WO2021095770A1 - Antiglare layer-provided substrate, image display apparatus, and antiglare layer-provided substrate manufacturing method - Google Patents

Abstract

The present invention has a substrate and an antiglare layer that is formed on the substrate directly or via another layer and that has a projection-recess structure on the surface. The antiglare layer is formed from a cured product of an antiglare coating forming composition that contains a polysiloxane having a fluorine-containing organic group.

Description

Manufacturing method of base material with antiglare layer, image display device, and base material with antiglare layer

The present invention has an antiglare layer (anti-glare function), a base material with an antiglare layer that gives good visibility without glare (sparkling), an image display device provided with the base material, and an antiglare layer. Regarding a method for producing a base material.

Image display devices (liquid crystal displays, organic EL displays, plasma displays, etc.) provided in various devices such as televisions, personal computers, and smartphones reflect external light such as indoor lighting (fluorescent lamps, etc.) and sunlight on the display surface. As a result, the visibility of the image may decrease due to the reflected image.

As a method of suppressing the reflection of external light, there is a method of applying antiglare treatment (anti-glare treatment) to the display surface of the image display device. As a method of antiglare treatment, a treatment of etching the surface of a transparent base material such as glass with a chemical such as hydrofluoric acid (see Patent Document 1) and a treatment of forming an organic antiglare layer having irregularities on the surface (Patent). Reference 2) and the like have been proposed.

Japanese Patent No. 5839134 International Publication No. 2018/070426

However, in the process of etching the surface of the glass substrate with a chemical, the danger of the chemical becomes a problem, and in the process of forming an organic antiglare layer on the surface, the applicability to the glass substrate and further on the film are further improved. Problems arise in coatability and adhesion when forming a functional layer.

In addition, with the recent increase in the definition of image display devices, when the antiglare layer is arranged on the display surface side, there is also a problem that a glare phenomenon in which random light intensity appears on the surface is likely to occur.

From the above points, the present invention provides a base material with an antiglare layer which is excellent in antiglare property (anti-glare function) and gives good visibility without causing glare, and an image display device provided with the base material with an antiglare layer. The purpose. Furthermore, it is an object of the present invention to provide a base material with an antiglare layer having excellent coatability and adhesion when forming a functional layer, an image display device provided with the base material, and a method for manufacturing the base material with an antiglare layer.

The inventors have found that the above problems can be achieved by the following configuration, and have completed the present invention.
The present invention
1. 1. It has a base material and an antiglare layer formed directly on the base material or via another layer and having an uneven structure on the surface, and the antiglare layer contains a polysiloxane having a fluorine-containing organic group. A base material with an antiglare layer, which is formed from a cured product of a composition for forming an antiglare film and has a convex surface coverage of 5% to 70%.
2. The base material with an antiglare layer according to 1, wherein the height of the convex portion of the uneven structure is 50 nm to 2,000 nm.
3. 3. The base material with an antiglare layer according to 1 or 2, wherein the HAZE of the antiglare layer is 0.3% to 40%.
4. The base material with an antiglare layer according to any one of 1 to 3, wherein the refractive index of the antiglare layer is in the range of 1.3 to 1.49.
5. The antiglare layer is formed on the high refractive index layer, and the refractive index of the high refractive index layer is higher than the refractive index of the antiglare layer 1 to 4. Substrate with anti-glare layer according to any of
6. The base material with an antiglare layer according to 5, wherein the refractive index of the high refractive index layer is in the range of 1.5 to 2.1.
7. The base material with an antiglare layer according to any one of 1 to 6, further comprising a functional layer formed on the antiglare layer.
An image display device comprising the base material with an antiglare layer according to any one of 8.1 to 7.
9. A method for producing a base material with an antiglare layer, which comprises a step of applying a coating liquid for forming an antiglare film containing a polysiloxane having a fluorine-containing organic group onto the base material to form an antiglare layer.
It is in.

According to the present invention, there is provided a base material with an antiglare layer which is excellent in antiglare (anti-glare function) and gives good visibility without causing glare (sparkling), and an image display device provided with the base material. be able to. Further, it is possible to provide a base material with an antiglare layer having excellent coatability and adhesion when forming a functional layer, an image display device provided with the base material, and a method for manufacturing the base material with an antiglare layer.

Hereinafter, the present invention will be described in more detail.

<Composition for forming an antiglare coating layer>
The antiglare-forming composition used in the present invention includes at least a polysiloxane having a fluorine-containing organic group (hereinafter, also referred to as component (A)), and further comprises a solvent for dissolving the polysiloxane.

<Ingredient (A)>
The component (A) is a polysiloxane having an organic group substituted with a fluorine atom in the side chain. Such an organic group substituted with a fluorine atom is an organic group in which a part or all of hydrogen atoms of an aliphatic group or an aromatic group is substituted with a fluorine atom. The organic groups substituted with fluorine atoms are, among others, alkyl groups in which some or all of hydrogen atoms are substituted with fluorine atoms and alkyl groups containing ether bonds in which some or all of hydrogen atoms are substituted with fluorine atoms. , An organic group containing a phenyl group in which a part or all of a hydrogen atom is substituted with a fluorine atom and the like are preferable. The number of fluorine atoms contained in the organic group substituted with the fluorine atom is also not particularly limited. The organic group substituted with the fluorine atom has a preferable carbon number of 1 to 20, more preferably 3 to 15, and particularly preferably 3 to 8. Specific examples of these include a trifluoropropyl group, a tridecafluorooctyl group, a heptadecafluorodecyl group, and a pentafluorophenylpropyl group.

Among these, an organic group having a perfluoroalkyl group is preferable, and an organic group represented by the following formula (F) is more preferable, from the viewpoint of easily obtaining a highly transparent film.
CF ₃ (CF ₂ ) _k CH ₂ CH _2- * (F)
(In the formula, k is an integer from 0 to 12. * Indicates the connection position.)
Specific examples of the organic group represented by the above formula (F) include a trifluoropropyl group, a tridecafluorooctyl group, and a heptadecafluorodecyl group.

In the present invention, a plurality of types of polysiloxane having a side chain as described above may be used in combination.

The method for obtaining the polysiloxane having the above-mentioned organic group substituted with a fluorine atom in the side chain is not particularly limited. Generally, it is obtained by polycondensing the above-mentioned alkoxysilane compound having an organic group in the side chain.

Of these, a polysiloxane obtained by polycondensing an alkoxysilane component containing an alkoxysilane compound represented by the formula (1) is preferable.
R ¹¹ Si (OR ¹² ) ₃ (1)

^{Here, R 11} of the formula (1) represents an organic group substituted with the above-mentioned fluorine atom, but the number of fluorine atoms contained in this organic group is not particularly limited.

