JP2007168429A - Antireflection film, its manufacturing method and polarizing plate using the same, and display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antireflection film improving further a scratch resistance while having a sufficient reflection prevention capability, a manufacturing method of manufacturing the same at low costs, a polarizing plate provided with the antireflection film, and a display device. <P>SOLUTION: The antireflection film includes at least a hard coat layer 2 and a low refractive index layer 5 on a transparent supporter 1. The antireflection film is characterized in that the low refractive index layer is formed by a composition for forming a low refractive index layer containing a binder polymer, at least one kind of polymerization initiators, and a curing compound having an ethylenic unsaturated group. The manufacturing method, and the polarizing plate provided with the antireflection film, and the display device are provided. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an antireflection film having a low reflectance and improved scratch resistance and a method for producing the same, and more particularly to an antireflection film used for a display device such as a liquid crystal display device and a method for producing the same.

  In applications such as adhesives, exterior paints, hard coats, anti-reflection coatings containing organic and inorganic materials, it is possible to improve scratch resistance, strength of cured products, adhesion to other materials in contact It is being considered.

  Among these, in combination with polymerization-curing organic materials, alkoxysilanes containing a polymerization group and / or hydrolysis condensates thereof have attracted attention. For example, Patent Document 1 proposes the combined use of a specific polyalkoxypolysiloxane and a polymerizable silane coupling agent.

  On the other hand, an antireflection film is generally used for a display device such as a cathode ray tube display (CRT), a plasma display (PDP), an electroluminescence display (ELD), or a liquid crystal display (LCD) to reduce contrast due to reflection of external light. In order to prevent the reflection of images and images, it is arranged on the outermost surface of the display device so as to reduce the reflectance by using the principle of optical interference.

  Such an antireflection film can be produced by forming a high refractive index layer such as a hard coat layer on a support, and further forming a low refractive index layer having an appropriate film thickness thereon. In order to realize a low reflectance, a material having a refractive index as low as possible is desired for the low refractive index layer. Further, since the antireflection film is used on the outermost surface of the display device, in many cases, the low refractive index layer which is the uppermost layer of the antireflection film is required to have high scratch resistance. However, in order to realize high scratch resistance in a low refractive index layer which is a thin film having a thickness of about 100 nm, the strength of the coating itself and the adhesion to the lower layer are required.

  To lower the refractive index of the layer, there are means such as (1) introducing fluorine atoms and (2) reducing the density (introducing voids). The lowering of the refractive index and the high scratch resistance was a difficult problem.

For example, Patent Documents 2 to 4 describe means for improving scratch resistance by lowering the coefficient of friction on the coating surface by introducing a polysiloxane structure into the fluorine-containing polymer.
JP-A-9-169847 JP-A-11-189621 Japanese Patent Laid-Open No. 11-228631 JP 2000-313709 A

  In the technique of Patent Document 1, since the reaction between the polyalkoxypolysiloxane and the polymerizable silane coupling agent does not proceed sufficiently and the introduction rate of the polymerizable group is low, the scratch resistance and strength of the cured product are sufficient. is not.

  Although the techniques of Patent Documents 2 to 4 are effective to some extent for improving the scratch resistance, this method alone has sufficient scratch resistance for a film that lacks essential film strength and interfacial adhesion. I can't get it.

  On the other hand, as one means for increasing the film strength, there is a method of introducing an inorganic filler into the low refractive index layer. By using the inorganic fine particles having a low refractive index as a filler, the film strength can be increased without increasing the refractive index of the layer itself. However, with the introduction of the inorganic filler, it is difficult to obtain adhesion to the lower layer, and the scratch resistance is not yet sufficient.

  An object of the present invention is to provide an antireflection film having sufficient antireflection performance and further improved scratch resistance, and a method for producing the antireflection film. In particular, an object of the present invention is to provide an inexpensive method for producing such an antireflection film. It is a further object of the present invention to provide a polarizing plate and a display device provided with such an antireflection film.

The inventors of the present invention have a great effect that rapid curing and the resulting scratch resistance are improved by localizing the polymerization initiator and the curable compound having an ethylenically unsaturated group at the lower part of the low refractive index layer. And the present invention has been made.
That is, the present invention achieves the object by the following configuration.

1) An antireflection film having at least a hard coat layer and a low refractive index layer on a transparent support, wherein the low refractive index layer is a binder polymer, at least one polymerization initiator, and an ethylenically unsaturated group The antireflective film formed with the composition for low-refractive-index layer formation containing the curable compound which has this.
2) The antireflection film as described in 1) above, wherein the polymerization initiator and the curable compound are localized and cured at the lower part of the low refractive index layer.
3) The antireflection film as described in 1) or 2) above, wherein the polymerization initiator is a heat and / or photodegradable initiator.
4) The antireflection film as described in any one of 1) to 3) above, wherein the binder polymer is a thermosetting and / or ionizing radiation curable fluorine-containing polymer, and the curable compound is a non-fluorine compound.
5) The antireflection film as described in any one of 1) to 4) above, wherein the SP value of the polymerization initiator and the curable compound is larger than that of the binder polymer.
6) The antireflection film according to any one of 1) to 5) above, wherein the curable compound is a hydrolyzate of organosilane and / or a partial condensate thereof.
7) The antireflection film as described in any one of 1) to 6) above, wherein the low refractive index layer contains a compound in which a curable compound and a polymerization initiator are linked and bonded in the molecule.
8) The antireflection film as described in any one of 1) to 7) above, wherein the low refractive index layer further contains an inorganic filler selected from silica particles and hollow silica particles.
9) A method for producing an antireflection film having at least a hard coat layer and a low refractive index layer on a transparent support, wherein the composition for forming a low refractive index layer is applied and dried, and then an oxygen concentration of 3 The method for producing an antireflection film according to any one of 1) to 8) above, wherein the film is formed by irradiation with ionizing radiation in an atmosphere of volume% or less.
10) The reflection according to 9) above, wherein the composition for forming a low refractive index layer is applied, dried, further heat-cured, and then cured by irradiation with ionizing radiation in an atmosphere of 3% by volume or less. The manufacturing method of a prevention film.
11) Two protective films of the polarizing film in a polarizing plate using the antireflection film according to any one of 1) to 8) above or the antireflection film produced by the production method according to 9) or 10) above. A polarizing plate used for at least one of them.
12) The antireflection film according to any one of 1) to 8) above, the antireflection film produced by the production method according to 9) or 10) above, or the display having the polarizing plate according to 11) above. A display device, wherein the low refractive index layer is disposed on the viewing side.

In the present invention, the following modes are also preferable.
13) The antireflection film as described in 8) above, wherein the inorganic filler is obtained by surface-treating silica particles and hollow silica particles with an organosilane compound represented by the following general formula (a).
Formula (a): (R ¹¹ ) _m1 -SiX ¹¹ _4-m1
(In the formula, R ¹¹ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. X ¹¹ represents a hydroxyl group or a hydrolyzable group. M1 represents an integer of 0 to 3)

14) The antireflection film as described in 13) above, wherein the substituent R ¹¹ of the organosilane compound in the general formula (a) is a group containing a (meth) acryloyl group or an epoxy group.

  According to the present invention, it is possible to manufacture an antireflection film having a higher scratch resistance while having sufficient antireflection performance by an inexpensive manufacturing method. Moreover, according to the manufacturing method of this invention, such an antireflection film can be stably obtained with high productivity. Furthermore, the display device provided with the antireflection film or the polarizing plate manufactured according to the present invention has a feature of extremely high visibility with little reflection of external light and reflection of the background.

  Hereinafter, the present invention will be described in detail. In the present specification, when a numerical value represents a physical property value, a characteristic value, etc., the description “(numerical value 1) to (numerical value 2)” means “(numerical value 1) or more and (numerical value 2) or less”. . The term “polymerization” as used in the present invention is intended to include copolymerization. Furthermore, the term “on the support” in the present invention includes both the case where the surface directly refers to the support and the case where the surface includes a layer (film) provided on the support. is there.

<Antireflection film>
[Layer structure of antireflection film]
The antireflection film of the present invention has a hard coat layer to be described later on a transparent support (hereinafter also referred to as a base material or a base film), and the reflectance is reduced by optical interference thereon. And an antireflection layer laminated in consideration of the refractive index, the film thickness, the number of layers, the layer order, and the like. The simplest configuration of the antireflection layer is preferably configured by combining a hard coat layer having a refractive index higher than that of the substrate film and a low refractive index layer having a refractive index lower than that of the substrate. As a structural example, a hard coat layer is provided on a base film and a low refractive index layer is further provided, or a hard coat layer is provided on a base film, and a high refractive index layer / low refractive index layer 2 Three layers having different refractive indexes on the hard coat layer, ie, a medium refractive index layer (having a higher refractive index than the base film or the hard coat layer, and a lower refractive index than the high refractive index layer) Layer) / high refractive index layer / low refractive index layer, and the like, and more layers of antireflection layers have been proposed. The antireflection film of the present invention may have a functional layer such as an antiglare layer or an antistatic layer.

The example of the preferable structure of the antireflection film of this invention is shown below. A schematic diagram is shown in FIGS.
a. Transparent support / hard coat layer / low refractive index layer (FIG. 1),
b. Transparent support / hard coat layer / antiglare layer / low refractive index layer,
c. Transparent support / hard coat layer / high refractive index layer / low refractive index layer (FIG. 2),
d. Transparent support / hard coat layer / medium refractive index layer / high refractive index layer / low refractive index layer (FIG. 3),
e. Transparent support / antistatic layer / hard coat layer / medium refractive index layer / high refractive index layer / low refractive index layer,
f. Antistatic layer / transparent support / hard coat layer / medium refractive index layer / high refractive index layer / low refractive index layer.

  When the hard coating layer (2) is applied on the transparent support (1) and the low refractive index layer (5) is laminated as shown in a (FIG. 1) above, it can be suitably used as an antireflection film. it can. The low refractive index layer (5) is formed by forming the low refractive index layer (5) on the hard coat layer (2) with a film thickness of about 1/4 of the wavelength of light, thereby reflecting the surface reflection by the principle of thin film interference. Can be reduced.

  Further, as shown in c (FIG. 2), the hard coat layer (2) is applied on the transparent support (1), and the high refractive index layer (4) and the low refractive index layer (5) are laminated. It can be suitably used as an antireflection film. Further, as shown in FIG. 3 (d), the transparent support (1), the hard coat layer (2), the medium refractive index layer (3), the high refractive index layer (4), and the low refractive index layer (5) are ordered. By installing this layer structure, the reflectance can be reduced to 1% or less.

  In the layer configuration of the antireflection films a to f, the hard coat layer (2) can be an antiglare hard coat layer having antiglare properties. The antiglare property may be imparted by dispersing the matte particles as shown in FIG. 4 or by surface shaping by a method such as embossing as shown in FIG. The antiglare hard coat layer formed by dispersing the matte particles is composed of a binder and translucent particles dispersed in the binder. The antiglare hard coat layer has both antiglare properties and hard coat properties, but the hard coat layer may be composed of a plurality of layers such as an antiglare hard coat layer and a smooth hard coat layer. . In addition to the hard coat layer, an antiglare layer can be provided.

  In addition, interference unevenness (rainbow unevenness) prevention layer, antistatic layer (reduction of surface resistance value from the display side, etc.) may be provided between the support and the surface side layer or the outermost layer. If there is a dust, there is a problem with dust on the surface, etc.), another hard coat layer (when only one hard coat layer or antiglare hard coat layer is insufficient in hardness), gas barrier layer, water Examples include an absorption layer (moisture-proof layer), an adhesion improving layer, an antifouling layer (contamination-preventing layer), and the like.

The refractive index of each layer constituting the antireflection film having the antireflection layer in the invention preferably satisfies the following relationship.
Refractive index of hard coat layer> refractive index of transparent support> refractive index of low refractive index layer

  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 high refractive index layer may be a light diffusing layer having no antiglare property. 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.

[Hard coat layer]
The antireflection film of the present invention has a hard coat layer on a transparent support, and further has a low refractive index layer thereon. Furthermore, it can also be set as the anti-reflective film which used this hard-coat layer as the glare-proof hard coat layer according to the performance requested | required. In the antireflection film of the present invention, for the purpose of improving the film strength, a hard coat layer that is not antiglare can be further provided under the antiglare hard coat layer.

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

(Binder polymer having a saturated hydrocarbon chain as the main chain)
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 preferable.

  In order to make the layer have a high refractive index, it is preferable that 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. .

  Examples of the monomer having two or more ethylenically unsaturated groups include (meth) acrylic acid esters of polyhydric alcohols {eg, ethylene glycol di (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, pentaerythritol Tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Dipentaerythritol hexa (meth) acrylate, 1,2,3-cyclohexanetriol tri (meth) acrylate, polyurethane polyacrylate, polyester polyacrylate, etc.}, Stell's modified ethylene oxide, vinylbenzene and its derivatives {eg 1,4-divinylbenzene, 4-vinylbenzoic acid-2- (meth) acryloylethyl ester, 1,4-divinylcyclohexanone, etc.}, vinyl sulfone (eg Divinylsulfone), (meth) acrylamide (for example, methylenebisacrylamide) and the like. 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.

  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 isocyanate group, epoxy group, aziridine group, oxazoline group, aldehyde group, carbonyl group, hydrazine group, carboxyl group, methylol group and 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.

(Polymerization initiator)
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. Accordingly, a coating liquid containing a monomer having an ethylenically unsaturated group, a photo radical initiator or a thermal radical initiator, an inorganic filler, and, if necessary, matte particles is prepared, and the coating liquid is coated on a transparent support. It can be cured by a post-ionizing radiation or a polymerization reaction with heat to form a hard coat layer of the antireflection film.

(Photo radical polymerization initiator)
As radical photopolymerization initiators, acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides (described in JP 2001-139663 A), Examples include 2,3-dialkyldione compounds, disulfide compounds, fluoroamine compounds, aromatic sulfoniums, onium salts, borate salts, and active halogen compounds.

  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.

  “Latest UV Curing Technology” {Publisher: Kazuhiro Takasato, Publisher; Technical Information Association, 1991}, p. 159, and “UV Curing System” (written by Kiyotsugu Kato, published by General Technology Center in 1989), pages 65 to 148, are described in various examples and are useful for the present invention.

  As a commercially available photocleavable photoradical polymerization initiator, a trade name “Irgacure (651, 184, 907)” manufactured by Ciba Geigy Japan, Inc. can be mentioned as a preferred example.

  It is preferable to use a photoinitiator in the range of 0.1-15 mass parts with respect to 100 mass parts of polyfunctional monomers, More preferably, it is the range of 1-10 mass parts.

(Photosensitizer)
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.

(Thermal radical initiator)
As the thermal radical initiator, organic or inorganic peroxides, organic azo, diazo compounds, and the like can be used.

  Specifically, benzoyl peroxide, halogen benzoyl peroxide, lauroyl peroxide, acetyl peroxide, dibutyl peroxide, cumene hydroperoxide, butyl hydroperoxide as organic peroxides; hydrogen peroxide, peroxides as inorganic peroxides Ammonium sulfate, potassium persulfate, etc .; 2,2′-azobis (isobutyronitrile), 2,2′-azobis (propionitrile), 1,1′-azobis (cyclohexanedinitrile), etc. as azo compounds; diazo compounds Examples thereof include diazoaminobenzene, p-nitrobenzenediazonium and the like.

(Binder polymer with polyether as main chain)
The binder polymer having a polyether 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.

  Accordingly, a coating liquid containing a polyfunctional epoxy compound, a photoacid generator or a thermal acid generator, matte particles and an inorganic filler is prepared, and the coating liquid is applied onto a transparent support and then subjected to a polymerization reaction by ionizing radiation or heat. It can be cured to form a hard coat layer.

[Inorganic filler]
It is preferable to add an inorganic filler to each layer including the hard coat layer formed on the support. The inorganic filler added to each layer may be the same or different, and the type and amount added are preferably adjusted according to the required performance such as the refractive index, film strength, film thickness, and coatability of each layer.

  The shape of the inorganic filler used in the present invention is not particularly limited, and for example, any of a spherical shape, a plate shape, a fiber shape, a rod shape, an indeterminate shape, a hollow shape, and the like are preferably used, but from the viewpoint of good dispersibility To spherical is more preferable.

  Further, the kind of the inorganic filler is not particularly limited, but an amorphous one is preferably used, and is preferably made of a metal oxide, nitride, sulfide or halide. Particularly preferred. Examples of metal atoms include Zr, Na, K, Mg, Ca, Ba, Al, Zn, Fe, Cu, Ti, Sn, In, W, Y, Sb, Mn, Ga, V, Nb, Ta, Ag, and Si. , B, Bi, Mo, Ce, Cd, Be, Pb, Ni and the like.

  In order to obtain a transparent cured film, the average particle diameter of the inorganic filler is preferably set to a value within the range of 0.001 to 0.2 μm, more preferably 0.001 to 0.1 μm, and still more preferably. 0.001 to 0.06 μm. Here, the average particle diameter of the particles is measured by a Coulter counter.

  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 75%. The addition amount of the inorganic filler can be appropriately selected within the same use amount range in both cases of the antiglare hard coat layer and the smooth hard coat layer described later.

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 method of using the inorganic filler in the present invention is not particularly limited, and can be used in a dry state, for example, or can be used in a state dispersed in water or an organic solvent.

[Dispersion stabilizer]
In the present invention, it is also preferable to use a dispersion stabilizer in combination for the purpose of suppressing aggregation and sedimentation of the inorganic filler. Examples of the dispersion stabilizer include polyvinyl alcohol, polyvinyl pyrrolidone, cellulose derivatives, polyamides, phosphate esters, polyethers, surfactants, hydrolysates of organosilane compounds and / or partial condensates thereof, silane coupling agents, A titanium coupling agent or the like can be used. In particular, a silane coupling agent is preferable because the film after curing is strong.

  Although the addition amount of the silane coupling agent as a dispersion stabilizer is not particularly limited, for example, the value is preferably 1 part by mass or more with respect to 100 parts by mass of the inorganic filler. Further, the addition method of the silane coupling agent as a dispersion stabilizer is not particularly limited, but a hydrolyzed one can be added, and the silane coupling agent which is a dispersion stabilizer and Although the method of further hydrolyzing and condensing after mixing with an inorganic filler can be taken, the latter is more preferable.

  As mentioned above, the hydrolyzate of organosilane compound and / or its partial condensate can be used as a dispersion stabilizer for inorganic fillers. As a part of the matrix constituent components of each layer such as the curable compound, it can also be used as an additive in preparing the coating solution. In particular, in the present invention, it is preferable to use a hydrolyzate of a specific organosilane compound and / or a partial condensate thereof for the low refractive index layer, which will be described in detail later.

[Anti-glare hard coat layer]
Next, the antiglare hard coat layer preferably used in the present invention will be described. The antiglare hard coat layer is formed from a binder for imparting hard coat properties, mat particles for imparting antiglare properties, and an inorganic filler for increasing the refractive index, preventing crosslinking shrinkage, and increasing the strength. The

(Matte particles)
The antiglare hard coat layer has an average particle size of 1.0 to 10.0 μm, preferably 1.5 to 7.0 μm, larger than cohesive silica particles and filler particles for the purpose of imparting antiglare properties. Matt particles, for example, particles of an inorganic compound or translucent resin particles are contained.

Specific examples of the particles include preferably particles of inorganic compounds such as silica particles and TiO ₂ particles; resin particles such as crosslinked acrylic particles, crosslinked styrene particles, melamine resin particles, and benzoguanamine resin particles.
The silica particles may be spherical particles having a primary particle diameter of 0.5 to 10 μm, but agglomerated silica in which particles having a primary particle diameter of several tens of nm form an aggregate is preferable for preventing whitening.
The cohesive silica can be obtained by a so-called wet method synthesized by a neutralization reaction between sodium silicate and sulfuric acid, but is not limited thereto.
The wet method is further roughly classified into a precipitation method and a gelation method, and the present invention may be any method.
The secondary particle size of the cohesive silica is preferably in the range of 0.1 to 10.0 μm.
In particular, the value obtained by dividing the secondary particle diameter of the cohesive silica particles by the film thickness of the hard coat layer is 0.1 to 1.
0 is preferable, and 0.3 to 0.8 is more preferable.

The translucent resin particles that can be used in combination with the aforementioned silica particles, preferably cohesive silica particles, are described.
Specific examples of translucent resin particles that can be used in combination include, for example, poly ((meth) acrylate) particles, crosslinked poly ((meth) acrylate) particles, polystyrene particles, crosslinked polystyrene particles, crosslinked poly (acryl-styrene) particles, Preferred are resin particles such as melamine resin particles and benzoguanamine resin particles. Of these, crosslinked polystyrene particles, crosslinked poly ((meth) acrylate) particles, and crosslinked poly (acryl-styrene) particles are preferable, and crosslinked poly ((meth) acrylate) particles and crosslinked poly (acryl-styrene) particles are most preferably used. It is done. By adjusting the refractive index of the translucent resin and the addition amount in accordance with the refractive index of each translucent fine particle selected from these particles, the internal haze and the surface haze can be in a desired range. it can.
The average particle size of the translucent resin particles that can be used in combination is preferably 0.5 to 10 μm, more preferably 2.0 to 6.0 μm.

