JP7010324B2 - Hypokeimenon with anti-glare film - Google Patents

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

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

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

International Publication No. 2016/021560 Japanese Unexamined Patent Publication No. 64-1527 Japanese Patent Application Laid-Open No. 2003-344608 Japanese Unexamined Patent Publication No. 2002-79616 International Publication No. 2005/121265

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

An antiglare film is formed on the front plate of the image display device on the visible side, and black printing is performed on the peripheral portion of the non-visual side surface on which the antiglare film is not provided for the purpose of improving the design and aesthetics. A light shielding portion such as a layer is provided. At this time, if the haze of the antiglare film is high, cloudiness may be visually recognized when the black print layer is viewed through the antiglare film, which causes a problem of spoiling the aesthetic appearance.

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

The present invention has the following aspects.

(1) It has a transparent substrate and an antiglare film provided on the transparent substrate, the antiglare film contains silica as a main component, and the skewness Rsk of the roughness curve of the surface of the antiglare film is 1.3. It is characterized in that the average length RSm of the element 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 glazing film.

The definitions of the following terms apply throughout the 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 main component is silica" means that the SiO ₂ is contained 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.
By "scaly particles" is meant particles 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 size" of the scaly particles is the particle size at the point where it becomes 50% in the cumulative volume distribution curve with the total volume of the particle size (maximum length) distribution obtained on a volume basis as 100%, that is, the volume-based cumulative 50. It means% diameter (D50). The particle size distribution is determined by the frequency distribution and the cumulative volume distribution curve measured by the laser diffraction / scattering type particle size distribution measuring device.
"Aspect ratio" means the ratio of the particle diameter to the thickness of the particles (maximum length / thickness), and "average aspect ratio" is the average value of the aspect ratios of 50 randomly selected particles. Is. The thickness of the particles is measured by an atomic force microscope (hereinafter, also referred to as AFM), and the longest length is measured by TEM.

According to the present invention, it is possible to obtain a substrate with an antiglare film having excellent antiglare properties and low haze.
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, which has excellent antiglare properties and has a low haze.

It is sectional drawing which shows the substrate with antiglare film which concerns on 1st Embodiment. It is sectional drawing which shows the substrate with antiglare film which concerns on 2nd Embodiment. It is a schematic bottom view of the substrate with antiglare film of FIG.

Hereinafter, embodiments will be described in detail with reference to the drawings.
(First Embodiment)
FIG. 1 is a schematic cross-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 CF ₃ (CH ₂ ) _n − groups (where n is an integer of 1 to 6; the same applies hereinafter). Further, the skewness Rsk of the roughness curve on the surface of the antiglare film 3 is 1.3 or less, and the arithmetic mean roughness Ra is 0.01 μm or more. The antiglare film 1 has excellent antiglare properties due to the antiglare film 3 having the above-mentioned characteristics, and the haze is lowered, for example, the black printed layer is seen through the antiglare film substrate 1. At that time, it is possible to prevent the white turbidity from being visually recognized. Hereinafter, each configuration of the substrate 1 with an 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 be imparted with antiglare by an antiglare film, and is, for example, 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, non-alkali glass and the like. Examples of the resin include polyethylene terephthalate, polycarbonate, triacetyl cellulose, polymethyl methacrylate and the like.

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

The surface (hereinafter, also referred to as “main surface”) on which the antiglare film 3 of the transparent substrate 2 is formed may be smooth or may have irregularities. Smoothing is preferable in terms of the usefulness of providing the antiglare film 3 (the point where desired optical characteristics can be obtained). 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 region to which antiglare property is imparted on the main surface of the transparent substrate 2, and may not be formed in other regions.

The shape of the transparent substrate 2 may be not only a flat shape as shown in the figure but also a shape having a curved surface. In this case, the whole may be composed of a curved surface, or may be composed of a curved surface portion and a flat portion. Recently, in various devices (televisions, personal computers, smartphones, car navigation systems, etc.) equipped with an image display device, those having a curved display surface of the image display device have appeared. The substrate 1 with an antiglare film, in which the transparent substrate 2 has a curved surface, is useful for such an image display device.

As the transparent substrate 2, a glass substrate is preferable. The method for manufacturing the glass substrate is not particularly limited. The glass substrate can be produced by putting a desired glass raw material into a melting furnace, heating and melting the glass substrate to clarify the glass substrate, supplying the glass substrate to a molding apparatus to form the molten glass, and slowly cooling the glass substrate. The method for forming the glass substrate is not particularly limited, and for example, a glass substrate formed by a float method, a fusion method, a down draw method, or the like can be used.

The thickness of the transparent substrate 2 can be appropriately selected depending on the intended use, 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 in which the main surface of the glass substrate is strengthened is preferable. The strengthening treatment improves the strength of the glass, for example, the thickness can be reduced while maintaining the strength. An antiglare film may be formed on the untempered 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 a wind 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 is thin (for example, less than 2 mm).

In the chemical strengthening method, a glass plate is immersed in a molten salt at a temperature below the strain point temperature of the glass, and ions on the surface layer of the glass plate (for example, sodium ions) are exchanged for ions having a larger ionic radius (for example, potassium ions). do. As a result, compressive stress is generated on 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 alkaline barrier layer or a wide band low refractive index layer. As the undercoat layer, a layer formed by applying an undercoat forming composition containing a hydrolyzate of alkoxysilane (sol-gel silica) to the transparent substrate 2 is preferable.

(Anti-glare film)
The antiglare film 3 has an uneven structure on the surface, and diffusely reflects the external light applied to the transparent substrate 2 to suppress the surface reflection of the external light. For example, in various image display devices such as liquid crystal displays (LCDs) and plasma displays (PDPs), in general, when external light such as indoor lighting (fluorescent lamps) and sunlight is reflected on the display surface, it is visually recognized by a reflected image. The sex is reduced. On the other hand, by providing the antiglare film 3 on the transparent substrate 2 and diffusely reflecting the external light, it is possible to suppress the deterioration of visibility due to the reflected image.

