Other I 5 unsaturated mono's which are used in the preparation of these (fluorenyl) acrylic polymers (al), (a2) and (a3) may be used singly or in combination of two or more. The (meth)acrylic polymers (al), (a2), and (a3) are obtained by polymerization (copolymerization) by a conventionally known method, and the copolymerization method is not particularly limited. It may be produced by addition polymerization in the presence of a catalyst (polymerization initiator), and may be any of a random copolymer, a block copolymer, a graft copolymer and the like. Further, as the polymerization method, a known polymerization method such as bulk polymerization, solution polymerization, suspension polymerization, or emulsion polymerization may be used. Here, a solvent may be used as the solution polymerization or the like, and examples of the agent include acetone, methyl ethyl ketone, methyl n-propyl hydrazine, methyl isopropyl ketone, and methyl n-butyl ketone. Methyl-n-propyl ketone, methyl ketone & n-pentahedral] methyl-n-hexyl ketone, diethyl ketone, ethyl n-butyl ketone ketone, diisobutyl ketone, cyclohexanone 'Furzen, etc. Ketone solvent Ethyl ethyl hydrazine, isopropyl acetonide, n-butyl squama, diisoamyl ether alcohol methyl test, ethylene glycol di-n-butyl test, diethylene glycol dimethyl sulphate, dioxane, tetrahydrofuran Ether-based solvent; 201127480 Ethyl citrate, propyl formate, n-butyl formate, ethyl acetate, acetic acid, isopropyl acetate, monodecyl ether acetate, ethylene, n-butyl acetate, N-amyl acetate, ethylene glycol glycol monoethyl ether acetate, diethylene glycol monodecyl ether acetate 'diethylene glycol monoethyl ether acetate' propylene glycol monomethyl ether acetate, ethyl 3-ethoxy Ester solvent such as propyl propionate; n-butanol, isobutanol, diacetone alcohol, 2 methoxy-1-butanol, 3-mercapto-3-3-toluene, SOLVESSO 1〇〇, SOLVESSO 150,

Naphtha 5、Exxon Naphtha 6等烴系溶劑。這些溶劑可以單A hydrocarbon solvent such as Naphtha 5 or Exxon Naphtha 6. These solvents can be single

—曱氧基一1—丙醇、3-甲氧基丁醇等醇系溶劑； 曱苯、二甲苯、SO 獨使用，也可以同時使用2種以上。 聚η (甲基）丙烯酸系聚合物（al)或（a2)時所使用的溶 劑由於作為3亥等聚合的後續第二階段反應的（甲基）丙烯酸 系聚口物(al)與單體⑷的反應、（曱基)丙烯酸系聚合物㈣ 與:體⑷的反應在_〜15(rc的高溫下進行時在反應效率 上疋較佳的，因此較佳為使用沸點在l〇〇°C以上（較佳在1〇〇 C )的心劑。作為聚合（甲基）丙烯酸系聚合物（a3)時所 使用的冷劑’由於作為該聚合的後續第二階段反應的（甲基） 丙烯西文系聚合物（a3)與單體⑷的反應在〜nc的範圍 進了時’在反應效率上是較佳的，因此較佳為使用沸點 6〇 C以上（較佳在60〜150°C )的溶劑。 ^外，作為上述催化劑，可以使用通常已知作為自由 土 ： 5起始劑者，例如可舉出2,2’—偶氮二異丁腈、2,2，_ 离氣一（2,4 —二甲基戍腈）、2,2，-偶氮二（4-甲氧基—24 14 201127480 -二甲基戊腈)等偶氮化合物；過氧化苯甲酿、過氧化月桂 醯、一級丁基過氧化特戊 叹馱s曰、二級丁基過氧乙基己酸酯、 ，—二(過氧化三級丁基）環己貌、過氧化三級戊基—2_乙 土己酉夂酉日、過氧化三級己美—甘 基2 —乙基己酸酯等有機過氧化 物及過氧化氫等。 使用過氧化物作為催化劑時，也可以將過氧化物與還 原劑-起使用，形成氧化還原型起始劑。 上述反應生成物（bl)係使如上所述具有環氧基的（甲基） 烯咬系聚口物(a ”與具有(曱基)丙烯醯基及羧基的單體⑷ 進行反應而得。具有（甲基）丙稀醯基及竣基的單體⑷，例如 可舉出（甲基）丙烯酸；基乙基（甲基）丙稀酸g旨、2—丙 烯醯氧基乙基琥珀酸酯、2_丙烯醢氧基乙基鄰苯二甲酸 酷、2-丙烯醯氧基乙基六氫鄰苯二甲酸醋及該等之内醋改 質物等具有酯鍵的不飽和單羧酸；馬來酸等。 另外，作為單體（c)，也可以使用使琥知酸酐及馬來酸 酐等酸酐與季戊四醇三丙烯酸酯等含有羥基的多官能（甲基） 丙烯酸醋單體反應後，形成的含有羧基的多官能（甲基）丙烯 酸酯單體。具有（甲基）丙烯醯基與羧基的單體（c)可以分別單 獨使用’也可以同時使用2種以上。 (甲基）丙烯酸系聚合物（al)與上述單體（c)的反應，通常 疋藉由將兩種成分加以混合，加熱到8〇〜l2〇t>c左右來進 行。對於（曱基）丙烯酸系聚合物（al)與單體（(;）的使用量，只 要使得到的反應生成物（bl)的（甲基）丙烯醯基當量處於2〇〇 〜600g/eq的範圍即可，沒有特別的限制，通常較佳為相對 於（曱基）丙烯酸系聚合物（a 1)令的環氧基1莫耳，使單體^) 15 201127480 中的羧基的莫耳數處於0.4〜ι·ι莫耳的範圍。 上述反應生成物（b2)係使如上所述具有羧基的（f基）丙 烯酸系聚合物（a2)與具有（甲基）丙烯醯基及環氧基的單體 進行反應而得。具有（甲基）丙烯醯基及環氧基的單體，例 如可舉出（甲基）丙烯酸縮水甘油酯、α —乙基（甲基）丙烯酸 縮水甘油醋、α —正丙基（曱基）丙烯酸縮水甘油酯、α —正 丁基（甲基）丙烯酸縮水甘油酯、（甲基）丙烯酸_3,4_環氧基 丁醋、（甲基）丙烯酸一 4,5 —環氧基戊酯、（曱基）丙烯酸_ 6,7 _環氧基戊醋、α —乙基（曱基）丙烯酸_6,7 —環氧基戊 酯、/5 —甲基縮水甘油基（甲基）丙烯酸酯、（甲基）丙烯酸一 3，4 一環氧基環己酯、内酯改質（甲基）丙烯酸一 3，4 _環氧基 環己醋、乙烯基環氧己烷等。這些單體可以單獨使用，也 可以同時使用2種以上。 (甲基）丙烯酸系聚合物（a2)與上述單體（d)的反應，通常 是藉由將兩種成分加以混合，加熱到8〇〜12〇左右來進 行。（曱基）丙烯酸系聚合物（a2)與單體（d)的使用量，只要使 得到的反應生成物（b2)的（甲基）丙烯醯基當量處於200〜 600g/eq的範圍内即可，沒有特別的限制，通常較佳為相對 於（曱基）丙烯酸系聚合物（a2)中的羧基丨莫耳，使單體（d) 中的環氧基的莫耳數處於0.4〜1.1莫耳的範圍。 上述反應生成物（b3)，係使如上所述具有經基的（甲基） 丙烯酸系聚合物（a3)與具有一個異氰酸酯基及（甲基）丙烯醯 基的單體（e)進行反應而得。具有一個異氰酸酯基及（曱基） 丙烯醯基的單體（e)，例如可舉出具有一個異氰酸酯基與一 個（曱基）丙烯醯基的單體、具有一個異氰酸酯基與兩個（甲 201127480 基）丙烯醯基的單體、具有一個異氰酸酯基與三個（曱基）丙 烯醯基的單體、具有一個異氰酸酯基與四個（曱基）丙烯醯基 的單體'具有一個異氰酸酯基與五個（曱基）丙烯醯基的單體 等。作為這種單體’例如可以較佳地例示下述通式1表示 的化合物。 〇CN-R^ C-C=CH2 通式（1)中，R!為氫原子或曱基。r2為碳原子數為2至 4的亞烷基。n表示1〜5的整數。這些化合物可舉出，例 如2—（曱基）丙烯醯氧基乙基異氰酸酯、u一二（丙烯醯氧 基曱基）乙基異氰酸酯等，具體來說有Karenz Α〇Ι、 MOI、Karenz BEI(商品名’昭和電工股份有限公旬製）等商 品。作為其他例子，有二異氰酸酯化合物與羥基丙烯酸酯 的反應加成物等。此處，作為二異氰酸酯化合物，可以沒 有特別限制地使用公知物質，例如可舉出甲苯二異氰酸 酉曰、六亞甲基二異氰酸酯、異佛爾酮二異氰酸酯等。作為 、！基丙烯馱g曰，只要是具有羥基及（甲基）丙烯醯基的化合物 即可，沒有特別地限制，可以使用公知的物質，例如可舉 出丙烯2~羥基乙酯、丙烯酸2_羥基丙酯、丙烯酸4 — &基丁自曰、甘油二丙烯酸酯、三羥甲基丙烷二丙烯酸酯、 季戊四醇二丙稀酸醋、二季戊四醇五丙稀酸醋等。其中， 從能夠提高交聯密度上考慮，較佳如Karenz BEI這樣的_ 個分子中具有兩個以上（甲基）丙稀醯基的物質。這些化合物 17 201127480 可以單獨使用，也可以同使用2種以上。 使（甲基）丙烯酸系聚合物（a3)與單體（e)反應的方法沒 有特別地限制，可以採用公知的方法。具體來說，例如可 以一邊在（甲基）丙烯酸系聚合物03)中滴加單體（e)，一邊加 熱到50〜120°C，更佳為加熱到60〜90。(：進行反應。又， 對於（曱基）丙烯酸系聚合物（a3)與單體（e)的使用量只要使 得到的反應生成物（b3)的（曱基）丙烯醯基當量處於2〇〇〜 600g/eq的範圍即可，沒有特別的限制，通常較佳為相對於 (甲基）丙烯酸系聚合物（a3)中的羥基1莫耳，使單體中的 異氰酸酯基的莫耳數處於0.8〜1.2莫耳的範圍。 上述具有環氧基的（甲基）丙烯酸系聚合物（al)與具有 (曱基）丙烯醢基及羧基的單體（c)的反應 '具有羧基的（曱基） 丙烯酸系聚合物（a2)與具有（曱基）丙烯醯基及環氧基的單體 (d)的反應、以及具有羥基的（甲基）丙烯酸系聚合物（a3)與具 有一個異氰酸酯基及（甲基）丙烯醯基的單體（e)的反應也可 以通過例如以下方法進行。 方法1 :藉由溶液聚合法聚合（甲基）丙烯酸系聚合物 (al)’在反應體系中加入具有（甲基）丙烯醯基及羧基的單體 (с) 進行反應。 方法2:藉由溶液聚合法聚合（曱基）丙烯酸系聚合物 (a2) ’在反應體系中加入具有（甲基）丙烯醯基及環氧基的單 體（d)進行反應。 方法3:藉由溶液聚合法聚合（甲基）丙烯酸系聚合物 (аз) ，在反應體系中加入具有一個異氰酸酯及（曱基）丙烯醯 基的單體（e)進行反應。 18 201127480 另外’本發明中使用的（曱基）丙烯酸系聚合物（B)，較 佳係將每個分子中具有一個聚合性不飽和雙鍵的單體進行 聚合而得到的結構作為主骨架的聚合物，亦可在聚合時不 發生凝膠化的範圍内併用具有兩個以上聚合性不飽和雙鍵 的單體。 本發明中使用的（甲基）丙烯酸系聚合物（B)，較佳為使 具有（甲基）丙烯醯基及羧基的單體&)與具有環氧基的（甲基） 丙烯酸系聚合物（al)進行加成反應而形成的反應生成物 (bl)，其中更佳為使（甲基）丙烯酸與具有環氧基的（曱基）丙 烯酸系聚合物（由含有（甲基）丙烯酸縮水甘油酯的聚合性單 體聚合而得到者）進行加成反應而形成的反應生成物。 上述具有環氧基的（甲基）丙烯酸系聚合物（al)的環氧當 量，較佳在140〜5〇〇g/eq的範圍，更佳在14〇〜3〇〇g/eq的 範圍。並且，具有環氧基的（甲基）丙烯酸系聚合物（al)的玻 璃化轉變溫度，較佳在3(rc以上，更佳在3〇〜1〇〇充的範 圍。 又’本發明中的環氧當量是根據JIS_K一 7236所定義 的值。 本發明中重量平均分子量與數量平均分子量的測定是 使用凝膠滲透層析法（GPC)，依據以下條件求得。 測定裝置：東曹股份有限公司製HLc — 8220 B 枝.東曹股份有限公司製Guide Column Hr — Η +東曹股份有限公司製TSKgel G5000Hxlj +東曹股份有限公司製TSKgel G4000HXi^ +東曹股份有限公司製TSKgel G3000Hxlj 19 201127480 +東曹股份有限公司製TSKgelG2〇〇〇HXL 檢測器：RI (差示折射計）- an alcohol solvent such as decyloxy-1-propanol or 3-methoxybutanol; benzene, xylene, and SO may be used alone or in combination of two or more. The solvent used in the poly(η) (meth)acrylic polymer (al) or (a2) is a (meth)acrylic polymer (al) and a monomer which are the second-stage reaction of the polymerization of 3H or the like. The reaction of (4), the reaction of the (fluorenyl)acrylic polymer (4) with the body (4) is preferably carried out at a reaction temperature of _15 (the high temperature of rc), so it is preferred to use a boiling point of l〇〇°. a core agent of C or higher (preferably 1 〇〇C). The refrigerant used as the polymerized (meth)acrylic polymer (a3) is due to the (meth) as the subsequent second-stage reaction of the polymerization. When the reaction of the propylene-based polymer (a3) with the monomer (4) is carried out in the range of nn nc, it is preferable in terms of reaction efficiency, and therefore it is preferred to use a boiling point of 6 〇 C or more (preferably 60 to 150 °). The solvent of C). In addition, as the above catalyst, those generally known as free soil: 5 initiators can be used, for example, 2,2'-azobisisobutyronitrile, 2,2, _ gassing off An azo compound such as mono(2,4-dimethylcarbonitrile), 2,2,-azobis(4-methoxy-24 14 201127480 -dimethylvaleronitrile); Oxidized benzoate, laurel, butyl sulphate, butyl peroxyethylhexanoate, bis(perylene tributyl peroxide), Oxidation of tertiary organic peroxides such as pentyl- 2 - ethane hexanyl, peroxidized tertiary hexyl-glycolyl 2-ethylhexanoate, etc. When using peroxide as a catalyst It is also possible to use a peroxide and a reducing agent to form a redox type initiator. The above reaction product (bl) is a (meth) enebatch polyether having an epoxy group as described above ( a" is obtained by reacting a monomer (4) having a (fluorenyl) acrylonitrile group and a carboxyl group. The monomer (4) having a (meth) propyl fluorenyl group and a fluorenyl group may, for example, be (meth)acrylic acid; Ethyl (meth) acrylate acid, 2-propenyloxyethyl succinate, 2- propylene methoxyethyl phthalate, 2-propenyloxyethyl hexahydroortylene An unsaturated monocarboxylic acid having an ester bond such as a dicarboxylic acid vinegar or such a vinegar modified substance; maleic acid, etc. Further, as the monomer (c), it may be used. a carboxyl group-containing polyfunctional (meth) acrylate monomer formed by reacting an acid anhydride such as an acid anhydride or maleic anhydride with a polyfunctional (meth)acrylic acid hydroxy monomer having a hydroxyl group such as pentaerythritol triacrylate. The monomer (c) having an acryloyl group and a carboxyl group may be used singly or in combination of two or more kinds. The reaction of the (meth)acrylic polymer (al) with the above monomer (c) is usually carried out by The two components are mixed and heated to about 8 〇 l 2 〇 t > c. For the amount of (mercapto) acrylic polymer (al) and monomer ((;), as long as the reaction is formed The (meth) acrylonitrile group equivalent of the substance (bl) may be in the range of 2 Å to 600 g/eq, and is not particularly limited, and is usually preferably used with respect to the (fluorenyl) acryl-based polymer (a 1). The epoxy group is 1 molar, so that the molar number of the carboxyl group in the monomer ^) 15 201127480 is in the range of 0.4 to ι·mole. The reaction product (b2) is obtained by reacting a (f-) acryl-based polymer (a2) having a carboxyl group as described above with a monomer having a (meth)acrylonyl group and an epoxy group. Examples of the monomer having a (meth) acrylonitrile group and an epoxy group include glycidyl (meth)acrylate, glycidyl acrylate of α-ethyl (meth)acrylate, and α-n-propyl group. ) glycidyl acrylate, glycidyl α-n-butyl (meth)acrylate, _3,4_epoxy butyl vinegar (meth) acrylate, 4,5-epoxy pentyl methacrylate Ester, (mercapto)acrylic acid _ 6,7 _ epoxy pentyl vinegar, α-ethyl (fluorenyl) acrylic acid _6,7-epoxypentyl ester, /5-methyl glycidyl (methyl) Acrylate, 3,4-epoxycyclohexyl (meth)acrylate, lactone modified (meth)acrylic acid-3,4-epoxycyclohexanoic acid, vinyl hexylene oxide, and the like. These monomers may be used singly or in combination of two or more kinds. The reaction of the (meth)acrylic polymer (a2) with the above monomer (d) is usually carried out by mixing the two components and heating to about 8 Torr to about 12 Torr. The amount of the (meth)acrylic polymer (a2) and the monomer (d) used is such that the (meth) acrylonitrile equivalent of the obtained reaction product (b2) is in the range of 200 to 600 g/eq. However, it is not particularly limited, and it is usually preferred to have a molar number of the epoxy group in the monomer (d) in the range of 0.4 to 1.1 with respect to the carboxyl group in the (fluorenyl)acrylic polymer (a2). The scope of Moore. The reaction product (b3) is obtained by reacting a (meth)acrylic polymer (a3) having a trans group as described above with a monomer (e) having one isocyanate group and (meth)acrylonyl group. Got it. The monomer (e) having one isocyanate group and (fluorenyl) acrylonitrile group, for example, a monomer having one isocyanate group and one (fluorenyl) propylene group, having one isocyanate group and two (A 201127480) a monomer having an isocyanate group, a monomer having one isocyanate group and three (fluorenyl) propylene groups, a monomer having one isocyanate group and four (fluorenyl) fluorenyl groups having one isocyanate group and Five (fluorenyl) acrylonitrile-based monomers and the like. As such a monomer, for example, a compound represented by the following formula 1 can be preferably exemplified. 〇CN-R^ C-C=CH2 In the formula (1), R! is a hydrogen atom or a fluorenyl group. R2 is an alkylene group having 2 to 4 carbon atoms. n represents an integer of 1 to 5. These compounds include, for example, 2-(indenyl)acryloxyethyl isocyanate, u-di(acryloxyfluorenyl)ethyl isocyanate, and the like, specifically Karenz®, MOI, Karenz BEI. (Product name 'Showa Denko Co., Ltd.'). As another example, there is a reaction adduct of a diisocyanate compound and a hydroxy acrylate. Here, as the diisocyanate compound, a known one can be used without particular limitation, and examples thereof include toluene diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate. As,! The acryl oxime is not particularly limited as long as it is a compound having a hydroxyl group and a (meth) acryl fluorenyl group, and a known one can be used, and examples thereof include 2-hydroxyethyl acrylate and 2-hydroxy propyl acrylate. Ester, acrylic acid 4 - & butyl ketone, glycerin diacrylate, trimethylolpropane diacrylate, pentaerythritol diacrylic acid vinegar, dipentaerythritol pentaacetic acid vinegar and the like. Among them, from the viewpoint of being able to increase the crosslinking density, a substance having two or more (meth) acrylonitrile groups in _ molecules such as Karenz BEI is preferable. These compounds 17 201127480 may be used singly or in combination of two or more. The method of reacting the (meth)acrylic polymer (a3) with the monomer (e) is not particularly limited, and a known method can be employed. Specifically, for example, the monomer (e) may be added dropwise to the (meth)acrylic polymer 03) while heating to 50 to 120 ° C, more preferably to 60 to 90. (: The reaction is carried out. Further, the amount of the (fluorenyl) acrylic polymer (a3) and the monomer (e) used is such that the (mercapto) acrylonitrile equivalent of the obtained reaction product (b3) is at 2 〇. The range of 〇~600 g/eq is not particularly limited, and it is usually preferably 1 mol with respect to the hydroxyl group in the (meth)acrylic polymer (a3), and the number of moles of the isocyanate group in the monomer. It is in the range of 0.8 to 1.2 mol. The reaction of the above-mentioned epoxy group-containing (meth)acrylic polymer (al) with the monomer (c) having a (fluorenyl) acrylonitrile group and a carboxyl group has a carboxyl group ( Mercapto group) The reaction of the acrylic polymer (a2) with the monomer (d) having a (fluorenyl) acrylonitrile group and an epoxy group, and the (meth)acrylic polymer (a3) having a hydroxyl group and having one The reaction of the isocyanate group and the (meth)acrylonitrile group monomer (e) can also be carried out, for example, by the following method. Method 1: Polymerization of a (meth)acrylic polymer (al) in a reaction system by a solution polymerization method Adding a monomer having a (meth) acryloyl group and a carboxyl group (с) Method 2: Polymerization of (indenyl)acrylic polymer (a2) by solution polymerization method. A monomer (d) having a (meth) acrylonitrile group and an epoxy group is added to the reaction system to carry out a reaction. 3: A (meth)acrylic polymer (аз) is polymerized by a solution polymerization method, and a monomer (e) having one isocyanate and a (fluorenyl) fluorenyl group is added to the reaction system to carry out a reaction. 18 201127480 The (fluorenyl) acrylic polymer (B) used in the invention is preferably a polymer obtained by polymerizing a monomer having one polymerizable unsaturated double bond per molecule as a main skeleton. A monomer having two or more polymerizable unsaturated double bonds is used in combination in the range where gelation does not occur during polymerization. The (meth)acrylic polymer (B) used in the present invention preferably has (a) a reaction product (bl) formed by an addition reaction of a monomer having a propylene group and a carboxyl group and a (meth)acrylic polymer (al) having an epoxy group, more preferably Methyl)acrylic acid with an epoxy group Yue-yl) acrylic polymer (containing (meth) acrylate polymerizable monomer is obtained by polymerizing a) an addition reaction to form a reaction product. The epoxy equivalent of the above epoxy group-containing (meth)acrylic polymer (al) is preferably in the range of 140 to 5 Å/eq, more preferably in the range of 14 Å to 3 Å/eq. . Further, the glass transition temperature of the (meth)acrylic polymer (al) having an epoxy group is preferably 3 (rc or more, more preferably 3 Torr to 1 Torr). The epoxy equivalent is a value defined in accordance with JIS_K-7236. The weight average molecular weight and the number average molecular weight in the present invention are determined by gel permeation chromatography (GPC) according to the following conditions: Measuring device: Tosoh Corporation Ltd. HLc — 8220 B 枝. Dong Cao Co., Ltd. Guide Column Hr — Η + TSKgel G5000Hxlj from Tosoh Corporation + TSKgel G4000HXi^ from Tosoh Corporation + TSKgel G3000Hxlj from Tosoh Corporation 19 201127480 + TSKgelG2〇〇〇HXL detector manufactured by Tosoh Corporation: RI (differential refractometer)

