TWI480571B - A low reflection member, a reflection preventing film, a polarizing member, and a portrait display device - Google Patents

Description

Low reflection member, antireflection film, polarizing plate and image display device

The present invention relates to a low-reflection member, an anti-reflection film, a polarizing plate, and an image display device, and more particularly to a binder resin containing cerium oxide-containing fine particles on a support substrate such as a glass plate, a plastic film, and a plastic plate. It is a low-reflection member that is excellent in scratch resistance and adhesion.

In the past, a composition for an optical material containing yttrium oxide fine particles or the like is applied onto a support substrate such as a glass plate, a plastic film or a plastic plate to form a film (low refractive index layer) which imparts a function of preventing reflection and the like. Low reflection member. Therefore, the low refractive index layer mostly fixes the cerium oxide microparticles on the surface of the supporting substrate by the binder component. Specifically, for example, a binder resin such as an acrylic resin, an epoxy resin, or a decane resin is used as a binder component, and is fixed to the surface of the support substrate.

The low-reflection member to which the cerium oxide fine particles are fixed is exemplified by the following Patent Document 1 or Patent Document 2 below. Patent Document 1 describes an image display panel (low reflection member) in which tetraethoxy decane is used as a binder component and cerium oxide microparticles are fixed to a light-transmitting substrate (support substrate). Further, it has been disclosed that the ruthenium oxide fine particles can be formed on the light-transmitting substrate by using tetraethoxysilane as a binder component to form an external light-reflecting film (low-refractive-index layer).

Further, Patent Document 2 discloses a low-reflection member in which cerium oxide fine particles are fixed in a single particle layer on at least one surface of a support substrate, and the cerium oxide fine particles are fixed by a binder component composed of a cationic polymerizable monomer as a main component. .

The low-reflection member in which the cerium oxide microparticles are fixed on the support substrate is required to inhibit the detachment of the ruthenium oxide microparticles from the low-refractive-index layer containing cerium oxide microparticles formed on the support substrate, and further requires a low refractive index layer. It has high scratch resistance and high adhesion to the support substrate of the low refractive index layer.

When tetraethoxy decane is used as a binder component as described in Patent Document 1, in order to improve the adhesion to the support substrate, it is necessary to make tetraethoxy decane a decane-based resin by a high-temperature treatment. That is, when tetraethoxy decane is used, it takes a long time for high-temperature treatment, and in particular, when a plastic sheet having low heat resistance is used as a supporting substrate, sufficient adhesion cannot be obtained, and thermal deformation occurs. That is, when a decane-based resin is used as the binder resin, it takes a long time for high-temperature treatment to improve the adhesion. Further, the adhesion after the light resistance test tends to be worse than that of the cationically polymerizable binder resin such as an epoxy resin.

Further, when an acrylic resin is used as the binder resin component, the initial adhesion to the support substrate is excellent, but after the light resistance test, the adhesion tends to be lowered.

Therefore, when a cationically polymerizable binder resin such as an epoxy resin is used as the binder resin, the initial adhesion is not limited, and the adhesion after the light resistance test tends to be excellent. However, in the case of using a cationically polymerizable binder resin such as an epoxy resin, when the cerium oxide particles are disposed only in a single particle layer, the cerium oxide particles are liable to fall off and the scratch resistance is weak. .

Prior technical literature Patent literature

Patent Document 1: JP-A-1-15444

Patent Document 2: Patent No. 3120916

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a low-reflection member which is excellent in scratch resistance and adhesion and which can suppress the occurrence of cerium oxide fine particles from falling off, and the reflection preventing by the low-reflection member. A film, a polarizing plate using the antireflection film, and an image display device.

The low-reflection member of the present invention has (a) a cationically polymerizable binder resin, (b) a phosphonium-based acid generator, and (c) an outer shell layer on at least one side of the support substrate, and has a porous inner portion or The low refractive index layer of the hollow cerium oxide microparticles, wherein the thickness of the low refractive index layer is more than one time and less than three times the average particle diameter of the cerium oxide microparticles, and the surface roughness Ra of the low refractive index layer is less than 5 nm.

According to the above configuration, it is possible to provide a low-reflection member which is excellent in scratch resistance and adhesion, can suppress the occurrence of cerium oxide fine particles from falling off, an antireflection film made of the low reflection member, a polarizing plate using the antireflection film, and an image. Display device.

The above and other objects, features, and advantages of the present invention will become more apparent from the description and appended claims.

Hereinafter, the form of the present invention will be described in detail, but the present invention is not limited thereto.

A low-reflection member according to an embodiment of the present invention is characterized in that (a) a cationically polymerizable binder resin, (b) a phosphonium-based acid generator, and (c) an outer shell layer are provided on at least one surface of a support substrate. a low refractive index layer containing ruthenium oxide microparticles having a porous or voided inner portion, wherein the thickness of the low refractive index layer is more than one time and less than three times the average particle diameter of the cerium oxide microparticles, and the surface of the low refractive index layer is rough The degree Ra is less than 5 nm.

In this configuration, the binder resin is excellent in adhesion to the support substrate, and the cationically polymerizable binder resin which is ultraviolet-cured due to high reactivity and productivity. Since the cationically polymerizable binder resin has low reactivity, it is easy to generate hardness by using a specific lanthanic acid generator having high reactivity. As for the cerium oxide microparticles, in order to reduce the reflectance, the specific gravity is lower than that of the general cerium oxide microparticles. The thickness of the low refractive index layer is more than one time and less than three times the average particle diameter of the cerium oxide microparticles. If it is more than this, the strength of the binder resin itself may greatly affect the hardness of the cerium oxide microparticles, and the scratch resistance may be deteriorated. Further, it has been found that scratch resistance can be improved by making Ra less than 5 nm.

This phenomenon is presumed as follows.

First, it is considered that the cationically polymerizable binder resin is generally low in reactivity, but by using a sulfonium-based acid generator having high reactivity to improve reactivity, it is possible to obtain a polymerization reaction as appropriate. Therefore, it is considered that the low refractive index layer containing the cationically polymerizable binder resin is not only easy to obtain a high hardness but also has a high adhesion to the lower layer.

Further, since the cerium oxide microparticles have an outer shell layer and are porous or hollow inside, the specific gravity is lower than that of the solid cerium oxide microparticles. Therefore, it is considered that by using such cerium oxide fine particles having a low specific gravity, the refractive index of the formed low refractive index layer can be adjusted to be appropriate, and the reflectance can be lowered.

Further, it is considered that the thickness of the low refractive index layer is more than one time and less than three times the average particle diameter of the cerium oxide fine particles, and the surface roughness Ra of the low refractive index layer is less than 5 nm, which is reduced to be exposed to the foregoing. The cerium oxide microparticles are fixed in the state of the surface of the low refractive index layer, and the occurrence of detachment of the cerium oxide microparticles can be suppressed.

Further, since the cerium oxide fine particles have a shell layer and are porous or void inside, when the cerium oxide fine particles are contained, the layer is easily buffered, and the hardness of the layer is specifically low, for example, the pencil hardness is low. There is a tendency to become a vulnerable layer. Therefore, it is considered that by setting the thickness of the low refractive index layer to be more than one time and less than three times the average particle diameter of the cerium oxide fine particles, the hardness of the low refractive index layer can be suppressed from being lowered, and scratch resistance can be suppressed. Reduced.

Therefore, it is considered that it is excellent in scratch resistance and adhesion, and in particular, it is excellent in scratch resistance and adhesion after the light resistance test, and it is possible to suppress the occurrence of oxidized cerium particles falling off. A reflection preventing film made of a reflecting member, a polarizing plate using the antireflection film, and an image display device.

The adhesion level of the low-reflection member according to one embodiment of the present invention can reach the cross-cut adhesion test according to JIS K 5600-5-6 after the light resistance test, and the affected area is 5% or less. grade.

In the above-mentioned cross-cutting method, for example, a film having a width of 1 mm is cut out on the film after the light resistance test using a dicing blade to form 100 squares of 1 mm square (cross cut), which are commercially available. Next, the tape was pressed and subjected to a peeling test for about 3 to 5 times on the cross cut, and the average area of the number of peeled squares was obtained. The smaller the ratio of the area, the better the adhesion is better.

The pencil hardness is determined by using the pencil for testing specified in JIS-S6006, using the pencil hardness evaluation method specified in JIS-K5400, using a 500 gram method, and drawing the surface of the refractive index layer five times with a pencil of each hardness to measure the flaw. Achieve a hardness of one. The higher the number, the higher the hardness.

Further, the low-reflection member according to an embodiment of the present invention is not limited to a specific shape. As the low-reflection member, for example, a transparent film substrate may be used as the support substrate, and the reflective film may be used. That is, the antireflection film according to another embodiment of the present invention is composed of the above-described low reflection member.

Further, by including the cellulose ester resin or the cellulose ester resin and the acrylic resin, and further containing the cellulose ester resin, the acrylic resin, and the acrylic particles, the support substrate can provide a superior adhesion to the antistatic layer. Reflective member.

Hereinafter, each element of the low reflection member according to an embodiment of the present invention will be described in detail.

<low refractive index layer>

First, the low refractive index layer of the present embodiment will be described. The low refractive index layer of the present embodiment has at least (a) a cationically polymerizable binder resin, (b) a sulfonium acid generator, and (c) an outer shell layer, and contains cerium oxide fine particles having a porous or void inside. The thickness of the low refractive index layer is more than one time and less than three times the average particle diameter of the cerium oxide fine particles, and the surface roughness Ra of the low refractive index layer is less than 5 nm. Further, the low refractive index layer may further contain (d) an ionizing radiation curable resin, (e) a photo radical initiator, and the like.

The low refractive index layer refers to a layer having a lower refractive index than the supporting substrate. The specific refractive index is preferably in the range of 23 ° C and the wavelength of 550 nm of 1.20 to 1.45, more preferably in the range of 1.25 to 1.40, and most preferably in the range of 1.30 to 1.37. 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, from the characteristics of the optical interference layer.

(cationic polymerizable binder resin)

In the present embodiment, at least the low refractive index layer contains a cationically polymerizable binder resin. The cationically polymerizable binder resin is not particularly limited, but preferably has at least one of an epoxy group and a vinyl ether group. Further, the cationically polymerizable binder resin is preferably one which cures the cationically polymerizable monomer by ultraviolet irradiation.

Further, the cationically polymerizable binder resin having an epoxy group is not particularly limited, but is preferably an alkoxydecane compound having an epoxy group, and specifically preferably contains, for example, an organic compound represented by the following formula (5). A hydrazine compound or a hydrolyzate thereof or a polycondensate thereof.

R ¹⁸ _m SiX ² _4-m (5)

In the formula (5), R ¹⁸ is a substituent having an epoxy group, X ² is a hydroxyl group or a hydrolyzable substituent, and m is an integer of 0 to 3.

R ¹⁸ of the cationically polymerizable binder resin represented by the formula (5) is not particularly limited, but is exemplified by, for example, 2-glycidoxyethyl group, 3-glycidoxypropyl group, and 3-epoxy group. A glycidyloxy C1~C4 alkyl group such as a propoxybutyl group, preferably a glycidoxy C1~C3 alkyl group, a glycidyl group, or a 2-(3,4-epoxycyclohexyl) , 3-(3,4-epoxycyclohexyl)propyl, 2-(3,4-epoxycycloheptyl)ethyl, 2-(3,4-epoxycyclohexyl)propyl , 2-(3,4-epoxycyclohexyl)butyl, 2-(3,4-epoxycyclohexyl)pentyl, etc., substituted by a C5-C8 cycloalkyl group having an epoxy group C1~C5 alkyl. Among these, 2-glycidoxyethyl, 3-glycidoxypropyl and 2-(3,4-epoxycyclohexyl)ethyl are preferred. Preferred specific examples of the compound which can be used as the compound of the formula (5) having the substituent R ² are exemplified as 2-glycidoxyethyltrimethoxydecane, 2-glycidoxyethyl Triethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, 2-(3,4)-epoxycyclohexylethyl Triethoxy decane and the like. These may be used alone or in combination of two or more.

The X ² of the cationically polymerizable binder resin represented by the formula (5) is not particularly limited, and examples thereof include alkoxy groups such as a methoxy group, an ethoxy group, and a propoxy group. Among them, a methoxy group and an ethoxy group are preferred.

The alkoxydecane compound used in the present embodiment can be obtained by, for example, condensing an alkoxydecane compound of the formula (5) under a basic catalyst. At this time, in order to promote (co)condensation, water may be added as needed. The amount of water added is usually from 0.05 to 1.5 moles, preferably from 0.1 to 1.2 moles, per mole of the alkoxy group of the reaction mixture. The catalyst used in the condensation reaction is not particularly limited as long as it is alkaline, and an inorganic base such as sodium hydroxide, potassium hydroxide, lithium hydroxide, barium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate or potassium hydrogencarbonate can be used. An organic base such as ammonia, triethylamine, di-ethyltriamine, n-butylamine, dimethylaminoethanol, triethanolamine or tetramethylammonium hydroxide. Among them, in particular, from the viewpoint of easily removing the catalyst from the product, an inorganic base or ammonia is preferred. The amount of the catalyst added is usually 5 × 10 ^-4 to 7.5% by mass, preferably 1 × 10 ^-3 to 5% by mass based on the amount of the alkoxydecane compound. The above condensation reaction can be carried out without a solvent or in a solvent. The solvent in the case of using a solvent is not particularly limited as long as it is a solvent which can dissolve the alkoxydecane compound. Examples of such solvents include non-polar solvents such as dimethylformamide, dimethylacetamide, tetrahydrofuran, methyl ethyl ketone, and methyl isobutyl ketone, and aromatic hydrocarbons such as toluene and xylene. Good is methyl ethyl ketone, methyl isobutyl ketone. The alkoxy decane compound to be used in the present embodiment can be produced by a known method, and the method described in JP-A-2006-348061, JP-A-2006-348061, and JP-A-2006-348061 Manufacturing.

Further, the cationically polymerizable binder resin having a vinyl ether group is not particularly limited, but it is preferably one obtained by curing a cationically polymerizable monomer having a vinyl ether group by ultraviolet irradiation. The cationically polymerizable monomer having a vinyl ether group is specifically, for example, a polyalkylene glycol such as diethylene glycol divinyl ether or polyethylene glycol divinyl ether, and 1,4-cyclohexane. A cycloalkaneditanyl divinyl ether such as methanol divinyl ether.

(鋶 salt acid generator)

The sulfonium-based acid generator used in the present embodiment can be used by all the well-known ones disclosed in "Application and Market of UV EB Hardening Technology" (CMC Publishing, Edited by Tamura Miho / Edited by RadTech Research Society), but Among them, the triarylsulfonium salt is excellent in storage stability and has good solubility in a polymerizable compound, so that the amount of addition thereof can be easily increased, and the residue of the polymerizable compound can be suppressed, which is preferable.

The triarylsulfonium salt type photoinitiator is preferably a phosphonium salt represented by any one of the following general formulae (1) to (4):

In the formula (1), R ¹ to R ³ each independently represent a hydrogen atom or a substituent, and at least one of R ¹ to R ³ represents a substituent; and in the formula (2), R ⁴ to R ⁷ each represent hydrogen. At least one or more of R ⁴ to R ⁷ represents a substituent; and in the formula (3), R ⁸ to R ¹¹ each independently represent a hydrogen atom or a substituent, and at least one of R ⁸ to R ¹¹ represents at least one of In the formula (4), R ¹² to R ¹⁷ each independently represent a hydrogen atom or a substituent, and at least one of R ¹² to R ¹⁷ represents a substituent, and X ^- each represents a non-nucleophilic anion residue] .

