JP2009042628A - Anti-glare film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an anti-glare film including an anti-glare layer excellent in both anti-glare property and hard coat property. <P>SOLUTION: The anti-glare film includes the anti-glare layer with an irregularly-shaped outermost surface provided on a transparent substrate film. The ant-glare film can have both excellent anti-glare property and excellent hard coat property by unevenly distributing a reactive inorganic fine particle B having crosslinking property capable of forming a crosslinkage with a binder component C forming an irregular layer of the anti-glare layer and having a specific average particle size in a surface layer area in the interface opposite to the transparent substrate film side of the irregular layer. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention is intended to prevent reflection of external light and make an image easy to see by pasting or arranging it on the front surface of a display such as a liquid crystal display, a cathode ray tube display (CRT), or a plasma display panel. The present invention relates to an antiglare film used in the above.

In the display as described above, an anti-glare film having a fine uneven surface is provided on the display surface in order to prevent reflection of light irradiated from the outside on the display surface.
The antiglare film has a type in which an antiglare layer having a concavo-convex shape is formed on the surface by coating a resin composition containing a large particle size or cohesive particles on the surface of the transparent substrate. Does not include spinodal decomposition, forms a phase separation structure, cures the curable resin, forms an antiglare layer with an uneven shape on the surface, or laminates a film with unevenness on the surface of the layer to make unevenness There is a type in which an antiglare layer having an uneven shape is formed on the surface by transferring the shape.

  Moreover, as a film for preventing the reflection of light from an external light source on the surface of various displays as described above, an antireflection film having a low refractive index layer having a low refractive index lower than the refractive index of the lower layer is formed. Films are known (for example, Patent Documents 1 to 3).

For example, in Patent Document 1, a cured layer containing low refractive index fine particles, high refractive index fine particles and a binder is formed on a transparent plastic film substrate, and the surface of the cured layer (the opposite surface of the substrate film). It is described that, by making hollow silica, which is a low refractive index fine particle, unevenly distributed on the side, an apparent low refractive index layer is formed and excellent antireflection properties can be obtained. Further, in Patent Document 2, as in Patent Document 1, the low refractive index fine particles are unevenly distributed on the surface side of the cured layer, and at the same time, the high refractive index fine particles are unevenly distributed on the substrate side, thereby improving the antireflection effect. Further, it is described that antistatic properties are imparted by using conductive fine particles as high refractive index fine particles.
In Patent Documents 1 and 2, as hollow silica (low refractive index particles) unevenly distributed on the hardened layer surface side, the average particle diameter is 30 nm or more in order to increase the ratio of the cavity and further lower the refractive index. In the examples, those having an average particle diameter of 40 nm are used. In order to make the hollow silica unevenly distributed on the surface side of the hardened layer, a method of reducing the surface free energy of the hollow silica by surface treatment with a fluorine-containing compound is employed.

  Furthermore, in Patent Document 3, by coating a coating composition in which a plurality of types of fine particles having different specific gravities and refractive indexes are dispersed in a binder resin, a difference in specific gravities causes an upper part to an intermediate part of the coating film to be formed. An antireflection film having a coating film in which low refractive index fine particles are unevenly distributed and medium to high refractive index fine particles are unevenly distributed in an intermediate portion or a lower portion is described.

On the other hand, it is required that the image display surface of the image display device in the display as described above is provided with scratch resistance so as not to be scratched during handling. On the other hand, a hard coat film in which a hard coat (HC) layer is formed on a base film and a hard coat film (optical laminate) provided with optical functions such as antireflection and antiglare properties are used. Thus, it is common to improve the scratch resistance of the image display surface of the image display device (for example, Patent Document 1, Patent Document 2, and Patent Document 4).
When laminating a hard coat layer and other functional layers such as an antireflection layer and an antiglare layer, in order to obtain high scratch resistance, ensure interlayer adhesion between the hard coat layer and the functional layer. Is very important, but the actual situation is that it is difficult to obtain interlayer adhesion that realizes sufficient scratch resistance.

  Patent Document 1 and Patent Document 2 have a description that the use of silica fine particles as low refractive index fine particles unevenly distributed on the surface side of the hardened layer for the purpose of preventing reflection improves the scratch resistance of the hardened layer.

JP 2007-86764 A JP 2007-133236 A JP 2007-121993 A JP 2007-23107 A

  When a hard coat layer and a functional layer such as an antireflection layer or an antiglare layer are respectively formed and laminated using a curable resin composition, it is difficult to ensure interlayer adhesion and sufficient scratch resistance. In addition to being obtained, there is also a problem of low manufacturing efficiency due to the formation of a plurality of layers. In addition, as described in Patent Documents 1 to 3, it can be formed with one coat of one kind of curable resin composition, and has both a hard coat property and optical functionality such as an antireflection effect and an antiglare effect. For the hard coat layer, sufficient hard coat properties and optical functions are not realized at the same time.

  The present invention has been accomplished in view of the above circumstances, and can be formed by one coat of one kind of curable resin composition, and has an antiglare layer having excellent hard coat properties as well as excellent antiglare properties. An object is to provide an antiglare film.

  As a result of intensive studies, the present inventors have made a reactive inorganic fine particle B having a specific average particle diameter and a crosslinking property capable of forming a crosslinking bond with the binder component C forming the uneven layer of the antiglare layer. Has been found to be able to obtain an antiglare film having both excellent antiglare properties and high hard coat properties by being unevenly distributed in the surface layer region on the side opposite to the transparent substrate film side of the uneven layer. The present invention has been completed.

  That is, the antiglare film of the present invention is an antiglare film in which an antiglare layer having an uneven shape on the outermost surface is provided on a transparent substrate film, and the antiglare layer is a single layer composed only of an uneven layer. Or, it has a laminated structure composed of two or more layers including a concavo-convex layer and a surface shape adjusting layer disposed on the viewer side of the concavo-convex layer, and the concavo-convex layer has (1) an average particle diameter of 1 μm or more and 10 μm. Translucent fine particles A in the following range, (2) Reactive functional groups having an average particle diameter in the range of 5 nm to 30 nm, at least part of which is coated with an organic component, and introduced by the organic component a reactive inorganic fine particle B having b on the surface, and (3) a binder component C having a reactive functional group c having cross-linking reactivity with the reactive functional group b of the reactive inorganic fine particle B. Curing bar that also has curing reactivity The hardened resin composition containing the inder system, and the surface of the uneven layer opposite to the transparent substrate film and the surface layer region in the vicinity thereof are closer to the transparent substrate film than the surface layer region. The skin layer has a larger average number of particles of the reactive inorganic fine particles B per unit area in the cross section in the thickness direction of the uneven layer than in the region, and the unit per unit area in the cross section in the thickness direction of the skin layer. The average number of particles of the reactive inorganic fine particles B is at least twice the average number of particles of the reactive inorganic fine particles B per unit area in the cross section in the thickness direction of the uneven layer.

  According to the present invention, in the skin layer where the reactive inorganic fine particles B are unevenly distributed, the number of crosslinking points due to the reactive functional groups b of the reactive inorganic fine particles B and the reactive functional groups c of the binder component C, and the reactive inorganic fine particles are increased. Due to the hardness of B, it is possible to obtain an antiglare film having high hardness and film strength and exhibiting excellent hard coat properties.

  In the antiglare film according to the present invention, in order to further enhance the effect of improving the hard coat property by the skin layer, the thickness of the skin layer is such that the reactive inorganic fine particles B are formed from the interface opposite to the transparent substrate film. It is preferable that the thickness is from 1 to 5 times the average particle diameter, and the reactive inorganic fine particles B are preferably concentrated in the skin layer.

Further, the average number of the reactive inorganic fine particles B per unit area in the cross section in the thickness direction of the skin layer is 800 particles / μm ² or more, and the per unit area in the cross section in the thickness direction of the entire concavo-convex layer. The average number of reactive inorganic fine particles B is preferably 500 / μm ² or less.

  When the inorganic fine particles serving as the core of the reactive inorganic fine particles B and the translucent inorganic fine particles A are made of the same material, the internal scattering property in the concavo-convex layer is increased, and the antiglare property can be further enhanced.

In the antiglare film according to the present invention, at least a part of the surface of the reactive inorganic fine particle B is coated with an organic component, and the reactive functional group b of the reactive inorganic fine particle B is formed by the organic component. It is preferable from the point which improves the hardness of a cured film that it is introduce | transduced into the surface and the said organic component is contained more than 1.00 * 10 < ^-3 > g / m < ² > per unit surface area of the inorganic fine particle before coating | cover.

  As the reactive inorganic fine particles B, those not containing fluorine can be used.

  The reactive functional group b of the reactive inorganic fine particle B and the reactive functional group c of the binder component C are preferably those having a polymerizable unsaturated group from the viewpoint of hard coat properties.

  Further, since it is possible to improve the film strength even if the organic component content is small, the reactive inorganic fine particle B is a saturated or unsaturated carboxylic acid, an acid anhydride corresponding to the carboxylic acid, an acid chloride, Surface modification with one or more molecular weights of 500 or less selected from the group consisting of esters and acid amides, amino acids, imines, nitriles, isonitriles, epoxy compounds, amines, β-dicarbonyl compounds, silanes, and functional metal compounds Those obtained by dispersing inorganic fine particles in water and / or an organic solvent as a dispersion medium in the presence of a compound are preferred.

  Since the reactive inorganic fine particle B can be efficiently surface-modified with an organic component, the surface-modifying compound is preferably a compound having a hydrogen bond-forming group. Further, since the reactive functional group b introduced into the reactive inorganic fine particle B and the reactive functional group c of the binder component C are easy to form a cross-linked bond, and the film strength can be further improved, the surface It is preferable that at least one of the modifying compounds has a polymerizable unsaturated group that becomes the reactive functional group b.

The reactive inorganic fine particle B includes a reactive functional group b introduced into the surface of the reactive inorganic fine particle B, a group represented by the following chemical formula (1), and a silanol group or a group that generates a silanol group by hydrolysis. In view of improving dispersibility in organic components and film strength, it is preferable that the metal oxide fine particles are obtained by bonding the fine particles to metal oxide fine particles.
Chemical formula (1)
^{-Q 1 -C (= Q 2)} -NH-
(In the chemical formula (1), Q ¹ represents NH, O (oxygen atom), or S (sulfur atom), and Q ² represents O or S.)

  The binder component C is preferably a compound having three or more reactive functional groups c that can bind to the reactive functional groups b of the reactive inorganic fine particles B.

  The content of the reactive inorganic fine particles B is preferably 5 to 30% by weight with respect to the total solid content.

  In the antiglare film of the present invention, it is preferable that the transparent base film is mainly composed of cellulose acylate, cycloolefin polymer, acrylate polymer, or polyester.

According to the present invention, in the steel wool test in which the surface of the antiglare layer is subjected to 10 reciprocating frictions at a speed of 50 mm / sec with # 0000 steel wool while applying a load of 300 g / cm ² , It is possible to provide an antiglare film excellent in hard coat properties provided with an antiglare layer that does not damage the surface of the layer.

  In the antiglare film of the present invention, it is preferable that the uneven layer has a film thickness of 0.5 μm or more and 30 μm or less because a favorable uneven shape can be formed on the uneven layer.

The antiglare film of the present invention has an antiglare layer having an irregular shape on the outermost surface, and has a specific particle size in the surface layer region opposite to the transparent substrate film and in the vicinity thereof, and the antiglare layer The anti-glare property and the hard anti-glare property are obtained by providing hard coating properties to the anti-glare layer by unevenly distributing the reactive inorganic fine particles having a reactive functional group capable of forming a crosslink with the binder component to be formed. It also has coat properties.
In addition, the antiglare layer can be formed by one coat of the curable resin composition containing the reactive inorganic fine particles, the binder component, and translucent fine particles having a specific average particle diameter. Therefore, the production efficiency is excellent, and there is no problem of interlayer adhesion, unlike the case where the hard coat layer and the antiglare layer are separately formed using a composition.

The antiglare film of the present invention is an antiglare film in which an outermost surface has an uneven shape on a transparent substrate film, and the antiglare layer is a single layer consisting only of an uneven layer, Or, it has a laminated structure consisting of two or more layers including a concavo-convex layer and a surface shape adjusting layer disposed on the viewer side of the concavo-convex layer,
(1) Translucent fine particles A having an average particle diameter in the range of 1 μm to 10 μm,
(2) Reactive inorganic fine particles B having an average particle diameter in the range of 5 nm or more and 30 nm or less, having at least a part of the surface coated with an organic component, and having a reactive functional group b introduced by the organic component on the surface; And (3) a curable binder system including a binder component C having a reactive functional group c having a crosslinking reactivity with the reactive functional group b of the reactive inorganic fine particle B, and also having a curing reactivity in the system. It consists of a cured product of a curable resin composition containing,
Compared with the area on the opposite side of the transparent substrate film of the uneven layer and the surface layer region in the vicinity thereof, compared to the region on the transparent substrate film side of the surface layer region, per unit area in the thickness direction cross section of the uneven layer The reactive inorganic fine particle B has a skin layer with a large average particle number, and the average particle number of the reactive inorganic fine particle B per unit area in the thickness direction cross section of the skin layer is the thickness direction of the uneven layer. The average particle number of the reactive inorganic fine particles B per unit area in the cross section is twice or more.

  Here, the skin layer is a layer of reactive inorganic fine particles B in a surface layer region extending from the interface (so-called air interface) opposite to the transparent substrate film side of the uneven layer constituting the antiglare layer to a certain depth. It is a layered structure formed unevenly and constitutes the outermost surface of the uneven layer on the air interface side. The skin layer contains a larger amount of reactive inorganic fine particles B than the region on the transparent substrate film side of the surface layer region of the concavo-convex layer. After a certain depth from the interface, the average number of reactive inorganic fine particles B per unit area in the cross section in the thickness direction decreases rapidly toward the transparent substrate film side, and the presence of the boundary of the skin layer It can be clearly distinguished. The average number of reactive inorganic fine particles B per unit area in the cross section in the thickness direction of the skin layer is at least twice the average number of particles per unit area in the cross section in the thickness direction of the entire concavo-convex layer including the skin layer. .

Here, the distribution state of the reactive inorganic fine particles B in the uneven layer of the antiglare film according to the present invention will be described with reference to FIG.
First, in the cross section in the thickness direction of the concavo-convex layer 3, on the transparent substrate film side interface, the interface opposite to the transparent substrate film (air side interface), and two sides parallel to the thickness direction of the concavo-convex layer The surrounded region S is cut out, and the average number A of reactive inorganic fine particles B per unit area of the region S is determined as the average of the reactive inorganic fine particles B per unit area in the cross section in the thickness direction of the entire concavo-convex layer 3. The number of particles.
In the region S, The measured average particle number a ₁ per unit area in the region s ₁ from the air side interface to a certain depth D _1, a a _{1> A} × 2. The depth D from the air side interface were deeper than D _1, when we measure the average particle number a per unit area in the region s to a depth of D from the air side interface, the average number of particles per unit area There is a depth D _m where a _m is such that a _m = A × 2. Then, is deeper than _{D m} depth from the air side interface, the region _{s m + 1} of the depth _{D m + 1,} the average number of particles _{a m + 1} per unit area _{becomes a m + 1 <A × 2} . At this time, the region s _m from the air interface side to the depth D _m can be considered as a skin layer.

