JP5303836B2 - Curable resin composition for antiglare layer and antiglare film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable resin composition for an anti-glaring layer capable of forming an anti-glaring film with a high hard coating property, and to provide the anti-glaring film using the curable resin composition for the anti-glaring layer. <P>SOLUTION: The curable resin composition for the anti-glaring layer comprises a curable binder system, which includes: (1) translucent particles A with a mean particle diameter of larger than 500 nm; (2) reactive inorganic particles B, of which the mean particle diameter is 20 nm or larger but 500 nm or smaller, at least one part of the surfaces are coated with organic components, and the surfaces have a reactive functional group b; and (3) binder components C having a reactive functional group c having cross-linking reactivity with the reactive functional group b of the above reactive inorganic particles B, and also has curing reactivity in the system. <P>COPYRIGHT: (C)2008,JPO&amp;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 a curable resin composition for forming an antiglare layer of an antiglare film, and an antiglare film provided with an antiglare layer using the curable resin composition.

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 (Patent Document 1).

JP 2006-103070 A

On the other hand, the image display surface of the image display device such as the display as described above is required to be provided with scratch resistance so as not to be damaged 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.

However, an anti-glare layer having both anti-glare properties and hard coat properties (abrasion resistance) has not been sufficiently studied.
In view of the above circumstances, the present invention is capable of forming an antiglare film having high hard coat properties, and an antiglare film using the curable resin composition for an antiglare layer, and the curable resin composition for the antiglare layer. Is intended to provide.

As a result of intensive studies, the present inventors have included anti-glare layer curable resin compositions containing reactive inorganic fine particles B that can undergo a crosslinking reaction with binder component C, thereby preventing anti-glare properties having high hard coat properties. The inventors have found that a dazzling film can be obtained and have completed the present invention.
That is, the present invention is an antiglare film provided with an antiglare layer having an uneven surface on the observer side of the transparent substrate,
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 concavo-convex layer has the following component (1) translucent fine particles A selected from inorganic fine particles having an average particle size larger than 500 nm,
(2) The average particle diameter is 20 nm or more and 500 nm or less, and at least a part of the surface is coated with an organic component, and the organic component is 3.50 × 10 ⁻³ g / m ² per unit area of the inorganic fine particles before coating. contains more than, the reactive inorganic fine particles B having a group having an ethylenic double bond as a reactive functional group b that is introduced by the organic component to the surface, and (3) an ethylenic double bond as reactivity functional group c Comprising a cured product of a curable resin composition for an antiglare layer containing a binder component C having a group having a curable binder system having curing reactivity in the system ,
And the film thickness of the said uneven | corrugated layer is 0.5 micrometer or more and 3.5 micrometers or less, The anti-glare film characterized by the above-mentioned is provided.

  According to the present invention, the reactive functional group b of the reactive inorganic fine particle B contained in the curable binder system and the reactive functional group c of the binder component C form a crosslink, thereby having high hard coat properties. An antiglare film can be obtained.

In the curable resin composition for an antiglare layer according to the present invention, the content of the reactive inorganic fine particles B is 100 parts by weight of the total amount of the reactive inorganic fine particles B and the constituent components of the curable binder system. On the other hand, it is preferably 1 to 50 parts by weight from the viewpoint of increasing the film strength.

In the curable resin composition for an antiglare layer according to the present invention, the reactive inorganic fine particle B is a saturated or unsaturated carboxylic acid, an acid anhydride corresponding to the carboxylic acid, an acid chloride, an ester, and an acid amide. In the presence of one or more surface modification compounds having a molecular weight of 500 or less selected from the group consisting of amino acids, imines, nitriles, isonitriles, epoxy compounds, amines, β-dicarbonyl compounds, silanes, and metal compounds having functional groups, Obtaining by dispersing inorganic fine particles in water and / or an organic solvent as a dispersion medium is preferable from the viewpoint of improving the film strength even if the organic component content is small.

In the curable resin composition for an antiglare layer according to the present invention, it is preferable that the surface modifying compound is a compound having at least one hydrogen bond forming group from the viewpoint that the organic component can be efficiently surface modified.

In the antiglare film of the present invention, the transparent substrate is preferably mainly composed of cellulose acylate, cycloolefin polymer, acrylate polymer, or polyester.

In the antiglare film of the present invention, the antiglare layer preferably has a pencil hardness of 3H or more.

  In the curable resin composition for an antiglare layer of the present invention, 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 curable binder system form a crosslink. Therefore, the antiglare film using the curable resin composition for an antiglare layer can have high hard coat properties. Further, by making the particle diameter of the reactive inorganic fine particle B smaller than the particle diameter of the translucent fine particle A, the reactive inorganic fine particle B has the reactive inorganic fine particle B even if the content of the reactive inorganic fine particle B is not so large. The number of crosslinking points can be increased, and the hard coat property of the antiglare film can be further improved.

