WO2021153423A1

WO2021153423A1 - Antiglare film, and film having antiglare properties and low reflectivity

Info

Publication number: WO2021153423A1
Application number: PCT/JP2021/002092
Authority: WO
Inventors: 穂高佐貫; 知之井上; 竜太郎國岡
Original assignee: パナソニックＩｐマネジメント株式会社
Priority date: 2020-01-27
Filing date: 2021-01-21
Publication date: 2021-08-05
Also published as: JPWO2021153423A1; CN115038995A; TW202132093A

Abstract

Provided is an antiglare film in which a reflection reducing layer that is less likely to reduce light reflection performance can be formed. This antiglare film 1 comprises, on at least one surface of a transparent base material layer 2, an antiglare layer 3 which contains a binder resin (A), and organic fine particles (B) and inorganic fine particles (C) dispersed in the binder resin (A). The absolute value of the difference in refractive index between the binder resin (A) and the organic fine particles (B) is 0.005-0.25. The average primary particle diameter of the inorganic fine particles (C) is smaller than the average primary particle diameter of the organic fine particles (B). The arithmetic average roughness (Ra) of the surface of the antiglare layer 3 is in the range of 0.080-0.210 μm. The average interval (Sm) of the irregularities on the surface of the antiglare layer 3 is 0.100-0.200 μm.

Description

Anti-glare film and anti-glare and low-reflection film

The present disclosure relates to an antiglare film and a film having antiglare and low reflectivity. More specifically, an antiglare film having a transparent base material layer and an antiglare layer in which organic fine particles and inorganic fine particles are dispersed in a binder resin on at least one surface of the transparent base material layer, and the antiglare film. The present invention relates to a film having antiglare property and low reflectivity using a film.

Patent Document 1 describes an antiglare film. This antiglare film has an antiglare layer having an uneven shape on the surface on at least one surface of the light transmissive base material. The antiglare layer contains an agglomerate in which two or more kinds of spherical fine particles are aggregated. A convex portion is formed on the surface of the antiglare layer by the aggregate, and an uneven shape on the surface of the antiglare layer is formed. Further, the two or more kinds of spherical fine particles include at least one kind or more organic fine particles and one or more kinds of inorganic fine particles. The organic fine particles have an average particle size of 0.3 to 10.0 μm, and the inorganic fine particles have an average particle size of 500 nm to 5.0 μm.

In the antiglare film described in Patent Document 1, when an attempt is made to form a functional layer such as a reflection reduction layer on the uneven surface of the antiglare layer, the functional layer is affected by the uneven shape of the surface of the antiglare layer. Sometimes it became difficult to perform its function.

For example, when the functional layer is a reflection reduction layer, if the reflection reduction layer is formed on the surface of the antiglare layer, the thickness of the functional layer tends to be non-uniform, and the light reflection suppression ability of the reflection reduction layer may decrease. there were.

Japanese Patent No. 5974894

An object of the present disclosure is to provide an antiglare film that easily forms a reflection reduction layer in which the light reflection suppression ability is less likely to decrease, and a film having antiglare and low reflection properties.

The antiglare film according to one aspect of the present disclosure includes a binder resin (A) and organic fine particles dispersed in the binder resin (A) on at least one surface of the transparent base material layer and the transparent base material layer. An antiglare layer containing (B) and inorganic fine particles (C) is provided. The absolute value of the difference in refractive index between the binder resin (A) and the organic fine particles (B) is 0.005 or more and 0.25 or less. The average primary particle size of the inorganic fine particles (C) is smaller than the average primary particle size of the organic fine particles (B). The arithmetic mean roughness (Ra) of the antiglare layer surface is in the range of 0.080 μm or more and 0.210 μm or less, and the average interval (Sm) of the irregularities on the antiglare layer surface is 0.100 μm or more and 0.200 μm. It is as follows.

The film having antiglare property and low reflectivity according to one aspect of the present disclosure includes a high refractive index layer, an ultrahigh refractive index layer, and a low refractive index layer on the antiglare layer in the antiglare film. Are prepared in this order. The high refractive index layer has a refractive index of 1.60 or more and 1.70 or less. The ultra-high refractive index layer has a refractive index of 1.75 or more and 1.90 or less. The low refractive index layer has a refractive index of 1.30 or more and 1.40 or less.

FIG. 1 is a cross-sectional view showing an embodiment of the antiglare film according to the present disclosure. FIG. 2 shows an embodiment of the antiglare film according to the present disclosure, and is a partially enlarged schematic view. FIG. 3 is a cross-sectional view showing an embodiment of a film having antiglare and low reflectivity according to the present disclosure. FIG. 4 shows an embodiment of a film having antiglare and low reflectivity according to the present disclosure, and is a partially enlarged schematic view. FIG. 5 shows a comparative example with respect to the antiglare film according to the present disclosure, and is a partially enlarged schematic view. FIG. 6 shows a comparative example with respect to the film having antiglare property and low reflection property according to the present disclosure, and is a partially enlarged schematic view. FIG. 7 shows another comparative example with respect to the film having antiglare property and low reflection property according to the present disclosure, and is a partially enlarged schematic view. FIG. 8 shows another comparative example with respect to the antiglare film according to the present disclosure, and is a partially enlarged schematic view. FIG. 9 shows another comparative example with respect to the film having antiglare property and low reflection property according to the present disclosure, and is a partially enlarged schematic view.

(1) Outline The antiglare film 1 of the present embodiment is dispersed in a binder resin (A) and the binder resin (A) on at least one surface of the transparent base material layer 2 and the transparent base material layer 2. The antiglare layer 3 containing the organic fine particles (B) and the inorganic fine particles (C) is provided (see FIG. 1). The absolute value of the difference in refractive index between the binder resin (A) and the organic fine particles (B) is 0.005 or more and 0.25 or less. The average primary particle size of the inorganic fine particles (C) is smaller than the average primary particle size of the organic fine particles (B). The arithmetic mean roughness (Ra) on the surface of the antiglare layer 3 is in the range of 0.080 μm or more and 0.210 μm or less, and the average interval (Sm) of the unevenness on the surface of the antiglare layer 3 is 0.100 μm or more and 0.200 μm or less. Is.

Since the antiglare film 1 has the antiglare layer 3 in which the organic fine particles (B) and the inorganic fine particles (C) are dispersed in the binder resin (A), the organic fine particles (B) of the binder resin (A) are present. The portion of the binder resin (A) is likely to be convex, and the portion of the binder resin (A) in which the organic fine particles (B) are not present is likely to be concave. Can be formed. Further, since the absolute value of the difference in refractive index between the binder resin (A) and the organic fine particles (B) is 0.005 or more and 0.25 or less, it is prevented by the interaction with the unevenness of the surface of the antiglare layer 3. The glare layer 3 has antiglare properties. The "anti-glare property" is a property that suppresses a decrease in visibility caused by reflection of external light due to diffuse reflection of incident light on an uneven surface. Therefore, by providing the antiglare film 1 on the surface of the display or the like, it is possible to reduce the reflection of fluorescent lamps, external light, and the like, and it is possible to improve the visibility.

Further, in the antiglare film 1, the arithmetic average roughness (Ra) of the surface of the antiglare layer 3 is in the range of 0.080 μm or more and 0.210 μm or less, and the average spacing (Sm) of the irregularities on the surface of the antiglare layer 3 is. Since it is 0.100 μm or more and 0.200 μm or less, the functional layer formed on the surface of the antiglare layer 3 is likely to be formed on the concave portion and the convex portion of the surface of the antiglare layer 3 with the same thickness. Therefore, when the functional layer is a reflection reduction layer, the thickness of the reflection reduction layer is uniformly formed, so that the function of the reflection reduction layer, that is, the function of suppressing the reflection of incident light is not easily impaired.

Further, since the average primary particle size of the inorganic fine particles (C) is smaller than the average primary particle size of the organic fine particles (B), the arithmetic mean roughness (Ra) of the surface of the antiglare layer 3 and the surface of the antiglare layer 3 The average spacing (Sm) of the unevenness can be easily formed in a desired range.

In the antiglare film 1, it is preferable that the hydroxyl group concentration of the binder resin (A) is larger than 0 mmol / g and 2.50 mmol / g or less. In this case, the aggregated state of the organic fine particles (B) and the inorganic fine particles (C) can be easily controlled, and the arithmetic mean roughness (Ra) and the average spacing (Sm) of the irregularities on the surface of the antiglare layer 3 can be easily controlled.

In the antiglare film 1, the binder resin (A) preferably contains a hydroxyl group-containing acrylate. In this case, it is easy to adjust the hydroxyl group concentration of the binder resin (A).

In the antiglare film 1, it is preferable that the average primary particle diameter of the organic fine particles (B) is 2 μm or more and 7 μm or less. In this case, an appropriate uneven shape is likely to be formed on the surface of the antiglare layer, and the antiglare performance of the antiglare film is unlikely to be insufficient.

In the antiglare film 1, the average primary particle diameter of the inorganic fine particles (C) is preferably 1 nm or more and 200 nm or less. In this case, aggregates of organic fine particles (B) are likely to be formed in the antiglare layer, and inorganic fine particles (C) are likely to enter between the organic fine particles (B) and the transparent base material layer 2, so that the antiglare film 1 However, it becomes easier to obtain anti-glare properties.

In the antiglare film 1, it is preferable that the inorganic fine particles (C) contain fumed silica. In this case, the inorganic fine particles (C) can have a high affinity for the organic fine particles (B), and the inorganic fine particles (C) can easily enter between the organic fine particles (B) and the transparent base material layer 2. Become.

The film 10 having antiglare and low reflectance has a high refractive index layer having a refractive index of 1.60 or more and 1.70 or less and a refractive index of 1.75 on the antiglare layer of the antiglare film. An ultra-high refractive index layer having a refractive index of 1.90 or less and a low refractive index layer having a refractive index of 1.30 or more and 1.40 or less are provided in this order. In this case, the film 10 can easily obtain antiglare property and low reflectivity.

(2) Details (anti-glare film)
The antiglare film 1 has an antiglare layer 3 in which organic fine particles (B) and inorganic fine particles (C) are dispersed in a binder resin (A) on at least one surface of the transparent base material layer 2 (FIG. 1). reference). The antiglare layer 3 may be formed on only one of the two surfaces of the transparent base material layer 2 facing each other in the thickness direction, or may be formed on both surfaces. The antiglare layer 3 is formed by containing organic fine particles (B) and inorganic fine particles (C) in a binder resin (A).

