JP2005148623A - Antireflection film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antireflection film having satisfactory antireflection improving its scratch resistance, and a polarizer plate and a display unit using this antireflection film. <P>SOLUTION: This is an antireflection film having a light scattering layer and a low refractive index layer at least on a transparent support. The light scattering layer is a layer formed by dispersing at least a kind of light transmissive particles diagonally 0.5-5 μm in a light transmissive resin. The difference of the refractive index of the particles and the resin is 0.02-0.2, and the particles are contained in 3-30 mass% in the total solid content of the light scattering layer. The low refractive index layer contains fluorine atoms in the extent of 35-80 mass%. And the refractive index obtained by coating a curable composite consisting mainly of the fluorine polymer containing a functional group of cross-linking or polymerization is 1.30-1.55. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an antireflection film, and more specifically, relates to an antireflection film that has both antireflection properties and scratch resistance and is also excellent in antiglare properties.

  In general, the antireflection film is used in 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), and a contrast reduction or image due to reflection of external light. In order to prevent reflection of light, it is arranged on the outermost surface of the display so as to reduce the reflectance by using the principle of optical interference.

  Such an antireflection film is generally produced by forming a film with a low refractive index layer having an appropriate film thickness and a lower refractive index than that of the transparent support on the transparent support. 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, high scratch resistance is required. In order to realize high scratch resistance in 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.

  Therefore, in order to lower the refractive index of the material, means of (1) introducing fluorine atoms and (2) lowering the density (introducing voids) have been proposed. There is a problem that the adhesion at the interface is lowered and the scratch resistance is lowered, and it is difficult to achieve both a low refractive index and a high scratch resistance.

  Thus, as methods for increasing the film strength to some extent so as to improve the scratch resistance, Patent Documents 1 and 2 propose a method using a fluorine-containing sol-gel film. However, (1) long heating is required for curing. However, there are significant restrictions such as (2) not having resistance to saponification solution (alkali treatment solution) and not being able to do after antireflection film formation when the surface of transparent plastic film substrate is saponified Will occur.

  On the other hand, Patent Documents 3 to 5 propose means for improving scratch resistance by lowering the coefficient of friction of the coating surface by introducing a polysiloxane structure into the fluorine-containing polymer. These means are effective to some extent for improving the scratch resistance, but sufficient scratch resistance cannot be obtained only by this method for a film having an essential film strength and interface adhesion.

Furthermore, with the recent high definition of image display devices, the interaction between the display pixel and the light scattering layer can no longer be ignored, and glare that causes the screen to appear glaring in red, green, and blue has become a problem. For this problem, it is known that introduction of internal scattering into the light scattering layer described in Patent Document 6 is effective. However, even this proposal does not satisfy all of sufficient antireflection properties, scratch resistance, and high productivity.
JP 2002-265866 A JP 2002-317152 A JP-A-11-189621 Japanese Patent Laid-Open No. 11-228631 JP 2000-313709 A Japanese Patent Laid-Open No. 11-30501

In short, the present situation is that no antireflection film has been proposed which has both antireflection properties and high scratch resistance, satisfies high productivity, and further eliminates glare.
Accordingly, an object of the present invention is to provide an antireflection film having sufficient antiglare properties, antireflection properties, scratch resistance, and high productivity.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have constituted a light scattering layer with a translucent resin and translucent particles having a specific refractive index difference, and further a particle of translucent particles. The inventors have found that the object can be achieved by adjusting the diameter and the fluorine content and refractive index in the constituent polymer of the low refractive index layer, and have completed the present invention.
That is, the present invention achieves the object by the following configuration.
(1) An antireflection film having at least a light scattering layer and a low refractive index layer on a transparent support, the light scattering layer comprising at least one kind of translucent particles having an average particle diameter of 0.5 to 5 μm. A layer formed by dispersing in a light-transmitting resin, wherein a difference in refractive index between the light-transmitting particles and the light-transmitting resin is 0.02 to 0.2, and the light-transmitting particles are scattered by light. 3 to 30% by mass in the total solid content of the layer, and the low refractive index layer is coated with a curable composition mainly composed of a fluorinated polymer containing a crosslinkable or polymerizable functional group. An antireflective film characterized by being a layer having a refractive index of 1.30 to 1.55.
(2) The fluorine-containing polymer is a copolymer comprising a fluorine-containing vinyl monomer polymerization unit and a polymerization unit having a (meth) acryloyl group in a side chain, and the main chain is composed of only carbon atoms. The antireflection film as described in (1).
(3) The curable composition is (A) the fluoropolymer, (B) the average particle diameter is 30% to 100% of the thickness of the low refractive index layer, and the refractive index is 1. An inorganic fine particle of 17 to 1.40, (C) a hydrolyzate of an organosilane compound represented by the following general formula [A] and / or a partial condensate thereof produced in the presence of an acid catalyst, The antireflection film as described in (1) or (2) above, which is a curable composition containing at least one of each.
Formula [A]
(R ¹⁰ ) _m -Si (X) _4-m
(In the formula, R ¹⁰ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. X represents a hydroxyl group or a hydrolyzable group. M represents an integer of 1 to 3.)
(4) The curable composition further comprises a polyfunctional polymerizable compound containing at least two polymerizable groups selected from radical polymerizable groups and / or cationic polymerizable groups and a polymerization initiator. The antireflection film as described in (3) above, which is a product.

  The antireflection film of the present invention is excellent in scratch resistance and productivity while having sufficient antireflection properties. Furthermore, it has excellent antiglare properties. Therefore, a display device such as a liquid crystal display device having the antireflection film of the present invention directly or via a polarizing plate provided with the antireflection film is a glare or reflection of external light or background even if it is a high-definition panel. There are few reflections and the visibility is extremely high.

A basic configuration of one preferred embodiment of the antireflection film of the present invention will be described with reference to the drawings.
Here, FIG. 1 is a cross-sectional view schematically showing a preferred embodiment of the antireflection film of the present invention.
The antireflection film 1 of this embodiment shown in FIG. 1 includes a transparent support 2, a light scattering layer 3 formed on the transparent support pair 2, and a low refractive index layer 4 formed on the light scattering layer 3. It consists of.
The light scattering layer 3 includes a translucent resin and translucent particles 5 dispersed in the translucent resin.
The refractive index of each layer constituting the antireflection film in the present invention preferably satisfies the following relationship.
Refractive index of light scattering layer> refractive index of transparent support> refractive index of low refractive index layer In the present invention, the light scattering layer has antiglare properties and hard coat properties. Although what was formed with the layer is illustrated, you may be comprised by multiple layers, for example, 2 layers-4 layers. Moreover, although you may provide directly on a transparent support body like this embodiment, you may provide via other layers, such as an antistatic layer and a moisture-proof layer.

The antireflection film of the present invention has a surface roughness of 0.08 to 0.40 μm as the center line average roughness, 10 points or less of the average roughness Rz of 10 points or less, and an average mountain valley distance Sm of 1 to 100 μm. The standard deviation of the height of the convex part from the deepest part of the concavo-convex part is 0.5 μm or less, the standard deviation of the average mountain-valley distance Sm with respect to the center line is 20 μm or less, and the surface with the inclination angle of 0 to 5 degrees is 10% or more. It is preferable to design so that sufficient anti-glare properties and a visually uniform mat feeling can be achieved.
Further, the ratio of the minimum value and the maximum value of the reflectance within the range of a ^* value −2 to 2, b ^* value −3 to 3, and 380 nm to 780 nm under the light source C is 0.5. ˜0.99 is preferable because the color of the reflected light is neutral. Moreover, when the b ^* value of the transmitted light under the C light source is set to 0 to 3, the yellow color of white display when applied to a display device is reduced, which is preferable. In addition, when a 120 μm × 40 μm grid is inserted between the surface light source and the antireflection film of the present invention and the luminance distribution is measured on the film, the standard deviation of the luminance distribution is set to 20 or less, and this is applied to a high-definition panel. The glare when applying the film of the invention is reduced, which is preferable.

  In addition, the antireflection film of the present invention can suppress reflection of external light by setting its optical characteristics to a specular reflectance of 2.5% or less, a transmittance of 90% or more, and a 60 ° gloss of 70% or less. Since visibility improves, it is preferable. In addition, haze 20% to 50%, internal haze / total haze value 0.3 to 1, haze value after formation of low refractive index layer from haze value up to light scattering layer within 15%, comb width 0. The transmission image sharpness at 5 mm is 20% to 50%, and the transmittance ratio of vertical transmitted light / vertical direction at 2 degrees is 1.5 to 5.0, which prevents glare on a high-definition LCD panel and characters This is preferable because reduction of blur such as is achieved.

Next, the low refractive index layer will be described below.
<Low refractive index layer>
The refractive index of the low refractive index layer in the antireflection film of the present invention is 1.30 to 1.55, preferably 1.35 to 1.40.
When the refractive index is less than 1.30, the antireflection performance is improved, but the mechanical strength of the film is lowered, and when it exceeds 1.55, the antireflection performance is remarkably deteriorated.
Further, the low refractive index layer preferably satisfies the following formula (I) from the viewpoint of reducing the reflectance.
Formula (I)
(M / 4) × 0.7 <n1 × d1 <(m / 4) × 1.3
In the formula, m is a positive odd number, n1 is the refractive index of the low refractive index layer, and d1 is the film thickness (nm) of the low refractive index layer. Further, λ is a wavelength, which is a value in the range of 500 to 550 nm.
In addition, satisfy | filling said numerical formula (I) means that m (positive odd number, usually 1) which satisfy | fills numerical formula (I) exists in the said wavelength range.

The material for forming the low refractive index layer will be described below.
The low refractive index layer is a cured film formed by applying, drying and curing a curable composition containing a fluorine-containing polymer as a main component.
<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 ionization. A polymer that is cross-linked by radiation is preferable in terms of improving productivity in the case of coating and curing a roll film while transporting the web.
In addition, when the antireflection film of the present invention is mounted on an image 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, 300 gf or less 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 for the low refractive index layer is a fluorine-containing polymer containing a fluorine atom in a range of 35 to 80% by mass and containing a crosslinkable or polymerizable functional group, for example, containing a perfluoroalkyl group In addition to hydrolysates and dehydration condensates of silane compounds [for example, (heptadecafluoro-1,1,2,2-tetrahydrodecyl) triethoxysilane], fluorinated monomer units and crosslinking reactive units are used as constituent units. A fluorine-containing copolymer is mentioned. In the case of a fluorinated copolymer, the main chain preferably consists of only carbon atoms. That is, it is preferable that the main chain skeleton does not have an oxygen atom or a nitrogen atom.

  Specific examples of the fluorine-containing monomer unit include, for example, fluoroolefins (for example, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, perfluorooctylethylene, hexafluoropropylene, perfluoro-2,2-dimethyl-1,3- Dioxoles, etc.), (meth) acrylic acid partial or fully fluorinated alkyl ester derivatives (for example, Biscoat 6FM (manufactured by Osaka Organic Chemicals) and M-2020 (manufactured by Daikin)), fully or partially fluorinated vinyl ethers, etc. However, perfluoroolefins are preferable, and hexafluoropropylene is particularly preferable from the viewpoint of refractive index, solubility, transparency, availability, and the like.

  Examples of the crosslinking reactive unit include a structural unit obtained by polymerization of a monomer having a self-crosslinking functional group in the molecule such as glycidyl (meth) acrylate and glycidyl vinyl ether; carboxyl group, hydroxy group, amino group, sulfo group A structural unit obtained by polymerization of a monomer having, for example, (meth) acrylic acid, methylol (meth) acrylate, hydroxyalkyl (meth) acrylate, allyl acrylate, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, maleic acid, crotonic acid, etc. And a structural unit in which a crosslinkable reactive group such as a (meth) acryloyl group is introduced by a polymer reaction (for example, it can be introduced by a technique such as allowing acrylic acid chloride to act on a hydroxy group).

  In addition to the fluorine-containing monomer unit and the cross-linking reactive unit, from the viewpoint of solubility in a solvent, film transparency, and the like, a monomer not containing a fluorine atom is appropriately copolymerized to introduce another polymerization unit. You can also. There are no particular limitations on the monomer units that can be used in combination, such as olefins [ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride, etc.], acrylic esters [methyl acrylate, methyl acrylate, ethyl acrylate, acrylic acid 2 -Ethylhexyl], 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, etc.], vinyl esters [vinyl acetate, vinyl propionate, vinyl cinnamate, etc.], acrylamides [N-tertbutylacrylamide, N-silane] B hexyl acrylamide], methacrylamides, and acrylonitrile derivatives.

  As described in JP-A-10-25388 and JP-A-10-147739, a curing agent may be appropriately used in combination with the fluoropolymer.