Further, R ¹² of formula (1) represents a hydrocarbon group having 1 to 5 carbon atoms, preferably a saturated hydrocarbon group having 1 to 5 carbon atoms, more preferably a methyl group, an ethyl group, a propyl group, Or it is a butyl group.

Among the alkoxysilanes represented by the formula (1), an alkoxysilane in which R ¹¹ is a perfluoroalkyl group is preferable, ^{and an alcoholic silane in which R 11} is an organic group represented by the above formula (F) is more preferable. ..

Specific examples of the alkoxysilane having an organic group represented by the formula (F) include trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, tridecafluorooctyltrimethoxysilane, tridecafluorooctylriethoxysilane, and hepta. Examples thereof include decafluorodecyltrimethoxysilane and heptadecafluorodecyltriethoxysilane.

In particular, from the viewpoint of easily obtaining a highly transparent film, it is preferable that k is an integer of 2 to 12.

In the present invention, at least one of the alkoxysilanes represented by the formula (1) may be used, but a plurality of types may be used if necessary.

Further, the polysiloxane having the organic group substituted with the fluorine atom in the side chain is an alkoxysilane compound other than the alkoxysilane compound represented by the above formula (1) (hereinafter, also referred to as other alkoxysilane compound). It may be a polysiloxane obtained by polycondensing the containing alkoxysilane component. Specific examples of other alkoxysilane compounds include at least one selected from the group consisting of the alkoxysilane compound represented by the following formula (2) and the alkoxysilane compound represented by the following formula (3). Not limited to these.
Si (OR ² ) ₄ (2)
R ³¹ _n Si (OR ³² ) _4-n (3)
(In the formula, R ³¹ represents an organic group or a hydrogen atom not substituted with a fluorine atom, R ³² represents a hydrocarbon group having 1 to 5 carbon atoms, and n is an integer of 1 to 3).

^{R 2} of the formula (2) represents a hydrocarbon group, but a saturated hydrocarbon group having 1 to 5 carbon atoms is preferable, and a methyl group and an ethyl group are more preferable, because the smaller the number of carbon atoms, the higher the reactivity. It is a propyl group or a butyl group.

Specific examples of such tetraalkoxysilanes include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, etc., which are easily available as commercial products.

^{R 32} of the formula (3) independently represents a hydrocarbon group having 1 to 5 carbon atoms. R ³² may be the same or different from each other.

^{R 31} in the formula (3) is preferably an organic group having 1 to 20 carbon atoms, and more preferably an organic group having 1 to 15 carbon atoms. R ³¹ may be the same or different from each other. Examples of the organic group not substituted with a fluorine atom include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a stearyl group (octadecyl group) and the like. ~ 18 alkyl groups; 2-18 alkenyl groups such as vinyl groups; cycloalkyl groups such as cyclohexyl groups; (meth) such as 3- (meth) acrylicoxypropyl groups (γ- (meth) acryloxypropyl groups) Acrylicoxy group-containing alkyl group; hydroxyl group-containing alkyl group such as 3-hydroxypropyl group; γ-ureido (3-ureido) propyl group, ureido group-containing alkyl group; γ-amino (3-amino) propyl group, 2- Amino group-containing alkyl groups such as aminoethylaminomethyl group, 3- (N-styrylmethyl-2-aminoethylamino) propyl group; γ-glycidoxy (3-glycidyloxy) propyl group, 2- (3,4-epoxy) Epoxy group-containing alkyl groups such as cyclohexyl) ethyl groups; mercapto group-containing alkyl groups such as γ-mercapto (3-mercapto) propyl groups; isocyanate group-containing alkyl groups such as 3-isocyanuppropyl groups; aryl groups such as phenyl groups, etc. Can be mentioned.
Among these, methyl group, ethyl group, propyl group, butyl group, pentyl group, heptyl group, octyl group, dodecyl group, hexadecyl group, octadecyl group, phenyl group, vinyl group, γ-aminopropyl group, γ-glycid. A xypropyl group and a γ-methacryloxypropyl group are more preferable.

Specific examples of the alkoxysilane represented by the formula (3) include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, and butyl. Trimethoxysilane, Butyltriethoxysilane, Pentyltrimethoxysilane, Pentyltriethoxysilane, Heptiltrimethoxysilane, Heptiltilriethoxysilane, Octiltrimethoxysilane, Octiltriethoxysilane, Dodecyltrimethoxysilane, Dodecyltriethoxysilane, Hexa Decyltrimethoxysilane, hexadecyltriethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-isocyanuppropyltrimethoxysilane, 3 -Isocyanoxide triethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane , Γ-Mercaptopropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-ureidopropyltri Examples thereof include, but are not limited to, trialkoxysilanes such as methoxysilane and γ-ureidopropyltriethoxysilane and dialkoxysilanes such as dimethyldimethoxysilane and dimethyldiethoxysilane.

The total amount of the alkoxysilane compound represented by the formula (1) is 3 mol% or more with respect to the total 100 mol% of the alkoxysilane compound used to obtain the component (A) from the viewpoint of easily obtaining a film. Is preferable, and 5 mol% or more is more preferable. Further, from the viewpoint of suppressing the formation of gel or foreign matter, 40 mol% or less is preferable, and 30 mol% or less is more preferable.

The upper limit of the amount of the other alkoxysilane compound used is preferably 97 mol% or less, more preferably 95 mol% or less, based on 100 mol% of the total total alkoxysilane compound used to obtain the component (A). The lower limit is preferably 60 mol% or more, more preferably 70 mol% or more.

(Synthesis of polysiloxane)
The method for condensing the polysiloxane used in the present invention is not particularly limited, and examples thereof include a method for hydrolyzing and condensing alkoxysilane in a solvent such as alcohol or glycol. At that time, the hydrolysis / condensation reaction may be either partial hydrolysis or complete hydrolysis. In the case of complete hydrolysis, theoretically, 0.5 times by mole of water of all the alkoxy groups in the alkoxysilane may be added, but usually, an excess amount of water is added by more than 0.5 times by mole.

In the present invention, the amount of water used in the above reaction can be appropriately selected as desired, but is usually 0.1 to 7 times the molar amount, preferably 0.1 to 5 times the molar amount of all the alkoxy groups in the alkoxysilane. It is a mole.

