TWI338597B - - Google Patents

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Publication number
TWI338597B
TWI338597B TW094108478A TW94108478A TWI338597B TW I338597 B TWI338597 B TW I338597B TW 094108478 A TW094108478 A TW 094108478A TW 94108478 A TW94108478 A TW 94108478A TW I338597 B TWI338597 B TW I338597B
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TW
Taiwan
Prior art keywords
layer
refractive index
metal oxide
oxide particles
index layer
Prior art date
Application number
TW094108478A
Other languages
Chinese (zh)
Other versions
TW200536620A (en
Inventor
Hiroomi Shimomura
Mitsunobu Doimoto
Yasunobu Suzuki
Tetsuya Yamamura
Yuichi Eriyama
Takayoshi Tanabe
Hideaki Takase
Original Assignee
Jsr Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Priority claimed from JP2004331087A external-priority patent/JP4419809B2/en
Priority claimed from JP2004331086A external-priority patent/JP4774722B2/en
Application filed by Jsr Corp filed Critical Jsr Corp
Publication of TW200536620A publication Critical patent/TW200536620A/en
Application granted granted Critical
Publication of TWI338597B publication Critical patent/TWI338597B/zh

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • 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
    • C08K3/10—Metal compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Laminated Bodies (AREA)
  • Paints Or Removers (AREA)
  • Surface Treatment Of Optical Elements (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Description

1338597 ' (1) 九、發明說明 【發明所屬之技術領域】 本發明有關液狀硬化性樹脂組成物及使用其之層合體 的製造方法，特別是有關能從1層塗膜形成2層以上的層 之液狀硬化性樹脂組成物以及用其之層合體的製造方法。 【先前技術】 % 現在，隨著多媒體（multimedia )之發達，而在各種 顯示裝置（display裝置）方面，有了各種發展。並且， 在各種顯示裝置之中，特別是以行動型爲中心而爲屋外使 用者，其目認性愈來愈顯得重要，在大型顯示裝置方面， 使用者愈來愈要求更能容易視認，以致此種目認性之提升 即成爲技術上的課題。 在來，爲提升顯示裝置之目認性的手段之一，在實施 將由低析射率材料所構成的反射防止膜被覆於顯示裝置之 # 基板上的作法，而形成反射防止膜的方法而言，例如，周 知有依沈積法形成含氟化合物之薄膜的方法。然而，近年 來，有對液晶顯示裝置爲中心，而以低成本，在大型顯示 裝置上亦能形成反射防止膜的技術的開發之需求。惟如採 用沈積法時，對大面積之基板則難於高效率下形成均勻的 反射防止膜，且因需要真空裝置之故，難於降低成本。 鑑於此種情況，正在進行將折射率低的氟系聚合物溶 解於有機溶劑中以調製液狀組成物，並將此組成物塗佈於 基板表面以形成反射防止膜的方法。例如，有對基板表面 -5- (2) (2)1338597 塗佈氟化烷基矽烷之提案（例如，參照專利文獻1及專利 文獻2) 〇又，有塗佈具有特定構造的氟系聚合物的方法 之提案（例如’參照專利文獻3 )。 專利文獻1 :日本專利特開昭6 1 - 4 0 8 4 5號公報 專利文獻2 :日本專利特開昭6 · 9 8 7 0 3號公報 專利文獻3 :日本專利特開昭6 - 1 1 5 0 2 3號公報 此等在來之反射防止膜，多半是在基材上形成有不相 同的折射率之層、抗靜電層、硬質覆膜（head coat)層等 層合體。在來之製造方法中，係在基材上反覆實施各層之 分別塗佈的步驟者。 本發明，係鑑於如上述的狀況作爲背景所開發者，其 目的在於提供一種能有效製造低折射率層與高折射率層等 之任意連續的二層以上之層的液狀硬化性樹脂組成物。 本發明之其他目的在於提供一種透明性高，對基材的 密合性佳，且具有優異的耐擦傷性及灰塵擦淨性的硬化膜 〇 本發明之其他目的在於提供一種能從塗佈組成物所得 1層塗膜形成2層以上的層之層合體之製造方法以及由此 所得層合體。 本發明之其他目的在於提供一種具有良好的反射防止 效果的層合體之製造方法以及由此所得層合體。 本發明之其他目的在於提供一種對基材的密合性優異 ’且耐擦傷性高的層合體之製造方法以及由此所得層合體 -6 - 13385971338597' (1) The invention relates to a liquid curable resin composition and a method for producing a laminate using the same, and particularly relates to a method capable of forming two or more layers from a single layer coating film. A liquid curable resin composition of a layer and a method for producing a laminate using the same. [Prior Art] % Nowadays, with the development of multimedia, various developments have been made in various display devices. Moreover, among various display devices, especially for mobile users, the visibility is becoming more and more important, and in large display devices, users are increasingly demanding more visual recognition. This increase in visibility is a technical issue. In order to improve the visibility of the display device, a method of forming an anti-reflection film by coating an anti-reflection film made of a material having a low reflectance on a # substrate of a display device is used. For example, a method of forming a film of a fluorine-containing compound by a deposition method is known. However, in recent years, there has been a demand for development of a technique for forming an anti-reflection film on a large-sized display device centering on a liquid crystal display device at a low cost. However, when a deposition method is employed, it is difficult to form a uniform anti-reflection film for a large-area substrate with high efficiency, and it is difficult to reduce the cost due to the necessity of a vacuum device. In view of such a situation, a method of dissolving a fluorine-based polymer having a low refractive index in an organic solvent to prepare a liquid composition, and applying the composition to the surface of the substrate to form an antireflection film is being carried out. For example, there is a proposal to apply a fluorinated alkyl decane to the surface of the substrate -5 - (2) (2) 1338597 (for example, refer to Patent Document 1 and Patent Document 2), and further, a fluorine-based polymerization having a specific structure is applied. Proposal of the method of the object (for example, 'refer to Patent Document 3). Patent Document 1: Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. In the antireflection film of the above-mentioned publication, most of the antireflection films are formed of a laminate having a different refractive index, an antistatic layer, and a head coat layer on the substrate. In the production method, the step of separately coating the respective layers is carried out on the substrate. The present invention has been made in view of the above circumstances, and it is an object of the invention to provide a liquid curable resin composition capable of efficiently producing a layer of two or more layers of a continuous low refractive index layer and a high refractive index layer. . Another object of the present invention is to provide a cured film which has high transparency, good adhesion to a substrate, and excellent scratch resistance and dust cleanability. Another object of the present invention is to provide a coating composition. A method for producing a laminate of two or more layers obtained by forming one layer of a coating film, and a laminate obtained thereby. Another object of the present invention is to provide a method for producing a laminate having a good antireflection effect and a laminate obtained thereby. Another object of the present invention is to provide a method for producing a laminate having excellent adhesion to a substrate and having high scratch resistance, and a laminate obtained thereby - 6338738

【發明內容】 爲達成上述目的，本發明人等，爲瞭解能賦予從一層 塗膜具有二層以上之層構造的硬化膜的液狀硬化性樹脂組 成物，以及分離爲二層以上的機構起見，專心硏究之結果 ，發現如對具有特定構造之含氟聚合物及特定金屬氧化物 粒子，從按對分子內具有羥基的含氟聚合物的溶解性及對 φ 金屬氧化物粒子的分散安定性，以及相對蒸發速度可分爲 2種的溶劑種類分別選擇1種以上組合，並將此種液狀硬 化性樹脂組成物塗佈所得的一層塗膜，即可分離爲複數層 的事實，以及如選擇溶劑種類、其他條件，即不論任何種 類之金屬氧化物粒子仍能分離爲複數層之事實，而完成本 發明。 本發明，可提供如下述之液狀硬化性樹脂組成物等。 〔1〕. 一種液狀硬化性樹脂組成物，其特徵爲：含有下 φ 述成分（A)至（F); (A)分子內具有羥基的含氟聚合物 (B )數平均粒子徑爲100nm以下，且折射率爲丨.5〇 以上之丨種或2種以上之金屬氧化物粒子（以下’簡稱「 (B )金屬氧化物粒子」） (C) 對（A)分子內具有羥基的含氟聚合物的溶解性 高的1種或2種以上之溶劑（以下，簡稱「（ C)速揮發 溶劑」） (D) 對（B )金屬氧化物粒子的分散安定性高’且與 (4) 1338597 (C)速揮發溶劑相溶性的1種或2種以上之溶劑（以下 ，簡稱「（ D )遲揮發溶劑」） (E )硬化性化合物 (F )熱引發酸產生劑 ，且（C)速揮發溶劑之相對蒸發速度，係較（D )遲揮發 劑之相對蒸發速度爲大。 〔2〕 ·如〔1〕所記載之液狀硬化性樹脂組成物，其中（ φ C)速揮發溶劑，係對（B )金屬氧化物粒子的分散安定性 低的1種或2種以上之溶劑，而（D )遲揮發溶劑，係對 (A)分子內具有羥基的含氟聚合物的溶解性低的丨種或 2種以上之溶劑。 〔3〕.如〔1〕或〔2〕所記載之液狀硬化性樹脂組成物 ，其中（B )金屬氧化物粒子，係以選自氧化鈦、氧化锆 、含有銻之氧化錫、含有錫之氧化銦、氧化鋁、氧化铈、 氧化鋅、含有鋁之氧化鋅、氧化錫、含有銻之氧化鋅以及 # 含有銦之氧化鋅、含有磷之氧化錫的1種或2種以上之金 屬氧化物作爲主成分的粒子。 〔4〕.如〔3〕所記載之液狀硬化性樹脂組成物，其中（ B )金屬氧化物粒子，係以氧化鈦作爲主成分的粒子》 〔5〕.如〔〗〕至〔4〕中之任一項所記載之液狀硬化性 樹脂組成物，其中（Β )金屬氧化物粒子，係具有多層構 造的金屬氧化物粒子。 〔6〕.一種硬化膜，係使〔1〕至〔5〕中之任一項所記 載之液狀硬化性樹脂組成物硬化所製得，其特徵爲：具有 -8- (5) 1338597 2層以上之多層構造。 〔7〕.如〔6〕所記載之硬化膜，其中構成該多層構造的 各層，係高密度方式存在有（B)金屬氧化物粒子的層或 實質上不存在有（B)金屬氧化物粒子的層，而至少一層 ’係高密度方式存在有（B )金屬氧化物粒子的層。 〔8〕 ·一種硬化膜之製造方法，其特徵爲：具有藉由〔1 〕至〔5〕中之任一項所記載之液狀硬化性樹脂組成物之 B 加熱、或放射線之照射而使硬化的步驟。 〔9〕.一種層合體之製造方法，係基材，與在其上具有 多層構造的層合體之製造方法，其特徵爲：於前述其材上 或基材上所形成的層之上，塗佈〔1〕至〔5〕中之任一項 所記載之液狀硬化性樹脂組成物以形成塗膜，並 從此1層塗膜蒸發溶劑，以形成2層以上之層。 〔10〕.如〔9〕所記載之層合體之製造方法，其中該2 層以上之層之各層，係高密度方式存在有金屬氧化物粒子 • 的層或實質上不存在有金屬氧化物粒子的層，而至少1層 係高密度方式存在有金屬氧化物粒子的層。 〔11〕.如〔10〕所記載之層合體之製造方法，其中該2 層以上之層，係2層者。 〔12〕.如〔9〕至〔1 1〕中之任一項所記載之層合體之 製造方法，其中再藉由加熱而使該2層以上之層硬化。 〔13〕.如〔9〕至〔1 2〕中之任一項所記載之層合體之 製造方法，其中層合體係光學用零件。 (14].如〔9〕至〔12〕中之任一項所記載之層合體之 -9- (6) (6)1338597 製造方法，其中層合體係反射防止膜。 〔15〕 ·如〔11〕所記載之層合體之製造方法’其中該層 合體，係至少高折射率層及低折射率層經從靠近基材側按 此順序層合於基材上的反射防止膜，而〔】1〕所sS載之2 層，係由 高折射率層及 低折射率層所成。 〔1 6〕.如〔1 5〕所記載之層合體之製造方法，其中低折 射率層在589nm下的折射率爲1.20至1.55，而 高折射率層在589nm下的折射率爲1.5〇至2.20，且 較低折射率層之折射率爲高。 〔17〕 ·如〔11〕所記載之層合體之製造方法，其中該層 合體’係至少中折射率層、高折射率層以及低折射率層經 從靠近基材側按此順序層合於基材上的反射防止膜，而〔 1 1〕所記之2層，係由 商折射率層及 低折射率層所成。 〔18〕.如〔17〕所記載之層合體之製造方法，其中低折 射率層在589nm下的折射率爲1.20至1.55， 中折射率層在589nm下的折射率爲1.5〇至1.9〇，而 較低折射率層之折射率爲高， 高折射率層在589nm下的折射率爲151至2.20，而 較中折射率層之折射率爲高。 〔19〕 ·如〔15〕至〔18〕中之任一項所記載之層合體之 -10- (7) 1338597 製造方法，其中再於基板上形成硬質覆膜層及/或抗靜電 層。 〔20〕.一種層合體，係依〔9〕至〔1 9〕中之任一項所 記載的層合體之製造方法所製造者。 本發明之液狀硬化性樹脂組成物，由於可從一層塗膜 形成具有高折射率層與低折射率層等多層構造的硬化膜之 故，可簡化硬化膜之製造步驟。 p 本發明之液狀硬化性樹脂組成物，由於可從經塗佈組 成物所得的1層塗膜形成2層以上之層之故，可簡化具有 多層構造的層合體之製造步驟。 又，可藉由金屬氧化物粒子之偏在化，而提升硬化膜 或層合體之耐擦傷性。 本發明之液狀硬化性樹脂組成物，可特別適合使用於 反射防止膜、選擇透射膜濾光器等光學材料之形成，又， 利用含氟量高之特徵，可適合使用於對需要耐氣候性的基 • 材的塗料用材料、耐氣候性軟片用材料、塗層用材料、以 及其他材料。並且，該硬化膜，係對基材的密合性優異， 耐擦傷性高，能賦予良好的反射防止效果。因而，本發明 之硬化膜或層合體，係作爲反射防止膜極爲有用者，故如 適用於各種顯示裝置時，即可提升其目認性。 【實施方式】 〔發明之最佳實施形態〕 茲將本發明分爲液狀硬化性樹脂組成物、硬化膜以及 -11 - (8) 1338597 層合物，加以詳細說明。 1.液狀硬化性樹脂組成物 本發明之液狀硬化性樹脂組成物’含有下述成分（A )至（F)。 (A) 分子內具有羥基的含氟聚合物 (B) 數平均粒子徑爲lOOnm以下，且折射率爲1.50 以上之1種或2種以上之金屬氧化物粒子（以下’簡稱「 p ( B)金屬氧化物粒子」） (C )對（A )分子內具有羥基的含氟聚合物的溶解性 高的1種或2種以上之溶劑（以下，簡稱「（ C )速揮發 溶劑」） (D) 對（B)金屬氧化物粒子的分散安定性高，且與 (C )速揮發溶劑相溶性的1種或2種以上之溶劑（以下 ，簡稱「（ D )遲揮發溶劑」） (E) 硬化性化合物 φ ( F )熱引發酸產生劑 以下，就此等成分，分別加以說明。 (A)分子內具有羥基的含氟聚合物 含氟聚合物，係分子內具有碳-氟鍵的聚合物，其含 氟量較佳爲30質量％以上，更佳爲從凝膠滲透色譜法所得 之依聚苯乙烯換算所得數平均分子量，較佳爲5,000以上 。在此，含氟量係依茜素配位劑（alizarin compl exon)法 所測定的値，數平均分子量係作爲展開溶劑而使用四氫呋 喃時的値。 -12- (9) 1338597 本發明中所用的含氟聚合物之例而言，係分子內具有 經基的含氟聚合物（以下’簡稱「含有羥基之含氟聚合物 」）。較佳的含有控基之含氟聚合物之例而言，可例舉： 將源自含有經基的單體構造單元含有10莫耳％至5〇莫耳 /〇而成之主鏈中具有聚砂氧院段（segment)者。此種含有 經基之含氟聚合物’係主鏈上具有可以下述式（1)表示 的聚矽氧烷段的烯烴系聚合物，而含氟聚合物中的該聚矽 φ 氧烷段之比例，通常較佳爲0. 1至20莫耳％。 R1 —Si——0 — (1) R2 式中’ R1及R2可爲相同或不相同，而表示氫原子、 烷基、鹵化烷基或芳基。 又’含有經基之含氟聚合物’較佳爲含氟量在3〇質 量％以上。更佳爲40至60質量％者，再者，從凝膠滲透 φ 色譜法所得之依聚苯乙烯換算所得數平均分子量，較佳爲 5,000以上，更佳爲ι〇,〇00至50〇 〇〇〇者。 含有經基之含氟聚合物，可由（a )含有氟之烯烴化 合物（以下’簡稱「（a)成分」），（b)含有能與該（ a )成分共聚合的羥基的單體化合物（以下，簡稱「（ b ) 成分」）以及（c)含有偶氮基之聚矽氧烷化合物（以下 ’簡稱「c成分」）’並且，需要時，（d )反應性乳化劑 (以下’簡稱「（ d )成分」、及/或（e )能與前述（a ) 成分共聚合的（b)成分以外之單體化合物之反應而製得 -13- 1338597 do) 屬心（a )成分的含氟烯烴化合物而言，可例舉：具 至夕1個聚口性之不飽和雙鍵、及至少1個氟原子的化 合物’其具體例而言’可例舉：（."四氟乙嫌、六氟乙 烯。，3,3-三氟丙烯等氟代烯烴類；（2)全氟代（烷基乙 烯醚）類或全氟代（烷氧基烷基乙烯醚）類：（3)全氟 代（甲基乙烯醚）、全氟代（乙基乙烯醚）、全氟代（丙 籲基乙烧酸）、全氟代（丁基乙難）、全氟代（異丁基乙 烯醚）等全氟代（烷基乙烯醚）類：（4 )全氟代（丙氧 基丙基乙稀酸）等全氟代（院氧基嫁基乙场酸）類；等。 此等化合物可以單獨或倂用2種以上。上述者中，特佳爲 六氣丙稀、全氟代（烷基乙烯醚）或全氟代（烷氧基乙烯 醚）’再者’較佳爲組合此等使用。 屬於（b )成分的含有羥基之單體化合物而言，可例 舉：（1 ) 2-羥基乙基乙烯醚、3-羥基丙基乙烯醚、2_羥基 # 丙基乙烯醚、4-羥基丁基乙烯醚、3-羥基丁基乙烯醚、5_ 羥基戊基乙烯醚、6-羥基己基乙烯醚等含有羥基之乙烯醚 類；（2) 2 -羥基乙基烯丙醚、4 -羥基丁基烯丙醚、甘油-烯丙醚等含有羥基之烯丙醚類；（3)烯丙醇；（4)羥基 乙基（甲基）丙烯酸酯；等。此等化合物，可以單獨或倂 用2種以上。較佳爲含有經基之烷基乙烯醚類。 屬於（c)成分之含有偶氮基之聚矽氧烷化合物而言 ，係有可以-N = N -表示的容易熱解理的偶氮基之同時，具 有可以前述一般式（】）表示的聚氧烷段的化合物，而例 -14- (11) 1338597 如，可依日本專利特開平6-93 1 00號公報中所記載的方法 製造者。（c)成分之具體例而言，可例舉：可以下述一 般式（2 )表示的化合物。 HO-In order to achieve the above object, the inventors of the present invention have known a liquid curable resin composition capable of imparting a cured film having a layer structure of two or more layers from one coating film, and a mechanism of separating into two or more layers. See, as a result of concentration, found that the solubility of fluoropolymers having hydroxyl groups in the molecule and the dispersion of φ metal oxide particles, for fluoropolymers and specific metal oxide particles having a specific structure The fact that the stability and the relative evaporation rate can be divided into two or more types of solvent types, and one layer of the coating film obtained by applying the liquid curable resin composition can be separated into a plurality of layers. And the present invention can be accomplished by selecting the solvent type and other conditions, that is, the fact that any kind of metal oxide particles can be separated into a plurality of layers. In the present invention, a liquid curable resin composition or the like as described below can be provided. [1]. A liquid curable resin composition comprising: the components (A) to (F) of the lower φ; (A) the fluoropolymer (B) having a hydroxyl group in the molecule has a number average particle diameter of a metal oxide particle having a refractive index of 丨.5〇 or more and two or more kinds of metal oxide particles (hereinafter referred to as "(B) metal oxide particle") (C) (A) having a hydroxyl group in the molecule (A) One or two or more solvents having a high solubility in a fluoropolymer (hereinafter referred to as "(C) fast-volatile solvent") (D) high dispersion stability of (B) metal oxide particles' 4) 1338597 (C) Solvent-soluble one or more solvents (hereinafter referred to as "(D) late-volatile solvent") (E) The curable compound (F) is thermally induced to generate an acid generator, and C) The relative evaporation rate of the fast volatile solvent is greater than the relative evaporation rate of the (D) delayed volatile agent. [2] The liquid curable resin composition according to the above [1], wherein the (φ C)-based volatile solvent is one or more of the (B) metal oxide particles having low dispersion stability. The solvent and (D) a late-volatile solvent are those having a low solubility in the (A) fluoropolymer having a hydroxyl group in the molecule or two or more solvents. [3] The liquid curable resin composition according to [1] or [2] wherein the (B) metal oxide particles are selected from the group consisting of titanium oxide, zirconium oxide, tin oxide containing antimony, and tin containing Oxidation of one or more kinds of indium oxide, aluminum oxide, cerium oxide, zinc oxide, zinc oxide containing aluminum, tin oxide, zinc oxide containing cerium, # zinc oxide containing indium, and tin oxide containing phosphorus Particles as the main component. [4] The liquid curable resin composition according to [3], wherein (B) the metal oxide particles are particles having titanium oxide as a main component [5]. such as [〗 〖 to [4] The liquid curable resin composition according to any one of the preceding claims, wherein the (?) metal oxide particles are metal oxide particles having a multilayer structure. [6] A cured film obtained by curing the liquid curable resin composition according to any one of [1] to [5], which is characterized in that it has -8-(5) 1338597 2 Multilayer construction above the layer. [7] The cured film according to [6], wherein each layer constituting the multilayer structure has a layer of (B) metal oxide particles or substantially no (B) metal oxide particles present in a high-density manner. The layer, while at least one layer is a layer of (B) metal oxide particles present in a high density manner. [8] A method for producing a cured film, which comprises heating B or a radiation of a liquid curable resin composition according to any one of [1] to [5] The step of hardening. [9] A method for producing a laminate, which is a substrate, and a method for producing a laminate having a multilayer structure thereon, characterized in that it is coated on the above-mentioned material or on a layer formed on the substrate. The liquid curable resin composition according to any one of [1] to [5], wherein a coating film is formed, and a solvent is evaporated from the one layer coating film to form two or more layers. [10] The method for producing a laminate according to the above [9], wherein each of the two or more layers is a layer in which metal oxide particles are present in a high-density manner or substantially no metal oxide particles are present. The layer, while at least one layer is a layer of metal oxide particles in a high density manner. [11] The method for producing a laminate according to [10], wherein the two or more layers are two layers. [12] The method for producing a laminate according to any one of [9] to [1], wherein the two or more layers are further cured by heating. [13] The method for producing a laminate according to any one of [9] to [1], wherein the laminated system optical component. (14) A method for producing a laminate according to any one of [9] to [12], wherein the laminate system is an antireflection film. [15] (11) The method for producing a laminate according to the invention, wherein the laminate is an antireflection film in which at least a high refractive index layer and a low refractive index layer are laminated on a substrate from the substrate side in this order, and [] 1] The second layer of the sS is a high refractive index layer and a low refractive index layer. [16] The method for producing a laminate according to [15], wherein the low refractive index layer is at 589 nm. The refractive index is 1.20 to 1.55, and the refractive index of the high refractive index layer at 589 nm is 1.5 Å to 2.20, and the refractive index of the lower refractive index layer is high. [17] The laminate as described in [11] The manufacturing method, wherein the laminate ' is at least a medium refractive index layer, a high refractive index layer, and a low refractive index layer, which are laminated on the substrate from the substrate side in this order, and [11] The two layers described are made of a commercial refractive index layer and a low refractive index layer. [18] The manufacturer of the laminate described in [17]. Wherein the low refractive index layer has a refractive index of 1.20 to 1.55 at 589 nm, the medium refractive index layer has a refractive index of 1.5 Å to 1.9 Å at 589 nm, and the lower refractive index layer has a high refractive index, and the high refractive index layer The refractive index at 589 nm is 151 to 2.20, and the refractive index of the medium refractive index layer is higher. [19] The laminate of the laminate according to any one of [15] to [18] And a layer of the layer according to any one of [9] to [19]. In the liquid curable resin composition of the present invention, since a cured film having a multilayer structure such as a high refractive index layer and a low refractive index layer can be formed from a single coating film, the cured film can be simplified. In the liquid curable resin composition of the present invention, since two or more layers can be formed from the one-layer coating film obtained by coating the composition, the manufacturing steps of the laminate having the multilayer structure can be simplified. Moreover, the hardening can be achieved by the partialization of the metal oxide particles. The scratch-resistant property of the film or the laminate. The liquid curable resin composition of the present invention can be suitably used for the formation of an optical material such as an antireflection film or a selective transmission film filter, and also has a high fluorine content. It can be suitably used for coating materials, weathering film materials, coating materials, and other materials that require weather resistance. Moreover, the cured film is excellent in adhesion to the substrate. It has high scratch resistance and can provide a good antireflection effect. Therefore, the cured film or laminate of the present invention is extremely useful as an antireflection film, so that it can be improved when applied to various display devices. . [Embodiment] BEST MODE FOR CARRYING OUT THE INVENTION The present invention is divided into a liquid curable resin composition, a cured film, and a -11 - (8) 1338597 laminate, which will be described in detail. 1. Liquid curable resin composition The liquid curable resin composition 'of the present invention' contains the following components (A) to (F). (A) fluoropolymer having a hydroxyl group in the molecule (B) One or two or more kinds of metal oxide particles having a number average particle diameter of 100 nm or less and a refractive index of 1.50 or more (hereinafter referred to as "p (B)" (C) One or two or more solvents having a high solubility in the fluoropolymer having a hydroxyl group in the molecule (A) (hereinafter, simply referred to as "(C)-speed volatile solvent") (D) (B) one or two or more solvents (hereinafter, abbreviated as "(D) late-volatile solvent") (E) which have high dispersion stability of the metal oxide particles and are compatible with the (C)-speed volatile solvent (E) The curable compound φ ( F ) is a thermally initiating acid generator, and the components are described below. (A) a fluoropolymer fluoropolymer having a hydroxyl group in the molecule, which is a polymer having a carbon-fluorine bond in the molecule, and preferably has a fluorine content of 30% by mass or more, more preferably from gel permeation chromatography. The number average molecular weight obtained by conversion in terms of polystyrene is preferably 5,000 or more. Here, the fluorine content is a ruthenium measured by the alizarin compl exon method, and the number average molecular weight is ruthenium when tetrahydrofuran is used as a developing solvent. -12- (9) 1338597 An example of the fluorine-containing polymer used in the present invention is a fluorine-containing polymer having a radical in the molecule (hereinafter referred to as "hydroxy group-containing fluoropolymer"). For example, a preferred fluoropolymer containing a controlled group may be exemplified by a main chain derived from a monomer-containing structural unit containing 10 mol% to 5 mol%/〇. A group of sand sands. Such an olefin-based polymer having a polysiloxane group represented by the following formula (1) in a main chain of a fluoropolymer containing a base group, and the polyfluorene oxyalkylene group in the fluoropolymer The ratio is usually from 0.1 to 20 mol%. R1 - Si - 0 - (1) R2 wherein 'R1 and R2' may be the same or different and represent a hydrogen atom, an alkyl group, a halogenated alkyl group or an aryl group. Further, the fluorine-containing polymer containing a radical is preferably a fluorine content of not more than 3% by mass. More preferably, it is 40 to 60% by mass, and further, the number average molecular weight obtained by gel permeation φ chromatography is preferably 5,000 or more, more preferably ι 〇, 〇 00 to 50 〇〇. The leader. The fluorine-containing polymer containing a radical may be (a) a fluorine-containing olefin compound (hereinafter referred to as "(a) component"), (b) a monomer compound containing a hydroxyl group copolymerizable with the component (a) ( Hereinafter, it is abbreviated as "(b) component") and (c) azo-containing polyoxyalkylene compound (hereinafter referred to as "c component") and, if necessary, (d) reactive emulsifier (hereinafter referred to as 'abbreviation' "(d) component" and/or (e) can be reacted with a monomer compound other than the component (b) copolymerized with the above component (a) to obtain a composition of the heart (a) The fluorine-containing olefin compound may, for example, be a compound having at least one polyunsaturated unsaturated double bond and at least one fluorine atom, and a specific example thereof may be exemplified by (."tetrafluoro B, hexafluoroethylene, fluoroolefins such as 3,3-trifluoropropene; (2) perfluoro(alkyl vinyl ether) or perfluoro(alkoxyalkyl vinyl ether): 3) perfluoro(methyl vinyl ether), perfluoro(ethyl vinyl ether), perfluoro(propyl acetoin), perfluorinated (butyl ethane) Perfluoro(alkyl ethene ether) such as perfluoro(isobutyl vinyl ether): (4) perfluoro(propoxy ethoxylate) and other perfluorinated These compounds may be used alone or in combination of two or more. Among the above, particularly preferred are hexa-propylene, perfluoro(alkyl vinyl ether) or perfluoro(alkoxy vinyl ether). The 'renewer' is preferably used in combination. The hydroxyl group-containing monomer compound belonging to the component (b) may, for example, be (1) 2-hydroxyethyl vinyl ether or 3-hydroxypropyl vinyl ether. 2_hydroxy# propyl vinyl ether, 4-hydroxybutyl vinyl ether, 3-hydroxybutyl vinyl ether, 5-hydroxypentyl vinyl ether, 6-hydroxyhexyl vinyl ether and other hydroxyl-containing vinyl ethers; (2) 2 a hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether, glycerol-allyl ether, etc., a hydroxyl group-containing allyl ether; (3) allyl alcohol; (4) hydroxyethyl (meth) acrylate These compounds may be used alone or in combination of two or more. Preferred are alkyl vinyl ethers containing a trans group. The azo group-containing polyoxane belonging to the component (c) The compound is a compound having a polyoxyalkylene group which can be represented by the above general formula (]) while having an easily thermally cleaved azo group represented by -N = N - , and Example-14- (11) 1338597, for example, can be produced by the method described in Japanese Patent Laid-Open No. Hei 6-93 1 00. Specific examples of the component (c) include compounds represented by the following general formula (2) HO-

