JP2006251666A - Optical film, polarizing plate and image display device using them - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an optical film which has a low reflectance, is capable of suppressing glare and is excellent in scratch resistance and, further, to provide a polarizing plate and a display device using such an antireflection film. <P>SOLUTION: In the optical film having at least one layer on a substrate, a thin film layer comprising inorganic particles and a binder is formed on the uppermost surface, and the percent content of the inorganic fine particles varies in the thickness direction in thin film layer, wherein the inorganic fine particles have the minimum percent content (A) on a region of the reverse side (upper side) to the substrate and have the maximum percent content (B) on a region of the substrate side (lower side) from the region showing the minimum percent content and the rate R (=A/B) of the minimum percent content (A) to the maximum percent content (B) exceeds 1. Further, the antireflection film, and the polarizing plate and the image display device using the antireflection film are also disclosed. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

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

When blended with fine particles and a binder and used for applications such as adhesives, exterior paints, hard coats, anti-reflective coatings, etc., the scratch resistance of the resulting coating, the strength of the cured product, and other materials that come into contact with the coating Improving the adhesiveness of the material has been studied.
When blending the fine particles and the binder, it is necessary that inorganic materials such as fine particles do not cause unnecessary aggregation. One of the commonly used methods is a method in which fine particles are dispersed in a solvent having affinity for the binder and then mixed with the binder to form a film. In order to obtain stable performance, it is important that the fine particles are stably dispersed in the solvent. Specifically, it is important to control hydrophilicity / hydrophobicity and steric hindrance on the surface of the fine particles, and it is known that inorganic oxide fine particles are surface-treated with alkoxysilane. For example, Non-Patent Document 1 describes a method of dispersing inorganic particles in an organic solvent using a silane coupling agent.

  After the coating composition containing the fine particles and the binder has been stably prepared, the composition is coated on a support to achieve the desired performance. At that time, if the state of the fine particles in the coating film cannot be controlled, performances such as the intended scratch resistance, the strength of the cured product, and the adhesion with other materials that have come into contact with each other will fluctuate. In particular, since the coating composition containing fine particles having a particle size of 1 micron or less has a large specific surface area, the interaction between the fine particles is large in the drying process of the organic solvent, and aggregation tends to occur. As a result, aggregation and phase separation may occur in the coating film, which may adversely affect the coating film performance.

  On the other hand, an antireflection film is generally used in display devices such as a cathode ray tube display (CRT), a plasma display (PDP), an electroluminescence display (ELD), and a liquid crystal display (LCD). In order to prevent image reflection, it is placed on the outermost surface of the display to reduce reflectivity using the principle of optical interference.

  Such an antireflection film has a low refractive index layer with an appropriate thickness on the outermost surface, and optionally a high refractive index layer, a medium refractive index layer, a hard coat layer between the low refractive index layer and the support. It can produce by providing. 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, it is expected to function as a protective film for the display device. Therefore, it is required that dirt and dust are difficult to adhere and that scratch resistance is strong. In order to realize high scratch resistance in a thin film having a thickness of around 100 nm, the strength of the coating itself and the adhesion to the lower layer are required.

  In order to lower the refractive index of the material, there are means of introducing fluorine atoms into the coating material or lowering the density (introducing voids), but in any case the coating strength and adhesion are impaired and the scratch resistance is lowered. This is a difficult task to achieve both a low refractive index and high scratch resistance.

  Patent Document 1, Patent Document 2 and Patent Document 3 describe means for reducing the coefficient of friction of the film surface and improving the scratch resistance by introducing a polysiloxane structure into the fluorine-containing polymer of the film material. Although this means is effective to some extent for improving scratch resistance, sufficient scratch resistance cannot be obtained only by this method for a film having an insufficient film strength and interfacial adhesion.

  On the other hand, Patent Document 4 describes that the scratch resistance is greatly improved by adding a silane coupling agent to a low refractive index layer material using a fluorine-containing polymer. However, the silane coupling agent having a low boiling point has a problem that it volatilizes in the coating and drying process, and requires an excessive amount of addition in consideration of the volatilized content, and there is a problem that it is difficult to obtain stable performance.

  In addition, regarding the low refractive index layer, when inorganic fine particles are dispersed in the binder as described above, the strength of the film is expected to improve, but the aggregation and phase separation of the inorganic fine particles in the coating film are likely to occur. It is also conceivable that the presence state of the inorganic fine particles changes greatly and the scratch resistance changes in an inconvenient manner.

The prior art according to the present invention is as follows.
Pigment dispersion technology, surface treatment and usage of dispersants and evaluation of dispersibility (published in 1999 by Technical Information Association) Japanese Patent Laid-Open No. 11-189621 Japanese Patent Laid-Open No. 11-228631 JP 2000-313709 A JP 2003-222704 A

  An object of the present invention is to provide an optical film having low reflectivity and excellent scratch resistance. Furthermore, it is providing the polarizing plate and display apparatus which used the antireflection film as such an optical film.

As a result of intensive studies, the present inventor has found that the effects of the present invention can be obtained by the following means.
(Please correct it according to the following claims.)
(1) An optical film in which at least one layer is formed on a support, and a thin film layer having a thickness of 200 nm or less containing inorganic fine particles and a binder is formed on the outermost surface. The particle size is less than 1/2 of the film thickness of the thin film layer, and is in a non-uniform existence state where the inorganic fine particles have a honey area and a sparse area in the film thickness direction, The average particle filling in the 50% film thickness opposite to the support (upper side) with respect to the average particle filling ratio (A) in the 50% film thickness on the support side (lower side) of the thin film layer. An optical film, wherein the ratio (B) ratio R1 [= (B / A) × 100 (%)] is 5% or more and less than 100%.
(2) The content of the inorganic fine particles takes the minimum content (C) in the ½-thickness region on the opposite side (upper side) from the support, and the support side (lower side) from the region showing the minimum content The maximum content rate (D) is taken in the region of), and the ratio R2 [= (C / D) × 100 (%)] of the minimum content rate (D) to the maximum content rate (C) is 8% or more. The optical film as described in (1) above, which is characterized.
(3) The optical film as described in (1) or (2) above, which contains 10% by mass or more of inorganic fine particles (4) A compound in which the surface of the inorganic fine particles forms a covalent bond with the inorganic fine particles. The optical film according to any one of (1) to (3), wherein the optical film is processed.
(5) The optical film as described in any one of (1) to (4) above, wherein the inorganic oxide particles contain silicon dioxide as a main component.
(6) The optical film as described in any one of (1) to (5) above, wherein the inorganic fine particles are hollow silica.
(7) The optical film as described in any one of (1) to (6) above, wherein the binder contains at least one ionizing radiation curable resin.
(8) The optical film as described in any one of (1) to (6) above, wherein the binder contains a thermosetting resin.
(9) The optical film as described in any one of (1) to (8) above, wherein the binder contains a compound containing at least a fluorocarbon and / or dimethylsiloxane.
(10) The optical film according to any one of (1) to (9) above, wherein the support is a transparent support, and the optical film has at least a hard coat layer and a low refractive index layer laminated. A multilayer antireflection film characterized by comprising

(11) At least one high refractive index layer containing inorganic fine particles between a layer having a hard coat property and a low refractive index layer, and having an average mirror reflectivity of 5 ° at a wavelength of 450 nm to 650 nm The multilayer antireflection film as described in (10) above, wherein the value is 1% or less.
(12) The method for producing an optical film as described in any one of (1) to (11) above, wherein the coating composition containing fine particles and a binder contains at least two volatile solvents. A method for producing an optical film.
(13) A polarizing plate comprising the optical film according to any one of (1) to (11).
(14) A polarizing plate comprising the optical film according to any one of (1) to (11) and a retardation film.
(15) A display device comprising the optical film according to any one of (1) to (11) or the polarizing plate according to (13) or (14).

  The optical film of the present invention provided with the above low refractive index layer has low reflectance and excellent scratch resistance. Further, the display device provided with the optical film of the present invention or the polarizing plate using the optical film of the present invention as an antireflection film has little reflection of external light and background reflection, high visibility, and scratch resistance. High nature.

  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”. .

[Distribution of particles in the layer]
In the optical film of the present invention, a composition containing inorganic fine particles and a binder is coated on a support directly or via another layer to form a thin film layer of 200 nm or less. As the inorganic fine particles, particles having a small particle size are preferably used in order to suppress an increase in haze due to scattering at the interface between the binder and the particles and scattering due to surface irregularities. In the present invention, the particle size is the film thickness of the thin film layer. Less than 1/2 of the inorganic fine particles. The state of the presence of the inorganic fine particles in the binder is generally considered to be uniformly dispersed. When excessive aggregation proceeds, problems such as an increase in haze and a decrease in hardness occur. However, regarding scratch resistance, which is important when an optical film is used on the outermost surface of a display or the like, the present invention is more effective in taking a specific non-uniform state in the thickness direction than the presence of inorganic fine particles uniformly. This is based on the new finding that good scratch resistance can be obtained by making the abundance ratio of the body side (lower side) and the opposite side of the support (upper side) within a specific range.

[Filling ratio R1]
In the optical film of the present invention, the ratio R1 [= (B / A) of the average particle filling ratio (B) in the upper 50% film thickness to the average particle filling ratio (A) in the lower 50% film thickness. × 100 (%)] was used as an index of the abundance ratio in the thickness direction. Each average particle filling factor (A) and (B) was determined by the following method. The optical film was taken as a section having a thickness of 50 nm, and the cross section was photographed at 150,000 magnifications using five fields of view using a transmission electron microscope. Dividing the layer thickness in half in the thickness direction into the upper side and the lower side, for each of the upper side and the lower side, the ratio of the occupied area of the inorganic fine particles to the total area was obtained and averaged, and this was used as the average particle filling rate . In the calculation, the width of 50 times the film thickness was targeted.
In the optical film of the present invention, R1 is 5% or more and less than 100%. Preferably they are 8% or more and less than 100%, More preferably, they are 10% or more and less than 90%.
If the value of R1 is too small, the presence of inorganic fine particles in the upper part is scarce and good scratch resistance cannot be obtained. I can't get it. Therefore, it is preferable to fall within the range described in the present invention in order to obtain good scratch resistance.

[Content Ratio R2]
In the optical film of the present invention, the ratio R2 [= (C / D) × 100 of the minimum content ratio (C) to the maximum content ratio (D) in the film thickness direction with respect to the content ratio represented by (General Formula 1). (%)] Was used as an index of the abundance ratio in the thickness direction. In the present invention, the content of the inorganic fine particles is represented by the general formula (1).
(General formula 1)
M element content / (carbon content + M element content + oxygen content) × 100 (%)
The M element content here refers to the content of the metal element M contained in the inorganic fine particles. When a plurality of metal elements are contained, the content of each metal element is obtained and the sum is obtained. The content of each element in the thin film layer can be measured using an X-ray photoelectron spectrometer (XPS apparatus). There is no particular limitation on the XPS device, and any model can be used. The change in content of each element in the depth direction of the film can be obtained by repeatedly performing measurement after etching using rare gas ions. The end point of the thin film layer (interface with the lower layer) is the point where the M element content is 20% or less, and the portion where the etching time is within half of the etching time at that point is the upper side, the etching time is more than half This point is the lower side. Further, when the same M element is contained in the lower layer, it can be obtained by taking data of the M element content of only the lower layer and correcting it. When M element is contained in the binder component, the M element content of only the binder component can be obtained and corrected by the general formula (1). The minimum content rate (C) and the maximum content rate (D) are the minimum value and the maximum value among the data in the depth direction of the content rate of the inorganic fine particles expressed by the general formula (1).

