TWI448719B - Anti-reflection film, and anti-reflection film, and a polarizing plate using the same, and a display device - Google Patents

Description

Antireflection film, and manufacturing method of antireflection film, polarizing plate using the same, and display device

The present invention relates to an antireflection film, a method for producing the antireflection film, a polarizing plate using the same, and a display device.

Generally, the anti-reflection film is used in an image display device such as a cathode tube display device (CRT), a plasma display (PDP), an electroluminescence display (ELD), or a liquid crystal display device (LCD), because it can prevent external light reflection. The contrast is reduced or the image is taken up by the light of the multilayer film, which has the function of reducing the reflectivity and is disposed on the outermost surface of the display.

In recent years, the use environment of the antireflection film has various forms such as outdoor or indoor. It is particularly required to have excellent film strength which can be used under large-screen use for outdoor use, and has an excellent anti-reflection film for environmental changes.

In the past, in the antireflection film, a film made of cerium oxide was used in order to improve the film strength or chemical resistance under the function of reducing the reflectance (reduced refractive index). On the other hand, when the film formed of the cerium oxide system is alkaline, the polycondensation reaction proceeds, and the basic skeleton of the formed film becomes large. Generally, as the polycondensation reaction proceeds, the mechanical strength of the film is improved (see Non-Patent Document 1).

However, in the antireflection film for optical use, when an alkaline cerium oxide film is used, the reaction of the film is difficult to control, and the adhesion to the substrate becomes sufficient, and it is difficult to obtain satisfactory strength, particularly for environmental changes. (Under high temperature and high humidity), deterioration of film strength or chemical resistance becomes large.

Patent Document 1 describes, for example, a technique in which hollow ceria particles having a shell layer and having a porous or hollow interior are used. This patent document can improve the film strength or chemical resistance under the function of reducing the reflectance (reduced refractive index).

Patent Document 2 discloses that (a) a hard coat layer containing an active energy ray-curable resin and (b) a refraction containing a conductive metal oxide fine particle are provided on a transparent film having an elastic modulus of 3,500 to 5,500 MPa. The rate layer, (c) a high refractive index layer containing titanium oxide fine particles, and (d) an antireflection film containing a low refractive index layer of hollow ceria-based fine particles having an outer shell layer and having a porous or void inside.

[Patent Document 1] JP-A-2002-79616 [Patent Document 2] JP-A-2005-266051

[Non-Patent Document 1] S. Shibata, F. Hanawa and M. Nakahara, Electron. Ltt, 21, 24 (1985) 1145.

However, the film containing the hollow cerium oxide microparticles produced in Patent Document 1 has a pH at the surface (film surface) which is alkaline, and when the film is used for an antireflection film for optical use, the film strength is not sufficient, particularly When it is predicted to be used outdoors, there is a practical problem in film strength, scratch resistance, chemical resistance, and adhesion under high temperature and high humidity.

Moreover, the antireflection film described in Patent Document 2 is actually a film strength (scratch resistance) after the forced deterioration test, but the antireflection layer is The three-layer constructor has a problem of high cost.

An object of the present invention is to provide a problem that can solve the above-mentioned problems of the prior art, and the chemical resistance, adhesion, and film strength after the endurance test under high temperature and high humidity can be achieved by the antireflection layer formed by one layer of the low refractive index layer. An antireflection film excellent in low cost, a polarizing plate using the same, and a display device.

The above object of the present invention can be achieved by the following constitution.

An antireflection film which is an antireflection film having a low refractive index layer on at least one of the outermost surfaces of a transparent film substrate, characterized in that the low refractive index layer contains at least one hollow having a porous or void inside. The cerium oxide microparticles have a pH of 2.0 to 7.5 on the surface (film surface) of the low refractive index layer.

2. The antireflection film according to 1, wherein the surface of the low refractive index layer (film surface) has a pH of from 2.0 to 4.0.

3. The antireflection film according to 1. or 2. wherein the surface of the low refractive index layer (film surface) is measured under the conditions of a temperature of 50 ° C in a bath for 2 hours.

4. The antireflection film according to any one of 1 to 3, wherein the low refractive index layer contains a reactive modified polyoxyalkylene resin.

5. The antireflection film according to any one of 1 to 4, wherein the low refractive index layer contains an imidazole or a derivative thereof represented by the following general formula (1); (R1)nA.........(1) In the formula, R1 represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms which may be substituted by an amine group or a hydroxyl group, an alkenyl group and a halogen atom, and when R1 is plural, they may be the same or Different from each other; the amine group represented by R1 may be substituted by 1 or 2 methyl groups or ethyl groups; and the alkyl group and the alkenyl group may be substituted by an alkyl group having 1 to 3 carbon atoms; n is an integer of 1 to 3; A represents an imidazolyl group.

A method for producing an antireflection film, which is characterized in that the antireflection film according to any one of 1. to 5.

A polarizing plate characterized in that the antireflection film according to any one of 1. to 5. is used on one surface.

A display device, which is characterized in that the antireflection film according to any one of 1. to 5.

A display device characterized by using a polarizing plate as described in 7.

The present invention provides an antireflection film which is excellent in low-cost resistance to chemicals and adhesion after the endurance test under high temperature and high humidity, and which has improved film strength. Moreover, by using the antireflection film of the present invention, it is possible to neglect the noise intrusion of light, and to obtain a display device using the polarizing plate excellent in visibility and the polarizing plate.

A preferred form of implementing the invention

Continuing, the embodiments of the present invention will be described, but the present invention is not limited thereto.

The antireflection film of the present invention has at least one of the outermost surfaces of the transparent film substrate formed of the transparent resin film, and has a lower fold than the transparent film substrate. The low refractive index layer of the rate of incidence described below.

Further, in the antireflection film of the present invention, in addition to the low refractive index layer, a high refractive index layer having a higher refractive index than the transparent film substrate is provided between the low refractive index layer and the transparent film substrate, thereby reducing the optical The reflectance caused by dryness is preferred. Further, in the present invention, a single layer of a low refractive index layer or a laminated layer such as a low refractive index layer or a high refractive index layer is also referred to as an antireflection layer.

The antireflection layer is formed by laminating three layers having different refractive indices on the transparent film substrate side in the order of the medium refractive index layer/high refractive index layer/low refractive index layer, and is preferably from the viewpoint of reducing reflectance. . Here, the medium refractive index layer is a layer which is higher in refractive index than the transparent film substrate and lower in refractive index than the high refractive index layer.

Continuing, the low refractive index layer of the antireflection film of the present invention will be described.

The low refractive index layer of the antireflection film of the present invention is a layer having a lower refractive index than that of the transparent film substrate, and is referred to as a low refractive index layer. The specific refractive index is preferably in the range of 1.30 to 1.45 at 23 ° C and 550 nm. Further, the film thickness of the low refractive index layer is preferably from 5 nm to 0.5 μm, more preferably from 10 nm to 0.3 μm, even more preferably from 30 nm to 0.2 μm.

The low refractive index layer of the antireflection film of the present invention is characterized in that it contains at least one type of hollow ceria particles having a porous or void inside, and has a pH of 2.0 to 7.5.

When the surface of the low refractive index layer (film surface) is controlled to have a pH of 2.0 to 7.5, it is found that a reaction in the layer having a low layer folding ratio can be provided, and the substrate is adhered to the substrate. The present invention is also excellent in the properties of the antireflection film which is excellent in chemical resistance under high temperature and high humidity, and excellent in film strength and adhesion.

More preferably, the surface (film surface) of the low refractive index layer has a pH of 2.0 to 4.0, and in this range, an excellent film strength (scratch resistance) effect can be exhibited. Further, when the pH of the surface (film surface) after immersion in a 50 ° C warm bath for 2 hours is controlled to the above range, the object of the present invention can be stably obtained, which is particularly preferable.

Further, as the water of a 50 ° C warm bath, ion exchange water having a pH of 6 to 8 was used.

In the present invention, at least one type of hollow cerium oxide fine particles (hereinafter simply referred to as hollow fine particles) which are porous or void inside the low refractive index layer of the antireflection film will be described.

The hollow fine particles are (1) composite particles formed by a porous particle and a coating layer provided on the surface of the porous particle, or (2) voids having voids inside, and the contents are filled with a solvent, a gas or a porous substance. particle.

Moreover, the hollow particles are particles having voids inside, and the voids are surrounded by the particle walls. The cavity is filled with contents such as a solvent, a gas, or a porous substance used in the preparation. The average particle diameter of the hollow fine particles is 5 to 200 nm, preferably 10 to 70 nm. The particle size of the hollow fine particles is preferably a monodisperse with a coefficient of variation of 1 to 40%.

The average particle diameter of the hollow cerium oxide microparticles used in the present invention can be measured by an electron micrograph by a scanning electron microscope (SEM) or the like. The measurement is carried out by using a particle size distribution meter such as a dynamic astigmatism method or a static astigmatism method.

The average particle diameter of the empty microparticles used in the present invention may be appropriately selected in accordance with the transparent coating thickness of the formed low refractive index layer, and the film thickness of the transparent envelope is preferably 3/2 to 1/10, preferably 2 /3~1/10. Among them, the hollow fine particles are preferably formed in a state of being dispersed in an appropriate medium due to the formation of a low refractive index layer.

As the dispersing medium, water, alcohols (for example, methanol, ethanol, isopropanol), and ketones (for example, methyl ethyl ketone, methyl isobutyl ketone), ketone alcohols (for example, diacetone alcohols), and Propyl monomethyl ether, propylene glycol monomethyl ether acetate, and the like are preferred.

The thickness of the coating layer of the composite particles or the particle wall thickness of the void particles is 1 to 40 nm, preferably 1 to 20 nm, more preferably 2 to 15 nm. In the case of the composite particles, when the thickness of the coating layer is less than 1 nm, the particles may not be completely coated, and the coating liquid component may easily enter the inside of the composite particles, thereby reducing the internal porosity and achieving a sufficient effect of lowering the refractive index. When the thickness of the coating layer exceeds 20 nm, the coating liquid component does not enter the inside, and the porosity (pore volume) of the composite particles is lowered, and a sufficient effect of lowering the refractive index may not be obtained.

Further, in the case of the void particles, when the thickness of the particle wall is less than 1 nm, the particle shape may not be maintained, and even if the thickness exceeds 20 nm, the sufficient effect of lowering the refractive index cannot be achieved.

It is preferred that the coating layer of the composite particles or the particle walls of the void particles have cerium oxide as a main component. Further, components other than cerium oxide may be contained, and specific examples thereof include Al ₂ O ₃ , B ₂ O ₃ , TiO ₂ , ZrO ₂ , SnO ₂ , CeO ₂ , P ₂ O ₃ , Sb ₂ O ₃ , and MoO _{3 .} , ZnO ₂ , WO _3, and the like. Examples of the porous particles constituting the composite particles include those obtained by cerium oxide, inorganic compounds other than cerium oxide and cerium oxide, and CaF ₂ , NaF, NaAlF ₆ , MgF, and the like. Among them, a porous particle composed of a composite oxide of an inorganic compound other than cerium oxide and cerium oxide is preferred.

Examples of the inorganic compound other than cerium oxide include Al ₂ O ₃ , B ₂ O ₃ , TiO ₂ , ZrO ₂ , SnO ₂ , CeO ₂ , P ₂ O ₃ , Sb ₂ O ₃ , MoO ₃ , ZnO ₂ , One type or two or more types of WO ₃ or the like. In such porous particles, silicon dioxide as a representative of SiO _2, an inorganic compound other than silicon dioxide molar ratio in terms of oxide when MOx (MOx) / SiO ₂ of 0.0001 to 1.0, preferably from 0.001 to 0.3 of range.

When it is difficult to obtain a porous particle having a molar ratio of MOx/SiO _{2 of} less than 0.0001, even if the pore volume is small, a particle having a low refractive index cannot be obtained. Further, when the molar ratio MOx/SiO _{2 of the} porous particles exceeds 1.0, the ratio of cerium oxide becomes small, so that the pore volume becomes large, and it is difficult to obtain a refractive index lower.

The pore volume of such a porous particle is in the range of 0.1 to 1.5 ml/g, preferably 0.2 to 1.5 ml/g. When the pore volume is less than 0.1 ml/g, particles having a sufficiently lowered refractive index cannot be obtained. When the pore volume exceeds 1.5 ml/g, the strength of the fine particles is lowered, and the strength of the obtained coating film is lowered.

Moreover, the pore volume of such a porous particle can be obtained by mercury intrusion. Moreover, as a content of the hollow particle, a solvent, a gas, a porous substance, etc. used at the time of particle preparation are mentioned. The solvent may contain an unreacted material of the particle precursor used in the preparation of the void particles, a catalyst to be used, and the like.

Further, examples of the porous material include those exemplified as the porous particles. These contents can be made up of a single component or a complex A mixture of several ingredients.

As a method for producing the hollow fine particles, for example, a method of preparing composite oxide colloidal particles disclosed in paragraphs [0010] to [0033] of JP-A-7-133105 can be employed. When the specific composite particles are made of an inorganic compound other than cerium oxide or cerium oxide, hollow fine particles can be produced by performing the following first to third steps.

(Step 1: Modulation of porous particle precursor)

In the first step, an aqueous alkali solution of a raw material of an inorganic compound other than cerium oxide raw material and cerium oxide is prepared in advance, or a mixed aqueous solution of a raw material of an inorganic compound other than cerium oxide raw material and cerium oxide is prepared. The composite ratio of the aqueous solution as the intended composite oxide is gradually added to the aqueous alkali solution having a pH of 10 or more to prepare a porous particle precursor.

As the raw material of cerium oxide, an alkali metal, ammonium or an organic base citrate can be used. As the alkali metal citrate, sodium citrate (water glass) or potassium citrate can be used. Examples of the organic base include amines such as a fourth-order ammonium salt such as a tetraethylammonium salt, monoethanolamine, diethanolamine or triethanolamine. Further, the ammonium citrate or the organic acid citrate also contains an alkaline solution of ammonia, a fourth-order ammonium hydroxide, an amine compound or the like in the citric acid solution.

Further, as a raw material of an inorganic compound other than cerium oxide, an alkali-soluble inorganic compound can be used. Specific examples thereof include an oxidizing acid of an element selected from the group consisting of Al, B, Ti, Zr, Sn, Ce, P, Sb, Mo, Zn, and W, an alkali metal salt of the oxidizing acid, an alkaline earth metal salt, and an ammonium salt. Grade 4 ammonium salt. More The body is sodium aluminate, sodium tetraborate, ammonium zirconium carbonate, potassium citrate, potassium stannate, sodium aluminosilicate, sodium molybdate, ammonium cerium nitrate, sodium citrate.

Although the pH of the mixed aqueous solution changes while the addition of these aqueous solutions, it is not particularly necessary to control the pH to a predetermined range. The aqueous solution ultimately determines its pH based on the type of inorganic oxide and its mixing ratio. The rate of addition of the aqueous solution at this time is not particularly limited. Further, in the production of the composite oxide particles, the dispersion of the seed particles can be used as a starting material.

The particles are not particularly limited, and inorganic oxides such as SiO ₂ , Al ₂ O ₃ , TiO ₂ or ZrO ₂ or fine particles of the composite oxides thereof can be used, and generally, they can be used. Further, the porous particle precursor dispersion obtained by the above production method can also be used as a seed particle dispersion.

When the seed particle dispersion liquid is used, the pH of the seed particle dispersion liquid is adjusted to 10 or more, and then the aqueous solution of the above compound is added to the aqueous alkali solution with stirring in the particle dispersion liquid. At this time, it is not necessary to carry out dispersion pH control. When such a seed particle is used, it is easy to control the particle size of the prepared porous particle, and a uniform particle size can be obtained.

The above-mentioned ceria raw material and inorganic compound raw material have a high solubility in alkali. However, when the two are mixed in a large pH region of the solubility, the solubility of oxidized acid ions such as citrate ions and aluminate ions is lowered, and these complexes are precipitated to grow into fine particles or cause growth of particles precipitated on the seed particles. . Therefore, it is not necessary to perform pH control as in the past method when the fine particles are precipitated and grown.

The composite ratio of the inorganic compound other than cerium oxide and cerium oxide in the first step is converted to an oxide (MO _x ) for the inorganic compound of cerium oxide, and the molar ratio of MO _x /SiO ₂ is 0.05 to 2.0. Preferably, it is in the range of 0.2 to 2.0. Within this range, the smaller the ratio of cerium oxide, the larger the pore volume of the porous particles. However, even if the molar ratio exceeds 2.0, the pore volume of the porous particles hardly increases. On the other hand, when the molar ratio is less than 0.05, the pore volume becomes small.

When modulating the void particles, the molar ratio of MO _x /SiO ₂ is preferably in the range of 0.25 to 2.0.

(Step 2: removal of inorganic compounds other than cerium oxide from porous particles)

In the second step, at least a part of the inorganic compound (an element other than cerium and oxygen) other than cerium oxide is selectively removed from the porous particle precursor obtained in the first step. As a specific removal method, the inorganic compound in the porous particle precursor is dissolved or removed by using a citric acid or an organic acid, or is contacted with a cation exchange resin, and then ion-exchange-removed.

Further, the porous particle precursor system obtained in the first step is a mesh structure particle in which an element of an inorganic compound and an inorganic compound are bonded to each other via oxygen. By thus removing the inorganic compound (the element other than cerium and oxygen) from the porous particle precursor, a porous particle having a large pore volume in the porous body can be obtained. Further, by removing the amount of the inorganic oxide (the element other than cerium and oxygen) from the porous particle precursor, the void particles can be prepared.

Further, before removing the inorganic compound other than cerium oxide from the porous particle precursor, the porous particle precursor dispersion obtained in the first step It is preferred to add a citric acid solution or a hydrolyzable organic ruthenium compound containing a decane compound of a substituted alkyl group to a fluorine-containing alkali metal salt containing an alkali metal salt of cerium oxide to form a cerium oxide protective film. The thickness of the ruthenium dioxide protective film may be 0.5 to 40 nm, preferably 0.5 to 15 nm. Further, even if the ruthenium dioxide protective film is formed, the protective film in this step is porous and has a small thickness, so that the inorganic compound other than the above cerium oxide can be removed from the porous particle precursor.

By forming such a cerium oxide protective film, the inorganic compound other than the above-mentioned cerium oxide can be removed from the porous particle precursor while maintaining the particle shape. Further, when the ceria coating layer described later is formed, the pores of the porous particles are not blocked by the coating layer, so that the pore volume can be formed without forming a ceria coating layer to be described later. Further, when the amount of the inorganic compound to be removed is small, the particles are not destroyed, and it is not necessary to form a protective film.

Further, when the void particles are prepared, it is preferable to form the ceria protective film. When the void particles are prepared, when the inorganic compound is removed, a precursor of the void particles formed by the cerium oxide protective film, the solvent in the cerium oxide protective film, and the undissolved porous solid component can be obtained. When a coating layer to be described later is formed in the body, the formed coating layer becomes a particle wall to form void particles.

The amount of the ceria source to be added in order to form the above-mentioned ceria protective film is preferably less in the range in which the shape of the particles can be maintained. When the amount of the cerium oxide source is too large, the cerium oxide protective film is too thick, and it is difficult to remove the inorganic compound other than cerium oxide from the porous particle precursor.

Hydrolyzable organic deuteration for use in the formation of a cerium oxide protective film As the compound, the alkoxydecane represented by the following general formula (2) can be used.

R _n Si(OR') _4-n (2) wherein R and R' represent a hydrocarbon group such as an alkyl group, an aryl group, a vinyl group or a propenyl group, and n represents 0, 1, 2 or 3. In particular, tetraalkoxy decane such as tetramethoxy decane, tetraethoxy decane or tetraisopropoxy decane which is substituted by fluorine is preferably used.

As a method of addition, a solution of a small amount of a base or an acid as a catalyst is added to a mixed solution of alkoxysilane, pure water, and an alcohol, and added to a dispersion of porous particles, which will be alkoxydecane. a solution of a small amount of a base or an acid as a catalyst added to a mixed solution of pure water and an alcohol, added to a dispersion of porous particles, and a citric acid polymer formed by hydrolysis of alkoxydecane is attached to the inorganic On the surface of the oxide particles.

At this time, an alkoxysilane, an alcohol, and a catalyst can be simultaneously added to the dispersion. As the base catalyst, ammonia, an alkali metal hydroxide or an amine can be used. Further, as the acid catalyst, various inorganic acids and organic acids can be used.

When the dispersion medium of the porous particle precursor is water alone or when the ratio of water to the organic solvent is high, a cerium oxide protective film can be formed using a citric acid solution. When a citric acid solution is used, a predetermined amount of citric acid solution is added to the dispersion, and a base is added to attach the citric acid solution to the surface of the porous particle. Further, a cerium oxide protective film may be prepared by using a citric acid solution together with the above alkoxy decane.

(Step 3: Formation of a cerium oxide coating layer) In the third step, in the porous particle dispersion (the cavity particle precursor dispersion in the case of void particles) prepared in the second step, a hydrolyzable organic ruthenium compound having a fluorene-containing alkyl group-containing decane compound or The surface of the particles is coated with a polymer such as a hydrolyzable organic hydrazine compound or a citric acid solution to form a cerium oxide coating layer.

Further, the citric acid solution is obtained by subjecting an aqueous solution of an alkali metal ruthenate such as water glass to an alkali-removed low-polymer aqueous solution of citric acid.

The amount of the organic cerium compound or the ceric acid solution used for forming the coating layer is only sufficient to coat the surface of the colloidal particles, and the thickness of the cerium oxide coating layer finally obtained is 1 to 40 nm, preferably It is added in an amount of 1 to 20 nm, and is added to a dispersion of porous particles (the void particles are actually hollow particle precursors). Moreover, when the ceria protective film is formed, the total thickness of the ceria protective film and the ceria coating layer is 1 to 40 nm, and it is preferable to add an organic antimony compound or a tannic acid solution in an amount of 1 to 20 nm.

Then, the dispersion of the particles forming the coating layer is heat-treated by adhesion. By the heat treatment, in the case of the porous particles, the ceria coating layer covering the surface of the porous particles is densified to obtain a dispersion of the composite particles in which the porous particles are coated with the ceria coating layer. Further, in the case of the void particle precursor, the formed coating layer is densified to become a void particle wall, and a dispersion liquid having void particles having voids filled with a solvent, a gas or a porous solid component is obtained.

The heat treatment temperature at this time is only to the extent that the fine pores of the ceria coating layer can be blocked, and is not particularly limited, and is in the range of 80 to 300 ° C. good. When the heat treatment temperature is less than 80 ° C, the fine pores of the ceria coating layer may be completely blocked, and densification may not be performed, and the treatment time must be long. When the heat treatment temperature exceeds 300 ° C for a long period of time, it becomes a dense particle, and the effect of lowering the refractive index cannot be obtained.

The refractive index of the inorganic fine particles thus obtained is lower at less than 1.42. It is presumed that the inorganic fine particles maintain the porosity inside the porous particles, but the inside is void, so that the refractive index is lowered.

Further, as the hollow fine particles from the viewpoint of the stability at the time of application of the coating composition, it is preferred that the polymer having a hydrocarbon main chain on the surface thereof is covalently bonded to the hollow fine particles.

Continuing, the hollow microparticles in which the polymer having a hydrocarbon main chain is easily covalently bonded will be described. The polymer having a hydrocarbon main chain is a direct covalent bond, or a cerium oxide on the surface of the hollow cerium oxide microparticles and a polymer having a hydrocarbon main chain, and a coupling agent is interposed between the cerium oxide and the binder. In combination with the valence bond, it can also be said that the binding agent and the polymer are covalently bonded. It is preferred to use a coupling agent as a binder.

The hollow fine particles in which the polymer having a hydrocarbon main chain is easily covalently bonded can be surface-treated with the surface of the hollow cerium oxide particles by treating the surface of the hollow cerium oxide particles with an untreated or a coupling agent or the like. a method of reacting a polymer having a functional group capable of forming a covalent bond, grafting the polymer on the surface of the hollow ceria particle, or (2) treating the surface of the hollow ceria particle with an untreated or coupling agent In the state of being treated, a monomer is polymerized from the surface of the hollow ceria microparticles to grow a polymer chain, and the surface is grafted. As a specific manufacturing As a method, the method described in JP-A-2006-257308 can be used.

In the above production method, from the viewpoint of improving the surface modification ratio, a method of polymerizing a monomer from the surface of the hollow ceria particles to grow a polymer chain and grafting the surface thereof is preferred. The surface treatment of the hollow ceria particles by a coupling agent containing a functional group having a polymerization initiation energy or a chain shifting energy, and a method of polymerizing a monomer to grow a polymer chain to graft the surface thereof is more preferable. A functional group having a polymerization initiation energy or a chain shifting energy, as a surface treatment agent (coupling agent) used for introducing hollow cerium oxide microparticles, an alkoxy metal compound (for example, a titanium coupling agent, an alkoxy decane compound ( A decane coupling agent)) is preferred.

Further, as the hollow ceria particles, hollow ceria-based particles having a conductive metal oxide coating layer can be used. It is preferable that the conductive metal oxide coating layer is a ruthenium oxide coating layer.

The hollow ceria particles may contain two or more kinds of hollow ceria particles having different average particle diameters.

Continuing, a coating composition used when a low refractive index layer other than hollow ceria particles is formed which is porous or void inside is described.

When the pH of the surface (film surface) of the low refractive index layer is controlled to 2.0 to 7.5, the reaction in the low layer folding layer can be suppressed, and the effects of the present invention can be exhibited. Preferably, the surface (film surface) of the low refractive index layer has a pH of from 2.0 to 4.0. In the composition for forming the low refractive index layer, it is preferred to add at least one compound having a pKa value in the range of pKa2 to 7 to control the pH of the surface (film surface) of the low refractive index layer.

Further, pKa is an acid-dissociation number in the acid dissociation reaction described below, which is a logarithm of Ka and a value represented by pKa = -log10Ka.

HA ← → [H ⁺ ][A ^- ] Ka=[H ⁺ ][A ^- ]/[HA] wherein H ⁺ represents an acid species and A ^- represents a conjugate base.

Specific examples of the specific compound having at least one pKa value in the range of pKa 2 to 7 include an aliphatic dibasic acid or an imidazole represented by the following general formula (1) or a derivative thereof. In particular, when the imidazole or the derivative thereof represented by the following general formula (1) is contained in the low refractive index layer-forming composition, it is preferable to exhibit the object of the present invention even after an excessively severe endurance test.

