WO2015111660A1

WO2015111660A1 - Base material with anti-glare layer and production method therefor

Info

Publication number: WO2015111660A1
Application number: PCT/JP2015/051695
Authority: WO
Inventors: あずさ ▲高▼井; 敏本谷; 義美大谷
Original assignee: 旭硝子株式会社
Priority date: 2014-01-24
Filing date: 2015-01-22
Publication date: 2015-07-30
Also published as: JPWO2015111660A1; JP6551235B2

Abstract

Provided are: a base material with anti-glare layer, that is capable of highly efficient diffuse reflection of external light, is capable of sufficiently suppressing glare, and has excellent anti-glare properties; and a production method for the base material with anti-glare layer. The base material (1) with anti-glare layer has a base material (10) and an anti-glare layer (12) formed upon the base material (10). The anti-glare layer (12) contains a silica-based matrix and does not contain silica microparticles or contains both a silica-based matrix and silica microparticles. The number of protrusions (N_P) on the surface of the anti-glare layer (12), measured using a specific protrusion number measurement method, is at least 37. In the production method for the base material with anti-glare layer, a coating fluid including a silica-based matrix precursor and a dispersion medium is sprayed, using a spray method, on to the base material (10) that has been heated, and the anti-glare layer (12) is formed.

Description

Base material with antiglare layer and method for producing the same

The present invention relates to a substrate with an antiglare layer and a method for producing the same.

For example, in various image display devices such as a liquid crystal display (LCD) and a plasma display (PDP), when external light such as indoor lighting (fluorescent lamps) and sunlight is reflected on the display surface, the reflected image provides visibility. descend. As a method for suppressing a reduction in visibility due to a reflected image, a so-called antiglare process is known in which an antiglare layer (hereinafter also referred to as an AG layer) is formed on a display surface to diffusely reflect external light.

Examples of the base material with an AG layer subjected to the anti-glare treatment include a base material with an AG layer in which an AG layer is formed by etching the surface of a glass plate using a reagent (hydrogen fluoride or the like). However, it is necessary to use a reagent that is dangerous for the antiglare treatment in the base material with the AG layer, the latent scratches are remarkable in the glass plate after etching, and the processing yield is bad, especially in the glass plate having a large area, the etching is not uniform. There are problems such as being easy to become.

As a base material with an AG layer that solves the above problem, a base material with an AG layer in which an AG layer containing a silica-based matrix is formed on the base material has been proposed (for example, see Patent Document 1).
As a method for forming the AG layer of the substrate with the AG layer, for example, there is a method in which a coating liquid containing a silica-based matrix precursor (ethyl silicate, etc.) and a dispersion medium is applied to a heated substrate and then heated and cured. Can be mentioned.

JP-A-60-109134

However, in the case of a substrate with an AG layer as in Patent Document 1, when the gloss of the AG layer is lowered by repeatedly applying a coating solution in order to increase the efficiency of irregular reflection, the surface of the AG layer is glaring and visibility is reduced. May decrease.

An object of the present invention is to provide a substrate with an AG layer that can sufficiently suppress glare and diffuse excellently diffuse external light with high efficiency, and has an excellent antiglare property, and a method for producing the substrate with an AG layer That is.

The present invention provides a substrate with an AG layer having the following configurations [1] to [9] and a method for producing the same.
[1] A base material and an AG layer formed on the base material, wherein the AG layer contains a silica-based matrix and does not contain silica fine particles. convex parts measurement convex parts N _P measured by the method is 37 or more, AG-layer-substrates.
(Method for measuring the number of convex parts)
In each cross-section curve graph measured in accordance with JIS B0601 (2001) at any three points on the surface of the AG layer, the difference in height relative to the minimum cross-section height is within a range of 500 μm in length in the horizontal axis direction. There was measured the number of protrusions having the above section height 100 nm, and the average value and the convex parts N _P.
[2] A base material and an AG layer formed on the base material, wherein the AG layer contains a silica-based matrix and silica fine particles, and the average primary particle diameter of the silica fine particles is 0.1 to a 1.0 .mu.m, the convex parts N _P measured by the convex parts measuring method on the surface of the AG layer is 37 or more, AG layer-substrate.
[3] The substrate with an AG layer according to [1] or [2], wherein the surface gloss of the AG layer is 130 or less.
[4] The substrate with an AG layer according to any one of [1] to [3], wherein the surface roughness Ra of the AG layer is 0.01 μm or more.
[5] The substrate with an AG layer according to any one of [1] to [4], wherein the substrate is a tempered glass plate having a thickness of 0.05 to 2.5 mm.
[6] A method for producing a base material with an AG layer having a base material and an AG layer formed on the base material, the method including a silica-based matrix precursor and a dispersion medium and no silica fine particles liquid, said as convex parts N _P of the AG layer surface measured by the convex parts measuring method is 37 or more, to form the AG layer was sprayed in a spraying method on a heated substrate, AG layer A manufacturing method of a substrate with a mark.
[7] A method for producing a base material with an AG layer comprising a base material and an AG layer formed on the base material, wherein the silica-based matrix precursor and the average primary particle size are 0.1 to 1. a coating solution containing a silica fine particles 0μm and a dispersion medium, wherein as the convex parts N _P of the AG layer surface measured by the convex parts measuring method is 37 or more, in spraying onto a heated substrate The manufacturing method of the base material with an AG layer which sprays and forms an AG layer.
[8] The method for producing a substrate with an AG layer according to [6] or [7], wherein the solid content concentration of the coating solution is 0.3 to 6.0% by mass.
[9] The method for producing a substrate with an antiglare layer according to any one of [6] to [8], wherein the coating liquid is sprayed using a spray spraying device having a two-fluid spray nozzle structure.