ch3 ch3 ch3ch3 .OC(CH2)20-N=N-C-(CH2)2CONH(CH2)3sl(Osl)y(CH2)3NHCh3 ch3 ch3ch3 .OC(CH2)20-N=N-C-(CH2)2CONH(CH2)3sl(Osl)y(CH2)3NH

CNCN

CN CH3CH3CN CH3CH3

⑵ 式中，y=10 至 500，z=l 至 50。 上述之（a)成分、（b)成分以及（c)成分之較佳 組合，係例如，（1 )氟代烯烴/含有羥基之烷基乙烯醚/聚 二甲基氧烷單元，（2 )氟代烯烴/全氟代（烷基乙烯醚）/ 含有羥基之烷基乙烯醚/聚二甲基矽氧烷單元，（3)氟代 烯烴/全氟代（烷氧烷基乙烯醚）/含有羥基之烷基乙烯醚/ 聚二甲基矽氧烷單元，（4)氟化烯烴/全氟代（烷基乙烯 φ 醚）/含有羥基之烷基乙烯醚/聚二甲基矽氧烷單元，（5) 氟代烯烴/全氟代（烷氧（烷基乙烯醚）/含有羥基之烷基 乙烯醚/聚二甲基矽氧烷單元。 於此種含有羥基之含氟聚合物中，源自（a)成分的 構造單元，較佳爲20至70莫耳％，更佳爲25至65莫耳 %，特佳爲3 0至60莫耳％。如源自（a )成分的構造單元 之比例在2 0莫耳％以下時，則所得含氟聚合物中之含氟量 容易變成過少，而所得液狀硬化性樹脂組成物之硬化物， 係難於成爲折射率足夠低者。另一方面，如源自（a )成 分的構造單元之比例在70莫耳％以上時，則所得含氟聚合 -15- (12) 1338597 物對有機溶劑中的溶解性會顯著降低之同時，所得液狀硬 化性樹脂組成物之透明性及對基材的密合性會降低。 於含有羥基之含氟聚合物中’源自（b)成分的構造 單兀’較佳爲1 0至5 0寞耳％。更佳爲下限値在1 3莫耳％ 以上，更佳爲20莫耳％以上2 1莫耳％以下，又，較佳爲 上限値在45莫耳％以下，更佳爲3 5莫耳％以下。如使用 含有此種（b )成分既定量的含氟聚合物以構成液狀硬化 φ 性樹脂組成物’則其硬化物能呈現良好的耐擦傷性與灰塵 擦淨性。另一方面，如源自（b )成分的構造單元之比例 在1 0莫耳％以下時’則含氟聚合物將成爲對有機溶劑的溶 解性劣差者，而如在5 0莫耳％以上埘，則液狀硬化性樹脂 組成物所製得硬化物，將成爲透明性以及低反射率之光學 特性惡化者。 (c)成分之含有偶氮基之聚矽氧烷化合物，其本身 爲熱引發自由基產生劑，而爲製造含氟聚合物的聚合反應 # 中具有作爲聚合起始劑之作用，惟亦可倂用其他自由基起 始劑。於含氟聚合物中，源自（C )成分的構造單元之比 例’係可以一般式（1 )表示的聚矽氧烷段較佳爲0 · 1至 2 0莫耳°/。，更佳爲0 . 1至1 5莫耳％，特佳爲〇. 1至1 0莫 耳％ ’最佳爲0 · 1至5莫耳％的比例。如可以一般式（1 ) 表示的聚矽氧烷段之比例在2 0莫耳％以上時，則所得含有 羥基之含氟聚合物將成爲透明性劣差者，又，如作爲塗佈 劑使用時，在塗佈時容易發生收縮斑（cratering )。 除上述（Ο至（c)成分以外，再作爲（d)成分， -16- (13) 1338597 較佳爲將反應性乳化劑作爲單體成分使用。$ d )成分’則在將含有羥基之含氟聚合物作| 時，可獲得良好的塗佈性及塗平性（level in 應性乳化劑而言’特佳爲使用非離子性反應个 離子性反應性乳化劑之具體例而言，可例舉 般式（3)或一般式（4)表示的化合物。(2) where y=10 to 500, z=l to 50. Preferred combinations of the above (a) component, (b) component and (c) component are, for example, (1) fluoroolefin/hydroxyl-containing alkyl vinyl ether/polydimethyloxane unit, (2) Fluoroolefin/perfluoro(alkyl vinyl ether)/alkyl vinyl ether/polydimethyloxane unit containing hydroxyl group, (3) fluoroolefin/perfluoro(alkoxyalkyl vinyl ether)/ Alkyl vinyl ether/polydimethyloxane unit containing a hydroxyl group, (4) a fluorinated olefin/perfluoro(alkylethylene φ ether)/alkyl vinyl ether/polydimethyl methoxy oxane containing a hydroxyl group Unit, (5) fluoroolefin / perfluoro (alkoxy (alkyl vinyl ether) / hydroxyl group-containing alkyl vinyl ether / polydimethyl siloxane unit. In such hydroxy-containing fluoropolymer The structural unit derived from the component (a) is preferably 20 to 70 mol%, more preferably 25 to 65 mol%, particularly preferably 30 to 60 mol%, as derived from the component (a). When the ratio of the structural unit is 20% by mole or less, the fluorine content in the obtained fluoropolymer tends to be too small, and the cured product of the obtained liquid curable resin composition is difficult to be folded. On the other hand, if the proportion of the structural unit derived from the component (a) is 70 mol% or more, the solubility of the obtained fluorine-containing polymerization-15-(12) 1338597 in an organic solvent will be The transparency of the obtained liquid curable resin composition and the adhesion to the substrate are lowered. The structure of the fluoropolymer containing hydroxyl group is preferably 'structured from the component (b)'. It is preferably from 10 to 50%, more preferably at a lower limit of more than 13% by mole, more preferably 20% by mole or more and 2% by mole or less, and more preferably, the upper limit is at 45% by mole. In the following, it is more preferably 3 5 mol% or less. If a fluoropolymer containing such a component (b) is used to constitute a liquid-hardenable φ-resin composition, the cured product exhibits good scratch resistance. On the other hand, if the ratio of the structural unit derived from the component (b) is less than 10 mol%, the fluoropolymer will become a poor solubility to an organic solvent, and When it is more than 50% by mole, the cured product obtained from the liquid curable resin composition will become transparent. And the optical property of the low reflectance is deteriorated. (c) The azo-containing polyoxyalkylene compound of the component itself is a thermally initiated radical generating agent, and has a function as a polymerization reaction for producing a fluoropolymer. The role of the polymerization initiator may be other than the use of other radical initiators. In the fluoropolymer, the ratio of the structural unit derived from the component (C) is a polyoxane represented by the general formula (1). The alkane segment is preferably from 0. 1 to 2 0 mol/°, more preferably from 0.1 to 1 5 mol%, particularly preferably from 〇. 1 to 10 mol% 'best is 0 · 1 to a ratio of 5 mol%. If the proportion of the polyoxymethane segment represented by the general formula (1) is more than 20 mol%, the resulting fluoropolymer containing a hydroxyl group will become a poor transparency, and When used as a coating agent, cratering tends to occur at the time of coating. In addition to the above (Ο) component (c), as a component (d), -16-(13) 1338597 preferably uses a reactive emulsifier as a monomer component. The $d) component will contain a hydroxyl group. When the fluoropolymer is used as a method, good coatability and leveling property can be obtained (in terms of level in emulsifier, it is particularly preferable to use a nonionic reaction ionic reactive emulsifier). A compound represented by the formula (3) or the general formula (4) can be exemplified.

CH20(CH2)mCH=CH2 ^ ^-QCH2CH(OCH2CH2)sOH 式中，n=l至20、m及S表示反覆單元， s=3 至 50°CH20(CH2)mCH=CH2 ^^-QCH2CH(OCH2CH2)sOH wherein n=l to 20, m and S represent repetitive units, s=3 to 50°

CH20(CH2)mCH=CH2 R3-~OCH2~C—CH(OCH2CH2)s〇H 式中，m及s爲與一般式（3)者相同。 φ 狀或分枝狀的烷基，較佳爲碳數1至40之烷； 於含有羥基之含氟聚合物中，源自（d) 單元之比例，較佳爲〇至1 〇莫耳％，更佳爲 %，特佳爲〇. 1至1莫耳％。如此種比例在1 時，則由於所得液狀硬化性樹脂組成物將成怎 之故處理上會有困難，如作爲塗佈劑使用時耐 〇 作爲（e )成分之能與（a )成分共聚合白 以外之單體化合物而言，可例舉：（1 )甲基 基乙烯醚、正丙基乙烯醚、異丙基乙烯醚、正 -17- ]使用此種（ 塗佈劑使用 I )。此種反 i乳化劑。非 可以下述一 (3) rn = 0 至 4、 (4) R3可爲直鏈 i。 成分之構成 ).】至5莫耳 〕莫耳％以上 「帶黏著性者 濕性會降低 勺（b )成分 乙烯醚、乙 丁基乙烯醚 (14) 1338597 、輿丁基乙燦醚、第三丁基乙烯醚、正戊基乙烯醚、正己 基乙烯醚、正辛基乙烯醚、正十二烷基乙烯醚、2_乙基己 基乙烯醚、環己基乙烯醚等烷基乙烯醚或者環烷基乙烯醚 類；（2)乙酸乙烯、丙酸乙烯、丁酸乙烯、三甲基乙酸 (pivalic acid)乙稀、己酸（capr〇ic acid)乙烯、巴他 酸（batatic acid)乙烯、硬脂酸乙烯等羧酸乙烯酯類：（ 3)甲基（甲基）丙烯酸酯、乙基（甲基）丙烯酸酯 '正 Φ 丁基（甲基）丙烯酸酯、異丁基（甲基）丙烯酸酯、2 -甲 氧乙基（甲基）丙烯酸酯、2-乙氧乙基（甲基）丙烯酸酯 、2-(正丙氧）乙基（甲基）丙烯酸酯等（甲基）丙烯酸 酯類；（4)(甲基）丙烯酸、巴豆酸、馬來酸、富馬酸 、衣康酸等含有羧基之單體化合物等而不含有羥基者。較 佳爲烷基乙烯醚。 於含有羥基之含氟聚合物中，源自（e)成分之構成 單元之比例，較佳爲0至70莫耳％，更佳爲5至35莫耳 # %。如此種比例在70莫耳％以上時，則由於所得液狀硬化 性樹脂組成物會成爲帶有黏著性者之故處理上有困難，而 在作爲塗佈劑使用時，耐濕性會降低。 在含有（d)成分時之（a)成分、（b)成分、（c) 成分、（d )成分以及（e )成分之較佳組合係如下所示。 (〇氟代烯烴/含有羥基之乙烯醚/聚二甲基矽氧烷單 元/非離子性反應性乳化劑/烷基乙烯醚、（2 )氟代烯烴/ 全氟代（烷基乙烯醚）/含有羥基乙烯醚/聚二甲基矽氧烷 單元/非離子性反應性乳化劑/烷基乙烯醚、（3 )氟代烯烴 -18- (15) 1338597 /全氟代（烷氧烷基乙烯醚）/含有羥基之乙烯醚/聚二甲基 矽氧烷單元/非離子性反應性乳化劑/烷基乙烯醚、（4 )氟 代烯烴/全氟化（烷基乙烯醚）/含有羥基之乙烯醚/聚二甲 基矽氧烷單元/非離子性反應性乳化劑/烷基乙烯醚、（5 ) 氟代烯烴/全氟代（烷氧烷基乙烯醚）/含有羥基之乙烯醚/ 聚二甲基矽氧烷單元/非離子性反應性乳化劑/烷基乙烯醚 〇 p 可與（C )成分倂用的自由基聚合起始劑而言，可例 舉：（1)過氧化乙醯、過氧化苯甲醯等過氧化二醯類； (2) 過氧化甲基乙基酮、過氧化環己酮等過氧化酮類； (3) 過氧化氫、第三丁基過氧化氫、氫過氧化茴香素等 過氧化氫類；（4)二第三丁基化過氧、過氧化二異丙苯 、過氧化二月桂醯等二烷基化過氧類；（5)第三丁基過 乙酸酯、第三丁基過三甲基乙酸酯等過氧化酯類；（6) 一偶氮二異丁腈、偶氮二異戊腈等偶氮系化合物類；（7 ) φ 過硫酸銨、過硫酸鈉、過硫酸胛等過硫酸鹽；等。 ±述之自由基聚合起始劑以外之具體例而言，可例舉 :全氟代乙基碘、全氟代丙基碘、全氟代丁基碘、（全氟 代丁基）乙基碘、全氟代己基碘、2-(全氟代己基）乙基 碘、全氟代庚基碘、全氟代辛基碘、2-(全氟代辛基）乙 基碘、全氟代癸基碘、2-(全氟代癸基）乙基碘、七氟代· 2-碘丙烷、全氟代-3-甲基丁基碘、全氟-5-甲基己基碘、 2-(全氟-5-甲基己基）乙基碘、全氟代_7_甲基辛基碘、 2-(全氟代_7_甲基辛基）乙基碘、全氟代甲基癸基碘 -19- (16) 1338597 、2-(全氟代-9-甲基癸基）乙基碘、2,2,3,3-四氟代丙基 碘' 1H，1H，5H-八氟代戊基碘、1义11{，7^十二氟代庚基碘 '四氟代-1，2 -二碘乙烷、乞氟代-1,4 -二碘丁烷、十二氟 代-1，6-二碘己烷等含有碘之氟化合物。含有碘之氟化合物 可以單獨，或倂用上述之有機過氧化物、偶氮系化合物$ 過硫酸鹽。 爲製造含有羥基之含氟聚合物的聚合型式而言，可@ • 用：使用自由基聚合起始劑的乳化聚合法、懸浮聚合法、 塊狀聚合法或溶液聚合法之任一，聚合操作方面，亦可從 分批式、半連續式或連續式之操作等中適當選擇。 爲製得含有羥基之含氟聚合物的聚合反應，較佳爲於 使用溶劑的溶劑系中進行。較佳的有機溶劑而言，可例舉 :(1)乞酸乙酯、乙酸丁酯、乙酸異丙酯、乙酸異丁酯 、乙酸溶纖劑等酯類：（2)丙酮、甲基乙基酮、甲基異 丁基酮、環己基酮等酮類：（3)四氫呋喃、二喟烷等環 • 狀醚類；（4) Ν,Ν -二甲基甲醯胺、N，N -二甲基乙醯胺等 醯胺類；（5)甲苯、二甲苯等芳香族烴類：等。再者， 需要時亦可混合使用醚類、脂肪族烴類等。 如上述方式所得含有羥基之含氟聚合物，有時能以其 聚合反應所得反應溶液直接作爲液狀硬化性樹脂組成物使 用，惟亦可對聚合反應溶液實施適當的後處理。此種後處 理而言，例如，可實施將聚合反應溶液滴加於由醇等所成 該含有羥基之含氟聚合物之不溶化溶劑中，以使該含有羥 基之含氟聚合物凝固的精製方法所代表的一般性再沈澱處 -20- (17) 1338597 理’接著，將所得固態之共聚合物溶解於溶劑中 製含有羥基之含氟聚合物之溶液。又，亦可將經 應溶液去除殘留單體者，直接作爲含有羥基之会 之溶液使用。 本發明之液狀硬化性樹脂組成物之固體成分 %中之（A )含有羥基之含氟聚合物之調配比例， 至7 0質量％，如作成較佳爲1 〇至5 0質量％時， φ 之透明性會更好。 (B)金屬氧化物粒子 本發明中所用（B )金屬氧化物粒子，係數 徑在1 0 Onm以下，且折射率在1 . 5 0以上（波長 之金屬氧化物粒子。如數平均粒子徑在l〇〇nm以 有時難於使金屬氧化物粒子均勻分散。又，有時 物容易沈降而缺少保存安定性。再者，有時所得 Φ 透明性降低，或混濁度（Hoze値）增高。 數平均粒子徑，更佳爲1〇至 8〇nm ’再佳 5 0 n m。 另外，「數平均粒子徑」係指使用電子顯微 定的「數平均粒子徑」之意，如金屬氧化物粒子 時（例如，針狀ΑΤΟ (含有銻之氧化錫粒子）等 長徑（縱向長度）與短徑（橫向長度）之平均。 子形狀爲桿狀（縱寬比在1以上〗0以下的形狀 ，則以短徑作爲粒子徑。 ，即可調 從聚合反 氟聚合物 1 00質量 通常爲5 則硬化膜 平均粒子 5 5 0 n m ) 上時，則 金屬氧化 硬化膜之 爲20至 鏡法所測 係非球形 )，則爲 又，如粒 之意）時 -21 - (18) 1338597 作爲金屬氧化物粒子，可使用較佳爲選自氧化鈦、氧 化錆（Zircon ia )、含有銻之氧化錫、含有錫之氧化銦、 氧化鋁（A I u m i n a )、氧化铈、氧化碎、含有鋁之氧化鋅 、氧化錫、含有銻之氧化鋅以及含有銦之氧化鋅、含有磷 之氧化錫的1種或2種以上之金屬氧化物作爲主成分的粒 子。 在此，亦可採用將金屬氧化物粒子使用該金屬氧化物 # 以外之前述一種或二種以上之金屬氧化物加以被覆之具有 多層構造的金屬氧化物粒子。具有多層構造的金屬氧化物 粒子之具體例而言，可例舉：被覆氧化矽之氧化鈦粒子、 被覆氧化鋁之氧化鈦粒子、被覆鉻之氧化鈦粒子、氧化鋁 、被覆銷之氧化鈦粒子等。在此等金屬氧化物粒子之中， 特佳爲以氧化鈦作爲主成分的粒子或氧化鋁、被覆鉻之氧 化鈦粒子。 如採用具有多層構造的金屬氧化物粒子，即可抑制氧 φ 化鈦之光觸媒活性以防止硬化物之分解。其結果，可製得 高折射率而耐光性異的硬化膜。 又，如採用含有銻之氧化錫粒子（ΑΤΟ )等，即可對 硬化膜賦予帶電防止性。此時，如後所述，由於ΑΤΟ粒 子會偏在化之故，可以更少量之粒子添加量即可同時達成 有效的帶電防止性與良好的透明性。 以氧化鈦作爲主成分的粒子而言，可使用周知者，且 其形狀亦可爲中空粒子、多孔質粒子、蕊•殻（Core · S h e丨丨）型粒子等。又’不限定爲球狀，亦可爲桿狀（係指 -22- (19)1338597 縱寬比在 佳爲桿狀 爲在1至 1以上1 0以下之形狀者）或不定形粒子，而較 依電子顯微鏡法所求得的數平均粒子徑，較佳 1 0 0 n m之範圍內。 又，分散介質，較佳爲水或有機溶劑。有機溶劑而言 ，可例舉：甲酉享、異丙醇、乙二醇、丁醇、乙二醇·丙基 醚等酵類；甲基乙基酮、甲基異丁基等酮類；甲苯、二甲 苯等芳香族烴類；二甲基甲醯胺、二甲基乙醯胺、N_甲基 • 吡咯烷酮等醯胺類；乙酸乙酯、乙酸丁酯、7 -丁內酯等 酯類’四氫呋喃、1，4·二Df烷等醚類等有機溶劑，其中較 佳爲醇類及酮類。其中較爲醇類及酮類。此等有機溶劑， 可以單獨’或混合2種以上後作爲分散介質使用。 以氧化鈦作爲主成分的粒子之市售品而言，可例舉： 黛尹卡（股）製成西埃化成（股）之製品等。 液狀硬化性樹脂組成物對固體成分1 00質量％的（B )金屬氧化物粒子之調配比例，通常爲丨〇至9 0質量。/。， # 較佳爲2〇至8〇質量％。 (C)速揮發溶劑CH20(CH2)mCH=CH2 R3-~OCH2~C—CH(OCH2CH2)s〇H wherein m and s are the same as those of the general formula (3). a φ-like or branched alkyl group, preferably an alkyl group having 1 to 40 carbon atoms; and a ratio of the unit derived from (d) to the fluoropolymer containing a hydroxyl group, preferably from 〇 to 1 〇 mol % More preferably, % is especially good for 〇. 1 to 1% by mole. When the ratio is 1, the treatment of the liquid curable resin composition may be difficult. For example, when used as a coating agent, the resistance to the component (e) is compatible with the component (a). The monomer compound other than the polymerization white can be exemplified by (1) methyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n--17-] using this (coating agent using I) . This anti-im emulsifier. Non can be one of the following (3) rn = 0 to 4, (4) R3 can be a straight chain i. Composition of the ingredients).] to 5 moles of Moer% or more "The adhesiveness of the adhesive will lower the scoop (b) component vinyl ether, butyl butyl vinyl ether (14) 1338597, butyl butyl ether, the first An alkyl vinyl ether or a ring such as tributyl vinyl ether, n-pentyl vinyl ether, n-hexyl vinyl ether, n-octyl vinyl ether, n-dodecyl vinyl ether, 2-ethylhexyl vinyl ether or cyclohexyl vinyl ether Alkyl vinyl ethers; (2) vinyl acetate, ethylene propionate, ethylene butyrate, ethylene pivatic acid, capr〇ic acid ethylene, batatic acid ethylene, Vinyl carboxylates such as stearic acid ethylene: (3) methyl (meth) acrylate, ethyl (meth) acrylate 'n-Φ butyl (meth) acrylate, isobutyl (methyl) (meth)acrylic acid such as acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-(n-propoxy) ethyl (meth) acrylate Ester; (4) (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, etc. In the fluoropolymer containing a hydroxyl group, the proportion of the constituent unit derived from the component (e) is preferably from 0 to 70 mol%, more preferably from 5 to 35. Mohr #%. When the ratio is 70 mol% or more, the obtained liquid curable resin composition may be difficult to handle due to adhesion, and when used as a coating agent, it is resistant. The wetness is lowered. The preferred combination of the component (a), the component (b), the component (c), the component (d), and the component (e) when the component (d) is contained is as follows. Olefin/hydroxyl-containing vinyl ether/polydimethyloxane unit/nonionic reactive emulsifier/alkyl vinyl ether, (2) fluoroolefin/perfluoro(alkyl vinyl ether)/hydroxyethylene-containing Ether/polydimethyloxane unit/nonionic reactive emulsifier/alkyl vinyl ether, (3) fluoroolefin-18- (15) 1338597 / perfluoro(alkoxyalkyl vinyl ether) / Hydroxy-containing vinyl ether/polydimethyloxane unit/nonionic reactive emulsifier/alkyl vinyl ether, (4) fluoroolefin/perfluorinated ( Vinyl ether)/hydroxyl-containing vinyl ether/polydimethyloxane unit/nonionic reactive emulsifier/alkyl vinyl ether, (5) fluoroolefin/perfluoro(alkoxyalkyl vinyl ether) )/hydroxyl-containing vinyl ether/polydimethyloxane unit/nonionic reactive emulsifier/alkyl vinyl ether 〇p can be used as the radical polymerization initiator for the (C) component. For example: (1) bismuth peroxides such as acetoxime and benzamidine peroxide; (2) ketone peroxides such as methyl ethyl ketone or cyclohexanone peroxide; (3) peroxidation Hydrogen peroxide, hydrogen peroxide such as hydrogen peroxide, tert-butyl hydroperoxide or hydrogen peroxide; (4) dialkylation of di-tert-butyl peroxygen, dicumyl peroxide, dilaurate peroxide, etc. Peroxygen; (5) peroxy esters such as t-butyl peracetate and t-butyl pertrimethyl acetate; (6) azobisisobutyronitrile, azobisisovaleronitrile An azo compound; (7) a persulfate such as φ ammonium persulfate, sodium persulfate or barium persulfate; Specific examples other than the radical polymerization initiator described above may be exemplified by perfluoroethyl iodide, perfluoropropyl iodide, perfluorobutyl iodide, (perfluorobutyl)ethyl group. Iodine, perfluorohexyl iodide, 2-(perfluorohexyl)ethyl iodide, perfluoroheptyl iodide, perfluorooctyl iodide, 2-(perfluorooctyl)ethyl iodide, perfluorinated Mercapto iodide, 2-(perfluorodecyl)ethyl iodide, heptafluoro-2-iodopropane, perfluoro-3-methylbutyl iodide, perfluoro-5-methylhexyl iodide, 2- (Perfluoro-5-methylhexyl)ethyl iodide, perfluoro-7-methyloctyl iodide, 2-(perfluoro-7-methyloctyl)ethyl iodide, perfluoromethyl hydrazine Iodine-19-(16) 1338597, 2-(perfluoro-9-methylindolyl)ethyl iodide, 2,2,3,3-tetrafluoropropyl iodide 1H,1H,5H-eight Fluoropentyl iodide, 1 sense 11{,7^dodefluoroheptyl iodide'tetrafluoro-1,2-diiodoethane, fluorinated-1,4-diiodobutane, dodecafluoro A fluorine compound containing iodine such as 1,6-diiodohexane. The fluorine compound containing iodine may be used alone or in combination with the above organic peroxide or azo compound persulfate. For the production of a fluoropolymer containing a hydroxyl group, it is possible to use: an emulsion polymerization method, a suspension polymerization method, a bulk polymerization method or a solution polymerization method using a radical polymerization initiator, and a polymerization operation. In terms of batch, semi-continuous or continuous operation, etc., it can be appropriately selected. The polymerization for producing a fluoropolymer containing a hydroxyl group is preferably carried out in a solvent system using a solvent. Preferred organic solvents include (1) ethyl decanoate, butyl acetate, isopropyl acetate, isobutyl acetate, cellosolve acetate, and the like: (2) acetone, methyl ethyl Ketones such as ketone, methyl isobutyl ketone and cyclohexyl ketone: (3) cycloethers such as tetrahydrofuran and dioxane; (4) hydrazine, hydrazine-dimethylformamide, N,N- Amidoxime such as dimethylacetamide; (5) aromatic hydrocarbons such as toluene and xylene: and the like. Further, an ether or an aliphatic hydrocarbon may be used in combination as needed. The fluoropolymer containing a hydroxyl group obtained as described above may be used as a liquid curable resin composition as it is, but the polymerization reaction solution may be subjected to an appropriate post treatment. In such a post-treatment, for example, a purification method in which a polymerization reaction solution is added dropwise to an insoluble solvent of the hydroxyl group-containing fluoropolymer formed of an alcohol or the like to solidify the hydroxyl group-containing fluoropolymer can be carried out. Representation of general reprecipitation -20-(17) 1338597 </ RTI> Next, a solution of a hydroxy-containing fluoropolymer is prepared by dissolving the obtained solid copolymer in a solvent. Further, the residual monomer may be removed from the solution to be used as a solution containing a hydroxyl group. In the solid content % of the liquid curable resin composition of the present invention, (A) the proportion of the fluorine-containing polymer having a hydroxyl group is 70% by mass, and when it is preferably from 1 Torr to 50% by mass, The transparency of φ will be better. (B) Metal Oxide Particles The (B) metal oxide particles used in the present invention have a coefficient diameter of 10 or less and a refractive index of 1.50 or more (wavelength metal oxide particles. In the case of 〇〇nm, it is difficult to uniformly disperse the metal oxide particles. In some cases, the material is likely to settle and the storage stability is lacking. Further, the Φ transparency may be lowered or the turbidity (Hoze値) may be increased. The particle diameter is more preferably 1 〇 to 8 〇 nm 'more preferably 50 nm. In addition, the "number average particle diameter" means the "number average particle diameter" determined by electron microscopy, such as metal oxide particles. (For example, the average of the long diameter (longitudinal length) and the short diameter (lateral length) such as acicular enamel (tin oxide particles containing bismuth). The sub shape is a rod shape (a shape having a width ratio of 1 or more and 0 or less) When the short diameter is used as the particle diameter, it can be adjusted from the polymerization of the reverse fluoropolymer to 100 masses, usually 5, and the average particle size of the cured film is 550 nm. Non-spherical), it is again, such as the meaning of grain When -21(18) 1338597, as the metal oxide particles, it is preferably selected from the group consisting of titanium oxide, cerium oxide (Zircon ia), tin oxide containing cerium, indium oxide containing tin, and aluminum oxide (AI umina). And cerium oxide, oxidized ash, zinc oxide containing aluminum, tin oxide, zinc oxide containing cerium, zinc oxide containing indium, and tin oxide containing phosphorus, or one or more metal oxides as a main component. Here, metal oxide particles having a multilayer structure in which the metal oxide particles are coated with the one or more metal oxides other than the metal oxide # may be used. Specific examples of the metal oxide particles having a multilayer structure include titanium oxide particles coated with cerium oxide, titanium oxide particles coated with alumina, titanium oxide particles coated with chromium, alumina, and titanium oxide particles coated with a pin. Wait. Among these metal oxide particles, particles containing titanium oxide as a main component, alumina, and chromium oxide-coated titanium oxide particles are particularly preferable. If metal oxide particles having a multilayer structure are used, the photocatalytic activity of the titanium oxide can be suppressed to prevent decomposition of the cured product. As a result, a cured film having a high refractive index and different light resistance can be obtained. Further, if a tin oxide particle containing ruthenium or the like is used, the cured film can be provided with charge prevention property. At this time, as will be described later, since the ruthenium particles are biased, an effective amount of charge prevention and good transparency can be simultaneously achieved with a smaller amount of particles. The particles containing titanium oxide as a main component can be used by a known one, and the shape thereof may be a hollow particle, a porous particle, or a Core · S h e type particle. Further, 'not limited to a spherical shape, and may be a rod shape (referring to a -22-(19)1338597 aspect ratio in a shape in which a rod shape is preferably 1 to 1 or more and 10 or less) or an amorphous particle, and The number average particle diameter determined by electron microscopy is preferably in the range of 100 nm. Further, the dispersion medium is preferably water or an organic solvent. The organic solvent may, for example, be a fermentation such as formazan, isopropanol, ethylene glycol, butanol or ethylene glycol propyl ether; or a ketone such as methyl ethyl ketone or methyl isobutyl; An aromatic hydrocarbon such as toluene or xylene; decylamine such as dimethylformamide, dimethylacetamide or N-methylpyrrolidone; esters such as ethyl acetate, butyl acetate and 7-butyrolactone; An organic solvent such as an ether such as tetrahydrofuran or 1,4-di Dfane is preferably an alcohol or a ketone. Among them, more alcohols and ketones. These organic solvents may be used singly or in combination of two or more kinds as a dispersion medium. In the case of a commercially available product of the particles containing titanium oxide as a main component, a product of the yin yinhua (stock) can be exemplified. The proportion of the liquid curable resin composition to the (B) metal oxide particles having a solid content of 100% by mass is usually from 丨〇 to 90% by mass. /. , # is preferably 2〇 to 8〇% by mass. (C) fast volatile solvent