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 crosslinking reaction alone (radical reactive group such as (meth) acryloyl group, ring-opening polymerizable group such as epoxy group and oxetanyl group).
These crosslinkable group-containing polymerized units preferably occupy 5 to 70 mol%, particularly preferably 30 to 60 mol% of the total polymerized units of the polymer.

  A preferred form of the copolymer used in the present invention is that of general formula 1.

In General Formula 1, L represents a linking group having 1 to 10 carbon atoms, more preferably a linking group having 1 to 6 carbon atoms, particularly preferably a linking group having 2 to 4 carbon atoms, It may have a branched structure, may have a ring structure, or 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 the linking site on the polymer main chain side, ** represents the linking on the (meth) acryloyl group side Represents a part). m represents 0 or 1;

  In general formula 1, X represents a hydrogen atom or a methyl group. From the viewpoint of curing reactivity, a hydrogen atom is more preferable.

  In the general formula 1, 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 the mol% of each constituent component, and preferably 30 ≦ x ≦ 60, 5 ≦ y ≦ 70, and 0 ≦ z ≦ 65, and more preferably 35 ≦ x ≦ 55 and 30 ≦ y ≦. 60, 0 ≦ z ≦ 20, particularly preferably 40 ≦ x ≦ 55, 40 ≦ y ≦ 55, and 0 ≦ z ≦ 10. However, x + y + z = 100.
A particularly preferred form of the copolymer used in the present invention is General Formula 2.

In General Formula 2, X represents the same meaning as in General Formula 1, and the preferred range is also the same.
n represents an integer of 2 ≦ n ≦ 10, preferably 2 ≦ n ≦ 6, and particularly preferably 2 ≦ n ≦ 4.
B represents a unit of a repeating unit derived from an arbitrary vinyl monomer, and may be composed of a single composition or a plurality of compositions. As an example, what was demonstrated as an example of A in the said General formula 1 is applicable.
x, y, z1 and z2 each represent mol% of each repeating unit, and x and y preferably satisfy 30 ≦ x ≦ 60 and 5 ≦ y ≦ 70, respectively, more preferably 35 ≦ x ≦ 55. 30 ≦ y ≦ 60, particularly preferably 40 ≦ x ≦ 55 and 40 ≦ y ≦ 55. z1 and z2 preferably satisfy 0 ≦ z1 ≦ 65 and 0 ≦ z2 ≦ 65, more preferably 0 ≦ z1 ≦ 30 and 0 ≦ z2 ≦ 10, and 0 ≦ z1 ≦ 10, 0 It is particularly preferable that ≦ z2 ≦ 5. However, x + y + z1 + z2 = 100.
The copolymer represented by the general formula 1 or 2 is obtained, for example, by introducing a (meth) acryloyl group into a copolymer comprising a hexafluoropropylene component and a hydroxyalkyl vinyl ether component by any of the above-described methods. Can be synthesized. As the reprecipitation solvent used in this case, isopropanol, hexane, methanol and the like are preferable.

The curable composition preferably contains (A) the fluoropolymer, (B) inorganic fine particles, and (C) an organosilane compound described later.
<Inorganic fine particles>
The amount of the inorganic fine particles is preferably ^{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 amount is too small, the effect of improving the scratch resistance is reduced. If the amount is too large, fine irregularities are formed on the surface of the low refractive index layer, and the appearance such as black tightening and the integrated reflectance may be deteriorated. It is preferable to be inside.
Since the inorganic fine particles are contained in the low refractive index layer, it is desirable that the inorganic fine particles have a low refractive index. Examples thereof include fine particles of magnesium fluoride and silica. In particular, silica fine particles are preferable in terms of refractive index, dispersion stability, and cost.
The average particle size of the inorganic fine particles is preferably 30% or more and 100% or less, more preferably 35% or more and 80% or less, and still more preferably 40% or more and 60% or less of the thickness of the low refractive index layer. That is, when the thickness of the low refractive index layer is 100 nm, the particle size of the silica fine particles is preferably 30 nm to 100 nm, more preferably 35 nm to 80 nm, and still more preferably 40 nm to 60 nm.
If the particle size of the inorganic fine particles is too small, the effect of improving the scratch resistance is reduced, and if it is too large, fine irregularities are formed on the surface of the low refractive index layer, and the appearance such as black tightening and the integrated reflectance may deteriorate. Therefore, it is preferable to be within the above range. The inorganic fine particles may be either crystalline or amorphous, and may be monodispersed particles or aggregated particles as long as a predetermined particle size is satisfied. The shape is most preferably a spherical diameter, but there is no problem even if the shape is indefinite.
Here, the average particle diameter of the inorganic fine particles is measured by a Coulter counter.

In order to further reduce the increase in the refractive index of the low refractive index layer, the inorganic fine particles preferably have a hollow structure, and the refractive index of the inorganic fine particles is 1.17 to 1.40, more preferably 1. It is 17-1.35, More preferably, it is 1.17-1.30. Here, the refractive index represents the refractive index of the entire particle, and does not represent the refractive index of only the inorganic material of the outer shell in the case of inorganic fine particles having a hollow structure. At this time, assuming that the radius of the cavity inside the particle is a and the radius of the outer shell of the particle is b, the porosity x expressed by the following formula (II) is (formula II)
^{x = (4πa 3/3)} / (4πb 3/3) × 100
Preferably it is 10 to 60%, More preferably, it is 20 to 60%, Most preferably, it is 30 to 60%.
If the refractive index of hollow inorganic fine particles is made lower and the porosity is increased, the thickness of the outer shell becomes thinner and the strength of the particles becomes weaker. Therefore, from the viewpoint of scratch resistance, the refractive index is 1 Particles with a low refractive index of less than .17 do not hold.
The refractive index of the inorganic fine particles was measured with an Abbe refractometer (manufactured by Atago Co., Ltd.).

In addition, at least one kind of inorganic fine particles (hereinafter referred to as “small size inorganic fine particles”) having an average particle size of less than 25% of the thickness of the low refractive index layer is referred to as “inorganic fine particles (hereinafter referred to as“ small size inorganic fine particles ”). It may be used in combination with “large-size inorganic fine particles”.
Since the small-sized inorganic fine particles can be present in the gaps between the large-sized inorganic fine particles, they can contribute as a retaining agent for the large-sized inorganic fine particles.
When the low refractive index layer is 100 nm, the average particle size of the small-sized inorganic fine particles 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 inorganic fine particles is preferable in terms of raw material costs and a retaining agent effect.
As described above, the inorganic fine particles have an average particle size of 30 to 100% of the thickness of the low refractive index layer as described above, have a hollow structure, and have a refractive index of 1.17 to 1. What is 40 is used especially preferably.

Inorganic fine particles are treated with physical surface treatment such as plasma discharge 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. Further, chemical surface treatment with a surfactant, a coupling agent or the like may be performed. Of these, the use of a coupling agent is particularly preferred. As the coupling agent, an alkoxy metal compound (eg, titanium coupling agent, silane coupling agent) is preferably used. Among these, silane coupling treatment is particularly effective.
The coupling agent is used as a surface treatment agent for the inorganic fine particles of the low refractive index layer in advance for surface treatment prior to the preparation of the layer coating solution, and is further added as an additive during preparation of the layer coating solution. It is preferable to make it contain in a layer.
The inorganic fine particles are preferably dispersed in the medium in advance before the surface treatment in order to reduce the load of the surface treatment.

Next, (C) the organosilane compound will be described.
<Organosilane compound>
When the curable composition contains a hydrolyzate of an organosilane compound and / or a partial condensate thereof (hereinafter, the obtained reaction solution is also referred to as “sol component”), the scratch resistance is improved. In particular, it is preferable in terms of achieving both the antireflection ability and the scratch resistance.
This sol component functions as a binder for the low refractive index layer by applying the curable composition and then condensing in a drying and heating process to form a cured product. Moreover, in this invention, since it has the said fluorine-containing polymer, the binder which has a three-dimensional structure is formed by irradiation of actinic light.
The organosilane compound is preferably represented by the following general formula [A].
Formula [A]
(R ¹⁰ ) _m -Si (X) _4-m
In the general formula [A], R ¹⁰ 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 preferably has 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 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 or the like). ), And R ² COO (R ² 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 An alkoxy group, particularly preferably a methoxy group or an ethoxy group.
m represents an integer of 1 to 3, preferably 1 or 2, and particularly preferably 1.

When R ¹⁰ or X there are a plurality, a plurality of R ¹⁰ or X groups may be different, even the same, respectively.
The substituent contained in R ¹⁰ 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 ^{10 s} , at least one of them is preferably a substituted alkyl group or a substituted aryl group.
Among the organosilane compounds represented by the general formula [A], an organosilane compound having a vinyl polymerizable substituent represented by the following general formula [B] is preferable.

In the general formula [B], R ¹ represents a hydrogen atom, a methyl group, a methoxy group, an alkoxycarbonyl group, a cyano group, a fluorine atom, or a chlorine atom. Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group. A hydrogen atom, a methyl group, a methoxy group, a methoxycarbonyl group, a cyano group, a fluorine atom and a chlorine atom are preferred, a hydrogen atom, a methyl group, a methoxycarbonyl group, a fluorine atom and a chlorine atom are more preferred, and a hydrogen atom and a methyl group Is particularly preferred.
Y represents a single bond or * -COO-**, * -CONH-** or * -O-**, preferably a single bond, * -COO-** or * -CONH-**, * -COO-** is more preferable, and * -COO-** is particularly preferable. * Represents a position bonded to ═C (R ¹ ) —, and ** represents a position bonded to L.

  L represents a divalent linking chain. Specifically, a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted alkylene group having a linking group (for example, ether, ester, amide, etc.) inside, and a linking group inside. A substituted or unsubstituted arylene group, a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, an alkylene group having a linking group therein is preferred, an unsubstituted alkylene group, an unsubstituted arylene group Further, an alkylene group having an ether or ester linking group inside is more preferable, an unsubstituted alkylene group, and an alkylene group having an ether or ester linking group inside is particularly preferable. Examples of the substituent include a halogen, a hydroxyl group, a mercapto group, a carboxyl group, an epoxy group, an alkyl group, and an aryl group, and these substituents may be further substituted.

n represents 0 or 1. When there are a plurality of Xs, the plurality of Xs may be the same or different. n is preferably 0.
R ¹⁰ has the same meaning as in formula [A], preferably a substituted or unsubstituted alkyl group or an unsubstituted aryl group, and more preferably an unsubstituted alkyl group or an unsubstituted aryl group.
X has the same meaning as in the general formula [A], preferably a halogen atom, a hydroxyl group or an unsubstituted alkoxy group, more preferably a chlorine atom, a hydroxyl group or an unsubstituted alkoxy group having 1 to 6 carbon atoms, a hydroxyl group or a carbon number of 1 -3 alkoxy groups are more preferred, and methoxy groups are particularly preferred.

  Two or more compounds of the general formula [A] and general formula [B] may be used in combination. Although the specific example of a compound represented by general formula [A] and general formula [B] is shown below, it is not limited.

  Of these, (M-1), (M-2), and (M-5) are particularly preferable.

  The hydrolyzate and / or partial condensate of the organosilane compound is generally produced by treating the organosilane compound 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, Examples thereof include organic bases such as pyridine; metal alkoxides such as triisopropoxyaluminum and tetrabutoxyzirconium; metal chelate compounds having a metal such as Zr, Ti or Al as a central metal. In the present invention, it is preferable to use acid catalysts of inorganic acids and organic acids. Of these, hydrochloric acid and sulfuric acid are preferable for inorganic acids, and acid dissociation constants (pKa value (25 ° C.)) in water are preferably 4.5 or less for organic acids. Furthermore, hydrochloric acid, sulfuric acid, and acids in water are preferable. An organic acid having a dissociation constant of 3.0 or less is preferable, particularly an organic acid having an acid dissociation constant of 2.5 or less in hydrochloric acid, sulfuric acid or water, and an organic acid having an acid dissociation constant of 2.5 or less in water. More specifically, methanesulfonic acid, oxalic acid, phthalic acid, and malonic acid are more preferable, and oxalic acid is particularly preferable.

  In the present invention, it is preferable that a β-diketone compound and / or a β-ketoester compound is further added to the curable composition. This will be further described below.

The β-diketone compound and / or β-ketoester compound represented by the general formula R ⁴ COCH ₂ COR ⁵ is used in the present invention, and is used as a stability improver for the curable composition used in the present invention. It works. Here, R ⁴ represents an alkyl group having 1 to 10 carbon atoms, and R ⁵ represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. That is, by coordinating with a metal atom in the metal chelate compound (zirconium, titanium and / or aluminum compound), the condensation reaction of the hydrolyzate and / or partial condensate of the organosilane compound by these metal chelate compounds is performed. It is considered that the promoting action is suppressed and the storage stability of the resulting composition is improved. R ⁴ and R ⁵ constituting the β- diketone compound and / or β- ketoester compound are the same as R ⁴ and R ⁵ constituting the metal chelate compound.