In the optical film of the present invention, the inorganic fine particles take the minimum content (C) in the region opposite to the support (upper side), and the region closer to the support (lower side) than the region showing the minimum minimum content. The ratio R2 [= C / D (%)) of the minimum content (C) to the maximum content (D) is 5% or more and less than 100%, when the maximum content (D) is used. To do. Preferably it is 8 to 100%, More preferably, it is 10 to 90%.
If the value of R2 is too small, the presence of inorganic fine particles in the upper part is scarce and good scratch resistance cannot be obtained. If it is too large, the uneven distribution of inorganic fine particles in the lower part is insufficient and good scratch resistance is obtained. I can't get it. Therefore, it is preferable to fall within the range described in the present invention in order to obtain good scratch resistance.

  An example of the presence state of the inorganic fine particles is shown in FIG. 1, but the presence state of the inorganic fine particles is not limited to the example of FIG. The five examples shown in FIG. 1 show that the side farther from the support has a lower average particle filling rate than the side closer to the support, and the region with the lowest content is also on the side farther from the support.

  In the present invention, in the thin film layer containing the fine particles and the binder, the mass ratio of the fine particles to the total solid content is preferably 5 to 85%, more preferably 10 to 80%, and most preferably 20 to 75%. . If this ratio is too high, the film becomes brittle, and if it is too low, the purpose of containing the original fine particles cannot be exhibited. In the present invention, the thickness of the thin film layer is preferably 10 to 200 nm, more preferably 50 to 150 nm, and particularly preferably 70 to 120 nm. The binder preferably contains at least a compound containing a fluorocarbon or dimethylsiloxane moiety.

Next, the process for improving the dispersibility of the fine particles in the thin film layer will be described. In the present invention, the fine particles are preferably inorganic fine particles, and particularly preferably inorganic oxide fine particles.
The inorganic oxide fine particles have been subjected to a treatment for improving dispersibility by the hydrolyzate of organosilane represented by the following general formula (I) and / or a partial condensate thereof. In the treatment for improving dispersibility, it is preferable to use either an acid catalyst or a metal chelate compound, or both.
In the dispersibility improving treatment, organosilane, inorganic oxide fine particles, and water as necessary are brought into contact in the presence of at least one of a catalyst having a hydrolysis function and a metal chelate compound having a condensation function. Is done. The organosilane may be partially hydrolyzed or partially condensed. The organosilane undergoes partial condensation subsequent to hydrolysis, which modifies the surface of the inorganic oxide fine particles to improve the dispersibility and obtain a stable dispersion of inorganic oxide fine particles.
Moreover, it is also possible to add and use the organosilane represented by the following general formula (I) and / or its hydrolyzate and / or its partial condensate separately from the inorganic fine particles.

Formula (I)
(R ¹⁰ ) _m Si (X) _4-m
(In the formula, R ¹⁰⁰ 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.)
Metal chelate compound An alcohol represented by a general formula R ³ OH (wherein R ³ represents an alkyl group having 1 to 10 carbon atoms) and a general formula R ⁴ COCH ₂ COR ⁵ (wherein R ⁴ is the number of carbon atoms) Zr, Ti, and Al having a ligand of a compound represented by 1 to 10 alkyl groups, R ⁵ represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. At least one metal chelate compound having a metal selected from

[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. As the hydrolyzable group, for example, an alkoxy group (preferably an alkoxy group having 1 to 5 carbon atoms, such as a methoxy group and an ethoxy group), a halogen atom (for example, Cl, Br, I and the like), and R ^{2 are used.} 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 groups (acetoxy groups, acryloyloxy groups, methacryloyloxy groups, etc.), alkoxycarbonyl groups (me Toxylcarbonyl group, ethoxycarbonyl group, etc.), aryloxycarbonyl group (phenoxycarbonyl group, etc.), carbamoyl group (carbamoyl group, N-methylcarbamoyl group, N, N-dimethylcarbamoyl group, N-methyl-N-octylcarbamoyl group) Etc.), acylamino groups (acetylamino group, benzoylamino group, acrylamino group, methacrylamino group, etc.) and the like, and these substituents may be further substituted. In the present specification, even if a hydrogen atom is replaced by a single atom, it is treated as a substituent for convenience.
When there are a plurality of R ¹⁰ , 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.
Formula (III)
_{^{(Rf-L 1) n -Si}} (R 11) 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 which 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. R ¹¹ represents a hydroxyl group or a hydrolyzable group, preferably an alkoxy group having 1 to 5 carbon atoms or a halogen atom, more preferably a methoxy group, an ethoxy group, or a chlorine atom. n represents an integer of 1 to 3.

Next, among the fluorine-containing silane coupling agents represented by the general formula (III), a fluorine-containing silane coupling agent represented by the following general formula (IV) is preferable.
Formula _{(IV) C n F 2n +} 1 - (CH 2) m -Si (R) 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 R is preferably a methoxy group, an ethoxy group, or a chlorine atom.

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

  Among these specific examples, (M-1), (M-2), (M-56), and (M-57) are particularly preferable. Further, the compounds of A, B and C described in Reference Example 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 the general formula (I) is not particularly limited, but is preferably 1% by mass to 300% by mass, more preferably 3% by mass to the inorganic oxide fine particles. 100% by mass, most preferably 5% by mass to 50% by mass. It is preferably 1 to 300 mol%, more preferably 5 to 300 mol%, and most preferably 10 to 200 mol% per normal concentration (Formol) based on hydroxyl groups 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 at the same time, or the reaction can be carried out by shifting the addition time. Also, it is preferable to add a plurality of kinds of compounds in the form of partial condensates in advance because the reaction control is easy.

In the present invention, the dispersibility of the inorganic oxide fine particles is improved by causing the hydrolyzate and / or partial condensate thereof to act on the surface of the inorganic oxide 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), and the acid catalyst used in the present invention. Or it is preferable to carry out by stirring at 15-100 degreeC in presence of a metal chelate compound.

[Solvent for dispersibility improvement treatment]
The dispersibility improving treatment with the hydrolyzate and / or condensation reaction product of organosilane can be carried out in the absence of a solvent or in a solvent. When a solvent is used, the concentration of the hydrolyzate of organosilane and / or the partial condensate thereof can be appropriately determined. As the solvent, an organic solvent is preferably used in order to uniformly mix the components. For example, alcohols, aromatic hydrocarbons, ethers, ketones, esters and the like are preferable.
The solvent is preferably one that dissolves the organosilane hydrolyzate and / or condensation reaction product and the catalyst. In addition, it is preferable in the process that an organic solvent is used as a coating solution or a part of the coating solution, and those that do not impair the solubility or dispersibility when mixed with other materials such as a fluorine-containing polymer are preferable.

  Among these, examples of the alcohols include monohydric alcohols and dihydric alcohols. Among these, monohydric alcohols are preferably saturated aliphatic alcohols having 1 to 8 carbon atoms. Specific examples of these alcohols include methanol, ethanol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol. Examples thereof include monobutyl ether and ethylene glycol monoethyl ether acetate.

Specific examples of aromatic hydrocarbons include benzene, toluene and xylene, specific examples of ethers include tetrahydrofuran and dioxane, and specific examples of ketones include acetone, methyl ethyl ketone, and methyl isobutyl ketone. Specific examples of esters such as diisobutylketone and the like include ethyl acetate, propyl acetate, butyl acetate, and propylene carbonate.
These organic solvents can be used alone or in combination of two or more. The concentration of the organosilane with respect to the solvent in the treatment is not particularly limited, but is usually in the range of 0.1% by mass to 70% by mass, and preferably in the range of 1% by mass to 50% by mass.
In the present invention, it is preferable to disperse the inorganic oxide fine particles with an alcohol solvent and then perform a dispersibility improvement treatment, and subsequently replace the dispersion solvent with an aromatic hydrocarbon solvent or a ketone solvent. Substitution with a ketone solvent is preferable from the viewpoint of improving the affinity with the binder used at the time of coating and the stability of the dispersion itself.

[Catalyst for improving dispersibility]
The treatment for improving the dispersibility by the hydrolyzate of organosilane and / or the condensation reaction product 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. For inorganic acids, hydrochloric acid and sulfuric acid, for organic acids, the acid dissociation constant in water (pKa value (25 ° C.)) is preferably 4.5 or less, and the acid dissociation constant in hydrochloric acid, sulfuric acid or water is 3.0 or less. More preferred is an organic acid having an acid dissociation constant of 2.5 or less in hydrochloric acid, sulfuric acid or water, more preferred is an organic acid having an acid dissociation constant of 2.5 or less in water, and methanesulfone. Acid, 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.

The amount of the acid catalyst used is 0.01 to 10 mol%, preferably 0.1 to 5 mol%, based on the hydrolyzable group when the acid catalyst is an inorganic acid, and the acid catalyst is an organic acid. However, when water is added, the optimal amount used is 0.01 to 10 mol%, preferably 0.1 to 5 mol%, based on the hydrolyzable group. When substantially no water is added, it is 1 to 500 mol%, preferably 10 to 200 mol%, more preferably 20 to 200 mol%, still more preferably 50 to 50 mol% with respect to the hydrolyzable group. 150 mol%, particularly preferably 50 to 120 mol%.
The dispersibility improving treatment is performed by stirring at 15 to 100 ° C., but it is preferably adjusted according to the reactivity of the organosilane.

[Metal chelate compounds]
The metal chelate compound is an alcohol represented by a general formula R ₃ OH (wherein R ₃ represents an alkyl group having 1 to 10 carbon atoms) and / or a general formula R ₄ COCH ₂ COR ₅ (where R 3 ₄ is an alkyl group having 1 to 10 carbon atoms, and R ₅ is an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.) As long as a metal selected from Ti or Al is used as a central metal, it can be suitably used without any particular limitation. Within this category, two or more metal chelate compounds may be used in combination. The metal chelate compound used in the present invention has the general formula Zr (OR ₃ ) p ₁ (R ₄ COCHCOR ₅ ) p ₂ ,
Ti (OR ₃ ) q ₁ (R ₄ COCHCOR ₅ ) q ₂ and Al (OR ₃ ) r ₁ (R ₄ COCHCOR ₅ ) r ₂
Are preferably selected from the group of compounds represented by the formula (1), which have the effect of promoting the condensation reaction of the organosilane compound.
R ₃ and R ₄ in the metal chelate compound may be the same or different, and an alkyl group having 1 to 10 carbon atoms, specifically, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, an n-pentyl group, a phenyl group, and the like. R ₅ represents an alkyl group having 1 to 10 carbon atoms as described above, or an alkoxy group having 1 to 10 carbon atoms such as a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, and n-butoxy. Group, sec-butoxy group, t-butoxy group and the like. _{Further, p 1, p 2, q} 1, q 2, r 1 and _{r 2} in the metal chelate compound is an integer which is determined to be 4 or 6-coordinated.