The present invention relates to a curable resin composition for an antiglare layer and an antiglare film using the curable resin composition. Hereinafter, the curable resin composition for the antiglare layer and the antiglare film will be described in order.

I. First, the curable resin composition for an antiglare layer of the present invention will be described.
The curable resin composition for an antiglare layer of the present invention is
(1) Translucent fine particles A having an average particle diameter larger than 500 nm,
(2) Reactive inorganic fine particles B having an average particle diameter of 20 nm or more and 500 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; 3) 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 a curable binder system having a curing reactivity in the system. It is characterized by this.

According to the curable resin composition for an antiglare layer of the present invention, the reactive functional group b of the reactive inorganic fine particle B contained in the curable binder system and the reactive functional group c of the binder component C form a crosslink. By doing so, an antiglare film having high hard coat properties can be obtained.

Hereafter, each structure of the curable resin composition for anti-glare layers of this invention is demonstrated in detail in order.
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 b and the reactive functional group c in the present specification include a photocurable functional group and a thermosetting functional group. The photocurable functional group means a functional group capable of curing a coating film by proceeding a polymerization reaction or a crosslinking reaction by light irradiation. For example, photo radical polymerization, photo cation polymerization, photo anion polymerization Examples of the polymerization reaction include those in which the reaction proceeds by a reaction mode such as addition polymerization or condensation polymerization that proceeds through 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 b and the reactive functional group c used in the present invention, in particular, from the viewpoint of improving the hardness of the cured film, a polymerizable unsaturated group is preferably used, and 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.

<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. 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 larger than 500 nm, preferably 0.5 μm or more and 20 μm or less, more preferably 0.5 μm or more and 10.0 μm or less. preferable. When the average particle size is less than 0.5 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. Since the amount of the fine particles A to be added must be very large, the film properties of the antiglare layer are deteriorated. On the other hand, when the average particle diameter exceeds 20 μm, the surface shape of the antiglare layer becomes rough, and the surface quality may be deteriorated, or the 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 contained particle is a monodisperse type particle (particle 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 A 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. The amorphous silica has a particle size of 0. It is preferred to use 5-5 μm silica beads. In order to improve the dispersibility of the above-mentioned amorphous silica without causing an increase in the viscosity of the coating solution for forming an antiglare layer, which will be described in detail below, the amorphous silica that has been subjected to organic treatment on the particle surface to make it hydrophobic Is preferably used. 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 above-described 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 may be used at the terminal or intermediate part of the alkyl chain.
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 light-transmitting fine particles A is preferably 5% by mass or more and 40% by mass or less with respect to the total solid content of the concavo-convex layer. More preferably, it is 10 mass% or more and 30 mass% or less. When it is less than 5% by mass, sufficient antiglare property cannot be imparted, and when it exceeds 40% by mass, the film strength is lowered and hard coat property cannot be imparted to the antiglare layer, which is not preferable.

  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 types of fine particles comprising different components are mixed and used, the two or more types of fine particles preferably have different average particle sizes as described above, but those having the same average particle size 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 such that the total mass per unit area of the first fine particles is 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.
In particular, 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 an organic component is coated on at least a part of the surface of the inorganic fine particle serving as a core and has a reactive functional group introduced by the organic component on the surface. The reactive inorganic fine particles B include those having two or more inorganic fine particles as a core per particle. Moreover, the reactive inorganic fine particle B can raise the crosslinking point in a matrix instead of content by making a particle diameter small.

The antiglare layer according to the present invention contains the reactive inorganic fine particles B for the purpose of remarkably improving the hardness so as to have sufficient scratch resistance. The reactive inorganic fine particles B may be those that further impart a function to the antiglare layer, and are 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. In addition, in order to form a high refractive index layer in phase, 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.
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 have at least a part of the surface coated with an organic component and have a reactive functional group 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 the 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 covering 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 aspect 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 the aspect in which the polymer particles contain inorganic fine particles, the organic component covering 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, the organic component weight / inorganic component weight is measured by differential thermogravimetric analysis (TGA). 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 whole inorganic component and the volume per inorganic fine particle before coating, the number of inorganic fine particles before coating is obtained. 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 average particle size of the reactive inorganic fine particles B is preferably 20 nm or more and 500 nm or less from the viewpoint of hardness, more preferably 30 nm or more and 250 nm or less, and particularly preferably 30 nm or more and 150 nm or less. This is because by reducing the particle diameter of the reactive inorganic fine particles B, the crosslinking point in the matrix can be increased instead of the content.
In addition, the reactive inorganic fine particle B has a narrow particle size distribution and is monodispersed from the viewpoint of significantly improving the hardness while maintaining the restoration rate when using only the resin without impairing the transparency. preferable.
The average particle size here is a 50% average particle size, and can be determined using, for example, a Microtrac 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 introduced by the organic component on at least a part of the surface, the kind of the inorganic fine particles and the reactive functional to be introduced A conventionally known method can be appropriately selected and used depending on the group b.
Among them, in the present invention, the organic component to be coated can be contained in the reactive inorganic fine particles B in an amount of 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 of the following inorganic fine particles (i), (ii) and (iii).
(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.
(Ii) After a monomer in which inorganic fine particles having a particle diameter of 500 nm or less are dispersed in a hydrophobic vinyl monomer is discharged into water through a hydrophilicized porous membrane to form an aqueous dispersion of monomer droplets in which inorganic fine particles are dispersed. Inorganic fine particles having reactive functional groups on the surface, obtained by polymerization.
(Iii) 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 particle B (i) is 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. 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), wherein the residue Q is independently 1-12, in particular 1-6, 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 A trimethoxysilane etc. can be mentioned.

