JP2016001200A - Antifouling antireflection film, article and production method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antifouling antireflection film that has an improved antifouling property while maintaining the antireflection performance of a silica porous film, and can maintain a good appearance for the long term, an article comprising the antifouling antireflection film and a production method thereof.SOLUTION: An antifouling antireflection film comprises a silica porous film, and an antifouling layer that covers the surface of the silica porous film. The antifouling layer comprises a plurality of nanosheets. The plurality of nanosheets are each composed of low refractive materials with refractive indexes 1.4-1.65. The antifouling layer has an average thickness of 0.4-40 nm.

Description

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

Articles having an antireflection film on the surface of a transparent substrate such as a glass plate are used as cover members for solar cells, various displays and their front plates, various window glasses, touch panel cover members, and the like.
The antireflection film is disposed on the outermost layer of the article because of its function. For this reason, the antireflection film is required to have antifouling properties (that dirt is difficult to adhere and can be easily removed even if it adheres).

One example of an antireflection film used for a transparent substrate such as a glass plate is a silica-based porous film (for example, Patent Document 1). Since the silica-based porous film has pores in a matrix containing silica as a main component, the refractive index is lower than that in the case where there are no pores.
However, since the silica-based porous film has many fine open holes and irregularities on the surface, there are problems that dirt such as oil dirt and resin is likely to adhere, and that the attached dirt is difficult to remove.
For example, in the manufacturing process of the solar cell, a step of bonding the cover member and the solar cell with a sealing material is performed. When a silica-based porous film is used as the antireflection film, there is a problem that EVA, which is a sealing material, penetrates into the silica-based porous film in the manufacturing process and the antireflection performance is lowered. In addition, the soaked EVA is difficult to peel off from the silica-based porous film, and even after peeling, the color of the silica-based porous film where the EVA has soaked becomes different from the other parts. There are also problems such as.

As a countermeasure against the problems in the above manufacturing process and the like, a protective film is provided on a silica-based porous film. However, the method of providing the protective film increases the cost.
A method of applying a fluorine-based coating agent to the surface of a silica-based porous film has also been proposed (for example, Patent Document 2).
The method of applying a fluorine-based coating agent can improve the antifouling property against oil stains and EVA easily and at a lower cost than when a protective film is provided. However, depending on the coating agent, there is a concern that the antireflection performance may be deteriorated by dipping into the silica-based porous film during coating. In addition, the silica-based porous film imparted with the antifouling property by the above method is likely to remain after being installed as a solar cell module outdoors due to water repellency, and dirt is not scattered evenly due to rainwater. For example, it is difficult to maintain a good appearance for a long time.

Special table 2010-509175 JP-A-5-330856

  The present invention has been made in view of the above circumstances, and has improved antifouling properties while maintaining the antireflection performance of the silica-based porous film, and the antifouling antireflection film capable of maintaining a good appearance over a long period of time, An object is to provide an article provided with an antifouling antireflection film and a method for producing the same.

The present invention has the following aspects.
[1] A silica-based porous membrane, and an antifouling layer covering the surface of the silica-based porous membrane,
The antifouling layer contains a plurality of nanosheets, and the plurality of nanosheets is made of a low refractive material having a refractive index of 1.4 to 1.65,
An antifouling antireflection film, wherein the antifouling layer has an average film thickness of 0.4 to 40 nm.
[2] the nanosheet, and an average mean area of thickness and 100～1000000Nm ² of 0.7～20Nm, antifouling antireflection film according to [1].
[3] The antifouling antireflection film according to [1] or [2], wherein the nanosheet is derived from an inorganic layered compound selected from layered polysilicates and clay minerals.
[4] The antifouling antireflection film according to any one of [1] to [3], wherein the nanosheet is surface-modified with a surfactant.
[5] An article having the antifouling antireflection film according to any one of [1] to [4] on a transparent substrate.

[6] A step of forming a silica-based porous film on a transparent substrate;
Applying a coating solution for forming an antifouling layer to the surface of the silica-based porous membrane, and drying to form an antifouling layer,
The antifouling layer forming coating solution contains a plurality of nanosheets and a dispersion medium of the nanosheets,
Each of the plurality of nanosheets is made of a low refractive material having a refractive index of 1.4 to 1.65,
The manufacturing method of the articles | goods whose average film thickness of the said pollution protection layer is 0.4-40 nm.
[7] the nanosheets has a mean average area of thickness and 100～1000000Nm ² of 0.7～20Nm, method of manufacturing an article according to [6].
[8] The antifouling layer forming solution further includes a binder or a precursor thereof,
[6] or [7], wherein a mass ratio of a content of the nanosheet to a total amount of the nanosheet and the binder or a precursor thereof in the antifouling layer forming coating solution is 0.25 or more. Antifouling antireflection film.
[9] The method for producing an article according to any one of [6] to [8], wherein the solid content concentration in the antifouling layer forming coating solution is 0.05 to 0.50 mass%.
[10] The antifouling layer forming coating solution further comprises a surfactant,
The method for producing an article according to any one of [6] to [9], wherein a mass ratio of the content of the surfactant to the content of the nanosheet is 1.5 or less.
[11] The antifouling layer forming coating solution contains only the nanosheet as a solid content,
The method for producing an article according to [6] or [7], wherein drying after applying the antifouling layer forming coating solution is performed at 300 ° C. or lower.
[12] The dispersion medium contains water,
The content of water in the antifouling layer forming coating solution is 60% by mass or less based on the total mass of the antifouling layer forming coating solution, according to any one of [6] to [11]. Manufacturing method of the article.

  According to the present invention, the antifouling antireflection film capable of maintaining a good appearance over a long period of time while improving the antifouling property while maintaining the antireflection performance of the silica-based porous film, and the antifouling antireflection film are provided. Articles and methods for manufacturing the same can be provided.

It is a schematic sectional drawing which shows one Embodiment of the articles | goods of this invention. [Example] It is the SEM photograph of the outermost surface by the side of the silica type porous membrane of the glass plate with a silica type porous membrane before forming an antifouling layer produced in Example 2 in FIG. It is a SEM photograph ((a) outermost surface on the antifouling layer side, (b) cross section) of the article obtained in Example 2.

Hereinafter, the present invention will be described with reference to exemplary embodiments.
<First embodiment>
FIG. 1 is a cross-sectional view showing a first embodiment of an article having the antifouling antireflection film of the present invention on a transparent substrate.
The article 10 of the present embodiment includes a transparent base material 12 and an antifouling antireflection film 18 formed on the surface of the transparent base material 12. The antifouling antireflection film 18 includes a silica-based porous film 14 and an outermost layer 16 formed on the surface of the silica-based porous film 14.

(Transparent substrate 12)
Examples of the shape of the transparent substrate 12 include a plate and a film.
Examples of the material of the transparent substrate 12 include glass and resin.
Examples of the glass include soda lime glass, borosilicate glass, aluminosilicate glass, and alkali-free glass.
Examples of the resin include polyethylene terephthalate, polycarbonate, triacetyl cellulose, polymethyl methacrylate, and the like.

As the transparent substrate 12, a glass plate is preferable.
The glass plate may be a smooth glass plate formed by a float method or the like, or may be a template glass having irregularities on the surface. Further, not only flat glass but also glass having a curved surface shape may be used.
The thickness of the glass plate is not particularly limited, and glass having a thickness of 0.2 to 10 mm can be used. The thinner the thickness, the lower the light absorption, which is preferable for the purpose of improving the transmittance.

When the glass plate is an architectural or vehicle window glass, soda lime glass having the following composition is preferred.
In mass percentage display based on oxide,
SiO _2: 65~75%,
Al ₂ O _3: 0~10%,
CaO: 5 to 15%,
MgO: 0 to 15%,
Na ₂ O: 10~20%,
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 to 3%,
BaO: 0 to 5%,
SrO: 0 to 5%,
B ₂ O _3: 0~15%,
ZnO: 0 to 5%,
ZrO ₂ : 0 to 5%,
SnO ₂ : 0 to 3%,
SO ₃ : 0 to 0.5%.

When a glass plate is an alkali free glass, what has the following composition is preferable.
In mass percentage display based on oxide,
SiO _2: 39~70%,
Al ₂ O ₃ : 3 to 25%,
B ₂ O _3: 1~30%,
MgO: 0 to 10%,
CaO: 0 to 17%,
SrO: 0 to 20%,
BaO: 0 to 30%.

When the glass plate is a mixed alkali glass, those having the following composition are preferred.
In mass percentage display based on oxide,
SiO _2: 50~75%,
Al ₂ O _3: 0~15%,
MgO + CaO + SrO + BaO + ZnO: 6 to 24%,
_{Na 2 O + K 2 O:} 6~24%, including.

  When the glass plate is a cover glass for a solar cell, a satin-patterned template glass with an uneven surface is preferable. As the template glass, soda lime glass (white plate glass) having a lower iron component ratio (high transparency) than soda lime glass (blue plate glass) used for ordinary window glass or the like is preferable.