The substituent represented by R ¹ to R ¹⁷ may preferably be an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group or a hexyl group, and a methoxy group. Alkoxy groups such as ethoxy, propoxy, butoxy, hexyloxy, decyloxy, dodecyloxy, ethenyloxy, propenyloxy, decylcarbonyloxy, twelve a carbonyl group such as an alkylcarbonyloxy group, a methoxycarbonyl group, an ethoxycarbonyl group or a benzhydryloxy group; a halogen atom such as a phenylthio group, a fluorine atom such as fluorine, chlorine, bromine or iodine; a cyano group; a nitro group;

X ^- represents an anion, and may, for example, be a halogen atom such as F ^- , Cl ^- , Br ^- or I ^- , B(C ₆ F ₅ ) ₄ ^- , R ¹⁹ COO ^- , R ²⁰ SO ₃ ^- , SbF ₆ ^- , AsF _6. Anions such as PF ₆ ^- and BF ₄ ^- . Wherein R ¹⁹ and R ²⁰ each represent an alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group, and may be a halogen atom such as fluorine, chlorine, bromine or iodine, a nitro group, a cyano group, a methoxy group or an ethoxy group. An alkoxy-substituted alkyl or phenyl group. Among them, B(C ₆ F ₅ ) ₄ ^- and PF ₆ ^{- are} preferred from the viewpoint of safety.

In the present embodiment, an example of a cerium salt which is particularly excellent in curability is a phthalic acid salt which does not generate benzene after light irradiation as a photopolymerization initiator. The phrase "no benzene is generated by irradiation of light" means that benzene is not substantially produced. The above-mentioned conditions are satisfied if the onium salt has a substituent on the benzene ring bonded to S ⁺ , and is, for example, listed in the above formulas (1) to (4).

Specific examples of the compounds represented by the general formulae (1) to (4) are, for example, those represented by the following formulas (6) to (14) (S-1 to S-9), but are not limited thereto.

The above compounds can be easily synthesized by a known method. If an example is to be enumerated, it can be edited with the Bullettin of the Chemical Society of Japan Vol. 71 No. 11, 1998, Organic Electron Materials Research Society, "Organic Materials for Imaging", published in the text (1993). The method for producing the initiator is produced in the same manner.

(hollow cerium oxide microparticles)

Next, a hollow cerium oxide fine particle having an outer shell layer and having a porous or void inside will be described.

Specific examples of the hollow cerium oxide microparticles having a shell layer and having a porous or void inside are (1) composite particles composed of a porous particle and a coating layer provided on the surface of the porous particle, or (2) voids inside. The void particles filled with the content as a solvent, a gas or a porous substance.

Further, the hollow particles are particles having voids inside, and the voids are surrounded by the particle walls. The inside of the cavity is filled with a content such as a solvent, a gas, or a porous substance used for preparation. The average particle diameter of the hollow cerium oxide microparticles is preferably from 5 to 200 nm, preferably from 10 to 70 nm. The particle size of the hollow cerium oxide microparticles is preferably a monodispersion with a coefficient of variation of 1 to 40%. These hollow cerium oxide fine particles are preferably used in a state of being dispersed in a suitable solvent in order to form a low refractive index layer.

Further, the average particle diameter of the hollow cerium oxide microparticles used in the present embodiment can be measured by an electron micrograph obtained by a scanning electron microscope (SEM) or the like. It can also be measured by a particle size distribution meter using a dynamic light scattering method or a static light scattering method.

The dispersing agent is preferably water, alcohols (such as methanol, ethanol, isopropanol), and ketones (such as methyl ethyl ketone, methyl isobutyl ketone), keto alcohols (such as acetol), and propylene. Monomethyl ether, propylene glycol monomethyl ether acetate, and the like.

The thickness of the coating layer of the composite particles or the particle wall thickness of the void particles is preferably from 1 to 40 nm, preferably from 1 to 20 nm, more preferably from 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 failing to sufficiently obtain the low refractive index. The effect. In addition, when the thickness of the coating layer exceeds 20 nm, the coating liquid component does not enter the inside, but the porosity (pore volume) of the composite particles is lowered, and the effect of lowering the refractive index cannot be sufficiently obtained. In the case of a hollow particle, when the thickness of the particle wall is less than 1 nm, the particle shape may not be maintained, and when the thickness exceeds 20 nm, the effect of lowering the refractive index may not be sufficiently exhibited.

The particle wall of the coating layer of the composite particles or the hollow particles is preferably composed mainly of cerium oxide. 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 Sb _{2 .} O ₅ , SbO ₂ , MoO ₃ , ZnO ₂ , WO ₃ and the like. The porous particles constituting the composite particles are exemplified by those composed of cerium oxide and composed of inorganic compounds other than cerium oxide and cerium oxide, and are composed of CaF ₂ , NaF, NaAlF ₆ , MgF or the like. Among these, a porous particle composed of a composite oxide of an inorganic compound other than cerium oxide and cerium oxide is particularly preferable.

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 , Sb ₂ O ₅ , SbO ₂ , One or two or more of MoO ₃ , ZnO ₂ , and WO ₃ . The porous particles are represented by SiO ₂ as cerium oxide, and the molar ratio of the inorganic compound other than cerium oxide in terms of oxide (MO _x ): MO _x /SiO 2 is preferably 0.0001 to 1.0, preferably 0.001 to 0.3. The scope.

The molar ratio of the porous particles: MO _x /SiO _{2 is} less than 0.0001, which is difficult to obtain, and even if the pore volume thereof is small, particles having a low refractive index cannot be obtained. Further, the molar ratio of the porous particles: when MO _x /SiO ₂ exceeds 1.0, since the ratio of cerium oxide is small, the pore volume becomes large, and it is more difficult to obtain a case where the refractive index is low.

The pore volume of the porous particles is preferably from 0.1 to 1.5 ml/g, preferably from 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, and when the amount exceeds 1.5 ml/g, the strength of the particles is lowered, and the strength of the obtained film is lowered.

Further, the pore volume of the porous particles can be determined by mercury intrusion. Further, the contents of the void particles are exemplified by solvents, gases, porous substances, and the like used in particle preparation. The solvent may also 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, the porous substance is exemplified by a compound exemplified by a porous particle. The contents may be composed of a single component, but may also be a mixture of plural components.

Specifically, when the composite particles are composed of an inorganic compound other than cerium oxide or cerium oxide, the hollow particles can be produced by performing the following first to third steps. For example, a method of preparing composite oxide colloidal particles disclosed in paragraphs [0010] to [0033] of JP-A-7-133105 is preferably used.

(First step: modulation of porous particle precursor)

In the first step, an alkaline aqueous 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, which corresponds to a composite oxide of a target. In the compounding ratio, the aqueous solution was slowly added to an aqueous alkaline solution having a pH of 10 or more while stirring to prepare a porous particle precursor.

As the cerium oxide raw material, an alkali metal, ammonium or organic base citrate is used. The alkali metal citrate is sodium citrate (water glass) or potassium citrate. The organic base may, for example, be a quaternary ammonium salt such as a tetraethylammonium salt or an amine such as monoethanolamine, diethanolamine or triethanolamine. Further, the ammonium citrate or the organic base citrate also contains an alkaline solution obtained by adding ammonia, a quaternary ammonium hydroxide, an amine compound or the like to a citric acid solution.

Further, as the raw material of the inorganic compound other than cerium oxide, an alkali-soluble inorganic compound is used. Specific examples thereof include an oxo acid selected from the group consisting of elements of Al, B, Ti, Zr, Sn, Ce, P, Sb, Mo, Zn, and W, and an alkali metal salt or an alkaline earth metal salt of the oxyacid , ammonium salt, quaternary ammonium salt. More specifically, sodium aluminate, sodium tetraborate, ammonium zirconium carbonate, potassium citrate, potassium stannate, sodium aluminosilicate, sodium molybdate, cerium ammonium nitrate or sodium phosphate are preferred.

The pH of the mixed aqueous solution is changed while the aqueous solution is added, but the pH is not particularly necessary for the operation to be controlled within a specific range. The aqueous solution is a pH value defined by the type of the final, the inorganic oxide, and the mixing ratio thereof. The rate of addition of the aqueous solution at this time is not particularly limited. Further, when the composite oxide particles are produced, a dispersion of the seed particles may be used as a starting material.

The seed crystal 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 can be used. Usually, such sols can be used. Further, the porous particle precursor dispersion obtained by the above production method may 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 in the seed crystal particle dispersion liquid is added to the alkaline aqueous solution while stirring. At this time, it is not necessary to carry out the necessary dispersion pH control. When such a seed particle is used, the particle size of the prepared porous particle is easily controlled, and a uniform particle size can be obtained.

The above cerium oxide raw material and inorganic compound raw material have high solubility on the alkaline side. However, when the two are mixed in the pH region where the solubility is large, the solubility of the oxo acid ions such as citric acid ions and aluminate ions is lowered, and the composites are precipitated to cause particle growth, or in the seed particles. Precipitation causes particle growth. Accordingly, when the particles are precipitated and grown, it is not necessary to perform pH control as in the conventional method.

The composite ratio of cerium oxide to inorganic compound other than cerium oxide in the first step is an inorganic compound converted to oxide (MOx) relative to cerium oxide, and the molar ratio of MOx/SiO ₂ is preferably 0.05 to 2.0. Good in the range of 0.2~2.0. Within this range, the proportion of cerium oxide becomes small, and the pore volume of the porous particles increases. However, even if the molar ratio exceeds 2.0, the pore volume of the porous particles tends to hardly increase. 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 MOx/SiO ₂ is preferably in the range of 0.25 to 2.0.

(Second step: removal of inorganic compounds other than cerium oxide from porous particles)

The second step is to selectively remove at least a portion of the inorganic compound other than cerium oxide (an element other than cerium and oxygen) from the porous particle precursor obtained in the first step. The specific removal method is to remove the inorganic compound in the precursor of the porous particle by using a mineral acid or an organic acid, or to perform ion exchange removal by contacting with the cation exchange resin.

Further, the porous particle precursor obtained in the first step is a particle of a mesh structure in which an element is bonded to an inorganic compound by oxygen. The inorganic compound (an element other than cerium and oxygen) is removed from the porous precursor precursor to obtain a porous particle having a large pore volume in a porous layer. Further, if the amount of the inorganic oxide (the element other than cerium and oxygen) is removed 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, it is preferred to obtain a citric acid solution containing a fluorine-substituted alkyl group-containing decane compound or a hydrolyzable property obtained by deactivating the alkali metal salt of cerium oxide. The organic cerium compound is added to the porous particle precursor dispersion obtained in the first step to form a cerium oxide protective film. The thickness of the ruthenium oxide protective film is preferably 0.5 to 40 nm, preferably 0.5 to 15 nm. Further, even if a ruthenium oxide protective film is formed, since the protective film in this step is porous and thin, the inorganic compound other than the above cerium oxide can be removed from the porous particle precursor.

By forming the cerium oxide protective film, the particle shape is maintained, and the inorganic compound other than the cerium oxide can be removed from the porous particle precursor. Further, when the cerium oxide coating layer described later is formed, the pores of the porous particles are not blocked by the coating layer, so that the pore volume is not lowered, and a cerium oxide coating layer to be described later can be formed. Further, when the amount of the inorganic compound to be removed is small, since the particles are not destroyed, it is not necessary to form a protective film.

Further, when the void particles are prepared, it is preferred to form the ruthenium oxide protective film. When the void particles are prepared, if the inorganic compound is removed, a void particle precursor composed of a solvent in the ruthenium oxide protective film and the ruthenium oxide protective film and an undissolved porous solid component is obtained, and is formed on the precursor of the void particle. In the coating layer described later, the formed coating layer is formed as a void particle of the particle wall.

The amount of the cerium oxide source added to form the above cerium oxide protective film is less preferable in the range in which the particle shape can be maintained. When the amount of the oxidation source is too large, the cerium oxide protective film becomes too thick, so that it is difficult to remove the inorganic compound other than cerium oxide from the porous particle precursor.

As the hydrolyzable organic ruthenium compound used for the formation of the ruthenium oxide protective film, an alkoxy decane represented by the following formula (15) can be used. In particular, tetraalkyloxydecane such as fluorine-substituted tetramethoxynonane, tetraethoxysilane or tetraisopropoxydecane is preferably used.

R ²¹ _m Si(OR ²² ) _4-m (15)

In the formula (15), R ²¹ and R ²² represent a hydrocarbon group such as an alkyl group, an aryl group, a vinyl group or a propenyl group, and m represents 0, 1, 2 or 3.

The addition method is a solution in which a small amount of a base or an acid as a catalyst is added to a mixed solution of the alkoxysilane, the pure water, and the alcohol in the dispersion of the porous particles, and the dispersion in the porous particles a solution in which 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 a tannic acid formed by hydrolyzing an alkoxydecane on the surface of the inorganic oxide particles is deposited on the surface of the inorganic oxide particles. polymer.

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

The dispersion medium of the porous particle precursor can also form a ruthenium oxide protective film using a tannic acid solution when the ratio of water alone or water to the organic solvent is high. When a citric acid solution is used, a citric acid solution is added to the dispersion in a specific amount, and a base is added to deposit a citric acid solution on the surface of the porous particle. Further, a ruthenium oxide protective film may be prepared by using a tannic acid solution together with the above alkoxysilane.

(Third step: formation of cerium oxide coating)

The third step is a porous particle dispersion prepared by adding a hydrolyzable organic hydrazine compound or a citric acid solution containing a fluorinated compound having a fluorine-substituted alkyl group to the second step (in the case of a hollow particle, a precursor of a hollow particle) The material dispersion liquid is formed by coating a surface of the particle 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 an aqueous solution of a low polymer of citric acid which is subjected to ion exchange and alkalization of an aqueous solution of an alkali metal ruthenate such as water glass.

The amount of the organic cerium compound or the ceric acid solution to be used for forming the coating layer may be such that the surface of the colloidal particles can be sufficiently coated, so that the thickness of the finally obtained cerium oxide coating layer is 1 to 40 nm, preferably 1 to 1. An amount of 20 nm was added to the dispersion of the porous particles (the void particle precursor in the case of void particles). When the ruthenium oxide protective film is formed, the organic ruthenium compound or the ruthenium acid solution is added in an amount of 1 to 40 nm, preferably 1 to 20 nm, in total thickness of the ruthenium oxide protective film and the ruthenium oxide coating layer.

Next, the particle dispersion liquid in which the coating layer is formed is heat-treated. In the case of the porous particles, the cerium oxide coating layer on the surface of the porous substrate is densified by heat treatment, and a dispersion of the composite particles in which the porous particles are coated with the cerium oxide coating layer is obtained. In the case of a void particle precursor, the formed coating layer is densified into a void particle wall, and a dispersion of void particles having a cavity filled with a solvent, a gas or a porous solid component is obtained.

The heat treatment temperature at this time is not particularly limited as long as it can occlude the fine pores of the cerium oxide coating layer, and is preferably in the range of 80 to 300 °C. When the heat treatment temperature is less than 80 ° C, the fine pores of the cerium oxide coating layer may not be completely closed and densified, and there is a case where a long processing time is required. Further, when the heat treatment temperature exceeds 300 ° C and is treated for a long period of time, it may be a case of dense particles, and a low refractive index effect may not be obtained.

The hollow cerium oxide microparticles thus obtained have a refractive index as low as less than 1.42. It is presumed that these hollow cerium oxide microparticles retain the porosity inside the porous particles, but they have a low refractive index because they are hollow inside.

Further, as for the stability of the coating composition, the hollow particles are preferably hollow particles having a polymer having a hydrocarbon main chain covalently bonded to the surface.

Next, hollow particles in which a polymer having a hydrocarbon main chain is co-bonded will be described. The polymer having a hydrocarbon main chain is called a direct covalent bond, or a ruthenium oxide on the surface of the hollow cerium oxide microparticles and a polymer having a hydrocarbon main chain pass through a binder to covalently bond the ruthenium oxide to the binder. Also refers to the bond between the binder and the polymer. As the binder, a coupling agent is preferably used.

