JP2005266782A - Anti reflection film, polarizer using it, picture display device using them, and manufacturing method of anti reflection film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an anti reflection film whose reflectivity is low and excellent in anti-scratching property, antifouling property and durability, and to provide a polarizer and a picture display device using the anti reflection film. <P>SOLUTION: In an anti reflection film containing a low refractive index layer formed by applying at least a component for forming the low refractive index layer on a transparent support, the component for forming the low refractive index layer contains at least either of the hydrolyzate of organic Cyril compound shown by the following general formula (1) and its partial condensate, and the center line surface roughness Ra of the outermost surface of the anti-reflection film is 0.005 to 0.30 μm. In general formula (1):R<SP>11</SP><SB>m</SB>Si(X<SP>11</SP>)<SB>n</SB>, X<SP>11</SP>expresses -OH, halogen atom, -OR<SP>12</SP>group or -OCOR<SP>12</SP>. R<SP>11</SP>expresses an alkyl group, an alkenyl group or an aryl group, R<SP>12</SP>expresses an alkyl group. m+n is 4, and m and n are respectively positive integers. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an antireflection film having a low reflectance and excellent scratch resistance, antifouling properties and durability, a polarizing plate using the same, and an image display device using them. Furthermore, the present invention relates to an antireflection film with reduced glare and an increased viewing angle, a polarizing plate using the same, and an image display device using them.

  In general, an antireflection film is used for an image display device such as a cathode ray tube display (CRT), a plasma display (PDP), an electroluminescence display (ELD), and a liquid crystal display (LCD). Is used for the purpose of reducing reflectivity using the principle of optical interference. In addition, in order to obtain display performance with less glare, an anti-glare layer that scatters the reflected light with an uneven surface is introduced, or light from the inside of the image display device is introduced by introducing particles having a refractive index different from that of the binder. Consideration has been made to improve the viewing angle by diffusing.

  Since the image display device is used for a long period of time in various environments, durability is required. In particular, when the reflectance is lowered using optical interference, the effect of suppressing the reflectance is lost due to deterioration of the optical interference layer. Further, when the optical thin film deteriorates unevenly, unevenness occurs and becomes a conspicuous defect. Furthermore, since the antireflection film is used on the outermost surface, it is expected to have a function as a protective film of an image display device, and it is required that dirt and dust are difficult to adhere and that scratch resistance is strong.

  As a protective film having high scratch resistance, it is known to use a sol-gel film of a hydrolytic condensate of alkoxysilane. For example, Patent Document 1 discloses a three-layer optical interference type antireflection film using a sol-gel film, Patent Document 2 discloses a method of reducing the reflectance by applying a sol-gel film on a plastic substrate, and Patent Document 3 discloses an alkoxy film. Sol-gel film containing silane and low refractive index inorganic fine particles, Patent Document 4 is a sol-gel film of an ethylenically unsaturated group-containing organic silyl compound, Patent Document 5 is a combination of a sol-gel film and an antifouling layer, Patent Document 6 describes a low refractive index coating agent comprising a fluorine-containing organosilane.

However, in general, although the sol-gel film has a high initial strength, it has a drawback that the film is fragile and easily soiled. In particular, it is insufficient in terms of storage conditions under high humidity, severe temperature changes, and durability under an ozone-containing atmosphere, and improvement has been demanded. In addition, when combined with a fluorine-based organic silyl compound, the antifouling property is improved, but the film strength is lowered, or the charging property is increased and the adhesion of dust is increased. .
JP-A-10-728 Japanese Patent Laid-Open No. 63-21601 JP-A-8-211202 JP 2002-275403 A JP 2002-277604 A JP 2002-265866 A

As described above, the conventionally proposed antireflection films are insufficient in terms of both excellent display performance with low reflectivity and scratch resistance, antifouling properties and durability. Development of an antireflection film capable of satisfying the above has been demanded.

  An object of the present invention is to provide an antireflection film having a low reflectance and excellent scratch resistance, antifouling properties and durability. Furthermore, it is providing the antireflection film with which the glare was suppressed and the viewing angle was expanded. Moreover, it is providing the polarizing plate using such an antireflection film, and an image display apparatus using them.

As a result of intensive studies, the inventors of the present invention constituted a low refractive index layer using at least one of a hydrolyzate of a specific organic silyl compound and a partial condensate thereof, and the center line of the outermost surface at that time. It has been found that the above object can be achieved by controlling the surface roughness within a specific range.
That is, the present invention achieves the above object by the following configuration.

(1) In an antireflection film provided with an antireflection layer including a low refractive index layer formed by coating at least a composition for forming a low refractive index layer on a transparent support, the composition for forming a low refractive index layer The product contains at least one of a hydrolyzate of an organic silyl compound represented by the following general formula (1) and a partial condensate thereof, and the centerline surface roughness Ra of the outermost surface of the antireflection film is 0.005. An antireflection film having a thickness of ˜0.30 μm.
General formula (1): R ¹¹ _m Si (X ¹¹ ) _n
(In the formula, X ¹¹ represents —OH, a halogen atom, —OR ¹² group, or —OCOR ¹² group. R ¹¹ represents an alkyl group, an alkenyl group, or an aryl group, and R ¹² represents an alkyl group. M + n represents 4 and m and n are each a positive integer.)

(2) The low refractive index layer contains inorganic fine particles having an average particle size of 30% to 120% of the thickness of the low refractive index layer and having a hollow structure and a refractive index of 1.17 to 1.40. The antireflection film according to (1) above.
(3) The antireflection film as described in (1) or (2) above, wherein the surface free energy on the outermost surface is 26 mJ / m ² or less.

(4) The antireflection film is a multilayer structure film further comprising a hard coat layer, and at least one of the constituent layers of the antireflection layer contains at least one translucent particle having an average particle diameter of 0.1 to 5 μm. A light diffusing layer dispersed in a seed, a translucent resin, and the difference in refractive index between the translucent particle and the translucent resin is 0.02 to 0.2, and the translucent particle Is an antireflection film as described in (1) to (3) above, wherein 3 to 30% by mass is contained in the total solid content of the light diffusion layer.

(5) The antireflection film according to any one of (1) to (4), wherein the antireflection film further comprises a transparent antistatic layer having a conductive material, and the surface resistance value logSR of the antireflection film is 12 or less. .
(6) The hard coat layer is formed by coating a composition for forming a hard coat layer containing at least one of the organic silyl compound represented by the general formula (1), a hydrolyzate thereof, and a partial condensate thereof. The antireflection film as described in (4) above.

(7) The antireflection film as described in (4) or (6) above, wherein the composition for forming a hard coat layer contains a polyfunctional isocyanate compound.
(8) The antireflection film as described in (4), (6) or (7) above, wherein the center line surface roughness Ra of the hard coat layer is 0.005 to 0.20 μm.

(9) The antireflection film according to any one of (1) to (8), wherein at least one of the constituent layers of the antireflection film contains a thixotropic agent.
(10) The antireflection film as described in (1) to (9) above, which has an antifouling layer on the upper layer of the low refractive index layer.
(11) The antireflection film as described in (1) to (9) above, wherein the low refractive index layer is provided on the surface treated with alkali.

(12) The reflection according to any one of (1) to (11) above, wherein a limit load in a water swab rubbing test on the surface of the antireflection film after exposure to 10 ppm ozone for 192 hours is 400 g or more. Prevention film.

(13) A polarizing plate comprising the antireflection film according to any one of (1) to (11) above.
(14) The polarizing plate according to (13), wherein the Re retardation value of at least one film constituting the polarizing plate is 20 to 70 nm and the Rth retardation value is 70 to 400 nm.

(15) The polarizing plate as described in (13) or (14) above, wherein a limit load in a water swab rubbing test on the surface of the antireflection film after exposure to 10 ppm ozone for 192 hours is 400 g or more.

(16) A display device comprising the antireflection film according to any one of (1) to (12) above or the polarizing plate according to any one of (13) to (15) above.

(17) The display device according to (16) above, wherein a limit load in a water swab rubbing test on the surface of the antireflection film after exposure to 10 ppm ozone for 192 hours is 400 g or more.

  The antireflection film of the present invention has sufficient antireflection properties and is excellent in scratch resistance, antifouling properties and durability. Furthermore, the image display device provided with the antireflection film of the present invention and the image display device provided with the polarizing plate using the antireflection film of the present invention have little external light and background reflection and glare, and have a viewing angle. Wide and extremely high visibility.

Hereinafter, the present invention will be described in more detail.
In the specification of the present application, the description “(numerical value A) to (numerical value B)” representing a characteristic value, a physical property value, etc. means “(numerical value A) or more and (numerical value B) or less”.

The antireflective film of the present invention comprises an antireflective layer including a low refractive index layer formed by coating at least a composition for forming a low refractive index layer on a transparent support. The composition for forming the rate layer contains at least one of a hydrolyzate of a specific organic silyl compound and a partial condensate thereof, and the center line surface roughness Ra of the outermost surface of the antireflection film is in a specific range. Features.
Hereinafter, the low refractive index layer will be described first, and then the other layers and the support will be described.

<Antireflection film>
(Low refractive index layer)
The composition for forming a low refractive index layer constituting the antireflection layer of the antireflection film of the present invention contains at least one of a hydrolyzate of a specific organic silyl compound and a partial condensate thereof.

[Organic silyl compounds]
The specific organic silyl compound used in the composition for forming a low refractive index layer in the present invention is a compound represented by the following general formula (1).
General formula (1): R ¹¹ _m Si (X ¹¹ ) _n
(In the formula, X ¹¹ represents —OH, a halogen atom, —OR ¹² group, or —OCOR ¹² group. R ¹¹ represents an alkyl group, an alkenyl group, or an aryl group, and R ¹² represents an alkyl group. M + n represents 4 and m and n are each a positive integer.)

Specifically, R ¹¹ is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms (for example, methyl group, ethyl group, propyl group, i-propyl group, butyl group, hexyl group, octyl group), carbon number 2 -10 substituted or unsubstituted alkenyl group (for example, vinyl group, allyl group, 2-buten-1-yl group), or substituted or unsubstituted aryl group having 6 to 10 carbon atoms (for example, phenyl group) R ¹² represents a group having the same meaning as the alkyl group represented by R ¹¹ . When the group represented by R ¹¹ or R ¹² has a substituent, preferred substituents are halogen (for example, fluorine, chlorine, bromine, etc.), hydroxyl group, mercapto group, carboxyl group, epoxy group, alkyl group (for example, Methyl group, ethyl group, i-propyl group, propyl group, t-butyl group, etc.), aryl group (for example, phenyl group, naphthyl group, etc.), aromatic heterocyclic group (for example, furyl group, pyrazolyl group, pyridyl group) Etc.), alkoxy groups (eg methoxy group, ethoxy group, i-propoxy group, hexyloxy group etc.), aryloxy groups (eg phenoxy group etc.), alkylthio groups (eg methylthio group, ethylthio group etc.), arylthio Group (for example, phenylthio group), alkenyl group (for example, vinyl group, allyl group, etc.), acyloxy group (for example, acetoxy group) , Acryloyloxy group, methacryloyloxy group, etc.), alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, etc.), aryloxycarbonyl group (eg, phenoxycarbonyl group, etc.), carbamoyl group (eg, carbamoyl group, N- Methylcarbamoyl group, N, N-dimethylcarbamoyl group, N-methyl-N-octylcarbamoyl group, etc.), acylamino group (for example, acetylamino group, benzoylamino group, acrylamino group, methacrylamino group, etc.) and the like. .

The compound of the general formula (1) forms a matrix by a so-called sol-gel method in which it is hydrolyzed and condensed with each other. The compound of general formula (1) is represented by the following four general formulas.
General formula (1a): Si (X ¹¹ ) ₄
General formula (1b): R ¹¹ Si (X ¹¹ ) ₃
Formula (1c): R ¹¹ ₂ Si (X ¹¹ ) ₂
Formula (1d): R ¹¹ ₃ SiX ¹¹

First, the component of General formula (1a) is demonstrated concretely.
Specific examples of the compound represented by the general formula (1a) include tetramethoxysilane, tetraethoxysilane, tetra-i-propoxysilane, tetra-n-propoxysilane, tetra-n-butoxysilane, and tetra-s-. Examples include butoxysilane and tetra-t-butoxysilane. Tetramethoxysilane or tetraethoxysilane is particularly preferable.

Next, the component of general formula (1b) is demonstrated. In the component of the general formula (1b), R ¹¹ represents a group having the same meaning as R ¹¹ in the general formula (1), for example, an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, In addition, γ-chloropropyl group, vinyl group, CF ₃ CH ₂ CH ₂ CH ₂ —, C ₂ F ₅ CH ₂ CH ₂ CH ₂ —, C ₃ F ₇ CH ₂ CH ₂ CH ₂ —, C ₂ F ₅ CH _{2 CH 2 -, CF 3 OCH 2} CH 2 CH 2 -, C 2 F 5 OCH 2 CH 2 CH 2 -, C 3 F 7 OCH 2 CH 2 CH 2 -, (CF 3) 2 CHOCH 2 CH 2 CH 2 - , C ₄ F ₉ CH ₂ OCH ₂ CH ₂ CH ₂ —, 3- (perfluorocyclohexyloxy) propyl group, H (CF ₂ ) ₄ CH ₂ OCH ₂ CH ₂ CH ₂ —, H (CF ₂ ) ₄ CH ₂ CH ₂ CH ₂ -, 3-glycidoxypropyl group, 3-acryloxy propyl Group, 3-methacryloxypropyl group, 3-mercaptopropyl group, a phenyl group, a 3,4-epoxycyclohexylethyl group.

X ¹¹ represents —OH, a halogen atom, —OR ¹² group, or —OCOR ¹² group. R ¹² represents a group having the same meaning as R ¹² in the general formula (1). Preferably, it is a C1-C5 alkoxy group or a C1-C4 acyloxy group, for example, a chlorine atom, a methoxy group, an ethoxy group, n-propyloxy group, i-propyloxy group, n-butyloxy group , S-butyloxy group, t-butyloxy group, acetyloxy group and the like.

Specific examples of these components of the general formula (1b) include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i -Propyltrimethoxysilane, i-propyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3 -Glycidoxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltri Toxisilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3,4-epoxycyclohexylethyltrimethoxysilane, 3,4-epoxycyclohexylethyltriethoxysilane, _{CF 3 CH 2 CH 2 CH 2} Si (OCH 3) 3 -, C 2 F 5 CH 2 CH 2 CH 2 Si (OCH 3) 3 -, C 2 F 5 CH 2 CH 2 Si (OCH 3) 3 -, _{C 3 F 7 CH 2 CH 2} CH 2 Si (OCH 3) 3 -, C 2 F 5 OCH 2 CH 2 CH 2 Si (OCH 3) 3 -, C 3 F 7 OCH 2 CH 2 CH 2 Si (OC 2 _{H 5) 3 -, (CF} 3) 2 CHOCH 2 CH 2 CH 2 Si (OCH 3) 3 -, C 4 F 9 CH 2 OCH 2 CH 2 CH 2 Si (OCH 3) 3 - _{H (CF 2) 4 CH 2} OCH 2 CH 2 CH 2 Si (OCH 3) 3 -, 3- can be mentioned (perfluorocyclohexyl) propyl silane.

Among these, an organic silyl compound having a fluorine atom is preferable. In the case of using an organic silyl compound having no fluorine atom as R ^11, it is preferable to use methyltrimethoxysilane or methyltriethoxysilane. Said organic silyl compound may be used individually by 1 type, and can also use 2 or more types together.

Next, the component of general formula (1c) is demonstrated. The component of the general formula (1c) has the general formula R ¹¹ ₂ Si (X ¹¹ ) ₂ {wherein R ¹¹ and X ¹¹ are defined as the organic silyl compound used for the component of the general formula (1b), It is the same as R ¹¹ and X ¹¹ }. However, the plurality of R ¹¹ may not be the same group. In the composition of the present invention, it becomes a hydrolyzate and / or a partial condensate obtained by hydrolysis and condensation, which acts as a binder in the composition and softens the coating film to improve alkali resistance. It is.

Specific examples of these organic silyl compounds are dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di-i-propyl. dimethoxysilane, di -i- propyl diethoxy silane, diphenyl dimethoxy silane, diphenyl diethoxy _{silane, (CF 3 CH 2 CH 2} ) 2 Si (OCH 3) 2, (CF 3 CH 2 CH 2 CH 2) 2 Si ( _{OCH 3) 2, (C 3} F 7 OCH 2 CH 2 CH 2) 2 Si (OCH 3) 2, [H (CF 2) 6 CH 2 OCH 2 CH 2 CH 2] 2 Si (OCH 3) 2, ( C ₂ F ₅ OCH ₂ CH ₂ ) ₂ Si (OCH ₃ ) _{2 and the} like can be mentioned, and an organic silyl compound having a fluorine atom is preferred. In the case of using an organic silyl compound having no fluorine atom as R ¹¹ is, dimethyldimethoxysilane, dimethyldiethoxysilane are preferred. Moreover, the organic silyl compound represented by the component of general formula (1c) may be used individually by 1 type, or can also use 2 or more types together.

Next, the component of general formula (1d) is demonstrated. The components of the general formula (1d), the general formula R ¹¹ ₃ SiX ¹¹ {wherein, R ¹¹ and X ¹¹ R ¹¹ as defined in the organosilyl compound used in component of the general formula (1b) is and X ¹¹ It is an organic silyl compound represented by However, the plurality of R ¹¹ may not be the same group. In the composition of this invention, while functioning to make a film | membrane hydrophobic, it improves the alkali resistance of a coating film.

  Specific examples of these organic silyl compounds are trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane, triethylethoxysilane, tri-n-propylmethoxysilane, tri-n-propylethoxysilane, tri-i-propylmethoxysilane. , Tri-i-propylethoxysilane, triphenylmethoxysilane, triphenylethoxysilane and the like.

  In the present invention, the components of the general formulas (1a) to (1d) can be used alone, but may be used in combination. The mixing ratio in that case is that the component (1a) is 100 masses. When it is made into a part, (1b) component is 0-100 mass parts, Preferably it is 1-60 mass parts, More preferably, it is 1-40 mass parts. The component (1c) is preferably 0 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, and still more preferably 0.5 to 3 parts by mass when the component (1a) is 100 parts by mass. The component (1d) is preferably 0 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, and further preferably 0.5 to 3 parts by mass when the component (1a) is 100 parts by mass. Among the components (1a) to (1d), the proportion of the component (1a) is preferably 30% by mass or more in 100% by mass of the total organic silyl compound. If the ratio of the component (1a) is 30% by mass or more, it is preferable because problems such as a decrease in adhesion and curability of the obtained coating film do not occur.

[Polymerizable monomer]
In the present invention, it is preferable to use a polymerizable monomer in combination with the organic silyl compound. In particular, a monomer containing a fluorine atom (hereinafter sometimes referred to as a fluorine-containing monomer) is preferably used from the viewpoint that the refractive index of the resulting low refractive index layer film can be lowered. The fluorine-containing monomer is not particularly limited as long as the monomer contains a fluorine atom, but those having a fluorine atom as a perfluoroalkyl group are particularly preferred from the viewpoint of fluorine content.

  Specific examples of polymerizable monomers include, for example, partially or fully fluorinated alkyl, alkenyl, aryl esters, fully or partially fluorinated vinyl ethers, fully or partially fluorinated vinyl esters, fully or partially fluorine of acrylic acid or methacrylic acid. Vinyl chlorides and the like. It is preferable that the compounding quantity of a polymerizable monomer shall be 1-50 mass% in the total solid of a low refractive index layer.

