TW201708449A - Coating solution for forming film, method for producing the coating solution and method for producing substrate with film - Google Patents

Coating solution for forming film, method for producing the coating solution and method for producing substrate with film Download PDF

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TW201708449A
TW201708449A TW105108808A TW105108808A TW201708449A TW 201708449 A TW201708449 A TW 201708449A TW 105108808 A TW105108808 A TW 105108808A TW 105108808 A TW105108808 A TW 105108808A TW 201708449 A TW201708449 A TW 201708449A
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component
coating liquid
film
concentration
mass
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TW105108808A
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TWI682010B (en
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Hirotada Arakane
Miki Egami
Ryo Muraguchi
Michio Komatsu
Mitsuaki Kumazawa
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Jgc Catalysts & Chemicals Ltd
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Priority claimed from JP2015074530A external-priority patent/JP6480781B2/en
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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
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • 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
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
    • B05D3/0254—After-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
    • B05D3/0254—After-treatment
    • B05D3/0263—After-treatment with IR heaters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
    • B05D3/061—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation using U.V.
    • B05D3/065—After-treatment
    • B05D3/067—Curing or cross-linking the coating
    • 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
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Paints Or Removers (AREA)

Abstract

The invention relates to a coating solution for forming film and a method for producing substrate with the film. The coating solution is prepared by: dissolving or dispering an orgnaic compound (A) which can form a chelate with metal alcoholate, at least on of a silane compound having more than 3 functional groups and repreated as the formula (2) and hydrolyzed condensates thereof (B), and at least one of a metal alcoholate represetned as (3) and a hydrolyzed condensate thereof. Molar ratio of A (M1) to C (M3) is 0.25 < (M1/M3) < 2.0; the molar ratio of B (M2) to C (M3) is 0.1 < (M2/M3) < 9.0; (R3)(4-m)Si(R4)m(2)M(OR5)n(3).

Description

被膜形成用之塗佈液及其製造方法、以及附被膜基材之製造方法 Coating liquid for forming a film, method for producing the same, and method for producing the same

本發明係關於一種被膜形成用之塗佈液。 The present invention relates to a coating liquid for forming a film.

詳細而言，本發明係關於一種儘管於相對低溫下進行硬化，亦可形成硬度及抗龜裂性之兼顧性優異之透明被膜的塗佈液。 In particular, the present invention relates to a coating liquid for a transparent film which is excellent in both hardness and crack resistance, although it is cured at a relatively low temperature.

先前，為了對玻璃或塑膠等之基材賦予功能而於基材表面形成被膜。例如，為了提高玻璃、塑膠片、塑膠透鏡、樹脂膜、及顯示裝置前面板等基材表面之耐擦傷性，而於基材表面形成硬塗膜。作為此種硬塗膜，已知有有機樹脂膜及無機膜。進而，亦已知有於有機樹脂膜及無機膜中摻合樹脂粒子或二氧化矽(silica)等無機粒子，而進一步提高耐擦傷性之情況。 Previously, a film was formed on the surface of a substrate in order to impart a function to a substrate such as glass or plastic. For example, in order to improve the scratch resistance of the surface of a substrate such as a glass, a plastic sheet, a plastic lens, a resin film, and a front panel of a display device, a hard coat film is formed on the surface of the substrate. As such a hard coat film, an organic resin film and an inorganic film are known. Further, it is also known that inorganic particles such as resin particles or silica are blended in the organic resin film and the inorganic film to further improve the scratch resistance.

又，亦已知有於透明被膜中摻合導電性粒子而賦予抗靜電性能、電磁波屏蔽性能之附透明被膜基材。進而，亦已知有於透明被膜中摻合有高折射率粒子之高折射率透明被膜、於透明被膜中摻合低折射率粒子而賦予抗反射性能之低折射率透明被膜、摻合有著色顏料粒子之透明性被膜等。 Further, a transparent film substrate to which an electroconductive particle is blended in a transparent film to impart antistatic properties and electromagnetic wave shielding performance is known. Further, a high refractive index transparent film in which a high refractive index particle is blended in a transparent film, a low refractive index transparent film in which a low refractive index particle is blended in a transparent film, and a low refractive index transparent film which imparts antireflection properties are blended with coloring A transparent film of a pigment particle or the like.

又，亦已知有為了調節基材之折射率或介電常數，而使用烷 氧化物化合物、或於其中摻合有膠體粒子之塗佈液，藉由溶膠-凝膠法而形成觸控面板用之被膜之情況。然而，於該方法中，為了使被膜硬化，需要於500℃左右之溫度下進行加熱，僅能使用耐熱性較高之基材。 Further, it is also known to use an alkane in order to adjust the refractive index or dielectric constant of the substrate. The oxide compound or the coating liquid in which the colloidal particles are blended is formed by a sol-gel method to form a film for a touch panel. However, in this method, in order to cure the film, it is necessary to heat at a temperature of about 500 ° C, and only a substrate having high heat resistance can be used.

相對於此，已知有若使用包含乙醯丙酮螯合物化合物、矽烷化合物、除矽以外之金屬烷氧化物的塗佈液，(於乾燥時或乾燥後)，則可藉由紫外線照射，於相對低溫下進行硬化，而形成耐久性優異之透明陶瓷被膜(例如參照文獻1(日本特開平2-48403號公報))。 On the other hand, it is known that when a coating liquid containing an acetonitrile chelate compound, a decane compound, or a metal alkoxide other than cerium is used (at the time of drying or after drying), it can be irradiated by ultraviolet rays. The transparent ceramic film which is excellent in durability is formed by hardening at a relatively low temperature (for example, refer to Japanese Laid-Open Patent Publication No. Hei-4-48403).

又，已知有使用由如下者所構成之塗佈溶液，而形成具有微細之凹凸狀表層之溶膠凝膠膜：使添加有利用乙醯丙酮進行穩定化之金屬烷氧化物之四烷氧基矽烷進行水解及脫水縮合而成之溶膠A、與使將1個官能基進行烷基化之烷基三烷氧基矽烷水解及脫水縮合而成之溶膠B之混合物；以異丙醇為主成分之溶劑；以及與該等混合存在之二醇類(例如參照文獻2(日本特開2005-281132號公報))。 Further, it has been known to form a sol-gel film having a fine uneven surface layer by using a coating solution composed of the following: a tetraalkoxy group to which a metal alkoxide stabilized by acetonitrile is added a mixture of sol A obtained by hydrolysis and dehydration condensation of decane, and sol B obtained by hydrolysis and dehydration condensation of an alkyltrialkoxydecane which alkylates one functional group; and isopropanol as a main component The solvent and the diol which is mixed with the above (for example, refer to Document 2 (JP-A-2005-281132)).

利用文獻1所揭示之塗佈液，雖然可提供於相對低溫下進行硬化之透明被膜，但例如於基底為樹脂之情形時，存在難以抑制龜裂之產生的問題。 The coating liquid disclosed in Document 1 can be provided as a transparent film which is cured at a relatively low temperature. However, when the substrate is a resin, for example, it is difficult to suppress the occurrence of cracks.

又，文獻2中揭示有使用將3官能矽烷(例如烷基三烷氧基矽烷)進行水解及脫水縮合(水解縮合)而獲得之溶膠，而形成微細之凹凸狀表層之情況。然而，由於在低溫下難以成為硬度充分之被膜，故而需要在至少600℃左右之溫度下進行焙燒。因此，無法使用耐熱性較低之基材。 Further, in Document 2, a sol obtained by subjecting a trifunctional decane (for example, an alkyltrialkoxy decane) to hydrolysis and dehydration condensation (hydrolytic condensation) to form a fine uneven surface layer is disclosed. However, since it is difficult to form a film having a sufficient hardness at a low temperature, it is necessary to perform baking at a temperature of at least about 600 °C. Therefore, a substrate having low heat resistance cannot be used.

本發明之目的在於提供一種於塗佈至基材後具有充分之硬度並且難以產生龜裂之被膜形成用之塗佈液。 An object of the present invention is to provide a coating liquid for forming a film which has sufficient hardness after application to a substrate and which is less likely to cause cracks.

本發明者等人為了解決上述問題而進行努力研究，結果發現，若使用將可與金屬烷氧化物形成螯合物之有機化合物、3官能以上之矽烷化合物、及金屬烷氧化物(其中，除了矽烷氧化物)溶解或分散至由水及有機溶劑所構成之混合溶劑中而成之塗佈液，則可獲得具有充分之硬度並且難以產生龜裂之被膜。本發明係基於該見解而完成者。 The present inventors have made an effort to solve the above problems, and have found that an organic compound capable of forming a chelate compound with a metal alkoxide, a trifunctional or higher decane compound, and a metal alkoxide are used. When the decane oxide is dissolved or dispersed in a coating liquid composed of a mixed solvent of water and an organic solvent, a film having sufficient hardness and being hard to be cracked can be obtained. The present invention has been completed based on this finding.

即，本發明之被膜形成用之塗佈液係將可與金屬烷氧化物形成螯合物之有機化合物(A成分)、3官能以上之矽烷化合物及其水解縮合物之至少一者(B成分)、及金屬烷氧化物及其水解縮合物之至少一者(C成分)溶解或分散至包含水及有機溶劑之混合溶劑中而成。此時，A成分之莫耳數(M1)與C成分之莫耳數(M3)之莫耳比(M1/M3)為0.25以上且未達2.0，B成分之莫耳數(M2)與C成分之莫耳數(M3)之莫耳比(M2/M3)為0.1以上且9.0以下。再者，B成分與C成分分別如下述式(2)及式(3)所示。 In other words, the coating liquid for forming a film of the present invention is an organic compound (component A) which can form a chelate compound with a metal alkoxide, at least one of a trifunctional or higher decane compound and a hydrolysis condensate thereof (component B) And at least one of the metal alkoxide and the hydrolysis condensate thereof (component C) is dissolved or dispersed in a mixed solvent containing water and an organic solvent. At this time, the molar ratio (M1/M3) of the molar fraction (M1) of the component A to the molar number (M3) of the component C is 0.25 or more and less than 2.0, and the molar number (M2) and C of the component B are The molar ratio (M2/M3) of the molar number (M3) of the component is 0.1 or more and 9.0 or less. Further, the component B and the component C are each represented by the following formulas (2) and (3).

進而，將源自B成分之SiO2換算濃度(濃度C2)設為0.005~12質量%之範圍，將源自C成分之元素M之MOx換算濃度(濃度C3)設為0.02~14.25質量%之範圍，將濃度C2與濃度C3之合計(CT)設為0.1~15質量%之範圍。藉此，可提高被膜之抗龜裂性。 In addition, the SiO 2 conversion concentration (concentration C2) derived from the component B is in the range of 0.005 to 12% by mass, and the MO x conversion concentration (concentration C3) of the element M derived from the component C is 0.02 to 14.25 mass%. In the range, the total of the concentration C2 and the concentration C3 (CT) is in the range of 0.1 to 15% by mass. Thereby, the crack resistance of the film can be improved.

進而，於B成分為3官能矽烷化合物及其水解縮合物之至少一者之情形時，將莫耳比(M2/M3)設為0.5~8.0之範圍。 Further, when the component B is at least one of a trifunctional decane compound and a hydrolysis condensate thereof, the molar ratio (M2/M3) is in the range of 0.5 to 8.0.

又，本發明之塗佈液之製造方法具備以下步驟1~3。 Moreover, the manufacturing method of the coating liquid of this invention has the following procedures 1-3.

步驟1：將有機溶劑、水、3官能以上之矽烷化合物(B成分)、及水解觸媒進行摻合，而製備預備液1之步驟 Step 1: Step of preparing the preliminary liquid 1 by blending an organic solvent, water, a trifunctional or higher decane compound (component B), and a hydrolysis catalyst

步驟2：將有機溶劑、可與金屬烷氧化物形成螯合物之有機化合物(A成分)、及金屬烷氧化物(C成分)進行摻合，而製備預備液2之步驟 Step 2: a step of preparing an initial liquid 2 by blending an organic solvent, an organic compound capable of forming a chelate with a metal alkoxide (component A), and a metal alkoxide (component C)

此處，A成分之摻合量相對於C成分之金屬元素1莫耳而為0.25莫耳以上且未達2.0莫耳之範圍。 Here, the blending amount of the component A is in the range of 0.25 mol or more and less than 2.0 mol with respect to the metal element 1 mol of the component C.

步驟3：將預備液1、預備液2、及水進行摻合，於5℃以上且40℃以下進行攪拌之步驟 Step 3: mixing the preliminary liquid 1, the preliminary liquid 2, and the water, and stirring the mixture at 5 ° C or higher and 40 ° C or lower

再者，B成分與C成分分別如下述式(2)與式(3)所示。 Further, the component B and the component C are each represented by the following formulas (2) and (3).

進而，本發明之附被膜基材係使用上述任一構成之塗佈液而於基材上形成被膜。 Further, in the film-attached substrate of the present invention, a coating liquid is formed on the substrate by using the coating liquid of any of the above configurations.

進而，本發明之附被膜基材之製造方法具備：塗佈步驟，其係將上述任一構成之塗佈液塗佈至基材；乾燥步驟，其係於塗佈步驟後將基材於80℃以上且150℃以下進行加熱；照射步驟，其係於乾燥步驟後對形成於基材上之塗佈膜照射紫外線；及加熱步驟，其係於照射步驟後對塗佈膜於80℃以上且300℃以下進行加熱。由於可在300℃以下之製程中進行成膜，故而可於耐熱性較低之基材上，製作兼顧硬度及抗龜裂性之被膜。 Further, the method for producing a film-attached substrate of the present invention comprises: a coating step of applying a coating liquid of any one of the above structures to a substrate; and a drying step of applying the substrate to the substrate after the coating step Heating at a temperature above °C and below 150 ° C; an irradiation step of irradiating the coating film formed on the substrate with ultraviolet rays after the drying step; and a heating step of applying the coating film to 80 ° C or more after the irradiation step Heating is carried out below 300 °C. Since the film formation can be carried out in a process of 300 ° C or lower, a film having both hardness and crack resistance can be produced on a substrate having low heat resistance.

若應用本發明，即便不對塗佈液摻合高折射率粒子亦可形成高折射率(折射率1.3~2.3)之透明被膜。 According to the present invention, a transparent film having a high refractive index (refractive index of 1.3 to 2.3) can be formed without blending the high refractive index particles with the coating liquid.

以下，對本發明之被膜形成用之塗佈液、塗佈液之製造方法、附被膜基材、及附被膜基材之製造方法進行說明。 Hereinafter, a coating liquid for forming a film, a method for producing a coating liquid, a film substrate, and a method for producing a film substrate will be described.

[被膜形成用之塗佈液] [Coating liquid for film formation]

被膜形成用之塗佈液(以下，稱為「本塗佈液」)係將可與金屬烷氧化物形成螯合物之有機化合物(A成分)、式(2)所表示之3官能以上之矽烷化合物及其水解縮合物之至少一者(B成分)、及式(3)所表示之金屬烷氧化物及其水解縮合物之至少一者(C成分)溶解或分散至包含水及有機溶劑之混合溶劑中而成。 The coating liquid for forming a film (hereinafter referred to as "the present coating liquid") is an organic compound (component A) which can form a chelate compound with a metal alkoxide, and a trifunctional or higher compound represented by the formula (2). At least one of the decane compound and the hydrolysis condensate thereof (component B), and at least one of the metal alkoxide and the hydrolysis condensate represented by the formula (3) (component C) are dissolved or dispersed to contain water and an organic solvent. It is made from a mixed solvent.

(R3)(4-m)Si(R4)m (2) (R 3 ) (4-m) Si(R 4 ) m (2)

(此處，m為3與4之至少一者；R3為碳數1至8之未經取代或經取代之烷基、未經取代或經取代之芳基、及乙烯基之任一者；R4為碳數1至8之未經取代或經取代之烷氧基、未經取代或經取代之芳氧基、乙烯氧基、羥基、氫原子、及鹵素原子之任一者，可相同亦可不同) (wherein m is at least one of 3 and 4; and R 3 is an unsubstituted or substituted alkyl group having 1 to 8 carbon atoms, an unsubstituted or substituted aryl group, and a vinyl group; ; R 4 is an unsubstituted or substituted alkoxy group having 1 to 8 carbon atoms, an unsubstituted or substituted aryloxy group, a vinyloxy group, a hydroxyl group, a hydrogen atom, and a halogen atom; Same or different)

M(OR5)n (3) M(OR 5 ) n (3)

(此處，M為選自Be、Al、Sc、Ti、V、Cr、Fe、Ni、Zn、Ga、Ge、As、Se、Y、Zr、Nb、In、Sn、Sb、Te、Hf、Ta、W、Pb、B、Bi、Ce、及Cu中之1種元素，R5為碳數1至10之未經取代或經取代之烷基；n為與M之原子價相同之數) (here, M is selected from the group consisting of Be, Al, Sc, Ti, V, Cr, Fe, Ni, Zn, Ga, Ge, As, Se, Y, Zr, Nb, In, Sn, Sb, Te, Hf, One of Ta, W, Pb, B, Bi, Ce, and Cu, R 5 is an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms; n is the same as the valence of M)

根據上述式(2)可知，B成分有m=3之情形時之「3官能矽烷化合物及其水解縮合物之至少一者(B3成分)」、及m=4之情形時之 「4官能矽烷化合物及其水解縮合物之至少一者(B4成分)」。而且，本塗佈液包含B3成分及B4成分之至少一者作為B成分。再者，本塗佈液亦可包含將B成分與C成分水解縮合而生成之水解縮合物。 According to the above formula (2), when the component B has m = 3, "at least one of the trifunctional decane compound and its hydrolysis condensate (B3 component)", and when m = 4 "At least one of a 4-functional decane compound and a hydrolysis condensate thereof (B4 component)". Further, the coating liquid contains at least one of the B3 component and the B4 component as the component B. Further, the coating liquid may further contain a hydrolysis condensate formed by hydrolyzing and condensing the component B and the component C.

此時，A成分之莫耳數(M1)與C成分之莫耳數(M3)之莫耳比(M1/M3)需為0.25以上且未達2.0之範圍。進而，B成分之莫耳數(M2)與C成分之莫耳數(M3)之莫耳比(M2/M3)需為0.1以上且9.0以下之範圍。此處，於將各成分進行水解之情形時，莫耳數(M1~M3)亦使用以水解前之結構為基準之值。 At this time, the molar ratio (M1/M3) of the molar number (M1) of the component A and the molar number (M3) of the component C is required to be 0.25 or more and less than 2.0. Further, the molar ratio (M2/M3) of the molar number (M2) of the B component to the molar number (M3) of the C component is required to be in the range of 0.1 or more and 9.0 or less. Here, in the case where each component is hydrolyzed, the molar number (M1 to M3) is also a value based on the structure before hydrolysis.

若莫耳比(M1/M3)為2.0以上，則有A成分配位於C成分中之OR5部之大半部分，而抑制B成分與C成分之反應之虞。因此，有硬化時難以形成-M-O-Si-之交聯，所獲得之被膜之硬度變得不充分之虞。又，亦有殘存於被膜之A成分之量增加，膜之表面電阻值等電特性隨著時間經過而發生變化，從而降低可靠性之虞。又，於莫耳比(M1/M3)未達0.25之情形時，由於C成分過度反應，故而於塗佈液體中之水解縮合物之穩定性變差，塗佈液壽命縮短，因此有對所獲得之被膜之抗龜裂性產生不良影響之虞。尤其是，莫耳比(M1/M3)較佳為0.5以上且1.0以下之範圍。 When the molar ratio (M1/M3) is 2.0 or more, A is distributed to the majority of the OR 5 portion of the C component, and the reaction between the component B and the component C is suppressed. Therefore, it is difficult to form a cross-linking of -MO-Si- at the time of hardening, and the hardness of the obtained film becomes insufficient. Further, the amount of the A component remaining in the film increases, and the electrical characteristics such as the surface resistance value of the film change with time, thereby reducing the reliability. Further, when the molar ratio (M1/M3) is less than 0.25, since the C component is excessively reacted, the stability of the hydrolysis condensate in the coating liquid is deteriorated, and the life of the coating liquid is shortened, so that there is a right place. The obtained film has an adverse effect on the crack resistance of the film. In particular, the molar ratio (M1/M3) is preferably in the range of 0.5 or more and 1.0 or less.