(R ¹ )nA.........(1)

R ¹ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms which may be substituted with an amine group or a hydroxyl group, an alkenyl group and a halogen atom, and when R ¹ is plural, they may be the same or different from each other. The amine group represented by R ¹ may be substituted by 1 or 2 methyl groups or ethyl groups. Further, the alkyl group and the alkenyl group may be substituted by an alkyl group having 1 to 3 carbon atoms. n is an integer from 1 to 3. A represents an imidazolyl group.

The following are specific examples of the imidazole or the derivative thereof represented by the above general formula (1), but are not limited thereto. Further, commercially available products can be used as the imidazole or a derivative thereof.

1-methylimidazole 2-methylimidazole 4-methylimidazolium 4-(2-hydroxyethyl)imidazole 4-(2-aminoethyl)imidazole 2-(2-hydroxyethyl)imidazole 2-ethylimidazole 2-vinylimidazole 4-propylimidazole 2,4-dimethylimidazole 2-chloroimidazole 4,5-bis(2-hydroxyethyl)imidazolium

Examples of the aliphatic dibasic acid include formic acid, propionic acid, malonic acid, succinic acid, tartaric acid, malic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, acetic acid, and the like. Acetic acid is preferred.

The aliphatic dibasic acid or the imidazole or the derivative thereof represented by the following general formula (1) is 0.05 to 10.0% by mass in the coating composition of the low refractive index layer, but from the viewpoint of the stability of the coating composition and the like Preferably.

The coating composition forming the low refractive index layer preferably contains an organic solvent. Examples of specific organic solvents include alcohols (for example, methanol, ethanol, isopropanol, butanol, benzyl alcohol) and ketones (for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, Cyclohexanone), ester (eg, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl formate, ethyl formate, propyl formate, butyl formate), aliphatic hydrocarbons (eg, hexane) ,ring Hexane), halogenated hydrocarbons (eg, dichloromethane, chloroform, carbon tetrachloride), aromatic hydrocarbons (eg, benzene, toluene, xylene), decylamine (eg, dimethylformamide, dimethyl Acetamide, n-methylpyrrolidone), ether (eg, diethyl ether, dioxane, tetrahydrofuran), ether alcohols (eg, 1-methoxy-2-propanol), propylene glycol monomethyl ether, propylene glycol Methyl ether acetate. Among them, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and butanol are particularly preferred.

The solid content concentration in the coating composition forming the low refractive index layer is preferably from 1 to 4% by mass, and when the solid content concentration is 4% by mass or less, coating unevenness is less likely to occur, and when it is 1% by mass or more, the drying load can be reduced. .

It is preferred that the coating composition forming the low refractive index layer contains a fluorine-based or polyoxyalkylene-based surfactant. When the above surfactant is contained, it is effective in reducing coating unevenness or improving the antifouling property of the film surface.

Examples of the fluorine-based surfactant include a monomer containing a perfluoroalkyl group, an oligomer, a polyethylene oxide alkyl ether having a polymer core, a polyethylene oxide alkyl allyl ether, and a polycondensation. Derivatives such as ethylene oxide.

When a fluorine-based surfactant is used, for example, Surflon "S-381", "S-382", "SC-101", "SC-102", "SC-103", and "SC-104" are mentioned. (all are manufactured by Asahi Glass Co., Ltd.) Fluorad "FC-430", "FC-431", "FC-173" (all are Fluorochemicals Sumitomo 3M), EFTOP "EF352", "EF301", "EF303" (all For the new Akita Chemical Co., Ltd.), repairing Begofya "8035", "8036" (all manufactured by Beckman), "BM1000", "BM1100" (both BM. Hemi) , Megaface "F-171", "F-470" (all manufactured by Dainippon Ink Chemical Industry Co., Ltd.).

The fluorine-based surfactant has a fluorine content of 0.05 to 2% by mass, preferably 0.1 to 1% by mass. One type of the above-mentioned fluorine-based surfactants may be used alone or two or more types may be used in combination.

Continue with the description of polyoxyalkylene surfactants.

The polyoxyalkylene surfactant is roughly classified into a pure polyoxane oil and a modified polyoxane oil depending on the kind of the organic group bonded to the ruthenium atom.

Here, the pure polysiloxane oil is a combination of a methyl group, a phenyl group, and a hydrogen atom as a substituent. The modified polyoxyalkylene oil is a component having a secondary derivatization from pure polysiloxane oil. On the one hand, it can also be classified by the reactivity of polyoxyalkylene oil. The above is summarized as follows.

(polyoxane oil) Pure polyoxyalkylene oil

1-1. Non-reactive polyoxane oil: dimethyl, methylphenyl substitution, etc.

1-2. Reactive polyoxane oil: methyl hydrogen substitution, etc.

2. Modified polyoxyalkylene oil

A modified polyoxane oil produced by introducing various organic groups into dimethyl polysiloxane oil.

2-1. Non-reactive polyoxyalkylene oil: alkyl, alkyl/aralkyl, alkyl/polyether, polyether, higher fatty acid ester substitution, and the like.

The alkyl/aralkyl modified polyoxyalkylene oil is a polyoxyalkylene oil in which a part of the methyl group of the dimethyl polysiloxane oil is replaced by a long-chain alkyl group or a phenylalkyl group.

The polyether-modified polyoxyalkylene oil is a polyoxyalkylene-based polymer surfactant in which a hydrophilic polyoxyalkylene group is introduced into a hydrophobic dimethylpolysiloxane.

The higher fatty acid modified polyoxyalkylene oil is a polyoxyalkylene oil in which a methyl group of a dimethylpolysiloxane oil is partially substituted with a higher fatty acid ester.

The amine-modified polyoxyalkylene oil is a polyoxyalkylene oil having a structure in which a part of a methyl group of a polysiloxane oil is substituted with an aminoalkyl group.

The epoxy-modified polyoxyalkylene oil is a polyoxyalkylene oil having a structure in which a part of a methyl group of a polyoxyalkylene oil is substituted with an alkyl group containing an epoxy group.

The carboxyl group-modified or alcohol-modified polyoxyalkylene oil is a polyoxyalkylene oil having a structure in which a part of a methyl group of a polysiloxane oil is substituted with an alkyl group having a carboxyl group or a hydroxyl group.

Among them, polyether modified polyoxyalkylene oil can be added. The number average molecular weight of the polyether modified polyoxyalkylene oil is, for example, 1,000 to 100,000, preferably 2,000 to 50,000, and when the number average molecular weight is less than 1,000, the drying property of the coating film is lowered, and if the number average molecular weight is more than At 100,000, it is not easy to extravasate on the surface of the coating film.

Specific products include L-45, L-9300, FZ-3704, FZ-3703, FZ-3720, FZ-3786, FZ-3501, FZ-3504, FZ-3508, FZ of Japan Unicar Co., Ltd. -3705, FZ-3707, FZ-3710, FZ-3750, FZ-3760, FZ-3785, FZ-3785, Y-7499, Shin-Etsu Chemical Co., Ltd. KF96L, KF96, KF96H, KF99, KF54, KF965, KF968, KF56, KF995, KF351, KF351A, KF352, KF353, KF354, KF355, KF615, KF618, KF945, KF6004, FL100, BYK Japan company's surfactant BYK series, BYK-300/302, BYK-306 , BYK-307, BYK-310, BYK-315, BYK-320, BYK-322, BYK-323, BYK-325, BYK-330, BYK-331, BYK-333, BYK-337, BYK-340, BYK -344, BYK-370, BYK-375, BYK-377, BYK-352, BYK-354, BYK-355/356, BYK-358N/361N, BYK-357, BYK-390, BYK-392, BYK-UV3500 , BYK-UV3510, BYK-UV3570, BYK-Silclean3700, GE Toshiba Polyoxane Co., Ltd. dimethyl polyoxane series, XC96-723, YF3800, XF3905, YF3057, YF3807, YF3802, YF3897 and so on.

Further, the polyoxyalkylene surfactant is a surfactant in which a part of a methyl group of the polyoxyalkylene oil is substituted with a hydrophilic group. The substitution position is a branch of polyoxyalkylene oil, two ends, a single end, two end branches, and the like. Examples of the hydrophilic group include a polyether, polyglycerin, pyrrolidone, betaine, sulfate, phosphate, and a 4-stage salt.

As the polyoxyalkylene surfactant, a hydrophobic group is preferably a nonionic surfactant composed of dimethyl polyoxyalkylene and a hydrophilic group of a polyoxyalkylene group.

The nonionic surfactant is a general term for a surfactant which does not have a group which dissociates into an ion in an aqueous solution. In addition to having a hydrophobic group, it also has a hydroxyl group as a hydrophilic group and a polyoxyalkylene chain. (Polyethylene oxide) or the like as a hydrophilic group. Hydrophilicity is the number of hydroxyl groups with alcohol The increase is further enhanced by the lengthening of the polyoxyalkylene chain (polyethylene oxide chain). When a nonionic surfactant composed of a dimethylpolysiloxane and a hydrophilic group is a polyoxyalkylene group is used, the unevenness of the low refractive index layer or the antifouling property of the film surface is enhanced. It is presumed that when the hydrophobic group formed of polymethyl siloxane is aligned to the surface, a surface of the film which is difficult to be contaminated can be formed.

Specific examples of the nonionic surfactant include, for example, a polyoxonane surfactant SILWET L-77, L-720, L-7001, L-7002, L-7604, Y manufactured by Nippon Unicar Co., Ltd. -7006, FZ-2101, FZ-2104, FZ-2105, FZ-2110, FZ-2118, FZ-2120, FZ-2122, FZ-2123, FZ-2130, FZ-2154, FZ-2161, FZ-2162 , FZ-2163, FZ-2164, FZ-2166, FZ-2191, SUPERSILWET SS-2801, SS-2802, SS-2803, SS-2804, SS-2805, etc.

These are preferably a structure in which a hydrophobic group is composed of dimethyl polyoxane, and a hydrophilic group is a nonionic surfactant composed of a polyoxyalkylene group, and a dimethyl polyoxyalkylene moiety is used. Preferably, the polyoxyalkylene chain is a linear repeat block copolymer which is alternately and repeatedly bonded. The unevenness suppression or the leveling property when coating a coating composition having a low inflection rate layer is preferred. As such a specific example, a polyoxonane surfactant ABN SILWET FZ-2203, FZ-2207, FZ-2208, FZ-2222, etc., manufactured by Nippon Unicar Co., Ltd., may be mentioned.

The coating composition forming the low refractive index layer contains the reactive modified polyoxyalkylene resin (hereinafter also referred to as the following description) from the viewpoint that the object of the present invention can be easily exhibited after the endurance test under more severe conditions. Reactive modification Polyoxane oil is preferred.

2-2. Reactive modified polyoxyalkylene oil: amine group, epoxy group, carboxyl group, alcohol substitution, and the like.

The reactive modified polyoxyalkylene resin may be an amine group, an epoxy group, a carboxyl group, a hydroxyl group, a methacryl group, a thiol group, or the like at the end or both ends of the polyoxyalkylene. A reactive type modified polyoxyalkylene resin substituted with a phenol or the like. Specific examples of the amine-modified polyoxyalkylene resin include KF-860, KF-861, X-22-161A, X-22-161B (above, Shin-Etsu Chemical Co., Ltd.), FM-3311, FM-3325 (above, chisso Co., Ltd.), as the epoxy-modified polyoxyalkylene resin, KF-105, X-22-163A, X-22-163B, KF-101, KF-1001 (The above, manufactured by Shin-Etsu Chemical Co., Ltd.), as the polyether-modified polyoxyalkylene resin, X-22-4272 and X-22-4952, and a carboxyl modified polyoxyalkylene resin can be mentioned. X-22-3701E, X-22-3710 (above, Shin-Etsu Chemical Co., Ltd.), as a methanol-modified polyoxyalkylene resin, KF-6001, KF-6003 (above, Shin-Etsu Chemical Industry) As a methacrylic acid-modified polyoxyalkylene resin, X-22-164C (above, Shin-Etsu Chemical Co., Ltd.) can be used as a hydrogen-sulfur-modified polyoxyalkylene resin. KF-2001 (above, Shin-Etsu Chemical Co., Ltd.), as a phenol-modified polyoxyalkylene resin, X-22-1821 (X-22-1821) Above, Shin-Etsu Chemical Co., Ltd.). Examples of the hydroxy-modified polyoxyalkylene resin include FM-4411, FM-4421, FM-DA21, and FM-DA26 (above, Chisso Co., Ltd.) System). Others include X-22-170DX, X-22-2426, and X-22-176F (manufactured by Shin-Etsu Chemical Co., Ltd.) which have a single-end reactive polyoxyalkylene resin.

The above surfactant may be used in combination with other surfactants, and may be used in combination with an anionic surfactant such as a suitable sulfonate, sulfate or phosphate ester, and may also have a polyethylene oxide chain. A nonionic surfactant such as an ether group or an ether ester type of a hydrophilic group is used in combination. When the amount of the surfactant added is 0.05 to 3.0% by mass in the low refractive index coating composition, not only the water repellency, oil repellency, and antifouling properties of the coating film can be improved, but also the surface scratch resistance can be exhibited. The effect is preferred.

The coating composition forming the low refractive index layer may contain other cerium oxide microparticles. The other cerium oxide fine particles are not particularly limited, and examples thereof include colloidal cerium oxide. As a specific example of the colloidal cerium oxide, in the case where the cerium oxide is dispersed in a colloidal form in water or an organic solvent, it may be in the form of a spherical shape, a needle shape or a bead group.

The average particle size of the colloidal ceria is preferably in the range of 50 to 300 nm, and the coefficient of variation is preferably from 1 to 40%. The average particle diameter can be measured by an electron micrograph using a scanning electron microscope (SEM) or the like. It can also be measured by a particle size distribution meter or the like using a dynamic astigmatism method or a static astigmatism method.

The colloidal cerium oxide may be a seller, and examples thereof include the Snowtex series of Nissan Chemical Industries Co., Ltd., the Cataloid-S series of Catalyst Chemical Industries, and the Rebala series of Bayer. Further, the primary particles of the colloidal ceria or cerium oxide which are cationically modified with alumina sol or aluminum hydroxide are bonded to each other by metal ions having a valence of 2 or more, and then It is also preferred that the bead group colloidal cerium oxide is formed into a bead group. Examples of the bead group colloidal cerium oxide include the Snowtex AK series, the Snowtex PS series, and the Snowtex UP series of Nissan Chemical Industries Co., Ltd., specifically, IPS-ST-L (isopropyl alcohol dispersion, particle diameter 40 to 50 nm, solid content 30%) ), MEK-ST-MS (methyl ethyl ketone dispersion, particle diameter 17 to 23 nm, solid content 35).

When the low refractive index layer-forming coating composition contains colloidal cerium oxide, the solid content in the low refractive index layer is preferably from 10 to 60% by mass, and from 30 to 60% by mass, from the viewpoint of film strength.

Further, it is preferable that the low refractive index layer is formed in the coating composition in an amount of 5 to 80% by mass based on the solid content in the low refractive index layer. The adhesive is a function of adhering hollow ceria particles or colloidal ceria to maintain a structure of a low refractive index layer containing voids. The amount of the adhesive can be used not only to fill the voids but also to maintain the strength of the low refractive index layer.

Examples of the adhesive include a metal alkoxide compound, a hydrolyzate thereof or a polycondensate thereof, and polyvinyl alcohol, polyethylene oxide, polymethyl methacrylate, and polymethacrylate. , diethyl acetyl cellulose, triethylene fluorenyl cellulose, nitro cellulose, polyester, alkyd resin, fluoroacrylate, fluoropolymer, and the like. Examples of the fluoropolymer include fluoroolefins (for example, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, perfluorooctylethylene, hexafluoropropylene, perfluoro-2,2-dimethyl-1,3). - a partially or fully fluorinated alkyl ester derivative such as dioxetane (for example, VISCOAT6FM (made by Osaka Organic Chemical Co., Ltd.) or M-2020 (made by Daikin)), completely or partially fluorinated a vinyl ether or the like. Among them, perfluoroolefins are preferred, and the refractive index is From the viewpoints of solubility, transparency, and availability, hexafluoropropylene is particularly preferred.

Further, as the alkoxide metal compound, a decane coupling agent is particularly preferable from the viewpoint of excellent properties of the binder of the hollow cerium oxide microparticles. The following describes the decane coupling agent. As the decane coupling agent, a decane coupling agent represented by the following general formula (3) is preferred.

(Z-L ¹ ) _m -Si-(R ² ) _n R ³ _4-m+n (3) wherein Z is a functional group having a polymerization initiation energy or a chain shifting energy. L ¹ is a divalent linking group having 10 or less carbon atoms.

Among them, L ^{1 is} preferably an alkylene group having 1 to 10 carbon atoms or a plurality of alkylene groups bonded via a linking group (for example, an ether, an ester or a decylamine). The alkylene group may have a branch. The alkylene group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, a hydrogenthio group, a carboxyl group, an epoxy group, an alkyl group, and an aryl group.

Further, in the above general formula (3), R ² is an alkyl group having 1 to 10 carbon atoms. R ³ is a hydroxyl group or a hydrolyzable group. R ³ is preferably an alkoxy group having 1 to 5 carbon atoms or a halogen atom, and more preferably a methoxy group, an ethoxy group or a chlorine atom. And 1≦m≦3, 0≦n≦2, and 1≦m+n≦3.

Examples of the substituent having the decane coupling agent represented by the above general formula (3) may contain a hydroxyl group, a halogen atom (for example, Cl, Br, F, I), a cyano group, a nitro group, a substituent group, a sulfo group, and a carbon. An alkyl group having 1 to 8 atoms (for example, methyl, ethyl, isopropyl, butyl, hexyl, cyclopropyl, cyclohexyl) , 2-hydroxyethyl, 4-carboxybutyl, 2-methoxyethyl, 2-diethylaminoethyl), an alkenyl group having 2 to 8 carbon atoms (for example, ethylene, allyl, 2 -hexenyl), an alkynyl group having 2 to 8 carbon atoms (for example, an ethynyl group, a 1-butynyl group, a 3-hexynyl group), an aralkyl group having 7 to 12 carbon atoms (for example, a benzyl group) , phenethyl), an aryl group having 6 to 10 carbon atoms (for example, phenyl, naphthyl, 4-carboxyphenyl, 4-ethylguanidinylphenyl, 3-methanesulfonamide phenyl, 4-methyl) An oxyphenyl group, a 3-carboxyphenyl group, a 3,5-dicarboxyphenyl group, a 4-methanesulfonamide phenyl group, a 4-butylsulfonylamine phenyl group, and a fluorenyl group having 1 to 10 carbon atoms (for example) , ethyl hydrazino, benzhydryl, propyl fluorenyl, butyl fluorenyl), alkoxycarbonyl group having 2 to 10 carbon atoms (for example, methoxycarbonyl group, ethoxycarbonyl group), aromatic group having 7 to 12 carbon atoms An oxycarbonyl group (for example, a phenoxycarbonyl group, a naphthyloxycarbonyl group), an aminomethylcarbenyl group having 1 to 10 carbon atoms (for example, an unsubstituted aminomethyl fluorenyl group, a methylaminomethyl fluorenyl group, a diethyl group) Aminomethyl fluorenyl, anilinomethyl fluorenyl), alkoxy group having 1 to 8 carbon atoms (for example, methoxy, ethoxy, butyl a group, a methoxyethoxy group, an aryloxy group having 6 to 12 carbon atoms (for example, a phenoxy group, a 4-carboxyphenoxy group, a 3-methylphenoxy group, a naphthyloxy group), and a carbon number 2 to 12 decyloxy groups (for example, acetoxy group, benzamethyleneoxy group), sulfonyloxy group having 1 to 12 carbon atoms (for example, methylsulfonyloxy group, phenylsulfonyloxy group), amine a substituted amino group having 1 to 10 carbon atoms (for example, dimethylamino group, diethylamino group, 2-carboxyethylamino group) or a decylamino group having 1 to 10 carbon atoms (for example, acetaminophen, Benzoylamine), a sulfonylamino group having 1 to 8 carbon atoms (for example, methanesulfonamide, benzenesulfonamide, butazone, octanesulfonamide), and a ureido group having 1 to 10 carbon atoms (for example, urea group, methylurea group), alkoxycarbonylamino group having 2 to 10 carbon atoms (for example) For example, methoxycarbonylamino group, ethoxycarbonylamino group), alkylthio group having 1 to 12 carbon atoms (for example, methyl sulfide, ethyl sulfur, octyl sulfide), carbon number 6 to 12 Arylthio group (for example, phenylsulfide, naphthylsulfide), alkylsulfonyl group having 1 to 8 carbon atoms (for example, methylsulfonyl group, butylsulfonyl group), carbon number 7~ An arylsulfonyl group of 12 (for example, phenylsulfonyl, 2-naphthylsulfonyl), an aminesulfonyl group, a substituted aminesulfonyl group having 1 to 8 carbon atoms (for example, methylaminesulfonyl) And a heterocyclic group (for example, 4-pyridine, 1-piperidinyl, 2-furyl, fluorenyl, 2-thiol, 2-pyrrolyl, 2-quinolinylmorpholino).

Further, the decane coupling agent represented by the following general formula (4) is also preferable.

_{Z- (CH 2) n -Si-} R 4 3 ......... (4) the formula, Z is the case of the above general formula (3) of the same, n represents an integer of 1 to 10.

R ⁴ represents an alkoxy group having 1 to 5 carbon atoms or a halogen atom, and a methoxy group, an ethoxy group, and a chlorine atom are preferred.

Continuing to mention a preferred example of a decane coupling agent containing a functional group having a polymerization initiation property represented by the above general formula (3).

XCH ₂ C(O)O(CH ₂ ) ₃ Si(OCH ₃ ) ₃ CH ₃ C(H)(X)C(O)O(CH ₂ ) ₃ Si(OCH ₃ ) ₃ (CH ₃ ) ₂ C( X)C(O)O(CH ₂ ) ₃ Si(OCH ₃ ) ₃ XCH ₂ C(O)O(CH ₂ ) ₆ Si(OCH ₃ ) ₃ CH ₃ C(H)(X)C(O)O (CH ₂ ) ₆ Si(OCH ₃ ) ₃ (CH ₃ ) ₂ C(X)C(O)O(CH ₂ ) ₆ Si(OCH ₃ ) ₃ XCH ₂ C(O)O(CH ₂ ) ₃ Si( OC ₂ H ₅ ) ₃ CH ₃ C(H)(X)C(O)O(CH ₂ ) ₃ Si(OC ₂ H ₅ ) ₃ (CH ₃ ) ₂ C(X)C(O)O(CH _{2 ) 3 Si (OC 2 H 5} ) 3 XCH 2 C (O) O (CH 2) 6 Si (OC 2 H 5) 3 CH 3 C (H) (X) C (O) O (CH 2) 6 Si (OC ₂ H ₅ ) ₃ (CH ₃ ) ₂ C(X)C(O)O(CH ₂ ) ₆ Si(OC ₂ H ₅ ) ₃ XCH ₂ C(O)O(CH ₂ ) ₃ SiCl ₃ CH ₃ C(H)(X)C(O)O(CH ₂ ) ₃ SiCl ₃ (CH ₃ ) ₂ C(X)C(O)O(CH ₂ ) ₃ SiCl ₃

In the formula, X is a chlorine, bromine or iodine atom, and particularly preferably a bromine atom.

Further, specific examples of the decane coupling agent include methyltrimethoxydecane, methyltriethoxydecane, methyltrimethoxyethoxydecane, methyltriacetoxydecane, and methyltributyloxide. Base decane, ethyl trimethoxy decane, ethyl triethoxy decane, ethylene trimethoxy decane, ethylene triethoxy decane, ethylene triacetoxy decane, ethylene trimethoxy ethoxy decane, phenyl trimethoxy Base decane, phenyl triethoxy decane, phenyl triacetoxy decane, γ-chloropropyl trimethoxy decane, γ-chloropropyl triethoxy decane, γ-chloropropyl triacetoxy decane, 3 , 3,3-trifluoropropyltrimethoxydecane, γ-glycidoxypropyltrimethoxydecane, γ-glycidoxypropyltriethoxydecane, γ-(β-epoxy Propoxyethoxy)propyltrimethoxydecane, β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, β-(3,4-epoxycyclohexyl)ethyltri Ethoxy decane, γ-propylene methoxy propyl trimethoxy decane, γ-methyl propylene methoxy propyl trimethoxy decane, γ-amino propyl Trimethoxy decane, γ-aminopropyl triethoxy decane, γ-hydrothiopropyltrimethoxy decane, γ-hydrothiopropyltriethoxy decane, N-β-(amino group Ethyl)-γ-aminopropyltrimethoxydecane, and β-cyanoethyltriethoxydecane, dimethyldimethoxydecane, phenylmethyldimethoxydecane, dimethyl Diethoxydecane, phenylmethyldimethoxydecane, dimethyldiethoxydecane, phenylmethyldiethoxydecane, γ-glycidoxypropylmethyldiethoxy Decane, γ-glycidoxypropylmethyldimethoxydecane, γ-glycidoxypropylphenyldiethoxydecane, γ-chloropropylmethyldiethoxydecane, II Methyl diacetoxy decane, γ-propylene methoxy propyl methyl dimethoxy decane, γ-propylene methoxy propyl methyl diethoxy decane, γ-methyl propylene methoxy propyl group Dimethoxy decane, γ-methyl propylene methoxy propyl methyl diethoxy decane, γ-hydrothiopropyl methyl dimethoxy decane, γ-hydrothiopropyl methyl group Ethoxy decane, γ-aminopropyl Methyl dimethoxy decane, γ-aminopropyl methyl diethoxy decane, methyl ethylene dimethoxy decane, and methyl ethylene diethoxy decane.

Among them, ethylene trimethoxy decane, ethylene triethoxy decane, ethylene triacetoxy decane, ethylene trimethoxy ethoxy decane, γ-acryloxypropyl trimethoxy decane having a double bond in the molecule, And γ-methacryloxypropyltrimethoxydecane, and those having a 2-substituted alkyl group, γ-propylene methoxypropyl methyl dimethoxy decane, γ-propylene oxime Propyl methyl diethoxy decane, γ-methyl propylene methoxy propyl methyl dimethoxy decane, γ-methyl propylene methoxy propyl methyl diethoxy decane, methyl ethylene Dimethoxydecane, and methylethylene diethoxynonane, preferably γ-acryloxypropyltrimethoxydecane, and γ-methylpropenyloxypropane Trimethoxy decane, γ-propylene methoxy propyl methyl dimethoxy decane, γ-propylene methoxy propyl methyl diethoxy decane, γ-methyl propylene methoxy propyl methyl Dimethoxydecane and γ-methacryloxypropylmethyldiethoxydecane are particularly preferred.

