TW201423142A - Antifouling antireflection film, article and method for manufacturing same - Google Patents

Abstract

Provided are: an antifouling antireflection film that has improved antifouling properties while sustaining an antireflection performance of a porous silica film and can maintain a good appearance over a long period of time; an article equipped with the antifouling antireflection film; and a method for manufacturing the same. The antifouling antireflection film comprises a porous silica film and an antifouling layer coating the surface of the porous silica film, wherein the antifouling layer comprises a plurality of nanosheets, the nanosheets are formed of a low refraction material having a refractive index of 1.4-1.65, and the average film thickness of the antifouling layer is 0.4-40 nm.

Description

Antifouling antireflection film, article and method of manufacturing same Field of invention

The present invention relates to an antifouling antireflection film, an article comprising the antifouling antireflection film, and a method for producing the same.

Background of the invention

An article having an antireflection film on the surface of a transparent substrate such as a glass plate can be used as a cover member for a solar cell, various displays, and such front panels, various window glasses, a cover member for a touch panel, and the like.

The antireflection film is disposed on the outermost layer of the article in its function. Therefore, the antireflection film is required to have antifouling properties (i.e., the dirt is not easily attached, or is easily removed even if it is attached).

A cerium oxide-based porous film is known as one of the antireflection films used for a transparent substrate such as a glass plate (see, for example, Patent Document 1). Since the cerium oxide-based porous film has pores in the base material containing cerium oxide as a main component, the refractive index is lower than that in the case where no pores are provided.

However, since there are many fine open pores or irregularities on the surface of the ceria-based porous film, there is a problem in that it is easy to adhere to dirt such as oil stains or resins, and it is difficult to remove the adhered dirt.

For example, in the manufacturing step of a solar cell, it is carried out with a sealing material. The step of covering the member with the solar cell. When the anti-reflection film is made of a ceria-based porous film, in the production step, EVA (ethylene-vinyl acetate copolymer resin) which is a sealing material permeates into the ceria-based porous film, and is lowered. Anti-reflective performance issues. In addition, the infiltrated EVA is not easily peeled off by the ceria-based porous film, and even after the peeling, the color of the ceria-based porous film of the EVA-permeable portion becomes a problem similar to the color of the other portions.

A countermeasure against the problem in the above manufacturing step is to provide a protective film on the ceria porous film. However, the method of providing a protective film makes the cost higher.

Further, a method of applying a fluorine-based coating agent to the surface of a ceria-based porous film has been proposed (see, for example, Patent Document 2)

The method of coating the fluorine-based coating agent is lower in cost and easier to improve the antifouling property against grease stains or EVA than in the case of providing a protective film. However, the coating agent penetrates into the cerium oxide-based porous film at the time of coating, and there is a concern that the anti-reflection property is lowered. In addition, after the solar dioxide module is installed outside the house, the cerium oxide-based porous film which is provided with the antifouling property in this way is not easily washed away by rain or the like due to the influence of water repellency. It is a spot-like residue, and it is easy to cause problems such as running water marks due to rain or the like, and it is difficult to maintain a good appearance for a long period of time.

Prior technical literature Patent literature

Patent Document 1: Japanese Patent Publication No. 2010-509175

Patent Document 2: Japanese Patent Laid-Open No. Hei 5-330856

Summary of invention

The present invention has been made in view of the above circumstances, and an object of the invention is to provide an antifouling antireflection film which can maintain anti-reflection performance of a cerium oxide-based porous film, can improve antifouling property, and can maintain a good appearance for a long period of time; An article of an antifouling antireflection film and a method of manufacturing the same.

The invention includes the following aspects:

[1] An antifouling antireflection film comprising a ceria-based porous film and an antifouling layer covering a surface of the ceria-based porous film; the anti-fouling layer comprising a plurality of nanoparticles, and the nano-side The sheet is composed of a low refractive material having a refractive index of 1.4 to 1.65; and the average thickness of the antifouling layer is 0.4 to 40 nm.

[2] [1] The antifouling properties of the anti-reflection film described, wherein the nano-sheet has an average thickness of 0.7 to 20nm and an average area of 100 ~ 1,000,000nm ^2.

[3] The antifouling antireflection film according to [1], wherein the nanosheet is derived from an inorganic layered compound selected from the group consisting of a layered polysilicate. And at least one of the group consisting of clay minerals.

[4] The antifouling antireflection film according to any one of [1] to [3] wherein the nanosheet is modified by a surface of a surfactant.

[5] An article having the antifouling antireflection film according to any one of [1] to [4], which is provided on a transparent substrate.

[6] A method for producing an article having an antifouling antireflection film, comprising the steps of: forming a ceria-based porous film on a transparent substrate; and surface of said ceria-based porous film The coating liquid for forming an antifouling layer is applied and dried to form an antifouling layer, wherein the coating liquid for forming an antifouling layer contains a plurality of nano tablets and a dispersion medium of the nanosheet; and the nano tablet It is composed of a low refractive material having a refractive index of 1.4 to 1.65; and this method is an antifouling antireflection film having an average thickness of the antifouling layer of 0.4 to 40 nm.

[7] [6] The manufacturing method described in the article, wherein the nano-sheet has an average thickness of 0.7 to 20nm and an average area of 100 ~ 1,000,000nm ^2.

[8] The method for producing an article according to [6], wherein the nano-sheet is derived from an inorganic layered compound selected from the group consisting of layered polysilicates and clays. At least one of the group consisting of minerals.

[9] The method for producing an article according to any one of [6] to [8] wherein the coating liquid for forming an antifouling layer further contains a binder or a precursor thereof; and the coating for forming an antifouling layer In the cloth liquid, the mass ratio of the above-mentioned nanosheet to the total amount of the above-mentioned nanosheet and the above-mentioned binder or its precursor is 0.25 or more.

[10] The method for producing an article according to any one of [6] to [9] wherein the solid content concentration in the coating liquid for forming an antifouling layer is 0.05~ 0.50% by mass.

[11] The method for producing an article according to any one of [6] to [10] wherein the coating liquid for forming an antifouling layer further contains a surfactant; and the content of the surfactant is relative to the nanometer. The mass ratio of the tablet content is 1.5 or less.

[12] The method for producing an article according to any one of [6] to [8] wherein the coating liquid for forming an antifouling layer contains only a nanosheet as a solid component; and the method is applied to the coating The coating liquid for forming an antifouling layer is dried at 300 ° C or lower.

[13] The method for producing an article according to any one of [6], wherein the dispersion medium contains water; and the water content in the coating liquid for forming an antifouling layer is relative to the antifouling layer. The total mass of the coating liquid for formation is 60% by mass or less.

According to the present invention, it is possible to provide an antifouling antireflection film which can maintain the antireflection property of the ceria porous film, can improve the antifouling property, and can maintain a good appearance for a long period of time; and has the antifouling antireflection film. Articles and methods of making them.

10‧‧‧ Items

12‧‧‧ glass plate

14‧‧‧cerium dioxide porous membrane

16‧‧‧Anti-fouling layer

18‧‧‧Antifouling anti-reflection film

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing an embodiment of an article of the present invention.

2 is a SEM photograph of the outermost surface of the ceria-based porous film side of the cerium oxide-based porous film glass plate before the formation of the antifouling layer in Example 2 in [Example].

Fig. 3 is a SEM photograph of the article obtained in Example 2 ((a) the outermost surface on the antifouling layer side, and (b) the cross section).

Form for implementing the invention

The invention will now be described by way of examples of embodiments.

<First Embodiment>

Fig. 1 is a cross-sectional view showing a first embodiment of an article having an antifouling antireflection film of the present invention on a transparent substrate.

The article 10 of the present embodiment has a transparent substrate 12 and an antifouling antireflection film 18 formed on the surface of the transparent substrate 12. The antifouling antireflection film 18 is composed of a ceria-based porous film 14 and an antifouling layer 16 formed on the surface of the ceria-based porous film 14.

(transparent substrate 12)

The shape of the transparent substrate 12 may be a plate, a film, or the like.

Examples of the material of the transparent substrate 12 include glass, resin, and the like.

Examples of the glass include soda lime glass, borosilicate glass, aluminosilicate glass, and alkali-free glass.

Examples of the resin include polyethylene terephthalate, polycarbonate, triethylenesulfonyl cellulose, polymethyl methacrylate, and the like.

The transparent substrate 12 is preferably a glass plate.

The glass plate may be a smooth glass plate formed by a float method or the like, or may be an embossed glass plate having irregularities on its surface. Further, it is not only a flat glass plate but also a glass plate having a curved shape.

The thickness of the glass plate is not particularly limited, and the thickness can be used 0.2~ 10mm glass plate. The thinner the thickness, the lower the absorption of light, and therefore it is suitable for use in order to increase the transmittance.

In the case where the glass plate is a window glass for construction or a vehicle, it is preferable to use soda lime glass having the following composition.

It is expressed by the mass percentage based on the oxide (hereinafter, "% of mass percentage" is abbreviated as "%", and the same applies hereinafter), and contains: SiO ₂ : 65 to 75%, Al ₂ O ₃ : 0 to 10%, CaO: 5~ 15%, MgO: 0 to 15%, Na ₂ O: 10 to 20%, K ₂ O: 0 to 3%, Li ₂ O: 0 to 5%, Fe ₂ O ₃ : 0 to 3%, TiO ₂ : 0~5%, CeO ₂ :0~3%, BaO:0~5%, SrO:0~5%, B ₂ O ₃ :0~15%, ZnO:0~5%, ZrO ₂ :0~5 %, SnO ₂ : 0 to 3%, SO ₃ : 0 to 0.5%.

In the case where the glass plate is an alkali-free glass, it has the following composition It is better.

It is expressed by mass percentage based on oxide, and contains: SiO ₂ : 39 to 70%, Al ₂ O ₃ : 3 to 25%, B ₂ O ₃ : 1 to 30%, MgO: 0 to 10%, and CaO: 0~ 17%, SrO: 0~20%, BaO: 0~30%.

In the case where the glass plate is a mixed alkali glass, it is preferred to have the following composition.