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 the colloidal inorganic fine particles obtained by pulverizing the surface modifying compound and at least partially 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 monomer in which inorganic fine particles having a particle diameter of 500 nm or less are dispersed in a hydrophobic vinyl monomer is discharged into water through a hydrophilicized porous membrane to obtain an aqueous dispersion of monomer droplets in which inorganic fine particles are dispersed. Inorganic fine particles having reactive functional groups on the surface, obtained by polymerization.
When the reactive inorganic fine particle B (ii) is used, there are advantages that monodispersity is further enhanced from the viewpoint of particle size distribution, and irregular performance can be suppressed when coarse particles are included.

  Since the reactive inorganic fine particle B used in the present invention is an inorganic fine particle having a reactive functional group introduced on the surface of which at least a part of the surface is coated with an organic component, the type (ii) The hydrophobic vinyl monomer used for the polymerization in producing the reactive inorganic fine particle B has a reactive functional group b, or a desired reactive functional group b can be introduced later. At least one having another reactive functional group is contained. For example, after using a hydrophobic vinyl monomer having a carboxyl group in advance and polymerizing it, the carboxyl group is reacted with glycidyl methacrylate to introduce a polymerizable unsaturated group.

  Specific examples of the hydrophobic vinyl monomer include aromatic vinyl compounds such as styrene, vinyl toluene, α-methylstyrene, divinylbenzene; methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meth) T-butyl acrylate, n-hexyl (meth) acrylate, isobutyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, (meth) acrylic acid Stearyl, benzyl (meth) acrylate, mono- or di (meth) acrylate of (poly) ethylene glycol, mono- or di (meth) acrylate of (poly) propylene glycol, mono- or di- (1,4-butanediol) Mono) of (meth) acrylate and trimethylolpropane Unsaturated carboxylic acid esters such as di- or tri- (meth) acrylate; allyl compounds such as diallyl phthalate, diallyl acrylamide, triallyl (iso) cyanurate, triallyl trimellitate; (poly) ethylene glycol di (meth) And (poly) oxyalkylene glycol di (meth) acrylates such as acrylate and (poly) propylene glycol di (meth) acrylate. In addition, conjugated diene compounds such as butadiene, isoprene and chloroprene. Furthermore, reactive functional group-containing monomers such as acrylic acid, methacrylic acid, itaconic acid, fumaric acid, glycidyl methacrylate, vinylpyridine, diethylaminoethyl acrylate, N-methylmethacrylamide, acrylonitrile and the like can be mentioned. Among these, highly water-soluble monomers such as acrylic acid, methacrylic acid, and itaconic acid can be used as long as the water solubility of the whole monomer is high and an oil-in-water monomer emulsion cannot be formed.

The inorganic fine particles used in (ii) must have a small particle size and be well dispersed in the hydrophobic vinyl monomer. The particle size of the inorganic particles used here is 500 nm or less, preferably 300 nm or less, more preferably 150 nm or less. In addition, when the inorganic fine particles are not familiar with the hydrophobic vinyl monomer, the surface of the inorganic fine particles is preferably pretreated. For the surface treatment, a known method such as a dispersant treatment for adsorbing the pigment dispersant on the inorganic surface, a coupling agent treatment with a silane coupling agent, a titanate coupling agent, or a polymer coating treatment by capsule polymerization may be applied. it can.

In (ii), in order to emulsify the hydrophobic vinyl monomer in which the inorganic fine particles are dispersed in water, the hydrophobic vinyl monomer is discharged into the water through the hydrophilicized porous membrane. These porous pores must have an average pore diameter of 0.01 to 5 μm, a uniform pore diameter, and must penetrate the front and back of the membrane. Glass is preferable as the material of the film. As a specific example, SiO ₂ —Al ₂ O ₃ —B ₂ O ₃ —CaO-based glass fired using volcanic ash shirasu as a main raw material is microphase-separated by heat treatment and rich in boric acid. Porous glass (referred to as SPG) obtained by dissolving and removing the phase with an acid is preferred.

