TW201012882A - Coating liquid, cured film, resin multilayer body, method for producing the cured film and method for producing the resin multilayer body - Google Patents

Abstract

Disclosed is a coating liquid containing: (A) a hydrolysis-condensation product of silane compounds having an alkoxy group, namely (A-1) a tetraalkoxysilane compound, (A-2) an organoalkoxysilane compound containing no amino group, no epoxy group and no isocyanate group, (A-3) a silane compound having an amino group and an alkoxy group, (A-4) a silane compound having an epoxy group and an alkoxy group and (A-5) a blocked isocyanate silane compound having an alkoxy group; (B) organic polymer fine particles composed of a copolymer containing a monomer unit having an ultraviolet-absorbing group; (C) a colloidal silica; (D) a curing catalyst and (E) a dispersion medium. A cured film using the coating liquid, a resin multilayer body, a method for producing the cured film and a method for producing the resin multilayer body are also disclosed.

Description

[Technical Field] The present invention relates to a coating liquid, a cured film, a resin laminate, and a method for producing the cured film and the resin laminate. [Prior Art] Thermoplastic plastics, especially polycarbonate resins, are widely used as structural materials instead of glass because of their excellent transparency, light weight, and excellent impact resistance. However, since the surface properties are poor due to abrasion resistance, scratch resistance, weather resistance, and chemical resistance, the use thereof is limited, and it is highly desired to improve the surface characteristics of the polycarbonate base material. As a method for improving the surface characteristics, there is a method in which the surface of the molded article is coated with a polycarbonate treatment with a surface treatment agent. For example, a method of forming a cured layer containing a polyfunctional acrylic photocurable resin, a melamine-based or an organopolyoxygenated thermosetting resin on the surface of a polycarbonate substrate has been proposed. Among these, those covered with an organic siloxane-based resin are considered to be useful because they are excellent in abrasion resistance, scratch resistance, and chemical resistance. However, the coating of the organic siloxane-based resin has a problem in adhesion to the polycarbonate resin, and in particular, when it is used outdoors for a long period of time, there is a problem that the coating layer is peeled off. Further, even if the film thickness of the organic fluorene f-based resin is increased in order to improve the adhesion or the abrasion resistance, it is likely to be broken at the time of curing. About patent improvement, patent document! Among them, there are proposed methods for adjusting various kinds of polymers to be used in hard coating or hard coating materials, but resistance is not sufficient. 141326.doc 201012882 The scratch resistance is not sufficient. Further, in Patent Documents 2 and 3, the cured film is applied to the surface of the substrate and the inorganic hard layer is provided thereon, but sufficient adhesion is not obtained. Patent Documents 4 and 5 disclose a resin laminate including a coating layer and a substrate. The sheath layer has a film internal structure in which a polymer nanoparticle having an ultraviolet absorbing ability is dispersed in a siloxane matrix (Si_〇 skeleton). The resin laminate has excellent abrasion resistance and initial adhesion between the substrate and the coating layer. However, when the resin laminate is used for a member such as a window with a wiper, which is accompanied by severe friction, it is resistant to abrasion. There is still room for improvement in terms of sex and wear resistance. In addition, there is still room for improvement in durability (boil resistance). Patent Document 1: Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. 5: WO 2007/099784 SUMMARY OF INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION The present invention has been made in view of the above circumstances, and an object thereof is to provide a coating liquid which forms a cured film which does not use a primer even if it is not used. It also has good adhesion to the substrate or inorganic hard layer, transparent conductive film and photocatalyst layer, and has excellent wear resistance, scratch resistance, flex resistance, weather resistance (UV absorption capacity), and durability. Properties such as properties (boil resistance), a cured film having the above characteristics, and a base material, a resin laminate having the cured film, and a cured film and resin A method of manufacturing a laminate. MEANS FOR SOLVING THE PROBLEMS The present inventors have conducted intensive studies on the formation of a coating liquid for forming a cured film having the above characteristics, and as a result, obtained the following knowledge. The present inventors have found that a hydrolyzed condensate comprising a decane compound having an alkoxy group, an organic cerium molecular microparticle containing a copolymer containing a monomer unit having an ultraviolet absorbing group, a colloidal cerium oxide, a hardening catalyst, and The coating liquid of the dispersion medium is heated to be hardened to obtain a cured film having desired characteristics and formed by forming the cured film on the substrate or the layers of the inorganic hard layer, the transparent conductive film and the photocatalyst layer, and the substrate. In order to obtain the desired resin laminate. The present invention has been completed based on the above knowledge findings. That is, the present invention provides a coating liquid, a cured film, a resin laminate, and a method for producing the cured film and the resin laminate. [1] A coating liquid characterized by comprising the following components (A) to (E): (A) Hydrolysis condensation of a decyl compound having an alkoxy group of the following components (A-1) to (A-5) (A-1) a tetraalkoxy decane compound, (A-2) an organoalkoxy oxime compound containing no amine group, epoxy group and isocyanate group, (A-3) having an amine group and an alkoxy group a decane compound, (A-4) a decane compound having an epoxy group and an alkoxy group, (A-5) a blocked isocyanatodecane compound having an alkoxy group; 141326.doc 201012882 (B) Organic polymer microparticles comprising a copolymer of monomer units having an ultraviolet absorbing group; (C) colloidal cerium oxide; (D) a hardening catalyst; (E) a dispersion medium. [2] The coating liquid according to [1], which further comprises (F) an oxidizing agent treated with a decane compound, and (G) a dispersion stabilizer. [3] The coating liquid according to [1] or [2], wherein the component (A-1) is a tetraalkoxydecane compound represented by the following formula (1):

Si(〇R1)4 (1) wherein R1 represents an alkyl group having 1 to 4 carbon atoms or an alkyl group having an ether bond; a plurality of R1's may be the same or different. [4] The coating liquid according to [1] or [2], wherein the component (A-2) is an organoalkoxy group having no amine group, epoxy group or isocyanate group represented by the following formula (2) Calcined compound: R2aSi(〇R3)4.a (2) wherein R2 represents an alkyl group having 1 to 10 carbon atoms or a fluoroalkyl group; a vinyl group; a stupid group; or a mercaptopropenyloxy group Substituting an alkyl group having a carbon number of 1 to 3, R3 represents an alkyl group having a carbon number of 1 to 4 or an alkyl group having an ether bond 'a represents 1 or 2; when R2 is plural, a plurality of R2 may be The same or different, multiple OR3s can be the same or different]. [5] The coating liquid according to [1] or [2], wherein the component (A-3) is a decane compound having an amine group and an alkoxy group represented by the following formula (3): R4bSi(〇R5)4 .b ......(3) 141326.doc -6 * 201012882 [wherein R4 represents an alkyl group having a carbon number of 1 to 4; a vinyl group; a phenyl group; or an alkyl group selected from the group consisting of methacryloxy groups and amine groups ( -NH2 group), aminoalkyl group [•(chJx-NH2 group (wherein 'X is an integer of 1 to 3)], an alkylamino group [-NHR group (wherein R is a carbon number of 1 to 3) a compound having one or more substituents substituted with a carbon number of 1 to 3, and at least one of R4 representing a carbon substituted with an amine group, or an aminoalkyl group or an alkylamine group The number is 1 to 3 alkyl groups; R5 represents a carbon number of 1 to 4, and b represents 1 or 2; when R4 is plural, the plurality may be the same or different, and the plurality of OR5 may be the same [6] The coating liquid according to [1] or [2], wherein the component (A-4) is a decane compound having an epoxy group and an alkoxy group represented by the following formula (4): R6 〇Si(OR7)4.c (4) [wherein R6 represents an alkyl group having a carbon number of 1 to 4; a vinyl group; a phenyl group; An alkyl group having 1 to 3 carbon atoms substituted with one or more groups selected from the group consisting of mercaptopropyloxycarbonyl, glycidoxy, and 3,4-epoxycyclohexyl, and at least i of r6 The alkyl group having a carbon number of 1 to 3 substituted by a glycidoxy group or a 3,4-epoxycyclohexyl group, R represents a burning group having a carbon number of 1 to 4, and c represents 1 or 2; In the case of plural cases, a plurality of R6 may be the same or different, and a plurality of 〇R7 may be the same or different.] [7] The coating liquid of [1] or [2], wherein the component (A-5) is the following The blocked isocyanatodecane compound having an alkoxy group represented by the formula (5): R8dSi(OR9)4_d (5) wherein R8 represents an alkyl group having a carbon number of 1 to 4; a stupid group; or an alkyl group having 1 to 3 carbon atoms substituted with an anthracene group selected from a methacryloxy group and a blocked isocyanate group; at least one of R8 represents a blocked group 141326.doc 201012882 The cyanate group is substituted with an alkyl group having 1 to 3 carbon atoms; R9 is a shinyl group having a carbon number of 1 to 4, and d is 1 or 2, and when R8 is plural, a plurality of r8 Can be the same or different 'multiple OR9 can be the same or different】 [8] The coating liquid according to any one of [1] to [7], which is a hydrolysis condensate of (A1) component, (A-2) component and (A-4) component, and (B) The component (A-5) is added to the reaction product obtained by contacting the component, and then reacted, and then the component (A-3) is further added and reacted. [9] As described in [1] to [7] The coating liquid according to any one of the preceding claims, which is obtained by heating a mixture comprising the components (A-1), (A-2), (A-4) and (B) to (E) After the component (A-5) is added to the reaction product and reacted, the component (A-3) is further added and reacted. [10] A cured film which is obtained by hardening the coating liquid according to any one of the above [1] to [9]. [11] A resin laminate comprising: a substrate; and a cured film of [10] directly formed on the substrate. [12] A resin laminated body comprising: a substrate; a cured film of [10] formed on the substrate; and an inorganic layer formed on the cured film. [13] A resin laminated body comprising: a substrate; a cured film of [10] formed on the substrate; and a transparent conductive film formed on the cured film. [14] A resin laminate] characterized by comprising: a substrate, a cured film such as [10] formed on the substrate, and a photocatalyst layer formed on the cured film 141326.doc 201012882 [15] The resin laminate in which the thickness of the cured film is 0.1 to 50 μm 〇 [16], such as the tree sap structure of [13], wherein the carrier concentration of the transparent conductive film is lxl018/cm3 or more. [17] The resin laminate according to [13], wherein the substrate is a resin substrate. [18] The resin laminate according to any one of [11], wherein the substrate has irregularities. [19] The resin laminate according to any one of [11], [12], [17], or [18] wherein the substrate is an elliptical cylinder. [20] The resin laminate according to any one of [11], [12], [17], or [18] wherein the substrate is cylindrical. [21] The resin laminate according to any one of [11], wherein the resin substrate is provided on a surface of the substrate on which the cured film is not formed. [22] The resin laminate of any one of [11], [12], [14], [17] to [21] wherein the thickness of the cured film is 〇.5 to 6 μmη. [23] The resin laminate of any one of [11], [12], [14], [17] to [22] wherein the substrate is a polyester resin, a polycarbonate resin or a polyolefin resin. [24] A method for producing a cured film, which comprises the step of heating and hardening the coating liquid according to any one of the above [9]. [25] A method for producing a resin layered product, comprising the steps of: applying a coating liquid according to any one of [1] to [9] to a substrate, and drying the coating liquid, The step of thermoforming the substrate, and curing the coating liquid to form a coating layer. The method for producing a resin laminate according to [25], further comprising the step of providing a resin layer on a surface of the resin laminate obtained by curing the coating liquid without a coating layer. [27] A method for producing a resin laminated body, comprising: forming a cured film obtained by hardening a coating liquid according to any one of the above (1) to [9] on a substrate, and the cured film The step of forming a transparent conductive film thereon. [28] A method of producing a resin laminated body, comprising: forming a cured film obtained by hardening a coating liquid according to any one of (1) to [9] above, on the substrate, and the cured film The step of forming a photocatalyst layer thereon. Advantageous Effects of Invention According to the present invention, it is possible to provide a coating liquid which forms a cured film which is excellent in adhesion to a layer of a ruthenium or a material, a transparent conductive mold and a photocatalyst layer, and which is excellent in a coating film. Characteristics such as abrasion resistance, <scratch resistance, flex resistance, financial property (ultraviolet absorbing ability), durability (boil resistance). According to the present invention, it is possible to provide a curing medium having the above characteristics obtained by curing the coating liquid, and to have the substrate or the substrate between the layers of the inorganic hard layer and the photoconductive layer and the photocatalyst layer. The resin product of the cured film (4), and the method for producing the cured film and the difficult-to-layer layer. [Embodiment] First, the coating liquid of the present invention will be described. [Coating Liquid] The coating liquid of the present invention is characterized by comprising the following components (A) to (8). (Component (A)) 141326.doc -10- 201012882 The coating liquid of the present month contains a hydrolysis condensate of five compounds of the following (A.1) to (Ad) as the component (A) having an alkoxy group. A hydrolysis condensate of a stone mb complex. The hydrolysis condensate may be a hydrolyzed condensate of (a single compound in Α_υ~(Α·5)' may be a hydrolysis condensate containing a mixture of any two or more of (Α·1)~(Α-5) In the present invention, a decane compound having an alkoxy group means an alkoxy decane compound and/or a partial condensate thereof; a so-called alum condensate of an alkoxy decane compound means a oxy-oxyl compound A part of a polyalkoxy decane compound or a polyorgano alkoxy decane compound formed by condensation of a decane bond (Si-Ο bond) in a molecule. Further, a hydrolytic condensation of a decane compound having an alkoxy group The term "containing a hydrolyzed condensate of a decane compound having an alkoxy group, and a state of the alkoxy group-containing decane compound before hydrolysis and condensation. - (A-1) compound > 1) The compound is a tetraalkoxydecane compound. Further, a partial condensate (polyalkoxydecane compound) bonded by a sulphur-oxygen bond (Si-oxime bond) may be used. These compounds may be used alone. One type may be used in combination of two or more types. Of (A-1) compound, an alkoxy silicon tetraalkoxy compound and a partial condensate of example by the following general formula (1), is a particularly suitable compound of the following general formula (6) represented by the.

Si(OR,)4 (1) [wherein R1 is an alkyl group having 1 to 4 carbon atoms or an alkyl group having an ether bond; and a plurality of R's may be the same or different]. 141326.doc 201012882 [化i]

R’O

...· ($) [In the formula, R1 is the same as above,! ! is an integer of hi 5]. In the above formulae (1) and (6), examples of the alkyl group having a carbon number of [~4] include a mercapto group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, and various butyl groups; Examples of the ruthenium R1 in which R1 is an alkyl group having an ether bond and the carbon number is 4, and examples thereof include a 2-methoxyethoxy group and a 3-methoxyoxypropoxy group. The tetraalkoxydecane compound of the compound (A-1) may, for example, be tetradecyloxydecane, tetraethoxydecane, tetra-n-propoxydecane, tetraisopropyldecyldecane or tetra-n-butoxydecane. , tetraisobutoxy decane, and the like. Further, examples of the polyalkoxydecane compound include "M Silicate 51", "Silicate 4Q/," "Sihcate 45" manufactured by Tama Chemical Industry Co., Ltd.; and "methyl citrate 51 manufactured by Colcoat Co., Ltd." "Methyl decanoate 53A", "Ethyl citrate 4", "Ethyl citrate 48, etc." <(A-2) compound> (A-2) The compound is an amine group-free, Epoxy and isocyanate-based organoalkoxydecane compounds. Further, a partial condensate thereof can also be used. These compounds may be used alone or in combination of two or more. As the compound (A-2), the organoalkoxydecane compound and a partial condensate thereof are preferably a bifunctional alkoxydecane or a trifunctional alkoxydecane, for example, 141326.doc -12-201012882 may have the following formula (2) It is a compound which is represented by the following general formula (?). R2aSi(〇R3)4-a (2) wherein R2 is an alkyl group having 1 to 10 carbon atoms or a fluoroalkyl group; a vinyl group; a phenyl group; or a methacryloxy group Substituting an alkyl group having a carbon number of 1 to 3, R3 is an alkyl group having 1 to 4 carbon atoms or an alkyl group having an ether bond, and a is 1 or 2; when R2 is plural, a plurality of R2 may be the same It can also be different, and multiple 〇R3 can be the same or different].

[Chemical 2]

[wherein, R and R3 are the same as described above, and the claw is an integer of 丨~^]. In the above formulas (2) and (7), the alkyl group having a carbon number of (7) may be

Examples of the linear or branched form include a mercapto group, an ethyl 'n-propyl group, an isopropyl group, various butyl groups, various hexyl groups of various octyl groups, various fluorenyl groups, and the like; For example, a triterpene ethyl group, a trimethyl propyl group, etc. are mentioned. Further, examples of the alkyl group having a carbon number of 1 to 3 include a mercapto group, an ethyl group, an alkyl group having an isopropyl group number of 1 to 4, or a system having an ether bond such as the above formula (1). Explained. In the organoxyloxy zephyr compound represented by the formula (2), 3 is an alkoxy decane, and 1 is exemplified by methyltrimethoxydecane, methyltriethyllacylate, and kiwi. Propoxydecane, methyl tributoxydecane, methyl 141326.doc -13- 201012882 ki-tris(2-methoxyethoxy)decane, ethyltrimethoxydecane, ethyltriethoxydecane , ethyl tripropoxydecane, ethyl tributoxydecane, ethyl-tris(2-methoxyethoxy)decane, hexyltrimethoxydecane, hexyltriethoxydecane, hexyltripropoxy Base decane, hexyl tributoxy decane, decyl trimethoxy decane, decyl triethoxy decane, decyl tripropoxy decane, decyl tributoxy decane, having a fluorine atom introduced into the substituent Fluoroalkyl (trialkoxy) decane such as trifluoropropyltrimethoxydecane, phenyltrimethoxy oxime, phenyldiethoxy deflagration, ethylene trimethoxy octyl, ethylene Triethoxy decocting, γ-methyl propyl madoxypropyltrimethoxy pulverization, and the like. Further, examples thereof include mercapto dimethoxy (ethoxy) decane and ethyl diethoxy (methoxy) decane having two kinds of alkoxy groups. Examples of the bifunctional alkoxydecane include dimethyldimethoxydecane, dimethyldiethoxydecane, bis(2-methoxyethoxy)dimethyloxime, and diethyldicarboxylate. Ethoxylated calcined, diphenyldimethoxy calcined, diphenyldiethoxydecane, and the like. Specific examples of the polyorgano alkoxydecane compound include "MTMS-A" manufactured by Tama Chemical Industry Co., Ltd.; "SS-101" manufactured by Colcoat Co., Ltd.; Toray-Dow Corning "AZ-6101", "SR2402", "AY42-163" manufactured by the company. <(A-3) Compound> The compound (A-3) is a decane compound having an amine group and an alkoxy group, and is an alkoxydecane compound containing no epoxy group or isocyanate group. Further, a partial condensate thereof (polyorgano alkoxydecane compound containing an amine group 141326.doc • 14-201012882) can also be used. These compounds may be used singly or in combination of two or more. The organoalkoxydecane compound containing an amine group and a partial condensate thereof as the compound (A-3) can be represented, for example, by the following formula (3). R4bSi(OR5)4.b (3) [wherein R is an alkyl group having 1 to 4 carbon atoms; a vinyl group; a phenyl group; or an alkyl group selected from a methacryloxy group, an amine group (-NH2 group), an amine Alkyl group (CH2h_NH2 group (wherein X is an integer of 1 to 3, an alkylamino group NHR group (wherein the alkyl group having a carbon number of 1 to 3) is substituted with a carbon number In the alkyl group of 3, at least one of R4 is an alkyl group having a carbon number of i to 3 substituted with an amine group or an aminoalkyl group or an alkylamine group; R5 is a carbon number of 1 The alkyl group '4 of 4' is 1 or 2. When R4 is plural, the plurality of R4 may be the same or different. 'Multiple OR5 may be the same or different.' In the above formula (3), 'carbon The alkyl group having a number of alkyl groups and having a carbon number of i to 4 is as described in the above formula (1) or (2). The organoalkoxy group having an amine group represented by the formula (3) Specific examples of the decane compound include N-(2-aminoethyl)-3-aminopropyl decyl decyloxydecane and N-(2-aminoethyl)-3-aminopropyl Trimethoxy oxime, N-(2-aminoethyl)·3_aminopropyl decyl diethoxy decane, ν·(; 2_Aminoethyl)-3-aminopropyltriethoxydecane, 3·Aminopropyltrimethoxycarbazide, 3-Aminopropyltriethoxydecane, N-decylaminopropyl Further, as a polyorgano alkoxydecane compound containing an amine group, for example, a share of Shin-Etsu Silicones can be cited as a trimethoxydecane, N-decylaminopropyltriethoxydecane, and the like. 141326.doc -15- 201012882 manufactured by the company "KBP-90 j, etc. <(A-4) compound> (A-4) The compound is a decane compound having an epoxy group and an alkoxy group and is not contained An amine group and an isocyanate s. A partial condensate (a polyorgano alkoxy decane compound containing an epoxy group) may be used. These compounds may be used alone or in combination. Two or more kinds of the compound (A-4), the epoxy group-containing organoalkoxydecane compound and a partial condensate thereof, which can be represented by the following formula (4): [R6cSi(OR7)4.c (4) [wherein, R6 is an alkyl group having 1 to 4 carbon atoms; a vinyl group; a phenyl group; or a methyl propylene oxide group, a glycidoxy group, 3, 4: The alkyl group substituted by the above upper group in the epoxycyclohexyl group is an alkyl group of 丨~3; at least one of R6 is substituted by a glycidoxy group or a 3,4-epoxycyclohexyl group. The carbon number is an alkyl group of 丨~3; R7 is an alkyl group having a carbon number of 1 to 4, and 0 is ! or 2; when the ruler 6 is plural, the plurality of R6 may be the same or different, and a plurality of 〇R7 may be used. The same or different in the above formula (4), the alkyl group having 1 to 3 carbon atoms and the alkyl group having 1 to 4 carbon atoms are as described in the above formula (1) or (2). Specific examples of the epoxy group-containing organoalkoxydecane compound represented by the formula (4) include 3-glycidoxypropyl decyl decyl decane and 3-epoxy propylene. Oxypropylmethyldiethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxysulfonate, 2-(3,4-ring Oxycyclohexyl)ethyltrimethoxydecane, 2·(3,4-epoxycyclohexyl)ethyltriethoxydecane, and the like. 141326.doc 201012882 <(A-5) compound> (A-5) compound is a blocked isocyanatodecane compound having an alkoxy group (generally 'also known as blocked isocyanate decane compound And an alkoxy sinter compound containing an blocked isocyanate group but not containing an amine group and an epoxy group. Further, a partial condensate (polyorgano alkoxy decane compound containing a blocked isocyanate group) may also be used. These compounds may be used alone or in combination of two or more.

