JP2010061044A - Anti-reflection film, polarizing plate, and image forming device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an anti-reflection film with a low reflective index layer which does not cause a failure due to whitening, has high abrasion resistance and sufficient anti-reflection effect without causing phase separation, resulting in an irregular face shape. <P>SOLUTION: The anti-reflection film has an anti-glare layer and a low refractive index layer in this order on a transparent support. The low refractive index layer is a cured product having a composition containing the following components (A), (B), (C), (D) and (E): (A) is solid inorganic fine particles with the diameter of 40 to 100 nm; (B) is solid inorganic fine particles with the diameter of 1 to 30 nm; (C) is a photocurable fluorine-containing polymer having an ethylenic unsaturated group; (D) is a photocurable acrylate monomer; and (E) is a photopolymerization initiator. The content of the solid inorganic fine particles (A) is 3.5 to 13 mass% to the whole solid content of the low refractive index layer, the total content of the solid inorganic fine particles (A) and the solid inorganic fine particles (B) is 10 to 40 mass% to the whole solid content of the low refractive index layer, and also, the refractive index of the low refractive index layer is 1.440 to 1.465. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an antireflection film, a polarizing plate, and an image display device.

  In general, an antireflection film is used for an image display device such as a cathode ray tube display (CRT), a plasma display (PDP), an electroluminescence display (ELD), and a liquid crystal display (LCD). In order to prevent image reflection, it is placed on the top surface of the display to reduce reflectivity using the principle of optical interference. Therefore, in addition to high antireflection performance, the antireflection film is required to have high physical strength (such as scratch resistance), surface uniformity, chemical resistance, and weather resistance (wet heat resistance, light resistance).

  Such an antireflection film can be generally produced by forming a low refractive index layer having an appropriate film thickness having a lower refractive index than that of the support on the support.

  Further, as described above, 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 low refractive index layer having a thickness of around 100 nm, a substance having a high hardness is contained in the layer, or the strength of the binder itself, which is one of the components of the antireflection film, is increased. It is necessary to increase.

  In order to improve the scratch resistance of the antireflection film, a technique of adding silica particles to a low refractive index layer in the antireflection film is widely used. In order to further improve the scratch resistance, it is effective to use a larger silica. However, when the particle diameter of the silica used exceeds 40 nm with respect to a low refractive index layer having a thickness of about 100 nm, When the filling rate is increased in order to improve the scratch resistance, a phenomenon that silica particles are exposed on the film surface after the coating film is formed occurs. As a result, the silica exposed on the surface becomes a scattering source, and when this antireflection film is bonded to a display, there is a problem that the surface appears whitish (whitening due to silica, hereinafter also referred to as whitening). .

  In addition, when the silica particles are exposed on the surface as described above, the exposed silica may be peeled off by rubbing the surface. As a result, since there is no scattering source only in the rubbed part, there is a problem that whiteness disappears there and unevenness in the surface shape occurs. For this reason, when silica particles having a particle diameter exceeding 40 nm are used alone, it is difficult to simultaneously achieve high scratch resistance and prevention of whitening.

  In the case of curing the coating film, in the case of using a photocuring reaction, after coating, the coating film is cured after passing through the drying process. On the other hand, in the case of using thermal curing, the coating is dried after coating. At the same time, curing is performed. For this reason, when photocuring is used, it takes time to cure after coating, and the coating solution for the low refractive index layer coated on the antiglare particles tends to flow down from the upper part to the lower part of the antiglare particles. As a result, in the photocuring, the coating film around the antiglare particles became thin, and the silica particles as described above were more easily exposed and easily whitened.

  In the low refractive index layer, it has been known so far to use a fluorine-containing polymer in order to lower the refractive index of the material (see, for example, Patent Document 1). However, although the fluorine-containing polymer has a low refractive index and is excellent in transparency and chemical resistance, there is a problem that it is difficult to form a coating film excellent in scratch resistance.

  Therefore, as a method for improving the scratch resistance, it is known to use a low molecular weight material having a polymerizable group in addition to the fluorine-containing polymer.

  However, in such a case, increasing the ratio of the low molecular weight material in order to increase the scratch resistance not only increases the reflectance as a result of the increase in the refractive index of the layer, but also the fluorine-containing polymer. There is a problem that phase separation occurs between the low molecular weight material and a uniform surface state cannot be obtained.

Japanese Patent Laid-Open No. 11-305010

The object of the present invention is to have a low refractive index layer that does not cause failure due to whitening, has high scratch resistance, sufficient antireflection ability, and does not cause phase separation that makes the surface shape non-uniform. An antireflection film is provided. Here, the failure due to whitening means that the surface of the coating film becomes white enough to be recognized at a glance and that the surface becomes uneven by rubbing the surface although it is only slightly whitened.
Another object of the present invention is to provide a polarizing plate and an image display device provided with the antireflection film.

  As a result of intensive studies to solve the above problems, the present inventors have achieved the above problems by the following means.

1. An antiglare layer and a low refractive index layer are provided in this order on a transparent support, and the low refractive index layer contains the following components (A), (B), (C), (D) and (E): A cured product of the containing composition,
(A) Solid inorganic fine particles having an average particle diameter of 40 to 100 nm (B) Solid inorganic fine particles having an average particle diameter of 1 to 30 nm (C) A photocurable fluorine-containing polymer (D) containing an ethylenically unsaturated group Photocurable acrylate monomer (E) photopolymerization initiator The content of the solid inorganic fine particles (A) is 3.5% by mass or more and 13% by mass or less based on the total solid content of the low refractive index layer, The total content of the solid inorganic fine particles (A) and the solid inorganic fine particles (B) is 10% by mass to 40% by mass with respect to the total solid content of the low refractive index layer, and the low refractive index layer The antireflective film whose refractive index is 1.440 or more and 1.465 or less.
2. The antireflection film as described in 1 above, wherein the solid inorganic fine particles (A) and the solid inorganic fine particles (B) are both silica fine particles.
3. The above 1 or 2 wherein the surfaces of the solid inorganic fine particles (A) and the solid inorganic fine particles (B) are surface-treated with at least one selected from a hydrolyzate of an organosilane compound and a partial condensate thereof. The antireflection film as described in 1.
4. The photo-curable fluorine-containing polymer (C) containing the ethylenically unsaturated group is a copolymer (P) whose main chain is composed of only carbon atoms, and the copolymer (P) is a fluorine-containing polymer. 4. The antireflection film as described in any one of 1 to 3 above, comprising a polymer unit derived from a vinyl monomer and a polymer unit having a (meth) acryloyl group in a side chain.
5. The antireflection film as described in 4 above, wherein the copolymer (P) is represented by the following general formula 1.

In General Formula 1, L represents a linking group having 1 to 10 carbon atoms, and m represents 0 or 1. X represents a hydrogen atom or a methyl group. A represents a polymerization unit derived from an arbitrary vinyl monomer, and may be a single component or a plurality of components. x, y, and z represent the mol% of each polymerization unit, and represent values satisfying 30 ≦ x ≦ 60, 5 ≦ y ≦ 70, and 0 ≦ z ≦ 65. However, x + y + z is 100 mol%.
6. The antireflection film as described in any one of 1 to 5 above, wherein the composition further contains a fluorine-containing acrylate monomer (F).
7. A polarizing plate having a polarizing film and protective films provided on both sides of the polarizing film, wherein at least one of the protective films is the antireflection film according to any one of 1 to 6 above.
8. An image display device in which the antireflection film according to any one of 1 to 6 or the polarizing plate according to 7 is disposed on an image display surface.

  According to the present invention, it has a low refractive index layer that does not cause failure due to whitening, has high scratch resistance, sufficient antireflection ability, and does not cause phase separation that makes the surface shape non-uniform. An antireflection film can be provided. In addition, a polarizing plate and an image display device provided with the antireflection film can be provided.

  Hereinafter, the present invention will be described in more detail. In the present specification, when a numerical value represents a physical property value, a characteristic value, etc., the description “(numerical value 1) to (numerical value 2)” means “(numerical value 1) or more and (numerical value 2) or less”. . In the present specification, the description “(meth) acrylate” means “at least one of acrylate and methacrylate”. The same applies to “(meth) acrylic acid” and the like.

The antireflection film of the present invention has an antiglare layer and a low refractive index layer in this order on a transparent support, and the low refractive index layer comprises the following components (A), (B), (C), (D ) And (E), a cured product of the composition,
(A) Solid inorganic fine particles having an average particle diameter of 40 to 100 nm (B) Solid inorganic fine particles having an average particle diameter of 1 to 30 nm (C) A photocurable fluorine-containing polymer (D) containing an ethylenically unsaturated group The photocurable acrylate monomer (E) photopolymerization initiator The mass of the solid inorganic fine particles (A) is from 3.5% by mass to 13% by mass with respect to the total solid content of the low refractive index layer. The sum of the actual inorganic fine particles (A) and the solid inorganic fine particles (B) is 10% by mass to 40% by mass with respect to the total solid content of the low refractive index layer, and the refractive index of the low refractive index layer is It is 1.440 or more and 1.465 or less.

(Photocurable fluorinated polymer (C))
Examples of the photocurable fluorine-containing polymer (C) (hereinafter also simply referred to as fluorine-containing polymer) contained in the composition for forming the low refractive index layer include perfluoroalkyl group-containing silane compounds (for example, (heptadecafluoro- 1,1,2,2-tetrahydrodecyl) triethoxysilane) hydrolysis, dehydration condensate, fluorine-containing monomer units and structural units for imparting crosslinking reactivity (addition of ethylenically unsaturated groups in the molecule) And a fluorine-containing copolymer having a structural component as a structural component.

  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-dioxole. Etc.), partially (meth) acrylic acid or fully fluorinated alkyl ester derivatives (for example, Biscoat 6FM (manufactured by Osaka Organic Chemicals) or M-2020 (manufactured by Daikin)), fully or partially fluorinated vinyl ethers, etc. However, perfluoroolefins are preferred, and hexafluoropropylene is particularly preferred from the viewpoints of refractive index, solubility, transparency, availability, and the like.

  As structural units for imparting crosslinking reactivity, structural units obtained by polymerization of monomers having a self-crosslinkable functional group in advance in the molecule such as glycidyl (meth) acrylate and glycidyl vinyl ether, carboxyl groups, hydroxy groups, amino groups , Obtained by polymerization of a monomer having a sulfo group or the like (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 obtained by introducing a crosslinking reactive group such as a (meth) acryloyl group into these structural units 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) And the like.

  In addition to the above-mentioned fluorine-containing monomer units and structural units for imparting crosslinking reactivity, monomers not containing fluorine atoms can be copolymerized as appropriate from the viewpoints of solubility in solvents and film transparency. There are no particular limitations on the monomer units that can be used in combination. For example, 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-tert-butylacrylamide, N- Black 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 above polymer.