A functional layer may be formed on the surface of the transparent substrate 12 in advance.
Examples of the functional layer include an undercoat layer, an adhesion improving layer, and a protective layer.
Examples of the undercoat layer include those having a function as an alkali barrier layer or a wide band low refractive index layer. The undercoat layer is preferably a layer formed by applying an undercoat coating composition containing a hydrolyzate of alkoxysilane (silane hydrolysis sol) on a substrate. When applying the coating composition mentioned later on an undercoat layer, the undercoat layer may be baked beforehand and may be in a wet state. When a coating composition is applied on the undercoat layer, the application temperature is preferably room temperature to 80 ° C, and the firing temperature is preferably 30 to 700 ° C. The thickness of the undercoat layer is preferably 10 to 500 nm.

(Silica-based porous film 14)
The “silica-based porous membrane” is a membrane having a plurality of pores in a matrix mainly composed of silica. The silica-based porous film has a relatively low refractive index (reflectance) because the matrix is mainly composed of silica. Moreover, it is excellent in chemical stability, adhesiveness with the transparent base material 12 such as a glass plate, and wear resistance. Furthermore, by having holes in the matrix, the refractive index is lower than when there are no holes.

That the matrix is mainly composed of silica means that the proportion of silica is 90% by mass or more of the matrix (100% by mass).
As a matrix, what consists essentially of silica is preferable. The phrase “substantially composed of silica” means that it is composed only of silica excluding inevitable impurities (for example, a structure derived from the compound (a2) described later).
The matrix may contain a small amount of components other than silica. The components include Li, B, C, N, F, Na, Mg, Al, P, S, K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, and Sr. , Y, Zr, Nb, Ru, Pd, Ag, In, Sn, Hf, Ta, W, Pt, Au, Bi and compounds such as one or more ions and oxides selected from lanthanoid elements .
The matrix may include not only two-dimensionally polymerized matrix components but also three-dimensionally polymerized nanoparticles. Examples of the composition of the nanoparticles include Al ₂ O ₃ , SiO ₂ , SnO ₂ , TiO ₂ , ZnO, and ZrO ₂ . The size of the nanoparticles is preferably 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 square shape.

The silica-based porous film 14 is not particularly limited, and a known silica-based porous film can be used.
As an example of a preferable silica-based porous membrane, a dispersion medium (a), fine particles (b) dispersed in the dispersion medium (a), and a matrix precursor (c) dissolved or dispersed in the dispersion medium (a) ) And a film obtained by baking. As the matrix precursor (c), a hydrolyzate of alkoxysilane is used.
The film is a film in which fine particles (b) are dispersed in a matrix made of a fired product (SiO ₂ ) of a matrix precursor (c). The film exhibits an antireflection effect by voids selectively formed around the fine particles (b). In particular, when the core part of the fine particles (b) is hollow, a more excellent antireflection effect is exhibited. The coating liquid and a method for forming a silica-based porous film using the coating liquid will be described in detail later.

50-300 nm is preferable and, as for the film thickness of the silica type porous membrane 14, 80-200 nm is more preferable. When the thickness of the silica-based porous film 14 is 50 nm or more, light interference occurs and antireflection performance is exhibited. If the thickness of the silica-based porous film 14 is 300 nm or less, the film can be formed without generating cracks.
The film thickness of the silica-based porous film 14 is measured by a reflection spectral film thickness meter.

The surface of the porous silica film 14 preferably has an open hole. When the article 10 of the present embodiment is exposed to ultraviolet rays or wind and rain outdoors to remove the antifouling layer, if the surface has an open hole, it tends to be a hydrophilic surface, and dirt such as sand and dust is caused by rainwater or the like. It becomes easy to flow down evenly.

(Anti-fouling layer 16)
The antifouling layer 16 contains a plurality of nanosheets. Each of the plurality of nanosheets is made 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 calculating from the reflectance obtained by spectral reflectance measurement.

By providing the antifouling layer 16 on the surface of the silica-based porous film 14, the antifouling property can be enhanced without deteriorating the antireflection performance.
As will be described in detail later, the antifouling layer 16 is formed by applying an antifouling layer forming coating solution in which a plurality of nanosheets are dispersed in a liquid medium to the surface of the silica-based porous film 14 and drying it. However, since the nanosheet is contained and the content is equal to or greater than a predetermined amount, the nanosheet is deposited on the openings and irregularities on the surface of the porous silica film 14 when the antifouling layer forming coating solution is applied. To do. Further, the penetration of the liquid medium of the antifouling layer forming coating liquid into the silica-based porous film 14 is also suppressed, and even when an optional component such as a binder is dissolved in the liquid medium, the optional component is silica-based. It is difficult for the antireflection performance to deteriorate due to soaking in the porous film 14.
And since the antifouling layer 16 formed by depositing a plurality of nanosheets is dense and has high surface smoothness compared to the silica-based porous film 14, it is difficult for dirt to enter. Therefore, it is difficult for dirt to adhere, and even if dirt is attached, it is easy to remove. Further, since the nanosheet is made of a low refractive material and the total thickness of the antifouling layer is thin, it is denser than the silica-based porous film, but hardly affects the antireflection performance of the silica-based porous film 14.

The low refractive material having a refractive index of 1.4 to 1.65 may be any material having a refractive index within the above range, and can be appropriately selected from known nanosheets.
The nanosheet made of the low refractive index material is preferably derived from an inorganic layered compound selected from layered polysilicate (refractive index 1.45) and clay mineral (refractive index 1.56 to 1.58). The nanosheet derived from the inorganic layered compound has a lower hydrophobicity than the fluorine-based coating agent, and has a relatively low water repellency on the surface of the antifouling layer formed. For this reason, even when the article 10 is installed outdoors, even when the antifouling layer 16 is present, the dirt does not flow uniformly due to rainwater or the like and remains scattered, and the problem of running water marks due to rainwater or the like hardly occurs. It is easy to maintain a good appearance across the board.
The inorganic layered compound has a structure in which a plurality of nanosheets are laminated, and natural products and synthetic products are commercially available. A nanosheet can be obtained by peeling off the layer constituting the inorganic layered compound.
In the present invention, the clay mineral means one having an octahedral structure such as AlO _{6 in the} crystal structure, and the layered polysilicate is different from the clay mineral in that it does not have the octahedral structure.

Examples of the layered polysilicate include kanemite, macatite, magadiite, kenyanite, octosilicate and the like.
The composition of the layered polysilicate 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)
[Wherein, 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 smectite, vermiculite, layered double hydroxide (LDH) and the like. Examples of the smectite include 2-octahedron type (saponite, hectorite, etc.) and 3-octahedron type (montmorillonite, beidellite, etc.).

The composition of 2-octahedral smectite can be represented by the following composition formula (ii) (including interlayer cations). The composition of 3-octahedral smectite can be represented by the following composition formula (iii) (including interlayer cations).
(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. Examples of the alkali metal atom are the same as described above. Examples of the alkaline earth metal include Mg and Ca. Examples of transition metal atoms include Fe and Al.

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 represented by the following composition formula (v) (including interlayer anions).
[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.), M6 is a trivalent metal ion (Al ³⁺ , Fe ³⁺ , Cr ^3+, etc.), and A Is an n-valent anion, and n is an integer of 1 to 3. Examples of A include Cl ⁻ , NO ₃ ⁻ , CO ₃ ^{2− and the} like.

  Of the above, the inorganic layered compound is preferably a clay mineral, and particularly preferably smectite. In the layered polysilicate, hydroxyl groups are exposed on the layer surface, whereas in the clay mineral, the hydroxyl groups are not exposed on the layer surface. For this reason, compared with the nanosheet obtained from the layered polysilicate, the nanosheet obtained from the clay mineral has weak adhesion to the silica-based porous film 14, and the antifouling layer 16 is easily washed away by exposure outdoors. By eliminating the antifouling layer 16 over time, the low-reflective property of the silica-based porous film 14 is sufficiently developed. Further, when the surface of the porous silica membrane 14 has open holes, when the article 10 is exposed to ultraviolet rays or wind and rain outdoors to remove the antifouling layer and the porous silica membrane 14 is exposed, The outermost surface of the article 10 is likely to be a hydrophilic surface, and dirt such as sand and dust is likely to flow evenly with rainwater or the like. Therefore, a good appearance can be maintained over a long period.

As the nanosheet material, titanium oxides such as Ti _0.91 O ₂ and Ti _1.73 Li _0.27 O ₂ , manganese oxides such as MnO ₂ , oxidations such as Nb ₆ O ₁₇ and Nb ₃ O _8, etc. Transition metal oxides such as niobium and tungsten oxides such as WO ₃ ; transition metal chalcogenides such as MoS ₂ ; layered perovskites such as Ca ₂ Nb ₃ O ₁₀ and La ₂ Nb ₂ O ₇ However, these materials have low transparency or are transparent but have a high refractive index. Therefore, when 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 nanosheet is preferably 0.7 to 20 nm, more preferably 0.7 to 15 nm, and further preferably 0.7 to 10 nm. If the average thickness of the nanosheet is 0.7 nm or more, the structure of the individual nanosheets is not easily destroyed, and the durability of the antifouling layer is increased. If the average thickness of the nanosheet is 20 nm or less, it is easy to form a thin antifouling layer, for example, an antifouling layer having an average thickness of 40 nm or less.