In addition, the distribution state of the reactive inorganic fine particles B in the concavo-convex layer can be confirmed by a transmission electron microscope (STEM) photograph of the concavo-convex layer. The boundary can be clearly identified visually.
Further, the average number of reactive inorganic fine particles B per unit area in the cross section in the thickness direction of the uneven layer can be determined as follows. That is, the density per unit area can be calculated by counting the number of reactive inorganic fine particles based on the STEM photograph of the cross section in the depth direction of the concavo-convex layer and dividing by the area where the counted particles exist.

  In FIG. 1, the one example of an anti-glare film of this invention is shown. In the antiglare film 100 shown in FIG. 1, an antiglare layer 2 having an uneven surface on the outermost surface is directly provided on one surface of the transparent substrate film 1. The antiglare layer 2 has a single structure consisting only of the concavo-convex layer 3 having the concavo-convex shape on the outermost surface. It has a skin layer 3 ′ in which inorganic fine particles 5 are unevenly distributed.

Thus, in the uneven layer constituting the antiglare layer having the antiglare effect, the reactive inorganic fine particles B are unevenly distributed on the interface opposite to the transparent substrate film side and the surface layer region in the vicinity thereof, and other than the surface layer region By making the reactive inorganic fine particles B more present than in the region, first, the hardness of the antiglare layer can be improved by the high hardness of the reactive inorganic fine particles B themselves. Furthermore, the film strength can be improved by uneven distribution of cross-linking points between the reactive inorganic fine particles B and the binder component C. By unevenly distributing the reactive inorganic fine particles B in this way, the hard coat property on the surface of the antiglare layer is remarkably and efficiently improved as compared with the case where the same amount of the reactive inorganic fine particles B is dispersed throughout the uneven layer. It is possible.
Moreover, in the antiglare film of the present invention, the reactive inorganic fine particles B are unevenly distributed from the surface of the concavo-convex layer to a certain depth (skin layer), and the reactive inorganic fine particles B per unit area in the cross section in the thickness direction. The average number of particles rapidly decreases when the above-mentioned fixed depth is exceeded. Thus, by distributing the reactive inorganic fine particles B so that the boundary of the region (skin layer) where the reactive inorganic fine particles B are unevenly distributed becomes clear, the density of the reactive inorganic fine particles gradually increases from the surface of the uneven layer. The hard coat property of the uneven layer can be effectively improved as compared with the case where the uneven structure is unevenly distributed.

The thickness of the skin layer is the same thickness as the average particle diameter of the reactive inorganic fine particles B from the interface opposite to the transparent base film, and particularly the average particle diameter of the reactive inorganic fine particles B. It is preferable that the thickness is from 1 to 3 times. Thus, by making the reactive inorganic fine particles B unevenly distributed in a very limited narrow surface region on the air interface side of the concavo-convex layer, the hard coat property of the antiglare layer can be improved efficiently.
Further, in order to enhance the effect of improving the hard coat property by the skin layer, it is preferable that the reactive inorganic fine particles B are concentrated in the skin layer. Here, the fact that the reactive inorganic fine particles are dense is a state where the adjacent reactive inorganic fine particles B are in contact with each other. Thus, by increasing the uneven distribution of the reactive inorganic fine particles B in the skin layer, the hardness and film strength of the uneven layer surface can be further increased.

The average number of reactive inorganic fine particles B per unit area in the thickness direction cross section of the skin layer is 2 of the average number of reactive inorganic fine particles B per unit area in the entire thickness direction cross section of the uneven layer including the skin layer. If it is twice or more, the hard coat property of the antiglare layer can be sufficiently improved, but it is particularly preferably 3 times or more, and more preferably 5 times or more.
More specifically, the average number of reactive inorganic fine particles B per unit area in the cross section in the thickness direction of the skin layer is 800 particles / μm ² or more, and per unit area in the cross section in the thickness direction of the entire concavo-convex layer. The average number of reactive inorganic fine particles B is preferably 500 / μm ² or less. From the viewpoint of hard coat properties of the antiglare layer, in particular, the average number of reactive inorganic fine particles B per unit area in the cross section in the thickness direction of the skin layer is 800 particles / μm ² or more, and The average number of reactive inorganic fine particles B per unit area in the cross section in the thickness direction is preferably 400 particles / μm ² or less.

In the antiglare film, the antiglare layer is always disposed on the surface on the viewer side. Here, in this invention, the observer side means the surface which turns to an observer, when arrange | positioning the anti-glare film which concerns on this invention in an image display apparatus. In the present invention, the display device side means a surface directed to the image display device main body when the antiglare film according to the present invention is arranged on the image display device.
Moreover, although the glare-proof film shown in FIG. 1 is provided with the glare-proof layer directly on the transparent base film, you may provide a glare-proof layer on a transparent base film through another layer. . Further, the antiglare layer only needs to have a concavo-convex shape that forms the outermost surface of the antiglare layer, and is not limited to a single structure consisting only of the concavo-convex layer. You may have the laminated structure which consists of two or more layers containing the arrange | positioned surface shape adjustment layer. A specific laminated structure will be described later.

Hereinafter, the antiglare film of the present invention will be described in detail.
In the present specification, (meth) acryloyl represents acryloyl and methacryloyl, (meth) acrylate represents acrylate and methacrylate, and (meth) acryl represents acryl and methacryl. The light in this specification includes not only electromagnetic waves having wavelengths in the visible and invisible regions, but also particle beams such as electron beams, and radiation or ionizing radiation that collectively refers to electromagnetic waves and particle beams.

The reactive functional group includes a photocurable functional group and a thermosetting functional group. The photo-curable functional group means a functional group capable of curing a coating film by proceeding a polymerization reaction or a crosslinking reaction by light irradiation, such as photo radical polymerization, photo cation polymerization, or photo anion polymerization. And a reaction that proceeds by a reaction method such as addition polymerization or condensation polymerization that proceeds via photodimerization. In addition, the thermosetting functional group in the present specification is a functional group capable of curing a coating film by causing a polymerization reaction or a crosslinking reaction to proceed between the same functional groups or other functional groups by heating. For example, a hydroxyl group, a carboxyl group, an amino group, an epoxy group, an isocyanate group and the like can be exemplified.
As the reactive functional group used in the present invention, particularly from the viewpoint of improving the hardness of the cured film, a polymerizable unsaturated group is preferably used, preferably a photocurable unsaturated group, particularly preferably an ionization. It is a radiation curable unsaturated group. Specific examples thereof include an ethylenic double bond such as a (meth) acryloyl group, a vinyl group, and an allyl group, and an epoxy group.

[Transparent substrate film]
The material of the transparent substrate film is not particularly limited, but general materials used for anti-glare films can be used, for example, those mainly composed of cellulose acylate, cycloolefin polymer, acrylate polymer, or polyester. Is mentioned. Here, “mainly” means a component having the highest content ratio among the constituent components of the base material.

Specific examples of cellulose acylate include cellulose triacetate, cellulose diacetate, and cellulose acetate butyrate.
Examples of the cycloolefin polymer include a norbornene polymer, a monocyclic olefin polymer, a cyclic conjugated diene polymer, a vinyl alicyclic hydrocarbon polymer resin, and more specifically, ZEONEX and ZEONOR (norbornene resin) manufactured by ZEON CORPORATION, Sumitrite Bakelite Co., Ltd. Sumilite FS-1700, JSR Co., Ltd. Arton (modified norbornene resin), Mitsui Chemicals, Inc. Appel (cyclic olefin) Copolymer), Ticona's Topas (cyclic olefin copolymer), Hitachi Chemical Co., Ltd.'s Optrez OZ-1000 series (alicyclic acrylic resin), and the like.

Specific examples of the acrylate polymer include methyl poly (meth) acrylate, poly (meth) ethyl acrylate, methyl (meth) acrylate-butyl (meth) acrylate, and the like. Here, (meth) acryl means acryl, methacryl or a mixture of both.
Specific examples of the polyester include polyethylene terephthalate and polyethylene naphthalate.

  In the present invention, when the transparent substrate is used as a film-like body rich in thin film flexibility, the thickness is 20 μm or more and 300 μm or less, preferably the upper limit is 200 μm or less, and the lower limit is 30 μm or more. is there. In the case where the transparent substrate is a rigid plate-like body, the thickness may exceed the above thickness range, and a thickness of about 1 to 5 mm is used. When forming an antiglare layer on the transparent substrate film, in order to improve adhesion, in addition to physical treatment such as corona discharge treatment and oxidation treatment, a coating called an anchor agent or primer is applied. It may be performed in advance. Further, the transparent substrate film is not limited to only one layer, and two or more layers may be present.

[Anti-glare layer]
The antiglare layer is an essential layer for the antiglare film of the present invention, and is provided on the surface on the viewer side. The antiglare layer is composed of one layer or two or more layers, has at least an uneven layer, and the outermost surface has an uneven shape.
In this invention, you may laminate | stack the uneven | corrugated layer previously shape | molded on the surfaces, such as the said transparent base film.

(Uneven layer)
The concavo-convex layer in the antiglare layer film of the present invention has adhesiveness to translucent fine particles A for imparting antiglare properties, reactive inorganic fine particles B for imparting hard coat properties, and substrates and adjacent layers. Containing a component that forms a matrix of a concavo-convex layer after curing of the curable binder system, and further, if necessary, additives such as an antistatic agent and a leveling agent, It is formed containing an inorganic filler for adjusting the refractive index, preventing crosslinking shrinkage, and imparting high indentation strength.

<Translucent fine particles A>
The translucent fine particles A are fine particles contained in the antiglare layer in order to form surface irregularities and impart antiglare properties. Depending on the purpose, the translucent fine particles A can be used not only in one type but also in a mixture of two or more types having different components, different shapes, different particle size distributions, and the like. Preferably, 1 to 3 types are used, particularly 1 to 2 types. However, various kinds of particles can be used for purposes other than forming irregularities.

The one or more kinds of translucent fine particles A used in the present invention may be spherical, for example, spherical, spheroid, etc., and more preferably spherical. Each average particle diameter (μm) of one or more kinds of translucent fine particles A is 1 μm or more and 10 μm or less, preferably 1 μm or more and 7 μm or less, and more preferably 1.5 μm or more and 5 μm or less.
When the average particle size is less than 1 μm, it is difficult to provide a concavo-convex shape having a size capable of exhibiting sufficient anti-glare property on the surface of the antiglare layer. Therefore, the physical properties of the antiglare layer are deteriorated. On the other hand, when the average particle diameter exceeds 10 μm, the surface shape of the antiglare layer becomes rough, and the surface quality may be deteriorated, or whiteness may increase due to an increase in surface haze.
The average particle size of the translucent fine particles A represents the average particle size if each of the contained particles is monodisperse type particles (particles having a single shape), and has a broad particle size distribution. In the case of an irregular-shaped particle having a particle size, the particle size of the most abundant particles is expressed as an average particle size by particle size distribution measurement. The particle diameter of the fine particles can be measured mainly by the Coulter counter method. In addition to this method, measurement can also be performed by laser diffraction or SEM photography. The translucent fine particles A may be agglomerated particles, and in the case of agglomerated particles, the secondary particle diameter is preferably within the above range.

  In each of the translucent fine particles A, 80% or more (preferably 90% or more) of the entire translucent fine particles are preferably in the range of each average particle diameter ± 300 nm. Thereby, the uniformity of the uneven shape of the antiglare layer can be improved.

  The translucent fine particles A are not particularly limited, and inorganic and organic particles can be used. It is particularly preferable to use inorganic fine particles from the viewpoint of increasing the film strength.

  Specific examples of the fine particles formed of an organic material include plastic beads. Plastic beads include polystyrene beads (refractive index 1.60), melamine resin beads (refractive index 1.57), acrylic beads (refractive index 1.50 to 1.53), acrylic-styrene beads (refractive index 1.54). To 1.58), benzoguanamine beads, benzoguanamine / formaldehyde condensation beads, polycarbonate beads, polyethylene beads, and the like. The plastic beads preferably have a hydrophobic group on the surface, and examples thereof include styrene beads.

Examples of the inorganic fine particles include amorphous silica and inorganic silica beads. As the amorphous silica, it is preferable to use silica beads having a particle diameter of 1 to 10 μm with good dispersibility.
Further, in order to improve the dispersibility of the amorphous silica without causing an increase in the viscosity of the antiglare layer forming coating liquid described in detail below, the surface of the particles was treated with an organic substance to be hydrophobized. It is preferable to use amorphous silica. In the organic treatment, there is a physical method in which a compound is chemically bonded to the bead surface, or a physical substance that does not chemically bond to the bead surface and penetrates into voids existing in the composition forming the bead. There are methods and either one can be used.

In general, a chemical treatment method using an active group on a silica surface such as a hydroxyl group or a silanol group is preferably used from the viewpoint of treatment efficiency. As the compound used for the treatment, a silane-based, siloxane-based, or silazane-based material having high reactivity with the active group is used. For example, linear alkyl monosubstituted silicone materials such as methyltrichlorosilane, branched alkyl monosubstituted silicone materials, linear alkyl polysubstituted silicone compounds such as di-n-butyldichlorosilane and ethyldimethylchlorosilane, Examples include substituted silicone compounds. Similarly, mono-substituted, poly-substituted siloxane materials, and silazane materials having a linear alkyl group or a branched alkyl group can also be used effectively.
Depending on the required function, those having a hetero atom, an unsaturated bond group, a cyclic bond group, an aromatic functional group or the like at the terminal or intermediate part of the alkyl chain may be used.
In these compounds, the alkyl group contained is hydrophobic, so that the surface of the material to be treated can be easily converted from hydrophilic to hydrophobic, and both the high-molecular material with poor affinity when untreated is high. Affinity can be obtained.

  In the concavo-convex layer, the content of the translucent fine particles A is preferably 5% by mass or more and 40% by mass or less based on the total solid content of the concavo-convex layer. More preferably, it is 10 mass% or more and 30 mass% or less. If it is less than 5% by mass, sufficient antiglare property cannot be imparted, and if it exceeds 40% by mass, the film strength may be lowered, and sufficient hard coat property may not be imparted to the antiglare layer.

  When a large amount of the above-mentioned translucent fine particles A are added, the translucent fine particles A easily settle in the resin composition. Therefore, an inorganic filler such as silica may be added to prevent sedimentation. The inorganic filler is more effective in preventing sedimentation of the translucent fine particles A as the amount added is increased, but depending on the particle size and the amount used, the transparency of the coating film is adversely affected. Therefore, it is preferable that an inorganic filler having a particle size of 0.5 μm or less is contained so as not to impair the transparency of the coating film with respect to the binder.