Specific examples of these metal chelate compounds include tri-n-butoxyethylacetoacetate zirconium, di-n-butoxybis (ethylacetoacetate) zirconium, n-butoxytris (ethylacetoacetate) zirconium, tetrakis (n-propylacetate). Zirconium chelate compounds such as acetate) zirconium, tetrakis (acetylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium; diisopropoxy bis (ethylacetoacetate) titanium, diisopropoxy bis (acetylacetate) titanium, diiso Titanium chelate compounds such as propoxy bis (acetylacetone) titanium; diisopropoxyethyl acetoacetate aluminum, diisopropoxy Cetylacetonate aluminum, isopropoxybis (ethylacetoacetate) aluminum, isopropoxybis (acetylacetonate) aluminum, tris (ethylacetoacetate) aluminum, tris (acetylacetonate) aluminum, monoacetylacetonate bis (ethylacetate) And aluminum chelate compounds such as acetate) aluminum.
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.

  The metal chelate compound used in the present invention is preferably from 0.01 to 50% by mass, more preferably from 0.1 to 50% by mass, based on the organosilane, from the viewpoint of the speed of the condensation reaction and the film strength when formed into a coating film. It is used in a proportion of 50% by mass, more preferably 0.5 to 10% by mass.

[Dispersion stabilization additive]
In addition to the organosilane, acid catalyst and / or chelate compound, the following component (c) is preferably added to the dispersion or coating composition used in the present invention.
The component (c) used in the present invention will be described below. The component (c) is a β-diketone compound and / or β-ketoester compound represented by the general formula R ₄ COCH ₂ COR ₅ , and serves as a stability improver for the dispersion or coating composition used in the present invention. It works. That is, by coordinating to the metal atom in the metal chelate compound (zirconium, titanium and / or aluminum compound), the action of promoting the condensation reaction of organosilane and metal chelate component by these metal chelate compounds is suppressed, It is considered that it acts to improve the storage stability of the resulting composition. R ₄ and R ₅ constituting the component (c) has the same meaning as R ₄ and R ₅ constituting the metal chelate compound.

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

[Inorganic oxide fine particles]
Next, inorganic oxide fine particles that can be used in the present invention will be described.
The inorganic oxide particles are at least one selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, germanium, indium, tin, antimony and cerium from the viewpoint of the colorlessness of the cured film of the resulting curable composition. Elemental oxide particles are preferred.

  As these inorganic oxide particles, for example, silica, alumina, zirconia, titanium oxide, zinc oxide, germanium oxide, indium oxide, tin oxide, indium tin oxide (ITO), antimony oxide, cerium oxide and the like are the main components. Can be mentioned. Of these, particles of silica, alumina, zirconia and antimony oxide are preferred from the viewpoint of high hardness. These may be used alone or in combination of two or more. In addition, when used in the low refractive index layer, it is particularly desirable to use particles mainly composed of silica. Furthermore, the inorganic oxide particles are preferably used as an organic solvent dispersion. When used as an organic solvent dispersion, the dispersion medium is preferably an organic solvent from the viewpoint of compatibility with other components and dispersibility. Examples of such an organic solvent include alcohols such as methanol, ethanol, isopropanol, butanol, and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethyl acetate, butyl acetate, ethyl lactate, and γ-butyrolactone. , Esters such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; ethers such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; aromatic hydrocarbons such as benzene, toluene and xylene; dimethylformamide, dimethylacetamide, Examples thereof include amides such as N-methylpyrrolidone. Of these, methanol, isopropanol, butanol, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, toluene, and xylene are preferable.

  The inorganic fine particles have a particle size of 1/2 or less of the film thickness. The number average particle diameter of the particles is preferably 1 nm to 100 nm, more preferably 3 nm to 80 nm, and particularly preferably 5 nm to 50 nm. When the number average particle size is large, the transparency when cured is lowered, or the surface state when coated is liable to deteriorate. If the number average particle size is small, the surface area becomes too large, causing the problem of particle aggregation, and the effect of improving the scratch resistance may be diminished. The inorganic fine particles may be either crystalline or amorphous, and may be monodispersed particles or aggregated particles as long as a predetermined particle size is satisfied. The shape is most preferably a spherical diameter, but there is no problem even if the shape is indefinite. Here, the average particle diameter of the inorganic fine particles is measured by a Coulter counter. Various surfactants and amines may be added to improve the dispersibility of the particles.

When the thin film layer of the optical film is a low refractive index layer of the antireflection film, it is preferable to use fine particles having micropores in the particles in order to reduce the refractive index, hollow fine particles are particularly preferable, It is particularly preferable to use silica fine particles. The hollow silica fine particles have a refractive index of 1.17 to 1.40, more preferably 1.17 to 1.35, and still more preferably 1.17 to 1.30. The refractive index here represents the refractive index of the entire particle, and does not represent the refractive index of only the outer shell silica forming the hollow silica particles. At this time, when the radius of the cavity in the particle is a and the radius of the particle outer shell is b, the porosity x (%) is calculated by the following formula (VIII).
(Formula VIII)
^{x = (4πa 3/3)} / (4πb 3/3) × 100 (%)
The porosity x is preferably 10 to 60%, more preferably 20 to 60%, and most preferably 30 to 60%. If hollow silica particles are made to have a lower refractive index and a higher porosity, the thickness of the outer shell becomes thinner and the strength of the particles becomes weaker. Rate particles are not preferred.
In addition, the refractive index of these hollow silica particles is measured by, for example, an Abbe refractometer (manufactured by Atago Co., Ltd.).

  Moreover, the refractive index of this layer can be reduced by containing hollow particles in the low refractive index layer. When the hollow particles are used, the refractive index of the layer is preferably 1.20 or more and 1.46 or less, more preferably 1.25 or more and 1.41 or less, and most preferably 1.30 or more and 1.39 or less. It is.

Although the example of the particle | grains which can be used is described below, the particle | grains which can be used are not restricted to this. From the following particles, particles having a particle size of 1/2 or less of the film thickness can be selected and used.
Examples of the silicon oxide particle dispersion (for example, silica particles) include colloidal silica, methanol silica sol manufactured by Nissan Chemical Industries, Ltd., MA-ST-MS, IPA-ST, IPA-ST-MS, IPA- ST-L, IPA-ST-ZL, IPA-ST-UP, EG-ST, NPC-ST-30, MEK-ST, MEK-ST-L, MIBK-ST, NBA-ST, XBA-ST, DMAC- ST, ST-UP, ST-OUP, ST-20, ST-40, ST-C, ST-N, ST-O, ST-50, ST-OL, etc., hollow silica CS60- manufactured by Catalyst Kasei Kogyo Co., Ltd. Examples include IPA. As the powdered silica, Aerosil 130, Aerosil 300, Aerosil 380, Aerosil TT600, Aerosil OX50, Silex H31, H32, H51, H52, H121, H122, Asahi Glass Co., Ltd., Nippon Silica Industry, Nippon Aerosil Co., Ltd. Examples include E220A and E220 manufactured by Fuji Electric, SYLYSIA470 manufactured by Fuji Silysia Co., Ltd., SG flake manufactured by Nippon Sheet Glass Co., Ltd., and the like.

  In addition, as alumina water dispersion, alumina sol-100, -200, -520 manufactured by Nissan Chemical Industries, Ltd .; as isopropanol dispersion of alumina, AS-150I manufactured by Sumitomo Osaka Cement Co., Ltd .; toluene dispersion of alumina AS-150T manufactured by Sumitomo Osaka Cement Co., Ltd .; HXU-110JC manufactured by Sumitomo Osaka Cement Co., Ltd. as a toluene dispersion of zirconia; Nissan Chemical Industries, Ltd. as an aqueous dispersion of zinc antimonate powder ) Celnax; Alumina, Titanium oxide, Tin oxide, Indium oxide, Zinc oxide, etc. Powder and solvent dispersion products are nanotech made by CI Kasei Co., Ltd .; Antimony-doped tin oxide water dispersion sol is Ishihara Sangyo ( SN-100D, manufactured by Mitsubishi Materials Corporation, as ITO powder; cerium oxide aqueous dispersion As such, there may be mentioned Nidral manufactured by Taki Chemical Co., Ltd.

The oxide particles have a spherical shape, a hollow shape, a porous shape, a rod shape, a plate shape, a fiber shape, or an indefinite shape, preferably a spherical shape or a hollow shape. The hollow silica particles will be described later. The specific surface area of the oxide particles (by the BET specific surface area measurement method using nitrogen) is preferably 10 to 1000 m ² / g, and more preferably 100 to 500 m ² / g. These inorganic oxide particles can be obtained by dispersing powder in a dry state in an organic solvent. For example, a dispersion of fine oxide particles known in the art as a solvent dispersion sol of the above oxide is directly used. Can be used.

[Distribution method]
In the present invention, a dispersant may be used to prepare the inorganic oxide 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 the dispersibility. The average number is preferably 2 or more, more preferably 5 or more, and particularly preferably 10 or more. Moreover, the anionic group contained in a dispersing agent may contain multiple types in 1 molecule.
The dispersant may further contain a crosslinking or polymerizable functional group. Examples of the crosslinkable or polymerizable functional group include ethylenically unsaturated groups (for example, (meth) acryloyl group, allyl group, styryl group, vinyloxy group, etc.) capable of addition reaction / polymerization reaction by radical species, cationic polymerizable group (epoxy) 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.
In the present invention, a disperser can be used to grind inorganic oxide particles. 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.

[Solvent of coating solution]
The organic solvent dispersion of inorganic oxide fine particles according to the present invention described above is used as a fine particle component and combined with a binder to form a coating composition, and each layer of the optical film can be formed from this composition. Although there is no restriction | limiting in the solvent of a coating composition, It is preferable to contain at least 2 type of volatile solvent. For example, it is preferable to use a combination of at least two selected from alcohol and derivatives thereof, ethers, ketones, hydrocarbons, and esters. A solvent can be selected from the viewpoint of the solubility of the binder component, the stability of the inorganic fine particles, and the adjustment of the viscosity of the coating liquid. By using a combination of two or more solvents, the fine particles can be arranged in the film while being controlled so as to have the R ¹ value or R ² value defined in the present invention. The boiling point of the solvent used in the present invention is preferably 50 ° C. or higher and 250 ° C. or lower, more preferably 65 ° C. or higher and 200 ° C. or lower. Further, the preferable dielectric constant is preferably 1 or more and 50 or less, more preferably 5 or more and 30 or less at 20 ° C. It is preferable in terms of dispersion stability that a solvent having a dielectric constant of 10 or more is contained in an amount of 10% by mass or more based on the inorganic fine particles.