The base material with an AG layer of the present invention can sufficiently suppress glare while efficiently reflecting external light with high efficiency, and has excellent antiglare properties.
According to the method for producing a base material with an AG layer of the present invention, it is possible to obtain a base material with an AG layer that can sufficiently suppress glare and highly excellent anti-glare properties while efficiently reflecting external light with high efficiency. .

It is sectional drawing which showed an example of the base material with AG layer of this invention. It is a figure explaining the convex part number measuring method in this invention. It is the figure which showed the spray pitch and spray pattern in an Example. 2 is a cross-sectional curve graph of an AG layer of a base material with an AG layer of Example 1.

<Base material with AG layer>
Hereinafter, an example of the substrate with an AG layer of the present invention will be described and described.
As shown in FIG. 1, the substrate 1 with an AG layer of the present embodiment includes a substrate 10 and an AG layer 12 formed on the substrate 10.

[Base material]
Examples of the material of the substrate 10 include glass and plastic.
Examples of the glass include soda lime glass, aluminosilicate glass, alkali-free glass, borosilicate glass, and quartz glass.
Examples of the plastic include polycarbonate, polyethylene terephthalate, and triacetyl cellulose. When the material of the base material 10 is plastic, the surface of the base material 10 may be primed with a silane coupling agent or the like from the viewpoint of adhesion to the AG layer 12.
The shape of the substrate 10 is not particularly limited, and examples thereof include a plate shape, a film shape, a spherical shape, and a curved surface shape.

When the substrate 10 is a glass plate, the thickness of the substrate 10 is preferably 0.05 to 2.5 mm, more preferably 0.1 to 2.2 mm.
As the substrate 10, a glass plate is preferable from the viewpoint of strength and scratch resistance, and a tempered glass plate having a thickness of 0.05 to 2.5 mm is particularly preferable. Moreover, when making the base material 10 into a thin tempered glass board, the chemically strengthened glass which strengthened the aluminosilicate glass by the chemical strengthening process is preferable.

[AG layer]
The AG layer 12 is classified into the following AG layer (i) or AG layer (ii) depending on whether or not it contains silica fine particles.
(I) AG layer not containing silica fine particles.
(Ii) AG layer containing silica fine particles.
Hereinafter, each of the AG layer (i) and the AG layer (ii) will be described.

(AG layer (i))
The AG layer (i) is a layer that does not contain silica fine particles and satisfies the following conditions (1) and (2).
(1) Contains a silica-based matrix.
(2) convex parts N _P measured by the convex parts measuring method described later in the AG layer surface is 37 or more.

As the silica-based matrix, a known silica-based matrix used for the formation of the AG layer can be used. For example, a silica or silicone resin comprising a hydrolysis polymer of an alkoxysilane or a hydrolysis polymer of a silane coupling agent described later. Etc.

The method for measuring the number of convex portions is as follows.
In each cross-section curve graph measured in accordance with JIS B0601 (2001) at any three points on the surface of the AG layer, the difference in height relative to the minimum cross-section height is within a range of 500 μm in length in the horizontal axis direction. There was measured the number of protrusions having the above section height 100 nm, and the average value and the convex parts N _P.
For example, in the cross-sectional curve graph illustrated in FIG. 2, the height at the point a having the lowest height in the range of 500 μm in the horizontal axis direction is the lowest cross-sectional height, and the cross-sectional height of the cross-sectional height is the minimum cross-sectional height. The number of convex parts b by measuring the number of convex parts c and convex parts e having a height difference of 100 nm or more among convex parts b having a height difference of 50 nm, convex parts c having 120 nm, convex parts d having 80 nm, and convex parts e having 100 nm. Let it be _NP .

Convex parts _{N P} which is measured at the surface of the AG layer (i) is at 37 or more, more preferably 37 to 100, more preferably from 40 to 60, 44-55 amino are especially preferred. If convex parts N _P is the lower limit or more, it can be suppressed to occur glare on AG layer surface. If convex parts N _P is less than the upper limit, difficult compromise scratch resistance.

