JP4856880B2 - Antireflection film, polarizing plate and image display device - Google Patents

Description

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

  In general, the antireflection film is a film that reduces the reflectivity by using the principle of optical interference. For example, an antireflection film such as a cathode ray tube display (CRT), a plasma display (PDP), an electroluminescence display (ELD), or a liquid crystal display (LCD). In such an image display device, in order to prevent a decrease in contrast and reflection of an image due to reflection of external light, the image display device is disposed on the outermost surface of the display so as to reduce the reflectance.

  Such an antireflection film has a low refractive index layer having an appropriate film thickness on the outermost surface on the support, and optionally a high refractive index layer, a medium refractive index layer, between the support and the low refractive index layer, It can be produced by forming a hard coat layer or the like. In order to realize a low reflectance, a material having a refractive index as low as possible is desired for the low refractive index layer. Further, since the antireflection film is used on the outermost surface, a function as a protective film of the display of the image display device is expected. That is, it is required that dirt and dust are difficult to adhere and that scratch resistance is strong.

In order to lower the refractive index of the material, there are means of introducing an organic group containing a fluorine atom into the binder and lowering the density (introducing voids). When organic groups containing fluorine atoms are used in the binder, the cohesive force of the binder itself is reduced, and there is a limit in reducing the refractive index practically by introducing the necessary linking group to compensate for it. , 1.40 or less was difficult. On the other hand, the method of reducing the refractive index by introducing microscopic voids in the low refractive index layer can be less than 1.40, but the film strength is weak, and defects such as fingerprints and oil are liable to enter. was there.
For example, Patent Document 1, Patent Document 2 and Patent Document 3 have an attempt to lower the refractive index by forming micropores in the binder. Patent Document 4 has an attempt to lower the refractive index using porous silica. None of these were practically satisfactory in terms of film strength, fingerprint contamination, and the like.
Patent Document 5, Patent Document 6, Patent Document 7, Patent Document 8 and Patent Document 9 have a description of an antireflection film containing hollow silica particles in a low refractive index layer.
JP-A-6-3501 JP-A-9-222502 Japanese Patent Laid-Open No. 9-222503 JP 7-48527 A JP 2001-233611 A JP 2002-79616 A JP 2002-317152 A JP 2003-202406 A JP 2003-292831 A

The antireflection film containing hollow silica particles in the low refractive index layer has improved the scratch resistance and the adhesion resistance of dirt such as fingerprints to the conventional one, but it is used for image display devices such as liquid crystal display devices. The problem that the film was destroyed by the saponification at the time of making the polarizing plate, or the trace remained when water droplets newly adhered was revealed. Since the antireflection film is used on the outermost surface of the display, water drops may adhere in daily use, and improvement is necessary from the viewpoint of imparting practical durability.
An object of the present invention is to provide an antireflection film having a low reflectance, improved adhesion of water droplets, and excellent antifouling properties. Furthermore, it is providing the polarizing plate and image display apparatus using such an antireflection film, and providing the manufacturing method of such an antireflection film.

As a result of intensive studies, the inventor has found that the above-described target of the present invention can be achieved by an antireflection film having the following constitution, a production method thereof, a polarizing plate, and an image display device.
<1>
On a transparent support, porous and / or hollow inorganic fine particles having an adsorbed water amount of 6.1% by mass or less and a particle size of 20 to 100 nm, a compound for reducing surface free energy, and a saturated hydrocarbon having a crosslinked structure An antireflection film having a low refractive index layer containing a binder polymer having a chain as a main chain,
The compound for reducing the surface free energy is a silicone compound containing at least one active energy ray-curable (meth) acryloyl group in the molecule,
The binder polymer having a saturated hydrocarbon chain having a crosslinked structure as a main chain is composed of a (co) polymer of monomers having two or more ethylenically unsaturated groups, and the monomers are selected from the following: Anti-reflection film.
Esters of polyhydric alcohol and (meth) acrylic acid, vinylbenzene and its derivatives, vinyl sulfone, acrylamide, and methacrylamide
<2>
The binder polymer having a saturated hydrocarbon chain having a crosslinked structure as a main chain is a (co) polymer of a monomer having two or more ethylenically unsaturated groups, and the monomer is selected from the following: The antireflection film as described in <1> above.
Ethylene glycol di (meth) acrylate, 1,4-cyclohexanediacrylate, pentaerythritol tetra (meth) acrylate), pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate , Dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,2,3-cyclohexanetetramethacrylate, polyurethane polyacrylate, polyester polyacrylate, 1,4- Divinylbenzene, 4-vinylbenzoic acid-2-acryloylethyl ester, 1,4-divinylcyclohexanone, divinylsulfone, methylenebisacrylic Luamide
<3>
Silicone and / or fluoroalkyl groups segregate on the surface of the low refractive index layer, and the photoelectron spectral intensity ratio Si / C and / or F / C in the lowermost layer and 80% below the outermost surface of the low refractive index layer The antireflection film as described in <1> or <2> above, wherein the outermost surface is at least 5 times larger than the lower layer of 80%.
<4>
The surface of the inorganic fine particles is treated with a hydrolyzate of organosilane represented by the following general formula (I) and / or a partial condensate thereof using an acid catalyst and / or a metal chelate compound. The antireflection film as described in any one of <1> to <3> above,
Formula (I): (R ¹⁰ ) _m Si (X) _4-m
(In the formula, R ¹⁰ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. X represents a hydroxyl group or a hydrolyzable group. M represents an integer of 1 to 3.)
<5>
A polarizing plate comprising the antireflection film according to any one of <1> to <4> above.
<6>
An image display device comprising the antireflection film according to any one of <1> to <4> or the polarizing plate according to <5>.
In addition, although this invention is related to said <1>-<6>, the other matter (For example, the matter of following 1-14, etc.) was also described for reference.
1. On a transparent support, it has a low refractive index layer containing porous and / or hollow inorganic fine particles having an adsorbed water amount of 6.1% by mass or less and a particle size of 20 to 100 nm and a compound for reducing surface free energy. Antireflection film characterized by
2. The compound for reducing the surface free energy includes at least one selected from a silicone compound and a fluorine-based compound. 2. Antireflection film according to 3. 2. The compound as described in 2 above, wherein the compound for reducing the surface free energy is a silicone compound. The antireflection film as described in 1.
4). The compound for reducing the surface free energy contains at least one group having reactivity with a binder in the molecule. ~ 3. The antireflection film according to any one of the above.
5. The compound for reducing the surface free energy contains at least one active energy ray-curable (meth) acryloyl group in the molecule. ~ 4. The antireflection film according to any one of the above.
6). On the transparent support, the layer has a low refractive index including porous and / or hollow inorganic fine particles having an adsorbed water amount of 6.1% by mass or less and a particle size of 20 to 100 nm and a binder having a surface free energy reducing ability. An antireflection film characterized by that.
7). Silicone and / or fluoroalkyl groups segregate on the surface of the low refractive index layer, and the photoelectron spectral intensity ratio Si / C and / or F / C in the lowermost layer and 80% below the outermost surface of the low refractive index layer The above-mentioned 1. characterized in that the outermost surface is at least 5 times larger than the 80% lower layer. ~ 6. The antireflection film according to any one of the above.
8). 5. The binder according to the above 6, wherein the binder having a surface free energy reducing ability contains silicone and / or fluorine. Or 7. The antireflection film as described in 1.
9. 5. The binder according to 6 above, wherein the binder having a surface energy reducing ability is a fluoropolymer. ~ 8. The antireflection film according to any one of the above.
10. 5. The binder having the ability to reduce the surface free energy is a polymer having an active energy ray-curable (meth) acryloyl group. ~ 9. The antireflection film according to any one of the above.
11. 5. The binder having the ability to lower the surface free energy is represented by the general formula 1. -10. The antireflection film according to any one of the above.

12 . The surface of the inorganic fine particles is treated with a hydrolyzate of organosilane represented by the following general formula (I) and / or a partial condensate thereof using an acid catalyst and / or a metal chelate compound. Characteristic 1. ~ 11 . The antireflection film according to any one of the above.
Formula (I): (R ¹⁰ ) _m Si (X) _4-m
(In the formula, R ¹⁰ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. X represents a hydroxyl group or a hydrolyzable group. M represents an integer of 1 to 3.)
13 . Above 1. To 12. A polarizing plate comprising the antireflection film according to any one of the above.
14 . Above 1. To 12. 12. The antireflection film according to any one of the above or 13 . An image display device comprising the polarizing plate described in 1.

  The antireflection film of the present invention has a low reflectivity, is less likely to leave water droplets, and has excellent antifouling properties. Furthermore, a polarizing plate or a display using the antireflection film of the present invention has very high visibility because there is little reflection of external light and reflection of the background.

  Hereinafter, the present invention will be described in detail. In the present specification, when a numerical value represents a physical property value, a characteristic value, etc., the description “(numerical value 1) to (numerical value 2)” means “(numerical value 1) or more and (numerical value 2) or less”. .

[Low refractive index layer]
First, the low refractive index layer of the present invention will be described.
The refractive index of the low refractive index layer of the antireflection film of the present invention is preferably 1.20 to 1.46, more preferably 1.25 to 1.40, and 1.25 to 1.38. It is particularly preferred that Further, the low refractive index layer preferably satisfies the following formula (I) from the viewpoint of reducing the reflectance.
(Mλ / 4) × 0.7 <n ₁ d ₁ <(mλ / 4) × 1.3 (Equation (I))
In the formula, m is a positive odd number, n ₁ is the refractive index of the low refractive index layer, and d ₁ is the film thickness (nm) of the low refractive index layer. Further, λ is a wavelength, which is a value in the range of 500 to 550 nm. In addition, satisfy | filling said numerical formula (I) means that m (positive odd number, usually 1) which satisfy | fills numerical formula (I) exists in the said wavelength range.

In the present invention, the low refractive index layer contains porous and / or hollow inorganic fine particles having an adsorbed water amount of 6.1% by mass or less and a particle size of 20 to 100 nm, and a compound for reducing the surface free energy. It is characterized by that.
The porous and / or hollow inorganic fine particles in which the amount of adsorbed water contained in the low refractive index layer of the present invention is 6.1% by mass or less and the particle size is 20 to 100 nm will be described below.

[Method for preparing pore-containing fine particles]
When these pore-containing fine particles (porous or hollow fine particles) are used, the structure and type are not limited, but porous or hollow inorganic oxide fine particles are preferable. In the case of inorganic oxide fine particles, fine particles mainly composed of aluminum oxide, silicon oxide, and tin oxide are preferable.
A preferred method for producing hollow fine particles comprises the following steps. The first step is the formation of core particles that can be removed by post-treatment, the second step is the formation of a shell layer, the third step is the dissolution of core particles, and the fourth step is the formation of an additional shell phase if necessary. Specifically, the hollow particles can be produced according to the method for producing hollow silica fine particles described in, for example, JP-A-2001-233611.
A preferred method for producing porous particles is to produce porous core particles by controlling the degree of hydrolysis and condensation of alkoxide and the type and amount of coexisting substances as the first step, and a shell layer on the surface as the second step. It is a method of forming. Specifically, the production of porous particles can be performed by the methods described in JP-A Nos. 2003-327424, 2003-335515, 2003-226516, 2003-238140, and the like. it can.
In the present invention, it is preferable to reduce the amount of water adsorbed by inorganic fine particles, which will be described later, and it can be controlled by changing the particle size, changing the shell thickness, hydrothermal treatment conditions, and the like. Also, the amount of adsorbed water can be reduced by firing the particles.

[Measurement of adsorbed water content of pore-containing fine particles]
In the present invention, the amount of adsorbed water of the pore-containing fine particles can be determined by the following measuring method. The particle powder was dried for 1 hour at 20 ° C. under a condition of about 1 hPa using a rotary pump. Thereafter, it was stored at 20 ° C.-55% relative humidity for 1 hour. Using a DTG-50 manufactured by Shimadzu Corporation, about 10 mg of the dried sample was weighed into a platinum cell, and the temperature was increased from 20 ° C. to 950 ° C. at a heating rate of 20 ° C./min. The amount of adsorbed water was calculated by the following formula as a percentage of mass decrease when the temperature was raised to 200 ° C.
Adsorbed water amount (%) = 100 × (W20−W200) / W200
(W20: initial mass at the start of temperature rise, W200: mass at the time when the temperature is raised to 200 ° C.)
In the case where the particles are a dispersion, the solvent can be distilled off with an evaporator (25 ° C., reduced pressure to 10 hPa), and the residue can be ground in an agate mortar to obtain a powder, and then measured in the above step.
In the present invention, the amount of adsorbed water is preferably 6.1% by mass or less, more preferably 5.5% by mass or less, and most preferably 5.0% by mass or less.
When a plurality of particles having different particle sizes and preparation conditions are included in the layer, the amount of adsorbed water of at least one of these particles may be 6.1% by mass or less. However, the ratio of the amount of adsorbed water to all particles of 6.1% by mass or less is preferably 30% by mass or more, more preferably 50% by mass or more, and further preferably 70% by mass or more. preferable.

[Measurement of particle size of pore-containing fine particles]
In the measurement of the size of the pore-containing fine particles of the present invention, the particles were observed with a transmission electron microscope, and the equivalent circle diameter was calculated as an average of 1,000 particles. The diameter is preferably 20 to 100 nm, more preferably 35 to 100 nm, and most preferably 45 to 80 nm. If the particle size is too small, an increase in the refractive index and an increase in the amount of adsorbed water are observed, which is not preferable.
In the present invention, the pore-containing fine particles may have a size distribution, and the coefficient of variation thereof is preferably 60% to 5%, more preferably 50% to 10%. In addition, two or more kinds of particles having different average particle sizes can be mixed and used.