資料處理：東曹股份有限公司製SC — 80 1 〇 測定條件：管柱溫度40°C 溶劑 四氫呋喃 流速 1.0ml/分鐘 標準樣品：聚苯乙烯 武 樣：將換算成樹脂固體成分為0.4重量％之四氫 呋喃溶液利用微篩進行過濾得到者（丨〇〇# η 從硬化收縮效果與調平性方面考慮，本發明中使用的 (曱基）丙烯酸系聚合物（Β)的重量平均分子量較佳為5,〇〇〇 〜100,000的範圍，更佳為5,000〜50,000的範圍。 本發明中使用的（甲基）丙烯酸系聚合物（Β)具有經基。 在不損害本發明效果的範圍，（甲基）丙烯酸系聚合物具 有的羥基亦可與具有一個異氰酸酯基及（甲基）丙烯醯基的 單體的異氰酸酯基進行反應。由此，可以適當地調節（曱基） 丙烯醯基當量與羥基當量。 上述具有一個異氰酸酯基及（曱基）丙烯醯基的單體，例 如可舉出具有一個異氰酸酯基與一個（曱基）丙烯醯基的單 體具有一個異氰酸醋基與兩個（甲基）丙稀酿基的單體、具 有一個異氰酸酯基與三個（甲基）丙嫦酿基的單體、具有一個 異氰酸酯基與四個（甲基）丙烯醯基的單體、具有一個異氛酉λ 醋基與五個（甲基）丙烯醯基的單體。作為這種單體，例如可 以較佳地例示下述通式1表示的化合物。 20 201127480Data processing: SC - 80 1 from Tosoh Corp. 〇 Measurement conditions: column temperature 40 ° C Solvent tetrahydrofuran flow rate 1.0 ml / min Standard sample: polystyrene sample: converted to resin solid content 0.4% by weight The tetrahydrofuran solution is filtered by a microsieve (丨〇〇# η, the weight average molecular weight of the (fluorenyl) acrylic polymer (Β) used in the present invention is preferably 5 from the viewpoint of hardening shrinkage effect and leveling property. The range of 〇〇〇~100,000, more preferably in the range of 5,000 to 50,000. The (meth)acrylic polymer (Β) used in the present invention has a warp group. In the range which does not impair the effects of the present invention, (methyl The hydroxyl group of the acrylic polymer may also be reacted with an isocyanate group of a monomer having one isocyanate group and (meth)acryl fluorenyl group, whereby the (fluorenyl) propylene group equivalent and the hydroxyl group equivalent can be appropriately adjusted. The above monomer having one isocyanate group and (indenyl) acrylonitrile group may, for example, be a single one having one isocyanate group and one (fluorenyl) acryl group. a monomer having one isocyanate group and two (meth) propylene groups, a monomer having one isocyanate group and three (meth) propylene groups, having one isocyanate group and four ( a monomer having a methyl methacrylate group, a monomer having an isomeric 酉 λ vine group and five (meth) acryl fluorenyl groups. As such a monomer, for example, the following formula 1 is preferably exemplified. The compound. 20 201127480

通式（1)中，R!為氫眉1 子或甲基。R2為碳原子數為2$ 1?^ 基曱基乙Γ稀醯f基乙基異氱酸si、u-二(丙稀醯氧 " 土異狀酉日等，具體來說有Karenz A01、Karenz MOI、Karen? RFTf黹。々 。 （商。〇名，昭和電工股份有限公司製）等商 為其他例+，有二異氰酸®旨化合物與經基㈣酸gg 的反應加成物等。此處，作為二異氰酸醋化合物，可以沒 有/寺:限制地使用公知物質，例如可舉出曱笨二異氰= -曰/、亞曱基一異氰酸酯、異佛爾酮二異氰酸酯等。作為 羥基丙烯酸酿，只要是具有羥基及（曱基）丙烯醯基的化合物 即可，沒有特別地限制，可以使用公知的物質例如可舉 出丙烯酸2 —羥基乙酯、丙烯酸2 —羥基丙酯、丙烯酸4 — 羥基丁酯、甘油二丙烯酸酯、三羥甲基丙烷二丙烯酸酯、 季戊四醇三丙烯酸酯、二李戊四醇五丙烯酸酯等。其中， 從月b夠k尚父聯饮度上考慮，較佳如Karenz βει般，一個 分子中具有兩個以上（曱基）丙烯醯基的物質。 使本發明所使用的（甲基）丙烯酸系聚合物（Β)、與具有 一個異氰酸酯基及（甲基）丙烯醯基之單體反應的方法，沒有 特別地限制，可以採用公知的方法。具體來說，例如可以 在本發明的（甲基）丙烯酸系聚合物（Β)中滴加具有一個異氰 酸醋基及（甲基）丙烯醯基的單體，加熱到5〇〜12〇。(：，更佳 21 201127480 維加熱到60〜90°C進行反應即可。另，（甲基）丙烯酸系聚 合物（B)與具有一個異氰酸酯基及（甲基）丙稀醯基之單體的 使用量’通常（曱基）丙烯酸系聚合物（B)的羥基（莫耳）：具有 一個異氰酸酯基及（甲基）丙浠gg基之單體的異氰酸酯基（莫 耳）為1 : 0.1〜1 : 0.9的範圍，較佳為1 : (U〜1 : 〇 7的範 圍。 在本發明的分散體製造方法中，適宜使用各種二氧化 矽微粒。二氧化矽微粒，可舉出乾式二氧化矽微粒、濕式 一氧化矽微粒等。乾式二氧化矽微粒，例如藉由使四氣化 石夕在氧或氫焰中燃燒而得到的二氧化矽微粒。又，濕式二 氧化矽，例如用無機酸中和矽酸鈉而得到的二氧化矽微 粒根據本發明的製造方法，即使是使用任何二氧化石夕微 粒的情況，所得到的分散體亦可長時間地保持良好的分散 穩疋！·生又，即使將該分散體添加到胺甲酸乙酯（曱基）丙烯 酸酯、環氧（甲基）丙烯酸酯等活性能量線硬化型寡聚物或活 I·生月b里線硬化型單體中’來製備活性能量線硬化型樹脂組 成物的情況，在該活性能量線硬化型樹脂組成物中，二氧 化矽微粒亦可長時間地穩定分散。 本發明所使用的二氧化石夕微粒（F)，較佳為平均一次 徑在Hhm〜300nm的範@，更佳為平均一次粒徑在⑽ 〜200nm的範圍。 在本發明巾，係將：氧切微粒（F)分散在上述（曱邊 丙烯酸系聚合物(B)，_分散體。得到的分散體中各 分的含量沒有特別地限制，較佳為使〔（甲基）丙烯酸系聚 物（B)〕.〔二氧切微粒（F)〕A 10〜90質量份：90〜 22 201127480 質量份的範圍（更佳為30〜90質量份：7〇〜1〇f量份的範 圍）含有（甲基）丙稀酸系聚合物（B)與二氧化石夕微粒（F)。又， 本發明所得到之分散體中的（甲基）丙稀酸系聚合物（b)與二 氧化矽微粒（F)的合計含有率，較佳為以固體成分換算在！ 〜50質量％的範圍，更佳在i〜3〇質量％的範圍。 本發明所使用的漿料，係含有（甲基）丙烯酸系聚合物（B) 與二氧化矽微粒（F) ’但除了此等外，亦可含有（曱基）丙烯 酸系聚合物（B)以外之具有（甲基）丙烯醯基的化合物。（甲基） 丙烯酸系聚合物（B)以外之具有（曱基）丙烯醯基的化合物， 例如可舉出活性能量線硬化型單體（M)& /或活性能量線硬 化型养聚物（0)等。各成分的含量沒有特別的限制，較佳為 使〔（甲基）丙烯酸系聚合物（B)〕：〔活性能量線硬化型單 體（M)及/或活性能量線硬化型寡聚物（〇)〕為1〇〜9〇質量 份：90〜10質量份的範圍（更佳為3〇〜9〇質量份：7〇〜1〇 質量份）含有（甲基）丙烯酸系聚合物（B)與活性能量線硬化型 單體（M)及/或活性能量線硬化型寡聚物（〇) β 此處，使用（曱基）丙稀酸系聚合物（Β)以外之具有（曱基） 丙烯醯基的化合物時，（曱基）丙烯酸系聚合物（Β)可以用作 為使二氧化矽微粒（F)分散於該（曱基）丙烯酸系聚合物（Β)以 外之具有（甲基）丙烯醯基的化合物的分散劑。 上述活性能量線硬化型單體（Μ)，例如除了作為（曱基） 丙烯酸系聚合物（Β)的原料使用的聚合性單體等以外，可列 舉乙二醇二（曱基）丙烯酸酯、丙二醇二（曱基）丙烯酸酯、二 乙二醇二（甲基）丙烯酸酯、三乙二醇二（曱基）丙烯酸酯、四 乙二醇二（曱基）丙烯酸酯、聚乙二醇二（甲基）丙烯酸酯、二 23 201127480 丙二醇二（甲基）丙烯酸酯、三丙二醇二（甲基）丙烯酸酯、四 丙二醇二（甲基）丙烯酸酯、聚丙二醇二（曱基）丙烯酸酯、1，3 —丁二醇二（曱基）丙烯酸酯、1，4 — 丁二醇二（曱基）丙烯酸 酯' 1>6—六亞甲基二醇二（曱基）丙烯酸酯、1，9一壬二醇二 (曱基）丙烯酸酯、新戊二醇二（甲基）丙烯酸酯、羥基新戊酸 新戊二醇二（甲基）丙烯酸酯、在羥基新戊酸新戊二醇上加成 己内酯而形成的化合物的二（甲基）丙烯酸酯、新戊二醇己二 酸酯二（曱基）丙烯酸酯、三羥曱基丙烷、二三羥曱基丙院、 季戊四醇、二季戊四醇、四羥甲基曱烷及對該等化合物加 成1〜20莫耳的環氧院烴而形成的含經基化合物等具有3 個以上羥基的化合物與3個以上（曱基）丙烯酸分子形成酉旨 鍵所得到的化合物等。 上述活性能量線硬化型寡聚物（〇) ’例如可舉出選自丙 烯酸系聚合物（B)以外的丙烯醯（甲基）丙烯酸酯、胺曱酸乙 酉曰（甲基）丙稀酸醋、聚醋（曱基）丙烯酸醋、環氧（甲基）丙稀 酸S旨等所構成之群中的一種以上的（甲基）丙烯酸酯化合物。 上述細曱酸乙醋（曱基）丙稀酸g旨，例如可舉出使異氮於 醋化合物與含有羥基的（甲基）丙烯酸酯化合物反應而形成 的多官能胺曱酸乙酯（甲基）丙烯酸酯。此處所使用的異氰酸 酯化合物，例如可舉出六亞甲基二異氰酸酯、異佛爾酮二 異氰酸酯、二曱苯二異氰酸酯、氩化二甲笨二異氰酸酯、 二環己基甲烷二異氰酸酯、降冰片烯二異氰酸酯等脂肪族 或脂環式二異氰酸酯化合物；甲苯二異氰酸酯、4 4，__二 基曱烷二異氰酸酯等芳香族二異氰酸酯；為二異氰酸酯2 合物三聚物的異氰脲酸酯型異氰酸酯預聚物等。另外，亦 24 201127480 可為在製造該多官能胺甲酸乙酯（曱基）丙烯酸酯時，用2元 〜4元醇及/或多元醇化合物取代含經基的（甲基）丙稀酸酯 化合物（與異氰酸酯化合物反應）的一部分加以聚合而得者。 上述聚酯（曱基）丙烯酸酯，可舉出使選自乙二醇、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、乙氧基化氫化雙酚A、丙氧基化雙酚A、丙氧基化 氫化雙酚A及二元以上的多元醇中的一種以上物質和選自 以鄰苯二甲酸酐、間苯二甲酸、對苯二甲酸、己二酸、四 氫鄰苯二曱酸酐、$氫鄰苯二曱酸酐、馬來酸酐、反丁烯 二酸、偏苯三酸酐、均苯四酸酐等為代表的多元酸中的一 種以上物質進行醋化反應而得到含有羥基的醋多元醇，再 對該I旨多元醇進行（曱基）丙烯酸s旨化而形成的多官能醋（甲 基）丙烯酸酯等。 酵、丁二醇、戊二醇、己二醇、二乙二醇、二丙二醇、三 乙二酵、三丙二醇、四乙二醇、$乙二醇、聚丙二醇、新 f二醇、録新戊酸新戊二醇、雙紛A、乙氧基化雙^ 醇的三縮水甘油基喊化物等二環氧基化合物進行加 價衣乳（甲基）丙稀酸醋化合物；對三 :等=三經甲基丙燒、丙氧基化…基丙燒、： 油荨二兀醇進行環氧化而得 甘 酸酯與該環氧化合物進行加\ ° ’再使（甲基）丙烯 自由基聚合性不飽和雙:::f到的具有…個以上 物；使縮水甘油㈣具有至的；(甲基）丙烯酸騎化合 氧烧烴加成物進行反應而㈤Μ環的多讀或其環 成％虱化合物，再使（甲基）丙烯 25 201127480 酸醋與㈣氧化合物進行加成反應而得到的苯㈣駿樹 脂、甲㈣酸樹脂等多官能芳香族環氧丙婦酸醋；這此多 官能方香族環氧丙稀酸醋的氫化型式即多官能脂環式環氧 丙烯酸醋；進-步藉由存在於分子中的二級經基和二異氛 酸醋化合物的-個異氰酸醋進行胺甲酸乙醋化後，使殘留 的單個末端的異氰酸3旨基和含經基的（甲基）丙稀酸酯進行 反應而得到的胺甲酸乙酯改質環氧丙烯酸酯等。 在這些化合物中，具有平均3個以上自由基聚合 飽和雙鍵的聚㈣甲基）丙烯酸醋和胺甲酸乙酯（甲基）丙稀酸 酯的硬化塗膜的耐磨損性良好，因此是特佳的。 在本發明中使用的漿料中’亦可根據需要添加有機溶 劑。較佳為漿料中含有有機溶劑（s)。 本發明中使用的有機溶劑⑻，例如可舉出丙酮、甲基 乙基胴（MEK)、甲基異丁基酮等酮類，四氫。夫喃⑽f)、2 氧雜環戊烷(cH0X0lane)等環狀醚類’醋酸甲醋、醋酸乙酿、 醋酸丁醋等酷類，曱苯 '二曱苯等芳香族類卡必醇、2 — 乙氧乙醇、甲醇 '異丙醇、丁醇、丙二醇單甲基㈣醇類， 這些溶劑可以單獨或同時使用，其中，從塗布時的揮發性 及溶劑回收方面考廣，及雁，托公勒為丨&人 田哼恿反應〖生刀散劑的合成溶劑較佳為曱 基乙基嗣。 上述有機溶劑的使用量，較佳為相對於（甲基）丙稀酸系 聚合物（Β)和二氧切微粒（F)的合計⑽f量份為l Z質量人份，其中於扇〜3〇〇質量份時，在珠磨機操作時 ’二與介質分離良好，❿且漿料濃縮時的步驟於短時間即 可完成，因此是較佳的。 26 201127480 製備聚料時，較佳為在上述（甲基）丙燁酸系聚合物（b) 中添加有機③劑而得到有機溶劑溶液€，添加二氧化矽微 粒（F)。 根據需要也可以在本發明中使用的漿料中添加各種添 加劑。 本發明中使用的各種添加劑，例如可舉出偶聯劑。偶 聯劑’例如可舉出乙烯基系錢偶聯劑、環氧系錢偶聯 劑、苯乙烯系矽烷偶聯劑、甲基丙烯醯氧基系矽烷偶聯劑、 丙烯醯氧基系石夕烧偶聯劑、氨基系石夕烧偶聯劑、醢腺系矽 烷偶聯劑、氣丙基系矽烷偶聯劑、巯基系矽烷偶聯劑、硫 化物系矽烷偶聯劑、異氰酸酯系矽烷偶聯劑、鋁系矽烷偶 聯劑等。 乙烯基系矽烷偶聯劑，例如可舉出乙烯基三氣矽烷、 乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、2—(3,4 一環 氧環己基）乙基三甲氧基矽烷、3_環氧丙氧基丙基三曱氧基 矽烷、3—環氧丙氡基丙基曱基二乙氧基矽烷、3_環氧丙 氧基三乙氧基矽烷、對苯乙烯基三甲氧基矽烷、3_甲基丙 烯醯氧丙基曱基二甲氧基矽烷、3一曱基丙烯醯氧丙基三甲 氧基石夕烧、3—甲基丙烯醯氧丙基甲基二乙氧基矽烷、3 — 曱基丙烯醯氧丙基三乙氧基矽烷、3一丙烯醯氧丙基三曱氧 基矽烷、N— 2—(氨基乙基）—3 —氨基丙基曱基二曱氧基矽 烷、N—2—（氨基乙基）_3—氨基丙基三甲氧基矽烧、2 (氨基乙基）一3~氨基丙基三乙氧基矽烧、3 一氨基丙基三 曱氧基矽烷、3 —氨基丙基三乙氧基矽烷、3_三乙氧基甲 矽烷基一N—(l，3—二曱基.·亞丁基）丙基胺、N —苯基—3 — 27 201127480 氨基丙基三甲氧基石夕烧、N—(乙烯基苄基）—2 一氨義厂 土 基 3 —氨基丙基三曱氧基矽烷的鹽酸鹽 '特殊氧基石夕燒、3 醯腺丙基三乙氧基矽烧、3—氣丙基三甲氧基矽俨、 土 ’ λό、_3 —疏 基丙基曱基二曱氧基矽烧、3—巯基丙基三曱氧基矽燒、_ (三乙氧基曱矽烷基丙基）四硫化物' 3 —異氰酸酯基丙基二 乙氧基矽烷、烯丙基三氣矽烷、烯丙基三乙氧基矽烷、烯 丙基二曱氧基矽烷、二乙氧基甲基乙烯基矽烷、三氣乙烯 基矽烷、乙烯基三氣矽烷、乙烯基三甲氧基矽烷、乙烯基 二乙氧基矽烷、乙烯基三（2 —曱氧基乙氧基）矽烷。 環氧系矽烷偶聯劑，例如可舉出二乙氧基（環氧丙氧基 丙基)甲基石夕烧、2-(M-環氧環己基)乙基三甲氧基石夕：、 3-環氧丙氧基丙基三甲氧基矽烷、3_環氧丙氧基丙基甲 基二乙氧基矽烷、3 —環氧丙氧基丙基三乙氧基矽烷等。 苯乙烯系矽烷偶聯劑，例如可舉出對笨乙烯基三曱 基矽烷等。 甲基丙烯醯氧基系钱偶聯劑，例如可以例示3_甲基 丙烯醯氧丙基甲基二甲氧基矽烷、 土 ^ 基丙烯醯氧丙基三 曱氧基矽烷、3 —甲基丙烯醯氧丙某 %叼丞甲基—乙氧基矽烷、3 一曱基丙烯醯氧丙基三乙氧基矽院。 丙烯酿氧基系㈣偶聯劑，例如可舉出3—丙烯酿氧丙 基三甲氧基矽烷等。 氣基系石夕烧偶聯劑，例如可盛 卜 举出Ν—2-(氨基乙基）—3 一氛基丙基甲基二曱氧基矽烷、 好 2—(虱基乙基）_3_氨 基丙基三甲氧基矽烷、Ν—2 —(者其7贫、 ,.^ ^ 1虱基乙基）~3—氨基丙基三 乙軋基矽烷、3—氨基丙基三甲氧 τ乳基矽烷、3 —氨基丙基三 28 201127480 乙氧基梦貌、3 ~ =乙#^其® —乙氧基尹矽烷基一N—(1，3_二f基一亞 丁基）丙基胺、N -苯基—3〜* 虱基丙基三f氧基石夕炫等。 醯脲系矽烷偶聯劑，例如可舉出3-醯脲丙基三乙氧基 矽烷等。 氯丙基系料偶制，例如可以例示3-氯丙基三甲氧 基矽烷。 疏基系㈣偶聯劑，例如可舉出3-録丙基甲基二f 氧基石夕炫、3-疏基丙基三子氧基石夕院等。 硫化物系石夕烧偶聯劑，例 例如可舉出二（三乙氧基甲矽烷 基丙基）四硫化物等。 異氰酸醋系石夕烧偶聯劑，例如可舉出3 一異氛酸醋基丙 基三乙氧基矽燒等。 銘系偶聯劑’例如可舉出 燒氧基紹二異丙醇化物 等。 本發明的分散體製造方法的特徵在於，將上述漿料從 包含以下構件之濕式球磨機的毁料供給口供給到定子内· 1) 内部填充有介質的圓筒形定子、 2) 設置於上述定子下端的锻料供給口、 3) 位於上述定子的軸心，並且 排放通道之進行旋轉驅動的旋轉轴、^置有中空狀液體 4) 與上述旋轉軸進行同軸旋轉驅動的轉子 5) 以同轴狀設置於上述旋轉轴上部且、 液體排放通道連通而排出分齙为 、上迷中空狀. 退埂逋而排出刀離液之方式所構 驅動的葉輪型分離器； 進仃紅轉 在定子内旋轉驅動上述轉子 撥拌混合介質與激料， 29 201127480 使知椠料中的一氧化石夕微粒粉碎並分散至分散劍，同時在 進行紅轉驅動之分離器部藉由離心力作用使製料與介質分 離’將被誘導到分離器轴心部的衆料從上述旋轉軸内的中 空排放通道排出。 ，以下’利用圖式對使用如上所述之濕式球磨機的本發 明製造方法進行詳細說明。 圖1中，將以原料泉2從貯存驳料的原料槽 的衆料，從供給口 16供給至濕式球磨機3中。該： 機具體可舉出圖2中沾（11 質，藉由形定子7,子7内填充有介 ""驅動之轉子11將漿料和介質攪拌混合，使漿 :中的二氧切微粒（F)粉碎並分散在（曱基）丙稀酸系聚合 :，且利用旋轉驅動的葉輪型分離器4藉由 料與介質分離。此時，比重大的介質沿徑向朝外 呷，通過目：於此，比重小的漿料被誘導往分離器4的軸心 二過’置於旋轉軸5上部的中空狀液體排放通道9,經 由泵64返回到槽1中，囍 、！ 碎。在循援& 藉匕來進行二氧化矽微粒的循環粉 值時終止。 過田柳疋漿料的粒度，達到預期 在本發明的製造方本& 磨機3之德措士喜 中，漿料經原料泵供給至濕式球 通常為3G〜⑽L/小時，較佳、j磨機3的每1升内容量， 流量處於該範圍内，衆料小時。藉由使循環 常較佳為5 ^ 時，分散所花費的時間通 為5〜6G分鐘，更佳為1〇〜4〇分鐘。 定子7中填充的介質，伽4 J如可以使用各種微小珠粒。 30 201127480 微小珠粒的原料，彳 矽酸錘等。 °可牛出氧化㉘、玻璃、氧化鈦、銅、 對於介質的粒徑 好，且轉子"中二，“離器4中㈣和介質的分離良 間也不易變長、對:切微粒的粉碎也良好、分散所需時 因二氧切微粒破：ΓΓ微粒的衝擊不會過強、不容易 貝 生過度分散現象之方面考慮，較 '立料的平均粒徑為15〜30—，更佳為15〜50 μ m。 上述過度刀政現象是指二氧化矽微粒破損導致新的活 性表面生《’出現再凝集的現象。如果過度分散，則分散 液變為凝膠狀。 定子内；|貝的填充率通常較佳為定子内容積的8〇〜 體積/。。藉由使填充率為定子内容積的8〇〜9〇體積％，則 得到單位重量的製品漿料所需要的動力最少。即，可以進 行最有效地粉碎。 將聚料供給於定子7時的順序如下。在濕式球磨機。3 的定子7内填充介質後，在關閉閥門58 ' 59及6〇並且打 開閥門61、62及64的狀態下首先驅動電動機12，接著驅 動原料泵2。驅動轉子11及分離器4藉由前者電動機12的 驅動而旋轉，另一方面原料槽1中的原料漿料藉由後者原 料泵2的驅動以每次一定量送入供給口 μ的導入口 27,從 而通過閥座24的邊緣與閥體25之間所形成的狹縫而供給 至濕式球磨機内。 驅動電動機12使轉子11及分離器4旋轉時，轉數越 大周向速度越大，所受離心力越大，另外，介質和二氧化 31 201127480 石夕微粒撞擊時的衝擊也越大。當介質是使 =時’較佳周向速度為一以上。當介^ :為的介質時，較佳周向速度為以上。 用以1中所示的濕式球磨機3係具備在分散完成後 …排出之取出。19，但是在本發明中’該球磨機 亦可不具備取出口 19。 按如上方式進行分散，衆料粒度達到預期值，終止分 散時的順序如下。 首先，就於濕式球磨機3沒有取出口 19的形態方面， 了舉出以下方法：先停止原料栗2 ’接著停止電動機η , ^使濕式球磨機3停止運轉，終止粉碎。之後關閉閥 門61後’打開閥門59。然後，藉由再次啟動原料系2,將 原㈣1内的製品⑽從排出σ 66輸送至製品槽67内。 方面’為了抽出殘留於定子7之製品聚料，係將原料 系2停止並同時關閉閱門59。接著，將經由間門“返回到 j枓槽！的管線轉換連接至製品槽67。於置空的原料槽i 填充作為原料的㈣，按照與上述於定子7中供給聚料 :相同的順序進行操作，再次驅動電動機12，同時再次驅 原枓果W 7中殘留的製品毁料回收到製品槽中。 於濕式球磨機3具有取出口 9的形態方面，終止分散 時的順序如下。 “先t止原料泵2,接著停止電動冑12,從而使濕式球 3兮止運轉’終止粉碎 '然後打開閥門π及59且關 ::門6卜62及64,並且再次啟動原料果2及電動機12, 開間門6〇°由此’原料槽1内的製品襞料被原料系 32 201127480 2抽出並從排出口 66輸送到製品槽67内。另—方面，濕式 球磨機3中的製品漿料由於轉子7的旋轉而一邊被攪拌， 一邊通過閥門60及中空狀液體排放通道9，並藉由供給到 濕式球磨機3中的壓縮空氣或N2氣而通過篩網18，進而被 擠出，經過取出口 19從排出口 65輸送到製品槽67中。按 以上方式’原料槽1中及濕式球磨機3中的製品漿料被回 收到製品槽6 7中。 又，使用具有取出口 19的濕式球磨機時，回收製品時 使轉子7旋轉是為了進行混合使得介質不會沉降而偏在於 濕式球磨機3的下層部位，從而防止篩網18的篩孔堵塞。 進而為了消除篩孔堵塞，也可以適當地打開閥門63從取出 口 19導入壓縮空氣或化氣，從而對筛網18進行反向沖洗。 基於圖1〜圖4對本發明的製造方法中使用的裝置進行 更詳細地說明。 上述濕式球磨機3，々口圖2中詳細所示，為縱向的圓筒 形，具有：配備了流通有冷卻水之夾套6的定子7、設置於 定子下端的漿料供給口 16、位於定子7的軸心且其上部設 有與原料槽1連通的中空狀液體排放通道9之用以進行旋 轉驅動的旋轉軸5、在上述旋轉軸下端部分朝徑向突出設置 之與旋轉軸進行同軸旋轉驅動的針狀或盤狀的轉子1 1、固 定於旋轉轴上部之圖1中所示的電動機12的皮帶輪13和 掛皮帶的皮帶㊣14、安裝在旋轉軸上端的開口端之旋轉接 頭15'與位於定子内上部附近固定於旋轉軸5上的用於分 離介質的分離器4。 另外’定子底部具有上述取出σ 19日夺，該取出口 19 33 201127480 配置於定子底部的偏心位置，具體來說，由格子狀筛網支 架1 7和安裝於該篩網支架1 7上的用於分離介質的筛網^ 8 構成。 分離器4由在旋轉軸5上隔著一定間隔固定之—對圓 盤21與連接兩圓盤21之葉片22所組成，以構成葉輪，與 上述旋轉軸5進行同軸旋轉’以對進入圓盤之間的介質和 漿料施加離心力，利用其比重差使介質沿徑向向外飛出， 另一方面’漿料通過設置於旋轉軸5軸心之上述中空狀液 體排放通道9而被排出。 原料漿料的供給口 16 〜 τ汁珊所不，由形成方 定子底部的閥座24、可升降地嵌合於閥座24的倒梯形閥骨 25、從定子底部向下突出並形成有原料漿料導入口 之等 底圓筒體26及從該圓筒體向下突出並具備壓縮空氣或n 乱導入口 29之有底圓筒28、可升降地嵌合在圓筒體28』 的活塞3卜連接活塞31和閥體25的桿32、安裝於圓筒儀 28内的活塞上並且在壓下活塞31時-直將閥體25往下拍 之彈箸33、和突出於圓筒體28並检入桿的端部且位置可巧 :地安裝的螺母34的組成，若由於原料聚料的供給而將閥 25往上壓，則與閥座24之間形成環狀縫隙，原料漿料 二此被供給到球磨機内，但是上述縫隙的寬度可藉由螺 使在Λ㈣、放鬆進行㈣，從而可以㈣寬度設定為即 圓行體％ 。供給原料時的閥體25由於送入 内的原料聚料的供給星而抵抗 壓力及彈菁33之作用而上升，與闕座“之間形成縫：之 34 201127480 但是原料漿料的供給壓因供給原料而形成的縫隙寬度，稍 微小於螺母34所規定最大縫隙寬度，因此螺母34的圓筒 體28之間還稍有充裕。 在通過閥座24和閥體25之間所形成.的縫隙而被供給 到球磨機内之原料漿料中含有粗粒子，可預料其會失入閥 座和閥體之間而產生堵塞，因夾入而發生了堵塞時，藉由 提问供給壓使閥體25上升到極限，縫隙寬度達到最大d因 此夾入的粗粒子會流出，堵塞消除。如果堵塞消除，則供 給壓便下降，閥體25會落下。 ’、 為了消除縫隙處的堵塞’在圖示的例子中，進而使壓 =氣或n2氣從圖示中省略之壓縮空氣或N2氣源通過調 卽β 23,再經過電磁切換閥3〇從導入口 29供給至圓筒體 28内’壓縮空氣或ν2氣藉由在較短週期内反覆進行⑽一 〇FF :刀換而被不連續地供給，由此閥體25在較短週期中反 覆進:丁上升到上限位置的上下動作，可以消除夹入問題。 該閥體25的振動可以—直進行，亦可在原㈣料令含In the formula (1), R! is a hydrogen eyebrow or a methyl group. R2 is a carbon atom number of 2$1?^ 曱 曱 Γ Γ 醯 醯 基 基 乙基 乙基 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 , Karenz MOI, Karen? RFTf黹.々. (Shang. Anonymous, Showa Denko Co., Ltd.) and other quotients are other examples +, there are reaction products of diisocyanate® and compound (tetra) acid gg. Here, as the diisocyanate compound, a known substance may be used without limitation, and examples thereof include, for example, diisopropyl diisocyanide = -曰/, fluorenylene-isocyanate, isophorone diisocyanate. The hydroxy acrylic acid is not particularly limited as long as it is a compound having a hydroxy group and a (fluorenyl) acryl fluorenyl group, and a known one can be used, for example, 2-hydroxyethyl acrylate or 2-hydroxy acrylate. Ester, 4-hydroxybutyl acrylate, glycerin diacrylate, trimethylolpropane diacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, etc. Among them, from the month b enough k is still the father's drink Considered, preferably like Karenz βει, with one molecule Two or more (fluorenyl) acrylonitrile-based materials. Method for reacting a (meth)acrylic polymer (Β) used in the present invention with a monomer having one isocyanate group and (meth)acryl fluorenyl group There is no particular limitation, and a known method can be employed. Specifically, for example, an isocyanate group and (meth) propylene oxime may be added dropwise to the (meth)acrylic polymer (Β) of the present invention. Base monomer, heated to 5 〇~12 〇. (:, better 21 201127480 dimension heating to 60~90 ° C for reaction. In addition, (meth)acrylic polymer (B) with one isocyanate The amount of the monomer used in the (meth) acrylonitrile group. The hydroxyl group (mole) of the usual (fluorenyl) acrylic polymer (B): having one isocyanate group and (meth) propyl gg group The monomeric isocyanate group (mole) is in the range of 1:0.1 to 1:0.9, preferably 1: (U~1: 〇7). In the dispersion production method of the present invention, various kinds of dioxide are suitably used. Helium particles. As the cerium oxide particles, dry cerium oxide can be cited. Granular, wet cerium oxide microparticles, etc. Dry cerium oxide microparticles, for example, cerium oxide microparticles obtained by burning four gas fossils in an oxygen or hydrogen flame. Further, wet cerium oxide, for example, inorganic The cerium oxide fine particles obtained by neutralizing sodium citrate with an acid According to the production method of the present invention, even if any of the silica fine particles are used, the obtained dispersion can maintain good dispersion for a long time! Further, even if the dispersion is added to an active energy ray-hardening oligomer such as urethane (mercapto) acrylate or epoxy (meth) acrylate, or a live I·shengyue b line hardening type In the case where the active energy ray-curable resin composition is prepared in the body, the cerium oxide fine particles can be stably dispersed for a long period of time in the active energy ray-curable resin composition. The silica fine particles (F) used in the present invention preferably have an average primary diameter in the range of Hhm to 300 nm, more preferably an average primary particle diameter in the range of (10) to 200 nm. In the towel of the present invention, the oxygen-cut fine particles (F) are dispersed in the above-mentioned (acrylic polymer (B), dispersion). The content of each component in the obtained dispersion is not particularly limited, and it is preferred to [(Meth)acrylic polymer (B)]. [Dioxy-cut particles (F)] A 10 to 90 parts by mass: 90 to 22 201127480 Parts by mass (more preferably 30 to 90 parts by mass: 7〇) The range of ~1〇f parts) contains (meth)acrylic acid polymer (B) and silica dioxide particles (F). Further, (meth) propylene in the dispersion obtained by the present invention The total content of the acid polymer (b) and the cerium oxide fine particles (F) is preferably in the range of from ～50% by mass in terms of solid content, more preferably in the range of i to 3% by mass. The slurry to be used contains a (meth)acrylic polymer (B) and cerium oxide microparticles (F), but may contain a (fluorenyl) acrylic polymer (B) in addition to these. a compound having a (meth)acryl fluorenyl group. A compound having a (fluorenyl) acrylonitrile group other than the (meth)acrylic polymer (B) For example, an active energy ray-curable monomer (M) & / or an active energy ray-curable nucleus (0) may be mentioned. The content of each component is not particularly limited, and it is preferred to [(methyl) Acrylic polymer (B)]: [Active energy ray-curable monomer (M) and/or active energy ray-curable oligomer (〇)] is 1 〇 9 9 parts by mass: 90 to 10 parts by mass The range (more preferably 3 〇 to 9 〇 parts by mass: 7 〇 to 1 〇 by mass) contains a (meth)acrylic polymer (B) and an active energy ray-curable monomer (M) and/or an active energy ray Hardening type oligomer (〇) β Here, when a compound having a (fluorenyl) acrylonitrile group other than a (fluorenyl) acrylic acid polymer (Β) is used, a (fluorenyl) acrylic polymer (Β) A dispersant which is a compound having a (meth) acrylonitrile group other than the (fluorenyl) acrylic polymer (F) dispersed in the cerium oxide fine particle (F). The above active energy ray-hardening monomer (Μ), for example, a polymerizable monomer used as a raw material of a (fluorenyl) acrylic polymer (Β) Further, examples thereof include ethylene glycol di(decyl)acrylate, propylene glycol di(decyl)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(decyl)acrylate, and tetraethyl b. Diol bis(mercapto) acrylate, polyethylene glycol di(meth) acrylate, bis 23 201127480 propylene glycol di(meth) acrylate, tripropylene glycol di(meth) acrylate, tetrapropylene glycol di(methyl) Acrylate, polypropylene glycol bis(indenyl) acrylate, 1,3-butanediol bis(indenyl) acrylate, 1,4-butanediol bis(indenyl) acrylate '1>6-six Methyl diol di(indenyl) acrylate, 1,9-nonanediol bis(indenyl) acrylate, neopentyl glycol di(meth) acrylate, hydroxypivalic acid neopentyl glycol di(a) Bis(meth)acrylate, neopentyl glycol adipate bis(indenyl)acrylate, three compounds of acrylate, a compound formed by adding caprolactone to hydroxypivalic acid neopentyl glycol Hydroxymercaptopropane, ditrihydroxyindolyl, pentaerythritol, dipentaerythritol, tetrahydroxymethyl hydrazine And a compound having three or more hydroxyl groups, such as a trans group-containing compound, which is formed by adding an alkylene compound having 1 to 20 mols to the compound, and a molecule of three or more (fluorenyl)acrylic acid molecules Compounds, etc. The above-mentioned active energy ray-curable oligomer (〇) can be exemplified by acrylonitrile (meth) acrylate other than acrylic polymer (B), and acetoacetic acid (meth) acrylate vinegar. One or more (meth) acrylate compounds in a group consisting of polyacetal (mercapto) acryl vinegar and epoxy (meth) acrylic acid S. The above-mentioned fine acetoacetate (mercapto) acrylic acid g is, for example, a polyfunctional amine