Further, 'so-called blocked isocyanatodecane compound' means that the isocyanate group is protected from blocking by a blocking agent such as hydrazine, and then deblocked by heating to make the isocyanate A base activated (regenerated) isocyanatodecane compound (generally, also known as an isocyanate decane compound). The (A-5) compound, an organoalkoxydecane compound containing a blocked isocyanate group, and a partial condensate thereof, for example, can be represented by the following formula (5): 0 R8dSi(OR9)4.d .... (5) [wherein R8 is a hospital base of carbon number; ethylene group; phenyl group; or one or more groups selected from the group consisting of methacryloxy group and blocked isocyanate The substituted carbon number is a pyridyl group of 1, 3, and at least t of R8 is a group of 1 to 3 substituted by a blocked n(tetra) group; R9 is a burning group of 1 to 4 carbon atoms d is 1 Or 2 'When R is a plural case, the plural number can be the same or several OR9 can be the same or different]. The alkyl group having a carbon number of 1 to 3 and a carbon number of 1 to 4 in the formula (5) is as described in the above formula (1) or (2). 141326.doc -17. 201012882 Specific examples of the organic alkoxy group-containing compound having a blocked isocyanate group represented by the above formula (5) include 3-isocyanatopropyltrimethoxy group. Decane, 3-isocyanatopropyltriethoxydecane, 3-isocyanatepropylmercaptodimethoxydecane, 3-Isocyanatepropylmercaptodiethoxylate, 3 The isocyanate group in the compound such as isocyanatopropylethyldiethoxylate is protected with a blocking agent. Among these, the compound 'is exemplified by 3-blocked isogas propyl triethoxy oxane. As the terminal blocking agent for the isocyanate group, acetone sulfonium, 2-butanone ketone ketone, if f-isobutyl ketone, etc., and sulfonamides such as succinylamine can be used. (A5, 壬基龄, etc.) and other burning base ages; w-toluene, di-tert-butyl benzophenone, etc.; trimethyl phenols; trimethyl phenols; Malonic acid diesters such as esters; active methylene compounds such as acetamidineacetone, acetamidine acetate, ethyl acetate, etc.; methanol, ethanol, n-butanol, etc.; methyl cellosolve, butyl cellosolve An ether containing a hydroxyl group; an ester containing a hydroxyl group such as ethyl lactate or amyl lactate; a mercaptan such as butyl mercaptan or hexyl mercaptan; an anthranilil, a pro-ylamine or a dimer acid guanamine; Amines; imidazoles such as imidazole and 2-ethylimidazole; 3,5-dimethyl is a pyrazole such as sitting. , 2,4_triazole and other triazoles, such as butyl succinimide, ortho-imine, and the like. χ In order to control the dissociation of the blocking agent, it is also possible to use a catalyst such as dibutyltin dilaurate. (Component (B)) The organic polymer fine particles (hereinafter referred to as "knife ultraviolet absorbing resin fine particles") are contained as the component (B), and the organic high score 141326.doc 201012882 submicroparticle contains A copolymer of monomer units of ultraviolet absorbing groups. As the outer-side absorbing resin fine particles of the above-mentioned ifj molecule, for example, an acrylic monomer having a skeleton (such as a diterpenoid, a benzotriazole, or a tri-till) which functions as an ultraviolet absorber in the side chain can be exemplified. (hereinafter referred to as ultraviolet absorbing acrylic monomer) and other ethylenically unsaturated compounds (acrylic acid, methacrylic acid and derivatives thereof, stupid ethylene, vinyl acetate)

Etc.) Co-aggregation. The conventional ultraviolet absorber is generally a low molecular weight having a molecular weight of 200 to 700. On the other hand, the weight average molecular weight of the polymer ultraviolet absorbing resin fine particles usually exceeds 1. The polymer ultraviolet-ray absorbing resin particles are compatible with plastics and heat resistance, and the disadvantages of the low-molecular-weight ultraviolet absorbers which have existed since the prior art are improved, and the long-term financial performance can be obtained. The ultraviolet absorbing acrylic monomer is not particularly limited as long as it has at least one of an ultraviolet absorbing group and an acryl fluorenyl group in the molecule. As such a compound, for example, a benzotris-based compound represented by the formula (8) and a benzylnet-based compound represented by the formula (9) can be used. No [3]

141326.doc •19· 201012882 [wherein, x represents a hydrogen atom or a gas atom, Rl. Represents a hydrogen atom, a &, or a carbon number of 4, a tertiary alkyl group of 'Rnu straight or branched, 2 to H), f represents a hydrogen atom or an f group, and p represents ...]. [Chemical 4]

(9)

The linear or branched carbon number is 2 to 1 Å of an alkylene group, Rls represents a hydrogen atom or a hydroxyl group, and R16 represents a hydrogen atom, a hydroxyl group, or an alkoxy group having a carbon number of 丨6. Specific examples of the stupidized trisalt compound represented by the above formula (8) include, for example, 2-(2,-carbyl-5ι-(meth)acryloxyphenyl)-2H- Triazole, 2_(2,-hydroxy-3,_t-butyl-5,methyl)propenyloxymethylphenyl)-2Η·benzotrisole, 2_[2,_ vial_5, _(2_(f-based) propyl ethyl oxyethyl) phenyl]-2H-benzotriazole, 2_[2,_hydroxy·3,_t-butyl _5,_

(2_(Methyl)acryloxyethyl)phenyl]_5_gas_2Η-benzotriazole, 2[21 hydroxy-3-indolyl_5_(8-(methyl)propene oxime octyl Phenyl] 2 benzotriazole and the like. Specific examples of the benzophenone-based compound represented by the above formula (9) include, for example, a 2-hydroxy- 4-(2·(methyl)acryloxyethoxyethoxy)-benzoyl network. 2-yl-4-(4-(methyl)propenyloxybutoxy)diphenyl, 2·-di-diyl-4-(2-(methyl)propenyloxyethoxy) Diphenyl m 2,4~di-based-4'-(2-(methyl)acryloxyethoxyethoxy)diphenyl 141326.doc •20- 201012882 ketone, 2,2,,4-three Hydroxy-4·-(2-(methyl)acryloxyethoxyethoxy)dibenzopyrene, 2-yl-4-(3-(methyl)propenyloxy-2-ylpropoxy Benzo) benzophenone, 2-hydroxy-4-(3-(indenyl) propylene oxy-p-hydroxypropoxy) dioxin, and the like. These ultraviolet absorbing acrylic monomers may be used alone or in combination of two or more. The above-mentioned polymer ultraviolet absorbing resin particles as the component (B)

The content of the ultraviolet absorbing acrylic monomer unit is usually from about 5 to 70% by mass, preferably from 1 to 6 Å, from the viewpoints of the ultraviolet absorbing ability, other physical properties, and economy of the cured film. About % by mass. In the coating liquid of the present invention, the polymer ultraviolet absorbing resin fine particles used as the component (B) are averaged from the viewpoints of manufacturability, dispersibility in a coating liquid, coating properties of a coating liquid, and transparency of a cured film. The particle diameter is preferably in the range of 1 to 200 nm, more preferably in the range of 丨~丨(10) nm. Further, the average particle diameter of the high molecular ultraviolet absorbing resin particles can be measured by a laser diffraction scattering method. In the present invention, the polymer ultraviolet absorbing resin fine particles are preferably used in a form dispersed in a dispersion medium; and as the dispersion medium f, for example, water, methanol, ethanol, propanol, and buckwheat are preferably used. Oxypropanol and the like: grade:; cellosolve such as methyl cellosolve; By using such a dispersion medium knife, the dispersibility of the ultraviolet absorbing resin particles is improved, and it is possible to prevent the dispersion from being a water. When the dispersion medium is water, it is used in the hydrolysis and condensation reaction of the money compound necessary for forming a matrix having the _ bond from the above (4) component, and thus is more suitable than 141326.doc 21 201012882. The method for producing the polymer ultraviolet absorbing resin fine particles used as the component (B) is not particularly limited, and a conventionally known method such as an emulsification polymerization method or a fine suspension polymerization method can be employed. The emulsion polymerization method is a method of using an emulsifier comprising an aqueous dispersion medium, an anionic or nonionic surfactant, and a water-soluble polymerization initiator γ to form a UV-absorbing acrylic monomer as a monomer, and A mixture of the monomer-polymerized ethylenically unsaturated monomers is emulsified into fine droplets, and polymerized in a surfactant microcap layer containing the above monomer mixture to obtain dispersion of the polymer ultraviolet absorbing resin particles. liquid. On the other hand, the fine suspension polymerization method is as follows: # First, the above-mentioned single exemplified compound, oil-soluble polymerization initiator, emulsifier and other additives as needed are added to the aqueous medium and premixed, and then the homogenizer is used. The homogenization treatment is carried out to adjust the particle size of the oil droplets. Then, the homogenized solution is sent to a polymerization vessel to carry out a polymerization reaction, and a dispersion of the polymer ultraviolet absorbing resin fine particles is obtained. The polymerization temperature in any of the above methods is about 3 〇 8 8 (r). 〇 As a water-soluble polymerization initiator for emulsion polymerization, for example, water-soluble hydrazine, ammonium persulfate, hydrogen peroxide, etc. a peroxide; such a starter or hydroperoxide hydroquinone (eumene hydr-hydroperoxide such as tributyl oxyperoxide; combined with a reducing agent such as acidic sodium sulfite, ammonium sulfite, ascorbic acid a redox-based initiator; a water-soluble azo compound such as 2,2-.-azobis(2-:propylpropane spleen) dihydrochloride; etc. Further, as an oil-soluble polymerization for fine suspension polymerization 141326.doc • 22- 201012882 agents, for example, diacyl peroxide, ketone peroxide, peroxyester, peroxydicarbonate ( An oil-soluble organic peroxide such as peroxydicarbonate); an azo compound such as 2,2'-azobisisobutyronitrile or 2,2'-azobis(2,4-dimercaptophthalonitrile). Specific examples of the polymer ultraviolet absorbing resin fine particles usable as the component (B) include Polymer UV absorber for coating manufactured by Yosho Oil & Fat Industry Co., Ltd. 111^-700, 1; 1^-1770, 1; 1^· 383MA 'ULS-1383MA ' ULS-383MG ' ULS-385MG ' ULS-1383MG , ULS-1385MG, ULS-635MH, etc.; UV-absorbing resin coatings NCI-905-20EM and NCI-905-20EMA manufactured by Nikko Chemical Research Institute Co., Ltd. (with styrene monomer and benzotriazole monomer) In the present invention, the polymer ultraviolet absorbing resin fine particles may be used singly or in combination of two or more kinds as the component (B). (C) The coating liquid of the present invention contains colloidal cerium oxide as the component (C). The so-called colloidal cerium oxide used in the present invention also refers to colloidal cerium oxide or colloidal ceric acid. In water, it means hydration. A colloidal suspension of Si-OH-based cerium oxide on the surface is formed by adding hydrochloric acid to an aqueous solution of sodium citrate. Recently, a new preparation method has been developed, which is dispersed in a non-aqueous solution, and in a gas phase method. Made of micro-powder, grain Also from the number of nm to the number of μηι, various. The average particle size is preferably about 1 ~ 200 nm. The composition of the particles is uncertain, there is also the formation of broken oxygen key (-Si-O-, 141326.doc • 23· 201012882 -Si-O-Si-) is still molecularized. The surface of the particles is porous and generally negatively charged in water. Further, the above average particle diameter can be measured by a laser diffraction scattering method. As a commercial item, the "Ultra High Purity Colloidal Antimony Oxide" Quartron PL series manufactured by Fuso Chemical Industry Co., Ltd. (product name: 卩!^ 1, PL-3, PL-7); "High-purity organosol", manufactured by Nissan Chemical Industries Co., Ltd. "Colloidal cerium oxide (product name: Snowtex 20, Snowtex 30, Snowtex 40, Snowtex Ο, Snowtex 0-40 ' Snowtex C ' Snowtex N ' Snowtex S ' Snowtex 20L , Snowtex OL, etc.) and "Organic dioxide dioxide sol (product name: methanol dioxide sol,]\/[eight-81'-]^8, 14 people-81:-1^, 1?8-ST , IPA-ST-MS, IPA-ST-L, IPA-ST-ZL, IPA-ST-UP, EG-ST, NPC-ST-30, MEK-ST, MEK-ST-MS, MIBK-ST, XBA -ST, PMA-ST, DMAC-ST, ΡΑΜ-ST, etc.). In the present invention, the above-mentioned colloidal cerium oxide may be used singly or in combination of two or more kinds. (Component (D)) The coating liquid of the present invention contains a curing catalyst as the component (D). The catalyst for hydrolyzing and condensing (curing) the decane compounds (A-1) to (A-5) in the component (A), for example, hydrochloric acid, sulfuric acid, nitric acid, and acid acid, Inorganic acids such as citric acid, peroxyacid, and amino acid; citric acid, acetic acid, propionic acid, butyric acid, oxalic acid, citric acid, tartaric acid, succinic acid, maleic acid, glutamic acid, lactic acid, For organic acids such as toluenesulfonic acid. Further, there may be mentioned: hydrogen hydroxide, sodium hydroxide, potassium hydroxide, n-hexyl 141326.doc -24· 201012882 amine, dimethylamine, tributylamine, diazabicycloundecene, ethanolamine, formic acid Dimethylaniline, tetraethylammonium benzoate, sodium acetate, potassium acetate, sodium propionate, sodium lamelinate, potassium propionate, sodium formate, potassium formate, benzamidine trimethylammonium acetate, acetic acid Organic metal salts such as methylammonium and tin octylate; tetraisopropyl titanate, tetrabutyl titanate, triisobutoxyaluminum, aluminum triisopropoxide, aluminum acetoacetate, SnCU, TiCU, ZnCU, etc. Acid, etc.

In the hardening catalyst, even if the amount of the components (B) and (c) is increased, the dispersion can be increased, and the transparency of the obtained film can be improved. Therefore, an organic acid can be preferably used. In particular, an organic carboxylic acid can be used, of which acetic acid can be preferably used. ., ~ '•卞W Ί Also, you can use two or more combinations. (Component (E)) The coating liquid of the present invention contains a dispersion medium as a (Ε) component. The coating liquid of the present invention is used in a state in which the above-mentioned respective component particles are dispersed in a dispersion medium. The dispersion medium f used in the present invention is not particularly limited as long as the particles of the above-mentioned respective components are uniformly mixed and dispersed, and examples thereof include: alcohols, hydrocarbons, and _ Organic dispersion media such as hydrazines and vinegars. Specific examples of the organic dispersions include alcohols, methanol, 7-hexanol, n-propanol, propylene glycol, n-butanol, second butanol, butanol, and n-hexanol. , n-octanol, ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol ether ether ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether, 1_A. Oxy-2·propanol (propylene glycol mono 141326.doc -25- 201012882 decyl ether), propylene glycol monoterpene ether acetate, diacetone fermentation, methyl cellosolve, ethyl cellosolve, propyl cellosolve , butyl cellosolve, and the like. Specific examples of the other dispersion medium include cyclohexanone, acetone, mercaptoethyl ketone, decyl isobutyl ketone, tetrahydrofuran, 丨 '心二^, 1, 2-dimethoxy Ethylethane, xylene, dichloroethane, toluene, methyl acetate, ethyl acetate, ethoxyethyl acetate, and the like. Among these dispersion media, water and alcohols are preferred from the viewpoint of the performance of the dispersion medium. In the present invention, the above-mentioned dispersion medium may be used singly or in combination of two or more kinds as the component (E). (Component (F)) The coating liquid of the present invention preferably contains cerium oxide treated (pretreated) with a decane compound as the component (F). Here, the term "pretreatment" refers to a surface-like bear which changes the cerium oxide by reacting a ruthenium oxide group of ruthenium oxide with a decyl group of a decane compound to form a covalent bond. The decane-treated cerium oxide does not generate agglomerates or precipitates even when mixed with a sol (for example, colloidal cerium oxide or the like) in which anionic particles are dispersed, and the decane-treated cerium oxide can be dispersed in both water and alcohol. in. The cerium oxide to be used is not particularly limited, but is preferably in the form of particles and has an average particle diameter of 丨~? ^ nm, in terms of transparency, it is preferred that the average particle diameter is from 1 to 100 11111. In addition, when the component (F) is added to the coating liquid of the present invention, it is preferred to disperse it in a dispersion medium such as water or alcohol and then add it. The term "dispersion" of the component (F) means the state of the dispersed phase (solid) floating suspension 141326.doc •26- 201012882 in the dispersion medium (liquid). Further, the term "sol" refers to a colloid which uses a liquid as a dispersion medium and a solid as a dispersed particle, which is sometimes referred to as a colloidal solution. Further, the average particle diameter of the above cerium oxide microparticles can be measured by a laser diffraction scattering method. The dispersion medium is based on the above component (E), and preferably water or alcohol. In particular, the alcohol is an alcohol produced from the decane compound described in the (8-1) to (A-5) component of the component (A) and the alcohol described in the above (E) component, and particularly preferably dispersed. In methanol, ethanol, n-propanol, isopropanol, dike? Oxygen 2 - propylene in lower alcohols. Further, the water or the alcohol as the dispersion medium may be used singly or in combination of two or more. * The hai (F) component is a dispersion obtained by reacting a surface-charged cerium oxide sol with a decane compound to modify the surface thereof, and is preferably added to the present invention without causing aggregation, precipitation, or gelation. In the coating solution. The decane compound also completely contains an alkoxydecane or a hydrolyzed condensate thereof. Therefore, since it is impossible to determine the correct solid concentration in the dispersion state, φ, the total amount of the amount of cerium oxide which is the raw material and the amount of the complete condensate of the alkoxy decane is divided by the total amount of the input amount. The percentage expressed as a percentage is taken as the calculated solid concentration. ° ' <Production Method of (F) Component> The method for producing the cerium oxide microparticles to be used as the raw material to be used is not particularly limited, but it is difficult to react with the smelting compound in the powder state, so it is suitable as a dispersion. To use. The acid-stabilized cationic oxidized gold sol using an acidic dispersion stabilizer can be suitably used from the viewpoint of promoting the hydrolysis of the compound by the use of an acid-stabilizing stabilizer, and is preferably an average particle of 141,326.doc. -27- 201012882 For those of only 1 to 200 nm, the average particle size is preferably 1 100 nm from the viewpoint of imparting transparency. As the acid dispersion stabilizer to be added, an inorganic acid such as bovine hydrochloric acid, nitric acid or peroxy acid; or an organic acid such as acetic acid, formic acid or lactic acid may be mentioned. These can be used alone or in combination. Among the oxime, the organic citric acid has a coordination effect on the metal, and therefore, from the viewpoint of further reacting the cerium oxide with the decane compound, it is preferred to use a mineral acid, more preferably a cerium oxide sol of hydrochloric acid. As a commercial item, a plant manufactured by Toki Chemical Co., Ltd. Needral H-15, etc. may be mentioned. The decane compound of the raw material to be used may be defined in the same manner as the above-mentioned component (A). It is preferred to form a decyl alcohol bond with a sterol group of the component (A) and the component (c) when the cured film is produced. It is the above (Ad) compound. These can be used alone or in combination. Further, as the decane compound in the component (F), in addition to the above tetraalkoxy oxime and its hydrolysis condensate or polyalkoxydecane, an organic alkoxy decane or a hydrolysis condensate thereof or a polyorganic organic compound may be used in combination. Alkoxydecane is used. Specific examples of the organoalkoxydecane include those having at least one organic substituent in the component (A), and more preferably (A_2) to (A-5). The surface treatment structure may be a completely two-layer structure, or may be a structure in which a respective alkoxydecane or a hydrolysis condensate thereof or a polyalkoxydecane is mixed. The OH group of the surface layer of the cerium oxide particles has high reactivity, so if only the organoalkoxy decane is directly used in the surface treatment, since the reaction rate is not 141,326.doc • 28-201012882, there is agglomeration which promotes only cerium oxide. Gelatinization. Therefore, as the surface treatment of (F) cerium oxide in the knives, it is preferable that, first, the surface layer of cerium oxide is treated with a highly reactive four-silver or its hydrolysis condensate, and second, organic The alkoxy group (tetra) or its hydrolysis condensate is reacted and treated. " Thus, a structure having a part of an organic substituent is formed in the decane-treated layer of the component (F), whereby the sterol group of the component (A) and the component (C) can be suitably formed in the production of the cured film. The oxygen chain bond can further increase the softness of the cured film. When the surface of the cationic cerium oxide sol is not subjected to surface treatment with a decane compound, aggregation with a component having an anionic property in the coating liquid of the present invention causes aggregation and gelation, which makes it difficult to add. Therefore, in order to stably disperse it in the coating liquid of the present invention, it is necessary to react the 〇H group of the surface layer of the cerium oxide microparticles of the cationic cerium oxide sol with the ceramide group of the decane compound as described above, and then perform surface treatment. use. The amount of the decane compound used for the surface treatment in the component (F) is considered as the quality of the metal oxide as the dream burning compound. The metal oxide of the decane compound is, for example, defined by the following formula. R mR nSiO((4-mn)/2) (wherein R1 and R2 are each independently an alkyl group or a fluoroalkyl group having a carbon number of 丨~(7); an ethyl group; a phenyl group; or The number of carbon atoms substituted by one or more of an oxy group, an amine group, an aminoalkyl group, an alkylamino group, a glycidoxy group, a 3,4-epoxycyclohexyl group, and a blocked isocyanate group is The alkyl groups, m and η are each independently 0, 1 or 2, and m+n is 0, 1 or 2). 141326.doc -29- 201012882 The total mass of metal oxides in the sol (the total mass of decane compounds in the total amount of Ce02 and R'R^SiO ((4-mn)/2)) (R^R^SiOwnp)) The ratio is preferably 50% by mass or less, more preferably 2 to 40% by mass. If it is less than this, the cerium oxide itself is agglomerated and gelled, and if it is more than this, the decane compound itself reacts to aggregate and gel. The specific method for producing the component (F) can be carried out by the following method. A second mixed liquid comprising a cationic cerium oxide sol and the above-mentioned (E) component is prepared, followed by mixing one or more decane compound (A) components. After the aging at room temperature, the mixture is further stirred at room temperature or under heating to prepare a component (F). The component (E) may be further added after the preparation of the component (F) for dilution, or may be added to another dispersion medium for dispersion medium replacement. Further, in the case of using an alkoxysilane in combination, it is more preferable to employ the following method. A first mixed liquid containing a cationic cerium oxide sol and the following component (E) was prepared, followed by mixing with a tetraalkoxy decane (component (A)), whereby a second liquid was prepared. After aging at room temperature, the organoalkoxydecane ((A) component) was mixed to prepare a third mixed liquid. Further, the component (F) is prepared by stirring at room temperature or by heating. The component (E) may be further added after the preparation of the component (F) to be diluted, or may be added to another dispersion medium for dispersion medium replacement. The decane-treated cerium oxide sol added to the coating liquid of the present invention did not visually recognize the aggregated sediment at the bottom of the container even after being allowed to stand at room temperature for one week after the production. There is no particular limitation on the sol standing time of the 141326.doc • 30-201012882 until it is added to the coating liquid of the present invention. In the present invention, the cerium oxide sol may be used singly or in combination of two or more kinds as the component (F). (Component (G)) The coating liquid of the present invention preferably contains a dispersion stabilizer as the component (G). The dispersion stabilizer is used to stably disperse the reactants, (B), and (F) components of the decane compound (A)) to (A-5) in the coating liquid to suppress aggregation and gelation. In the coating liquid of the present invention, the fine particles of the components (B), (C) and (F) are preferably in a state in which they are dispersed without causing agglomeration, sedimentation and gelation, and for example, it is preferably a stable floating suspension. Colloidal state. In order to utilize the condensation reaction during thermal hardening, the coating liquid of the present invention binds the metal alkoxide to the oxime 11 before coating. Therefore, it is desirable to maintain the hydrolysis promoting reaction and suppress it. The acidic condition of the condensation reaction. Further, the carboxylic acid itself not only has an effect as an acid, but also has a coordination effect on the metal, and thus becomes an effective additive for stabilizing the alkoxide, and thus an organic acid can be utilized. The organic citric acid is preferably used as the component (G), and examples thereof include formic acid, acetic acid, propionic acid, butyric acid, citric acid, pivalic acid, oxalic acid, and malonic acid succinic acid. Glutaric acid Further, the coating liquid of the present invention forms a cured film by thermal hardening, and therefore it is preferable to have a degree of not remaining in the cured film at the time of heat curing, and it is better to use acetic acid. In the present invention, as the component (G), the above-mentioned dispersion stabilizer may be used alone or in combination of two or more kinds of U1326.doc • 31 · 201012882. (Optional addition component) In the coating liquid of the present invention, In addition to the above-mentioned (A) [(A-1) to (A_5) (8) components, various known additives to be used in the previous coating liquid may be appropriately contained as necessary. Examples of the additive component contained as needed may be, for example, : a leveling agent and a flexibility imparting agent, and further, a turbidity-imparting agent, an antioxidant, a blueing agent, an antistatic antifoaming agent (foaming suppressing agent), and a light stabilizer , a fugitive agent, a coloring agent, a dispersing agent for fine particles _ (precipitation preventing agent), a modifying agent for surface active particles, etc. <Leveling agent>