(Film with anti-glare and low reflectivity)
The film having antiglare and low reflectance (hereinafter, may be simply referred to as “antiglare low reflection film”) 10 has a high refractive index layer 41 and a super-refractive index layer 41 on the antiglare layer 3 of the antiglare film 1. The high refractive index layer 42 and the low refractive index layer 43 are provided in this order.

(Transparent base material layer)
The transparent base material layer 2 is a transparent film that supports the antiglare layer 3 and the reflection reduction layer 4. Here, the term "transparent" includes translucency, and the light transmittance is 80% or more and 100% or less, preferably 85% or more and 100% or less, and more preferably 90% or more and 100% or less. When the light transmittance of the transparent base material layer 2 is 90% or more, there is an advantage that it can be suitably used as an optical film.

The transparent base material layer 2 can be formed of a material containing a synthetic resin. As the synthetic resin, for example, polyester (PET), cellulose triacetate (TAC), or the like is preferable, whereby the transparent base material layer 2 is excellent in mechanical strength and also excellent in optical properties. In addition to PET and TAC, synthetic resins include cellulose diacetate, cellulose acetate butyrate, polyamide, polyimide, polyether sulphon, poly sulphon, polypropylene, polymethylpentene, polyvinyl chloride, polyvinyl acetal, polyetherketone, and poly. Examples thereof include thermoplastic resins such as methyl methacrylate, polycarbonate, and polyurethane.

Among polyester films, polyethylene terephthalate (PET) and polyethylene naphthalate biaxially stretched films have excellent mechanical properties, heat resistance, chemical resistance, etc., and therefore are used for magnetic tapes, ferromagnetic thin film tapes, and packaging. It is suitable as a material for films, films for electronic parts, electrically insulating films, laminating films, films to be attached to the surface of displays, and protective films for various members. In particular, for display applications, base films such as prism lens sheets, touch panels, and backlights, which are members of liquid crystal display devices, base films for antiglare film 1 and antiglare low reflection film 10 for televisions, and front optical filters for plasma televisions. It is suitable as an antiglare film 1 and an antiglare low reflection film 10, a near infrared cut film, a base film of an electromagnetic wave shielding film, and the like.

Examples of the polyester include aromatic dicarboxylic acid components such as terephthalic acid, isophthalic acid, 2,6-naphthalindicarboxylic acid, and 4,4'-diphenyldicarboxylic acid, and ethylene glycol, 1,4-butanediol, 1,4-. Aromatic polyesters produced by reacting with glycol components such as cyclohexanedimethanol and 1,6-hexanediol are preferable, and polyethylene terephthalate, polyethylene-2,6-naphthalindicarboxylate and the like are particularly preferable. Further, the polyester may be a copolymerized polyester containing a plurality of the above-exemplified components.

The transparent base material layer 2 may contain organic or inorganic particles. In this case, the takeability, transportability, etc. of the transparent base material layer 2 are improved. Examples of such particles include calcium carbonate particles, calcium oxide particles, aluminum oxide particles, kaolin, silicon oxide particles, zinc oxide particles, crosslinked acrylic resin particles, crosslinked polystyrene resin particles, urea resin particles, melamine resin particles, and crosslinked silicone resin particles. And so on. The transparent base material layer 2 may also contain a colorant, an antistatic agent, an ultraviolet absorber, an antioxidant, a lubricant, a catalyst, another resin and the like as long as the transparency is not impaired.

The haze of the transparent base material layer 2 is preferably 3% or less. In this case, the visibility of the image or the like passed through the antiglare film 1 and the antiglare low reflection film 10 is improved, and the antiglare film 1 and the antiglare film 1 and the antiglare film 10 are improved in visibility. The low-reflection film 10 is particularly suitable as a film for optical applications. It is more preferable that the haze is 1.5% or less.

The thickness of the transparent base material layer 2 is not particularly limited, but is preferably in the range of 20 μm or more and 200 μm or less. In particular, when the thickness of the transparent base material layer 2 is 25 μm or more and 100 μm or less, the antiglare film 1 and the antiglare low reflection film 10 can be made thinner and lighter, and the antiglare film 1 and the antiglare low reflection film 10 can be made thinner and lighter. The occurrence of interference on both surfaces (front and back) is suppressed, and the heat shrinkage when the transparent base material layer 2 is heated is suppressed, and problems such as deterioration of workability due to the heat shrinkage of the transparent base material layer 2 are suppressed. Will be done.

The surface reflectance of the transparent base material layer 2 is preferably in the range of 4% or more and 6% or less. When the surface reflectance of the transparent base material layer 2 is within this range, the occurrence of interference on both surfaces (front and back surfaces) of the transparent base material layer 2 is suppressed, and it becomes easy to secure low reflectance characteristics.

In the present embodiment, it is preferable that the surface of the transparent base material layer 2 is subjected to an easy-adhesion treatment. Examples of the easy-adhesion treatment include plasma treatment, dry treatment such as corona treatment, chemical treatment such as alkali treatment, and coating treatment for forming an easy-adhesion layer. The easy-adhesion treatment suppresses the occurrence of blocking when the single film of the transparent base material layer 2 which is the material of the antiglare film 1 and the antiglare low-reflection film 10 is wound in a roll shape and is laminated. It is applied to improve slipperiness. Among the above-mentioned easy-adhesion treatments, it is preferable to laminate the easy-adhesion layer on the surface (on the first main surface) of the transparent base material layer 2. In this case, it is preferable that an easy-adhesion layer is interposed between the transparent base material layer 2 and the high refractive index layer 41. Further, the easy-adhesion treatment can be used to improve the adhesiveness between the transparent base material layer 2 and the antiglare layer 3. The material of the easy-adhesion layer is not limited, but it is particularly preferable that the layer is formed of a polyester resin, an acrylic resin, or the like. In order to suppress the increase in the reflectance of the antiglare film 1 and the antiglare low reflection film 10 due to interfacial reflection on the surface of the easy-adhesion layer, the refractive index of the easy-adhesion layer is the refractive index of the transparent base material layer 2. It is desirable that the refractive index is close to that of the antiglare layer 3, and particularly preferably in the range of 1.58 to 1.75. The optical film thickness of the easy-adhesion layer is preferably in the range of 120 to 160 nm. In this case, while ensuring high adhesion between the transparent base material layer 2 and the high refractive index layer 41, an increase in reflectance and occurrence of interference unevenness due to the presence of the easy-adhesion layer are suppressed.

(Anti-glare layer)
The antiglare layer 3 is formed by dispersing organic fine particles (B) and inorganic fine particles (C) in a binder resin (A). The organic fine particles (B) and the inorganic fine particles (C) are not uniformly dispersed in the binder resin (A), and the plurality of organic fine particles (B) and the plurality of inorganic fine particles (C) are appropriately contained in each. It is unevenly distributed. In particular, the plurality of organic fine particles (B) form secondary particles, and the secondary particles form the surface of the antiglare layer 3 (the surface not facing the transparent base material layer 2) in an uneven shape. There is. That is, the surface convexity of the antiglare layer 3 is likely to be formed corresponding to the portion where the secondary particles of the plurality of organic fine particles (B) are present, and the portion where the secondary particles of the plurality of organic fine particles (B) are not present. Correspondingly, recesses on the surface of the antiglare layer 3 are likely to be formed.

The arithmetic mean roughness (Ra) on the surface of the antiglare layer 3 is in the range of 0.080 μm or more and 0.210 μm or less, and the average interval (Sm) of the unevenness on the surface of the antiglare layer 3 is 0.100 μm or more and 0. It is 200 μm or less. The arithmetic average roughness (Ra) and the average spacing (Sm) of the unevenness are measured by a method according to JIS B 0601-1994. If the arithmetic average roughness (Ra) on the surface of the antiglare layer 3 and the average spacing (Sm) of the irregularities on the surface of the antiglare layer 3 are each within the above-mentioned predetermined ranges, it is easy to uniformly form the thickness of the reflection reduction layer. Therefore, the function of the reflection reduction layer 4 that suppresses the reflection of the incident light is not easily impaired.

The arithmetic mean roughness (Ra) of the surface of the antiglare layer 3 is more preferably in the range of 0.080 μm or more and 0.200 μm or less, and further preferably in the range of 0.080 μm or more and 0.130 μm or less. When the arithmetic mean roughness (Ra) is smaller than 0.080 μm, when the reflection reduction layer 4 is laminated on the antiglare layer 3, the unevenness formed on the surface of the antiglare layer 3 is formed by the reflection reduction layer 4. It is easy to be buried and it may be difficult to develop antiglare property. When the arithmetic mean roughness (Ra) is larger than 0.210 μm, the surface roughness of the antiglare layer 3 becomes too large to prevent glare. When the reflection reduction layer 4 is laminated on the layer 3, the thickness of the reflection reduction layer 4 tends to be uneven.

The average spacing (Sm) of the irregularities on the surface of the antiglare layer 3 is more preferably 0.100 μm or more and 0.150 μm or less, and further preferably 0.100 μm or more and 0.140 μm or less. When the average spacing (Sm) of the unevenness is smaller than 0.100 μm, it is possible that the organic fine particles (B) do not form aggregates of an appropriate size in the antiglare layer 3, and at the same time, the arithmetic mean. Roughness (Ra) may be too small. When the average spacing (Sm) of the unevenness is larger than 0.200 μm, the spacing between the irregularities on the surface of the antiglare layer 3 becomes too large, and the reflection is reduced when the reflection reducing layer 4 is laminated on the antiglare layer 3. The thickness of the layer 4 tends to be uneven.

FIG. 2 schematically shows the antiglare layer 3. The antiglare layer 3 is formed on one surface of the transparent base material layer 2, and a plurality of organic fine particles (B) and a plurality of inorganic fine particles (C) are dispersed in a layered binder resin (A). .. The average primary particle size of the inorganic fine particles (C) is smaller than the average primary particle size of the organic fine particles (B). Since the inorganic fine particles (C) are much finer particles than the organic fine particles (B), they are not clearly shown.

The surface of the antiglare layer 3 (the surface not facing the transparent base material layer 2) is formed in an uneven shape (see FIG. 2). At the convex portion of the surface of the antiglare layer 3, a plurality of organic fine particles (B) are aggregated in the binder resin (A) to form secondary particles. That is, the binder resin (A) is raised by the secondary particles of the plurality of organic fine particles (B) to form protrusions. On the other hand, in the concave portion on the surface of the antiglare layer 3, a plurality of organic fine particles (B) are not aggregated in the binder resin (A), or the organic fine particles (B) are not present. That is, in the portion where the plurality of organic fine particles (B) are not aggregated or in the portion where the organic fine particles (B) do not exist, the binder resin (A) is lower than the convex and the concave is formed.