The low refractive index layer can be applied by coating a low refractive index layer by a known method such as a gravure coater, a dip coater, a reverse coater, a coil bar coater, a die coater, or a spray method. The composition is dried by heating after application, and is formed after hardening treatment as necessary.

The coating amount is suitably from 0.05 to 100 μm in wet film thickness, preferably from 0.1 to 50 μm. Further, the solid content concentration of the coating composition was adjusted to a dry film thickness of the above film pressure.

Further, after the low refractive index layer is formed, it may be subjected to a heat treatment at a temperature of 50 to 160 °C. The heat treatment period may be appropriately determined by the set temperature, for example, only 50 ° C, preferably 3 days or more and less than 30 days, and only 160 ° C for 10 minutes or more and 1 day or less. It is better. As a curing method, a method of thermally hardening by heating, a method of curing by irradiation with light such as ultraviolet rays, or the like. When it is thermally hardened, the heating temperature is preferably from 50 to 300 ° C, preferably from 60 to 250 ° C, more preferably from 80 to 150 ° C. When it is cured by light irradiation, the exposure amount of the irradiation light is preferably 10 mJ/cm ² to 10 J/cm ^{2 , and more} preferably 100 mJ/cm ² to 500 mJ/cm ² .

The wavelength region of the light to be irradiated is not particularly limited, but it is preferably a wavelength having an ultraviolet region. Specifically, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used. The irradiation conditions vary depending on the light, but the irradiation amount of the active line is generally 5 to 500 mJ/cm ² , preferably 5 to 150 mJ/cm ² , and particularly preferably 20 to 100 mJ/cm ² .

Continuing, a high refractive index layer having a higher refractive index than the support disposed between the low refractive index layer and the transparent resin film will be described.

(high refractive index layer)

The high refractive index layer is a layer having a higher refractive index than the transparent film substrate. The preferred refractive index of the high refractive index layer is preferably in the range of 1.5 to 2.2 measured at a wavelength of 550 nm at 23 ° C. As a means for adjusting the refractive index of the high refractive index layer, the type and amount of the metal oxide fine particles to be used are preferably 1.80 to 2.60, and more preferably 1.85 to 2.50, of the metal oxide fine particles described below. Further, the film pressure of the high refractive index layer is preferably 5 nm to 1 μm, more preferably 10 nm to 0.2 μm, and most preferably 30 nm to 0.1 μm, as the characteristics of the optical dry layer.

Continuing, the metal oxide fine particles used for adjusting the refractive index of the high refractive index layer will be described. The type of the metal oxide fine particles is not particularly limited, and at least one selected from the group consisting of Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si can be used. Metal oxides of elements of P and S. These metal oxide fine particles may be doped with a trace atom of Al, In, Sn, Sb, Nb, a halogen element, Ta or the like. Also, these may be mixtures. Wherein at least one metal oxide fine particle selected from the group consisting of zirconium oxide, cerium oxide, tin oxide, zinc oxide, indium tin oxide (ITO), antimony-doped tin oxide (ATO), and zinc antimonate is used as a main component. It is especially good. It is especially preferred to contain zinc silicate particles.

The average particle diameter of the primary particles of these metal oxide fine particles is in the range of 10 nm to 200 nm, and particularly preferably 10 to 150 nm. The average particle diameter of the metal oxide fine particles can be measured by an electron micrograph such as a scanning electron microscope (SEM), and can be measured by a particle size distribution meter or the like using a dynamic astigmatism method or a static astigmatism method. When the particle diameter is too small, aggregation tends to occur, and the dispersibility is deteriorated. When the particle size is too large, the fog value will be significantly improved. The shape of the metal oxide fine particles is preferably a rice grain shape, a spherical shape, a cubic shape, a spindle shape, a needle shape or an indefinite shape.

The metal oxide fine particles can be surface-treated by an organic compound. When the surface of the metal oxide fine particles is surface-modified by an organic compound, the dispersion stability in the organic solvent can be improved, and the dispersed particle diameter can be easily controlled, and aggregation and precipitation can be suppressed over time. Therefore, the amount of surface modification of the organic compound is preferably 0.1% by mass to 5% by mass, and preferably 0.5% by mass to 3% by mass, based on the metal oxide particles. Examples of the organic compound used for the surface treatment include a polyhydric alcohol, an alkanolamine, a stearic acid, a decane coupling agent, and a titanate coupling agent. The decane coupling agent described later is preferred. It is also possible to combine two or more kinds of surface treatments.

The ratio of the metal oxide fine particles to be used and the adhesive such as the active light-curing resin to be described later differs depending on the type of the metal oxide fine particles, the particle size, and the like, but the volume ratio is 2 to the latter for the former 1 The former 2 is preferably the latter.

The amount of the metal oxide fine particles used is preferably 5% by mass to 85% by mass in the high refractive index layer, and preferably 10% by mass to 80% by mass, and 20 to 75% by mass. The mass % is the best. If the amount used is too small, the desired refractive index or the effect of the present invention cannot be obtained, and when it is too large, deterioration of film strength or the like occurs.

The metal oxide fine particles are provided in a dispersion state in a medium, and are provided in a coating liquid for forming a high refractive index layer. As the dispersion medium of the metal oxide particles, a liquid having a boiling point of 60 to 170 ° C is preferably used. Specific examples of the dispersion solvent include water, alcohols (for example, methanol, ethanol, isopropanol, butanol, benzyl alcohol), and ketones (for example, acetone, methyl ethyl ketone, and methyl isobutyl group). Ketones, cyclohexanone), keto alcohols (eg, diacetone alcohols), esters (eg, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl formate, ethyl formate, propyl formate) , butyl formate), aliphatic hydrocarbons (eg, hexane, cyclohexane), halogenated hydrocarbons (eg, dichloromethane, chloroform, carbon tetrachloride), aromatic hydrocarbons (eg, benzene, toluene, xylene) , guanamine (eg, dimethylformamide, dimethylacetamide, n-methylpyrrolidone), ether (eg, diethyl ether, dioxane, tetrahydrofuran), ether alcohols (eg, 1-a Oxy-2-propanol), propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate. Among them, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and butanol are particularly preferred.

Further, the metal oxide fine particles can be dispersed in the medium using a disperser. Examples of the dispersing machine include a sanding mill (for example, a bead mill), a high-speed impeller mill, a quartz disc grinder, a roll grinder, a stirring ball mill, and a colloid mill. It is especially good for scrub sanders and high speed impeller mills. Further, a preliminary dispersion treatment can be performed. Examples of the dispersing machine used in the preliminary dispersion treatment include a ball mill, a three-roll mill, a kneader, and an extruder. It is preferred to contain a dispersing agent.

Further, metal oxide fine particles having a core/shell structure may be contained. The shell can be formed in one layer around the core, and a plurality of layers can be formed to further improve light resistance. The core is preferably covered by the shell.

The core may use titanium oxide (rutile type, anatase type, amorphous type, etc.), zirconia, zinc oxide, cerium oxide, indium oxide doped tin oxide, tin oxide doped with antimony, etc., but rutile may also be used. The type of titanium oxide is used as a main component.

The shell is preferably composed of an inorganic compound other than titanium oxide as a main component, and is formed of an oxide or sulfide of a metal. For example, an inorganic compound containing ceria (ceria), alumina, zirconia, zinc oxide, tin oxide, cerium oxide, indium oxide, iron oxide, zinc sulfide or the like as a main component can be used. Among them, alumina, ceria, and zirconia are preferred. Also, it may be a mixture of them.

For the coverage of the core shell, the average coverage is 2 to 50% by mass. It is preferably from 3 to 40% by mass, more preferably from 4 to 25% by mass. When the amount of coverage of the shell is too large, the refractive index of the fine particles is lowered, and when the amount of coverage is too small, the light resistance is deteriorated. Two or more kinds of metal oxide fine particles may be used in combination.

As the core titanium oxide, it can be produced by a liquid phase method or a gas phase method. Further, as a method of forming a shell around a core, for example, U.S. Patent No. 3,410,708, Japanese Patent No. Sho 58-47061, U.S. Patent No. 2,885,366, the same as No. 3,437,502, British Patent No. 1,134,249, and U.S. Patent No. 3,383,231 The method described in British Patent No. 2,629,953 and the same as No. 1,365,999. The high refractive index layer or the low refractive index layer may contain a compound represented by the following general formula (5) or a chelate compound thereof, and the physical properties such as hardness can be improved.

AnMBx-n.........(5) In the formula, M represents a metal atom, A represents a hydrolyzable functional group or a hydrocarbyl group having a hydrolyzable functional group, and B represents an atomic group in which a metal atom M is covalently bonded or ionically bonded. x represents the valence of the metal atom M, and n represents an integer of 2 or more and x or less.

Examples of the hydrolyzable functional group A include a halogen such as an alkoxy group or a chlorine atom, an ester group, and a guanamine group.

The metal compound belonging to the above formula (5) contains an alkoxide having two or more alkoxy groups directly bonded to a metal atom, or a chelating compound thereof. The preferred metal compound may, for example, be a titanium alkoxide, a zirconium alkoxide or a chelating compound thereof. Titanium alkoxide has a high reaction rate and a high refractive index and is easy to handle. However, it has a photocatalytic action and deteriorates light resistance when added in a large amount. Since zirconium alkoxide has a high refractive index but is easily cloudy, it is necessary to pay attention to exposure management at the time of coating.

Further, the titanium alkoxide has an effect of promoting the reaction of the ultraviolet curable resin and the metal alkoxide, and the physical properties of the coating film can be improved by adding only a small amount.

Examples of the titanium alkoxide include tetramethoxytitanium, tetraethoxytitanium, tetra-iso-propoxytitanium, tetra-n-propoxytitanium, tetra-n-butoxytitanium, and tetra. -sec-butoxytitanium, tetra-tert-butoxytitanium, and the like.

Examples of the zirconium alkoxide include tetramethoxy zirconium, tetraethoxy zirconium, tetra-iso-propoxy zirconium, tetra-n-propoxy zirconium, and tetra-n-butoxy zirconium. Tetra-sec-butoxyzirconium, tetra-tert-butoxyzirconium, and the like.

Preferred examples of the chelating agent to form a chelating compound to be a free metal compound include alkanolamines such as diethanolamine and triethanolamine, glycols such as ethylene glycol, diethylene glycol and propylene glycol, and acetamidine. A molecular weight of 10,000 or less such as acetone or ethyl acetate. By using these chelating agents, it is also stable in the mixing of water and the like, and a chelate compound having an excellent reinforcing effect of the coating film can be formed. The addition amount of the above chelate compound is preferably adjusted to 0.3 to 5% by mass in the high refractive index layer. When the amount is less than 0.3% by mass, the scratch resistance may be insufficient, and when it exceeds 5% by mass, the light resistance tends to be deteriorated.

Further, it is preferable that the high refractive index layer contains an ionizing radiation-curable resin as an adhesive of metal oxide fine particles to improve the film forming property or physical properties of the coating film. As the ionizing radiation-curable resin, a monomer or oligomer having two or more functional groups which are directly or accepting a photopolymerization initiator by irradiation with active light such as ultraviolet rays or electron beams can be used. The polymerization reaction is carried out indirectly. Examples of the functional group include a group having an unsaturated double bond such as a (meth)acrylenyloxy group, an epoxy group, a decyl alcohol group, and the like. Among them, a radical polymerizable monomer or oligomer having two or more unsaturated double bonds can also be used. The photopolymerization initiator can be combined as necessary. As such an ionizing radiation-curable resin, a polyol acrylate, an epoxy acrylate, a urethane acrylate, a polyester acrylate, or a mixture thereof can be used. For example, a polyfunctional acrylate compound or the like is exemplified by a compound selected from the group consisting of pentaerythritol polyfunctional acrylate, dipentaerythritol polyfunctional acrylate, pentaerythritol polyfunctional methacrylate, and dipentaerythritol polyfunctional methacrylate. good. Among them, the multifunctional acrylate compound is A compound having two or more acryloxy groups and/or methacryloxy groups in the molecule.

Examples of the monomer of the polyfunctional acrylate compound include ethylene glycol diacrylate, diethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, and three. Hydroxymethylpropane triacrylate, trimethylolethane triacrylate, tetramethylol methane triacrylate, tetramethylol methane tetraacrylate, pentaglycerol triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate Ester, pentaerythritol tetraacrylate, glycerol triacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, ginseng (propylene oxyethyl) trimeric isocyanate, B Diol dimethacrylate, diethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethyl Acrylate, trimethylolethane trimethacrylate, tetramethylol methane trimethacrylate, tetramethylol methane tetramethacrylate, pentaglycerol trimethacrylate, Pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, glycerol trimethacrylate, dipentaerythritol trimethacrylate, dipentaerythritol tetramethacrylate, dipentaerythritol penta A acrylate or dipentaerythritol hexamethacrylate is preferred. These compounds may be used alone or in combination of two or more. Further, it may be an oligomer such as a dimer or a trimer of the above monomer.

The amount of the ionizing radiation-curable resin to be added is preferably 15% by mass or more and less than 50% by mass of the solid content in the high refractive index composition.

In order to promote the hardening of the ionizing radiation-curable resin, a photopolymerization initiator having a mass ratio of 3:7 to 1:9 and a propylene-based compound having two or more polymerizable unsaturated bonds in the molecule are preferred.

Specific examples of the photopolymerization initiator include acetophenone, benzophenone, hydroxybenzophenone, michelone, α-amine oxime ester, thioxanthone, and the like, but It is not particularly limited.

It is preferred to use an organic solvent when coating the high refractive index layer. As the organic solvent, for example, an alcohol (for example, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, second butanol, third butanol, pentanol, hexanol, cyclohexanol) may be mentioned. , benzyl alcohol, etc.), polyols (for example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butanediol, hexanediol, pentane Alcohols, glycerol, hexanetriol, thiodiethanol, etc.), polyol ethers (eg, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether) , diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether, triethylene glycol single Ethyl ether, ethylene glycol monophenyl ether, propylene glycol monophenyl ether, etc., amines (for example, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethyl Morpholine, Ethyldiamine, Diethyl Ethyldiamine, Tri-Extended Ethyltetramine, Tetraethylidene Ethylpentamine, Polyethylenimine, Pentamethyldiethylidene Triamine, Tetramethylextension a base diamine or the like), a guanamine (for example, formamide, N,N-dimethylformamide, N,N-dimethylacetamide, etc.), a heterocyclic ring (for example, 2-pyrrolidone, N-methyl-2-pyrrolidone, cyclohexyl pyrrolidone, 2-oxazolone, 1,3-dimethyl-2-imidazolidone, etc.), anthraquinones (eg, dimethyl It is preferable to use an alcohol, a polyhydric alcohol or a polyhydric alcohol ether in particular, such as hydrazine or the like (for example, cyclobutyl hydrazine), urea, acetonitrile or acetone.

The high refractive index layer may be a gravure coater, a dip coater, a reverse coater, a coil bar coater, a die coater, or a spray coating or a spray coating using the above composition, which is equal to a transparent resin film, Or the surface of the hard coating layer is applied to a wet film thickness of 0.1 to 100 μm, and after drying, it is dried by heating and hardened as necessary. The hardening step can use the contents described in the low refractive index layer.

Further, in order to make the dry film thickness the film pressure, it is necessary to adjust the solid content concentration of the coating composition.

(hard coating layer: active wire hardening resin layer)

In the antireflection film of the present invention, when a layer containing a living line-curable resin as a hard coat layer is provided between the transparent resin film and the antireflection layer, the antireflection film can be used as a polarizing plate as described later. In the step, it is not easy to be hurt and is better.

The active-strand-hardened resin layer is a layer formed by a resin which is cured by a crosslinking reaction or the like by irradiation with an active line such as ultraviolet rays or electron beams (hereinafter also referred to as an active energy ray). As the active wire-curable resin, a component containing a monomer having an ethylenically unsaturated double bond is preferably used, and it is cured by irradiation with an active wire such as an ultraviolet ray or an electron beam to form an active ray-curable resin layer. The active-ray-curing resin is preferably represented by an ultraviolet curable resin or an electron-curable resin, but it is preferably a resin which is cured by ultraviolet irradiation.

As the ultraviolet curable resin, for example, ultraviolet curable urethane is used. Acrylic resin, ultraviolet curable polyester acrylate resin, ultraviolet curable epoxy acrylate resin, ultraviolet curable polyol acrylate resin, or ultraviolet curable epoxy resin, etc. An ultraviolet curable acrylate resin is preferred.

The ultraviolet curable urethane acrylate resin is generally a product obtained by reacting a polyester polyol with an isocyanate monomer or a prepolymer, and further having 2-hydroxyethyl acrylate and 2-hydroxyethyl group. A methacrylate (hereinafter, a methacrylate containing methacrylate is represented only by acrylate) or a hydroxyl group acrylate monomer such as 2-hydroxypropyl acrylate can be easily obtained by a reaction. For example, those described in JP-A-59-151110 can be used.

For example, it is preferred to use a mixture with 100 parts of Unitek 17-806 (manufactured by Dainippon Ink Co., Ltd.) and 1 part of CORONET L (manufactured by Nippon Polyurethane Co., Ltd.).

The ultraviolet curable polyester acrylate-based resin is generally formed by reacting a polyester polyol with a 2-hydroxyethyl acrylate or a 2-hydroxy acrylate monomer, and can be easily formed. - 151112.

Specific examples of the ultraviolet curable epoxy acrylate-based resin include an epoxy acrylate as an oligomer, and a reactive diluent and a photopolymerization initiator are added thereto and reacted. For example, those described in Japanese Laid-Open Patent Publication No. Hei 1-105738 can be used.

Specific examples of the ultraviolet curable polyol acrylate resin include trimethylolpropane triacrylate and ditrimethylolpropane tetrapropene. An acid ester, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, alkyl-modified dipentaerythritol pentaacrylate, and the like.

Specific examples of the photopolymerization initiator of these ultraviolet curable resins include benzo and its derivatives, acetophenone, benzophenone, hydroxybenzophenone, michelone, and α-amine oxime ester. , thioxanthone, etc. and their derivatives. A photosensitizer can be used at the same time. The above photopolymerization initiator can also be used as a photosensitizer. Further, in the case of using an epoxy acrylate-based photopolymerization initiator, a sensitizer such as n-butylamine, triethylamine or tri-n-butylphosphine can be used. The photopolymerization initiator or the photosensitizer used in the ultraviolet curable resin composition is 0.1 to 15 parts by mass, preferably 1 to 10 parts by mass, per 100 parts by mass of the composition.

As the resin monomer, for example, when the unsaturated double bond is one of the monomers, methacrylate, ethacrylate, butyl acrylate, benzyl acrylate, cyclohexyl acrylate, vinyl acetate may be mentioned. , general monomers such as styrene. Further, examples of the monomer having two or more unsaturated double bonds include ethylene glycol diacrylate, propylene glycol diacrylate, divinylbenzene, 1,4-cyclohexane diacrylate, and 1,4-cyclohexyl group. Dimethyl diacrylate, trimethylolpropane triacrylate, pentaerythritol tetrapropenyl ester, and the like. AdekoptomerKR is available as a vending product. BY series: KR-400, KR-410, KR-550, KR-566, KR-567, BY-320B (made by Asahi Denki Co., Ltd.); Koeihard A-101-KK, A-101-WS, C-302 , C-401-N, C-501, M-101, M-102, T-102, D-102, NS-101, FT-102Q8, MAG-1-P20, AG-106, M-101-C (produced by Guangrong Chemical Co., Ltd.); SecabeamPHC2210(S), PHC X-9 ( K-3), PHC2213, DP-10, DP-20, DP-30, P1000, P1100, P1200, P1300, P1400, P1500, P1600, SCR900 (made by Dairi Seiki Co., Ltd.); KRM7033, KRM7039, KRM7130 , KRM7131, UVECRYL29201, UVECRYL29202 (manufactured by DAICEL.UCB Co., Ltd.); RC-5015, RC-5016, RC-5020, RC-5031, RC-5100, RC-5102, RC-5120, RC-5122, RC- 5152, RC-5171, RC-5180, RC-5181 (made by Dainippon Ink Chemical Industry Co., Ltd.); Orex No. 340 Kelly (manufactured by China National Paint Co., Ltd.); Shan Lado H-601 , RC-750, RC-700, RC-600, RC-500, RC-611, RC-612 (made by Sanyo Chemical Industry Co., Ltd.); SP-1509, SP-1507 (made by Showa Polymer Co., Ltd.) ; RCC-15C (manufactured by Graee Japan Co., Ltd.), Jalonix M-6100, M-8030, M-8060 (manufactured by Toagosei Co., Ltd.) NK ester A-DOG, NK ester A-IBD-2E ( New Nakamura Chemical Industry Co., Ltd.) and other suitable candidates. Further, examples of specific compounds include trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, and dioxanediol. Acrylate, ethoxylated acrylate, alkyl-modified dipentaerythritol pentaacrylate, and the like.

Further, in the cured resin layer, fine particles having an inorganic compound or an organic compound may be contained in order to adjust the scratch resistance, lubricity, or refractive index.

Examples of the inorganic fine particles include cerium oxide, titanium oxide, aluminum oxide, tin oxide, indium oxide, ITO, zinc oxide, zirconium oxide, magnesium oxide, and carbonic acid. Calcium, calcium carbonate, talc, clay, fired clay, calcined calcium citrate, water and calcium citrate, aluminum citrate, magnesium citrate and calcium phosphate. In particular, cerium oxide, titanium oxide, aluminum oxide, zirconium oxide, magnesium oxide or the like is preferably used. Polymethacrylic acid methacrylate resin powder, acryl styrene resin powder, polymethyl methacrylate resin powder, oxime resin powder, polystyrene resin powder, polycarbonate resin may be added as the organic particles. Powder, benzoguanamine resin powder, melamine resin powder, polyolefin resin powder, polyester resin powder, polyamine resin powder, polyamidene resin powder, or polyvinyl fluoride resin Powder, etc. Preferred examples of the fine particles include crosslinked polystyrene particles (for example, SX-130H, SX-200H, and SX-350H manufactured by Soken Chemical Co., Ltd.) and polymethyl methacrylate-based particles (for example, MX150 and MX300 manufactured by Zaken Chemical Co., Ltd.). .

Other fluorine-containing acrylic resin particles can be used. As the fluorine-containing acrylic resin particles, for example, particles formed of a monomer or polymer of a fluorine-containing acrylate or methacrylate. Specific examples of the fluorine-containing acrylate or methacrylate include 1H, 1H, 3H-tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate. ,1H,1H,7H-dodecafluoroheptyl (meth) acrylate, 1H, 1H, 9H-hexadecafluorodecyl (meth) acrylate, 2,2,2-trifluoroethyl (methyl Acrylate, 2,2,3,3,3-pentafluoropropyl (meth) acrylate, 2-(perfluorobutyl)ethyl (meth) acrylate, 2-(perfluorohexyl) (meth) acrylate, 2-(perfluorooctyl)ethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, 3-perfluorobutyl-2-hydroxyl Propyl (meth) acrylate, 3-perfluorohexyl-2-hydroxypropyl (meth) acrylate, 3-perfluorooctyl 2-hydroxypropyl (meth) acrylate, 2-(perfluoro-3-methylbutyl)ethyl (meth) acrylate, 2-(perfluoro-5-methylhexyl)ethyl (Meth) acrylate, 2-(perfluoro-7-methyloctyl)ethyl (meth) acrylate, 3-(perfluoro-3-methylbutyl-2-hydroxypropyl (methyl) Acrylate, 3-(perfluoro-5-methylhexyl)-2-hydroxypropyl (meth) acrylate, 3-(perfluoro-7-methyloctyl)-2-hydroxypropyl (A) Acrylate, 1H-1-(trifluoromethyl)trifluoroethyl (meth) acrylate, 1H, 1H, 3H-hexafluorobutyl (meth) acrylate, trifluoroethyl methacrylate Ester, tetrafluoropropyl methacrylate, perfluorooctylethyl acrylate, 2-(perfluorobutyl)ethyl-α-fluoroacrylate. Also, the fluorine-containing acrylic resin particles are also 2- Particles formed of (perfluorobutyl)ethyl-α-fluoroacrylate, fluorine-containing polymethyl methacrylate particles, and fluorine-containing methacrylic acid copolymerized with ethylene monomer in the presence of a crosslinking agent More preferably, it is a fluorine-containing polymethyl methacrylate particle.

The vinyl monomer copolymerizable with the fluorine-containing (meth)acrylic acid may be a vinyl group alone, and specifically, an alkyl methacrylate such as methyl methacrylate or butyl methacrylate or an acrylic acid may be mentioned. An alkyl acrylate such as an ester or ethyl acrylate, or a styrene such as styrene or α-methyl styrene may be used singly or in combination. The crosslinking agent to be used in the polymerization reaction is not particularly limited, and those having two or more unsaturated groups are preferably used, and examples thereof include ethylene glycol dimethacrylate and polyethylene glycol. A bifunctional dimethacrylate such as a acrylate or trimethylolpropane trimethacrylate or divinylbenzene.

Moreover, the polymerization reaction when producing fluorine-containing polymethyl methacrylate particles It should be any of random copolymerization and block copolymerization. Specifically, for example, the method described in JP-A-2000-169658 and the like can be mentioned.

As a sales item, a commercial product such as MF-0043 can be cited. Further, these fluorine-containing acrylic resin particles may be used singly or in combination of two or more. Further, the state of these fluorine-containing acrylic resin particles may be added in any state such as a powder or a latex.

Further, the fluorine-containing crosslinked particles described in paragraphs 0028 to 0055 of JP-A-2004-83707 can also be used.

Further, the refractive index of the particles is preferably from 1.45 to 1.70, preferably from 1.45 to 1.65. Further, the refractive index of the particles is determined by dispersing the particles in a solvent having a change in refractive index at a mixing ratio of two kinds of solvents having different refractive indexes, and then measuring the turbidity of the particles, and refracting the solvent having a very small turbidity. The rate was measured by an Abbe refractometer.

The content of the above particles is preferably from 1 part by mass to 30 parts by mass per 100 parts by mass of the above resin.

The average particle diameter of these fine particles is preferably 0.01 to 5 μm, more preferably 0.1 to 5.0 μm, still more preferably 0.1 to 4.0 μm, and the composition is stabilized by the composition added to the coating composition for forming the hard coating layer. It is better to look at it.

