TW200536620A - Curable liquid resin composition and method for producing multilayer body using same - Google Patents

Abstract

Disclosed is a curable liquid resin composition characterized by comprising the following components (A)-(F): (A) a fluorine-containing polymer having a hydroxyl group in a molecule; (B) particles of one or more metal oxides having a number average particle diameter of not more than 100 nm and a refractive index of not less than 1.50 (hereinafter referred to as metal oxide particles (B)); (C) one or more solvents having a high solubility for the fluorine-containing polymer (A) (hereinafter referred to as a highly volatile solvent (C)); (D) one or more solvents which has high dispersion stability for the metal oxide particles (B) and is compatible with the highly volatile solvent (C) (hereinafter referred to as a less volatile solvent (D)); (E) a curable compound; and (F) a thermal acid generator. The curable liquid resin composition is also characterized in that the relative evaporation rate of the highly volatile solvent (C) is higher than that of the less volatile solvent (D).

Description

200536620 (1) IX. Description of the invention [Technical field to which the invention belongs] The present invention relates to a manufacturing method of a liquid hardening resin composition and a laminated body using the same, and particularly to a method capable of forming two or more layers from one coating film. A layer of a liquid curable resin composition and a method for producing a laminate using the same. [Previous technology] • Nowadays, with the development of multimedia, there have been various developments in various display devices. In addition, among various display devices, especially for mobile users, the visibility of outdoor users is becoming more and more important. In large display devices, users are increasingly demanding that they be more easily visible, so that This improvement in visibility has become a technical issue. In the past, in order to improve the visibility of a display device, a method of forming an anti-reflection film by coating an anti-reflection film made of a low-emissivity material on a substrate of a display device has been implemented. For example, a method of forming a thin film of a fluorine-containing compound by a deposition method is known. However, in recent years, there has been a demand for the development of a technology that can form an anti-reflection film even on a large-scale display device at a low cost, mainly for liquid crystal display devices. However, when a deposition method is used, it is difficult to form a uniform anti-reflection film at a high efficiency for a large-area substrate, and it is difficult to reduce costs because a vacuum device is required. In view of this, a method of dissolving a fluoropolymer having a low refractive index in an organic solvent to prepare a liquid composition, and coating the composition on the surface of a substrate to form an anti-reflection film is being performed. For example, there is a proposal for applying a fluorinated alkylsilane to the surface of a substrate (for example, refer to Patent Document 1 and Patent Document 2). There is also a proposal for a method for coating a fluorine-based polymer having a specific structure (for example, refer to Patent Document 3). _ Patent Literature 1: Japanese Patent Laid-Open No. 6 1-40845, Patent Literature 2: Japanese Patent Laid-Open No. 6-98703 Patent Literature 3: Japanese Patent Laid-Open No. 6- 1 5 023 and so on Most of the anti-reflection films are laminated bodies having different refractive index layers, antistatic layers, and hard coat layers on the substrate. In the conventional manufacturing method, the steps of separately coating each layer on the substrate are repeated. The present invention has been developed as a background in view of the above-mentioned circumstances, and an object thereof is to provide a liquid curable resin composition capable of efficiently producing any two or more layers of continuous layers such as a low refractive index layer and a high refractive index layer. . Another object of the present invention is to provide a hardened film having high transparency, excellent adhesion to a substrate, and excellent scratch resistance and dust cleaning performance. Another object of the present invention is to provide a method for producing a laminated body capable of forming two or more layers from one coating film obtained from a coating composition, and a laminated body obtained therefrom. Another object of the present invention is to provide a method for producing a laminate having a good antireflection effect, and a laminate obtained therefrom. Another object of the present invention is to provide a method for producing a laminate having excellent adhesion to a substrate and high abrasion resistance, and a laminate obtained therefrom-200536620 (3) [Summary of the Invention] To achieve the above object, The present inventors have intensively studied the liquid hardening resin composition capable of imparting a hardened film having a layer structure of two or more layers from a single coating film, and a mechanism for separating the hardened film into two or more layers. It was found that, for a fluoropolymer with a specific structure and a specific metal oxide particle, the solubility of the fluoropolymer with a hydroxyl group in the molecule and the dispersion stability of # metal oxide particles, and the relative evaporation rate can be determined. The fact that one or more combinations of two types of solvents are selected, and one layer of the coating film obtained by applying such a liquid curable resin composition can be separated into a plurality of layers, and the type of solvent and other conditions are selected. That is, the fact that no matter what kind of metal oxide particles can still be separated into multiple layers, the present invention is completed. The present invention can provide a liquid curable resin composition and the like as described below. [1] A liquid curable resin composition characterized by containing the following components (A) to (F); (A) the number average particle diameter of the fluoropolymer (B) having a hydroxyl group in the molecule is One or two or more metal oxide particles below 100 nm and a refractive index of 1.50 or more (hereinafter, referred to as "-(B) metal oxide particles"), (C) pair (A) has One or two or more solvents with high solubility of hydroxyl-containing fluoropolymer (hereinafter, referred to as "(C) fast-evaporating solvent") (D) has high dispersion stability for (B) metal oxide particles, and One or two or more solvents compatible with 200536620 (4) (C) fast-evaporating solvents (hereinafter, referred to as "(D) late-evaporating solvents") (E) hardening compounds, (F) thermally-induced acid generators And (C) the relative evaporation rate of the fast-evaporating solvent is greater than the relative evaporation rate of the (D) late-evaporating solvent. [2] The liquid curable resin composition according to [1], wherein (φ C) a rapidly volatile solvent is one or two or more of which have low dispersion stability for (B) metal oxide particles. A solvent, and (D) a late volatilization solvent are one or two or more solvents having low solubility in a fluoropolymer having a hydroxyl group in the molecule (A). [3] The liquid curable resin composition according to [1] or [2], wherein (B) the metal oxide particles are selected from titanium oxide, hafnium oxide, antimony-containing tin oxide, and tin Indium oxide, aluminum oxide, hafnium oxide, zinc oxide, zinc oxide containing aluminum, tin oxide, zinc oxide containing antimony, and one or more metals oxidized with zinc oxide containing indium and tin oxide containing phosphorus Particles as the main component. [4] The liquid curable resin composition according to [3], wherein (B) the metal oxide particles are particles containing titanium oxide as a main component. [5] The liquid curable resin composition according to any one of [1] to [4], wherein (B) the metal oxide particles are metal oxide particles having a multilayer structure. [6] A hardened film produced by hardening the liquid hardening resin composition according to any one of [1] to [5], characterized in that it has -8-200536620 (5) Multilayer structure with 2 or more layers. [7] The hardened film according to [6], wherein each layer constituting the multilayer structure is a layer in which (B) metal oxide particles are present in a high-density manner or (B) metal oxides are not substantially present. A layer of particles, and at least one layer, is a layer in which (B) metal oxide particles are present in a high-density manner. [8] A method for producing a cured film, characterized in that the method comprises heating by liquid sclerosing resin composition described in any one of [1] to [5], or irradiation with radiation. Steps of hardening. [9] A method for producing a laminated body, which is a base material and a method for producing a laminated body having a multilayer structure thereon, which is characterized in that: a coating is formed on the material or the layer formed on the base material; The liquid curable resin composition according to any one of [1] to [5] to form a coating film, and the solvent is evaporated from the one coating film to form two or more layers. [1〇]. The method for producing a laminate as described in [9], wherein each of the two or more layers is a layer in which metal oxide particles are present in a high-density manner or a metal oxide is not substantially present A layer of particles, and at least one layer is a layer in which metal oxide particles are present in a high-density manner. [11] The method for producing a laminate as described in [10], wherein the two or more layers are two-layer ones. [12] The method for producing a laminate according to any one of [9] to [11], wherein the two or more layers are hardened by heating. [13] The method for producing a laminated body according to any one of [9] to [12], wherein the optical system member for a laminated system is used. [14] The laminated body according to any one of [9] to [1 2], -9-200536620 (6) Clothing method, wherein the anti-reflection film of the laminated system is used. [15] The method for producing a laminated body as described in [Π], wherein the laminated body is at least a local refractive index layer and a low refractive index layer, and the reflection is laminated on the substrate in this order from the side near the substrate. The protective film, and the two layers described in [1 1] are made of a cylindrical refractive index layer and a low refractive index layer. [16] The method for manufacturing a laminate as described in [1 5], wherein the refractive index of the low refractive index layer at 5.89 nm is 1.20 to 1.55, and the refractive index of the high refractive index layer at 589 nm is 1.5. 0 to 2.20, and the refractive index of the lower refractive index layer is high. [17] The method for producing a laminated body according to [11], wherein the laminated body is at least a middle refractive index layer, a high refractive index layer, and a low refractive index layer laminated in this order from the side closer to the substrate. The antireflection film on the substrate, and the two layers described in [1 1] are made of a high refractive index layer and a low refractive index layer. [18] The method for producing a laminate as described in [17], wherein the refractive index of the low refractive index layer at 589 nm is K20 to 1,55 ', and the refractive index of the intermediate refractive index layer at 589 nm is 1,5 〇 to 190, and the refractive index of the lower refractive index layer is high. The refractive index of the high refractive index layer at 589 nm is 2.20, and the refractive index of the medium refractive index layer is local. [1 9] · As [1 5] The laminated body described in any one of [1 to 8] -10- 200536620 (7) A manufacturing method in which a hard coating layer and / or an antistatic layer are further formed on a substrate. [20] A laminated body produced according to the method for producing a laminated body according to any one of [9] to [19]. Since the liquid curable resin composition of the present invention can form a cured film having a multilayer structure such as a high refractive index layer and a low refractive index layer from one coating film, the manufacturing steps of the cured film can be simplified. β Since the liquid curable resin composition of the present invention can form two or more layers from one coating film obtained by applying the composition, the manufacturing steps of a laminate having a multilayer structure can be simplified. Moreover, the abrasion resistance of the cured film or the laminate can be improved by the bias of the metal oxide particles. The liquid curable resin composition of the present invention is particularly suitable for the formation of optical materials such as antireflection films and selective transmission film filters. It also has a high fluorine content and is suitable for use in weather-resistant applications. Materials for coatings, materials for weather-resistant films, materials for coatings, and other materials. In addition, the cured film is excellent in adhesion to a substrate, has high abrasion resistance, and can provide a good antireflection effect. Therefore, the cured film or laminate of the present invention is extremely useful as an anti-reflection film, and therefore, when it is applied to various display devices, its visibility can be improved. [Embodiment] [Best Embodiment of the Invention] The present invention is divided into a liquid curable resin composition, a cured film, and a -11-200536620 (8) laminate, and will be described in detail. 1. Liquid hardening resin composition The liquid hardening resin composition of this invention contains the following components (A) to (F). (A) One or two or more metal oxide particles (hereinafter abbreviated as "metal oxide particles") having a number average particle diameter of fluoropolymer (B) having a hydroxyl group in the molecule of 100 nm or less and a refractive index of 1.50 or more "(B) metal oxide particles") (C) One or two or more solvents (hereinafter, referred to as "(C) fast-volatile solvents") having high solubility in fluoropolymers having a hydroxyl group in the molecule (A) ”) (D) One or two or more solvents (hereinafter, referred to as“ (D) late volatilization solvent ”) with high dispersion stability for (B) metal oxide particles and compatibility with (C) fast volatilization solvent ) (E) The curable compound (F) below the thermally-induced acid generator will be described separately for these components. (A) Fluoropolymer having a hydroxyl group in the molecule Fluoropolymer The polymer having a carbon-fluorine bond in the molecule, the fluorine content thereof is preferably 30% by mass or more, and more preferably by gel permeation chromatography The number average molecular weight obtained in terms of polystyrene is preferably 5,000 or more. Here, the fluorine content is a fluorene measured by the method of alizarin complex (a 1 i z a r n c 0 m p 1 e X ο η) method, and the number average molecular weight is a fluorene when tetrahydrofuran is used as a developing solvent. -12- 200536620 (9) As an example of the fluoropolymer used in the present invention, it is a fluoropolymer having a hydroxyl group in the molecule (hereinafter, referred to as "hydroxyl-containing fluoropolymer"). Examples of preferred hydroxyl-containing fluoropolymers include: • Polysand oxygen in the main chain of monomer-derived structural units derived from hydroxyl groups containing 10 to 50 mol% Hospital segment (segment). Such a hydroxyl-containing fluoropolymer is an olefin-based polymer having a polysiloxane segment represented by the following formula (1) in the main chain, and the proportion of the polysand oxygen segment in the fluoropolymer It is usually preferably 0.1 to 20 mole%. R1 —Si—0— (1) In the formula, R1 and R2 may be the same or different, and represent a hydrogen atom, an alkyl group, a halogenated alkyl group, or an aryl group. The fluoropolymer containing a hydroxyl group preferably has a fluorine content of 30% by mass or more. More preferably, it is 40 to 60% by mass, and further, the number average molecular weight in terms of polystyrene obtained from gel permeation φ chromatography is preferably 5,000 or more, and more preferably 10,000 to 500,000. The fluoropolymer containing a hydroxyl group can be composed of (a) a fluorine-containing olefin compound (hereinafter, referred to as "(a) component"), (b) a monomer compound containing a hydroxyl group that can be copolymerized with the (a) component (hereinafter , Referred to as "(b) component") and (c) siloxane-containing polysiloxane compounds (hereinafter, referred to as "c component"), and (d) a reactive emulsifier (hereinafter, referred to as "" (D) component "and / or (e) can be reacted with monomer compounds other than (b) component copolymerized with the aforementioned (a) component to obtain -13- 200536620 (10) component of k (a) As for the fluorinated olefin compound, an unsaturated double bond having at least one polymerizable property and at least a "fluorine-fixing fluorine atom" can be exemplified. Specific examples include: (1) Tetrafluoroethylene, hexafluoroethylene, _, 3,3,3-trifluoropropene and other fluorinated olefins; (2) Perfluorinated " endyl vinyl ether) or perfluoro (alkoxyalkylethylene) Ethers); (3) perfluoro (methyl vinyl ether), perfluoro (ethyl vinyl ether), perfluoro (propylene vinyl ether), perfluoro Butyl vinyl ether), perfluoro (isobutyl ethyl brewing) and other perfluoro (alkyl vinyl ether); (4) perfluoro (propoxypropyl ethyl ether) and other gas substitution ( Hospital oxygen hospital Jiyiyao _) class; etc. These compounds may be used alone or in combination of two or more. Among the above, hexafluoropropylene, perfluoro (alkyl vinyl ether) or perfluoro (alkoxy vinyl ether) is particularly preferred, and more preferably, these are used in combination. Examples of the hydroxy-containing monomer compound belonging to the component (b) include (1) 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 4 -Hydroxy-containing vinyl acids such as hydroxybutyl vinyl ether, 3-hydroxybutyl vinyl ether, 5-hydroxypentyl vinyl ether, 6-hydroxyhexyl vinyl ether; (2) 2-hydroxyethyl allyl ether, 4- Allyl ethers containing hydroxy groups, such as hydroxybutyl allyl ether, glycerol-allyl ether; (3) allyl alcohol; (4) mesityl ethyl (meth) acrylate; etc. These compounds may be used singly or in combination. Alkyl vinyl ethers containing a hydroxyl group are preferred. The polysiloxane compound containing an azo group, which belongs to the component (c), has an easily cleavable azo group that can be represented by =, and has a polyoxyalkyl segment that can be represented by the general formula (1). -14-200536620 (11) For example, according to the method described in Japanese Patent Laid-Open No. 6-93 1 00? Go to the maker. Specific examples of the component (c) include compounds represented by the following formulae (2).