In the present embodiment, the unevenness of the surface of the antiglare layer 3 is relatively gentle. That is, the height difference between the concave and convex surfaces of the antiglare layer 3 is relatively small. Therefore, as shown in FIGS. 3 and 4, when the reflection reduction layer 4 is formed (laminated) on the antiglare layer 3 by wet coating, when the reflection reduction layer 4 is formed on the surface of the antiglare layer 3, the reflection reduction layer 4 is formed. , Easy to form to a uniform thickness. That is, when the surface of the antiglare layer 3 has an appropriate uneven shape, the film thickness unevenness of the reflection reduction layer 4 formed on the surface of the antiglare layer 3 is small, and the expected optical characteristics (low reflection, etc.) are exhibited. It's easy to do. Moreover, since the unevenness can be maintained, both anti-glare property and low reflection property can be achieved at the same time.

On the other hand, in the antiglare layer 3 shown in FIG. 5, the arithmetic average roughness (Ra) of the surface is larger than 0.210 μm, and the average interval (Sm) of the unevenness is smaller than 0.100 μm. In the antiglare layer 3, the aggregated particle size of the organic fine particles (B) aggregated in the binder resin (A) is larger on average and the number is larger than in the case of FIG. In addition, there are many parts of the binder resin (A) in which the organic fine particles (B) do not exist. Therefore, the height difference between the concave and convex surfaces of the antiglare layer 3 is larger than that in FIG. 2. Therefore, when the reflection reduction layer 4 is formed (laminated) on the antiglare layer 3 by wet coating, the thickness of the reflection reduction layer 4 is unlikely to be uniform as shown in FIG. That is, the reflection reduction layer 4 is often thickened at the concave portion of the antiglare layer 3 and thinned at the convex portion, and liquid pools occur in the concave portion, resulting in uneven film thickness. Therefore, the expected optical characteristics (low). (Reflection, etc.) is unlikely to occur. Further, as shown in FIG. 7, when the reflection reduction layer 4 is laminated on the antiglare layer 3 by dry coating, it is possible to form the reflection reduction layer 4 having high thickness uniformity, but the reflection reduction layer 4 Unevenness on the surface of the antiglare layer 3 may appear on the surface, and the desired reflection performance may not be obtained. Here, the dry coating means a PVD (physical vapor deposition) method or a CVD (chemical vapor deposition) method, and the wet coating means a liquid substance such as a coating method or a spray method. It means a method of supplying and coating.

Further, in the antiglare layer 3 shown in FIG. 8, the arithmetic average roughness (Ra) of the surface is smaller than 0.080 μm, and the average interval (Sm) of the unevenness is larger than 0.200 μm. In the antiglare layer 3, the aggregated particle size of the organic fine particles (B) aggregated in the binder resin (A) is smaller and smaller on average than in the case of FIG. 2, and the organic fine particles (B) Is hardly agglomerated, and there are few portions of the binder resin (A) in which the organic fine particles (B) are not present. Therefore, the height difference between the concave and convex surfaces of the antiglare layer 3 is smaller than in the case of FIG. Therefore, as shown in FIG. 9, the thickness of the reflection reduction layer 4 tends to be uniform. The anti-glare performance due to the uneven shape of the anti-glare layer 3 is lowered, and it becomes difficult to obtain the anti-glare low-reflection film 10 having both excellent anti-glare and reflective properties.

Since the uneven state of the antiglare layer 3 is mainly affected by the primary particle size, the aggregated particle size, and the dispersed state of the organic fine particles (B), the organic fine particles (B) are the transparent base material layer of the antiglare layer 3. It is preferable that the inorganic fine particles (C) are mainly dispersed on the surface side opposite to the second, and the inorganic fine particles (C) are dispersed between the organic fine particles (B) of the antiglare layer 3 and the transparent base material layer 2. Is preferable.

Further, since the average primary particle size of the inorganic fine particles (C) is smaller than the average primary particle size of the organic fine particles (B), the arithmetic mean roughness (Ra) of the surface of the antiglare layer 3 and the surface of the antiglare layer 3 The average spacing (Sm) of the unevenness can be easily formed in a desired range. Although the details are not clear, the inorganic fine particles (C) that have entered between the organic fine particles (B) and the transparent base material layer 2 unevenly distribute the organic fine particles (B) on the surface side of the transparent base material layer 2. The inventor thinks that the inorganic fine particles (C) are smaller than the organic fine particles (B), so that the effect of the organic fine particles (B) on the unevenness of the surface of the antiglare layer 3 is fine. The inventor believes that it is controllable.

The antiglare layer 3 is a composition for an antiglare layer containing, for example, organic fine particles (B), inorganic fine particles (C), an uncured binder resin such as an ionizing radiation curable resin, a photopolymerization initiator, and a solvent. It can be formed by applying an object to a transparent base film, drying the coating film, and curing the coating film by ionizing radiation irradiation or the like.

Further, the thickness of the antiglare layer 3 is preferably 2 μm or more and 10 μm or less. If the thickness of the antiglare layer 3 is less than 2 μm, the surface of the antiglare layer 3 may be easily scratched, and if the thickness of the antiglare layer 3 exceeds 10 μm, the antiglare layer 3 is easily cracked. Sometimes. The thickness of the antiglare layer 3 is more preferably 3 μm or more and 8 μm or less, and the thickness of the antiglare layer 3 is more preferably 3 μm or more and 6 μm or less.

(Binder resin)
The binder resin (A) is preferably transparent, and is preferably an ionizing radiation curable resin that is cured by ultraviolet rays or electron beams, for example. The "resin" includes a monomer, an oligomer, and the like.

Examples of the ionizing radiation curable resin include compounds having one or two or more unsaturated bonds such as compounds having a functional group such as an acrylate-based resin. Examples of the compound having an unsaturated bond of 1 include ethyl (meth) acrylate, ethylhexyl (meth) acrylate, styrene, methylstyrene, N-vinylpyrrolidone and the like. Examples of the compound having two or more unsaturated bonds include polymethylol propantri (meth) acrylate, hexanediol (meth) acrylate, tripropylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and pentaerythritol tri (). Polyfunctional compounds such as meta) acrylate, dipentaerythritol hexa (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, or the above polyfunctional compound and (meth) acrylate. Reaction products such as (for example, poly (meth) acrylate ester of polyhydric alcohol), and the like can be mentioned. In addition, "(meth) acrylate" refers to methacrylate and acrylate. Further, in the present invention, as the ionizing radiation curable resin, the above-mentioned compound modified with PO, EO or the like can also be used.

In addition to the above compounds, relatively low molecular weight polyester resins, polyether resins, acrylic resins, epoxy resins, urethane resins, alkyd resins, spiroacetal resins, polybutadiene resins, polythiol polyene resins and the like having unsaturated double bonds are also mentioned above. It can be used as an ionizing radiation curable resin.

The above-mentioned ionizing radiation curable resin is used in combination with a solvent-drying resin (a resin such as a thermoplastic resin that forms a film simply by drying a solvent added to adjust the solid content at the time of coating). You can also do it. By using the solvent-drying resin in combination, the viscosity of the coating liquid can be easily adjusted when the antiglare layer 3 is formed, and film defects on the coating surface of the coating liquid can be effectively prevented. The solvent-drying resin that can be used in combination with the ionizing radiation curable resin is not particularly limited, and in general, a thermoplastic resin can be used.

The thermoplastic resin is not particularly limited, and for example, a styrene resin, a (meth) acrylic resin, a vinyl acetate resin, a vinyl ether resin, a halogen-containing resin, an alicyclic olefin resin, a polycarbonate resin, and a polyester resin. Examples thereof include resins, polyamide resins, cellulose derivatives, silicone resins and rubbers or elastomers. The thermoplastic resin is preferably amorphous and soluble in an organic solvent (particularly a common solvent capable of dissolving a plurality of polymers and curable compounds). In particular, from the viewpoint of film forming property, transparency and weather resistance, styrene resin, (meth) acrylic resin, alicyclic olefin resin, polyester resin, cellulose derivative (cellulose ester, etc.) and the like are preferable.

Further, the antiglare layer may contain a thermosetting resin. The thermosetting resin is not particularly limited, and for example, phenol resin, urea resin, diallyl phthalate resin, melamine resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, aminoalkyd resin, melamine-urea cocondensation resin. , Silicon resin, polysiloxane resin and the like.

The binder resin (A) preferably contains a hydroxyl group-containing polyfunctional acrylate. This makes it easy to adjust the hydroxyl group concentration of the binder resin (A). Examples of the hydroxyl group-containing polyfunctional acrylate include those in Table 1. Here, PE2A is pentaerythritol diacrylate, PE3A is pentaerythritol triacrylate, and PE4A is pentaerythritol tetraacrylate. Further, DP5A is dipentaerythritol pentaacrylate, and DP6A is dipentaerythritol hexaacrylate. Further, GR2A is a glycerin diacrylate, and GR3A is a glycerin triacrylate.

The hydroxyl group concentration of the binder resin (A) is preferably greater than 0 mmol / g and less than 2.50 mmol / g. Thereby, the aggregated state of the organic fine particles (B) and the inorganic fine particles (C) can be controlled, and the arithmetic average roughness (Ra) of the surface of the antiglare layer 3 and the average spacing (Sm) of the irregularities can be easily controlled. Become.

The hydroxyl group concentration of the binder resin (A) is represented by the following formula 1 as the number of hydroxyl groups contained in one molecule of the resin when the binder resin (A) is composed of a single resin.
Hydroxy group concentration (mmol / g) = (number of hydroxyl groups in one molecule) / (molecular weight) x 1000 (Equation 1)
When the binder resin (A) is composed of a plurality of resins, the weighted average value can be calculated and obtained from the hydroxyl group concentration calculated from the formula 1 of each binder resin.

The hydroxyl group concentration of the binder resin (A) is more preferably greater than 0 mmol / g and 1.50 mmol / g or less, and further preferably greater than 0 mmol / g and 1.00 mmol / g or less.