Although the solvent which can be used for this invention below is mentioned, it is not limited to these.
・ Alcohol and its derivatives (methanol, ethanol, n-propanol, isopropyl alcohol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-amyl alcohol, isoamyl alcohol, sec amyl alcohol, 3-pentanol , Tertiary amyl alcohol, n-hexanol, methyl amyl alcohol, 2-ethylbutanol, n-heptanol, 2-heptanol, 3-heptanol, n-octanol, 2-octanol, 2-ethylhexanol, 3,5,5- Trimethylhexanol, nonanol, benzyl alcohol, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether, ethylene glycol diethyl ether Ter, ethylene glycol monoethyl ether acetate, ethylene glycol isopropyl ether, ethylene glycol monobutyl ether, ethylene glycol dibutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol isoamyl ether, methoxymethoxyethanol, methoxypropanol, butoxyethanol, ethylene glycol monoacetate, Ethylene glycol diacetate, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether Le, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether)

-Ethers (isopropyl ether, n-butyl ether, diisoamyl ether, methylphenyl ether, ethylphenyl ether)-Ketones (acetone, methylacetone, methylethylketone, methyl-n-propylketone, methyl-n-butyl, methylisobutylketone) , Methyl-n-amyl ketone, methyl-n-hexyl ketone, diethyl ketone, ethyl-n-butyl ketone, di-n-propyl ketone, diisobutyl ketone, acetonyl acetone, diacetone alcohol, cyclohexanone, methylcyclohexanone)

・ Hydrocarbons (n-hexane, isohexane, n-heptane, n-octane, isooctane, n-decane, toluene, xylene, ethylbenzene, diethylbenzene, isopropylbenzene, amylbenzene)
Esters (propyl formate, n-butyl formate, isobutyl formate, amyl formate, ethyl acetate, acetic acid n-propyl, isopropyl acetate, acetic acid n-butyl, isobutyl acetate, sec-butyl acetate, acetic acid n-amyl , Isoamyl acetate, methyl isoamyl acetate, methoxybutyl acetate, sec-hexyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, cyclohexyl acetate, methyl cyclohexyl acetate, benzyl acetate, methyl propionate, ethyl propionate , N-butyl propionate, isoamyl propionate, methyl butyrate, ethyl butyrate, n-butyl butyrate, isoamyl butyrate, ethyl oxyisobutyrate, methyl acetoacetate, ethyl acetoacetate, isoamyl isovalerate, methyl lactate, ethyl lactate, Lactic acid-n-butyl, lactyl isobutyl, lactate-n-amyl, lactate isoa Le, methyl benzoate, diethyl oxalate)

  A particularly preferred combination is the use of at least two, more preferably three, of alcohol and its derivatives, ketones and esters. As a preferred example, for example, two or three of methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 2-methoxypropanol, 2-butoxyethanol, isopropyl alcohol, and toluene can be used in combination.

  In the present invention, in order to dispose the inorganic fine particles in the layer while controlling the dispersion state and the like, the binder is at least one polymerizable composition having a weight average molecular weight of 5000 or more and at least one polymerization having a weight average molecular weight of less than 5000. It is preferable that it is comprised from an ionic compound. Specific examples of the composition having a weight average molecular weight exceeding 5000 are preferably a copolymer having a (meth) acryloyl group in the side chain and a high molecular weight compound containing a fluorocarbon or dimethylsiloxane. Moreover, as a compound with a weight average molecular weight of less than 5000, the polyfunctional acrylate monomer, the partial condensate of the compound of general formula (II) which has a (meth) acryloyl group, etc. are preferable. Detailed compounds are described in the section of film forming binder and low refractive index material.

[Layer structure of optical film]
The optical film of the present invention has a layer having a hard coat property, which will be described later, on a transparent substrate, if necessary, and a refractive index, a film thickness, and a layer so that the reflectance is reduced by optical interference. Are stacked in consideration of the number of layers, the order of layers, and the like. The simplest configuration of the low reflection laminate is 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 composed of a combination of a high refractive index layer having a higher refractive index than the substrate and a low refractive index layer having a lower refractive index than the substrate. 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 lower refractive index than a high refractive index layer) / a high refractive index layer / a low refractive index layer, and the like. Among them, it is preferable to apply the medium refractive index layer / high refractive index layer / low refractive index layer in this order on a substrate having a layer having a hard coat property in view of durability, optical characteristics, cost, productivity, and the like.

Examples of preferred layer configurations of the low reflection laminate of the present invention are shown below. In the following configuration, the base film refers to a support composed of a film.
・ 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 / Anti-static layer / Anti-glare 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 antiglare layer may be a light scattering layer, or may be a layer having both antiglare properties and light scattering properties. Further, the hard coat layer and the antiglare layer can be made to have a high refractive index by dispersing fine particles having a high refractive index as required.
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.

[Film-forming binder]
In the present invention, it is preferable to use a compound having an ethylenically unsaturated group as a main film-forming binder component of the film-forming composition in terms of film strength, coating solution stability, and coating film productivity. The main film-forming binder refers to one that accounts for 10% by mass or more of the film-forming components excluding inorganic particles. Preferably, they are 20 mass% or more and 100 mass% or less, More preferably, they are 30 mass% or more and 95% or less.
A polymer having a saturated hydrocarbon chain or a polyether chain as a main chain is preferable, and a polymer having a saturated hydrocarbon chain as a main chain is more 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 a halogen atom other than fluorine, a sulfur atom, a phosphorus atom, and a nitrogen atom.

  Monomers having two or more ethylenically unsaturated groups include esters of polyhydric alcohols 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, pentaerythritol hexa (meth) acrylate, 1,2,3-cyclohexanetetramethacrylate, polyurethane polyacrylate, polyester poly Acrylate), vinylbenzene and its derivatives (eg, 1,4-divinylbenzene, 4-vinylbenzoic acid-2-acryloylethyl ester, 1,4-divinylcyclohexanone), vinylsulfone (eg, divinylsulfone), acrylamide (eg, , Methylenebisacrylamide) and methacrylamide. Two or more of these monomers may be used in combination. In the present specification, “(meth) acrylate” represents “acrylate or methacrylate”.

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

  Polymerization of the monomer having an ethylenically unsaturated group can be performed by irradiation with ionizing radiation or heating in the presence of a photo radical initiator or a thermal radical initiator.

As photo radical polymerization initiators, acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkyldione compounds, disulfide compounds , Fluoroamine compounds and aromatic sulfoniums. Examples of acetophenones include 2,2-diethoxyacetophenone, p-dimethylacetophenone, 1-hydroxydimethylphenylketone, 1-hydroxycyclohexylphenylketone, 2-methyl-4-methylthio-2-morpholinopropiophenone and 2 -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone is included. Examples of benzoins include benzoin benzene sulfonate, benzoin toluene sulfonate, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether. Examples of benzophenones include benzophenone, 2,4-dichlorobenzophenone, 4,4-dichlorobenzophenone and p-chlorobenzophenone. Examples of phosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
Further, various examples are described on page 159 of the latest UV curing technology (issuer: Kazuhiro Takasagi, publisher; Technical Information Association, Inc., published in 1991), which is useful for the present invention.
Preferable examples of commercially available photocleavable photoradical polymerization initiators include Irgacure (651, 184, 907) manufactured by Ciba Specialty Chemicals.
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.

  In the present invention, a polymer having a polyether as a main chain can also be used. Such a polymer is preferably a ring-opening polymer of a polyfunctional epoxy compound. The ring-opening polymerization of the polyfunctional epoxy compound can be performed by irradiation with ionizing radiation or heating in the presence of a photoacid generator or a thermal acid generator.

Further, in place of or in addition to the 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 the reaction of the crosslinkable functional group is performed. Thus, 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.

[Material for low refractive index layer]
The low refractive index layer of the present invention preferably contains a fluorine-containing polymer as a low refractive index binder. The fluoropolymer is preferably a fluoropolymer that is crosslinked by heat or ionizing radiation having a coefficient of dynamic friction of 0.03 to 0.15 and a contact angle with water of 90 to 120 °. As described above, an inorganic filler for improving the film strength can be used in the low refractive index layer of the present invention.

Examples of the fluorine-containing polymer preferably used for the low refractive index layer include hydrolysis and dehydration condensation products of fluoroalkyl group-containing silane compounds (for example, (heptadecafluoro-1,1,2,2-tetrahydrodecyl) triethoxysilane). In addition, a fluorine-containing copolymer having a fluorine-containing monomer unit and a structural unit for imparting crosslinking reactivity as constituent components can be mentioned.
As the fluoroalkyl group-containing silane compound that can be used for the former, CF ₃ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ , CF ₃ CF ₂ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₂ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₄ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₆ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₈ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₉ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ , CF ₃ (CH _{2) 2 Si (OC 2 H} 5) 3, CF 3 CF 2 (CH 2) 2 Si (OC 2 H 5) 3, CF 3 (CF 2) 2 (CH 2) 2 S i (OC ₂ H ₅ ) ₃ , CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₂ Si (OC ₂ H ₅ ) ₃ , CF ₃ (CF ₂ ) ₄ (CH ₂ ) ₂ Si (OC ₂ H ₅ ) ₃ CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OC ₂ H ₅ ) ₃ , CF ₃ (CF ₂ ) ₆ (CH ₂ ) ₂ Si (OC ₂ H ₅ ) ₃ , CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OC ₂ H ₅ ) ₃ , CF ₃ (CF ₂ ) _{8 (} CH ₂ ) ₂ Si (OC ₂ H ₅ ) ₃ , CF ₃ (CF ₂ ) ₉ (CH ₂ ) ₂ Si (OC ₂ H ₅ ) _{3 and the} like, especially CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OC ₂ H ₅ ) ₃ Can be preferably used.

  Specific examples of the fluorinated monomer unit for constituting the fluorinated copolymer having the fluorinated monomer unit and a structural unit for imparting crosslinking reactivity as constituents include, for example, fluoroolefins (for example, fluoroethylene, vinylidene fluoride). , Tetrafluoroethylene, perfluorooctylethylene, hexafluoropropylene, perfluoro-2,2-dimethyl-1,3-dioxole, etc.), (meth) acrylic acid partial or fully fluorinated alkyl ester derivatives (for example, biscoat) 6FM (manufactured by Osaka Organic Chemical Co., Ltd., M-2020 (manufactured by Daikin), etc.), fully or partially fluorinated vinyl ethers, and the like. Preferred are perfluoroolefins, refractive index, solubility, transparency, and availability. From the viewpoint of properties and the like, hexafluoropro is particularly preferred. Is Ren.

  As structural units for imparting crosslinking reactivity, structural units obtained by polymerization of monomers having a self-crosslinkable functional group in advance in the molecule such as glycidyl (meth) acrylate and glycidyl vinyl ether, carboxyl groups, hydroxy groups, amino groups , Obtained by polymerization of a monomer having a sulfo group or the like (for example, (meth) acrylic acid, methylol (meth) acrylate, hydroxyalkyl (meth) acrylate, allyl acrylate, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, maleic acid, crotonic acid, etc.) And a structural unit obtained by introducing a crosslinking reactive group such as a (meth) acryloyl group into these structural units by a polymer reaction (for example, it can be introduced by a technique such as allowing acrylic acid chloride to act on a hydroxy group) And the like.