Further, two or more kinds of fine particles having different particle diameters may be contained. The ratio of the ultraviolet curable resin to the fine particles is preferably from 0.1 to 30 parts by mass based on 100 parts by mass of the resin.

Further, the hard coat layer can be applied by coating a hard coat layer by a known method such as a gravure coater, a dip coater, a reverse coater, a coil bar coater, a die coater, or a spray method. The cloth composition is heated and dried after coating. It is formed by UV hardening treatment. The coating amount is preferably from 0.1 to 40 μm in wet film thickness, preferably from 0.5 to 30 μm. Further, the dry film thickness has an average film thickness of 0.1 to 30 μm, preferably 1 to 20 μm.

As a light source for the UV curing treatment, a light source that can generate only ultraviolet light is not limited. For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used. The irradiation conditions differ depending on the respective lamps, but the irradiation amount of the active rays is generally 5 to 500 mJ/cm ² , preferably 5 to 150 mJ/cm ² , and particularly preferably 20 to 100 mJ/cm ² .

Further, when the active wire is irradiated, it is preferable to apply tension in the direction in which the film is conveyed, and it is more preferable to apply tension in the width direction. The tension imparted is preferably 30 to 300 N/m. The method of imparting the tension is not particularly limited, and the tension may be applied to the back roller in the conveying direction, or the tensioner may be applied in the width direction or the two-axis direction. Thereby, a film having better planarity can be obtained.

The coating composition formed of the hard coat layer may contain a solvent. Examples of the organic solvent to be contained in the coating composition include hydrocarbons (toluene, xylene), alcohols (methanol, ethanol, isopropanol, butanol, cyclohexanol), and ketones (acetone, methyl group). Ethyl ketone, methyl isobutyl ketone), esters (methyl acetate, ethyl acetate, methyl lactate), glycol ethers, may also be suitably selected from other organic solvents, or mixtures thereof.

The organic solvent is preferably propylene glycol monoalkyl ether (alkyl group having 1 to 4 carbon atoms) or propylene glycol monoalkyl ether acetate (alkyl group having 1 to 4 carbon atoms). Further, the content of the organic solvent is 5~ in the coating composition. 80% by mass is preferred.

The hard coat layer is a transparent hard coat layer having a center line average roughness (Ra) of 0.001 to 0.1 μm as defined in JIS B 0601, or an anti-glare hard coat layer having an Ra adjusted to 0.1 to 1 μm, such as fine particles. It is better. The center line average roughness (Ra) is preferably measured by a light dry type surface roughness measuring device, and can be measured, for example, by using a non-contact surface fine shape measuring device "WYKO NT-2000" manufactured by WYKO Co., Ltd.

Further, the hard coat layer may preferably contain the above-mentioned polyoxyalkylene-based surfactant or polyoxyether compound described in the low refractive index layer. In order to improve the coating property, it is preferred to add the components in the range of 0.01 to 3% by mass to the solid component in the coating liquid.

Examples of the polyoxy ether compound include polyepoxides such as polyethylene oxide alkyl ether, polyethylene oxide lauryl ether, polyethylene oxide cetyl ether, and polyethylene oxide stearyl ether. a polyoxyalkyl phenyl ether compound such as an oxyethane alkyl ether compound, a polyethylene oxide nonyl phenyl ether or a polyethylene oxide octyl phenyl ether; a polyoxyalkylene alkyl ether; a polyethylene oxide higher alcohol Ethers, polyethylene oxide octyl lauryl ether, and the like. EMULGEN 1108, EMULGEN 1118S-70 (above, Kao Corporation), and as a commercial product of polyethylene oxide lauryl ether, EMULGEN 103, EMULGEN are mentioned as a commercial item of the polyethylene oxide alkyl ether. 104P, EMULGEN 105, EMULGEN 106, EMULGEN 108, EMULGEN 109P, EMULGEN 120, EMULGEN 123P, EMULGEN 147, EMULGEN 150, EMULGEN 130K (above, Kao Corporation), as a sale of polyethylene oxide cetyl ether , EMULGEN 210P, EMULGEN 220 (above, Kao Corporation), as a sales item of polyethylene oxide stearyl ether, EMULGEN 220, EMULGEN 306P (above, Kao Corporation), as a polyoxyalkylene ether EMULGEN LS-106, EMULGEN LS-110, EMULGEN LS-114, EMULGEN MS-110 (above, Kao Corporation), as a commercial product of polyethylene oxide higher alcohol ether, EMULGEN 705, EMULGEN 707, EMULGEN 709, and the like.

Among these nonionic polyoxyether compounds, preferred are polyethylene oxide oleyl ether compounds, and compounds represented by the following general formula (6).

C ₁₈ H ₃₅ -O(C ₂ H ₄ O)nH (6) wherein n represents 2 to 40.

The average number of additions (n) of the ethylene oxide in the oil-based portion is 2 to 40, preferably 2 to 10. Further, the compound of the general formula (6) is obtained by reacting ethylene oxide with oleyl alcohol.

Specific products include EMULGEN 404 [polyethylene oxide (4) oleyl ether], EMULGEN 408 [polyethylene oxide (8) oleyl ether], and EMULGEN 409P [polyethylene oxide (9). Oleic ether], EMULGEN 420 [polyethylene oxide (13) oleyl ether], EMULGEN 430 [polyethylene oxide (30) oleyl ether] (above, Kao Corporation), NOFABLEEAO-9905 (polyethylene oxide (5) oleyl ether) and the like.

And ( ) represents the number of n. The nonionic polyoxyether compound may be used alone or in combination of two or more.

The mass ratio of the polyoxonane surfactant to the hard coat layer of the polyoxyether compound is 1.0:1.0 to 0.10:1.0, more preferably 0.70:1.0 to 0.20:1.0, and the system can be obtained by the above mass ratio. The effects of the present invention are preferred.

The preferred content of the nonionic polyoxyether compound and the polyoxyalkylene surfactant in the hard coat layer is preferably 0.1% by mass to 8.0% by mass, more preferably 0.2% by mass. %~4.0% by mass, when added in this range, the hard coat layer can be present under stability.

Further, the above-mentioned fluorine surfactant, acrylic copolymer, acetylene glycol compound, nonionic surfactant, or radically polymerizable nonionic surfactant may be used in combination.

Examples of the nonionic surfactant include polyoxyalkyl ester compounds such as polyethylene oxide monolaurate, polyethylene oxide monostearate, and polyethylene oxide monooleate, and sorbitol. A sorbitan ester compound such as anhydride monolaurate, sorbitan monostearate or sorbitan monooleate.

Examples of the acetylene glycol-based compound include Surfynol 104E, Surfynol 104PA, Surfynol 420, Surfynol 440, Dinol 604 (above, manufactured by Nissin Chemical Industry Co., Ltd.), and the like.

Examples of the radically polymerizable nonionic surfactant include "RMA-564", "RMA-568", and "RMA-1114" (above, trade name, manufactured by Japan Emulsifier Co., Ltd.). An alkylene alkyl phenyl ether (meth) acrylate-based polymerizable surfactant or the like.

Others may also contain a fluororesin. As the fluororesin, a deuterium oxide (containing polyoxyalkylene oxide) and/or an organic germanium alkane (containing organic polyoxyalkylene) can be used. The polymer obtained by copolymerization by grafting or the like is preferred. Specific examples include ZX-022H, ZX-007C, ZX-049, and ZX-047-D manufactured by Fuji Chemical Industry Co., Ltd. These compounds can be used after mixing.

Further, the hard coat layer may have a double layer structure of two or more layers. One of the layers is, for example, a so-called antistatic layer containing conductive fine particles, a conjugated conductive polymer, or an ionic polymer, and may be used as a color correction filter for various display elements, and may have a color tone adjustment function. The color tone adjusting agent (dye, pigment, etc.) may have various functions including an electromagnetic wave blocking agent or an infrared ray absorbing agent.

As the π-conjugated conductive polymer, only an organic polymer having a main chain of a π-conjugated system may be used. For example, polythiophenes, polypyrroles, polyanilines, polyphenylenes, polyacetylenes, polyphenylene vinyls, polyacenes, polythiophene ethylene, and these copolymers are mentioned. From the viewpoint of easiness of polymerization and stability, polythiophenes, polyanilines, and polyacetylenes are preferred.

Examples of the ionic compound include an imidazolium system, a pyridinium system, an alicyclic amine system, an aliphatic amine system, an aliphatic lanthanoid cation, an inorganic ion such as BF ₄ ^- or PF ₆ ^- , and CF ₃ SO ₂ ^- a compound of a fluorine-based anion such as (CF ₃ SO ₂ ) ₂ N ^- or CF ₃ CO ₂ ^- .

The conjugated conductive polymer or the ionic compound is a solid content concentration of the coating composition for forming a hard coat layer of 0.01% by mass or more, and may be stabilized in the composition when it is less than 50% by mass. Preferably. Further, the conjugated conductive polymer or the ionic compound may be added to the high refractive index layer.

(back coating layer)

In the antireflection film of the present invention, it is preferred to provide a back coat layer on the reverse side of the active energy ray-curable resin layer which is a cellulose ester film which is a transparent substrate. The back coating layer is provided to correct the curl generated by the active energy ray-curable resin layer or other layers. That is, the surface on which the back coating layer is provided is made to have an inner side and has a curved property to balance the bending. Further, the back coating layer is preferably coated so as to have an agglomeration preventing layer. In this case, fine particles having a blocking preventing function may be added to the back coating layer coating composition.

Examples of the inorganic compound to be added to the fine particles of the back coating layer include ceria, titania, alumina, zirconia, calcium carbonate, calcium carbonate, talc, clay, calcined clay, calcined calcium citrate, and oxidation. Tin, indium oxide, zinc oxide, ITO, water and calcium citrate, aluminum citrate, magnesium citrate and calcium phosphate. The microparticles are preferred because they have a low haze value, especially cerium oxide.

As the fine particles, for example, trade names of Aerosil R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, TT600 (manufactured by Japan Aerosil Co., Ltd.) can be used. As the fine particles of zirconia, for example, the trade names of Aerosil R976 and R811 (manufactured by Japan Aerosil Co., Ltd.) can be used.

Examples of the polymer include a polyoxyalkylene resin, a fluororesin, and a propylene-based resin. Preferably, the polyoxyalkylene resin is used, and particularly preferably a network structure having a three-dimensional structure, for example, Tospearl 103, the same 105, and the same 108. Trade names of the same 120, the same 145, the same 3120 and the same 240 (above the Toshiba polyoxane (stock) system).

Among them, Aerosil 200V and Aerosil R972V are particularly preferable because they can maintain a low haze value and have a caking prevention effect. The antireflection film used in the present invention has a dynamic friction coefficient of 0.9 or less on the back side of the active energy ray-curable resin layer, and particularly preferably 0.1 to 0.9.

The fine particles contained in the back coating layer are preferably 0.1 to 50% by mass, and preferably 0.1 to 10% by mass, based on the adhesive. The increase in the haze value when the back coating layer is provided is preferably 1% or less, preferably 0.5% or less, and particularly preferably 0.0 to 0.1%.

Examples of the solvent used for the coating of the back coating layer include dioxane, acetone, methyl ethyl ketone, methyl isobutyl ketone, N,N-dimethylformamide, and methyl acetate. , ethyl acetate, trichloroethylene, methylene chloride, ethyl chloride, tetrachloroethane, trichloroethane, chloroform, water, methanol, ethanol, n-propanol, i-propanol, n - Butanol, cyclohexanone, cyclohexanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, or hydrocarbons (toluene, xylene), etc., may be used in combination as appropriate.

Examples of the resin used as the adhesive of the back coating layer include a vinyl chloride-vinyl acetate copolymer, a vinyl chloride resin, a vinyl acetate resin, a copolymer of vinyl acetate and a vinyl alcohol, and a part. Hydrolyzed chlorinated ethylene-vinyl acetate copolymer, chlorinated ethylene-vinylidene copolymer, chlorinated ethylene-propylene fluorenyl copolymer, ethylene vinyl alcohol copolymer, chlorinated polyvinyl chloride, ethylene-chlorine Ethylene copolymer, ethylene-vinyl acetate copolymer, etc., ethylene-based polymer or copolymer, nitrocellulose, cellulose acetate Ester propionate (preferably having an acetyl group substitution degree of 1.8 to 2.3, a propyl ketone substitution degree of 0.1 to 1.0), a cellulose derivative such as a diacetyl cellulose or a cellulose acetate butyrate resin, or a horse Copolymer of acid and/or acrylic acid, acrylate copolymer, acrylonitrile-styrene copolymer, chlorinated polyethylene, acrylonitrile-chlorinated polyethylene styrene copolymer, methyl methacrylate-butyl Diene styrene copolymer, acrylic resin, polyvinyl alcohol resin, polyvinyl acetal resin, polyvinyl butyral resin, urethane resin, polyester polyurethane resin, polyether polyurethane resin, polycarbonate poly Rubber resin such as urethane resin, polyester resin, polyether resin, polyamide resin, amine resin, styrene butadiene resin, butadiene acryl resin, polyoxyalkylene resin, fluorine resin Etc., but not limited to this.

For example, ACRYPETMD, VH, MF, V (manufactured by Mitsubishi Rayon Co., Ltd.), Hiba M-4003, M-4005, M-4006, M-4202, M-5000, and M-5001 can be cited as the acrylic resin. , M-4501 (made by Gensei Industrial Co., Ltd.), Taiana Road BR-50, BR-52, BR-53, BR-60, BR-64, BR-73, BR-75, BR-77, BR -79, BR-80, BR-82, BR-83, BR-85, BR-87, BR-88, BR-90, BR-93, BR-95, BR-100, BR-101, BR-102 , BR-105, BR-106, BR-107, BR-108, BR-112, BR-113, BR-115, BR-116, BR-117, BR-118, etc. (Mitsubishi Rayon Co., Ltd.) Commercially available products such as various homopolymers and copolymers produced by using a propylene group and a methacrylic monomer as a raw material can be suitably selected as appropriate.

For example, the resin used as an adhesive to use cellulose 2 A blend of a cellulose ester such as an acid ester or a cellulose acetate acrylate and an acrylic resin is preferred, and a fine particle formed of an acrylic resin is used to make the refractive index difference between the fine particles and the adhesive less than 0~ 0.02 high back coating layer with high transparency.

These coating compositions are used in a transparent resin film using a gravure coater, a dip coater, a reverse coater, a coil bar-coater, a die coater, or a spray coating, a spray coating, or the like. The surface is applied to a wet film thickness of preferably 1 to 100 μm, particularly preferably 5 to 30 μm.

Further, after coating, heat drying is performed, and if necessary, a back coating layer can be formed by a hardening treatment. The hardening treatment can use the contents described in the low refractive index layer.

The back coating layer can be applied in two or more stages. The back coating layer may also have an easy adhesion layer because it can improve the adhesion to the polarizer.

When the above layers are formed by coating, the transparent resin film can be repeatedly wound up in a roll shape at a width of 1.4 to 4 m, and the above coating is carried out and dried. After the hardening treatment, it is preferable to roll into a roll shape. Further, after the antireflection layer is laminated, it is produced by a production method in which a heat treatment at 50 to 160 ° C is performed in a roll form, and the efficiency or stability when the antireflection film is applied to a long length is compared. good. The heat treatment period can be appropriately determined by the set temperature. For example, at 50 ° C, it is preferable to carry out the period of 3 days or more and less than 30 days, and the temperature of 160 ° C for 10 minutes or more, preferably 1 day or less. Generally, it is preferable that the heat treatment effect of the outer portion of the roll, the center portion of the roll, and the core portion of the roll does not vary, and it is preferably set at a lower temperature, and it is preferably carried out at a temperature of about 50 to 60 ° C for 7 days.

In order to allow the heat treatment to be carried out under stability, it is preferably carried out in a place where the temperature and humidity can be adjusted, and it is preferably carried out in a heat treatment chamber such as dust-free and dust-free.

When the anti-reflection film is wound into a roll shape, the core of the roll may be only the core on the cylinder, and may be any material, but is preferably a hollow plastic core, which is resistant to heating as a plastic material. The heat-resistant plastic material of the treatment temperature may be a resin such as a phenol resin, a xylene resin, a melamine resin, a polyester resin or an epoxy resin. Further, it is preferred to use a reinforced thermosetting resin such as a glass fiber. For the number of volumes of these volume cores, preferably 100 rolls or more, more preferably 500 rolls or more, and the roll thickness is preferably 5 cm or more.

(reflectance of anti-reflection film)

The reflectance of the anti-glare antireflection film of the present invention can be measured by a spectrophotometer. At this time, the inside of the sample measurement side was subjected to roughening treatment, and then light absorption treatment was performed using a black spray, and then the reflected light in the visible light region (400 to 700 nm) was measured.

From the viewpoint of obtaining a preferable external light reflection preventing function for use on the outermost surface of an image display device such as an LCD, the lower the reflectance, the better the average reflectance in the wavelength of the visible light region (hereinafter simply referred to as reflectance). It is preferably 2.5% or less, and the lowest reflectance is preferably 1.5% or less. Further, it is more preferable that the reflectance is 1.5% or less and the minimum reflectance is 1.0% or less. Further, when the reflectance is 2.5% or less, it can be used as the antireflection film of the present invention.

In the wavelength region of visible light, a reflection spectrum having a flat shape is preferred.

Moreover, the reflected hue of the surface of the display device subjected to the anti-reflection treatment is reversed by the design of the anti-reflection film in the short-wavelength region or the long-wavelength region in the visible region. The rate of incidence is high, so most of them are dyed red or blue, but the color of the reflected light has different requirements depending on the application. When used on the outermost surface of a thin TV, it is required to be a natural color.

In this case, it is generally preferred that the range of the reflected hue is on the XYZ color system (CIE 1931 color system), 0.17 ≦ x ≦ 0.27, 0.07 ≦ y ≦ 0.17.

The film thickness of the high refractive index layer and the low refractive index layer is a reflection ratio of the refractive index of each layer in consideration of the refractive index of each layer, and can be calculated by a usual method.

It is preferred to carry out surface treatment before coating each layer. Examples of the surface treatment method include a washing method, an alkali treatment method, a surface plasma treatment method, a high frequency discharge plasma method, an electron beam method, an ion beam method, a sputtering method, an acid treatment, a corona treatment method, and an atmospheric pressure. Luminous discharge plasma method, etc.

In the corona treatment, a high voltage of 1 kV or more is applied between the electrodes under atmospheric pressure, and the treatment is performed under discharge, and it can be carried out using a device sold by Kasuga Electric Co., Ltd. or Toyo Electric Co., Ltd. The intensity of the corona discharge treatment is determined by the distance between the electrodes, the output per unit area, and the frequency of the generator.

A commercially available product may be used for one electrode (A electrode) of the corona treatment device, but the material may be selected from aluminum, stainless steel, or the like. The other is an electrode (B electrode) to enclose the plastic film, and the roller electrode to be placed at a certain distance from the A electrode to be stabilized and uniformly performed by the corona treatment. This can also be used as a lining roller for ceramics, polyoxyalkylene, EPT rubber, Heplon rubber, etc., which are made of aluminum, stainless steel, and other metals. good.

The frequency used for the corona treatment is a frequency of 20 kHz or more and 100 kHz or less, and preferably a frequency of 30 to 60 kHz. When the frequency is lowered, the uniformity of the corona treatment is deteriorated, and corona treatment is uneven. Further, when the number of frequencies is too large, there is no particular problem in performing corona treatment with high output. However, when corona treatment with low output is performed, it is difficult to perform stable treatment, and as a result, processing unevenness occurs.

The output of corona treatment is 1~5W. Min./m ² to 2~4W. min./m output ² of the preferred. The distance between the electrode and the film is 5 to 50 mm, but preferably 10 to 35 mm. When the gap is too open, it is necessary to maintain a certain output and a high voltage is required, which tends to cause unevenness. Moreover, when the gap is too narrow, the applied voltage is too low, and unevenness is likely to occur. Further, when the film is continuously processed, the film is in contact with the film to cause scratches.

Further, as a plasma treatment such as an atmospheric piezoelectric slurry treatment or a normal piezoelectric slurry treatment, for example, the plasma disclosed in JP-A-2004-352777, JP-A-2004-352777, JP-A-2007-314707, and the like can be referred to. Processing technology.

Further, as the processing device, an AP-T series or the like of a normal piezoelectric slurry processing apparatus manufactured by Sekisui Chemical Co., Ltd. can be used.

The alkali treatment method is not particularly limited as long as the film coated with the hard coat layer is immersed in an aqueous alkali solution.

As the aqueous alkali solution, an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution, an aqueous ammonia solution or the like can be used, and among them, an aqueous sodium hydroxide solution is preferred.

The alkali concentration of the aqueous alkali solution, for example, the sodium hydroxide concentration is preferably 0.1 to 25% by mass, and preferably 0.5 to 15% by mass. The alkali treatment temperature is generally 10 ~80 ° C, preferably 20 to 60 ° C.

The alkali treatment time is from 5 seconds to 5 minutes, preferably from 30 seconds to 3 minutes. After the alkali-treated film is neutralized with acidic water, it is preferably washed with water.

(transparent resin film)

A transparent film substrate made of a transparent resin film used in the present invention will be described.

Examples of the transparent film substrate include those which are easy to manufacture, have good adhesion to the active wire-curable resin layer, and are optically isotropic and optically transparent.

The transparent portion is preferably a light transmittance of 60% or more, preferably 80% or more, and particularly preferably 90% or more.

The above properties are not particularly limited, and examples thereof include a cellulose diacetate film, a cellulose triacetate film, a cellulose acetate propionate film, and cellulose acetate butyric acid. A cellulose ester film such as an ester film, a polyester film, a polycarbonate film, a polyacrylate film, a polyfluorene (also containing a polyether oxime) film, polyethylene terephthalate, and polyethylene naphthalene. Polyester film such as acid ester, polyethylene film, polypropylene film, cellophane, polyvinyl chloride film, polyvinyl alcohol film, ethyl vinyl alcohol film, syndiotactic polystyrene film, cycloolefin Polymer film (Alton (manufactured by JSR), ZEONEX, ZEONOA (above, manufactured by Zeon Corporation, Japan), polyvinyl acetal, polymethylpentene film, polyether ketone film, polyether ketimide film, poly Indole film, fluororesin film, nylon film, polymethyl methacrylate film, acryl film Or glass plates, etc.

Among them, a cellulose ester-based film, a polycarbonate-based film, a polyfluorene-containing (polyether-containing) film, and a cycloolefin polymer film are preferred. In the present invention, a cellulose ester-based film (for example, Konicaminolta tak) is particularly preferable. Product name KC8UX, KC4UX, KC5UX, KC8UCR3, KC8UCR4, KC8UCR5, KC8UY, KC4UY, KC4UE, KC12UR (above, manufactured by Konicaminolta opt Co., Ltd.) is preferable from the viewpoints of manufacturing, cost, transparency, adhesion, etc. .

These films may be films produced by melt casting film formation or films produced by solution casting film formation.

As the transparent film substrate, a cellulose ester film (hereinafter also referred to as a cellulose ester film) is preferably used. As the cellulose ester, cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate is preferred, and cellulose acetate butyrate and cellulose acetate are also used. The acid ester, cellulose acetate propionate is preferred.

In particular, the degree of substitution of the acetyl group is represented by X, and when the degree of substitution of the propyl group or the butyl group is represented by Y, it is preferred to use a cellulose ester film having X and Y in the following ranges.

2.3≦X+Y≦3.0 0.1≦Y≦2.0

Especially when 2.5≦X+Y≦2.9 3≦Y≦1.2 is preferred.

Hereinafter, a cellulose ester film of a preferred transparent resin film will be described in detail.

The cellulose ester film is an antireflection film having less deformation of the substrate and having excellent planarity due to heat treatment, and the free volume radius obtained by the Positron annihilation lifetime is 0.250 to 0.310 nm. good. Further, a cellulose ester film having a total free volume parameter of 1.0 to 2.0 is preferred.

Further, the above free volume means a void portion of a molecular chain which does not occupy the transparent resin film. This can be measured using the positive electron elimination life method. Specifically, the time during which the positron is injected into the sample to the extinction is measured, and the information on the size and number concentration of the atomic pore or the free volume can be observed nondestructively from the erasing life.

(Measurement of the free volume radius and the full free volume parameter by the positive electron elimination life method)

The cation lifetime and relative intensity were measured under the following measurement conditions.

(measurement conditions) Yang electronic line source: 22NaCl (strength 1.85MBq) γ line detector: plastic scintillator + photoelectron multiplier tube device time decomposition energy: 290ps measurement temperature: 23 ° C total count: 1 million sample size: 20mm × 15mm

The sample piece cut into 20 mm × 15 mm was formed into 20 pieces of overlap, which was about 2 mm thick. The sample was vacuum dried for 24 hours before the measurement.

Irradiation area: about 10mm Time per channel: 23.3ps/ch

According to the above measurement conditions, the positive electron elimination life measurement is performed, and the three-component analysis is performed by the nonlinear least squares method, and the one with the smaller lifetime is used as τ ₁ , τ ₂ , and τ ₃ , and the intensity is taken as I ₁ , I ₂ , I ₃ (I ₁ +I ₂ +I ₃ =100%).

From the average lifetime τ _{3 of the} longest life, the free volume radius R ₃ (nm) of the following formula was obtained. Corresponding to the positron electron elimination of τ ₃ in the void, it is presumed that the larger the τ ₃ is, the larger the pore size is.

τ ₃ =(1/2)[1-{R ₃ /(R ₃ +0.166)}+(1/2π)sin{2πR ₃ /(R ₃ +0.166)}]-1 where 0.166(nm ) equivalent to the thickness of the electron layer leached from the wall of the void.

Moreover, the full free volume parameter V _p is obtained by the following equation.

V ₃ ={(4/3)π(R ₃ )3}(nm ³ ) V _p =I ₃ (%)×V ₃ (nm ³ ) where I ₃ (%) corresponds to the relative concentration of the pores , so that V _p corresponds to the relative amount of voids.

The above measurement was repeated twice, and the average value was obtained.

Yang Electronics eliminates life methods, such as MATERIAL STAGE vol.4, No.5 2004 p21-25, Toray Research Center THE TRC NEWS No. 80 (Jul. 2002) p20-22, "Analysis" (1988, pp. 11-20), "The Freedom of Polymers by the Method of Elimination of Positive Electrons" For the evaluation of the volume, please refer to this.