It is expressed by mass percentage based on oxide, and contains: SiO ₂ : 50 to 75%, Al ₂ O ₃ : 0 to 15%, MgO + CaO + SrO + BaO + ZnO: 6 to 24%, Na ₂ O + K ₂ O: 6~24%,.

In the case where the glass plate is a cover glass for a solar cell, it is preferable to use an embossed glass plate having a embossed satin on the surface. The embossed glass plate is a soda-lime glass (so-called slate glass: a general term for a slightly blue soda-lime glass) with a lower iron content than ordinary window glass, and has high transparency and no color sodium. Calcium glass (so-called white glass) is preferred.

An organic energy layer may be formed in advance on the surface of the transparent substrate 12.

The functional layer may, for example, be an undercoat layer, a adhesion improving layer, a protective layer or the like.

The undercoat layer may be exemplified by a low refractive index layer having an alkali shielding layer or a wide band. Functional person. The undercoat layer is preferably a layer formed by applying a coating composition for undercoating containing a hydrolyzate (decane hydrolyzed sol) containing an alkoxysilane to a substrate. In the case where the undercoating liquid described later is applied to the undercoat layer, the undercoat layer may be preliminarily baked or may be kept in a wet state. In the case of forming the undercoat layer, the coating temperature is preferably from room temperature to 80 ° C, and the firing temperature is preferably from 30 to 700 ° C. The film thickness of the undercoat layer is preferably from 10 to 500 nm.

(cerium oxide porous film 14)

The "cerium oxide-based porous film" refers to a film having a plurality of pores in a substrate mainly composed of cerium oxide. Since the ruthenium dioxide-based porous film is mainly composed of ruthenium dioxide as a base material, the refractive index is low and the reflectance is low. In addition, the cerium oxide-based porous film is excellent in chemical stability, adhesion to a transparent substrate 12 such as a glass plate, and abrasion resistance. Further, by having voids in the substrate, the refractive index becomes lower as compared with the case without voids.

The base material is ruthenium dioxide as a main component, and the ratio of ruthenium dioxide is 90% by mass or more based on the base material (100% by mass).

The substrate is preferably composed of substantially cerium oxide. Substantially consisting of cerium oxide means that impurities which are unavoidable (for example, a structure derived from the compound (a2) described later) are removed, and only cerium oxide is formed.

The substrate may also contain a small amount of components other than cerium oxide. The component may be selected from the group consisting of Li, B, C, N, F, Na, Mg, Al, P, S, K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, One or more ions and or oxides in a group of Ga, Sr, Y, Zr, Nb, Ru, Pd, Ag, In, Sn, Hf, Ta, W, Pt, Au, Bi, and lanthanides Wait compound of.

The substrate may contain not only a two-dimensionally polymerized substrate component but also three-dimensionally polymerized nanoparticle. Examples of the composition of the nanoparticles include Al ₂ O ₃ , SiO ₂ , SnO ₂ , TiO ₂ , ZnO, and ZrO ₂ . The particle size of the nanoparticles is preferably from 1 to 100 nm. The shape of the nanoparticles is not particularly limited, and examples thereof include a spherical shape, a needle shape, a hollow shape, a sheet shape, and a polygonal shape. The ratio of the nanoparticles is preferably 20% by mass or less based on the solid content of the substrate. If it is in this range, sufficient film strength can be maintained.

The ceria-based porous film 14 is not particularly limited, and a well-known ceria-based porous film can be used.

An example of a suitable ceria-based porous film is a microparticle (b) containing a dispersion medium (a), dispersed in the dispersion medium (a), and dissolved or dispersed in the dispersion medium (a). The coating liquid of the substrate precursor (c) is fired and the obtained film is fired. The substrate precursor (c) may be a hydrolyzate of alkoxydecane.

This film is a film in which fine particles (b) are dispersed in a substrate composed of a fired product (SiO ₂ ) of the substrate precursor (c). This film exhibits an antireflection effect by selectively forming voids around the microparticles (b). Especially in the case where the core portion of the fine particles (b) is hollow, it exhibits an excellent antireflection effect. The coating liquid and the method of forming the ceria-based porous film using the same will be described in detail later.

The film thickness of the ceria-based porous film 14 is preferably 50 to 300 nm, and more preferably 80 to 200 nm. When the film thickness of the ceria-based porous film 14 is 50 nm or more, light interference occurs and the anti-reflection performance is exhibited. When the film thickness of the ceria-based porous film 14 is 300 nm or less, the film can be formed without cracking.

The film thickness of the ceria-based porous film 14 can be measured by a reflection spectroscopic film thickness meter.

The surface of the ceria porous film 14 preferably has open pores. When the article 10 of the present embodiment is exposed to ultraviolet rays or wind and rain, and the antifouling layer is removed, the surface of the article 10 is likely to be a hydrophilic surface, and the dirt such as sand or enamel is easily washed away by rain or the like. .

(anti-fouling layer 16)

The antifouling layer 16 contains a plurality of pieces of nano tablets. The plurality of nanosheets are each composed of a low refractive material having a refractive index of 1.4 to 1.65.

The refractive index of the low refractive material is 1.4 to 1.65, preferably 1.4 to 1.6.

The refractive index of the low refractive material constituting the nanosheet is a value obtained by calculation from the reflectance obtained by measuring the spectral reflectance.

By providing the antifouling layer 16 on the surface of the ceria-based porous film 14, the antifouling property can be improved without lowering the antireflection performance.

The antifouling layer 16 is formed by applying a coating liquid for forming an antifouling layer in which a plurality of nano sheets are dispersed in a liquid medium to the surface of the ceria porous film 14 and drying it, and the details thereof will be described later. When the coating liquid for forming an antifouling layer is applied by containing a nano tablet and the content thereof is a predetermined amount or more, the nanosheet is deposited on the opening or the unevenness of the surface of the ceria-based porous film 14. In addition, the liquid medium of the coating liquid for forming an antifouling layer is also inhibited from permeating into the ceria-based porous film 14. For example, even when any component such as a binder is dissolved in a liquid medium, it is unlikely to occur arbitrarily. ingredient Penetration into the cerium oxide-based porous film 14 causes a decrease in anti-reflection performance.

Further, the antifouling layer 16 formed by stacking a plurality of pieces of nano-sheets is denser than the ceria-based porous film 14 and has high surface smoothness, so that dirt is less likely to enter. Therefore, the dirt is less likely to adhere, and it is easy to remove even when the dirt adheres. Further, since the nanosheet is composed of a low refractive material and the entire thickness of the antifouling layer is thin, it is denser than the ceria porous film, but the antireflection property to the ceria porous film 14 is obtained. Almost no effect.

The low refractive material having a refractive index of 1.4 to 1.65 may be appropriately selected from known nanosheets as long as the refractive index is within the above range.

The nanosheet composed of the low refractive index material is preferably derived from an inorganic layered compound selected from the group consisting of a layered polysilicate (refractive index of 1.45) and a clay mineral (refractive index of 1.56 to 1.58). At least one of the groups formed. The nanosheet derived from the inorganic layered compound is less hydrophobic than the fluorine-based coating agent, and the water-repellent surface of the formed antifouling layer is low. Therefore, when the article 10 is placed outside the house, even in the state in which the antifouling layer 16 is provided, it is difficult to cause the dirt to be uniformly washed away by rain or the like and to remain in a spot shape, and the running water is caused by rain or the like. It is easy to maintain a good appearance for a long time.

The inorganic layered compound has a structure in which a plurality of nano-sheets are laminated, and natural products and synthetic products are commercially available. A nanosheet can be obtained by peeling off the layer which comprises this inorganic layered compound.

In the present invention, the clay mineral means an octahedron structure having AlO ₆ or the like in a crystal structure, and from the viewpoint of not having the octahedral structure, the layered polysilicate is different from the clay mineral.

Examples of the layered polyphthalate include, for example, soda sulphate, sodium sulphate, natural sodium citrate, smectite, octosilicate, and the like.

The composition of the layered polyphthalate can be represented by the following composition formula (i). Examples of the alkali metal atom in M include Na, K, and Li.

M ₂ O. xSiO ₂ . yH ₂ O...(i)

In the formula, M is an alkali metal atom, x is an integer of 2 to 40, and y is an integer of 1 to 20.

Examples of the clay mineral include bentonite, vermiculite, and layered double hydroxide (LDH). Examples of the bentonite include a 2-octahedral type (saponite, hectorite, etc.), a 3-octahedral type (montmorillonite, beadite, etc.).

The composition of the 2-octahedral type bentonite can be represented by the following composition formula (ii) (containing an interlayer cation). The composition of the 3-octahedral type bentonite can be represented by the following composition formula (iii) (containing an interlayer cation).

(M ¹ , M ² ) _0.3 (M ³ , M ⁴ ) ₃ (Si, Al) ₄ O ₁₀ (F, OH) ₂ . 4H ₂ O...(ii)

(M ¹ , M ² ) _0.3 (M ³ , M ⁴ ) ₂ (Si, Al) ₄ O ₁₀ (F, OH) ₂ . 4H ₂ O...(iii)

In the formula, M ¹ to M ⁴ are each independently an alkali metal atom, an alkaline earth metal atom or a transition metal atom. The alkali metal atom may be the same as the above. Examples of the alkaline earth metal include Mg, Ca, and the like. Examples of the transition metal atom include Fe, Al, and the like.

The composition of vermiculite can be represented by the following composition formula (iv).

(Mg, Fe, Al) ₃ (Al, Si) ₄ O ₁₀ (OH) ₂ . 4H ₂ O...(iv)

The composition of LDH can be expressed by the following composition formula (v) ion).

[M ⁵ _1-p M ⁶ _p (OH) ₂ ]. [A _p/n . qH ₂ O]...(v)

In the formula, M ⁵ is a divalent metal ion (Mg ²⁺ , Ca ²⁺ , Zn ²⁺ , Ni ^{2+ ,} etc.), and M ⁶ is a trivalent metal ion (Al ³⁺ , Fe ³⁺ , Cr ^{3+ ,} etc.) , A is an n-valent anion, and n is an integer from 1 to 3. A may, for example, be Cl ^- , NO ₃ ^- , CO ₃ ^2- or the like.