ch3 ch3 CH3CH3 HO—h〇C (CH2) 2C-N = N-Thousand One (CH2) 2CONH (CH2) 3Si (OSi) y (CH2) 3NH CN CN CH3CH3 (2) where y = 10 to 500, z = l to 50. A preferred combination of the above-mentioned (a) component, (b) component and (c) component is, for example, (1) a fluorinated olefin / a hydroxyl vinyl-containing alkyl vinyl ether / polydimethyloxane unit, (2) Fluorinated olefins / Perfluoro (alkyl vinyl ether) / Ethylene glycol storage ether / Polydimethyl sand oxygenation unit with base, (3) Fluorinated olefin / Perfluoro (alkoxyalkyl vinyl ether) ) / Hydroxy-containing alkyl vinyl ethers / Polydimethylsiloxane units, (4) Fluorinated olefins / Perfluorinated (alkyl ethylene φ ether) / Hydroxy-containing alkyl vinyl ethers / Polydimethylsiloxane Oxane units, (5) fluoroolefins / perfluoro (alkoxy (alkyl vinyl ether) / hydroxy vinyl-containing alkyl vinyl ether / polydimethylsiloxane units. In this kind of fluorine-containing polymerization containing hydroxyl groups Among them, the structural unit derived from the component (a) is preferably 20 to 70 mole%, more preferably 25 to 65 mole%, and particularly preferably 30 to 60 mole%. If derived from (a When the ratio of the structural unit of the component is less than 20 mol%, the fluorine content in the obtained fluoropolymer tends to become too small, and the hardened product of the obtained liquid curable resin composition is difficult to become The emissivity is sufficiently low. On the other hand, if the proportion of the structural unit derived from the component (a) is 70 mol% or more, the obtained fluoropolymer-15-200536620 (12) is dissolved in an organic solvent At the same time, the properties will be significantly reduced, and the transparency and adhesion to the substrate of the resulting liquid curable resin composition will be reduced. In a fluoropolymer with 3 alkoxy groups, the structure derived from (b) component * The unit 'preferably is 10 to 50 mole%. More preferably, the lower limit is 13 mole% i or more, more preferably 20 mole% or more 2 [mol% or less], and the upper limit is more preferable.値 is 45 mol% or less, and more preferably 35 mol% or less. If a fluorinated polymer containing a predetermined amount of the component (b) is used to form a liquid hardening resin composition, the hardened product can be displayed. Good abrasion resistance and dust cleaning performance. On the other hand, if the proportion of the structural unit derived from the component (b) is less than 10% by mole, the fluoropolymer will have poor solubility in organic solvents. Poor 'and if it is more than 50 mol%, the hardened product made from the liquid hardening resin composition will be (C) A polysiloxane compound containing an azo group, which is a thermally-initiated radical generator itself, is a polymerization reaction for the production of fluoropolymers. It has the function as a polymerization initiator, but other free radical initiators can also be used. The proportion of the structural unit derived from the (C) component in the fluoropolymer can be expressed by the general formula (I) The polysand oxygen section is preferably from 0.1 to 20 mole%, more preferably from 0.1 to 15 mole%, particularly preferably from. To 10 mole%, and most preferably from 0.1 to 5 moles. The ratio of ° /. If the ratio of the polysiloxane segment represented by the general formula (1) is more than 20 mol%, the resulting fluoropolymer containing hydroxyl groups will become poor in transparency. When used as a coating agent, cracking is liable to occur in the valley during coating. In addition to the above components (a) to (c), as the component (d), -16-200536620 (13) It is preferable to use a reactive emulsifier as a monomer component. When such a component (d) is used, when a fluoropolymer containing a hydroxyl group is used as a coating agent, good coatability and leveling can be obtained. For such a reactive emulsifier, it is particularly preferable to use a nonionic reactive emulsifier. Specific examples of the non-ionic reactive emulsifier include compounds represented by the following general formula (3) or general formula (4).

H2n.lCn / =. CH20 (CH2) mCH = CH2 V / -〇CH2CH (OCH2CH2) sOH ⑶ In the formula, n = 1 to 20, m and S represent repeating units, m = 0 to 4, s = 3 to 5 0. CH20 (CH2) mCH = CH2 r3-och2-—C-CH (OCH2CH2) sOHH In the formula, m and s are the same as those in the general formula (3). R3 may be a linear φ-shaped or branched alkyl group, and is preferably an alkyl group having 1 to 40 carbon atoms. In the fluoropolymer containing a hydroxyl group, the proportion of the constituent unit derived from the component (d) is preferably 0 to 10 mole%, more preferably 0.1 to 5 mole%, and particularly preferably 0.1. To 1 mole%. If such a ratio is 10 mol% or more, the obtained liquid curable resin composition will become difficult to handle because it will become sticky. If it is used as a coating agent, the moisture resistance will decrease. (E) Component monomers other than component (b) which can be copolymerized with component (a) include (1) methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl Propyl vinyl ether, n-butyl vinyl ether-17- 200536620 (14), isobutyl vinyl acid, third butyl vinyl ether, n-pentyl vinyl ether, n-hexyl vinyl ether, n-butyl vinyl ether, n-decyl Dialkyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether and other alkyl vinyl ethers or cycloalkyl vinyl ethers. Classes; (2) vinyl acetate, vinyl propionate, vinyl butyrate, trimethylacetic acid (pivalic acid) ethylene, caproic acicl, batatic acid, ethylene stearate, and other carboxylic acid vinyl esters; (3) methyl (meth) acrylate, ethyl (methyl Base) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate (Meth) acrylates such as esters, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- (n-propoxy) ethyl (meth) acrylate (4) (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid and other monomer compounds containing a carboxyl group, etc., and those which do not contain a hydroxyl group. More preferred is alkyl vinyl ether. In the fluorinated polymer containing a warp group, the proportion of the constituent units derived from the component (e) is preferably 0 to 70 mole%, and more preferably 5 to 35 mole%. If such a ratio is 70 mol% or more, it is difficult to handle the obtained liquid curable resin composition because it has adhesive properties, and when used as a coating agent, the moisture resistance is reduced. . When (d) component is contained, the preferable combination of (a) component, (b) component, (c) component, (d) component, and (e) component is as follows. (1) Fluorinated olefin / hydroxyl-containing vinyl ether / polydimethylsiloxane unit / non-ionic reactive emulsifier / alkyl vinyl ether, (2) fluorinated dilute hydrocarbon / perfluoro (alkyl ethylene Ether) / Hydroxyethylene ether / Polydimethyl Sand Oxygen Unit / Nonionic Reactive Emulsifier / Alkyl Vinyl Ether, (3) Fluorohydrocarbon-18-18200536620 (15) / Perfluoro (alkane) Oxyalkyl vinyl ether) / Hydroxy-containing vinyl ether / Polydimethyl sand oxygen unit / Nonionic reactive emulsifier / Alkyl vinyl ether, (4) Fluorinated olefin / Perfluorinated (alkyl vinyl ether) ) / Hydroxy-containing vinyl ether / Polydimethyl sand oxide unit / Non-ionic reactive emulsifier / Alkyl vinyl ether, (5) Fluorinated olefin / Perfluoro (alkoxyalkyl vinyl ether) / Contained Hydroxyl vinyl ethers / polydimethylsiloxane units / nonionic reactive emulsifiers / alkyl vinyl ethers. As radical polymerization initiators that can be used with component (c), examples include: (1) Diperoxides such as acetamidine peroxide and benzoyl peroxide; (2) ketones such as methyl ethyl ketone peroxide and cyclohexanone peroxide; (3) hydrogen peroxide, Hydrogen peroxides such as tributyl hydroperoxide and anisin hydroperoxide; (4) Dialkylated peroxides such as di-tertiary butyl peroxide, dicumyl peroxide, and dilaurin peroxide ; (5) Peroxy esters such as third butyl peracetate and third butyl pertrimethyl acetate; (6) azo systems such as azobisisobutyronitrile and azobisisovaleronitrile Compounds; (7) ® persulfates such as ammonium persulfate, sodium persulfate, osmium persulfate; etc. Specific examples other than the above-mentioned radical polymerization initiator include perfluoroethyl iodide, perfluoropropyl iodide, perfluorobutyl iodide, and (perfluorobutyl) ethyl iodide. , Perfluorohexyl iodide, 2- (perfluorohexyl) ethyl iodide, perfluoroheptyl iodide, perfluorooctyl iodide, 2- (perfluorooctyl) ethyl iodide, perfluorodecane Iodine, 2- (perfluorodecyl) ethyl iodide, heptafluoro-2-iodopropane, perfluoro-3-methylbutyl iodide, perfluoro-5-methylhexyl iodide, 2- ( Perfluoro-5-methylhexyl) ethyl iodide, perfluoro-7-methyloctyl iodide, 2- (perfluoro-7-methyloctyl) ethyl iodide, perfluoro-9_methyl Decyl iodine-19- 200536620 (16), 2- (perfluoro-9-methyldecyl) ethyl iodide, 2,2,3,3-tetrafluoropropyl iodide, 1H, 1H, 5H -Octafluoropentyl iodide, 1Η, 1Η, 7Η · dodecylfluoroheptyl iodide, tetrafluoro-1,2-diiodoethane, befluorofluoro-1,4-diiodobutane, twelve Fluorine, iodine-containing fluorine compounds such as -1,6-diiodohexane. The iodine-containing fluorine compound may be used alone or in combination with the above-mentioned organic peroxide, azo-based compound or persulfate. For the production of polymerization types of hydroxyl-containing fluoropolymers, the following can be used: Any of an emulsion polymerization method, a suspension polymerization method, a block polymerization method, or a solution polymerization method using a radical polymerization initiator, and a polymerization operation On the other hand, it can be appropriately selected from batch type, semi-continuous type, or continuous operation. In order to obtain a polymerization reaction of a fluorinated polymer containing a base, it is preferably carried out in a solvent system using a solvent. As the preferred organic solvent, (1) ethyl benzyl acetate, butyl acetate, isopropyl acetate, isobutyl acetate, cellulose acetate, etc .; (2) acetone, methyl ethyl Ketones such as methyl ketones, methyl isobutyl ketones, cyclohexyl ketones; (3) cyclic ethers such as tetrahydrofuran, dihumane; (4) Ν, Ν-dimethylformamide, Ν, Ν- (2) aromatic hydrocarbons such as toluene and xylene; etc. Moreover, ethers, aliphatic hydrocarbons, etc. may be mixed and used as needed. The fluorinated polymer containing a hydroxyl group obtained as described above may be used directly as a liquid curable resin composition in the reaction solution obtained by the polymerization reaction, but an appropriate post-treatment may be performed on the polymerization reaction solution. For such post-treatment, for example, a purification method in which a polymerization reaction solution is added dropwise to an insoluble solvent of the fluoropolymer containing a hydroxyl group formed by an alcohol or the like, so that the fluoropolymer containing a hydroxyl group can be solidified can be implemented. Representative general re-precipitation place-20-200536620 (17) After the solid copolymer is dissolved in a solvent, the solution containing the radical-containing fluoropolymer can be prepared. Alternatively, those remaining monomers removed from the polymerization reaction solution may be directly used as a solution of a fluoropolymer containing a hydroxyl group. The blending ratio of the (A) hydroxyl-containing fluoropolymer in the solid content of the liquid curable resin composition of the present invention is usually 5 to 70% by mass, and if it is made, it is preferably 1%. When it is 50% by mass, the transparency of the cured film is better. (B) Metal oxide particles (B) The metal oxide particles used in the present invention are metal oxide particles having a coefficient average particle diameter of 100 nm or less and a refractive index of 1.50 or more (wavelength 5500 nm). When the number average particle diameter is 100 nm or more, it is sometimes difficult to uniformly disperse the metal oxide particles. In addition, metal oxides tend to settle and lack storage stability. Moreover, the transparency of the obtained cured film may be reduced, or the turbidity (Hoze 値) may be increased. The number average particle diameter is more preferably from 10 to 80 nm, and even more preferably from 20 to 50 nm. In addition, the "number average particle diameter" refers to the "number average particle diameter" measured using an electron microscope method, such as metal oxidation When the object particles are non-spherical (for example, acicular ATO (tin oxide particles containing antimony), etc.), the average is the average of the major axis (longitudinal length) and minor axis (lateral length). When the particle shape is a rod shape (a shape having an aspect ratio of 1 to 10), the short diameter is used as the particle diameter. -21-200536620 (18) As the metal oxide particles, a material selected from the group consisting of zirconia (zirconia), tin oxide containing antimony, indium oxide containing tin, aluminum oxide (Alumina), One or two or more kinds of metal oxides containing hafnium oxide, zinc oxide, zinc oxide containing aluminum, tin oxide, zinc oxide containing antimony, zinc oxide containing indium, and tin oxide containing phosphorus as a main component. Here, a metal oxide particle having a multi-layer structure in which metal oxide particles are coated with one or two or more of the foregoing metal oxides other than the metal oxide may be used. Specific examples of the metal oxide particles having a multilayer structure include silicon oxide-coated titanium oxide particles, aluminum oxide-coated titanium oxide particles, coated titanium oxide particles, aluminum oxide, and chromium-coated titanium oxide particles. Wait. Among these metal oxide particles, particles containing titanium oxide as a main component, aluminum oxide, and chromium oxide-coated titanium oxide particles are particularly preferred. By using metal oxide particles with a multilayer structure, the photocatalytic activity of titanium oxide ® can be suppressed to prevent decomposition of the hardened material. As a result, a cured film having a high refractive index and a different light resistance can be obtained. In addition, if antimony-containing tin oxide particles (ATO) are used, it is possible to impart antistatic properties to the cured film. At this time, as will be described later, since ATTO particles are biased, a smaller amount of particles can be added to achieve both effective charge prevention and good transparency. As the particle containing titanium oxide as a main component, a known one can be used, and the shape may be a hollow particle, a porous particle, a core-shell type particle, or the like. In addition, it is not limited to a spherical shape, and may be a rod shape (referring to a shape of -22-200536620 (19) whose aspect ratio is 1 or more and 10 or less) or an amorphous particle, which is more standard than {± 1 The number average particle diameter obtained by the electron-micromirror method is preferably in a range of 1 to 100 nm. b and j | zhen, preferably water or an organic solvent. Organic solvents include, for example, yeasts such as methanol, isopropanol, ethylene glycol, butanol, and ethylene glycol-propyl ether; ketones such as methyl ethyl ketone and methyl isobutyl; toluene Aromatic hydrocarbons such as xylene, dimethylformamide, dimethylacetamide, N-methyl Φ pyrrolidone, and other amines; ethyl acetate, butyl acetate, r-butyrolactone, etc. Organic solvents such as tetrahydrofuran, 1,4-Df and other ethers, among which alcohols and ketones are preferred. Among them are alcohols and ketones. These organic solvents can be used as a dispersion medium alone 'or as a mixture of two or more kinds. Examples of commercially available particles containing titanium oxide as a main component include products made from Daiyinka (shares) and made into siemens (shares). The liquid curable resin composition has a solid content of 100 mass. The ratio of (B) metal oxide particles per mol is usually 10 to 90 mass. /. , ® is preferably 20 to 80 mass. / 〇. (C) fast volatilizing solvent