Hollow particles covalently bonded to a polymer having a hydrocarbon main chain can be produced by the following method: (1) Hollow oxidation of the surface of the hollow cerium oxide microparticles without treatment or treatment with a coupling agent or the like a method in which a surface of a fine particle is reacted with a polymer having a functional group capable of forming a covalent bond, a polymer is grafted onto a surface of the hollow cerium oxide microparticle, or (2) a surface of the hollow cerium oxide microparticle is left untreated, or In the state of the treatment with a coupling agent or the like, a method of polymerizing a monomer from the surface of the hollow cerium oxide microparticles to grow a polymer chain, and performing surface grafting. As an example of the production method, the method described in JP-A-2006-257308 can be used.

In the above production method, from the viewpoint of increasing the surface modification ratio, a method of polymerizing a monomer from the surface of the hollow cerium oxide fine particles to grow a polymer chain and performing surface grafting is preferred. More preferably, the hollow cerium oxide fine particles are surface-treated with a coupling agent containing a functional group having a polymerization initiation energy or a chain transfer energy, thereby polymerizing the monomers to grow a polymer chain for surface grafting. A surface treatment agent (coupling agent) for introducing a functional group having a polymerization initiation energy or a chain transfer energy into the hollow fine particles, preferably an alkoxy metal compound (for example, a titanium coupling agent or an alkoxydecane compound (decane) Coupling agent)).

The hollow cerium oxide microparticles may further contain two or more kinds of hollow cerium oxide microparticles having different average particle diameters.

In the present embodiment, hollow yttrium oxide fine particles having a conductive metal oxide coating layer are also used for the low refractive index layer, and conductivity can be further improved. The metal oxide forming the conductive metal oxide coating layer is not particularly limited, and examples thereof include, for example, tin oxide, antimony tin oxide, indium tin oxide, antimony oxide, aluminum zinc oxide, gallium zinc oxide, and the like. The mixture of people. Among them, the hollow cerium oxide fine particles coated with cerium oxide are preferred.

When the average thickness of the conductive metal oxide coating layer is from 1 to 40 nm, more preferably from 1 to 20 nm, the hollow cerium oxide fine particles can be sufficiently coated, and the conductivity of the hollow cerium oxide fine particles coated with the obtained conductive metal oxide is changed. From a sufficient viewpoint, the thickness of the coating layer is preferably 1 nm or more. The thickness of the coating layer is preferably 40 nm or less from the viewpoint of the fact that the average particle diameter of the hollow cerium oxide fine particles coated with the conductive metal oxide is sufficient for the conductivity to be sufficiently improved.

In the present embodiment, hollow cerium oxide fine particles having an optimum cerium oxide coating layer will be described.

The cerium oxide may be any of Sb ₂ O ₃ , Sb ₂ O ₅ , and SbO _{2 ,} and the cerium oxide coating layer may contain tin oxide or the like. The total content of the cerium oxide in the cerium oxide coating layer is preferably 10% or more. Further, the cerium oxide coating layer may be further coated with cerium oxide or the like.

The volume resistivity of the yttria-coated hollow cerium oxide particles is preferably from 10 to 5,000 Ω/cm, more preferably from 10 to 2,000 Ω/cm. When the volume resistance value is in this range, on the one hand, the refractive index of the particles can be kept low, and on the other hand, the surface resistance of the low refractive index coating film can be lowered. The volume resistance value can be controlled by adjusting the particle size of the core particles, the thickness of the surface-coated metal oxide layer, and the composition.

The volume resistance value was measured by the following method.

A ceramic cell having a cylindrical hollowed out (sectional area of 0.5 cm ² ) was placed, and the cells were placed on the gantry electrode, and 0.6 g of the sample powder (yttria particles) was filled therein, and the insertion was cylindrical. The protrusion of the upper electrode of the protrusion was pressed against the upper and lower electrodes by a hydraulic press, and the resistance value (Ω) at the time of pressurization of 100 kg/cm ² and the height (cm) of the sample were measured, and the height was multiplied by the resistance value.

A method for producing hollow cerium oxide fine particles coated with cerium oxide will be described.

First, a porous cerium oxide particle or a dispersion of cerium oxide particles having voids therein is prepared by the above method or the like. The solid content concentration of the dispersion is preferably in the range of 0.1 to 40% by mass, more preferably 0.5 to 20% by mass. When the solid content concentration is less than 0.1% by mass, the production efficiency is low, and when the solid content concentration is more than 40% by mass, the obtained cerium oxide-coated hollow cerium oxide fine particles are aggregated, and the transparency of the film is lowered and the turbidity is deteriorated.

Further, a dispersion of citric acid (aqueous solution) was prepared. The method of preparing the citric acid is not particularly limited as long as the porous cerium oxide particles or the pores or voids of the cerium oxide particles having voids therein are buried, but the coating layer of cerium oxide is formed on the surface of the particles. The method shown can be formed to form a uniform and thin yttria coating.

Specifically, a citric acid (gel) dispersion is prepared by treating a citric acid base aqueous solution with a cation exchange resin, followed by treatment with an anion exchange resin. As the aqueous citric acid solution, a conventional aqueous citric acid solution can be used. For example, an aqueous citric acid solution used in the method for producing a cerium oxide sol described in JP-A-2-1801717 is preferably used.

The aqueous citric acid solution is preferably obtained by reacting antimony trioxide (Sb ₂ O ₃ ), a basic substance and hydrogen peroxide, and setting the molar ratio of cerium oxide to alkaline substance and hydrogen peroxide to 1; ~2.5: 0.8~1.5, preferably 1:2.1~2.3:0.9~1.2, adding hydrogen peroxide to each of the 3 moles of antimony trioxide at a rate of 0.2 mol/hr or less to contain antimony trioxide In the system of alkaline substances.

The antimony trioxide used at this time is preferably a powder, especially a fine powder having an average particle diameter of 10 μm or less, and the basic substance may be LiOH, KOH, NaOH, Mg(OH) ₂ or Ca(OH) _{2 .} Etc., among them, an alkali metal hydroxide such as KOH or NaOH is preferred. These basic substances have an effect of stabilizing the obtained citric acid solution.

First, a specific amount of a basic substance and antimony trioxide are added to water to prepare a ceria suspension. The antimony trioxide concentration of the antimony trioxide suspension is preferably in the range of 3 to 15% by mass in terms of Sb ₂ O ₃ . Next, the suspension is heated to 50 ° C or higher, preferably 80 ° C or higher, and a hydrogen peroxide aqueous solution having a concentration of 5 to 35% by mass is added to each of the molybdenum trioxide at a rate of 0.2 mol/hr. In it. When the addition rate of the aqueous hydrogen peroxide solution is higher than 0.2 mol/hr, the particle diameter of the obtained cerium oxide particles becomes large, and the particle size distribution is wide, which is not preferable. Further, when the addition rate of the aqueous hydrogen peroxide solution is extremely slow, the productivity is poor, so that the preferable addition rate is in the range of 0.04 to 0.2 mol/hr.

The aqueous solution of the citric acid base (MHSbO ₃ : M is an alkali metal) obtained by the above reaction, and the undissolved residue is separated as needed, further diluted as needed, treated with a cation exchange resin, and the alkali ion is removed to prepare a citric acid. Gel (HSbO ₃ ^- ) _n dispersion.

Further, the aqueous citric acid solution may also contain an aqueous solution containing a dopant such as an aqueous stannic acid solution or an aqueous solution of sodium phosphate. When such a dopant is contained, hollow cerium oxide fine particles coated with cerium oxide having higher conductivity can be obtained.

Among them, citric acid can be represented by (HSbO ₃ ^- ) _n (polymer of n=2 or more), and is composed of a polymer of citric acid (HSbO ₃ ^- ) having a particle diameter of about 1 to 5 nm, and is in a state in which fine particles are aggregated and gelled.

The concentration of the aqueous citric acid solution in the case of treatment with a cation exchange resin is 0.01 to 5% by mass, more preferably 0.1 to 3% by mass, based on the solid content Sb ₂ O ₅ . When the amount is less than 0.01% by mass based on the solid content, the production efficiency is low, and when it exceeds 5% by mass, a large aggregate of tannic acid is generated, and it is difficult to coat the hollow cerium oxide fine particles with tannic acid, and even if it is coated, it may become uneven. .

The cation exchange resin is used in an amount such that the pH of the obtained citric acid dispersion is from 1 to 4, preferably from 1.5 to 3.5. When the pH is less than 1, the chain particles are not formed to form aggregated particles, and when it exceeds pH 4, monodisperse particles tend to be formed. Further, when the pH is less than 1, the solubility of cerium oxide is high, so that it is difficult to coat a specific amount of cerium oxide. When the pH exceeds 4, the hollow cerium oxide fine particles coated with cerium oxide are aggregated, and the dispersibility in the coating is lowered. The antistatic effect is insufficient.

Next, the ceric acid dispersion liquid and the porous cerium oxide particles or the dispersion of cerium oxide particles having voids therein are mixed, and the aging is carried out at a temperature of 50 to 250 ° C, preferably 70 to 120 ° C, usually for 1 to 24 hours. Thereby, a cerium oxide-coated hollow cerium oxide fine particle dispersion can be obtained.

The mixing ratio of the ceric acid dispersion and the cerium oxide-based particle dispersion is preferably 1 to 200 parts by mass in terms of Sb ₂ O ₅ based on 100 parts by mass of the cerium oxide-based particles of the solid content. It becomes 5 to 100 parts by mass. When the mixing ratio of citric acid is less than 1 part by mass, the coating is uneven and the thickness of the coating layer is insufficient, and the effect of coating with cerium oxide, that is, the effect of imparting and improving conductivity, may not be sufficiently obtained. Even if the mixing ratio of tannic acid exceeds 200 mass, it does not contribute to the increase in the coated cerium oxide, and the conductivity of the hollow cerium oxide fine particles coated with cerium oxide cannot be further improved, and the refractive index may be as high as more than 1.60.

The concentration of the mixed dispersion is preferably from 1 to 40% by mass, more preferably from 2 to 30% by mass, based on the solid content. When the concentration of the mixed dispersion is less than 1% by mass, the coating efficiency of cerium oxide is insufficient, and the production efficiency is lowered. On the other hand, when it exceeds 40 mass%, the amount of the cerium oxide-coated hollow cerium oxide fine particles may be aggregated when the amount of citric acid used is large.

(ionizing radiation hardening resin)

The low refractive index layer of the present embodiment may contain an ionizing radiation curable resin as described above. The ionizing radiation-curable resin refers to a resin which is cured by a crosslinking reaction or the like by irradiation with an active wire such as ultraviolet rays or an electron beam (hereinafter also referred to as an active energy ray). As the ionizing radiation-curable resin, a component containing a monomer having an ethylenically unsaturated double bond is preferably used, and is hardened by irradiation with an active wire such as ultraviolet rays or an electron beam to form an ionizing radiation-curable resin layer. The ionizing radiation-curable resin is exemplified by an ultraviolet curable resin or an electron beam curable resin, but the resin cured by ultraviolet irradiation is excellent in mechanical film strength (scratch resistance, pencil hardness). In terms of aspect, it is preferred.

In the present embodiment, the ionizing radiation-curable resin is preferably an acrylic compound having two or more polymerizable unsaturated bonds in its molecule.

The ultraviolet curable resin is preferably a polyfunctional acrylate. The polyfunctional acrylate is preferably selected from the group consisting of pentaerythritol polyfunctional acrylate, dipentaerythritol polyfunctional acrylate, pentaerythritol polyfunctional methacrylate, and dipentaerythritol polyfunctional methacrylate. . Among them, the polyfunctional acrylate is a compound having two or more acryloxy groups and/or methacryloxy groups in the molecule.

The polyfunctional acrylate monomer is preferably exemplified by, for example, ethylene glycol diacrylate, diethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, trishydroxyl Propane triacrylate, trimethylolethane triacrylate, tetramethylol methane triacrylate, tetramethylol methane tetraacrylate, pentatriol triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate Ester, pentaerythritol tetraacrylate, glycerol triacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tris(propylene methoxyethyl) isocyanurate Acid ester, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane Trimethacrylate, trimethylolethane trimethacrylate, tetramethylol methane trimethacrylate, tetramethylol methane tetramethacrylate, pentatriol trimethacrylate, Pentaerythritol II Methacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, glycerol trimethacrylate, dipentaerythritol trimethacrylate, dipentaerythritol tetramethacrylate, dipentaerythritol pentamethacrylic acid Ester, dipentaerythritol hexamethacrylate, isophorone acrylate, and the like. These compounds may be used alone or in combination of two or more. Further, it may be an oligomer of a dimer or a trimer of the above monomer.

(photoradical initiator)

Further, when the ionizing radiation curable resin is contained, it is preferred to contain a photoradical initiator. The photoradical initiator is acetophenone, benzoin, benzophenone, ketal, anthraquinone, thioxanthone, azo compound, peroxide, 2,3- Dialkyldiketone compounds, disulfide compounds, thiuram compounds, fluoroamine compounds, oxime esters, and the like. Specific examples of the photopolymerization initiator are 2,2'-diethoxyacetophenone, p-dimethylacetophenone, 1-hydroxycyclohexylacetophenone, 1-hydroxydimethylphenyl ketone, 2-methyl-4'-methylthio-2-morpholinylpropiophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone, 1,2 - Acetophenones such as methyl-1[4-(methylthio)phenyl]-2-morpholinylpropan-1-one, α-hydroxyacetophenone, α-aminoacetophenone, etc., benzene Benzene, such as methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyl dimethyl ketal, benzophenone, 2,4'-dichlorobenzophenone , 4,4'-dichlorobenzophenone, p-chlorobenzophenone and other benzophenones, 1,2-octanedione-1-[4-(phenylthio)-2-(O -benzhydryl hydrazide)], ethane-1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-1-(O-acetamidine) Base 肟) is an ester such as oxime. These photopolymerization initiators may be used singly or in combination of two or more and in a mixture. In particular, acetophenones and oxime esters such as α-hydroxyacetophenone and α-aminoacetophenone are preferably used in terms of stability of the curable composition, polymerization reactivity, and the like.

(colloidal cerium oxide, magnesium fluoride)

Further, the low refractive index layer of the present embodiment may contain colloidal cerium oxide or magnesium fluoride.

The specific example of the colloidal cerium oxide is not particularly limited as long as the cerium oxide is dispersed in a colloidal form in water or an organic solvent, but may be spherical, needle-like or beaded.

The average particle size of the colloidal cerium oxide 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 electron microscopy using a scanning electron microscope (SEM) or the like. The measurement can also be carried out by using a particle size distribution meter such as a dynamic light scattering method or a static light scattering method.

Colloidal antimony oxide is commercially available, for example, the SNOWTEX series of Nissan Chemical Industries, the CATALOID S series of Catalyst Chemical Industries, and the LAVASIL series of Bayer. Further, it is also preferred to use a metal ion having a divalent or higher metal ion to bond between particles of a colloidal cerium oxide or cerium oxide which is cation-modified with an alumina sol or aluminum hydroxide, and to form a bead-like number of beads. Colloidal cerium oxide. The beaded colloidal cerium oxide is SNOWTEX-AK series, SNOWTEX-PS series, SNOWTEX-UP series, etc. of Nissan Chemical Industry Co., Ltd., specifically IPS-ST-L (isopropyl alcohol dispersion, particle size 40~50 nm , solid content: 30%), MEK-ST-MS (methyl ethyl ketone dispersion, particle size: 17 to 23 nm, solid content: 35%).

Magnesium fluoride is exemplified by an isopropanol-dispersed magnesium fluoride sol of Nissan Chemical Industries Co., Ltd., or a NANOTEC series of C.I. Chemical Corporation.