In the present invention, when two or more kinds of translucent fine particles A are mixed and used, the average particle size of the first fine particles is R ₁ (μm), and the average particle size of the second fine particles is R ₂ (μm). ), The following formula (I):
0.25R ₁ (preferably 0.50R ₁ ) ≦ R ₂ ≦ 1.0R ₁ (preferably 0.75R ₁ ) (I)
Those satisfying these conditions are preferred.
When R ₂ is 0.25R ₁ or more, the coating liquid is easily dispersed and the particles are not aggregated. Moreover, a uniform uneven | corrugated shape can be formed, without receiving to the influence of the wind at the time of floating in the drying process after application | coating. This relationship holds true for the third fine particles relative to the second fine particles. When the third fine particles are R ₃ , those satisfying 0.25R ₂ ≦ R ₃ ≦ 1.0R ₂ are preferable.
When two or more kinds of fine particles comprising different components are mixed and used, the two or more kinds of fine particles preferably have different average particle diameters as described above, but those having the same average particle diameter are also suitable. Used for.

According to another aspect of the present invention, the total mass ratio per unit area of the binder, the first fine particles, and the second fine particles is the total mass per unit area of the first fine particles as M _1. When the total mass per unit area of the second fine particles is M ₂ and the total mass per unit area of the binder is M, the following formulas (II) and (III):
_{0.08 ≦ (M 1 + M 2} ) /M≦0.36 (II)
0 ≦ M ₂ ≦ 4.0M ₁ (III)
Those satisfying these conditions are preferred.
Among them, the content of the second fine particles is preferably 3 to 100% by mass with respect to the content of the first fine particles. Moreover, when 3 or more types of microparticles | fine-particles are included, it is preferable that content of 3rd microparticles is 3-100 mass% of 2nd microparticles. The particle content after the fourth fine particles also preferably follows this relationship.

<Reactive inorganic fine particles B>
Generally, hard coat properties are improved by incorporating inorganic fine particles in the hard coat layer. Moreover, hard coat property can further be improved by carrying out the crosslinking reaction of the inorganic fine particle which has crosslinking reactivity, and a sclerosing | hardenable binder, and forming a crosslinked structure. The reactive inorganic fine particle B is an inorganic fine particle in which at least a part of the surface of the inorganic fine particle as a core is coated with an organic component and the surface has a reactive functional group b introduced by the organic component. The reactive inorganic fine particles B include those having two or more inorganic fine particles as a core per particle.

  The antiglare layer according to the present invention contains reactive inorganic fine particles B for the purpose of improving the hardness so as to have sufficient scratch resistance. The reactive inorganic fine particle B may be one that further imparts a function to the antiglare layer, and is appropriately selected and used according to the purpose.

  Examples of the inorganic fine particles include metal oxide fine particles such as silica, aluminum oxide, zirconia, titania, zinc oxide, germanium oxide, indium oxide, tin oxide, indium tin oxide (ITO), antimony oxide, cerium oxide, and fluoride. Examples thereof include metal fluoride fine particles such as magnesium and sodium fluoride. Metal fine particles, metal sulfide fine particles, metal nitride fine particles and the like may be used.

  From the viewpoint of high hardness, silica and aluminum oxide are preferable. Further, in order to obtain a relatively high refractive index layer, fine particles having a high refractive index when a film such as zirconia, titania or antimony oxide is formed can be appropriately selected and used. Similarly, in order to obtain a relatively low refractive index layer, fluoride fine particles such as magnesium fluoride and sodium fluoride, and fine particles having a low refractive index during film formation such as hollow silica fine particles are appropriately selected and used. be able to. Furthermore, when it is desired to impart antistatic properties and conductivity, indium tin oxide (ITO), tin oxide, or the like can be appropriately selected and used. These can be used alone or in combination of two or more.

  In the antiglare film of the present invention, when a hollow reactive inorganic fine particle B such as hollow silica or a reactive inorganic fine particle B having a porous structure is used, its apparent specific gravity (averaged including the hollow portion) The mass per unit volume) can also be expected to promote the uneven distribution of the reactive inorganic fine particles B on the air interface side. However, the hollow and porous inorganic fine particles are structurally solid and solid inorganic fine particles. In comparison, the hardness is lowered. Therefore, in the present invention, it is preferable that the hardness is typically ensured by using solid reactive inorganic fine particles B, and the uneven distribution of reactive inorganic fine particles B is promoted by controlling the particle size. .

Further, the combination of the reactive inorganic fine particles B and the light transmitting fine particles A is not particularly limited, but when the light transmitting fine particles A made of the same material as the inorganic fine particles serving as the core of the reactive inorganic fine particles B are used in combination, An improvement in the haze property of the antiglare layer can be expected. When the core of the reactive inorganic fine particle B and the translucent fine particle A are made of the same inorganic material, the reactive inorganic fine particle B aggregates around the translucent fine particle A due to the affinity thereof, and the aggregate in the uneven layer This is because internal scattering increases.
Here, as the combination of the inorganic fine particles serving as the core of the reactive inorganic fine particles and the translucent fine particles made of the same material, specifically, silica is used as the core of the reactive inorganic fine particles B and the translucent fine particles A. Combinations are listed.

  The surface of the inorganic fine particles usually has groups that cannot exist in this form in the inorganic fine particles. These surface groups are usually relatively reactive functional groups. For example, a metal oxide has, for example, a hydroxyl group and an oxy group, for example, a metal sulfide, a thiol group and a thio group, or, for example, a nitride, an amino group, an amide group, and an imide group.

  The reactive inorganic fine particles B used in the present invention are coated with an organic component on at least a part of the surface, and have a reactive functional group b introduced by the organic component on the surface. Here, the organic component is a component containing carbon. Further, as an aspect in which at least a part of the surface is coated with an organic component, for example, a compound containing an organic component such as a silane coupling agent reacts with a hydroxyl group present on the surface of the metal oxide fine particles, thereby In addition to the mode in which the organic component is bonded to the part, for example, the mode in which the organic component is attached to the hydroxyl group present on the surface of the metal oxide fine particle by the interaction such as hydrogen bond, or one or two or more in the polymer particle An embodiment containing inorganic fine particles is included.

The coating organic component covers almost the entire particle surface from the viewpoint of suppressing aggregation of inorganic fine particles and increasing the number of reactive functional groups on the surface of the inorganic fine particles to improve the hardness of the film. It is preferable. From such a viewpoint, the organic component coating the reactive inorganic fine particles B is 1.00 × 10 ⁻³ g / m ² or more per unit area of the inorganic fine particles before coating in the reactive inorganic fine particles B. It is preferably included.
In an embodiment in which an organic component is attached to or bonded to the surface of the inorganic fine particles, the organic component covering the reactive inorganic fine particles B is included in the reactive inorganic fine particles B per unit area of the inorganic fine particles before coating. More preferably, it is contained at least 00 × 10 ⁻³ g / m ^{2, and} particularly preferably at least 3.50 × 10 ⁻³ g / m ² .
In an aspect in which the polymer particles contain inorganic fine particles, the organic component coating the reactive inorganic fine particles B is 3.50 × 10 per unit area of the inorganic fine particles before coating in the reactive inorganic fine particles B. ^-3 g / m ² or more is more preferable, and 5.50 × 10 ⁻³ g / m ² or more is particularly preferable.

The ratio of the organic component to be coated is usually determined by a thermogravimetric analysis in the air from room temperature to usually 800 ° C., for example, as a constant weight value when the dry powder is completely burned in the air. Can be sought.
The amount of organic component per unit area is determined by the following method. First, organic component weight / inorganic component weight is measured by differential thermogravimetric analysis TG-DTA. Next, the volume of the entire inorganic component is calculated from the weight and the specific gravity of the used inorganic fine particles. Further, assuming that the inorganic fine particles before coating are spherical, the volume per inorganic fine particle before coating is calculated from the average particle diameter of the inorganic fine particles before coating. From the volume of the entire inorganic component and the volume per inorganic fine particle B before coating, the number of inorganic fine particles before coating is determined. Next, by dividing the organic component weight per reactive inorganic fine particle B by the surface area per inorganic fine particle before coating, the amount of organic component per unit area of the inorganic fine particle before coating can be obtained.

The reactive inorganic fine particles B used in the present invention have an average particle size of 5 nm to 30 nm. In the present invention, by using the reactive inorganic fine particles B having a relatively small particle diameter as described above, a certain region of the reactive inorganic fine particles B in the antiglare layer (the interface on the side opposite to the transparent base film and the vicinity thereof). In the surface layer region) and the improvement of the hard coat property of the antiglare layer by the reactive inorganic fine particles B is achieved.
The reactive inorganic fine particle B having a small particle size having an average particle size in the above range has a large specific surface area, and therefore tends to undergo phase separation in the curable resin composition based on the compatibility with the binder component. Power increases. As a result, in the curable resin composition applied on the transparent substrate film, part of the reactive inorganic fine particles B naturally diffuses to the air interface side and is unevenly distributed.

  As described above, the antiglare film of the present invention promotes the uneven distribution of the reactive inorganic fine particles B by utilizing the increase in phase separation and diffusibility by reducing the particle size of the reactive inorganic fine particles B, The improvement of the hard coat property of the antiglare layer is realized.

  By setting the average particle size of the reactive inorganic fine particles B to 5 nm or more, it is possible to sufficiently improve the hard coat property of the antiglare layer. On the other hand, by using the reactive inorganic fine particles B having an average particle size of 30 nm or less, the uneven distribution of the reactive inorganic fine particles B can be sufficiently promoted, and sufficient hard coat properties can be improved by the uneven distribution of the reactive inorganic fine particles B. An effect is obtained. In addition, the reactive inorganic fine particles B having an average particle size of 30 nm or less have an advantage that the specific surface area is large, so that the cross-linking point in the matrix can be increased, and an uneven layer having high film strength can be obtained.

The average particle diameter of the reactive inorganic fine particles B is preferably 10 nm or more, particularly preferably 15 nm or more, from the viewpoint of the hardness of the uneven layer. Further, from the viewpoint of uneven distribution on the surface, it is preferably 25 nm or less, and particularly preferably 20 nm or less.
In addition, the reactive inorganic fine particles B have a narrow particle size distribution and are monodispersed from the point that the hardness is remarkably improved while maintaining the restoration rate of the concavo-convex layer when formed using only a resin without impairing transparency. It is preferable that
In addition, the average particle diameter here observes by the cross-sectional TEM photograph of the anti-glare film produced using the reactive inorganic fine particle B, measures the particle size of the reactive inorganic fine particle B, and calculates the average value. In addition, the reactive inorganic fine particles B can be used as a solvent-dispersed sol, and the 50% average particle size in the sol can be determined using, for example, Nanotrac or a particle size analyzer manufactured by Nikkiso Co., Ltd.

  In addition, as the reactive functional group b of the reactive inorganic fine particle B, particularly from the viewpoint of improving the hardness of the cured film, a polymerizable unsaturated group is preferably used, preferably a photocurable unsaturated group, Particularly preferred are ionizing radiation curable unsaturated groups. Specific examples thereof include an ethylenic double bond such as a (meth) acryloyl group, a vinyl group, and an allyl group, and an epoxy group.

As a method of preparing reactive inorganic fine particles B having a reactive functional group b introduced by the organic component on at least a part of the surface, the kind of the inorganic fine particles and the reactivity to be introduced A conventionally known method can be appropriately selected and used depending on the functional group b.
Among them, in the present invention, the organic component to be coated can be contained in the reactive inorganic fine particles B at 1.00 × 10 ⁻³ g / m ² or more per unit area of the inorganic fine particles before coating, From the viewpoint of suppressing aggregation of inorganic fine particles and improving the hardness of the film, it is preferable to select and use any one of the following inorganic fine particles (i).
(I) saturated or unsaturated carboxylic acid, acid anhydride, acid chloride, ester and acid amide corresponding to the carboxylic acid, amino acid, imine, nitrile, isonitrile, epoxy compound, amine, β-dicarbonyl compound, silane, And by dispersing inorganic fine particles in water and / or an organic solvent as a dispersion medium in the presence of one or more surface modification compounds having a molecular weight of 500 or less selected from the group consisting of metal compounds having functional groups. Inorganic fine particles having a reactive functional group b on the surface.
(Ii) The reactive functional group b to be introduced into the inorganic fine particles, the group represented by the following chemical formula (1), and a compound containing a silanol group or a group that generates a silanol group by hydrolysis are bonded to the metal oxide fine particles. Inorganic fine particles having reactive functional groups on the surface, obtained by
Chemical formula (1)
^{-Q 1 -C (= Q 2)} -NH-
(In the chemical formula (1), Q ¹ represents NH, O (oxygen atom), or S (sulfur atom), and Q ² represents O or S.)

Hereinafter, the reactive inorganic fine particles B preferably used in the present invention will be described in order.
(I) saturated or unsaturated carboxylic acid, acid anhydride, acid chloride, ester and acid amide corresponding to the carboxylic acid, amino acid, imine, nitrile, isonitrile, epoxy compound, amine, β-dicarbonyl compound, silane, And by dispersing inorganic fine particles in water and / or an organic solvent as a dispersion medium in the presence of one or more surface modification compounds having a molecular weight of 500 or less selected from the group consisting of metal compounds having functional groups. Inorganic fine particles having a reactive functional group on the surface.
When the reactive inorganic fine particles B (i) are used, there is an advantage that the film strength can be improved even if the organic component content is small.

  The surface modifying compound used for the reactive inorganic fine particle B of (i) is a carboxyl group, an acid anhydride group, an acid chloride group, an acid amide group, an ester group, an imino group, a nitrile group, an isonitrile group, a hydroxyl group, Such as thiol groups, epoxy groups, primary, secondary and tertiary amino groups, Si-OH groups, hydrolyzable residues of silanes, or C-H acid groups such as β-dicarbonyl compounds, It has a functional group capable of chemically bonding with a group present on the surface of the inorganic fine particle under dispersion conditions. The chemical bond here preferably includes a covalent bond, an ionic bond or a coordinate bond, but also includes a hydrogen bond. The coordination bond is considered to be complex formation. For example, acidic / base reaction, complex formation or esterification according to Bronsted or Lewis occurs between the functional group of the surface modifying compound and the group on the surface of the inorganic fine particle. The surface modifying compound used in the reactive inorganic fine particles B of (i) can be used alone or in combination of two or more.

The surface modifying compound is usually added to the surface modifying compound via the functional group in addition to at least one functional group (hereinafter referred to as a first functional group) capable of participating in chemical bonding with the surface group of the inorganic fine particles. After linking, it has molecular residues that impart new properties to the inorganic particulates. The molecular residue or a part thereof is hydrophobic or hydrophilic and, for example, stabilizes, integrates, or activates inorganic fine particles.
For example, examples of the hydrophobic molecular residue include an alkyl, aryl, alkaryl, aralkyl, or fluorine-containing alkyl group that causes inactivation or repulsion. Examples of the hydrophilic group include a hydroxy group, an alkoxy group, and a polyester group.