As the translucent resin particles that can be used in combination, in order to improve the scratch resistance, the resin particles preferably have a compressive strength of 2.2 to 10.0 kgf / mm ² , and 2.5 to 8.0 kgf / mm ^2. more preferably mm ^2. In order to increase the compressive strength of the resin particles, it is effective to select a crosslinking agent and increase the degree of crosslinking.

  As the shape of the matte particle, either a true sphere or an indefinite shape can be used. Further, two or more different kinds of mat particles may be used in combination.

The mat particles are formed on the anti-glare hard coat layer so that the amount of the mat particles in the formed anti-glare hard coat layer is preferably 10 to 1000 mg / m ² , more preferably 30 to 100 mg / m ^2. Contained.

  Further, in a particularly preferred embodiment, cross-linked styrene particles are used as the matte particles, and the cross-linked styrene particles having a particle size larger than a half of the film thickness of the antiglare hard coat layer are 40 to 100 of the entire cross-linked styrene particles. %.

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

Two or more kinds of mat particles having different particle diameters may be used in combination.
It is possible to impart anti-glare properties with mat particles having a larger particle size and to impart other optical characteristics with mat particles having a smaller particle size. For example, when an antireflection film is attached to a high-definition display device of 133 dpi or more, it is required that there is no optical performance defect called glare. This is because the pixels are enlarged or reduced due to unevenness present on the film surface and the uniformity of display performance is lost, but this is 5 to 50% more than the matte particles that impart antiglare properties. It can be greatly improved by using mat particles having a small diameter.

Furthermore, the particle size distribution of the mat particles is preferably monodispersed, and the particle size of all particles is preferably as close as possible. For example, when particles having a particle size different from the average particle size by 20% or more are defined as coarse particles, the ratio of the coarse particles is preferably 1% or less of the total number of particles, more preferably 0.1%. % Or less, more preferably 0.01% or less. The mat particles having such a particle size distribution are obtained by classification after a normal synthesis reaction, and mat particles having a more preferable distribution can be obtained by increasing the number of classifications or increasing the degree of classification.

(Inorganic filler)
In order to increase the refractive index of the antiglare hard coat layer, in addition to the above mat particles, at least one metal selected from titanium, zirconium, aluminum, indium, zinc, tin and antimony is used. It is preferably made of an oxide, and the average particle size is preferably in the range of 0.001 to 0.2 μm, more preferably 0.001 to 0.1 μm, still more preferably 0.001 to 0.06 μm. is there. It is preferable that an inorganic filler is contained.

  Conversely, in the antiglare hard coat layer using the high refractive index mat particles in order to increase the refractive index difference from the mat particles, silicon oxide is used to keep the refractive index of the layer low. It is also preferable. The preferred particle size is the same as that of the inorganic filler.

Specific examples of the inorganic filler for use in the antiglare hard coat _{layer, TiO 2, ZrO 2, Al} 2 O 3, In 2 O 3, ZnO, SnO 2, Sb 2 O 3, ITO ( indium - tin oxide ), SiO _{2 and the} like. TiO ₂ and ZrO ₂ are particularly preferable in terms of increasing the refractive index. As described above, the surface of these inorganic fillers is preferably subjected to silane coupling treatment or titanium coupling treatment, and a surface treatment agent having a functional group capable of reacting with a binder on the filler surface is preferably used.

  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 total refractive index of the mixture of binder and inorganic filler in the antiglare hard coat layer in the antireflection film of the present invention is preferably 1.48 to 2.00, more preferably 1.50 to 1.50. 80. In order to make the refractive index within the above range, the type and amount ratio of the binder and the inorganic filler may be selected. It can be known experimentally in advance how to select.

(Surfactant)
The antiglare hard coat layer in the present invention has a surface activity of either fluorine or silicone, particularly in order to prevent surface failure such as coating unevenness, drying unevenness, point defects and the like to ensure surface uniformity. It is preferable to contain an agent or both in the coating composition for forming the antiglare hard coat layer. In particular, a fluorine-based surfactant is preferably used because an effect of improving surface defects such as coating unevenness, drying unevenness, and point defects of the antireflection film of the present invention appears in a smaller addition amount.

  Preferable examples of the fluorosurfactant include “Megafac F-171”, “Megafac F-172”, “Megafac F-173”, “Megafac F-176” manufactured by Dainippon Ink, Inc. (All are trade names) and other perfluoroalkyl group-containing oligomers. Examples of the silicone-based surfactant include polydimethylsiloxane in which a side chain or a main chain terminal is modified with various substituents such as oligomers such as ethylene glycol and propylene glycol.

However, by using the surfactant as described above, the functional group containing F atoms and / or the functional group having Si atoms segregates on the surface of the antiglare hard coat layer, and thus the antiglare hard coat layer. When the surface energy of the low-refractive index layer is overcoated on the antiglare hard coat layer, the antireflection performance may be lowered. This is presumed to be due to the fact that the wettability of the coating solution for forming the low refractive index layer with respect to the surface of the antiglare hard coat layer is reduced, resulting in minute unevenness that cannot be detected by visual observation of the film thickness of the low refractive index layer. .

In order to solve such a problem, the surface energy of the antiglare hard coat layer is preferably adjusted to 25 to 70 mN · by adjusting the structure and addition amount of the fluorine-based and / or silicone-based surfactant. to m ^-1, more preferably effective to control the 35~70mN · m ^-1, as described further below, the 50 to 100% by weight of the coating solvent of the low refractive index layer having a boiling point 100 ° C. of less It is more effective to use a solvent.

  Further, in order to realize the surface energy as described above, F / C, which is a ratio of a peak derived from a fluorine atom and a peak derived from a carbon atom, measured by X-ray photoelectron spectroscopy is 0.40 or less, and / or Or it is preferable to make Si / C which is the ratio of the peak derived from a silicon atom and the peak derived from a carbon atom into 0.30 or less.

  The film thickness of the antiglare hard coat layer is preferably 1 to 10 μm, and more preferably 1.2 to 6 μm.

[Smooth hard coat layer]
In the antireflection film of the present invention, a so-called smooth hard coat layer which is not antiglare is also preferably used for the purpose of further improving the film strength. The smooth hard coat layer is more preferably used in combination with the antiglare hard coat layer, and is coated between the transparent support and the antiglare hard coat layer.

  The material used for the smooth hard coat layer is the same as that mentioned in the anti-glare hard coat layer except that the matte particles for imparting anti-glare properties are not used. From the binder and preferably the inorganic filler It is formed.

  In the smooth hard coat layer in the present invention, as the inorganic filler, silica and alumina are preferable in terms of strength and versatility, and silica is particularly preferable. The inorganic filler is preferably subjected to silane coupling treatment on the surface, and a surface treatment agent having a functional group capable of reacting with the binder species on the filler surface is preferably used.

  The film thickness of the smooth hard coat layer is preferably 1 to 10 μm, more preferably 1.2 to 6 μm.

(Low refractive index layer)
The low refractive index layer of the antireflection film of the present invention will be described below.
The refractive index of the low refractive index layer in the antireflection film of the present invention is preferably 1.38 to 1.49, more preferably 1.38 to 1.44.

  Further, the low refractive index layer preferably satisfies the following formula (1) from the viewpoint of reducing the reflectance.

Formula (1): (jλ / 4) × 0.7 <n ₁ d ₁ <(jλ / 4) × 1.3

In the formula, j is a positive odd number, n ₁ is the refractive index of the low refractive index layer, and d ₁ is the film thickness (nm) of the low refractive index layer. Further, λ is a wavelength and is a value in the range of 500 to 550 nm. The film thickness (d ₁ ) of the low refractive index layer is preferably 70 to 150 nm, more preferably 80 to 120 nm, and most preferably 85 to 115 nm.

  In addition, satisfy | filling said Numerical formula (1) means that j (positive odd number, usually 1) which satisfy | fills Numerical formula (1) exists in the said wavelength range.

  Each material for forming the low refractive index layer in the present invention will be described below.

  The low refractive index layer used in the present invention is formed of a composition for forming a low refractive index layer containing a binder polymer, at least one polymerization initiator, and a curable compound having an ethylenically unsaturated group. Furthermore, it is preferable that the polymerization initiator and the curable compound are localized and cured at the lower part of the low refractive index layer.

  Preferably, the polymerization initiator (C) is a thermal and / or photodegradable initiator. The binder polymer (A) is preferably a fluorine-containing polymer having a crosslinkable or polymerizable functional group, and the curable compound (B) is preferably a non-fluorine compound.

[Binder polymer] (A)
{Fluoropolymer}
The fluoropolymer has a cured film with a coefficient of dynamic friction of 0.03 to 0.20, a contact angle with water of 90 to 120 °, and a sliding angle of pure water of 70 ° or less, and heat or ionizing radiation. The polymer that is crosslinked by the above is preferable in terms of productivity improvement in the case of coating and curing the roll film while transporting the web.

  Further, when the antireflection film of the present invention is mounted on a display device, the lower the peel strength from a commercially available adhesive tape, the easier it is to peel off after sticking a seal or memo, so the peel strength is preferably 500 gf or less, and 300 gf The following is more preferable, and 100 gf or less is most preferable. Further, the higher the surface hardness measured with a microhardness meter, the harder it is to scratch. Therefore, the surface hardness is preferably 0.3 GPa or more, and more preferably 0.5 GPa or more.

The fluorine-containing polymer used in the low refractive index layer is preferably a fluorine-containing compound containing a crosslinkable or polymerizable functional group, such as a perfluoroalkyl group-containing silane compound {for example, (heptadecafluoro-1,1,2 , 2-tetradecyl) triethoxysilane} hydrolyzate and dehydration condensate, and fluorine-containing copolymers of fluorine-containing monomers and monomers for imparting crosslinkable groups. In the case of a fluorinated copolymer, the main chain is preferably composed of only carbon atoms. That is, it is preferable that the main chain skeleton does not have an oxygen atom or a nitrogen atom.
The fluorine atom content of the fluoropolymer is preferably 35 to 80% by mass.

  Specific examples of the fluorine-containing monomer include, for example, fluoroolefins (for example, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoroethylene, hexafluoropropylene, perfluoro-2,2-dimethyl-1,3-dioxole, etc.), (Meth) acrylic acid partial or fully fluorinated alkyl ester derivatives [e.g. "Biscoat 6FM" {manufactured by Osaka Organic Chemical Industry Co., Ltd.} or "M-2020" {manufactured by Daikin Industries Ltd.}], complete or Partially fluorinated vinyl ethers and the like can be mentioned, and perfluoroolefins are preferable, and hexafluoropropylene is particularly preferable from the viewpoint of refractive index, solubility, transparency, availability, and the like. Increasing the composition ratio of these fluorine-containing monomers can lower the refractive index, but lowers the film strength. In the present invention, it is preferable to introduce the fluorine-containing monomer so that the fluorine content of the copolymer is 20 to 60% by mass, more preferably 25 to 55% by mass, and particularly preferably 30 to 50% by mass. %.

Examples of the structural unit for imparting a crosslinkable group include units represented by the following (a), (b), and (c).
(A): A structural unit obtained by polymerization of a monomer having a self-crosslinkable functional group in the molecule in advance such as glycidyl (meth) acrylate or glycidyl vinyl ether.
(B): a monomer having a carboxyl group, a hydroxyl group, an amino group, a sulfo group or the like (
For example, structural units obtained by polymerization of (meth) acrylic acid, methylol (meth) acrylate, hydroxyalkyl (meth) acrylate, allyl acrylate, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, maleic acid, crotonic acid, etc., in this case copolymerization Thereafter, it is described in JP-A-10-25388 and JP-A-10-147739 that a crosslinked structure can be introduced.
(C): reacting a compound having a crosslinkable functional group separately from the group reacting with the functional group of (a) or (b) in the molecule with the structural unit of (a) or (b). The resulting structural unit (for example, a structural unit that can be synthesized by a technique such as allowing acrylic acid chloride to act on a hydroxyl group).

  In the present invention, the structural unit (c) is preferably such that the crosslinkable functional group is a photopolymerizable group. Examples of the photopolymerizable group include (meth) acryloyl group, alkenyl group, cinnamoyl group, cinnamylideneacetyl group, benzalacetophenone group, styrylpyridine group, α-phenylmaleimide group, phenylazide group, sulfonylazide group, carbonyl Azide group, diazo group, o-quinonediazide group, furylacryloyl group, coumarin group, pyrone group, anthracene group, benzophenone group, stilbene group, dithiocarbamate group, xanthate group, 1,2,3-thiadiazole group, cyclopropene group, An azadioxabicyclo group etc. can be mentioned, These may be not only 1 type but 2 or more types. Of these, a (meth) acryloyl group and a cinnamoyl group are preferable, and a (meth) acryloyl group is particularly preferable.

Specific methods for preparing the photopolymerizable group-containing copolymer include, but are not limited to, the following methods.
(1) A method of esterifying a crosslinkable functional group-containing copolymer containing a hydroxyl group by reacting (meth) acrylic acid chloride,
(2) A method of urethanizing a crosslinkable functional group-containing copolymer containing a hydroxyl group with a (meth) acrylic acid ester containing an isocyanate group,
(3) A method of esterifying by reacting (meth) acrylic acid with a crosslinkable functional group-containing copolymer containing an epoxy group,
(4) A method in which a crosslinkable functional group-containing copolymer containing a carboxyl group is esterified by reacting a containing (meth) acrylic acid ester containing an epoxy group.

  The amount of the photopolymerizable group introduced can be arbitrarily adjusted. From the viewpoints of surface stability of the coating film, reduction of surface failure when coexisting with inorganic fine particles, and improvement of film strength, carboxyl groups, hydroxyl groups, etc. It is also preferable to leave a certain amount.

  Further, not only a copolymer of the above-mentioned fluorine-containing monomer and a monomer for imparting a crosslinkable group, but also a copolymer obtained by copolymerizing other monomers may be used. A plurality of these vinyl monomers may be combined depending on the purpose, and are preferably introduced in the range of 0 to 65 mol% in the copolymer in total, and in the range of 0 to 40 mol%. More preferably, it is particularly preferably in the range of 0 to 30 mol%.

The monomer that can be used in combination is not particularly limited. For example, olefins (ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride, etc.), acrylic esters (methyl acrylate, methyl acrylate, ethyl acrylate, 2-acrylic acid 2- Ethyl hexyl), methacrylates (methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate, etc.), styrene derivatives (styrene, divinylbenzene, vinyl toluene, α-methylstyrene, etc.), vinyl ethers (methyl vinyl ether) , Ethyl vinyl ether, cyclohexyl vinyl ether, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, etc.), vinyl esters (vinyl acetate, vinyl propionate, vinyl cinnamate, etc.) Examples include unsaturated carboxylic acids (acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, etc.), acrylamides (Nt-butylacrylamide, N-cyclohexylacrylamide, etc.), methacrylamides, acrylonitrile derivatives, etc. it can.

  Examples of the binder that can be preferably used in the low refractive index layer of the antireflection film of the present invention include copolymers described in JP-A-2004-45462, [0030] to [0047].

  The fluorine-containing polymer particularly useful in the present invention is a random copolymer of perfluoroolefin and vinyl ethers or vinyl esters. In particular, it preferably has a group capable of undergoing a crosslinking reaction alone {a radical reactive group such as a (meth) acryloyl group, a ring-opening polymerizable group such as an epoxy group or an oxetanyl group}. These cross-linking reactive group-containing polymer units preferably occupy 5 to 70 mol%, particularly preferably 30 to 60 mol%, of the total polymerized units of the polymer.

  Regarding preferred polymers, JP-A-2002-243907, JP-A-2002-372601, JP-A-2003-26732, JP-A-2003-222702, JP-A-2003-294911, JP-A-2003-329804, JP-A-2004. -4444 and JP, 2004-45462, A can be mentioned.

Moreover, it is preferable that the polysiloxane structure is introduce | transduced into the fluorine-containing polymer used by this invention in order to provide antifouling property. The method for introducing the polysiloxane structure is not limited. For example, as described in JP-A-6-93100, JP-A-11-189621, JP-A-11-228631, and JP-A-2000-313709, silicone macroazo A method for introducing a polysiloxane block copolymer component using an initiator; a method for introducing a polysiloxane graft copolymer component using a silicone macromer as described in JP-A-2-251555 and JP-A-2-308806. Etc. are preferred. Particularly preferred compounds include the polymers of Examples 1, 2, and 3 of JP-A-11-189621, and copolymers A-2 and A-3 of JP-A-2-251555. These polysiloxane components are preferably 0.5 to 10% by mass, particularly preferably 1 to 5% by mass in the polymer.

  The preferred molecular weight of the polymer that can be preferably used in the present invention is a mass average molecular weight of 5,000 or more, preferably 10,000 to 500,000, most preferably 15,000 to 200,000. By using polymers having different average molecular weights in combination, it is possible to improve the surface state of the coating film and the scratch resistance.

(Preferred form of fluoropolymer)
As a preferable form of the fluorine-containing polymer used in the present invention, a fluorine-containing polymer described by the following general formula 6 or 7 is preferably used.

  General formula 6

In General Formula 6, L represents a linking group having 1 to 10 carbon atoms, more preferably a linking group having 1 to 6 carbon atoms, and particularly preferably a linking group having 2 to 4 carbon atoms. It may have a branched structure, may have a ring structure, and may have a heteroatom selected from O, N, and S.
Preferred examples include * — (CH ₂ ) ₂ —O — **, * — (CH ₂ ) ₂ —NH — **, * — (CH ₂ ) ₄ —O — **, * — (CH ₂ ). _{6 -O - **, - (CH} 2) 2 -O- (CH 2) 2 -O - **, * - CONH- (CH 2) 3 -O - **, * - CH 2 CH (OH) CH ₂ —O — **, * —CH ₂ CH ₂ OCONH (CH ₂ ) ₃ —O — ** (* represents a connecting site on the polymer main chain side, and ** represents a connecting site on the (meth) acryloyl group side) And the like. m represents 0 or 1;

  In general formula 6, X represents a hydrogen atom or a methyl group. From the viewpoint of curing reactivity, a hydrogen atom is more preferable.

  In general formula 6, A represents a repeating unit derived from an arbitrary vinyl monomer, and is not particularly limited as long as it is a constituent component of a monomer copolymerizable with hexafluoropropylene. Tg (contributes to film hardness), solubility in solvents, transparency, slipperiness, dust / antifouling properties, etc., can be selected as appropriate, depending on the purpose, depending on the single or multiple vinyl monomers It may be configured.

  Preferred examples include methyl vinyl ether, ethyl vinyl ether, t-butyl vinyl ether, cyclohexyl vinyl ether, isopropyl vinyl ether, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, glycidyl vinyl ether, vinyl ethers such as allyl vinyl ether, vinyl acetate, vinyl propionate, butyric acid. (Meth) such as vinyl esters such as vinyl, methyl (meth) acrylate, ethyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycidyl methacrylate, allyl (meth) acrylate, (meth) acryloyloxypropyltrimethoxysilane Acrylates, styrene, styrene derivatives such as p-hydroxymethylstyrene, crotonic acid, maleic acid, itaconic acid Can be mentioned unsaturated carboxylic acids and derivatives thereof, more preferably ether derivatives, vinyl ester derivatives, particularly preferably a vinyl ether derivative.

  x, y, and z represent mol% of each constituent component, and represent values satisfying 30 ≦ x ≦ 60, 5 ≦ y ≦ 70, and 0 ≦ z ≦ 65. Preferably, 35 ≦ x ≦ 55, 30 ≦ y ≦ 60, and 0 ≦ z ≦ 20, and particularly preferably 40 ≦ x ≦ 55, 40 ≦ y ≦ 55, and 0 ≦ z ≦ 10.

  General formula 7 is also mentioned as a more preferable form of the copolymer used for this invention.

  Formula 7

In the general formula 7, R may be an alkyl group having 1 to 10 carbon atoms or an ethylenically unsaturated group (—C (═O) C (—X) ═CH ₂ ) as in the general formula 6.
m represents an integer of 1 ≦ m ≦ 10, preferably 1 ≦ m ≦ 6, and particularly preferably 1 ≦ m ≦ 4.
n represents an integer of 2 ≦ n ≦ 10, preferably 2 ≦ n ≦ 6, and particularly preferably 2 ≦ n ≦ 4.
B represents a repeating unit derived from an arbitrary vinyl monomer, and may be composed of a single composition or a plurality of compositions. Moreover, the silicone site | part may be included.
x, y, z1 and z2 represent mol% of each repeating unit, and x and y preferably satisfy 30 ≦ x ≦ 60 and 0 ≦ y ≦ 70, respectively, more preferably 35 ≦ x ≦ 55. 0 ≦ y ≦ 60, particularly preferably 40 ≦ x ≦ 55 and 0 ≦ y ≦ 55. z1 and z2 preferably satisfy 1 ≦ z1 ≦ 65 and 1 ≦ z2 ≦ 65, more preferably 1 ≦ z1 ≦ 40, and 1 ≦ z2 ≦ 10, preferably 1 ≦ z1 ≦ 30, It is particularly preferable that ≦ z2 ≦ 5. However, x + y + z1 + z2 = 100.
The fluorine-containing polymer of the present invention preferably has a constitutional unit having the following polysiloxane structure in order to impart antifouling properties. The fluorine-containing polymer having a polysiloxane structure useful in the present invention includes (a) a fluorine-containing vinyl monomer polymerization unit, (b) a hydroxyl group-containing vinyl monomer polymerization unit, and (c) a side chain represented by the following general formula 1. Examples thereof include fluorine-containing polymers each containing at least one kind of polymerized unit having a graft site containing a polysiloxane repeating unit, the main chain of which is composed of only carbon atoms.