The AG layer (i) may contain components other than the silica-based matrix and the silica fine particles. Examples of the other components include matrix and fine particles, metal fine particles, inorganic pigments and the like containing metal oxides such as titania, zirconia, alumina, indium tin oxide (ITO), and antimony tin oxide (ATO).

The glossiness of the AG layer (i) is an index of the AG effect.
The glossiness of the AG layer (i) is preferably 130 or less, and more preferably 110 or less.
The glossiness of the AG layer is measured by a method defined in 60 ° specular glossiness of JIS Z8741 (1997).

The surface roughness Ra of the AG layer (i) is preferably 0.01 μm or more, more preferably 0.01 to 1.0 μm, further preferably 0.03 to 0.5 μm, and particularly preferably 0.04 to 0.3 μm. preferable. If the surface roughness of the AG layer (i) is not less than the lower limit, the glossiness can be sufficiently suppressed and the AG effect is sufficiently exhibited. If the surface roughness Ra of the AG layer (i) is less than or equal to the above upper limit value, the resolution is hardly lowered and the haze tends to be sufficiently small.
The surface roughness Ra of the AG layer is an arithmetic average roughness measured according to JIS B0601 (2001).

The refractive index of the AG layer (i) is preferably 1.1 to 1.8, and more preferably 1.2 to 1.6. If the refractive index of the AG layer (i) is not less than the lower limit, a sufficient AG effect can be easily obtained. If the refractive index of the AG layer (i) is less than or equal to the upper limit value, the reflected light is unlikely to become strong.
The refractive index means a refractive index at 550 nm and is measured by a refractometer.

(AG layer (ii))
The AG layer (ii) contains silica fine particles and satisfies the following conditions (1) to (3).
(1) Contains a silica-based matrix.
(2) convex parts N _P measured by the convex parts measuring method in AG layer surface is 37 or more.
(3) The average particle diameter of the silica fine particles contained in the AG layer (ii) is 0.1 to 1.0 μm.
Conditions (1) and (2) in the AG layer (ii) are the same as the conditions (1) and (2) in the AG layer (i), and preferred embodiments are also the same.

The AG layer (ii) contains silica fine particles having an average primary particle diameter of 0.1 to 1.0 μm (hereinafter also referred to as silica fine particles (P)), and therefore is more out of the AG layer (i). The effect of sufficiently suppressing glare while reflecting light with high efficiency is high.

The average primary particle diameter of the silica fine particles (P) is preferably from 0.1 to 1.0 μm, more preferably from 0.3 to 0.7 μm. If the average primary particle diameter of the silica fine particles (P) is within the above range, a sufficient glare suppressing effect is easily obtained.

Examples of the silica fine particles (P) include solid silica fine particles, porous silica fine particles, and hollow silica fine particles.
The silica fine particles (P) may contain a metal other than Si. Examples of other metals include Al, Cu, Ce, Sn, Ti, Cr, Co, Fe, Mn, Ni, Zn, and Zr. Other metals may form a complex oxide with Si.

In the AG layer (ii), the ratio of the SiO ₂ converted mass of the silica fine particles (P) to the SiO ₂ converted mass of the silica-based matrix (hereinafter also referred to as SiO ₂ ratio M1) is 0.01 to 20% by mass. Preferably, 0.1 to 10% by mass is more preferable. If the SiO ₂ ratio M1 is equal to or greater than the lower limit, even if the surface roughness Ra of the AG layer is reduced, the AG effect of improving the visibility by irregularly reflecting external light is easily exhibited. If SiO ₂ ratio M1 is less than the upper limit, adhesion strength between the base material of the AG layer tends to increase.

The AG layer (ii) may contain components other than the silica-based matrix and the silica fine particles. As this other component, the same thing as what was mentioned by AG layer (i) is mentioned, for example.

[Haze]
The haze of the substrate 1 with an AG layer is preferably 15% or less, and more preferably 10% or less. If the haze is less than or equal to the above upper limit value, it is easy to sufficiently suppress a decrease in image contrast. The haze of the base material 1 with an AG layer is preferably as low as possible.
The haze is measured using a commercially available haze meter according to JIS K7105 (1981).

[Usage]
The use of the substrate 1 with an AG layer is not particularly limited, and examples thereof include various image display devices (LCD, PDP, etc.), filters or protective plates for image display devices, and cover glasses for solar cells.

[Function and effect]
In the base material with an AG layer of the present invention described above, since the AG layer satisfying the above condition (2) is formed, the surface of the AG layer can be obtained even when the coating liquid is applied and the glossiness is lowered. It is possible to suppress glare. Therefore, the glare can be sufficiently suppressed while externally reflecting external light with high efficiency, and excellent antiglare properties can be obtained. The factors for obtaining such an effect are considered as follows.
Even if the coating solution is applied repeatedly, the surface of the AG layer is roughened and the glossiness is lowered, if the AG layer satisfies the condition (2), the light refracted in each of the uneven portions on the surface of the AG layer is reflected in the AG layer. It is thought that it becomes difficult to interfere with each other in the vicinity of the surface. As a result, it is considered that glare can be sufficiently suppressed while externally reflecting external light with high efficiency. Further, when silica fine particles are further contained, a further high glare suppressing effect can be obtained by simultaneously satisfying the conditions (2) and (3).