The (C) fast volatilizing solvent contained in the liquid curable resin composition of the present invention is one or more solvents having a high solubility in the above-mentioned (A) hydroxyl-containing fluoropolymer. Here, the high solubility of the fluoropolymer containing a hydroxyl group means that when (A) the fluoropolymer containing a hydroxyl group is added to each solvent so that it can become 50% by mass, and it is stirred at room temperature In 8 hours, it can be seen as a uniform solution. In addition, the relative evaporation rate of the (C-23-200536620 (20)) fast-volatile solvent must be higher than the relative evaporation rate of the (D) late-volatile solvent described later. Here, the "relative evaporation rate" refers to the evaporation based on the time required for butyl acetate to evaporate 90% by mass. The relative speed is sloppy. The details are as described in Chemical Technology, Volume 2, Organic Solvents. , Physical properties and purification methods, 4th edition (Science Press, 1986, p. 62). The (C) fast-volatile solvent is preferably one having a low dispersion stability to the metal oxide particles (B). (C) A fast-evaporating solvent, if the relative evaporation rate is greater than (0), the solubility to hydroxyl-containing fluoropolymers is high, and the dispersion stability to (B) metal oxide particles is low, then In the step of applying the liquid curable resin composition of the present invention to a substrate and evaporating the solvents (C) and (D), the (B) metal oxide particles can be biased. In the present invention, for a solvent equivalent to a (C) fast volatilizing solvent, a solvent having a relative evaporation rate of about 1.7 or more, and examples thereof include methyl ethyl ketone (MEK: relative evaporation rate of 3.8), Propanol (IPA: 1.7) ®, methyl isobutyl ketone (MIBK: relative evaporation rate 1.6), methyl amyl ketone (ΜΑΚ: 0 · 3), acetone, methyl propyl ketone, etc. (D) Late volatilizing solvent The (D) late volatilizing solvent contained in the liquid curable resin composition of the present invention is one or two or more solvents having high dispersion stability to the (B) metal oxide particles. . Here, the dispersion stability of the (B) metal oxide particles is high, which means that the glass plate is immersed in the (B) metal oxide particle dispersion liquid so that the (B) metal oxide particles adhere to the glass wall-24 -200536620 (21) 'When (B) metal oxide particles are adhered to the glass agent' (B) The metal oxide particles can be visually recognized as being in a solvent. Further, (D) a late volatilizing solvent, preferably, a fluoropolymer containing a hydroxyl group has low solubility.

In the present invention, a solvent equivalent to a late volatilizing solvent is a solvent having a speed of about 1 · 7 or less, and specific examples thereof include an evaporation rate of 2.1), isopropyl alcohol (IPA ·· 1.7), and I φ ΒυΟΗ: 0.5 ), Tertiary butanol, propylene glycol-methyl ether, ether, propylene glycol-propyl ether, ethyl cellosolve, propyl cellosolve, and the like. The (C) fast-volatile solvent and / or (solvent) used in the present invention can usually be directly used as the solvent used in the production of the above-mentioned (A) hydroxyl-containing substance. The (C) fast-volatile solvent and (D) used in the present invention ), Need to be compatible with each other. Compatibility, in the specific composition of the present invention #, if there is (C) the degree of compatibility between the solvent and the solvent does not separate enough is sufficient. Here, the selected The solvent is intended to be equivalent to 4) the fast volatilizing solvent or (D) the late volatilizing solvent of the present invention, which is determined by the relativity between a plurality of solvents. In addition, “1% of isopropyl alcohol can be equivalent to (C) fast volatilizing solvents; any of 5 hair solvents” can only be used as other (C) fast volatilizing solvents and can only be used as (D) late volatilizing solvent users. Furthermore, the liquid hard resin composition of the present invention is immersed in each of the solvents and dispersed therein. The above (A, relative evaporation: methanol (phase butanol (n-g diol-ethyl agent, Butyl solution D) Late volatilization composition containing per polymerized late volatilization solvent: D) Late volatilization 1 (C After the selected evaporation rate is at L (D) Late volatility solvent combination, in the solvent -25- 200536620 (22) In order to improve the coating properties of the composition or other purposes, solvents other than the above (c) fast-volatile solvents and (D) slow-volatile solvents can be blended. For the solvents that can be blended for this purpose, Examples include ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and esters such as ethyl acetate and butyl acetate. Furthermore, in the solution of the liquid hardening resin composition of the present invention, You can use a solution that does not dissolve the fluoropolymer, such as water, alcohols, esters, and other bad solvents, in a range that will not precipitate the fluoropolymer. Therefore #, sometimes this contains The solution of fluoropolymer can be one with good preservation and better coatability. Specific examples include ethanol, isopropyl alcohol, tertiary butanol, ethyl cellosolve, butyl cellosolve, etc. For solvents (including (C) component and (D)) in the liquid hardening resin composition The total amount of ingredients other than ingredients) is 100 parts by mass. The total metered amount of the solvent (c) and the solvent (D) is usually 300 to 5000 parts by mass, preferably 300 to 4000 parts by mass, and more preferably It is 300 to 3000 parts by mass. The mixing ratio (mass ratio) of the solvent (C) and the solvent (D) can be arbitrarily set in the range of 1: 99 to 99: 1. (E) Hardenable Compound (E) Hardenability Compounds are those which are polymerized by heating, etc., and which impart sclerosis to the composition of the present application. Examples of the sclerosing compound include various amine compounds, or various hydroxyl-containing compounds such as pentaerythritol, polyphenol, and ethylene glycol. Compounds, etc. Amine compounds that can be used as hardening compounds are amine groups that react with the radicals present in fluoropolymers with 3 radicals, such as -26- 200536620 (23) Either one or both of the yuan-based fee-based group and the i-based oxygen-based amino group contain two or more Specific examples of the above compounds include melamine-based compounds, urea-based compounds, benzoguanidine-based compounds, alycolulil-based compounds, and the like. Melamine-based compounds are generally known to have three compounds. (Triazine) A compound having a nitrogen atom skeleton bonded to a ring, specifically, melamine, fluorinated melamine, methyl melamine, methylated melamine, etc. Preferably, one or both of the methyl group and the oxygenated methyl group have two or more in one molecule. Specifically, the methylol group obtained by reacting melamine with formaldehyde under alkaline conditions is preferable. Alkylated melamine, alkoxylated methyl melamine, or derivatives thereof are particularly preferred because they can obtain good storage stability and good reactivity on the liquid curable resin composition. Methylated melamine. There are no restrictions on the methylolated melamine and alkoxylated methyl melamine that can be used as the hardening compound. For example, from the article "Plastic Materials Lecture" 8 "Urea · Melamine Resin" Various types of resins obtained by the method described in the Industrial News Agency. In addition to urea-based compounds, examples other than urea include polymethylolated urea, alkoxylated methylurea which is a derivative thereof, and a urone ring having a uronic ring. Hydroxymethylated uronic acid lactones and alkoxylated methyluronic acid lactones. For compounds such as urea derivatives, various resins described in the above-mentioned documents can also be used. The blending ratio of the curable compound contained in the solid content of 1000 mass% of the liquid curable resin composition is usually 3 to 70 mass%, preferably -27 to 200536620 (24) 3 to 50 mass%, More preferably, it is 5 to 30% by mass. If the amount of the curable compound used is too small, the durability of the film formed from the obtained liquid curable resin composition may be insufficient. If it exceeds the range of 3 to 70% by mass, then In the reaction of the fluoropolymer, gelation tends to occur, and the cured product may become vulnerable. (A) The reaction of a hydroxyl-containing fluoropolymer with (E) a hardening compound. For example, a hardening compound is added to a solution in which an organic solvent # containing a hydroxyl-containing fluoropolymer is dissolved, Heating, stirring, and the like may be performed after the reaction system is homogenized. The heating temperature for this reaction is preferably in the range of 30 to 150 ° C, and more preferably in the range of 50 to 120 ° C. If the heating temperature is below 30 ° C, the reaction will proceed very slowly, while if it is above 150 ° C, in addition to the intended reaction, hydrazone may occur due to hydroxymethyl or It is not suitable to form a gel by the crosslinking reaction caused by the reaction of alkoxymethyl groups with each other. The reaction can be carried out by quantification by infrared spectroscopic analysis of methylol or alkoxymethyl, etc., or by recovering the dissolved polymer by the reprecipitation method and measuring the increase. Confirmation. When the (A) hydroxyl-containing fluoropolymer is reacted with the (E) curable compound, it is preferably the same as the organic solvent used in the production of the hydroxyl-containing fluoropolymer. In the present invention, 'the reaction solution formed by the fluorinated polymer containing a hydroxyl group and the hardening compound thus obtained' can be directly used as a solution of the liquid hardening resin composition, and various additives can be used as required before use. . -28- 200536620 (25) (F) The thermal initiating acid generator which can be blended in the liquid curable resin composition of the present invention is for heating the coating film and the like of the liquid curable resin composition. When hardened, it can improve its heating conditions to a milder substance. Specific examples of such a thermally-induced acid generator include various aliphatic sulfonic acids and their salts, various aliphatic carboxylic acids and their salts such as citric acid, acetic acid, and maleic acid, benzoic acid, and phthalic acid. Various aromatic carboxylic acids and their salts, alkylbenzene sulfonic acids and their ammonium salts, various metal salts, phosphoric acid or organic acid esters, etc. The proportion of the thermally-initiated acid generator that can be contained in 100% by mass of the solid content of the liquid curable resin composition is usually from 0.01 to 10% by mass, preferably from 0.1 to 5% by mass. . / 〇. If the ratio is too large, the storage stability of the liquid hardening resin composition may be inferior. (G) Additive The liquid hardening resin composition of the present invention is composed of the liquid hardening resin composition. For the purpose of improving the coating properties of the material and the cured film, or the imparting of the photosensitivity to the coating film, it may contain, for example, various polymers or monomers having hydroxyl groups, pigments, or dyes Various additives such as stabilizers, anti-aging agents, UV stabilizers, stabilizers, photosensitive acid generators, surfactants, and polymerization inhibitors. In particular, the purpose is to improve the hardness and durability of the formed cured film. It is preferable to add a photo-initiated acid generator, and in particular, it is preferable to select and use a solution that does not reduce the transparency of the liquid curable resin composition after hardening and can be uniformly dissolved in the solvent. 29- 200536620 (26) In the middle. (1) A polymer having a hydroxyl group. A polymer having a hydroxyl group that can be blended in the liquid curable resin composition of the present invention may be exemplified by a polymer containing a hydroxyl group with hydroxyethyl (meth) acrylate or the like. A polymer obtained by copolymerizing a copolymerizable monomer, a resin having a phenol skeleton and the like known as an acid-formaldehyde resin or a soluble phenol resin. (2) A coloring agent such as a pigment or a dye can be blended in the liquid hardening resin composition of the present invention. The coloring agent can be exemplified by: (1) a base of aluminous white, clay, barium carbonate, barium sulfate, etc. Quality pigments; (2) zinc white, lead white, meditation monk, red dan, ultramarine, Prussian blue, titanium oxide, zinc chromate, iron oxide red, carbon black and other inorganic frequency materials; (3) brilliant magenta 6B, Organic pigments such as permanent red 6B, permanent red R, benzidine yellow, phthalocyanine blue, and phthalocyanine green; (4) basic dyes such as magenta and rhodamine; (5) direct scarlet, direct orange, etc. Direct dyes; (6) acid dyes such as Luo Serin, Mitanil Yellow, etc .; etc. (3) Stabilizing agents such as anti-aging agents and ultraviolet absorbers As known anti-aging agents and ultraviolet absorbents that can be blended in the liquid curable resin composition of the present invention, known ones can be used. Specific examples of the anti-aging agent include di-tert-butylbenzene, gallophenol, benzoquinone, hydroquinone, methylene blue, tert-butylcatechol, monobenzyl ether, and methylhydroquinone. , Pentylbenzoquinone, pentoxyhydroquinone, n-butylphenol, -30- 200536620 (27) phenol, hydroquinone-propyl ether, 4,4 '-[1- [4- [4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl] ethylene] diphenol, 1,1,3-ginseng (2,5-dimethyl-4-hydroxyphenyl) -3- Phenylpropane, diphenylamines, phenylenediamines, phe η thiazine, sulfobenzimidazole and the like. As specific examples of the ultraviolet absorber, for example, a salicylic acid-based ultraviolet absorber represented by phenylsalicylate and dihydroxybenzophenone can be used. Diphenyl ketone UV absorbers such as 2-hydroxy-4-methoxydiphenyl ketone, UV absorbers for benzotriazole, UV absorbers for cyanoacrylate, etc. as additives for various plastics The ultraviolet absorber used. (4) Photosensitive acid generator The photoacid generator that can be blended in the liquid curable resin composition of the present invention is for imparting photosensitivity to the coating film of the liquid curable resin composition, for example, irradiation with light Such radiation is a substance that can harden the coating film. Examples of such a photosensitive acid generator include: (1) various key salts such as iodine key salts, phosphonium salts, phosphonium salts, diazo iron salts, ammonium salts, and iron pyridine salts; (2) / 5- Ketone esters, / 5-sulfonamidine and other α-diazo compounds, etc .; (3) Alkyl sulfonates, haloalkyl sulfonates, aromatic sulfonates, imine disulfonic acids Sulfonic acid esters such as esters; (4) sulfonylimine compounds represented by the following general formula (5); (5) diazomethane compounds represented by the following general formula (6); and the like. -31-200536620 (28) 〇