  General formula 1

In general formula 1, R ¹ and R ² may be the same or different and each represents an alkyl group or an aryl group. As an alkyl group, C1-C4 is preferable and a methyl group, a trifluoromethyl group, an ethyl group etc. are mentioned as an example. The aryl group preferably has 6 to 20 carbon atoms, and examples thereof include a phenyl group and a naphthyl group. Among these, a methyl group and a phenyl group are preferable, and a methyl group is particularly preferable. p represents an integer of 2 to 500, preferably 5 to 350, and particularly preferably 8 to 250.

  The polymer having a polysiloxane structure represented by the general formula 1 in the side chain is, for example, an epoxy group, a hydroxyl group as described in J. Appl. Polym. Sci. 2000, 78, 1955, JP-A-56-28219, etc. The reactive group (for example, an amino group, a mercapto group, a carboxyl group, a hydroxyl group, etc. with respect to an epoxy group or an acid anhydride group) is separated from a polymer having a reactive group such as a carboxyl group or an acid anhydride group. It can be synthesized by a method of introducing a polysiloxane having a terminal (for example, Silaplane series (manufactured by Chisso Corporation)) by a polymer reaction or a method of polymerizing a polysiloxane-containing silicon macromer, and both methods are preferably used. Can do. In the present invention, a method of introducing by polymerization of silicon macromer is more preferable.

  Any silicon macromer may be used as long as it has a polymerizable group capable of copolymerization with a fluorine-containing olefin, and preferably has a structure represented by any one of formulas 2 to 5.

In General Formulas 2 to 5, R ¹ , R ² and p represent the same meaning as in General Formula 1, and preferred ranges are also the same. R ^{3 to} R ⁵ each independently represents a substituted or unsubstituted monovalent organic group or a hydrogen atom, an alkyl group having 1 to 10 carbon atoms (for example, a methyl group, an ethyl group, an octyl group, etc.), a carbon number of 1 10 to 10 alkoxy groups (for example, methoxy group, ethoxy group, propyloxy group and the like), aryl groups having 6 to 20 carbon atoms (for example, phenyl group, naphthyl group and the like) are preferable, and alkyl groups having 1 to 5 carbon atoms are particularly preferable. . R ⁶ represents a hydrogen atom or a methyl group. L ₁ represents an arbitrary linking group having 1 to 20 carbon atoms, and examples thereof include a substituted or unsubstituted linear, branched or alicyclic alkylene group, or a substituted or unsubstituted arylene group. It is an unsubstituted linear alkylene group of 1 to 20, particularly preferably an ethylene group or a propylene group. These compounds are synthesized, for example, by the method described in JP-A-6-322053.

  Any of the compounds represented by the general formulas 2 to 5 can be preferably used in the present invention. Among them, the structure represented by the general formula 2, 3 or 4 is particularly preferred from the viewpoint of copolymerization with the fluorinated olefin. Those are preferred. The polysiloxane moiety preferably occupies 0.01 to 20% by mass of the graft copolymer, more preferably 0.05 to 15% by mass, and particularly preferably 0.5 to 10% by mass. %.

  Although the preferable example of the polymer unit of the polymer graft part which contains a polysiloxane part in the side chain useful for this invention below is shown, this invention is not limited to these.

S- (36) Silaplane FM-0711 (manufactured by Chisso Corporation)
S- (37) Silaplane FM-0721 (same as above)
S- (38) Silaplane FM-0725 (same as above)

  By introducing the polysiloxane structure, the film is imparted with antifouling property and dustproof property, and the film surface is provided with slipperiness, which is advantageous for scratch resistance.

(Curing agent)
By blending a crosslinkable compound as a curing agent in the fluoropolymer, further curability can be imparted. For example, when the polymer body contains a hydroxyl group, the compound that can be used as the curing agent is not particularly limited as long as it is a curing agent having two or more functional groups capable of reacting with a hydroxyl group in one molecule. , Partial condensation products of isocyanate compounds, adducts with multimers, polyhydric alcohols, low molecular weight polyester films, blocked polyisocyanate compounds in which isocyanate groups are blocked with a blocking agent such as phenol, aminoplasts, polybasic An acid or its anhydride can be mentioned. When using these curing agents, the content of the hydroxyl group-containing monomer unit is preferably 1% to 65%, more preferably 1% to 50%.

  Among the curing agents that react with hydroxyl groups, in the present invention, a crosslinking reaction with a hydroxyl group-containing compound under acidic conditions from the viewpoints of both stability during storage and activity of crosslinking reaction, and strength of the film to be formed. Aminoplasts are preferred. Aminoplasts contain an amino group capable of reacting with a hydroxyl group present in the fluorine-containing polymer, that is, a hydroxyalkylamino group or an alkoxyalkylamino group, or a carbon atom adjacent to a nitrogen atom and substituted with an alkoxy group. A compound. Specific examples include melamine compounds, urea compounds, benzoguanamine compounds, and the like.

  The melamine compounds are generally known as compounds having a skeleton in which a nitrogen atom is bonded to a triazine ring, and specific examples include melamine, alkylated melamine, methylol melamine, and alkoxylated methyl melamine. . In particular, methylolated melamine and alkoxylated methyl melamine obtained by reacting melamine and formaldehyde under basic conditions and derivatives thereof are preferable, and alkoxylated methyl melamine is particularly preferable in view of storage stability. There are no particular restrictions on methylolated melamine and alkoxylated methylmelamine. For example, use of various resins obtained by the method described in “Plastic Materials Course [8] Urea Melamine Resin” (Nikkan Kogyo Shimbun) Is also possible.

  As the urea compound, in addition to urea, an alkoxylated methylurea which is a polymethylolated urea derivative thereof, and a compound having a glycoluril skeleton or a 2-imidazolidinone skeleton having a cyclic urea structure are also preferable. As for the amino compounds such as the urea derivatives, various resins described in the above-mentioned “Yurea / Melamine resin” can be used.

As the compound suitably used as the crosslinking agent in the present invention, a melamine compound or a glycoluril compound is particularly preferable from the viewpoint of compatibility with the fluorine-containing copolymer, and among these, from the viewpoint of reactivity, the crosslinking agent is in the molecule. The compound preferably contains a nitrogen atom and contains two or more carbon atoms substituted with an alkoxy group adjacent to the nitrogen atom. Particularly preferred compounds are compounds having structures represented by the following H-1 and H-2, and partial condensates thereof. Wherein ^{R 31, R 32} represents an alkyl group or a hydroxyl group having 1 to 6 carbon atoms.

  As addition amount of aminoplast with respect to a fluorine-containing polymer, it is 1-50 mass parts per 100 mass parts of copolymers, Preferably it is 3-40 mass parts, More preferably, it is 5-30 mass parts. If it is 1 part by mass or more, the durability as a thin film can be sufficiently exhibited, and if it is 50 parts by mass or less, it is preferable because the low refractive index of the low refractive index layer can be maintained when used for optical applications. . From the viewpoint of keeping the refractive index low even when a curing agent is added, a curing agent that has a small increase in refractive index even when added is preferable, and from this viewpoint, the above compound has a skeleton represented by H-2. Compounds are more preferred.

(Curing catalyst)
When the antireflective film of the present invention is cured by a crosslinking reaction between the hydroxyl group of the fluorine-containing polymer and the curing agent while heating, the curing is accelerated by an acid in this system, so that the curable resin composition In addition, it is desirable to add an acidic substance. However, if a normal acid is added, a crosslinking reaction proceeds even in the coating solution, causing failure (unevenness, repellency, etc.). Therefore, in order to achieve both storage stability and curing activity in a thermosetting system, it is more preferable to add a compound that generates an acid by heating as a curing catalyst.

  The curing catalyst is preferably a salt composed of an acid and an organic base. Examples of the acid include organic acids such as sulfonic acid, phosphonic acid, and carboxylic acid, and inorganic acids such as sulfuric acid and phosphoric acid. From the viewpoint of compatibility with the polymer, organic acids are more preferable, and sulfonic acid and phosphonic acid are more preferable. Sulphonic acid is most preferred. Preferred sulfonic acids include p-toluenesulfonic acid (PTS), benzenesulfonic acid (BS), p-dodecylbenzenesulfonic acid (DBS), p-chlorobenzenesulfonic acid (CBS), 1,4-naphthalenedisulfonic acid (NDS). ), Methanesulfonic acid (MsOH), nonafluorobutane-1-sulfonic acid (NFBS), etc., and any of them can be preferably used {the abbreviation in parentheses}.

  The curing catalyst varies greatly depending on the basicity and boiling point of the organic base combined with the acid. The curing catalyst preferably used in the present invention is described below from each viewpoint.

  The lower the basicity of the organic base, the higher the acid generation efficiency during heating, which is preferable from the viewpoint of curing activity. However, if the basicity is too low, the storage stability becomes insufficient. Therefore, it is preferable to use an organic base having an appropriate basicity. When expressed using pKa of a conjugate acid as a basic index, the pKa of the organic base used in the present invention needs to be 5.0 to 10.5, and more preferably 6.0 to 10.0. 6.5 to 10.0 is more preferable. The value of pKa of organic base in aqueous solution is described in Chemistry Handbook Basic Edition (5th revised edition, edited by The Chemical Society of Japan, Maruzen, 2004) Volume II, pages II-334-340. An organic base having an appropriate pKa can be selected. In addition, a compound that can be presumed to have a pKa that is structurally appropriate even if not described in this document can be preferably used. Table 1 shows compounds having an appropriate pKa described in the literature, but compounds that can be preferably used in the present invention are not limited thereto.

  The lower the boiling point of the organic base, the higher the acid generation efficiency during heating, which is preferable from the viewpoint of curing activity. Therefore, it is preferable to use an organic base having an appropriate boiling point. The boiling point of the base is preferably 120 ° C. or lower, more preferably 80 ° C. or lower, and further preferably 70 ° C. or lower.

Examples of the organic base that can be preferably used in the present invention include the following compounds, but are not limited thereto. Figures in parentheses indicate boiling points.
b-3: pyridine (115 ° C), b-14: N-methylmorpholine (115 ° C), b-20: diallylmethylamine (111 ° C), b-19: triethylamine (88.8 ° C), b-21 : T-butylmethylamine (67-69 ° C), b-22: dimethylisopropylamine (66 ° C), b-23: diethylmethylamine (63-65 ° C), b-24: dimethylethylamine (36-38 ° C) ), B-18: trimethylamine (3-5 ° C.).

  The boiling point of the organic base that can be preferably used in the present invention is 35 ° C. or higher and 85 ° C. or lower. If the temperature is higher than this, the scratch resistance deteriorates, and if it is lower than 35 ° C., the coating solution becomes unstable. The boiling point is more preferably 45 ° C. or higher and 80 ° C. or lower, and most preferably 55 ° C. or higher and 75 ° C. or lower.

  When used as an acid catalyst used in the present invention, a salt composed of the acid and the organic base may be isolated and used, or the acid and the organic base are mixed to form a salt in the solution, and the solution is used. Also good. Moreover, only one kind of acid or organic base may be used, or a plurality of kinds may be mixed and used. When the acid and the organic base are mixed and used, it is preferable that the equivalent ratio of the acid and the organic base is 1: 0.9 to 1.5, preferably 1: 0.95 to 1.3. Is more preferable, and 1: 1.0 to 1.1 is preferable.

  The use ratio of the acid catalyst is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, and still more preferably 100 parts by mass of the fluoropolymer in the curable resin composition. 0.2 to 3 parts by mass.

  In the present invention, in addition to the thermal acid generator described above, a compound that generates an acid upon irradiation with light, that is, a photosensitive acid generator may be further added. Examples of the acid generator include a photoinitiator for photocationic polymerization, a photodecolorant for dyes, a photochromic agent, a known acid generator used in a microresist, and the like, a known compound, and a mixture thereof. Is mentioned. The photosensitive acid generator is a substance that imparts photosensitivity to the coating film of the curable resin composition and enables the coating film to be photocured by, for example, irradiation with radiation such as light.

  Examples of the photosensitive acid generator include (1) iodonium salt, sulfonium salt, phosphonium salt, diazonium salt, ammonium salt, iminium salt, pyridinium salt, arsonium salt, selenonium salt and the like (preferably diazonium salt, iodonium salt, (2) β-ketoester, β-sulfonylsulfone and sulfone compounds such as these α-diazo compounds; (3) alkylsulfonic acid ester, haloalkylsulfonic acid ester, arylsulfonic acid Examples thereof include sulfonic acid esters such as esters and imino sulfonates; (4) sulfonimide compounds; (5) diazomethane compounds; (6) trihalomethyltriazines; Examples of the above (1) include compounds described in paragraphs [0058] to [0059] of JP-A-2002-29162.

  In addition, as specific compounds and methods of use, for example, the contents described in JP-A-2005-43876 can be used.

  These photosensitive acid generators can be used alone or in combination of two or more, and can also be used in combination with the thermal acid generator. The proportion of the photosensitive acid generator used is preferably 0 to 20 parts by mass, more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the fluoropolymer in the composition for forming a low refractive index layer. . If the ratio of the photosensitive acid generator is less than or equal to the upper limit, it is preferable because the resulting cured film has excellent strength and good transparency.

  Next, the curable compound (B) having an ethylenically unsaturated group will be described.

{Curable compound containing ethylenically unsaturated group (B)}
Examples of the curable compound (B) include monomers having two or more ethylenically unsaturated groups. Examples of the monomer include (saturated hydrocarbon chain as main chain in [binder polymer] of [hard coat layer]. Can be appropriately selected from the various monomers exemplified in the binder polymer). These monomers can increase the density of cross-linking groups in the binder and form a cured film with high hardness, but the refractive index is not lower than that of a fluorine-containing polymer binder. However, when used in combination with inorganic fine particles having a hollow structure, a sufficiently effective refractive index can be obtained as the low refractive index layer of the antireflection film of the present invention.

(Hydrolyzate of organosilane compound and / or partial condensate thereof)
Further, the curable compound is preferably a non-fluorine compound from the viewpoint of making the surface free energy higher than that of the fluorine compound in order to localize it below the fluorine-containing binder. Among them, a hydrolyzate of an organosilane compound and / or a partial condensate thereof, which has an ethylenically unsaturated group and a hydroxyl group or a hydrolyzable group is directly bonded to silicon, may be a so-called sol component. Particularly preferred.

The organosilane compound is preferably represented by the following general formula (b).
Formula (b): (R ³¹ ) _{m 3} —SiX ³¹ _{4-m 3}

In the general formula (b), R ³¹ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, hexyl, decyl, hexadecyl and the like. The alkyl group is preferably an alkyl group having 1 to 30 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 6 carbon atoms. Examples of the aryl group include phenyl and naphthyl, and a phenyl group is preferable.

X ³¹ represents a hydroxyl group or a hydrolyzable group, for example, an alkoxy group (preferably an alkoxy group having 1 to 5 carbon atoms, such as a methoxy group or an ethoxy group), a halogen atom (for example, Cl, Br, I And a group represented by R ³² COO (R ³² is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, such as CH ₃ COO, C ₂ H ₅ COO, etc.), preferably Is an alkoxy group, particularly preferably a methoxy group or an ethoxy group.
m3 represents an integer of 0 to 3, and is preferably 1 or 2.

When R ³¹ or the X ³¹ there are a plurality, even more R ³¹ or X ³¹ is the same, respectively, may be different.

The substituent contained in R ³¹ is not particularly limited, but a halogen atom (fluorine, chlorine, bromine, etc.), hydroxyl group, mercapto group, carboxyl group, epoxy group, alkyl group (methyl, ethyl, i-propyl, propyl, t-butyl etc.), aryl groups (phenyl, naphthyl etc.), aromatic heterocyclic groups (furyl, pyrazolyl, pyridyl etc.), alkoxy groups (methoxy, ethoxy, i-propoxy, hexyloxy etc.), aryloxy (phenoxy etc.) ), Alkylthio groups (methylthio, ethylthio, etc.), arylthio groups (phenylthio, etc.), alkenyl groups (vinyl, 1-propenyl, etc.), acyloxy groups (acetoxy, acryloyloxy, methacryloyloxy, etc.), alkoxycarbonyl groups (methoxycarbonyl, ethoxy) Carbonyl, etc.), aryloxy Carbonyl groups (phenoxycarbonyl, etc.), carbamoyl groups (carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N-methyl-N-octylcarbamoyl, etc.), acylamino groups (acetylamino, benzoylamino, acrylicamino, methacrylamino) Etc.), and these substituents may be further substituted.

When there are a plurality of R ³¹ , at least one is preferably a substituted alkyl group or a substituted aryl group.
The organosilane compounds may be used alone or in combination of a plurality of types to prepare a hydrolyzate and / or a partial condensate thereof.
The organosilane compound hydrolyzate and / or its partial condensate preferably used as the curable compound (B) contains an ethylenically unsaturated group and is used for the preparation of a sol component. Can be prepared by using at least one of R ^{31 of the} above general formula (b) having an ethylenically unsaturated group.

  In order to obtain the effect of the present invention, the content of the organosilane compound having an ethylenically unsaturated group in the hydrolyzate of the organosilane compound and / or the partial condensate thereof is 30% by mass to 100% by mass. Preferably, 50 mass%-100 mass% are more preferable, and 70 mass%-95 mass% are still more preferable. If the content of the organosilane compound having an ethylenically unsaturated group is 30% by mass or more, an insoluble matter is generated, the liquid becomes cloudy, the pot life is deteriorated, or the molecular weight is difficult to control (the molecular weight This is preferable because it does not cause problems such as improvement in performance (for example, scratch resistance of the antireflection film) when the polymerization treatment is performed because the content of the polymerizable group is small.

  At least one of the hydrolyzate of the organosilane compound and / or its partial condensate used in the present invention is preferably suppressed in volatility in order to stabilize the performance of the coated product. The volatilization amount per hour at ° C. is preferably 5% by mass or less, more preferably 3% by mass or less, and particularly preferably 1% by mass or less.

(Method for preparing organosilane sol)
Next, the preparation method of organosilane sol is demonstrated.
In the hydrolysis and / or condensation reaction of the organosilane compound, for example, 0.3 to 2.0 mol, preferably 0.5 to 1.0 mol of water is added to 1 mol of the hydrolyzable group, It is carried out by stirring at 25-100 ° C. in the presence of a chelate compound.

  The mass average molecular weight of the obtained organosilane sol is preferably 450 to 20000, more preferably 500 to 10,000, still more preferably 550 to 5000, and particularly preferably 600 to 3000, when a component having a molecular weight of less than 300 is excluded. 1000-2000 is most preferred. Of the components having a molecular weight of 300 or more in the organosilane sol, the component having a molecular weight of more than 20000 is preferably 20% by mass or less, more preferably 15% by mass or less, and preferably 10% by mass or less. More preferably, it is more preferably 6% by mass or less, and particularly preferably 5% by mass or less. If the component having a molecular weight greater than 20000 is 20% by mass or less, a cured film obtained by curing a composition containing such a hydrolyzate of an organosilane compound and / or a partial condensate thereof has transparency, This is preferable because the adhesiveness to the substrate is excellent.

  Furthermore, among the components having a molecular weight of 300 or more in the organosilane sol, the components having a molecular weight of 450 to 20000 are preferably 80% by mass or more. If the component having a molecular weight of 450 to 20000 is at least the lower limit, the cured film obtained by curing such a composition containing an organosilane sol has excellent transparency and adhesion to a substrate film. Therefore, it is preferable.

  Here, the mass average molecular weight and molecular weight were measured using a solvent tetrahydrofuran (THF) by a GPC analyzer using a column of “TSKgel GMHxL”, “TSKgel G4000HxL”, “TSKgel G2000HxL” (both trade names manufactured by Tosoh Corporation). ), Molecular weight expressed in terms of polystyrene by differential refractometer detection, and the content is area% of the peak in the molecular weight range when the peak area of the component having a molecular weight of 300 or more is defined as 100%.

  The dispersity (mass average molecular weight / number average molecular weight) is preferably 3.0 to 1.1, more preferably 2.5 to 1.1, still more preferably 2.0 to 1.1, and 1.5 to 1. 1 is particularly preferred.

  The hydrolysis and / or condensation reaction of the organosilane compound can be performed without a solvent or in a solvent. By this reaction, a curable compound can be produced.

(solvent)
When a solvent is used, the concentration of the organosilane sol can be appropriately determined. As the solvent, an organic solvent is preferably used in order to mix the components uniformly. For example, alcohols, aromatic hydrocarbons, ethers, ketones, esters and the like are preferable. The solvent is preferably one that dissolves the organosilane and the catalyst. Moreover, it is preferable on a process that an organic solvent is used as a coating liquid or a part of coating liquid, and the thing which does not impair solubility or dispersibility when mixed with other raw materials, such as a fluorine-containing polymer, is preferable.