Among the above, the inorganic layered compound is preferably a clay mineral, and the bentonite is particularly preferred. The hydroxyl group of the layered polyphthalate exposes the surface of the layer, whereas the hydroxyl groups of the clay mineral do not expose the surface of the layer. Therefore, compared with the nanosheet obtained from the layered polysilicate, the nanosheet obtained from the clay mineral has a weaker adhesion to the ceria porous film 14, and the antifouling layer 16 is easy because Lost when exposed outside the house. By the anti-fouling layer 16 disappearing with time, the low-reflection characteristics of the ceria-based porous film 14 are sufficiently exhibited. Further, in the case where the surface of the ceria porous film 14 has open pores, the article 10 is exposed to ultraviolet rays or wind and rain outside the house, and the antifouling layer is removed to expose the ceria porous film 14 to the outermost surface of the article 10. It is easy to become a hydrophilic surface, and dirt such as sand or angstrom is easily washed away by rain or the like. Therefore, a good appearance can be maintained for a long time.

Further, as a material of the _nanosheet , a titanium oxide system such as Ti _0.91 O ₂ or Ti _1.73 Li _0.27 O ₂ , a manganese oxide system such as MnO _{2 ,} or a lanthanum oxide system such as Nb ₆ O ₁₇ or Nb ₃ O ₈ is known. a transition metal oxide-based material such as tungsten oxide such as WO ₃ ; a transition metal chalcogenide-based material such as MoS ₂ ; and a layered calcium-titanium such as Ca ₂ Nb ₃ O ₁₀ or La ₂ Nb ₂ O ₇ Mineral materials, etc., however, these materials have low transparency or high refractive index even. Therefore, in the case where a nanosheet derived from these materials is used for the antifouling layer, the antireflection performance is lowered, which is not preferable.

The average thickness of the plurality of the above-mentioned nanosheets contained in the antifouling layer is preferably 0.7 to 20 nm, more preferably 0.7 to 15 nm, and more preferably 0.7 to 10 nm. When the average thickness of the nanosheet is 0.7 nm or more, the structure of each nanosheet is less likely to be broken, and the durability of the antifouling layer is increased. When the average thickness of the nanosheet is 20 nm or less, it is easy to form an antifouling layer of a film, for example, an antifouling layer having an average film thickness of 40 nm or less.

The area of the plurality of nanosheets contained in the antifouling layer is preferably 100 nm ² or more, more preferably 200 nm ² or more, and still more preferably 400 nm ² or more. If the area of the sheet nm 100nm ² or more, after coating said coating liquid for forming an antifouling layer to form an antifouling layer, nano-silicon dioxide-based sheet does not easily enter the porous film 14, and silicon dioxide The surface of the porous membrane is smoothly covered by the nanosheet. The upper limit of the area of nano-sheet has not been specifically limited, but in consideration of the antifouling layer is formed in the dispersibility of the coating liquid, easiness to obtain, preferably less places 1,000,000nm ^2, 250,000nm ² or less is preferred .

In consideration of these, the nano-sheets preferably have an average thickness of 0.7 to 20 nm and an average area of 100 to 1,000,000 nm ² , and have an average thickness of 0.7 to 15 nm and an average area of 200 to 1,000,000 nm ² . It has an average thickness of 0.7 to 10 nm and an average area of 200 to 250,000 nm ² is more preferable.

The nanosheet may be a nanosheet which has been surface-modified with a treating agent such as a surfactant, and the nanosheet may further contain a nanosheet which has been surface-modified with a treating agent such as a surfactant. By using a surface-modified nanosheet, the adhered dirt is easily peeled off and can be obtained in a small amount. Full antifouling properties.

The surfactant may, for example, be an alkyl carboxylate such as sodium octoate, potassium octoate, sodium citrate, potassium citrate, sodium laurate, potassium laurate, sodium stearate or potassium stearate; An alkyl sulfonate such as potassium hexanesulfonate, sodium octane sulfonate, potassium octane sulfonate, sodium decane sulfonate, potassium decane sulfonate, sodium dodecane sulfonate or potassium dodecane sulfonate a sulfate such as sodium lauryl sulfate, potassium lauryl sulfate, sodium myristyl sulfate, potassium myristyl sulfate, a phosphate such as sodium lauryl phosphate or sodium tripolyphosphate, tetramethylammonium bromide or tetramethyl Ammonium chloride, tetrabutylammonium bromide, tetrabutylammonium chloride, octyltrimethylammonium chloride, octyltrimethylammonium bromide, decyltrimethylammonium chloride, decyltrimethyl Grade 4 of ammonium bromide, triethanolamine chloride, triethanolamine bromide, tripropanolamine chloride, tripropanolamine bromide, polyoxyethylene alkylammonium chloride, polyoxyethylene alkylammonium bromide, etc. A nonionic surfactant such as alkylammonium, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, cetyl alcohol or oleyl alcohol.

The treatment agent other than the surfactant may, for example, be trimethylformamidine chloride, triethylformamidine chloride, tert-butyldimethyloxane, triisopropylformamidine chloride or chloromethyltrimethyl A mercaptan alkylating agent such as decane, triethyl decane, butyl dimethyl decane, trimethyl vinyl decane, allyl trimethyl decane or hexamethyldioxane.

Further, when the nanosheet is peeled off from the inorganic layered compound, the peeling may be carried out in water containing a surfactant. As a result, the obtained nanosheet dispersion may contain a nanosheet which has been surface-modified with a surfactant.

The number of the nano sheets contained in the antifouling layer 16 may be one type or two or more types.

The antifouling layer 16 may contain a binder in addition to the nanosheet. By containing a binder, the adhesion between the plurality of nano sheets, the denseness of the antifouling layer 16, and the removal property of the antifouling layer 16 when exposed from the outside can be improved.

The binder is not particularly limited, and is preferably dissolved in a coating liquid for forming an antifouling layer. The dispersion medium of the coating liquid for forming an antifouling layer contains a large amount of water. Therefore, the binder is preferably water-soluble as the binder itself or its precursor, and examples thereof include a hydrolyzate of a hydrolyzable decane compound (a decane hydrolyzed sol). Or a condensate thereof, a water-soluble polymer or the like. The binder is preferably a water-soluble polymer. When the water-soluble polymer is exposed to the outside, it is likely to be deteriorated by ultraviolet rays, wind and rain, etc., and therefore the effect of improving the removability of the antifouling layer 16 is obtained.

The hydrolyzable decane compound may, for example, be a compound represented by SiX _m Y _4-m (m is an integer of 2 to 4, X is a hydrolyzable group, and Y is a non-hydrolyzable group). The hydrolyzate of the hydrolyzable decane compound has a structure in which Si-X groups of SiX _m Y _4-m are hydrolyzed to become Si-OH, and Si-OH can be bonded to the surface of the nanosheet. Since the hydrolyzate has two or more Si—OH, the nanosheets can be bonded to each other. Further, the hydrolyzate may also be condensed with each other to form a condensate.

The m system is preferably 3 or 4.

The hydrolyzable group X means a group which converts a Si-X group into a Si-OH group by hydrolysis. Examples of the hydrolyzable group include a halogen atom (for example, a chlorine atom), an alkoxy group, a decyloxy group, an amineoxy group, a decylamino group, a ketoximino group, a hydroxyl group, an epoxy group, a glycidyl group, an isocyanate group, etc., and an alkoxy group. The base is especially good.

The non-hydrolyzable group Y means a functional group whose structure does not change under the condition that the Si—X group becomes a Si—OH group by hydrolysis. The non-hydrolyzable group is not particularly limited, and may be a non-hydrolyzable group known as a decane coupling agent or the like.

Specific examples of the hydrolyzable decane compound include tetraalkoxy decane (tetramethoxy decane, tetraethoxy decane, tetrapropoxy decane, tetrabutoxy decane, etc.), and alkoxy decane having an alkyl group ( Methyl trimethoxy decane, methyl triethoxy decane, ethyl trimethoxy decane, ethyl triethoxy decane, propyl trimethoxy decane, propyl triethoxy decane, decyl trimethoxy a decane, a mercaptotriethoxydecane, etc., an alkoxydecane having an aryl group (phenyltrimethoxydecane, phenyltriethoxydecane, etc.), an alkoxydecane having a perfluoropolyether group ( Perfluoropolyether triethoxydecane, etc.), alkoxydecane having a perfluoroalkyl group (perfluoroethyltriethoxydecane, etc.), alkoxydecane having a vinyl group (vinyltrimethoxydecane) , vinyl triethoxy decane, etc.), alkoxy decane having an epoxy group (2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-glycidyl ether propyltrimethoxy Base decane, 3-glycidyl ether propyl methyl diethoxy decane, 3-glycidyl ether propyl triethoxy decane, etc., having an acryloxy group Alkoxydecane (3-propenyloxypropyltrimethoxydecane, etc.) and the like.

Among the above, in the case where the antifouling layer 16 is hydrophilic, a tetraalkyloxydecane such as tetramethoxynonane, tetraethoxysilane, tetrapropoxydecane or tetrabutoxydecane is preferred. In the case where the antifouling layer 16 has water repellency, it is preferred to use an alkoxysilane having an alkyl group or an alkoxy decane having a perfluoroalkyl group.

The hydrolysis of the hydrolyzable decane compound is water in an amount such that all of the hydrolyzable groups of the hydrolyzable decane compound are hydrolyzed (for example, in the case of tetraalkoxy decane, water of 4 or more moles of tetraalkoxy decane) ) and the acid or base as a catalyst. Examples of the acid include inorganic acids (HNO ₃ , H ₂ SO ₄ , HCl, etc.) and organic acids (antacid, oxalic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, etc.). Examples of the base include ammonia, sodium hydroxide, potassium hydroxide, and the like. From the standpoint of long-term preservation, the catalyst is preferably acid. Further, the catalyst is preferably such that it does not interfere with the dispersion of the nanosheet.