In addition, the base material with AG layer of this invention is not limited to the above-mentioned base material 1 with AG layer. For example, the base material with an AG layer of the present invention may be a base material with an AG layer in which AG layers are formed on both surfaces of the base material.
The substrate with an AG layer of the present invention may have one or more intermediate layers such as an antireflection layer, an alkali barrier layer, a colored layer, and an antistatic layer between the substrate and the AG layer. Good.
Further, the substrate with an AG layer of the present invention has one or more upper layers such as an antireflection (AR) layer, a fingerprint adhesion prevention (AAFP) layer, a colored layer, and a scratch resistance improving layer on the surface of the AG layer. It may be.

<Method for producing substrate with AG layer>
Hereinafter, the manufacturing method of the base material 1 with an AG layer will be described as an example of the manufacturing method of the base material with an AG layer.
The manufacturing method of the substrate 1 with an AG layer is classified into the following method (X) and method (Y) according to the type of the AG layer 12 to be formed.
(X) A method of forming the AG layer (i) as the AG layer 12.
(Y) A method of forming the AG layer (ii) as the AG layer 12.
Hereinafter, the methods (X) and (Y) will be described.

[Method (X)]
The method (X), wherein the precursor and the dispersion medium of the silica-based matrix, a coating solution containing no silica fine particles (hereinafter, the coating solution (Z1) and also referred.) And convex parts N _P of the AG layer surface 37 There is a method in which the AG layer 12 is formed by spraying on the heated base material 10 by a spray method so as to be more than one, and heat curing as necessary.

(Coating solution (Z1))
The coating solution (Z1) is a dispersion containing a silica matrix precursor and a dispersion medium, and no silica fine particles.
Examples of the precursor of the silica-based matrix include a hydrolysis polymer of alkoxysilane, a hydrolysis polymer of silane coupling agent, and the like.

Examples of the alkoxysilane include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, methyltrimethoxysilane, and ethyltriethoxysilane.

Examples of the silane coupling agent include an alkoxysilane having a vinyl group (such as vinyltrimethoxysilane), an alkoxysilane having an epoxy group (such as 3-glycidoxypropyltrimethoxysilane), and an alkoxysilane having an acrylic group (3 -Acryloxypropyltrimethoxysilane, etc.).

Examples of the dispersion medium include water, alcohols (methanol, ethanol, isopropanol, etc.), ketones (acetone, methyl ethyl ketone, etc.), ethers (tetrahydrofuran, 1,4-dioxane, etc.), esters (ethyl acetate, methyl acetate, etc.). Etc.), glycol ethers (ethylene glycol monoalkyl ether, etc.), nitrogen-containing compounds (N, N-dimethylacetamide, N, N-dimethylformamide, etc.), sulfur-containing compounds (dimethyl sulfoxide, etc.) and the like.

The solid content concentration of the coating liquid (Z1) is preferably 0.3 to 6.0% by mass, and more preferably 1.0 to 5.0% by mass. If the solid content concentration of the coating solution (Z1) is equal to or higher than the lower limit, it is easy to form the AG layer 12 that exhibits a sufficient AG effect by the spray method. If the solid content concentration of the coating solution (Z1) is not more than the above upper limit value, the film thickness control of the AG layer 12 becomes easy.

[Coating method]
Coating Solution (Z1) is convex parts N _P of the AG layer surface which is formed such that 37 or more are sprayed with a spray method onto the heated substrate 10.
Convex parts N _P of the AG layer 12 surface to be formed, the coating liquid sprayed droplet diameter, the distance between the spray nozzle tip and the substrate 10, coating surface speed by a spray method (recoating times), the substrate 10 It can be controlled by adjusting the heating temperature or the like.

The droplet diameter of the coating liquid (Z1) can be appropriately adjusted by the type of spray nozzle, the spray pressure, the amount of liquid, etc. in the spray spraying apparatus. For example, in a two-fluid nozzle, the higher the spray pressure, the smaller the droplet, and the larger the liquid volume, the larger the droplet.
The conditions for spraying the coating liquid (Z1), such as the type of nozzle, spray pressure, liquid volume, etc., are preferably such that the droplet diameter is 30 μm or less when water is sprayed. Is more preferable, and conditions of 3 to 15 μm are more preferable. If the droplet diameter is equal to or greater than the lower limit, the coating efficiency does not extremely decrease. If the droplet diameter is less than the upper limit, the convex parts N _p tends to be 37 or more, thus easily obtained sufficient AG effect.
The droplet diameter is the Sauter average particle diameter measured by a laser measuring instrument.