  Among these, as alcohols, a monohydric alcohol or a dihydric alcohol can be mentioned, for example, As a monohydric alcohol, a C1-C8 saturated aliphatic alcohol is preferable. Specific examples of these alcohols include methanol, ethanol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, s-butyl alcohol, t-butyl alcohol, ethylene glycol, diethylene glycol, and triethylene glycol. be able to.

  Specific examples of aromatic hydrocarbons include benzene, toluene, xylene, etc .; specific examples of ethers include tetrahydrofuran, dioxane, ethylene glycol monobutyl ether; specific examples of ketones include acetone, methyl ethyl ketone, Methyl isobutyl ketone, diisobutyl ketone and the like; Specific examples of esters include ethyl acetate, propyl acetate, butyl acetate, propylene carbonate, ethylene glycol monoethyl ether acetate and the like.

  These organic solvents can also be used individually by 1 type or in mixture of 2 or more types. The concentration of the solid content with respect to the solvent in the reaction is not particularly limited, but is usually in the range of 1 to 90% by mass, and preferably in the range of 20 to 70% by mass.

(catalyst)
The hydrolysis and / or condensation reaction of the organosilane compound is preferably performed in the presence of a catalyst. Catalysts include inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid; organic acids such as oxalic acid, acetic acid, formic acid, methanesulfonic acid and toluenesulfonic acid; inorganic bases such as sodium hydroxide, potassium hydroxide and ammonia; triethylamine and pyridine Organic bases such as: metal alkoxides such as triisopropoxyaluminum and tetrabutoxyzirconium, and the like. From the viewpoint of production stability of the sol solution and storage stability of the sol solution, an acid catalyst ( Inorganic acids and organic acids) are used. Of inorganic acids, hydrochloric acid, sulfuric acid, and organic acids preferably have an acid dissociation constant {pKa value (25 ° C.)} of 4.5 or less in water, and an acid dissociation constant of 3.0 or less in hydrochloric acid, sulfuric acid, or water. More preferred is an organic acid, hydrochloric acid, sulfuric acid, an organic acid having an acid dissociation constant of 2.5 or less in water is more preferred, an organic acid having an acid dissociation constant in water of 2.5 or less is more preferred, and methanesulfonic acid Succinic acid, phthalic acid and malonic acid are more preferred, and succinic acid is particularly preferred.

  The hydrolysis and / or condensation reaction is usually performed by adding 0.3 to 2 mol, preferably 0.5 to 1 mol of water to 1 mol of the hydrolyzable group of the organosilane compound, and in the presence of the solvent. Alternatively, it is carried out by stirring at 25 to 100 ° C. in the absence and in the presence of an acid catalyst and a metal chelate compound.

  When the hydrolyzable group is an alkoxy group and the acid catalyst is an organic acid, since the carboxyl group or sulfo group of the organic acid supplies protons, the amount of water added can be reduced, and the alkoxy group of the organosilane compound can be reduced. The amount of water added to 1 mol of the hydrolyzable group such as 0 to 2 mol, preferably 0 to 1.5 mol, more preferably 0 to 1 mol, particularly preferably 0 to 0.5 mol. . When alcohol is used as the solvent, it is also preferred that substantially no water is added.

  When the acid catalyst is an inorganic acid, the acid catalyst is used in an amount of 0.01 to 10 mol%, preferably 0.1 to 5 mol%, based on the hydrolyzable group. In this case, the optimum amount of use varies depending on the amount of water added, but when water is added, it is 0.01 to 10 mol%, preferably 0.1 to 5 mol% based on the hydrolyzable group. In the case where water is not substantially added, it is 1 to 500 mol%, preferably 10 to 200 mol%, more preferably 20 to 200 mol%, still more preferably 50%, based on the hydrolyzable group. It is -150 mol%, Most preferably, it is 50-120 mol%.

(Metal chelate compound)
Metal chelate compounds (wherein, R ⁴¹ represents an alkyl group having 1 to 10 carbon atoms) Formula R ⁴¹ OH and an alcohol represented by the general formula R ⁴² COCH ₂ COR ⁴³ (wherein, R ⁴² is an alkyl group having 1 to 10 carbon atoms, R ⁴³ is a compound represented by the an alkyl group or an alkoxy group having 1 to 10 carbon atoms having 1 to 10 carbon atoms) as a ligand, Zr, Ti or Any metal having a central metal selected from Al can be suitably used without particular limitation. Within this category, two or more metal chelate compounds may be used in combination.

The metal chelate compound used in the present invention has the general formula Zr (OR ⁴¹ ) _p1 (R ⁴² COCHCOR ⁴³ ) _{p 2} , Ti (OR ⁴¹ ) _q1 (R ⁴² COCHCOR ⁴³ ) _{q 2} and Al (OR ⁴¹ ) _r1 (R ⁴² COCHCOR ⁴³ ) Those selected from the group of compounds represented by _r2 are preferred, and act to promote the condensation reaction of the organosilane compound.

R ⁴¹ and R ⁴² in the metal chelate compound may be the same or different and each is an alkyl group having 1 to 10 carbon atoms (specifically, an ethyl group, n-propyl group, i-propyl group, n-butyl group, s -Butyl group, t-butyl group, n-pentyl group), or phenyl group. R ⁴³ represents an alkyl group having 1 to 10 carbon atoms as described above, or an alkoxy group having 1 to 10 carbon atoms such as a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, and n-butoxy. Group, s-butoxy group, t-butoxy group and the like. Moreover, p1, p2, q1, q2, r1, and r2 in a metal chelate compound represent the integer determined so that it may become a 4 or 6-coordinate.

Specific examples of these metal chelate compounds include tri-n-butoxyethyl acetoacetate zirconium, di-n-butoxybis (ethyl acetoacetate) zirconium,
Zirconium chelate compounds such as n-butoxytris (ethylacetoacetate) zirconium, tetrakis (n-propylacetoacetate) zirconium, tetrakis (acetylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium; diisopropoxy bis (ethylacetate) Titanium chelate compounds such as acetate) titanium, diisopropoxy bis (acetylacetate) titanium, diisopropoxy bis (acetylacetonato) titanium; diisopropoxyethyl acetoacetate aluminum, diisopropoxyacetylacetonato aluminum, isopropoxy Bis (ethylacetoacetate) aluminum, isopropoxybis (acetylacetonate) aluminum Tris (ethylacetoacetate) aluminum, tris (acetylacetonate) aluminum, mono-acetylacetonate · bis (ethylacetoacetate) and the like aluminum chelate compounds such as 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, as a metal chelate compound, the partial hydrolyzate of these metal chelate compounds can also be used.

  The metal chelate compound is preferably 0.01 to 50% by mass, more preferably 0.1 to 50% by mass, and still more preferably 0.1 to 50% by mass with respect to the organosilane compound represented by the general formula (b). It is used at a ratio of 5 to 10% by mass. If the metal chelate compound component is at least the lower limit, the condensation reaction of the organosilane compound proceeds smoothly, and the resulting coating film has excellent durability. On the other hand, if the metal chelate compound is at most the upper limit, the organosilane compound And a composition containing a metal chelate compound component are preferable because the storage stability of the composition does not deteriorate.

  The hydrolysis and / or condensation reaction of the organosilane compound is carried out by stirring at 25 to 100 ° C., but is preferably controlled by the reactivity of the individual organosilane compound used.

The addition amount of the organosilane sol to the low refractive index layer is preferably 0.1 to 50% by mass, more preferably 0.5 to 20% by mass, and more preferably 1 to 10% by mass of the total solid content of the low refractive index layer. Particularly preferred.
The organosilane sol can be added to layers other than the low refractive index layer. In this case, the addition amount is preferably 0.001 to 50% by mass based on the total solid content of the layer to be added. 0.01 to 20 mass% is more preferable, 0.05 to 10 mass% is still more preferable, and 0.1 to 5 mass% is particularly preferable.

  The use amount (ratio) of the organosilane sol is, for example, preferably 5 to 100% by mass, more preferably 5 to 40% by mass, and still more preferably 8 to 35% by mass with respect to the fluorine-containing polymer in the low refractive index layer. 10-30 mass% is especially preferable. If the amount used is greater than or equal to the lower limit, the effects of the present invention will be sufficiently exerted, and if the amount used is less than or equal to the upper limit, the refractive index will increase or the shape / surface shape of the film will deteriorate. This is preferable because there is no inconvenience.

As described above, the polymerization initiator (C) contained in the low refractive index forming composition is preferably a heat and / or photodegradable initiator. The polymerization initiator (C) is not particularly limited as long as it is usually used, and can be used. The SP value of the polymerization initiator (C) used in the present invention and the curable compound (B) having an ethylenically unsaturated group is preferably larger than that of the binder polymer (A) used together. The method exemplified below is that the at least one polymerization initiator (C) and the curable compound having an ethylenically unsaturated group (B) to be added due to the difference in SP value are localized in the lower part of the low refractive index layer. Can be confirmed.
A low refractive index layer formed by coating and curing using a fluorine-containing binder polymer, an organosilane sol compound having a vinyl polymerizable substituent and an initiator (1C-1) described later is prepared. A surface obtained by cutting this sample with a microtome at an angle of 0.2 ° with respect to the sample surface was measured with TOF-SIMS, an image was drawn with a mass number peculiar to the material, and the distribution in the film was evaluated. For TOF-SIMS measurement, TOF-SIMS IV manufactured by ION-TOF was used. The sample was irradiated with Bi ₃ ⁺ with an acceleration voltage of 25 keV with a pulse width of 2 nsec, and secondary ions up to m / z 1000 were detected with a time-of-flight mass spectrometer. During the measurement, low-energy electrons of 20 eV were irradiated to suppress sample charging.
Although also described in the Examples below, by the measurement, _SiO 3 H from the organosilane sol, derived from the initiator (1C-1) Cl, a _C 3 _{F 5} from fluorine-containing binder polymer, respectively, m / z Detected at 76.974, 34.969, 130.992. From these three signal profiles, it is clear that the organosilane sol and the initiator (1C-1) are localized in the lower part of the low refractive index layer, and the fluorine-containing binder polymer is localized in the upper part of the low refractive index layer. It was.
Further, from the section TEM (transmission electron microscope) of the sample, it can be seen that the low refractive index layer has a two-layer structure, and the thickness of the lower layer of the low refractive index layer increases as the organosilane sol compound is increased. It became clear that the fluorine-containing binder polymer was localized at the top of the low refractive index layer, while the organosilane sol compound and the polymerization initiator of the present invention were localized at the bottom of the low refractive index layer. .

(SP value)
The SP value of a compound is a solubility parameter and is a numerical value of how easily it is soluble in a solvent. It is synonymous with the polarity often used in organic compounds. The greater the SP value, the greater the polarity. Represents that. The binder polymer of the low refractive index layer used in the present invention is preferably a thermosetting and / or ionizing radiation curable fluorine-containing polymer, and the SP value calculated by Fedor's estimation method is, for example, 20 or less. The SP value of the organosilane sol described in the previous section can be calculated in the same manner, and the SP value of the organosilane sol using the sol liquid b-1 used in the present invention in Examples described later is 22.4. The SP value referred to above is, for example, a value calculated by Fedor's estimation method (SP value basics / applications and calculation method p. 66: written by Hideki Yamamoto: Information Organization (issued March 31, 2005)).

[Polymerization initiator]
The polymerization initiator localized in the lower part of the low refractive index layer in the present invention is preferably a heat and / or light as long as it is an initiator that exhibits a value larger than the SP value of a binder polymer, particularly a fluorine-containing binder polymer. Any decomposable polymerization initiator may be used. Moreover, you may have any structure of the polymerization initiator frame | skeleton shown below. Furthermore, if the SP value is larger than that of the fluorine-containing binder polymer, the fluorine-containing binder polymer is localized at the upper part of the low refractive index layer, while the polymerization initiator is likely to be localized at the lower part of the low refractive index layer. Similarly, it is considered that the polymerization of the curable compound that is localized in the lower portion of the low refractive index layer proceeds efficiently.

  In a compound in which these initiator and curable compound are linked and bonded in the molecule, the same effect is obtained if the SP value of the linked and bonded compound is larger than that of the binder polymer. The curable compound is a compound having an ethylenically unsaturated group, and is linked to the polymerization initiator.

(Photoradical polymerization initiator skeleton)
The radical photopolymerization initiator skeleton is a compound similar to the photoradical polymerization initiator exemplified in the section of the binder polymer for forming a hard coat layer, and is a binder polymer for forming a low refractive index layer, particularly a fluorine-containing polymer. Any initiator may be used as long as it is an initiator exhibiting a value larger than the SP value of the binder polymer.

(Thermal radical initiator skeleton)
The thermal radical initiator skeleton is also a compound similar to the thermal radical polymerization initiator exemplified in the section of the binder polymer for forming a hard coat layer, and is a binder polymer for forming a low refractive index layer, particularly a fluorine-containing binder. Any initiator can be used as long as the initiator exhibits a value larger than the SP value of the polymer.

These initiators may be used alone or in combination.
Initiators that can be preferably used in the present invention and their SP values (calculated by Fedor's estimation method) are shown below, but are not limited thereto.

  Next, a curable compound having an ethylenically unsaturated group and a self-polymerization initiating curable compound in which a polymerization initiator is linked and bonded in the molecule will be exemplified.

  Further, specific compounds of the initiator that can be used in the present invention are shown below.

  Although there is no restriction | limiting in particular in the usage-amount of these polymerization initiators, it is preferable to use in the range of 0.1-20 mass parts with respect to 100 mass parts of curable compounds used together, More preferably, it is 1- 10 parts by mass.

  These polymerization initiator compounds may be used alone or in combination of two or more with other photosensitizers. Specific examples of the photosensitizer include n-butylamine, triethylamine, tri-n-butylphosphine, Michler's ketone and thioxanthone. Further, one or more auxiliary agents such as an azide compound, a thiourea compound, and a mercapto compound may be used in combination.

[Anti-fouling agent]
A compound having a known polysiloxane structure for the purpose of imparting antifouling properties, water resistance, chemical resistance, slipping properties, etc. to the antireflective film of the present invention, particularly the low refractive index layer as the uppermost layer. It is preferable to add a fluorine compound antifouling agent, a slip agent and the like as appropriate.

(Compound having polysiloxane structure)
By adding the compound having the polysiloxane structure to the low refractive index layer, it is possible to impart slipping property and improve scratch resistance and antifouling property. There is no restriction | limiting in particular in the structure of a compound, The thing which has a substituent in the terminal and / or side chain of a compound chain | strand which contains two or more dimethylsilyloxy units as a repeating unit is mentioned. The compound chain containing dimethylsilyloxy as a repeating unit may contain a structural unit other than dimethylsilyloxy.

  Although there is no restriction | limiting in particular in the molecular weight of the compound which has a polysiloxane structure, It is preferable that it is 100,000 or less, It is especially preferable that it is 50,000 or less, It is most preferable that it is 3000-30000.

  In general, an antireflection film is a product having a protective film attached to and wound around an adhesive layer for the purpose of surface protection, so that the compound having a polysiloxane structure contained in the low refractive index layer is an adhesive. The compound tends to be transferred to an agent layer or a protective film, and the compound easily moves to a layer below the low refractive index layer, for example, a high refractive index layer or a hard coat layer. From the viewpoint of preventing such transfer and migration, the compound preferably contains a hydroxyl group or a functional group that reacts with the hydroxyl group to form a bond.

  This bond formation reaction preferably proceeds rapidly under heating conditions and / or in the presence of a catalyst. Examples of such a substituent include an epoxy group and a carboxyl group. Examples of the compound having a preferred polysiloxane structure include, but are not limited to, the following.

(Including hydroxyl group)
“X-22-160AS”, “KF-6001”, “KF-6002”, “KF-6003”, “X-22-170DX”, “X-22-176DX”, “X-22-176D”, “X-22-176F” {manufactured by Shin-Etsu Chemical Co., Ltd.}; “FM-4411”, “FM-4421”, “FM-4425”, “FM-0411”, “FM-0421”, “ "FM-0425", "FM-DA11", "FM-DA21", "FM-DA25" {above, manufactured by Chisso Corp.}; "CMS-626", "CMS-222" {above, manufactured by Gelest} .

(Containing functional groups that react with hydroxyl groups)
"X-22-162C", "KF-105" {manufactured by Shin-Etsu Chemical Co., Ltd.}; "FM-5511", "FM-5521", "FM-5525", "FM-6611", " FM-6621 "," FM-6625 "{above, manufactured by Chisso Corporation}.

  In addition to the polysiloxane compound, another polysiloxane compound may be used in combination. Preferable examples include those having a substituent at the terminal and / or side chain of a compound chain containing a plurality of dimethylsilyloxy units as repeating units. The compound chain containing dimethylsilyloxy as a repeating unit may contain a structural unit other than dimethylsilyloxy. The substituents may be the same or different, and a plurality of substituents are preferable. Examples of preferred substituents include groups containing acryloyl group, methacryloyl group, vinyl group, aryl group, cinnamoyl group, oxetanyl group, fluoroalkyl group, polyoxyalkylene group, carboxyl group, amino group and the like.

  Although there is no restriction | limiting in particular in molecular weight, It is preferable that it is 100,000 or less, It is more preferable that it is 50,000 or less, It is especially preferable that it is 3000-30000, It is most preferable that it is 10,000-20000.

  Although there is no restriction | limiting in particular in silicon atom content of a silicone type compound, it is preferable that it is 18.0 mass% or more, It is especially preferable that it is 25.0-37.0 mass%, 30.0-37.0 Most preferably, it is mass%.

(Fluorine compounds)
As the fluorine compound used as an antifouling agent, a compound having a fluoroalkyl group is preferred. The fluoroalkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and a straight chain {for example, —CF ₂ CF ₃ , —CH ₂ (CF ₂ ) 4 H, —CH ₂ (CF ₂ ) ₈ CF ₃ , —CH ₂ CH ₂ (CF ₂ ) ₄ H, etc.}, branched structures {eg, CH (CF ₃ ) ₂ , CH ₂ CF (CF ₃ ) ₂ , CH (CH ₃ ) CF ₂ CF ₃ , CH (CH ₃ ) (CF ₂ ) ₅ CF ₂ H, etc.} may be an alicyclic structure (preferably a 5- or 6-membered ring such as a perfluorocyclohexyl group, a perfluorocyclopentyl group, or these Or an ether bond (for example, CH ₂ OCH ₂ CF ₂ CF ₃ , CH ₂ CH ₂ OCH ₂ C ₄ F ₈ H, CH ₂ CH ₂ OCH ₂ CH ₂ C ₈ F). ₁₇ , CH ₂ CH ₂ OCF ₂ CF ₂ OCF ₂ CF ₂ H, etc.) You may have. A plurality of the fluoroalkyl groups may be contained in the same molecule.

  These fluorine-based compounds preferably further have a substituent that contributes to bond formation or compatibility with the low refractive index layer film. The substituents may be the same or different, and a plurality of substituents are preferable. Examples of preferred substituents include acryloyl group, methacryloyl group, vinyl group, aryl group, cinnamoyl group, epoxy group, oxetanyl group, hydroxyl group, polyoxyalkylene group, carboxyl group, amino group and the like.

  The fluorine-based compound may be a polymer or an oligomer with a compound not containing a fluorine atom, and the molecular weight is not particularly limited. Although there is no restriction | limiting in particular in fluorine atom content of a fluorine-type compound, It is preferable that it is 20 mass% or more, It is especially preferable that it is 30-70 mass%, It is most preferable that it is 40-70 mass%.

  Examples of preferable fluorine-based compounds include “R-2020”, “M-2020”, “R-3833”, “M-3833” (above trade names) manufactured by Daikin Industries, Ltd .; Dainippon Ink and Chemicals, Inc. "Megafuck F-171", "Megafuck F-172", "Megafuck F-179A", "Defenser MCF-300" (named above), etc. manufactured by Co., Ltd. are mentioned, but it is limited to these. It is not something.

  When these antifouling agents are added, they are preferably added in the range of 0.01 to 20% by mass of the total solid content of the low refractive index layer, more preferably in the range of 0.05 to 10% by mass. Particularly preferably 0.1 to 5% by mass.

[Dustproofing agent, antistatic agent, etc.]
For the purpose of imparting properties such as dust resistance and antistatic property, a known cationic surfactant or a dustproof agent such as a polyoxyalkylene compound, an antistatic agent, or the like may be added as appropriate. These dustproofing agent and antistatic agent may contain the structural unit as a part of the function in the above-mentioned silicone compound or fluorine compound.

  When these are added as additives, it is preferably added in the range of 0.01 to 20% by mass of the total solid content of the low refractive index layer, more preferably in the range of 0.05 to 10% by mass. Particularly preferred is 0.1 to 5% by mass. Examples of preferred compounds include “Megafac F-150” (trade name) manufactured by Dainippon Ink and “SH-3748” (trade name) manufactured by Toray Dow Corning Co., Ltd. It is not limited to.

