JP6091691B1 - Aqueous coating material and film forming method - Google Patents

Abstract

[PROBLEMS] To provide excellent performance derived from a metal oxide, exhibit sufficient adhesion at normal times, and can fully exhibit its performance over a long period of time. An aqueous coating material that can be easily peeled off by application is obtained. The aqueous coating material of the present invention is an aqueous coating material capable of forming a transparent film, the aqueous coating material comprising a binder capable of forming a transparent film, and metal oxide having an average particle diameter of 1 to 200 nm. The binder comprises an organic component (a) and an inorganic component (b), and the ratio of the inorganic component (b) to 100 parts by weight of the organic component (a) is 3 to 80 wt. The ratio of the metal oxide (c) to 20 to 1000 parts by weight relative to 100 parts by weight of the organic component (a), the organic component (a) contains a water-soluble organic resin, and the inorganic component The component (b) contains an inorganic alkoxide compound. [Selection figure] None

Description

  The present invention relates to a novel aqueous coating material.

  Conventionally, various base materials are used as shields and barriers that separate spaces. The purpose of using these base materials is, for example, improvement of living environment in facilities, residences, vehicles, etc., control of plant growth environment in greenhouses, suppression of deterioration of articles in showcases, and stable operation of equipment by housing. For example.

  In recent years, various functionalities have been demanded for such substrates, such as weather resistance, strength, antifouling properties, heat insulation properties, heat resistance, or electromagnetic wave shielding properties such as ultraviolet shielding properties and infrared shielding properties. It has been. In addition to such functionality, it may be required to utilize the appearance and other characteristics of the substrate. As a technique for imparting functionality while utilizing the characteristics of such a base material, a coating technique using metal oxide fine particles or the like is known.

  For example, coating materials containing metal oxide fine particles such as titanium oxide, cerium oxide, and indium-doped tin oxide have been proposed using various organic polymer compounds as binders. However, when such an organic polymer compound is used as a binder, physical properties such as adhesion to a substrate and durability may be insufficient. On the other hand, the use of inorganic compounds as binders has also been studied. For example, Patent Document 1 describes a coating technique in which a coating material using a cross-linked silicon resin solution as a binder is applied and baked.

JP-A-8-134432

  The functional coating as described above may be directly affected by sunlight, wind and rain, or temperature / humidity changes over a long period of time. For this reason, such a film is heavily loaded with light, heat, water, dust, or the like, and may require repair / repair. However, when an inorganic compound is used as a binder as in Patent Document 1, it may be difficult to remove the film even if a release agent or the like is used.

  The present invention has been made in view of the above-described problems, and has excellent performance derived from a metal oxide, and at the same time, exhibits sufficient adhesion and sufficiently exhibits its performance over a long period of time. Further, it is an object to obtain an aqueous coating material that can be easily peeled off by applying a peeling agent or the like at the time of repair / renovation.

  As a result of intensive studies to achieve the above object, the present inventor has found a binding material containing an organic component and an inorganic component at a specific weight ratio, and a coating material containing a metal oxide at a specific solid content weight ratio. The invention has been completed.

That is, the present invention has the following characteristics.
1. An aqueous coating material capable of forming a transparent film, wherein the aqueous coating material includes a binder capable of forming a transparent film and a metal oxide (c) having an average particle diameter of 1 to 200 nm, Including the organic component (a) and the inorganic component (b), the ratio of the inorganic component (b) to 3 parts by weight with respect to 100 parts by weight of the organic component (a) is 100 parts by weight of the organic component (a). The ratio of the metal oxide (c) to 20 parts by weight is 20 to 1000 parts by weight, the organic component (a) contains a water-soluble organic resin, and the inorganic component (b) contains an inorganic alkoxide compound. An aqueous coating material characterized by
2. 1. The weight ratio {(b) / (c)} between the inorganic component (b) and the metal oxide (c) is 0.01 / 1 to 0.5 / 1. The water-based coating material described in 1.
3. The organic component (a) contains a curing agent (a2). Or 2. The water-based coating material described in 1.
4). 1. An organic amine compound (d) is contained. ~ 3. The water-based coating material according to any one of the above.
5). A film forming method for forming a transparent film on a substrate, the first step of treating the substrate with a treatment liquid containing a silane compound, and then applying an aqueous coating material capable of forming a transparent film. A second step, wherein the aqueous coating material comprises: ~ 4. A method for forming a film, which is the aqueous coating material according to any one of the above.

  The aqueous coating material of the present invention has excellent performance derived from metal oxides (especially infrared shielding properties) and also exhibits sufficient adhesion at normal times, and can fully demonstrate its performance over a long period of time. Furthermore, it can be easily peeled off during repairs and repairs.

  Hereinafter, modes for carrying out the present invention will be described.

[Water-based coating material]
The aqueous coating material of the present invention includes a binding material (hereinafter also simply referred to as “binding material”) capable of forming a transparent film, and a specific metal oxide (c). Component (a) (hereinafter also simply referred to as “(a) component”) and inorganic component (b) (hereinafter also simply referred to as “(b) component”) include the organic component (a). Includes a water-soluble organic resin, and the inorganic component (b) includes an inorganic alkoxide compound. And these (a) component, (b) component, and (c) component are included by specific ratio. By having such a configuration, the aqueous coating material of the present invention exhibits excellent performance derived from a metal oxide, and at the same time, exhibits sufficient adhesion and sufficiently exhibits its performance over a long period of time. Furthermore, it can be easily peeled off by applying a peeling agent or the like at the time of repair / renovation.

  The binder in the present invention can form a transparent film. Such a transparent film should just have transparency which the base material can visually recognize.

  Among these, the component (a) is a component having various organic resins as the main chain. The component (a) may have an inorganic functional group containing an organic resin as a main chain and an atom such as phosphorus or silicon. As the component (a), for example, epoxy resin, urethane resin, acrylic resin, acrylic silicon resin, alkyd resin, melamine resin, polycarbonate resin, phenol resin, polyester resin, polyether resin, vinyl resin, polyamide resin, fluororesin, An amino resin etc. are mentioned. Examples of the mode include water-dispersed resins and water-soluble resins.

  The component (a) of the present invention preferably contains at least a crosslinking reaction type organic resin. The crosslinking reaction type organic resin is a resin that forms a three-dimensional crosslinked structure by curing. Examples of the crosslinking reaction type organic resin include those that form a three-dimensional crosslinked structure by reaction of a reactive functional group or the like.

