JP2020118992A - Substrate with antiglare film - Google Patents

Abstract

To provide a substrate with an antiglare film, which has excellent antiglare property and reduced haze such that, for example, when a black printed layer is seen through the substrate with the antiglare film, cloudiness is less likely to be visible on the black printed layer, a liquid composition for forming an antiglare film for forming the above antiglare film, and a method for manufacturing a substrate with an antiglare film.SOLUTION: A substrate 1 with an antiglare film has a transparent substrate 2 and an antiglare film 3 disposed on the transparent substrate 2. The antiglare film 3 essentially comprises silica, a surface roughness curve skewness Rsk of the antiglare film 3 is 1.3 or less, a surface roughness curve element average length RSm of the antiglare film 3 is 10 μm or more and 20.2 μm or less, and an arithmetic average roughness Ra is 0.01 μm or more.SELECTED DRAWING: Figure 1

Description

The present invention relates to a substrate with an antiglare film, a liquid composition for forming an antiglare film, and a method for producing a substrate with an antiglare film.

In various devices (for example, televisions, personal computers, smartphones, mobile phones, image display devices (for example, liquid crystal displays, organic EL displays, plasma displays, etc.) provided in vehicles) indoor lighting such as fluorescent lamps and the sun When external light such as light is reflected on the display surface, the visibility is reduced due to the reflected image.

As a method of suppressing the reflection of external light, there is a method of disposing an antiglare film on the display surface side of the image display device. The antiglare film has unevenness on the surface and diffuses and reflects external light to make a reflected image unclear. Such an antiglare film is, for example, a coating liquid containing a hydrolyzable organosilicon compound such as a hydrolyzed condensate of an alkoxysilane as a silica precursor, is applied to a substrate surface by a spray method, and then baked. Are formed (see, for example, Patent Document 1).

There is also a method in which a low-reflection film is arranged on the display surface of the image display device to suppress reflection of incident light on the transparent substrate itself to make the reflected image unclear. As the low-reflection film, a single-layer film made of a low-refractive index material and a multilayer film made by combining a layer made of a low-refractive index material and a layer made of a high-refractive index material are known. A film formed of a fluorine-containing hydrolyzable organosilicon compound is also known as a low-reflection film (see, for example, Patent Documents 2 to 5).

International Publication No. 2016/021560 JP-A-64-1527 JP, 2003-344608, A JP-A-2002-79616 International Publication No. 2005/121265

By disposing the antiglare film on the display surface of the image display device, it is possible to suppress deterioration of the visibility of the image due to external light reflected on the display surface. However, at the same time, the higher the antiglare property of the antiglare film, the higher the haze is likely to be.

On the front plate of the image display device, an anti-glare film is formed on the viewing side, and black printing is performed on the peripheral part of the surface on the non-viewing side where the anti-glare film is not provided for the purpose of improving design and aesthetics. Providing light shields such as layers has been practiced. At this time, if the haze of the antiglare film is high, white turbidity may be visually recognized when looking at the black print layer through the antiglare film, and there is a problem of impairing aesthetics.

The present invention provides an antiglare film-coated substrate having excellent antiglare properties and reduced haze, a liquid composition for forming an antiglare film and a method for producing an antiglare film-coated substrate. The purpose is to provide.

The present invention has the following aspects.

(1) A transparent substrate and an antiglare film provided on the transparent substrate. The antiglare film contains silica as a main component and has a skewness Rsk of the roughness curve of the surface of the antiglare film of 1.3. The average length RSm of the elements of the roughness curve of the surface of the antiglare film is 10 μm or more and 20.2 μm or less, and the arithmetic average roughness Ra is 0.01 μm or more. Substrate with dazzle.

The following definitions of terms apply throughout the present specification and claims.
The “silica precursor” means a substance capable of forming a matrix containing silica as a main component as a component involved in network bonding.
The term "having silica as a main component" means containing SiO ₂ in an amount of 50% by mass or more.
The “hydrolyzable group bonded to a silicon atom” means a group that can be converted into an OH group bonded to a silicon atom by hydrolysis.
The "scaly particle" means a particle having a flat shape. The shape of the particles can be confirmed using a transmission electron microscope (hereinafter, also referred to as TEM).
The "average particle diameter" of the scaly particles is the particle diameter at a point at which the total volume of the particle size (longest length) distribution obtained on a volume basis is 100%, which is 50%, that is, the volume-based cumulative 50 It means% diameter (D50). The particle size distribution is determined by the frequency distribution and cumulative volume distribution curve measured by a laser diffraction/scattering particle size distribution measuring device.
“Aspect ratio” means the ratio of particle diameter to particle thickness (longest length/thickness), and “average aspect ratio” means the average value of the aspect ratios of 50 randomly selected particles. Is. The particle thickness is measured by an atomic force microscope (hereinafter, also referred to as AFM), and the maximum length is measured by TEM.

According to the present invention, a substrate with an antiglare film having excellent antiglare properties and reduced haze can be obtained.
According to the present invention, it is possible to provide a liquid composition for forming an antiglare film and a method for producing a substrate with an antiglare film for obtaining a base with an antiglare film having excellent antiglare properties and reduced haze.

It is a cross-sectional schematic diagram showing the base body with an anti-glare film which concerns on 1st Embodiment. It is a cross-sectional schematic diagram showing the base|substrate with an anti-glare film which concerns on 2nd Embodiment. It is a bottom schematic diagram of the base|substrate with an anti-glare film of FIG.

Hereinafter, embodiments will be described in detail with reference to the drawings.
(First embodiment)
FIG. 1 is a schematic sectional view showing a substrate with an antiglare film according to an embodiment of the present invention. The substrate 1 with an antiglare film shown in FIG. 1 has a transparent substrate 2 and an antiglare film 3 provided on the transparent substrate 2.

In the substrate 1 with an antiglare film, the antiglare film 3 contains silica as a main component and contains a CF ₃ (CH ₂ ) _n -group (where n is an integer of 1 to 6; the same applies below). The skewness Rsk of the roughness curve of the surface of the antiglare film 3 is 1.3 or less, and the arithmetic average roughness Ra is 0.01 μm or more. Since the antiglare film 3 has the above-mentioned characteristics, the antiglare film base 1 has excellent antiglare properties and has a low haze, and for example, the black printed layer is seen through the antiglare film base 1. At that time, it is possible to prevent the white turbidity from being visually recognized. Hereinafter, each configuration of the substrate 1 with the antiglare film will be described.

(Transparent substrate 2)
The transparent substrate 2 is not particularly limited as long as it is made of a transparent material that is required to have antiglare properties imparted by the antiglare film, and examples thereof include glass, resin, or a combination thereof (composite material, laminated material). Etc.) are preferably used. 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.

Also, the form of the transparent substrate 2 is not particularly limited, and may be, for example, a plate having rigidity, a film having flexibility, or the like.

The surface of the transparent substrate 2 on which the antiglare film 3 is formed (hereinafter also referred to as “main surface”) may be smooth or may have irregularities. In terms of usefulness of providing the antiglare film 3 (where desired optical characteristics can be obtained), smoothness is preferable. The antiglare film 3 provided on the transparent substrate 2 may not be formed over the entire main surface of the transparent substrate 2. That is, the antiglare film 3 may be formed in a predetermined area on the main surface of the transparent substrate 2 to which antiglare property is imparted, and may not be formed in other areas.

The shape of the transparent substrate 2 is not limited to the flat shape shown in the figure, but may be a shape having a curved surface. In this case, the whole may be configured by a curved surface, or may be configured by a curved surface portion and a flat portion. Recently, in various devices (TVs, personal computers, smartphones, car navigation systems, etc.) equipped with an image display device, a display surface of the image display device has become a curved surface. The antiglare film-coated substrate 1 in which the transparent substrate 2 has a curved surface is useful for such an image display device.

The transparent substrate 2 is preferably a glass substrate. The method for manufacturing the glass substrate is not particularly limited. The glass substrate can be manufactured by charging a desired glass raw material into a melting furnace, heating and melting the mixture to clarify it, and then supplying it to a molding apparatus to mold the molten glass and gradually cooling it. The method for molding the glass substrate is not particularly limited, and for example, a glass substrate molded by the float method, the fusion method, the downdraw method or the like can be used.

The thickness of the transparent substrate 2 can be appropriately selected according to the application, and when a glass substrate is used as the transparent substrate 2, the thickness thereof is preferably 0.1 to 5 mm, more preferably 0.2 to 2.5 mm.

When a glass substrate is used as the transparent substrate 2, a glass substrate having the main surface of the glass substrate subjected to a strengthening treatment is preferable. The strength of the glass is improved by the strengthening treatment, and for example, the thickness can be reduced while maintaining the strength. An antiglare film may be formed on the unstrengthened glass substrate, and then tempered.

Examples of the strengthening treatment include a treatment of forming a compressive stress layer on the surface of the glass plate by an air cooling strengthening method (physical strengthening method) or a chemical strengthening method. The compressive stress layer on the surface of the glass substrate improves the strength of the glass substrate against scratches and impacts. Of these, the chemical strengthening method is preferable because the glass substrate can be sufficiently strengthened even when the thickness of the glass substrate becomes thin (for example, less than 2 mm).

In the chemical strengthening method, a glass plate is immersed in a molten salt at a temperature equal to or lower than the strain point temperature of the glass to exchange ions (eg sodium ions) on the surface of the glass plate with ions having a larger ionic radius (eg potassium ions). To do. As a result, compressive stress is generated in the surface layer of the glass plate.

