JP2015200880A - Anti-reflection film, polarizing plate, cover glass, image display device, and manufacturing method for anti-reflection film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an anti-reflection film having a moth-eye structure which has high pencil hardness and prevents particles from dropping out therefrom when stress is applied thereto.SOLUTION: An anti-reflection film comprises a base material and an anti-reflection layer containing a binder resin that contains at least one of a structure derived from (B) below and a structure derived from (C) below and has a moth-eye structure comprising a concavo-convex pattern formed by metal oxide particles (A) described below on a surface thereof on a side opposite an interface with the base material. (A) metal oxide particles having hydroxyl groups on surfaces thereof and having an average primary diameter of 50 to 380 nm, inclusive. (B) a compound having a polymerizable group comprising a (meth)acryloyl group, or a polymerizable group other than a (meth)acryloyl group constituted only of atoms selected from a group of a hydrogen atom, carbon atom, nitrogen atom, and oxygen atom. (C) a compound having a (meth)acryloyl group and a silicon atom directly bonded with at least one of a hydroxyl group and hydrolyzable group.

Description

  The present invention relates to an antireflection film, a polarizing plate, a cover glass, an image display device, and a method for producing an antireflection film.

  In image display devices such as cathode ray tube display (CRT), plasma display (PDP), electroluminescence display (ELD), fluorescent display (VFD), field emission display (FED), and liquid crystal display (LCD), An antireflection film may be provided in order to prevent a decrease in contrast and reflection of an image due to reflection of external light on the display surface. In addition to the image display device, an antireflection function may be provided by an antireflection film.

  As an antireflection film, an antireflection film having a fine uneven shape with a period equal to or less than the wavelength of visible light on the surface of the substrate, that is, an antireflection film having a so-called moth eye structure is known. With the moth-eye structure, it is possible to create a refractive index gradient layer in which the refractive index continuously changes from air to the bulk material inside the substrate, thereby preventing light reflection.

As an antireflection film having a moth-eye structure, Patent Document 1 discloses that a coating liquid containing a transparent resin monomer and fine particles is applied on a transparent substrate and cured to form a transparent resin in which the fine particles are dispersed. An antireflection film having an uneven structure manufactured by etching a resin is described.
Patent Document 2 describes an antireflection member in which ultrafine particles are exposed in a state where they are fixed in the remaining portion of the cured binder layer by dry etching a cured binder layer containing ultrafine particles provided on a substrate. .
In Patent Document 3, a coating liquid containing tetraethoxysilane and ultrafine particles is applied onto a glass substrate and baked to fix ultrafine particles with a thin SiO ₂ film formed by decomposition of tetraethoxysilane. Manufacturing an antireflection body is described.

JP 2009-139796 A JP-A-7-104103 Japanese Patent Laid-Open No. 5-13021

  However, it has been found that the antireflection members described in Patent Documents 1 to 3 have a problem that the particles fall off when a strong stress is applied to the moth-eye structure formed by the particles.

  An object of the present invention is to provide an antireflection film having a moth-eye structure on the surface, which has a high pencil hardness of the moth-eye structure and does not drop particles even when a strong stress is applied to the moth-eye structure. Another object of the present invention is to provide a polarizing plate, a cover glass, an image display device, and a method for producing the antireflection film including the antireflection film.

As a result of intensive studies, the present inventors have found that the above problem can be solved by using a specific component as a material for forming an antireflection layer having a moth-eye structure.
That is, the present invention has the following configuration.

[1]
A substrate;
An antireflection film having an antireflection layer formed from the composition for forming an antireflection layer containing the following (A), (B) and (C),
The antireflection layer includes a binder resin including at least one of a structure derived from the following (B) and a structure derived from the following (C), and the following (on the surface opposite to the interface on the substrate side) ( A) having a moth-eye structure composed of irregularities formed of metal oxide particles of A),
The concave-convex shape of the antireflection layer is such that B / A, which is a ratio of the distance A between the apexes of adjacent convex portions and the distance B between the centers of the adjacent convex portions and the concave portions, is 0.5 or more. An anti-reflection film.
(A) Metal oxide particles having a hydroxyl group on the surface and an average primary particle size of 50 nm or more and 380 nm or less.
(B) having a polymerizable group other than a (meth) acryloyl group composed of only a (meth) acryloyl group or an atom selected from a hydrogen atom, a carbon atom, a nitrogen atom and an oxygen atom as a polymerizable group; A compound having a weight average molecular weight of 1000 or less and having 3 or more polymerizable groups in the molecule.
(C) A compound having a (meth) acryloyl group and having a silicon atom to which at least one of a hydroxyl group and a hydrolyzable group is directly bonded, having a weight average molecular weight of 300 to 1,000.
[2]
The compound (C) is a carbon atom between a carbon atom constituting the carbonyl group in the (meth) acryloyl group and a silicon atom to which at least one of the hydroxyl group and the hydrolyzable group is directly bonded. The antireflective film according to [1], which is a compound having 4 or more.
[3]
The ratio of the number of (meth) acryloyl groups to the number of silicon atoms to which at least one of the hydroxyl group and hydrolyzable group of the compound (C) is directly bonded is 1.1 or more and 3.0 or less, The antireflection film according to [1] or [2].
[4]
The compound (C) is a urethane bond between the carbon atom constituting the carbonyl group in the (meth) acryloyl group and the silicon atom to which at least one of the hydroxyl group and the hydrolyzable group is directly bonded. The antireflection film according to any one of [1] to [3], wherein the antireflection film is a compound having:
[5]
Any one of [1] to [4], wherein the ratio of the mass of (C) to the sum of the mass of (B) and the mass of (C) is 0.2 or more and 0.8 or less. The antireflection film as described in 1.
[6]
The antireflection film according to any one of [1] to [5], wherein the metal oxide particles (A) are metal oxide particles whose surfaces are modified with a compound having a (meth) acryloyl group.
[7]
The antireflection layer according to any one of [1] to [5], wherein in the composition for forming an antireflection layer, the metal oxide particles (A) are surface-modified with the compound (C). the film. [8]
The antireflection film according to any one of [1] to [7], wherein the metal oxide particles are silica particles.
[9]
The antireflection film according to any one of [1] to [8], wherein the metal oxide particles are fired silica particles.
[10]
The antireflection film according to any one of [1] to [9], which has a hard coat layer between the substrate and the antireflection layer.
[11]
A polarizing plate having a polarizer and at least one protective film for protecting the polarizer, wherein at least one of the protective films is the antireflection film according to any one of [1] to [10]. A polarizing plate.
[12]
A cover glass having the antireflection film according to any one of [1] to [10] as a protective film.
[13]
The image display apparatus which has an antireflection film of any one of [1]-[10], or a polarizing plate of [11].
[14]
A method for producing an antireflection film having a substrate and an antireflection layer,
The antireflection layer has a moth-eye structure having a concavo-convex shape formed by the metal oxide particles of the following (A) on the surface opposite to the interface on the substrate side,
The concave-convex shape of the antireflection layer is such that B / A, which is a ratio of the distance A between the apexes of adjacent convex portions and the distance B between the centers of the adjacent convex portions and the concave portions, is 0.5 or more. And
The antireflection film which has the process of apply | coating the composition for antireflection layer containing the following (A), (B) and (C) on the said base material, and hardening the following (B) and (C). Manufacturing method.
(A) Metal oxide particles having a hydroxyl group on the surface and an average primary particle size of 50 nm or more and 380 nm or less.
(B) A compound having three or more (meth) acryloyl groups in one molecule and having a weight average molecular weight of 1,000 or less. However, when the compound (B) has a polymerizable group other than the (meth) acryloyl group, the polymerizable group is a polymerization composed only of atoms selected from a hydrogen atom, a carbon atom, a nitrogen atom and an oxygen atom. Sex group.
(C) A compound having a (meth) acryloyl group and having a silicon atom to which at least one of a hydroxyl group and a hydrolyzable group is directly bonded, having a weight average molecular weight of 300 to 1,000.