於莫耳比(M2/M3)未達0.1之情形時，塗佈液之穩定性降低，塗佈液壽命縮短。因此，有無法穩定地獲得膜厚、折射率、硬度等被膜特性之虞。另一方面，若莫耳比(M2/M3)超過9.0，則有於將由塗佈液所形成之塗佈膜於300℃以下之溫度下進行加熱之情形時，被膜之硬度變得不充分之虞。 When the molar ratio (M2/M3) is less than 0.1, the stability of the coating liquid is lowered, and the life of the coating liquid is shortened. Therefore, there is a possibility that the film properties such as film thickness, refractive index, and hardness cannot be stably obtained. On the other hand, when the molar ratio (M2/M3) exceeds 9.0, when the coating film formed of the coating liquid is heated at a temperature of 300 ° C or lower, the hardness of the coating film becomes insufficient. Hey.

若使用此種塗佈液，則藉由UV處理及低溫(80~300℃) 下之加熱處理，可形成具備充分之硬度及耐擦傷性之被膜。因此，即便對耐熱性較差之基材亦可形成具有充分之硬度及耐擦傷性之被膜，可獲得具有充分之硬度並且難以產生龜裂之附被膜基材。 If this coating solution is used, it is treated by UV and low temperature (80~300 °C) Under the heat treatment, a film having sufficient hardness and scratch resistance can be formed. Therefore, even if the substrate having poor heat resistance and scratch resistance can be formed on the substrate having poor heat resistance, an adhesive film substrate having sufficient hardness and being hard to be cracked can be obtained.

即，根據本發明，可在不向塗佈液中摻合高折射率粒子之情況下實現被膜之高折射率化(折射率1.3~2.3)。因此，可防止習知之摻合有高折射率粒子之塗佈液之課題(因藉由高活性之微粒子包圍溶劑並且進行增黏而產生之空隙而導致膜之緻密性之降低、硬度之降低、耐化學品性之降低等)。 That is, according to the present invention, the high refractive index (refractive index of 1.3 to 2.3) of the film can be achieved without blending the high refractive index particles into the coating liquid. Therefore, it is possible to prevent the problem of the conventional coating liquid in which the high refractive index particles are blended (the voids generated by the high-activity fine particles surrounding the solvent and being thickened, resulting in a decrease in the denseness of the film and a decrease in hardness, Reduced chemical resistance, etc.).

又，源自B成分之SiO2換算濃度(濃度C2)較佳為0.005~12質量%。若濃度C2為0.005質量%以上，則可使水解反應順利地進行，而充分地提高被膜之抗龜裂性。又，若濃度C2為12質量%以下，則水解反應不會過度進行，可獲得穩定之塗佈液。尤佳為0.01~8質量%。 Further, the concentration of SiO 2 derived from the component B (concentration C2) is preferably 0.005 to 12% by mass. When the concentration C2 is 0.005% by mass or more, the hydrolysis reaction can be smoothly performed, and the crack resistance of the film can be sufficiently improved. In addition, when the concentration C2 is 12% by mass or less, the hydrolysis reaction does not proceed excessively, and a stable coating liquid can be obtained. More preferably, it is 0.01 to 8 mass%.

源自C成分之元素M之MOx換算濃度(濃度C3)較佳為0.02~14.25質量%。 The MO x conversion concentration (concentration C3) of the element M derived from the component C is preferably 0.02 to 14.25 mass%.

若濃度C3為0.02質量%以上，則水解反應順利地進行，被膜之抗龜裂性充分變高。又，若濃度C3為14.25質量%以下，則水解反應不會過度進行，而獲得穩定之塗佈液。尤佳為0.04~9.5質量%。 When the concentration C3 is 0.02% by mass or more, the hydrolysis reaction proceeds smoothly, and the crack resistance of the film is sufficiently increased. In addition, when the concentration C3 is 14.25% by mass or less, the hydrolysis reaction does not proceed excessively, and a stable coating liquid is obtained. More preferably, it is 0.04 to 9.5 mass%.

進而，濃度C2與濃度C3之合計之濃度CT較佳為0.1~15質量%。若濃度CT為0.1質量%以上，則於通常之塗佈條件下亦可獲得充分之厚度之膜，亦可減少為了獲得硬度及抗龜裂性較高之膜而重複進行塗佈之必要性。若濃度CT為15質量%以下，則通常之塗佈條件下亦可控制所獲得之膜厚，容易抑制龜裂之產生。又，塗佈液之穩定性亦變得充分， 因而可抑制經時性之黏度之上升。因此，所獲得之被膜之膜厚、折射率、硬度等特性較穩定。進而，濃度CT更佳為0.2~10質量%。 Further, the concentration CT of the total of the concentration C2 and the concentration C3 is preferably 0.1 to 15% by mass. When the concentration CT is 0.1% by mass or more, a film having a sufficient thickness can be obtained under normal coating conditions, and the necessity of repeating coating for obtaining a film having high hardness and crack resistance can be reduced. When the concentration CT is 15% by mass or less, the film thickness obtained can be controlled under normal coating conditions, and the occurrence of cracks can be easily suppressed. Moreover, the stability of the coating liquid is also sufficient. Therefore, the increase in viscosity over time can be suppressed. Therefore, the film thickness, refractive index, hardness, and the like of the obtained film are relatively stable. Further, the concentration CT is more preferably 0.2 to 10% by mass.

又，於本塗佈液包含3官能矽烷化合物及其水解縮合物中之至少一者(B3成分)作為B成分之情形時，塗佈液之pH值較佳為4~8，進而更佳為4~7.5。若包含B3成分之摻合液為酸性，則3官能矽烷化合物容易以不溶性之固形物成分之形式析出，故而欠佳。 In addition, when the coating liquid contains at least one of a trifunctional decane compound and a hydrolysis condensate thereof (component B3) as the component B, the pH of the coating liquid is preferably 4 to 8, and more preferably 4~7.5. When the blending liquid containing the component B3 is acidic, the trifunctional decane compound is easily precipitated as an insoluble solid component, which is not preferable.

又，本塗佈液所含之B成分為3官能矽烷化合物及其水解縮合物中之至少一者(B3成分)時，即，作為B成分僅包含B3成分時，B成分之莫耳數(M2)與C成分之莫耳數(M3)之莫耳比(M2/M3)需為0.5以上且8.0以下之範圍。若莫耳比(M2/M3)未達0.5，則塗佈液之穩定性降低，塗佈液壽命縮短。因此，存在無法穩定地獲得膜厚、折射率、硬度等被膜特性之情況。進而，亦有抗龜裂性降低之虞。若莫耳比(M2/M3)超過8.0，則有所獲得之被膜之硬度變得不充分，抗龜裂性降低之虞。進而，莫耳比(M2/M3)更佳為0.6以上且7.5以下。 In addition, when the component B contained in the coating liquid is at least one of a trifunctional decane compound and a hydrolysis condensate thereof (B3 component), that is, when the B component contains only the B3 component, the molar content of the component B ( The molar ratio (M2/M3) of the M2) to the molar fraction (M3) of the C component needs to be in the range of 0.5 or more and 8.0 or less. If the molar ratio (M2/M3) is less than 0.5, the stability of the coating liquid is lowered, and the life of the coating liquid is shortened. Therefore, there is a case where the film properties such as film thickness, refractive index, and hardness cannot be stably obtained. Further, there is also a problem that the crack resistance is lowered. When the molar ratio (M2/M3) exceeds 8.0, the hardness of the obtained film becomes insufficient, and the crack resistance is lowered. Further, the molar ratio (M2/M3) is more preferably 0.6 or more and 7.5 or less.

同樣地，本塗佈液僅包含B3成分作為B成分時，源自C成分之元素M之MOx換算濃度(濃度C3)較佳為0.02~14質量%，進而更佳為0.04~9.5質量%。若濃度C3為14質量%以下，則水解反應不會過度進行，而獲得穩定之塗佈液。 Likewise, the coating solution contains only the component B3 as a component B, component C from the MO element M of x in terms of concentration (concentration C3) is preferably 0.02 to 14% by mass, and further more preferably 0.04 to 9.5 mass% . When the concentration C3 is 14% by mass or less, the hydrolysis reaction does not proceed excessively, and a stable coating liquid is obtained.

其次，對塗佈液包含3官能矽烷化合物及其水解縮合物之至少一者(B3成分)、與4官能矽烷化合物及其水解縮合物之至少一者(B4成分)之情形進行說明。B3成分之莫耳數(MB3)、與B4成分之莫耳數(MB4)之莫耳比(MB4/MB3)之值較佳為0.01以上且1以下。若莫耳比(MB4/MB3) 為0.01以上，則膜之硬度提高，若為1以下，則難以引起抗龜裂性之降低。進而，莫耳比尤佳為0.01以上且0.5以下。 Next, the coating liquid contains at least one of a trifunctional decane compound and a hydrolysis condensate thereof (component B3), and at least one of a tetrafunctional decane compound and a hydrolysis condensate thereof (component B4). The value of the molar ratio (M B3 ) of the B3 component and the molar ratio (M B4 /M B3 ) of the molar number of the B4 component (M B4 ) is preferably 0.01 or more and 1 or less. When the molar ratio (M B4 /M B3 ) is 0.01 or more, the hardness of the film is increased, and when it is 1 or less, it is difficult to cause a decrease in crack resistance. Further, the molar ratio is preferably 0.01 or more and 0.5 or less.

此處，於B3成分或B4成分進行水解之情形時，莫耳數亦為以水解前之結構為基準之值。又，亦可包含B3成分與B4成分與C成分部之水解縮合物。 Here, in the case where the B3 component or the B4 component is hydrolyzed, the molar number is also a value based on the structure before hydrolysis. Further, it may contain a hydrolysis condensate of the B3 component and the B4 component and the C component.

以下，對本發明之塗佈液所含之各成分進行詳細說明。 Hereinafter, each component contained in the coating liquid of the present invention will be described in detail.

<A成分> <Component A>

A成分係可與金屬烷氧化物形成螯合物之有機化合物，可使用1種有機化合物，亦可將2種以上混合而使用。就作為螯合劑之效果之觀點而言，尤佳為使用乙醯丙酮。 The component A is an organic compound which can form a chelate with a metal alkoxide, and one type of organic compound can be used, and two or more types can also be used for mixing. From the viewpoint of the effect of the chelating agent, it is particularly preferred to use acetamidine.

除此以外，作為A成分，可例示：三氟乙醯丙酮、六氟乙醯丙酮、苯甲醯丙酮、苯甲醯三氟丙酮、二苯甲醯甲烷、呋喃甲醯丙酮、三氟呋喃甲醯丙酮、苯甲醯呋喃甲醯甲烷、噻吩甲醯丙酮、三氟噻吩甲醯丙酮、呋喃甲醯噻吩甲醯丙酮、8-羥基喹啉(oxine)、2-甲基-8-羥基喹啉、4-甲基-8-羥基喹啉、5-甲基-8-羥基喹啉、6-甲基-8-羥基喹啉、7-甲基-8-羥基喹啉、8-羥基喹啉-5-磺酸、7-碘-8-羥基喹啉-5-磺酸、喹啉-2-羧酸、喹啉-8-羧酸、8-羥基啉、4-羥基-1,5-萘啶、8-羥基-1,6-萘啶、8-羥基-1,7-萘啶、5-羥基喹啉、8-羥基喹唑啉、2,2'-聯吡啶、2-(2'-噻吩基)吡啶、1,10-啡啉、2-甲基-1,10-啡啉、5-甲基-1,10-啡啉、2,9-二甲基-1,10-啡啉、4,7-二甲基-1,10-啡啉、5-氯-1,10-啡啉、6-溴-1,10-啡啉、5-硝基-1,10-啡啉、5-苯基-1,10-啡啉、4,7-二苯基-1,10-啡啉、丁二酮肟、丁二酮肟-O-甲酯、二甲基二硫代胺基甲酸、二乙基二硫代胺基甲酸、N-亞硝基苯基羥胺、1-亞硝基-2-萘酚、2-亞硝 基-1-萘酚、3-羥基黃酮、5-羥基黃酮、1-(2-吡啶基偶氮)-2-萘酚、4-(2-吡啶基偶氮)間苯二酚、2-(4'-二甲胺基苯基偶氮)吡啶、羊毛鉻黑A(Eriochrome Black A)、羊毛鉻黑T、羊毛鉻藍黑B、羊毛鉻藍黑R、酞錯合劑、烷醇胺、及羥基酸等。 In addition, as the component A, trifluoroacetamidine acetone, hexafluoroacetamidine acetone, benzamidine acetone, benzamidine trifluoroacetone, benzotrimethane, furanone, and trifluorofuran can be exemplified. Acetone, benzamidine, methane, thiophene, acetone, trifluorothiophene, acetone, furan, oxine, oxine, 2-methyl-8-hydroxyquinoline , 4-methyl-8-hydroxyquinoline, 5-methyl-8-hydroxyquinoline, 6-methyl-8-hydroxyquinoline, 7-methyl-8-hydroxyquinoline, 8-hydroxyquinoline -5-sulfonic acid, 7-iodo-8-hydroxyquinoline-5-sulfonic acid, quinoline-2-carboxylic acid, quinoline-8-carboxylic acid, 8-hydroxyl Porphyrin, 4-hydroxy-1,5-naphthyridine, 8-hydroxy-1,6-naphthyridine, 8-hydroxy-1,7-naphthyridine, 5-hydroxyquinoline Porphyrin, 8-hydroxyquinazoline, 2,2'-bipyridine, 2-(2'-thienyl)pyridine, 1,10-morpholine, 2-methyl-1,10-morpholine, 5-A 1,10-morpholine, 2,9-dimethyl-1,10-morpholine, 4,7-dimethyl-1,10-morpholine, 5-chloro-1,10-morpholine, 6-bromo-1,10-morpholine, 5-nitro-1,10-morpholine, 5-phenyl-1,10-morpholine, 4,7-diphenyl-1,10-morpholine, Dimethylglyoxime, dimethylglyoxime-O-methyl ester, dimethyldithiocarbamic acid, diethyldithiocarbamic acid, N-nitrosophenylhydroxylamine, 1-nitroso- 2-naphthol, 2-nitroso-1-naphthol, 3-hydroxyflavone, 5-hydroxyflavone, 1-(2-pyridylazo)-2-naphthol, 4-(2-pyridyl) Nitrogen) Resorcinol, 2-(4'-dimethylaminophenylazo)pyridine, Eriochrome Black A, Wool Chrome Black T, Wool Chrome Blue Black B, Wool Chrome Blue Black R , 酞 wrong mixture, alkanolamine, and hydroxy acid.

作為A成分，尤其適合為下述式(1)所表示之具有2個以上羰基之羰基化合物。 The component A is particularly preferably a carbonyl compound having two or more carbonyl groups represented by the following formula (1).

式(1)中，R1為碳數1~10之有機基。R2為碳數1~10之有機基或羥基。作為R1，例如可列舉：甲基、乙基、異丙基、苯基、呋喃基、噻吩基、三氟甲基、甲氧基、及乙氧基等。尤佳為甲基、乙基、及乙氧基。關於R2，例如可例示：甲基、乙基、異丙基、苯基、呋喃基、噻吩基、三氟基、甲氧基、及乙氧基等作為有機基。 In the formula (1), R 1 is an organic group having 1 to 10 carbon atoms. R 2 is an organic group or a hydroxyl group having 1 to 10 carbon atoms. Examples of R 1 include a methyl group, an ethyl group, an isopropyl group, a phenyl group, a furyl group, a thienyl group, a trifluoromethyl group, a methoxy group, and an ethoxy group. More preferably, it is a methyl group, an ethyl group, and an ethoxy group. Examples of R 2 include , as an organic group, a methyl group, an ethyl group, an isopropyl group, a phenyl group, a furyl group, a thienyl group, a trifluoro group, a methoxy group, and an ethoxy group.

<B成分> <B ingredient>

藉由摻合B成分(3官能以上之矽烷化合物)，塗佈膜(透明被膜)之硬度或抗龜裂性提高。尤其是，3官能矽烷化合物由於具有大體積之非官能性之有機基(碳數1至8之未經取代或經取代之烷基、未經取代或經取代之芳基、及乙烯基)，故而對被膜賦予可撓性，進而提高被膜與基材(有機材料)之潤濕性。因此，抗龜裂性進一步提高。又，於藉由成膜步驟中之紫外線照射而使有機基之至少一部分發生分解之情形時，亦可緩和應力集中，因此此情況亦有助於提昇抗龜裂性。 By blending the B component (a tri- or higher-functional decane compound), the hardness or crack resistance of the coating film (transparent film) is improved. In particular, the trifunctional decane compound has a large volume of a non-functional organic group (an unsubstituted or substituted alkyl group having 1 to 8 carbon atoms, an unsubstituted or substituted aryl group, and a vinyl group), Therefore, flexibility is imparted to the film, and the wettability between the film and the substrate (organic material) is further improved. Therefore, the crack resistance is further improved. Further, when at least a part of the organic group is decomposed by ultraviolet irradiation in the film forming step, stress concentration can be alleviated, and this also contributes to improvement of crack resistance.

於上述式(2)之R3及R4中，作為碳數1至8之未經取代烷 氧基，可列舉：甲氧基、乙氧基、異丙氧基、及丁氧基等。同樣地，作為經取代之烷氧基，可列舉將上述未經取代烷氧基之氫原子取代為甲基、乙基等而成之基。作為芳氧基，可列舉：苯氧基、及萘氧基等。作為鹵素原子，可列舉：氟原子、氯原子、溴原子、及碘原子等。 In R 3 and R 4 of the above formula (2), examples of the unsubstituted alkoxy group having 1 to 8 carbon atoms include a methoxy group, an ethoxy group, an isopropoxy group, and a butoxy group. Similarly, examples of the substituted alkoxy group include a group in which a hydrogen atom of the above unsubstituted alkoxy group is substituted with a methyl group, an ethyl group or the like. Examples of the aryloxy group include a phenoxy group and a naphthyloxy group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

又，作為3官能矽烷化合物，可較佳地列舉：甲基三甲氧基矽烷(MTMS)、甲基三乙氧基矽烷(MTES)、乙基三乙氧基矽烷(ETES)、甲基三異丙氧基矽烷、乙基三甲氧基矽烷、乙基三異丙氧基矽烷、辛基三甲氧基矽烷、辛基三乙氧基矽烷、乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、苯基三甲氧基矽烷、苯基三乙氧基矽烷、三氟甲基三甲氧基矽烷、三氟甲基三乙氧基矽烷、γ-(甲基)丙烯醯氧基丙基二甲氧基矽烷、及γ-(甲基)丙烯醯氧基丙基二乙氧基矽烷等。該等可使用1種，亦可將任意2種以上混合而使用。但是，若R3成為過長之長鏈，則有難以獲得充分之硬度之虞。又，若R3互不相同，則水解速度產生差異，變得難以引起均勻之反應，因此較佳為使用甲基三甲氧基矽烷(MTMS)。 Further, examples of the trifunctional decane compound include methyltrimethoxydecane (MTMS), methyltriethoxydecane (MTES), ethyltriethoxydecane (ETES), and methyltrimethylene. Propoxydecane, ethyltrimethoxydecane, ethyltriisopropoxydecane, octyltrimethoxydecane, octyltriethoxydecane, vinyltrimethoxydecane, vinyltriethoxydecane , phenyl trimethoxy decane, phenyl triethoxy decane, trifluoromethyl trimethoxy decane, trifluoromethyl triethoxy decane, γ-(methyl) propylene methoxy propyl dimethoxy Base decane, and γ-(meth) propylene methoxy propyl diethoxy decane. These may be used alone or in combination of two or more. However, if R 3 is a long chain which is too long, it is difficult to obtain sufficient hardness. Further, when R 3 is different from each other, the hydrolysis rate is different and it becomes difficult to cause a uniform reaction. Therefore, methyltrimethoxydecane (MTMS) is preferably used.