The chemically strengthened glass substrate (chemically strengthened glass substrate) has, for example, a surface compressive stress (CS) of 450 MPa to 1200 MPa and a stress layer depth (DOL) of 10 μm to 50 μm.

The substrate 1 with an antiglare film may have a functional layer such as an undercoat layer, an adhesion improving layer, and a protective layer between the transparent substrate 2 and the antiglare film 3. The undercoat layer has 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 a composition for forming an undercoat containing a hydrolyzate of alkoxysilane (sol-gel silica) onto the transparent substrate 2.

(Anti-glare film)
The antiglare film 3 has a concave-convex structure on the surface, diffusely reflects the external light with which the transparent substrate 2 is irradiated, and suppresses the surface reflection of the external light. For example, in various image display devices such as a liquid crystal display (LCD) and a plasma display (PDP), generally, when external light such as indoor lighting (fluorescent lamp, etc.) and sunlight is reflected on the display surface, it is visually recognized as a reflected image. Sex decreases. On the other hand, by providing the anti-glare film 3 on the transparent substrate 2 and diffusing external light, it is possible to suppress deterioration of visibility due to a reflected image.

The antiglare film 3 contains silica as a main component and contains a CF ₃ (CH ₂ ) _n − group. The skewness Rsk of the roughness curve on the surface of the antiglare film 3 is 1.3 or less, and the arithmetic average roughness Ra is 0.01 μm or more.

The antiglare film 3 contains, for example, a silica precursor (fluorine-containing silica precursor) (A) containing a CF ₃ (CH ₂ ) _n -group, scaly particles (B), and a liquid medium (C). It is formed using a liquid composition for forming an antiglare film containing the composition. In this case, the fluorine-containing silica precursor (A) contains silica as a main component and forms a matrix containing CF ₃ (CH ₂ ) _n − groups. Then, the scale-like particles (C) are dispersed in this matrix to form the antiglare film 3. A method for forming the antiglare film 3 using such a liquid composition for forming an antiglare film will be described in detail later.

Since the CF ₃ (CH ₂ ) _n -group contained in the antiglare film 3 has a fluorine atom, it is difficult to burn when heated. Therefore, it is possible to prevent the antiglare film 3 obtained by firing the liquid composition for forming an antiglare film from becoming porous. Further, the antiglare film 3 exhibits excellent chemical resistance and moisture resistance by containing a CF ₃ (CH ₂ ) _n -group having a fluorine atom inside the film.

The CF ₃ (CH ₂ ) _n − group in the antiglare film 3 was scraped off the antiglare film 3 from the transparent substrate 2, and a powder sample prepared using the shaved antiglare film 3 was subjected to nuclear magnetic resonance spectroscopy (NMR). ), by infrared spectroscopy (IR) and the like. When an antifouling film described later is formed on the surface of the antiglare film 3, the above analysis can be performed after removing the antifouling film. The antifouling film can be removed by corona treatment or plasma treatment. If the contact angle of water on the surface after removing the antifouling film is about 20° or less, it can be determined that the antifouling film has been removed.

The arithmetic average roughness Ra of the surface of the antiglare film 3 is 0.01 μm or more. The arithmetic average roughness Ra is a value obtained by averaging the absolute value deviations from the reference surface in the roughness curve included in the reference length taken on the reference surface. When the arithmetic average roughness Ra is 0.01 μm or more, the antiglare film 3 exhibits excellent antiglare properties. The arithmetic average roughness Ra of the antiglare film 3 is preferably 0.1 μm or less. The arithmetic average roughness Ra of 0.1 μm or less is one factor for making it possible to achieve both excellent antiglare properties and low haze by the antiglare film 3 without the haze becoming too high.

The skewness Rsk of the roughness curve of the surface of the antiglare film 3 is 1.3 or less. Here, the skewness Rsk of the roughness curve represents the cubic mean of the heights Z(x) in the reference length made dimensionless by the cube of the root mean square height (Zq), with respect to the mean line of the uneven shape. It is an index showing the bias. When the value of the skewness Rsk of the roughness curve is positive (Rsk>0), the uneven shape is biased to the concave side and the projection shape is sharp, and when the value is negative (Rsk<0), the uneven shape is biased to the convex side. The protruding shape tends to be dull. Haze is lower when the protrusion shape of the roughness curve is dull than when it is sharp.

The skewness Rsk of the roughness curve of the surface of the antiglare film 3 is 1.3 or less, which is one factor for maintaining excellent antiglare property and reducing the haze. In addition, it is possible to prevent white turbidity from being visually recognized when the black printed portion is viewed through the antiglare film-attached substrate 1. The skewness Rsk of the roughness curve of the surface of the antiglare film 3 is more preferably 1.05 or less in order to maintain excellent antiglare property and lower the haze.

The average length RSm of the element of the surface roughness curve of the antiglare film 3 is preferably 18 μm or less, more preferably 17.8 μm or less, and further preferably 17.5 μm or less. Further, RSm is preferably 10 μm or more, more preferably 11 μm or more, still more preferably 14 μm or more. This is because if the average length RSm of the elements of the roughness curve is too large, the haze and glaring index value (Sparkle) of the substrate 1 with an antiglare film are likely to be large, and if it is too small, the antiglare property is likely to be deteriorated.

The arithmetic average roughness Ra, the skewness Rsk of the roughness curve and the average length RSm of the elements of the roughness curve on the surface of the antiglare film 3 are the same as those of the liquid composition for forming the antiglare film 3 when the antiglare film 3 is formed. Composition (solid content concentration, primary particle diameter of scaly particles, secondary particle diameter, content of each component, etc.), coating conditions of the liquid composition for forming an antiglare film on the transparent substrate 2 (for example, coating by a spray method) In that case, it can be adjusted by the spray pressure, the liquid amount, the temperature of the transparent substrate, the number of times of coating, etc.) of the liquid composition for forming an antiglare film.

The arithmetic mean roughness Ra of the surface of the antiglare film 3, the skewness Rsk of the roughness curve, and the average length RSm of the elements of the roughness curve are specified in JIS B0601-2001 using SURFCOM1500SD3-12 manufactured by Tokyo Seimitsu Co., Ltd. It can be measured according to the method.

The antiglare film 3 preferably has an average film thickness of 15 to 1500 nm. When the average film thickness of the antiglare film 3 is 15 to 50 nm, it is easy to lower the haze and lower the glare index value. It is more preferable that the average film thickness of the antiglare film 3 is 50 nm or more, since sufficient antiglare properties can be imparted to the substrate 1 with the antiglare film. The average film thickness of the antiglare film 3 of 1500 nm or less is one factor for making the optical properties such as the antiglare index value and haze within a good range. Here, the average film thickness of the antiglare film 3 is obtained by observing a cross section of the antiglare film 3 with a scanning ion microscope (SEM) after processing the cross section of the antiglare film 3 at a magnification of, for example, 10,000 times and taking a photograph. It can be measured by measuring the thickness from the interface between the transparent substrate 2 and the antiglare film 3 to the surface of the antiglare film 3 over the entire range. The film thickness can be calculated using digital data obtained by SEM imaging and image processing software.

The antiglare film 3 may be formed so as to cover the entire main surface of the transparent substrate 2 (or a region on the main surface to which antiglare property is provided) without a gap, and for example, a preferable antiglare index described later. As long as the value and haze can be obtained, a part of the main surface (or the above-mentioned region) of the transparent substrate 2 is exposed without the antiglare film being formed, for example, the antiglare film 3 is formed in an island shape. May be. When the thickness of the antiglare film 3 is, for example, 300 nm or less, the antiglare film 3 is discontinuously formed on the main surface of the transparent substrate 2, and the antiglare film is formed on a part of the main surface of the transparent substrate 2. However, the transparent substrate 2 may be exposed.

The antiglare film 3 may be composed of a first convex portion having a diameter of 1 μm or more and a second convex portion having a diameter of less than 1 μm, and the first convex portions or the second convex portions, Alternatively, the first protrusion and the second protrusion may overlap. Such a surface structure can be observed by analyzing laser microscope measurement data with image processing software.

The film thickness of the antiglare film 3 is the coating conditions of the liquid composition for forming the antiglare film on the transparent substrate 2 (for example, when applying by a spray method, the liquid amount and the application of the liquid composition for forming the antiglare film). The number of times) and the composition of the liquid composition for forming an antiglare film (solid content concentration, content of each component, etc.) and the like.

Regarding the fluorine content in the antiglare film 3, the standard sample is glass having a specific gravity of 2.48 containing 1.0% by mass of fluorine (F), and the measured fluorine value of the antiglare film 3 is divided by the measured fluorine value of the standard sample. The fluorine content is preferably 2.5 or less, more preferably 2.2 or less, still more preferably 1.8% or less. This is to suppress an increase in RSm. The amount of F is preferably 0.23 or more, more preferably 0.3 or more, still more preferably 0.4 or more. This is due to temperature and humidity durability. The F amount can be measured, for example, by the following method. Using Rigaku ZSX100e, measurement diameter 30 mm, measurement line F-Kα, filter OUT, slit Std. , Analysis crystal RX35, detector PC, PHA100-300, peak angle 38.794 deg. (20 sec), B.I. G. Angle 43.000 deg. Under the condition of (10 sec), the fluorine content (mass %) of the film to be measured and the fluorine content in the standard sample are measured. The F content is calculated by dividing the measured fluorine content of the film to be measured by the measured fluorine content of the standard sample.

When an antifouling film described later is formed on the surface of the antiglare film 3, the F amount in the antiglare film 3 is measured after removing the antifouling film. The antifouling film can be removed by corona treatment or plasma treatment. If the contact angle of water on the surface after removing the antifouling film is about 20° or less, it can be determined that the antifouling film can be removed.