Also, usually, for the purpose of promoting hydrolysis / condensation reaction, acids such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, oxalic acid and maleic acid; alkalis such as ammonia, methylamine, ethylamine, ethanolamine and triethylamine; hydrochloric acid, A metal salt such as sulfuric acid or nitric acid may be used as a catalyst. In this case, the amount of the catalyst used in the reaction is preferably about 0.001 to 0.1 times the molar amount of all the alkoxy groups in the alkoxysilane, and more preferably 0.01 to 0.06 times the molar amount. Further, it is also common to promote the hydrolysis / condensation reaction by heating the solution in which the alkoxysilane is dissolved. At that time, the heating temperature and the heating time can be appropriately selected as desired, preferably from several tens of minutes in a closed container or under reflux so that the reaction system is set to 50 ° C. to 180 ° C. and the liquid does not evaporate or volatilize. It takes place for dozens of hours. For example, a method of heating / stirring at 50 ° C. for 24 hours or heating / stirring at reflux for 2 to 10 hours can be mentioned.

Another method is to heat a mixture of alkoxysilane, solvent and oxalic acid, for example. Specifically, it is a method in which oxalic acid is added to alcohol in advance to prepare an alcohol solution of oxalic acid, and then the solution and alkoxysilane are mixed and heated. At that time, the amount of oxalic acid is generally 0.2 to 2 mol, preferably 0.5 to 2 mol, based on 1 mol of all the alkoxy groups contained in the alkoxysilane. The heating in this method can be performed at a liquid temperature of 50 ° C. to 180 ° C., and preferably, for example, in a closed container or under reflux for several tens of minutes to several tens of hours so that evaporation, volatilization, etc. of the liquid do not occur. Will be done.

When a plurality of alkoxysilanes are used in each of the above methods, a plurality of alkoxysilanes may be mixed in advance, or a plurality of alkoxysilanes may be added in sequence.

When polycondensing alkoxysilane by the above method, the concentration obtained by converting the total amount of silicon atoms of the charged alkoxysilane into SiO _{2 (hereinafter referred to as SiO 2} equivalent concentration) is 20% by mass or less. Generally, 15% by mass or less is preferable. By selecting an arbitrary concentration in such a concentration range, gel formation can be suppressed and a homogeneous polysiloxane solution can be obtained.

The solvent used for polycondensing the alkoxysilane is not particularly limited as long as it dissolves the above-mentioned alkoxysilane compound. Generally, since alcohol is produced by the polycondensation reaction of alkoxysilane, an organic solvent having good compatibility with alcohols and alcohols is used.

Specific examples of the solvent used for the above-mentioned polycondensation include alcohols such as methanol, ethanol, propanol and n-butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether and diethylene glycol monoethyl ether. Glycol ether and the like can be mentioned. In the present invention, a plurality of types of the above organic solvents may be mixed and used.

<Composition for forming an antiglare film>
The method for preparing the coating liquid (hereinafter, also simply referred to as a coating liquid or a coating liquid for forming an antiglare film), which is the composition for forming an antiglare film of the present invention, is not particularly limited. As an example, the following solvent group (A), solvent group (B) and other solvent groups may be added to the polysiloxane solution obtained above, if necessary. Further, if necessary, a method of preparing the polysiloxane solution after concentrating it or replacing it with another solvent may be used.

<Solvent group (A)>
The solvent group (A) contained in the coating liquid for forming an antiglare film of the present invention is at least one selected from glycol ethers having a boiling point of less than 160 ° C. and derivatives thereof, or ketones. Specifically, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, Glycol ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol dimethyl ether and propylene glycol diethyl ether and derivatives thereof, and ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone can be mentioned. Among them, from the viewpoint of coating stability, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, methyl Isobutyl ketone is preferred.

The content of the solvent group (A) in the coating liquid for forming an antiglare film is 0.1 to 300 with respect to 1 part by mass of _{the total amount of silicon atoms contained in the component (A) converted to SiO 2.} It is by mass, preferably 0.3 to 100 parts by mass, and particularly preferably 0.8 to 50 parts by mass.

<Solvent group (B)>
The solvent group (B) contained in the coating liquid for forming an antiglare film of the present invention is at least one selected from alcohols having a boiling point of 120 ° C. or lower. Specific examples thereof include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol and 2-methyl-2-propanol. Among them, the composition. From the viewpoint of storage stability, methanol, ethanol, 2-propanol, 2-butanol, and 2-methyl-1-propanol are preferable.

The content of the solvent group (B) in the coating liquid for forming an antiglare film is 0.5 to 500 with respect to 1 part by mass of _{the total amount of silicon atoms contained in the component (A) converted to SiO 2.} It is a part by mass, preferably 1 to 200 parts by mass, and particularly preferably 2 to 150 parts by mass.

<Other solvents>
The coating liquid for forming an antiglare film of the present invention contains a solvent other than the solvent groups (A) and (B) (hereinafter, also referred to as other solvents) as necessary from the viewpoint of the stability of the coating liquid. It may be.

Examples of other solvents include alcohols such as hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, diacetone alcohol, ethylene glycol, diethylene glycol, dipropylene glycol, 2-methyl-2,4-pentanediol, Glycos such as propanediol, butanediol, pentanediol, hexanediol, heptanediol, ethylene glycol monobutyl ether, ethylene glycol dibutyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene Glycoldipropyl ether, propylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, glycol ethers such as diethylene glycol dibutyl ether, acetic acid Ethers such as methyl, ethyl acetate, ethyl lactate, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, γ-butyrolactone, dimethylsulfoxide, tetramethylurea, hexamethylphosphotriamide , M-cresol, tetrahydrofuran and the like. Among them, from the viewpoint of availability and storage stability of the composition, ethylene glycol, diethylene glycol, 2-methyl-2,4-pentanediol, propanediol, butanediol, ethylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene. Glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, N-methyl -2-Pyrrolidone, N, N-dimethylformamide and tetrahydrofuran are preferably used.

The concentration obtained by converting the total amount of silicon atoms contained in the component (A) in the coating liquid for forming an antiglare film into SiO _{2 (SiO 2} conversion concentration) is preferably 0.2 to 10% by mass, preferably 0.5 to 10. 8% by mass is more preferable.

<Other ingredients>
In the present invention, components other than the component (A), the solvent group (A) and (B), for example, inorganic fine particles, metalloxane oligomer, metalloxane polymer, leveling agent, surfactant and the like are included. May be.

As the inorganic fine particles, fine particles such as silica fine particles, alumina fine particles, titania fine particles, and magnesium fluoride fine particles are preferable, and a colloidal solution of these inorganic fine particles is particularly preferable. This colloidal solution may be one in which inorganic fine particle powder is dispersed in a dispersion medium, or may be a commercially available colloidal solution.