  Specific examples of the β-diketone compound and / or β-ketoester compound include acetylacetone, methyl acetoacetate, ethyl acetoacetate, acetoacetate-n-propyl, acetoacetate-i-propyl, acetoacetate-n-butyl, acetoacetate. Acetic acid-sec-butyl, acetoacetic acid-t-butyl, 2,4-hexane-dione, 2,4-heptane-dione, 3,5-heptane-dione, 2,4-octane-dione, 2,4-nonane -Dione, 5-methyl-hexane-dione and the like can be mentioned. Of these, ethyl acetoacetate and acetylacetone are preferred, and acetylacetone is particularly preferred. These β-diketone compounds and / or β-ketoester compounds may be used alone or in combination of two or more. In the present invention, the β-diketone compound and / or β-ketoester compound is preferably used in an amount of 2 mol or more, more preferably 3 to 20 mol, per 1 mol of the metal chelate compound. If it is less than 2 mol, the storage stability of the resulting composition may be inferior, which is not preferable.

The compounding amount of the organosilane compound is preferably 0.1 to 50% by mass, more preferably 0.5 to 20% by mass, and most preferably 1 to 10% by mass based on the total solid content of the low refractive index layer.
The organosilane compound may be added directly to the curable composition (coating liquid for light scattering layer, low refractive index layer, etc.), but the organosilane compound is treated in the presence of a catalyst in advance. It is preferable to prepare a hydrolyzate and / or partial condensate of a silane compound and prepare the curable composition using the obtained reaction solution (sol solution). In the present invention, first, the organosilane compound A composition containing a hydrolyzate and / or a partial condensate and a metal chelate compound is prepared, and a liquid obtained by adding a β-diketone compound and / or a β-ketoester compound thereto is added to at least a light scattering layer or a low refractive index layer. It is preferable to coat it in a single layer coating solution.

  5-100 mass% is preferable, the usage-amount of the sol component of the organosilane with respect to a fluorine-containing polymer in a low refractive index layer has more preferable 5-40 mass%, 8-35 mass% is still more preferable, 10-30 mass % Is particularly preferred. If the amount used is small, it is difficult to obtain the effect of the present invention, and if the amount used is too large, the refractive index increases or the shape / surface shape of the film deteriorates.

  An inorganic filler other than the above-described inorganic fine particles can be added to the curable composition in an addition amount within a range that does not impair the desired effect of the present invention. Details of the inorganic filler will be described later.

[Other substances contained in the curable composition]
The curable composition is prepared by adding various additives, a radical polymerization initiator, and a cationic polymerization initiator to the (A) fluorine-containing polymer, (B) inorganic fine particles, and (C) the organosilane compound as necessary. Further, they are prepared by dissolving them in a suitable solvent. At this time, the concentration of the solid content is appropriately selected according to the use, but is generally about 0.01 to 60% by mass, preferably 0.5 to 50% by mass, particularly preferably 1% to 20% by mass. %.

  Curing agents such as polyfunctional (meth) acrylate compounds, polyfunctional epoxy compounds, polyisocyanate compounds, aminoplasts, polybasic acids or anhydrides thereof from the viewpoint of interfacial adhesion with the lower layer directly in contact with the low refractive index layer Can also be added in small amounts. When adding these, it is preferable to set it as the range of 30 mass% or less with respect to the total solid of a low-refractive-index layer film, It is more preferable to set it as the range of 20 mass% or less, The range of 10 mass% or less It is particularly preferable that

  In addition, for the purpose of imparting properties such as antifouling properties, water resistance, chemical resistance, and slipping properties, a known silicone compound or fluorine compound antifouling agent, slipping agent, and the like may be appropriately added. When these additives are added, 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.

  Preferable examples of the silicone compound 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 acryloyl group, methacryloyl group, vinyl group, aryl group, cinnamoyl group, epoxy group, oxetanyl group, hydroxyl group, fluoroalkyl group, polyoxyalkylene group, carboxyl group, amino group and the like. It is done. Although there is no restriction | limiting in particular in molecular weight, 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. Although there is no restriction | limiting in particular in silicone 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 25.0-37.8 mass%, and 30.0-37.0. Most preferably, it is mass%. Examples of preferable silicone compounds include X-22-174DX, X-22-2426, X-22-164B, X22-164C, X-22-170DX, X-22-176D, X, manufactured by Shin-Etsu Chemical Co., Ltd. -22-1821 (named above), Chisso Corporation, FM-0725, FM-7725, DMS-U22, RMS-033, RMS-083, UMS-182 (named above), etc. It is not limited to.

As the fluorine compound, a compound having a fluoroalkyl group is preferable. 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.), even 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.), but also alicyclic structures (preferably 5-membered or 6-membered rings such as perfluorocyclohexyl groups, perfluorocyclopentyl, etc. Group or an alkyl group substituted with these, and may have 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.). A plurality of the fluoroalkyl groups may be contained in the same molecule.
It is preferable that the fluorine-based compound further has 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 preferred fluorine-based compounds include Daikin Chemical Industries, R-2020, M-2020, R-3833, M-3833 (named above), Dainippon Ink, Megafac F-171. , F-172, F-179A, Defender MCF-300 (named above), but not limited thereto.

  For the purpose of imparting properties such as dust resistance and antistatic properties, a known cationic surfactant or a dustproof agent such as a polyoxyalkylene compound, an antistatic agent, or the like can be appropriately added. 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, more preferably in the range of 0.05 to 10% by mass of the total solid content of the low n layer. Particularly preferably 0.1 to 5% by mass. Examples of preferable compounds include, but are not limited to, Dainippon Ink Co., Ltd., MegaFuck F-150 (trade name), Toray Dow Corning Co., Ltd., SH-3748 (trade name), and the like. Do not mean.

Next, the light scattering layer will be described below.
<Light scattering layer>
The light scattering layer is formed for the purpose of contributing to the film light diffusibility due to surface scattering and / or internal scattering and hard coat properties for improving the scratch resistance of the film. Therefore, a translucent resin for imparting hard coat properties, and translucent particles for imparting light diffusibility are essential components, and if necessary, higher refractive index, prevention of cross-linking shrinkage, higher strength can be achieved. For containing an inorganic filler.

  The thickness of the light scattering layer is preferably 1 to 10 μm and more preferably 1.2 to 6 μm for the purpose of imparting hard coat properties. If it is too thin, the hard property is insufficient, and if it is too thick, curling and brittleness may be deteriorated and workability may be lowered.

The translucent resin is preferably a binder polymer having a saturated hydrocarbon chain or a polyether chain as a main chain, and more preferably a binder polymer having a saturated hydrocarbon chain as a main chain. The binder polymer preferably has a crosslinked structure.
As the binder polymer having a saturated hydrocarbon chain as a main chain, a polymer of an ethylenically unsaturated monomer is preferable. As the binder polymer having a saturated hydrocarbon chain as the main chain and having a crosslinked structure, a (co) polymer of monomers having two or more ethylenically unsaturated groups is preferable.
In order to increase the refractive index of the binder polymer, the monomer structure has a high refractive index including 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. The rate monomer can also be selected.

  Examples of the monomer having two or more ethylenically unsaturated groups include esters of polyhydric alcohol and (meth) acrylic acid [for example, ethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, hexanediol di ( (Meth) acrylate, 1,4-cyclohexanediacrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, dipentaerythritol tetra (Meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol hexa (meth) acrylate, 1,2,3- Chlorohexane tetramethacrylate, polyurethane polyacrylate, polyester polyacrylate], modified ethylene oxide of the above ester, vinylbenzene and derivatives thereof (eg, 1,4-divinylbenzene, 4-vinylbenzoic acid-2-acryloylethyl ester, 1,4-divinylcyclohexanone], vinylsulfone (eg, divinylsulfone), acrylamide (eg, methylenebisacrylamide) and methacrylamide. Two or more of these monomers may be used in combination.

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

Polymerization of these monomers having an ethylenically unsaturated group can be carried out by irradiation with ionizing radiation or heating in the presence of a photo radical initiator or a thermal radical initiator.
Therefore, the light-scattering layer contains a monomer for forming a light-transmitting resin such as the above-mentioned ethylenically unsaturated monomer, a photo radical initiator or a heat radical initiator, light-transmitting particles, and an inorganic filler as necessary. It can be formed by preparing a coating liquid and curing the coating liquid on a transparent support by ionizing radiation or a polymerization reaction with heat.

Photo radical (polymerization) initiators include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkyldione compounds, disulfides Examples include compounds, fluoroamine compounds and aromatic sulfoniums. Examples of acetophenones include 2,2-diethoxyacetophenone, p-dimethylacetophenone, 1-hydroxydimethylphenyl ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-4-methylthio-2-morpholinopropiophenone and 2 -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone is included. Examples of benzoins include benzoin benzene sulfonate, benzoin toluene sulfonate, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether. Examples of the benzophenones include benzophenone, 2,4-dichlorobenzophenone, 4,4-dichlorobenzophenone and p-chlorobenzophenone. Examples of phosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
Various examples are described in the latest UV curing technology (p.159, issuer; Kazuhiro Takashiro, publisher; Technical Information Association, Inc., published in 1991), and are useful for the present invention.
Preferable examples of commercially available photocleavable photoradical (polymerization) initiators include Irgacure (651, 184, 907) manufactured by Ciba Geigy Japan.
The photo radical (polymerization) initiator is preferably used in the range of 0.1 to 15 parts by mass, more preferably in the range of 1 to 10 parts by mass with respect to 100 parts by mass of the polyfunctional monomer.
In addition to the photoradical (polymerization) initiator, a photosensitizer may be used. Specific examples of the photosensitizer include n-butylamine, triethylamine, tri-n-butylphosphine, Michler's ketone and thioxanthone.

As the thermal radical initiator, organic or inorganic peroxides, organic azo, diazo compounds, and the like can be used.
Specifically, 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-azo-bis-isobutyronitrile, 2-azo-bis-propionitrile, 2-azo-bis-cyclohexanedinitrile, etc. as diazo compounds, diazoaminobenzene, p -Nitrobenzenediazonium etc. can be mentioned.

The 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, translucent particles and an inorganic filler is prepared, and the coating liquid is applied onto a transparent support and then polymerized by ionizing radiation or heat. It can be cured by reaction to form a light diffusion layer.

Instead of or in addition to a monomer having two or more ethylenically unsaturated groups, a monomer having a crosslinkable functional group is used to introduce a crosslinkable functional group into the polymer, and by reaction of this crosslinkable functional group, 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.

The translucent particles used in the light scattering layer are used for the purpose of imparting light diffusibility and antiglare properties, and have an average particle size of 0.5 to 5 μm, preferably 1.0 to 4.0 μm. It is. If the average particle size is less than 0.5 μm, the light scattering angle distribution spreads to a wide angle, resulting in a decrease in the character resolution of the display, and it becomes difficult to form surface irregularities, resulting in insufficient antiglare properties. Therefore, it is not preferable. On the other hand, when the thickness exceeds 5 μm, it is necessary to increase the thickness of the light scattering layer, which causes problems such as an increase in curl and an increase in material cost.
Specific examples of the translucent particles include particles of inorganic compounds such as silica particles and TiO ₂ particles; acrylic particles, crosslinked acrylic particles, methacrylic particles, crosslinked methacrylic particles, polystyrene particles, crosslinked styrene particles, melamine resin particles, Preferred examples include resin particles such as benzoguanamine resin particles. Of these, crosslinked styrene particles, crosslinked acrylic particles, crosslinked acrylic styrene particles, and silica particles are preferable.
The translucent particles can be either spherical or indefinite.

  Moreover, you may use together and use 2 or more types of translucent particle | grains from which a particle diameter differs. It is possible to impart an antiglare property with a light-transmitting particle having a larger particle size and to impart another optical characteristic with a light-transmitting particle having a smaller particle size. For example, when an antireflection film is attached to a high-definition display of 133 ppi or higher, it is required that there is no problem in optical performance called glare as described above. Glare is derived from the fact that the unevenness of the film surface (which contributes to antiglare properties) causes the pixels to be enlarged or reduced and loses brightness uniformity, but is smaller than the light-transmitting particles that impart antiglare properties. The diameter can be greatly improved by using translucent particles different from the refractive index of the binder.

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

The translucent particles are blended in the formed light scattering layer so as to be contained in an amount of 3 to 30% by mass in the total solid content of the light scattering layer. Preferably it is 5-20 mass%. If it is less than 3% by mass, the light scattering effect is insufficient, and if it exceeds 30% by mass, problems such as a decrease in image resolution, surface turbidity and glare occur.
The density of the translucent particles is preferably 10 to 1000 mg / m ² , more preferably 100 to 700 mg / m ² .
The particle size distribution of the translucent particles is measured by a Coulter counter method, and the measured distribution is converted into a particle number distribution.