In the coating liquid of the present invention, a leveling agent may be added in order to improve the smoothness of the obtained cured film and the fluidity at the time of coating, and examples of the additives include a halogen-based leveling agent and a fluorine-based leveling agent. An acrylic-based leveling agent, an ethylene-based leveling agent, and a leveling agent obtained by combining (4) with propylene (4). All of the above leveling agents can act on the surface of the coating film, thereby lowering the surface tension. The above leveling agents have various characteristics and can be used as intended. The surface tension reduction ability is stronger than the polyfluorene-based leveling agent and the fluorine-based leveling agent, and the propylene-based leveling agent and the ethylene-based leveling agent are less likely to be wetted when recoating. Bad and more favorable. As a poly-based leveling agent, it is a copolymer of polyepoxy-fired and polydidecyloxane. As a commercial product of a polyfluorene-based leveling agent, Fz_2ii8, fz_77, FZ-2161, etc. manufactured by Toray Dow Corning Co., Ltd., etc., 141326.doc-32-201012882 KP321, manufactured by Shin-Etsu Chemical Co., Ltd., KP323, KP324, KP326, KP340, KP341, etc.; TSF4440, TSF4441, TSF4445, TSF4450, TSF4446, TSF4452, TSF4453, TSF4460, etc. manufactured by Momentive Performance Materials Japan Co., Ltd.; BYK-300, BYK- manufactured by BYK Chemie Japan Co., Ltd. 302, BYK-306, BYK-' 307, BYK-320, BYK-325, BYK-330, BYK-331, BYK--333, BYK-337, BYK-341, BYK-344, BYK-345, BYK, 346, BYK-348, BYK-377, BYK-378, BYK-UV3500, ❹ BYK-3510, BYK-3570 and other polyether modified eucalyptus oil (polyalkylene oxide modified eucalyptus oil). Further, in the case where it is necessary to have heat resistance of 150 ° C or higher, it is preferred to modify the polyester or the aralkyl modified sulfonate having a benzene ring. As a commercial product of the polyester modified oyster sauce, BYK-310, BYK-315, BYK-370, etc., manufactured by BYK Chemie Japan Co., Ltd., and the like; The sales item 'is exemplified by BYK-322, BYK-323, etc. manufactured by BYK Chemie Japan Co., Ltd. ^ As the fluorine-based leveling agent, a copolymer of a polyalkylene oxide and a fluorocarbon compound can be used. • As a commercial product of a fluorine-based leveling agent, DIC Co., Ltd. - manufactured MEGAFAC series, FC series manufactured by Sumitomo 3M Co., Ltd., etc. can be cited. As a commercial product of an acrylic leveling agent, the product is manufactured by BYK Chemie Japan Co., Ltd. 3丫1^-350 '8丫1352, 6丫1 354, BYK-355, BYK-358N, BYK-361N , BYK-380N, 141326.doc -33· 201012882 BYK 381, BYK-392, etc., introduced fluorine ΒΥΚ · 340 and so on. : The preparation of the leveling agent can improve the finished appearance of the hardening medium, and even if the film is formed, it can be coated. With respect to the total amount of the coating liquid, the amount of the leveling agent used is preferably 0.01 to 10% by mass, and more preferably m% by weight. As a method of blending the leveling agent, it can be formulated in the preparation of the coating material. The human coating liquid may be blended before the formation of the cured film, or may be formulated in two stages before the preparation of the coating liquid and the formation of the cured film. <Flexibility imparting agent> In order to increase the softness of the obtained cured film, the coating liquid of the present invention may contain a flexibility imparting agent as a stress relieving agent. As the flexibility-imparting agent, for example, a polyfluorene resin or the like can be used. As a commercial product of a polyoxyxene resin, a ReSin MK series manufactured by Wacker Co., Ltd., for example, Beisil PMS MK (which is a polymer containing a repeating unit of CH3Si〇w (monoterpene T), and also contains 1 mass. %(Jsh-SiO2/2 unit (unit D)); and KR-242A manufactured by Shin-Etsu Chemical Co., Ltd. (containing 98 mass/〇 unit τ and 2 mass% dimethyl unit D and containing Si - ΟΗ end group), KR-251 (containing 88 ❶/〇 of single tlT and 12% by mass of bismuth unit d and including Si-ΟΗ end group), KR-220L (including CHsSiO3, 2 The unit γ includes a Si-〇H (sterol) terminal group, etc. (Preparation of a coating liquid containing the components (A) to (E)) <Content of each component> Each component in the coating liquid of the present invention The content of 141326.doc •34·201012882 of each component is preferably selected as the range shown below. In addition to the dispersion medium of the component (E), it is expressed by mass% relative to (A) The content of each component of the total amount of [(A-1) to (A-5)] to (D) components. Further, it is preferably used in a dispersed state. The components (B) and (C) are calculated using only the respective solid materials, and the dispersion medium contained in each component is contained in the component (E). The content of the component (A-1) is usually 0.01~. 40% by mass or so, preferably 0.1 to 20% by mass. The content of the component (A-2) is usually 0.1 to 40% by mass left to right, preferably 1 to 30% by mass. (A-3) The content is usually from 0.1 to 30% by mass, preferably from 0.3 to 20% by mass. The content of the component (Α-4) is usually from about 0.1 to 30% by mass, preferably from 0.3 to 20% by mass. The content of the component is usually from 0.1 to 50% by mass, preferably from 1 to 40% by mass. The content of the component is usually from 0.1 to 50% by mass, preferably from 1 to 40% by mass. The content of the component (C) is usually from about 0.1 to 70% by mass, preferably from 1 to 50% by mass. The content of the component (D) is usually from 0.001 to 30% by mass, preferably from 0.001 to 20% by mass. %. Relative to the total mass parts of (Α)[(Α-1)~(Α-5)]~ (D), the content of the (Ε) component is usually about 5 to 1000 mass* parts, preferably Is 20~800 quality Further, there is no particular limitation on the molar ratio of the (Α-3) component to the (Α-5) component, and it is preferably 1:1 to 1:5, more preferably 1:2. ～1: 4. If the molar ratio of the (Α-3) component to the (Α-5) component is within the above range, the durability of the obtained cured film is further improved. <Preparation method of coating liquid containing (Α)~(Ε) component> 141326.doc -35- 201012882 The coating liquid of the present invention preferably has a component (A-1) and a component (A-2) And (A-5) component is added to the reaction product obtained by contacting the hydrolysis condensate of the component (A-4) with the components (B) to (E), and the component (A-3) is further reacted, and then the component (A-3) is further added and It is the reaction. Further, it is further preferred to use a reaction product obtained by heating a mixture containing the components (A-1), (A-2), (A-4) and (B) to (E). After the component (A-5) is added and reacted, the component (A-3) is further added and reacted. Specifically, it is preferred to carry out the following operations to prepare a coating liquid. Preferably, first, a first mixed liquid containing at least (Al), (A-2), (A-4), (B), (D), and (E) components is prepared, followed by mixing into the (C) component. The second mixed liquid was prepared, and the mixture was further mixed into the component (A-5) to prepare a third mixed liquid. Finally, the component (A-3) was mixed to prepare a coating liquid. When the components are separated and prepared as described above, the stability of the solution of the coating liquid (without gelation or the like) is improved, which is preferable. In particular, when the amount of water in the solution is increased by the addition amount of the components (B) and (C), the effect is further exerted. For example, after mixing (A-1) '(A-2), (A-4), (B), (D), and (E) components, the component (C) is added. Then, the component (A-5) is mixed, and finally, the component (A-3) is mixed. Further, after the preparation of the coating liquid, the component (E) is further added, whereby the coating liquid can be diluted. It is known that the solution storage stability of the mixed material of the coating liquid of the present invention easily affects the pH value of the solution (for example, "Application of Sol-Gel Method in Nanotechnology/Editor-in-Chief" by CMC). In the preparation of the coating liquid of the present invention, since the acidic component is mixed as the component (D) and the inspecting component is mixed as the component (A-3) and the component (D), the pH of the solution changes with the mixing order of 141,326. Doc *36- 201012882 0 As the pH value of the 7-grain solution, you can use the pH standard solution to correct the portable pH meter (Hanna company. -Ι) to evaluate

Preferably, the pH of the cold liquid is such that the first mixed liquid and the second mixed liquid are 6, $6 so that the third mixed liquid and the final mixed liquid are pHS 7. In particular, if the pH of the solution is more than 8 when the first-spreading liquid is mixed with the component (A_3), the stability of the liquid is lowered. From the start of the preparation of the coating liquid to the preparation, it is preferred that the solution remain in an acidic state. That is, it is preferred to prepare a coating liquid in the order in which such conditions are maintained. It is preferred that the above-mentioned mixed δ liquid, the second mixed liquid, and the third mixed liquid are subjected to heat treatment after mixing the respective components. The temperature is preferably 〇C 130C, more preferably 5 〇 ° c to 90 ° C, and the heat treatment time is preferably 3 Torr to 24 hours, more preferably 1 hour to 8 hours. The mixing and heating method is not particularly limited as long as it can be uniformly mixed and heated. By heating in this manner, the condensation reaction of the components 3) and (Ad) and (A-5) in the solution proceeds, and the boiling resistance and other durability are improved. The reaction of (A-丨), (Α·2), (A_3) '(A_4) and (A 5) components can be analyzed by solution Si-NMR (nuclear magnetic resonance), which can be designed to be suitable The structure. If it is less than 3 (rc or less than 30 minutes, the reaction is extremely slow, and when it exceeds 130 C or exceeds 24 hours, (Al), (A-2), (A-3) The reaction of the components (A-4) and (A-5) is excessively carried out, and the solution is gelled or highly viscous, so that there is no coating which can not be coated. The final solution after mixing the component (A-3) (coating) It is also preferable to carry out the heat treatment of 141326.doc -37-201012882. When it is mixed at room temperature, it is easily affected by the mixing efficiency, which results in the dispersion of the component (A-3). In the case of low, there is a decrease in the transparency (total decrease in light transmittance and increase in haze) of the cured film. The temperature is preferably from 30 ° C to 130 ° C, more preferably from 50 ° C to 90 ° C. The time is preferably from 5 minutes to 10 hours. More preferably, it is from 15 minutes to 6 hours. Regarding the method of mixing and heating, there is no particular limitation on the method of uniform mixing and heating. If it is less than 30 ° C or not For 5 minutes, the effect of heat treatment is insufficient, and if the temperature exceeds 130 ° C or exceeds 1 〇, the solution gelatinizes or is high. In the examples described later, the evaluation results of the cured film produced by using the coating liquid obtained after standing for one week are described, and the solution standing time until the cured film is produced is described. (Preparation of coating liquid containing components (A) to (G)) <Content of each component> Content of each component in the coating liquid containing the components (A) to (G) of the present invention The content of each of the components (A) to (E) may be appropriately selected from the (A) [(A1) to (A5)] to The content of each component of the total amount of the component G) may be the same as the case of the coating liquid containing the components (A) to (E). The content of the component (F) is usually 〇1 to 3 〇% by mass. The content of the component (G) is usually from about 1 to 60 parts by mass, preferably from about 10 to 50 parts by mass, based on the amount of the component (A) to (G). The preparation method of the liquid> "Hai coating liquid is preferably to make (A_1), (A-2), (A-4) and (A-5) components 141326.doc •38- 201012882 When the (A-3) component is added to the reaction product obtained by contacting the (B) to (G) component and the reaction product is reacted, specifically, it is preferred to prepare a coating liquid by the following operation. Preferably, first, a first mixed liquid containing at least (Al), (A-2), (A-4), (B), and (D), (E), (G) components is produced, and then The second mixed liquid was prepared by mixing the components (C) and (F), and further mixing the component (A-5) to prepare a third mixed liquid. Finally, the component (A-3) was mixed to prepare a coating liquid. When the components are separated and prepared as described above, the stability of the solution of the coating liquid (without gelation or the like) is improved, which is preferable. This effect is further exerted especially when the amount of water in the solution is increased by the addition of the components (B), (C) and (F). For example, after mixing the components (A-1), (A-2), (A-4), (B), and (D), (E), and (G), the components (C) and (F) are added. Then, the component (A-5) is mixed and finally mixed into the component (A-3). Further, the component (E) can be diluted by further adding a coating liquid after the preparation of the coating liquid. Further, as a further preferred method for preparing a coating liquid, the hydrolysis condensate of the components (A-1), (A-2), and (A-4) and (B), (C), (D), and (E) can be used. (F) and (A-5) are added to the reaction product obtained by contacting the component (G), and reacted, and (A-3) component is added to the obtained reaction product, and reacted to prepare a reaction product. Coating solution. Specifically, it is obtained by heating a mixture containing the components (Al), (A-2), (A-4), (B), (C), (D), (E), and (G). Reaction product 141326.doc •39· 201012882 The components (F) and (A-5) are added and heated, and then the component (A-3) is added to the obtained reaction product and heated to obtain a coating liquid. By using such a production method, the dispersibility of the coating liquid can be further improved, and the transparency of the cured film can be improved. Further, the hydrolysis condensate of the components (Al), (A-2), (A-4) and (A-5) and (B), (C), (D), (E) and (G) The component (F) is added to the reaction product obtained by the component contact and reacted, and the component (A-3) is added to the obtained reaction product and allowed to react, whereby a coating liquid can also be prepared. Specifically, for example, it includes components (Al), (A-2), (A-4), (A-5), (B), (C), (D), (E), and (G). The component (F) is added to the reaction product obtained by heating the mixture and heated, and then the component (A-3) is added to the obtained reaction product and heated, whereby a coating liquid is obtained. By adopting such a production method, the dispersibility of the coating liquid can be further improved, and the transparency of the hardened film can be improved. Further, (A-5) may be added to the reaction product obtained by bringing the hydrolysis condensate of the components (Al), (A-2) and (A-4) into contact with the components (B) to (G). The component was reacted, and the component (A-3) was added to the obtained reaction product and reacted to prepare a coating liquid. Specifically, for example, a component (A-5) is added to a reaction product obtained by heating a mixture containing the components (A1), (A-2), (A-4), and (B) to (G). Heating is carried out, and then the component (A-3) is added to the obtained reaction product and heated to obtain a coating liquid. By adopting such a preparation method, the dispersibility of the coating liquid can be further improved, and the transparency of the cured film can be improved. It is known that the storage stability of the mixed material of the coating liquid of the present invention is easy to be 141326.doc -40- 201012882 affecting the pH value of the solution (for example, "Application of Sol-Gel Method in Nanotechnology / Editor-in-Chief: CMC Publishing). In the preparation of the coating liquid of the present invention, since the acidic component is mixed as the components (D) and (G), and the alkaline component is mixed as the components (A-3) and (D), the pH of the solution varies depending on the mixing order. Variety. • As the pH value of the solution, for example, the pH of the solution to be evaluated by a portable pH meter (manufactured by Hanna: trade name: Checker-Ι) corrected by the pH standard solution is preferably used to make the first mixed liquid described above. And the second mixture is Lu pHS 6, so that the third mixture and the final mixture are pHS 7. In particular, if the pH of the solution exceeds 8 when the third mixture is mixed with the component (A-3), the stability of the solution is lowered. It is preferred that the solution remains in an acidic state from the start of preparation of the coating liquid until the completion of the preparation. Namely, it is preferred to prepare a coating liquid in the order of maintaining the above conditions. Further, it is preferred that the first mixed liquid, the second mixed liquid, and the third mixed liquid are subjected to heat treatment after mixing the respective components. The temperature is preferably from 30 ° C to 130 ° C, more preferably from 50 ° C to 90 ° C, and the heat treatment time is preferably from 30 minutes to 24 hours, more preferably from 1 hour to 8 hours. The mixing and heating method is not particularly limited as long as it can be uniformly mixed and heated. By heating in this manner, the condensation reaction of the components (A-1), (A-2), (A-.3), (A-4), and (A-5) in the solution proceeds. Durability (boiling resistance) and other properties are improved. The reaction of the components (A-1), (A-2), (A-3), (A-4), and (A-5) can be carried out by solution Si-NMR, whereby a suitable structure can be designed. If it is less than 30 ° C or less than 30 minutes, the reaction is extremely slow, and when it exceeds 130 ° C or exceeds 24 hours, 141326.doc -41 - 201012882 (A 1), (A -2) The reaction of the components (A-3), (A-4), and (A-5) is excessively carried out, and the solution is gelled or highly viscous, so that there is no possibility of coating. Further, it is also preferred that the final liquid (coating liquid) after mixing the component (A-3) is subjected to heat treatment. When mixing at room temperature, it is easily affected by the stirring efficiency, and thus the dispersion of the (A-3) component is low, and the transparency of the cured film is lowered (the total light transmittance is lowered). After the haze rises. The temperature is preferably 3 (TC~130t, more preferably 5(rc~9(rc, better time is 5 minutes~10 hours', more preferably 15 minutes~6 hours. About mixing and heating The method is not particularly limited as long as it can be uniformly mixed and heated. If it is less than 3 (TC or less than 5 minutes, the effect of the heat treatment is insufficient, and if it exceeds 13 〇. (: or exceeds When the solution is gelled or highly viscous for 1 hour, there is a problem that the coating cannot be applied. In the following examples, the evaluation results of the cured film produced by using the coating liquid obtained after standing still are described. The solution standing time until the production of the cured film is not particularly limited. Further, since the component (F) used in the present invention is acid-stable, when mixed with other dispersions, 'in order to prevent agglutination during mixing. , precipitation, kneading, and more preferably mixing in the same acidic solution. For example, if the sol of the amorphous anionic fine particles is directly mixed with the component (F), it will be separated from the stable dispersion. pH range, there is no way to maintain the score (The use of the coating liquid) The transparency of the coating liquid of the present invention, the adhesion to the resin, the weather resistance, and the resistance to 141326.doc • 42· 201012882 Excellent abrasion resistance and scratch resistance, and can be used as various transparent Specifically, it can be used as a coating material for organic members, such as a resin-made window, a resin solid for a building, a large-area transparent member such as a road sound-blocking wall or an arcade, a measuring instrument such as an instrument panel, and a pepper of a building. f 曰 曰, transparent plastic parts, spectacle lenses, 胄 eyepieces, transfer film, "surface coating materials or primer materials for transparent organic components such as greenhouses. · Because of the high (four) material color, so coloring, and It has excellent compatibility with various color pigments, so it can also be used as a raw material for various coatings or as a primer material before painting. For example, it can be applied to interior and exterior decoration of automobiles, industrial machinery, steel furniture, interior and exterior decoration for construction. Coatings for household appliances, plastic products, etc. Moreover, the coating liquid of the present invention is also sufficiently resistant to the metal and is resistant to acidity, so it is also resistant to acid rain which has recently been regarded as a problem. Therefore, it is particularly suitable for the body or the body. Wheels, etc. A member for outdoor use, which is very similar to paint, can be used in various inks because of its high colorability and compatibility with pigments. • The coating liquid of the present invention utilizes high transparency and high adhesion. Excellent wear resistance and scratch resistance, and can also be applied to precision components used in electrical and electronic fields, optical fields, etc. For example, in plasma displays, liquid crystals, organic devices, and organic EL (electroluminescence) (Light) display. In various displays, various anti-reflection films, polarizing films, gas barrier films, retardation films, conductive films, etc., which have hard coat properties as one of their functions, can be used as these. In addition, hard coating materials for optical disk substrates, coating materials for optical fibers, touch panels, and coating materials for solar cell panels are also used as high-through (four), high-density, and excellent wear resistance 141326.doc •43. Listed for use in 201012882 for scratch and scratch resistance. Various protective films are used in holly mirrors, hologram elements, ccd (charge coupled device) cameras, etc. These protective dies are not only required to have transparency, abrasion resistance, scratch resistance and density. Sexuality, and consideration of manufacturing issues also requires a certain degree of low viscosity. The coating liquid of the present invention can be controlled to a desired viscosity by composition adjustment, and thus can also be used as the above protective film. Further, the coating liquid of the present invention is a material which not only has a hard coating property but also can be deformed and deformed, and can also be used for a flexible display which has recently been studied. Further, the coating liquid of the present invention can also transmit electromagnetic waves in the near-infrared region well. Therefore, it can also be applied to an antenna for radio wave transmission and reception, and RFID (Ra(ji)

Frequency Identificati〇n, radio frequency identification) data carrier vehicle radar, etc. Examples of other uses include coating agents for various transparent decorations, various skin materials (car seats, interior doors for automobiles, sofas, furniture, etc.), β-moving parts (brake pads, etc.), and bundles of fibers. Agent, gas barrier coating agent, and the like. Hereinafter, the cured film of the present invention will be described. 〇 [Cured film] The cured film of the present invention is a cured film obtained by hardening the above-described coating liquid of the present invention by a usual method. In the case of a resin molded article (injection molding (10), film, sheet, or the like) which is a target of a cured film, it is known by spraying, dipping, shower coating, bar coating, or roll coating. In the method, a coating liquid is applied to form a coating film. 141326.doc .44- 201012882 The thickness of the film depends on the formation. In the final form of the cured film, the thickness of the cured film is adjusted to a thickness of 0.5 to 6 μηι, more preferably J疋0.5. ~3 μιη. Thereafter, it is suitably hardened, usually at room temperature, preferably (9) to under the war. Hard (four) minutes to about 24 hours, preferably 3 minutes to 3 hours, thereby obtaining the desired hardening. Membrane ^

In the second aspect, as the thickness of the coating film, the thickness of the cured film is adjusted to be υο μιη, more preferably 2 to 2 〇 μηι. Thereafter, in a suitable hardening condition, it is usually carried at 80~. C, preferably 1 〇 (1) is subjected to heat hardening for 10 minutes to 24 hours, preferably 3 minutes to 3 hours, whereby a desired cured film is obtained. The cured film obtained by the coating liquid containing the components (4) to (8) of the present invention has organic south molecular fine particles (component (8)) and colloidal silica dioxide (component (c)) dispersed in the film. The dispersed state is preferably an island structure of inorganic organic mixture. The particle size of the organic polymer microparticles and the colloidal dioxide particle component corresponding to the island of the island structure is preferably 200 nm or less, and more preferably 100 nm or less is not aggregated and uniformly dispersed. The total light transmittance of the cured film of the present invention is preferably 80% or more, more preferably 85% or more, and the haze value is preferably 1% by weight or less, more preferably the following. Such a cured film has high transparency. Further, the matrix having the Si-O bond dispersed by the organic microparticle (B component) and the colloidal dioxide dimer (c) component are derived from (Ai), (Α·2), (A_3), and 141326. Doc -45_ 201012882 (A-4) and (A-5) ingredients. Further, the present invention provides a method for producing a cured film, which comprises the steps of heating and hardening the above-described coating liquid of the present invention. Further, the cured film obtained from the coating liquid containing the components (A) to (G) of the present invention has organic polymer fine particles (component (B)) dispersed therein, colloidal cerium oxide (component (C)), and oxidation.钸 particle composition ;). The cured film of the present invention preferably has a haze value of 10% or less, more preferably 5. /〇The following. Such a cured film is excellent in ultraviolet resistance and has high transparency. Further, the organic polymer microparticles (component (B)), colloidal cerium oxide ((:) component), and cerium oxide particles (component (F)) are dispersed in a matrix having Si-germanium bonds from each (A). Further, the present invention provides a method for producing a cured film, which comprises the step of heating and hardening the coating liquid of the present invention. The resin laminate of the present invention will be described below. [Resin laminate] The tree-layered laminate includes a substrate and a resin layer formed on the substrate. The resin layer formed on the substrate may be one layer or two or more layers. Hereinafter, the resin laminate of the present invention will be described in detail. The first resin laminate system of the present invention has the laminate of the above-described cured film of the present invention on a substrate or between an inorganic layer (inorganic hard layer) and a substrate. Further, the second resin laminate system of the present invention has a substrate. And a laminated body of the cured film of the present invention formed on the substrate and the transparent conductive film formed on the cured film. Further, the third resin layered system of the present invention has a substrate and is formed at 141326.doc 201012882 In the laminated body of the cured film of the present invention and the photocatalyst layer formed on the cured film, the third resin laminate is collectively referred to as the resin laminate of the present invention. The coating liquid of the present invention is used to form the above. The method of curing the film is as shown in the above description of the cured film of the present invention. The resin laminate of the present invention has excellent abrasion resistance, scratch resistance, flex resistance and boiling resistance, and its use is as described above. It is shown in the description of the use in the coating liquid of the present invention.