  In addition to the above-mentioned fluorine-containing monomer units and structural units for imparting crosslinking reactivity, monomers not containing fluorine atoms can be copolymerized as appropriate from the viewpoints of solubility in solvents and film transparency. There are no particular limitations on the monomer units that can be used in combination. For example, olefins (ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride, etc.), acrylic esters (methyl acrylate, methyl acrylate, ethyl acrylate, acrylic acid 2) -Ethylhexyl), methacrylates (methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate, etc.), styrene derivatives (styrene, divinylbenzene, vinyltoluene, α-methylstyrene, etc.), vinyl ethers (methyl) Vinyl ether, ethyl vinyl ether, cyclohexyl vinyl ether, etc.), vinyl esters (vinyl acetate, vinyl propionate, vinyl cinnamate etc.), acrylamides (N-tertbutylacrylamide, N-silane) B hexyl acrylamide), methacrylamides, and acrylonitrile derivatives.

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

  The low refractive index layer is preferably formed by a cured film of a copolymer having a repeating unit derived from a fluorine-containing vinyl monomer and a repeating unit having a (meth) acryloyl group in the side chain as essential constituent components. The copolymer-derived component preferably occupies 60% by mass or more, more preferably 70% by mass or more, and particularly preferably 80% by mass or more. From the viewpoint of achieving both low refractive index and film hardness, a curing agent such as polyfunctional (meth) acrylate is also preferably used in an addition amount within a range that does not impair the compatibility.

The refractive index of the low refractive index layer is preferably 1.20 to 1.46, more preferably 1.25 to 1.46, and particularly preferably 1.30 to 1.46. More preferably, it is 1.30-1.40.
The thickness of the low refractive index layer is preferably 50 to 200 nm, more preferably 50 to 150 nm, and further 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.
In order to improve the antifouling performance of the optical film, it is preferable that the contact angle of the surface with respect to water is 90 degrees or more. More preferably, it is 95 degrees or more, and particularly preferably 100 degrees or more.

The copolymer preferably used for the low refractive index layer of the present invention will be described below.
Fluorinated vinyl monomers include fluoroolefins (for example, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, etc.), (meth) acrylic acid moieties or fully fluorinated alkyl ester derivatives (for example, Biscoat 6FM (trade name) , Osaka Organic Chemical Co., Ltd.) and R-2020 (trade name, manufactured by Daikin Co., Ltd.), fully or partially fluorinated vinyl ethers, and the like. Preferred are perfluoroolefins, refractive index, solubility, and transparency. From the viewpoint of availability, hexafluoropropylene is particularly preferable. Increasing the composition ratio of these fluorine-containing vinyl monomers can lower the refractive index but lowers the film strength. In the present invention, it is preferable to introduce the fluorine-containing vinyl monomer so that the fluorine content of the copolymer is 20 to 60% by mass, more preferably 25 to 55% by mass, and particularly preferably 30 to 50% by mass. This is a case of mass%.

  The copolymer of the present invention preferably has a repeating unit having a (meth) acryloyl group in the side chain as an essential component. If the composition ratio of these (meth) acryloyl group-containing repeating units is increased, the film strength is improved, but the refractive index is also increased. Generally, the (meth) acryloyl group-containing repeating unit preferably accounts for 5 to 90% by mass, more preferably 30 to 70% by mass, although it varies depending on the type of repeating unit derived from the fluorine-containing vinyl monomer. It is particularly preferred to account for ~ 60% by weight.

  In the copolymer useful for the present invention, in addition to the repeating unit derived from the above-mentioned fluorine-containing vinyl monomer and the repeating unit having a (meth) acryloyl group in the side chain, it contributes to adhesion to the substrate and Tg of the polymer (film hardness). And other vinyl monomers can be copolymerized as appropriate from various viewpoints such as solubility in a solvent, transparency, slipperiness, dust resistance and antifouling properties. A plurality of these vinyl monomers may be combined depending on the purpose, and are preferably introduced in the range of 0 to 65 mol% in the copolymer in total, and in the range of 0 to 40 mol%. More preferably, it is particularly preferably in the range of 0 to 30 mol%.

  The vinyl monomer unit that can be used in combination is not particularly limited. For example, olefins (ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride, etc.), acrylic esters (methyl acrylate, methyl acrylate, ethyl acrylate, acrylic acid) 2-ethylhexyl, 2-hydroxyethyl acrylate), methacrylic acid esters (methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-hydroxyethyl methacrylate, etc.), styrene derivatives (styrene, p-hydroxymethylstyrene, p -Methoxystyrene, etc.), vinyl ethers (methyl vinyl ether, ethyl vinyl ether, cyclohexyl vinyl ether, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, etc.), vinyl esters (vinyl acetate, pro Vinyl pionate, vinyl cinnamate, etc.), unsaturated carboxylic acids (acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, etc.), acrylamides (N, N-dimethylacrylamide, N-tert-butylacrylamide, N -Cyclohexyl acrylamide), methacrylamides (N, N-dimethylmethacrylamide), acrylonitrile and the like.

  In the present invention, it is preferable to add a hydrolyzate of organosilane and / or a partial condensate thereof from the viewpoint of improving the film strength. For the synthesis of the partial condensate (abbreviated as sol) of the organosilane compound, the acid catalyst or metal chelate compound used in the treatment for improving the dispersibility of the inorganic oxide fine particles of the present invention can be used. The preferable addition amount of sol is preferably 2 to 200% by mass of the inorganic oxide particles, more preferably 5 to 100% by mass, and most preferably 10 to 50% by mass.

In the present invention, it is preferable to reduce the surface free energy on the surface of the antireflection film from the viewpoint of improving the antifouling property. Specifically, it is preferable to use a fluorine-containing compound or a compound having a polysiloxane structure for the low refractive index layer, and it is particularly preferable to use a compound having a polysiloxane structure. A compound containing a portion having a polysiloxane structure in the main binder molecule may be used, or a compound having a polysiloxane structure may be used as an additive separately from the main binder. In the case of the low refractive index layer, it is particularly preferable to use a fluorine compound having a polysiloxane structure in the molecule as the main binder.
Examples of the additive having a polysiloxane structure include reactive group-containing polysiloxanes (for example, KF-100T, X-22-169AS, KF-102, X-22-3701IE, X-22-164B, X-22-5002, X-22-173B, X-22-174D, X-22-167B, X-22-161AS (above trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), AK-5, AK-30, AK-32 (above trade name) Toray Gosei Co., Ltd.), Silaplane FM0725, Silaplane FM0721 (above, trade name, manufactured by Chisso Corporation), etc.) are also preferably added. Moreover, the silicone type compound of Table 2 and Table 3 of Unexamined-Japanese-Patent No. 2003-112383 can also be used preferably. These polysiloxanes are preferably added in the range of 0.1 to 10% by mass of the total solid content of the low refractive index layer, particularly preferably 1 to 5% by mass.

[Layer with hard coat properties]
In the present invention, a layer having hard coat properties is preferably provided. The layer having hard coat properties may contain a binder, an antiglare property, and mat particles for imparting light scattering properties. In addition, an inorganic filler for increasing the refractive index, preventing crosslinking shrinkage, and increasing the strength can also be contained.

For the layer having hard coat properties, for the purpose of imparting antiglare property and light scattering property, mat particles having a larger average particle size of 0.1 to 5.0 μm, preferably 1.5 to 3.5 μm, than filler particles. For example, particles of inorganic compounds or resin particles can be contained. If the refractive index difference between the matte particles and the binder is too large, the film becomes cloudy, and if it is too small, a sufficient light diffusing effect cannot be obtained, so 0.02 to 0.25 is preferable. Particularly preferred is 0.20. If the addition amount of the mat particles to the binder is too large, the film becomes cloudy if it is too large, and if it is too small, a sufficient light diffusion effect cannot be obtained. A percentage is particularly preferred.
Specific examples of the mat particles include, for example, inorganic compound particles mainly composed of silica particles, TiO ₂ particles, etc .; acrylic particles, crosslinked acrylic particles, polystyrene particles, crosslinked styrene particles, melamine resin particles, benzoguanamine resin particles, and the like. The resin particle which has as a main component is mentioned preferably. Of these, crosslinked styrene particles, crosslinked acrylic particles, crosslinked acrylic styrene particles, and silica particles are preferable. By changing the component ratio of acrylic and styrene in the crosslinked acrylic styrene particles, the difference in refractive index from the binder can be controlled to obtain preferable scattering properties.
The shape of the mat particles can be either a true sphere or an indefinite shape.

  Two or more different kinds of mat particles may be used in combination. When two or more kinds of mat particles are used, the difference in refractive index is preferably 0.02 or more and 0.20 or less, and particularly preferably 0.03 or more and 0.20 or less. Further, it is possible to impart an antiglare property with mat particles having a larger particle size and to impart another optical characteristic with mat particles having a smaller particle size. For example, when an optical film is attached to a high-definition display of 133 ppi or more, it is required that there is no problem in optical performance called glare. Glare originates from the fact that the pixels are enlarged or reduced due to unevenness existing on the film surface (contributing to anti-glare properties) and lose uniformity of brightness, but with a particle size smaller than that of mat particles that provide anti-glare properties. It can be greatly improved by using mat particles having a different refractive index from the binder. Of course, the two effects can be imparted by one kind of particle.

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

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

In order to increase the refractive index of the layer and to reduce curing shrinkage, the layer having hard coat properties includes titanium, zirconium, aluminum, indium, zinc, tin, and antimony in addition to the above mat particles. It is preferable to contain an inorganic filler composed of an oxide of at least one selected metal and having an average particle size of 0.2 μm or less, preferably 0.1 μm or less, more preferably 0.06 μm or less.
In order to increase the difference in refractive index from the mat particles, it is also preferable to use a silicon oxide in order to keep the refractive index of the hard coat layer using the high refractive index mat particles low. The preferred particle size is the same as that of the aforementioned inorganic filler.
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 , ITO and SiO ₂ . TiO ₂ and ZrO ₂ are particularly preferable in terms of increasing the refractive index. The surface of the inorganic filler is preferably subjected to a silane coupling treatment or a titanium coupling treatment, and a surface treatment agent having a functional group capable of reacting with a binder species on the filler surface is preferably used.
The amount of these inorganic fillers added is preferably 10 to 90% of the total mass of the hard coat layer, more preferably 20 to 80%, and particularly preferably 30 to 70%.
In addition, since such a filler has a particle size sufficiently smaller than the wavelength of light, scattering does not occur, and a dispersion in which the filler is dispersed in a binder polymer behaves as an optically uniform substance.

  The bulk refractive index of the mixture of binder and inorganic filler in the hard coat layer of the present invention is preferably 1.48 to 2.00, more preferably 1.50 to 1.80. In order to make the refractive index within 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 optical film of the present invention thus formed has a haze value of 3 to 70%, preferably 4 to 60%, and an average reflectance of 450 nm to 650 nm is 3.0% or less, preferably 2.5% or less.
When the optical film of the present invention has a haze value and an average reflectance in the above ranges, good antiglare properties and antireflection properties can be obtained without causing deterioration of the transmitted image.