作為4官能矽烷化合物，可列舉：四甲氧基矽烷、四乙氧基矽烷、四丙氧基矽烷、四異丙氧基矽烷、四丁氧基矽烷、四氯矽烷、三甲氧基矽烷等。尤佳為四乙氧基矽烷。 The tetrafunctional decane compound may, for example, be tetramethoxy decane, tetraethoxy decane, tetrapropoxy decane, tetraisopropoxy decane, tetrabutoxy decane, tetrachloro decane or trimethoxy decane. More preferably tetraethoxy decane.

4官能矽烷化合物可單獨使用1種，亦可將多種組合而使用。 The tetrafunctional decane compound may be used singly or in combination of two or more.

〈C成分〉 <C component>

如上所述，C成分係式(3)所表示之金屬烷氧化物及其水解縮合物之至少一者。C成分之金屬元素M係選擇除Si以外之金屬元素。具體而言，使用金屬元素M為選自Be、Al、Sc、Ti、V、Cr、Fe、Ni、Zn、 Ga、Ge、As、Se、Y、Zr、Nb、In、Sn、Sb、Te、Hf、Ta、W、Pb、B、Bi、Ce及Cu中之至少1種元素之烷氧化物。尤佳為Ti、Al、Zr。 As described above, the C component is at least one of a metal alkoxide represented by the formula (3) and a hydrolysis condensate thereof. The metal element M of the component C is a metal element other than Si. Specifically, the metal element M is selected from the group consisting of Be, Al, Sc, Ti, V, Cr, Fe, Ni, Zn, An alkoxide of at least one of Ga, Ge, As, Se, Y, Zr, Nb, In, Sn, Sb, Te, Hf, Ta, W, Pb, B, Bi, Ce, and Cu. Especially preferred are Ti, Al, and Zr.

關於作為C成分之金屬烷氧化物，可列舉：三甲醇鋁、三乙醇鋁、三丙醇鋁、三異丙醇鋁、三正丁醇鋁、三異丁醇鋁、三第三丁醇鋁、三戊醇鋁、三己醇鋁、三辛醇鋁、三苄醇鋁、三苯酚鋁、三甲氧基乙醇鋁、三甲氧基乙氧基乙醇鋁、三甲氧基丙醇鋁、四甲醇鈦、四乙醇鈦、四丙醇鈦、四異丙醇鈦、四甲氧基乙醇鈦、四丁醇鈦、四甲醇鋯、四乙醇鋯、四丙醇鋯、四異丙醇鋯、四甲氧基乙醇鋯、四丁醇鋯、五乙醇鈮、三甲醇銦、三乙醇銦、三丙醇銦、三異丙醇銦、三正丁醇銦、三異丁醇銦、三第三丁醇銦、三戊醇銦、三己醇銦、三辛醇銦、三苄醇銦、三苯酚銦、三甲氧基乙醇銦、三甲氧基乙氧基乙醇銦、三甲氧基丙醇銦、三甲醇銻、三乙醇銻、三丙醇銻、三異丙醇銻、三正丁醇銻、及三異丁醇銻等。該等可使用1種亦可將任意2種以上混合而使用，就水解速度適當且容易取得之觀點而言，較佳為使用四異丙醇鈦、四丙醇鋯。 Examples of the metal alkoxide as the component C include trimethyl aluminum oxide, aluminum triethoxide, aluminum tripropoxide, aluminum triisopropoxide, aluminum tri-n-butoxide, aluminum triisobutoxide, and aluminum tris-butoxide. , aluminum lauryl alcohol, aluminum tridecoxide, aluminum trioctoxide, aluminum tribenzyl alcohol, aluminum trisphenol, aluminum trimethoxyethanol, aluminum trimethoxyethoxyethanol, aluminum trimethoxypropoxide, titanium tetramethoxide , titanium tetraethoxide, titanium tetrapropoxide, titanium tetraisopropoxide, titanium tetramethoxyethanol, titanium tetrabutoxide, zirconium tetramethoxide, zirconium tetraethoxide, zirconium tetrapropoxide, zirconium tetraisopropoxide, tetramethoxy Zirconium glycolate, zirconium tetrabutoxide, barium pentoxide, indium triacetate, indium triethoxide, indium tripropoxide, indium triisopropoxide, indium tri-n-butoxide, indium triisobutoxide, indium trisuccinate , indium trieol, indium trihexoxide, indium trioctyl alcohol, indium tribenzyl alcohol, indium trisphenol, indium trimethoxyethanol, indium trimethoxyethoxyethanol, indium trimethoxypropoxide, trimethyl hydrazine , triethanol oxime, tripropion oxime, triisopropanol oxime, tri-n-butanol oxime, and triisobutanol oxime. These may be used alone or in combination of two or more kinds. From the viewpoint of appropriate hydrolysis rate and easy availability, it is preferred to use titanium tetraisopropoxide or zirconium tetrapropoxide.

〈D成分〉 <D component>

於本塗佈液中，存在源自製造步驟之水解用觸媒殘留0.2質量%左右之情況。根據本塗佈液之用途，期望將水解用觸媒去除。於該情形時，例如可藉由離子交換、中和、蒸餾等將水解用觸媒去除。於進行中和之情形時，酸中和物質殘留於本塗佈液體中。以下，對中和處理之情形進行詳細說明。 In the coating liquid, the catalyst for hydrolysis derived from the production step may remain in an amount of about 0.2% by mass. According to the use of the coating liquid, it is desirable to remove the catalyst for hydrolysis. In this case, the hydrolysis catalyst can be removed, for example, by ion exchange, neutralization, distillation, or the like. In the case of neutralization, the acid neutralizing substance remains in the coating liquid. Hereinafter, the case of the neutralization process will be described in detail.

D成分係為了將塗佈液之pH值設為4~8而添加之酸中和物質。於包含3官能矽烷化合物(B3成分)作為上述B成分之情形時，B3 成分被酸觸媒等水解用觸媒所水解。為了將摻合液恢復至中性而添加酸中和物質。若摻合液為酸性之狀態，則3官能矽烷化合物容易以不溶性之固形物成分之形式析出，故而欠佳。本塗佈液體中所含之D成分較佳為1質量%以下。 The D component is an acid neutralizing substance added to adjust the pH of the coating liquid to 4 to 8. When a trifunctional decane compound (component B3) is contained as the above component B, B3 The component is hydrolyzed by a hydrolysis catalyst such as an acid catalyst. An acid neutralizing substance is added in order to restore the blending solution to neutrality. When the blending liquid is in an acidic state, the trifunctional decane compound is easily precipitated as an insoluble solid component, which is not preferable. The component D contained in the coating liquid is preferably 1% by mass or less.

關於酸中和物質，就金屬雜質之混入、向有機溶劑中之溶解性之觀點而言，適宜為胺化合物。作為胺化合物，可列舉：三乙醇胺、二乙醇胺、單乙醇胺、三甲基胺、乙二胺、哌啶、苯胺、及吡啶等。可使用1種酸中和物質，亦可將任意2種以上酸中和物質混合而使用。 The acid neutralizing substance is preferably an amine compound from the viewpoint of mixing metal impurities and solubility in an organic solvent. Examples of the amine compound include triethanolamine, diethanolamine, monoethanolamine, trimethylamine, ethylenediamine, piperidine, aniline, and pyridine. One type of acid neutralizing substance may be used, and any two or more types of acid neutralizing substances may be used in combination.

〈混合溶劑〉 <mixed solvent>

本塗佈液中使用水及有機溶劑之混合溶劑。但是，作為有機溶劑，排除可與上述成分(A)金屬烷氧化物形成螯合物之有機化合物(A成分)。作為水與有機溶劑之混合比率，較佳為水/有機溶劑(質量比)為20/80~0.1/99.9，更佳為10/90~1/99。關於有機溶劑，沸點較佳為120℃以上。更佳為150℃以上。其中，沸點較佳為300℃以下。又，於20℃之有機溶劑之黏度較佳為1~400mPa‧s之範圍，更佳為20~350mPa‧s之範圍。又，於混合多種有機溶劑之情形時，沸點為120℃以上、於20℃之黏度為1~400mPa‧s之有機溶劑較佳為50質量%以上，更佳為60質量%以上。 A mixed solvent of water and an organic solvent is used in the coating liquid. However, as the organic solvent, an organic compound (component A) which can form a chelate compound with the metal alkoxide of the above component (A) is excluded. As a mixing ratio of water and an organic solvent, it is preferred that the water/organic solvent (mass ratio) is 20/80 to 0.1/99.9, more preferably 10/90 to 1/99. Regarding the organic solvent, the boiling point is preferably 120 ° C or higher. More preferably 150 ° C or more. Among them, the boiling point is preferably 300 ° C or less. Further, the viscosity of the organic solvent at 20 ° C is preferably in the range of 1 to 400 mPa ‧ s, more preferably in the range of 20 to 350 mPa ‧ s. Further, in the case of mixing a plurality of organic solvents, the organic solvent having a boiling point of 120 ° C or higher and a viscosity at 20 ° C of 1 to 400 mPa ‧ is preferably 50% by mass or more, and more preferably 60% by mass or more.

作為有機溶劑，可列舉：甲醇、乙醇、異丙醇、丁醇、二丙酮醇、呋喃甲醇、乙二醇、己二醇等醇類；乙酸甲酯、乙酸乙酯等酯類；二***、乙二醇單甲醚、乙二醇單***、二乙二醇單甲醚、二乙二醇單***、二乙二醇單丁醚、丙二醇單甲醚、丙二醇單丙醚等醚類；丙酮、及甲基乙基酮等酮類等。 Examples of the organic solvent include alcohols such as methanol, ethanol, isopropanol, butanol, diacetone alcohol, furan methanol, ethylene glycol, and hexanediol; esters such as methyl acetate and ethyl acetate; diethyl ether; Ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monopropyl ether; acetone And ketones such as methyl ethyl ketone.

再者，於本塗佈液中，於不妨礙其效果之範圍，可添加任意成分。例如，亦可添加無機氧化物微粒子、有機樹脂微粒子、有機聚矽氧烷樹脂微粒子、顏料、著色料、抗靜電劑、及界面活性劑等。 Further, in the coating liquid, an optional component may be added in a range that does not impair the effect. For example, inorganic oxide fine particles, organic resin fine particles, organic polyoxyalkylene resin fine particles, pigments, coloring materials, antistatic agents, and surfactants may be added.

[本塗佈液之製造方法] [Method for Producing the Coating Liquid]

本塗佈液之製造方法包括下述步驟1、步驟2及步驟3。 The manufacturing method of the coating liquid includes the following steps 1, 2, and 3.

步驟1：將有機溶劑、水、B成分(式(2)所表示之3官能以上之矽烷化合物)及水解觸媒進行摻合，而製備預備液1之步驟 Step 1: Step of preparing the preliminary liquid 1 by blending an organic solvent, water, a component B (a tri- or higher-functional decane compound represented by the formula (2)), and a hydrolysis catalyst

此處，於B成分使用4官能矽烷化合物之情形時，B成分之摻合量相對於步驟2中之C成分之金屬元素M之1莫耳，為0.1莫耳以上且9.0莫耳以下之範圍。 Here, in the case where a tetrafunctional decane compound is used for the component B, the blending amount of the component B is in the range of 0.1 mol or more and 9.0 mol or less with respect to 1 mol of the metal element M of the component C in the step 2. .

又，於B成分使用3官能矽烷化合物之情形時，B成分之摻合量相對於步驟2中之C成分之金屬元素M之1莫耳，為0.5莫耳以上且8.0莫耳以下之範圍。進而，實施中和處理，而將預備液1之pH值調整為5~8之範圍。 Further, when a trifunctional decane compound is used for the component B, the blending amount of the component B is in the range of 0.5 mol or more and 8.0 mol or less with respect to 1 mol of the metal element M of the component C in the step 2. Further, the neutralization treatment is carried out, and the pH of the preliminary liquid 1 is adjusted to a range of 5 to 8.

步驟2：將有機溶劑、A成分、及C成分(式(3)所表示之金屬烷氧化物)進行摻合，而製備金屬烷氧化物溶液(預備液2)之步驟 Step 2: a step of preparing a metal alkoxide solution (preparation liquid 2) by blending an organic solvent, a component A, and a component C (metal alkoxide represented by the formula (3))

此處，A成分相對於C成分之金屬元素M之1莫耳，為0.25莫耳以上且未達2莫耳之範圍。 Here, the A component is in a range of 0.25 mol or more and less than 2 mol with respect to 1 mol of the metal element M of the C component.

步驟3：將於步驟1中所獲得之預備液1、於步驟2中所獲得之預備液2、及水進行摻合，且於5℃以上且40℃以下之溫度下進行攪拌之步驟 Step 3: mixing the preliminary liquid obtained in the step 1, the preliminary liquid 2 obtained in the step 2, and water, and stirring at a temperature of 5 ° C or higher and 40 ° C or lower.

以下，對上述各步驟進行詳細說明。 Hereinafter, each step described above will be described in detail.

<步驟1> <Step 1>

於B成分使用4官能矽烷化合物之情形時，於有機溶劑、水及水解用觸媒之存在下，使4官能矽烷化合物水解縮合，而製備4官能矽烷化合物及其水解縮合物之至少一者分散至混合溶劑中而成之溶液(預備液1)。或者，於B成分使用3官能矽烷化合物之情形時，於有機溶劑、水及水解用觸媒之存在下，使3官能矽烷化合物水解縮合，進而實施中和而將溶液之pH值設為5~8之範圍。藉由上述方式，可獲得3官能矽烷化合物及其水解縮合物中之至少一者分散至混合溶劑中而成之預備液1。通常，於該步驟1中，於有機溶劑中添加水、水解用觸媒、B成分，於5~40℃進行5~120分鐘之攪拌，而獲得預備液1。 When a tetrafunctional decane compound is used for the component B, the tetrafunctional decane compound is hydrolyzed and condensed in the presence of an organic solvent, water and a catalyst for hydrolysis to prepare at least one of the tetrafunctional decane compound and its hydrolysis condensate. A solution (prepared solution 1) in a mixed solvent. Alternatively, when a trifunctional decane compound is used for the component B, the trifunctional decane compound is hydrolyzed and condensed in the presence of an organic solvent, water and a catalyst for hydrolysis, and further neutralized to set the pH of the solution to 5~ The scope of 8. According to the above aspect, the preliminary liquid 1 obtained by dispersing at least one of a trifunctional decane compound and a hydrolysis condensate thereof in a mixed solvent can be obtained. Usually, in this step 1, water, a catalyst for hydrolysis, and a component B are added to an organic solvent, and the mixture is stirred at 5 to 40 ° C for 5 to 120 minutes to obtain a preliminary liquid 1.

作為水解用觸媒，可使用(a)硝酸、乙酸、鹽酸、硫酸、硝酸、磷酸、氟化氫等無機酸、(b)草酸、順丁烯二酸等羧酸、(c)甲磺酸等磺酸、及(d)酸性或弱酸性之無機鹽等觸媒。但是，並不限定於該等。又，亦可將多種該等觸媒任意地進行混合。水解觸媒之量相對於B成分之3官能以上之矽烷化合物，較佳為0.001~1莫耳%(SiO2換算、外加比例)之範圍內。 As the catalyst for hydrolysis, (a) a mineral acid such as nitric acid, acetic acid, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid or hydrogen fluoride; (b) a carboxylic acid such as oxalic acid or maleic acid or (c) a sulfonic acid such as methanesulfonic acid can be used. A catalyst such as an acid or (d) an acidic or weakly acidic inorganic salt. However, it is not limited to these. Further, a plurality of such catalysts may be arbitrarily mixed. The amount of the hydrolysis catalyst is preferably in the range of 0.001 to 1 mol% (in terms of SiO 2 and addition ratio) with respect to the trifunctional or higher decane compound of the component B.

水之量相對於B成分之3官能以上之矽烷化合物1莫耳，較佳為0.5~10莫耳(SiO2換算、外加比例)之範圍。只要為該莫耳比之範圍，則於有效地促進B成分之水解方面有效。再者，水之量更佳為1~8莫耳之範圍。 The amount of water is preferably in the range of 0.5 to 10 moles (in terms of SiO 2 in terms of addition ratio) with respect to 1 part or more of the decane compound 1 mol of the component B. As long as it is the range of the molar ratio, it is effective in effectively promoting the hydrolysis of the component B. Furthermore, the amount of water is preferably in the range of 1 to 8 moles.

關於B成分於預備液1中之量，只要為可進行水解縮合之程度，則無特別限定，較佳為0.01~8質量%(SiO2換算)之範圍。 The amount of the component B in the preliminary liquid 1 is not particularly limited as long as it can be hydrolyzed and condensed, and is preferably in the range of 0.01 to 8% by mass (in terms of SiO 2 ).

又，於B成分為3官能矽烷化合物之情形時，產生3官能 矽烷化合物之水解縮合物後，為了將摻合液恢復至中性而添加酸中和物質。若包含B成分之摻合液為酸性之狀態，則3官能矽烷化合物容易以不溶性之固形物成分之形式析出，故而欠佳。此處，推薦3官能矽烷溶液之pH值較佳為5~8，更佳為pH值6~7.5。 Further, when the component B is a trifunctional decane compound, a trifunctional group is produced. After the hydrolysis condensate of the decane compound, an acid neutralizing substance is added in order to restore the blending liquid to neutrality. When the blending liquid containing the component B is in an acidic state, the trifunctional decane compound is easily precipitated as an insoluble solid component, which is not preferable. Here, the pH of the trifunctional decane solution is preferably from 5 to 8, more preferably from 6 to 7.5.

再者，酸中和物質(D成分)並非必須。亦可不藉由添加酸中和物質，而使用離子交換樹脂，將水解用觸媒去除，而將pH值設為5~8。 Further, the acid neutralizing substance (component D) is not essential. Instead of adding an acid neutralizing substance, an ion exchange resin may be used to remove the hydrolysis catalyst, and the pH may be set to 5-8.

<步驟2> <Step 2>

於該步驟中，於有機溶劑中添加A成分及C成分(式(3)所表示之金屬烷氧化物)，並進行攪拌，藉此製備包含金屬烷氧化物或其水解縮合物之金屬烷氧化物溶液(預備液2)。有機溶劑、A成分或C成分如上所述。 In this step, the component A and the component C (metal alkoxide represented by the formula (3)) are added to an organic solvent and stirred to prepare a metal alkoxide containing a metal alkoxide or a hydrolysis condensate thereof. Solution (preparation solution 2). The organic solvent, component A or component C is as described above.