The antiglare film 3 contains silica as a main component and contains a CF ₃ (CH ₂ ) _n -group. Further, 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 comprises, 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 by using a liquid composition for forming an antiglare film. In this case, the fluorine-containing silica precursor (A) forms a matrix containing silica as a main component and CF ₃ (CH ₂ ) _n − groups. Then, the scaly 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 suppress the porosity of the antiglare film 3 obtained by firing this liquid composition for forming the antiglare film. 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 membrane 3 is obtained by scraping the antiglare membrane 3 from the transparent substrate 2 and using the scraped antiglare membrane 3 to prepare a powder sample by nuclear magnetic resonance spectroscopy (NMR). ), Infrared spectroscopy (IR), etc., can be identified. When the 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 mean roughness Ra of the surface of the antiglare film 3 is 0.01 μm or more. The arithmetic mean roughness Ra is a value obtained by averaging the absolute value deviations from the reference plane in the roughness curve included in the reference length taken on the reference plane. When the arithmetic mean roughness Ra is 0.01 μm or more, the antiglare film 3 exhibits excellent antiglare properties. Further, the antiglare film 3 preferably has an arithmetic mean roughness Ra of 0.1 μm or less. The fact that the arithmetic mean roughness Ra is 0.1 μm or less is one of the factors for preventing the haze from becoming too high and enabling the antiglare film 3 to achieve both excellent antiglare and low haze.

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 cubed average of the height Z (x) at the reference length made dimensionless by the cube of the root mean square height (Zq), with respect to the average line of the uneven shape. It is an index showing the bias. When the skewness Rsk value of the roughness curve is positive (Rsk> 0), the uneven shape is biased toward the concave side and the protruding shape becomes sharper, and when it is negative (Rsk <0), the uneven shape is biased toward the convex side. The protruding shape tends to be dull. The blunt shape of the roughness curve has a lower haze than the sharp one.

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

The average length RSm of the element of the roughness curve on the surface of the antiglare film 3 is preferably 18 μm or less, more preferably 17.8 μm or less, still more 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 glare index value (Sparkle) of the antiglare film-attached substrate 1 tends to be large, and if it is too small, the antiglare property tends to decrease.

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 liquid composition for forming the antiglare film at the time of forming the antiglare film 3. Composition (solid content concentration, primary particle size of scaly particles, secondary particle size, content of each component, etc.), application conditions of the liquid composition for forming an antiglare film on the transparent substrate 2 (for example, application by a spray method). In this case, it can be adjusted by the spray pressure, the amount of the liquid, the temperature of the transparent substrate, the number of times of application, 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 SURFCOM 1500SD3-12 manufactured by Tokyo Seimitsu Co., Ltd. It can be measured according to the method used.

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 or lower the glare index value. It is more preferable that the average film thickness of the antiglare film 3 is 50 nm or more because sufficient antiglare property can be imparted to the substrate 1 with the antiglare film. The average film thickness of the antiglare film 3 is 1500 nm or less, which is one of the factors for achieving both the antiglare index value and the optical characteristics such as haze in a good range. Here, the average film thickness of the antiglare film 3 is obtained by treating the cross section of the antiglare film 3 by focused ion beam processing and then observing it with a scanning microscope (SEM) at a magnification of, for example, 10,000 times. 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 taken by SEM or 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 where antiglare property is imparted on the main surface) without gaps, and for example, a preferable antiglare property index described later. As long as the value and haze can be obtained, a part of the main surface (or the above region) of the transparent substrate 2 is exposed without the antiglare film formed, for example, the antiglare film 3 is formed in an island shape. You may. 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. The transparent substrate 2 may not 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 may be used. Alternatively, the structure may be such that the first convex portion and the second convex portion overlap. Such a surface structure can be observed by analyzing the laser microscope measurement data with image processing software.

The film thickness of the antiglare film 3 is the application condition of the liquid composition for forming the antiglare film on the transparent substrate 2 (for example, in the case of application by the spray method, the amount of the liquid composition for forming the antiglare film and the application). It can be adjusted by the number of times, etc.) and the composition of the liquid composition for forming an antiglare film (solid content concentration, content of each component, etc.).

For the fluorine content in the antiglare film 3, a glass having a specific gravity of 2.48 containing 1.0% by mass of fluorine (F) is used as a standard sample, and the fluorine measurement value of the antiglare film 3 is divided by the fluorine measurement 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 the increase in RSm. The amount of F is preferably 0.23 or more, more preferably 0.3 or more, and even more preferably 0.4 or more. This is due to temperature and humidity durability. The F amount can be measured by, for example, the following method. Using ZSX100e manufactured by Rigaku Co., Ltd., a measurement diameter of 30 mm, a measurement line FKα, a filter OUT, and a slit Std. , Spectral crystal RX35, detector PC, PHA100-300, peak angle 38.794 deg. (20 sec), B. 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, respectively. The F amount is calculated by dividing the measured fluorine content of the film to be measured by the measured fluorine content of the standard sample.

When the antifouling film described later is formed on the surface of the antiglare film 3, the amount of F in the antiglare film 3 is measured after the antifouling film is removed. 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 amount of F in the antiglare film 3 is the composition of the liquid composition for forming the antiglare film, the amount of CF ₃ (CH ₂ ) _n − groups in the liquid composition for forming the antiglare film, and the fluorine-containing silica precursor (). It can be adjusted by the type of A) and the amount of CF ₃ (CH ₂ ) _n -group of the fluorine-containing silica precursor (A).

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 printing portion on the opposite surface to the antiglare film 3, it suppresses the appearance of white turbidity in the black printing portion and is an excellent antiglare film. Attached substrate 1 can be obtained.

The surface gloss of the substrate 1 with an antiglare film is preferably 135 ° or less, more preferably 130% or less, still more preferably 120% or less. The 60 ° mirror gloss (%) (Gloss) is preferably 50% or more, more preferably 60% or more, still more preferably 70% or more. Here, the 60 ° mirror gloss of the substrate 1 with an antiglare film is, for example, the method specified in the 60 ° mirror gloss of JIS Z8741: 1997, and is an all-in-one gloss meter (manufactured by Lowpoint Instruments, Rhоpоint IQ). ), A black felt is laid on the back surface side to eliminate the back surface reflection of the antiglare film-attached substrate 1, and the value is measured at the substantially central portion of the plane of the antiglare film 3.