In (ii), a surfactant or a water-soluble polymer needs to be present as a monomer droplet stabilizer in the aqueous phase for extruding the hydrophobic vinyl monomer containing inorganic fine particles through the porous membrane. Without the stabilizer, the monomer droplets ejected through the film merge with each other and have a wide particle size distribution. A preferable stabilizer is a water-soluble polymer stabilizer such as polyvinyl alcohol, hydroxypropylcellulose, polyvinylpyrrolidone or the like when the monomer droplets are about 1 μm or more, and a small amount of anionic surfactant or It is also preferable to add a nonionic emulsifier. For example, a combination of sodium lauryl sulfate as an emulsifier and 1-hexadecanol as a co-emulsifier is particularly preferable as the stabilizer in (ii) because it strongly adsorbs to the droplet surface and has a large stabilizing effect.

In (ii), in order to polymerize the aqueous dispersion of monomer droplets containing emulsified inorganic fine particles, an oil-soluble radical initiator is mainly used. Examples of initiators that can be used as oil-soluble radical initiators include azo initiators such as azobisisobutyronitrile, aromatic peroxides such as benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, isobutyl peroxide, diisopropyl Examples thereof include aliphatic peroxides such as peroxydicarbonate and di (2-ethylhexylperoxy) dicarbonate. These can be used by dissolving in the monomer phase in advance before emulsification. Moreover, you may add water-soluble radical polymerization inhibitors, such as hydroquinone and iron chloride.

(Iii) 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 the inorganic fine particles serving as a core Inorganic fine particles having reactive functional groups 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 particle B (iii) is used, there is an advantage that dispersibility and film strength are further increased from the viewpoint 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 with 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 particles B of (iii), after separately hydrolyzing the reactive functional group-modified hydrolyzable silane, this is mixed with the inorganic fine particles, 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 (iii), 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.

As the reactive inorganic fine particles B, powdery fine particles not containing a dispersion medium may be used. However, it is preferable to use a fine particle in a solvent-dispersed sol from the viewpoint of high productivity because the dispersion step can be omitted.
The content of the reactive inorganic fine particles B is preferably 1 to 50 parts by weight, and more preferably 2 to 30 parts per 100 parts by weight of the total amount of the reactive inorganic fine particles B and the constituent components of the curable binder system. It is preferable that it is a weight part. If the amount is less than 1 part by weight, the hardness of the surface of the antiglare layer may be insufficient, and if it exceeds 50 parts by weight, the filling rate may increase too much and the film strength may decrease.

<Curable binder system>
In the present specification, the constituent component of the curable binder system is an uneven layer which will be described later after curing of a curable binder component other than the binder component C, a polymer component, a polymerization initiator and the like, in addition to the binder component C. Represents a matrix component.
[Binder component C]
In the curable resin composition for an antiglare layer according to the present invention, the binder component C has a reactive functional group c having a crosslinking reactivity with the reactive functional group b of the reactive inorganic fine particle B, and the reactivity. The functional group b and the reactive functional group c are 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.

The binder component C is preferably a translucent material that transmits light when coated, and specific examples thereof include an ionizing radiation curable resin that is a resin curable by ionizing radiation typified by ultraviolet rays or electron beams, Mixtures of ionizing radiation curable resins and solvent-drying resins (such as thermoplastic resins that can be used as coatings by simply drying the solvent to adjust the solid content during coating), or thermosetting resin There are three types, and 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.

[Other ingredients]
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 coating composition mentioned later. A coating composition with a leveling agent can provide coating stability, slipperiness and antifouling properties to the coating surface during application or drying, and can also provide an effect of scratch resistance. And

<Preparation of resin composition>
The curable resin composition for an antiglare layer according to the present invention 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.

II. Anti-glare film The anti-glare film according to the present invention is an anti-glare film provided with an anti-glare layer having an uneven surface on the observer side of the transparent substrate,
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 said uneven | corrugated layer consists of hardened | cured material of the said curable resin composition for glare-proof layers, It is characterized by the above-mentioned.
The antiglare film according to the present invention is provided with an antiglare layer made of a cured product of the curable resin composition for an antiglare layer according to the present invention on a transparent substrate, whereby the hard coat property of the entire antiglare film is provided. Can be improved.

Hereinafter, the layer configuration of the antiglare film according to the present invention will be described.
FIG. 1 is a cross-sectional view of an example of a basic layer structure of an antiglare film according to the present invention. The anti-glare layer 1 is provided on any one surface of the transparent substrate 2, and the anti-glare layer 1 is always disposed on the surface on the viewer side.
In addition, 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. Further, the transparent substrate is not limited to only one layer, and two or more layers may be present.
The antiglare layer 1 has at least an uneven layer. In the present invention, the uneven layer is a layer having an uneven shape on the outermost surface of the antiglare layer.

Since the antiglare film of the present invention can provide various functions required for an image display device, the antiglare layer 1 comprises two or more layers as shown in FIG. However, it is good also as a laminated structure which has the surface shape adjustment layer 12 in the observer side of the uneven | corrugated layer 11. FIG. By forming the surface shape adjusting layer 12 on the concavo-convex layer, the concavo-convex layer 11 may have a fine concavo-convex shape or an excessively large concavo-convex shape in order to exhibit appropriate anti-glare performance, for example. Even when there is a difference, the surface of the antiglare layer 1 on the viewer side 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 12 may further contain an antistatic agent, a refractive index adjusting agent, a stainproofing agent, a water repellent agent, an oil repellent agent, a fingerprint adhesion preventing agent, a high curing agent and a hardness adjusting agent.

