JP2018063419A - Substrate with antiglare film, liquid composition for forming antiglare film and method for manufacturing substrate with antiglare film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a substrate with an antiglare film, which has an excellent antiglare property and a reduced haze such that, for example, when a black printed layer is seen through the substrate with an antiglare film, cloudiness is less likely to be visible on the black printed layer, a liquid composition for forming an antiglare film for forming the above antiglare film, and a method for manufacturing a substrate with an antiglare film.SOLUTION: A substrate 1 with an antiglare film has a transparent substrate 2 and an antiglare film 3 disposed on the transparent substrate 2. The antiglare film 3 essentially comprises silica and contains a CF(CH)- group, where n is an integer of 1 to 6, therein; and the antiglare film 3 has a surface roughness curve skewness Rsk of 1.3 or less and an arithmetic average roughness Ra of 0.01 μm or more.SELECTED DRAWING: Figure 1

Description

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

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

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

  Further, there is a method in which a low reflection film is disposed on the display surface of the image display device, and reflection of incident light to the transparent substrate itself is suppressed to blur the reflected image. As the low reflection 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. Moreover, the film | membrane formed from a fluorine-containing hydrolysable organosilicon compound is also known as a low reflection film (for example, refer patent documents 2-5).

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

  By disposing the anti-glare film on the display surface of the image display device, it is possible to suppress a decrease in the visibility of the image due to external light reflected on the display surface. However, at the same time, the higher the antiglare property, the higher the haze of the antiglare film.

  The front plate of the image display device is formed with an antiglare film on the viewing side, and black printing is performed on the non-viewing side surface where the antiglare film is not provided for the purpose of improving design and aesthetics. A light shielding part such as a layer is provided. At this time, when the haze of the antiglare film is high, when the black print layer is viewed through the antiglare film, white turbidity may be visually recognized, resulting in a problem of deteriorating the aesthetic appearance.

  The present invention relates to a substrate with an antiglare film having excellent antiglare properties and a low haze, a liquid composition for forming an antiglare film for forming the antiglare film, and a method for producing the 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, and the antiglare film contains silica as a main component, and a CF ₃ (CH ₂ ) _n -group (where n is 1 to 1). The anti-glare film surface roughness curve has a skewness Rsk of 1.3 or less and an arithmetic average roughness Ra of 0.01 μm or more.

(2) A liquid composition for forming an antiglare film comprising trifluoropropyltrimethoxysilane, scaly silica particles, and a liquid medium.
(3) A liquid coating composition for forming an antiglare film containing trifluoropropyltrimethoxysilane, scaly silica particles, and a liquid medium is applied on a transparent substrate by a spray coating method to form a coating film, By baking the coating film, the main component is silica, CF ₃ (CH ₂ ) _n — group (where n is an integer of 1 to 6), and the surface roughness curve skewness Rsk is 1. A method for producing a substrate with an antiglare film, wherein an antiglare film having an arithmetic average roughness Ra of 0.01 μm or more is formed on the transparent substrate to produce a substrate with an antiglare film.

It should be noted that the following definitions of terms apply throughout the present specification and claims.
“Silica precursor” means a substance capable of forming a matrix mainly composed of silica as a component involved in network bonding.
“Containing silica as a main component” means containing 50 mass% or more of SiO ₂ .
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.
“Scaly particle” means a particle having a flat shape. The shape of the particles can be confirmed using a transmission electron microscope (hereinafter also referred to as TEM).
The “average particle size” of the scaly particles is the particle size at which the particle size (longest length) distribution obtained on a volume basis is 50% in the cumulative volume distribution curve with the total volume of the distribution being 100%, that is, the volume-based cumulative 50 It means% diameter (D50). The particle size distribution is obtained from a frequency distribution and a cumulative volume distribution curve measured with a laser diffraction / scattering particle size distribution measuring apparatus.
“Aspect ratio” means the ratio of the particle diameter to the thickness of the particles (longest length / thickness), and “average aspect ratio” is the average value of the aspect ratios of 50 randomly selected particles It 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.

ADVANTAGE OF THE INVENTION According to this invention, while having the outstanding anti-glare property, the base | substrate with an anti-glare film | membrane which made haze low can be obtained.
ADVANTAGE OF THE INVENTION According to this invention, while having the outstanding anti-glare property, the manufacturing method of the liquid composition for glare-proof film formation for obtaining the base | substrate with an anti-glare film which lowered haze, and the base | substrate with an anti-glare film can be provided.

It is a cross-sectional schematic diagram showing the base | substrate with an anti-glare film which concerns on 1st Embodiment. It is a cross-sectional schematic diagram showing the base | substrate with an anti-glare film which concerns on 2nd Embodiment. It is a bottom face schematic diagram of the base | substrate with a glare-proof 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. A 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 includes a CF ₃ (CH ₂ ) _n — group (where n is an integer of 1 to 6, and 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 average roughness Ra is 0.01 μm or more. The antiglare film-coated substrate 1 has an antiglare film 3 having the above-described characteristics, and thus has an excellent antiglare property and has a low haze. For example, the black printed layer is seen through the antiglare film-coated substrate 1. In this case, it is possible to prevent the cloudiness from being visually recognized. Hereinafter, each structure of the base | substrate 1 with an anti-glare film is demonstrated.

(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 provided with antiglare property by an antiglare film. For example, glass, resin, or a combination thereof (composite material, laminated material) Etc.) is preferably used. Examples of the glass include soda lime glass, borosilicate glass, aluminosilicate glass, and alkali-free glass. Examples of the resin include polyethylene terephthalate, polycarbonate, triacetyl cellulose, polymethyl methacrylate, and the like.

  Moreover, it does not specifically limit about the form of the transparent base | substrate 2, For example, it can be set as the plate shape which has rigidity, the film shape which has a softness | flexibility, etc.

  The surface of the transparent substrate 2 on which the antiglare film 3 is formed (hereinafter also referred to as “main surface”) may be smooth or may have irregularities. From the point of usefulness of providing the antiglare film 3 (a point where desired optical characteristics can be obtained), smoothness is preferable. The antiglare film 3 provided on the transparent substrate 2 may not be formed over the entire main surface of the transparent substrate 2. That is, the antiglare film 3 may be formed in a predetermined region to which the 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 is not limited to a flat shape as illustrated, and may be a shape having a curved surface. In this case, the whole may be configured by a curved surface, or may be configured by a curved surface portion and a flat portion. In recent years, various devices including an image display device (televisions, personal computers, smartphones, car navigation systems, etc.) in which the display surface of the image display device is curved 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 producing the glass substrate is not particularly limited. The glass substrate can be manufactured by putting a desired glass raw material into a melting furnace, heating and melting and clarifying, then supplying it to a molding apparatus to form molten glass and slowly cooling it. 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 downdraw method, or the like can be used.