The diffusion of the surface of the substrate 1 with an antiglare film is preferably 0.05 or more, more preferably 0.1 or more, still more preferably 0.2 or more. When the antiglare index value on the surface of the substrate 1 with an antiglare film is 0.05 or more, excellent antiglare property is exhibited when used in an image display device.

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

Next, the angle θ for measuring the brightness of the light reflected on the main surface of the antiglare film substrate 1 is changed in the range of 5 ° to 85 °, and the same operation is performed to perform the same operation. The brightness distribution of the reflected light in the range of 5 ° to 85 ° reflected on the main surface of the above is measured and totaled, and the value is defined as "the brightness of the total reflected light".

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

Anti-glare index value =
{(Brightness of total reflected light-45 ° brightness of reflected light) / (Brightness of total reflected light)} Equation (1)

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

The surface glare index value (Sparkle) of the antiglare film-attached substrate 1 is preferably 90 or less, more preferably 80 or less, still more preferably 70 or less. For the glare index value, place a substrate with an antiglare film on the display surface of the liquid crystal display so that the antiglare film forming surface (surface with irregularities) faces up, and use the Eye Scale ISC-A manufactured by Eye System. Can be measured using. The larger the value of the glare index value, the larger the glare. Glittering 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 to which visibility is impaired, and the lower the glare, the less likely it is that light particles are observed, and the better the visibility.

As described above, the haze, 60 ° mirror surface gloss, antiglare index value, and glare index value of the substrate 1 with antiglare film are the skewness Rsk of the surface roughness curve of antiglare film 3 and the arithmetic mean roughness. 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 by using a liquid composition for forming an antiglare film. The liquid composition for forming an antiglare film contains a silica precursor (A) containing a CF3 (CH2) n- group, scaly particles (B), and a liquid medium (C). In addition to the fluorine-containing silica precursor (A), scaly particles (B) and the liquid medium (C), the liquid composition for forming an antiglare film contains other components as long as the characteristics of the obtained antiglare film 3 are not impaired. It may be contained. Examples of other components include binders made of metal oxide precursors other than silica (metals such as titanium and zirconium), thermoplastic resins, thermosetting resins, and ultraviolet curable resins. 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 CF ₃ (CH ₂ ) _n − groups (where n is an integer of 1 to 6) by a hydrolysis condensation reaction.

Examples of the fluorine-containing silica precursor (A) that can form the matrix include a fluorine-containing silane compound (A1) bonded to a silicon atom and having a CF ₃ (CH ₂ ) _n − group and a hydrolyzable group. Examples thereof include the hydrolyzed condensate, and may further contain alkoxysilane, a hydrolyzed condensate thereof (sol-gel silica), silazane and the like. The fluorine-containing 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 consist of either or both of the fluorine-containing silane compound (A1) and its hydrolyzed condensate, and the fluorine-containing silane compound (A1) and It may contain either or both of the hydrolyzed condensate and either or both of alkoxysilane and the hydrolyzed condensate thereof. From the viewpoint of preventing cracks and peeling of the antiglare film 3, the fluorine-containing silica precursor (A) includes either one or both of the fluorine-containing silane compound (A1) and its hydrolyzed condensate, and alkoxysilane and its hydrolyzed condensate. It is preferable to contain either one or both of the hydrolyzed condensates.

In the fluorine-containing silane compound (A1), examples of the hydrolyzable group bonded to the silicon atom include an alkoxy group, an acyloxy group, a ketooxime 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 or 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 groups, and the same groups are preferable in terms of 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 2 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, an aryl group and the like. Examples of the divalent hydrocarbon group include an alkylene group, an alkenylene group, an arylene group and the like. Further, in the fluorine-containing silane compound (A1), instead of this hydrocarbon group, -O-, -S-, -CO- and NR'-(where R'is a hydrogen atom or It may have one or two or more inserted groups selected from monovalent hydrocarbon groups).

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 lowered as compared with the case where the fluorine atom 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 lowered, and the haze of the substrate 1 with the antiglare film can be lowered.

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 suppress the porosity of the antiglare film 3 obtained by firing this liquid composition for forming the antiglare film. Further, since the CF ₃ (CH ₂ ) _n -group contains a fluorine atom, excellent chemical resistance and moisture resistance can be imparted to the antiglare film 3.

In the CF ₃ (CH ₂ ) _n -group of the fluorine-containing silane compound (A1), n is an integer of 1 to 6, 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.

As the fluorine-containing silane compound (A1), the compound represented by the following formula (I) is preferable.
{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 described above, and the same applies to preferred embodiments. R is a hydrogen atom or a monovalent hydrocarbon group. Examples of the monovalent hydrocarbon include those described above.

In formula (I), p and q are numbers satisfying p + q ≦ 4. p is an integer of 1 to 3. p is preferably 3 or 2 from the viewpoint of increasing adhesion, and 3 is particularly preferable. q is 1 or 2. If there are a plurality of q, it may cause a decrease in reactivity, so 1 is preferable from the viewpoint of ensuring adhesion.

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

The fluorine-containing silica precursor (A) has an effect of the present invention other than one or both of the above-mentioned fluorine-containing silane compound (A1) and its hydrolyzed condensate, and one or both of the alkoxysilane and its hydrolyzed condensate. It may contain other silane compounds that can form a matrix within a range that does not impair. Other silane compounds include an alkoxysilane having a vinyl group (vinyltrimethoxysilane, vinyltriethoxysilane, etc.), an alkoxysilane having an epoxy group (2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycid). Xipropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, etc.), alkoxysilane having an acryloyloxy group (3-acryloyloxypropyltrimethoxysilane, etc.) and the like. Be done.

The hydrolysis 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 of 4 times or more the molar amount of the tetraalkoxysilane and an acid or an alkali as a catalyst are added to the tetraalkoxysilane.