[Measurement of refractive index of pore-containing fine particles]
The refractive index of the pore-containing fine particles that can be preferably used in the present invention is preferably 1.15 to 1.40, more preferably 1.15 to 1.35, and most preferably 1.18 to 1.30. . The refractive index of the particles can be determined by the following method.
(1) Preparation of matrix-forming component liquid A mixed solution of 55 g of tetraethoxysilane (TEOS) (SiO ₂ concentration 28 mass%), 200 g of ethanol, 1.4 g of concentrated nitric acid and 34 g of water was stirred at room temperature for 5 hours. A liquid (M-1) containing a matrix-forming component was prepared by adjusting the amount of ethanol so that the concentration when converted to SiO ₂ was 5% by mass.
(2) Preparation of coating film The matrix-forming component liquid (M-1) and the pore-containing fine particles are converted into an oxide-converted mass ratio [matrix (SiO ₂ ): pore-containing fine particles (MO _x + SiO ₂ )]. The coating solutions for refractive index measurement were prepared so as to be 100: 0, 90:10, 80:20, 60:40, 50:50, and 25:75, respectively. Here, inorganic compounds other than silica are represented by MO _x . Each coating solution was applied on a silicon wafer having a surface maintained at 50 ° C. by a spinner method at 300 rpm, and then heat-treated at 160 ° C. for 30 minutes. It was measured.
(3) Calculation of Refractive Index Next, the obtained refractive index and the particle mixing ratio (particle: (MO _x + SiO ₂ ) / [particle: (MO _x + SiO ₂ ) + matrix: SiO ₂ ]) are plotted and extrapolated. Was used to determine the refractive index when the particles were 100%. If the proportion of pore-containing fine particles is too large, voids may occur in the coating film for measurement and the refractive index of the coating film may be lowered. Eliminated.

[Method of surface treatment of pore-containing fine particles]
Next, a method for treating the surface of pore-containing fine particles (porous or hollow inorganic fine particles) will be described. In order to improve dispersibility in a binder for a low refractive index layer containing an alkyl fluoride portion and / or a dimethylsiloxane portion, which will be described later, the surface of the inorganic fine particles is hydrolyzed with an organosilane represented by the following general formula (I). It is preferable to treat with a decomposition product and / or a partial condensate thereof, and it is more preferred to use either or both of an acid catalyst and a metal chelate compound during the treatment.

[Organosilane compound]
The organosilane compound used in the present invention will be described in detail.
Formula (I)

(R ¹⁰ ) _m -Si (X) _4-m

In the general formula (I), 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, isopropyl group, hexyl group, t-butyl group, sec-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 represents a hydroxyl group or a hydrolyzable group. Examples of the hydrolyzable group include an alkoxy group (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 _2. COO groups (R ₂ is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Examples include CH ₃ COO groups and C ₂ H ₅ COO groups), preferably alkoxy groups, particularly preferably. Is a methoxy group or an ethoxy group.
m represents an integer of 1 to 3. When R ¹⁰ or X there are a plurality, a plurality of R ¹⁰ or X groups may be different, even the same, respectively. m is preferably 1 or 2, particularly preferably 1.

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 (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), an acylamino group (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 , at least one 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 (I) is a vinyl polymerizable compound represented by the following general formula (II). It can be expressed as an organosilane compound having a substituent.

  Formula (II)

In the general formula (II), R ¹ represents a hydrogen atom, a methyl group, a methoxy group, an alkoxycarbonyl group, a cyano group, a fluorine atom or a chlorine atom. Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group. R ¹ 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 methyl groups are particularly preferred.
Y 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 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 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.

n represents 0 or 1. When there are a plurality of Xs, the plurality of Xs may be the same or different. n is preferably 0.
R ¹⁰ has the same meaning as R ^{10 in} formula (I), preferably a substituted or unsubstituted alkyl group or an unsubstituted aryl group, and more preferably an unsubstituted alkyl group or an unsubstituted aryl group.
X has the same meaning as X in formula (I), 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 or a carbon number. 1-3 alkoxy groups are more preferable, and a methoxy group is particularly preferable.

As the organosilane compound used in the present invention, those represented by the following general formula (III) are also preferred.
General formula (III)

_{^{(Rf-L 1) n -Si}} (X 1) n-4

In the above formula, 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 ¹ 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. X ¹ has the same meaning as X in formula (I), 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 or a carbon number. 1-3 alkoxy groups are more preferable, and a methoxy group is particularly preferable.

Next, among the fluorine-containing silane coupling agents represented by the general formula (III), fluorine-containing silane coupling agents represented by the following general formula (IV) are preferable.
Formula (IV)

_{C n F 2n + 1 - (} CH 2) m -Si (X 2) 3

In the above formula, n represents an integer of 1 to 10, and m represents an integer of 1 to 5. R represents an alkoxy group having 1 to 5 carbon atoms or a halogen atom. n is preferably 4 to 10, m is preferably 1 to 3, and X ² represents a methoxy group, an ethoxy group, and a chlorine atom.

  Two or more compounds represented by the general formula (I) to the general formula (IV) may be used in combination. Specific examples of the compounds represented by general formula (I) to general formula (IV) are shown below, but the present invention is not limited thereto.

Among these specific examples, (M-1), (M-2), (M-5) and the like are particularly preferable. 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. In the present invention, the amount of the organosilane compound represented by general formula (I) to general formula (IV) is not particularly limited, but is preferably 1% by mass to 300% by mass, more preferably, per inorganic fine particle. It is 3 mass%-100 mass%, Most preferably, it is 5 mass%-50 mass%. It is preferably 1 to 300 mol%, more preferably 5 to 300 mol%, and most preferably 10 to 200 mol% per mol concentration based on the hydroxyl group on the surface of the inorganic oxide.
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. 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 organosilane to hydrolyze and / or its partial condensate to act on the surface of the inorganic fine particles.
In the hydrolysis condensation reaction, 0.3 to 2.0 mol, preferably 0.5 to 1.0 mol of water is added to 1 mol of the hydrolyzable group (X, X ¹ , X ² ). It is preferably carried out by stirring at 15 to 100 ° C. in the presence of the acid catalyst or metal chelate compound used in the invention.

[Catalyst for improving dispersibility]
The treatment for improving the dispersibility by the hydrolyzate and / or condensation reaction product of 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. Among inorganic acids, hydrochloric acid, sulfuric acid, and organic acids preferably have an acid dissociation constant in water (pKa value (25 ° C.)) of 4.5 or less, and an acid dissociation constant in hydrochloric acid, sulfuric acid, or water of 3.0 or less. 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 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. Further, when alcohol is used as a solvent, it is also preferable that water is not substantially added.

In the present invention, the metal chelate compound used for improving the dispersibility by the hydrolyzate and / or condensation reaction product of organosilane has the general formula R ³ OH (wherein R ³ represents an alkyl group having 1 to 10 carbon atoms). And an alcohol represented by the general formula R ⁴ COCH ₂ COR ⁵ (wherein R ⁴ is an alkyl group having 1 to 10 carbon atoms, R ⁵ is an alkyl group having 1 to 10 carbon atoms or 1 to 1 carbon atoms). And at least one metal chelate compound having a metal selected from Zr, Ti, and Al as a central metal, wherein the compound represented by 10) is a ligand.
The metal chelate compound can be suitably used without particular limitation as long as it has a metal selected from Zr, Ti or Al as a central metal. Within this category, two or more metal chelate compounds may be used in combination. Specific examples of the metal chelate compound used in the present invention include tri-n-butoxyethyl acetoacetate zirconium, di-n-butoxybis (ethylacetoacetate) zirconium, n-butoxytris (ethylacetoacetate) zirconium, tetrakis (n Zirconium chelate compounds such as propylacetoacetate) zirconium, tetrakis (acetylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium; diisopropoxy bis (ethylacetoacetate) titanium, diisopropoxy bis (acetylacetate) titanium , Titanium chelate compounds such as diisopropoxy bis (acetylacetone) titanium; diisopropoxyethyl acetoacetate aluminum Diisopropoxyacetylacetonate aluminum, isopropoxybis (ethylacetoacetate) aluminum, isopropoxybis (acetylacetonate) aluminum, tris (ethylacetoacetate) aluminum, tris (acetylacetonato) aluminum, monoacetylacetonate bis (Ethyl acetoacetate) Aluminum chelate compounds such as aluminum can be mentioned.
Among these metal chelate compounds, tri-n-butoxyethyl acetoacetate zirconium, diisopropoxybis (acetylacetonato) 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.

[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 and a phosphoric acid group are 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. Crosslinkable or polymerizable functional groups include ethylenically unsaturated groups (for example, (meth) acryloyl groups, allyl groups, styryl groups, vinyloxy groups, etc.) that can undergo addition reactions and polymerization reactions with radical species, and cationic polymerizable groups (epoxies). Groups, oxatanyl groups, vinyloxy groups, etc.), polycondensation reactive groups (hydrolyzable silyl groups, etc., N-methylol groups) and the like, and functional groups having an ethylenically unsaturated group are preferred.

The surface free energy (γs ^v : unit, mN / m) of the antireflective film of the present invention is D.E. K. Owens: J.M. Appl. Polym. Sci. , 13, 1741 (1969), from the contact angles θ _H2O and θ _{CH2I2 of} pure water H ₂ O and methylene iodide CH ₂ I ₂ experimentally determined on the antireflection film, the following simultaneous equations ( 1), it is defined by the surface tension of the antireflection film to be calculated by (2) from the obtained gamma] s ^d and gamma] s value is expressed by the sum of ^{h γs v (= γs d +} γs h). The smaller this γs ^v and the lower the surface free energy, the higher the surface repellency and the better the antifouling property. The surface free energy of the antireflection film is preferably 25 mN / m or less, and particularly preferably 20 mN / m or less.
_{(1): 1 + cosθ H2O} = 2√γs d (√γ H2O d / γ H2O v) + 2√γs h (√γ H2O h / γ H2O v)
_{(2): 1 + cosθ CH2I2} = 2√γs d (√γ CH2I2 d / γ CH2I2 v) + 2√γs h (√γ CH2I2 h / γ CH2I2 v)
* Γ _H2O ^d = 21.8, γ _H2O ^h = 51.0, γ _H2O ^v = 72.8, γ _CH2I2 ^d = 49.5, γ _CH2I2 ^h = 1.3, γ _CH2I2 ^v = 50.8, The measurement of the contact angle is carried out under the same condition after conditioning the antireflection film for 1 hour or more at 25 ° C. and 60%.

  The compound for reducing the surface free energy and the binder having the ability to reduce the surface free energy used in the present invention are a compound or a compound that significantly reduces the surface free energy of the antireflection film defined above by using the compound or the binder, respectively. If it is a binder, a structure and a composition will not be limited. In general, when the compound or binder is used, the decrease in surface free energy does not become linear with respect to the amount used, and eventually saturates as the amount used increases. For example, the surface free energy at the addition amount of the compound at the point where the decrease in surface free energy obtained by plotting the decrease in surface free energy against the amount used in a cured matrix system formed with a binder such as DPHA is saturated. Is preferably 10 mN / m or more, more preferably 20 mN / m or more, particularly preferably 25 mN / m or more, and most preferably 30 mN / m or more.

  As the compound for reducing the surface free energy, a known silicone compound or fluorine-based compound can be used. In the case of adding these, it is preferably added in the range of 0.01 to 20% by mass of the total solid content of the low refractive index layer, more preferably in the range of 0.05 to 10% by mass. Yes, particularly preferably 0.1 to 5% by mass.

  Preferable examples of the silicone compound include those having a substituent at the terminal and / or side chain of a compound chain containing a plurality of dimethylsilyloxy units as repeating units. The compound chain containing dimethylsilyloxy as a repeating unit may contain a structural unit other than dimethylsilyloxy. The substituents may be the same or different, and a plurality of substituents are preferable. Examples of preferred substituents include acryloyl group, methacryloyl group, vinyl group, aryl group, cinnamoyl group, epoxy group, oxetanyl group, hydroxyl group, fluoroalkyl group, polyoxyalkylene group, carboxyl group, amino group and the like. It is done. Although there is no restriction | limiting in particular in molecular weight, It is preferable that it is 100,000 or less, It is more preferable that it is 50,000 or less, It is especially preferable that it is 3000-30000, It is most preferable that it is 10,000-20000. Although there is no restriction | limiting in particular in silicone atom content of a silicone type compound, it is preferable that it is 18.0 mass% or more, it is especially preferable that it is 25.0-37.8 mass%, and 30.0-37.0. Most preferably, it is mass%. Examples of preferred silicone compounds are X-22-174DX, X-22-2426, X-22-164B, X22-164C, X-22-170DX, X-22-176D, X, manufactured by Shin-Etsu Chemical Co., Ltd. -22-1821 (named above), Chisso Corporation, FM-0725, FM-7725, FM-4421, FM-5521, FM6621, FM-1121, Gelest DMS-U22, RMS-033, RMS- 083, UMS-182, DMS-H21, DMS-H31, HMS-301, FMS121, FMS123, FMS131, FMS141, FMS221 (named above) but not limited thereto.

As the fluorine compound, a compound having a fluoroalkyl group is preferable. The fluoroalkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and a straight chain (for example, —CF ₂ CF ₃ , —CH ₂ (CF ₂ ) ₄ H, —CH ₂ (CF ₂ ) ₈ CF ₃ , —CH ₂ CH ₂ (CF ₂ ) ₄ H, etc.), for example, a branched structure (eg, CH (CF ₃ ) ₂ , CH ₂ CF (CF ₃ ) ₂ , CH (CH ₃ ) CF ₂ CF ₃ , CH (CH ₃ ) (CF ₂ ) ₅ CF ₂ H, etc.) and alicyclic structures (preferably 5-membered or 6-membered rings such as perfluorocyclohexyl group, perfluorocyclopentyl Group or an alkyl group substituted with these, and may have an ether bond (for example, CH ₂ OCH ₂ CF ₂ CF ₃ , CH ₂ CH ₂ OCH ₂ C ₄ F ₈ H, CH _{2 CH 2 OCH 2 CH 2 C} 8 F 17, CH 2 CH 2 OCF 2 CF 2 OCF 2 CF 2 H , etc. . A plurality of the fluoroalkyl groups may be contained in the same molecule.
It is preferable that the fluorine-based compound further has a substituent that contributes to bond formation or compatibility with the low refractive index layer film. The substituents may be the same or different, and a plurality of substituents are preferable. Examples of preferred substituents include acryloyl group, methacryloyl group, vinyl group, aryl group, cinnamoyl group, epoxy group, oxetanyl group, hydroxyl group, polyoxyalkylene group, carboxyl group, amino group and the like. The fluorine-based compound may be a polymer or an oligomer with a compound not containing a fluorine atom, and the molecular weight is not particularly limited. Although there is no restriction | limiting in particular in fluorine atom content of a fluorine-type compound, It is preferable that it is 20 mass% or more, It is especially preferable that it is 30-70 mass%, It is most preferable that it is 40-70 mass%. Examples of preferred fluorine-based compounds include Daikin Chemical Industries, Ltd., R-2020, M-2020, R-3833, M-3833 (named above), Dainippon Ink Co., Ltd., Megafac F-171. , F-172, F-179A, defender MCF-300 (trade name) and the like, but are not limited thereto.