(catalyst)

In the present embodiment, the low refractive index layer preferably contains a catalyst. The catalysts are listed as inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid; organic acids such as oxalic acid, acetic acid, formic acid, and methanesulfonic acid; inorganic bases such as sodium hydroxide, potassium hydroxide, and ammonia; and organic bases such as triethylamine and pyridine. A metal alkoxide such as aluminum triisopropoxide or a tetrabutyloxy zirconium, a metal chelate compound described later, and the like, among which an acid catalyst and a metal chelate compound are preferably used.

As the acid catalyst, hydrochloric acid, sulfuric acid, oxalic acid, acetic acid, phthalic acid or the like is preferably used.

The metal chelate compound is preferably a metal chelate compound containing at least one selected from the group consisting of Zr, Ti, and Al. These metal chelate compounds are considered to have an effect of promoting the above respective polymerization reactions. Further, the metal chelate compound is specifically exemplified by a compound represented by the general formula (16) and the general formula (17) as a ligand, and at least one selected from the group consisting of Zr, Ti and Al as a center. Metal metal chelate compound, and the like.

R ²³ OH (16)

(In the formula (16), R ²³ represents an alkyl group having 1 to 10 carbon atoms).

R ²⁴ COCH ₂ COR ²⁵ (17)

(In the formula (17), R ²⁴ represents an alkyl group having 1 to 10 carbon atoms, and R ²⁵ represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms).

Further, the metal chelate compound may be, for example, the above compounds alone or in combination of two or more.

Further, specific examples of the metal chelate compound are, for example, compounds represented by the general formulae (18) to (20). These compounds are preferred from the viewpoint of further promoting the above respective polymerization reactions.

Zr(OR ²⁶ ) _p1 (R ²⁷ COCHCOR ²⁸ ) _p2 (18) (In the formula (18), R ²⁶ and R ²⁷ independently represent an alkyl group having 1 to 10 carbon atoms or a phenyl group, and R ²⁸ represents a carbon number of 1 to 10 An alkyl group, an alkoxy group having 1 to 10 carbon atoms, or a phenyl group, and p1 and p2 represent an integer determined by a tetracoordinate or a hexacoordination).

Ti(OR ²⁹ ) _q1 (R ³⁰ COCHCOR ³¹ ) _q2 (19) (In the formula (19), R ²⁹ and R ³⁰ independently represent an alkyl group having 1 to 10 carbon atoms or a phenyl group, and R ³¹ represents a carbon number of 1 to 10 An alkyl group, an alkoxy group having 1 to 10 carbon atoms, or a phenyl group, and q1 and q2 represent an integer determined by a tetracoordinate or a hexacoordination).

Ti(OR ³² ) _r1 (R ³³ COCHCOR ³⁴ ) _r2 (20) (In the formula (20), R ³² and R ³³ independently represent an alkyl group having 1 to 10 carbon atoms or a phenyl group, and R ³⁴ represents a carbon number of 1 to 10 An alkyl group, an alkoxy group having 1 to 10 carbon atoms, or a phenyl group, and r1 and r2 represent an integer determined by a tetracoordinate or a hexacoordination).

The alkyl group in the above formulae (18) to (20) is exemplified by an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a second butyl group, a tert-butyl group, a n-pentyl group or the like. The alkoxy group in the above formula (18) to (20) is, for example, a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, a second butoxy group, and a third group. Oxyl and the like.

The above metal chelate compound is more specifically exemplified by, for example, zirconium tri-n-butoxyethylacetate, zirconium di-n-butoxybis(ethyl acetate), n-butoxytri(ethylethenyl) Zirconium, yttrium (n-propoxyacetoxyacetic acid) zirconium, zirconium (ethanoacetonitrile) zirconium, zirconium (ethyl acetoacetate) zirconium and the like zirconium chelate compound; diisopropoxy ‧ Titanium chelate compound such as bis(ethylacetylacetic acid) titanium, diisopropoxy ‧ bis(acetic acetone) titanium; aluminum diisopropoxyethyl acetoxyacetate, diisopropoxy Aluminum acetonitrile, aluminum isopropoxide bis(ethyl acetoacetate), aluminum bis(ethylene acetonate), aluminum tris(ethyl acetonitrile), tris(acetonitrile) An aluminum chelate compound such as aluminum, monoethyl phthalate, bis (ethyl acetonitrile) aluminum or the like.

Among these, zirconium tri-n-butoxyethylacetate, titanium diisopropoxy bis(ethyl sulfonate), aluminum diisopropoxyethyl acetoxyacetate, and tri (ethyl ethyl) Barium acetate) aluminum or the like is preferred. Further, these metal chelate compounds may be used singly or in combination of two or more. Further, as the component (b), a partial hydrolyzate of the metal chelate compound may be used.

(conductive microparticles)

In the present embodiment, the low refractive index layer preferably contains conductive fine particles. The conductive fine particles are the same as those of the conductive fine particles contained in the antistatic layer to be described later. Specifically, for example, metal oxide particles and π-conjugated conductive polymer particles are exemplified. Further, examples of the conductive fine particles include fine particles composed of a carbon material.

The carbon material is not particularly limited as long as it can improve the antistatic property of the low refractive index layer. Specifically, it is a structure having a spherical shape, a cylindrical shape, a cylindrical shape, or the like having a diameter of a nanometer, which is composed of carbon atoms. More specifically, for example, fullerene, carbon nanotubes, amorphous carbon, carbon nanofibers, vapor-grown carbon fibers, and carbon nanoparticles as components, nanocapsules, carbon Carbon nanohorn, nanowhiskers, etc. Further, the diameter of the carbon material is preferably a nanometer grade as described above.

(Organic solvents)

The coating composition forming the low refractive index layer preferably contains an organic solvent. Specific examples of the organic solvent are exemplified by alcohols (for example, methanol, ethanol, isopropanol, butanol, benzyl alcohol), ketones (for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexyl). Ketones, 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), decylamine (eg, dimethylformamide, dimethyl Ethyl acetamide, n-methylpyrrolidone), ethers (eg, diethyl ether, dioxane, tetrahydrofuran), ether alcohols (eg, 1-methoxy-2-propanol), propylene glycol Monomethyl ether, propylene glycol monomethyl ether acetate. Among them, toluene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethanol, isopropanol and propylene glycol monomethyl ether are preferred.

The solid content concentration in the coating composition forming the low refractive index layer is preferably from 1 to 4% by mass, and the solid content concentration is not more than 4% by mass, and coating unevenness is not caused, and is 1% by mass. Above, the drying load can be reduced.

(surfactant)

The coating composition forming the low refractive index layer preferably contains a fluorine-based or polyfluorene-based surfactant. By containing the above surfactant, the coating unevenness can be effectively reduced and the antifouling property of the film surface can be improved.

The fluorine-based surfactant is a monomer containing a perfluoroalkyl group, an oligomer, or a polymer, and examples thereof include polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, and polyoxygen. A derivative such as ethylene. A commercially available product can be used as the fluorine-based surfactant, and examples thereof include, for example, SURFLON S-381, SURFLON S-382, SURFLON SC-101, SURFLON SC-102, SURFLON SC-103, and SURFLON SC-104 (made by Asahi Glass Co., Ltd.). ), FLORIDE FC-430, FLORIDE FC-431, FLORIDE FC-173 (Fluorine Chemicals Sumitomo 3M), FTOP EF352, FTOP EF301, FTOP EF303 (made by New Akita Chemical Co., Ltd.), SHUBEGORFLRA 8035, SHUBEGORFLRA 8036 (SHUBEGUMAN ( )Company Co., Ltd.), BM1000, BM1100 (BIEMU HIMI ( MEGAFACE F-171, MEGAFACE F-470 (made by DIC Corporation), etc.

The fluorine-containing surfactant has a fluorine content of 0.05 to 2% by mass, preferably 0.1 to 1% by mass, and the fluorine-based surfactant may be used alone or in combination of two or more.

Next, the polyfluorene surfactant will be described.

The polyoxynized surfactant is roughly classified into a linear polyoxo oil and a modified polyoxyxide oil depending on the type of organic group bonded to the ruthenium atom.

Here, the linear polyfluorene oxide oil is bonded by a methyl group, a phenyl group or a hydrogen atom as a substituent. The modified polyoxygenated oil has a component which is secondarily derived from a linear polyfluorene oxide oil. On the other hand, it can also be classified from the reactivity of polyoxygenated oil. The consolidation is as follows:

(polyoxygenated oil)

Linear polyoxylized oil

1-1. Non-reactive polyoxalate oil: substituted by dimethyl, methylphenyl, etc.

1-2. Reactive polyoxalate oil: substituted by methyl hydrogen, etc.

2. Modified polyoxyl oil

The introduction of various organic groups into the dimethylpolyphthalic acid oil is a modified polyoxo oil.

2-1. Non-reactive modified polyoxygenated oil: substituted by alkyl, alkyl/aralkyl, alkyl/polyether, polyether, higher fatty acid ester, and the like.

The alkyl/aralkyl modified polyoxygenated oil is a polyoxyxamic oil in which a part of the methyl group of the dimethylpolyphthalic acid oil is substituted with a long-chain alkyl group or a phenylalkyl group.

The polyether modified polyoxygenated oil is a surfactant obtained by introducing hydrophobic dimethyl polyfluorene into a hydrophilic polyoxyalkylene.

The higher fatty acid modified polyoxygenated oil is a polyoxyxane oil in which a part of the methyl group of the dimethylpolyphthalic acid oil is substituted with a higher fatty acid ester.

The amine-based modified polyoxygenated oil is a polyoxygenated 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 polyoxyxane oil is a polyoxyxane oil having a structure in which one part of a methyl group of a polyoxyxane oil is substituted with an alkyl group containing an epoxy group.

The carboxy-modified or alcohol-modified polyoxyxaic oil is a polyoxyxene 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 these, it is preferred to add a polyether modified polysiloxane. The number average molecular weight of the polyether modified polyoxygenated oil is preferably, for example, 1,000 to 100,000, preferably 2,000 to 50,000. When the number average molecular weight is less than 1,000, the drying property of the coating film is lowered. Conversely, if the number average molecular weight exceeds 100,000, it is likely to bleed out from the surface of the coating film.

Specific examples of products are Toray Dow Corning's L-45, L-9300, FZ-3704, FZ-3703, FZ-3720, FZ-3786, FZ-3501, FZ-3504, FZ-3508, FZ-3705, FZ-3707, FZ-3710, FZ-3750, FZ-3760, FZ-3785, Y-7499, KF96L, KF96, KF96H, KF99, KF54, KF965, KF968, KF56, KF995, KF351, KF351A, KF352, KF353, KF354, KF355, KF615, KF618, KF945, KF6004, FL100, BYK CHEM JAPAN Co., Ltd. surfactant 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-Silclean 3700, dimethyl polyfluorene series manufactured by GE Toshiba Polyoxane Co., Ltd., XC96-723, YF3800, XF3905, YF3057, YF3807, YF3802, YF3897, etc.

Further, the polyfluorene surfactant is a surfactant obtained by substituting a hydrophilic group for a part of the methyl group of the polyoxygenated oil. Substituted positions include side chains of polyoxylized oil, both ends, single-end, and two-end side chains. The hydrophilic group is a polyether, a polyglycerol, a pyrrolidone, a betaine, a sulfate, a phosphate, a quaternary salt or the like.

The polyoxymethylene surfactant is preferably a nonionic surfactant composed of a hydrophobic group dimethyl polyoxyalkylene and a hydrophilic group polyoxyalkylene.

The nonionic surfactant is a general term for a surfactant which does not have a base which decomposes into an ion in an aqueous solution, and may have a hydroxyl group of a polyol as a hydrophilic group in addition to a hydrophobic group, and has a polyoxyalkylene. A chain (polyoxyethylene) or the like is used as a hydrophilic group. The hydrophilicity becomes larger as the number of alcoholic hydroxyl groups increases, or becomes longer as the polyoxyalkylene chain (polyoxyethylene chain) becomes longer. When a nonionic surfactant composed of a hydrophobic base dimethylpolysiloxane or a hydrophilic group polyoxyalkylene is used, unevenness of the low refractive index layer or improvement of the antifouling property of the film surface can be improved. The hydrophobic group composed of polymethyl siloxane is considered to be attached to the surface to form a film surface which is less susceptible to contamination.

Specific examples of the nonionic surfactant are, for example, Toray Dow Corning's polyoxyn surfactants SILWET L-77, L-720, L-7001, L-7002, L-7604, Y-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, and the like.

The preferred structure of the nonionic surfactant composed of a hydrophobic group dimethyl polyoxyalkylene or a hydrophilic group polyoxyalkylene is preferably a dimethyl polyoxyalkylene moiety and a poly The oxyalkylene chain is alternately repeatedly bonded to form a linear block copolymer. It is preferable in terms of suppressing unevenness or in terms of advection property when coating a coating composition for forming a low refractive index layer. Specific examples of such are, for example, Toray Dow Corning's polyoxyn surfactants ABN SILWET FZ-2203, FZ-2207, FZ-2208, FZ-2222 and the like.

The coating composition for forming the low refractive index layer is preferably a polyoxyalkylene resin containing the reactive modification described below from the viewpoint of easily exhibiting better performance after the endurance test under more severe conditions. It is called a reactive modified polyoxygenated oil).

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

The reactive modified polyoxynoxy resin is a reactive type substituted with a metal group, an epoxy group, a carboxyl group, a hydroxyl group, a methacryl group, a decyl group, a phenol or the like at the side chain, single or both ends of the polyoxyalkylene. The modified polyoxynized resin. The amine-modified polyanion resin is specifically KF-860, KF-861, X-22-161A, X-22-161B (above, Shin-Etsu Chemical Co., Ltd.), FM-3311, FM -3325 (above is produced by CHISSO Co., Ltd.), epoxy modified polyoxyl resin is KF-105, X-22-163A, X-22-163B, KF-101, KF-1001 (above is Shin-Etsu Chemical Industrial Co., Ltd.), polyether modified polyoxyl resin is X-22-4272, X-22-4952, carboxyl modified polyoxyl resin is X-22-3701E, X-22-3710 ( The above is manufactured by Shin-Etsu Chemical Co., Ltd.), the polyoxyl resin modified by carbitol is KF-6001, KF-6003 (the above is manufactured by Shin-Etsu Chemical Co., Ltd.), and the poly-oxygen modified by methacrylic acid The resin is X-22-164C (the above is manufactured by Shin-Etsu Chemical Co., Ltd.), and the ruthenium-modified polyoxyl resin is KF-2001 (the above is manufactured by Shin-Etsu Chemical Co., Ltd.), and the phenol-modified polyoxyl The resin is X-22-1821 (the above is manufactured by Shin-Etsu Chemical Co., Ltd.) and the like. The hydroxy-modified polyoxyl resin is exemplified by FM-4411, FM-4429, FM-DA21, and FM-DA26 (the above is manufactured by CHISSO Co., Ltd.). In addition, X-22-170DX, X-22-2426, X-22-176F (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like which are single-ended reactive polysiloxane resins are also included.

The above surfactant may be used in combination with other surfactants, and is preferably an anionic surfactant such as a sulfonate, a sulfate or a phosphate salt, or a polyoxyalkylene chain. A nonionic surfactant such as an ether group or an ether ester type of a hydrophilic group is used in combination. The amount of the surfactant added is 0.05 to 3.0% by mass in the low refractive index coating composition, which not only has high water repellency, oil repellency, and antifouling properties, but also exhibits surface scratch resistance. In terms of effect, it is preferable.

Further, the above surfactant may be contained in the antistatic layer in order to reduce coating unevenness.