The resin laminate of the present invention is not particularly limited as long as it has the above configuration. For example, it can be used for: windshields for two-wheeled vehicles, tricycles, automobiles, rail vehicles, construction machinery vehicles (four) f, construction machinery vehicles, automotive interior components, automotive exterior components, motorcycle components, trucks. The outer cover of the cargo box, the internal and external equipment of various vehicles such as trams, airplanes, ships, etc. (4) Components: audiovisual equipment (audiQvisual), washing machine, IH (InducUon Heating) cooking stove, household electric thieves, furniture, etc. Components, mobile phones, notebook computers, remote control devices, etc.; exterior decorative materials for furniture, building materials, window shades for windows, buildings, etc., interior finishes for walls, ceilings, floors, etc. Exterior wall such as siding, cofferdam w ® wall roof, door leaf, gable wall sealing sheet, exterior decoration for building, window frame, door leaf, (4), _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Illumination of street lamps, etc. = various displays such as electro-convergence, liquid crystal, organic anus, solar cells, lenses, optical discs, mirrors, bridge glasses, and sun glasses Mirrors, glasses lenses such as goggles and safety glasses, optical component containers such as window glass, lotion, bath 4, hand soap, etc. 141326.doc •47- 201012882 'Confectionery and snacks, beverage containers , small boxes and other various packaging, packaging materials; in addition, can be used for: Japanese-style pinball, etc.:, portable equal bag, bathroom toilet, table, clock, whiteboard shield and groceries. It is not only used as the above-mentioned automotive interior decorative member, but for example, a board, a console box, a meter cover, an instrument panel, an indicator panel, a door trim, a door lock ring, a steering wheel, a window lift switch seat, a central instrument cluster, and a control Plates, shift lever sleeves, switches, ashtrays, etc. As the member for the exterior decoration of the automobile, for example, a weatherproof, a bumper, a bumper protector, a body panel, a door panel, a spoiler, a hood, a body guard, a tank cover, Front grille, branch building: wheel cover, center pillar, rear view mirror, center enamel trim, side trim strip, door sill strip, window trim strip, etc., window, headlight, taillight, lamp mirror, door shade Board, windshield parts, etc. Further, the above-mentioned components for the motorcycle include, for example, a casing, a fender, a fuel tank cap, a tank lid, and the like. =The above-mentioned audio-visual equipment, washing machine, rice cooker, electric power, m cooking oven, electrical appliances, furniture and other components, for example, front panel, control = touch panel "membrane switch panel, button, standard" surface Decorative materials, etc. : Road light transmissive soundproof panels, windproof panels, snow shelters, car light chambers, verandas, etc., roofs, buildings, etc., windows, plastics, etc. As such building materials, for example, soundproof panels and arcades around railways and factories can be cited. Lighting materials for sheds and bicycle parking lots, bus stops, and entrance or hemispherical roofs 141326.doc -48· 201012882 Greenhouses, etc. Examples of the components of the mobile phone, the notebook computer, and the remote control device include a casing, a display window, a keypad, a button, and the like. (Substrate) As the substrate, at least any one of resin, metal, wood, rubber, concrete, stone, ceramic, leather, paper, cloth, and fiber can be used, but it is preferable to use a resin substrate. (Resin substrate).

Examples of the substrate include a resin, a film, a sheet, and the like. The film or sheet is produced by a known molding method such as an extrusion molding method, an aeration method, or a solution casting method, and the like may be extended in a uniaxial and/or biaxial direction as needed. The kind of the resin in the substrate is not particularly limited, and can be appropriately selected from various resins depending on the use of the obtained resin laminate. Further, the substrate of the present invention may have irregularities and may have a cylindrical shape, an elliptical cylindrical shape, a prismatic shape or the like regardless of the shape of the substrate. Further, when the resin laminate of the present invention has a space inside it and has an internal space, it is also possible to laminate another resin layer on the inner wall portion. Therefore, the shape of the substrate of the present invention is not particularly limited. The resin laminate of the present invention comprises a resin laminate obtained by insert molding or insert molding as described below. -% <Rouge, for example, polyethylene, polypropylene, and cycloaliphatic resin (for example, "Arton, 曰太 7" manufactured by Micro Co., Ltd." Polyolefin resin such as Zeonor, Zeonex, M ® ^ glutaryl; publicly available ethylene phthalate, poly(p-phenylene tert-butyrate), polyphthalic acid 141326.doc •49- 201012882 Polyester resin such as ethylene diacetate; cellulose resin such as cellulose diacetate, cellulose triacetate or cellulose acetate butyrate; polystyrene, aligned polystyrene, acrylonitrile butadiene benzene A styrene-based resin such as a vinyl resin (ABS resin), such as a polyimine, a polyether quinone, or a polyamidamine, and a nylon polyamine phthalamide resin; a ketone resin such as polyether ketone, a sulfone resin such as polyfluorene or polyether sulfone; a polyvinyl chloride resin such as polyvinyl chloride or polyvinylidene; an acrylic resin such as polymethyl methacrylate; Therefore, acid s曰 resin, polyphenylene sulfide, polycondensation, modified polyphenylene ether, polyvinyl alcohol, epoxy resin, fluororesin ;. The above polymer alloy may also be a polymer obtained by mixing a plurality of kinds _ polymer blend. Further, it may be a laminated structure in which a plurality of layers of the above resin are laminated. Among the above resins, preferred are polyester resins, polyolefin resins and polycarbonate resins. With this special 掏 grease as a good sister I u __

A polycarbonate excellent in mechanical properties, heat resistance, and the like.

Examples of the plasma treatment such as the plasma method or the atmospheric piezoelectric slurry method include corona discharge treatment, plasma treatment at a low pressure, chromic acid treatment (wet), and I41326.doc • 50. 201012882 Fire treatment, hot air treatment In addition, as the embossing method, for example, a blasting method, a solvent treatment method, or the like can be mentioned. These surface treatment methods can be appropriately selected depending on the kind of the substrate, and in general, in terms of hardening and workability, a corona discharge treatment method is preferred. x, can also be surface treated or provided with a primer coating. (Inorganic Hard Layer) The inorganic hard f layer in the smectic layer may be selected depending on the function to be imparted, and is not particularly limited. For example, in the case where the inorganic hard layer is to be subjected to abrasion resistance, the inorganic hard layer is preferably a SKM1.GK2) film, a SiNy (1^yS4/3) film or an amorphous carbon film. The Si〇x (1.8 to 2) film and the SiNy (1 2 in 4/3) film are formed by a chemical vapor deposition method or a physical vapor deposition method, for example, so that stoichiometry is performed. The reaction was not completed. Therefore, in the filler layer +, a defect portion into which an oxygen atom or a nitrogen atom is not introduced can be formed, and X and y have a range in the SiOx and SiNy films. Further, it is also suitable to combine a combination of oxygen and nitriding which can be produced by simultaneously injecting oxygen and nitrogen. Further, the hardness of the inorganic hard layer may be such that the increase in haze in the evaluation using the TABERS tester as shown in the examples is less than iq%. Alternatively, it may be about 500 HV or more in terms of micro Vickers hardness (mi (10) viekers ^ as coffee). The thickness of the inorganic hard layer is, for example, preferably 丨μπ1 or more, more preferably 1 to 8 μm. Further, in the method for producing an inorganic hard material layer described below, inorganic = 141326.doc • 51 - 201012882 The physical layer is preferably laminated directly on the cured film. The inorganic hard layer of the resin laminate of the present invention is preferably formed by chemical vapor deposition (CVD) or physical vapor deposition (PVD). Specific examples of the CVD method include a plasma CVD method and a photo CVD method. Specific examples of the PVD method include an ion key method, a vacuum vapor deposition method, and a sputtering method. The inorganic hard layer formed by the thin film forming technique carried out under vacuum as described above usually has a property of being in close contact with the inorganic component but not easily adhered to the organic component. In the case of the resin laminate of the present invention, since the cured film has an inorganic-organic hybrid structure in which the organic fine particles are sealed in the Si-O matrix, the adhesion between the inorganic hard layer and the cured film is good. As a specific example of laminating an inorganic hard material layer by a CVD method, a case where Si〇x (1 8 $ χ $2) is formed on a cured film by a plasma CVD method will be described. The plasma CVD method refers to a method in which a material gas is introduced into a plasma state having a high energy density to be decomposed, and a target material is coated on a substrate by a chemical reaction. In the present invention, a laminate including a substrate and a cured film is placed in a plasma CVD apparatus to evacuate the inside of the apparatus, and an argon gas is introduced into the plasma CVD apparatus to introduce a Si〇x (18 $ 2) film. When the flow rate of each gas becomes stable, electric power is applied to generate plasma, and a Si〇x (1_8$xS2) film is formed on the cured film. In the case where the inorganic hard material layer is a Si〇x(l_8^x^2) film, the raw material for forming the Si〇x (1.8SxS 2) film is, for example, a bismuth source gas and an oxygen source gas 141326.doc -52- 201012882 The Si〇x (1.8sxg2) film is preferably a ruthenium gas or an organic ruthenium compound gas. Examples of the decane gas to be suitably used include SiH4 gas, 2116 gas, Si3HA body, and the like. The organic ruthenium compound is preferably selected from those having a carbon-containing group bonded to the ruthenium. Specific examples of the organic pulverized compound to be suitably used include, for example, tetramethoxy decane, tetraethoxy decane, methyl trimethoxy decane, ethyl trimethoxy hydroxy, tetradecyl oxazepam, and Methoxy dimethyl sinter, diethoxy dimethyl sulphur, methyl triethoxy sulphur, octamethyl alkane, and the like. These organic 7 compounds may be used singly or in combination with two or more kinds of oxysulfide raw materials, which are suitable for use in the case where the gas of the SK>X (1.8SU2) film is used as a money gas. In the case where the raw material gas of the Si〇x (1.KG2) film is an organic compound gas, the oxygen source gas which is suitably used may be, for example, n2o gas or helium gas. And the flow rate of the above-mentioned stone raw material gas and oxygen raw material gas is, for example, i rhyme (10) 3 / minute, preferably 1 to 300 cm 3 / minute... the flow rate of argon gas is, for example, 20 to 400 CmV minutes, preferably The plasma CVD apparatus to be used is not particularly limited as long as it is a commonly used device, and for example, a parallel plate electrode type, a capacitance light type, an inductance consumption type, or the like can be used. The plasma (10) device can be used. The internal force of M is, for example, better 岐h33~133^left 141326.doc -53·201012882 Right' particularly good is about 2.7 Pa. The frequency of the power source used in power application can be widely used in the range of acoustic wave to microwave. Si〇x (1 8$χ) is formed on the cured film by the above plasma CVD method. In the case of the film, when an organic ruthenium compound is used as the ruthenium raw material gas and the organic ruthenium compound is a liquid or a solid at normal temperature, the entire organic ruthenium compound-containing container is heated and vaporized and used. The flow rate of the organic hydrazine compound gas and the oxygen source gas is controlled, for example, to 1 to 10 cm 3 /min, and the flow rate is controlled to, for example, 2 〇 to 4 〇〇.

The argon gas of Cm3/min was introduced into the plasma CVD apparatus (direct gasification introduction method). Further, in addition to the above-described direct gasification introduction method, when the organic ruthenium compound is a liquid, argon gas may be used as a carrier gas, for example, argon gas may be introduced into the organic phase at a flow rate of 2 〇 to 4 〇〇 cm 3 /min. In a temperature-controllable container of the hydrazine compound, the organic hydrazine compound is foamed, and the organic hydrazine compound vapor is introduced into the plasma CVD apparatus together with argon gas (foaming introduction method using a carrier gas). In the method for producing the inorganic hard material layer, when the inorganic hard material layer is a SiNy (1.2^y$4/3) film, the material gas for forming the SiNy (12 syg4/3) film is, for example, a bismuth material gas and a nitrogen material. gas. Examples of the raw material gas which is suitably used include a decane gas such as SiH4 gas, 81-out 6 gas, and Si3H8 gas. Further, examples of the nitrogen source gas which is suitably used include n2 gas and Nh3 gas. In the case of the inorganic hard material layer being an amorphous carbon film, a hydrocarbon gas is suitably used as a material gas for forming an amorphous carbon film. In the case of the south of the Ι gas, it is also possible to introduce the gas at the same time for dilution. In the method for producing an inorganic hard material layer according to the above (10) method, the fourth material gas is used as the raw material of the inorganic hard material layer, but the invention is not limited thereto. For example, φ h can also be used after vaporizing the steamed raw material of the inorganic hard material layer described below. As a specific example of laminating an inorganic hard substance layer by the PVD method, a case where an inorganic hard substance layer is laminated by an ion-mine method will be described. The ion plating method is a method in which a reactive gas or the like is introduced into a vacuum-based plating f, and a gas plasma is generated in the device by various methods to partially ionize the generated vapor-deposited particles (atoms and molecules). Accelerating a method of irradiating a substrate placed in a vacuum with molten metal particles and ions thereof to form a thin film of a vaporized material on a substrate. That is, the so-called ionization method refers to a composite technology of vacuum evaporation φ plating technology and plasma technology. The above ion plating method is disclosed, for example, in Japanese Patent Laid-Open Publication No. SHO 58-29835. In the present invention, the laminate of the substrate and the cured film and the vapor deposition material of the inorganic hard layer are disposed at predetermined positions in the vacuum vapor deposition apparatus, and an inert gas such as argon gas or helium gas is generated to generate plasma. And, if necessary, in a reactive gas introduction device such as N2, N2, acetylene or air, a high-frequency voltage is applied in the vicinity of the vapor deposition material to plasma the vapor deposition material, thereby laminating the inorganic hard material on the cured film. on. 141326.doc -55- 201012882

乍 is a vapor deposition material for the hard layer of '·, and the inorganic hard material layer is Si〇x (in the case of 1.8SU2m, oxidized smash, etc., & inorganic hard layer is SiNy (1.2gy $ 4/) 3) In the case of a film, a gasification stone or the like may be mentioned, and when the hard material layer is an amorphous carbon film, DLC (diamond-like carbon) or the like may be mentioned. The vapor deposition material of the inorganic hard material layer The money is intended to be formed into the raw material of the inorganic hard layer itself. Further, the steamed bond material of the inorganic hard layer in the ion-recording method is not limited to the solid W such as 'difficult to steam In the case where the raw material of the mineral raw material is evaporated, the gas oxygen source material of the inorganic hard material layer may be introduced into the vacuum plug plating body and the inorganic hard material layer. In the mine equipment, the reactor is subjected to a reaction test and the pressure in the right vacuum distillation unit is, for example, Pa. The application of the high-frequency electric discharge device is limited to the high-frequency discharge. The above-mentioned high-frequency voltage is, for example, from about ～8.GkV, and φ is used in the above-mentioned ion-electric money method, in order to perform the discharge on the surface of the cured film, it is possible to use a resistor, a heater, a heater, and a laser. The beam adds demon and other forces..., electron beam heating, high frequency induction. ‘,、, special heating method, as needed, steaming the raw materials of the steaming method, the method of laminating the inorganic hard layer and the electro-mine method. As described above, it is possible to utilize the ionic inorganic hard layer. The so-called vacuum evaporation method, such as sputtering, means that the raw material is evaporated by heat in the true two, and the 141326.doc • 56 - 201012882 evaporating particles are transported to the surface of the substrate, and the evaporated particles are rearranged on the surface of the substrate. And a method of forming a film. In the vacuum evaporation method, the degree of vacuum is usually 1 · 3 χ 2 2 Pa or less. The term "sputtering method" means that the inert gas is made into a plasma, and the obtained positive ions are struck against the raw material to knock out elemental atoms on the surface of the raw material, and adhere to and/or accumulate on the substrate located in the vicinity thereof to form a thin film. The method. (transparent conductive film)

