TW201807085A - Surface-treated metal oxide sol - Google Patents

Surface-treated metal oxide sol Download PDF

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TW201807085A
TW201807085A TW106105884A TW106105884A TW201807085A TW 201807085 A TW201807085 A TW 201807085A TW 106105884 A TW106105884 A TW 106105884A TW 106105884 A TW106105884 A TW 106105884A TW 201807085 A TW201807085 A TW 201807085A
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metal oxide
mass
treated metal
oxide sol
same manner
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TW106105884A
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TWI720136B (en
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二神涉
村口良
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日揮觸媒化成股份有限公司
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    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
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    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/36—Compounds of titanium
    • C09C1/3607—Titanium dioxide
    • C09C1/3653—Treatment with inorganic compounds
    • C09C1/3661—Coating
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    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/36—Compounds of titanium
    • C09C1/3607—Titanium dioxide
    • C09C1/3684—Treatment with organo-silicon compounds
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    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/12—Treatment with organosilicon compounds
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    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/66—Additives characterised by particle size
    • C09D7/67—Particle size smaller than 100 nm
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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    • C09D7/66—Additives characterised by particle size
    • C09D7/68—Particle size between 100-1000 nm
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    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
    • C01P2004/84—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases one phase coated with the other
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    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
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    • C08K3/20—Oxides; Hydroxides
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    • C08K2003/2241—Titanium dioxide
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    • 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
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Abstract

The invention provides a surface-treated metal oxide sol and a manufacture method thereof. The surface-treated metal oxide sol can be used for making a slushing compound film having high index of refraction and high light transmittance, low haze, small shot size, high sensibility, high film residue rate, high resolution, high marresistance and high weather fastness. The surface-treated metal oxide sol contains metal oxide particles subjected to surface treatment and a dispersion medium. The metallic oxide particles subjected to surface treatment are obtained through arranging a speficied amount of organosilicon compound containing (methyl) acrylic acid series perssads on the surface of the metal oxide particles. The metal oxide particles contain over 50% titanium dioxide in mass by TiO2. 0.1 to 60% in mass by Rn-SiO(4-n)/2 organosilicon compound containing (methyl) acrylic acid series perssads is arranged on the metal oxide particles subjected to surface treatment relative to 100 parts of metal oxide particles by mass.

Description

表面處理金屬氧化物溶膠Surface treatment metal oxide sol

本發明係關於一種表面處理金屬氧化物溶膠。詳細而言，本發明係關於一種用於形成高折射率且高硬度之覆膜之包含表面處理金屬氧化物與分散介質之表面處理金屬氧化物溶膠，該表面處理金屬氧化物係於金屬氧化物粒子之表面設有包含(甲基)丙烯醯基之有機矽化合物者。The present invention relates to a surface-treated metal oxide sol. In detail, the present invention relates to a surface-treated metal oxide sol including a surface-treated metal oxide and a dispersion medium for forming a high-refractive-index and high-hardness coating film. The surface-treated metal oxide is based on the metal oxide. The surface of the particle is provided with an organosilicon compound containing a (meth) acrylfluorenyl group.

近年來，於用於製造半導體元件、印刷基板、印刷版、液晶顯示面板、電漿顯示面板等之光微影法中，藉由將感光性物質塗佈於基板上使其於圖案上曝光及顯影而進行加工之技術逐漸普及。用於該光微影法之感光性材料(抗蝕劑材料)係使例如高折射率膜等功能膜以圖案狀形成於基板表面之材料。因此，要求高感度、高殘膜率、高解像度、較高之透明性及較高之膜硬度。該感光性材料(抗蝕劑材料)包含樹脂黏合劑成分與所謂酸產生劑、交聯劑、溶劑之成分。 至今，作為提高覆膜之折射率或硬度之方法，已知塗佈液使用所謂二氧化鈦粒子之高折射率之粒子成分之方法。例如，於日本專利特開平5-173319號公報(專利文獻1)中，為了提高耐蝕刻性用作抗蝕劑材料，揭示有於酚醛樹脂等感光性樹脂中含有0.05～20重量%之平均粒徑為0.002～0.2 μm之金屬氧化物或羥基金屬氧化物之微粉末之光阻劑用組合物。又，於日本專利特開2009-020520號公報(專利文獻2)中，記載有低介電性、接著力、耐熱性等優異之感光性樹脂組合物，揭示有藉由有機矽烷進行表面處理之膠體狀奈米粒子無機物之使用。進而，於日本專利特開2014-152226號公報(專利文獻3)中，揭示有藉由有機矽化合物或其部分水解物對無機複合氧化物粒子進行表面處理而成之無機複合氧化物粒子，該無機複合氧化物粒子用於形成易分散於樹脂或有機溶劑等疏水性介質、透明性或硬度較高、耐擦傷性、與基材之密接性、耐候性優異之塗膜。 [先前技術文獻] [專利文獻] [專利文獻1]日本專利特開平5-173319號公報 [專利文獻2]日本專利特開2009-020520號公報 [專利文獻3]日本專利特開2014-152226號公報In recent years, in a photolithography method for manufacturing a semiconductor element, a printed substrate, a printing plate, a liquid crystal display panel, a plasma display panel, and the like, a photosensitive substance is coated on a substrate to expose it on a pattern and The technology of development and processing is gradually spreading. The photosensitive material (resist material) used in this photolithography method is a material in which a functional film such as a high refractive index film is formed in a pattern on the surface of a substrate. Therefore, high sensitivity, high residual film rate, high resolution, higher transparency, and higher film hardness are required. This photosensitive material (resist material) contains components of a resin adhesive component and a so-called acid generator, a crosslinking agent, and a solvent. Heretofore, as a method for increasing the refractive index or hardness of a coating, a method of using a so-called titanium dioxide particle with a high refractive index particle component as a coating liquid is known. For example, in Japanese Patent Application Laid-Open No. 5-173319 (Patent Document 1), in order to improve the etching resistance and use as a resist material, it is disclosed that an average particle content of 0.05 to 20% by weight is contained in a photosensitive resin such as a phenol resin. A composition for a photoresist of fine powder of a metal oxide or a hydroxy metal oxide having a diameter of 0.002 to 0.2 μm. In addition, Japanese Patent Laid-Open No. 2009-020520 (Patent Document 2) describes a photosensitive resin composition having low dielectric properties, excellent adhesion, heat resistance, and the like, and has disclosed a surface treatment with an organic silane. Use of colloidal nanoparticle inorganics. Furthermore, Japanese Patent Laid-Open No. 2014-152226 (Patent Document 3) discloses an inorganic composite oxide particle obtained by surface-treating an inorganic composite oxide particle with an organic silicon compound or a partial hydrolysate thereof. The inorganic composite oxide particles are used to form a coating film that is easily dispersed in a hydrophobic medium such as a resin or an organic solvent, has high transparency or hardness, abrasion resistance, excellent adhesion to a substrate, and weather resistance. [Prior Art Literature] [Patent Literature] [Patent Literature 1] Japanese Patent Laid-Open No. 5-173319 [Patent Literature 2] Japanese Patent Laid-Open No. 2009-020520 [Patent Literature 3] Japanese Patent Laid-Open No. 2014-152226 Bulletin

[發明所欲解決之問題] 於專利文獻1中所記載之抗蝕劑材料使用二氧化鈦粒子之情形時，雖可期待較高之折射率與較高之膜硬度，但與抗蝕劑材料樹脂之分散性不充分。因此，形成抗蝕劑膜之時，存在粒子凝集且透明性降低、耐擦傷性降低之問題。又，專利文獻2及3中雖藉由對粒子進行表面處理，抗蝕劑膜中之分散性較專利文獻1有所提高，但存在與抗蝕劑材料樹脂之結合不充分、形成抗蝕劑膜時之感度或殘膜率變得不良、膜之解像度亦變得不良之問題。 [解決問題之技術手段] 為了解決該等問題並實現上述對抗蝕劑材料之要求，本發明提供一種可作為抗蝕劑材料之成分使用之表面處理金屬氧化物粒子。具體而言，本發明提供一種包含表面處理金屬氧化物與分散介質之表面處理金屬氧化物溶膠，該表面處理金屬氧化物係於包含以TiO2 計為50質量%以上之二氧化鈦之金屬氧化物粒子之表面，包含(甲基)丙烯醯基之有機矽化合物以R1 n -SiO(4-n)/2 (其中，R1 係選自甲基丙烯醯基及丙烯醯基中之至少一者，相互可相同，亦可不同。n係1～3之整數)計，設有0.1～60質量份者。 [發明之效果] 本發明之表面處理金屬氧化物溶膠於將其用於抗蝕劑材料之情形時，可實現兼具較高之折射率與透光性、較低之霧度及隆起、高感度、高殘膜率、高解像度、較高之耐擦傷性及較高之耐候性之抗蝕劑膜。[Problems to be Solved by the Invention] In the case where titanium dioxide particles are used as the resist material described in Patent Document 1, although higher refractive index and higher film hardness can be expected, it is similar to that of the resist material resin. Insufficient dispersion. Therefore, when the resist film is formed, there are problems in that particles are aggregated, transparency is reduced, and scratch resistance is reduced. In addition, in Patent Documents 2 and 3, the surface of the particles is treated to improve the dispersibility in the resist film compared to Patent Document 1. However, there is insufficient bonding with the resin of the resist material to form a resist. The problem is that the sensitivity or the residual film rate at the time of the film becomes poor, and the resolution of the film also becomes poor. [Technical means to solve the problem] In order to solve these problems and realize the above-mentioned requirements for the resist material, the present invention provides a surface-treated metal oxide particle that can be used as a component of the resist material. Specifically, the present invention provides a surface-treated metal oxide sol including a surface-treated metal oxide and a dispersion medium. The surface-treated metal oxide is a metal oxide particle containing 50% by mass or more of titanium dioxide as TiO 2 . On the surface, the organosilicon compound containing a (meth) acrylfluorenyl group is R 1 n -SiO (4-n) / 2 (wherein R 1 is at least one selected from methacrylfluorenyl and acrylfluorenyl) , May be the same as or different from each other. N is an integer of 1 to 3), and 0.1 to 60 parts by mass are provided. [Effect of the Invention] When the surface-treated metal oxide sol of the present invention is used in a resist material, it can achieve both a high refractive index and light transmittance, a low haze and a bulge, and a high Resist film with sensitivity, high residual film rate, high resolution, higher scratch resistance and higher weather resistance.

本發明之表面處理金屬氧化物溶膠包含於金屬氧化物粒子之表面設有包含(甲基)丙烯醯基之有機矽化合物之表面處理金屬氧化物粒子與分散介質。該金屬氧化物粒子係包含以TiO2 計為50質量%以上之二氧化鈦之粒子。表面處理金屬氧化物粒子相對於該金屬氧化物粒子100質量份，其式(1)所表示之上述有機矽化合物以R1 n -SiO(4-n)/2 (其中，R1 係選自甲基丙烯醯基及丙烯醯基中之至少一者，相互可相同，亦可不同。n係1～3之整數)計，設有0.1～60質量份， R1 n -SiX1 (4-n) (1) (其中，R1 係選自甲基丙烯醯基及丙烯醯基中之至少一者，相互可相同，亦可不同。n係1～3之整數。X1 係烷氧基)。 就此種構成之表面處理金屬氧化物溶膠，以下詳細對其加以說明。 [金屬氧化物粒子] 為了使表面處理金屬氧化物粒子之折射率較高，較佳為以金屬氧化物粒子本身之折射率為2.0以上之方式，包含以TiO2 計為50質量%以上之二氧化鈦。具體而言，較佳為二氧化鈦或包含鈦與其他金屬之複合氧化物。該等可單獨使用，亦可混合使用。作為金屬，例示有矽、錫、鐵、鈰。該等之金屬種類可為1種，亦可為複數種。 然而，已知二氧化鈦由於一般具有光觸媒功能，故具有光活性，可分解膜中共存之有機物等。因此，若光活性過強，則膜之耐候性降低。因此，較佳為使用二氧化鈦與折射率較低之二氧化矽或氧化錫之複合氧化物調整光活性。具體而言，例示有較佳之二氧化鈦二氧化矽(TiO2 /SiO2 )、二氧化鈦二氧化矽氧化錫(TiO2 /SiO2 /SnO2 )之複合氧化物粒子。作為二氧化鈦之形態，金紅石型、銳鈦礦型均可，該等之混合物亦可。特別是作為抗蝕劑材料，為了使折射率大於1.6，較佳為複合氧化物粒子中之二氧化鈦以TiO2 計含有50質量%以上。 於TiO2 /SiO2 之情形時，較佳為含有TiO2 75質量%以上，含有SiO2 25質量%以下。此處，TiO2 /SiO2 之比率若小於75/25，則折射率有可能變低。更佳為TiO2 為80～90質量%，SiO2 為10～20質量%。 於TiO2 /SiO2 /SnO2 之情形時，較佳為TiO2 為50～95質量%，SiO2 為3～25質量%，SnO2 為2～47質量%。此處，若TiO2 /(SiO2 ＋SnO2 )之比率小於50/50，則折射率有可能變低。相反，若TiO2 /(SiO2 ＋SnO2 )之比率大於95/5，則存在與二氧化鈦單獨之粒子之差異難以表示、結果光活性、耐候性成為問題之情況。更佳為TiO2 為70～90質量%，SiO2 為10～20質量%，SnO2 為2～30質量%，TiO2 /(SiO2 ＋SnO2 )更佳為70/30～90/10。 又，為了調整抗蝕劑材料之光活性，亦可於所謂TiO2 /SiO2 、TiO2 /SiO2 /SnO2 之複合氧化物粒子中添加鐵或二氧化鈰等第三成分。 鐵或二氧化鈰摻雜處理於光活性抑制之方面而言較佳。較佳為摻雜量相對於對象之粒子100質量份，作為Fe2 O3 或CeO2 ，未達10質量份。若鐵或二氧化鈰之摻雜量作為Fe2 O3 或CeO2 為10質量份以上，則存在塗膜外觀著色之情況。摻雜量更佳為未達5質量份，進而較佳為未達3質量份。 [表面處理金屬氧化物粒子] ＜包含(甲基)丙烯醯基之有機矽化合物之層＞ 表面處理金屬氧化物粒子係於金屬氧化物粒子之表面被覆有式(1)所表示之有機矽化合物作為表面處理劑者， R1 n -SiX1 (4-n) (1) (其中，R1 係選自甲基丙烯醯基及丙烯醯基中之至少一者，相互可相同，亦可不同。n係1～3之整數。X1 係烷氧基)。 該包含(甲基)丙烯醯基之有機矽化合物相對於金屬氧化物粒子100質量份，以R1 n -SiO(4-n)/2 (其中，R1 係選自甲基丙烯醯基及丙烯醯基中之至少一種，相互可相同，亦可不同。n係1～3之整數)計，設有0.1～60質量份。藉由於金屬氧化物粒子表面設置包含(甲基)丙烯醯基之有機矽化合物，表面處理金屬氧化物粒子與抗蝕劑材料中之樹脂之分散性或結合性提高。此處，若有機矽化合物之量少於0.1質量份，則存在與樹脂之相溶性不足、粒子之凝集發生、霧度上升、總透光率降低之情況。又，存在曝光、顯影時之感度、殘膜率不足之情況。相反，粒子之表面積上較難被覆多於60質量份。有機矽化合物之量較佳為1～50質量份，更佳為3～30質量份。 該有機矽化合物可於溶膠中作為未進行表面處理之未反應物游離存在。其量相對於金屬氧化物粒子100質量份，以R1 n -SiO(4-n)/2 (其中，R1 係選自甲基丙烯醯基及丙烯醯基中之至少一者，相互可相同，亦可不同。n係1～3之整數)計，為99.9質量份以下。游離之有機矽化合物為0質量份之時，表面處理金屬氧化物溶膠中之有機矽化合物僅為設於金屬氧化物表面之有機矽化合物。又，即便存在多於99.9質量份，亦無法期待分散性之提高，膜之折射率亦降低。即，表面處理金屬氧化物溶膠中之包含(甲基)丙烯醯基之有機矽化合物之量若累加設於金屬氧化物粒子之表面者與除此之外游離存在於溶膠中者，則較佳為相對於金屬氧化物粒子100質量份，以R1 n -SiO(4-n)/2 (其中，R1 係選自甲基丙烯醯基及丙烯醯基中之至少一者，相互可相同，亦可不同。n係1～3之整數)計，設有0.1～100質量份。此處，若有機矽化合物之量少於0.1質量份，則無法獲得表面處理之效果。相反，若多於100質量份，則存在膜之折射率降低之情況。有機矽化合物之量更佳為1～70質量份，進而較佳為5～40質量份。 作為有機矽化合物，若為式(1)所表示之包含(甲基)丙烯醯基之有機矽化合物式，則並未特別指定，其中可列舉：3-甲基丙烯醯氧基丙基二甲氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基三乙氧基矽烷、3-丙烯醯氧基丙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基二乙甲基矽烷、3-丙烯醯氧基丙基三乙氧基矽烷等。其中特佳為3-甲基丙烯醯氧基丙基三甲氧基矽烷。 該等有機矽化合物可於單體之狀態下使用，亦可為選自該等有機矽化合物中之1種聚合物或複數種聚合物、或該等之混合物。 於表面處理金屬氧化物粒子上，可於金屬氧化物粒子與該粒子表面之包含(甲基)丙烯醯基之有機矽化合物之間進而設置選自二氧化矽氧化鋯、二氧化矽氧化鋁、二氧化矽二氧化鈦、二氧化矽氧化錫中之二氧化矽複合氧化物之層，與二氧化矽單獨之層中之至少一者。 藉由設置該等層，較金屬氧化物粒子之表面僅被覆有包含(甲基)丙烯醯基之有機矽化合物之表面處理金屬氧化物粒子，折射率、感度、解像度、光活性之調整變得容易。 ＜二氧化矽複合氧化物層＞ 此處，二氧化矽複合氧化物之層以SiO2 /MOX (其中，MOX 係選自ZrO2 、Al2 O3 、TiO2 、SnO2 中之任一種)之莫耳比計，較佳為33.3/66.7～99.5/0.5。藉由設置該層，主要可調整金屬氧化物粒子之光活性及折射率。此處，若SiO2 /MOX 莫耳比小於33.3/66.7，則存在難以獲得均一之被覆層、金屬氧化物粒子凝集之情況。相反，若大於99.5/0.5，則由於難以與二氧化矽層區別，故無需與二氧化矽層區別設置。莫耳比更佳為50.0/50.0～95.2/4.8，進而較佳為50.0/50.0～76.9/23.1。 又，二氧化矽複合氧化物之量相對於金屬氧化物粒子100質量份，以(SiO2 ＋MOX )計為1～180質量份。若二氧化矽複合氧化物之量少於1質量份，則存在耐候性不充分之情況。相反，若多於180質量份，則存在無法獲得所需之折射率之情況。量較佳為2～30質量份，更佳為3～10質量份。 ＜二氧化矽層＞ 二氧化矽層之二氧化矽之量相對於金屬氧化物粒子100質量份，以SiO2 計為0.1～100質量份。藉由設置二氧化矽層，主要可實現金屬氧化物粒子之光活性調整與粒子之分散性提高。此處，若二氧化矽之量少於0.1質量份，則存在利用光活性調整之耐候性不充分、其後之包含(甲基)丙烯醯基之有機矽化合物難以被覆於金屬氧化物之情況。相反，若多於100質量份，則存在無法獲得所需之折射率之情況。較佳之量為0.5～30質量份，更佳為1～10質量份。 該二氧化矽單獨之層可藉由水玻璃等矽酸鹼鹽水溶液或矽酸液等無機矽化合物設置，亦可藉由正矽酸乙酯(TEOS)或正矽酸甲酯(TMOS)等有機矽化合物設置。 於表面處理金屬氧化物粒子上，該等金屬氧化物粒子與該粒子表面之包含(甲基)丙烯醯基之有機矽化合物之間之層進而較佳為自靠近金屬氧化物粒子之側依次設為二氧化矽複合氧化物之層、繼而設為二氧化矽單獨之層、其最表面設為包含(甲基)丙烯醯基之有機矽化合物之層。其係由於依次組合3層，折射率、感度、解像度及光活性可階段性地調整，特別是第2層二氧化矽層之表面OH基生成，從而於此處賦予(甲基)丙烯醯基變得容易，故可提高與抗蝕劑材料之分散性或結合性。 《平均粒徑》 表面處理金屬氧化物粒子之平均粒徑較佳為5～500 nm。平均粒徑若小於5 nm，則製造該尺寸之粒子本身較難，若大於500 nm，則雖亦按照其含量，但難以實現抗蝕劑材料之透明性。更佳之平均粒徑為5～200 nm，進而較佳為10～25 nm。 《折射率》 為了使作為抗蝕劑材料之折射率大於1.6，表面處理金屬氧化物粒子之折射率較佳為1.7以上。 [分散介質] 表面處理金屬氧化物溶膠之分散介質可使用先前公知之有機溶劑。特別是用作抗蝕劑材料時，該分散介質若亦考慮作為抗蝕劑材料之作業性，則使用分散介質中至少包含1種溶解參數(Solubility Parameter：SP值)為10以上且大氣壓下沸點超過100℃之有機溶劑者。該有機溶劑較佳為於分散介質中含有30～95質量%。此處，若SP值未達10，則表面處理金屬氧化物粒子之分散性變低。又，若為沸點為100℃以下之有機溶劑，則由於塗佈時之乾燥迅速、流平前已造膜，故有塗膜上發生隆起之虞。進而，若分散介質中之有機溶劑之量少於30質量%，則表面處理金屬氧化物粒子之分散性降低。相反，若多於95質量%，則難以獲得所需之膜厚。更佳之量為40～90質量%，進而較佳為50～80質量%。 作為SP值為10以上且沸點超過100℃之有機溶劑，可列舉丙二醇單甲醚(PGM)、丙二醇單甲醚乙酸酯(PGMEA)、乙二醇單甲醚、乙二醇單乙醚、乙二醇單正丁基醚、乙醯丙酮、乙二醇、二苯醚、丙三醇、甲醯胺、苄醇、N-甲基吡咯啶酮、甘油、環己酮、二乙二醇單乙醚、乙二醇單苯醚、γ-丁內酯、鄰苯二甲酸二乙酯、鄰苯二甲酸二甲酯、二甲基亞碸、4-羥基-4-甲基-2-戊酮(DAA)、1-丁醇、2-丁醇、1,3-丁二醇、1,4-丁二醇、1,4-二㗁烷等。其中特佳為丙二醇單甲醚(PGM)。 上述分散介質中，為了進而提高分散性，可至少含有1種SP值為13以上、且大氣壓下沸點為100℃以下之溶劑。分散介質中之該溶劑之含量較佳為未達20質量%。由於含有該溶劑，溶劑融合，溶膠之穩定性提高。若該溶劑含有20質量%以上，則存在塗膜之隆起發生、硬度變得不充分之情況。更佳之量為1～15質量%，進而較佳為3～12質量%。 作為SP值為13以上且沸點為100℃以下之溶劑，可列舉低級醇與水。其中特佳為甲醇與乙醇。 ＜雜質成分＞ 存在表面處理金屬氧化物溶膠中作為雜質成分含有鈉或鉀、氨之情況。若該等中之任1種大量存在，則溶膠之穩定性降低。