decanoate formed by reacting an anaerobic compound with a hydroxy group-containing (meth) acrylate compound. Base) acrylate. Examples of the isocyanate compound used herein include hexamethylene diisocyanate, isophorone diisocyanate, dinonyl diisocyanate, dimethyl diisocyanate, dicyclohexylmethane diisocyanate, and norbornene. An aliphatic or alicyclic diisocyanate compound such as an isocyanate; an aromatic diisocyanate such as toluene diisocyanate or 4,4-didecane diisocyanate; an isocyanurate type isocyanate which is a diisocyanate 2 terpolymer. Prepolymer, etc. In addition, 24 201127480 may be substituted for the trans-group-containing (meth) acrylate with a 2 to 4 membered alcohol and/or a polyol compound in the production of the polyfunctional urethane (mercapto) acrylate. A part of the compound (which is reacted with an isocyanate compound) is polymerized. The polyester (mercapto) acrylate may be selected from the group consisting of ethylene glycol, propylene glycol, diethylene glycol, neopentyl glycol, bisphenol A, hydrogenated bisphenol A, ethoxylated bisphenol A, and B. One or more selected from the group consisting of oxylated hydrogenated bisphenol A, propoxylated bisphenol A, propoxylated hydrogenated bisphenol A, and a dihydric or higher polyhydric alcohol and selected from the group consisting of phthalic anhydride and isophthalic acid In the polybasic acid represented by terephthalic acid, adipic acid, tetrahydrophthalic anhydride, hydrogen phthalic anhydride, maleic anhydride, fumaric acid, trimellitic anhydride, pyromellitic anhydride, and the like. One or more substances are subjected to a acetation reaction to obtain a hydroxy group-containing acetal polyol, and a polyfunctional vinegar (meth) acrylate which is formed by subjecting the polyol to a (meth)acrylic acid s. Yeast, butanediol, pentanediol, hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, tetraethylene glycol, ethylene glycol, polypropylene glycol, new f-diol, new record a di-epoxy compound such as a triglycidyl-based compound of valeric acid neopentyl glycol, bis-A, ethoxylated bis-alcohol, and a bidentate (meth)acrylic acid vinegar compound; Trimethyl propylene hydride, propoxylated propyl ketone, epoxidized by hydrazine didecyl alcohol to obtain the esterification of the glyceride with the epoxy compound and then the (meth) propylene radical polymerization Sexually unsaturated double:::f to have more than ...; to make glycidol (4) have; (meth)acrylic acid to ride oxygenated hydrocarbon adducts to react (5) multi-read of anthracene ring or its ring % a polyfunctional aromatic epoxidized acetoacetate such as benzene (tetra) resin or methyl (tetra) acid resin obtained by addition reaction of (meth) propylene 25 201127480 acid vinegar with (tetra) oxy compound; The hydrogenated version of the Fangxiang epoxy acrylate is a polyfunctional alicyclic epoxy acrylate; the step by After the acetylation of the carbamide with the secondary thiol group and the isocyanic acid vinegar of the diisocyanate compound, the residual single terminal isocyanate 3 group and the trans group-containing (meth) group are obtained. The ethyl urethane obtained by the reaction of the acrylate is modified with epoxy acrylate or the like. Among these compounds, a cured coating film of poly(tetra)methyl)acrylic acid vinegar and ethyl urethane (meth) acrylate having an average of three or more radically polymerized saturated double bonds has good abrasion resistance, and therefore Very good. In the slurry used in the present invention, an organic solvent may be added as needed. Preferably, the slurry contains an organic solvent (s). The organic solvent (8) used in the present invention may, for example, be a ketone such as acetone, methylethyl hydrazine (MEK) or methyl isobutyl ketone or tetrahydrogen. Cyclic ethers such as flu (10)f) and 2 oxolane (cH0X0lane), such as methyl acetate, acetic acid, acetic acid, butyl vinegar, etc., aromatic carbitol, etc. — ethoxyethanol, methanol 'isopropanol, butanol, propylene glycol monomethyl (tetra) alcohol, these solvents can be used alone or in combination, which is widely used in terms of volatility and solvent recovery during coating, and The composition solvent of the 哼恿 amp amp 人 生 生 生 生 生 生 生 生 生 生 生 生 生 生 生 生 生 生 生The amount of the organic solvent to be used is preferably 1 part by mass based on the total (10)f of the (meth)acrylic acid polymer (Β) and the dioxygen particles (F), wherein the fan is 3 In the case of 〇〇 by mass, the separation between the two and the medium is good during the operation of the bead mill, and the step of concentrating the slurry can be completed in a short time, and therefore it is preferable. 26 201127480 When preparing a polymer, it is preferred to add an organic solvent to the (meth)propionic acid-based polymer (b) to obtain an organic solvent solution, and to add cerium oxide particles (F). Various additives may also be added to the slurry used in the present invention as needed. The various additives used in the present invention include, for example, a coupling agent. Examples of the coupling agent include a vinyl-based money coupling agent, an epoxy-based money coupling agent, a styrene-based decane coupling agent, a methacryloxy decyl coupling agent, and an acryloxy lanthanide. Ekima coupling agent, amino-based zebra coupling agent, parotid decane coupling agent, gas propyl decane coupling agent, sulfhydryl decane coupling agent, sulfide decane coupling agent, isocyanate decane A coupling agent, an aluminum decane coupling agent, or the like. Examples of the vinyl decane coupling agent include vinyl trioxane, vinyl trimethoxy decane, vinyl triethoxy decane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxy. Decane, 3-glycidoxypropyltrimethoxy decane, 3-epoxypropyl propyl decyl diethoxy decane, 3-epoxypropoxy triethoxy decane, p-styrene Trimethoxy decane, 3-methylpropenyl methoxypropyl decyl dimethoxy decane, 3-mercapto propylene oxypropyl trimethoxy zeoxime, 3-methyl propylene oxiranyl methyl Ethoxy decane, 3-mercapto propylene oxypropyl triethoxy decane, 3- propylene methoxy propyl trimethoxy decane, N-2-(aminoethyl)-3-aminopropyl fluorenyl Dimethoxydecane, N-2-(aminoethyl)_3-aminopropyltrimethoxysulfonium, 2 (aminoethyl)-3-aminopropyltriethoxysulfonate, 3-aminopropyl Trimethoxy decane, 3-aminopropyl triethoxy decane, 3-triethoxymethyl sulfonyl-N-(l,3-diindolyl)butylene, N-phenyl —3 — 27 201127480 Propyl trimethyl oxycarbazide, N-(vinylbenzyl)-2, an amine-based plant, 3-aminopropyltrimethoxy decane hydrochloride, 'Special oxy-stone smelting, 3 sputum C Triethoxy oxime, 3-propyl propyl trimethoxy sulfonium, earth 'λλ, _3 — sulfhydryl decyl decyloxy oxime, 3-mercaptopropyltrimethoxy oxime, _ (triethoxydecylpropyl) tetrasulfide ' 3 - isocyanate propyl diethoxy decane, allyl trioxane, allyl triethoxy decane, allyl dioxane Base decane, diethoxymethyl vinyl decane, triethylene vinyl decane, vinyl trioxane, vinyl trimethoxy decane, vinyl diethoxy decane, vinyl tris (2- methoxy B Oxy) decane. Examples of the epoxy decane coupling agent include diethoxy(glycidoxypropyl)methyl sulphate and 2-(M-epoxycyclohexyl)ethyltrimethoxy sulphate: 3 - glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldiethoxydecane, 3-glycidoxypropyltriethoxydecane, and the like. The styrene-based decane coupling agent may, for example, be a p-vinyltrimethyl decane or the like. The methacryloxyloxy-based money coupling agent may, for example, be exemplified by 3-methacryloxypropylmethyldimethoxydecane, propylene propyleneoxypropyltrimethoxy decane, or 3-methyl group. Acryloxypropane 5% methyl ethoxylate, 3-mercapto propylene oxypropyl triethoxy fluorene. Examples of the propylene-based oxy-based (tetra) coupling agent include 3-propylene oxypropyltrimethoxydecane. The gas-based system is a coupling agent, for example, 2-(aminoethyl)-3-aminopropylmethyldimethoxy decane, preferably 2-(mercaptoethyl)_3 _Aminopropyltrimethoxydecane, Ν—2 — (the 7 is poor, , .^ ^ 1 thioethyl)~3-aminopropyltriethyl decyl decane, 3-aminopropyltrimethoxy τ Base decane, 3-aminopropyl three 28 201127480 Ethoxy dream, 3 ~ = B#^其® - ethoxy fluorenyl-N-(1,3-di-f-butylene) propylamine , N-phenyl-3~* mercaptopropyltri-foxide, Xi Xuan, etc. The uret urea-based olefin coupling agent may, for example, be 3-ureidopropyltriethoxy decane. The chloropropyl group is monovalent, and for example, 3-chloropropyltrimethoxydecane can be exemplified. Examples of the coupling agent of the sparingly-based (IV)-based coupling agent include 3-camperyl-di-f-oxyxanthine, 3-sulfopropyltrioxyxanthene, and the like. Examples of the sulfide-based zebra-fired coupling agent include bis(triethoxymethanepropylpropyl) tetrasulfide. The isocyanate-based sulphur-burning coupling agent may, for example, be 3-isoacetoic acid propyltriethoxy oxime or the like. The term "coupling agent" may, for example, be an alkoxydiisopropoxide or the like. The method for producing a dispersion of the present invention is characterized in that the slurry is supplied from a reject supply port of a wet ball mill including the following members to a stator. 1) a cylindrical stator filled with a medium, 2) a forging supply port at the lower end of the stator, 3) a rotating shaft that is located at the axial center of the stator, and that is rotationally driven by the discharge passage, and a hollow liquid 4) a rotor that rotates coaxially with the rotating shaft 5) An impeller-type separator that is axially disposed on the upper portion of the above-mentioned rotating shaft and that communicates with the liquid discharge passage and discharges the branching and is hollow. The impeller-type separator driven by the method of discharging the knife away from the liquid; Rotating and driving the above-mentioned rotor to mix the mixed medium and the stimulating material, 29 201127480 pulverizes and disperses the smectite particles in the sputum material to the dispersing sword, and at the same time, the centrifugal force is used to make the material in the separator portion which is driven by the red rotation. Separating from the medium 'the mass that is induced to the core of the separator is discharged from the hollow discharge passage in the above-mentioned rotating shaft. Hereinafter, the manufacturing method of the present invention using the wet ball mill as described above will be described in detail using the drawings. In Fig. 1, the raw material spring 2 is supplied from the raw material tank of the storage material to the wet ball mill 3 from the supply port 16. The machine can be specifically illustrated in Figure 2 (11, by means of the stator 7, the sub-7 is filled with a "" driven rotor 11 to mix the slurry and the medium to make the dioxin in the slurry: The cut particles (F) are pulverized and dispersed in (mercapto)acrylic acid polymerization: and are separated from the medium by a rotary driven impeller type separator 4. At this time, the medium having a large specific gravity is radially outward. By this purpose, the slurry having a small specific gravity is induced to pass through the hollow liquid discharge passage 9 of the upper portion of the rotary shaft 5 to the axial center of the separator 4, and is returned to the tank 1 via the pump 64, 囍, ! The granules are terminated when the circulating powder value of the cerium oxide particles is carried out by the Assisting & 。 。. The particle size of the 田 疋 疋 疋 slurry is expected to be in the manufacturing method of the present invention & In the slurry, the slurry is usually supplied to the wet bulb by the raw material pump to be 3G to (10) L/hour, preferably, the amount of the liter of the mill 3 is in the range of 1 liter, and the flow rate is within the range, and the mass is hourly. When the ratio is 5 ^, the time taken for the dispersion is 5 to 6 G minutes, more preferably 1 to 4 minutes. Quality, gamma 4 J If you can use a variety of tiny beads. 30 201127480 Small beads of raw materials, citric acid hammer, etc. ° can be oxidized 28, glass, titanium oxide, copper, good particle size for the medium, and the rotor "Secondary, "the separation between the separator 4 and the medium is not easy to become long, and the comminution of the cut particles is also good. When the dispersion is required, the dioxin particles are broken: the impact of the ruthenium particles is not too strong. In view of the fact that it is not easy to over-disperse, the average particle size of the 'material is 15~30-, more preferably 15~50 μm. The above excessive knife-like phenomenon means that the cerium oxide particles are broken to cause new ones. The active surface produces "the phenomenon of re-aggregation. If it is excessively dispersed, the dispersion becomes gelatinous. The inside of the stator; | The filling rate of the shell is usually preferably 8 〇 ~ volume / of the internal volume of the stator. The filling rate is 8 〇 to 9 〇 vol% of the internal volume of the stator, and the power required to obtain a product slurry per unit weight is the least. That is, the most effective pulverization can be performed. The order of supplying the granules to the stator 7 is as follows. Fill in the stator 7 of the wet ball mill. After the medium, the motor 12 is first driven in a state where the valves 58'59 and 6'' are closed and the valves 61, 62, and 64 are opened, and then the material pump 2 is driven. The drive rotor 11 and the separator 4 are rotated by the driving of the former motor 12. On the other hand, the raw material slurry in the raw material tank 1 is fed into the introduction port 27 of the supply port μ by a certain amount of driving by the latter raw material pump 2, thereby forming between the edge of the valve seat 24 and the valve body 25. The slit is supplied to the wet ball mill. When the motor 12 is driven to rotate the rotor 11 and the separator 4, the larger the number of revolutions, the larger the circumferential speed, the greater the centrifugal force, and the medium and the dioxide 31 201127480 The impact of the impact of the particles is also greater. When the medium is made =, the preferred circumferential speed is one or more. When the medium is medium, the preferred circumferential speed is above. The wet ball mill 3 shown in Fig. 1 has a take-out after the completion of the dispersion. 19. However, in the present invention, the ball mill may not have the outlet 19 . Dispersion was carried out as above, the mass particle size reached the desired value, and the order in which the dispersion was terminated was as follows. First, in the case where the wet ball mill 3 does not take the outlet 19, the following method is employed: first, the raw material pump 2 is stopped, then the motor η is stopped, and the wet ball mill 3 is stopped, and the pulverization is terminated. After closing the valve 61, the valve 59 is opened. Then, by starting the raw material system 2 again, the product (10) in the original (four) 1 is transported from the discharge σ 66 into the product tank 67. In order to extract the product material remaining in the stator 7, the raw material system 2 is stopped and the door 59 is closed at the same time. Next, the line returning to the j-tank via the door is switched to the product tank 67. The raw material tank i which is vacant is filled with the raw material (i), and is carried out in the same order as the above-mentioned supply of the aggregate in the stator 7. In operation, the motor 12 is driven again, and the product residue remaining in the original W 7 is again recovered into the product tank. In the form in which the wet ball mill 3 has the outlet 9 , the sequence in which the dispersion is terminated is as follows. The material pump 2 is stopped, and then the electric cymbal 12 is stopped, so that the wet bulb 3 stops operating 'stop pulverization' and then the valves π and 59 are opened and closed: the door 6 62 and 64, and the raw material 2 and the motor 12 are activated again. The opening door is 6°°, whereby the product material in the raw material tank 1 is taken out by the raw material system 32 201127480 2 and transported from the discharge port 66 into the product tank 67. On the other hand, the product slurry in the wet ball mill 3 is stirred while being rotated by the rotor 7, passes through the valve 60 and the hollow liquid discharge passage 9, and is supplied with compressed air or N2 in the wet ball mill 3. The gas passes through the screen 18 and is then extruded and conveyed through the take-out port 19 from the discharge port 65 into the product tank 67. In the above manner, the product slurry in the raw material tank 1 and in the wet ball mill 3 is returned to the product tank 67. Further, when a wet ball mill having a take-out port 19 is used, when the product is recovered, the rotor 7 is rotated for mixing so that the medium does not settle and is biased to the lower portion of the wet ball mill 3, thereby preventing clogging of the screen of the screen 18. Further, in order to eliminate the clogging of the screen, the valve 63 may be appropriately opened by introducing the compressed air or the condensed gas from the take-out port 19, thereby performing backwashing of the screen 18. The apparatus used in the manufacturing method of the present invention will be described in more detail based on Figs. 1 to 4 . The wet ball mill 3, which is shown in detail in Fig. 2, has a