The low refractive index layer is coated to form a low refractive index layer by a conventional method such as a gravure coater, a dip coater, a reverse roll coater, a wire coater, a die coater, or an inkjet method. The coating composition described above is formed by drying after heating and hardening treatment.

The coating amount is preferably from 0.05 to 100 μm, preferably from 0.1 to 50 μm, in terms of wet film thickness. Further, the dry film thickness is adjusted so as to have the film thickness as described above by the solid content concentration of the coating composition.

The hardening method is exemplified by a heat hardening method by heating, a hardening method by light irradiation such as ultraviolet rays, or the like. In the case of heat hardening, the heating temperature is preferably from 50 to 300 ° C, more preferably from 60 to 250 ° C, most preferably from 80 to 150 ° C. When hardened by light irradiation, the exposure amount of the irradiation light is preferably from 10 mJ/cm ² to 10 J/cm ² , more preferably from 100 mJ/cm ² to 500 mJ/cm ² .

Here, the wavelength range of the irradiation light is not particularly limited, but it is preferred to use light having a wavelength in the ultraviolet range. 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.

Further, after the low refractive index layer is formed, the step of heat treatment at 50 to 160 ° C is also included. The heat treatment period may be appropriately determined depending on the set temperature. For example, if it is 50 ° C, it is preferably 3 days or longer and less than 30 days, and if it is 160 ° C, it is preferably 10 minutes or more and 1 day or less. .

Moreover, in the antireflection film according to another embodiment of the present invention, a transparent film substrate is used as the support substrate, and can be produced, for example, as will be described later. The low refractive index layer in the antireflection film can be formed by, for example, a manufacturing apparatus of the optical film shown in Fig. 1. 1 is a schematic view showing a manufacturing apparatus of an optical film.

The optical film manufacturing apparatus includes the delivery roller 1, the transport roller 2, the coating device 3, the first drying device 5, the active wire irradiation device 6, the second drying device 7, the winding device 8, and the like.

The delivery roller 1 is a long film Y for forming the low refractive index layer on the surface. For example, a transparent film substrate including the transparent film substrate or the intermediate layer is sequentially fed to the transport roller. 2.

The transport roller 2 sequentially transports the fed film Y to the coating device 3, the first drying device 5, the active wire irradiation device 6, the second drying device 7, the winding device 8, and the like.

The coating device 3 performs the above-described coating on the surface of the film Y which is maintained at the traveling position by the opposing roller 4 at a position facing the coating device 3. The coating device 3 is exemplified by, for example, an extrusion coater.

The first drying device 5 is a roller having a plurality of rollers, and the coated coating liquid for forming a low refractive index layer is dried during the transfer of the film Y. In this case, it may be dried by using heated air, infrared rays, or the like alone, or may be dried by using heated air and infrared rays. From the standpoint of simplicity, heated air is preferably used. The drying temperature is suitably selected depending on the amount of the solvent which is preferably used, but is preferably from 50 to 120 °C. Moreover, it can also be dried at a certain temperature, or can be divided into three to four stages of temperature, and dried in several stages.

The active-line irradiation device 6 includes an active-line irradiation lamp 6a, a cooling medium supply unit 6b, and an atmosphere gas supply unit 6c. The active-line irradiation lamp 6a irradiates the coating liquid for forming a low refractive index layer with an active line. Specifically, for example, the above-described low pressure mercury lamp, medium pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp, carbon arc lamp, metal halide lamp, xenon lamp, or the like can be cited. The cooling medium supply unit 6b supplies a medium to cool the active-line irradiation lamp 6a. The aforementioned medium is exemplified by air or the like. The atmosphere gas supply unit 6c supplies an atmosphere gas suitable for curing the coating liquid for forming a low refractive index layer to the periphery of the film Y coated with the coating liquid for forming a low refractive index layer. The atmosphere gas is exemplified by an inert gas such as nitrogen gas or argon gas.

The second drying device 7 has a plurality of rolls which are used to dry the coated film Y for coating the low refractive index layer during transfer. That is, a device for performing heat treatment after forming the aforementioned low refractive index layer.

The winding device 8 includes a winding core 15 and a warm air blowing port 10 and the like. A film having the aforementioned low refractive index layer is wound up on the winding core 15 described above. At this time, the warm air can be blown to the film Y from the warm air blowing port 10.

Further, the apparatus for producing an optical film shown in Fig. 1 can be used for forming an intermediate layer by using a coating liquid for forming an intermediate layer such as an antistatic layer or a hard coat layer instead of a coating liquid for forming a low refractive index layer.

When each layer is formed by coating as described above, it is preferred that the width of the transparent film substrate is taken up in a roll shape at 1.4 to 4 m, and the coating is carried out, dried, and hardened, and then wound into a roll shape. In addition, after the antireflection film is laminated in the antireflection film, it is wound into a roll and is manufactured by a manufacturing method of heat treatment at a temperature of 50 to 160 ° C to coat the antireflection film in a long strip. It is preferred in terms of sex and stability. The heat treatment period is appropriately determined depending on the set temperature. For example, if the temperature is 50 ° C, it is preferably 3 days or longer and less than 30 days, and if the temperature is 160 ° C, it is preferably 10 minutes or longer and 1 day or shorter. range. In general, it is preferred to set the temperature at a relatively low temperature, preferably at a temperature of 50 to 60 ° C for about 7 days, so that the heat treatment effect of the outer portion of the reel, the central portion of the reel, and the winding core portion is not different.

In order to stabilize the heat treatment, it is necessary to carry out the temperature and humidity adjustment, and it is preferably carried out in a heat treatment chamber such as a clean room.

When the anti-reflective film is taken up into a roll shape, the core of the coil is not particularly limited as long as it is a core on the cylinder, but it is preferably a hollow plastic core, and the plastic material is preferably a heat-resistant plastic resistant to heat treatment temperature. For example, a resin such as a phenol resin, a xylene resin, a melamine resin, a polyester resin, or an epoxy resin. Further, it is preferably a thermosetting resin which is reinforced by a filler such as glass fiber. The number of coils taken to the coils is preferably 100 or more, more preferably 500 or more, and the coiling thickness is preferably 5 cm or more.

Further, in the low-reflection member of the present embodiment, the low refractive index layer has a thickness exceeding 1 time and less than 3 times, preferably 1.2 to 2.5 times the average particle diameter of the cerium oxide fine particles. Further, the thickness of the low refractive index layer may be within the above range, but is preferably, for example, 0.05 to 0.15 μm, more preferably 0.08 to 0.12 μm. When the low refractive index layer is too thin, the amount of cerium oxide fine particles fixed in a state exposed from the surface of the low refractive index layer increases, and the tendency of the cerium oxide fine particles to fall off is not sufficiently suppressed. Further, when the low refractive index layer is too thick, the reflectance increases, and the interference fringe pattern tends to become large.

Further, the thickness of the low refractive index layer in the low reflection member of the present embodiment can be measured by photographing a cross-sectional photograph of a low refractive index layer of a low reflection member by TEM (transmission electron microscope). Further, the ratio of the thickness of the low refractive index layer to the average particle diameter of the cerium oxide microparticles (the thickness of the low refractive index layer) can be calculated from the thickness of the measured low refractive index layer and the average particle diameter of the cerium oxide microparticles. / Average particle diameter of the aforementioned cerium oxide microparticles).

The surface roughness Ra of the low refractive index layer is less than 5 nm, preferably 4 nm or less, more preferably 3 nm or less. Further, the surface roughness Ra of the low refractive index layer is preferably as small as possible, but is actually about 1 nm or more. When the surface roughness Ra of the low refractive index layer is too large, the amount of cerium oxide fine particles fixed in a state in which the surface of the low refractive index layer is exposed is increased, and there is a tendency that the cerium oxide fine particles are not sufficiently prevented from falling off.

Further, the surface roughness Ra herein is based on JIS B0601 2001, and specifically, it can be obtained, for example, by measuring the surface of the low refractive index layer of the low reflection member by AFM (atomic force microscope).

(layer composition)

An example of a preferred layer structure of the antireflection film according to another embodiment of the present invention is shown below. Also, "/" shows the laminated configuration. However, the present invention is not limited to the layer builders described below.

Film substrate / low refractive index layer

Film substrate / antistatic layer / low refractive index layer

Back coating / film substrate / low refractive index layer

Back coating / film substrate / antistatic layer / low refractive index layer

Back Coating / Film Substrate / Hard Coating / Antistatic Layer / Low Refractive Index Layer

Back coating / film substrate / anti-glare layer / anti-static layer / low refractive index layer

<Antistatic layer and hard coating>

The following antistatic layer and hard coat are described below.

The antistatic layer and the hard coat layer of the present embodiment may be provided as different layers, and may also be used as a hard coat layer for preventing damage of the antistatic layer.

The hard coat layer is usually a layer composed of an ionizing radiation curable resin such as a thermosetting resin or an ultraviolet curable resin, and a certain degree of film thickness is required in terms of mechanical strength (pencil hardness, scratch resistance). Preferably, the pencil hardness is 2H or more, preferably 3H or more, and more preferably 4H or more.

The antistatic layer is preferably a layer mainly containing conductive fine particles and a binder resin. Further, the refractive index of the antistatic layer is measured at a wavelength of 550 nm, preferably in the range of 1.45 to 1.60. Further, the antistatic layer is preferably a layer having a surface specific resistance adjusted to 10 ¹³ Ω/cm ² (25 ° C, 55% RH) or less. More preferably, it is 10 ¹⁰ Ω/cm ² (25 ° C, 55% RH) or less, preferably 10 ⁹ Ω/cm ² (25 ° C, 55% RH) or less.

Here, the surface specific resistance was measured by adjusting the sample at 25 ° C and 55% RH for 24 hours, and using a value measured by a resistivity meter. Further, the resistivity meter device can use, for example, HIRESTA UP MCP-HT450 manufactured by Mitsubishi Chemical Corporation.

Further, the conductive fine particles in the antistatic layer of the present embodiment are preferably metal oxide particles or π-conjugated conductive polymers. Further, the binder resin is preferably an ionizing radiation curable resin as described above.

The ionizing radiation-curable resin used in the antistatic layer and the hard coat layer is preferably an acrylic compound used for the low refractive index layer.

The amount of the ionizing radiation-curable resin to be added is preferably 15% by mass or more and less than 80% by mass in the solid content in the antistatic layer and the hard coat layer forming composition (hereinafter also referred to as an antistatic layer coating liquid). .

Further, in order to promote the hardening of the ionizing radiation-curable resin in the antistatic layer and the hard coat layer, a photopolymerization initiator is preferably contained. As for the photopolymerization starting dose, it is preferably contained by a photopolymerization initiator: ionizing radiation-curable resin = 20:100 to 0.01:100 in terms of a mass ratio.

Specific examples of the photopolymerization initiator include acetophenone, benzophenone, hydroxybenzophenone, micher's ketone, amyloxime ester, thioxanthone, and the like. And such derivatives, but are not particularly limited.

Next, the conductive fine particles will be described. The conductive fine particles in the antistatic layer of the present embodiment are preferably metal oxides or π-conjugated conductive polymers.

First, the metal oxide particles will be described.

The type of the metal oxide particles is not particularly limited, and may be selected from the group consisting of Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P, and a metal oxide of at least one element of S. Further, the metal oxide particles may be doped with a trace atom such as Al, In, Sn, Sb, Nb, a halogen element or Ta. Also, it may be a mixture of these. In the present embodiment, it is preferred to use cerium oxide, tin oxide, zinc oxide, tin-containing indium oxide (ITO), antimony-containing tin oxide (ATO), phosphorus-containing tin oxide (PTO), and zinc silicate. At least one metal oxide particle is used as a main component. In particular, it is preferably one containing phosphorus-containing tin oxide (PTO) or zinc antimonate particles.

The average particle diameter of the primary particles of the metal oxide particles is in the range of 10 nm to 200 nm, preferably 20 to 150 nm, more preferably 30 to 100 nm. The average particle diameter of the metal oxide particles can be measured by an electron micrograph obtained by a scanning electron microscope (SEM) or the like. Further, it may be measured by a particle size distribution meter such as a dynamic light scattering method or a static light scattering method. If the particle size is too small, aggregation tends to occur, and the dispersibility is deteriorated. If the particle size is too large, the turbidity is remarkably increased. The shape of the metal oxide 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 particles can also be surface treated with an organic compound. By modifying the surface of the metal oxide particles with the surface of the organic compound, the dispersion stability in the organic solvent can be improved, the control of the dispersed particle diameter can be easily performed, and the aggregation and sedimentation over time can be suppressed. Accordingly, the amount of surface modification by the organic compound is preferably from 0.1 to 5% by mass, more preferably from 0.5 to 3% by mass, based on the metal oxide particles. Examples of the organic compound used for the surface treatment include a polyol, an alkanolamine, a stearic acid, a decane coupling agent, and a titanate coupling agent. Preferred among these are the decane coupling agents described later. It is also possible to combine two or more kinds of surface treatments.

The metal oxide particles are supplied to the coating liquid for forming the antistatic layer in a dispersion state dispersed in the medium. The dispersion medium of the metal oxide particles is preferably a liquid having a boiling point of 60 to 170 °C. Specific examples of the dispersing solvent are water, alcohols (e.g., methanol, ethanol, isopropanol, butanol, benzyl alcohol), ketones (e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone, ring). Hexanone), keto alcohols (eg, diacetone alcohol), esters (eg, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl formate, ethyl formate, propyl formate, formic acid) Ester), aliphatic hydrocarbons (eg, hexane, cyclohexane), halogenated hydrocarbons (eg, dichloromethane, chloroform, carbon tetrachloride), aromatic hydrocarbons (eg, benzene, toluene, xylene), guanamine (eg, dimethylformamide, dimethylacetamide, n-methylpyrrolidone), ethers (eg, diethyl ether, dioxane, tetrahydrofuran), ether alcohols (eg, 1- Methoxy-2-propanol), propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate. Among them, the most preferred ones are toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methanol and isopropanol.

Further, the metal oxide particles can be dispersed in the medium using a disperser. Examples of the dispersing machine are a sand mill (for example, a fin-grinding bead mill), a high-speed blade grinder, a Banbury grinder, a roll grinder, a micro-pulverizer, and a colloid mill. It is best to use a sand mill and a high speed blade mill. In addition, pre-dispersion treatment can also be performed. Examples of the dispersing machine used in the pre-dispersion treatment are a ball mill, a three-roll mill, a kneader, and an extruder. It is also preferred to contain a dispersing agent.

It may also contain metal oxide particles having a core/shell structure. The shell is preferably formed on the periphery of the core, and a plurality of layers may be formed in order to further improve light resistance. The core is preferably completely covered with the shell.

Next, the π-conjugated conductive polymer will be described.

The π-conjugated conductive polymer used in the present embodiment can be an organic polymer having a π-conjugated main chain. For example, polythiophenes, polypyrroles, polyanilines, polyphenyls, polyacetylenes, polyphenylenes, vinyls, polyacenes, polythiophenes, and copolymers thereof. From the viewpoint of ease of polymerization and stability, polythiophenes, polypyrroles, and polyanilines are preferred.

The π-conjugated conductive polymer can obtain sufficient conductivity and solubility to the binder resin even without substitution, but can further introduce an alkyl group, a carboxyl group, a thiol group, or an alkoxy group in order to further improve conductivity or solubility. a functional group such as a hydroxy group or a cyano group.