  The thickness of the transparent substrate 2 can be appropriately selected depending on the application. When a glass substrate is used as the transparent substrate 2, the thickness is preferably 0.1 to 5 mm, and 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 tempered is preferable. The strength of the glass is improved by the strengthening treatment, and for example, the thickness can be reduced while maintaining the strength. An antiglare film may be formed on the unstrengthened glass substrate, and then a tempering treatment may be performed.

  Examples of the strengthening treatment include a treatment for forming a compressive stress layer on the glass plate surface by an air cooling strengthening method (physical strengthening method) or a chemical strengthening method. The compressive stress layer on the surface of the glass substrate improves the strength of the glass substrate against scratches and impacts. Among 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 lower than the strain point temperature of the glass, and ions (for example, sodium ions) on the surface of the glass plate are exchanged for ions having a larger ion radius (for example, potassium ions). To do. Thereby, compressive stress arises in a glass plate surface layer.

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

  The substrate 1 with an antiglare film may have a functional layer such as an undercoat layer, an adhesion improving layer, or a protective layer between the transparent substrate 2 and the antiglare film 3. The undercoat layer functions as an alkali barrier layer or a wide band low refractive index layer. The undercoat layer is preferably a layer formed by applying an undercoat forming composition containing a hydrolyzate of alkoxysilane (sol-gel silica) to the transparent substrate 2.

(Anti-glare film)
The antiglare film 3 has a concavo-convex structure on the surface, and diffuses external light irradiated on the transparent substrate 2 to suppress surface reflection of external light. For example, in various image display devices such as a liquid crystal display (LCD) and a plasma display (PDP), in general, when external light such as indoor lighting (fluorescent lamp, etc.) or sunlight is reflected on the display surface, it is visually recognized by a reflected image. Sex is reduced. On the other hand, by providing the antiglare film 3 on the transparent substrate 2 and irregularly reflecting the external light, it is possible to suppress a decrease in visibility due to the reflected image.

The antiglare film 3 is mainly composed of silica 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 includes, for example, a silica precursor (fluorinated silica precursor) (A) containing a CF ₃ (CH ₂ ) _n — group, a scaly particle (B), and a liquid medium (C). It forms using the liquid composition for anti-glare film formation containing. In this case, the fluorine-containing silica precursor (A) forms a matrix containing silica as a main component and containing CF ₃ (CH ₂ ) _n — groups. In addition, the scale-like particles (C) are dispersed in the matrix to form the antiglare film 3. A method of 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 during heating. Therefore, the formation of a porous antiglare film 3 obtained by baking the liquid composition for forming an antiglare film can be suppressed. Moreover, the anti-glare film 3 exhibits excellent chemical resistance and moisture resistance by including a CF ₃ (CH ₂ ) _n — group having a fluorine atom inside the film.

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

  The arithmetic average roughness Ra of the surface of the antiglare film 3 is 0.01 μm or more. The arithmetic average roughness Ra is a value obtained by averaging the absolute value deviations from the reference plane in the roughness curve included in the reference length taken on the reference plane. When the arithmetic average roughness Ra is 0.01 μm or more, the antiglare film 3 exhibits excellent antiglare properties. The antiglare film 3 preferably has an arithmetic average roughness Ra of 0.1 μm or less. Arithmetic average roughness Ra of 0.1 μm or less is one factor for enabling the antiglare film 3 to achieve both excellent antiglare property and low haze without excessively increasing the haze.

  The skewness Rsk of the surface roughness curve of the antiglare film 3 is 1.3 or less. Here, the skewness Rsk of the roughness curve represents the cube average of the height Z (x) at the reference length made dimensionless by the cube of the root mean square height (Zq), and is relative to the uneven average line. It is an index representing 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 sharp, and when the negative value (Rsk <0) is uneven, the uneven shape is biased toward the convex side. The protrusion shape tends to become dull. The haze is lower when the protruding shape of the roughness curve is dull than when it is sharp.

  The skewness Rsk of the surface roughness curve of the antiglare film 3 is 1.3 or less, which is one factor for maintaining excellent antiglare properties and reducing haze. In addition, it is possible to suppress the white turbidity from being visually recognized when the black printed portion is viewed through the base 1 with the 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 haze.

  The average length RSm of the elements of the surface roughness curve of the antiglare film 3 is preferably 18 μm or less, more preferably 17.8 μm or less, and further preferably 17.5 μm or less. RSm is preferably 10 μm or more, more preferably 11 μm or more, and further preferably 14 μm or more. This is because if the average length RSm of the roughness curve element is too large, the haze and glare index value (Sparkle) of the substrate 1 with an antiglare film tends to increase, 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 values of the liquid composition for forming the antiglare film when the antiglare film 3 is formed. Composition (solid content concentration, primary particle size, secondary particle size, content of each component, etc.), application conditions of liquid composition for forming antiglare film on transparent substrate 2 (for example, applied by spray method) In this case, it can be adjusted by the spray pressure, the liquid amount, the temperature of the transparent substrate, the number of coatings, etc. of the liquid composition for forming an antiglare film.

  The arithmetic average 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 defined in JIS B0601-2001 using SURFCOM 1500SD3-12 manufactured by Tokyo Seimitsu Co., Ltd. Can be measured according to the method.

  The antiglare film 3 preferably has an average film thickness of 15 to 1500 nm. When the average film thickness of the anti-glare film 3 is 15 to 50 nm, it is easy to lower the haze or lower the glaring index value. Since the average film thickness of the antiglare film 3 is 50 nm or more, sufficient antiglare property can be imparted to the substrate 1 with the antiglare film, which is more preferable. The average film thickness of the antiglare film 3 is 1500 nm or less, which is one factor for achieving both optical characteristics such as an antiglare index value and haze in a favorable range. Here, the average film thickness of the anti-glare film 3 is obtained by processing the cross section of the anti-glare film 3 by focused ion beam processing, and then observing it with a scanning microscope (SEM) at a magnification of 10,000 times, for example. It can be measured by measuring the thickness from the interface between the transparent substrate 2 and the antiglare film 3 to the surface of the antiglare film 3 over the entire range. The film thickness can be calculated using digital data obtained by SEM and image processing software.