又，作為抗蝕劑材料之加工性亦惡化，難以圖案狀曝光及顯影。因此，鈉較佳為以Na2 O濃度計為25 ppm以下，更佳為未達20 ppm，鉀較佳為以K2 O濃度計未達0.5質量%，氨較佳為以NH3 濃度計未達1000 ppm。 《表面處理金屬氧化物溶膠之濃度》 表面處理金屬氧化物溶膠之固形物成分濃度較佳為5～70質量%。若固形物成分濃度低於5質量%，則存在無法獲得所需之折射率或膜硬度之情況。若固形物成分濃度高於70質量%，則難以實現抗蝕劑材料之透明性。更佳之量為10～60質量%，進而較佳為20～40質量%。 [表面處理金屬氧化物溶膠之製造方法] ＜第1步驟＞ 第1步驟係製造金屬氧化物粒子之步驟。以下就其製造方法加以說明。 ＜金屬氧化物溶膠之製造方法＞ ≪鈦酸水溶液之製造≫ 藉由先前公知之方法製備含水鈦酸凝膠或溶膠。含水鈦酸凝膠藉由於例如氯化鈦、硫酸鈦等之水溶液中添加鹼中和而獲得。又，含水鈦酸溶膠係藉由使氯化鈦、硫酸鈦等之水溶液通過離子交換樹脂而去除陰離子而獲得。此處所謂之含水鈦酸意味著氧化鈦水合物或鈦之氫氧化物。 其次，於所得之含水鈦酸凝膠或含水鈦酸溶膠或該等之混合物中添加過氧化氫溶解含水鈦酸而製備均一之水溶液。此時，較佳為加熱或攪拌。此時，若含水鈦酸之濃度變得過高，則由於含水鈦酸之溶解需要較長時間，進而未溶解狀態之凝膠之沈澱生成，或所得之水溶液之黏度變高，故而不佳。因此，以TiO2 濃度計為約10質量%以下，較佳為約5質量%以下。應添加之過氧化氫之量若以H2 O2 /TiO2 質量比計為1以上，則可完全溶解含水鈦酸。若H2 O2 /TiO2 比未達1，則由於含水鈦酸未完全溶解而殘存有未反應之凝膠或溶膠，故而不佳。又，雖H2 O2 /TiO2 比越大，含水鈦酸之溶解速度越快，反應於短時間內結束，但若過度使用過氧化氫，則由於未反應之過氧化氫大量殘存於系內，對後續之步驟產生不良影響，故而不佳。因此，以H2 O2 /TiO2 比為1～6、較佳為2～6左右之量使用過氧化氫較佳。若以此種量使用過氧化氫，則含水鈦酸於0.5～20小時左右內完全溶解。此時之反應溫度為50℃以上，較佳為70℃以上。 ≪二氧化鈦(TiO2 )水分散液之製造≫ 繼而，將如上所述獲得之含水鈦酸溶解之水溶液(鈦酸水溶液)加熱至60℃以上、較佳為80℃以上，使鈦酸水解。藉此，獲得TiO2 粒子之水分散液。 ≪二氧化鈦二氧化矽(TiO2 /SiO2 )水分散液之製造≫ 於上述鈦酸水溶液中以特定量混合矽化合物，加熱至60℃以上、較佳為80℃以上，使鈦酸水解。藉此，獲得TiO2 /SiO2 粒子之水分散液。 此處，作為矽化合物，使用利用陽離子交換樹脂對矽酸鹼鹽水溶液進行脫鹼而得之矽酸液、利用酸中和矽酸鹼鹽而得之矽溶膠、或矽酸乙酯等烷氧化物或其水解物等矽化合物之溶液或分散液。又，亦可使用市售之矽溶膠。該等情形時，二氧化矽之平均粒徑較佳為500 nm以下。TiO2 /SiO2 之比率為75/25以上。又，TiO2 /SiO2 之比率較佳為80/20以上。 作為向鈦酸水溶液添加矽化合物之溶液或分散液之方法，一面加熱鈦酸水溶液一面緩慢添加矽化合物之溶液或分散液之方法、將二氧化鈦溶膠前驅物與矽化合物之溶液或分散液一併混合之後再加熱之方法均可，應根據二氧化鈦濃度、矽化合物之溶液或分散液中之二氧化矽濃度選擇。雖於二氧化鈦濃度未達1質量%之較稀薄之情形時，即便為將兩者一併混合之方法亦不造成任何阻礙，但由於在二氧化鈦濃度為1質量%以上之較濃厚之情形時，存在二氧化矽使二氧化鈦凝集之情況，並且若二氧化矽濃度較高則發生二氧化矽單獨之凝集、聚合，故而較佳為緩慢添加之方法。 為了促進矽化合物與二氧化鈦之反應，添加或混合時之溫度通常較佳為加熱至約60℃以上進行。然而，使用矽酸乙酯等烷氧化物時，由於該等之水解速度較快，混合液中易生成二氧化矽之膠體粒子，故而採用於約40℃以下之較低溫下緩慢添加烷氧化物、添加結束後升溫至約60℃以上之溫度、使反應完結之方法。添加矽化合物時之混合液之pH自鈦酸水溶液及生成二氧化鈦溶膠之穩定性之方面而言，較佳為中性或鹼性，通常於約6～10之範圍內進行。於對TiO2 /SiO2 水分散液進行濃縮之情形時，可採用蒸發法、超濾法等公知之方法。 ≪二氧化鈦二氧化矽氧化錫(TiO2 /SiO2 /SnO2 )水分散液之製造≫ 於上述鈦酸水溶液中以特定量混合矽化合物或錫化合物，加熱至60℃以上、較佳為80℃以上，使鈦酸水解。藉此，獲得TiO2 /SiO2 /SnO2 粒子之水分散液。 此處，作為矽化合物，可使用與上述TiO2 /SiO2 之製造中所使用者相同者。 作為添加於鈦酸水溶液中之錫化合物，使用氯化錫、硫酸錫或氧氯化錫等錫化合物之水溶液或分散液。向鈦酸水溶液添加此種錫化合物之方法可與添加上述TiO2 /SiO2 之矽化合物相同。添加之順序可為先添加任一，亦可為同時添加。TiO2 /SiO2 /SnO2 之比率為TiO2 為70～90質量%、SiO2 為10～20質量%、SnO2 為2～30質量%，TiO2 /(SiO2 ＋SnO2 )之比率於50/50～95/5之範圍內。其他製造條件與上述TiO2 /SiO2 相同。較佳為TiO2 為70～90質量%、SiO2 為10～20質量%、SnO2 為2～30質量%，TiO2 /(SiO2 ＋SnO2 )之比率於70/30～90/10之範圍內。 ≪鐵或二氧化鈰摻雜處理≫ 向TiO2 /SiO2 或TiO2 /SiO2 /SnO2 摻雜鐵或二氧化鈰之處理藉由於上述鈦酸水溶液之製造中、製備鐵或鈰之氯化物與鈦鹽之水溶液並於其中添加鹼中和而獲得。之後之製造方法與鈦酸水溶液之製造方法及TiO2 /SiO2 之製造方法或TiO2 /SiO2 /SnO2 之製造方法相同地進行。摻雜量相對於對象之TiO2 /SiO2 或TiO2 /SiO2 /SnO2 100質量份，作為Fe2 O3 或CeO2 ，未達10質量份。摻雜量較佳為未達5質量份，更佳為未達3質量份。 ≪有機溶劑置換≫ 於後述「第2步驟」之前，將對象之金屬氧化物粒子之水分散液置換為先前公知之有機溶劑。該有機溶劑可使用醇類、酯類、二醇類、醚類。具體而言，作為醇類，有甲醇、乙醇、丙醇、2-丙醇等。作為酯類，有乙酸甲酯、乙酸乙酯、乙酸異丙酯、乙酸丙酯等。作為二醇類，有乙二醇、己二醇等。作為醚類，有二乙醚、乙二醇單甲醚、乙二醇單乙醚、乙二醇單丁醚、乙二醇異丙醚、二乙二醇單甲醚、二乙二醇單乙醚等。該等可單獨使用，又，亦可將2種以上混合使用。該等之中，特佳為作為低級醇之甲醇、乙醇。 溶劑置換可藉由使用超濾裝置等先前公知之方法進行。溶劑置換後之分散介質中之水之含量較佳為至多未達20質量%。 ＜第2步驟＞ 第2步驟係對金屬氧化物粒子之表面藉由式(1)所表示之包含(甲基)丙烯醯基之有機矽化合物進行處理、於金屬氧化物粒子之表面設置包含(甲基)丙烯醯基之有機矽化合物之層者。以下就其製造方法加以說明。 ＜包含(甲基)丙烯醯基之有機矽化合物之層之製造＞ 於該金屬氧化物粒子之有機溶劑分散液中添加式(1)所表示之包含(甲基)丙烯醯基之有機矽化合物。添加之方法雖並未特別限制，但較佳為以兩者充分混合之方式一面攪拌一面添加。又，為了促進反應，亦可加熱至40～60℃左右。 該包含(甲基)丙烯醯基之有機矽化合物之添加量僅按照以下添加：相對於金屬氧化物粒子100質量份，於金屬氧化物粒子之表面以R1 n -SiO(4-n)/2 (其中，R1 係選自甲基丙烯醯基及丙烯醯基中之至少一者，相互可相同，亦可不同。n係1～3之整數)計，設有0.1～60質量份；且若累加設於該金屬氧化物粒子之表面者與除此之外游離存在於溶膠中者，則相對於金屬氧化物粒子100質量份，以R1 n -SiO(4-n)/2 (其中，R1 係選自甲基丙烯醯基及丙烯醯基中之至少一種，相互可相同，亦可不同。n係1～3之整數)計，設有0.1～100質量份。較佳之有機矽化合物之量為1～70質量份，更佳為5～40質量份。 ≪溶劑置換≫ 繼而，藉由先前公知之方法，以SP值為10以上且沸點超過100℃之有機溶劑藉由先前公知之方法進行溶劑置換。該有機溶劑於分散介質中含有30～95質量%。 藉此，獲得本發明之表面處理金屬氧化物溶膠。 於上述表面處理金屬氧化物溶膠中，為了進而提高分散性，低級醇及水之含量可未達20質量%。其中，鈉較佳為以Na2 O濃度計為25 ppm以下，更佳為未達20 ppm，鉀較佳為以K2 O濃度計未達0.5%，氨較佳為以NH3 濃度計未達1000 ppm。 ＜第3步驟＞ 第3步驟係於金屬氧化物粒子之表面設置選自二氧化矽氧化鋯、二氧化矽氧化鋁、二氧化矽二氧化鈦、二氧化矽氧化錫中之二氧化矽複合氧化物之層者。以下就其製造方法加以說明。 ＜二氧化矽複合氧化物之層之製造＞ 為了設置設於對象之金屬氧化物粒子之二氧化矽複合氧化物之層，使用選自矽化合物、鋯化合物、鋁化合物、鈦化合物、錫化合物中之化合物作為原料。 此處，作為矽化合物，可使用利用陽離子交換樹脂對矽酸鹼鹽水溶液進行脫鹼而得之矽酸液、利用酸中和矽酸鹼鹽而得之矽溶膠、或矽酸乙酯等烷氧化物或其水解物等矽化合物之溶液或分散液。又，亦可使用市售之矽溶膠。 作為除矽化合物之外之金屬化合物，使用氯化物或硫酸化合物、碳酸銨化合物、羥基氯化化合物等之水溶液或分散液、及金屬烷氧化物等。於向該等中添加鹼中和、或水解而得者中添加過氧化氫，獲得選自鋯、鋁、鈦及錫中之金屬酸水溶液。 其次，於對象之金屬氧化物粒子之分散液中添加矽化合物之溶液或分散液與上述金屬酸水溶液。添加之方法雖並未特別限制，但優選為以兩者充分混合之方式一面攪拌一面添加。又，為了促進反應，亦可加熱。矽化合物與除矽化合物之外之金屬化合物以SiO2 /MOX (其中，MOX 係選自ZrO2 、Al2 O3 、TiO2 、SnO2 中之任一種)之莫耳比計分別為33.3/66.7～99.5/0.5。較佳之莫耳比為50.0/50.0～95.2/4.8，更佳為50.0/50.0～76.9/23.1。又，其量相對於金屬氧化物粒子100質量份，以(SiO2 ＋MOX )計為1～180質量份。較佳之量為2～30質量份，更佳為3～10質量份。 ＜第4步驟＞ 第4步驟係於金屬氧化物粒子之表面設置二氧化矽層者。以下就其製造方法加以說明。 ＜二氧化矽層之製造＞ 為了設置設於對象之金屬氧化物粒子之二氧化矽層，使用利用陽離子交換樹脂對矽酸鹼鹽水溶液進行脫鹼而得之矽酸液、利用酸中和矽酸鹼鹽而得之矽溶膠、或矽酸乙酯等烷氧化物或其水解物等矽化合物之溶液或分散液作為原料。又，亦可使用市售之矽溶膠。 於對象之金屬氧化物粒子之分散液中添加矽化合物之溶液或分散液。添加之方法雖並未特別限制，但優選為以兩者充分混合之方式一面攪拌一面添加。又，為了促進反應，亦可加熱。矽化合物相對於金屬氧化物粒子100質量份，以SiO2 計為0.1～100質量份。較佳之量為0.5～30質量份，更佳為1～10質量份。 《步驟之順序》 構成本發明之表面處理金屬氧化物粒子其表面設有式(1)所表示之包含(甲基)丙烯醯基之有機矽化合物。若為可實現該構成者，則步驟之順序並未特別限制。其中，若考慮製造時之生產性、品質穩定性，則實施其之「第2步驟」於上述第1～第4步驟中實施者之中，較佳為最後進行。又，製造金屬氧化物粒子之「第1步驟」於上述第1～第4步驟中實施者之中，較佳為最初進行。 作為製造表面處理金屬氧化物粒子之步驟之順序， 例示有： 製造金屬氧化物粒子(第1步驟)，其次於該金屬氧化物粒子之表面設置包含(甲基)丙烯醯基之有機矽化合物(第2步驟)之順序； 製造金屬氧化物粒子(第1步驟)，其次於該金屬氧化物粒子之表面設置選自二氧化矽氧化鋯、二氧化矽氧化鋁、二氧化矽二氧化鈦、二氧化矽氧化錫中之二氧化矽複合氧化物之層(第3步驟)，此後設置包含(甲基)丙烯醯基之有機矽化合物(第2步驟)之順序； 製造金屬氧化物粒子(第1步驟)，其次於該金屬氧化物粒子之表面設置二氧化矽層(第4步驟)，此後設置包含(甲基)丙烯醯基之有機矽化合物(第2步驟)之順序； 製造金屬氧化物粒子(第1步驟)，其次於該金屬氧化物粒子之表面設置選自二氧化矽氧化鋯、二氧化矽氧化鋁、二氧化矽二氧化鈦、二氧化矽氧化錫中之二氧化矽複合氧化物之層(第3步驟)，進而設置二氧化矽層(第4步驟)，此後設置包含(甲基)丙烯醯基之有機矽化合物(第2步驟)之順序。 ≪脫鹼步驟≫ 於上述第1～第4步驟中，為了使反應進行，較佳為根據需要進行脫鹼處理。脫鹼處理可使用使用離子交換樹脂或超濾裝置等先前公知之方法。脫鹼步驟以第2步驟中所得之本發明之表面處理氧化物溶膠中之鈉較佳為以Na2 O濃度計為25 ppm以下、更佳為未達20 ppm、鉀以K2 O濃度計未達0.5%、氨以NH3 濃度計未達1000 ppm之方式適當實施。 [實施例] 以下，對實施例具體加以說明。本發明並非藉由該等實施例而限定者。 [實施例1] ＜二氧化鈦系粒子之製造(利用第1步驟)＞ 將包含以TiO2 換算為2質量%之四氯化鈦之四氯化鈦水溶液450 g與15質量%之氨水176 g混合，製備pH為8.6之白色漿料液。繼而，對該漿料進行過濾之後，用純水進行清洗，獲得固形物成分含量為5質量%之含水鈦酸濾餅180 g。 其次，於該濾餅180 g中添加35質量%之過氧化氫水205.6 g與純水514.4 g之後，於80℃之溫度下加熱1小時，獲得以TiO2 換算包含2質量%之過氧化鈦酸之過氧化鈦酸水溶液900 g。該過氧化鈦酸水溶液為透明之黃褐色、且pH為8.1。 繼而，於該過氧化鈦酸水溶液450 g中混合包含15質量%之平均粒徑為7 nm之二氧化矽粒子之矽溶膠(日揮觸媒化成(股)製造：CATALOID SN-350)8.2 g與純水589 g，於高壓釜中於165℃下進行18小時水熱處理。 其次，將所得之水溶液冷卻至室溫之後，利用超濾膜裝置進行濃縮，獲得固形物成分濃度為10質量%之二氧化鈦系粒子(1-A)水分散液。 二氧化鈦系微粒子(1-A)之粒子之折射率為2.3。 ＜二氧化矽複合氧化物層之製造(利用第3步驟)＞ 於包含以ZrO2 換算為2質量%之氧氯化鋯之氧氯化鋯水溶液263 g中於攪拌下緩慢添加15質量%之氨水，獲得包含鋯之水合物之pH為8.5之漿料液。繼而，對該漿料進行過濾之後，用純水進行清洗，獲得包含以ZrO2 換算為10質量%之鋯成分之濾餅52.6 g。 其次於該濾餅20 g中添加純水180 g，進而添加10質量%之氫氧化鉀水溶液12 g使其為鹼性之後，添加35質量%之過氧化氫水40 g，加溫至50℃溶解濾餅。進而添加純水148 g，獲得包含以ZrO2 計為0.5質量%之過氧化鋯酸之過氧化鋯酸水溶液400 g。 另一方面，於以SiO2 計為2質量%之水玻璃中緩慢添加陽離子交換樹脂(三菱樹脂(股)製造)進行脫鹼之後，分離離子交換樹脂，獲得以SiO2 計為2質量%之矽酸水溶液。 其次，於以TiO2 計為10質量%之二氧化鈦系粒子(1-A)水分散液80 g中添加純水320 g，加溫至90℃。於其中緩慢添加上述過氧化鋯酸水溶液26.7 g與矽酸水溶液21.2 g。添加結束後維持90℃攪拌1小時之後，對該混合液於高壓釜中於165℃下進行18小時水熱處理。 繼而，將該混合液冷卻至室溫之後，利用超濾膜裝置進行濃縮，獲得設有二氧化矽氧化鋯之複合氧化物層之固形物成分濃度為10質量%之二氧化鈦系粒子(1-B)水分散液128 g。 ＜二氧化矽層之製造(利用第4步驟)＞ 於二氧化鈦系粒子(1-B)水分散液117 g中緩慢添加陽離子交換樹脂(三菱樹脂(股)製造)進行脫鹼之後，分離離子交換樹脂。於該溶液中緩慢添加溶解有四乙氧基矽烷(多摩化學(股)製造，SiO2 成分28.8質量%)8.96 g之甲醇溶液126.0 g，於50℃下加熱攪拌1小時，獲得二氧化鈦系粒子(1-C)之水/甲醇分散液。 將所得之二氧化鈦系粒子(1-C)之水/甲醇分散液冷卻至室溫，利用超濾膜將分散介質置換為甲醇。其後進行濃縮，獲得設有二氧化矽層之固形物成分濃度為30質量%之二氧化鈦系粒子(1-C)甲醇分散液40 g。 如此所得之二氧化鈦系粒子(1-C)甲醇分散液中所含之水分量為0.3質量%。 ＜表面處理金屬氧化物溶膠之製造：利用包含(甲基)丙烯醯基之有機矽化合物之表面處理(利用第2步驟)＞ 於二氧化鈦系粒子(1-C)甲醇分散液40 g中緩慢添加3-甲基丙烯醯氧基丙基三甲氧基矽烷(商品名：KBM-503，信越化學工業(股)製造)1.47 g之後，於50℃下加熱攪拌19小時。 冷卻至室溫之後，利用超濾膜將分散介質置換為丙二醇單甲醚(PGME)，獲得固形物成分濃度為30質量%之表面處理金屬氧化物溶膠(1-D)40 g。將所得之表面處理金屬氧化物溶膠之組成示於表1。 《平均粒徑之測定》 平均粒徑係拍攝電子顯微鏡照片並測定任意100個粒子之粒徑取其平均值而得者。 《粒子之折射率之測定方法》 1)將分散液採集至蒸發器，使分散介質蒸發。 2)將其於120℃下乾燥，製成粉末。 3)於玻璃板上滴加2、3滴折射率已知之基準折射液，於其中混合上述粉末。 4)藉由種種基準折射液進行上述3)之操作，將混合液變成透明時之基準折射液之折射率作為粒子之折射率。 ＜透明覆膜形成用塗料(1)之製造＞ 添加將丙二醇單甲醚84.1 g與乙氧化雙酚A二丙烯酸酯(新中村化學(股)製造：NK ESTER ABE-300)1.2 g、乙氧化季戊四醇四丙烯酸酯(新中村化學(股)製造：NK ESTER ATM-4E)0.6 g混合而得者，充分混合。繼而，添加2,2-二甲氧基-1,2-二苯基乙烷-1-酮(BASF(股)製造：IRGACURE651)0.05 g與苯基雙(2,4,6-三甲基苯甲醯基)-氧化膦(BASF(股)製造：IRGACURE819)0.04 g並充分混合，製備透明覆膜用黏合劑。 繼而，於上述透明覆膜用黏合劑中混合表面處理金屬氧化物溶膠(1-D)14.0 g而製備固形物成分濃度6質量%之透明覆膜形成用塗料(1)。 ＜附透明覆膜之基材(1-FA)之製造＞ 將透明覆膜形成用塗料(1)藉由刮棒塗佈機法(刮棒＃10)塗佈於易接著PET膜(東洋紡製造：COSMOSHINE A-4300，厚度188 μm，總透光率92.0%，霧度0.7%)，於80℃下乾燥1分鐘之後，藉由高壓水銀燈(日本電池製造：UV(ultraviolet，紫外線)照射裝置CS30L21-3)以120 mJ/cm2 照射使其硬化，製備附透明覆膜之基材(1-FA)。此時透明覆膜之厚度為400 nm。 藉由以下方法對所得之膜之霧度、總透光率、折射率、耐擦傷性、耐候性進行評價。 《霧度、總透光率之測定》 所得之透明覆膜之霧度及總透光率藉由霧度計(日本電色(股)製造：NDH-2000)測定。按照以下標準對霧度及總透光率進行評價，將結果示於表中。 ＜評價標準＞ 霧度； 1.0%以下：◎ 1.1～2.0%：○ 2.1%以上：× ＜評價標準＞ 總透光率； 85～100%：◎ 75～84%：○ 74%以下：× 《折射率之測定》 覆膜之折射率利用光譜式橢圓儀(日本SEMILAB公司製造：SE-2000)測定。按照以下標準對折射率進行評價，將結果示於表中。 ＜評價標準＞ 1.70以上：◎ 1.60～1.69：○ 1.59以下：× 《耐擦傷性之測定》 使用＃0000鋼絲絨以負載500 g/cm2 滑動50次，對膜之表面進行目視觀察。按照以下標準對耐擦傷性進行評價，將結果示於表中。 ＜評價標準＞ 看不到筋狀擦傷：◎ 可看到少量筋狀擦傷：○ 可看到大量筋狀擦傷：△ 面整體摩擦：× 《耐候性之測定》 藉由褪色試驗用水銀燈(東芝(股)製造：H400-E)對附透明導電性覆膜之基材(1-FA)照射紫外線24小時，對顏色進行目視確認。按照以下標準對耐候性進行評價，將結果示於表中。再者，燈與試驗片之照射距離設為70 mm，燈之輸出以試驗片之表面溫度為45±5℃之方式調整。 ＜評價標準＞ 看不到變色：◎ 可看到少許變色：○ 可看到明顯變色：× ＜附透明覆膜之基材(1-FB)之製造＞ 將透明覆膜形成用塗料(1)藉由旋轉塗佈機塗佈於6英吋之矽晶圓上，於80℃下乾燥1分鐘之後，使用曝光裝置NSR-S302(尼康公司製造)照射ArF準分子雷射(193 nm)使其硬化，製備附透明覆膜之基材(1-FB)。此時透明覆膜之厚度為400 nm。 藉由以下方法對所得之膜之隆起及感度進行評價。 《隆起之測定》 藉由掃描型電子顯微鏡對附透明導電性覆膜之基材(1-FB)之剖面進行觀察，測定較膜中心部之膜厚更厚10%以上之膜端部之寬度。按照以下評價標準對隆起進行評價，將結果示於表中。 ＜評價標準＞ 厚10%以上之膜端部之寬度未達0.5 mm：◎ 厚10%以上之膜端部之寬度為0.5～1.0 mm：○ 厚10%以上之膜端部之寬度為1.1 mm以上：× 《感度、殘膜率之測定》 ＜評價標準＞ 將附透明導電性覆膜之基材(1-FB)浸漬於1質量%之Na2 CO3 水溶液中10分鐘而去除未硬化部分之後，於80℃下乾燥1晩，根據浸漬前後之質量差對感度、殘膜率進行評價，將結果示於表中。 ＜評價標準＞ Na2 CO3 水溶液浸漬前後之質量差為0～3%：◎ Na2 CO3 水溶液浸漬前後之質量差為4～10%：○ Na2 CO3 水溶液浸漬前後之質量差為11%以上：× ＜附透明覆膜之基材(1-FC)之製造＞ 將透明覆膜形成用塗料(1)藉由旋轉塗佈機塗佈於6英吋之矽晶圓上，於80℃下乾燥1分鐘之後，使用曝光裝置NSR-S302(尼康公司製造)介隔光罩(1：1之比率之線圖)照射ArF準分子雷射(193 nm)使其硬化。其後，噴霧1質量%之Na2 CO3 水溶液溶解去除未曝光部分，於150℃下加熱3分鐘，製備附透明覆膜之基材(1-FC)。 使用所得之帶透明膜之基材(1-FC)，藉由以下方法對解像度進行評價。 《解像度之測定》 變化製作附透明導電性覆膜之基材(1-FC)時之光罩之間距寬度，將間距寬度正常形成之最小間距寬度作為解像度之值如下進行評價，將結果示於表中。 ＜評價標準＞ 間距寬度30 μm以下：◎ 間距寬度31 μm～50 μm：○ 間距寬度51 μm以上：× [實施例2] 除於第2步驟中，使用3-甲基丙烯醯氧基丙基三甲氧基矽烷(信越化學工業(股)製造：KBM-503)0.06 g以外，與實施例1相同地進行，獲得表面處理金屬氧化物溶膠(2-D)。將所得之表面處理金屬氧化物溶膠之組成示於表1。 除使用表面處理金屬氧化物溶膠(2-D)以外，與實施例1相同地進行，製造透明覆膜形成用塗料。繼而，與實施例1相同地製造帶透明覆膜之基材，並對其進行評價。 [實施例3] 除於第2步驟中，使用3-甲基丙烯醯氧基丙基三甲氧基矽烷(信越化學工業(股)製造：KBM-503)7.2 g以外，與實施例1相同地進行，獲得表面處理金屬氧化物溶膠(3-D)。將所得之表面處理金屬氧化物溶膠之組成示於表1。 除使用表面處理金屬氧化物溶膠(3-D)以外，與實施例1相同地進行，製造透明覆膜形成用塗料。繼而，與實施例1相同地製造帶透明覆膜之基材，並對其進行評價。 [實施例4] 於第2步驟中，添加3-甲基丙烯醯氧基丙基三甲氧基矽烷(信越化學工業(股)製造：KBM-503)0.06 g以後，添加2.9質量%氨水溶液0.29 g，除此之外，與實施例1相同地進行，獲得表面處理金屬氧化物溶膠(4-D)。將所得之表面處理金屬氧化物溶膠之組成示於表1。 除使用表面處理金屬氧化物溶膠(4-D)以外，與實施例1相同地進行，製造透明覆膜形成用塗料。繼而，與實施例1相同地製造帶透明覆膜之基材，並對其進行評價。 [實施例5] 於第2步驟中，添加3-甲基丙烯醯氧基丙基三甲氧基矽烷(信越化學工業(股)製造：KBM-503)7.2 g以後，添加2.9質量%氨水溶液0.29 g，除此之外，與實施例1相同地進行，獲得表面處理金屬氧化物溶膠(5-D)。 除使用表面處理金屬氧化物溶膠(5-D)以外，與實施例1相同地進行，製造透明覆膜形成用塗料。繼而，與實施例1相同地製造帶透明覆膜之基材，並對其進行評價。 [實施例6] 除於第4步驟中，使用溶解有四乙氧基矽烷(多摩化學(股)製造，SiO2 成分28.8質量%)0.90 g之甲醇溶液126.0 g以外，與實施例1相同地進行，獲得表面處理金屬氧化物溶膠(6-D)。將所得之表面處理金屬氧化物溶膠之組成示於表1。 除使用表面處理金屬氧化物溶膠(6-D)以外，與實施例1相同地進行，製造透明覆膜形成用塗料。繼而，與實施例1相同地製造附透明覆膜之基材，並對其進行評價。 [實施例7] 除於第4步驟中，使用溶解四乙氧基矽烷(多摩化學(股)製造，SiO2 成分28.8質量%)44.8 g之甲醇溶液126.0 g以外，與實施例1相同地進行，獲得表面處理金屬氧化物溶膠(7-D)。將所得之表面處理金屬氧化物溶膠之組成示於表1。 除使用表面處理金屬氧化物溶膠(7-D)以外，與實施例1相同地進行，製造透明覆膜形成用塗料。繼而，與實施例1相同地製造帶透明覆膜之基材，並對其進行評價。 [實施例8] 除於第3步驟中，使用過氧化鋯酸水溶液7.6 g、矽酸水溶液6.1 g以外，與實施例1相同地進行，獲得表面處理金屬氧化物溶膠(8-D)。將所得之表面處理金屬氧化物溶膠之組成示於表1。 除使用表面處理金屬氧化物溶膠(8-D)以外，與實施例1相同地進行，製造透明覆膜形成用塗料。繼而，與實施例1相同地製造帶透明覆膜之基材，並對其進行評價。 [實施例9] 除於第3步驟中，使用過氧化鋯酸水溶液171.6 g、矽酸水溶液142.3 g以外，與實施例1相同地進行，獲得表面處理金屬氧化物溶膠(9-D)。將所得之表面處理金屬氧化物溶膠之組成示於表1。 除使用表面處理金屬氧化物溶膠(9-D)以外，與實施例1相同地進行，製造透明覆膜形成用塗料。繼而，與實施例1相同地製造附透明覆膜之基材，並對其進行評價。 [實施例10] 除於第3步驟中，使用過氧化鋯酸水溶液6.02 g、矽酸水溶液23.7 g以外，與實施例1相同地進行，獲得表面處理金屬氧化物溶膠(10-D)。將所得之表面處理金屬氧化物溶膠之組成示於表1。 除使用表面處理金屬氧化物溶膠(10-D)以外，與實施例1相同地進行，製造透明覆膜形成用塗料。繼而，與實施例1相同地製造帶透明覆膜之基材，並對其進行評價。 [實施例11] 除於第3步驟中，使用過氧化鋯酸水溶液120.5 g、矽酸水溶液9.8 g以外，與實施例1相同地進行，獲得表面處理金屬氧化物溶膠(11-D)。將所得之表面處理金屬氧化物溶膠之組成示於表1。 除使用表面處理金屬氧化物溶膠(11-D)以外，與實施例1相同地進行，製造透明覆膜形成用塗料。繼而，與實施例1相同地製造帶透明覆膜之基材，並對其進行評價。 [實施例12] 除於第3步驟中，使用Al2 O3 換算濃度1.0質量%之鋁酸鈉水溶液11.5 g與SiO2 換算濃度3.0質量%之矽酸鈉水溶液14.8 g代替過氧化鋯酸水溶液與矽酸水溶液以外，與實施例1相同地進行，獲得設有二氧化矽氧化鋁之複合氧化物層之固形物成分濃度為10質量%之二氧化鈦系粒子(12-B)水分散液。 之後亦與實施例1相同地進行，獲得表面處理金屬氧化物溶膠(12-D)。將所得之表面處理金屬氧化物溶膠之組成示於表1。 除使用表面處理金屬氧化物溶膠(12-D)以外，與實施例1相同地進行，製造透明覆膜形成用塗料。繼而，與實施例1相同地製造帶透明覆膜之基材，並對其進行評價。 [實施例13] 除於第3步驟中。使用Al2 O3 換算濃度1.0質量%之鋁酸鈉水溶液11.5 g與SiO2 換算濃度3.0質量%之矽酸鈉水溶液14.8 g代替過氧化鋯酸水溶液與矽酸水溶液以外，與實施例1相同地進行，獲得設有二氧化矽氧化鋁之複合氧化物層之固形物成分濃度為10質量%之二氧化鈦系粒子(13-B)水分散液。 繼而，除重複進行第4步驟中之使用陽離子交換樹脂之脫鹼處理以外，與實施例1相同地進行，獲得設有二氧化矽層之固形物成分濃度為30質量%之二氧化鈦系粒子(13-C)甲醇分散液。 之後亦與實施例1相同地進行，獲得表面處理金屬氧化物溶膠(13-D)。將所得之表面處理金屬氧化物溶膠之組成示於表1。 除使用表面處理金屬氧化物溶膠(13-D)以外，與實施例1相同地進行，製造透明覆膜形成用塗料。繼而，與實施例1相同地製造帶透明覆膜之基材，並對其進行評價。 [實施例14] 除於第3步驟中，使用TiO2 換算濃度1.0質量%之四氯化鈦水溶液9.5 g與SiO2 換算濃度3.0質量%之矽酸鈉水溶液15.5 g代替過氧化鋯酸水溶液與矽酸水溶液以外，與實施例1相同地進行，獲得設有二氧化矽二氧化鈦之複合氧化物層之固形物成分濃度為10質量%之二氧化鈦系粒子(14-B)水分散液。 之後亦與實施例1相同地進行，獲得表面處理金屬氧化物溶膠(14-D)。將所得之表面處理金屬氧化物溶膠之組成示於表1。 除使用表面處理金屬氧化物溶膠(14-D)以外，與實施例1相同地進行，製造透明覆膜形成用塗料。繼而，與實施例1相同地製造帶透明覆膜之基材，並對其進行評價。 [實施例15] 除於第3步驟中，使用SnO2 換算濃度1.0質量%之錫酸鉀水溶液15.5 g與SiO2 換算濃度2.0質量%之矽酸水溶液13.5 g代替過氧化鋯酸水溶液與矽酸水溶液以外，與實施例1相同地進行，獲得設有二氧化矽氧化錫之複合氧化物層之固形物成分濃度為10質量%之二氧化鈦系粒子(15-B)水分散液。 之後亦與實施例1相同地進行，獲得表面處理金屬氧化物溶膠(15-D)。將所得之表面處理金屬氧化物溶膠之組成示於表1。 除使用表面處理金屬氧化物溶膠(15-D)以外，與實施例1相同地進行，製造透明覆膜形成用塗料。繼而，與實施例1相同地製造附透明覆膜之基材，並對其進行評價。 [實施例16] 除於第1步驟中，於以TiO2 換算為2質量%之過氧化鈦酸水溶液450 g中不使用矽溶膠而混合純水599 g以外，與實施例1相同地進行，獲得固形物成分濃度為10質量%之二氧化鈦粒子(16-A)水分散液。 之後亦與實施例1相同地進行，獲得表面處理金屬氧化物溶膠(16-D)。將所得之表面處理金屬氧化物溶膠之組成示於表1。 除使用表面處理金屬氧化物溶膠(16-D)以外，與實施例1相同地進行，製造透明覆膜形成用塗料。繼而，與實施例1相同地製造附透明覆膜之基材，並對其進行評價。 [實施例17] 除於第1步驟中，於以TiO2 換算為2質量%之過氧化鈦酸水溶液450 g中混合包含以SiO2 計為15質量%之平均粒徑為7 nm之二氧化矽粒子之矽溶膠(日揮觸媒化成(股)製造：CATALOID SN-350)17.9 g與純水581 g以外，與實施例1相同地進行，獲得固形物成分濃度為10質量%之二氧化鈦系粒子(17-A)水分散液。 之後亦與實施例1相同地進行，獲得表面處理金屬氧化物溶膠(17-D)。將所得之表面處理金屬氧化物溶膠之組成示於表1。 除使用表面處理金屬氧化物溶膠(17-D)以外，與實施例1相同地進行，製造透明覆膜形成用塗料。繼而，與實施例1相同地製造附透明覆膜之基材，並對其進行評價。 [實施例18] 於第1步驟中，於與實施例1相同地製造之以TiO2 換算為2質量%之過氧化鈦酸水溶液729.0 g中混合陽離子交換樹脂35.0 g，於其中於攪拌下緩慢添加以SnO2 換算為1質量%之錫酸鉀水溶液91.0 g以後，分離陽離子交換樹脂。 繼而，混合包含以SiO2 計為15質量%之平均粒徑為7 nm之二氧化矽粒子之矽溶膠(日揮觸媒化成(股)製造：CATALOID SN-350)8.0 g與純水180.0 g，於高壓釜中於165℃下進行18小時水熱處理。 其次，將所得之水溶液冷卻至室溫之後，利用超濾膜裝置進行濃縮，獲得固形物成分濃度為10質量%之二氧化鈦系微粒子(18-A)水分散液。 之後與實施例1相同地進行，獲得表面處理金屬氧化物溶膠(18-D)。將所得之表面處理金屬氧化物溶膠之組成示於表2。 除使用表面處理金屬氧化物溶膠(18-D)以外，與實施例1相同地進行，製造透明覆膜形成用塗料。繼而，與實施例1相同地製造附透明覆膜之基材，並對其進行評價。 [實施例19] 於第1步驟中，混合包含以TiO2 換算為2質量%之四氯化鈦之四氯化鈦水溶液444.9 g與以Fe2 O3 換算為2質量%之氯化鐵水溶液5.1 g，混合15質量%之氨水176 g，除此以外，與實施例1相同地進行，獲得固形物成分濃度為10質量%之摻雜鐵之二氧化鈦系粒子(19-A)水分散液。 之後亦與實施例1相同地進行，獲得表面處理金屬氧化物溶膠(19-D)。將所得之表面處理金屬氧化物溶膠之組成示於表2。 除使用表面處理金屬氧化物溶膠(19-D)以外，與實施例1相同地進行，製造透明覆膜形成用塗料。繼而，與實施例1相同地製造附透明覆膜之基材，並對其進行評價。 [實施例20] 於第1步驟中，混合包含以TiO2 換算為2質量%之四氯化鈦之四氯化鈦水溶液404.0 g與以Fe2 O3 換算為2質量%之氯化鐵水溶液46.0 g，混合15質量%之氨水176 g，除此以外，與實施例1相同地進行，獲得固形物成分濃度為10質量%之摻雜鐵之二氧化鈦系粒子(20-A)水分散液104.9 g。 之後與實施例1相同地進行，獲得表面處理金屬氧化物溶膠(20-D)。將所得之表面處理金屬氧化物溶膠之組成示於表2。 除使用表面處理金屬氧化物溶膠(20-D)以外，與實施例1相同地進行，製造透明覆膜形成用塗料。繼而，與實施例1相同地製造附透明覆膜之基材，並對其進行評價。 [實施例21] 於第1步驟中，混合包含以TiO2 換算為2質量%之四氯化鈦之四氯化鈦水溶液444.9 g與以CeO2 換算為2質量%之氯化鈰水溶液5.1 g，混合15質量%之氨水176 g，除此以外，與實施例1相同地進行，獲得固形物成分濃度為10質量%之摻雜鈰之二氧化鈦系粒子(21-A)水分散液。 之後與實施例1相同地進行，獲得表面處理金屬氧化物溶膠(21-D)。將所得之表面處理金屬氧化物溶膠之組成示於表2。 除使用表面處理金屬氧化物溶膠(21-D)以外，與實施例1相同地進行，製造透明覆膜形成用塗料。繼而，與實施例1相同地製造附透明覆膜之基材，並對其進行評價。 [實施例22] 於第1步驟中，混合包含以TiO2 換算為2質量%之四氯化鈦之四氯化鈦水溶液404.0 g與以CeO2 換算為2質量%之氯化鈰水溶液46.0 g，混合15質量%之氨水176 g，除此以外，與實施例1相同地進行，獲得固形物成分濃度為10質量%之摻雜鈰之二氧化鈦系粒子(22-A)水分散液。 之後與實施例1相同地進行，獲得表面處理金屬氧化物溶膠(22-D)。將所得之表面處理金屬氧化物溶膠之組成示於表2。 除使用表面處理金屬氧化物溶膠(22-D)以外，與實施例1相同地進行，製造透明覆膜形成用塗料。繼而，與實施例1相同地製造附透明覆膜之基材，並對其進行評價。 [實施例23] 除於第1步驟中，於以TiO2 換算為2質量%之過氧化鈦酸水溶液450 g中混合包含以SiO2 計為15質量%之平均粒徑為7 nm之二氧化矽粒子之矽溶膠(日揮觸媒化成(股)製造：CATALOID SN-350)8.2 g與純水239.1 g以外，與實施例1相同地進行，獲得固形物成分濃度為10質量%之二氧化鈦系粒子(23-A)水分散液。 之後與實施例1相同地進行，獲得表面處理金屬氧化物溶膠(23-D)。將所得之表面處理金屬氧化物溶膠之組成示於表2。 除使用表面處理金屬氧化物溶膠(23-D)以外，與實施例1相同地進行，製造透明覆膜形成用塗料。繼而，與實施例1相同地製造附透明覆膜之基材，並對其進行評價。 [實施例24] 除於第1步驟中，於以TiO2 換算為2質量%之過氧化鈦酸水溶液450 g中混合包含以SiO2 計為15質量%之平均粒徑為7 nm之二氧化矽粒子之矽溶膠(日揮觸媒化成(股)製造：CATALOID SN-350)8.2 g與純水1637.1 g以外，與實施例1相同地進行，獲得固形物成分濃度為10質量%之二氧化鈦系粒子(24-A)水分散液。 