  ADVANTAGE OF THE INVENTION According to this invention, the antireflection film which has a moth eye structure on the surface can provide the antireflection film which has high pencil hardness of a moth eye structure, and a particle | grain does not drop even if a strong stress is given to a moth eye structure. Moreover, according to this invention, the polarizing plate containing this antireflection film, a cover glass, an image display apparatus, and the manufacturing method of an antireflection film can be provided.

It is a cross-sectional schematic diagram which shows an example of the antireflection film of this invention.

Hereinafter, preferred embodiments of the present invention will be described in detail. The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
In the present specification, when a numerical value represents a physical property value, a characteristic value, etc., the description “(numerical value 1) to (numerical value 2)” means “(numerical value 1) or more and (numerical value 2) or less”.
Further, “(meth) acrylate” represents at least one of acrylate and methacrylate, “(meth) acryl” represents at least one of acrylic and methacryl, and “(meth) acryloyl” represents at least one of acryloyl and methacryloyl. .

[Antireflection film]
The antireflection film of the present invention is
A substrate;
An antireflection film having an antireflection layer formed from the composition for forming an antireflection layer containing the following (A), (B) and (C),
The antireflection layer includes a binder resin including at least one of a structure derived from the following (B) and a structure derived from the following (C), and the following (on the surface opposite to the interface on the substrate side) ( A) having a moth-eye structure composed of irregularities formed of metal oxide particles of A),
The concave-convex shape of the antireflection layer is such that B / A, which is a ratio of the distance A between the apexes of adjacent convex portions and the distance B between the centers of the adjacent convex portions and the concave portions, is 0.5 or more. It is an antireflection film.
(A) Metal oxide particles having a hydroxyl group on the surface and an average primary particle size of 50 nm or more and 380 nm or less.
(B) having a polymerizable group other than a (meth) acryloyl group composed of only a (meth) acryloyl group or an atom selected from a hydrogen atom, a carbon atom, a nitrogen atom and an oxygen atom as a polymerizable group; A compound having a weight average molecular weight of 1000 or less and having 3 or more polymerizable groups in the molecule.
(C) A compound having a (meth) acryloyl group and having a silicon atom to which at least one of a hydroxyl group and a hydrolyzable group is directly bonded, having a weight average molecular weight of 300 to 1,000.

  Hereinafter, the antireflection film of the present invention will be described in detail.

An example of a preferred embodiment of the antireflection film of the present invention is shown in FIG.
The antireflection film 10 in FIG. 1 has a base material 1 and an antireflection layer 2. The antireflection layer 2 has a moth-eye structure having a concavo-convex shape formed by metal oxide particles 3 on the surface opposite to the interface on the substrate 1 side.
The antireflection layer 2 includes metal oxide particles 3 and a binder resin 4.

(Moth eye structure)
The antireflection layer provided on one side or both sides of the base material of the antireflection film of the present invention has a moth-eye structure having a concavo-convex shape formed by the metal oxide particles of (A).
Here, the moth-eye structure is a processed surface of a substance (material) for suppressing light reflection, and refers to a structure having a periodic fine structure pattern. In particular, for the purpose of suppressing the reflection of visible light, it refers to a structure having a fine structure pattern with a period of less than 780 nm. It is preferable that the period of the fine structure pattern is less than 380 nm because the color of the reflected light is eliminated. A period of 100 nm or more is preferable because light with a wavelength of 380 nm can recognize a fine structure pattern and is excellent in antireflection properties. The presence or absence of the moth-eye structure can be confirmed by observing the surface shape with a scanning electron microscope (SEM), an atomic force microscope (AFM), or the like, and examining whether the fine structure pattern is formed.

The concavo-convex shape of the antireflection layer of the antireflection film of the present invention is B / A, which is a ratio of the distance A between the apexes of adjacent convex portions and the distance B between the center and the concave portion between the apexes of adjacent convex portions. Is 0.5 or more. When B / A is 0.5 or more, the depth of the concave portion increases with respect to the distance between the convex portions, and a refractive index gradient layer in which the refractive index changes more gradually from the air to the inside of the antireflection layer is formed. Therefore, the reflectance can be reduced.
B / A can be controlled by the volume ratio of the binder resin and the metal oxide particles in the antireflection layer after curing. Therefore, it is important to appropriately design the blending ratio between the binder resin and the metal oxide particles. Further, the volume ratio of the binder resin and the metal oxide particles in the antireflection layer is increased in the composition for forming the antireflection layer by allowing the binder resin to permeate the substrate or volatilize in the process of producing the moth-eye structure. Therefore, it is also important to set the matching with the base material appropriately.
Furthermore, in order to make B / A 0.5 or more and reduce the reflectance, it is preferable that the metal oxide particles forming the convex portions are uniformly spread with a high filling rate. In addition, it is important that the filling rate is not too high. If the filling rate is too high, adjacent particles come into contact with each other and the B / A of the concavo-convex structure is reduced. From the above viewpoint, it is preferable that the content of the metal oxide particles forming the convex portion is adjusted so as to be uniform throughout the antireflection layer. The filling rate can be measured as the area occupancy of the particles located on the most surface side when observing the metal oxide particles forming the convex portions from the surface by SEM or the like, and is preferably 30% to 95%, -90% is more preferable, and 50-85% is still more preferable.

A method for measuring B / A, which is a ratio of the distance A between the apexes of adjacent convex portions and the distance B between the center between the apexes of adjacent convex portions and the concave portion, will be described in more detail below.
B / A can be measured by cross-sectional SEM observation of the antireflection film. The antireflection film sample is cut with a microtome to obtain a cross section, and SEM observation is performed at an appropriate magnification (about 5000 times). For easy observation, the sample may be subjected to appropriate processing such as carbon deposition and etching. B / A is the distance between the vertices of adjacent protrusions at the interface between the air and the sample, and the vertices of adjacent protrusions in the plane perpendicular to the substrate surface including the vertices of the adjacent protrusions. The distance between the straight line connecting the two and the vertical bisector reaching the particle or the binder resin is B, and when 100 points are measured, the average value of B / A is calculated.
In the SEM photograph, there are cases where the distance A between the vertices of the adjacent convex portions and the distance B between the vertices of the adjacent convex portions and the concave portion B cannot be measured accurately with respect to all the projected and recessed portions. However, in that case, the length may be measured by paying attention to the convex portion and the concave portion shown on the near side in the SEM image.
Note that the concave portion needs to be measured at the same depth as the particles forming the two adjacent convex portions to be measured in the SEM image. This is because if the distance to a particle or the like reflected on the near side is measured as B, B may be estimated small.