[Support]
As the transparent support of the optical film of the present invention, it is preferable to use a plastic film. Examples of the polymer forming the plastic film include cellulose esters (eg, triacetyl cellulose, diacetyl cellulose, typically TAC-TD80U, TD80UF, etc. manufactured by Fuji Photo Film), polyamides, polycarbonates, polyesters (eg, polyethylene terephthalate, polyethylene). Naphthalate), polystyrene, polyolefin, norbornene-based resin (Arton: trade name, manufactured by JSR Corporation), amorphous polyolefin (ZEONEX: trade name, manufactured by Nippon Zeon Corporation), and the like. Of these, triacetyl cellulose, polyethylene terephthalate, and polyethylene naphthalate are preferable, and triacetyl cellulose is particularly preferable. Also, the cellulose acylate film substantially free of halogenated hydrocarbons such as dichloromethane and the production method thereof are disclosed in JIII Journal of Technical Disclosure (Publication No. 2001-1745, published on March 15, 2001; The cellulose acylate described here can also be preferably used in the present invention.

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

When the optical film of the present invention is disposed on the outermost surface of a display by providing an adhesive layer on one side or used as it is as a protective film for a polarizing plate, it is contained on a transparent support for sufficient adhesion. It is preferable to carry out a saponification treatment after forming the outermost layer mainly composed of a fluoropolymer. The saponification treatment is performed by a known method, for example, by immersing the film in an alkali solution for an appropriate time. After being immersed in the alkaline solution, it is preferable to sufficiently wash with water or neutralize the alkaline component by dipping in a dilute acid so that the alkaline component does not remain in the film.
By saponification treatment, the surface of the transparent support opposite to the side having the outermost layer is hydrophilized.
The hydrophilized surface is particularly effective for improving the adhesion with a deflection film containing polyvinyl alcohol as a main component. In addition, the hydrophilic surface makes it difficult for dust in the air to adhere to it, making it difficult for dust to enter between the deflection film and the optical film when bonded to the deflection film, and is effective in preventing point defects due to dust. It is.
The saponification treatment is preferably carried out so that the contact angle of water on the surface of the transparent support opposite to the side having the outermost layer is 40 ° or less. More preferably, it is 30 ° or less, particularly preferably 20 ° or less.

Specific means for the alkali saponification treatment can be selected from the following two means (1) and (2). (1) is superior in that it can be processed in the same process as a general-purpose triacetylcellulose film, but since the surface of the antireflection film is saponified, the surface is alkali-hydrolyzed and the film deteriorates. The point that it becomes dirty when the liquid remains can be a problem. In that case, although it becomes a special process, (2) is excellent.
(1) After the antireflection layer is formed on the transparent support, the back surface of the film is saponified by immersing it in an alkaline solution at least once.
(2) Before or after the formation of the antireflection layer on the transparent support, the alkaline liquid is applied to the surface of the optical film opposite to the surface on which the optical film is formed, and is heated, washed and / or neutralized. Thus, only the back surface of the film is saponified.

[Coating method]
The optical film of the present invention can be formed by the following method, but is not limited to this method.
First, a coating solution containing components for forming each layer is prepared. The coating solution is applied onto a transparent support by dip coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating or extrusion coating (see US Pat. No. 2,681,294). Heat and dry.
Of these coating methods, coating by gravure coating is preferable because a coating solution with a small coating amount such as each layer of the antireflection film can be applied with high film thickness uniformity. Among the gravure coating methods, the micro gravure method has a high film thickness uniformity and is more preferable.
In addition, a coating solution with a small coating amount can be applied with high film thickness uniformity even by using a die coating method. Further, since the die coating method is a pre-measuring method, film thickness control is relatively easy, and the solvent in the coating part Is preferred because of less transpiration. Two or more layers may be applied simultaneously. The method of simultaneous application is described in US Pat. Nos. 2,761,791, 2,941,898, 3,508,947, and 3,526,528 and Yuji Harasaki, Coating Engineering, page 253, Asakura Shoten (1973).

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

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

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

  When the optical film of the present invention is used as one side of a surface protective film of a polarizing film, twisted nematic (TN), super twisted nematic (STN), vertical alignment (VA), in-plane switching (IPS), optically It can be preferably used for a transmissive, reflective, or transflective liquid crystal display device in a mode such as a compensated 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. 2). 176625) (2) Liquid crystal cell (SID97, Digest of tech. Papers (Preliminary Collection) 28 (1997) 845 in which the VA mode is converted into a multi-domain (MVA mode) for viewing angle expansion ), (3) 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 Japanese Liquid Crystal Society) (1998)) and (4) SURVAIVAL mode liquid crystal cells (announced at LCD International 98).
For a VA mode liquid crystal cell, a polarizing plate prepared by combining a biacetyl-stretched triacetyl cellulose film with the optical film of the present invention is preferably used. As for a method for producing a biaxially stretched triacetyl cellulose film, for example, the methods described in JP-A Nos. 2001-249223 and 2003-170492 are preferably used.

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

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

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

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

A multilayer antireflection film shown below was prepared.
(Preparation of coating solution for hard coat layer)
The following composition was put into a mixing tank and stirred to obtain a hard coat layer coating solution.
750.0 parts by mass of trimethylolpropane triacrylate (TMPTA, Nippon Kayaku Co., Ltd.), 270.0 parts by mass of poly (glycidyl methacrylate) having a weight average molecular weight of 15000, 730.0 parts by mass of methyl ethyl ketone, 500.0 cyclohexanone 50.0 parts by mass and 50.0 parts by mass of a photopolymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) and 25.0 parts by mass of di (t-butylphenyl) iodonium hexafluorophosphate are added and stirred. did. The solution was filtered through a polypropylene filter having 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 surface-treated with 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 (Chemical Formula 11) 41.1 parts by mass and cyclohexanone 701.8 parts by mass were added to 257.1 parts by mass of these particles and dispersed by dynomill to prepare a titanium dioxide dispersion having a mass average diameter of 70 nm. .

(Preparation of coating solution 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), 3.6 parts by mass of a photopolymerization initiator (Irgacure 907), light A sensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.) 1.2 parts by mass, methyl ethyl ketone 279.6 parts by mass and cyclohexanone 1049.0 parts by mass were added and stirred. After sufficiently stirring, the solution was filtered through a polypropylene filter having a pore diameter of 0.4 μm to prepare a coating solution for a medium refractive index layer.

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

(Preparation of coating solution A for low refractive index layer)
69 parts by mass of a fluorine-containing copolymer (P-3) described in JP-A No. 2004-45462 and 4 parts by mass of a terminal methacrylate group-containing silicone RMS-033 (manufactured by Gelest Co., Ltd.) with respect to 200 parts by mass of methyl ethyl ketone , Photoradical generator Irgacure 907 (manufactured by Ciba Specialty Chemicals), 3 parts by mass of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, Nippon Kayaku Co., Ltd., average molecular weight of about 560) ) 24 parts by mass was added and dissolved. A coating solution A was prepared by diluting with cyclohexanone and methyl ethyl ketone so that the solid content concentration of the entire coating solution was 6 mass% and the ratio of cyclohexane and methyl ethyl ketone was 6:94.

(Preparation of antireflection film 101)
The hard coat layer coating solution was applied on a triacetyl cellulose film (TD80UF, manufactured by Fuji Photo Film Co., Ltd.) having a thickness of 80 μm using a gravure coater. After drying at 100 ° C., using a 160 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) while purging with nitrogen so that the atmosphere has an oxygen concentration of 1.0 vol% or less, an irradiance of 400 mW / The coating layer was cured by irradiating with ultraviolet rays of cm ² and an irradiation amount of 300 mJ / cm ² to form a hard coat layer having a thickness of 8 μm.
On the hard coat layer, a medium refractive index layer coating solution, a high refractive index layer coating solution, and a low refractive index layer coating solution A were successively applied using a gravure coater having three coating stations.

The drying condition of the medium refractive index layer is 90 ° C. for 30 seconds, and the ultraviolet curing condition is a 180 W / cm air-cooled metal halide lamp (I Graphics The amount of irradiation was 400 mW / cm ² and the irradiation amount was 400 mJ / cm ² .
The medium refractive index layer after curing had a refractive index of 1.630 and a film thickness of 67 nm.

The drying condition of the high refractive index layer is 90 ° C. for 30 seconds, and the ultraviolet curing condition is a 240 W / cm air-cooled metal halide lamp (eye graphics) while purging with nitrogen so that the atmosphere has an oxygen concentration of 1.0 volume% or less. The irradiance was 600 mW / cm ² and the irradiation amount was 400 mJ / cm ² .
The high refractive index layer after curing had a refractive index of 1.91 and a film thickness of 107 nm.

The low refractive index layer is dried at 90 ° C. for 15 seconds, and the ultraviolet curing condition is 240 W / cm air-cooled metal halide lamp (eye graphics) while purging with nitrogen so that the oxygen concentration is 0.03% by volume or less. The irradiance was 600 mW / cm ² and the irradiation amount was 600 mJ / cm ² .
The low refractive index layer after curing had a refractive index of 1.50 and a film thickness of 85 nm.

(Preparation of antireflection film 102)
The antireflection film 101 was the same as the antireflection film 101 except that the fluorine-containing copolymer (P-3) of the coating solution A for low refractive index layer was 91 parts by mass and DPHA was 2 parts by mass. 102 was produced. The low refractive index layer after curing had a refractive index of 1.45.

(Preparation of antireflection film 103)
A sample 103 in which the low refractive index layer in the sample 101 was changed as follows was prepared.
(Preparation of sol solution a)
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 (Kelope EP-12 ( (Product name) and 3 parts of Hope Pharmaceutical Co., Ltd.) were added and mixed, 30 parts of ion-exchanged water was added, and the mixture was reacted at 60 ° C. for 4 hours, and then cooled to room temperature to obtain sol solution a. The mass average molecular weight was 1600, and among the components higher than the oligomer component, the component having a molecular weight of 1000 to 20000 was 100%. Further, from the gas chromatography analysis, the raw material acryloyloxypropyltrimethoxysilane did not remain at all.

(Preparation of dispersion A-1)
Hollow silica fine particle sol (Isopropyl alcohol silica sol, manufactured by Catalyst Chemical Industry Co., Ltd., average particle diameter 60 nm, shell thickness 10 nm, silica concentration 20 mass%, silica particle refractive index 1.31, preparation of JP 2002-79616 A 500 parts by weight, 30 parts of acryloyloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) and 1.5 parts of diisopropoxyaluminum ethyl acetate were mixed and mixed, 9 parts of exchange water was added. After reacting at 60 ° C. for 8 hours, the mixture was cooled to room temperature, and 1.8 parts of acetylacetone was added. While adding methyl ethyl ketone so that the content of silica was almost constant in 500 g of this dispersion, solvent substitution by vacuum distillation was performed at a pressure of 20 kPa. There was no generation of foreign matter in the dispersion, and the viscosity when adjusted to a solid content concentration of 20% by mass with methyl ethyl ketone was 5 mPa · s at 25 ° C.
When the residual amount of isopropyl alcohol in the obtained dispersion A-1 was analyzed by gas chromatography, it was 1.5%.