[Inorganic filler]
As the inorganic filler used in the low refractive index layer, those having a low refractive index are preferably used. Preferred inorganic fillers are silica particles and hollow silica particles, and hollow silica particles are particularly preferable. The average particle size of the inorganic filler is preferably 0.001 to 0.2 μm, and more preferably 0.001 to 0.05 μm. The particle diameter of the filler is preferably as uniform (monodispersed) as possible.

(Silica particles)
The average particle diameter of the silica 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 still more preferably 40% or more and 60% or less. That is, if the thickness of the low refractive index layer is 100 nm, the particle size of the silica 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 particles is equal to or greater than the lower limit value, the effect of improving the scratch resistance is exhibited. If the particle size is equal to or smaller than the upper limit value, fine irregularities are formed on the surface of the low refractive index layer, and the appearance such as black tightening or This is preferable because it does not cause problems such as poor integrated reflectance.

  The silica 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.

(Hollow silica particles)
In order to lower the refractive index of the low refractive index layer, it is preferable to use hollow silica particles. The hollow silica particles preferably have a refractive index of 1.15 to 1.40, more preferably 1.17 to 1.35, and most 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 silica 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 (2). The porosity x of the hollow silica particles is preferably 10 to 60%, more preferably 20 to 60%, and most preferably 30 to 60%.

Equation (2): x = (4πr i 3/3) / (4πr o 3/3) × 100

  Since the thickness of the outer shell is sufficiently thick and the strength of the particles is increased, particles having a refractive index of 1.15 or more are preferable from the viewpoint of scratch resistance.

  A method for producing hollow silica particles is described in, for example, Japanese Patent Application Laid-Open Nos. 2001-233611 and 2002-79616. In particular, particles having cavities inside the shell and having fine pores in the shell are particularly preferred. The refractive index of these hollow silica particles can be calculated by the method described in JP-A-2002-79616.

The coating amount of the hollow silica is preferably from ^{1mg / m 2 ~100mg / m 2} , more preferably ^{5mg / m 2 ~80mg / m 2} , more preferably from ^{10mg / m 2 ~60mg / m 2} . If the coating amount of the hollow silica is equal to or greater than the lower limit value, the effect of lowering the refractive index and the effect of improving scratch resistance are exhibited. If the coating amount is equal to or smaller than the upper limit value, fine irregularities are formed on the surface of the low refractive index layer. This is preferable because it does not cause defects such as black appearance and poor integrated reflectance.

The average particle diameter of the hollow silica 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 size of the hollow silica particles is preferably 30 nm or more and 150 nm or less, more preferably 35 nm or more and 100 nm or less, and still more preferably 40 nm or more and 65 nm or less. If the particle size of the silica particles is equal to or greater than the lower limit value, the ratio of the cavities is not too small, so that the refractive index lowering effect is exhibited. If the particle size is equal to or smaller than the upper limit value, the surface of the low refractive index layer is fine. This is preferable because irregularities are formed and appearance such as black tightening and inconveniences such as deterioration in integrated reflectance do not occur.

  The hollow silica particles may be either crystalline or amorphous, and monodisperse particles are preferred. The shape is most preferably a spherical diameter, but there is no problem even if the shape is indefinite.

  Further, two or more kinds of hollow silica having different particle average particle sizes can be used in combination. Here, the average particle diameter of the hollow silica can be determined from an electron micrograph.

In the present invention, the specific surface area of the hollow silica particles is preferably 20 to 300 m ² / g, more preferably 30~120m ² / g, most preferably 40~90m ² / g. The surface area can be determined by the BET method using nitrogen.

  In the present invention, silica particles having no voids can be used in combination with hollow silica particles. The preferred particle size of silica without voids is 30 nm to 150 nm, more preferably 35 nm to 100 nm, and most preferably 40 nm to 80 nm.

  Further, at least one kind of silica particles having an average particle size of less than 25% of the thickness of the low refractive index layer (referred to as “small size particle size silica particles”) is used as silica particles having the above particle size (“large size particles”). It can also be used in combination with “silica particles having a diameter”.

  Since the silica particles having a small particle size can exist in the gaps between the silica particles having a large particle size, the silica particles can contribute as a retaining agent for the silica particles having a large particle size.

  The average particle size of the silica particles having a small size is preferably 1 nm to 20 nm, more preferably 5 nm to 15 nm, and particularly preferably 10 nm to 15 nm. Use of such silica particles is preferable in terms of raw material costs and a retaining agent effect.

(surface treatment)
Silica particles and hollow silica particles are used in plasma dispersion treatment or corona discharge treatment in order to stabilize dispersion in the dispersion or coating solution, or to improve the affinity and binding properties with the binder component. Physical surface treatment, chemical surface treatment with a surfactant, a coupling agent, or the like may be performed. These surface treatment agents are preferably added and treated in an amount of 0.1 to 100% by weight, more preferably 1.0 to 50% by weight, and 5.0 to 35% by weight with respect to the inorganic filler. % Is even more preferred.

  As the coupling agent, an alkoxy metal compound (for example, a titanium coupling agent, a silane coupling agent, etc.) is preferably used. Especially, it is preferable that at least any one of said inorganic fine particle and hollow silica particle is surface-treated with the organosilane compound represented by the following general formula (a).

Formula (a): (R ¹¹ ) _m1 -SiX ¹¹ _4-m1

In the general formula (a), R ¹¹ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, hexyl, decyl, hexadecyl and the like. The alkyl group is preferably an alkyl group having 1 to 30 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 6 carbon atoms. Examples of the aryl group include phenyl and naphthyl, and a phenyl group is preferable.

X ¹¹ represents a hydroxyl group or a hydrolyzable group, for example, an alkoxy group (preferably an alkoxy group having 1 to 5 carbon atoms, such as a methoxy group or an ethoxy group), a halogen atom (for example, Cl, Br, I And a group represented by R ¹² COO (R ¹² is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, such as CH ₃ COO, C ₂ H ₅ COO, etc.), preferably Is an alkoxy group, particularly preferably a methoxy group or an ethoxy group.
m1 represents an integer of 0 to 3, and is preferably 1 or 2.

When R ¹¹ or the X ¹¹ there are a plurality, even more R ¹¹ or X ¹¹ is the same, respectively, may be different.

The substituent contained in R ¹¹ is not particularly limited, but a halogen atom (fluorine, chlorine, bromine, etc.), hydroxyl group, mercapto group, carboxyl group, epoxy group, alkyl group (methyl, ethyl, i-propyl, propyl, t-butyl etc.), aryl groups (phenyl, naphthyl etc.), aromatic heterocyclic groups (furyl, pyrazolyl, pyridyl etc.), alkoxy groups (methoxy, ethoxy, i-propoxy, hexyloxy etc.), aryloxy (phenoxy etc.) ), Alkylthio groups (methylthio, ethylthio, etc.), arylthio groups (phenylthio, etc.), alkenyl groups (vinyl, 1-propenyl, etc.), acyloxy groups (acetoxy, acryloyloxy, methacryloyloxy, etc.), alkoxycarbonyl groups (methoxycarbonyl, ethoxy) Carbonyl, etc.), aryloxy Carbonyl groups (phenoxycarbonyl, etc.), carbamoyl groups (carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N-methyl-N-octylcarbamoyl, etc.), acylamino groups (acetylamino, benzoylamino, acrylicamino, methacrylamino) Etc.), and these substituents may be further substituted.

When there are a plurality of R ¹¹ , at least one is preferably a substituted alkyl group or a substituted aryl group.

In the present invention, the organosilane compound that can be particularly preferably used is preferably an organosilane compound having a vinyl polymerizable substituent in the general formula (a), and among them, R ¹¹ in the general formula (a) is (meta ) It is particularly preferred that it is a group containing an acryloyl group, that is, the substituent contained in R ¹¹ is a (meth) acryloyloxy group.

The R ¹¹ in the general formula (a) is a group containing an epoxy group, that the organosilane compound substituent is an epoxy group contained in R ¹¹ likewise can be particularly preferably used.

  The silica particles are preferably dispersed in the medium in advance before the surface treatment in order to reduce the load of the surface treatment. Specific examples of the surface treating agent and the catalyst that can be preferably used in the present invention include organosilane compounds and catalysts described in WO 04/017105.

  As the inorganic filler used for the low refractive index layer, two types of fillers having different particle diameters may be used in combination. In particular, by using an inorganic filler having a particle diameter of 0.02 to 0.08 μm and an inorganic filler having a particle diameter of 0.02 μm or less in combination, both reflectance and scratch resistance can be achieved. The ratio of the added amount of each of the two types of inorganic fillers having different particle diameters can be freely changed between 0 and 1 depending on the desired balance between reflectivity and scratch resistance. When it is desired to reduce the reflectance, it is preferable that the inorganic filler having a small particle diameter occupies the majority, and when it is desired to enhance the scratch resistance, it is preferable to increase the ratio of the inorganic filler having a large particle diameter.

  The addition amount of the inorganic filler is preferably 5 to 90% by mass of the total mass of the low refractive index layer, more preferably 10 to 70% by mass, and particularly preferably 10 to 50% by mass.

[Dispersion stabilizer]
In the present invention, it is also preferred to use a dispersion stabilizer in combination for the purpose of suppressing aggregation and sedimentation of the inorganic filler in the low refractive index layer. As the dispersion stabilizer here, the same dispersion stabilizer used in the hard coat layer can be used in the same manner. The preferable addition amount is the same.

[Solvent of coating solution for forming each layer]
The solvent composition of the coating solution used for forming the hard coat layer and the low refractive index layer according to the present invention may be either single or mixed. When mixed, the solvent has a boiling point of 100 ° C. or less in all the solvents. Is preferably 50 to 100% by mass, more preferably 80 to 100% by mass, more preferably 90 to 100% by mass, and still more preferably 100% by mass. If the solvent having a boiling point of 100 ° C. or lower is equal to or higher than the lower limit, the drying rate will not be too slow, the coated surface shape will not be deteriorated, and the coating film thickness will not be uneven, the reflectance, etc. This is preferable because problems such as deterioration of the optical properties of the film do not occur. In the present invention, these problems can be solved by using a coating liquid containing a large amount of a solvent having a boiling point of 100 ° C. or less.

  Examples of the solvent having a boiling point of 100 ° C. or lower include hexane (boiling point 68.7 ° C., hereinafter “° C.” is omitted), heptane (98.4), cyclohexane (80.7), benzene (80.1), and the like. Hydrocarbons; halogenated carbonization such as dichloromethane (39.8), chloroform (61.2), carbon tetrachloride (76.8), 1,2-dichloroethane (83.5), trichloroethylene (87.2), etc. Hydrogens; for example, ethers such as diethyl ether (34.6), diisopropyl ether (68.5), dipropyl ether (90.5), tetrahydrofuran (66); for example ethyl formate (54.2), methyl acetate ( 57.8), ethyl acetate (77.1), esters such as isopropyl acetate (89); for example, acetone (56.1), 2-butanone ( Ketones such as tilethylketone = MEK, 79.6); alcohols such as methanol (64.5), ethanol (78.3), 2-propanol (82.4), 1-propanol (97.2) Cyano compounds such as acetonitrile (81.6) and propionitrile (97.4); carbon disulfide (46.2). Of these, ketones and esters are preferable, and ketones are particularly preferable. Among the ketones, 2-butanone is particularly preferable.

  Examples of the solvent having a boiling point of 100 ° C. or higher include octane (125.7), toluene (110.6), xylene (138), tetrachloroethylene (121.2), chlorobenzene (131.7), and dioxane (101.3). , Dibutyl ether (142.4), isobutyl acetate (118), cyclohexanone (155.7), 2-methyl-4-pentanone (methyl isobutyl ketone = MIBK, 115.9), 1-butanol (117.7), N, N-dimethylformamide (153), N, N-dimethylacetamide (166), dimethyl sulfoxide (189), and the like. Cyclohexanone and 2-methyl-4-pentanone are preferable.

  By diluting the hard coat layer and the low refractive index layer component according to the present invention with the solvent having the above composition, coating solutions for forming these layers are prepared. The concentration of the coating solution is preferably adjusted in consideration of the viscosity of the coating solution and the specific gravity of the layer material, but is preferably 0.1 to 20% by mass, more preferably 1 to 10% by mass.

(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 {e.g., triacetyl cellulose, diacetyl cellulose, typically “TAC-TD80U” (trade name) manufactured by FUJIFILM Corporation), polyamide, polycarbonate, polyester ( For example, polyethylene terephthalate, polyethylene naphthalate, etc.), polystyrene, polyolefin, norbornene resin {“Arton” (trade name), manufactured by JSR Corporation}, amorphous polyolefin {“ZEONEX” (trade name), Nippon Zeon ( Etc.}. Of these, triacetyl cellulose, polyethylene terephthalate, and polyethylene naphthalate are preferable, and triacetyl cellulose is particularly preferable.
Although the thickness of a support body can use the thing of about 25 micrometers-1000 micrometers normally, Preferably it is 25 micrometers-250 micrometers, and it is more preferable that it is 30 micrometers-90 micrometers.
Any width of the support can be used, but from the viewpoint of handling, yield, and productivity, a width of 100 to 5000 mm is usually used, preferably 800 to 3000 mm, and preferably 1000 to 2800 mm. More preferably.
The surface of the support is preferably smooth, and the average roughness Ra is preferably 1 μm or less, preferably 0.0001 to 0.5 μm, and 0.001 to 0.1 μm. Is more preferable.

  The triacetyl cellulose film is composed of a single layer or a plurality of layers. A single-layer triacetyl cellulose film is produced by drum casting or band casting disclosed in JP-A No. 7-11055 and the like. It is produced by the so-called co-casting method disclosed in Japanese Patent Publication No. 61-94725 and Japanese Patent Publication No. 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. Dissolve in a solvent, and add a solution (called a dope) to which various additives such as plasticizer, ultraviolet absorber, deterioration inhibitor, slipping agent, peeling accelerator and the like are added as necessary. When casting by a dope supply means (called a die) on a support composed of a metal belt or a rotating drum, a single dope is cast in a single layer if it is a single layer, and a high concentration in the case of multiple layers. A low-concentration dope is co-cast on both sides of the cellulose ester dope, and the film is dried to some extent on the support to release the rigid film, and then peeled off from the support. Is a method by passing the drying section by the species of the conveying means consists of removing the solvent.

  A typical solvent for dissolving triacetylcellulose 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). In preparing a triacetyl cellulose dope using a solvent substantially free of dichloromethane or the like, the following special dissolution method is essential.

The first dissolution method is called a cooling dissolution method and will be described below.
First, triacetyl cellulose 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 manner, the mixture of triacetyl cellulose and solvent solidifies. Furthermore, 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 triacetyl cellulose 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 dissolution method and will be described below.
First, triacetyl cellulose is gradually added to a solvent at a temperature around room temperature (−10 to 40 ° C.) while stirring. The triacetyl cellulose solution used in the present invention is preferably swollen beforehand by adding triacetyl cellulose to a mixed solvent containing various solvents. In this method, the dissolution concentration of triacetyl cellulose 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 triacetylcellulose solution may be left at room temperature, and more preferably, the apparatus may be cooled using a coolant such as cooling water.

  A cellulose acetate film substantially free of halogenated hydrocarbons such as dichloromethane and a method for producing the same are disclosed in JIII Journal of Technical Disclosure (Publication No. 2001-1745, published on March 15, 2001; No. 1745).

(Formation of antireflection film)
Each layer of the antireflection film having a multilayer structure is formed by a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a die coating method, a wire bar coating method, a gravure coating method, an extrusion coating method (US Pat. No. 2,681,294) Can be formed by coating, but is preferably coated by a die coating method, and more preferably by using a new die coater described later. Two or more layers may be applied simultaneously. The method of simultaneous application is described in US Pat. Nos. 2,761,791, 2,941,898, 3,508,947, 3,526,528, and Yuji Harasaki, “Coating Engineering”, Asakura Shoten (1973), page 253. There is.

  In order to continuously produce the antireflection film of the present invention, for example, a step of continuously unwinding a roll-shaped base film (transparent support), a step of applying and drying a coating solution, and a coating film are cured. And a step of winding up the base film having the cured layer.

Specifically, it can be performed as follows.
The base film is continuously unwound from the roll-type base film into the clean room. In the clean room, the static electricity charged in the base film is removed by an electrostatic static neutralizer, and then adhered to the base film. Remove foreign matter using a dust remover. Next, the coating solution is applied onto the base film at the coating unit installed in the clean room, and the coated base film is sent to the drying room and dried.

  The substrate film having a dried coating layer is sent from the drying chamber to the thermosetting section, heated and cured, and then sent to the radiation curing chamber, where the monomer contained in the coating layer is polymerized by irradiation with radiation. Harden. In some cases, the film is directly sent to the radiation curing chamber, irradiated with radiation, the monomer contained in the coating layer is polymerized to complete the curing, and the base film having the layer that has been cured is wound up into a roll shape. It becomes.

In the present invention, a die coating method is preferably used as a coating method from the viewpoint of a higher production rate. The die coating method can achieve a high level of productivity and surface condition without uneven coating.
Preferably used. As a manufacturing method of the antireflection film of the present invention, the following coating method using such a die coating method is preferable.

  That is, the manufacturing method includes a coating step of applying a coating liquid from the slot of the tip lip by bringing the land of the tip lip of the slot die close to the surface of the web supported continuously by the backup roll. The slot die has a slot die whose land length in the web traveling direction of the tip lip on the web traveling direction side of the slot die is 30 μm or more and 100 μm or less, and is opposite to the web traveling direction when the slot die is set at the coating position. The gap between the tip lip on the side and the web is larger by 30 μm or more and 120 μm or less than the gap between the tip lip on the web traveling direction side and the web (hereinafter, this numerical limitation is referred to as “over bit length”). It is preferable to apply | coat using the coating device installed so that it might become.

In particular, a die coater that can be preferably used in the production method of the present invention will be described below with reference to the drawings. The die coater can be used when the wet coating amount is small (20 mL / m ² or less), which is preferable.

[Configuration of die coater]
FIG. 6 is a cross-sectional view of an example of a coater (coating device) using a slot die that can suitably implement the present invention.
The coater 10 includes a backup roll 11 and a slot die 13, and the coating liquid 14 is discharged from the slot die 13 in a bead shape 14 a and applied to the web W that is continuously supported by the backup roll 11. Thus, the coating film 14b is formed on the web W.

  Inside the slot die 13, a pocket 15 and a slot 16 are formed. The pocket 15 has a curved section and a straight section, and may be substantially circular or semicircular. The pocket 15 extends with its cross-sectional shape in the width direction of the slot die 13 (here, the width direction of the slot die 13 refers to the front side or the back side toward the drawing shown in FIG. 6). In the liquid storage space for the applied coating solution, the effective extension length is generally equal to or slightly longer than the coating width. The supply of the coating liquid 14 to the pocket 15 is performed from the side surface of the slot die 13 or from the center of the surface opposite to the slot opening 16a. The pocket 15 is provided with a stopper (not shown) that prevents the coating liquid 14 from leaking out.

  The slot 16 is a flow path of the coating liquid 14 from the pocket 15 to the web W, and has a cross-sectional shape in the width direction of the slot die 13 similarly to the pocket 15, and the opening 16a located on the web side is generally Using a thing such as a width regulating plate (not shown), the length is adjusted to be approximately the same as the coating width. The angle between the slot tip of the slot 16 and the tangent in the running direction of the web W of the backup roll 11 is preferably 30 ° or more and 90 ° or less.

  The tip lip 17 of the slot die 13 where the opening 16a of the slot 16 is located is tapered, and the tip is a flat portion 18 called a land. The upstream side of the land 18 in the traveling direction of the web W with respect to the slot 16 (the traveling direction, that is, the direction opposite to the arrow direction in the drawing) is the upstream lip land 18a, and the downstream side (the traveling direction side) is downstream. This is called side lip land 18b.

7A and 7B show the cross-sectional shape of the slot die 13 in comparison with the conventional one. FIG. 7A shows the slot die 13 preferably used in the present invention, and FIG. 7B shows the conventional slot die 30. Show. In the conventional slot die 30, the distance between the upstream lip land 31a and the web of the downstream lip land 31b is equal. Reference numeral 32 denotes a pocket, and 33 denotes a slot. On the other hand, in the slot die 13 suitable for the present invention, the downstream side lip land length I _LO is shortened, and this makes it possible to accurately apply a wet film thickness of 20 μm or less.

The land length I _UP of the upstream lip land 18a is not particularly limited, but is preferably used in the range of 500 μm to 1 mm. The land length I _LO of the downstream lip land 18b is not less than 30 μm and not more than 100 μm, preferably not less than 30 μm and not more than 80 μm, more preferably not less than 30 μm and not more than 60 μm. If the land length I _LO of the downstream lip is shorter than 30 μm, the edge or land of the tip lip is likely to be chipped, streaks are likely to occur in the coating film, and consequently application is impossible. In addition, it becomes difficult to set the position of the wetting line on the downstream side, and there is a problem that the coating liquid tends to spread on the downstream side. It has been conventionally known that this wet spreading of the coating solution on the downstream side means non-uniform wetting lines and leads to a problem of causing a defective shape such as a streak on the coated surface. On the other hand, when the land length I _LO of the downstream lip is longer than 100 μm, the bead itself cannot be formed, so that it is impossible to apply the thin layer.