  B / A is preferably 0.6 or more, more preferably 0.7 or more, and still more preferably 0.8 or more. Moreover, from the viewpoint that the moth-eye structure can be firmly fixed and has excellent scratch resistance, it is preferably 0.9 or less.

(Metal oxide particles)
The metal oxide particles forming the moth-eye structure of the antireflection layer will be described.
The metal oxide particles (A) contained in the composition for forming an antireflection layer are metal oxide particles having an average primary particle size having a hydroxyl group on the surface of 50 nm to 380 nm.
In the completed antireflection layer, the hydroxyl group on the surface of the metal oxide particle (A) is a hydroxyl group (silanol group) directly bonded to a silicon atom of the compound (C) or a hydrolyzed bond directly bonded to a silicon atom. A part or all of the decomposable group may disappear due to a condensation reaction with a silanol group formed by hydrolysis. Since the metal oxide particles are strongly bonded to the compound (C) by this condensation reaction, it is preferable because the metal oxide particles are more difficult to fall off even when a strong stress is applied.

The average primary particle size of the metal oxide particles (A) is from 50 nm to 380 nm, preferably from 100 nm to 320 nm, and more preferably from 120 nm to 250 nm. It is preferable that the average primary particle diameter of the metal oxide particles is 50 nm or more because aggregation of the particles can be suppressed. Further, from the viewpoint of haze suppression, it is preferably 380 nm or less, more preferably 300 nm or less, and particularly preferably 220 nm or less.
The average primary particle size of the metal oxide particles refers to the 50% cumulative particle size of the volume average particle size. When measuring the average primary particle diameter of the metal oxide particles contained in the antireflection layer, it can be measured by an electron micrograph. For example, a section TEM image of the antireflection film is taken, the diameter of each of the 100 primary particles is measured to calculate the volume, and the 50% cumulative particle size of the volume average particle size is defined as the average primary particle size. be able to. When the particle is not a spherical diameter, the average value of the major axis and the minor axis is regarded as the diameter of the primary particle.

In the present invention, the amount of hydroxyl groups on the particle surface is defined as follows. The amount of hydroxyl groups is measured by solid ²⁹ Si NMR ( ²⁹ Si CP / MAS). Although the metal element M on the surface of the metal oxide particle is bonded to n hydroxyl groups, the amount of hydroxyl group on the particle surface is Qn × n ÷ (particle radius (unit: nm ) Squared). For example, when the particle is silica (with a particle radius R), silicon bonded to 4 neutral oxygen atoms (signal intensity Q0), silicon bonded to 3 neutral oxygen atoms and one hydroxyl group (signal intensity Q1) , there silicon bonded to two neutral oxygen 2 atoms and hydroxyl groups (signal intensity Q2) is, the particle surface hydroxyl group content is (Q1 × 1 + Q2 × 2 ) ÷ R 2. In the case of silica, the signal giving signal intensity Q2 has a chemical shift of −91 to −94 ppm, the signal giving signal intensity Q1 has a chemical shift of −100 to −102 ppm, and the signal giving signal intensity Q0 has a chemical shift of −109 to −111 ppm.
The more hydroxyl groups on the surface, the greater the amount of reaction, which is preferable. 1.00 × 10 ^{−4 to} 4.00 × 10 ⁻¹ is preferable, 5.00 × 10 ^{−4 to} 3.50 × 10 ⁻¹ is more preferable, and 1.00 × 10 ^{−3 to} 3.00 × 10. ^-1 is more preferable.

The metal oxide particles (A) are preferably metal oxide particles that are surface-modified with a compound having a (meth) acryloyl group. This preferred embodiment is referred to as the first embodiment. The compound having a (meth) acryloyl group is preferably a silane coupling agent having a (meth) acryloyl group. The surface treatment is preferably a silane coupling treatment.
By using metal oxide particles surface-modified with a compound having a (meth) acryloyl group, the (meth) acryloyl group of the compound (C) and the (meth) acryloyl group of the compound (B) are cross-linked. Since the metal oxide particles are firmly fixed to the binder resin and the pencil hardness of the resulting moth-eye structure is higher, and even when a strong stress is applied, the metal oxide particles are more difficult to drop off, which is preferable.
For specific examples of the surface treatment method and preferred examples thereof, reference can be made to the descriptions in [0119] to [0147] of JP-A-2007-298974.
In 1st aspect, it is preferable that content of (C) is 0.01 or more and 6.0 or less by mass ratio with respect to content of (A).

Moreover, in the composition for forming an antireflection layer, an embodiment in which the metal oxide particles (A) are surface-modified with the compound (C) is also preferable. This preferred embodiment is referred to as the second embodiment. According to this aspect, as described above, the hydroxyl group on the surface of the metal oxide particle (A) is directly bonded to the hydroxyl group (silanol group) or silicon atom directly bonded to the silicon atom of the compound (C). When the hydrolyzable group undergoes a condensation reaction with a silanol group formed by hydrolysis, the metal oxide particles are firmly bonded to the compound (C). Further, since the (meth) acryloyl group of the compound (C) modified on the surface of the metal oxide particle (A) is cross-linked with the (meth) acryloyl group of the compound (B), the metal oxide particles are bonded to the binder. The pencil hardness of the resulting moth-eye structure is firmly fixed to the resin, and even after the pencil hardness test, the metal oxide particles fall off more even after checking the adhesion of the particles after applying stress such as rubbing with an eraser. Since it becomes difficult, it is preferable. Further, the second aspect has an advantage that the same effect can be obtained by using a small amount of the compound (C) as compared with the first aspect.
In 2nd aspect, it is preferable that content of (C) modified on the surface of (A) is 0.001 or more and 0.3 or less by mass ratio with respect to content of (A).

  Examples of the metal oxide particles include silica particles, titania particles, zirconia particles, and antimony pentoxide particles. From the viewpoint that moth-eye structures are easily formed because haze is hardly generated because the refractive index is close to that of many binders. Silica particles are preferred.

The metal oxide particles are particularly preferably calcined silica particles.
The calcined silica particles are manufactured by a known technique in which silica particles are obtained by hydrolyzing and condensing a hydrolyzable silicon compound in an organic solvent containing water and a catalyst, and then the silica particles are calcined. For example, JP2003-176121A, JP2008-137854A, and the like can be referred to.
Although it does not specifically limit as a raw material silicon compound which manufactures a burning silica particle, Chlorosilanes, such as tetrachlorosilane, methyltrichlorosilane, phenyltrichlorosilane, dimethyldichlorosilane, diphenyldichlorosilane, methylvinyldichlorosilane, trimethylchlorosilane, methyldiphenylchlorosilane Compounds: tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, trimethoxyvinylsilane, triethoxyvinylsilane, 3-glycidoxypropyltrimethoxysilane, 3-chloro Propyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3- (2-aminoethylamino) propyltrimethoxy Silane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-chloropropylmethyldimethoxysilane, Alkoxysilane compounds such as diphenyldimethoxysilane, diphenyldiethoxysilane, dimethoxydiethoxysilane, trimethylmethoxysilane, trimethylethoxysilane; tetraacetoxysilane, methyltriacetoxysilane, phenyltriacetoxysilane, dimethyldiacetoxysilane, diphenyldiacetoxysilane Acyloxysilane compounds such as trimethylacetoxysilane; dimethylsilanediol, diphenylsilanediol, tri Silanol compounds such as chill silanol; and the like. Of the above-exemplified silane compounds, the alkoxysilane compound is particularly preferred because it is more easily available and the resulting fired silica particles do not contain halogen atoms as impurities. As a preferred form of the calcined silica particles according to the present invention, it is preferred that the halogen atom content is substantially 0% and no halogen atoms are detected.
Although a calcination temperature is not specifically limited, 800-1300 degreeC is preferable and 1000 degreeC-1200 degreeC is more preferable.