  The anti-glare film 3 may be formed so as to cover the entire main surface of the transparent substrate 2 (or a region to which anti-glare properties are imparted on the main surface) without any gap. For example, a preferable anti-glare index described later is used. 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 forming the antiglare film, for example, the antiglare film 3 is formed in an island shape. May be. When the thickness of the antiglare film 3 is, for example, 300 nm or less, the antiglare film 3 is discontinuously formed on the main surface of the transparent substrate 2, and the antiglare film is formed on a part of the main surface of the transparent substrate 2. Otherwise, the transparent substrate 2 may be exposed.

  The antiglare film 3 may be composed of a first convex portion having a diameter of 1 μm or more and a second convex portion having a diameter of less than 1 μm, and the first convex portions or the second convex portions, Or the structure which the 1st convex part and the 2nd convex part overlapped may be sufficient. Such a surface structure can be observed by analyzing laser microscope measurement data with image processing software.

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

  The fluorine content in the antiglare film 3 is obtained by dividing the glass with a specific gravity of 2.48 containing 1.0% by mass of fluorine (F) as a standard sample and dividing the fluorine measurement value of the antiglare film 3 by the fluorine measurement value of the standard sample. The fluorine content is preferably 2.5 or less, more preferably 2.2 or less, and even more preferably 1.8% or less. This is to suppress an increase in RSm. The amount of F is preferably 0.23 or more, more preferably 0.3 or more, and still more preferably 0.4 or more. This is for temperature and humidity durability. The amount of F can be measured, for example, by the following method. Using ZSX100e manufactured by Rigaku Corporation, measurement diameter 30 mm, measurement line F-Kα, filter OUT, slit Std. , Spectral crystal RX35, detector PC, PHA100-300, peak angle 38.794 deg. (20 sec), B.E. G. Angle 43.000 deg. Under the condition of (10 sec), the fluorine content (% by mass) of the measurement target film and the fluorine content in the standard sample are measured. The F content is calculated by dividing the measured fluorine content of the measurement target film 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 F amount in the antiglare film 3 is measured after removing the antifouling film. The antifouling film can be removed by corona treatment or plasma treatment. In addition, 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 depends on the composition of the liquid composition for forming an antiglare film, the amount of CF ₃ (CH ₂ ) _n -group in the liquid composition for forming an antiglare film, and a fluorine-containing silica precursor ( It can be adjusted by the type of A), the amount of CF ₃ (CH ₂ ) _n -group of the fluorine-containing silica precursor (A), and the like.

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

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

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

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

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

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

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

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

  The glare index value (Sparkle) of the surface of the substrate 1 with antiglare film is preferably 90 or less, more preferably 80 or less, and even more preferably 70 or less. The glare index value is determined by placing an anti-glare film-coated substrate on the display surface of a liquid crystal display so that the anti-glare film-forming surface (surface having irregularities) is on top, and an eye scale ISC-A made by Eye System Co., Ltd. Can be measured. The larger the value of the glare index value, the greater the glare. Note that glare means that when the substrate 1 with an antiglare film is used for a pixel matrix type display element, a large number of light particles having a longer period than the pixel matrix are observed on the surface of the substrate 1 with an antiglare film. The degree of hindering visibility means that the lower the glare, the less likely the light particles are observed, and the better the visibility.

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

<Liquid composition for antiglare film formation>
The antiglare film 3 can be formed using a liquid composition for forming an antiglare film. The liquid composition for forming an antiglare film includes a silica precursor (A) containing a CF ₃ (CH ₂ ) _n — group, scaly particles (B), and a liquid medium (C). In addition to the fluorine-containing silica precursor (A), the scaly particles (B) and the liquid medium (C), the liquid composition for forming the antiglare film contains other components as long as the properties of the obtained antiglare film 3 are not impaired. You may contain. Examples of other components include metal oxide precursors other than silica (such as titanium and zirconium as metals), and binders made of thermoplastic resins, thermosetting resins, ultraviolet curable resins, and the like. Hereinafter, each component contained in the liquid composition for forming an antiglare film will be described.

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

Examples of the fluorine-containing silica precursor (A) that can form the matrix include a fluorine-containing silane compound (A1) having a CF ₃ (CH ₂ ) _n — group and a hydrolyzable group bonded to a silicon atom, and The hydrolysis condensate is mentioned, Furthermore, you may contain alkoxysilane, its hydrolysis condensate (sol-gel silica), silazane, etc. The fluorine-containing silane compound (A1) may further have a hydrocarbon group bonded to a silicon atom. A fluorine-containing silica precursor (A) may be used individually by 1 type, or may use 2 or more types together.

  More specifically, the fluorine-containing silica precursor (A) may consist of either or both of the fluorine-containing silane compound (A1) and its hydrolysis condensate, or the fluorine-containing silane compound (A1) and Either one or both of the hydrolysis condensate and either one or both of alkoxysilane and its hydrolysis condensate may be included. From the viewpoint of preventing cracks and film peeling of the antiglare film 3, the fluorine-containing silica precursor (A) includes one or both of the fluorine-containing silane compound (A1) and its hydrolysis condensate, alkoxysilane and its It is preferable that one or both of the hydrolysis condensates are included.

  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 ketoxime group, an alkenyloxy group, an amino group, an aminoxy group, an amide group, an isocyanate group, and a halogen atom. Can be mentioned. Among these, an alkoxy group such as a methoxy group and an ethoxy group, an isocyanate group, and a halogen atom (particularly a chlorine atom) are preferable from the viewpoint of the balance between the stability of the fluorinated 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 group is 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. A valent hydrocarbon group may be used. Examples of the monovalent hydrocarbon group include an alkyl group, an alkenyl group, and an aryl group. Examples of the divalent hydrocarbon group include an alkylene group, an alkenylene group, and an arylene group. Further, in the fluorine-containing silane compound (A1), in place of the hydrocarbon group, —O—, —S—, —CO— and NR′— (where R ′ is a hydrogen atom or It is a monovalent hydrocarbon group.) One or two or more selected from the group may be inserted.