該步驟中之A成分之莫耳數(M1)相對於C成分之莫耳數(M3)之莫耳比(M1/M3)為0.25以上且未達2.0之範圍。於該步驟中，A成分會與C成分之烷氧基進行配位，若莫耳比(M1/M3)為0.25以上且未達2.0之範圍，則會殘存未與A成分所具有之螯合物配位基進行配位之金屬烷氧化物，故而可控制C成分之反應性。再者，莫耳比(M1/M3)更佳為0.5以上且1.0以下之範圍。 The molar ratio (M1) of the A component in the step to the molar ratio (M1/M3) of the molar component (M3) of the C component is 0.25 or more and less than 2.0. In this step, the component A is coordinated with the alkoxy group of the component C. If the molar ratio (M1/M3) is 0.25 or more and less than 2.0, the residual component of the component A does not remain. Since the ligand has a metal alkoxide coordinated, the reactivity of the component C can be controlled. Further, the molar ratio (M1/M3) is more preferably in the range of 0.5 or more and 1.0 or less.

於莫耳比(M1/M3)為2.0以上之情形時，由於過度進行金屬烷氧化物針對烷氧基之配位，故而有金屬烷氧化物之穩定化過大，對與B成分之共水解縮合產生影響，而變得不適合於被膜形成用塗佈液之低溫硬化(80~300℃)之虞。 When the molar ratio (M1/M3) is 2.0 or more, since the coordination of the metal alkoxide with respect to the alkoxy group is excessively performed, the stabilization of the metal alkoxide is excessive, and the co-hydrolysis condensation with the component B is carried out. It is not suitable for the low-temperature hardening (80 to 300 ° C) of the coating liquid for film formation.

藉由該步驟所獲得之金屬烷氧化物溶液包含配位有A成分 之金屬烷氧化物或其水解縮合物。 The metal alkoxide solution obtained by this step comprises a coordinated A component a metal alkoxide or a hydrolysis condensate thereof.

<步驟3> <Step 3>

於步驟1中所製備之3官能以上之矽烷溶液(預備液1)中，添加步驟2中所製備之金屬烷氧化物溶液(預備液2)，繼而添加水，於5~40℃進行攪拌，而獲得本塗佈液。 Adding the metal alkoxide solution (preparation solution 2) prepared in the step 2 to the trifunctional or higher decane solution (preparation solution 1) prepared in the step 1, followed by adding water and stirring at 5 to 40 ° C. The coating liquid was obtained.

就抗龜裂性之觀點而言，於該步驟前，預備液1所含之B成分、即水解縮合後之B成分之重量平均分子量(聚苯乙烯換算)較佳為300~3000之範圍。再者，B成分之重量平均分子量更佳為500~1500之範圍。此處，重量平均分子量係藉由GPC而求出。 From the viewpoint of the crack resistance, the weight average molecular weight (in terms of polystyrene) of the component B contained in the preliminary liquid 1 and the component B after hydrolysis and condensation is preferably in the range of 300 to 3,000. Further, the weight average molecular weight of the component B is more preferably in the range of 500 to 1,500. Here, the weight average molecular weight is determined by GPC.

此處，於B成分為4官能矽烷化合物之情形時，B成分之莫耳數(M2)與C成分之莫耳數(M3)之莫耳比(M2/M3)為0.1以上且9.0以下，較佳為0.2以上且5.0以下之範圍。於B成分為3官能矽烷化合物之情形時，B成分之莫耳數(M2)與C成分之莫耳數(M3)之莫耳比(M2/M3)為0.5以上且8以下，較佳為0.6以上且7.5以下之範圍。其原因在於，若莫耳比(M2/M3)為該等範圍內，則共水解反應會順利進行。 Here, when the component B is a tetrafunctional decane compound, the molar ratio (M2/M3) of the molar number (M2) of the component B and the molar number (M3) of the component C is 0.1 or more and 9.0 or less. It is preferably in the range of 0.2 or more and 5.0 or less. When the component B is a trifunctional decane compound, the molar ratio (M2/M3) of the molar fraction (M2) of the component B to the molar fraction (M3) of the component C is preferably 0.5 or more and 8 or less, preferably A range of 0.6 or more and 7.5 or less. The reason for this is that if the molar ratio (M2/M3) is within these ranges, the co-hydrolysis reaction proceeds smoothly.

藉由添加水，可促進3官能以上之矽烷之水解縮合物、與金屬烷氧化物之至少一者之共水解縮合反應，因此於獲得緻密之被膜之方面而言較佳。 By adding water, a hydrolysis-condensation product of a trifunctional or higher decane and a co-hydrolysis condensation reaction with at least one of the metal alkoxides can be promoted, and therefore, it is preferable in terms of obtaining a dense film.

再者，於B成分包含3官能矽烷化合物之情形時，本塗佈液之pH值較佳為4~8，更佳為4~7.5。 Further, in the case where the component B contains a trifunctional decane compound, the pH of the coating liquid is preferably from 4 to 8, more preferably from 4 to 7.5.

[附被膜基材之製造方法] [Method of Manufacturing Film Attached Substrate]

附被膜基材之製造方法包括：塗佈步驟，其係將本塗佈液塗 佈至基材；乾燥步驟，其使基材上之塗佈液乾燥而形成塗佈膜；及硬化步驟，其係使基材上之塗佈膜硬化而形成附被膜基材。對該乾燥步驟及硬化步驟進而詳細地進行說明，乾燥步驟係由將基材上之塗佈液於80℃以上且150℃以下之溫度下進行加熱之步驟所構成，硬化步驟係由對乾燥步驟後之附塗佈膜之基材照射紫外線之照射步驟及於80℃以上且300℃以下之溫度下進行加熱之加熱步驟所構成。 The manufacturing method of the film-attached substrate includes a coating step of coating the coating liquid a coating to a substrate; a drying step of drying the coating liquid on the substrate to form a coating film; and a curing step of curing the coating film on the substrate to form an adhesive film substrate. The drying step and the hardening step are further described in detail. The drying step is performed by a step of heating the coating liquid on the substrate at a temperature of 80 ° C or higher and 150 ° C or lower, and the curing step is performed by a drying step. The substrate to which the coating film is attached is irradiated with ultraviolet rays and a heating step of heating at a temperature of 80 ° C or higher and 300 ° C or lower.

作為將本塗佈液塗佈至基材之塗佈方法，可採用浸漬法、旋轉塗佈法、棒式塗佈法、噴霧法、輥式塗佈法、軟版印刷法、狹縫式塗佈法等先前公知之方法。作為基材，例如可列舉：使用有玻璃、經ITO膜處理之基材、聚碳酸酯、丙烯酸樹脂、PET、及TAC等素材之片、膜、及板等。 As a coating method for applying the coating liquid to a substrate, a dipping method, a spin coating method, a bar coating method, a spray method, a roll coating method, a soft printing method, or a slit coating method may be employed. A previously known method such as cloth method. Examples of the substrate include sheets, films, and sheets of materials such as glass, ITO-treated substrates, polycarbonate, acrylic, PET, and TAC.

於乾燥步驟中，只要可於不使基材變質之情況下獲得所需之硬度、抗龜裂性等，則對加熱溫度並無特別限定，較佳為80~150℃之範圍，更佳為90~140℃之範圍。又，於乾燥步驟中，較佳為加熱1~10分鐘左右。 In the drying step, the heating temperature is not particularly limited as long as the desired hardness, crack resistance, and the like can be obtained without deteriorating the substrate, and it is preferably in the range of 80 to 150 ° C, more preferably Range of 90~140 °C. Further, in the drying step, it is preferably heated for about 1 to 10 minutes.

於乾燥步驟中，只要可獲得具有所需之硬度、抗龜裂性等之被膜，則可於一次之步驟操作中實施乾燥及加熱，亦可於乾燥後於高於乾燥溫度之溫度下進行加熱。作為乾燥方法或加熱方法，可使用先前公知之方法。又，亦可併用電磁波照射處理。 In the drying step, as long as a film having a desired hardness, crack resistance, or the like is obtained, drying and heating may be performed in one step operation, or may be performed at a temperature higher than the drying temperature after drying. . As the drying method or the heating method, a previously known method can be used. Further, electromagnetic wave irradiation treatment may be used in combination.

於乾燥步驟中之加熱溫度未達80℃之情形時，因溶劑之殘存、或者-M-O-M-、或-M-O-Si-之交聯不足，而無法獲得充分之膜強度，若加熱乾燥溫度超過150℃，則存在B成分之有機基發生分解，而無法獲得所需膜特性之情況。 When the heating temperature in the drying step is less than 80 ° C, sufficient film strength cannot be obtained due to the residual solvent or insufficient crosslinking of -MOM- or -MO-Si-, if the heating and drying temperature exceeds 150 At °C, the organic group of the component B is decomposed, and the desired film characteristics cannot be obtained.

於照射步驟中，對藉由乾燥步驟而乾燥之透明被膜照射紫外線(UV)。例如使用2kw之高壓水銀燈照射3,000mJ/cm2之紫外線。藉由UV照射，於被膜內產生A成分之脫附，被膜成為於加熱步驟中容易交聯之狀態。 In the irradiation step, the transparent film dried by the drying step is irradiated with ultraviolet rays (UV). For example, a high-pressure mercury lamp of 2 kW is used to irradiate 3,000 mJ/cm 2 of ultraviolet rays. Desorption of the A component occurs in the film by UV irradiation, and the film is in a state of being easily crosslinked in the heating step.

於照射步驟之後，將被膜於80~300℃之範圍進行加熱。藉由該加熱步驟，透明被膜成為充分地進行交聯之狀態。若加熱溫度為80~300℃之範圍，例如可抑制ITO配線之電阻變化。再者，加熱時間較佳為1~10分鐘。 After the irradiation step, the film is heated in the range of 80 to 300 °C. By this heating step, the transparent film is in a state of being sufficiently crosslinked. When the heating temperature is in the range of 80 to 300 ° C, for example, the resistance change of the ITO wiring can be suppressed. Furthermore, the heating time is preferably from 1 to 10 minutes.

[附被膜基材] [With film substrate]

藉由上述成膜方法所獲得之被膜之平均膜厚(T)較佳為20~200nm，更佳為40~150nm之範圍。若被膜之平均膜厚(T)為20nm以上，則因膜厚較充分而難以產生無法成膜之部分(塗佈不均)，亦可充分地獲得成膜之效果。另一方面，若平均膜厚(T)為200nm以下，則可充分地抑制龜裂之產生，又，膜之硬度亦變得充分。 The film thickness (T) of the film obtained by the above film forming method is preferably from 20 to 200 nm, more preferably from 40 to 150 nm. When the average film thickness (T) of the film is 20 nm or more, the film thickness is sufficient, and it is difficult to form a portion (uneven coating) that cannot be formed, and the film forming effect can be sufficiently obtained. On the other hand, when the average film thickness (T) is 200 nm or less, the occurrence of cracks can be sufficiently suppressed, and the hardness of the film is also sufficient.

本發明之被膜可較佳地用於液晶顯示裝置之電極基板與配向膜間所使用之絕緣膜、觸控面板之透明電極上之保護膜等。 The film of the present invention can be preferably used for an insulating film used between an electrode substrate and an alignment film of a liquid crystal display device, a protective film on a transparent electrode of a touch panel, or the like.

實施例Example

以下，對用以形成透明被膜之塗佈液之實施例進行具體說明。本塗佈液可應用於觸控面板之透明電極上之保護膜等。本發明並不限定於該等實施例。 Hereinafter, an embodiment of a coating liquid for forming a transparent film will be specifically described. The coating liquid can be applied to a protective film or the like on a transparent electrode of a touch panel. The invention is not limited to the embodiments.

[實施例1] [Example 1]

《透明被膜形成用之塗佈液之製備》 "Preparation of Coating Liquid for Forming Transparent Film"

(步驟1) (step 1)

將己二醇(和光純藥股份有限公司製造)4507.86g、純水214.93g及濃度61質量%之硝酸3.58g進行混合，並攪拌5分鐘。繼而，一面進行攪拌一面添加作為B成分(4官能矽烷化合物)之矽酸乙酯(多摩化學股份有限公司製造：SiO2濃度28.8質量%)1243.78g，並攪拌30分鐘。如此，獲得固形物成分濃度6.0質量%之預備液1。 4507.86 g of hexanediol (manufactured by Wako Pure Chemical Co., Ltd.), 214.93 g of pure water, and 3.58 g of nitric acid having a concentration of 61% by mass were mixed and stirred for 5 minutes. Then, 1243.78 g of ethyl decanoate (manufactured by Tama Chemical Co., Ltd.: SiO 2 concentration: 28.8% by mass) as a component B (tetrafunctional decane compound) was added while stirring, and the mixture was stirred for 30 minutes. Thus, the preliminary liquid 1 having a solid content concentration of 6.0% by mass was obtained.

(步驟2) (Step 2)

將己二醇(和光純藥股份有限公司製造)297.97g、作為A成分之乙醯丙酮(和光純藥股份有限公司製造)149.25g、作為C成分之鈦酸四異丙酯(Matsumoto Fine Chemical股份有限公司製造：Orgatix TA-10，TiO2濃度28質量%)852.88g進行混合，並攪拌5分鐘。藉此，獲得固形物成分濃度6.0質量%之預備液2。 297.97 g of hexanediol (manufactured by Wako Pure Chemical Co., Ltd.), 149.25 g of acetonitrile acetone (manufactured by Wako Pure Chemical Co., Ltd.) as component A, and tetraisopropyl titanate (Matsumoto Fine Chemical Co., Ltd.) as component C Co., Ltd. manufactured: Orgatix TA-10, TiO 2 concentration: 28% by mass) 852.88 g was mixed and stirred for 5 minutes. Thereby, the preliminary liquid 2 having a solid content concentration of 6.0% by mass was obtained.

(步驟3) (Step 3)

一面進行攪拌一面將預備液2混合至預備液1中，攪拌10分鐘後，添加純水49.75g，於5℃攪拌144小時。攪拌結束後，利用0.2μm之過濾器進行過濾，將凝集物等去除而製備濃度CT為6.0質量%之塗佈液。 The preliminary liquid 2 was mixed into the preliminary liquid 1 while stirring, and after stirring for 10 minutes, 49.75 g of pure water was added, and the mixture was stirred at 5 ° C for 144 hours. After completion of the stirring, the mixture was filtered through a 0.2 μm filter to remove aggregates or the like to prepare a coating liquid having a concentration CT of 6.0% by mass.

將所獲得之塗佈液中之各成分之濃度、莫耳比等示於表1。再者，於表1中將A成分(可與金屬烷氧化物形成螯合物之有機化合物)之莫耳數設為M1，將B成分(3官能以上之二氧化矽化合物及其水解縮合物之至少一者)之莫耳數設為M2。又，作為B成分，於3官能二氧化矽化合物及其水解縮合物之至少一者(B3成分)、與4官能二氧化矽化合物及其水解縮合物之至少一者(B4成分)共存時，將B3成分之莫耳數設為MB3， 將B4成分之莫耳數設為MB4。 The concentration, molar ratio, and the like of each component in the obtained coating liquid are shown in Table 1. Further, in Table 1, the number of moles of the component A (the organic compound capable of forming a chelate with the metal alkoxide) is M1, and the component B (the trifunctional or higher cerium oxide compound and its hydrolysis condensate) The number of moles of at least one of them is set to M2. In addition, when at least one of the trifunctional cerium oxide compound and the hydrolysis condensate thereof (component B3) and at least one of the tetrafunctional cerium oxide compound and the hydrolysis condensate thereof (component B4) are present as the component B, The number of moles of the B3 component is M B3 , and the number of moles of the B4 component is M B4 .

將式(3)所表示之金屬烷氧化物及其水解縮合物之至少一者(C成分)之莫耳數設為M3。 The number of moles of at least one of the metal alkoxides represented by the formula (3) and the hydrolysis-condensation product thereof (component C) is M3.

於塗佈液中，將源自B成分之SiO2換算濃度設為濃度C2，將源自C成分之MOx換算濃度設為濃度C3，將濃度C2與濃度C3之合計設為濃度CT。 In the coating liquid, the concentration of SiO 2 derived from the B component is set to the concentration C2, the concentration of the MO x derived from the component C is the concentration C3, and the total of the concentration C2 and the concentration C3 is the concentration CT.

關於塗佈液，藉由下述方法對經時穩定性進行評價。將結果示於表1。 Regarding the coating liquid, the stability over time was evaluated by the following method. The results are shown in Table 1.

《經時穩定性》 Stability over time

將塗佈液於40℃加熱72小時後，利用E型黏度計(東機產業股份有限公司製造：TV-25型)對黏度進行測定，根據以下基準進行評價。 After the coating liquid was heated at 40 ° C for 72 hours, the viscosity was measured by an E-type viscometer (manufactured by Toki Sangyo Co., Ltd.: TV-25 type), and evaluated according to the following criteria.

◎：未見黏度變化 ◎: No change in viscosity

○：可見黏度略微增加(未達5mPa‧s) ○: Visible viscosity increased slightly (less than 5mPa‧s)

×：可見黏度明顯增加(5mPa‧s以上) ×: Visible viscosity is significantly increased (5 mPa‧s or more)

《附透明被膜基材之評價》 "Evaluation of Transparent Film Substrate"

針對附透明被膜基材，藉由下述方法對膜厚、表面電阻值及鉛筆硬度進行測定。將結果示於表1。 The film thickness, the surface resistance value, and the pencil hardness were measured by the following methods for the transparent film substrate. The results are shown in Table 1.

《膜厚》 Film Thickness

利用表面粗糙度測定機(東京精密股份有限公司製造：Surfcom)進行測定。 The measurement was performed by a surface roughness measuring machine (manufactured by Tokyo Precision Co., Ltd.: Surfcom).

《表面電阻值》 Surface resistance value

表面電阻值係利用表面電阻測定機(Mitsubishi Chemical Analytech股份有限公司製造：Hiresta-UX MCP-HT800)進行測定。 Surface resistance value is measured by surface resistance measuring machine (Mitsubishi Chemical Analytech Co., Ltd. manufactured by Hiresta-UX MCP-HT800).

《鉛筆硬度》 Pencil Hardness

依據JIS-K-5600，利用鉛筆硬度試驗器進行測定。即，以與透明被膜表面呈45度之角度設置鉛筆，負載特定之負荷，以一定速度進行拉伸，觀察有無擦傷。 The measurement was carried out by a pencil hardness tester in accordance with JIS-K-5600. That is, a pencil was placed at an angle of 45 degrees to the surface of the transparent film, and a specific load was applied thereto, and the film was stretched at a constant speed to observe the presence or absence of scratches.

膜厚、表面電阻值及鉛筆硬度之評價用之附透明被膜基材係藉由如下方法而準備。 The transparent film substrate to be used for evaluation of film thickness, surface resistance value, and pencil hardness was prepared by the following method.

將實施例1中所獲得之塗佈液藉由軟版印刷法塗佈於附ITO膜之玻璃基板(AGC Fabritech股份有限公司製造，厚度：1.1mm)上。於90℃乾燥5分鐘，繼而於照射波長365nm之紫外線(3000mJ/cm2)與波長254nm之紫外線(2000mJ/cm2)後，於230℃加熱30分鐘，而獲得附透明被膜基材。 The coating liquid obtained in Example 1 was applied onto a glass substrate (manufactured by AGC Fabritech Co., Ltd., thickness: 1.1 mm) coated with an ITO film by a soft printing method. After drying at 90 ℃ 5 minutes and then irradiated at a wavelength of 365nm ultraviolet (3000mJ / cm 2) with a wavelength of 254nm ultraviolet light (2000mJ / cm 2), heated for 30 minutes at 230 deg.] C, to obtain a substrate with a transparent film.