  Moreover, although the surface shape adjustment layer 12 may serve as a low refractive index layer, the antiglare layer 1 may be provided with antireflection performance. However, as shown in FIG. Thus, the low refractive index layer 13 may be further provided on the viewer side separately from the surface shape adjusting layer 12. The low refractive index layer 13 has a shape that follows the concavo-convex shape of the surface of the concavo-convex layer 11 or the surface shape adjusting layer 12 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 13, an arbitrary layer may exist on the viewer side. The low refractive index layer 13 has a refractive index lower than the refractive index of the layer on the image display device side on which the low refractive index layer 13 is laminated.

  Hereinafter, each layer which comprises the anti-glare film of this invention is demonstrated in order.

<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, 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 or ZEONOR (norbornene resin) manufactured by Nippon Zeon Co., Ltd., Sumitrite FS-1700 manufactured by Sumitomo Bakelite Co., Ltd., Arton (modified norbornene resin) manufactured by JSR Corporation, Appel (cyclic olefin) manufactured by Mitsui Chemicals, Inc. 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, 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 in advance. You may do it.

<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 the present invention, an uneven layer prepared in advance may be laminated on the surface of the transparent substrate or the like. In this case, the uneven | corrugated layer prepared separately may be sufficient.

[Uneven layer]
The concavo-convex layer of the present invention is for imparting adhesion to translucent fine particles A for imparting antiglare properties, reactive inorganic fine particles B for imparting hard coat properties, and substrates and adjacent layers. Contains the binder component C as an essential component, contains a component that forms a matrix of the concavo-convex layer after curing of the curable binder system, and further, if necessary, additives such as antistatic agents, leveling agents, refractive index adjustment, crosslinking It is formed by containing an inorganic filler for preventing shrinkage and imparting high indentation strength.

(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, and the concavo-convex layer is translucent to the surface of the transparent substrate on the observer side. An anti-glare film formed by a method of forming a concavo-convex layer by applying a composition for concavo-convex layer to which fine particles A and reactive inorganic fine particles B are added can be mentioned.
The concavo-convex layer is formed by coating a transparent substrate with a coating composition obtained by mixing translucent fine particles A, reactive inorganic fine particles B, and photocurable binder-based components in an appropriate solvent. be able to. 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.

Examples of a method for applying the coating composition to the transparent substrate include application methods such as a roll coating method, a Miya bar coating method, and a gravure coating method. After application of the coating composition, drying and ultraviolet curing are performed. Specific examples of the ultraviolet light source include ultrahigh pressure mercury lamps, high pressure mercury lamps, low pressure mercury lamps, carbon arc lamps, black light fluorescent lamps, and metal halide lamp lamps. As the wavelength of the ultraviolet light, a wavelength range of 190 to 380 nm can be used. Specific examples of the electron beam source include various types of electron beam accelerators such as a cockcroft-wald type, a bandegraft type, a resonant transformer type, an insulating 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 of the binder component C contained in the constituent component of the photocurable binder system. c is cross-linked 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, an ink containing components other than the light-transmitting fine particles A, such as a monomer, an oligomer, a polymer, and other additives, among the components of the uneven layer composition, is prepared, and 5 μm thick on a 50 μm-thick PET substrate. Each of the samples was applied by changing the UV irradiation conditions at 10 mJ intervals 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 A 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 A before being immersed in the solvent and the dried sample B is taken, and this value is taken as C. Finally, the gel fraction (%) for each dose is calculated using the following formula.
“Gel fraction (%)” = 100−C / A

The film thickness of the antiglare layer according to the present invention 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, Productivity is also preferable from the viewpoint of good performance. If the film thickness is less than 0.5 μm, sufficient hard coat properties cannot be imparted, and if it exceeds 30 μm, cracks tend to occur, which is not preferable.
In the antiglare film of the present invention, the antiglare layer preferably has a pencil hardness of 3H or more.

<Other layers>
The antiglare film according to the present invention is basically composed of a transparent substrate and an 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.

(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 adjusting layer fills fine unevenness existing along the uneven shape with a scale of 1/10 or less of the uneven surface scale (irregularity peak height and interval) in the surface roughness of the uneven layer, and applies smoothing. Smooth the uneven surface, or adjust the crest pitch, crest height, and crest frequency (number). 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. In addition, the thickness of the said surface adjustment layer is the value measured similarly to the measuring method of the layer thickness of an anti-glare layer by laser microscope observation mentioned later, SEM, or TEM observation.