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

  The fluorine-containing polymer useful in the present invention is a copolymer (P) whose main chain is composed only of carbon atoms, and the copolymer (P) is a polymer unit derived from a fluorine-containing vinyl monomer and a side chain ( It is a polymer containing a polymer unit having a (meth) acryloyl group.

  As a preferred form of the copolymer (P) used in the present invention, one having the following general formula 1 can be mentioned.

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, and may have a heteroatom selected from O, N, and S. Preferred examples include * — (CH ₂ ) ₂ —O — **, * — (CH ₂ ) ₂ —NH — **, * — (CH ₂ ) ₄ —O — **, * — (CH ₂ ). _{6 -O - **, * - (} CH 2) 2 -O- (CH 2) 2 -O - **, * - CONH- (CH 2) 3 -O - **, * - CH 2 CH (OH ) CH ₂ —O — **, * —CH ₂ CH ₂ OCONH (CH ₂ ) ₃ —O — ** (* represents a connecting site on the polymer main chain side, and ** represents a connection 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 general formula 1, A represents a polymerization unit derived from any vinyl monomer, and is particularly limited as long as it is a polymerization unit obtained from a monomer copolymerizable with a monomer constituting another polymerization unit in general formula 1. It can be appropriately selected from various viewpoints such as adhesion to a transparent support, polymer Tg (contributing to film hardness), solubility in a solvent, transparency, slipperiness, dustproof / antifouling properties, etc. Depending on the purpose, it may be composed of a single or a plurality of vinyl monomers.

  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 polymerization unit, and represent values satisfying 30 ≦ x ≦ 60, 5 ≦ y ≦ 70, and 0 ≦ z ≦ 65. Preferably, 35 ≦ x ≦ 55, 30 ≦ y ≦ 60, and 0 ≦ z ≦ 20, and particularly preferably 40 ≦ x ≦ 55, 40 ≦ y ≦ 55, and 0 ≦ z ≦ 10. However, x + y + z is 100 mol%.

General formula 2 is mentioned as a particularly preferable form of the copolymer (P) used in the present invention.
General formula 2

In general formula 2, X, x, and y have the same meaning as in general formula 1, and the preferred ranges are also the same.
n represents an integer of 2 ≦ n ≦ 10, preferably 2 ≦ n ≦ 6, and particularly preferably 2 ≦ n ≦ 4.
B represents a repeating unit derived from an arbitrary vinyl monomer, and may be composed of a single composition or a plurality of compositions. As an example, what was demonstrated as an example of A in the said General formula 1 is applicable.
z1 and z2 represent mol% of each repeating unit, and represent values satisfying 0 ≦ z1 ≦ 65 and 0 ≦ z2 ≦ 65. It is preferable that 0 ≦ z1 ≦ 30 and 0 ≦ z2 ≦ 10 respectively, and it is particularly preferable that 0 ≦ z1 ≦ 10 and 0 ≦ z2 ≦ 5. However, x + y + z1 + z2 is 100 mol%.
The fluorine-containing polymer used in the present invention may be a single polymer having a single molecular structure or a plurality of polymers having different molecular structures.

  For example, the copolymer (P) represented by the general formula 1 or 2 is obtained by adding a (meth) acryloyl group to a copolymer comprising a hexafluoropropylene component and a hydroxyalkyl vinyl ether component by any one of the methods described above. It can be synthesized by introduction.

  The fluorine-containing polymer used in the present invention is synthesized by synthesizing a precursor such as a hydroxyl group-containing polymer by various polymerization methods such as solution polymerization, precipitation polymerization, suspension polymerization, precipitation polymerization, bulk polymerization, and emulsion polymerization. It can be carried out by introducing a (meth) acryloyl group by the polymer reaction. The polymerization reaction can be performed by a known operation such as a batch system, a semi-continuous system, or a continuous system.

  The polymerization initiation method includes a method using a radical initiator, a method of irradiating light or radiation, and the like. These polymerization methods and polymerization initiation methods are, for example, the revised version of Tsuruta Junji “Polymer Synthesis Method” (published by Nikkan Kogyo Shimbun, 1971), Takatsu Otsu, Masato Kinoshita, “Experimental Methods for Polymer Synthesis” It is described in pp. 47-154 published in 1972.

  Among the above polymerization methods, a solution polymerization method using a radical initiator is particularly preferable. Solvents used in the solution polymerization method include, for example, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, tetrahydrofuran, dioxane, N, N-dimethylformamide, N, N-dimethylacetamide, benzene, toluene, acetonitrile, A single organic solvent such as methylene chloride, chloroform, dichloroethane, methanol, ethanol, 1-propanol, 2-propanol, and 1-butanol, or a mixture of two or more thereof may be used, or a mixed solvent with water may be used.

  The polymerization temperature needs to be set in relation to the molecular weight of the polymer to be produced, the type of initiator, etc., and can be from 0 ° C. or lower to 100 ° C. or higher, but it is preferable to carry out the polymerization in the range of 50 to 100 ° C.

The reaction pressure can be selected as appropriate, but it is usually 1-100 kg / cm ² , particularly about 1-30 kg / cm ² . The reaction time is about 5 to 30 hours.

  As the reprecipitation solvent for the obtained polymer, isopropanol, hexane, methanol and the like are preferable.

  The mass average molecular weight of the fluorine-containing polymer used in the present invention is 5000 or more, preferably 10,000 to 500,000, most preferably 15,000 to 200,000 in terms of standard polystyrene by gel permeation chromatography.

  The refractive index of the fluoropolymer used in the present invention is preferably 1.15 to 1.49, more preferably 1.20 to 1.45, and particularly preferably 1.20 to 1.43. .

(Inorganic fine particles)
The inorganic fine particles used in the low refractive index layer of the present invention will be described. In the present invention, scratch resistance can be improved by using inorganic fine particles in the low refractive index layer. In the present invention, two types of particles having different average particle diameters (solid inorganic fine particles (A) and solid inorganic fine particles (B)) are used, and scratch resistance and whitening prevention are improved. Moreover, the solid of solid inorganic fine particles means not hollow.

  The average particle diameter of the inorganic fine particles is such that the larger average particle diameter (average particle diameter of the solid inorganic fine particles (A)) is 40 nm to 100 nm, preferably 40 to 80 nm, more preferably 40 to 60 nm. The smaller average particle diameter (average particle diameter of the solid inorganic fine particles (B)) is 1 nm to 30 nm, preferably 5 nm to 25 nm, more preferably 10 nm to 20 nm.

  The inorganic fine particles are preferably monodispersed in both solid inorganic fine particles (A) and solid inorganic fine particles (B). The coefficient of variation (CvA) is preferably 30% or less, and more preferably 20% or less. Furthermore, 10% or less is particularly preferable.

  Examples of the inorganic fine particles include inorganic fine particles such as magnesium fluoride and silica. In particular, silica fine particles are preferable in terms of refractive index, dispersion stability, and cost. It is more preferable that both the solid inorganic fine particles (A) and the solid inorganic fine particles (B) are silica fine particles.

  When only silica particles having a single particle size are used, if the particle size is too small, the effect of improving the scratch resistance is reduced, and if it is too large, the silica particles are exposed on the surface of the low refractive index layer. As a result, whitening of the film occurs. The silica fine particles may be either crystalline or amorphous, and may be monodispersed particles or aggregated particles as long as a predetermined particle size is satisfied. The shape is most preferably a spherical diameter, but there is no problem even if the shape is indefinite. What has been described above for silica fine particles also applies to other inorganic particles. Here, the particle size of the inorganic fine particles is measured from observation by TEM, and the average particle size and particle size distribution are calculated from the measurement results.

  A method for treating the surface of the inorganic fine particles will be described. In order to improve the dispersibility in the binder for forming a low refractive index layer, the surface of the inorganic fine particles is preferably treated with at least one selected from a hydrolyzate of organosilane and a partial condensate thereof, More preferably, it is treated with a hydrolyzate of organosilane represented by the following general formula 3 and / or a partial condensate thereof, and either or both of the acid catalyst and the metal chelate compound are treated during the treatment. More preferably it is used. More preferably, the surfaces of the solid inorganic fine particles (A) and the solid inorganic fine particles (B) are surface-treated with at least one selected from hydrolysates of organosilane compounds and partial condensates thereof.

(Organosilane compound)
The organosilane compound used in the present invention will be described in detail.
Formula _{^{3: (R 10) a1 -Si}} (X 11) 4-a1

In General Formula 3, R ¹⁰ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. Examples of the alkyl group include methyl group, ethyl group, propyl group, i-propyl group, hexyl group, t-butyl group, s-butyl group, hexyl group, decyl group, hexadecyl group 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 a phenyl group and a naphthyl group, and a phenyl group is preferable.

X ¹¹ represents a hydroxyl group or a hydrolyzable group. Examples of the hydrolyzable group include an alkoxy group (preferably an alkoxy group having 1 to 5 carbon atoms, such as a methoxy group and an ethoxy group), a halogen atom (for example, Cl, Br, I and the like), and R ^12. A group represented by COO (R ¹² is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, such as CH ₃ COO, C ₂ H ₅ COO, etc.), preferably an alkoxy group, Particularly preferred is a methoxy group or an ethoxy group.
a1 represents an integer of 1 to 3. 1 or 2 is preferable, and 1 is particularly preferable. When R ¹⁰ or the X ¹¹ there are a plurality, a plurality of R ¹⁰ or X ¹¹ may be different, respectively.

The substituent contained in R ¹⁰ is not particularly limited, but is a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), hydroxyl group, mercapto group, carboxyl group, epoxy group, alkyl group (methyl group, ethyl group, i -Propyl group, propyl group, t-butyl group etc.), aryl group (phenyl group, naphthyl group etc.), aromatic heterocyclic group (furyl group, pyrazolyl group, pyridyl group etc.), alkoxy group (methoxy group, ethoxy group) I-propoxy group, hexyloxy group, etc.), aryloxy group (phenoxy group etc.), alkylthio group (methylthio group, ethylthio group etc.), arylthio group (phenylthio group etc.), alkenyl group (vinyl group, 1-propenyl group) Etc.), acyloxy group (acetoxy group, acryloyloxy group, methacryloyloxy group, etc.), alkoxycarbonyl group Methoxycarbonyl group, ethoxycarbonyl group, etc.), aryloxycarbonyl group (phenoxycarbonyl group, etc.), carbamoyl group (carbamoyl group, N-methylcarbamoyl group, N, N-dimethylcarbamoyl group, N-methyl-N-octylcarbamoyl group) Etc.), acylamino groups (acetylamino group, benzoylamino group, acrylamino group, methacrylamino group, etc.) and the like, and these substituents may be further substituted. In the present specification, even if a hydrogen atom is replaced by a single atom, it is treated as a substituent for convenience.