針對附透明被膜基材，藉由下述方法對全光線穿透率、霧度及耐擦傷性進行測定。將結果示於表1。 For the transparent film substrate, the total light transmittance, haze, and scratch resistance were measured by the following methods. The results are shown in Table 1.

《全光線穿透率及霧度》 "Full Light Transmittance and Haze"

全光線穿透率及霧度係利用測霧計(Suga Test Instruments股份有限公司製造)進行測定。 The total light transmittance and the haze were measured by a fog meter (manufactured by Suga Test Instruments Co., Ltd.).

《耐擦傷性之測定》 "Determination of scratch resistance"

使#0000鋼絲絨接觸透明被膜表面，以負載2kg/cm2滑動10次，以目視觀察膜之表面，根據以下基準對耐擦傷性進行評價。 The #0000 steel wool was brought into contact with the surface of the transparent film, and was slid 10 times under a load of 2 kg/cm 2 to visually observe the surface of the film, and the scratch resistance was evaluated according to the following criteria.

評價基準： Evaluation criteria:

未見條紋狀之傷痕：◎ No streaky scars: ◎

略微可見條紋狀之傷痕：○ Slightly visible striped scars: ○

大量可見條紋狀之傷痕：△ A large number of striped scars are visible: △

整個面被刮削：× The entire surface is scraped: ×

全光線穿透率、霧度及耐擦傷性之評價用之附透明被膜基材係藉由如下方法而準備。 The transparent film substrate to be used for evaluation of total light transmittance, haze, and scratch resistance was prepared by the following method.

將實施例1中所獲得之塗佈液藉由軟版印刷法塗佈於附二氧化矽膜之玻璃基板(AGC Fabritech股份有限公司製造，厚度：1.1mm)上。於90℃乾燥5分鐘，繼而於照射波長365nm之紫外線(3000mJ/cm2)與波長254nm之紫外線(2000mJ/cm2)後，於230℃加熱30分鐘，而獲得附透明被膜基材。 The coating liquid obtained in Example 1 was applied onto a glass substrate (manufactured by AGC Fabritech Co., Ltd., thickness: 1.1 mm) with a ruthenium dioxide film by a soft printing method. After drying at 90 ℃ 5 minutes and then irradiated at a wavelength of 365nm ultraviolet (3000mJ / cm 2) with a wavelength of 254nm ultraviolet light (2000mJ / cm 2), heated for 30 minutes at 230 deg.] C, to obtain a substrate with a transparent film.

針對附透明被膜基材，藉由下述方法測定折射率。將結果示於表1。 The refractive index was measured by the following method with respect to the transparent film substrate. The results are shown in Table 1.

《折射率》 Refractive Index

利用光譜式橢圓儀(SOPRA股份有限公司製造：ES4G，@ 550nm)進行測定。 The measurement was carried out using a spectroscopic ellipsometer (manufactured by SOPRA Co., Ltd.: ES4G, @550nm).

折射率之評價用之附透明被膜基材係藉由如下方法而準備。 The transparent film substrate to which the refractive index was evaluated was prepared by the following method.

將實施例1中所獲得之塗佈液藉由軟版印刷法塗佈於6英吋之矽晶圓(松崎製作所股份有限公司製作，厚度：0.625mm)上。於90℃乾燥5分鐘，繼而於照射波長365nm之紫外線(3000mJ/cm2)與波長254nm之紫外線(2000mJ/cm2)後，於230℃加熱30分鐘，而獲得附透明被膜基材。 The coating liquid obtained in Example 1 was applied onto a 6-inch crucible wafer (manufactured by Matsuzaki Seisakusho Co., Ltd., thickness: 0.625 mm) by a soft printing method. After drying at 90 ℃ 5 minutes and then irradiated at a wavelength of 365nm ultraviolet (3000mJ / cm 2) with a wavelength of 254nm ultraviolet light (2000mJ / cm 2), heated for 30 minutes at 230 deg.] C, to obtain a substrate with a transparent film.

針對附透明被膜基材，藉由下述方法測定抗龜裂性。將結果 示於表1。 The crack resistance was measured by the following method with respect to the transparent film base material. Will result Shown in Table 1.

《塗佈膜之抗龜裂性》 "Cracking resistance of coated film"

以目視觀察塗佈膜之表面，根據以下基準對抗龜裂性進行評價。 The surface of the coating film was visually observed, and the crack resistance was evaluated according to the following criteria.

◎：塗佈面內未見龜裂 ◎: No cracks were seen in the coated surface.

○：邊緣部略微可見龜裂 ○: cracks are slightly visible at the edge

×：塗佈面內產生龜裂 ×: Cracking occurred in the coated surface

塗佈膜之抗龜裂性之評價用之附透明被膜基材係藉由如下方法而準備。 The transparent film substrate to be used for evaluation of the crack resistance of the coating film was prepared by the following method.

於附二氧化矽膜之玻璃基板(AGC Fabritech股份有限公司製造，厚度：1.1mm)上形成厚度2μm之丙烯酸樹脂層。丙烯酸樹脂層係使用棒式塗佈機(No.4)進行塗佈，繼而於80℃乾燥2分鐘後，照射波長365nm之紫外線(300mJ/cm2)。將實施例1中所獲得之塗佈液藉由軟版印刷法塗佈於附該丙烯酸樹脂層之玻璃基板上，於90℃乾燥5分鐘，繼而於照射3000mJ/cm2之紫外線(波長365nm)後，於230℃加熱30分鐘，而獲得附透明被膜基材。 An acrylic resin layer having a thickness of 2 μm was formed on a glass substrate (manufactured by AGC Fabritech Co., Ltd., thickness: 1.1 mm) to which a ruthenium dioxide film was attached. The acrylic resin layer was applied by a bar coater (No. 4), and then dried at 80 ° C for 2 minutes, and then irradiated with ultraviolet rays (300 mJ/cm 2 ) having a wavelength of 365 nm. The coating liquid obtained in Example 1 was applied onto a glass substrate with the acrylic resin layer by a soft printing method, and dried at 90 ° C for 5 minutes, followed by irradiation with ultraviolet rays of 3000 mJ/cm 2 (wavelength 365 nm). Thereafter, the film was heated at 230 ° C for 30 minutes to obtain a transparent film substrate.

[實施例2] [Embodiment 2]

《透明被膜形成用之塗佈液之製備》 "Preparation of Coating Liquid for Forming Transparent Film"

於步驟2中，使用己二醇(和光純藥股份有限公司製造)255.917g、乙醯丙酮(和光純藥股份有限公司製造)568.05g，除此以外，以與實施例1相同之方式製備濃度CT為6.0質量%之塗佈液。 In the same manner as in Example 1, except that 255.917 g of hexanediol (manufactured by Wako Pure Chemical Co., Ltd.) and 568.05 g of acetamidine acetone (manufactured by Wako Pure Chemical Industries, Ltd.) were used in the second step. The CT was 6.0% by mass of the coating liquid.

將所獲得之塗佈液之各成分之濃度、莫耳比等示於表1。 The concentration, molar ratio, and the like of each component of the obtained coating liquid are shown in Table 1.

《附透明被膜基材之評價》 "Evaluation of Transparent Film Substrate"

除了使用該塗佈液以外，以與實施例1相同之方式進行測定、評價。將結果示於表1。 The measurement and evaluation were carried out in the same manner as in Example 1 except that the coating liquid was used. The results are shown in Table 1.

[實施例3] [Example 3]

《透明被膜形成用之塗佈液之製備》 "Preparation of Coating Liquid for Forming Transparent Film"

於步驟2中，使用己二醇(和光純藥股份有限公司製造)3052.48g、乙醯丙酮(和光純藥股份有限公司製造)74.74g，除此以外，以與實施例1相同之方式製備濃度CT為6.0質量%之塗佈液。 In the same manner as in Example 1, except that 3052.48 g of hexanediol (manufactured by Wako Pure Chemical Co., Ltd.) and 74.74 g of acetamidine acetone (manufactured by Wako Pure Chemical Industries, Ltd.) were used in the second step. The CT was 6.0% by mass of the coating liquid.

將所獲得之塗佈液之各成分之濃度、莫耳比等示於表1。 The concentration, molar ratio, and the like of each component of the obtained coating liquid are shown in Table 1.

《附透明被膜基材之評價》 "Evaluation of Transparent Film Substrate"

除了使用該塗佈液以外，以與實施例1相同之方式進行測定、評價。將結果示於表1。 The measurement and evaluation were carried out in the same manner as in Example 1 except that the coating liquid was used. The results are shown in Table 1.

[實施例4] [Example 4]

《透明被膜形成用之塗佈液之製備》 "Preparation of Coating Liquid for Forming Transparent Film"

(步驟1) (step 1)

將己二醇(和光純藥股份有限公司製造)6536.14g、純水311.64g及濃度61質量%之硝酸5.19g混合，並攪拌5分鐘。繼而，一面進行攪拌一面添加作為B成分(4官能矽烷化合物)之矽酸乙酯(多摩化學股份有限公司製造：SiO2濃度28.8質量%)1803.48g，攪拌30分鐘而製備固形物成分濃度6.0質量%之預備液1。 6536.14 g of hexanediol (manufactured by Wako Pure Chemical Co., Ltd.), 311.64 g of pure water, and 5.19 g of nitric acid having a concentration of 61% by mass were mixed and stirred for 5 minutes. Then, 1803.48 g of ethyl decanoate (manufactured by Tama Chemical Co., Ltd.: SiO 2 concentration: 28.8% by mass) as a component B (tetrafunctional decane compound) was added while stirring, and the mixture was stirred for 30 minutes to prepare a solid content concentration of 6.0. % of the preparation liquid 1.

(步驟2) (Step 2)

將己二醇(和光純藥股份有限公司製造)967.76g、作為A 成分之乙醯丙酮(和光純藥股份有限公司製造)48.58g、作為C成分之鈦酸四異丙酯(Matsumoto Fine Chemical股份有限公司製造：Orgatix TA-10，TiO2濃度28質量%)277.19g混合，並攪拌5分鐘，而製備固形物成分濃度6.0質量%之預備液2。 967.76 g of hexanediol (manufactured by Wako Pure Chemical Co., Ltd.), 48.58 g of ethyl acetonide (manufactured by Wako Pure Chemical Co., Ltd.) as component A, and tetraisopropyl titanate (Matsumoto Fine Chemical Co., Ltd.) as component C Co., Ltd. manufactured: Orgatix TA-10, TiO 2 concentration: 28% by mass) 277.19 g was mixed and stirred for 5 minutes to prepare a preliminary liquid 2 having a solid content concentration of 6.0% by mass.

(步驟3) (Step 3)

一面進行攪拌一面將預備液2混合至預備液1中，攪拌10分鐘後，添加純水49.75g，於5℃攪拌144小時。攪拌結束後，利用0.2μm之過濾器進行過濾，將凝集物等去除，而製備濃度CT為6.0質量%之塗佈液。 The preliminary liquid 2 was mixed into the preliminary liquid 1 while stirring, and after stirring for 10 minutes, 49.75 g of pure water was added, and the mixture was stirred at 5 ° C for 144 hours. After completion of the stirring, the mixture was filtered through a 0.2 μm filter to remove aggregates and the like, thereby preparing a coating liquid having a concentration CT of 6.0% by mass.

將所獲得之塗佈液之各成分之濃度、莫耳比等示於表1。 The concentration, molar ratio, and the like of each component of the obtained coating liquid are shown in Table 1.

《附透明被膜基材之評價》 "Evaluation of Transparent Film Substrate"

除了使用該塗佈液以外，以與實施例1相同之方式進行測定、評價。將結果示於表1。 The measurement and evaluation were carried out in the same manner as in Example 1 except that the coating liquid was used. The results are shown in Table 1.

[實施例5] [Example 5]

《透明被膜形成用之塗佈液之製備》 "Preparation of Coating Liquid for Forming Transparent Film"

(步驟1) (step 1)

將己二醇(和光純藥股份有限公司製造)1126.97g、純水53.73g及濃度61質量%之硝酸0.90g混合，並攪拌5分鐘。繼而，一面進行攪拌一面添加作為B成分(4官能矽烷化合物)之矽酸乙酯(多摩化學股份有限公司製造：SiO2濃度28.8質量%)310.95g，攪拌30分鐘，而製備固形物成分濃度6.0質量%之預備液1。 1126.97 g of hexanediol (manufactured by Wako Pure Chemical Co., Ltd.), 53.73 g of pure water, and 0.90 g of nitric acid having a concentration of 61% by mass were mixed and stirred for 5 minutes. Then, 310.95 g of ethyl decanoate (manufactured by Tama Chemical Co., Ltd.: SiO 2 concentration: 28.8% by mass) as a component B (4-functional decane compound) was added while stirring, and the mixture was stirred for 30 minutes to prepare a solid content concentration of 6.0. % by mass of the preparation liquid 1.

(步驟2) (Step 2)

將己二醇(和光純藥股份有限公司製造)6327.69g、作為A成分之乙醯丙酮(和光純藥股份有限公司製造)317.66g、作為C成分之鈦酸四異丙酯(Matsumoto Fine Chemical股份有限公司製造：Orgatix TA-10，TiO2濃度28質量%)1812.37g混合，並攪拌5分鐘，而製備固形物成分濃度6.0質量%之預備液2。 6327.69g of hexanediol (manufactured by Wako Pure Chemical Co., Ltd.), 317.66g of acetonitrile acetone (manufactured by Wako Pure Chemical Co., Ltd.) as component A, and tetraisopropyl titanate (Matsumoto Fine Chemical Co., Ltd.) as component C Co., Ltd. manufactured: Orgatix TA-10, TiO 2 concentration: 28% by mass) 1812.37 g, and stirred for 5 minutes to prepare a preliminary liquid 2 having a solid content concentration of 6.0% by mass.

(步驟3) (Step 3)

一面進行攪拌一面將預備液2混合至預備液1中，攪拌10分鐘後，添加純水49.75g，於5℃攪拌144小時。攪拌結束後，利用0.2μm之過濾器進行過濾，將凝集物等去除，而製備濃度CT為6.0質量%之塗佈液。將所獲得之塗佈液中之各成分之濃度、莫耳比等示於表1。 The preliminary liquid 2 was mixed into the preliminary liquid 1 while stirring, and after stirring for 10 minutes, 49.75 g of pure water was added, and the mixture was stirred at 5 ° C for 144 hours. After completion of the stirring, the mixture was filtered through a 0.2 μm filter to remove aggregates and the like, thereby preparing a coating liquid having a concentration CT of 6.0% by mass. The concentration, molar ratio, and the like of each component in the obtained coating liquid are shown in Table 1.

《附透明被膜基材之評價》 "Evaluation of Transparent Film Substrate"

除了使用該塗佈液以外，以與實施例1相同之方式進行測定、評價。將結果示於表1。 The measurement and evaluation were carried out in the same manner as in Example 1 except that the coating liquid was used. The results are shown in Table 1.

[實施例6] [Embodiment 6]

《透明被膜形成用之塗佈液之製備》 "Preparation of Coating Liquid for Forming Transparent Film"

(步驟1) (step 1)

將己二醇(和光純藥股份有限公司製造)5239.00g、純水107.46g及濃度61質量%之硝酸1.79g混合，並攪拌5分鐘。繼而，一面進行攪拌一面添加作為B成分(4官能矽烷化合物)之矽酸乙酯(多摩化學股份有限公司製造：SiO2濃度28.8質量%)621.89g，並攪拌30分鐘，而製備固形物成分濃度6.0質量%之預備液1。 5239.00 g of hexanediol (manufactured by Wako Pure Chemical Co., Ltd.), 107.46 g of pure water, and 1.79 g of nitric acid having a concentration of 61% by mass were mixed and stirred for 5 minutes. Then, 621.89 g of ethyl decanoate (manufactured by Tama Chemical Co., Ltd.: SiO 2 concentration: 28.8% by mass) as a component B (tetrafunctional decane compound) was added while stirring, and stirred for 30 minutes to prepare a solid content concentration. 6.0% by mass of the preliminary solution 1.

(步驟2) (Step 2)

將己二醇(和光純藥股份有限公司製造)3478.92g、作為A成分之乙醯丙酮(和光純藥股份有限公司製造)74.74g、作為C成分之鈦酸四異丙酯(Matsumoto Fine Chemical股份有限公司製造：Orgatix TA-10，TiO2濃度28質量%)426.44g混合，並攪拌5分鐘，而製備固形物成分濃度6.0質量%之預備液2。 3,465.92 g of hexanediol (manufactured by Wako Pure Chemical Co., Ltd.), 74.74 g of ethyl acetonide (manufactured by Wako Pure Chemical Co., Ltd.) as component A, and tetraisopropyl titanate (Matsumoto Fine Chemical Co., Ltd.) as component C Co., Ltd. manufactured: Orgatix TA-10, TiO 2 concentration: 28% by mass) 426.44 g, and stirred for 5 minutes to prepare a preliminary liquid 2 having a solid content concentration of 6.0% by mass.

(步驟3) (Step 3)

一面進行攪拌一面將預備液2混合至預備液1中，攪拌10分鐘後，添加純水49.75g，於5℃攪拌144小時。攪拌結束後，利用0.2μm之過濾器進行過濾，將凝集物等去除，而製備濃度CT為6.0質量%之塗佈液。將所獲得之塗佈液之各成分之濃度、莫耳比等示於表1。 The preliminary liquid 2 was mixed into the preliminary liquid 1 while stirring, and after stirring for 10 minutes, 49.75 g of pure water was added, and the mixture was stirred at 5 ° C for 144 hours. After completion of the stirring, the mixture was filtered through a 0.2 μm filter to remove aggregates and the like, thereby preparing a coating liquid having a concentration CT of 6.0% by mass. The concentration, molar ratio, and the like of each component of the obtained coating liquid are shown in Table 1.

《附透明被膜基材之評價》 "Evaluation of Transparent Film Substrate"

將紫外線照射後之加熱條件設為120℃、30分鐘，除此以外，以與實施例1相同之方式進行測定、評價。將結果示於表1。 The measurement and evaluation were carried out in the same manner as in Example 1 except that the heating conditions after the ultraviolet irradiation were 120 ° C for 30 minutes. The results are shown in Table 1.

[實施例7] [Embodiment 7]

《透明被膜形成用之塗佈液之製備》 "Preparation of Coating Liquid for Forming Transparent Film"

(步驟1) (step 1)

將己二醇(和光純藥股份有限公司製造)3776.72g、純水322.39g及濃度61質量%之硝酸5.37g混合，並攪拌5分鐘。繼而，一面進行攪拌一面添加作為B成分(4官能矽烷化合物)之矽酸乙酯(多摩化學股份有限公司製造：SiO2濃度28.8質量%)1865.67g，並攪拌30分鐘，而製備固形物成分濃度9.0質量%之預備液1。 3776.72 g of hexanediol (manufactured by Wako Pure Chemical Co., Ltd.), 322.39 g of pure water, and 5.37 g of nitric acid having a concentration of 61% by mass were mixed and stirred for 5 minutes. Then, 1856.67 g of ethyl decanoate (manufactured by Tama Chemical Co., Ltd.: SiO 2 concentration: 28.8% by mass) as a component B (tetrafunctional decane compound) was added while stirring, and stirred for 30 minutes to prepare a solid content concentration. 9.0% by mass of the preliminary solution 1.