Further, the downstream lip land 18b has an overbite shape closer to the web W than the upstream lip land 18a. Therefore, the degree of decompression can be reduced, and a bead suitable for thin film coating can be formed. The difference in the distance between the downstream lip land 18b and the web W of the upstream lip land 18a (hereinafter referred to as the overbite length LO) is preferably 30 μm to 120 μm, more preferably 30 μm to 100 μm, and most preferably 30 μm. It is 80 μm or less. When the slot die 13 has an overbite shape, the gap _GL between the tip lip 17 and the web W indicates the gap between the downstream lip land 18b and the web W.

FIG. 8 is a perspective view showing a slot die and its periphery in a coating process suitable for the present invention. On the opposite side of the web W from the traveling direction side, the decompression chamber 40 is installed at a position where it does not come into contact so that sufficient decompression adjustment can be performed on the bead 14a. The decompression chamber 40 includes a back plate 40a and a side plate 40b for maintaining its operating efficiency, and there are gaps G _B , G between the back plate 40a and the web W and between the side plate 40b and the web W, respectively. _S exists.

9 and 10 are sectional views showing the decompression chamber 40 and the web W which are close to each other. The side plate and the back plate may be integrated with the chamber main body as shown in FIG. 9, or may be structured to be fastened to the chamber with screws 40c or the like so that the gap can be appropriately changed as shown in FIG. . In any structure, portions actually opened between the back plate 40a and the web W and between the side plate 40b and the web W are defined as gaps G _B and G _S , respectively. The gap G _B between the back plate 40a and the web W in the vacuum chamber 40, when the vacuum chamber 40 is placed under the web W and the slot die 13 as shown in FIG. 8, the uppermost end of the back plate 40a to the web W The gap is shown.

The gap G _B between the back plate 40a and the web W, it is preferable to install and larger than the gap G _L between the end lip 17 and the web W of the slot die 13, thereby, due to the eccentricity of the backup roll 11 A change in the degree of decompression near the bead can be suppressed. For example, when the gap G _L between the end lip 17 and the web W of the slot die 13 is 30μm or more 100μm or less, the gap G _B between the back plate 40a and the web W is preferably 100μm or 500μm or less.

[Coating method]
In the present invention, it may be cured by direct irradiation with ionizing radiation after drying, or may be cured by heating after drying and further irradiation with ionizing radiation. In any case, when curing by irradiating with ionizing radiation, the ionizing radiation is irradiated in an atmosphere having an oxygen concentration of 3% by volume or less, and the oxygen concentration is 3% by volume for 0.5 seconds or more from the start of the ionizing radiation irradiation. It is preferable to harden by the process of maintaining the following atmosphere. By supplying inert gas to the ionizing radiation irradiation chamber and slightly blowing out to the web entrance side of the irradiation chamber, it is possible to eliminate the carry air accompanying the web conveyance and effectively reduce the oxygen concentration in the reaction chamber Thus, the substantial oxygen concentration at the extreme surface where oxygen is largely inhibited from curing can be efficiently reduced. The direction of the flow of the inert gas on the web entrance side of the irradiation chamber can be controlled by adjusting the balance between supply and exhaust of the irradiation chamber.

  Direct blowing of an inert gas onto the web surface is also preferably used as a method for removing the carried air. In particular, it is preferable that the low refractive index layer which is the outermost layer and has a small film thickness is cured by this method.

  Further, by providing a front chamber in front of the reaction chamber and excluding oxygen on the web surface in advance, the curing can proceed more efficiently. Further, the side surface constituting the web entrance side of the ionizing radiation reaction chamber or the front chamber is preferably 0.2 to 15 mm in gap with the web surface in order to use the inert gas efficiently, more preferably, 0. The thickness is preferably 2 to 10 mm, and most preferably 0.2 to 5 mm.

  However, in order to continuously produce webs, it is necessary to join the webs together and a method of attaching them with a joining tape or the like is widely used for joining. For this reason, when the gap between the entrance surface of the ionizing radiation reaction chamber or the front chamber and the web is too narrow, there arises a problem that the joining member such as the joining tape is caught. For this reason, in order to narrow the gap, it is preferable that at least a part of the entrance surface of the ionizing radiation reaction chamber or the front chamber is movable and the gap is widened by the junction thickness when the junction enters. In order to achieve this, the entrance surface of the ionizing radiation reaction chamber or the front chamber is made movable in the forward and backward directions, and when the joint passes, it moves forward and backward to widen the gap, or the ionizing radiation reaction chamber or the front chamber. It is possible to move the chamber entrance surface vertically with respect to the web surface and move up and down to widen the gap as the joint passes.

  The oxygen concentration of the atmosphere when irradiating with ionizing radiation is 3% by volume or less, preferably 1% by volume or less, and more preferably 0.5% by volume or less. In order to reduce the oxygen concentration, a large amount of an inert gas such as nitrogen is required. From the viewpoint of production cost, it is preferable not to lower the oxygen concentration more than necessary. As a means for reducing the oxygen concentration, it is preferable to replace the atmosphere (nitrogen concentration of about 79% by volume, oxygen concentration of about 21% by volume) with another inert gas, and particularly preferably with nitrogen (nitrogen purge). It is.

  In the present invention, at least one layer laminated on the transparent substrate is irradiated with ionizing radiation in an atmosphere having an oxygen concentration of 3% by volume or less, and an atmosphere having an oxygen concentration of 3% by volume or less from 0.5 second or more after the start of ionizing radiation irradiation. Is preferably maintained. The time maintained in the low oxygen concentration atmosphere is preferably 0.7 seconds or more and 60 seconds or less, and more preferably 0.7 seconds or more and 10 seconds or less. The low oxygen concentration maintaining time is preferably 0.5 seconds or longer because the curing reaction proceeds sufficiently and sufficient curing can be performed. Further, maintaining the low oxygen condition for a long time increases the size of the equipment and requires a large amount of inert gas, so the time is preferably 60 seconds or less.

In the present invention, at least one layer laminated on the transparent substrate can be cured by multiple times of ionizing radiation. In this case, it is preferable that at least two ionizing radiations are performed in a continuous reaction chamber in which the oxygen concentration does not exceed 20% by volume. By performing multiple times of ionizing radiation irradiation in the same low oxygen concentration reaction chamber, the reaction time required for curing can be effectively ensured. In particular, when increasing the production speed for high productivity, it is preferable to perform multiple ionizing radiation irradiations in order to ensure the energy of ionizing radiation necessary for the curing reaction, ensuring the reaction time necessary for the curing reaction. In addition, the above aspect is effective.

  The ionizing radiation species in the present invention is not particularly limited, and is appropriately selected from ultraviolet rays, electron beams, near ultraviolet rays, visible light, near infrared rays, infrared rays, X-rays and the like according to the type of curable composition forming the film. Although it can be selected, irradiation with ultraviolet rays is preferred in the present invention. Ultraviolet curing is preferred because the polymerization rate is fast, the equipment can be made compact, and there are many types of compounds that can be selected and the price is low.

  In the case of ultraviolet rays, ultra-high pressure mercury lamps, high pressure mercury lamps, low pressure mercury lamps, carbon arcs, xenon arcs, metal halide lamps and the like can be used. In the case of electron beam irradiation, energy of 50 to 1000 keV emitted from various electron beam accelerators such as Cockloft Walton type, bandegraph type, resonant transformation type, insulated core transformer type, linear type, dynamitron type, and high frequency type. An electron beam having the following is used.

[Use of antireflection film]
When the antireflection film of the present invention is used in a display device such as a liquid crystal display device, it can be disposed on the outermost surface of the display device by providing an adhesive layer on one side. A triacetyl cellulose film is often used as a protective film for protecting the polarizing film of the polarizing plate. When the transparent support of the antireflection film of the present invention is a triacetyl cellulose film, the antireflection film is used as it is. It is preferable in view of cost.

[Saponification]
The antireflective film of the present invention is disposed on the outermost surface of a display device by providing an adhesive layer on one side, or when used as it is as a protective film for a polarizing plate, it is transparently supported for sufficient adhesion. It is preferable to carry out a saponification treatment after forming the outermost layer on the body.

  The saponification treatment is performed by a known method, for example, by immersing the antireflection film in an alkali 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. By saponification treatment, the surface of the transparent support opposite to the side having the outermost layer is hydrophilized.

  The hydrophilized surface 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 when adhering to the polarizing film, it is difficult for dust to enter between the polarizing film and the anti-reflection film, thereby preventing point defects due to dust. It is effective for.

  The saponification treatment is preferably carried out so that the contact angle of water on the surface of the transparent support opposite to the side having the outermost layer 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 two. The following (1) is excellent in that it can be processed in the same process as a general-purpose triacetyl cellulose film, but since the saponification treatment is performed up to the antireflection film surface, the surface is alkali-hydrolyzed and the film deteriorates. The problem that the treatment liquid becomes dirty can be a problem. In that case, although it becomes a special process, the following (2) is excellent.

(1) After the antireflection film is formed on the transparent support, the back surface of the film is saponified by immersing it in an alkaline solution at least once.
(2) Before or after the formation of the antireflection film on the transparent support, the alkaline solution is applied to the surface of the antireflection film opposite to the surface on which the antireflection film is formed, and is heated, washed and / or washed By summing, only the back surface of the film is saponified.

<Use of antireflection film>
〔Polarizer〕
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.

[Polarizing film]
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 in which the absorption axis of the polarizing film is neither parallel nor perpendicular to the longitudinal direction is produced by the following method.

  That is, both ends of a continuously supplied polymer film are stretched by applying a tension while being held by holding means and stretched at least 1.1 to 20.0 times in the film width direction, The longitudinal movement speed difference of the holding device 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 °. It can be manufactured by a stretching method in which the traveling direction is bent while both ends of the film are held.

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

  Of the two protective films of the polarizing film, the film other than the antireflection film is preferably an optical compensation film comprising an optically anisotropic layer. The optical compensation film (retardation film) can improve the viewing angle characteristics of the liquid crystal display screen. A known film can be used as the optical compensation film, but the optical compensation film described in JP-A-2001-100042 is preferable in terms of widening the viewing angle.

[Display device]
The antireflection film of the present invention is used in a 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).

[Liquid Crystal Display]
The antireflection film of the present invention and the polarizing plate using the same can be advantageously used in a display device such as a liquid crystal display device, and is preferably used as the outermost layer of the display.

  The liquid crystal display device has a liquid crystal cell and two polarizing plates arranged on both sides thereof, and the liquid crystal cell carries a liquid crystal between two electrode substrates. Furthermore, one optically anisotropic layer may be disposed between the liquid crystal cell and one polarizing plate, or two optically anisotropic layers may be disposed between the liquid crystal cell and both polarizing plates.

The liquid crystal cell is preferably in TN mode, VA mode, OCB mode, IPS mode or ECB mode.

(TN mode)
In the TN mode liquid crystal cell, rod-like liquid crystal molecules are substantially horizontally aligned when no voltage is applied, and are twisted and aligned at 60 to 120 °.
The TN mode liquid crystal cell is most frequently used as a color TFT liquid crystal display device, and is described in many documents.

(VA mode)
In a VA mode liquid crystal cell, rod-like liquid crystalline molecules are aligned substantially vertically when no voltage is applied.

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) A liquid crystal cell (“SID97, Digest of tech. Papers” (Preliminary Collection), Vol. 28 (1997), p. 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. 58-59 (1998) description}, and
(4) Includes SURVAVAL mode liquid crystal cells (announced at "LCD International 98").

(OCB mode)
The OCB mode liquid crystal cell is 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 and lower portions of the liquid crystal cell. Nos. 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.

(IPS mode)
The IPS mode liquid crystal cell is a type in which a nematic liquid crystal is switched by applying a lateral electric field. For details, refer to “Proc. IDRC” (Asia Display '95), p. 577-580 and p. 707-710.

(ECB mode)
In the ECB mode liquid crystal cell, rod-like liquid crystalline molecules are substantially horizontally aligned when no voltage is applied. The ECB mode is one of the liquid crystal display modes having the simplest structure, and is described in detail in, for example, JP-A-5-203946.

[Displays other than liquid crystal display devices]
(PDP)
A plasma display panel (PDP) is generally composed of a gas, a glass substrate, an electrode, an electrode lead material, a thick film printing material, and a phosphor. Two glass substrates are a front glass substrate and a rear glass substrate. An electrode and an insulating layer are formed on the two glass substrates. A phosphor layer is further formed on the rear glass substrate. Two glass substrates are assembled and gas is sealed between them.

  Plasma display panels (PDP) are already commercially available. The plasma display panel is described in JP-A-5-205643 and JP-A-9-306366.

  The front plate may be disposed on the front surface of the plasma display panel. The front plate preferably has sufficient strength to protect the plasma display panel. The front plate can be used with a gap from the plasma display panel, or can be used by directly pasting the front plate to the plasma display body.

  In a display device such as a plasma display panel, the antireflection film of the present invention can be directly attached to the display surface as an optical filter. When a front plate is provided in front of the display, an antireflection film as an optical filter can be attached to the front side (outside) or the back side (display side) of the front plate.

(Touch panel)
The antireflection film of the present invention can be applied to touch panels described in JP-A Nos. 5-127822 and 2002-48913.

(Organic EL device)
The antireflection film of the present invention can be used as a protective film for organic EL elements and the like.

  When the antireflection film of the present invention is used for an organic EL device or the like, JP-A-11-335661, JP-A-11-335368, JP-A-2001-192651, JP-A-2001-192652, JP-A-2001-192653. JP, 2001-335776, JP 2001-247859, JP 2001-181616, JP 2001-181617, JP 2002-181816, JP 2002-181617, JP 2002-056776. It is possible to apply the contents described in each publication. Moreover, it is preferable to use together with the content of each gazette of Unexamined-Japanese-Patent No. 2001-148291, Unexamined-Japanese-Patent No. 2001-221916, and Unexamined-Japanese-Patent No. 2001-231443.

[Various characteristic values]
Various measurement methods and preferred characteristic values relating to the antireflection film of the present invention are shown below.

[Reflectance]
The specular reflectance and color are measured by attaching an adapter “ARV-474” to a spectrophotometer “V-550” [manufactured by JASCO Corporation], and an incident angle of 5 ° in a wavelength region of 380 to 780 nm. By measuring the specular reflectance at an exit angle of -5 °, the average reflectance of 450 to 650 nm is calculated, and the antireflection property can be evaluated.

[Color]
The polarizing plate using the antireflection film of the present invention as its protective film is a color of regular reflection light with respect to incident light having an incident angle of 5 ° in the wavelength range of 380 nm to 780 nm of the CIE standard light source D ₆₅ , that is, By obtaining the L ^* , a ^* , and b ^* values of the CIE 1976 L ^* a ^* b ^* color space, the color can be evaluated.

The L ^* , a ^* , and b ^* values are preferably in the ranges of 3 ≦ L ^* ≦ 20, −7 ≦ a ^* ≦ 7, and −10 ≦ b ^* ≦ 10, respectively. By setting it within this range, the color of reflected light from red purple to blue purple, which has been a problem with conventional polarizing plates, is reduced, and 3 ≦ L ^* ≦ 10, 0 ≦ a ^* ≦ 5, and − 7 ≦ b ^* ≦ 0 is greatly reduced, and when applied to a liquid crystal display device, when applied to a liquid crystal display device, such as indoor fluorescent light, the color tone when a little bright external light is reflected. Neutral, don't mind. Specifically, if a ^* ≦ 7, the reddishness will not be too strong, and if a ^* ≧ −7, the cyanishness will not be too strong. If b ^* ≧ −7, the bluish color does not become too strong, and if b ^* ≦ 0, the yellowish color does not become too strong.

Furthermore, the color uniformity of the reflected light is determined according to the following formula (3) from a ^* b ^* on the L ^* a ^* b ^* chromaticity diagram obtained from the reflection spectrum of the reflected light from 380 nm to 680 nm. It can be obtained as the rate of change in taste.

Formula (3):

Where a ^* _max and a ^* _min are the maximum and minimum values of a ^* values, respectively; b ^* _max and b ^* _min are the maximum and minimum values of b ^* values, respectively; a ^* _av and b ^* _av Are average values of a ^* and b ^* values, respectively. The color change rate is preferably 30% or less, more preferably 20% or less, and most preferably 8% or less.

In the antireflection film of the present invention, ΔE _w which is a change in color before and after the weather resistance test is preferably 15 or less, more preferably 10 or less, and most preferably 5 or less. In this range, low reflection and reduction of the color of reflected light can be achieved at the same time. For example, when applied to the outermost surface of a display device, external light with high brightness such as an indoor fluorescent lamp is slightly reflected. The color tone is neutral, and the quality of the displayed image is good, which is preferable.

The color change ΔE _w can be obtained according to the following mathematical formula (4).

Formula (4): ΔE _w = [(ΔL _w ) ² + (Δa _w ) ² + (Δb _w ) ² ] ^1/2

Here, ΔL _w , Δa _w , and Δb _w are amounts of change of the L ^* value, the a ^* value, and the b ^* value before and after the weather resistance test.

[Transparent image clarity]
The transmitted image definition can be measured using an optical comb having a slit width of 0.5 mm with an image clarity measuring device “ICM-2D type” manufactured by Suga Test Instruments Co., Ltd. according to JIS K-7105.

  The transmitted image definition of the antireflection film of the present invention is preferably 60% or more. The transmitted image definition is generally an index indicating the degree of blur of an image reflected through a film, and the larger this value, the clearer and better the image viewed through the film. The transmitted image definition is preferably 70% or more, and more preferably 80% or more.

[Surface roughness]
The centerline average roughness (Ra) in the antireflection film of the present invention can be measured according to JIS B-0601.

[Haze]
The haze of the antireflection film of the present invention is automatically measured as haze = (diffuse light / total transmitted light) × 100 (%) measured using a turbidimeter “NDH-1001DP” manufactured by Nippon Denshoku Industries Co., Ltd. The value to be used was used.
The haze of the antireflection film of the present invention is preferably 1.5% or less, more preferably 1.2% or less, and most preferably 1.0% or less.

[Goniophotometer scattering intensity ratio]
Using an automatic goniophotometer “GP-5 type” {Murakami Color Research Laboratory Co., Ltd.}, an antireflection film is placed perpendicular to the incident light, and the scattered light profile is measured in all directions. did. It can be determined from the scattered light intensity at an exit angle of 30 ° with respect to the light intensity at an exit angle of 0 °.

[Abrasion resistance]
(Steel wool scratch resistance evaluation)
A rubbing test using a “rubbing tester” under the following conditions can be used as an index of scratch resistance.
Evaluation environmental conditions: 25 ° C., 60% RH.
Rubbing material: steel wool {made by Nippon Steel Wool Co., Ltd. 0000} is wound around the rubbing tip (1 cm × 1 cm) of a tester that comes into contact with the sample, and the band is fixed.
Travel distance (one way): 13 cm.
Rubbing speed: 13 cm / sec.
Load: 500 g / cm ² and 200 g / cm ² .
Tip contact area: 1 cm × 1 cm.
Number of rubbing: 10 round trips.
Evaluation is performed by applying oil-based black ink to the back side of the rubbed sample, visually observing the scratch on the rubbed portion with reflected light, and observing the difference in the amount of reflected light from other than the rubbed portion.

(Eraser scuff resistance evaluation)
A rubbing test using a “rubbing tester” under the following conditions can be used as an index of scratch resistance.
Evaluation environmental conditions: 25 ° C., 60% RH.
Rubbing material: A plastic eraser {Tonbo Pencil Co., Ltd. MONO} is fixed to the rubbing tip (1 cm × 1 cm) of the tester in contact with the sample.
Travel distance (one way): 4 cm.
Rubbing speed: 2 cm / sec.
Load: 500 g / cm ² .
Tip contact area: 1 cm × 1 cm.
Number of rubbing: 100 reciprocations.
An oil-based black ink is applied to the back side of the rubbed sample, the scratches on the rubbing portion are visually observed with reflected light, and evaluation is made based on the difference in the amount of reflected light from other than the rubbed portion.

(Taber test)
In the Taber test according to JIS K5600-5-8, the scratch resistance can be evaluated from the wear amount of the test piece before and after the test. The smaller the amount of wear, the better.

[hardness]
(Pencil hardness)
The hardness of the antireflection film of the present invention can be evaluated by a pencil hardness test according to JIS K-5400. The pencil hardness is preferably H or higher, more preferably 2H or higher, and most preferably 3H or higher.

(Surface elastic modulus)
The surface elastic modulus in the antireflection film of the present invention is a value determined using a micro surface hardness meter {manufactured by Fisher Instruments: “Fischer Scope H100VP-HCU”}. Specifically, using a diamond pyramid indenter (tip-to-face angle: 136 °), the indentation depth is measured under an appropriate test load within a range where the indentation depth does not exceed 1 μm. This is the elastic modulus obtained from the change in load and displacement over time.

(Universal hardness)
Further, the surface hardness can be obtained as a universal hardness by using the micro surface hardness tester. The universal hardness is a value obtained by measuring the indentation depth of a quadrangular pyramid indenter under a test load and dividing the test load by the surface area of the indent calculated from the geometric shape of the indent generated by the test load. It is known that there is a positive correlation between the surface elastic modulus and the universal hardness.