Area of the nanosheet is preferably 100 nm ² or more, more preferably 200 nm ² or more, more preferably 400 nm ² or more. If the area of the nanosheet is 100 nm ² or more, when the antifouling layer forming coating solution described later is applied to form the antifouling layer, the nanosheet is less likely to enter the silica-based porous film 14, and the silica-based porous The surface of the membrane is successfully coated with nanosheets. The upper limit of the area of nanosheets is not particularly limited, dispersibility in an antifouling layer forming coating solution, considering the easy availability and the like, preferably 1000000Nm ² or less, 250000Nm ² or less being more preferred.

In view of these, examples of the nanosheet, preferably has an average mean area of thickness and 100～1000000Nm ² of 0.7～20Nm, mean average thickness and 200～1000000Nm ² of 0.7~15nm Those having an area are more preferable, and those having an average thickness of 0.7 to 10 nm and an average area of 200 to 250,000 nm ² are more preferable.

As a nanosheet, you may contain the nanosheet surface-modified with processing agents, such as surfactant. By containing the surface-modified nanosheet, the attached dirt can be easily peeled off, and sufficient antifouling property can be obtained with a small amount.
Surfactants include alkyl carboxylic acid salts such as sodium octoate, potassium octoate, sodium decanoate, potassium decanoate, sodium laurate, potassium laurate, sodium stearate, potassium stearate, sodium hexanesulfonate, hexane Alkyl sulfonates such as potassium sulfonate, sodium octane sulfonate, potassium octane sulfonate, sodium decane sulfonate, potassium decane sulfonate, sodium dodecane sulfonate, potassium dodecane sulfonate, sodium lauryl sulfate, potassium lauryl sulfate, myristyl sulfate Sulfate esters such as sodium and potassium myristyl sulfate, phosphate esters such as sodium lauryl phosphate and sodium tripolyphosphate, tetramethylammonium Mubromide, tetramethylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium chloride, octyltrimethylammonium chloride, octyltrimethylammonium bromide, decyltrimethylammonium chloride, decyltrimethylammonium bromide, triethanolamine chloride, triethanolamine bromide, tripropanolamine Non-ionic such as quaternary alkyl ammonium such as chloride, tripropanolamine bromide, polyoxyethylene alkyl ammonium chloride, polyoxyethylene alkyl ammonium bromide, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, cetanol, oleyl alcohol, etc. Surface activity Agent, and the like.
Treatment agents other than surfactants include trimethylsilyl chloride, triethylsilyl chloride, t-butyldimethylsilane, tri-i-propylsilyl chloride, chloromethyltrimethylsilane, triethylsilane, butyldimethylsilane, trimethylvinylsilane, allyltrimethylsilane, Examples of the silylating agent include hexamethyldisilazane.
In addition, when peeling a nanosheet from an inorganic layered compound, this peeling may be performed in water containing a surfactant. The nanosheet dispersion liquid thus obtained contains nanosheets surface-modified with a surfactant.

  The nanosheet 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 including a binder, the adhesion between the plurality of nanosheets, the denseness of the antifouling layer 16, the removability of the antifouling layer 16 when exposed outdoors, and the like can be improved.
Although it does not specifically limit as a binder, The thing melt | dissolved in the coating liquid for antifouling layer formation is preferable. Since the dispersion medium of the coating solution for forming the antifouling layer often contains water, the binder itself or its precursor is preferably water-soluble. For example, a hydrolyzate of a hydrolyzable silane compound ( Silane hydrolysis sol), condensates thereof, and water-soluble polymers. A water-soluble polymer is more preferable as the binder. The water-soluble polymer is easily deteriorated by ultraviolet rays, wind and rain, etc. when exposed outdoors, and therefore has an effect of improving the removal property of the antifouling layer 16.

The hydrolyzable silane compound is represented by, for example, 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). Compounds. The hydrolyzate of the hydrolyzable silane compound has a structure in which the Si—X group of SiX _m Y _4-m becomes Si—OH by hydrolysis, and Si—OH can be bonded to the nanosheet surface. The hydrolyzate can bind nanosheets by having two or more Si—OH. Moreover, hydrolyzate may condense and form a condensate.

m is preferably 3 or 4.
The hydrolyzable group of X is a group that can convert 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, an acyloxy group, an aminoxy group, an amide group, a ketoximate group, a hydroxyl group, an epoxy group, a glycidyl group, and an isocyanate group, and an alkoxy group is particularly preferable. .
The non-hydrolyzable group of Y is a functional group whose structure does not change under conditions where the Si—X group becomes a Si—OH group by hydrolysis. The non-hydrolyzable group is not particularly limited, and may be a known group as a non-hydrolyzable group in a silane coupling agent or the like.

Specific examples of hydrolyzable silane compounds include tetraalkoxysilane (tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, etc.), alkoxysilane having an alkyl group (methyltrimethoxysilane, methyltriethoxysilane, Ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, etc.), alkoxysilanes having aryl groups (phenyltrimethoxysilane, phenyltriethoxysilane, etc.) , Alkoxysilane having a perfluoropolyether group (perfluoropolyether triethoxysilane, etc.), alkoxysilane having a perfluoroalkyl group (perfluoro Tiltriethoxysilane, etc.), alkoxysilanes having vinyl groups (vinyltrimethoxysilane, vinyltriethoxysilane, etc.), alkoxysilanes having epoxy groups (2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3- Glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, etc.), alkoxysilanes having an acryloyloxy group (3-acryloyloxypropyltrimethoxysilane, etc.), etc. Is mentioned.
Among the above, when making the antifouling layer 16 hydrophilic, tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane are preferable. When making the antifouling layer 16 water-repellent, an alkoxysilane having an alkyl group or an alkoxysilane having a perfluoroalkyl group is preferable.

Hydrolysis of the hydrolyzable silane compound is carried out by using an amount of water that can hydrolyze all hydrolyzable groups of the hydrolyzable silane compound (for example, in the case of tetraalkoxysilane, four times or more moles of water of tetraalkoxysilane) and a catalyst. Perform using acid or alkali. Examples of the acid include inorganic acids (HNO ₃ , H ₂ SO ₄ , HCl, etc.) and organic acids (formic acid, oxalic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, etc.). Examples of the alkali include ammonia, sodium hydroxide, potassium hydroxide and the like. The catalyst is preferably an acid from the viewpoint of long-term storage. Moreover, as a catalyst, what does not disturb dispersion | distribution of a nanosheet is preferable.

Examples of the water-soluble polymer include polyvinyl alcohol, polyethylene glycol, polyethylene oxide, polyvinyl pyrrolidone, polyethylene imine, polydiallyl dimethyl ammonium chloride, sodium polyacrylate, polyacrylamide, polylactic acid, sodium polystyrene sulfonate, sodium polyvinyl sulfate, carboxy Vinyl polymer, carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose, guar gum, cationized guar gum, carrageenan, sodium alginate, corn starch, xanthan gum, sodium chondroitin sulfate, sodium hyaluronate, starch, modified starch, glue, gelatin, gum arabic, sodium alginate, pectin Etc.
The molecular weight of the water-soluble polymer is preferably 1000 to 100,000. When the molecular weight is less than 1000, the water-soluble polymer is likely to enter the inside of the silica-based porous film 14 and the transmittance is likely to decrease. When the molecular weight is larger than 100,000, it becomes difficult to dissolve in a solvent, and nanosheets and aggregates are generated in the paint, which may reduce the stability of the paint.

  The antifouling layer 16 may contain other components other than the nanosheet and the binder as needed, as long as the effects of the present invention are not impaired. Examples of the other components include surfactants that do not modify the surface of the nanosheet, silica fine particles, and titania fine particles. In the case of containing titania fine particles, it is expected that the attached dirt is decomposed by the photocatalytic effect.

The average film thickness of the antifouling layer 16 is 0.4 to 40 nm, and preferably 1 to 20 nm. Sufficient antifouling property is acquired as the average film thickness of the antifouling layer 16 is 0.4 nm or more. When it is 40 nm or less, the antifouling layer 16 has little influence on the antireflection performance of the silica-based porous film 14, and the decrease in maximum transmittance due to the provision of the antifouling layer 16 can be suppressed.
The measuring method of the average film thickness of the antifouling layer 16 is as shown in the examples described later.
The antifouling layer 16 does not necessarily have to cover the entire surface of the silica-based porous film 14. For example, the surface of the silica-based porous film 14 may be partially covered, and the surface of the silica-based porous film 14 may be partially exposed.

(Method for manufacturing article 10)
The article 10 is, for example, a step of applying a silica-based porous film-forming coating solution on the transparent substrate 12 and firing to form a silica-based porous film 14 (hereinafter “first step”);
A step of applying an antifouling layer-forming coating solution containing a plurality of nanosheets and a dispersion medium of the nanosheets on the surface of the silica-based porous membrane and drying to form an antifouling layer (hereinafter referred to as “second” It can be manufactured by performing the process ")."