Since the fluorine-containing silane compound (A1) has a fluorine atom in the CF ₃ (CH ₂ ) _n -group, the surface tension of the liquid composition for forming an antiglare film is reduced as compared with the case where it does not have a fluorine atom. To do. For this reason, the skewness Rsk of the roughness curve of the antiglare film 3 obtained by baking this can be lowered, and the haze of the base 1 with the antiglare film can be lowered.

In addition, the CF ₃ (CH ₂ ) _n — group has a fluorine atom, and thus hardly burns during heating. Therefore, the formation of a porous antiglare film 3 obtained by baking the liquid composition for forming an antiglare film can be suppressed. _{Also, CF 3 (CH 2) n} - that groups containing a fluorine atom, can impart excellent chemical resistance and moisture resistance anti-glare film 3.

In the CF ₃ (CH ₂ ) _n — group contained in the fluorine-containing silane compound (A1), n is an integer of 1 to 6, 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 fluorine-containing silane compounds (A1), the values of n in the CF ₃ (CH ₂ ) _n — group may be the same or different.

As the fluorine-containing silane compound (A1), a 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 preferred embodiments are also the same. 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. When q is plural, it may cause a decrease in reactivity, and therefore 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) is an effect of the present invention in addition to one or both of the above-mentioned fluorine-containing silane compound (A1) and its hydrolysis condensate, and one or both of alkoxysilane and its hydrolysis condensate. Other silane compounds that can form a matrix may be included as long as they are not impaired. Other silane compounds include vinyl silane alkoxysilanes (vinyltrimethoxysilane, vinyltriethoxysilane, etc.), epoxy groups alkoxysilane (2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycid Xylpropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, etc.), alkoxysilanes having an acryloyloxy group (3-acryloyloxypropyltrimethoxysilane, etc.), etc. It is done.

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

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

(Scale-like particles (B))
The scaly particles (B) constitute the antiglare film 3 by being contained alone or in a matrix derived from the fluorine-containing silica precursor (A). The scaly particles (B) are not only those that become the scaly particles (B) alone, but also the preferred average particle diameter of the scaly particles (B) of the present embodiment, the thickness of the primary particles, and the secondary particles. In addition, a combination of particles having other shapes and the like, as appropriate, so as to obtain a shape satisfying the thickness, aspect ratio, and the like.

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

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

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

  The thickness of the silica primary particles is preferably 0.001 to 0.1 μm. If the thickness of the silica primary particles is within the above range, scaly silica secondary particles in which one or a plurality of sheets are overlapped with the planes oriented in parallel with each other can be formed. The aspect ratio of the silica primary particles is preferably 2 or more, more preferably 5 or more, and still more preferably 10 or more.

  The thickness of the silica secondary particles is preferably 0.001 to 1 μm, and 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 still more preferably 10 or more. The silica secondary particles are preferably present independently of each other without fusing.

  For the preparation of the liquid composition for forming an antiglare film, a powder that is an aggregate of a plurality of scaly silica particles or a dispersion in which the powder is dispersed in a liquid medium is used. The silica particle concentration in the dispersion is preferably 1 to 80% by mass.

(Liquid medium (C))
The liquid medium (C) has a function as a solvent for dissolving the fluorine-containing silica precursor (A) or a dispersion medium for dispersing, and a function as a dispersion medium for dispersing the scaly particles (B). A liquid medium (C) may be used individually by 1 type, and may use 2 or more types together.

  The liquid medium (C) preferably includes 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.

  If the boiling point of the liquid medium (C1) is 160 ° C. or less, the liquid composition for forming an antiglare film is applied onto the transparent substrate 2 using an electrostatic coating apparatus having an electrostatic coating gun having a rotary atomizing head. Then, the antiglare film 3 formed by firing has more excellent antiglare properties. The boiling point of the liquid medium (C1) is preferably 50 to 150 ° C, more preferably 55 to 140 ° C. If the boiling point of the liquid medium (C1) is equal to or higher than the lower limit of the above range, after the droplets of the liquid composition for forming an antiglare film adhere on the transparent substrate 2, the droplets spread and spread uniformly on the substrate. Easy to form a film. If the boiling point of a liquid medium (C1) is below the upper limit of the said range, it will be easy to form an uneven structure.

  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.), ketones (acetone, methyl ethyl ketone). , Methyl isobutyl ketone, etc.), ethers (tetrahydrofuran, 1,4-dioxane, etc.), cellosolves (methyl cellosolve, ethyl cellosolve, etc.), esters (methyl acetate, ethyl acetate, etc.), glycol ethers (ethylene glycol monomethyl ether) , 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 properties 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 over 160 ° C. Examples of alcohols include diacetone alcohol, 1-hexanol, ethylene glycol, and propylene glycol. Examples of nitrogen-containing compounds 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.

  The content ratio of the liquid medium (C1) with respect 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, the liquid medium (C) preferably contains at least water as the liquid medium (C1). In this case, the liquid medium (C) may be water alone, or may include at least one of the liquid medium (C1) and the liquid medium (C2) other than water. As the liquid medium (C1) other than water, alcohols are preferable, and methanol, ethanol, isopropyl alcohol, and butanol are particularly preferable. Moreover, when a liquid medium (C) contains water, as a liquid medium (C2) contained in a liquid medium (C), diacetone alcohol and propylene glycol are preferable.

(composition)
The liquid composition for forming an antiglare film is either one or both of the fluorine-containing silane compound (A1) and its hydrolysis condensate, and one or both of the tetraalkoxysilane and its hydrolysis condensate. Is included, the proportion of either one or both of the fluorine-containing silane compound (A1) and its hydrolysis-condensation product is based on the total amount (100% by mass) of the SiO ₂ converted solid content of the fluorine-containing silica precursor (A). It is 3 to 50% by mass (more preferably 5 to 30% by mass), and the ratio of one or both of tetraalkoxysilane and its hydrolysis condensate is 50 to 97% by mass (more preferably 70 to 90% by mass). Is preferred. If the content of either one or both of the fluorine-containing silane compound (A1) and its hydrolysis 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 hydrolysis condensate is not less than the lower limit of the above range, the antiglare film 3 is cracked even if the antiglare film 3 is thick. And film peeling can be 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 solid content (100% by mass) in the antiglare film-forming liquid composition. Preferably, 5 to 10% by mass is more preferable. If the content of the scaly particles (B) is not less than the lower limit of the above range, the antiglare property with the antiglare film-coated substrate 1 is exhibited. Moreover, the generation of cracks in the film can be prevented. If content of scale-like particle | grains (B) is below the upper limit of the said range, haze can be made low, maintaining the outstanding anti-glare 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. 0.1-8 mass% is preferable with respect to the whole quantity (100 mass%) of the liquid composition for anti-glare film formation, and solid content concentration of the liquid composition for anti-glare film formation is 0.2-1 mass%. Is more preferable. If solid content concentration is more than the lower limit of the said range, the liquid quantity of the liquid composition for glare-proof film formation can be decreased. If solid content concentration is below the upper limit of the said range, the uniformity of the film thickness of an anti-glare film will improve.