[Inorganic fine particles]
In addition, it is preferable to use inorganic fine particles for the low refractive index layer.
The coating amount of the inorganic fine particles is preferably 1 to 100 mg / m ^2, more preferably 5-80 mg / m ^2, more preferably from 10~60mg / m ^2. If the amount of the inorganic fine particles is not less than the lower limit value, it is preferable because defects such as a reduction in the effect of improving the scratch resistance are not caused. If the amount is not more than the upper limit value, fine irregularities can be formed on the surface of the low refractive index layer. In view of this, it is preferable that the appearance such as black tightening and the integrated reflectance are not deteriorated. Since the inorganic fine particles are contained in the low refractive index layer, it is desirable that the inorganic fine particles have a low refractive index. Examples thereof include fine particles of magnesium fluoride and silica. In particular, silica fine particles are preferable in terms of refractive index, dispersion stability, and cost.

(Silica fine particles)
Hereinafter, the silica fine particles will be described in detail on behalf of the inorganic fine particles.
The average particle diameter of the silica fine particles is preferably 30% or more and 150% or less of the thickness of the low refractive index layer, more preferably 35% or more and 80% or less, and further preferably 40% or more and 60% or less. That is, when the thickness of the low refractive index layer is 100 nm, the particle diameter of the silica fine particles is preferably 30 nm to 150 nm, more preferably 35 nm to 80 nm, and still more preferably 40 nm to 60 nm.

  If the particle size of the silica fine particles is too small, the effect of improving the scratch resistance may be reduced. If it is too large, fine irregularities are formed on the surface of the low refractive index layer, and the appearance such as black tightening and the integrated reflectance are deteriorated. In some cases, it is preferable to use silica fine particles having a particle size within the above range. The silica fine particles may be either crystalline or amorphous, and may be monodispersed particles or aggregated particles as long as a predetermined particle size is satisfied. The shape is most preferably a spherical diameter, but there is no problem even if the shape is indefinite. Here, the average particle diameter of the inorganic fine particles is measured by a Coulter counter.

In order to further reduce the increase in the refractive index of the low refractive index layer, it is preferable to use hollow silica fine particles (hereinafter sometimes referred to as hollow particles), and such hollow particles preferably have a refractive index of 1. .17 to 1.40, more preferably 1.17 to 1.35, and even more preferably 1.17 to 1.30. The refractive index here represents the refractive index of the entire particle, and does not represent the refractive index of only the outer shell silica forming the hollow particles. At this time, if the radius of the cavity in the particle is r _i and the radius of the particle outer shell is r _o , the porosity x is expressed by the following formula (1).
Formula (1): x = (r _i / r _o ) ³ × 100 (%)

The porosity of the hollow particles is preferably 10 to 60%, more preferably 20 to 60%, and most preferably 30 to 60%. From the viewpoint of the strength of the hollow silica particles and the scratch resistance of the low refractive index layer, the hollow particles are made to have a lower refractive index than the above range and the porosity is made larger than the above range, so that the thickness of the outer shell becomes thin. The refractive index of the hollow particles is preferably 1.17 or more.
The refractive index of these hollow particles was measured with an Abbe refractometer (manufactured by Atago Co., Ltd.).

  In the low refractive index layer, at least one kind of silica fine particles (hereinafter sometimes referred to as small size fine particles) having an average particle size of less than 25% of the thickness of the low refractive index layer is added to the above preferable average particle size. It is preferable to use in combination with silica fine particles within the range (hereinafter sometimes referred to as large size fine particles).

  Silica fine particles are used in plasma discharge treatment and corona discharge treatment in order to stabilize dispersion in a dispersion or a composition for forming a low refractive index layer, or to increase affinity and binding properties with a matrix component. Such physical surface treatment, chemical surface treatment with a surfactant, a coupling agent, or the like may be performed. The use of a coupling agent is particularly preferred. As the coupling agent, an alkoxy metal compound (for example, a titanium coupling agent or a silane coupling agent) is preferably used. Of these, silane coupling treatment is particularly effective.

  The above-mentioned coupling agent is used as a surface treatment agent for the inorganic fine particles of the low refractive index layer in order to perform surface treatment in advance before preparing the composition for forming the low refractive index layer. Sometimes, it is preferable to add it as an additive to be contained in the low refractive index layer. The silica fine particles are preferably dispersed in the medium in advance before the surface treatment in order to reduce the load of the surface treatment.

What has been described above for the silica fine particles is also applicable to other inorganic particles. That is, the low refractive index layer contains inorganic fine particles having an average particle diameter of 30% to 120% of the thickness of the low refractive index layer and having a hollow structure and a refractive index of 1.17 to 1.40. It is preferable to do this. Examples of the particles that can be preferably used in the present invention include particles produced according to the techniques described in JP-A Nos. 2001-233611 and 2002-79616.

  The inorganic fine particles that can be preferably used in the low refractive index layer in the invention are preferably dispersed in advance. As the dispersion medium, a liquid having a boiling point of 60 to 170 ° C. is preferably used. Examples of dispersion media include water, alcohols (eg, methanol, ethanol, isopropanol, butanol, benzyl alcohol), ketones (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone), esters (eg, methyl acetate, ethyl acetate, Propyl acetate, butyl acetate, methyl formate, ethyl formate, propyl formate, butyl formate), aliphatic hydrocarbons (eg, hexane, cyclohexane), halogenated hydrocarbons (eg, methylene chloride, chloroform, carbon tetrachloride), aromatic Hydrocarbons (eg, benzene, toluene, xylene), amides (eg, dimethylformamide, dimethylacetamide, n-methylpyrrolidone), ethers (eg, diethyl ether, dioxane, tetrahydrofurane), Chromatography ether alcohols (e.g., 1-methoxy-2-propanol) are included. In particular, water, methanol, ethanol, and isopropyl alcohol are preferable.

  The concentration of the inorganic fine particles in the dispersion of inorganic fine particles is preferably 3 to 300 g / L.

[catalyst]
In the composition for forming a low refractive index layer in the present invention, various catalyst compounds can be preferably used for the purpose of promoting the hydrolysis / partial condensation reaction of the organic silyl compound represented by the general formula (1). . The catalyst used is not particularly limited, and an appropriate amount may be used according to the constituent components of the sol liquid used. Generally effective catalysts are the following compounds (c ₁ ) to (c ₅ ), and a necessary amount of a preferable compound can be added from these compounds. Further, two or more of these groups can be appropriately selected and used in combination as long as the mutual promoting effects are not inhibited.

(C ₁ ) Organic or inorganic acid Examples of the inorganic acid include hydrochloric acid, hydrogen bromide, hydrogen iodide, sulfuric acid, sulfurous acid, nitric acid, nitrous acid, phosphoric acid, phosphorous acid, heteropolyacid (for example, phosphomolybdic acid, phosphotungstic acid) Organic acid compounds include carboxylic acids (eg, formic acid, succinic acid, acetic acid, propionic acid, butyric acid, succinic acid, cyclohexanecarboxylic acid, octanoic acid, maleic acid, 2-chloropropionic acid, cyanoacetic acid, trifluoroacetic acid) Perfluorooctanoic acid, benzoic acid, pentafluorobenzoic acid, phthalic acid, etc.), sulfonic acids (e.g. methanesulfonic acid, ethanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, pentafluorobenzenesulfonic acid, etc.), Phosphoric acid partial esters and phosphonic acids (eg phosphoric acid dimethyl ester, phenyl Phosphonic acid, etc.) and Lewis acids (for example, boron trifluoride etherate, scandium triflate, alkyl titanic acid, aluminate, etc.).

(C ₂ ) Organic or inorganic base As the inorganic base, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, ammonia and the like; As the organic base compound, amines (for example, ethylenediamine, diethylenetriamine, Triethylenetetramine, tetraethylenepentamine, triethylamine, dibutylamine, tetramethylethylenediamine, piperidine, piperazine, morpholine, ethanolamine, diazabicycloundecene,
Quinuclidine, aniline, pyridine, etc.), phosphines (eg, triphenylphosphine, trimethylphosphine, etc.), metal alkoxides (eg, sodium methylate, potassium ethylate, etc.).

(C ₃ ) Metal chelate compound An alcohol represented by the general formula R ⁰¹ OH (wherein R ⁰¹ represents an alkyl group having 1 to 6 carbon atoms) and R ⁰² COCH ₂ COR ⁰³ (where R ⁰² represents alkyl group having 1 to 6 carbon atoms, R ⁰³ is a diketone represented by an alkyl group or an alkoxy group having 1 to 16 carbon atoms having 1 to 5 carbon atoms) as a ligand, a central metal of the metal Any material can be suitably used without particular limitation. Within this category, two or more metal chelate compounds may be used in combination. Particularly preferred as the metal chelate compound of the present invention is one having Al, Ti, Zr as the central metal, and the following general formula:
Zr (R ⁰¹ ) _p1 (R ⁰² COCHCOR ⁰³ ) _p2
Ti (OR ⁰¹ ) _q1 (R ⁰² COCHCOR ⁰³ ) _q2 and Al (OR ⁰¹ ) _r1 (R ⁰² COCHCOR ⁰³ ) _r2
Are preferably selected from the group of compounds represented by the formula (1a) to (1d), which promote the condensation reaction of the components (1a) to (1d).

R ⁰¹ and R ⁰² in the metal chelate compound may be the same or different, and an alkyl group having 1 to 6 carbon atoms, specifically, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, Examples thereof include s-butyl group, t-butyl group, n-pentyl group, and phenyl group. R ⁰³ is an alkyl group having 1 to 6 carbon atoms as in R ⁰¹ and R ⁰² , or an alkoxy group having 1 to 16 carbon atoms, such as a methoxy group, an ethoxy group, an n-propoxy group, or an i-propoxy group. N-butoxy group, s-butoxy group, t-butoxy group, lauryl group, stearyl group and the like. In addition, p1, p2, q1, q2, r1, and r2 in the metal chelate compound represent integers determined so as to be tetradentate or hexadentate.

  Specific examples of these metal chelate compounds include tri-n-butoxyethylacetoacetate zirconium, di-n-butoxybis (ethylacetoacetate) zirconium, n-butoxytris (ethylacetoacetate) zirconium, tetrakis (n-propylacetate). Zirconium chelate compounds such as acetate) zirconium, tetrakis (acetylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium; diisopropoxy bis (ethylacetoacetate) titanium, diisopropoxy bis (acetylacetate) titanium, diiso Titanium chelate compounds such as propoxy bis (acetylacetone) titanium; diisopropoxyethyl acetoacetate aluminum, diisopropyl Poxyacetylacetonate aluminum, isopropoxybis (ethylacetoacetate) aluminum, isopropoxybis (acetylacetonate) aluminum, tris (ethylacetoacetate) aluminum, tris (acetylacetonato) aluminum, monoacetylacetonate bis (ethyl) An aluminum chelate compound such as acetoacetate) aluminum. Among these metal chelate compounds, tri-n-butoxyethyl acetoacetate zirconium, diisopropoxy bis (acetylacetonate) titanium, diisopropoxyethyl acetoacetate aluminum, and tris (ethyl acetoacetate) aluminum are preferable. . These metal chelate compounds can be used individually by 1 type or in mixture of 2 or more types. Moreover, the partial hydrolyzate of these metal chelate compounds can also be used.

(C ₄ ) Organometallic compound The preferred organometallic compound is not particularly limited, but an organic transition metal is preferred because of its high activity. Of these, tin compounds are particularly preferred because of their good stability and activity. Specific examples of these compounds include (C ₄ H ₉ ) ₂ Sn (OCOC ₁₁ H ₂₃ ) ₂ , (C ₄ H ₉ ) ₂ Sn (OCOCH = CHCOOCH ₃ ) ₂ , (C ₄ H ₉ ) ₂ Sn ( OCOCH = CHCOOC ₄ H ₉ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (OCOC ₁₁ H ₂₃ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (OCOCH═CHCOOCH ₃ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn ( Carboxylic acid type organotin compounds such as OCOCH = CHCOOC ₄ H ₉ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (OCOCH═CHCOOC ₈ H ₁₇ ) ₂ ; (C ₄ H ₉ ) ₂ Sn (SCH ₂ COOC ₈ H ₁₇ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (SCH ₂ COOC ₈ H ₁₇ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (SCH ₂ CH ₂ COOC ₈ H ₁₇ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn ( SCH ₂ COOC ₈ H ₇ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (SCH ₂ COOC ₁₂ Mercaptide-type organotin compounds such as H ₂₅ ) ₂ ; or organotin oxides such as (C ₄ H ₉ ) ₂ SnO, (C ₈ H ₁₇ ) ₂ SnO, and ethyl silicate, dimethyl maleate, diethyl maleate, dioctyl phthalate And organotin compounds such as reaction products with ester compounds.

The (c ₅₎ metal salts metal salts, alkali metal salts (e.g., sodium naphthenate, potassium naphthenate, sodium octanoate, sodium 2-ethylhexanoate, and potassium laurate) of organic acids are preferably used.

  The ratio of these catalysts in the composition for forming a low refractive index layer is preferably 0.01 to 50 parts by mass, more preferably 0.1 to 50 parts by mass, and further preferably 100 parts by mass of the organic silyl compound. Is 0.5 to 10 parts by mass.

[Chelate coordination compounds]
When the metal chelate compound is used as a catalyst, it is also preferable to use a compound having a chelate coordination ability from the viewpoint of adjusting the curing reaction rate and improving the liquid stability. Preferably used are β-diketones and / or β-ketoesters represented by the general formula R ⁰¹ COCH ₂ COR ^02, which act as stability improvers for the composition for forming a low refractive index layer It is. That is, by coordinating with metal atoms in metal chelate compounds (preferably zirconium, titanium and / or aluminum compounds) present in the composition for forming a low refractive index layer, these metal chelate compounds (1a) It is considered that the action of promoting the condensation reaction of the component (1d) is suppressed and the curing rate of the resulting film is controlled. R ⁰¹ and R ⁰² are synonymous with R ⁰¹ and R ⁰² constituting the metal chelate compound, but need not have the same structure when used.

  Specific examples of the β-diketone and / or β-ketoester include acetylacetone, methyl acetoacetate, ethyl acetoacetate, acetoacetate-n-propyl, acetoacetate-i-propyl, acetoacetate-n-butyl, acetoacetate Acetic acid-s-butyl, acetoacetic acid-t-butyl, 2,4-hexanedione, 2,4-heptanedione, 3,5-heptanedione, 2,4-octanedione, 2,4-nonanedione, 5-methyl Examples include hexane-dione. Of these, ethyl acetoacetate and acetylacetone are preferred, and acetylacetone is particularly preferred. These β-diketones and / or β-ketoesters may be used alone or in combination of two or more. The amount of such β-diketone and / or β-ketoester used is 2 mol or more, preferably 3 to 20 mol, per 1 mol of the metal chelate compound. By using 2 mol or more, the storage stability of the composition is improved.

[Preparation of composition for forming low refractive index layer]
The composition for forming a low refractive index layer is for forming a low refractive index layer, and is a liquid material that can be applied.
That is, the composition for forming a low refractive index layer used in the present invention comprises at least one of a hydrolyzate of the organic silyl compound and a partial condensate thereof, a solvent, and optionally the polymerizable monomer and the inorganic fine particles. It is only necessary to have a fluorine-containing compound or polysiloxane described later.

  Examples of the solvent that can be used at this time include alcohols (methanol, ethanol, isopropyl alcohol, butanol, 2-butanol, etc.) and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.).

  In the present invention, it is preferable to add water to the composition for a low refractive index layer for hydrolysis / condensation reaction of the organic silyl compound which is a component of the general formulas (1a) to (1d). The usage-amount of water is 1.2-3.0 mol normally with respect to 1 mol of (1a)-(1d) components, Preferably it is about 1.3-2.0 mol.

  Furthermore, the total solid content concentration of the composition for forming a low refractive index layer is preferably 0.1 to 50% by mass, more preferably 1 to 40% by mass. A total solid content concentration of 50% by mass or less is preferable because problems such as deterioration in storage stability of the composition do not occur.

  When preparing the composition for forming a low refractive index layer, it is preferable that an organic silyl compound is reacted in advance in the presence of water and a catalyst, and partially subjected to condensation polymerization after hydrolysis. The relative molecular weight in terms of ethylene glycol / polyethylene oxide calculated by GPC of the siloxane oligomer is preferably 700 to 1500, and more preferably 900 to 1000. The reaction temperature is preferably 5 to 50 ° C, more preferably 10 to 40 ° C, and most preferably 15 to 30 ° C.

[Thickness of low refractive index layer]
The thickness of the low refractive index layer in the present invention is preferably 50 to 200 nm, more preferably 60 to 150 nm, and most preferably 70 to 120 nm. If the film thickness is less than or equal to the upper limit value, it will not cause a problem that the layer becomes brittle with excellent strength, and if the film thickness is greater than or equal to the lower limit value, there will be no problem such as a decrease in film strength. Therefore, the film thickness of the low refractive index layer is preferably in the above range.

[Surface free energy]
In the present invention, from the viewpoint of improving antifouling properties, it is preferable to reduce the surface free energy of the antireflection film surface. Specifically, this can be achieved by allowing a surface free energy reducing compound such as a fluorine-containing compound or a compound having a polysiloxane structure to be present on the outermost surface. The surface free energy is preferably 26 mJ / m ² or less, still more preferably not more than 24 mJ / m ^2, and most preferably 22 mJ / m ² or less.

  Preferred examples of the fluorine-containing compound include compounds having a fluorine atom among the organic silyl compounds represented by the general formula (1).

  Examples of the additive having a polysiloxane structure include reactive group-containing polysiloxanes (for example, “KF-100T”, “X-22-169AS”, “KF-102”, “X-22-3701IE”, “X-”). 22-164B "," X-22-5002 "," X-22-173B "," X-22-174D "," X-22-1667B "," X-22-161AS "{Since, Shin-Etsu Chemical Co., Ltd. "AK-5", "AK-30", "AK-32" {above, manufactured by Toa Gosei Co., Ltd.}; "Silaplane FM0725", "Silaplane FM0721" {above, Chisso ( Co., Ltd.} etc. It is also preferable to use silicone compounds described in Tables 2 and 3 of JP-A No. 2003-112383.

When the low refractive index layer is the outermost surface layer of the antireflective film of the present invention, these surface free energy reducing compounds are used in an amount of 0.1 to 10 based on the total solid content of the low refractive index layer forming composition. mass%
It is preferable to add in the range of 1-5 mass%.

[Anti-fouling layer]
When the low refractive index layer is the outermost surface layer, the surface free energy reducing compound may be premixed with the organic silyl compound and condensed, or condensed at the time of drying and curing. You can also. Further, after forming a low refractive index layer, a composition containing the compound for reducing surface free energy is applied on the layer to form an antifouling layer, whereby the above-mentioned preferable surface free energy range is obtained. You can also.

  A compound that can be preferably used in forming the antifouling layer is a perfluoropolyether group-containing silane coupling agent represented by the following general formula (2).