之後與實施例1相同地進行，獲得表面處理金屬氧化物溶膠(24-D)。將所得之表面處理金屬氧化物溶膠之組成示於表2。 除使用表面處理金屬氧化物溶膠(24-D)以外，與實施例1相同地進行，製造透明覆膜形成用塗料。繼而，與實施例1相同地製造附透明覆膜之基材，並對其進行評價。 [實施例25] 除於第1步驟中，於以TiO2 換算為2質量%之過氧化鈦酸水溶液450 g中混合包含以SiO2 計為15質量%之平均粒徑為7 nm之二氧化矽粒子之矽溶膠(日揮觸媒化成(股)製造：CATALOID SN-350)8.2 g與純水122.6 g以外，與實施例1相同地進行，獲得固形物成分濃度為10質量%之二氧化鈦系粒子(25-A)水分散液。 之後與實施例1相同地進行，獲得表面處理金屬氧化物溶膠(25-D)。將所得之表面處理金屬氧化物溶膠之組成示於表2。 除使用表面處理金屬氧化物溶膠(25-D)以外，與實施例1相同地進行，製造透明覆膜形成用塗料。繼而，與實施例1相同地製造附透明覆膜之基材，並對其進行評價。 [實施例26] 除第1步驟中於以TiO2 換算為2質量%之過氧化鈦酸水溶液450 g中混合包含以SiO2 計為15質量%之平均粒徑為7 nm之二氧化矽粒子之矽溶膠(日揮觸媒化成(股)製造：CATALOID SN-350)8.2 g與純水122.6 g以外，與實施例1相同地進行，獲得固形物成分濃度為10質量%之二氧化鈦系粒子(26-A)水分散液。 之後除重複進行第4步驟中之使用陽離子交換樹脂之脫鹼處理以外，與實施例1相同地進行，獲得表面處理金屬氧化物溶膠(26-D)。將所得之表面處理金屬氧化物溶膠之組成示於表2。 除使用表面處理金屬氧化物溶膠(26-D)以外，與實施例1相同地進行，製造透明覆膜形成用塗料。繼而，與實施例1相同地製造附透明覆膜之基材，並對其進行評價。 [實施例27] 於第1步驟及第3步驟中，於與實施例1相同地製造之固形物成分濃度為10質量%之二氧化鈦系粒子(1-B)水分散液中緩慢添加陽離子交換樹脂(三菱樹脂(股)製造)進行脫鹼之後，分離離子交換樹脂。其後，利用超濾膜將分散介質置換為甲醇。其後進行濃縮，獲得固形物成分濃度為30質量%之二氧化鈦系微粒子(27-B)甲醇分散液。所得之二氧化鈦系粒子(27-B)甲醇分散液中所含之水分量為0.3質量%。 進而，於第2步驟中，於該二氧化鈦系粒子(27-B)甲醇分散液40 g中緩慢添加3-甲基丙烯醯氧基丙基三甲氧基矽烷(信越化學工業(股)製造：KBM-503)1.47 g。此後，於50℃下加熱攪拌19小時。繼而，將其冷卻至室溫之後，利用超濾膜將分散介質置換為丙二醇單甲醚(PGME)，獲得固形物成分濃度為30質量%之表面處理金屬氧化物溶膠(27-D)。將所得之表面處理金屬氧化物溶膠之組成示於表2。再者，於本實施例中，不進行第4步驟。 除使用表面處理金屬氧化物溶膠(27-D)以外，與實施例1相同地進行，製造透明覆膜形成用塗料。繼而，與實施例1相同地製造附透明覆膜之基材，並對其進行評價。 [實施例28] 於第1步驟中，於與實施例1相同地製造之固形物成分濃度為10質量%之二氧化鈦系粒子(1-A)水分散液117 g中緩慢添加陽離子交換樹脂(三菱樹脂(股)製造)進行脫鹼之後，分離離子交換樹脂。 其次，於第4步驟之二氧化矽層之製造中，於該溶液中緩慢添加溶解有四乙氧基矽烷(多摩化學(股)製造)8.96 g之甲醇溶液126.0 g，於50℃下加熱攪拌1小時，獲得二氧化鈦系粒子(28-C)之水/甲醇分散液。將該二氧化鈦系粒子(28-C)之水/甲醇分散液冷卻至室溫，利用超濾膜將分散介質置換為甲醇。其後進行濃縮，獲得固形物成分濃度為30質量%之二氧化鈦系粒子(28-C)甲醇分散液。所得之二氧化鈦系粒子(28-C)甲醇分散液中所含之水分量為0.3質量%。 進而，於第2步驟中，於該二氧化鈦系粒子(28-C)甲醇分散液40 g中緩慢添加3-甲基丙烯醯氧基丙基三甲氧基矽烷(信越化學工業(股)製造：KBM-503)1.47 g。此後，於50℃下加熱攪拌19小時。繼而，將其冷卻至室溫之後，利用超濾膜將分散介質置換為丙二醇單甲醚(PGME)，獲得固形物成分濃度為30質量%之表面處理金屬氧化物溶膠(28-D)。將所得之表面處理金屬氧化物溶膠之組成示於表2。再者，於本實施例中，不進行第3步驟之二氧化矽複合氧化物層之製造。 除使用表面處理金屬氧化物溶膠(28-D)以外，與實施例1相同地進行，製造透明覆膜形成用塗料。繼而，與實施例1相同地製造附透明覆膜之基材，並對其進行評價。 [實施例29] 除於第2步驟中，使用3-丙烯醯氧基丙基三甲氧基矽烷(信越化學工業(股)製造：KBM-5103)1.47 g代替3-甲基丙烯醯氧基丙基三甲氧基矽烷(信越化學工業(股)製造：KBM-503)以外，與實施例1相同地進行，獲得表面處理金屬氧化物溶膠(29-D)。將所得之表面處理金屬氧化物溶膠之組成示於表2。 除使用表面處理金屬氧化物溶膠(29-D)以外，與實施例1相同地進行，製造透明覆膜形成用塗料。繼而，與實施例1相同地製造附透明覆膜之基材，並對其進行評價。 [實施例30] 除於第2步驟中，使用3-丙烯醯氧基丙基三乙氧基矽烷(信越化學工業(股)製造：KBE-503)1.47 g代替3-甲基丙烯醯氧基丙基三甲氧基矽烷(信越化學工業(股)製造：KBM-503)以外，與實施例1相同地進行，獲得表面處理金屬氧化物溶膠(30-D)。將所得之表面處理金屬氧化物溶膠之組成示於表2。 除使用表面處理金屬氧化物溶膠(30-D)以外，與實施例1相同地進行，製造透明覆膜形成用塗料。繼而，製造附透明覆膜之基材並對其進行評價。 [實施例31] 除於第2步驟中，使用3-丙烯醯氧基丙基二乙甲基矽烷(信越化學工業(股)製造：KBE-502)1.47 g代替3-甲基丙烯醯氧基丙基三甲氧基矽烷(信越化學工業(股)製造：KBM-503)以外，與實施例1相同地進行，獲得表面處理金屬氧化物溶膠(31-D)。將所得之表面處理金屬氧化物溶膠之組成示於表2。 除使用表面處理金屬氧化物溶膠(31-D)以外，與實施例1相同地進行，製造透明覆膜形成用塗料。繼而，與實施例1相同地製造附透明覆膜之基材，並對其進行評價。 [實施例32] 除於第2步驟中，使用丙二醇單甲醚乙酸酯(PGMEA)代替丙二醇單甲醚(PGME)以外，與實施例1相同地進行，獲得固形物成分濃度為30質量%之表面處理金屬氧化物溶膠(32-D)。將所得之表面處理金屬氧化物溶膠之組成示於表2。 除使用表面處理金屬氧化物溶膠(32-D)以外，與實施例1相同地進行，製造透明覆膜形成用塗料。繼而，與實施例1相同地製造附透明覆膜之基材，並對其進行評價。 [實施例33] 於第4步驟中，於與實施例1相同地製造之二氧化鈦系粒子(1-C)之水/甲醇分散液中緩慢添加陽離子交換樹脂(三菱樹脂(股)製造)進行脫鹼之後，分離離子交換樹脂。將所得之二氧化鈦系粒子(33-C)之水/甲醇分散液冷卻至室溫，利用超濾膜將分散介質置換為甲醇。其後進行濃縮，獲得固形物成分濃度為30質量%之二氧化鈦系微粒子(33-C)甲醇分散液40 g。 之後與實施例1相同地進行，獲得表面處理金屬氧化物溶膠(33-D)。將所得之表面處理金屬氧化物溶膠之組成示於表2。 除使用表面處理金屬氧化物溶膠(33-D)以外，與實施例1相同地進行，製造透明覆膜形成用塗料。繼而，與實施例1相同地製造附透明覆膜之基材，並對其進行評價。 [比較例1] 於第4步驟中，於與實施例1相同地製造之固形物成分濃度為30質量%之二氧化鈦系粒子(1-C)甲醇分散液中利用超濾膜將分散介質置換為丙二醇單甲醚(PGME)。藉此，獲得未藉由包含(甲基)丙烯醯基之有機矽化合物進行表面處理之固形物成分濃度為30質量%之金屬氧化物溶膠(C1-D)40 g。將所得之金屬氧化物溶膠之組成示於表3。 除使用表面處理金屬氧化物溶膠(C1-D)以外，與實施例1相同地進行，製造透明覆膜形成用塗料。繼而，與實施例1相同地製造附透明覆膜之基材，並對其進行評價。 [比較例2] 除於第2步驟中，將3-甲基丙烯醯氧基丙基三甲氧基矽烷(信越化學工業(股)製造：KBM-503)之量設為15.6 g以外，與實施例1相同地進行，獲得表面處理金屬氧化物溶膠(C2-D)。將所得之金屬氧化物溶膠之組成示於表3。 除使用表面處理金屬氧化物溶膠(C2-D)以外，與實施例1相同地進行，製造透明覆膜形成用塗料。繼而，與實施例1相同地製造附透明覆膜之基材，並對其進行評價。 [比較例3] 除於第1步驟中，於與實施例1相同地製造之以TiO2 換算為2質量%之過氧化鈦酸水溶液450 g中混合包含15質量%之平均粒徑為7 nm之二氧化矽粒子之矽溶膠(日揮觸媒化成(股)製造：CATALOID SN-350)65.0 g與純水532 g以外，與實施例1相同地進行，獲得固形物成分濃度為10質量%之二氧化鈦系粒子(C3-A)水分散液。 之後亦與實施例1相同地進行，獲得表面處理金屬氧化物溶膠(C3-D)。將所得之表面處理金屬氧化物溶膠之組成示於表3。 除使用表面處理金屬氧化物溶膠(C3-D)以外，與實施例1相同地進行，製造透明覆膜形成用塗料。繼而，與實施例1相同地製造附透明覆膜之基材，並對其進行評價。 [比較例4] 於第1步驟中，於與實施例1相同地製造之以TiO2 換算為2質量%之過氧化鈦酸水溶液280.4 g中混合陽離子交換樹脂35.0 g，於其中於攪拌下緩慢添加以SnO2 換算為1質量%之錫酸鉀水溶液527.8 g之後，分離陽離子交換樹脂。 繼而，混合包含15質量%之平均粒徑為7 nm之二氧化矽粒子之矽溶膠(日揮觸媒化成(股)製造：CATALOID SN-350)8.0 g與純水180.0 g，於高壓釜中於165℃下進行18小時水熱處理。 其次，將所得之水溶液冷卻至室溫之後，利用超濾膜裝置進行濃縮，獲得固形物成分濃度為10質量%之二氧化鈦系微粒子(C4-A)水分散液。 之後與實施例1相同地進行，獲得表面處理金屬氧化物溶膠(C4-D)。將所得之表面處理金屬氧化物溶膠之組成示於表3。 除使用表面處理金屬氧化物溶膠(C4-D)以外，與實施例1相同地進行，製造透明覆膜形成用塗料。繼而，與實施例1相同地製造附透明覆膜之基材，並對其進行評價。 [參考例1] 於第1步驟中，於與實施例1相同地製造之固形物成分濃度為10質量%之二氧化鈦系微粒子(1-A)水分散液中緩慢添加陽離子交換樹脂(三菱樹脂(股)製造)進行脫鹼之後，分離離子交換樹脂。其後利用超濾膜將分散介質置換為甲醇。其後進行濃縮，獲得固形物成分濃度為30質量%之二氧化鈦系粒子(R1-A)甲醇分散液。所得之二氧化鈦系粒子(R1-A)甲醇分散液中所含之水分量為0.3質量%。 進而，於第2步驟中，於該二氧化鈦系粒子(R1-A)甲醇分散液40 g中緩慢添加3-甲基丙烯醯氧基丙基三甲氧基矽烷(信越化學工業(股)製造：KBM-503)1.47 g。此後，於50℃下加熱攪拌19小時。繼而，將其冷卻至室溫之後，利用超濾膜將分散介質置換為丙二醇單甲醚(PGME)，獲得固形物成分濃度為30質量%之表面處理金屬氧化物溶膠(R1-D)。將所得之表面處理金屬氧化物溶膠之組成示於表2。 除使用表面處理金屬氧化物溶膠(R1-D)以外，與實施例1相同地進行，製造透明覆膜形成用塗料。繼而，與實施例1相同地製造附透明覆膜之基材，並對其進行評價。 [表1] [表2] [表3] The surface-treated metal oxide sol of the present invention comprises a surface-treated metal oxide particle and a dispersion medium provided on the surface of the metal oxide particle with an organosilicon compound containing a (meth) acrylfluorene group. The metal oxide particles contain TiO2 Calculated as 50% by mass or more of titanium dioxide particles. With respect to 100 parts by mass of the surface-treated metal oxide particles, the above-mentioned organosilicon compound represented by formula (1) is represented by R1 n -SiO(4-n) / 2 (Where R1 It is at least one selected from the group consisting of a methacryl group and an acryl group, and may be the same as or different from each other. n is an integer of 1 to 3), and 0.1 to 60 parts by mass is provided. R1 n -SiX1 (4-n) (1) (where R1 It is at least one selected from the group consisting of a methacryl group and an acryl group, and may be the same as or different from each other. n is an integer of 1 to 3. X1 Alkoxy). The surface-treated metal oxide sol having such a structure will be described in detail below. [Metal Oxide Particles] In order to make the surface-treated metal oxide particles have a higher refractive index, it is preferable that the refractive index of the metal oxide particles itself is 2.0 or more, and the method includes TiO2 Calculated as 50% by mass or more of titanium dioxide. Specifically, titanium dioxide or a composite oxide containing titanium and other metals is preferred. These can be used alone or in combination. Examples of the metal include silicon, tin, iron, and cerium. These kinds of metals may be one kind or plural kinds. However, it is known that titanium dioxide has a photocatalyst function, so it has photoactivity, and can decompose organic substances coexisting in the film. Therefore, if the photoactivity is too strong, the weather resistance of the film is reduced. Therefore, it is preferable to use a composite oxide of titanium dioxide and silicon dioxide or tin oxide with a lower refractive index to adjust the photoactivity. Specifically, exemplified is a preferred titanium dioxide2 / SiO2 ), Titanium dioxide, silicon dioxide, tin oxide (TiO2 / SiO2 / SnO2 ) Of composite oxide particles. As the form of the titanium dioxide, either a rutile type or an anatase type may be used, and a mixture of these may also be used. Especially as a resist material, in order to make the refractive index greater than 1.6, it is preferred that the titanium dioxide in the composite oxide particles be TiO2 It contains more than 50% by mass. TiO2 / SiO2 In that case, it is preferable to contain TiO2 75% by mass or more, containing SiO2 25% by mass or less. Here, TiO2 / SiO2 If the ratio is less than 75/25, the refractive index may decrease. More preferably TiO2 80 to 90% by mass, SiO2 It is 10 to 20% by mass. TiO2 / SiO2 / SnO2 In this case, TiO is preferred2 50 to 95% by mass, SiO2 3 to 25% by mass, SnO2 It is 2 to 47% by mass. Here, if TiO2 / (SiO2 ＋ SnO2 ) Is less than 50/50, the refractive index may be lowered. In contrast, if TiO2 / (SiO2 ＋ SnO2 If the ratio of) is more than 95/5, it may be difficult to express the difference from the particles of titanium dioxide alone, and as a result, the photoactivity and weather resistance may become problems. More preferably TiO2 70 to 90% by mass, SiO2 10 to 20% by mass, SnO2 2 to 30% by mass, TiO2 / (SiO2 ＋ SnO2 ) Is more preferably 70/30 to 90/10. In addition, in order to adjust the photoactivity of the resist material,2 / SiO2 TiO2 / SiO2 / SnO2 A third component such as iron or cerium oxide is added to the composite oxide particles. The iron or cerium dioxide doping treatment is preferable in terms of suppression of photoactivity. 100 parts by mass of the doping amount relative to the target particle is preferred as Fe2 O3 Or CeO2 , Less than 10 parts by mass. If the doping amount of iron or cerium dioxide is Fe2 O3 Or CeO2 If it is 10 parts by mass or more, the appearance of the coating film may be colored. The doping amount is more preferably less than 5 parts by mass, and even more preferably less than 3 parts by mass. [Surface-treated metal oxide particle] <Layer of an organosilicon compound containing a (meth) acrylfluorene group> The surface-treated metal oxide particle is coated on the surface of the metal oxide particle with an organosilicon compound represented by formula (1) As a surface treatment agent, R1 n -SiX1 (4-n) (1) (where R1 It is at least one selected from the group consisting of a methacryl group and an acryl group, and may be the same as or different from each other. n is an integer of 1 to 3. X1 Alkoxy). The organosilicon compound containing a (meth) acrylfluorenyl group is represented by R with respect to 100 parts by mass of the metal oxide particles.1 n -SiO(4-n) / 2 (Where R1 It is at least one selected from the group consisting of methacrylfluorenyl and acrylfluorenyl, and may be the same as or different from each other. n is an integer of 1 to 3), and 0.1 to 60 parts by mass is provided. By disposing the organosilicon compound containing a (meth) acrylfluorenyl group on the surface of the metal oxide particles, the dispersibility or binding property of the surface-treated metal oxide particles and the resin in the resist material is improved. Here, if the amount of the organosilicon compound is less than 0.1 parts by mass, the compatibility with the resin may be insufficient, aggregation of particles may occur, haze may increase, and total light transmittance may decrease. In addition, the sensitivity and the residual film rate during exposure and development may be insufficient. In contrast, it is difficult to cover more than 60 parts by mass on the surface area of the particles. The amount of the organic silicon compound is preferably 1 to 50 parts by mass, and more preferably 3 to 30 parts by mass. The organosilicon compound can exist in the sol as an unreacted substance without surface treatment. The amount is based on 100 parts by mass of the metal oxide particles.1 n -SiO(4-n) / 2 (Where R1 It is at least one selected from the group consisting of a methacryl group and an acryl group, and may be the same as or different from each other. n is an integer of 1 to 3) and is 99.9 parts by mass or less. When the free organic silicon compound is 0 parts by mass, the organic silicon compound in the surface-treated metal oxide sol is only an organic silicon compound provided on the surface of the metal oxide. In addition, even if it is more than 99.9 parts by mass, improvement in dispersibility cannot be expected, and the refractive index of the film also decreases. That is, it is preferable that the amount of the organosilicone compound containing a (meth) acrylfluorene group in the surface-treated metal oxide sol is added to the surface of the metal oxide particles and those that are freely present in the sol. Is 100 parts by mass with respect to the metal oxide particles, and R is1 n -SiO(4-n) / 2 (Where R1 It is at least one selected from the group consisting of a methacryl group and an acryl group, and may be the same as or different from each other. n is an integer of 1 to 3), and 0.1 to 100 parts by mass is provided. Here, if the amount of the organic silicon compound is less than 0.1 parts by mass, the effect of surface treatment cannot be obtained. On the contrary, if it is more than 100 parts by mass, the refractive index of the film may decrease. The amount of the organic silicon compound is more preferably 1 to 70 parts by mass, and still more preferably 5 to 40 parts by mass. The organosilicon compound is not particularly specified as long as it is an organosilicon compound containing a (meth) acrylfluorenyl group represented by formula (1), and examples thereof include 3-methacryloxypropyldimethyl Oxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, Methacryloxypropyldiethoxysilane, 3-propenyloxypropyltriethoxysilane, and the like. Especially preferred is 3-methacryloxypropyltrimethoxysilane. These organosilicon compounds may be used in the state of a monomer, or may be one polymer or a plurality of polymers selected from the organosilicon compounds, or a mixture thereof. On the surface-treated metal oxide particles, a material selected from the group consisting of silicon oxide zirconia, silicon oxide alumina, and At least one of a silicon dioxide composite oxide layer of silicon dioxide titanium dioxide, silicon dioxide tin oxide, and a separate layer of silicon dioxide. By providing these layers, the surface of the metal oxide particles is only covered with a surface-treated metal oxide particle containing an organosilicon compound containing a (meth) acrylfluorene group, and the adjustment of the refractive index, sensitivity, resolution, and photoactivity becomes easily. <Silicon dioxide composite oxide layer> Here, the layer of the silicon dioxide composite oxide is SiO2 / MOX (Of which MOX Selected from ZrO2 , Al2 O3 TiO2 , SnO2 The molar ratio of any one of them) is preferably 33.3 / 66.7 to 99.5 / 0.5. By providing this layer, the light activity and refractive index of the metal oxide particles can be mainly adjusted. Here, if SiO2 / MOX When the molar ratio is less than 33.3 / 66.7, it may be difficult to obtain a uniform coating layer and the metal oxide particles may aggregate. On the contrary, if it is larger than 99.5 / 0.5, it is difficult to distinguish it from the silicon dioxide layer, so it is not necessary to provide a separate arrangement from the silicon dioxide layer. The molar ratio is more preferably 50.0 / 50.0 to 95.2 / 4.8, and still more preferably 50.0 / 50.0 to 76.9 / 23.1. In addition, the amount of the silicon dioxide composite oxide is based on 100 parts by mass of the metal oxide particles, with (SiO2 ＋ MOX ) Is 1 to 180 parts by mass. When the amount of the silicon dioxide composite oxide is less than 1 part by mass, the weather resistance may be insufficient. On the contrary, if it is more than 180 parts by mass, the required refractive index may not be obtained. The amount is preferably 2 to 30 parts