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

  The total content of the fluorine-containing silica precursor (A) and the scaly particles (B) in the antiglare film-forming liquid composition is the total solid content (100 mass) in the antiglare film-forming liquid composition. %) Is preferably 30 to 100% by mass, and more preferably 40 to 100% by mass. If the total content of the fluorinated silica precursor (A) and the scaly particles (B) is not less than the lower limit of the above range, the resulting antiglare film 3 is excellent in adhesion to the transparent substrate 2. If 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 film peeling of the antiglare film 3 can be suppressed.

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

<Method of manufacturing substrate with antiglare film>
The method for producing a substrate with an antiglare film according to this embodiment comprises forming the coating film by applying the liquid composition for forming an antiglare film described above on the transparent substrate 2 by a spray coating method. In this method, the antiglare film 3 is formed by firing to obtain the antiglare film-coated substrate 1. The manufacturing method may include a step of forming a functional layer on the surface of the transparent substrate 2 main body before forming the antiglare film 3 as necessary. Moreover, after forming the anti-glare film 3, another post-processing step may be performed.

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

(Application)
The liquid composition for forming an antiglare film is applied onto the transparent substrate 2 by a spray coating method. This is performed, for example, by charging the liquid composition for forming an antiglare film and spraying it toward the transparent substrate 2 using an electrostatic coating apparatus including an electrostatic coating gun including a rotary atomizing head. 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 apparatus includes a gun body and a rotary atomizing head, and rotates and rotates the rotary atomizing head to atomize and discharge the antiglare film-forming liquid composition supplied to the rotary atomizing head, Spray toward the transparent substrate 2.

  When applying the liquid composition for forming an antiglare film to the transparent substrate 2, the transparent substrate from the nozzle tip of the electrostatic coating gun (that is, the front end of the rotary atomizing head in the spray direction of the liquid composition for forming the antiglare film) The distance up 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, and even more preferably 230 to 240 mm. If the distance to the transparent substrate 2 is too close, the haze of the substrate 1 with antiglare film tends to increase, and if it is too close, the possibility of causing 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.

  In this case, the particle size (discharge particle size) of the droplets of the antiglare film-forming liquid composition sprayed from the electrostatic coating apparatus is preferably 12 μm or less, more preferably 10 μm or less in terms of the Sauter average particle size. When the Sauter average particle diameter is 12 μm or less, the antiglare film 3 exhibits excellent antiglare properties.

Here, the Sauter average particle diameter is a value obtained from the ratio of the total volume of the measured droplets and the total surface area, assuming that the total surface area of the droplets is equal to the total volume. Sauter mean diameter, the particle size of the _{x i,} the _{n i} the number of particles of a particle diameter _{x i,} represented by the following formula (2).

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

(Baking)
Next, the coating film of the liquid composition for forming an antiglare film formed on the transparent substrate 2 is baked.
Thereby, the liquid medium (C) in the coating film is volatilized and removed, and conversion of the fluorine-containing silica precursor (A) remaining in the coating film into a silica-based matrix proceeds (for example, 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). The glare film 3 is formed.

  The coating film may be baked when the antiglare film-forming liquid composition is applied to the transparent substrate 2, by heating the transparent substrate 2 and simultaneously with the application. The antiglare film-forming liquid composition is applied to the transparent substrate 2. After coating, the coating film may be heated. The baking temperature is preferably 30 ° C. or higher. For example, when the transparent substrate 2 is glass, 100 to 750 ° C. is more preferable, and 150 to 550 ° C. is more preferable.

  The surface temperature of the transparent substrate 2 when the antiglare film-forming liquid composition is applied is preferably 60 ° C. or less, preferably 15 to 50 ° C., and more preferably 20 to 40 ° C. If the surface temperature of the transparent substrate 2 is equal to or higher than the lower limit of the above range, the liquid medium (C) contained in the liquid composition for forming an antiglare film evaporates quickly, so that desired irregularities are easily 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 (application temperature) of the antiglare film-forming liquid composition sprayed from the electrostatic coating gun is the same as described above.

  According to the production method of the embodiment described above, the antiglare film-forming liquid composition is preferably sprayed using an electrostatic coating apparatus having a rotary atomizing head, thereby providing excellent antiglare properties. The anti-glare film 3 can be formed. This is because the droplets of the liquid composition for forming an antiglare film have a slower speed than when a conventionally used spray method other than the electrostatic coating apparatus is applied (for example, a method using a two-fluid nozzle). And the liquid medium (C) in the attached droplets volatilizes quickly, so that the droplets are difficult to spread on the transparent substrate 2 and the shape at the time of attachment is sufficiently maintained. This is presumably because the film is formed in a wet state.

  Moreover, in the manufacturing method of embodiment described above, the surface shape of the anti-glare film 3 formed can be controlled by the viscosity of the liquid composition for forming an anti-glare film, 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 according to this embodiment. FIG. 3 is a schematic bottom view showing the base 10 with the antiglare film. A 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. Although it differs from the base 1 with an anti-glare film in that the printed layer 6 is provided on the peripheral edge of the surface opposite to the anti-glare film 3 of the substrate 1 with coating, other configurations are common. Therefore, in the base | substrate 10 with an anti-glare film, the same code | symbol is attached | subjected to the structure corresponding to the base | substrate 1 with an anti-glare film, and the detailed description is abbreviate | omitted. In addition, it is not necessary to provide all of the low reflection film 4, the antifouling film 5, and the printing layer 6, and any 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 reflection of incident light to the transparent substrate 2 and blurs the reflected image. As a configuration of the low reflection film 4, for example, a configuration in which a high refractive index layer having a refractive index of 1.9 or more at a wavelength of 550 nm and a low refractive index layer having a refractive index of 1.6 or less at a wavelength of 550 nm are laminated. it can. The low reflection film 4 is not limited as long as it can suppress light reflection.