In order to increase the refractive index of the light scattering layer, in addition to the above light-transmitting particles, an oxidation of at least one metal selected from titanium, zirconium, aluminum, indium, zinc, tin, and antimony is added to the light scattering layer. It is preferable that an inorganic filler having an average particle diameter of 0.2 μm or less, preferably 0.1 μm or less, more preferably 0.06 μm or less is contained.
Conversely, in order to increase the difference in refractive index with the light-transmitting particles, the light scattering layer using the high-refractive index light-transmitting particles uses silicon oxide to keep the refractive index of the layer low. It is also preferable. The preferred particle size is the same as that of the aforementioned inorganic filler.
Specific examples of the inorganic filler used in the light scattering layer include TiO ₂ , ZrO ₂ , Al ₂ O ₃ , In ₂ O ₃ , ZnO, SnO ₂ , Sb ₂ O ₃ , ITO and SiO ₂ . TiO ₂ and ZrO ₂ are particularly preferable from the viewpoint of increasing the refractive index. The surface of the inorganic filler is preferably subjected to a silane coupling treatment or a titanium coupling treatment, and a surface treatment agent having a functional group capable of reacting with a binder species on the filler surface is preferably used.
When using these inorganic fillers, the addition amount is preferably 10 to 90% of the total mass of the light scattering layer, more preferably 20 to 80%, and particularly preferably 30 to 75%.
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 above-mentioned organosilane compound can also be used for the light scattering layer.
The amount of the organosilane compound added to the layers other than the low refractive index layer is preferably 0.001 to 50% by mass, more preferably 0.01 to 20% by mass, based on the total solid content of the containing layer (added layer). 0.05 to 10% by mass is more preferable, and 0.1 to 5% by mass is particularly preferable.

The bulk refractive index of the mixture of translucent resin and translucent particles in the present invention is preferably 1.48 to 2.00, more preferably 1.50 to 1.80. In order to set the refractive index within the above range, the kind and amount ratio of the light-transmitting resin and the light-transmitting particles may be appropriately selected. How to select it can be easily known experimentally in advance.
In the present invention, the difference in refractive index between the translucent resin and the translucent particles (the refractive index of the translucent particles−the refractive index of the translucent resin) is 0.02 to 0.2. , Preferably 0.05 to 0.15. If this difference is less than 0.02, the effect of internal scattering is insufficient and glare deteriorates. If it exceeds 0.2, the problem of cloudiness on the film surface arises.
The refractive index of the translucent resin is preferably 1.45 to 2.00, and more preferably 1.48 to 1.60.
Further, the refractive index of the translucent particles is preferably 1.40 to 1.80, and more preferably 1.50 to 1.70.
Here, the refractive index of the translucent resin can be quantitatively evaluated by directly measuring it with an Abbe refractometer or by measuring a spectral reflection spectrum or a spectral ellipsometry.

The light scattering layer of the present invention is formed with a light diffusing layer in order to ensure surface uniformity such as coating unevenness, drying unevenness, point defects, etc. Contained in the coating composition. 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.
The purpose is to increase productivity by giving high-speed coating suitability while improving the surface uniformity.

  Preferable examples of the fluorosurfactant include a fluoroaliphatic group-containing copolymer (sometimes abbreviated as “fluorine polymer”), and the fluoropolymer includes the following monomer (i): An acrylic resin, a methacrylic resin, and a vinyl monomer copolymerizable therewith, characterized by containing a corresponding repeating unit, or containing a repeating unit corresponding to the monomer (ii) below: Copolymers are useful.

(I) Fluoroaliphatic group-containing monomer represented by the following general formula 3

In General Formula 3, R ¹¹ represents a hydrogen atom or a methyl group, X represents an oxygen atom, a sulfur atom or —N (R ¹² ) —, m is an integer of 1 to 6 and n is an integer of 2 to 4. Represent. R ¹² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, specifically a methyl group, an ethyl group, a propyl group or a butyl group, preferably a hydrogen atom or a methyl group. X is preferably an oxygen atom.

(Ii) Monomer represented by the following general formula 4 copolymerizable with the above (i)

In General Formula 4, R ¹³ represents a hydrogen atom or a methyl group, Y represents an oxygen atom, a sulfur atom or —N (R ¹⁵ ) —, R ¹⁵ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, specifically Specifically, it represents a methyl group, an ethyl group, a propyl group, or a butyl group, preferably a hydrogen atom or a methyl group. Y is an oxygen atom, -N (H) -, and -N (CH ₃₎ - it is preferred.
R ¹⁴ represents a linear, branched or cyclic alkyl group having 4 to 20 carbon atoms which may have a substituent. Examples of the substituent for the alkyl group of R ¹⁴ include a hydroxyl group, an alkylcarbonyl group, an arylcarbonyl group, a carboxyl group, an alkyl ether group, an aryl ether group, a halogen atom such as a fluorine atom, a chlorine atom, and a bromine atom, a nitro group, and a cyano group. , Amino groups and the like, but not limited thereto. Examples of the linear, branched or cyclic alkyl group having 4 to 20 carbon atoms include a butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group and undecyl group which may be linear or branched. , Dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, octadecyl group, eicosanyl group, etc., and monocyclic cycloalkyl groups such as cyclohexyl group, cycloheptyl group and bicycloheptyl group, bicyclodecyl group, tricycloundecyl group, A polycyclic cycloalkyl group such as a tetracyclododecyl group, an adamantyl group, a norbornyl group, a tetracyclodecyl group, or the like is preferably used.

  The amount of the fluoroaliphatic group-containing monomer represented by the general formula 3 used in the fluoropolymer used in the present invention is 10 mol% or more based on each monomer of the fluoropolymer, preferably Is 15 to 70 mol%, more preferably in the range of 20 to 60 mol%.

The preferred weight average molecular weight of the fluoropolymer used in the present invention is preferably 3000 to 100,000, more preferably 5,000 to 80,000.
Furthermore, the preferable addition amount of the fluoropolymer used in the present invention is in the range of 0.001 to 5% by mass, preferably in the range of 0.005 to 3% by mass, and more preferably, with respect to the coating solution. It is the range of 0.01-1 mass%. If the addition amount of the fluorine-based polymer is less than 0.001% by mass, the effect is insufficient. Adversely affect the scratch resistance).

  Hereinafter, an example of a specific structure of the fluoropolymer composed of the fluoroaliphatic group-containing monomer represented by the general formula 3 is shown, but the present invention is not limited thereto. In addition, the number in a formula shows the molar ratio of each monomer component. Mw represents a mass average molecular weight.

However, by using the fluorine-based polymer as described above, the surface energy of the light scattering layer is reduced due to segregation of the functional group containing F atoms on the surface of the light scattering layer, and the low refractive index on the light scattering layer When the rate layer is overcoated, there arises a problem that the antireflection performance deteriorates. This is presumably because minute unevenness that cannot be visually detected in the low refractive index layer deteriorates because the wettability of the curable composition used for forming the low refractive index layer deteriorates. To solve such problems, by adjusting the structure and amount of the fluorine-based polymer, the surface energy of the light scattering layer preferably in ^{20mN · m -1 ~50mN · m -1} , more preferably it was found that it is effective to control the ^{30mN · m -1 ~40mN · m -1} . 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 0.1 to 1.5. is required.

  Alternatively, by selecting a fluorine-based polymer that is extracted by the solvent that forms the upper layer when the upper layer is applied, it is not unevenly distributed on the lower layer surface (= interface), so that the adhesion between the upper layer and the lower layer is provided. The surface energy of the light-scattering layer before coating the low refractive index layer can be reduced by preventing the surface free energy from being lowered, which can maintain the surface uniformity even during high-speed coating and can provide an antireflection film with high scratch resistance. The purpose can also be achieved by controlling the range. Examples of such materials include an acrylic resin, a methacrylic resin, and a vinyl monomer copolymerizable therewith, containing a repeating unit corresponding to a fluoroaliphatic group-containing monomer represented by the following general formula 5 And a copolymer.

(Ii) Fluoroaliphatic group-containing monomer represented by the following general formula 5

In the general formula 5, R ¹⁶ represents a hydrogen atom, a halogen atom or a methyl group, more preferably a hydrogen atom or a methyl group. X represents an oxygen atom, a sulfur atom or —N (R ¹⁷ ) —, more preferably an oxygen atom or —N (R ¹⁷ ) —, and still more preferably an oxygen atom. m represents an integer of 1 to 6, and n represents an integer of 1 to 18. R ¹⁷ represents a hydrogen atom or an optionally substituted alkyl group having 1 to 8 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and further preferably a hydrogen atom or a methyl group. X is preferably an oxygen atom.
M in the general formula 5 represents an integer of 1 to 6, more preferably 1 to 3, and still more preferably 1.
N in the general formula 5 represents an integer of 1 to 18, more preferably 4 to 12, and still more preferably 6 to 8.
Further, two or more kinds of fluoroaliphatic group-containing monomers represented by the general formula 5 may be contained in the fluoropolymer as a constituent component.

(Ii) Monomer represented by the following general formula 6 copolymerizable with the above (i)

In the general formula 6, R ¹⁸ represents a hydrogen atom, a halogen atom or a methyl group, more preferably a hydrogen atom or a methyl group. Y represents an oxygen atom, a sulfur atom or —N (R ²⁰ ) —, more preferably an oxygen atom or —N (R ²⁰ ) —, and still more preferably an oxygen atom. R ²⁰ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and further preferably a hydrogen atom or a methyl group.
R ¹⁹ is a C 1-20 linear, branched or cyclic alkyl group which may have a substituent, an alkyl group containing a poly (alkyleneoxy) group, and an aromatic group which may have a substituent. (For example, a phenyl group or a naphthyl group). A linear, branched or cyclic alkyl group having 1 to 12 carbon atoms or an aromatic group having 6 to 18 carbon atoms is more preferable, and a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms is more preferable. .

  Hereinafter, an example of a specific structure of a fluorine-based polymer including a repeating unit corresponding to the fluoroaliphatic group-containing monomer represented by the general formula 5 is shown, but the present invention is not limited thereto. In addition, the number in a formula shows the molar ratio of each monomer component. Mw represents a mass average molecular weight.

  Further, if the surface energy is prevented from being lowered when the low refractive index layer is overcoated on the light scattering layer, the deterioration of the antireflection performance can be prevented. When coating the light scattering layer, the surface tension of the coating solution is lowered using a fluoropolymer to improve surface uniformity and maintain high productivity by high-speed coating. After coating the light scattering layer, corona treatment, UV treatment, heat treatment, saponification Corona treatment is particularly preferred using surface treatment methods such as treatment and solvent treatment, but the surface energy of the light scattering layer before coating the low refractive index layer is controlled within the above range by preventing the surface free energy from decreasing. You can also achieve your goals.

In addition, the present inventors have confirmed that the intensity distribution of scattered light measured with a goniophotometer correlates with the viewing angle improvement effect. That is, the more the light emitted from the backlight is diffused by the light diffusion film installed on the polarizing plate surface on the viewing side, the better the viewing angle characteristics. However, if it is diffused too much, backscattering will increase and the front luminance will decrease, or the scattering will be too great and the image clarity will deteriorate. Therefore, it is necessary to control the scattered light intensity distribution within a certain range. Therefore, as a result of intensive studies, in order to achieve the desired visual characteristics, the scattered light intensity at 30 °, which correlates particularly with the visual angle improvement effect, is 0.01 with respect to the light intensity at the output angle 0 ° of the scattered light profile. % To 0.2% is preferable, and 0.02% to 0.15% is more preferable.
The scattered light profile can be measured using the automatic variable angle photometer GP-5 manufactured by Murakami Color Research Laboratory Co., Ltd. for the created light scattering film.

  Moreover, you may add a thixotropic agent in the coating composition for forming the light-scattering layer of this invention. Examples of the thixotropic agent include silica and mica of 0.1 μm or less. In general, the content of these additives is preferably about 1 to 10 parts by mass with respect to 100 parts by mass of the ultraviolet curable resin.

[High refractive index layer, middle refractive index layer]
In the antireflection film of the present invention, a high refractive index layer or a medium refractive index layer can be provided in order to impart better antireflection performance.
The refractive index of the high refractive index layer is 1.55 to 2.40, and if there is a layer within this range, it can be said that the high refractive index layer in the present invention exists. The range of this refractive index is a range called a so-called high refractive index layer or medium refractive index layer, but in the following specification, these layers may be collectively referred to as a high refractive index layer.
When a high refractive index layer and a medium refractive index layer are mixed, a layer having a refractive index higher than that of the support, light scattering layer, and medium refractive index layer is referred to as a high refractive index layer, and the refractive index is determined as a support, light A layer higher than the scattering layer and the middle refractive index layer and lower than the high refractive index layer is referred to as a middle refractive index layer. The refractive index can be adjusted as appropriate by adjusting the amount of inorganic fine particles to be added and the amount of binder used.