[Anti-fouling test]
(Magic ink wiping property)
An anti-reflection film is fixed on the glass surface with an adhesive, and a black “magic ink” (“Mckey extra fine”) {trade name: manufactured by Zebra Co., Ltd.} nib (narrow) under the conditions of 25 ° C. and 60 RH%. Write a circle of 5 mm in diameter 3 times, and “Bencot” {Brand name: Asahi Kasei Co., Ltd.}, which was folded 10 times after 5 seconds, and wiped it back and forth 20 times with a load enough to dent the “Bencot” bundle. This writing and wiping are repeated under the same conditions until the “magic ink” mark disappears by wiping, and the antifouling property can be evaluated by the number of times of wiping.
The number of times until it no longer disappears is preferably 5 times or more, and more preferably 10 times or more.

  For black "Magic Ink", use "Magic Ink No. 700 (M700-T1 Black) Extra Fine", paint a circle with a diameter of 1cm on the sample, leave it for 24 hours and rub it with "Bencot". It can also be evaluated by whether or not the “ink” can be wiped off.

[surface tension]
In the present invention, the surface tension of a coating solution for forming a functional layer such as a low refractive index layer is measured with a surface tension meter {manufactured by Kyowa Interface Science Co., Ltd., “KYOWA CBVP SURFACE TENSIOMETER A3”} in an environment of 25 ° C. Can be measured.

[Contact angle]
Using a contact angle meter [“CA-X” type contact angle meter, manufactured by Kyowa Interface Science Co., Ltd.], using a pure water as a liquid in a dry state (20 ° C., 65% RH), a diameter of 1.0 mm A droplet was made on the needle tip, which was brought into contact with the surface of the antireflection film to form a droplet on the film. The angle between the tangent to the liquid surface and the antireflection film surface at the point where the antireflection film and the liquid are in contact, and the angle on the side containing the liquid is defined as the contact angle.

[Surface free energy]
Surface energy is “basic and applied wetness” {Published, Inc., 1989.12.
. 10 issue} can be obtained by a contact angle method, a wet heat method, and an adsorption method. In the case of the film of the present invention, it is preferable to use a contact angle method. Specifically, two kinds of solutions having known surface energies are dropped on a cellulose acylate film, and at the intersection of the surface of the droplet and the surface of the film, the angle formed between the tangent line drawn on the droplet and the film surface, The surface angle of the film can be calculated by defining the angle containing the droplet as the contact angle.

The surface free energy (γs ^v : unit, mN / m) of the antireflection film of the present invention is defined as D.I. K. Owens, “J. Appl. Polym. Sci.”, Volume 13, p. From the contact angles θ _H2O and θ _{CH2I2 of} pure water H ₂ O and methylene iodide (CH ₂ I ₂ ) obtained experimentally on an antireflection film with reference to 1741 (1969), equation a, defined in b {equation (5)} than determined value gamma] s ^d and gamma] s ^h values are expressed as the sum ^{γs v (= γs d + γs} h), it represents the surface tension of the antireflection film. The gamma] s ^v is small, as the surface of the repellent can of high a low surface free energy, generally excellent antifouling property.

Formula (5):
a. ^{_{1 + cosθ H2O = 2√γs d (}} √γ H2O d / γ H2O v) + 2√γs h (√γ H2O h / γ H2O v)
b. ^{_{1 + cosθ CH2I2 = 2√γs d (}} √γ CH2I2 d / γ CH2I2 v) + 2√γs h (√γ CH2I2 h / γ CH2I2 v)
γ _H2O ^d = 21.8, γ _H2O ^h = 51.0, γ _H2O ^v = 72.8,
γ _CH2I2 ^d = 49.5, _γCH2I2 ^h = 1.3, _γCH2I2 ^v = 50.8

  The contact angle is measured using an automatic contact angle meter “CA-V150 type” manufactured by Kyowa Interface Science Co., Ltd. after conditioning the antireflection film at 25 ° C. and 60% RH for 1 hour or more. The contact angle was determined 30 seconds after 2 μL of the droplet was dropped on the film.

  The surface free energy of the film of the present invention is preferably 25 mN / m or less, and particularly preferably 20 mN / m or less.

[curl]
The curl is measured using the curl measurement template of Method A in “Measuring Method of Curling of Photographic Film” of JIS K-7619-1988.
The measurement conditions are 25 ° C., 60% RH, and a humidity control time of 10 hours.

  In the antireflection film of the present invention, the value when curl is expressed by the following formula (6) is preferably in the range of −15 to +15, more preferably in the range of −12 to +12. Is -10 to +10. The measurement direction of the curl in the sample at this time is measured in the conveyance direction of the base material in the case of application in a web form.

Formula (6): Curl = 1 / R
R represents a radius of curvature (m).

  This is an important characteristic for preventing cracks and film peeling during film production, processing, and market handling. It is preferable that the curl value is in the above range and the curl is small. Here, the curl “+” means a curl in which the coating side of the film is inside the curve, and “−” means a curl in which the coating side is outside the curve.

In the film according to the present invention, the absolute value of the difference between the curl values when the relative humidity is changed to 80% and 10% based on the curl measurement method is preferably 24 to 0, and preferably 15 to 0. Is more preferable, and 8 to 0 is most preferable. This is a property related to handling, peeling and cracking when films are attached under various humidity.

[Adhesion evaluation]
The adhesion between the layers of the antireflection film or between the support and the coating layer can be evaluated by the following method.

  On the surface having the coating layer, 11 square and 11 horizontal cuts are made at 1 mm intervals in a grid pattern with a cutter knife, and a total of 100 square squares are engraved, and polyester adhesive made by Nitto Denko Corporation. The tape “NO.31B” is pressure-bonded, and left for 24 hours and then peeled off. The test is repeated three times at the same place, and the presence or absence of peeling is visually observed. Of 100 squares, peeling is preferably within 10 mm, and more preferably within 2 mm.

[Brittleness test (crack resistance)]
Crack resistance is an important characteristic for preventing crack defects by handling such as application of antireflection film, processing, cutting, application of pressure-sensitive adhesive, and adhesion to various objects.
Cut the antireflection film sample to 35mm x 140mm, leave it for 2 hours under the conditions of temperature 25 ° C and 60% RH, then measure the curvature diameter at which cracking starts when rolled up into a cylinder, and check the surface crack Can be evaluated.

  The crack resistance of the film of the present invention is preferably 50 mm or less, more preferably 40 mm or less, and most preferably 30 mm or less, when the film is rolled with the coating layer side facing outward. About the crack of an edge part, it is preferable that there is no crack or the length of a crack is less than 1 mm on average.

[Surface resistance]
The film surface resistance of the present invention was measured under the conditions of 25 ° C. and 60% RH using a super insulation resistance / microammeter “TR8601” {manufactured by Advantest Co., Ltd.}. The log SR value is calculated by taking the common logarithm of the surface resistance (Ω / □).

[Dust removal]
The antireflection film of the present invention can be attached to a monitor, dust (futon, fiber waste from clothes) can be sprinkled on the monitor surface, dust can be wiped off with a cleaning cloth, and dust removal can be evaluated.
It is preferable to remove completely by wiping 6 times, and it is more preferable to remove dust completely by wiping within 3 times.

[Drawing performance of liquid crystal display]
Below, the evaluation method of a characteristic when using the antireflection film of this invention on a display apparatus, and a preferable condition are described.

  The polarizing plate on the viewing side provided in the liquid crystal display device “TH-15TA2” {manufactured by Matsushita Electric Industrial Co., Ltd.} using a TN type liquid crystal cell is peeled off, and the antireflection film or polarizing plate of the present invention is used instead. It sticks through an adhesive so that the application surface is on the viewing side and the transmission axis of the polarizing plate matches the polarizing plate attached to the product. In a 500 Lx bright room, the liquid crystal display device is displayed in black, and the following various characteristics can be evaluated visually from various viewing angles.

(Drawing image unevenness, tint evaluation)
Using a measuring instrument (“EZ-Contrast 160D”, manufactured by ELDIM), the drawing unevenness and the color change during black display (L1) are visually evaluated by a plurality of observers.
It is preferable that three people or less can recognize the unevenness, left-right color change, color change due to temperature and humidity, and white blur, and more preferably no one can recognize it.
In addition, reflection of external light is performed using a fluorescent lamp, and a change in reflection can be relatively evaluated visually.

(Light leakage of black display)
The light leakage rate of black display in the azimuth direction 45 ° and polar angle direction 70 ° from the front of the liquid crystal display device is measured. The light leakage rate is preferably 0.4% or less, and more preferably 0.1% or less.

(Contrast and viewing angle)
Contrast and viewing angle are measured using the measuring instrument “EZ-Contrast 160D” (manufactured by ELDIM). The contrast ratio and the viewing angle in the left-right direction (direction orthogonal to the rubbing direction of the cell) Can be checked.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited to these.

<Preparation of antireflection film>
[Preparation of coating solution for forming each layer]
(Synthesis of Compound IC-6 described in this Specification)
Compound A (5.27 g) and 3-isocyanatopropyltriethoxysilane (2.97 g) were dissolved in 2-butanone (25 cm ³⁾ , di-n-butyltin diacetate (25 mg) was added, and the mixture was heated and stirred at 50 ° C. for 10 hours. Thereafter, the mixture was cooled to room temperature, filtered, and added dropwise to 300 cm ³ of hexane. The precipitated crystals were filtered under reduced pressure, washed with hexane, and then dried under vacuum to obtain 3.90 g of a silane coupling group-containing photoradical polymerization initiator (Compound No .: IC-6), which is an organosilane compound.
¹ H-NMR (DMSO-d ₆ ): 0.60 (m, 2H), 1.17 (t, J = 9.4 Hz, 9H), 1.55 (m, 2H), 3.07 (m, 2H), 3.77 (q, J = 9.4 Hz, 6H), 7.29 (d, J = 11.2 Hz, 2H), 7.92 (t, J = 7.5 Hz, 1H), 8 .03 (d, J = 11.6 Hz, 2H), 8.13 (d, J = 11.6 Hz, 2H), 8.58 (d, J = 12.0 Hz, 2H), 10.76 (s, 1H). Melting point: 177.2-180.0 ° C.

Compound A

Compound IC-6

[Preparation of Sol Solution (a-1)]
In a 1000 mL reaction vessel equipped with a thermometer, a nitrogen inlet tube, and a dropping funnel, 187 g (0.80 mol) of 3-acryloxyoxypropyltrimethoxysilane, 27.2 g (0.20 mol) of methyltrimethoxysilane, methanol 320 g (10 mol) and 0.06 g (0.001 mol) of potassium fluoride (KF) were charged, and 15.1 g (0.86 mol) of water was slowly added dropwise at room temperature with stirring. After completion of the dropwise addition, the mixture was stirred at room temperature for 3 hours, and then heated and stirred for 2 hours under methanol reflux. Then, 120 g of sol liquid (a-1) was obtained by depressurizingly distilling a low boiling-point component and further filtering.

As a result of measuring the substance thus obtained by GPC, the mass average molecular weight was 1500, and among the components higher than the oligomer component, the component having a molecular weight of 1000 to 20000 was 30% by mass. Moreover, from the measurement result of ¹ H-NMR, the structure of the obtained substance was a structure represented by the following general formula.

Furthermore, the condensation rate α as determined by ²⁹ Si-NMR was 0.56. From this analysis result, it was found that the silane coupling agent sol was mostly composed of a linear structure. From the gas chromatography analysis, the raw material acryloxypropyltrimethoxysilane had a residual ratio of 5% by mass or less.

[Preparation of Sol Solution (b-1)]
In a reactor equipped with a stirrer and a reflux condenser, 119 parts by mass of methyl ethyl ketone, 3-acryloyloxypropyltrimethoxysilane “KBM-5103” {manufactured by Shin-Etsu Chemical Co., Ltd.} 101 parts by mass, diisopropoxyaluminum ethylacetate After adding 3 parts by mass of acetate and mixing, 30 parts by mass of ion-exchanged water was added and reacted at 60 ° C. for 4 hours, and then cooled to room temperature to obtain a sol solution (b-1).

  The mass average molecular weight of the sol liquid (b-1) was 1600, and among the components higher than the oligomer component, the component having a molecular weight of 1000 to 20000 was 100% by mass. Further, from the gas chromatography analysis, the raw material acryloyloxypropyltrimethoxysilane did not remain at all. The SP value of this sol solution (b-1) was 22.4.

[Preparation of hard coat layer forming coating solution (HC-1)]
“DPHA” 150.0g
Methyl ethyl ketone / cyclohexanone (50/50) 206.0 g
“MEK-ST” (silica particles) 333.0 g
"Irgacure 184" 7.5g
Methyl ethyl ketone (MEK) 49.0g

The mixed liquid was filtered through a polypropylene filter having a pore diameter of 30 μm to prepare a hard coat layer forming coating liquid (HC-1).

[Preparation of hard coat layer forming coating solution (HC-2)]
"Desolite Z7526" 347.0g
MEK / cyclohexanone (50/50) 403.0 g

  The mixed solution was filtered through a polypropylene filter having a pore size of 30 μm to prepare a hard coat layer forming coating solution (HC-2).

[Preparation of hard coat layer forming coating solution (HC-3)]
"DPHA" 135.0g
MEK / cyclohexanone (50/50) 196.0 g
“MEK-ST” (silica particles) 300.0 g
Sol solution (a-1) 25.0 g
MEK 82.0g

  The mixed solution was filtered through a polypropylene filter having a pore size of 30 μm to prepare a hard coat layer forming coating solution (HC-3).

[Preparation of hard coat layer forming coating solution (HC-4)]
"PETA" 50.0g
"Irgacure 184" 2.0g
“SX-350” (30% by mass) 1.7 g
Cross-linked acrylic-styrene particles (30% by mass) 13.3 g
"FP-132" 0.75g
"KBM-5103" 10.0g
Toluene 38.5g

  The mixed solution was filtered through a polypropylene filter having a pore size of 30 μm to prepare a hard coat layer forming coating solution (HC-4).

[Preparation of hard coat layer forming coating solution (HC-5)]
"PETA" 50.0g
"Irgacure 184" 2.0g
“SX-350” (30% by mass) 1.7 g
Cross-linked acrylic-styrene particles (30% by mass) 13.3 g
"FP-132" 0.75g
Toluene 38.5g

  The liquid mixture was filtered through a polypropylene filter having a pore size of 30 μm to prepare a hard coat layer forming coating solution (HC-5).

[Preparation of hard coat layer forming coating solution (HC-6)]
"Desolite Z7401" 195.0g
“DPHA” 82.0g
Sol solution (a-1) 25.8 g
“SX-350” (30% by mass) 1.7 g
MEK / cyclohexanone (50/50) 368.0 g

The mixed solution was filtered through a polypropylene filter having a pore size of 30 μm to prepare a hard coat layer forming coating solution (HC-6).

[Preparation of hard coat layer forming coating solution (HC-7)]
PETA 285.0g
"Irgacure 184" 15.0g
Sol solution (a-1) 25.8 g
Agglomerated silica (secondary particle system 1.0 μm-30 mass%) 1.7 g
Fluorine leveling agent R-30 0.5g
Methyl isobutyl ketone 175.0g

  The mixed solution was filtered through a polypropylene filter having a pore size of 30 μm to prepare a hard coat layer forming coating solution (HC-7).

[Preparation of hard coat layer forming coating solution (HC-8)]
PETA 285.0g
"Irgacure 184" 15.0g
Agglomerated silica (secondary particle system 1.0 μm-30 mass%) 1.7 g
Fluorine leveling agent R-30 0.5g
Methyl isobutyl ketone 175.0g

  The mixed liquid was filtered through a polypropylene filter having a pore size of 30 μm to prepare a hard coat layer forming coating liquid (HC-8).

[Preparation of hard coat layer forming coating solution (HC-9)]
The following composition was put into a mixing tank and stirred to obtain a hard coat layer coating solution.
750.0 parts by weight of trimethylolpropane triacrylate (Biscoat # 295 (manufactured by Osaka Organic Chemical Co., Ltd.)), 270.0 parts by mass of polyglycidyl methacrylate having a mass average molecular weight of 15000, 730.0 parts by mass of methyl ethyl ketone, 500.0 cyclohexanone Mass parts and 50.0 parts by mass of a photopolymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) were added and stirred, and filtered through a polypropylene filter having a pore size of 0.4 μm for the hard coat layer. A polyglycidyl methacrylate was dissolved in methyl ethyl ketone (MEK) and reacted at 80 ° C. for 2 hours while adding a thermal polymerization initiator (V-65 (manufactured by Wako Pure Chemical Industries, Ltd.)). The obtained reaction solution was dropped into hexane, and the precipitate was Obtained by pressure dry.

The compounds used are shown below.
“PETA”: a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate, manufactured by Nippon Kayaku Co., Ltd.
“DPHA”: a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.
“Desolite Z7526”: a commercially available silica-containing UV curable hard coat solution, solid content concentration 72% by mass, silica content 38% by mass, average particle diameter 20 nm, manufactured by JSR Corporation.
“Desolite Z7401”: Commercially available silica-containing UV curable hard coat solution, solid content concentration 70.1% by mass, silica content 35% by mass, average particle size 22 nm, manufactured by JSR Corporation.
Agglomerated silica (secondary particle system 1.0 μm), Fluorine leveling agent R-30 made by Nippon Silica Dainippon Ink and Chemicals (commercially available)

“MEK-ST”: Silica sol, average particle size 15 nm, solid content concentration 30% by mass, manufactured by Nissan Chemical Co., Ltd.
“Irgacure 184”: Photopolymerization initiator, manufactured by Ciba Specialty Chemicals.
“SX-350”: Cross-linked polystyrene particles having an average particle size of 3.5 μm (refractive index of 1.60), 30% by mass toluene dispersion, manufactured by Soken Chemical Co., Ltd. Used after dispersion for 20 minutes at 10,000 rpm in a Polytron disperser.
Cross-linked acrylic-styrene particles: average particle size 3.5 μm (refractive index 1.55), 30% by weight toluene dispersion, manufactured by Soken Chemical Co., Ltd.
“KBM-5103”: silane coupling agent, 3-acryloyloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.
“FP-132”: a fluorine-based surface modifier having the following structural formula.

[Preparation of low refractive index layer-forming coating solution (LL-1)]
“Fluorine-containing thermosetting binder: H-1” 177.0 g
“MEK-ST” (silica particles, 30.0 mass%) 15.2 g
MEK 116.0g
Cyclohexanone 9.0g

  The mixed solution was filtered through a polypropylene filter having a pore diameter of 1 μm to prepare a coating solution for forming a low refractive index layer (LL-1).

[Preparation of coating liquid for low refractive index layer formation (LL-2)]
“Fluorine-containing thermosetting binder: H-1” 177.0 g
“MEK-ST” (silica particles, 30.0 mass%) 15.2 g
Sol solution (b-1) 7.3 g
MEK 90.0g
Cyclohexanone 9.0g

  The mixed solution was filtered through a polypropylene filter having a pore diameter of 1 μm to prepare a coating solution for forming a low refractive index layer (LL-2).

[Preparation of low refractive index layer-forming coating solution (LL-3)]
“Fluorine-containing thermosetting binder: H-1” 177.0 g
“MEK-ST” (silica particles, 30.0 mass%) 15.2 g
Sol solution (b-1) 7.3 g
Initiator compound (IC-1) 0.4 g
MEK 90.0g
Cyclohexanone 9.0g

  The mixed solution was filtered through a polypropylene filter having a pore size of 1 μm to prepare a coating solution for forming a low refractive index layer (LL-3).

[Preparation of coating solution for forming a low refractive index layer (LL-4)]
“Fluorine-containing thermosetting binder: H-1” 177.0 g
“MEK-ST” (silica particles, 30.0 mass%) 15.2 g
Sol solution (b-1) 7.3 g
Initiator compound (IC-6) 0.4 g
MEK 90.0g
Cyclohexanone 9.0g

  The mixed solution was filtered through a polypropylene filter having a pore size of 1 μm to prepare a coating solution for forming a low refractive index layer (LL-4).

[Preparation of coating solution for low refractive index layer formation (LL-5)]
“Fluorine-containing thermosetting binder: H-1” 177.0 g
“MEK-ST” (silica particles, 30.0 mass%) 15.2 g
Sol solution (b-1) 7.3 g
Initiator compound (IC-7) 0.4 g
MEK 90.0g
Cyclohexanone 9.0g

  The mixed solution was filtered through a polypropylene filter having a pore size of 1 μm to prepare a coating solution for forming a low refractive index layer (LL-5).

[Preparation of coating solution for low refractive index layer formation (LL-6)]
“Fluorine-containing thermosetting binder: H-1” 177.0 g
“MEK-ST” (silica particles, 30.0 mass%) 15.2 g
Sol solution (b-1) 7.3 g
Initiator compound (IC-1) 0.4 g
MEK 90.0g
Cyclohexanone 9.0g

  The mixed solution was filtered through a polypropylene filter having a pore diameter of 1 μm to prepare a coating solution for forming a low refractive index layer (LL-6).