於本發明之液狀硬化性樹脂組成物中所含（C )速揮 發溶劑’係對上述（A )含有羥基之含氟聚合物的溶解度 高的1種或2種以上之溶劑。在此，對含有羥基之含氟聚 合物的溶解性高，係指當將（A )含有羥基之含氟聚合物 按能成爲50質量％之方式添加於各溶劑中，並在室溫下攪 拌8小時，能在目視下成爲均勻的溶液之意。並且，（C -23- (20) 1338597 )速揮發溶劑之相對蒸發速度，需要爲較後述的（D )遲 揮發溶劑之相對蒸發速度爲高。在此’ 「相對蒸發速度」 ，係指以乙酸丁酯能蒸發90質量％所需時間爲基準的蒸發 速度之相對値之意，詳細內容係如於化學技術，第2卷， 有機溶劑、物理性質及精製方法，第4版（科學間出版社 ，1 98 6年出版，第62頁）所記載者。又，（C)速揮發 溶劑，較佳爲對上述（B )金屬氧化物粒子的分散安定性 φ 低者。（C )速揮發溶劑，如相對蒸發速度較（D )者爲大 ，對含有羥基之含氟聚合物的溶解性高，且對（B)金屬 氧化物粒子的分散安定性低，則在將本發明之液狀硬化性 樹脂組成物塗佈於基材上，並蒸發溶劑（C )及（D )的步 驟中，能使（B )金屬氧化物粒子偏在化。 本發明中，能相當於（C )速揮發溶劑的溶劑而言， 相對蒸發速度大約在1 .7以上的溶劑，而可例舉：甲基乙 基酮（MEK:相對蒸發速度3.8)、異丙醇（IPA:I.7) ® 、甲基異丁基酮（MIBK:相對蒸發速度1.6)、甲基戊基 酮（MAK:0.3)、丙酮、甲基丙基酮等。 (D)遲揮發溶劑 本發明之液狀硬化性樹脂組成物中所含（D )遲揮發 溶劑’係對上述（B )金屬氧化物粒子的分散安定性高的 】種或2種以上之溶劑。在此’對（B )金屬氧化物粒子 的分故安疋性闻’係指在將（B )金屬氧化物粒子分散液 中浸潰玻璃板以使（B )金屬氧化物粒子附著於玻璃壁上 -24- (21) 1338597 ’並將其附著有（B )金屬氧化物粒子的玻璃 劑中時’ （B )金屬氧化物粒子能在目視下均 溶劑中之意。又，（D )遲揮發溶劑，較佳爲 )含有羥基之含氟聚合物的溶解性低者。The (C)-speed volatile solvent contained in the liquid curable resin composition of the present invention is one or two or more solvents having high solubility in the (A) hydroxyl group-containing fluoropolymer. Here, the solubility of the fluoropolymer containing a hydroxyl group is high, and the fluoropolymer containing a hydroxyl group (A) is added to each solvent so as to be 50% by mass, and stirred at room temperature. 8 hours, can be a visually uniform solution. Further, the relative evaporation rate of the (C -23-(20) 1338597) fast-volatile solvent needs to be higher than the relative evaporation rate of the late-releasing solvent (D) which will be described later. Here, 'relative evaporation rate' means the relative enthalpy of evaporation rate based on the time required for butyl acetate to evaporate by 90% by mass. Details are as in Chemical Technology, Volume 2, Organic Solvents, Physics. Nature and purification methods, as described in the 4th edition (Science Press, published in 1978, p. 62). Further, the (C) volatile solvent preferably has a lower dispersion stability φ of the above (B) metal oxide particles. (C) a fast-volatile solvent, if the relative evaporation rate is larger than (D), has high solubility to a hydroxyl group-containing fluoropolymer, and has low dispersion stability to (B) metal oxide particles, When the liquid curable resin composition of the present invention is applied onto a substrate and the solvents (C) and (D) are evaporated, the (B) metal oxide particles can be biased. In the present invention, the solvent corresponding to the (C)-rate volatile solvent may be a solvent having a relative evaporation rate of about 1.7 or more, and may be, for example, methyl ethyl ketone (MEK: relative evaporation rate: 3.8) or different. Propanol (IPA: I.7) ® , methyl isobutyl ketone (MIBK: relative evaporation rate 1.6), methyl amyl ketone (MAK: 0.3), acetone, methyl propyl ketone, and the like. (D) a late-volatile solvent (D) a late-volatile solvent contained in the liquid curable resin composition of the present invention is a solvent having a high dispersion stability to the (B) metal oxide particles or a solvent of two or more kinds. . Here, 'the ampoules of the (B) metal oxide particles' means that the (B) metal oxide particle dispersion is impregnated into the glass plate to cause the (B) metal oxide particles to adhere to the glass wall. When -24-(21) 1338597 'and attaching it to the glass agent of (B) metal oxide particles, '(B) metal oxide particles can be visually observed in the solvent. Further, (D) a late-volatile solvent, preferably a polymer having a hydroxyl group, has a low solubility.

本發明中’相當於遲揮發溶劑的溶劑而言 速度大約在1 · 7以下之溶劑，而具體上可例舉 對蒸發速度2.1)、異丙醇（IPa :1.7) 、I # BuOH:0.5)、第三丁醇、丙二醇-甲基醚、p 醚、丙二醇-丙基醚 '乙基溶纖劑、丙基溶纖 纖劑等。 本發明中所用的（C )速揮發溶劑及/或（ 溶劑’通常可直接使用在上述（A )含有羥基 物之製造時所用的溶劑。 本發明中所用的（C)速揮發溶劑與（D) ’需要爲互相相溶性者。相溶性，係在本發明 # 具體性構成中，如存在有（C )速揮發溶劑與！ 溶劑不致於分離的程度之相溶性即足夠。 在此，所選擇的溶劑究意相當於本發明年 )速揮發溶劑或（D )遲揮發溶劑之何種，係 複數種溶劑之間相對性方式決定者。又，相對 1 . 7之異丙醇，均可相當於（C )速揮發溶劑5 發溶劑之任一種，惟作成與其他（C )速揮發 僅作（D )遲揮發溶劑使用者。 又，在本發明之液狀硬化性樹脂組成物中 浸漬於各溶 勻分散於該 ,對上述（A ，相對蒸發 :甲醇（相 Ξ 丁醇（正-弓二醇-乙基 劑、丁基溶 D )遲揮發 之含氟聚合 遲揮發溶劑 之組成物之 〔D)遲揮發 1所用的（C 在所選擇的 蒸發速度在 〔（D)遲揮 溶劑組合後 ，於溶劑中 -25-In the present invention, the solvent corresponding to the solvent of the late-volatile solvent is about 1.7 or less, and specifically, the evaporation rate is 2.1), isopropyl alcohol (IPa: 1.7), and I # BuOH: 0.5). , third butanol, propylene glycol-methyl ether, p ether, propylene glycol-propyl ether 'ethyl cellosolve, propyl cellosolve, and the like. The (C)-speed volatile solvent and/or (solvent ' used in the present invention can be used as it is in the above (A) solvent for the production of a hydroxyl group. The (C) volatile solvent and (D) used in the present invention "It is necessary to be compatible with each other. The compatibility is in the present invention. In the specific configuration, it is sufficient to have the compatibility of the (C)-speed volatile solvent and the solvent not to be separated. The solvent is equivalent to the speed of the present invention, or the (D) delayed solvent, which is determined by the relative manner between the plurality of solvents. Further, the isopropanol of 1.7 may be equivalent to any one of the five solvents of the (C)-speed volatile solvent, and may be used as a solvent for the late-volatile solvent (D). Further, the liquid curable resin composition of the present invention is immersed in each of the above-mentioned melt-dissolved and dispersed in the above (A, relative evaporation: methanol (phase-butanol (n-chelate diol-ethyl agent, butyl solution D) The late volatilization of the composition of the latent volatile solvent of the fluorine-containing polymer [D) is used for the late volatilization (C at the selected evaporation rate after [(D) delayed solvent combination, in the solvent - 25-