The reactive functional group b introduced to the surface so that the reactive inorganic fine particles B can react with the binder component C is appropriately selected according to the binder component C. As the reactive functional group b, a polymerizable unsaturated group is suitably used, preferably a photocurable unsaturated group, and particularly preferably an ionizing radiation curable unsaturated group. Specific examples thereof include an ethylenic double bond such as a (meth) acryloyl group, a vinyl group, and an allyl group, and an epoxy group.
When a reactive functional group b capable of reacting with the binder component C is contained in the molecular residue of the surface modifying compound, the first functional group contained in the surface modifying compound is reacted with the surface of the inorganic fine particles. By doing so, it is possible to introduce the reactive functional group b capable of reacting with the binder component C onto the surface of the reactive inorganic fine particle B of (i). For example, in addition to the first functional group, a surface modification compound further having a polymerizable unsaturated group is preferable.

  On the other hand, a second reactive functional group is contained in the molecular residue of the surface modification compound, and the reactive inorganic fine particle B of (i) is used as a foothold based on the second reactive functional group. A reactive functional group b capable of reacting with the binder component C may be introduced on the surface. For example, a group capable of hydrogen bonding (hydrogen bond forming group) such as a hydroxyl group and an oxy group is introduced as the second reactive functional group, and another hydrogen bond forming group introduced on the surface of the fine particles It is preferable that the reactive functional group b capable of reacting with the binder component C is introduced by the reaction of the hydrogen bond forming group of the surface modification compound. That is, as the surface modification compound, a compound having a hydrogen bond forming group and a compound having a reactive functional group b capable of reacting with the binder component C such as a polymerizable unsaturated group and a hydrogen bond forming group are used in combination. Is a suitable example. Specific examples of the hydrogen bond-forming group indicate a functional group such as a hydroxyl group, a carboxyl group, an epoxy group, a glycidyl group, an amide group, or an amide bond. Here, the amide bond indicates that the bond unit contains —NHC (O) or> NC (O) —. Among the hydrogen bond forming groups used in the surface modification compound of the present invention, among them, a carboxyl group, a hydroxyl group, and an amide group are preferable.

The surface-modifying compound used in the reactive inorganic fine particle B (i) has a molecular weight of 500 or less, more preferably 400, particularly 200. Since it has such a low molecular weight, it is presumed that the surface of the inorganic fine particles can be rapidly occupied and aggregation of the inorganic fine particles can be prevented.
The surface modifying compound used for the reactive inorganic fine particles B of (i) is preferably a liquid under the reaction conditions for surface modification, and is preferably soluble or at least emulsifiable in a dispersion medium. Among these, it is preferable that the polymer is dissolved in the dispersion medium and uniformly distributed as discrete molecules or molecular ions in the dispersion medium.

  Saturated or unsaturated carboxylic acids have 1 to 24 carbon atoms, such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, acrylic acid, methacrylic acid, crotonic acid, citric acid, adipine Examples include acids, succinic acid, glutaric acid, oxalic acid, maleic acid, fumaric acid, itaconic acid and stearic acid, and the corresponding acid anhydrides, chlorides, esters and amides such as caprolactam. The carboxylic acid includes those having a carbon chain blocked by an O-group, S-group or NH-group. Particularly preferred are carboxylic acid ethers such as carboxylic acid monoethers and carboxylic acid polyethers, and the corresponding acid hydrates, esters and amides (eg, methoxyacetic acid, 3,6-dioxaheptanoic acid and 3,6,6 9-trioxadecanoic acid) and the like. Further, when an unsaturated carboxylic acid is used, a polymerizable unsaturated group can be introduced.

Examples of preferred amines are those having the general formula _{Q 3-n NH n (n} = 0,1 or 2), residues Q are independently 1 to 12, especially 1 to 6, particularly preferably 1 Alkyls having ˜4 carbon atoms (eg methyl, ethyl, n-propyl, i-propyl and butyl), and aryls, alkaryls or aralkyls having 6-24 carbon atoms (eg phenyl, naphthyl, tolyl and benzyl) ). Examples of preferred amines include polyalkyleneamines, and specific examples are methylamine, dimethylamine, trimethylamine, ethylamine, aniline, N-methylaniline, diphenylamine, triphenylamine, toluidine, ethylenediamine, and diethylenetriamine. .

Preferred β-dicarbonyl compounds are those having 4 to 12, particularly 5 to 8 carbon atoms, such as diketones (such as acetylacetone), 2,3-hexanedione, 3,5-heptanedione, acetoacetic acid, acetoacetate. Examples include acetic acid-C ₁ -C ₄ -alkyl esters (such as acetoacetic acid ethyl ester), diacetyl and acetonylacetone.
Examples of amino acids include β-alanine, glycine, valine, aminocaproic acid, leucine and isoleucine.

Preferred silanes are hydrolyzable organosilanes having at least one hydrolyzable group or hydroxy group and at least one non-hydrolyzable residue. Here, examples of the hydrolyzable group include a halogen, an alkoxy group, and an acyloxy group. As the non-hydrolyzable residue, a non-hydrolyzable residue having a reactive functional group b and / or not having a reactive functional group b is used. Silanes having at least partially organic residues substituted with fluorine may also be used.
As the silane used is not particularly limited, for _{example, CH 2 = CHSi (OOCCH 3} ) 3, CH 2 = CHSiCl 3, CH 2 = CHSi (OC 2 H 5) 3, CH 2 = CHSi (OC 2 H _{5) 3, CH 2 = CH} -Si (OC 2 H 4 OCH 3) 3, CH 2 = CH-CH 2 -Si (OC 2 H 5) 3, CH 2 = CH-CH 2 -Si (OC 2 H ₅ ) ₃ , CH ₂ = CH—CH ₂ —Si (OOCCH ₃ ) ₃ , γ-glycidyloxypropyltrimethoxysilane (GPTS), γ-glycidyloxypropyldimethylchlorosilane, 3-aminopropyltrimethoxysilane (APTS), 3-aminopropyltriethoxysilane (APTES), N- (2-aminoethyl) -3aminopropyltrimethoxy Silane, N- [N ′-(2′-aminoethyl) -2-aminoethyl] -3-aminopropyltrimethoxysilane, hydroxymethyltrimethoxysilane, 2- [methoxy (polyethyleneoxy) propyl] trimethoxysilane, Bis- (hydroxyethyl) -3-aminopropyltriethoxysilane, N-hydroxyethyl-N-methylaminopropyltriethoxysilane, 3- (meth) acryloxypropyltriethoxysilane and 3- (meth) acryloxypropyl And trimethoxysilane.

As a metal compound which has a functional group, the metal compound of the metal M from 1st group III-V and / or 2nd group II-IV of an element periodic table is mentioned. Zirconium and titanium alkoxides, M (OR) ₄ (M = Ti, Zr), wherein part of the OR group is replaced by a complexing agent such as a β-dicarbonyl compound or a monocarboxylic acid. Can be mentioned. When a compound having a polymerizable unsaturated group (such as methacrylic acid) is used as a complexing agent, a polymerizable unsaturated group can be introduced.

As the dispersion medium, water and / or an organic solvent is preferably used. A particularly preferred dispersion medium is distilled (pure) water. As the organic solvent, polar, nonpolar and aprotic solvents are preferred. Examples thereof include alcohols such as aliphatic alcohols having 1 to 6 carbon atoms (particularly methanol, ethanol, n- and i-propanol and butanol), ketones such as acetone and butanone, esters such as ethyl acetate; , Ethers such as tetrahydrofuran and tetrahydropyran; amides such as dimethylacetamide and dimethylformamide; sulfoxides and sulfones such as sulfolane and dimethylsulfoxide; and aliphatic (optionally halogenated) such as pentane, hexane and cyclohexane And hydrocarbons. These dispersion media can be used as a mixture.
The dispersion medium preferably has a boiling point that can be easily removed by distillation (optionally under reduced pressure), and a solvent having a boiling point of 200 ° C. or lower, particularly 150 ° C. or lower is preferable.

  In preparing the reactive inorganic fine particles B of (i), the concentration of the dispersion medium is usually 40 to 90, preferably 50 to 80, particularly 55 to 75% by weight. The rest of the dispersion is composed of untreated inorganic fine particles and the surface modifying compound. Here, the weight ratio of the inorganic fine particles / surface modification compound is preferably 100: 1 to 4: 1, more preferably 50: 1 to 8: 1, and even more preferably 25: 1 to 10: 1. .

  The preparation of the reactive inorganic fine particles B of (i) is preferably performed at room temperature (about 20 ° C.) to the boiling point of the dispersion medium. Particularly preferably, the dispersion temperature is 50 to 100 ° C. The dispersion time depends in particular on the type of material used, but is generally from a few minutes to a few hours, for example 1 to 24 hours.

When preparing the reactive inorganic fine particles B of (i) above, the inorganic fine particles are subjected to mechanical reaction pulverization in a dispersion medium in which the surface modifying compound is present, and at least partially colloidal inorganic fine particles obtained by pulverizing the surface modifying compound. A mode of chemically bonding to is also preferably used.
In this case, the mechanical pulverization is generally performed by a mill, a kneader (kneader), a cylinder mill or, for example, a high-speed disperser. Grinding machines suitable for machine grinding are homogenizer, turbo stirrer, mill with remote grinding tool (ball mill, rod mill, drum mill, cone mill, tube mill, self-pulverizing mill, planetary mill, vibration mill and stirrer mill), heavy roller Kneader, colloid mill and cylinder mill. Among them, a particularly preferable mill is a stirring ball mill having a motion stirrer and pulverized balls as pulverizing means.
Milling with grinding and homogenizing is preferably performed at room temperature. The required time is appropriately adjusted according to the type of mixing and the grinder used.

(Ii) a compound containing a reactive functional group b desired to be introduced into the inorganic fine particles, a group represented by the following chemical formula (1), and a silanol group or a group that generates a silanol group by hydrolysis, and a metal as an inorganic fine particle serving as a core Inorganic fine particles having reactive functional groups b on the surface, obtained by bonding with oxide fine particles.
Chemical formula (1)
^{-Q 1 -C (= Q 2)} -NH-
(In the chemical formula (1), Q ¹ represents NH, O (oxygen atom), or S (sulfur atom), and Q ² represents O or S.)
When the reactive inorganic fine particles B (ii) are used, there is a merit that dispersibility and film strength are further increased in terms of increasing the amount of organic components.

First, a compound containing a reactive functional group b to be introduced into the inorganic fine particles, a group represented by the above chemical formula (1), and a silanol group or a group that generates a silanol group by hydrolysis (hereinafter, reactive functional group-modified hydrolyzable) The silane may be described.
In the reactive functional group-modified hydrolyzable silane, the reactive functional group b desired to be introduced into the inorganic fine particles is not particularly limited as long as it is appropriately selected so that it can react with the binder component C. Suitable for introducing polymerizable unsaturated groups as described above.

In the reactive functional group-modified hydrolyzable silane, the group [—Q ¹ —C (═Q ² ) —NH—] represented by the chemical formula (1) is specifically [—O—C (═O ) —NH—], [—O—C (═S) —NH—], [—S—C (═O) —NH—], [—NH—C (═O) —NH—], [— NH-C (= S) -NH-] and [-S-C (= S) -NH-]. These groups can be used individually by 1 type or in combination of 2 or more types. Among them, from the viewpoint of thermal stability, [—O—C (═O) —NH—] group, [—O—C (═S) —NH—] group and [—S—C (═O) — It is preferable to use at least one NH-] group in combination. The group [—Q ¹ —C (= Q ² ) —NH—] represented by the chemical formula (1) generates an appropriate cohesive force due to hydrogen bonding between molecules, and has excellent mechanical strength when formed into a cured product. It is considered that properties such as adhesion to the substrate and heat resistance can be imparted.

  Examples of the group that generates a silanol group by hydrolysis include groups having an alkoxy group, an aryloxy group, an acetoxy group, an amino group, a halogen atom, etc. on the silicon atom. An oxysilyl group is preferred. A silanol group or a group that forms a silanol group by hydrolysis can be combined with the metal oxide fine particles by a condensation reaction or a condensation reaction that occurs following hydrolysis.

  Preferable specific examples of the reactive functional group-modified hydrolyzable silane include, for example, compounds represented by the following chemical formula (2).

In the chemical formula (2), R ^a and R ^b may be the same or different, and are a hydrogen atom or a C ₁ to C ₈ alkyl group or aryl group, for example, methyl, ethyl, propyl, butyl, octyl, Examples thereof include phenyl and xylyl groups. Here, m is 1, 2 or 3.
Examples of the group represented by [(R ^a O) _m R ^b _3-m Si—] include a trimethoxysilyl group, a triethoxysilyl group, a triphenoxysilyl group, a methyldimethoxysilyl group, and a dimethylmethoxysilyl group. Can be mentioned. Of these groups, a trimethoxysilyl group or a triethoxysilyl group is preferable.

R ^c is a divalent organic group having a C ₁ to C ₁₂ aliphatic or aromatic structure and may contain a chain, branched or cyclic structure. Examples of such an organic group include methylene, ethylene, propylene, butylene, hexamethylene, cyclohexylene, phenylene, xylylene, and dodecamethylene. Among these, preferred examples are methylene, propylene, cyclohexylene, phenylene and the like.
R ^d is a divalent organic group and is usually selected from divalent organic groups having a molecular weight of 14 to 10,000, preferably a molecular weight of 76 to 500. For example, chain polyalkylene groups such as hexamethylene, octamethylene, dodecamethylene; alicyclic or polycyclic divalent organic groups such as cyclohexylene and norbornylene; divalent groups such as phenylene, naphthylene, biphenylene and polyphenylene Aromatic group; and these alkyl group-substituted and aryl group-substituted products. In addition, these divalent organic groups may contain an atomic group containing an element other than carbon and hydrogen atoms, and include a polyether bond, a polyester bond, a polyamide bond, a polycarbonate bond, and a group represented by the chemical formula (1). Can also be included.

R ^e is an (n + 1) -valent organic group, and is preferably selected from a chain, branched or cyclic saturated hydrocarbon group and unsaturated hydrocarbon group.
Y ′ represents a monovalent organic group having a reactive functional group. The reactive functional group itself as described above may be used. For example, when the reactive functional group b is selected from a polymerizable unsaturated group, a (meth) acryloyl (oxy) group, a vinyl (oxy) group, a propenyl (oxy) group, a butadienyl (oxy) group, a styryl (oxy) group, Examples include ethynyl (oxy) group, cinnamoyl (oxy) group, maleate group, (meth) acrylamide group and the like. N is preferably a positive integer of 1 to 20, more preferably 1 to 10, particularly preferably 1 to 5.