(binder)
The binder (including resin components such as monomers and oligomers) is preferably transparent, and specific examples thereof include ionizing radiation curable resins and ionizing radiation curable resins which are resins curable by ultraviolet rays or electron beams. And a mixture of a solvent-drying resin and a thermosetting resin, preferably an ionizing radiation curable resin.
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” (the above are 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 may be formed by applying the composition for surface shape adjusting layer to a transparent substrate or the like. Examples of the method for applying the composition for the surface shape adjusting layer include application methods such as a roll coating method, a Miya bar coating method, and a gravure coating method. After application of the composition for the surface shape adjusting layer, drying and ultraviolet curing are performed. Specific examples of the ultraviolet light source include ultrahigh pressure mercury lamps, high pressure mercury lamps, low pressure mercury lamps, carbon arc lamps, black light fluorescent lamps, and metal halide lamp lamps. As the wavelength of the ultraviolet light, a wavelength range of 190 to 380 nm can be used. Specific examples of the electron beam source include various types of electron beam accelerators such as a cockcroft-wald type, a bandegraft type, a resonant transformer type, an insulating 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, the 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 the antiglare 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 a 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.

[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 with almost no haze and good total light transmittance can be produced when the average particle diameter is within the range of the above-described average particle diameter. . 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 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 electron beams 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 emitted from light such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, and 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 within the range of 1.46 to 2.00, and the medium refractive index agent has a refractive index within 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. Resin composition for anti-glare layer added with leveling agent improves coating suitability to the coating film surface during application or drying, and can provide slipping and antifouling properties, and also has an effect of scratch resistance. It is possible to do.

[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.

  Hereinafter, the present invention will be specifically described with reference to examples. These descriptions do not limit the present invention. In the examples, “part” and “%” are based on mass unless otherwise specified. As the particle size distribution of the monodisperse fine particles blended in the composition, those having an average particle diameter of ± 0.3 to ± 1 μm are used. However, when the particle diameter is 3.5 μm or less, the particle size distribution is not limited.

(Production Example 1-1: Preparation of reactive inorganic fine particles B (1-1))
(1) Surface adsorbed ion removal Water-dispersed colloidal silica (Snowtex ZL, trade name, manufactured by Nissan Chemical Industries, Ltd., pH 9 to 10) having a particle diameter of 90 nm is exchanged with 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 anion exchange resin (Diaion SA20A, manufactured by Mitsubishi Chemical Corporation), followed by washing and 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 the silica fine particle aqueous dispersion subjected to the treatment of (1) above, and the mixture is 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 = 92 nm as a result of measurement with a Microtrac 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 4.05 × 10 ⁻³ g / m ² as a result of measurement by thermogravimetric analysis.

(Production Example 1-2: Preparation of reactive inorganic fine particles B (1-2))
(1) Surface Adsorbed Ion Removal As in Production Example 1-1, an aqueous dispersion of silica fine particles from which surface adsorbed ions were removed was obtained.
(2) Surface treatment (introduction of polyfunctional monomer)
The surface treatment was performed in the same manner as in Production Example 1-1 except that the production method was changed to dipentaerythritol pentaacrylate (SR399, trade name, manufactured by Sartomer Co., Ltd.) in Production Example 1-1.
The reactive inorganic fine particles B (1-2) thus obtained had an average particle diameter of d ₅₀ = 93 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.

(Production Example 2: Preparation of reactive inorganic fine particles B (2))
40 g of an oily dispersion of ferrite magnetic material (Teiho Kogyo Co., Ltd. ferricolloid, particle size 20 nm), 94 g of styrene, 1 g of vinylbenzene, 5 g of glycidyl methacrylate, and 3 g of azobisisobutyronitrile are mixed and cooled. A hydrophobic vinyl monomer in which inorganic fine particles were dispersed was obtained by dispersing for a minute. As a porous film, a SiO ₂ —Al ₂ O ₃ —B ₂ O ₃ —CaO-based glass was microphase-separated by heat treatment, and a boric acid-rich phase was dissolved and removed with an acid to make a porous tube (Ise Chemical Co., Ltd. ) SPG manufactured, pore diameter 0.3 μm) was immersed in 2N sulfuric acid at 70 ° C. for 2 hours, and sufficiently washed with water for hydrophilic treatment. Subsequently, a solution of 10 g of sodium lauryl sulfate and 25.3 g of 1-hexadecanol added to 2 liters of water was subjected to ultrasonic irradiation for 10 minutes and immersed in an aqueous solution whose gel structure was destroyed. The air bubbles inside the porous glass were removed. Next, the aqueous solution was flowed inside the porous glass tube at a flow rate of 200 ml / min, and a hydrophobic vinyl monomer in which inorganic fine particles were dispersed was flowed outside at a pressure of 1.3 kg / cm ² . In the aqueous phase flowing out from the inside of the porous glass, fine droplets in which the hydrophobic vinyl monomer phase was emulsified existed and became cloudy. One liter of the aqueous dispersion of hydrophobic vinyl monomer droplets in which the obtained inorganic fine particles are dispersed is stirred at 70 ° C. for 8 hours to carry out a polymerization reaction to obtain magnetic substance-containing polymer particles (reactive inorganic fine particles B (2)). Obtained. The reactive inorganic fine particles B (2) thus obtained had an average particle diameter of d ₅₀ = 63 nm as a result of measurement by the particle size analyzer. The amount of the organic component covering the surface was 5.35 × 10 ⁻³ g / m ² as a result of measurement by thermogravimetric analysis.