Formula _{(2): R f - (} OC 3 F 6) s1 -O- (CF 2) s2 - (CH 2) s3 -O- (CH 2) s4 -Si (OR 21) 3

In the general formula (2), R _f represents a linear or branched perfluoroalkyl group having 1 to 16 carbon atoms, in _{particular, CF 3 -, C 2 F} 5 -, C 3 F 7 - is preferred. R ²¹ is a linear or branched alkyl group having 1 to 5 carbon atoms, and —CH ₃ and —C ₂ H ₅ are particularly preferable. Moreover, s1 is an integer of 1-50, s2 is an integer of 0-3, s3 is an integer of 0-3, s4 is an integer of 0-6, provided that 6 ≧ s2 + s3> 0.

  Any coating method may be used as long as it is a uniform coating method. For example, various wet coating methods (dip coating method, spin coating method, flow coating method, spray coating method, roll coating method, gravure coating method, air doctor coating method, blade coating method, wire doctor coating method, knife coating method, reverse Coating method, transfer roll coating method, micro gravure coating method, kiss coating method, cast coating method, slot orifice coating method, calendar coating method, die coating method, etc.) or vacuum deposition method, reactive deposition method, ion beam assist method, PVD (Physical Vapor Deposition) methods such as sputtering and ion plating, or There are known methods such as CVD (Chemical Vapor Deposition).

  If necessary after film formation of the antifouling layer, heating, humidification, ultraviolet irradiation, electron beam irradiation, or the like may be performed.

  Although the film thickness of an antifouling layer is not specifically limited, 1-50 nm is preferable from the point of antifouling property, abrasion resistance, and the optical performance of an optical member.

[Layer structure of antireflection film]
The antireflection film of the present invention comprises a transparent support and a low refractive index layer as essential layers, and further, if necessary, a refractive index, so that the reflectance decreases due to a hard coat layer described later and optical interference, Various layers can be stacked in consideration of the film thickness, the number of layers, the layer order, and the like. The simplest configuration is a configuration in which only a low refractive index layer is coated on a transparent support. In order to further reduce the reflectance, the antireflection film may be composed of a combination of a high refractive index layer having a higher refractive index than that of the transparent support and a low refractive index layer having a lower refractive index than that of the transparent support. preferable. Examples of configurations include two layers of a high refractive index layer / low refractive index layer from the transparent support side, and three layers having different refractive indices, and a medium refractive index layer (with a refractive index higher than that of the transparent support or hard coat layer). And a layer having a lower refractive index than a high refractive index layer) / a high refractive index layer / a low refractive index layer are laminated in this order, and an antireflection film in which more layers are laminated is also proposed. . Above all, from the viewpoint of durability, optical properties, cost, productivity, etc., a hard coat layer is placed on a transparent support, and a reflective layer coated in the order of medium refractive index layer / high refractive index layer / low refractive index layer thereon. A prevention film is preferred.

The example of the preferable layer structure of the antireflection film of this invention is shown below. In addition, in the following illustration, the description in the case of providing an antifouling layer is omitted.
Transparent support / low refractive index layer,
Transparent support / antiglare layer / low refractive index layer,
Transparent support / antiglare layer / antistatic layer / low refractive index layer,
Transparent support / antistatic layer / antiglare layer / low refractive index layer,
Transparent support / hard coat layer / antistatic layer / low refractive index layer,
Transparent support / antistatic layer / hard coat layer / low refractive index layer,
Transparent support / hard coat layer / high refractive index layer / low refractive index layer,
Transparent support / hard coat layer / medium refractive index layer / high refractive index layer / low refractive index layer,
Transparent support / antiglare layer / high refractive index layer / low refractive index layer,
Transparent support / antiglare layer / medium refractive index layer / high refractive index layer / low refractive index layer,
Transparent support / antistatic layer / hard coat layer / medium refractive index layer / high refractive index layer / low refractive index layer,
Antistatic layer / transparent support / hard coat layer / medium refractive index layer / high refractive index layer / low refractive index layer,
Transparent support / antistatic layer / antiglare layer / medium refractive index layer / high refractive index layer / low refractive index layer,
Antistatic layer / transparent support / antiglare layer / medium refractive index layer / high refractive index layer / low refractive index layer,
Antistatic layer / transparent support / antiglare layer / high refractive index layer / low refractive index layer / high refractive index layer / low refractive index layer From the viewpoint of reducing the reflectance, for example, described in JP-A No. 2003-262702 An antireflection layer including a structure of medium refractive index layer / high refractive index layer / low refractive index layer is preferable.

The layer configuration of the antireflection film of the present invention is not particularly limited to these layer configurations as long as the reflectance can be reduced by optical interference.
The antistatic layer is preferably a layer containing conductive polymer particles or metal oxide fine particles (for example, SnO ₂ , ITO), and can be provided by coating or atmospheric pressure plasma treatment.
Hereinafter, each layer and transparent support that can be employed in the present invention will be described.

[Hard coat layer]
The hard coat layer used in the present invention will be described below.
The hard coat layer is an arbitrary combination of components selected from binders, matte particles for imparting antiglare properties or internal scattering properties, and inorganic fillers for adjusting the refractive index, preventing crosslinking shrinkage, and increasing strength. Can be formed.

  In the present invention, a hard coat layer functioning as a light diffusion layer, which uses a light-transmitting resin as a binder and light-transmitting particles as matte particles, is preferably employed. In other words, the hard coat layer in the present invention is not a hard coat layer in a narrow sense as a layer having a function of increasing the hardness of the film, but a layer capable of exhibiting a function by arbitrarily combining the above constituent elements. Therefore, depending on the component to be combined, it can be a hard coat layer in a narrow sense, a high refractive index layer, a medium refractive index layer, an antiglare layer, a light diffusion layer, an internal scattering layer, or an antistatic layer.

[binder]
The translucent resin used as the binder of the hard coat layer is preferably a binder polymer having a saturated hydrocarbon chain or a polyether chain as a main chain, and more preferably a binder polymer having a saturated hydrocarbon chain as a main chain. The binder polymer preferably has a crosslinked structure.

As the binder polymer having a saturated hydrocarbon chain as a main chain, a polymer of an ethylenically unsaturated monomer is preferable. As the binder polymer having a saturated hydrocarbon chain as the main chain and having a crosslinked structure, a (co) polymer of monomers having two or more ethylenically unsaturated groups is preferred. In order to achieve a high refractive index, the monomer structure contains at least one atom selected from an aromatic ring, a halogen atom other than fluorine, a sulfur atom, a phosphorus atom, and a nitrogen atom in the structure of these monomers. Is preferably used.

  Examples of the monomer having two or more ethylenically unsaturated groups include esters of polyhydric alcohol and (meth) acrylic acid {for example, ethylene glycol di (meth) acrylate, 1,4-cyclohexanediacrylate, pentaerythritol tetra ( (Meth) acrylate), pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, di Pentaerythritol hexa (meth) acrylate, pentaerythritol hexa (meth) acrylate, 1,2,3-cyclohexanetetramethacrylate, polyurethane polyacrylate, polyester Polyacrylate}, divinylbenzene and its derivatives (eg, 1,4-divinylbenzene, 4-vinylbenzoic acid-2-acryloylethyl ester, 1,4-divinylcyclohexanone), vinyl sulfone (eg, divinyl sulfone) and (meta ) Derivatives of acrylamide (for example, methylenebis (meth) acrylamide). Two or more of these monomers may be used in combination.

  Specific examples of the high refractive index monomer include bis (4-methacryloylthiophenyl) sulfide, vinyl naphthalene, vinyl phenyl sulfide, 4-methacryloxyphenyl-4′-methoxyphenyl thioether, and the like. Two or more of these monomers may be used in combination.

  Polymerization of these monomers having an ethylenically unsaturated group can be performed by irradiation with ionizing radiation or heating in the presence of a photo radical initiator or a thermal radical initiator. Therefore, a coating liquid of a composition for forming a hard coat layer containing a monomer having an ethylenically unsaturated group, a photo radical initiator or a thermal radical initiator, translucent particles and an inorganic filler is prepared, and the coating liquid is After coating on the surface on which the hard coat layer is to be placed, it can be cured by a polymerization reaction with ionizing radiation or heat to form a hard coat layer.

  As radical photopolymerization initiators, acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkyldione compounds, disulfide compounds And fluoroamine compounds and aromatic sulfoniums.

  Examples of acetophenones include 2,2-diethoxyacetophenone, p-dimethylacetophenone, 1-hydroxydimethylphenyl ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-4-methylthio-2-morpholinopropiophenone and 2 -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone is included.

  Examples of benzoins include benzoin benzene sulfonate, benzoin toluene sulfonate, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether.

  Examples of benzophenones include benzophenone, 2,4-dichlorobenzophenone, 4,4-dichlorobenzophenone and p-chlorobenzophenone. Examples of phosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

  Various examples are also described in “Latest UV Curing Technology” {page 159, publisher: Kazuhiro Takasato, publisher; Technical Information Association, Inc., published in 1991}, which is useful for the present invention. Preferable examples of commercially available photocleavable photoradical polymerization initiators include “Irgacure” (651, 184, 907) manufactured by Ciba Geigy Japan.

  It is preferable to use a photoinitiator in the range of 0.1-15 mass parts with respect to 100 mass parts of total amounts of the monomer mentioned above, More preferably, it is the range of 1-10 mass parts.

  In addition to the photopolymerization initiator, a photosensitizer may be used. Specific examples of the photosensitizer include n-butylamine, triethylamine, tri-n-butylphosphine, Michler's ketone and thioxanthone.

As the thermal radical initiator, organic or inorganic peroxides, organic azo, diazo compounds, and the like can be used.
Specifically, organic peroxides include benzoyl peroxide, halogen benzoyl peroxide, lauroyl peroxide, acetyl peroxide, dibutyl peroxide, cumene hydroperoxide, butyl hydroperoxide; inorganic peroxides such as hydrogen peroxide, Ammonium persulfate, potassium persulfate, etc .; 2-azobisisobutyronitrile, 2-azobispropionitrile, 2-azobiscyclohexanedinitrile, etc. as azo compounds; diazoaminobenzene, p-nitrobenzenediazonium, etc. as diazo compounds Can be mentioned.

  The binder polymer having a polyether chain as the main chain is preferably a ring-opening polymer of a polyfunctional epoxy compound. The ring-opening polymerization of the polyfunctional epoxy compound can be performed by irradiation with ionizing radiation or heating in the presence of a photoacid generator or a thermal acid generator. Therefore, a coating liquid of a composition for forming a hard coat layer containing a polyfunctional epoxy compound, a photoacid generator or a thermal acid generator, translucent particles and an inorganic filler is prepared, and the coating liquid is applied to the hardcoat layer. After coating on the surface to be installed, it can be cured by a polymerization reaction with ionizing radiation or heat to form a hard coat layer.

  Instead of or in addition to a monomer having two or more ethylenically unsaturated groups, a monomer having a crosslinkable functional group is used to introduce a crosslinkable functional group into the polymer, and this crosslinkable functional group reacts. A crosslinked structure may be introduced into the binder polymer.

  Examples of the crosslinkable functional group include an isocyanate group, an epoxy group, an aziridine group, an oxazoline group, an aldehyde group, a carbonyl group, a hydrazine group, a carboxyl group, a methylol group, and an active methylene group. Vinylsulfonic acid, acid anhydride, cyanoacrylate derivative, melamine, etherified methylol, ester and urethane, and metal alkoxide such as tetramethoxysilane can also be used as a monomer for introducing a crosslinked structure. A functional group that exhibits crosslinkability as a result of the decomposition reaction, such as a block isocyanate group, may be used. That is, in the present invention, the crosslinkable functional group may not react immediately but may exhibit reactivity as a result of decomposition.

  These binder polymers having a crosslinkable functional group can form a crosslinked structure by heating after coating.

  In the present invention, in order to improve the durability of the antireflection film, the polarizing plate, and the display device, the hard coat layer includes an organic silyl compound represented by the general formula (1), a hydrolyzate thereof, and a partial condensate thereof. It is preferably formed by coating a composition for forming a hard coat layer containing at least one of the above or a polyfunctional isocyanate compound.

  When an organic silyl compound is used, the addition amount of the organic silyl compound is 0.1% by mass or more and 120% by mass or less based on the solid content (binder, particles, etc.) excluding the compound in the hard coat layer. Is preferably 0.5% by mass or more and 60% or less, and most preferably 1.0% by mass or more and 40% by mass or less. The organic silyl compound may be added to the coating solution of the composition for forming a hard coat layer in an unhydrolyzed state, or may be added after partially or completely hydrolyzed. The organosilyl compound may be added to the hard coat layer in the form of a dimer to 15-mer condensate, particularly from the viewpoint of improving storage conditions under severe temperature changes and durability under an ozone-containing atmosphere. preferable. The degree of condensation can be calculated by gas permeation chromatography. In the case where the hard coat layer contains an inorganic filler, the organic silyl compound is also preferably used in a state of being hydrogen bonded and / or covalently bonded to the surface of the inorganic filler. As an inorganic filler, it is preferable to use especially for the tin oxide and indium oxide which have the below-mentioned electroconductivity.

  Preferred organic silyl compounds include, but are not limited to, the following: Tetramethoxysilane, tetraethoxysilane, tetra-i-propoxysilane, tetra-n-propoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycyl Sidoxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane 3,4-epoxycyclohexylethyltriethoxysilane.

  Further, preferred organic silyl compounds as condensates are 1 to 9 (mass ratio) condensates (5 to 10-mer) of tetraethoxysilane and 3-acryloxypropyltrimethoxysilane, and 3-acryloxypropyltrimethoxysilane. 2 to 10-mer, 1 to 9 (mass ratio) condensate (5 to 10-mer) of tetraethoxysilane and 3-methacryloxypropyltrimethoxysilane, 2 to 10 of 3-glycidoxypropyltriethoxysilane And the like.

As the polyfunctional isocyanate compound that can be used in the hard coat layer, a compound represented by the following general formula (3) is preferable.
Formula ^{(3): R 31 - (} NCO) m
In the general formula (3), R ³¹ represents an m-valent arbitrary group, and m represents an integer of 2 or more.

A known compound can be used as the compound represented by the general formula (3). These are bifunctional, trifunctional or higher polyfunctional isocyanate compounds. In the general formula (3), R ³¹ is not particularly limited, but is an aliphatic group having 2 to 30 carbon atoms, an aromatic group having 6 to 30 carbon atoms, or a saturated or unsaturated group having 3 to 30 carbon atoms. A saturated heterocyclic group and an m-valent group obtained by combining these groups are represented. m is preferably 2 to 5, and 2 or 3 is particularly preferable.

  The compound represented by the general formula (3) can be produced by a conventional method. Examples of the compound represented by the general formula (3) include aromatic isocyanate compounds and aliphatic isocyanate compounds.

Examples of the bifunctional isocyanate represented by the general formula (3) include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, m-xylylene diisocyanate, p. -Xylylene diisocyanate, 4-chloroxylylene-1,3-diisocyanate, 2-methylxylylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenylpropane diisocyanate, 4,4'-diphenylhexafluoropropane Aromatic difunctional isocyanates such as diisocyanate, 1,4-naphthalene diisocyanate, 3,3′-dimethoxybiphenyl diisocyanate, 3,3′-dimethyldiphenylmethane-4,4′-diisocyanate; 1 3-trimethylene diisocyanate, propylene-1,2-diisocyanate, butylene-1,2-diisocyanate, 1,6-hexamethylene diisocyanate, cyclohexylene-1,2-diisocyanate, cyclohexylene-1,3-diisocyanate, cyclohexylene Fats such as 1,4-diisocyanate, isophorone diisocyanate, hydrogenated m-xylylene diisocyanate, hydrogenated p-xylylene diisocyanate, hydrogenated 4,4′-diphenylmethane diisocyanate, 2,5-di (isocyanatomethyl) norbornane Group bifunctional isocyanates; or bifunctional alcohols such as ethylene glycol and bisphenols, and addition reaction products of phenols.

  As the trifunctional or higher functional isocyanate represented by the general formula (3), for example, the aforementioned bifunctional isocyanate is used as a main raw material, and these trimers (biuret or isocyanurate), trifunctional alcohols such as trimethylolpropane, and the like Adducts with trifunctional phenols such as phloroglycine, formalin condensates of benzene isocyanate (for example, polymethylene polyphenylene polyisocyanate), polymers of isocyanate compounds having polymerizable groups such as methacryloyloxyethyl isocyanate, lysine A triisocyanate etc. are mentioned.

  As the compound represented by the general formula (3), 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-xylylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,5- Examples thereof include at least one compound selected from di (isocyanatomethyl) norbornane, 4,4′-diphenylmethane diisocyanate, hydrogenated m-xylylene diisocyanate, hydrogenated 4,4′-diphenylmethane diisocyanate, and mixtures thereof.

[Translucent particles]
For the purpose of imparting antiglare properties and / or internal scattering properties, the hard coat layer is larger than the inorganic filler and preferably has a mean particle size of 0.1 to 5.0 μm, preferably 1.5 to 3.5 μm. It is preferable that optical particles, for example, inorganic compound particles or resin particles are contained. The difference in refractive index between the translucent particles and the translucent resin is preferably in the range of 0.02 to 0.20, and particularly preferably in the range of 0.04 to 0.10. If the difference in refractive index is less than or equal to the upper limit value, it is preferable because inconveniences such as clouding of the film do not occur, and if the difference is greater than or equal to the lower limit value, a sufficient light diffusion effect can be provided.

The addition amount of the translucent particles is preferably 3 to 30% by mass and particularly preferably 5 to 20% by mass in the total solid content of the hard coat layer. If the addition amount of the translucent particles is less than or equal to the upper limit value, it is preferable because inconveniences such as clouding of the film do not occur, and if it is equal to or more than the lower limit value, a sufficient light diffusion effect can be provided. When the addition amount of the translucent particles is expressed by the translucent particle amount in the hard coat layer as the formed light diffusion layer, it is preferably 10 to 3000 mg / m ² , more preferably 90 to 2000 mg / m ² . Become.

Specific examples of the translucent particles include inorganic compound particles such as silica particles and TiO ₂ particles; resin particles such as acrylic particles, crosslinked acrylic particles, polystyrene particles, crosslinked styrene particles, melamine resin particles, and benzoguanamine resin particles. Is preferred. Of these, crosslinked styrene particles, crosslinked acrylic particles, and silica particles are preferred.
As the shape of the translucent particle, either a true sphere or an indefinite shape can be used.

  In the hard coat layer in the invention, two or more different kinds of translucent particles may be used in combination. When two or more kinds of translucent particles are used, in order to effectively exert the refractive index control by mixing them, the difference in refractive index between the highest refractive index particle and the lowest refractive index particle is It is preferably 0.02 or more and 0.10 or less, and particularly preferably 0.03 or more and 0.07 or less. It is also possible to impart anti-glare properties with translucent particles having a larger particle size and to impart other optical characteristics with translucent particles having a smaller particle size. For example, when an antireflection film is attached to a high-definition image display device of 133 ppi or more, it is required that there is no problem in optical performance called glare. Glare is derived from the fact that the unevenness of the film surface (which contributes to antiglare properties) causes the pixels to be enlarged or reduced and loses brightness uniformity, but is smaller than the light-transmitting particles that impart antiglare properties. The diameter can be greatly improved by using translucent particles different from the refractive index of the binder.

  Furthermore, the particle size distribution of the translucent particles is most preferably monodisperse, and the particle size of each particle is preferably as close as possible. For example, when particles having a particle size of 20% or more than the average particle size are defined as coarse particles, the proportion of coarse particles is preferably 1% or less, more preferably 0.1% or less of the total number of particles. More preferably, it is 0.01% or less. Translucent particles having such a particle size distribution are obtained by classification after a normal synthesis reaction, and particles having a more preferable distribution can be obtained by increasing the number of classifications or increasing the degree of classification. .