  For the synthesis of the reactive functional group-modified hydrolyzable silane used in the present invention, for example, a method described in JP-A-9-100111 can be used. That is, for example, when it is desired to introduce a polymerizable unsaturated group, (i) it can be carried out by an addition reaction of a mercaptoalkoxysilane, a polyisocyanate compound, and an active hydrogen group-containing polymerizable unsaturated compound capable of reacting with an isocyanate group. . Further, (b) the reaction can be carried out by a direct reaction between a compound having an alkoxysilyl group and an isocyanate group in the molecule and an active hydrogen group-containing polymerizable unsaturated compound. Furthermore, (c) it can also be directly synthesized by an addition reaction of a compound having a polymerizable unsaturated group and an isocyanate group in the molecule with mercaptoalkoxysilane or aminosilane.

For example, mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane, or the like can be suitably used as the mercaptoalkoxysilane.
Examples of the polyisocyanate compound include 2,4-tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, methylene bis (4-cyclohexyl isocyanate), 1,3-bis (isocyanate methyl) cyclohexane, and the like. Can be suitably used.
Examples of the active hydrogen-containing polymerizable unsaturated compound include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, trimethylolpropane di (meth) acrylate, and pentaerythritol. -Lutri (meth) acrylate, dipentaerythritol rupenta (meth) acrylate and the like. Moreover, the compound obtained by addition reaction of glycidyl group containing compounds, such as alkyl glycidyl ether, allyl glycidyl ether, and glycidyl (meth) acrylate, and (meth) acrylic acid can be used.

  In the production of the reactive inorganic fine particle B of (ii), a reactive functional group-modified hydrolyzable silane is separately hydrolyzed and then mixed with the inorganic fine particle, followed by heating and stirring, or A method of hydrolyzing a reactive functional group-modified hydrolyzable silane in the presence of inorganic fine particles, and in the presence of other components such as polyunsaturated organic compounds, monounsaturated organic compounds, radiation polymerization initiators, etc. A method of performing surface treatment of inorganic fine particles can be selected, but a method of hydrolyzing a reactive functional group-modified hydrolyzable silane in the presence of inorganic fine particles is preferable. When producing the reactive inorganic fine particles B of (ii), the temperature is usually 20 ° C. or higher and 150 ° C. or lower, and the treatment time is in the range of 5 minutes to 24 hours.

  In order to accelerate the hydrolysis reaction, an acid, salt or base may be added as a catalyst. Preferable examples of the acid include organic acids and unsaturated organic acids; examples of the base include tertiary amines or quaternary ammonium hydroxides. The amount of the acid or base catalyst added is 0.001 to 1.0% by weight, preferably 0.01 to 0.1% by weight, based on the reactive functional group-modified hydrolyzable silane.

In the present invention, the reactive inorganic fine particles B may not contain fluorine. Here, “containing no fluorine” means that the inorganic fine particles forming the core of the reactive inorganic fine particles B do not contain fluorine, and the organic component covering a part of the surface of the reactive inorganic fine particles B contains fluorine. However, typically, it is sufficient that fluorine is not present on the surface of the reactive inorganic fine particles B. Specifically, the reactive inorganic fine particles B are not subjected to surface treatment with a fluorine-containing surface treatment agent. Refers to that.
The reactive inorganic fine particles B whose surface has been surface-treated with a fluorine-containing surface treatment agent are more likely to be phase-separated and unevenly distributed because the familiarity in the composition for the uneven layer is further reduced. However, in the present invention, by setting the average particle size of the reactive inorganic fine particles B to 30 nm or less, the uneven distribution of the reactive inorganic fine particles B is sufficiently promoted. It is possible to form a concavo-convex layer in which the reactive inorganic fine particles B are unevenly distributed on the air interface side surface layer of the concavo-convex layer to such an extent that sufficient hard coat properties are exhibited without performing surface treatment with a fluorine-containing surface treatment agent. is there.
It can be confirmed as follows that the reactive inorganic fine particles B do not contain fluorine. That is, the anti-glare film produced using the reactive inorganic fine particles B is obliquely cut, and the reactive inorganic fine particles B using a TOF-SIMS (time-of-flight secondary ion mass spectrometer, for example, ULVAC-PHI). It can confirm by detecting the component contained in. If the reactive inorganic fine particle B does not contain fluorine, no fluorine atom is detected.

Further, as the reactive inorganic fine particles B, powdery fine particles not containing a dispersion medium may be used, but a dispersion step can be omitted, and from the viewpoint of high productivity, a fine particle in a solvent dispersion sol is used. preferable.
In the uneven layer, the content of the reactive inorganic fine particles B is 5 to 30% by weight with respect to the total solid content of the uneven layer (the total amount of components of the reactive inorganic fine particles B and the curable binder system). It is preferable that it is 5 to 20 weight% especially. By setting the amount to 5% by weight or more, the hardness of the antiglare layer surface can be sufficiently improved. be able to.

<Curable binder system>
In the present specification, the constituent component of the curable binder system is not only the binder component C but also the unevenness described later after curing of the curable binder component other than the binder component C, the polymer component, the polymerization initiator, and the like. Represents the matrix component of the layer.
[Binder component C]
The binder component C forming the uneven layer has the reactive functional group b of the reactive inorganic fine particle B and the reactive functional group c having crosslinking reactivity, and the reactive functional group b and the reactive functional group. c is cross-linked to form a network structure. The binder component C preferably has three or more reactive functional groups c in order to obtain sufficient crosslinkability. As the reactive functional group c, a polymerizable unsaturated group is suitably used, preferably a photocurable unsaturated group, and particularly preferably an ionizing radiation curable unsaturated group. Specific examples thereof include an ethylenic double bond such as a (meth) acryloyl group, a vinyl group, and an allyl group, and an epoxy group.

  As the binder component C, a curable resin is preferable, and a light-transmitting material that transmits light when formed into a coating film is preferable. Specific examples include ionizing radiation curable resins that are cured by ionizing radiation typified by ultraviolet rays or electron beams, ionizing radiation curable resins and solvent-drying resins (such as thermoplastic resins). The resin for forming the coating only by drying the solvent for adjustment, or a thermosetting resin, preferably an ionizing radiation curable resin.

Specific examples of the ionizing radiation curable resin include a compound having a radical polymerizable functional group such as a (meth) acrylate group, for example, a (meth) acrylate oligomer, a prepolymer, or a monomer (monomer). .
More specifically, (meth) acrylate oligomers or prepolymers include relatively low molecular weight polyester resins, polyether resins, acrylic resins, epoxy resins, urethane resins, alkyd resins, spiroacetal resins, polybutadiene resins, polythiols. Examples include oligomers or prepolymers composed of (meth) allyllic acid esters of polyfunctional compounds such as polyene resins and polyhydric alcohols.
In addition, (meth) acrylate monomers include ethyl (meth) acrylate, ethylhexyl (meth) acrylate, hexanediol (meth) acrylate, hexanediol (meth) acrylate, tripropylene glycol di (meth) acrylate, diethylene glycol di (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate Etc.
Examples other than (meth) acrylate compounds include monofunctional or polyfunctional monomers such as styrene, methylstyrene, N-vinylpyrrolidone, bisphenol type epoxy compounds, novolac type epoxy compounds, aromatic vinyl ethers, aliphatic vinyl ethers. And compounds having a cationically polymerizable functional group such as an oligomer or a prepolymer.

When the ionizing radiation curable resin is used as an ultraviolet curable resin, a sensitizer can be added as a photopolymerization initiator or a photopolymerization accelerator.
As specific examples of the photopolymerization initiator, in the case of a resin system having a radical polymerizable functional group, acetophenones, benzophenones, Michler benzoylbenzoate, α-amyloxime ester, tetramethylchuram monosulfide, benzoins, Examples include benzoin methyl ether, thioxanthones, propiophenones, benzyls, acylphosphine oxides, 1-hydroxy-cyclohexyl-phenyl-ketone, and the like, which are used alone or in combination. 1-Hydroxy-cyclohexyl-phenyl-ketone is available, for example, under the trade name Irgacure 184 (manufactured by Ciba Specialty Chemicals). Moreover, as α-aminoalkylphenones, for example, trade names Irgacure 907 and 369 are available.
In the case of a resin system having a cationic polymerizable functional group, an aromatic diazonium salt, an aromatic sulfonium salt, an aromatic iodonium salt, a metatheron compound, a benzoin sulfonic acid ester or the like is used alone or as a mixture as a photopolymerization initiator.
Further, it is preferable to use a mixture of photosensitizers, and specific examples thereof include n-butylamine, triethylamine, poly-n-butylphosphine and the like.
The addition amount of a photoinitiator is 0.1-10 weight part with respect to 100 weight part of ionizing radiation-curable compositions.

  The solvent-drying resin used by mixing with the ionizing radiation curable resin mainly includes a thermoplastic resin. As the thermoplastic resin, those generally exemplified are used. By adding the solvent-drying resin, coating film defects on the coated surface can be effectively prevented. Specific examples of preferable thermoplastic resins include, for example, styrene resins, (meth) acrylic resins, organic acid vinyl ester resins, vinyl ether resins, halogen-containing resins, and olefin resins (including alicyclic olefin resins). ), Polycarbonate resin, polyester resin, polyamide resin, thermoplastic polyurethane resin, polysulfone resin (eg, polyethersulfone, polysulfone), polyphenylene ether resin (eg, polymer of 2,6-xylenol), cellulose Derivatives (eg, cellulose esters, cellulose carbamates, cellulose ethers), silicone resins (eg, polydimethylsiloxane, polymethylphenylsiloxane), rubbers or elastomers (eg, polybutadiene, polyisoprene) Diene rubber, styrene - butadiene copolymer, acrylonitrile - butadiene copolymer, acrylic rubber, urethane rubber, silicone rubber) and the like are preferable.

  Specific examples of the thermosetting resin include 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. And polysiloxane resin. When a thermosetting resin is used, a curing agent such as a crosslinking agent and a polymerization initiator, a polymerization accelerator, a solvent, a viscosity modifier and the like can be further added as necessary.

[Formation of uneven layer]
As an embodiment of the antiglare film of the present invention, a photocurable binder system is used as the curable binder system containing the binder component C, and the uneven layer is formed on the surface of the transparent substrate film on the observer side. The anti-glare film formed by the method of coating the uneven | corrugated layer curable resin composition which added the translucent fine particle A and the reactive inorganic fine particle B to the type | system | group, and forming an uneven | corrugated layer can be mentioned.
The concavo-convex layer is a curable resin composition for concavo-convex layers obtained by mixing the light-transmitting fine particles A, the reactive inorganic fine particles B, and the components of the photocurable binder system in an appropriate solvent (hereinafter, concavo-convex layer composition May be applied to a transparent substrate film. At this time, the translucent fine particles A are preferably composed of the first fine particles and the second fine particles, or the first fine particles, the second fine particles, and the third fine particles.

(Preparation of resin composition)
The curable resin composition for an uneven layer is prepared by mixing and dispersing the above components according to a general preparation method. A paint shaker or a bead mill can be used for mixing and dispersing. When the translucent fine particles A and the reactive inorganic fine particles B are obtained in a dispersed state in a solvent, the curable binder system and other components including the solvent are appropriately added and mixed in the dispersed state. It is prepared by dispersion treatment.
Examples of the solvent include alcohols such as isopropyl alcohol, methanol, ethanol, butanol, and isobutyl alcohol; ketones such as methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), and cyclohexanone; methyl acetate, ethyl acetate, butyl acetate, and the like. Esters: Halogenated hydrocarbons such as chloroform, methylene chloride, and tetrachloroethane; aromatic hydrocarbons such as toluene and xylene, or mixtures thereof.

  According to the preferable aspect of this invention, it is preferable to add leveling agents, such as a fluorine type or a silicone type, to the composition for uneven | corrugated layers. The uneven layer composition containing a leveling agent can impart coating stability, slipperiness and antifouling properties to the coating surface during application or drying, and can also provide an effect of scratch resistance. And

Examples of the method for applying the uneven layer composition to the transparent substrate film include application methods such as a roll coating method, a Miya bar coating method, and a gravure coating method. Drying and ultraviolet curing are performed after application of the composition for the uneven layer. The reactive fine particle B is unevenly distributed on the air interface side (interface opposite to the transparent substrate film) by drying the composition for the uneven layer after application for several tens of seconds to several minutes.
Specific examples of the ultraviolet light source include a light source of an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black light fluorescent lamp, and a metal halide lamp. As an ultraviolet wavelength, a wavelength range of 190 to 380 nm can be used. Specific examples of the electron beam source include various electron beam accelerators such as a cockcroft-wald type, a bandegraft type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type.

  By curing the constituent component of the photocurable binder system, the reactive functional group b of the reactive inorganic fine particle B and the reactive functional group c of the binder component C contained in the constituent component of the photocurable binder system are changed. Crosslinks to form a network structure. In addition, the translucent fine particles A in the constituent components of the photocurable binder system are fixed, and a desired uneven shape is formed on the outermost surface of the uneven layer.

When the uneven layer is formed by applying the uneven layer composition, the uneven layer composition has a gel fraction of 30% to 80%, preferably the lower limit is 35% or more, more preferably 40%. The above is preferable, and the upper limit is preferably 70% or less, and more preferably 60% or less, from the viewpoint of good adhesion between the uneven layer and the surface shape adjusting layer and scratch resistance.
In addition, a gel fraction can be calculated | required with the following method, for example, when this composition is an ultraviolet curable resin. First, as a sample, out of the components of the uneven layer composition, a monomer, an oligomer, a polymer, and other additives, such as an ink containing components other than the particles containing the light-transmitting fine particles A and the reactive inorganic fine particles B, are prepared. A sample having a thickness of 5 μm is applied onto a PET substrate having a thickness of 50 μm, and each sample irradiated with UV irradiation conditions is changed at intervals of 10 mJ in the range of 10 to 100 mJ. Next, the sample is cut into a 10 cm square, the n number is taken at three points, and the weight X is measured. Next, it is immersed in a solvent (acetone, methyl ethyl ketone, methyl acetate, toluene, and a mixed solvent thereof, and the like. In the case of an acrylate composition, typically acetone, methyl ethyl ketone) for 12 hours or more, and the solvent is dissolved. Each sample is taken out from the sample, sufficiently dried in an oven (60 ° C. × 2 minutes), and the weight B of the dried sample is measured. Next, the difference between the weight X before immersion in the solvent and the dried sample Y is taken, and this value is taken as Z. Finally, the gel fraction (%) for each dose is calculated using the following formula.
“Gel fraction (%)” = 100−Z / X

  In the antiglare film according to the present invention, the thickness of the uneven layer is preferably 0.5 μm or more and 30 μm or less, and more preferably 0.5 μm or more and 3 μm or less in terms of physical properties such as hardness and scratch resistance. It is preferable from the viewpoint of good and productivity. When the film thickness is 0.5 μm or more, sufficient hard coat properties can be imparted, and when it is 30 μm or less, the occurrence of cracks can be suppressed. Here, the film thickness of the concavo-convex layer is the thickness from the transparent base film side interface of the concavo-convex layer to the concave surface at the interface opposite to the transparent base film.