  Examples of the reactive functional group include a carboxyl group, a carbodiimide group, an epoxy group, an aziridine group, an oxazoline group, a hydroxyl group, an isocyanate group, a carbonyl group, a hydrazide group, an epoxy group, an amino group, and an alkoxysilyl group. Examples of such combinations of reactive functional groups include carboxyl group and carbodiimide group, carboxyl group and epoxy group, carboxyl group and aziridine group, carboxyl group and oxazoline group, hydroxyl group and isocyanate group, carbonyl group and hydrazide group, epoxy Combinations of groups, amino groups, alkoxysilyl groups, and the like can be given.

  The crosslinking reaction type organic resin in the present invention has one or more kinds of combinations of such reactive functional groups. In particular, a preferable combination of reactive functional groups includes at least one selected from a carboxyl group and an epoxy group, a hydroxyl group and an isocyanate group, an epoxy group and an amino group, and an alkoxysilyl group.

  In particular, in the present invention, the crosslinking reaction type organic resin preferably has at least an alkoxysilyl group. In a suitable aspect, it has an alkoxy silyl group, and also has 1 or more types of the combination of the said reactive functional group (except for alkoxy silyl groups). The use of such a crosslinking reaction type organic resin is advantageous for improving the adhesion to the base material at normal times.

  As the cross-linking reaction type organic resin, an aqueous organic resin (a1) having a reactive functional group (hereinafter also simply referred to as “(a1) component”) and its curing agent (a2) (hereinafter simply referred to as “(a2)”). An embodiment including “component” is also preferable.

Examples of the form of the component (a1) include water-dispersible organic resins and water-soluble organic resins. Among these, in the present invention, the component (a) includes the water-soluble organic resin. The use of a water-soluble organic resin is advantageous for improving the above-described effects of the present invention, and is also advantageous in terms of film-forming properties at room temperature, adhesion to a substrate, stain resistance, and the like. Further, in the present invention, the use of the water-soluble organic resin improves the smoothness despite the relatively high proportion of the component (c), and can prevent distortion in the finished appearance. Although the mechanism of this action is not clear, it has low thixotropic properties and can form a dense film compared to water-dispersible organic resins (organic resin emulsions) in which a film is formed by fusion of synthetic resin particles. Etc. are presumed to have contributed.
The weight ratio of the water-soluble organic resin in the component (a1) (water-soluble organic resin / component (a1)) is preferably 0.7 / 1 or more, more preferably 0.9 / 1 or more. An embodiment in which the component (a1) is composed only of a water-soluble organic resin is also suitable.

  For the water-solubilization of the component (a1), for example, a method such as an aqueous solution polymerization method or a post-aqueous solution method can be employed. Among these, the aqueous solution polymerization method is a method of obtaining a water-soluble resin by radical polymerization of a monomer component such as an acrylic monomer in an aqueous medium. The post-aqueous solution method is a method for obtaining a water-soluble resin by dissolving a water-soluble resin having a hydrophilic functional group in an aqueous medium.

  In the present invention, a water-soluble acrylic resin in which a copolymer having at least an acrylic monomer as a constituent component is dissolved in an aqueous medium is particularly preferable as the component (a1).

  Hereinafter, the water-soluble acrylic resin will be described in detail as the component (a1). As the acrylic monomer, a compound having a (meth) acryl group can be used. In the present invention, “acryl” and “methacryl” are collectively referred to as “(meth) acryl”. Examples of such acrylic monomers include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, n-amyl (meth) acrylate, isoamyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl ( (Meth) acrylic acid alkyl esters such as meth) acrylate and cyclohexyl (meth) acrylate;

Carboxyl group-containing acrylic monomers such as acrylic acid and methacrylic acid;
Hydroxyl group-containing acrylic monomers such as 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 4-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate;

  Amino group-containing acrylic monomers such as dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, t-butylaminoethyl (meth) acrylate, monomethylaminoethyl (meth) acrylate; (meth) acrylic acid amide, N -Amyl group-containing acrylic monomers such as methylol (meth) acrylamide, N-methylacrylamide, N-isobutylacrylamide, N-ethoxymethylacrylamide; aminoethyl (meth) acrylamide, dimethylaminomethyl (meth) acrylamide, methylaminoethyl ( Amino and amide group-containing acrylic monomers such as (meth) acrylamide, methylaminopropyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide;

  Epoxy group-containing acrylic monomers such as glycidyl (meth) acrylate and diglycidyl (meth) acrylate; Nitrile group-containing acrylic monomers such as acrylonitrile and methacrylonitrile; Carbonyl-containing acrylic monomers such as diacetone (meth) acrylamide and acetoacetoxyethyl methacrylate; And aromatic group-containing acrylic monomers such as benzyl (meth) acrylate and phenyl (meth) acrylate; heterocyclic ring-containing acrylic monomers such as pyridyl (meth) acrylate and pyrrole (meth) acrylate; and the like. These can be used alone or in combination of two or more.

  The component (a1) suitable in the present invention includes a water-soluble acrylic resin having a reactive silyl group and a reactive functional group (other than the reactive silyl group). The method for introducing the reactive functional group into the component (a1) is not particularly limited, and for example, the above-mentioned acrylic monomer having a reactive functional group may be used. In the present invention, a carboxyl group is preferred as the reactive functional group of the component (a1). The carboxyl group is advantageous for water-solubilizing the component (a1) and stabilizing the coating material.

  The reactive silyl group in component (a1) is, for example, one or more functional groups selected from an alkoxyl group, a phenoxy group, a hydroxyl group, a mercapto group, an amino group, an acetoxy group, an oxime group, an amide group, a halogen group, etc. It is bonded to an atom. As such a reactive silyl group, one in which one or more functional groups selected from an alkoxyl group and a hydroxyl group are bonded to a silicon atom is particularly preferable.

  In the component (a1), a method for introducing a reactive silyl group is not particularly limited. For example, (I) a method of copolymerizing an acrylic monomer and a reactive silyl group-containing vinyl compound as essential components, (II) A method of copolymerizing an acrylic monomer and a reactive silyl group-containing mercapto compound as essential components, (III) reacting a functional group in the acrylic resin with a silane coupling agent having a functional group capable of reacting with the functional group Method, etc.