  The particle size distribution of the translucent particles is measured by a Coulter counter method, and the measured distribution is converted into a particle number distribution.

[Inorganic filler]
The hard coat layer is selected from titanium, zirconium, aluminum, indium, zinc, tin, and antimony in addition to the above light-transmitting particles in order to increase the refractive index of the layer and to reduce curing shrinkage. It is preferable that an inorganic filler having an average particle size of 0.2 μm or less, preferably 0.1 μm or less, and more preferably 0.06 μm or less is contained.

  In addition, in order to increase the refractive index difference between the hard coat layer and the translucent particles, in the hard coat layer using the high refractive index translucent particles, in order to keep the refractive index as a layer low, It is also preferable to use an oxide. The preferred particle size is the same as that of the aforementioned inorganic filler.

Specific examples of the inorganic filler used in the hard coat layer include TiO ₂ , ZrO ₂ , Al ₂ O ₃ , In ₂ O ₃ , ZnO, SnO ₂ , Sb ₂ O ₃ , ITO, SiO _{2 and the} like. TiO ₂ and ZrO ₂ are particularly preferable in terms of increasing the refractive index. The surface of the inorganic filler is preferably subjected to a silane coupling treatment or a titanium coupling treatment, and a surface treatment agent having a functional group capable of reacting with a binder species on the filler surface is preferably used.

  The amount of these inorganic fillers added is preferably 10 to 90% of the total mass of the hard coat layer, more preferably 20 to 80%, and particularly preferably 30 to 70%.

  Such an inorganic filler does not scatter because its particle size is sufficiently smaller than the wavelength of light, and a dispersion in which the filler is dispersed in a binder polymer behaves as an optically uniform substance.

The bulk refractive index of the mixture of binder and inorganic filler in the hard coat layer in the present invention is preferably 1.48 to 2.00, more preferably 1.50 to 1.80. In order to make the refractive index within this range, the type and amount ratio of the binder and the inorganic filler may be appropriately selected. How to select it can be easily known experimentally in advance.

  The translucent particles and the inorganic filler are preferably added to the hard coat layer in a dispersion state. As the dispersion medium, a liquid having a boiling point of 60 to 170 ° C. is preferably used. Examples of dispersion media include water, alcohols (eg, methanol, ethanol, isopropanol, butanol, benzyl alcohol), ketones (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone), esters (eg, methyl acetate, ethyl acetate, Propyl acetate, butyl acetate, methyl formate, ethyl formate, propyl formate, butyl formate), aliphatic hydrocarbons (eg hexane, cyclohexane), halogenated hydrocarbons (eg methylene chloride, chloroform, carbon tetrachloride), aromatic Hydrocarbon (eg, benzene, toluene, xylene), amide (eg, dimethylformamide, dimethylacetamide, n-methylpyrrolidone), ether (eg, diethyl ether, dioxane, tetrahydrofuran) Ether alcohols (e.g., 1-methoxy-2-propanol) are included. Toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and butanol are particularly preferred.

  Particles such as translucent particles and inorganic filler can be dispersed in the medium using a disperser. Examples of dispersers include sand grinder mills (eg, bead mill with pins), high speed impeller mills, pebble mills, roller mills, attritors and colloid mills. A sand grinder mill and a high-speed impeller mill are particularly preferred. Further, preliminary dispersion processing may be performed. Examples of the disperser used for the preliminary dispersion treatment include a ball mill, a three-roll mill, a kneader, and an extruder.

  The thickness of the hard coat layer is preferably 0.05 to 10 μm, more preferably 0.10 to 7 μm, and still more preferably 3 μm to 5 μm.

[Thixotropic agent]
Moreover, in the antireflection film of the present invention, it is preferable that any layer contains a thixotropic agent. In particular, it is preferable that a thixotropic agent is used in combination with the above particles when forming the resin film of the hard coat layer. A thixotropic agent exhibits a low viscosity characteristic when a high shear force is applied when a dispersion is applied to a thin film, exhibits good coating properties, and exhibits a high viscosity characteristic in a stationary state after the thin film is developed, whereby fine particles settle. The purpose is to give difficult characteristics. As a result, it is possible to suppress sedimentation of the contained particles until the coating layer is cured, and a large number of particles remain on the surface portion and are distributed with high density, and display light from small pixels with excellent fineness. In contrast, a sufficiently small uneven structure can be formed.

  Accordingly, as the thixotropic agent, one that is transparent and can suppress sedimentation of the contained particles by increasing the viscosity of the coating solution can be used as appropriate, and any known thixotropic agent can be used. Examples thereof include aerosil, layered organic clay, polyacrylic acid and ethyl cellulose.

  The amount of the thixotropic agent can be appropriately determined according to the viscosity characteristics of the dispersion, etc., but generally, from the viewpoint of compatibility between coating properties and fine particle settling, etc., with respect to 100 parts by mass of the binder. Preferably, it is 0.01-10 mass parts, More preferably, it is 0.05-8 mass parts, Most preferably, it is 0.1-5 mass parts.

[Antistatic layer]
In the present invention, it is preferable to provide an antistatic layer from the viewpoint of preventing static electricity on the film surface. The method for forming the antistatic layer is, for example, a method of applying a coating solution of a composition for forming a conductive layer containing conductive fine particles and a reactive curable resin, or a metal or metal oxide that forms a transparent film. A conventionally known method such as a method of forming a conductive thin film by vapor deposition or sputtering can be used.

  The antistatic layer can be formed directly on the transparent support or via a primer layer that strengthens adhesion to the transparent support. Further, when the antistatic layer is used as a layer close to the outermost layer in the structure of the antireflection film, sufficient antistatic properties can be obtained even if the film is thin. The coating method is not particularly limited, and an optimum method may be selected from known methods such as roll coating, gravure coating, bar coating, extrusion coating, etc., depending on the characteristics and coating amount of the coating solution. . It is also preferable to adjust the refractive index of the antistatic layer so as to serve as a medium refractive index layer and a high refractive index layer.

  The thickness of the antistatic layer is preferably from 0.01 to 10 μm, more preferably from 0.03 to 7 μm, and even more preferably from 0.05 to 5 μm.

The surface resistance of the antistatic layer is preferably from 10 ⁵ to 10 is ¹² Omega / □, more preferably 10 ⁵ to 10 ⁹ Omega / □ is the most be 10 ⁵ to 10 ⁸ Omega / □ is preferable. In addition, by providing an antistatic layer, the surface resistance value logSR of the antireflection film is preferably 12 or less from the viewpoint of preventing dust adhesion to the surface of the antireflection film, and logSR is more preferably 10 or less. . The surface resistance of the antistatic layer can be measured using a super insulation resistance / microammeter “TR8601” {manufactured by Advantest Co., Ltd.) at 25 ° C. and a humidity of 60% RH.

  The antistatic layer is preferably substantially transparent. Specifically, the haze of the antistatic layer is preferably 10% or less, more preferably 5% or less, further preferably 3% or less, and most preferably 1% or less. Further, the transmittance of light having a wavelength of 550 nm is preferably 50% or more, more preferably 60% or more, further preferably 65% or more, and most preferably 70% or more.

  The antistatic layer also preferably has a high hardness, and the specific antistatic layer has a pencil hardness of 1 kg (as defined in JIS K-5400), preferably H or higher, and preferably 2H or higher. Is more preferably 3H or more, and most preferably 4H or more.

[Conductive fine particles of antistatic layer]
The conductive fine particles are preferably inorganic particles formed from a metal oxide or nitride. Examples of metal oxides or nitrides include tin oxide, indium oxide, zinc oxide and titanium nitride. Tin oxide and indium oxide are particularly preferred.

  The conductive fine particles are mainly composed of oxides or nitrides of these metals, and may further contain other elements. The main component means a component having the largest content (mass%) among the components constituting the particles. Examples of other elements include Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P, S, B, Nb, In, V and halogen atoms are included. In order to increase the conductivity of tin oxide and indium oxide, it is preferable to add Sb, P, B, Nb, In, V and a halogen atom. Particularly preferred are tin oxide (ATO) containing Sb and indium oxide (ITO) containing Sn. The ratio of Sb in ATO is preferably 3 to 20% by mass. The ratio of Sn in ITO is preferably 5 to 20% by mass.

  The average particle diameter of the primary particles of the conductive fine particles used for the antistatic layer is preferably 1 to 150 nm, more preferably 5 to 100 nm, and most preferably 5 to 70 nm. The average particle diameter of the conductive fine particles in the antistatic layer to be formed is 1 to 200 nm, preferably 5 to 150 nm, more preferably 10 to 100 nm, and most preferably 10 to 80 nm. preferable. The average particle diameter of the conductive fine particles is an average diameter weighted by the mass of the particles, and can be measured by a light scattering method or an electron micrograph.

The specific surface area of the conductive inorganic fine particles is preferably from 10 to 400 m ² / g, more preferably from 20 to 200 m ² / g, and most preferably from 30 to 150 m ² / g.

  The conductive fine particles may be surface-treated. The surface treatment is performed using an inorganic compound or an organic compound. Examples of inorganic compounds used for the surface treatment include alumina and silica. Silica treatment is particularly preferred. Examples of the organic compound used for the surface treatment include polyols, alkanolamines, stearic acid, silane coupling agents, and titanate coupling agents. Silane coupling agents are most preferred. Two or more types of surface treatments may be combined.

  The shape of the conductive fine particles is preferably a rice grain shape, a spherical shape, a cubic shape, a spindle shape or an indefinite shape. Two or more kinds of conductive fine particles may be used in combination in the antistatic layer.

  The proportion of the conductive fine particles in the antistatic layer is preferably 20 to 90% by mass, preferably 25 to 85% by mass, and more preferably 30 to 80% by mass.

  The conductive fine particles are used for forming an antistatic layer in the form of a dispersion. As the preferred dispersion medium, those mentioned as the dispersion medium in the above description of [Inorganic filler] can be used.

[Production of antireflection film]
Each layer of the antireflection film of the present invention is prepared by dissolving each layer-forming composition in a coating dispersion medium described later as a coating solution, a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a die coating method, It can be formed by a coating method such as a wire bar coating method, a gravure coating method or an extrusion coating method (described in US Pat. No. 2,681,294). Two or more layers may be applied simultaneously. Regarding the method of simultaneous application, the methods described in the specifications of US Pat. Nos. 2,761,789, 2,941,898, 3,508,947, and 3,526,528 and Yuji Harasaki, Coating Engineering, page 253, Asakura Shoten (1973) are particularly limited. It can be done without using it.

In the antireflection film of the present invention, at least the low refractive index layer is laminated, so that a bright spot defect is easily noticeable when foreign matter such as dust or dust is present. The bright spot defect in the present invention is a defect that can be visually observed by reflection on the coating film, and can be detected by an operation such as black coating on the back surface of the antireflection film after coating. The bright spot defects that can be visually observed are generally 50 μm or more.
In the antireflection film of the present invention, the number of bright spot defects is preferably 20 or less per square meter, more preferably 10 or less, still more preferably 5 or less, and particularly preferably 1 or less. If it is in said range, it is preferable from a viewpoint of the yield at the time of manufacture, and it can be used without a problem also in manufacture of a large area antireflection film, and is preferable.

In order to continuously produce the antireflection film of the present invention, a step of continuously feeding a roll-shaped transparent support film, a step of applying a coating liquid, a step of drying, a step of curing a coating film,
A step of winding up the support film having the cured layer is performed.
From the roll-shaped support film, the support film is continuously sent out to the clean room. In the clean room, the static electricity charged in the support film is removed by an electrostatic charge-removing device, and then attached to the support film. Remove foreign matter using a dust remover. Subsequently, the coating liquid is applied onto the support film in the application section installed in the clean room, and the applied support film is sent to the drying room and dried.
The support film having the dried coating layer is fed from the drying chamber to the radiation curing chamber, and irradiated with radiation, the curable resin contained in the coating layer is polymerized and cured. Furthermore, the support film having a layer cured by radiation is sent to the thermosetting portion and heated to complete the curing, and the support film having the layer having been completely cured is wound up into a roll shape.

Each of the above steps may be performed every time each layer is formed, or a plurality of coating units-drying chambers-radiation curing units-thermosetting chambers may be provided to form each layer continuously. From the viewpoint of property, it is preferable to form each layer continuously.
A specific description will be given with reference to an embodiment of a manufacturing apparatus preferably used in the present invention shown in FIG.
Here, FIG. 1 is a schematic view showing one embodiment of a manufacturing apparatus used in the present invention.
The manufacturing apparatus shown in FIG. 1 includes a web W for performing the above-described continuous feeding process, a roll 1 thereof, a plurality of guide rollers (not shown), and a winding process for performing the above-described winding process. A roll 2 and a necessary number of film forming units 100, 200, 300, and 400 for performing the coating step, the drying step, and the step of curing the coating film are appropriately installed. In the present embodiment, the film forming unit 100 is for forming a hard coat layer, the film forming unit 200 is for forming a medium refractive index layer, and the film forming unit 300 is for forming a high refractive index layer, The film forming unit 400 is for forming a low refractive index layer.
Since each film forming unit has the same structure, the film forming unit 100 will be described. The film forming unit 100 includes a coating unit 101 for performing the process of applying the coating liquid, a drying unit 102 for performing the process of drying the coated liquid, and the dried coating liquid. And a curing device 103 for performing a curing process.
The apparatus shown in FIG. 1 is an example of a configuration in which four layers are continuously applied without winding up, but it is of course possible to change the number of film forming units according to the layer configuration.
Using an apparatus in which three film forming units are installed, the roll-shaped support film coated with the hard coat layer is continuously sent out, and a hard coat layer, a high refractive index layer, and a low refractive index layer are produced. It is more preferable to wind up after sequentially coating with a membrane unit, using the apparatus shown in FIG. 1 in which four film-forming units are installed, continuously feeding a roll-shaped support film, a hard coat layer, More preferably, the intermediate refractive index layer, the high refractive index layer, and the low refractive index layer are sequentially coated on each film forming unit and then wound.

  Among the above coating methods, the microgravure method is generally preferably used. The high refractive index layer and the low refractive index layer of the present invention can also be produced by the microgravure method. A satisfactory surface shape can be obtained against the coating amount distribution in the width direction and various surface failures, and satisfactory performance is achieved by optimizing the material and shape of the metal blade used for scraping the coating amount distribution in the longitudinal direction. Is obtained.

  In order to produce an antireflection film with a small number of bright spot defects within the above-mentioned range, the dispersion of inorganic fine particles in the coating for forming a low refractive index layer must be precisely controlled, and the precision of the coating solution A filtration operation may be performed. At the same time, each layer forming the antireflection layer is formed on the film before the application process in the application unit and the drying process performed in the drying chamber are performed in a high clean air atmosphere and the application is performed. It is preferable that dust and dust are sufficiently removed. The air cleanliness of the coating process and the drying process is desirably class 10 (353 particles / 0.5 m or more / (cubic meter) or less) based on the standard of air cleanliness in the US Federal Standard 209E. Preferably it is class 1 (35.5 particles / (cubic meter) or less) having a particle size of 0.5 μm or more. Moreover, it is more preferable that the degree of air cleanliness is high also in the feeding and winding parts other than the coating-drying process.

As a dust removal method used in a dust removal step as a pre-process for coating, a method of pressing a nonwoven fabric, a blade or the like against the film surface described in JP-A-59-150571, described in JP-A-10-309553 Highly clean air is blown at a high speed to peel off the deposit from the film surface, and suction is performed at a suction port adjacent to the film. Ultrasonic-vibrated compressed air described in JP-A-7-333613 is sprayed onto the deposit. And a dry dust removal method such as a method of peeling and suctioning (manufactured by Shinkosha, New Ultra Cleaner, etc.).
In addition, a method of introducing a film into a cleaning tank and peeling off deposits with an ultrasonic vibrator, supplying a cleaning liquid to the film described in Japanese Patent Publication No. 49-13020, and then blowing and sucking high-speed air As described in JP-A-2001-38306, a wet dust removal method such as a method in which a web is continuously rubbed with a roll wetted with a liquid and then the liquid is sprayed onto the rubbed surface for cleaning. be able to. Among such dust removal methods, a method using ultrasonic dust removal or a method using wet dust removal is particularly preferable from the viewpoint of dust removal effect.

  In addition, it is particularly preferable to remove static electricity on the support film before performing such a dust removal step from the viewpoint of increasing dust removal efficiency and suppressing adhesion of dust. As such a static elimination method, a corona discharge ionizer, a light irradiation ionizer such as UV or soft X-ray, or the like can be used. The charged voltage of the support film before and after dust removal and coating is desirably 1000 V or less, preferably 300 V or less, and particularly preferably 100 V or less.

[Dispersion medium for coating]
It does not specifically limit as a dispersion medium for a coating used for the said coating liquid, You may use it individually or in mixture of 2 or more types. Preferred dispersion media include aromatic hydrocarbons such as toluene, xylene and styrene, chlorinated aromatic hydrocarbons such as chlorobenzene and orthodichlorobenzene, methane derivatives such as monochloromethane, ethane derivatives such as monochloroethane, and the like. Chlorinated aliphatic hydrocarbons, alcohols such as methanol, isopropyl alcohol and isobutyl alcohol, esters such as methyl acetate and ethyl acetate, ethers such as ethyl ether and 1,4-dioxane, acetone, methyl ethyl ketone, methyl isobutyl ketone, Examples include ketones such as cyclohexanone, glycol ethers such as ethylene glycol monomethyl ether, alicyclic hydrocarbons such as cyclohexane, aliphatic hydrocarbons such as normal hexane, and mixtures of aliphatic or aromatic hydrocarbons. Among these solvents, a dispersion medium for coating prepared by alone or mixing two or more ketones is particularly preferable.

[Surface tension of coating solution]
The surface tension of the coating solution is preferably in the range of 15 to 36 [mN / m]. If it is this range, since the nonuniformity at the time of drying is suppressed, it is preferable. More preferably, it is the range of 17 [mN / m]-32 [mN / m], and the range of 19 [mN / m]-26 [mN / m] is especially preferable. If it is this range, the upper limit speed | rate which can be apply | coated is not dropped, and it is preferable. The surface tension can be controlled by adding a leveling agent.

[filtration]
The coating solution used for coating is preferably filtered before coating. As a filter for filtration, it is preferable to use a filter having a pore diameter as small as possible within a range in which components in the coating solution are not removed. For the filtration, it is preferable to use a filter having an absolute filtration accuracy of 0.1 to 10 μm, and it is more preferable to use a filter having an absolute filtration accuracy of 0.1 to 5 μm. The thickness of the filter is preferably 0.1 to 10 mm, and more preferably 0.2 to 2 mm. In that case, the filtration pressure is preferably 1.5 MPa or less, more preferably 1.0 MPa or less, and further preferably 0.2 MPa or less.
The filtration filter member is not particularly limited as long as it does not affect the coating solution. Specifically, the same thing as the filtration member of the wet dispersion of an inorganic compound mentioned above is mentioned.
It is also preferable to ultrasonically disperse the filtered coating solution immediately before coating to assist defoaming and dispersion holding of the dispersion.

  The drying and curing conditions are not particularly limited, but can be performed at a low temperature of 50 ° C. to 150 ° C., preferably 70 to 120 ° C., for 100 hours or less, and further for 0.5 hours to 10 hours.