The amount of F in the antiglare film 3 is the composition of the liquid composition for forming an antiglare film, the amount of CF ₃ (CH ₂ ) _n − groups in the liquid composition for forming an antiglare film, the fluorine-containing silica precursor ( It can be adjusted by the type of A), the amount of CF ₃ (CH ₂ ) _n -groups contained in the fluorine-containing silica precursor (A), and the like.

The haze of the substrate 1 with an antiglare film is preferably 8 or less, more preferably 6.8 or less. When the haze is 8 or less, when the substrate 1 with an antiglare film has a black printed portion on the surface opposite to the antiglare film 3, white turbidity is suppressed from being visually recognized in the black printed portion, and the antiglare film has an excellent appearance. The attached substrate 1 can be obtained.

Regarding the surface gloss of the substrate 1 with an antiglare film, the 60° specular gloss (%) (Gloss) is preferably 135% or less, more preferably 130% or less, and further preferably 120% or less. The 60° specular gloss (%) (Gloss) is preferably 50% or more, more preferably 60% or more, still more preferably 70% or more. Here, the 60° specular gloss of the substrate 1 with an antiglare film is, for example, a method defined in JIS Z8741: 1997 as the 60° specular gloss, which is an all-in-one gloss meter (manufactured by Low Point Instruments Co., Rhopeint IQ). ), a black felt is laid on the back surface side to turn off the back surface reflection of the antiglare film-attached substrate 1, and the value is measured at a substantially central portion of the plane of the antiglare film 3.

The antiglare index value (Diffusion) of the surface of the substrate 1 with an antiglare film is preferably 0.05 or more, more preferably 0.1 or more, and further preferably 0.2 or more. When the index value of the antiglare property on the surface of the antiglare film-attached substrate 1 is 0.05 or more, excellent antiglare property is exhibited when used in an image display device.

The measurement of the antiglare index value on the surface of the antiglare film-attached substrate 1 can be carried out by the following procedure using a goniophotometer GC5000L manufactured by Nippon Denshoku Industries Co., Ltd. First, the direction parallel to the thickness direction of the substrate 1 with the antiglare film is set at an angle of 0°. At this time, on the main surface side of the antiglare film-coated substrate 1, from the direction of the angle θ=−45°±0.5° (hereinafter, also referred to as “angle −45° direction”), the antiglare film provided substrate 1 The first surface is irradiated with the first light. The first light is reflected by the main surface of the base body 1 with the antiglare film. The brightness of the 45° reflected light reflected in the direction of an angle of 45° from the main surface of the anti-glare film-coated substrate 1 is measured to be “brightness of 45° reflected light”.

Next, the angle θ for measuring the brightness of the light reflected by the main surface of the antiglare film-coated substrate 1 was changed in the range of 5° to 85°, and the same operation was carried out to obtain the antiglare film-coated substrate 1 The luminance distribution of the reflected light in the range of 5° to 85° reflected by the main surface is measured and summed to obtain the “luminance of the total reflected light”.

Next, the antiglare index value (Diffusion) is calculated from the following equation (1).

Anti-glare index value =
{(Luminance of totally reflected light-luminance of 45° reflected light)/(luminance of totally reflected light)} Formula (1)

It has been confirmed that the anti-glare index value correlates with the judgment result of the anti-glare property by the observer's visual observation, and exhibits a behavior close to the human visual sense. For example, a substrate with an antiglare film having a small (close to 0) antiglare index value is inferior in antiglare property, and conversely, a substrate with an antiglare film having a large antiglare index value is good. It has antiglare properties.

90 or less is preferable, 80 or less is more preferable, and 70 or less is still more preferable for the glare index value (Sparkle) of the surface of the base body 1 with an antiglare film. The glare index value was determined by placing an anti-glare film-coated substrate on the display surface of a liquid crystal display with the anti-glare film forming surface (the surface having irregularities) facing upward, and using an eye system ISC-A. It can be measured using. The higher the glare index value, the greater the glare. It should be noted that the term “glare” means that when the substrate 1 with an antiglare film is used for a pixel matrix type display element, many light particles having a period larger than that of the pixel matrix are observed on the surface of the substrate 1 with an antiglare film, It means the degree of hindrance to visibility, and the lower the glare, the less observable the light particles are, and the more the visibility is improved.

As described above, the haze, the 60° specular gloss, the antiglare index value, and the glare index value of the antiglare film-coated substrate 1 are the skewness Rsk of the surface roughness curve of the antiglare film 3, the arithmetic mean roughness, and the like. It can be adjusted by Ra, the average length RSm of the elements of the roughness curve, and the like.

<Liquid composition for forming antiglare film>
The antiglare film 3 can be formed using a liquid composition for forming an antiglare film. The liquid composition for forming an antiglare film includes a silica precursor (A) containing a CF3(CH2)n- group, scale particles (B), and a liquid medium (C). The liquid composition for forming an antiglare film contains, in addition to the fluorine-containing silica precursor (A), the scaly particles (B) and the liquid medium (C), other components unless the characteristics of the resulting antiglare film 3 are impaired. May be included. Other components include metal oxide precursors other than silica (such as titanium and zirconium as metals), and binders made of thermoplastic resin, thermosetting resin, ultraviolet curable resin, or the like. Hereinafter, each component contained in the liquid composition for forming an antiglare film will be described.

(Fluorine-containing silica precursor (A))
The fluorine-containing silica precursor (A) forms a matrix containing silica as a main component and a CF ₃ (CH ₂ ) _n -group (where n is an integer of 1 to 6) by a hydrolytic condensation reaction.

The fluorinated silica precursor capable of forming the matrix (A), for example, bonded to a silicon _{atom, CF 3 (CH 2) n} - fluorine-containing silane compound having a group and a hydrolyzable group (A1) and The hydrolysis-condensation product is mentioned, and it may further contain an alkoxysilane and its hydrolysis-condensation product (sol-gel silica), silazane and the like. The fluorinated silane compound (A1) may further have a hydrocarbon group bonded to a silicon atom. The fluorine-containing silica precursor (A) may be used alone or in combination of two or more.

More specifically, the fluorine-containing silica precursor (A) may be composed of either or both of the fluorine-containing silane compound (A1) and its hydrolysis-condensation product, or the fluorine-containing silane compound (A1) and One or both of the hydrolysis-condensation products and one or both of the alkoxysilane and the hydrolysis-condensation products may be contained. From the viewpoint of preventing cracks and film peeling of the antiglare film 3, the fluorine-containing silica precursor (A) includes one or both of the fluorine-containing silane compound (A1) and its hydrolysis-condensation product, and alkoxysilane and its It is preferable to include either or both of the hydrolysis-condensation products.

In the fluorine-containing silane compound (A1), examples of the hydrolyzable group bonded to a silicon atom include an alkoxy group, an acyloxy group, a ketoxime group, an alkenyloxy group, an amino group, an aminoxy group, an amide group, an isocyanate group and a halogen atom. Can be mentioned. Among these, an alkoxy group such as a methoxy group and an ethoxy group, an isocyanate group and a halogen atom (particularly a chlorine atom) are preferable from the viewpoint of the balance between the stability of the fluorine-containing silane compound (A1) and the ease of hydrolysis. .. When a plurality of hydrolyzable groups are present in the fluorine-containing silane compound (A1), the hydrolyzable groups may be the same or different, and the same group is preferable from the viewpoint of easy availability.

When the fluorine-containing silane compound (A1) has a hydrocarbon group bonded to a silicon atom, the hydrocarbon group may be a monovalent hydrocarbon group bonded to one silicon atom, or a monovalent hydrocarbon group bonded to two silicon atoms. It may be a valent hydrocarbon group. Examples of the monovalent hydrocarbon group include an alkyl group, an alkenyl group and an aryl group. Examples of the divalent hydrocarbon group include an alkylene group, an alkenylene group and an arylene group. Further, the fluorine-containing silane compound (A1) has a structure in which, in place of this hydrocarbon group, -O-, -S-, -CO- and NR'- (where R'is a hydrogen atom or It is a monovalent hydrocarbon group.), or one or more selected from the group may be included.

Since the fluorine-containing silane compound (A1) has a fluorine atom in the CF3(CH2)n- group, the surface tension of the liquid composition for forming an antiglare film is reduced as compared with the case where it does not have a fluorine atom. Therefore, the skewness Rsk of the roughness curve of the antiglare film 3 obtained by firing this can be reduced, and the haze of the substrate 1 with the antiglare film can be reduced.

Further, since the CF ₃ (CH ₂ ) _n -group has a fluorine atom, it is difficult to burn when heated. Therefore, it is possible to prevent the antiglare film 3 obtained by firing the liquid composition for forming an antiglare film from becoming porous. Further, the CF ₃ (CH ₂ ) _n − group containing a fluorine atom can impart excellent chemical resistance and moisture resistance to the antiglare film 3.

In the CF ₃ (CH ₂ ) _n -group contained in the fluorine-containing silane compound (A1), n is an integer of 1 to 6, and preferably an integer of 1 to 3. The CF ₃ (CH ₂ ) _n -group is particularly preferably a trifluoropropyl group in which n is 2. When the liquid composition for forming an antiglare film contains two or more kinds of fluorine-containing silane compounds (A1), the value of n in the CF ₃ (CH ₂ ) _n − group may be the same or different.