cylindrical shape in a longitudinal direction, and has a stator 7 provided with a jacket 6 through which cooling water flows, a slurry supply port 16 provided at a lower end of the stator, and a shaft of the stator 7 and an upper portion thereof is provided with a hollow liquid discharge passage 9 communicating with the material tank 1 for rotating the shaft 5 for rotation, and a lower end portion of the rotating shaft is coaxially disposed coaxially with the rotating shaft A needle-shaped or disk-shaped rotor 11 that is rotationally driven, a pulley 13 of the motor 12 shown in Fig. 1 fixed to the upper portion of the rotating shaft, and a belt 14 of the hanging belt, and a rotary joint 15 that is attached to the open end of the upper end of the rotating shaft 'Separator 4 for separating the medium fixed to the rotating shaft 5 near the upper inner portion of the stator. In addition, the bottom of the stator has the above-mentioned take-up σ 19 days, and the take-out port 19 33 201127480 is disposed at an eccentric position of the bottom of the stator, specifically, the grid-like mesh bracket 17 and the mounting on the screen bracket 17 It is composed of a screen mesh 8 of separation medium. The separator 4 is composed of a pair of discs 21 and blades 22 connecting the two discs 21 fixed on the rotating shaft 5 to form an impeller, coaxially rotating with the rotating shaft 5 to enter the disc. A centrifugal force is applied between the medium and the slurry, and the medium is caused to fly outward in the radial direction by the difference in specific gravity. On the other hand, the slurry is discharged through the hollow liquid discharge passage 9 provided in the axial center of the rotating shaft 5. The supply port 16 to the τ juice of the raw material slurry are not covered, and the valve seat 24 at the bottom of the stator is formed, and the inverted trapezoidal valve bone 25 that is liftably fitted to the valve seat 24 protrudes downward from the bottom of the stator to form a raw material. a bottom cylindrical body 26 such as a slurry introduction port, and a bottomed cylinder 28 that protrudes downward from the cylindrical body and that is provided with compressed air or n-introduction port 29, and is fitted to the piston of the cylindrical body 28 3, the rod 32 connecting the piston 31 and the valve body 25, the piston mounted on the piston in the cylinder 28 and when the piston 31 is depressed - the magazine 33 is directly pulled down by the valve body 25, and protrudes from the cylinder 28 and check the end of the rod and the position may be: the composition of the nut 34 installed, if the valve 25 is pressed upward due to the supply of the raw material, an annular gap is formed with the valve seat 24, the raw material slurry The second is supplied to the ball mill, but the width of the slit can be made to Λ (4) and relaxed (4), so that the width of (4) can be set to be the circle body %. When the raw material is supplied, the valve body 25 rises due to the pressure and the action of the elastic crystal 33 due to the supply star of the raw material aggregate fed therein, and forms a seam with the squat: 34 201127480 However, the supply pressure of the raw material slurry The width of the slit formed by the supply of the raw material is slightly smaller than the maximum slit width defined by the nut 34, so that the cylindrical body 28 of the nut 34 is slightly richer. The slit formed between the valve seat 24 and the valve body 25 is formed. The raw material slurry supplied into the ball mill contains coarse particles, and it is expected that it will fall between the valve seat and the valve body to cause clogging. When clogging occurs due to the pinching, the valve body 25 is raised by asking the supply pressure. At the limit, the gap width reaches the maximum d, so the coarse particles that are trapped will flow out and the clogging will be eliminated. If the clogging is eliminated, the supply pressure will drop and the valve body 25 will fall. ', in order to eliminate the clogging at the gap'. Further, the compressed air or the N2 gas, which is omitted from the drawing, is passed through the 卽β 23, and then supplied to the cylindrical body 28 through the electromagnetic switching valve 3〇 to the compressed air or Ν2 gas by Repeatedly in a short cycle (10) one FF: the knife is replaced and supplied discontinuously, whereby the valve body 25 is reversed in a short period: the up and down movement of the swell to the upper limit position can eliminate the pinching problem. The vibration of 25 can be carried out directly or in the original (four) material order.

有大里粗粒子時，s al I f進订$外’由於堵塞而使原料聚料的供 °上升時，也可以與其進行聯動。 务碎終止後，將授拌後的介質與製品浆料一起取出， ::抽出製品激料後取出時，如圖所示降低螺 將電磁切換閱3。切換到•藉此，間體 ： 導入口 29所道百口攸 緣以上。 之垄縮空氣或％氣而上升到閥座24的邊 軸5上，:實二方式中’轉子U和分離器4均固定在旋轉 —疋在其他實施方式中則是固定於配置於同軸上 35 201127480 =不同旋轉軸上’分別進行旋轉驅動4轉子和分離器安 裝於同-旋轉軸上的上述實施方式中，有一驅動裝 可’因此結構簡單，與此㈣，於轉子和分離器安裳於不 同旋轉軸上並用不同驅動裝置進行旋轉驅動的實施形離方 面，可以使轉子和分離器分別按最適宜的轉數進行旋轉驅 動。圖5是該實施方式中的濕式欖拌球磨機的縱截面圖， 圖6是表示圖5所示的濕式授拌球磨機的分離器的橫截面 圖。 圖5所示的球磨機，旋轉軸43做成附有段差之軸，從 旋轉軸下端嵌插分離器44’接著交替地嵌插隔板45和圓盤 狀或針狀轉子46,然後在旋轉軸下端用螺釘48固定塞子 47 ’藉由軸43的段差43a和塞子47夾住分離器…_ 45及轉+ 46’使其連接固定，分離器料如圖6所示，由 面對内側之面上分別形成有葉片嵌合槽51之一對圓盤52、 介於兩圓#52間嵌合於葉片嵌合槽51之葉片53、使兩個 圓盤52保持一定間隔並形成有連通排放通道54的孔55之 環狀隔板56所組成而構成了葉輪。 本發明的分散體製造方法中使用濕式球磨機。濕式球 磨機’例如可舉出Ashizawa Finetech股份有限公司製造的 珠磨機STAR- MIL(商品名）；三井鑛山股份有限公司製造 的 MSC- MILL、SC— MILL、Attritor MA01SC ;淺田鐵工 股份有限公司的 NANO GRAIN MILL、Pico Grain Mm、PureWhen there are large and coarse particles, s al I f can be interlocked with when the supply of the raw material is increased due to clogging. After the termination of the crushing, the mixed medium is taken out together with the product slurry. :: When the product is extracted and taken out, the screw is lowered as shown in the figure. Switch to • By this, the inter-body: the entrance to the entrance 29 is more than 100 points. The air or the air is raised to the side shaft 5 of the valve seat 24, and in the second embodiment, the rotor U and the separator 4 are both fixed in rotation - in other embodiments, they are fixed on the coaxial line. 35 201127480=In the above-mentioned embodiment in which the rotary rotor is separately driven and the separator is mounted on the same-rotating shaft on different rotating shafts, there is a driving device, so the structure is simple, and (4), in the rotor and the separator The rotor and the splitter can be rotationally driven at an optimum number of revolutions, respectively, in terms of the rotational displacement of the different rotational axes and the different driving means. Fig. 5 is a longitudinal sectional view of the wet type ball mill in the embodiment, and Fig. 6 is a cross-sectional view showing the separator of the wet type ball mill shown in Fig. 5. In the ball mill shown in Fig. 5, the rotating shaft 43 is formed with a shaft having a step, and the separator 44' is inserted from the lower end of the rotating shaft, and then the partition plate 45 and the disk-shaped or needle-shaped rotor 46 are alternately inserted, and then the rotating shaft The lower end is fixed with a screw 48 to the plug 47' by the step 43a of the shaft 43 and the plug 47 clamps the separator ... _ 45 and the turn + 46' to make the connection fixed, and the separator material is as shown in Fig. 6, facing the inner side. Each of the blade fitting grooves 51 is formed with a pair of discs 52, and the blades 53 fitted between the two circles #52 are fitted to the blade fitting grooves 51, and the two discs 52 are kept at a certain interval to form a communication discharge passage. The annular partition 56 of the hole 55 of 54 is formed to constitute an impeller. A wet ball mill is used in the dispersion production method of the present invention. The wet ball mill 'for example, a bead mill STAR- MIL (trade name) manufactured by Ashizawa Finetech Co., Ltd.; MSC- MILL, SC- MILL, Attritor MA01SC manufactured by Mitsui Mining Co., Ltd.; Asada Iron Works Co., Ltd. Company's NANO GRAIN MILL, Pico Grain Mm, Pure

Grain Mill ^ Mechagaper Grain Mill > Cerapower Grain Mill ^ Dual Gram Mill ^ AD Mill' Twin AD Mill. Basket Mill ' Twin basket mill ’壽工業股份有限公司製造的Apex Mill、Ultra 36 201127480 AW MlU、_ MU1等商品。其中較佳為Ultra Apex Mill。 另外，本發明的製造方法中也偏好使肖 Fmetech股份有限公司製造的珠磨機_ — Mm。該珠磨 機STAR-MILL係具備：—端具有聚料人口之筒狀容器、 在上述容器内以縱向延展方向配置之可自由旋轉的搜掉 軸、於上述容器外連接於上述授拌軸的驅動裝置，而上述 搜拌轴具有攪拌構件，於上述攪拌軸與上述容器内面之間 的空間加入有粉碎介質，一邊從上述聚料入口導入毁料一 邊利用上述驅動裝置旋轉驅動上述搜拌轴，藉此使該毅料 内的二氧切微粒粉碎，上錢拌軸在上述容Η 一端附 近形成有具有介質入口的中空部’於上述㈣軸形成有縫 隙’此縫隙係使該中空部連通於上述檀拌軸與上述容器内 面之間的空間’而隨著聚料移動，到達上述容器之另一端 附近的介質從上述聚料入口進入上述授拌軸之中空部進 行從上述縫隙返回上㈣拌轴與上述容器内面之間的空間 之循環運動。該介請拌型粉碎裝置的特徵在於，上述撥 拌軸的中空部内配置有漿料出σ，且於上述中空部心將 上述聚料出口包圍之方式設置有篩網，並旋轉驅動上 網。 在上述介質授拌型粉碎裝置中，由於用於從浆料中分 離出介質的筛網被驅動進行旋轉，到達篩網附近的激料及 介質也誘發了旋轉運動’該旋轉運動導致的離心力為介質 方高於襞料方，因此介質就產生了從激料中分離的偏離 力。因此，介質就不接近篩網地進行循環。因而可以有效 37 201127480 地從漿料中除去介質。 由本發明的製造方法得到的分散體可通過添加適當溶 劑、使溶劑揮發而調節到適合於塗布方法的濃度。添加的 溶劑’可舉出上述的有機溶劑（s)。 由本發明的製造方法得到的分散體本身亦可作為活性 能量線硬化型樹脂組成物使用，也可以根據需要與其他化 合物混合使用。這些化合物，可舉出上述活性能量線硬化 型單體（M)、活性能量線硬化型寡聚物（〇)、紫外線吸收劑、 抗氧化劑 '矽系添加劑、有機珠粒、^系添加劑、流變性 控制劑、消泡劑、脫模劑、矽烷偶聯劑、抗靜電劑、防霧 劑、著色劑等。 上述紫外線吸收劑，例如可舉出2 一〔 4 一丨（2 —羥連 ―3—十二烷基氧丙基）氧丨一2—羥基苯基〕—46_二（2 -二甲基苯基H，3,5-三唤、2一〔4—丨(2—經基二; 二烷基巩丙基)氧卜2-羥基笨基〕-4,6-二(2 4一二曱遵 苯基卜…一三.等三嗪衍生物、卜(2、氧I : 甲基笨基)苯并三唾、2—(2，—鄰硕基节氧基— Π 苯基）笨并三。坐、2—^ —本并哌喃鲮基一 4—十二烷氧基二与 甲卟 imhene carboxy—4 —do—— 鄰硝基节氧基一 4 一十二貌氧基二笨曱嗣等。 域抗氧化劑，例如可舉出受_系抗氧化劑、受阳 胺系抗氧化劑、有機访备k ~ _ "系抗氧化劑、磷酸酯系抗氧化劑等, 刚述矽系添加劑，你丨 苯基W二::::二曱T氧院， «改質二甲基”氧氧烧、曱基―、 礼烷共聚物、聚酯改質二甲基聚矽辈 38 201127480 烷共聚物、氟改質二甲基聚矽氧烷共聚物、氨基改質二甲 基聚石夕氧烧共聚物等之具有㈣、苯基之聚有”㈣類。 上述有機珠粒，例如可舉出聚曱基丙烯酸甲酯珠粒、 聚碳酸酯珠粒、聚苯乙稀珠粒、$丙烯酸苯乙料粒、聚 石夕氧珠粒、玻璃珠粒、麗克力珠粒、苯并胍胺系樹脂珠粒、 三聚氰胺系樹脂珠粒、聚烯烴系樹脂珠粒、聚g旨系樹脂珠 粒、聚醯胺樹脂珠粒、聚醯亞胺系樹脂珠粒、聚氟乙烯樹 脂珠粒、聚乙烯樹脂珠粒等。這些有機珠粒的平均粒徑為又 〜10微米’可以單獨使用任—帛，也可以同時使用2種以 上。 如上所述的各種添加劑的使用量，考慮到充分發揮其 效果，以及於不妨礙紫外線硬化的範圍内，較佳為相對於 該注模聚合用活性能量線硬化型樹脂組成物〗〇〇質量份， 分別處於0.01〜40質量份的範圍内。 可添加到本發明的分散體中的光聚合起使劑，例如可 舉出二笨曱酮、3,3，_二曱基—4_曱氧基二苯曱酮、4，斗， —雙二曱基氨基二苯曱酮、4,4,一雙二乙基氨基二苯甲_、 4,4’一二氣二苯甲酮、米其勒_、3,3’，4,4，—四（三級丁基過 氧Ik基）—苯甲酮等二苯曱酮類；口山酮、嗟π頓酮、2 —甲基 噻噸酮、2—氣噻噸酮、2,4~二乙基噻噸酮等氧雜蒽酮、噻 噸酮類；苯偶因、苯偶因曱基醚、苯偶因乙醚、苯偶因異 丙基鱗4偶因鍵類；苯偶醯、雙乙醯等α 一二酮類；二硫 化四甲胺硫曱醯基、對甲笨二硫醚（t〇lyldisulfide)等硫醚 類，4 —二曱基氨基笨甲酸、4一二曱基氨基苯曱酸乙酯等 苯曱酸類；3,3，一羰基一雙（7 ~二乙基氨基）香豆素、丨—羥 39 201127480 基環己基苯基酮' 2,2，一二甲氧基一1，2—二苯基乙烷一1 — 酮、2—甲基一1—〔4-(曱硫基）苯基〕一2 —嗎啉基丙烷一 1_酮、2—苄基一2—二曱基氨基一丨一（4 —嗎啉基苯基）_ 丁烧一1_酮、2 —經基一 2 —甲基一苯基丙院一1—酮' 2,4,6 —三曱基笨曱醯基二苯基氧化膦 '二（2,4,6—三曱基苯 曱醢基）苯基氧化膦、1一〔4_(2 一羥基乙氧基）苯基〕一 2 —羥基一2—曱基~1_丙烷—丨—酮、[―(4_異丙基苯基） —2—羥基一 2 —甲基丙烷—丨一酮、丨_ (4 —十二烷基苯基） —2 -羥基一2—甲基丙烷一丨—酮、4_苯曱醯基—4, 一甲基 二甲硫醚、2,2’一二乙氧基苯乙酮 '偶苯醯二曱基縮酮、苄 基一卢—曱氧基乙基縮醛、鄰苯甲醯基苯甲酸曱基、二（4 一二曱基氨基苯基）酮、對二甲基氨基苯乙酮、α,α—二氯 —4 一苯氧基苯乙酮、戊基—4 一二甲基氨基苯甲酸酯、2 — (鄰氣苯基）一4,5 —二苯基咪唑二聚物、2,4一雙三氣曱基—6 一〔雙（乙氧基羰基甲基）氨基〕苯基—s_三嗪、2,4一雙三 氣甲基6 (4一乙氧基）苯基一S—三》秦、2,4—雙三氯甲基 (3溴4 —乙氧基）苯基—§ 一三嗪蒽醌、2 _三級丁 基蒽醌、2-戊基蒽醌、冷-氣蒽醌等。 上述光聚合起始劑可以單獨使用或2種以上組合使 用。其用量沒有特別地限制，但是為了保持良好的感光度， …析出、塗膜特性變差等，較佳為相對於活性能量 線硬化型樹脂組成物100質量份為〇〇5〜2〇質量份，其中 特佳為0.1〜10質量份的範圍進行使用。 上述光聚合起始劑’選自卜經基環己基苯基酮、2— 經基—2一甲基-1-苯基丙烧-1-明、1-〔4一(2一經基 40 201127480 乙氧基）苯基〕一2 —羥基_2—曱基一1 一丙院一 1 一酮、噻 噸酮及噻噸酮衍生物、2,2’ 一二甲氧基一 1，2 —二苯基乙烷一 1 一酮、2,4,6 —三甲基苯曱醯基二苯基氧化膦、二（2,4,6 — 三甲基苯甲醯基）笨基氧化膦、2_甲基一 1一〔4—(甲硫基） 苯基〕_2_嗎啉基一 1—丙酮、2 —苄基一 2_二曱基氨基 —1 — (4 —嗎琳基苯基）—丁烧一 1 一酮中的1種或2種以上 混合體系，因可以得到硬化性高的塗布用活性能量線硬化 型樹脂組成物，故為特佳。 上述光聚合起始劑的市售品，例如可舉出Irgacure — 184、Irgacure— 149、Irgacure— 261、Irgacure— 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(Ciba Specialty Chemicals 公司製）、Lucirin TP0(BASFF 公司製）、 KAYACURE- DETX ' KAYACURE- MBP ' KAYACURE-DMBI、KAYACURE- EPA、KAYACURE— 〇A〔曰本化藥（股） 製〕、VICURE— 10、VICURE— 55(STAUFFER Co. LTD 製）、 TRIG0NALP1(AK Z 0 Co. LTD 製）、SANDOR Y 1000(SANDO Z Co. LTD 製）、DEAP(APJOHN Co. LTD 製）、QUANTACURE - PDO、QUANTACURE — ITX、 QUANTACURE-EPD(WARD BLEKINSOP Co. LTD 製）等。 另外，對於活性能量線硬化型樹脂組成物，還可以在 上述光聚合起始劑中同時使用各種光敏劑。光敏劑，例如 可舉出胺類、脲類、含硫化合物、含磷化合物、含氣化合 201127480 物或腈類或其他含氮化合物等β 另外’為了改進對膜基材的接著性，對於活性 硬化型樹脂組成物，可以同時使用其他樹脂。 線 上述其他樹脂，例如可舉出甲基丙稀酸甲酉旨樹脂 土丙烯酉夂甲酯系共聚物等丙烯酸樹脂；聚苯乙烯 烯酸甲醋-苯乙稀系共聚物；聚醋樹脂；聚胺 二： 月:：聚丁二稀及丁二缔—丙稀猜系共聚物等聚丁；： 月^’雙Μ環氧樹脂' 笨氧樹脂及祕環氧樹脂等環 脂等。 了 使用由本發明的製造方法得到的分散體的活性能量線 硬化型樹脂組成物具有以下特徵：特別是塗布到膜基材ί 的4膜狀塑膠基材上時也可獲得硬度，並且硬化時具有低 收縮，較少發生膜的赵曲（捲曲）。而因此可以適用㈣_ 的塗布。 •^布於上述膜基材上時的塗布量’例如較佳在各種獏 基材上’以乾燥後重量為Gl〜3Gg/m2的範圍，較佳為1〜 的範圍進行塗布。又，關於硬化層的膜厚，相對於 膜狀基材的膜厚為3%以上的膜係容易達到作為硬塗層的硬 度’故較佳。其中，關於硬化層的臈厚’更佳為相對於膜 狀基材的膜厚A 3〜1()()%範圍内之膜，進_步較佳硬化層 的膜厚為相對於膜狀基材的膜厚4 5〜⑽％範圍内，特佳 硬化層的膜厚為相對於膜狀基材的臈厚為5〜5G%範圍内。 塗布活性能量線硬化型樹脂組成物的膜狀基材，可以 使用各種么知的基材β具體來說’可舉出例如塑膠膜狀基 材等。塑膠膜狀基材’例如可舉出聚碳酸醋、聚ρ基丙烯 42 201127480 酸甲酯、聚苯乙烯、聚酯、聚烯烴、環氧樹脂、三聚氰胺 樹脂、三醋酸纖維素樹脂、ABS樹脂、AS樹脂、降冰片稀 系樹脂 '環狀烯烴、聚醯亞胺樹脂等膜基材等。 活性能量線硬化型樹脂組成物的塗布方法， 特別限制地使用公知的方法’例如可舉出棒塗布法、絲棒 塗布法以、氣刀塗布法以、凹版塗布法、反轉凹版塗布法、 膠版印刷法、柔版印刷法、網版印刷法等。 照射的活性能量線，例如可舉出紫外線或電子束。用 紫外線進行硬化時，使用具有氙燈、高壓水銀燈、金屬_ 化物燈的紫外線照射裝置作為光源，視需要而調節光量、 光源配置等，在使用高壓水銀燈的情況下，通常較佳為相 對於具有80〜160W/Cm範圍之光量的一個燈，按5〜5〇m/ 分鐘範圍之的輸送速度進行硬化。另一方面，用電子束進 行硬化時，通常較佳為使用具有1〇〜3〇〇kv範圍之加速電 壓的電子束加速裝置，以5〜50m/分鐘範圍的輸送速度進行 硬化。 上述活性能量線硬化型樹脂組成物係如上所述，硬化 時收縮性小，並且硬度高。因此，藉由使用該組成物’可 以提供在膜基材上設置有該組成物的硬化層而形成的膜。 這種膜適合用於例如以偏光板保護膜、觸摸板等光學物品 用硬塗層膜為代表的各種保護膜、防反射膜、散射膜及等 稜鏡片的背面塗層等。 此外，上述活性能量線硬化型樹脂組成物不僅適合用 於上述保護偏光板、觸摸板等平面狀物品的保護膜，也適 用於上述平面狀物品以外之塑膠物品，例如用來保護行動 43 201127480 電話等家電製品及汽車緩衝器等成型品的表面。 十於使用/舌性月巨量線硬化型樹脂組成物形成保護成型 ::表面之保護層的方法，可舉出塗裝法、料法、片材接 著法等。 塗裝法h將由活性能量線硬化性樹脂組成物所構成之 裝劑進行噴塗’或用簾塗機、親塗機、凹版塗布機等印 機在成5L 上塗成外塗層後，照射活性能量線使外塗層 交聯的方法。 轉印法是詩具有脫模十生的基體片#塗布冑活性能量 線硬化型樹脂組成物所形成的轉印材料接著於成形品表 面’然後藉由剝離基體片材將表塗層轉印於成型品表面， 接著照射活性能量線製成交聯塗膜，或者將該轉印材料接 著在成型品表面上，然後照射活性能量線製成交聯塗膜， 接著藉由剝離基體片材將外塗層轉印於成型品表面的方 法。 片材接著法是將於基體片材上具有保護層和視需要使 用之修飾層之保護片接著在塑膠成型品上，從而在成型品 表面形成保護層的方法。其中，本發明的塗布用活性能量 線硬化型樹脂組成物可較佳用於轉印法和片材接著法的用 途。以下對利用轉印法、片材接著法形成保護層的方法進 行詳細說明。 使用轉印法將活性能量線硬化型樹脂組成物形成保護 層係先製作轉印材料。轉印材料可以藉由例如單獨配合活 性能量線硬化型樹脂組成物、或與多官能異氰酸酯、混合 後塗布在基材片上，進行加熱使硬化型樹脂組成物半硬化 201127480 (B -階化）而加以製造。 t與活性能量線硬化型樹脂組成物併用的多官能異氰酸 醋，沒有特別地限制，可以使用公知的各種多官能異氰酸 酷。例如可以使用異佛爾酮二異氮酸醋、二甲苯二異氣酸 酉曰氫化—曱苯二異氰酸酷、曱苯二異氰酸醋、二笨基甲 異氰酸醋、U6—己烷二異氰酸酷、上述物質的三聚：、 夕7°醇和上述二異氰酸酯反應所形成的預聚物等。即，使 聚合物中所含的經基與多官能異氰酸醋的異氰酸醋基進行 反應而進行B —階化。 對於活性能量線硬化型樹脂組成物和多官能異氰酸酿 的使用比例，通常較佳為活性能量線硬化型樹脂組成物的 每ϋα多官能異氛酸s|的異氛酸醋基的比例& m 1/1 ’ 更佳為 1/〇.〇5〜1/〇 8。 基材片，較佳為具有脫模性的片材。該基材片，例如 可舉出塑膠片、金屬、纖維素片、這些片材的複合物等。 上述塑膠片，例如可舉出上述塑膠狀膜等。 片 金屬落，例如可舉出紹箱、銅笛等。又，上述纖維素 例如可舉出破璃紙、塗布紙、赛璐玢等。 基材片，較佳為塑膠片，纟中更佳為聚酯片。 製每轉P材料係，首先在基材片上塗布活性能量線硬 化型樹脂組成物。該樹脂組成物在後述的保護層形成方法 :，形成成型品表面的最外層，而形成保護成型品及成型 的圖案層免文试劑及摩擦損害的層。塗布轉印材料用 硬化性樹脂組成物Μ 士、土 .,, 的方法’例如可舉出凹版塗布法、輥塗 法喷塗法π塗法（Hp coating)、點塗法（_邮⑶扣⑻ 45 201127480 等塗布法，凹版印刷法、網版印刷法等印刷法等。塗布時， 從形成良好的耐磨損性及耐試劑性上考慮，較 伴’ 的方式進行塗布，其中更佳為使保: 層厚度為1〜的方式進行塗布。 上述保護層對基體片材的剝離性優良時，在基體片材 上直接設置保護層的方式塗布轉印用硬化性樹脂：成物即 可’但是為了改善保護層對基體片材的剝離性亦可在基 體片材上設置保護層之前，f面形成脫模層。脫模層在 後述的成型品的保護層形成方法中…將轉印材料的保 遵層轉印到成型品表面，而從成型品上剝離基體片材時， 與基體片材-起從保護層上脫除。用於形成脫模層的脫模 劑：例如可以使用三聚氰胺樹脂系脫模劑、有機聚石夕氧系 脫模劑、氟樹脂系脫模劑 '纖維素衍生物系脫模劑、尿素 樹脂系脫模劑、聚稀烴系脫模劑、石壤系脫模劑 '該等之 複合型脫模劑等。形成脫模層的方法，可舉出凹版塗布法、 親塗法、f塗法、浸塗法（Hp c〇ating)、點塗法，凹版印刷 法、網版印刷法等印刷法。 在基材片上塗布轉印用硬化性樹脂組成物後，使其乾 燥。乾燥可以藉由例如加熱來進行。塗布用活性能量線硬 化型樹脂組成物会右古_,, 风物3有有機溶劑時，有機溶劑藉由該加轨而 被除去。加熱溫度通常為55〜咳，較佳& i〇〇〜n 加熱時間通常為30秒〜3〇分鐘，較佳為卜⑺分鐘，更佳 為1〜5分鐘。 對於本發明的轉印材料上的B-階化樹脂層，從能夠容 易地在該樹脂層上刷覆其他層捲取轉印材料方面考慮較 46 201127480 佳為在照射活性能量總益沾π比讯丄 '策剐的階奴中，處於不黏的狀態。 轉印材料上也可以开> 士園安_ a 形成圖案層。在B ~階化樹脂層上通 常形成圖案層作為印刷層 冲J赝。印刷層的材質，可以使用以聚 乙烯系樹脂、$醯胺系樹脂、聚醋系樹脂、聚丙稀酸系樹 月田聚胺曱Ϊ文乙醋系樹脂、聚乙烤縮酿系樹脂、聚酿胺甲 乙S曰系樹月日纖維素顆系樹脂 '醇酸樹脂等樹脂作為黏 結劑’含有適當顏色的顏料或染料作為著色劑之著色油 墨。作為形成圖案層的士、t ,, 增的方法，例如可以使用膠版印刷法、 凹版印刷法、網版印刷、本望a m . 『叫法等沐用之印刷法等。特別是為了 進行多色印刷和色階顯現， ^ 凡仗用膠版印刷法和凹版印刷法 較為適宜。另外，在單色愔 巴It况下，也可以採用凹版塗布法、 親塗法、點塗法、浸塗法i + t 复法4塗布法。對於圖案層，根據 要顯現的圖案，有整面机番从法 很像心 负^•面β又置的情況及局部設置的情況。 外，圖案層亦可由今麗$ 屬4鍍層形成或由印刷層和金屬蒸 層組合形成。 …'又 另外$保濩層及圖案層對成型品有足夠的接著性 時，可以不設詈技鍫思 , 接者層，也可以視需要形成接著層。 層疋在成型品表面t技名· g . 面上接者具有上述各層的轉印材料的層。 接者層係形成於^早思—、 、’、羞a或圖案層上想要進行接著的部分。 即’如果想要接著的部分 “ 疋整®，則整面形成接著層。如 果L要接著的部分是戶^ β ^ 疋局口ρ的，則局部地形成接著層。作Α 接著層，適宜借闲彳南人认上、 α ;成型品材料的感熱性或感壓性樹 曰。歹’。’成型品的材質為聚丙烯酸系樹脂時，可使 :稀酸系樹脂。另外’成型品的材質是聚苯系 樹脂、聚碳酸醋系樹脂、苯乙稀共聚物系樹脂、聚；= 47 201127480 谢物樹月日時，使用與該等樹脂親和性好的聚丙稀酸系 樹月曰、聚苯乙稀系樹脂 '聚醢胺系樹脂等即可。另外，成 5L -的材質為聚丙烯樹脂時’可以使用氣化聚烯烴樹脂、 氣乙稀S“夂乙烯酯共聚物樹脂、環化橡膠、香豆酮—茚 樹脂。作為接著層的形成方&，可舉出凹版塗布法、輥塗 法、點塗法等塗布法’凹版印刷法、網版印刷法等印刷法。 又，轉印材料的構成不限於上述形式，例如在使用呈 現成型品本身形態及透明性且僅以表㈣護處理為目的之 轉印材料的情況時’可以按照上述方式依序於基體片材上 y成B匕化樹月曰層及接著層，從轉印材料中省略圖案層。 另外，轉印材料在B一階化樹脂層上具有圖案層及接著 層/亦可在些層之間設置錫固層。錯固層是用於提高 /等層間的密合性’保護成型品及圆案層免受化學試劑損 :的樹脂層，例如可以使用雙液硬化型聚胺曱酸乙酿樹 脂'三聚氰胺系樹脂、環氧系樹脂等熱硬化性樹脂、氣乙 烯共聚物樹脂等熱塑性樹脂。作為形成錨固層的形成方 法，有凹版塗布法、輥塗法'點塗法等塗布法，凹版印刷 法及網版印刷法等印刷法。 為了使用上述轉印材料形成成型品的保護層，例如， 將作為上述轉印材料的B階化樹脂層與成型品接著昭 ，、、、 射活性能量線使樹脂層硬化即可。具體來說，可舉出以下 方法：例如將作為轉印材料的B—階化樹脂層接著於成型品 表面，然後將轉印材料的基體片材剝離，藉此使得作為轉 P材料的B —階化樹脂層轉印到成型品表面上，之後藉由活 吐也置線照射使之進行能量線硬化，從而進行樹脂層的交 48 201127480 聯硬化之方法（轉印法）、以 具内’於模腔内注射充滿樹脂:;：：夹入於成型模 使轉印材料接著於其表面，,:離=:'成型品的同時 品上’然後藉由照射活性能量線進二=而轉印到成型 •層的交聯硬化的方法（同時成型轉印法）等。 方：：：：樹脂層的交聯硬化和轉印步驟，較佳為上述 :斤不依序使得轉印材料接著到成型品表面上，然 由剝離基體片材而轉印到 、、、曰 绩日“ + ▲ 轉成型。口表面，之後進行活性能量 表面=之步驟’但亦可為依序使得轉印材料接著於成型品 :其攸基體片材側照射活性能量線，使保護層硬化， 接者將基體片材剝離來進行轉印之步驟。 、作為上述成型品，材質並沒有限制，例如可舉出樹脂 成型品、木工製品、它們的複合製品等。這些成型品可以 明、半透明、不透明中的任-種。另外，成型品可以 疋者色的’也可以是未著色的。樹脂可舉出聚笨乙稀系樹 脂、聚烯烴系樹脂、ABS樹脂' As樹脂等通用性樹脂。另 外，也可以使用聚笨峻.聚苯乙婦系樹脂、聚碳酸醋系樹 脂、聚縮醛系樹脂、丙烯酸系樹脂、聚碳酸_改質聚笨醚 樹脂、聚對苯二甲酸乙二醋樹脂、聚對苯二甲酸丁二醋樹 脂、超高分子量聚乙烯樹脂等通用工程樹脂，以及聚砜樹 脂、聚苯硫醚系樹脂、聚苯醚系樹脂、聚丙烯酸酯樹脂、 聚醚醯亞胺樹脂、聚醯亞胺樹脂、液晶聚醋樹脂、聚芳基 系而寸熱樹脂等超級工程樹脂。另外，亦可使用添加了玻璃 纖維及無機填料荨增強材料的複合樹脂。 本發明的成型品的保護層的形成方法中使用的活性能 49 201127480 量線’例如可舉出電子束、料線、τ射線等。照射條件 可以根據為了得到保護層而使用的轉印材料用硬化性樹脂 組成物的組成來決定’通常較佳為照射累積光量為5〇二 5〇〇〇mj/cm2進行照射’更佳為照射累積光量為50〜 2000mj/cm2進行照射。 、以下具體說明利用上述轉印法來形成成型品保護層之 方法。首先，在成型品上以接著層側在下的方式配置“ 材料。接著，使用具備耐熱之橡膠狀彈性體，例如具備多 橡膠的輥式轉印機、可逆（up_d〇wn)轉印機等轉印機，經由 設定為溫度80〜戰、壓力5〇〜2〇〇kg/m2的條件的耐教 橡膠狀彈性體，從轉印材料的基體片材側施加熱及/或屢 力。藉由此方式將接著層接著在成型品表面。接著，如果 在冷卻後剝離基體片材’則基體片材和樹脂層的交界面。上 會發生剝離。又，當於基體片材上設置脫模層時，若將基 體片材剝離，則脫模層和樹脂層的交界面上會發生剝離。 最後’藉由照射活性能量線，使轉印到成型 完全交聯硬化，形成了俘嘈麻,. 的樹月曰層 形成了保濩層。再者，照射活性能量線的 乂驟也可以在剝離基體片材步驟之前進行。 、 以下’具體說明使用注射成型之同時成型轉印法來形 成成型品保護層之方法。首先，在 ^ ,^ m ^ 在由，舌動模和固定模所組 ::成型用模具内以接著層為内側，亦即以基體片材接於 固疋模的方式送入轉印材料。此時， 、 轉印材料片，也可以間歇性地放入長型轉 :。使用長型轉印材料時，使用具有位置決定裝置的輸； d ’使轉印材料的圖案層和成型用模具的方位達到一致 50 201127480 即可。另外，間歇性地送入轉印材料時，由感測器檢測到 轉印材料的位置後’若以活動模和固定模固定轉印材料， 可以將轉印材料一直固定在相同的位置，不會發生圖案層 的位置偏離’因此是便利的。