I (22) 1338597 爲改善組成物之塗佈性等或其他目的，而可調配上述（C )速揮發溶劑及（D )遲揮發溶劑以外之溶劑。爲此種目 的可調配的溶劑而言，可例舉：甲基乙基酮、甲基異丁基 酮、環己酮等酮類、乙酸乙酯、乙酸丁酯等酯類。再者， 本發明之液狀硬化性樹脂組成物之溶液中，可在不致於析 出含氟聚合物的範圍內，倂用不能溶解含氟聚合物的溶液 ，例如’水、醇類、酯類等弱溶劑（b a d s ο 1 v e n t )。由此 • ’有時該含氟聚合物之溶液能成爲具有良好的保存性及較 佳塗佈性者。此種弱溶液而言，可例舉：乙醇、異丙醇、 第三丁醇、乙基溶纖劑、丁基溶纖劑等。 對液狀硬化性樹脂組成物中之溶劑（包括（C )成分 及（D)成分）以外之成分總量1 〇 〇質量份，溶劑（c )和 溶劑（D )之合計量使用通常爲30〇至5000質量份、較佳 爲3 00至4000質量份、更佳爲300至3000質量份。溶劑 (C )與溶劑（D )之調配比（質量比），可在I : 99至 • 99 : 1之範圍任意設定。 (E )硬化性化合物 (E )硬化性化合物，係因加熱等而進行聚合，並對 本申請案組成物賦與硬化性者。 硬化性化合物而言，可例舉：各種胺基化合物，或季 戊四醇、多酚、乙二醇等各種含有羥基之化合物等。 可作爲硬化性化合物使用的胺基化合物，係一種將其 含有羥基之含氟聚合物中所存在的羥基反應的胺基，例如 -26- (23) 1338597 ，經基院基胺基及院氧院基胺基之任一方或雙方按合計含 有2個以上的化合物’具體上可例舉：三聚氰胺系化合物 、脲系化合物、苯并胍系化合物、甘脲（a丨y c 〇丨u r丨丨）系化 合物等。 三聚氰胺系化合物’係一般周知爲具有三畊（ triazine )環上結合有氮原子的骨架的化合物，具體上可 例舉：三聚氰胺、烷基化三聚氰胺、羥甲基三聚氰胺、烷 ^ 氧基化甲基三聚氰胺等，惟較佳爲1分子中將羥甲基及院 氧基化甲基之任一或兩者按合計具有2個以上者。具體上 較佳爲使三聚氰胺與甲醛在鹼性條件下進行反應所得羥甲 基化三聚氰胺、烷氧基化甲基三聚氰胺、或者此等衍生物 ，由於能在液狀硬化性樹脂組成物上獲得良好的保存安定 性、以及獲得良好的反應性之故，特佳爲烷氧基化甲基三 聚氰胺。可作爲硬化性化合物使用的羥甲基化之聚氰胺及 院氧化甲基三聚氰胺方面並無限定，亦可使用例如，從文 # 獻「塑膠材料講座「8」脲.三聚氰胺樹脂」（日刊工業 新聞社出刊）所記載的方法所得各種樹脂狀物。 又，脲系化合物而言，除脲之外，尙可例舉：聚羥甲 基化脲、屬於其衍生物的烷氧基化甲基脲、具有糖醛酸內 酯環（urone ring)的羥甲基化糖醛酸內酯及烷氧基化甲 基糖醛內酯等。並且，就脲衍生物等之化合物而言，亦可 使用上述文獻中所記載的各種樹脂狀物。 液狀硬化性樹脂組成物之固體成分I 〇〇質量％中所含 硬化性化合物之調配比例，通常爲3至70質量％、較佳爲 -27- (24) 1338597 3至5 0質量％、更佳爲5至3 0質量％。如硬化性化合物之 使用量過少時，則從所得液狀硬化性樹脂組成物所形成的 薄膜之耐久性會有不足夠的情形，如超出3至70質量％之 範圍時，則在與含氟聚合物的反應中容易發生凝膠化而硬 化物可能成爲脆弱者的情形。 (A)含有羥基之含氟聚合物與（Ε )硬化性化合物的 反應，例如，在溶解有含有羥基之含氟聚合物的有機溶劑 φ 之溶液中添加硬化性化合物，並藉由適當時間之加熱、攪 拌等使反應系均勻化之下實施即可。爲此種反應的加熱溫 度，較佳在30至150 °C之範圍，更佳爲50至120 °C之範 圍。如加熱溫度在3 0 °C以下時，則反應之進行極爲緩慢， 而如在1 5 0 t以上時，由於除作爲目的之反應之外，尙會 發生因硬化性化合物之羥甲基或烷氧化甲基互相間之反應 所引起的交聯反應而生成凝膠之故不宜。反應之進行，可 藉由羥甲基或烷氧化甲基之紅外分光分析等加以定量的方 φ 法 '或者依再沈澱法回收所溶解的聚合物以測定其增加量 之方式，即可實施定量式的確認。 又’ （A)含有羥基之含氟聚合物與（E)硬化性化合 物之反應時，較佳爲例如，與含有羥基之含氟聚合物之製 造時所用有機溶劑同樣者。本發明中，可將如此所得因含 有羥基之含氟聚合物與硬化性化合物所生成的反應溶液， 直接作爲液狀硬化性樹脂組成物之溶液使用，亦可按需要 調配各種添加劑後再行使用。 -28- (25) 1338597 (F )熱引發酸產生劑 能調配於本發明之液狀硬化性樹脂組成物的熱引發酸 產生劑，係使該液狀硬化性樹脂組成物之塗膜等加熱硬化 時，可改善其加熱條件爲更溫和者的物質。此種熱引發酸 產生劑之具體例而言，可例舉：各種脂肪族磺酸及其鹽、 檸檬酸、乙酸、馬來酸等各種脂肪族羧酸及其鹽、安息香 酸、酞酸等各種芳香族羧酸及其鹽、烷基苯磺酸及其銨鹽 、各種金屬鹽、磷酸或有機酸酯等。 可含於液狀硬化性樹脂組成物之固體成分1 00質量％ 中的此種熱引發酸產生劑之使用比例，通常爲0.01至10 質量％、較佳爲0 · 1至5質量％。如此種比例過大時，則液 狀硬化性樹脂組成物之保存安定性會成爲劣差者之故不宜 (G )添加劑 Φ 本發明之液狀硬化性樹脂組成物中，以該液狀硬化性 樹脂組成物之塗佈性及硬化後之薄膜之薄膜之物性之改善 、或對塗膜的感光性之賦與爲目的，可含有例如：具有羥 基的種種聚合物或單體 '顔料或染料等之著色劑、老化防 止劑或紫外線吸收劑等的安定化劑、感光性酸產生劑、表 面活性劑、聚合抑制劑等各種添加劑。特別是，以所形成 的硬化膜之硬度及耐久性之改善爲目的。較佳爲添加光引 發酸產生劑，特別是，較佳爲選擇使用不致於降低液狀硬 化性樹脂組成物之硬化後之透明性，且能均勻溶解於其溶 -29- (26) 1338597 液中者。 (1 )具有羥基的聚合物 具有能調配於本發明之液狀硬化性樹脂組成物的羥基 的聚合物而言，可例舉：與羥基乙基（甲基）丙烯酸酯等 含有經基之共聚合性單體進行共聚合所得聚合物、作爲添 用酚醒樹脂或可溶酚醛而周知之具有苯酚骨架的樹脂等。 (2 )顏料或染料等之著色劑 能調配於本發明之液狀硬化性樹脂組成物的著色劑而 言’可例舉：（1 )鋁氧白、黏土、碳酸鋇、硫酸鋇等的 底質顏料；（2 )鋅白、鉛白、密陀僧、紅丹、群青、普 魯士藍、氧化鈦、鉻酸鋅、氧化鐵紅、碳黑等的無機頻料 :(3 )艷洋紅6 B、永久紅6 B、永久紅R、聯苯胺黃、酞 青藍、酞青綠等的有機顏料；（4 )品紅、若丹明等的鹼 • 性染料；（5 )直接猩紅、直接橘橙等的直接染料；（6 ) 羅色靈、米塔尼爾黃等的酸性染料；等。 (3 )老化防止劑、紫外線吸收劑等的安定化劑 能調配於本發明之液狀硬化性樹脂組成物的老化防止 劑、紫外線吸收劑而言，可使用周知者。 老化防止劑之具體例而言，可例舉：二第三丁基苯、 五倍子酚、苯醌、氫醌、亞甲藍、第三丁基鄰苯二酚、一 苄醚、甲基氫醌、戊基苯醌、戊氧基氫醌、正丁基苯酚、 -30- (27) 1338597 苯酚、氫醌-丙基醚、4, V-〔 1-〔 4-〔 4- ( 1- (4-羥基苯基 )-1-甲基乙基）苯基〕亞乙基〕二苯酚、1,1，3·參（2,5-二甲基-4 -羥基苯基）-3 -苯基丙烷、二苯胺類、伸苯基二 胺類' 啡噻哄（p h e η 01 h i a z i n e )、疏基苯并咪哩等。 又，紫外線吸收劑之具體例而言，例如，可利用：苯 基水楊酸酯所代表的水楊酸系紫外線吸收劑、二羥基二苯 基甲酮。2-羥基-4-甲氧二苯基甲酮等的二苯基甲酮系紫外 φ 線吸收劑、苯并***系紫外線吸收劑、氰基丙烯酸酯系紫 外線吸收劑等作爲各種塑膠之添加劑所使用的紫外線吸收 劑。 (4 )感光性酸產生劑 能調配於本發明之液狀硬化性樹脂組成物的感光性酸 產生劑，係由於對該液狀硬化性樹脂組成物之塗膜賦予感 光性，例如，照射光等的放射線，即能使該塗膜進行光硬 # 化的物質。此種感光性酸產生劑而言，可例舉：（1 )碘 鎰鹽、銃鹽 '鱗鹽、重氮鎗鹽、銨鹽、吡啶鑰鹽等的各種 鎰鹽；（2)yS-酮酯、yS-磺醯砚與此等之Ο：·重氮基化合 物等的碾化合物；（3 )烷基磺酸酯、鹵代烷基磺酸酯、 芳香基磺酸酯、亞胺二磺酸酯等的磺酸酯類；（4)下述 一般式（5 )所示的磺醯亞胺化合物類；（5 )下述一般式 (6 )所示的重氮甲烷化合物類；等。 -31 - (28) 1338597 Ο υ/\η-βο2κα Υ ⑸ ο 式中’ X表不伸烷基、伸芳基、伸烷氧基等的2元基 ，R4表示烷基、芳香基、鹵素取代烷基、鹵素取代芳香基 等的1元基。 ·ν2I (22) 1338597 A solvent other than the above (C)-speed volatile solvent and (D) a late-volatile solvent may be blended for the purpose of improving the coating property of the composition or the like. The solvent to be formulated for this purpose may, for example, be a ketone such as methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, or an ester such as ethyl acetate or butyl acetate. Further, in the solution of the liquid curable resin composition of the present invention, a solution in which the fluoropolymer cannot be dissolved, such as 'water, alcohols, esters, can be used within a range in which the fluoropolymer is not precipitated. Wait for weak solvents (bads ο 1 vent ). Thus, the solution of the fluoropolymer may be a good storage property and a good coating property. Such a weak solution may, for example, be ethanol, isopropanol, tert-butanol, ethyl cellosolve or butyl cellosolve. The total amount of the solvent (including the components (C) and (D)) in the liquid curable resin composition is 1 part by mass, and the total amount of the solvent (c) and the solvent (D) is usually 30. The amount is 5,000 parts by mass, preferably 300 to 4000 parts by mass, more preferably 300 to 3,000 parts by mass. The mixing ratio (mass ratio) of the solvent (C) to the solvent (D) can be arbitrarily set in the range of I:99 to •99:1. (E) Curable compound (E) The curable compound is polymerized by heating or the like, and imparts curability to the composition of the present application. The curable compound may, for example, be various amine-based compounds or various hydroxyl group-containing compounds such as pentaerythritol, polyphenols and ethylene glycol. An amine compound which can be used as a curable compound is an amine group which reacts with a hydroxyl group present in a hydroxyl group-containing fluoropolymer, for example, -26-(23) 1338597, a basal amine group and a hospital oxygen One or both of the hospital amine groups may contain two or more compounds in total. Specific examples thereof include a melamine compound, a urea compound, a benzofluorene compound, and a glycoluril (a丨yc 〇丨ur丨丨). A compound or the like. The melamine-based compound is generally known as a compound having a skeleton to which a nitrogen atom is bonded to a triazine ring, and specific examples thereof include melamine, alkylated melamine, methylol melamine, and alkyloxymethyl group. Melamine or the like is preferably one or more of two or more of a hydroxymethyl group and a hospitaloxylated methyl group in one molecule. Specifically, it is preferred that methylolated melamine, alkoxylated methyl melamine, or the like obtained by reacting melamine with formaldehyde under alkaline conditions can be obtained well on a liquid curable resin composition. The alkoxylated methyl melamine is particularly preferred for its preservation stability and good reactivity. The methylolated melamine and the hospital oxidized methyl melamine which can be used as a curable compound are not limited, and for example, it is also possible to use the "plastic material lecture "8" urea melamine resin" (Japanese Journal of Industry) Various resin materials obtained by the method described in the news agency. Further, as the urea compound, in addition to urea, hydrazine may, for example, be a polymethylolated urea, an alkoxylated methylurea belonging to the derivative thereof, or a urone ring. Hydroxymethylated uronic acid lactone and alkoxylated methyl alditol lactone. Further, as the compound such as a urea derivative, various resin materials described in the above documents can also be used. The blending ratio of the curable compound contained in the solid content I 〇〇 mass % of the liquid curable resin composition is usually from 3 to 70% by mass, preferably from -27 to (24) 1338597 3 to 50% by mass, More preferably, it is 5 to 30% by mass. When the amount of the curable compound used is too small, the durability of the film formed from the obtained liquid curable resin composition may be insufficient, and if it exceeds the range of 3 to 70% by mass, the fluorine is contained. In the reaction of the polymer, gelation easily occurs and the cured product may become a weak one. (A) a reaction of a hydroxyl group-containing fluoropolymer with a (Ε) hardenable compound, for example, adding a curable compound to a solution in which an organic solvent φ containing a hydroxyl group-containing fluoropolymer is dissolved, and by appropriate time Heating, stirring, etc. may be carried out while homogenizing the reaction system. The heating temperature for this reaction is preferably in the range of from 30 to 150 ° C, more preferably in the range of from 50 to 120 ° C. If the heating temperature is below 30 °C, the reaction proceeds very slowly, and if it is above 150t, the hydroxymethyl or alkane of the hardening compound may occur due to the reaction other than the target. It is not preferable to form a gel by a crosslinking reaction caused by a reaction between oxidized methyl groups. The reaction can be carried out by quantitative φ method by infrared spectroscopic analysis of methylol or alkoxylated methyl group or by recovering the dissolved polymer by reprecipitation method to determine the amount of increase. Confirmation of the formula. Further, when the reaction of the (A) fluoropolymer containing a hydroxyl group and the (E) curable compound is carried out, for example, it is preferably the same as the organic solvent used in the production of the fluoropolymer containing a hydroxyl group. In the present invention, the reaction solution formed by the fluoropolymer containing a hydroxyl group and the curable compound can be directly used as a solution of a liquid curable resin composition, and various additives can be formulated as needed before use. . -28- (25) 1338597 (F) A thermally induced acid generator which can be formulated in the liquid curable resin composition of the present invention, and is heated by a coating film or the like of the liquid curable resin composition When hardened, it can improve the heating condition to a milder substance. Specific examples of such a thermally induced acid generator include various aliphatic sulfonic acids and salts thereof, various aliphatic carboxylic acids such as citric acid, acetic acid, and maleic acid, and salts thereof, benzoic acid, citric acid, and the like. Various aromatic carboxylic acids and salts thereof, alkylbenzenesulfonic acids and ammonium salts thereof, various metal salts, phosphoric acid or organic acid esters, and the like. The ratio of use of such a thermally initiating acid generator in the solid content of 100% by mass of the liquid curable resin composition is usually 0.01 to 10% by mass, preferably 0 to 1 to 5% by mass. When the ratio is too large, the storage stability of the liquid curable resin composition may be inferior (G) additive Φ. The liquid curable resin composition of the present invention, the liquid curable resin For the purpose of improving the coating property of the composition and the physical properties of the film of the film after curing, or for imparting sensitivity to the coating film, for example, various polymers having a hydroxyl group or a monomer 'pigment or dye may be contained. Various additives such as a stabilizer such as a coloring agent, an anti-aging agent, or an ultraviolet absorber, a photosensitive acid generator, a surfactant, and a polymerization inhibitor. In particular, it is intended to improve the hardness and durability of the formed cured film. It is preferred to add a photoinitiating acid generator, and in particular, it is preferably selected so as not to lower the transparency after curing of the liquid curable resin composition, and to be uniformly dissolved in the solution -29-(26) 1338597 The middle. (1) A polymer having a hydroxyl group, which has a hydroxyl group which can be blended in the liquid curable resin composition of the present invention, may be a mixture of a hydroxyethyl (meth) acrylate or the like A polymer obtained by copolymerization of a polymerizable monomer, a resin having a phenol skeleton known as a phenolic resin or a resol phenol, and the like. (2) A coloring agent such as a pigment or a dye can be formulated in the coloring agent of the liquid curable resin composition of the present invention, and may be exemplified by: (1) a bottom of aluminum oxychloride, clay, barium carbonate, barium sulfate, or the like. Pigment; (2) Inorganic frequency materials such as zinc white, lead white, mitochondria, red dan, ultramarine blue, Prussian blue, titanium oxide, zinc chromate, iron oxide red, carbon black, etc.: (3) Yanhonghong 6 B , permanent red 6 B, permanent red R, benzidine yellow, indigo blue, indigo green and other organic pigments; (4) magenta, rhodamine and other alkali dyes; (5) direct scarlet, direct orange Such as direct dyes; (6) acid dyes such as roxaline, mitane yellow, etc.; (3) An anti-aging agent such as an anti-aging agent or an ultraviolet absorber. The anti-aging agent and the ultraviolet absorber which can be used in the liquid curable resin composition of the present invention can be used. Specific examples of the aging preventive agent include di-tert-butylbenzene, gallic phenol, benzoquinone, hydroquinone, methylene blue, t-butyl catechol, monobenzyl ether, and methylhydroquinone. , amyl phenyl hydrazine, pentyl hydroxyhydroquinone, n-butyl phenol, -30- (27) 1338597 phenol, hydroquinone-propyl ether, 4, V-[ 1-[ 4-[ 4- ( 1- ( 4-hydroxyphenyl)-1-methylethyl)phenyl]ethylidene diphenol, 1,1,3·g (2,5-dimethyl-4-hydroxyphenyl)-3-benzene Propane, diphenylamine, phenylenediamine phe η 01 hiazine, sulfhydryl benzopyrene, and the like. Further, as a specific example of the ultraviolet absorber, for example, a salicylic acid-based ultraviolet absorber represented by phenyl salicylate or dihydroxydiphenyl ketone can be used. A diphenyl ketone-based ultraviolet ray ray absorbing agent such as 2-hydroxy-4-methoxydiphenyl ketone, a benzotriazole-based ultraviolet absorbing agent, a cyanoacrylate-based ultraviolet absorbing agent, or the like as an additive for various plastics The UV absorber used. (4) The photosensitive acid generator which can be used in the photosensitive resin generator of the liquid curable resin composition of the present invention is provided with photosensitivity to the coating film of the liquid curable resin composition, for example, irradiation light Radiation, etc., is a substance that enables the coating film to be hardened. The photosensitive acid generator may, for example, be (1) various sulfonium salts such as iodonium salt, sulfonium salt, scallop salt, diazo gun salt, ammonium salt or pyridyl salt; and (2) yS-ketone. Ester, yS-sulfonate and the like: · milled compounds such as diazo compounds; (3) alkyl sulfonates, haloalkyl sulfonates, aryl sulfonates, imine disulfonates The sulfonate esters, etc.; (4) the sulfonimide compounds represented by the following general formula (5); (5) the diazomethane compounds represented by the following general formula (6); -31 - (28) 1338597 Ο υ/\η-βο2κα Υ (5) ο where X is a 2-membered group such as an alkyl group, an aryl group or an alkoxy group, and R4 represents an alkyl group, an aromatic group or a halogen. A substituted monovalent group such as an alkyl group or a halogen-substituted aryl group. ·ν2