The fluorine-containing silane compound (A1) is preferably a compound represented by the following formula (I).
_{{CF 3 (CH 2) n} } q -Si-R (4-p-q) L p ··· (I)
In formula (I), L is a hydrolyzable group. Examples of the hydrolyzable group include those mentioned above, and the preferred embodiments are also the same. R is a hydrogen atom or a monovalent hydrocarbon group. Examples of the monovalent hydrocarbon include those mentioned above.

In the formula (I), p and q are numbers satisfying p+q≦4. p is an integer of 1 to 3. From the viewpoint of improving the adhesiveness, p is preferably 3 or 2, and particularly preferably 3. q is 1 or 2. Since there are cases where a plurality of qs cause a decrease in reactivity, 1 is preferable from the viewpoint of ensuring the adhesiveness.

Alkoxysilane is a silane compound having an alkoxy group bonded to a silicon atom. Examples of the alkoxysilane include tetraalkoxysilane such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane.

The fluorine-containing silica precursor (A) is an effect of the present invention in addition to one or both of the above-mentioned fluorine-containing silane compound (A1) and its hydrolysis-condensation product, and one or both of alkoxysilane and its hydrolysis-condensation product. Other silane compounds capable of forming a matrix may be contained within the range not impairing the above. Other silane compounds include alkoxysilanes having a vinyl group (vinyltrimethoxysilane, vinyltriethoxysilane, etc.), alkoxysilanes having an epoxy group (2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycid Xypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, etc.), alkoxysilane having an acryloyloxy group (3-acryloyloxypropyltrimethoxysilane, etc.) and the like. To be

The hydrolytic condensation reaction of the fluorine-containing silane compound (A1) and the alkoxysilane can be carried out by a known method. For example, when tetraalkoxysilane is used as the alkoxysilane, water is added to the tetraalkoxysilane in an amount of 4 times the mole of the tetraalkoxysilane or more, and an acid or an alkali is added as the catalyst.

Examples of the acid used as a catalyst include inorganic acids such as nitric acid, sulfuric acid and hydrochloric acid and organic acids such as formic acid, oxalic acid, monochloroacetic acid, dichloroacetic acid and trichloroacetic acid. Examples of the alkali used as the catalyst include ammonia, sodium hydroxide, potassium hydroxide and the like. As the catalyst, an acid is preferable from the viewpoint of long-term storage stability of the hydrolyzed condensate of the fluorine-containing silane compound (A1).

(Scale-like particles (B))
The scaly particles (B) constitute the antiglare film 3 either alone or in a matrix derived from the fluorine-containing silica precursor (A). In addition to the scaly particles (B) which become the scaly particles (B) alone, the scaly particles (B) have a preferable average particle diameter, a primary particle thickness, and a secondary particle in the scaly particles (B) of the present embodiment. Including those in which particles having other shapes are appropriately combined so as to obtain a shape satisfying the thickness, aspect ratio, and the like.

The average particle diameter of the scaly particles (B) is preferably 0.08 to 0.42 μm, more preferably 0.17 to 0.21 μm. When the average particle size of the scale-like particles (B) is 0.08 μm or more, cracks and film peeling of the antiglare film 3 can be sufficiently suppressed even if the film thickness is large. When the average particle size of the scaly particles (B) is 0.42 μm or less, the dispersion stability in the liquid composition for forming an antiglare film becomes good.

Examples of the scaly particles (B) include scaly silica particles, scaly alumina particles, scaly titania particles, and scaly zirconia particles. Among them, scale-like silica particles are preferable from the viewpoint of imparting excellent antiglare properties to the antiglare film 3.

The flake-shaped silica particles are, for example, silica secondary particles formed by laminating flaky silica primary particles and a plurality of flaky silica primary particles with their planes oriented parallel to each other. The silica secondary particles usually have a laminated structure particle morphology. The scaly silica particles may be composed of only one of primary silica particles and secondary silica particles.

The thickness of the silica primary particles is preferably 0.001 to 0.1 μm. When the thickness of the silica primary particles is within the above range, it is possible to form scaly silica secondary particles in which one surface or a plurality of sheets are stacked by mutually aligning the surfaces in parallel. The silica primary particles have an aspect ratio of preferably 2 or more, more preferably 5 or more, still more preferably 10 or more.

The thickness of the secondary silica particles is preferably 0.001 to 1 μm, more preferably 0.005 to 0.5 μm. The aspect ratio with respect to the thickness of the secondary silica particles is preferably 2 or more, more preferably 5 or more, still more preferably 10 or more. It is preferable that the secondary silica particles exist independently of each other without being fused.

To prepare the liquid composition for forming an antiglare film, a powder which is an aggregate of a plurality of scale-like silica particles, or a dispersion liquid in which the powder is dispersed in a liquid medium is used. The silica particle concentration in the dispersion is preferably 1 to 80% by mass.

(Liquid medium (C))
The liquid medium (C) has a function as a solvent for dissolving the fluorine-containing silica precursor (A) or a dispersion medium for dispersing it, and a function as a dispersion medium for dispersing the scaly particles (B). As the liquid medium (C), one type may be used alone, or two or more types may be used in combination.

The liquid medium (C) preferably contains at least a liquid medium (C1) having a boiling point of 160° C. or lower and a liquid medium (C2) having a boiling point higher than 160° C.

When the boiling point of the liquid medium (C1) is 160° C. or less, the liquid composition for forming an antiglare film is applied onto the transparent substrate 2 using an electrostatic coating device equipped with an electrostatic coating gun having a rotary atomizing head. After that, the antiglare film 3 formed by firing has more excellent antiglare properties. The boiling point of the liquid medium (C1) is preferably 50 to 150°C, more preferably 55 to 140°C. When the boiling point of the liquid medium (C1) is at least the lower limit value of the above range, after the droplets of the liquid composition for forming an antiglare film adhere to the transparent substrate 2, the droplets wet and spread on the substrate and become uniform. Easy to form a film. When the boiling point of the liquid medium (C1) is not more than the upper limit value of the above range, it is easy to form an uneven structure.

Examples of the liquid medium (C1) include water, alcohols (methanol, ethanol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, 1-pentanol, etc.) having a boiling point of 160° C. or less, 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 monomethyl ether, etc.) , Ethylene glycol monoethyl ether, etc.) can be used.

When the boiling point of the liquid medium (C2) is higher than 160° C., the skewness Rsk of the roughness curve of the antiglare film 3 can be lowered when the liquid composition for forming an antiglare film contains the liquid medium (C2), which is excellent. It is easy to achieve both anti-glare property and low haze.

Examples of the liquid medium (C2) include alcohols, ketones, ethers, cellosolves, esters, glycol ethers, nitrogen-containing compounds and sulfur-containing compounds having a boiling point of higher than 160°C. Examples of alcohols include diacetone alcohol, 1-hexanol, ethylene glycol, propylene glycol and the like. Examples of the nitrogen-containing compound include N,N-dimethylacetamide, N,N-dimethylformamide, N-methylpyrrolidone and the like. Examples of glycol ethers include ethylene glycol monobutyl ether. Examples of the sulfur-containing compound include dimethyl sulfoxide and the like.

The content ratio of the liquid medium (C1) to the total amount of the liquid medium (C) is preferably 80 to 99.9% by mass, and the content ratio of the liquid medium (C2) is preferably 0.01 to 20% by mass.

Water is required to hydrolyze the alkoxysilane and the like in the fluorine-containing silica precursor (A). Therefore, the liquid medium (C) preferably contains at least water as the liquid medium (C1). In this case, the liquid medium (C) may be only water, or may contain one or more of the liquid medium (C1) and the liquid medium (C2) other than water. As the liquid medium (C1) other than water, alcohols are preferable, and methanol, ethanol, isopropyl alcohol and butanol are particularly preferable. When the liquid medium (C) contains water, the liquid medium (C2) contained in the liquid medium (C) is preferably diacetone alcohol or propylene glycol.

(composition)
The liquid composition for forming an antiglare film has both one or both of a fluorine-containing silane compound (A1) and a hydrolysis-condensation product thereof, and one or both of a tetraalkoxysilane and a hydrolysis-condensation product thereof. In the case where the fluorine-containing silica precursor (A) is contained, the ratio of either or both of the fluorine-containing silane compound (A1) and its hydrolyzed condensate is 3 with respect to the total amount (100 mass%) of the solid content of the fluorine-containing silica precursor (A). Is 50 to 50% by mass (more preferably 5 to 30% by mass), and the proportion of either or both of the tetraalkoxysilane and its hydrolyzed condensate is 50 to 97% by mass (more preferably 70 to 90% by mass). preferable. When the content of either or both of the fluorine-containing silane compound (A1) and its hydrolyzed condensate is not more than the upper limit of the above range, sufficient adhesion strength between the antiglare film 3 and the transparent substrate 2 can be obtained. .. If the content of either or both of the fluorine-containing silane compound (A1) and its hydrolyzed condensate is at least the lower limit value of the above range, cracks in the antiglare film 3 even if the antiglare film 3 is thick. And film peeling can be sufficiently suppressed.

The content of the scale-like particles (B) in the liquid composition for forming an antiglare film is 3 to 15% by mass based on the total amount (100% by mass) of solids in the liquid composition for forming an antiglare film. It is preferably 5-10% by mass. When the content of the scaly particles (B) is at least the lower limit value of the above range, the substrate 1 with an antiglare film exhibits excellent antiglare properties. In addition, cracking of the film can be prevented. When the content of the scaly particles (B) is at most the upper limit value of the above range, the haze can be lowered while maintaining excellent antiglare property.