In particular, when the organic fine particles (B) are particles made of a copolymer having generally low polarity, such as acrylic-styrene copolymer particles, the polarity of the binder resin (A), which is a matrix (dispersion medium), is low. That is, the lower the hydroxyl group concentration of the binder resin (A), the higher the dispersibility of the dispersoid organic fine particles (B), the less likely it is to form aggregates, and the closer the primary particles are dispersed alone. On the other hand, the higher the polarity of the binder resin (A), that is, the higher the hydroxyl group concentration of the binder resin (A), the lower the dispersibility of the dispersible organic fine particles (B), the easier it is to form aggregates, and the more organic the binder resin (A) is. Aggregates of fine particles (B) also tend to grow large.

In the present invention, when the hydroxyl group concentration of the binder resin (A) is larger than 2.50 mmol / g, the aggregates of the organic fine particles (B) may become too large, and the average interval (Sm) may become too large. There is sex.

The hydroxyl group concentration of the binder resin (A) can be adjusted by mixing a plurality of types of resin components having different hydroxyl group concentrations. For example, of the 100% resin component of the binder resin (A), 40% is a high-viscosity urethane acrylate (hydroxyl concentration 0 mmol / g), and the remaining 60% is a hydroxyl group such as a combination of PE2A / PE3A / PE4A. The hydroxyl group concentration can be controlled as a mixture of pentaerythritol polyacrylates having different concentrations. In particular, the performance of the antiglare layer 3 is likely to be exhibited in the range of mass ratio of PE3A / PE4A = 70/30 to 10/90. A mixture of dipentaerythritol polyacrylate may be used instead of the mixture of pentaerythritol polyacrylate.

(Organic fine particles)
The organic fine particles (B) are also called diffusion particles, and are mainly fine particles for forming the surface uneven shape of the antiglare layer 3. When the aggregate contains such organic fine particles (B), it becomes easy to control the size of the uneven shape formed on the antiglare layer 3 and the refractive index of the antiglare layer 3, and the antiglare property is controlled and low. Reflectivity can be suppressed. The organic fine particles (B) are preferably transparent.

As the organic fine particles (B), at least one material selected from the group consisting of acrylic resin, polystyrene resin, styrene-acrylic copolymer resin, polyethylene resin, epoxy resin, silicone resin, polyvinylidene fluoride resin and polyfluorinated ethylene resin. It is preferably a fine particle composed of. Of these, fine particles of a styrene-acrylic copolymer are preferable because the refractive index can be easily controlled.

The absolute value of the difference in refractive index between the binder resin (A) and the organic fine particles (B) is 0.005 or more and 0.25 or less. Therefore, the antiglare layer 3 has antiglare properties due to the interaction with the unevenness of the surface of the antiglare layer 3. The absolute value of the difference in refractive index between the binder resin (A) and the organic fine particles (B) is more preferably 0.005 or more and 0.15 or less, and further preferably 0.005 or more and 0.10 or less. be.

The organic fine particles (B) are preferably contained in the antiglare layer 3 in an amount of 5% by mass or more and 20% by mass or less. If the content of the organic fine particles (B) is less than 5% by mass, the aggregates of the organic fine particles (B) may decrease, and the antiglare performance of the antiglare layer 3 may deteriorate. If the content of the organic fine particles (B) exceeds 20% by mass, the number of aggregates may increase or the aggregates may become too large, and the antiglare performance of the antiglare layer 3 may deteriorate. The organic fine particles (B) are more preferably contained in the antiglare layer 3 in an amount of 6% by mass or more and 15% by mass or less, and are contained in the antiglare layer 3 in an amount of 8% by mass or more and 12% by mass or less. Is even more preferable. Further, the organic fine particles (B) are preferably contained in the antiglare layer 3 in an amount of 5% by volume or more and 20% by volume or less. It is more preferably 6.0% by volume or more and 15.0% by volume or less, and further preferably 8.0% by volume or more and 12.0% by volume or less.

The average primary particle size of the organic fine particles (B) is preferably 2 μm or more and 7 μm or less. If the average primary particle size of the organic fine particles (B) is less than 2 μm, it becomes difficult to form a sufficient uneven shape on the surface of the antiglare layer 3, and the antiglare performance of the antiglare film 1 may be insufficient. If the average primary particle size of the organic fine particles (B) exceeds 7 μm, the uneven shape on the surface of the antiglare layer 3 becomes too large, and the antiglare performance of the antiglare film 1 may be insufficient. The average primary particle size of the organic fine particles (B) is more preferably 3 μm or more and 6 μm or less, and the average primary particle size of the organic fine particles (B) is more preferably 3 μm or more and 5 μm or less.

In the present disclosure, the "average primary particle size" may be any method as long as the average particle size of the primary particles can be calculated, and examples thereof include an image analysis method, a Coulter method, a centrifugal sedimentation method, and a laser diffraction / scattering method. Can be mentioned.

(Inorganic fine particles)
Inorganic fine particles are also called binder particles, and are contained in the antiglare layer 3 so as to enter between adjacent organic fine particles (B) and above and below the organic fine particles (B). In particular, the arithmetic average roughness is caused by the inclusion of the inorganic fine particles (C) between the adjacent organic fine particles (B) and the inclusion of the inorganic fine particles (C) between the organic fine particles (B) and the transparent base material layer 2. The roughness (Ra) and the average spacing (Sm) of the unevenness can be maintained appropriately.

The density of the inorganic fine particles (C) is preferably higher than the density of the organic fine particles (B). As a result, when the composition for the antiglare layer containing the binder resin (A), the organic fine particles (B) and the inorganic fine particles (C) is applied to the transparent base material layer 2, the inorganic fine particles (C) are more organic fine particles. It becomes easier to settle before (B), and as a result, the inorganic fine particles (C) easily enter between the organic fine particles (B) and the transparent base material layer 2.

The density of the organic fine particles (B) ^{is preferably in the range of 0.8 to 1.5 g / cm 3} , and the density of the inorganic fine particles (C) is in the range of ^{1.8 to 3.0 g / cm 3.} Is preferable.

Such inorganic fine particles (C) are preferably at least one kind of fine particles selected from the group consisting of, for example, aluminosilicate, talc, mica and silica. The inorganic fine particles (C) preferably contain fumed silica. As a result, the inorganic fine particles (C) can have a high affinity for the organic fine particles (B). Fused silica refers to amorphous silica having a particle size of 200 nm or less produced by a dry method, and is obtained by reacting a volatile compound containing silicon in a gas phase.

Silanol groups are present on the surface of fumed silica, but fumed silica is preferably surface-treated, and the surface treatment is preferably hydrophobized. By surface-treating the fumed silica, the fumed silica can be suitably unevenly distributed on the surface of the organic fine particles, and the agglomerates of the organic fine particles (B) are formed by the cohesive force of the fumed silica itself. be able to. In addition, the chemical resistance and saponification resistance of the fumed silica itself can be improved. When the surface treatment (hydrophobic treatment) is not performed, fumed silica may be excessively present on the surface of the organic fine particles and the cohesive force may increase, so that a suitable uneven shape may not be formed. As the hydrophobizing treatment, for example, methyl treatment, octylsilane treatment, dimethyl silicone oil treatment and the like are suitable.

The average primary particle size of the inorganic fine particles (C) is preferably 1 nm or more and 200 nm or less. If the average primary particle size of the inorganic fine particles (C) is less than 1 nm, agglomerates of the organic fine particles (B) may not be sufficiently formed in the antiglare layer 3, and the average primary particle size of the inorganic fine particles (C) may not be sufficiently formed. If it exceeds 200 nm, it becomes difficult for the inorganic fine particles (C) to enter between the organic fine particles (B) and the transparent base material layer 2, and the arithmetic mean roughness (Ra) of the surface of the antiglare layer 3 becomes too small. It may be difficult to obtain anti-glare properties. The average primary particle size of the inorganic fine particles (C) is more preferably 10 nm or more and 200 nm or less, and the average primary particle size of the inorganic fine particles (C) is more preferably 12 nm or more and 40 nm or less.

The content of the inorganic fine particles (C) is preferably 1% by mass or more and 10% by mass or less in the antiglare layer 3. When the content of the inorganic fine particles (C) is less than 1% by mass, the inorganic fine particles (C) are difficult to enter between the organic fine particles (B) and it is difficult to form an agglomerate, and the antiglare layer 3 having an uneven shape is formed. It is hard to be done. If the content of the inorganic fine particles (C) exceeds 10% by mass, the arithmetic mean roughness (Ra) of the surface of the antiglare layer 3 may become too large, making it difficult to obtain antiglare properties. The inorganic fine particles (C) are more preferably contained in the antiglare layer 3 in an amount of 1% by mass or more and 5% by mass or less, and are contained in the antiglare layer 3 in an amount of 1% by mass or more and 3% by mass or less. Is even more preferable. Further, the content of the inorganic fine particles (C) is preferably 0.5% by volume or more and 5% by volume or less in the antiglare layer 3. It is more preferably 0.5% by volume or more and 2.5% by volume or less, and further preferably 0.5% by volume or more and 1.5% by volume or less.

(Reflection reduction layer)
The reflection reduction layer 4 is formed by including a high refractive index layer 41, an ultrahigh refractive index layer 42, and a low refractive index layer 43 (see FIG. 3). The reflection reduction layer 4 is formed on the antiglare layer 3. A high refractive index layer 41 is formed on the surface of the antiglare layer 3, an ultrahigh refractive index layer 42 is formed on the surface of the high refractive index layer 41, and a low refractive index layer 43 is formed on the surface of the ultrahigh refractive index layer 42. Is formed.

(High refractive index layer)
The high refractive index layer 41 is formed as a high refractive index layer having a higher refractive index than the antiglare layer 3. The refractive index of the high refractive index layer 41 is preferably in the range of 1.60 or more and 1.70 or less, and the thickness (actual film thickness) is preferably in the range of 50 nm or more and 80 nm or less. When the refractive index and thickness of the high refractive index layer 41 are in the above ranges, the light reflectivity of the antiglare film 1 and the antiglare low reflection film 10 is suppressed, and the antiglare film 1 and the antiglare low reflection film 1 and the antiglare low reflection film 10 are suppressed. The color of the light reflected from the film 10 is adjusted to an appropriate color. When the refractive index of the high refractive index layer 41 becomes larger than the above range, the light reflectivity of the antiglare film 1 and the antiglare low reflection film 10 is further reduced, but the color of the reflected light becomes too strong, which is not preferable. Further, when the thickness of the high refractive index layer 41 is larger than the above range, the color of the reflected light from the antiglare film 1 and the antiglare low reflection film 10 becomes bluish, and when the thickness is further increased, the antiglare film 1 and the antiglare low reflection film 10 become bluish. This is not preferable because the reflectances of the glare film 1 and the antiglare low-reflection film 10 are significantly increased. Further, if the thickness of the high refractive index layer 41 is smaller than the above range, the reflected color becomes a strong purple-tinged color, which is not preferable.