Specific examples of the π-conjugated conductive polymers are polythiophene, poly(3-methylthiophene), poly(3-ethylthiophene), poly(3-propylthiophene), poly(3-butylene). Thiophene), poly(3-hexylthiophene), poly(3-octylthiophene), poly(3-mercaptothiophene), poly(3-dodecylthiophene), poly(3-bromothiophene), poly (3-chlorothiophene), poly(3-cyanothiophene), poly(3-phenylthiophene), poly(3,4-dimethylthiophene), poly(3,4-dibutylthiophene), poly (3-hydroxythiophene), poly(3-methoxythiophene), poly(3-ethoxythiophene), poly(3-butoxythiophene), poly(3-hexyloxythiophene), poly(3) -octyloxythiophene), poly(3-decyloxythiophene), poly(3-dodecyloxythiophene), poly(3,4-dihydroxythiophene), poly(3,4-dimethoxy) Thiophene), poly(3,4-diethoxythiophene), poly(3,4-dipropoxythiophene), poly(3,4-dibutoxythiophene), poly(3,4-dihexyl) Oxythiophene), poly(3,4-dioctyloxythiophene), poly(3,4-dimethoxyoxythiophene), poly(3,4-di-dodecyloxythiophene), poly(3) , 4-extended ethylenedioxythiophene), poly(3,4-propanedioxythiophene), poly(3,4-butyleneoxythiophene), poly(3-methyl-4-methoxy) Thiophene), poly( 3-methyl-4-ethoxythiophene), poly(3-carboxythiophene), poly(3-methyl-4-carboxythiophene), poly(3-methyl-4-carboxyethylthiophene), poly (3-methyl-4-carboxybutylthiophene), polypyrrole, poly(N-methylpyrrole), poly(3-methylpyrrole), poly(3-ethylpyrrole), poly(3-N- Propylpyrrole), poly(3-butylpyrrole), poly(3-octylpyrrole), poly(3-mercaptopyrrole), poly(3-dodecylpyrrole), poly(3,4-di Methylpyrrole), poly(3,4-dibutylpyrrole), poly(3-carboxypyrrole), poly(3-methyl-4-carboxypyrrole), poly(3-methyl-4-carboxyethyl) Pyrrole), poly(3-methyl-4-carboxybutylpyrrole), poly(3-hydroxypyrrole), poly(3-methoxypyrrole), poly(3-ethoxypyrrole), poly(3- Butoxypyrrole), poly(3-hexyloxypyrrole), poly(3-methyl-4-hexyloxypyrrole), polyaniline, poly(2-methylaniline), poly(3-isobutyl) Aniline), poly(2-anilinosulfonic acid), poly(3-anilinosulfonic acid), and the like. These may be used alone or in combination of two or more.

A dopant component may also be added to the π-conjugated conductive polymer.

The dopant component is exemplified by a low molecular weight dopant such as a halogen, a Lewis acid, a protic acid, or a transition metal halide, or a polymer such as a polyanion.

The polyanion is a polymer having an anionic group function as a dopant with respect to a π-conjugated conductive polymer, and is a substituted or unsubstituted polyalkylene, a substituted or unsubstituted polyalkylene, Substituted or unsubstituted polyimine, substituted or unsubstituted polyamine, substituted or unsubstituted polyester, and copolymers thereof, which are composed of anionic groups and It is composed of constituent units having an anionic group.

The term "polyalkylene" as a main chain is a polymer composed of methyl repeats, and is exemplified by, for example, polyethylene, polypropylene, polybutene, polypentene, polyhexene, polyvinyl alcohol, polyvinylphenol, Polyacrylonitrile, polyacrylate, polystyrene, and the like.

The polyalkylene is a polymer composed of one or more unsaturated bonds in the main chain, and is exemplified by, for example, a compound selected from the group consisting of an exopropylene group, a 1-methylpropenyl group, a 1-butyl-propenyl group, and a 1-fluorene group. Propylene group, 1-cyano propenyl group, 1-phenylpropenyl group, 1-hydroxypropenyl group, 1-butenbutenyl group, 1-methyl-1-exetylene group, 1-ethyl-1 - a butenyl group, a 1-octyl-1-butenyl group, a 2-methyl-1-butenyl group, a 2-ethyl-1-butenyl group, a 2-butyl-1-stretch Butenyl, 2-hexyl-1-enbutenyl, 2-octyl-1-enbutenyl, 2-mercapto-1-enbutenyl, 2-phenyl-1-exetylene , 2-butenyl, 1-methyl-2-exenbutyl, 1-ethyl-2-enbutenyl, 1-octyl-2-exenbutyl, 2-methyl-2 - a butenyl group, a 2-ethyl-2-enbutenyl group, a 2-butyl-2-butenyl group, a 2-hexyl-2-enbutenyl group, a 2-octyl-2-butylene group Alkenyl, 2-mercapto-2-enbutenyl, 2-phenyl-2-exenbutenyl, 2-extended propyl-2-exenbutenyl, 2-pentenyl, 4 -ethyl-2-pentopentyl, 4-propyl-2-endopentyl, 4-butyl-2-endopentyl, 4-hexyl-2-endopentyl, 4-cyano 2-pentenenyl a polymer of one or more constituent units of 3-methyl-2-endopentyl, 3-phenyl-2-pentopentenyl, 4-hydroxy-2-pentopentyl, and hexenyl .

Polyimine is exemplified by pyromellitic dianhydride, biphenyltetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride, 2,2',3,3'-tetracarboxydiphenyl ether dianhydride, Anhydride such as 2,2'-[4,4'-bis(dicarboxyphenyloxy)phenyl]propane dianhydride and oxydiamine, p-phenylenediamine, m-phenylenediamine, benzophenone diamine A polyimine composed of a diamine.

The polyamines are exemplified by polyamine 6, polyamine 6,6, polyamine 6, 10 and the like.

The polyester is exemplified by polyethylene terephthalate, polybutylene terephthalate or the like.

The anionic group of the polyanion is preferably a functional group which initiates chemical oxidation doping to the π-conjugated conductive polymer, but from the viewpoint of ease of manufacture and stability, it is preferably a monosubstituted sulfate group or a single A substituted phosphate group, a phosphate group, a carboxyl group, a sulfo group or the like. Further, from the viewpoint of the doping effect of the functional group on the π-conjugated conductive polymer, a sulfo group, a monosubstituted sulfate group or a carboxyl group is more preferable.

Specific examples of the polyanion are exemplified by polyvinylsulfonic acid, polystyrenesulfonic acid, polyallylsulfonic acid, polyacrylic acid ethanesulfonic acid, polyacrylic acid butanesulfonic acid, poly(2-propenylamine-2-methyl Propane sulfonic acid), polyisoprene sulfonic acid, polyvinyl carboxylic acid, polystyrene carboxylic acid, polyallyl carboxylic acid, polypropylene carboxylic acid, polymethacrylic carboxylic acid, poly(2-propene Guanidine-2-methylpropane sulfonic acid), polyisoprene dicarboxylic acid, polyacrylic acid, and the like. These may be homopolymers, or may be two or more kinds of copolymers. Among these, polystyrenesulfonic acid, polyisoprene disulfonic acid, polyacrylic acid ethanesulfonic acid, and polyacrylic acid butanesulfonic acid are preferable. The polyanion has high compatibility with the binder resin, and the conductivity of the obtained conductive layer can be further improved.

In the present embodiment, in addition to the polyanion, as long as the π-conjugated conductive polymer can be redoxed, a donor or acceptor-like dopant such as the following can be used.

The donor dopants are listed as alkali metals such as sodium and potassium, alkaline earth metals such as calcium and magnesium, tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium, methyltriethylammonium, A quaternary amine compound such as dimethyldiethylammonium or the like.

As the acceptor dopant, a halogen compound such as Cl ₂ , Br ₂ , I ₂ , ICl, IBr, or IF, or a Lewis acid such as PF ₅ , AsF ₅ , SbF ₅ , BF ₅ , BCl ₅ , BBr ₅ , or SO _{3 may be used} . , organic cyano compounds such as tetracyanoethylene, tetracyanoethylene oxide, tetracyanobenzene, dichlorodicyanobenzoquinone, tetracyanoquinodimethane, tetracyanazinene, protonic acid, organometallic compound, Fuller Alkene, hydrogenated fullerene, fullerene hydroxide, carboxylated fullerene, sulfonated fullerene, and the like.

As for the protic acid, it is enumerated as an inorganic acid or an organic acid. The inorganic acid is exemplified by, for example, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, hydrofluoric acid, perchloric acid or the like. Further, the organic acid is exemplified by an organic carboxylic acid or an organic sulfonic acid.

The organic carboxylic acid can be used for one or two or more carboxyl groups in aliphatic, aromatic, cyclic aliphatic or the like. Listed as, for example, formic acid, acetic acid, oxalic acid, benzoic acid, phthalic acid, maleic acid, fumaric acid, malonic acid, tartaric acid, citric acid, lactic acid, succinic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, Trifluoroacetic acid, nitroacetic acid, triphenylacetic acid, and the like.

The organic sulfonic acid can be used for a polymer containing one or two or more sulfo groups in an aliphatic, aromatic, cyclic aliphatic or the like, or a polymer containing a sulfo group.

The inclusion of a sulfo group is exemplified by, for example, methanesulfonic acid, ethanesulfonic acid, 1-propanesulfonic acid, 1-butanesulfonic acid, 1-hexanesulfonic acid, 1-heptanesulfonic acid, 1-octanesulfonic acid. , 1-decanesulfonic acid, 1-decanesulfonic acid, 1-pentadecanesulfonic acid, 2-bromoethanesulfonic acid, 3-chloro-2-hydroxypropanesulfonic acid, trifluoromethanesulfonic acid, trifluoro Ethanesulfonic acid, Colistin methanesulfonic acid, 2-propenylamine-2-methylpropanesulfonic acid, aminomethanesulfonic acid, 1-amino-2-naphthalene-4-sulfonic acid, 2 -Amino-5-naphthalene-7-sulfonic acid, 3-aminopropanesulfonic acid, N-cyclohexyl-3-aminopropanesulfonic acid, benzenesulfonic acid, alkylbenzenesulfonic acid, p-toluenesulfonic acid, Xylenesulfonic acid, ethylbenzenesulfonic acid, propylbenzenesulfonic acid, butylbenzenesulfonic acid, pentylbenzenesulfonic acid, hexylbenzenesulfonic acid, heptylbenzenesulfonic acid, octylbenzenesulfonic acid, mercaptobenzenesulfonate Acid, nonylbenzenesulfonic acid, cetylbenzenesulfonic acid, 2,4-dimethylbenzenesulfonic acid, dipropylbenzenesulfonic acid, 4-aminobenzenesulfonic acid, o-aminobenzenesulfonic acid, m-Aminobenzenesulfonic acid, 4-amino-2-chlorotoluene-5-sulfonic acid, 4-amino-3-methylbenzene-1-sulfonic acid, 4-amino-5-methoxy- 2-methylbenzenesulfonic acid, 2-amino-5-methylbenzene-1-sulfonic acid, 4 -Amino-2-methylbenzene-1-sulfonic acid, 5-amino-2-methylbenzene-1-sulfonic acid, 4-amino-3-methylbenzene-1-sulfonic acid, 4-B Indole-3-chlorobenzenesulfonic acid, 4-chloro-3-nitrobenzenesulfonic acid, p-chlorobenzenesulfonic acid, naphthalenesulfonic acid, methylnaphthalenesulfonic acid, propylnaphthalenesulfonic acid, butylnaphthalenesulfonic acid , amyl naphthalenesulfonic acid, 4-amino-1-naphthalenesulfonic acid, 8-chloronaphthalene-1-sulfonic acid, naphthalenesulfonic acid formaldehyde polycondensate, melaminesulfonic acid formaldehyde polycondensate, sulfonic acid, embedded Dinaphthalenesulfonic acid, etc. Further, these metal salts can also be used.

Those containing two or more sulfo groups are exemplified by, for example, ethane disulfonic acid, butane disulfonic acid, pentane disulfonic acid, decane disulfonic acid, o-benzene disulfonic acid, m-benzene disulfonic acid, p- Phenyl disulfonic acid, toluene disulfonic acid, xylene disulfonic acid, chlorobenzene disulfonic acid, fluorobenzene disulfonic acid, dimethylbenzene disulfonic acid, diethylbenzene disulfonic acid, aniline-2,4- Disulfonic acid, aniline-2,5-disulfonic acid, 3,4-dihydroxy-1,3-benzenedisulfonic acid, naphthalene disulfonic acid, methylnaphthalene disulfonic acid, ethylnaphthalene disulfonic acid, ten Pentaalkylnaphthalene disulfonic acid, 3-amino-5-hydroxy-2,7-naphthalene disulfonic acid, 1-acetamido-8-hydroxy-3,6-naphthalene disulfonic acid, 2-amino group- 1,4-benzenedisulfonic acid, 1-amino-3,8-naphthalene disulfonic acid, 3-amino-1,5-naphthalene disulfonic acid, 8-amino-1-naphthyl-3,6 -disulfonic acid, 4-amino-5-naphthyl-2,7-disulfonic acid, 4-acetamide-4'-isothiocyanate stilbene-2,2'-disulfonic acid, 4-acetamide-4'-maleimide stilbene-2,2'-disulfonic acid, naphthalene trisulfonic acid, dinaphthylene disulfonic acid, sulfonium disulfonic acid, hydrazine sulfonic acid Wait. Further, these metal salts can also be used.

Further, the conductive fine particles may also contain an ionic compound. The ionic compound is exemplified by an imidazolinium, a pyridinium, an alicyclic amine, an aliphatic amine, an aliphatic cation, an inorganic ion such as BF ₄ ^- or PF ₆ ^- , or a CF ₃ SO ₂ ^- a compound composed of a fluorine-based anion such as (CF ₃ SO ₂ ) ₂ N ^- or CF ₃ CO ₂ ^- .

The conductive fine particles are preferably used in an amount of from 0.01 part by mass to 300 parts by mass, more preferably from 0.1 part by mass to 100 parts by mass, per 100 parts by mass of the ionizing radiation curable resin used as a binder.

A binder such as a thermoplastic resin, a thermosetting resin, or a hydrophilic resin such as gelatin may be used as the antistatic layer and the hard coat layer. Further, the antistatic layer and the hard coat layer may further contain particles of an inorganic compound or an organic compound for adjusting the slidability 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, calcium carbonate, talc, clay, calcined kaolin, calcined calcium citrate, and hydrated. Calcium acid, 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.

Further, the organic particles may be a polymethyl methacrylate resin powder, an acrylic styrene resin powder, a polymethyl methacrylate resin powder, an anthraquinone resin powder, a polystyrene resin powder, a polycarbonate resin powder, or the like. A benzoquinone resin powder, a melamine resin powder, a polyolefin resin powder, a polyester resin powder, a polyamide resin powder, a polyamidene resin powder, or a polyvinyl fluoride resin powder. Preferred fine particles are listed as 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.) Fluorine-containing acrylic resin microparticles. The fluorine-containing acrylic resin fine particles are, for example, commercially available products such as FS-701 manufactured by PAINT Japan. Further, the acrylic particles are, for example, S-4000 manufactured by PAINT, Japan, and the acrylic-styrene particles are, for example, manufactured by PAINT, Japan: S-1200, MG-251, and the like.

The average particle diameter of the fine particle powder is not particularly limited, but is preferably 0.5 μm or less, more preferably 0.1 μm or less, and most preferably 0.001 to 0.1 μm from the viewpoint of not exhibiting the antiglare property described below. .

The average particle diameter of the microparticles can be measured by, for example, a laser diffraction type particle size distribution measuring apparatus.

Further, it is also possible to contain two or more kinds of fine particles having different particle diameters. The ratio of the ultraviolet curable resin to the fine particles is preferably 0.1 to 30 parts by mass based on 100 parts by mass of the resin.

Further, the antistatic layer and the hard coat layer can be coated by a conventional method such as a gravure coater, a dip coater, a reverse roll coater, a wire coater, a die coater, or an inkjet method. The cloth forms a coating composition of an antistatic layer and a hard coat layer, and after coating, it is dried by heating and formed by UV hardening treatment. The coating amount is suitably from 0.1 to 40 μm in terms of 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, more preferably 6 to 15 μm.