Examples of the water-soluble polymer include polyvinyl alcohol, polyethylene glycol, polyethylene oxide, polyvinyl pyrrolidone, polyethyleneimine, polydiallyldimethylammonium chloride, sodium polyacrylate, and polypropylene. Indoleamine, polylactic acid, sodium polystyrene sulfonate, sodium polyvinyl sulfate, carboxyvinyl polymer, carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose, guar gum, cationic guar gum , carrageenan, sodium alginate, corn starch, sanxian gum, sodium chondroitin sulfate, sodium hyaluronate, starch, processed starch, animal glue, gelatin, gum arabic, sodium alginate, pectin and the like.

The molecular weight of the water-soluble polymer is preferably from 1,000 to 100,000. When the molecular weight is less than 1,000, the water-soluble polymer easily permeates into the inside of the ceria-based porous film 14, and the transmittance is liable to lower. If the molecular weight is more than 100,000, it becomes less soluble in the solvent, and in the coating, aggregates are formed with the nanosheet, and the stability of the coating may be lowered.

The antifouling layer 16 may contain other components than the nanoparticles and the binder in a range that does not impair the effects of the present invention as necessary. Examples of the other component include a surfactant which does not modify the surface of the nanosheet, cerium oxide microparticles, and titanium dioxide microparticles. In the case of containing titanium oxide fine particles, decomposition of adhering dirt can be expected by the photocatalytic effect.

The anti-fouling layer 16 has an average film thickness of 0.4 to 40 nm, preferably 1 to 20 nm. If the average thickness of the antifouling layer 16 is 0.4 nm or more, sufficient Antifouling properties. When it is 40 nm or less, the antifouling layer 16 has little influence on the antireflection performance of the ceria porous film 14 and can suppress the decrease in the maximum transmittance by providing the antifouling layer 16.

The method for measuring the average film thickness of the antifouling layer 16 is as shown in the examples below.

The antifouling layer 16 does not have to cover the entire surface of the ceria-based porous film 14. For example, a part of the surface of the ceria-based porous film 14 may be coated to partially expose the surface of the ceria-based porous film 14.

(Manufacturing method of article 10)

The article 10 can be produced, for example, by applying a coating liquid for forming a ceria-based porous film on a transparent substrate 12 and baking it to form a ceria-based porous film 14 ( The coating liquid for forming an antifouling layer containing a plurality of nano tablets and a dispersion medium of the nanosheet is applied to the surface of the above-mentioned ceria porous film and dried. The step of forming an antifouling layer (hereinafter referred to as "second step").

{first step}

The first step can be carried out by a known production method in accordance with the known ceria-based porous film, and is not particularly limited, and can be dispersed in the dispersion medium by, for example, containing a dispersion medium (a). The fine particles (a) in a) and the coating liquid (hereinafter referred to as "top coating liquid") of the substrate precursor (c) dissolved or dispersed in the dispersion medium (a) are applied to a transparent substrate. 14 is carried out and fired to carry out. Thereby, a film in which fine particles (b) are dispersed in a base material composed of a fired product (SiO ₂ ) of a hydrolyzate of alkoxysilane can be formed.

The dispersion medium (a) is a liquid in which the fine particles (b) are dispersed. Dispersion The substance (a) may also be a solvent capable of dissolving the substrate precursor (c).

In the case where the substrate precursor (c) is a hydrolyzate of alkoxydecane, water must be present during the hydrolysis, and therefore the dispersion medium (a) is preferably at least water.

Water can also be used in combination with other liquids. Examples of the other liquid include alcohols (methanol, ethanol, isopropanol, butanol, diacetone alcohol, etc.), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), and ethers (tetrahydrofuran). 1,4-two Alkane, etc., celluloids (methyl acesulfame, ethyl acesulfame, etc.), esters (methyl acetate, ethyl acetate, etc.), glycol ethers (ethylene glycol monoalkyl ether, etc.), A nitrogen-containing compound (N,N-dimethylacetamide, N,N-dimethylformamide, N-methylpyrrolidone, etc.), a sulfur-containing compound (dimethylammonium or the like), and the like.

Among the above other liquids, the solvent of the substrate precursor (c) is preferably an alcohol, and particularly preferably methanol or ethanol.

Examples of the fine particles (b) include metal oxide fine particles, metal fine particles, fine pigment particles, and resin fine particles.

Examples of the material of the metal oxide fine particles include Al ₂ O ₃ , SiO ₂ , SnO ₂ , TiO ₂ , ZrO ₂ , ZnO, CeO ₂ , Sb-containing SnO _X (ATO), and Sn-containing In ₂ O ₃ (ITO). RuO ₂ and the like, from the viewpoint of low refractive index, SiO _{2 is} preferred.

Examples of the material of the metal fine particles include a metal (such as Ag or Ru), an alloy (such as AgPd or RuAu), and the like.

Examples of the pigment-based fine particles include inorganic pigments (such as titanium black and carbon black) and organic pigments.

Examples of the material of the resin fine particles include polystyrene, melanin resin, and the like.

Examples of the shape of the fine particles (b) include a spherical shape, an elliptical shape, a needle shape, a plate shape, a rod shape, a conical shape, a cylindrical shape, a cubic shape, a rectangular parallelepiped shape, and a drill. Stone, star, indefinite shape, etc. Further, the fine particles (b) may be hollow or open-celled. Further, the fine particles (b) can exist in a state in which the respective fine particles are independent, and each of the fine particles can be connected in a chain shape, and aggregation can also occur.

The microparticles (b) may be used alone or in combination of two or more.

The average agglomerated particle diameter of the fine particles (b) is preferably from 1 to 1,000 nm, more preferably from 3 to 500 nm, more preferably from 5 to 300 nm. When the average agglomerated particle diameter of the fine particles (b) is 1 nm or more, the antireflection effect is sufficiently improved. When the average agglomerated particle diameter of the fine particles (b) is 1,000 nm or less, the haze of the ceria porous film 14 can be lowered.

The average agglomerated particle diameter of the fine particles (b) is the average agglomerated particle diameter of the fine particles (b) in the dispersion medium (a), which can be measured by a dynamic light scattering method. Further, in the case where the agglomerated monodisperse fine particles (b) are not observed, the average aggregated particle diameter is equal to the average primary particle diameter.

The substrate precursor (c) is preferably a hydrolyzate of alkoxydecane.

Examples of the alkoxydecane include a tetraalkoxydecane (tetramethoxydecane, tetraethoxydecane, tetrapropoxydecane, tetrabutoxydecane, etc.), and alkoxydecane having a perfluoropolyether group ( Perfluoropolyether triethoxydecane, etc.), alkoxydecane having a perfluoroalkyl group (perfluoroethyltriethoxydecane, etc.), alkoxydecane having a vinyl group (vinyltrimethoxydecane) , vinyl triethoxy decane, etc.), alkoxy decane having an epoxy group (2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-glycidyl ether propyltrimethoxy Alkoxydecane (3-propene oxime) having a propylene decyloxy group, a decyl alkane, a 3-glycidyl ether propyl methyl diethoxy decane, a 3-glycidyl propyl triethoxy decane, etc. Oxypropyltrimethoxydecane, etc.).

The hydrolysis of the alkoxydecane can be carried out by the same method as the hydrolysis of the hydrolyzable decane compound described above. The catalyst used in the hydrolysis is preferably such that the dispersion of the fine particles (b) is not hindered.

The top coating liquid may also contain a terpene derivative (d), other additives, and the like as necessary.

Terpene means a hydrocarbon having a composition of (C ₅ H ₈ ) _n (however, n is an integer of 1 or more) having isoprene (C ₅ H ₈ ) as a constituent unit. The terpene derivative means a terpene having a functional group derived from a terpene. The terpene derivative (d) also includes those having different degrees of unsaturation. In addition, in the terpene derivative (d), there is a terpene which can exhibit the function of the dispersion medium (a), but "a hydrocarbon having a composition of (C ₅ H ₈ ) _n having isoprene as a constituent unit", It refers to those belonging to the terpene derivative (d) and not belonging to the dispersion medium (a).

From the viewpoint of the antireflection effect of the ceria-based porous film 14, the terpene derivative (d) is preferably a terpene derivative having a hydroxyl group and/or a carbonyl group in the molecule, and has a hydroxyl group selected from the group consisting of a hydroxyl group. One or more kinds of terpenes in the group consisting of aldehyde group (-CHO), keto group (-C(=O)-), ester bond (-C(=O)O-), and carboxyl group (-COOH) The derivative is preferably one or more kinds of terpene derivatives selected from the group consisting of a hydroxyl group, an aldehyde group and a ketone group in the molecule.

Examples of the terpene derivative (d) include terpene alcohol (α-terpineol, terpinene-4-ol, L-menthol, (±) citronellol, myrtenol, nerol, anthraquinone Alcohol, farnesol, phytol, etc.), nonenal (citral, beta-cyclocitral, perillaldehyde, etc.), decenone ((±) camphor, β-ionone, etc.), terpene carboxylic acid ( Citronellic acid, rosin acid, etc.), terpene esters (decyl acetate, menthyl acetate, etc.), and the like. In particular, terpene alcohol is preferred.

The terpene derivative (d) may be used alone or in combination of two or more.

Other additives include a surfactant for improving the leveling property, a metal compound for improving the durability of the cerium oxide-based porous film 14, and the like.

Examples of the surfactant include a polyoxyphthalic acid system and an acrylic resin.

The metal compound is preferably a zirconium chelate compound, a titanium chelate compound, an aluminum chelate compound or the like. Examples of the zirconium chelate compound include zirconium tetraacetate pyruvate and zirconium tributoxystearate.

The viscosity of the top coating liquid is 1.0~10.0mPa. s is better, 2.0~5.0mPa. s is preferred. The viscosity of the top coating solution is 1.0mPa. When it is s or more, it is easy to control the film thickness of the top coating liquid applied on the transparent substrate 12. The viscosity of the top coating solution is at 10.0mPa. Below s, the drying or firing time or coating time is shortened.

The viscosity of the top coating can be determined by a B-type viscometer.

The solid content concentration of the top coating liquid is preferably from 1 to 9% by mass, and preferably from 2 to 6% by mass. When the solid content concentration is 1% by mass or more, the coating film thickness of the top coating liquid applied to the transparent substrate 12 can be reduced, and the film thickness of the finally obtained ceria-based porous film 14 can be made uniform. When the solid content concentration is 9% by mass or less, the coating film thickness of the top coating liquid applied to the transparent substrate 12 is easily made uniform.