As described above, when the thickness of the high refractive index layer 41 is increased, the reflected light tends to be bluish, but if the thickness of the high refractive index layer 41 is in the range of 40 nm or more and 110 nm or less, the reflected light tends to be bluish. The color of is close enough to white. However, in order to bring the color of the reflected light closer to white, the thickness of the high refractive index layer 41 is preferably in the range of 50 nm or more and 80 nm or less as described above. It is more preferable if this thickness is in the range of more than 60 nm and 70 nm or less.

The high refractive index layer 41 is preferably formed from a reactive curable resin composition, for example, preferably formed from at least one of a thermosetting resin composition and an ionizing radiation curable resin composition. The thermosetting resin composition contains a thermosetting resin such as a phenol resin, a urea resin, a diallyl phthalate resin, a melamine resin, an unsaturated polyester resin, a polyurethane resin, an epoxy resin, an aminoalkyd resin, a silicon resin, and a polysiloxane resin. do. A cross-linking agent, a polymerization initiator, a curing agent, a curing accelerator, a solvent and the like may be used together with the thermosetting resin, if necessary. By applying such a thermosetting resin composition on, for example, the transparent base material layer 2 (the surface of the easy-adhesion layer, if any), and then the thermosetting resin composition is heated and heat-cured. , High refractive index layer 41 can be formed.

The ionizing radiation curable resin composition preferably contains a resin having an acrylate-based functional group. Examples of the resin having an acrylate-based functional group include oligomers such as (meth) acrylates, which are polyfunctional compounds having a relatively low molecular weight, and prepolymers. Examples of the polyfunctional compound include polyester resin, polyether resin, acrylic resin, epoxy resin, urethane resin, alkyd resin, spiroacetal resin, polybutadiene resin, polythiol polyene resin, polyhydric alcohol and the like. It is also preferable that the ionizing radiation curable resin composition further contains a reactive diluent. Examples of the reactive diluent include monofunctional monomers such as ethyl (meth) acrylate, ethylhexyl (meth) acrylate, styrene, methylstyrene, and N-vinylpyrrolidone, and trimethylpropantri (meth) acrylate and hexanediol (meth) acrylate. , Tripropylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di Examples include polyfunctional monomers of (meth) acrylates.

When the ionizing radiation curable resin composition is a photocurable resin composition such as an ultraviolet curable resin composition, it is preferable that the photocurable resin composition contains a photopolymerization initiator. Examples of the photopolymerization initiator include acetophenones, benzophenones, α-amyloxime esters, thioxanthones and the like. The photocurable resin composition may contain a photosensitizer in addition to the photopolymerization initiator or in place of the photopolymerization initiator. Examples of the photosensitizer include n-butylamine, triethylamine, tri-n-butylphosphine, thioxanthone and the like. Such a photocurable resin composition is applied onto, for example, the transparent base material layer 2, and then the photocurable resin composition is irradiated with light such as ultraviolet rays to be photocured, whereby the high refractive index layer 41 is formed. Can be formed.

The refractive index of the high refractive index layer 41 can be easily adjusted by the composition of the resin composition for forming the high refractive index layer 41. It is also preferable that the refractive index of the high refractive index layer 41 is adjusted by containing the particles for adjusting the refractive index and adjusting the ratio thereof.

The particle size of the particles for adjusting the refractive index is sufficiently small, that is, the particles for adjusting the refractive index are preferably so-called ultrafine particles, and in this case, the light transmittance of the high refractive index layer 41 is sufficiently maintained. become. The particle size of the particles for adjusting the refractive index is particularly preferably in the range of 0.5 nm or more and 200 nm or less. The particle size of the particles for adjusting the refractive index is the diameter of a circle (circle equivalent to the area) having the same area as the projected area calculated from the electron micrograph image of the particles. The particles for adjusting the refractive index are preferably particles having a relatively high refractive index, and particularly preferably particles having a refractive index of 1.6 or more. The particles are preferably metal or metal oxide particles.

The content of the particles for adjusting the refractive index in the high refractive index layer 41 is appropriately adjusted so that the refractive index of the high refractive index layer 41 becomes an appropriate value, and the refractive index in the high refractive index layer 41 is particularly adjusted. It is preferable that the proportion of the particles for adjustment is adjusted to be 5% by volume or more and 70% by volume or less. Specific examples of the particles for adjusting the refractive index include particles containing one or more oxides selected from titanium, aluminum, cerium, yttrium, zirconium, niobium, and antimony. Specific examples of the oxide include ZnO (refractive index 1.90), TiO ₂ (refractive index 2.3 to 2.7), CeO ₂ (refractive index 1.95), and Sb ₂ O ₅ (refractive index 1. 71), SnO ₂ (refractive index 1.8-2.0), ITO (refractive index 1.95), Y ₂ O ₃ (refractive index 1.87), La ₂ O ₃ (refractive index 1.95), Examples _{thereof include ZrO 2} (refractive index 2.05) and Al ₂ O ₃ (refractive index 1.63). It is also preferable that the high refractive index layer 41 is provided with antistatic performance. In this case, the charging of the antiglare film 1 and the antiglare low reflection film 10 is suppressed, and the adhesion of dust to the antiglare film 1 and the antiglare low reflection film 10 is suppressed. For that purpose, it is preferable that the high refractive index layer 41 contains conductive particles.

The conductive particles may also function as particles for adjusting the refractive index at the same time. The conductive particles are preferably nanoparticles, and particularly preferably ultrafine particles having a particle size of 0.5 nm or more and 200 nm or less. The particle size of the conductive particles is also the diameter of the circle corresponding to the area. Examples of the material of the conductive particles include appropriate metals having conductivity, metal oxides, and the like, and specific examples thereof include oxides of one or more kinds of metals selected from indium, zinc, tin, and antimony. More specifically, indium oxide (ITO), tin oxide (SnO ₂ ), antimon / tin oxide (ATO), lead / titanium oxide (PTO), antimon oxide (Sb ₂ O ₅ ) and the like can be mentioned. .. In order to impart sufficient antistatic performance to the high refractive index layer 41, ^{it is preferable that the sheet resistance of the high refractive index layer 41 is 10 15} Ω / □ or less by containing conductive particles. Since the antistatic property is improved as the sheet resistance of the high refractive index layer 41 is small, a lower limit is not set in particular, but since there is a limit to reducing the sheet resistance, the sheet resistance of the high refractive index layer 41 is substantially reduced. a lower limit is 10 ⁶ Ω / □. The content of the conductive particles in the high-refractive-index layer 41 is appropriately adjusted so that the antistatic performance of the high-refractive-index layer 41 becomes an appropriate degree, and in particular, the conductive particles in the high-refractive-index layer 41 It is preferable that the ratio is adjusted to be 5% by mass or more and 70% by mass or less.

As described above, the high refractive index layer 41 may contain a cured product of the first ultraviolet curable resin containing at least one of an alkoxysilane having a reactive organic functional group and a partially hydrolyzed polymer thereof. .. For that purpose, for example, when the high refractive index layer 41 is formed from the ultraviolet curable resin composition, it is preferable that the ultraviolet curable resin composition contains the first ultraviolet curable resin.

Examples of the reactive organic functional group in the alkoxysilane having a reactive organic functional group include an acryloyl group, a methacryloyl group, a glycidyl group, an isocyanate group and the like. Examples of the alkoxysilane having a reactive organic functional group include 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, and 3-. Examples thereof include acryloxipropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-isocyanuppropyltriethoxysilane, and 3-isocyanuppropyltriethoxysilane.

As described above, when the high refractive index layer 41 contains a cured product of the first ultraviolet curable resin, the alkoxysilane in the first ultraviolet curable resin and its partially hydrolyzed polymer with respect to the high refractive index layer 41. Is preferably 3% by mass or more. This ratio is further preferably in the range of 5 to 10% by mass. In this case, the scratch resistance of the antiglare film 1 and the antiglare low-reflection film 10 is further improved, and the adhesion between the layers is further improved.

(Ultra-high refractive index layer)
The ultra-high refractive index layer 42 is formed as a high refractive index layer having a higher refractive index than the low refractive index layer 43. The refractive index of the ultra-high refractive index layer 42 is preferably in the range of 1.75 or more and 1.90 or less, and the thickness (actual film thickness) is preferably in the range of 100 nm or more and 160 nm or less. When the refractive index and thickness of the ultrahigh refractive index layer 42 are in the above ranges, the light reflectivity of the antiglare film 1 and the antiglare low reflection film 10 is suppressed, and the antiglare film 1 and the antiglare low The color of the light reflected from the reflective film 10 is adjusted to an appropriate color. When the refractive index of the ultrahigh refractive index layer 42 becomes larger than the above range, the light reflectivity of the antiglare film 1 and the antiglare low reflection film 10 is further reduced, but the color of the reflected light becomes too strong, which is not preferable. .. Further, when the thickness of the ultrahigh reflectance layer 42 is larger than the above range, the color of the reflected light from the antiglare film 1 and the antiglare low reflection film 10 becomes bluish, and when this thickness is further increased. This is not preferable because the reflectances of the antiglare film 1 and the antiglare low reflection film 10 are significantly increased. Further, if the thickness of the ultra-high refractive index layer 42 is smaller than the above range, the reflected color becomes a strong purple-tinged color, which is not preferable.

As described above, when the thickness of the ultra-high refractive index layer 42 is increased, the reflected light tends to be bluish, but if the thickness of the ultra-high refractive index layer 42 is in the range of 100 nm or more and 180 nm or less, The color of the reflected light is sufficiently close to white. However, in order to bring the color of the reflected light closer to white, the thickness of the ultrahigh refractive index layer 42 is preferably in the range of 100 nm or more and 160 nm or less as described above. It is more preferable if this thickness is larger than 130 nm and is in the range of 160 or less.

The ultra-high refractive index layer 42 is preferably formed from a reactive curable resin composition, for example, preferably formed from at least one of a thermosetting resin composition and an ionizing radiation curable resin composition. Examples of the thermosetting resin composition, the ionizing radiation curable resin composition, and the photopolymerization initiator are the same as those of the resin mentioned in the description of the high refractive index layer 41.

The refractive index of the ultra-high refractive index layer 42 can be easily adjusted by the composition of the resin composition for forming the ultra-high refractive index layer 42. It is also preferable that the refractive index of the ultra-high refractive index layer 42 is adjusted by containing the particles for adjusting the refractive index and adjusting the ratio thereof.