The spray pressure is preferably from 0.1 to 0.7 MPa, more preferably from 0.2 to 0.5 MPa.

Examples of the nozzle in the spraying apparatus used for the spray method include a two-fluid spray nozzle and a one-fluid spray nozzle. In the present invention, from the viewpoint of the convex parts N _P tends to form a 37 or more AG layer 12, it is preferable to spray the coating solution by using a spraying device having a two-fluid spray nozzle structure. The two-fluid spray nozzle here is a type having a nozzle that sprays a liquid by mixing it with a gas to form a fine mist, and a finer particle diameter is obtained than a one-fluid spray nozzle, and the liquid flow rate adjustment range Has the advantage of widening.

The distance between the tip of the spray nozzle and the substrate 10 when spraying the coating liquid onto the substrate is preferably 80 to 300 mm, more preferably 100 to 200 mm. If the distance between the tip of the spray nozzle and the substrate 10 is within the above range, an AG layer having excellent antiglare properties can be easily formed.

The heating temperature of the substrate 10 when the coating solution (Z1) is applied to the substrate surface is preferably 30 to 100 ° C., more preferably 40 to 95 ° C. If the heating temperature of the substrate 10 is the range, the convex parts N _P tends to form a 37 or more AG layer 12. If the heating temperature of the base material 10 is equal to or higher than the lower limit value, the dispersion medium evaporates quickly, so that the AG layer 12 can be easily formed. If the heating temperature of the base material 10 is not more than the above upper limit value, it is easy to form the AG layer 12 having good adhesion to the base material 10.

When applying the coating solution (Z1) to the surface of the base material, a heated heat insulating plate may be disposed under the base material to suppress the temperature drop of the base material.
When the heat curing of the coating layer is performed after coating the coating solution (Z1), the heat curing temperature is preferably 100 to 700 ° C, more preferably 200 to 700 ° C.

[Method (Y)]
The method (Y), the precursor and silica fine particles (P) and the coating liquid containing a dispersion medium of the silica-based matrix (hereinafter, the coating liquid (Z2) and also referred.) And convex parts N _P of the AG layer surface 37 There is a method in which the AG layer 12 is formed by spraying on the heated base material 10 by a spray method so as to be more than one, and heat curing as necessary.

(Coating solution (Z2))
Examples of the silica-based matrix precursor and the dispersion medium in the coating liquid (Z2) include the same ones as mentioned in the coating liquid (Z1).
In the coating liquid (Z2), the ratio of the SiO ₂ equivalent mass of the silica fine particles (P) to the SiO ₂ equivalent mass of the silica-based matrix precursor is preferably 0.01 to 20% by mass, preferably 0.1 to 10% by mass. Is more preferable.

The solid content concentration of the coating solution (Z2) is preferably 0.3 to 6.0% by mass, and more preferably 1.0 to 5.0% by mass. If the solid content concentration of the coating solution (Z2) is equal to or higher than the lower limit, it is easy to form the AG layer 12 that exhibits a sufficient AG effect by the spray method. If the solid content concentration of the coating solution (Z2) is equal to or lower than the upper limit, the film thickness control of the AG layer 12 becomes easy.

(Application method)
Application of the coating liquid (Z2) to the substrate surface in the method (Y) can be performed in the same manner as in the method (X) except that the coating liquid (Z2) is used instead of the coating liquid (Z1). The preferred embodiment is also the same.

[Function and effect]
According to the manufacturing method of the AG layer-substrate of the present invention described above (X) and (Y), the convex parts N _P is 37 or more AG layer is formed, by diffused reflection of external light at a high efficiency On the other hand, the base material with an AG layer having an excellent antiglare property capable of sufficiently suppressing glare is obtained.

Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited by the following description. Examples 1 to 12 are examples, and examples 13 to 18 are comparative examples.

[Glossiness]
As the glossiness of the AG layer, using a gloss meter (PG-3D type, manufactured by Nippon Denshoku Industries Co., Ltd.), the AG layer has a glossiness of 60 ° according to the method defined in JIS Z8741 (1997). The glossiness including the back surface reflection of the attached substrate was measured at the approximate center of the AG layer.

[Haze]
The haze of the substrate with the AG layer was measured at a substantially central portion of the AG layer using a haze meter (manufactured by Murakami Color Research Laboratory, Model HR-100).

[Glitter]
The glare of the base material with an AG layer was determined by visual observation according to the following criteria in a state where a green screen was displayed on an iPad (manufactured by Apple, Retina display model) and the base material with an AG layer was placed on the display. .
“◎”: No glare is observed.
“◯”: The glare is very slight.
“Δ”: slight glare.
“×”: Glare is recognized.
“XX”: Glare is strongly recognized.

[Microscopic observation]
The observation of the AG layer of the substrate with the AG layer was performed using a system microscope BX51 manufactured by OLYMPUS, and the magnification was 500 times. For observation with a scanning electron microscope, model S-4300 manufactured by Hitachi, Ltd. was used.