閉上成型用模具後，從設置 於活動模之澆口對模具中注射填充熔融樹脂，在形成成型 品的同時’使轉印材料接著於其表面上。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，將基體片 材剝離後’藉由照射活性能量線使樹脂層完全交聯硬化， 從而形成保護層。另外，亦可在照射活性能量線後，剝離 基體片材。 又本發明的轉印材料用硬化性樹脂組成物不僅可作 為轉印材料製造用組成物，還可以藉由上述凹版塗布法、 輥塗法、點塗法等塗布法，凹版印刷法及網版印刷法等印 刷法喷塗法等來塗裝於膜、片材、成型物等成型品上。 以下針對片材接著法進行說明。作為片材接著法，例 如可舉出使預先製成的保護層形成用片材的基體片材與成 型Π〇相接著，然後藉由加熱使之熱硬化，以進行B —階化之 樹脂層的交聯硬化的方法（後接著法）、以及將上述保護層形 成用片材失入於成型模具内，於模腔内注射充滿樹脂，在 付至:樹月曰成型品的同時，使其表面與保護層形成用片材相 接著後藉由加熱使之熱硬化，從而進行樹脂層的交聯 硬化的方法（同時成型接著法）等。 上述保濩層形成用片材可以藉由例如製造上述轉印材 料的方法等來製造。此時’⑨基體片材上塗裝硬化性樹脂 組成物時’在基體片材和硬化性樹脂組成物的接著力不足 51 201127480 的情況下二利用以下方法可提升基體片材與硬化性樹脂組 成物之接著性·· 1.在基體片材之塗裝硬化性樹脂組成物的面 上塗布底彡並於其上塗裝硬化性樹脂組成物、2藉由電晕 放電等來活化基體片材的表面等方法。域1中使用的底 漆例如可以使用雙液硬化性聚胺甲酸乙醋樹脂、三聚氰胺 系樹脂、環氧系樹脂等熱硬化性樹脂，氣乙烯共聚物樹脂' 由丙烯酸樹脂組成的水性乳膠等熱塑性樹脂。接著劑之黏 布方法例如可舉出凹版塗布法、輥塗法、點塗法等塗布法， 凹版印刷法 '網版印刷法等印刷法。 在上述製造轉印材料的方法中’將活性能量線硬化型 樹脂組成物塗裝於基體片材後’照射活性能量線。利用該 活性能量線使硬化性樹脂組成物中的（甲基）丙烯醯基因自 由基聚合反應而鍵結’形成三維交聯’使硬化性樹脂組成 物硬化。 當活性能量線硬化性樹脂組成物係使用含有有機溶劑 的活性能量線硬化型樹脂組成物時，亦可在塗布到基體片 材上後除去有機溶劑。有機溶劑的除去，例如可以在照射 活性能量線後進行，也可以在照射活性能量線前進行。作 為除去方法，可以直接放置等待揮發，也可以使用乾燥機 等進行乾燥，但疋通常較佳為除去有機溶劑時的溫度為7〇 〜130°C，進行10秒〜1〇分鐘左右。 再者，保護層形成用片材的構成並不局限於上述形 式，例如在使用呈現成型品本身形態及透明性且僅以表面 保護處理為目的之保護層形成用片材的情況時，可於基體 片材上依序形成硬化的樹脂層及接著層，從保護層形成用 52 201127480 片材中省略圖案層。 又，當保護層形成用片材的圖宰 上π—你 系層上具有樹脂層時， 也可以在該#之層間設置錨固層， 麻叫★私入l 馬固層是用於提高該等 層間之黏合性的樹脂層，可使用 7 ,t.. , ^ ^ j如雙液硬化性聚胺甲酸 乙s曰树月曰、二聚虱胺系樹脂、環氧 ^ r ^ u s , 乳糸刼脂等熱硬化性樹脂、 氣乙稀共聚物樹脂等熱塑性樹脂。 ..JL. . 形成錯固層的形成方 法，有凹版塗布法、輥塗法、點 龙去等塗布法，凹版印刷 法及網版印刷法等印刷法。 片材接著法中使用的成型品例 土士办丨-Μ > · 列如可以使用在上述轉印 法中例不的成型品。 後接著法中接著成型.品和保讀居丄 1蔓層形成用片材的方法， 可舉出例如以下方法：將接著 „ . ^ μ ^ 按者幻塗布於保護層形成用片材 的基體片材及/或成型品表面， Α ^ ^ , 使诗保蠖層形成用片材的 基體片材與成型品表面相接著的 ^ a 方法、將雙面黏著帶貼附 於保濩層形成用片材的基體片材 ^ Μ ^ ^ 何及/次成型品表面之後，剝 離雙面黏者帶的脫模保護片 更點者面露出，以使得保護 2 = Γ的基體片材與成型品表面相接著的方法、將 於保護層形成用片材的基體片材以形成接著面 後’預先製成以剝離保護片伴 .保4接者面之保護層形成片 材，剝離該保護層形成片材的f <幻剩離保護片，以使得基體片 材的接者面與成型品表面相接 ^ . 按者的方法等。在同時成型接 者法中’係不使用接著劑， ^ P ^ 而疋鞛由模内成型時的熱使基 體片材熔融，藉此使保護層 於h 更^成用片材與成型品成為- 體從而可以接著保護層形成用K， A , ., ^ 〜战用片材與成型品。此處，作 為上述後接著法中使用的接著 則可舉出例如胺甲酸乙酯 53 201127480 系接著劑、環氧系接著劑、酯系接著劑、丙烯酸系接著劑 及熱熔型接著劑等。 以下，具體說明利用上述後接著法來形成成型品之保 護層的方法。首先，在成型品上以接著層側在下的方式配 置保護層形成用片材。接著，使用具備耐熱橡膠狀彈性體， 例如矽橡膠的輥式轉印機、可逆轉印機等轉印機，藉由設 定為溫度80〜260°C、壓力50〜200kg/m2的條件的耐熱橡 膠狀彈性體，從保護層形成用片材的保護層側施加熱及/或 壓力。利用這種方式將接著層接著在成型品表面。最後， 措由加熱使成型品上形成的樹脂層完全交聯硬化，形成保 護層。 下，具體說明使用注射成型之同時成型轉印法來形 成成型品的保護層的方法。首先，在由活動模和固定模組 成的成型用模具内以接著層作為内側，亦即以基體 於固定模的方式送入轉印材料 心释叩材枓。此時，也可以一片一片地 送入轉印材料片，纟可以間歇性地送人長型轉印材料的必 需部分。使用長型轉印材料時M吏用具有位置決定裝置的 輸送裝置使轉印材料的圖案層和成型用模具的方位達到 一致即可。另夕卜’間歇性地送人轉印材料時，由感測器檢 測到轉印材料的位罟 、 後，右以活動模和固定模固定轉印 料，可以將棘Hp #m P#ff—直固定在相同的位置，不會發生圖 案層的位置偏離，因士 θ 因此疋便利的。閉上成型用模具後，從 活動模上設置的潘口别_祕 成型品的同時，使…=射填充炼融樹脂，在形成 品冷卻後，打開成㈣接者到其表面上。將樹脂成型 1用模具取出樹脂成型品。最後，用熱 54 201127480 而使樹脂層完全交聯硬化，以形 風式供相等進行加熱，從 成保護層。 (貫施例） 以下列舉實施例及比較例， 〜 权例對本發明進行更具體地說 明。貫例中的份及％，除非有牲丨托。口 井秃特別指明，否則基準均為質 量。 實施例1 在具備了授拌裝置、冷卻管、滴液漏斗及氮氣導入管 的反應裝置中，加入甲基丙稀酸縮水甘油醋(以下，簡記為 GMA ’’ ）250g、曱基異丁基酮（以下，簡記為 MIBK”）lGG0g及過氧化三級丁基乙基己酸醋（以下，簡記 為“P-O”）l〇g後，在氮氣流下以約i小時使體系内的溫 度升溫到約90°C，保溫1小時。接著，從預先加入了由gma 750g，P— 〇 3〇g所組成之混合液的滴液漏斗，在氮氣流下 向系内滴加混合液約2小時，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60。(：後，將氮 氣導入管替換成空氣導入管，加入丙烯酸（以下，簡記為 AA )507g、甲氧基醌（meth〇quinone)2.3g 及三苯膦 9.3g 並加以混合後，在空氣起泡下，升溫到n〇°c。在相同的溫 度下保溫8小時後，加入曱氧基醌1 6g，再進行冷卻，添 加MIBK使不揮發成分為50%，得到二氧化矽微粒用反應 性分散劑（A — 1)的溶液。該反應性分散劑（A —丨）的丙烯醯基 當量為約214g/eq，羥基值為約262mgKOH/g、重量平均分 子量約30,000。 實施例2 55 201127480 使用與實施例1相同的反應裝置，加入GMA 125g，曱 基丙烯酸曱酯（以下’簡記為‘‘ MMA”）125g，MIBK 1000g 及P — Ο 10g後，在氮氣流下以約i小時使體系内的溫度升 溫到約90°C ’保溫1小時。接著，從預先加入了由GMA 3 75g、MMA 3 75g、P- 〇 30g組成之混合液的滴液漏斗，在 氮氣流下向體系内滴加混合液作用約2小時，在相同溫度 下保溫3小時。然後，升溫到12(rc，保溫2小時。冷卻到 60°C後’將氮氣導入管替換成空氣導入管，加入aa 254g、 甲氧基酿2 · 3 g及二本膦9 · 3 g進行混合後’在空氣起泡下， 升溫到110°C。在相同的溫度下保溫8小時後，加入曱氧基 覼1.6g’進行冷卻，進而添加MIBK使不揮發成分為5〇%， 得到二氧化矽微粒用反應性分散劑（A — 2)的溶液。該反應性 分散劑（A — 2)的丙稀醯基當量為約356g/eq，經基值為約 158mgKOH/g、重量平均分子量約40,000。 實施例3 使用與實施例1相同的反應裝置，加入GM A 75 g，MM A 175g ’ MIBK 1000g及P - 〇 8g後’在氮氣流下作用約1小 時’使體系内的溫度升溫到約9(TC，保溫1小時。接著， 從預先加入了由GMA 300g、MMA 700g、p— 〇 23g組成之 混合液的滴液漏斗，在氮氣流下向體系内滴加混合液作用 約2小時，在相同溫度下保溫3小時。然後，升溫到12〇 °C，保溫2小時。冷卻到60。(：後，將氮氣導入管替換成空 氣導入管，加入AA 152g、甲氧基酿2.3g及三苯膦5.6g進 行 昆合後’在空氣起泡下，升溫到110°C。在相同的溫度下 保溫8小時後，加入甲氧基醌1.6g ’進行冷卻，進而添加 56 201127480 MIBK使不揮發成分為50%，得到二氧化石夕微粒用反應性 分散劑（Α — 3)的溶液。該反應性分散劑（Α — 3)的丙烯醯基當 量為約545g/eq，羥基值為約i〇3mgK：〇H/g、重量平均分子 量約 70,000 。 實施例4 將以固體成分計為2 5 g的反應性分散劑（a — i )、二季戊 四醇六丙烯酸酯（DPHA)25g、二氧化矽微粒（日本aer〇sil 股份有限公司製造的“ Aerosil 200” ，平均一次粒徑約 12nm)50g及MIBK 20〇g進行混合，得到混合物。 使用壽工業股份有限公司製造的Ultra Apex Miu UAM015”將該混合物中的二氧化矽微粒加以分散。此處 使用的Ultra Apex Mill “UAM015”是具有定子内徑為 = ，内容積為0.17公升，分離器的直徑為4〇爪爪必， 刀離器的轉盤間隔設置為5mm的濕式球磨機（圖2中，不具 備取出口 19的類型）者。製造分散體時，在濕式球磨機中以 相對於濕式球磨機容積為50體積％的量填充中值粒徑為％ 以m的氧化鍅珠。 利用泵從供給口將原料槽内的上述混合物供給到濕式 球磨機中。使轉子具有恒定旋轉速度（轉子前端的周向速度 2 8m/sec)地運轉濕式球磨機，以每分鐘2〇〇mi的流量對混 合物進行循環粉碎。進行30分鐘循環粉碎，得到二氧化矽 微粒分散在反應性分散劑（A—小則^ ΜΙΒκ之混合物 中而成的分散體。用蒸發器將所得之分散體中的Μ·除 去，得到不揮發成分濃度為50%的反應性分散體。 在該反應性分散體100份中加入光起始劑「Irgacure 一 57 201127480 184」2份’得活性能量線硬化性樹脂組成物。將活性能 量線硬化性樹脂組成物在室溫（25<t)下保# 2個月也不產 生沉降物，貯存轉定姓肖# , 廿摁疋性良好。另外，在下述條件下製作硬 化塗膜’測定鉛筆硬度時，為5H。 鉛筆硬度的測定方法 1. 硬化塗膜的製作方法 用棒塗布機將活性能量線硬化性樹脂組成物塗布在三 醋酸纖維素（TAC)膜（臈厚40um)上（膜厚10 y m)，在70。匚乾 燥1分鐘，在氮氣下使用高壓水銀燈’在250mJ/cm2照射量 下使之通過，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 K 5400，藉由載荷為500g的鉛筆畫線試驗評 價上述試驗片的硬化覆膜。 實施例5〜1 〇 除了進行表1中所示之混合外，按照與實施例4相同 之方式製造反應性分散體。使用得到的反應性分散體，按 與實施例4相同的方式得到活性能量線硬化性樹脂組成 物。按照與實施例4相同的方式測定貯存穩定性和硬化塗 膜的錯筆硬度’其結果示於表1中。 58 201127480 表1Grain Mill ^ Mechagaper Grain Mill > Cerapower Grain Mill ^ Dual Gram Mill ^ AD Mill' Twin AD Mill. Basket Mill ' Twin basket mill 'Apex Mill, Ultra 36 201127480 AW MlU, _ MU1, etc. . Among them, Ultra Apex Mill is preferred. Further, in the manufacturing method of the present invention, a bead mill manufactured by Xiao Fmetech Co., Ltd. is also preferred. The bead mill STAR-MILL is provided with: a cylindrical container having a collecting population at the end, a freely rotatable search shaft disposed in the longitudinal direction of the container, and being connected to the mixing shaft outside the container a driving device, wherein the picking shaft has a stirring member, and a grinding medium is added to a space between the stirring shaft and the inner surface of the container, and the picking shaft is rotationally driven by the driving device while introducing a material from the collecting inlet; Thereby, the dioxo-cut particles in the material are pulverized, and a hollow portion having a medium inlet is formed in the vicinity of one end of the accommodating shaft, and a slit is formed in the (four) axis. The slit is such that the hollow portion communicates with the hollow portion. a space between the sandalwood shaft and the inner surface of the container, and as the material moves, the medium reaching the other end of the container enters the hollow portion of the mixing shaft from the collecting inlet to return from the gap (four) A cyclical movement of the space between the shaft and the inner surface of the container. In the above-described mixing type pulverizing apparatus, a slurry σ is disposed in a hollow portion of the mixing shaft, and a screen is provided so as to surround the aggregate outlet in the hollow portion, and the upper mesh is rotatably driven. In the above-described medium-mixing type pulverizing apparatus, since the screen for separating the medium from the slurry is driven to rotate, the exciting material and the medium reaching the vicinity of the screen also induce a rotational motion 'the centrifugal force caused by the rotating motion is the medium The square is higher than the side of the feed, so the medium produces a biasing force that separates from the charge. Therefore, the medium circulates without approaching the screen. Therefore, it is possible to remove the medium from the slurry in an effective manner. The dispersion obtained by the production method of the present invention can be adjusted to a concentration suitable for the coating method by adding a suitable solvent and volatilizing the solvent. The solvent to be added 'is exemplified above as the organic solvent (s). The dispersion obtained by the production method of the present invention may be used as an active energy ray-curable resin composition, or may be used in combination with other compounds as needed. Examples of the compound include the active energy ray-curable monomer (M), an active energy ray-curable oligomer (〇), an ultraviolet absorber, an antioxidant, a lanthanide additive, an organic bead, an additive, and a stream. A denaturing controlling agent, an antifoaming agent, a releasing agent, a decane coupling agent, an antistatic agent, an antifogging agent, a coloring agent, and the like. The above ultraviolet absorbing agent may, for example, be a bis(2-hydroxyl-(3-dodecyloxypropyl)oxyindole-2-hydroxyphenyl]-46-bis(2-dimethyl group). Phenyl H,3,5-tripa, 2-[4-quinone (2-diyldiamine; dialkylglylideyloxy)oxy-2-hydroxyphenyl]-4,6-di (2 41-2) Phenyl b...three. et al. Triazine derivatives, Bu (2, Oxygen I: Methyl strepyl) benzotrisodium, 2-(2,------------ phenyl) Sit, 2-^-benzol-piperidinyl- 4-dodecyloxydi- and indole imhene carboxy-4-do--o-nitro-oxyloxy- 4-12-oxyl域 。. The domain antioxidants include, for example, antioxidants, cation-based antioxidants, organic access k ~ _ " antioxidants, phosphate-based antioxidants, etc.丨Phenyl W II:::: 二曱T oxygen institute, «modified dimethyl oxy-oxygen, sulfhydryl-, cyclane copolymer, polyester modified dimethyl poly-generation 38 201127480 alkane copolymer Fluorine modified dimethyl polyoxyalkylene copolymer, amino modified dimethyl polychlorite The polymer (4) and the phenyl group are classified as "(4). The above organic beads may, for example, be polymethyl methacrylate beads, polycarbonate beads, polystyrene beads, or acrylonitrile acrylate. E-grain, poly-stone oxide beads, glass beads, rickett beads, benzoguanamine resin beads, melamine resin beads, polyolefin resin beads, poly g-residue resin beads , polyamide resin beads, polyimide resin beads, polyvinyl fluoride resin beads, polyethylene resin beads, etc. These organic beads have an average particle size of ~ 10 microns 'can be used alone -帛 2 2 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 The hardening type resin composition is in the range of 0.01 to 40 parts by mass, respectively, in the range of 0.01 to 40 parts by mass. The photopolymerization initiator which can be added to the dispersion of the present invention is, for example, dicuminone, 3, 3 , _ dimercapto- 4_nonyloxybenzophenone, 4, , — bisdidecylaminodibenzophenone, 4,4, mono-diethylaminobiphenyl-, 4,4′-di-benzophenone, Michelin _, 3, 3', 4 , 4, - 4 (tertiary butyl peroxy Ik group) - benzophenones such as benzophenone; ornithrone, oxime ketone, 2-methyl thioxanthone, 2-ox thioxanthone, 2,4~diethyl thioxanthone and other oxaxanthone, thioxanthone; benzoin, benzoin decyl ether, benzoin ether, benzoin isopropyl scale 4 susceptibility bond; Α-diketones such as benzophenone and diacetamidine; tetramethylammonium sulfide disulfide, thioethers such as t〇lyldisulfide, 4-dimercaptoamino acid, 4 Benzoic acid such as ethyl dimethylaminobenzoate; 3,3, monocarbonyl-bis(7-diethylamino)coumarin, hydrazine-hydroxy 39 201127480 Cyclohexyl phenyl ketone ' 2,2 ,1-dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1-[4-(indolyl)phenyl]-2-oxalinylpropane-1-one , 2-benzyl-2-oxanylamino-indenyl (4-morpholinylphenyl)-butylene-1-one, 2-hydroxy- 2-methyl-benzene丙院一1-ketone ' 2,4,6 —tridecyl aglyldiphenylphosphine oxide bis (2,4,6-trimethylphenyl) phenyl phosphine oxide, 1 4-(2-hydroxyethoxy)phenyl]-2-hydroxyl-2-mercapto~1-propane-fluorenone, [-(4-isopropylphenyl)-2-hydroxy-2-methyl Propane-nonanone, 丨_(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-phenylindole-4, monomethyl dimethyl sulfide, 2,2'-diethoxyacetophenone' benzoquinonedidecyl ketal, benzyl-l-decyloxyethyl acetal, phthalyl benzoyl benzoate, two (4 one two Nonylaminophenyl) ketone, p-dimethylaminoacetophenone, α,α-dichloro-4-phenoxyacetophenone, pentyl-4-dimethylaminobenzoate, 2 — ( O-phenyl)- 4,5-diphenylimidazolium dimer, 2,4-di-tris-mercapto-6-bis(ethoxycarbonylmethyl)amino]phenyl-s-triazine, 2,4-double-trimethylmethyl 6 (4-ethoxy)phenyl-S-trisyl, 2,4-di-trichloromethyl(3bromo-4-ethoxy)phenyl-§ one three Azin, 2 _ third-grade butyl hydrazine, 2-pentyl hydrazine, cold-gas hydrazine, and the like. The above photopolymerization initiators may be used singly or in combination of two or more kinds. The amount of use is not particularly limited, but in order to maintain good sensitivity, precipitation, deterioration of coating film properties, etc., it is preferably 〇〇5 to 2 parts by mass relative to 100 parts by mass of the active energy ray-curable resin composition. It is preferably used in a range of 0.1 to 10 parts by mass. The above photopolymerization initiator ' is selected from the group consisting of p-cyclohexyl phenyl ketone, 2--based 2-methyl-1-phenylpropan-1-ol, 1-[4-(2-amino-based 40 201127480 ethoxy) Phenyl]phenyl]-2-hydroxy-2-indenyl-1-1-propan-1-one, thioxanthone and thioxanthone derivative, 2,2'-dimethoxy-1,2-diphenyl Ethyl ethane-1-one, 2,4,6-trimethylphenylnonyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzylidene)phenylphosphine oxide, 2_ Methyl-1 -[4-(methylthio)phenyl]_2-morpholinyl- 1 -acetone, 2-benzyl- 2-didecylamino-1 - (4-cylinylphenyl)- One or a mixture of two or more kinds of butyl ketones is particularly preferable since a coating active energy ray-curable resin composition having high curability can be obtained. The commercially available product of the photopolymerization initiator may, for example, be Irgacure-184, Irgacure-149, Irgacure-261, Irgacure-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 (manufactured by Ciba Specialty Chemicals), Lucirin TP0 (BASFF) KAYACURE-DETX ' KAYACURE- MBP ' KAYACURE-DMBI, KAYACURE- EPA, KAYACURE - 〇A [曰本化药(股)制], VICURE-10, VICURE-55 (manufactured by STAUFFER Co. LTD), TRIG0NALP1 (manufactured by AK Z 0 Co. LTD), SANDOR Y 1000 (manufactured by SANDO Z Co. LTD), DEAP (manufactured by APJOHN Co. LTD), QUANTACURE - PDO, QUANTACURE - ITX, QUANTACURE-EPD (manufactured by WARD BLEKINSOP Co. LTD) Wait. Further, as the active energy ray-curable resin composition, various photosensitizers may be simultaneously used in the above photopolymerization initiator. The photosensitizer may, for example, be an amine, a urea, a sulfur-containing compound, a phosphorus-containing compound, a gas-containing compound 201127480 or a nitrile or other nitrogen-containing compound, etc. Further 'in order to improve adhesion to a film substrate, for activity As the hardening type resin composition, other resins can be used at the same time. The other resin of the above-mentioned line may, for example, be an acrylic resin such as a methyl methacrylate methyl phthalate resin acryl oxime methyl ester copolymer; a polystyrene oleic acid-styrene copolymer; a polyester resin; Polyamine II: Month:: Polybutadiene and Dingsii- propylene-like copolymers and other poly-butyl;: Moon ^ 'double bismuth epoxy resin' stupid resin and epoxy resin and other epoxy resin. The active energy ray-curable resin composition using the dispersion obtained by the production method of the present invention has the following characteristics: in particular, hardness can be obtained even when applied to a film-formed plastic substrate of 4 film-like substrates, and hardened. Low shrinkage, less film curvature (curl). Therefore, the coating of (4)_ can be applied. The amount of coating when the film is placed on the film substrate is preferably applied to a range of G1 to 3 Gg/m2, preferably 1 to 1, for example, on various ruthenium substrates. In addition, it is preferable that the film thickness of the hardened layer is 3% or more with respect to the thickness of the film-form substrate, and the film thickness of the hard coat layer is easily achieved. Wherein, the thickness of the hardened layer is more preferably a film thickness in the range of A 3 to 1 ()% relative to the film thickness of the film-form substrate, and the film thickness of the hardened layer is relatively film-like. The thickness of the base material is in the range of 4 to 10% by weight, and the thickness of the particularly hardened layer is in the range of 5 to 5 G% with respect to the thickness of the film-form substrate. For the film-form substrate to which the active energy ray-curable resin composition is applied, various known substrates β can be used, and specific examples thereof include a plastic film-like substrate. Examples of the plastic film-like substrate include polycarbonate, polyρ-propylene propylene 42 201127480 methyl acrylate, polystyrene, polyester, polyolefin, epoxy resin, melamine resin, cellulose triacetate resin, ABS resin, AS resin, norbornene thin resin, film substrate such as cyclic olefin or polyimine resin. The coating method of the active energy ray-curable resin composition is particularly limited to a known method, and examples thereof include a bar coating method, a wire bar coating method, an air knife coating method, a gravure coating method, and a reverse gravure coating method. Offset printing, flexographic printing, screen printing, and the like. Examples of the active energy ray to be irradiated include ultraviolet rays or electron beams. When curing with ultraviolet light, an ultraviolet irradiation device having a xenon lamp, a high pressure mercury lamp, or a metal lamp is used as a light source, and the amount of light, the arrangement of the light source, and the like are adjusted as needed. In the case of using a high pressure mercury lamp, it is generally preferable to have 80 A lamp having