Further, according to the present invention, in the steel wool resistance test performed by the following method, the surface was provided with an antiglare layer having a high hard coat property, in which no more than 5 scratches were formed on the surface, and no scratches were formed. It is possible to provide an antiglare film.
(Steel wool resistance test)
The antiglare layer surface is subjected to 10 reciprocating friction with # 0000 steel wool at a speed of 50 mm / sec while applying a load of 300 g / cm ² . The stroke width for reciprocating friction is preferably 5 to 15 cm.

(Other layers)
The antiglare film according to the present invention is basically composed of the transparent base film and the antiglare layer as described above. However, in consideration of the function or use as an antiglare film, in addition to the antiglare layer according to the present invention, one or more layers as described below may be further contained. Furthermore, you may form including a middle refractive index layer and a high refractive index layer.

Since the antiglare film of the present invention can provide various functions required for an image display device, the antiglare layer 2 is composed of two or more layers as shown in FIG. It is good also as a laminated structure which has the surface shape adjustment layer 6 in the 3 observer side. By forming a surface shape adjusting layer on the concavo-convex layer, the concavo-convex layer has, for example, a fine concavo-convex shape or an excessively large concavo-convex difference in order to exhibit appropriate antiglare performance. Even when the antiglare layer 2 is provided, the surface on the viewer side of the antiglare layer 2 can be formed into a smooth and gentle desired uneven shape, and various functions can be imparted to the antiglare film.
The surface shape adjusting layer may further contain an antistatic agent, a refractive index adjusting agent, a stainproofing agent, a water repellent, an oil repellent, a fingerprint adhesion preventive, a high curing agent and a hardness adjuster.

  In addition, the anti-glare layer 2 may be provided with antireflection performance by the surface shape adjusting layer also serving as a low refractive index layer. However, as shown in FIG. The low refractive index layer 7 may be further provided on the viewer side separately from the surface shape adjusting layer 6. The low refractive index layer 7 has a shape that follows the concavo-convex shape of the surface of the concavo-convex layer 3 or the surface shape adjusting layer 6 serving as a base of the layer, and the concavo-convex shape of the surface is the surface of the layer serving as the base. Equivalent uneven shape. In addition to the low refractive index layer 7, an arbitrary layer may exist on the viewer side. The low refractive index layer 7 has a refractive index lower than the refractive index of the layer on the image display device side where the low refractive index layer 7 is laminated.

Hereinafter, the surface shape adjusting layer and the low refractive index layer will be described in detail.
<Surface shape adjustment layer>
In the present invention, in order to adjust the uneven shape on the surface of the antiglare layer, a surface shape adjusting layer may be formed on the uneven layer. The surface shape adjustment layer fills the fine unevenness existing along the uneven shape with a scale of 1/10 or less of the uneven surface scale (the height and interval of the uneven surface) in the surface roughness of the uneven layer, and applies smoothing. Smooth the uneven surface, or adjust the interval, height, and frequency (number) of peaks. Moreover, you may further provide functions, such as antistatic, refractive index adjustment, high hardness, and antifouling property, to a surface shape adjustment layer.
The film thickness (when cured) of the surface adjustment layer is preferably 0.6 μm or more and 15 μm or less, more preferably the lower limit is 3 μm or more and the upper limit is 8 μm or less. The thickness of the surface adjustment layer can be measured by laser microscope observation, SEM or TEM observation in the same manner as the method for measuring the layer thickness of the antiglare layer.

As the binder (including resin components such as monomers and oligomers) for forming the surface shape adjusting layer, a transparent one is preferable, and specific examples thereof include an ionizing radiation curable resin that is a resin curable by ultraviolet rays or electron beams. Three types of resins, a mixture of an ionizing radiation curable resin and a solvent-drying resin, or a thermosetting resin are exemplified, and an ionizing radiation curable resin is preferably used.
Specific examples of the ionizing radiation curable resin include the resins described in the uneven layer. In addition, photopolymerization initiators, photopolymerization accelerators, photosensitizers, solvent-drying resins, etc. that can be used by mixing with ionizing radiation curable resins as needed are also those described in the uneven layer, respectively. Can be used.

  The surface adjustment layer may contain organic fine particles or inorganic fine particles for adjusting fluidity. Among the fine particles, colloidal silica is preferable. Conventionally, when trying to smooth the surface by forming fine surface irregularities by forming the surface adjustment layer, the anti-glare property has been remarkably lowered due to excessive smoothing. However, when a film is formed with the composition containing the colloidal silica, it is possible to achieve both anti-glare properties and black reproducibility. The effect of obtaining such an effect is not clear, but the composition containing colloidal silica has good followability to the uneven shape of the surface by controlling its fluidity. Therefore, it is presumed that it can be left without being completely crushed while imparting moderate smoothness to the fine concavo-convex shape in the underlying concavo-convex layer that is completely crushed by the conventional surface adjustment layer.

  The shape of the organic fine particles or inorganic fine particles that can be used as the fluidity adjusting agent is not particularly limited, and may be any shape such as a spherical shape, a plate shape, a fiber shape, an amorphous shape, and a hollow shape. Particularly preferred fluidity modifier is colloidal silica.

  In the present invention, “colloidal silica” means a colloidal solution in which colloidal silica particles are dispersed in water or an organic solvent. The colloidal silica preferably has an ultrafine particle diameter (diameter) of about 1 to 50 nm. The particle diameter of the colloidal silica in the present invention is an average particle diameter according to the BET method (a surface area is measured by the BET method, and the average particle diameter is calculated by converting the particles to be true spheres).

  The colloidal silica is a known one, and commercially available ones include, for example, “methanol silica sol”, “MA-ST-M”, “IPA-ST”, “EG-ST”, “EG-ST-ZL”. ”,“ NPC-ST ”,“ DMAC-ST ”,“ MEK ”,“ XBA-ST ”,“ MIBK-ST ”(all products of Nissan Chemical Industries, Ltd., all trade names),“ OSCAL1132, ” “OSCAL1232”, “OSCAL1332”, “OSCAL1432”, “OSCAL1532”, “OSCAL1632”, “OSCAL1132” (above, products of Catalytic Chemical Industry Co., Ltd., all trade names) may be mentioned. it can.

  The addition amount of the organic fine particles or inorganic fine particles varies depending on the fine particles to be added. In the case of colloidal silica, the addition amount is preferably 5 to 80 with respect to the mass 100 of the binder resin of the surface adjustment layer. If it exceeds 80, it becomes a region where the antiglare property does not change even if it is added more, so the meaning of adding is lost, and if it exceeds this, poor adhesion with the lower layer occurs, so it should be within this range Is good.

[Method for forming surface shape adjusting layer]
The surface shape adjusting layer can be formed by applying a composition for surface shape adjusting layer obtained by dispersing and / or dissolving the above components in a solvent, followed by drying and ultraviolet curing. Examples of the method for applying the surface shape adjusting layer composition include application methods such as a roll coating method, a Miya bar coating method, and a gravure coating method.
Specific examples of the ultraviolet light source in the ultraviolet curing include a light source of an ultra high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black light fluorescent lamp, and a metal halide lamp lamp. As an ultraviolet wavelength, a wavelength range of 190 to 380 nm can be used. Specific examples of the electron beam source include various electron beam accelerators such as a cockcroft-wald type, a bandegraft type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type.

<Low refractive index layer>
The low refractive index layer is a layer that plays a role of lowering the reflectivity due to the light interference effect in the multilayer film when external light (for example, fluorescent lamp, natural light, etc.) is reflected on the surface of the optical laminate. It is. According to a preferred embodiment of the present invention, a low-refractive index layer is formed on the surface of an antiglare layer consisting of a single layer, that is, on an uneven layer, or an antiglare layer consisting of two or more layers, or a surface shape adjusting layer. Is preferred. A low refractive index layer is one whose refractive index is lower than that of the layer below the layer.
According to a preferred embodiment of the present invention, the refractive index of the uneven layer or the surface shape adjusting layer adjacent to the low refractive index layer is 1.5 or more, and the refractive index of the low refractive index layer is 1.45 or less, preferably Is preferably composed of 1.42 or less.

The low refractive index layer is preferably 1) a resin containing silica or magnesium fluoride, 2) a fluorine resin which is a low refractive index resin, 3) a fluorine resin containing silica or magnesium fluoride, and 4) silica. Alternatively, it is composed of either a magnesium fluoride thin film or the like. About resin other than a fluororesin, resin similar to resin which comprises an uneven | corrugated layer can be used.
As the fluororesin, a polymerizable compound containing a fluorine atom in at least a molecule or a polymer thereof can be used. The polymerizable compound is not particularly limited, but for example, those having a curing reactive group such as a functional group that is cured by ionizing radiation and a polar group that is thermally cured are preferable.
Moreover, the compound which has these reactive groups simultaneously may be sufficient. In contrast to this polymerizable compound, a polymer has no reactive groups as described above.

  As the polymerizable compound having an ionizing radiation curable group, fluorine-containing monomers having an ethylenically unsaturated bond can be widely used. More specifically, to illustrate fluoroolefins (eg, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, perfluorobutadiene, perfluoro-2,2-dimethyl-1,3-dioxole, etc.) Can do. As having a (meth) acryloyloxy group, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3,3-pentafluoropropyl (meth) acrylate, 2- (perfluorobutyl) Ethyl (meth) acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate, 2- (perfluorooctyl) ethyl (meth) acrylate, 2- (perfluorodecyl) ethyl (meth) acrylate, α-trifluoromethacryl (Meth) acrylate compounds having fluorine atoms in the molecule, such as methyl acrylate and ethyl α-trifluoromethacrylate; C 1-14 fluoroalkyl groups having at least 3 fluorine atoms in the molecule, fluorocyclo An alkyl group or a fluoroalkylene group and at least two (meta And fluorine-containing polyfunctional (meth) acrylic acid ester compounds having an acryloyloxy group.

Preferable examples of the thermosetting polar group include hydrogen bond forming groups such as a hydroxyl group, a carboxyl group, an amino group, and an epoxy group. These are excellent not only in adhesion to the coating film but also in affinity with inorganic ultrafine particles such as silica. Examples of the polymerizable compound having a thermosetting polar group include 4-fluoroethylene-perfluoroalkyl vinyl ether copolymer; fluoroethylene-hydrocarbon vinyl ether copolymer; epoxy, polyurethane, cellulose, phenol, polyimide, and the like. Fluorine modified products of each resin can be mentioned.
Polymerizable compounds having both ionizing radiation curable groups and thermosetting polar groups include acrylic or methacrylic acid moieties and fully fluorinated alkyl, alkenyl, aryl esters, fully or partially fluorinated vinyl ethers, fully or partially fluorine. Illustrative examples include fluorinated vinyl esters, fully or partially fluorinated vinyl ketones, and the like.

  Moreover, together with the polymerizable compound or polymer having a fluorine atom, each resin component as described in the curable resin composition for an uneven layer can be mixed and used. Furthermore, various additives and solvents can be used as appropriate in order to improve the curing agent for curing reactive groups and the like, to improve the coating property, and to impart antifouling properties.

  According to a preferred embodiment of the present invention, it is preferable to use “fine particles having voids” as the low refractive index agent. The “fine particles having voids” can reduce the refractive index while maintaining the layer strength of the low refractive index layer. In the present invention, the term “fine particles having voids” means a structure in which fine particles are filled with gas and / or a porous structure containing gas, and the gas in the fine particles has a refractive index compared to the original refractive index of the fine particles. It means fine particles whose refractive index decreases in inverse proportion to the occupation ratio. The present invention also includes fine particles capable of forming a nanoporous structure inside and / or at least part of the surface depending on the form, structure, aggregation state, and dispersion state of the fine particles inside the coating film. It is. The low refractive index layer using these fine particles can adjust the refractive index to 1.30 to 1.45.

  As specific examples of the inorganic fine particles having voids, silica fine particles prepared by using the technique disclosed in Japanese Patent Application Laid-Open No. 2001-233611 are preferably exemplified. Further, silica fine particles obtained by the production methods described in JP-A-7-133105, JP-A-2002-79616, JP-A-2006-106714 and the like may be used. Since silica fine particles having voids are easy to manufacture and have high hardness, when a low refractive index layer is formed by mixing with a binder, the layer strength is improved and the refractive index is 1.20-1. It is possible to prepare within the range of about 45. In particular, as specific examples of the organic fine particles having voids, hollow polymer fine particles prepared by using the technique disclosed in JP-A-2002-80503 are preferably exemplified.

  The fine particles capable of forming a nanoporous structure inside and / or at least part of the surface of the coating film are manufactured for the purpose of increasing the specific surface area in addition to the silica fine particles, and the packing column and the surface porosity Examples include controlled release materials that adsorb various chemical substances in the mass part, porous fine particles used for catalyst fixation, or dispersions and aggregates of hollow fine particles intended to be incorporated into heat insulating materials and low dielectric materials. it can. As a specific example, aggregates of porous silica fine particles and silica fine particles manufactured by Nissan Chemical Industries, Ltd. were linked in a chain form from the product names Nippon and Nippon manufactured by Nippon Silica Kogyo Co., Ltd. as commercial products. From the colloidal silica UP series (trade name) having a structure, those within the range of the preferable particle diameter of the present invention can be used.

  The average particle diameter of the “fine particles having voids” is 5 nm or more and 300 nm or less, preferably the lower limit is 8 nm or more and the upper limit is 100 nm or less, more preferably the lower limit is 10 nm or more and the upper limit is 80 nm or less. When the average particle diameter of the fine particles is within this range, excellent transparency can be imparted to the low refractive index layer.

(Formation of low refractive index layer)
In forming the low refractive index layer, an appropriate solvent is used as necessary, and the viscosity is 0.5 to 5 cps (25 ° C.), preferably 0.7 to 3 cps (25 ° C.), which provides a preferable coating property as the resin composition. 25 ° C.). A low refractive index layer that can realize an antireflection film excellent in visible light by adjusting the viscosity appropriately, can form a uniform and uniform coating thin film, and has particularly excellent adhesion to a substrate. Can be formed.

  The resin curing means may be the same as described in the section of the uneven layer. When a heating means is used for the curing treatment, it is preferable to add a thermal polymerization initiator that generates, for example, a radical by heating to start polymerization of the polymerizable compound, to the fluororesin composition.

Furthermore, the antiglare film according to the present invention may be provided with the following antifouling layer.
<Anti-fouling layer>
According to a preferred embodiment of the present invention, an antifouling layer may be provided for the purpose of preventing the outermost surface of the low refractive index layer from being stained, preferably opposite to one surface of the base film on which the low refractive index layer is formed. What is provided with an antifouling layer on the surface side is preferable. The antifouling layer can further improve the antifouling property and scratch resistance with respect to the antiglare film.