In the present invention, by containing the inorganic fine particles, it is possible to impart the surface shape and other functions of the cured film to be formed. The average particle size of the inorganic fine particles is preferably 0.001 to 0.2 μm, more preferably 0.001 to 0.1 μm. When the average particle size of the inorganic fine particles exceeds 0.2 μm, the transparency of the cured film formed by using the prepared coating liquid may decrease.

Examples of the dispersion medium for the inorganic fine particles include water and an organic solvent. As the colloidal solution, it is preferable that the pH or pKa is adjusted to 1 to 10 from the viewpoint of the stability of the coating liquid for film formation. More preferably, it is 2 to 7.

Organic solvents used as the dispersion medium for the colloidal solution include methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, butanediol, pentanediol, 2-methyl-2,4-pentanediol, diethylene glycol, dipropylene glycol, and ethylene. Alcohols such as glycol monopropyl ether; ketones such as methyl ethyl ketone and methyl isobutyl ketone; aromatic hydrocarbons such as toluene and xylene; amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone; ethyl acetate and butyl acetate , Esters such as γ-butyrolactone; Esters such as tetrahydrofuran and 1,4-dioxane can be mentioned. Of these, alcohols and ketones are preferred. These organic solvents can be used alone or in admixture of two or more as a dispersion medium.

As the metalloxane oligomer or metalloxane polymer, single or composite oxide precursors such as silicon, titanium, zirconium, aluminum, tantalum, antimony, bismuth, tin, indium, and zinc are used. The metalloxane oligomer or metalloxane polymer may be a commercially available product or may be obtained from a monomer such as a metal alkoxide, a nitrate, a hydrochloride, or a carboxylate by a conventional method such as hydrolysis. ..

<Formation of anti-glare layer and anti-glare layer>
The antiglare layer of the present invention can be obtained by applying the above-mentioned coating liquid for forming an antiglare film to a base material and heat-curing it. That is, the antiglare layer is made of a cured product of polysiloxane having a fluorine-containing organic group contained in the coating liquid for forming an antiglare film.

Here, the antiglare layer has an uneven structure on the surface. The concavo-convex structure is a fine concavo-convex structure in which the height of the convex portion is 50 nm to 2,000 nm. The thickness of the entire antiglare layer is 50 nm to 3,000 nm, and the surface side of the antiglare layer has a fine uneven structure. That is, since the fine concavo-convex structure is formed on the uniform and flat film, it can be expressed that the convex portion is intermittently formed on the flat film. In this case, the portion where the convex portion is not formed becomes the concave portion. The convex portion surface coverage ratio, which is the occupancy ratio of the convex portion of the fine concavo-convex structure, is 5% to 70%, preferably 10% to 60%.

Specifically, the convex surface coverage can be measured by the following method. That is, the surface shape is measured using a white light interference type optical microscope (ContourGT, manufactured by BRUKER), and the shape is further analyzed. For surface shape measurement, a high-density CCD camera is used by the VSI measurement method, the zoom lens magnification is 0.55 times, the objective lens magnification is 50 times, the measurement area is 230 μm × 170 μm, the light source is a white light source, the amount of light and Threshhold are. Perform under appropriate conditions so that noise does not enter the measurement as much as possible. Further, as a shape analysis, the image is processed into a gray scale of 256 gradations after the filter processing is performed by TermsRemoval (CylinderandTilt). The measurement of the convex surface coverage was performed at an arbitrary position on the film surface, the processed image was divided into 1900, the brightness of the area was obtained, and the high-brightness region was made uniform by the convex portion and the low-brightness region. The region is defined as a flat portion, and the value calculated as convex portion / flat portion × 100 is defined as the convex portion surface coverage of the film surface. The environment at the time of measurement is 23 ° C. and 30 RH% below.

The antiglare layer preferably has a HAZE of 0.3% to 40%, more preferably 0.5% to 30%, from the viewpoint of obtaining an image display device having high visibility while suppressing glare. .. In the present specification and claims, HAZE can be measured using a haze meter (haze meter HZ-V3 manufactured by Suga Test Instruments Co., Ltd.) in accordance with JIS K7163.

The flat coating portion and the fine concavo-convex structure can be formed by a single application, but after the flat coating portion is formed, the fine concavo-convex structure can also be formed. Further, the coating liquid for forming an antiglare film forming a flat coating portion and the coating liquid for forming an antiglare film forming a fine concavo-convex structure may be the same coating liquid, but the two coating liquids may be different. .. For example, although the solid content compositions of both are the same, the solid content concentration of the coating liquid forming the fine concavo-convex structure may be higher than that of the flat coating portion, or the solid content compositions of both may be different. .. Furthermore, although the composition of the solid content of both is the same, the solvent composition of both may be different, but the composition is not limited thereto.

The fine uneven structure may be formed by, for example, applying a coating liquid for forming an antiglare film and then blowing wind on the surface before curing to form fine irregularities on the surface, or a flat coating portion may be formed. After the formation, a coating liquid having a slightly higher concentration may be spray-applied so that a convex portion is partially formed. At the time of spray coating, the flow rate of the coating liquid for forming an antiglare film and the gas flow rate described later are adjusted. By adjusting, fine irregularities may be formed, but the present invention is not limited to these.

The refractive index of the antiglare layer is selected from, for example, the range of 1.3 to 1.49 from the viewpoint of suppressing reflected light.

The application liquid for forming an antiglare film for forming an antiglare layer is, for example, a dip coating method, a flow coating method, a spin coating method, a flexo printing method, an inkjet coating method, a bar coating method, and a gravure roll coating method. , Roll coat method, Blade coat method, Air doctor coat method, Air knife coat method, Wire doctor coat method, Reverse coat method, Transfer roll coat method, Micro gravure coat method, Kiss coat method, Cast coat method, Slot orifice coat method, Although it can be applied to known or well-known methods such as a calendar coating method and a die coating method, the coating liquid for forming an antiglare film of the present invention is characterized in that it is particularly suitable for a spray coating method. ..

Examples of the base material include known or well-known base materials such as plastic, glass, and ceramics. Plastics include polycarbonate, poly (meth) acrylate, polyether sulphon, polyarylate, polyurethane, polysulfone, polyether, polyetherketone, trimethylpentene, polyolefin, polyethylene terephthalate, (meth) acrylonitrile, triacetyl cellulose, diacetyl cellulose. , Plates and films of acetate butyrate cellulose and the like.

The uniform film thickness as described above obtained by the spray coating method can be adjusted by adjusting the amount of chemical solution, nozzle / stage distance (distance between nozzle and stage), coating speed, gas flow rate, gas pressure, and the like.