[Preparation of coating solution for low refractive index layer (LL-7)]
“Fluorine-containing thermosetting binder: H-1” 177.0 g
“MEK-ST” (silica particles, 30.0 mass%) 15.2 g
Sol solution (b-1) 7.3 g
Initiator compound (IC-4) 0.4 g
MEK 90.0g
Cyclohexanone 9.0g

  The mixed solution was filtered through a polypropylene filter having a pore diameter of 1 μm to prepare a coating solution for forming a low refractive index layer (LL-7).

[Preparation of coating solution for low refractive index layer (LL-8)]
9.0 g of photocrosslinkable fluorine-containing polymer “P-3”
"RMS-033" 3.3g
“MEK-ST” (silica particles, 30.0% by mass) 7.34 g
"MP-Triazine" 0.11g
Sol solution (b-1) 1.14 g
Initiator compound (IC-1) 0.06 g
MEK 90.0g
Cyclohexanone 9.0g

  The mixed solution was filtered through a polypropylene filter having a pore size of 1 μm to prepare a coating solution for forming a low refractive index layer (LL-8).

[Preparation of coating solution for forming a low refractive index layer (LL-9)]
9.0 g of photocrosslinkable fluorine-containing polymer “P-3”
"RMS-033" 3.3g
Hollow silica dispersion (18.0% by mass) 12.2 g
"MP-Triazine" 0.11g
Sol solution (b-1) 1.14 g
MEK 85.0g
Cyclohexanone 5.5g

  The mixed solution was filtered through a polypropylene filter having a pore diameter of 1 μm to prepare a coating solution for forming a low refractive index layer (LL-9).

[Preparation of coating solution for forming low refractive index layer (LL-10)]
9.0 g of photocrosslinkable fluorine-containing polymer “P-3”
"RMS-033" 3.3g
Hollow silica dispersion (18.0% by mass) 12.2 g
"MP-Triazine" 0.11g
Sol solution (b-1) 1.14 g
Initiator compound (IC-1) 0.04 g
MEK 85.0g
Cyclohexanone 5.5g

  The mixed solution was filtered through a polypropylene filter having a pore diameter of 1 μm to prepare a coating solution for forming a low refractive index layer (LL-10).

[Preparation of low refractive index layer forming coating solution (LL-11)]
9.0 g of photocrosslinkable fluorine-containing polymer “P-3”
"RMS-033" 3.3g
Hollow silica dispersion (18.0% by mass) 12.2 g
"MP-Triazine" 0.11g
Sol solution (b-1) 1.14 g
Initiator compound (IC-4) 0.04 g
MEK 85.0g
Cyclohexanone 5.5g

  The mixed solution was filtered through a polypropylene filter having a pore size of 1 μm to prepare a coating solution for forming a low refractive index layer (LL-11).

(Preparation of titanium dioxide fine particle dispersion)
As the titanium dioxide fine particles, titanium dioxide fine particles (MPT-129C, manufactured by Ishihara Sangyo Co., Ltd., TiO ₂ : Co ₃ O ₄ : containing cobalt and subjected to surface treatment using aluminum hydroxide and zirconium hydroxide: Al ₂ O ₃ : ZrO ₂ = 90.5: 3.0: 4.0: 0.5
Weight ratio) was used.
The following dispersant (41.1 parts by mass) and cyclohexanone (701.8 parts by mass) were added to 257.1 parts by mass of the particles and dispersed by dynomill to prepare a titanium dioxide dispersion having a weight average diameter of 70 nm.

Dispersant

(Preparation of Medium Refractive Index Layer Coating Liquid ML-1)
In 99.1 parts by mass of the above titanium dioxide dispersion, 68.0 parts by mass of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.), a photopolymerization initiator (Irgacure 907) 3.6 parts by mass, manufactured by Ciba Specialty Chemicals Co., Ltd., 1.2 parts by mass of photosensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.), 279.6 parts by mass of methyl ethyl ketone, and 1049.0 of cyclohexanone. A part by mass was added and stirred. After sufficiently stirring, the solution was filtered through a polypropylene filter having a pore size of 0.4 μm to prepare a coating solution for a medium refractive index layer.

(Preparation of coating liquid HL-1 for high refractive index layer)
To 469.8 parts by mass of the above titanium dioxide dispersion, 40.0 parts by mass of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, Nippon Kayaku Co., Ltd.), a photopolymerization initiator (Irgacure 907) 3.3 parts by mass, manufactured by Ciba Specialty Chemicals Co., Ltd., 1.1 parts by mass of photosensitizer (Kayacure-DETX, manufactured by Nippon Kayaku Co., Ltd.), 526.2 parts by mass of methyl ethyl ketone, and cyclohexanone 459 .6 parts by mass was added and stirred. The solution was filtered through a polypropylene filter having a pore size of 0.4 μm to prepare a coating solution for a high refractive index layer.

The compounds used above are shown below.
“Fluorine-containing thermosetting binder: H-1”:
80 g of fluorine-containing thermosetting polymer described in JP-A-11-189621, Example 1,
As a curing agent, Cymel 303 20g (Nippon Cytec Industries, Ltd.)
A catalyst obtained by dissolving 2.0 g of Catalyst 4050 (manufactured by Nippon Cytec Industries, Ltd.) in MEK as a curing catalyst to 6%. SP value = 18.9
“P-3”: a fluorine-containing copolymer (P-3) described in JP-A No. 2004-45462, a mass average molecular weight of about 50000, and a solid content concentration of 23.8% by mass / MEK. SP value = 19.2
“MEK-ST-L”: silica sol, silica particle size difference of “MEK-ST”, average particle size 45 nm, solid content concentration 30% by mass, manufactured by Nissan Chemical Co., Ltd.
Hollow silica dispersion: CS-60 IPA (Catalyst Chemical Industries, Ltd.) Refractive index 1.31, average particle size 60 nm, shell thickness 10 nm, solid content concentration 18.2% “KBM-5103” surface modified hollow silica sol (surface Modification rate vs. 30% by weight silica)
“RMS-033”: Reactive silicone resin, manufactured by Gelest.
“MP-triazine”: photopolymerization initiator, manufactured by Sanwa Chemical Co., Ltd.

[Preparation of antireflection film]
Examples 1-1 to 1-21 and Comparative Examples 1-1 to 1-4
Each of the hard coat layers (HC-1) to (HC-8) and the low refractive index layers (LL-1) to (LL-11) was applied as follows to obtain an antireflection film sample. . Table 2 shows the main composition and combination of each layer, and Table 3 shows the curing conditions of each layer.
Also, the hard coat layer (HC-9), the medium refractive index layer (ML-1), the high refractive index layer (HL-1), and the low refractive index layers (LL-9) to (LL-11) are respectively Coating was carried out as follows to obtain an antireflection film sample. Table 4 shows the main composition and combination of each layer, and Table 5 shows the curing conditions of each layer.

[Coating of hard coat layer]
An 80 μm-thick triacetyl cellulose film “TAC-TD80U” (trade name) {manufactured by Fuji Film Co., Ltd.} is unwound in a roll form, and the above-described coating liquid for forming a hard coat layer (HC-1) to ( HC-6), using a gravure roll with a diameter of 180 mm / in and a gravure pattern with a depth of 40 μm, a micro gravure roll with a diameter of 50 mm and a doctor blade, a gravure roll rotation speed of 30 rpm and a conveyance speed of 10 m / min. After coating at 120 ° C. for 2 minutes, using an “air-cooled metal halide lamp” {manufactured by Eye Graphics Co., Ltd.] of 160 W / cm under a nitrogen purge with an oxygen concentration of 0.1% by volume or less, illuminance 400 mW / cm ^2, irradiation amount 110 mJ / cm ² of ultraviolet was irradiated to cure the coating layer, form a hard coat layer having a thickness of 6.0μm, respectively It was wound up with.

[Coating of low refractive index layer (1) (thermal curing + ionizing radiation curing system)]
The triacetyl cellulose film coated with each hard coat layer as described above is unwound again, and the above-mentioned coating solution for low refractive index layer has a gravure pattern with a line number of 180 lines / inch and a depth of 40 μm, and a micro gravure with a diameter of 50 mm. Using a roll and a doctor blade, it was applied under the conditions of a gravure roll rotation speed of 30 rpm and a conveyance speed of 10 m / min, dried at 80 ° C. for 2 minutes, heat-cured at 110 ° C. for 10 minutes, and further purged with nitrogen (oxygen) A low-refractive-index layer having a thickness of 95 nm is irradiated with ultraviolet rays having an irradiation amount of 300 mJ / cm ² using an “air-cooled metal halide lamp” {made by Eye Graphics Co., Ltd.) at a concentration of 0.5% or less) and 240 W / cm. Was formed and wound up.

[Coating of low refractive index layer (2) (ionizing radiation curing system)]
The triacetyl cellulose film coated with each hard coat layer as described above was unwound again, and the low refractive index layer coating solution was applied at a coating speed of 25 m / min using a die coater. After drying at 120 ° C. for 70 seconds and using a 240 W / cm air-cooled metal halide lamp (made by Eye Graphics Co., Ltd.) under a nitrogen purge (oxygen concentration of 0.5% or less), the irradiation amount is 400 mJ / cm ² . A low refractive index layer having a thickness of 95 nm was formed by irradiating with ultraviolet rays and wound.

  On the hard coat layer, a medium refractive index layer coating solution, a high refractive index layer coating solution, and a low refractive index layer coating solution were successively coated using a slot die coater having three coating stations.

The medium refractive index layer was dried at 90 ° C. for 30 seconds, and the ultraviolet curing condition was 180 W / cm air-cooled metal halide lamp (eye graphics) while purging with nitrogen so that the atmosphere had an oxygen concentration of 1.0% by volume or less. ), And the irradiation dose was 400 mW / cm ² and the irradiation dose was 400 mJ / cm ² .
The medium refractive index layer after curing had a refractive index of 1.630 and a film thickness of 67 nm.

The drying condition of the high refractive index layer is 90 ° C. for 30 seconds, and the ultraviolet curing condition is a 240 W / cm air-cooled metal halide lamp (eye graphics) while purging with nitrogen so that the atmosphere has an oxygen concentration of 1.0 vol. ), And the irradiation dose was 600 mW / cm ² and the irradiation dose was 400 mJ / cm ² .
The cured high refractive index layer had a refractive index of 1.905 and a film thickness of 107 nm.

The drying conditions for the low refractive index layer were 90 ° C. and 30 seconds. The UV curing conditions were as follows: an air cooling metal halide lamp (manufactured by Eye Graphics Co., Ltd.) having an illuminance of 600 mW / cm ² while purging with nitrogen so that the atmosphere had an oxygen concentration of 0.1% by volume or less. The irradiation dose was 600 mJ / cm ² .
The low refractive index layer after curing had a refractive index of 1.380 and a film thickness of 85 nm.

[Evaluation of antireflection film sample]
The following items were evaluated for the obtained antireflection film sample. The results are shown in Tables 3 and 5.

(Specular reflectance)
Spectral reflectivity of specular hardness meter “V-550” {manufactured by JASCO Corp.} with adapter “ARV-474” and an output angle of −5 ° with respect to an incident angle of 5 ° in the wavelength range of 380 to 780 nm. Was measured, the average reflectance of 450 nm to 650 nm was calculated, and the antireflection property was evaluated.

(Pencil hardness)
The pencil hardness evaluation described in JIS K-5400 was performed.
After conditioning the antireflection film at a temperature of 25 ° C. and 60% RH for 2 hours, it was evaluated using the H-5H test pencil specified in JIS S-6006 at a load of 500 g as follows. The highest hardness that results in OK was taken as the evaluation value.
In evaluation of n = 5, no scratch to one scratch: OK
In evaluation of n = 5, 3 or more scratches: NG

(Steel wool scuff resistance)
A load of 200 g / cm ² was applied to # 0000 steel wool, and the state of scratches after 10 reciprocations was observed and evaluated according to the following 5 levels.
(Double-circle): The thing which did not scratch at all.
○: Slightly invisible scratches.
Δ: Scratches clearly visible.
X: Scratches clearly visible.
XX: The film peeled off.

  It can be seen that by using the initiator compound and the organosilane sol liquid as the curable compound in the present invention, the antireflection film becomes a film excellent in scratch resistance while having sufficient antireflection performance.

Moreover, about the sample 106 in a table | surface, it measured by TOF-SIMS which showed the measuring method previously, the image image was drawn with the mass number peculiar to a raw material, and the distribution in a film | membrane was evaluated. As a result, from the surface of the low refractive index layer of the sample 106, Cl derived from the Si initiator (1C-1) derived from the organosilane sol compound.
The element was not detected. On the other hand, both elements were detected in layers from the hard coat layer side of the low refractive index layer (the lower layer of the low refractive index layer). From this, it is clear that the fluorine-containing binder polymer is localized above the low refractive index layer, while the organosilane sol compound and the polymerization initiator of the present invention are localized below the low refractive index layer. Became.

Examples 2-1 to 2-19 and comparative examples 2-1 to 2-3
In the coating of the low refractive index layer in the production methods of Samples 101 to 407 of Examples 1-1 to 1-19 and Comparative Examples 1-1 to 1-3, the ultraviolet irradiation amount was set as shown in Table 6 below. Samples 101-1 to 407-1 differing only in that were prepared and subjected to the same evaluation.
The amount of ultraviolet irradiation was adjusted by changing the amount of light emitted from the ultraviolet light source or changing the coating speed.

  By using an organosilane sol liquid that is an initiator compound and a curable compound in the present invention, even with an antireflection film in which the amount of UV irradiation is reduced to 1/8, it has scratch resistance while having sufficient antireflection performance. It is clear that it is also advantageous for high-speed productivity.

<Preparation of protective film for polarizing plate>
Example 3
A saponification solution was prepared by keeping a 1.5 mol / L sodium hydroxide aqueous solution at 50 ° C. Furthermore, a 0.005 mol / L dilute sulfuric acid aqueous solution was prepared.

  About the antireflection film produced in Examples 1 and 2, the surface of the transparent support opposite to the side having the low refractive index layer of the antireflection film was saponified using the saponification solution. Next, the aqueous sodium hydroxide solution on the surface of the saponified transparent support is thoroughly washed with water, then washed with the above dilute sulfuric acid aqueous solution, and further, the dilute sulfuric acid aqueous solution is thoroughly washed with water and sufficiently dried at 100 ° C. I let you.

  When the contact angle with water of the surface of the transparent support on the side of the antireflection film on which saponification was applied was evaluated, it was 40 ° or less. Thus, the protective film for polarizing plates was produced.

[Preparation of polarizing plate]
[Preparation of polarizing film]
A polyvinyl alcohol film {made by Kuraray Co., Ltd.} having a film thickness of 75 μm was immersed in an aqueous solution consisting of 1000 parts by mass of water, 7 parts by mass of iodine, and 105 parts by mass of potassium iodide to adsorb iodine. Subsequently, this film was uniaxially stretched 4.4 times in the longitudinal direction in a 4% by mass boric acid aqueous solution, and then dried in a tension state to produce a polarizing film.

  Using a polyvinyl alcohol-based adhesive as an adhesive, the saponified triacetyl cellulose surface of the saponified antireflection film (protective film for polarizing plate) was bonded to one surface of the polarizing film. Further, a triacetyl cellulose film saponified in the same manner as described above was bonded to the other surface of the polarizing film using the same polyvinyl alcohol-based adhesive.

[Evaluation with display device]
TN, STN, IPS, VA, OCB modes in which each polarizing plate of Example 3 using the antireflection film of the present invention thus produced was mounted so that the antireflection film was the outermost surface of the display. The transmissive, reflective, or transflective liquid crystal display device has excellent antireflection performance and extremely excellent visibility. In particular, the effect is remarkable in the VA mode.

Example 4
[Preparation of polarizing plate]
The surface of the optical compensation film “Wide View Film SA 12B” {manufactured by FUJIFILM Corporation} having an optical compensation layer was subjected to saponification treatment under the same conditions as in Example 3 on the side opposite to the side having the optical compensation layer.

  Saponification of the antireflection film (protective film for polarizing plate) prepared in Examples 1 and 2 on one surface of the polarizing film using a polyvinyl alcohol-based adhesive as an adhesive for the polarizing film prepared in Example 3 The treated surfaces were bonded together. Further, on the other surface of the polarizing film, the surface opposite to the side having the optical compensation layer of the saponified optical compensation film was bonded using the same polyvinyl alcohol-based adhesive.

[Evaluation with display device]
TN, STN, IPS, VA, OCB modes in which the polarizing plates of Example 4 using the antireflection film of the present invention thus prepared were mounted so that the antireflection film was the outermost surface of the display. The transmissive, reflective, or transflective liquid crystal display device has better contrast in a bright room than the liquid crystal display device equipped with a polarizing plate that does not use an optical compensation film, and has a very high vertical, horizontal, and horizontal viewing angle. In addition, the antireflection performance was excellent, and the visibility and display quality were excellent. In particular, the effect is remarkable in the VA mode.

FIG. 1 is a schematic cross-sectional view schematically showing a preferred embodiment of the antireflection film of the present invention. FIG. 2 is a schematic cross-sectional view schematically showing another preferred embodiment of the antireflection film of the present invention. FIG. 3 is a schematic sectional view schematically showing still another preferred embodiment of the antireflection film of the present invention. FIG. 4 is a schematic cross-sectional view schematically showing a preferred embodiment of an antireflection film having an antiglare hard coat layer of the present invention. FIG. 5 is a schematic cross-sectional view schematically showing another preferred embodiment of the antireflection film having the antiglare hard coat layer of the present invention. FIG. 6 is a cross-sectional view of the coater 10 using the slot die 13 used in the practice of the present invention. 7A shows the sectional shape of the slot die 13 used in the practice of the present invention, and FIG. 7B shows the sectional shape of the conventional slot die 30. FIG. 8 is a perspective view showing the slot die 13 and its periphery in the coating process employed in the practice of the present invention. FIG. 9 is a cross-sectional view showing the vacuum chamber 40 and the web W that are close to each other. (The back plate 40a is integrated with the main body of the chamber 40) FIG. 10 is a cross-sectional view showing another embodiment of the decompression chamber 40 and the web W that are close to each other (the back plate 40a is fastened to the chamber 40 with screws 40c).

Explanation of symbols

1: Support 2: Hard coat layer 3: Medium refractive index layer 4: High refractive index layer 5: Low refractive index layer

10: Coater 11: Backup roll W: Web 13: Slot die 14: Coating liquid 14a: Bead 14b: Coating film 15: Pocket 16: Slot 16a: Slot opening 17: Tip lip 18: Land 18a: Upstream lip land 18b : Ripland on the downstream side

I _UP : Land length of the upstream lip land 18a I _LO : Land length of the downstream lip land 18b LO: Over bite length (difference in distance between the downstream lip land 18b and the web W of the upstream lip land 18a )
G _L : gap between the tip lip 17 and the web W (gap between the downstream lip land 18b and the web W)

30: conventional slot-die 31a: upstream lip land 31b: downstream lip land 32: Pocket 33: Slot 40: vacuum chamber 40a: back plate 40b: side plate 40c: threaded G _B: between the back plate 40a and the web W G _S : Gap between the side plate 40b and the web W

Claims (12)

  An antireflection film having at least a hard coat layer and a low refractive index layer on a transparent support, the low refractive index layer having a binder polymer, at least one polymerization initiator, and an ethylenically unsaturated group An antireflection film formed from a composition for forming a low refractive index layer containing a curable compound.   2. The antireflection film according to claim 1, wherein the polymerization initiator and the curable compound are localized and cured at the lower part of the low refractive index layer.   The antireflection film according to claim 1 or 2, wherein the polymerization initiator is a heat and / or photodegradable initiator.   The antireflection film according to any one of claims 1 to 3, wherein the binder polymer is a thermosetting and / or ionizing radiation curable fluorine-containing polymer, and the curable compound is a non-fluorine compound.   The antireflection film according to any one of claims 1 to 4, wherein the SP value of the polymerization initiator and the curable compound is larger than that of the binder polymer.   The antireflective film according to any one of claims 1 to 5, wherein the curable compound is a hydrolyzate of organosilane and / or a partial condensate thereof.   The antireflection film according to any one of claims 1 to 6, wherein the low refractive index layer contains a compound in which a curable compound and a polymerization initiator are linked and bonded in the molecule.   The antireflection film according to any one of claims 1 to 7, further comprising an inorganic filler selected from silica particles and hollow silica particles in the low refractive index layer.   A method for producing an antireflection film having at least a hard coat layer and a low refractive index layer on a transparent support, wherein the composition for forming a low refractive index layer is applied and dried, and then an oxygen concentration of 3% by volume. The method for producing an antireflection film according to claim 1, wherein the film is formed by irradiation with ionizing radiation in the following atmosphere.   The antireflective film according to claim 9, wherein the composition for forming a low refractive index layer is applied, dried, further heat-cured, and then cured by irradiation with ionizing radiation in an atmosphere of 3% by volume or less. Manufacturing method.   The antireflection film according to any one of claims 1 to 8, or the antireflection film produced by the production method according to claim 9 or 10, at least of two protective films of a polarizing film in a polarizing plate. A polarizing plate used on one side.   A display device comprising the antireflection film according to any one of claims 1 to 8, the antireflection film produced by the production method according to claim 9 or 10, or the polarizing plate according to claim 11. The display device is arranged such that the low refractive index layer is on the viewing side.