(Preparation of coating solution B for low refractive index layer)
40.0 parts by mass of the fluorine-containing copolymer (P-3) used in the coating solution A for low refractive index layer with respect to 200 parts by mass of methyl ethyl ketone, and terminal methacrylate group-containing silicone RMS-033 (manufactured by Gelest Co., Ltd.) )) 4 parts by mass, 3 parts by mass of photo radical generator Irgacure 907 (manufactured by Ciba Specialty Chemicals Co., Ltd.) were added and dissolved, and then 25.3 parts by mass of the sol solution a (solid content after solvent volatilization) 10 parts by mass) and 175 parts by mass of the above dispersion A-1 (35 parts by mass as a solid content of silica + surface treatment agent) were added. The coating liquid B for low refractive index layer was prepared by diluting with cyclohexanone and methyl ethyl ketone so that the solid content concentration of the entire coating liquid was 6% by mass and the ratio of cyclohexane and methyl ethyl ketone was 6:94.

  The low-refractive-index layer coating solution B thus obtained was applied according to Sample 101, and the low-refractive-index layer film thickness was adjusted to 85 nm to prepare Sample 103. The refractive index of the low refractive index layer after curing was 1.40.

(Preparation of antireflection films 104 to 105)
In the antireflection film 103, the low refractive index layer fluorine-containing copolymer (P-3) and DPHA (mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, Nippon Kayaku Co., Ltd., average molecular weight of about 560) The antireflection films 104 and 105 were produced in the same manner as the antireflection film 103 except that the ratio of) was changed as shown in Table 1. The refractive indexes of the low refractive index layer after curing were 1.41 and 1.43, respectively.

(Preparation of antireflection film 106)
A sample 106 in which the low refractive index layer in the sample 101 was changed as follows was produced.
(Preparation of coating solution C for low refractive index layer)
3 parts by mass of cyclohexanone is added to 100 parts by mass of OPSTAR JTA113 (thermally crosslinkable fluorine-containing silicone polymer composition liquid (solid content 6%), solvent methyl ethyl ketone, manufactured by JSR Corporation), and coating solution C for low refractive index layer Was prepared.
Using the thus obtained coating solution C for low refractive index layer, coating was performed according to Sample 101, and the sample was prepared by adjusting the film thickness of the low refractive index layer to 85 nm. The low refractive index layer was dried at 120 ° C. for 12 minutes, and the ultraviolet curing condition was 240 W / cm air-cooled metal halide lamp (eye graphics) while purging with nitrogen so that the atmosphere had an oxygen concentration of 0.1% by volume or less. Ltd.)) using irradiance 120 mW / cm ^2, and the irradiation amount of dose 120 mJ / cm ^2. The refractive index of the low refractive index layer after curing was 1.45.

(Preparation of antireflection film 107)
A sample 107 in which the low refractive index layer in the sample 106 was changed as follows was prepared.

(Preparation of coating solution D for low refractive index layer)
OPSTAR JTA113 (thermally crosslinkable fluorine-containing silicone polymer composition liquid (solid content: 6%): manufactured by JSR Corporation) 933.3 parts by mass (56.0 parts by mass as solid content), 195 masses of dispersion A-1 34 parts by mass of cyclohexanone to 12 parts by mass (39.0 parts by mass of silica + surface treatment agent solid content) and 12.65 parts by mass of sol liquid a (5.0 parts by mass of solid content), for a low refractive index layer Coating solution D was prepared.
Using the coating solution D for the low refractive index layer thus obtained, coating and curing were performed according to the sample 106. A sample 107 was prepared by adjusting the thickness of the low refractive index layer to 85 nm. The refractive index of the low refractive index layer after curing was 1.385.

(Preparation of antireflection film 108)
In the antireflection film 107, instead of the dispersion A-1, MEK-ST [silica sol (silica dispersion), average particle diameter 15 nm, solid content concentration 30%, manufactured by Nissan Chemical Industries, Ltd.] was used, and JTA113 and MEK- An antireflection film 108 was produced in the same manner as the antireflection film 107 except that the amount of ST was changed as shown in Table 1. The concentration of MEK-ST was adjusted to 25 parts by mass only with silica. The refractive index of the low refractive index layer after curing was 1.46.

(Evaluation of antireflection film)
The obtained film was evaluated for the following items.
(Evaluation 1) Inorganic fine particle content ratio R1
The ratio R1 [= (B / A) × 100 (%)) of the average particle filling rate (B) in the upper side 50% film thickness to the average particle filling rate (A) in the lower side 50% film thickness is obtained. It was. Each average particle filling rate (A), (B) was determined by the following method. The optical film was taken as a section having a thickness of 50 nm, and the cross section was photographed at 150,000 magnifications using five fields of view using a transmission electron microscope. The layer thickness was divided in half in the thickness direction into the upper side and the lower side, and the ratio of the occupied area of the inorganic fine particles to the total area for each of the upper side and the lower side was defined as the average particle filling rate. In the calculation, the width of 50 times the film thickness was targeted.
(Evaluation 2) Inorganic fine particle content ratio R2
Since the inorganic fine particles used in this example are silica, the M element is silicon. Rare gas ion etching was performed from the surface of each sample, and the content of carbon, silicon, and oxygen was measured by XPS at each point in the depth direction in the low refractive index layer film. Etching conditions and measurement conditions were as described below. The detected content of each element was determined as the atomic number concentration, and the silicon content was determined by the general formula (1).
(General Formula 1):
M element content / (carbon content + silicon content + oxygen content) × 100
The point where the silicon content was 20% or less of the maximum value was taken as the end point (boundary surface with the lower layer), and the etching time at that time was taken as the end point etching time (te minutes). In order to remove the effect of surface contamination, the first (1/50) te of data was ignored. The ratio R (= C / D) of the minimum content (C) to the maximum content (D) of the silicon content was determined. Whether the region having the minimum content appears within (1/2) te of the etching time (that is, whether it is on the surface side of 1/2 thickness of the outermost layer), and whether the minimum content or the maximum content is It was confirmed whether the position of is on the upper side.

(Etching conditions)
Accelerating voltage: 2kV, emission current: 20mA Ar ion (measurement conditions)
Measuring device: ESCA-3400 manufactured by KRATOS ANALYTICAL
X-ray anode: Mg
Output: 240W (acceleration voltage: 12kV emission current: 20mA)
Energy resolution: about 1.1eV
(Data import)
Narrow scan was performed in the range of bond energy: carbon C1s; 300 to 275 eV, oxygen O1s; 543 to 523 eVF1s, silicon Si2p; 112 to 90 eV.
(Data analysis method (how to obtain at%))
Background treatment was performed by a linear method to determine the peak area.
The concentration was determined based on the fact that the value obtained by dividing the area intensity of each peak by the photoionization cross section is proportional to the number of atoms.

(Evaluation 3) Steel wool scratch resistance evaluation A rubbing test was performed using a rubbing tester under the following conditions.
Evaluation environmental conditions: 25 ° C., 60% RH
Rubbing material: Steel wool (No. 0000, manufactured by Nippon Steel Wool Co., Ltd.) was wound around the rubbing tip (1 cm × 1 cm) of a tester that was in contact with the sample, and the band was fixed so as not to move. Then, the reciprocating rubbing motion under the following conditions was given.
Moving distance (one way): 13 cm, rubbing speed: 13 cm / second,
Load: 500 g / cm ² , tip contact area: 1 cm × 1 cm,
Number of rubs: 10 round trips.
An oil-based black ink was applied to the back side of the rubbed sample and visually observed with reflected light, and scratches on the rubbed portion were evaluated according to the following criteria.
○: At first glance, scratches are not visible.
○ △: Scratches are visible if you look carefully △: Weak scratches are visible ×: Clear scratches are visible

(Evaluation 4) Eraser scuff resistance evaluation A rubbing test was conducted under the following conditions using a rubbing tester.
Evaluation environmental conditions: 25 ° C., 60% RH,
Rubbing material: A plastic eraser (manufactured by Dragonfly Pencil Co., Ltd., MONO) was fixed to the tip (1 cm × 1 cm) of the rubbing of the tester in contact with the sample.
Travel distance (one way): 4cm, rubbing speed: 2cm / sec,
Load: 500 g, tip contact area: 0.8 mmφ,
Number of rubs: 100 round trips.
An oil-based black ink was applied to the back side of the rubbed sample and visually observed with reflected light, and scratches on the rubbed portion were evaluated according to the following criteria.
○: At first glance, scratches are not visible.
◯: Scratches are visible when you look closely △: Weak scratches are visible.
×: Clear scratches are visible

From the results shown in Table 1, the following is clear.
Those containing fine particles with a distribution defined in the present invention and having an R value within the range of the present invention are excellent in both steel wool scratch resistance and eraser scratch resistance. It should be noted that in any sample of the present invention, the region having the minimum content is within 1/2 te (that is, on the surface side with respect to 1/2 thickness of the outermost layer), and the minimum content is relative to the maximum content. It was confirmed that it was on the upper side.

A sample in which the inorganic fine particles of the low refractive index layer and the solvent composition were changed as shown in Table 2 with respect to the sample 104 of Example 1 was prepared. The solvent composition was adjusted by changing the amount of cyclohexanone when the solid content concentration of the entire coating solution was adjusted to 6% by mass.
The dispersion of inorganic fine particles used is shown below.

(Preparation of dispersion A-2)
Except for the dispersion A-1, except that acryloyloxypropyltrimethoxysilane was reduced to 20 parts and 10 parts of tridecafluorooctyltrimethoxysilane (GE Toshiba Silicone Co., Ltd.) was newly added. Dispersion A-2 was prepared in the same manner. No foreign matter was generated in the dispersion, and the viscosity when the solid content was adjusted to 20% by mass with methyl ethyl ketone was 5 mPa · s at 25 ° C. When the residual amount of isopropyl alcohol in the obtained final dispersion was analyzed by gas chromatography, it was 1.5% by mass.

(Preparation of dispersion B-1)
To 333 parts of silica fine particle sol (Isopropyl alcohol sol manufactured by Nissan Chemical Industries, Ltd., average particle diameter 50 nm, silica concentration 30%), 30 parts of acryloyloxypropyltrimethoxysilane and 1.5 parts of diisopropoxyaluminum ethyl acetate are added. After mixing, 9 parts of ion exchange water was added. After reacting at 60 ° C. for 8 hours, the mixture was cooled to room temperature, and 1.8 parts of acetylacetone was added. While adding methyl ethyl ketone to 333 g of this dispersion so that the silica content was almost constant, the solvent was replaced 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% with methyl ethyl ketone was 6 mPa · s at 25 ° C. When the residual amount of isopropyl alcohol in the obtained dispersion was analyzed by gas chromatography, it was 1.5% by mass.