The amount of chemical solution is a parameter that determines the film thickness. Increasing the amount of chemical solution increases the film thickness, and decreasing it decreases the film thickness. In spray application, the amount of the chemical solution is, for example, 0.5 to 20 mL (milliliter) / min, preferably 0.8 to 12 mL / min.

The gas flow rate is a parameter for forming fine droplets, and examples of the gas used include, but are not limited to _{, N 2 and dry air.} In spray coating, the gas flow rate is, for example, 3 to 70 L (liter) / min, preferably 6 to 60 L / min. In the case of gas pressure, it is 30 to 700 kPa, preferably 50 to 650 kPa.

The preferable flow rate of the gas from the viewpoint of forming fine irregularities is 150 to 140,000 times, preferably 500 to 75,000 times the flow rate of the gas in the air atmosphere with respect to the flow rate of the coating liquid for forming the antiglare film. It is preferable to apply the coating liquid for forming an antiglare film to the surface of the base material by ventilating the particles while making them finer.

Nozzle / stage distance is a parameter related to film thickness, coatability, and amount of protrusion on the surface. For example, the film thickness increases as the distance increases, but decreases as the distance increases. The preferred nozzle / stage distance is, for example, 30-200 mm, more preferably 50-150 mm.

The coating rate is a parameter related to the film thickness and the amount of the convex portion coated on the surface. For example, the film thickness becomes thinner as the rate increases, and increases as the rate decreases. In spray coating, the coating speed is, for example, 50 to 2000 mm / sec, preferably 100 to 1500 mm / sec.

The thickness of the coating film formed on the base material can be adjusted by the above-mentioned parameters at the time of coating, but can also be easily adjusted by _{the SiO 2 conversion concentration of the coating liquid.}

The coating film formed on the base material can be obtained by heating. Considering the heat resistance of the base material and the like, the firing temperature is preferably in the range of 80 ° C. to 300 ° C., and more preferably in the range of 100 ° C. to 250 ° C.

A high refractive index layer having a higher refractive index than the antiglare layer may be provided under the antiglare layer of the present invention. In this case, by appropriately adjusting the refractive indexes of the antiglare layer and the high refractive index layer, the reflected light reflected on the surface of the antiglare layer and the reflected light reflected on the surface of the high refractive index layer interfere with each other in opposite phases. The effect of reducing the reflected light can be further added.

Here, the high refractive index layer is not particularly limited as long as it is a layer having a higher refractive index than the antiglare layer, but in consideration of the adhesion to the antiglare layer, the coating liquid containing the metal alkoxide and the alkoxysilane is cured. It is preferably a product, and for example, the coating film disclosed in International Publication No. WO2012-057165 can be used.

The high refractive index layer disclosed in the above publication is coated with, for example, a coating liquid containing one or more of the metal alkoxide of the following formula (A), the alkoxysilane of the formula (B), and a condensate thereof. A cured film can be mentioned.

M ₁ (OR ¹ ) n (A)
(In the formula, M ₁ is silicon (Si), titanium (Ti), tantalum (Ta), zirconium (Zr), boron (B), aluminum (Al), magnesium (Mg), tin (Sn) and zinc (Zn). ), Etc., R ¹ represents an alkyl group having 1 to 5 carbon atoms, and n represents the valence _{of M 1.)}
(R ¹⁰² ) _n Si (OR ¹⁰³ ) _4-n (B)
(In the formula, R ¹⁰² contains an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, or a heteroatom containing a group having a heteroatom between carbons of the alkyl group, alkenyl group, cycloalkyl group and aryl group. Represents a group. However, some or all of the hydrogen atoms of the above alkyl group, alkenyl group, cycloalkyl group, aryl group and hetero atom-containing group may be substituted with a substituent, and the above alkyl group and alkenyl group may be substituted. , It may have a cycloalkyl group or an aryl group as a part thereof. R ¹⁰³ represents an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 1 or 2).

Examples of the group having a hetero atom include a group having at least one selected from the group consisting of an oxygen atom, a nitrogen atom and a sulfur atom, and -O-, -NR- (R is a hydrogen atom or (Representing an alkyl group having 1 to 6 carbon atoms), -CO-, -S-, -CO-, and a group combining these can be mentioned.

Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, cyano group, nitro group, hydroxy group, amino group, ureido group, isocyanate group, mercapto group and the like.

As a typical example of the metal alkoxide represented by the formula (A), when M ₁ is titanium, tetramethoxytitanium, tetraethoxytitanium, tetraisopropoxytitanium, tetran-propoxytitanium, tetran-butoxytitanium, Examples thereof include alkoxy titanium such as tetraisobutoxytitanium, tetrat-butoxytitanium, and tetrapentoxytitanium.
When M ₁ is silicon, alkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane can be mentioned.

^{Specific examples of R 102} in the formula (B) include alkyl groups having 1 to 18 carbon atoms such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group and stearyl group; Alkenyl groups such as vinyl groups; Cycloalkyl groups such as cyclohexyl groups; (meth) acrylicoxy group-containing alkyl groups such as 3- (meth) acrylicoxypropyl groups; 3-chloropropyl groups, trifluoropropyl groups, tridecafluoro Halogen atom-containing alkyl group such as octyl group and heptadecafluorodecyl group; hydroxy group-containing alkyl group such as 3-hydroxypropyl group; γ-ureido (3-ureido) propyl group and ureido group-containing alkyl group; γ-amino ( Amino group-containing alkyl groups such as 3-amino) propyl group, 2-aminoethylaminomethyl group, 3- (N-styrylmethyl-2-aminoethylamino) propyl group; γ-glycidoxy (3-glycidyloxy) propyl group , 2- (3,4-epoxycyclohexyl) ethyl group and other epoxy group-containing alkyl groups; γ-mercapto (3-mercapto) propyl group and other mercapto group-containing alkyl groups; 3-isocyanuppropyl group and other isocyanate group-containing alkyl Group: An aryl group such as a phenyl group can be mentioned.