by mass, and more preferably 3 to 10 parts by mass. <Silicon dioxide layer> The amount of silicon dioxide in the silicon dioxide layer is 100 parts by mass with respect to the metal oxide particles, and SiO2 It is 0.1 to 100 parts by mass. By providing a silicon dioxide layer, the photoactivity adjustment of the metal oxide particles and the improvement of the dispersibility of the particles can be mainly realized. Here, if the amount of silicon dioxide is less than 0.1 parts by mass, weather resistance adjusted by photoactivity may be insufficient, and it may be difficult to coat the metal oxide with an organic silicon compound containing a (meth) acrylfluorenyl group thereafter. . On the other hand, if it is more than 100 parts by mass, the required refractive index may not be obtained. The preferable amount is 0.5 to 30 parts by mass, and more preferably 1 to 10 parts by mass. The separate layer of silicon dioxide can be provided by an inorganic silicon compound such as an aqueous solution of a silicic acid alkali such as water glass or a silicic acid solution, or by using ethyl orthosilicate (TEOS) or methyl orthosilicate (TMOS). Organosilicon compound set. On the surface-treated metal oxide particles, a layer between the metal oxide particles and the (meth) acrylfluorene-containing organosilicon compound on the surface of the particle is further preferably provided in order from the side close to the metal oxide particles. It is a layer of a silicon dioxide composite oxide, followed by a separate layer of silicon dioxide, and its outermost surface is a layer of an organosilicon compound containing a (meth) acrylfluorene group. This is because three layers are combined in sequence, and the refractive index, sensitivity, resolution, and photoactivity can be adjusted in stages. In particular, the surface OH groups of the second silicon dioxide layer are generated, so that a (meth) acrylfluorene group is given here. Since it becomes easy, the dispersibility or binding property with a resist material can be improved. << Average particle diameter >> The average particle diameter of the surface-treated metal oxide particles is preferably 5 to 500 nm. If the average particle diameter is less than 5 nm, it is difficult to manufacture particles of this size. If it is larger than 500 nm, the transparency of the resist material is difficult to achieve although the content is also determined. A more preferable average particle diameter is 5 to 200 nm, and even more preferably 10 to 25 nm. << Refractive Index >> In order to make the refractive index of the resist material larger than 1.6, the refractive index of the surface-treated metal oxide particles is preferably 1.7 or higher. [Dispersion medium] As the dispersion medium of the surface-treated metal oxide sol, a conventionally known organic solvent can be used. In particular, when used as a resist material, if the dispersing medium also considers the workability of the resist material, the dispersing medium should contain at least one solubility parameter (SP value) of 10 or more and a boiling point at atmospheric pressure. Organic solvents exceeding 100 ℃. The organic solvent is preferably contained in the dispersion medium in an amount of 30 to 95% by mass. Here, if the SP value is less than 10, the dispersibility of the surface-treated metal oxide particles becomes low. In addition, if the organic solvent has a boiling point of 100 ° C or lower, drying may be rapid during coating and a film may be formed before leveling. Therefore, there is a risk of bumps on the coating film. Furthermore, when the amount of the organic solvent in the dispersion medium is less than 30% by mass, the dispersibility of the surface-treated metal oxide particles is reduced. Conversely, if it is more than 95% by mass, it is difficult to obtain a desired film thickness. A more preferable amount is 40 to 90% by mass, and still more preferably 50 to 80% by mass. Examples of the organic solvent having an SP value of 10 or more and a boiling point exceeding 100 ° C include propylene glycol monomethyl ether (PGM), propylene glycol monomethyl ether acetate (PGMEA), ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethyl acetate. Glycol mono-n-butyl ether, acetoacetone, ethylene glycol, diphenyl ether, glycerol, formamidine, benzyl alcohol, N-methylpyrrolidone, glycerol, cyclohexanone, diethylene glycol mono Diethyl ether, ethylene glycol monophenyl ether, γ-butyrolactone, diethyl phthalate, dimethyl phthalate, dimethyl sulfene, 4-hydroxy-4-methyl-2-pentanone (DAA), 1-butanol, 2-butanol, 1,3-butanediol, 1,4-butanediol, 1,4-dioxane, and the like. Especially preferred is propylene glycol monomethyl ether (PGM). In order to further improve the dispersibility in the dispersion medium, at least one solvent having an SP value of 13 or more and a boiling point of 100 ° C. or less at atmospheric pressure may be contained. The content of the solvent in the dispersion medium is preferably less than 20% by mass. By containing the solvent, the solvent is fused and the stability of the sol is improved. When the solvent contains 20% by mass or more, bumps of the coating film may occur and hardness may be insufficient. A more preferable amount is 1 to 15% by mass, and still more preferably 3 to 12% by mass. Examples of the solvent having an SP value of 13 or higher and a boiling point of 100 ° C or lower include lower alcohols and water. Especially preferred are methanol and ethanol. <Impurity Components> In the surface-treated metal oxide sol, sodium, potassium, or ammonia may be contained as impurity components. If any one of these is present in a large amount, the stability of the sol is reduced. In addition, the workability as a resist material is also deteriorated, making it difficult to expose and develop a pattern. Therefore, sodium is preferably Na2 O concentration meter is 25 ppm or less, more preferably less than 20 ppm, and potassium is preferably K2 O concentration is less than 0.5% by mass, ammonia is preferably NH3 The density meter did not reach 1000 ppm. "Concentration of Surface-treated Metal Oxide Sol" The solid component concentration of the surface-treated metal oxide sol is preferably 5 to 70% by mass. When the solid component concentration is less than 5 mass%, the required refractive index or film hardness may not be obtained. If the solid component concentration is higher than 70% by mass, it becomes difficult to achieve transparency of the resist material. A more preferable amount is 10 to 60% by mass, and still more preferably 20 to 40% by mass. [Production method of surface-treated metal oxide sol] <First step> The first step is a step of producing metal oxide particles. The manufacturing method will be described below. <Production method of metal oxide sol> ＞ Production of titanic acid aqueous solution≫ An aqueous titanate gel or sol is prepared by a conventionally known method. An aqueous titanate gel is obtained by adding an alkali to an aqueous solution such as titanium chloride, titanium sulfate, and the like to neutralize it. The aqueous titanate sol is obtained by passing an aqueous solution such as titanium chloride or titanium sulfate through an ion exchange resin to remove anions. The term "hydrated titanic acid" used herein means titanium oxide hydrate or titanium hydroxide. Next, hydrogen peroxide is added to the obtained aqueous titanate gel or aqueous titanate sol or a mixture thereof to dissolve the aqueous titanic acid to prepare a uniform aqueous solution. In this case, heating or stirring is preferred. At this time, if the concentration of the hydrous titanic acid becomes too high, it takes a long time to dissolve the hydrous titanic acid, and precipitation of the gel in an undissolved state is formed, or the viscosity of the obtained aqueous solution becomes high, which is not preferable. So with TiO2 The density meter is about 10% by mass or less, and preferably about 5% by mass or less. If the amount of hydrogen peroxide to be added is H2 O2 / TiO2 When the mass ratio is 1 or more, water-containing titanic acid can be completely dissolved. If H2 O2 / TiO2 If the ratio is less than 1, the unreacted gel or sol remains because the water-containing titanic acid is not completely dissolved, which is not preferable. Also, although H2 O2 / TiO2 The larger the ratio, the faster the dissolution rate of the hydrous titanic acid, and the reaction ends in a short time. However, if hydrogen peroxide is used excessively, the unreacted hydrogen peroxide will remain in the system in large quantities, which will adversely affect the subsequent steps. So bad. So taking H2 O2 / TiO2 It is preferable to use hydrogen peroxide in an amount of about 1 to 6, preferably about 2 to 6. When hydrogen peroxide is used in such an amount, the hydrous titanic acid is completely dissolved within about 0.5 to 20 hours. The reaction temperature at this time is 50 ° C or higher, and preferably 70 ° C or higher.氧化钛 Titanium dioxide (TiO2 ) Production of aqueous dispersion ≫ Next, the aqueous titanate-dissolved aqueous solution (aqueous titanate solution) obtained as described above is heated to 60 ° C or higher, preferably 80 ° C or higher, to hydrolyze titanic acid. Thereby, TiO is obtained2 Water dispersion of particles.氧化钛 Titanium dioxide (TiO2)2 / SiO2 ) Production of water dispersion liquid: A silicon compound is mixed with a specific amount in the above titanic acid aqueous solution, and heated to 60 ° C or higher, preferably 80 ° C or higher, to hydrolyze the titanic acid. Thereby, TiO is obtained2 / SiO2 Water dispersion of particles. Here, as the silicon compound, a silicic acid solution obtained by debasing an alkali silicic acid salt solution using a cation exchange resin, a silica sol obtained by neutralizing an alkali silicic acid with an acid, or an alkoxide such as ethyl silicate is used. A solution or dispersion of a silicon compound such as an organic compound or its hydrolysate. Alternatively, a commercially available silica sol may be used. In these cases, the average particle diameter of the silicon dioxide is preferably 500 nm or less. TiO2 / SiO2 The ratio is above 75/25. Also, TiO2 / SiO2 The ratio is preferably 80/20 or more. As a method for adding a solution or dispersion of a silicon compound to an aqueous titanate solution, a method of slowly adding a solution or dispersion of a silicon compound while heating the aqueous titanate solution, and mixing a titanium dioxide sol precursor with a solution or dispersion of a silicon compound The method of heating afterwards can be selected according to the concentration of titanium dioxide, the concentration of silicon dioxide in the solution or dispersion of the silicon compound. Although when the concentration of titanium dioxide is thinner than 1% by mass, the method of mixing the two does not cause any obstacle, but when the concentration of titanium dioxide is thicker than 1% by mass, there is a case In the case where silicon dioxide aggregates titanium dioxide, and if the concentration of silicon dioxide is high, aggregation and polymerization of silicon dioxide alone occur, so a method of slow addition is preferred. In order to promote the reaction between the silicon compound and titanium dioxide, it is generally preferred that the temperature at the time of addition or mixing is heated to about 60 ° C or higher. However, when alkoxides such as ethyl silicate are used, the hydrolysis rate is faster, and colloidal particles of silicon dioxide are easily formed in the mixed solution. Therefore, the alkoxide is slowly added at a lower temperature of about 40 ° C 3. A method of raising the temperature to about 60 ° C or higher after the addition is completed to complete the reaction. The pH of the mixed solution when the silicon compound is added is preferably neutral or alkaline from the viewpoint of the stability of the titanic acid aqueous solution and the formation of the titania sol, and it is usually performed within a range of about 6 to 10. Yu TiO2 / SiO2 When the aqueous dispersion is concentrated, a known method such as an evaporation method or an ultrafiltration method can be used.氧化钛 Titanium dioxide, silicon dioxide, tin oxide (TiO2 / SiO2 / SnO2 ) Production of water dispersion liquid: A silicon compound or a tin compound is mixed with a specific amount in the above titanic acid aqueous solution, and heated to 60 ° C or higher, preferably 80 ° C or higher to hydrolyze the titanic acid. Thereby, TiO is obtained2 / SiO2 / SnO2 Water dispersion of particles. Here, as the silicon compound, the same as the above-mentioned TiO can be used.2 / SiO2 The same users in the manufacturing. As the tin compound to be added to the titanic acid aqueous solution, an aqueous solution or dispersion of a tin compound such as tin chloride, tin sulfate, or tin oxychloride is used. The method for adding such a tin compound to an aqueous titanic acid solution is the same as adding the above-mentioned TiO2 / SiO2 The silicon compounds are the same. The order of addition can be either first or simultaneously. TiO2 / SiO2 / SnO2 The ratio is TiO2 70 to 90% by mass, SiO2 10 to 20% by mass, SnO2 2 to 30% by mass, TiO2 / (SiO2 ＋ SnO2 ) The ratio is in the range of 50/50 to 95/5. Other manufacturing conditions and the above TiO2 / SiO2 the same. TiO is preferred2 70 to 90% by mass, SiO2 10 to 20% by mass, SnO2 2 to 30% by mass, TiO2 / (SiO2 ＋ SnO2 ) Is in the range of 70/30 to 90/10. Thallium-iron or cerium oxide doped ≫oriented TiO2 / SiO2 Or TiO2 / SiO2 / SnO2 The treatment doped with iron or cerium dioxide is obtained by preparing an aqueous solution of iron or cerium chloride and a titanium salt and adding an alkali to neutralize it during the production of the titanic acid aqueous solution described above. Manufacturing method thereafter, manufacturing method of titanic acid aqueous solution, and TiO2 / SiO2 Manufacturing method or TiO2 / SiO2 / SnO2 The manufacturing method is performed in the same manner. Doping amount relative to the object's TiO2 / SiO2 Or TiO2 / SiO2 / SnO2 100 parts by mass as Fe2 O3 Or CeO2 , Less than 10 parts by mass. The doping amount is preferably less than 5 parts by mass, and more preferably less than 3 parts by mass. (Replacement of Organic Solvents) Prior to the "second step" described later, the aqueous dispersion of the target metal oxide particles is replaced with a conventionally known organic solvent. As the organic solvent, alcohols, esters, glycols, and ethers can be used. Specific examples of the alcohol include methanol, ethanol, propanol, and 2-propanol. Examples of the esters include methyl acetate, ethyl acetate, isopropyl acetate, and propyl acetate. Examples of glycols include ethylene glycol and hexanediol. As the ethers, there are diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol isopropyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, etc. . These can be used alone or in combination of two or more. Among these, particularly preferred are methanol and ethanol as lower alcohols. The solvent replacement can be performed by a conventionally known method such as using an ultrafiltration device. The content of water in the dispersion medium after the solvent replacement is preferably at most 20% by mass. 