(Preparation of dispersion C-1)
30 parts of acryloyloxypropyltrimethoxysilane was added to 333 parts of silica fine particle sol (manufactured by Nissan Chemical Industries, Ltd., methyl ethyl ketone sol, average particle diameter 50 nm, silica concentration 30%). The mixture was reacted at 60 ° C. for 8 hours and then cooled to room temperature. The viscosity when the solid content concentration was adjusted to 20% by mass with methyl ethyl ketone was 5 mPa · s at 25 ° C.

  The results of evaluation according to Example 1 are also shown in Table 2.

From the results shown in Table 2, the following is clear.
It can be seen that by using cyclohexanone and methyl ethyl ketone together in the coating solution solvent, the R value is improved and the scratch resistance is improved. It can also be seen that the use of surface-treated hollow silica is excellent in scratch resistance. It should be noted that in any sample of the present invention, the region having the minimum content is within 1/2 te (that is, on the surface side with respect to 1/2 thickness of the outermost layer), and the minimum content is relative to the maximum content. It was confirmed that it was on the upper side.

The multilayer antireflection film shown below was produced.
(Preparation of coating liquid A for hard coat layer)
PET-30 50.0g
Irgacure 184 2.0g
SX-350 (30%) 1.5g
Cross-linked acrylic-styrene particles (30%) 13.9g
FP-132 0.75g
KBM-5103 10.0g
Toluene 38.5g

  The mixed solution was filtered through a polypropylene filter having a pore size of 30 μm to prepare a hard coat layer coating solution.

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

  KBM-5103: acryloyloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.).

(Coating of hard coat layer)
An 80 μm-thick triacetyl cellulose film (TAC-TD80U, manufactured by Fuji Photo Film Co., Ltd.) is unwound in a roll form and directly coated with the above coating liquid A for hard coat layer 180 lines / inch, depth 40 μm Using a microgravure roll having a diameter of 50 mm and a doctor blade having a gravure pattern, the coating was applied at a gravure roll rotational speed of 30 rpm and a conveying speed of 30 m / min, dried at 60 ° C. for 150 seconds, and further purged with nitrogen Using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) with an oxygen concentration of 0.1%, irradiance of 400 mW / cm ² and an irradiation amount of 250 mJ / cm ² were applied to irradiate the coating layer. Cured to form a 6 μm thick layer and wound up. The surface roughness of the hard coat 301 obtained as a sample thus prepared was Ra of 0.18 μm, Rz of 1.40 μm, and haze of 35%.

  As a result of coating the low refractive index layers of Examples 1 and 2 on the hard coat 301 and performing the evaluation according to Examples 1 and 2, antiglare excellent in scratch resistance and antifouling properties according to the present invention. It was found that an antireflection film can be obtained.

(Preparation of coating solution for hard coat layer)
Desolite Z7404 (zirconia fine particle-containing hard coat composition: manufactured by JSR Corporation) 100 parts by mass, DPHA (UV curable resin: Nippon Kayaku Co., Ltd.) 31 parts by mass, KBM-5103 (silane coupling agent: Shin-Etsu) Chemical Industry Co., Ltd.) 10 parts by mass, KE-P150 (1.5 μm silica particles: Nippon Shokubai Co., Ltd.) 8.9 parts by mass, MXS-300 (3 μm crosslinked PMMA particles: manufactured by Soken Chemical Co., Ltd.) 3.4 parts by mass, 29 parts by mass of MEK, and 13 parts by mass of MIBK were put into a mixing tank and stirred to obtain a hard coat layer coating solution.

(Preparation of antireflection film)
A triacetyl cellulose film (TD80U, manufactured by Fuji Photo Film Co., Ltd.) as a support is unwound in a roll form, and the above coating liquid for hard coat layer has a diameter of 135 lines / inch and a gravure pattern with a depth of 60 μm. Using a 50 mm micro gravure roll and a doctor blade, the coating was carried out under conditions of a conveyance speed of 10 m / min, dried at 60 ° C. for 150 seconds, and further under a nitrogen purge, an air-cooled metal halide lamp (Igraphics Corporation) )), The coating layer was cured by irradiating ultraviolet rays having an irradiance of 400 mW / cm ² and an irradiation amount of 250 mJ / cm ² to form a hard coat layer and wound up. The hard coat 401 was prepared by adjusting the rotation speed of the gravure roll so that the thickness of the hard coat layer after curing was 4.0 μm. The surface roughness of the hard coat 401 thus obtained was Ra = 0.02 μm, RMS = 0.03 μm, and Rz = 0.25 μm. (Ra (center line average roughness), RMS (root mean square roughness), Rz (n-point average roughness) are measured by scanning probe microscope system SPI3800, manufactured by Seiko Instruments Inc.).

  The low refractive index layers of Examples 1 and 2 were coated on the hard coat 401. According to the present invention, it was found that an antireflection film having excellent scratch resistance and antifouling properties and having scattering properties can be obtained.

(Saponification treatment of antireflection film)
A 1.5 mol / l aqueous sodium hydroxide solution was prepared and kept at 55 ° C. A 0.005 mol / lN 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.
In this way, a saponified antireflection film was produced.

(Preparation of polarizing plate with antireflection film)
A polarizing film was prepared by adsorbing iodine to a stretched polyvinyl alcohol film. A saponified antireflection film was attached to one side of the polarizing film using a polyvinyl alcohol adhesive so that the support side (triacetylcellulose) of the antireflection film was the polarizing film side. In addition, a viewing angle widening film (wide view film SA12B, manufactured by Fuji Photo Film Co., Ltd.) was saponified and attached to the other side of the polarizing film using a polyvinyl alcohol-based adhesive. In this way, a polarizing plate was produced.

  In Examples 1 to 4, antireflection film samples in which the coating method was changed from a gravure coater to a die coater for all layers were prepared, and evaluations according to Examples 1 to 4 were performed. As a result, it was found that a sample prepared using a die coater according to the present invention was excellent in coating film surface, had a low reflectance, and formed a coating film excellent in scratch resistance and antifouling property of the film.

  When the polarizing plate produced in Example 5 was used as the polarizing plate on the viewing side of the transmission type liquid crystal cell so that the antireflection film was on the viewing side, the surface was hardly damaged, the contrast in the bright room was excellent, and it was extremely visible A liquid crystal display device having excellent properties and high display quality was obtained. When the antireflection film of Example 3 was used in combination with a transmission type VA liquid crystal cell, the surface was hard to be damaged, the contrast in the bright room was excellent, and the visibility was extremely excellent, and the contrast improvement effect in the oblique direction Was confirmed. When the antireflection film of Example 4 was used in combination with a transmissive TN liquid crystal cell, the surface was hard to be damaged, the contrast in a bright room was excellent, and the visibility was extremely excellent. The color has been improved.

As the 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 inventive sample of Examples 1 to 4 is attached, and the protective film on the liquid crystal cell side of the polarizing plate on the backlight side, the viewing angle When an enlarged film (Wideview Film Ace, manufactured by Fuji Photo Film Co., Ltd.) is used, it has excellent contrast in a bright room, very wide viewing angles in the vertical and horizontal directions, extremely excellent visibility, and high display quality. A liquid crystal display device was obtained.
The sample of the present invention of Example 4 has a scattered light intensity of 30 ° with respect to an output angle of 0 ° of 0.06%, and this light diffusibility particularly improves the downward viewing angle and the yellowness in the left-right direction. It was a very good liquid crystal display device. For comparison, the film produced in the same manner as in Example 4 except that the cross-linked PMMA particles and silica particles were removed from the hard coat coating solution, and the scattered light intensity at 30 ° with respect to an emission angle of 0 ° was substantially 0%. Yes, the downward viewing angle was increased and the yellowing improvement effect was not obtained at all.

  When the inventive samples of Examples 1 to 4 were bonded to the glass plate on the surface of the organic EL display device via an adhesive, reflection on the glass surface was suppressed, and a display device with high visibility was obtained. .

  A polarizing plate with a single-sided antireflection film was prepared using the samples of Examples 1 to 4, and a λ / 4 plate was bonded to the opposite surface of the polarizing plate on the side having the antireflection film. When affixed to the surface glass plate, surface reflection and reflection from the inside of the surface glass were cut, and a display with extremely high visibility was obtained.

It is five typical examples of the presence state of the inorganic fine particles in the low refractive index layer according to the invention.

Claims (15)

  An optical film in which at least one layer is formed on a support, and a thin film layer having a thickness of 200 nm or less containing inorganic fine particles and a binder is formed on the outermost surface. Is less than 1/2 of the thickness of the thin film layer and is in a non-uniform existence state where the inorganic fine particles have a honey region and a sparse region in the film thickness direction, and is a dense region on the support side The average particle filling rate (B) in the 50% film thickness opposite to the support (upper side) relative to the average particle filling rate (A) in the 50% film thickness on the support side (lower side) of the thin film layer ) Ratio R1 [= (B / A) × 100 (%)] is 5% or more and less than 100%.   An optical film in which at least one layer is formed on a support, and a thin film layer having a thickness of 200 nm or less containing inorganic fine particles and a binder is formed on the outermost surface. Is less than 1/2 of the thickness of the thin film layer and is in a non-uniform existence state where the inorganic fine particles have a honey region and a sparse region in the film thickness direction, and is a dense region on the support side And the content of inorganic fine particles takes the minimum content (C) in the ½-thickness region opposite to the support (upper side), and the support side (lower part) from the region showing the minimum content The maximum content (D) is taken in the region of the side), and the ratio R2 [= (C / D) × 100 (%)) of the minimum content (C) to the maximum content (D) is 5% or more and less than 100% An optical film characterized in that   The optical film according to claim 1 or 2, which contains 10% by mass or more of inorganic fine particles.   4. The optical film according to claim 1, wherein the surface of the inorganic fine particles is treated with a compound that forms a covalent bond with the inorganic fine particles.   The optical film according to claim 1, wherein the inorganic oxide particles contain silicon dioxide as a main component.   The optical film according to claim 1, wherein the inorganic fine particles are hollow silica.   The optical film according to any one of claims 1 to 6, wherein the binder contains at least one ionizing radiation curable resin.   The optical film according to any one of claims 1 to 6, wherein the binder contains a thermosetting resin.   The optical film according to claim 1, wherein the binder contains a compound containing at least a fluorocarbon and / or dimethylsiloxane.   The optical film according to any one of claims 1 to 9, wherein the support is a transparent support, and the optical film is formed by laminating at least a layer having a hard coat property and a low refractive index layer. Multi-layer anti-reflection film.   There is at least one high refractive index layer containing inorganic fine particles between the layer having a hard coat property and the low refractive index layer, and the average value of the specular reflectance at 5 ° incidence at a wavelength of 450 nm to 650 nm is 1. The multilayer antireflection film according to claim 10, wherein the multilayer antireflection film is at most%.   12. The method for producing an optical film according to claim 1, wherein the coating composition containing fine particles and a binder contains at least two kinds of volatile solvents. Method.   A polarizing plate comprising the optical film according to claim 1.   A polarizing plate comprising the optical film according to claim 1 and a retardation film.   An image display device comprising the optical film according to claim 1 or the polarizing plate according to claim 13 or 14.

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