II r5o2s-c-so2r6 ⑹ 式中’R5及R6表示可互爲相同或不相同的院基、芳 香基、鹵素取代烷基、鹵素取代芳香基等的1元基。 感光性酸產生劑，可以單獨或倂用2種以上，亦可再 倂用前述熱引發酸產生劑。液狀硬化性樹脂組成物之固體 成分1 〇 〇質量份中之感光性酸產生劑之比例，較佳爲〇至 2 〇質量份，更佳爲〇. 1至1 〇質量份。如此種比例過大， 則由於磺化膜之強度會成爲劣差者，且透明性亦會降低之 故不宜。 (5 )表面活性劑 本發明之液狀硬化性樹脂組成物中，以改善該液狀硬 化性樹脂組成物之塗佈性爲目的，而可調配表面活性劑。 此種表面活性劑而言，可使用用知者，具體而言，可使用 例如，各種陰離子系表面活性劑、陽離子系表面活性劑、 非離子系表面活性劑，惟特別是爲作成硬化膜能具有優異 -32 - (29) 1338597 的強度’且具有良好的光學特性起見，較佳爲使用陽離子 系表面活性劑。再者，較佳爲四級銨鹽，其中，如使用四 級聚醚型銨鹽’則由於更能改善灰塵擦淨性之故特佳。屬 於四級聚醚型銨鹽的陽離子系表面活性劑而言，可例舉： 旭電化工業社製阿得卡克爾CC-15、CC-36、CC-42等。 表面活性劑之使用比例，對液狀硬化性樹脂組成物1 00質 量份，較佳爲5質量份以下。 (6 )聚合抑制劑 能調配於本發明之液狀硬化性樹脂組成物中的熱引發 聚合抑制劑而言，可例舉：五倍子酚、苯醌、氫醌、亞甲 藍、第三丁基鄰苯二酚、一苄醚、甲基氫醌、戊基苯醌、 戊氧基氫醌、正丁基苯酚、苯酚、氫醌-丙基醚、4,4'-〔 1-〔4-(1-(4-羥基苯基）-1-甲基乙基）苯基〕亞乙基〕二 苯酚、1,丨，3_參（2,5-二甲基-4-羥基苯基）Ο-苯基丙烷等 # 。此種熱引發聚合抑制劑，對液狀硬化性樹脂組成物之固 體成分1 〇〇質量份，較佳爲按5質量份以下使用。 2.硬化膜 本發明之硬化膜，係使上述本發明之液狀硬化性樹脂 組成物硬化所得者，其特徵爲：具有2層以上之多層構告 。特別是，具有高密度方式存在有上述（B)金屬氧化物 粒子的1層以上之層，與實上不存在有上述（B)金屬氧 化物粒子的1層以下之層爲宜。 -33- (30) 1338597 如從本發明之液狀硬化性樹脂組成物形 較佳爲對基材（所使用的構件）加以塗層。 ，可採用：液浸法、噴霧法、鑲條塗佈法、 垂簾塗佈法、凹版印刷法、絲網印製法或噴; 又，使液狀硬化性樹脂組成物硬化的手 限定，惟較佳爲例如，實施加熱。此時，較 200 °C下，加熱1至180分鐘。由於此種方 φ 可在不損傷基材或所形成的硬化膜之下，更 反射防止性方面優異的硬化膜。較佳爲在5 C 熱1至120分鐘，更佳爲在80至150 °C下力| 鐘。 又，如添加前述之光引發酸產生劑，或 亦可使其硬化。此時，可採用例如，紫外線 屬鹵化物燈、高壓水銀燈等），在0.0 0 1至 照射條件下實施，惟照射條件並不特別限定 # 至 5 J/cm2，再佳爲 0.1 至 3 J/cm2。 另外，硬化膜之硬化程度，例如，作爲 而採用三聚氰胺化合物時，如實施三聚氰胺 基或烷氧化甲基之量之紅外分光分析，或者 累特萃取器（Soxhlet extracton)測定凝膠 定量方式加以確認。 在塗佈液狀硬化性樹脂組成物後，組成 B )及溶劑（D )被蒸發的步驟中，（Β )金 即往塗佈底層側（即與鄰接層的境界附近） 成硬化膜時， 塗層方法而言 輥式塗佈法、 墨法等方法。 段，亦不特別 佳爲在 3 0至 式之加熱1即 有效方式製得 |至1 8 0 °C下加 ]熱1至60分 照射放射線， 照射裝置（金 10 J/cm2 之光 。更佳爲〇.〇1 硬化性化合物 化合物之羥甲 ，使用索克斯 化率，即可按 物中之溶劑（ 屬氧化物粒子 或其相反側進 -34- (31) 1338597 行偏在化。因此，在硬化膜之一方的界面附近，以高密度 方式存在有（B)金屬氧化物粒子，而在硬化膜之另一方 的界面附近，則由於實質上不存在有（B )金屬氧化物粒 子之故，將形成一種低折射率之樹脂層。因而，使由液狀 硬化性樹脂組成物所成一層塗膜進行硬化，即可得實質上 具有二層以上之層構造的硬化膜。此等經分離後所形成的 各層，可由例如，對所得膜之斷面的電子顯微鏡之觀察， φ 而加以確認。在此，以高密度方式存在有（B )金屬氧化 物粒子的層，係指聚集有金屬氧化物粒子的部分之意，係 實質上以金屬氧化物粒子作爲主成分所構成的層，惟有時 在層內部共存有（A)成分等的情形。另一方面，實質上 不存在有（B)金屬氧化物粒子的層，係指未存在金屬氧 化物粒子的部分之意，惟可在不妨礙本發明之效果之範圍 內含有若干金屬氧化物粒子。此層，實質上係由（A)成 分與（E )成分之硬化物等的金屬氧化物粒子以外之成分 Φ 所構成的層。本發明之硬化膜，在多半情形，具有分別連 續形成以高密度方式存在有金屬氧化物粒子的層與實上不 存在有金屬氧化物粒子的層的層之二層構造。爲基材而使 用聚對苯二甲酸乙二醇酯（PET)樹脂（包括具有易黏接 層的PET樹脂）等時，通常，將依序相鄰接方式形成本身 爲基材的層、高密度方式存在有金屬氧化物粒子的層、實 質上不存在有金屬氧化物粒子的層。對二層以上之層構造 ’則後述中加以詳細說明。 所得硬化膜，折射率較佳爲往其膜厚方向變化〇 〇 5 -35- (32) 1338597 至0.8、更佳爲0.1至0.6。再者，上述折射率較佳爲在前 述實質的二層構造的境界附近具有主要的變化。 折射率的變化之程度，可藉由（B )金屬氧化物之含 量、種類、（A)含氟聚合物之含量、組成、以及（E)硬 化性化合物之含量、種類而加以調整。 又，於硬化膜之低折射率部分的折射率，例如，爲 1 .3至1 .5，而於高折射率部分的折射率，爲1 .6至2.2。 3.層合體 本發明之層合體之製造方法中，如從基材上或基材上 所形成的層上塗佈上述液狀硬化性樹脂組成物所得1層塗 膜蒸發溶劑，即可形成2層以上的層。在此，乾燥後的狀 態可爲溶劑並非完全消失的狀態，而可在能獲得作爲硬化 膜的特性的範圍的殘留有溶劑。又，在本發明中，可實施 從丨層塗膜形成2層以上之層2次以上。 • 如依通常之方法塗佈特定之液狀硬化性樹脂組成物， 然後進行乾燥，即分離爲2層以上之層。在此，2層以上 之層；可爲同時含有「高密度方式存在有金屬氧化物粒子 的層」與「實質上不存在有金屬氧化物粒子的層」的2層 以上的層的情形，或者，亦可爲僅由「高密度方式存在有 金屬氧化物粒子的層」所成2層以上的層的情形。 以下，利用圖面，就「2層以上的層，係高密度方式 存在有金屬氧化物粒子的層或者實質上不存在有金屬氧化 物粒子的層’而至少1層係高密度方式存在有金屬氧化物 -36- (33) 1338597 的層」加以說明。第1 A圖表示2層以上的層，係「高密 度方式存在有金屬氧化物粒子的層1」與「實質上不存在 有金屬氧化物粒子的層3」之2層的情形。第1 B圖表示2 層以上的層，係「高密度方式存在有金屬氧化物粒子的層 1、1 a」之2層的情形。第1C圖表示2層以上的層，係「 高密度方式存在有金屬氧化物粒子的層1、la」與「實質 上不存在有金屬氧化物粒子的層3」之3層的情形。第1 D % 圖表示2層以上的層，係「高密度方式存在有金屬氧化物 粒子的層1、la」與「實質上不存在有金屬氧化物粒子的 層3」之3層的情形。第1 E圖表示2層以上的層，係「 高密度方式存在有金屬氧化物粒子的層lb」與「實質上不 存在有金屬氧化物粒子的層3」之2層的情形。 如液狀硬化性樹脂組成物含有2種以上的金屬氧化物 粒子時，如第1 B圖 '第1C圖、第1D圖所示，則可形成 「高密度方式存在有金屬氧化物粒子的層」2種以上。 # 再者，「高密度方式存在有金屬氧化物粒子的層」中 的「金屬氧化物粒子」，係指至少1種，亦即，I種或2 種以上的「金屬氧化物粒子」之意。如液狀硬化性樹脂組 成物含有2種以上之金屬氧化物粒子時，則「高密度方式 存在有金屬氧化物粒子的層」可由2種以上之金屬氧化物 粒子所構成（例如，第1 E圖）。第1 E圖中’ 「高密度方 式存在有金屬氧化物粒子的層lb」係由粒子X與粒子Y 所構成。由於粒子Y係較「高密度方式存在有金屬氧化物 粒子的層lb」之厚度爲大之故’突出於「實質上不存在有 -37 - (34) 1338597 金屬氧化物粒子的層3」中，惟此種突出部分亦包括在「 高密度方式存在有金屬氧化物粒子的層lb」中。 另外，第1A至第1E圖中，於「實質上不存在有金屬 氧化物粒子的層3」中通常不存有金屬氧化物粒子，惟可 在不妨礙本發明之效果的範圍內，含有若干金屬氧化物粒 子。又，「高密度方式存在有金屬氧化物粒子的層l、la 、：I b」亦同樣可含有金屬氧化物粒子以外的其他物質。 • 液狀硬化性樹脂組成物之塗佈法而言，可使用周知之 塗佈方法，特別是可應用液漬法、塗佈機法、印刷法等各 種方法。 乾燥，通常係依從室溫至1 〇〇°c程度之加熱，而實施 1至60分鐘程度。 較佳爲藉由加熱而使此等2層以上的層硬化。具體的 硬化條件則容後詳述。 本發明中，如按溶液狀將液狀硬化性樹脂組成物塗佈 # 於各種基材上，並使所得塗膜乾燥/硬化，即可得層合體 。例如，基板爲透明基材的情形，如於最外層設置低折射 率層，即可形成優異的反射防止膜。 反射防止膜之具體構造，通常係依序層合有基材及低 折射率膜 '或者基材、高折射率膜以及低折射率膜者。此 外，可於基材、高折射率膜以及低折射率膜之間，介在有 其他層，例如，可設置硬質塗膜層、抗靜電層、中折射率 層、低折射率層、高折射率層之組合等之層。 第2圖表示，於基材10上依序層合有高折射率層40 -38- (35) 1338597 及低折射率層50的反射防止膜。 於該反射防止膜中，高折射率層40相當於高密度方 式存在有金屬氧化物粒子的層，而低折射率層5 0相當於 實質上不存在有金屬氧化物粒子的層。 如依本發明，則可由1的塗膜形成高折射率層40與 低折射率層5 0。 第3圖表示，於基材10上依序層合有硬質覆膜層20 • 、抗靜電層30、高折射率層40以及低折射率層50的反射 防止膜。 於該反射防止膜中，高折射率層40相當於高密度方 式存在有金屬氧化物粒子的層，而低折射率層5 0相當於 實質上不存在有金屬氧化物粒子的層。 如依本發明，則可由1的塗膜形成高折射率層40與 低折射率層5 0。 第4圖表示，於基材10上依序層合有抗靜電層30、 Φ 硬質覆膜層20、高折射率層40以及低折射率層50的反射 防止膜。 於該反射防止膜中，高折射率層40相當於高密度方 式存在有金屬氧化物粒子的層，而低折射率層50相當於 實質上不存在有金屬氧化物粒子的層。 如依本發明，則可由1的塗膜形成高折射率層40與 低折射率層5 0。 第5圖表示，於基材1〇上依序層合有硬質覆膜層20 、抗靜電層3 0、中折射率層6 0、高折射率層4 0以及低折 -39- (36) 1338597 射率層5 0的反射防止膜。 於該反射防止膜中，高折射率層40相當於高密度方 式存在有金屬氧化物粒子的層，而低折射率層5 0相當於 實質上不存在有金屬氧化物粒子的層。或者，中折射率層 60、及高折射率層40均相當於高密度方式存在有金屬氧 化物粒子、或中折射率層60相當於高密度方式存在有金 屬氧化物粒子的層，而高折射率層40相當於實質上不存 Φ 在有金屬氧化物粒子的層。 如依本發明，則可由1的塗膜形成中折射率層60與 高折射率層4 0、或高折射率層4 0與低折射率層5 0。較佳 爲由1的塗膜形成高折射率層40與低折射率層50。 第6圖表示，於基材上依序層合有抗靜電層3〇、硬質 覆膜層20、中折射率層60、闻折射率層40以及低折射率 層5 0的反射防止膜。 於該反射防止膜中，高折射率層4 0相當於高密度方 ^ 式存在有金屬氧化物粒子的層，而低折射率層50相當於 實質上不存在有金屬氧化物粒子的層。或者，中折射率層 6〇、及高折射率層40均相當於高密度方式存在有金屬氧 化物粒子的層，或中折射率層6 0相當於高密度方式存在 有金屬氧化物粒子的層，而高折射率層4〇相當於實質上 不存在有金屬氧化物粒子的層。 如依本發明’則可由1的塗膜形成中折射率層60與 尚折射率層4 0、或高折射率層4 0與低折射率層5 〇。較佳 爲由1的塗膜形成高折射率層40與低折射率層5〇。 -40- (37) 1338597 第7圖表示，於基材1 0上依序層合有硬質覆膜層20 、高折射率層4 0以及低折射率層5 0的反射防止膜。 於該反射防止膜中，高折射率層40相當於高密度方 式存在有金屬氧化物粒子的層，而低折射率層5 0相當於 實質上不存在有金屬氧化物粒子的層。 如依本發明，則可由1的塗膜形成高折射率層4 0與 低折射率層5 0。 ρ 第8圖表示，於基材10上依序層合有硬質覆膜層20 、中折射率層6 0、高折射率層4 0以及低折射率層5 0的反 射防止膜。 於該反射防止膜中，高折射率層40相當於高密度方 式存在有金屬氧化物粒子的層，而低折射率層5 0相當於 實質上不存在有金屬氧化物粒子的層。或者，中折射率層 60、及高折射率層40均相當於高密度方式存在有金屬氧 化物粒子的層，或中折射率層60相當於高密度方式存在 # 有金屬氧化物粒子的層，而高折射率層40相當於實質上 不存在有金屬氧化物粒子的層。 如依本發明，則可由1的塗膜形成中折射率層60與 高折射率層40、或高折射率層40與低折射率層50。較佳 爲由1的塗膜形成高折射率層40與低折射率層5 0。 第9圖表示，於基材10上依序層合有抗靜電層30、 高折射率層4 0以及低折射率層5 0的反射防止膜。 於該反射防止膜中，高折射率層40相當於高密度方 式存在有金屬氧化物粒子的層，而低折射率層5 0相當於 -41 - (38) 1338597 實質上不存在有金屬氧化物粒子的層。 如依本發明，則可由1的塗膜形成高折射率層4 0與 低折射率層5 0。 第10圖表示，於基材10上依序層合有抗靜電層30、 中折射率層60、高折射率層40以及低折射率層50的反射 防止膜。 於該反射防止膜中，高折射率層4 0相當於高密度方 φ 式存在有金屬氧化物粒子的層，而低折射率層50相當於 實質上不存在有金屬氧化物粒子的層。或者，中折射率層 60、及闻折射率層40均相當於局密度方式存在有金屬氧 化物粒子的層、或中折射率層6 0相當於高密度方式存在 有金屬氧化物粒子的層，而高折射率層40相當於實質上 不存在有金屬氧化物粒子的層。 如依本發明，則可由1的塗膜形中折射率層6 0與高 折射率層40、或高折射率層40與低折射率層50。較佳爲 Φ 由1的塗膜形成高折射率層40與低折射率層50。 另外，於上述之反射防止膜中，如作爲將使用的液狀 硬化性樹脂組成物中所含金屬氧化物，而添加含有銻之氧 化錫（ΑΤΟ )粒子等的導電性粒子，則所得高密度方式含 有金屬氧化物的層即成爲具有帶電防止性的膜。因而，例 如，將高折射率層或中折射率層，作爲高密度方式含有具 有此種帶電防止性的金屬氧化物的層加以形成時，則高折 射率層或中折射率層即可作成兼具帶電防止性的膜。此時 ，可省略帶電防止膜之形成。 -42 · (39) 1338597 於反射防止膜的本發明之硬化膜之膜厚，例如，爲 〇·〇5μιη至50μηι，惟並不特別限定。 其次，就上述反射防止膜之各層加以說明。 (1 )基材 本發明之反射防止膜所用基材種類並不特別限定，惟 作爲基材之具體例而言’可例舉：三乙醯纖維素、聚對苯 ♦ 二甲醇乙二醇酯樹脂（東麗（股）製盧米勒等）、玻璃、 聚碳酸酯樹脂、丙烯酸樹脂、苯乙烯基樹脂、烯丙基化物 樹脂、降冰片烯系樹脂（J S R (股）製阿爾頓、日本哲翁 (股）製哲翁尼克斯等）、甲基丙烯酸甲酯/苯乙烯共聚 物樹脂、聚烯烴樹脂等各種透明塑膠板、軟片等。較佳爲 三乙醯纖維素、聚對苯二甲酸乙二醇酯樹脂（東麗（股） 製盧米勒等）、降冰片烯系樹脂（J S R (股）製阿爾頓等 )等。 (2 )低折射率層 低折射率層，係指在波長5 8 9 n m下的折射率在1 . 2 0 至1 .55的層。 低折射率層所使用的材料而言，祗要是能獲得作爲目 的之特性者則並不特別限定，惟可例舉：含有含氟聚合物 的硬化性組成物、丙烯酸單體、含氟丙烯酸單體、含有環 氧基之化合物等的硬化物、又，爲提升低折射率層之強度 起見，亦可調配二氧化矽微粒子等。 -43- (40) 1338597 (3 )高折射率層 高折射率層’係指在波長5 8 9 nm下的折射率在1 . 5 0 至2.20，而具有較低折射率層爲高的折射率的層。 爲形成高折射率層，可調配高折射率之無機粒子’例 如金屬氧化物粒子。 金屬氧化物粒子之具體例而言’可例舉：含有銻之氧 φ 化錫（ΑΤΟ )粒子、含有錫之氧化銦（ITO )粒子、氧化 鋅（ΖηΟ )粒子、含有銻之氧化鋅、含有鋁之氧化鋅粒子 、氧化锆（Zr02 )粒子、氧化鈦（Ti02 )粒子、氧化矽被 覆氧化鈦粒子、Al203/Zr02被覆 Ti02粒子、氧化铈（ Ce02 )粒子、含有磷之氧化錫（PTO )粒子等。較佳爲含 有銻之氧化錫（ΑΤΟ )粒子、含有錫之氧化銦（ITO )粒 子' 含有磷之氧化錫粒子、含有鋁之氧化鋅粒子、 Al203/Zr02被覆Ti02粒子》此金屬氧化物粒子，可以一 • 種單獨或二組以上的組合使用。 又，亦可使高折射率層具有硬質覆膜層或抗靜電層之 功能。 (4 ) 在組合具有3種以上之折射率的層時，將波長5 8 9 nm 下的折射率在1.50至1.90，而具有較低折射率層爲高， 較高折射率層爲低的折射率的層，稱爲中折射率層。中折 射率層之折射率，較佳爲1 .5 0至1 . 8 0、更佳爲1 . 5 0至 -44- (41) 1338597 1.75。 爲形成中折射率層起見，可調配高折射率之無機粒子 、例如，金屬氧化物粒體。 金屬氧化物粒子之具體例而言，可例舉：含有銻之氧 化錫（A T 0 )粒子、含有錫之氧化銦（IΤ Ο )粒子、氧化 鋅粒子、含有銻之氧化鋅、含有鋁之氧化鋅粒子、氧化鉻 (Zr02 )粒子、氧化鈦粒子、氧化矽被覆氧化鈦、 _ Al2〇3/Zr〇2被覆Ti〇2粒子、氧化鈽（Ce〇2)粒子等。較 佳爲含有銻之氧化錫（ΑΤΟ )粒子、含有錫之氧化銦（ ΙΤΟ )粒子、含有鋁之氧化鋅粒子、氧化锆（Zr02 )粒木 、含有磷之氧化錫（PTO )粒子。此金屬氧化物粒子，可 以單獨或二組以上的組合使用。 又，亦可使用中折射率層具有硬質覆膜層或抗靜電層 之功能。 如組合低折射率層與高折射率層，即可降低反射率， # 再者，如組合低折射率層、高折射率層、中折射率層，即 可降低反射率之同時，可降低如耀眼（glittering )、帶藍 色（bluish)的色調（顏色的調配）。 (5 )硬質覆膜（jar d coat )層 硬質覆膜之具體例而言，較佳爲從Si〇2 (二氧化砂） 、環氧系樹脂、丙烯酸系樹脂、三聚氰胺系樹脂等材料所 構成者。又，亦可於此等樹脂中調配二氧化矽。 硬質覆膜層，對提升層合物之機械強度上有效。 -45- (42) 1338597 (6 )抗靜電層 抗靜電層之具體例而言，可例舉：經添加含有銻之氧 化錫（ΑΤΟ )粒子、含有錫之氧化銦（ITO )粒子、含有 鋁之氧化鋅粒子、含有磷之氧化錫粒子等具有導電性的金 屬氧化物粒子、或有機、無機之導電性化合物的硬化腊； 因前述金屬氧化物之沈積或賤鍍（sputtering )所製得金 φ 屬氧化物膜：由導電性有機高分子所成膜。導電性有機高 分子而言，可例示：聚乙炔系導電性高分子、聚苯胺系導 電性高分子、聚噻吩系導電性高分子、聚吡咯系導電性高 分子' 聚對伸苯亞乙烯系導電性高分子等。另外，如上所 述’如作爲本發明所使用的液狀硬化性樹脂組成物中所含 的金屬氧化物，而添加ΑΤΟ粒子、ITO粒子、含有銻之氧 化鋅粒子、含有鋁之氧化鋅粒子、含有磷之氧化錫粒子等 導電性粒子，則所得高密度方式含有金屬氧化物的層，將 • 成爲具有帶電防止性的膜。此時，可省略另行形成帶電防 止膜之步驟。 抗靜電層’因會對層合體賦予導電性之故，可防止因 帶電所引起的灰塵等的附著。 此等層’可僅形成一層’亦可形成不相同的層兩層 以上。 又’低、中、高折射層之膜厚，通常分別爲60至 15 0nm '抗靜電層之膜厚通常爲〇〇5至、硬質覆膜層 之膜厚通常爲1至20μπι。 -46- (43) 1338597 本發明中’可依本發明之製造方法形成層合物之任意 連續的2層以上的層’惟如不依本發明之製造方法的層之 製造方法’則可藉由周知之塗佈與硬化、沈積、濺鍍等方 法加以製造。 又’由本發明之液狀硬化性樹脂組成物所成的層，爲 使其硬化以形成具有優異的光學特性與耐久性的硬化膜起 見，特別是賦因加熱所經過的熱歷程爲宜。當然，在常溫 # 下放置時，隨著時間之經過所進行硬化反應，亦能形成作 爲目的之硬化膜，惟實際上，加熱使其硬化的作法，因能 縮短所需時間之故較爲有效。又，如作爲硬化觸媒而添加 熱引發酸產生劑，則更能促進硬化反應。此種硬化觸媒而 言，並不特別限定，而可利用爲一般脲樹脂、三聚氰胺樹 脂等的硬化劑所使用的各種酸類或其鹽類，而特佳爲使用 銨鹽。又，爲進行硬化反應的加熱條件，可適當選擇，惟 加熱溫度則需要在作爲塗佈的對象的基材之耐熱極限溫度 # 以下。 如依本發明，由於可由1層塗膜形成2層以上之層之 故，可簡化層合體之製造步驟。 又，由於使金屬氧化物粒子偏在化之故，可提升層合 體之耐擦傷性。 本發明之層合體，除反射防止膜之外，尙可使用爲例 如，透鏡、選擇透射膜濾光器等的光學用零件。 〔實施例〕 -47- (44) 1338597 在下述說明中，「份」或〔％〕 ’除非特定註解，係 分別表示「質量份」或「質量％」。 製造例1 (1)具有聚合物不飽和基的有機化合物之合成 於附有攪拌機之容器內之锍基丙基三甲氧矽烷22 1份 與二丁基錫二月桂酸鹽1份之混合溶液中，在乾燥空氣中 5 0°C下耗費1小時滴下異佛爾酮二異氰酸酯222份後，再 φ 在7〇。(：下攪拌3小時。 接著，對該反應溶液中在3 0°C下耗費1小時滴下新中 村化學製NK酯 A-TMM-3LM-N (由季戊四醇二丙烯酸酯 60質量％與季戊四醇四丙烯酸酯40質量％所成者。此中， 能參與反應者，僅爲具有羥基的季戊四醇三丙烯酸酯。） 5 49份後，再在60 °C下攪拌10小時，製得反應液。 使用FT-IR (傅立葉轉換（Fourier transform)紅外線 光譜儀（infra-red spectroscopy ))測定該反應液中之生 ♦ 成物，亦即，具有聚合性不飽和基的有機化合物中的殘留 異氰酸酯量的結果’爲〇 . 1質量％以下，而經確認各反應 已按略定量方式實施。由上製得具有硫尿烷鍵、與尿烷鍵 、與甲氧甲矽烷基、以及聚合性不飽和基的化合物773份 、與未參與反應的季戊四醇四丙烯酸酯220份的組成物（ A- 1 )。 製造例2 (2)尿烷丙烯酸酯之合成 -48- (45) 1338597 對附有攪拌機之容器內之異氟爾酮二異氰酸酯18.8 份、與二丁基錫二月桂酸鹽〇 · 2份所成溶液，在1 〇 t下依 1小時之條件滴下新中村化學製N K酯A - Τ Μ Μ - 3 L Μ - N (能 參與反應者，僅爲具有羥基的季戊四醇二丙烯酸酯。）93 份後，再在60 °C下攪拌6小時，製得反應液。 與製造1同樣方式使用FI-IR測定該反應液中之生成 物’亦即殘留異氰酸酯量的結果，爲0. 1質量％以下，而 φ 經確認各反應已按略定量方式實施。又，經確認於分子內 含有尿烷鍵，及丙烯醯基（聚合性不飽和基）的情形。 由上製得尿烷六丙烯酸酯化合物75份之外，尙得混 在有未參與反應的季戊四醇四丙烯酸酯37份的組成物（ A-2 )。 製造例3 〔含有二氧化矽粒子之硬質覆膜層用組成物之調製〕 0 在60°C下攪拌製造例1中所製造的含有聚合性不飽和 基的組成物（A - 1 ) 2.3 2份、二氧化粒子溶膠（甲基乙基 酮二氧化矽溶膠、日產化學工業（股）製MEK-ST、數平 均粒子徑0.02 2 μηι、二氧化矽濃度30%) 91.3份（二氧化 矽粒子計時，爲2 7份）、離子交換水0 · 1 2份、以及對羥 基苯基-甲基醚0 · 0 1份之混合液4小時後，添加原甲酸甲 酯1 .36份，並再在同一溫度下加熱攪拌1小時，製得反 應性粒子（分散液（Α-3 ))。於鋁皿上稱取該分散液（ A - 3 ) 2 g後，在1 7 5 °C之熱板上乾燥1小時，並稱重以求 -49 - (46) 1338597 出固體成分含量的結果，爲30.7%。又，於磁性坩堝中稱 取分散液（A-3 ) 2g後，在80°C之熱板上預備乾燥30分 鐘，並從75(TC之馬弗爐（Muffle )中燒成1小時後之無 機殘渣求出固體成分中之無機含量的結果，當90%。 將該分散液（A-3) 98.6g、組成物（A-2) 3.4g、I -羥 基環己基苯基酮2.1g、伊爾加求亞（IRGACURE) 907 ( 2-甲基-1-〔 4-(甲基硫代）本基〕-2-嗎琳基丙院-1-嗣、奇 φ 巴•特殊化學品（股）製）1 .2g、二季戊四醇六丙烯酸酯 (DPHA ) 33.2g、環己酮7g加以混合攪拌，製得含有二 氧化矽粒子之硬質覆膜層用組成物（固體成分濃度50%) 1 4 5 g ° 製造例4 〔含有氧化锆粒子之組成物之調製〕 將第1稀有元素化學工業（股）製、UEP· 100 (—次 φ 粒徑爲10至30nm ) 3 00份添加於甲基乙基酮（MEK ) 700 份中，使用玻璃小珠進行分散1 6 8小時，在去除玻璃小珠 後製得氧化锆分散溶膠95 0份。於鋁皿上稱取氧化锆分散 溶膠2g後，在1 20°C之熱板上乾燥1小時，並稱重以求出 固體成分含量的結果，爲30% »於該氧化锆分散溶膠l〇〇g 中，在60 °C下攪拌製造例1中所製造的組成物（Α· 1 ) 〇.86g、雙季戊四醇六丙烯酸酯（DPHA) 13.4g、對甲氧苯 酚〇.〇16g、離子交換水〇.〇33g之混合液3小時後，添加 原甲酸甲酯0.3 32g，並再在同一溫度加熱攪拌1小時，製 -50- (47) 1338597 得表面改性氧化鍩粒子之分散液1〗6g。將該分散液〗】6g 、組成物（A-2 ) 1.3 4g、1-羥基環己基苯基酮1.26g '伊 爾加求亞（1RGACURE) 907 ( 2 -甲基-〗-〔4-(甲基硫化 )苯基〕-2-嗎啉基丙烷-1-酮 '奇巴•特殊化學品（股） 製）0.76g、MEK2846g加以混合攪拌’製得含有氧化锆之 組成物（固體成分濃度4% ) 2964g。 # 製造例5 〔含有含有錫之氧化銦（ITO )之組成物之調製〕 混合富士化學（股）製ITO溶膠（10wt% ’ IPA (異 丙醇）溶膠）7〇〇g' DPHA 29.5g、2 -甲基甲基硫 代）苯基〕_2_嗎啉基丙烷-1-酮lg、異丙醇（IPA) 1 7 69.5 g，以製得固體成分濃度4%之含有ITO粒子之組成 物。II r5o2s-c-so2r6 (6) wherein 'R5 and R6 represent a monovalent group such as a deutero group, an aromatic group, a halogen-substituted alkyl group or a halogen-substituted aryl group which may be the same or different from each other. The photosensitive acid generator may be used singly or in combination of two or more kinds, and the above-mentioned thermally initiating acid generator may be further used. The ratio of the photosensitive acid generator in the solid component 1 〇 by mass of the liquid curable resin composition is preferably from 〇 to 2 parts by mass, more preferably from 1 to 1 part by mass. If the ratio is too large, the strength of the sulfonated film will be inferior and the transparency will be lowered. (5) Surfactant The liquid curable resin composition of the present invention is formulated with a surfactant for the purpose of improving the coatability of the liquid hard resin composition. As such a surfactant, those skilled in the art can be used. Specifically, for example, various anionic surfactants, cationic surfactants, and nonionic surfactants can be used, but in particular, it can be used as a cured film. It is preferred to use a cationic surfactant for the purpose of having an excellent strength of -32 - (29) 1338597 and having good optical properties. Further, a quaternary ammonium salt is preferable, and if a quaternary polyether ammonium salt is used, it is particularly preferable because it can improve dust cleanability. The cationic surfactant which is a quaternary polyether ammonium salt may, for example, be Adekakel CC-15, CC-36 or CC-42 manufactured by Asahi Kasei Kogyo Co., Ltd. The proportion of the surfactant to be used is preferably 1 part by mass or less based on 100 parts by mass of the liquid curable resin composition. (6) The thermally initiating polymerization inhibitor which the polymerization inhibitor can be formulated in the liquid curable resin composition of the present invention may, for example, be gallic phenol, benzoquinone, hydroquinone, methylene blue or t-butyl group. Catechol, monobenzyl ether, methylhydroquinone, amyl phenylhydrazine, pentyloxyhydroquinone, n-butylphenol, phenol, hydroquinone-propyl ether, 4,4'-[ 1-[4- (1-(4-Hydroxyphenyl)-1-methylethyl)phenyl]ethylidene]diphenol, 1, hydrazine, 3 gin (2,5-dimethyl-4-hydroxyphenyl) Ο-phenylpropane, etc. #. The heat-initiating polymerization inhibitor is preferably used in an amount of 1 part by mass or less based on 1 part by mass of the solid content of the liquid curable resin composition. 2. Curing film The cured film of the present invention is obtained by curing the liquid curable resin composition of the present invention described above, and has a multilayer structure of two or more layers. In particular, it is preferable that a layer having one or more layers of the above-mentioned (B) metal oxide particles is present in a high-density manner, and that one layer or less of the above-mentioned (B) metal oxide particles are not actually present. -33- (30) 1338597 It is preferred to coat the substrate (the member to be used) from the liquid curable resin composition of the present invention. , can be: liquid immersion method, spray method, strip coating method, vertical curtain coating method, gravure printing method, screen printing method or spray; in addition, the hand curing of the liquid curable resin composition is limited, but For example, heating is performed. At this time, heat at 200 ° C for 1 to 180 minutes. Since such a square φ can be used without damaging the substrate or the formed cured film, it is more excellent in the antireflection property. It is preferably 1 to 120 minutes at 5 C, more preferably at 80 to 150 °C. Further, if the photo-initiating acid generator described above is added, it may be cured. In this case, for example, an ultraviolet ray halide lamp, a high pressure mercury lamp, or the like can be used, and it is carried out under irradiation conditions of 0.01 to 1, but the irradiation conditions are not particularly limited to #5 to 5 J/cm2, and more preferably 0.1 to 3 J/ Cm2. Further, the degree of hardening of the cured film is confirmed, for example, by using an infrared spectroscopic analysis of the amount of the melamine group or the alkoxylated methyl group, or by measuring the gel quantitative method by a Soxhlet extracton. After the liquid curable resin composition is applied, in the step of evaporating the composition B) and the solvent (D), when the (Β) gold is applied to the coating underlayer (that is, near the boundary of the adjacent layer), the cured film is formed. The coating method is a roll coating method, an ink method, or the like. The segment is also not particularly good for heating in the form of 30 to 10, which is an effective method to produce | to 1 to 80 ° C, and to heat 1 to 60 minutes to irradiate the radiation, and the irradiation device (gold 10 J/cm 2 light.佳为〇.〇1 The hydroxymethyl group of the sclerosing compound compound, using the Soxification rate, can be biased according to the solvent (the oxide particles or the opposite side of the -34- (31) 1338597. (B) metal oxide particles are present in a high-density manner near the interface of one of the cured films, and in the vicinity of the interface of the other of the cured films, since (B) metal oxide particles are substantially absent Therefore, a resin layer having a low refractive index is formed. Therefore, a coating film formed of a liquid curable resin composition is cured to obtain a cured film having a layer structure of substantially two or more layers. The layers formed after the separation can be confirmed, for example, by electron microscopy of the cross section of the obtained film, φ. Here, the layer of (B) metal oxide particles is present in a high-density manner, which means that the layers are aggregated. Part of metal oxide particles In the case of a layer composed mainly of metal oxide particles as a main component, the layer (A) may be present in the layer. On the other hand, there is substantially no layer of (B) metal oxide particles. Means that the metal oxide particles are not present, but may contain a plurality of metal oxide particles within a range that does not impair the effects of the present invention. This layer is substantially composed of the components (A) and (E). A layer composed of a component Φ other than the metal oxide particles such as a cured product. In most cases, the cured film of the present invention has a layer in which metal oxide particles are present in a high-density manner and a metal is not present in reality. a two-layer structure of a layer of a layer of oxide particles. When a polyethylene terephthalate (PET) resin (including a PET resin having an easy-adhesion layer) is used as a substrate, usually, it will be sequentially The adjacent method forms a layer which is itself a base material, a layer in which metal oxide particles are present in a high-density manner, and a layer in which metal oxide particles are substantially absent. A layer structure of two or more layers is described later. The obtained cured film preferably has a refractive index which varies in the film thickness direction by -5 - 35 - (32) 1338597 to 0.8, more preferably 0.1 to 0.6. Further, the above refractive index is preferably in the foregoing essence. There is a major change in the vicinity of the boundary of the two-layer structure. The degree of change in the refractive index can be obtained by (B) the content and type of the metal oxide, (A) the content, composition of the fluoropolymer, and (E) hardening. Further, the content and type of the compound are adjusted. Further, the refractive index of the low refractive index portion of the cured film is, for example, 1.3 to 1.5, and the refractive index at the high refractive index portion is 1.6 to 2.2. Laminate The method for producing a laminate according to the present invention, wherein one layer of the coating film evaporating solvent obtained by applying the liquid curable resin composition onto a layer formed on a substrate or a substrate Two or more layers are formed. Here, the state after drying may be a state in which the solvent does not completely disappear, and a solvent may remain in a range in which the characteristics as a cured film can be obtained. Further, in the present invention, it is possible to form two or more layers from the ruthenium layer coating film twice or more. • If a specific liquid curable resin composition is applied by a usual method and then dried, it is separated into two or more layers. Here, the layer of two or more layers may be a layer containing two or more layers of "a layer in which metal oxide particles are present in a high-density manner" and "a layer in which metal oxide particles are substantially absent", or Further, it may be a case where two or more layers are formed only by "a layer in which metal oxide particles are present in a high-density manner". Hereinafter, in the drawing, "a layer having two or more layers is a layer in which a metal oxide particle is present in a high-density manner or a layer in which a metal oxide particle is substantially absent", and at least one layer is in a high-density manner. The layer of oxide-36-(33) 1338597 is described. Fig. 1A shows a layer of two or more layers, which is a layer of "layer 1 in which metal oxide particles are present in a high-density manner" and "layer 3 in which metal oxide particles are substantially absent". Fig. 1B shows a case where two or more layers are two layers of "layers 1 and 1 a in which metal oxide particles are present in a high-density manner". Fig. 1C shows a layer of two or more layers, which is a layer of "layers 1a and 1a of metal oxide particles in a high-density manner" and "layer 3" in which metal oxide particles are substantially absent. The first D% graph shows a layer of two or more layers, and is a layer of three layers of "layers 1a and 1a of metal oxide particles in a high-density manner" and "layer 3 in which metal oxide particles are substantially absent". Fig. 1E shows a layer of two or more layers, which is a layer of "layer lb in which metal oxide particles are present in a high-density manner" and "layer 3 in which metal oxide particles are substantially absent". When the liquid curable resin composition contains two or more kinds of metal oxide particles, as shown in FIG. 1B and FIG. 1C and FIG. 1D, a layer having a high density of metal oxide particles can be formed. "Two or more types." # Further, "metal oxide particles" in the "layer in which metal oxide particles are present in a high-density manner" means at least one type, that is, one type or two or more types of "metal oxide particles". . When the liquid curable resin composition contains two or more kinds of metal oxide particles, the "layer having metal oxide particles in a high-density manner" may be composed of two or more kinds of metal oxide particles (for example, the first E Figure). In Fig. 1E, the "layer lb in which metal oxide particles are present in a high-density manner" is composed of particles X and particles Y. Since the thickness of the particle Y is larger than the thickness of the layer lb in which the metal oxide particles are present in a high-density manner, it is protruded from "the layer 3 of the metal oxide particles which is substantially absent---37-(34) 1338597" However, such a prominent portion is also included in the "layer lb in which metal oxide particles are present in a high-density manner". In addition, in the first layer to the first aspect, the metal oxide particles are not usually present in the layer 3 in which the metal oxide particles are substantially absent, but may be contained in a range that does not impair the effects of the present invention. Metal oxide particles. Further, the layer "1, la, or Ib" in which the metal oxide particles are present in a high-density manner may contain other substances than the metal oxide particles. • For the coating method of the liquid curable resin composition, a known coating method can be used, and in particular, various methods such as a liquid stain method, a coater method, and a printing method can be applied. Drying is usually carried out at a temperature of from room temperature to 1 〇〇 °c, and is carried out for an extent of from 1 to 60 minutes. It is preferred that these two or more layers are hardened by heating. The specific hardening conditions are detailed later. In the present invention, the liquid curable resin composition is applied to various substrates in the form of a solution, and the resulting coating film is dried/cured to obtain a laminate. For example, in the case where the substrate is a transparent substrate, an excellent antireflection film can be formed by providing a low refractive index layer on the outermost layer. The specific structure of the antireflection film is usually a combination of a substrate and a low refractive index film 'or a substrate, a high refractive index film, and a low refractive index film. In addition, between the substrate, the high refractive index film, and the low refractive index film, there may be other layers, for example, a hard coating layer, an antistatic layer, a medium refractive index layer, a low refractive index layer, and a high refractive index may be provided. A layer such as a combination of layers. Fig. 2 shows an antireflection film of a high refractive index layer 40-38-(35) 1338597 and a low refractive index layer 50 laminated on a substrate 10 in this order. In the antireflection film, the high refractive index layer 40 corresponds to a layer in which metal oxide particles are present in a high density manner, and the low refractive index layer 50 corresponds to a layer in which metal oxide particles are substantially absent. According to the present invention, the high refractive index layer 40 and the low refractive index layer 50 can be formed by the coating film of 1. Fig. 3 shows a reflection preventing film of the hard coating layer 20, the antistatic layer 30, the high refractive index layer 40, and the low refractive index layer 50 laminated on the substrate 10 in this order. In the antireflection film, the high refractive index layer 40 corresponds to a layer in which metal oxide particles are present in a high density manner, and the low refractive index layer 50 corresponds to a layer in which metal oxide particles are substantially absent. According to the present invention, the high refractive index layer 40 and the low refractive index layer 50 can be formed by the coating film of 1. Fig. 4 shows a reflection preventing film in which the antistatic layer 30, the Φ hard film layer 20, the high refractive index layer 40, and the low refractive index layer 50 are laminated on the substrate 10 in this order. In the antireflection film, the high refractive index layer 40 corresponds to a layer in which metal oxide particles are present in a high density manner, and the low refractive index layer 50 corresponds to a layer in which metal oxide particles are substantially absent. According to the present invention, the high refractive index layer 40 and the low refractive index layer 50 can be formed by the coating film of 1. Fig. 5 shows that a hard film layer 20, an antistatic layer 30, a medium refractive index layer 60, a high refractive index layer 40, and a low-fold-39- (36) are sequentially laminated on a substrate 1A. 1338597 The anti-reflection film of the luminosity layer 50. In the antireflection film, the high refractive index layer 40 corresponds to a layer in which metal oxide particles are present in a high density manner, and the low refractive index layer 50 corresponds to a layer in which metal oxide particles are substantially absent. Alternatively, both the medium refractive index layer 60 and the high refractive index layer 40 correspond to a metal oxide particle in a high-density manner, or a medium refractive index layer 60 corresponds to a layer in which a metal oxide particle exists in a high-density manner, and high refractive index The rate layer 40 corresponds to a layer in which substantially no Φ exists in the presence of metal oxide particles. According to the present invention, the medium refractive index layer 60 and the high refractive index layer 40, or the high refractive index layer 40 and the low refractive index layer 50 can be formed by the coating film of 1. It is preferable that the high refractive index layer 40 and the low refractive index layer 50 are formed of a coating film of 1. Fig. 6 shows an antireflection film in which an antistatic layer 3A, a hard coating layer 20, a medium refractive index layer 60, a smear refractive index layer 40, and a low refractive index layer 50 are laminated in this order on a substrate. In the antireflection film, the high refractive index layer 40 corresponds to a layer in which metal oxide particles are present in a high density manner, and the low refractive index layer 50 corresponds to a layer in which metal oxide particles are substantially absent. Alternatively, the medium refractive index layer 6〇 and the high refractive index layer 40 correspond to a layer in which metal oxide particles are present in a high-density manner, or the medium refractive index layer 60 corresponds to a layer in which metal oxide particles are present in a high-density manner. The high refractive index layer 4 〇 corresponds to a layer in which metal oxide particles are substantially absent. According to the present invention, the medium refractive index layer 60 and the still refractive index layer 40, or the high refractive index layer 40 and the low refractive index layer 5 can be formed by the coating film of 1. It is preferable that the high refractive index layer 40 and the low refractive index layer 5 are formed of a coating film of 1. -40- (37) 1338597 Fig. 7 shows an antireflection film in which a hard coating layer 20, a high refractive index layer 40, and a low refractive index layer 50 are laminated on the substrate 10 in this order. In the antireflection film, the high refractive index layer 40 corresponds to a layer in which metal oxide particles are present in a high density manner, and the low refractive index layer 50 corresponds to a layer in which metal oxide particles are substantially absent. According to the present invention, the high refractive index layer 40 and the low refractive index layer 50 can be formed by the coating film of 1. ρ Fig. 8 shows a reflection preventing film of a hard coating layer 20, a medium refractive index layer 60, a high refractive index layer 40, and a low refractive index layer 50, which are sequentially laminated on a substrate 10. In the antireflection film, the high refractive index layer 40 corresponds to a layer in which metal oxide particles are present in a high density manner, and the low refractive index layer 50 corresponds to a layer in which metal oxide particles are substantially absent. Alternatively, both the medium refractive index layer 60 and the high refractive index layer 40 correspond to a layer in which metal oxide particles are present in a high-density manner, or the medium refractive index layer 60 corresponds to a layer in which a metal oxide particle is present in a high-density manner. The high refractive index layer 40 corresponds to a layer in which metal oxide particles are not substantially present. According to the present invention, the medium refractive index layer 60 and the high refractive index layer 40, or the high refractive index layer 40 and the low refractive index layer 50 can be formed of a coating film of 1. It is preferable that the high refractive index layer 40 and the low refractive index layer 50 are formed of a coating film of 1. Fig. 9 shows an antireflection film in which the antistatic layer 30, the high refractive index layer 40, and the low refractive index layer 50 are laminated on the substrate 10 in this order. In the anti-reflection film, the high refractive index layer 40 corresponds to a layer in which metal oxide particles are present in a high-density manner, and the low refractive index layer 50 corresponds to -41 - (38) 1338597, and substantially no metal oxide is present. The layer of particles. According to the present invention, the high refractive index layer 40 and the low refractive index layer 50 can be formed by the coating film of 1. Fig. 10 shows a reflection preventing film in which the antistatic layer 30, the medium refractive index layer 60, the high refractive index layer 40, and the low refractive index layer 50 are laminated on the substrate 10 in this order. In the antireflection film, the high refractive index layer 40 corresponds to a layer in which metal oxide particles are present in a high density, and the low refractive index layer 50 corresponds to a layer in which metal oxide particles are substantially absent. Alternatively, both the medium refractive index layer 60 and the scent refractive index layer 40 correspond to a layer in which metal oxide particles are present in a local density manner, or a medium refractive index layer 60 corresponds to a layer in which metal oxide particles are present in a high-density manner. The high refractive index layer 40 corresponds to a layer in which metal oxide particles are not substantially present. According to the present invention, the refractive index layer 60 and the high refractive index layer 40, or the high refractive index layer 40 and the low refractive index layer 50 may be formed by the coating film of 1. Preferably, the high refractive index layer 40 and the low refractive index layer 50 are formed of a coating film of 1. In addition, in the above-mentioned anti-reflection film, as the metal oxide contained in the liquid curable resin composition to be used, conductive particles such as antimony-containing tin oxide particles are added to obtain a high density. A layer containing a metal oxide is a film having charge prevention properties. Therefore, for example, when a high refractive index layer or a medium refractive index layer is formed as a layer containing a metal oxide having such a charge prevention property in a high-density manner, the high refractive index layer or the medium refractive index layer can be formed into a combination. A film with electricity prevention. At this time, the formation of the electrification preventing film can be omitted. -42 · (39) 1338597 The film thickness of the cured film of the present invention in the antireflection film is, for example, 〇·5 μm to 50 μm, but is not particularly limited. Next, each layer of the above-described antireflection film will be described. (1) Substrate The type of the substrate used for the antireflection film of the present invention is not particularly limited, but as a specific example of the substrate, 'exemplified by: triethyl fluorene cellulose, polyparaphenyl benzene dimethanol ethylene glycol ester Resin (Tomil, etc.), glass, polycarbonate resin, acrylic resin, styrene-based resin, allylated resin, norbornene-based resin (JSR (share) Alden, Japan Zhe Weng (shares) Zeon Knicks, etc.), methyl methacrylate / styrene copolymer resin, polyolefin resin and other transparent plastic plates, films and so on. Preferred are triacetonitrile cellulose, polyethylene terephthalate resin (Tomil, etc.), norbornene-based resin (Alston, etc. by J S R). (2) Low refractive index layer The low refractive index layer refers to a layer having a refractive index of 1.20 to 1.55 at a wavelength of 5 8 9 n m. The material used for the low refractive index layer is not particularly limited as long as it can obtain the intended properties, and examples thereof include a curable composition containing a fluorine-containing polymer, an acrylic monomer, and a fluorine-containing acrylic acid. Further, in order to enhance the strength of the low refractive index layer, a hardened material such as a compound containing an epoxy group or the like may be prepared. -43- (40) 1338597 (3) High refractive index layer High refractive index layer' means a refractive index at a wavelength of 589 nm at 1.50 to 2.20, while a layer having a lower refractive index is high. The layer of the rate. In order to form a high refractive index layer, inorganic particles having a high refractive index, such as metal oxide particles, may be formulated. Specific examples of the metal oxide particles include: argon-containing arsenic arsenide (ITO) particles, tin-containing indium oxide (ITO) particles, zinc oxide (ΖηΟ) particles, cerium-containing zinc oxide, and the like. Aluminum zinc oxide particles, zirconium oxide (Zr02) particles, titanium oxide (Ti02) particles, cerium oxide-coated titanium oxide particles, Al203/Zr02 coated TiO 2 particles, cerium oxide (Ce02) particles, and phosphorus-containing tin oxide (PTO) particles Wait. Preferably, it is tin oxide (tellurium) particles containing antimony, tin oxide-containing indium oxide (ITO) particles, phosphorus-containing tin oxide particles, aluminum-containing zinc oxide particles, and Al203/ZrO 2 coated TiO 2 particles. It can be used alone or in combination of two or more groups. Further, the high refractive index layer may have a function as a hard coating layer or an antistatic layer. (4) When combining layers having three or more refractive indices, the refractive index at a wavelength of 589 nm is 1.50 to 1.90, while the layer having a lower refractive index is high, and the layer having a lower refractive index is low. The rate of the layer is called the medium refractive index layer. The refractive index of the medium refractive index layer is preferably from 1.50 to 1.80, more preferably from 1.50 to -44- (41) 1338597. For the formation of the medium refractive index layer, inorganic particles having a high refractive index, for example, metal oxide granules, may be formulated. Specific examples of the metal oxide particles include tin oxide (AT 0 ) particles containing cerium, indium oxide (I Τ Ο ) particles containing tin, zinc oxide particles, zinc oxide containing cerium, and oxidation containing aluminum. Zinc particles, chromium oxide (ZrO 2 ) particles, titanium oxide particles, cerium oxide-coated titanium oxide, _Al2〇3/Zr〇2 coated Ti〇2 particles, cerium oxide (Ce〇2) particles, and the like. More preferably, it is tin oxide (yttrium) particles containing cerium, indium oxide (yttrium) particles containing tin, zinc oxide particles containing aluminum, zirconia (Zr02) particles, and phosphorus-containing tin oxide (PTO) particles. These metal oxide particles may be used singly or in combination of two or more. Further, the medium refractive index layer may have a function of having a hard coating layer or an antistatic layer. If the low refractive index layer and the high refractive index layer are combined, the reflectance can be reduced. # Further, if the low refractive index layer, the high refractive index layer, and the medium refractive index layer are combined, the reflectance can be reduced, and the Glittering, bluish tones (color blending). (5) A concrete example of a hard coating of a jar d coat is preferably made of a material such as Si〇2 (sand dioxide), an epoxy resin, an acrylic resin, or a melamine resin. By. Further, cerium oxide may be formulated in such a resin. The hard coating layer is effective for improving the mechanical strength of the laminate. -45- (42) 1338597 (6) Specific examples of the antistatic layer antistatic layer include tin oxide (ΑΤΟ) particles containing antimony, indium oxide (ITO) particles containing tin, and aluminum. a hardened wax having conductive metal oxide particles such as phosphorus oxide particles or phosphorus-containing tin oxide particles or an organic or inorganic conductive compound; gold obtained by deposition of the above metal oxide or sputtering φ is an oxide film: a film is formed from a conductive organic polymer. The conductive organic polymer may, for example, be a polyacetylene-based conductive polymer, a polyaniline-based conductive polymer, a polythiophene-based conductive polymer, or a polypyrrole-based conductive polymer' poly(p-phenylene vinylene). Conductive polymer and the like. In addition, as described above, the metal oxide contained in the liquid curable resin composition used in the present invention is added with cerium particles, ITO particles, zinc oxide particles containing cerium, zinc oxide particles containing aluminum, When a conductive particle such as a phosphorus-containing tin oxide particle is obtained, a layer containing a metal oxide in a high-density manner is obtained, and it is a film having charge prevention property. At this time, the step of separately forming the charging preventing film can be omitted. Since the antistatic layer ' imparts conductivity to the laminate, adhesion of dust or the like due to charging can be prevented. These layers ' may form only one layer' or may form two or more layers of different layers. Further, the film thicknesses of the low, medium and high refractive layers are usually 60 to 150 nm, respectively. The film thickness of the antistatic layer is usually 〇〇5 to, and the film thickness of the hard film layer is usually 1 to 20 μm. -46- (43) 1338597 In the present invention, any continuous two or more layers which can form a laminate according to the production method of the present invention can be produced by the method of manufacturing a layer which is not according to the production method of the present invention. It is known to be coated and cured, deposited, sputtered, and the like. Further, the layer formed of the liquid curable resin composition of the present invention is cured to form a cured film having excellent optical properties and durability, and in particular, it is preferable to impart a heat history through heating. Of course, when placed under normal temperature #, a hardening reaction can be formed as time passes, but in practice, heating and hardening can be effective because it can shorten the required time. . Further, if a heat-initiating acid generator is added as a curing catalyst, the curing reaction can be further promoted. The curing catalyst is not particularly limited, and various acids or salts thereof used for a curing agent such as a general urea resin or a melamine resin can be used, and an ammonium salt is particularly preferably used. Further, the heating conditions for the hardening reaction can be appropriately selected, but the heating temperature is required to be below the heat-resistant limit temperature # of the substrate to be coated. According to the present invention, since two or more layers can be formed by one coating film, the manufacturing steps of the laminate can be simplified. Further, since the metal oxide particles are biased, the scratch resistance of the laminate can be improved. In addition to the antireflection film, the laminate of the present invention can be used, for example, as an optical component such as a lens or a selective transmission film filter. [Embodiment] -47- (44) 1338597 In the following description, "parts" or [%]' means "parts by mass" or "% by mass" unless otherwise specified. Production Example 1 (1) An organic compound having a polymer unsaturated group was synthesized in a mixed solution of 22 parts of mercaptopropyltrimethoxysilane and 1 part of dibutyltin dilaurate in a container equipped with a stirrer, After 222 parts of isophorone diisocyanate was dropped in dry air at 50 ° C for 1 hour, the φ was again 7 〇. (: stirring for 3 hours. Next, the Nakamura Chemical NK ester A-TMM-3LM-N (60% by mass of pentaerythritol diacrylate and pentaerythritol tetraacrylic acid) was dropped in the reaction solution at 30 ° C for 1 hour. 40% by mass of the ester. Among them, only the pentaerythritol triacrylate having a hydroxyl group can be involved in the reaction.) After 5 49 parts, the mixture was stirred at 60 ° C for 10 hours to obtain a reaction liquid. IR (Fourier transform infra-red spectroscopy) measures the amount of residual isocyanate in the reaction liquid, that is, the amount of residual isocyanate in the organic compound having a polymerizable unsaturated group. 1% by mass or less, and it was confirmed that each reaction was carried out in a slightly quantitative manner. From the above, 773 parts of a compound having a thiourethane bond, a urethane bond, a methoxymethyl sulfonyl group, and a polymerizable unsaturated group were obtained. Composition (A-1) with 220 parts of pentaerythritol tetraacrylate which did not participate in the reaction. Production Example 2 (2) Synthesis of urethane acrylate -48- (45) 1338597 For the isoflur in the container with the stirrer Ketone diisocyanate 18.8 parts, and dibutyltin dilaurate 〇· 2 parts of the solution, under the conditions of 1 〇t, the new ZHONG ester chemical NK ester A - Τ Μ Μ - 3 L Μ - N (can participate in the reaction) Only 93 parts of pentaerythritol diacrylate having a hydroxyl group were added, and then stirred at 60 ° C for 6 hours to obtain a reaction liquid. The product in the reaction liquid was measured by FI-IR in the same manner as in Production 1. That is, the amount of the residual isocyanate was 0.1% by mass or less, and φ was confirmed to have been carried out in a slightly quantitative manner. Further, it was confirmed that the molecule contained a urethane bond and a propylene group (polymerizable unsaturated). In the case of the base of the urethane hexaacrylate compound, 37 parts of the composition (A-2) having pentaerythritol tetraacrylate which is not involved in the reaction was obtained. Production Example 3 [containing cerium oxide Preparation of a composition for a hard coating layer of particles] 0 2. 2 parts of a polymerizable unsaturated group-containing composition (A - 1 ) produced in Production Example 1 was stirred at 60 ° C, and a oxidized particle sol (A) Ethyl ketone cerium oxide sol, Nissan Chemical Industry MEK-ST, number average particle diameter 0.02 2 μηι, cerium oxide concentration 30%) 91.3 parts (27 times for cerium oxide particles), ion exchange water 0 · 12 parts, and p-hydroxybenzene After 4 hours of the mixture of the methyl-methyl ether 0·0 1 part, 1.36 parts of methyl orthoformate was added, and the mixture was further heated and stirred at the same temperature for 1 hour to obtain a reactive particle (dispersion liquid (Α-3) )). Weigh 2 g of the dispersion (A - 3 ) on an aluminum dish, dry it on a hot plate at 175 ° C for 1 hour, and weigh it to obtain -49 - (46) 1338597 The result of the content was 30.7%. Further, 2 g of the dispersion (A-3) was weighed in a magnetic crucible, and then preliminarily dried on a hot plate at 80 ° C for 30 minutes, and fired from 75 (muffle) in a TC for 1 hour. The inorganic residue was determined to have an inorganic content in the solid content, and was 90%. 98.6 g of the dispersion (A-3), 3.4 g of the composition (A-2), and 2.1 g of I-hydroxycyclohexyl phenyl ketone. IRGACURE 907 (2-Methyl-1-[4-(methylthio)benyl]-2-methyllinylpropyl-1-pyrene, odd φ Ba•special chemicals ( (2) 2 g of dipentaerythritol hexaacrylate (DPHA) and 7 g of cyclohexanone were mixed and stirred to obtain a composition for a hard coating layer containing cerium oxide particles (solid content concentration: 50%) 1 4 5 g ° Production Example 4 [Preparation of Composition Containing Zirconia Particles] Adding 300 parts of UEP 100 (-times φ particle size of 10 to 30 nm) to the first rare element chemical industry (stock) In 700 parts of methyl ethyl ketone (MEK), the glass beads were used for dispersion for 168 hours, and after removing the glass beads, 95 parts of the zirconia dispersion sol was prepared. The zirconia dispersion sol 2g was weighed on the aluminum dish. , dried on a hot plate at 1200 ° C for 1 hour, and weighed to obtain a solid content of 30% » in the zirconia dispersion sol l〇〇g, stirred at 60 ° C. The composition (Α·1) 〇.86g produced in the first step, 13.4 g of dipentaerythritol hexaacrylate (DPHA), 16 g of p-methoxyphenol hydrazine, 〇16 g, and ion exchanged hydrazine. 〇33 g, 3 hours later, Add 0.3 32 g of methyl orthoformate and heat and stir at the same temperature for 1 hour to prepare a dispersion of surface-modified cerium oxide particles of 1 - 6 g from -50 to 1338597. The dispersion is 6 g, composition (A-2) 1.3 4g, 1-hydroxycyclohexyl phenyl ketone 1.26g 'IRGACURE 907 (2-methyl-)-[4-(methylsulfonyl)phenyl]-2-吗 morpholinylpropan-1-one 'Chiba special chemical (manufactured)) 0.76 g and MEK 2846 g were mixed and stirred to obtain a composition containing zirconia (solid content concentration: 4%) 2964 g. # Manufacturing Example 5 Preparation of a composition containing tin-containing indium oxide (ITO)] Mixed ITO sol (10 wt% 'IPA (isopropanol) sol) manufactured by Fuji Chemical Co., Ltd. 7〇〇g' DPHA 29. 5 g, 2-methylmethylthio)phenyl]_2-morpholinopropan-1-one lg, isopropanol (IPA) 1 7 69.5 g, to obtain ITO particles containing 4% solid content Composition.