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

The materials for the high refractive index layer and the low refractive index layer are not particularly limited, and can be appropriately selected in consideration of the required low reflectivity and productivity. As a material constituting the high refractive index layer, for example, niobium oxide (Nb ₂ O ₅ ), titanium oxide (TiO ₂ ), zirconium oxide (ZrO ₂ ), tantalum oxide (Ta ₂ O ₅ ), silicon nitride (Si ₃ N _4). One or more selected from (1) can be preferably used. The material constituting the low refractive index layer includes 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 materials containing can be preferably used.

  The low reflective film 4 is a layer in which the high refractive index layer is made of one 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 structure which is is preferable.

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

  For example, when a film is formed by a pulse sputtering method, the transparent substrate 2 is placed in a chamber of a mixed gas atmosphere of an inert gas and oxygen gas, and a target is formed as an adhesion layer forming material so as to have a desired composition. Select and deposit. 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 the high refractive index layer and the low refractive index layer are formed by the pulse sputtering method, the layer thickness of each layer can be adjusted, for example, by adjusting the discharge power, adjusting the film formation time, or the like.

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

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

  The antifouling film 5 is not limited as long as it has water and oil repellency and can impart antifouling properties to the resulting antiglare film-coated substrate 10. However, the fluorine-containing organosilicon compound is cured by a hydrolysis condensation reaction. It is preferable that it consists of a fluorine-containing organosilicon compound film obtained.

  The antifouling film 5 has a thickness of 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. If the film thickness of the antifouling film 5 is 2 nm or more, the antifouling property and the abrasion resistance of the antifouling film 5 are excellent. Moreover, if the film thickness of the antifouling film 5 is 30 nm or less, the optical characteristics such as antiglare property and haze of the antiglare film-coated substrate 10 in a state where the antifouling film 5 is formed are good.

  As a method for forming a fluorine-containing organosilicon compound film, a composition of a silane coupling agent having a fluoroalkyl group such as a perfluoroalkyl group; a fluoroalkyl group containing a perfluoro (polyoxyalkylene) chain, 4 is applied to the surface of the low reflective film 4 by spin coating, dip coating, casting, slit coating, spray coating, etc., or by applying a heat treatment as necessary. Examples include a vacuum 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, vacuum deposition is preferred. The formation of the fluorine-containing organosilicon compound film by a vacuum deposition method is preferably performed using a film-forming 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 deposition method. The hydrolyzable silicon compound may contain a partial hydrolysis condensate and a partial hydrolysis cocondensate in addition to the compound itself.

  Specifically, the fluorine-containing hydrolyzable silicon compound used for forming the fluorine-containing organosilicon compound film of this embodiment is selected from the group consisting of a perfluoropolyether group, a perfluoroalkylene group, and a perfluoroalkyl group. Examples thereof include fluorine-containing hydrolyzable silicon compounds having one or more groups. These groups exist as a fluorine-containing organic group bonded directly to the silicon atom of the hydrolyzable silyl group via a linking group.

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

At this time, the antifouling film 5 may be formed directly on the surface of the antiglare film 3 without forming the low reflection film 4. In this case, as described above, the anti-glare film 3 includes CF ₃ (CH ₂ ) n − groups in the film, so that the formation of a porous film is suppressed and the film forming composition is soaked into the porous film. Does not occur. Therefore, the antifouling film 5 having excellent adhesion with the antiglare film 3 and excellent antifouling properties can be obtained.

  The antifouling film 5 can be formed, for example, by applying a film forming composition using a known spray device or the like. The film forming composition is applied by moving the nozzle of the spray device in the first direction from one end to the other end with respect to the substrate 1 with antiglare film. The nozzle that has reached the other end is translated in a second direction perpendicular to the first direction by a predetermined interval (hereinafter referred to as pitch). The nozzle is again translated from the other end toward the one end. This is repeated so that the coating region extends over the entire surface of the antiglare film-coated substrate 1.

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

  From the results shown in Table 1, even when the discharge amount per unit area is constant, the nozzle moving speed is made faster and the pitch is made smaller than the nozzle moving speed is made slower and the pitch is made larger. It can be seen that the coating efficiency of the film-forming composition is better. In particular, the pitch is preferably 12 mm or less 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 not formed with an antiglare film and measuring the amount of F atoms. The same tendency is observed.

(Print layer)
The printed layer 6 is, for example, a wiring circuit arranged in the vicinity of the outer periphery of an image display device such as a portable device or an adhesive portion between the casing of the portable device and the antiglare film-coated substrate 10 for the purpose of enhancing the visibility and aesthetics of the display Provided as necessary to conceal etc. Here, the peripheral portion means a band-like region having a predetermined width from the outer periphery toward the central portion. The print layer 6 may be provided on the entire periphery of the surface opposite to the main surface of the transparent substrate 2 or may be provided on a part of the periphery.

  The print layer 6 is formed in a desired color according to the purpose, for example, with a width that can conceal the wiring circuit and the adhesive portion. The print layer 6 is formed using, for example, ink.

  Examples of the ink include inorganic ink containing a ceramic fired body and the like, and organic ink containing a colorant such as a dye or a pigment and an organic resin. For example, when the printing layer 6 is formed in black, 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, mica, and the like. Can be mentioned. The black printed layer 6 is obtained by melting the ink made of the ceramic and silica, printing it in a desired pattern, and then drying it. This inorganic ink requires a melting and drying process and is generally used as a glass-only ink.

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

  Among the inorganic inks and organic inks, it is preferable to use organic inks because the drying temperature is low. From the viewpoint of chemical resistance, an organic ink containing a pigment is preferable.

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

  When the substrate 10 with the antiglare film provided with the printing layer 6 is used as a front plate of an image display device or the like, the substrate 10 with the antiglare film is arranged so that the printing layer side is disposed on the image display device side. Is provided on the viewing side (front surface). When the image display device provided with the base 10 with the antiglare film is viewed from the front, the black printed portion is on the peripheral portion and the display portion is on the inner side of the peripheral portion via the antiglare film 3 and the transparent base 2, respectively. Is visually recognized.

  At this time, when the haze of the front plate is high, the black printed portion appears clouded, and when the display portion turns black without energizing the display panel, the black printed portion and the black portion of the display portion seen through the front plate A boundary may be created between them and the beauty may be impaired. Since the base 10 with the antiglare film of the present embodiment has a low haze, no boundary is generated between the black printed portion and the black color of the display portion seen through the front plate, and the substrate is visually recognized without these boundaries. It is excellent in aesthetics.