  The reactive silyl group-containing vinyl compound in the above (I) is a compound having a reactive silyl group and an ethylenically unsaturated double bond, such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-n-butoxy. Silane, vinyltris (β-methoxyethoxy) silane, allyltrimethoxysilane, trimethoxysilylethyl vinyl ether, triethoxysilylethyl vinyl ether, trimethoxysilylpropyl vinyl ether, triethoxysilylpropyl vinyl ether, γ- (meth) acryloyloxypropyltrimethoxy Silane, γ- (meth) acryloyloxypropyltriethoxysilane, γ- (meth) acryloyloxypropylmethyldimethoxysilane, vinylmethyldimethoxysilane, methyldimethoxysilane Le ethyl vinyl ether, methyldimethoxysilylpropyl vinyl ether, etc., and can be used one or two or more thereof.

  The reactive silyl group-containing mercapto compound in the above (II) is a compound having a reactive silyl group and a mercapto group. These act as chain transfer agents such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, 3- Mercaptopropyldimethylmethoxysilane, 3-mercaptopropyldimethylethoxysilane, 3-mercaptopropyltriacetoxysilane, 3-mercaptopropylmethyldiacetoxysilane, 3-mercaptopropyldimethylacetoxysilane, 3-mercaptopropyltrioxime silane, etc. 1 type, or 2 or more types of these can be used.

  Examples of combinations of functional groups in (III) above include hydroxyl group and isocyanate group, amino group and isocyanate group, carboxyl group and epoxy group, carboxyl group and carbodiimide group, carboxyl group and aziridine group, carboxyl group and oxazoline group, amino group Groups, epoxy groups, alkoxysilyl groups, and the like.

  The silane coupling agent is, for example, a compound having at least one reactive silyl group and another functional group in one molecule, such as 3-isocyanatepropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane. Isocyanurate group-containing silane compounds such as tris- (trimethoxysilylpropyl) isocyanurate; 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxy Epoxy group-containing silane compounds such as silane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, and polymer type polyfunctional epoxysilane; 3-triethoxysilylpropyl succinic anhydride, 3-trimethoxy Acid anhydride groups (carboxyl) such as rylpropyl succinic anhydride, 3-methyldimethoxysilylpropyl succinic anhydride, methyldiethoxysilylpropyl succinic anhydride, 1-carboxy-3-triethoxysilylpropyl succinic anhydride Group) containing silane compounds;

  N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3- (triethoxysilyl) -N- (1,3-dimethylbutylidene) propanamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2 -Aminoethyl-3-aminopropyltrimethoxysilane, N, N'-bis- [3- (triethoxysilyl) propyl] ethylenediamine, N, N'-bis- [3- (methyldimethoxysilyl) propyl] ethylenediamine, N, N′-bis- [3- (trimethoxysilyl) propyl] hexame Diamine, N, N'-bis - [3- (triethoxysilyl) propyl] amino group-containing silane compound such as hexamethylene diamine; and the like. These can be used alone or in combination of two or more.

  In the above (III), the method for introducing the functional group into the acrylic resin is not particularly limited, and for example, the above-mentioned acrylic monomer having a reactive functional group may be used.

  In this invention, two or more methods can also be used together among said (I)-(III). In particular, the component (a1) of the present invention is obtained by a method using the methods (I) and (II) in combination, that is, an acrylic monomer, a reactive silyl group-containing vinyl compound, and a reactive silyl group-containing mercapto. A copolymer containing a compound as an essential component is preferred. In this case, discoloration of the component (a1) can be suppressed, and a highly transparent film can be formed.

  In the component (a1), various monomers other than those described above can also be used as a constituent component. Such a monomer is not particularly limited as long as it is a compound having an ethylenically unsaturated double bond, and examples thereof include aromatic hydrocarbon-containing monomers such as styrene, methylstyrene, chlorostyrene, vinyltoluene; maleic acid, itacon Carboxyl group-containing monomers such as acid, crotonic acid, fumaric acid and citraconic acid; hydroxyl group-containing monomers such as hydroxyethyl vinyl ether and hydroxypropyl vinyl ether; α-olefins such as ethylene, propylene and isobutylene; vinyl acetate, vinyl propionate and vinyl butyrate And vinyl esters such as vinyl pivalate; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, and cyclohexyl vinyl ether; In addition, an ethylenically unsaturated double bond-containing ultraviolet absorber, an ethylenically unsaturated double bond-containing light stabilizer, and the like can also be used.

  When the component (a1) is included, the curing agent (a2) includes, for example, one containing a compound having one or more reactive functional groups selected from a carbodiimide group, an epoxy group, an aziridine group, an oxazoline group, and the like. it can. Among these, as the component (a2), a reactive compound having an epoxy group is particularly suitable.

  Examples of the reactive compound having an epoxy group include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol poly Examples thereof include glycidyl ether, diglycerol polyglycidyl ether, polyhydroxyalkane polyglycidyl ether, and sorbitol polyglycidyl ether. In addition, a water-soluble resin or emulsion made of a polymer (homopolymer or copolymer) of an epoxy group-containing monomer can also be used. The mixing amount of the component (a2) is preferably 0.1 to 100 parts by weight (more preferably 1 to 80 parts by weight, further preferably 5 to 60 parts by weight based on 100 parts by weight of the resin solid content of the component (a1). Parts by weight).

The component (b) of the present invention may be any inorganic component that acts as a binder, and examples thereof include colloidal silica or inorganic alkoxide compounds such as silicon, titanium, zirconium, and aluminum. In addition, the said (b) component produces | generates an inorganic oxide by baking (900 degreeC). Among these, in the present invention, the component (b) includes the inorganic alkoxide compound. As an inorganic alkoxide compound, the compound shown by following formula (1) and its condensate are mentioned, for example.
M (OR) n (X) a-n (1)
(M is an inorganic atom selected from Si, Ti, Zr, Al, Ca, Fe, V, Sn, Li, Be, B, and P. R is an alkyl group. X is an alkyl group, An alkyl group having a functional group, or a halogen; a is a valence of M. n is an integer from 1 to a.)
The weight ratio of the inorganic alkoxide compound in the component (b) (inorganic alkoxide compound / component (b)) is preferably 0.7 / 1 or more, more preferably 0.9 / 1 or more. An embodiment in which the component (b) is composed only of an inorganic alkoxide compound is also suitable.