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

(Scale particles (B))
The scaly particles (B) form the antiglare film 3 alone or by being contained in a matrix derived from the fluorine-containing silica precursor (A). In addition to the scaly particles (B) that become scaly particles (B) by themselves, the scaly particles (B) have a preferable average particle diameter in the scaly particles (B) of the present embodiment, the thickness of the primary particles, and the secondary particles. It also includes particles of other shapes that are appropriately combined so as to have a shape that satisfies the thickness, aspect ratio, and the like.

The average particle size 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 scaly particles (B) is 0.08 μm or more, cracks and peeling of the antiglare film 3 can be sufficiently suppressed even if the film thickness is thick. 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 is good.

Examples of the scaly particles (B) include scaly silica particles, scaly alumina particles, scaly titania particles, and scaly zirconia particles. Of these, scaly silica particles are preferable from the viewpoint of imparting excellent antiglare properties to the antiglare film 3.

The flaky silica particles are, for example, composed of flaky silica primary particles and a plurality of flaky silica primary particles formed by overlapping the planes of the flaky silica primary particles in parallel orientation with each other. Silica secondary particles usually have a particle morphology with a laminated structure. The scaly silica particles may be composed of only one of the primary silica particles and the secondary silica particles.

The thickness of the silica primary particles is preferably 0.001 to 0.1 μm. As long as the thickness of the primary silica particles is within the above range, it is possible to form scaly secondary silica particles in which one or more of the primary silica particles are oriented in parallel with each other and overlapped with each other. The aspect ratio of the silica primary particles is preferably 2 or more, more preferably 5 or more, and even more preferably 10 or more.

The thickness of the silica secondary 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 silica secondary particles is preferably 2 or more, more preferably 5 or more, and even more preferably 10 or more. It is preferable that the silica secondary particles exist independently of each other without being fused.

For the preparation of the liquid composition for forming an antiglare film, a powder which is an aggregate of a plurality of scaly silica particles or a dispersion liquid in which the powder is dispersed in a liquid medium is used. The concentration of silica particles 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, 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 lower, 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 equipped with a rotary atomizing head. After that, the antiglare film 3 formed by firing has better 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 equal to or higher than the lower limit of the above range, the droplets of the liquid composition for forming an antiglare film adhere to the transparent substrate 2, and then the droplets wet and spread on the substrate and are uniform. Easy to form a film. When the boiling point of the liquid medium (C1) is not more than the upper limit of the above range, an uneven structure is likely to be formed.

Examples of the liquid medium (C1) include water, alcohols having a boiling point of 160 ° C. or lower (methanol, ethanol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, 1-pentanol, etc.), and ketones (acetone, methyl ethyl ketone). , Methyl isobutyl ketone, etc.), ethers (tetratetra, 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 the antiglare film contains the liquid medium (C2), which is excellent. It is easy to achieve both anti-glare and low haze.

Examples of the liquid medium (C2) include alcohols, ketones, ethers, cellosolves, esters, glycol ethers, nitrogen-containing compounds, sulfur-containing compounds and the like having a boiling point of more 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 for hydrolysis of alkoxysilane and the like in the fluorine-containing silica precursor (A). Therefore, it is preferable that the liquid medium (C) contains at least water as the liquid medium (C1). In this case, the liquid medium (C) may be water alone, or may contain one or more of a liquid medium (C1) other than water and a liquid medium (C2). 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, diacetone alcohol and propylene glycol are preferable as the liquid medium (C2) contained in the liquid medium (C).

(composition)
The liquid composition for forming an antiglare film is both one or both of the fluorine-containing silane compound (A1) and its hydrolyzed condensate, and one or both of tetraalkoxysilane and its hydrolyzed condensate. When, the ratio of either one or both of the fluorine-containing silane compound (A1) and its hydrolyzed condensate to the total amount (100% by mass) of the SiO2 equivalent solid content of the fluorine-containing silica precursor (A) is 3. In an amount of about 50% by mass (more preferably 5 to 30% by mass), the proportion of either one or both of tetraalkoxysilane and its hydrolyzed condensate is 50 to 97% by mass (more preferably 70 to 90% by mass). preferable. When the content of either one 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 one or both of the fluorine-containing silane compound (A1) and its hydrolyzed condensate is at least the lower limit of the above range, cracks in the antiglare film 3 even if the film thickness of the antiglare film 3 is thick. And film peeling is sufficiently suppressed.

The content of the scaly particles (B) in the antiglare film forming liquid composition is 3 to 15% by mass with respect to the total amount (100% by mass) of the solid content in the antiglare film forming liquid composition. It is preferable, 5 to 10% by mass is more preferable. When the content of the scaly particles (B) is at least the lower limit of the above range, the substrate 1 with an antiglare film exhibits excellent antiglare properties. In addition, it is possible to prevent the occurrence of cracks in the film. When the content of the scaly particles (B) is not more than the upper limit of the above range, the haze can be lowered while maintaining the excellent antiglare property.

The content of the liquid medium (C) in the liquid composition for forming an antiglare film is an amount corresponding to the solid content concentration of the liquid composition for forming an antiglare film. The solid content concentration of the antiglare film forming liquid composition is preferably 0.1 to 8% by mass, preferably 0.2 to 1% by mass, based on the total amount (100% by mass) of the antiglare film forming liquid composition. Is more preferable. When the solid content concentration is at least the lower limit of the above range, the 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 uniformity of the film thickness of the antiglare film is improved.

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

The total content of the fluorine-containing silica precursor (A) and the scaly particles (B) in the antiglare film forming liquid composition is the total amount of solid content (100 mass) in the antiglare film forming liquid composition. %), More preferably 30 to 100% by mass, and more preferably 40 to 100% by mass. When the total content of the fluorine-containing silica precursor (A) and the scaly particles (B) is at least the lower limit of the above range, the obtained antiglare film 3 is excellent in adhesion to the transparent substrate 2. When the total content of the fluorine-containing silica precursor (A) and the scaly particles (B) is not more than the upper limit of the above range, cracks and peeling of the antiglare film 3 are suppressed.

When the fluorine-containing silica precursor (A) contains a hydrolyzed condensate of tetraalkoxysilane, a solution of tetraalkoxysilane or a solution of tetraalkoxysilane can be produced at a high level with good reproducibility. After mixing a solution of a mixture of tetraalkoxysilane and its hydrolyzed condensate with a dispersion of scaly particles (B), tetraalkoxysilane is hydrolyzed and condensed in the presence of scaly particles (B). Is preferable.