(步驟2) (Step 2)

將己二醇(和光純藥股份有限公司製造)2476.55g、作為A成分之乙醯丙酮(和光純藥股份有限公司製造)224.23g、作為C成分之鈦酸四異丙酯(Matsumoto Fine Chemical股份有限公司製造：Orgatix TA-10，TiO2濃度28質量%)1279.32g混合，並攪拌5分鐘，而製備固形物成分濃度9.0質量%之預備液2。 2,465.55 g of hexanediol (manufactured by Wako Pure Chemical Co., Ltd.), 224.23 g of ethyl acetonide (manufactured by Wako Pure Chemical Co., Ltd.) as component A, and tetraisopropyl titanate (Matsumoto Fine Chemical Co., Ltd.) as component C Co., Ltd. manufactured: Orgatix TA-10, TiO 2 concentration: 28% by mass) 1279.32 g, and stirred for 5 minutes to prepare a preliminary liquid 2 having a solid content concentration of 9.0% by mass.

(步驟3) (Step 3)

一面進行攪拌一面將預備液2混合至預備液1中，攪拌10分鐘後，添加純水49.75g，於5℃攪拌144小時。攪拌結束後，利用0.2μm之過濾器進行過濾，將凝集物等去除，而製備濃度CT為9.0質量%之塗佈液。將所獲得之塗佈液之各成分之濃度、莫耳比等示於表1。 The preliminary liquid 2 was mixed into the preliminary liquid 1 while stirring, and after stirring for 10 minutes, 49.75 g of pure water was added, and the mixture was stirred at 5 ° C for 144 hours. After completion of the stirring, the mixture was filtered through a 0.2 μm filter to remove aggregates and the like, thereby preparing a coating liquid having a concentration CT of 9.0% by mass. The concentration, molar ratio, and the like of each component of the obtained coating liquid are shown in Table 1.

《附透明被膜基材之評價》 "Evaluation of Transparent Film Substrate"

將紫外線照射後之加熱條件設為280℃、30分鐘，除此以外，以與實施例1相同之方式進行測定、評價。將結果示於表1。 The measurement and evaluation were carried out in the same manner as in Example 1 except that the heating conditions after the ultraviolet irradiation were 280 ° C for 30 minutes. The results are shown in Table 1.

[實施例8] [Embodiment 8]

《透明被膜形成用之塗佈液之製備》 "Preparation of Coating Liquid for Forming Transparent Film"

(步驟1) (step 1)

將己二醇(和光純藥股份有限公司製造)3681.42g、純水175.52g及濃度61質量%之硝酸2.93g混合，並攪拌5分鐘。繼而，一面進行攪拌一面添加作為B成分(4官能矽烷化合物)之矽酸乙酯(多摩化學股份有限公司製造：SiO2濃度28.8質量%)1015.75g，並攪拌30分鐘，而製備固形物成分濃度6.0質量%之預備液1。 3681.42 g of hexanediol (manufactured by Wako Pure Chemical Co., Ltd.), 175.52 g of pure water, and 2.93 g of nitric acid having a concentration of 61% by mass were mixed and stirred for 5 minutes. Then, 1015.75 g of ethyl decanoate (manufactured by Tama Chemical Co., Ltd.: SiO 2 concentration: 28.8% by mass) as a component B (tetrafunctional decane compound) was added while stirring, and stirred for 30 minutes to prepare a solid content concentration. 6.0% by mass of the preliminary solution 1.

(步驟2) (Step 2)

將己二醇(和光純藥股份有限公司製造)3416.09g、作為A成分之乙醯丙酮(和光純藥股份有限公司製造)218.93.g、作為C成分之鋯酸正丙酯(Matsumoto Fine Chemical股份有限公司製造Orgatix ZA-45，ZrO2濃度21.2質量%)1439.61g混合，並攪拌5分鐘，而製備固形物成分濃度6.0質量%之預備液2。 3,160.09 g of hexanediol (manufactured by Wako Pure Chemical Co., Ltd.), 218.93 g of acetonitrile acetone (manufactured by Wako Pure Chemical Co., Ltd.) as component A, and n-propyl zirconate as component C (Matsumoto Fine Chemical Co., Ltd.) The company prepared Orgatix ZA-45, ZrO 2 concentration 21.2% by mass) 1439.61 g, and stirred for 5 minutes to prepare a preliminary liquid 2 having a solid content concentration of 6.0% by mass.

(步驟3) (Step 3)

一面進行攪拌一面將預備液2混合至預備液1中，攪拌10分鐘後，添加純水49.23g，於5℃攪拌144小時。攪拌結束後，利用0.2μm之過濾器進行過濾，將凝集物等去除，而製備濃度CT為6.0質量%之塗佈液。將所獲得之塗佈液之各成分之濃度、莫耳比等示於表1。 The preliminary liquid 2 was mixed into the preliminary liquid 1 while stirring, and after stirring for 10 minutes, 49.23 g of pure water was added, and the mixture was stirred at 5 ° C for 144 hours. After completion of the stirring, the mixture was filtered through a 0.2 μm filter to remove aggregates and the like, thereby preparing a coating liquid having a concentration CT of 6.0% by mass. The concentration, molar ratio, and the like of each component of the obtained coating liquid are shown in Table 1.

《附透明被膜基材之評價》 "Evaluation of Transparent Film Substrate"

除了使用該塗佈液以外，以與實施例1相同之方式進行測定、評價。將結果示於表1。 The measurement and evaluation were carried out in the same manner as in Example 1 except that the coating liquid was used. The results are shown in Table 1.

[實施例9] [Embodiment 9]

《透明被膜形成用之塗佈液之製備》 "Preparation of Coating Liquid for Forming Transparent Film"

(步驟1) (step 1)

將作為B成分(3官能矽烷化合物)之KBM-13(信越化學工業股份有限公司製造：SiO2濃度44.1質量%)713.22g及Solmix AP-11(Japan Alcohol Trading股份有限公司製造)1875.40g混合，並攪拌30分鐘。繼而，一面進行攪拌一面歷時30分鐘逐次添加濃度0.1質量%之硝酸570.50g，並攪拌30分鐘。此時之pH值為2.0。於其中一面進行攪拌一面添加三乙醇胺(林純藥工業股份有限公司製造)5.06g，攪拌10分鐘而製備固形物成分濃 度10.0質量%之預備液1-1。此時之pH值為7.1。 Between 713.22 g of KBM-13 (manufactured by Shin-Etsu Chemical Co., Ltd.: SiO 2 concentration: 44.1% by mass) and 1875.40 g of Solmix AP-11 (manufactured by Japan Alcohol Trading Co., Ltd.) as a component B (trifunctional decane compound), Stir for 30 minutes. Then, while stirring, 570.50 g of nitric acid having a concentration of 0.1% by mass was successively added over 30 minutes, and stirred for 30 minutes. The pH at this time was 2.0. To the mixture, 5.06 g of triethanolamine (manufactured by Lin Chun Pharmaceutical Co., Ltd.) was added thereto, and the mixture was stirred for 10 minutes to prepare a preliminary liquid 1-1 having a solid content concentration of 10.0% by mass. The pH at this time was 7.1.

繼而，於己二醇(和光純藥股份有限公司製造)2109.45g中，一面進行攪拌一面添加預備液1-1並攪拌30分鐘，而製備固形物成分濃度6.0質量%之預備液1。 Then, the pre-liquid 1-1 was added while stirring at 2109.45 g of hexanediol (manufactured by Wako Pure Chemical Co., Ltd.), and the mixture was stirred for 30 minutes to prepare a preliminary liquid 1 having a solid content concentration of 6.0% by mass.

(步驟2) (Step 2)

將己二醇(和光純藥股份有限公司製造)3498.84g、作為A成分之乙醯丙酮(和光純藥股份有限公司製造)175.65g、作為C成分之鈦酸四異丙酯(Matsumoto Fine Chemical股份有限公司製造：Orgatix TA-10，TiO2濃度28質量%)1002.13g混合，攪拌5分鐘，而製備固形物成分濃度6.0質量%之預備液2。 3498.84 g of hexanediol (manufactured by Wako Pure Chemical Co., Ltd.), 175.65 g of acetonitrile acetone (manufactured by Wako Pure Chemical Co., Ltd.) as component A, and tetraisopropyl titanate (Matsumoto Fine Chemical Co., Ltd.) as component C Co., Ltd. manufactured: Orgatix TA-10, TiO 2 concentration: 28% by mass) 1002.13 g, and stirred for 5 minutes to prepare a preliminary liquid 2 having a solid content concentration of 6.0% by mass.

(步驟3) (Step 3)

一面進行攪拌一面將預備液2混合至預備液1中，攪拌10分鐘後，添加純水49.75g，於25℃攪拌30分鐘。攪拌結束後，利用0.2μm之過濾器進行過濾，將凝集物等去除，而製備濃度CT為6.0質量%之塗佈液。將結果示於表1。 The preliminary liquid 2 was mixed into the preliminary liquid 1 while stirring, and after stirring for 10 minutes, 49.75 g of pure water was added, and the mixture was stirred at 25 ° C for 30 minutes. After completion of the stirring, the mixture was filtered through a 0.2 μm filter to remove aggregates and the like, thereby preparing a coating liquid having a concentration CT of 6.0% by mass. The results are shown in Table 1.

《附透明被膜基材之評價》 "Evaluation of Transparent Film Substrate"

除了使用該塗佈液以外，以與實施例1相同之方式進行測定、評價。將結果示於表1。 The measurement and evaluation were carried out in the same manner as in Example 1 except that the coating liquid was used. The results are shown in Table 1.

[實施例10] [Embodiment 10]

《透明被膜形成用之塗佈液之製備》 "Preparation of Coating Liquid for Forming Transparent Film"

除了以下之預備步驟以外，以與實施例1相同之方式製備塗佈液。將所獲得之塗佈液之各成分之濃度、莫耳比等示於表1。 A coating liquid was prepared in the same manner as in Example 1 except for the following preliminary steps. The concentration, molar ratio, and the like of each component of the obtained coating liquid are shown in Table 1.

(步驟1) (step 1)

將作為B成分(3官能矽烷化合物)之KBM-13(信越化學工業股份有限公司製造：SiO2濃度44.1質量%)1009.27g及Solmix AP-11(Japan Alcohol Trading股份有限公司製造)2653.86g混合，並攪拌30分鐘。繼而，一面進行攪拌一面歷時30分鐘逐次添加濃度0.1質量%之硝酸807.32g，並攪拌30分鐘。此時之pH值為2.1。於其中一面進行攪拌一面添加三乙醇胺(林純藥工業股份有限公司製造)7.16g，攪拌10分鐘而製備固形物成分濃度9.9質量%之預備液1-1。此時之pH值為7.2。 KBM-13 (manufactured by Shin-Etsu Chemical Co., Ltd.: SiO 2 concentration: 44.1% by mass) 1009.27 g and Solmix AP-11 (manufactured by Japan Alcohol Trading Co., Ltd.) 2653.86 g were mixed as a component B (trifunctional decane compound). Stir for 30 minutes. Then, 807.32 g of nitric acid having a concentration of 0.1% by mass was successively added for 30 minutes while stirring, and stirred for 30 minutes. The pH at this time was 2.1. To the mixture, 7.16 g of triethanolamine (manufactured by Lin Chun Pharmaceutical Co., Ltd.) was added thereto, and the mixture was stirred for 10 minutes to prepare a preliminary liquid 1-1 having a solid content concentration of 9.9% by mass. The pH at this time was 7.2.

繼而，於己二醇(和光純藥股份有限公司製造)2985.07g中，一面進行攪拌一面添加預備液1-1，攪拌30分鐘，而製備固形物成分濃度6.0質量%之預備液1-2。 Then, the preparation liquid 1-1 was added while stirring with 2985.07 g of hexanediol (manufactured by Wako Pure Chemical Co., Ltd.), and the mixture was stirred for 30 minutes to prepare a preparation liquid 1-2 having a solid content concentration of 6.0% by mass.

(步驟2) (Step 2)

將己二醇(和光純藥股份有限公司製造)1861.08g、作為A成分之乙醯丙酮(和光純藥股份有限公司製造)93.43g、作為C成分之鈦酸四異丙酯(Matsumoto Fine Chemical股份有限公司製造：Orgatix TA-10，TiO2濃度28質量%)533.05g混合，攪拌5分鐘，而製備固形物成分濃度6.0質量%之預備液2。 1861.08 g of hexanediol (manufactured by Wako Pure Chemical Co., Ltd.), 93.43 g of acetonitrile acetone (manufactured by Wako Pure Chemical Co., Ltd.) as component A, and tetraisopropyl titanate (Matsumoto Fine Chemical Co., Ltd.) as component C Co., Ltd. manufactured: Orgatix TA-10, TiO 2 concentration: 28% by mass) 533.05 g was mixed and stirred for 5 minutes to prepare a preliminary liquid 2 having a solid content concentration of 6.0% by mass.

《附透明被膜之基材之評價》 Evaluation of Substrate with Transparent Film

除了使用該塗佈液以外，以與實施例1相同之方式進行測定、評價。將結果示於表1。 The measurement and evaluation were carried out in the same manner as in Example 1 except that the coating liquid was used. The results are shown in Table 1.

[實施例11] [Example 11]

除了以下之步驟以外，以與實施例1相同之方式製備透明被 膜形成用之塗佈液。 A transparent quilt was prepared in the same manner as in Example 1 except for the following steps. A coating liquid for film formation.

將所獲得之塗佈液之各成分之濃度、莫耳比等示於表1。 The concentration, molar ratio, and the like of each component of the obtained coating liquid are shown in Table 1.

(步驟1) (step 1)

將作為B成分(3官能矽烷化合物)之KBM-13(信越化學工業股份有限公司製造：SiO2濃度44.1質量%)1143.84g及Solmix AP-11(Japan Alcohol Trading股份有限公司製造)3007.71g混合，並攪拌30分鐘。繼而，一面進行攪拌一面歷時30分鐘逐次添加濃度0.1質量%之硝酸914.96g，並攪拌30分鐘。此時之pH值為2.1。於其中一面進行攪拌一面添加三乙醇胺(林純藥工業股份有限公司製造)8.11g，攪拌10分鐘，而製備固形物成分濃度9.9質量%之預備液1-1。此時之pH值為7.1。 In the B component (trifunctional decane compound), KBM-13 (manufactured by Shin-Etsu Chemical Co., Ltd.: SiO 2 concentration: 44.1% by mass), 1143.84 g, and Solmix AP-11 (manufactured by Japan Alcohol Trading Co., Ltd.), 3007.71 g, were mixed. Stir for 30 minutes. Then, 914.96 g of nitric acid having a concentration of 0.1% by mass was successively added over 30 minutes while stirring, and stirred for 30 minutes. The pH at this time was 2.1. To the mixture, 8.11 g of triethanolamine (manufactured by Lin Chun Pharmaceutical Co., Ltd.) was added and stirred for 10 minutes to prepare a preliminary liquid 1-1 having a solid content concentration of 9.9% by mass. The pH at this time was 7.1.

繼而，於己二醇(和光純藥股份有限公司製造)3383.08g中，一面進行攪拌一面添加預備液1-1，攪拌30分鐘，而製備固形物成分濃度6.0質量%之預備液1。 Then, the preliminary liquid 1-1 was added while stirring in 3383.08 g of hexanediol (manufactured by Wako Pure Chemical Co., Ltd.), and the mixture was stirred for 30 minutes to prepare a preliminary liquid 1 having a solid content concentration of 6.0% by mass.

(步驟2) (Step 2)

將己二醇(和光純藥股份有限公司製造)1116.65g、作為A成分之乙醯丙酮(和光純藥股份有限公司製造)56.06g、作為C成分之鈦酸四異丙酯(Matsumoto Fine Chemical股份有限公司製造：Orgatix TA-10，TiO2濃度28質量%)319.83g混合，攪拌5分鐘，而製備固形物成分濃度6.0質量%之預備液2。 1116.65 g of hexanediol (manufactured by Wako Pure Chemical Co., Ltd.), 56.06 g of acetonitrile acetone (manufactured by Wako Pure Chemical Co., Ltd.) as component A, and tetraisopropyl titanate (Matsumoto Fine Chemical Co., Ltd.) as component C Co., Ltd. manufactured: Orgatix TA-10, TiO 2 concentration: 28% by mass) 319.83 g, and stirred for 5 minutes to prepare a preliminary liquid 2 having a solid content concentration of 6.0% by mass.

《附透明被膜基材之評價》 "Evaluation of Transparent Film Substrate"

除了使用該塗佈液以外，以與實施例1相同之方式進行測定、評價。將結果示於表1。 The measurement and evaluation were carried out in the same manner as in Example 1 except that the coating liquid was used. The results are shown in Table 1.

[實施例12] [Embodiment 12]

《透明被膜形成用之塗佈液之製備》 "Preparation of Coating Liquid for Forming Transparent Film"

除了以下之步驟以外，以與實施例1相同之方式製備塗佈液。 A coating liquid was prepared in the same manner as in Example 1 except for the following steps.

將所獲得之塗佈液之各成分之濃度、莫耳比等示於表1。 The concentration, molar ratio, and the like of each component of the obtained coating liquid are shown in Table 1.

(步驟1) (step 1)

將作為B成分(3官能矽烷化合物)之KBM-13(信越化學工業股份有限公司製造：SiO2濃度44.1質量%)403.71g及Solmix AP-11(Japan Alcohol Trading股份有限公司製造)1061.55g混合，並攪拌30分鐘。繼而，一面進行攪拌一面歷時30分鐘逐次添加濃度0.1質量%之硝酸322.92g，並攪拌30分鐘。此時之pH值為2.0。於其中一面進行攪拌一面添加三乙醇胺(林純藥工業股份有限公司製造)2.86g，攪拌10分鐘，而製備固形物成分濃度9.9質量%之預備液1-1。此時之pH值為7.0。 403.71 g of KBM-13 (manufactured by Shin-Etsu Chemical Co., Ltd.: SiO 2 concentration: 44.1% by mass) and 1061.55 g of Solmix AP-11 (manufactured by Japan Alcohol Trading Co., Ltd.) were mixed as a component B (trifunctional decane compound). Stir for 30 minutes. Then, 329.22 g of nitric acid having a concentration of 0.1% by mass was successively added over 30 minutes while stirring, and the mixture was stirred for 30 minutes. The pH at this time was 2.0. 2.86 g of triethanolamine (manufactured by Lin Chun Pharmaceutical Co., Ltd.) was added while stirring, and the mixture was stirred for 10 minutes to prepare a preliminary liquid 1-1 having a solid content concentration of 9.9% by mass. The pH at this time was 7.0.

繼而，於己二醇(和光純藥股份有限公司製造)1194.03g中，一面進行攪拌一面添加預備液1-1，攪拌30分鐘，而製備固形物成分濃度6.0質量%之預備液1。 Then, the pre-liquid 1-1 was added while stirring in 1194.03 g of hexanediol (manufactured by Wako Pure Chemical Co., Ltd.), and the mixture was stirred for 30 minutes to prepare a preliminary liquid 1 having a solid content concentration of 6.0% by mass.