<Use of substrate with antiglare film>
Applications of the base with an antiglare film of the present invention include, for example, vehicle transparent parts (headlight covers, side mirrors, front transparent substrates, side transparent substrates, rear transparent substrates, instrument panel surfaces, etc.), meters, architectural windows , Show windows, displays (notebook computers, monitors, LCDs, PDPs, ELDs, CRTs, PDAs, etc.), LCD color filters, touch panel substrates, pickup lenses, optical lenses, eyeglass lenses, camera parts, video parts, CCD covers Substrate, optical fiber end face, projector part, copier part, transparent substrate for solar cell (cover glass, etc.), mobile phone window, backlight unit part (light guide plate, cold cathode tube, etc.), backlight unit part, LCD brightness enhancement film (Prism, transflective film, etc.), LCD brightness enhancement film, organic EL Optical device components, inorganic EL light emitting device component, a phosphor light emitting device component, an optical filter, the end face of the optical component, the illumination lamp, the cover of the luminaire, amplified laser light source, an antireflection film, a polarizing film, an agricultural film, or the like.

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

EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated in detail, it is not limited to a following example. 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 property evaluation method>
(Roughness curve skewness Rsk, arithmetic average roughness Ra, roughness curve element average length RSm)
The roughness curve skewness Rsk, arithmetic average roughness Ra, and average length RSm of roughness curve elements on the surface of the antiglare film are defined in JIS B0601-2001 using SURFCOM 1500SD3-12 manufactured by Tokyo Seimitsu Co., Ltd. Measured according to the method being 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 imaging range can be calculated from the number of pixels in the direction perpendicular to the scale bar and film thickness by counting the number of pixels in the entire cross section of the antiglare film on the digital data. Further, it may be calculated using commercially available image processing software. In the SEM observation, the observation was performed over a visual field of 70 μm in the direction perpendicular to the film thickness, and the average value was defined 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 Corporation, measurement diameter 30 mm, measurement line F-Kα, filter OUT, slit Std. , Spectral crystal RX35, detector PC, PHA100-300, peak angle 38.794 deg. (20 sec), B.E. G. Angle 43.000 deg. Under the condition of (10 sec), the fluorine content (mass%) in the measurement target film and the fluorine content (mass%) in the standard sample were measured. The amount of F 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 base with an antiglare film was measured according to the method specified in JIS K7136: 2000 using a haze meter (HR-100 model, manufactured by Murakami Color Research Laboratory).

(60 ° specular gloss (Gloss))
As the glossiness of the surface of the substrate with antiglare film, 60 ° specular glossiness (%) was measured. The 60 ° specular glossiness is a method specified in 60 ° specular glossiness of JIS Z8741: 1997, using an all-in-one gloss meter (Rohopint IQ, manufactured by Low Point Instruments Co., Ltd.), and the back surface (on the opposite side of the main surface) A black felt was laid on the (surface) side, the back surface reflection of the substrate with antiglare film was eliminated, and the measurement was made at almost the center of the antiglare film.

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

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

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

  Next, an anti-glare index value (Diffusion) is calculated from the equation (1).

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

(Temperature durability)
The durability of the anti-glare 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). What was there was rated as “bad”, and what was less than 0.5% as “good”.

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

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

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

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

(Example 1)
Tetraethoxysilane, trifluoropropyltrimethoxysilane as organic silane, and SLV liquid, and the fluorine-containing silica precursor (tetraethoxysilane, organic silane, SLV particles) has a solid content concentration in terms of SiO ₂ of 3.11% by mass. The amount of each component relative to the total amount of solids was adjusted to the ratio shown in Table 2. At this time, tetraethoxysilane, organosilane, and SLV liquid were added to the liquid medium while stirring the liquid medium using a magnetic stirrer, and mixed at 25 ° C. for 30 minutes. Thereafter, a nitric acid aqueous solution having a concentration of 60% by mass was dropped by 0.54% by mass with respect to the amount of the mixture of tetraethoxysilane, trifluoropropyltrimethoxysilane, SLV liquid and liquid medium, and further at 60 ° C. The mixture was mixed for 60 minutes to obtain a precursor liquid of a liquid composition for forming an antiglare film.

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

As the transparent substrate, manufactured by Asahi Glass Co., Ltd. Chemical strengthening special glass Dragontrail (TM) (Size: 100 mm × 100 mm, thickness: 1.1 mm) with respect to, with KNO ₃ molten salt, 2.5 410 ° C. A glass substrate subjected to chemical strengthening treatment for hours was used. The glass substrate subjected to the chemical strengthening treatment had a compressive stress layer depth of 25 μm and a surface compressive stress of 750 MPa.

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

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

  The temperature in the coating booth of the electrostatic coating apparatus was adjusted within the range of 25 ± 3 ° C. and the humidity within the range of 50% ± 10%. A cleaned transparent substrate that had been heated to 30 ° C. ± 3 ° C. in advance was placed on a chain conveyor of the electrostatic coating apparatus via a stainless steel plate. Electrostatic discharge with 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 at the time of manufacturing by the float process) while transporting at a constant speed of 3.0 m / min with a chain conveyor After applying twice the liquid composition for forming an antiglare film having a temperature within a range of 25 ± 3 ° C. by a coating method, the antiglare film is formed by baking at 450 ° C. for 30 minutes in the air. An attached substrate was obtained. Said evaluation was performed about the obtained base | substrate with an anti-glare film. The results are shown in Table 3.

(Examples 2-28)
The same procedure as in Example 1 was applied except that the types and amounts of organosilane, the amounts of tetraethoxysilane and SLV liquid, and the amounts of each component relative to the total amount of solids were adjusted to the ratios shown in Table 2. A liquid composition for forming a glare film was obtained. Using the obtained liquid composition for forming an antiglare film, the gun height shown in Table 2 was used, and in the same manner as in Example 1, a substrate with an antiglare film was produced. Went. The results are shown in Table 3. Only in Example 16, the number of times of application of the liquid composition for forming an antiglare film was set to one.