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 these, the substituted alkyl group or substituted aryl group preferably further has a vinyl polymerizable group. In this case, the compound represented by the general formula 3 is a vinyl polymerizable substituent represented by the following general formula 3-1. It can be expressed as an organosilane compound having
General formula 3-1:

In General Formula 3-1, R ¹¹ 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. R ¹¹ is preferably a hydrogen atom, a methyl group, a methoxy group, a methoxycarbonyl group, a cyano group, a fluorine atom or a chlorine atom, more preferably a hydrogen atom, a methyl group, a methoxycarbonyl group, a fluorine atom or a chlorine atom, And a methyl group are particularly preferred.

Y ¹¹ represents a single bond, an ester group, an amide group, an ether group or a urea group. Single bonds, ester groups and amide groups are preferred, single bonds and ester groups are more preferred, and ester groups are particularly preferred.

L ¹¹ is a divalent linking chain, specifically, a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, and a linking group (for example, an ether group, an ester group, an amide group) inside. A substituted or unsubstituted alkylene group, or a substituted or unsubstituted arylene group having a linking group therein, among which a substituted or unsubstituted alkylene group having 2 to 10 carbon atoms, a substituted or unsubstituted carbon number of 6 An alkylene group having 3 to 10 carbon atoms having a linking group therein and an unsubstituted alkylene group, an unsubstituted arylene group, and an alkylene group having an ether linking group or an ester linking group therein. An unsubstituted alkylene group and an alkylene group having an ether linking group or an ester linking group therein are particularly preferred. 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.

a2 represents 0 or 1. When X ¹¹ there are a plurality, it may be different even multiple X ¹¹ is the same, respectively. a2 is preferably 0.

R ¹⁰ has the same meaning as R ^{10 in} Formula 3, and is 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 ^{11 is} also synonymous with X ^{11 in} formula 3, preferably halogen, hydroxyl group and unsubstituted alkoxy group, more preferably chlorine, hydroxyl group and unsubstituted alkoxy group having 1 to 6 carbon atoms, hydroxyl group and carbon number 1 -3 alkoxy groups are more preferred, and methoxy groups are particularly preferred.

As the organosilane compound used in the present invention, those represented by the following general formula 4 are also preferable.
Formula ^{4: (Rf-L 21)} b1 -Si (X 21) 4-b1

In the general formula 4, Rf represents a linear, branched or cyclic fluorinated alkyl group having 1 to 20 carbon atoms or a fluorinated aromatic group having 6 to 14 carbon atoms. Rf is preferably a linear, branched or cyclic fluoroalkyl group having 3 to 10 carbon atoms, and more preferably a linear fluoroalkyl group having 4 to 8 carbon atoms. L ²¹ represents a divalent linking group having 10 or less carbon atoms, preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms. The alkylene group is a linear or branched, substituted or unsubstituted alkylene group that may have a linking group (for example, ether, ester, amide) inside. The alkylene group may have a substituent, and preferable substituents in that case include a halogen atom, a hydroxyl group, a mercapto group, a carboxyl group, an epoxy group, an alkyl group, and an aryl group. X21 has the same meaning as X11 in formula 3, preferably a halogen, a hydroxyl group, or an unsubstituted alkoxy group, more preferably a chlorine, a hydroxyl group, or an unsubstituted alkoxy group having 1 to 6 carbon atoms, a hydroxyl group, 3 is more preferable, and a methoxy group is particularly preferable.
b1 is synonymous with a1 of the said General formula 3, and represents the integer of 1-3. 1 or 2 is preferable, and 1 is particularly preferable.

Next, among the organosilane compounds represented by the general formula 4, a fluorine-containing organosilane compound represented by the following general formula 4-1 is preferable.
Formula _{4-1: C n F 2n + 1} - (CH 2) m -Si (X 22) 3
In the general formula 4-1, n represents an integer of 1 to 10, and m represents an integer of 1 to 5. n is preferably 4 to 10, m is preferably 1 to 3, X ²² are each independently if there are a plurality, a methoxy group, an ethoxy group or a chlorine atom.

  Two or more kinds of the compounds represented by General Formula 3, General Formula 3-1, General Formula 4, and General Formula 4-1 may be used in combination.

  Specific examples of the compounds represented by General Formula 3, General Formula 3-1, General Formula 4, and General Formula 4-1, are shown below, but the present invention is not limited thereto.

  Among the specific compounds (M-1) to (M-88), (M-1), (M-2), (M-30), (M-35), (M-49), (M-51), (M-56) and (M-57) are preferred. Further, the compounds of A, B and C described in Reference Examples of Japanese Patent No. 3474330 are also preferable because of excellent dispersion stability.

  Disiloxane compounds can also be used as surface treating agents, such as hexamethyldisiloxane, 1,3-dibutyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane, 1,3-divinyltetra. Examples thereof include methyldisiloxane, hexaethyldisiloxane, and 3-glycidoxypropylpentamethyldisiloxane.

  In the present invention, the amount of the organosilane compound represented by the general formula 3, the general formula 3-1, the general formula 4, and the general formula 4-1 is not particularly limited, but is 1 to 300 mass per inorganic fine particle. % Is preferable, more preferably 3 to 100% by mass, and most preferably 5 to 50% by mass. It is preferably 1 to 300 mol%, more preferably 5 to 300 mol%, most preferably 10 to 200 mol% per hydroxyl group on the surface of the inorganic fine particles. When the amount of the organosilane compound used is in the above range, a sufficient stabilizing effect of the dispersion can be obtained, and the film strength is also increased during coating film formation. In the present invention, it is also preferable to use a plurality of types of organosilane compounds in combination, and a plurality of types of compounds can be added simultaneously, or the addition time can be shifted for reaction. Also, it is preferable to add a plurality of types of compounds after making them into partial condensates in advance because the reaction control is easy.

In the present invention, the dispersibility of the inorganic fine particles can be improved by allowing the hydrolyzate and / or partial condensate thereof described above to act on the surface of the inorganic fine particles. The hydrolysis / condensation reaction of the organosilane compound is 0.3 to 2.0 mol, preferably 0.5 to 1.0 mol, relative to 1 mol of the hydrolyzable group (X ¹¹ , X ²¹ and X ²² ). It is preferable to carry out by stirring at 15-100 degreeC in the presence of the acid catalyst used for this invention, or the metal chelate compound.

(catalyst)
The treatment for improving the dispersibility by the hydrolyzate and / or condensation reaction product of the organosilane is preferably performed in the presence of a catalyst. Catalysts include inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid; organic acids such as oxalic acid, acetic acid, formic acid, methanesulfonic acid and toluenesulfonic acid; inorganic bases such as sodium hydroxide, potassium hydroxide and ammonia; triethylamine, Examples include organic bases such as pyridine; metal alkoxides such as triisopropoxyaluminum and tetrabutoxyzirconium. From the viewpoint of production stability and storage stability of the inorganic oxide fine particle liquid, an acid catalyst is used in the present invention. (Inorganic acids, organic acids) and / or metal chelate compounds are used. Of inorganic acids, hydrochloric acid, sulfuric acid, and organic acids preferably have an acid dissociation constant (pKa value (25 ° C.)) of 4.5 or less in water, and an acid dissociation constant of 3.0 or less in hydrochloric acid, sulfuric acid, or water. More preferred is an organic acid, hydrochloric acid, sulfuric acid, an organic acid having an acid dissociation constant of 2.5 or less in water is more preferred, an organic acid having an acid dissociation constant in water of 2.5 or less is more preferred, and methanesulfonic acid Further, oxalic acid, phthalic acid, and malonic acid are more preferable, and oxalic acid is particularly preferable.

  When the hydrolyzable group of the organosilane compound is an alkoxy group and the acid catalyst is an organic acid, the amount of water added can be reduced because the carboxyl group or sulfo group of the organic acid supplies protons. The amount of water added to 1 mol of the alkoxide group of the organosilane is 0 to 2 mol, preferably 0 to 1.5 mol, more preferably 0 to 1 mol, and particularly preferably 0 to 0.5 mol. Moreover, when alcohol is used for the solvent, an embodiment in which water is not substantially added is also suitable.

(Metal chelate compound)
In this invention, the metal chelate compound used for the improvement process of the dispersibility by the hydrolyzate and / or condensation reaction product of an organosilane compound is an alcohol represented by the following general formula (5-1) and the following general formula (5- At least one metal chelate compound having a metal selected from Zr, Ti or Al as a central metal and having the compound represented by 2) as a ligand is preferred. As long as the metal chelate compound has a metal selected from Zr, Ti or Al as the central metal, it can be suitably used without any particular limitation. Within this category, two or more metal chelate compounds may be used in combination.
Formula (5-1): R ₃₁ OH
Formula (5-2): R ₃₂ COCH ₂ COR ₃₃
(In the formula, R ₃₁ and R ₃₂ may be the same or different and each represents an alkyl group having 1 to 10 carbon atoms, and R ₃₃ represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. Show.)

  Specific examples of the metal chelate compound suitably used in the present invention include tri-n-butoxyethyl acetoacetate zirconium, di-n-butoxybis (ethyl acetoacetate) zirconium, n-butoxy tris (ethyl acetoacetate) zirconium, tetrakis Zirconium chelate compounds such as (n-propylacetoacetate) zirconium, tetrakis (acetylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium; diisopropoxy bis (ethylacetoacetate) titanium, diisopropoxy bis (acetylacetate) ) Titanium chelate compounds such as titanium, diisopropoxy bis (acetylacetone) titanium; diisopropoxyethyl acetoacetate aluminum , Diisopropoxyacetylacetonate aluminum, isopropoxybis (ethylacetoacetate) aluminum, isopropoxybis (acetylacetonate) aluminum, tris (ethylacetoacetate) aluminum, tris (acetylacetonate) aluminum, monoacetylacetonate -Aluminum chelate compounds, such as bis (ethyl acetoacetate) aluminum, etc. are mentioned.

  Among these metal chelate compounds, tri-n-butoxyethyl acetoacetate zirconium, diisopropoxy bis (acetylacetonate) titanium, diisopropoxyethyl acetoacetate aluminum, and tris (ethyl acetoacetate) aluminum are preferable. . These metal chelate compounds can be used individually by 1 type or in mixture of 2 or more types. Moreover, the partial hydrolyzate of these metal chelate compounds can also be used. The amount of these metal chelate compounds is preferably 0.1 to 10.0% by mass, more preferably 0.5 to 5.0% by mass, and most preferably 1.0 to 3.0% with respect to the organosilane compound. % By mass.

(Dispersant)
In the present invention, a dispersant may be used to prepare inorganic fine particles by dispersing them from a powder in a solvent. In the present invention, it is 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 (sulfo), a phosphoric acid group (phosphono), a sulfonamide group, or a salt thereof is effective, and in particular, a carboxyl group, a sulfonic acid group, A phosphoric acid group or a salt thereof is preferable, and a carboxyl group or a phosphoric acid group is particularly preferable. A plurality of anionic groups may be contained for the purpose of further improving dispersibility. The average number is preferably 2 or more, more preferably 5 or more, and particularly preferably 10 or more. Moreover, the anionic group contained in a dispersing agent may contain multiple types in 1 molecule.