a light amount in the range of ~160 W/cm is hardened at a conveying speed in the range of 5 to 5 〇m/min. On the other hand, when hardening with an electron beam, it is generally preferred to use an electron beam accelerating device having an acceleration voltage in the range of 1 〇 to 3 〇〇 kv to be hardened at a conveying speed in the range of 5 to 50 m/min. As described above, the active energy ray-curable resin composition has a small shrinkage property at the time of curing and a high hardness. Therefore, a film formed by providing a hardened layer of the composition on the film substrate can be provided by using the composition'. Such a film is suitably used for, for example, various protective films such as a polarizing film protective film, a hard coat film for optical articles such as a touch panel, an antireflection film, a scattering film, and a back coating of a ruthenium sheet. Further, the active energy ray-curable resin composition is suitable not only for the protective film for protecting a planar article such as a polarizing plate or a touch panel, but also for a plastic article other than the planar article, for example, for protecting the action 43 201127480 The surface of molded articles such as home appliances and automobile bumpers. The method of forming a protective layer of the protective layer of the surface of the surface-curable resin composition is described in the following paragraphs: a coating method, a material method, a sheet joining method, and the like. The coating method h sprays the agent composed of the active energy ray-curable resin composition or irradiates the active energy with an overcoat layer formed on a 5L by a screen coater, a pro-coater, a gravure coater or the like. A method of cross-linking the outer coating. The transfer method is a substrate sheet in which poetry has a mold release. The transfer material formed by coating the active energy ray-curable resin composition is then applied to the surface of the molded article. Then the surface coating is transferred by peeling off the substrate sheet. Forming the surface of the molded article, then irradiating the active energy ray to form a crosslinked coating film, or applying the transfer material to the surface of the molded article, then irradiating the active energy ray to form a crosslinked coating film, and then peeling the base sheet to form the overcoat layer A method of transferring onto the surface of a molded article. The sheet joining method is a method in which a protective sheet having a protective layer and a decorative layer as needed, which is to be provided on a base sheet, is then applied to a plastic molded article to form a protective layer on the surface of the molded article. Among them, the active energy ray-curable resin composition for coating of the present invention can be preferably used for the transfer method and the sheet joining method. Hereinafter, a method of forming a protective layer by a transfer method or a sheet joining method will be described in detail. The active energy ray-curable resin composition is formed into a protective layer by a transfer method to produce a transfer material. The transfer material can be semi-cured by the active energy ray-curable resin composition or the polyfunctional isocyanate, and then coated on the substrate sheet, and heated to make the curable resin composition semi-hardened 201127480 (B-staged). Made. The polyfunctional isocyanuric acid to be used in combination with the active energy ray-curable resin composition is not particularly limited, and various known polyfunctional isocyanic acid can be used. For example, isophorone diisoxamate vinegar, xylene diisoxanthate hydrazine hydrogenation - phthalic acid diisocyanate, acenaphthyl diisocyanate vinegar, dipyridyl isocyanate vinegar, U6 - The hexane diisocyanate is cool, the trimerization of the above substances: the prepolymer formed by the reaction of the alcohol and the above diisocyanate. Namely, the trans group contained in the polymer is reacted with an isocyanate group of polyfunctional isocyanuric acid to carry out B-stage formation. The ratio of the active energy ray-curable resin composition and the polyfunctional isocyanate to the ratio of the isocyanate group per ϋα polyfunctional succinic acid s| & m 1/1 ' is preferably 1/〇.〇5~1/〇8. The substrate sheet is preferably a release sheet. Examples of the base material sheet include a plastic sheet, a metal, a cellulose sheet, and a composite of these sheets. The plastic sheet may, for example, be the above-mentioned plastic film or the like. For the metal falling, for example, a box, a copper flute or the like can be cited. Further, examples of the cellulose include glass paper, coated paper, celluloid, and the like. The substrate sheet is preferably a plastic sheet, and more preferably a polyester sheet. For the P material system per revolution, the active energy ray-hardening resin composition is first coated on the substrate sheet. In the resin composition, a protective layer forming method to be described later is formed to form an outermost layer on the surface of the molded article, thereby forming a layer for protecting the molded article and the patterned pattern layer exempting agent and frictional damage. The method of coating the curable resin composition for a transfer material, such as sputum and soil, may, for example, be a gravure coating method, a roll coating method, a π coating method (Hp coating), or a spot coating method (a postal (3) buckle. (8) 45 201127480, such as coating method, gravure printing method, screen printing method, etc., etc. When coating, it is better to form a coating with good abrasion resistance and chemical resistance, and more preferably When the protective layer has a good peeling property to the base sheet, the protective layer is directly applied to the base sheet to apply a curable resin for transfer: a product can be used. However, in order to improve the releasability of the protective layer to the base sheet, a release layer may be formed on the f-plane before the protective layer is provided on the base sheet. The release layer is formed in a protective layer forming method of a molded article to be described later... The protective layer is transferred to the surface of the molded article, and when the base sheet is peeled off from the molded article, the base sheet is removed from the protective layer. The release agent for forming the release layer: for example, melamine can be used. Resin release agent, organic Shiyue oxygen-based release agent, fluororesin-based release agent 'cellulose derivative-based release agent, urea resin-based release agent, poly-hydrocarbon-based release agent, stone-based release agent' A mold release agent, etc. The method of forming a mold release layer may be a gravure coating method, a co-coating method, an f coating method, a dip coating method, a dot coating method, a gravure printing method, or a screen printing method. The printing method is applied to a substrate sheet, and then dried, and then dried. The drying can be carried out, for example, by heating. The active energy ray-curable resin composition for coating will be _,, and the wind object 3 When there is an organic solvent, the organic solvent is removed by the addition. The heating temperature is usually 55~cough, preferably & i〇〇~n, and the heating time is usually 30 seconds to 3 minutes, preferably bu (7) minutes. More preferably, it is 1 to 5 minutes. For the B-staged resin layer on the transfer material of the present invention, it is considered that the transfer material can be easily wound on the resin layer by another layer. In the step of slaves, the total energy of the active energy is viscous. The transfer material may also be opened. The pattern layer is formed on the B-staged resin layer. The pattern layer is usually formed as a printing layer. The material of the printed layer can be made of polyethylene resin. , amide-based resin, polyester resin, polyacrylic acid tree, Yuetian polyamine 曱Ϊ 乙 乙 乙 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 A resin such as a resin such as an alkyd resin, which is a coloring ink containing a pigment or a dye of a suitable color as a coloring agent. As a method of forming a pattern layer, t, t, and the like, for example, an offset printing method or a gravure printing method can be used. , screen printing, wangwang am. "Printing method such as naming, etc. Especially for multi-color printing and color gradation, ^ is suitable for offset printing and gravure printing. Further, in the case of a single color, it may be a gravure coating method, a co-coating method, a spot coating method, or a dip coating method i + t complex method 4 coating method. For the pattern layer, according to the pattern to be visualized, there is a case where the whole surface machine is very similar to the case where the surface is set to be negative and the surface is set. Alternatively, the pattern layer may be formed of a enamel coating or a combination of a printed layer and a metal evaporation layer. ...' In addition, when the protective layer and the pattern layer have sufficient adhesion to the molded article, the bonding layer may be omitted, and the bonding layer may be formed as needed. The layer is on the surface of the molded article t. The name is g. The surface has a layer of the transfer material of each layer described above. The layer of the connector is formed on the portion of the pattern, the layer, the shy a or the pattern layer that is desired to be followed. That is, 'If you want the next part to 疋 ® , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , By the way, I can recognize the heat or pressure-sensitive tree of the molded material. 歹'. When the material of the molded product is a polyacrylic resin, it can be: a dilute acid resin. The material is polyphenylene resin, polycarbonate resin, styrene copolymer resin, poly; = 47 201127480 Xie Wushu, using a polyacrylic acid tree with a good affinity for these resins, polystyrene Ethylene resin 'polyamide type resin, etc.. When 5L - is made of polypropylene resin, 'vaporized polyolefin resin, ethylene sulphur S 夂 vinyl ester copolymer resin, cyclized rubber can be used. , coumarone - oxime resin. Examples of the forming layer of the adhesive layer include a coating method such as a gravure coating method, a roll coating method, and a spot coating method, and a printing method such as a gravure printing method or a screen printing method. Further, the configuration of the transfer material is not limited to the above-described form, and for example, in the case of using a transfer material for the purpose of the shape and transparency of the molded article itself and only for the purpose of the surface treatment, the substrate sheet may be sequentially arranged in the above manner. The y is formed into a B-tree layer and a subsequent layer, and the pattern layer is omitted from the transfer material. Further, the transfer material has a pattern layer and a subsequent layer on the B first-order resin layer or a tin-solid layer may be provided between the layers. The staggered layer is a resin layer for improving the adhesion between the layers and the 'protection of the molded article and the round layer from the chemical agent. For example, a two-liquid hardening type polyamine phthalate resin 'melamine resin can be used. A thermoplastic resin such as a thermosetting resin such as an epoxy resin or a gas-ethylene copolymer resin. As a method of forming the anchor layer, there are a coating method such as a gravure coating method, a roll coating method, a spot coating method, a gravure printing method, and a screen printing method. In order to form the protective layer of the molded article using the transfer material, for example, the B-staged resin layer as the transfer material and the molded article may be cured by exposing the active energy rays to the resin layer. Specifically, for example, a B-staged resin layer as a transfer material is attached to the surface of the molded article, and then the base sheet of the transfer material is peeled off, thereby making B as a P-transfer material. The layered resin layer is transferred onto the surface of the molded article, and then subjected to energy ray hardening by a live squirting, thereby performing a method of bonding the resin layer (transfer method). Injection into the cavity filled with resin:;:: sandwiched in the molding die to make the transfer material follow the surface, :: = ''the simultaneous appearance of the molded article' and then by the irradiation of the active energy line into the two = turn A method of cross-linking hardening (simultaneous molding transfer method) printed on a molding layer. The side:::: cross-linking hardening and transfer step of the resin layer, preferably the above: the transfer material is not sequentially applied to the surface of the molded article, but is transferred from the base sheet to be transferred, and Day "+ ▲ transfer molding. The surface of the mouth, followed by the step of active energy surface = 'but can also be followed by the transfer material followed by the molded article: the active substrate of the base sheet is irradiated with active energy rays to harden the protective layer The step of transferring the base sheet to carry out the transfer. The material is not limited as the molded article, and examples thereof include a resin molded article, a wood product, and a composite product thereof. Any of the transparent and opaque types. The molded article may be of a color that is not colored. The resin may be versatile such as a polystyrene resin, a polyolefin resin, or an ABS resin. Resin. In addition, polystyrene, polystyrene resin, polyacetal resin, polyacetal resin, acrylic resin, polycarbonate-modified polyether ether resin, polyethylene terephthalate can also be used. Divine tree , general engineering resins such as polybutylene terephthalate resin, ultra high molecular weight polyethylene resin, and polysulfone resin, polyphenylene sulfide resin, polyphenylene ether resin, polyacrylate resin, polyether sulfimine A super-engineered resin such as a resin, a polyimide resin, a liquid crystal polyester resin, a polyaryl-based resin, or a heat-resistant resin. A composite resin to which a glass fiber and an inorganic filler lanthanum reinforcing material are added may be used. The activity energy used in the method of forming the protective layer 49 201127480 is, for example, an electron beam, a material line, a τ ray, etc. The irradiation condition can be based on a curable resin composition for a transfer material used to obtain a protective layer. The composition determines that 'it is generally preferred that the irradiation cumulative light amount is 5〇2〇〇〇5〇〇〇mj/cm2 for irradiation', and it is more preferable that the irradiation cumulative light amount is 50 to 2000 mj/cm2 for irradiation. A method of forming a protective layer of a molded article. First, a "material" is disposed on the molded article such that the adhesive layer side is on the lower side. Next, a heat-resistant rubber-like elastic body, for example, a multi-rubber roll transfer machine or a reversible transfer machine such as a transfer machine is used, and the temperature is set to 80°, and the pressure is 5〇2. The rubber-resistant elastic body of the 耐kg/m2 condition applies heat and/or repeated force from the side of the base sheet of the transfer material. In this way, the adhesive layer is subsequently applied to the surface of the molded article. Next, if the base sheet 'is peeled off after cooling, the interface between the base sheet and the resin layer. Peeling will occur on it. Further, when the release layer is provided on the base sheet, if the base sheet is peeled off, peeling occurs at the interface between the release layer and the resin layer. Finally, by irradiating the active energy ray, the transfer to the molding is completely cross-linked and hardened to form a captive ramie, and the eucalyptus layer forms a protective layer. Further, the step of irradiating the active energy ray may be performed before the step of peeling off the base sheet. Hereinafter, a method of forming a protective layer of a molded article by a simultaneous transfer molding method using injection molding will be specifically described. First, the transfer material is fed in the form of ^ , ^ m ^ in the mold of the tongue mold and the mold set: the mold is formed with the back layer as the inner side, that is, the base sheet is attached to the mold. At this time, the transfer material sheet may be intermittently placed in a long shape: When a long transfer material is used, the transfer with the position determining means is used; d' is such that the orientation of the pattern layer of the transfer material and the molding die are uniform 50 201127480. In addition, when the transfer material is intermittently fed, after the position of the transfer material is detected by the sensor, 'If the transfer material is fixed by the movable mold and the fixed mold, the transfer material can be fixed at the same position at all times, It is convenient to have the positional deviation of the pattern layer. After the molding die is closed, the molten resin is injected into the mold from the gate provided in the movable