The shape of the metal oxide particles is most preferably spherical, but there is no problem even if the shape is not spherical such as indefinite.
The silica particles may be either crystalline or amorphous.
The metal oxide particles may be used by firing commercially available particles. As specific examples, IPA-ST-L (average primary particle size 50 nm, silica sol manufactured by Nissan Chemical Industries, Ltd.), IPA-ST-ZL (average primary particle size 80 nm, silica sol manufactured by Nissan Chemical Industries, Ltd.) , Snowtex MP-1040 (average primary particle size 100 nm, silica manufactured by Nissan Chemical Industries, Ltd.), Snowtex MP-2040 (average primary particle size 200 nm, silica manufactured by Nissan Chemical Industries, Ltd.), Seahoster KE-P10 ( Average primary particle size 150 nm, Nippon Shokubai Co., Ltd. amorphous silica), Seahoster KE-P20 (average primary particle size 200 nm, Nippon Shokubai Co., Ltd. amorphous silica), ASFP-20 (average primary particle size 200 nm, Nippon Electrochemical) (Alumina manufactured by Kogyo Co., Ltd.) and the like can be preferably used. Furthermore, as long as the requirements of the present application are satisfied, commercially available particles may be used as they are.

  The content of the metal oxide particles (A) with respect to the total solid content in the composition for forming an antireflection layer is preferably 10% by mass to 95% by mass, more preferably 35% by mass to 90% by mass, and more preferably 65% by mass. % To 85% by mass is more preferable.

(Binder resin)
The binder resin for the antireflection layer will be described.
The binder resin of the antireflection layer contains at least one of a structure derived from the following (B) and a structure derived from the following (C) in the composition for forming an antireflection layer.
(B) having a polymerizable group other than a (meth) acryloyl group composed of only a (meth) acryloyl group or an atom selected from a hydrogen atom, a carbon atom, a nitrogen atom and an oxygen atom as a polymerizable group; A compound having a weight average molecular weight of 1000 or less and having 3 or more polymerizable groups in the molecule.
(C) A compound having a (meth) acryloyl group and having a silicon atom to which at least one of a hydroxyl group and a hydrolyzable group is directly bonded, having a weight average molecular weight of 300 to 1,000.
Here, the structure derived from (B) is a structure obtained by the reaction of the polymerizable group of compound (B), and the structure derived from (C) is the (meth) acryloyl of compound (C). It is a structure obtained by reacting at least one of a group, a hydroxyl group and a hydrolyzable group.

<Compound (B)>
The compound (B) contained in the composition for forming an antireflection layer will be described.
Compound (B) has a polymerizable group other than a (meth) acryloyl group or a (meth) acryloyl group composed only of an atom selected from a hydrogen atom, a carbon atom, a nitrogen atom and an oxygen atom as a polymerizable group. And a compound having 3 or more polymerizable groups in one molecule and having a weight average molecular weight of 1000 or less.
Specific examples of the polymerizable group other than the (meth) acryloyl group composed only of an atom selected from a hydrogen atom, a carbon atom, a nitrogen atom and an oxygen atom include any of the following formulas (Q-1) to (Q-14). The group represented by these is mentioned, However, It is not limited to these.

  As the polymerizable group that the compound (B) has, a (meth) acryloyl group is preferable.

The compound (B) preferably has 3.0 or more polymerizable groups in one molecule, more preferably 4.0 or more, and still more preferably 5.0 or more.
Specific examples of the compound (B) include alkylene glycol (meth) acrylic acid esters, polyoxyalkylene glycol (meth) acrylic acid diesters, alcohol (meth) acrylic acid esters, ethylene oxide or propylene oxide adducts. (Meth) acrylic acid esters, epoxy (meth) acrylates, urethane (meth) acrylates, polyester (meth) acrylates, and the like.

  Among these, esters of alcohol and (meth) acrylic acid are preferable, and esters of polyhydric alcohol and (meth) acrylic acid are particularly preferable. For example, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, EO modified trimethylolpropane tri (meth) acrylate, PO modified trimethylolpropane tri (meth) acrylate, EO Modified tri (meth) acrylate phosphate, trimethylolethane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa ( (Meth) acrylate, pentaerythritol hexa (meth) acrylate, 1,2,3-cyclohexanetetramethacrylate, urethane acrylate Polyester polyacrylate and caprolactone-modified tris (acryloyloxyethyl) isocyanurate.

The weight average molecular weight of the compound (B) is 1000 or less, preferably 100 or more and 800 or less, and more preferably 200 or more and 700 or less. When the weight average molecular weight of the compound (B) is 1000 or less, the crosslinking density can be increased, which is preferable from the viewpoint of hardness.
The weight average molecular weight is a value expressed in terms of polystyrene by detection with a solvent THF (tetrahydrofuran) and a differential refractometer by GPC (gel permeation chromatography) measured under the following conditions using the following apparatus and column.
[Device Name] TOSOH HLC-8220GPC
[Column] TOSOH TSKgel Super HZM-H
Three (4.6 mm x 15 cm) are connected and used.
[Column temperature] 25 ° C
[Sample concentration] 0.1% by mass
[Flow rate] 0.35 ml / min
[Calibration Curve] A calibration curve with 7 samples from TSKOH TSK standard polystyrene Mw = 2800000 to 1050 is used.

  The content of (B) with respect to the total solid content in the composition for forming an antireflection layer is preferably 1.0% by mass or more and 70.0% by mass or less, and more preferably 2.5% by mass or more and 42.0% by mass or less. Preferably, it is more preferably 6.0% by mass or more and 20.0% by mass or less.

<Compound (C)>
The compound (C) contained in the composition for forming an antireflection layer will be described.
The compound (C) is a compound having a (meth) acryloyl group and having a silicon atom to which at least one of a hydroxyl group and a hydrolyzable group is directly bonded, having a weight average molecular weight of 300 to 1,000.

  The hydrolyzable group of the compound (C) is preferably an alkoxy group, preferably an alkoxy group having 1 to 3 carbon atoms, and most preferably a methoxy group.

From the viewpoint that both the (meth) acryloyl group, the hydroxyl group and the hydrolyzable group in the same molecule easily react, the compound (C) contains a carbon atom constituting a carbonyl group in the (meth) acryloyl group, a hydroxyl group A compound having 4 or more carbon atoms between a silicon atom to which at least one of a group and a hydrolyzable group is directly bonded is preferable.
In the compound (C), the number of carbon atoms between the carbon atom constituting the carbonyl group in the (meth) acryloyl group and the silicon atom to which at least one of a hydroxyl group and a hydrolyzable group is directly bonded is 4 It is more preferably 12 or less and further preferably 6 or more and 10 or less.
Specific examples of such compounds include the following.