〇

X n ~ so2r4 Y 中 In the formula, X represents a two-membered group such as an alkylene group, an arylene group, or an alkoxy group, and R4 represents a 1 group such as an alkyl group, an aromatic group, a halogen-substituted alkyl group, or a halogen-substituted aromatic group. Yuan base.

Ν2 r5o2s-c-so2r6 中 In the formula, R5 and R6 represent a 1-membered group such as an alkyl group, an aromatic group, a halogen-substituted alkyl group, or a halogen-substituted aromatic group, which may be the same or different from each other. The photosensitive acid generator may be used singly or in combination of two or more kinds, and the aforementioned thermally-induced acid generator may be used in combination. The ratio of the photosensitive acid generator in the solid content of the liquid curable resin composition in the mass of 1,000 parts is preferably 0 to φ 20 parts by mass, and more preferably 0. 1 to 10 parts by mass. If this ratio is too large, it is not suitable because the strength of the sulfonated film will be inferior and the transparency will be reduced. (5) Surfactant In the liquid hardening resin composition of the present invention, a surfactant may be blended for the purpose of improving the coatability of the liquid hardening resin composition. Such a surfactant can be used by a user. Specifically, for example, various anionic surfactants, cationic surfactants, and nonionic surfactants can be used, but in particular, it can be used as a hardened film. Cationic surfactants are preferred because they have excellent strength of -32-200536620 (29) and good optical properties. Furthermore, a quaternary ammonium salt is preferred. Among them, the use of a quaternary polyether-type ammonium salt is particularly preferable because it can further improve the dust-cleaning property. As the cationic surfactant belonging to the quaternary polyether-type ammonium salt, it can be exemplified by Adkaker CC-15, CC-36, CC-42, etc., manufactured by Asahi Denka Kogyo Co., Ltd. The use ratio of the surfactant is preferably 100 parts by mass of the liquid curable resin composition, preferably 5 parts by mass or less. (6) The polymerization inhibitor that can be blended in the liquid curable resin composition of the present invention can be exemplified by gallophenol, benzoquinone, hydroquinone, methylene blue, and third butyl. Catechol, monobenzyl ether, methylhydroquinone, pentylbenzoquinone, pentoxyhydroquinone, n-butylphenol, phenol, hydroquinone-propyl ether, 4,4 '-[1- [4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl] ethylene] diphenol, 1,1,3 · ginseng (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane etc. ®. Such a thermally-initiated polymerization inhibitor is used in an amount of 100 parts by mass, preferably 5 parts by mass or less, with respect to the solid content of the liquid curable resin composition. 2. Hardened film The hardened film of the present invention is obtained by hardening the liquid curable resin composition of the present invention, and is characterized by having a multilayer structure of two or more layers. In particular, it is preferable to have one or more layers in which the (B) metal oxide particles are present in a high-density manner, and one or less layers in which the (B) metal oxide particles are not actually present. -33- 200536620 (30) When forming a cured film from the liquid curable resin composition of the present invention, it is preferable to coat the substrate (member used). As for the coating method, methods such as liquid immersion method, spray method, strip coating method, roll coating method, curtain coating method, gravure printing method, screen printing method, or inkjet method can be used. The means for hardening the liquid curable resin composition is not particularly limited, but it is preferable to perform heating, for example. At this time, it is preferable to be '' heated at 30 to 200 C for 1 to 180 minutes. Due to this method of heating, it is possible to produce a cured film with excellent anti-reflection properties more effectively without damaging the substrate or the formed cured film. It is preferably in the range of 50 to 180. (: Heating for 1 to 120 minutes, more preferably for 1 to 60 minutes at 80 to 150 ° C. It can also be hardened by adding the aforementioned photo-initiating acid generator or irradiating radiation. At this time ' For example, ultraviolet irradiation devices (metal halide lamps, high-pressure mercury lamps, etc.) can be used at 0. It is performed under the light irradiation conditions of 001 to 10 j / cm2, but the irradiation conditions are not particularly limited. More preferably, it is 0. 0 i to 5J / cm2, preferably 0. 1 to 3J / cm2. In addition, the degree of hardening of the cured film, for example, when a melamine compound is used as a hardening compound, such as the infrared spectroscopic analysis of the amount of hydroxymethyl or jbt oxidized methyl groups of the melamine compound, or using a Soxhlet extractor (S ο X h 1 ete X tract ο η) The gelation rate can be determined by quantitative measurement. After the liquid curable resin composition is applied, the solvent (B) and the solvent (D) in the composition are evaporated, and the (B) metal oxide particles are applied to the bottom layer side (that is, the layer adjacent to the adjacent layer). Near the realm) or the opposite side -34- 200536620 (31) The line is biased. Therefore, (B) metal oxide particles are present in high density near the interface on one side of the cured film, and (B) metal oxide particles are substantially absent near the interface on the other side of the cured film. For this reason, a resin layer with a low refractive index will be formed. Therefore, by curing a coating film formed of a liquid curable resin composition, a cured film having substantially a two-layer or more layer structure can be obtained. The layers formed after such separation can be confirmed, for example, by observing the cross section of the obtained film with an electron microscope. Here, a layer in which (B) metal oxide particles exist in a high-density manner means a portion where metal oxide particles are aggregated, and refers to a layer composed of metal oxide particles as a main component, but sometimes When (A) component coexists inside a layer. On the other hand, a layer where (B) metal oxide particles do not substantially exist means a portion where metal oxide particles are not present, but may contain a number of metal oxide particles within a range that does not prevent the effect of the present invention. . This layer is essentially a layer composed of components other than metal oxide particles such as a hardened product of the component (A) and the component (E). In most cases, the cured film of the present invention has a two-layer structure in which a layer in which metal oxide particles are present in a high-density manner and a layer in which metal oxide particles are not actually present are successively formed, respectively. When a polyethylene terephthalate (PET) resin (including a PET resin having an easily-adhesive layer) is used as a base material, a layer which is itself a base material is usually formed next to each other in order. A layer in which the metal oxide particles are present in the density method, and a layer in which the metal oxide particles are not substantially present. The structure of two or more layers will be described in detail later. The resulting cured film preferably has a refractive index that varies from 0.05 to 35-200536620 (32) to 0. 8, more preferably 0. 1 to 0. 6. Furthermore, it is preferable that the refractive index has a major change in the vicinity of the boundary of the substantially two-layer structure. The degree of change in refractive index 'can be adjusted by the content and type of (B) metal oxide, the content and composition of (A) fluoropolymer, and the content and type of (E) hardening compound. In addition, the refractive index ′ at the low refractive index portion of the cured film is, for example, 1.  3 to 1.  5, while the refractive index at the high refractive index portion is 1 · 6 to 2 · 2. 3. Laminated body In the method for producing a laminated body of the present invention, two or more layers can be formed by evaporating the solvent of one layer of the coating film obtained by applying the liquid curable resin composition from the substrate or a layer formed on the substrate. Layers. Here, the state after drying may be a state in which the solvent does not completely disappear, but the solvent may remain in a range where the characteristics as a cured film can be obtained. In the present invention, it is possible to form two or more layers from a single coating film twice or more. If a specific liquid curable resin composition is applied according to a usual method, and then dried, it is separated into two or more layers. Here, a layer of two or more layers may be a layer containing two or more layers of "a layer in which metal oxide particles are present in a high density system" and "a layer in which metal oxide particles are not substantially present", or It may also be a case where two or more layers are formed only by the "layer having metal oxide particles in a high-density method". In the following, using the drawing, "two or more layers are a layer in which metal oxide particles are present in a high-density method or a layer in which metal oxide particles are not substantially present" and at least an i-layer is a metal in which a high-density method is present. Oxide-36-200536620 (33) ". Fig. 1A shows two or more layers, which are two layers of "layer 1 in which metal oxide particles are present in a high density system" and "layer 3 in which metal oxide particles are not substantially present". Fig. 1B shows a layer of 2 t or more layers, which is a case of two layers of "layers 1 and 1 a in which metal oxide particles are present in a high density method". Fig. 1C shows two or more layers, which are three layers of "Layer 1 and la in which metal oxide particles are present in a high-density method" and "Layer 3 in which metal oxide particles are not substantially present". Figure 1 D ® shows two or more layers, which are the three layers of "layer 1 and 1 a in which metal oxide particles are present in a high-density method" and "layer 3 in which metal oxide particles are not substantially present". . Fig. 1E shows two or more layers, which are two layers of "a layer 1b having metal oxide particles in a high-density method" and "a layer 3 having substantially no metal oxide particles." When the liquid curable resin composition contains two or more kinds of metal oxide particles, as shown in Fig. 1B, Fig. 1C, and Fig. 1D, "the presence of metal oxide particles in a high-density method can be formed. "Layer" 2 or more. ^ In addition, the "metal oxide particles" in the "layers having metal oxide particles in a high-density manner" means at least one kind, that is, one or two or more kinds of "metal oxide particles" . If the liquid curable resin composition contains two or more kinds of metal oxide particles, the "layer having metal oxide particles in a high-density method" may be composed of two or more kinds of metal oxide particles (for example, Fig. 1E ). In Fig. 1E, the "layer 1b in which metal oxide particles are present in a high density" is composed of particles X and Y. Since the particle Y is thicker than the "layer 1b in which metal oxide particles are present in a high-density manner", it is prominent in "the layer 3 in which -37- 200536620 (34) metal oxide particles are not substantially present" However, such a protruding portion is also included in the "layer lb in which metal oxide particles exist in a high density manner". In addition, in FIGS. 1A to 1E, the metal oxide particles are generally not present in the "layer 3 in which metal oxide particles are substantially absent", but may contain a small amount within a range that does not prevent the effect of the present invention. Metal oxide particles. In addition, the "layers 1, 1 and 1b in which metal oxide particles are present in a high-density manner" may also contain other substances other than metal oxide particles. As the coating method of the liquid curable resin composition, a known coating method can be used, and in particular, various methods such as a liquid stain method, a coater method, and a printing method can be applied. Drying is usually carried out at a temperature ranging from room temperature to about 100 ° C for about 1 to 60 minutes. These two or more layers are preferably hardened by heating. Specific hardening conditions will be described in detail later. In the present invention, if a liquid curable resin composition is applied to various substrates in the form of a solution, and the resulting coating film is dried / cured, a laminate can be obtained. For example, when the substrate is a transparent substrate, an excellent antireflection film can be formed by providing a low refractive index layer on the outermost layer. The specific structure of the antireflection film is usually a substrate in which a base material and a low refractive index film, or a base material, a high refractive index film, and a low refractive index film are sequentially laminated. In addition, other layers may be interposed between the substrate, the high refractive index film, and the low refractive index film. For example, a hard coating layer, an antistatic layer, a medium refractive index layer, a low refractive index layer, and a high refractive index may be provided. A combination of layers, etc. FIG. 2 shows an antireflection film in which a high refractive index layer 40-38-200536620 (35) and a low refractive index layer 50 are laminated on the substrate 10 in this order. In this antireflection film, the high refractive index layer 40 corresponds to a layer in which metal oxide particles are present in a high density, and the low refractive index layer 50 corresponds to a layer in which metal oxide particles are not substantially present. According to the present invention, the high-refractive index layer 40 and the low-refractive index layer 50 can be formed from a coating film of one. Fig. 3 shows an antireflection film in which a hard coating layer 20, an antistatic layer 30, a high refractive index layer 40, and a low refractive index layer 50 are laminated on the substrate 10 in this order. In this antireflection film, the high refractive index layer 40 corresponds to a layer in which metal oxide particles are present in a high density, and the low refractive index layer 50 corresponds to a layer in which metal oxide particles are not substantially present. According to the present invention, the high refractive index layer 40 and the low refractive index layer 50 can be formed from the coating film. FIG. 4 shows an anti-reflection film in which an antistatic layer 30, a hard coating layer 20, a high refractive index layer 40, and a low refractive index layer 50 are sequentially laminated on a substrate 10. In this antireflection film, the high refractive index layer 40 corresponds to a layer in which metal oxide particles are present in a high density, and the low refractive index layer 50 corresponds to a layer in which metal oxide particles are not substantially present. According to the present invention, the high-refractive index layer 40 and the low-refractive index layer 50 can be formed from a coating film of one. Fig. 5 shows that a hard coating layer 20, an antistatic layer 30, a medium refractive index layer 60, a high refractive index layer 40, and a low-fold-39-200536620 (36 ) Anti-reflection film of the emissivity layer 50. In this anti-reflection film, the high refractive index layer 40 corresponds to a layer in which metal oxide particles are present in a high density manner, and the low refractive index layer 50 corresponds to a layer in which metal oxide particles are not substantially present. Alternatively, each of the medium refractive index layer 60 and the high refractive index layer 40 corresponds to a layer in which metal oxide particles are present in a high-density method, or the medium refractive index layer 60 corresponds to a layer in which metal oxide particles are present in a high-density method. The refractive index layer 40 corresponds to a layer where substantially no metal oxide particles are present. According to the present invention, the middle refractive index layer 60 and the high refractive index layer 40, or the high refractive index layer 40 and the low refractive index layer 50 can be formed from a single coating film. The high refractive index layer 40 and the low refractive index layer 50 are preferably formed of a coating film of 1. Fig. 6 shows an anti-reflection film in which an antistatic layer 30, a hard coating layer 20, a middle refractive index layer 60, a high refractive index layer 40, and a low refractive index layer 50 are laminated in this order on a substrate. In this antireflection film, the high refractive index layer 40 corresponds to a layer in which metal oxide particles are present in a high-density manner, and the low refractive index layer 50 corresponds to a layer in which metal oxide particles are not substantially present. Alternatively, both the medium refractive index layer 60 and the high refractive index layer 40 correspond to a layer in which metal oxide particles are present in a high density method, or the medium refractive index layer 60 corresponds to a layer in which metal oxide particles are present in a high density method, and The high refractive index layer 40 corresponds to a layer in which metal oxide particles are not substantially present. According to the present invention, the middle refractive index layer 60 and the high refractive index layer 40, or the high refractive index layer 40 and the low refractive index layer 50 can be formed from a single coating film. The high refractive index layer 40 and the low refractive index layer 50 are preferably formed of a coating film of 1. -40- 200536620 (37) FIG. 7 shows an antireflection film in which a hard coating layer 20, a high refractive index layer 40, and a low refractive index layer 50 are laminated on the substrate 10 in this order. In this antireflection film, the high refractive index layer 40 corresponds to a layer in which metal oxide particles are present in a high density, and the low refractive index layer 50 corresponds to a layer in which metal oxide particles are not substantially present. According to the present invention, the high-refractive index layer 40 and the low-refractive index layer 50 can be formed from a coating film of one. # FIG. 8 shows an antireflection film in which a hard coating layer 20, a medium refractive index layer 60, a high refractive index layer 40, and a low refractive index layer 50 are laminated on the substrate 10 in this order. In this antireflection film, the high refractive index layer 40 corresponds to a layer in which metal oxide particles are present in a high density, and the low refractive index layer 50 corresponds to a layer in which metal oxide particles are not substantially present. Alternatively, both the medium refractive index layer 60 and the high refractive index layer 40 correspond to a layer having metal oxide particles in a high density method, or the medium refractive index layer 60 corresponds to a layer having metal oxide particles in a high density method, The high refractive index layer 40 corresponds to a layer in which metal oxide particles are not substantially present. According to the present invention, the middle refractive index layer 60 and the local refractive index layer 40, or the high refractive index layer 40 and the low refractive index layer 50 can be formed from a coating film of 1. The high refractive index layer 40 and the low refractive index layer 50 are preferably formed of a coating film of 1. In the ninth diagram, the anti-reflection film of the antistatic layer 30, the high refractive index layer 40, and the low refractive index layer 50 is sequentially laminated on the substrate 10. In this antireflection film, the high refractive index layer 40 corresponds to a layer in which metal oxide particles are present in a high-density manner, and the low refractive index layer 50 corresponds to -41-200536620 (38) substantially no metal oxide exists. Particle layer. According to the present invention, a high refractive index layer 40 and a low refractive index layer 50 can be formed from a coating film of 1. FIG. 10 shows an anti-reflection film in which an antistatic layer 30, a medium refractive index layer 60, a high refractive index layer 40, and a low refractive index layer 50 are laminated in this order on a substrate. In this antireflection film, the high refractive index layer 40 corresponds to a layer in which metal oxide particles are present in a high-density formula, and the low refractive index layer 50 corresponds to a layer in which metal oxide particles are not substantially present. Alternatively, both the medium refractive index layer 60 and the high refractive index layer 40 correspond to a layer in which metal oxide particles are present in a high density method, or the medium refractive index layer 60 corresponds to a layer in which metal oxide particles are present in a high density method. The high refractive index layer 40 corresponds to a layer in which metal oxide particles are not substantially present. According to the present invention, the middle refractive index layer 60 and the high refractive index layer 40, or the high refractive index layer 40 and the low refractive index layer 50 can be formed in a coating film shape of 1. Preferably, the high refractive index layer 40 and the low refractive index layer 50 are formed from a coating film of 1. In addition, in the antireflection film described above, if conductive particles such as tin oxide (ATO) particles containing antimony are added as a metal oxide contained in the liquid curable resin composition to be used, a high density can be obtained. The layer containing a metal oxide becomes a film having a charge prevention property. Therefore, for example, when a high-refractive index layer or a middle-refractive index layer is formed as a layer containing a metal oxide having such a charge prevention property in a high-density method, the high-refractive index layer or the middle-refractive index layer can be used as both Anti-charge film. In this case, the formation of the antistatic film can be omitted. -42- 200536620 (39) The film thickness of the cured film of the present invention in the antireflection film, for example, 0 · 0 5 µ1Ώ to 50 µm, but it is not particularly limited. Next, each layer of the anti-reflection film will be described. .  (1) Substrate The type of the substrate used in the antireflection film of the present invention is not particularly limited as a specific example of the substrate. Triethyl cellulose, ® dimethanol glycol resin (Toray Lumiler, etc.), polycarbonate resins, acrylic resins, styrene-based resins, allyl resins, norbornene-based resins (Alton, JSR (shares), Jeonnicks (Japan)) Etc.), methyl methacrylate / styrene resin, polyolefin resin and other transparent plastic plates, films, etc. Triethyl cellulose, polyethylene terephthalate resin (Lumiler, manufactured by Toray Industries, etc.), norbornene-based resin (Arsenic, manufactured by J s R (stock)), etc. (2) Low-refractive index layer Low-refractive index layer refers to the refractive index at a wavelength of 5 9 9 m: to 1.  5 5 layers. The material used for the low refractive index layer is not particularly limited as long as it has properties that can be obtained, but it can be exemplified by a fluorine-containing curable composition, an acrylic monomer, a fluorine-containing acrylic monomer, and oxygen. In order to improve the low refractive index layer, it is also possible to mix silicon dioxide fine particles and the like with hardened materials such as base compounds. For example, it is definite, but the copolymerization of poly (p-phenylene) glass and the basic compound Benzenonene is preferably (ton), etc. ± 1. 20 As the target polymer, the strength of the ring is -43- 200536620 (40) (3) High refractive index layer The high refractive index layer means that the refractive index is 1 at a wavelength of 5 8 9 nm.  5 〇. To 2. 20, while the lower refractive index layer is the higher refractive index layer. In order to form a high refractive index layer, inorganic particles with high refractive index, such as metal oxide particles, may be blended. Specific examples of the metal oxide particles include: chain-containing oxygen φ tin oxide (ATO) particles, tin-containing indium oxide (ITO) particles, zinc oxide (Zηθ) particles, antimony-containing zinc oxide, Aluminum zinc oxide particles, zinc oxide (Zr02) particles, titanium oxide (Ti02) particles, silicon oxide coated titanium oxide particles, Al203 / Zr〇2 coated Ti〇2 particles, hafnium oxide (Ce02) particles, tin oxide containing phosphorus (PTO) particles and so on. Preferred are antimony tin oxide (ATO) particles, tin containing indium oxide (ITO) particles, tin oxide containing particles, zinc oxide particles containing inscriptions, and Al203 / Zr02 coated Ti02 particles. These metal oxide particles can be used singly or in combination of two or more groups. Also, the high refractive index layer may be provided with a function of a hard coating layer or an antistatic layer. (4) When combining layers having more than three kinds of refractive indices, the refractive index at a wavelength of 5 to 89 nm is 1. 50 to 1. 90, and the layer with a lower refractive index is high, and the layer with a higher refractive index is a layer with a low refractive index, which is called a medium refractive index layer. The refractive index of the middle refractive layer is preferably 1. 50 to 1. 80, better is 1. 50 to -44- 200536620 (41) 1. 75. In order to form a medium refractive index layer, inorganic particles having a high refractive index, such as metal oxide particles, may be provided. Specific examples of the metal oxide particles include tin oxide (ANTO) particles containing antimony, indium oxide (ITO) particles containing tin, zinc oxide particles, zinc oxide containing antimony, and zinc oxide particles containing aluminum. , Zirconia (Zr02) particles, titanium oxide particles, silica-coated titanium oxide, # Al203 / Zr02-coated Ti02 particles, hafnium oxide (Ce02) particles, and the like. More preferred are tin oxide (ATO) particles containing antimony, indium oxide (ITO) particles containing tin, zinc oxide particles containing aluminum, chromium oxide (Zr02) grain wood, and tin oxide (PTO) particles containing phosphorus. These metal oxide particles can be used alone or in combination of two or more groups. Also, the medium refractive index layer may be used as a hard coating layer or an antistatic layer. If you combine a low-refractive index layer and a high-refractive index layer, you can reduce the reflectance. Furthermore, if you combine a low-refractive index layer, a high-refractive index layer, and a middle-refractive index layer, you can reduce the reflectance and reduce Glittering (b 1 uish) hue (color blending). (5) Specific examples of the hard coating of the hard coat layer (bard coat layer) are preferably made of materials such as SiO 2 (May 2nd >, epoxy resin, acrylic resin, melamine resin, etc.) And, it is also possible to blend silicon dioxide in these resins. The hard coating layer is effective in improving the mechanical strength of the laminate. -45-200536620 (42) (6) Specific examples of antistatic layer For example, after the addition of zinc oxide particles containing tin oxide (ATO) particles, tin oxide particles containing indium oxide (ITO) particles of aluminum, tin oxide particles containing phosphorus, or organic, Inorganic conductive compounds are caused by the deposition or sputtering of the aforementioned metal oxides. # An oxide film; a film made of a conductive organic polymer. Examples of conductive molecules include polyacetylene-based conductive polymers. , Polyelectrolyte, polythiophene-based conductive polymer, polypyrrole-based molecule, poly-p-phenylene vinylene-based conductive polymer, etc. In addition, as the liquid hardening resin used in the present invention, Metal oxide while adding Atto particles, ITO particles, zinc-containing particles, aluminum-containing zinc oxide particles, and phosphorus-containing oxidizing conductive particles, the resulting high-density method contains a metal oxide ^ to form a film with antistatic properties. In this case, it can be omitted The step of forming a stop film. The antistatic layer, because it imparts electrical conductivity to the laminate, adheres to dust and the like caused by electrification. These layers can form only one layer or different layers. The film thickness of the middle and high refractive layers is usually 150 nm, and the film thickness of the antistatic layer is usually 0. 〇5 to 3 μm, hard film thickness is usually 1 to 20 μm. Oxygen with antimony and electric hardened wax containing gold; The gold organic high aniline series produced has high conductivity, and the layers such as tin oxide particles of antimony contained in the above will be charged to prevent electricity. The two layers of the layer are from 60 to the quality coating layer-46- 200536620 (43) In the present invention, any continuous two or more layers of the laminate can be formed according to the manufacturing method of the present invention, but if it is not manufactured according to the present invention The method for manufacturing the layer can be manufactured by a known method such as coating and hardening, deposition, sputtering, and the like. In addition, the layer formed of the liquid curable resin composition of the present invention is suitable for forming a cured film having excellent optical characteristics and durability, and is particularly suitable for the thermal history of heating. Of course, when placed under normal temperature®, the hardening reaction can also be formed as the hardening reaction progresses over time. In fact, the method of hardening by heating is more effective because it can shorten the required time. . Further, if a thermally-induced acid generator is added as a curing catalyst, the curing reaction can be further promoted. Such a hardening catalyst is not particularly limited, and various acids or salts thereof used as hardeners such as general urea resins and melamine resins can be used, and an ammonium salt is particularly preferably used. The heating conditions for the curing reaction can be appropriately selected, but the heating temperature needs to be lower than the heat resistance limit temperature of the substrate to be coated. According to the present invention, since two or more layers can be formed from one coating film, the manufacturing steps of the laminated body can be simplified. In addition, since the metal oxide particles are biased, the abrasion resistance of the laminate can be improved. In addition to the antireflection film, the laminated body of the present invention can be used as optical components such as lenses and selective transmission film filters. [Example] -47- 200536620 (44) In the following description, "parts" or [%], unless a specific note indicates "mass parts" or "mass%", respectively. Production Example 1, (1) Synthesis of organic compound having a polymer unsaturated group In a mixed solution of 1 part of fluorenylpropyltrimethoxysilane and dibutyltin dilaurate in a container equipped with a stirrer, dry 5 It took 1 hour at 0 ° C to drip 222 parts of isophorone diisocyanate. ♦ Stir at 70 ° C for 3 hours. Next, NK ester A-TMM-3LM-N (made by Dimura Chemical Co., Ltd., 60% by mass of pentaerythritol dipropylene and 40% by mass of pentaerythritol tetraacrylate) was prepared in the reaction solution at 1 ° C for 1 hour. The responder was only 5 4 9 parts of pentaerythritol triacrylic acid having a hydroxyl group, and then stirred at 60 ° C for 10 hours to prepare a reaction solution. FT-IR (Fourier transform) spectrometer (infra -redspectroscopy)) As a result of measuring the reaction solution ^ product, that is, the amount of isocyanate in the organic compound having a polymerizable unsaturated group, it was 0.  1 mass% or less, and it has been confirmed that it has been implemented in a slightly quantitative manner. From the above, a compound A-2 having 20 parts of pentaerythritol tetraacrylate and non-reacted pentaerythritol tetraacrylate was obtained, which has a compound having a thiourethane bond, and a methoxysilyl group, and a polymerizable unsaturated group. Production Example 2 (2) Synthetic decomposition of urethane acrylate was 22 1 parts in air, and then a new methacrylate was used as the ester. ) Residues in the infrared rays Each reaction 773 parts Urinary key product (• 48- 200536620 (45) For isoflurone diisocyanate in a container with a mixer 18. NK ester A-TMM-3LM-N made by Shin Nakamura Chemical Co., Ltd. was dripped at a solution of 8 parts and 0.2 parts with dibutyltin dilaurate at 1 hour at 10 ° C. It is pentaerythritol diacrylate having a hydroxyl group.) After 93 parts, it was stirred at 60 ° C for 6 hours to prepare a reaction solution. In the same manner as in Production 1, FI-IR was used to measure the product in the reaction solution, that is, the amount of residual isocyanate was 0.1% by mass or less. It was confirmed that each reaction was performed in a slightly quantitative manner. In addition, it was confirmed that a urethane bond and a propylene fluorenyl group (polymerizable unsaturated group) were contained in the molecule. In addition to 75 parts of the urethane hexaacrylate compound prepared above, a composition (A-2) mixed with 37 parts of pentaerythritol tetraacrylate not participating in the reaction was obtained. Production Example 3 [Hardness containing silicon dioxide particles Preparation of the composition for the coating layer] The polymerizable unsaturated group-containing composition (A -1) produced in Production Example 1 was stirred at 60 ° C for 2 · 3 2 parts, and the particle particle sol (methyl ethyl Ketone silica sol, MEK-ST manufactured by Chemical Industries, Ltd., number average particle diameter 0 · 0 2 2 μ m, sand dioxide concentration 30%) 9 1 · 3 parts (silicon dioxide particle timing , For 2 7 parts), ion-exchanged water 0.  12 parts, and p-hydroxyphenyl-methyl ether.  〇 After 1 hour of the mixed solution, methyl orthoformate 1. Thirty-six parts were heated and stirred at the same temperature for an additional hour 'to obtain reactive particles (dispersion (A-3)). 2g of this dispersion (A-3) was weighed on an aluminum dish, dried on a hot plate at 175 ° C for 1 hour, and weighed to obtain -49- 200536620 (46) The result of solid content was 3 0. 7%. In addition, 2 g of the dispersion liquid (A-3) was weighed in a magnetic crucible, and preliminarily dried on a hot plate at 80 ° C for 30 minutes, and fired in a muffle furnace (750 ° C for 1 hour). The following inorganic residue was used to determine the inorganic content in the solid content. 'When 90% ° The dispersion (A-3) 9 8 · 6 g, the composition (A-2) 3 · 4 g, 1- Cyclohexylphenyl ketone 2. 1g, IRGACURE 9〇7 (2-methyl-1-[4--(methylthio) phenyl] -2 -morpholinylpropanone-1 -one, Qi φ bar • Special chemical (stock) system 1.2 g, dipentaerythritol hexapropionic acid vinegar (DPHA) 33. 2 g and 7 g of cyclohexanone were mixed and stirred to obtain a composition for a hard coating layer containing silicon dioxide particles (solid content concentration: 50%). 1 4 5 g 〇 Production Example 4 [The composition of the composition containing chromium oxide particles [Modulation] Add 300 parts of the first rare element chemical industry (stock), UEP-100 (—time # particle size 10 to 30nm) to 700 parts of methyl ethyl ketone (MEK), and use glass beads After dispersing for 1 68 hours, 95.0 parts of an oxide cone dispersing sol was obtained after removing the glass beads. After weighing 2 g of the chromium oxide dispersion sol on an aluminum dish, it was dried on a 12 ° C hot plate for 1 hour, and was weighed to obtain a solid content of 30%. The chromium oxide dispersion sol was 100%. In g, the composition (Α · 1) produced in Production Example 1 was stirred at 60 ° C. 86g, dipentaerythritol hexaacrylate (DPHA) 1 3. 4g, p-methoxyphenol 016 g, ion-exchanged water. 033 g of the mixed solution was added for 3 hours, and then methyl orthoformate was added. 3 32g, and then heating and stirring at the same temperature for 1 hour to prepare -50- 200536620 (47) to obtain a surface-modified chromium oxide particle dispersion 1 116g. This dispersion liquid 1 16 g, composition (A-2) 1 · 3 4 g, hydroxycyclohexyl phenyl ketone 1.2 · 6 g, IRGACURE 907 (2 -methyl-1) -[4- (Methylsulfide) phenyl] -2 _morpholinylpropane-; [-Ketone, Chiba · Special Chemicals (Stock)) 0. 7 6 g, and 46 g of MEK 2 8 were mixed and stirred to obtain 2964 g of a rhenium oxide-containing composition (solid content concentration: 4%). Production Example 5 [Preparation of composition containing tin-containing indium oxide (ITO)] ITO sol (10 wt%, IPA (isopropyl alcohol) sol) manufactured by Fuji Chemical Co., Ltd., 700 g, DPHA 29. 5g, 2-methyl-1- [4 · (methylthio) phenyl] -2-morpholinylpropane-1-one lg, isopropanol (ΙΡΑ) 1 769. 5 g to obtain a ITO particle-containing composition having a solid content concentration of 4%. Production Example 6 [Preparation of composition containing antimony-containing tin oxide (AT 0)] ATO particles (manufactured by Ishihara Technology Co., Ltd., SN-1 OOP, primary particle size 10 to 30 nm), dispersant (Asahi Denka Industrial (stock) system, Atticaplenic TR-701), and methanol, press 90/2. 78/2 1 1 (weight ratio) is mixed (the total solid content is 31%, the total inorganic content is 2 9 -6%). A 50 m 1 polyester bottle of a paint shaker was filled with 40 g of glass beads (manufactured by TOSHINRIKO, BZ-01) (bead diameter 0 mm) (about 16 ml in volume) and the above mixed solution (30 g). After 3 hours of dispersion, a dispersion sol with a median size of 8 Onm was prepared. In this sol 3 04 g, the composition (A-1) was stirred at 60 ° C. 5. 7g, p-methoxyphenol. After a mixture of lg and ion exchange water 0.12 g for 3 hours, methyl formate 1 was added. 3 g, and then heated and stirred at the same temperature for 1 hour, to obtain a surface-modified A TO particle dispersion 3 1 1 g. Add this dispersion 2 7 8. 3 g, composition (A-2) 1. 7g, pentaerythritol triacrylate 8. 59§, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinylpropan-1-one 0. 88 g, 33 g of methanol, and 1 675 g of propylene glycol-methyl ether were mixed and stirred to obtain 2000 g of a composition (solid content concentration: 5%) with ATTO particles. Production Example 7 [Preparation of composition containing aluminum-containing zinc oxide (ZnO doped with A1) particles] Zinc oxide particles (Zeta particles doped with A1 made of Samarium Chemical Co., Ltd., having a primary particle diameter of 10 to 20 nm ), Dispersant (Nanben Chemicals Co., Ltd., Hey Music Special ED 1 5 1) and propylene glycol-methyl ether, press 27. 6/4. 8/67. 6 (weight ratio) blending amount (full solid content 30%, total inorganic content 27. 6%). 40g of oxidation pin beads (bead diameter 0. 1 mm) was dispersed with the above-mentioned mixed solution (30 g) for 8 hours, to obtain a dispersion sol having a medium hafnium particle size of 40 nm. To this 290 g of sol, 10 g of pentaerythritol triacrylate, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinylpropane-1-one 0. 5 g, 2138 g of propylene glycol-methyl ether were mixed and stirred to obtain a composition (solid content concentration: 4%) of 243 8 g containing zinc oxide particles. -52- 200536620 (49) Production Example 8 [Production of hydroxyl-containing fluoropolymer] Using nitrogen, the inner volume was 1.  After 5 liters of stainless steel pressure cooker with electromagnetic stirrer was fully replaced, 500 g of ethyl acetate and perfluoro (propyl vinyl ether) 43 were added. 2g, ethyl vinyl ether 41. 2 g, hydroxyethyl vinyl ether 2 1 · 5 g, "Aticaliya Fertilizer • Soap Ν · 3〇" (manufactured by Asahi Denka Kogyo Co., Ltd.) 40 as a nonionic reactive emulsifier 40. 5g, "VPS-1001" (made by Wako Pure Chemical Industries, Ltd.) as a polydimethylsiloxane containing an azo group 6. 0g and dilaurin peroxide 1. 25g, and cooled to -50 ° C with dry ice-methanol, then use nitrogen again to remove oxygen in the system. Next, add hexafluoropropylene 97. 4g and start to warm up. When the temperature in the pressure cooker reaches 60 ° C, the pressure is 5. 3 X 1 05Pa. Then, the reaction was continued under stirring at 70 t for 20 hours, and the pressure cooker was cooled with water to stop the reaction when the pressure dropped to 1.7 X 105 Pa. After reaching room temperature, the unreacted monomer ® was released and the pressure cooker was opened to obtain a solid concentration of 26. 4% polymer solution. The obtained polymer solution was poured into methanol to precipitate a polymer, washed with methanol, and vacuum-dried at 5 ° C. to obtain 220 g of a fluoropolymer containing a hydroxyl group. It was confirmed that a gel was used for the obtained polymer. The polystyrene-equivalent number average molecular weight (Μη) of permeation chromatography was 48,000, and the glass transition temperature (Tg) using differential scanning calorimetry (DSC) was 26. The fluorine content at 8 ° C and the Alizarin complex method is 50. 3%. -53- 200536620 (50) Production Example 9 [Silica dioxide-coated Ti0 2 (titanium oxide) particle dispersion liquid] To 3 50 parts by mass of titanium dioxide fine powder coated with silicon dioxide was added ethylene oxide- Propylene oxide copolymer (average degree of polymerization: about 2) 8 0 parts by mass, 1000 parts by mass of isopropanol, 1 000 parts by mass of butyl cellosolve, dispersed using glass beads for 10 hours, and after removing the glass beads 243 parts by mass of a silica-coated titanium oxide particle dispersion was prepared. Weighed on a glass dish, took the obtained silica-coated Ti02 particle dispersion, and dried it on a 120 t hot plate for 1 hour to obtain the total solid content concentration, which was 17% by volume. In addition, the sand dioxide-coated T i 0 2 particle dispersion · 1 was weighed magnetically; in an I-pot, preliminarily dried on a hot plate at 80 ° C for 30 minutes, and then dried at 750. (It was fired in a muffle furnace for 3 hours, and the inorganic content in the total solid content was obtained from the amount of the obtained inorganic residue and the concentration of the total solid content, and it was 82% by mass. As a result of electron microscope observation of the solid, It was confirmed that the short-axis average particle diameter was 15 nm, the long-axis average particle diameter was 46 nm, and the aspect ratio was 3. 1 ®, the number average particle diameter is 15 nm. Example 1 and Comparative Example 1 [Production of liquid curable composition] (1) Production of liquid curable resin composition (compositions 1 to 5) The silicon dioxide-coated titanium oxide dispersion liquid obtained in Production Example 9 2 4 g (solid content 4. 08g), 2g of a hydroxyl-containing fluoropolymer obtained in Production Example 8, and a cross-linking compound of methoxymethyl melamine "Seymel 3 0 3" (Mitsui Say Technology Co., Ltd.) 1.2 g, and Catalyst-54- 200536620 (51) 4 0 5 0 (Aromatic sulfonic acid compound produced by Mitsui Sae Technology Co., Ltd.) which is a hardening catalyst 〇. 68 g was dissolved in 32 g of methyl ethyl ketone, 24 g of methyl isobutyl ketone, and 16 g of third butanol as a solvent to obtain a composition 1. As a result of measuring the total solid content concentration of this liquid composition in the same manner as in Production Example 9, it was 7. 5 mass%. In the same manner, the components were blended in such a manner as to achieve the blending ratios in Table 1 below to obtain compositions 2 to 5. Here, in Compositions 2 to 5, alumina was used without coating the titanium oxide dispersion with silicon dioxide, and a Ti02 particle dispersion (made by Dai Yinka) was used without coating with oxide pins, and n-butanol was used without using tertiary butanol. (N-BuOH), the composition of the solvent is methyl ethyl ketone (MEK) / isopropanol (IPA) / methyl isobutyl ketone (MIBK) / n-butanol (n-BuOH) = 40/20 / 30/10 ratio. As a result of measuring the particle diameter in the same manner as in Production Example 9, the number average particle diameter (minor axis average particle diameter) was 20 nm.