  The dispersant may further contain a crosslinking or polymerizable functional group. Examples of the crosslinkable or polymerizable functional group include an ethylenically unsaturated group {for example, (meth) acryloyl group, allyl group, styryl group, vinyloxy group, etc.} capable of addition reaction / polymerization reaction by radical species, cationic polymerizable group ( Epoxy group, oxatanyl group, vinyloxy group, etc.), polycondensation reactive groups (hydrolyzable silyl group, etc., N-methylol group), etc., and the like, preferably a functional group having an ethylenically unsaturated group. The amount of these dispersants to be used is preferably 0.5 to 30% by mass, more preferably 1 to 20% by mass, and most preferably 2 to 15% by mass with respect to the inorganic fine particles.

((D) photocurable acrylate monomer)
The film of the present invention can be formed by a crosslinking reaction or a polymerization reaction of an ionizing radiation curable compound. That is, it can be formed by applying a composition containing an ionizing radiation-curable polyfunctional monomer as a binder onto a transparent support and causing the polyfunctional monomer to undergo a crosslinking reaction or a polymerization reaction.
The functional group of the ionizing radiation curable polyfunctional monomer is preferably a light, electron beam or radiation polymerizable group, and among them, a photopolymerizable functional group is preferable.
Examples of the photopolymerizable functional group include unsaturated polymerizable functional groups such as a (meth) acryloyl group, a vinyl group, a styryl group, and an allyl group. Among them, a (meth) acryloyl group is preferable. Particularly preferably, a compound containing two or more (meth) acryloyl groups in one molecule described below can be used.

As a specific example of a photopolymerizable polyfunctional monomer having a photopolymerizable functional group,
(Meth) acrylic acid diesters of alkylene glycol such as neopentyl glycol acrylate, 1,6-hexanediol (meth) acrylate, propylene glycol di (meth) acrylate;
(Meth) acrylic acid diesters of polyoxyalkylene glycols such as triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate;
(Meth) acrylic acid diesters of polyhydric alcohols such as pentaerythritol di (meth) acrylate;
(Meth) acrylic acid diesters of ethylene oxide or propylene oxide adducts such as 2,2-bis {4- (acryloxy · diethoxy) phenyl} propane and 2-bis {4- (acryloxy · polypropoxy) phenyl} propane ;
Etc.

  Furthermore, epoxy (meth) acrylates, urethane (meth) acrylates, and polyester (meth) acrylates are also preferably used as the photopolymerizable polyfunctional monomer.

  Among these, esters of polyhydric alcohol and (meth) acrylic acid are preferable. More preferably, a polyfunctional monomer having 3 or more (meth) acryloyl groups in one molecule is preferable. Specifically, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, 1,2,4-cyclohexanetetra (meth) acrylate, pentaglycerol triacrylate, pentaerythritol tetra (meth) acrylate, penta Erythritol tri (meth) acrylate, (di) pentaerythritol triacrylate, (di) pentaerythritol pentaacrylate, (di) pentaerythritol tetra (meth) acrylate, (di) pentaerythritol hexa (meth) acrylate, tripentaerythritol triacrylate , Tripentaerythritol hexatriacrylate and the like. In the present specification, “(meth) acrylate”, “(meth) acrylic acid”, and “(meth) acryloyl” represent “acrylate or methacrylate”, “acrylic acid or methacrylic acid”, and “acryloyl or methacryloyl”, respectively. .

  As the monomer binder, monomers having different refractive indexes can be used to control the refractive index of each layer.

  Polymerization of the acrylate monomer can be performed by irradiation with ionizing radiation in the presence of a photo radical initiator. 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.

((E) Photopolymerization initiator)
The photopolymerization initiator effective for curing the low refractive index layer of the present invention will be described. When the constituent component of the low refractive index layer is a radical polymerizable compound, the polymerization of these compounds can be performed by irradiation with ionizing radiation in the presence of a photo radical initiator.

  As radical photopolymerization initiators, acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkyldione compounds, disulfide compounds , Fluoroamine compounds, aromatic sulfoniums, lophine dimers, onium salts, borate salts, active esters, active halogens, inorganic complexes, coumarins and the like.

  Examples of acetophenones include 2,2-dimethoxyacetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, 1-hydroxy-dimethylphenylketone, 1-hydroxy-dimethyl-p-isopropylphenylketone, 1-hydroxy Cyclohexyl phenyl ketone, 2-methyl-4-methylthio-2-morpholinopropiophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, 4-phenoxydichloroacetophenone, 4-t-butyl -Dichloroacetophenone and the like are included.

  Examples of benzoins include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyl dimethyl ketal, benzoin benzene sulfonate, benzoin toluene sulfonate, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether. included.

  Examples of benzophenones include benzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 2,4-dichlorobenzophenone, 4,4-dichlorobenzophenone and p-chlorobenzophenone, 4,4'-dimethylaminobenzophenone (Michler ketone), 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone and the like are included.

  Examples of phosphine oxides include 2,4,6-trimethylbenzoyl diphenylphosphine oxide. Examples of the active esters include 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], sulfonic acid esters, cyclic active ester compounds, and the like. Specifically, compounds described in Examples in JP-A No. 2000-80068 are particularly preferable.

  Examples of the onium salts include aromatic diazonium salts, aromatic iodonium salts, and aromatic sulfonium salts. Examples of borate salts include ion complexes with cationic dyes.

  Specific examples of the active halogens include Wakabayashi et al., “Bull Chem. Soc Japan”, 42, 2924 (1969), US Pat. No. 3,905,815, JP-A-5-27830, P. The compounds described in Hutt “Jurnalof Heterocyclic Chemistry”, Vol. 1 (No. 3), (1970), and the like are mentioned, and in particular, an oxazole compound substituted with a trihalomethyl group: an s-triazine compound. More preferred are s-triazine derivatives in which at least one mono-, di- or trihalogen-substituted methyl group is bonded to the s-triazine ring. Specific examples include S-triazine and oxathiazole compounds, such as 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl). -4,6-bis (trichloromethyl) -s-triazine, 2- (p-styrylphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3-Br-4-di (ethyl) Acetate) amino) phenyl) -4,6-bis (trichloromethyl) -s-triazine, 2-trihalomethyl-5- (p-methoxyphenyl) -1,3,4-oxadiazole. Specifically, p.14 to p30 in JP-A-58-15503, p6-p10 in JP-A-55-77742, and p287 in JP-B-60-27673. 1-No. 8, No. pp. 443 to p444 of JP-A-60-239736. 1-No. 17, No. 4,701,399. Compounds such as 1-19 are particularly preferred.

  Specific examples of the active halogens are as follows.

  Examples of inorganic complexes include bis (η5-2,4-cyclopentadien-1-yl) -bis [2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl] titanium. Examples of coumarins include 3-ketocoumarin. These initiators may be used alone or in combination.

In the present invention, an oligomer type polymerization initiator is preferred as the compound having a high molecular weight and hardly volatilizing from the coating film. The oligomer type radiation polymerization initiator is not particularly limited as long as it has a site that generates a photo radical upon irradiation. In order to prevent volatilization due to heat treatment, the molecular weight of the polymerization initiator is preferably 250 or more and 10,000 or less, more preferably 300 or more and 10,000 or less. More preferably, the mass average molecular weight is 400 to 10,000. A mass average molecular weight of 400 or more is preferable because of low volatility, and 10,000 or less is preferable because hardness of the resulting cured coating film is sufficient. Specific examples of the oligomer type radiation polymerization initiator include oligo [2-hydroxy-2-methyl-1- {4- (1-methylvinyl) phenyl} propanone] represented by the following general formula 5.
General formula 5:

In the general formula 5, R ⁵¹ represents a monovalent group, preferably a monovalent organic group, and q represents an integer of 2 to 45.

  As a commercially available product of the oligo [2-hydroxy-2-methyl-1- {4- (1-methylvinyl) phenyl} propanone] represented by the above general formula 5, trade name “Ezacure KIP150” (manufactured by Fratelli Lamberti) ( CAS-No. 163702-01-0, q = 4-6), “Ezacure KIP65LT” (a mixture of “Ezacure KIP150” and tripropylene glycol diacrylate), “Ezacure KIP100F” (“Ezacure KIP150” and 2-hydroxy- 2-Methyl-1-phenylpropan-1-one), “Ezacure KT37”, “Ezacure KT55” (above, “Ezacure KIP150” and a mixture of methylbenzophenone derivatives), “Ezacure KTO46” (“Ezacure KIP150”, Methylbenzopheno Derivatives, a mixture of 2,4,6-trimethylbenzoyldiphenylphosphine oxide), “Ezacure KIP75 / B” (a mixture of “Ezacure KIP150” and 2,2-dimethoxy-1,2-diphenylethane-1-one), etc. Can be mentioned.

  “Latest UV Curing Technology” {Technical Information Association, Inc.} (1991), p. 159 and “UV Curing System” written by Kiyotsugu Kato (published by the General Technology Center in 1989), pages 65-148, are also useful in the present invention.

Commercially available photocleavable photoradical polymerization initiators include “Irgacure 651”, “Irgacure 184”, “Irgacure 819”, “Irgacure 907”, “Irgacure 1870” (CGI) manufactured by Ciba Specialty Chemicals Co., Ltd. -403 / Irg184 = 7/3 mixed initiator), “Irgacure 500”, “Irgacure 369”, “Irgacure 1173”, “Irgacure 2959”, “Irgacure 4265”, “Irgacure 4263”, “OXE01”, etc .; “Kaya Cure DETX-S”, “Kaya Cure BP-100”, “Kaya Cure BDK”, “Kaya Cure CTX”, manufactured by Yakuhin Co., Ltd.
“Kaya Cure BMS”, “Kaya Cure 2-EAQ”, “Kaya Cure ABQ”, “Kaya Cure CPTX”, “Kaya Cure EPD”, “Kaya Cure ITX”, “Kaya Cure QTX”, “Kaya Cure BTC”, “Kaya Cure MCA”, etc .; Preferred examples include “Esacure (KIP100F, KB1, EB3, BP, X33, KTO46, KT37, KIP150, TZT)” and combinations thereof.

  In addition to the photopolymerization initiator, a photosensitizer may be used. Specific examples of the photosensitizer include n-butylamine, triethylamine, tri-n-butylphosphine, Michler's ketone and thioxanthone. Further, one or more auxiliary agents such as an azide compound, a thiourea compound, and a mercapto compound may be used in combination.

  Examples of commercially available photosensitizers include “Kaya Cure (DMBI, EPA)” manufactured by Nippon Kayaku Co., Ltd.