The free volume radius in the cellulose ester film is 0.250 to 0.315 nm, preferably 0.250 to 0.310 nm, and more preferably 0.285 to 0.305 nm. The free volume radius is less than 0.250 nm. When the free volume radius is 0.250 to 0.315 nm, the substrate for heat treatment is less deformed, and an antireflection film excellent in planarity can be obtained.

The raw material of the cellulose ester forming the cellulose ester film is not particularly limited, and examples thereof include cotton linters, wood pulp (from conifers, from broadleaf trees), and kenaf. Further, these obtained cellulose esters can be used in combination at any ratio. When the cellulose ester is an acid anhydride (acetic anhydride, propionic anhydride, butyric anhydride), an organic solvent such as acetic acid or an organic solvent such as dichloromethane is used, and a protonic catalyst such as sulfuric acid and a cellulose raw material are used. It is obtained by carrying out a reaction.

When the thiolating agent is an acid chloride (CH ₃ COCl, C ₂ H ₅ COCl, C ₃ H ₇ COCl), the reaction can be carried out using a basic compound such as an amine as a catalyst. Specifically, the synthesis can be carried out by referring to the method described in JP-A-10-45804.

Further, the cellulose ester is reacted by mixing the above-mentioned thiolation amount with each degree of substitution, and the thiolation agent in the cellulose ester reacts with the hydroxyl group of the cellulose molecule. The cellulose molecule is formed by a majority of the glucose unit and has three hydroxyl groups on the glucose unit. The thiol group is derived from the three hydroxyl groups The number of births is called the degree of substitution (% of moles). For example, for example, cellulose triacetate is such that all three hydroxyl groups of the glucose unit are bound to the acetamidine group (actually 2.6 to 3.0).

The method for determining the degree of substitution of the thiol group can be determined in accordance with ASTM-D817-96.

The number average molecular weight of the cellulose ester is 50,000 to 250,000, and the mechanical strength at the time of molding is strong, and it is preferably a moderate blending viscosity, and more preferably 80,000 to 150,000.

The cellulose ester film can be used for casting a cellulose ester solution (blending), for example, by an infinite metal transfer belt or a rotating metal drum, which is generally referred to as a solution casting film forming method. The support is produced by a method in which a compression molding is performed to cast a film by casting (casting).

As the organic solvent to be blended, it is preferred to dissolve the cellulose ester and have an appropriate boiling point, and examples thereof include dichloromethane, methyl acetate, ethyl acetate, amyl acetate, and ethyl acetate. Acetone, tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, cyclohexanone, ethyl formate, 2,2,2-trifluoroethanol, 2,2,3,3-tetrafluoro 1-propanol, 1,3-difluoro-2-propanol, 1,1,1,3,3,3-hexafluoro-2-methyl-2-propanol, 1,1,1,3 , 3,3-hexafluoro-2-propanol, 2,2,3,3,3-pentafluoro-1-propanol, nitroethane, 1,3-dimethyl-2-imidazolidone, etc. Further, an organic halogen compound such as dichloromethane, a dioxalane derivative, methyl acetate, ethyl acetate, acetone or methyl acetacetate may be mentioned as a preferred organic solvent (that is, a good solvent).

Further, as shown in the film forming step described below, when the solvent is dried from the web (blending film) formed on the casting support in the solvent evaporation step From the viewpoint of preventing foaming in the woven fabric, the boiling point of the organic solvent to be used is preferably from 30 to 80 ° C. For example, the boiling point of the good solvent described above is dichloromethane (boiling point: 40.4 ° C), and acetic acid Ester (boiling point 56.32 ° C), acetone (boiling point 56.3 ° C), ethyl acetate (boiling point 76.82 ° C) and the like.

Among the above good solvents, dichloromethane or methyl acetate having excellent solubility is preferred.

In addition to the above organic solvent, it is preferred to contain 0.1 to 40% by mass of an alcohol having 1 to 4 carbon atoms. It is particularly preferred to contain 5 to 30% by mass of the above alcohol.

When the ratio of the alcohol in which the solvent starts to evaporate is increased after the blend is cast on the support for casting, the woven fabric (blend film) is gelated, and the fabric can be stably supported by the casting support. When peeling is carried out, it is used as a gelling solvent, or when the ratio is small, it can play a role which accelerates the dissolution of the cellulose ester of a non-chlorine-type organic solvent.

Examples of the alcohol having 1 to 4 carbon atoms include methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol, and tert-butanol.

Among these solvents, ethanol is preferred from the viewpoints of good blending stability, low boiling point, good drying property, and no toxicity. It is preferred to use a solvent containing 5 to 30% by mass of ethanol for 70 to 95% by mass of methylene chloride. Instead of dichloromethane, methyl acetate can be used. At this time, the blend can be prepared by a cooling dissolution method.

The cellulose ester film may preferably contain the following plasticizer. As the plasticizer, for example, a phosphate-based plasticizer, a polyol ester-based plasticizer, or the like can be used. Phthalate plasticizer, trimellitate plasticizer, pyromellitic plasticizer, glycolate plasticizer, citrate plasticizer, polyester plasticizer, fatty acid ester It is preferably a plasticizer, a polycarboxylic acid ester type plasticizer or the like.

Among them, polyol ester-based plasticizers, phthalate-based plasticizers, citrate-based plasticizers, fatty acid ester-based plasticizers, glycolate-based plasticizers, and polycarboxylate-based plasticizers are also used. It is better. In particular, it is preferable to use a polyol ester-based plasticizer, and it is preferable to obtain a hard coating layer having a pencil hardness of 4H or more.

The polyol ester-based plasticizer is a plasticizer composed of an ester of a divalent or higher aliphatic polyol and a monocarboxylic acid, and preferably has an aromatic ring or a cycloalkyl ring in the molecule. It is preferably an aliphatic polyol ester of 2 to 20 valence.

The polyols are represented by the following general formula (7).

R ¹ -(OH)n (7) wherein R ¹ represents an n-valent organic group, n represents a positive integer of 2 or more, and OH group represents an alcoholic property and/or a phenolic hydroxyl group.

Examples of preferred polyhydric alcohols include, for example, the following, but the present invention is not limited thereto.

Examples thereof include ribitol, arabitol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, and tripropylene glycol. 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, dibutylene glycol, 1,2,4-butanetriol, 1,5-pentanediol, 1, 6-hexanediol, hexanetriol, Galactitol, mannitol, 3-methylpentane-1,3,5-triol, pinacol, sorbitol, trimethylolpropane, trimethylolethane, xylitol, and the like. Particularly preferred are triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, sorbitol, trimethylolpropane, and xylitol.

The monocarboxylic acid to be used for the polyol ester is not particularly limited, and a known aliphatic monocarboxylic acid, alicyclic monocarboxylic acid, aromatic monocarboxylic acid or the like can be used. When an alicyclic monocarboxylic acid or an aromatic monocarboxylic acid is used, moisture permeability and retention are improved, which is preferable.

As an example of a preferable monocarboxylic acid, the following are mentioned, However, this invention is not limited to this.

As the aliphatic monocarboxylic acid, a linear or branched fatty acid having 1 to 32 carbon atoms is preferably used. It is better when the carbon number is 1 to 20, and it is particularly good when it is 1 to 10. When acetic acid is contained, the compatibility with the cellulose ester is increased, and it is preferable to use acetic acid and other monocarboxylic acids.

Preferred examples of the aliphatic monocarboxylic acid include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, capric acid, capric acid, 2-ethyl-hexane acid, and undecyl group. Acid, lauric acid, tridecyl acid, myristic acid, pentadecyl acid, palmitic acid, heptadecanoic acid, stearic acid, nonadecyl acid, arachidic acid, behenic acid, carnaubanic acid , waxy acid, heptadecyl acid, octadecanoic acid, tridecyl acid, tridecyl acid and other saturated fatty acids, undecylenic acid, oleic acid, sorbic acid, linoleic acid, Unsaturated fatty acids such as linolenic acid and arachidonic acid.

Examples of preferred alicyclic monocarboxylic acids include cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, cyclooctanecarboxylic acid, and the like.

Examples of the preferred aromatic monocarboxylic acid include those in which one to three alkyl groups such as benzoic acid and toluic acid are introduced into an alkyl group such as an alkyl group, a methoxy group or an ethoxy group. More than one aromatic monocarboxylic acid of the benzene ring, or a derivative thereof, particularly preferably benzoic acid.

Although the molecular weight of the polyol ester is not particularly limited, it is preferably from 300 to 1,500, more preferably from 350 to 750. The larger the molecular weight, the more difficult it is to volatilize, and it is preferably smaller from the viewpoint of compatibility with moisture permeability and cellulose ester.

The carboxylic acid to be used in the polyol ester may be one type or a mixture of two or more types. Further, the OH groups in the polyols may be all esterified or partially maintained in the OH group.

Specific compounds of the polyol esters are exemplified below.

The glycolate plasticizer is not particularly limited, but an alkylphthalic acid alkyl glycolate is preferably used. Examples of the alkylphthalic acid alkyl glycolate include methyl phthalyl methyl glycolate, ethyl phthalic acid ethyl glycolate, and propyl phthalate. Mercaptopropyl glycolate, butyl phthalyl butyl glycolate, octyl phthalyl octyl glycolate, methyl phthalyl ethyl glycolate, ethyl Benzoyl methyl glycolate, ethyl phthalyl propyl glycolate, methyl phthalyl butyl glycolate, ethyl phthalate butyl glycolate, butyl O-phthalyl methyl glycolate, butyl phthalyl ethyl glycolate, propyl phthalyl butyl glycolate, butyl phthalyl propyl glycolate Methylphthalic acid octyl glycolate, ethyl phthalate Mercaptooctyl glycolate, octyl phthalyl methyl glycolate, octyl phthalyl ethyl glycolate, and the like.

Examples of the phthalate-based plasticizer include diethyl phthalate, dimethoxyethyl phthalate, dimethyl phthalate, dioctyl phthalate, and dibutyl phthalate. , di-2-ethylhexyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, dicyclohexyl terephthalate, and the like.

Examples of the citrate-based plasticizer include etidinyltrimethyl citrate, ethionyltriethyl citrate, and ethyltributyl citrate.

Examples of the fatty acid ester-based plasticizer include oleic acid butyl group, ricinoleic acid methyl ethyl sulfonate group, and dibutyl sebacate.

A polycarboxylic acid ester type plasticizer can also be used. Specifically, it is preferred to add the polyvalent carboxylate described in paragraphs [0015] to [0020] of JP-A-2002-265639 as one of plasticizers.

Further, as other plasticizers, a phosphate-based plasticizer can be used, and triphenyl phosphate, tricresol phosphate, cresol diphenyl phosphate, octyl diphenyl phosphate, and diphenyl linkage can be used. Phenyl phosphate, trioctyl phosphate, tributyl phosphate, and the like.

Others may preferably contain a propylene-based polymer described in JP-A-2003-12859.

<propylene-based polymer>

The cellulose ester film is preferably a propylene-based polymer containing a weight average molecular weight of 500 or more and 30,000 or less which exhibits a negative complex birefringence in the extending direction.

When the composition of the polymer is controlled so that the weight average molecular weight of the polymer is 500 or more and 30,000 or less, the compatibility between the cellulose ester and the polymer can be improved.

In particular, the propylene-based polymer, the propylene-based polymer having an aromatic ring in a branched chain or the propylene-based polymer having a cyclohexyl group in a branched chain may preferably have a weight average molecular weight of 500 or more and 10,000 or less, in addition to the above, The cellulose ester film after film formation is excellent in transparency and extremely low in moisture permeability, and can exhibit excellent properties as an antireflection film.

The polymer has a weight average molecular weight of 500 or more and 30,000 or less, and can be considered as an oligomer to a low molecular weight polymer. The synthesis of such a polymer makes it difficult to control the molecular weight in general polymerization, and it is expected to use a method of controlling the molecular weight as much as possible without excessive molecular weight.

As a related polymerization method, a method of using a peroxide polymerization initiator such as cumene peroxide or a third butyl hydroperoxide, a method of using a polymerization initiator other than a general polymerization, and a polymerization initiator are used. a method of using a chain shifting agent such as a hydrosulfide compound or carbon tetrachloride, or a method of using a polymerization stopper such as benzoquinoline or dinitrobenzene other than a polymerization initiator, and having the publication No. 2000-128911 or A compound of a thiol group and a hydroxy group described in JP-A-2000-344823, or a block polymerization method using a polymerization catalyst of the compound and an organometallic compound. The above is applicable, but it is particularly preferable to use the method described in the publication.

Further, the propylene-based polymer is a homopolymer or copolymer of acrylic acid or alkyl methacrylate which does not have a monomer unit containing an aromatic ring or a cyclohexyl group. The so-called propylene-based polymer having an aromatic ring on the branch must contain A propylene-based polymer having an aromatic ring of acrylic or methacrylic monomer units.

Further, the propylene-based polymer having a cyclohexyl group on the branched chain is a propylene-based polymer containing a monomer unit of an acrylic acid or a methacrylate having a cyclohexyl group.

Examples of the acrylate monomer having no aromatic ring or cyclohexyl group include methyl acrylate, ethyl acrylate, propyl acrylate (i-, n-), and butyl acrylate (n-, i-, s-, T-), pentyl acrylate (n-, i-, s-), hexyl acrylate (n-, i-), heptyl acrylate (n-, i-), octyl acrylate (n-, i-), Acyl acrylate (n-, i-), acrylonitrile myristate (n-, i-), acrylic acid (2-ethylhexyl), acrylic acid (ε-caprolactone), acrylic acid (2-hydroxyethyl), Acrylic acid (2-hydroxypropyl), acrylic acid (3-hydroxypropyl), acrylic acid (4-hydroxybutyl), acrylic acid (2-hydroxybutyl), acrylic acid (2-methoxyethyl), acrylic acid (2 -Ethoxyethyl) or the like, or the above acrylate is changed to methacrylate.

The propylene-based polymer is a homopolymer or a copolymer of the above monomers, preferably having a methyl acrylate monomer unit of 30% by mass or more, and further preferably having a methyl methacrylate monomer unit of 40% by mass or more. . In particular, a homopolymer of methyl acrylate or methyl methacrylate is preferred.

Examples of the acrylic or methacrylic ester monomer having an aromatic ring include phenyl acrylate, phenyl methacrylate, acrylic acid (2 or 4-chlorophenyl), and methacrylic acid (2 or 4-chlorophenyl). ), acrylic acid (2 or 3 or 4-ethoxycarbonylphenyl), methacrylic acid (2 or 3 or 4-ethoxyl) Carbonyl phenyl), acrylic acid (o or m or p-tolyl), methacrylic acid (o or m or p-tolyl), benzyl acrylate, benzyl methacrylate, phenylethyl acrylate, methyl As the phenylethyl acrylate or the acrylic acid (2-naphthyl group), benzyl acrylate, benzyl methacrylate, phenylethyl acrylate or phenethyl methacrylate is preferred.

In the propylene-based polymer having an aromatic ring on the branch, the monomer having acrylic or methacrylic ester having an aromatic ring is 20 to 40% by mass, and has an acrylic or methyl methacrylate monomer unit of 50 to 80 mass. % is better. The polymer preferably contains 2 to 20% by mass of the acrylic acid or methacrylic acid monomer unit having a hydroxyl group.

Examples of the acrylate monomer having a cyclohexyl group include cyclohexyl acrylate, cyclohexyl methacrylate, acrylic acid (4-methylcyclohexyl), methacrylic acid (4-methylcyclohexyl), and acrylic acid ( 4-ethylcyclohexyl), methacrylic acid (4-ethylcyclohexyl), etc., preferably cyclohexyl acrylate and cyclohexyl methacrylate are used.

The propylene-based polymer having a cyclohexyl group in the branched chain contains 20 to 40% by mass of the monomer having acrylic acid or methacrylic acid ester having a cyclohexyl group, and preferably 50 to 80% by mass. Further, the polymer preferably contains 2 to 20% by mass of the acrylic acid or methacrylic acid monomer unit having a hydroxyl group.

The polymer obtained by polymerizing the above ethylenically unsaturated monomer, the propylene-based polymer, the propylene-based polymer having an aromatic ring on the branch, and the propylene-based polymer having a cyclohexyl group on the branch are excellent in compatibility with the cellulose resin. .

These acrylic or methacrylic acid ester monomers having a hydroxyl group are not homopolymers and are constituent units of the copolymer. At this time, it is preferred to have a hydroxyl group C The content of the olefinic acid or methacrylic acid ester monomer unit in the propylene-based polymer is preferably 2 to 20% by mass.

Further, it can also be used for a polymer having a hydroxyl group in a branched chain. The monomer unit having a hydroxyl group is the same as the above-mentioned monomer, but preferably acrylic acid or methacrylic acid ester, and examples thereof include acrylic acid (2-hydroxyethyl), acrylic acid (2-hydroxypropyl), and acrylic acid ( 3-hydroxypropyl), (4-hydroxybutyl) acrylate, (2-hydroxybutyl) acrylate, p-hydroxymethylphenyl acrylate, p-(2-hydroxyethyl) phenyl acrylate, or These acrylic acid are substituted by methacrylic acid, preferably 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate. The content of the acrylate or methacrylate monomer having a hydroxyl group in the polymer is preferably from 2 to 20% by mass, preferably from 2 to 10% by mass.

As described above, the polymer is 2 to 20% by mass of the monomer unit having the above-mentioned hydroxyl group, and is inevitably excellent in compatibility, retention, and dimensional stability with the cellulose ester, and the moisture permeability is not only small, but also acts as a protective film for the polarizing plate. The polarizer has excellent adhesion and has the effect of improving the durability of the polarizing plate.

The method of providing a hydroxyl group in at least one terminal of the main chain of the propylene-based polymer is not particularly limited, and a method of providing a hydroxyl group at the terminal of the main chain is not particularly limited, and examples thereof include using azobis(2-hydroxyl group). A method of radical polymerization initiator of a hydroxyl group of ethyl butyrate, a method of using a chain shifting agent having a hydroxyl group such as 2-hydrothioethanol, a method of using a polymerization stopper having a hydroxyl group, and a reactive ion A method of polymerizing a terminal having a hydroxyl group, or a compound having a thiol group and a hydroxyl group of a second order, or a combination thereof, as disclosed in JP-A-2000-128911 or JP-A-2000-344823 It is obtained by a block polymerization method of a polymerization catalyst of an organometallic compound, etc., and it is especially preferable to use the method as described in this publication.

The polymer produced by the method described in this publication is ACTFLOW manufactured by Ivy Research Chemical Co., Ltd. The series is sold and is suitable for use in the present invention. The polymer having a hydroxyl group at the terminal and/or a polymer having a hydroxyl group in the branched group has an effect of remarkably improving the compatibility and transparency of the polymer of the cellulose ester in the present invention.

Further, as the ethylenically unsaturated monomer exhibiting a negative alignment birefringence in the extending direction, it is preferred to use a styrene-based polymer to exhibit negative refractive properties. As the styrene, for example, styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, chloromethyl styrene, methoxy styrene, Acetyl styrene, chlorostyrene, dichlorostyrene, bromostyrene, methyl benzoic acid methyl ester, etc., but are not limited thereto.

It is possible to copolymerize with a monomer exemplified as the unsaturated ethylenic monomer, and to use two or more kinds of the above polymers to be dissolved in a cellulose ester for the purpose of controlling birefringence.

Further, the cellulose ester film contains an ethylenically unsaturated monomer Xa having no aromatic ring and a hydrophilic group in the molecule, and an ethylenically unsaturated monomer Xb having a hydrophilic group in the molecule and having a hydrophilic group. The polymer X obtained by polymerization and having a weight average molecular weight of 5,000 or more and 30,000 or less is preferably a polymer Y having a weight average molecular weight of 500 or more and 3000 or less obtained by polymerization of the ethylenically unsaturated monomer Ya having no aromatic ring.

(Polymer X, Polymer Y)

The polymer X used in the present invention is an ethylenically unsaturated monomer Xa having no aromatic ring and hydrophilic group in the molecule, and an ethylenically unsaturated monomer Xb having a hydrophilic group in the molecule and having a hydrophilic group. A polymer having a weight average molecular weight of 5,000 or more and 30,000 or less obtained by copolymerization.

Preferably, Xa is a propylene group or a methacrylic monomer having no aromatic ring and a hydrophilic group in the molecule, and Xb is a propylene group or a methacrylic monomer having a hydrophilic group in the molecule and having a hydrophilic group.

The polymer X is represented by the following general formula (8).

-(Xa)m-(Xb)n-(Xc)p-.........(8)

More preferably, it is a polymer represented by the following general formula (9).

-[CH ₂ -C(-R ¹ )(-CO ₂ R ² )]m-[CH ₂ -C(-R ³ )(-CO ₂ R ⁴ -OH)-]n-[Xc]p-... (9) (wherein R ¹ and R ³ represent H or CH _{3 .} R ² represents an alkyl group having 1 to 12 carbon atoms or a cycloalkyl group. R ⁴ represents -CH ₂ -, -C ₂ H ₄ - Or -C ₃ H _{6 -.} Xc represents a monomer unit in which Xa and Xb are polymerizable. m, n and p represent a molar composition ratio. However, m≠0, n≠0, k≠0, m+n+p=100) .

In the present invention, the monomer constituting the monomer unit of the acrylic polymer X is as follows, but is not limited thereto.

In the acrylic polymer X, the hydrophilic group has a hydroxyl group and a ring. Oxygen ethane linkage base.

Examples of the ethylenically unsaturated monomer Xa having no aromatic ring and hydrophilic group in the molecule include methyl acrylate, ethyl acrylate, propyl acrylate (i-, n-), and butyl acrylate (n-, i). -, s-, t-), pentyl acrylate (n-, i-, s-), hexyl acrylate (n-, i-), heptyl acrylate (n-, i-), octyl acrylate (n- , i-), fluorenyl acrylate (n-, i-), acrylic acid myristyl (n-, i-), acrylic acid (2-ethylhexyl), acrylic acid (ε-caprolactone), etc., or The acrylate is changed to methacrylate.

Among them, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, and propyl methacrylate (i-, n-) are preferred.

The ethylenically unsaturated monomer Xb having no aromatic ring and having a hydrophilic group in the molecule, and the monomer unit having a hydroxyl group is preferably acrylic acid or methacrylic acid ester, and examples thereof include acrylic acid (2-hydroxyethyl). Acrylic acid (2-hydroxypropyl), acrylic acid (3-hydroxypropyl), acrylic acid (4-hydroxybutyl), acrylic acid (2-hydroxybutyl), or those obtained by substituting these acrylic acids with methacrylic acid, preferably It is acrylic acid (2-hydroxyethyl), and methacrylic acid (2-hydroxyethyl), acrylic acid (2-hydroxypropyl), acrylic acid (3-hydroxypropyl).

Xc is not particularly limited as long as it is a copolymerizable ethylenic unsaturated monomer other than Xa or Xb, and is preferably an aromatic ring.

The moir composition ratio of Xa, Xb and Xc is preferably in the range of 99:1 to 65:35, more preferably in the range of 95:5 to 75:25. The p of Xc is 0~10. Xc is a plural monomer unit.

When the molar composition ratio of Xa is too large, the compatibility with the cellulose ester is improved, but the value of the film thickness retention value (Rt) is increased. When the molar composition ratio of Xb is too large, the above-described compatibility is deteriorated, and the effect of reducing the thickness direction retention value (Rt) is improved. Further, when the molar composition ratio of Xb exceeds the above range, fogging tends to occur during film formation, and these are optimized by setting the molar composition ratio of Xa and Xb.

The molecular weight of the polymer X is a weight average molecular weight of 5,000 or more and 30,000 or less, more preferably 8,000 or more and 25,000 or less.

When the weight average molecular weight is 5,000 or more, the cellulose ester film can be obtained with less dimensional change under high temperature and high humidity, and it is preferable because the polarizing plate protective film has less bending. When the weight average molecular weight is 30,000 or less, the compatibility with the cellulose ester is further improved, and the extravasation under high temperature and high humidity and the generation of mist after film formation can be suppressed.

The weight average molecular weight of the polymer X can be adjusted by a known molecular weight adjustment method. As such a molecular weight adjustment method, for example, a method of adding a chain shifting agent such as carbon tetrachloride, lauryl mercaptan or octyl thioglycolate may be mentioned. Further, the polymerization temperature is usually from room temperature to 130 ° C, preferably from 50 ° C to 100 ° C, but the temperature or the polymerization reaction time can be adjusted.

The polymer Y is a polymer having a weight average molecular weight of 500 or more and 3,000 or less obtained by polymerizing the ethylenically unsaturated monomer Ya having no aromatic ring.

Among them, when the weight average molecular weight of the polymer Y is 500 or more, the residual monomer of the polymer is reduced, which is preferable. Further, when the weight average molecular weight of the polymer Y is 3,000 or less, the thickness direction retention value (Rt) can be maintained. The lowering of the value is better.

Ya is preferably a propylene or methacrylic monomer having no aromatic ring.

The polymer Y is represented by the following general formula (10).

-(Ya)k-(Yb)q-.........(10)

More preferably, it is a polymer represented by the following general formula (11).

-[CH ₂ -C(-R ⁵ )(-CO ₂ R ⁶ )]k-[Yb]q-... (11) (wherein R ⁵ represents H or CH _{3 .} R ⁶ represents a carbon number of 1 Alkyl or cycloalkyl of ~12. Yb represents a monomer unit copolymerizable with Ya. k and q represent a molar composition ratio. However, k≠0, k+q=100).

Yb is only an ethylenically unsaturated monomer copolymerizable with Ya, and is not particularly limited. Yb can be plural. k+q=100, q is preferably 0~30.

The ethylenically unsaturated monomer Ya of the polymer Y obtained by polymerizing an ethylenically unsaturated monomer having no aromatic ring, and examples of the acrylate include methyl acrylate, ethyl acrylate, and propyl acrylate (i). -, n-), butyl acrylate (n-, i-, s-, t-), pentyl acrylate (n-, i-, s-), hexyl acrylate (n-, i-), heptyl acrylate (n-, i-), octyl acrylate (n-, i-), fluorenyl acrylate (n-, i-), acrylic myristyl (n-, i-), cyclohexyl acrylate, acrylic acid (2 -ethylhexyl ), acrylic acid (ε-caprolactone), acrylic acid (2-hydroxyethyl), acrylic acid (2-hydroxypropyl), acrylic acid (3-hydroxypropyl), acrylic acid (4-hydroxybutyl), acrylic acid (2) - hydroxybutyl), the methacrylate is exemplified by changing the above acrylate to methacrylate; examples of the unsaturated acid include acrylic acid, methacrylic acid, maleic anhydride, crotonic acid, and itacon. Acid, etc.