{First step}
The first step can be performed by a known production method according to the silica-based porous film to be formed, and is not particularly limited. For example, the dispersion medium (a) and the fine particles dispersed in the dispersion medium (a) By applying a coating liquid (hereinafter referred to as “topcoat liquid”) containing (b) and a matrix precursor (c) dissolved or dispersed in the dispersion medium (a) onto the transparent substrate 14 and baking it. Can be implemented. As a result, a film is formed in which fine particles (b) are dispersed in a matrix made of a calcined product (SiO ₂ ) of a hydrolyzate of alkoxysilane.

The dispersion medium (a) is a liquid that disperses the fine particles (b). The dispersion medium (a) may be a solvent that dissolves the matrix precursor (c).
When the matrix precursor (c) is a hydrolyzate of alkoxysilane, water is required for hydrolysis, and therefore it is preferable that the dispersion medium (a) contains at least water.
Water and other liquids may be used in combination. Examples of the other liquid include alcohols (methanol, ethanol, isopropanol, butanol, diacetone alcohol, etc.), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), ethers (tetrahydrofuran, 1,4-dioxane, etc.). ), Cellosolves (methyl cellosolve, ethyl cellosolve, etc.), esters (methyl acetate, ethyl acetate, etc.), glycol ethers (ethylene glycol monoalkyl ether, etc.), nitrogen-containing compounds (N, N-dimethylacetamide, N, N -Dimethylformamide, N-methylpyrrolidone, etc.), sulfur-containing compounds (dimethylsulfoxide, etc.) and the like.
Among the other liquids, as the solvent for the matrix precursor (c), alcohols are preferable, and methanol and ethanol are particularly preferable.

Examples of the fine particles (b) include metal oxide fine particles, metal fine particles, pigment-based fine particles, and resin fine particles.
As the material of the metal oxide fine particles, Al ₂ O ₃ , SiO ₂ , SnO ₂ , TiO ₂ , ZrO ₂ , ZnO, CeO ₂ , Sb-containing SnO _X (ATO), Sn-containing In ₂ O ₃ (ITO), RuO ₂ and the like, from the viewpoint of low refractive index, SiO ₂ is preferable.
Examples of the material of the metal fine particles include metals (Ag, Ru, etc.), alloys (AgPd, RuAu, etc.) and the like.
Examples of the pigment-based fine particles include inorganic pigments (titanium black, carbon black, etc.) and organic pigments.
Examples of the resin fine particle material include polystyrene and melanin resin.

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 shape, a diamond shape, a star shape, and an indefinite shape. The fine particles (b) may be hollow or perforated. In addition, the fine particles (b) may be present in a state where each fine particle is independent, each fine particle may be linked in a chain shape, or each fine particle may be aggregated.
The fine particles (b) may be used alone or in combination of two or more.

The average aggregate particle diameter of the fine particles (b) is preferably 1 to 1000 nm, more preferably 3 to 500 nm, and still more preferably 5 to 300 nm. When the average aggregate particle diameter of the fine particles (b) is 1 nm or more, the antireflection effect is sufficiently high. If the average aggregate particle diameter of the fine particles (b) is 1000 nm or less, the haze of the silica-based porous film 14 can be kept low.
The average aggregate particle diameter of the fine particles (b) is an average aggregate particle diameter of the fine particles (b) in the dispersion medium (a), and is measured by a dynamic light scattering method. In the case of monodispersed fine particles (b) in which no aggregation is observed, the average aggregate particle size is equal to the average primary particle size.

As the matrix precursor (c), a hydrolyzate of alkoxysilane is preferable.
Examples of alkoxysilane include tetraalkoxysilane (tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, etc.), alkoxysilane having a perfluoropolyether group (perfluoropolyether triethoxysilane, etc.), perfluoroalkyl. Group-containing alkoxysilane (perfluoroethyltriethoxysilane, etc.), vinyl group-containing alkoxysilane (vinyltrimethoxysilane, vinyltriethoxysilane, etc.), epoxy group-containing alkoxysilane (2- (3,4-epoxycyclohexyl), etc. ) Ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, etc.) Alkoxysilanes (3-acryloyloxy propyl trimethoxysilane and the like) or the like having a Riroiruokishi group.
Hydrolysis of the alkoxysilane can be carried out in the same manner as the hydrolysis of the hydrolyzable silane compound. As a catalyst used at the time of hydrolysis, a catalyst that does not disturb the dispersion of the fine particles (b) is preferable.

The topcoat liquid may contain a terpene derivative (d), other additives, and the like as necessary.
The terpene means a hydrocarbon having a composition of (C ₅ H ₈ ) _n (where n is an integer of 1 or more) having isoprene (C ₅ H ₈ ) as a structural unit. The terpene derivative means terpenes having a functional group derived from terpene. The terpene derivative (d) includes those having different degrees of unsaturation. Although some terpene derivatives (d) function as a dispersion medium (a), those that are “hydrocarbons having a composition of (C ₅ H ₈ ) _n having isoprene as a structural unit” are terpene derivatives ( It corresponds to d), and shall not correspond to the dispersion medium (a).
The terpene derivative (d) is preferably a terpene derivative having a hydroxyl group and / or a carbonyl group in the molecule from the viewpoint of the antireflection effect of the silica-based porous film 14, and the hydroxyl group, aldehyde group (—CHO), A terpene derivative having one or more selected from the group consisting of a keto group (—C (═O) —), an ester bond (—C (═O) O—), and a carboxy group (—COOH) is more preferred. Further, a terpene derivative having at least one selected from the group consisting of a hydroxyl group, an aldehyde group, and a keto group is more preferable.

Examples of the terpene derivative (d) include terpene alcohol (α-terpineol, terpinene 4-ol, L-menthol, (±) citronellol, myrtenol, nerol, borneol, farnesol, phytol, etc.), terpene aldehyde (citral, β-cyclohexane). Citral, perilaldehyde, etc.), terpene ketones ((±) camphor, β-ionone, etc.), terpene carboxylic acids (citronellic acid, abietic acid, etc.), terpene esters (terpinyl acetate, menthyl acetate, etc.) and the like. In particular, terpene alcohol is preferable.
A terpene derivative (d) may be used individually by 1 type, and may use 2 or more types together.

Examples of other additives include surfactants for improving leveling properties and metal compounds for improving durability of the silica-based porous film 14.
Examples of the surfactant include silicone oil and acrylic.
As the metal compound, a zirconium chelate compound, a titanium chelate compound, an aluminum chelate compound and the like are preferable. Examples of the zirconium chelate compound include zirconium tetraacetylacetonate and zirconium tributoxy systemate.

The viscosity of the top coat liquid is preferably 1.0 to 10.0 mPa · s, and more preferably 2.0 to 5.0 mPa · s. If the viscosity of the topcoat liquid is 1.0 mPa · s or more, it is easy to control the film thickness of the topcoat liquid applied on the transparent substrate 12. If the viscosity of the topcoat solution is 10.0 mPa · s or less, the drying or baking time and the coating time are shortened.
The viscosity of the topcoat solution is measured with a B-type viscometer.

1-9 mass% is preferable and, as for the solid content density | concentration of a topcoat liquid, 2-6 mass% is more preferable. If the solid content concentration is 1% by mass or more, the film thickness of the top coat liquid applied on the transparent substrate 12 can be reduced, and the film thickness of the finally obtained silica-based porous film 14 is uniform. Easy to do. If solid content concentration is 9 mass% or less, it will be easy to make the film thickness of the coating film of the topcoat liquid apply | coated on the transparent base material 12 uniform.
The solid content of the topcoat liquid means the sum of the fine particles (b) and the matrix precursor (c) (where the solid content of the matrix precursor (c) is the amount of alkoxysilane converted to SiO ₂ ). .

The mass ratio (fine particles / binder) between the fine particles (b) and the matrix precursor (c) in the top coat solution is preferably 95/5 to 10/90, more preferably 70/30 to 90/10. When the fine particles / binder is 95/5 or less, the adhesion between the silica-based porous film 14 and the transparent substrate 12 is sufficiently high. When the fine particle / binder is 10/90 or more, the antireflection effect is sufficiently high.
When mix | blending a terpene derivative (d) with a topcoat liquid, 0.01-2 mass parts is preferable with respect to 1 mass part of solid content of a topcoat liquid, and 0.03-1 mass part is the compounding quantity. More preferred. When the terpene derivative (d) is 0.01 parts by mass or more, the antireflection effect is sufficiently high as compared with the case where the terpene derivative (d) is not added. If the terpene derivative (d) is 2 parts by mass or less, the strength of the silica-based porous film 14 will be good.

  The top coat liquid is, for example, a mixture of a fine particle (b) dispersion, a matrix precursor (c) solution, and an additional dispersion medium (a), a terpene derivative (d), and other additives as necessary. It is prepared by.