  The compound for reducing the surface free energy preferably contains at least one group having reactivity with the binder in the molecule. Examples of preferable reactive groups include thermosetting active hydrogen atoms, hydroxyl groups, melamine, active energy ray-curable (meth) acryloyl groups, and epoxy groups, and are melamine or (meth) acryloyl groups. Particularly preferred.

  For the purpose of imparting properties such as dust resistance and antistatic properties, a known cationic surfactant or a dustproof agent such as a polyoxyalkylene compound, an antistatic agent, or the like can be appropriately added. These dustproofing agent and antistatic agent may contain the structural unit as a part of the function in the above-mentioned silicone compound or fluorine compound. When these are added as additives, it is preferably added in the range of 0.01 to 20% by mass of the total solid content of the low refractive index layer, more preferably in the range of 0.05 to 10% by mass. Particularly preferred is 0.1 to 5% by mass. Examples of preferred compounds include, but are not limited to, Dai Nippon Ink Co., Ltd., MegaFace F-150 (trade name), Toray Dow Corning Co., Ltd., SH-3748 (trade name), and the like. Do not mean.

  The binder that can be used for the low refractive index layer of the antireflection film of the present invention will be described. The binder is preferably a polymer having a saturated hydrocarbon chain or a polyether chain as a main chain, and more preferably a polymer having a saturated hydrocarbon chain as a main chain. The binder polymer preferably has a crosslinked structure.

  As the binder polymer having a saturated hydrocarbon chain as a main chain, a polymer of an ethylenically unsaturated monomer is preferable. As the binder polymer having a saturated hydrocarbon chain as the main chain and having a crosslinked structure, a (co) polymer of monomers having two or more ethylenically unsaturated groups is preferable.

  Examples of the monomer having two or more ethylenically unsaturated groups include esters of polyhydric alcohol and (meth) acrylic acid (eg, ethylene glycol di (meth) acrylate, 1,4-cyclohexanediacrylate, pentaerythritol tetra ( (Meth) acrylate), pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, di Pentaerythritol hexa (meth) acrylate, 1,2,3-cyclohexanetetramethacrylate, polyurethane polyacrylate, polyester polyacrylate), vinylbenzene and its derivatives Examples include 1,4-divinylbenzene, 4-vinylbenzoic acid-2-acryloylethyl ester, 1,4-divinylcyclohexanone), vinyl sulfone (eg, divinyl sulfone), acrylamide (eg, methylenebisacrylamide) and methacrylamide. Can be mentioned. Two or more of these monomers may be used in combination. In the present specification, “(meth) acrylate” represents “acrylate or methacrylate”.

  Polymerization of these monomers having an ethylenically unsaturated group can be performed by irradiation with active energy rays or heating in the presence of a photo radical initiator or a thermal radical initiator. Accordingly, a coating liquid containing a monomer having an ethylenically unsaturated group, a photo radical initiator or a thermal radical initiator, mat particles and an inorganic filler is prepared, and the coating liquid is applied on a transparent support, and then an active energy ray. Or it can harden | cur by the polymerization reaction by a heat | fever and can form an antireflection film.

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

  As the thermal radical initiator, organic or inorganic peroxides, organic azo, diazo compounds, and the like can be used. Specifically, benzoyl peroxide, halogen benzoyl peroxide, lauroyl peroxide, acetyl peroxide, dibutyl peroxide, cumene hydroperoxide, butyl hydroperoxide as organic peroxides, hydrogen peroxide, peroxides as inorganic peroxides. Ammonium sulfate, potassium persulfate, etc., 2-azo-bis-isobutyronitrile, 2-azo-bis-propionitrile, 2-azo-bis-cyclohexanedinitrile, etc. as diazo compounds, diazoaminobenzene, p -Nitrobenzenediazonium etc. can be mentioned.

  The polymer having a polyether as a main chain used as a binder for the low refractive index layer is preferably a ring-opening polymer of a polyfunctional epoxy compound. The ring-opening polymerization of the polyfunctional epoxy compound can be performed by irradiation with active energy rays or heating in the presence of a photoacid generator or a thermal acid generator. Therefore, a coating liquid containing a polyfunctional epoxy compound, a photoacid generator or a thermal acid generator, matte particles and an inorganic filler is prepared, and the coating liquid is applied onto a transparent support and then subjected to a polymerization reaction by active energy rays or heat. Can be cured to form an antireflection film.

A monomer having a crosslinkable functional group instead of or in addition to the monomer having two or more ethylenically unsaturated groups for obtaining a binder polymer having a saturated hydrocarbon chain as a main chain and having a crosslinked structure It is also possible to introduce a crosslinkable functional group into the polymer and introduce a crosslink structure into the binder polymer by the reaction of the crosslinkable functional group.
Examples of the crosslinkable functional group include isocyanate group, epoxy group, aziridine group, oxazoline group, aldehyde group, carbonyl group, hydrazine group, carboxyl group, methylol group and active methylene group. Vinylsulfonic acid, acid anhydride, cyanoacrylate derivative, melamine, etherified methylol, ester and urethane, and metal alkoxide such as tetramethoxysilane can also be used as a monomer for introducing a crosslinked structure. A functional group that exhibits crosslinkability as a result of the decomposition reaction, such as a block isocyanate group, may be used. That is, in the present invention, the crosslinkable functional group may not react immediately but may exhibit reactivity as a result of decomposition. These binder polymers having a crosslinkable functional group can form a crosslinked structure by heating after coating.

  The binder having a surface free energy lowering ability used for the low refractive index layer of the antireflection film of the present invention is to add the binder to the surface free energy of the layer formed by curing with an alkyl acrylate monomer typified by DPHA. The binder is not particularly limited as long as the binder can lower the surface free energy. A binder having a surface free energy of 30 mN / m or less is particularly preferred, a binder having a surface density of 25 mN / m or less is more preferred, and a binder having a density of 20 mN / m or less is particularly preferred. The binder preferably contains at least one selected from a fluoroalkyl group, a dimethylsiloxane group, and a polydimethylsiloxane (so-called silicone) compound in the compound. The binder may be a monomer or a polymer before curing, and may be a mixture of a monomer and a polymer or a mixture of a plurality of compounds.

  Preferred examples of the binder having the ability to reduce the surface free energy used for the low refractive index layer will be described below. The binder having a surface free energy reducing ability preferably contains a fluorine-containing polymer as a low refractive index binder. The fluoropolymer is preferably a fluoropolymer that is crosslinked by heat or active energy rays having a dynamic friction coefficient of 0.03 to 0.15 and a contact angle with water of 90 to 120 °.

  Examples of the fluorine-containing polymer used in the low refractive index layer include hydrolysis and dehydration condensate of perfluoroalkyl group-containing silane compounds (for example, (heptadecafluoro-1,1,2,2-tetrahydrodecyl) triethoxysilane). And a fluorine-containing copolymer having a fluorine-containing monomer unit and a structural unit for imparting crosslinking reactivity as structural components.

  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 in which a crosslinking reactive group such as a (meth) acryloyl group is introduced 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). It is below.

  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 for the low refractive index layer of 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.

  As a preferred form of the copolymer used for the low refractive index layer, one of the following general formula 1 can be mentioned.

In general formula 1, L represents a linking group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, particularly preferably 2 to 4 carbon atoms, and may be a linear structure or a branched structure. It may have a ring structure and may have a heteroatom selected from O, N, and S. Preferred examples of L 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 (meth) acryloyl group side. And the like.) And the like. 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 preferred.

  In the general formula 1, A represents a repeating unit derived from an arbitrary vinyl monomer, and is not particularly limited as long as it is a constituent component of a monomer copolymerizable with hexafluoropropylene. Tg (contributes to film hardness), solubility in solvent, transparency, slipperiness, dust / antifouling properties, etc., can be selected as appropriate. From single or plural vinyl monomers depending on the purpose You may be comprised by the repeating unit guide | induced.

  Examples of preferred vinyl monomers 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, propionic acid Vinyl esters such as vinyl and vinyl butyrate, methyl (meth) acrylate, ethyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycidyl methacrylate, allyl (meth) acrylate, (meth) acryloyloxypropyltrimethoxysilane, etc. (Meth) acrylates, styrene, styrene derivatives such as p-hydroxymethylstyrene, crotonic acid, male Acid, can be mentioned and unsaturated carboxylic acids and derivatives thereof such as itaconic acid, more preferably a vinyl ether derivative, vinyl ester derivatives, particularly preferably a vinyl ether derivative.

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

  The following general formula 2 is mentioned as a particularly preferred form of the copolymer used for the low refractive index layer of the antireflection film of the present invention.

  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 unit of a repeating unit derived from an arbitrary vinyl monomer, and may be composed of a single composition or a plurality of compositions. As an example, what was demonstrated as an example of A in the said General formula 1 is applicable. 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.

  In the copolymer represented by the general formula 1 or 2, for example, a (meth) acryloyl group is introduced into a copolymer comprising a hexafluoropropylene component and a hydroxyalkyl vinyl ether component by any one of the methods described above. Can be synthesized.

  Although the preferable example of the copolymer useful by this invention is shown below, this invention is not limited to these.

  The copolymer 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.

Although the reaction pressure can be selected as appropriate, it is usually preferably 1 to 100 kg / cm ² , particularly about 1 to 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.

Next, a method for measuring the segregation of silicone or fluoroalkyl groups on the surface of the low refractive index layer will be described. Si2p, F1s, C1s on the outermost surface of each antireflection film measured with ESCA-3400 manufactured by Shimadzu Corporation (vacuum degree 1 × 10 ⁻⁵ Pa, X-ray source; target Mg, voltage 12 kV, current 20 mA) The photoelectron spectrum intensity ratio Si2p / C1s (= Si (a)), F1s / C1s (= F (a)) and the ion etching apparatus attached to ESCA-3400 (ion gun, voltage 2 kV, current 20 mA) has a low refractive index. The intensity ratio Si2p / C1s (= Si (b)), F1s / C1s (= F () of the photoelectron spectrum measured from the surface where the layer was shaved until the layer thickness became 1/5 (± 5%). b)), the change in the respective strength ratios before and after etching, Si (a) / Si (b), F (a) / F (b), are obtained, and the respective Si2p / C1s ratio, F1 The degree of surface segregation is determined by the change in the s / C1s ratio before and after etching (the intensity ratio of the photoelectron spectrum at the top of the low refractive index layer / the intensity ratio of the photoelectron spectrum near the lower layer 80% deep from the surface of the low refractive index layer). it can. F1s and C1s determine the intensity at the peak position of each photoelectron spectrum, and Si2p uses the intensity at the peak position derived from the Si atom of silicone (polydimethylsiloxane) (bonding energy is around 105 eV) for the above intensity ratio calculation. It was distinguished from Si atoms derived from inorganic silica particles. Preliminary experiments are carried out in which the surface of the low refractive index layer is gradually scraped under various etching conditions in advance, and the depth from the surface is 80% based on the etching conditions required to reach the lower hard coat layer or high refractive index layer. Measure after obtaining the following conditions. When controlling only the surface properties, the surface segregation compounds described in this specification can be used appropriately to selectively place only the necessary components on the surface. It can be controlled independently.

[Physical properties of low refractive index layer]
The refractive index of the low refractive index layer is preferably 1.20 to 1.46, more preferably 1.25 to 1.40, and particularly preferably 1.25 to 1.38.
The thickness of the low refractive index layer is preferably 50 to 200 nm, and more preferably 70 to 120 nm. The haze of the low refractive index layer is preferably 3% or less, more preferably 2% or less, and most preferably 1% or less. The specific strength of the low refractive index layer is preferably H or higher, more preferably 2H or higher, and most preferably 3H or higher in a pencil hardness test under a 500 g load.
Further, in order to improve the antifouling performance of the optical film, it is preferable that the contact angle of water on the surface is 90 degrees or more. More preferably, it is 95 degrees or more, and particularly preferably 100 degrees or more.

[Layer structure of antireflection film]
The antireflection film of the present invention has a hard coat layer, which will be described later, on a transparent substrate, if necessary, and has a refractive index, a film thickness, and the number of layers so that the reflectance decreases due to optical interference. The layers are laminated in consideration of the layer order and the like. In the simplest configuration, the antireflection film has a configuration in which only a low refractive index layer is coated on a substrate. In order to further reduce the reflectance, the antireflection layer is preferably constituted by combining a high refractive index layer having a higher refractive index than that of the base material and a low refractive index layer having a lower refractive index than that of the base material. Examples of configurations include two layers of a high refractive index layer / low refractive index layer from the base material side, and three layers having different refractive indices, a medium refractive index layer (having a higher refractive index than the base material or the hard coat layer , A layer having a refractive index lower than that of a high refractive index layer) / a layer having a high refractive index / a layer having a low refractive index, and the like. Especially, it is preferable to apply | coat in order of a middle refractive index layer / high refractive index layer / low refractive index layer on the base material which has a hard-coat layer from durability, an optical characteristic, cost, productivity, etc.

The example of the preferable layer structure of the antireflection film of this invention is shown below. In the following configuration, the base film functions as a support.
・ Base film / low refractive index layer,
・ Base film / Antistatic layer / Low refractive index layer,
・ Base film / Anti-glare layer / Low refractive index layer,
・ Base film / Anti-glare layer / Antistatic layer / Low refractive index layer ・ Base film / Hard coat layer / Anti-glare layer / Low refractive index layer,
-Base film / hard coat layer / antiglare layer / antistatic layer / low refractive index layer-Base film / hard coat layer / antistatic layer / antiglare layer / low refractive index layer-Base film / hard coat layer / High refractive index layer / Low refractive index layer,
・ Base film / hard coat layer / antistatic layer / high refractive index layer / low refractive index layer,
Base film / hard coat layer / medium refractive index layer / high refractive index layer / low refractive index layer,
Base film / antiglare layer / high refractive index layer / low refractive index layer,
Base film / antiglare layer / medium refractive index layer / high refractive index layer / low refractive index layer,
Base film / antistatic layer / hard coat layer / medium refractive index layer / high refractive index layer / low refractive index layer,
Antistatic layer / base film / hard coat layer / medium refractive index layer / high refractive index layer / low refractive index layer,
Base film / antistatic layer / antiglare layer / medium refractive index layer / high refractive index layer / low refractive index layer,
Antistatic layer / base film / antiglare layer / medium refractive index layer / high refractive index layer / low refractive index layer,
Antistatic layer / base film / antiglare layer / high refractive index layer / low refractive index layer / high refractive index layer / low refractive index layer,
As long as the reflectance can be reduced by optical interference, it is not limited to these layer configurations. The high refractive index layer may be a light diffusing layer having no antiglare property.
The antistatic layer is preferably a layer containing conductive polymer particles or metal oxide fine particles (for example, ATO, ITO), and can be provided by coating or atmospheric pressure plasma treatment.