Yb is not particularly limited as long as it is an ethylenically unsaturated monomer copolymerizable with Ya, and examples of the vinyl ester include vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl valerate. Trimethyl vinyl acetate, vinyl hexanoate, vinyl decanoate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, vinyl cyclohexanecarboxylate, octyl acid Vinyl ester, vinyl methacrylate, vinyl crotonate, vinyl sorbate, vinyl cinnamate, etc. are preferred. Yb can be plural.

When synthesizing the polymer X and the polymer Y, it is difficult to control the molecular weight in the polymerization, and it is expected to use a method of controlling the molecular weight as much as possible without excessive molecular weight.

As the polymerization method of the polymer X and the polymer Y, a method of using a peroxide polymerization initiator such as cumene peroxide or a third butyl hydroperoxide, and using a polymerization initiator other than the general polymerization can be used. a method of using a chain shifting agent such as another hydrosulfide compound or carbon tetrachloride other than a polymerization initiator, and a method of using a polymerization stopper such as benzoquinoline or dinitrobenzene other than a polymerization initiator, Further, a compound having a thiol group and a hydroxyl group of the second order or a polymerization catalyst using the compound and the organometallic compound in combination with JP-A-2000-128911 or JP-A-2000-344823 Block polymerization methods, etc.

The polymer Y is preferably a polymerization method in which a compound having a thiol group and a secondary hydroxyl group in the molecule is used as a chain shifting agent. At this time, the terminal of the polymer Y has a hydroxyl group or a thioether caused by a polymerization catalyst and a chain shifting agent. The compatibility of the polymer Y with the cellulose ester can be adjusted by the terminal residue.

The hydroxyl group of the polymer X and the polymer Y is preferably 30 to 150 [mgKOH/g].

Among them, the measurement of the hydroxyl value can be carried out in accordance with JIS K 0070 (1992). The hydroxyl value is defined as the number of mg of potassium hydroxide required to neutralize acetic acid bound to a hydroxyl group when 1 g of the sample is subjected to acetylation. Specifically, after the sample xg (about 1 g) was accurately weighed in a flask, 20 ml of an acetamidine reagent (a pyridine was added to 20 ml of acetic anhydride to make it into a 400 ml) was correctly added thereto. An air cooling tube was placed at the mouth of the flask and heated in a glycerin bath at 95 to 100 °C. After cooling for 1 hour and 30 minutes, 1 ml of pure water was added from an air cooling tube to decompose acetic anhydride into acetic acid. Next, titration was carried out using a potentiometric titration apparatus in a 0.5 mol/L potassium hydroxide ethanol solution, and the obtained curve of the titration curve was used as an end point. Further, as a blank test, titration was carried out without placing the sample, and the inflection point of the titration curve was obtained. The hydroxyl value was calculated by the following formula.

Hydroxyl value = {(B-C) × f × 28.05 / x} + D (wherein B represents 0.5 mol / L of potassium hydroxide ethanol used in the blank test The amount of the solution (ml), C represents the amount of potassium hydroxide solution (ml) used for titration of 0.5 mol/L, f represents the factor of 0.5 mol/L potassium hydroxide ethanol solution, D represents the acid value, and 28.05 represents The amount of 1 mol of potassium hydroxide is 1/2 of 56.11.

The content of the cellulose X film of the polymer X and the polymer Y is preferably such that it satisfies the following formula (i) or formula (ii). The content of the polymer X is yg (% by mass) as xg (% by mass = mass of the polymer X / mass of the cellulose ester × 100), and the content of the polymer Y is yg (% by mass). Formula (i) 5 ≦ xg + yg ≦ 35 (% by mass) Formula (ii) 0.05 ≦ yg / (xg + yg) ≦ 0.4 The preferred range of the formula (i) is 10 to 25% by mass.

Further, the weight average molecular weight Mw of the polymer can be measured by gel permeation chromatography.

The measurement conditions are as follows.

Solvent: Dichloromethane column: Shodex K806, K805, K803G (used by connecting 3 Showa Denko Co., Ltd.) Column temperature: 25 °C Sample concentration: 0.1% by mass Detector: RI Model 504 (manufactured by GLS Science) Ur: L6000 (made by Hitachi, Ltd.) Flow: 1.0ml/min Proofreading curve: standard polystyrene STK

A calibration curve obtained from 13 samples of standard polystyrene (manufactured by Tosoh Co., Ltd.) Mw = 1,000,000 to 500 was used. The 13 samples used almost equal intervals.

The total amount of the polymer X and the polymer Y is only 5% by mass or more, and it is sufficient to sufficiently reduce the retention value (Rt) in the thickness direction. Moreover, when the total amount is 35% by mass or less, the adhesion to the polarizer PVA is good.

The polymer X and the polymer Y can be directly added, dissolved, or dissolved in an organic solvent in which a cellulose ester is dissolved in advance as a material constituting a blending liquid to be described later, and then added to the blending liquid.

The total content of the above-mentioned plasticizer in the cellulose ester film is preferably 5 to 20% by mass, more preferably 6 to 16% by mass, even more preferably 8 to 13% by mass, based on the total amount of the solid content. Further, the content of the two kinds of plasticizers is at least 1% by mass or more, and preferably 2% by mass or more.

The polyol ester-based plasticizer is preferably 1 to 15% by mass, particularly preferably 3 to 11% by mass. When the content of the polyol ester-based plasticizer is too small, planarity is deteriorated, and when it is too large, it is easy to be extravasated. The mass ratio of the polyol ester-based plasticizer to other plasticizers is preferably in the range of 1:4 to 4:1, more preferably 1:3 to 3:1. If the amount of the plasticizer added is too large or too small, the film may be easily deformed.

(solution casting film forming method)

The cellulose ester film is produced by a solution casting film forming method in which a blend is prepared by dissolving a cellulose ester and an additive in a solvent. a step of casting the blend on a conveyor belt-shaped or roll-shaped metal support, a step of drying the cast blend as a web, a step of peeling off from the metal support, The step of stretching or widening is carried out, the step of further drying, and the step of winding up the processed film are carried out.

First, the steps for preparing the blend are explained. The concentration of the cellulose ester in the blend is preferably such that the drying load after casting on the metal support can be reduced when the concentration is high, but if the concentration of the cellulose ester is too high, the load during filtration increases, so that the filtration is performed. The purity is deteriorated. The concentration which can be made two is preferably 10 to 35 mass%, more preferably 15 to 25 mass%.

The solvent to be used for the blending may be used singly or in combination of two or more. However, when a good solvent of a cellulose ester is mixed with a weak solvent, it is preferably from the viewpoint of production efficiency, and when the good solvent is large, the cellulose ester is used. The solubility is preferred. A preferred range of the mixing ratio of the good solvent to the weak solvent is 70 to 98% by mass of the good solvent and 2 to 30% by mass of the weak solvent. The term "good solvent" or "weak solvent" is defined as a good solvent in which the cellulose ester to be used alone is dissolved, and a weak solvent in the case where it is swellable or insoluble. Therefore, by the degree of substitution of the thiol group of the cellulose ester, it can be changed to a good solvent or a weak solvent. For example, when acetone is used as a solvent, the cellulose ester acetate (acetylation degree of 2.4), cellulose acetate The ester propionate becomes a good solvent, and the cellulose acetate (the degree of substitution of acetonitrile is 2.8) becomes a weak solvent.

The good solvent is not particularly limited, and examples thereof include an organic halogen compound such as dichloromethane, a dioxapentane group, acetone, methyl acetate, and ethyl acetacetate. Particularly preferred are dichloromethane or methyl acetate.

Further, the weak solvent is not particularly limited, and for example, methanol, ethanol, n-butanol, cyclohexane, cyclohexanone or the like can be used. Further, it is preferred that the blend contains 0.01 to 2% by mass of water.

When the above blend is prepared, a general method can be used as a method of dissolving the cellulose ester. When heating and pressurizing are combined, heating can be performed at a boiling point or higher at normal pressure. When the solvent is heated at a temperature higher than the boiling point of normal pressure and does not boil the solvent under pressure, it can prevent the occurrence of gel or blocky undissolved matter called mamaco (caking) while stirring and dissolving. Therefore, it is better. Further, it is also preferred to mix the cellulose ester with a weak solvent to form a wet or swell, and then add a good solvent to dissolve.

The pressurization can be carried out by a method of pressurizing an inert gas such as nitrogen or a method of increasing the vapor pressure of the solvent by heating. It is preferable that the heating is performed by the outside, and for example, the jacket type is preferable because it is easy to control the temperature.

The heating temperature at which the solvent is added is preferably from the viewpoint of solubility of the cellulose ester, and when the heating temperature is too high, the productivity is deteriorated because the necessary pressure is excessive. The preferred heating temperature is 45 to 120 ° C, preferably 60 to 110 ° C, and 70 ° C to 105 ° C is preferred. Also, the pressure can be adjusted to the extent that the solvent does not boil at the set temperature.

Further, a cooling dissolution method can also be used, whereby a cellulose ester can be dissolved in a solvent such as methyl acetate.

Further, the cellulose ester solution is filtered using a suitable filter material such as filter paper. As the filter material, it is preferable to remove the insoluble matter or the like with a small absolute filtration accuracy. However, if the absolute filtration accuracy is too small, the filter material is likely to be clogged. Therefore, it is preferable to use a filter material having an absolute filtration accuracy of 0.008 mm or less. 0.001~0.008mm filter material is preferred, and 0.003~0.006mm filter material is better.

The material of the filter medium is not particularly limited, and a general filter medium can be used. A plastic filter material such as polypropylene or Teflon (registered trademark) or a metal filter material such as stainless steel is preferable because no fiber is detached. By filtering, the impurities contained in the cellulose ester of the raw material are particularly preferably used for removing and reducing bright foreign matter.

In the present specification, the bright spot foreign matter is such that the sheet polarizing plate is placed in a crossed Nicols state, and a cellulose ester film is provided therebetween, and light is irradiated from one polarizing plate side and viewed from the other polarizing plate side. side light leak points (foreign matter), of diameter less than 0.01mm or less in order to highlight the number ² 200 / cm is preferred. It is preferably 100 pieces/cm ² or less, more preferably 50 pieces/m ² or less, and particularly preferably 0 to 10 pieces/cm ² or less. Also, the highlights below 0.01 mm are also less preferred.

The filtration of the blend can be carried out by a general method, and the method of filtering while heating at a temperature above the boiling point of the solvent under normal pressure and under the pressure of boiling under the pressure can reduce the filtration pressure difference before and after the filtration ( It is better to refer to the rise of the differential pressure. The preferred temperature is 45 to 120 ° C, preferably 45 to 70 ° C, and more preferably 45 to 55 ° C.

A smaller filter pressure is preferred. The filtration pressure is preferably 1.6 MPa or less, more preferably 1.2 MPa or less, and even more preferably 1.0 MPa or less.

Continue to explain the casting of the blend.

The metal support in the casting (casting) step is preferably one which can be mirror-finished on the surface, and as the metal support, a roll which is surface-plated with a stainless steel conveyor belt or a cast is preferably used.

The casting width can be 1~4m. The surface temperature of the metal support in the casting step is set to be -50 ° C to a temperature at which the solvent does not foam. When the temperature is high, the drying speed of the fabric can be increased, so that the fabric is foamed or the flatness is deteriorated. The temperature of the preferred metal support is preferably from 0 to 100 ° C, more preferably from 5 to 30 ° C. Further, it is also preferable to gel the web by cooling and peeling from the metal support in a state containing a large amount of residual solvent.

The method of controlling the temperature of the metal support is not particularly limited, but a method of blowing warm air or cold air or a method of bringing warm water into contact with the back side of the metal support can be used. When warm water is used, heat can be efficiently transmitted, so that the temperature of the metal support reaches a certain period of time and is preferable. When using warm air, the temperature of the fabric is lowered in consideration of the latent heat of evaporation of the solvent, and the warm air above the boiling point of the solvent can be used to prevent foaming, and a wind higher than the target temperature can also be used.

In particular, it is preferable to carry out drying efficiently from the time of self-casting to peeling, changing the temperature of the metal support, and the temperature of the dry wind.

In order to make the cellulose ester film exhibit good planarity, the residual solvent amount when peeling the fabric from the metal support is preferably 10 to 150% by mass, more preferably 20 to 40% by mass or 60 to 130% by mass, particularly preferably 20 ~30% by mass or 70~120% by mass.

The amount of residual solvent is defined by the following formula.

Residual solvent amount (% by mass) = {(M - N) / N} × 100

Wherein M is the mass of the sample taken at any point during or after manufacture of the woven fabric or film, and N is the mass of M after heating at 115 ° C for 1 hour.

Further, in the drying step of the cellulose ester film, the woven fabric is peeled off from the metal support and then dried, and the residual solvent amount is preferably 1% by mass or less, more preferably 01% by mass or less, and particularly preferably 0 to 0.01% by mass. %the following.

In the film drying step, drying is generally carried out by a roll drying method (a method in which a plurality of rolls disposed on the upper and lower sides are passed through a web and dried) or a tenter method to carry the fabric under drying.

When the cellulose ester film used in the anti-glare film of the present invention is to be produced, the amount of residual solvent of the fabric after peeling from the metal support is immediately extended in the conveying direction, and the ends of the fabric are sandwiched by a press plate or the like. It is particularly good to extend the stenter in the width direction. The preferred stretching ratio in both the longitudinal direction and the lateral direction is preferably 1.01 to 1.3 times, more preferably 1.05 to 1.15 times. By extending in the longitudinal direction and the lateral direction, it is preferable that the area is 1.12 to 1.44 times, and it is more preferably 1.15 to 1.32 times. This can be obtained by the stretching ratio in the longitudinal direction × the stretching ratio in the lateral direction. When the stretching ratio in the longitudinal direction and the lateral direction is less than 1.01 times, ultraviolet irradiation at the time of forming the hard coating layer causes deterioration in planarity.

It is preferable to extend in the longitudinal direction immediately after peeling, and it is preferable to extend by the peeling tension and the conveyance tension thereafter. For example, the peeling tension is preferably 210 N/m or more, and particularly preferably 220 to 300 N/m.

The means for drying the web is not particularly limited, and generally can be carried out by hot air, infrared rays, heating rolls, microwaves, etc., but from the viewpoint of simplicity. Look, it is better to carry out hot air.

The drying temperature in the drying step of the fabric is preferably from 30 to 200 ° C in a stepwise manner, and the dimensional stability is better and better when carried out in the range of from 50 to 180 ° C.

The film thickness of the cellulose ester film is not particularly limited to 10 to 200 μm. In particular, in the film film of 10 to 70 μm, it is difficult to obtain an antireflection film excellent in planarity and scratch resistance, and the present invention can provide an antireflection film of a film excellent in both planarity and scratch resistance, and is excellent in productivity. Therefore, the film thickness of the cellulose ester film is particularly preferably 10 to 70 μm. More preferably 20 to 60 μm. The best is 35~60μm. Further, a cellulose ester film composed of a plurality of layers of a co-casting method may also be used. When the cellulose ester has a multilayer structure, it also has a layer containing a UV absorber and a plasticizer, which may be a core layer, a surface layer, or both.

The antireflection film of the present invention has a width of 1 m or more, and preferably has a width of 1.4 to 4 m. Very good is 1.4~3m. When it exceeds 4m, it is difficult to transport. Further, the surface center line average roughness (Ra) of the hard coat layer provided with the cellulose ester film can be 0.001 to 1 μm.

(melt casting film forming method)

The cellulose ester film can also be preferably formed by a melt casting film forming method.

The solvent used in the solution casting film forming method (for example, methylene chloride or the like) is not specifically classified into a melt extrusion molding method, a pressure molding method, or a blowing method by a melt-melt casting method by heating and melting. Plastic method, injection molding method, air blowing method, extension molding method, and the like. Among them, want to get excellent A cellulose ester film such as mechanical strength and surface precision is preferably a melt extrusion method.

The mixture of the cellulose ester and the additive is subjected to hot air drying or vacuum drying, followed by melt extrusion, and is extruded into a film shape by a T-die, and is adhered to the cooling drum by electrostatic external addition or the like, and is cooled and solidified. , an unstretched film is obtained. The temperature of the cooling drum is preferably maintained at 90 to 150 ° C.

The cellulose resin and other additives such as stabilizers to be added as needed may be preferably mixed before melting. It is preferred that the cellulose resin and the stabilizer are initially mixed. The mixing can be carried out using a mixer or the like, or can be mixed in the cellulose resin preparation process. When a mixer is used, a general mixer such as a V-type mixer, a conical spiral type mixer, a horizontal cylinder type mixer, a Henschel mixer, or a ribbon mixer can be used.

After the film constituting material is mixed as described above, the mixture can be directly melted by an extruder to form a film. However, once the film constituting material is granulated, the granules can be melted by an extruder to form a film. Further, when the film constituent material contains a plurality of materials having different melting points, the so-called rice pass semi-molten is produced only at the temperature of the material having a lower melt melting point, and the semi-melt is introduced into the extruder. And film making. When the film constituting material contains a material which is easily thermally decomposed, it is preferably a method of directly forming a film without granules for the purpose of reducing the number of times of melting, or a method of forming a film such as a semi-melt of rice tong as described above. .

As the extruder, various types of extruders can be used, but a melt-kneading extruder is preferred, and a single-axis extruder or a 2-axis extruder can be used. When the film is made directly from the film, the film is directly formed, and the proper kneading degree is necessary. Therefore, it is preferable to use a two-axis extruder, or a single-axis extruder, or a spiral shape that is changed to a mixed type of Maddock type, Unimelt type, or Dulmage, and can be appropriately kneaded, so that it can be used. As the film constituent material, when a pellet or a rice pass semi-molten is used, a uniaxial extruder or a 2-axis extruder can be used.

The cooling step in the extruder and after the extrusion may be replaced by an inert gas such as nitrogen or the pressure may be lowered to reduce the oxygen concentration.

The melting temperature of the film constituent material in the extruder varies depending on the viscosity or the amount of the film constituent material, the thickness of the sheet to be produced, and the like, but generally, the glass transition temperature (Tg) of the film is Tg. The above is Tg + 100 ° C or less, preferably Tg + 10 ° C or more, and Tg + 90 ° C or less. Specifically, the temperature at the time of melt extrusion is preferably 150 to 300 ° C, and particularly preferably 180 to 270 ° C. More preferably in the range of 200 to 250 ° C.

The melt viscosity at the time of extrusion is 10 to 100,000 poise, preferably 100 to 10,000 poise.

Further, the residence time of the film constituent material in the extruder is preferably shorter, preferably within 5 minutes, preferably within 3 minutes, more preferably within 2 minutes. The residence time is easily controlled by the type and extrusion condition of the extruder 1, but the residence time can be shortened by adjusting the supply amount of the material or the L/D, the number of spiral rotations, the depth of the spiral groove, and the like.

The film is extruded by the above-mentioned extruder, adhered to the cooling drum by electrostatic addition or the like, and cooled and solidified to obtain an unstretched film. The temperature of the cooling drum is preferably maintained at 90 to 150 ° C.

The cellulose ester film used in the present invention is in the wide direction or the film forming side. It is particularly preferable to form a film for extending film formation.

The unstretched film obtained by peeling off the cooling drum is heated by a heating device such as a plurality of rolls and/or an infrared heater, and is heated in a range of a glass transition temperature (Tg) of the cellulose ester to a temperature of Tg + 100 ° C for one or more stages. Longitudinal extension is preferred.

Continuing, the cellulose ester film extending in the longitudinal direction obtained as described above is transversely stretched, and heat treatment is preferably carried out.

The heat treatment is in the range of glass transition temperature (Tg) -20 ° C - extension temperature, and it is generally carried out for 0.5 to 300 seconds under transportation.

The heat-treated film is generally cooled to a temperature below the glass transition temperature (Tg), and the plate holding portion at both ends of the film is cut and then taken up. Further, it is preferable that the cooling is performed at a cooling rate of 100 ° C or less per second from the final heat treatment temperature to the glass transition temperature (Tg).

The means for cooling is not particularly limited, and it can be carried out by a conventionally known means, and in particular, it is preferably cooled in a plurality of temperature regions, and it is preferable to carry out the treatment to improve the dimensional stability of the film. Further, the cooling rate is such that the final heat treatment temperature is represented by T1, and the value obtained by (T1-Tg)/t when the film reaches the Tg from the final heat treatment temperature is represented by t.

The cellulose ester film is preferably an ultraviolet absorber.

As the ultraviolet absorber, the absorption energy of ultraviolet rays having a wavelength of 370 nm or less is excellent, and from the viewpoint of good liquid crystal display properties, it is preferable that the visible light having a wavelength of 400 nm or more is less absorbed.

Specific examples of the ultraviolet absorber include an oxybenzophenone compound, a benzotriazole compound, a salicylate compound, and An benzophenone compound, a cyanoacrylate compound, a triazine compound, a nickel zirconium salt compound, or the like. However, it is not limited to this.

Specific examples of the benzotriazole-based ultraviolet absorber include the following ultraviolet absorbers, but the present invention is not limited thereto.

UV-1: 2-(2'-hydroxy-5'-methylphenyl)benzotriazole UV-2: 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole UV-3: 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)benzotriazole UV-4: 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole UV-5: 2-(2'-hydroxy-3'-(3",4",5",6"-tetrahydroindeninemethyl)-5'-methylphenyl)benzotriazole UV-6: 2,2-extended methyl bis(4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol) UV-7: 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole UV-8: 2-(2H-benzotriazol-2-yl)-6-(linear and branched lauryl)-4-methylphenol (TINUVIN171, manufactured by Ciba) UV-9: Octyl-3-[3-tert-butyl-4-hydroxy-5-(chloro-2H-benzotriazol-2-yl)phenyl]propionate and 2-ethylhexyl- Mixture of 3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate (TINUVIN 109, manufactured by Ciba)

Further, examples of the benzophenone-based ultraviolet absorber include the following specific examples. However, the invention is not limited thereto.

UV-10: 2,4-dihydroxybenzophenone UV-11: 2,2'-dihydroxy-4-methoxybenzophenone UV-12: 2-hydroxy-4-methoxy-5-sulfobenzophenone UV-13: bis(2-methoxy-4-hydroxy-5-benzylidenephenylmethane)

A preferred benzotriazole-based ultraviolet absorber or benzophenone-based ultraviolet absorber having a high transparency and having an effect of preventing deterioration of a polarizing plate or a liquid crystal is preferable as a preferred ultraviolet absorber, and less colored benzoic acid is preferred. Triazole-based ultraviolet absorbers are particularly preferred. In addition, TINUVIN 326, TINUVIN 109, TINUVIN 171, TINUVIN 900, TINUVIN 928, TINUVIN 360 (all manufactured by Ciba Specialty Chemicals Co., Ltd.), LA31 (made by Asahi Kasei Co., Ltd.), and Sumisorb 250 (manufactured by Sumitomo Chemical Co., Ltd.) ), RUVA-100 (manufactured by Otsuka Chemical Co., Ltd.).

Further, the ultraviolet absorber having a partition coefficient of 9.2 or more as described in JP-A-2001-187825 can improve the surface quality of the long-length film and also has excellent coatability. In particular, it is preferred to use an ultraviolet absorber having a partition coefficient of 10.1 or more.

Further, in order to impart lubricity to the cellulose ester film, the same fine particles described in the coating layer containing the active wire-curable resin can be used.

Examples of the fine particles, which are inorganic compounds, include ceria, titania, alumina, zirconia, calcium carbonate, calcium carbonate, talc, clay, calcined clay, calcined calcium citrate, water, and calcium citrate. , aluminum citrate, magnesium citrate and calcium phosphate. The microparticles have a lower turbidity and are better. In particular, cerium oxide is preferred.

The average particle diameter of the primary particles of the microparticles is preferably 5 to 50 nm, more preferably 7 to 20 nm. It is preferable to contain two secondary aggregates having a main particle diameter of 0.05 to 0.3 μm. The content is preferably 0.05 to 1% by mass, particularly preferably 0.1 to 0.5% by mass.

For the fine particles of cerium oxide, for example, fine particles sold under the trade names of Aerosil R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, TT600 (manufactured by Japan Aerosil Co., Ltd.) can be used.

As the fine particles of zirconia, for example, a commercial name of Aerosil R976 and R811 (above, manufactured by Nippon Aerosil Co., Ltd.) can be used.

When polymer particles are used as the fine particles, examples of the polymer include a polyoxyalkylene resin, a fluororesin, and an acrylic resin. Polyoxyalkylene resin is preferred, especially those having a three-dimensional network structure, for example, Tospearl 103, the same 105, the same 108, the same 120, the same 145, the same 3120 and the same 240 (above Toshiba polyoxyl Trade name vendor of alkane co., Ltd.).

Among them, Aerosil 200V and Aerosil R972V are particularly good at maintaining a low turbidity and having a friction coefficient lowering effect.

Further, the cellulose ester film may preferably contain a deterioration preventing agent described below. The deterioration preventing agent will be described.

(deterioration inhibitor)

The deterioration preventing agent is a material which can be inhibited by chemical action due to decomposition of the polymer by heat, oxygen, moisture, acid or the like. The optical film of the invention is formed at a high temperature of 200 ° C or higher, so that it is easy to cause decomposition of the polymer. In the system of deterioration, it is preferred that the deterioration preventing agent is contained in the optical film.

Using an acid generated by oxidation prevention or decomposition of an optical film to capture, inhibit or inhibit decomposition reaction of a radical gene caused by light or heat, etc., and a deterioration or material containing an unresolved decomposition reaction and suppressing coloration or molecular weight reduction. Deterioration inhibitor which is formed by decomposition of volatile components.

Examples of the deterioration preventing agent include an antioxidant, a hindered amine light stabilizer, an acid scavenger, and a metal inerting agent, but are not limited thereto. These are described in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Among them, in order to achieve the object of the present invention, it is preferred that the optical film contains an antioxidant as a deterioration preventing agent.

The amount of the deterioration preventing agent in the optical film forming material of the present invention may be at least one selected from the group consisting of the amount of the cellulose ester of the present invention, and the amount of the deterioration preventing agent added is 0.01% by mass or more and 10% by mass or less. Preferably, it is 0.1% by mass or more and 5.0% by mass or less, more preferably 0.2% by mass or more and 2.0% by mass or less.