製造例6 〔含有含有銻之氧化錫（ΑΤΟ )之組成物之調製〕 將A Τ Ο粒子（石原科技（股）製、S Ν - 1 0 0 Ρ、一次粒 徑1 0至3 0 n m ) '分散劑（旭電化工業（股）製、阿替卡 普樂尼克TR-701)、以及甲醇，按90/2.78/2 11 (重量比 )之調配量加以混合（全固體成分含量3 1 %、全無機含量 2 9 · 6 % )。於油漆搖器之5 0 m 1聚酯瓶中裝入玻璃小珠4 〇 g (TOSHINRIKO 製 ’BZ-01)(小珠徑 〇.lmni)(體積約 1 6 m 1 )與上述混合液（3 0 g )並分散3小時後，製得中値 -51 - (48) 1338597 粒徑（median size ) 8Onm之分散溶膠。於該溶膠3〇4g中 ’在60°C下攪拌組成物（A-l) 5_7g'對甲氧基苯酚〇.〇lg 、離子交換水〇 . 1 2 g之混合物3小時後，添加甲酸甲酯 1 _ 3 g ’並再在同一溫度加熱攪拌1小時，製得表面改性 A T 0粒子之分散液3 1 1 g。將該分散液2 7 8 3 g '組成物（ A-2) 1.7g、季戊四醇三丙烯酸酯8.59g、2 -甲基-1-〔4-( 甲基硫代）苯基〕-2 -嗎啉基丙烷· 1 -酮〇 . 8 8 g、甲醇3 3 g、 % 丙二醇-甲基醚】6 7 5 g加以混合攪拌，製得有A Τ Ο粒子之 組成物（固體成分濃度5%) 2 000g。 製造例7 〔含有含有鋁之氧化鋅（摻雜有A1之ZnO)粒子之組成 物之調製〕 將氧化鋅粒子（堺化學（股）製摻雜有A1之ZnO粒 子、一次粒徑1 〇至20_ )、分散劑（楠本化成（股）製 # 、何伊音樂特 ED 1 5 1 )以及丙二醇-甲基醚，按 27.6/4.8/67.6 (重量比）之調配量加以混合（全固體成分 含量30%、全無機含量27.6% )。於油漆搖動器之50ml 聚酯瓶中裝入氧化鉻小珠40g (小珠徑0.1mm )與上述混 合液（30g)並分散8小時後，製得中値粒徑40nm之分散 溶膠。於該290g的溶膠中，添加季戊四醇三丙烯酸酯10g 、2 -甲基-1 -〔 4 -(甲基硫代）苯基〕-2 -嗎啉基丙烷-1 -酮 〇 . 5 g、丙二醇-甲基醚2 1 3 8 g並加以混合攪拌，製得含有氧 化鋅粒子之組成物（固體成分濃度4% ) 243 8g。 -52- (49) 1338597 製造例8 〔含有羥基之含氟聚合物之製造〕 使用氮氣’將內容積1.5公升之附有電磁攪拌機之 銹鋼製高壓鍋內充分取代後，添加乙酸乙酯500g、全氟 (丙基乙烯醚）43.2g、乙基乙烯醚4 1.2g、羥基乙基乙 醚2 1 . 5 g、作爲非離子性反應性乳化劑的「阿替卡利亞 φ 皂NE-3 0」（旭電化工業（股）製）40.5g、作爲含有偶 基之聚二甲基ϊ夕氧焼的「VPS-1001」（和光純藥（股） )6.0 g以及過氧化二月桂酿1 .2 5 g，並使用乾冰-甲醇冷 爲-5(TC後，再度使用氮氣以去除系內之氧氣。 接著，添加六氟代丙烯9 7 · 4 g，並開始升溫。當壓 鍋內溫度到達6 0 °C時的壓力爲5.3 X 1 0 5 P a »然後，在 °C之攪拌20小時之下繼續反應，壓力降至1.7xl05Pa 以水冷卻壓力鍋，以停止反應。到達室溫後釋放未反應 • 體並開放壓力鍋，製得固體成分濃度26.4%之聚合物溶 。將所得聚合物溶液投入甲醇中以析出聚合物後，使用 醇加以洗淨，在50°C下進行真空乾燥，製得含有羥基之 氟聚合物220g。 就所得聚合物，經確認使用凝膠滲透色譜法的聚苯 烯換算數平均分子量（Mn )爲4 8000、使用差示掃瞄式 熱法（DSC)的玻璃化溫度（Tg)爲26.8°C以及使用茜 配位劑法的氟含量爲50.3% ° 不 代 烯 肥 氮 製 卻 力 70 時 單 液 甲 含 乙 量 素 -53- (50) 1338597 製造例9 〔二氧化矽被覆Ti02 (氧化鈦）粒子分散液〕 於經二氧化矽被覆的氧化鈦微粉末3 5 0質量份中，添 加環氧乙烷-環氧丙烷共聚物（平均聚合度··約20 ) 80質 量份、異丙醇]000質量份、丁基溶纖劑1 000質量份，使 用玻璃小珠進行分散1 〇小時，在去除玻璃小珠後製得二 氧化矽被覆氧化鈦粒子分散液2430質量份。於鋁皿上稱 φ 取所得二氧化矽被覆Ti02粒子分散液後，在120°C之熱板 上乾燥1小時以求出全固體成分濃度的結果，爲1 7質量％ 。又，將該二氧化矽被覆Ti02粒子分散液_ 1稱取磁性坩 堝中，在80 °C之熱板上預備乾燥30分鐘，並在750 °C之 馬弗爐中燒成1小時，從所得無機殘渣量，及全固體成分 濃度求出全固體成分中之無機含量的結果，爲82質量％。 該固形物之電子顯微鏡觀察之結果，經確認短軸平均 粒子徑爲15nm、長軸平均粒子徑爲46nm、縱寬比爲3.1 # 、數平均粒子徑爲15nm。 實施例1、比較例1 〔液狀硬化性組成物之製造〕 (1 )液狀硬化性樹脂組成物（組成1至5)之製造 將製造例9所得二氧化矽被覆氧化鈦分散液24g (固 體成分4.0 8g)、製造例8所得含有羥基之含氟聚合物2g '交聯性化合物之甲氧化甲基三聚氰胺「塞伊美爾3 0 3」 (三井塞伊科技（股）製）1.2g、與屬於硬化觸媒的觸媒 -54- (51) 1338597 405 0 (三井塞伊科技（股）製、芳香族磺酸化合物） 0.68g，溶解於作爲溶劑的甲基乙基酮32g、甲基異丁基酮 24 g、第三丁醇〗6 g中，以製得組成1。按與製造例9同樣 方式測定該液狀組成物中之全固體成分濃度之結果，爲 7 · 5質量％。 同樣方式，按能成爲下述表1的調配比例的方式調配 各成分，製得組成2至5。在此，組成2至5中，不用二 φ 氧化矽被覆氧化鈦分散液而使用氧化鋁、氧化锆被覆Ti〇2 粒子分散液（黛尹卡（股）製）、不用第三丁醇而使用正 丁醇（n-BuOH )，溶劑之組成則採用甲基乙基酮（MEK )/異丙醇（IPA) /甲基異丁基酮（MIBK) /正丁醇（n-BuOH ) =40/20/30/10 之比例。 與製造例9同樣方式測定粒子徑的結果，數平均粒子 徑（短軸平均粒子徑）爲2 0 n m。 # ( 2 )液狀硬化性樹脂組成物（組成6 )之製造 除不用製造例8中所得有羥基之含氟聚合物而使用凱 拿A DS (埃佛•阿托化學•日本（股）製。係六氟代丙烯 、四氟代乙烯以及二氟代乙烯之共聚物。不具有羥基及聚 合性不飽和基。）以外，其餘則按與液狀硬化性樹脂組成 物（組成1 )之製造同樣方式，製得液狀硬化性樹脂組成 物（組成6 )。 實施例2、比較例2 -55- (52) 1338597 〔硬化膜之製造〕 將二氧化矽粒子溶膠（甲基乙基酮二氧化矽溶膠、日 產化學工業（股）製MEK-ST、數平均粒子徑〇.〇22μηι、 二氧化矽濃度30%) 98.6g、1-羥基環己基苯基酮2.1g、 IRGACURE 907 ( 2-甲基-1·〔 4-(甲基硫代）苯基〕-2·嗎 啉基丙烷-1 -酮、奇巴特殊化學品（股）製）1 · 2 g、雙季戊 四醇六丙烯酸酯（DPHA ) 33_2g、環己基酮7g加以混合 φ 攪拌，製得含有二氧化矽粒子之硬質覆膜層用組成物。使 用鋼絲桿塗佈機（# 1 2 )將該含有二氧化矽粒子之硬質覆 膜層用組成物塗工於三乙醯纖維素軟片（LOFO製、膜厚 8〇μιη )上，並在烘箱內8 0 °C下乾燥1分鐘。接著，在空 氣中，使用高壓水銀燈，依J/cm2之光照射條件下照 射紫外線，以形成硬質覆膜層。使用觸針式膜厚計測定硬 質覆膜層之膜厚的結果’爲5 μηι。 使用鋼絲桿塗佈機（#3 )將實施例1及比較例1所得 φ 組成1至6塗工於所得硬質覆膜層上，並在烘箱內1 2 0 °C 下加熱10分鐘，以形成膜厚爲〇·2μιη之硬化膜層。 評價例1 〔硬化膜之評價〕 使用顯微鏡觀察實施例2及比較例2所得硬化膜斷面 ，以評價是否分離爲二層。評價基準係如下所示。第11 圖中表示各狀態下的典型例。 〈評價基準〉 -56- (53) (53)1338597 二層分離 並未分離（部分凝聚） 均勻的構造 混濁度（haze値）（％ )，係使用 Haze計測定所得 層合體中的混濁度，依據下述基準加以評價。 〇：混濁度在]%以下者。 △:混濁度在5%以下者。 X :混濁度在5%以上者。 其結果如下述表1所示。Production Example 6 [Preparation of a composition containing antimony tin oxide (ΑΤΟ)] A Τ Ο particles (made by Ishihara Satoshi Co., Ltd., S Ν - 1 0 0 Ρ, primary particle diameter 10 to 30 nm) 'Dispersant (Asahi Chemical Industry Co., Ltd., Ateka Plexic TR-701), and methanol, mixed according to the amount of 90/2.78/2 11 (weight ratio) (all solid content of 31% The total inorganic content is 2 9 · 6 % ). In a 50 m 1 polyester bottle of a paint shaker, a glass bead 4 〇g (TOSHINRIKO 'BZ-01) (small bead 〇.lmni) (volume about 16 m 1 ) and the above mixture were placed ( After 30 hours of dispersing and dispersing for 3 hours, a dispersion sol of medium 値-51 - (48) 1338 597 (median size) 8 Onm was obtained. In the sol 3〇4g, the mixture of the composition (Al) 5_7g' p-methoxyphenol 〇.〇lg, ion exchanged hydrazine. 1 2 g was stirred at 60 ° C for 3 hours, and then methyl formate 1 was added. _ 3 g ' and heating and stirring at the same temperature for 1 hour to obtain a dispersion of surface-modified AT 0 particles of 31 1 g. The dispersion 2 687 g of composition (A-2) 1.7 g, pentaerythritol triacrylate 8.59 g, 2-methyl-1-[4-(methylthio)phenyl]-2 - Phytylpropane·1 -ketooxime. 8 8 g, methanol 3 3 g, % propylene glycol-methyl ether] 6 7 5 g was mixed and stirred to obtain a composition of A Τ Ο particles (solid content concentration 5%) 2 000g. Production Example 7 [Preparation of a composition containing particles of aluminum-containing zinc oxide (ZnO doped with A1)] ZnO particles doped with A1 by a zinc oxide particle (manufactured by Nippon Chemical Co., Ltd.) 20_), dispersing agent (Nan Ben Hua Cheng (share) system #, He Yi music special ED 1 5 1 ) and propylene glycol-methyl ether, mixed according to the amount of 27.6/4.8/67.6 (weight ratio) (full solid content 30%, total inorganic content 27.6%). Into a 50 ml polyester bottle of a paint shaker, 40 g of chrome oxide beads (small bead diameter: 0.1 mm) and the above mixed solution (30 g) were dispersed and dispersed for 8 hours to obtain a dispersed sol having a medium ruthenium size of 40 nm. To the sol of 290 g, pentaerythritol triacrylate 10 g, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one oxime. 5 g, propylene glycol 2-methyl ether 2 1 3 8 g was mixed and stirred to obtain a composition containing zinc oxide particles (solid content concentration: 4%) 243 8 g. -52- (49) 1338597 Production Example 8 [Production of Hydroxyl Group Containing Hydroxyl Group] 500 g of ethyl acetate was added to the autoclave of a stainless steel pressure cooker equipped with an electromagnetic stirrer with an internal volume of 1.5 liters. 43.2 g of perfluoro(propyl vinyl ether), 4 1.2 g of ethyl vinyl ether, 21.5 g of hydroxyethyl ether, and "Aticaglia φ soap NE-3 0 as a nonionic reactive emulsifier" 40.5g (made by Asahi Kasei Co., Ltd.), "VPS-1001" (Wako Pure Chemicals Co., Ltd.) as a polydimethyl oxime oxime containing a diradical group, and 6.0 g of peroxidized laurel. 2 5 g, and use dry ice-methanol to cool to -5 (after TC, use nitrogen again to remove the oxygen in the system. Next, add hexafluoropropylene 9 7 · 4 g, and start to heat up. When the temperature in the pressure pot reaches The pressure at 60 ° C is 5.3 X 1 0 5 P a » Then, the reaction is continued under stirring at ° C for 20 hours, the pressure is lowered to 1.7×10 5 Pa, and the pressure cooker is cooled with water to stop the reaction. Reaction • Open the pressure cooker and prepare a polymer with a solid concentration of 26.4%. The resulting polymer solution The polymer was precipitated in methanol, washed with an alcohol, and vacuum-dried at 50 ° C to obtain 220 g of a fluoropolymer containing a hydroxyl group. The obtained polymer was confirmed to be polyphenylene by gel permeation chromatography. The olefin conversion number average molecular weight (Mn) is 4 8000, the glass transition temperature (Tg) using differential scanning thermal method (DSC) is 26.8 ° C, and the fluorine content using the ruthenium complexing agent method is 50.3% ° When the olefinic fertilizer has a nitrogen force of 70, the single liquid liquid contains the hexagram-53-(50) 1338597. Production Example 9 [cerium oxide coated Ti02 (titanium oxide) particle dispersion] The titanium oxide fine powder coated with cerium oxide 80 parts by mass of ethylene oxide-propylene oxide copolymer (average degree of polymerization: about 20) 80 parts by mass, isopropyl alcohol] 000 parts by mass, and butyl cellosolve 1 000 parts by mass, using glass small After the beads were dispersed for 1 hour, 2430 parts by mass of the cerium oxide-coated titanium oxide particle dispersion liquid was obtained after removing the glass beads. The obtained cerium oxide-coated TiO 2 particle dispersion liquid was weighed on an aluminum dish and then at 120 ° C. Dry on a hot plate for 1 hour to find the total solid content The result was 17.7% by mass. Further, the cerium oxide-coated TiO 2 particle dispersion _ 1 was weighed into a magnetic crucible, and preliminarily dried on a hot plate at 80 ° C for 30 minutes, and at 750 ° C. When the amount of the inorganic residue in the whole solid content was determined from the obtained inorganic residue amount and the total solid content concentration in the furnace, the result was 82% by mass. The results of electron microscopic observation of the solid matter confirmed the minor axis average. The particle diameter was 15 nm, the long-axis average particle diameter was 46 nm, the aspect ratio was 3.1 #, and the number average particle diameter was 15 nm. Example 1 and Comparative Example 1 [Production of liquid curable composition] (1) Production of liquid curable resin composition (compositions 1 to 5) The cerium oxide-coated titanium oxide dispersion obtained in Production Example 9 was 24 g ( Solid component 4.0 8 g), hydroxy group-containing fluoropolymer obtained in Production Example 8 2g 'crosslinkable compound methacrylic acid methyl melamine "Seimer 3 0 3" (manufactured by Mitsui Sei Technology Co., Ltd.) 1.2 g, Catalyst-54- (51) 1338597 405 0 (manufactured by Mitsui Sui Technology Co., Ltd., aromatic sulfonic acid compound) 0.68 g, dissolved in methyl ethyl ketone as a solvent, 32 g, methyl Composition 1 was obtained by using isobutyl ketone 24 g and tert-butanol 6 g. The total solid content concentration in the liquid composition was measured in the same manner as in Production Example 9, and was 7.5 % by mass. In the same manner, the components were blended in such a manner that the blending ratios shown in Table 1 below were obtained, and compositions 2 to 5 were obtained. Here, in the compositions 2 to 5, the titanium oxide dispersion liquid is not coated with the di-φ yttria, and the Ti 2 dispersion (disinfected with yttrium oxide) is used, and the third-butanol is used. n-Butanol (n-BuOH), solvent composition using methyl ethyl ketone (MEK) / isopropanol (IPA) / methyl isobutyl ketone (MIBK) / n-butanol (n-BuOH) = 40 /20/30/10 ratio. As a result of measuring the particle diameter in the same manner as in Production Example 9, the number average particle diameter (short axis average particle diameter) was 20 n. # (2) Production of a liquid curable resin composition (composition 6) Except that the fluoropolymer having a hydroxyl group obtained in Production Example 8 was used, Kena A DS (Evo Ato Chemical Co., Ltd., Japan) was used. It is a copolymer of hexafluoropropylene, tetrafluoroethylene, and difluoroethylene. It has no hydroxyl group or polymerizable unsaturated group, and the rest is made of a liquid curable resin composition (composition 1). In the same manner, a liquid curable resin composition (composition 6) was obtained. Example 2, Comparative Example 2 -55- (52) 1338597 [Production of cured film] A cerium oxide particle sol (methyl ethyl ketone cerium oxide sol, MEK-ST manufactured by Nissan Chemical Industries Co., Ltd., number average) Particle diameter 〇.〇22μηι, cerium oxide concentration 30%) 98.6g, 1-hydroxycyclohexyl phenyl ketone 2.1g, IRGACURE 907 (2-methyl-1·[4-(methylthio)phenyl] -2·morpholinylpropan-1-one, manufactured by Chiba Specialty Chemicals Co., Ltd.) 1 · 2 g, dipentaerythritol hexaacrylate (DPHA) 33_2g, cyclohexyl ketone 7g, mixed φ, stirred to obtain two A composition for a hard coating layer of cerium oxide particles. The composition of the hard coating layer containing the cerium oxide particles was applied to a triethylene fluorene cellulose film (manufactured by LOFO, film thickness 8 〇 μιη) using a wire bar coater (#1 2 ), and placed in an oven. Dry at 80 ° C for 1 minute. Next, in a high-pressure mercury lamp, ultraviolet rays were irradiated under a light irradiation condition of J/cm2 to form a hard film layer. The result of measuring the film thickness of the hard coating layer using a stylus type film thickness meter was 5 μηι. The φ compositions 1 to 6 obtained in Example 1 and Comparative Example 1 were applied to the obtained hard coating layer using a wire bar coater (#3), and heated in an oven at 120 ° C for 10 minutes to form. The film thickness is a hardened film layer of 〇·2 μm. Evaluation Example 1 [Evaluation of cured film] The cross-sections of the cured films obtained in Example 2 and Comparative Example 2 were observed under a microscope to evaluate whether or not the layers were separated into two layers. The evaluation criteria are as follows. A typical example in each state is shown in Fig. 11. <Evaluation Criteria> -56- (53) (53) 1338597 Two-layer separation is not separated (partially agglomerated) Uniform structure haze (haze値) (%), and the turbidity in the obtained laminate is measured using a Haze meter. The evaluation was based on the following criteria. 〇: The turbidity is below %%. △: The turbidity is 5% or less. X: The turbidity is 5% or more. The results are shown in Table 1 below.