(Compound having polysiloxane structure)
For the purpose of imparting antifouling properties, it is preferable that a polysiloxane structure is introduced into the fluoropolymer of the present invention. There is no limitation on the method of introducing the polysiloxane structure, but for example, as described in JP-A-6-93100, JP-A-11-189621, JP-A-11-228631 and JP-A-2000-313709, the initiation of silicone macroazo A method of introducing a polysiloxane block copolymer component using an agent, and a method of introducing a polysiloxane graft copolymer component using a silicone macromer as described in JP-A-2-251555 and JP-A-2-308806. preferable. Particularly preferred compounds include the polymers of Examples 1, 2, and 3 of JP-A-11-189621, and the copolymers A-2 and A-3 of JP-A-2-251555. These polysiloxane components are preferably 0.5 to 10% by mass in the polymer, and particularly preferably 1 to 5% by mass.

The blending ratio of each of the above components in the composition of the present invention will be described.
In order to achieve the effect of the present invention, the solid inorganic fine particles (A) are 3.5% by mass or more and 13% by mass or less, preferably 5% by mass or more and 9% by mass with respect to the total solid content of the low refractive index layer. The total amount of the solid inorganic fine particles (A) and the solid inorganic fine particles (B) is 10% by mass or more and 40% by mass or less, preferably 20%, based on the total solid content of the low refractive index layer. It is at least 35% by mass and not more than 35% by mass.
It is preferable to use a photoinitiator (E) in the range of 0.1-15 mass parts with respect to 100 mass parts of photocurable acrylate monomers (D), More preferably, it is the range of 1-10 mass parts. It is.

The low refractive index layer in the present invention has a refractive index of 1.440 or more and 1.465 or less because it does not cause a failure due to whitening and can have high scratch resistance and sufficient antireflection ability. is necessary. A more preferable refractive index is 1.445 or more and 1.455 or less.
Further, the thickness of the low refractive index layer in the present invention is preferably 50 nm or more and 200 nm or less, more preferably 70 nm or more and 110 nm or less,

(Fluorine-containing acrylate monomer (F))
In the present invention, the phase separation of the fluoropolymer (C) and the photocurable acrylate monomer (D) can be more effectively prevented, and a more uniform planar antireflection film can be produced. The composition for forming a low refractive index layer preferably contains a fluorine-containing acrylate monomer. The structure of the fluorine-containing acrylate monomer is not particularly limited, but the fluorine content is preferably 10.0% by mass or more and 20.0% by mass or more from the viewpoint of further improving the compatibility. Is more preferable. Specifically, compounds f-1 to f-10 described in paragraph No. [0018] of JP-A-2006-28409 and X-1 to X-32 described in paragraph Nos. [0023] to [0027]. The following compounds (X-33), (X-34), and (X-35) can also be preferably used.

In addition, compounds described in paragraph numbers 0135 to 0149 of International Publication No. 2005/059601 pamphlet and compounds described in paragraph numbers 0014 to 0028 of JP-A-2006-291077 can also be suitably used.
The amount of the fluorine-containing acrylate monomer used is preferably 5% to 40%, more preferably 10% to 30%, based on the solid content of the low refractive index layer.

An organic solvent can be added to the composition according to the present invention.
Examples of the organic solvent include alcohol, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, isoamyl alcohol, 1-pentanol, n-hexanol, methyl amyl alcohol. In the ketone system, methyl isobutyl ketone, methyl ethyl ketone, diethyl ketone, acetone, cyclohexanone, diacetone alcohol, etc., in the ester system, methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, isobutyl acetate, n-butyl acetate, Isoamyl acetate, n-amyl acetate, methyl propionate, ethyl propionate, methyl butyrate, ethyl butyrate, methyl acetate, methyl lactate, ethyl lactate, ether, acetal, 1,4 dioxane, te In hydrocarbons such as lahydrofuran, 2-methylfuran, tetrahydropyran, diethyl acetal, etc., hexane, heptane, octane, isooctane, ligroin, cyclohexane, methylcyclohexane, toluene, xylene, ethylbenzene, styrene, divinylbenzene, etc., halogen hydrocarbons In, carbon tetrachloride, chloroform, methylene chloride, ethylene chloride, 1,1,1-trichloroethane, 1,1,2-trichloroethane, trichloroethylene, tetrachloroethylene, 1,1,1,2-tetrachloroethane In the case of polyhydric alcohols and derivatives thereof, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoacetate, diethylene glycol, Formic acid such as lenglycol, dipropylene glycol, butanediol, hexylene glycol, 1,5-pentanediol, glycerin monoacetate, propylene glycol monomethyl ether acetate, glycerin ethers, 1,2,6-hexanetriol , Acetic acid, propionic acid, entangling acid, isoentangled acid, isovaleric acid, lactic acid, etc., nitrogen compounds, formamide, N, N-dimethylformamide, acetamide, acetonitrile, etc., sulfur compounds, dimethyl sulfoxide, etc. It is done.

(Anti-glare layer)
An anti-glare layer is a layer provided in order to provide the anti-reflective film with the anti-glare property by surface scattering. In the present invention, the antiglare layer preferably has hard coat properties and antistatic properties for improving the scratch resistance of the film.

  Examples of a method for imparting antiglare properties include a method of forming surface irregularities by utilizing phase separation in the process of evaporation of a solvent from a mixed solution of a plurality of resins as described in JP-A-2005-195919. These known methods can be used.

  The film thickness of the antiglare layer is preferably 1 to 20 μm. By setting it within the above range, hard coat properties, curling, and brittleness can be satisfied.

  On the other hand, the center line average roughness (Ra) of the antiglare layer is preferably in the range of 0.09 to 0.40 μm from the viewpoint of glare or whitening of the surface when external light is reflected. Further, it is preferable that the value of the transmitted image definition is 5 to 60%.

  The strength of the antiglare layer is preferably H or more, more preferably 2H or more, and most preferably 3H or more in a pencil hardness test.

  The antiglare layer can be formed using a technique for forming irregularities on the surface of the coating film by spinodal decomposition of a plurality of resins. Moreover, it becomes possible to provide favorable anti-glare property by giving a difference in the refractive index of the phase which isolate | separated especially the phase. The antiglare layer prepared by spinodal decomposition is composed of a plurality of resins having different refractive indexes, and is usually a phase having at least a co-continuous phase structure in an operating atmosphere (especially at room temperature of about 10 to 30 ° C.). A separation structure is formed. The co-continuous phase structure is formed by spinodal decomposition from a liquid phase containing a plurality of resins (a liquid phase at room temperature, for example, a mixed solution or a solution). The co-continuous phase structure is usually formed by spinodal decomposition using a composition containing a plurality of resins and forming a liquid phase at room temperature (for example, a mixed solution or a solution) and evaporating the solvent. Since such a light scattering layer is formed from a liquid phase, it has a uniform and fine co-continuous phase structure. When such an antireflection film imparted with antiglare properties is used, incident light is substantially isotropically scattered, and directivity can be imparted to transmitted scattered light. Therefore, both high light scattering and directivity can be achieved.

  In order to enhance light scattering properties, a plurality of resins can be used in combination so that the difference in refractive index is, for example, about 0.01 to 0.2, and preferably about 0.1 to 0.15. If the difference in refractive index is less than 0.01, the intensity of the transmitted scattered light decreases. If the difference in refractive index is greater than 0.2, high directivity cannot be imparted to the transmitted scattered light.

Further, for the purpose of imparting light scattering properties, translucent particles can be used in combination in a plurality of resins. The translucent particles can be used in combination so that the difference in refractive index between the resin used and the translucent particles is, for example, about 0.01 to 0.2, preferably about 0.1 to 0.15. . If the difference in refractive index is less than 0.01, the intensity of the transmitted scattered light decreases. If the difference in refractive index is greater than 0.2, high directivity cannot be imparted to the transmitted scattered light. Examples of the translucent particles include the following particles. Such as silica particles, particles of inorganic compounds such as TiO ₂ particles, acrylic particles, crosslinked acryl particles, polystyrene particles, crosslinked styrene particles, melamine resin particles and benzoguanamine resin particles. Of these, crosslinked styrene particles, crosslinked acrylic particles, and silica particles are preferred. The shape of the light-transmitting particles can be either spherical or irregular.

  Moreover, you may use together and use 2 or more types of translucent particle | grains from which a particle diameter differs. For example, when an antireflection film is attached to a high-definition display of 133 ppi or higher, a problem in display image quality called “glare” may occur. “Glitter” originates from the fact that the pixels are enlarged or reduced due to the unevenness present on the surface of the antireflection film and loses the uniformity of brightness, but it is greatly increased by using translucent particles different from the refractive index of the binder. Can be improved.

The translucent particles are contained in the antiglare layer so that the amount of particles in the formed antiglare layer is preferably 10 to 1000 mg / m ² , more preferably 100 to 700 mg / m ² .

  The plurality of resins include, for example, styrene resins, (meth) acrylic resins, vinyl ester resins, vinyl ether resins, halogen-containing resins, olefin resins (including alicyclic olefin resins), polycarbonate resins, and polyesters. Resin, polyamide resin, thermoplastic polyurethane resin, polysulfone resin (polyethersulfone, polysulfone, etc.), polyphenylene ether resin (2,6-xylenol polymer, etc.), cellulose derivatives (cellulose esters, cellulose carbamates) , Cellulose ethers, etc.), silicone resins (polydimethylsiloxane, polymethylphenylsiloxane, etc.), rubbers or elastomers (diene rubbers such as polybutadiene, polyisoprene, styrene-butadiene copolymers, Ronitoriru - butadiene copolymer, acrylic rubber, urethane rubber, silicone rubber, etc.) can be chosen a suitable combination and the like.

  Preferred resins include, for example, styrene resins, (meth) acrylic resins, vinyl ester resins, vinyl ether resins, halogen-containing resins, alicyclic olefin resins, polycarbonate resins, polyester resins, polyamide resins, Cellulose derivatives, silicone resins, rubbers or elastomers are included. As the plurality of resins, a resin that is amorphous and is soluble in an organic solvent (particularly a common solvent capable of dissolving the plurality of resins) is usually used. In particular, resins with high moldability or film formability, transparency and weather resistance, such as styrene resins, (meth) acrylic resins, alicyclic olefin resins, polyester resins, cellulose derivatives (cellulose esters, etc.) Etc. are preferable.

  These plural resins can be used in appropriate combination. For example, in a combination of resins, at least one resin may be selected from cellulose derivatives, particularly cellulose esters (eg, cellulose C2-4 alkyl carboxyls such as cellulose diacetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate). Acid esters) and may be combined with other resins.

  The glass transition temperature of the resin can be selected from the range of, for example, −100 ° C. to 250 ° C., preferably −50 to 230 ° C., more preferably about 0 to 200 ° C. (for example, about 50 to 180 ° C.). From the viewpoint of sheet strength and rigidity, the glass transition temperature of at least one of the constituent resins is 50 ° C. or higher (for example, about 70 to 200 ° C.), preferably 100 ° C. or higher (for example, 100 to 170 ° C.). It is advantageous that The mass average molecular weight of the resin can be selected from the range of, for example, 1,000,000 or less (about 10,000 to 1,000,000), preferably about 10,000 to 700,000.