The transparent conductive film in the second resin laminate of the present invention can be selected depending on the function to be imparted, and is not particularly limited. For example, when it is desired to impart a low-resistance electrical property to the transparent conductive film, the transparent conductive film is preferably zinc oxide, AZ0 (aluminum-doped oxidized) 4GZ lanthanum (gallium-doped zinc oxide), or the like. Main component material, or IT〇 (tin-doped indium oxide), Sn〇2 (tin oxide), antimony (zinc-doped indium oxide), ic〇 (indium-doped indium oxide), ATO (doped with tin oxide), A material that is transparent and electrically conductive, such as FT〇 (fluorinated tin oxide), which is not mainly composed of oxidation. One of the indexes of the conductivity of the transparent conductive film is the carrier concentration, and the higher the carrier concentration, the higher the conductivity. When the carrier concentration is above lxl() 18/em3 or more, a surface resistance value of 10000 Ω/□ or less is obtained, which is preferable. In addition, if the carrier/agronomy is 1 X1 〇丨 9/cm or more, it is suitable for use as an anti-reflection film. (9) When the carrier concentration is 5xlQl9/em3 or more, a resin layered body having a surface resistance value of 1 〇 to 100 () Ω/□ which is used for a touch panel for a touch panel can be produced. When the transparent conductive film is made into an amorphous film, the film thickness can be further reduced, which is preferable. The coating coverage becomes good as amorphous transparent conductive 141326.doc •57· 201012882 Membrane material, exemplified by IZ〇(zinc-doped tin)糸Μ胜τ) 'ΖΤ〇(zinc oxide-tin oxide) Phase, l2T 〇 (oxidized steel _ oxide film, etc., π μ jia, f emulsified tin), tin oxide thin characteristics, + added oxides that impart electrical, optical and mechanical properties to the films Department and so on. Optical material: == When the resistance value is set to a high resistance value, it can be adjusted by selecting == thick or medium. For example, in the case of a valence of a value of ..., a crystalline material having a good (low) resistivity such as ιτ〇 can be used for the transparent conductive medium. Further, it is expected to reduce the surface resistance by increasing the film thickness. However, if the film thickness of the transparent conductive medium is made small, the transmittance can be expected to be improved. In addition, the surface resistance value may be appropriately determined depending on the purpose of use, and if it is used for photoelectric 4, photoelectric conversion, liquid crystal, touch panel, etc., the surface resistance value is preferably 1 G_ or more and side (10) or less. More preferably, it is _ Ω / □ or more and 2 Ω / α or less. Further, the thickness of the transparent conductive film is, for example, preferably 5 nm or more, more preferably 1 〇 to 3 Å... Further, in the method of forming a transparent conductive film described below, the transparent conductive film is preferably directly laminated on the transparent conductive film. On the hardened film. Further, the optimum film thickness of each layer can be determined, for example, by the following method. First, the film thickness of the transparent conductive film in which the necessary surface resistance value can be obtained is determined according to the use. Next, the refractive index of the material used in the cured film is set to a fixed value, and the film thickness of the cured film is changed by an optimization algorithm to determine the film thickness of the cured film which can obtain the highest transmittance or the lowest reflectance. . Further, the transparent conductive film provided on the cured film may be a single layer or a multilayer film of two or more layers. For example, a transparent conductive film of two or more layers may be provided in consideration of the transmittance (reflectance) of a substrate having a conductive multilayer film of 141326.doc -58 - 201012882, and the anti-reflection with a high refractive index may be improved. membrane. Further, even when the antireflection film is formed, it is not limited to one layer, and a multilayer structure (e.g., two to six layers) having a desired transmittance (reflectance) can be formed. (Method for Producing Resin Laminate) Hereinafter, a method for producing a second resin laminate according to the present invention will be described. The method for producing a resin laminate according to the present invention includes the step of forming the above-mentioned (A) to The step (a) of curing the cured coating film of the component (E) and the step (b) of forming a transparent conductive film on the cured film. Further, the above step (a) is as shown in the above description of the coating liquid and the cured film. (Formation of Transparent Conductive Film) The second resin laminated system of the present invention has a cured film formed between the transparent conductive film and the substrate, and the transparent conductive film is preferably a chemical vapor deposition method (CVD method) or a physical gas. A phase deposition method (PVD method) or a coating method is formed on the cured film. Specific examples of the CVD method include an electric CVD method, a photo CVD method, and a mist method. Specific examples of the Pvd method include an ion plating method, a vacuum vapor deposition method, and a sputtering method. Specific examples of the coating method include a spray method, a spin coating method, a bar coating method, a knife coating method, and an inkjet method. The transparent conductive film formed by the thin film formation technique under vacuum generally has a property of being intimate with the inorganic component but having difficulty in adhering to the organic component 141326.doc -59- 201012882. In the case of the resin laminate of the present invention, since the cured film has an inorganic-organic hybrid structure in which the organic fine particles are encapsulated in the Si-ruthenium matrix, the adhesion between the transparent conductive film and the cured film is good. As a specific example of laminating a transparent conductive film by a sputtering method, a case where an ITO film is formed on a cured film by a bismuth method will be described. The sputtering method refers to the process of causing an inert gas to be a plasma, and causing the obtained positive ions to strike the raw material to knock out elemental atoms on the surface of the raw material, causing them to adhere and/or accumulate in the vicinity thereof. A method of forming a thin crucible on a substrate. In this case, the target system uses an ITO sintered body. A layered body including a substrate and a cured film is placed in a sputtering apparatus, and a vacuum of 1 〇·5 or less is usually placed in the apparatus, and argon gas is introduced thereto, and 0. W0 kWW is applied under a vacuum of about 0. HiO Pa. The left and right DC power is generated to cause electric cracking to form an ITO film on the cured film. In the case where the transparent conductive film is an ITO medium, the material for forming the ITC) film is, for example, an indium oxide sintered body target to which 10% by mass is added. In order to control conductivity and optical characteristics, there is also a case where oxygen is mixed into argon gas. The method of laminating the transparent conductive film by the PVD method is not limited to the above-described plating method, and a transparent conductive layer can be laminated by a vacuum vapor deposition method, an ion plating method, or the like, and a double-heat evaporation of the MP is carried out to transport the evaporated particles. A method of forming a film by evaporating particles on the surface of the substrate to form a film on the surface of the substrate. In the vacuum evaporation method, the hollowness is usually 1.3 x 10 2 Pa or less. 141326.doc 201012882 The ion plating method is a method in which a reactive gas or the like is introduced into a vacuum vapor deposition apparatus, and gas plasma is generated in the apparatus by various methods to partially ionize the generated vapor deposition particles (atoms and molecules). Further, the method of irradiating the substrate placed in a vacuum with the vapor-deposited particles and ions thereof to form a thin film of the vapor-deposited material on the substrate is accelerated. That is, the so-called ion plating method refers to a composite technology of vacuum evaporation technology and plasma technology. As a specific example of laminating a transparent conductive film by a CVD method, a case where a Zn film is formed on a cured film by a plasma CVD method will be described. The plasma CVD method refers to a method in which a material gas is introduced into a plasma state having a high energy density to be decomposed, and a target material is coated on a substrate by a chemical reaction. In the second resin laminate of the present invention, a laminate including a substrate and a cured film is placed in a plasma cvd device, and after the inside of the device is vacuumed, Zn film is introduced into the plasma CVD device while adding argon gas. When the flow rate of each gas becomes stable, electric power is applied to generate plasma, thereby forming a ZnO film on the cured film. (Photocatalyst layer) The photocatalyst material used in the photocatalyst layer of the third resin laminate of the present invention is not particularly limited, and conventionally known ones such as titanium dioxide, titanate, barium titanate, sodium titanate, and the like can be used. Oxidation record, tungsten oxide, cadmium sulfide, vulcanization, etc. These may be used singly or in combination of plural kinds. Among these, titanium dioxide, especially anatase type dioxide, can be used as a practical photocatalyst. Further, a conventionally known photocatalyst promoter may be added to promote the activity of the photocatalysts. As the photocatalyst, for example, a platinum group metal such as platinum, palladium, rhodium or iridium may be preferably used, and these may be used singly or in combination of plural kinds. From the viewpoint of photocatalytic activity, the amount of the photocatalyst promoter to be added is usually selected in the range of 1 to 20% by mass based on the photocatalyst. The formation method of the photocatalyst layer is as follows. In the case of the wet method, a polyfluorene-based compound is usually used in the matrix of the photocatalyst layer. For example, an alkoxydecane such as polyorganosiloxane or tetraethoxysilane is hydrolyzed and then condensed to form a matrix. (Method for Producing Resin Laminate) Hereinafter, a method for producing the third resin laminate of the present invention will be described. The method for producing a resin laminate of the present invention comprises the step (4) of forming the cured film of the present invention on a substrate, and the step (b) of forming a photocatalyst layer on the cured film. Further, the above step (4) is as shown in the above description of the hardened film.并无 There is no particular limitation on the method of forming the photocatalyst layer on the cured film.

Use a variety of methods. For example, a dry method such as a vacuum distillation method or a reduced ore method, or a dry method such as a metal spray method or a wet method using a (four) cloth liquid may be mentioned. The liquid of the wetness of the spleen is more preferably dispersed in an appropriate hood or the like. "", the machine point. Sword (for example, the polyoxygenated coating liquid can be known by the use of too much, soil, method, (four) coating method, rod, for example, dip coating method, spin coating to knife coating method, die coating method, The concave cloth is removed, coated, etc., and dried to form a photocatalyst layer. The thickness of the photocatalyst layer is usually 5 nm~2 μπι', preferably 10 nm~2 μιη, especially Preferably, it is 2 〇 nmM μιη. If it is less than 5 nm, the photocatalytic function is not fully utilized. If it exceeds 2 μm, the photocatalytic function is not significantly improved even if the thickness is larger than this. The resin laminate of the present invention may also be used. The molded body (molded body of the resin laminated body). The molded body of the resin laminated body can be produced by thermoforming. Examples of the hot forming include vacuum forming, vacuum forming, pressure forming, plug assist forming, and the like. Tightly-molding. (Substrate for thermoforming) The following is a description of a substrate for thermoforming (hereinafter, simply referred to as "r-substrate"). The softening point of the material is 50~30 The sheet or film in which the thermoplastic resin is in the range of about 0 ° C, for example, polycarbonate, polypropylene, polyethylene, polystyrene, acrylonitrile-butadiene-stupid vinyl resin (ABS resin), An acrylonitrile-styrene resin (AS resin), a methyl methacrylate-styrene resin), a polyester resin, an acrylic resin, an ethylene-based resin, a fluorine-based resin, or the like, or a mixture of the above polymers A plurality of polymer alloys and polymer blends. Further, it may be a laminated structure in which a plurality of layers of the above resin are laminated. A decorative layer may also be provided on the surface of the substrate on which the cured film is not formed. The decorative layer 'is an ink layer, a high-brightness ink layer, a metal vapor-deposited layer, or the like. Further, the decorative layer may be a single layer or a laminated layer combined with each other. Next, the thickness of the substrate will be described. 141326.doc -63- 201012882 The thickness of the substrate sheet or film for insert molding is preferably 5 μm to 〇 7 mm. In the case of less than 5 μηη, there is a problem that the film strength is low and the film is broken at the time of forming. In addition, when it exceeds 0.7 mm, it is difficult to form a sheet for insert molding in a wound state, which is inferior in productivity. Hereinafter, an example of the thermoforming method will be described, but the present invention is not limited to the description described below. In the injection molding die, a substrate sheet which is not thermoformed is placed so that the surface on the side of the cured film faces the movable mold, and vacuum forming is performed by vacuum suction holes of the movable mold to perform preliminary molding. Then, the injection resin is molded in the mold on the side where the cured film is not formed, and the injection resin is integrated with the substrate sheet. Further, after the base material sheet which has been subjected to hot forming is provided in the injection molding die, the injection resin is formed by filling the injection resin on the surface side of the surface on which the cured film is not formed, and the injection resin is integrated with the base material sheet. In order to form the base material sheet for forming into irregularities or cylindrical shapes, an elliptical cylindrical shape is formed by hot forming. Examples of the thermoforming method include hollow forming (including molding, etc.), vacuum forming, pressure forming, press molding, and extrusion molding. In order to mount the substrate sheet which has been thermoformed in the injection molding die, the incoming lamp cuts the unnecessary portion and trims it. The shape of the injection-molding mold is not limited to the method of dressing, the laser cutting method, or the mouth water method; the V column can be exemplified by die cutting (Thom-stamping method, etc.. Thomson repaired 141326.doc -64 - 201012882 at the same time as hot forming. In the injection molding die, the substrate which is not thermoformed is placed in such a manner that the surface of the cured film faces the movable mold, and the vacuum of the movable mold is utilized. The suction hole is subjected to vacuum suction to perform preliminary molding. Then, the injection resin is filled on the surface side where the cured film is not formed. The conditions for in-mold injection molding are not particularly limited, and can be in the range of usual injection molding conditions. Further, the injection molding machine can use either a vertical injection molding machine or a horizontal injection molding machine. The base material sheet that has been thermoformed is placed in an injection molding die, and the injection resin is not formed. The surface side of the cured film is not particularly limited, and can be adjusted within the conditions of normal injection molding. Further, the injection molding machine can be used. Any one of a vertical injection molding machine and a horizontal injection molding machine. The injection molding die has a mechanism for filling the surface of the base material sheet on which the injection resin is thermoformed without forming a cured film. In the case of a vertical injection molding machine, if it is placed in the lower mold of the mold, it is fixed by gravity. When it is necessary to be placed in the mold above the mold, vacuum suction from the mold will be performed. a method of fixing a base sheet to be thermoformed, a method of covering with a convex portion of a mold, a method of fixing by a lock, etc. In the case of a horizontal injection molding machine, it is disposed at a solid state. In the case of either side of the side or the movable side, vacuum suction is applied to fix it, a method of covering with a convex portion of the mold, a method of fixing with a pin, etc. Further, the present invention also provides A method for producing a hardened crucible, characterized in that the package I41326.doc-65·201012882 includes a step of heating and hardening the coating liquid of the present invention; and a method for producing a resin laminate, characterized in The method includes the steps of applying the coating liquid of the present invention to the step of immersing the substrate, drying the coating liquid, and thermally forming the substrate, and curing the coating liquid to form a coating layer. In the method for producing a resin laminated body, the method further includes a step of providing a resin layer on the surface of the resin layer which is obtained by curing the coating liquid, and the coating layer is provided. The embodiment will be described in more detail by way of examples. The present invention is not limited to the examples, and the characteristics in each of the examples are as follows. (1) Oxidation of inorganic components in the cured film. The content of the substance (% by mass) was measured by thermogravimetric measurement on a Teflon (registered trademark) petri dish on a Teflon (registered trademark) petri dish, and the sample solution was thermally hardened (nitrogen was heated at 2 Torr. Temperature ~800eC), according to its 8〇〇. Find the residue of your arm. (2) The content (% by mass) of the organic polymer fine particles in the cured film is calculated by calculation. Specifically, the total mass of the organic polymer microparticles ((B) component) and the knee biodegradation ((〇 component)) is calculated (the component of the A (A-5) component is hydrolyzed and reduced. % of the organic polymer microparticles in the solution. (3) The solution stability of the coating solution was sealed and stored at room temperature for 14 days, and it was judged by visual observation that the gelation was 141326.doc 201012882. For non-gelling, The viscosity measurement by the tuning fork vibrating viscometer 8^10 of A & D Co., Ltd. is described as "〇" when the rate of change is less than 3 times, and is marked as "Γχ". (4) Appearance of the film The appearance of the cured film was visually observed, and the foreign matter, the speckle pattern, and the white turbidity were identified. The case where the above was not confirmed was described as "good". (5) The total light transmittance and the haze were straight. The total light transmittance and haze of the laminate were measured by a direct-read haze computer (manufactured by Suga Test Machine Co., Ltd., HGM_2DP). (6) Wear resistance using the wear wheel CS-1 OF and TABER Abrasion Tester (Rotary Abrasion Tester) (Toyo Seiki Co., Ltd.) Manufactured, model: TS), 500 ton TABER abrasion test at a load of 4.9 N, and the difference between the haze before the TABER abrasion test and the haze after the TABER abrasion test (δη) is less than 15 as "•" In the case of the first to eleventh and the comparative examples 1 to 6, the steel wire field #〇〇〇〇 'After reciprocating 50 times at 2000 mm/sec, the surface damage was evaluated by visual inspection. Those who were completely intact were recorded as "1", and those who were slightly damaged were recorded as "2", and the parts to be rubbed were The damage of more than half of the faces is marked as "3". In Examples 12 to 16 and Comparative Examples 7 to 11, steel wool #〇〇〇〇 (load 9.8 N) was used, and reciprocating at 2000 mm/sec 50 After that, the damage of the surface of 141326.doc -67. 201012882 was evaluated by visual inspection. The person who was completely undamaged was recorded as "1", and the person who was slightly damaged was "2", and the part that would be rubbed The damage of more than half of the face is marked as "3". (8) Adhesiveness According to Jis K 5400, the sample (hardened film) is cut into the vertical and horizontal directions at intervals of 2 mm using a razor blade. The strip was slit to form 100 grids, and the commercially available cellophane tape ("CT-24 (width: 24 mm)", manufactured by Nichiban Co., Ltd.) was sufficiently adhered to the sample with the fingertips. The angle of 0 was quickly peeled off in the near J direction, and the number of meshes (X) in which the cured film was not peeled off and represented by X/100 was evaluated to evaluate the adhesion of the cured film. (9) Boiling resistance (boil 5) Adhesiveness after hours) The sample of the laminate was immersed in boiling water in a stainless steel beaker for 5 hours, and then the male and the traits were evaluated. The evaluation of the adhesion was carried out in the same manner as in the above (8). (10) Weather resistance The Xenon arc lamp weathering test was carried out for 1000 hours (Ci65 from Atlas, the output power was 6.5 kW, the black panel temperature was 63 °c, and the relative humidity was 5〇%). The weather resistance was evaluated by the change in the adhesion of the cured film before and after the test. (11) Refractor resistance is the same as in each case except that a polycarbonate standard plate (trade name: ECK100) manufactured by Sumitomo Bakelite Co., Ltd., which is 100 mm x width 50 tnmx and 1 mm thick, is used as the substrate. A method of producing a sample of a resin laminate. Hold the two ends of the specimen with your fingers, and perform the forced bending of the 141326.doc -68 *- 201012882 line with a radius of 5 〇mni, and record the crack on the layer as "〇". Those who have cracks are recorded as Γχ." (12) Heat resistance The heat resistance test (manufactured by Konica Minolta, PS-222) was carried out at 110 ° C for 720 hours. The heat resistance was evaluated by the change in the adhesion of the cured film before and after the test. (13) Organic particle dispersion structure

The TEM (transmission electron microscope) was used to observe the cross-section of the cured film, and one organic particle present in the region of 1 μιη square was selected, and the NIH (Nati〇nal) was used.

Freesoft: NIH Image 1.63 manufactured by the Institute of Health). Those whose average particle diameter of organic fine particles is 200 nm or less are referred to as "〇", those whose average particle diameter is larger than 200 nm are referred to as "X", and those having a particle diameter of 200 nm or less are present, but there is particle melting. The case of an amoeba having a particle diameter of 200 nm or more is referred to as "Δ". (14) Inorganic fine particle dispersion structure The average particle diameter of each of the colloidal cerium oxide particles in the cured film was determined in the same manner as in the above (13). Those whose average particle diameter is 2 〇〇 nm or less are 〇 "〇", and those whose average particle diameter is larger than 2 〇〇 nm are denoted as rx". Further, in the examples and comparative examples, the contents are as follows. 'The original name recorded in the trade name

Fine (A-1) component: M Silicate 51 "Poly alkoxy decane as a part of tetradecyloxydecane (average three to pentamer)" Tama Chemical Condensation Co., Ltd. Manufacturing Hard 1 141326.doc -69· 201012882 (A-2) Component: MTMS-Α "Polyorganoalkoxydecane which is a partial condensate of methyltrimethoxydecane" manufactured by Tama Chemical Industry Co., Ltd. (A-2) Component: SR2402" Polyorganoalkoxydecane which is a partial condensate of methyltrimethoxydecane" manufactured by Toray Dow Corning Co., Ltd. (B) Component: ULS-1385MG (UV absorption skeleton: benzotriazole) Manufactured by the company of the company (water dispersion/solids concentration: 30% by mass) (B) Ingredients: ULS-385MG (ultraviolet absorbing skeleton: benzophenone) Manufactured by Yokosuka Oil & Fats Co., Ltd. (water dispersion/solids) Concentration: 30% by mass) (C) Component: IPA-ST-L (colloidal cerium oxide) Manufactured by 曰Production Chemical Industry Co., Ltd. (isopropyl alcohol dispersion, colloidal cerium oxide concentration of 30% by mass, average particle size 40~50 nm (manufacturer announced )) [Examples 1~11 and Comparative Examples 1~6] Example 1 (1) Preparation of coating solution prepared in accordance with the embodiment of the composition and the blending amount shown in Table 1. Into a sample tube having a volume of 50 ml, an organic polymer microparticle: ULS-1385MG ((B) component + (E) component) 0.80 g was placed, and the mixture was stirred at 500 rpm while being sequentially added dropwise for 1 minute.曱oxy-2-propanol ((E) component) 4.25 g, water ((E) component) 0.50 g, acetic acid ((D) component) 0.50 g, M Silicate 51 ((A-1) component 0.40 g, MTMS-A ((A-2) component) 1.10 g, dimethoxy-3-glycidoxypropylmethyldecane (component (A-4)) 0.55 g, 20 mass 141326.doc -70- 201012882