<Inorganic fine particles mainly composed of titanium dioxide>
The high refractive index layer contains inorganic fine particles mainly composed of titanium dioxide containing at least one element selected from cobalt, aluminum, and zirconium. The main component means a component having the largest content (mass%) among the components constituting the particles.
The inorganic fine particles mainly composed of titanium dioxide in the present invention preferably have a refractive index of 1.90 to 2.80, and most preferably 2.20 to 2.80. The mass average diameter of the primary particles is preferably 1 to 200 nm, more preferably 2 to 100 nm, and particularly preferably 2 to 80 nm.

By incorporating at least one element selected from Co, Al and Zr into inorganic fine particles mainly composed of titanium dioxide, the photocatalytic activity of titanium dioxide can be suppressed, and the weather resistance of the high refractive index layer is improved. can do.
The inorganic fine particles mainly composed of titanium dioxide used in the present invention may be surface-treated. The surface treatment is performed using an inorganic compound containing cobalt, an inorganic compound such as Al (OH) ₃ or Zr (OH) ₄ , or an organic compound such as a silane coupling agent. The inorganic fine particles mainly composed of titanium dioxide of the present invention may have a core / shell structure by surface treatment as described in JP-A No. 2001-166104.
The shape of the inorganic fine particles mainly composed of titanium dioxide contained in the high refractive index layer is preferably a rice grain shape, a spherical shape, a cubic shape, a spindle shape or an indefinite shape, and particularly preferably an indefinite shape or a spindle shape. is there.

<Dispersant>
A dispersant can be used for dispersing the inorganic fine particles. For dispersion, it is particularly preferable to use a dispersant having an anionic group.
As the anionic group, a group having an acidic proton such as a carboxyl group, a sulfonic acid group (and a sulfo group), a phosphoric acid group (and a phosphono group), or a sulfonamide group, or a salt thereof is effective. A sulfonic acid group, a phosphoric acid group and a salt thereof are preferable, and a carboxyl group and a phosphoric acid group are particularly preferable. The number of anionic groups contained in the dispersant per molecule may be one or more, but it is preferably 2 or more on average, more preferably 5 or more, and particularly preferably 10 It is more than one. Multiple types of anionic groups may be contained in one molecule. Furthermore, the dispersant preferably contains a cross-linkable or polymerizable functional group.

<High refractive index layer and formation method thereof>
The inorganic fine particles mainly composed of titanium dioxide used for the high refractive index layer are used for forming the high refractive index layer in a dispersion state.
In the dispersion of the inorganic fine particles, it is dispersed in a dispersion medium in the presence of the dispersant.
As the dispersion medium, a liquid having a boiling point of 60 to 170 ° C. is preferably used. Examples of the dispersion medium include water, alcohol, ketone, ester, aliphatic hydrocarbon, halogenated hydrocarbon, aromatic hydrocarbon, amide, ether, ether alcohol. Toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and butanol are preferred.
Particularly preferred dispersion media are methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.

The inorganic fine particles are dispersed using a disperser. Examples of dispersers include sand grinder mills (eg, pin bead mills), high speed impeller mills, pebble mills, roller mills, attritors and colloid mills. A sand grinder mill and a high-speed impeller mill are particularly preferred. Further, preliminary dispersion processing may be performed. Examples of the disperser used for the preliminary dispersion treatment include a ball mill, a three-roll mill, a kneader, and an extruder.
The inorganic fine particle dispersion is preferably made as fine as possible in the dispersion medium, and has a mass average diameter of 1 to 200 nm. Preferably it is 5-150 nm, More preferably, it is 10-100 nm, Most preferably, it is 10-80 nm.
By refining the inorganic fine particles to 200 nm or less, a high refractive index layer that does not impair the transparency can be formed.

  The high-refractive index layer used in the present invention is preferably a dispersion containing inorganic fine particles dispersed in a dispersion medium as described above, preferably a binder precursor necessary for matrix formation (the above-mentioned antiglare hard coat layer and The same), a photopolymerization initiator or the like to form a coating composition for forming a high refractive index layer, and a coating composition for forming a high refractive index layer on a transparent support, It is preferably formed by curing by a crosslinking reaction or a polymerization reaction (for example, a polyfunctional monomer or a polyfunctional oligomer).

  It is preferable to use a photopolymerization initiator for the polymerization reaction of the photopolymerizable polyfunctional monomer. As the photopolymerization initiator, a photoradical polymerization initiator and a photocationic polymerization initiator are preferable, and a photoradical polymerization initiator is particularly preferable. As the radical photopolymerization initiator, the same one as the above-mentioned antiglare hard coat layer is used.

In the high refractive index layer, the binder preferably further has a silanol group. When the binder further has a silanol group, the physical strength, chemical resistance, and weather resistance of the high refractive index layer are further improved.
For example, a silanol group may be formed by adding a compound having a cross-linkable or polymerizable functional group to the coating composition for forming the high refractive index layer, and coating the coating composition on a transparent support. Monomers, polyfunctional oligomers, and the like can be introduced into the binder by a crosslinking reaction or a polymerization reaction.

  In the high refractive index layer, the binder preferably has an amino group or a quaternary ammonium group. A monomer having an amino group or a quaternary ammonium group maintains good dispersibility of the inorganic fine particles in the high refractive index layer, and can produce a high refractive index layer excellent in physical strength, chemical resistance, and weather resistance. .

  The crosslinked or polymerized binder has a structure in which the main chain of the polymer is crosslinked or polymerized. Examples of the polymer main chain include polyolefin (saturated hydrocarbon), polyether, polyurea, polyurethane, polyester, polyamine, polyamide and melamine resin. A polyolefin main chain, a polyether main chain and a polyurea main chain are preferable, a polyolefin main chain and a polyether main chain are more preferable, and a polyolefin main chain is most preferable.

  The binder is preferably a copolymer having a repeating unit having an anionic group and a repeating unit having a crosslinked or polymerized structure. The proportion of the repeating unit having an anionic group in the copolymer is preferably 2 to 96 mol%, more preferably 4 to 94 mol%, and most preferably 6 to 92 mol%. The repeating unit may have two or more anionic groups. The proportion of the repeating unit having a crosslinked or polymerized structure in the copolymer is preferably 4 to 98 mol%, more preferably 6 to 96 mol%, and most preferably 8 to 94 mol%.

The high refractive index layer can contain fine inorganic fine particles in addition to the inorganic fine particles mainly composed of titanium dioxide. As the other inorganic fine particles, the inorganic fine particles contained in the antiglare hard coat layer may be used, and are preferably finely dispersed. The preferable post-dispersion particle size and primary particle size are the antiglare property. As described in the column of the hard coat layer.
The content of the inorganic fine particles in the high refractive index layer is preferably 10 to 90% by mass, more preferably 15 to 80% by mass, and particularly preferably 15 to 75% by mass with respect to the mass of the high refractive index layer. . Two or more inorganic fine particles may be used in combination in the high refractive index layer.
When the low refractive index layer is provided on the high refractive index layer, the refractive index of the high refractive index layer is preferably higher than the refractive index of the transparent support.
The high refractive index layer contains an ionizing radiation curable compound containing an aromatic ring, an ionizing radiation curable compound containing a halogenated element other than fluorine (for example, Br, I, Cl, etc.), and atoms such as S, N, P, etc. Binders obtained by crosslinking or polymerization reaction such as ionizing radiation curable compounds can also be preferably used.
In order to construct an antireflection film by constructing a low refractive index layer on a high refractive index layer, the refractive index of the high refractive index layer is preferably 1.55 to 2.40, more preferably 1.60 to 2.20, more preferably 1.65 to 2.10, and most preferably 1.80 to 2.00.

In addition to the above components (inorganic fine particles, polymerization initiators, photosensitizers, etc.), the high refractive index layer includes resins, surfactants, antistatic agents, coupling agents, thickeners, anti-coloring agents, and coloring. Agents (pigments, dyes), anti-glare imparting particles, antifoaming agents, leveling agents, flame retardants, ultraviolet absorbers, infrared absorbers, adhesion promoters, polymerization inhibitors, antioxidants, surface modifiers, conductivity It is also possible to add metal fine particles.
The film thickness of the high refractive index layer can be appropriately designed depending on the application. When using a high refractive index layer as an optical interference layer described later, the thickness is preferably 30 to 200 nm, more preferably 50 to 170 nm, and particularly preferably 60 to 150 nm.

  In the formation of the high refractive index layer, the crosslinking reaction or the polymerization reaction of the ionizing radiation curable compound is performed with an oxygen concentration of 10% by volume or less, preferably an oxygen concentration of 6% by volume or less, particularly preferably an oxygen concentration of 2% by volume. Hereinafter, it is most preferable to carry out in an atmosphere of 1% by volume or less.

<Inorganic filler>
It is preferable to add an inorganic filler to each layer described above. The inorganic filler added to each layer may be the same or different, and the type and amount added are preferably adjusted appropriately according to the required performance of each layer, such as refractive index, film strength, film thickness, and coatability. .
The inorganic filler used for the low refractive index layer is other than the above-described inorganic fine particles, and the inorganic filler used for the light scattering layer is an inorganic filler other than the above-described translucent particles.

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. Good and more preferable. Further, the kind of the inorganic filler is not particularly limited, but an amorphous one is preferably used, and a metal oxide, nitride, sulfide or halide is preferably used. Is particularly preferred. As metal atoms, Na, K, Mg, Ca, Ba, Al, Zn, Fe, Cu, Ti, Sn, In, W, Y, Sb, Mn, Ga, V, Nb, Ta, Ag, Si, B Bi, Mo, Ce, Cd, Be, Pb, Zr, 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.
Although the usage method of the inorganic filler in this invention is not restrict | limited in particular, For example, it can use in a dry state or can also be used in the state disperse | distributed to water or the organic solvent.

  In the present invention, for the purpose of suppressing aggregation and sedimentation of the inorganic filler, it is also preferable to use a dispersion stabilizer in combination with the coating solution for forming each layer. As the dispersion stabilizer, polyvinyl alcohol, polyvinyl pyrrolidone, cellulose derivative, polyamide, phosphate ester, polyether, surfactant, silane coupling agent, titanium coupling agent and 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. Also, the method of adding the dispersion stabilizer is not particularly limited, but a hydrolyzed one can be added, or a dispersion stabilizer silane coupling agent and an inorganic filler are mixed. Thereafter, a method of further hydrolysis and condensation can be employed, but the latter is more preferable.

<Transparent support>
As the transparent support of the antireflection film of the present invention, a plastic film is preferably used. As the polymer forming the plastic film, cellulose acylate (eg, triacetylcellulose, diacetylcellulose, cellulose acetate propionate, cellulose acetate butyrate, typically TAC-TD80U, TD80UF, etc. manufactured by Fuji Photo Film Co., Ltd.), Polyamide, polycarbonate, polyester (eg, polyethylene terephthalate, polyethylene naphthalate), polystyrene, polyolefin, norbornene resin (Arton: trade name, manufactured by JSR), amorphous polyolefin (ZEONEX: trade name, manufactured by ZEON Corporation), Etc. Among these, triacetyl cellulose, polyethylene terephthalate, norbornene resin, and amorphous polyolefin are preferable, and triacetyl cellulose is particularly preferable.
Cellulose acylate consists of a single layer or a plurality of layers. A single-layer cellulose acylate is prepared by drum casting or band casting disclosed in JP-A No. 7-11055 and the like. The latter cellulose acylate comprising a plurality of layers is a feature of the published patent publication. It is prepared by the so-called co-casting method disclosed in Japanese Utility Model Publication Nos. 61-94725 and 62-43846. That is, the raw material flakes are solvents such as halogenated hydrocarbons (dichloromethane, alcohols (methanol, ethanol, butanol, etc.), esters (methyl formate, methyl acetate, etc.), ethers (dioxane, dioxolane, diethyl ether, etc.), etc. A solution (called a dope) containing various additives such as a plasticizer, an ultraviolet absorber, an anti-degradation agent, a slipping agent and a peeling accelerator as required is dissolved in a horizontal endless. When casting by a dope supply means (called a die) on a support consisting of a metal belt or a rotating drum, a single dope is cast as a single layer, and a high concentration is used as a plurality of 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. A process comprising passed through a drying section by species of the conveying means to remove the solvent.

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

Various cellulose acylate films (films made of triacetyl cellulose and the like) as described above and methods for producing the same are disclosed in the Japan Society for Invention and Technology (Publication No. 2001-1745, published on March 15, 2001, the following public technical bulletin). 2001-1745).