[High (medium) refractive index layer]
Next, the high (medium) refractive index layer will be described.
When a high refractive index layer is used in the present invention, the refractive index is preferably 1.65 to 2.40, and more preferably 1.70 to 2.20. When the middle refractive index layer is used, the refractive index is adjusted to be a value between the refractive index of the low refractive index layer and the refractive index of the high refractive index layer. The refractive index of the middle refractive index layer is preferably 1.55 to 1.80. The haze of the high refractive index layer and the medium refractive index layer is preferably 3% or less.

  In the high refractive index layer and the medium refractive index layer of the present invention, a cured product of a composition in which inorganic fine particles having a high refractive index are dispersed in the monomer and initiator exemplified in the hard coat layer and an organically substituted silicon compound. Is preferably used. As the inorganic fine particles, metal (eg, aluminum, titanium, zirconium, antimony) oxides are preferable, and from the viewpoint of refractive index, titanium dioxide fine particles are most preferable. In the case of using a monomer and an initiator, a medium refractive index layer or a high refractive index layer having excellent scratch resistance and adhesion can be formed by curing the monomer by a polymerization reaction using active energy rays or heat after coating. The average particle size of the inorganic fine particles is preferably 10 to 100 nm.

  As the titanium dioxide fine particles, inorganic fine particles mainly containing titanium dioxide containing at least one element selected from cobalt, aluminum, and zirconium are particularly preferable. The main component means a component having the largest content (mass%) among the components constituting the particles. The inorganic fine particles mainly composed of titanium dioxide in the present invention preferably have a refractive index of 1.90 to 2.80, more preferably 2.10 to 2.80, and 2.20 to 2.80. 80 is most preferred. The mass average diameter of primary particles of inorganic fine particles mainly composed of titanium dioxide is preferably 1 to 200 nm, more preferably 1 to 150 nm, still more preferably 1 to 100 nm, and particularly preferably 1 to 80 nm.

The particle diameter of the inorganic fine particles can be measured by a light scattering method or an electron micrograph. The specific surface area of the inorganic fine particles is preferably 10 to 400 m ² / g, more preferably from 20 to 200 m ² / g, and most preferably from 30 to 150 m ² / g. The crystal structure of the inorganic fine particles containing titanium dioxide as a main component is preferably a rutile, rutile / anatase mixed crystal, anatase or amorphous structure, particularly preferably a rutile structure. The main component means a component having the largest content (mass%) among the components constituting the particles.

  By containing at least one element selected from Co (cobalt), Al (aluminum) and Zr (zirconium) in the inorganic fine particles mainly composed of titanium dioxide, the photocatalytic activity of titanium dioxide can be suppressed, The weather resistance of the high refractive index layer and the medium refractive index layer of the present invention can be improved. A particularly preferable element is Co (cobalt). It is also preferable to use two or more types in combination.

<Dispersant>
A dispersant can be used for dispersing inorganic fine particles mainly composed of titanium dioxide used in the high refractive index layer and the medium refractive index layer of the present invention. In order to disperse the inorganic fine particles mainly composed of titanium dioxide of the present invention, it is particularly preferable to use a dispersant having an anionic group. As the anionic group, a group having an acidic proton such as a carboxyl group, a sulfonic acid group (and a sulfo group), a phosphoric acid group (and a phosphono group), or a sulfonamide group, or a salt thereof is effective. A sulfonic acid group, a phosphoric acid group and a salt thereof are preferable, and a carboxyl group and a phosphoric acid group are particularly preferable. The number of anionic groups contained in the dispersant per molecule may be one or more. A plurality of anionic groups may be contained for the purpose of further improving the dispersibility of the inorganic fine particles. 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 preferably further contains a crosslinkable or polymerizable functional group. Crosslinkable or polymerizable functional groups include ethylenically unsaturated groups (for example, (meth) acryloyl groups, allyl groups, styryl groups, vinyloxy groups, etc.) that can undergo addition reactions and polymerization reactions with radical species, and cationic polymerizable groups (epoxies). Groups, oxatanyl groups, vinyloxy groups, etc.), polycondensation reactive groups (hydrolyzable silyl groups, etc., N-methylol groups) and the like, and functional groups having an ethylenically unsaturated group are preferred. A preferred dispersant used for dispersing inorganic fine particles mainly composed of titanium dioxide used in the high refractive index layer of the present invention has an anionic group and a crosslinkable or polymerizable functional group, and the crosslinkable or polymerizable functional group. It is a dispersant having a group in the side chain. The weight average molecular weight (Mw) of the dispersant having an anionic group and a crosslinkable or polymerizable functional group and having the crosslinkable or polymerizable functional group in the side chain is not particularly limited, but may be 1000 or more. preferable. The more preferable mass average molecular weight (Mw) of the dispersant is 2000 to 1000000, more preferably 5000 to 200000, and particularly preferably 10000 to 100000.

  The amount of the dispersant used relative to the inorganic fine particles is preferably in the range of 1 to 50% by mass, more preferably in the range of 5 to 30% by mass, and most preferably 5 to 20% by mass. Two or more dispersants may be used in combination.

<Method for forming high (medium) refractive index layer>
The inorganic fine particles mainly composed of titanium dioxide used for the high refractive index layer and the medium refractive index layer are used for forming the high refractive index layer and the medium refractive index layer in the state of dispersion. In the dispersion of the inorganic fine particles, it is dispersed in a dispersion medium in the presence of the dispersant. As the dispersion medium, a liquid having a boiling point of 60 to 170 ° C. is preferably used. Examples of dispersion media include water, alcohol (eg, methanol, ethanol, isopropanol, butanol, benzyl alcohol), ketone (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone), ester (eg, methyl acetate, ethyl acetate, Propyl acetate, butyl acetate, methyl formate, ethyl formate, propyl formate, butyl formate), aliphatic hydrocarbons (eg, hexane, cyclohexane), halogenated hydrocarbons (eg, methylene chloride, chloroform, carbon tetrachloride), aromatic Hydrocarbon (eg, benzene, toluene, xylene), amide (eg, dimethylformamide, dimethylacetamide, n-methylpyrrolidone), ether (eg, diethyl ether, dioxane, tetrahydrofuran), ether alcohol (eg, 1-methyl) Carboxymethyl-2-propanol) are included. Toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and butanol are preferred. Particularly preferred dispersion media are methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.

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

  The high refractive index layer and medium refractive index layer used in the present invention are preferably a binder precursor (for example, described later) required for forming a matrix in a dispersion liquid in which inorganic fine particles are dispersed in a dispersion medium as described above. Active energy ray-curable polyfunctional monomers and polyfunctional oligomers), photopolymerization initiators, etc. are added to form a coating composition for forming a high refractive index layer and a medium refractive index layer, and a high refractive index layer on a transparent support. In addition, it is preferable to form by applying a coating composition for forming a medium refractive index layer and curing it by a crosslinking reaction or a polymerization reaction of an active energy ray-curable compound (for example, a polyfunctional monomer or a polyfunctional oligomer).

  Furthermore, it is preferable to cause the binder of the high refractive index layer and the medium refractive index layer to undergo a crosslinking reaction or a polymerization reaction with the dispersant simultaneously with or after the coating of the layer. The binder of the high refractive index layer and the medium refractive index layer produced in this way is, for example, a binder or active energy ray-curable polyfunctional monomer or polyfunctional oligomer that undergoes crosslinking or polymerization reaction to form a binder. In this form, the anionic group of the dispersant is incorporated. Furthermore, the binder of the high refractive index layer and the medium refractive index layer has a function in which the anionic group maintains the dispersion state of the inorganic fine particles, and the crosslinked or polymerized structure imparts a film forming ability to the binder and contains the inorganic fine particles. To improve the physical strength, chemical resistance and weather resistance of the high refractive index layer and medium refractive index layer.

  The functional group of the active energy ray-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. In the present specification, descriptions such as “(meth) acrylate” and “(meth) acryloyl” mean “acrylate or methacrylate” and “acryloyl or methacryloyl”.

  Specific examples of the photopolymerizable polyfunctional monomer having a photopolymerizable functional group include those of alkylene glycols such as neopentyl glycol acrylate, 1,6-hexanediol di (meth) acrylate, propylene glycol di (meth) acrylate (meta ) Acrylic acid diesters; (Meth) acrylic 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 Acid diesters;

(Meth) acrylic acid diesters of polyhydric alcohols such as pentaerythritol di (meth) acrylate; 2,2-bis {4- (acryloxy-diethoxy) phenyl} propane, 2-bis {4- (acryloxy-poly) (Meth) acrylic acid diesters of ethylene oxide or propylene oxide adducts such as propoxy) phenyl} propane; and the like.

  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, glycerol triacrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol Tri (meth) acrylate, dipentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol triacrylate, tripentaerythritol hexatriacrylate, etc. Can be mentioned.

  Two or more polyfunctional monomers may be used in combination. 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. Examples of the photo radical polymerization initiator include acetophenones, benzophenones, Michler's benzoylbenzoate, α-amyloxime ester, tetramethylthiuram monosulfide, and thioxanthones.

  Commercially available radical photopolymerization initiators include KAYACURE (DETX-S, BP-100, BDMK, CTX, BMS, 2-EAQ, ABQ, CPTX, EPD, ITX, QTX, BTC, manufactured by Nippon Kayaku Co., Ltd. MCA, etc.), Irgacure (651, 184, 500, 907, 369, 1173, 2959, 4265, 4263, etc.) manufactured by Ciba Geigy Co., Ltd., Esacure (KIP100F, KB1, EB3, BP, X33, KT046) manufactured by Sartomer , KT37, KIP150, TZT) and the like.

  In particular, photocleavable photoradical polymerization initiators are preferred. The photocleavable photoradical polymerization initiator is described in the latest UV curing technology (P.159, issuer; Kazuhiro Takahisa, publisher; Technical Information Association, published in 1991). Examples of commercially available photocleavable photoradical polymerization initiators include Irgacure (651, 184, 907) manufactured by Ciba Geigy Japan.

  It is preferable to use a photoinitiator in the range of 0.1-15 mass parts with respect to 100 mass parts of polyfunctional monomers, More preferably, it is the range of 1-10 mass parts. In addition to the photopolymerization initiator, a photosensitizer may be used. Specific examples of the photosensitizer include n-butylamine, triethylamine, tri-n-butylphosphine, Michler's ketone and thioxanthone. Examples of commercially available photosensitizers include KAYACURE (DMBI, EPA) manufactured by Nippon Kayaku Co., Ltd. The photopolymerization reaction is preferably performed by ultraviolet irradiation after the high refractive index layer is applied and dried. The high refractive index layer used in the present invention may contain the compound represented by the general formula (A) and / or a derivative compound thereof.

  In order to construct an antireflection film by constructing a low refractive index layer on a high refractive index layer, the refractive index of the high refractive index layer is preferably 1.55 to 2.40, more preferably It is 1.60 to 2.20, more preferably 1.65 to 2.10, and most preferably 1.80 to 2.00.

  In addition to the above components (inorganic fine particles, polymerization initiators, photosensitizers, etc.), the high refractive index layer includes resins, surfactants, antistatic agents, coupling agents, thickeners, anti-coloring agents, and coloring. Agents (pigments, dyes), antifoaming agents, leveling agents, flame retardants, ultraviolet absorbers, infrared absorbers, adhesion-imparting agents, polymerization inhibitors, antioxidants, surface modifiers, conductive metal particles, etc. It can also be added.

  In the formation of the high refractive index layer, the crosslinking reaction or polymerization reaction of the active energy ray-curable compound is preferably carried out in an atmosphere having an oxygen concentration of 10% by volume or less. By forming the high refractive index layer in an atmosphere having an oxygen concentration of 10% by volume or less, the physical strength, chemical resistance, and weather resistance of the high refractive index layer, and further, the high refractive index layer and the high refractive index layer are adjacent to each other. Adhesion with the layer can be improved. Preferably, the active energy ray-curable compound is formed by a crosslinking reaction or a polymerization reaction in an atmosphere having an oxygen concentration of 6% by volume or less, more preferably an oxygen concentration of 4% by volume or less, particularly preferably an oxygen concentration. 2% by volume or less, most preferably 1% by volume or less.

  In addition, when an antireflection film is applied to a liquid crystal display device, an undercoat layer to which particles having an average particle diameter of 0.1 to 10 μm are added is newly constructed or a hard coat layer for the purpose of improving viewing angle characteristics. The above particles can be added to form a light scattering hard coat layer. The average particle diameter of the particles is preferably 0.2 to 5.0 μm, more preferably 0.3 to 4.0 μm, and particularly preferably 0.5 to 3.5 μm.

The refractive index of the particles is preferably 1.35 to 1.80, more preferably 1.40 to 1.75, and still more preferably 1.45 to 1.75. The narrower the particle size distribution, the better. The S value indicating the particle size distribution of the particles is represented by the following formula, preferably 1.5 or less, more preferably 1.0 or less, and particularly preferably 0.7 or less.
S = [D (0.9) -D (0.1)] / D (0.5)
D (0.1): Particle size equivalent to 10% of the integrated value of the volume converted particle size D (0.5): Particle size equivalent to 50% of the integrated value of the volume converted particle size D (0.9): Volume converted particle Diameter equivalent to 90% of the integrated diameter

  The difference in refractive index between the refractive index of the particles and the refractive index of the undercoat layer is preferably 0.02 or more. More preferably, the difference in refractive index is 0.03 to 0.5, more preferably the difference in refractive index is 0.05 to 0.4, and particularly preferably the difference in refractive index is 0.07 to 0.3. . Examples of the particles added to the undercoat layer include inorganic particles and organic particles described in the antiglare layer. The undercoat layer is preferably constructed between the hard coat layer and the transparent support. It can also serve as a hard coat layer. When particles having an average particle size of 0.1 to 10 μm are added to the undercoat layer, the haze of the undercoat layer is preferably 3 to 60%. More preferably, it is 5 to 50%, further preferably 7 to 45%, particularly preferably 10 to 40%.