% p-toluenesulfonic acid methanol solution ((D) component + (E) component) 0.05 g. Then, after stirring at 500 rpm for 60 minutes at room temperature, it was allowed to stand for one day, and it was made into the A liquid. To a sample tube having a volume of 20 ml, 0.37 g of 3-isocyanatopropyltriethoxydecane and 0.35 g of 2-butanone oxime (isocyanate-based blocking agent) were introduced at room temperature at 500 rpm. After stirring for 10 minutes, it was allowed to stand for one day and used as a liquid C. The blocking of the isocyanate group was confirmed by the disappearance of the signal of the isocyanate group in the 13C-NMR. The total amount of 3-isocyanatepropyltriethoxydecane and 2-butanone oxime is defined as the amount of the blocked isocyanatodecane compound: (A-5). Add a liquid A and a stirrer to a 200 ml three-necked flask equipped with a cooling tube, and stir at 500 rpm while mixing, and add IPA-ST-L as a liquid B for 5 minutes ((C) component + (E) Ingredient) 6.50 g, stirred at room temperature for 60 minutes. Then, it was heated under a nitrogen stream at 600 rpm and 80 ° C for 3 hours. Then, the solution C was added, and the mixture was stirred at 80 ° C for 4 hours under the same conditions, and then allowed to stand at room temperature overnight. Further, 0.40 g of 3-aminopropyltrimethoxydecane (component (A-3)) as a solution D was added dropwise thereto over 2 minutes. After stirring at room temperature for 10 minutes, it was further heated under a nitrogen stream at 700 rpm and 80 ° C for 3 hours. Then, it was allowed to stand for 1 week to obtain a coating liquid. (2) The production of the laminate was carried out using a polycarbonate substrate [manufactured by Idemitsu Kosan Co., Ltd., trade name: Tarflon, product number·· IV2200R (weathering grade), thickness: 3 mm (total light transmittance: 90%). The haze value was 0.5%)] as a substrate. 141326.doc -71 · 201012882 The coating liquid obtained in the above (1) was applied to the surface of a polycarbonate molded body having a thickness of 3 mm by a bar coater at a thickness of 3 μm to 13 (TC, The layered body including the base material and the cured film was produced by thermosetting for 2 hours. The obtained coating liquid and laminated body were evaluated. The evaluation results are shown in Table 2. Examples 2 to 11 In the same manner as in Example 1, the coating liquid was produced in accordance with the components and the amounts shown in Table i, and a laminate was produced. The evaluation results of the obtained coating liquid and laminate were shown in Table 2. Comparative Example 1 According to Table 3 Prepare the ingredients and the amount of the preparation shown in the figure. Into the sample tube with a volume of 50 ml, put ULS-1385MG ((B) component + (E) component) 0.90 g ' while stirring at 5 rpm, using 1 1-methoxy-2-propanol ((E) component) 2.00 g, water ((E) component) 0.09 g, acetic acid ((d) component) 3.20 g, decyltridecyloxy group were added dropwise in sequence.矽 ( ((A-2) component) 2.00 g, dimethoxy _3_glycidoxypropyl decyl decane ((A_ 4) component) 0.96 g 5 mass% p-toluenesulfonic acid methanol solution ((d) component + (E) component) 0.20 g. Then, after stirring at 5 rpin for 60 minutes at room temperature, it was allowed to stand for one day, and it was used as liquid A. To a sample of 20 ml of grain, 3 -isopropoxypropyltriethoxydecane 1·10 g and 2-butanone oxime (isocyanate-based blocking agent) 〇.36 g, in room After stirring at 500 rpm for 10 minutes under temperature, the mixture was allowed to stand for one day, and this was referred to as liquid C. The blocking of the isocyanate group was confirmed by the disappearance of the signal of isocyanate group 141326.doc-72-201012882 in 13C-NMR. The total amount of 3-isocyanatepropyltriethoxydecane and 2-butanone oxime is defined as the amount of the blocked isocyanatodecane compound: (A-5). Add a liquid A and a stir-mixer to a 200 ml three-necked flask, and mix at 500 rpm while adding IPA-ST-L ((C) component + (E) component) 7.20 g as liquid B in 5 minutes. The mixture was stirred at room temperature for 1 minute, and then heated under a nitrogen stream at 600 rpm and 80 ° C for 3 hours. Then, liquid C was added, and the mixture was stirred at 80 ° C for 4 hours under the same conditions, and then placed in a chamber. The mixture was allowed to stand overnight at room temperature. Further, 0.40 g of 3·aminopropyltrimethoxy decane (component (A-3)) as a D solution was added dropwise thereto over 2 minutes. After stirring at room temperature for 10 minutes, Further, it was heated under a nitrogen stream at 700 rpm and 8 (TC) for 3 hours. Then, it was allowed to stand for 1 week to obtain a coating liquid. (Comparative Example 1 shows that the coating liquid of Example 1 was not used (A-1). In the case of the coating liquid to be produced, the content of the organic polymer fine particles in the cured film is the same as in the first embodiment. Then, using the coating liquid, a laminate including a substrate and a cured film was produced in the same manner as in Example 1 (2). The obtained coating liquid and laminated body were evaluated. The evaluation results are shown in Table 4. 〇 Comparative Examples 2 to 6 A coating liquid was produced in the same manner as in Comparative Example 1 in accordance with the components and the amounts shown in Table 3, and a laminate was produced. (Comparative Examples 2 and 3 show the coating liquid produced by using the component (A_1} in the coating liquids of Examples 2 and 3) and the content of the organic polymer fine particles in the cured film and Example 141326. Doc-73·201012882 2, 3 are the same amount. Further, Comparative Example 4 is a coating liquid produced by using the component (A-5) in the coating liquid of Example 3, and is made into a cured film. The content of the organic polymer is the same as that of the third embodiment. The comparative example $ indicates that the coating liquid produced in the example 3 does not use the component (A-5) and the coating liquid produced by the bismuth component. The content of the organic polymer in the cured film is the same as that in the third embodiment. The comparative example 6 shows the coating liquid produced by using the component (A-1) and the component (C) in the coating liquid of the third embodiment. In addition, the content of the organic polymer in the iodinated film was the same as in Example 3. The obtained coating liquid and the laminated body were evaluated. The evaluation results are shown in Table 4. 141326.doc •74· 201012882 1<[1<] 1 inch? s? rn v〇i w> oo o ^ oo 5 "S 〇5 <r> 〇〇o ^京*rt 〇〇1 〇篆S〇〇1 1 s| ^ so 1 »nr〇°2 一芝〇»n °S 寸冢〇一Ο ^ 〇)Q %η ^ 〇\ rs 5 2§ — V£; 3° |1 v〇g 〇i 2§ ώ >〇5 m oo d oo 1 5 〇i" Vi oo o ^ 〇? 2pan°κ 1 |l 1 1 4 \〇<w> 1 °oo 〇V) °5 Beer 5 〇 — 〇-ο: d $ 〇? 2 1 3| 〇? 2〇g Os W 1 1 if rn m On i 〇9 »r> m 〇-r 匕O? u·) rn < 〇爹sc ώ —录——CJ 1 1 1 〇°°S 呀5 〇卜〇^ 〇安s Ci· i 寸塞·—1 vi SI 〇? 2F 141.23 | 00 |1 i' »n 〇\ 〇1 1 5 "g 〇5 v> md -: 〇S' tn rn 1 ο ? —— • 1 1 2 » o ^ °5, inch 5 〇 〇〇 ss — δ g °| —I/S n? 2I 〇衮141.23 | Γ- 卜(N 〇〇r^i —rS 4.375 _(31.〇8 copies) 1 t 5 in 〇i «λ O ^ rn §| "" 1 1 sS ^ oo —d 1 rn^ ss s inch i] 〇〇〇ο ο n 10.01 (71.12 copies) Cp *N wS 〇? 2| §鋈161.09 | sO 1.125 (13.14%) 2.625 (30· 67 copies) 1 ' 5 ss 'f σ; oi «Λ々o °〇o pan s ώ • ll s °K — w^m w* 1 1 1 2? Sm -5 〇 ο ^. ο 2.625 (30.67%) «ηΦ <Ν *η —Vi vd —^ 〇g 2§ °s og 51 158.18 | χη ¥ π荽“ rS « Λ 5 (NO 〇 Ν (Ν rn 1 1 i 呀—: vr> 〇5 *n ★ o ® O? W si \〇• 1 3l rn 1 1 S3 〇r>i ώΞ ο 〇0 ο ο 2.625 ( 31.70%) 6.125 (73.97 copies) 2°3 1§ 163.52 1 —1 2.625 (33.40 copies) 1 1 s oi m ό do? «Λ Ό °g 1 〇2 1 4 cn 1 <<n 〇〇PO °S ο — ο ^ ο 2.625 (33.40%) 6.125 (77.93 copies) ^ rn ll to 172.27 1 π荽« Γ〇2.625 (32.17 copies) 1 1 i «i ^ <N \n 〇immov〇*nr* "t 1 ll 1 4 ^ rn 1 • 2苎w 〇<N °Ξ Ο ο ο^: ο 2.625 (32.17%) 6.125 (75.06 copies) 〇I 2 2| 〇| 51 165.93 1 (N d· i —匕1 1 i 〇i vrv O Ci ® 匕of 2| 1 ll ώ 1 Λ 1 1 0 6 o inch°5 ο \〇ο ^ ο 〇\ p-—J VO <N 〇=l 匕〇 ?—U~j 2| !| 156.3 1 i £ si r〇V> OO « 1 i 〇δ VT} 00 G ^ Extensive S* °k • if °s〇s| ·-1 \£) 1 1 wi m °g 〇ΧΠ °S ο — θ'® ο it» Ci 5 ,o d 〇? =1 2° 〇? 5 rate § S ω £ ws ω § (Al) (A_2) (A-2) (A-2) , (A-4) (A-4) § SS ω (A -5) (A-3) im face; m 衮 ω USL-1385MG (solid concentration 30 mass f%) (g) ULS_385 (solid concentration 30% by mass) 3 1-methoxy-2- Propyl alcohol (g) water (g) acetic acid (g) tetramethyl decyl decane (g) M Silicate 51 (g) methyl trimethoxy decane (g) MTMS-A (g) SR2402 (g) 1 3-ring Oxypropoxypropyltrimethoxydecane IM_ Dimethoxy-3-glycidoxypropylmethyl oxime (9) 20% by mass of a benzoic acid solution (g) 1 IPA-ST-L (solid content concentration: 30% by mass) (g) 3-isodecyl propyl triethoxy decane (g) 2-butyl hydrazine (isocyanate group blocking agent) (g) 3-aminopropyl trimethyl Oxy oxime (g) < CO u D quite. Umbrella ¥铋W Umbrella¥铋001¥璨>令哒〇)~(5 葙 葙 & & ( ( ( 拿 3 3 3 φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ αΜν) dimension length <(%)!>柘w M^龙* 141326.doc •75· 201012882

(N 141326.doc (N ♦ Example 11 〇90% 0.7% 〇100/100 100/100 100/100 〇100/100 〇〇Example 10 〇 90 90% 0.7% 〇1 1 100/100 1 100/ 100 1 100/100 〇100/100 〇〇Example 9 a 〇90% 0.7% 〇1—^ 丽 100 1 100/100 100/100 〇100/100 〇〇Example 8 〇泶90% 0.7% 〇 100/100 100/100 100/100 〇100/100 〇〇Example 7 oo 〇90% 0.6% 〇(Ν 1 100/100 1 100/100 100/100 〇100/100 〇〇Example 6 oo 〇1 90% ί 0.6% 〇100/100 100/100 1 ί 100/100 〇100/100 〇〇Example 5 oo 〇索J〇^i 90% | 0.6% 〇100/100 [ i 100/100 1 100/ 100 〇100/100 〇〇Example 4 oo 〇90% ! 1 0.7% 〇100/100 I 100/100 100/100 〇100/100 〇〇Example 3 oo 〇Ί 90% ί 0.7% 〇一100/ 100 100/100 100/100 〇100/100 〇〇Example 2 o 〇90% 0.7% 〇100/100 100/100 〇100/100 〇〇Example 1 ίο Vi j本jsid 90% 0.7% 〇一100/100 100/100 〇100/100 〇〇Evaluation project from oxygen of inorganic components Content converted by compound (% by mass) Organic polymer fine particle content (% by mass: calculated value) Solution stability film appearance Total light transmittance Haze abrasion resistance Scratch resistance Adhesiveness Baked after 5 minutes of adhesion Weatherability (1000 hours) Flexibility-resistant organic particulate dispersion structure Inorganic particulate dispersion structure-76- 201012882 [εί·· 141326.doc Ό 鸾0.66 (11.02%) 1.54 (25.71 servings) 5.00 (83.47 servings) 〇i •ο Ηη〇〇0.50 (8.35%) 1 ON cn trl cn 〇(N 1 0,96 (16.03%) 1 1 0.01 (0.17%) 0.04 (0.67 parts) 1 1 1.10 (18.36%) 0.36 (6.01%) 0.40 ( 6.68%) 118.2 I ¥ £ 0.36 (10.84%) 0.84 (25.30 copies) i !/*> — ts Ο rt 00 (N 0.50 (15.06 parts) 0.50 (15.06%) 1 0.40 (12.05%) ! 1 1.10( 33.13%) 0.55 (16.57%) 1 1 0.01 (0.30%) Inch sign 〇d^. 'w1 1 1 1 1 0.40 (12.05%) 169.6 I vs. £0.72 (13.66%) 1.68 (31.88 copies) 4.25 (80.65 Share). $ Os Os 0.50 (9.49%) i 0.40 (7.59%) 1 1.10 (20.87%) 0.55 Π0.44%) 1 1 0.01 (0.19%) 〇s〇〇-dm 3.71 (70_40 servings) _ 1 1 0.40 (7.59 %) 193.2 I cn osg ^P: · ON 3.01 (21.86 parts) 2.80 (20.33 parts) 1 4.80 (34.86%) 1 — 〇 (N 1 0.96 (6.97%) 0.01 (0.07%) 00 • 1 9 oc 1 ( 20.70%) 6.65 (48.29 copies) 1.10 (7.99%) 0.36 (2.61%) 0.40 (2.90%) 91.9 1 CN ¥ 0.60 (5.43%) 1.40 (12.69 servings) 2.00 Π8.13 copies) 1 3.20 (29.01%) 1芝 cn od w- (N 1 0.96 (8.70%) 0.01 (0.09%) 0.19 (Ί.72 copies) 1 1 2.40 (21.76%) 5.60 (50.77 servings) 1.10 (9.97%) cn Ό rn 0,40 (3.63 %) 83.3 | £ 0.27 (2.58%) 0.63 (6.02 servings) 2.00 i Π9.Π portion) 0.09 (0.86 parts) i 3.20 (30.59%) 1 哀 (N 〇< CN 1 0.96 (9.18%) 0.01 (0.10 %) ci —(N 1 1 2.16 I (20.65%) 1 5.04 (48.18 copies) 1.10 (10.52%) 0.36 (3.44%) 0.40 (3.82%) gg W g S'" (Al) 1 < (Α -2) (Α-4) g S' gg (A-5) (A-3) Umbrella 铋 S S Φ ULS-1385MG (solid content concentration: 30% by mass) (g) 1-methoxy-2 -propanol (g) water (g) acetic acid (g) M Silicate 51(g) _i ¢ - MTMS -A(g) &- νϋ in 1 '1^ 5 mass% p-toluenesulfonic acid methanol solution (g) 1 1 : 20 mass% p-toluenesulfonic acid methanol solution (g) IPA-ST-L (solids concentration 30% by mass) (g) 3-iso(L-acid propyl triethoxy oxetane (g) 2-butanone oxime (isocyanate-based blocking agent) 3-aminopropyltrimethoxy fluorene ( g) Liquid A 1 D. . /0驷铋^^. /0001 Carbon porphyrin smear 4 哒〇)~(<绔桕<(%)1> alkali" €:Shulong* •77- 201012882 inch 崦【inch<】 Comparative example 6 m 〇〇〇 88% 0.8% X m 100/100 100/100 100/100 〇100/100 〇1 Comparative Example 5 On 00 X 87% 0.9% X (N 100/100 50/100 20/100 〇100/100 〇1 Comparison Example 4 00 X 87% 0.9% 〇 (N 100/100 50/100 20/100 〇100/100 〇〇Comparative Example 3 00 00 〇4? Af>j 90% 0.7% 〇cn 100/100 100/100 100 /100 〇100/100 〇〇Comparative Example 2 CN Ο 〇〇本JTtifi 90% 0.7% 〇m 100/100 100/100 100/100 〇100/100 〇〇Comparative Example 1 〇90% 0.7% 〇100/100 100/100 100/100 〇100/100 〇〇Evaluation item from oxide content of inorganic component (% by mass) Organic polymer particle content (% by mass: calculated value) Solution stability film appearance Total light transmittance haze磨Abrasion resistance, scratch resistance, adhesion, and adhesion resistance after boiling for 5 hours (1000 hours) Condensation heat-resistant organic fine particle dispersion structure, inorganic fine particle dispersion structure 141326.doc -78 - 201012882 It is known from Tables 1 to 4. , the invention The cloth liquid, the cured film obtained by the film, and the laminate (Examples 1 to 11) were all qualified in almost all evaluation items. The solutions of Comparative Examples 1 to 3 and Comparative Example without the component (A-1) were contained. The stability, the film appearance, the transparency, the adhesion, and the boiling resistance were good, but the scratch resistance was inferior to those of Examples 1 to 11. Further, the film appearances of Comparative Examples 4 and 5 containing no (Α_5) component were obtained. The transparency and the adhesion were good, but the solution stability and the boiling resistance were inferior to those of Examples 1 to 11. Examples 12 to 16 The coating liquid of Example 以 was obtained as a cured film by a bar coater. 3 μιη by coating on the surface of a polycarbonate (pc) molded body having a thickness of 3 mm or a corona-treated polypropylene sheet [Manufactured by Idemitsu Uniteeh Co., Ltd.] Trade name: Superpurelay, product number: SG_ 14〇1 '(:'The thickness is 3〇〇0„1 (the total light transmittance is 94%, the haze value is 2.3%)] The upper part is thermally cured at 130 ° C for 2 hours, thereby producing A laminate of a substrate and a cured film. Further, a layered body was obtained by forming an inorganic hard substance layer on the layered body produced as described above by the following method. The obtained laminate including the substrate, the cured film, and the inorganic hard layer was evaluated. The evaluation results are shown in Table 5. Film formation of inorganic hard layer (1) Si〇x The laminated body including the substrate and the cured film was placed in a plasma CVD apparatus to perform evacuation until the vacuum in the apparatus reached 2.7 χ 1 (Γ3 Pa, The temperature of the substrate is raised to 10 ° C for 5 minutes, and the substrate is degassed. After that, after returning to room temperature, the gas is exhausted until the vacuum in the device is 141326.doc -79· 201012882 2.7χ1 (Γ4 Pa. After the vacuum degree is 2.7乂1〇-4卩&, introduce 8 out of 4 gas, :〇 gas and Ar gas into the device, the gas flow rate is: siH4 gas flow rate is i cm3/min , n2 helium gas flow rate is 200 cm3 / min, Ar gas flow rate is 3 〇〇 cm3 / min, when the vacuum is stable at about 2.7 Pa, electric power is applied to generate plasma, thereby forming a film thickness of 5 μηι on the cured film. SiOx (l.8Sxg2) film (inorganic hard layer). (2) Amorphous carbon film

The produced laminate including the substrate and the cured film is placed in a plasma CVD apparatus, and evacuated until the degree of vacuum in the apparatus reaches 27 x 1 〇 -3 pa, and the temperature of the substrate is raised to 1 〇〇 ° C ' After the substrate was removed for 5 minutes, it was returned to the temperature, and then evacuated until the degree of vacuum in the apparatus reached 2.7 x 10 4 Pa. To a plasma CVD apparatus with a vacuum of 2.7 x 1 〇 -4 Pa, a gas flow rate of 1 cm 3 /min with a gas flow rate of 150 cm 3 /min and an Ar gas flow rate of 300 cm 3 /min was introduced. Eh gas, Η2 gas and heart, when the true working degree is about 2.7 Pa, electric power is applied to generate electropolymerization, and an amorphous carbon film (inorganic hard material layer) having a film thickness of 7 μm is formed. (3) SiNy The laminated body including the substrate and the cured film was placed in an electropolymerization CVD apparatus, and evacuated until the vacuum in the apparatus reached 2.7x1()_3 pa, and the temperature of the substrate was raised to 1. Hey. (:, hold for 5 minutes, degas the substrate. Then 'restore to room temperature' and vent until the vacuum in the device reaches 2.7x10·4 Pa. 141326.doc • 80 · 201012882 Plasma CVD In the apparatus, SiH4 gas, NH3 gas and Ar gas are introduced into the gas flow rate of SiH4 gas flow rate of 1 cm3/min, NH3 gas flow rate of 200 cm3/min, and Αγ gas flow rate of 400 cm3/min, when the vacuum degree is stable to 2.7 Pa. On the left and right sides, 'electricity is applied to generate plasma' to form a SiNy (l_2$4/3) film (inorganic hard layer) having a film thickness of 7 μη. (4) Si02 is a laminate comprising a substrate and a cured film. It is installed in the ion key device. 'The evaporation source is Si〇2 crystal grain. Exhaust until the vacuum in the device reaches 2.7χ1 (Γ4 Pa. Apply high frequency voltage ι·5 kV to the high frequency coil, and introduce argon gas and helium gas. 2 gas. After the introduction of the gas is stopped, the vacuum degree in the apparatus is 1·33 χ UT3 Pa ', and the Si〇2 ion plating is performed for 2 minutes. Thereafter, the vacuum inside the apparatus is left and left to cool for 20 minutes, thereby being cured on the cured film. Forming a SiO 2 (1.8SxS2) film with a film thickness of 1.5 μη (inorganic hard layer Comparative Examples 7 to 11 Using the coating liquid of Comparative Example 1, a laminate was obtained in the same manner as in Examples 12 to 16. The obtained laminate including the substrate, the cured film, and the inorganic hard layer was evaluated. The evaluation results are shown in Table 5. 141326.doc -81 - 201012882 Comparative Example 11 Comparative Example 1 U CU Si02 jni>j 90% 0.7% 〇50/100 50/100 10/100 〇50/100 Comparative Example 10 Comparative Example 1 U CX, 1 SiNv , ^>i 90% 0.7% 〇r < 40/100 40/100 10/100 〇40/100 Comparative Example 9 Comparative Example 1 〇Amorphous carbon film joai 90% i 1 0.7% 〇 50/100 50/100 10/100 〇50/100 Comparative Example 8 Comparative Example 1 & Η Si〇x cable -1 92% i 2.5% 〇30/100 30/100 10/100 〇30/100 Comparative Example 7 -1 Comparative Example 1, 〇Pm 1 SiOx , 汝90% 0.7% 〇50/100 50/100 10/100 〇50/100 Example 16 Example 1 U Ο, Si02 90% 0.7% 〇ί-Ή 100 /100 〇100/100 Example 15 Example 1 U Ph SiNv 90% 0.7% 〇100/100 100/100 100/100 〇100/100 Example 14 Example 1 U Oh -1 amorphous carbon film 90 % 0.7% 〇100/100 100/100 1 100/100 〇100/100 implementation Example 13 Example 1 Oh Ph SiOx 92% i 2.5% 〇100/100 1 100/100 100/100 〇100/100 Example 12 Example 1 U P-. -csi 1 90% I 0.7% 〇100/100 100/100 100/100 〇100/100 Evaluation item Coating liquid resin substrate 1 Inorganic hard material layer 1 Film appearance J Total light transmittance Haze to abrasion resistance Scuffing adhesion After 5 hours of boiling adhesion Weather resistance (1000 hours) Flexibility heat resistance 141326.doc · 82· 201012882 It can be seen from Table 5 that the laminates using the coating liquid of Example 1 (Examples 12 to 16) were all qualified in substantially all evaluation items. . In Comparative Examples 7 to 11, the laminate of the coating liquid of Comparative Example 1 was used, and the film appearance, transparency, abrasion resistance, and scratch resistance were good, but the adhesion and boiling resistance were compared with those of Examples 12 to 16. difference. [Examples 17 to 20 and Comparative Examples 12 to 14] The characteristics in the above examples were obtained in accordance with the following procedures. (1) The content of the oxide derived from the inorganic component in the cured film (mass 0 / 〇) is thermolyzed by a sample obtained by thermally hardening the coating liquid on a Teflon (registered trademark) culture. Next, the temperature is raised at 2 ° C / min, room temperature ~ 800 ° c), according to the residue at 80 (TC). (2) The content of organic polymer particles in the cured film (mass 0 / 〇) Calculated by calculation. Specifically, the hydrolysis/condensation reaction of the (into_5) component is completed ((A) component), organic polymer microparticle (component (B)), and colloidal ceria component) And the mass % of the organic polymer fine particles in the total mass of the cerium oxide (component (F)). (3) The cerium oxide content (% by mass) in the cured film was calculated by calculation. (4) The solution stability of the coating liquid was sealed and stored at room temperature for 14 days, and the presence or absence of gelation was visually observed. For the gel, the viscosity is measured by the tuning fork vibrating vibrometer SV-10 of A & D Co., Ltd., and the rate of change compared with the initial period is less than 3 times, which is more than 3 times. (5) Film appearance 141326.doc • 83 - 201012882 The appearance of the hardened enamel was visually observed, and the foreign matter, the speckle pattern, and the white turbidity were confirmed, and those who did not confirm the above were recorded as "good". ) Total light transmittance and haze The total light transmittance and haze of the laminate were measured by a direct reading haze meter (manufactured by Suga Testing Machine Co., Ltd., HGM-2DP). (7) Abrasion resistance and scratch resistance For the evaluation of wear resistance, a 500 rpm TABER abrasion test was carried out using a wear wheel cs_1〇F and a TABER abrasion tester (rotary wear tester) (manufactured by Toyo Seiki Co., Ltd., model.TS) under a load of 4.9 N. , the haze before TABER abrasion test and TABER The difference in haze (ΔΗ) after the consumption test is less than 15 and is referred to as "〇", and the difference in haze is 15 or more as "X". The evaluation of scratch resistance is based on Example 1 7~ 2〇 and Comparative Example 4, using steel wool #0000 (load 4.9 N), reciprocating 5 times in 2〇〇〇mm/sec, visually assessing the damage of the surface. The damage is recorded as "1", the person who is slightly damaged is referred to as r 2", and the person whose surface is damaged by more than half of the friction is recorded as "3". (8) Adhesiveness is used in accordance with JIS K 5400 The razor blade cuts the sample (hardened film) into 11 slits at intervals of 2 mm to form i 网格 a grid, and uses commercially available cellophane tape with a finger pad ("CT-24 (width 24 mm) )), Nichiban Co., Ltd.) After fully adhering to the sample, it is quickly peeled off at an angle of 9 〇. The number of meshes in which the cured film is not peeled off and remains is indicated by Χ/100. The adhesion of the film was evaluated. 141326.doc -84 - 201012882 (9) Boiling resistance The sample of the laminate was immersed in boiling water in a stainless steel beaker. After the hour, the adhesion was evaluated. The evaluation of the adhesion was carried out in the same manner as in the above (8). (10) The weather resistance test was carried out for 2400 hours of the xenon arc lamp (Atlas ci65, the output was 6.5 kW, black panel temperature is 63 ° C, relative humidity is 50%). Weather resistance is evaluated by changes in the hardening film adhesion before and after the test. (11) Flexibility is limited to 100 mm x width 50 mm x thickness 1 A sample of a resin laminate was produced in the same manner as in each example except that a polycarbonate standard plate (trade name: p〇lyca_Ace, product number: ECK100) manufactured by Sumitomo Bakelite Co., Ltd. was used as the substrate. The both ends of the sample were held with a finger, and forced bending of a curve having a radius of 5 mm was performed 10 times. A person who does not have a crack on the layer is referred to as "〇", and a person who has a crack is referred to as "X". (12) Heat resistance was measured by heat resistance test (manufactured by TABAI, PS-222) at ll (TC, 720 hours). The heat resistance was evaluated by the change in the cured film adhesion before and after the test. (13) Organic particles The dispersed structure was observed by a TEM (transmission electron microscope) for the cross-section of the cured film, and 10 organic fine particles present in the region of 1 μm square were selected, and Freesoft: ΝΙΗ 141326 manufactured by National Institute of Health, USA. Doc -85- 201012882