The thickness of the cellulose acylate film is preferably 40 μm to 120 μm. In consideration of handling suitability, coating suitability, etc., about 80 μm is preferable. However, there is a great need for thinning the polarizing plate from the recent trend of thinning the display device. When such a thin cellulose acylate film is used as the transparent support of the antireflection film of the present invention, the solvent, film thickness, crosslinking shrinkage ratio, etc. of the layer directly applied to the cellulose acylate film should be optimized. Therefore, it is preferable to avoid the problems such as handling and application suitability.
<About other layers>
As another layer that may be provided between the transparent support and the light scattering layer of the present invention, an antistatic layer (when there is a demand to reduce the surface resistance value from the display side, there is a problem of dust on the surface, etc. And a hard coat layer (when the light scattering layer alone is insufficient in hardness), a moisture-proof layer, an adhesion improving layer, a rainbow unevenness (interference unevenness) preventing layer, and the like.
These layers can be formed by a known method.

The antireflection film of the present invention can be formed by the following method, but is not limited to this method.
[Adjustment of coating solution]

  First, a coating solution containing components for forming each layer is prepared. In that case, the raise of the moisture content in a coating liquid can be suppressed by suppressing the volatilization amount of a solvent to the minimum. The moisture content in the coating solution is preferably 5% or less, more preferably 2% or less. The suppression of the volatilization amount of the solvent is achieved by improving the sealing property at the time of stirring after putting each material into the tank, minimizing the air contact area of the coating liquid at the time of liquid transfer operation, and the like. Moreover, you may provide the means to reduce the moisture content in a coating liquid during application | coating, or before and behind that.

  Filtration capable of removing almost all foreign substances (pointing to 90% or more) corresponding to the dry film thickness (about 50 nm to 120 nm) of the low refractive index layer directly formed on the coating liquid for forming the light scattering layer It is preferable to Since the translucent particles for imparting light diffusivity are equal to or greater than the film thickness of the low refractive index layer, the filtration should be performed on the intermediate liquid to which all materials other than the translucent particles are added. Is preferred. In addition, when a filter capable of removing foreign substances having a small particle diameter as described above is not available, almost all foreign substances corresponding to the wet film thickness (about 1 to 10 μm) of the layer directly formed thereon are removed. It is preferable to perform filtration. By such means, the point defects of the layer formed directly thereon can be reduced.

Next, a coating solution for forming the light scattering layer is prepared by using a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, a gravure coating method or an extrusion coating method (US Pat. No. 2,681,294). Apply to a transparent support according to the description), and heat and dry. Thereafter, the monomer for forming the light scattering layer is polymerized and cured by light irradiation and / or heating. Thereby, a light scattering layer is formed.
Here, if necessary, the light scattering layer may be formed into a plurality of layers, and smooth light scattering layer application and curing may be performed by the same method before the light scattering layer application.
Next, in the same manner, a coating liquid for forming a low refractive index layer is applied on the light scattering layer, and after drying the solvent, light irradiation and / or heating is performed to form the low refractive index layer. In this way, the antireflection film of the present invention is obtained.

  When forming a light-scattering layer, it is preferable to apply | coat the said coating liquid in the range of 1-20 micrometers as wet coating film thickness directly or via another layer on a base film. Moreover, when forming a low refractive index layer, it is preferable to apply | coat the said liquid in the range of 1-10 micrometers as a wet coating film thickness on a light-scattering layer, and it is apply | coated in the range of 2-5 micrometers. More preferred.

  The light scattering layer and the low refractive index layer are applied directly on the base film or via other layers, and then conveyed in a web to a heated zone to dry the solvent. In this case, the temperature of the drying zone is preferably 25 ° C. to 140 ° C., the first half of the drying zone is relatively low temperature, and the second half is preferably relatively high temperature. However, it is preferably below the temperature at which components other than the solvent contained in the coating composition of each layer start to volatilize. For example, some of the commercially available photo radical generators used in combination with ultraviolet curable resins volatilize around several tens of percent within a few minutes in warm air at 120 ° C. Some acrylate monomers and the like undergo volatilization in warm air at 100 ° C. In such a case, it is preferable that it is below the temperature at which components other than the solvent contained in the coating composition of each layer start to volatilize as described above.

Moreover, the dry wind after apply | coating the coating composition of each layer on a base film is 0.1-2 m / sec on the surface of a coating film, when the solid content concentration of the said coating composition is 1 to 50%. It is preferable to be in the range in order to prevent drying unevenness.
Moreover, after apply | coating the coating composition of each layer on a base film, the temperature difference of the conveyance roll and base film which contacts the surface opposite to the coating surface of a base film in a drying zone is 0 degreeC-20. Within the range of ° C., drying unevenness due to heat transfer unevenness on the transport roll can be prevented, which is preferable.

After the solvent drying zone, the coating is cured by passing through a zone where the coating is cured by ionizing radiation and / or heat on the web. For example, if the coating film is UV curable, it is to cure each layer by irradiating an irradiation amount of ultraviolet rays of 10mJ / cm ² ~1000mJ / cm ² by an ultraviolet lamp preferred. At that time, the irradiation distribution in the width direction of the web is preferably 50 to 100%, more preferably 80 to 100%, including both ends with respect to the central maximum irradiation. Further, when it is necessary to purge nitrogen gas or the like to lower the oxygen concentration in order to promote surface hardening, the oxygen concentration is preferably 0.01% to 5%, and the distribution in the width direction is 2% or less in terms of oxygen concentration. Is preferred.

  In addition, when the curing rate (100-residual functional group content) of the light scattering layer becomes a certain value less than 100%, the low refractive index layer of the present invention is provided on the light scattering layer to reduce the light scattering layer by ionizing radiation and / or heat. When the refractive index layer is cured, if the curing rate of the lower light scattering layer is higher than before the low refractive index layer is provided, the adhesion between the light scattering layer and the low refractive index layer is improved, which is preferable.

  The antireflection film of the present invention produced as described above can be used for a liquid crystal display device by making a polarizing plate using the antireflection film. In this case, it arrange | positions on the outermost surface of a display by providing an adhesive layer on one side. The antireflection film of the present invention is preferably used for at least one of the two protective films sandwiching the polarizing film in the polarizing plate 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.

  When producing a polarizing plate using the antireflection film of the present invention as one of the surface protective films of two polarizing films, the antireflection film is on the side opposite to the side having the antireflection structure. It is preferable to improve the adhesion on the adhesive surface by hydrophilizing the surface of the transparent support, that is, the surface to be bonded to the polarizing film.

[Saponification]
(1) Method of immersing in alkaline solution This is a technique in which an antireflection film is immersed in an alkaline solution under appropriate conditions to saponify all surfaces reactive with alkali on the entire surface of the film. Is preferable from the viewpoint of cost. The alkaline liquid is preferably a sodium hydroxide aqueous solution. A preferred concentration is 0.5 to 3 mol / L, particularly preferably 1 to 2 mol / L. The liquid temperature of a preferable alkali liquid is 30-75 degreeC, Most preferably, it is 40-60 degreeC.
The combination of the saponification conditions is preferably a combination of relatively mild conditions, but can be set depending on the material and configuration of the antireflection film and the target contact angle.
After being immersed in the alkaline solution, it is preferable to sufficiently wash with water or neutralize the alkaline component by immersing in a dilute acid so that the alkaline component does not remain in the film.

By saponification treatment, the surface of the transparent support opposite to the surface having the antireflection layer is hydrophilized. The protective film for polarizing plate is used by adhering the hydrophilic surface of the transparent support to the polarizing film.
The hydrophilized surface is effective for improving the adhesiveness with the adhesive layer mainly composed of polyvinyl alcohol.
In the saponification treatment, the lower the contact angle of water on the surface of the transparent support opposite to the side having the low refractive index layer, the better from the viewpoint of adhesiveness to the polarizing film. Since it is damaged by alkali from the surface having the rate layer to the inner light scattering layer, it is important to set the reaction conditions to the minimum necessary. As an index of the damage received by the antireflection layer due to alkali, when the contact angle to water of the transparent support on the opposite surface is used, particularly when the transparent support is triacetylcellulose, preferably 10 to 50 degrees, More preferably, it is 30 to 50 degrees, and further preferably 40 to 50 degrees. If it is 50 degrees or more, a problem arises in the adhesion to the polarizing film, which is not preferable. On the other hand, if the angle is less than 10 degrees, the damage received by the antireflection film is too large, so that the physical strength is impaired, which is not preferable.

(2) Method of applying alkaline solution As a means for avoiding damage to the antireflection film in the above immersion method, the alkaline solution is applied only to the surface opposite to the surface having the antireflection film under appropriate conditions, heated, An alkaline solution coating method of washing with water and drying is preferably used. The application in this case means that an alkaline solution or the like is brought into contact only with the surface to be saponified, and in addition to the application, it may be carried out by spraying or contacting a belt containing the solution. Including. By adopting these methods, a separate facility and process for applying an alkaline solution are required, which is inferior to the immersion method (1) from the viewpoint of cost. On the other hand, since the alkali solution contacts only the surface to be saponified, the opposite surface can have a layer using a material that is weak against the alkali solution. For example, vapor deposition films and sol-gel films have various effects such as corrosion, dissolution, peeling, etc. caused by alkaline liquids. Is possible.

  In any of the saponification methods (1) and (2), since each layer can be formed by unwinding from a roll-shaped support, a series of operations can be performed in addition to the above-described antireflection film manufacturing process. You can go. Furthermore, the polarizing plate can be produced more efficiently than the same operation with a single wafer by continuously performing the pasting step with the polarizing plate made of the unwound support.

(3) Method of saponification by protecting the antireflection film with a laminate film As in the case of (2) above, when the light scattering layer and / or the low refractive index layer has insufficient resistance to an alkaline solution, After laminating the laminate film on the surface on which the low refractive index layer is formed after forming the layer, the surface of the triacetyl cellulose opposite to the surface on which the low refractive index layer is formed is hydrophilized by immersing in an alkali solution, Thereafter, the laminate film can be peeled off. Even in this method, only the surface opposite to the surface on which the antireflective layer of the triacetyl cellulose film is formed is subjected to the hydrophilization treatment necessary for the polarizing plate protective film without damage to the light scattering layer and the low refractive index layer be able to. Compared with the method (2), there is an advantage that a laminate film is generated as waste, but a device for applying a special alkaline solution is unnecessary.

(4) Method of immersing in an alkali solution after forming up to the light scattering layer Although the light scattering layer is resistant to the alkali solution, if the low refractive index layer is insufficiently resistant to the alkali solution, after forming up to the light scattering layer It is also possible to soak both surfaces in an alkali solution to hydrophilize both sides, and then form a low refractive index layer on the light scattering layer. Although the manufacturing process is complicated, there is an advantage that the interlayer adhesion between the light scattering layer and the low refractive index layer is improved particularly when the low refractive index layer has a hydrophilic group such as a fluorine-containing sol-gel film.

(5) Method of forming an antireflection film on a pre-saponified triacetyl cellulose film A triacetyl cellulose film is preliminarily immersed in an alkaline solution and saponified, either directly or via another layer. A light scattering layer and a low refractive index layer may be formed. In the case of saponification by dipping in an alkali solution, interlayer adhesion between the light scattering layer or other layers and the triacetyl cellulose surface hydrophilized by saponification may deteriorate. In such a case, after the saponification, only the surface on which the light scattering layer or other layer is formed is treated by corona discharge, glow discharge or the like to remove the hydrophilic surface, and then the light scattering layer or other layer. Can be dealt with by forming Further, when the light scattering layer or other layer has a hydrophilic group, the interlayer adhesion may be good.

Below, the polarizing plate using the antireflection film of this invention and the liquid crystal display device using this polarizing plate are demonstrated.
[Polarizer]
The preferable polarizing plate of this invention has the antireflection film of this invention as at least one of the protective film (polarizing plate protective film) of a polarizing film. As described above, the protective film for polarizing plate has a contact angle with water of 10 to 50 degrees on the surface of the transparent support opposite to the side having the antireflection structure, that is, the surface to be bonded to the polarizing film. It is preferable to be in the range.
By using the antireflection film of the present invention as a protective film for a polarizing plate, a polarizing plate having an antireflection function excellent in physical strength and light resistance can be produced, and the cost can be greatly reduced and the display device can be thinned. .
Further, by preparing a polarizing plate using the antireflection film of the present invention as one of the protective films for polarizing plates and an optical compensation film having optical anisotropy described later as the other protective film of the polarizing film, Thus, a polarizing plate capable of improving the contrast in the bright room of the liquid crystal display device and greatly widening the vertical and horizontal viewing angles can be produced.