The particle size of the particles for adjusting the refractive index is sufficiently small, that is, the particles for adjusting the refractive index are preferably so-called ultrafine particles, and in this case, the light transmittance of the ultrahigh refractive index layer 42 is sufficiently maintained. Will be. The particle size of the particles for adjusting the refractive index is particularly preferably in the range of 0.5 nm or more and 200 nm or less. The particle size of the particles for adjusting the refractive index is the diameter of a circle (circle equivalent to the area) having the same area as the projected area calculated from the electron micrograph image of the particles.

The particles for adjusting the refractive index are preferably particles having a relatively high refractive index, and particularly preferably particles having a refractive index of 1.6 or more. The particles are preferably metal or metal oxide particles.

The content of the particles for adjusting the refractive index in the ultra-high refractive index layer 42 is appropriately adjusted so that the refractive index of the ultra-high refractive index layer 42 becomes an appropriate value, but particularly in the ultra-high refractive index layer 42. It is preferable that the proportion of the particles for adjusting the refractive index of the above is adjusted to be 5% by volume or more and 70% by volume or less.

Specific examples of the particles for adjusting the refractive index include particles containing one or more oxides selected from titanium, aluminum, cerium, yttrium, zirconium, niobium, and antimony. Specific examples of the oxide include ZnO (refractive index 1.90), TiO ₂ (refractive index 2.3 to 2.7), CeO ₂ (refractive index 1.95), and Sb ₂ O ₅ (refractive index 1. 71), SnO ₂ (refractive index 1.8-2.0), ITO (refractive index 1.95), Y ₂ O ₃ (refractive index 1.87), La ₂ O ₃ (refractive index 1.95), Examples _{thereof include ZrO 2} (refractive index 2.05) and Al ₂ O ₃ (refractive index 1.63).

The ultra-high refractive index layer 42 contains particles containing one or more oxides selected from titanium, aluminum, cerium, yttrium, zirconium, niobium, and antimony, as well as methacryl-functional silane and acrylic-functional silane. It is also preferable to contain at least one of them. In this case, the adhesion between the ultra-high refractive index layer 42 and the low refractive index layer 43 is improved. Examples of the methacryl-functional silane include 3-methacryloxypropyltrimethoxysilane and 3-methacryloxypropylmethyldimethoxysilane. Examples of the acrylic functional silane include 3-acryloxypropyltrimethoxysilane and 3-acryloxypropylmethyldimethoxysilane.

The contents of the methacryl-functional silane and the acrylic-functional silane in the ultra-high refractive index layer 42 are not particularly limited, but the ratio of the total amount of the methacryl-functional silane and the acrylic-functional silane in the ultra-high refractive index layer 42 is 5 mass. It is preferably in the range of% or more and 30% by mass or less. When the ratio is 5% by mass or more, the adhesion between the ultra-high refractive index layer 42 and the low refractive index layer 43 is sufficiently high, and when the ratio is 30% by mass or less, the ultra-high refractive index layer 42 is contained. The cross-linking density of the ultra-high refractive index layer 42 is sufficiently improved, and the hardness of the ultra-high refractive index layer 42 is sufficiently high.

It is preferable that the main surface of the ultra-high refractive index layer 42 opposite to the high refractive index layer 41 is surface-treated before the low refractive index layer 43 is formed. In this case, it is possible to improve the wettability, adhesion, and the like between the ultra-high refractive index layer 42 and the low refractive index layer 43. Examples of the surface treatment method include physical surface treatment such as plasma treatment, corona discharge treatment and frame treatment, and chemical surface treatment with a coupling agent, acid and alkali.

As described above, even if the ultrahigh refractive index layer 42 contains a cured product of a second ultraviolet curable resin containing at least one of an alkoxysilane having a reactive organic functional group and a partially hydrolyzed polymer thereof. good. For that purpose, for example, when the ultrahigh refractive index layer 42 is formed from the ultraviolet curable resin composition, it is preferable that the ultraviolet curable resin composition contains a second ultraviolet curable resin.

As described above, when the ultra-high refractive index layer 42 contains a cured product of the second ultraviolet curable resin, the alkoxysilane and its partial hydrolysis in the second ultraviolet curable resin with respect to the ultra-high refractive index layer 42. The proportion of the polymer is preferably 3% by mass or more. This ratio is further preferably in the range of 5 to 10% by mass. In this case, the scratch resistance of the antiglare film 1 and the antiglare low-reflection film 10 is further improved, and the adhesion between the layers is further improved.

(Low refractive index layer)
The refractive index of the low refractive index layer 43 is lower than that of any of the transparent base material layer 2, the high refractive index layer 41, and the ultra-high refractive index layer 42. The refractive index of the low refractive index layer 43 is preferably in the range of 1.30 or more and 1.40 or less, and the thickness (actual film thickness) thereof is preferably in the range of 70 nm or more and 110 nm or less.

When the refractive index of the low refractive index layer 43 is in the above range, the reflectances of the antiglare film 1 and the antiglare low reflection film 10 due to the interference action between the high refractive index layer 41 and the ultrahigh refractive index layer 42. And further, when the thickness of the low refractive index layer 43 is in the above range, the color of the reflected light from the antiglare film 1 and the antiglare low reflection film 10 is appropriately adjusted.

If the thickness of the low refractive index layer 43 is in the range of 70 nm or more and 130 nm or less, the color of the reflected light is sufficiently close to white. However, in order to bring the color of the reflected light closer to white, the thickness of the low refractive index layer 43 is preferably in the range of 70 nm or more and 110 nm or less as described above. It is more preferable that the thickness is in the range of 70 nm or more and less than 80 nm.

Further, as described above, when the antiglare film 1 and the antiglare low reflection film 10 are used in combination with the ITO film, the reflected light from the antiglare film 1 and the antiglare low reflection film 10 and the reflected light from the ITO film are used. In order to bring the color of the light overlapping with the light closer to white, the thickness of the low refractive index layer 43 is preferably in the range of 80 nm or more and 130 nm or less. It is more preferable if this thickness is in the range of more than 110 nm and 130 nm or less.

The low refractive index layer 43 is formed from, for example, a composition containing a binder material and particles for adjusting the refractive index used as needed. When the binder material and the particles for adjusting the refractive index are used in combination, the refractive index of the low refractive index layer 43 is appropriately adjusted depending on the combination of both, the compounding ratio, and the like.

As the binder material, a polymer having at least one of a silicon alkoxide resin, a saturated hydrocarbon and a polyether as a main chain (for example, a UV curable resin composition, a thermosetting resin composition, etc.), and a fluorine atom in the polymer chain. Examples thereof include a resin containing a unit containing.

As the silicon alkoxide-based resin, partial hydrolysis of the silicon alkoxide represented by RmSi (OR') n (R and R'are alkyl groups having 1 to 10 carbon atoms, m + n = 4, m and n are integers, respectively). Examples thereof include oligomers and polymers which are condensates. Specific examples of the silicon alkoxide include tetramethoxysilane, tetraethoxysilane, tetra-iso-propoxysilane, tetra-n-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, and tetra-tert-butoxysilane. Silane, tetrapentaethoxysilane, tetrapenta-iso-propoxysilane, tetrapenta-n-propoxysilane, tetrapenta-n-butoxysilane, tetrapenta-sec-butoxysilane, tetrapenta-tert-butoxysilane, methyltrimethoxysilane, methyltriethoxy Silane, methyltripropoxysilane, methyltributoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethylethoxysilane, dimethylmethoxysilane, dimethylpropoxysilane, dimethylbutoxysilane, methyldimethoxysilane, methyldiethoxysilane, hexyltrimethoxysilane Etc. are exemplified.

As the binder material, a reactive organic silicon compound having a plurality of groups (polymerizable double bond groups, etc.) that are reactively crosslinked by heat or ionizing radiation may be used. The molecular weight of this organic silicon compound is preferably 5000 or less. Such reactive organic silicon compounds are obtained by reacting one-terminal vinyl-functional polysilane, both-terminal vinyl-functional polysilane, one-terminal vinyl-functional polysiloxane, both-terminal vinyl-functional polysiloxane, and these compounds. Examples thereof include vinyl-functional polysilane and vinyl-functional polysiloxane. In addition to these, examples of the reactive organic silicon compound include (meth) acryloxysilane compounds such as 3- (meth) acryloxypropyltrimethoxysilane and 3- (meth) acryloxipropylmethyldimethoxysilane.

As the particles for adjusting the refractive index, it is preferable to use particles having a relatively low refractive index. Examples of the material of the particles for adjusting the refractive index include silica, magnesium fluoride, lithium fluoride, aluminum fluoride, calcium fluoride, and sodium fluoride. It is preferable that the particles for adjusting the refractive index include hollow particles. Hollow particles are particles having cavities surrounded by an outer shell. The refractive index of the hollow particles is preferably 1.20 to 1.45. If necessary, the particles for adjusting the refractive index are preferably surface-treated to improve the wettability with the binder material.

It is preferable that the particle size of the particles for adjusting the refractive index is sufficiently small, that is, the particles for adjusting the refractive index are so-called ultrafine particles, and in this case, the light transmittance of the low refractive index layer 43 is sufficiently maintained. Will be. The particle size of the particles for adjusting the refractive index is particularly preferably in the range of 0.5 nm to 200 nm. The particle size of the particles for adjusting the refractive index is the diameter of a circle (circle equivalent to the area) having the same area as the projected area calculated from the electron micrograph image of the particles.

The content of the particles for adjusting the refractive index in the low refractive index layer 43 is appropriately adjusted so that the value of the refractive index of the low refractive index layer 43 becomes an appropriate value, but particularly in the low refractive index layer 43. It is preferable that the proportion of the particles for adjusting the refractive index is adjusted to be 20 to 99% by volume.

The composition may further contain a water-repellent and oil-repellent material. In this case, antifouling property can be imparted to the low refractive index layer 43. As the water-repellent and oil-repellent material, a general wax-based material or the like can be used. In particular, when a fluorine-containing compound is used, the removability of stains, fingerprints, etc. of the low refractive index layer 43 is particularly improved, and the frictional resistance on the surface of the low refractive index layer 43 is reduced to reduce the resistance of the low refractive index layer 43. Abrasion is improved.