mold, and the transfer material is attached to the surface while forming the molded article. After the resin molded article is cooled, the resin molded article is taken out by opening the molding die. Finally, after the base sheet is peeled off, the resin layer is completely cross-linked and hardened by irradiation of an active energy ray to form a protective layer. Alternatively, the base sheet may be peeled off after the active energy ray is irradiated. Further, the curable resin composition for a transfer material of the present invention can be used not only as a composition for producing a transfer material, but also by a gravure coating method, a roll coating method, a spot coating method, or the like, a gravure printing method, and a screen printing method. A printing method such as a printing method or the like is applied to a molded article such as a film, a sheet, or a molded article. The sheet following method will be described below. As a sheet-following method, for example, a base sheet obtained by forming a sheet for forming a protective layer prepared in advance is bonded to a formed crucible, and then thermally cured by heating to perform a B-staged resin layer. The method of cross-linking hardening (follow-up method), and the sheet for forming a protective layer are lost in a molding die, and the resin is filled in a cavity, and the resin is added to the molded product of the tree. A method of performing cross-linking and hardening of a resin layer (simultaneous molding and bonding method), etc., after the surface is bonded to the sheet for forming a protective layer and then thermally cured by heating. The sheet for forming a protective layer can be produced, for example, by a method of producing the above-mentioned transfer material. In the case where the '9 base sheet is coated with a curable resin composition', the adhesion between the base sheet and the curable resin can be improved by the following method when the adhesion between the base sheet and the curable resin composition is less than 51 201127480. Adhesiveness of the material 1. The base sheet is coated on the surface of the coating-curable resin composition of the base sheet, and the curable resin composition is applied thereon, and the base sheet is activated by corona discharge or the like. Surface and other methods. For the primer used in the domain 1, for example, a thermosetting resin such as a two-liquid curable polyurethane resin, a melamine resin, or an epoxy resin, or a thermoplastic resin such as an aqueous latex composed of an acrylic resin can be used. Resin. Examples of the adhesion method of the adhesive agent include a coating method such as a gravure coating method, a roll coating method, and a spot coating method, and a printing method such as a gravure printing method. In the above method of producing a transfer material, 'the active energy ray-curable resin composition is applied to the base sheet,' and the active energy ray is irradiated. By using the active energy ray, the (meth) acrylonitrile gene in the curable resin composition is polymerized by a radical polymerization to form a three-dimensional crosslink, and the curable resin composition is cured. When the active energy ray-curable resin composition is an active energy ray-curable resin composition containing an organic solvent, the organic solvent may be removed after being applied onto the base sheet. The removal of the organic solvent may be carried out, for example, after irradiation with the active energy ray, or before irradiation of the active energy ray. As the removal method, it may be left to stand for volatilization, or may be dried using a dryer or the like. However, it is usually preferred that the temperature at which the organic solvent is removed is from 7 Torr to 130 ° C for about 10 seconds to about 1 minute. In addition, the configuration of the sheet for forming a protective layer is not limited to the above-described form, and for example, when a sheet for forming a protective layer which exhibits the form and transparency of the molded article itself and is only used for the surface protective treatment is used, A hardened resin layer and an adhesive layer are sequentially formed on the base sheet, and the pattern layer is omitted from the protective layer forming 52 201127480 sheet. Further, when the sheet for forming a protective layer is formed on the π-your layer having a resin layer, an anchor layer may be provided between the layers of the layer #, 麻叫★私入1 马固层 is used to improve the For the adhesive layer between the layers, 7 , t.. , ^ ^ j can be used as a two-liquid hardening polyurethane, bismuth oxime resin, dimeric amide resin, epoxy ^ r ^ us , chyle A thermoplastic resin such as a thermosetting resin such as rouge or a gas-diethyl copolymer resin. .. JL. The formation method of the erroneous layer is a printing method such as a gravure coating method, a roll coating method, a spot coating method, a gravure printing method, and a screen printing method. The molding article used in the sheet-following method is as follows. For example, a molded article which is not exemplified in the above transfer method can be used. In the following method, a method of forming a sheet for forming a vine layer and a sheet for forming a layer of vine layer is used, and for example, a method of applying a sheet of a sheet for forming a protective layer to a sheet of a protective layer can be applied. On the surface of the sheet and/or the molded article, Α ^ ^ , the base sheet of the sheet for forming a pouch layer and the surface of the molded article are attached, and the double-sided adhesive tape is attached to the sheet for forming a protective layer. The base sheet of the material ^ Μ ^ ^ After the surface of the molded article, the release protective sheet of the double-sided adhesive tape is exposed more evenly, so that the substrate sheet protecting the 2 = Γ is formed on the surface of the molded article. In the following method, a base sheet of a sheet for forming a protective layer is formed to form a sheet with a protective layer which is prepared in advance to peel off the protective sheet, and the protective layer is formed to form a sheet. f <There is a residual protective sheet so that the contact surface of the base sheet is in contact with the surface of the molded article. In the simultaneous molding method, 'the adhesive is not used, ^ P ^, and the base sheet is melted by the heat in the in-mold molding, thereby making the protective layer into a sheet and a molded article. - The body can then be used to form K, A, ., ^ ~ warfare sheets and molded articles. Here, as the subsequent use in the above-mentioned subsequent method, for example, a urethane 53 201127480-based adhesive, an epoxy-based adhesive, an ester-based adhesive, an acrylic adhesive, a hot-melt adhesive, or the like can be given. Hereinafter, a method of forming a protective layer of a molded article by the above-described subsequent bonding method will be specifically described. First, a sheet for forming a protective layer is placed on the molded article such that the adhesive layer side is on the lower side. Next, using a transfer machine such as a roll transfer machine or a reversible transfer machine having a heat-resistant rubber-like elastic body such as ruthenium rubber, heat resistance is set by a condition of a temperature of 80 to 260 ° C and a pressure of 50 to 200 kg/m 2 . The rubber-like elastic body applies heat and/or pressure from the side of the protective layer of the sheet for forming a protective layer. In this way, the adhesive layer is then applied to the surface of the molded article. Finally, the resin layer formed on the molded article is completely cross-linked and hardened by heating to form a protective layer. Next, a method of forming a protective layer of a molded article by a simultaneous transfer molding method using injection molding will be specifically described. First, in the molding die formed by the movable mold and the fixing module, the transfer material is fed as the inner side, that is, the transfer material is released into the mold by the base. At this time, it is also possible to feed the transfer material sheets one by one, and the crucible can intermittently deliver the necessary portion of the long transfer material. When a long transfer material is used, the conveying means having the position determining means may be used to make the orientation of the pattern layer of the transfer material and the molding die uniform. In addition, when the transfer material is intermittently delivered, the position of the transfer material is detected by the sensor, and then the transfer material is fixed by the movable mold and the fixed mold, and the spine Hp #m P#ff can be used. - Straight fixed at the same position, the positional deviation of the pattern layer does not occur, and it is convenient because of the θ. After the mold for molding is closed, the smelting resin is filled with the squirting material from the movable mold, and the smelting resin is filled with the product. After the product is cooled, it is opened (4) to the surface. Molding the resin 1 The resin molded article was taken out by a mold. Finally, the resin layer is completely cross-linked and hardened by heat 54 201127480, and heated in the form of a wind to form a protective layer. (Examples) Hereinafter, the present invention will be more specifically described by way of examples and comparative examples. The percentage and % in the example, unless there is a sacrifice. Oral baldness is specified, otherwise the benchmark is qualitative. Example 1 In a reaction apparatus equipped with a mixing device, a cooling tube, a dropping funnel, and a nitrogen introduction tube, methacrylic acid glycidol vinegar (hereinafter, abbreviated as GMA '') 250 g, decyl isobutyl group was added. Ketone (hereinafter abbreviated as MIBK)) lGG0g and tertiary butyl ethyl hexanoic acid vinegar (hereinafter abbreviated as "PO") l〇g, and then the temperature in the system was raised to about i hours under a nitrogen stream. The mixture was kept at about 90 ° C for 1 hour. Then, from the dropping funnel which was previously added with a mixture of gma 750 g, P - 〇 3 〇 g, the mixture was added dropwise to the system under a nitrogen stream for about 2 hours. The temperature was kept at the same temperature for 3 hours. Then, the temperature was raised to 120 ° C, and the temperature was kept for 2 hours. After cooling to 60. (:, the nitrogen gas introduction tube was replaced with an air introduction tube, and acrylic acid (hereinafter, abbreviated as AA) 507 g, methoxy After meth〇quinone (2.3 g) and triphenylphosphine (9.3 g) were mixed and mixed, the temperature was raised to n〇°c under air bubbling. After incubation at the same temperature for 8 hours, 曱oxy 醌 16 6g was added. , and then cooling, adding MIBK to make the non-volatile component 50%, to obtain dioxide A solution of a reactive dispersant (A-1) for fine particles. The reactive dispersant (A-丨) has 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. Example 2 55 201127480 Using the same reaction apparatus as in Example 1, 125 g of GMA, decyl decyl acrylate (hereinafter abbreviated as ''MMA') 125 g, MIBK 1000 g and P-Ο 10 g were added, and under a nitrogen stream, about i The temperature in the system was raised to about 90 ° C for 1 hour. Then, a dropping funnel containing a mixture of GMA 3 75 g, MMA 3 75 g, and P- 30 g was added in advance to the system under a nitrogen stream. The mixture was added dropwise for about 2 hours, and kept at the same temperature for 3 hours. Then, the temperature was raised to 12 (rc, kept for 2 hours. After cooling to 60 ° C, the nitrogen inlet tube was replaced with an air introduction tube, and aa 254 g was added. , methoxy 2·3 g and diphosphine 9 · 3 g were mixed and then heated to 110 ° C under air bubbling. After holding at the same temperature for 8 hours, add 曱 覼 覼 1.6g 'Cooling, and then adding MIBK to make the non-volatile content 5〇% A solution of a reactive dispersant (A-2) for cerium oxide microparticles is obtained. The reactive emulsifier (A-2) has an acrylonitrile equivalent of about 356 g/eq and a base value of about 158 mgKOH/g. The weight average molecular weight was about 40,000. Example 3 Using the same reaction apparatus as in Example 1, after adding GM A 75 g, MM A 175 g 'MIBK 1000 g and P - 〇 8 g, 'acting under a nitrogen stream for about 1 hour' The temperature was raised to about 9 (TC, held for 1 hour. Then, a dropping funnel having a mixture of GMA 300 g, MMA 700 g, and p- 23 g was added in advance, and a mixed solution was added dropwise to the system under a nitrogen stream for about 2 hours, and the mixture was kept at the same temperature for 3 hours. Then, the temperature was raised to 12 ° C and kept for 2 hours. Cool to 60. (: After that, replace the nitrogen gas inlet pipe with the air inlet pipe, add AA 152g, methoxy styrene 2.3g and triphenylphosphine 5.6g to knead the mixture. After air bubbling, heat up to 110 ° C. In the same After the temperature was kept for 8 hours, methoxy ruthenium 1.6 g was added for cooling, and 56 201127480 MIBK was added to make the nonvolatile content 50%, and a solution of a reactive dispersant (Α 3 ) for the silica dioxide particles was obtained. The reactive dispersant (Α 3) has an acrylonitrile equivalent of about 545 g/eq, a hydroxyl value of about i〇3 mg K: 〇H/g, and a weight average molecular weight of about 70,000. Example 4 will be 2 in terms of solid content. 5 g of reactive dispersant (a — i ), dipentaerythritol hexaacrylate (DPHA) 25 g, cerium oxide microparticles (“Aursil 200” manufactured by Aer〇sil Co., Ltd., average primary particle size of about 12 nm) 50 g The mixture was mixed with MIBK 20 〇g to obtain a mixture. The cerium oxide microparticles in the mixture were dispersed using Ultra Apex Miu UAM015 manufactured by Shou Industrial Co., Ltd. The Ultra Apex Mill "UAM015" used here has a stator. The path is = , inside The volume of the separator is 0.17 liter, the diameter of the separator is 4 〇 claws, and the diameter of the cutter is set to 5 mm. The wet ball mill (the type of the outlet 19 is not shown in Fig. 2). When manufacturing the dispersion, In the wet ball mill, cerium oxide beads having a median diameter of % by mol were filled in an amount of 50% by volume with respect to the volume of the wet ball mill. The above mixture in the raw material tank was supplied from a supply port to a wet ball mill by a pump. The rotor was operated at a constant rotational speed (circumferential speed of the rotor tip of 28 m/sec), and the mixture was subjected to cyclic pulverization at a flow rate of 2 〇〇mi per minute. The pulverization was carried out for 30 minutes to obtain cerium oxide particles. A dispersion obtained by dispersing a mixture of a reactive dispersant (A-small ^ κ) was removed by a vaporizer to obtain a reactive dispersion having a nonvolatile content of 50%. To 100 parts of the reactive dispersion, two parts of the photoinitiator "Irgacure-57 201127480 184" were added to obtain an active energy ray-curable resin composition. The active energy ray-curable resin composition was placed in the chamber. (25 <t) Xiabao #2 months does not produce sediment, storage transferred to the name of Xiao #, good sputum. Further, a hard coating film was produced under the following conditions. When the pencil hardness was measured, it was 5H. Method for measuring pencil hardness 1. Method for producing a cured coating film An active energy ray-curable resin composition was applied onto a cellulose triacetate (TAC) film (thickness: 40 μm) by a bar coater (film thickness: 10 μm). 70. The crucible was dried for 1 minute, passed through a high-pressure mercury lamp under nitrogen at a dose of 250 mJ/cm2, and hardened to obtain a test piece having a cured coating film. 2. Evaluation method of hardened coating film According to JIS K 5400, the cured film of the above test piece was evaluated by a pencil drawing test with a load of 500 g. Examples 5 to 1 反应 A reactive dispersion was produced in the same manner as in Example 4 except that the mixing shown in Table 1 was carried out. Using the obtained reactive dispersion, an active energy ray-curable resin composition was obtained in the same manner as in Example 4. The storage stability and the erroneous hardness of the cured coating film were measured in the same manner as in Example 4, and the results are shown in Table 1. 58 201127480 Table 1

實施例 4 5 6 7 8 9 10 分散劑 (固體成分） (A-1) 25g 25g 25g 25g 50g (A-2) 25g (A-3) 25g 添加劑 DPHA 25g 25g 25g 25g 25g 25g 二氧化矽微粒 Aerosil 200 50g 5〇g 5〇g 50g Aerosil 50 50g EMIX-100 50g EMIX-300 5〇g 分散溶劑 MBK 200g 2〇〇g 2〇〇g 200g 200g 200g 200g 分散穩定性 〇 〇 〇 〇 〇 〇 〇 鉛筆硬度 5H 5H 5H 5H 4H 3H 4H 表1的註腳Example 4 5 6 7 8 9 10 Dispersant (solid content) (A-1) 25 g 25 g 25 g 25 g 50 g (A-2) 25 g (A-3) 25 g Additive DPHA 25 g 25 g 25 g 25 g 25 g 25 g cerium oxide particles Aerosil 200 50g 5〇g 5〇g 50g Aerosil 50 50g EMIX-100 50g EMIX-300 5〇g Dispersing solvent MBK 200g 2〇〇g 2〇〇g 200g 200g 200g 200g Dispersion stability 〇〇〇〇〇〇〇 pencil hardness 5H 5H 5H 5H 4H 3H 4H Table 1 footnote

Aerosil 200 :日本AEROSIL股份有限公司製造的二氧 化矽微粒。一級粒徑1 7nm。Aerosil 200: cerium oxide particles manufactured by AEROSIL Co., Ltd., Japan. The primary particle size is 17 nm.