  In the present invention, a silicon alkoxide compound is particularly preferable as the inorganic alkoxide compound. The silicon alkoxide compound is a compound in which M is Si in the above formula (1), and a condensate thereof. Examples of the silicon alkoxide compound represented by the above formula (1) include tetrafunctional alkoxysilane compounds such as tetraethoxysilane, tetramethoxysilane, and tetrabutoxysilane; methyltrimethoxysilane, methyltriethoxysilane, methyltributoxysilane, Ethyltrimethoxysilane, ethyltriethoxysilane, ethyltributoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltributoxysilane, etc. Trifunctional alkoxysilane compound: dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldibutoxysilane, diethyldimethoxysilane, diethyldiethoxysilane Difunctional alkoxy such as dipropyldimethoxysilane, dipropyldiethoxysilane, dibutyldimethoxysilane, dibutyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldibutoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane Silane compounds;

  Chlorosilane compounds such as tetrachlorosilane, methyltrichlorosilane, ethyltrichlorosilane, propyltrichlorosilane, phenyltrichlorosilane, vinyltrichlorosilane, dimethyldichlorosilane, diethyldichlorosilane, diphenyldichlorosilane, methylphenyldichlorosilane; tetraacetoxysilane, methyltri Examples thereof include acetoxysilane compounds such as acetoxysilane, phenyltriacetoxysilane, dimethyldiacetoxysilane, and diphenyldiacetoxysilane, and one or more of these can be used. Moreover, the compound which has one reactive silyl group in 1 molecule can also be used together. Among these, the trifunctional alkoxysilane compound and / or the bifunctional alkoxysilane compound are preferable from the viewpoint of the effect of the present invention.

  The binder of the present invention is a mixture of the component (a) and the component (b), and may be obtained by reacting at least part of the component (a) and the component (b). Such a binder is obtained, for example, by mixing the component (b) during or after the polymerization of the component (a). The weight ratio of the component (b) is 3 to 80 parts by weight (preferably 5 to 50 parts by weight, more preferably 8 to 40 parts by weight, most preferably 10 to 10 parts by weight based on 100 parts by weight of the solid content of the component (a). 35 parts by weight). In such a case, sufficient adhesiveness is exhibited at normal times, and when the coating is repaired or repaired, it can be easily peeled off by application of a release agent or the like.

  In the present invention, by containing the component (b) in the above ratio, the affinity for the substrate is excellent, and the hardness, antistatic property, hydrophilicity, thermal conductivity and the like of the formed film can be increased. It is presumed that effects such as adhesion to materials, contamination resistance, and thermal load suppression can be obtained.

  In the aqueous coating material of the present invention, water, a water-soluble organic solvent, a mixed solvent thereof or the like can be used as the aqueous medium. Examples of the water-soluble organic solvent include alcohols such as methanol, ethanol, isopropyl alcohol, and butyl alcohol; glycols such as ethylene glycol, propylene glycol, diethylene glycol, and tripropylene glycol; ketones such as methyl ethyl ketone; ethylene glycol monomethyl ether, Glycols such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether Ether such; and the like. These can be used alone or in combination of two or more.

  In the aqueous coating material of the present invention, when water and a water-soluble organic solvent are mixed, the water: water-soluble organic solvent (weight ratio) is preferably 95: 5 to 50:50 (more preferably 90:10 to 60: 40). In such a case, it is excellent in stability, and it is excellent in film forming property and can form a uniform film.

  The metal oxide (c) of the present invention (hereinafter also simply referred to as “component (c)”) imparts various functions to the formed film. Examples of the component (c) include aluminum, zirconium, titanium, iron, copper, zinc, lead, tungsten, germanium, indium, tin, antimony, niobium, vanadium, tantalum, manganese, cobalt, nickel, lanthanum, Examples thereof include oxides such as cerium, ruthenium, rhenium, and composite oxides thereof. Specifically, aluminum oxide (alumina), zirconium oxide (zirconia), titanium oxide (titania), iron oxide, copper oxide, lead oxide, tungsten oxide, germanium oxide, indium oxide, zinc oxide, tin oxide, antimony oxide, Antimony-containing zinc oxide, antimony-containing tin oxide, tin-containing indium oxide, niobium oxide, vanadium oxide, tantalum oxide, manganese oxide, cobalt oxide, nickel oxide, cerium oxide, ruthenium oxide, cerium oxide, ruthenium oxide, rhenium oxide, silicon Examples thereof include aluminum composite oxide, titanium-cerium composite oxide, silicon-aluminum-titanium composite oxide, silicon-lithium oxide composite oxide, and the like. These can be used alone or in combination of two or more.

The component (c) can be appropriately selected and used depending on the desired functionality, and two or more types can be used in combination.
As a specific example, when imparting antifouling properties, for example, one or more selected from titanium oxide, zinc oxide and the like can be used.
In the case of imparting ultraviolet shielding properties, for example, one or more selected from titanium oxide, zinc oxide, aluminum oxide and the like can be used.
When providing infrared shielding properties, for example, zinc oxide, antimony-containing zinc oxide, aluminum-containing zinc oxide, gallium-containing zinc oxide, tin oxide, antimony-containing tin oxide, phosphorus-containing tin oxide, antimony oxide, indium oxide, tin-containing One or more selected from indium oxide, silicon oxide, aluminum oxide, copper oxide, magnesium oxide, titanium oxide, vanadium oxide, tungsten oxide, composite tungsten oxide, lanthanum boride, ruthenium oxide, composite ruthenium oxide and the like can be used. . Among these, in particular, use one or more selected from antimony-containing zinc oxide, aluminum-containing zinc oxide, antimony-containing tin oxide, tin-containing indium oxide, gallium-containing zinc oxide, composite tungsten oxide, composite ruthenium oxide, and the like. Is preferred.

  The shape of the component (c) is not particularly limited, and examples thereof include a spherical shape, a hollow shape, a porous shape, a rod shape, a fiber shape, a plate shape, and an indefinite shape. The average particle size of the metal oxide is 1 to 200 nm (more preferably 2 to 180 nm, still more preferably 3 to 150 nm). In such a range, a transparent film can be formed. As a result, various functions can be effectively imparted while utilizing the characteristics of the substrate. The average particle diameter can be measured by a dynamic light scattering particle size distribution measuring device.