  Since the present invention employs a wet method in which a solvent is evaporated from a liquid phase containing a plurality of resins and spinodal decomposition is performed, in principle, a substantially isotropic common property is used regardless of the compatibility of the plurality of resins. A light scattering layer having a continuous phase structure can be formed. For this reason, it may be configured by combining a plurality of mutually compatible resins. However, in order to easily control the phase separation structure by spinodal decomposition and to form a co-continuous phase structure efficiently, incompatible (phase separation) In many cases, a plurality of resins are combined.

  The plurality of resins can be configured by a combination of the first resin and the second resin, and each of the first resin and the second resin may be composed of a single resin or a plurality of resins. Also good. A combination of the first resin and the second resin is not particularly limited. For example, when the first resin is a cellulose derivative (for example, cellulose esters such as cellulose acetate propionate), the second resin is a styrene resin (polystyrene, styrene-acrylonitrile copolymer, etc.), (meta ) Acrylic resins (such as polymethyl methacrylate), alicyclic olefin resins (such as polymers using norbornene as monomers), polycarbonate resins, polyester resins (such as poly C2-4 alkylene arylate copolyester) Or the like.

  The ratio of the first resin to the second resin is, for example, the former / the latter = about 10/90 to 90/10 (mass ratio), preferably about 20/80 to 80/20 (mass ratio), and more preferably. Is about 30/70 to 70/30 (mass ratio), particularly about 40/60 to 60/40 (mass ratio). If the proportion of one resin is too large, the volume ratio between the separated phases is biased, so that the intensity of scattered light decreases. In addition, when forming a sheet | seat with 3 or more several resin, content of each resin is 1-90 mass% normally (for example, 1-70 mass%, Preferably 5-70 mass%, More preferably, it is 10 Can be selected from a range of about 70 mass%.

  The antiglare layer constituting the antireflection film of the present invention preferably has at least a co-continuous phase structure. The co-continuous phase structure is sometimes referred to as a co-continuous structure or a three-dimensional continuous or connected structure, and means a structure in which at least two constituent resin phases are continuous (for example, a network structure). . The light scattering layer only needs to have at least a co-continuous phase structure, and may have a structure in which a co-continuous phase structure and a droplet phase structure (independent or isolated phase structure) are mixed. In spinodal decomposition, a co-continuous phase structure is formed as the phase separation progresses, and when the phase separation is further advanced, the continuous phase becomes discontinuous due to its surface tension, and the droplet phase structure (spherical, true spherical) Sea island structure of independent phase). Therefore, depending on the degree of phase separation, an intermediate structure between the co-continuous phase structure and the droplet phase structure, that is, a phase structure in the process of shifting from the co-continuous phase to the droplet phase can be formed. In the present invention, the intermediate structure is also referred to as a co-continuous phase structure. When the phase separation structure is a mixed structure of a co-continuous phase structure and a droplet structure, the ratio of the droplet phase (independent resin phase) is, for example, 30% or less (volume ratio), preferably 10% or less ( Volume ratio). The shape of the co-continuous phase structure is not particularly limited, and may be a network shape, particularly a random network shape.

  The bicontinuous phase structure is generally isotropic with reduced anisotropy in the layer or sheet plane. Note that isotropic means that the average interphase distance of the co-continuous phase structure is substantially equal in any direction in the sheet plane.

  The bicontinuous phase structure usually has regularity in the interphase distance (distance between the same phases). For this reason, the light scattered on the sheet is directed to a specific direction by Bragg reflection. Therefore, even when mounted on a reflective liquid crystal display device, the transmitted scattered light can be directed in a certain direction, the display screen can be made highly bright, and a conventional particle-dispersed transmissive light scattering sheet Thus, a problem that cannot be solved, that is, reflection of a light source (for example, a fluorescent lamp) on the panel can be avoided.

  In the antireflection film, the average interphase distance between the co-continuous phases is, for example, about 0.5 to 20 μm (for example, 1 to 20 μm), preferably about 1 to 15 μm (for example, 1 to 10 μm). If the average interphase distance is too small, it is difficult to obtain high scattered light intensity, and if the average interphase distance is too large, the directivity of transmitted scattered light decreases.

  In addition, the average interphase distance of the co-continuous layer can be calculated from a micrograph (such as a transmission microscope, a phase contrast microscope, or a confocal laser microscope) of the antiglare layer. Alternatively, the scattering angle θ at which the scattered light intensity becomes maximum may be measured, and the average interphase distance d of the co-continuous phase may be calculated from the following Bragg reflection condition equation.

2d · sin (θ / 2) = λ
(Where d is the average interphase distance of co-continuous phases, θ is the scattering angle, and λ is the wavelength of light)

(Hard coat layer)
The antireflection film of the present invention can be provided with a hard coat layer in addition to the antiglare layer in order to impart the physical strength of the film. The hard coat layer may be composed of two or more layers.

  The refractive index of the hard coat layer in the present invention is preferably in the range of 1.48 to 2.00, more preferably 1.52 to 1, from the optical design for obtaining an antireflection film. .90, more preferably 1.55 to 1.80. In the present invention, since there is at least one low refractive index layer on the hard coat layer, if the refractive index is too small, the antireflection property is lowered, and if it is too large, the color of the reflected light tends to be strong. is there.

  From the viewpoint of imparting sufficient durability and impact resistance to the film, the thickness of the hard coat layer is usually about 0.5 μm to 50 μm, preferably 1 μm to 20 μm, more preferably 2 μm. 10 μm, most preferably 3 μm to 7 μm. Further, the strength of the hard coat layer is preferably H or more, more preferably 2H or more, and most preferably 3H or more in a pencil hardness test. Furthermore, in the Taber test according to JISK5400, the smaller the amount of wear of the test piece before and after the test, the better.

  The hard coat layer is preferably formed by a crosslinking reaction or a polymerization reaction of an ionizing radiation curable compound. For example, it can be formed by applying a composition containing an ionizing radiation-curable polyfunctional monomer or polyfunctional oligomer on a transparent support and subjecting the polyfunctional monomer or polyfunctional oligomer to a crosslinking reaction or a polymerization reaction. . The functional group of the ionizing radiation curable polyfunctional monomer or polyfunctional oligomer is preferably a light, electron beam, or radiation polymerizable group, and among them, a photopolymerizable functional group is preferable. Examples of the photopolymerizable functional group include unsaturated polymerizable functional groups such as a (meth) acryloyl group, a vinyl group, a styryl group, and an allyl group. Among them, a (meth) acryloyl group is preferable.

  The hard coat layer contains matte particles having an average particle diameter of 1.0 to 10.0 μm, preferably 1.5 to 7.0 μm, such as inorganic compound particles or resin particles, for the purpose of imparting internal scattering properties. May be.

  For the purpose of controlling the refractive index of the hard coat layer, a high refractive index monomer, inorganic particles, or both can be added to the binder of the hard coat layer. In addition to the effect of controlling the refractive index, the inorganic particles also have the effect of suppressing cure shrinkage due to the crosslinking reaction.

  In order to maintain the sharpness of the image, it is preferable to adjust the clarity of the transmitted image in addition to adjusting the uneven shape of the surface. The clearness of the transmitted image of the clear antireflection film is preferably 60% or more. The transmitted image clarity is generally an index indicating the degree of blurring of an image reflected through a film, and the larger this value, the clearer and better the image viewed through the film. The transmitted image definition is preferably 70% or more, and more preferably 80% or more.

(Antistatic layer, conductive layer)
In the present invention, it is preferable to provide an antistatic layer from the viewpoint of preventing static electricity on the film surface. The antistatic layer can be formed by, for example, applying a conductive coating solution containing conductive fine particles and a reactive curable resin, or depositing or sputtering a metal or metal oxide that forms a transparent film. Conventionally known methods such as a method of forming a conductive thin film and a conductive polymer such as polythiophene or polyaniline can be mentioned. The conductive layer can be formed directly on the support or via a primer layer that strengthens adhesion to the support. The antistatic layer can also be used as a part of the antireflection film.

The thickness of the antistatic layer is preferably from 0.01 to 10 μm, more preferably from 0.03 to 7 μm, and even more preferably from 0.05 to 5 μm. The surface resistance of the antistatic layer is ^preferably from ¹⁰ 5 ~10 ¹² Ω / ^sq, more preferably from 10 5 ~10 ⁹ Ω / ^sq, most be 10 5 ~10 ⁸ Ω / sq preferable. The surface resistance of the antistatic layer can be measured by a four probe method.

  The antistatic layer is preferably substantially transparent. Specifically, the haze of the antistatic layer is preferably 10% or less, more preferably 5% or less, further preferably 3% or less, and most preferably 1% or less. . The transmittance of light having a wavelength of 550 nm is preferably 50% or more, more preferably 60% or more, further preferably 65% or more, and most preferably 70% or more. The antistatic layer of the present invention has excellent strength, and the specific antistatic layer has a pencil hardness of 1 kg, preferably H or higher, more preferably 2H or higher, more preferably 3H or higher. Is more preferable, and 4H or more is most preferable.

(Support)
The support for the film of the present invention is not particularly limited, such as a transparent resin film, a transparent resin plate, a transparent resin sheet, or transparent glass. Transparent resin films include cellulose acylate films (for example, cellulose triacetate film (refractive index 1.48), cellulose diacetate film, cellulose acetate butyrate film, cellulose acetate propionate film), polyethylene terephthalate film, polyethersulfone. Films, polyacrylic resin films, polyurethane resin films, polyester films, polycarbonate films, polysulfone films, polyether films, polymethylpentene films, polyetherketone films, (meth) acrylonitrile films, and the like can be used.

  Among them, a cellulose acylate film having high transparency, optically low birefringence, easy production, and generally used as a protective film for a polarizing plate is preferable, and a cellulose triacetate film is particularly preferable. The thickness of the transparent support is usually about 25 μm to 1000 μm.

In the present invention, it is preferable to use cellulose acetate having an acetylation degree of 59.0 to 61.5% for the cellulose acylate film.
The degree of acetylation means the amount of bound acetic acid per unit mass of cellulose. The degree of acetylation follows the measurement and calculation of the degree of acetylation in ASTM: D-817-91 (test method for cellulose acetate and the like). The viscosity average degree of polymerization (DP) of cellulose acylate is preferably 250 or more, and more preferably 290 or more.
The cellulose acylate used in the present invention has a Mw / Mn (Mw is a mass average molecular weight, Mn is a number average molecular weight) value by gel permeation chromatography close to 1.0, in other words, a molecular weight distribution. Narrow is preferred. The specific value of Mw / Mn is preferably 1.0 to 1.7, more preferably 1.3 to 1.65, and most preferably 1.4 to 1.6. preferable.