(2) Production of the liquid curable resin composition (composition 6) P was used instead of the fluoropolymer having a hydroxyl group obtained in Production Example 8 and manufactured by Cana ADS (Ever Ato Chemical Co., Ltd. Japan). It is a copolymer of hexafluoropropylene 'tetrakis-methyl; C Greek and difluoroethylene. It does not have hydroxyl groups and polymerizable unsaturated groups.) The rest are based on liquid hardening resin composition (composition 1). In the same manner as in the production, a liquid curable resin composition (composition 6) was obtained. Example 2 and Comparative Example 2 -55- 200536620 (52) [Manufacture of hardened film] Sand dioxide particle sol (methyl ethyl ketone silica sol, MEK-ST manufactured by Nissan Chemical Industry Co., Ltd., number average) Particle size: 0,022 μηι, silica concentration 30%) 9 8 · 6 g, 1-hydroxycyclohexylphenyl ketone 2 · g, IRGACURE 907 (2-methyl small [4- (methylthio)) Phenyl] -2-morpholinylpropane-1-one, 1.2 g of Chiba Specialty Chemicals (stock), 33.2 g of dipentaerythritol hexaacrylate (DPHA), and 7 g of cyclohexyl ketone are mixed and stirred ' A composition for a hard coating layer containing silicon dioxide particles was obtained. Using a wire rod coater (#i 2), the composition for the hard coating layer containing silica particles was coated on a triethyl cellulose soft sheet (manufactured by LOFO with a film thickness of 80 μm) and dried in an oven. Dry at 80 ° C for 1 minute. Next, a high-pressure mercury lamp was used in the air to irradiate ultraviolet rays under a light irradiation condition of 0.6 J / cm2 to form a hard coating layer. As a result of measuring the film thickness of the hard coating layer using a stylus-type film thickness meter, it was 5 μm. Using a wire rod coater (# 3), the ® compositions 1 to 6 obtained in Example 1 and Comparative Example 1 were coated on the obtained hard coating layer, and heated at 120 ° c in an oven for 10 minutes to form a film thickness. It is a hardened film layer of 0.2 μm. Evaluation Example 1 [Evaluation of Hardened Film] The cross-sections of the hardened films obtained in Example 2 and Comparative Example 2 were observed with a microscope to evaluate whether they separated into two layers. The evaluation criteria are shown below. Figure 11 shows typical examples in each state. <Evaluation Criteria> -56- 200536620 (53) The two-layer separation was not separated (partially agglomerated). The uniform structure turbidity (haze 値) (%) was measured by using a Haze meter to determine the turbidity in the obtained laminate. Benchmark. 〇: A turbidity of 1% or less. △: The turbidity is below 5%. X: The turbidity is above 5%. The results are shown in Table 1 below.