  In addition, the component (c) can be used in a powder state or in a state dissolved or dispersed in a medium such as water or a water-soluble organic solvent. Particularly in the present invention, those dispersed in water are preferred.

  In the aqueous coating material of the present invention, the component (c) is 20 to 1000 parts by weight (preferably 50 to 800 parts by weight, more preferably 80 to 500 parts by weight, based on 100 parts by weight of the component (a). More preferably, it is 110 to 300 parts by weight. In such a case, the function of each metal oxide can be effectively imparted while ensuring the adhesion in normal times and the releasability when a release agent or the like is applied. In addition, the dispersibility of the component (c) can be ensured and a highly transparent film can be formed, and the shrinkage during the film formation (curing) is alleviated, so that warping, cracking, and the like of the substrate can be prevented. Furthermore, since the formed coating film has high thermal conductivity derived from the component (c), it is possible to suppress a thermal load on the base material, cracking of the base material, and the like.

  The weight ratio {(b) / (c)} of the component (b) to the component (c) is preferably 0.01 / 1 to 0.5 / 1 (more preferably 0.03 / 1). ~ 0.3 / 1). In such a case, it has excellent adhesion to the substrate and can be easily peeled off by applying a release agent or the like when the coating is repaired or repaired.

  The aqueous coating material of the present invention may be either a one-component type or a two-component type as long as it contains the components (a) to (c). When the component (a1) and the component (a2) are included, a two-component coating material is particularly preferable. For example, the main component including the component (a1), the component (b), and the component (c). And a curing agent containing the component (a2), and these components may be used in a predetermined amount when used. The solid content of the aqueous coating material of the present invention is preferably 5 to 50% by weight (more preferably 8 to 40% by weight). In such a case, the effect of the component (c) is easily obtained.

  In the aqueous coating material of the present invention, in addition to the above components, an organic amine compound (d) (hereinafter also simply referred to as “component (d)”) is preferably mixed. Since the component (d) can suppress aggregation of the component (c), the dispersibility of the component (c) can be secured, and a highly transparent coating film can be formed. Furthermore, even when a diluent is mixed in the aqueous coating material, aggregation of the component (c) can be suppressed, and a highly transparent coating film can be formed.

  Examples of such component (d) include triethylamine, N, N-dimethylethanolamine, aminoethanolamine, N-methyl-N, N-diethanolamine, isopropylamine, iminobispropylamine, ethylamine, diethylamine, 3- Examples include ethoxypropylamine, 3-diethylaminopropylamine, sec-butylamine, propylamine, methylaminopropylamine, 3-methoxypropylamine, monoethanolamine, morpholine, N-methylmorpholine, N-ethylmorpholine. You may use these in mixture of 2 or more types. In the present invention, triethylamine or trimethylamine is preferred.

  The component (d) is preferably 0.01 to 10% by weight (more preferably 0.03 to 7% by weight, still more preferably 0.05 to 5% by weight) in the aqueous coating material. In such a case, the effect of the present invention is easily obtained.

  The aqueous coating material of the present invention can contain various additives in addition to the above components to the extent that the effects of the present invention are not impaired. Examples of such additives include thickeners, dispersants, curing accelerators, antifoaming agents, reaction regulators, antiseptics, algaeproofing agents, antifungal agents, antibacterial agents, plasticizers, antifreezing agents, Examples thereof include a pH adjuster, an ultraviolet absorber, a light stabilizer, and an antioxidant.

[Film formation method]
In this invention, the transparent film containing a metal oxide can be formed by apply | coating the said aqueous coating material to various base materials. A laminate having such a transparent coating on a substrate can sufficiently exhibit desired performance over a long period of time. The thickness of the transparent film may be appropriately set depending on the desired functionality, and is preferably about 0.5 to 250 μm (more preferably 1 to 150 μm, still more preferably 1 to 100 μm). In the application of the aqueous coating material of the present invention, for example, a spray, a roller, a brush, a spatula, a sponge or the like can be used. At the time of application, the aqueous coating material of the present invention can be diluted with water, a water-soluble organic solvent, a mixed solvent thereof or the like. The dilution ratio is preferably 0 to 30% by weight. The coating amount (in terms of solid content) is preferably 1 to 100 g / m ² , more preferably ² to 50 g / m ² . Moreover, what is necessary is just to set the temperature and time at the time of drying hardening suitably, Preferably it is about 1 minute-24 hours at normal temperature (5-40 degreeC).

  It does not specifically limit as a base material, For example, it can apply to what is used for a facility, a residence, a vehicle, a greenhouse, a showcase, equipment, a lens, a display, a lamp, a signboard, a mirror, a packaging, etc. Specific examples of the material constituting the substrate include metal, ceramics, plastic, glass, resin, wood, fiber, and the like. Examples of the shape of the substrate include a board, a plate, a sheet, a film, a slab, a lamina, and a blanket. In particular, the present invention is suitable for a transparent substrate (plastic, glass, resin, etc.) and is suitable for glazing and the like. When these substrates are inorganic substrates, particularly advantageous effects can be obtained.

  The above-mentioned aqueous coating material can be applied directly to the base material, or can be applied after any treatment such as polishing treatment, washing treatment, primer treatment or the like. In the present invention, a first step of treating the substrate with a treatment liquid (L) containing a silane compound (hereinafter also referred to as “treatment liquid (L)”), and then applying the aqueous coating material. A film forming method including two steps is preferable. Such a coating method facilitates the formation of a uniform transparent film on the substrate. Furthermore, the releasability when applying a release agent or the like can be secured while enhancing the adhesion between the base material and the transparent film in a normal state, which is preferable in terms of improving the effect of the present invention.

  In the treatment liquid (L), the silane compound has a reactive silyl group, plays a role of modifying the surface of the base material, and enhances physical properties such as adhesion between the base material and the transparent film. . As the silane compound in the treatment liquid (L), a compound having a reactive silyl group and other functional groups in one molecule is suitable. Here, examples of the functional group include one or more functional groups selected from an isocyanate group, an isocyanurate group, an epoxy group, an acid anhydride group (carboxyl group), an amino group, a vinyl group, a mercapto group, and the like.

  Specifically, for example, an isocyanate group-containing silane compound, an isocyanurate group-containing silane compound, an epoxy group-containing silane compound, an acid anhydride group (carboxyl group) -containing silane compound, an amino group-containing silane compound, a reactive silyl group-containing vinyl Compounds, reactive silyl group-containing mercapto compounds, and the like. These can be used alone or in combination of two or more. In particular, the treatment liquid (L) preferably contains an amino group-containing silane compound.