(步驟2) (Step 2)

將己二醇(和光純藥股份有限公司製造)5211.04g、作為A成分之乙醯丙酮(和光純藥股份有限公司製造)261.60g、作為C成分之鈦酸四異丙酯(Matsumoto Fine Chemical股份有限公司製造：Orgatix TA-10，TiO2濃度28質量%)1492.54g混合，攪拌5分鐘，而製備固形物成分濃度6.0質量%之預備液2。 5211.04 g of hexanediol (manufactured by Wako Pure Chemical Co., Ltd.), 261.60 g of acetonitrile acetone (manufactured by Wako Pure Chemical Co., Ltd.) as component A, and tetraisopropyl titanate (Matsumoto Fine Chemical Co., Ltd.) as component C Co., Ltd. manufactured: Orgatix TA-10, TiO 2 concentration: 28% by mass) 1492.54 g, and stirred for 5 minutes to prepare a preliminary liquid 2 having a solid content concentration of 6.0% by mass.

《附透明被膜基材之評價》 "Evaluation of Transparent Film Substrate"

除了使用該塗佈液以外，以與實施例1相同之方式進行測定、評價。將結果示於表1。 The measurement and evaluation were carried out in the same manner as in Example 1 except that the coating liquid was used. The results are shown in Table 1.

[實施例13] [Example 13]

《透明被膜形成用之塗佈液之製備》 "Preparation of Coating Liquid for Forming Transparent Film"

除了以下之步驟以外，以與實施例1相同之方式製備塗佈液。 A coating liquid was prepared in the same manner as in Example 1 except for the following steps.

將所獲得之塗佈液之各成分之濃度、莫耳比等示於表1。 The concentration, molar ratio, and the like of each component of the obtained coating liquid are shown in Table 1.

(步驟1) (step 1)

將作為B3成分(3官能矽烷化合物)之KBM-13(信越化學工業股份有限公司製造：SiO2濃度44.1質量%)484.25g及Solmix AP-11(Japan Alcohol Trading股份有限公司製造)1273.85g混合，攪拌30分鐘。繼而，一面進行攪拌一面歷時30分鐘逐次添加濃度0.1質量%之硝酸387.51g，攪拌30分鐘。此時之pH值為2.0。於其中一面進行攪拌一面添加三乙醇胺(林純藥工業股份有限公司製造)3.44g，攪拌10分鐘，而製備固形物成分濃度9.9質量%之預備液1-1。此時之pH值為6.9。 4.8.25 g of KBM-13 (manufactured by Shin-Etsu Chemical Co., Ltd.: SiO 2 concentration: 44.1% by mass) and 1273.85 g of Solmix AP-11 (manufactured by Japan Alcohol Trading Co., Ltd.) were mixed as a B3 component (trifunctional decane compound). Stir for 30 minutes. Then, 387.51 g of a 0.1% by mass nitric acid was added successively over 30 minutes while stirring, and the mixture was stirred for 30 minutes. The pH at this time was 2.0. After stirring, 3.44 g of triethanolamine (manufactured by Lin Chun Pharmaceutical Co., Ltd.) was added and stirred for 10 minutes to prepare a preliminary liquid 1-1 having a solid content concentration of 9.9% by mass. The pH at this time was 6.9.

繼而，於己二醇(和光純藥股份有限公司製造)2710.06g中，將純水60.90g及濃度61質量%之硝酸1.01g混合，並攪拌5分鐘。繼而，一面進行攪拌一面添加作為B4成分(4官能矽烷化合物)之矽酸乙酯(多摩化學股份有限公司製造：SiO2濃度28.8質量%)352.40g，並攪拌30分鐘。進而，一面進行攪拌一面添加預備液1-1，攪拌30分鐘，而製備固形物成分濃度6.0質量%之預備液1。 Then, 60.90 g of pure water and 1.01 g of nitric acid having a concentration of 61% by mass were mixed in 2710.06 g of hexanediol (manufactured by Wako Pure Chemical Co., Ltd.), and stirred for 5 minutes. Then, 352.40 g of ethyl decanoate (manufactured by Tama Chemical Co., Ltd.: SiO 2 concentration: 28.8% by mass) as a component B4 (tetrafunctional decane compound) was added while stirring, and the mixture was stirred for 30 minutes. Further, the preliminary liquid 1-1 was added while stirring, and the mixture was stirred for 30 minutes to prepare a preliminary liquid 1 having a solid content concentration of 6.0% by mass.

(步驟2) (Step 2)

將己二醇(和光純藥股份有限公司製造)3498.84g、作為A成分之乙醯丙酮(和光純藥股份有限公司製造)175.65g、作為C成分之鈦酸四異丙酯(Matsumoto Fine Chemical股份有限公司製造：Orgatix TA-10，TiO2濃度28質量%)1002.13g混合，攪拌5分鐘，而製備固形物成分濃度6.0質量%之預備液2。 3498.84 g of hexanediol (manufactured by Wako Pure Chemical Co., Ltd.), 175.65 g of acetonitrile acetone (manufactured by Wako Pure Chemical Co., Ltd.) as component A, and tetraisopropyl titanate (Matsumoto Fine Chemical Co., Ltd.) as component C Co., Ltd. manufactured: Orgatix TA-10, TiO 2 concentration: 28% by mass) 1002.13 g, and stirred for 5 minutes to prepare a preliminary liquid 2 having a solid content concentration of 6.0% by mass.

《附透明被膜基材之評價》 "Evaluation of Transparent Film Substrate"

除了使用該塗佈液以外，以與實施例1相同之方式進行測定、評價。將結果示於表1。 The measurement and evaluation were carried out in the same manner as in Example 1 except that the coating liquid was used. The results are shown in Table 1.

[比較例1] [Comparative Example 1]

《透明被膜形成用之塗佈液之製備》 "Preparation of Coating Liquid for Forming Transparent Film"

將己二醇(和光純藥股份有限公司製造)4507.86g、純水214.93g及濃度61質量%之硝酸3.58g混合，並攪拌5分鐘。繼而，一面進行攪拌一面添加作為B成分(4官能矽烷化合物)之矽酸乙酯(多摩化學股份有限公司製造：SiO2濃度28.8質量%)1243.78g，並攪拌30分鐘，而製備固形物成分濃度6.0質量%之4官能矽烷化合物溶液。 4507.86 g of hexanediol (manufactured by Wako Pure Chemical Co., Ltd.), 214.93 g of pure water, and 3.58 g of nitric acid having a concentration of 61% by mass were mixed and stirred for 5 minutes. Then, 1237.78 g of ethyl decanoate (manufactured by Tama Chemical Co., Ltd.: SiO 2 concentration: 28.8% by mass) was added as a component B (tetrafunctional decane compound) while stirring, and stirred for 30 minutes to prepare a solid content concentration. 6.0% by mass of a solution of a 4-functional decane compound.

將己二醇(和光純藥股份有限公司製造)2527.95g、以TiO2濃度計16.4質量%之乙醯丙酮酸鈦(Matsumoto Fine Chemical股份有限公司製造：Orgatix TC-100，TiO2濃度16.4%)238.81g混合，並攪拌5分鐘，而製備固形物成分濃度6.0質量%之金屬烷氧化物溶液。 The hexylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.) 2527.95g, TiO 2 concentration of 16.4% by mass meter titanium acetyl pyruvate (Matsumoto Fine Chemical Co., manufactured: Orgatix TC-100, TiO 2 concentration of 16.4%) 238.81 g was mixed and stirred for 5 minutes to prepare a metal alkoxide solution having a solid content concentration of 6.0% by mass.

繼而，一面進行攪拌一面將金屬烷氧化物溶液混合至4官能矽烷化合物溶液中，攪拌10分鐘後，添加純水49.75g，於5℃攪拌144小 時。攪拌結束後，利用0.2μm之過濾器進行過濾，將凝集物等去除，而製備濃度CT為6.0質量%之透明被膜形成用之塗佈液。 Then, while stirring, the metal alkoxide solution was mixed into the tetrafunctional decane compound solution, and after stirring for 10 minutes, 49.75 g of pure water was added, and 144 hours was stirred at 5 ° C. Time. After completion of the stirring, the mixture was filtered through a 0.2 μm filter to remove aggregates and the like, thereby preparing a coating liquid for forming a transparent film having a concentration CT of 6.0% by mass.

將所獲得之塗佈液之各成分之濃度、莫耳比等示於表2。 The concentration, molar ratio, and the like of each component of the obtained coating liquid are shown in Table 2.

《附透明被膜基材之評價》 "Evaluation of Transparent Film Substrate"

使用該塗佈液，將紫外線照射後之加熱條件設為350℃、30分鐘，除此以外，以與實施例1相同之方式進行測定、評價。將結果示於表2。 The coating liquid was measured and evaluated in the same manner as in Example 1 except that the heating conditions after the ultraviolet irradiation were 350 ° C for 30 minutes. The results are shown in Table 2.

[比較例2] [Comparative Example 2]

《附透明被膜基材之評價》 "Evaluation of Transparent Film Substrate"

於比較例1中，使用該塗佈液，將紫外線照射後之加熱條件設為200℃、30分鐘，除此以外，以與實施例1相同之方式進行測定、評價。將結果示於表2。 In Comparative Example 1, the coating liquid was used for measurement and evaluation in the same manner as in Example 1 except that the heating conditions after the ultraviolet irradiation were changed to 200 ° C for 30 minutes. The results are shown in Table 2.

[比較例3] [Comparative Example 3]

《附透明被膜基材之評價》 "Evaluation of Transparent Film Substrate"

於比較例1中，使用該塗佈液，將紫外線照射後之加熱條件設為120℃、30分鐘，除此以外，以與實施例1相同之方式進行測定、評價。將結果示於表2。 In Comparative Example 1, the coating liquid was used for measurement and evaluation in the same manner as in Example 1 except that the heating conditions after the ultraviolet irradiation were 120 ° C for 30 minutes. The results are shown in Table 2.

[比較例4] [Comparative Example 4]

《透明被膜形成用之塗佈液之製備》 "Preparation of Coating Liquid for Forming Transparent Film"

(步驟1) (step 1)

將己二醇(和光純藥股份有限公司製造)4507.86g、純水214.93g及濃度61質量%之硝酸3.58g混合，攪拌5分鐘。繼而，一面進行 攪拌一面添加作為B成分(4官能矽烷化合物)之矽酸乙酯(多摩化學股份有限公司製造：SiO2濃度28.8質量%)1243.78g，並攪拌30分鐘，而製備固形物成分濃度6.0質量%之預備液1。 4507.86 g of hexanediol (manufactured by Wako Pure Chemical Co., Ltd.), 214.93 g of pure water, and 3.58 g of nitric acid having a concentration of 61% by mass were mixed and stirred for 5 minutes. Then, 1237.78 g of ethyl decanoate (manufactured by Tama Chemical Co., Ltd.: SiO 2 concentration: 28.8% by mass) was added as a component B (tetrafunctional decane compound) while stirring, and stirred for 30 minutes to prepare a solid content concentration. 6.0% by mass of the preliminary solution 1.

(步驟2) (Step 2)

將己二醇(和光純藥股份有限公司製造)1931.33g、作為A成分之乙醯丙酮(和光純藥股份有限公司製造)1195.89g、作為C成分之鈦酸四異丙酯(Matsumoto Fine Chemical股份有限公司製造：Orgatix TA-10，TiO2濃度28質量%)852.88g混合，並攪拌5分鐘，而製備固形物成分濃度6.0質量%之預備液2。 193.33g of hexanediol (manufactured by Wako Pure Chemical Co., Ltd.), 119.89g of ethyl acetonide (manufactured by Wako Pure Chemical Co., Ltd.) as component A, and tetraisopropyl titanate (Matsumoto Fine Chemical Co., Ltd.) as component C Co., Ltd. manufactured: Orgatix TA-10, TiO 2 concentration: 28% by mass) 852.88 g, and stirred for 5 minutes to prepare a preliminary liquid 2 having a solid content concentration of 6.0% by mass.

(步驟3) (Step 3)

一面進行攪拌一面將預備液2混合至預備液1中，攪拌10分鐘後，添加純水49.75g，於5℃攪拌144小時。攪拌結束後，利用0.2μm之過濾器進行過濾，將凝集物等去除，而製備濃度CT為6.0質量%之透明被膜形成用之塗佈液。 The preliminary liquid 2 was mixed into the preliminary liquid 1 while stirring, and after stirring for 10 minutes, 49.75 g of pure water was added, and the mixture was stirred at 5 ° C for 144 hours. After completion of the stirring, the mixture was filtered through a 0.2 μm filter to remove aggregates and the like, thereby preparing a coating liquid for forming a transparent film having a concentration CT of 6.0% by mass.

將所獲得之塗佈液之各成分之濃度、莫耳比等示於表2。 The concentration, molar ratio, and the like of each component of the obtained coating liquid are shown in Table 2.

《附透明被膜基材之評價》 "Evaluation of Transparent Film Substrate"

除了使用該塗佈液以外，以與實施例1相同之方式進行測定、評價。將結果示於表2。 The measurement and evaluation were carried out in the same manner as in Example 1 except that the coating liquid was used. The results are shown in Table 2.

[比較例5] [Comparative Example 5]

《透明被膜形成用之塗佈液之製備》 "Preparation of Coating Liquid for Forming Transparent Film"

(步驟1) (step 1)

將己二醇(和光純藥股份有限公司製造)4507.86g、純水 214.93g及濃度61質量%之硝酸3.58g混合，並攪拌5分鐘。繼而，一面進行攪拌一面添加作為B成分(4官能矽烷化合物)之矽酸乙酯(多摩化學股份有限公司製造：SiO2濃度28.8質量%)1243.78g，攪拌30分鐘，而製備固形物成分濃度6.0質量%之預備液1。 4507.86 g of hexanediol (manufactured by Wako Pure Chemical Co., Ltd.), 214.93 g of pure water, and 3.58 g of nitric acid having a concentration of 61% by mass were mixed and stirred for 5 minutes. Then, 1237.78 g of ethyl decanoate (manufactured by Tama Chemical Co., Ltd.: SiO 2 concentration: 28.8% by mass) as a component B (tetrafunctional decane compound) was added while stirring, and the mixture was stirred for 30 minutes to prepare a solid content concentration of 6.0. % by mass of the preparation liquid 1.

(步驟2) (Step 2)

將己二醇(和光純藥股份有限公司製造)3067.43g、作為A成分之乙醯丙酮(和光純藥股份有限公司製造)59.79g、作為C成分之鈦酸四異丙酯(Matsumoto Fine Chemical股份有限公司製造：Orgatix TA-10，TiO2濃度28質量%)852.88g混合，並攪拌5分鐘，而製備固形物成分濃度6.0質量%之預備液2。 3067.43g of hexanediol (manufactured by Wako Pure Chemical Co., Ltd.), 59.79g of ethyl acetonide (manufactured by Wako Pure Chemical Co., Ltd.) as component A, and tetraisopropyl titanate (Matsumoto Fine Chemical Co., Ltd.) as component C Co., Ltd. manufactured: Orgatix TA-10, TiO 2 concentration: 28% by mass) 852.88 g, and stirred for 5 minutes to prepare a preliminary liquid 2 having a solid content concentration of 6.0% by mass.

(步驟3) (Step 3)

一面進行攪拌一面將預備液2混合至預備液1中，攪拌10分鐘後，添加純水49.75g，於5℃攪拌144小時，但於攪拌途中觀察到凝膠化，而未進行附透明被膜基材之製作、評價。 While stirring, the preliminary liquid 2 was mixed into the preliminary liquid 1, and after stirring for 10 minutes, 49.75 g of pure water was added, and the mixture was stirred at 5 ° C for 144 hours. However, gelation was observed during the stirring, and the transparent film base was not attached. Production and evaluation of materials.

將所獲得之塗佈液(包含凝膠)中之各成分之濃度、莫耳比等示於表2。 The concentration, molar ratio, and the like of each component in the obtained coating liquid (including a gel) are shown in Table 2.

[比較例6] [Comparative Example 6]

《透明被膜形成用之塗佈液之製備》 "Preparation of Coating Liquid for Forming Transparent Film"

除了以下之步驟以外，以與實施例1相同之方式製備塗佈液。 A coating liquid was prepared in the same manner as in Example 1 except for the following steps.

將所獲得之塗佈液之各成分之濃度、莫耳比等示於表2。 The concentration, molar ratio, and the like of each component of the obtained coating liquid are shown in Table 2.

(步驟1) (step 1)

將作為B成分(3官能矽烷化合物)之KBM-13(信越化學工業股份有限公司製造：SiO2濃度44.1質量%)1184.22g及Solmix AP-11(Japan Alcohol Trading股份有限公司製造)3113.87g混合，並攪拌30分鐘。繼而，一面進行攪拌一面歷時30分鐘逐次添加濃度0.1質量%之硝酸947.25g，並攪拌30分鐘。此時之pH值為2.0。於其中一面進行攪拌一面添加三乙醇胺(林純藥工業股份有限公司製造)8.40g，攪拌10分鐘，而製備固形物成分濃度9.9質量%之預備液1-1。此時之pH值為7.0。 Into a B component (a trifunctional decane compound), KBM-13 (manufactured by Shin-Etsu Chemical Co., Ltd.: SiO 2 concentration: 44.1% by mass), 1184.22 g, and Solmix AP-11 (manufactured by Japan Alcohol Trading Co., Ltd.) 3113.87 g were mixed. Stir for 30 minutes. Then, 947.25 g of nitric acid having a concentration of 0.1% by mass was successively added for 30 minutes while stirring, and stirred for 30 minutes. The pH at this time was 2.0. To the mixture, 8.40 g of triethanolamine (manufactured by Lin Chun Pharmaceutical Co., Ltd.) was added while stirring, and the mixture was stirred for 10 minutes to prepare a preliminary liquid 1-1 having a solid content concentration of 9.9% by mass. The pH at this time was 7.0.

於己二醇(和光純藥股份有限公司製造)3502.49g中，一面進行攪拌一面添加上述預備液1-1，攪拌30分鐘，而製備固形物成分濃度6.0質量%之預備液1。 The raw liquid 1-1 was added to 350.49 g of hexanediol (manufactured by Wako Pure Chemical Co., Ltd.) while stirring, and the mixture was stirred for 30 minutes to prepare a preliminary liquid 1 having a solid content concentration of 6.0% by mass.

(步驟2) (Step 2)

將己二醇(和光純藥股份有限公司製造)893.32g、作為A成分之乙醯丙酮(和光純藥股份有限公司製造)44.85g、作為C成分之鈦酸四異丙酯(Matsumoto Fine Chemical股份有限公司製造：Orgatix TA-10，TiO2濃度28質量%)255.86g混合，攪拌5分鐘，而製備固形物成分濃度6.0質量%之預備液2。 893.32 g of hexanediol (manufactured by Wako Pure Chemical Co., Ltd.), 44.85 g of ethyl acetonide (manufactured by Wako Pure Chemical Co., Ltd.) as component A, and tetraisopropyl titanate (Matsumoto Fine Chemical Co., Ltd.) as component C Co., Ltd. manufactured: Orgatix TA-10, TiO 2 concentration: 28% by mass) 255.86 g, and stirred for 5 minutes to prepare a preliminary liquid 2 having a solid content concentration of 6.0% by mass.

《附透明被膜基材之評價》 "Evaluation of Transparent Film Substrate"

除了使用該塗佈液以外，以與實施例1相同之方式進行測定、評價。將結果示於表2。 The measurement and evaluation were carried out in the same manner as in Example 1 except that the coating liquid was used. The results are shown in Table 2.

[比較例7] [Comparative Example 7]

《透明被膜形成用之塗佈液之製備》 "Preparation of Coating Liquid for Forming Transparent Film"

除了以下之步驟以外，以與實施例1相同之方式製備塗佈 液。 Coating was prepared in the same manner as in Example 1 except for the following steps. liquid.

將所獲得之塗佈液之各成分之濃度、莫耳比等示於表2。 The concentration, molar ratio, and the like of each component of the obtained coating liquid are shown in Table 2.