〈Second Step〉 The second step is to treat the surface of the metal oxide particles with an organosilicon compound containing a (meth) acrylfluorenyl group represented by formula (1), and include ( A layer of a methyl) acrylfluorenyl organosilicon compound. The manufacturing method will be described below. <Production of a layer of an organosilicon compound containing a (meth) acrylfluorenyl group> To the organic solvent dispersion of the metal oxide particles, an organosilicon compound containing a (meth) acrylfluorenyl group represented by the formula (1) is added. . Although the method of addition is not particularly limited, it is preferable to add the two while stirring them in such a manner that the two are sufficiently mixed. In order to promote the reaction, it may be heated to about 40 to 60 ° C. The addition amount of the (meth) acrylfluorene-based organosilicon compound is only added as follows: with respect to 100 parts by mass of metal oxide particles, R1 n -SiO(4-n) / 2 (Where R1 It is at least one selected from the group consisting of a methacryl group and an acryl group, and may be the same as or different from each other. n is an integer of 1 to 3), and it is set to 0.1 to 60 parts by mass; and if it is accumulated on the surface of the metal oxide particles and those other than freely present in the sol, it is 100 parts by mass with R1 n -SiO(4-n) / 2 (Where R1 It is at least one selected from the group consisting of methacrylfluorenyl and acrylfluorenyl, and may be the same as or different from each other. n is an integer of 1 to 3), and 0.1 to 100 parts by mass is provided. The preferable amount of the organic silicon compound is 1 to 70 parts by mass, and more preferably 5 to 40 parts by mass. ≪Solvent Replacement≫ Then, the solvent replacement is performed by an organic solvent having an SP value of 10 or more and a boiling point exceeding 100 ° C. by a previously known method. The organic solvent is contained in the dispersion medium in an amount of 30 to 95% by mass. Thereby, the surface-treated metal oxide sol of the present invention is obtained. In the surface-treated metal oxide sol, in order to further improve the dispersibility, the content of the lower alcohol and water may be less than 20% by mass. Among them, sodium is preferably Na2 O concentration meter is 25 ppm or less, more preferably less than 20 ppm, and potassium is preferably K2 O concentration is less than 0.5%, ammonia is preferably NH3 The density meter did not reach 1000 ppm. 〈3rd step〉 The third step is to install a silicon dioxide composite oxide selected from the group consisting of silica zirconia, silica alumina, silica titanium dioxide, and silica tin oxide on the surface of the metal oxide particles. Layers. The manufacturing method will be described below. <Production of a layer of a silicon dioxide composite oxide> In order to provide a layer of a silicon dioxide composite oxide of metal oxide particles provided on an object, a layer selected from a silicon compound, a zirconium compound, an aluminum compound, a titanium compound, and a tin compound is used. Compounds as raw materials. Here, as the silicon compound, a silicic acid solution obtained by debasing an alkali silicic acid salt solution using a cation exchange resin, a silica sol obtained by neutralizing an alkali silicic acid with an acid, or an alkane such as ethyl silicate can be used. A solution or dispersion of a silicon compound such as an oxide or a hydrolyzate thereof. Alternatively, a commercially available silica sol may be used. As the metal compound other than the silicon compound, an aqueous solution or dispersion of a chloride or a sulfuric acid compound, an ammonium carbonate compound, a hydroxychloride compound, or the like, and a metal alkoxide or the like are used. Hydrogen peroxide is added to those obtained by adding an alkali to neutralize or hydrolyze to obtain an aqueous metal acid solution selected from zirconium, aluminum, titanium, and tin. Next, a solution or dispersion of a silicon compound and the above-mentioned metal acid aqueous solution are added to the dispersion of the target metal oxide particles. The method of addition is not particularly limited, but it is preferably added while stirring the two so that they are sufficiently mixed. Moreover, in order to promote a reaction, you may heat. Silicon compounds and metal compounds other than silicon compounds2 / MOX (Of which MOX Selected from ZrO2 , Al2 O3 TiO2 , SnO2 Any one of them) has a molar ratio of 33.3 / 66.7 to 99.5 / 0.5. The preferred molar ratio is 50.0 / 50.0 to 95.2 / 4.8, and more preferably 50.0 / 50.0 to 76.9 / 23.1. In addition, the amount thereof is (SiO2 ＋ MOX ) Is 1 to 180 parts by mass. The preferable amount is 2 to 30 parts by mass, and more preferably 3 to 10 parts by mass. <Fourth Step> The fourth step is a method in which a silicon dioxide layer is provided on the surface of the metal oxide particles. The manufacturing method will be described below. ＜ Production of silicon dioxide layer ＞ In order to provide a silicon dioxide layer of metal oxide particles provided on an object, a silicic acid solution obtained by dealkaliating a silicic acid alkali solution with a cation exchange resin is used, and silicon is neutralized with an acid A solution or dispersion of a silicon sol obtained from an acid or alkali salt, or an alkoxide such as ethyl silicate or a hydrolyzate thereof, or a silicon compound is used as a raw material. Alternatively, a commercially available silica sol may be used. A solution or dispersion of a silicon compound is added to the dispersion of the target metal oxide particles. The method of addition is not particularly limited, but it is preferably added while stirring the two so that they are sufficiently mixed. Moreover, in order to promote a reaction, you may heat. Silicon compound is 100 parts by mass of metal oxide particles, and2 It is 0.1 to 100 parts by mass. The preferable amount is 0.5 to 30 parts by mass, and more preferably 1 to 10 parts by mass. «Order of Steps» The surface-treated metal oxide particles constituting the present invention are provided on the surface with an organosilicon compound containing a (meth) acrylfluorenyl group represented by the formula (1). The order of steps is not particularly limited as long as the constituent can be realized. Among them, if the productivity and quality stability at the time of production are considered, the "second step" in which it is carried out is preferably performed last among the above-mentioned first to fourth steps. The "first step" for producing metal oxide particles is preferably performed first among the above-mentioned first to fourth steps. As a sequence of steps for manufacturing the surface-treated metal oxide particles, an example is as follows: manufacturing metal oxide particles (first step), and secondly, the surface of the metal oxide particles is provided with an organosilicon compound containing a (meth) acrylfluorene group ( The second step) sequence; manufacturing metal oxide particles (first step), followed by the surface of the metal oxide particles is selected from the group consisting of silicon dioxide zirconia, silicon dioxide alumina, silicon dioxide titania, silicon dioxide A layer of a silicon dioxide composite oxide in tin oxide (third step), and thereafter a sequence of an organosilicon compound containing a (meth) acrylfluorenyl group (second step) is set; and metal oxide particles are produced (first step) Secondly, a silicon dioxide layer is provided on the surface of the metal oxide particles (the fourth step), and then an organic silicon compound containing a (meth) acrylfluorenyl group is provided (the second step); the production of the metal oxide particles (the second step) 1 step), next to the surface of the metal oxide particles, a composite oxide of silicon dioxide selected from the group consisting of silicon dioxide zirconia, silicon dioxide alumina, silicon dioxide titania, and silicon dioxide tin oxide is provided. The layer (Step 3), silicon dioxide layer is further provided (Step 4), after which the organic silicon compound is provided comprising a (meth) Bing Xixi group of (Step 2) of the order. ≪Dealkalizing step≫ In the above-mentioned first to fourth steps, in order to allow the reaction to proceed, it is preferable to perform a dealkaliizing treatment as necessary. For the debasing treatment, a conventionally known method such as the use of an ion exchange resin or an ultrafiltration device can be used. In the debasing step, the sodium in the surface-treated oxide sol of the present invention obtained in the second step is preferably Na2 O concentration meter is 25 ppm or less, more preferably less than 20 ppm, potassium is K2 O concentration meter is less than 0.5%, ammonia is NH3 Appropriately implement the method with the concentration meter below 1000 ppm. [Examples] Examples will be specifically described below. The invention is not limited by these examples. [Example 1] <Production of titanium dioxide-based particles (using the first step)>2 450 g of a titanium tetrachloride aqueous solution converted into 2 mass% of titanium tetrachloride and 176 g of 15 mass% ammonia water were mixed to prepare a white slurry solution having a pH of 8.6. Then, the slurry was filtered, and then washed with pure water to obtain 180 g of a water-containing titanate filter cake having a solid content of 5% by mass. Next, 180 g of the filter cake was added with 205.6 g of 35% by mass hydrogen peroxide water and 514.4 g of pure water, and then heated at 80 ° C. for 1 hour to obtain TiO2 900 g of an aqueous solution of peroxytitanic acid containing 2% by mass of peroxytitanic acid is converted. This aqueous solution of peroxytitanic acid was transparent yellow-brown and had a pH of 8.1. Then, 450 g of the peroxytitanic acid aqueous solution was mixed with 8.2 g of a silica sol (manufactured by Nippon Kasei Kasei Co., Ltd .: CATALOID SN-350) containing 15% by mass of silicon dioxide particles having an average particle diameter of 7 nm, and 8.2 g of 589 g of pure water was hydrothermally treated in an autoclave at 165 ° C for 18 hours. Next, the obtained aqueous solution was cooled to room temperature and then concentrated using an ultrafiltration membrane device to obtain a titanium dioxide-based particle (1-A) aqueous dispersion having a solid content concentration of 10% by mass. The refractive index of the particles of the titanium dioxide-based fine particles (1-A) was 2.3. <Production of silicon dioxide composite oxide layer (using the third step)> Including ZrO2 15% by mass of ammonia was slowly added to 263 g of an aqueous zirconium oxychloride solution converted to 2% by mass of zirconium oxychloride under stirring to obtain a slurry solution containing zirconium hydrate having a pH of 8.5. Then, the slurry was filtered, and then washed with pure water to obtain a solution containing ZrO.2 52.6 g of a cake having a zirconium component converted into 10% by mass. Next, add 180 g of pure water to 20 g of the filter cake, and then add 12 g of 10% by mass potassium hydroxide aqueous solution to make it alkaline, then add 40 g of 35% by mass hydrogen peroxide water, and warm to 50 ° C. Dissolve the filter cake. 148 g of pure water was added to obtain2 400 g of an aqueous solution of zirconia peroxyzirconic acid was 0.5 mass%. On the other hand, SiO2 After the cation exchange resin (manufactured by Mitsubishi Resin Co., Ltd.) was slowly added to 2% by mass of water glass to remove alkali, the ion exchange resin was separated to obtain SiO2 Calculated as a 2% by mass aqueous solution of silicic acid. Secondly, TiO2 320 g of pure water was added to 80 g of a titanium dioxide-based particle (1-A) aqueous dispersion at 10% by mass, and the temperature was increased to 90 ° C. 26.7 g of the above zirconium peroxide aqueous solution and 21.2 g of the silicic acid aqueous solution were slowly added thereto. After the completion of the addition, the mixture was stirred and maintained at 90 ° C for 1 hour, and then the mixture was subjected to hydrothermal treatment in an autoclave at 165 ° C for 18 hours. Then, the mixed solution was cooled to room temperature, and then concentrated using an ultrafiltration membrane device to obtain titanium dioxide particles (1-B) having a solid content concentration of 10% by mass of the solid content of the composite oxide layer provided with zirconia. ) Water dispersion 128 g. <Production of the silicon dioxide layer (using the fourth step)> After cation exchange resin (manufactured by Mitsubishi Resin Co., Ltd.) was slowly added to 117 g of a titanium dioxide-based particle (1-B) aqueous dispersion to dealkaliate, ion exchange was separated. Resin. Tetraethoxysilane (manufactured by Tama Chemical Co., Ltd., SiO) was slowly added to the solution.2 126.0 g of a methanol solution of 8.96 g of a component (28.8% by mass) was heated and stirred at 50 ° C. for 1 hour to obtain a water / methanol dispersion of titanium dioxide particles (1-C). The obtained water / methanol dispersion of the titanium dioxide-based particles (1-C) was cooled to room temperature, and the dispersion medium was replaced with methanol using an ultrafiltration membrane. Thereafter, it was concentrated to obtain 40 g of a titanium dioxide-based particle (1-C) methanol dispersion having a solid content concentration of 30% by mass provided with a silicon dioxide layer. The amount of water contained in the methanol dispersion of the titanium dioxide-based particles (1-C) thus obtained was 0.3% by mass. ＜ Production of surface-treated metal oxide sol: Surface treatment using (meth) acrylfluorene-containing organosilicon compound (using the second step) ＞ Slowly added to 40 g of titanium dioxide-based particles (1-C) methanol dispersion After 1.47 g of 3-methacryloxypropyltrimethoxysilane (trade name: KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.), it was heated and stirred at 50 ° C for 19 hours. After cooling to room temperature, the dispersion medium was replaced with propylene glycol monomethyl ether (PGME) using an ultrafiltration membrane to obtain 40 g of a surface-treated metal oxide sol (1-D) having a solid content concentration of 30% by mass. The composition of the obtained surface-treated metal oxide sol is shown in Table 1. "Measurement of average particle diameter" The average particle diameter is obtained by taking an electron microscope photograph and measuring the particle diameter of any 100 particles and taking the average value. "Measurement method of refractive index of particles" 1) The dispersion liquid is collected in an evaporator, and the dispersion medium is evaporated. 