The solid content of the top coating liquid means the total of the fine particles (b) and the substrate precursor (c) (however, the solid content of the substrate precursor (c) is a SiO ₂ equivalent amount of the alkoxysilane).

The quality of the fine particles (b) and the substrate precursor (c) in the top coating liquid The amount ratio (microparticle/substrate precursor) is preferably 95/5 to 10/90, and 70/30 to 90/10 is preferred. When the amount of the fine particles/substrate precursor is 95/5 or less, the adhesion between the ceria-based porous film 14 and the transparent substrate 12 is sufficiently improved. When the microparticle/substrate precursor is 10/90 or more, the antireflection effect is sufficiently improved.

In the case where the terpene derivative (d) is blended into the top coating liquid, the blending amount thereof is preferably 0.01 to 2 parts by mass based on 1 part by mass of the solid content of the top coating liquid, 0.03~ 1 part by mass is preferred. When the terpene derivative (d) is 0.01 parts by mass or more, the antireflection effect is sufficiently improved as compared with the case where the terpene derivative (d) is not added. When the terpene derivative (d) is at least 2 parts by mass, the strength of the cerium oxide-based porous film 14 is good.

The top coating liquid can be prepared by, for example, mixing a fine particle (b) dispersion, a substrate precursor (c) solution, a dispersion medium (a) which is added as necessary, a terpene derivative (d), and other additives.

Since the top coating liquid described above contains the dispersion medium (a) and the fine particles (b) and the substrate precursor (c), it is possible to form a cerium oxide having an antireflection effect at low cost and even at a lower temperature. A porous membrane. In other words, when the ceria-based porous film is formed using the top coating liquid, voids are selectively formed around the fine particles (b) in the ceria-based porous film, so that the void is resistant. The reflection effect is improved.

Further, in the case where the top coating liquid contains the terpene derivative (d), since the volume of the void portion is increased, the antireflection effect is increased.

The coating method of the top coating liquid can be carried out by a known wet coating method (spin coating method, spray coating method, dip coating method, mold coating method, Curtain coating method, screen coating method, inkjet method, flow coating method, gravure coating method, bar coating method, flexographic coating method, slit coating method, roll coating method, sponge roller coating Covering method, blade coating method, etc.).

Among these, a roll coating method is preferred, and a reverse roll coating method by a coating roll of a reverse roll coater is particularly preferred.

The coating temperature is preferably from room temperature to 80 ° C, and room temperature to 60 ° C is preferred.

The baking of the top coating liquid coating film formed on the transparent substrate may be performed after the application of the top coating liquid, or the transparent substrate 12 may be previously heated to the firing temperature, and then on the surface of the transparent substrate 12. The top coating solution was applied.

The firing temperature is preferably 30° C. or higher, and may be appropriately determined depending on the material of the transparent substrate 12, the fine particles (b), or the substrate precursor (c). In order to rapidly form a hydrolyzate of alkoxydecane into a fired product, it may be calcined at 80 ° C or higher, preferably at 100 ° C or higher, and preferably at 200 to 700 ° C. When the firing temperature is 100 ° C or more, the fired product is densified and the durability is improved.

In the case where the transparent substrate 12 is glass, the baking step in forming the ceria-based porous film 12 may be a physical strengthening step of the glass. In the physical strengthening step, the glass is heated to near the softening temperature. In this case, the firing temperature is set before and after about 600 to 700 °C. The firing temperature is usually set to be lower than the heat distortion temperature of the transparent substrate 12. The lower limit of the firing temperature can be determined by the formulation of the top coating solution.

Even if it is naturally dried, the polymerization will reach a certain degree, so as long as there is no limitation on the time, it is theoretically possible to set the drying or baking temperature to a temperature near room temperature.

{Second step}

In the second step, the surface of the ceria-based porous film 14 formed on the surface of the transparent substrate 12 by the first step is coated with a dispersion medium containing a plurality of nanosheets and the nanosheet. The coating liquid for forming a stain layer (hereinafter also referred to as "external coating liquid") is dried to form the antifouling layer 16. Thereby, the article 10 can be obtained.

The external coating liquid contains a plurality of nano tablets and a dispersion medium of the nano tablets.

The description of the nanosheet is the same as described above.

The nanosheet may be layer-peeled by a layered compound such as a commercially available layered polysilicate or a layered clay mineral, or may be produced by a known production method.

The nanosheet can be obtained, for example, by peeling off a layer constituting the above-mentioned inorganic layered compound which is natural or synthetic. For example, by adding an inorganic layered compound to water, swelling it, and stirring it, a nanosheet dispersion in which a nanosheet is dispersed in water can be obtained. Further, the inorganic layered compound may be previously treated with a surfactant or the like in order to improve the dispersibility in a solvent.

The nanosheet dispersion can be used directly as an external coating liquid, and can also be used for the preparation of an external coating liquid. For example, an external coating liquid can be prepared by mixing a nanosheet dispersion with a solution of an optional component (adhesive or its precursor). It is also possible to recover the nanosheet from the nanosheet dispersion and use it for the preparation of the external coating liquid.

In the external coating liquid, the content of the nanosheet is not particularly limited as long as it is within the range in which the external coating liquid can be applied, and is opposed to the external coating liquid. The total amount (100% by mass) is preferably 0.05 to 0.50% by mass, and preferably 0.10 to 0.35% by mass. When the content of the nanosheet is 0.05% by mass or more, when the external coating liquid is applied, the optional component dissolved in the external coating liquid does not easily penetrate into the cerium oxide-based porous membrane 14. When the content of the nanosheet is 0.50% by mass or less, the coating property of the external coating liquid is good, and the antifouling layer of the film can be formed, and the uniformity of the film thickness of the formed antifouling layer is also good.

The dispersion medium is a liquid in which a nanosheet is dispersed. In the case where the binder is blended in the external coating liquid, the dispersion medium is preferably a solvent which dissolves the binder. The dispersion medium may be a single liquid or a mixed liquid in which two or more liquids are mixed.

The dispersion medium is suitable for using water. Water and organic solvents can also be used as necessary. The dispersion medium may also be an organic solvent alone.

Examples of the organic solvent include alcohols (methanol, ethanol, isopropanol, butanol, diacetone alcohol, etc.), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), and ethers (tetrahydrofuran, 1,4-two Alkane, etc., celluloids (methyl acesulfame, ethyl acesulfame, etc.), esters (methyl acetate, ethyl acetate, etc.), glycol ethers (ethylene glycol monoalkyl ether, etc.), A nitrogen-containing compound (N,N-dimethylacetamide, N,N-dimethylformamide, N-methylpyrrolidone, etc.), a sulfur-containing compound (dimethylammonium or the like), and the like. From the viewpoints of the drying property of the solvent, the compatibility with water, and the surface tension, among these, an alcohol is preferable, and methanol and ethanol are particularly preferable.

When the dispersion medium contains water, the water content in the external coating liquid is preferably 60% by mass or less based on the total mass of the external coating liquid, and preferably 50% by mass or less. If the water content in the external coating liquid is more than 60% by mass, the drying of the solvent in the drying step after coating is not good, and the appearance of the coating film is not Good is easy to happen.

In the case where a layer containing a binder is formed as the antifouling layer 16, a binder or a precursor thereof may be blended in the external coating liquid. For example, in the case where the binder is a condensate of a hydrolyzate of a hydrolyzable decane compound, a binder precursor may be blended in the external coating liquid. The binder precursor may be a hydrolyzate of a hydrolyzable decane compound or a hydrolyzable decane compound which may be a precursor thereof.

The description of the binder and its precursor is the same as described above.

In the case where the external coating liquid contains a binder, the content thereof is a mass ratio of the nanosheet content to the total amount of the nanosheet and the binder or its precursor (nano sheet/(nano sheet+adhesive)) It is preferable to be a quantity of 0.25 or more. The value of the nanosheet/(nano sheet + binder) is preferably 0.375 or more, and more preferably 0.50 or more. When the nanosheet/(nano sheet + binder) is at least 0.25, the penetration of the binder can be suppressed to cause a decrease in the antireflection performance of the cerium oxide-based porous membrane 14, and the maximum transmission of the antifouling layer 16 can be sufficiently suppressed. The rate is reduced. The total amount of the nanosheet and the binder or the precursor thereof is preferably 80 to 100% by mass based on the total mass of the solid component in the external coating liquid, and preferably 90 to 100% by mass.

In the case where the binder is a hydrolyzate of a hydrolyzable decane compound, the content of the binder or its precursor is a solid component in terms of SiO ₂ .

In the case of containing a binder or a precursor thereof, the external coating liquid can be prepared by, for example, mixing a nanosheet dispersion with a solution of a binder or a precursor thereof.

In the external coating liquid, other components other than the nanosheet, the binder, and the precursor thereof may be blended as necessary.

The other component is preferably a surfactant.

The blending amount of the surfactant is preferably such that the mass ratio of the surfactant to the nanosheet content (the surfactant/nanosheet) is 1.5 or less. If the surfactant/nanosheet exceeds 1.5, the surfactant component easily permeates into the ceria porous film to cause a decrease in transmittance.

The solid content concentration in the external coating liquid is preferably 0.05 to 0.50% by mass, and preferably 0.1 to 0.4% by mass. When the solid content concentration in the external coating liquid is less than 0.05% by mass, the antifouling property is likely to be insufficient. On the other hand, when it is more than 0.50 mass%, the antifouling layer becomes too thick, and the transmittance is likely to be insufficient.

The coating method of the external coating liquid may be a well-known wet coating method (rotary coating method, spray coating method, dip coating method, mold coating method, curtain coating method, screen coating method, Ink jet method, flow coating method, gravure coating method, bar coating method, flexographic coating method, slit coating method, roll coating method, sponge roll coating method, blade coating method, and the like).

The coating temperature is preferably from room temperature to 80 ° C, and preferably from 35 to 60 ° C.

The coating liquid for forming an antifouling layer is applied onto the surface of the ceria porous film, and after drying, the antifouling layer 16 is formed.