From the viewpoint of reacting one or more (meth) acryloyl groups in one molecule with the compound (B), the number of silicon atoms to which at least one of the hydroxyl group and the hydrolyzable group of the compound (C) is directly bonded ( The ratio of the number of (meth) acryloyl groups is preferably 1.1 or more and 3.0 or less.
Specific examples of such compounds include the following.

From the viewpoint of securing the film strength of the binder, the compound (C) is a silicon atom in which a carbon atom constituting a carbonyl group in the (meth) acryloyl group is directly bonded to at least one of a hydroxyl group and a hydrolyzable group. It is preferable that it is a compound which has a urethane bond between these.
Specific examples of such compounds include the following.

The weight average molecular weight of the compound (C) is from 300 to 1,000, preferably from 300 to 800, and more preferably from 300 to 600. When the weight average molecular weight of the compound (C) is 300 or more and 1000 or less, both the (meth) acryloyl group, the hydroxyl group and the hydrolyzable group in the same molecule are easily reacted, and a moth-eye shape is easily obtained. preferable.
The weight average molecular weight is a value expressed in terms of polystyrene by detection with a solvent THF (tetrahydrofuran) and a differential refractometer by GPC (gel permeation chromatography) measured under the following conditions using the following apparatus and column.
[Device Name] TOSOH HLC-8220GPC
[Column] TOSOH TSKgel Super HZM-H
Three (4.6 mm x 15 cm) are connected and used.
[Column temperature] 25 ° C
[Sample concentration] 0.1% by mass
[Flow rate] 0.35 ml / min
[Calibration Curve] A calibration curve with 7 samples from TSKOH TSK standard polystyrene Mw = 2800000 to 1050 is used.

  The number of (meth) acryloyl groups in the compound (C) is preferably 1 to 8 and more preferably 2 to 4 in one molecule.

  The content of (C) with respect to the total solid content in the composition for forming an antireflection layer is preferably 1.0% by mass or more and 70.0% by mass or less, and more preferably 2.5% by mass or more and 42.0% by mass or less. Preferably, it is more preferably 6.0% by mass or more and 20.0% by mass or less.

  Although the specific example of a compound (C) is also shown below, this invention is not limited to these.

  From the viewpoint of firmly adhering the particle-binder and ensuring the binder strength, in the case of the second embodiment described above and other than the embodiment not including (C) as the binder resin forming compound, The mass ratio of the content of (C) to the sum of the content and the content of (C) is preferably 0.1 or more and 0.9 or less, and more preferably 0.2 or more and 0.8 or less. And more preferably 0.3 or more and 0.7 or less, and particularly preferably 0.4 or more and 0.6 or less.

(Base material)
The base material in the antireflection film of the present invention is not particularly limited as long as it is a base material having translucency generally used as the base material of the antireflection film, but a plastic base material and a glass base material are preferable.
Various plastic substrates can be used, such as cellulose resin; cellulose acylate (triacetate cellulose, diacetyl cellulose, acetate butyrate cellulose), polyester resin; polyethylene terephthalate, (meth) acrylic resin, polyurethane, etc. Base materials containing polycarbonate resins, polycarbonates, polystyrenes, olefin resins, etc., preferably cellulose acylates, polyethylene terephthalates, or substrates containing (meth) acrylic resins, and substrates containing cellulose acylates Is more preferable. As the cellulose acylate, the base material described in JP 2012-093723 A can be preferably used.
The thickness of the plastic substrate is usually about 10 μm to 1000 μm, but 20 μm to 200 μm is preferable, and 25 μm to 100 μm is preferable from the viewpoint of good handleability, high translucency, and sufficient strength. More preferred. As a light-transmitting property of the plastic substrate, a material having a visible light transmittance of 90% or more is preferable.

(Other functional layers)
The antireflection film of the present invention may have a functional layer other than the antireflection layer.
For example, the aspect which has a hard-coat layer between a base material and an antireflection layer is mentioned preferably. Further, an easy adhesion layer for imparting adhesion, a layer for imparting antistatic properties, or the like may be provided, or a plurality of these may be provided.

[Method for producing antireflection film]
Although the manufacturing method of the antireflection film of the present invention is not particularly limited, a manufacturing method using a coating method is preferable from the viewpoint of production efficiency.
That is, the manufacturing method of the antireflection film is:
A method for producing an antireflection film having a substrate and an antireflection layer,
The antireflection layer has a moth-eye structure having a concavo-convex shape formed by the metal oxide particles of the following (A) on the surface opposite to the interface on the substrate side,
The concave-convex shape of the antireflection layer is such that B / A, which is a ratio of the distance A between the apexes of adjacent convex portions and the distance B between the centers of the adjacent convex portions and the concave portions, is 0.5 or more. And
The antireflection film which has the process of apply | coating the composition for antireflection layer containing the following (A), (B) and (C) on the said base material, and hardening the following (B) and (C). It is a manufacturing method.
(A) Metal oxide particles having a hydroxyl group on the surface and an average primary particle size of 50 nm or more and 380 nm or less.
(B) A compound having three or more (meth) acryloyl groups in one molecule and having a weight average molecular weight of 1,000 or less. However, when the compound (B) has a polymerizable group other than the (meth) acryloyl group, the polymerizable group is a polymerization composed only of atoms selected from a hydrogen atom, a carbon atom, a nitrogen atom and an oxygen atom. Sex group.
(C) A compound having a (meth) acryloyl group and having a silicon atom to which at least one of a hydroxyl group and a hydrolyzable group is directly bonded, having a weight average molecular weight of 300 to 1,000.