2) The powder is dried at 120 ° C. 3) Add 2 or 3 drops of a reference refracting solution having a known refractive index to a glass plate, and mix the above powders. 4) The operations of 3) are performed with various reference refracting liquids, and the refractive index of the reference refracting liquid when the mixed liquid becomes transparent is taken as the refractive index of the particles. <Production of the coating (1) for forming a transparent film> Added 1.2 g of propylene glycol monomethyl ether and ethoxylated bisphenol A diacrylate (manufactured by Shin Nakamura Chemical Co., Ltd .: NK ESTER ABE-300), ethoxylated Pentaerythritol tetraacrylate (manufactured by Shin Nakamura Chemical Co., Ltd .: NK ESTER ATM-4E) was obtained by mixing 0.6 g and thoroughly mixed. Next, 0.05 g of 2,2-dimethoxy-1,2-diphenylethane-1-one (manufactured by BASF (stock): IRGACURE651) and phenylbis (2,4,6-trimethyl) were added. 0.04 g of benzamidine) -phosphine oxide (manufactured by BASF (stock): IRGACURE819) was mixed well to prepare an adhesive for a transparent film. Next, 14.0 g of a surface-treated metal oxide sol (1-D) was mixed with the above-mentioned adhesive for a transparent film to prepare a transparent film-forming coating material (1) having a solid content concentration of 6% by mass. <Production of the base material (1-FA) with a transparent film> A coating film (1) for forming a transparent film was applied to an easy-to-adhere PET film by a bar coater method (bar # 10) (manufactured by Toyobo) : COSMOSHINE A-4300, thickness 188 μm, total light transmittance 92.0%, haze 0.7%), after drying at 80 ° C for 1 minute, a high-pressure mercury lamp (manufactured by Japan Battery: UV (ultraviolet, ultraviolet)) irradiation device CS30L21 -3) at 120 mJ / cm2 The substrate was hardened by irradiation to prepare a substrate (1-FA) with a transparent film. At this time, the thickness of the transparent film was 400 nm. The obtained film was evaluated for haze, total light transmittance, refractive index, abrasion resistance, and weather resistance by the following methods. "Measurement of Haze and Total Light Transmittance" The haze and total light transmittance of the obtained transparent film were measured with a haze meter (manufactured by Nippon Denshoku Co., Ltd .: NDH-2000). The haze and total light transmittance were evaluated according to the following criteria, and the results are shown in the table. <Evaluation criteria> Haze; 1.0% or less: ◎ 1.1 to 2.0%: ○ 2.1% or more: × <Evaluation criteria> Total light transmittance; 85 to 100%: ◎ 75 to 84%: ○ 74% or less: × " Measurement of Refractive Index "The refractive index of the coating was measured with a spectroscopic ellipsometer (manufactured by SEMILAB, Japan: SE-2000). The refractive index was evaluated according to the following criteria, and the results are shown in the table. <Evaluation criteria> 1.70 or more: ◎ 1.60 to 1.69: ○ 1.59 or less: × "Measurement of Scratch Resistance" Using # 0000 steel wool with a load of 500 g / cm2 Visually observe the surface of the film by sliding 50 times. The abrasion resistance was evaluated according to the following criteria, and the results are shown in the table. <Evaluation Criteria> No scaly abrasions can be seen: ◎ A few scaly abrasions can be seen: ○ A large number of scaly abrasions can be seen: △ Overall friction of the surface: × "Measurement of weather resistance" Using a mercury lamp (Toshiba (Toshiba ( Production): H400-E) The substrate (1-FA) with a transparent conductive film was irradiated with ultraviolet rays for 24 hours, and the color was visually confirmed. The weather resistance was evaluated according to the following criteria, and the results are shown in the table. In addition, the irradiation distance between the lamp and the test piece was set to 70 mm, and the output of the lamp was adjusted such that the surface temperature of the test piece was 45 ± 5 ° C. <Evaluation Criteria> Discoloration is not visible: ◎ Slight discoloration is visible: ○ Significant discoloration is visible: × <Manufacture of base material (1-FB) with transparent film> Coating (1) for forming a transparent film It was coated on a 6-inch silicon wafer by a spin coater, and dried at 80 ° C for 1 minute, and then irradiated with an ArF excimer laser (193 nm) using an exposure device NSR-S302 (manufactured by Nikon). Hardened to prepare a substrate (1-FB) with a transparent film. At this time, the thickness of the transparent film was 400 nm. The bulge and sensitivity of the obtained film were evaluated by the following methods. "Measurement of the bulge" The cross section of the base material (1-FB) with a transparent conductive film was observed with a scanning electron microscope, and the width of the film end portion that was 10% thicker than the film thickness at the center of the film was measured. . The uplift was evaluated in accordance with the following evaluation criteria, and the results are shown in the table. <Evaluation Criteria> The width of the film end of 10% or more is less than 0.5 mm: ◎ The width of the film end of 10% or more is 0.5 to 1.0 mm: ○ The width of the film end of 10% or more is 1.1 mm Above: × "Measurement of Sensitivity and Residual Film Rate" <Evaluation Criteria> The substrate (1-FB) with a transparent conductive film was immersed in 1% by mass of Na2 CO3 After removing the unhardened portion in the aqueous solution for 10 minutes, it was dried at 80 ° C. for 1 晩, and the sensitivity and the residual film rate were evaluated based on the mass difference before and after immersion, and the results are shown in the table. ＜ Evaluation Criteria ＞ Na2 CO3 The mass difference before and after immersion in the aqueous solution is 0 to 3%: ◎ Na2 CO3 Mass difference before and after immersion in aqueous solution is 4-10%: ○ Na2 CO3 The mass difference before and after the immersion in the aqueous solution is 11% or more: × <Production of the base material (1-FC) with a transparent coating layer> A coating (1) for forming a transparent coating layer is applied to a 6-inch layer by a spin coater. After drying at 80 ° C for 1 minute on a silicon wafer, an exposure device NSR-S302 (manufactured by Nikon Corporation) was used to irradiate the ArF excimer laser (193 nm) through a reticle (1: 1 line diagram). Let it harden. Thereafter, 1% by mass of Na was sprayed.2 CO3 The aqueous solution was dissolved to remove unexposed portions, and heated at 150 ° C for 3 minutes to prepare a substrate (1-FC) with a transparent film. Using the obtained transparent film-containing substrate (1-FC), the resolution was evaluated by the following method. "Measurement of Resolution" The width of the mask gap when the base material (1-FC) with a transparent conductive film was produced was changed. The minimum gap width normally formed by the gap width was evaluated as the value of the resolution as shown below. In the table. <Evaluation criteria> Pitch width 30 μm or less: ◎ Pitch width 31 μm to 50 μm: ○ Pitch width 51 μm or more: × [Example 2] Except for the second step, 3-methacryloxyoxypropyl was used Except for 0.06 g of trimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-503), the same procedure as in Example 1 was performed to obtain a surface-treated metal oxide sol (2-D). The composition of the obtained surface-treated metal oxide sol is shown in Table 1. A coating for forming a transparent film was produced in the same manner as in Example 1 except that the surface-treated metal oxide sol (2-D) was used. Then, a substrate with a transparent film was produced in the same manner as in Example 1 and evaluated. [Example 3] The same procedure as in Example 1 was carried out except that 7.2 g of 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Industry Co., Ltd .: KBM-503) was used in the second step. This was performed to obtain a surface-treated metal oxide sol (3-D). The composition of the obtained surface-treated metal oxide sol is shown in Table 1. A coating for forming a transparent film was produced in the same manner as in Example 1 except that a surface-treated metal oxide sol (3-D) was used. Then, a substrate with a transparent film was produced in the same manner as in Example 1 and evaluated. [Example 4] In the second step, after adding 0.06 g of 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Industry Co., Ltd .: KBM-503), 2.9% by mass ammonia solution 0.29 was added. g was carried out in the same manner as in Example 1 to obtain a surface-treated metal oxide sol (4-D). The composition of the obtained surface-treated metal oxide sol is shown in Table 1. A coating for forming a transparent film was produced in the same manner as in Example 1 except that the surface-treated metal oxide sol (4-D) was used. Then, a substrate with a transparent film was produced in the same manner as in Example 1 and evaluated. [Example 5] In the second step, 7.2 g of 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Industry Co., Ltd .: KBM-503) was added, and then a 2.9% by mass ammonia solution 0.29 was added. g was carried out in the same manner as in Example 1 to obtain a surface-treated metal oxide sol (5-D). A coating for forming a transparent film was produced in the same manner as in Example 1 except that the surface-treated metal oxide sol (5-D) was used. Then, a substrate with a transparent film was produced in the same manner as in Example 1 and evaluated. [Example 6] Except for the fourth step, tetraethoxysilane (manufactured by Tama Chemical Co., Ltd., SiO) was used.2 Except for 126.0 g of a methanol solution (component 28.8% by mass) and 0.90 g, a surface-treated metal oxide sol (6-D) was obtained in the same manner as in Example 1. The composition of the obtained surface-treated metal oxide sol is shown in Table 1. A coating for forming a transparent film was produced in the same manner as in Example 1 except that the surface-treated metal oxide sol (6-D) was used. Then, a substrate with a transparent film was produced in the same manner as in Example 1 and evaluated. [Example 7] Except for the fourth step, a solution of tetraethoxysilane (manufactured by Tama Chemical Co., Ltd., SiO) was used.2 Except for 126.0 g of a methanol solution (48.8 g of component 28.8% by mass), a surface-treated metal oxide sol (7-D) was obtained in the same manner as in Example 1. The composition of the obtained surface-treated metal oxide sol is shown in Table 1. A coating for forming a transparent film was produced in the same manner as in Example 1 except that the surface-treated metal oxide sol (7-D) was used. Then, a substrate with a transparent film was produced in the same manner as in Example 1 and evaluated. [Example 8] A surface-treated metal oxide sol (8-D) was obtained in the same manner as in Example 1 except that 7.6 g of an aqueous solution of zirconium acid and 6.1 g of an aqueous solution of silicic acid were used in the third step. The composition of the obtained surface-treated metal oxide sol is shown in Table 1. A coating for forming a transparent film was produced in the same manner as in Example 1 except that the surface-treated metal oxide sol (8-D) was used. Then, a substrate with a transparent film was produced in the same manner as in Example 1 and evaluated. [Example 9] A surface-treated metal oxide sol (9-D) was obtained in the same manner as in Example 1 except that 171.6 g of an aqueous solution of zirconium acid and 142.3 g of an aqueous solution of silicic acid were used in the third step. The composition of the obtained surface-treated metal oxide sol is shown in Table 1. A coating for forming a transparent film was produced in the same manner as in Example 1 except that the surface-treated metal oxide sol (9-D) was used. Then, a substrate with a transparent film was produced in the same manner as in Example 1 and evaluated. [Example 10] A surface-treated metal oxide sol (10-D) was obtained in the same manner as in Example 1 except that 6.02 g of a zirconium peroxide aqueous solution and 23.7 g of a silicic acid aqueous solution were used in the third step. The composition of the obtained surface-treated metal oxide sol is shown in Table 1. A coating for forming a transparent film was produced in the same manner as in Example 1 except that the surface-treated metal oxide sol (10-D) was used. Then, a substrate with a transparent film was produced in the same manner as in Example 1 and evaluated. [Example 11] A surface-treated metal oxide sol (11-D) was obtained in the same manner as in Example 1 except that 120.5 g of an aqueous solution of zirconium acid and 9.8 g of an aqueous solution of silicic acid were used in the third step. The composition of the obtained surface-treated metal oxide sol is shown in Table 1. A coating for forming a transparent film was produced in the same manner as in Example 1 except that the surface-treated metal oxide sol (11-D) was used. Then, a substrate with a transparent film was produced in the same manner as in Example 1 and evaluated. [Example 12] Except in the third step, Al was used2 O3 11.5 g of sodium aluminate aqueous solution with a concentration of 1.0% by mass and SiO2 14.8 g of a sodium silicate aqueous solution having a conversion concentration of 3.0% by mass was used in the same manner as in Example 1 except that the zirconium peroxide aqueous solution and the silicic acid aqueous solution were replaced to obtain a solid component concentration of a composite oxide layer provided with silica alumina. It is a 10% by mass titanium dioxide-based particle (12-B) aqueous dispersion. Then, it carried out similarly to Example 1, and obtained the surface-treated metal oxide sol (12-D). The composition of the obtained surface-treated metal oxide sol is shown in Table 1. A coating for forming a transparent film was produced in the same manner as in Example 1 except that the surface-treated metal oxide sol (12-D) was used. Then, a substrate with a transparent film was produced in the same manner as in Example 1 and evaluated. [Example 13] Divided in the third step. Use Al2 O3 11.5 g of sodium aluminate aqueous solution with a concentration of 1.0% by mass and SiO2 14.8 g of a sodium silicate aqueous solution having a conversion concentration of 3.0% by mass was used in the same manner as in Example 1 except that the zirconium peroxide aqueous solution and the silicic acid aqueous solution were replaced to obtain a solid component concentration of a composite oxide layer provided with silica alumina. It is a 10% by mass titanium dioxide-based particle (13-B) aqueous dispersion. Then, the same procedure as in Example 1 was performed except that the alkali-removal treatment using a cation exchange resin in the fourth step was repeated to obtain a titanium dioxide-based particle having a solid content concentration of 30% by mass provided with a silicon dioxide layer (13 -C) methanol dispersion. Then, it carried out similarly to Example 1, and obtained the surface-treated metal oxide sol (13-D). The composition of the obtained surface-treated metal oxide sol is shown in Table 1. A coating for forming a transparent film was produced in the same manner as in Example 1 except that the surface-treated metal oxide sol (13-D) was used. Then, a substrate with a transparent film was produced in the same manner as in Example 1 and evaluated. [Example 14] Except for the third step, TiO was used2 9.5 g of titanium tetrachloride aqueous solution with a concentration of 1.0% by mass and SiO2 The same procedure as in Example 1 was carried out except that 15.5 g of a sodium silicate aqueous solution with a concentration of 3.0% by mass was used instead of the zirconium peroxide aqueous solution and the silicic acid aqueous solution. 