  As the transparent support of the antireflection film of the present invention, a plastic film is preferably used. Polymers that form plastic films include cellulose esters (eg, triacetyl cellulose, diacetyl cellulose), polyamides, polycarbonates, polyesters (eg, polyethylene terephthalate, polyethylene naphthalate), polystyrenes, polyolefins, norbornene resins (Arton: trade names) , Manufactured by JSR Corporation), amorphous polyolefin (ZEONEX: trade name, manufactured by Nippon Zeon Co., Ltd.), and the like. Of these, triacetyl cellulose, polyethylene terephthalate, and polyethylene naphthalate are preferable, and triacetyl cellulose is particularly preferable. When the antireflection film of the present invention is used in a liquid crystal display device, it is disposed on the outermost surface of the display by means such as providing an adhesive layer on one side. When the transparent support is triacetylcellulose, triacetylcellulose is used as a protective film for protecting the polarizing layer of the polarizing plate. Therefore, it is preferable in terms of cost to use the antireflection film of the present invention as it is for the protective film. .

<Transparent substrate>
Unless the antireflection film is directly provided on the CRT image display surface or the lens surface, the antireflection film preferably has a transparent substrate (transparent support). The light transmittance of the transparent substrate is preferably 80% or more, and more preferably 86% or more. The haze of the transparent substrate is preferably 2.0% or less, and more preferably 1.0% or less. The refractive index of the transparent substrate is preferably 1.4 to 1.7. As the transparent substrate, a plastic film is preferable to a glass plate. Examples of plastic film materials include cellulose esters, polyamides, polycarbonates, polyesters (eg, polyethylene terephthalate, polyethylene naphthalate, poly-1,4-cyclohexanedimethylene terephthalate, polyethylene-1,2-diphenoxyethane-4, 4′-dicarboxylate, polybutylene terephthalate), polystyrene (eg, syndiotactic polystyrene), polyolefin (eg, polypropylene, polyethylene, polymethylpentene), polysulfone, polyethersulfone, polyarylate, polyetherimide, polymethyl Methacrylate and polyether ketone are included. Cellulose ester, polycarbonate, polyethylene terephthalate and polyethylene naphthalate are preferred. In particular, when used in a liquid crystal display device, a cellulose acylate film is preferable, and cellulose acylate is produced by esterification from cellulose. The particularly preferable cellulose described above is not necessarily usable as it is, but is used by refining linter, kenaf and pulp.

  In the present invention, cellulose acylate means a fatty acid ester of cellulose, and a lower fatty acid ester is particularly preferable. Furthermore, a fatty acid ester film of cellulose is preferable. Lower fatty acid means a fatty acid having 6 or less carbon atoms. A cellulose acylate having 2 to 4 carbon atoms is preferred. Cellulose acetate is particularly preferred. It is also preferable to use mixed fatty acid esters such as cellulose acetate propionate and cellulose acetate butyrate.

  The viscosity average degree of polymerization (DP) of cellulose acylate is preferably 250 or more, and more preferably 290 or more. Cellulose acylate preferably has a narrow molecular weight distribution of Mw / Mn (Mw is a mass average molecular weight, Mn is a number average molecular weight) by gel permeation chromatography. The specific value of Mw / Mn is preferably 1.0 to 5.0. More preferably, it is 1.0-3.0, Most preferably, it is 1.0-2.0. As the transparent substrate of the present invention, it is preferable to use cellulose acylate having an acetylation degree of 55.0 to 62.5%. The acetylation degree is more preferably 57.0 to 62.0%, and particularly preferably 59.0 to 61.5%. The degree of acetylation means the amount of bound acetic acid per unit mass of cellulose. The degree of acetylation is determined by measurement and calculation of the degree of acylation in ASTM: D-817-91 (testing method for cellulose acylate, etc.).

  In cellulose acylate, the hydroxyl groups at the 2-position, 3-position and 6-position of cellulose are not evenly substituted, but the substitution degree at the 6-position tends to be small. In the cellulose acylate used in the present invention, it is preferable that the degree of substitution at the 6-position of cellulose is the same or greater than that at the 2- and 3-positions. The ratio of the substitution degree at the 6-position to the total substitution degree at the 2-position, the 3-position, and the 6-position is preferably 30 to 40%, more preferably 31 to 40%, and more preferably 32 to 40%. Most preferably it is. In addition, a cellulose acylate film substantially free of halogenated hydrocarbons such as dichloromethane and a method for producing the same are disclosed in JIII Journal of Technical Disclosure No. 2001-1745 (issued on March 15, 2001, hereinafter “Public No. 2001-1745 ”), and the cellulose acylate described therein can also be preferably used in the present invention.

For transparent substrates, various additives are used to adjust the film's mechanical properties (film strength, curl, dimensional stability, slipperiness, etc.) and durability (wet heat resistance, weather resistance, etc.). Can be used. For example, plasticizers (phosphate esters, phthalate esters, esters of polyols and fatty acids, etc.), UV inhibitors (eg, hydroxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, cyanoacrylate compounds) Etc.), deterioration inhibitors (eg, antioxidants, peroxide decomposers, radical inhibitors, metal deactivators, acid scavengers, amines, etc.), fine particles (eg, SiO ₂ , Al ₂ O ₃ , TiO ₂₎ BaSO ₄ , CaCO ₃ , MgCO ₃ , talc, kaolin, etc.), release agents, antistatic agents, infrared absorbers, and the like. These details are disclosed in published technical bulletin 2001-1745, p. Materials described in detail in 17-22 are preferably used.
The amount of the additive used is preferably 0.01 to 20% by mass of the transparent substrate, and more preferably 0.05 to 10% by mass.

  Surface treatment may be performed on the transparent substrate. Examples of the surface treatment include chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment and ozone oxidation treatment. Specifically, for example, published technical bulletin 2001-1745, p. The content described in 30-31, the content described in JP 2001-9973 A, and the like can be given. Preferably, glow discharge treatment, ultraviolet irradiation treatment, corona discharge treatment and flame treatment, and more preferably glow discharge treatment and ultraviolet treatment.

  In the antireflection film of the present invention, it is preferable to add an inorganic filler to each layer as appropriate for the purpose of improving the film strength. The inorganic filler added to each layer may be the same or different, and it is preferable that the type, addition amount, etc. are appropriately adjusted according to the required performance such as refractive index, film strength, film thickness, and coating property of each layer. . The shape of the inorganic filler used in the present invention is not particularly limited, and for example, any of a spherical shape, a plate shape, a fiber shape, a rod shape, an irregular shape, a hollow shape, and the like are preferably used. preferable. Further, the kind of the inorganic filler is not particularly limited, but an amorphous one is preferably used, and is preferably made of a metal oxide, nitride, sulfide or halide. Particularly preferred.

  As metal atoms of the metal oxide, Na, K, Mg, Ca, Ba, Al, Zn, Fe, Cu, Ti, Sn, In, W, Y, Sb, Mn, Ga, V, Nb, Ta, Examples include Ag, Si, B, Bi, Mo, Ce, Cd, Be, Pb, and Ni. In order to obtain a transparent cured film, the average particle diameter of the inorganic filler is preferably set to a value within the range of 0.001 to 0.2 μm, more preferably 0.001 to 0.1 μm, and still more preferably. 0.001 to 0.06 μm. Here, the average particle diameter of the particles is measured by a Coulter counter. Although the usage method of the inorganic filler in this invention is not restrict | limited in particular, For example, it can use in a dry state or can also be used in the state disperse | distributed to water or the organic solvent. In the present invention, it is also preferable to use a dispersion stabilizer in combination for the purpose of suppressing aggregation and sedimentation of the inorganic filler. As the dispersion stabilizer, polyvinyl alcohol, polyvinyl pyrrolidone, cellulose derivative, polyamide, phosphate ester, polyether, surfactant, silane coupling agent, titanium coupling agent and the like can be used. In particular, a silane coupling agent is preferable because the film after curing is strong. Although the addition amount of the silane coupling agent as a dispersion stabilizer is not particularly limited, for example, the value is preferably 1 part by mass or more with respect to 100 parts by mass of the inorganic filler. Also, the method of adding the dispersion stabilizer is not particularly limited, but a hydrolyzed one can be added, or a dispersion stabilizer silane coupling agent and an inorganic filler are mixed. Thereafter, a method of further hydrolysis and condensation can be employed, but the latter is more preferable. The inorganic filler suitable for each layer will be described later.

[Hard coat layer]
The hard coat layer of the antireflection film of the present invention will be described below.
The hard coat layer is formed from a binder for imparting hard coat properties, mat particles for imparting anti-glare properties as necessary, and an inorganic filler for increasing the refractive index, preventing crosslinking shrinkage, and increasing the strength. Is done. The binder is preferably a polymer having a saturated hydrocarbon chain or a polyether chain as the main chain, and more preferably a polymer having a saturated hydrocarbon chain as the main chain. The binder polymer preferably has a crosslinked structure. As the binder polymer having a saturated hydrocarbon chain as a main chain, a polymer of an ethylenically unsaturated monomer is preferable. As the binder polymer having a saturated hydrocarbon chain as the main chain and having a crosslinked structure, a (co) polymer of monomers having two or more ethylenically unsaturated groups is preferable. In order to obtain a high refractive index, the monomer structure preferably contains an aromatic ring or at least one atom selected from halogen atoms other than fluorine, sulfur atoms, phosphorus atoms, and nitrogen atoms.

  Examples of the monomer having two or more ethylenically unsaturated groups include esters of polyhydric alcohol and (meth) acrylic acid (eg, ethylene glycol di (meth) acrylate, 1,4-dichlorohexane diacrylate, pentaerythritol tetra). (Meth) acrylate), pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Pentaerythritol hexa (meth) acrylate, 1,3,5-cyclohexanetriol triacrylate, polyurethane polyacrylate, polyester polyacrylate), vinylbenzene and derivatives thereof (Eg, 1,4-divinylbenzene, 4-vinylbenzoic acid-2-acryloylethyl ester, 1,4-divinylcyclohexanone), vinyl sulfone (eg, divinyl sulfone), acrylamide (eg, methylenebisacrylamide) and methacryl Amides are mentioned.

  Specific examples of the high refractive index monomer include bis (4-methacryloylthiophenyl) sulfide, vinyl naphthalene, vinyl phenyl sulfide, 4-methacryloxyphenyl-4′-methoxyphenyl thioether, and the like.

  Polymerization of these monomers having an ethylenically unsaturated group can be performed by irradiation with active energy rays or heating in the presence of a photo radical initiator or a thermal radical initiator. Accordingly, a coating liquid containing a monomer having an ethylenically unsaturated group, a photo radical initiator or a thermal radical initiator, mat particles and an inorganic filler is prepared, and the coating liquid is applied on a transparent support and then an active energy ray or It can be cured by a polymerization reaction by heat to form an antireflection film.

  The polymer having a polyether as the main chain is preferably a ring-opening polymer of a polyfunctional epoxy compound. The ring-opening polymerization of the polyfunctional epoxy compound can be performed by irradiation with active energy rays or heating in the presence of a photoacid generator or a thermal acid generator. Therefore, a coating liquid containing a polyfunctional epoxy compound, a photoacid generator or a thermal acid generator, matte particles and an inorganic filler is prepared, and the coating liquid is applied onto a transparent support and then subjected to a polymerization reaction by active energy rays or heat. Can be cured to form an antireflection film.

  Instead of or in addition to a monomer having two or more ethylenically unsaturated groups, a monomer having a crosslinkable functional group is used to introduce a crosslinkable functional group into the polymer, and by reaction of this crosslinkable functional group, A crosslinked structure may be introduced into the binder polymer. Examples of the crosslinkable functional group include isocyanate group, epoxy group, aziridine group, oxazoline group, aldehyde group, carbonyl group, hydrazine group, carboxyl group, methylol group and active methylene group. Vinylsulfonic acid, acid anhydride, cyanoacrylate derivative, melamine, etherified methylol, ester and urethane, and metal alkoxide such as tetramethoxysilane can also be used as a monomer for introducing a crosslinked structure. A functional group that exhibits crosslinkability as a result of the decomposition reaction, such as a block isocyanate group, may be used. That is, in the present invention, the crosslinkable functional group may not react immediately but may exhibit reactivity as a result of decomposition. These binder polymers having a crosslinkable functional group can form a crosslinked structure by heating after coating.

The hard coat layer contains matte particles having an average particle diameter of 1 to 10 μm, preferably 1.5 to 7.0 μm, for example, inorganic compound particles or resin particles, if necessary. Specific examples of the mat particles preferably include inorganic particles such as silica particles and TiO ₂ particles; resin particles such as crosslinked acrylic particles, crosslinked styrene particles, melamine resin particles, and benzoguanamine resin particles. Of these, crosslinked styrene particles are preferred. As the shape of the mat particle, either a true sphere or an indefinite shape can be used. Further, two or more different kinds of mat particles may be used in combination. The mat particles are contained in the antiglare hard coat layer so that the amount of mat particles in the formed antiglare hard coat layer is preferably 10 to 1000 mg / m ² , more preferably 30 to 100 mg / m ^2. Is done. In a particularly preferred embodiment, cross-linked styrene particles are used as mat particles, and the cross-linked styrene particles having a particle size larger than one half of the film thickness of the hard coat layer occupy 40 to 100% of the entire cross-linked styrene particles. It is an aspect. Here, the particle size distribution of the mat particles is measured by a Coulter counter method, and the measured distribution is converted into a particle number distribution.

The hard coat layer is made of an oxide of at least one metal selected from titanium, zirconium, aluminum, indium, zinc, tin, and antimony, in addition to the above mat particles, in order to increase the refractive index of the layer. Therefore, it is preferable that an inorganic filler having an average particle diameter of 0.001 to 0.2 μm or less, preferably 0.001 to 0.1 μm, more preferably 0.001 to 0.06 μm or less is contained. Specific examples of the inorganic filler used for the hard coat layer include TiO ₂ , ZrO ₂ , Al ₂ O ₃ , In ₂ O ₃ , ZnO, SnO ₂ , Sb ₂ O ₃ and ITO. TiO ₂ and ZrO ₂ are particularly preferable from the viewpoint of increasing the refractive index. The surface of the inorganic filler is preferably subjected to a silane coupling treatment or a titanium coupling treatment, and a surface treatment agent having a functional group capable of reacting with a binder species on the filler surface is preferably used. The amount of these inorganic fillers added is preferably 10 to 90% of the total mass of the hard coat layer, more preferably 20 to 80%, and particularly preferably 30 to 75%. Such a filler does not scatter because the particle size is sufficiently smaller than the wavelength of light, and a dispersion in which the filler is dispersed in a binder polymer behaves as an optically uniform substance.