[Optical compensation layer]
By providing the polarizing plate with an optical compensation layer (retardation layer), the viewing angle characteristics of the liquid crystal display screen can be improved.
A known layer can be used as the optical compensation layer, but it has optical anisotropy made of a compound having a discotic structural unit described in JP-A-2001-100042 in terms of widening the viewing angle. An optical compensation layer having a layer, wherein the angle formed by the discotic compound and the transparent support varies with the distance from the transparent support, is preferable.
The angle preferably increases as the distance from the transparent support surface side of the optically anisotropic layer made of the discotic compound increases.
When the optical compensation layer is used as a protective film for a polarizing film, the surface on the side to be bonded to the polarizing film is preferably saponified, and is preferably performed according to the saponifying process.

[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 whose absorption axis is neither parallel nor perpendicular to the longitudinal direction is produced by the following method.
That is, with a polarizing film stretched by applying tension while holding both ends of a continuously supplied polymer film by a holding means, stretched at least 1.1 to 20.0 times in the film width direction, The progress of the film is such that the difference between the moving speeds in the longitudinal direction of the holding device is within 3%, and the angle formed between the moving direction of the film at the exit of the process of holding both ends of the film and the substantial stretching direction of the film is inclined by 20 to 70 °. It can be produced by a stretching method in which the direction is bent while holding both ends of the film. In particular, those inclined by 45 ° are preferably used from the viewpoint of productivity.

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

<Liquid crystal display device>
The antireflection film of the present invention can be applied to an image display device such as a liquid crystal display device (LCD), a plasma display panel (PDP), an electroluminescence display (ELD), or a cathode ray tube display device (CRT). Since the antireflection film of the present invention has a transparent support, the transparent support side is adhered to the image display surface of the image display device.

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

  The VA mode liquid crystal cell includes (1) a narrowly defined VA mode liquid crystal cell in which rod-like liquid crystalline molecules are aligned substantially vertically when no voltage is applied, and substantially horizontally when a voltage is applied (Japanese Patent Laid-Open No. Hei 2-). (2) In addition to (2) Liquid crystal cell (SID97, Digest of tech. Papers (Preliminary Collection) 28 (1997) 845 in which the VA mode is converted into a multi-domain (MVA mode) for viewing angle expansion ), (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 (Preliminary collections 58-59 of the Japan Liquid Crystal Society) (1998)) and (4) SURVAVAL mode liquid crystal cells (announced at LCD International 98).

  The OCB mode liquid crystal cell is a liquid crystal display device using a bend alignment mode liquid crystal cell in which rod-like liquid crystalline molecules are aligned in a substantially opposite direction (symmetrically) between the upper part and the lower part of the liquid crystal cell. It is disclosed in the specifications of Japanese Patent Nos. 45882525 and 5410422. 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. Therefore, this liquid crystal mode is also called an OCB (Optically Compensatory Bend) liquid crystal mode. The bend alignment mode liquid crystal display device has an advantage of high response speed.

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

  Particularly for TN mode and IPS mode liquid crystal display devices, as described in JP-A-2001-100043, an optical compensation film having an effect of widening the viewing angle is used as a protective film on the back and front surfaces of the polarizing film. By using it on the surface opposite to the antireflection film of the present invention, a polarizing plate having an antireflection effect and a viewing angle expansion effect can be obtained with the thickness of one polarizing plate, which is particularly preferable.

  In order to describe the present invention in detail, examples will be described below, but the present invention is not limited thereto. Unless otherwise specified, “part” and “%” are based on mass.

(Synthesis of perfluoroolefin copolymer (1))

Into a stainless steel autoclave with a stirrer of 100 ml, 40 ml of ethyl acetate, 14.7 g of hydroxyethyl vinyl ether and 0.55 g of dilauroyl peroxide were charged, and the inside of the system was deaerated and replaced with nitrogen gas. Furthermore, 25 g of hexafluoropropylene (HFP) was introduced into the autoclave and the temperature was raised to 65 ° C. The pressure when the temperature in the autoclave reached 65 ° C. was 5.4 kg / cm ² . The reaction was continued for 8 hours while maintaining the temperature, and when the pressure reached 3.2 kg / cm ² , the heating was stopped and the mixture was allowed to cool. When the internal temperature dropped to room temperature, unreacted monomers were driven out, the autoclave was opened, and the reaction solution was taken out. The obtained reaction solution was poured into a large excess of hexane, and the polymer was precipitated by removing the solvent by decantation. Further, this polymer was dissolved in a small amount of ethyl acetate and reprecipitated twice from hexane to completely remove the residual monomer. After drying, 28 g of polymer was obtained. Next, 20 g of the polymer was dissolved in 100 ml of N, N-dimethylacetamide, and 11.4 g of acrylic acid chloride was added dropwise under ice cooling, followed by stirring at room temperature for 10 hours. Ethyl acetate was added to the reaction solution, washed with water, the organic layer was extracted and concentrated, and the resulting polymer was reprecipitated with hexane to obtain 19 g of perfluoroolefin copolymer (1). The resulting polymer had a refractive index of 1.421.

(Preparation of sol solution a)
A stirrer, a reactor equipped with a reflux condenser, 120 parts of methyl ethyl ketone, 100 parts of acryloyloxypropyltrimethoxysilane (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.), 3 parts of diisopropoxyaluminum ethyl acetoacetate were added and mixed. After that, 30 parts of ion-exchanged water was added and reacted at 60 ° C. for 4 hours, and then cooled to room temperature to obtain sol solution a. The mass average molecular weight was 1600, and among the components higher than the oligomer component, the component having a molecular weight of 1000 to 20000 was 100%. Further, from the gas chromatography analysis, the raw material acryloyloxypropyltrimethoxysilane did not remain at all.

(Preparation of sol liquid b)
After cooling to room temperature after the reaction, a sol solution b was obtained in the same manner as the sol solution a except that 6 parts of acetylacetone was added.

(Preparation of coating solution A for light scattering layer)
50 g of a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (PETA, Nippon Kayaku Co., Ltd.) was diluted with 38.5 g of toluene. Furthermore, 2 g of a polymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) was added and mixed and stirred. The refractive index of the coating film obtained by applying this solution and curing with ultraviolet rays was 1.51.
Further, a 30% toluene dispersion of crosslinked polystyrene particles having an average particle size of 3.5 μm (refractive index 1.61, SX-350, manufactured by Soken Chemical Co., Ltd.) dispersed in this solution for 20 minutes at 10,000 rpm with a Polytron disperser. Add 13.3 g of a 30% toluene dispersion of 1.7 g and crosslinked acrylic-styrene particles having an average particle size of 3.5 μm (refractive index 1.55, manufactured by Soken Chemical Co., Ltd.) 0.75 g of an agent (FP-107) and 10 g of a silane coupling agent (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.) were added to obtain a finished solution.
The mixed solution was filtered through a polypropylene filter having a pore diameter of 30 μm to prepare a coating solution A for a light scattering layer.

(Preparation of coating solution B for light scattering layer)
285 g of commercially available zirconia-containing UV curable hard coat liquid (Desolite Z7404, manufactured by JSR Corporation, solid content concentration of about 61%, ZrO ₂ content of solid content of about 70%, polymerizable monomer, polymerization initiator contained), dipenta 85 g of a mixture of erythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.) was mixed, and further diluted with 60 g of methyl isobutyl ketone and 17 g of methyl ethyl ketone. Furthermore, 28 g of a silane coupling agent (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.) was mixed and stirred. The refractive index of the coating film obtained by applying this solution and curing with ultraviolet rays was 1.61.
Further, a 30% methyl isobutyl ketone dispersion of classified strengthened crosslinked PMMA particles (refractive index: 1.49, MXS-300, manufactured by Soken Chemical Co., Ltd.) having an average particle size of 3.0 μm was added to this solution at 10,000 rpm with a Polytron disperser. 35 g of a dispersion dispersed for 20 minutes was added, and then a 30% methyl ethyl ketone dispersion of silica particles having an average particle diameter of 1.5 μm (refractive index 1.46, Seahosta KE-P150, manufactured by Nippon Shokubai Co., Ltd.) 90 g of a dispersion dispersed at 10,000 rpm for 30 minutes was added, and finally 0.12 g of a fluorine-based surface modifier (FP-1) was mixed and stirred to obtain a finished solution.
The mixed solution was filtered through a polypropylene filter having a pore diameter of 30 μm to prepare a coating solution B for a light scattering layer.

(Preparation of coating solution C for light scattering layer)
In the light scattering layer coating solution B, instead of silica particles having an average particle diameter of 1.5 μm, classified reinforcing highly crosslinked PMMA particles having an average particle diameter of 1.5 μm (MXS-150H, a crosslinking agent ethylene glycol dimethacrylate, an amount of crosslinking agent of 30 %, A coating solution C for a light scattering layer was prepared in the same manner as the coating liquid A, including the addition amount, except that 130 g of 30% methyl ethyl ketone dispersion liquid manufactured by Soken Chemical Co., Ltd., refractive index 1.49) was used. .

(Preparation of coating solution D for light scattering layer)
In the light scattering layer coating liquid A, instead of crosslinked polystyrene particles having an average particle size of 3.5 μm and crosslinked acrylic-styrene particles having an average particle size of 3.5 μm, classified strengthening highly crosslinked PMMA particles (crosslinked) Coating solution D for light scattering layer in the same manner as coating solution A, including the added amount, except that 15 g of 30% toluene dispersion of the agent ethylene glycol dimethacrylate, crosslinker amount 40%, refractive index 1.50) was used. It was created.

(Adjustment of coating solution A for low refractive index layer)
Thermally crosslinkable fluorine-containing polymer having a refractive index of 1.42 (JN7228, solid content concentration 6%, manufactured by JSR Corporation) 13 g, silica sol (silica, MEK-ST particle size difference, average particle size 45 nm, solid content concentration 30 %, Manufactured by Nissan Chemical Co., Ltd.) 1.3 g, sol solution 0.6 g, methyl ethyl ketone 5 g, and cyclohexanone 0.6 g were added. After stirring, the mixture was filtered with a polypropylene filter having a pore size of 1 μm for a low refractive index layer. A coating solution A was prepared. The refractive index of the layer formed with this coating solution was 1.43.

(Adjustment of coating liquid B for low refractive index layer)
In the coating liquid A for the low refractive index layer, the coating liquid including the addition amount was used except that 1.95 g of hollow silica sol (refractive index 1.31, average particle size 60 nm, solid content concentration 20%) was used instead of silica sol. In the same manner as A, a coating solution B for a low refractive index layer was prepared. The refractive index of the layer formed with this coating solution was 1.38.

(Preparation of coating solution C for low refractive index layer)
Thermally crosslinkable fluorine-containing polymer having a refractive index of 1.42 (JN7228, solid content concentration 6%, manufactured by JSR Corporation) 15 g, silica sol (silica, MEK-ST, average particle size 15 nm, solid content concentration 30%, Nissan Chemical) 0.6 g, silica sol (silica, MEK-ST particle size difference, average particle size 45 nm, solid content concentration 30%, manufactured by Nissan Chemical Co., Ltd.) 0.8 g, sol solution a 0.4 g and methyl ethyl ketone 3 g Then, 0.6 g of cyclohexano was added, stirred, and then filtered through a polypropylene filter having a pore size of 1 μm to prepare a coating solution C for a low refractive index layer. The refractive index of the layer formed with this coating solution was 1.43.

(Preparation of coating solution D for low refractive index layer)
15.2 g of perfluoroolefin copolymer (1), silica sol (silica, MEK-ST with different particle size, average particle size 45 nm, solid content concentration 30%, manufactured by Nissan Chemical Industries) 1.4 g, reactive silicone X-22-164B (trade name; manufactured by Shin-Etsu Chemical Co., Ltd.) 0.3 g, sol solution a 7.3 g, photopolymerization initiator (Irgacure 907 (trade name), manufactured by Ciba Geigy) 0.76 g, methyl ethyl ketone 301 g, cyclohexanone After adding 9.0 g and stirring, it was filtered through a polypropylene filter having a pore size of 5 μm to prepare a coating solution D for a low refractive index layer. The refractive index of the layer formed with this coating solution was 1.44.

(Adjustment of coating liquid E for low refractive index layer)
In the coating liquid D for the low refractive index layer, the coating liquid including addition amount is used except that 1.95 g of hollow silica sol (refractive index 1.31, average particle size 60 nm, solid content concentration 20%) is used instead of silica sol. In the same manner as D, a coating solution E for a low refractive index layer was prepared. The refractive index of the layer formed by this coating solution was 1.396.

(Adjustment of coating liquid F for low refractive index layer)
Add 13 g of heat-crosslinkable fluoropolymer having a refractive index of 1.42 (JN7228, solid concentration 6%, manufactured by JSR Corporation) and 0.3 g of cyclohexanone, and after stirring, filter through a polypropylene filter with a pore size of 1 μm. Thus, a coating solution F for a low refractive index layer was prepared. The refractive index of the layer formed with this coating solution was 1.42.