Aerosil 50:日本AEROSIL股份有限公司製造的二氧化 石夕微粒。一級粒徑30nm。 EMIX - 100 :龍森股份有限公司製造的二氧化矽微粒。 一級粒徑1 OOnm。 EMIX — 3 00 :龍森股份有限公司製造的二氧化矽微粒。 一級粒徑300nm。 分散安定性〇：2個月間無沉降。 比較例1 使用二氧化矽微粒（日本AEROSIL股份有限公司製， Aerosil 50 '平均一級粒徑約30nm)50g、雙酚A環氧丙烯酸 酯（DIC 股份有限公司製，UNIDIC V- 5500)50g、MIBK200 59 201127480 伤除此之外，按照與貫施例4相同之方式得到不揮發成 分濃度為50%的比較對照用反應性分散體。 在該比較對照用反應性分散體100份中添加2份 Irgacure— 184’得到比較對照用活性能量線硬化性樹脂組成 物。比較對照用活性能量線硬化性樹脂組成物在室溫（25艺） 下保存1小時未產生沉降物。另外，按照與實施例4相同 的方式製作硬化塗膜，測定鉛筆硬度時，為。 比較例2 將一氧化矽微粒（Aerosil 50、平均一級粒徑約3〇nm)5〇 份、DPHA50份、MIBK2〇()份與氧化鍅珠6〇〇份（珠粒直徑 〇.3mm)一起加入到玻璃瓶中，在PAINT SHAKER中混合2 小時，取出後’用蒸發器除去MIBK，得到不揮發成分濃度 為50%的比較對照用反應性分散體。 於该比較對照用反應性分散體100份中添加2份 Ifgacure ~ 1 84 ’得到比較對照用活性能量線硬化型樹脂組成 比較對照用活性能量線硬化型樹脂組成物在室溫（2 $。〇) 下保存1周未產生沉降物。另外，按照與實施例4相同的 方式製作硬化塗膜，測定鉛筆硬度時，為3H。 比較例3 &在乾燥空氣中，於50〇c、以i小時邊攪拌異佛爾酮二 、氛自文S曰222g邊將其滴加於由疏基丙基三甲氧基石夕烧 8 一丁基二月桂酸錫1 g組成的溶液，然後在60。(：攪拌 】時°在30 C、以1小時於該混合液中滴加ar〇nIX Μ 5〔東亞合成（股）製’季戊四醇三丙烯酸酯/季戊四醇四 丙烯酸S曰—60/40(重量％)〕549g,然後在60。(：下加熱攪拌 201127480 1 0小時，從而得到有機化合物。在氮氣流下，將有機化合 物3.0g、曱基乙基酮矽溶膠（日產化學工業股份有限公司 製，商品名：MEK—ST，數量平均粒徑22nm，二氧化矽濃 度3 0%)89_9g、離子交換水〇.lg的混合液在6〇t3c下攪拌4 小時後，添加原曱酸甲酉旨1.4g，再於同一溫度下加熱攪拌ι 小時，然後脫除溶劑，得到不揮發成分濃度為3〇%的比較 對照用反應性分散體。 添加該比較對照用反應性分散體i 〇〇份、DpH A4〇份、 hgacure —丨84(光起始劑）2份，得到比較對照用活性能量線 硬化性樹脂組成物。比較對照用活性能量線硬化性樹脂組 錢在室溫（25。〇下保存丨料未產生沉降物。另外，按照 與實施例1相同的方式製作硬化塗膜，測定錯筆硬度時， 為2H。 【圖式簡單說明】 圓具備本發明之分散體製造方法中使用的上述滿式 球磨機的原料漿料粉碎處理回路的概略圖。 圖2 |發明的分散體製造方法中使用的上述濕式球磨 機的縱截面圖。 圖3,本發明的分散體製造方法中使用的上述濕式球磨 之供、漿料時的供給口的縱截面圖。 圖4 w質排出時供給口的縱截面圖。 本發明的分散體製造方法中使用的上述 A· I ， . 機的另一個例；沾此 扪子的縱截面圖 圖 6，圖 <；由化_ 斤不的濕式球磨機的分離器的橫截面圖2 61 201127480 表示圖。 【主要元件符號說明】 1 原料槽 2 原料泵 3 磨碎型濕式攪拌球磨機 4 分離器 5 旋轉軸 6 夾套 7 定子 9 排放通道 11 轉子 12 電動機 · 13 皮帶輪 14 皮帶輪 15 旋轉接頭 16 供給口 17 篩網支架 18 肖帛網 19 取出口 21 轉盤 22 葉片 23 調節器 24 閥座 25 閥體 62 201127480 26 圓筒體 27 導入口 28 圓筒體 29 壓縮空氣或N2氣導入口 30 電磁切換閥 31 活塞 32 桿 33 彈簧 34 螺母 43 旋轉軸 43a 旋轉軸43的段差 44 分離器 45 隔板 46 轉子 47 塞子 48 螺紋 51 葉片欲合槽 52 圓盤 53 葉片 54 排放通道 55 56 環狀隔板 58 閥門 59 閥門 壓縮空氣或N2氣閥 60 63 201127480 61 閥門 62 壓縮空氣或 Ν2氣閥 63 壓縮空氣或 Ν2氣閥 64 閥門 65 排出口 66 排出口 67 製品槽 64Aerosil 50: Semen dioxide particles manufactured by AEROSIL Co., Ltd., Japan. The primary particle size is 30 nm. EMIX-100: cerium oxide particles manufactured by Longsen Co., Ltd. The primary particle size is 10,000 nm. EMIX — 3 00: cerium oxide particles manufactured by Longsen Co., Ltd. The primary particle size is 300 nm. Dispersion stability 〇: no sedimentation within 2 months. Comparative Example 1 50 g of cerium oxide microparticles (manufactured by AEROSIL Co., Ltd., Aerosil 50 'average primary particle diameter: about 30 nm), bisphenol A epoxy acrylate (UNIDIC V-5500, manufactured by DIC Co., Ltd.), 50 g, MIBK200 59 201127480 In addition to the injury, a comparative control reactive dispersion having a nonvolatile content of 50% was obtained in the same manner as in Example 4. To the comparative control reactive dispersion 100 parts, 2 parts of Irgacure-184' was added to obtain a comparative active energy ray-curable resin composition. The comparative active energy ray-curable resin composition was stored at room temperature (25%) for 1 hour without sedimentation. Further, a cured coating film was produced in the same manner as in Example 4, and when the pencil hardness was measured, it was determined. Comparative Example 2 5 parts of cerium oxide microparticles (Aerosil 50, average primary particle diameter of about 3 〇 nm), 50 parts of DPHA, MIBK 2 〇 () parts and 6 parts of cerium oxide beads (bead diameter 〇. 3 mm) The mixture was placed in a glass bottle, mixed in a PAINT SHAKER for 2 hours, and after removal, the MIBK was removed by an evaporator to obtain a comparative control reactive dispersion having a nonvolatile content of 50%. Two parts of Ifgacure ~ 1 84 ' were added to 100 parts of the comparative control reactive dispersion to obtain a comparative control active energy ray-curable resin composition comparative control active energy ray-curable resin composition at room temperature (2 $. There was no sedimentation after 1 week of storage. Further, a cured coating film was produced in the same manner as in Example 4, and when the pencil hardness was measured, it was 3H. Comparative Example 3 & In a dry air, the isophorone was stirred at 50 ° C for 1 hour, and the mixture was added dropwise to the sulfopropyltrimethoxy sulphide 8 A solution consisting of 1 g of butyl dilaurate and then at 60. (: stirring) ° at 30 C, 1 hour in the mixture was added ar〇nIX Μ 5 [East Asia Synthetic (stock) made of pentaerythritol triacrylate / pentaerythritol tetraacrylic acid S 曰 - 60 / 40 (% by weight ) 549g, then at 60. (: heating under stirring 201127480 for 10 hours, to obtain an organic compound. Under the nitrogen flow, 3.0 g of an organic compound, mercaptoethyl ketone oxime (manufactured by Nissan Chemical Industry Co., Ltd., Name: MEK-ST, number average particle size 22nm, cerium oxide concentration 30%) 89_9g, ion exchanged water 〇. lg mixture is stirred at 6〇t3c for 4 hours, then add the original ruthenium ruthenium to 1.4g Then, the mixture was heated and stirred at the same temperature for 1 hour, and then the solvent was removed to obtain a comparative control reactive dispersion having a nonvolatile content of 3% by weight. The comparative control reactive dispersion i 〇〇, DpH A4 was added. 2 parts of sputum, hgacure - 丨84 (photoinitiator), and a comparative active energy ray-curable resin composition were obtained. The comparative active energy ray-curable resin group was compared at room temperature (25. No sediment was produced. A hardened coating film was produced in the same manner as in Example 1, and when the wrong pen hardness was measured, it was 2H. [Simplified description of the drawing] The round material was subjected to the raw material slurry pulverization treatment of the above-described full ball mill used in the method for producing a dispersion of the present invention. Fig. 2 is a longitudinal cross-sectional view of the wet ball mill used in the method for producing a dispersion of the invention. Fig. 3 is a view showing the supply of the wet ball mill and the slurry used in the method for producing a dispersion of the present invention. Fig. 4 is a longitudinal cross-sectional view of the supply port at the time of discharge of the w mass. Another example of the above-mentioned A·I, used in the method for producing a dispersion of the present invention; a longitudinal section of the tweezers Figure 6, Figure <; Cross-section of the separator of the wet ball mill from _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Separator 5 Rotary shaft 6 Jacket 7 Stator 9 Discharge passage 11 Rotor 12 Motor · 13 Pulley 14 Pulley 15 Rotary joint 16 Supply port 17 Screen bracket 18 Shaw mesh 19 Take-out 2 1 Turntable 22 Blade 23 Regulator 24 Seat 25 Valve body 62 201127480 26 Cylindrical body 27 Guide inlet 28 Cylinder 29 Compressed air or N2 gas inlet 30 Electromagnetic switching valve 31 Piston 32 Rod 33 Spring 34 Nut 43 Rotary shaft 43a Step difference of the rotating shaft 43 44 Separator 45 Separator 46 Rotor 47 Plug 48 Thread 51 Blade for the groove 52 Disc 53 Blade 54 Discharge passage 55 56 Annular baffle 58 Valve 59 Valve compressed air or N2 gas valve 60 63 201127480 61 Valve 62 Compressed air or helium 2 gas valve 63 Compressed air or helium 2 gas valve 64 Valve 65 Discharge port 66 Discharge port 67 Product slot 64

Claims (1)

201127480 七、申請專利範圍： ^一種分散體之製造方法，其特徵在於： 將含有（甲基）丙烯酸系聚合物（B)與二氧化矽微粒（f)之 聚料，從包含以下構件的濕式球磨機之漿料供給口供給到 定子内，該（甲基）丙烯酸系聚合物（B)係分子結構中具有（甲 基）丙烯醯基與羥基，且（甲基）丙烯醯基當量在2⑻〜 600g/eq的範圍、羥基值在9〇〜28〇mgK〇H/g的範圍： 1) 内部填充有介質的圓筒形定子、 2) 設置於該定子下端的漿料供給口、 3) 位於該定子的軸心’且其上部設置有中空狀液體排放 通道之進行旋轉驅動的旋轉軸、 4) 與該旋轉軸進行同軸旋轉驅動的轉子 與 5) 以同軸狀設置於該旋轉軸上部且以與該中空狀液體 排放通道連通而排出分離液之方式構成之進行旋轉驅動的 葉輪型分離器； 在定子内旋轉驅動該轉子以攪拌混合介質與聚料，使 漿料中的二氧化矽微粒（F)粉碎並分散至（曱基）丙烯酸系聚 合物（B) ’且在旋轉驅動的分離器部藉由離心力作用使聚料 與介質分離’將被誘導到分.離器軸心部的毅料從該旋轉轴 内的中空狀排放通道排出。 2. 如申請專利範圍第1項之分散體之製造方法，其中， 該（曱基）丙烯酸系聚合物（B)之（曱基）丙烯醯基當量為〜 400g/eq，經基值為 140〜280mgKOH/g。 3. 如申請專利範圍第1項之分散體之製造方 /ZC ’具中， 該（曱基）丙烯酸系聚合物（B)的重量平均分子番炎 J刀丁置為5,〇〇〇〜 65 201127480 1 〇〇,〇〇〇。 4. 如申請專利範圍第1項之分散體之製造方法，其中， 該二氧化矽微粒（F)的一次粒徑為i〇nm〜300ητη。 5. 如申請專利範圍第1項之分散體之製造方法，其中， 該（甲基）丙烯酸系聚合物（B)係使具有（曱基）丙烯醯基及羧 基的單體（c)與具有環氧基的（曱基）丙烯酸系聚合物（al)進 行加成反應而形成的反應生成物（bl)，或者是使具有（甲基） 丙烯醯基及環氧基的單體（d)與具有羧基的（甲基）丙烯酸系 聚合物（a2)進行加成反應而形成的反應生成物（b2)。 6. 如申請專利範圍第1項之分散體之製造方法，其中， 該（曱基）丙烯酸系聚合物（B)係使（甲基）丙烯酸與具有環氧 基的（甲基）丙烯酸系聚合物進行加成反應而形成的反應生 成物，該具有環氧基的（甲基）丙烯酸系聚合物係以（曱基）丙 烯酸縮水甘油酯為必需單體成分的聚合性單體經聚合而得 者。 7. 如申請專利範圍第1項之分散體之製造方法，其中， 該介質係平均粒徑以中值粒徑計為15〜3〇〇#m的氧化鍅微 粒。 8 · —種能量線硬化型樹脂組成物，其特徵在於，含有以 申請專利範圍第1〜7項中任一項之製造方法所得到的分散 體。 9 ·種膜，其特徵在於，在膜狀基材上具有使申請專利 範圍第8項之能量線硬化型樹脂組成物硬化而得到之硬化 層。 10.如申請專利範圍帛9項之膜，其中，該膜狀基材係 66 201127480 選自聚對笨二甲酸乙二酯樹脂（PET)膜狀基材、聚碳酸酯樹 脂之膜狀基材及醋酸纖維素樹脂之膜狀基材所組成的群中 的一種以上。 11 ·如申請專利範圍第9項之膜，其中，該硬化層的膜 厚相對於膜狀基材之膜厚為3〜100〇/〇。 12_ —種二氧化矽微粒用反應性分散媒介，其特徵在 於’含有（甲基）丙烯酸系聚合物（B)，該（曱基）丙烯酸系聚合 物（B)之分子結構中具有（甲基）丙烯醯基與羥基，且（曱基） 丙稀醯基當量為200〜600g/eq、羥基值為90〜 280mgKOH/g。 1 3. —種二氧化石夕微粒用反應性分散劑，其特徵在於， 含有（曱基）丙烯酸系聚合物（B)，該（曱基）丙烯酸系聚合物（B) 分子結構中具有（甲基）丙烯醯基與羥基，且（甲基）丙烯醯基 當量為200〜600g/eq、經基值為9〇〜280mgKOH/g。 八、圖式： (如次頁） 67201127480 VII. Patent application scope: ^ A method for producing a dispersion, characterized in that a polymer containing a (meth)acrylic polymer (B) and cerium oxide microparticles (f) is wet from a component comprising the following components The slurry supply port of the ball mill is supplied into the stator, and the (meth)acrylic polymer (B) has a (meth)acryloyl group and a hydroxyl group in the molecular structure, and the (meth)acryl fluorenyl equivalent is 2 (8). a range of ~600g/eq and a hydroxyl value in the range of 9〇28〇mgK〇H/g: 1) a cylindrical stator filled with a medium, 2) a slurry supply port provided at the lower end of the stator, 3) a rotating shaft that is rotatably driven by a hollow liquid discharge passage at an upper portion of the stator, 4) a rotor that is coaxially driven to rotate with the rotating shaft, and 5) coaxially disposed on the upper portion of the rotating shaft An impeller-type separator configured to rotate and drive the separation liquid in communication with the hollow liquid discharge passage; the rotor is rotationally driven in the stator to agitate the mixed medium and the aggregate to make the dioxin in the slurry The bismuth particles (F) are pulverized and dispersed to the (fluorenyl) acrylic polymer (B) 'and the particles are separated from the medium by centrifugal force in the rotationally driven separator portion' will be induced to the separator shaft The susceptibility of the heart is discharged from the hollow discharge passage in the rotating shaft. 2. The method for producing a dispersion according to claim 1, wherein the (mercapto)acrylic polymer (B) has a (mercapto)acrylonitrile equivalent of from -400 g/eq and a base value of 140. ~280 mg KOH / g. 3. In the manufacturer of the dispersion of the first application of the patent scope/ZC', the weight average molecular weight of the (meth)acrylic polymer (B) is set to 5, 〇〇〇~ 65 201127480 1 Hey, hey. 4. The method for producing a dispersion according to the first aspect of the invention, wherein the primary particle diameter of the cerium oxide microparticles (F) is from i 〇 nm to 300 η τη. 5. The method for producing a dispersion according to the first aspect of the invention, wherein the (meth)acrylic polymer (B) is a monomer (c) having a (fluorenyl) acrylonitrile group and a carboxyl group; a reaction product (bl) formed by an addition reaction of an epoxy group-containing (fluorenyl) acrylic polymer (al), or a monomer having a (meth) acrylonitrile group and an epoxy group (d) A reaction product (b2) formed by an addition reaction with a (meth)acrylic polymer (a2) having a carboxyl group. 6. The method for producing a dispersion according to the first aspect of the invention, wherein the (meth)acrylic polymer (B) polymerizes (meth)acrylic acid with a (meth)acrylic group having an epoxy group. A reaction product formed by an addition reaction, wherein the (meth)acrylic polymer having an epoxy group is obtained by polymerizing a polymerizable monomer having (indenyl) glycidyl acrylate as an essential monomer component. By. 7. The method of producing a dispersion according to the first aspect of the invention, wherein the medium has an average particle diameter of 15 to 3 Å #m of cerium oxide microparticles by a median diameter. And an energy ray-curable resin composition comprising the dispersion obtained by the production method according to any one of claims 1 to 7. In the film-form substrate, the hardened layer obtained by curing the energy ray-curable resin composition of the eighth aspect of the patent application is cured. 10. The film of claim 9 wherein the film substrate is 66 201127480 selected from the group consisting of a polyethylene terephthalate resin (PET) film substrate and a polycarbonate resin film substrate. And one or more of the group consisting of a film-form substrate of a cellulose acetate resin. The film according to claim 9, wherein the film thickness of the hardened layer is from 3 to 100 Å/〇 with respect to the film substrate. A reactive dispersion medium for a cerium oxide microparticle, characterized in that it contains a (meth)acrylic polymer (B) having a molecular structure in the molecular structure of the (meth)acrylic polymer (B) And an acryloyl group and a hydroxyl group, and the (mercapto) acrylonitrile group equivalent is 200 to 600 g/eq, and the hydroxyl value is 90 to 280 mgKOH/g. 1 3. A reactive dispersant for a rare earth oxide particle comprising a (fluorenyl)acrylic polymer (B) having a molecular structure (()) The methyl group has a fluorenyl group and a hydroxyl group, and the (meth) acrylonitrile group has an equivalent weight of 200 to 600 g/eq and a base value of 9 〇 to 280 mg KOH/g. Eight, the pattern: (such as the next page) 67
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