[Number of convex portions N _P ]
For any three locations on the surface of the AG layer, cross-sectional curves were measured using SURFCOM 1500DX2 manufactured by Tokyo Seimitsu Co., Ltd. in accordance with JIS B0601 (2001). in the range of 500 [mu] m, measured number of protrusions height difference for the lowest section height has more section height 100 nm, and the average value thereof and convex parts N _P.

[Surface roughness Ra]
The surface roughness Ra of the AG layer was measured at substantially the center of the AG layer using a surface roughness measuring machine (Surfcom 130A, manufactured by Tokyo Seimitsu Co., Ltd.) in accordance with JIS B0601 (2001). The measurement length was 4 mm, and the cut-off value was 0.25 mm.

[Average primary particle diameter of silica fine particles in the AG layer]
A cross section of the AG layer of the obtained base material with an AG layer was cut out, the cross section was observed with a scanning electron microscope, the diameters of 10 silica fine particles were measured, and averaged to obtain an average primary particle diameter.

[Content of silica fine particles]
The content of silica fine particles in the AG layer was measured as follows.
The AG layer was observed with an optical microscope, the number of silica fine particles in three fields of 50 μm square in the observed image was measured, and the average value thereof was n. Next, the volume V ₁ (%) occupied by the silica fine particles in a 50 μm square visual field was calculated by the following formula (1), and the content W of the silica fine particles was further calculated by the following formula (2). As the radius r of the silica fine particles, a value calculated from the average primary particle diameter of the silica fine particles in the AG layer was used. In the AG layer formed using a porous silica fine particle dispersion (σ) described later, the specific gravity (1.15) of the porous silica fine particles and the specific gravity (2.2) of the silica matrix are greatly different. Therefore, for the AG layer, volume V ₁ (%) occupied by silica fine particles in a 50 μm square field of view was calculated by the following equation (3) instead of the following equation (1).
_{V 1 = n × 4 × π} × r 3/3 ··· (1)
W = (100 × V ₁ ) / (2500 × Ra) (2)
V ₁ = n × 4 × π × r ³ /3×(1.15/2.2) (3)
(In formula (1) and formula (3), r is the radius of the silica fine particles. In formula (2), Ra is the surface roughness of the AG layer.)

[Droplet diameter]
The droplet diameter during application of the coating liquid by the spray method was determined by measuring the Sauter average particle diameter when water was sprayed under the same conditions with a laser measuring instrument (manufactured by Malvern, Mastersizer S).

[Production Example 1]
(Preparation of matrix precursor solution (α))
While stirring 72.1 g of denatured ethanol (manufactured by Nippon Alcohol Sales Co., Ltd., Solmix AP-11 (trade name), a mixed solvent containing ethanol as a main ingredient; the same shall apply hereinafter), 6.0 g of ion-exchanged water was added thereto. A mixed solution of 61 mass% nitric acid with 1.23 g was added, and the mixture was further stirred for 5 minutes. Next, 9.0 g of ethyl silicate 40 (solid content concentration of SiO ₂ : 40% by mass) was added and stirred at room temperature for 30 minutes to obtain a solution (α1). Further, while stirring 7.2 g of denatured ethanol, 0.7 g of ion exchange water, 0.15 g of 61 mass% nitric acid, and 1.04 g of 1,6-bistrimethoxysilylhexane were added and stirred for 5 minutes. The solution (α2) was stirred at 60 ° C. for 15 minutes. Solution ([alpha] 1) solution ([alpha] 2) was added, further 2.8g of ethylene glycol was added, stirred for 30 minutes at room temperature, a solution of SiO ₂ in terms solid concentration 3.78% by weight of the matrix precursor (alpha (Hereinafter also referred to as solution (α)).
Incidentally, SiO ₂ in terms of solid concentration is a solid content concentration when all Si of tetraethoxysilane was converted to SiO _2.

[Production Example 2]
(Solid silica fine particle dispersion (β))
Solid silica fine particles (manufactured by Nippon Shokubai Co., Ltd., KE-P10 (trade name)) are mixed with dimethylacetamide so that the solid content concentration in terms of SiO ₂ is 23% by mass, and a solid silica fine particle dispersion (β) (Hereinafter also referred to as dispersion (β)).

[Production Example 3]
(Solid silica fine particle dispersion (γ))
Solid silica fine particles (manufactured by Nippon Shokubai Co., Ltd., KE-P30 (trade name)) are mixed with dimethylacetamide so that the solid content concentration in terms of SiO ₂ is 23% by mass, and a solid silica fine particle dispersion (γ) (Hereinafter also referred to as dispersion (γ)).

[Production Example 4]
(Solid silica fine particle dispersion (δ))
Solid silica fine particles (manufactured by Nippon Shokubai Co., Ltd., KE-P50 (trade name)) are mixed with dimethylacetamide so that the solid content concentration in terms of SiO ₂ is 23% by mass, and a solid silica fine particle dispersion (δ) (Hereinafter also referred to as dispersion (δ)).