The content of the liquid medium (C) in the liquid composition for forming an antiglare film is an amount according to the solid content concentration of the liquid composition for forming an antiglare film. The solid content concentration of the liquid composition for forming an antiglare film is preferably 0.1 to 8% by mass, and 0.2 to 1% by mass based on the total amount (100% by mass) of the liquid composition for forming an antiglare film. Is more preferable. When the solid content concentration is at least the lower limit value of the above range, the liquid amount of the liquid composition for forming an antiglare film can be reduced. When the solid content concentration is not more than the upper limit of the above range, the film thickness uniformity of the antiglare film is improved.

The solid content concentration of the liquid composition for forming an antiglare film is the total content of all components other than the liquid medium (C) in the liquid composition for forming an antiglare film. However, in the present specification, unless otherwise specified, the content of the fluorine-containing silica precursor (A) when calculating the solid content concentration of the liquid composition for forming an antiglare film is in terms of SiO ₂ .

The total content of the fluorine-containing silica precursor (A) and the scaly particles (B) in the liquid composition for forming an antiglare film is the total amount of solids in the liquid composition for forming an antiglare film (100 mass. %), 30 to 100 mass% is preferable, and 40 to 100 mass% is more preferable. When the total content of the fluorinated silica precursor (A) and the scaly particles (B) is at least the lower limit value of the above range, the obtained antiglare film 3 has excellent adhesion to the transparent substrate 2. When the total content of the fluorinated silica precursor (A) and the scaly particles (B) is not more than the upper limit value of the above range, cracks and film peeling of the antiglare film 3 can be suppressed.

When the fluorine-containing silica precursor (A) contains a hydrolyzed condensate of tetraalkoxysilane, a solution of tetraalkoxysilane, or a solution of tetraalkoxysilane, from which antiglare film 3 having desired performance can be produced with high reproducibility, or After mixing a solution of a mixture of tetraalkoxysilane and its hydrolyzed condensate with a dispersion liquid of the scale-like particles (B), the tetraalkoxysilane is hydrolyzed and condensed in the presence of the scale-like particles (B). It is preferable.

<Method of manufacturing substrate with antiglare film>
The method for producing a substrate with an antiglare film according to the present embodiment comprises applying the liquid composition for forming an antiglare film described above onto the transparent substrate 2 by a spray coating method to form a coating film, and forming the coating film. It is a method of forming the antiglare film 3 by firing to obtain the substrate 1 with the antiglare film. The above-described manufacturing method may include a step of forming a functional layer on the surface of the transparent substrate 2 main body before forming the antiglare film 3, if necessary. In addition, after forming the antiglare film 3, a step of performing other post-processing may be included.

(Preparation of liquid composition for forming antiglare film)
The liquid composition for forming an antiglare film is prepared, for example, by preparing a solution in which the fluorinated silane precursor (A) is dissolved in the liquid medium (C), and adding the dispersion liquid of the scale-like particles (B) and, if necessary, the solution. Accordingly, it can be prepared by mixing with an additional liquid medium (C).

(Application)
The liquid composition for forming an antiglare film is applied onto the transparent substrate 2 by a spray coating method. This is performed, for example, by using an electrostatic coating device equipped with an electrostatic coating gun having a rotary atomizing head to charge the liquid composition for forming an antiglare film and spraying it toward the transparent substrate 2. As a result, a coating film of the liquid composition for forming an antiglare film is formed on the transparent substrate 2. The electrostatic coating device includes a gun body and a rotary atomizing head, and rotationally drives the rotary atomizing head to atomize and discharge the anti-glare film forming liquid composition supplied to the rotary atomizing head by centrifugal force, It is sprayed toward the transparent substrate 2.

When the liquid composition for forming an antiglare film is applied to the transparent substrate 2, the transparent substrate is formed from the nozzle tip of the electrostatic coating gun (that is, the front end of the rotary atomizing head in the spray direction of the liquid composition for forming the antiglare film). The distance to 2 (hereinafter also referred to as “gun height”) is appropriately adjusted according to the width of the transparent substrate 2, the film thickness of the liquid composition for forming an antiglare film applied on the transparent substrate 2, and the like. ..

The height of the gun is preferably 150 to 280 mm, more preferably 180 to 240 mm, further preferably 230 to 240 mm. If the distance to the transparent substrate 2 is too close, the haze of the substrate 1 with an antiglare film is likely to increase, and if it is too close, the possibility of electric discharge increases. On the other hand, when the distance to the transparent substrate 2 is too large, the coating efficiency is lowered, and the skewness Rsk of the roughness curve becomes too high, so that the antiglare property is likely to be lowered.

Further, at this time, the particle diameter (discharge particle diameter) of the droplet of the liquid composition for forming an antiglare film sprayed from the electrostatic coating device is preferably 12 μm or less, more preferably 10 μm or less in terms of Sauter mean particle diameter. When the Sauter average particle size is 12 μm or less, the antiglare film 3 exhibits excellent antiglare properties.

Here, the Sauter average particle size is a value calculated from the ratio of the total sum of the measured droplet volumes and the total surface area, assuming that the total surface area and the total volume of the droplets are equal. The Sauter average particle diameter is represented by the following equation (2), where xi is the particle diameter and ni is the number of particles having the particle diameter xi.

The Sauter average particle diameter is 60 mm in height from the surface of the transparent substrate, and can be measured as a value at a position where the Sauter average particle diameter becomes maximum when the measurement position is horizontally shifted from the cup center of the electrostatic coating gun. ..

(Baking)
Next, the coating film of the liquid composition for forming an antiglare film formed on the transparent substrate 2 is baked.
As a result, the liquid medium (C) in the coating film is volatilized and removed, and the conversion of the fluorine-containing silica precursor (A) remaining in the coating film into a silica-based matrix proceeds (for example, the fluorine-containing silica precursor. In the case where the body (A) is a silane compound having a hydrolyzable group bonded to a silicon atom, the hydrolyzable group is almost decomposed and condensation of the hydrolyzate proceeds, and the film is densified to prevent The glare film 3 is formed.

The baking of the coating film may be carried out at the same time as applying the liquid composition for forming an antiglare film to the transparent substrate 2 by applying the liquid composition for forming an antiglare film to the transparent substrate 2 when the liquid composition for forming an antiglare film is applied to the transparent substrate 2. After coating, the coating film may be heated. The firing temperature is preferably 30° C. or higher. For example, when the transparent substrate 2 is glass, 100 to 750° C. is more preferable, and 150 to 550° C. is further preferable.

The surface temperature of the transparent substrate 2 when the liquid composition for forming an antiglare film is applied is preferably 60°C or lower, preferably 15 to 50°C, and more preferably 20 to 40°C. When the surface temperature of the transparent substrate 2 is equal to or higher than the lower limit value of the above range, the liquid medium (C) contained in the liquid composition for forming an antiglare film is quickly evaporated, so that desired irregularities can be easily formed. When the surface temperature of the transparent substrate 2 is at most the upper limit value of the above range, the adhesion between the transparent substrate 2 and the antiglare film 3 will be good. The temperature (application temperature) of the liquid composition for forming an antiglare film sprayed from the electrostatic coating gun is the same as above.

According to the manufacturing method of the embodiment described above, by spraying the liquid composition for forming an antiglare film, preferably using an electrostatic coating device having a rotary atomizing head, excellent antiglare property is obtained. The anti-glare film 3 which it has can be formed. This is because the droplets of the liquid composition for forming an antiglare film have a slower speed than in the case of applying a conventionally widely used spray method other than the electrostatic coating device (for example, a method using a two-fluid nozzle). And the liquid medium (C) in the adhered droplets volatilizes rapidly, so that the droplets are less likely to spread on the transparent substrate 2 and the shape at the time of attachment is sufficiently maintained. It is considered that this is because the film is formed in the state of

Further, in the manufacturing method of the embodiment described above, the surface shape of the antiglare film 3 to be formed can be controlled by the viscosity of the liquid composition for forming an antiglare film, the coating conditions, the firing temperature, and the like.

(Second embodiment)
FIG. 2 is a schematic cross-sectional view showing the substrate 10 with an antiglare film of this embodiment. FIG. 3 is a schematic bottom view showing the substrate 10 with an antiglare film. The antiglare film-coated substrate 10 shown in FIGS. 2 and 3 includes a low reflection film 4 and an antifouling film 5 on the antiglare film 3 of the antiglare film substrate 1 shown in FIG. The substrate 1 with an antiglare film is different from the substrate 1 with an antiglare film in that the printed layer 6 is provided on the peripheral portion of the surface opposite to the antiglare film 3, but other configurations are common. Therefore, in the base 10 with the antiglare film, the components corresponding to those of the base 1 with the antiglare film are designated by the same reference numerals, and detailed description thereof will be omitted. It should be noted that the low reflection film 4, the antifouling film 5 and the printing layer 6 may not all be provided, and any one or two may be provided.

(Low reflection film)
The low reflection film 4 is a film that is provided on the antiglare film 3 to suppress reflection of incident light on the transparent substrate 2 and to make a reflected image unclear. As the structure of the low reflection film 4, for example, a structure in which a high refractive index layer having a refractive index of 1.9 or more at a wavelength of 550 nm and a low refractive index layer having a refractive index of 1.6 or less at a wavelength of 550 nm are laminated. it can. The low reflection film 4 is not limited as long as it can suppress the reflection of light.

When the low reflective film 4 has a structure in which a high refractive index layer and a low refractive index layer are laminated, the high reflective index layer and the low refractive index layer in the low reflective film may include one layer each. Alternatively, the structure may include two or more layers. When each of the high refractive index layer and the low refractive index layer includes two or more layers, it is preferable that the high refractive index layer and the low refractive index layer are alternately laminated.