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

(Measurement condition)
Spray type: Rotating atomizing electrostatic automatic gun Gun height: 235mm from substrate surface to 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 shifted in the horizontal direction from directly below the center of the cup of the rotary atomizing electrostatic automatic gun. Position at which drop flying frequency becomes maximum Number of measured particles: 1000 particles Calculation of average particle size: Sauter average particle size was calculated for 1000 measured particle sizes.
Measurement area at each measurement position: 2623 μm (height) × 1475 μm (width) × 1795 μm (depth)

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

  From Tables 2 and 3, the antiglare film-coated substrates of Examples (Examples 1 to 17) have an antiglare index value of 0.05 or more and a haze of 8 or less, and excellent antiglare properties. And low haze can be achieved. In the substrate with antiglare film of Examples (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 because Rsk is over 1.3. Therefore, according to this invention, it turned out that the base | substrate with an anti-glare property in which the outstanding anti-glare property and low haze were compatible was obtained.

<Oil and fat wiping property evaluation test>
The oil and fat wiping property was carried out as follows. 0.05 g of Nivea cream manufactured by Kao Corporation was placed as an oil on the anti-glare film of a clean substrate with an anti-glare film. Next, oil and fat were transferred to the silicone plug by placing a silicone plug having a bottom of φ15 mm on which a 1 kg load was placed. Subsequently, a silicone plug with 1 kg of load to which the oil and fat was transferred was placed on a paper waste for 80 seconds to remove excess oil and fat. Subsequently, a silicon stopper loaded with a 1 kg load was placed on the sample surface, and oil and fat were transferred to the sample surface to obtain an evaluation sample.
It is necessary to transfer the oil and fat of the evaluation sample to a wiping cloth (Toroshi MK MK24H-CPMK manufactured by Toray Industries, Inc.) cut into a strip shape with a bottom area of 20 mm × 20 mm and a load of 100 g, and the oil and fat cannot be visually recognized. Counted the number of times. The part of the wiping cloth that was in contact with the oil and fat was not reused, and wiping was performed so that the clean part was always in contact with the oil and fat. If it can be wiped within 20 times, the wiping property is good as “good”, and if it is within 10 times, it is very good as “excellent”. When the wiping required 21 times or more, it was judged as “bad” and the result is shown in Table 4.

<Abrasion resistance test>
Attach the surface of the scratch-resistant sample to a 20 mm x 20 mm indenter with Kanakin No. 3 (attached white cloth cotton for testing conforming to JIS L 0803) and apply a load of 1 kg. Reciprocating was performed 100,000 times at 80 reciprocations and a rubbing distance of 40 mm. If the sample surface after rubbing is not visually changed at all, the scratch resistance is very good as “excellent”, and if there are 3 scratches having a width of 0.8 mm or less, the scratch resistance is good and “good”. It was. When scratches with a width of 0.8 mm or more were confirmed, or when four or more scratches with a width of 0.8 mm or less were confirmed, the scratch resistance was judged as “bad”, and the results are shown in Table 4.

  From Table 4, the antiglare film-coated substrates (Examples 1 to 17) among the examples were also excellent in oil and fat wiping property and scratch resistance. This is considered to be related to Rsk, and if Rsk is too large, the uneven shape of the concavo-convex shape derived from the anti-glare film becomes sharp, so it is difficult to remove oil and fat, and the tip of the convex shape is likely to be destroyed. It is thought that the nature becomes low. In the base with an antiglare film of the present invention, by setting Rsk to 1.3 or less, not only good optical characteristics are obtained, but also oil and fat wiping properties related to ease of fingerprint wiping and wear properties are related. Good results were also obtained with respect to scratch resistance. Furthermore, it was also found that by making Rsk less than 1.07, better oil and fat wiping properties and scratch resistance can be obtained.

DESCRIPTION OF SYMBOLS 1,10 ... Base | substrate with anti-glare film, 2 ... Transparent base | substrate, 3 ... Anti-glare film, 4 ... Low reflection film, 5 ... Anti-fouling film, 6 ... Printing layer

Claims (18)

A transparent substrate and an antiglare film provided on the transparent substrate;
The antiglare film contains silica as a main component and includes a CF ₃ (CH ₂ ) _n — group (where n is an integer of 1 to 6),
A substrate with an antiglare film, wherein the skewness Rsk of the roughness curve of the antiglare film surface is 1.3 or less and the arithmetic average roughness Ra is 0.01 μm or more.   The antiglare film-coated substrate 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 an average length RSm of elements of a roughness curve on 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 a skewness Rsk of a roughness curve of the surface of the antiglare film is 1.05 or less.   The substrate with an antiglare film according to any one of claims 1 to 6, wherein an arithmetic average roughness Ra of the surface of the antiglare film is 0.1 µm or less.   The substrate with an antiglare film according to any one of claims 1 to 7, wherein an average length RSm of an element of a roughness curve on the surface of the antiglare film is 10 µm or more.   When a glass having a specific gravity of 2.48 containing 1.0% by mass of fluorine is used as a standard sample, a value (F amount) obtained by dividing the measured value of the fluorine content of the antiglare film by the measured fluorine value of the standard sample is The substrate with an antiglare film according to any one of claims 1 to 8. The substrate with an antiglare film according to claim 1, wherein the CF ₃ (CH ₂ ) _n — group is a CF ₃ CH ₂ CH ₂ — group.   The substrate with an antiglare film according to any one of claims 1 to 10, wherein a 60 ° specular 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 11, wherein the transparent substrate comprises a glass substrate.   The substrate with an antiglare film according to any one of claims 1 to 11, wherein the transparent substrate comprises a chemically strengthened glass substrate.   The substrate with an antiglare film as a substrate according to any one of claims 1 to 13, wherein the transparent substrate has a curved surface.   The substrate with an antiglare film according to any one of claims 1 to 14, wherein the transparent substrate has a thickness of 0.1 to 5 mm.   A liquid composition for forming an antiglare film, comprising trifluoropropyltrimethoxysilane, scaly silica particles, and a liquid medium. An antiglare film-forming liquid composition containing trifluoropropyltrimethoxysilane, scaly silica particles, and a liquid medium is applied onto a transparent substrate by a spray coating method to form a coating film. By firing,
The main component is silica, CF ₃ (CH ₂ ) _n — group (where n is an integer of 1 to 6), the skewness Rsk of the surface roughness curve is 1.3 or less, and A method for producing a substrate with an antiglare film, wherein an antiglare film having an arithmetic average roughness Ra of 0.01 μm or more is formed on the transparent substrate to produce a substrate with an antiglare film.   The method for producing a substrate with an antiglare film according to claim 17, wherein the liquid composition for forming an antiglare film is applied onto the transparent substrate by an electrostatic spray coating method.

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