  The total refractive index of the mixture of binder and inorganic filler of the hard coat layer of the present invention is preferably 1.57 to 2.00, more preferably 1.60 to 1.80. In order to make the refractive index within the above range, the kind and amount ratio of the binder and the inorganic filler may be appropriately selected. How to select can be easily known experimentally in advance.

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

  The antireflection film of the present invention thus formed has a haze value of 3 to 20%, preferably 4 to 15%, and an average reflectance of 450 nm to 650 nm is preferably 1.8% or less, preferably Is 1.5% or less. When the antireflection film of the present invention has a haze value and an average reflectance in the above range, good antiglare properties and antireflection properties can be obtained without causing deterioration of the transmitted image.

  The polarizing plate of the present invention uses the antireflection film as at least one of the two protective films of the polarizing layer. 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 excellent in scratch resistance, antifouling property and the like can be obtained. Moreover, in the polarizing plate of this invention, when an antireflection film serves as a protective film, manufacturing cost can be reduced.

[Application method]
As a method for applying the antireflection film of the present invention, a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, a gravure coating method and a die coating method are preferable, and a gravure coating method and a wire bar A coating method and a die coating method are more preferable, and a die coating method is particularly preferable. Further, it is most preferable to apply using a die whose configuration is devised as described later.

[Configuration of die coater]
FIG. 1 is a cross-sectional view of a coater using a slot die used in the practice of the present invention. The coater 10 is applied to the web W supported by the backup roll 11 and continuously applied from the slot die 13 as a bead 14a to form a coating film 14b on the web W.

  Inside the slot die 13, a pocket 15 and a slot 16 are formed. The pocket 15 has a cross section constituted by a curve and a straight line, and may be, for example, a substantially circular shape as shown in FIG. A or a semicircular shape. The pocket 15 is a liquid storage space for the coating liquid extended in the width direction of the slot die 13 with its cross-sectional shape, and the length of the effective extension is generally equal to or slightly longer than the coating width.

  The supply of the coating liquid 14 to the pocket 15 is performed from the side surface of the slot die 13 or from the center of the surface opposite to the slot opening 16a. The pocket 15 is provided with a stopper that prevents the coating liquid 14 from leaking out.

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

  The tip lip 17 of the slot die 13 where the opening 16a of the slot 16 is located is formed in a tapered shape, and the tip is a flat portion 18 called a land. In this land 18, the upstream side in the running direction of the web W with respect to the slot 16 is referred to as an upstream lip land 18 a and the downstream side is referred to as a downstream lip land 18 b.

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

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

  The VA mode liquid crystal cell includes (1) a narrowly defined VA mode liquid crystal cell in which rod-like liquid crystalline molecules are aligned substantially vertically when no voltage is applied, and substantially horizontally when a voltage is applied (Japanese Patent Laid-Open No. Hei 2-). 176625) (2) Liquid crystal cell (SID97, Digest of tech. Papers (Proceedings) 28 (1997) 845 in which the VA mode is converted into a multi-domain (MVA mode) in order to enlarge the viewing angle. ), (3) A liquid crystal cell in a mode (n-ASM mode) in which rod-like liquid crystalline molecules are substantially vertically aligned when no voltage is applied and twisted multi-domain alignment is applied when a voltage is applied (Preliminary collections 58-59 of the Japan Liquid Crystal Society) (1998)) and (4) SURVAVAL mode liquid crystal cells (announced at LCD International 98).

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

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

  In particular, for TN mode and IPS mode liquid crystal display devices, as described in JP-A-2001-100043, an optical compensation film having an effect of widening a viewing angle is used as a protective film having two polarizing films on both sides. Of these, a polarizing plate having an antireflection effect and a viewing angle widening effect can be obtained with the thickness of one polarizing plate by using it on the surface opposite to the antireflection film of the present invention.

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

Preparation Example 1 [Preparation of inorganic fine particles (P-1)]
360 g of tetraethoxysilane (TEOS, SiO ₂ concentration 28% by mass) and 530 g of methanol are mixed, and 100 g of ion-exchanged water and ammonia water (containing 28% ammonia) are added dropwise to the mixture at 25 ° C., followed by stirring for 24 hours. And matured. Heat treatment was carried out at 180 ° C. for 4 hours in an autoclave, and the solvent was replaced with ethanol using an ultrafiltration membrane to prepare a dispersion of inorganic fine particles (P-1) having a solid content concentration of 20% by mass. It was confirmed to be porous particles by observation with a transmission electron microscope.

Preparation Example 2 [Preparation of inorganic fine particles (P-2)]
A mixture obtained by adding 900 g of ion exchange water and 800 g of ethanol to 100.0 g of the inorganic fine particle (P-1) dispersion prepared in Preparation Example 1 was heated to 30 ° C., and then tetraethoxysilane (SiO ₂ concentration). (28% by mass) 360 g and 28% ammonia water 626 g were added, and a silica outer shell layer was formed on the particle surface with a hydrolyzed polycondensate of tetraethoxysilane. Next, after concentrating to 5% by mass of solid content with an evaporator, add ammonia water with a concentration of 15% by mass to pH 10, heat-treat in an autoclave at 180 ° C. for 4 hours, and use an ultrafiltration membrane to convert the solvent to ethanol. A dispersion of substituted inorganic fine particles (P-2) having a solid content concentration of 20% by mass was prepared.

Preparation Example 3 [Preparation of inorganic fine particles (P-3)]
The inorganic fine particles (P-2) were prepared in the same manner as the inorganic fine particles (P-2) preparation step except that the addition amount of tetraethoxysilane (SiO ₂ concentration 28 mass%) was changed from 360 g to 470 g. Fine particles (P-3) were prepared.

Preparation Example 4 [Preparation of inorganic fine particles (P-4)]
A reaction mother liquor was prepared by mixing 90 g of silica sol having an average particle diameter of 5 nm and a SiO ₂ concentration of 20% by mass with 1710 g of ion-exchanged water, and heated to 95 ° C. The reaction pH of the mother liquor is 10.5, and the aqueous sodium silicate of 1.5 wt% as SiO ₂ 24,900g in uterine fluid, Al ₂ O ₃ as a 0.5 wt% aqueous sodium aluminate solution 36, 800 g was added simultaneously. Meanwhile, the temperature of the reaction solution was maintained at 91 ° C. After completion of the addition, the reaction solution was cooled to room temperature and washed with an ultrafiltration membrane to prepare a dispersion (A) of SiO ₂ · Al ₂ O ₃ core particles having a solid content concentration of 20% by mass. (First preparation step)
Next, 500 g of the core particle dispersion (A) is collected, 1,700 g of ion exchange water is added and heated to 98 ° C., and the sodium silicate aqueous solution is removed with a cation exchange resin while maintaining this temperature. A silica protective film was formed on the surface of the core particles by adding 2,100 g of silicic acid solution (SiO ₂ concentration 3.5 mass%) obtained by alkali. The obtained dispersion of core particles having a silica protective film was washed with an ultrafiltration membrane to adjust the solid content concentration to 13% by mass, and then 1,125 g of ion-exchanged water was added to 500 g of the dispersion of core particles. Concentrated hydrochloric acid (35.5%) was added dropwise to adjust the pH to 1.0, and after dealumination treatment, the aluminum salt dissolved in the ultrafiltration membrane was separated while adding 10 L of hydrochloric acid aqueous solution of pH 3 and 5 L of ion-exchanged water. Then, a particle precursor dispersion was prepared. (Second preparation step)
A mixture of 1500 g of the particle precursor dispersion, 500 g of ion-exchanged water and 1,750 g of ethanol is heated to 30 ° C., and then 40 g of tetraethoxysilane (SiO ₂ 28% by mass) and 626 g of 28% ammonia water are added at a speed. Were added while controlling, and a silica outer shell layer was formed on the surface of the particle precursor with a hydrolyzed polycondensate of tetraethoxysilane, thereby producing particles having cavities inside the outer shell layer. Next, after concentrating to 5% by mass of solid content with an evaporator, add ammonia water with a concentration of 15% by mass to pH 10, heat-treat in an autoclave at 180 ° C. for 4 hours, and use an ultrafiltration membrane to convert the solvent to ethanol. A dispersion of substituted hollow silica fine particle sol (hole-containing inorganic fine particles) (P-4) having a solid content concentration of 20% by mass was prepared. (Third preparation step)

Preparation Example 5 [Preparation of inorganic fine particles (P-5)]
In the third preparation step of inorganic fine particles (P-4), hollow silica is obtained in the same manner as the preparation step of inorganic fine particles (P-4) except that the amount of tetraethoxysilane (SiO ₂ 28 mass%) is changed to 60 g. A fine particle sol (P-5) was prepared.

Preparation Example 6 [Preparation of inorganic oxide particles (P-6)]
In the third preparation step of the inorganic oxide particles (P-4), the same procedure as in the preparation step of the inorganic fine particles (P-4) was performed except that the addition amount of tetraethoxysilane (SiO ₂ 28% by mass) was changed to 70 g. Hollow silica fine particle sol (P-6) was prepared.

Preparation Example 7 [Preparation of inorganic fine particles (P-7)]
In the third preparation step of the inorganic fine particles (P-4), hollow silica is obtained in the same manner as the preparation step of the inorganic fine particles (P-4) except that the amount of tetraethoxysilane (SiO ₂ 28% by mass) is changed to 160 g. A fine particle sol (P-7) was prepared.

In the preparation of the inorganic oxide particles (P-4), particles (P-8) to (P-11) having different particle sizes, adsorbed water amounts, and refractive indexes were prepared by adjusting the following steps.
[Change particle size]
In the first preparation step, the particle size was changed by changing the amount of silica sol having an average particle size of 5 nm.
[Change of amount of adsorbed water]
In the second preparation step, the amount of silicic acid solution (SiO ₂ concentration 3.5% by mass) is changed, or in the third preparation step, the amount of tetraethoxysilane, ammonia amount, addition timing, temperature, time, etc. are changed as appropriate. Particles were formed.

[Evaluation of inorganic fine particles]
The following evaluation was performed using the particles thus obtained.
(Evaluation 1) Particle size measurement The dispersion was diluted and skimmed on a grid and observed with a transmission electron microscope. The average particle size of 1000 particles was determined.
(Evaluation 2) Amount of adsorbed water After the dispersion was dried with an evaporator and powdered, it was calculated by the following formula as a percentage of mass reduction when the temperature was raised to 200 ° C.
Adsorbed water amount (%) = 100 × (W20−W200) / W200
(W20: initial mass at the start of temperature rise, W200: mass at the time when the temperature is raised to 200 ° C.)
(Evaluation 3) Particle Refractive Index A coating film was formed by changing the content of particles in the matrix by the method described herein. The refractive index of the film was measured, and the refractive index when the inorganic fine particles were 100% was extrapolated to obtain the particle refractive index.
The results of evaluation (1) to (3) are shown in Table 1.

[Example 1]
The multilayer antireflection film shown below was produced.
(Preparation of sol solution a)
In a reactor equipped with a stirrer and a reflux condenser, 120 parts of methyl ethyl ketone, 100 parts of acryloyloxypropyltrimethoxysilane (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.), diisopropoxyaluminum ethyl acetoacetate (trade name, Kerope) EP-12 (manufactured by Hope Pharmaceutical Co., Ltd.) was added and mixed, and then 30 parts of ion-exchanged water was added and reacted at 60 ° C. for 4 hours. The mass average molecular weight was 1600, and among the components higher than the oligomer component, the component having a molecular weight of 1000 to 20000 was 100%. Further, from the gas chromatography analysis, the raw material acryloyloxypropyltrimethoxysilane did not remain at all. Sol solution a was adjusted with methyl ethyl ketone so that the solid content was 29%.

(Preparation of dispersion A-6)
While adding isopropyl alcohol so that the content of silica is substantially constant with respect to 500 parts of the hollow silica fine particle sol (P-6) prepared in Preparation Example 6 (silica concentration 20 mass%, ethanol dispersion) Solvent replacement by vacuum distillation was performed at a pressure of 20 kPa. 500 parts of the silica dispersion thus obtained (silica concentration 20%), 30 parts of acryloyloxypropyltrimethoxysilane (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.), and diisopropoxyaluminum ethyl acetate ( After adding 1.5 parts of a trade name, Kerope EP-12, manufactured by Hope Pharmaceutical Co., Ltd. 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. While adding cyclohexanone to 500 g of this dispersion so that the silica content was almost constant, solvent substitution was performed by distillation under reduced pressure at a pressure of 20 kPa. There was no generation of foreign matter in the dispersion, and the viscosity when the solid content concentration was adjusted to 20% by mass with cyclohexanone was 5 mPa · s at 25 ° C. When the residual amount of isopropyl alcohol in the obtained dispersion (A-6) was analyzed by gas chromatography, it was 1.5%.
The other inorganic fine particles (P-1) to (P-5) and (P-7) to (P-11) prepared in the respective preparation examples are treated according to the preparation of the dispersion liquid (A-6). Corresponding dispersions (A-1) to (A-5) and (A-7) to (A-11) were prepared.