The film forming material may be formed by dividing the constituent material into one or a plurality of kinds of particles for the purpose of avoiding deterioration or hygroscopicity of the material. Granulation improves the miscibility or compatibility of the melt during heating, or ensures that the resulting thin Optical uniformity of the film.

(Antioxidants)

Further, the cellulose ester film preferably contains the antioxidant described below. The antioxidant is not particularly limited as long as it can suppress deterioration of the thin film forming material by oxygen, and examples thereof include a phenolic antioxidant, a phosphorus antioxidant, a sulfur antioxidant, and an alkyl radical scavenging. Agent, peroxide decomposing agent, oxygen sweeping agent, and the like. Among them, a phenolic antioxidant, a phosphorus antioxidant, an alkyl radical scavenger is preferred, and a combination of a phenolic antioxidant and a phosphorus antioxidant is preferred, and a phenolic antioxidant and a phosphorus antioxidant and an alkane are combined. The three radical scavengers are the best. By adding these compounds, not only the transparency, heat resistance and the like are not lowered, but also the coloring or strength reduction of the molded body due to heat or thermal oxidative degradation during melt molding can be prevented. These antioxidants may be used singly or in combination of two or more kinds, and the amount thereof is appropriately selected insofar as the object of the present invention is not impaired, and the quality of the cellulose ester of the present invention is 0.01% by mass or more and 10% by mass. The following is preferable, and it is preferably 0.1% by mass or more and 5.0% by mass or less, more preferably 0.2% by mass or more and 2.0% by mass or less.

(phenolic antioxidants)

The phenolic compound is a known compound, and examples of the alkyl-substituted phenol such as p-t-butylphenol or p-(1,1,3,3-tetramethylbutyl)phenol include, for example, U.S. Patent No. 4,839,405. The 2,6-dialkylphenol derivative compound described in the columns 12 to 14 of the specification, the so-called hindered phenol compound, A hindered phenolic compound is preferred.

Specific examples of the hindered phenol phenol-based compound include n-octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)-propionate and n-octadecyl group. 3-(3,5-di-t-butyl-4-hydroxyphenyl)-acetate, n-octadecyl 3,5-di-t-butyl-4-hydroxybenzoate, N-hexyl 3,5-di-t-butyl-4-hydroxyphenyl benzoate, n-lauryl 3,5-di-t-butyl-4-hydroxyphenyl benzoate, new - lauryl 3-(3,5-di-t-butyl-4-hydroxyphenyl)acetate, lauryl β(3,5-di-t-butyl-4-hydroxyphenyl)propionic acid Ester, ethyl α-(4-hydroxy-3,5-di-t-butylphenyl) isobutyrate, octadecyl α-(4-hydroxy-3,5-di-t-butyl Phenyl)isobutyrate, octadecyl α-(4-hydroxy-3,5-di-t-butyl-4-hydroxyphenyl)propionate, 2-(n-octylthio)B 3,5-di-t-butyl-4-hydroxy-benzoate, 2-(n-octylthio)ethyl 3,5-di-t-butyl-4-hydroxy-phenylethylene Acid ester, 2-(n-octadecylthio)ethyl 3,5-di-t-butyl-4 Hydroxyphenyl acetate, 2-(n-octadecylthio)ethyl 3,5-di-t-butyl-4-hydroxy-benzoate, 2-(2-hydroxyethylsulfide) Ethyl 3,5-di-t-butyl-4-hydroxybenzoate, diethyl bis-bis(3,5-di-t-butyl-4-hydroxy-phenyl)propionate , 2-(n-octadecylthio)ethyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, stearylamine N,N-bis-[stretch Ethyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], n-butylimine N,N-bis-[stretch ethyl 3-(3,5- Di-t-butyl-4-hydroxyphenyl)propionate], 2-(2-stearyloxyethylthio)ethyl 3,5-di-t-butyl-4-hydroxybenzoate Acid ester, 2-(2-stearyloxyethylthio)ethyl 7-(3-methyl-5-t-butyl-4-hydroxyphenyl)heptanoate, 1,2-propanediol double -[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], ethylene glycol bis-[3-( 3,5-di-t-butyl-4-hydroxyphenyl)propionate], neopentyl glycol bis-[3-(3,5-di-t-butyl-4-hydroxyphenyl) Propionate], ethylene glycol bis-(3,5-di-t-butyl-4-hydroxyphenyl acetate), glycerol-l-n-octadecanoate-2,3-bis- (3,5-di-t-butyl-4-hydroxyphenyl acrylate), pentaerythritol-indole-[3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propane Acid ester], 1,1,1-trishydroxymethylethane-para-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], sorbitol six- [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2-hydroxyethyl 7-(3-methyl-5-tbutyl-4-hydroxyphenyl) Propionate, 2-stearyloxyethyl 7-(3-methyl-5-t-butyl-4-hydroxyphenyl)heptanoate, 1,6-n-hexanediol-double [(3',5'-Di-t-butyl-4-hydroxyphenyl)propionate], pentaerythritol-indole (3,5-di-t-butyl-4-hydroxyhydrocinnamate). The phenolic compound of the above type is commercially available, for example, from Ciba Specialty Chemicals under the trade names "IRGANOX 1076" and "IRGANOX 1010".

(phosphorus antioxidants)

Examples of the phosphorus-based antioxidant include a phosphite-based compound and a phosphonite-based compound. Specific examples of the phosphite-based compound include triphenyl phosphite, diphenyl isononyl phosphite, phenyl di-isodecyl phosphite, and decyl (decylphenyl) phosphorous acid. Ester, ginseng (di-nonylphenyl) phosphite, ginseng (2,4-di-t-butylphenyl) phosphite, ginseng (2,4-di-t-butyl-5-methyl) Phenyl phosphite, 10-(3,5-di-t-butyl-4-hydroxybenzyl)-9,10-di-hydro-9-oxo-10-phosphaphenan-10-oxidation ,6-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10- a monophosphite compound such as tetra-t-butyldi-benzo[d,f][1.3.2]dioxaphosphepine or tridecylphosphite; 4,4'-butylene-bis(3-甲-6-t-butylphenyl-di-tridecyl phosphite), 4,4'-isopropylidene-bis(phenyl-di-alkyl (C12-C15) phosphite) A di-phosphite compound or the like. For the phosphite-based compound of the above type, for example, "Sumilizer GP" available from Sumitomo Chemical Co., Ltd., "ADK STAB PEP-24G" purchased from Asahi Kasei Kogyo Co., Ltd., and "ADK STAB PEP-36" can be used. The trade names of "ADK STAB 3010", "ADK STAB HP-10" and "ADK STAB 2112".

Specific examples of the phosphonite-based compound include dimethyl-phenylphosphinate, di-t-butyl-phenylphosphinate, and diphenyl-phenylphosphinate. Di-(4-pentyl-phenyl)-phenylphosphinate, bis-(2-t-butyl-phenyl)-phenylphosphinate, bis-(2-methyl-3- Amyl-phenyl)-phenylphosphinate, bis-(2-methyl-4-octyl-phenyl)-phenylphosphinate, bis-(3-butyl-4-methyl -phenyl)-phenylphosphinate, bis-(3-hexyl-4-ethyl-phenyl)-phenylphosphinate, bis-(2,4,6-trimethylphenyl) -phenylphosphonite, bis-(2,3-dimethyl-4-ethyl-phenyl)-phenylphosphinate, bis-(2,6-diethyl-3-butyl Phenyl)-phenylphosphinate, bis-(2,3-dipropyl-5-butylphenyl)-phenylphosphinate, di-(2,4,6-tri-t- Butylphenyl)-phenylphosphinate, bis(2,4-di-t-butyl-5-methylphenyl)biphenyl-4-yl-phosphinate, bis(2, 4-di-t-butyl-5-methylphenyl)-4'-(bis(2,4-di-t-) Butyl-5-methylphenoxy)phosphine)biphenyl-4-yl-phosphinate, bismuth(2,4-di-t-butyl-phenyl)-4,4'-subcontinent Phenyl di-phosphinate, bismuth (2,5-di-t-butyl-phenyl)- 4,4'-biphenylene di-phosphinate, bismuth (3,5-di-t-butyl-phenyl)-4,4'-biphenylene di-phosphinate, hydrazine (2,3,4-trimethylphenyl)-4,4'-biphenylene di-phosphinate, bismuth (2,3-dimethyl-5-ethyl-phenyl)-4 , 4'-biphenylene di-phosphinate, bismuth (2,3-dimethyl-4-propylphenyl)-4,4'-biphenylene di-phosphinate, hydrazine (2,3-Dimethyl-5-t-butylphenyl)-4,4'-biphenylene di-phosphinate, bismuth (2,5-dimethyl-4-t-butyl Phenyl)-4,4'-biphenylene di-phosphinate, bismuth (2,3-diethyl-5-methylphenyl)-4,4'-biphenylene di- Phosphonate, bismuth (2,6-diethyl-4-methylphenyl)-4,4'-biphenylene di-phosphinate, bismuth (2,4,5-triethyl) Phenyl)-4,4'-biphenylene di-phosphinate, bismuth (2,6-diethyl-4-propylphenyl)-4,4'-biphenylene di-- Phosphonate, bismuth (2,5-diethyl-6-butylphenyl)-4,4'-biphenylene di-phosphinate, bismuth (2,3-diethyl-5-) T-butylphenyl)-4, 4'-biphenylene di-phosphinate, bismuth (2,5-diethyl-6-t-butylphenyl)-4,4'-biphenylene di-phosphinate, Bis(2,3-dipropyl-5-methylphenyl)-4,4'-biphenylene di-phosphinate, bismuth (2,6-dipropyl-4-methylphenyl) -4,4'-biphenylene di-phosphinate, bismuth (2,6-dipropyl-5-ethylphenyl)-4,4'-biphenylene di-phosphinic acid Ester, bismuth (2,3-dipropyl-6-butylphenyl)-4,4'-biphenylene di-phosphinate, hydrazine (2,6-dipropyl-5-butyl Phenyl)-4,4'-biphenylene di-phosphinate, bismuth (2,3-dibutyl-4-methylphenyl)-4,4'-biphenylene di-- Phosphonate, bismuth (2,5-dibutyl-3-methylphenyl)-4,4'-biphenylene di-phosphinate, bismuth (2,6-dibutyl-4- Methylphenyl)-4,4'-biphenylene di-phosphinate, bismuth (2,4-di-t-butyl-3-methylphenyl)-4,4'-Asian Phenyl di-phosphinate, bismuth (2,4-di-t-butyl-5-A Phenyl)-4,4'-biphenylene di-phosphinate, bismuth (2,4-di-t-butyl-6-methylphenyl)-4,4'-biphenyl Di-phosphonite, bismuth (2,5-di-t-butyl-3-methylphenyl)-4,4'-biphenylene di-phosphinate, bismuth (2,5 -di-t-butyl-4-methylphenyl)-4,4'-biphenylene di-phosphinate, bismuth (2,5-di-t-butyl-6-methylbenzene -4,4'-biphenylene di-phosphinate, bismuth (2,6-di-t-butyl-3-methylphenyl)-4,4'-biphenylene - phosphonite, bismuth (2,6-di-t-butyl-4-methylphenyl)-4,4'-biphenylene di-phosphinate, bismuth (2,6-di -t-butyl-5-methylphenyl)-4,4'-biphenylene di-phosphinate, bismuth (2,3-dibutyl-4-ethylphenyl)-4, 4'-biphenylene di-phosphinate, bismuth (2,4-dibutyl-3-ethylphenyl)-4,4'-biphenylene di-phosphinate, hydrazine 2,5-Dibutyl-4-ethylphenyl)-4,4'-biphenylene di-phosphinate, bismuth (2,4-di-t-butyl-3-ethylbenzene Base)-4,4' Biphenylene diphosphite, bismuth (2,4-di-t-butyl-5-ethylphenyl)-4,4'-biphenylene di-phosphinate, hydrazine 2,4-di-t-butyl-6-ethylphenyl)-4,4'-biphenylene di-phosphinate, hydrazine (2,5-di-t-butyl-3- Ethylphenyl)-4,4'-biphenylene di-phosphinate, bismuth (2,5-di-t-butyl-4-ethylphenyl)-4,4'-Asian Phenyl di-phosphinate, bismuth (2,5-di-t-butyl-6-ethylphenyl)-4,4'-biphenylene di-phosphinate, bismuth (2, 6-di-t-butyl-3-ethylphenyl)-4,4'-biphenylene di-phosphinate, bismuth (2,6-di-t-butyl-4-ethyl Phenyl)-4,4'-biphenylene di-phosphinate, bismuth (2,6-di-t-butyl-5-ethylphenyl)-4,4'-biphenylene Di-phosphonite, bismuth (2,3,4-tributylphenyl)-4,4'-biphenylene di-phosphinate, bismuth (2,4,6-tri-t- Butylphenyl)-4,4'-biphenylene di-phosphinate. Phosphorus compounds of the above type can be used, for example, by Ciba "IRGAFOSP-EPQ" purchased by Specialty Chemicals Co., Ltd., and "GSY-P101" trade name purchased by Daiei Chemical Industry Co., Ltd.

As the phosphorus-based antioxidant, a phosphonite-based compound is preferable, and bis(2,4-di-t-butyl-phenyl)-4,4'-biphenylene di-phosphinic acid is also used. 4,4'-biphenylene di-phosphonite compound such as ester is preferred, and bis(2,4-di-t-butyl-5-methylphenyl)-4,4' is particularly preferred. - a biphenylene di-phosphinate.

(alkyl radical scavenger)

The cellulose ester film preferably contains an alkyl radical scavenger described below. The alkyl radical scavenger is a compound having a group which rapidly reacts with an alkyl radical and which does not cause a subsequent reaction after reacting with an alkyl radical.

As the alkyl radical scavenger, the trade names of "Sumilizer GM" and "Sumilizer GS" available from Sumitomo Chemical Co., Ltd. can be used.

(hindered amine light stabilizer)

In the cellulose ester film, the deterioration preventing agent in the case of heat-melting of the film forming material, and the deterioration preventing agent for the light of the backlight which is exposed as a polarizer protective film after the production or the backlight of the liquid crystal display are hindered from being added. Amine light stabilizer (HALS) compounds are preferred. As the hindered amine light stabilizer, for example, the 2,2,6,6-tetraalkylpiperidines described in the columns 5 to 11 of the specification of U.S. Patent No. 4,619,956 and the third to fifth columns of the specification of U.S. Patent No. 4,839,405. a compound, or an acid addition salt or these A complex with a metal compound.

Specific examples of the hindered amine light stabilizer include bis(2,2,6,6-tetramethyl-4-piperidine) sebacate and bis(2,2,6,6-tetramethyl). 4-piperidine) succinate, bis(1,2,2,6,6-pentamethyl-4-piperidine) sebacate, bis(N-octyloxy-2,2,6 ,6-tetramethyl-4-piperidine) sebacate, bis(N-benzyloxy 2,2,6,6-tetramethyl-4-piperidine) sebacate, double (N -cyclohexyloxy 2,2,6,6-tetramethyl-4-piperidine) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidine)2- (3,5-di-t-butyl-4-hydroxybenzyl)-2-butylmalonate, bis(1-propenyl-2,2,6,6-tetramethyl-4- Piperidine) 2,2-bis(3,5-di-t-butyl-4-hydroxybenzyl)-2-butylmalonate, bis(1,2,2,6,6-five Methyl-4-piperidine) sebacate, 2,2,6,6-tetramethyl-4-piperidine methacrylate, 4-[3-(3,5-di-t-butyl 4-hydroxyphenyl)propanyloxy]-1-[2-(3-(3,5-di-t-butyl-4-hydroxyphenyl)propanyloxy)ethyl]- 2,2,6,6-tetramethylpiperidine, 2-methyl-2-(2,2,6,6-tetramethyl 4-piperidinyl)amino-N-(2,2,6,6-tetramethyl-4-piperidine)propanamine, hydrazine (2,2,6,6-tetramethyl-4-piperidine ) 1,2,3,4-butanetetracarboxylate, hydrazine (1,2,2,6,6-pentamethyl-4-piperidine) 1,2,3,4-butanetetracarboxylate, etc. .

Further, it may be a polymer type compound, and specific examples thereof include N,N',N",N"'-肆-[4,6-bis-[butyl-(N-methyl-2,2) ,6,6-tetramethylpiperidin-4-yl)amino]-triazine 2-yl]-4,7-di-azaindole-1,10-diamine, dibutylamine and 1, 3,5-triazine N,N'-bis(2,2,6,6-tetramethyl-4-piperidine)-1,6-hexamethyldiamine and N-(2,2,6 , 6-tetramethyl-4-piperidine) butylamine polycondensate, dibutylamine and 1,3,5-triazine with N,N'-bis(2,2,6,6-tetramethyl Polycondensate of benzyl-4-piperidine)butylamine, poly[{(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine 2,4-di-yl} {(2,2,6,6-tetramethyl-4-piperidine)imide}hexamethyl{(2,2,6,6-tetramethyl-4-piperidine)imine}], 1,6-hexanediamine-N,N'-bis(2,2,6,6-tetramethyl-4-piperidine) and morpholine-2,4,6-trichloro-1,3, Polycondensate of 5-triazine, poly[(6-morpholino-s-triazine 2,4-di-yl)[(2,2,6,6-tetramethyl-4-piperidine)imine a high molecular weight HALS with a plurality of piperidine rings via a triazine skeleton; a succinic acid dimethyl group; a polymer of 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6- Pentamethyl-4-piperidinol and 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxo-spiro-[5,5] A piperidine ring such as a mixed ester of monoalkane is a compound in which an ester bond is bonded, but is not limited thereto.

Among them, polycondensate of dibutylamine and 1,3,5-triazine with N,N'-bis(2,2,6,6-tetramethyl-4-piperidine)butylamine, poly[{( 1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine 2,4-di-yl}{(2,2,6,6-tetramethyl-4-piperidin Acridine)imine}hexamethyl{(2,2,6,6-tetramethyl-4-piperidine)imine}], dimethyl succinate and 4-hydroxy-2,2,6,6 The polymer having a number average molecular weight (Mn) of tetramethyl-1-piperidineethanol is preferably 2,000 to 5,000.

For the hindered amine compound of the above type, for example, "TINUVIN 144" and "TINUVIN 770" available from Ciba Specialty Chemicals, and "ADK STAB LA-52" available from Asahi Kasei Kogyo Co., Ltd. can be used.

The hindered amine light stabilizer is preferably added in an amount of 0.1 to 10% by mass, preferably 0.2 to 5 by mass, based on the mass of the cellulose ester of the present invention. %, more preferably 0.5 to 2% by mass. These can be used in combination of 2 or more types.

(acid scavenger)

The cellulose ester can also be decomposed by an acid in a high-temperature environment by melt film formation, and it is preferable that the optical film of the present invention contains an acid scavenger as a deterioration preventing agent. The acid scavenger is preferably a compound which is inert to the acid after the reaction with the acid, and is preferably an epoxy group-containing compound described in the specification of U.S. Patent No. 4,137,201.

The epoxy compound as such an acid scavenger is known in the art field and contains various polyglycol diglycidyl ethers, particularly about 8 to 40 moles of epoxy per 1 gram of polyglycol. A metal epoxy compound such as a condensation-derived polyglycol or a glycerol diglycidyl ether (for example, a vinyl chloride polymer composition, which is used simultaneously with a vinyl chloride polymer composition) ) an epoxidized ether condensation product, a diglycidyl ether of bisphenol A (ie, 4,4'-dihydroxydiphenyldimethylmethane), an epoxidized unsaturated fatty acid ester (especially 2 to 22) An alkyl ester of a carbon atom having 4 to 2 carbon atoms (for example, butyl epoxy stearate), and various epoxidized long-chain fatty acid triglycerides (for example, a ring) The composition of oxidized soybean oil, epoxidized linseed oil, etc., as representative examples of epoxidized vegetable oils and other unsaturated natural oils (sometimes referred to as epoxidized natural glycerides or unsaturated fatty acids, these fatty acids generally contain 12 ~22 carbon atoms). Further, as the commercially available epoxy group-containing epoxide resin compound, EPON 815C or another epoxidized ether oligomer condensation product can also be used.

Further, as an acid scavenger other than the above, an oxetane compound or an oxazoline compound or an alkaline earth metal organic acid salt or an acetoacetate complex is used. The paragraphs [0068] to [0105] are described.

In the present invention, the acid scavenger is preferably added in an amount of 0.1 to 10% by mass based on the mass of the cellulose ester of the present invention, preferably 0.2 to 5% by mass, more preferably 0.5 to 2% by mass. These can be used in combination of 2 or more types.

Further, the acid scavenger may be referred to as an acid scavenger, an acid scavenger, an acid scavenger or the like, and may be used in the present invention.

(metal inert agent)

It is also preferred that the cellulose ester film contains a metal inert agent. The metal inert agent is a compound which is inactivated by a metal ion which acts as a starter or a catalyst in the oxidation reaction, and examples thereof include an anthraquinone compound, a ruthenium oxalate compound, a triazole compound, and the like, and examples thereof include, for example, N,N'-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propanyl]anthracene, 2-hydroxyethyl oxalate diamine, 2-hydroxy-N-( 1H-1,2,4-triazol-3-yl)benzamide, N-(5-yert-butyl-2-ethoxyphenyl)-N'-(2-ethylphenyl) Oxalic acid amide and the like.

The metal inert agent is preferably added in an amount of 0.0002 to 2% by mass based on 100% by mass of the resin of the transparent base film, and is preferably added in an amount of 0.0005 to 2% by mass, more preferably 0.001 to 1% by mass. . These can be used in combination of 2 or more types.

(other additives)

Examples of the cellulose ester film include a dye, a pigment, a phosphor, a dichroic dye, a slippage controlling agent, a refractive index adjusting agent, a gas permeation inhibitor, an antibacterial agent, and a biodegradability imparting agent.

As a method of containing these additives in a cellulose ester, each material may be directly mixed in the form of a solid or a liquid, heated and melted, and then kneaded into a uniform melt, followed by casting to form an optical film, or in advance. After all the materials are dissolved in a uniform solution using a solvent or the like, the solvent is removed, and it is also preferable to contain the mixture of the additive and the cellulose ester film.

(polarizer)

A polarizing plate using the antireflection film of the present invention will be described.

The polarizing plate can be produced by a general method. In the polarizing plate of the present invention, for example, the back side of the anti-glare antireflection film of the present invention is alkalized, and at least one surface of the polarizing film produced by immersing the treated antireflection film in an iodine solution is used. It is preferred to carry out the lamination of a fully alkalized polyvinyl alcohol aqueous solution. On the other hand, the antireflection film is also used, and other polarizing plates can be used to protect the film.

In the anti-glare antireflection film of the present invention, the polarizing plate protective film used on the other side has a phase difference in the in-plane direction (Ro) of 20 to 70 nm and a retardation value (Rt) in the thickness direction of 100 to 400 nm. The optical compensation film (phase difference film) is preferred.

Further, the retention values Ro and Rt can be measured using an automatic complex refractometer. For example, use KOBRA-21ADH (Prince Measurement Machine Co., Ltd. The system is obtained at a temperature of 23 ° C and a humidity of 55% RH at a wavelength of 590 nm.

For example, it can be produced by the method described in JP-A-2002-71957, and the like. Further, it is preferable to use a polarizing plate protective film having an optical compensation film having an optical heterogeneous layer formed by aligning a liquid crystal compound such as a discotic liquid crystal. For example, an optical anisotropic layer can be formed by the method described in JP-A-2003-98348. Or an in-plane retardation value (Ro) of 0 to 5 nm and a thickness-direction retention value (Rt) of -20 to +20 nm may be used.

By using in combination with the antiglare film or the antiglare antireflection film of the present invention, a polarizing plate having excellent planarity and a stable viewing angle expansion effect can be obtained.

As a polarizing plate protective film used for the inside side, as a cellulose ester film for sale, KC8UX2MW, KC4UX, KC5UX, KC4UY, KC8UY, KC12UR, KC4UEW, KC8UCR-3, KC8UCR-4, KC8UCR-5, KC4FR-1 are used. KC4FR-2 (manufactured by Konicaminolta opt Co., Ltd.) or the like is preferred.

The polarizing film which is a main component of the polarizing plate is a light element which passes only a polarizing surface in a certain direction. A representative polarizing film which is known today is a polyvinyl alcohol-based polarizing film, and the polyvinyl alcohol-based film is dyed with iodine. The obtained one is obtained by dyeing a dichroic dye, but is not limited thereto. The polarizing film is formed by forming a film of a polyvinyl alcohol aqueous solution, stretching it by one axis, or dyeing it, and then performing one-axis stretching after dyeing, and it is preferable to use a boron compound for durability treatment. The film thickness of the polarizing film is 5 to 30 μm, preferably 8 ~15μm polarizing film. A polarizing plate is formed by laminating the surface of the anti-glare anti-reflective film of the present invention on the surface of the polarizing film. It is preferred to use a water-based adhesive which is a main component of fully alkalized polyvinyl alcohol or the like.

(display device)

By mounting the antireflection film surface of the present invention on the viewing surface side of the image display device, it is possible to manufacture various image display devices having excellent visibility.

The antireflection film of the present invention is incorporated in a polarizing plate to use a reflective, transmissive, semi-transmissive LCD or TN type, STN type, OCB type, HAN type, VA type (PVA type, MVA type), IPS. LCDs of various driving modes such as the type are preferred. Further, the antireflection film of the present invention is excellent in durability and film strength. It can be used in various display devices such as plasma displays, field emission displays, organic EL displays, inorganic EL displays, and electronic paper.

A specific example of the liquid crystal display device incorporating the antireflection film of the present invention is shown in Fig. 1. The liquid crystal display device of the present invention is adjacent to the light reflecting plate 4, the backlight 7, the light guide plate 5, and the light diffusing plate 6. In the order of the polarizing plate 10 of the present invention (the polarizing plate protective film 1 / the dichroic polarizing film 2 / the polarizing plate protective film 3 as the antireflection film of the present invention), the liquid crystal display panel 8, and the identification side polarizing plate 9 The composition of the lamination is preferred.

[Examples]

The embodiments of the present invention are described below, but the present invention is not limited thereto.