The top coat liquid described above includes a dispersion medium (a), fine particles (b), and a matrix precursor (c), so that a silica-based porous film having an antireflection effect can be compared with a low cost at a low cost. It can be formed even at low temperatures. That is, when the silica-based porous film is formed using the above-described topcoat liquid, voids are selectively formed around the fine particles (b) in the silica-based porous film, and the voids have an antireflection effect. It has improved.
Further, when the topcoat liquid contains the terpene derivative (d), the volume of the voids increases, and the antireflection effect is increased.

As a method for applying the top coat liquid, known wet coat methods (spin coat method, spray coat method, dip coat method, die coat method, curtain coat method, screen coat method, ink jet method, flow coat method, gravure coat method, bar (Coating method, flexo coating method, slit coating method, roll coating method, sponge roll coating method, squeegee coating method, etc.) can be used.
Among these, a roll coating method is preferable, and a reverse roll coating method in which coating is performed with a coating roll of a reverse roll coater is particularly preferable.
The coating temperature is preferably room temperature to 80 ° C, more preferably room temperature to 60 ° C.

The firing may be performed after the top coat liquid is applied, or the transparent base 12 may be heated to the firing temperature in advance and the top coat liquid may be applied to the surface of the transparent base 12.
The firing temperature is preferably 30 ° C. or higher, and may be appropriately determined according to the material of the transparent substrate 12, the fine particles (b), or the matrix precursor (c). In order to rapidly convert the hydrolyzate of alkoxysilane into a fired product, it may be fired at 80 ° C. or higher, preferably 100 ° C. or higher, and more preferably 200 to 700 ° C. When the firing temperature is 100 ° C. or higher, the fired product is densified and durability is improved.
When the transparent base material 12 is glass, it can also serve as the baking process at the time of forming the silica type porous membrane 12, and the physical strengthening process of glass. In the physical strengthening step, the glass is heated to near the softening temperature. In this case, the firing temperature is set to about 600 to 700 ° C. In general, the firing temperature is preferably equal to or lower than the thermal deformation temperature of the transparent substrate 12. The lower limit value of the firing temperature is determined according to the composition of the topcoat liquid.
Since the polymerization proceeds to some extent even in natural drying, it is theoretically possible to set the drying or calcination temperature to a temperature setting near room temperature if there is no restriction on time.

{Second step}
In the second step, an antifouling layer forming coating solution containing a plurality of nanosheets and a dispersion medium of the nanosheets on the surface of the silica-based porous film 14 formed on the surface of the transparent substrate 12 in the first step. (Hereinafter also referred to as “overcoat solution”) is applied and dried to form the antifouling layer 16. Thereby, the article 10 is obtained.
The overcoat liquid contains a plurality of nanosheets and a dispersion medium for the nanosheets.

The description of the nanosheet is the same as described above.
As the nanosheet, a layered product of a layered compound such as a commercially available layered polysilicate or layered clay mineral may be used, or one manufactured by a known manufacturing method may be used.
The nanosheet can be obtained, for example, by peeling off a layer constituting the natural or synthetic inorganic layered compound by a conventional method. For example, a nanosheet dispersion liquid in which nanosheets are dispersed in water can be obtained by adding an inorganic layered compound to water to swell and stirring. Moreover, as an inorganic layered compound, in order to improve the dispersibility to a solvent, you may use what processed the surface and the interlayer previously with surfactant etc.
The nanosheet dispersion liquid can be used as it is as an overcoat liquid or for the preparation of an overcoat liquid. For example, an overcoat liquid can be prepared by mixing a nanosheet dispersion and a solution of an optional component (such as a binder or a precursor thereof). Moreover, you may collect | recover nanosheets from a nanosheet dispersion liquid, and use it for preparation of an overcoat liquid.

  In the overcoat liquid, the content of the nanosheet is not particularly limited as long as the overcoat liquid can be applied, but is 0.05 to 0.50 mass% with respect to the total amount of the overcoat liquid (100 mass%). Is preferable, and 0.10 to 0.35 mass% is more preferable. If the content of the nanosheet is 0.05% by mass or more, an arbitrary component dissolved in the overcoat liquid is less likely to penetrate into the silica-based porous film 14 when the overcoat liquid is applied. If the content of the nanosheet is 0.50% by mass or less, the coating property of the overcoat liquid is good, a thin antifouling layer can be formed, and the uniformity of the film thickness of the antifouling layer to be formed is also good. .

The dispersion medium is a liquid that disperses the nanosheet. When a binder is blended in the overcoat liquid, the dispersion medium is preferably a solvent that dissolves the binder. The dispersion medium may be a single liquid or a mixed liquid obtained by mixing two or more liquids.
As the dispersion medium, water is preferably used. You may use water and an organic solvent together as needed. As the dispersion medium, an organic solvent may be used alone.
Examples of the organic solvent include alcohols (methanol, ethanol, isopropanol, butanol, diacetone alcohol, etc.), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), ethers (tetrahydrofuran, 1,4-dioxane, etc.), Cellosolves (methyl cellosolve, ethyl cellosolve, etc.), esters (methyl acetate, ethyl acetate, etc.), glycol ethers (ethylene glycol monoalkyl ether, etc.), nitrogen-containing compounds (N, N-dimethylacetamide, N, N-dimethyl) Formamide, N-methylpyrrolidone, etc.), sulfur-containing compounds (dimethyl sulfoxide, etc.) and the like. Among these, alcohols are preferable and methanol and ethanol are particularly preferable in terms of solvent drying property, water compatibility, and surface tension.
When the dispersion medium contains water, the content of water in the overcoat liquid is preferably 60% by mass or less, and more preferably 50% by mass or less with respect to the total mass of the overcoat liquid. When the content of water in the overcoat liquid is more than 60% by mass, the solvent is not sufficiently dried in the drying step after coating, and the appearance of the coating film is liable to occur.

When a layer containing a binder is formed as the antifouling layer 16, a binder or a precursor thereof is blended in the overcoat liquid. For example, when the binder is a condensate of a hydrolyzate of a hydrolyzable silane compound, a binder precursor is blended in the overcoat liquid. The binder precursor may be a hydrolyzate of a hydrolyzable silane compound or a hydrolyzable silane compound that is a precursor thereof.
The description of the binder and its precursor is the same as described above.

When the overcoat liquid contains a binder, the content is such that the mass ratio of the nanosheet content to the total amount of the nanosheet and the binder or its precursor (nanosheet / (nanosheet + binder)) is 0.25 or more. Is preferred. The value of nanosheet / (nanosheet + binder) is more preferably 0.375 or more, and particularly preferably 0.50 or more. When the nanosheet / (nanosheet + binder) is 0.25 or more, the decrease in the antireflection performance of the silica-based porous film 14 due to the penetration of the binder is suppressed, and the maximum transmittance by providing the antifouling layer 16 is reduced. The decrease can be sufficiently suppressed. 80-100 mass% is preferable with respect to the total mass of the solid content in an overcoat liquid, and, as for the total amount of a nanosheet and a binder or its precursor, 90-100 mass% is more preferable.
When the binder is a hydrolyzate of a hydrolyzable silane compound, the content of the binder or its precursor is in terms of SiO ₂ solids.

  When the binder or the precursor thereof is included, the overcoat liquid is prepared by, for example, mixing the nanosheet dispersion and a solution of the binder or the precursor thereof.

You may mix | blend other components other than a nanosheet, a binder, and its precursor with an overcoat liquid as needed.
As the other component, a surfactant is preferable.
The compounding amount of the surfactant is preferably such that the mass ratio of the surfactant content to the nanosheet content (surfactant / nanosheet) is 1.5 or less. When the surfactant / nanosheet exceeds 1.5, the transmittance tends to decrease due to the penetration of the surfactant component into the porous silica membrane.

  The solid content concentration in the overcoat liquid is preferably 0.05 to 0.5% by mass, and more preferably 0.1 to 0.4% by mass. If the solid content concentration in the overcoat liquid is less than 0.05% by mass, the antifouling property tends to be insufficient. On the other hand, if it exceeds 0.5% by mass, the antifouling layer becomes too thick and the transmittance tends to be insufficient.

As a method for applying the overcoat liquid, known wet coat methods (spin coat method, spray coat method, dip coat method, die coat method, curtain coat method, screen coat method, ink jet method, flow coat method, gravure coat method, bar (Coating method, flexo coating method, slit coating method, roll coating method, sponge roll coating method, squeegee coating method, etc.) can be used.
The coating temperature is preferably room temperature to 80 ° C, more preferably 35 to 60 ° C.

After application, the antifouling layer 16 is formed by drying or the like.
When the overcoat liquid contains only the nanosheet as a solid content, that is, when it does not contain any optional component other than the nanosheet (binder or precursor thereof, surfactant, etc.), drying after coating only needs to be able to remove the dispersion medium. The drying conditions are not particularly limited, but preferably satisfy the following drying conditions 1.
Drying condition 1: It is performed at a drying temperature of 300 ° C. or lower (more preferably 250 ° C. or lower, more preferably 200 ° C. or lower). If it is 300 degrees C or less, it can prevent sintering between a nanosheet and a silica type porous membrane, and nanosheets strongly, and the removal property of the antifouling layer at the time of outdoor exposure is not sacrificed.
The lower limit of the drying temperature is not particularly limited, but the substrate temperature is preferably 60 ° C. or higher, and more preferably 80 ° C. or higher. If it is 60 degreeC or more, a dispersion medium will fully be removed.