  Specific examples of the antifouling agent include fluorine compounds and / or silicon that have low compatibility with the photocurable resin composition having fluorine atoms in the molecule and are difficult to add to the low refractive index layer. And a fluorine-based compound and / or a siliceous compound having compatibility with fine particles, a photocurable resin composition having a fluorine atom in the molecule, and fine particles.

<Additives>
Each of the above layers may further have another function, for example, it may be formed of a composition containing function-added components such as an antistatic agent, a refractive index adjusting agent, an antifouling agent, and a hardness adjusting agent. Good. Of these layers, the function-added component is preferably contained in the surface shape adjusting layer.
[Antistatic agent (conductive agent)]
By including an antistatic agent in each of the above layers, particularly the surface shape adjusting layer, it is possible to effectively prevent dust from adhering to the surface of the optical laminate. Specific examples of the antistatic agent include quaternary ammonium salts, pyridinium salts, various cationic compounds having cationic groups such as primary to tertiary amino groups, sulfonate groups, sulfate ester bases, and phosphate ester bases. , Anionic compounds having an anionic group such as phosphonates, amphoteric compounds such as amino acids and aminosulfate esters, nonionic compounds such as amino alcohols, glycerols and polyethylene glycols, and alkoxides of tin and titanium And metal chelate compounds such as acetylacetonate salts thereof, and compounds obtained by increasing the molecular weight of the compounds listed above. In addition, a monomer or oligomer having a tertiary amino group, a quaternary ammonium group, or a metal chelate portion and polymerizable by ionizing radiation, or an organometallic compound such as a coupling agent having a functional group, etc. Polymerizable compounds can also be used as antistatic agents.

Moreover, electroconductive ultrafine particles are mentioned. Specific examples of the conductive fine particles include those made of a metal oxide. Examples of such metal oxides include ZnO (refractive index 1.90, the numerical value in parentheses below represents the refractive index), CeO ₂ (1.95), Sb ₂ O ₂ (1.71), SnO. ₂ (1.997), indium tin oxide (1.95) often referred to as ITO, In ₂ O ₃ (2.00), Al ₂ O ₃ (1.63), antimony-doped tin oxide (abbreviation) ATO, 2.0), aluminum-doped zinc oxide (abbreviation: AZO, 2.0), and the like. The fine particles refer to those having a so-called submicron size of 1 micron or less, and preferably those having an average particle size of 0.1 nm to 0.1 μm. It is preferable from the viewpoint that a composition capable of forming a highly transparent film having almost no haze and good total light transmittance can be produced when the average particle diameter is within this range. . The average particle diameter of the conductive metal oxide fine particles can be measured by a dynamic light scattering method or the like.

Examples of the antistatic agent include conductive polymers. Specific examples thereof include aliphatic conjugated polyacetylene, aromatic conjugated poly (paraphenylene), heterocyclic conjugated polypyrrole, polythiophene, Examples include atomic conjugated polyaniline and mixed conjugated poly (phenylene vinylene). In addition to these, a double-chain conjugated system having a plurality of conjugated chains in the molecule, the conjugated polymer chain described above Examples thereof include a conductive composite which is a polymer grafted or block co-polymerized on a saturated polymer.
The antistatic agent is preferably added in an amount of 5 to 250% by mass based on the amount of the binder resin (excluding the solvent). More preferably, the upper limit of the addition amount is 100 or less, and the lower limit is 7 or more. By adjusting the addition amount to the above numerical range, it is preferable in that the transparency as the optical laminate can be maintained and the antistatic performance can be imparted without adversely affecting properties such as antiglare property.

According to another aspect of the present invention, an antistatic layer (conductive layer) may be formed as an arbitrary layer between the layers constituting the antiglare layer according to the present invention.
Specific examples of the formation of the antistatic layer include a method of forming a deposited film by depositing or sputtering a conductive metal or a conductive metal oxide on the upper surface of each layer of the antiglare layer, or conductive fine particles in a resin. The method of forming a coating film by apply | coating the dispersed resin composition is mentioned.

  When the antistatic layer is formed by vapor deposition, examples of the antistatic agent include conductive metals or conductive metal oxides such as antimony-doped indium / tin oxide (hereinafter referred to as “ATO”), indium / tin oxide ( Hereinafter, it is referred to as “ITO”. The thickness of the deposited film as the antistatic layer is 10 nm or more and 200 nm or less, preferably the upper limit is 100 nm or less, and the lower limit is 50 nm or more.

  The antistatic layer may be formed by a coating liquid containing an antistatic agent. In this case, the same antistatic agent as described in the antistatic agent as a function-added component can be used. In the case of coating with conductive fine particles, a curable resin is preferably used. The curable resin may be the same as that for forming the uneven layer. In order to form a coating film, a coating solution containing conductive fine particles contained in a curable resin is applied by a coating method such as a roll coating method, a Miya bar coating method, or a gravure coating method. After application, drying and UV curing are performed.

  As a method for curing the ionizing radiation curable resin composition, the ionizing radiation curable resin composition is cured by irradiation with an electron beam or ultraviolet rays. In the case of electron beam curing, an electron beam having energy of 100 KeV to 300 KeV is used. In the case of ultraviolet curing, ultraviolet rays or the like emitted from light such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, or a metal halide lamp are used.

(Refractive index modifier)
By adding a refractive index adjusting agent to the antiglare layer, it is possible to adjust the antireflection characteristics of the surface of the antiglare layer. Examples of the refractive index adjusting agent include a low refractive index agent, a medium refractive index agent, and a high refractive index agent.
(1) Low refractive index agent The low refractive index agent has a refractive index lower than that of the antiglare layer. According to a preferred embodiment of the present invention, the refractive index of the antiglare layer is 1.5 or more, and the refractive index of the low refractive index agent is less than 1.5, preferably 1.45 or less. Is preferred.
Specifically, the low refractive index agents mentioned in the description of the low refractive index layer can be preferably used. The film thickness of the surface shape adjusting layer containing the low refractive index agent is preferably thicker than 1 μm. This is because this layer is the outermost layer, so that scratch resistance and hardness are required.

(2) High refractive index agent / Medium refractive index agent In order to further improve the antireflection property, a high refractive index agent and a medium refractive index agent may be contained in the surface shape adjusting layer. The refractive index of the high refractive index agent and the medium refractive index agent may be set in the range of 1.46 to 2.00, and the refractive index of the medium refractive index agent is in the range of 1.46 to 1.80. The high refractive index agent means one having a refractive index in the range of 1.65 to 2.00.
The high refractive index agent / medium refractive index agent includes fine particles, and specific examples thereof (indicated by the refractive index in parentheses) include zinc oxide (1.90) and titania (2.3 to 2.7). ), Ceria (1.95), tin-doped indium oxide (1.95), antimony-doped tin oxide (1.80), yttria (1.87), and zirconia (2.0).

(Leveling agent)
A leveling agent can be added to the antiglare layer. Preferable leveling agents include fluorine or silicone leveling agents. The resin composition for an uneven layer to which a leveling agent is added improves coating suitability for the coating film surface during coating or drying, can impart slipperiness and antifouling properties, and imparts an effect of scratch resistance. Make it possible.

[Contaminant]
The antiglare layer can contain an antifouling agent. The antifouling agent is mainly intended to prevent the outermost surface of the optical laminate from being stained, and can further impart scratch resistance to the optical laminate. As specific examples of the antifouling agent, additives that exhibit water repellency, oil repellency, and fingerprint wiping are effective. More specific examples include fluorine-based compounds, silicon-based compounds, or mixed compounds thereof. More specifically, silane coupling agents having a fluoroalkyl group, such as 2-perfluorooctylethyltriaminosilane, and the like can be mentioned, and those having an amino group can be preferably used.

[Hardness adjuster (high curing agent)]
The antiglare layer can be added with a hardness adjusting agent (high curing agent) for the purpose of imparting an effect of scratch resistance. Specific examples of the hardness adjusting agent include, for example, a polyfunctional (meth) acrylate prepolymer such as polyester (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, or trimethylolpropane tri (meth) acrylate, Ionizing radiation curing in which trifunctional or more polyfunctional (meth) acrylate monomers such as pentaerythritol tetra (meth) acrylate and dipentaerythritol hexa (meth) acrylate are used alone or in combination of two or more of these. Can be mentioned.

(Production Example 1-1: Preparation of reactive inorganic fine particle B (1-1))
(1) Removal of surface adsorbed ions Water-dispersed colloidal silica (Snowtex XS, trade name, manufactured by Nissan Chemical Industries, Ltd., pH 9-10) with a particle diameter of 5 nm was converted into a cation exchange resin (Diaion SK1B, Mitsubishi Chemical Corporation). The product was ion-exchanged for 3 hours using 400 g, and then ion-exchanged for 3 hours using 200 g of an anion exchange resin (Diaion SA20A, manufactured by Mitsubishi Chemical Corporation), followed by washing and a solid content concentration of 20 An aqueous dispersion of silica fine particles of wt% was obtained.
At this time, the Na ₂ O content of the aqueous dispersion of silica fine particles was 7 ppm for each silica fine particle.
(2) Surface treatment (introduction of monofunctional monomer)
150 g of isopropanol, 4.0 g of 3,6,9-trioxadecanoic acid, and 4.0 g of methacrylic acid are added to 10 g of an aqueous dispersion of silica fine particles subjected to the above treatment (1), and stirred for 30 minutes. Mixed.
The obtained mixed liquid was stirred while heating at 60 ° C. for 5 hours to obtain a silica fine particle dispersion in which a methacryloyl group was introduced on the surface of the silica fine particles. Distilled water and isopropanol were distilled off using a rotary evaporator, and the resulting silica fine particle dispersion was added with methyl ethyl ketone so as not to dry, while finally making the remaining water and isopropanol 0.1% by weight, A silica-dispersed methyl ethyl ketone solution having a solid content of 50% by weight was obtained.
The silica fine particles (reactive inorganic fine particles B (1-1)) thus obtained have an average particle diameter of d ₅₀ = 5 nm as a result of measurement using a Nanotrac particle size analyzer manufactured by Nikkiso Co., Ltd. It was. The amount of the organic component covering the surface of the silica fine particles was 4.68 × 10 ⁻³ g / m ² as a result of measurement by thermogravimetric analysis. Further, the specific gravity of the obtained reactive inorganic fine particles B (1-1) was 2.1.

(Production Example 1-2: Preparation of reactive inorganic fine particles B (1-2))
(1) Surface adsorption ion removal Surface adsorption using water-dispersed colloidal silica (Snowtex S, trade name, manufactured by Nissan Chemical Industries, Ltd., pH 9 to 10) having a particle diameter of 10 nm, as in Production Example 1-1 An aqueous dispersion of silica fine particles from which ions were removed was obtained.
(2) Surface treatment (introduction of polyfunctional monomer)
Surface treatment was performed in the same manner as in Production Example 1-1.
The reactive inorganic fine particles B (1-2) thus obtained had an average particle diameter of d ₅₀ = 10 nm as a result of measurement by the particle size analyzer. The amount of the organic component covering the surface of the silica fine particles was 3.84 × 10 ⁻³ g / m ² as a result of measurement by thermogravimetric analysis. Further, the specific gravity of the obtained reactive inorganic fine particles B (1-2) was 2.1.

(Production Example 1-3: Preparation of reactive inorganic fine particles B (1-3))
(1) Surface adsorption ion removal Surface adsorption using water-dispersed colloidal silica (Snowtex 50, trade name, manufactured by Nissan Chemical Industries, Ltd., pH 9 to 10) having a particle diameter of 30 nm, as in Production Example 1-1 An aqueous dispersion of silica fine particles from which ions were removed was obtained.
(2) Surface treatment (introduction of polyfunctional monomer)
Surface treatment was performed in the same manner as in Production Example 1-1.
The reactive inorganic fine particles B (1-3) thus obtained had an average particle diameter of d ₅₀ = 30 nm as a result of measurement by the particle size analyzer. The amount of the organic component covering the surface of the silica fine particles was 2.73 × 10 ⁻³ g / m ² as a result of measurement by thermogravimetric analysis. The specific gravity of the obtained reactive inorganic fine particles (1-3) B was 2.1.

(Production Example 1-4: Preparation of reactive inorganic fine particles (1-4))
(1) Surface adsorbed ion removal Surface adsorbed in the same manner as in Production Example 1-1 using water-dispersed colloidal silica (Snowtex ZL, trade name, manufactured by Nissan Chemical Industries, Ltd., pH 9 to 10) having a particle diameter of 80 nm. An aqueous dispersion of silica fine particles from which ions were removed was obtained.
(2) Surface treatment (introduction of polyfunctional monomer)
Surface treatment was performed in the same manner as in Production Example 1-1.
The reactive inorganic fine particles (1-4) thus obtained had an average particle diameter of d ₅₀ = 80 nm as a result of measurement by the particle size analyzer. The amount of the organic component covering the surface of the silica fine particles was 2.15 × 10 ⁻³ g / m ² as a result of measurement by thermogravimetric analysis. The specific gravity of the obtained reactive inorganic fine particles (1-4) was 2.1.

(Production Example 2: Preparation of reactive inorganic fine particles B (2))
To a solution consisting of 7.8 parts by weight of mercaptopropyltrimethoxysilane and 0.2 parts by weight of dibutyltin dilaurate in dry air, 20.6 parts by weight of isophorone diisocyanate was added dropwise at 50 ° C. over 1 hour with stirring. Stir at 60 ° C. for 3 hours. To this was added dropwise 71.4 parts by weight of pentaerythritol triacrylate at 30 ° C. over 1 hour, and then heated and stirred at 60 ° C. for 3 hours to obtain Compound (1).
Under a nitrogen stream, 88.5 parts by weight (solid content 26.6 parts by weight) of the compound (1) synthesized above (8) by weight, methanol silica sol having a particle diameter of 20 nm (manufactured by Catalytic Chemical Industry Co., Ltd., trade name, OSCAL series) A mixed solution of 5 parts by weight and 0.01 parts by weight of p-methoxyphenol was stirred at 60 ° C. for 4 hours. Subsequently, 3 parts by weight of methyltrimethoxysilane was added to this mixed solution, and after stirring for 1 hour at 60 ° C., 9 parts by weight of methyl orthoformate was added, and the reaction was continued by heating and stirring at the same temperature for 1 hour. Inorganic fine particles B (2) were obtained.
The reactive inorganic fine particles B (2) thus obtained had an average particle diameter of d ₅₀ = 22 nm as a result of measurement by the particle size analyzer. Moreover, the amount of organic components covering the surface was 7.08 × 10 ⁻³ g / m ² as a result of measurement by thermogravimetric analysis. Further, the specific gravity of the obtained reactive inorganic fine particles B (2) was 2.1.