The materials for the high refractive index layer and the low refractive index layer are not particularly limited, and can be appropriately selected in consideration of the required degree of low reflectivity and productivity. Examples of materials forming the high refractive index layer include niobium oxide (Nb ₂ O ₅ ), titanium oxide (TiO ₂ ), zirconium oxide (ZrO ₂ ), tantalum oxide (Ta ₂ O ₅ ), and silicon nitride (Si ₃ N _{4 ).} One or more selected from the above) can be preferably used. As a material forming the low refractive index layer, silicon oxide (SiO ₂ ), a material containing a mixed oxide of Si and Sn, a material containing a mixed oxide of Si and Zr, a mixed oxide of Si and Al One or more selected from materials including can be preferably used.

From the viewpoint of productivity and refractive index, the low reflective film 4 is a layer in which the high refractive index layer is made of one kind selected from niobium oxide, tantalum oxide and silicon nitride, and the low refractive index layer is made of silicon oxide. Is preferable.

The method for forming each layer constituting the low reflective film 4 is not particularly limited, and, for example, a vacuum vapor deposition method, an ion beam assisted vapor deposition method, an ion plate method, a sputtering method, a plasma CVD method or the like can be used. Among these film forming methods, the use of the sputtering method is preferable because a dense and highly durable film can be formed. In particular, a sputtering method such as a pulse sputtering method, an AC sputtering method or a digital sputtering method is preferable.

For example, when the film is formed by the pulse sputtering method, the transparent substrate 2 is placed in a chamber of a mixed gas atmosphere of an inert gas and an oxygen gas, and a target is used as an adhesion layer forming material so as to have a desired composition. Select and form a film. At this time, the gas species of the inert gas in the chamber is not particularly limited, and various inert gases such as argon and helium can be used. When the high refractive index layer and the low refractive index layer are formed by the pulse sputtering method, the layer thickness of each layer can be adjusted, for example, by adjusting the discharge power and the film forming time.

In the antiglare film-coated substrate 10 of the present embodiment, the antiglare film 3 is mainly composed of silica, and the low reflection film 4 including a high refractive index layer and a low refractive index layer is formed on the antiglare film 3. In addition to high antiglare property and low haze ratio, excellent low reflectivity can be realized.

(Anti-fouling film)
The antifouling film 5 is provided on the low reflection film 4. The antifouling film 5 is a film that suppresses the adhesion of organic substances and inorganic substances to the surface, or a film that, even when organic substances and inorganic substances adhere to the surface, has the effect of easily removing the attached substances by cleaning such as wiping. is there.

The antifouling film 5 is not limited as long as it has water repellency and oil repellency and can impart antifouling property to the substrate 10 with an antiglare film obtained. However, a fluorine-containing organosilicon compound is cured by a hydrolysis condensation reaction. It is preferably composed of a fluorine-containing organosilicon compound film obtained by the above.

Further, the thickness of the antifouling film 5 is preferably 2 to 30 nm, and more preferably 5 to 20 nm when the antifouling film 5 is composed of a fluorine-containing organic silicon compound film. When the film thickness of the antifouling film 5 is 2 nm or more, the antifouling film 5 has excellent abrasion resistance as well as antifouling property. When the film thickness of the antifouling film 5 is 30 nm or less, the optical properties such as haze and haze of the antiglare film-coated substrate 10 in the state where the antifouling film 5 is formed are good.

As a method for forming a fluorine-containing organosilicon compound film, a composition of a silane coupling agent having a perfluoroalkyl group; a fluoroalkyl group such as a fluoroalkyl group containing a perfluoro(polyoxyalkylene) chain is used as a low reflection film. The surface of 4 is coated with a spin coating method, a dip coating method, a casting method, a slit coating method, a spray coating method or the like and then heat-treated as necessary, or a fluorine-containing organosilicon compound is applied to the surface of the low reflection film 4. A vacuum vapor deposition method in which heat treatment is performed as necessary after vapor phase vapor deposition, and the like can be mentioned. In order to obtain a fluorine-containing organosilicon compound film having high adhesion, a vacuum vapor deposition method is preferable. The formation of the fluorine-containing organosilicon compound film by the vacuum vapor deposition method is preferably performed using a film-forming composition containing a fluorine-containing hydrolyzable silicon compound.

The film forming composition is a composition containing a fluorine-containing hydrolyzable silicon compound, and is not limited as long as it is a composition capable of forming a film by a vacuum vapor deposition method. The hydrolyzable silicon compound may include a partially hydrolyzed condensate or a partially hydrolyzed cocondensate in addition to the compound itself.

The fluorine-containing hydrolyzable silicon compound used for forming the fluorine-containing organosilicon compound film of the present embodiment is specifically selected from the group consisting of a perfluoropolyether group, a perfluoroalkylene group and a perfluoroalkyl group. Fluorine-containing hydrolyzable silicon compounds having one or more groups are mentioned. These groups are present as a fluorine-containing organic group bonded directly to the silicon atom of the hydrolyzable silyl group via a linking group or directly.

A film-forming composition containing such a fluorine-containing hydrolyzable silicon compound is attached to the surface of the low reflection film 4 and reacted to obtain a fluorine-containing organosilicon compound film. Note that conventionally known methods and conditions can be applied to specific vacuum deposition methods and reaction conditions.

At this time, the antifouling film 5 may be directly formed on the surface of the antiglare film 3 without forming the low reflection film 4. In this case, as described above, the antiglare film 3 contains a CF ₃ (CH ₂ ) _n − group inside the film, so that the film is prevented from becoming porous and the composition for forming a film permeates into the film. Does not occur. Therefore, the antifouling film 5 having excellent adhesion to the antiglare film 3 and excellent antifouling property can be obtained.

The antifouling film 5 can be formed, for example, by applying the composition for forming a film using a known spray device or the like. The nozzle of the spray device is moved in parallel with respect to the antiglare film-coated substrate 1 in the first direction from one end to the other end to apply the film-forming composition. The nozzles that have reached the other end are translated in the second direction perpendicular to the first direction by a predetermined distance (hereinafter referred to as the pitch). The nozzle is translated again from the other end toward the one end. By repeating this, application is performed so that the application region covers the entire surface of the substrate 1 with the antiglare film.

When the pitch is small, the number of times the nozzle reciprocates on the antiglare film-attached substrate 1 is larger than when the pitch is large, so that the discharge speed per unit area can be made constant by increasing the moving speed of the nozzle. it is conceivable that. Table 1 shows the measurement results of the amount of F atoms on the substrate by the moving speed and pitch of the nozzle.

From the results of Table 1, even when the discharge amount per unit area is constant, the nozzle moving speed is made faster and the pitch is made smaller than the nozzle moving speed is made slower to make the pitch larger. It can be seen that the coating efficiency of the film-forming composition is better. In particular, it is preferable that the pitch is 12 mm or less because the coating efficiency of the film forming composition is improved. The results in Table 1 are obtained by applying the composition for forming a film to a glass plate on which an antiglare film has not been formed and measuring the amount of F atoms. The same tendency will occur.

(Print layer)
The printed layer 6 is, for example, for the purpose of enhancing the visibility and aesthetics of the display, a wiring circuit arranged near the outer periphery of an image display device such as a mobile device, or an adhesive portion between the housing of the mobile device and the base 10 with an antiglare film. It is provided as needed to hide the information. Here, the peripheral portion means a band-shaped region having a predetermined width from the outer periphery toward the central portion. The printed layer 6 may be provided on the entire circumference of the surface of the transparent substrate 2 opposite to the main surface, or may be provided on a part of the circumference.

The printed layer 6 is formed in a desired color according to the purpose, for example, with a width capable of hiding the wiring circuit and the adhesive portion. The print layer 6 is formed using ink, for example.

Examples of the ink include an inorganic ink containing a ceramics sintered body and the like, and an organic ink containing a color material such as a dye or a pigment and an organic resin. For example, when the printed layer 6 is formed in black, the ceramics contained in the black inorganic ink include chromium oxide, oxides such as iron oxide, carbides such as chromium carbide and tungsten carbide, carbon black, mica and the like. Can be mentioned. The black printed layer 6 is obtained by melting the ink composed of the ceramics and silica, printing it in a desired pattern, and then drying it. This inorganic ink requires melting and drying steps and is generally used as a glass ink.

The organic ink is a composition containing a dye or pigment of a desired color and an organic resin. As the organic resin, epoxy resin, acrylic resin, polyethylene terephthalate, polyether sulfone, polyarylate, polycarbonate, acrylonitrile-butadiene-styrene (ABS) resin, phenol resin, transparent ABS resin, polyurethane, polymethyl methacrylate. Examples of the resin include homopolymers of polyvinyl, polyvinyl butyral, polyetheretherketone, polyethylene, polyester, polypropylene, polyamide, polyimide, and copolymers of monomers of these resins and copolymerizable monomers.

Among the above-mentioned inorganic ink and organic ink, it is preferable to use the organic ink because the drying temperature is low. In addition, from the viewpoint of chemical resistance, organic ink containing a pigment is preferable.

The printing layer 6 is formed by printing the ink on a predetermined portion of the surface opposite to the main surface of the transparent substrate 2. Printing methods include bar coating method, reverse coating method, gravure coating method, die coating method, roll coating method, screen method, inkjet method, etc. The screen printing method is preferable because it is possible. The printing layer 6 may be composed of multiple layers in which a plurality of layers are laminated, or may be composed of a single layer. When the printing layer 6 is composed of multiple layers, the printing layer 6 can be formed by repeatedly printing and drying the ink.