The composition for forming an antireflection layer may contain a solvent, a polymerization initiator, a metal complex compound, a particle dispersant, a leveling agent, an antifouling agent, and the like.
A solvent having a polarity close to that of the fine particles is preferably selected from the viewpoint of improving dispersibility. Specifically, for example, when the fine particles are metal oxide particles, an alcohol solvent is preferable, and examples thereof include methanol, ethanol, 2-propanol, 1-propanol, and butanol. For example, when the fine particles are metal resin particles having a hydrophobic surface modified, ketone-based, ester-based, carbonate-based, alkane, aromatic-based solvents are preferable, and methyl ethyl ketone (MEK), dimethyl carbonate, methyl acetate are preferable. , Acetone, methylene chloride, cyclohexanone and the like. These solvents may be used in a mixture of a plurality of types as long as the dispersibility is not significantly deteriorated.
The particle dispersing agent can facilitate uniform arrangement of the particles by reducing the cohesive force between the particles. The dispersant is not particularly limited, but is preferably an anionic compound such as a sulfate or phosphate, a cationic compound such as an aliphatic amine salt or a quaternary ammonium salt, a nonionic compound or a polymer compound. And a steric repulsion group are more preferred because they have a high degree of freedom in selection. A commercial item can also be used as a dispersing agent. For example, BYK Japan made of (stock) DISPERBYK160, DISPERBYK161, DISPERBYK162, DISPERBYK163, DISPERBYK164, DISPERBYK166, DISPERBYK167, DISPERBYK171, DISPERBYK180, DISPERBYK182, DISPERBYK2000, DISPERBYK2001, DISPERBYK2164, Bykumen, BYK-P104, BYK-P104S, BYK-220S, Anti-Terra 203, Anti-Terra 204, Anti-Terra 205 (named above) are listed.
By reducing the surface tension of the coating solution, the leveling agent can stabilize the solution after coating and facilitate the uniform arrangement of particles and binder resin. For example, the compounds described in JP-A-2004-331812 and JP-A-2004-163610 can be used.
The antifouling agent can suppress adhesion of dirt and fingerprints by imparting water and oil repellency to the moth-eye structure. For example, compounds described in JP 2012-88699 A can be used.
By adding the metal complex compound, hydrolysis of the compound (C) can be promoted and the reactivity can be increased. The metal complex compound is not particularly limited as long as it contains a metal atom and a ligand coordinated thereto, and can be appropriately selected depending on the purpose. For example, di-n-propoxy bis (acetyl Acetonato) zirconium, di-iso-propoxy bis (acetylacetonato) zirconium, di-n-butoxy bis (acetylacetonato) zirconium, di-tert-butoxy bis (acetylacetonato) zirconium, mono-n -Propoxy-tris (acetylacetonato) zirconium, mono-iso-propoxy-tris (acetylacetonato) zirconium, mono-n-butoxy-tris (acetylacetonato) zirconium, mono-tert-butoxy-tris (acetylacetonate) ) Zirconium, zirconi Mutaacetylacetonate, di-n-propoxy bis (ethyl acetoacetate) zirconium, di-iso-propoxy bis (ethyl acetoacetate) zirconium, di-n-butoxy bis (ethyl acetoacetate) zirconium, di- tert-butoxy bis (ethyl acetoacetate) zirconium, mono-n-propoxy tris (ethyl acetoacetate) zirconium, mono-iso-propoxy tris (ethyl acetoacetate) zirconium, mono-n-butoxy tris (ethyl acetoacetate) Acetate) zirconium, mono-tert-butoxy-tris (ethylacetoacetate) zirconium, zirconium tetraethylacetoacetate, mono (acetylacetonato) tris (ethylacetoacetate) ) Zirconium, bis (acetylacetonato) bis (ethylacetoacetate) zirconium, tris (acetylacetonato) mono (ethylacetoacetate) zirconium, di-n-propoxy mono (acetylacetonato) aluminum, di-iso -Propoxy mono (acetylacetonato) aluminum, di-n-butoxy mono (acetylacetonato) aluminum, di-tert-butoxy mono (acetylacetonato) aluminum, mono-n-propoxybis (acetylacetonate) ) Aluminum, mono-iso-propoxy bis (acetylacetonate) aluminum, mono-n-butoxy bis (acetylacetonate) aluminum, mono-tert-butoxy bis (acetylacetonate) ) Aluminum, aluminum trisacetylacetonate, di-n-propoxy mono (ethyl acetoacetate) aluminum, di-iso-propoxy mono (ethyl acetoacetate) aluminum, di-n-butoxy mono (ethyl acetoacetate) aluminum , Di-tert-butoxy mono (ethyl acetoacetate) aluminum, mono-n-propoxy bis (ethyl acetoacetate) aluminum, mono-iso-propoxy bis (ethyl acetoacetate) aluminum, mono-n-butoxy bis (Ethyl acetoacetate) aluminum, mono-tert-butoxy bis (ethyl acetoacetate) aluminum, aluminum trisethyl acetoacetate, mono (acetylacetonate) bis (d Le acetoacetate) aluminum, bis (acetylacetonate) mono (ethylacetoacetate) and aluminum. These may be used alone or in combination of two or more.

(Polymerization initiator)
The composition for forming an antireflection layer preferably contains a polymerization initiator, and more preferably contains a photopolymerization initiator.
As photopolymerization initiators, acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkyldione compounds, disulfide compounds, Examples include fluoroamine compounds, aromatic sulfoniums, lophine dimers, onium salts, borate salts, active esters, active halogens, inorganic complexes, and coumarins. Specific examples, preferred embodiments, commercially available products, and the like of the photopolymerization initiator are described in paragraphs [0133] to [0151] of JP-A-2009-098658, and can be suitably used in the present invention as well. it can.
“Latest UV Curing Technology” {Technical Information Association, Inc.} (1991), p. 159, and “UV Curing System” written by Kiyomi Kato (published by the General Technology Center in 1989), p. Various examples are also described in 65-148 and are useful in the present invention.

  A method for applying the composition for forming an antireflection layer is not particularly limited, and a known method can be used. Examples include dip coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating, and die coating.

  From the viewpoint of easy application uniformly, the solid content concentration of the composition for forming an antireflection layer is preferably 10% by mass or more and 80% by mass or less, and more preferably 20% by mass or more and 60% by mass or less.

[Polarizer]
The polarizing plate of the present invention is a polarizing plate having a polarizer and at least one protective film for protecting the polarizer, and at least one of the protective films is the antireflection film of the present invention.

  Examples of the polarizer include an iodine polarizing film, a dye polarizing film using a dichroic dye, and a polyene polarizing film. The iodine-based polarizing film and the dye-based polarizing film can be generally produced using a polyvinyl alcohol film.

[cover glass]
The cover glass of the present invention has the antireflection film of the present invention as a protective film. The base material of the antireflection film may be made of glass, or an antireflection film having a plastic film base material may be pasted on a glass support.

[Image display device]
The image display device of the present invention has the antireflection film or the polarizing plate of the present invention.
The antireflection film and polarizing plate of the present invention are preferably used for image display devices such as liquid crystal display devices (LCD), plasma display panels (PDP), electroluminescence displays (ELD), and cathode ray tube display devices (CRT). In particular, a liquid crystal display device is preferable.
In general, a liquid crystal display device has a liquid crystal cell and two polarizing plates arranged on both sides thereof, and the liquid crystal cell carries a liquid crystal between two electrode substrates. Furthermore, one optically anisotropic layer may be disposed between the liquid crystal cell and one polarizing plate, or two optically anisotropic layers may be disposed between the liquid crystal cell and both polarizing plates. The liquid crystal cell is preferably in TN mode, VA mode, OCB mode, IPS mode or ECB mode.

  The present invention will be described more specifically with reference to the following examples. The amounts, ratios and operations of materials, reagents, and substances shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the following specific examples.

(Production of substrate with hard coat layer)
A cellulose triacetate film (TDH60UF, manufactured by Fuji Film Co., Ltd.) is coated with a coating solution for forming a hard coat layer having the following composition, and irradiated with ultraviolet rays having an irradiation amount of 60 mJ / cm ² with an air-cooled metal halide lamp while purging with nitrogen. It hardened | cured and formed the hard-coat layer with a film thickness of 8 micrometers. Thus, the base material with a hard-coat layer was produced.