When the external coating liquid contains only a nano tablet as a solid component, that is, when no component other than the nano tablet (adhesive or its precursor, surfactant, etc.) is contained, the drying after coating may be performed. The dispersion medium may be removed, and the drying conditions are not particularly limited, and it is preferred to satisfy the following drying conditions 1.

(Drying condition 1)

The drying is carried out at a drying temperature of 300 ° C or lower (preferably 250 ° C or lower, more preferably 200 ° C or lower). If it is below 300 ° C, it can prevent nano tablets and dioxane The ruthenium-based porous membranes and the nanosheets are strongly sintered with each other without sacrificing the removal of the anti-fouling layer when exposed to the outside.

The lower limit of the drying temperature is not particularly limited, and it is preferred that the substrate temperature be 60 ° C or higher and 80 ° C or higher. If it is 60 ° C or more, the dispersion medium is sufficiently removed.

In the case where the external coating liquid contains a binder or a precursor thereof, drying after coating is carried out at a temperature not exceeding the thermal decomposition temperature of the binder to satisfy the drying condition 1 described above. When heated to a temperature higher than the thermal decomposition temperature, the binder in the antifouling layer is thermally decomposed, which may impair the effect of the inclusion of the binder (for example, adhesion of the nanosheets in the antifouling layer) , raising the density of the antifouling layer, etc.).

The lower limit of the drying temperature is not particularly limited, and it is desirable that the substrate temperature be 60 ° C or higher, preferably 80 ° C. If it is 60 ° C or more, the dispersion medium is sufficiently removed.

When the external coating liquid contains an organic substance other than the binder and its precursor, such as a surfactant, it is preferable to satisfy the drying condition 1 and dry at a temperature not exceeding the thermal decomposition temperature of the organic substance. . When heated to a temperature higher than the thermal decomposition temperature, the organic matter is thermally decomposed, which may impair the effect of the inclusion of the binder.

The lower limit of the drying temperature is not particularly limited, and it is desirable that the substrate temperature be 60 ° C or higher, preferably 80 ° C. If it is 60 ° C or more, the dispersion medium is sufficiently removed.

The thermal decomposition temperature of the organic substance can be measured by differential thermal-thermal weight simultaneous measurement (TG-DTA).

The present invention has been described above by way of embodiments, but the present invention is not limited to the above embodiments. The components, the combinations, and the like in the above-described embodiments are merely examples, and the additions, omissions, substitutions, and other modifications may be made without departing from the scope of the invention.

Since the antifouling antireflection film of the present invention has an antifouling layer on the surface of the ceria porous film, the antireflection performance of the ceria porous film can be maintained and the antifouling property can be improved.

Therefore, the article of the present invention having the antifouling antireflection film of the present invention on the surface of the transparent substrate has a higher maximum transmittance than the transparent substrate and also has better antifouling properties.

The article of the present invention can be used as a transparent part for a vehicle (a headlight housing, a side mirror, a front transparent substrate, a side transparent substrate, a rear transparent substrate, an instrument panel, etc.), a meter, a building window, a display window, a display (note type) Computer, monitor, LCD, PDP, ELD, CRT, PDA, etc.), LCD color filter, touch panel substrate, read head lens, optical lens, spectacle lens, camera part, camera part, CCD cover substrate , fiber end face, projector parts, photocopier parts, transparent substrate for solar cells, mobile phone window, backlight unit parts (such as light guides, cold cathode tubes, etc.), backlight unit parts (such as enamel, semi-transparent film, etc.) , liquid crystal brightness enhancement film, organic EL light-emitting element parts, inorganic EL light-emitting element parts, phosphor light-emitting element parts, optical filters, end faces of optical parts, illumination lamps, housings for lighting fixtures, amplified laser light sources, anti-reflection films , polarizing film, agricultural film, etc.

Example

The invention is further illustrated in detail below by way of examples. but It is to be understood that the invention is not limited by the following examples.

Among the following examples 1 to 29, examples 1 to 21 are examples, and examples 22 to 29 are comparative examples.

The measurement method, the evaluation method, and the raw materials (nano tablet dispersion and other raw materials) used in each example are disclosed below.

(refractive index of nanosheets)

The nano-sheet dispersion was applied onto a ruthenium substrate, and the obtained film-attached substrate was measured by an ellipsometer (manufactured by JA Woollam Co., Ltd., model: M-2000DI) to obtain a refraction of the nanosheet at a wavelength of 589 nm. rate.

(average thickness, average width, average area of the nanosheet)

The average thickness of the nanosheets was calculated as described below. The nanosheet dispersion was applied onto a glass substrate by a spin coating method, and the surface was observed with an atomic force microscope (manufactured by SII Nanotechnology Co., Ltd.), and the average value of 10 nanosheets was arbitrarily selected from the measurement range of 2 μm square. The average thickness is used.

The average width of the nanosheets is calculated as described below. Observed by the aforementioned atomic force microscope, the length of the line segment connecting the two points farthest from one nano sheet was obtained. Find the longest segment length among the segments on the nanoslice perpendicular to this segment. The average of the two segments is determined as the width of the nanosheet, and for any of the 10 nanosheets, the average of the widths of the 10 segments is set to the average width.

The average area is calculated as described below. For a piece of nanosheet, the product of the two line segments calculated in the same manner as described above is obtained, and then divided by 2, and the obtained value is defined as the area of the nanosheet. For any 10 nanosheets, the average of the area of the 10 is the average area.

(Average transmittance (0° incident), maximum transmittance (0° incident))

The anti-fouling layer side surface of the article produced by each of the examples produced at an incident angle of 0° (or the ceria-based porous film side of the transparent substrate with the ceria-based porous film before the formation of the antifouling layer) The transmittance of light on the surface is measured by a spectrophotometer (manufactured by Hitachi, Ltd., model: U-4100), and the average transmittance (%) and maximum transmittance in the range of 400 to 1,100 nm are obtained. (%).

(film thickness of antifouling layer)

Comparing the wavelength of the maximum transmittance which can be obtained by the measurement of the maximum transmittance (0° incidence) before and after application of the external coating liquid (that is, the coating liquid for forming an antifouling layer), the formed antifouling layer is calculated. Film thickness.

(the maximum amount of transmittance change caused by coating)

The maximum transmittance (hereinafter referred to as "maximum transmittance before coating") of the transparent base material with the cerium oxide-based porous film before the formation of the anti-staining layer was measured in the same manner as described above, and the anti-fouling layer was formed. The maximum transmittance of the obtained article (hereinafter referred to as "maximum transmittance after coating"), and the amount of change in each maximum transmittance (maximum transmittance after coating (%) - maximum transmittance before coating) (%)).

The larger the value of the amount of change, the less the decrease in the antireflection performance of the ceria-based porous film caused by the application of the external coating liquid (coating liquid for forming an antifouling layer). Further, the closer the amount of change is to 0, the less the influence of the antifouling layer on the antireflection performance of the ceria porous film. The amount of change is preferably in the range of -0.2 to 0.2, and particularly preferably in the range of -0.1 to 0.2.

(Resin peel strength test)

The peeling force of the ethylene-vinyl acetate copolymer resin (EVA) film was measured in the following order as an index of antifouling property.

The EVA film having a thickness of 0.8 mm was cut into a width of 5 mm and a length of 80 mm, and placed on the surface of the antifouling layer side of each article obtained, and kept at 160 ° C for 30 minutes in a drying oven. After taking out from the drying furnace and measuring the temperature of the substrate to room temperature, the force required to tear the EVA film attached to the antifouling layer (hereinafter referred to as "peeling force", unit: g/5 mm) was measured using a spring balance. The smaller the peeling force, the more easily the EVA film is peeled off, that is, the antifouling property is excellent.

(maximum transmittance after exposure from outside the house)

The removal of the antifouling layer during outdoor exposure was evaluated in the following order.

The antifouling low-reflection film of Examples 2, 7, 10, 21, and 29 described later was placed outside the house. After 1 week, the maximum transmittance of the article was measured in the same manner as described above. The removal of the antifouling layer was evaluated by comparing the maximum transmittance before and after the exposure. The maximum transmittance after exposure, as compared with the maximum transmittance before exposure, the closer to the maximum transmittance before the formation of the antifouling layer, the higher the removal of the antifouling layer.

<Modulation of top coating liquid>

24.5 g of denatured ethanol was stirred, and 24.0 g of isobutanol was added thereto, and 20.0 g of the substrate precursor solution (c1) prepared in the following order, and the following chain SiO ₂ fine particle dispersion (b1) 15.5 g. Further, 15.0 g of diacetone alcohol (hereinafter referred to as DAA) and 1.0 g of α-terpineol of a terpene derivative were added to prepare a top coating liquid (a1) having a solid concentration of 3.0% by mass.

Chain SiO ₂ fine particle dispersion (b1):

"SNOWTEX (trade name) OUP" manufactured by Nissan Chemical Industries Co., Ltd., a solid content concentration of 15.5 mass% in terms of SiO ₂ , an average primary particle diameter of 10 to 20 nm, and an average agglomerated particle diameter of 40 to 100 nm.

Modulation of the substrate precursor solution (c1):

The denatured ethanol (manufactured by Nippon Alcohol Trading Co., Ltd., Solmix AP-11 (trade name), a mixed solvent containing ethanol as the main agent, the same as the following) was stirred at 77.6 g, and 11.9 g of ion-exchanged water and 0.19% by mass of nitric acid were added thereto. Mix the mixture with g and stir for 5 minutes. Further, 10.4 g of tetraethoxy decane (solid content concentration: 29% by mass in terms of SiO ₂ ) was added thereto, and the mixture was stirred at room temperature for 30 minutes to prepare a substrate precursor solution having a solid content concentration of 3.0% by mass in terms of SiO ₂ ( C1). Further, SiO ₂ solid content concentration calculated as tetraethyl orthosilicate Si into the entire solid content concentration of ₂ SiO.

<Modulation of nanosheet dispersion>

. Preparation of nanosheet dispersion (A):

99.0 g of distilled water was stirred, and 1.0 g of synthetic bentonite ("Lucentite SWN" (trade name) manufactured by Co-op Chemical Co., Ltd.) was added thereto, and the mixture was stirred for 24 hours to prepare a nanosheet dispersion (A).