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成分 組成(質量％) 組成1 (貿施例) 組成2 (實施例) 組成3 (實施例) 組成4 (比較例) 組成5 (實施例) 組成6 (比較例） (A) 含有羥基之含氟 聚合物 製造例8 25.1 46 26 0 26 - 含氟聚合物(無含 羥基） 凱拿ADS - - - - 25.1 (B) 金屬氧化物粒子 氧化鋁、氧化锆 被覆耵〇2粒子分 散液 學 49 49 49 49 - 二氧化矽被覆 Ti02 513 - - - - 51.3 (E) 硬化性化合物 塞伊美爾303 15.1 0 20 26 25 15.1 (F) 熱引發酸產生劑 觸媒4050 8.5 二層分 離 5 層分離 5 層分離 26 均勻的 構造 0 層分離 8.5 並未分離 (部分凝聚) 層分離性 混濁度 〇 〇 〇 〇 〇 〇 表1中之名稱之說明如下： (A)含氟聚合物：於上述製造例1所製造的含氟聚 合物。 凱拿ADS :埃佛•阿托化學·日本（股）製、六氟代 丙烯、四氟代乙烯以及二氟代乙烯之共聚物。不具有羥基 及聚合性不飽和基。 -58- (55) 1338597 (B)金屬氧化物粒子 氧化鋁、氧化鉻被覆Ti02粒子分散液：黛尹卡（股 )製 '全固體成分濃度2 8 %、粒子濃度24 %、數平均粒子 徑 2 〇 n m 二氧化矽被覆Ti02粒子分散液：於製造例2所製造 者。 (E)塞伊美爾303:甲氧化甲基三聚氰胺、三井塞 φ 伊科技（股）製 (F )觸媒4050 ··三井塞伊科技（股）製、芳香族磺 酸化合物 由表1結果可知，即使未經調配（E )硬化性化合物 及（F )熱引發酸產生劑，仍能發生二層分離的情形（組 成2及5 )。 可知’如不存在有（A )含有羥基之含氟聚合物，則 不會發生二層分離的情形（組成4及6 )。 • 實施例3、比較例3 〔液狀硬化性樹脂組成物及硬化膜之製造〕 於實施例1的組成3之固體成分調配比例之液狀硬化 性樹脂組成物中’如表2所示方式改變所用溶劑，以製得 組成7至1 〇之液狀硬化性樹脂組成物。 使用組成3及7至1 〇之液狀硬化性樹脂組成物，按 與實施例2同樣方式，且同樣條件以製作硬化膜。 (A )含有羥基之含氟聚合物之溶解性，係將（a )含 -59- (56) (56)1338597 有羥基之含氟聚合物按能5 0質量％之方式添加於各溶劑中 ，在室溫下攪拌既定時間後，以目視判斷是否均勻的溶液 ，依據下述基準所評價者。其結果如表2所示。 〈評價基準〉 〇··攪拌2小時後爲均勻的溶液。 △:攪拌8小時後爲均勻的溶液。 X :攪拌8小時後仍非均勻溶液。 (B ) Ti〇2粒子之分散安定性’係將玻璃板浸漬於（ B)金屬氧化物粒子分散液中以使（B )金屬氧化物粒子附 著於玻璃壁上，當將附著有（B )金屬氧化物粒子的玻璃 板浸漬於各溶劑中時，以目視判斷（B )金屬氧化物粒子 是否均勻分散於該溶劑中，並依據下述基準所評價者。其 結果如表2所示。 〈評價基準〉 〇：在均勻分散 X :未均勻分散 表2中’溶劑係從左往右按溶劑之相對蒸發速度減少 之順序排列者。 溶劑之縮寫所表示之意義如下。 MEK:甲基乙基酮Composition (% by mass) Composition 1 (Trade Example) Composition 2 (Example) Composition 3 (Example) Composition 4 (Comparative Example) Composition 5 (Example) Composition 6 (Comparative Example) (A) Containing hydroxyl group Fluoropolymer Production Example 8 25.1 46 26 0 26 - Fluoropolymer (without hydroxyl group) Kaina ADS - - - - 25.1 (B) Metal oxide particles Alumina, zirconia coated 耵〇 2 particle dispersion liquid 49 49 49 49 - Ceria coated Ti02 513 - - - - 51.3 (E) Hardening compound Seimer 303 15.1 0 20 26 25 15.1 (F) Thermally initiated acid generator catalyst 4050 8.5 Separation of 5 layers Separation of 5 layers 5 Layer separation 26 Uniform structure 0 Layer separation 8.5 Not separated (partially agglomerated) Layer separation turbidity 说明 The names in Table 1 are as follows: (A) Fluoropolymer: in the above production example 1 The fluoropolymer produced. Kaina ADS: Effort-Atochem Chemical Co., Ltd., a copolymer of hexafluoropropylene, tetrafluoroethylene and difluoroethylene. It does not have a hydroxyl group or a polymerizable unsaturated group. -58- (55) 1338597 (B) Metal oxide particles of alumina and chrome oxide coated TiO 2 particle dispersion: 黛Yinka (stock) made of 'all solids concentration of 28%, particle concentration of 24%, number average particle diameter 2 〇nm cerium oxide coated TiO 2 particle dispersion: The manufacturer of the production example 2 was produced. (E) Seimer 303: methyl methoxide melamine, Mitsui φ yue technology (share) system (F) catalyst 4050 · · Mitsui Sei technology (stock) system, aromatic sulfonic acid compounds from the results of Table 1 Even in the case where the (E) hardening compound and (F) the heat-initiating acid generator are not formulated, the two-layer separation can occur (compositions 2 and 5). It can be seen that if there is no (A) fluoropolymer containing a hydroxyl group, the separation of the two layers does not occur (compositions 4 and 6). Example 3 and Comparative Example 3 [Production of liquid curable resin composition and cured film] The liquid curable resin composition of the solid content ratio of the composition 3 of Example 1 was as shown in Table 2 The solvent used was changed to obtain a liquid curable resin composition having a composition of 7 to 1 Torr. A liquid curable resin composition having a composition of 3 and 7 to 1 Torr was used, and a cured film was produced in the same manner as in Example 2 under the same conditions. (A) Solubility of a fluoropolymer containing a hydroxyl group, wherein (a) a fluorine-containing polymer having -59-(56) (56) 1338597 hydroxyl group is added to each solvent in an amount of 50% by mass After stirring for a predetermined period of time at room temperature, it was visually judged whether or not the solution was uniform, and it was evaluated according to the following criteria. The results are shown in Table 2. <Evaluation Criteria> 〇·· After stirring for 2 hours, it was a homogeneous solution. △: A homogeneous solution after stirring for 8 hours. X: A non-homogeneous solution remained after stirring for 8 hours. (B) Dispersion stability of Ti〇2 particles' is a glass plate immersed in (B) metal oxide particle dispersion so that (B) metal oxide particles adhere to the glass wall, when (B) When the glass plate of the metal oxide particles was immersed in each solvent, it was visually judged whether (B) metal oxide particles were uniformly dispersed in the solvent, and evaluated according to the following criteria. The results are shown in Table 2. <Evaluation criteria> 〇: uniform dispersion X: non-uniform dispersion In Table 2, the solvent is arranged from left to right in the order of decreasing relative evaporation rate of the solvent. The meaning of the abbreviation of solvent is as follows. MEK: methyl ethyl ketone

MeOH :甲醇 IPA :異丙醇 MIBK :甲基異丁基酮 n-BuOH ：正丁醇 -60- (57)1338597 MAK :甲基戊基酮 評價例2 〔硬化膜之評價〕 按與評價〗同樣方式評價實施例3及比較例3所得硬 化膜之層分離性及混濁度。其結果如表示所示。 溶劑之卷 6類及調配比例（質量％) 混濁 度 層分離性 MEK MeOH 1PA MIBK n-BuOH MAK 溶劑之相對蒸發速度 3.8 2.1 1.7 1.6 0.4 0.3 (A)母料樹脂之溶解性 〇 X △ 〇 X 〇 (B)Ti02粒子之分散安定性 X 〇 〇 20 X 〇 X 組成3(實施例） 40 30 10 〇 二層分離 組成7(實施例） 55 45 △ 二層分離 組成8(比較例） - 55 45 - - - X 未分離 (部分凝聚） 組成9(比較例） - - 45 • 55 - X 未分離 (部分凝聚） 組成1〇(比較例） - - 45 - - 55 X 未分離 (部分凝聚）MeOH: methanol IPA: isopropanol MIBK: methyl isobutyl ketone n-BuOH: n-butanol-60- (57) 1338597 MAK: methyl amyl ketone evaluation example 2 [evaluation of hardened film] The layer separation property and turbidity of the cured films obtained in Example 3 and Comparative Example 3 were evaluated in the same manner. The results are shown in the figure. Solvent Volume 6 and blending ratio (% by mass) Turbidity Layer Separation MEK MeOH 1PA MIBK n-BuOH MAK Relative evaporation rate of solvent 3.8 2.1 1.7 1.6 0.4 0.3 (A) Solubility of masterbatch resin 〇X △ 〇X 〇(B)Dispersion stability of TiO 2 particles X 〇〇20 X 〇X Composition 3 (Example) 40 30 10 〇Two-layer separation composition 7 (Example) 55 45 △ Two-layer separation composition 8 (Comparative Example) - 55 45 - - - X Not separated (partially agglomerated) Composition 9 (Comparative Example) - - 45 • 55 - X Not separated (partially agglomerated) Composition 1〇 (Comparative Example) - - 45 - - 55 X Not separated (partial condensation)