<Composition of coating liquid for forming hard coat layer>
A-TMMT 44.6 parts by mass Irgacure 127 1.9 parts by mass Methyl ethyl ketone 10.7 parts by mass Methyl isobutyl ketone 37.5 parts by mass Methyl acetate 5.4 parts by mass

(Preparation of coating solution for antireflection layer formation)
Each component is put into a mixing tank so as to have the composition shown in Table 1 below, stirred for 60 minutes, dispersed with an ultrasonic disperser for 30 minutes, and filtered through a polypropylene filter having a pore size of 5 μm to form a coating solution for forming an antireflection layer. It was.
As (A), (B) and (C) in Table 1 below, compositions for forming an antireflection layer in each Example and Comparative Example were prepared using the materials described in Table 2 below.

In Table 1 above, the unit of the amount of each component represents “parts by mass”.
Moreover, (B) and (C) were used as a binder resin forming compound so that it might become 32.4 mass parts in total.

(Preparation of antireflection film)
On the hard coat layer of the substrate with a hard coat layer, each antireflection layer forming composition using the materials shown in Table 2 below as (A), (B) and (C) is applied using a gravure coater. Then, after drying at 120 ° C. for 5 minutes, it was cured by irradiating with an ultraviolet ray with an irradiation amount of 600 mJ / cm ² with an air-cooled metal halide lamp while purging with nitrogen so that the atmosphere had an oxygen concentration of 0.1% by volume or less. The antireflection film of Examples 1-34 and Comparative Examples 1-5 was produced.

  Example except that Fujitac TG60UL (manufactured by FUJIFILM Corporation) was used instead of the cellulose triacetate film (TDH60UF, manufactured by FUJIFILM Corporation), and the composition for forming an antireflection layer having the composition shown in Table 3 below was used. In the same manner as in Example 1, antireflection films of Examples 35 to 51 were produced.

(Evaluation of antireflection film)
Various characteristics of the antireflection film were evaluated by the following methods. The results are shown in Table 2.

(Integral reflectance)
The back surface of the antireflection film (cellulose triacetate film side) is roughened with sandpaper, then treated with black ink, and the back surface reflection is eliminated. The adapter is attached to the spectrophotometer V-550 (manufactured by JASCO Corporation). With ARV-474 attached, the integrated reflectance at an incident angle of 5 ° was measured in the wavelength region of 380 to 780 nm, and the average reflectance was calculated to evaluate the antireflection property.

(Pencil hardness test and eraser rub test after pencil hardness test)
A pencil hardness test (H / 2H / 3H) was performed on the surface of the antireflection layer, and then the pencil was removed with an eraser.
The pencil hardness test was performed by the pencil hardness evaluation method specified by JIS-K5400 using a test pencil specified by JIS-S6006 after humidity was adjusted for 2 hours at 25 ° C. and a relative humidity of 60%.
Using a rubbing tester, the pencil test part was rubbed with an eraser.
Evaluation environmental conditions: 25 ° C., 60% RH.
Rubbing material: A plastic eraser {"MONO" manufactured by Dragonfly Pencil Co., Ltd.) was fixed to the rubbing tip (1 cm x 1 cm) of the tester that was in contact with the sample.
Rub speed: 2 cm / sec
Load: 250 g / cm ²
Tip contact area: 1 cm x 1 cm
Number of rubbing: 50 reciprocations The number of particles was counted from SEM photographs of the pencil test unexecuted part and the implemented part, and the residual ratio of the particles was calculated.
Particle residual ratio = (number of particles per unit area of pencil hardness test execution part / number of particles per unit area of pencil hardness test non-execution part) × 100
A: Particle residual ratio of 80% or more B: Particle residual ratio of 60% or more and less than 80% C: Particle residual ratio of less than 60%

(B / A)
The antireflection film sample was cut with a microtome to obtain a cross section, and the cross section was etched for 10 minutes after carbon deposition. Using a scanning electron microscope (SEM), 20 fields of view were observed and photographed at a magnification of 5000 times. In the obtained image, at the interface between the air and the sample, the distance A between the vertices of the adjacent convex portions and the distance B between the vertices of the adjacent convex portions and the concave portion are measured by 100 points, and B / A It was calculated as an average value.

In Table 2 and Table 3, (C) / ((B) + (C)) is a mass ratio of the content of the compound (C) to the total content of the compound (B) and the compound (C).
In Examples 19 to 28 and 39 to 48, a compound corresponding to the compound (C) is used as the surface treatment coupling agent for the metal oxide particles (A) (corresponding to the second aspect described above).

The compounds used are shown below.
Irgacure 127: Photopolymerization initiator (manufactured by BASF Japan Ltd.)
KE-S10: Sea Hoster KE-S10 Nippon Shokubai KE-S30: Sea Hoster KE-S30 Nippon Shokubai

[Synthesis of Silica Particle A1]
A 200 L reactor equipped with a stirrer, a dropping device and a thermometer was charged with 67.54 kg of methyl alcohol and 26.33 kg of 28% by mass aqueous ammonia (water and catalyst), and the liquid temperature was kept at 33 ° C. while stirring. Adjusted. Meanwhile, a dropping device was charged with a solution prepared by dissolving 12.70 kg of tetramethoxysilane in 5.59 kg of methyl alcohol. While maintaining the liquid temperature in the reactor at 33 ° C., the above solution was dropped from the dropping device over 1 hour, and after completion of the dropping, stirring was further performed for 1 hour while maintaining the liquid temperature at the above temperature. Hydrolysis and condensation of methoxysilane was performed to obtain a dispersion containing a silica particle precursor. Silica particles were obtained by air-drying this dispersion under the conditions of a heated tube temperature of 175 ° C. and a reduced pressure of 200 torr (27 kPa) using an instantaneous vacuum evaporator (Crox System CVX-8B type manufactured by Hosokawa Micron Corporation). A1 was obtained. The average particle size was 200 nm, and the degree of dispersion (Cv value) of the particle size was 3.5%.

[Preparation of calcined silica particles A2]
5 kg of silica particles A1 were put in a crucible, fired at 1050 ° C. for 1 hour using an electric furnace, cooled, and then ground using a grinder to obtain pre-classified fired silica particles. Furthermore, the pulverized silica particles A2 were obtained by crushing and classifying using a jet pulverizing and classifying machine (IDS-2 type manufactured by Nippon Puma Co., Ltd.). The average particle size of the obtained silica particles was 0.20 μm, and the degree of particle size dispersion (Cv value) was 3.5%.

[Production of Silane Coupling Agent-treated Silica Particles A3-C1 to A3-C6]
5 kg of pre-classified sintered silica particles A2 were charged into a 20 L Henschel mixer (FM20J type, manufactured by Mitsui Mining Co., Ltd.) equipped with a heating jacket. While the fired silica particles A2 were being stirred, a solution prepared by dissolving 45 g of C1 to C6 in 90 g of methyl alcohol was added dropwise and mixed. Then, it heated up to 150 degreeC over about 1 hour, mixing and stirring, and heat-processed by hold | maintaining at 150 degreeC for 12 hours. In the heat treatment, scrapes on the wall surface were scraped while the scraping device was always rotated in the direction opposite to the stirring blade. Moreover, the wall deposits were also scraped off using a spatula as appropriate. After heating, the mixture was cooled and pulverized and classified using a jet pulverizer to obtain silane coupling agent-treated silica particles A3-C1 to A3-C6. In all cases, the average particle size was 0.21 μm, and the degree of particle size dispersion (Cv value) was 3.7%.