. Preparation of nanosheet dispersion (A'):

98.0 g of distilled water was stirred, and 2.0 g of synthetic bentonite ("Lucentite SWN" manufactured by Co-op Chemical Co., Ltd.) was added thereto, and the mixture was stirred for 24 hours to prepare a nanosheet dispersion (A ' ).

. Preparation of nanosheet dispersion (B):

A synthetic bentonite ("Lucentite SWN" manufactured by Co-op Chemical Co., Ltd.) was chemically modified by the means described in JP-A-6-2870146 to prepare a nanosheet dispersion (B) in which the material was dispersed. in particular, 2 g of synthetic bentonite ("Lucentite SWN" manufactured by Co-op Chemical Co., Ltd.) was dispersed in 100 mL of distilled water to prepare a suspension. 60 mL of an aqueous solution in which 3.5 g of polyoxyethylene alkylmethylammonium chloride was dissolved was added to the above-mentioned synthetic bentonite suspension, and the mixture was reacted at room temperature for 2 hours with stirring. The product is subjected to solid-liquid separation, washed, and the by-produced salt is removed, followed by drying to obtain a nanosheet surface-modified with a treating agent such as a surfactant. 2.6 g of the nanosheet obtained by surface-treating the treatment agent such as a surfactant was added to 97.4 g of ethanol under stirring, and the mixture was stirred for 24 hours to prepare a nanosheet dispersion (B).

. Preparation of nanosheet dispersion (C):

The synthesis of the layered polysilicate nanosheet was carried out by the means described in the following Document 1.

SiO ₂ and NaOH were mixed with water to make SiO ₂ :NaOH:water = 4:1:25.8 (mass ratio), and the mixture was reacted at 100 ° C for 2 hours in a polytetrafluoroethylene container. An aqueous solution of cetyltrimethylammonium chloride was added to the resultant, and the mixture was stirred for 1 day. The solid and liquid were separated, and the resultant was dried. To 1 g of the powder obtained in this manner, 100 mL of toluene and 1-butyl-3-(3-triethoxycarbamidopropyl)-4,5-dihydroimidazolinium were added under a nitrogen atmosphere. Chloride 3.7 g was allowed to react at 70 ° C for 1 hour. After the reaction, solid-liquid separation was carried out, and 40 mg of the washed and dried product was dispersed in 20 g of water by ultrasonic treatment to obtain a 0.25 mass% nanosheet dispersion (C).

Document 1: Chemistry of Materials, 2011, 23, 266-273

. Preparation of nanosheet dispersion (D):

An aqueous colloidal solution of nanocrystalline titanate was prepared as described below. A mixture of the stoichiometric composition of Cs ₂ CO ₃ and TiO ₂ was fired at 800 ° C for 20 hours to prepare a ruthenium titanate precursor. 70 g of the obtained cerium titanate precursor was immersed in 2 L of a 1 mol/L HCl solution. The acid solution was treated with the HCl solution, and a new solution was replaced every 24 hours for a total of 3 times. The obtained acid substitute was filtered, washed with water, and then dried in the air. The obtained proton titanate was added to a 0.0017 mol/L tetrabutylammonium hydroxide solution, and vigorously shaken at room temperature for 10 days to obtain a milky white colloidal suspension. The liquid obtained was concentrated to adjust the solid content to 0.4% by mass to obtain a nanosheet dispersion (D).

The composition of the prepared nanosheet dispersion is disclosed in Table 1. In Table 1, SWN represents "Lucentite SWN" manufactured by Co-op Chemical Co., Ltd. Any of the SWNs are powdered bentonites.

As a result of observing the SWN by a transmission electron microscope and an atomic force microscope, the morphology was a sheet (nano sheet). The refractive index, average thickness, average width, and average area of each of the nanosheets were measured, and as a result, the results shown in Table 1 were obtained.

<Modulation of the binder solution>

. Modification of the binder solution (E) (polymer solution):

99.0 g of distilled water was stirred, and 1.0 g of polyvinyl alcohol (manufactured by Polymer Science, molecular weight 25,000, saponification degree 88%) was added thereto, and stirred in a 60-degree warm bath for 1 hour to prepare a binder solution (E). .

. Modification of the binder solution (F) (decane dilution):

93.0 g of ethanol was stirred while 7 g of tetraethoxydecane was added thereto, and the mixture was stirred at room temperature for 30 minutes to prepare a binder solution (F).

. Modification of the binder solution (G) (decane hydrolyzed sol):

80.5 g of denatured ethanol was stirred, and a mixed liquid of 11.4 g of ion-exchanged water and 0.5 g of 10% by mass of nitric acid was added thereto, and the mixture was stirred for 5 minutes. It was added to a tetraethyl orthosilicate (calculated as SiO ₂ solid content concentration: 29 mass%) 7.6 g of, stirred for 30 minutes at room temperature, to prepare a solid content concentration calculated as SiO ₂ of 2.2% by mass of the sol (binder solution ( G)).

<Modulation of other raw materials>

. Modulation of surfactant solution (H):

95.0 g of water was stirred while 5.0 g of a tetrabutylammonium 40% aqueous solution was added thereto, and the mixture was stirred for 30 minutes to prepare a surfactant solution (H).

[example 1]

An article having the same layer constitution as the article 10 shown in Fig. 1 was produced in the following order. A bottom coating layer is provided on the surface of the embossed glass plate to be used as the transparent substrate 12.

(washing of glass)

Prepare embossed glass plate (made by Asahi Glass Co., Ltd., Solite (trade name), low iron A content of soda lime glass (whiteboard glass) and a satin-shaped embossed glass plate. Dimensions: 100 mm × 100 mm, thickness: 3.2 mm), the surface of the smooth surface of the embossed glass plate was ground with a cerium oxide aqueous dispersion, and washed with water to remove cerium oxide, rinsed with ion-exchanged water, and dried.

(bottom coating)

85.7 g of denatured ethanol was stirred, and a mixed liquid of 6.6 g of ion-exchanged water and 0.1 g of 61% by mass of nitric acid was added thereto, and the mixture was stirred for 5 minutes. It was added to a tetraethyl orthosilicate (calculated as SiO ₂ solid content concentration: 29 mass%) 7.6 g of, stirred at room temperature for 30 minutes to prepare a solid content concentration calculated as SiO ₂ of 2.2% by mass of the bottom of the coating liquid. This was applied to the surface of the smooth surface of the above-mentioned washed embossed glass plate by spray coating, and fired to form a film.

(top coating)

The embossed glass plate which was subjected to the bottom coating as described above was preheated in a preheating furnace (VTR-115, manufactured by ISUZU Co., Ltd.), and was coated by reverse roll while maintaining the surface temperature at 30 °C. A coating roller (manufactured by Sanwa Seiki Co., Ltd.) was applied to coat the top coating liquid (a1). Then, it was baked at 500 ° C for 30 minutes in the air to obtain a transparent substrate with a cerium oxide-based porous film.

(external coating)

25 g of distilled water was stirred, and 25 g of a nanosheet dispersion (A) was added thereto, and 50 g of ethanol was further added thereto, and the mixture was stirred for 10 minutes to prepare an external coating liquid. The obtained external coating liquid was applied to a ceria-based porous film of a transparent substrate with a cerium oxide-based porous film prepared by using 2 cc of a plastic dropper, and was subjected to spin coating. After coating (2,000 rpm, 20 seconds), it was dried at 200 ° C for 1 minute in a drying oven to obtain a target article.

[Example 2~17]

A glass cleaning, a bottom coating, a top coating, and an external coating were carried out in the same manner as in Example 1 except that the composition of the external coating liquid was changed, and an article was obtained.

The external coating liquid used in each example was prepared in the following order. The raw materials and blending amounts used in the preparation of each example are disclosed in Tables 2 to 3. The application and drying of these external coating liquids were also carried out in exactly the same manner as in Example 1.

The external coating liquid used in Example 2 was prepared by stirring 15 g of distilled water while adding 35 g of a nanosheet dispersion (A) thereto, further adding 50 g of ethanol, and stirring for 10 minutes.

The external coating liquid used in Example 3 was prepared by stirring 50 g of the nanochip dispersion (A) while adding 50 g of ethanol thereto and stirring for 10 minutes.

The external coating liquid used in Example 4 was prepared by stirring 98.08 g of ethanol and adding 1.92 g of a nanosheet dispersion (B) thereto, followed by stirring for 10 minutes.

The external coating liquid used in Example 5 was prepared by stirring 96.15 g of ethanol and adding 3.85 g of a nanosheet dispersion (B) thereto, followed by stirring for 10 minutes.

The external coating liquid used in Example 6 was prepared by stirring 94.23 g of ethanol and adding 5.77 g of a nanosheet dispersion (B) thereto, followed by stirring for 10 minutes.

The external coating liquid used in Example 7 was prepared by stirring 90.38 g of ethanol and adding 9.62 g of a nanosheet dispersion (B) thereto, followed by stirring for 10 minutes.

The external coating liquid used in Example 8 was prepared by stirring 80.8 g of ethanol and adding 19.2 g of a nanosheet dispersion (B) thereto, followed by stirring for 10 minutes.

The external coating liquid used in Example 9 was prepared by stirring 24 g of water while adding 25 g of a nanosheet dispersion (A) to further dissolve the binder. The liquid (E) was 1 g, and finally 50 g of ethanol was added, and the mixture was stirred for 10 minutes to prepare.

The external coating liquid used in Example 10 was stirred by adding 20 g of water, and 25 g of the nanosheet dispersion (A) was further added thereto, 5 g of the binder solution (E) was further added, and finally 50 g of ethanol was added, and the mixture was stirred for 10 minutes. modulation.

The external coating liquid used in Example 11 was stirred by adding 15 g of water while adding 25 g of the nanosheet dispersion (A), further adding 10 g of the binder solution (E), and finally adding 50 g of ethanol, and stirring for 10 minutes. modulation.

The external coating liquid used in Example 12 was stirred by adding 10 g of water while adding 25 g of the nanosheet dispersion (A), further adding 15 g of the binder solution (E), and finally adding 50 g of ethanol, and stirring for 10 minutes. modulation.