[Physical properties of the entire antireflection film]
[Haze value and average reflectance]
The antireflection film of the present invention thus formed has a haze value of preferably 0.3 to 70%, more preferably 0.5 to 60%, and an average reflectance of 450 nm to 650 nm. Preferably it is 3.0% or less, More preferably, it is 2.5% or less. When the antireflection film of the present invention has a haze value and an average reflectance in the above range, good antiglare property or internal scattering property and antireflection property can be obtained without causing deterioration of the transmitted image, which is preferable.

[Center line average roughness (Ra) of antireflection film]
In the present invention, from the viewpoint of improving the visibility and the viewpoint of improving the strength of the film, the outermost surface of the antireflection film according to the present invention needs to have controlled fine irregularities. The range of the unevenness on the outermost surface is such that the center line average surface roughness Ra specified by JIS B-0601 is in the range of 0.005 to 0.30 μm, preferably 0.05 to The range is 0.30 μm, more preferably 0.10 to 0.30 μm. If Ra is within this range, the film strength of the antireflection film does not decrease, and the durability does not decrease. On the other hand, when Ra is 0.30 μm or less, there is no reduction in contrast due to an increase in light scattering on the surface of the antireflection film and no deterioration in image quality due to an increase in whiteness of the film.

  In order to adjust the centerline average roughness (Ra) of the antireflection film within this range, there are roughly two means. One is to adjust by controlling the kind, particle size, amount, and film thickness of the above-mentioned translucent particles. Another method is a method of adjusting by controlling the drying speed and viscosity of the coating liquid and the temperature of the coating liquid, and adding a gelling agent (polyacrylamides, cellulose derivatives, polysaccharides, etc.) or a thixotropic agent. Is also preferable. In this method, the hard coat layer may or may not contain translucent particles.

[10-point average roughness (Rz) of antireflection film, average length (RSm) of contour curve element] In the present invention, from the viewpoint of further improving the strength and durability of the film, the antireflection film according to the present invention. It is preferable that Rz and RSm of the outermost surface are in the following ranges. Here, Rz represents the 10-point average roughness defined by JIS B-0601, and RSm represents the average length of the contour curve elements defined by JIS B-0601. Rz is preferably 0.02 to 3.0 μm, more preferably 0.10 to 2.5 μm, and most preferably 0.20 to 2.0 μm. RSm is preferably 10 to 200 μm, more preferably 15 to 150 μm, and most preferably 20 to 100 μm.

[Center line average roughness of hard coat layer (Ra)]
In the present invention, from the viewpoint of improving the durability of the resulting antireflection film and improving the strength of the film, the surface of the hard coat layer on which the low refractive index layer is coated preferably has fine irregularities. .

  From the viewpoint of improving durability after storage under conditions of high humidity and severe temperature changes, as preferable irregularities, the centerline average surface roughness Ra defined by JIS B-0601 is 0.005 to 0.30 μm. More preferably, it is the range of 0.05-0.30 micrometers, Most preferably, it is 0.10-0.30 micrometers.

  Moreover, from the point of the durability improvement after preserve | saving in ozone-containing air | atmosphere, preferable centerline average surface roughness Ra is the range of 0.007-0.20 micrometers. In order to adjust to this range, there are mainly two means as described above, and any method is effective. However, the hard coat layer containing the antistatic inorganic fine particles is particularly preferable because the surface unevenness can be easily controlled.

[Abrasion resistance of antireflection film]
The antireflection film of the present invention preferably has a limit load of 400 g or more in a water swab rubbing test on the surface of the antireflection film after exposure to 10 ppm of ozone for 192 hours. More preferably, it is 500 g or more, More preferably, it is 600 g or more.
The limit load in the water swab rubbing test is obtained as follows.
Each sample is processed into a polarizing plate, stored in an environment of ozone 10 ppm, 30 ° C., 60% RH for 192 hours (8 days), and then taken out into the atmosphere. A cotton swab (Health Refre (trade name) manufactured by Toyo Sanyo Co., Ltd.) is fixed to the rubbing tip of a rubbing tester, and the sample is fixed with clips on the top and bottom of a smooth dish. Is immersed in water at 25 ° C., a load is applied to a cotton swab, and a 20 reciprocating rubbing test is performed. Rubbing distance (one way): 1 cm, rubbing speed: about 2 reciprocations / second After the water on the surface of the sample after rubbing is dried, it is visually observed whether the film is peeled off. The test is performed 10 times on the same sample, and the test is started by starting with an initial load of 100 g and increasing the load by 50 g until film peeling occurs 5 times or more. The load at which film peeling is less than 5 times in 10 tests is defined as the critical load. The film peeling is judged based on whether the reflection state of the surface is visually changed. When the section of the film in which the reflection state is changed is observed with an electron microscope, it is observed that the film thickness of the uppermost layer is 5% or more thinner, or the uppermost layer and other constituent layers are peeled off.

(Transparent support)
As the transparent support of the antireflection film of the present invention, a plastic film is preferably used. Examples of the polymer forming the plastic film include cellulose esters (for example, triacetyl cellulose, diacetyl cellulose, typically “Fujitac TAC-TD80U”, “Fujitac TD80UF”, etc., manufactured by Fuji Photo Film Co., Ltd.), polyamide, polycarbonate, Polyester (for example, polyethylene terephthalate, polyethylene naphthalate), polystyrene, polyolefin, norbornene resin {"Arton", manufactured by JSR Corporation}, amorphous polyolefin {"Zeonex", manufactured by Nippon Zeon Corporation}, etc. It is done. Of these, triacetyl cellulose, polyethylene terephthalate, and polyethylene naphthalate are preferable, and triacetyl cellulose is particularly preferable.

  Cellulose acylate such as triacetyl cellulose is composed of a single layer or a plurality of layers. A single-layer cellulose acylate is produced by drum casting or band casting disclosed in Japanese Patent Application Laid-Open No. 7-11055, etc. The cellulose acylate comprising the latter plurality of layers is disclosed in It can be produced by the so-called co-casting method disclosed in JP-A-61-94725 and JP-B-62-43846. That is, raw material flakes such as halogenated hydrocarbons (dichloromethane, etc.), alcohols (methanol, ethanol, butanol, etc.), esters (methyl formate, methyl acetate, etc.), ethers (dioxane, dioxolane, diethyl ether, etc.), etc. A solution obtained by dissolving in a solvent and adding various additives such as a plasticizer, an ultraviolet absorber, a deterioration preventing agent, a slipping agent, a peeling accelerator as necessary (hereinafter sometimes referred to as a dope), When cast by a dope supply means (hereinafter sometimes referred to as a die) on a support composed of a horizontal endless metal belt or a rotating drum, a single dope is cast as a single layer. In the case of multiple layers, a low-concentration dope is co-cast on both sides of a high-concentration cellulose ester dope and dried to some extent on the support to give a rigid film. It was detached from the support and then a process comprising the removal of various solvents and passed through a drying section by the conveying means.

A typical solvent for dissolving cellulose acylate as described above is dichloromethane. However, from the viewpoint of the global environment and working environment, the solvent preferably does not substantially contain a halogenated hydrocarbon such as dichloromethane. “Substantially free” means that the proportion of halogenated hydrocarbon in the organic solvent is less than 5% by mass (preferably less than 2% by mass).
When preparing a cellulose acylate dope using a solvent substantially free of dichloromethane or the like, a special dissolution method as described later is essential.

The first dissolution method is called a cooling dissolution method and will be described below.
First, cellulose acylate is gradually added to a solvent at a temperature around room temperature (−10 to 40 ° C.) while stirring. The mixture is then cooled to -100 to -10 ° C (preferably -80 to -10 ° C, more preferably -50 to -20 ° C, most preferably -50 to -30 ° C). The cooling can be performed, for example, in a dry ice / methanol bath (−75 ° C.) or a cooled diethylene glycol solution (−30 to −20 ° C.). When cooled in this way, the mixture of cellulose acylate and solvent solidifies. Further, when this is heated to 0 to 200 ° C. (preferably 0 to 150 ° C., more preferably 0 to 120 ° C., most preferably 0 to 50 ° C.), a solution in which cellulose acylate flows in the solvent is obtained. The temperature may be increased by simply leaving it at room temperature or in a warm bath.

The second method is called a high temperature melting method and will be described below.
First, cellulose acylate is gradually added to a solvent at a temperature around room temperature (−10 to 40 ° C.) while stirring. The cellulose acylate solution of the present invention is preferably swelled in advance by adding cellulose acylate to a mixed solvent containing various solvents. In this method, the dissolution concentration of cellulose acylate is preferably 30% by mass or less, but is preferably as high as possible from the viewpoint of drying efficiency during film formation. Next, the organic solvent mixed solution is heated to 70 to 240 ° C. under a pressure of 0.2 MPa to 30 MPa (preferably 80 to 220 ° C., more preferably 100 to 200 ° C., most preferably 100 to 190 ° C.). Next, since these heated solutions cannot be applied as they are, it is necessary to cool them below the lowest boiling point of the solvent used. In that case, it is common to cool to -10-50 degreeC and to return to a normal pressure. For cooling, the high-pressure and high-temperature vessel or line containing the cellulose acylate solution may be left at room temperature, and more preferably, the apparatus may be cooled using a coolant such as cooling water. A cellulose acylate film substantially free of halogenated hydrocarbons such as dichloromethane and a method for producing the same are disclosed in JIII Journal of Technical Disclosure No. 2001-1745 (issued on March 15, 2001, hereinafter published Technical Report 2001- Abbreviated to No. 1745).

[Use of antireflection film in liquid crystal display devices]
When the antireflection film of the present invention is used in a liquid crystal display device, it is disposed on the outermost surface of the image display device by providing an adhesive layer on one side. When the transparent support is triacetyl cellulose, triacetyl cellulose is used as a protective film for protecting the polarizing film of the polarizing plate. Therefore, it is preferable from the viewpoint of cost to use the antireflection film of the present invention as it is as a protective film. .

[Saponification]
When the antireflection film of the present invention is disposed on the outermost surface of the image display device or used as it is as a protective film for a polarizing plate, the antireflection layer of the antireflection film is used to improve the adhesion. It is preferable to hydrophilize the surface on the side opposite to the side provided with (hereinafter sometimes referred to as the back surface of the antireflection film) by alkali treatment. The saponification treatment is carried out by a known method, for example, by immersing the film in an alkaline solution for an appropriate time. After being immersed in the alkali solution, it is preferable to wash the substrate sufficiently with water or neutralize the alkali component by immersing in a dilute acid so that the alkali component does not remain in the film.

  The hydrophilized surface of the transparent support on the back surface of the antireflection film is particularly effective for improving the adhesion with a polarizing film containing polyvinyl alcohol as a main component. In addition, the hydrophilic surface makes it difficult for dust in the air to adhere to it, so it is difficult for dust to enter between the deflection film and the antireflection film when bonded to the deflection film, thus preventing point defects due to dust. It is valid.

  The saponification treatment is preferably carried out so that the contact angle with water on the transparent support surface on the back surface of the antireflection film is 40 ° or less. More preferably, it is 30 ° or less, particularly preferably 20 ° or less.

  Specific means for the alkali saponification treatment can be selected from the following four means (1) to (4). Among these, (1) is excellent in that it can be processed in the same process as a general-purpose cellulose acylate film. On the other hand, if the saponification solution remains, it may become a problem. On the other hand, the method (2) is preferable because it can improve the adhesion between the low refractive index layer and the lower layer in the antireflection film of the present invention.

(1) After forming the low refractive index layer of the antireflection layer on the transparent support, the surface and the back surface of the antireflection film are saponified by immersing in an alkaline solution at least once.
(2) Before the low refractive index layer is formed on the transparent support, the surface of the transparent support having a layer formed before the low refractive index layer is formed by immersing in an alkaline solution at least once. Saponify the back side. In this method, the surface on which the low refractive index layer is provided is also subjected to alkali treatment.
(3) After forming up to the low refractive index layer of the antireflection layer on the transparent support, the surface on the low refractive index layer side is protected with a laminate, and immersed in an alkaline solution at least once, Saponify the back side.
(4) Before or after forming the layer constituting the antireflection layer on the transparent support, an alkaline solution is applied to the surface of the transparent support opposite to the surface on which the antireflection layer is formed, and heated. Only the back surface of the antireflection film is saponified by washing with water and / or neutralizing.

  That is, in the antireflection film of the present invention, the surface on which the low refractive index layer is provided is preferably subjected to alkali treatment in advance.

  And the antireflection film of this invention is obtained by forming each layer as mentioned above in the said transparent support body.

[Polarizer]
The polarizing plate of the present invention has the above-described antireflection film of the present invention.

  In the polarizing plate of the present invention, the Re retardation value of at least one of the films constituting the polarizing plate is preferably 20 or more and 70 nm or less, and the Rth retardation value is preferably 70 or more and 400 nm or less.

In this specification, the Re retardation value and the Rth retardation value are defined by the following mathematical formulas (2) and (3), respectively.
Equation (2): Re = (n x -n y) × d
Equation (3): Rth = {( n x + n y) / 2-n z} × d

In Equation (2) and (3), n _x is a slow axis direction in the film plane is the refractive index of the (refractive index direction of maximum). _ny is the refractive index in the fast axis direction (the direction in which the refractive index is minimized) in the film plane. _nz is the refractive index in the thickness direction of the film. d is the thickness of the film whose unit is nm.

  The polarizing plate is mainly composed of two protective films that sandwich the polarizing film from both sides. The antireflection film of the present invention is preferably used for at least one of the two protective films sandwiching the polarizing film from both sides. Since the antireflection film of the present invention also serves as a protective film, the production cost of the polarizing plate can be reduced. Further, by using the antireflection film of the present invention as the outermost layer, reflection of external light and the like can be prevented, and a polarizing plate having excellent scratch resistance, antifouling property and the like can be obtained.

  As the polarizing film, a known polarizing film or a polarizing film cut out from a long polarizing film whose absorption axis is neither parallel nor perpendicular to the longitudinal direction may be used. A long polarizing film whose absorption axis is neither parallel nor perpendicular to the longitudinal direction is produced by the following method.

  That is, a polarizing film stretched by applying tension while holding both ends of a polymer film such as polyvinyl alcohol continuously supplied by a holding means, and stretched at least 1.1 to 20.0 times in the film width direction. The difference in the longitudinal direction traveling speed of the holding devices at both ends of the film is within 3%, and the angle formed by the film traveling direction at the exit of the step of holding both ends of the film and the substantial stretching direction of the film is inclined by 20 to 70 °. As described above, the film can be produced by a stretching method in which the traveling direction of the film is bent while holding both ends of the film. In particular, those inclined by 45 ° are preferably used from the viewpoint of productivity.

  The method for stretching the polymer film is described in detail in paragraphs [0020] to [0030] of JP-A-2002-86554.

[Display device, liquid crystal mode]
The display device of the present invention has the above-described antireflection film of the present invention.
That is, the antireflection film of the present invention can be applied to an image display device such as a liquid crystal display device (LCD), a plasma display panel (PDP), an electroluminescence display (ELD), or a cathode ray tube display device (CRT). . Since the antireflection film of the present invention has a transparent support, the transparent support side is adhered to the image display surface of the image display device.

  The antireflection film of the present invention, when used as one side of the surface protective film of the polarizing film, is twisted nematic (TN), super twisted nematic (STN), vertical alignment (VA), in-plane switching (IPS), optical It can be preferably used for a transmissive, reflective, or transflective liquid crystal display device of a mode such as a curry compensate bend cell (OCB).

In VA mode liquid crystal cell,
(1) In addition to a narrowly-defined VA mode liquid crystal cell (described in JP-A-2-176625) in which rod-like liquid crystalline molecules are aligned substantially vertically when no voltage is applied, and substantially horizontally when a voltage is applied. ,
(2) VA mode multi-domain (MVA mode) liquid crystal cell ("SID97, Digest of Tech. Papers" (Preliminary Collection) Vol. 28 (1997), page 845)
(3) A liquid crystal cell in a mode (n-ASM mode) in which rod-like liquid crystalline molecules are substantially vertically aligned when no voltage is applied and twisted multi-domain alignment is applied when a voltage is applied. Page (1998)}, and
(4) SURVAVAL mode liquid crystal cell (announced at LCD International 98)
Is included.

  For a VA mode liquid crystal cell, a polarizing plate prepared by combining a biaxially stretched triacetyl cellulose film with the antireflection film of the present invention is preferably used. As for the method for producing a biaxially stretched triacetyl cellulose film, for example, the methods described in JP-A Nos. 2001-249223 and 2003-170492 are preferably used.

  The OCB mode liquid crystal cell is a liquid crystal display device using a bend alignment mode liquid crystal cell in which rod-like liquid crystal molecules are aligned in a substantially opposite direction (symmetrically) between the upper part and the lower part of the liquid crystal cell. U.S. Pat. Nos. 4,583,825 and 5,410,422. Since the rod-like liquid crystal molecules are symmetrically aligned at the upper and lower portions of the liquid crystal cell, the bend alignment mode liquid crystal cell has a self-optical compensation function. For this reason, this liquid crystal mode is also called an OCB (Optically Compensatory Bend) liquid crystal mode. The bend alignment mode liquid crystal display device has an advantage of high response speed.

  In an ECB mode liquid crystal cell, rod-like liquid crystal molecules are substantially horizontally aligned when no voltage is applied, and is most frequently used as a color TFT liquid crystal display device, and is described in many documents. For example, it is described in “EL, PDP, LCD display” {issued by Toray Research Center (2001)}.

  In particular, for a TN mode or IPS mode liquid crystal display device, as described in Japanese Patent Application Laid-Open No. 2001-100043, an optical compensation film having an effect of widening the viewing angle is protected on the two sides of the polarizing film. By using the film on the side opposite to the antireflection film of the present invention, a polarizing plate having an antireflection effect and a viewing angle expansion effect can be obtained with the thickness of one polarizing plate, which is particularly preferable. .

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these. Unless otherwise specified, “part” and “%” are based on mass.

[Preparation of composition coating solution for forming each layer]
{Preparation of hard coat layer-forming composition coating solution (A-1)}
Mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate “KAYARAD PET-30” {manufactured by Nippon Kayaku Co., Ltd.} 45 g, mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate “DPHA” {Nippon Kayaku Co., Ltd. 5) was diluted with 23.5 g of toluene and 15.0 g of cyclohexanone. Further, 2 g of a 1: 1 mass ratio mixture of polymerization initiators “Irgacure 184” and “Irgacure 907” (both manufactured by Ciba Specialty Chemicals Co., Ltd.) was added and mixed and stirred. The refractive index of the coating film obtained by applying this solution and curing with ultraviolet rays was 1.51.
The obtained mixed liquid was filtered through a polypropylene filter having a pore size of 30 μm to prepare a hard coat layer forming composition coating liquid (A-1).

{Preparation of hard coat layer forming composition coating solution (A-2)}
Cross-linked polystyrene particles having an average particle diameter of 3.5 μm, further dispersed for 20 minutes at 10,000 rpm in a polytron disperser with the hard coat layer-forming composition coating liquid (A-1) ”
SX-350 "{refractive index 1.61, manufactured by Soken Chemical Co., Ltd.} 30% toluene dispersion 1.7 g, and crosslinked acrylic-styrene particles having an average particle size of 3.5 μm {refractive index 1.55, Soken Chemical 13.3 g of a 30% toluene dispersion manufactured by Co., Ltd., and finally, 0.75 g of a fluorine-based surface modifier (FP-1) represented by the following chemical formula (4), silane coupling agent “KBM” -5103 "{Shin-Etsu Chemical Co., Ltd.} 10 g was added.
The obtained mixed liquid was filtered through a polypropylene filter having a pore diameter of 30 μm to prepare a hard coat layer forming composition coating liquid (A-2).