[C1]
To a flask equipped with a reflux condenser and a thermometer, 13.6 g of Shin-Etsu Chemical KBE-9007, 16.4 g of pentaerythritol triacrylate, 0.1 g of dibutyltin dilaurate and 70.0 g of toluene were added, and 12 hours at room temperature. Stir. After stirring, 500 ppm of methylhydroquinone was added and distilled off under reduced pressure to obtain C1.

[C2]
To a flask equipped with a reflux condenser and a thermometer, 9.1 g of Shin-Etsu Chemical KBE-9007, 20.9 g of 1,3-diacryloyloxy-2-propanol, 0.1 g of dibutyltin dilaurate and 70.0 g of toluene were added. And stirred at room temperature for 12 hours. After stirring, 500 ppm of methylhydroquinone was added and distilled off under reduced pressure to obtain C2.

[C3]
In a flask equipped with a reflux condenser and a thermometer, 19.3 g of KBE-9007 manufactured by Shin-Etsu Chemical Co., Ltd., 3.9 g of glycerol 1,3-bisacrylate, 6.8 g of 2-hydroxyethyl acrylate, 0.1 g of dibutyltin dilaurate, 70.0 g of toluene was added and stirred at room temperature for 12 hours. After stirring, 500 ppm of methylhydroquinone was added and distilled off under reduced pressure to obtain C3.

[C5]
To a flask equipped with a reflux condenser and a thermometer, 9.1 g of KBE-9007 manufactured by Shin-Etsu Chemical Co., Ltd., 20.9 g of dipentaerythritol pentaacrylate, 0.1 g of dibutyltin dilaurate and 70.0 g of toluene were added, and 12 hours at room temperature. Stir. After stirring, it was distilled off under reduced pressure to obtain C5.

[C7] X-40-2671G manufactured by Shin-Etsu Chemical Co., Ltd.
X-40-2671G is represented by the general formula (2) described in JP2007-41495A. Here, R ¹ is a hydrogen atom, Y is * -COO-**, L is a linking group having 3 carbon atoms (C ₃ H ₆ ), R ² , R ³ and R ⁴ are methoxy groups, R ⁵ , R ⁶ is a methyl group. The weight average molecular weight was 1300-1900.

KAYARAD PET-30: A mixture of pentaerythritol tetraacrylate and pentaerythritol triacrylate (manufactured by Nippon Kayaku Co., Ltd.)
KAYARAD DPHA: Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.)
Light ester HO-250 (N): hydroxylethyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd.)
A-DPH: Dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Kogyo)
A-TMMT: Pentaerythritol tetraacrylate (manufactured by Shin-Nakamura Kogyo)

DESCRIPTION OF SYMBOLS 1 Base material 2 Antireflection layer 3 Metal oxide particle 4 Binder resin 10 Antireflection film A Distance between the vertices of the adjacent convex portions B Distance between the centers of the adjacent convex portions and the concave portions

Claims (14)

A substrate;
An antireflection film having an antireflection layer formed from the composition for forming an antireflection layer containing the following (A), (B) and (C),
The antireflection layer includes a binder resin including at least one of a structure derived from the following (B) and a structure derived from the following (C), and the following (on the surface opposite to the interface on the substrate side) ( A) having a moth-eye structure composed of irregularities formed of metal oxide particles of A),
The concave-convex shape of the antireflection layer is such that B / A, which is a ratio of the distance A between the apexes of adjacent convex portions and the distance B between the centers of the adjacent convex portions and the concave portions, is 0.5 or more. An anti-reflection film.
(A) Metal oxide particles having a hydroxyl group on the surface and an average primary particle size of 50 nm or more and 380 nm or less.
(B) having a polymerizable group other than a (meth) acryloyl group composed of only a (meth) acryloyl group or an atom selected from a hydrogen atom, a carbon atom, a nitrogen atom and an oxygen atom as a polymerizable group; A compound having a weight average molecular weight of 1000 or less and having 3 or more polymerizable groups in the molecule.
(C) A compound having a (meth) acryloyl group and having a silicon atom to which at least one of a hydroxyl group and a hydrolyzable group is directly bonded, having a weight average molecular weight of 300 to 1,000.   The compound (C) is a carbon atom between a carbon atom constituting a carbonyl group in the (meth) acryloyl group and a silicon atom to which at least one of the hydroxyl group and the hydrolyzable group is directly bonded. The antireflection film according to claim 1, which is a compound having 4 or more.   The ratio of the number of (meth) acryloyl groups to the number of silicon atoms to which at least one of the hydroxyl group and hydrolyzable group of the compound (C) is directly bonded is 1.1 or more and 3.0 or less, The antireflection film according to claim 1 or 2.   The compound (C) is a urethane bond between a carbon atom constituting a carbonyl group in the (meth) acryloyl group and a silicon atom to which at least one of the hydroxyl group and the hydrolyzable group is directly bonded. The antireflection film according to any one of claims 1 to 3, which is a compound having   The ratio of the mass of (C) to the sum of the mass of (B) and the mass of (C) is 0.2 or more and 0.8 or less. Antireflection film.   The antireflection film according to any one of claims 1 to 5, wherein the metal oxide particles (A) are metal oxide particles surface-modified with a compound having a (meth) acryloyl group.   The antireflection film according to any one of claims 1 to 5, wherein in the composition for forming an antireflection layer, the metal oxide particles (A) are surface-modified with the compound (C).   The antireflection film according to any one of claims 1 to 7, wherein the metal oxide particles are silica particles.   The antireflection film according to claim 1, wherein the metal oxide particles are fired silica particles.   The antireflection film according to claim 1, further comprising a hard coat layer between the substrate and the antireflection layer.   Polarized light having a polarizer and at least one protective film for protecting the polarizer, wherein at least one of the protective films is the antireflection film according to any one of claims 1 to 10. Board.   The cover glass which has an antireflection film of any one of Claims 1-10 as a protective film.   The image display apparatus which has an antireflection film of any one of Claims 1-10, or a polarizing plate of Claim 11. A method for producing an antireflection film having a substrate and an antireflection layer,
The antireflection layer has a moth-eye structure having a concavo-convex shape formed of metal oxide particles of the following (A) on the surface opposite to the interface on the substrate side,
The concave-convex shape of the antireflection layer is such that B / A, which is a ratio of the distance A between the apexes of adjacent convex portions and the distance B between the centers of the adjacent convex portions and the concave portions, is 0.5 or more. And
The antireflection film which has the process of apply | coating the composition for antireflection layer containing the following (A), (B) and (C) on the said base material, and hardening the following (B) and (C). Manufacturing method.
(A) Metal oxide particles having a hydroxyl group on the surface and an average primary particle size of 50 nm or more and 380 nm or less.
(B) A compound having three or more (meth) acryloyl groups in one molecule and having a weight average molecular weight of 1,000 or less. However, when the compound (B) has a polymerizable group other than the (meth) acryloyl group, the polymerizable group is a polymerization composed only of atoms selected from a hydrogen atom, a carbon atom, a nitrogen atom and an oxygen atom. Sex group.
(C) A compound having a (meth) acryloyl group and having a silicon atom to which at least one of a hydroxyl group and a hydrolyzable group is directly bonded, having a weight average molecular weight of 300 to 1,000.

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