Specific examples of the formula (B) include alkoxylans such as trialkoxysilane and dialkoxysilane.
Specific examples of the trialkoxysilane include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, and pentyl. Trimethoxysilane, pentyltrimethoxysilane, heptyltrimethoxysilane, heptiltilriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane , Octadecyltrimethoxysilane, octadecyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-aminoethylaminomethyltrimethoxysilane, γ-aminopropyltrimethoxysilane, 3 -(2-Aminoethylaminopropyl) trimethoxysilane, 3- (2-aminoethylaminopropyl) triethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxy Propyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, styrylethyltriethoxysilane, 3- (N-styrylmethyl-2-aminoethylamino) propyltrimethoxysilane, p-styryltrimethoxy Silane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ-ureidopropyltriethoxy. Silane, trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, tridecafluorooctyltrimethoxysilane, tridecafluorooctyltrimethoxysilane, heptadecafluorodecyltrimethoxysilane, heptadecafluorodecyltriethoxysilane, 3- Propyl isocyanate triethoxysilane can be mentioned.
Specific examples of the dialkoxysilane include dimethyldimethoxysilane and dimethyldiethoxysilane.

Specific examples of the above-mentioned condensate include methyl silicate 51, methyl silicate 53, ethyl silicate 40, ethyl silicate 48 (trade name, manufactured by Corcote), MKC silicate (trade name, manufactured by Mitsubishi Chemical Corporation), Toray Dow Corning Co., Ltd. Silicone resin manufactured by Momentive Performance Materials Japan, silicon resin manufactured by Shinetsu Chemical Industry Co., Ltd., hydroxyl group-containing polydimethylsiloxane manufactured by Dow Corning Asia, manufactured by Toray Dow Corning Co., Ltd. Silicon oligomers such as silicon oligomers; examples thereof include titanium oligomers such as titanium tetra-n-butoxide and tetramer (manufactured by Kanto Chemical Co., Ltd.).

The refractive index of the high refractive index layer is higher than that of the antiglare layer, and is the surface of the high refractive index layer which is the interface between the reflected light reflected on the surface of the antiglare layer and the antiglare layer and the high refractive index layer. The refractive index is preferably set so that the reflected reflected light has an opposite phase, and is selected from, for example, a range of 1.5 to 2.1, more preferably a range of 1.5 to 1.8.

The refractive index of the high refractive index layer may be adjusted by adjusting the curing temperature. In this case, it is preferable that the higher the curing temperature is, the higher the refractive index of the high refractive index layer is. From the viewpoint of considering the heat resistance of the base material and the like, the firing temperature is preferably in the range of 100 ° C. to 300 ° C., more preferably in the range of 150 ° C. to 250 ° C.

After the high refractive index layer is cured, the coating film may be further irradiated with ultraviolet rays (UV) to adjust the refractive index of the obtained high refractive index layer. In the high refractive index layer, ultraviolet irradiation for obtaining a desired refractive index can be performed using, for example, a high-pressure mercury lamp. Then, using a high-pressure mercury lamp, total light irradiation 1000 mJ / cm ² or more dose is preferably at 365nm ^terms, the dose of 2000mJ / cm 2 ~ 10000mJ / cm 2 is more preferable. Further, the UV light source is not particularly specified, and another UV light source may be used. When another light source is used, the same amount of integrated light as when the high-pressure mercury lamp is used may be irradiated.

Next, a functional layer obtained from a specific coating agent may be formed on the surface of the antiglare layer. In the present invention, since the antiglare layer is formed from the above-mentioned coating liquid, the coating property of the coating liquid forming the functional layer on the antiglare layer and the adhesion to the functional layer are good. ..

In the present invention, the functional layer provided on the antiglare layer is not particularly limited. Specific examples include functional layers obtained from antifouling agents, paints, adhesives, antireflection agents, water repellents, hydrophilic agents, oil repellents, lipophilic agents, hard coat agents, antislip agents and the like. it can.

The thickness of the antiglare layer and the functional layer is preferably 5 to 1000 nm, more preferably 10 to 400 nm.

The coating liquid for film formation of the present invention has excellent coatability and can form a film having high transmittance. In addition, it is also excellent in liquid landing efficiency when spray-applied. Therefore, it can be suitably used in fields such as televisions, computers, car navigation systems, and displays for mobile phones and the like.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.
The abbreviations used below are as follows.

TEOS: Tetraethoxysilane F13: Tridecafluorooctyltrimethoxysilane UPS: γ-ureidopropyltriethoxysilane TTE: Tetraethoxytitanium AN: Aluminum nitrate ninehydrate MeOH: Methanol EtOH: Ethanol IPA: Isopropanol PGME: Propylene glycol monomethyl Ether BCS: Butyl cellosolve PB: Propylene glycol Monobutyl ether PG: Propylene glycol HG: 2-Methyl-2,4-pentanediol NMP: N-methyl-2-pyrrolidone

<Synthesis example 1>
TEOS (31.6 g), F13 (6.2 g), and MeOH (30.3 g) were added to a 200 mL four-necked flask equipped with a reflux tube, and the mixture was stirred, and then MeOH (15.1 g) and water (15.1 g) and water ( 15.0 g) and oxalic acid (0.8 g) were added, and the mixture was stirred in an ice bath at 10 ° C. for 30 minutes. Then, the mixture was stirred at 65 ° C. for 2 hours, then UPS (0.5 g) and MeOH (0.5 g) were added, and the mixture was further reacted at 65 ° C. for 2 hours. Then, the mixture was allowed to cool to room temperature to obtain solution K1.

<Synthesis example 2>
AN (2.9 g), water (2.6 g) and EtOH (50.6 g) were added to a flask having a capacity of 200 mL and stirred to obtain an AN solution. TEOS (21.2 g) was added to the AN solution, and the mixture was stirred at room temperature for 30 minutes. Then, TTE (10.0 g) and EtOH (12.7 g) were added, and the mixture was further stirred at room temperature for 30 minutes to obtain a solution K2.

<Synthesis example 3>
AN (2.8 g), water (2.6 g) and EtOH (51.2 g) were added to a flask having a capacity of 200 mL and stirred to obtain an AN solution. TEOS (17.7 g) was added to the AN solution, and the mixture was stirred at room temperature for 30 minutes. Then, TTE (12.9 g) and EtOH (12.8 g) were added, and the mixture was further stirred at room temperature for 30 minutes to obtain a solution K3.

<Synthesis example 4>
AN (2.7 g), water (2.5 g) and EtOH (51.8 g) were added to a flask having a capacity of 200 mL and stirred to obtain an AN solution. TEOS (14.3 g) was added to the AN solution, and the mixture was stirred at room temperature for 30 minutes. Then, TTE (15.7 g) and EtOH (13.0 g) were added, and the mixture was further stirred at room temperature for 30 minutes to obtain a solution K4.