The external coating liquid used in Example 13 was obtained by stirring 10 g of water while adding 20 g of the nanosheet dispersion (A) thereto, further adding 20 g of the binder solution (E), and finally adding 50 g of ethanol, and stirring for 10 minutes. modulation.

The external coating liquid used in Example 14 was stirred by adding 10 g of water while adding 15 g of the nanosheet dispersion (A), further adding 25 g of the binder solution (E), and finally adding 50 g of ethanol, and stirring for 10 minutes. modulation.

The external coating liquid used in Example 15 was obtained by stirring 10 g of water while adding 10 g of the nanosheet dispersion (A), further adding 30 g of the binder solution (E), and finally adding 50 g of ethanol, and stirring for 10 minutes. modulation.

The external coating liquid used in Example 16 was prepared by stirring 25 g of water while adding 25 g of a nanosheet dispersion (A), further adding 42.5 g of ethanol, and finally adding a binder solution (F) of 7.5 g, stirring 10 Minutes to modulate.

The external coating liquid used in Example 17 was stirred by adding 50.4 g of ethanol, and 9.6 g of a nanosheet dispersion (B) was added thereto, and 25 g of water was further added. Thereafter, 15 g of the binder solution (E) was added to prepare.

The external coating liquid used in Example 18 was stirred by adding 72.9 g of ethanol, and 9.6 g of a nanosheet dispersion (B) was added thereto, further adding 7.5 g of a binder solution (F), and finally adding 10 g of water, stirring. 10 minutes to modulate.

[Example 19~20]

A glass cleaning, a bottom coating, a top coating, and an external coating were carried out in the same manner as in Example 1 except that the drying conditions after the application of the external coating liquid were changed, and an article was obtained. The composition and coating method of the external coating liquid were also the same as in Example 1.

The drying after the application of the external coating liquid was carried out in the case of Example 19 at 300 ° C for 1 minute, and in Example 20, at 400 ° C for 1 minute.

[Example 21]

A glass cleaning, a bottom coating, a top coating, and an external coating were carried out in the same manner as in Example 1 except that the nanosheet dispersion (C) was used as the external coating liquid. The composition, coating, and drying of the external coating liquid were also the same as in Example 1.

[Example 22]

Only the glass washing, the bottom coating, and the top coating were carried out in the same manner as in Example 1 to obtain a transparent substrate with a cerium oxide-based porous film. Thereafter, the substrate coated with the cerium oxide-based porous film was used as the article of Example 22 without external coating.

[Example 23~29]

The composition of the external coating liquid was changed in the same manner as in Example 1. The glass was washed, the bottom coating, the top coating, and the outer coating were carried out to obtain an article.

The external coating liquid used in each example was prepared in the following order.

The raw materials and blending amounts used in the preparation of each example are disclosed in Table 4. The application and drying of these external coating liquids were also carried out in exactly the same manner as in Example 1.

The external coating liquid used in Example 23 was prepared by stirring 50 g of a nanosheet dispersion (A') while adding 50 g of ethanol thereto and stirring for 10 minutes.

The external coating liquid used in Example 24 was prepared by stirring 99.04 g of ethanol while adding 0.96 g of a nanosheet dispersion (B) thereto and stirring for 10 minutes.

The external coating liquid used in Example 25 was prepared by stirring 35 g of water while adding 15 g of a binder solution (E) thereto, and finally adding 50 g of ethanol and stirring for 10 minutes.

The external coating liquid used in Example 26 was prepared by stirring 10 g of water while adding 40 g of a binder solution (E) thereto, and finally adding 50 g of ethanol and stirring for 10 minutes.

The external coating liquid used in Example 27 was prepared by stirring 60 g of ethanol while adding 40 g of a binder solution (G) thereto and stirring for 10 minutes.

The external coating liquid used in Example 28 was prepared by stirring 92.5 g of ethanol while adding 7.5 g of a surfactant solution (H) thereto and stirring for 10 minutes.

In Example 29, the nanosheet dispersion (D) was directly used as an external coating liquid.

The above measurements were carried out on the obtained articles. The results are disclosed in Tables 2 to 4.

In addition, in Example 2, there are many cerium oxide systems before the formation of the antifouling layer. The SEM photograph of the outermost surface of the ceria-based porous film side of the transparent substrate of the porous film is shown in Fig. 2, and the outermost surface of the antifouling layer side of the obtained article is shown in Fig. 3 (a), and the cross section is shown. Shown in Figure 3(b).

In Examples 1 to 21, the peeling force in the resin peel strength test was 740 g/5 mm or less, and the peeling force (840 g/) of the transparent substrate (Example 22) with the cerium oxide-based porous film before the formation of the antifouling layer. 5mm) is lower than 100g/5mm or more. From this result, it was confirmed that the antifouling property was imparted by forming the antifouling layer. Further, in Examples 1 to 21, the application of the external coating liquid caused the maximum transmittance change amount to be -0.16 to 0.13, and it was confirmed that the antireflection property was not lowered even if the antifouling layer was formed, or even if it was lowered, slight.

On the other hand, even in the case of using the external coating liquid containing a nanosheet, in the example 23 in which the film thickness of the formed antifouling layer was 41 nm, the antireflection performance was lowered. In Example 24 in which the film thickness of the antifouling layer was less than 0.4 nm, the effect of imparting antifouling properties was small, and the peeling force was large (780 g/5 mm).

In the case of using the binder as the solid component of the external coating liquid alone and having a solid content concentration of 0.15%, the effect of imparting antifouling properties was small, and the peeling force was as high as 760 g/5 mm. In Examples 26 and 27 in which the binder was used alone and the solid content concentration was increased to 0.40%, the antireflection performance was lowered.

In Example 28, in which the surfactant was used alone as a solid component of the external coating liquid, the effect of imparting antifouling properties was small, and the antireflection performance was also lowered.

In Example 29 in which a titanium oxide nanosheet was used, since the refractive index of the antifouling layer was high, the maximum transmittance was lowered by 0.55%.

If the removal efficiency of the antifouling layer is compared by the maximum transmittance after exposure of the examples 2, 7, 10, 21, and 29, in the examples 2, 7, and 10 using the bentonite nanosheet, after the exposure The maximum transmittance shows a value close to the maximum transmittance before the formation of the antifouling layer, and it is understood that the removal of the antifouling layer is continued because it is exposed outside the house.

On the other hand, in Examples 21 and 29 in which the antifouling layer was a layered polysilicate nanosheet or a titanium oxide nanosheet, the value of the maximum transmittance was substantially constant before and after the exposure, and no external exposure was observed. Removal of the antifouling layer.

Industrial availability

According to the present invention, it is possible to provide a stain-resistant antireflection film which can prevent the anti-reflection property of the porous cerium oxide-based porous film while improving the antifouling property and can maintain a good appearance for a long period of time, and the article having the antifouling anti-reflection film And a manufacturing method thereof; can be used as a cover member of a solar cell, various displays, and such front panels, various window glasses, cover members of touch panels, and the like.

In addition, the entire contents of the specification, the patent application, the drawings and the abstract of the Japanese Patent Application No. 2012-227967, filed on Jan.

10‧‧‧ Items

12‧‧‧ glass plate

14‧‧‧cerium dioxide porous membrane

16‧‧‧Anti-fouling layer

18‧‧‧Antifouling anti-reflection film

Claims (13)

An antifouling antireflection film comprising a ceria-based porous film and an antifouling layer covering a surface of the ceria-based porous film; the anti-fouling layer containing a plurality of nano-sheets, wherein the nano-sheet is The low refractive material having a refractive index of 1.4 to 1.65 is formed; and the average thickness of the antifouling layer is 0.4 to 40 nm. The antifouling antireflection film of claim 1, wherein the nanosheet has an average thickness of 0.7 to 20 nm and an average area of 100 to 1,000,000 nm ² . The antifouling antireflection film of claim 1 or 2, wherein the nanosheet is derived from an inorganic layered compound selected from the group consisting of layered polysilicates and clay minerals. At least one of the groups. The antifouling antireflection film according to any one of claims 1 to 3, wherein the aforementioned nanosheet is surface-modified by a surfactant. An article having an antifouling antireflective film according to any one of claims 1 to 4 on a transparent substrate. A method for producing an article having an antifouling antireflection film, comprising the steps of: forming a ceria-based porous film on a transparent substrate; and coating the surface of the ceria-based porous film a coating liquid for forming a stain layer, which is dried to form an antifouling layer, wherein the coating liquid for forming an antifouling layer contains a plurality of nanosheets and a dispersion medium of the nanosheet; and the nanosheet is refracted Low refractive material with a rate of 1.4~1.65 And the method is to form an antifouling antireflection film having an average thickness of the antifouling layer of 0.4 to 40 nm. The method of producing the article of claim 6, wherein the nanosheet has an average thickness of 0.7 to 20 nm and an average area of 100 to 1,000,000 nm ² . The method of producing the article of claim 6 or 7, wherein the nano-sheet is derived from an inorganic layered compound selected from the group consisting of layered polysilicates and clay minerals. At least one. The method for producing an article according to any one of claims 6 to 8, wherein the coating liquid for forming an antifouling layer further contains a binder or a precursor thereof; and the coating liquid for forming an antifouling layer, the nanometer The mass ratio of the sheet content to the total amount of the above-mentioned nanosheet and the above-mentioned binder or its precursor is 0.25 or more. The method for producing an article according to any one of claims 6 to 9, wherein the solid content concentration in the coating liquid for forming an antifouling layer is 0.05 to 0.50% by mass. The method for producing an article according to any one of claims 6 to 10, wherein the coating liquid for forming an antifouling layer further contains a surfactant; and the mass ratio of the surfactant to the content of the nanosheet is 1.5. the following. The method for producing an article according to any one of claims 6 to 8, wherein the coating liquid for forming an antifouling layer contains only a nanosheet as a solid component; and the method is applied to coating the antifouling layer. The solution was dried at 300 ° C or lower. The method of manufacturing an article according to any one of claims 6 to 12, wherein The dispersion medium contains water; and the water content in the coating liquid for forming an antifouling layer is 60% by mass or less based on the total mass of the coating liquid for forming an antifouling layer.