  Examples of amino group-containing silane compounds include N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, and 3-aminopropyltrimethoxy. Silane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-triethoxysilyl) -N- (1,3-dimethylbutylidene) propanamine, N-phenyl-3-aminopropyltrimethoxysilane N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane, N, N′-bis- [3- (triethoxysilyl) propyl] ethylenediamine, N, N′-bis- [3- (Methyldimethoxysilyl) propyl] ethylenediamine, N, N′-bis- [3- (trimethyl Kishishiriru) propyl] hexamethylenediamine, N, N'-bis - [3- (triethoxysilyl) propyl] hexamethylenediamine, and the like. These can be used alone or in combination of two or more.

  The content of the silane compound in the treatment liquid (L) is preferably 0.01 to 20% by weight (more preferably 0.02 to 10% by weight). When the treatment liquid (L) is diluted at the time of use, the content of the silane compound may be within the above range in the diluted treatment liquid (L).

  In addition to the above components, the treatment liquid (L) may contain, for example, a surfactant, water, a solvent, an abrasive, a thickener, a dispersant, a pH adjuster, an alkali agent, and the like.

  Among these, when a surfactant is included, the detergency with respect to the substrate can be improved and the surface of the substrate can be uniformly modified. Examples of such surfactants include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, and the like. These may be used alone or in combination of two or more. Can be used. Especially, in this invention, the aspect containing a nonionic surfactant or the aspect containing a nonionic surfactant and an anionic surfactant is preferable.

  In addition, the solvent can improve the wettability to the base material, and if the base material has an existing film, it can improve the peelability of the existing film, further improving the base material surface more uniformly. Can do. Examples of such solvents include alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol and 3-methoxy-3-methylbutanol; cellosolv esters such as methyl cellosolve acetate and ethyl cellosolve acetate; ethylene glycol Monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, etc. The glycol Water-soluble solvents such as ethers, N-alkyl-2-pyrrolidone such as N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-propyl-2-pyrrolidone, N-butyl-2-pyrrolidone; Dibasic acid esters such as dimethyl acid, dimethyl glutarate, dimethyl phthalate, and dimethyl adipate; ketones such as methyl isoamyl ketone; at least one high-boiling solvent such as alcohols such as benzyl alcohol and furfuryl alcohol, etc. These can be used alone or in combination of two or more. Such a treatment liquid (L) contains the above-mentioned silane compound and a solvent, thereby cleaning the substrate, removing the existing coating, uniformly modifying the substrate surface, It has a function to improve adhesion to the transparent film.

  The treatment method using the treatment liquid (L) is not particularly limited as long as the surface of the substrate can be modified with the treatment liquid (L), and the step of applying the treatment liquid (L) to the substrate. As long as it contains. As a method of applying the treatment liquid (L), a method of directly applying the treatment liquid (L) to the substrate, a method of applying (rubbing) with a sponge or waste impregnated with the treatment liquid (L), Or the method of immersing a base material in a process liquid (L) is mentioned. Further, after applying the treatment liquid (L), it can be rubbed with a sponge or a waste cloth. Furthermore, after the coating step, a water washing step, a wiping step, a drying step, and the like can be combined as necessary, and each step may be repeated. What is necessary is just to set and use the usage-amount of the process liquid (L) in a 1st process suitably according to the state of a base material.

  After the first step, the aqueous coating material of the present invention is applied as a second step. The method for applying the aqueous coating material in the second step is as described above.

  The transparent film formed by the aqueous coating material of the present invention can be peeled by applying a release agent or the like. Examples of the release agent include N-alkyl-2-pyrrolidone such as N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-propyl-2-pyrrolidone and N-butyl-2-pyrrolidone; Dibasic acid esters such as dimethyl, dimethyl glutarate, dimethyl phthalate, and dimethyl adipate; ketones such as methyl isoamyl ketone; those containing at least one high-boiling solvent such as alcohols such as benzyl alcohol and furfuryl alcohol Etc. In addition, the said process liquid (L) can also be used as a peeling agent of the aqueous coating material of this invention.

  The transparent coating formed by the aqueous coating material of the present invention has a high resistance to loads due to sunlight, wind and rain, temperature / humidity changes, condensation, and the like, and thus exhibits sufficient adhesion at normal times. When a release agent or the like is applied to the transparent film, the transparent film can be peeled by an action such as an appropriate swelling of the solvent. Such an effect is achieved by the fact that the covering material of the present invention contains the above-mentioned component (a), component (b) and component (c) in a specific ratio.

  Examples are given below to clarify the features of the present invention.

(Water-based coating material 1)
Organic component 1 [alkoxysilyl group / carboxyl group-containing water-soluble acrylic resin (BA, BMA, MMA, MAA, MPTM copolymer, monomer weight ratio 6: 44: 16: 17: 17)],
Binder obtained by mixing inorganic component 1 [dimethyldiethoxysilane] during polymerization [medium; water / water-soluble organic solvent (mixed weight ratio 75/25) mixed solution, solid content 30% by weight, organic component 1: 317 parts by weight (inorganic component 1 = 80: 15 (weight ratio)) (95 parts by weight in solid content)
Metal oxide 1 [antimony-containing tin oxide dispersion (medium; water, solid content 20% by weight, average particle size 75 nm)] 750 parts by weight (solid content 150 parts by weight), water 250 parts by weight, additive (antifoaming) Agent, ultraviolet absorber, light stabilizer, thickener, etc.) 3 parts by weight,
20 parts by weight of curing agent 1 [epoxy group-containing reactive compound (sorbitol polyglycidyl ether), solid content 100 wt%] was uniformly mixed by a conventional method to obtain an aqueous coating material 1.

(Aqueous coating materials 2-13, 15-18, 20-22)
Except for the raw materials and blending ratios shown in Tables 1 to 3, aqueous coating materials 2 to 13, 15 to 18, and 20 to 22 were obtained in the same manner as the aqueous coating material 1. In addition, the raw material used is shown below.