<Manufacturing method of substrate with antiglare film>
In the method for producing a substrate with an antiglare film of the present embodiment, the liquid composition for forming an antiglare film described above is applied onto the transparent substrate 2 by a spray coating method to form a coating film, and the coating film is formed. This is a method of forming an antiglare film 3 by firing to obtain a substrate 1 with an antiglare film. The above-mentioned manufacturing method may include, if necessary, a step of forming a functional layer on the surface of the transparent substrate 2 main body before forming the antiglare film 3. Further, it may have a step of performing other post-processing after the antiglare film 3 is formed.

(Preparation of liquid composition for forming antiglare film)
For the liquid composition for forming an antiglare film, for example, a solution in which the fluorine-containing silane precursor (A) is dissolved in the liquid medium (C) is prepared, and a dispersion of scaly particles (B) and a necessary solution are added to the solution. It can be prepared by mixing with an additional liquid medium (C) accordingly.

(Application)
The liquid composition for forming an antiglare film is applied onto the transparent substrate 2 by a spray coating method. This is done, for example, by using an electrostatic coating apparatus equipped with an electrostatic coating gun equipped with a rotary atomizing head to charge the liquid composition for forming an antiglare film and spray 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 is equipped with a gun body and a rotary atomizing head, and the rotary atomizing head is rotationally driven to atomize and release the antiglare film forming liquid composition supplied to the rotary atomizing head by centrifugal force. Spray 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 tip of the nozzle of the electrostatic coating gun (that is, the front end of the rotary atomizing head in the spraying 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 antiglare film forming liquid composition applied on the transparent substrate 2, and the like. ..

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

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

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

The apparent diameter of Sauter is 60 mm above the surface of the transparent substrate, and can be measured as the value at the position where the average diameter of Sauter is maximized when the measurement position is shifted horizontally from the center of the cup 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 fired.
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). When the body (A) is a silane compound having a hydrolyzable group bonded to a silicon atom, the hydrolyzable group is almost decomposed and the condensation of the hydrolyzate proceeds), and the film is densified to prevent it. The glare film 3 is formed.

The coating film may be fired at the same time as the coating of the transparent substrate 2 by heating the transparent substrate 2 when the liquid composition for forming the antiglare film is applied to the transparent substrate 2, and the liquid composition for forming the antiglare film may be 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, it is more preferably 100 to 750 ° C., and even more preferably 150 to 550 ° C.

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 at least the lower limit of the above range, the liquid medium (C) contained in the antiglare film forming liquid composition evaporates quickly, so that desired unevenness is likely to be formed. When the surface temperature of the transparent substrate 2 is not more than the upper limit of the above range, the adhesion between the transparent substrate 2 and the antiglare film 3 is good. The temperature (coating temperature) of the liquid composition for forming an antiglare film sprayed from the electrostatic coating gun is also the same as described above.

According to the manufacturing method of the embodiment described above, the liquid composition for forming an antiglare film is preferably sprayed using an electrostatic coating device provided with a rotary atomizing head to obtain excellent antiglare properties. The antiglare film 3 having can be formed. This is because the droplets of the liquid composition for forming an antiglare film have a slower speed than the case where a conventionally used spray method other than the electrostatic coating device (for example, a method using a two-fluid nozzle) is applied. The liquid medium (C) in the adhered droplets rapidly volatilizes on the transparent substrate 2 so that the droplets do not spread easily on the transparent substrate 2 and the shape at the time of adhesion is sufficiently maintained. It is thought that this is because the film is formed in the state of being in a state of being.

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 the 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 the present embodiment. FIG. 3 is a schematic bottom view showing the substrate 10 with an antiglare film. The substrate 10 with an antiglare film shown in FIGS. 2 and 3 includes a low-reflection film 4 and an antifouling film 5 on the antiglare film 3 of the substrate 1 with an antiglare film shown in FIG. It differs from the antiglare film 1 in that the printing layer 6 is provided on the peripheral edge of the surface of the substrate 1 opposite to the antiglare film 3, but other configurations are common. Therefore, in the substrate 10 with an antiglare film, the same reference numerals are given to the configurations corresponding to the substrate 1 with an antiglare film, and detailed description thereof will be omitted. It is not necessary to include all of the low-reflection film 4, the antifouling film 5, and the printing layer 6, and one or two of them may be provided.

(Low reflective film)
The low-reflection film 4 is provided on the antiglare film 3 and is a film that suppresses the reflection of incident light on the transparent substrate 2 and makes the reflected image unclear. As a configuration of the low reflective film 4, for example, 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. can. The low reflection film 4 is not limited as long as it can suppress the reflection of light.

When the low-refractive index film 4 has a structure in which a high-refractive index layer and a low-refractive index layer are laminated, the high-refractive index layer and the low-refractive index layer in the low-refractive index film may be included in one layer each. , Each may include two or more layers. When two or more layers of the high refractive index layer and the low refractive index layer are included, a form in which the high refractive index layer and the low refractive index layer are alternately laminated is preferable.

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

The low-refractive-index film 4 is a layer in which the high-refractive index layer is selected from niobium oxide, tantalum oxide, and silicon nitride from the viewpoint of productivity and refractive index, and the low-refractive index layer is a layer made of silicon oxide. The configuration is preferable.

The method for forming each layer constituting the low-reflection 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 and the like can be used. Among these film forming methods, it is preferable to use the sputtering method 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, in the case of forming a film by the pulse sputtering method, the transparent substrate 2 is placed in a chamber having a mixed gas atmosphere of an inert gas and an oxygen gas, and the target is set as a material for forming an adhesion layer so as to have a desired composition. Select and form a film. At this time, the gas type of the inert gas in the chamber is not particularly limited, and various inert gases such as argon and helium can be used. When a high-refractive index layer and a low-refractive index layer are formed by the pulse sputtering method, the layer thickness of each layer can be adjusted by, for example, adjusting the discharge power, adjusting the film forming time, and the like.