[Example 1]
(1) Coating of light scattering layer A triacetyl cellulose film (TAC-TD80U, manufactured by Fuji Photo Film Co., Ltd.) having a thickness of 80 μm is unwound in a roll form, and the coating liquid A for the light scattering layer is drawn into a wire. Using a gravure roll with a diameter of 40 mm and a doctor blade with a gravure pattern of several 180 lines / inch and a depth of 40 μm, it was applied at a gravure roll rotation speed of 30 rpm and a conveying speed of 30 m / min, and dried at 60 ° C. for 150 seconds. Then, using a 160 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) under a nitrogen purge, the coating layer is cured by irradiating ultraviolet rays with an illuminance of 400 mW / cm ² and an irradiation amount of 250 mJ / cm ^2. A functional layer having a thickness of 6 μm was formed and wound up.

(2) Coating of low refractive index layer The triacetyl cellulose film coated with the functional layer is unwound again, and the coating liquid A for low refractive index layer is formed into a gravure pattern with 180 lines / inch and a depth of 40 μm. Using a micro gravure roll having a diameter of 50 mm and a doctor blade, it was applied under the conditions of a gravure roll rotation speed of 30 rpm and a conveyance speed of 15 m / min, dried at 120 ° C. for 150 seconds, and further dried at 140 ° C. for 8 minutes. Using a 240 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) under a nitrogen purge, ultraviolet rays having an illuminance of 400 mW / cm ² and an irradiation amount of 900 mJ / cm ² are irradiated, and a low refractive index layer having a thickness of 100 nm And wound up.
(Saponification treatment of antireflection film)
After the film formation, the sample 1 was subjected to the following treatment.
A 1.5 mol / l aqueous sodium hydroxide solution was prepared and kept at 55 ° C. A 0.01 mol / l dilute sulfuric acid aqueous solution was prepared and kept at 35 ° C. The prepared antireflection film was immersed in the aqueous sodium hydroxide solution for 2 minutes, and then immersed in water to sufficiently wash away the aqueous sodium hydroxide solution. Subsequently, after being immersed in the dilute sulfuric acid aqueous solution for 1 minute, it was immersed in water to sufficiently wash away the dilute sulfuric acid aqueous solution. Finally, the sample was thoroughly dried at 120 ° C.
In this way, a saponified antireflection film was produced. This is designated as Example 1 Sample 1.

(Evaluation of antireflection film)
About the obtained film, the following items were evaluated. The results are shown in Table 1.

(1) Average reflectance Using a spectrophotometer (manufactured by JASCO Corporation), the spectral reflectance at an incident angle of 5 ° was measured in a wavelength region of 380 to 780 nm. For the results, an integrating sphere average reflectance of 450 to 650 nm was used.

(2) Scratch resistance: Steel wool scratch resistance evaluation (dry steel)
A rubbing test was conducted using a rubbing tester under the following conditions.
Evaluation environmental conditions: 25 ° C., 60% RH
Rubbing material: Steel wool (manufactured by Nippon Steel Wool Co., Ltd., Grade No. 0000) was wound around the rubbing tip (1 cm × 1 cm) of a tester in contact with the sample, and the band was fixed so as not to move.
Moving distance (one way): 13 cm, rubbing speed: 13 cm / sec, load: 500 g / cm ² , tip contact area: 1 cm × 1 cm, rubbing frequency: 10 reciprocations.
An oil-based black ink was applied to the back side of the rubbed sample and visually observed with reflected light, and scratches on the rubbed portion were evaluated according to the following criteria.
A: Even when viewed very carefully, no scratches are visible.
○: Slightly weak scratches are visible when viewed very carefully.
○ △: Weak scratches are visible.
Δ: Moderate scratches are visible.
Δ × ˜ ×: There is a scratch that can be seen at first glance.

(3) Scratch resistance; water swab rub resistance evaluation (wet swab)
A rubbing tester rubbed with a cotton swab fixed to the tip of the sample, and fixed the top and bottom of the sample with a clip in a smooth pan. The rubbing test was performed by changing the number of rubbing. The rubbing conditions are as follows.
Rubbing distance (one way): 1 cm, rubbing speed: about 2 reciprocations / second The sample after rubbing was observed, and the rubbing resistance was evaluated as follows according to the number of film peeling.
0-10 round trip film peeling ×
Film peeling after 10 to 30 round trips
30-50 reciprocating film peeling
50-100 reciprocating film peeling
100-150 round trip film peeling ○
No film peeling even after 150 reciprocations ◎

[Example 1 Sample 2 to Sample 7, Sample 8 (Comparative Example)]
As described in Table 1, in Sample 1 of Example 1, the light scattering layer coating liquid was changed to the light scattering layer coating liquid (B, C, D) or the low refractive index layer coating liquids (B to F). Except for changing, it was produced and evaluated in the same manner as Sample 1 in Example 1. The results are shown in Table 1.
The thickness of the light scattering layer after drying was 3.4 μm.

From the results shown in Table 1, the following is clear.
In the antireflection film of the present invention, an antireflection film having excellent surface uniformity and high scratch resistance can be obtained with high productivity.

Example 1 In Samples 1 and 4-7, when the diluent solvent used in the light scattering layer coating liquid A was made to have a solvent composition of toluene / anone = 85/15 and toluene / anone = 70/30 instead of toluene, the ratio of anone As the film height increased, the interface adhesion between the transparent support / light scattering layer was strengthened, and the scratch resistance was improved.
In Example 1 samples 1 to 7, when b was used in place of the organosilane sol solution a used in the low refractive index layer coating solution, the stability of the coating solution with time was improved and suitability for continuous coating. Became high.
In place of the thermally crosslinkable fluoropolymer used in the low refractive index layer coating solutions A, B and C, a thermally crosslinkable fluoropolymer having a refractive index of 1.44 (JTA-113, solid content concentration 6%) , Manufactured by JSR Co., Ltd.), the scratch resistance was remarkably improved.
Further, 10 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.) was added to the low refractive index layer coating liquids D and E. Improved significantly.

[Example 2]
The PVA film was immersed in an aqueous solution of 2.0 g / l iodine and 4.0 g / l potassium iodide at 25 ° C. for 240 seconds, and further immersed in an aqueous solution of boric acid 10 g / l at 25 ° C. for 60 seconds. It introduced into the tenter drawing machine of the form of FIG. 2 described in 2002-86554, it extended | stretched 5.3 time, the tenter was bent like FIG. 2 with respect to the extending | stretching direction, and the width | variety was kept constant hereafter. After drying in an atmosphere of 80 ° C., it was detached from the tenter. The difference in transport speed between the left and right tenter clips was less than 0.05%, and the angle between the center line of the introduced film and the center line of the film sent to the next process was 46 °. Here, | L1-L2 | is 0.7 m, W is 0.7 m, and | L1-L2 | = W. The substantial stretching direction Ax-Cx at the tenter outlet was inclined by 45 ° with respect to the center line 22 of the film sent to the next process. Wrinkles and film deformation at the tenter exit were not observed.
Furthermore, it was bonded to Fuji Photo Film Co., Ltd. Fujitac (cellulose triacetate, retardation value 3.0 nm), which was saponified with an aqueous solution of PVA (Pura-117H, Kuraray Co., Ltd.) 3%, and further 80 ° C. And dried to obtain a polarizing plate having an effective width of 650 mm. The absorption axis direction of the obtained polarizing plate was inclined 45 ° with respect to the longitudinal direction. The polarizing plate had a transmittance at 550 nm of 43.7% and a polarization degree of 99.97%. Further, as shown in FIG. 2, when the substrate was cut into a size of 310 × 233 mm, a polarizing plate having an absorption efficiency of 91.5% and a 45 ° absorption axis inclined with respect to the side was obtained.
Next, Example 1 Samples 1 to 7 (saponified) films were bonded to the polarizing plate to prepare a polarizing plate with antireflection. Using this polarizing plate, a liquid crystal display device having a low refractive index layer as the outermost layer was produced. As a result, there was no reflection of external light, and an excellent contrast was obtained. Had good visibility.

[Example 3]
An 80 μm-thick triacetylcellulose film (TAC-TD80U, manufactured by Fuji Photo Film Co., Ltd.), which was immersed in a 1.5 mol / l, 55 ° C. NaOH aqueous solution for 2 minutes, then neutralized and washed with water, and Examples A polarizing plate was prepared by adhering and protecting both sides of a polarizer prepared by adsorbing iodine to polyvinyl alcohol on the backside saponified triacetylcellulose film of Sample 1 and stretching. A liquid crystal display device of a notebook personal computer equipped with a transmissive TN liquid crystal display device (Sumitomo 3M Co., Ltd., which is a polarization separation film having a polarization selection layer) so that the anti-reflection film side is the outermost surface. When the polarizing plate on the viewing side of D-BEF made of the product between the backlight and the liquid crystal cell was replaced, a display device with very high display quality was obtained with very little background reflection.

[Example 4]
Example 1 A discotic structural unit as a protective film on the liquid crystal cell side of the polarizing plate on the viewing side of the transmissive TN liquid crystal cell to which samples 1 to 7 are attached, and a protective film on the liquid crystal cell side of the polarizing plate on the backlight side An optical compensation layer in which the disc surface is inclined with respect to the transparent support surface and the angle formed by the disc surface of the discotic structural unit and the transparent support surface varies in the depth direction of the optical anisotropic layer. When using the viewing angle widening film (wide view film SA 12B, manufactured by Fuji Photo Film Co., Ltd.), it has excellent contrast in bright rooms, very wide viewing angles in the vertical and horizontal directions, and extremely excellent visibility. A liquid crystal display device with high display quality was obtained.
Further, using an automatic goniophotometer GP-5 type (manufactured by Murakami Color Research Laboratory Co., Ltd.), the film was placed perpendicular to the incident light, and the scattered light profile was measured in all directions. From this profile, the scattered light intensity at 30 ° C. with respect to an emission angle of 0 ° was obtained. Example 1 Samples 2 and 3 (light scattering layer coating liquids B and C) have a scattered light intensity of 30 ° with respect to an emission angle of 0 ° of 0.06%. It was a very good liquid crystal display device with improved corners and left-right yellowness. As a comparison, in the film of Sample 8 (Comparative Example), the scattered light intensity at 30 ° with respect to the output angle of 0 ° was substantially 0%, and the effect of improving the downward viewing angle and improving the yellowness was not obtained at all.

[Example 5]
Example 1 When samples 1 to 7 were bonded to a glass plate on the surface of an organic EL display device via an adhesive, reflection on the glass surface was suppressed, and a display device with high visibility was obtained.

[Example 6]
Example 1 A polarizing plate with a single-sided antireflection film was prepared using the polarizing plates prepared in Samples 1 to 7 and Example 2, and λ / 4 was formed on the opposite side of the polarizing plate having the antireflection film. When the plates were bonded together and attached to the glass plate on the surface of the organic EL display device, the surface reflection and the reflection from the inside of the surface glass were cut, and a display with extremely high visibility was obtained.

FIG. 1 is a cross-sectional view schematically showing the layer structure of the antireflection film of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Antireflection film 2 Transparent support 3 Light scattering layer 4 Low refractive index layer 5 Translucent particle

Claims (4)

An antireflection film having at least a light scattering layer and a low refractive index layer on a transparent support,
The light scattering layer is a layer formed by dispersing at least one kind of translucent particles having an average particle diameter of 0.5 to 5 μm in a translucent resin, and the translucent particles, the translucent resin, The refractive index difference is 0.02 to 0.2, and the light-transmitting particles are contained in 3 to 30% by mass in the total solid content of the light scattering layer,
The low refractive index layer is a layer having a refractive index of 1.30 to 1.55 formed by applying a curable composition mainly composed of a fluorine-containing polymer containing a crosslinkable or polymerizable functional group. An antireflection film characterized by that.   2. The fluorine-containing polymer is a copolymer comprising a fluorine-containing vinyl monomer polymerization unit and a polymerization unit having a (meth) acryloyl group in a side chain, and a main chain consisting of only carbon atoms. The antireflection film as described. The curable composition comprises (A) the fluoropolymer, (B) an average particle diameter of 30% to 100% of the thickness of the low refractive index layer, and a refractive index of 1.17 to 1 consisting of a hollow structure. .40 inorganic fine particles, (C) a hydrolyzate of an organosilane compound represented by the following general formula [A] and / or a partial condensate thereof, each produced in the presence of an acid catalyst: The antireflective film according to claim 1, which is a seed-containing curable composition.
Formula [A]
(R ¹⁰ ) _m -Si (X) _4-m
(In the formula, R ¹⁰ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. X represents a hydroxyl group or a hydrolyzable group. M represents an integer of 1 to 3.)   The curable composition further comprises a polyfunctional polymerizable compound containing at least two polymerizable groups selected from radical polymerizable groups and / or cationic polymerizable groups and a polymerization initiator. The antireflection film according to claim 3.

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