When the substrate 10 with the antiglare film provided with the printed layer 6 is used as a front plate of an image display device or the like, the substrate 10 with the antiglare film is arranged so that the printed layer side is arranged on the image display device side. Is provided on the visible side (front side). When the image display device provided with the base 10 with the antiglare film is viewed from the front side, the black printed portion is provided on the peripheral portion and the display portion is provided inside the peripheral portion through the antiglare film 3 and the transparent substrate 2, respectively. To be seen.

At this time, when the haze of the front plate is high, the black printed part appears clouded, and when the display part turns black when the display panel is not energized, the black printed part and the black part of the display part seen through the front plate are black. A boundary may occur between the two and spoil the appearance. Since the haze is low in the substrate 10 with the antiglare film of the present embodiment, a boundary is unlikely to occur between the black printed portion and the black portion of the display portion seen through the front plate, and the border is continuously visible without these boundaries. It will be excellent in aesthetics.

<Use of substrate with antiglare film>
The application of the substrate with an antiglare film of the present invention is, for example, a vehicle transparent component (headlight cover, side mirror, front transparent substrate, side transparent substrate, rear transparent substrate, instrument panel surface, etc.), meter, architectural window. , Show window, display (notebook personal computer, monitor, LCD, PDP, ELD, CRT, PDA, etc.), LCD color filter, touch panel substrate, pickup lens, optical lens, spectacle lens, camera component, video component, CCD cover Substrates, optical fiber end faces, projector parts, copying machine parts, transparent substrates for solar cells (cover glass, etc.), mobile phone windows, backlight unit parts (light guide plates, cold cathode tubes, etc.), backlight unit parts LCD brightness enhancement film (Prism, semi-transmissive film, etc.), liquid crystal brightness enhancement film, organic EL light emitting device parts, inorganic EL light emitting device parts, phosphor light emitting device parts, optical filters, end faces of optical parts, illumination lamps, lighting equipment covers, amplification lasers Examples include light sources, antireflection films, polarizing films, and agricultural films.

The use of the substrate with an antiglare film of the present invention is preferably an interior article of a transport machine, and more preferably an in-vehicle article, from the viewpoint that both excellent antiglare properties and low haze can be achieved at a high level. The in-vehicle article is preferably an in-vehicle system including an image display device (car navigation, instrument panel, head-up display, dashboard, center console, shift knob).

Hereinafter, the present invention will be described in detail with reference to examples, but is not limited to the following examples. Among Examples 1-28, Examples 1-17 are Examples and Examples 18-28 are Comparative Examples.
The evaluation methods and materials used in each example are shown below.

<Optical property evaluation method>
(Roughness curve skewness Rsk, arithmetic average roughness Ra, roughness curve element average length RSm)
The skewness Rsk of the roughness curve, the arithmetic average roughness Ra, and the average length RSm of the elements of the roughness curve on the surface of the antiglare film are defined in JIS B0601-2001 using SURFCOM1500SD3-12 manufactured by Tokyo Seimitsu Co., Ltd., respectively. It measured according to the method currently described.

(Average film thickness)
The film thickness of the antiglare film was measured as follows. The cross section of the antiglare film processed by the focused ion beam processing was observed by SEM at a magnification of 10,000 to 100,000 times, and the thickness from the interface between the glass and the antiglare film to the surface of the antiglare film was measured over the entire imaging range. The film thickness over the entire imaging range can be calculated from the number of pixels in the cross section of the antiglare film on digital data, and the number of pixels in the direction perpendicular to the scale bar and film thickness. Alternatively, it may be calculated using commercially available image processing software. The SEM observation was performed in a direction perpendicular to the film thickness over a visual field of 70 μm or more, and the average value was taken as the average film thickness.

(F amount)
The amount of F in the antiglare film was measured by the following method. A glass having a specific gravity of 2.48 containing 1.0 mass% of fluorine (F) was used as a standard sample. Using Rigaku ZSX100e, measurement diameter 30 mm, measurement line F-Kα, filter OUT, slit Std. , Analysis crystal RX35, detector PC, PHA100-300, peak angle 38.794 deg. (20 sec), B.I. G. Angle 43.000 deg. Under the condition of (10 sec), the fluorine content (mass %) in the film to be measured and the fluorine content (mass %) in the standard sample were measured. The F content was calculated by dividing the measured value of the fluorine content in the film to be measured measured above by the measured value of the fluorine content of the standard sample.

(Haze)
The haze (%) of the substrate with an antiglare film was measured using a haze meter (HR-100 type manufactured by Murakami Color Research Laboratory) according to the method defined in JIS K7136:2000.

(60° specular gloss (Gloss))
The 60° specular glossiness (%) was measured as the glossiness of the surface of the substrate with the antiglare film. The 60° specular gloss is a method specified in JIS Z8741: 1997, which is the 60° specular gloss, and an all-in-one gloss meter (Rhopint IQ manufactured by Low Point Instruments Co., Ltd.) A black felt was laid on the (face) side to turn off the reflection on the back surface of the substrate with an antiglare film, and the measurement was performed at almost the center of the antiglare film.

(Anti-glare index value (Diffusion))
The measurement of the antiglare index value of the substrate with a dazzle film was performed by the following procedure using a goniophotometer, GC5000L manufactured by Nippon Denshoku Industries Co., Ltd.

The direction parallel to the thickness direction of the substrate with the antiglare film is 0°. At this time, on the main surface side of the substrate with an antiglare film, from the direction of the angle θ=−45°±0.5° (hereinafter, also referred to as “direction of angle −45°”), the main surface of the substrate with an antiglare film is The surface is irradiated with the first light. The first light is reflected by the main surface of the base body with the antiglare film. The brightness of the 45° reflected light reflected in the direction of an angle of 45° from the main surface of the substrate with the antiglare film is measured and defined as “45° reflected light brightness”.

Next, the angle θ for measuring the brightness of the light reflected by the main surface of the antiglare film-coated substrate 1 was changed in the range of 5° to 85°, and the same operation was carried out to obtain the antiglare film-coated substrate 1 The luminance distribution of the reflected light in the range of 5° to 85° reflected by the main surface is measured and summed to obtain the “luminance of the total reflected light”.

Next, the antiglare index value (Diffusion) is calculated from the above formula (1).

(Glitter index value (Sparkle) measurement)
A substrate with an anti-glare film is placed on the display surface of a liquid crystal display (i-Phone 4, manufactured by Apple Inc., pixel density 326 ppi), and the main surface (the surface having irregularities) on which the anti-glare film is formed faces upward. And the glare index value was measured using an eye scale ISC-A manufactured by Eye System Co., Ltd.

(Temperature durability)
The durability of the anti-glare film is such that, in a heat shock test (500 cycles of a treatment in which the conditions of -40° C. for 30 minutes and 90° C. for 30 minutes are repeated alternately) is 0.5% or more before and after the test. Those that were present were evaluated as “poor”, and those that were less than 0.5% were considered as “good”.

(Gun height)
The distance from the lowermost end of the center of the electrostatic coating gun (electrostatic automatic gun described later) spraying the antiglare film-forming composition to the transparent substrate surface was expressed as the gun height.

<Material>
(Silica precursor)
Tetraethoxysilane and organic silane were used as the silica precursor (A).
As the organic silane, any one of trifluoropropyltrimethoxysilane, bistrimethoxysilylethane, propyltrimethoxysilane, hexyltrimethoxysilane, and octyltriethoxysilane (all manufactured by Shin-Etsu Silicone Co., Ltd.) was used.

(Scaly particle dispersion liquid)
As the scaly particle dispersion liquid, an SLV liquid (a dispersion liquid of scaly silica particles obtained by crushing Sunlabry LFS HN150, manufactured by AGC SII Tech Co., Ltd. and dispersed in water) was used. The average particle diameter of scaly silica particles in the SLV liquid is 175 nm, the average aspect ratio (average particle diameter/average thickness) is 80, and the scaly silica particle concentration is 5% by mass.

(Liquid medium)
As the liquid medium, Solmix (registered trademark) AP-11 (manufactured by Nippon Alcohol Sales Co., Ltd.) mixed with diacetone alcohol or propylene glycol was used. Solmix AP-11 is a mixed solvent of ethanol 85 mass %, isopropyl alcohol 10 mass %, and methanol 5 mass %.

(Example 1)
The tetraethoxysilane, trifluoropropyltrimethoxysilane as an organic silane, and an SLV liquid are used, and the fluorine-containing silica precursor (tetraethoxysilane, organic silane, SLV particles) has a SiO2 equivalent solid content concentration of 3.11% by mass, The ingredients were prepared so that the ratio of the solid content of each component to the total content was as shown in Table 2. At this time, the liquid medium was stirred using a magnetic stirrer, the tetraethoxysilane, the organic silane, and the SLV liquid were added to the liquid medium and mixed at 25° C. for 30 minutes. Then, an aqueous nitric acid solution having a concentration of 60% by mass was added dropwise at 0.54% by mass with respect to the amount of the mixed solution of tetraethoxysilane, trifluoropropyltrimethoxysilane, the SLV liquid and the liquid medium, and further at 60°C. The mixture was mixed for 60 minutes to obtain a precursor liquid of a liquid composition for forming an antiglare film.

The precursor liquid obtained above was diluted with AP-11 so that the solid content concentration shown in Table 2 was obtained to obtain a liquid composition for forming an antiglare film.

As the transparent substrate, a special glass Dragontrail (registered trademark) for chemical strengthening manufactured by Asahi Glass Co., Ltd. (size: 100 mm×100 mm, thickness: 1.1 mm) was used at 410° C. for 2.5 hours using KNO3 molten salt. The glass substrate subjected to the chemical strengthening treatment of was used. The glass substrate subjected to the chemical strengthening treatment had a compressive stress layer depth of 25 μm and a surface compressive stress of 750 MPa.