(A) Organic component / organic component 1 [alkoxysilyl group / carboxyl group-containing water-soluble acrylic resin (BA, BMA, MMA, MAA, MPTM copolymer, monomer weight ratio 6: 44: 16: 17: 17)]
Organic component 2 [alkoxysilyl group / carboxyl group-containing water-soluble acrylic resin (BA, MMA, MAA, MPTM copolymer, monomer weight ratio 6: 60: 17: 17)]
Organic component 3 [alkoxysilyl group-carboxyl group-containing water-soluble acrylic resin (BA, BMA, MMA, CHMA, MAA, MPTM copolymer, monomer weight ratio 6: 22: 16: 22: 17: 17)]
Organic component 4 [alkoxysilyl group / carboxyl group-containing water-soluble acrylic resin (BA, BMA, MMA, CHMA, MAA, MPTM, MPS copolymer, monomer weight ratio 5: 20: 15: 20: 15: 15: 10)]
The monomer components are BA: n-butyl acrylate, BMA: t-butyl methacrylate, MMA: methyl methacrylate, MAA: methacrylic acid, CHMA: cyclohexyl methacrylate, MPTM: 3-methacryloxypropyltrimethoxysilane, MPS: 3 -Represents mercaptopropyltrimethoxysilane.
Curing agent 1 [epoxy group-containing reactive compound (sorbitol polyglycidyl ether), solid content 100 wt%]
Curing agent 2 [epoxy group-containing reactive compound (polyhydroxyalkane polyglycidyl ether), solid content: 100% by weight]

(B) Inorganic component / inorganic component 1 [dimethyldiethoxysilane]
・ Inorganic component 2 [methyltrimethoxysilane]
・ Inorganic component 3 [tetraethoxysilane]

(C) Metal oxide / metal oxide 1 [antimony-containing tin oxide dispersion (medium; water, solid content 20% by weight, average particle size 75 nm)]
Metal oxide 2 [antimony-containing zinc oxide dispersion (medium; water, solid content 30% by weight, average particle size 72 nm)]

(D) Organic amine compound / organic amine compound 1 [triethylamine (active ingredient 100% by weight)]

(Water-based coating material 14)
Obtained by mixing organic component 5 [alkoxysilyl group / carboxyl group-containing acrylic resin emulsion (copolymer of BA, BMA, MMA, MAA, MPTM)] and inorganic component 1 [dimethyldiethoxysilane] during polymerization. The aqueous coating material 14 was obtained in the same manner as the aqueous coating material 1 except that the binder [medium; water, solid content 30 wt%, organic component 5: inorganic component 1 = 80: 15 (weight ratio)] was used. It was.

(Water-based coating material 19)
Aqueous coating material 1 except that organic component 6 [acrylic resin emulsion (copolymer of BA, BMA, MMA, MAA), medium; water, solid content 30 wt%] is used as a binder and no curing agent is blended. An aqueous coating material 19 was obtained in the same manner as above.

<Manufacture of specimen>
On the base material 1 [transparent glass plate (100 mm × 50 mm × 3 mm)], the prepared aqueous coating material was applied with a sponge so that the coating amount was 30 g / m ^2, and was in a standard state (temperature 23 ° C.). The specimen I was cured for 48 hours at a humidity of 50% RH).
Moreover, the test body II was produced in the procedure similar to the manufacture of the said test body I except having used the aqueous coating material stored for 3 months in 50 degreeC environment.

(Examples 1-16, Comparative Examples 1-6)
The following evaluation was performed about the obtained test body.

<Evaluation>
(Adhesion evaluation 1)
About the produced test body I, adhesiveness was evaluated by the cross-cut method (4x4mm * 25 mass). In this test, the larger the value, the better the adhesion. The results are shown in Tables 1-3. In the table, 23/25 or more is a practical level.

(Adhesion evaluation 2)
The prepared specimen I was immersed in warm water at 50 ° C. for 48 hours, then pulled up from the warm water and dried in a standard state, and the adhesion test was performed as described above. The results are shown in Tables 1-3. In the table, 15/25 or more is a practical level.

(Adhesion evaluation 3)
The prepared specimen I was immersed in warm water at 50 ° C. for 1 week, then pulled up from the warm water and dried in a standard state, and the adhesion test was performed as described above. The results are shown in Tables 1-3. In the table, 5/25 or more is a practical level.

(Transparency evaluation 1)
About the produced test body I, the haze value was computed according to the prescription | regulation of JISK7136. The haze value was determined by using “UV-visible near-infrared spectrophotometer (V-670)” manufactured by JASCO Corporation, “diffuse transmittance” and “total light transmittance” in the visible light range (380-780 nm). Is obtained by dividing the diffuse transmittance by the total light transmittance. The evaluation criteria are shown below. Of the evaluations, A and B are practical levels.
A: Less than 3% (no cloudiness or distortion, and the background is clearly visible through the specimen)
B: 3% or more and less than 6% C: 6% or more and less than 10% D: 10% or more The haze value of the base material used for the specimen was 0.1%. The results are shown in Tables 1-3.

(Transparency evaluation 2)
About the produced test body II, it carried out similarly to the transparency evaluation 1, and computed the haze value. The obtained haze value was compared with the haze value obtained in the transparency evaluation 1, and the change in transparency was evaluated. The evaluation criteria are shown below. The results are shown in Tables 1-3. Of the evaluations, A to C are practical levels.
A: No change or increase of less than 1% B: Increase of 1% or more and less than 2% C: Increase of 2% or more and less than 5% D: Increase of 5% or more

(Solar radiation transmittance evaluation)
About the produced test body I, the solar radiation transmittance | permeability was measured according to the prescription | regulation of JISA5759. In addition, the measurement used the JASCO Corporation "ultraviolet visible near-infrared spectrophotometer (V-670)". The evaluation criteria are shown below. Of the evaluations, A to C are practical levels.
A: Less than 60% B: 60% or more and less than 65% C: 65% or more and less than 70% D: 70% or more The solar radiation transmittance of the base material used for the test specimen was 86%. The results are shown in Tables 1-3.

(Peelability evaluation)
The test specimen I was impregnated in a sponge with a release agent [dibasic acid ester (mixed solution of dimethyl succinate, dimethyl glutarate, dimethyl adipate) / N-methyl-2-pyrrolidone = 2/1 mixed solvent]. After being applied, it was wiped off with a waste cloth, and the removal property of the film was evaluated. The evaluation criteria were a four-step evaluation (excellent: A>B>C> D: inferior), with “A” being easily removed and “D” being difficult to remove. The results are shown in Tables 1-3. Of the evaluations, A to C are practical levels.