In the substrate 10 with an antiglare film of the present embodiment, the antiglare film 3 contains silica as a main component, and a low reflective film 4 composed of a high refractive index layer and a low refractive index layer is formed on the antiglare film 3. In addition to high anti-glare and low haze rate, excellent low reflectivity can be achieved.

(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 has an effect that even if organic substances and inorganic substances adhere to the surface, the adhered substances can be easily removed by cleaning such as wiping. be.

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

The thickness of the antifouling film 5 is preferably 2 to 30 nm, more preferably 5 to 20 nm, for example, when the antifouling film 5 is made of a fluorine-containing organosilicon compound film. When the film thickness of the antifouling film 5 is 2 nm or more, the antifouling film 5 is excellent in scratch resistance as well as antifouling property. Further, when the film thickness of the antifouling film 5 is 30 nm or less, the antiglare property and the optical characteristics such as haze of the antiglare film-attached substrate 10 in the state where the antifouling film 5 is formed are good.

As a method for forming a fluorosilicon-containing organosilicon compound film, a composition of a silane coupling agent having a fluoroalkyl group such as a perfluoroalkyl group; a fluoroalkyl group containing a perfluoro (polyoxyalkylene) chain is used as a low-reflection film. On the surface of the low reflective film 4, a method of applying 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-treating as necessary, or a fluorosilicon-containing organosilicon compound is applied to the surface of the low-reflection film 4. Examples thereof include a vacuum vapor deposition method in which heat treatment is performed as necessary after vapor deposition. 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-containing composition containing a fluorine-containing hydrolyzable silicon compound.

The film-forming composition is not limited as long as it is a composition containing a fluorine-containing hydrolyzable silicon compound and can form a film by a vacuum vapor deposition method. The hydrolyzable silicon compound may contain 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 organic silicon compound film of the present embodiment is specifically selected from the group consisting of a perfluoropolyether group, a perfluoroalkylene group and a perfluoroalkyl group1. Fluorine-containing hydrolyzable silicon compounds having one or more groups can be mentioned. These groups exist as fluorine-containing organic groups that are directly attached to the silicon atom of the hydrolyzable silyl group via a linking group.

A film-containing composition for forming a film containing such a fluorine-containing hydrolyzable silicon compound is adhered to and reacted with the surface of the low-reflection film 4, to obtain a fluorine-containing organosilicon compound film. As for the specific vacuum vapor deposition method and reaction conditions, conventionally known methods, conditions and the like can be applied.

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 the CF ₃ (CH ₂ ) _n -group inside the film, so that the porosity is suppressed and the film-forming composition permeates into the porosity. Does not occur. Therefore, an antifouling film 5 having excellent adhesion to the antiglare film 3 and having excellent antifouling properties can be obtained.

The antifouling film 5 can be formed by applying a film-forming composition using, for example, a known spray device or the like. The coating film forming composition is applied by moving the nozzle of the spray device in parallel with respect to the antiglare film-attached substrate 1 in the first direction from one end to the other end. The nozzles that reach the other end are translated by a predetermined interval (hereinafter referred to as pitch) in a second direction perpendicular to the first direction. Translate the nozzle again from the other end to one end. This is repeated, and the coating area is applied so as to cover the entire surface of the antiglare film-attached substrate 1.

When the pitch is small, the nozzle reciprocates more frequently on the antiglare film-equipped substrate 1 than when the pitch is large. Therefore, by increasing the moving speed of the nozzle, the discharge amount per unit area can be made constant. 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 in Table 1, even when the discharge amount per unit area is constant, the nozzle movement speed is increased and the pitch is reduced rather than the nozzle movement speed is slowed and the pitch is increased. It can be seen that the coating efficiency of the film-forming composition is better. In particular, setting the pitch to 12 mm or less is preferable because the coating efficiency of the film-forming composition is improved. The results in Table 1 are obtained by applying a film-forming composition to a glass plate on which an antiglare film has not been formed and measuring the amount of F atoms. The tendency is similar.

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

The print layer 6 is formed in a desired color, for example, with a width that allows the wiring circuit and the adhesive portion to be concealed. The print layer 6 is formed using, for example, ink.

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

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

Among the inorganic inks and organic inks, the use of organic inks is preferable because the drying temperature is low. Further, from the viewpoint of chemical resistance, organic ink containing a pigment is preferable.

The print layer 6 is formed by printing the ink on a predetermined portion on a surface opposite to the main surface of the transparent substrate 2. Examples of the printing method include a bar coating method, a reverse coating method, a gravure coating method, a die coating method, a roll coating method, a screen method, an inkjet method, etc., which can be easily printed and printed on various substrates in a desired size. Therefore, the screen printing method is preferable. The print layer 6 may be a plurality of layers in which a plurality of layers are laminated, or may be a single layer. When the print layer 6 is composed of a plurality of layers, the print layer 6 can repeatedly print and dry the ink.

When the substrate 10 with an antiglare film provided with the print layer 6 is used as a front plate of an image display device or the like, the substrate 10 with an antiglare film is arranged on the image display device side so that the print layer side is arranged on the image display device side. It is provided on the visual side (front side) of. When the image display device provided with the antiglare film-equipped substrate 10 is visually recognized from the front surface, a black printing portion is provided on the peripheral edge portion thereof, and a display portion is provided on the inside of the peripheral edge portion via the antiglare film 3 and the transparent substrate 2, respectively. Is visually recognized.

At this time, if the haze of the front plate is high, the black printed part looks cloudy, and when the display part becomes black when the display panel is not energized, the black printed part and the black part of the display part seen through the front board are black. Boundaries may be created between the two, which may spoil the aesthetics. Since the substrate 10 with an antiglare film of the present embodiment has a low haze, it is difficult for a boundary to occur between the black printing portion and the black color of the display portion seen through the front plate, and the substrate 10 is continuously visible without these boundaries. It will be aesthetically pleasing.