A preferred embodiment of the low refractive index layer 43 is a polymer composed of a polymer of a mixture of alkoxysilane and alkoxysilane having a fluorocarbon skeleton, and containing hollow silica particles. In this case, the effects of ensuring a low refractive index, imparting an antifouling function, and imparting chemical resistance are obtained, which is preferable. Examples of the above-mentioned alkoxysilane include polymethoxysilane. Further, as the alkoxysilane having a fluorocarbon skeleton, trimethoxysilyld decafluorohexane and the like can be exemplified. A mixture of an alkoxysilane and an alkoxysilane having a fluorocarbon skeleton can be prepared by mixing an alkoxysilane having a fluorocarbon skeleton in a ratio of 5 to 1900 parts by mass with respect to 100 parts by mass of the alkoxysilane. Further, a polymer of a mixture of an alkoxysilane and an alkoxysilane having a fluorocarbon skeleton can be produced by, for example, a polymerization method such as a sol-gel method. The molecular weight of the polymer of the mixture of alkoxysilane and alkoxysilane having a fluorocarbon skeleton is preferably 500 to 3000. Further, the hollow silica particles preferably have a refractive index of 1.20 to 1.45 and a particle size in the range of 0.5 nm to 200 nm, as described above. Further, the low refractive index layer 43 preferably contains hollow silica particles in a ratio of 5 to 233 parts by mass with respect to 100 parts by mass of a polymer of a mixture of alkoxysilane and an alkoxysilane having a fluorocarbon skeleton. ..

In the low refractive index layer 43, the composition as described above is applied on the ultrahigh refractive index layer 42, and the composition is further heated, humidified, irradiated with ultraviolet rays, irradiated with electron beams, etc. according to the properties of the binder material. It can be formed by being cured by being treated.

(3) Modified Example The embodiment is only one of the various embodiments of the present disclosure. The embodiment can be changed in various ways depending on the design and the like as long as the object of the present disclosure can be achieved.

The antiglare film 1 and the antiglare low reflection film 10 can be provided with an unevenness adjusting layer. The unevenness adjusting layer adjusts the degree of unevenness on the surface of the antiglare layer 3 to adjust the antiglare property and the reflectivity of the antiglare film 1 and the antiglare low reflection film 10.

(Example 1)
A light-transmitting transparent base material layer (thickness 80 μm triacetyl cellulose resin film, manufactured by Fuji Film Co., Ltd., TD80UL) is prepared, and a composition for an antiglare layer having the composition shown below is applied to one side of the transparent base material film. It was applied to form a coating film. Next, the formed coating film is dried in a circulating air dryer at 80 ° C. for 1 minute to evaporate the solvent in the coating film, and the coating film is irradiated with ^{ultraviolet rays so that the integrated light amount becomes 150 mJ / cm 2.} By curing, an antiglare layer having a thickness of 5 μm (when cured) was formed, and an antiglare film according to Example 1 was produced.

(Composition for antiglare layer)
Organic fine particles (acrylic-styrene copolymer particles, average primary particle diameter 3.5 μm, refractive index 1.555, manufactured by Sekisui Kasei Kogyo Co., Ltd.): 10 parts by mass Inorganic fine particles (fumed silica, octylsilane treatment; average primary particles Diameter 12 nm, Density: 2.2 g / cm ³ , manufactured by Nippon Aerodil Co., Ltd.): 2 parts by mass Pentaerythritol polyacrylate mixture with hydroxyl group concentration of 0.001 mmol / g or more and 0.15 mmol / g or less: 60 parts by mass Urethane acrylate (product name) : Luxidia V-4000BA, manufactured by DIC Co., Ltd.): 40 parts by mass Irgacure 184 (manufactured by BASF Japan, photopolymerization initiator): 5 parts by mass Branched fluorine-based surfactant (Futagent 681, manufactured by Neos Co., Ltd.): 3.3 parts by mass To a mixture of the above organic fine particles, inorganic fine particles, pentaerythritol polyacrylate mixture, urethane acrylate, Irgacure 184 and branched fluorine-based surfactant, toluene / cyclohexanone = 70 parts by mass / 30 parts by mass of a mixed solvent. Diluted to 30% of the active ingredient (vehicle).

The hydroxyl group concentration of the binder resin of this antiglare layer composition is calculated to be 0.0004 mmol / g or more and 0.06 mmol / g or less. The absolute value of the difference in refractive index between the binder resin and the organic fine particles was 0.05.

Subsequently, a concavo-convex adjustment layer was formed as a second layer on the antiglare layer. In forming the unevenness adjusting layer, urethane acrylate (product name: Luxidia V-4000BA, manufactured by DIC Corporation) is mixed with 95 parts by mass of Irgacure 184 (manufactured by BASF Japan, photopolymerization initiator) so as to be 5 parts by mass. , Propylene glycol monomethyl ether was diluted to 10% of the active ingredient (vehicle) to obtain an unevenness adjusting layer material. The unevenness adjusting layer material was applied to the surface of the antiglare layer with a wire bar coater # 6 to form a coating film. Next, the formed coating film is dried in a circulating air dryer at 80 ° C. for 1 minute to evaporate the solvent in the coating film, and the coating film is irradiated with ^{ultraviolet rays so that the integrated light amount becomes 150 mJ / cm 2.} It was cured to form a 0.9 μm unevenness adjusting layer.

Subsequently, a high refractive index layer was formed as a third layer on the surface of the unevenness adjusting layer. In forming the high refractive index layer, the acrylic ultraviolet curable resin (“Seika Beam MD-2 Clear” manufactured by Dainichi Seika Kogyo Co., Ltd.) is used for the total amount of the acrylic ultraviolet curable resin and the high refractive index particles. The active ingredient (solid content) 60% by mass) is mixed with titanium oxide particles (“760T” manufactured by Teika Co., Ltd., dispersion solvent: toluene, solid content 48% by mass) as high refractive index particles so as to be 40% by mass. (Acrylic ultraviolet curable resin, 60% by mass) was diluted with a toluene solvent to a solid content of 2% by mass to obtain a high refractive index layer material. The high refractive index material was applied onto the hard coat layer with a wire bar coater # 3, dried at 80 ° C. for 5 minutes, and then ^{cured by UV irradiation (500 mJ / cm 2} ) to form the material. The high refractive index layer has a refractive index of 1.63 and a film thickness of 60 nm.

Subsequently, an ultra-high refractive index layer was formed as a fourth layer on the surface of the high refractive index layer. In forming the ultra-high refractive index layer, the acrylic ultraviolet curable resin (“Seika Beam MD-2 Clear” manufactured by Dainichi Seika Kogyo Co., Ltd.) is used for the total amount of the acrylic ultraviolet curable resin and the high refractive index particles. , Active ingredient (solid content) 60% by mass), titanium oxide particles (“760T” manufactured by Teika Co., Ltd., dispersion solvent: toluene, solid content 48% by mass) as high refractive index particles so as to be 70% by mass. It was mixed (acrylic ultraviolet curable resin, 30% by mass) and diluted with a toluene solvent to a solid content of 12% by mass to obtain a high refractive index layer material. The high refractive index material was applied onto the hard coat layer with a wire bar coater # 3, dried at 80 ° C. for 5 minutes, and then ^{cured by UV irradiation (500 mJ / cm 2} ) to form the material. The high refractive index layer has a refractive index of 1.76 and a film thickness of 130 nm.

Subsequently, a low refractive index layer was formed as a fifth layer on the ultrahigh refractive index layer. In forming the low refractive index layer, 58% by mass of hollow silica fine particle sol (“Thruria 4320” manufactured by JGC Catalysts and Chemicals Co., Ltd., solvent-dispersed sol, solid content 20%) was added to the total amount of the low refractive index layer material. 40% by mass of pentaerythritol polyacrylate (“Aronix M-402” manufactured by Toa Synthetic Co., Ltd.) and 2% by mass of photopolymerization initiator Omnirad 127 (manufactured by BASF) are mixed, and the active ingredient (vehicle) is 2.4 with methylisobutylketone. The low refractive index layer material was obtained by diluting to%.

This low refractive index layer material is applied with a wire bar coater # 3 to form a coating film having a thickness of 90 nm, left at 120 ° C. for 1 minute to dry, and then the coating film is dried at 120 ° C. for 5 minutes under a nitrogen atmosphere. It was formed by curing by UV irradiation (500 mJ / cm ^2). The high refractive index layer has a refractive index of 1.37 and a film thickness of 90 nm.

From the above, an antireflection member having a structure in which a transparent base material layer, an antiglare layer, an unevenness adjusting layer, a high refractive index layer, an ultrahigh refractive index layer, and a low refractive index layer are laminated in this order was obtained.

(Example 2)
Prevention in the same manner as in Example 1 except that the composition for the antiglare layer was prepared in the same manner as in Example 1 except that the pentaerythritol polyacrylate mixture was replaced with the pentaerythritol polyacrylate mixture having a hydroxyl group concentration of 1.05 mmol / g. A glare film was created. The hydroxyl group concentration of the binder resin of this antiglare layer composition is calculated to be 0.63 mmol / g ((1.05 × 60 + 0 × 40) / (60 + 40) = 0.63). The absolute value of the difference in refractive index between the binder resin and the organic fine particles was 0.05.

(Example 3)
Prevention in the same manner as in Example 1 except that the composition for the antiglare layer was prepared in the same manner as in Example 1 except that the pentaerythritol polyacrylate mixture was replaced with the pentaerythritol polyacrylate mixture having a hydroxyl group concentration of 2.80 mmol / g. A glare film was created. The hydroxyl group concentration of the binder resin of this antiglare layer composition is calculated to be 1.68 mmol / g. The absolute value of the difference in refractive index between the binder resin and the organic fine particles was 0.05.

(Example 4)
Prevention in the same manner as in Example 1 except that the composition for the antiglare layer was prepared in the same manner as in Example 1 except that the pentaerythritol polyacrylate mixture was replaced with the pentaerythritol polyacrylate mixture having a hydroxyl group concentration of 3.85 mmol / g. A glare film was created. The hydroxyl group concentration of the binder resin of this antiglare layer composition is 2.31 mmol / g as a calculated value. The absolute value of the difference in refractive index between the binder resin and the organic fine particles was 0.05.

(Example 5)
The same as in Example 1 except that the composition for the antiglare layer was prepared in the same manner as in Example 1 except that the pentaerythritol polyacrylate mixture was replaced with the dipentaerythritol polyacrylate mixture having a hydroxyl group concentration of 0.63 mmol / g. An antiglare film was created. The hydroxyl group concentration of the binder resin of this antiglare layer composition is calculated to be 0.38 mmol / g. The absolute value of the difference in refractive index between the binder resin and the organic fine particles was 0.05.