When the overcoat liquid contains a binder or a precursor thereof, drying after coating is preferably performed at a temperature that satisfies the above-described drying condition 1 and does not exceed the thermal decomposition temperature of the binder. When heated to a temperature equal to or higher than the thermal decomposition temperature, the binder in the antifouling layer is thermally decomposed, and the effect of including the binder (for example, improved adhesion between nanosheets in the antifouling layer, improved denseness of the antifouling layer, etc. ) May be damaged.
The lower limit of the drying temperature is not particularly limited, but the substrate temperature is preferably 60 ° C. or higher and more preferably 80 ° C. If it is 60 degreeC or more, a dispersion medium will fully be removed.

When the overcoat liquid contains an organic substance other than the binder and its precursor, for example, a surfactant, etc., drying after coating is performed at a temperature that satisfies the above-mentioned drying condition 1 and does not exceed the thermal decomposition temperature of the organic substance. It is preferable to perform drying. When heated to a temperature equal to or higher than the thermal decomposition temperature, the organic substance may be thermally decomposed and the effects of inclusion may be impaired.
The lower limit of the drying temperature is not particularly limited, but the substrate temperature is preferably 60 ° C. or higher and more preferably 80 ° C. If it is 60 degreeC or more, a dispersion medium will fully be removed.
The thermal decomposition temperature of the organic substance can be measured by differential thermal-thermogravimetric simultaneous measurement (TG-DTA).

  While the present invention has been described with reference to the exemplary embodiments, the present invention is not limited to the above-described embodiments. Each configuration in the above embodiment, a combination thereof, and the like are examples, and the addition, omission, replacement, and other modifications of the configuration can be made without departing from the spirit of the present invention.

The antifouling antireflection film of the present invention has an antifouling layer on the surface of the silica-based porous film, so that the antifouling property is enhanced while maintaining the antireflection performance of the silica-based porous film.
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 maximum transmittance higher than that of the transparent substrate and also has a good antifouling property.
Articles of the present invention include transparent parts for vehicles (headlight covers, side mirrors, front transparent boards, side transparent boards, rear transparent boards, etc.), transparent parts for vehicles (instrument panel surfaces, etc.), meters, architectural windows, Show windows, displays (notebook computers, monitors, LCDs, PDPs, ELDs, CRTs, PDAs, etc.), LCD color filters, touch panel substrates, pickup lenses, optical lenses, eyeglass lenses, camera components, video components, CCD cover substrates , Optical fiber end face, projector parts, copying machine parts, transparent substrate for solar cell, mobile phone window, backlight unit parts (for example, light guide plate, cold cathode tube, etc.), backlight unit parts, liquid crystal brightness enhancement film (for example, prism, Transflective film, etc.), LCD 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, covers for lighting fixtures, amplified laser light sources, antireflection films, polarizing films, agricultural films, etc. Useful as.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.
Among Examples 1 to 29 described later, Examples 1 to 21 are examples, and Examples 22 to 29 are comparative examples.
The measurement method, evaluation method, and raw materials (nanosheet dispersion and other raw materials) used in each example are shown below.

(Nanosheet refractive index)
A film-coated substrate obtained by applying the nanosheet dispersion liquid on a silicon substrate was measured with an ellipsometer (JA Woollam, model: M-2000DI), and the refractive index of the nanosheet at a wavelength of 589 nm was determined.

(Average thickness, average width, average area of nanosheets)
The average thickness of the nanosheet was calculated as follows. The nanosheet dispersion was applied onto a glass substrate by spin coating, the surface was observed with an atomic force microscope (manufactured by SII Nanotechnology), and the average value of 10 nanosheets arbitrarily selected from a measurement range of 2 μm square Was used as the average thickness.
The average width of the nanosheet was calculated as follows. Observed with the atomic force microscope, the length of the line segment connecting the two most distant points on one nanosheet was determined. The length of the longest line segment was calculated | required among the line segments on the nanosheet orthogonal to this line segment. The average value of these two line segments was taken as the width of the nanosheet, this operation was performed on any 10 nanosheets, and the average value of the 10 widths was taken as the average width.
The average area was calculated as follows. The product of two line segments calculated in the same manner as described above for one nanosheet was obtained, and the value divided by 2 was defined as the area of the nanosheet. This operation was performed on any 10 nanosheets, and the average value of the 10 areas was defined as the average area.

(Average transmittance (0 ° incidence), maximum transmittance (0 ° incidence))
Transmittance of light incident on the antifouling layer side surface of the article prepared in each example (or the silica porous film side surface of the transparent base material with the silica porous film before forming the antifouling layer) at an incident angle of 0 ° Was measured with a spectrophotometer (manufactured by Hitachi, Ltd., model: U-4100), and average transmittance (%) and maximum transmittance (%) within a wavelength range of 400 to 1100 nm were determined.

(Thickness of antifouling layer)
The wavelength at which the maximum transmittance is obtained in the measurement of the maximum transmittance (0 ° incidence) is compared before and after applying the overcoat liquid (antifouling layer forming coating liquid). The film thickness was calculated.

(Maximum transmittance change by application)
Maximum transmittance of transparent base material with silica-based porous film before forming antifouling layer (hereinafter “maximum transmittance before application”), maximum transmittance of articles obtained by forming antifouling layer (hereinafter “maximum after application”) "Transmittance") was measured in the same manner as described above, and the amount of change in each maximum transmittance (maximum transmittance after application (%)-maximum transmittance before application (%)) was calculated.
It shows that the fall of the anti-reflective performance of the silica type porous film by application | coating of overcoat liquid (coating liquid for antifouling layer formation) is so small that the value of this change amount is large. Further, the closer the change amount is to 0, the less the influence of the antifouling layer on the antireflection performance of the silica-based porous film is. The amount of change is preferably within a range of -0.2 to 0.2, and particularly preferably within a range of -0.1 to 0.2.

(Resin peel strength test)
As an index of antifouling property, the peel strength of an ethylene-vinyl acetate copolymer resin (EVA) film was measured by the following procedure.
An EVA film having a thickness of 0.8 mm was cut into a width of 5 mm and a length of 80 mm, placed on the surface of the antifouling layer side of the article obtained in each example, and held in a drying furnace at 160 ° C. for 30 minutes. After removing from the drying oven and the substrate temperature has dropped to room temperature, the force necessary to peel off the EVA film adhering to the antifouling layer (hereinafter referred to as “peeling force”, unit: g / 5 mm) And measured. It shows that an EVA film is easy to peel, that is, it is excellent in antifouling property, so that this peeling force is small.

(Maximum transmittance after outdoor exposure)
The removability of the antifouling layer during outdoor exposure was evaluated by the following procedure.
The antifouling low-reflection films of Examples 2, 7, 10, 20, and 30 described later were left outdoors. One week later, the maximum transmittance of the article was measured as described above. The removal performance of the antifouling layer was evaluated by comparing the maximum transmittance before and after exposure. As the maximum transmittance after exposure is closer to the maximum transmittance before formation of the antifouling layer, the removability of the antifouling layer is higher than the maximum transmittance before exposure.

<Preparation of topcoat solution>
While stirring 24.5 g of denatured ethanol, 24.0 g of isobutyl alcohol, 20.0 g of the matrix precursor solution (c1) prepared by the following procedure, and the following chain SiO ₂ fine particle dispersion (b1) 15.0 g of diacetone alcohol (hereinafter referred to as DAA) and 1.0 g of α-terpineol, which is a terpene derivative, are added, and the topcoat solution has a solid content concentration of 3.0% by mass. (A1) was prepared.

Chain-like SiO ₂ fine particle dispersion (b1):
Nissan Chemical Industries, Snowtex OUP, SiO ₂ conversion solid content concentration 15.5% by mass, average primary particle size 10-20 nm, average aggregate particle size 40-100 nm.

Preparation of matrix precursor solution (c1):
While stirring 77.6 g of denatured ethanol (manufactured by Nippon Alcohol Sales Co., Ltd., Solmix AP-11, a mixed solvent mainly composed of ethanol, the same applies hereinafter), A mixed solution with 0.1 g was added and stirred for 5 minutes. To this, 10.4 g of tetraethoxysilane (SiO ₂ equivalent solid content concentration: 29% by mass) is added and stirred at room temperature for 30 minutes, and the matrix precursor solution having a SiO ₂ equivalent solid content concentration of 3.0% by mass ( c1) was prepared. Incidentally, SiO ₂ in terms of solid concentration is a solid content concentration when all Si of tetraethoxysilane was converted to SiO _2.