In general, the 2, 3, and 6 hydroxyl groups of cellulose acylate are not evenly distributed by 1/3 of the total substitution degree, and the substitution degree of the 6-position hydroxyl group tends to be small. In the present invention, it is preferable that the substitution degree of the 6-position hydroxyl group of cellulose acylate is larger than that of the 2- and 3-positions. The hydroxyl group at the 6-position with respect to the total substitution degree is preferably substituted with 32% or more of an acyl group, more preferably 33% or more, and particularly preferably 34% or more. Furthermore, the substitution degree of the 6-position acyl group of cellulose acylate is preferably 0.88 or more. The 6-position hydroxyl group may be substituted with a propionyl group, butyroyl group, valeroyl group, benzoyl group, acryloyl group or the like, which is an acyl group having 3 or more carbon atoms, in addition to the acetyl group. The degree of substitution at each position can be determined by NMR.
In the present invention, as cellulose acylate, paragraphs “0043” to “0044” [Example] [Synthesis Example 1], paragraphs “0048” to “0049” [Synthesis Example 2], and paragraph “ Cellulose acetate obtained by the method described in “0051” to “0052” [Synthesis Example 3] can be used.

  In the present invention, a polyethylene terephthalate film is also preferably used because it is excellent in transparency, mechanical strength, flatness, chemical resistance and moisture resistance, and is inexpensive. In order to further improve the adhesion strength between the transparent plastic film and the hard coat layer provided thereon, the transparent plastic film is more preferably subjected to an easy adhesion treatment. Examples of commercially available PET films with an easily adhesive layer for optics include Cosmo Shine A4100 and A4300 manufactured by Toyobo Co., Ltd.

(Layer structure of antireflection film)
In general, the antireflection film of the present invention has a simplest configuration in which only an antiglare layer and a low refractive index layer are coated on a transparent support. Further, it is also preferable to combine the antistatic layers in order to impart dust resistance.

  The example of the preferable layer structure of the antireflection film of this invention is shown below. In the following configuration, what is described as (antistatic layer) is a configuration in which a layer having other functions also has the function of an antistatic layer. Since the number of layers to be formed can be reduced by providing the antistatic layer with a function other than antistatic, this structure is preferable because productivity is improved.

Support / antiglare layer (hard coat layer) / low refractive index layerSupport / antiglare layer (antistatic layer) / low refractive index layer / support / hard coat layer / antiglare layer (antistatic layer) / Low refractive index layer / support / hard coat layer / antistatic layer / antiglare layer / low refractive index layer / support / hard coat layer (antistatic layer) / antiglare layer / low refractive index layer

  As long as the reflectance can be reduced by optical interference, it is not limited to these layer configurations.

(Curing conditions for low refractive index layer)
Preferred examples of the method for curing the low refractive index layer in the present invention are described below.
In the present invention, by using a photocurable fluoropolymer (C) containing an ethylenically unsaturated group and a photocurable acrylate monomer (D) in combination, the refractive index of the coating film is reduced and the strength of the coating film is improved. It is effective to cure by combining ionizing radiation irradiation with heat treatment before, at the same time as or after irradiation after the coating is formed.
Although the pattern of some manufacturing processes is shown below, it is not limited to these.
Before irradiation → simultaneous with irradiation → after irradiation (-indicates that heat treatment is not performed)
(1) Heat treatment → Ionizing radiation curing →-
(2) Heat treatment → Ionizing radiation curing → Heat treatment (3)-→ Ionizing radiation curing → Heat treatment In addition, a step of performing heat treatment simultaneously with ionizing radiation curing is also preferable.

(Heat treatment)
In the present invention, as described above, heat treatment is preferably performed in combination with irradiation with ionizing radiation. The heat treatment is not particularly limited as long as it does not damage the constituent layers including the support for the antireflection film and the low refractive index layer, but is preferably 60 to 200 ° C., more preferably 80 to 130 ° C., most preferably 80 to 110 ° C.

  By raising the temperature, the orientation and distribution of each component in the coating film can be adjusted, and the photocuring reaction can be controlled. Prior to curing with ionizing radiation or heat, each component is not immobilized and the orientation of each component occurs relatively quickly.However, after the initiation of curing, each component is fixed and orientation occurs only partially. Absent. The time required for the heat treatment varies depending on the molecular weight of the component used, interaction with other components, viscosity, etc., but is 30 seconds to 24 hours, preferably 60 seconds to 5 hours, and most preferably 3 minutes to 30 minutes.

  Although there is no limitation in particular in the method of setting the film surface temperature of a film to desired temperature, The method of heating a roll and contacting a film, the method of spraying heated nitrogen, irradiation of far infrared rays or infrared rays, etc. are preferable. A method described in Japanese Patent No. 2523574 may also be used, in which hot water or steam is passed through a rotating metal roll and heated. On the other hand, at the time of irradiation of ionizing radiation described below, when the film surface temperature of the film rises, a method of cooling the roll and bringing it into contact with the film can be used.

  The film surface temperature during irradiation with ionizing radiation is not particularly limited, but is generally 20 to 200 ° C., preferably 30 to 150 ° C., and most preferably 40 to 120 ° C. in view of handling properties and in-plane performance uniformity. It is. If the film surface temperature is not more than the above upper limit value, the fluidity of the low molecular component in the binder is excessively increased and the surface state is not deteriorated, and the problem that the support is damaged by heat does not occur. Moreover, if it is more than this lower limit, the curing reaction proceeds sufficiently and the film has good scratch resistance, which is preferable.

There is no restriction | limiting in particular about the kind of ionizing radiation, Although an X-ray, an electron beam, an ultraviolet-ray, visible light, infrared rays etc. are mentioned, an ultraviolet-ray is used widely. 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. When irradiating, the energy may be applied at once, or divided and irradiated. In particular, from the viewpoint of reducing the performance variation in the surface of the coating film, it is also preferable to irradiate by dividing into about 2 to 8 times.

  The time during which the film is kept at the above temperature after irradiation with ionizing radiation is preferably from 0.1 seconds to 300 seconds, more preferably from 0.1 seconds to 10 seconds from the end of irradiation with ionizing radiation. If the time for keeping the film surface temperature of the film within the above temperature range is too short, the reaction of the composition for forming a low refractive index layer that forms a film cannot be promoted. Problem arises.

  The oxygen concentration at the time of ionizing radiation irradiation is preferably 3% by volume or less, more preferably 1% by volume or less, and still more preferably 0.1% or less. In contrast to the step of irradiating with ionizing radiation at an oxygen concentration of 3% by volume or less, by providing a step of maintaining in an atmosphere at an oxygen concentration of 3% by volume immediately before or immediately after that, the curing of the film is sufficiently promoted, A film excellent in strength and chemical resistance can be formed.

  The heat treatment step before, simultaneously with or after the irradiation with ionizing radiation can be performed in the atmosphere, but it is also preferable to decrease the oxygen concentration as in the ionizing radiation irradiation. In particular, when the thermal stability of a polymerization initiator, a polymerizable compound, or the like is insufficient, the strength of the film after completion of the entire curing process can be kept strong by performing a heat treatment with a reduced oxygen concentration.

  As a means for reducing the oxygen concentration, it is preferable to replace the atmosphere (nitrogen concentration of about 79% by volume, oxygen concentration of about 21% by volume) with another inert gas, and particularly preferably with nitrogen (nitrogen purge). It is. By carrying it in an atmosphere having a low oxygen concentration before the step of irradiating with ionizing radiation, the oxygen concentration inside the coating film surface and inside can be effectively reduced, and curing can be promoted. The oxygen concentration in the transport step before ionizing radiation irradiation is preferably 3% by volume or less, more preferably 1% volume or less, and still more preferably 0.1% or less.

(Saponification treatment)
When the antireflection film of the present invention is disposed on the outermost surface of a display by providing an adhesive layer on one side, or is used as it is as a protective film for a polarizing plate, it is a transparent support for sufficient adhesion. It is preferable to carry out a saponification treatment after an outermost layer mainly composed of a fluoropolymer is formed thereon.

  The saponification treatment is performed by a known method, for example, by immersing the film in an alkali solution for an appropriate time. After being immersed in the alkaline solution, it is preferable to sufficiently wash with water or neutralize the alkaline component by dipping 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 side having the outermost layer is hydrophilized. The hydrophilized surface is particularly effective for improving the adhesion with a polarizing film containing polyvinyl alcohol as a main component. The hydrophilic surface makes it difficult for dust in the air to adhere to it, making it difficult for dust to enter between the polarizing film and the antireflective film when bonded to the polarizing film, and is effective in preventing point defects caused by dust. is there.

  The saponification treatment is preferably carried out so that the contact angle of water on the surface of the transparent support opposite to the side having the outermost layer is 40 ° or less. More preferably, it is 30 ° or less, particularly preferably 20 ° or less.

  Specific means for the alkali saponification treatment can be selected from the following two means (1) and (2). (1) is superior in that it can be processed in the same process as a general-purpose triacetyl cellulose film, but since the surface of the antireflection film is saponified, the surface is alkali-hydrolyzed and the film deteriorates. The point that it becomes dirty when the liquid remains can be a problem. In that case, although it becomes a special process, (2) is excellent.

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

  In the present invention, the conditions described below are the standard saponification conditions. In general, the polarizing plate in the state of being saponified and processed into a polarizing plate by a continuous treatment in the polarizing plate manufacturing process is also “antireflection after saponification” of the present invention. It is defined as “a polarizing plate having a film”.

Saponification standard conditions: The antireflection film is treated and dried in the following steps.
Alkaline bath: 1.5 mol / dm ³ aqueous sodium hydroxide solution at 55 ° C. for 120 seconds.
First washing bath: tap water, 60 seconds.
Neutralization bath: 0.05 mol / dm ³ sulfuric acid, 30 ° C. for 20 seconds.
Second washing bath: tap water, 60 seconds.
Drying: 120 ° C., 60 seconds.
The dynamic friction coefficient of the antireflection film of the present invention is preferably 0.03 to 0.40, more preferably 0.03 to 0.35 or less, and most preferably 0.03 to 0.30. preferable.

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

  The antireflection film of the present invention is used in image display devices such as liquid crystal display devices (LCD), plasma display panels (PDP), electroluminescence displays (ELD), cathode ray tube display devices (CRT), and surface electric field displays (SED). Can be applied. It is particularly preferably used for a liquid crystal display (LCD). Since the antireflection film of the present invention has a transparent support, the transparent support side is adhered to the image display surface of the image display device.

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

  In order to describe the present invention in detail, examples will be described below, but the present invention is not limited to these examples. In addition, with a part means a mass part.

(Preparation of coating solution for antiglare layer)
A coating solution was prepared with the following composition.
PET-30 44.0g
Viscoat 360 44.0g
Irgacure 127 3.0g
6μm cross-linked acrylic-styrene particle dispersion (30%) 26.4 g
6 μm cross-linked acrylic particle dispersion (30%) 9.9 g
SP-13 0.2g
Methyl isobutyl ketone (MIBK) 16.1 g
Methyl ethyl ketone (MEK) 40.4g

  The coating solution was filtered through a polypropylene filter having a pore size of 30 μm to prepare a coating solution for an antiglare layer. In the antiglare layer coating solution, the refractive index of the matrix after curing was 1.51.