(Production Example 3: Preparation of reactive inorganic fine particles B (3))
(1) Surface adsorbed ion removal Isopropyl alcohol-dispersed colloidal silica having a particle diameter of 30 nm (manufactured by Catalytic Chemical Industry Co., Ltd., trade name, Sururia DN-19) was used.
(2) Surface treatment (introduction of polyfunctional monomer)
Surface treatment was performed in the same manner as in Production Example 1-1.
The reactive inorganic fine particles B (3) thus obtained had an average particle diameter of d ₅₀ = 30 nm as a result of measurement by the particle size analyzer. Further, the amount of the organic component covering the surface of the silica fine particles was 5.35 × 10 ⁻³ g / m ² as a result of measurement by thermogravimetric analysis. The silica fine particles used in Production Example 3 have a hollow structure. When the specific gravity is converted with the volume of the hollow portion as a solid portion, the apparent appearance of the obtained reactive inorganic fine particles B (3) is apparent. The specific gravity was 1.68.

<Example 1>
“Anti-Glare” having the following composition containing reactive inorganic fine particles B (1-1) produced in Production Example 1-1 on one side of a 80 μm thick triacetylcellulose (TAC) film (transparent substrate film). “Layer coating solution” was applied by 3.5 g / m ² with a Miyabar coating, the solvent was evaporated and dried, and the oxygen concentration was kept at 0.1% or less, and 10 m / min with an 80 W / cm ultraviolet irradiation device. By irradiating twice at a speed, an antiglare layer composed of an uneven layer was formed, and an antiglare film was obtained.
In the obtained antiglare film of Example 1, the thickness of the concavo-convex layer (thickness from the surface of the transparent substrate film to the surface of the concave portion) was 2.1 μm. Further, the antiglare film of Example 1 has an average of the reactive inorganic fine particles per unit area in the cross section in the thickness direction of the skin layer with respect to the average number of reactive inorganic fine particles per unit area in the cross section in the thickness direction of the entire uneven layer. The magnification of the number of particles (hereinafter referred to as the skin layer magnification) was 3.
In addition, the thickness of the uneven | corrugated layer measured five places in the STEM photograph of a glare-proof film cross section, and made it the average value (hereinafter the same).
Moreover, when the anti-glare film of Example 1 was diagonally cut and the component contained in the reactive inorganic fine particle B (1-1) was detected using TOF-SIMS manufactured by ULVAC-PHI, fluorine atoms were detected. There wasn't.

"Anti-glare coating liquid"
Pentaerythritol triacrylate (PETA): 42.5 parts by weight Irgacure 184 (photopolymerization initiator): 0.25 parts by weight Silicone (leveling agent): 0.1 parts by weight Reactive inorganic fine particles B (1- 1): 7.5 parts by weight Silica (translucent fine particles A) (average particle size 1 μm): 12 parts by weight Toluene: 34 parts by weight

<Example 2>
In Example 1, it replaced with the reactive inorganic fine particle B (1-1), and except having used the reactive inorganic fine particle B (1-2) obtained by manufacture example 1-2, it carried out similarly to Example 1, and. An antiglare layer was formed on the TAC film to obtain an antiglare film.
In the obtained antiglare film of Example 2, the thickness of the concavo-convex layer was 2.1 μm. The antiglare film of Example 2 had a skin layer magnification of 2.5. Moreover, when the anti-glare film of Example 2 was diagonally cut and the components contained in the reactive inorganic fine particles B (1-2) were detected using TOF-SIMS manufactured by ULVAC-PHI, fluorine atoms were detected. There wasn't.

<Example 3>
In Example 1, except that the reactive inorganic fine particle B (1-3) obtained in Production Example 1-3 was used instead of the reactive inorganic fine particle B (1-1), the same procedure as in Example 1 was performed. An antiglare layer was formed on the TAC film to obtain an antiglare film.
In the obtained antiglare film of Example 3, the thickness of the uneven layer was 2.1 μm. The antiglare film of Example 3 had a skin layer magnification of 2.0. Moreover, when the anti-glare film of Example 3 was diagonally cut and the component contained in the reactive inorganic fine particle B (1-3) was detected using TOF-SIMS manufactured by ULVAC-PHI, fluorine atoms were detected. There wasn't.

<Example 4>
In Example 1, except that the reactive inorganic fine particle B (2) obtained in Production Example 2 was used instead of the reactive inorganic fine particle B (1-1), the same procedure as in Example 1 was repeated on the TAC film. An antiglare layer was formed on the film to obtain an antiglare film.
In the obtained antiglare film of Example 4, the thickness of the uneven layer was 2.1 μm. Moreover, the magnification of the skin layer of the antiglare film of Example 4 was 2.1. Moreover, when the anti-glare film of Example 4 was diagonally cut and the component contained in the reactive inorganic fine particle B (2) was detected using TOF-SIMS manufactured by ULVAC-PHI, no fluorine atom was detected. .

<Example 5>
In Example 1, except that the reactive inorganic fine particle B (3) obtained in Production Example 3 was used instead of the reactive inorganic fine particle B (1-1), in the same manner as in Example 1, on the TAC film An antiglare layer was formed on the film to obtain an antiglare film.
In the obtained antiglare film of Example 5, the thickness of the uneven layer was 2.1 μm. The antiglare film of Example 5 had a skin layer magnification of 3. Moreover, when the anti-glare film of Example 5 was diagonally cut and the component contained in the reactive inorganic fine particle B (3) was detected using TOF-SIMS manufactured by ULVAC-PHI, no fluorine atom was detected. .

<Example 6>
In Example 2, the antiglare layer was formed on the TAC film in the same manner as in Example 2 except that the coating amount of the antiglare layer coating solution was adjusted so that the thickness of the uneven layer was 1.2 μm. And an antiglare film was obtained.
The obtained antiglare film of Example 6 had a skin layer magnification of 4. The antiglare film of Example 6 had a skin layer magnification of 4.

<Example 7>
In Example 2, an antiglare layer was formed on the COP film in the same manner as in Example 2 except that a cycloolefin polymer (COP) film having a thickness of 80 μm was used instead of the triacetyl cellulose (TAC) film. An antiglare film was obtained.
In the obtained antiglare film of Example 7, the thickness of the uneven layer was 2.1 μm. The antiglare film of Example 7 had a skin layer magnification of 2.5.

<Example 8>
In Example 2, an antiglare layer was formed on the PET film in the same manner as in Example 2 except that an 80 μm-thick polyethylene terephthalate (PET) film was used instead of the triacetyl cellulose (TAC) film. An antiglare film was obtained.
In the obtained antiglare film of Example 8, the thickness of the uneven layer was 2.1 μm. The antiglare film of Example 8 had a skin layer magnification of 2.5.

<Example 9>
In Example 2, an antiglare layer was formed on the acrylic resin film in the same manner as in Example 2, except that an 80 μm thick acrylic resin film was used instead of the triacetyl cellulose (TAC) film. An antiglare film was obtained.
In the obtained antiglare film of Example 9, the thickness of the uneven layer was 2.1 μm. Moreover, the magnification of the skin layer of the antiglare film of Example 9 was 2.5.

<Comparative Example 1>
In Example 1, except that the reactive inorganic fine particles B were not contained, an antiglare layer was formed on the TAC film in the same manner as in Example 1 to obtain an antiglare film.
In the obtained antiglare film of Comparative Example 1, the thickness of the uneven layer was 2.1 μm. In addition, since the antiglare film of Comparative Example 1 did not contain reactive inorganic fine particles, no skin layer was formed.

<Comparative example 2>
In Example 1, TAC was used in the same manner as in Example 1 except that the reactive inorganic fine particles (1-4) obtained in Production Example 1-4 were used instead of the reactive inorganic fine particles B (1-1). An antiglare layer was formed on the film to obtain an antiglare film.
In the antiglare film of Comparative Example 2 obtained, the thickness of the uneven layer was 2.1 μm. Moreover, since the average particle diameter of the inorganic reaction fine particles (1-4) is 80 nm in the antiglare film of Comparative Example 2, the inorganic reaction fine particles cannot be sufficiently unevenly distributed on the uneven layer surface, and the skin layer The magnification of (region where reactive inorganic fine particles were unevenly distributed on the surface layer of the uneven layer) was 1.3 and less than 2.

〔Evaluation methods〕
About the anti-glare film obtained by the said each Example and the comparative example, the steel wool resistance was evaluated with the following method. The results are shown in Table 1 (SW resistance).
<Steel wool resistance test>
The antiglare film surface was rubbed 10 times with # 0000 steel wool at a speed of 50 mm / sec while applying a load of 300 g / cm ² , and the presence or absence of scratches on the antiglare film surface and the number of scratches were visually confirmed. did.

〔result〕
As shown in Table 1, the anti-glare film of Comparative Example 1 containing no reactive inorganic fine particles was confirmed to have many scratches (20 or more) on the surface in the steel wool resistance test. Moreover, although the reactive inorganic fine particles contained, the average particle size was as large as 80 nm, the reactive inorganic fine particles could not be sufficiently unevenly distributed in the air interface side surface layer of the uneven layer (magnification 1.3) comparison The antiglare film of Example 2 was also confirmed to have many scratches (20 or more) on its surface in the steel wool resistance test.

  On the other hand, the antiglare films of Examples 1 to 9 using the reactive inorganic fine particles B having an average particle diameter of 5 nm or more and 30 nm or less are the reactive inorganic fine particles B having a skin layer magnification of 2 or more. Uneven distribution occurred, and no more than 5 scratches were formed in the steel wool resistance test, indicating high steel wool resistance. Among them, Examples 1 to 4, Example 8 and Example 9 were confirmed to have excellent hard coat properties without formation of scratches in the steel wool resistance test.

It is sectional drawing which shows one example of an anti-glare film of this invention. It is sectional drawing which shows another example of another form of the anti-glare film of this invention. It is a figure explaining the distribution state of the reactive inorganic fine particle B in an uneven | corrugated layer.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Transparent substrate 2 ... Anti-glare layer 3 ... Uneven layer (3 ': skin layer)
4 ... Translucent fine particles 5 ... Reactive inorganic fine particles 6 ... Surface shape adjusting layer 7 ... Low refractive index layer

Claims (17)

An anti-glare film having an anti-glare layer having an uneven surface on the transparent substrate film,
The antiglare layer is a single layer consisting only of a concavo-convex layer, or has a laminated structure consisting of two or more layers including a concavo-convex layer and a surface shape adjusting layer disposed on the viewer side of the concavo-convex layer,
The uneven layer is
(1) Translucent fine particles A having an average particle diameter in the range of 1 μm to 10 μm,
(2) Reactive inorganic fine particles B having an average particle diameter in the range of 5 nm or more and 30 nm or less, having at least a part of the surface coated with an organic component, and having a reactive functional group b introduced by the organic component on the surface; And (3) a curable binder system comprising a binder component C having a reactive functional group c having a crosslinking reactivity with the reactive functional group b of the reactive inorganic fine particle B, and also having a curing reactivity in the system,
A cured product of a curable resin composition containing
Compared with the area on the opposite side of the transparent substrate film of the uneven layer and the surface layer region in the vicinity thereof, compared to the region on the transparent substrate film side of the surface layer region, the area per unit area in the cross section in the thickness direction of the uneven layer A skin layer having a large average number of particles of the reactive inorganic fine particles B;
The average number of particles of the reactive inorganic fine particles B per unit area in the cross section in the thickness direction of the skin layer is at least twice the average number of particles of the reactive inorganic fine particles B per unit area in the cross section in the thickness direction of the uneven layer. An anti-glare film characterized by being   The thickness of the skin layer is from 1 to 5 times the average particle diameter of the reactive inorganic fine particles B from the interface opposite to the transparent base film. The anti-glare film as described in 2.   The antiglare film according to claim 1, wherein the reactive inorganic fine particles B are densely packed in the skin layer. The average number of the reactive inorganic fine particles B per unit area in the cross section in the thickness direction of the skin layer is 800 particles / μm ² or more, and the reactivity per unit area in the cross section in the thickness direction of the entire uneven layer. The antiglare film according to any one of claims 1 to 3, wherein the average number of inorganic fine particles B is 500 particles / µm ² or less.   The antiglare film according to any one of claims 1 to 4, wherein the inorganic fine particles serving as the core of the reactive inorganic fine particles B and the translucent fine particles A are made of the same material. At least a part of the surface of the reactive inorganic fine particle B is coated with an organic component, the reactive functional group b is introduced to the surface of the reactive inorganic fine particle B by the organic component, and the organic component is The anti-glare film according to any one of claims 1 to 5, which is contained in an amount of 1.00 × 10 ⁻³ g / m ² or more per unit surface area of the inorganic fine particles before coating.   The anti-glare film according to any one of claims 1 to 6, wherein the reactive inorganic fine particle B does not contain fluorine.   The reactive functional group b of the reactive inorganic fine particle B and the reactive functional group c of the binder component C each have a polymerizable unsaturated group. The anti-glare film as described in 2.   The reactive inorganic fine particles B are saturated or unsaturated carboxylic acids, acid anhydrides corresponding to the carboxylic acids, acid chlorides, esters and acid amides, amino acids, imines, nitriles, isonitriles, epoxy compounds, amines, β-di Inorganic fine particles in water and / or an organic solvent as a dispersion medium in the presence of one or more surface modification compounds having a molecular weight of 500 or less selected from the group consisting of carbonyl compounds, silanes, and metal compounds having functional groups The antiglare film according to any one of claims 1 to 8, which is obtained by dispersing.   The antiglare film according to claim 9, wherein the surface modifying compound is a compound having a hydrogen bond-forming group.   The anti-glare film according to claim 10, wherein at least one of the surface modification compounds has a polymerizable unsaturated group to be the reactive functional group b. The reactive inorganic fine particle B includes a reactive functional group b introduced into the surface of the reactive inorganic fine particle B, a group represented by the following chemical formula (1), and a silanol group or a group that generates a silanol group by hydrolysis. The anti-glare film according to any one of claims 1 to 8, which is obtained by bonding a metal oxide fine particle.
Chemical formula (1)
^{-Q 1 -C (= Q 2)} -NH-
(In the chemical formula (1), Q ¹ represents NH, O (oxygen atom), or S (sulfur atom), and Q ²
Represents O or S. )   The prevention according to any one of claims 1 to 12, wherein the binder component C is a compound having three or more reactive functional groups c capable of binding to the reactive functional groups b of the reactive inorganic fine particles B. Dazzle film.   The anti-glare film according to any one of claims 1 to 13, wherein the content of the reactive inorganic fine particles B is 5 to 30% by weight with respect to the total solid content.   The antiglare film according to any one of claims 1 to 14, wherein the transparent base film is mainly composed of cellulose acylate, cycloolefin polymer, acrylate polymer, or polyester. In the steel wool test in which the surface of the antiglare layer is subjected to 10 reciprocating friction with a # 0000 steel wool at a speed of 50 mm / sec while applying a load of 300 g / cm ² , the surface of the antiglare layer is scratched. The anti-glare film according to any one of claims 1 to 15, wherein   The anti-glare film as described in any one of Claims 1 thru | or 16 whose film thickness of the said uneven | corrugated layer is 0.5-30 micrometers.

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