<Use of substrate with antiglare film>
Applications of the substrate with antiglare film of the present invention are, for example, transparent parts for vehicles (headlight cover, side mirror, front transparent substrate, side transparent substrate, rear transparent substrate, instrument panel surface, etc.), meter, building window, etc. , Show windows, displays (notebook computers, monitors, LCDs, PDPs, ELDs, CRTs, PDAs, etc.), LCD color filters, touch panel boards, pickup lenses, optical lenses, eyeglass lenses, camera parts, video parts, CCD covers. 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 plate, cold cathode tube, etc.), backlight unit parts LCD brightness improvement film (Prism, semi-transmissive film, etc.), LCD brightness improving film, organic EL light emitting element parts, inorganic EL light emitting element parts, phosphor light emitting element parts, optical filters, end faces of optical parts, lighting lamps, covers for lighting equipment, amplified lasers Light sources, antireflection films, polarizing films, agricultural films, etc.

The substrate with an antiglare film of the present invention is preferably used as an interior article of a transport aircraft, and more preferably an in-vehicle article, because it can achieve both excellent antiglare property and low haze at a high level. As the in-vehicle article, an in-vehicle system (car navigation system, instrument panel, head-up display, dashboard, center console, shift knob) including an image display device is preferable.

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

<Optical characterization method>
(Skewness Rsk of roughness curve, arithmetic mean roughness Ra, element average length RSm of roughness curve)
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 specified in JIS B0601-2001 using SURFCOM 1500SD3-12 manufactured by Tokyo Seimitsu Co., Ltd., respectively. Measured according to the method used.

(Average film thickness)
The film thickness of the antiglare film was measured as follows. The cross section of the antiglare film treated by 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 shooting range can be calculated from the scale bar and the number of pixels in the direction perpendicular to the film thickness by counting the number of pixels in the entire cross section of the antiglare film on digital data. Further, it may be calculated using commercially available image processing software. In the SEM observation, the observation was performed with a field of view of 70 μm or more in the direction perpendicular to the film thickness, 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% by mass of fluorine (F) was used as a standard sample. Using ZSX100e manufactured by Rigaku Co., Ltd., a measurement diameter of 30 mm, a measurement line FKα, a filter OUT, and a slit Std. , Spectral crystal RX35, detector PC, PHA100-300, peak angle 38.794 deg. (20 sec), B. 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, respectively. The F amount was calculated by dividing the measured value of the fluorine content in the measurement target film measured above by the measured value of the fluorine content of the standard sample.

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

(60 ° mirror gloss (Gloss))
The 60 ° mirror glossiness (%) was measured as the glossiness of the surface of the substrate with the antiglare film. The 60 ° mirror gloss is the method specified in the 60 ° mirror gloss of JIS Z8741: 1997, using an all-in-one gloss meter (Rhоpоint IQ, manufactured by Lowpoint Instruments), and the back surface (on the opposite side of the main surface). A black felt was laid on the surface) side to eliminate the reflection on the back surface of the substrate with the antiglare film, and the measurement was performed at almost the center of the antiglare film.

(Diffusion)
The antiglare index value of the substrate with a glare film was measured by the following procedure using a variable angle photometer manufactured by Nippon Denshoku Industries Co., Ltd., GC5000L.

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

Next, the angle θ for measuring the brightness of the light reflected on the main surface of the antiglare film substrate 1 is changed in the range of 5 ° to 85 °, and the same operation is performed to perform the same operation. The brightness distribution of the reflected light in the range of 5 ° to 85 ° reflected on the main surface of the above is measured and totaled, and the value is defined as "the brightness of the total reflected light".

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

(Measurement of glare index value (Sparkle))
A substrate with an antiglare film is placed on the display surface of a liquid crystal display (i-Phone4, manufactured by Apple Incorporated, pixel density 326ppi) so that the main surface (the surface having irregularities) on which the antiglare film is formed faces up. The glare index value was measured using an eye scale ISC-A manufactured by Eye System Co., Ltd.

(Temperature durability)
The durability of the antiglare film is such that the haze change before and after the test is 0.5% or more in the heat shock test (treatment of alternately repeating the conditions of -40 ° C for 30 minutes and 90 ° C for 30 minutes for 500 cycles). Those that were present were rated as "bad", and those that were less than 0.5% were rated as "good".

(Gun height)
The distance from the lowermost end of the center of the electrostatic coating gun (electrostatic automatic gun described later) for spraying the antiglare film forming solution-like composition to the surface of the transparent substrate is indicated 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 Shinetsu Silicone Co., Ltd.) was used.

(Scale particle dispersion)
As the scaly particle dispersion, an SLV solution (a dispersion of scaly silica particles obtained by crushing Sunlabry LFS HN150 manufactured by AGC SIITEC and dispersed in water) was used. The average particle size of the scaly silica particles in the SLV solution is 175 nm, the average aspect ratio (average particle size / average thickness) is 80, and the scaly silica particle concentration is 5% by mass.

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

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

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

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

The surface of the chemically strengthened glass substrate (transparent substrate) was washed with a neutral detergent, then washed with pure water, and dried.

The liquid composition for forming an antiglare film obtained above was applied on a transparent substrate after washing and drying by an electrostatic coating device (liquid electrostatic coater, manufactured by Asahi Sanac Co., Ltd.) to form a coating film. As the electrostatic coating gun of the electrostatic coating device, a rotary atomization type electrostatic automatic gun (manufactured by Asahi Sanac Co., Ltd., Sunbell, ESA120, cup diameter 70 mm) 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%. A washed transparent substrate previously heated to 30 ° C. ± 3 ° C. was placed on the chain conveyor of the electrostatic coating device via a stainless steel plate. Electrostatic coating due to the gun height shown in Table 2 on the top surface of the glass substrate (the surface opposite to the surface in contact with molten tin during manufacturing by the float method) while transporting at a constant speed of 3.0 m / min on a chain conveyor. By the coating method, a liquid composition for forming an antiglare film having a temperature within the range of 25 ± 3 ° C. is applied twice, and then baked in the air at 450 ° C. for 30 minutes to form an antiglare film to form an antiglare film. A substrate was obtained. The above-mentioned evaluation was performed on the obtained substrate with an antiglare film. The results are shown in Table 3.