(Example 6)
The same as in Example 1 except that the composition for the antiglare layer was prepared in the same manner as in Example 1 except that the pentaerythritol polyacrylate mixture was replaced with the dipentaerythritol polyacrylate mixture having a hydroxyl group concentration of 1.00 mmol / g. An antiglare film was created. The hydroxyl group concentration of the binder resin of this antiglare layer composition is a calculated value of 0.60 mmol / g. The absolute value of the difference in refractive index between the binder resin and the organic fine particles was 0.05.

(Example 7)
The same as in Example 1 except that the composition for the antiglare layer was prepared in the same manner as in Example 1 except that the pentaerythritol polyacrylate mixture was replaced with the dipentaerythritol polyacrylate mixture having a hydroxyl group concentration of 2.10 mmol / g. An antiglare film was created. The hydroxyl group concentration of the binder resin of this antiglare layer composition is calculated to be 1.26 mmol / g. The absolute value of the difference in refractive index between the binder resin and the organic fine particles was 0.05.

(Example 8)
The pentaerythritol polyacrylate mixture was a dipentaerythritol polyacrylate mixture having a hydroxyl group concentration of 0.27 mmol / g, and the organic fine particles were organic fine particles (acrylic-styrene copolymer particles, average primary particle diameter 3.5 μm, refractive index 1.525). An antiglare film was prepared in the same manner as in Example 1 except that the composition for the antiglare layer was prepared in the same manner as in Example 1 except that the composition was replaced with (manufactured by Sekisui Kasei Kogyo Co., Ltd.). The hydroxyl group concentration of the binder resin of this antiglare layer composition is a calculated value of 0.16 mmol / g. The absolute value of the difference in refractive index between the binder resin and the organic fine particles was 0.05.

Here, the refractive index of the organic fine particles is lowered by making the ratio of the acrylic component of the acrylic-styrene copolymer particles higher than that of Examples 1 to 7, whereby the density of the acrylic component is higher than the density of the styrene component. Because of the larger size, the density of organic fine particles is also higher. It is considered that the polarity of the organic fine particles is higher than that of Example 1 due to the increase in the components of the acrylic resin, but the hydroxyl group concentration of the binder resin (A) is also higher than that of Example 1. By ensuring the polarity similarity between the dispersion medium and the dispersoid to some extent, the dispersibility of the organic fine particles is ensured, and the aggregates of the organic fine particles affect the unevenness of the surface of the antiglare layer. It is considered that Ra and Sm suitable for the above were obtained.

(Example 9)
The pentaerythritol polyacrylate mixture was a dipentaerythritol polyacrylate mixture having a hydroxyl group concentration of 0.63 mmol / g, and the organic fine particles were organic fine particles (acrylic-styrene copolymer particles, average primary particle diameter 3.5 μm, refractive index 1.525). An antiglare film was prepared in the same manner as in Example 1 except that the composition for the antiglare layer was prepared in the same manner as in Example 1 except that the composition was replaced with (manufactured by Sekisui Kasei Kogyo Co., Ltd.). The hydroxyl group concentration of the binder resin of this antiglare layer composition is calculated to be 0.38 mmol / g. The absolute value of the difference in refractive index between the binder resin and the organic fine particles was 0.025.

(Comparative Example 1)
Anti-glare as in Example 1 except that the organic fine particles were replaced with organic fine particles (acrylic-styrene copolymer particles, average primary particle diameter 3.5 μm, refractive index 1.525, manufactured by Sekisui Plastics Co., Ltd.). An antiglare film was prepared in the same manner as in Example 1 except that the layer composition was prepared. The binder hydroxyl group concentration of this antiglare composition is calculated to be 0.0004 mmol / g or more and 0.06 mmol / g or less. The absolute value of the difference in refractive index between the binder resin and the organic fine particles was 0.025.

Here, similarly to Examples 8 and 9, the refractive index of the organic fine particles is lowered by making the ratio of the acrylic component of the acrylic-styrene copolymer particles higher than that of Examples 1 to 7. As a result, the density of the acrylic component is higher than that of the styrene component, so that the density of the organic fine particles is also higher. It is considered that the polarity of the organic fine particles is higher than that of Example 1 due to the increase in the components of the acrylic resin, but since the hydroxyl group concentration of the binder resin (A) is the same as that of Example 1, the organic fine particles are considered to be higher. The difference in polarity between the resin and the binder resin became large, and as a result, the organic fine particles aggregated larger than in Example 1, and the density of the organic fine particles increased, which made it easier to sink. It is probable that as a result of reducing the influence of the fine particles on the unevenness of the surface of the antiglare layer, Ra and Sm became smaller than in Example 1, and Ra and Sm suitable for the present invention could not be obtained.

(Comparative Example 2)
The same as in Example 1 except that the composition for the antiglare layer was prepared in the same manner as in Example 1 except that the pentaerythritol polyacrylate mixture was replaced with the pentaerythritol polyacrylate mixture having a hydroxyl group concentration of 4.9 mmol / g. An antiglare film was created. The hydroxyl group concentration of the binder resin of this antiglare layer composition is 2.94 mmol / g as a calculated value. The absolute value of the difference in refractive index between the binder resin and the organic fine particles was 0.05.

(Comparative Example 3)
The pentaerythritol polyacrylate mixture was a dipentaerythritol polyacrylate mixture having a hydroxyl group concentration of 2.1 mmol / g, and the organic fine particles were organic fine particles (acrylic-styrene copolymer particles, average primary particle diameter 3.5 μm, refractive index 1.525). An antiglare film was prepared in the same manner as in Example 1 except that the composition for the antiglare layer was prepared in the same manner as in Example 1 except that the composition was replaced with (manufactured by Sekisui Kasei Kogyo Co., Ltd.). The hydroxyl group concentration of the binder resin of this antiglare layer composition is calculated to be 1.26 mmol / g. The absolute value of the difference in refractive index between the binder resin and the organic fine particles was 0.025.

(Measurement method and evaluation)
(1) Ra: Arithmetic mean roughness of the surface of the antiglare layer, which is a value obtained by a method conforming to JIS B 0601-1994, and was measured by a surface roughness measuring instrument: ET3000i / manufactured by Kosaka Laboratory Co., Ltd. ..

(2) Sm: The average interval of the unevenness on the surface of the antiglare layer, which is a value obtained by a method conforming to JIS B 0601-1994, and was measured by a surface roughness measuring instrument: ET3000i / manufactured by Kosaka Laboratory Co., Ltd. ..

(3) T%: Transmittance, preferably 90% or more and 100% or less. The measurement was performed using a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., model number NDH2000) in accordance with JIS K 7361-1: 1997.

(4) Haze: Of the incident light, the ratio of the parallel light transmittance to the diffuse light transmittance, preferably 1% or more and 20% or less. The measurement was performed using a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., model number NDH2000) in accordance with JIS K 7361-1: 1997.

(5) Visual reflectance: SCI (Y)
The visual sensitivity reflectance including the specular reflected light and the scattered reflected light, preferably 0.7 or less. A spectrophotometer (manufactured by Konica Minolta Japan Co., Ltd., product number) with a black vinyl tape (Nitto Denko, No. 21) attached after painting the back surface of the transparent base material with black magic ink (registered trademark). Using CM-3600d), the visual reflectance SCI (Y) was measured under the conditions of a C light source, a 10 ° field, a measurement diameter of 4 mmΦ, and SCI.

(6) Reflective chromaticity (a ^* , b ^* )
The back side of the surface coated with the antiglare layer composition of the transparent base material is painted with black magic ink (registered trademark), and black vinyl tape (Nitto Denko, No. 21) is attached to the spectrophotometer. ^{Reflected chromaticity (a *} , b ^* ) was measured using a colorimeter (manufactured by Konica Minolta Japan Co., Ltd., product number CM-3600d) under the conditions of C light source, 10 ° field, measurement diameter 4 mmΦ, and SCI. .. SCI (a ^* ) is a red-green tint index including specularly reflected light and scattered reflected light, and is preferably in the range of -5 or more and 5 or less. SCI (b ^* ) is a yellow-blue tint index including specularly reflected light and scattered reflected light, and is preferably in the range of -5 or more and 5 or less.

(7) Anti-glare The surface on the back side of the surface coated with the anti-glare layer composition of the transparent base material is painted with black magic ink (registered trademark), and then black vinyl tape (Nitto Denko, No. 21) is applied. The reflection of the fluorescent lamp on the antiglare layer side was evaluated in the attached state. "A" is good without reflection, and "C" has conspicuous reflection.

1 Anti-glare film 10 Anti-glare and low-reflection film 2 Transparent base material layer 3 Anti-glare layer 41 High refractive index layer 42 Ultra-high refractive index layer 43 Low refractive index layer A Binder resin B Organic fine particles C Inorganic fine particles

Claims

A binder resin (A), organic fine particles (B) and inorganic fine particles (C) dispersed in the binder resin (A) are contained on the transparent base material layer and at least one surface of the transparent base material layer. Equipped with an anti-glare layer
The absolute value of the difference in refractive index between the binder resin (A) and the organic fine particles (B) is 0.005 or more and 0.25 or less.
The average primary particle size of the inorganic fine particles (C) is smaller than the average primary particle size of the organic fine particles (B).
The arithmetic mean roughness (Ra) of the antiglare layer surface is in the range of 0.080 μm or more and 0.210 μm or less, and the average interval (Sm) of the irregularities on the antiglare layer surface is 0.100 μm or more and 0.200 μm. Is below,
Anti-glare film.
The hydroxyl group concentration of the binder resin (A) is larger than 0 mmol / g and 2.50 mmol / g or less.
The antiglare film according to claim 1.
The binder resin (A) contains a hydroxyl group-containing acrylate.
The antiglare film according to claim 2.
The average primary particle size of the organic fine particles (B) is 2 μm or more and 7 μm or less.
The antiglare film according to any one of claims 1 to 3.
The average primary particle diameter of the inorganic fine particles (C) is 1 nm or more and 200 nm or less.
The antiglare film according to any one of claims 1 to 4.
The inorganic fine particles (C) contain fumed silica.
The antiglare film according to any one of claims 1 to 5.
On the antiglare layer in the antiglare film according to any one of claims 1 to 6,
A high-refractive index layer having a refractive index of 1.60 or more and 1.70 or less,
An ultra-high refractive index layer having a refractive index of 1.75 or more and 1.90 or less,
A low refractive index layer having a refractive index of 1.30 or more and 1.40 or less,
Are prepared in this order,
A film with anti-glare and low reflectivity.