The light source for the UV hardening treatment can be used without limitation as long as it is a light source capable of generating ultraviolet rays. 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 vary depending on various lamps, but the amount of active radiation is usually 5 to 500 mJ/cm ² , preferably 5 to 200 mJ/cm ² .

Further, when the active rays are irradiated, it is preferred to carry out the tension while applying the film in the film transport direction, and it is preferable to apply the tension in the width direction. The tension imparted is preferably from 30 to 300 N/m. The tension applying method is not particularly limited, and the tension can be imparted in the conveying direction on the reverse roller, or in the width direction or in the two-axis direction in the cloth stretching machine. Thereby, a film having superior planarity can be obtained.

The coating composition forming the antistatic layer and the hard coat layer may also contain a solvent. The organic solvent contained in the coating composition may be, for example, a hydrocarbon (toluene, xylene), an alcohol (methanol, ethanol, isopropanol, butanol, cyclohexanol), a ketone (acetone, methyl ethyl ketone). Methyl isobutyl ketone), esters (methyl acetate, ethyl acetate, methyl lactate), glycol ethers, and other organic solvents are appropriately selected or may be used in combination.

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

Further, the antistatic layer and the hard coat layer are preferably contained in the above-mentioned polyfluorene-based surfactant or polyoxyether compound described in the above-mentioned low refractive index layer. These are used to improve coatability. Further, the components are preferably added in a range of 0.01 to 3% by mass based on the solid content in the coating liquid.

The polyoxy ether compound is exemplified by polyoxyalkylene ether compounds such as polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oxime A polyoxyalkylphenyl ether compound such as a phenyl ether or a polyoxyethylene octylphenyl ether; a polyoxyalkylene alkyl ether, a polyoxyethylene higher alcohol ether, a polyoxyethylene octyl lauryl ether or the like. The commercially available products of the polyoxyethylene alkyl ethers listed are EMULGEN 1108, EMULGEN 1118S-70 (all manufactured by Kao Corporation), and the commercial products of polyoxyethylene lauryl ether are EMULGEN 103, EMULGEN 104P, EMULGEN 105, EMULGEN 106. , EMULGEN 108, EMULGEN 109P, EMULGEN 120, EMULGEN 123P, EMULGEN 147, EMULGEN 150, EMULGEN 130K (above is Kao company), polyoxyethylene cetyl ether commercially available products are EMULGEN 210P, EMULGEN 220 (above is Kao The company's products are EMULGEN 220, EMULGEN 306P (above is Kao), and polyoxyalkylene ethers are commercially available as EMULGEN LS-106 and EMULGEN LS-110. Commercial products such as EMULGEN LS-114, EMULGEN MS-110 (manufactured by Kao Co., Ltd.), and polyoxyethylene higher alcohol ether are EMULGEN 705, EMULGEN 707, EMULGEN 709, and the like.

Among these nonionic polyoxyether compounds, a polyoxyethylene oleyl ether compound and a compound represented by the following formula (21) are preferred.

C ₁₈ H ₃₅ -O(C ₂ H ₄ O) _n H (21)

In the formula (21), 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 above formula (21) is obtained by reacting ethylene oxide with an oleyl alcohol.

Specific products are listed as EMULGEN 404 [polyoxyethylene (4) oleyl ether], EMULGEN 408 [polyoxyethylene (8) oleyl ether], EMULGEN 409P [polyoxyethylene (9) oleyl ether], EMULGEN 420 [ Polyoxyethylene (13) oleyl ether], EMULGEN 430 [polyoxyethylene (30) oleyl ether] (above), NOFABLEEAO-9905 (polyoxyethylene (5) oleyl ether) manufactured by Nippon Oil & Fats Co., Ltd. )Wait. Also, the number in () indicates the number of n.

The polyoxy ether compounds may be used singly or in combination of two or more.

The content of the polyoxyether compound and the polyoxonium surfactant in the antistatic layer and the hard coat layer is preferably 0.1 to 8.0% by mass, more preferably 0.2 to 4.0% by mass, based on the total content of the polyoxyether compound and the polyoxonium surfactant. It is added in this range and can be stably present in the antistatic layer.

Further, a fluorine surfactant, an acrylic copolymer, an acetylene glycol compound, a nonionic surfactant, a radically polymerizable nonionic surfactant, or the like may be used in combination.

The nonionic surfactant is exemplified by a polyoxyalkyl ester compound such as polyoxyethylene monolaurate, polyoxyethylene monostearate or polyoxyethylene monooleate, sorbitan monolaurate, A sorbitan ester compound such as sorbitan monostearate or sorbitan monooleate.

The acetylene glycol-based compound is exemplified by SURFYNOL 104E, SURFYNOL 104PA, SURFYNOL 420, SURFYNOL 440, DAINOL 604 (above, manufactured by Nissin Chemical Industry Co., Ltd.).

The polyoxyalkylene alkylphenyl ether, such as RMA-564, RMA-568, RMA-1114 (The above is a brand name, manufactured by Nippon Emulsifier Co., Ltd.), etc. are mentioned as a non-ionic surfactant. (Meth) acrylate-based polymerizable surfactant.

Further, the antistatic layer and the hard coat layer may further contain a polyfunctional thiol compound as a hardening aid, and are exemplified by, for example, 1,4-bis(3-mercaptobutyloxy)butane, pentaerythritol ruthenium (3-mercaptobutyrate) , 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, and the like.

In addition, as a commercial item, the product name KARENZ MT series manufactured by Showa Denko Co., Ltd., etc. are listed. The polyfunctional thiol compound is preferably added in an amount of from 0.01 to 50 parts by mass, more preferably from 0.05 to 30 parts by mass, per 100 parts by mass of the ultraviolet curable resin. When it is added in this range, it can exhibit an appropriate function as a curing aid, and it can also be stably present in the antistatic layer and the hard coat layer.

The antistatic layer may also have an overlapping layer structure of two or more layers. One of the layers may be, for example, a so-called clear coat layer containing no metal oxide particles, or may be a color tone adjuster (dye or color tone) having a color tone adjustment function as a color correction filter for various display elements. Pigments, etc.). Further, it may have various functions including an electromagnetic wave blocking agent or an infrared absorbing agent.

<Back coating>

The antireflection film of the present embodiment may be provided with a back coat layer on the surface opposite to the antistatic layer and the hard coat layer on which the transparent film substrate is provided. The back coat layer is provided for correcting the curl generated when the antistatic layer and the hard coat layer are provided or the reflective layer is prevented. That is, by making the surface on which the back coat layer is provided has a property of being curled toward the inner side, the degree of curling can be balanced. Further, the back coat layer is preferably provided by coating with a blocking preventing layer, and in the case where the back coat coating composition is preferably added with an inorganic compound or organic compound having a blocking preventing function. Particles of the compound.

The particles added to the back coat layer are examples of inorganic compounds, and examples thereof include ceria, titania, alumina, zirconia, calcium carbonate, talc, clay, calcined kaolin, calcined calcium citrate, tin oxide, and oxidation. Indium, zinc oxide, ITO, hydrated calcium citrate, aluminum citrate, magnesium citrate and calcium phosphate.

For the particles, for example, AEROSIL R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, TT600 (above, Japan AEROSIL Co., Ltd.), SEAHOSTER KE-P10, SEAHOSTER KE-P30, SEAHOSTER KE can be used. - P50, SEAHOSTER KE-P100, SEAHOSTER KE-P150, SEAHOSTER KE-P250 (above is manufactured by Nippon Shokubai Co., Ltd.).

Examples of the organic compound include, for example, a polyfluorene oxide resin, a fluororesin, and an acrylic resin. Preferably, it is a polyoxynene resin, especially those having a three-dimensional network structure. For example, TOSPEARL 103, TOSPEARL 105, TOSPEARL 108, TOSPEARL 120, TOSPEARL 145, TOSPEARL 3120, and TOSPEARL 240 can be used (above GE Toshiba Poly Oxygen Co., Ltd. product name seller.

These AEROSIL 200V, AEROSIL R972V, SEAHOSTER KE-P30, SEAHOSTER KE-P50 and SEAHOSTER KE-P100 are most suitable for use because they retain low turbidity and prevent blockage.

The particles contained in the back coat layer are preferably from 0.1 to 50% by mass, more preferably from 0.1 to 10% by mass, based on the binder. The turbidity increase when the back coat layer is provided is preferably 1.5% or less, more preferably 0.5% or less, and most preferably 0.1% or less.

The coating composition used for the coating of the back coat layer preferably contains a solvent. The solvent is, for example, dioxane, acetone, methyl ethyl ketone, methyl isobutyl ketone, N,N-dimethylformamide, methyl acetate, ethyl acetate, trichloroethylene, dichloromethane, Dichloroethylene, tetrachloroethane, trichloroethane, chloroform, water, methanol, ethanol, n-propanol, isopropanol, n-butanol, cyclohexanone, cyclohexanol, propylene glycol monomethyl ether, propylene glycol Ethyl ether or a hydrocarbon (toluene, xylene) or the like can be used in combination as appropriate.

The resin used as the binder of the back coat layer may, for example, be a vinyl chloride-vinyl acetate copolymer, a vinyl chloride resin, a vinyl acetate resin, a copolymer of vinyl acetate and vinyl alcohol, or a partially hydrolyzed vinyl chloride. -vinyl acetate copolymer, chlorinated ethylene-vinylidene chloride copolymer, chlorinated ethylene-acrylonitrile copolymer, ethylene-vinyl alcohol copolymer, chlorinated polyvinyl chloride, ethylene-vinyl chloride copolymer, ethylene - a vinyl polymer or copolymer such as a vinyl acetate copolymer, nitrocellulose, cellulose acetate propionate (preferably having an ethyl sulfhydryl substitution degree of 1.8 to 2.3, and a propyl ketone group substitution degree of 0.1 to 1.0) a cellulose derivative such as diethyl acetyl cellulose, cellulose acetate butyrate resin, a copolymer of maleic acid and/or acrylic acid, an acrylate copolymer, an acrylonitrile-styrene copolymer, chlorine Polyethylene, acrylonitrile-chlorinated polyethylene-styrene copolymer, methyl methacrylate-butadiene-styrene copolymer, acrylic resin, polyvinyl alcohol resin, polyvinyl acetal resin, polyethylene Keal acetal resin, urethane resin, Ester polyurethane resin, polyether polyurethane resin, polycarbonate polyurethane resin, polyester resin, polyether resin, polyamide resin, amine resin, styrene - A rubber-based resin such as a butadiene resin or a butadiene-acrylonitrile resin, a polyfluorene-based resin, a fluorine-based resin, or the like is not limited thereto.

For example, the acrylic resin is ACRYPET MD, VH, MF, V (manufactured by Mitsubishi Rayon Co., Ltd.), HAIPERL M-4003, M-4005, M-4006, M-4202, M-5000, M-5001, M. -4501 (manufactured by Gensei Industrial Co., Ltd.), DIANALBR-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 Corporation) made of acrylic acid and methyl When the acrylic monomer is sold as various raw materials, copolymers, and the like which are produced as raw materials, those which are preferable may be appropriately selected.

For example, a resin used as a binder is preferably a blend of a cellulose ester such as cellulose diacetate or cellulose acetate propionate and an acrylic resin, and a particle composed of an acrylic resin is used. The difference in refractive index between the particles and the binder is from 0 to less than 0.02, which can be a highly transparent back coat layer.

Further, the dynamic friction coefficient of the back coat layer is 0.9 or less, preferably 0.1 to 0.9.

As a method of forming the back coat layer, a gravure coater, a dip coater, a reverse roll coater, a wire coater, a die coater, or a spray coating, an inkjet coating, or the like is used. The coating composition for forming the back coat layer is preferably applied to the surface of the transparent resin film at a wet film thickness of 1 to 100 μm, preferably at a wet film thickness of 5 to 30 μm.

Further, after coating, it may be dried by heating and hardened as needed to form a back coat layer. The hardening treatment can be used for the contents described in the low refractive index layer.

The back coat can also be applied in two or more portions. Further, the back coat layer is also preferably an easy-adhesive layer for improving the adhesion to the polarizer.

<Support substrate>

The support substrate is not particularly limited as long as it is a support substrate for the low reflection member, and a conventional support substrate can be used. Therefore, the transparent film base material which is a support base material at the time of antireflection film is the following.

<Transparent film substrate>

The transparent film substrate is preferably easy to manufacture, easy to adhere to a low refractive index layer or the like, and is optically isotropic. Any one of these properties may be used, for example, a triethylenesulfonated cellulose film, a cellulose acetate propionate film, a cellulose diacetate film, a cellulose acetate butyrate film, or the like. A cellulose ester film, a polyester film such as polyethylene terephthalate or polyethylene naphthalate, a polycarbonate film, a polyacrylate film, or a polyether (including a polyether oxime) Film, polyethylene film, polypropylene film, ceramide, polyvinylidene chloride film, polyvinyl alcohol film, ethylene vinyl alcohol film, syndiotactic polystyrene film, raw borneol resin film, polymethyl pentylene An ene film, a polyether ketone film, a polyether ketoximine film, a polyamide film, a fluororesin film, a nylon film, a cycloolefin polymer film, a polymethyl methacrylate film or an acrylic film, but not Limited to these. Among these, cellulose ester films (for example, KONICA MINOLTA TECH KC8UX, KC4UX, KC5UX, KC8UCR3, KC8UCR4, KC8UCR5, KC8UY, KC4UY, KC4UE, and KC12UR (above, KONICA MINOLTA OPTO)), polycarbonate In the present embodiment, the ester film, the cycloolefin polymer film, and the polyester film, in particular, the cellulose ester film can be suitably obtained in terms of production, cost, isotropic properties, adhesion, and effects of the present invention. Preferably.

(cellulose ester film)

Hereinafter, a preferred cellulose ester film (hereinafter also referred to as a cellulose ester film) as a transparent film substrate will be described.

The cellulose ester resin (hereinafter also referred to as cellulose ester) is preferably a lower fatty acid ester of cellulose. The so-called lower fatty acid in the lower fatty acid ester of cellulose means a fatty acid having 6 or less carbon atoms, and for example, cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate propionic acid can be used. A mixed fatty acid ester of an ester, cellulose acetate butyrate or the like. The above-mentioned mixed fatty acid ester is not limited to the conventional cellulose acetate propionate or cellulose acetate butyrate, and an example thereof is disclosed in JP-A-10-45804 and JP-A 08-231761. A mixed fatty acid ester such as cellulose acetate propionate or cellulose acetate butyrate described in U.S. Patent No. 2,319,052. In the above description, the lower fatty acid ester of cellulose which is preferably used is cellulose triacetate or cellulose acetate propionate. These cellulose esters may be used singly or in combination.

In the case of cellulose triacetate, it is preferred to use an average degree of acetification (combined amount of acetic acid) of 54.0 to 62.5%, more preferably an average acetate degree of 58.0 to 62.5% of cellulose acetate. If the average degree of vinegar is small, the dimensional change is large, and the degree of polarization of the polarizing plate is lowered. If the average degree of acetification is large, the solubility in the solvent is lowered to lower the productivity.

A preferred cellulose ester other than cellulose triacetate is a substituent having a fluorenyl group having 2 to 4 carbon atoms as a substituent, and a degree of substitution of the ethyl thiol group is X, a propyl fluorenyl group or a butyl group. When Y is a cellulose ester which simultaneously satisfies the cellulose esters of the following formulas (I) and (II):

2.6≦X+Y≦3.0 (I)

0≦X≦2.5 (II)

Among them, cellulose acetate propionate is particularly preferably used, and among them, preferably 1.9 ≦X ≦ 2.5, 0.1 ≦ Y ≦ 0.9. The portion which is not substituted by a thiol group is present as a usual hydroxyl group. These methods can be synthesized by conventional methods. The method for determining the degree of substitution of thiol can be determined in accordance with ASTM-D817-96.