The above dispersion of particles was prepared by gradually adding the following particles to the stirring MIBK solution until the solid concentration of the dispersion reached 30% by mass and stirring for 30 minutes. Resin particles manufactured by Sekisui Plastics Co., Ltd. were used.
6 μm crosslinked acrylic-styrene particles: refractive index 1.56 (acrylic / styrene ratio: 3/7)
6 μm crosslinked acrylic particles: refractive index 1.50

(Preparation of inorganic fine particle dispersion)
(Preparation of dispersion A-1)
1. 500 parts of silica sol (silica, MEK-ST-L, average particle size 45 nm, solid content concentration 30%, manufactured by Nissan Chemical Co., Ltd.) 20 parts acryloyloxypropyltrimethoxysilane and diisopropoxyaluminum ethyl acetate After adding 5 parts and mixing, 9 parts of ion-exchanged water was added. After reacting at 60 ° C. for 8 hours, the mixture was cooled to room temperature, and 1.8 parts of acetylacetone was added. Finally, dispersion A-1 was prepared by adjusting the solid content to 20% by mass.

(Preparation of dispersion A-2)
20 parts of acryloyloxypropyltrimethoxysilane and 1.5 parts of diisopropoxyaluminum ethyl acetate with respect to 500 parts of silica sol (silica, MEK-ST, average particle size 15 nm, solid concentration 30%, manufactured by Nissan Chemical Co., Ltd.) After addition and mixing, 9 parts of ion exchange water was added. After reacting at 60 ° C. for 8 hours, the mixture was cooled to room temperature, and 1.8 parts of acetylacetone was added. Finally, a dispersion A-2 was prepared by adjusting the solid content to 20% by mass.
Fluoropolymer (1)

(Synthesis of fluoropolymer (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 a fluoropolymer (1). The obtained polymer had a mass average molecular weight of 31,000 and a refractive index of 1.421.

(Preparation of coating solution for low refractive index layer)
7.6 g of the fluoropolymer (1) obtained as described above, 1.4 g of DPHA, 2.4 g of the dispersion A-1, a photopolymerization initiator (Irgacure 907 (trade name), manufactured by Ciba Geigy Corporation) ) 0.46 g, methyl ethyl ketone 190 g, and propylene glycol monomethyl ether acetate 48 g were added. After stirring, the mixture was filtered through a polypropylene filter having a pore size of 5 μm to prepare a coating solution Ln1 for a low refractive index layer.

The compounds used above are shown below.
PET-30: A mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate [manufactured by Nippon Kayaku Co., Ltd.]
Biscoat 360: ethylene oxide-modified trimethylolpropane triacrylate [manufactured by Osaka Organic Chemicals]
Irgacure 127: Polymerization initiator [Ciba Specialty Chemicals Co., Ltd.],
DPHA: a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate [manufactured by Nippon Kayaku Co., Ltd.]
SP-13: Fluorine-based surfactant (used after dissolving as a 10% by mass solution of MEK)

(Coating of antiglare layer)
An 80 μm-thick triacetyl cellulose film (TAC-TD80U, manufactured by Fuji Film Co., Ltd.) is unwound from a roll form, and the coating solution for the antiglare layer is used in Example 1 of JP-A-2006-122889. The die-coating method using the slot die described above was applied at a conveyance speed of 30 m / min, dried at 60 ° C. for 150 seconds, and further air-cooled metal halide lamp with an oxygen concentration of about 0.1% under a nitrogen purge at 160 W / cm. using (manufactured by eye graphics Co., Ltd.), intensity 400 mW / cm ^2, was wound to cure the coating layer by an irradiation dose of 100 mJ / cm ^2. The coating amount was adjusted so that the film thickness of the antiglare layer was 14 μm.

(Coating of low refractive index layer)
Unwind the triacetyl cellulose film coated with the antiglare layer again, and apply the coating solution Ln1 for the low refractive index layer under the condition of a conveyance speed of 30 m / min by the die coating method using the slot die. After drying at 90 ° C. for 75 seconds, using an air-cooled metal halide lamp (produced by Eye Graphics Co., Ltd.) with an oxygen concentration of 0.01 to 0.1% under a nitrogen purge, irradiation of 400 mW / cm ² and irradiation An ultraviolet ray having an amount of 240 mJ / cm ² was irradiated to form a low-refractive index layer having a thickness of 100 nm, and wound to prepare antiglare antireflection film sample 1.

(Saponification treatment of antireflection film)
The obtained antireflection film was treated and dried under the following saponification standard conditions.
Alkaline bath: 1.5 mol / dm ³ aqueous sodium hydroxide solution at 55 ° C. for 120 seconds.
First washing bath: tap water, 60 seconds.
Neutralization bath: 0.05 mol / dm ³ sulfuric acid, 30 ° C. for 20 seconds.
Second washing bath: tap water, 60 seconds.
Drying: 120 ° C., 60 seconds.

(Evaluation of antireflection film)
The following evaluation was performed using the saponified antireflection film.

(Evaluation 1) Evaluation of whitening Oil-based black ink was applied to the surface of the antireflective film sample opposite to the low refractive index layer and visually observed with reflected light, and the whitening of the low refractive index layer was evaluated according to the following criteria. .
A: Even if you look carefully, no whitening is visible. Or although whitening is seen slightly, even if the surface is rubbed, there is no change in surface shape.
B: When looked carefully, whitening is slightly seen, and when the surface is rubbed, the surface shape changes.
C: Whitening can be visually recognized at first glance, and the surface shape changes when the surface is rubbed.

(Evaluation 2) Eraser scratch resistance evaluation A rubbing test was conducted using a rubbing tester under the following conditions.
Evaluation environmental conditions: 25 ° C., 60% RH.
Rubbing material: A plastic eraser {"MONO" manufactured by Dragonfly Pencil Co., Ltd.) was fixed to the rubbing tip (1 cm x 1 cm) of the tester in contact with the sample.
Travel distance (one way): 4cm
Rubbing speed: 2 cm / second,
Load: 250 g / cm ² ,
Tip contact area: 1 cm × 1 cm.
Number of rubbing: 50 reciprocations.
The antireflective film sample tested by the above method and rubbed is coated with oily black ink on the surface opposite to the low refractive index layer, visually observed with reflected light, and scratches on the rubbed part are evaluated according to the following criteria: did.
A: Even if you look very carefully, no scratches are visible.
B: A weak wound is visible.
C: There is a scratch that can be seen at first glance.

(Evaluation 3) Measurement of Integral Reflectance Integral reflectivity was measured by roughening the transparent support surface of the film (the surface opposite to the low refractive index layer) with sandpaper, followed by light absorption treatment with black ink (380 A sample with a transmittance at 780 nm of less than 10%) and no back reflection was used as a measurement sample. A spectrophotometer “V-550” (manufactured by JASCO Corporation) is equipped with an adapter “ILV-471”, and an integrated reflectance is measured on a black table in a wavelength region of 380 to 780 nm. An average reflectance of ˜650 nm was calculated, and antireflection properties were evaluated.

(Evaluation 4) Evaluation of surface uniformity by phase separation Oil-based black ink is applied to the surface of the antireflective film sample opposite to the low refractive index layer, and the surface shape of the low refractive index layer is visually observed with reflected light. The uniformity was evaluated according to the following criteria.
A: Even if you look carefully, you can see no unevenness on the surface.
B: Slight unevenness can be seen when looking carefully.
C: Unevenness can be visually recognized at a glance.

(Preparation and evaluation of antireflection film samples 2 to 69)
In the production of the antireflection film sample 1, the antireflection film sample 2 was prepared in the same manner as the antireflection film sample 1 except that the coating liquid Ln1 for the low refractive index layer was changed to Ln2 to Ln69 shown in Tables 1 to 6. -69 were made. The evaluation results are shown in Tables 1-6. The numerical values of silica and fluorine-containing polymer in the table are the solid content concentration (% by mass) in the coating film. The refractive index indicates the refractive index of the low refractive index layer, and these are controlled by changing the solid content ratio of the fluoropolymer and the photocurable acrylate monomer. In the following table, the numerical value in the column of silica is the content (mass%) of silica fine particles with respect to the total solid content of the low refractive index layer.

  From the results shown in the above table, it has been found that the antireflection film of the present invention has no failure due to whitening, has sufficient antireflection properties, and provides a coating film with good scratch resistance.

Claims (8)

On the transparent support, it has an antiglare layer and a low refractive index layer in this order, and the low refractive index layer contains the following components (A), (B), (C), (D) and (E). A cured product of the composition;
(A) Solid inorganic fine particles having an average particle diameter of 40 to 100 nm (B) Solid inorganic fine particles having an average particle diameter of 1 to 30 nm (C) A photocurable fluorine-containing polymer (D) containing an ethylenically unsaturated group Photocurable acrylate monomer (E) photopolymerization initiator The content of the solid inorganic fine particles (A) is 3.5% by mass or more and 13% by mass or less based on the total solid content of the low refractive index layer, The total content of the solid inorganic fine particles (A) and the solid inorganic fine particles (B) is 10% by mass to 40% by mass with respect to the total solid content of the low refractive index layer, and the low refractive index layer The antireflective film whose refractive index is 1.440 or more and 1.465 or less.   The antireflection film according to claim 1, wherein both the solid inorganic fine particles (A) and the solid inorganic fine particles (B) are silica fine particles.   The surface of the said solid inorganic fine particle (A) and the said solid inorganic fine particle (B) is surface-treated by at least any one chosen from the hydrolyzate of an organosilane compound, and its partial condensate. The antireflection film as described.   The photocurable fluorine-containing polymer (C) containing an ethylenically unsaturated group is a copolymer (P) whose main chain is composed of only carbon atoms, and the copolymer (P) is a fluorine-containing vinyl monomer. The antireflection film according to any one of claims 1 to 3, comprising a polymer unit derived from the above and a polymer unit having a (meth) acryloyl group in a side chain. The antireflection film according to claim 4, wherein the copolymer (P) is represented by the following general formula 1.

In General Formula 1, L represents a linking group having 1 to 10 carbon atoms, and m represents 0 or 1. X represents a hydrogen atom or a methyl group. A represents a polymerization unit derived from an arbitrary vinyl monomer, and may be composed of a single component or a plurality of components. x, y, and z represent mol% of each polymerization unit, and represent values satisfying 30 ≦ x ≦ 60, 5 ≦ y ≦ 70, and 0 ≦ z ≦ 65. However, x + y + z is 100 mol%.   The antireflection film according to any one of claims 1 to 5, wherein the composition further contains a fluorine-containing acrylate monomer (F).   A polarizing plate comprising a polarizing film and protective films provided on both sides of the polarizing film, wherein at least one of the protective films is the antireflection film according to claim 1.   An image display device in which the antireflection film according to claim 1 or the polarizing plate according to claim 7 is disposed on an image display surface.