{Preparation of hard coat layer forming composition coating solution (A-3)}
For the hard coat layer-forming composition coating liquid (A-1), classification-strengthened crosslinked polymethyl methacrylate (PMMA) particles “MXS-300” having an average particle size of 3.0 μm {crosslinking agent ethylene glycol dimethacrylate, 35% of a 30% toluene dispersion of a cross-linking agent amount of 30%, a refractive index of 1.49, manufactured by Soken Chemicals Co., Ltd.} was added to 35 g of a dispersion liquid at 10,000 rpm for 20 minutes using a Polytron disperser, and then an average particle size of 1 Add 90 g of a 30% toluene dispersion of 5 μm silica particles “Seahoster KE-P150” {refractive index 1.46, manufactured by Nippon Shokubai Co., Ltd.} for 30 minutes at 10,000 rpm with a Polytron disperser and mix. Stir.
The obtained mixed liquid was filtered through a polypropylene filter having a pore diameter of 30 μm to prepare a hard coat layer forming composition coating liquid (A-3).

{Preparation of hard coat layer forming composition coating solution (A-4)}
In the composition coating liquid for forming a hard coat layer (A-3), instead of silica particles having an average particle diameter of 1.5 μm, classified strengthening highly crosslinked PMMA particles “MXS-150H” {crosslinking agent having an average particle diameter of 1.5 μm Except for using 130 g of 30% toluene dispersion of ethylene glycol dimethacrylate, cross-linking agent amount 30%, refractive index 1.49, manufactured by Soken Chemicals Co., Ltd. Similarly, a hard coat forming composition coating solution (A-4) was prepared.

{Preparation of composition coating liquid for hard coat layer formation (A-5)}
In the coating liquid for hard coat layer (A-2), instead of polystyrene particles having an average particle diameter of 3.5 μm, classified highly-crosslinked PMMA particles “MXS-300” having an average particle diameter of 3.0 μm {crosslinking agent ethylene glycol di Except for using 20 g of 30% methyl isobutyl ketone dispersion of methacrylate, cross-linking agent amount 30%, refractive index 1.49, manufactured by Soken Chemicals Co., Ltd. Thus, a hard coat layer forming composition coating solution (A-5) was prepared.

{Preparation of hard coat layer forming composition coating solution (B-1)}
285 g of a commercially available zirconia-containing UV curable hard coat solution “Desolite Z7404” {manufactured by JSR Corporation, solid content concentration of about 61%, solid content of ZrO _{2 of} about 70%, polymerizable monomer and polymerization initiator contained} A mixture “DPHA” of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) 85 g was mixed, and further diluted with 60 g of methyl isobutyl ketone and 17 g of methyl ethyl ketone. Furthermore, 28 g of silane coupling agent “KBM-5103” {manufactured by Shin-Etsu Chemical Co., Ltd.} was mixed and stirred. The refractive index of the coating film obtained by applying this solution and curing with ultraviolet rays was 1.61.

Further, 30% toluene dispersion of a crosslinked polystyrene particle “SX-350” {refractive index 1.61, manufactured by Soken Chemical Co., Ltd.} having an average particle size of 3.5 μm dispersed in this solution for 20 minutes at 10,000 rpm with a polytron disperser. 1.7 g of a liquid and 13.3 g of a 30% toluene dispersion of crosslinked acrylic-styrene particles {refractive index 1.55, manufactured by Soken Chemical Co., Ltd.} having an average particle size of 3.5 μm are added. 4) Fluorine-based surface modifier (FP-1) 0.75 g and silane coupling agent “KBM-5103” {Shin-Etsu Chemical Co., Ltd.} 10 g were added.
The obtained mixed liquid was filtered through a polypropylene filter having a pore diameter of 30 μm to prepare a hard coat layer forming composition coating liquid (B-1).

{Preparation of hard coat layer forming composition coating solution (C-1)}
In the hard coat layer forming composition coating liquid (A-2), the hard coat layer was exactly the same except that 1 part of the organic clay was added to 100 parts of the solid content of the coating liquid (A-2). A forming composition coating liquid (C-1) was prepared.

{Preparation of hard coat layer forming composition coating solution (C-2)}
In the hard coat forming composition coating liquid (A-3), fine-particle silica “AEROSIL 200” {average primary particle 12 nm, refractive index 1.46, with respect to 100 parts of the solid content of the coating liquid (A-3). A hard coat layer forming composition coating solution (C-2) was prepared in exactly the same manner except that 0.5 part of Nippon Aerosil Co., Ltd.} was added.

{Preparation of hard coat layer forming composition coating solution (C-3)}
In the hard coat layer-forming composition coating liquid (A-3), fine-particle silica “AEROSIL 200” {average primary particle 12 nm, refractive index 1.46 with respect to 100 parts of the solid content of the coating liquid (A-3). , Nippon Aerosil Co., Ltd.} and 0.5 parts of Bright 20GNR4.6-EH {benzoguanamine / melamine / formaldehyde condensate spherical powder plated with nickel and gold, Nippon Chemical Industry Co., Ltd. A hard coat layer forming composition coating solution (C-3) was prepared in exactly the same manner except that 0.1 part of) made} was added.

{Preparation of composition coating solution (D-1) for forming a low refractive index layer}
Thermally crosslinkable fluorine-containing polymer "JTA113" with a refractive index of 1.43 {solid content concentration 6%, main solvent methyl ethyl ketone, manufactured by JSR Corporation} 18g, methyl ethyl ketone 2g and cyclohexanone 0.6g were added, and after stirring, pore size The mixture was filtered through a 1 μm polypropylene filter to prepare a low refractive index layer-forming composition coating solution (D-1) for a comparative example.

{Preparation of low refractive index layer forming composition coating solution (D-2)}
A flask was charged with 100 g of trifluoropropyltrimethoxysilane, 200 g of tridecafluorooctyltrimethoxysilane, 1700 g of tetraethoxysilane, 200 g of isobutanol, and 6 g of aluminum acetylacetonate and stirred. Next, 500 g of 0.25 mol / L acetic acid water was added dropwise little by little. After completion of dropping, the mixture was stirred at room temperature for 3 hours. Thereafter, 600 g of diacetone alcohol was added, and the mixture was filtered through a polypropylene filter having a pore size of 1 μm to prepare a composition coating solution (D-2) for forming a low refractive index layer.

{Preparation of composition coating solution for forming a low refractive index layer (D-3)}
In the preparation step of the low refractive index layer-forming composition coating liquid (D-2), the silicone leveling agent “L-9000 (CS100)” {linear dimethyl silicone-EO block copolymer, Nippon Unicar Co., Ltd. ) Made} A composition coating solution for forming a low refractive index layer (D-3) was prepared in the same manner except that 30 g was added.

{Preparation of composition coating solution (D-4) for forming a low refractive index layer}
In the preparation step of the composition for forming a low refractive index layer (D-3), before adding 0.25 mol / L of acetic acid water dropwise, the silane coupling agent “KBM-5103” {3-acryloxy A low refractive index layer-forming composition coating solution (D-4) was prepared in exactly the same manner except that 50 g of propyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd. was added.

{Preparation of low refractive index layer-forming composition coating solution (D-5)}
A flask was charged with 100 g of 3-glycidoxypropyltrimethoxysilane, 1000 g of trifluoropropyltrimethoxysilane, 400 g of heptadecafluorodecyltrimethoxysilane, 500 g of tetraethoxysilane, and 200 g of isobutanol. Next, 419 g of 0.25 mol / L acetic acid water was added dropwise little by little. After completion of dropping, the mixture was stirred at room temperature for 3 hours. Next, 6 g of aluminum acetylacetonate was added, and stirring was further performed for 3 hours. Thereafter, 600 g of diacetone alcohol was added, and the mixture was filtered through a polypropylene filter having a pore size of 1 μm to prepare a composition coating solution for forming a low refractive index layer (D-5).

{Preparation of low refractive index layer-forming composition coating solution (D-6)}
In the preparation step of the composition for forming a low refractive index layer (D-5), 30 g of a silicone leveling agent “X-22-163C” {terminal epoxy-modified silicone, manufactured by Shin-Etsu Silicone Co., Ltd.} was added at the final stage. Except for this, a composition coating solution for forming a low refractive index layer (D-6) was prepared in the same manner.

{Preparation of low refractive index layer-forming composition coating solution (D-7)}
In the step of preparing the composition for forming a low refractive index layer (D-6), before adding 0.25N aqueous acetic acid dropwise, silane coupling agent “KBM-5103” {3-acryloxypropyltrimethoxy A composition coating solution for forming a low refractive index layer (D-7) was prepared in exactly the same manner except that 50 g of Silane, manufactured by Shin-Etsu Chemical Co., Ltd. was added.

{Preparation of composition coating solution (E-1) for forming a low refractive index layer}
Hollow silica dispersion {particle size: about 40-50 nm, shell thickness: 6-8 nm, refractive index: 1.31, solid content concentration: 20 with respect to 100 g of the above composition for forming a low refractive index layer (D-4) %, The main solvent isopropyl alcohol, and 97 g of the particle size changed according to Preparation Example 4 of JP-A-2002-79616} are added, and after stirring, the mixture is filtered through a polypropylene filter having a pore size of 30 μm, 10 μm, and 1 μm. Thus, a composition coating solution (E-1) for forming a low refractive index layer was prepared.

{Preparation of composition coating liquid for low refractive index layer formation (E-2)}
In addition to 100 g of the composition for forming a low refractive index layer (D-4), a hollow silica dispersion {particle size of about 40 to 50 nm, shell thickness of 6 to 8 nm, refractive index of 1.31, solid content 147 g of 20% concentration, main solvent isopropyl alcohol, prepared by changing the particle size according to Preparation Example 4 of JP-A-2002-79616}, and after stirring, multistage with a polypropylene filter having a pore size of 30 μm, 10 μm, 1 μm Filtration was performed to prepare a composition coating solution (E-2) for forming a low refractive index layer.

{Preparation of composition coating liquid for low refractive index layer formation (E-3)}
In addition to 100 g of the composition for forming a low refractive index layer (D-7), a hollow silica dispersion {particle size of about 40 to 50 nm, shell thickness of 6 to 8 nm, refractive index of 1.31, solid content 97 g of 20% concentration, main solvent isopropyl alcohol, prepared by changing the particle size in accordance with Preparation Example 4 of JP-A-2002-79616}, and after stirring, multistage with a polypropylene filter having a pore size of 30 μm, 10 μm, 1 μm Filtration was performed to prepare a composition coating solution (E-3) for forming a low refractive index layer.

{Preparation of antistatic layer forming composition coating solution (AS-1)}
100 g of ATO-dispersed hard coating agent “Pertron C-4456-S7” (solid content: 45%) manufactured by Nippon Pernox Co., Ltd., 30 g of cyclohexanone, 10 g of methyl ethyl ketone, silane coupling agent “KBM-5103” {3-acryloxypropyl Add 1.5 g of trimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd., and after stirring, filter through a polypropylene filter having a pore size of 10 μm to prepare a composition coating solution (AS-1) for forming an antistatic layer did.

{Preparation of antistatic layer forming composition coating solution (AS-2)}
“Desolite KZ6805” from JSR Co., Ltd. (solid content 5% hard coating agent, inorganic content 80% in solid content, acrylate binder used, the main component of inorganic substance is antimony-doped tin oxide particles with primary particle size of about 15 nm ) 1% of silane coupling agent “KBM-5103” {3-acryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.} per solid content, and after stirring, with a polypropylene filter having a pore size of 10 μm Filtration was performed to prepare an antistatic layer-forming composition coating liquid (AS-2).

Example 1
[Preparation of antireflection film]
Comparative Example 1-1
[Preparation of Antireflection Film Sample 101]
(1) Coating of hard coat layer A triacetyl cellulose film “Fujitac TAC-TD80U” {manufactured by Fuji Photo Film Co., Ltd.} having a thickness of 80 μm is unwound in a roll form, and the composition for forming a hard coat layer is applied. Liquid (A-1) was applied under the conditions of a gravure roll rotation speed of 30 rpm and a conveyance speed of 35 m / min using a micro gravure roll having a diameter of 180 lines / inch and a gravure pattern of 40 μm in depth and a doctor blade. Then, after drying at 60 ° C. for 150 seconds, using an air-cooled metal halide lamp {manufactured by Eye Graphics Co., Ltd.) under a nitrogen purge, an ultraviolet ray with an illuminance of 400 mW / cm ² and an irradiation amount of 250 mJ / cm ² Was applied to cure the coating layer to form a 4.6 μm thick hard coat layer and wound up.

(2) Coating of low refractive index layer 1% by mass with respect to the solid content (residue after evaporation of the volatile organic solvent) of the low refractive index layer forming composition coating liquid (D-1) Isophorone diisocyanate was mixed with the coating solution (D-1) immediately before coating, and coated on the hard coat layer formed above with a bar coater. After drying at 80 ° C. for 5 minutes, it was further cured at 120 ° C. for 20 minutes. Then, using a 240 W / cm air-cooled metal halide lamp {manufactured by Eye Graphics Co., Ltd.} under a nitrogen purge, ultraviolet rays having an illuminance of 400 mW / cm ² and an irradiation amount of 200 mJ / cm ² were irradiated, and a low refraction of 100 nm thickness was achieved. A rate layer was formed and wound up. The antireflection film sample thus obtained is designated as sample 101. In preparation of the antireflection film other than the sample 101, 1% by mass of isophorone diisocyanate was added to the solid content of each composition for forming a low refractive index layer.

[Evaluation of antireflection film]
About the obtained antireflection film, the following items were evaluated.

(1) Sample Storage / Forced Degradation Conditions (1-1) Standard Conditions The antireflection film sample prepared in the above step is stored for 7 days at 25 ° C. and 60% RH.

(1-2) High-humidity storage conditions Each sample was stored at 60 ° C. and 90% RH for 2 or 7 days.

(2) Cross-cut adhesion evaluation A cross-cut test based on JIS K-5400 was performed for each sample stored under the above conditions. Specifically, the surface of each sample on the side of the antireflection layer is provided with 11 cuts at 1 mm intervals in the vertical and horizontal directions to make 100 1 mm square grids, on which cellophane adhesive tape is applied, 90
Peel off quickly at ° and count the number of grids remaining without peeling. Those having this number of 90 or more are practical.

(3) Surface roughness About each sample preserve | saved on the said reference conditions, the centerline average surface roughness Ra of the surface was calculated | required by the method of JISB-0601.

(4) Measurement of surface free energy After each sample was conditioned at 25 ° C and 60% RH for 2 hours, the contact angle with water and methylene iodide was measured, and the surface free energy (mJ / m ² ) was calculated from these values. Calculated.

(5) Average reflectance Using a spectrophotometer {manufactured by JASCO Corp.}, a spectral reflectance at an incident angle of 5 ° was measured in a wavelength region of 380 to 780 nm. The average reflectance of 450-650 nm was used for the result.

Examples 1-1 to 1-10 and Comparative Example 1-2
[Preparation of antireflection film samples 102 to 112]
In preparation of the antireflection film sample 101 of Comparative Example 1-1, instead of using the hard coat layer forming composition coating liquid (A-1) and the low refractive index layer forming composition coating liquid (D-1), Antireflection film samples 102 to 112 were produced in the same manner as Comparative Example 1-1 except that the hard coat layer forming composition coating solution and the low refractive index layer forming composition coating solution shown in Table 1 were used. .

Examples 1-1-1 to 1-13 and Comparative Example 1-3
[Preparation of antireflection film samples 113 to 116]
In preparation of the antireflection film sample 101 of Comparative Example 1-1, instead of using the hard coat layer forming composition coating liquid (A-1) and the low refractive index layer forming composition coating liquid (D-1), Using the hard coat layer forming composition coating solution and the low refractive index layer forming composition coating solution shown in Table 1, samples 113, 114, and 115 have a hard coat layer thickness of 3.8 μm, and sample 116 has a hard coating. Antireflection film samples 113 to 116 were produced in the same manner as in Comparative Example 1-1 except that the thickness of the coat layer was changed to 3.5 μm.

  Table 1 shows the evaluation results of the used hard coat layer forming composition coating liquid and low refractive index layer forming composition coating liquid, and the obtained antireflection film samples 101 to 116.

From the results shown in Table 1, the following is clear.
The antireflective film sample satisfying the surface roughness of the present invention by using specific particles in the hard coat layer using a low refractive index layer that satisfies the requirements of the present invention is a cross-cut adhesion even after storage under high humidity conditions {Comparison between Samples 101, 102, 116 (Comparative Examples 1-1, 1-2, 1-3) and 103, 113 (Examples 1-1, 1-11), etc.}}.

  An antireflection film sample using a silicone compound or the like for the low refractive index layer and having a surface free energy within the preferred range of the present invention improves the adhesion of the board after storage under high humidity conditions {Sample 110 (Example 1-8) (Outside surface free energy range) and 103 (Example 1-1) (within range), Sample 112 (Example 1-10) (outside range) and 111 (Example 1-9) (within range) )comparison}.

  Moreover, the antireflection film sample in which the thixotropic agent is added to the hard coat layer improves the adhesion of the board after storage under high humidity conditions {Sample 103 (Example 1-1) (without addition) and 108 (Example) 1-6) (addition), comparison of sample 104 (Example 1-2) (no addition) and 109 (Example 1-7) (addition)}.

Example 2
[Preparation of antireflection film]
Comparative Example 2-1
[Preparation of Antireflection Film Sample 201]
(1) Coating of antistatic layer 80 μm thick triacetyl cellulose film “Fujitac TAC-TD80U” (manufactured by Fuji Photo Film Co., Ltd.) is unrolled in the form of a roll to form the above antistatic layer forming composition Using a microgravure roll having a diameter of 360 lines / inch and a gravure pattern with a depth of 40 μm, and a doctor blade, an object coating solution (AS-1), a gravure roll rotation speed of 30 rpm, a conveyance speed of 35 m / min After coating at 80 ° C. for 120 seconds and using a 160 W / cm air-cooled metal halide lamp {manufactured by Eye Graphics Co., Ltd.> under a nitrogen purge, the illuminance is 200 mW / cm ² and the irradiation amount is 250 mJ / cm ^2. The ultraviolet ray was irradiated to cure the coating layer, and an antistatic layer having a thickness of 1.0 μm was formed and wound up.

  On the antistatic layer, according to Example 1, the hard coating layer forming composition coating liquid (A-1) and the low refractive index layer forming composition {with respect to the solid content of (D-1) 1 mass% isophorone diisocyanate added} was sequentially applied and photocured to prepare an antireflection film sample 201. The thickness of the hard coat layer after photocuring was adjusted to 4.3 μm, and the thickness of the low refractive index layer was adjusted to 95 nm. In preparation of the antireflection film sample other than the sample 201, 1% by mass of isophorone diisocyanate was added to the solid content of each coating solution for the low refractive index layer.

Examples 2-1 to 2-20 and Comparative Examples 2-2 to 4
[Preparation of antireflection film samples 202 to 224]
In the preparation of the antireflection film sample 201 of Comparative Example 2-1, the antistatic layer forming composition coating solution, the hard coat layer forming composition coating solution and the low refractive index layer forming composition coating solution are listed in Table 2. The antireflection film samples 201 to 224 were produced in the same manner as the sample 201 except that the above changes were made.