<Synthesis example 5>
TEOS (33.0 g) and MeOH (32.5 g) were added to a 200 mL four-necked flask equipped with a reflux tube, and the mixture was stirred, and there were MeOH (13.8 g), water (15.0 g) and oxalic acid (0). 0.9 g) was added, and the mixture was stirred in an ice bath at 10 ° C. for 30 minutes. Then, the mixture was stirred at 60 ° C. for 2 hours, then UPS (2.4 g) and MeOH (2.4 g) were added, and the mixture was further reacted at 60 ° C. for 30 minutes. Then, the mixture was allowed to cool to room temperature to obtain solution K5.

<Preparation Example 1>
PGME (20 g) and EtOH (20 g) were added to K1 and K5 solutions (60 g) to obtain solutions KL1-1 and KM2-1, respectively.

<Preparation Example 2>
PG (5 g), NMP (20 g) and MeOH (63 g) were added to K1 solution (12 g) to obtain solution KL1-2.

<Preparation Example 3>
EtOH (2.5 g), IPA (42 g), BCS (9.4 g), PB (9.4 g) and HG (18.7 g) are added to the K2-K4 solution (18 g), and the solutions KL2-KL4 are added, respectively. Obtained.

<Preparation Example 4>
PGME (20 g) and EtOH (40 g) were added to the K1 solution (40 g) to obtain a solution KM1.

<Preparation Example 5>
MeOH (1.8 g), EtOH (18.5 g), PGME (18.5 g), PB (27.7 g) and HG (18.5 g) were added to K5 solution (15 g) to obtain solution KM2-2. It was.

[Spray application conditions]
Spray coating was performed with the equipment and conditions shown below.
Device name: Spray coater API-240-3D manufactured by Apirosu Co., Ltd.

<Applying condition I-1>
Nozzle model: LPVN45, nozzle height: 100 mm, Y-axis pitch: 2 mm, Air pressure: 550 kPa, chemical flow rate 1.0 mL / min, nozzle speed: 900 mm / sec

<Applying condition I-2>
The coating condition I-1 was changed to a Y-axis pitch: 3 mm, and the other conditions were the same.

<Applying condition I-3>
The coating condition I-1 was changed to a Y-axis pitch: 5 mm, and the other conditions were the same.

<Applying condition I-4>
The coating condition I-1 was changed to a Y-axis pitch: 1.4 mm, and the other conditions were the same.

<Applying condition II-1>
Nozzle model: LPVN12, nozzle height: 100 mm, Y-axis pitch: 7 mm, Air pressure: 560 kPa, chemical flow rate 4.9 mL / min, nozzle speed: 500 mm / sec

<Applying condition II-2>
The coating condition II-1 was changed to a nozzle speed of 550 mm / sec, and the other conditions were the same.

<Application condition III>
Nozzle model: LPVN45, nozzle height: 100 mm, Y-axis pitch: 7 mm, Air pressure: 470 kPa, chemical flow rate 4.9 mL / min, nozzle speed: 170 mm / sec

<Application condition IV>
Nozzle model: LPVN45, nozzle height: 100 mm, Y-axis pitch: 7 mm, Air pressure: 365 kPa, chemical flow rate 4.9 mL / min, nozzle speed: 500 mm / sec

<Applying condition V>
Nozzle model: LPVN45, nozzle height: 50 mm, Y-axis pitch: 3 mm, Air pressure: 550 kPa, chemical flow rate 1.0 mL / min, nozzle speed: 700 mm / sec

[Baking conditions]
<Baking condition A>
It was dried on a hot plate at a temperature of 70 ° C. for 5 minutes and baked in a hot air circulation oven at 160 ° C. for 30 minutes.

<Baking condition B>
It was dried in a hot air circulation oven at a temperature of 130 ° C. for 3 minutes, UV-irradiated at 3000 mJ / cm ² (365 nm conversion, high-pressure mercury lamp), and baked in a hot air circulation oven at 160 ° C. for 30 minutes.

<Baking condition C>
It was dried on a hot plate at a temperature of 40 ° C. for 5 minutes and baked in a hot air circulation oven at 160 ° C. for 30 minutes.

<Various evaluation conditions>
[HAZE]
Soda lime glass was used as a substrate, and a film was formed by spray coating under the same coating conditions as in Examples and Comparative Examples. HAZE was measured on the obtained coated substrate with a haze meter HZ-V3 manufactured by Suga Test Instruments Co., Ltd.

[Surface observation]
Using soda lime glass as the substrate, the prepared substrate with a coating was observed with a three-dimensional white interference microscope Contour GT manufactured by Bruker Japan Co., Ltd.

[Convex surface coverage]
From the image acquired by surface observation, the area ratio of the convex portion and the flat portion in an arbitrary measurement point was calculated from the brightness component of the image analysis, and the convex portion surface coverage was calculated. The convex surface coverage was calculated by the same method as the method for calculating the convex surface coverage described above.

[Reflectance]
<Specular reflection, reflection color>
Using soda lime glass as the substrate, the coated substrate was measured with a UV-3600 ultraviolet-visible near-infrared spectrophotometer manufactured by Shimadzu Corporation in the wavelength range of 380 nm to 800 nm at an incident angle of 5 °. From the obtained spectral reflectance curve, the average visual reflectance (normal reflection) and the reflection colors a ^* and b ^* were obtained according to JIS R 3106.

<SCI, SCE>
Using soda lime glass as the substrate, the coated substrate was measured with a spectrophotometer CM-3700A manufactured by Konica Minolta Co., Ltd. to determine the reflectance in the wavelength range of 360 nm to 740 nm at an incident angle of 8 °. The measurement was performed, and the average visual reflectance of SCI and SCE was determined according to JIS Z 8722. In addition, SCI (Special Component Industry) is a measurement in which specular reflected light is taken into consideration, and SCE (Specular Component Exclude) is a measurement in which specular reflected light is not taken into consideration.

[Sparkling]
On a liquid crystal display with a pixel density of 350 ppi, yellow-green is displayed on the front and the brightness is maximized, and a substrate with a coating is placed directly on the screen. Those that did not occur were evaluated as 〇.

[Refractive index]
Using a silicon substrate (100) as a substrate, solutions KL2 to KL2 to 4 are formed by spin coating so that the film thickness after firing is 100 nm, and the substrate is fired under the above firing condition B to obtain a coated substrate. The refractive index at a wavelength of 633 nm was measured with an ellipsometer (DVA-FLVW, manufactured by Mizojiri Optical Co., Ltd.).

<Example 1>
Using soda lime glass as a substrate, the solution KL1-2 obtained in Preparation Example 2 was spray-coated under coating condition III and then fired under firing condition A to form a lower layer. The solution KL1-1 obtained in Preparation Example 1 was spray-coated on the obtained substrate under coating condition I-1, and then fired under firing condition C to obtain a coated substrate.
Various evaluations were performed using the obtained coated substrate. The evaluation results are shown in Table 1-2.