[Production Example 5]
(Porous silica fine particle dispersion (σ))
Porous silica fine particles (manufactured by Nissan Chemical Industries, Light Star S23A (trade name)) are mixed with dimethylacetamide so that the solid content concentration in terms of SiO ₂ is 23% by mass, and a porous silica fine particle dispersion (σ) (Hereinafter also referred to as dispersion (σ)).

[Production Example 6]
(Solid silica fine particle dispersion (ε))
Solid silica fine particles (manufactured by Nippon Shokubai Co., Ltd., KE-P100 (trade name)) are mixed in a dimethylacetamide solution so that the solid content concentration in terms of SiO ₂ is 23% by mass, and a solid silica fine particle dispersion (ε (Hereinafter also referred to as dispersion (ε)).

[Production Example 7]
(Preparation of matrix precursor solution (ζ))
While stirring 268 g of denatured ethanol, a mixed solution of 47 g of ion exchange water and 0.36 g of 61% by mass nitric acid was added and stirred for 5 minutes. Furthermore, 84 g of tetraethoxysilane was added and stirred at room temperature for 90 minutes to prepare a matrix precursor solution (ζ) (hereinafter also referred to as solution (ζ)) having a solid content concentration of 3 mass% in terms of SiO ₂ . did.

[Production Example 8]
(Preparation of coating solution (A))
The solution (α) was used as it was to obtain a coating solution (A).

[Production Example 9]
(Preparation of coating solution (B))
In the solution (α) and the dispersion liquid (β), the ratio of the SiO ₂ converted mass of the silica fine particles of the dispersion liquid (β) to the SiO ₂ converted mass of the matrix precursor of the solution (α) is 1% by mass. It mixed and the coating liquid (B) was prepared.

[Production Examples 10 to 16]
(Preparation of coating solutions (C) to (I))
Coating solutions (C) to (I) were prepared in the same manner as in Production Example 9, except that the dispersion (β) was changed to the dispersion shown in Table 1.

[Production Example 17]
(Preparation of coating solution (J))
The solution (ζ) was used as it was to obtain a coating solution (J).

The compositions of the coating solutions obtained in Production Examples 8 to 17 are shown in Table 1. In addition, “SiO ₂ ratio M2” in Table 1 means the ratio of the SiO ₂ equivalent mass of silica fine particles to the SiO ₂ equivalent mass of the matrix precursor in the coating solution.

[Example 1]
A glass plate (soda lime glass, manufactured by Asahi Glass Co., Ltd., FL1.1, size: 300 mm × 300 mm, thickness 1.1 mm) was prepared as a transparent substrate. The surface of the glass plate was washed with sodium hydrogen carbonate water, rinsed with ion-exchanged water, and dried.
Next, the glass plate was heated in an oven so that the surface temperature was 80 ° C., and the coating liquid (A) was applied onto the glass plate by the spray method under the following conditions.
Spray pressure: 0.4 MPa
Coating liquid amount: 7 mL / min,
Nozzle moving speed: 750 mm / min,
Spray pitch: 22mm,
Distance between nozzle tip and glass plate: 115 mm
Droplet diameter: 6.59 μm.

The spray pitch and spray pattern are as shown in FIG. 3, and the nozzle 20 is moved on the glass plate 10A so as to repeat the following (x1) to (x4) from the upper end to the lower end of the glass plate 10A. The coating liquid (A) was applied to the entire surface of the plate 10A. This was used as a single-side coated product, and the same operation was further repeated 5 times to obtain a six-sided coated product, which was then heated and cured in an oven at 450 ° C. for 30 minutes to obtain a substrate with an AG layer.
(X1) The nozzle 20 is moved laterally from the first end 10a of the glass plate 10A to the second end 10b.
(X2) The nozzle 20 is moved 22 mm in the vertical direction.
(X3) The nozzle 20 is moved laterally from the second end 10b of the glass plate 10A to the second end 10b.
(X4) The nozzle 20 is moved 22 mm in the vertical direction.
For application by the spray method, a 6-axis coating robot (manufactured by Kawasaki Robotics, JF-5) was used. As the nozzle 20, a SU1A nozzle (manufactured by Spraying System Japan) was used.

[Examples 2 to 18]
A base material with an AG layer was obtained in the same manner as in Example 1 except that the coating conditions were changed as shown in Tables 2 and 3.

Table 2 and Table 3 show the spray conditions and evaluation results in each example. Further, as a representative example of the cross-sectional curve graph obtained by measurement on the surface of the AG layer, a cross-sectional curve graph of the AG layer in the base material with an AG layer of Example 1 is shown in FIG. In FIG. 4, a solid line shows a roughness curve.