由表2結果可知，爲發生二層分離，較佳爲調配2種 以上之溶劑，在選擇時，需要至少1種係（C )對（A )含 -61 - (58) (58)1338597 氟聚合物的溶解性較高，而其他至少1種係（D )對（B ) 金屬氧化物粒子的分散安定性較高者，另外需要，溶劑（ C )之相對蒸發速度較溶劑（D )之相對蒸發速度爲高的事 實。 實施例4、比較例4 〔層合體之製作〕 (1)硬質覆膜層之製作 使用鋼絲桿塗佈機1 2 )將製造例3所調製含有二 氧化矽粒子之硬質覆膜層用組成物（固體成分濃度5 0 % ) 塗工於三乙醯纖維素軟片（LOFO製、膜厚80μπ〇上，並 在烘箱內80 °C下乾燥1分鐘。接著，在空氣中，使用高壓 水銀燈，依0.6 J/cm2之光照射條件下照射紫外線，以形 成硬化膜層。使用觸針式膜厚計測定硬化膜層之膜厚的結 果爲5 μ m。 (2 )中折射率層之製作 使用鋼絲桿塗佈機（#3 )將製造例4所調製含氧化鉻 粒子之組成物（固體成分濃度4% )塗工於（1 )中所製作 的硬質覆膜層上，並在烘箱內80°C下乾燥1分鐘。接著， 在氮氣氣氛中，使用高壓水銀燈，依0,6 J/cm2之光照射 條件下照射紫外線，以形成硬化膜層。使用反射分光計算 出硬化膜層之膜厚的結果，爲65nm。 (3 )高折射率層與低折射率層之製作 使用鋼絲桿塗佈機（#3 )將實施例]及比較例1所得 -62- (59) (59)1338597 組成1至6之液狀硬化性樹脂組成物分別塗工於（2 )中 所製作的中折射率層上，並在烘箱內1 2 0。(：下加熱1 0分鐘 ，以形成膜厚爲〇.2μηι之硬化膜層。 實施例5、比較例5 〔層合體之製作〕 (丨）硬質覆膜層之製作 按與實施例4 ( 1 )同樣方式製作。 (2 )抗靜電層之製作 使用鋼絲桿塗佈機（#3 )將製造例5所調製含有ΙΤΟ 粒子之組成物（固體成分濃度4% )塗工於（1 )中所製作 的硬質覆膜層上，並在烘箱內80 °C下乾燥1分鐘。接著， 在氮氣氣氛中，使用高壓水銀燈，依〇 . 6 J / c m2之光照射 條件照射紫外線，以形成硬化膜層。使用反射分光計算出 硬化膜層之膜厚的結果，爲65 nm。 (3 )中折射率層之製作 按與實施例4 ( 2 )同樣方式製作。 (4 )高折射率層與低折射率層之製作 使用鋼絲桿塗佈機（#3 )將實施例1及比較例1所得 組成1至6之液狀硬化性樹脂組成物分別塗工於（3 )中 所製作的中折射率層上，並在烘箱內120 °C下加熱10分鐘 ，以形成膜厚爲0.2 μΐΏ之硬化膜層。 實施例6、7及比較例6、7 -63- (60) 1338597 〔層合體之製作〕 (1 )抗靜電層之製作 不用製造例5所調製的ITO粒子，而將製造例6或7 所調製的含有ΑΤΟ粒子之組成物（固體成分濃度5% )或 含有Α1摻雜ΖηΟ粒子之組成物（固體成分濃度4% ) ’使 用綱絲桿塗佈機（#3 )塗工於三乙醯纖維素軟片（LOFO 製、膜厚80μηι )上，並在烘箱內80t下乾燥1分鐘。接 φ 著，在氮氣氣氛中，使用高壓水銀燈，依0.6 J/cm2之光 照射條件照射紫外線，以形成硬化膜層。使用反射分光計 算出硬化膜層之膜厚的結果，爲6 5 n m。 (2)硬質覆膜層之製作 使用鋼絲桿塗佈機（# 1 2 )將製造例3所調製有二氧 化矽粒子之硬質覆膜層用組成物（固體成分濃度50% )塗 工後，在烘箱內80t下乾燥1分鐘。接著，在空氣中，使 用高壓水銀燈，依〇·6 J/cm2之光照射條件照射紫外線， # 以形成硬化膜層。 (3 )中折射率層之製作 按與實施例4 ( 2 )同樣方式製作。 (4 )高折射率層與低折射率層之製作 使用鋼絲桿塗佈機（#3 )將實施例1及比較例I所得 組成1至6之液狀硬化性樹脂組成物分別塗工於（3 )中 所製作的中折射率層上’並在烘箱內l2〇°C下加熱10分鐘 ，以形成膜厚爲0.2 μηι之硬化膜層。 -64- (61) 1338597 實施例8、比較例8 〔層合體之製作〕 按與實施例（1 )同樣方式製作。 (2 )高折射率層與低折射率層之製作 使用鋼絲桿塗佈機（#3 )將實施例1及比較例1所得 組成1至6之液狀硬化性樹脂組成物分別塗工於（1 )中 所製作的硬質覆膜層上，並在烘箱內120 °C下乾燥丨〇分鐘 i ’以形成膜厚爲0.2 μΐΏ之硬化膜層。 評價例3 〔層合體之評價〕 使用透射型電子顯微鏡觀察實施例4至8及比較例4 至8中所得層合體斷面的結果’在使用組成1、2、3、5 的層合體上，經確認低折射率層與高折射率層在層分離爲 2層的情形。此時，低折射率層爲實質上不存在有金屬氧 φ 化物粒子的層，而低折射率層爲高密度方式存在有金屬氧 化物粒子的層。在使用組成4的層合體上，係高折射率層 與低折射率層成爲均勻構造而並未層分離。使用組成6的 層合體上’則高折射率層與低折射率層發生部分凝聚而未 層分離。 使用分光反射率測定裝置（組裝有大型試料室積分球 附屬裝置1 50-09090的自動記錄式分光光度計υ-3410、日 立製作所（股）製）測定波長5 5 0 n m下的反射率，以評價 使用組成〗、2、3 ' 5的反射防止用層合體之反射防止性 -65 - (62) 1338597 。具體而言，將鋁的沈積膜的反射率作爲基準（1 〇〇% ) &gt; 測定反射防止用層合體（反射防止膜）之反射率。其結果 ，所有層合體在波長55 Onm下的反射率均在】％以下。 〔產業上之利用可能性〕 使本發明之液狀硬化性樹脂組成物硬化後所得硬化膜 ，由於可從一層塗膜形成具有低折射率層及高折射率層等 φ 連續的多層構造的硬化膜之故可簡化具有多層構造的硬化 膜之製造步驟。亦即，如使用本發明之液狀硬化性樹脂組 成物，則可簡化具有二層以上之多層構造的層合體之製造 步驟。因而，本發明之液狀硬化性樹脂組成物，特別是可 有利使用於反射防止膜 '透鏡、選擇透射膜濾光器等的光 學材料之形成。又，利用所得礙化膜或層合體，能包含氟 含量高的層的特點，很適合用於對需要耐氣候性的塗料、 耐氣候軟片、塗層等。並且，由於該硬化膜或層合體，係 # 對基材的密合性優異，耐擦傷性高，能賦與良好的反射防 止效果之故，作爲反射防止膜極爲有用，如適用於各種顯 示裝置上時，則可提升其視認性。 【圖式簡單說明】 第1A圖：爲說明「從丨層塗膜所形成的2層以上之 層」之用的圖。 第1B圖：爲說明「從】層塗膜所形成的2層以上之 層」之用的圖。 -66- (63) 1338597 第1 C圖：爲說明「從1層塗膜所形成的2層以上之 層」之用的圖。 第1 D圖：爲說明「從1層塗膜所形成的2層以上之 層」之用的圖。 第1E圖：爲說明「從1層塗膜所形成的2層以上之 層」之用的圖。 第2圖：有關本發明的一種實施形態的反射防止膜之 斷面圖。 第3圖：有關本發明的另一種實施形態的反射防止膜 之斷面圖。 第4圖：有關本發明的另一種實施形態的反射防止膜 之斷面圖。 第5圖：有關本發明的另一種實施形態的反射防止膜 之斷面圖。 第6圖：有關本發明的另一種實施形態的反射防止膜 φ 之斷面圖。 第7圖：有關本發明的另一種實施形態的反射防止膜 之斷面圖。 第8圖：有關本發明的另一種實施形態的反射防止膜 之斷面圖。 第9圖：有關本發明的另一種實施形態的反射防止膜 之斷面圖6 第1 〇圖：有關本發明的另一種實施形態的反射防止 膜之斷面圖 -67- (64) (64)1338597 第1 1圖：表示二層分離、未分離（部分凝聚）以及 均勻構造的各狀態之情況的電子顯微鏡。 【主要元件符號說明】 1=高密度方式存在有金屬氧化物粒子的層 1 a :高密度方式存在有金屬氧化物粒子的層 1 b ·‘高密度方式存在有金屬氧化物粒子的層 3:實質上不存在有金屬氧化物粒子的層 1 0 :基材 20 :硬質覆膜層 3 〇 :抗靜電層 4 0 :高折射率層 5 0 :低折射率層 6 0 :中折射率層From the results of Table 2, it is understood that in order to cause the two-layer separation, it is preferred to formulate two or more solvents. When selecting, at least one type of (C) pair (A) is required to contain -61 - (58) (58) 1338597 fluorine. The solubility of the polymer is high, and the dispersion stability of at least one of the other (D) pairs of (B) metal oxide particles is higher, and the relative evaporation rate of the solvent (C) is higher than that of the solvent (D). The fact that the relative evaporation rate is high. Example 4 and Comparative Example 4 [Preparation of a laminate] (1) Preparation of a hard coating layer A steel rod coating machine 1 2) A composition for a hard coating layer containing cerium oxide particles prepared in Production Example 3 (solid content concentration: 50%) The coating was applied to a triacetone cellulose film (LOFO, film thickness 80 μπ〇, and dried in an oven at 80 ° C for 1 minute. Then, in the air, using a high pressure mercury lamp, Ultraviolet rays were irradiated under light irradiation conditions of 0.6 J/cm 2 to form a cured film layer. The film thickness of the cured film layer was measured by a stylus type film thickness meter to be 5 μm. (2) The medium refractive index layer was produced using a steel wire. The bar coater (#3) applied the composition containing the chromium oxide particles prepared in Production Example 4 (solid content concentration: 4%) to the hard film layer prepared in (1), and 80° in an oven. It was dried for 1 minute at C. Then, under a nitrogen atmosphere, a high-pressure mercury lamp was used, and ultraviolet rays were irradiated under light irradiation conditions of 0,6 J/cm 2 to form a cured film layer. The film thickness of the cured film layer was calculated by using reflection spectrometry. As a result, it was 65 nm. (3) Production of high refractive index layer and low refractive index layer The liquid curable resin compositions of Examples - 6 - (59) (59) 1338597 Compositions 1 to 6 obtained in Example 1 and Comparative Example 1 were respectively coated in (2) with a wire bar coater (#3). The prepared medium refractive index layer was placed in an oven at 120 ° C. (: heated for 10 minutes to form a cured film layer having a film thickness of 〇.2 μηι. Example 5, Comparative Example 5 [Production of laminate] (丨) Preparation of a hard coating layer was carried out in the same manner as in Example 4 (1). (2) Preparation of antistatic layer The composition of ruthenium particles prepared in Production Example 5 was prepared using a wire rod coater (#3). The material (solid content concentration: 4%) was applied to the hard coating layer prepared in (1), and dried in an oven at 80 ° C for 1 minute. Then, in a nitrogen atmosphere, a high pressure mercury lamp was used, depending on the enthalpy. The light irradiation condition of 6 J / c m2 was irradiated with ultraviolet rays to form a cured film layer. The film thickness of the cured film layer was calculated by reflection splitting, and it was 65 nm. (3) The medium refractive index layer was produced in the same manner as in Example 4 (2) Manufactured in the same manner. (4) Fabrication of high refractive index layer and low refractive index layer using wire rod coater (#3) The liquid curable resin compositions of the compositions 1 to 6 obtained in Example 1 and Comparative Example 1 were respectively applied onto the medium refractive index layer prepared in (3), and heated in an oven at 120 ° C for 10 minutes to A cured film layer having a film thickness of 0.2 μΐΏ was formed. Examples 6 and 7 and Comparative Example 6, 7-63- (60) 1338597 [Production of Laminate] (1) Preparation of antistatic layer was not prepared by Production Example 5. ITO particles, and the composition containing the ruthenium particles prepared by Production Example 6 or 7 (solid content concentration: 5%) or the composition containing Α1-doped ΖηΟ particles (solid content concentration: 4%) was coated with a wire rod. The machine (#3) was applied to a triacetone cellulose film (LOFO system, film thickness 80 μηι) and dried in an oven at 80 t for 1 minute. After φ, a high-pressure mercury lamp was used in a nitrogen atmosphere, and ultraviolet rays were irradiated under light irradiation conditions of 0.6 J/cm 2 to form a cured film layer. The film thickness of the cured film layer was calculated using a reflection spectrometer, and it was 6 5 n m. (2) Preparation of a hard coating layer After coating a hard coating layer composition (solid content concentration: 50%) prepared with the cerium oxide particles in Production Example 3 using a wire rod coater (#1 2 ), Dry in an oven at 80 t for 1 minute. Next, in a high-pressure mercury lamp, ultraviolet rays were irradiated under light irradiation conditions of 6 J/cm 2 in the air to form a cured film layer. (3) Preparation of medium refractive index layer It was produced in the same manner as in Example 4 (2). (4) Preparation of High Refractive Index Layer and Low Refractive Index Layer The liquid curable resin compositions of Compositions 1 to 6 obtained in Example 1 and Comparative Example I were respectively coated on a steel bar coater (#3). 3) The medium refractive index layer produced in ') was heated in an oven at 10 ° C for 10 minutes to form a cured film layer having a film thickness of 0.2 μm. -64- (61) 1338597 Example 8 and Comparative Example 8 [Production of laminate] It was produced in the same manner as in Example (1). (2) Preparation of High Refractive Index Layer and Low Refractive Index Layer The liquid curable resin compositions of Compositions 1 to 6 obtained in Example 1 and Comparative Example 1 were respectively coated with a steel bar coater (#3). 1) The hard coating layer prepared in the film was dried in an oven at 120 ° C for a minute to form a cured film layer having a film thickness of 0.2 μΐΏ. Evaluation Example 3 [Evaluation of Laminates] The results of observing the cross-sections of the laminates obtained in Examples 4 to 8 and Comparative Examples 4 to 8 using a transmission electron microscope were carried out on the laminates using Compositions 1, 2, 3, and 5. It was confirmed that the low refractive index layer and the high refractive index layer were separated into two layers. In this case, the low refractive index layer is a layer in which metal oxide particles are not substantially present, and the low refractive index layer is a layer in which metal oxide particles are present in a high density manner. In the laminate using the composition 4, the high refractive index layer and the low refractive index layer have a uniform structure without layer separation. When the laminate of composition 6 is used, the high refractive index layer and the low refractive index layer are partially agglomerated without being separated. The reflectance at a wavelength of 550 nm was measured using a spectroscopic reflectance measuring device (automatic recording spectrophotometer υ-3410 equipped with a large-scale sample integrating sphere attachment device 50-09090, manufactured by Hitachi, Ltd.) to The reflection preventing property of the reflection preventing laminate using the composition, 2, and 3 '5 was evaluated - 65 - (62) 1338597 . Specifically, the reflectance of the deposited film of aluminum was used as a reference (1 〇〇%) &gt; The reflectance of the antireflection laminate (antireflection film) was measured. As a result, the reflectance of all the laminates at a wavelength of 55 Onm was below 5%. [Industrial Applicability] The cured film obtained by curing the liquid curable resin composition of the present invention can form a cured layer having a φ continuous multilayer structure such as a low refractive index layer and a high refractive index layer from a single coating film. The film can simplify the manufacturing steps of the cured film having a multilayer structure. In other words, when the liquid curable resin composition of the present invention is used, the production steps of the laminate having a multilayer structure of two or more layers can be simplified. Therefore, the liquid curable resin composition of the present invention can be advantageously used for the formation of an optical material such as an antireflection film 'lens, a selective transmission film filter, or the like. Further, the obtained barrier film or laminate can be characterized by containing a layer having a high fluorine content, and is suitably used for a paint, weather resistant film, coating or the like which requires weather resistance. In addition, the cured film or the laminate has excellent adhesion to the substrate, high scratch resistance, and good antireflection effect, and is extremely useful as an antireflection film, and is suitable for various display devices. When it is above, it can enhance its visibility. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1A is a view for explaining "a layer of two or more layers formed from a ruthenium coating film". Fig. 1B is a view for explaining the "two or more layers formed by the "coating layer" coating film". -66- (63) 1338597 Fig. 1C is a view for explaining "a layer of two or more layers formed by coating a single layer". Fig. 1D is a view for explaining "a layer of two or more layers formed by coating a single layer". Fig. 1E is a view for explaining "a layer of two or more layers formed from a single layer of a coating film". Fig. 2 is a cross-sectional view showing an antireflection film according to an embodiment of the present invention. Fig. 3 is a cross-sectional view showing an antireflection film according to another embodiment of the present invention. Fig. 4 is a cross-sectional view showing an antireflection film according to another embodiment of the present invention. Fig. 5 is a cross-sectional view showing an antireflection film according to another embodiment of the present invention. Fig. 6 is a cross-sectional view showing an antireflection film φ according to another embodiment of the present invention. Figure 7 is a cross-sectional view showing an antireflection film according to another embodiment of the present invention. Fig. 8 is a cross-sectional view showing an antireflection film according to another embodiment of the present invention. Fig. 9 is a cross-sectional view showing an antireflection film according to another embodiment of the present invention. Fig. 6 is a cross-sectional view showing an antireflection film according to another embodiment of the present invention. -67- (64) (64 1338597 Fig. 1 1 : An electron microscope showing the state of separation of two layers, unseparated (partial agglomeration), and uniform state. [Description of main component symbols] 1 = Layer 1 in which metal oxide particles are present in a high-density manner: Layer 1 in which a metal oxide particle exists in a high-density manner. Layer b in which a metal oxide particle exists in a high-density manner: Layer 10 in which metal oxide particles are substantially absent: Substrate 20: Hard film layer 3 〇: Antistatic layer 40: High refractive index layer 50: Low refractive index layer 6 0: Medium refractive index layer

-68--68-

Claims (1)

(1) 1338597 十、申請專利範圍 1. 一種液狀硬化性樹脂組成物，其特徵爲：含有下 述成分（A )至（F )； (A)分子內具有羥基的含氟聚合物 (B )數平均粒子徑爲l〇〇nm以下，且折射率爲1 .50 以上之1種或2種以上之金屬氧化物粒子（以下，簡稱「 (B)金屬氧化物粒子」） p (C)對（A)分子內具有羥基的含氟聚合物的溶解性 高的丨種或2種以上之溶劑（以下，簡稱「（ C )速揮發 溶劑j ) (D )對（B )金屬氧化物粒子的分散安定性高，且與 (C )速揮發溶劑相溶性的1種或2種以上之溶劑（以下 ，簡稱「（ D )遲揮發溶劑」） (E )硬化性化合物 (F )熱引發酸產生劑 •，且（C )速揮發溶劑之相對蒸發速度，係較（D )遲揮發 劑之相對蒸發速度爲大。 2. 如申請專利範圍第1項之液狀硬化性樹脂組成物 ，其中（C )速揮發溶劑，係對（B )金屬氧化物粒子的分 散安定性低的1種或2種以上之溶劑，而（D )遲揮發溶 劑，係對（A )分子內具有羥基的含氟聚合物的溶解性低 的1種或2種以上之溶劑。 3-如申請專利範圍第1項之液狀硬化性樹脂組成物 ，其中（B )金屬氧化物粒子’係以選自氧化鈦、氧化鍩 -69- (2) 1338597 、含有銻之氧化錫、含有錫之氧化銦、氧化鋁、氧化铈、 氧化鋅、含有鋁之氧化鋅、氧化錫、含有銻之氧化鋅以及 含有銦之氧化鋅、含有磷之氧化錫的I種或2種以上之金 屬氧化物作爲主成分的粒子。 4.如申請專利範圍第3項之液狀硬化性樹脂組成物 ，其中（B )金屬氧化物粒子，係以氧化鈦作爲主成分的 粒子。 p 5.如申請專利範圍第1項之液狀硬化性樹脂組成物 ，其中（B)金屬氧化物粒子，係具有多層構造的金屬氧 化物粒子。 6. 一種硬化膜，其特徵爲使申請專利範圍第1項之 液狀硬化性樹脂組成物硬化所製得，具有2層以上之多層 構造。 7. 如申請專利範圍第6項之硬化膜，其中構成該多 層構造的各層，係高密度方式存在有（B )金屬氧化物粒 φ 子的層或實質上不存在有（B)金屬氧化物粒子的層，而 至少一層，係高密度方式存在有（B)金屬氧化物粒子的 層。 8. —種硬化膜之製造方法，其特徵爲：具有藉由申 請專利範圍第1項之液狀硬化性樹脂組成物之加熱、或藉 由放射線之照射而使其硬化的步驟。 9. 一種層合體之製造方法，係基材，與在其上具有 多層構造的層合體之製造方法，其特徵爲：於前述基材上 或基材上所形成的層之上，塗佈申請專利範圍第1項之液 -70- (3) 1338597 狀硬化性樹脂組成物以形成塗膜，並 從此1層塗膜蒸發溶劑，以形成2層以上之層。 10. 如申請專利範圍第9項之層合體之製造方法，# 中該2層以上之層之各層，係高密度方式存在有金屬氧化 物粒子的層或實質上不存在有金屬氧化物粒子的層，而g 少1層係高密度方式存在有金屬氧化物粒子的層。 11. 如申請專利範圍第1 0項之層合體之製造方法， φ 其中該2層以上之層，係2層者。 12. 如申請專利範圍第9項之層合體之製造方法，其 中再藉由加熱而使該2層以上之層硬化。 1 3 ·如申請專利範圍第9項之層合體之製造方法 &gt; 其 中層合體係光學用零件。 14.如申請專利範圍第9項之層合體之製造方法，其 中層合體係反射防止膜。 1 5 .如申請專利範圍第1 1項之層合體之製造方法， φ 其中該層合體，係至少高折射率層及低折射率層經從靠近 基材側按此順序層合於基材上的反射防止膜，而申請專利 範圍第Π項所記載之2層，係由 闻折射率層及 低折射率層所成。 1 6 ·如申請專利範圍第1 5項之層合體之製造方法， 其中低折射率層在5 89nm的折射率爲1 .20至1 .55，而 高折射率層在589nm的折射率爲1.50至2.20，且比 低折射率層之折射率爲高。 -71 - (4) 1338597 1 7 .如申請專利範圍第1 1項之層合體 其中該層合體，係至少中折射率層、高折射 射率層經從靠近基材側按此順序層合於基材 膜’而申請專利範圍第1 1項所記載之2層， 高折射率層及 低折射率層所成。 1 8 ·如申請專利範圍第】7項之層合體 其中低折射率層在589nm的折射率爲1.2〇至 中折射率層在5 89nm的折射率爲i 5〇 低折射率層之折射率爲高， 高折射率層在589nm的折射率爲151 中折射率層之折射率爲高。 1 9 ·如申請專利範圍第1 5項或第1 7項 造方法’其中再於基板上形成硬質覆膜層万 〇 % 20· 一種層合體’係依申請專利範圔第 之製造方法所製造者。 之製造方法， 率層以及低折 上的反射防止 係由 之製造方法， 1.55' 至1.90 ，而比 至2.2 0，而比 之層合體之製 :/或抗靜電層 9項之層合體 -72-(1) 1338597 X. Patent Application No. 1. A liquid curable resin composition characterized by containing the following components (A) to (F); (A) a fluorine-containing polymer having a hydroxyl group in the molecule (B) One or two or more kinds of metal oxide particles having a number average particle diameter of 1 〇〇 nm or less and a refractive index of 1.5 or more (hereinafter referred to as "(B) metal oxide particles") p (C) (A) a solvent having a high solubility in a fluorine-containing polymer having a hydroxyl group in the molecule or a solvent of two or more kinds (hereinafter, simply referred to as "(C)-speed volatile solvent j) (D) to (B) metal oxide particles One or two or more solvents which are compatible with the (C)-speed volatile solvent (hereinafter referred to as "(D) late-volatile solvent") (E) The hardening compound (F) is thermally initiated The relative evaporation rate of the generating agent and (C) volatile solvent is greater than the relative evaporation rate of the (D) delayed volatile agent. 2. The liquid curable resin composition of the first aspect of the invention, wherein the (C) volatile solvent is one or two or more solvents having low dispersion stability to the (B) metal oxide particles. Further, the (D) late-volatile solvent is one or two or more solvents having low solubility in the fluoropolymer having a hydroxyl group in the molecule (A). The liquid curable resin composition according to claim 1, wherein the (B) metal oxide particles are selected from the group consisting of titanium oxide, cerium oxide-69-(2) 1338597, tin oxide containing cerium, Indium oxide, aluminum oxide, antimony oxide, zinc oxide, aluminum-containing zinc oxide, tin oxide, antimony-containing zinc oxide, indium-containing zinc oxide, phosphorus-containing tin oxide, or two or more metals A particle having an oxide as a main component. 4. The liquid curable resin composition according to claim 3, wherein the (B) metal oxide particles are particles containing titanium oxide as a main component. The liquid curable resin composition of the first aspect of the invention, wherein the (B) metal oxide particles are metal oxide particles having a multilayer structure. A cured film obtained by curing a liquid curable resin composition according to the first aspect of the invention, and having a multilayer structure of two or more layers. 7. The cured film of claim 6, wherein each of the layers constituting the multilayer structure is a layer of (B) metal oxide particles φ or a substantially absent (B) metal oxide in a high-density manner. The layer of particles, and at least one layer, is a layer of (B) metal oxide particles in a high density manner. A method for producing a cured film, which comprises the step of heating a liquid curable resin composition according to claim 1 of the patent application or curing it by irradiation with radiation. A method for producing a laminate, which is a substrate, and a method for producing a laminate having a multilayer structure thereon, characterized in that a coating application is applied to the substrate or the layer formed on the substrate The liquid-70-(3) 1338597-shaped curable resin composition of the first aspect of the patent is formed into a coating film, and the solvent is evaporated from the one-layer coating film to form two or more layers. 10. The method for producing a laminate according to claim 9 of the invention, wherein each of the two or more layers is a layer in which metal oxide particles are present in a high-density manner or substantially no metal oxide particles are present. One layer, and one less layer of g is a layer in which metal oxide particles are present in a high density manner. 11. The method for producing a laminate according to claim 10, wherein φ of the two or more layers is two layers. 12. The method for producing a laminate according to claim 9, wherein the two or more layers are hardened by heating. 1 3 · A method of manufacturing a laminate according to claim 9 of the patent application &gt; A component for optical components of a laminate system. 14. The method for producing a laminate according to claim 9, wherein the laminate system is an antireflection film. The manufacturing method of the laminate according to the first aspect of the patent application, wherein the laminate is at least a high refractive index layer and a low refractive index layer laminated on the substrate in this order from the side close to the substrate. The anti-reflection film is formed by the smear-refractive-index layer and the low-refractive-index layer in the two layers described in the scope of the patent application. The manufacturing method of the laminate according to the fifteenth aspect of the patent application, wherein the low refractive index layer has a refractive index of 1.20 to 1.55 at 589 nm, and the high refractive index layer has a refractive index of 1.50 at 589 nm. It is up to 2.20 and has a higher refractive index than the low refractive index layer. -71 - (4) 1338597 1 7 . The laminate of claim 1 wherein the laminate has at least a medium refractive index layer and a high refractive index layer laminated in this order from the side closer to the substrate The base film ′ is formed of two layers, a high refractive index layer and a low refractive index layer described in the first aspect of the patent application. 1 8 · The laminate of claim 7 wherein the low refractive index layer has a refractive index of 1.2 〇 at 589 nm to the medium refractive index layer has a refractive index of 5 5 nm and the refractive index of the low refractive index layer is The high, high refractive index layer has a refractive index of 151 at 589 nm and the refractive index of the refractive index layer is high. 1 9 · If the application of the patent scope of the 15th or 17th manufacturing method 'where the hard coating layer is formed on the substrate, 20%%. A laminate' is manufactured according to the manufacturing method of the patent application No. By. The manufacturing method, the rate layer and the reflection prevention on the low fold are manufactured by the method, 1.55' to 1.90, and compared to 2.20, and compared with the laminate: / or the antistatic layer 9 layer of the laminate - 72 -
TW094108478A 2004-03-18 2005-03-18 Curable liquid resin composition and method for producing multilayer body using same TW200536620A (en)

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