-57- 200536620

Component composition (mass%) Composition 1 (Example) Composition 2 (Example) Composition 3 (Example) Composition 4 (Comparative example) Composition 5 (Example) Composition 6 (Comparative example) (A) Fluorine containing hydroxyl group Polymer Manufacturing Example 8 25.1 46 26 0 26-Fluoropolymer (without hydroxyl group) Kena ADS-----25.1 (B) Metal oxide particles alumina, chromium oxide coated TiOdion dispersion-49 49 49 49-Silicon dioxide coated Ti02 51.3----51.3 (E) Hardening compound Seymel 303 15.1 0 20 26 25 15.1 (F) Thermally induced acid generator catalyst 4050 8.5 5 5 26 0 8.5 Layer separation Separated two-layer separation layer Separation layer separation Uniform structural layer separation No separation (partial agglomeration) Turbidity 100,000 The description of the names in Table 1 are as follows: (A) Fluoropolymer: In the above-mentioned manufacturing example 1 Manufactured fluoropolymer. Kainer ADS: Copolymer of hexafluoropropylene, tetrafluoroethylene, and difluoroethylene, manufactured by Ivor Ato Chemical Co., Ltd., Japan. Does not have hydroxyl groups and polymerizable unsaturated groups. -58- 200536620 (55) (B) Metal oxide particles made of alumina and hafnium oxide coated Ti02 particles), total solids concentration 28%, particle concentration diameter 20 nm

Sand dioxide coated T i 0 2 particle dispersion: J. (E) Seimeir 3 03: Methoxyl # Yi Technology (F) catalyst (F) catalyst 4 0 5 0: Mitsui Sey Technology (Acid compounds can be seen from the results in Table 1, even if not formulated (and ( F) Thermally-initiated acid generators can still produce 20% and 5). It can be seen that if there is no (A) two-layer separation will not occur if it contains a hydroxyl group (compositions 4 and 6) Example 3 and Comparative Example 3 [Production of liquid curable resin composition and cured film] In the solid content modulating resin composition of composition 3 of Example 1, the liquid curable resin composition of the composition 7 to 10 was changed as shown in Table 2. Liquid hardening using compositions 3 and 7 to 10 was performed in the same manner as in Example 2 under the same conditions, and the same conditions were used to make a dissolving dispersion of a fluorine-containing polymer containing hydroxyl groups (A): Dai Yinka (24%, In the case where the number-average particles make the melamine and Mitsui plugs manufactured in Production Example 2 and the aromatic sulfonate E) hardenable compound layer separate (group of fluoropolymers, the proportion of the liquid hardening solvent is used to obtain Resin composition, according to the reed hardened film .: Sex, (A) contains -59- 200536620 (56) Yes The hydroxyl-containing fluoropolymer can be added to each solvent so that it can be 50% by mass, and after stirring for a predetermined time at room temperature, the solution is judged visually to determine whether it is homogeneous. The results were evaluated according to the following criteria. Table 2 shows the results. <Evaluation Criteria> 〇: A homogeneous solution after stirring for 2 hours. △: A homogeneous solution after stirring for 8 hours. X · Disturbance of non-uniform sentences after 8 hours of stirring. (B) T i The dispersion stability of 〇2 particles is that the glass plate is immersed in the (B) metal oxide particle dispersion to make (B) metal oxide particles adhere to the glass wall. When (B) metal oxide particles are attached When the glass plate was immersed in each solvent, whether or not (B) metal oxide particles were uniformly dispersed in the solvent was visually judged, and evaluated according to the following criteria. The results are shown in Table 2. <Evaluation Criteria> 〇 : In uniform dispersion X: Not uniformly dispersed In Table 2, cereals are arranged from left to right in order of decreasing relative evaporation rate of the solvent. The meaning of the solvent abbreviation is as follows. MEK: methyl ethyl ketone

MeOH: methanol IPA: isopropanol MIBK: methyl isobutyl ketone n-BuOH: n-butanol-60. 200536620 (57) MAK: methyl amyl ketone Evaluation Example 2 [Evaluation of hardened film] Press and evaluate 1 The layer separation properties and turbidity of the cured films obtained in Example 3 and Comparative Example 3 were evaluated in the same manner. The results are shown below.