Image 1.63 Find the average particle size. The average particle diameter of the organic fine particles is referred to as "〇", and the average particle diameter is greater than 2 〇〇 (10), and the particle size is 2 〇〇 nm or less. In the case where the particles are fused and the shape of the worm having a particle diameter of fine (10) or more is "Δ". (14) Inorganic fine particle dispersion structure The average particle diameter of each of the oxidized cerium particles and the cerium dioxide cerium particles in the cured film was determined in the same manner as in the above (13). Those whose average particle diameter is 200 nm or less are referred to as "〇", and those whose average particle diameter is larger than nm are referred to as "X". Further, in the examples and comparative examples, the details of the raw materials described in the trade names are as follows. (A) Ingredients: M Silicate 51 "Polyalkyloxydecane as a partial condensate of tetradecyloxydecane (average three to pentamer)" Tama Chemical Industry Co., Ltd. (B) Ingredients: ULS- 1385MG (Ultraviolet absorption skeleton: benzotriazole) Manufactured by One Society Oil & Fat Industry Co., Ltd. (water dispersion/solid content concentration: 30% by mass) ^ (B) Component: ULS-385MG (UV absorption skeleton: diphenyl)曱_系) Manufactured by ONE Oil & Fat Industry Co., Ltd. (water dispersion/solid content concentration: 30% by mass) ^ (C) Component: IPA-ST-L (colloidal cerium oxide) 曰Production Chemical Industry Co., Ltd. Isopropanol dispersion, colloidal cerium oxide concentration of 30% by mass, average particle size of 4〇~50 nm (manufacturer announced 141326.doc -86 - 201012882 value)) (F') component: NeedralU-15 (cationic Hydrazine Hydroxide Dispersion (manufactured by Doki Chemical Co., Ltd.) (water dispersion, yttrium oxide concentration of 15% by mass, average particle size of 8 nm or less, pH of 3.5 (manufacturer catalogue value)) _ (again, Use the Zetasizer Nano series manufactured by Malvern Nano-ZS measured the zeta potential of Needral U-15 at 20 ° C with a dispersion medium of 50, and the result was +28.8 mV, confirming that the oxidized ® ruthenium particles were cationic). (F') component: NeedralH-15 (acid-stable cerium oxide aqueous dispersion) manufactured by Doki Chemical Co., Ltd. (water dispersion, cerium oxide concentration: 15 to 16% by mass, stabilizer: hydrochloric acid not up to 1.0% by mass, The pH value is 1 to 3 (manufacturer's published value)) (Further, using the Zetasizer Nano series Nano-ZS manufactured by Malvern, the temperature is 20 ° C, the dispersion medium is water, and the cumulative number of times is 50 times. The zeta potential was measured and found to be +53.7 mV, confirming that the oxidized Φ 钸 particles are cationic). (1) Preparation of component (F) (dispersion F1) Manufactured according to the components and the amounts of the amounts in Table 6. Into a sample tube having a volume of 50 ml, 10.0 g of Needral H-15 ((F') component) was placed, and while stirring at 500 rpm, 1-methoxy-2-propanol was sequentially added dropwise over 1 minute. ((E) component) 7.0 g, tetraethoxy decane (component (A)) 2.23 g. Then, after stirring at room temperature for 90 minutes, it was allowed to stand at room temperature for 90 minutes. This was placed in a 100 ml three-burner 141326.doc -87-201012882 bottle equipped with a cooling tube, and stirred at 500 rpm while being heated at 80 ° C for 4 hours under a nitrogen stream. Then, it was allowed to stand at room temperature for one week to prepare a dispersion F1 (component (F)) containing a reaction product of a decane compound and cerium oxide. (2) Dispersibility test of (F) component and anionic fine particle sol IPA-ST-L ((C) component, IPA dispersion in which anionic colloidal ceria is dispersed is introduced into a sample tube having a volume of 10 ml Sol) 1_0 g and a stirrer. While stirring at 400 rpm, 1.0 g of a dispersion F1 ((F) component) containing a reaction product of a smelting compound and cerium oxide was added dropwise over 1 minute, followed by room temperature Stir for 1 hour. It was visually confirmed that the dispersed state after the completion of the stirring was such that aggregation, precipitation, and gelation were not generated and dispersed. (3) Preparation of component (F) (dispersion F2) Manufactured according to the components and input amounts of Table 6. Into a sample tube having a volume of 50 ml, 10.0 g of Needral H-15 ((F') component) was placed, and while stirring at 500 rpm, 1-methoxy-2-propanol was added dropwise over 1 minute (( E) component) 7.0 g, tetraethoxy decane (component (A)) 1.49 g. Then, after stirring at room temperature for 90 minutes, it was allowed to stand at room temperature for 90 minutes. This and the stirrer were placed in a 100 ml three-necked flask equipped with a cooling tube, and while stirring at 500 rpm, 3-glycidoxypropyltrimethoxy decane (component (A)) 0.30 was added dropwise over 1 minute. g, stirred at room temperature for 120 minutes. One side was stirred at 500 rpm and heated at 80 ° C for 9 hours under a nitrogen stream. Then, it was allowed to stand at room temperature for one week to prepare a dispersion F2 (component (F)) containing a reaction product of a decane compound and an oxidized product. In the same manner as in the dispersibility test of the above (2), it was confirmed that the dispersion liquid F2 was not aggregated, precipitated, or gelated and dispersed. 141326.doc -88 - 201012882 [Table 6] Ingredient Fraction F1 Dispersion F2 Needral Η-15(g) (F) 10.0 10.0 L-methoxy-2-propanol (g) (G) 7.0 7.0 Four Oxyfluorene Xg) (8) - _ Tetraethoxydecane (g) (A) 2.23 1.49 M Silicate 51(g) (A)-3-Ethoxypropyloxypropyltrimethoxysulfonate (g) ( A) - 0.30 methoxy-2-propanol (for dilution for displacement of the dispersion medium) (g) (G) - - Examples 17 to 1 8 (4) Preparation of coating liquid According to the composition of Table 7 and The amount of input was prepared. The organic polymer microparticles were injected into a sample tube having a volume of 50 ml: ULS-1385MG (Example 17) or ULS-385MG (Example 18) ((B) component + (E) component) 0.85 g, one side was 500 After stirring at rpm, 1-methoxy-2-propanol ((E) component) 4.25 g, water ((E) component) 0.50 g, acetic acid ((G) component) 2.80 g, M were added dropwise over 1 minute. Silicate 51 ((A-1) component) 0.40 g, methyltrimethoxydecane ((A-2) component) 1.51 g, dimethoxy-3-glycidoxypropyldecyl decane (A -4) Ingredient) 0.55 g, 20 mass ° / 〇 p-toluenesulfonic acid decyl alcohol solution (component (D) + (E)) 〇. 5 g. Then, after stirring at 500 rpm for 60 minutes at room temperature, it was allowed to stand for one day as a liquid A. Add a liquid A and a stirrer to a 200 ml three-necked flask equipped with a cooling tube, and while stirring at 500 rpm, add IPA-ST-L as a liquid B in 5 minutes ((C) component + (E) component) 6.50 g 'Stir at room temperature for 20 minutes. Then, the mixture was heated and stirred under a nitrogen stream at 500 rpm and 80 ° C for 7 hours, and then allowed to stand overnight at a temperature to obtain an A' solution. 141326.doc -89- 201012882 To the sample tube with a volume of 20 ml, add 1.10 g of isocyanatopropyltriethoxydecane and 2-butanone oxime (blocking agent for isocyanate group) 〇.35 g, after stirring at 500 rpm for 1 minute at room temperature, it was allowed to stand for one day and used as a liquid c. The blocking of the isocyanate group was confirmed by the disappearance of the signal of the isocyanate group in i3c_NMR. The total amount of 3-isocyanatepropyltriethoxydecane and 2-butanone oxime is defined as the amount of the blocked isocyanatodecane compound: (A-5). While stirring A and liquid at 650 rpm, 3.26 g of a dispersion F1 ((F) component + (E) component) containing a reaction product of a decane compound and cerium oxide was added dropwise over 5 minutes, and stirred at room temperature for 2 minutes. . The mash was then added over 5 minutes and stirred at room temperature for 1 minute. Then, the mixture was heated and stirred under a nitrogen stream at 65 rpm and 80 ° C for 4 hours, and then allowed to stand at room temperature overnight. Further, 3-aminopropyltrimethoxydecane (component (A-3)) as a solution D was added dropwise thereto for 2 minutes to 〇.4〇 g. After stirring at room temperature for 1 minute, it was heated under a nitrogen stream at 45 rpm and 80 ° C for 3 hours. Then, it was allowed to stand for 1 week to obtain a coating liquid. (5) The production of the laminate was carried out using a polycarbonate substrate [manufactured by Idemitsu Kosan Co., Ltd., trade name: Tarflon, product number: IV22〇〇R (weathering grade), thickness: 3 mm (total light transmittance: 9) 〇%, haze value 〇5%)] as a resin substrate. The coating liquid obtained above was applied to the surface of a polycarbonate molded body having a thickness of 3 mm by a bar coater at a thickness of 7 μm, and was thermally cured at 130 ° C for 2 hours. Thereby making a laminate. 141326.doc •90· 201012882 The evaluation results are shown in the evaluation of the obtained coating liquid and laminate. Table 9 〇 Examples 19 to 20 In the above "(4) Production of Coating Liquid", "Dispersion (4) was used instead of Dispersion F1, and the coating liquid of the Example was prepared in accordance with the components and the amount of the ingredients in Table 7 and a laminate was produced. The evaluation results of the obtained coating liquid and laminate were not shown in Table 8. Comparative Example 12~14

In the above "(4) Production of coating liquid", Needral U-15 or Needral H-15 shown in Table 7 was used instead of the dispersion liquid F1, and the coating liquid of the comparative example was prepared in accordance with the composition of Table 7 and the crucible. And make a layered body. The evaluation results of the obtained coating liquid and laminate were shown in Table 8.

141326.doc 91- 201012882 【卜磷】 ϊ « 一 1 3° <^| ch$ 甘ο • 1 4.25 (66.82 servings) /— Λ拿Λ«Λ Ό 〇°® °b • 2.00 (21.45%) 0.95 (14.94%) 0.01 (0.16%) ο <-η ο^. ο ; 0.69 1 (10.85%) % 1 1 1 1 <s 0.85 Π 1.36 copies) 1 t 〇I —·ΓΤ) —* 0.35 (5.50%) _ 121.68 1 Ϊ 1 I 0.255 (2.66%) 0.595 (6.22 parts) i 0.50 (5.22m 2.80 ! (29.26%) 1.51 ; (15.78%) 1 0.55 (5.75%) 0.01 (0.10%) 0.04 (0.42 copies) 1.95 (20.38%) 1 4.55 · (47.54 copies) 1 • 1 • * 0.249 (2.60%) 1,411 (14.74 copies) 1.10 (11.48%) 2岑0.40 (4.18%) 118.55 1 <N Ϊ - O 0.255 (2.66%) 0.595 (6.22 servings) 1 5 Beer 5 0.50 ! 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'5 1.51 (15.58%) 2" 0.0! i (〇.!〇%) I inch i ο — ο 4.55 (46.96 copies) I 2.90 1 (29.93 copies j_ 1 1 1 1 • 1.10 (1135%) 0.40 (4.13 %) S § S ω g ω 〇(Al) (A-2) (A-4) § ω S g ε g ω e ω gs (Α-5) (A-3) $ ΦΙ Φ USL-1385MG The concentration of the substance is 30®f%) (g) ULS-385MG (solid concentration is 30% by weight) (g) 1-methane-2-propanyl (g) water (g) acetic acid (g) M Silicate 51(g) Methyl trimethyldecyl decane (g) .. _ _ _ one one ___ one _ 1 di-foxy-3-glycidoxypropyl methyl fluorene (g) 20% by mass p-Toluenesulfonic acid methylation solution (g) IPA-ST-L (solid content concentration: 30% by mass) (g) ρ Trial W * Review a < π 4d ^ ud 51 铋 2 • a Lifted U- 15 (solid content concentration: 丨5 mass%) (g) Needral H-15 (solid content concentration: 15% by mass) 3-isodecanoic acid propyl triethoxy oxime (g) 2-butyl silk肟 (isodecanoate-based blocking agent) (g) 3-aminopropyltrimethoxydecane (g) A liquid 1 I 1 Μ 鸾V ω . %ii,w*yoool%^l*wl,璨4噶噶(0~<) Constitutional Length<(%>Electricity"^€:Zilong* 141326.doc •92- 201012882 ο· 00&lt ;[8<] 141326.doc 1Comparative Example 14 1 vn 〇j〇Sti 88% [2.0% I 〇m 100/100 80/100 80/100 〇100/100 〇〇Comparative Example 13 ΓΟ vn X |White turbidity| 1 1 1 1 1 1 1 1 1 1 1 Comparative Example 12 r〇〇88% 2.0% 〇rH 100/100 80/100 80/100 〇100/100 〇〇|Example 20 ! ΓΛ VO 〇90% | 1.2 % | 〇100/100 100/100 100/100 〇100/100 〇〇Example 19 m 〇90% | 1.2% I 〇100/100 100/100 〇100/100 〇〇Example 18 1 iTi 〇89% 1.3% I 〇t Gang/Excited 100/100 100/100 〇100/100 〇〇Example 17 〇•ίώί 89% | 1.3% I 〇^—4 100/100 1_ 100/100 100/100 〇100/ 100 〇〇Evaluation item from oxide content of inorganic component (% by mass) Organic polymer microparticle content (% by mass: calculated value) Cerium oxide content (% by mass: calculated value) Solution stability film appearance Total transmittance haze Abrasion resistance, abrasion resistance, adhesion, boiling, adhesion after 5 hours Weatherability (2400 hours) for the flexural heat-resistant organic fine particle dispersion structure inorganic fine particle dispersion structure - 93 - 201012882 The coating liquids of Examples 17 to 2 are all good in the stability of the von/liquid mixture, and the laminate obtained therefrom The body also obtained excellent results in all evaluations. On the other hand, the coating liquid of Comparative Example 13 was low in stability and low in actual value, and was inferior in adhesion to (4) 12 and 14. [Examples 21 to 32, Comparative Examples 15 to 26J Examples 21 to 32 [Production of Resin Laminate] The coating liquid of ♦ Too%, * _ W is 盥 manufactured by Examples 1, 2, 5, and 6 was used as a cured film. The film is applied to the surface of the substrate in such a manner that the thickness thereof is 2 to 3 μΐη, and is thermally hardened as shown in the following <Temperature curing conditions of the substrate and the cured film>, at a temperature and time suitable for the substrate to be used. Thereby, a laminate including a substrate and a cured film was produced. Next, a transparent conductive film was formed on the produced laminate including the substrate and the cured film by the following method to obtain a resin laminate. The results of evaluation of the obtained resin laminate including the substrate, the cured film, and the transparent conductive film are shown in Table 9. <Heat-hardening conditions of substrate and cured film> (1) Polycarbonate [thickness: 400 μηι (total light transmittance: 92%, haze value: 0.4%)], 120 ° C, 2 hours (2) Polyethylene terephthalate [manufactured by Unitika Co., Ltd., trade name: Emblet 'grade: s, thickness 25 μιη (total light transmittance 89%, haze value 2.5 ° /.)], i 〇〇°c, 2 hours (3) Polypropylene [Manufactured by Idemitsu Unitech Co., Ltd., trade name: Purethermo, thickness 250 μηη (total light transmittance 94%, haze value 141326.doc -94· 201012882 8.5 %)], i〇〇°c, 2 hours <Formation method of transparent conductive film> (1) IZO film

The produced laminate including the substrate and the cured film was placed in a sputtering apparatus (Shimadzu HSM-552) to perform evacuation until the degree of vacuum in the apparatus reached 1. Οχ 1 (Γ4 Pa. Thereafter, argon was made Into the device, adjust the pressure inside the device to 0·2 Pa. The target system uses lz〇 (In203: ZnO=90: 1〇 mass〇/〇) sintered body. Splash DC (direct current 'DC' output) A transparent conductive film with a film thickness of 2 〇 nm or a film thickness of 120 nm is produced at a power of 1 。W. The substrate temperature is room temperature. (2) The IZTO target is used for the IZTO thin film target system (ln203 : ZnO : Sn02 = 20 : 40 40% by mass is formed in the same manner as described above. (3) The ZTO film is formed in the same manner as the above-mentioned target system using a ZTO target (ZnO: Sn〇2 = 10: 90% by mass) (1). 4) Sn02 thin film target system uses SnOJA junction target Sn02 film. The same as (1) above.

(5) The ITO thin film target was formed by the same method as the above (1) using an ITO target (ln203: Sn〇2 = 90 : 10 mass V, 0). After formation, brake m in the atmosphere. W was heat treated in an oven at 120 C for 1 hour. Comparative Example 15 to 26 141326.doc • 95-201012882 In the film of Example 21, the substrate was cured, and a transparent conductive film was directly formed to obtain a resin laminate. The results of evaluation of the obtained laminate including the substrate and the transparent conductive film are shown in Table 10. The characteristics of each of Examples 21 to 32 and Comparative Examples 5 to 26 were obtained in accordance with the following procedures. 0) Film appearance The appearance of the resin laminate was visually observed, and the presence or absence of foreign matter, speckle patterns, and cracks was confirmed. Those who did not confirm the above were referred to as "〇", and those who confirmed the above were referred to as "X". (2) Total light transmittance and haze The total light transmittance and haze of the resin laminate were measured by a direct reading haze meter (manufactured by Suga Test Machine Co., Ltd., HGM_ 2DP). (3) Surface hardness The surface of the transparent conductive film of the resin laminate was evaluated in accordance with JIS K5600-5-4' using a pencil scratch hardness tester (manual type) (manufactured by Imoto Seisakusho Co., Ltd.). (4) Scratch resistance The surface of the transparent conductive film was evaluated by visual inspection using steel wool #0000' after reciprocating the surface of the transparent conductive film of the resin laminate with a load of 4.9 N and 2000 mm/sec. Damaged state. The person who is completely undamaged is marked as "1", the person who is slightly damaged is marked as "2", and the person whose face is damaged by more than half is marked as "3". (5) Adhesion 14I326.doc -96· 201012882 According to JIS Κ 5400', the surface of the transparent conductive film of the resin laminate is cut into the slits of 11 vertical and horizontal lines at intervals of 2 mm using a razor blade to form i 〇〇 In the grid, the commercially available cellophane tape ("cT_24 (width: 24 mm)", manufactured by Nichiban Co., Ltd.) and the surface of the transparent conductive film were charged with the fingertips, and the film was quickly peeled off at an angle of 90 C. The number of meshes (X) in which the transparent conductive film was not peeled off and represented by X/100 was evaluated to evaluate the adhesion of the transparent conductive film. (6) Moisture resistance in the moisture resistance test (small environment tester, manufactured by Espec Co., Ltd. 'SH-221) in '5 in TC, 95 RH% environment, after standing for 1 hour, the dense The adhesion was evaluated in the same manner as in the above (5). (7) The buckling resistance was sandwiched between the ends of the resin laminated ruthenium sample by fingers, and the radius was 5 〇 mm. Forced bending of the curve, check for the presence or absence of cracks or peeling on the layer. 'The person who has not confirmed the number is marked as "〇" and will be identified as "X". (8) The specific resistance is measured by a low resistivity meter. L0resta-EP (manufactured by Mitsubishi Chemical Corporation), the specific resistance was measured on the surface of the transparent conductive film of the resin laminate by the four-probe method. (9) The concentration of the carrier was carried out by the van der Pole method. The Hall measuring device and its measurement conditions are as follows: 141326.doc -97- 201012882 • Hall measuring device manufactured by Dongyang Technology Co., Ltd.: Resi Test 8310 • Measurement conditions Measurement temperature: room temperature (25 ° C)

Measuring magnetic field: 0.5 T

Measurement current: 1〇_12~1〇_4 A Measurement mode: AC (alternating current) magnetic field (10) Crystallinity of transparent conductive film The determination of crystallinity was carried out by X-ray diffraction measurement. The measurement conditions of X-ray diffraction (XRD, X-ray diffraction) are as follows. Those who have no clear crystallographic peaks are regarded as amorphous. • X-ray diffraction measuring device

Manufactured by Rigaku Co., Ltd.: Ultima-Ill • Measurement conditions X-ray: Cu-Κα ray (wavelength not 1.5406 A, monochromatized with graphite monochromator)

Output power: 50 kV-120 mA 2Θ-Θ reflection method, continuous scanning (1.0°/min) 2Θ Measurement angle: 5~80° Sampling interval: 0.02° Slit DS, SS: 2/3. , RS: 0.6 mm 141326.doc •98- 201012882