  Antireflective film samples 216 to 224 were coated with an antistatic layer-forming composition coating solution (AS-1) on a 80 μm-thick triacetylcellulose film “Fujitac TAC-TD80U” (manufactured by Fuji Photo Film Co., Ltd.). Without performing, the process after application | coating of the composition coating liquid for hard-coat layer formation was implemented. Sample 215 was prepared such that the coating order was a hard coat layer, an antistatic layer, and a low refractive index layer in order from the support side, and the thickness of the antistatic layer was 100 nm.

  About the obtained antireflection film, the surface roughness was measured in the same manner as in Example 1. In addition, the following tests were conducted. Table 2 shows the evaluation results of each layer-forming composition coating solution used and the obtained antireflection film samples 201 to 224.

(1) Sample Storage / Forced Degradation Conditions (1-1) Standard Conditions The same conditions as in Example 1 and Comparative Example 1 were used.

(1-3) Heat cycle conditions For each sample, a cycle of temperature increase / decrease between −40 ° C. and + 90 ° C. is 1 cycle 30
Repeated 100 times or 200 times under the condition of minutes.

(6) Steel wool scratch resistance evaluation A rubbing test was performed using a rubbing tester under the following conditions.
Evaluation environmental conditions: 25 ° C., 60% RH
Rubbing material: Steel wool “No. 0000” {manufactured by Nippon Steel Wool Co., Ltd.} was wound around the tip (1 cm × 1 cm) of the rubbing of a tester in contact with the sample, and the band was fixed so as not to move.
Moving distance (one way): 13 cm, rubbing speed: 13 cm / sec, load: 500 g / cm ² , tip contact area: 1 cm × 1 cm, rubbing frequency: 10 reciprocations.

An oil-based black ink was applied to the back side of the rubbed sample and visually observed with reflected light, and scratches on the rubbed portion were evaluated according to the following criteria.
○: Even when viewed very carefully, no scratches are visible.
○ △: Slightly weak scratches are visible when viewed very carefully.
Δ: A weak scratch is visible.
Δ ×: moderate scratches are visible.
X: There are scratches that can be seen at first glance.

(7) Measurement of log SR (surface resistance) After adjusting the humidity at 25 ° C. and 60% RH for 2 hours, the surface resistance value (SR) was measured by the circular electrode method. The log SR was calculated by taking the common logarithm of SR.

From the results shown in Table 2, the following is clear.
The sample satisfying the surface roughness of the present invention by using specific particles in the hard coat layer using the low refractive index layer in the antireflection film of the present invention is excellent in steel wool rubbing resistance including after heat cycle { Comparison of Samples 201 and 202 (Comparative Examples 2-1 to 2-2) and 203 to 209 (Examples 2-1 to 2-7), 216, 217 (Comparative Examples 2-3 to 2-4) and 218 to 224 (Comparison of Examples 2-14 to 2-20)}.

  In particular, a sample containing hollow structure particles in the low refractive index layer is excellent in steel wool scuff resistance after heat cycle {Sample 219 (Example 2-15) (no hollow structure particles) and 220, 221 (implementation). Example 2-16 to 2-17) Comparison of (containing hollow structure particles) 223 (Example 2-19) (none) and 224 (Example 2-20) (containing) comparison, 204 (Example 2- 2) (None) and 205, 206 (Examples 2-3 to 2-4) (containing), 208 (Example 2-6) and 209 (Example 2-7) compared}.

  Further, it can be seen that the sample coated with the antistatic layer has a reduced surface resistance of the film and is excellent in chargeability. In particular, the sample 214 (Example 2-12) containing gold-nickel plating particles in the hard coat layer and the sample 215 (Example 2-13) having an antistatic layer directly under the low refractive index layer have reduced surface resistance. Is big.

Example 3
{Preparation of composition coating solution (F-1) for forming a low refractive index layer}
A flask was charged with 2000 g of tetraethoxysilane, 200 g of isobutanol, and 6 g of aluminum acetylacetonate and stirred. Next, 500 g of 0.25 mol / L acetic acid water was added dropwise little by little. After completion of dropping, the mixture was stirred at room temperature for 3 hours. Thereafter, 600 g of diacetone alcohol was added, and the mixture was filtered through a polypropylene filter having a pore size of 1 μm to prepare a composition solution (F-1) for forming a low refractive index layer.

{Preparation of composition coating solution for low refractive index layer formation (F-2)}
_{C 3 F 7 - (OC 3} F 6) 24 -O- (CF 2) 2 -C 2 H 4 -O-CH 2 Si (OCH 3) perfluoropolyether group-containing silane compound consisting of ₃ 160 g, tetraethoxysilane 1840 g, isobutanol 200 g, and aluminum acetylacetonate 6 g were charged into a flask and stirred. Next, 500 g of 0.25 mol / L acetic acid water was added dropwise little by little. After completion of dropping, the mixture was stirred at room temperature for 3 hours. Thereafter, 600 g of diacetone alcohol was added, and the mixture was filtered through a polypropylene filter having a pore size of 1 μm to prepare a composition coating liquid for low refractive index layer formation (F-2).

{Preparation of antifouling layer forming composition coating solution (G-1)}
A perfluoropolyether group-containing silane compound composed of C ₃ F ₇ — (OC ₃ F ₆ ) ₂₄ —O— (CF ₂ ) ₂ —C ₂ H ₄ —O—CH ₂ Si (OCH ₃ ) ₃ is obtained with perfluorohexane. A coating solution diluted to 9.5% by mass was prepared.

{Preparation of antifouling layer forming composition coating solution (G-2)}
A coating solution was prepared by diluting tridecafluorooctyltrimethoxysilane to 6.0% with isopropyl alcohol.

Example 3-1.
[Preparation of Antireflection Film Sample 301]
In preparation of the antireflection film sample 101 of Comparative Example 1-1, instead of using the hard coat layer forming composition coating liquid (A-1) and the low refractive index layer forming composition coating liquid (D-1). Sample 301 was produced in exactly the same manner except that the hard coat layer forming composition coating solution (A-3) and the low refractive index layer forming composition coating solution (F-1) were used.

Example 3-2
[Preparation of Antireflection Film Sample 302]
On the low refractive index layer of the antireflection film sample 301 produced above, the antifouling layer-forming composition coating liquid (G-1) was applied, dried at 120 ° C. for 1 minute, and a thickness of 8 nm. An antifouling layer was prepared, and an antireflection film sample 302 was prepared.

Example 3-3
[Preparation of Antireflection Film Sample 303]
Further, in the antireflection film sample 302, in the same manner as the sample 302 except that the antifouling layer forming composition coating solution (G-1) was used instead of using the antifouling layer forming composition coating solution (G-1). Thus, an antireflection film sample 303 was produced.

Example 3-4
[Preparation of Antireflection Film Sample 304]
Further, in the antireflection film sample 301, the same procedure was performed except that the low refractive index layer forming composition coating solution (F-2) was used instead of using the low refractive index layer forming composition coating solution (F-1). Sample 304 was prepared.

  For the obtained antireflection film samples 301 to 304, a cross-cut adhesion test before and after storage at high humidity was evaluated. The results are shown in Table 3.

  In the antireflection film of Example 3 of the present invention, it can be seen that the sample coated with the antifouling layer is further excellent in durability of the film strength.

Example 4
Using the same hard coat layer-forming composition coating liquid (C-1) and low-refractive index layer-forming composition coating liquid (D-4) as in the antireflection film sample 108 of Example 1, the following antireflection Film samples 401 to 403 were prepared.

Example 4-1
[Preparation of Antireflection Film Sample 401]
A sample that was coated with both the hard coat layer and the low refractive index layer and was photocured was saponified according to the following (1).
(1) After immersing in a 1.5 mol / L NaOH aqueous solution at 55 ° C. for 120 seconds, neutralize by immersing in a 0.05 mol / L H ₂ SO ₄ aqueous solution at 30 ° C. for 20 seconds, After washing with water for 20 seconds, it was dried at 120 ° C. for 2 minutes.

Example 4-2
[Preparation of Antireflection Film Sample 402]
About the sample in which the hard-coat layer was formed, after performing the saponification process of the following (2), the composition for low refractive index layer formation was apply | coated.
(2) After immersing in a 1.5 mol / L NaOH aqueous solution at 55 ° C. for 120 seconds, neutralize by immersing in a 0.05 mol / L H ₂ SO ₄ aqueous solution at 30 ° C. for 20 seconds, and then washing with water It was performed for 20 seconds and dried at 120 ° C. for 2 minutes. Thereafter, a low refractive index layer was applied.

Example 4-3
[Preparation of Antireflection Film Sample 403]
The following (3) saponification treatment was performed on the sample which was applied with both the hard coat layer and the low refractive index layer and was photocured.
(3) The side of the sample on which the low refractive index layer was coated was laminated with a protective masking film (PET with a slightly adhesive layer), and saponified under the same conditions as in (1) above. After saponification, the laminated film was peeled off and evaluated as follows.

  Table 4 shows the results of cross-cut adhesion evaluation after the heat cycle according to Example 1.

  According to Table 4, it can be seen that the interlayer adhesion of the film is further improved by performing the alkali saponification treatment before coating the low refractive index layer. The reason why the adhesion between the layers is improved by the alkali saponification treatment is not necessarily clear, but the adhesion with the low refractive material of the present invention is improved by increasing the polarity of the surface of the hard coat layer by the saponification treatment. Estimated.

Example 5
[Preparation of polarizing plate]
An 80 μm-thick triacetyl cellulose film “Fujitac TAC-TD80U” (manufactured by Fuji Photo Film Co., Ltd.) was immersed in a 1.5 mol / L, 55 ° C. NaOH aqueous solution for 2 minutes, and then neutralized and washed with water. The film obtained in this manner and the back-saponified triacetyl cellulose film of the antireflection film samples of Examples 1 and 2 were adhered to both sides of a polarizing film prepared by adsorbing iodine to polyvinyl alcohol and stretching, thereby protecting the film. Thus, a polarizing plate was produced.

[Liquid Crystal Display]
The thus-prepared polarizing plate is a liquid crystal display device of a notebook personal computer equipped with a transmission type TN liquid crystal display device so that the antireflection film side becomes the outermost surface {Sumitomo 3M Co., Ltd., which is a polarization separation film having a polarization selection layer] When the polarizing plate on the viewing side of “D-BEF” (made between the backlight and the liquid crystal cell) was attached, a very high display quality display device was obtained with very little background reflection. .

Example 6
[Preparation of polarizing plate]
[Production of triacetyl cellulose film]
A polarizing plate was prepared using the following support.
Support 1: A triacetylcellulose film produced according to Example 1 of JP-A-2001-249223.
Support 2: A triacetylcellulose film produced according to Example 2 of JP-A-2001-249223.
Support 3: A triacetylcellulose film produced according to Example 2 of JP-A-2003-170492.
Support 4: Triacetyl cellulose film “Fujitac TD-80U” having a thickness of 80 μm {manufactured by Fuji Photo Film Co., Ltd.}.

Each retardation value is shown below.
Support 1: Re = 40 nm, Rth = 130 nm.
Support 2: Re = 50 nm, Rth = 240 nm.
Support 3: Re = 64 nm, Rth = 120 nm.
Support 4: Re = 4 nm, Rth = 45 nm.

Examples 6-1 to 6-8
[Preparation of Polarizing Plate (P-1)]
Iodine was adsorbed on the stretched polyvinyl alcohol film to produce a polarizing film (PF-1). First, a commercially available triacetyl cellulose (support 4) was saponified and attached to one side of the polarizing film (PF-1) using a polyvinyl alcohol-based adhesive. Next, the support 1 was subjected to saponification treatment and attached to the opposite side of the polarizing film (PF-1) using a polyvinyl alcohol-based adhesive. At that time, the transmission axis of the polarizing film (PF-1) and the slow axis of the support 1 are arranged in parallel, and the transmission axis of the polarizing film (PF-1) and a commercially available triacetyl cellulose film ( A polarizing plate was produced by placing the support 4) so as to be orthogonal to the slow axis of the support 4). The polarizing plate thus obtained was designated as P-1.

[Preparation of Polarizing Plate (P-2)]
A polarizing plate (P-2) was produced in the same manner as in the polarizing plate (P-1) except that the support 2 was used instead of the support 1.

[Preparation of Polarizing Plate (P-3)]
A polarizing plate (P-3) was produced in the same manner as in the polarizing plate (P-1) except that the support 3 was used instead of the support 1.

[Preparation of Polarizing Plate (P-4)]
A polarizing plate (P-3) was produced in the same manner as in the polarizing plate (P-1) except that the support 4 was used instead of the support 1.

[Preparation of Polarizing Plate (P-1A)]
Instead of the support 4 in the polarizing plate (P-1), the antireflection film sample 2 of Example 2
A polarizing plate (P-1A) was produced in the same manner except that 14 was used.

[Preparation of Polarizing Plate (P-2A)]
A polarizing plate (P-2A) was produced in the same manner as in the polarizing plate (P-2) except that the antireflection film sample 214 of Example 2 was used instead of the support 4.

[Preparation of Polarizing Plate (P-3A)]
A polarizing plate (P-1A) was produced in exactly the same manner as in the polarizing plate (P-3) except that the antireflection film sample 214 of Example 2 was used instead of the support 4.

[Preparation of Polarizing Plate (P-4A)]
A polarizing plate (P-4A) was produced in the same manner as in the polarizing plate (P-1A) except that the support 4 was used instead of the support 1.

Example 7
[Liquid Crystal Display]
A pair of polarizing plates and a pair of optical compensation sheets provided in a liquid crystal display device “VL-1530S” {manufactured by Fujitsu Ltd.} using a vertical alignment type liquid crystal cell were peeled off, and instead produced in Example 6. As shown in Table 5, one polarizing plate was attached to each of the observer side and the backlight side via an adhesive. The crossed Nicols were arranged so that the transmission axis of the polarizing plate on the viewer side was in the vertical direction and the transmission axis of the polarizing plate on the backlight side was in the horizontal direction. The configuration is shown in Table 5. Images of the manufactured liquid crystal display device were displayed, and sensory evaluation of external light and background reflection, viewing angle, and glare was performed.

In Table 5, apparatuses having the antireflection film of the present invention are apparatus B (Example 7-1), apparatus D (Example 7-2), apparatus F (Example 7-3), apparatus H (Example). 7-4).
In addition, at least one retardation value of the protective film having the antireflection film of the present invention and constituting the polarizing plate is in a preferred range in the present invention (Re retardation value is 20 to 70 nm and Rth retardation is used. The devices having a value of 70 or more and 400 nm or less were devices B, D, and F, and indicated as Y type in the “Polarizing plate combination type” column. The others were indicated as Z type.

As a result, the apparatuses B, D, F and H (Examples 7-1 to 7-4) having the antireflection film of the present invention correspond to these apparatuses and do not have the antireflection film of the present invention. Compared to A, C, E, and G (Comparative Examples 7-1 to 7-4), it is recognized that the reflectance is reduced, the external light and background are less reflected, and the viewing angle is expanded without causing glare. It was.
Further, the devices B, D and F having the antireflection film of the present invention and having at least one retardation value of the protective film constituting the polarizing plate within the preferred range of the present invention have a particularly wide viewing angle, It was found that the visibility was extremely high.

Example 8
[Organic EL display device]
When the antireflection film samples of Examples 1 and 2 were bonded to the glass plate on the surface of the organic EL display device via an adhesive, reflection on the glass surface was suppressed, and a display device with high visibility was obtained. It was.

Example 9
[Preparation of antireflection film]
{Preparation of low refractive index layer-forming composition coating solution (H-1)}
For 100 g of the above low refractive index layer forming composition (D-2), hollow silica dispersion “CS60-IPA” {particle size 60 nm, shell thickness 10 nm, refractive index 1.31, solid content concentration 20 %, Main solvent isopropyl alcohol, manufactured by Catalyst Kasei Kogyo Co., Ltd.)} and stirred to prepare a low refractive index layer-forming composition coating solution (H-1).

{Preparation of low refractive index layer-forming composition coating solution (H-2)}
The low refractive index layer is obtained by further adding 1.5% by mass of isophorone diisocyanate to the solid content mass of the coating liquid (H-1) to the low refractive index layer forming composition coating liquid (H-1). A forming composition coating solution (H-2) was prepared.

{Preparation of composition coating liquid for forming a low refractive index layer (H-3)}
In the above-described composition for forming a low refractive index layer (H-1), 5 g of a silane coupling agent “KBM-5103” {3-acryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.} is added. Except that, a composition coating solution (H-3) for forming a low refractive index layer was prepared in the same manner.

{Preparation of low refractive index layer-forming composition coating solution (H-4)}
For 100 g of the low refractive index layer-forming composition coating solution (F-1) of Example 3, hollow silica dispersion “CS60-IPA” {particle size 60 nm, shell thickness 10 nm, refractive index 1.31. 147 g of a solid content concentration of 20%, main solvent isopropyl alcohol, manufactured by Catalyst Kasei Kogyo Co., Ltd.}, and a silane coupling agent “KBM-5103” {3-acryloxypropyltrimethoxysilane, Shin-Etsu Chemical Co., Ltd. )} 5 g was added to prepare a composition for forming a low refractive index layer (H-4).

{Preparation of composition coating liquid for hard coat layer formation (J-1)}
The silica particle “Seahoster KE-P150” having an average particle diameter of 1.5 μm {refractive index of 1.46, Nippon Shokubai (Nippon Catalyst) with respect to 95.5 g of the hard coat layer forming composition coating liquid (A-1) of Example 1 Co., Ltd.} 30% toluene dispersion was dispersed in a Polytron disperser at 10,000 rpm for 30 minutes, mixed and stirred to obtain a hard coat layer forming composition coating liquid (J-1).

{Preparation of hard coat layer forming composition coating solution (J-2)}
In the hard coat layer forming composition coating liquid (J-1), except that 1 part by mass of organic clay was added to 100 parts by mass of the solid content of the coating liquid (J-1), A hard coat layer forming composition coating solution (J-2) was prepared.

{Preparation of hard coat layer forming composition coating solution (J-3)}
In the hard coat forming composition coating liquid (J-1), the fine particle silica “AEROSIL 200” {average primary particle 12 nm, refractive index 1 with respect to 100 parts by mass of the solid content of the coating liquid (J-1). .46, Nippon Aerosil Co., Ltd.} was added in the same manner as described above, except that 1.0 part by mass of a hard coat layer forming composition coating solution (J-3) was prepared.

{Preparation of hard coat layer forming composition coating solution (J-4)}
In the said hard-coat layer formation composition coating liquid (J-1), it is the same except having added 1.5 mass parts of acetyl propionyl cellulose with respect to 100 mass parts of solid content of this coating liquid (J-1). Then, a hard coat layer forming composition coating solution (J-4) was prepared.

{Preparation of hard coat layer forming composition coating solution (J-5)}
In the hard coat layer-forming composition coating liquid (J-1), the same procedure except that 2.5 parts by mass of acetylpropionylcellulose was added to 100 parts by mass of the solid content of the coating liquid (J-1). Thus, a composition coating liquid (J-5) for forming a hard coat layer was prepared.

{Preparation of hard coat layer forming composition coating solution (J-6)}
In the hard coat layer forming composition coating liquid (J-1), the silane coupling agent “KBM-5103” {3-acryloxypropyl is used with respect to 100 parts by mass of the solid content of the coating liquid (J-1). A hard coat layer-forming composition coating solution (J-6) was prepared in the same manner except that 15 parts by mass of trimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd. was added.