(Production Example 3: Preparation of reactive inorganic fine particles B (3))
To a solution consisting of 7.8 parts of mercaptopropyltrimethoxysilane and 0.2 part of dibutyltin dilaurate in dry air, 20.6 parts of isophorone diisocyanate was added dropwise at 50 ° C. over 1 hour and then at 60 ° C. Stir for 3 hours. To this, 71.4 parts of pentaerythritol triacrylate was added dropwise at 30 ° C. over 1 hour, and then heated and stirred at 60 ° C. for 3 hours to obtain Compound (1).

Under nitrogen flow, methanol silica sol (manufactured by Nissan Chemical Industries, Ltd., trade name, methanol solvent colloidal silica dispersion (number average particle size 0.012 μm, silica concentration 30%)) 88.5 parts (solid content 26.6 parts) ), 8.5 parts of the compound (1) synthesized above and 0.01 parts of p-methoxyphenol were stirred at 60 ° C. for 4 hours. Subsequently, 3 parts of methyltrimethoxysilane as compound (2) is added to this mixed solution, and after stirring for 1 hour at 60 ° C., 9 parts of methyl orthoformate is added, and further heated and stirred at the same temperature for 1 hour. Thus, crosslinkable inorganic fine particles were obtained. The reactive inorganic fine particles B (3) thus obtained had an average particle diameter of d ₅₀ = 63 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.

<Example 1>
As a transparent substrate, an “antiglare layer coating solution” 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 film. "(Reactive inorganic fine particles B (1-1) introduction rate is 15%) is coated with 3.5 g / m ^{2 of} Miyabar Coat, the solvent is evaporated and dried, and the oxygen concentration is 0.1%. An anti-glare film with a film thickness of 2.1 μm was obtained by irradiating twice at a speed of 10 m / min with an 80 W / cm ultraviolet irradiation device while maintaining the following.
“Anti-glare coating solution”
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 the production of the antiglare film of Example 1, in the same manner as in Example 1 except that the introduction rate of the reactive inorganic fine particles B (1-1) obtained in Production Example 1-1 was set to 30%, An antiglare film was obtained.

<Example 3>
In the production of the antiglare film of Example 1, except that the introduction rate of the reactive inorganic fine particles B (1-1) obtained in Production Example 1-1 was 50%, the same as in Example 1, An antiglare film was obtained.

<Example 4>
In the production of the antiglare film of Example 1, the antiglare film was prepared in the same manner as in Example 1 except that urethane-containing pentaerythritol triacrylate (PETA) was used as the monomer having an ionizing radiation curable functional group. Obtained.

<Example 5>
In the production of the antiglare film of Example 1, the antiglare film was prepared in the same manner as in Example 1 except that the reactive inorganic fine particles B (1-2) obtained in Production Example 1-2 were used. Obtained.

<Example 6>
In the production of the antiglare film of Example 1, an antiglare film was obtained in the same manner as in Example 1 except that the reactive inorganic fine particles B (2) obtained in Production Example 2 were used.

<Example 7>
In the production of the antiglare film of Example 1, an antiglare film was obtained in the same manner as in Example 1 except that the reactive inorganic fine particles B (3) obtained in Production Example 3 were used.

<Example 8>
In the production of the antiglare film of Example 1, an antiglare film was obtained in the same manner as in Example 1 except that a cycloolefin polymer (COP) film having a thickness of 80 μm was used as the transparent substrate.

<Example 9>
In the production of the antiglare film of Example 1, an antiglare film was obtained in the same manner as in Example 1 except that an 80 μm thick polyethylene terephthalate (PET) film was used as the transparent substrate.

<Example 10>
In the production of the antiglare film of Example 1, an antiglare film was obtained in the same manner as in Example 1 except that an acrylic resin film having a thickness of 80 μm was used as the transparent substrate.

< Reference Example 1 >
In the production of the antiglare film of Example 1, polymethylmethacrylate (PMMA) / styrene was used as the light-transmitting fine particles A, and the film thickness of the antiglare layer was changed to 12 μm. An antiglare film was obtained.

< Reference Example 2 >
In the production of the antiglare film of Example 1, polymethyl methacrylate (PMMA) was used as the translucent fine particles A, and urethane-containing PETA was used as the monomer having an ionizing radiation curing group, and the film thickness of the antiglare layer was 20 μm. Except for the above, an antiglare film was obtained in the same manner as in Example 1.