10% by mass of a titanium dioxide-based particle (14-B) aqueous dispersion. Then, it carried out similarly to Example 1, and obtained the surface-treated metal oxide sol (14-D). The composition of the obtained surface-treated metal oxide sol is shown in Table 1. A coating for forming a transparent film was produced in the same manner as in Example 1 except that the surface-treated metal oxide sol (14-D) was used. Then, a substrate with a transparent film was produced in the same manner as in Example 1 and evaluated. [Example 15] Except for the third step, SnO was used2 15.5 g of potassium stannate aqueous solution with a concentration of 1.0% by mass and SiO2 13.5 g of a silicic acid aqueous solution with a concentration of 2.0% by mass was replaced in the same manner as in Example 1 except that the zirconium peroxide aqueous solution and the silicic acid aqueous solution were obtained. The solid component concentration of the composite oxide layer provided with silicon dioxide tin oxide was 10% by mass of a titanium dioxide-based particle (15-B) aqueous dispersion. Then, it carried out similarly to Example 1, and obtained the surface-treated metal oxide sol (15-D). The composition of the obtained surface-treated metal oxide sol is shown in Table 1. A coating for forming a transparent film was produced in the same manner as in Example 1 except that the surface-treated metal oxide sol (15-D) was used. Then, a substrate with a transparent film was produced in the same manner as in Example 1 and evaluated. [Example 16] In the first step, TiO2 450 g of a 2% by mass aqueous solution of peroxytitanic acid was mixed in the same manner as in Example 1 except that 599 g of pure water was mixed without using a silica sol. Titanium dioxide particles having a solid content concentration of 10% by mass (16-A ) Water dispersion. Then, it carried out similarly to Example 1, and obtained the surface-treated metal oxide sol (16-D). The composition of the obtained surface-treated metal oxide sol is shown in Table 1. A coating for forming a transparent film was produced in the same manner as in Example 1 except that a surface-treated metal oxide sol (16-D) was used. Then, a substrate with a transparent film was produced in the same manner as in Example 1 and evaluated. [Example 17] Except for the first step,2 450 g of a 2% by mass aqueous solution of peroxytitanic acid is mixed with SiO2 Silica sol (average particle size of 7 nm) of silica dioxide (average particle size: 7 nm): 15% by mass (Cataloid SN-350): 17.9 g and 581 g of pure water, the same as Example 1 This was performed to obtain a titanium dioxide-based particle (17-A) aqueous dispersion having a solid content concentration of 10% by mass. Then, it carried out similarly to Example 1, and obtained the surface-treated metal oxide sol (17-D). The composition of the obtained surface-treated metal oxide sol is shown in Table 1. A transparent coating film-forming coating material was produced in the same manner as in Example 1 except that the surface-treated metal oxide sol (17-D) was used. Then, a substrate with a transparent film was produced in the same manner as in Example 1 and evaluated. [Example 18] In the first step, TiO was produced in the same manner as in Example 1.2 35.0 g of a cation exchange resin was mixed with 729.0 g of a 2 mass% aqueous solution of peroxytitanic acid, and SnO was slowly added thereto under stirring.2 After 91.0 g of a 1% by mass potassium stannate aqueous solution was converted, the cation exchange resin was separated. Then, the mixture contains SiO2 15% by mass of 8.0 g of silica sol (manufactured by Nippon Kasei Kasei Co., Ltd .: CATALOID SN-350) and 180.0 g of pure water in a silica sol having an average particle diameter of 7 nm, in an autoclave at 165 ° C Under the conditions of 18 hours hydrothermal treatment. Next, the obtained aqueous solution was cooled to room temperature, and then concentrated using an ultrafiltration membrane device to obtain a titanium dioxide-based fine particle (18-A) aqueous dispersion having a solid content concentration of 10% by mass. Then, it carried out similarly to Example 1, and obtained the surface-treated metal oxide sol (18-D). The composition of the obtained surface-treated metal oxide sol is shown in Table 2. A coating for forming a transparent film was produced in the same manner as in Example 1 except that the surface-treated metal oxide sol (18-D) was used. Then, a substrate with a transparent film was produced in the same manner as in Example 1 and evaluated. [Example 19] In the first step, mixed with TiO2 444.9 g of titanium tetrachloride aqueous solution of 2% by mass of titanium tetrachloride and Fe2 O3 An iron dioxide-doped titanium dioxide system having a solid content concentration of 10% by mass was obtained in the same manner as in Example 1 except that 5.1 g of a 2% by mass ferric chloride aqueous solution was converted and 176g of 15% by mass ammonia water was mixed. Particle (19-A) aqueous dispersion. Then, it carried out similarly to Example 1, and obtained the surface-treated metal oxide sol (19-D). The composition of the obtained surface-treated metal oxide sol is shown in Table 2. A coating for forming a transparent film was produced in the same manner as in Example 1 except that the surface-treated metal oxide sol (19-D) was used. Then, a substrate with a transparent film was produced in the same manner as in Example 1 and evaluated. [Example 20] In the first step, mixed with TiO2 404.0 g of a titanium tetrachloride aqueous solution of 2% by mass of titanium tetrachloride and Fe2 O3 An iron oxide-doped titanium dioxide system having a solid content concentration of 10% by mass was obtained in the same manner as in Example 1 except that 46.0 g of a 2% by mass ferric chloride aqueous solution was converted and 176 g of 15% by mass ammonia water was mixed. 104.9 g of particles (20-A) aqueous dispersion. Then, it carried out similarly to Example 1, and obtained the surface-treated metal oxide sol (20-D). The composition of the obtained surface-treated metal oxide sol is shown in Table 2. A coating for forming a transparent film was produced in the same manner as in Example 1 except that the surface-treated metal oxide sol (20-D) was used. Then, a substrate with a transparent film was produced in the same manner as in Example 1 and evaluated. [Example 21] In the first step, mixed with TiO2 444.9 g of titanium tetrachloride aqueous solution of titanium tetrachloride converted to 2% by mass and CeO2 A conversion of 2 g% by mass of 5.1 g of cerium chloride aqueous solution and 15 mass% of ammonia by 176 g were performed in the same manner as in Example 1 to obtain a cerium-doped titanium dioxide system having a solid content concentration of 10 mass%. Particle (21-A) aqueous dispersion. Then, it carried out similarly to Example 1, and obtained the surface-treated metal oxide sol (21-D). The composition of the obtained surface-treated metal oxide sol is shown in Table 2. A coating for forming a transparent film was produced in the same manner as in Example 1 except that the surface-treated metal oxide sol (21-D) was used. Then, a substrate with a transparent film was produced in the same manner as in Example 1 and evaluated. [Example 22] In the first step, mixed with TiO2 404.0 g of titanium tetrachloride aqueous solution of titanium tetrachloride converted to 2% by mass and CeO2 A conversion of 26.0% by mass of 46.0 g of a cerium chloride aqueous solution and mixing of 176 g of 15% by mass of ammonia water were carried out in the same manner as in Example 1. A cerium-doped titanium dioxide system having a solid content concentration of 10% by mass was obtained. Particle (22-A) aqueous dispersion. Then, it carried out similarly to Example 1, and obtained the surface-treated metal oxide sol (22-D). The composition of the obtained surface-treated metal oxide sol is shown in Table 2. A coating for forming a transparent film was produced in the same manner as in Example 1 except that the surface-treated metal oxide sol (22-D) was used. Then, a substrate with a transparent film was produced in the same manner as in Example 1 and evaluated. [Example 23] Except for the first step, TiO2 450 g of a 2% by mass aqueous solution of peroxytitanic acid is mixed with SiO2 Silica sol (average particle size of 7 nm) of silica sol (average particle size: 7 nm, calculated as 15% by mass): 8.2 g and 239.1 g of pure water, except that 8.2 g was the same as in Example 1 This was performed to obtain a titanium dioxide-based particle (23-A) aqueous dispersion having a solid content concentration of 10% by mass. Then, it carried out similarly to Example 1, and obtained the surface-treated metal oxide sol (23-D). The composition of the obtained surface-treated metal oxide sol is shown in Table 2. A coating for forming a transparent film was produced in the same manner as in Example 1 except that the surface-treated metal oxide sol (23-D) was used. Then, a substrate with a transparent film was produced in the same manner as in Example 1 and evaluated. [Example 24] Except for the first step, TiO2 450 g of a 2% by mass aqueous solution of peroxytitanic acid is mixed with SiO2 Silica sol (average particle size of 7 nm) of silica sol (average particle size: 7 nm): sol. (Manufactured by Nippon Kasei Kasei Co., Ltd .: CATALOID SN-350) 8.2 g and pure water 1637.1 g, the same as Example 1 This was performed to obtain a titanium dioxide-based particle (24-A) aqueous dispersion having a solid content concentration of 10% by mass. Then, it carried out similarly to Example 1, and obtained the surface-treated metal oxide sol (24-D). The composition of the obtained surface-treated metal oxide sol is shown in Table 2. A coating for forming a transparent film was produced in the same manner as in Example 1 except that the surface-treated metal oxide sol (24-D) was used. Then, a substrate with a transparent film was produced in the same manner as in Example 1 and evaluated. [Example 25] Except for the first step,2 450 g of a 2% by mass aqueous solution of peroxytitanic acid is mixed with SiO2 Silica sol (manufactured by Nippon Kasei Kasei Co., Ltd .: CATALOID SN-350) having an average particle diameter of 7 nm and having a particle size of 15% by mass, except for 8.2 g and 122.6 g of pure water, was the same as in Example 1. This was performed to obtain a titanium dioxide-based particle (25-A) aqueous dispersion having a solid content concentration of 10% by mass. Then, it carried out similarly to Example 1, and obtained the surface-treated metal oxide sol (25-D). The composition of the obtained surface-treated metal oxide sol is shown in Table 2. A coating for forming a transparent film was produced in the same manner as in Example 1 except that the surface-treated metal oxide sol (25-D) was used. Then, a substrate with a transparent film was produced in the same manner as in Example 1 and evaluated. [Example 26] Except for TiO in the first step2 450 g of a 2% by mass aqueous solution of peroxytitanic acid is mixed with SiO2 Silica sol (manufactured by Nippon Kasei Kasei Co., Ltd .: CATALOID SN-350) having an average particle diameter of 7 nm and having a particle size of 15% by mass, except for 8.2 g and 122.6 g of pure water, was the same as in Example 1. This was carried out to obtain a titanium dioxide-based particle (26-A) aqueous dispersion having a solid content concentration of 10% by mass. Thereafter, the same procedure as in Example 1 was carried out except that the alkali removal treatment using a cation exchange resin in the fourth step was repeated to obtain a surface-treated metal oxide sol (26-D). The composition of the obtained surface-treated metal oxide sol is shown in Table 2. A coating for forming a transparent film was produced in the same manner as in Example 1 except that the surface-treated metal oxide sol (26-D) was used. Then, a substrate with a transparent film was produced in the same manner as in Example 1 and evaluated. [Example 27] In the first step and the third step, a cation exchange resin was slowly added to a titanium dioxide-based particle (1-B) aqueous dispersion having a solid content concentration of 10% by mass produced in the same manner as in Example 1. (Manufactured by Mitsubishi Resin Co., Ltd.) After alkali removal, the ion exchange resin was separated. Thereafter, the dispersion medium was replaced with methanol using an ultrafiltration membrane. Thereafter, it was concentrated to obtain a titanium dioxide-based fine particle (27-B) methanol dispersion liquid having a solid content concentration of 30% by mass. The amount of water contained in the obtained titanium dioxide-based particle (27-B) methanol dispersion was 0.3% by mass. Furthermore, in a second step, 3-methacryloxypropyltrimethoxysilane was slowly added to 40 g of the methanol dispersion of titanium dioxide particles (27-B). -503) 1.47 g. Thereafter, the mixture was heated and stirred at 50 ° C for 19 hours. Then, after cooling to room temperature, the dispersion medium was replaced with propylene glycol monomethyl ether (PGME) using an ultrafiltration membrane to obtain a surface-treated metal oxide sol (27-D) having a solid content concentration of 30% by mass. The composition of the obtained surface-treated metal oxide sol is shown in Table 2. Furthermore, in this embodiment, the fourth step is not performed. A coating for forming a transparent film was produced in the same manner as in Example 1 except that the surface-treated metal oxide sol (27-D) was used. Then, a substrate with a transparent film was produced in the same manner as in Example 1 and evaluated. [Example 28] In the first step, a cation exchange resin (Mitsubishi) was slowly added to 117 g of a titanium dioxide-based particle (1-A) aqueous dispersion having a solid content concentration of 10% by mass produced in