(Contamination resistance evaluation)
A 15% by weight carbon black aqueous dispersion paste solution was dropped on the prepared test body I and left in a thermostatic chamber at 50 ° C. for 2 hours. Thereafter, the film was washed in running water, and the degree of contamination of the coating film surface was visually evaluated. The evaluation criteria were a four-step evaluation (excellent: A>B>C> D: inferior), with “A” indicating no trace and “D” indicating an apparent trace. The results are shown in Tables 1-3. It is as follows. Of the evaluations, A to C are practical levels.

(Infrared shielding evaluation)
A base material 1 (however, 300 mm × 300 mm × 3 mm) was coated with the prepared aqueous coating material with a sponge so that the coating amount was 30 g / m ^2, and was cured in a standard state for 48 hours. Was designated as Specimen III.
The test body III was placed on the ceiling of a box [300 mm × 300 mm × 300 mm (plate thickness: 3 mm) acrylic 5 side] so that the coating side would be up, and the box was placed on a black table. An infrared lamp was placed at a distance of 30 cm from the test body, a thermocouple was fixed at the center of the bottom of the box, and the space temperature inside the box after irradiation with the infrared lamp for 15 minutes was measured. The results are shown in Tables 1-3. As an evaluation, within 45 ° C. is a practical level. In addition, it was 56 degreeC as a result of performing the same evaluation only with the base material 1. FIG.

(Shrinkage evaluation)
On the base material 2 [PET film (100 mm × 50 mm × 50 μm)], the prepared aqueous coating material was applied with a sponge so that the coating amount was 50 g / m ^2, and cured under standard conditions for 48 hours. This was used as test body IV, and the warpage of the substrate due to shrinkage of the film was evaluated. The evaluation criteria were a four-step evaluation (excellent: A>B>C> D: inferior), where “A” indicates that the substrate is not warped and “D” indicates that the substrate is warped. The results are shown in Tables 1-3. Of the evaluations, A to C are practical levels.

注）上記［重量部］は固形分を示す。

Note) The above [parts by weight] indicates the solid content.

注）上記［重量部］は固形分を示し、（ｄ）については有効成分を示す。また、実施例１５及び１６の水性被覆材中における（ｄ）の比率は０．４重量％である。

Note) The above [parts by weight] indicates the solid content, and (d) indicates the active ingredient. Further, the ratio of (d) in the aqueous coating materials of Examples 15 and 16 is 0.4% by weight.

注）上記［重量部］は固形分を示す。

Note) The above [parts by weight] indicates the solid content.

  Moreover, evaluation was implemented using the base material by which the surface treatment was given with the following process liquids L.

<Manufacture of processing liquid (L)>
Nonionic surfactant 10 parts by weight, anionic surfactant 2 parts by weight, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane 1 part by weight, water-soluble solvent 10 parts by weight, alkali agent 0.1 A mixture of parts by weight and 76.9 parts by weight of water was used as the treatment liquid (L).

(Example 17)
A sponge obtained by impregnating the treatment liquid (L) 10-fold with water was impregnated into the sponge, and the surface of the substrate 1 was rubbed, wiped with a waste cloth, and dried. Except having used the base material obtained by this method, the test bodies I-IV were produced similarly to Example 1, and the same evaluation was implemented. Furthermore, the following evaluation was implemented as an adhesive test. The results are shown in Table 4.

(Adhesion evaluation 4)
The prepared specimen I was immersed in warm water at 50 ° C. for 4 weeks, then pulled up from the warm water and dried in a standard state, and the adhesion test was performed as described above. In the table, 3/25 or more is a practical level.

  Also, for Example 1, adhesion evaluation 4 was performed. The results are shown in Table 4.

  In Example 17, compared with Example 1, a uniform transparent film was easily formed. Furthermore, in Example 17, even better adhesion was obtained.

Claims (4)

An aqueous coating material capable of forming a transparent film,
The aqueous coating material includes a binder capable of forming a transparent film, and a metal oxide (c) having an average particle diameter of 1 to 200 nm,
The binder includes an organic component (a) and an inorganic component (b),
The ratio of the inorganic component (b) to 100 parts by weight of the organic component (a) is 3 to 80 parts by weight,
The ratio of the metal oxide (c) to 100 parts by weight of the organic component (a) is 20 to 1000 parts by weight ,
The organic component (a) includes at least a crosslinking reaction type organic resin,
The crosslinking reaction type organic resin includes an aqueous organic resin (a1) having a reactive functional group, and a curing agent (a2),
The aqueous organic resin (a1) is a water-soluble acrylic resin having a reactive silyl group and a carboxyl group,
The curing agent (a2) is a compound having one or more reactive functional groups selected from a carbodiimide group, an epoxy group, an aziridine group, and an oxazoline group,
The inorganic component (b), see contains an inorganic alkoxide compound,
The inorganic alkoxide compound is a compound represented by the following formula (1) and a condensate thereof:
The metal oxide (c) is zinc oxide, antimony-containing zinc oxide, aluminum-containing zinc oxide, gallium-containing zinc oxide, tin oxide, antimony-containing tin oxide, phosphorus-containing tin oxide, antimony oxide, indium oxide, tin-containing indium oxide. And at least one selected from silicon oxide, aluminum oxide, copper oxide, magnesium oxide, titanium oxide, vanadium oxide, tungsten oxide, composite tungsten oxide, lanthanum boride, ruthenium oxide, and composite ruthenium oxide. Aqueous coating material.
M (OR) n (X) a-n (1)
(M is an inorganic atom selected from Si, Ti, Zr, Al, Ca, Fe, V, Sn, Li, Be, B, and P. R is an alkyl group. X is an alkyl group, An alkyl group having a functional group, or a halogen; a is a valence of M. n is an integer from 1 to a.)   The weight ratio {(b) / (c)} between the inorganic component (b) and the metal oxide (c) is 0.01 / 1 to 0.5 / 1. The aqueous coating material as described. Aqueous coating material according to claim 1 or 2, characterized in that it comprises an organic amine compound (d). A film forming method for forming a transparent film on a substrate,
A first step of treating the substrate with a treatment liquid containing a silane compound;
Next, a second step of applying an aqueous coating material capable of forming a transparent film,
Have
The said aqueous coating material is the aqueous coating material in any one of Claims 1-3 , The film formation method characterized by the above-mentioned.