<Preparation of nanosheet dispersion>
-Preparation of nanosheet dispersion (A):
While stirring 99.0 g of distilled water, 1.0 g of synthetic smectite (“Lucentite SWN” manufactured by Co-op Chemical Co.) was added thereto and stirred for 24 hours.
-Preparation of nanosheet dispersion (A '):
While stirring 98.0 g of distilled water, 2.0 g of synthetic smectite (“Lucentite SWN” manufactured by Coop Chemical Co., Ltd.) was added thereto and stirred for 24 hours.

-Preparation of nanosheet dispersion (B):
Synthetic smectite (“Lucentite SWN” manufactured by Coop Chemical Co., Ltd.) was chemically modified by the method described in JP-A-6-2870146, and a nanosheet dispersion liquid (B) in which this was dispersed was prepared. Specifically, 2 g of synthetic smectite (“Lucentite SWN” manufactured by Corp Chemical Co.) was dispersed in 100 mL of distilled water to obtain a suspension. 60 mL of an aqueous solution in which 3.5 g of polyoxyethylene alkylmethylammonium chloride was dissolved was added to the synthetic smectite suspension and reacted at room temperature for 2 hours with stirring. The product was subjected to solid-liquid separation and washing to remove by-product salts, and then dried to obtain an organoclay complex. 2.6 g of the obtained organoclay complex was added to 97.4 g of ethanol with stirring and stirred for 24 hours.

-Preparation of nanosheet dispersion (C):
A layered polysilicate nanosheet was synthesized by the method described in Reference 1 below.
SiO ₂ , NaOH and water were mixed so as to be SiO ₂ : NaOH: water = 4: 1: 25.8 (mass ratio), and reacted in a polytetrafluoroethylene container at 100 ° C. for 2 hours. A hexadecyltrimethylammonium chloride aqueous solution was added to the product and stirred for 1 day. This was solid-liquid separated and the product was dried. 100 g of toluene and 3.7 g of 1-butyl-3- (3-triethoxysilylpropyl) -4,5-dihydroimidazolium chloride are added to 1 g of the powder thus obtained under a nitrogen atmosphere, and the mixture is heated at 70 ° C. for 1 hour. Reacted. After the reaction, 40 mg of the solid-liquid separated, washed and dried product was dispersed in 20 g of water by ultrasonic treatment to obtain a 0.25 mass% dispersion.
Reference 1: Chemistry of Materials, 2011, 23, 266-273

-Preparation of nanosheet dispersion (D):
An aqueous colloidal titanate sheet was prepared as follows. A mixture of the stoichiometric composition of Cs ₂ CO ₃ and TiO ₂ was calcined at 800 ° C. for 20 hours to prepare a cesium titanate precursor. 70 g of the obtained cesium titanate precursor was immersed in 2 L of a 1 mol / L HCl solution. The acid treatment with the HCl solution was performed a total of 3 times by exchanging with a new solution every 24 hours. The obtained acid substitution product was filtered, washed with water, and dried in the air. The obtained proton titanate was added to a 0.0017 mol / L tetrabutylammonium hydroxide solution and shaken vigorously at room temperature for 10 days to obtain a milky white colloidal suspension. The obtained liquid was concentrated to adjust the solid content to 0.4% by mass.

The composition of the prepared nanosheet dispersion is shown in Table 1. In Table 1, SWN indicates “Lucentite SWN” manufactured by Corp Chemical. Both SWN and SPN are powdered smectites.
When observed with SWN, a transmission electron microscope, and an atomic force microscope, the form was a sheet form (nanosheet). When the refractive index, average thickness, average width, and average area of each nanosheet were measured, the results shown in Table 1 were obtained.

<Preparation of binder solution>
-Preparation of binder solution (E) (polymer solution):
While stirring 99.0 g of distilled water, 1.0 g of polyvinyl alcohol (manufactured by Polymer Science, molecular weight 25000, saponification degree 88%) was added thereto, followed by stirring in a 60 ° C. bath for 1 hour.
-Preparation of binder solution (F) (silane dilution):
While stirring 93.0 g of ethanol, 7 g of tetraethoxysilane was added thereto and stirred at room temperature for 30 minutes.
-Preparation of binder solution (G) (silane hydrolysis sol):
While stirring 80.5 g of denatured ethanol, a mixture of 11.4 g of ion-exchanged water and 0.5 g of 10% by mass nitric acid was added thereto and stirred for 5 minutes. To this, 7.6 g of tetraethoxysilane (SiO ₂ equivalent solid content concentration: 29% by mass) was added and stirred at room temperature for 30 minutes to prepare a sol having a SiO ₂ equivalent solid content concentration of 2.2% by mass.

<Preparation of other raw materials>
-Preparation of surfactant solution (H):
While stirring 95.0 g of water, 5.0 g of a 40% aqueous solution of tetrabutylammonium was added thereto and stirred for 30 minutes.

[Example 1]
An article having the same layer structure as that of the article 10 shown in FIG. 1 was produced by the following procedure. An undercoat layer was provided on the surface of the template glass, and this was used as the transparent substrate 12.

(Washing glass)
Prepare template glass (Solite manufactured by Asahi Glass Co., Ltd., low iron soda lime glass (white plate glass), size: 100 mm x 100 mm, thickness: 3.2 mm), and polish the surface of the template glass with a cerium oxide aqueous dispersion. The cerium oxide was washed off with water, rinsed with ion exchange water, and dried.

(Undercoat)
While stirring 85.7 g of denatured ethanol, a mixed solution of 6.6 g of ion-exchanged water and 0.1 g of 61 mass% nitric acid was added thereto, and the mixture was stirred for 5 minutes. To this, 7.6 g of tetraethoxysilane (SiO ₂ equivalent solid content concentration: 29% by mass) was added and stirred at room temperature for 30 minutes to prepare an undercoat solution having a SiO ₂ equivalent solid content concentration of 2.2% by mass. . This was applied to the surface of the template glass washed as described above by spray coating, and baked to form a film.

(Top coat)
The reverse roll coater (Sanwa Seiki Co., Ltd.) was preheated in a preheating furnace (ISUZU VTR-115) and the surface temperature was kept at 30 ° C. The topcoat solution (a1) was applied using a coating roll manufactured by Komatsu. Then, it baked for 30 minutes at 500 degreeC in air | atmosphere, and obtained the transparent base material with a silica type porous membrane.

(Overcoat)
While stirring 25 g of distilled water, 25 g of the nanosheet dispersion liquid (A) was added thereto, 50 g of ethanol was further added, and the mixture was stirred for 10 minutes to prepare an overcoat solution. 2 cc of the obtained overcoat solution was collected with a poly dropper, dropped onto the silica-based porous film of the transparent substrate with the silica-based porous film prepared above, and applied by spin coating (2000 rpm, 20 seconds). ) Thereafter, drying was performed at 200 ° C. for 1 minute in a drying furnace to obtain a target article.

[Examples 2 to 17]
Except for changing the composition of the overcoat solution, articles were obtained by carrying out glass washing, undercoat, topcoat and overcoat in exactly the same manner as in Example 1.
The overcoat solution used in each example was prepared by the following procedure. The raw materials and blending amounts used for the preparation in each example are shown in Tables 2-3. Application and drying of these overcoat solutions were performed in the same manner as in Example 1.

The overcoat liquid used in Example 2 was prepared by adding 35 g of the nanosheet dispersion (A) to 15 g of distilled water, stirring 50 g of ethanol, and stirring for 10 minutes.
The overcoat liquid used in Example 3 was prepared by adding 50 g of ethanol thereto and stirring for 10 minutes while stirring 50 g of the nanosheet dispersion liquid (A).
The overcoat solution used in Example 4 was prepared by adding 1.92 g of nanosheet dispersion (B) to 98.08 g of ethanol and stirring for 10 minutes.
The overcoat solution used in Example 5 was prepared by adding 3.85 g of nanosheet dispersion liquid (B) to 96.15 g of ethanol and stirring for 10 minutes.
The overcoat solution used in Example 6 was prepared by adding 5.77 g of nanosheet dispersion liquid (B) to 94.23 g of ethanol and stirring for 10 minutes.
The overcoat liquid used in Example 7 was prepared by adding 9.62 g of nanosheet dispersion liquid (B) to 90.38 g of ethanol and stirring for 10 minutes.
The overcoat liquid used in Example 8 was prepared by adding 19.2 g of nanosheet dispersion (B) to 80.8 g of ethanol and stirring for 10 minutes.