(步驟1) (step 1)

將作為B成分(3官能矽烷化合物)之KBM-13(信越化學工業股份有限公司製造：SiO2濃度44.1質量%)67.28g及Solmix AP-11(Japan Alcohol Trading股份有限公司製造)176.92g混合，並攪拌30分鐘。繼而，一面進行攪拌一面歷時30分鐘逐次添加濃度0.1質量%之硝酸53.82g，並攪拌30分鐘。此時之pH值為2.1。於其中一面進行攪拌一面添加三乙醇胺(林純藥工業股份有限公司製造)0.48g，攪拌10分鐘，而製備固形物成分濃度9.9質量%之預備液1-1。此時之pH值為7.1。 Mixing 67.28 g of KBM-13 (manufactured by Shin-Etsu Chemical Co., Ltd.: SiO 2 concentration: 44.1% by mass) and 176.92 g of Solmix AP-11 (manufactured by Japan Alcohol Trading Co., Ltd.) as component B (trifunctional decane compound), Stir for 30 minutes. Then, 53.82 g of nitric acid having a concentration of 0.1% by mass was successively added for 30 minutes while stirring, and stirred for 30 minutes. The pH at this time was 2.1. While stirring one side, 0.48 g of triethanolamine (manufactured by Lin Chun Pharmaceutical Co., Ltd.) was added, and the mixture was stirred for 10 minutes to prepare a preliminary liquid 1-1 having a solid content concentration of 9.9% by mass. The pH at this time was 7.1.

於己二醇(和光純藥股份有限公司製造)199.00g中，一面進行攪拌一面添加上述預備液1-1，攪拌30分鐘，而製備固形物成分濃度6.0質量%之預備液1。 In the 199.00 g of hexanediol (manufactured by Wako Pure Chemical Industries, Ltd.), the preliminary liquid 1-1 was added while stirring, and the mixture was stirred for 30 minutes to prepare a preliminary liquid 1 having a solid content concentration of 6.0% by mass.

(步驟2) (Step 2)

將己二醇(和光純藥股份有限公司製造)7072.12g、作為A成分之乙醯丙酮(和光純藥股份有限公司製造)355.03g、作為C成分之鈦酸四異丙酯(Matsumoto Fine Chemical股份有限公司製造：Orgatix TA-10，TiO2濃度28質量%)2025.59g混合，攪拌5分鐘，而製備固形物成分濃度6.0質量%之預備液2。 7072.12g of hexanediol (manufactured by Wako Pure Chemical Co., Ltd.), 355.03g of ethyl acetonide (manufactured by Wako Pure Chemical Co., Ltd.) as component A, and tetraisopropyl titanate (Matsumoto Fine Chemical Co., Ltd.) as component C Co., Ltd. manufactured: Orgatix TA-10, TiO 2 concentration: 28% by mass) 2055.59 g, and stirred for 5 minutes to prepare a preliminary liquid 2 having a solid content concentration of 6.0% by mass.

《附透明被膜基材之評價》 "Evaluation of Transparent Film Substrate"

除了使用該塗佈液以外，以與實施例1相同之方式進行測定、評價。將結果示於表2。 The measurement and evaluation were carried out in the same manner as in Example 1 except that the coating liquid was used. The results are shown in Table 2.

[比較例8] [Comparative Example 8]

《透明被膜形成用之塗佈液之製備》 "Preparation of Coating Liquid for Forming Transparent Film"

除了以下之步驟以外，以與實施例1相同之方式製備塗佈液。 A coating liquid was prepared in the same manner as in Example 1 except for the following steps.

將所獲得之塗佈液之各成分之濃度、莫耳比等示於表2。 The concentration, molar ratio, and the like of each component of the obtained coating liquid are shown in Table 2.

(步驟1) (step 1)

將作為B3成分(3官能矽烷化合物)之KBM-13(信越化學工業股份有限公司製造：SiO2濃度44.1質量%)134.57g及Solmix AP-11(Japan Alcohol Trading股份有限公司製造)353.85g混合，並攪拌30分鐘。繼而，一面進行攪拌一面歷時30分鐘逐次添加濃度0.1質量%之硝酸107.64g，並攪拌30分鐘。此時之pH值為2.0。於其中一面進行攪拌一面添加三乙醇胺(林純藥工業股份有限公司製造)0.95g，攪拌10分鐘，而製備固形物成分濃度9.9質量%之預備液1-1。此時之pH值為6.9。 134.57 g of KBM-13 (manufactured by Shin-Etsu Chemical Co., Ltd.: SiO 2 concentration: 44.1% by mass) and 353.85 g of Solmix AP-11 (manufactured by Japan Alcohol Trading Co., Ltd.) were mixed as a B3 component (trifunctional decane compound). Stir for 30 minutes. Then, 107.64 g of a 0.1% by mass nitric acid was added successively over 30 minutes while stirring, and the mixture was stirred for 30 minutes. The pH at this time was 2.0. On the other hand, 0.95 g of triethanolamine (manufactured by Lin Chun Pharmaceutical Co., Ltd.) was added while stirring, and the mixture was stirred for 10 minutes to prepare a preliminary liquid 1-1 having a solid content concentration of 9.9% by mass. The pH at this time was 6.9.

於己二醇(和光純藥股份有限公司製造)1524.98g中，將純水53.73g及濃度61質量%之硝酸0.90g混合，並攪拌5分鐘。繼而，一面進行攪拌一面添加作為B4成分(4官能矽烷化合物)之矽酸乙酯(多摩化學股份有限公司製造：SiO2濃度28.8質量%)310.95g，並攪拌30分鐘。進而，一面進行攪拌一面添加上述預備液1-1，攪拌30分鐘，而製備固形物成分濃度6.0質量%之預備液1。 In 1,524.98 g of hexanediol (manufactured by Wako Pure Chemical Co., Ltd.), 53.73 g of pure water and 0.90 g of nitric acid having a concentration of 61% by mass were mixed and stirred for 5 minutes. Then, 310.95 g of ethyl decanoate (manufactured by Tama Chemical Co., Ltd.: SiO 2 concentration: 28.8% by mass) as a B4 component (4-functional decane compound) was added while stirring, and the mixture was stirred for 30 minutes. Further, the preliminary liquid 1-1 was added while stirring, and the mixture was stirred for 30 minutes to prepare a preliminary liquid 1 having a solid content concentration of 6.0% by mass.

(步驟2) (Step 2)

將己二醇(和光純藥股份有限公司製造)3621.25g、作為A成分之乙醯丙酮(和光純藥股份有限公司製造)2242.29g、作為C成分之 鈦酸四異丙酯(Matsumoto Fine Chemical股份有限公司製造：Orgatix TA-10，TiO2濃度28質量%)1599.15g混合，攪拌5分鐘，而製備固形物成分濃度6.0質量%之預備液2。 3621.25 g of hexanediol (manufactured by Wako Pure Chemical Co., Ltd.), 2,42.29 g of ethyl acetonide (manufactured by Wako Pure Chemical Co., Ltd.) as component A, and tetraisopropyl titanate (Matsumoto Fine Chemical Co., Ltd.) as component C Co., Ltd. manufactured: Orgatix TA-10, TiO 2 concentration: 28% by mass) 1599.15 g, and stirred for 5 minutes to prepare a preliminary liquid 2 having a solid content concentration of 6.0% by mass.

《附透明被膜基材之評價》 "Evaluation of Transparent Film Substrate"

除了使用該塗佈液以外，以與實施例1相同之方式進行測定、評價。將結果示於表1。 The measurement and evaluation were carried out in the same manner as in Example 1 except that the coating liquid was used. The results are shown in Table 1.

再者，使用B成分(3官能矽烷化合物及其水解縮合物之至少一者)之實施例9~13及比較例6~8中所製備之各透明被膜形成用塗佈液之pH值如下。 In addition, the pH values of the coating liquids for forming transparent films prepared in Examples 9 to 13 and Comparative Examples 6 to 8 prepared using the components B (at least one of the trifunctional decane compound and the hydrolysis condensate thereof) were as follows.

實施例9(pH值5.0) Example 9 (pH 5.0)

實施例10(pH值5.5) Example 10 (pH 5.5)

實施例11(pH值6.0) Example 11 (pH 6.0)

實施例12(pH值4.5) Example 12 (pH 4.5)

實施例13(pH值4.0) Example 13 (pH 4.0)

比較例6(pH值6.0) Comparative Example 6 (pH 6.0)

比較例7(pH值4.0) Comparative Example 7 (pH 4.0)

比較例8(pH值3.3) Comparative Example 8 (pH 3.3)

[評價結果] [Evaluation results]

如表1所示，根據實施例1~13可知，使用本發明之塗佈液所製造之附透明被膜基材於鉛筆硬度、耐擦傷性及抗龜裂性方面優異。 As shown in Table 1, according to Examples 1 to 13, the transparent film base material produced by using the coating liquid of the present invention is excellent in pencil hardness, scratch resistance, and crack resistance.

另一方面，使用比較例1~8之塗佈液之附透明被膜基材無法滿足硬度及抗龜裂性之兩者。 On the other hand, the transparent film substrate to which the coating liquids of Comparative Examples 1 to 8 were used could not satisfy both hardness and crack resistance.

Claims (11)

一種被膜形成用之塗佈液，其係將可與金屬烷氧化物形成螯合物之有機化合物(A成分)、下述式(2)所表示之3官能以上之矽烷化合物及其水解縮合物之至少一者(B成分)、及下述式(3)所表示之金屬烷氧化物及其水解縮合物之至少一者(C成分)溶解或分散至包含水及有機溶劑之混合溶劑中而成者，其特徵在於：上述A成分之莫耳數(M1)與上述C成分之莫耳數(M3)之莫耳比(M1/M3)為0.25以上且未達2.0，上述B成分之莫耳數(M2)與上述C成分之莫耳數(M3)之莫耳比(M2/M3)為0.1以上且9.0以下，(R3)(4-m)Si(R4)m (2)(m為3與4之至少一者；R3為碳數1至8之未經取代或經取代之烷基、未經取代或經取代之芳基、及乙烯基之任一者；R4為碳數1至8之未經取代或經取代之烷氧基、未經取代或經取代之芳氧基、乙烯氧基、羥基、氫原子、及鹵素原子之任一者，可相同亦可不同)M(OR5)n (3)(M為選自Be、Al、Sc、Ti、V、Cr、Fe、Ni、Zn、Ga、Ge、As、Se、Y、Zr、Nb、In、Sn、Sb、Te、Hf、Ta、W、Pb、B、Bi、Ce、及Cu中之1種元素；R5為碳數1至10之未經取代或經取代之烷基；n為 與M之原子價相同之數)。 A coating liquid for forming a film, which is an organic compound (component A) which can form a chelate compound with a metal alkoxide, a trifunctional or higher decane compound represented by the following formula (2), and a hydrolysis condensate thereof At least one of the component (B component) and at least one of the metal alkoxide and the hydrolysis condensate represented by the following formula (3) (component C) is dissolved or dispersed in a mixed solvent containing water and an organic solvent. The composition is characterized in that the molar ratio (M1) of the A component and the molar ratio (M1/M3) of the molar component (M3) of the C component are 0.25 or more and less than 2.0, and the above B component The molar ratio (M2/M3) of the number of ears (M2) to the molar content (M3) of the above-mentioned C component is 0.1 or more and 9.0 or less, and (R3) (4-m) Si(R 4 ) m (2) ( m is at least one of 3 and 4; R 3 is any of an unsubstituted or substituted alkyl group having 1 to 8 carbon atoms, an unsubstituted or substituted aryl group, and a vinyl group; R 4 is The unsubstituted or substituted alkoxy group having 1 to 8 carbon atoms, the unsubstituted or substituted aryloxy group, the ethyleneoxy group, the hydroxyl group, the hydrogen atom, and the halogen atom may be the same or different. M(OR 5 ) n (3) (M is selected from Be, Al, Sc, Ti, V, Cr, Fe, Ni, Zn, Ga, Ge, As, Se, Y, Zr, Nb, In, Sn, Sb, Te, Hf, Ta, W, Pb, B, Bi, One element of Ce and Cu; R 5 is an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms; n is the same number as the valence of M). 如申請專利範圍第1項之透明被膜形成用之塗佈液，其中，源自上述B成分之SiO2換算濃度(濃度C2)為0.005~12質量%之範圍，源自上述C成分之元素M之MOx換算濃度(濃度C3)為0.02~14.25質量%之範圍，上述濃度C2與上述濃度C3之合計(濃度CT)為0.1~15質量%之範圍。 The coating liquid for forming a transparent film according to the first aspect of the invention, wherein the concentration of SiO 2 derived from the component B (concentration C2) is in the range of 0.005 to 12% by mass, and the element M derived from the above-mentioned component C The MO x conversion concentration (concentration C3) is in the range of 0.02 to 14.25 mass%, and the total concentration (concentration CT) of the concentration C2 and the concentration C3 is in the range of 0.1 to 15% by mass. 如申請專利範圍第1項之透明被膜形成用之塗佈液，其中，上述B成分為3官能矽烷化合物及其水解縮合物之至少一者時，上述B成分之莫耳數(M2)與上述C成分之莫耳數(M3)之莫耳比(M2/M3)為0.5~8.0之範圍。 The coating liquid for forming a transparent film according to the first aspect of the invention, wherein the component B is at least one of a trifunctional decane compound and a hydrolysis condensate thereof, the molar number (M2) of the component B and the above The molar ratio (M2/M3) of the molar fraction (M3) of the C component is in the range of 0.5 to 8.0. 如申請專利範圍第1項之透明被膜形成用之塗佈液，其中，上述塗佈液包含3官能之矽烷化合物及其水解縮合物之至少一者時，該塗佈液之pH值為4~8。 The coating liquid for forming a transparent film according to the first aspect of the invention, wherein the coating liquid contains at least one of a trifunctional decane compound and a hydrolysis condensate thereof, and the pH of the coating liquid is 4~ 8. 如申請專利範圍第1項之透明被膜形成用塗佈液，其中，上述塗佈液所含之上述有機溶劑之沸點為120℃以上，且於20℃之黏度為1~400mPa‧s之範圍。 The coating liquid for forming a transparent film according to the first aspect of the invention, wherein the organic solvent contained in the coating liquid has a boiling point of 120 ° C or more and a viscosity at 20 ° C of 1 to 400 mPa ‧ s. 一種透明被膜形成用塗佈液之製造方法，其實施以下之步驟：步驟1：將有機溶劑、水、式(2)所表示之3官能以上之矽烷化合物(B成分)、及水解觸媒進行摻合，而製備預備液1之步驟；步驟2：將有機溶劑、可與金屬烷氧化物形成螯合物之有機化合物(A成分)、及式(3)所表示之金屬烷氧化物(C成分)進行摻合，而 製備預備液2之步驟(其中，上述A成分之摻合量相對於上述C成分之元素M1莫耳為0.25莫耳以上且未達2.0莫耳之範圍)；步驟3：將上述預備液1、上述預備液2、及水進行摻合，於5℃以上且40℃以下之溫度下進行攪拌之步驟；(R3)(4-m)Si(R4)m (2)(m為3與4之至少一者；R3為碳數1至8之未經取代或經取代之烷基、未經取代或經取代之芳基、及乙烯基之任一者；R4為碳數1至8之未經取代或經取代之烷氧基、未經取代或經取代之芳氧基、乙烯氧基、羥基、氫原子、及鹵素原子之任一者，可相同亦可不同)M(OR5)n (3)(M為選自Be、Al、Sc、Ti、V、Cr、Fe、Ni、Zn、Ga、Ge、As、Se、Y、Zr、Nb、In、Sn、Sb、Te、Hf、Ta、W、Pb、B、Bi、Ce、及Cu中之1種元素，R5為碳數1至10之未經取代或經取代之烷基，n為與M之原子價相同之數)。 A method for producing a coating liquid for forming a transparent film, which comprises the steps of: an organic solvent, water, a trifunctional or higher decane compound (component B) represented by the formula (2), and a hydrolysis catalyst; a step of preparing the preliminary solution 1 by blending; Step 2: an organic solvent, an organic compound capable of forming a chelate with the metal alkoxide (component A), and a metal alkoxide represented by the formula (3) a component) is a step of preparing a preliminary solution 2 (wherein the blending amount of the above-mentioned A component is 0.25 mol or more and less than 2.0 mol of the element M1 molar of the above-mentioned C component); Step 3 : a step of mixing the above-mentioned preliminary liquid 1, the above-mentioned preliminary liquid 2, and water, and stirring at a temperature of 5 ° C or more and 40 ° C or less; (R 3 ) (4-m) Si(R 4 ) m ( 2) (m is at least one of 3 and 4; R 3 is an unsubstituted or substituted alkyl group having 1 to 8 carbon atoms, an unsubstituted or substituted aryl group, and a vinyl group; R 4 is not a carbon number of 1-8 of substituted or substituted alkoxy, unsubstituted or substituted aryloxy group of the ethylene group, a hydroxyl group, a hydrogen atom, a halogen and According to any one of the atoms may be the same or different) M (OR 5) n ( 3) (M is selected from Be, Al, Sc, Ti, V, Cr, Fe, Ni, Zn, Ga, Ge, As, One of Se, Y, Zr, Nb, In, Sn, Sb, Te, Hf, Ta, W, Pb, B, Bi, Ce, and Cu, and R 5 is an unsubstituted carbon number of 1 to 10. Or a substituted alkyl group, n being the same number as the valence of M). 如申請專利範圍第6項之被膜形成用之塗佈液之製造方法，其中，上述B成分為3官能矽烷化合物時，於上述步驟1中所獲得之預備液1之pH值為5~8之範圍。 In the method for producing a coating liquid for forming a film according to the sixth aspect of the invention, wherein the component B is a trifunctional decane compound, the pH of the preparation liquid 1 obtained in the above step 1 is 5 to 8. range. 如申請專利範圍第6項之被膜形成用之塗佈液之製造方法，其中，上述預備液1所含之上述B成分之重量平均分子量(聚苯乙烯換算)為300以上且3000以下。 In the method for producing a coating liquid for forming a film according to the sixth aspect of the invention, the weight average molecular weight (in terms of polystyrene) of the component B contained in the preliminary liquid 1 is 300 or more and 3,000 or less. 一種附被膜基材之製造方法，其具備：塗佈步驟，其係將申請專利範圍第1至5項中任一項之塗佈液塗佈 至基材；乾燥步驟，其係於上述塗佈步驟之後，使上述基材上之上述塗佈液乾燥而形成塗佈膜；及硬化步驟，其係使上述塗佈膜硬化而形成被膜。 A method for producing a film-attached substrate, comprising: a coating step of coating a coating liquid according to any one of claims 1 to 5 a substrate; a drying step of drying the coating liquid on the substrate to form a coating film after the coating step; and a curing step of curing the coating film to form a film. 如申請專利範圍第9項之附被膜基材之製造方法，其中，於上述乾燥步驟中，上述塗佈液係於80℃以上且150℃以下進行加熱。 The method for producing a film-attached substrate according to claim 9, wherein in the drying step, the coating liquid is heated at 80 ° C or higher and 150 ° C or lower. 如申請專利範圍第9項之附被膜基材之製造方法，其具備：於上述硬化步驟中，對形成於上述基材上之上述塗佈膜照射紫外線，且於80℃以上且300℃以下進行加熱之步驟。 The method for producing a film-attached substrate according to claim 9, comprising: irradiating the coating film formed on the substrate with ultraviolet rays in the curing step, and performing the film at 80° C. or higher and 300° C. or lower. The step of heating.
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