Example 1

(Manufacture of cellulose ester film 1) (modulation of blending solution A) The following materials were sequentially placed in a closed vessel, and the temperature in the vessel was raised from 20 ° C to 80 ° C, and the temperature was maintained at 80 ° C for 3 hours to completely dissolve the cellulose ester. The cerium oxide microparticles are added by dispersing in a previously added solvent and a small amount of a cellulose ester solution. This blend was filtered using a filter paper (Augmentation Filter Paper No. 244, manufactured by Anji Paper Co., Ltd.) to obtain a blending liquid A.

Subsequently, the obtained blending liquid A was cast by a casting mold which was kept at 35 ° C and cast at a temperature of 35 ° C which was formed by a stainless steel endless conveyor belt to form a woven fabric. Continue to dry the fabric on the support, on the fabric When the amount of the residual solvent reached 80% by mass, the fabric was peeled off from the support by the peeling roller.

The woven fabric which has been peeled off is dried while being dried at a drying temperature of 90 ° C in a transfer drying step of a plurality of rolls arranged one above the other, and then the both ends of the fabric are gripped by a tenter, and then the width is made at a temperature of 130 ° C. The direction extends to 1.1 times before the extension. After the extension of the tenter, the fabric was subjected to a transport drying step by means of rolls arranged up and down, and dried by a dry air having a temperature of 135 °C. In the drying step, the ambient gas substitution rate was 15 (times/hour) in an ambient gas for 15 minutes, and then cooled to room temperature and coiled to prepare a width of 1.5 m, a film thickness of 80 μm, a length of 4000 m, and a refractive index of 1.49. Long-length cellulose ester film 1. The stretching ratio of the fabric conveying direction after the peeling straightness calculated from the rotation speed of the stainless steel conveyor belt support and the running speed of the tenter was 1.1 times.

(Production of anti-reflection film) The cellulose ester film 1 produced above was produced into an antireflection film by the following procedure.

(Production of Hard Coating Film) The hard coating layer composition 1 described below was filtered through a polypropylene filter having a pore diameter of 0.4 μm to prepare a hard coating layer coating on the cellulose ester film 1 thus produced. This solution was applied to the surface of the cellulose ester film 1 by a micro gravure coating machine, and dried at a temperature of 90 ° C, and then an ultraviolet ray lamp was used, and the illuminance of the irradiation portion was 100 mW/cm ² , and the irradiation amount was 0.2. The coating layer was cured at J/cm ² to form a hard coating layer having a dry film thickness of 10 μm to prepare a hard coating film.

Continuing, the following back coating layer composition 1 is formed to have a wet film thickness of 14 μm, and coated on the surface of the hard coating layer on which the cellulose ester film 1 is applied, by an extrusion coater, and Drying was carried out at a temperature of 85 °C.

(hard coating layer composition 1) The following materials were stirred and mixed to prepare a hard coating layer composition 1.

(Aerosil 200V made by Aerosil Co., Ltd., Japan) On the surface of the hard coat film produced as described above, an antireflection film was applied in the order of the high refractive index layer and the low refractive index layer described below to prepare an antireflection film.

(Production of particle dispersion A) First, 6.0 kg of hydrazine complex oxide colloid (solid content 60%, manufactured by Nissan Chemical Industry Co., Ltd., zinc silicate sol, trade name: West Lukes CX-Z610M-F2), isopropanol 12.0 The kg was slowly added while stirring, and the particle dispersion A was prepared.

(High refractive index layer coating composition 1)

(High refractive index layer) The high refractive index coating composition 1 was applied onto the surface of the hard coating film by an extrusion coater, dried at a temperature of 80 ° C for 1 minute, and then ultraviolet light was 0.15. The J/cm ^{2 was} irradiated to harden it, and the thickness was set to 78 nm, and the high refractive index layer 1 was provided. The high refractive index layer has a refractive index of 1.6.

(modulation of tetraethoxy decane hydrolysate A) First, 230 g of tetraethoxy decane and 440 g of ethanol were mixed, and 120 g of a 2% aqueous acetic acid solution was added thereto, and the mixture was stirred at room temperature (25 ° C) for 18 hours to prepare a tetraethoxy decane hydrolyzate A.

(low refractive index layer coating composition 1)

(Low Refractive Index Layer) The low refractive index layer coating composition 1 was applied onto the surface of the high refractive index layer 1 of the hard coating film by an extrusion coater, and dried at 100 ° C for 1 minute. Thereafter, the film was irradiated with ultraviolet rays at 0.15 J/cm ² and cured, and further thermally cured at 120 ° C for 5 minutes, and a low refractive index layer was formed to have a thickness of 95 nm to prepare an antireflection film of the present invention.

The refractive index of the low refractive index layer of the obtained antireflection film was 1.37. Further, the antireflection film was immersed in a warm bath using ion exchange water at 50 ° C for 2 hours, and the pH of the surface (film surface) after immersion was measured and found to be 3.8. The microparticle-containing type and the surface (film surface) pH of the low refractive index layer of the antireflection film of Example 1 are shown in Table 1 below.

Further, as a pH measuring device, HM-30G (manufactured by East Asia DKK Co., Ltd.) and pH electrode were used as GST-5723S (East Asian DKK shares) Co., Ltd.). Further, the pH was measured by cutting the antireflection film into 2 cm × 2 cm, and the low refractive index layer of the antireflection film was made to be a surface, and air was not introduced, and attached to a substrate-free double-sided tape (based substrate-free double- A sample was prepared on the acrylic substrate of the coated tape.

Subsequently, the low refractive index layer of the sample attached to the acryl substrate was brought into contact with the pH electrode, and 10 μL of ion-exchanged water was dropped from the contact gap using a microtiter tube (DIGIFIT), and the value after dropping for 1 minute was measured. The pH of the ion-exchanged water was 6.5.

Production of Examples 2 to 9 (antireflection films 102 to 109) and Comparative Examples 1 to 4 (antireflection films 110 to 113)

The amount of acetic acid in the low refractive index layer coating composition 1 is adjusted, and the surface of the antireflection film after being impregnated for 2 hours in a warm bath using ion exchange water at 50 ° C is suitably added with 10% sodium hydroxide and 10% hydrochloric acid. (Thickness) pH As shown in Table 1, the antireflection films 102 to 109 of Examples 2 to 9 and the antireflection films 110 to 113 of Comparative Examples 1 to 4 were produced in the same manner as in Example 1.

Production of Comparative Example 5 (anti-reflection film 114)

The isopropyl alcohol-dispersed hollow cerium oxide microparticle sol of the low refractive index coating composition 1 was changed to the IPS-ST-L of the colloidal cerium oxide sol (isopropyl alcohol dispersion, solid content 30%, Nissan Chemical Industry Co., Ltd. limited The antireflection film 114 of Comparative Example 5 was produced in the same manner as the amount of addition to 30 parts by mass. 2 in a warm bath using ion exchange water at 50 ° C The surface of the antireflection film (film surface) after the hour of immersion had a pH of 3.8.

Production of Comparative Example 6 (antireflection film 115)

The isopropyl alcohol-dispersed hollow cerium oxide microparticle sol of the low refractive index coating composition 1 was changed to the IPS-ST-L of the colloidal cerium oxide sol (isopropyl alcohol dispersion, solid content 30%, Nissan Chemical Industry Co., Ltd. limited The amount of the anti-reflection film surface (film surface) pH of the anti-reflection film after the immersion in 10 minutes of immersion in a warm bath using 50 ° C ion-exchanged water was changed to 30 parts by mass. The antireflection film 115 of Comparative Example 6 was produced in the same manner.

Production of Example 10 (anti-reflection film 116)

The antireflection film 116 of Example 10 was produced in the same manner as the low refractive index layer coating composition 1 was changed to the following low refractive index layer coating composition 2. The surface (film surface) of the antireflection film after immersion in a warm bath using ion exchange water at 50 ° C for 2 hours had a pH of 4.2.

(Coating composition 2 for low refractive index layer) After the fluoropolymer 1 and the sol liquid I were prepared, the coating composition 2 for a low refractive index layer was prepared.

(Preparation of fluoropolymer 1) In an autoclave, a stainless steel stirrer having a content of 100 ml was charged with 40 ml of ethyl acetate, 14.7 g of hydroxyethyl vinyl ether, and 0.55 g of dilauroyl peroxide. Degassing was carried out and replaced with nitrogen. Further, 25 g of hexafluoropropylene (HFP) was introduced into the autoclave, and the temperature was raised to 65 °C. The pressure at the time when the temperature in the autoclave reached 65 ° C was 5.4 kg/cm ² . The reaction was continued for 8 hours while maintaining the temperature in the autoclave, and the heating was stopped at the time when the pressure reached ^3.2 kg/cm ² and left to cool. When the internal temperature was lowered to room temperature, the unreacted monomer was driven out, the autoclave was opened, and the reaction liquid was taken out.

The obtained reaction liquid was poured over excess hexane, and the solvent was removed by a decantation method, and the precipitated polymer was taken out. The polymer was dissolved in a small amount of ethyl acetate, and reprecipitated twice with hexane. The residual monomer was completely removed and dried to obtain 28 g of a polymer. Then, 20 g of this polymer was dissolved in 100 ml of N,N-dimethylacetamide, and 11.4 g of acryl chloride was added dropwise thereto under ice cooling, followed by stirring at room temperature for 10 hours. Ethyl acetate was added to the reaction mixture, and the mixture was washed with water. The organic layer was concentrated and concentrated, and the obtained polymer was re-precipitated with hexane to obtain 19 g of fluoropolymer.

(modulation of sol liquid I) The following materials were placed in a reactor equipped with a stirrer and a reflux condenser and mixed.

Thereafter, 30 parts by mass of ion-exchanged water was added to the mixture, and the reaction was carried out at a temperature of 60 ° C for 4 hours, and then cooled to room temperature to obtain a sol solution. I.

The mass average molecular weight of the reaction product in the sol liquid I was 1,600, and among the components having an oligomer component or more, the component having a molecular weight of 1,000 to 20,000 was 100% by mass. Further, from the gas chromatographic analysis, the propylene methoxypropyltrimethoxy decane of the starting material was completely absent.

(Coating composition 2 for low refractive index layer)

In the coating composition 2 for a low refractive index layer, a fluoropolymer 1 and a methacrylate prepared in advance for methyl ethyl ketone and cyclohexanone The base contains a polysiloxane catalyst, a photoradical generator, a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, and after being added and dissolved at the above-mentioned addition ratio, the sol solution I and the isopropanol are dispersed. The cerium oxide microparticle sol was added at the above-mentioned addition ratio, and finally acetic acid was added.

(assessment) The antireflection films of Examples 1 to 10 and Comparative Examples 1 to 6 prepared above were evaluated by the following methods. The results obtained are shown in Table 1.

(reflectance measurement) The antireflection films of Examples 1 to 10 and Comparative Examples 1 to 6 which were not subjected to the warm bath immersion were conditioned at a temperature of 23 ° C and a relative humidity of 60% for 2 hours, and then the inside reflection was prevented. The black acrylic substrate was attached to a substrate-free double-coated tape, and the reflectance was measured with a konicaminolta spectrophotometer and CM-3700d. Moreover, the lower the reflectance, the better the performance.

(Manufactured by endurance test specimens under high temperature and high humidity) The antireflection films of Examples 1 to 10 and Comparative Examples 1 to 6 were each cut into an A4 size, and the antireflection layer was used as a surface, and maintained at a temperature of 80 ° C and a humidity of 90% RH for 250 hours in a high temperature and high humidity environment. The antireflection film was conditioned at a temperature of 23 ° C and a relative humidity of 60% for 2 hours to prepare a film sample for wet heat durability test. Durable for these damp heat The film samples for the test were evaluated for the following rub resistance (film strength), adhesion, and chemical resistance, and subjected to a damp heat durability test.

(Film Strength) The film samples for the wet heat durability test of the antireflection films of Examples 1 to 10 and Comparative Examples 1 to 6, each of which was made of Nippon Steel Wool Co., Ltd., line #0000, steel wool (SW) The load was 1000 g/cm ² , and the number of scratches per 1 cm of the antireflection film at the time of 20 reciprocation was measured. The number of the scratches of the antireflection film is preferably 5 pieces/cm or less from the viewpoint of practical use, and preferably 3 pieces/cm width or less, more preferably 1 piece/cm width or less. The device for reciprocating the steel wool is a frictional wear tester (TRIBOSTATION TYPE: 32, moving speed 4000 mm/min.) using Xindong Science and Technology Co., Ltd. The results obtained are summarized in Table 1 below.

(adhesiveness) The anti-reflection film of the anti-reflection film of Examples 1 to 10 and Comparative Examples 1 to 6 was cut on the surface of the anti-reflection layer of the film sample facing the razor at an angle of 90 并 and cut into 11 vertical and horizontal sections at intervals of 1 mm. , made 100 square squares with a side length of 1mm. Attach the purchased cellophane tape to the top, hold it at one end, and stretch and peel it in the vertical direction. The ratio of the peeled area of the film to the area of the tape attached to the cut line is visually observed. Observe and evaluate on the basis of the following criteria. The results obtained are summarized in Table 1.

Adhesion evaluation ◎: completely unpeeled ○: area ratio of peeled off was less than 5% Δ: area ratio of peeled area was less than 10% ×: area ratio of peeled area was 10% or more

(drug resistance) Chemical resistance 1: ethanol The surface of the film sample for the wet heat durability test of the antireflection film of Examples 1 to 10 and Comparative Examples 1 to 6 was used in bemcot (product of Asahi Kasei Co., Ltd., product name M) which was dyed with ethanol (manufactured by Kanto Chemical Co., Ltd.). -3), rubbing back and forth 20 times in the same place, observing the state after wiping, and evaluating by the following criteria.

Chemical resistance 2: naphtha The surface of the film sample for the wet heat durability test of the antireflection film of Examples 1 to 10 and Comparative Examples 1 to 6 was made of bemcot (made by Asahi Kasei Co., Ltd.), which was dyed with naphtha (manufactured by Wako Pure Chemical Industries, Ltd.). The product name M-3) was rubbed back and forth 20 times at the same place, and the state after wiping was observed, and the evaluation was performed based on the following criteria.

The results obtained are summarized in Table 1. Further, the surface of the antireflection film was wiped using the following device.

Surface wiping device: Xindong Science Co., Ltd. friction wear test machine (TRIBOSTATION TYPE: 32, moving speed 4000mm/min.) Load 1000g/cm ² , tip contact area: 1cm × 1cm

Chemical resistance 1: Ethanol and chemical resistance 2: Evaluation criteria for naphtha ◎: Not peeled off ○: A slight peeling level was observed (no practical problem) △: Peeling was observed ×: After wiping All stripped.

As is apparent from the results of Table 1, the low refractive index layer contains hollow cerium oxide microparticles which are porous or void inside, and the surface of the low refractive index layer (film surface) after immersion in a 50 ° C warm bath for 2 hours has a pH of 2.0. The antireflection film of the present invention of ~7.5 is reflectance, adhesion after wet heat endurance test, film strength (scratch resistance), and chemical resistance (ethanol, naphtha) as compared with the antireflection film of the comparative example. ) are all excellent. It was found that the antireflection film of the present invention having a low refractive index layer surface (film surface) pH of 2.0 to 4.0 has excellent film strength (scratch resistance) and chemical resistance (ethanol) after the wet heat endurance test.

Production of Examples 11 to 22 (antireflection film 117 to 128)

In the production of the antireflection film of the first embodiment, the additive composition 1 for the low refractive index layer is further added to the additive described in Table 2, and after immersion in a warm bath using ion exchange water at 50 ° C for 2 hours. Antireflection films 117 to 128 were produced in the same manner as in Example 1 except that the pH of the antireflection film surface (film surface) was constant, the amount of acetic acid was adjusted, and 10% sodium hydroxide and 10% hydrochloric acid were appropriately added. Further, the surface (film surface) pH of the ion-exchanged water at 50 ° C of the antireflection film prepared above and immersed in a warm bath for 2 hours is shown in Table 2.

Continuing, the antireflection films 117 to 128 of the above-described 11th to 22nd embodiments, the antireflection film 101 of the first embodiment, and the antireflection film 108 of the eighth embodiment are cut into an A4 size, and the antireflection layer is used as a surface. After storage for 500 hours in a high temperature and high humidity environment at a temperature of 80 ° C and a humidity of 90% RH, the antireflection film was subjected to a temperature of 23 ° C and a relative humidity of 60%. The humidity was measured in the hour, and the adhesion, the scratch resistance (film strength), and the chemical resistance were evaluated by the above method, and the moist heat durability test was performed. The results obtained are shown in Table 2 below.

Further, the details of the additives described in Table 2 are as follows.

Hydroxy modified polyoxyalkylene resin: FM-DA26, manufactured by Chisso Co., Ltd. Epoxy modified polyoxyalkylene resin: X-22-163B, manufactured by Shin-Etsu Chemical Co., Ltd. Amine-modified polyoxyalkylene resin: X-22-161A, manufactured by Shin-Etsu Chemical Co., Ltd. Methanol modified polyoxyalkylene resin: KF-6003, manufactured by Shin-Etsu Chemical Co., Ltd. Imidazole (manufactured by JEOL Ltd.) 1-methylimidazole (manufactured by JEOL Ltd.)

From the results of the above Table 2, it is known that in the excessively severe wet heat durability evaluation, when the low refractive index layer contains a reactive modified polyoxyalkylene resin or imidazole or a derivative thereof, it is known that it has a superior heat and humidity durability test. Post-adhesiveness, film strength (scratch resistance) and chemical resistance (ethanol, naphtha).

Example 23

Using the antireflection films 101 to 128 produced in Examples 1 to 22 and Comparative Examples 1 to 6, polarizing plates were produced as follows, and these polarizing plates were placed in a liquid crystal display panel (image display device) to evaluate the visibility.

The antireflection film of the above Examples 1 to 22 and Comparative Examples 1 to 6 and KC8UCR5 (manufactured by Konicaminolta opt Co., Ltd.) of the cellulose ester-based optical compensation film were used as polarizing plates. In other words, each of the antireflection film and the optical compensation film is used as a polarizing plate protective film bonded to the front and back of the polarizing film to form polarizing plates 201 to 228.

(a) Production of polarizing film In 100 parts by mass of polyvinyl alcohol (hereinafter abbreviated as PVA) having a degree of alkalinity of 99.95 mol% and a degree of polymerization of 2400, 10 parts by mass of impregnated glycerin and 170 parts by mass of water are melt-kneaded, and T-plastic is obtained after defoaming. The mold was melted and extruded on a metal roll to form a film. Thereafter, it is dried. Heat treatment to obtain a PVA film. The obtained PVA film had an average thickness of 40 μm, a moisture content of 4.4%, and a film web of 3 m.

Continue, the resulting PVA film is prepared by swelling, dyeing, and damp After the method, the polarizing film is produced by performing continuous treatment in the order of one-axis stretching, fixing treatment, drying, and heat treatment.

Specifically, the PVA film was immersed in water at a temperature of 30 ° C for 30 seconds as a preliminary swell, and immersed in an aqueous solution having an iodine concentration of 0.4 g / liter and a potassium iodide concentration of 40 g / liter at a temperature of 35 ° C for 3 minutes. Continue to apply a tension of 700 N/m to a film at a concentration of 700 N/m in a 50% aqueous solution having a boric acid concentration of 4%, and to carry out one-axis extension to 6 times, a potassium iodide concentration of 40 g/liter, a boric acid concentration of 40 g/liter, and a zinc chloride concentration of 10 g/ The temperature was raised in a 30 ° C aqueous solution at a temperature of 5 ° C for 5 minutes to carry out a fixing treatment. Thereafter, the PVA film was taken out, dried by hot air at a temperature of 40 ° C, and further heat-treated at a temperature of 100 ° C for 5 minutes. The obtained polarizing film had an average thickness of 13 μm, a transmittance for polarizing performance of 43.0%, a degree of polarization of 99.5%, and a 2-color ratio of 40.1.

(b) Production of polarizing plate Continuing, according to the following steps 1 to 5, the antireflection films 101 to 128 of Examples 1 to 22 and Comparative Examples 1 to 6 and the cellulose ester-based optical compensation film are used as a polarizing plate protective film, and are bonded to the above polarizing film. In the table, polarizing plates 201 to 228 corresponding to the antireflection films 101 to 128 of Examples 1 to 22 and Comparative Examples 1 to 6 were produced.

Step 1: As a polarizing plate protective film, the antireflection films of Examples 1 to 22 and Comparative Examples 1 to 6 were immersed in a 2 mol/L sodium hydroxide solution at 60 ° C for 90 seconds, and then subjected to water washing, drying, and alkalization. The side that is attached to the polarizing film.

Similarly, as the polarizing plate protective film on the opposite side of the polarizing film, the alkalization of the commercially available cellulose ester film KC8UCR5 was also carried out.

Step 2: The polarizing film was immersed in a storage tank of a polyvinyl alcohol adhesive solution having a solid content of 2% by mass for 1 to 2 seconds.

Step 3: Gently wipe off the excess adhesive attached to the polarizing film in step 2. The polarizing film is sandwiched between the alkalized surface of the cellulose ester film KC8UCR5 treated in the step 1 and the alkalized surface of the antireflection film. It is used as a polarizing plate.

Step 4: The polarizing plate prepared in the step 3 is applied to the two rotating drums at a speed of about 20 m/min at a pressure of 20 to 30 N/cm ² .

Step 5: The polarizing plate prepared in the step 4 was dried in a dryer at a temperature of 80 ° C for 2 minutes to prepare polarizing plates 201 to 228.

Continuing, the following evaluations were carried out using the polarizing plates 201 to 228 prepared as described above.

The outermost polarizing plate of the commercially available liquid crystal display panel (VA type) was carefully peeled off, and the polarizing plates 201 to 228 which were combined with the polarizing direction were bonded to each other to form liquid crystal panels 301 to 328.

The liquid crystal panels 301 to 328 thus obtained are placed on a table having a height of 80 cm from the floor, and a fluorescent lamp with a daylight color straight tube (FLR40S.D/M-X, Matsushita Electric Co., Ltd.) Industrial Co., Ltd.) 40 W × 2 is used as one set, and 10 sets are placed at intervals of 1.5 m. At this time, the evaluator is on the front side of the display panel of the liquid crystal panel, and a fluorescent lamp is placed on the ceiling portion so that the fluorescent light can be irradiated from the head of the evaluator to the rear. For the LCD panel, infuse the fluorescent lamp from the direction in which the table is tilted in a vertical direction of 25 inches. And the visibility (identification) of the screen is evaluated according to the following levels. .

Moreover, the bright spot foreign matter of the liquid crystal panels 301-328 produced above was also evaluated by the following grade.

(assessment) (identification) A: The noise of the closest fluorescent light is not noticeable, and the text with a font size of 8 or less is also readable. B: The shadow of the nearby fluorescent light is slightly noticeable, but it is not noticeable in the distance. The font size is less than 8 and the text is barely readable. C: The ingestion of the fluorescent light in the distant place is noticeable, and the characters with a font size of 8 or less are difficult to read. D: The shadow of the fluorescent light is very interesting. The characters with a glyph size of 8 or less cannot be read.

(bright spot foreign body) The display of the liquid crystal panels 301 to 328 was made into a full black display, and the diameter and number of the bright foreign matter were calculated by a magnifying glass, and evaluated according to the following criteria. At this time, the magnification of the magnifying glass is 50 times.

○: No foreign matter of 100 μm or more was observed ×: Foreign matter of 100 μm or more was observed. It is a standard for practical problems.

The evaluation results are shown in Table 3.

It is known from the evaluation results of Table 3 that the antireflection film of the present invention is used. 101 to 109 and 116 to 128, and the liquid crystal panels 301 to 309 and 316 to 328 of the polarizing plates 201 to 209 and 216 to 228 of the present invention are all evaluation results of B or more, and the antireflection film 110 of the comparative example is used. 115, and the liquid crystal panels 310 to 315 of the polarizing plates 210 to 215 of the comparative example have better visibility. Moreover, the liquid crystal panel of the present invention is also a good product having a bright foreign matter of not more than 100 μm.

1‧‧‧Anti-reflection film (polarizing plate protective film) relating to the present invention

2‧‧‧ dichroic polarizing film

3‧‧‧Polarizer protective film

4‧‧‧Light diffuser

5‧‧‧Light guide plate

6‧‧‧ Backlight

7‧‧‧LCD panel

8‧‧‧ Identification side polarizer

Fig. 1 is a schematic view showing the configuration of a preferred liquid crystal display device of the present invention.

1‧‧‧Anti-reflection film (polarizing plate protective film) relating to the present invention

2‧‧‧ dichroic polarizing film

3‧‧‧Polarizer protective film

4‧‧‧Light diffuser

5‧‧‧Light guide plate

6‧‧‧ Backlight

7‧‧‧LCD panel

8‧‧‧ Identification side polarizer

Claims (5)

An antireflection film which is an antireflection film having a low refractive index layer on the outermost surface of at least one of the transparent film substrates, characterized in that the low refractive index layer contains at least one hollow dioxide which is porous or void inside. The fine particles and the additive as the pH of the control surface (film surface) contain the imidazole or the derivative thereof represented by the following general formula (1), and the antireflection film having the low refractive index layer is cut out by 2 cm × 2 cm, and is made low. The refractive index layer is a surface, and is intended to prevent air from entering, and is attached to a sample coated on a propylene substrate having no double-sided tape of the substrate, so that the low refractive index layer of the sample attached to the acryl substrate is in contact with the pH electrode, and the gap between the contacts is contacted. 10 μL of ion-exchanged water was dropped by using a microtiter tube, and the surface (film surface) of the low refractive index layer after dropping for 1 minute was measured to have a pH of 2.0 to 7.5; (R1) nA (1) where R ¹ represents hydrogen. An atom, an alkyl group having 1 to 3 carbon atoms which may be substituted by an amine group or a hydroxyl group, an alkenyl group and a halogen atom. When R ¹ is plural, they may be the same or different from each other; and 1 or 2 of the amine groups represented by R ¹ may be Substituting a methyl group or an ethyl group; further, the alkyl group and the alkenyl group may be carried out by an alkyl group having 1 to 3 carbon atoms. Substituted; n is an integer from 1 to 3; A represents an imidazolyl group. The antireflection film of claim 1, wherein the surface of the low refractive index layer (film surface) has a pH of 2.0 to 4.0. The antireflection film of claim 1, wherein the surface of the low refractive index layer (film surface) is measured under the conditions of a temperature of 50 ° C in a bath for 2 hours. A polarizing plate characterized in that an antireflection film according to any one of items 1 to 3 of the patent application is used on one side. A display device characterized by using an antireflection film according to any one of items 1 to 3 of the patent application.