{Preparation of hard coat layer forming composition coating solution (J-7)}
In the hard coat layer-forming composition coating liquid (J-1), except that 35 parts by mass of the following sol liquid a was added to 100 parts by mass of the solid content of the coating liquid (J-1). Thus, a hard coat layer forming composition coating solution (J-6) was prepared.

(Preparation of sol solution a)
In a reactor equipped with a stirrer and a reflux condenser, methyl ethyl ketone 120 parts by mass, silane coupling agent “KBM-5103” {3-acryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.} 100 parts by mass, diiso 3 parts by mass of propoxyaluminum ethyl acetoacetate {“Kelope EP-12” manufactured by Hope Pharmaceutical Co., Ltd.] is added and mixed, and then 30 parts by mass of ion-exchanged water is added and reacted at 60 ° C. for 4 hours. Sol was obtained by cooling. The mass average molecular weight was 1600, and among the components higher than the oligomer component, the component having a molecular weight of 1000 to 20000 was 100%. Further, from the gas chromatography analysis, the raw material acryloyloxypropyltrimethoxysilane did not remain at all.

{Preparation of hard coat layer forming composition coating solution (J-8)}
In the hard coat layer forming composition coating liquid (J-1), the low refractive index layer forming composition coating liquid (F-) of Example 3 is used with respect to 100 g of the solid content of the coating liquid (J-1). A hard coat layer forming composition coating solution (J-8) was prepared in the same manner except that 20 g of 1) was added.

{Preparation of hard coat layer forming composition coating solution (J-9)}
In the hard coat layer-forming composition coating liquid (J-1), the silane coupling agent “KBM-403” {3-glycidoxyxypropyltrimethyl is added to 100 g of the solid content of the coating liquid (J-1). A composition coating liquid for forming a hard coat layer (J-9) was prepared in the same manner except that 15 g of methoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd. was added.

{Preparation of hard coat layer forming composition coating solution (J-10)}
In the hard coat layer forming composition coating solution (J-4), the silane coupling agent “KBM-5103” {3-acryloxypropyltrimethoxy is used with respect to 100 g of the solid content of the coating solution (J-4). A composition coating liquid for forming a hard coat layer (J-10) was prepared in the same manner except that 15 g of Silane, manufactured by Shin-Etsu Chemical Co., Ltd. was added.

{Preparation of hard coat layer forming composition coating solution (J-11)}
In the hard coat layer forming composition coating liquid (J-4), 1.5% by mass of isophorone diisocyanate is added to 100 g of the solid content of the coating liquid (J-4) to form a hard coat layer. A composition coating liquid (J-11) was prepared.

{Preparation of hard coat layer forming composition coating solution (J-12)}
Commercially available zirconia-containing UV curable hard coat liquid “Desolite Z7404” {manufactured by JSR Corporation, solid content concentration of about 61%, solid content of ZrO ₂ content of about 70%, polymerizable monomer, polymerization initiator contained} 285 g, di 85 g of a mixture of pentaerythritol pentaacrylate and dipentaerythritol hexaacrylate “DPHA” {manufactured by Nippon Kayaku Co., Ltd.} was mixed, and further diluted with 60 g of methyl isobutyl ketone and 17 g of methyl ethyl ketone. Furthermore, 28 g of a silane coupling agent “KBM-5103” {manufactured by Shin-Etsu Chemical Co., Ltd.} was mixed and stirred. The refractive index of the coating film obtained by applying this solution and curing with ultraviolet rays was 1.61.

  To this liquid, 90 g of 30% methyl ethyl ketone dispersion of silica particles “Seahoster KE-P150” {refractive index 1.46, manufactured by Nippon Shokubai Co., Ltd.} having an average particle diameter of 1.5 μm was 10000 rpm with a Polytron disperser. Was added after being dispersed for 30 minutes, and mixed and stirred. Finally, 0.75 g of the fluorine-based surface modifier (FP-1) was added. The obtained mixed liquid was filtered through a polypropylene filter having a pore diameter of 30 μm to prepare a hard coat layer forming composition coating liquid (J-12).

{Preparation of antistatic layer forming composition coating solution (AS-3)}
A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate with respect to 100 parts by weight of “SNS-10M” (ATO 19.7% by mass, dispersant 10.7%, solvent methyl ethyl ketone) manufactured by Ishihara Sangyo Co., Ltd. "DPHA" {Nippon Kayaku Co., Ltd.} 15.0 parts by mass, silane coupling agent "KBM-5103" {3-acryloxypropyltrimethoxysilane, Shin-Etsu Chemical Co., Ltd.} 1.5 mass Part, photo radical generator “Irgacure 907” {manufactured by Ciba Specialty Chemicals Co., Ltd.) 1.0 part by mass, 30 parts by mass of methoxypropanol are added and mixed, and the solid content concentration becomes 10% by mass with methyl ethyl ketone. To obtain an antistatic layer coating solution (AS-3).

{Preparation of antistatic layer forming composition coating solution (AS-4)}
A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate with respect to 100 parts by weight of “SNS-10M” (ATO 19.7% by mass, dispersant 10.7%, solvent methyl ethyl ketone) manufactured by Ishihara Sangyo Co., Ltd. 10.0 parts by mass of “DPHA” {Nippon Kayaku Co., Ltd.}, silane coupling agent “KBM-5103” {3-acryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.} 1.5 mass Part, photo radical generator “Irgacure 907” {manufactured by Ciba Specialty Chemicals Co., Ltd.) 1.0 part by mass, 30 parts by mass of methoxypropanol are added and mixed, and the solid content concentration becomes 10% by mass with methyl ethyl ketone. To obtain a composition coating solution (AS-4) for forming an antistatic layer.

{Preparation of antistatic layer forming composition coating solution (AS-5)}
A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate with respect to 100 parts by weight of “SNS-10M” (ATO 19.7% by mass, dispersant 10.7%, solvent methyl ethyl ketone) manufactured by Ishihara Sangyo Co., Ltd. 5.0 parts by mass of “DPHA” {Nippon Kayaku Co., Ltd.}, silane coupling agent “KBM-5103” {3-acryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.} 1.5 mass Parts, photo radical generator “Irgacure 907” {manufactured by Ciba Specialty Chemicals Co., Ltd.) 0.7 parts by mass, 30 parts by mass of methoxypropanol are added and mixed so that the solid content concentration becomes 10% by mass with methyl ethyl ketone. To obtain a composition coating solution (AS-5) for forming an antistatic layer.

{Preparation of antistatic layer forming composition coating solution (AS-6)}
A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate with respect to 100 parts by weight of “SNS-10M” (ATO 19.7% by mass, dispersant 10.7%, solvent methyl ethyl ketone) manufactured by Ishihara Sangyo Co., Ltd. 2.0 parts by mass of "DPHA" {Nippon Kayaku Co., Ltd.}, silane coupling agent "KBM-5103" {3-acryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.} 1.5 mass Part, photo radical generator “Irgacure 907” {manufactured by Ciba Specialty Chemicals Co., Ltd.} 0.4 parts by mass, 30 parts by mass of methoxypropanol are added and mixed, so that the solid content concentration becomes 10% by mass with methyl ethyl ketone. To obtain a composition coating solution (AS-6) for forming an antistatic layer.

{Preparation of antistatic layer forming composition coating solution (AS-7)}
A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate with respect to 100 parts by weight of “SNS-10M” (ATO 19.7% by mass, dispersant 10.7%, solvent methyl ethyl ketone) manufactured by Ishihara Sangyo Co., Ltd. 1.0 parts by mass of “DPHA” {Nippon Kayaku Co., Ltd.}, silane coupling agent “KBM-5103” {3-acryloxypropyltrimethoxysilane, Shin-Etsu Chemical Co., Ltd.} 1.5 mass Part, photo radical generator “Irgacure 907” {manufactured by Ciba Specialty Chemicals Co., Ltd.} 0.4 parts by mass, 30 parts by mass of methoxypropanol are added and mixed, so that the solid content concentration becomes 10% by mass with methyl ethyl ketone. To obtain a composition coating solution for forming an antistatic layer (AS-7).

Comparative Example 9-1
[Preparation of Antireflection Film Sample 901]
(1) Coating of hard coat layer A triacetyl cellulose film “Fujitac TAC-TD80U” {manufactured by Fuji Photo Film Co., Ltd.} having a thickness of 80 μm is unwound in a roll form, and the hard coat layer forming composition is applied. Using a micro gravure roll with a diameter of 180 mm / inch and a gravure pattern with a depth of 40 μm and a doctor blade, the liquid (J-1) was subjected to a gravure roll rotation speed of 30 rpm and a conveyance speed of 35 m / min. After applying and drying at 60 ° C. for 150 seconds, using an air-cooled metal halide lamp {manufactured by Eye Graphics Co., Ltd.) under a nitrogen purge, an illuminance of 400 mW / cm ² and an irradiation amount of 120 mJ / cm ² The coating layer was cured by irradiating with ultraviolet rays to form a 5.6 μm thick hard coat layer and wound up.

(2) Coating of low refractive index layer The said low refractive index layer formation composition coating liquid (H-1) was apply | coated on the hard-coat layer coated above with the bar coater. After drying at 80 ° C. for 5 minutes, it was further cured at 120 ° C. for 20 minutes. Next, using a 240 W / cm air-cooled metal halide lamp {manufactured by Eye Graphics Co., Ltd.} under a nitrogen purge, ultraviolet rays having an illuminance of 400 mW / cm ² and an irradiation amount of 200 mJ / cm ² were irradiated, and the thickness was reduced to 100 nm. A refractive index layer was formed and wound up. Thus, the obtained sample is used as an antireflection film sample 901.

Examples 9-1 to 14
[Preparation of antireflection film samples 902 to 915]
In preparation of the antireflection film sample 901 of Comparative Example 9-1, instead of using the hard coat layer forming composition coating liquid (J-1) and the low refractive index layer forming composition coating liquid (H-1), As shown in Table 6, the sample of Comparative Example 9-1 except that the hard coat layer forming composition coating solution and the low refractive index layer forming composition coating solution were used in combination as shown in Table 6. In the same manner as 901, antireflection film samples 902 to 915 were produced.

Examples 9-15
[Preparation of Antireflection Film Sample 916]
In preparation of the antireflection film sample 901 of Comparative Example 9-1, instead of using the hard coat layer forming composition coating liquid (J-1), the hard coat layer forming composition coating liquid (J-12) was used. A hard coat layer was produced in the same manner as the sample 901 of Comparative Example 9-1 except for the above. On the obtained hard coat layer, the low refractive index layer-forming composition coating liquid (H-4) was coated with a bar coater. After drying at 80 ° C. for 5 minutes, it was further cured at 120 ° C. for 20 minutes. Next, using a 240 W / cm air-cooled metal halide lamp {manufactured by Eye Graphics Co., Ltd.} under a nitrogen purge, ultraviolet rays having an illuminance of 400 mW / cm ² and an irradiation amount of 200 mJ / cm ² were irradiated, and the thickness was reduced to 100 nm. A refractive index layer was formed and wound up.

  Next, the antifouling layer forming composition coating solution (G-1) used in Example 3 was applied on the low refractive index layer, dried at 120 ° C. for 1 minute, and a thickness of 8 nm. An antifouling layer was prepared, and an antireflection film sample 916 was prepared.

Examples 9-16
[Preparation of Antireflection Film Sample 917]
In the production of the antireflection film sample 901 of Comparative Example 9-1, instead of using the hard coat layer forming composition coating liquid (J-1), (J-12) was used as the hard coat layer forming composition coating liquid. A hard coat layer was produced in the same manner as the sample 901 of Comparative Example 9-1 except that. On the obtained hard coat layer, the antistatic layer forming composition coating solution (AS-3) was applied so that the film thickness after curing was 150 nm, and an air-cooled metal halide of 240 W / cm under a nitrogen purge. Using a lamp {manufactured by Eye Graphics Co., Ltd.}, ultraviolet rays having an illuminance of 400 mW / cm ² and an irradiation amount of 120 mJ / cm ² were irradiated for curing. On the obtained antistatic layer, according to the sample 901 of Comparative Example 9-1, a low refractive index layer-forming composition coating liquid (H-1) was applied and cured to prepare a sample 917.

Examples 9-17 to 19, Comparative Example 9-2
[Preparation of antireflection film samples 918 to 921]
Instead of using the antistatic layer-forming composition coating liquid (AS-3) in the production of the antireflection film sample 917 of Examples 9-16, as shown in Table 6, the antistatic layer-forming composition coating liquid is used. Except changing, it carried out similarly to preparation of the sample 917 of Example 9-16, and produced the anti-reflective film samples 918-921.

[Evaluation of antireflection film]
About the obtained film, the following items were evaluated.

(1) Surface roughness of hard coat layer Ra of the hard coat layer before coating the low refractive index layer was determined by the method defined in JIS B-0601. In the antireflection film samples 917 to 921, the antistatic layer was handled as a hard coat layer having antistatic ability.

(2) Limit load by rubbing with a cotton swab after ozone exposure After each sample was processed into a polarizing plate, it was stored in an environment of ozone 10 ppm, 30 ° C., 60% RH for 192 hours (8 days), and then taken out into the atmosphere. It was. A cotton swab (Health Refre (trade name) manufactured by Toyo Sanyo Co., Ltd.) is fixed to the rubbing tip of a rubbing tester, and the sample is fixed with clips on the top and bottom of a smooth dish. Was immersed in water at 25 ° C., a load was applied to a cotton swab, and a 20 reciprocating rubbing test was conducted.
Rubbing distance (one way): 1 cm, rubbing speed: about 2 reciprocations / second After drying the water on the surface of the sample after rubbing, it was visually observed whether the film was peeled off. The test was performed 10 times on the same sample, and the test was performed starting from an initial load of 100 g and increasing the load by 50 g until film peeling occurred 5 times or more. The load at which film peeling was less than 5 times during 10 tests was defined as the critical load. The film peeling was judged based on whether the reflection state of the surface was visually changed. A larger limit load corresponds to better scratch resistance.

  About antireflection film samples 901-921, the composition coating liquid for each layer formation used for formation of each layer of those samples and the evaluation result of the obtained antireflection film sample are shown according to Table 6.

From the results shown in Table 6, the following is clear.
In the present invention, it can be seen that the scratch resistance after ozone exposure is improved by increasing the surface roughness of the hard coat layer on which the low refractive index layer is coated as in 902 to 904 {Sample 901 ( Comparison of Comparative Example 9-1) and 902-904 (Examples 9-1 to 9-3)}. In particular, the sample having an antistatic layer containing antistatic particles immediately below the low refractive index layer, the scratch resistance after exposure to ozone becomes remarkable as the surface roughness increases within the scope of the present invention. Improved {Samples 917 to 921 (Examples 9-16 to 9-19)}.

  In addition, it can be seen that the sample in which the hard coat layer contains an organic silyl compound and a derivative thereof, or a polyfunctional isocyanate has a remarkable effect of improving ozone resistance without increasing the surface roughness {Sample 901 (Comparative Example 9- 1) and 906 to 916 (Examples 9-5 to 9-15)}.

Example 10 and Comparative Example 10
Samples 1001 to 911 were prepared in the same manner except that the silica particles “Seahoster KE-P150” having an average particle diameter of 1.5 μm were removed from the hard coat layer.
As a result of evaluation according to Example 9, the reflectivity, the surface roughness (Ra) of the hard coat layer immediately below the low refractive index layer, and the limit load of rubbing the swab after exposure to ozone are shown in Example 9 and Comparative Example 9 It was found that the results were almost the same as the corresponding samples.

It is the schematic which shows one Embodiment of the coating device used in this invention.

Explanation of symbols

W web 1 support film roll 2 take-up roll 100, 200, 300, 400 film forming unit 101 coating unit 102 drying unit 103 curing device

Claims (17)

In an antireflection film provided with an antireflection layer comprising a low refractive index layer formed by coating at least a low refractive index layer forming composition on a transparent support, the low refractive index layer forming composition comprises: It contains at least one of a hydrolyzate of an organic silyl compound represented by the following general formula (1) and a partial condensate thereof, and the center line surface roughness Ra of the outermost surface of the antireflection film is 0.005 to 0.005. An antireflection film characterized by being 30 μm.
General formula (1): R ¹¹ _m Si (X ¹¹ ) _n
(In the formula, X ¹¹ represents —OH, a halogen atom, —OR ¹² group, or —OCOR ¹² group. R ¹¹ represents an alkyl group, an alkenyl group, or an aryl group, and R ¹² represents an alkyl group. M + n represents 4 and m and n are each a positive integer.)   The low refractive index layer contains inorganic fine particles having an average particle diameter of 30% to 120% of the thickness of the low refractive index layer and having a hollow structure and a refractive index of 1.17 to 1.40. The antireflection film as described in 1. The antireflection film according to claim 1, wherein the surface free energy of the outermost surface is 26 mJ / m ² or less.   The antireflection film is a multilayer structure film further comprising a hard coat layer, and at least one of the constituent layers of the antireflection layer contains at least one kind of translucent particles having an average particle diameter of 0.1 to 5 μm. A light diffusing layer dispersed in a light-transmitting resin, wherein a difference in refractive index between the light-transmitting particles and the light-transmitting resin is 0.02 to 0.2, and the light-transmitting particles are light-diffusing The antireflection film according to claim 1, wherein 3 to 30% by mass is contained in the total solid content of the layer.   The antireflection film according to claim 1, wherein the antireflection film further comprises a transparent antistatic layer having a conductive material, and the antireflection film has a surface resistance value logSR of 12 or less.   The hard coat layer is formed by coating a composition for forming a hard coat layer containing at least one of the organic silyl compound represented by the general formula (1), a hydrolyzate thereof, and a partial condensate thereof. Item 5. The antireflection film according to Item 4.   The antireflection film according to claim 4 or 6, wherein the composition for forming a hard coat layer contains a polyfunctional isocyanate compound.   The antireflection film according to claim 4, 6 or 7, wherein the center line surface roughness Ra of the hard coat layer is 0.005 to 0.20 µm.   The antireflection film according to any one of claims 1 to 8, wherein at least one of the constituent layers of the antireflection film contains a thixotropic agent.   The antireflection film according to claim 1, further comprising an antifouling layer as an upper layer of the low refractive index layer.   The antireflection film according to claim 1, wherein the low refractive index layer is provided on the surface subjected to alkali treatment.   The antireflection film according to any one of claims 1 to 11, wherein a limit load in a water swab rubbing test on the surface of the antireflection film after exposure to 10 ppm of ozone for 192 hours is 400 g or more.   A polarizing plate comprising the antireflection film according to claim 1.   The polarizing plate according to claim 13, wherein the Re retardation value of at least one film constituting the polarizing plate is 20 or more and 70 nm or less, and the Rth retardation value is 70 or more and 400 nm or less.   The polarizing plate according to claim 13 or 14, wherein a limit load in a water swab rubbing test on the surface of the antireflection film after exposure to 10 ppm of ozone for 192 hours is 400 g or more.   A display device comprising the antireflection film according to any one of claims 1 to 12, or the polarizing plate according to any one of claims 13 to 15.   The display device according to claim 16, wherein a limit load in a water swab rubbing test on the surface of the antireflection film after exposure to 10 ppm of ozone for 192 hours is 400 g or more.

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