<Examples 2 to 3, Comparative Examples 1 to 4>
A substrate with a coating was obtained in the same manner as in Example 1 except that the solution to be used and each condition were changed as shown in Table 1-1 below. In Comparative Example 2 and Comparative Example 4, the lower layer was formed to form a coated substrate.
Various evaluations were performed using the obtained coated substrate. The evaluation results are shown in Table 1-2.

As shown in Table 1-2, in Examples 1 to 3, the specular reflection and the SCI value were suppressed to be low, and sparkling did not occur. Further, as compared with Comparative Example 2, since SCE, which is a light scattering component of the reflectance, is generated, the antiglare function can be exhibited, and from the above, the antiglare property to which the antireflection function is imparted. It is suggested that the functional membrane has been constructed.

In Comparative Example 1, the SCI value is very large and sparkling also occurs.

Comparative Example 3 is a case where a solution without a fluoroalkyl component is used, and a shape having a low convex surface coverage cannot be obtained, and the SCI value is high. Further, in Comparative Example 4, although there is no antiglare property, the reflected color is small. However, both SCI and specular reflection become high.

<Examples 4 to 6, Comparative Examples 5 to 7>
A substrate with a coating was obtained in the same manner as in Example 1 except that the solution to be used and each condition were changed as shown in Table 2-1 below.
Various evaluations were performed using the obtained coated substrate. The evaluation results are shown in Table 2-2.

As shown in Table 2-2, in Examples 4 to 6, the SCI value could be suppressed to a low level, and sparkling did not occur. Further, as compared with Comparative Examples 5 to 7, the absolute value of the reflected color value can be reduced and SCE is generated, so that the antiglare function can be exhibited. It is suggested that a functional antiglare film can be formed.

A laminate that can be formed on a glass substrate and has excellent antireflection and antiglare properties (anti-glare function) by using the coating liquid for forming a glare film of the present invention and a film composition using the same. It will be possible to provide. This can contribute to improving the display quality of image display devices (liquid crystal displays, organic EL displays, plasma displays, etc.) provided in various devices such as televisions, personal computers, and smartphones.

Claims (17)

1. It has a base material and an antiglare layer formed directly on the base material or via another layer and having an uneven structure on the surface, and the antiglare layer contains a polysiloxane having a fluorine-containing organic group. A base material with an antiglare layer, which is formed from a cured product of a composition for forming an antiglare film and has a convex surface coverage of 5% to 70%.
2. The base material with an antiglare layer according to claim 1, wherein the polysiloxane having a fluorine-containing organic group contains an organic group represented by the following formula (F).
   CF ₃ (CF ₂ ) _k CH ₂ CH _2- * (F)
   (In the formula, k is an integer from 0 to 12. * Indicates the connection position.)
3. The base material with an antiglare layer according to claim 1 or 2, wherein the polysiloxane is obtained by polycondensing an alkoxysilane component containing an alkoxysilane compound represented by the following formula (1).
   R ¹¹ Si (OR ¹² ) ₃ (1)
   (R ¹¹ represents an organic group substituted with the fluorine atom, and R ¹² represents a hydrocarbon group having 1 to 5 carbon atoms.)
4. The polysiloxane is further polycondensed with an alkoxysilane component containing at least one selected from the group consisting of an alkoxysilane compound represented by the following formula (2) and an alkoxysilane compound represented by the following formula (3). The base material with an antiglare layer according to claim 3.
   Si (OR ² ) ₄ (2)
   R ³¹ _n Si (OR ³² ) _4-n (3)
   (In the formula, R ² represents a hydrocarbon group, R ³¹ represents an organic group or a hydrogen atom not substituted with a fluorine atom, R ³² represents a hydrocarbon group having 1 to 5 carbon atoms, and n represents 1 to 1 to 5. It is an integer of 3.)
5. The organic group not substituted with a fluorine atom is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a cycloalkyl group, a (meth) acrylicoxy group-containing alkyl group, a hydroxy group-containing alkyl group, and the like. The base material with an antiglare layer according to claim 4, which is selected from a ureido group-containing alkyl group, an amino group-containing alkyl group, an epoxy group-containing alkyl group, a mercapto group-containing alkyl group, an isocyanate group-containing alkyl group or an aryl group.
6. The base material with an antiglare layer according to claim 4 or 5, wherein the alkoxysilane compound represented by the formula (2) is tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, or tetrabutoxysilane.
7. The alkoxysilane compound represented by the formula (3) is methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyl. Triethoxysilane, pentyltrimethoxysilane, penttiltriethoxysilane, heptyltrimethoxysilane, heptiltilriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, hexadecyltrimethoxysilane, Hexadecyltriethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-isocyanoxidetrimethoxysilane, 3-isocyanoxidetriethoxysilane Silane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyl Triethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-ureidopropyltrimethoxysilane or γ- The base material with an antiglare layer according to any one of claims 4 to 6, which is ureidopropyltriethoxysilane.
8. The composition for forming an antiglare film includes ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate and the like. The base material with an antiglare layer according to claims 1 to 7, which contains at least one selected from methyl isobutyl ketone.
9. The antiglare according to claims 1 to 8, wherein the antiglare film forming composition contains at least one selected from methanol, ethanol, 2-propanol, 2-butanol and 2-methyl-1-propanol. Layered substrate.
10. The base material with an antiglare layer according to any one of claims 1 to 9, wherein the height of the convex portion of the uneven structure is 50 nm to 2,000 nm.
11. The base material with an antiglare layer according to any one of claims 1 to 10, wherein the HAZE of the antiglare layer is 0.3% to 40%.
12. The base material with an antiglare layer according to any one of claims 1 to 11, wherein the refractive index of the antiglare layer is in the range of 1.3 to 1.49.
13. The antiglare layer is formed on the high refractive index layer, and the refractive index of the high refractive index layer is higher than the refractive index of the antiglare layer. The base material with an anti-glare layer according to any one of 12 to 12.
14. The base material with an antiglare layer according to claim 13, wherein the refractive index of the high refractive index layer is in the range of 1.5 to 2.1.
15. The base material with an antiglare layer according to any one of claims 1 to 14, further comprising a functional layer formed on the antiglare layer.
16. An image display device comprising the base material with an antiglare layer according to any one of claims 1 to 15.
17. A method for producing a base material with an antiglare layer, which comprises a step of applying a coating liquid for forming an antiglare film containing a polysiloxane having a fluorine-containing organic group onto the base material to form an antiglare layer.