the same manner as in Example 1. After the resin (strand) was dealkaliated, the ion exchange resin was separated. Next, in the production of the silicon dioxide layer in the fourth step, 126.0 g of a methanol solution of 8.96 g of tetraethoxysilane (manufactured by Tama Chemicals) was slowly added to the solution, and the mixture was heated and stirred at 50 ° C. One hour, a water / methanol dispersion of titanium dioxide-based particles (28-C) was obtained. The water / methanol dispersion of the titanium dioxide particles (28-C) was cooled to room temperature, and the dispersion medium was replaced with methanol using an ultrafiltration membrane. Thereafter, it was concentrated to obtain a titanium dioxide-based particle (28-C) methanol dispersion liquid having a solid content concentration of 30% by mass. The amount of water contained in the obtained titanium dioxide-based particle (28-C) methanol dispersion was 0.3% by mass. Furthermore, in a second step, 3-methacryloxypropyltrimethoxysilane was slowly added to 40 g of the titanium dioxide-based particle (28-C) methanol dispersion liquid (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM). -503) 1.47 g. Thereafter, the mixture was heated and stirred at 50 ° C for 19 hours. Then, after cooling to room temperature, the dispersion medium was replaced with propylene glycol monomethyl ether (PGME) using an ultrafiltration membrane to obtain a surface-treated metal oxide sol (28-D) having a solid content concentration of 30% by mass. The composition of the obtained surface-treated metal oxide sol is shown in Table 2. Furthermore, in this embodiment, the fabrication of the silicon dioxide composite oxide layer in the third step is not performed. A coating for forming a transparent film was produced in the same manner as in Example 1 except that the surface-treated metal oxide sol (28-D) was used. Then, a substrate with a transparent film was produced in the same manner as in Example 1 and evaluated. [Example 29] Except in the second step, 1.47 g of 3-propenyloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-5103) was used instead of 3-methacrylic acid oxypropyl A surface-treated metal oxide sol (29-D) was obtained in the same manner as in Example 1 except for trimethyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-503). The composition of the obtained surface-treated metal oxide sol is shown in Table 2. A coating for forming a transparent film was produced in the same manner as in Example 1 except that the surface-treated metal oxide sol (29-D) was used. Then, a substrate with a transparent film was produced in the same manner as in Example 1 and evaluated. [Example 30] Except for the second step, 1.47 g of 3-propenyloxypropyltriethoxysilane (manufactured by Shin-Etsu Chemical Industry Co., Ltd .: KBE-503) was used instead of 3-methacryloxy A surface-treated metal oxide sol (30-D) was obtained in the same manner as in Example 1 except for propyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-503). The composition of the obtained surface-treated metal oxide sol is shown in Table 2. A coating for forming a transparent film was produced in the same manner as in Example 1 except that the surface-treated metal oxide sol (30-D) was used. Then, a base material with a transparent film is manufactured and evaluated. [Example 31] Except for the second step, 1.47 g of 3-propenyloxypropyldimethylsilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBE-502) was used instead of 3-methacryloxy A surface-treated metal oxide sol (31-D) was obtained in the same manner as in Example 1 except for propyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-503). The composition of the obtained surface-treated metal oxide sol is shown in Table 2. A coating for forming a transparent film was produced in the same manner as in Example 1 except that the surface-treated metal oxide sol (31-D) was used. Then, a substrate with a transparent film was produced in the same manner as in Example 1 and evaluated. [Example 32] A propylene glycol monomethyl ether acetate (PGMEA) was used in place of the propylene glycol monomethyl ether (PGME) in the second step, and the same procedure as in Example 1 was performed to obtain a solid component concentration of 30% by mass Surface treated metal oxide sol (32-D). The composition of the obtained surface-treated metal oxide sol is shown in Table 2. A coating for forming a transparent film was produced in the same manner as in Example 1 except that the surface-treated metal oxide sol (32-D) was used. Then, a substrate with a transparent film was produced in the same manner as in Example 1 and evaluated. [Example 33] In the fourth step, a cation exchange resin (manufactured by Mitsubishi Resins (stock)) was slowly added to a water / methanol dispersion of the titanium dioxide-based particles (1-C) produced in the same manner as in Example 1 to remove the After the base, the ion exchange resin was separated. The obtained water / methanol dispersion of the titanium dioxide-based particles (33-C) was cooled to room temperature, and the dispersion medium was replaced with methanol using an ultrafiltration membrane. Thereafter, it was concentrated to obtain 40 g of a titanium dioxide-based fine particle (33-C) methanol dispersion having a solid content concentration of 30% by mass. Then, it carried out similarly to Example 1, and obtained the surface-treated metal oxide sol (33-D). The composition of the obtained surface-treated metal oxide sol is shown in Table 2. A coating for forming a transparent film was produced in the same manner as in Example 1 except that the surface-treated metal oxide sol (33-D) was used. Then, a substrate with a transparent film was produced in the same manner as in Example 1 and evaluated. [Comparative Example 1] In the fourth step, the dispersion medium was replaced with an ultrafiltration membrane in a titanium dioxide-based particle (1-C) methanol dispersion having a solid content concentration of 30% by mass produced in the same manner as in Example 1. Propylene glycol monomethyl ether (PGME). Thus, 40 g of a metal oxide sol (C1-D) having a solid content concentration of 30% by mass without surface treatment with an organosilicon compound containing a (meth) acrylfluorenyl group was obtained. The composition of the obtained metal oxide sol is shown in Table 3. A coating for forming a transparent film was produced in the same manner as in Example 1 except that the surface-treated metal oxide sol (C1-D) was used. Then, a substrate with a transparent film was produced in the same manner as in Example 1 and evaluated. [Comparative Example 2] In the second step, except that the amount of 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Industry Co., Ltd .: KBM-503) was set to 15.6 g, Example 1 was performed in the same manner to obtain a surface-treated metal oxide sol (C2-D). The composition of the obtained metal oxide sol is shown in Table 3. A coating for forming a transparent film was produced in the same manner as in Example 1 except that a surface-treated metal oxide sol (C2-D) was used. Then, a substrate with a transparent film was produced in the same manner as in Example 1 and evaluated. [Comparative Example 3] TiO was produced in the same manner as in Example 1 except in the first step.2 450 g of a 2% by mass aqueous solution of peroxytitanic acid mixed with 15% by mass of a silica sol containing silicon dioxide particles having an average particle diameter of 7 nm (manufactured by Nippon Shocata Chemical Co., Ltd .: CATALOID SN-350) 65.0 Except for g and 532 g of pure water, it was carried out in the same manner as in Example 1 to obtain a titanium dioxide-based particle (C3-A) aqueous dispersion having a solid content concentration of 10% by mass. Then, it carried out similarly to Example 1, and obtained the surface-treated metal oxide sol (C3-D). The composition of the obtained surface-treated metal oxide sol is shown in Table 3. A coating for forming a transparent film was produced in the same manner as in Example 1 except that a surface-treated metal oxide sol (C3-D) was used. Then, a substrate with a transparent film was produced in the same manner as in Example 1 and evaluated. [Comparative Example 4] In the first step, TiO was produced in the same manner as in Example 1.2 35.0 g of a cation exchange resin was mixed with 280.4 g of a 2 mass% aqueous solution of peroxytitanic acid, and SnO was slowly added thereto under stirring.2 The cation exchange resin was separated after 527.8 g of 1 mass% potassium stannate aqueous solution was converted. Next, 8.0 g of colloidal silica sol (manufactured by Nippon Kasei Chemical Industries, Ltd .: CATALOID SN-350) containing 15% by mass of silicon dioxide particles having an average particle diameter of 7 nm was mixed with 180.0 g of pure water in an autoclave. Hydrothermal treatment was performed at 165 ° C for 18 hours. Next, the obtained aqueous solution was cooled to room temperature, and then concentrated using an ultrafiltration membrane device to obtain a titanium dioxide-based fine particle (C4-A) aqueous dispersion having a solid content concentration of 10% by mass. Then, it carried out similarly to Example 1, and obtained the surface-treated metal oxide sol (C4-D). The composition of the obtained surface-treated metal oxide sol is shown in Table 3. A coating for forming a transparent film was produced in the same manner as in Example 1 except that a surface-treated metal oxide sol (C4-D) was used. Then, a substrate with a transparent film was produced in the same manner as in Example 1 and evaluated. [Reference Example 1] In the first step, a cation exchange resin (Mitsubishi Resin (Mitsubishi Resin ( (Manufactured)) After dealkalination, the ion exchange resin was separated. Thereafter, the dispersion medium was replaced with methanol using an ultrafiltration membrane. Thereafter, it was concentrated to obtain a titanium dioxide-based particle (R1-A) methanol dispersion liquid having a solid content concentration of 30% by mass. The amount of water contained in the obtained titanium dioxide-based particle (R1-A) methanol dispersion was 0.3% by mass. Further, in a second step, 3-methacryloxypropyltrimethoxysilane was gradually added to 40 g of the titanium dioxide-based particles (R1-A) methanol dispersion liquid (manufactured by Shin-Etsu Chemical Industry Co., Ltd .: KBM). -503) 1.47 g. Thereafter, the mixture was heated and stirred at 50 ° C for 19 hours. Then, after cooling to room temperature, the dispersion medium was replaced with propylene glycol monomethyl ether (PGME) using an ultrafiltration membrane to obtain a surface-treated metal oxide sol (R1-D) having a solid content concentration of 30% by mass. The composition of the obtained surface-treated metal oxide sol is shown in Table 2. A coating for forming a transparent film was produced in the same manner as in Example 1 except that the surface-treated metal oxide sol (R1-D) was used. Then, a substrate with a transparent film was produced in the same manner as in Example 1 and evaluated. [Table 1] [Table 2] [table 3]

無no

Claims (6)

一種表面處理金屬氧化物溶膠，其特徵在於： 其包含藉由式(1)所表示之包含(甲基)丙烯醯基之有機矽化合物對金屬氧化物粒子之表面進行處理而得之表面處理金屬氧化物粒子、與分散介質， 其中上述金屬氧化物粒子包含以TiO2 計為50質量%以上之二氧化鈦， 上述有機矽化合物相對於上述金屬氧化物粒子100質量份，以R1 n -SiO(4-n)/2 (其中，R1 係選自甲基丙烯醯基及丙烯醯基中之至少一者，相互可相同，亦可不同，n係1～3之整數)計，於上述金屬氧化物粒子表面設有0.1～60質量份， 上述有機矽化合物若累加設於上述金屬氧化物粒子表面者與除此之外存在於上述表面處理金屬氧化物溶膠中者，則相對於上述金屬氧化物粒子100質量份，以R1 n -SiO(4-n)/2 計，含有0.1～100質量份， 於上述金屬氧化物粒子與上述包含(甲基)丙烯醯基之有機矽化合物之間，具有選自二氧化矽氧化鋯、二氧化矽氧化鋁、二氧化矽二氧化鈦及二氧化矽氧化錫中之二氧化矽複合氧化物之層，與二氧化矽層中之至少一者， 鈉以Na2 O濃度計為25 ppm以下，鉀以K2 O濃度計未達0.5質量%，氨以NH3 濃度計未達1000 ppm， R1 n -SiX1 (4-n) (1) (其中，R1 係選自甲基丙烯醯基及丙烯醯基中之至少一者，相互可相同，亦可不同，n係1～3之整數，X1 係烷氧基)。A surface-treated metal oxide sol, characterized in that it comprises a surface-treated metal obtained by treating the surface of a metal oxide particle with an organic silicon compound containing a (meth) acrylfluorenyl group represented by formula (1). An oxide particle and a dispersion medium, wherein the metal oxide particle contains 50% by mass or more of titanium dioxide as TiO 2 , and the organosilicon compound is 100 parts by mass with respect to the metal oxide particle, and R 1 n -SiO (4 -n) / 2 (wherein R 1 is at least one selected from the group consisting of methacrylfluorenyl and acrylfluorenyl, which may be the same or different from each other, and n is an integer of 1 to 3). 0.1 to 60 parts by mass are provided on the surface of the object particle, and if the organosilicon compound is added to the surface of the metal oxide particle and is present in the surface-treated metal oxide sol in addition, it is relative to the metal oxide 100 parts by mass of the particles, based on R 1 n -SiO (4-n) / 2 , containing 0.1 to 100 parts by mass between the metal oxide particles and the organosilicone compound containing the (meth) acrylfluorenyl group, Dioxin Silicon dioxide zirconium oxide, silicon dioxide alumina, silicon dioxide titania and silicon dioxide composite oxide layer in silicon dioxide and at least one of the silicon dioxide layer, sodium is calculated as Na 2 O concentration 25 ppm or less, potassium less than 0.5% by mass as K 2 O concentration, ammonia less than 1000 ppm as NH 3 concentration, R 1 n -SiX 1 (4-n) (1) (wherein R 1 is selected Bing Xixi Bing Xixi methyl group, and the group from at least one of each other may be the same or different, an integer of 1 to 3 lines of n, X 1 containing alkoxy). 如請求項1之表面處理金屬氧化物溶膠，其中上述金屬氧化物粒子係二氧化鈦或包含鈦與其他金屬之複合氧化物。The surface-treated metal oxide sol according to claim 1, wherein the metal oxide particles are titanium dioxide or a composite oxide containing titanium and other metals. 如請求項2之表面處理金屬氧化物溶膠，其中上述其他金屬係矽、錫、鐵及鈰中之至少1種。The surface-treated metal oxide sol according to claim 2, wherein the other metal is at least one of silicon, tin, iron, and cerium. 如請求項1至3中任一項之表面處理金屬氧化物溶膠，其中上述表面處理金屬氧化物粒子之平均粒徑為5～500 nm，以固形物成分計含有5～70質量%。The surface-treated metal oxide sol according to any one of claims 1 to 3, wherein the surface-treated metal oxide particles have an average particle diameter of 5 to 500 nm and contain 5 to 70% by mass as a solid content. 如請求項1至4中任一項之表面處理金屬氧化物溶膠，其中上述分散介質至少包含1種SP值為10以上且沸點超過100℃之有機溶劑，該有機溶劑於上述分散介質中含有30～95質量%。The surface-treated metal oxide sol according to any one of claims 1 to 4, wherein the dispersion medium contains at least one organic solvent having an SP value of 10 or more and a boiling point exceeding 100 ° C, and the organic solvent contains 30 in the dispersion medium. ~ 95 mass%. 如請求項1至5中任一項之表面處理金屬氧化物溶膠，其中鈉以Na2 O濃度計未達20 ppm，鉀以K2 O濃度計未達0.5質量%，氨以NH3 濃度計未達1000 ppm。The surface-treated metal oxide sol according to any one of claims 1 to 5, wherein sodium is less than 20 ppm as Na 2 O concentration, potassium is less than 0.5 mass% as K 2 O concentration, and ammonia is NH 3 concentration Less than 1000 ppm.
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