(Examples 2-28)
The prevention of each example was carried out by the same operation as in Example 1 except that the type and amount of the organic silane, the amount of the tetraethoxysilane and the SLV solution, and the amount of each component to the total amount of the solid content were prepared in the ratio shown in Table 2. A liquid composition for forming a glazing film was obtained. Using the obtained liquid composition for forming an antiglare film, the gun height in Table 2 was set, 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. Was done. The results are shown in Table 3. In Example 16 only, the number of times the liquid composition for forming an antiglare film was applied was set to one.

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

(Measurement condition)
Spray type: Rotary atomization type electrostatic automatic gun Gun height: 235 mm from the substrate surface to the cup tip
Measurement position: Liquid composition for forming an antiglare film when measured at a height of 60 mm from the surface of the glass substrate and the measurement position is shifted horizontally from directly below the center of the cup of the rotary atomization type electrostatic automatic gun. Position where the frequency of flying drops is maximum Number of measured particles: 1000 pieces Calculation of average diameter: 1000 pieces The Sauter mean diameter was calculated for each measured particle size.
Measurement area at each measurement position: 2623 μm (height) x 1475 μm (width) x 1795 μm (depth)

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

From Tables 2 and 3, in the substrates with antiglare film (Examples 1 to 17) of Examples, the antiglare index value was 0.05 or more and the haze was 8 or less, and the excellent antiglare property was obtained. It can be seen that both low haze and low haze can be achieved. In the comparative examples of the substrate with antiglare film (Examples 18 to 28), the antiglare index value was good, but the haze was high and the visibility was deteriorated. This is considered to be due to the fact that Rsk exceeds 1.3. Therefore, according to the present invention, it has been found that a substrate with antiglare property having both excellent antiglare property and low haze can be obtained.

<Evaluation test for wiping off oils and fats>
The oil and fat wiping property was carried out as follows. 0.05 g of Nivea Cream manufactured by Kao Corporation was placed as oil and fat on the antiglare film of the substrate with the antiglare film. Next, the oil and fat was transferred to the silicon stopper by placing a silicon stopper having a bottom surface of φ15 mm on which a load of 1 kg was placed. Subsequently, a silicon stopper carrying a load of 1 kg to which the fat and oil was transferred was placed on a paper waste cloth for 80 seconds to remove excess fat and oil. Subsequently, a silicon stopper with a load of 1 kg was placed on the sample surface, and oils and fats were transferred to the sample surface to prepare an evaluation sample.
It takes time to transfer the oil and fat of the evaluation sample to a strip-shaped wiping cloth (Toray Industries, Inc. Toraysee MK MK24H-CPMK) with a bottom area of 20 mm x 20 mm and a load of 100 g on it so that the oil and fat cannot be visually recognized. I counted the number of times. The part of the wiping cloth that came in contact with the oil was not reused, and the clean part was always wiped so that it touched the oil. If it can be wiped within 20 times, it is regarded as "good" as a good wipeability, and if it is wiped within 10 times, it is regarded as very good and "excellent". If wiping took 21 times or more, it was regarded as "defective" and the results are shown in Table 4.

<Scratch resistance test>
Scratch-resistant sample surface, with Kanakin No. 3 (Japanese Standards Association JIS L 0803 compliant test attachment white cloth cotton) attached to an indenter with a bottom area of 20 mm × 20 mm, with a load of 1 kg, rubbing speed per minute It was rubbed 100,000 times with 80 reciprocations and a rubbing distance of 40 mm. If the surface of the sample after rubbing does not change at all visually, it is "excellent" as having very good scratch resistance, and if there are no more than 3 scratches with a width of 0.8 mm or less, it is "good" as having good scratch resistance. And said. When scratches having a width of 0.8 mm or more are confirmed or four or more scratches having a width of 0.8 mm or less are confirmed, the scratch resistance is regarded as "poor" and the results are shown in Table 4.

From Table 4, among the examples, the antiglare film-attached substrates (Examples 1 to 17) were also good in oil and fat wiping property and scratch resistance. It is thought that this is related to Rsk, and if Rsk is too large, the convex shape of the uneven shape derived from the antiglare film becomes sharp, so it is difficult to remove oil and fat, and the tip of the convex shape is easily destroyed, so that it is scratch resistant. It is thought that the sex will be low. In the substrate with an antiglare film of the present invention, by setting the Rsk to 1.3 or less, not only good optical characteristics are obtained, but also oil and fat wiping properties related to fingerprint wiping and wear resistance are related. Good results were also obtained for scratch resistance. Furthermore, it was also found that by setting the Rsk to less than 1.07, better oil and fat wiping resistance and scratch resistance can be obtained.

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

Claims (13)

It has a transparent substrate and an antiglare film provided on the transparent substrate.
When the antiglare film is mainly composed of silica and a glass having a specific gravity of 2.48 containing 1.0% by mass of fluorine is used as a standard sample, the measured value of the fluorine content of the antiglare film is used as the standard. The value (F amount) divided by the measured fluorine value of the sample is 0.23 to 2.5.
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 element of the roughness curve on the surface of the antiglare film is 10 μm or more and 20.2 μm or less.
The 60 ° mirror gloss on the surface of the antiglare film is 82% or more, and
A substrate with an antiglare film, characterized in that the arithmetic mean roughness Ra is 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 substrate with an antiglare film according to any one of claims 1 to 3, 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 the average length RSm of the 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 any one of claims 1 to 5, wherein the skewness Rsk of the roughness curve of the surface of the antiglare film is 1.05 or less. The substrate with an antiglare film according to any one of claims 1 to 6, wherein the arithmetic mean 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 the average length RSm of the element of the roughness curve on the surface of the antiglare film is 11 μm or more. The substrate with an antiglare film according to any one of claims 1 to 8 , wherein the 60 ° mirror surface gloss on the surface of the antiglare film is 135% or less. The substrate with an antiglare film according to any one of claims 1 to 9 , wherein the transparent substrate is a glass substrate. The substrate with an antiglare film according to any one of claims 1 to 9 , wherein the transparent substrate is a chemically strengthened glass substrate. The substrate with an antiglare film according to any one of claims 1 to 11 , wherein the transparent substrate has a curved surface. The substrate with an antiglare film according to any one of claims 1 to 12 , wherein the transparent substrate has a thickness of 0.1 to 5 mm.

Images