The surface of the glass substrate (transparent substrate) subjected to the chemical strengthening treatment was washed with a neutral detergent, followed by washing with pure water and drying.

The liquid composition for forming an antiglare film obtained above was applied on a transparent substrate after washing and drying with an electrostatic coating device (liquid electrostatic coater, manufactured by Asahi Sunac Co., Ltd.) to form a coating film. As the electrostatic coating gun of the electrostatic coating apparatus, a rotary atomizing type electrostatic automatic gun (Sanbell, ESA120, cup diameter 70 mm, manufactured by Asahi Sunac Co., Ltd.) was used.

The temperature inside the coating booth of the electrostatic coating device was adjusted within the range of 25±3° C., and the humidity was adjusted within the range of 50%±10%. On the chain conveyor of the electrostatic coating device, the cleaned transparent substrate that had been heated to 30° C.±3° C. in advance was placed via the stainless steel plate. While transporting at a constant speed of 3.0 m/min on a chain conveyor, the top surface of the glass substrate (the surface opposite to the surface in contact with the molten tin during the production by the float method) was charged with the gun height as shown in Table 2. After the liquid composition for forming an antiglare film having a temperature within the range of 25±3° C. is applied twice by the coating method, the antiglare film is formed by baking in the air at 450° C. for 30 minutes to form the antiglare film. An attached substrate was obtained. The above evaluation was performed on the obtained substrate with an antiglare film. The results are shown in Table 3.

(Examples 2 to 28)
The procedure of Example 1 was repeated except that the types and amounts of the organic silanes, the amounts of the tetraethoxysilane and the SLV liquid, and the amounts of the solid contents of the respective components with respect to the total amount of the solid components were adjusted to the ratios shown in Table 2. A liquid composition for forming a glare film was obtained. The obtained antiglare film-forming liquid composition was used to obtain a gun height in Table 2 and a substrate with an antiglare film was produced in the same manner as in Example 1, and the obtained substrate with an antiglare film was evaluated as described above. I went. The results are shown in Table 3. In Example 16 only, the liquid composition for forming the antiglare film was applied once.

In addition, the particle size (discharge particle size) of the droplet of the liquid composition for forming an antiglare film discharged from the rotary atomizing type electrostatic automatic gun of the electrostatic coating device is measured by an image analysis type particle size distribution manufactured by Japan Laser Co., Ltd. The measurement was performed using the measurement system VisiSize6. The conditions for measuring the discharge particle diameter are as follows.

(Measurement condition)
Spray type: Rotating atomizing type electrostatic automatic gun Gun height: 235mm from substrate surface to cup tip
Measurement position: A liquid composition of the liquid composition for forming an antiglare film when measured at a height of 60 mm from the surface of the glass substrate, with the measurement position being horizontally shifted from directly below the center of the cup of the rotary atomizing electrostatic automatic gun. The position where the drop flying frequency is the maximum Number of measured particles: 1000 Calculation of average particle size: 1000 The Sauter average particle size was calculated for each measured particle size.
Measurement area at each measurement position: 2623 μm (height)×1475 μm (width)×1795 μm (depth)

(Measurement result)
In Examples 1 to 28, in a case where the gun height is 235 mm, the position where the Sauter mean particle size becomes maximum when the height is 60 mm from the substrate surface and the measurement position is horizontally shifted from the center of the gun cup. The average Sauter particle size was 10.7 μm±1 μm.

From Tables 2 and 3, the antiglare film-attached substrates of Examples (Examples 1 to 17) have an antiglare index value of 0.05 or more and a haze of 8 or less, which shows excellent antiglare properties. It turns out that low haze can be achieved at the same time. In the substrates with antiglare film of Comparative Examples (Examples 18 to 28), the antiglare index value was good, but the haze was high and the visibility was poor. It is considered that this is because Rsk exceeds 1.3. Therefore, according to the present invention, it was found that an antiglare substrate having both excellent antiglare properties and low haze can be obtained.

<Fat/Wipeability Evaluation Test>
The oil-fat wiping property was implemented as follows. On the clean antiglare film of the substrate with an antiglare film, 0.05 g of NIVEA cream manufactured by Kao Corporation was placed as an oil and fat. Next, a silicone plug having a bottom surface of φ15 mm with a load of 1 kg was placed on it to transfer oil and fat. Subsequently, a silicone stopper on which a 1 kg load onto which the oil and fat was transferred was placed on a paper waste for 80 seconds to remove excess oil and fat. Subsequently, a silicon plug with a load of 1 kg was placed on the sample surface, and oils and fats were transferred to the sample surface to obtain an evaluation sample.
It is necessary to transfer the oil and fat of the evaluation sample to a wiping cloth (Toraysee MK MK24H-CPMK manufactured by Toray Industries, Inc.) that has a bottom area of 20 mm × 20 mm and is cut into a strip shape with a load of 100 g placed thereon until the oil and fat cannot be visually recognized. Counted the number of times. The part of the wiping cloth that came into contact with oil and fat was not reused, and the wiping was carried out so that the clean part was always in contact with the oil and fat. If it was wiped off within 20 times, the wiping property was good, and if within 10 times, it was very good. When it took 21 times or more for wiping, it was judged as "poor" and the result is shown in Table 4.

<Scratch resistance test>
The surface of the scratch-resistant sample was attached to an indenter with a bottom area of 20 mm x 20 mm, with Kanakin No. 3 (white cloth cotton attached to the Japanese Standards Association JIS L 0803 compliant test) with a load of 1 kg, and a rubbing speed per minute. It was rubbed back and forth 80 times and 100,000 times at a rub distance of 40 mm. If the sample surface after rubbing does not show any change visually, the scratch resistance is very good and "excellent". If there are 3 or less scratches with a width of 0.8 mm or less, the scratch resistance is good and "good". And When scratches with a width of 0.8 mm or more are confirmed or four or more scratches with a width of 0.8 mm or less are confirmed, the scratch resistance is considered to be “poor” and the results are shown in Table 4.

From Table 4, the anti-glare film-coated substrates (Examples 1 to 17) of the examples were good in terms of oil-fat wiping property and scratch resistance. This is considered to be related to Rsk, and if Rsk is too large, the convex and concave shapes of the uneven shape derived from the antiglare film become sharp, so that it is difficult to remove oil and fat, and the tip of the convex shape is easily broken, so that the scratch resistance is high. It is thought that it will become less active. In the substrate with an antiglare film of the present invention, by setting Rsk to be 1.3 or less, not only good optical properties are obtained, but also the oil and fat wiping property related to the ease of wiping fingerprints and the abrasion property are related. Good results were also obtained with respect to scratch resistance. Further, it was also found that by setting Rsk to be less than 1.07, better oil and fat wiping property and scratch resistance can be obtained.

1, 10... Substrate with antiglare film, 2... Transparent substrate, 3... Antiglare film, 4... Low reflection film, 5... Antifouling film, 6... Printing layer

Claims (15)

A transparent substrate and an antiglare film provided on the transparent substrate,
The antiglare film is mainly composed of silica,
The skewness Rsk of the roughness curve of the surface of the antiglare film is 1.3 or less,
The average length RSm of the elements of the roughness curve of the surface of the antiglare film is 10 μm or more and 20.2 μm or less, and
A substrate with an antiglare film, which has an arithmetic average roughness Ra of 0.01 μm or more. The substrate with an antiglare film according to claim 1, wherein the antiglare film has an average film thickness of 15 to 1500 nm. The substrate with an antiglare film according to claim 1 or 2, wherein the antiglare film has an average film thickness of 50 to 1500 nm. The antiglare film-attached substrate according to claim 1, wherein the antiglare film is provided so that a part of the transparent substrate is exposed. The substrate with an antiglare film according to any one of claims 1 to 4, wherein an average length RSm of an element of the roughness curve of the surface of the antiglare film is 18 µm or less. The substrate with an antiglare film according to claim 1, wherein a skewness Rsk of a roughness curve of the surface of the antiglare film is 1.05 or less. The substrate with an antiglare film according to claim 1, wherein the arithmetic average roughness Ra of the surface of the antiglare film is 0.1 μm or less. The substrate with an antiglare film according to any one of claims 1 to 7, wherein an average length RSm of an element of a roughness curve on the surface of the antiglare film is 11 µm or more. When a glass having a specific gravity of 2.48 containing 1.0 mass% of fluorine is used as a standard sample, a value (F amount) obtained by dividing the measured value of the fluorine content of the antiglare film by the measured fluorine value of the standard sample is , 0.23-2.5, The antiglare film-attached substrate according to any one of claims 1 to 8. Wherein _CF 3 _{(CH 2) n} - _group, CF 3 _{CH 2 CH} 2 - anti-glare film with a substrate according to any one of claims 1 to 9 is a group. The substrate with an antiglare film according to any one of claims 1 to 10, wherein the 60° specular glossiness on the surface of the antiglare film is 135% or less. The antiglare film-attached substrate according to any one of claims 1 to 11, wherein the transparent substrate is a glass substrate. The antiglare film-coated substrate according to claim 1, wherein the transparent substrate is a chemically strengthened glass substrate. The substrate with an antiglare film as a substrate according to any one of claims 1 to 13, wherein the transparent substrate has a curved surface. The substrate with an antiglare film according to any one of claims 1 to 14, wherein the transparent substrate has a thickness of 0.1 to 5 mm.

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