(Synthesis of Perfluoroolefin Copolymer (1) [Exemplary Fluoropolymer: P-1])

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

(Preparation of coating liquid A for hard coat layer)
PETA 50.0 parts by mass Irgacure 184 2.0 parts by mass SX-350 (30%) 1.7 parts by mass Cross-linked acrylic-styrene particles (30%) 13.3 parts by mass FP-132 0.75 parts by mass KBM-5103 10.0 parts by mass Toluene 38.5 parts by mass

(Preparation of coating liquid B for hard coat layer)
Desolite Z7404 100 parts by mass (Zirconia fine particle-containing hard coat composition solution: manufactured by JSR Corporation)
DPHA (UV curable resin: manufactured by Nippon Kayaku Co., Ltd.) 31 parts by mass KBM-5103 10 parts by mass KE-P150 (1.5 μm silica particles: manufactured by Nippon Shokubai Co., Ltd.) 8.9 parts by mass MXS-300 ( 3 μm cross-linked PMMA particles (manufactured by Soken Chemical Co., Ltd.) 3.4 parts by mass MEK (methyl ethyl ketone) 29 parts by mass MIBK (methyl isobutyl ketone) 13 parts by mass

(Preparation of coating liquid C for hard coat layer)
750.0 parts by mass of trimethylolpropane triacrylate (TMPTA: Biscoat # 295, manufactured by Nippon Kayaku Co., Ltd.), 270.0 parts by mass of poly (glycidyl methacrylate) having a mass average molecular weight of 15000, 730.0 parts by mass of methyl ethyl ketone, 500.0 parts by mass of cyclohexanone and 50.0 parts by mass of a photopolymerization initiator (Irgacure 184, manufactured by Ciba Geigy Japan Ltd.) were added and stirred.

  The coating solutions A and B were filtered through a polypropylene filter having a pore size of 30 μm, and C was a pore size of 0.4 μm to prepare a coating solution for a hard coat layer.

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

Dispersant

(Preparation of coating liquid A for medium refractive index layer)
In 99.1 parts by mass of the above titanium dioxide dispersion, 68.0 parts by mass of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA), a photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy Japan Ltd.) 3.6 parts by mass, 1.2 parts by mass of a photosensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.), 279.6 parts by mass of methyl ethyl ketone and 1049.0 parts by mass of cyclohexanone were added and stirred. After sufficiently stirring, the mixture was filtered through a polypropylene filter having a pore size of 0.4 μm.

(Preparation of coating liquid A for high refractive index layer)
To 469.8 parts by mass of the above-mentioned titanium dioxide dispersion A, 40.0 parts by mass of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.), a photopolymerization initiator (Irgacure 907) 3.3 parts by mass, manufactured by Ciba Geigy Co., Ltd.), 1.1 parts by mass of photosensitizer (Kayacure-DETX, manufactured by Nippon Kayaku Co., Ltd.), 526.2 parts by mass of methyl ethyl ketone, and 459.6 parts by mass of cyclohexanone. Parts were added and stirred. It filtered with the polypropylene filter with the hole diameter of 0.4 micrometer.

(Preparation of coating solution A for low refractive index layer)
JTA-113 (6%) 941.7 parts by mass MEK-ST-L (30%) 100.0 parts by mass Sol solution a 46.6 parts by mass The total solid content concentration of the coating solution is 6% by mass, and cyclohexanone The mixture was diluted with cyclohexanone and MEK so that the mass ratio of MEK was 3 to 97.

(Preparation of coating solution B for low refractive index layer)
JTA-113 (6%) 941.7 parts by mass Prepared particle dispersion: A-4 (20%) 195.0 parts by mass Sol solution a 15.6 parts by mass The total solid content concentration of the coating solution is 6% by mass. The solution was diluted with cyclohexanone and MEK so that the mass ratio of cyclohexanone and MEK was 10:90.

(Preparation of coating solution C for low refractive index layer)
JTA-113 (6%) 783.3 parts by mass Prepared particle dispersion: A-4 (20%) 195.0 parts by mass MEK-ST-L (30%) 30.0 parts by mass Sol solution a 17.2 parts by mass The whole coating liquid was diluted with cyclohexanone and MEK so that the solid content concentration of the whole coating solution was 6% by mass and the mass ratio of cyclohexanone and MEK was 10:90.

(Preparation of coating solution D for low refractive index layer)
DPHA 50.0 parts by weight Prepared particle dispersion: A-4 (20%) 195.0 parts by weight Irg-907 3.0 parts by weight Sol solution a 17.2 parts by weight The solid content concentration of the entire coating liquid is 6% by weight. And diluted with cyclohexanone and MEK so that the mass ratio of cyclohexanone and MEK was 10:90.

(Preparation of coating liquid E for low refractive index layer)
DPHA 50.0 parts by weight Prepared particle dispersion: A-6 (20%) 195.0 parts by weight Irg-907 3.0 parts by weight Sol solution a 17.2 parts by weight The total solid content concentration of the coating liquid is 6% by weight. And diluted with cyclohexanone and MEK so that the mass ratio of cyclohexanone and MEK was 10:90.

(Preparation of coating solution F for low refractive index layer)
DPHA 50.0 parts by weight Prepared particle dispersion: A-6 (20%) 195.0 parts by weight RMS-033 3.0 parts by weight Irg-907 3.0 parts by weight Sol solution a 17.2 parts by weight Whole coating liquid The solution was diluted with cyclohexanone and MEK so that the solid content concentration was 6 mass% and the mass ratio of cyclohexanone and MEK was 10:90.

(Preparation of coating solution G for low refractive index layer)
DPHA 5.0 parts by weight Illustrative fluoropolymer: P-1 45.0 parts by weight Prepared particle dispersion: A-4 (20%) 195.0 parts by weight Irg-907 3.0 parts by weight Sol solution a 17.2 parts by weight The whole coating liquid was diluted with cyclohexanone and MEK so that the solid content concentration of the whole coating solution was 6% by mass and the mass ratio of cyclohexanone and MEK was 10:90.

(Preparation of coating solution H for low refractive index layer)
DPHA 5.0 parts by weight Illustrative fluoropolymer: P-1 45.0 parts by weight Prepared particle dispersion: A-6 (20%) 195.0 parts by weight Irg-907 3.0 parts by weight Sol solution a 17.2 parts by weight The whole coating liquid was diluted with cyclohexanone and MEK so that the solid content concentration of the whole coating solution was 6% by mass and the mass ratio of cyclohexanone and MEK was 10:90.

(Preparation of coating liquid I for low refractive index layer)
DPHA 5.0 parts by weight Illustrative fluoropolymer: P-1 45.0 parts by weight Prepared particle dispersion: A-6 (20%) 195.0 parts by weight RMS-033 3.0 parts by weight Irg-907 3.0 parts by weight Part Sol solution a 17.2 parts by weight The whole coating liquid was diluted with cyclohexanone and MEK so that the solid content concentration was 6% by mass and the mass ratio of cyclohexanone and MEK was 10/90.

(Preparation of coating liquid J for low refractive index layer)
Illustrative fluoropolymer: P-1 93.0 parts by mass RMS-033 3.0 parts by mass Irg-907 4.0 parts by mass The total solid content concentration of the coating solution is 6% by mass, and the mass ratio of cyclohexanone to MEK is 10. Dilution was performed with cyclohexanone and MEK so that the ratio was 90.

(Preparation of coating solution K for low refractive index layer)
30 parts by mass of tetramethoxysilane and 240 parts by mass of methanol are put into a four-necked reaction flask and stirred while keeping the liquid temperature at 30 ° C. Then, an aqueous solution in which 2 parts by mass of nitric acid is added to 6 parts by mass of water is added. The mixture was stirred at 30 ° C. for 5 hours to obtain a siloxane oligomer alcohol solution (solution A). The relative molecular weight in terms of ethylene glycol / polyethylene oxide by GPC of the siloxane oligomer was 950.

  Separately, 300 parts by mass of methanol was added to a four-necked reaction flask, and then 30 parts by mass of oxalic acid was mixed with stirring. While heating and refluxing this solution, 30 parts by mass of tetramethoxysilane and 8 parts by mass of tridecafluorooctyltrimethoxysilane were added dropwise, heated under reflux for 5 hours, cooled, and fluorine having a fluoroalkyl structure and a polysiloxane structure. A solution of the compound (Solution B) was obtained.

  30 parts by mass of solution A and 100 parts by mass of solution B were stirred and mixed, and diluted with butyl acetate so that the solid content concentration in the mixed coating solution was 1% by mass, to obtain a coating solution K for a low refractive index layer. .

(Preparation of coating liquid L for low refractive index layer)
The solutions A and B were prepared in the same manner as the coating solution K for the low refractive index layer, and 30 parts by mass of the solution A and 100 parts by mass of the solution B were further added with 1 part by mass of hydrogen-terminated polydimethylsiloxane DMS-H21 (manufactured by Gelest). 80 parts by mass of particle dispersion A-4 (20.0%) of No. 1 was mixed with stirring, and diluted with butyl acetate so that the solid content concentration in the mixed coating liquid would be 1% by mass. A coating liquid L for the rate layer was obtained.

(Preparation of coating solution M for low refractive index layer)
JTA-113 (6%) 783.3 parts by mass Prepared particle dispersion: A-5 (20%) 195.0 parts by mass MEK-ST-L (30%) 30.0 parts by mass RMS-033 3.0 parts by mass Part Sol solution a 17.2 parts by weight The whole coating liquid was diluted with cyclohexanone and MEK so that the solid content concentration was 6% by mass and the mass ratio of cyclohexanone and MEK was 10/90.

(Preparation of coating liquid N for low refractive index layer)
JTA-113 (6%) 783.3 parts by mass Prepared particle dispersion: A-5 (20%) 195.0 parts by mass MEK-ST-L (30%) 30.0 parts by mass X22-163C 3.0 parts by mass Part Sol solution a 17.2 parts by weight The whole coating liquid was diluted with cyclohexanone and MEK so that the solid content concentration was 6% by mass and the mass ratio of cyclohexanone and MEK was 10/90.

(Preparation of coating solution O for low refractive index layer)
JTA-113 (6%) 783.3 parts by weight Prepared particle dispersion: A-5 (20%) 195.0 parts by weight MEK-ST-L (30%) 30.0 parts by weight KF-6003 3.0 parts by weight Part Sol solution a 17.2 parts by weight The whole coating liquid was diluted with cyclohexanone and MEK so that the solid content concentration was 6% by mass and the mass ratio of cyclohexanone and MEK was 10/90.

  The solution was stirred and then filtered through a polypropylene filter having a pore size of 1 μm to prepare a coating solution for a low refractive index layer.

The compounds used (for which detailed descriptions are omitted in the text) are shown below.
PETA: A mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (manufactured by Nippon Kayaku Co., Ltd.)
Irgacure 184: Polymerization initiator (Ciba Specialty Chemicals Co., Ltd.)
SX-350: Cross-linked polystyrene particles having an average particle size of 3.5 μm (refractive index: 1.60, manufactured by Soken Chemical Co., Ltd., 30% toluene dispersion. Used after dispersion at 10,000 rpm for 20 minutes in a Polytron disperser)
Cross-linked acrylic-styrene particles: average particle size 3.5 μm (refractive index 1.55, manufactured by Soken Chemical Co., Ltd., 30% toluene dispersion)
FP-132: Fluorine surface modifier

KBM-5103: Silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd.).
JTA-113: Thermally crosslinkable fluorine-containing polymer (refractive index 1.44, solid content concentration 6%, manufactured by JSR Corporation) “OPSTAR JTA-113: trade name”
P-1: Perfluoroolefin copolymer (1)
DPHA: A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.)
MEK-ST-L: Silica sol (silica, MEK-ST particle size difference, average particle size 45 nm, solid content concentration 30%, manufactured by Nissan Chemical Co., Ltd.)
KF96-1000CS: straight silicone (manufactured by Shin-Etsu Chemical Co., Ltd.)
KF-6003: Carbinol-modified silicone (manufactured by Shin-Etsu Chemical Co., Ltd.)
X22-164C: Methacryloxy-modified silicone (manufactured by Shin-Etsu Chemical Co., Ltd.)
X22-163C: Epoxy-modified silicone (manufactured by Shin-Etsu Chemical Co., Ltd.)
RMS-033: Methacryloxy-modified silicone (manufactured by Gelest Co., Ltd.)
R-2020: Fluoroalkyl acrylate monomer (Daikin Co., Ltd.)
FMS-121: Fluoroalkyl silicone (manufactured by Gelest Co., Ltd.)
Irg-907: Photopolymerization initiator (manufactured by Ciba Specialty Chemicals)

(1-1) Coating of hard coat layer A and hard coat layer C As a support, a triacetyl cellulose film (TD80U, manufactured by Fuji Photo Film Co., Ltd.) is unwound in a roll form and directly for the hard coat layer. Using a microgravure roll with a diameter of 50 mm and a doctor blade having a gravure pattern with a line number of 180 lines / inch and a depth of 40 μm and a doctor blade, the coating liquid was applied at a conveyance speed of 30 m / min, dried at 60 ° C. for 150 seconds, Further, using a 160 W / cm air-cooled metal halide lamp (made by Eye Graphics Co., Ltd.) under a nitrogen purge, the illuminance is 400 mW / cm ² , the hard coat layer A is irradiated 250 mJ / cm ² , and the hard coat layer C is irradiated The coating layer was cured by irradiating with 300 mJ / cm ² of ultraviolet rays to form a hard coat layer and wound up. After curing, the rotation speed of the gravure roll was adjusted so that the hard coat layer A had a thickness of 6 μm and the hard coat layer C had a thickness of 8 μm.

(1-2) Coating of hard coat layer B A triacetyl cellulose film (TD80U, manufactured by Fuji Photo Film Co., Ltd.) is unwound as a support in the form of a roll, and the above-mentioned coating liquid for hard coat layer is directly applied to the number of lines. Using a gravure pattern with a diameter of 135 mm / inch and a depth of 60 μm, a 50 mm diameter micro gravure roll and a doctor blade were applied at a transfer speed of 10 m / min, dried at 60 ° C. for 150 seconds, and then further purged with nitrogen Using a 160 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.), an ultraviolet ray having an illuminance of 400 mW / cm ² and an irradiation amount of 250 mJ / cm ² is irradiated to cure the coating layer to form a hard coat layer. Wound up. After curing, the gravure roll rotation speed was adjusted so that the thickness of the hard coat layer was 3.6 μm.

(2) Coating of medium refractive index layer A A triacetyl cellulose film (TD-80UF, manufactured by Fuji Photo Film Co., Ltd.) coated up to the hard coat layer is unwound again, and the coating solution for the medium refractive index layer is drawn. The coating was performed using a micro gravure roll having a diameter of 50 mm having a gravure pattern of several 180 lines / inch and a depth of 40 μm and a doctor blade. Drying conditions are 90 ° C. and 30 seconds, and ultraviolet curing conditions are 180 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) while purging with nitrogen so that the oxygen concentration is 1.0 volume% or less. The irradiance was 400 mW / cm ² and the irradiation amount was 400 mJ / cm ² . The medium refractive index layer was formed and wound up while adjusting the rotation speed of the gravure roll so that the thickness after application was 67 nm. The medium refractive index layer after curing had a refractive index of 1.630.