< Reference Example 3 >
In the production of the anti-glare film of Example 1, polymethyl methacrylate (PMMA) / ethylene glycol dimethacrylate (EtGDMA) is used as the light-transmitting fine particles A, and urethane-containing PETA is used as the monomer having an ionizing radiation curable group. An antiglare film was obtained in the same manner as in Example 1 except that the layer thickness was 20 μm.

<Example 14>
In the production of the antiglare film of Example 1, the reactive inorganic fine particles B (1-2) obtained in Production Example 1-2 were used as the reactive inorganic fine particles B, and the average particle size was d ₅₀ = 60 nm. Except for the above, an antiglare film was obtained in the same manner as in Example 1.

<Example 15>
In the production of the antiglare film of Example 1, an antiglare film was obtained in the same manner as in Example 1 except that the average particle size of the reactive inorganic fine particles B (1-1) was d ₅₀ = 120 nm.

<Example 16>
In the production of the antiglare film of Example 1, the same procedure as in Example 1 was conducted except that the introduction rate of the reactive inorganic fine particles B (1-1) obtained in Production Example 1-1 was 0.5%. Thus, an antiglare film was obtained.

<Example 17>
In the production of the antiglare film of Example 1, an antiglare film was obtained in the same manner as in Example 1 except that a bifunctional acrylate was used as the monomer having an ionizing radiation curable group.

< Reference Example 4 >
In the production of the antiglare film of Example 1, Example 1 except that the amount of the organic component covering the surface of the reactive inorganic fine particle B (1-1) was 0.80 × 10 ⁻³ g / m ^2. In the same manner as above, an antiglare film was obtained.

< Reference Example 5 >
In the production of the antiglare film of Example 1, an antiglare film was obtained in the same manner as in Example 1 except that the film thickness of the antiglare layer was 35 μm.

< Reference Example 6 >
In the production of the antiglare film of Example 1, an antiglare film was obtained in the same manner as in Example 1 except that the film thickness of the antiglare layer was 0.4 μm.

<Comparative Example 1>
In the production of the antiglare film of Example 1, an antiglare film was obtained in the same manner as in Example 1 except that the reactive inorganic fine particles B were not contained.

<Comparative example 2>
In the production of the antiglare film of Example 1, an antiglare film was obtained in the same manner as in Example 1 except that the average particle size of the reactive inorganic fine particles B (1-1) was d ₅₀ = 10 nm.

〔Evaluation method〕
The following points were evaluated with respect to the above examples and comparative examples. The results are listed in Table 1.
(1) Pencil hardness test Using a pencil having a different hardness, the test was performed in accordance with JIS K5600 under a load of 500 g. The scratch was confirmed visually.
(2) Haze The haze value of the outermost surface of the antiglare film was measured according to JIS K 7105: 1981 “Testing method for optical properties of plastics”.
(3) The presence or absence of cracks when the crack hard coat film was wound around a metal roll having a diameter of 0.5 cm was visually confirmed.

It is sectional drawing of an example of the basic layer structure of the anti-glare film which concerns on this invention. It is sectional drawing of an example of the anti-glare film which concerns on this invention. It is sectional drawing of an example of the anti-glare film which concerns on this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Anti-glare layer 2 Transparent base material 11 Uneven surface layer 12 Surface shape adjustment layer 13 Low refractive index layer

Claims (6)

On the viewer side of the transparent substrate, the outermost surface is an antiglare film comprising an antiglare layer having an uneven shape,
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 concavo-convex layer has the following component (1) translucent fine particles A selected from inorganic fine particles having an average particle size larger than 500 nm,
(2) The average particle diameter is 20 nm or more and 500 nm or less, and at least a part of the surface is coated with an organic component, and the organic component is 3.50 × 10 ⁻³ g / m ² per unit area of the inorganic fine particles before coating. contains more than, the reactive inorganic fine particles B having a group having an ethylenic double bond as a reactive functional group b that is introduced by the organic component to the surface, and (3) an ethylenic double bond as reactivity functional group c Comprising a cured product of a curable resin composition for an antiglare layer containing a binder component C having a group having a curable binder system having curing reactivity in the system ,
And the film thickness of the said uneven | corrugated layer is 0.5 micrometer or more and 3.5 micrometers or less, The anti-glare film characterized by the above-mentioned. The content of the reactive inorganic fine particles B is 1 to 50 parts by weight with respect to 100 parts by weight of the total amount of the reactive inorganic fine particles B and the constituent components of the curable binder system. Antiglare film . 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 anti-glare film according to claim 1 or 2 , which is obtained by dispersing. The anti-glare film according to claim 3 , wherein the surface modifying compound is a compound having at least one hydrogen bond-forming group. The antiglare film according to any one of claims 1 to 4, wherein the transparent substrate is mainly composed of cellulose acylate, cycloolefin polymer, acrylate polymer, or polyester. The antiglare film according to any one of claims 1 to 5, wherein the antiglare layer has a pencil hardness of 3H or more.

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