The overcoat liquid used in Example 9 was added with 25 g of nanosheet dispersion (A) while stirring 24 g of water, further added with 1 g of binder solution (E), and finally added 50 g of ethanol and stirred for 10 minutes. Was prepared.
The overcoat liquid used in Example 10 was stirred with 20 g of water while adding 25 g of the nanosheet dispersion (A), further adding 5 g of the binder solution (E), and finally adding 50 g of ethanol and stirring for 10 minutes. Was prepared.
The overcoat liquid used in Example 11 was added with 25 g of nanosheet dispersion (A) while stirring 15 g of water, added with 10 g of binder solution (E), and finally added 50 g of ethanol and stirred for 10 minutes. Was prepared.
The overcoat liquid used in Example 12 was stirred with 10 g of water, 25 g of nanosheet dispersion (A) was added thereto, 15 g of binder solution (E) was further added, and 50 g of ethanol was finally added, followed by stirring for 10 minutes. Was prepared.
The overcoat liquid used in Example 13 was stirred with 10 g of water, 20 g of nanosheet dispersion (A) was added thereto, 20 g of binder solution (E) was further added, and 50 g of ethanol was finally added, followed by stirring for 10 minutes. Was prepared.
The overcoat liquid used in Example 14 was stirred with 10 g of water, 15 g of nanosheet dispersion (A) was added thereto, 25 g of binder solution (E) was further added, and 50 g of ethanol was finally added, followed by stirring for 10 minutes. Was prepared.
The overcoat liquid used in Example 15 was stirred with 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. Was prepared.

In the overcoat liquid used in Example 16, 25 g of nanosheet dispersion (A) was added thereto while stirring 25 g of water, 42.5 g of ethanol was further added, and 7.5 g of binder solution (F) was finally added. Prepared by stirring for 10 minutes.
The overcoat liquid used in Example 17 was stirred with 50.4 g of ethanol, 9.6 g of nanosheet dispersion liquid (B) was added thereto, further 25 g of water was added, and finally 15 g of binder solution (E) was added. It was prepared with.
The overcoat solution used in Example 18 was stirred with 72.9 g of ethanol, 9.6 g of nanosheet dispersion (B) was added thereto, 7.5 g of binder solution (F) was added, and finally 10 g of water was added. In addition, it was prepared by stirring for 10 minutes.

[Examples 19 to 20]
Articles were obtained by performing glass washing, undercoat, topcoat, and overcoat in exactly the same manner as in Example 1 except that the drying conditions after application of the overcoat solution were changed. The composition of the overcoat solution and the coating method are the same as in Example 1.
In Example 19, drying after applying the overcoat solution was performed at 300 ° C. for 1 minute, and in Example 20, it was performed at 400 ° C. for 1 minute.

[Example 21]
Articles were obtained by performing glass washing, undercoat, topcoat, and overcoat in exactly the same manner as in Example 1 except that the nanosheet dispersion liquid (C) was used as it was as an overcoat liquid. The composition, coating and drying of the overcoat solution are the same as in Example 1.

[Example 22]
Only the glass washing, undercoat, and topcoat were performed in the same manner as in Example 1 to obtain a transparent substrate with a silica-based porous film. Subsequent overcoating was not performed, and the substrate with the silica-based porous film was used as the article of Example 22.

[Examples 23 to 29]
Except for changing the composition of the overcoat solution, articles were obtained by carrying out glass washing, undercoat, topcoat and overcoat in exactly the same manner as in Example 1.
The overcoat solution used in each example was prepared by the following procedure. Table 4 shows the raw materials and blending amounts used for the preparation in each example. Application and drying of these overcoat solutions were performed in the same manner as in Example 1.

The overcoat liquid used in Example 23 was prepared by adding 50 g of ethanol thereto and stirring for 10 minutes while stirring 50 g of the nanosheet dispersion liquid (A ′).
The overcoat liquid used in Example 24 was prepared by adding 0.96 g of the nanosheet dispersion liquid (B) and stirring for 10 minutes while stirring 99.04 g of ethanol.
The overcoat liquid used in Example 25 was prepared by adding 15 g of the binder solution (E) thereto while stirring 35 g of water, and finally adding 50 g of ethanol and stirring for 10 minutes.
The overcoat solution used in Example 26 was prepared by adding 40 g of the binder solution (E) to 10 g of water while stirring, and finally adding 50 g of ethanol and stirring for 10 minutes.
The overcoat solution used in Example 27 was prepared by adding 40 g of the binder solution (G) thereto while stirring 60 g of ethanol and stirring the mixture for 10 minutes.
The overcoat solution used in Example 28 was prepared by adding 7.5 g of a surfactant solution (H) to 92.5 g of ethanol and stirring for 10 minutes.
In Example 29, the nanosheet dispersion liquid (D) was used as it was as an overcoat liquid.

Said measurement and evaluation were performed about the obtained article | item. The results are shown in Tables 2-4.
Moreover, in Example 2, the SEM photograph of the outermost surface by the side of the silica type porous membrane of the transparent base material with a silica type porous membrane before forming an antifouling layer is shown in FIG. The outermost surface on the side is shown in FIG. 3A, and the cross section is shown in FIG.

In Examples 1 to 21, the peel force in the resin peel strength test was 740 g / 5 mm or less, and the peel force (840 g / 5 mm) in the transparent substrate with a silica-based porous film (Example 22) before forming the antifouling layer ) Is smaller than 100 g / 5 mm. From this, it was confirmed that the antifouling property was imparted by forming the antifouling layer. In Examples 1 to 21, the maximum transmittance change amount by application of the overcoat liquid is -0.16 to 0.13, and the antireflection performance does not decrease or decreases even when the antifouling layer is formed. It was also confirmed that it was slight.
On the other hand, even when an overcoat solution containing nanosheets was used, the antireflection performance of Example 23 in which the film thickness of the formed antifouling layer was 41 nm 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 Example 25, in which the binder was used alone as the solid content of the overcoat liquid and the solid content concentration was 0.15%, the effect of imparting antifouling properties was small, and the peel force was as large as 760 g / 5 mm. In Examples 26 and 27 in which the solid content concentration was increased to 0.40% with the binder alone, the antireflection performance was lowered.
In Example 28 in which the surfactant was used alone as the solid content of the overcoat liquid, the effect of imparting antifouling properties was small, and the antireflection performance was also lowered.
In Example 29 using the titanium oxide nanosheet, the maximum transmittance decreased by 0.55% due to the high refractive index of the antifouling layer.

Comparing the removability of the antifouling layer from the maximum transmittance after outdoor exposure of Examples 2, 7, 10, 21, and 29, in Examples 2, 7, and 10 using smectite nanosheets, the maximum transmittance after exposure was antifouling. The value was close to the maximum transmittance before layer formation, and it was found that the antifouling layer was being removed by outdoor exposure.
On the other hand, in Examples 21 and 29 using layered polysilicate nanosheets or titanium oxide nanosheets for the antifouling layer, the maximum transmittance was almost constant before and after exposure, and removal of the antifouling layer by outdoor exposure was not observed. It was.

DESCRIPTION OF SYMBOLS 10 Goods 12 Glass plate 14 Silica type porous film 16 Antifouling layer 18 Antifouling antireflection film

Claims (12)

A silica-based porous membrane, and an antifouling layer covering the surface of the silica-based porous membrane,
The antifouling layer contains a plurality of nanosheets, and the plurality of nanosheets is made of a low refractive material having a refractive index of 1.4 to 1.65,
An antifouling antireflection film, wherein the antifouling layer has an average film thickness of 0.4 to 40 nm. The nanosheets has a mean average area of thickness and 100～1000000Nm ² of 0.7～20Nm, antifouling antireflection film according to claim 1.   The antifouling antireflection film according to claim 1 or 2, wherein the nanosheet is derived from an inorganic layered compound selected from layered polysilicates and clay minerals.   The antifouling antireflection film according to any one of claims 1 to 3, wherein the nanosheet is surface-modified with a surfactant.   An article having the antifouling antireflection film according to any one of claims 1 to 4 on a transparent substrate. Forming a silica-based porous film on a transparent substrate;
Applying a coating solution for forming an antifouling layer to the surface of the silica-based porous membrane, and drying to form an antifouling layer,
The antifouling layer forming coating solution contains a plurality of nanosheets and a dispersion medium of the nanosheets,
Each of the plurality of nanosheets is made of a low refractive material having a refractive index of 1.4 to 1.65,
The manufacturing method of the articles | goods whose average film thickness of the said pollution protection layer is 0.4-40 nm. The method for producing an article according to claim 6, wherein the nanosheet has an average thickness of 0.7 to 20 nm and an average area of 100 to 1000000 nm ² . The antifouling layer forming solution further includes a binder or a precursor thereof,
The article according to claim 6 or 7, wherein a mass ratio of a content of the nanosheet to a total amount of the nanosheet and the binder or a precursor thereof in the coating solution for forming an antifouling layer is 0.25 or more. Manufacturing method.   The manufacturing method of the articles | goods as described in any one of Claims 6-8 whose solid content concentration in the said coating liquid for antifouling layer formation is 0.05-0.50 mass%. The antifouling layer forming coating solution further comprises a surfactant,
The method for producing an article according to any one of claims 6 to 9, wherein a mass ratio of the content of the surfactant to the content of the nanosheet is 1.5 or less. The antifouling layer forming coating solution contains only a nanosheet as a solid content,
The manufacturing method of the articles | goods of Claim 6 or 7 which performs drying after apply | coating the said coating liquid for antifouling layer formation at 300 degrees C or less. The dispersion medium contains water;
The article according to any one of claims 6 to 11, wherein a content of water in the antifouling layer forming coating solution is 60% by mass or less based on a total mass of the antifouling layer forming coating solution. Manufacturing method.