Table 2 Types of solvents and blending ratio (% by mass) Turbidity layer separation MEK MeOH IPA MIBK n-BuOH MAK Relative evaporation rate of solvent 3.8 2.1 1.7 1.6 0.4 0.3 〇 Solubility of two-layer separation (A) master batch resin. X Δ 〇X 〇 (B) Dispersion stability composition of Ti02 particles 3 (Example) X 40 〇20 X 30 〇10 x_ Composition 7 (Example) 55 45 △ Two-layer separation composition 8 (Comparative example)-55 45--X not separated (partially agglomerated) composition 9 (comparative example)--45-55-X not separated (partially agglomerated) composition 10 (comparative example)--45--55 X not separated (partially agglomerated) From the results in Table 2, it can be seen that for two-layer separation to occur, it is preferable to mix more than two solvents. In the selection, at least 丨 germline (c) to (A) containing -61-200536620 (58) Those with higher solubility and at least one other species (D) have higher dispersion stability of (B) metal oxide particles, and 'requires' the relative evaporation rate of the solvent (C) than the relative evaporation rate of the solvent (D) Example 4 and Comparative Example 4 [Production of Laminate] • (1) Hard coating For the production of the layer, a composition (for a solid content concentration of 50%) of a hard coating layer containing silicon dioxide particles prepared in Production Example 3 was coated on a triethyl cellulose soft sheet (using a wire rod coater (# 1 2)) LOFO, film thickness 80 μm), and dried in an oven at 80 ° C for 1 minute. Next, a high-pressure mercury lamp was used in the air to irradiate ultraviolet rays' under a light irradiation condition of 0.6 J / cm2 to form a cured film layer. The result of measuring the film thickness of the cured film layer using a stylus film thickness meter was 5 μm. ^ (2) Production of the middle refractive index layer Using a steel wire coater (# 3), the composition (solid content concentration: 4%) containing hafnium oxide particles prepared in Production Example 4 was coated in (1) On the hard coating layer, and dried in an oven at 80 ° C for 1 minute. Next, under a nitrogen atmosphere, a high-pressure mercury lamp was used to irradiate ultraviolet rays under a light irradiation condition of 0. 6 J / cm2 to form a cured film layer. The result of calculating the film thickness of the hardened film layer using reflection spectroscopy was 65 nm ° (3) Production of a high refractive index layer and a low refractive index layer. Example 1 and Comparative Example were performed using a wire rod coater (# 3). 1 obtained -62- 200536620 (59) The liquid curable resin compositions of the composition 1 to 6 were respectively coated on the medium refractive index layer prepared in (2), and heated in an oven at 1 2 (TC at 1 ℃). Minutes to form a hardened film layer with a film thickness of 0.2 μm. Example 5 and Comparative Example 5 [Production of Laminated Body] (1) Production of Hard Coating Layer # It was produced in the same manner as in Example 4 (1). 2) Preparation of antistatic layer Using a steel wire coater (# 3), the composition containing solid ITO particles (solid content concentration 4%) prepared in Production Example 5 was applied to the hard coating layer produced in (1) And dried in an oven at 8 ° C for 1 minute. Then, in a nitrogen atmosphere, a high-pressure mercury lamp was used to irradiate ultraviolet rays under a light irradiation condition of 0.6 J / cm2 to form a hardened film layer. The hardened film was calculated using reflection spectrometry As a result of the film thickness of the layer, it was 65 nm. (3) The production of the refractive index layer was as in Example 4 (2) Production in the same manner (4) Production of high-refractive index layer and low-refractive index layer Using a wire rod coater (# 3), the liquid hardening resins of the compositions 1 to 6 obtained in Example 1 and Comparative Example 1 were used. The composition was coated on the medium refractive index layer prepared in (3), and heated in an oven at 120 t for 10 minutes to form a hardened film layer having a film thickness of 0.2 μm. Examples 6, 7 and Comparative Examples 6, 7 -63- 200536620 (60) [Production of laminate] (1) Production of antistatic layer Instead of the ITO particles prepared in Production Example 5, the ITO particles prepared in Production Example 6 or 7 were prepared. Composition (solid content concentration: 5%) or composition containing A1 doped ZnO particles (solid content concentration: 4%) 'Apply to a triethyl cellulose soft sheet (L Ο) using a wire rod coater (# 3) F 0, film thickness 80μπι), and dried in an oven at 80 ° C for 1 minute. Then, in a nitrogen atmosphere, use a high-pressure mercury lamp and irradiate ultraviolet rays under the light irradiation conditions of 0.6 J / cm2 to form hardening Film layer. The result of calculating the film thickness of the hardened film layer using reflection spectroscopy was 65 nm. (2) Hard coating The layer was prepared using a wire rod coater (# 1 2). After coating the composition (solid content concentration 50%) of the hard film layer prepared with the silicon dioxide particles in Production Example 3, it was coated in an oven at 80 ° Dry for 1 minute at C. Then, in the air, use a high-pressure mercury lamp to irradiate ultraviolet rays under a light irradiation condition of 0.6 J / cm2 to form a 5th modified film layer. (3) Production of the middle refractive index layer is in accordance with the examples 4 (2) Made in the same way. (4) Production of high-refractive index layer and low-refractive index layer Using a wire rod coater (# 3), the liquid hardening resin compositions of the compositions 1 to 6 obtained in Example 1 and Comparative Example 1 were separately coated on ( 3) The middle refractive index layer prepared in 3) was heated in an oven at 120 ° C for 10 minutes to form a hardened film layer having a film thickness of 0.2 μm. -64- 200536620 (61) Example 8 and Comparative Example 8 [Production of Laminated Product] It was produced in the same manner as in Example (1). (2) Preparation of high-refractive index layer and low-refractive index layer Using a wire rod coater (# 3), the liquid hardening resin compositions of the compositions 1 to 6 obtained in Example 1 and Comparative Example 1 were separately coated on ( 1) on the hard coating layer prepared in step 1), and dried in an oven at 120 ° C for 10 minutes to form a hardened film layer with a film thickness of 0.2 μm. Evaluation Example 3 [Evaluation of Laminates] The results of observing the cross-sections of the laminates obtained in Examples 4 to 8 and Comparative Examples 4 to 8 using a transmission electron microscope were found on the laminates using the compositions 1, 2, 3, and 5, It was confirmed that the low-refractive index layer and the high-refractive index layer were separated into two layers. At this time, the low refractive index layer is a layer in which metal oxide particles are not substantially present, and the low refractive index layer is a layer in which metal oxide particles are present in a high density manner. On the laminate using composition 4, the 'high-refractive-index layer and the low-refractive-index layer have a uniform structure without layer separation. With the laminate of composition 6, the high-refractive index layer and the low-refractive index layer are partially aggregated without being separated. Using a spectroscopic reflectance measuring device (automatic recording spectrophotometer U-3410 equipped with a large sample chamber integrating sphere attachment device 150-09090, manufactured by Yuli Manufacturing Co., Ltd.), the reflectance at a wavelength of 5 50 nm was evaluated. The anti-reflection properties of the anti-reflection laminate for Compositions 1, 2, 3, and 5 were used -65- 200536620 (62). Specifically, the reflectance of the anti-reflection laminate (anti-reflection film) was measured using the reflectance of the deposited film of aluminum as a reference (1 ο 0%). As a result, the reflectance of all the laminates at a wavelength of 50 nm was below. [Industrial Applicability] Since the cured film obtained by curing the liquid curable resin composition of the present invention can be formed from a single coating film, it has a low-refractive index layer and a local refractive index layer. The film can simplify the manufacturing steps of the hardened film having a multilayer structure. That is, if the liquid curable resin composition of the present invention is used, the manufacturing steps of a laminate having a multilayer structure of two or more layers can be simplified. Therefore, the liquid curable resin composition of the present invention is particularly useful for the formation of optical materials such as antireflection films, lenses, and selective transmission film filters. In addition, the obtained barrier film or laminate can be used for coatings, weather-resistant films, and coatings that require high weather resistance because it can contain a layer with a high fluorine content. In addition, the cured film or laminate has excellent adhesion to the substrate, high abrasion resistance, and can provide a good anti-reflection effect. It is extremely useful as an anti-reflection film, and is suitable for various display devices. When you go up, you can improve its visibility. [Brief description of the drawings] Fig. 1A is a diagram for explaining "two or more layers formed from one coating film". Fig. 1B is a diagram for explaining "two or more layers formed from one coating film". -66- 200536620 (63) Figure 1C: This figure is used to explain the "two or more layers formed from one coating film". Fig. 1D is a diagram for explaining the "two or more layers formed from one coating film". Fig. 1E is a diagram for explaining the "two or more layers formed from one coating film". Fig. 2 is a cross-sectional view of an antireflection film according to an embodiment of the present invention. Fig. 3 is a sectional view of an antireflection film according to another embodiment of the present invention. Fig. 4 is a sectional view of an antireflection film according to another embodiment of the present invention. Fig. 5 is a sectional view of an antireflection film according to another embodiment of the present invention. Fig. 6 is a sectional view of an antireflection film ® according to another embodiment of the present invention. Fig. 7 is a sectional view of an antireflection film according to another embodiment of the present invention. Fig. 8 is a sectional view of an antireflection film according to another embodiment of the present invention. Fig. 9 is a sectional view of an antireflection film according to another embodiment of the present invention. Fig. 10 is a sectional view of an antireflection film according to another embodiment of the present invention. -67- 200536620 (64) Figure 11: Electron microscope showing the state of each state of two-layer separation, non-separation (partial condensation), and uniform structure. [Description of main component symbols] 1: Layer with metal oxide particles in high-density mode 1 a: Layer with metal oxide particles in high-density mode lb: Layer with metal oxide particles in high-density mode 3: Essentially Layer without metal oxide particles 1 0: Substrate 20: Hard coating layer 3 0: Antistatic layer 4 0: High refractive index layer 50 0: Low refractive index layer 60 0: Medium refractive index layer

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Claims (1)

200536620 (1) X. Patent application scope 1 · A liquid hardening resin composition characterized by containing the following components (A) to (F); (A) a fluoropolymer (B) having a hydroxyl group in the molecule ) Number-average particle diameter is below i00nm, and one or two or more kinds of metal oxide particles with a refractive index of 丨 .50 or more (hereinafter, referred to as "(B) metal oxide particles") # (C) pair (A ) One or two or more solvents with high solubility of the fluoropolymer having a hydroxyl group in the molecule (hereinafter, referred to as "(C) fast-volatile solvent") (D) Dispersion and stability of (B) metal oxide particles 1 or 2 or more solvents (hereinafter, referred to as "(D) late volatilization solvents") that are highly soluble and compatible with (C) fast-evaporating solvents (E) hardening compounds (F) thermally-induced acid generators # And (C) the relative evaporation rate of the fast-evaporating solvent is greater than the relative evaporation rate of the (D) late-evaporating solvent. 2. The liquid hardening resin composition according to item 1 of the patent application range, in which (C) the fast volatilizing solvent is one or more solvents having low dispersion stability for (B) metal oxide particles, The (D) late volatilizing solvent is one or two or more solvents having low solubility in a fluoropolymer having a hydroxyl group in the molecule (A). 3. The liquid hardenable resin composition as described in item 1 of the patent application range, wherein (B) the metal oxide particles are selected from titanium oxide, oxide pin-69-200536620 (2), tin oxide containing a chain, One or more metals containing tin oxide oxide, oxide oxide, zinc oxide, zinc oxide, zinc oxide containing aluminum, tin oxide, zinc oxide containing antimony, zinc oxide containing indium, and tin oxide containing phosphorus. Particles having an oxide as a main component. 4. The liquid curable resin composition according to item 3 of the patent application, wherein (B) the metal oxide particles are particles containing titanium oxide as a main component. 5. The liquid curable resin composition according to item 1 of the patent application, wherein (B) the metal oxide particles are metal oxide particles having a multilayer structure. 6. A hardened film, which is obtained by hardening a liquid hardening resin composition in the scope of patent application No. 1 and has a multilayer structure of two or more layers. 7 · The hardened film according to item 6 of the scope of patent application, wherein each layer constituting the multilayer structure is a layer in which (B) metal oxide particles are present in a high-density manner, or (B) metal oxide particles are substantially absent. A layer, and at least one layer, is a layer in which (B) metal oxide particles are present in a high-density manner. 8. A method for manufacturing a cured film, which comprises the steps of heating the liquid curable resin composition in accordance with the scope of the patent application No. 1 or curing it by irradiation of radiation. 9. A method for manufacturing a laminate, which is a substrate and a method for manufacturing a laminate having a multilayer structure thereon, characterized in that an application is applied on the aforementioned substrate or on a layer formed on the substrate Liquid-70-200536620 (3) of the patent scope of the patent forms a hardening resin composition to form a coating film, and the solvent is evaporated from the one coating film to form two or more layers. 10. According to the method for manufacturing a laminated body according to item 9 of the scope of patent application, each of the two or more layers in the _ is a layer in which metal particles are present in a high-density manner or a layer in which metal oxide particles are not substantially present. One layer is a layer in which metal oxide particles exist in a high-density method. 1 1 · If the manufacturer of the laminate of item 10 in the scope of patent application is removed, Φ Among the above 2 layers, those are 2 layers. 1 2. If the method for manufacturing a laminated body according to item 9 of the scope of patent application, the two or more layers are hardened by heating. 1 3 · If the method of manufacturing a laminated body according to item 9 of the scope of patent application, _ optical components for the middle laminated system. 14. If the method for manufacturing a laminated body according to item 9 of the scope of patent application, the anti-reflection film of the middle-layer system. 1 5 · According to the method for manufacturing a laminated body according to item 11 of the patent application scope, where the laminated body is at least a high refractive index layer and a low refractive index layer laminated on the substrate in this order from the side near the substrate. The anti-reflection film is composed of a high refractive index layer and a low refractive index layer. 1 6 · The method for manufacturing a laminate according to item 5 of the scope of patent application, wherein the refractive index of the low refractive index layer is 1.20 to 1.55 at 589 nm, and the refractive index of the high refractive index layer is 1.50 to 2.20 at 589 nm And has a higher refractive index than the low refractive index layer. -71-200536620 (4) 1 7 · The manufacturing method of the laminated body according to item Π of the patent application scope, wherein the laminated body is at least a medium refractive index layer, a high refractive index layer, and a low refractive index layer. The antireflection film is laminated on the substrate in this order, and the two layers described in the item 11 of the patent application range are made of a high refractive index layer and a low refractive index layer. 1 8 · According to the method of manufacturing a laminated body according to item 17 of the scope of patent application, # where the refractive index of the low refractive index layer at 5 8 9nm is 1.20 to 1.55, and the refractive index of the medium refractive index layer at 5 8 9nm is 1. 50 to 1.90, while the refractive index is higher than the low refractive index layer, the refractive index of the high refractive index layer is 1.51 to 2.20 at 589 nm, and the refractive index of the high refractive index layer is higher. 19. The method for manufacturing a laminated body according to item 15 or 17 of the scope of patent application, wherein a hard coating layer and / or an antistatic layer is formed on the substrate. 20. A laminated body is based on the Produced by the method for producing a laminate of 9 items. -72-