6 <[6<] 141326.doc Example 32 Example 6 〇ITO (20 nm) 〇90% 0.4% [Χι 100/100 1- 1 100/100 〇320 Crystallization Example 31 Example 6 U Oh Sn02 (20 nm) 〇90% 0.4% 100/100 100/100 〇1200 ON Amorphous Example 30 Example 5 U ZTO 1 (120 nm) 〇90% 0.4% (X) 100/100 100/100 〇1750 ΓΟ Rg Δϋ - Example 29 Example 2 cu cu ZTO (20 nm) 〇90% 0.4% Uh 100/100 100/100 〇2200 Amorphous Example 28 | Example 1 PET IZTO (120 nm) 〇87% 2.0% X 100/100 1 100/100 〇2630 0.88 Amorphous Example 27 Example 1 PET IZTO (20 nm) 〇87% 1.8% ! loo/ioo 1 ;100/100 〇2950 0.87 Amorphous Example 26 Example 1 Ok Oh IZO 1 (120 nm) 〇91% 5.0% CQ m ! loo/ioo 1_ 100/100 〇410 ON Amorphous Example 25 Example 1 Ph Oh IZO 1 (20 nm) 〇91% 5.0% PQ ro 100 /100 100/100 〇1 1 490 Amorphous Example 24 Example 1 u cu IZTO (120 nm) 1 〇90% 0.4% E-Lh 100/100 1 100/100 〇2750 0.98 Amorphous Example _23__| Example 1 U cu IZTO (20 nm) 〇90% 0.4% I-Ih 100/100 100/ 100 〇 3200 0.91 Amorphous Example 2, Example 1 U cu IZO (120 nm) 〇 90% 0.4% | Xt 100/100 100/100 〇 400 inch amorphous Example 21 Example 1 U Pk IZO (20 nm 〇90% 0.4% 100/100 1 100/100 〇480 «r; Amorphous evaluation item _1 Curing film (coating liquid) Resin substrate Transparent conductive film Appearance Total light transmittance 镞 Surface hardness Scratch resistance Moisture resistance, flexural resistance, specific resistance (μΩοιτι), carrier concentration (Xl020/cm3), crystallinity of transparent conductive film-99-201012882 141326.doc Comparative Example 26 U CU ITO (20 nm) Ο 88% 0.4% 1 >6Β m 100/100 100/100 X g yn 00 cn Crystallization Comparative Example 25 U PU Sn02 1 (20 nm) 〇88% 0.4% >6Β ΓΛ ί 100/100 丽100 ο 1695 rn Amorphous Comparative Example 24 U Pm ZTO (120 nm) ο 88% -1 0.4% >6Β cn 1 100/100 100/100 ο 2520 as o Amorphous Comparative Example 23 U PU ZTO (20 nm) j ο 88% 0.4% >6Β ΓΛ [ ! 100/100 ί 00/100 〇3251 0.86 Amorphous Comparative Example 22 PET IZTO (120 nm), ο 87% -1 2.5% CQ XC^) Γ 1 100/100 10/100 ο 3793 0.65 Amorphous comparison Example 21 PET IZTO (20 nm) i ο 87〇/« 2.4% CQ X m I 1 100/100 100/100 0 4329 0.61 Amorphous Comparative Example 20 IZTO (120 nm) X 1 90% 10.0% > 6Β m Γ ; 50/100 0/100 X 1 1 Amorphous Comparative Example 19 & IZO (120 nm) X 90% 10.0% >6Β 1 ι 50/100 0/100 X 1 1 Amorphous Comparative Example 18 IZTO (120 nm) ! ο 88% 0.4% >6Β m 1 100/100 100/100 ο 3745 0.75 Amorphous Comparative Example 17 IZTO (20 nm) 〇88% 1 0.4% 1 1 >6Β cn 100/100 100/100 ο 4542 0.67 Amorphous Comparative Example 16 IZO (120 nm) j 〇88 % 0.4% >6Β m 1- 100/100 1 100/100 0 00 Amorphous Comparative Example 15 IZO Ω.0 nm) ο 1 88% J 0.4% >6Β cn 1- 1 100/100 100/100 〇 〇\ <N Amorphous Evaluation Project Resin Substrate Transparent Conductive Film! Film Appearance Total Transmittance 铢 Surface Hardness Scratch Resistance Adhesion Humidity Flexibility Specific Resistance (μΩαη) Carrier Concentration (xl020/cm3 Crystallinity of Transparent Conductive Film - 〇 0 - 201012882 It can be seen from Tables 9 and 10 that the resin laminate including the substrate, the cured film, and the transparent conductive film (Examples 21 to 32) is used in substantially all evaluation items. Personality. In Comparative Examples 15 to 26 in which the cured film was not sandwiched, the film appearance, adhesion, and flexural resistance of Comparative Examples 15 to 18 and 23 to 26 using polycarbonate in the substrate were good, but transparency and surface were obtained. Hardness, scratch resistance, and electrical conductivity are inferior to those of Examples. 21 to 24 and 29 to 32. Further, in Examples 19 and 20 in which polypropylene was used as the substrate, the film appearance, surface hardness, scratch resistance, adhesion, and flex resistance were inferior to those of Examples 25 and 26. In Comparative Examples 21 and 22 in which polyethylene terephthalate was used as the substrate, the film appearance, optical properties, adhesion, and flex resistance were good, but surface hardness, scratch resistance, conductivity, and examples, 28 Relatively poor. [Examples 33 to 35, Comparative Examples 27 to 29] Example 33 (Production of Resin Laminate) 譬 The coating liquid obtained in Example 1 was cured to a thickness of 2 to 5 μm by a bar coater. It was applied to the surface of a polycarbonate molded body having a thickness of 3 mm, and was thermally cured by 丨3 (TC, 2 hours) to prepare a laminate including a substrate and a cured film. On the cured film of the laminate of the substrate and the cured film, the photocatalytic topcoat "ST_K211" manufactured by Ishihara Sangyo Co., Ltd. was applied to the cured film after the heat treatment to a thickness of about 0.5 μm. The photocatalyst layer was formed by heat treatment for 30 minutes. The results of evaluation of the obtained resin laminate 141326.doc -101 - 201012882 including the substrate, the cured film and the photocatalyst layer are shown in Table η β Example 34 A resin laminate including a substrate, a cured film, and a photocatalyst layer was produced in the same manner as in Example 33 except that the coating liquid obtained in Example 8 was used instead of the coating liquid obtained in Example i. It The results are shown in Table 11. Example 35 A substrate, a cured film, and the like were prepared in the same manner as in Example 33 except that the coating liquid obtained in Example 9 was used instead of the coating liquid obtained in the Example. The resin laminate of the photocatalyst layer was evaluated in Table 11. '° Comparative Example 27 A substrate was prepared in the same manner as in Example 33 except that the coating liquid obtained in Example 1 was not used. The resin laminate of the hardened mold and the photocatalyst layer, and the results of the evaluation thereof are shown in Table 2. Comparative Example 28 The primer "ST_K3〇〇" manufactured by Ishihara Sangyo Co., Ltd. was used instead of the one obtained in Example i. A resin layered product including a substrate, a cured film, and a photocatalyst layer was produced in the same manner as in Example 33 except that the coating liquid was applied so as to have a thickness of about 0.3 μm after drying. In Table 11, Comparative Example 29 was applied to the primer of Comparative Example 28, and further coated with a primer of "Ishihara Industry Co., Ltd." by a thickness of about 3 μm after drying and heating "141326.doc -102- 201012882The same amount of the mixed liquid (STK1〇2) of K102a" and "ST_K1〇2b" was dried at room temperature for 5 minutes, and then the base was prepared in the same manner as in Example 33 except that the temperature was heated for 30 minutes at TC. The resin laminate of the material, the cured film, and the photocatalyst layer was shown in Table 11. The characteristics of each of Examples 33 to 35 and Comparative Examples 27 to 29 were determined in accordance with the following procedures. (1) Evaluation of Resin Laminate (1) Photocatalyst function As an indicator of whether or not the photocatalyst function is expressed, the degree of hydrophilicity (generally, the contact angle with water is 40). The following hydrophilicity is referred to as having antifouling properties. As a measure of the extent to which the photocatalyst function is exhibited, the contact angle is measured by the following method. Ultraviolet rays of J mW/cm 2 were irradiated to the side of the photocatalyst layer by a black light blue lamp, and the change in the contact angle with time was measured. At the contact angle, 20 ml of ion-exchanged water was dropped onto the photocatalyst layer using a micro-syringe, and the water droplets were measured using an image processing contact angle meter (Concord Interface Science Co., Ltd., 匸8-8). (2) Total light transmittance and haze The total light transmittance and haze of the laminate were measured by a direct reading haze meter (manufactured by Suga Test Machine Co., Ltd., Η〇Μ 2 DP). (3) Yellowness (YI) Measured in accordance with JIS K7105 using SZ-_cal SENS0R (manufactured by Nippon Denshoku Industries Co., Ltd.). (4) Abrasion resistance 141326.doc -103- 201012882 «Using wear wheel cs_1()F&TABEI^s testing machine (rotary wear testing machine) (manufactured by Toyo Seiki Co., Ltd., model: ts), under load 4 9 Under the 50 〇 7 7 3 ft. abrasion test, the difference between the f-degree before the taber abrasion test and the haze after the TABER abrasion test (ΔΗ) is less than 15 as the difference between the haze Those who are 15 or more are referred to as "&. (5) The abrasion resistance is achieved by using steel wool #〇〇〇〇 (load is 4·9 Ν), and reciprocating at 2000 mm/sec on the surface of the photo-contact layer of the resin laminated body. After 50 times, the damage of the surface of the photocatalyst layer was evaluated by visual observation. Those who were completely unimpaired were recorded as "i", and those who were slightly damaged were recorded as "2", and more than half of the rubbed parts were subjected to The loss is recorded as "3". (6) Adhesiveness According to JIS K 5400, the surface of the photocatalyst layer of the resin laminate is cut into the slits of the vertical and horizontal girders at intervals of 2 mm using a razor blade to form a grid. The cellophane tape sold ("CT_24 (width: 24 mm)", manufactured by Nichiban Co., Ltd.) was sufficiently sealed with the surface of the photocatalyst to be '90. The angle was quickly peeled off in the near direction, and the number (X) of the grid in which the photocatalyst layer was not peeled off was expressed by X/100' to evaluate the adhesion of the photocatalyst layer. (7) Weather resistance performance of Xenon arc lamp weathering test (Ci65 of Atlas, the wheel power is 6 5 kw, the black panel temperature is 63 ° C, the humidity is 50%), with the above haze, yellowing, and adhesion The degree of change in the parameter of the sex is used to evaluate the weather resistance. 141326.doc -104- 201012882

[II<] Comparative Example 29 ST-K102 ST-K300 89% X m 0 jn ON 1.2% ι- 14.5% 1.1% 14.0% 100/100 10/100 Comparative Example 28 ST-K300 90% X ο JO Ο Ο 1.0 % 15.0% 1_______ 1 , 1.1% 1- 15.2% 100/100 0/100 Comparative Example 27 1 90% X cn ο 0 Ο 0.9% ( 1 1.2% 0/100 1 Example 35 Example 9 i 90% 〇ο 00 0.9% 丨 2.6% j 1.1% 2.8% 100/100 100/100 Example 34 1 Example 8 1 1 90% ί 〇 ο 0.9% 3.4% 1.1% 3.0% 100/100 100/100 Example 33 1 Implementation Example 1 90% 〇ο ΟΝ 0.9% 3.3% 1.1% 3.0% 100/100 100/100 Evaluation item 1 Coating liquid 1 _i Total light transmittance and ten abrasion resistance Scratch resistance Initial light irradiation (5 曰) Initial weather resistance ( 1000 hours) Initial 1_ Weather resistance (1000 hours) Initial weather resistance (1000 hours) Contact angle haze yellowness (YI) Adhesion 141326.doc -105- 201012882 Evaluation of any of Examples 33 to 35 Comparative Examples 27 to 29 were all excellent in abrasion resistance, scratch resistance, and weather resistance. Examples 36 to 43 and Comparative Examples 3 to 33 (molded bodies of resin laminate) Example 36 Example 1 The coating liquid has a film thickness of 2 to 3 The method of μιη was applied to a polycarbonate (PC) sheet having a thickness of 0.5 mm [manufactured by Mitsubishi Gas Co., Ltd., trade name: Iupilon Sheet], and dried at 2 (rc for 24 minutes) as a pre-hardening. A polycarbonate sheet was used, and the formed sheet for forming was vacuum-formed, and then placed in an injection molding die to contain polycarbonate at a resin temperature of 27 Å > C and a resin pressure of 50 MPa. The injection molding resin of the ester [manufactured by Idemitsu Kosan Co., Ltd., trade name: Tarflon] was injected onto the surface on which the pre-cured film was not formed, thereby producing a molded body of the eucalyptus layer. Further, the molded body was made at 12 °c> In the case of the molded article of the resin laminate, the evaluation results of the following items (丨) to (3) are shown in Table 12. (1) Film appearance The cured film surface of the molded body was visually observed. The appearance of the foreign object and the speckle pattern crack is confirmed, and those who have not confirmed such a mark are marked as "〇", and it is confirmed that the person is marked as "X". (2) Scratch resistance The surface damage was evaluated by visual inspection using steel wool #〇〇〇〇 (load: 49 N) after 1 reciprocation. If the person who is completely undamaged is recorded as Γ1", it will be called the sputum. It is "2", and the part that is rubbed is damaged by more than half of the surface. 141326.doc 201012882 is marked as "3". (3) Adhesiveness According to JIS K 5400, the cured film surface of the molded body is cut into the slits of 11 vertical and horizontal sides at intervals of 2 mm by a razor blade to form a grid of one of the commercially available ones. The cellophane tape ("CT-24 (width: 24 mm)", manufactured by Nichiban Co., Ltd.) is sufficiently adhered to the cured film surface of the molded body, and is quickly peeled off at an angle of 90°. The cured film is not self-substrate. The number of meshes (X) remaining on the peeling and peeling was represented by X/100, and the adhesion of the cured film was evaluated. Examples 37 to 39 A molded article was produced in the same manner as in Example 36. The polycarbonate sheet for molding was produced in accordance with the pre-hardening temperature, the pre-hardening time, the post-hardening temperature, and the post-hardening time shown in Table 6. The evaluation results are shown in Table 2. Example 40 The coating liquid of Example 1 was applied to a polypropylene (ρρ) sheet having a thickness of 0.3 mm as a film thickness of 2 to 3 μm [manufactured by Japan Polypropylene Co., Ltd., Name: wintec], it was dried at 20 C for 240 minutes as a pre-hardened 'preformed polypropylene sheet. The formed sheet for forming was vacuum-formed, and then placed in an injection molding die to have a resin temperature of 270. 〇, the resin pressure is 40 MPa, and the injection molding resin containing polypropylene [manufactured by Priline p〇iymer Co., Ltd., trade name: Prime Polypro] is ejected onto the surface on which the pre-cured film is not formed. The formed body. Further, the molded body was cured at 120 ° C for 30 seconds. The evaluation results are shown in Table 141326.doc -107-201012882 * 12 实施 Examples 41 to 43 A molded article was produced in the same manner as in Example 4A. The polypropylene sheet for molding was prepared in accordance with the pre-hardening temperature, the pre-hardening time, the post-hardening temperature, and the post-hardening time shown in Table 12, and the evaluation results are shown in Table 12. Comparative Example 3 0 to 3 3 Using the coating liquid of Comparative Example 1, a molded article was produced in the same manner as in Example 36, Example π, Example 40, and Example 43. The evaluation results are shown in Table 12. 141326.doc -108- 201012882

CNI <[21<] Comparative Example 33 Comparative Example 1 0- 〇d 1 1 〇cn Comparative Example 32 Comparative Example 1 240 § 〇〇1 1 100/100 Comparative Example 31 Comparative Example 1 〇ο 1 1 〇ί 100/ 100 Comparative Example 30 Comparative Example 1 240 1 -^ 〇m 1- 100/100 Example 43 Example 1 CU 〇*Τ) ο 1 1 〇1 100/100 Example 42 Example 1 CL, g a § 〇〇 100/100 Example 41 Example 1 s § 〇〇 ♦ H 100/100 Example 40 Example 1 & 240 ν〇d 〇 [100/100 Example 39 Example 1 ο to d 1 1 〇100/ 100 Example 38 Example 1 U § - Τ - Η · T · " ^ j : 100 / 100 Example 37 Example 1 U § f - Η 〇 1, 100 / 100 Example 36 Example 1 U 240 〇1 ;100/100 Evaluation item 丨 Hardening film (coating liquid) Resin substrate pre-hardening temperature (°c) Pre-hardening time (min) Post-hardening temperature (°C) Post-hardening time (min) Film appearance scratch-resistant 141 326.doc • 109- 201012882 It can be seen from Table U that Examples 36 to 43 are formed of the sapphire laminate using the coating liquid of Example i, and all of them are evaluated. Qualified in the project. In Comparative Examples 30 to 33, the molded article of the resin laminate using the coating liquid of Comparative Example was excellent in film appearance and adhesion, but the scratch resistance was inferior to those in Example (4). Industrial Applicability _ By using the coating liquid of the present invention, in addition to automobile interior parts such as instrument covers, windshields for two-wheeled vehicles and tricycles, resin-made windows (various windows), and resin building materials windows, For construction equipment, top, road light-transmissive panels (concealed soundboard), and other corrections, it can be deployed to sunglasses, sports glasses, safety glasses, and other spectacle lenses, plasma or liquid crystal, organic EL, etc. Electronic parts such as telephone parts, touch panels, and solar cells, various resin materials for lighting parts such as street lamps, windshields, and shields, especially polycarbonate materials; can be suitably used as glass substitute members. 141326.doc -110-

Claims (1)

201012882 VII. Patent Application Range: 1. A coating liquid characterized by comprising the following components (A) to (E): (A) alkoxy groups having the following components (A-1) to (A-5) a hydrolysis condensate of a decane compound, (A-1) a tetra-oxyalkyloxymethane compound, (A-2) an organoalkoxy sinter compound containing no amine group, epoxy group or isocyanate group, (A-3) a decane compound having an amine group and an alkoxy group, (A-4) a decane compound having an epoxy group and an alkoxy group, (A-5) a blocked isofluorinated decane compound having an alkoxy group; B) organic polymer microparticles composed of a copolymer comprising a monomer unit having an ultraviolet absorbing group; (C) colloidal cerium oxide; (D) a hardening catalyst; (E) a dispersion medium. 2. The coating liquid of claim 1 which further comprises (F) cerium oxide treated with a decane compound, and (G) a dispersion stabilizer. 3' The coating liquid according to Item 1 or 2, wherein the component (A-1) is a tetraalkoxydecane compound represented by the following formula (1): si(〇R,)4 ..... (1) "wherein, D _ represents an alkyl group having a carbon number of 1 to 4 or an alkyl group having an ether bond; and a plurality of R1 may be the same or different.] 4. A coating liquid according to item 1 or 2, wherein The component (A-2) is an organoalkoxy group having no amine group, epoxy group or isocyanate group represented by the following formula (): 141326.doc 201012882 decane compound: R2aSi(OR3)4.a.,·· (2) [wherein, R2 represents an alkyl group having a carbon number of i 10 or a fluoroalkyl group; a vinyl group; a stupid group; or an alkyl group substituted by a methacryloxy group having a hindrance of 1 to 3 'R represents an alkyl group having a carbon number of 1 to 4 or an alkyl group having an ether bond, and a represents 1 or 2; when R 2 is plural, plural R 2 's may be the same or different, and a plurality of OR 3 may be the same 5. The coating liquid according to claim 1 or 2, wherein the component (a-3) is a decane compound having an amine group and an alkoxy group represented by the following formula (3): R4bSi (〇R5) 4.b(3) [wherein R4 represents an alkyl group having a carbon number of 1 to 4; Alkenyl; phenyl; or selected from the group consisting of mercaptopropenyloxy, amine (_NH2), aminoalkyl KCH2)x_Nh2 (wherein X is an integer of 3), alkylamino [- The alkyl group having 1 or more carbon atoms substituted by i or more of the NHR group (wherein R is an alkyl group having 1 to 3 carbon atoms), and at least i of R4 represents an amine group or an amine group. The alkyl group substituted with any one of the succinyl group or the alkyl group is a decyl group of 丨~3, and R represents a group having a carbon number of 1 to 4, wherein b represents 1 or 2; and R4 is plural. In the case, a plurality of R4 may be the same or different, and a plurality of 〇R5 may be the same or different. 6. The coating liquid of claim 1 or 2 wherein the component (A_4) is represented by the following formula (4) a decane compound having an epoxy group and an alkoxy group: R6cSi(〇R7)4.c (4) wherein R6 represents a carbon group having a carbon number of 1 to 4; an ethyl group; a phenyl group; or a selected one. The alkyl group having a carbon number of U substituted by one or more groups of a methacryloxy group, a glycidoxy group, a 3,4 epoxy group 141326.doc 201012882 group, and at least 1 of R6 Means a glycidoxy or 3,4-epoxy ring The group has a carbon number of 1 to 3; R7 represents a carbon group having a carbon number of 1 to 4, and C represents 1 or 2; when R6 is plural, a plurality of R6 may be the same or different. The plurality of OR7 may be the same or different. The coating liquid of claim 1 or 2, wherein the component (A-5) is a blocked isocyanatodecane compound having an alkoxy group represented by the following formula (5) : R8dSi(〇R9)4.d (5) [wherein R8 represents an alkyl group having a carbon number of 1 to 4; a vinyl group; a phenyl group; or a terminal group selected from a methacryloxy group; One or more of the isocyanate groups are substituted with an alkyl group having 1 to 3 carbon atoms, and at least one of R8 represents an alkyl group having 1 to 3 carbon atoms substituted by a blocked isocyanate group; R9 represents carbon The number is 1 to 4, and d is 1 or 2. When R8 is plural, a plurality of R8s may be the same or different, and a plurality of 〇R9 may be the same or different. 8. The coating liquid according to any one of claims 1 to 7, which is characterized in that a hydrolysis condensate of (A_1}, a (A-2) component and (A-4) component is (B) The (A-5) component is added to the reaction product obtained by contacting the component (B) and reacted, and then the (Α·3) component is added and reacted. As in any of claims 1 to 7, The coating liquid is added to a reaction product obtained by heating a mixture containing (Α-1) component, (Α-2) component, (Α_4) component, and (Β)~(Ε) component (Α -5) A component obtained by reacting and reacting the component (Α-3) after the reaction. A cured film which is obtained by applying the coating liquid according to any one of claims 1 to 9 141326.doc 201012882 11. A resin laminate comprising: a substrate; and a cured film as claimed in claim 10 formed directly on the substrate. 12. A resin laminate comprising: a base a cured film according to claim 10 formed on the substrate, and an inorganic layer formed on the cured film. 13. A resin laminate, A substrate comprising: a substrate, a cured film of claim 10, and a transparent conductive film formed on the cured film. 14. A tree-layered layer body characterized by: a substrate The cured film of claim 10, and the photocatalyst layer formed on the cured film. The resin laminate according to claim 13, wherein the thickness of the cured film is 〇. 1 to 50 16. The resin laminate according to claim 13, wherein the transparent conductive film has a carrier concentration of 1 x 10 〇 18 / cm 3 or more. 17. The resin laminate according to claim 13, wherein the substrate is a resin substrate. The resin laminate according to any one of the preceding claims, wherein the substrate has a concavity and convexity. The resin laminate according to any one of claims n, 12, 17 and 18, wherein the base The resin laminate according to any one of claims n, 12, 17 and 18, wherein the substrate is cylindrical. 21. As claimed in any of claims u, 12, 17 to 20. Resin laminate, 141326.doc 201012882 in the above base The resin laminate according to any one of the preceding claims, wherein the thickness of the cured film is 〇5 to 6 pm. 23. The resin laminate according to any one of claims 11, 12, 14, 17 to 22, wherein the substrate is a polyester resin, a polycarbonate resin or a polyolefin resin. 24. Production of a cured film The method comprising the step of heating and hardening the coating liquid according to any one of claims 1 to 9. A method for producing a resin laminate, comprising: a step of applying a coating liquid according to any one of claims 1 to 9 to a substrate, a step of applying the coating liquid (4), and the substrate The step of thermoforming, the step of curing the coating liquid, and providing a coating layer. 26. The method of producing a resin laminate according to claim 25, further comprising the step of providing a resin layer on a surface of the resin laminate obtained by curing the coating liquid without a coating layer. 27. A method of producing a resin laminate, comprising: a step of forming a cured film on a substrate to harden a coating liquid as claimed in claim 9; A method of producing a transparent resin laminate by forming a step of forming a cured film as claimed in the substrate, and a step of forming a conductive film. 'It is characterized by the steps of: 1 to 9 of the coating liquid hardening to form a photocatalyst layer on the above cured film 141326.doc 201012882 ' IV. Designated representative figure: (1) The representative representative figure of the case is: (none) (2) A brief description of the symbol of the representative figure: 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: 141326.doc