As shown in Tables 2 and 3, Examples 1 to 12, which are base materials with an AG layer of the present invention, had low gloss and good antiglare properties, and also suppressed glare. Further, in the substrates with AG layers of Examples 1 to 12, the haze that causes a decrease in contrast was sufficiently low.
On the other hand, the glare was not sufficiently suppressed in the base material with an AG layer of Example 13 in which the average primary particle diameter of the silica fine particles contained in the AG layer was more than 1.0 μm.
Also in AG layer substrate with the convex parts N Example _P is less than 37 14-18 on the surface of the AG layer, glare is not sufficiently suppressed.

ADVANTAGE OF THE INVENTION According to this invention, a base material with an anti-glare layer which can fully suppress glare, and has the outstanding anti-glare property can be provided while diffusely reflecting external light with high efficiency. The base material with an antiglare layer of the present invention is useful for various image display devices (LCD, PDP, etc.), for image display device filters or protective plates, and for solar cell cover glasses.
The entire contents of the specification, claims, drawings, and abstract of Japanese Patent Application No. 2014-011674 filed on January 24, 2014 are incorporated herein as the disclosure of the present invention. .

DESCRIPTION OF SYMBOLS 1 Base material with AG layer 10 Base material 10A Glass plate 12 AG layer 20 Nozzle

Claims

A substrate and an antiglare layer formed on the substrate;
The antiglare layer contains a silica-based matrix and does not contain silica fine particles;
Convex parts N P measured by the convex parts measuring method described below is 37 or more at the surface of the antiglare layer, anti glare layer with the substrate.
(Method for measuring the number of convex parts)
In each of the cross-sectional curve graphs measured in accordance with JIS B0601 (2001) for any three points on the surface of the anti-glare layer, the height difference with respect to the minimum cross-section height is within a range of 500 μm in the horizontal axis direction. There was measured the number of protrusions having the above section height 100 nm, and the average value and the convex parts N P.
A substrate and an antiglare layer formed on the substrate;
The antiglare layer contains a silica-based matrix and silica fine particles,
The silica fine particles have an average primary particle size of 0.1 to 1.0 μm,
Convex parts N P measured by the convex parts measuring method described below is 37 or more at the surface of the antiglare layer, anti glare layer with the substrate.
(Method for measuring the number of convex parts)
In each of the cross-sectional curve graphs measured in accordance with JIS B0601 (2001) for any three points on the surface of the anti-glare layer, the height difference with respect to the minimum cross-section height is within a range of 500 μm in the horizontal axis direction. There was measured the number of protrusions having the above section height 100 nm, and the average value and the convex parts N P.
The base material with an antiglare layer according to claim 1 or 2, wherein the surface has a glossiness of 130 or less.
The substrate with an antiglare layer according to any one of claims 1 to 3, wherein the antiglare layer has a surface roughness Ra of 0.01 µm or more.
The substrate with an antiglare layer according to any one of claims 1 to 4, wherein the substrate is a tempered glass plate having a thickness of 0.05 to 2.5 mm.
A method for producing a substrate with an antiglare layer having a substrate and an antiglare layer formed on the substrate,
It includes a precursor and the dispersion medium of the silica-based matrix, a coating solution containing no silica fine particles, as the convex parts N P of the anti-glare layer surface measured by the convex parts measuring method described below is 37 or more, is heated A method for producing a base material with an antiglare layer, wherein the antiglare layer is formed by spraying on the base material by a spray method.
(Method for measuring the number of convex parts)
In each of the cross-sectional curve graphs measured in accordance with JIS B0601 (2001) for any three points on the surface of the anti-glare layer, the height difference with respect to the minimum cross-section height is within a range of 500 μm in the horizontal axis direction. There was measured the number of protrusions having the above section height 100 nm, and the average value and the convex parts N P.
A method for producing a substrate with an antiglare layer having a substrate and an antiglare layer formed on the substrate,
The coating liquid average primary particle diameter as the precursor of silica matrix containing a dispersion medium and the silica fine particles of 0.1 ~ 1.0 .mu.m, the convex parts N P of the anti-glare layer surface measured by the convex parts measuring method described below The manufacturing method of the base material with an anti-glare layer which sprays on a heated base material with a spray method so that it may become 37 or more and forms an anti-glare layer.
(Method for measuring the number of convex parts)
In each of the cross-sectional curve graphs measured in accordance with JIS B0601 (2001) for any three points on the surface of the anti-glare layer, the height difference with respect to the minimum cross-section height is within a range of 500 μm in the horizontal axis direction. There was measured the number of protrusions having the above section height 100 nm, and the average value and the convex parts N P.
The method for producing a substrate with an antiglare layer according to claim 6 or 7, wherein the solid concentration of the coating liquid is 0.3 to 6.0 mass%.
The method for producing a substrate with an antiglare layer according to any one of claims 6 to 8, wherein the coating liquid is sprayed using a spray spraying device having a two-fluid spray nozzle structure.