(3) Coating of high refractive index layer A The triacetyl cellulose film (TD-80UF, manufactured by Fuji Photo Film Co., Ltd.) coated up to the middle refractive index layer is unwound again, and the coating solution for the high refractive index layer is prepared. Coating was performed using a micro gravure roll having a diameter of 180 mm / inch and a gravure pattern having a depth of 40 μm and a diameter of 50 mm and a doctor blade. Drying conditions are 90 ° C., 30 seconds, and UV curing conditions are 240 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) while purging with nitrogen so that the oxygen concentration is 1.0 vol% or less. The irradiance was 600 mW / cm ² and the irradiation amount was 400 mJ / cm ² . A high refractive index layer was formed and wound up while adjusting the rotation speed of the gravure roll so that the thickness after coating was 107 nm. The high refractive index layer after curing had a refractive index of 1.905.

(4-1) Coating of low refractive index layer “Coating curing method A”
The triacetyl cellulose film coated up to the hard coat layer or the high refractive index layer is unwound again, and the above-mentioned coating solution for the low refractive index layer is a microgravure having a diameter of 180 lines / inch and a gravure pattern with a depth of 40 μm and a diameter of 50 mm. Using a roll and a doctor blade, it was applied at a conveyance speed of 15 m / min, pre-dried at 120 ° C. for 150 seconds, further post-dried at 140 ° C. for 8 minutes, and then 240 W / cm under nitrogen purge. Using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.), irradiating ultraviolet rays with an illuminance of 400 mW / cm ² and an irradiation amount of 900 mJ / cm ² , while adjusting the rotation speed of the gravure roll so that the thickness becomes 100 nm A low refractive index layer was formed and wound up.

(4-2) Coating of low refractive index layer “Coating curing method B”
The procedure was the same as “Coating and curing method A” except that post-drying was omitted.

(4-3) Coating of low refractive index layer “Coating and curing method C”
The coating solution for the low refractive index layer prepared above was applied using a wire bar so that the thickness after curing was about 100 nm, and heat-cured at 90 ° C. for 1 hour to form an antireflection layer.

(4-4) Coating of low refractive index layer “Coating curing method D”
The triacetyl cellulose film coated up to the hard coat layer was unwound again, and the low refractive index layer coating solution was applied by a die coating method. After drying at 120 ° C. for 150 seconds and further drying at 140 ° C. for 8 minutes, irradiation is carried out at an illuminance of 400 mW / cm ² using a 240 W / cm air-cooled metal halide lamp (made by Eye Graphics Co., Ltd.) under a nitrogen purge. An ultraviolet ray having a quantity of 900 mJ / cm ² was irradiated to form a low refractive index layer having a thickness of 100 nm and wound up.

(Preparation of antireflection film sample)
As shown in Tables 2 to 4, antireflection film samples were prepared by the above methods.
In Tables 2 and 5, Samples 004 to 008, 011, 012, 014, 015, and 018 to 021 should be read as “Reference Example” instead of “present invention”.
In Tables 3 and 6, Samples 109 to 116 should be read as “Reference Example” instead of “Invention”.
In Tables 4 and 7, samples 203, 206, and 207 are referred to as “reference examples” instead of “present invention”.

(Saponification treatment of antireflection film)
After the film formation, the following treatment was performed on the samples except for the samples 016 to 018.
A 1.5 mol / l aqueous sodium hydroxide solution was prepared and kept at 55 ° C. A 0.01 mol / l dilute sulfuric acid aqueous solution was prepared and kept at 35 ° C. The prepared antireflection film was immersed in the aqueous sodium hydroxide solution for 2 minutes, and then immersed in water to sufficiently wash away the aqueous sodium hydroxide solution. Subsequently, after being immersed in the above-mentioned dilute sulfuric acid aqueous solution for 1 minute, it was immersed in water to sufficiently wash away the dilute sulfuric acid aqueous solution. Finally, the sample was thoroughly dried at 120 ° C.

(Evaluation of antireflection film)
The following items were evaluated for the film samples obtained after the saponification treatment. However, for the samples 016 to 018, the following items were similarly evaluated for the film samples not subjected to the saponification treatment.

(1) Measurement of ΔE of water adhesion trace The outermost surface of an antireflection film of a film, a polarizing plate, or an image display device was installed horizontally. After leaving at 25 ° C.-55% relative humidity for 30 minutes or more, 2.0 ml of ion-exchanged water was dropped with a pipette (manufactured by Eppendorf) over about 2 seconds. Although the easiness of spreading differs depending on the surface of the antireflection film, water droplets were spread in a circular shape having a diameter of about 1.5 to 2.5 cm. After leaving for 15 minutes, the water droplets were wiped off with Bencot (manufactured by Asahi Kasei Corporation). The reflection spectrum of the antireflection film was measured before and after the water drop was dropped. The measurement was performed using a Model V-550UV / Vis Spectrophotometer manufactured by JASCO Corporation, and the change in chromaticity (ΔE) in the CIE1976L ^* a ^* b ^* color space under a D65 standard light source was determined.
(2) Average reflectance Using a spectrophotometer (manufactured by JASCO Corporation), the spectral reflectance at an incident angle of 5 ° was measured in a wavelength region of 380 to 780 nm. The average reflectance of 450-650 nm was used for the result.
(3) Magic wiping property An anti-reflection film is fixed on the glass surface with an adhesive, and the diameter of the black magic “Mackey Extra Fine (trade name: made by ZEBRA)” pen tip (thin) under the condition of 25 ° C. and 60 RH%. Write a 5-mm circle 3 times and wipe it back and forth 20 times with a load that dents the bundle of Bencot (Brand name, Asahi Kasei Co., Ltd.) that is folded into 10 layers after 5 seconds. The writing and wiping were repeated under the above-mentioned conditions until the magic mark was not erased by wiping, and the number of times of wiping was determined. The above test was repeated 4 times, and the following 4 grades were evaluated on average.
: Can be wiped 10 times or more.
○: Can be wiped off several times to less than 10 times.
Δ: Can be wiped off only once.
×: Cannot be wiped once

(4) Evaluation of surface segregation degree of silicone (Si atom) and fluoroalkyl (F atom) Measured for each antireflection film with ESCA-3400 manufactured by Shimadzu Corporation (vacuum degree 1 × 10 ⁻⁵ Pa, X-ray source Intensity ratio Si2p / C1s (= Si (a)), F1s / C1s (= F (a)) and ESCA- of target surface Mg, voltage 12 kV, current 20 mA) of the outermost surface Si2p, F1s, C1s The photoelectron spectrum measured from the surface of the low-refractive index layer cut to 1/5 (± 5%) with an ion etching apparatus (ion gun, voltage 2 kV, current 20 mA) attached to 3400 from the surface 80% below. From the intensity ratios Si2p / C1s (= Si (b)) and F1s / C1s (= F (b)), changes in the respective intensity ratios before and after etching, Si (a) / i (b) and F (a) / F (b) are obtained, and the respective Si2p / C1s ratio and F1s / C1s ratio change before and after etching (intensity ratio of photoelectron spectrum at the top of the low refractive index layer / low refractive index). The change in the intensity ratio of the photoelectron spectrum in the vicinity of the lower layer 80% deep from the surface of the rate layer) was evaluated in the following four stages. The above measurement was performed at three locations at least 2 cm apart from each other on the same film surface.
A: The strength ratio after etching is 5 times or more and 1 or more places.
○: The strength ratio after etching is less than 5 times, and 3 times or more is 1 place or more.
Δ: The strength ratio after etching is less than 3 times, and 1.5 times or more is one or more places.
-: Intensity ratio after etching is less than 1.5 times Note that F1s and C1s are obtained at the peak positions of the respective photoelectron spectra, and Si2p is derived from silicone (Si atom of polydimethylsiloxane) having a binding energy of around 105 eV. The intensity at the peak position was used for the above intensity ratio calculation to distinguish it from Si atoms derived from inorganic silica particles. Preliminary experiments in which the surface of the low-refractive index layer is gradually scraped under various etching conditions are performed, and the depth of 80% from the surface is reached from the etching conditions required to reach the lower hard coat layer or high-refractive index layer. Measured after obtaining.

From the results shown in Tables 5 to 7, the following is clear.
The antireflection film of the present invention has a small color change after adhesion of water droplets, is excellent in reflectance and magic wiping properties, and has improved performance as an antireflection film. The samples of the present invention can achieve low reflection and suppression of color change after adhesion of water droplets with respect to the comparative sample 001. Samples 103 to 106 to which silicone or a fluoroalkyl compound is added to the comparative sample 101 are water droplets. In addition to suppressing color change after adhesion, the magic wiping property is improved. Further, Samples 110 to 113 using silicone and a fluorine binder in combination were excellent in suppressing color change after adhesion of water droplets, and exhibited even higher magic wiping properties.

[Example 2]
Next, this invention sample film 004, 006, 015, 110 was bonded together with the polarizing plate, and the polarizing plate with reflection prevention was produced. When a liquid crystal display device having an antireflection layer disposed on the outermost layer using this polarizing plate was produced, there was little reflection of external light, and the reflected image was not noticeable and had excellent visibility. Moreover, after the water drop adhesion which becomes a problem in the actual use form, antifouling property, etc. were satisfied.

[Example 3]
An 80 μm-thick triacetyl cellulose film (TAC-TD80U, manufactured by Fuji Photo Film Co., Ltd.), which was immersed in a 1.5 mol / l, 55 ° C. NaOH aqueous solution for 2 minutes, then neutralized and washed with water, and Examples A polarizing plate was prepared by adhering and protecting both sides of a polarizing film prepared by adsorbing iodine to polyvinyl alcohol on the triacetyl cellulose film provided with the sample of the present invention used in No. 2 and stretching it. The thus-prepared polarizing plate is a liquid crystal display device of a notebook computer equipped with a transmission type TN liquid crystal display device (Sumitomo 3M Co., Ltd., which is a polarization separation film having a polarization selection layer) so that the antireflection film side is the outermost surface. When the polarizing plate on the viewing side of D-BEF made of the product between the backlight and the liquid crystal cell was replaced, a display device with very high display quality was obtained with very little background reflection.

[Example 4]
As a protective film on the liquid crystal cell side of the polarizing plate on the viewing side of the transmission type TN liquid crystal cell to which the sample of the present invention used in Example 2 was attached, and as a protective film on the liquid crystal cell side of the polarizing plate on the backlight side, discotic Optical compensation in which the disc surface of the structural unit is inclined with respect to the transparent support surface, and the angle formed by the disc surface of the discotic structural unit and the transparent support surface changes in the depth direction of the optical anisotropic layer When viewing film with wide viewing angle (Wide View Film SA-12B, manufactured by Fuji Photo Film Co., Ltd.) is used, the contrast in the bright room is excellent, and the viewing angles in the top, bottom, left and right are very wide and extremely visible. Thus, a liquid crystal display device with excellent display quality was obtained.

[Example 5]
When the sample of the present invention used in Example 2 was bonded to a glass plate on the surface of an organic EL display device via an adhesive, reflection on the glass surface was suppressed, visibility was high, and contamination to fingerprints and dust was caused. Thus, a display device that can withstand this problem was obtained.

[Example 6]
Using the sample of the present invention used in Example 2, a polarizing plate with a single-sided antireflection film was prepared, and a λ / 4 plate was laminated on the opposite side of the polarizing plate having the antireflection film, and the antireflection film When affixed to the glass plate on the surface of the organic EL display device so that the side became the outermost surface, the surface reflection and the reflection from the inside of the surface glass were cut, and a display with extremely high visibility was obtained.

It is sectional drawing of the coater using the slot die used in the case of implementation of this invention.

Explanation of symbols

10 Coater 11 Backup Roll W Web 13 Slot Die 14 Coating Solution 14a Bead 14b Coating 15 Pocket 16 Slot 17 Tip Lip 18 Land 18a Upstream Lip Land 18b Downstream Lip Land

Claims (6)

On a transparent support, a saturated hydrocarbon having compound reduces porous and / or hollow inorganic fine particle size is 6.1 wt% or less amount of adsorbed water is 20 to 100 nm, the surface free energy, and a cross-linked structure An antireflection film having a low refractive index layer containing a binder polymer having a chain as a main chain ,
The compound for reducing the surface free energy is a silicone compound containing at least one active energy ray-curable (meth) acryloyl group in the molecule,
The binder polymer having a saturated hydrocarbon chain having a crosslinked structure as a main chain is composed of a (co) polymer of monomers having two or more ethylenically unsaturated groups, and the monomers are selected from the following: Anti-reflection film.
Esters of polyhydric alcohol and (meth) acrylic acid, vinylbenzene and its derivatives, vinyl sulfone, acrylamide, and methacrylamide The binder polymer having a saturated hydrocarbon chain having a crosslinked structure as a main chain is a (co) polymer of a monomer having two or more ethylenically unsaturated groups, and the monomer is selected from the following: The antireflection film according to claim 1.
Ethylene glycol di (meth) acrylate, 1,4-cyclohexanediacrylate, pentaerythritol tetra (meth) acrylate), pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate , Dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,2,3-cyclohexanetetramethacrylate, polyurethane polyacrylate, polyester polyacrylate, 1,4- Divinylbenzene, 4-vinylbenzoic acid-2-acryloylethyl ester, 1,4-divinylcyclohexanone, divinylsulfone, methylenebisacrylic Luamide Silicone and / or fluoroalkyl groups segregate on the surface of the low refractive index layer, and the photoelectron spectrum intensity ratio Si / C and / or F / C in the lowermost layer and 80% below the outermost surface of the low refractive index layer 3. The antireflection film according to claim 1, wherein the antireflection film is 5 times or more larger than an 80% lower layer on the outermost surface. The surface of the inorganic fine particles is treated with a hydrolyzate of organosilane represented by the following general formula (I) and / or a partial condensate thereof using an acid catalyst and / or a metal chelate compound. the antireflection film according to any one of claims 1 to 3, characterized.
Formula (I): (R ¹⁰ ) _m Si (X) _4-m
(In the formula, R ¹⁰ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. X represents a hydroxyl group or a hydrolyzable group. M represents an integer of 1 to 3.) A polarizing plate comprising the antireflection film as described in any one of claims 1-4. The image display apparatus comprising the polarizing plate according to the antireflection film or claim 5 according to any one of claims 1-4.

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