The molecular weight of the cellulose ester is preferably from 60,000 to 300,000, more preferably from 70,000 to 200,000, and most preferably from 100,000 to 200,000, in terms of number average molecular weight (Mn). The weight average molecular weight (Mw) / number average molecular weight (Mn) ratio of the cellulose ester used in the present embodiment is preferably 4.0 or less, more preferably 1.4 to 2.3.

Since the average molecular weight and molecular weight distribution of the cellulose ester can be measured by high-speed liquid chromatography, the number average molecular weight (Mn) and the weight average molecular weight (Mw) can be calculated and the ratio can be calculated.

The measurement conditions are as follows:

Solvent: dichloromethane

Pipe column: Shodex K806, K805, K803G (made by Showa Denko Co., Ltd., three connections are used)

Column temperature: 25 ° C

Sample concentration: 0.1% by mass

Detector: RI model 504 (manufactured by GL Science)

Pump: L6000 (Hitachi Manufacturing Co., Ltd.)

Flow rate: 1.0ml/min

Calibration curve: Standard polystyrene STK standard polystyrene (Toray)

A calibration curve obtained from 13 samples of Mw = 1,000,000 to 500 was used. Thirteen samples were sampled at approximately equal intervals.

The cellulose ester may be used alone or in combination as a cellulose ester synthesized by using cotton short cotton, wood pulp, kenaf or the like as a raw material. It is preferred to use a cellulose ester synthesized from cotton short cotton (hereinafter referred to as short cotton) alone or in combination.

Further, the cellulose ester film preferably contains an acrylic resin from the viewpoint of more effectively exhibiting the object of the present invention.

(acrylic resin, acrylic particles)

The acrylic resin will be described below.

Acrylic resins also contain methacrylic resins. The resin is not particularly limited, but is preferably composed of 50 to 99% by mass of methyl methacrylate units and 1 to 50% by mass of other monomer units copolymerizable therewith.

The other monomers which can be copolymerized may be a combination of an alkyl methacrylate having an alkyl number of 2 to 18, an alkyl acrylate having an alkyl number of 1 to 18, an acrylic acid, a methacrylic acid or the like, α, β- An aromatic vinyl compound containing an unsaturated group such as an unsaturated acid, maleic acid, fumaric acid or itaconic acid, an unsaturated aromatic group, a styrene, an α-methylstyrene, a core-substituted styrene, or the like, propylene α,β-unsaturated nitrile such as nitrile or methacrylonitrile, maleic anhydride, maleimide, N-substituted maleimide, glutaric anhydride, etc., which may be used alone or in combination the above.

Among these, from the viewpoint of heat decomposition resistance or fluidity of the copolymer, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, dibutyl acrylate, 2-ethyl acrylate are preferred. For example, methyl acrylate and n-butyl acrylate are preferably used.

The acrylic resin preferably has a weight average molecular weight (Mw) of from 80,000 to 1,000,000 in terms of mechanical strength as a film and fluidity at the time of film production. The weight average molecular weight (Mw) can be measured using the above high speed liquid chromatography.

The method for producing the acrylic resin is not particularly limited, and any of conventional methods such as suspension polymerization, emulsion polymerization, bulk polymerization, or solution polymerization can be used. Among them, as the polymerization initiator, a general peroxide system or an azo group may be used, or a redox system may be used. The polymerization temperature is carried out at 30 to 100 ° C in suspension or emulsion polymerization, and at 80 to 160 ° C in bulk polymerization or solution polymerization. Further, in order to control the reduction viscosity of the resulting copolymer, it is also possible to carry out polymerization using an alkyl mercaptan or the like as a chain transfer agent. By setting this molecular weight, heat resistance and brittleness can coexist. As the acrylic resin, a commercially available one can also be used. For example, DELPET 60N, 80N (made by Asahi Kasei Chemicals Co., Ltd.), DIANAL BR52, BR80, BR83, BR85, BR88 (manufactured by Mitsubishi Rayon Co., Ltd.), KT75 (manufactured by Electric Chemical Industry Co., Ltd.), and the like.

Next, the cellulose ester film preferably contains acrylic particles in addition to the effect of the object of the present invention in addition to the effect of the object of the present invention.

The acrylic particles are explained. The acrylic particles are preferably, for example, a film containing an acrylic resin produced in a predetermined amount, dissolved in a solvent and stirred to be sufficiently dissolved. After dispersion, a film made of PTFE having a pore diameter smaller than the average particle diameter of the acrylic particles is used. The filter was filtered, and the weight of the insoluble matter collected by filtration was 90% by mass or more added to the acrylic particles containing the acrylic resin film.

The acrylic particles are not particularly limited, but are preferably acrylic particles having a layer structure of two or more layers, and are preferably an acrylic granular composite having a multilayer structure as described below.

The acrylic-type granular composite of the multilayer structure means that the innermost hard layer polymer is formed from the center portion toward the outer portion, the crosslinked soft layer polymer exhibiting rubber elasticity, and the outermost hard layer polymer are layered and overlapped. A particulate acrylic polymer constructed.

Preferred embodiments of the multilayer structure acrylic particulate composite used in the acrylic resin composition are as follows. The polyalkyl acrylate having a molecular weight of 80 to 98.9% by mass of methyl methacrylate, 1 to 8 carbon atoms of the alkyl group, and 1 to 20% by mass of the polyfunctional grafting agent are listed. % of the innermost hard layer polymer obtained by polymerization of the monomer mixture, (b) 75~98.5 mass of alkyl acrylate having an alkyl group having 4 to 8 carbon atoms in the presence of the innermost hard layer polymer %, a polyfunctional crosslinking agent, 0.01 to 5% by mass, and a polyfunctional grafting agent, 0.5 to 5% by mass, of a monomer mixture obtained by polymerizing a crosslinked soft layer polymer, (c) in the innermost hard layer and In the presence of a polymer composed of a crosslinked soft layer, a monomer mixture of 80 to 99% by mass of methyl methacrylate and 1 to 20% by mass of an alkyl acrylate having an alkyl group having 1 to 8 carbon atoms is obtained. The three-layer structure composed of the outermost hard layer polymer, and the obtained three-layer structure polymer is from 5 to 40% by mass of the innermost hard layer polymer (a), and 30 to 60% by mass of the soft layer polymer (b) And the outermost hard layer polymer (c) is composed of 20 to 50% by mass, and has an insoluble portion when it is distinguished by acetone, and the insoluble portion has a methyl ethyl ketone swelling degree of 1.5 to 4.0. Complex.

Further, by setting not only the composition or the particle diameter of each layer of the multilayer structure acrylic granulated composite, but also the elongation modulus of the multilayered acrylic granulated composite or the methyl ethyl ketone swelling of the acetone-insoluble portion is set to Within a specific range, a more balanced balance between impact resistance and stress whitening resistance can be achieved. In addition, as one of the examples of the composition or the particle size of each layer of the multi-layered structure of the acryl-based granulated composite, the disclosure of Japanese Patent Publication No. Sho 60-17406 or Japanese Patent No. Hei 3-39095 is hereby incorporated.

Among them, the innermost hard layer polymer (a) constituting the multilayer structure acrylic particulate composite is preferably an alkyl acrylate having 80 to 98.9% by mass of methyl methacrylate and 1 to 8 carbon atoms of the alkyl group. The monomer mixture obtained by polymerization of 1 to 20% by mass and 0.01 to 0.3% by mass of the polyfunctional grafting agent is obtained.

The alkyl acrylate having an alkyl group having 1 to 8 carbon atoms is exemplified by methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, second butyl acrylate, 2-ethylhexyl acrylate, and the like. It is preferred to use methyl acrylate or n-butyl acrylate.

The ratio of the alkyl acrylate unit in the innermost hard layer polymer (a) is 1 to 20% by mass, and when the unit is less than 1% by mass, the thermal decomposition property of the polymer becomes large, and on the other hand, the unit exceeds 20 mass%. In the case of %, the glass transition temperature of the innermost hard layer polymer (a) is lowered, and the impact resistance imparting effect of the three-layer structure acrylic granular composite is lowered, so that neither of them is preferable.

As the polyfunctional grafting agent, for example, a polyfunctional monomer having a different polymerizable functional group, for example, a grafting agent such as acrylic acid, methacrylic acid, maleic acid or allyl fumarate, is preferably used. Allyl methacrylate was used. The polyfunctional grafting agent is used to chemically bond the innermost hard layer polymer to the soft layer polymer, and the ratio used in the innermost hard layer polymerization is 0.01 to 0.3% by mass.

The crosslinked soft layer polymer (b) constituting the acrylic granular composite is preferably an alkyl acrylate 75 having an alkyl group having a carbon number of 1 to 8 in the presence of the innermost hard layer polymer (a). A monomer mixture polymerization of ~98.5 mass%, a polyfunctional crosslinking agent of 0.01 to 5% by mass, and a polyfunctional grafting agent of 0.5 to 5% by mass.

Among them, an alkyl acrylate having an alkyl group having 4 to 8 carbon atoms is preferably n-butyl acrylate or 2-ethylhexyl acrylate.

Further, 25% by mass or less of other copolymerizable monomer which is copolymerizable may be copolymerized with the polymerizable monomers.

Other monofunctional monomers which can be copolymerized are exemplified by styrene and substituted styrene derivatives. The ratio of the alkyl acrylate having a carbon number of 4 to 8 to styrene is the same as the former, and the resulting polymer (b) has a lower glass transition temperature, that is, it can be softened.

On the other hand, from the viewpoint of the transparency of the resin composition, the normal temperature index of the soft layer polymer (b) is closer to the innermost hard layer polymer (a), the outermost hard layer polymer (c), and the hard heat. The more advantageous the plastic acrylic resin, the ratio of the two can be ascertained.

For example, in applications where the thickness of the coating layer is small, it is not necessary to copolymerize styrene.

A polyfunctional grafting agent can be used as described in the item of the aforementioned innermost hard polymer (a). The polyfunctional grafting agent used herein is used to chemically bond the soft layer polymer (b) to the outermost hard layer polymer (c), and the ratio used in the polymerization of the innermost hard layer imparts resistance. From the viewpoint of the impact effect, it is preferably from 0.5 to 5% by mass.

As the polyfunctional crosslinking agent, a generally known crosslinking agent such as a divinyl compound, a diallyl compound, a diacrylic compound or a dimethacrylic compound can be used, but polyethylene glycol diacrylate (molecular weight 200~) is preferably used. 600).

The polyfunctional crosslinking agent used herein is used to produce a crosslinked structure at the time of polymerization of the soft layer (b), and exhibits an impact resistance imparting effect. However, when the soft layer is used in the polymerization of the previous polyfunctional grafting agent, the soft layer (b) crosslinked structure is formed to some extent, so the polyfunctional crosslinking agent is not an essential component, but the polyfunctional crosslinking is carried out. The ratio of the agent used in the polymerization of the soft layer is preferably from 0.01 to 5% by mass from the viewpoint of imparting an impact resistance effect.

The outermost hard layer polymer (c) constituting the multilayered acrylic particle composite is preferably made of methyl methacrylate in the presence of the innermost hard layer polymer (a) and the soft layer polymer (b). A monomer mixture obtained by polymerizing 80 to 99% by mass and 1 to 20% by mass of an alkyl acrylate having 1 to 8 carbon atoms of an alkyl group.

Among them, the above-mentioned one is used as the alkyl acrylate, but methyl acrylate or ethyl acrylate is preferably used. The proportion of the alkyl acrylate unit in the outermost hard layer (c) is preferably from 1 to 20% by mass.

Further, in the polymerization of the outermost hard layer (c), in order to improve the compatibility with the acrylic resin, an alkylthiol or the like for adjusting the molecular weight may be used as a chain transfer agent.

In particular, it is preferable to provide a gradient in which the outermost hard layer is gradually reduced in molecular weight from the inner side toward the outer side, thereby improving the balance between elongation and impact resistance. The specific method is to reduce the molecular weight from the inner side toward the outer side by dividing the monomer mixture for forming the outermost hard layer into two or more and sequentially increasing the chain transfer agent added each time. The molecular weight formed at this time can be investigated by polymerizing the monomer mixture used each time under the same conditions as those of the respective polymerizations, and measuring the molecular weight of the obtained polymer. The particle diameter of the acrylic particulate composite which is a multilayer structure polymer is not particularly limited, but is preferably 10 nm or more and 1000 nm or less, more preferably 20 nm or more and 500 nm or less, and more preferably 50 nm or more and 400 nm or less.

In the acrylic-based granular composite of the polymer of each layer, the mass ratio of the core to the shell is not particularly limited. When the total amount of the multilayer structure polymer is 100 parts by mass, the core layer is 50 parts by mass or more and 90 parts by mass or less. More preferably, it is 60 mass parts or more and 80 mass parts or less.

Examples of such a commercially available product of the multilayer structure of the acrylic granulated composite are, for example, "METABLEN" manufactured by Mitsubishi Corporation, "KANEACE" manufactured by Kaneka Chemical Industry Co., Ltd., and "PARALOID" manufactured by Wu Yu Chemical Industry Co., Ltd. "ACRYLOIDE" manufactured by Rohm & Haas Co., Ltd., "STAFILOIDE" manufactured by GANTZ Chemical Industry Co., Ltd., and "PARAPETSA" manufactured by KURARAY Co., Ltd., and the like. These may be used singly or in combination of two or more.

Specific examples of the acrylic particles (c-1) which are preferably used as the graft copolymer of acrylic particles include an unsaturated carboxylate monomer and an unsaturated carboxylic acid in the presence of a rubbery polymer. A graft copolymer obtained by copolymerizing a bulk, an aromatic vinyl monomer, and a monomer mixture which may be copolymerized with other vinyl monomers copolymerized as needed.

The rubbery polymer used in the acrylic particles of the graft copolymer is not particularly limited, and a diene rubber, an acrylic rubber, a vinyl rubber or the like can be used. Specific examples are polybutadiene, styrene-butadiene copolymer, block copolymer of styrene-butadiene, acrylonitrile-butadiene copolymer, butyl acrylate-butadiene copolymer, and poly Isoprene, butadiene-methyl methacrylate copolymer, butyl acrylate-methyl methacrylate copolymer, butadiene-ethyl acrylate copolymer, ethylene-propylene copolymer, ethylene-propylene- A diene copolymer, an ethylene-isoprene copolymer, and an ethylene-methyl acrylate copolymer. These rubbery polymers may be used singly or in combination of two or more.

Further, when the refractive indices of the acrylic resin and the acrylic particles are similar, it is preferable because the transparency of the transparent film substrate can be obtained. Specifically, the difference in refractive index between the acrylic particles and the acrylic resin is preferably 0.05 or less, more preferably 0.02 or less, still more preferably 0.01 or less.

In order to satisfy the refractive index conditions, the refractive index difference can be reduced by a method of adjusting the monomer unit composition ratio of the acrylic resin and/or adjusting the composition ratio of the rubbery polymer or monomer used in the acrylic particles. A film containing an acrylic resin excellent in transparency can be obtained.

Here, the refractive index difference herein means that a film containing an acrylic resin is sufficiently dissolved in a solvent capable of dissolving an acrylic resin under appropriate conditions to form a white turbid solution, and is separated into a solvent-soluble portion by a centrifugal separation or the like. The insoluble portion was purified from the difference between the soluble portion (acrylic resin) and the insoluble portion (acrylic particles), and the refractive index (23 ° C, measurement wavelength: 550 nm) was measured.

The method of disposing the acrylic particles in the acrylic resin is not particularly limited, and it is preferred to use uniaxial or double-added acrylic particles at 200 to 350 ° C after pre-blending the acrylic resin with other optional components. The method of uniformly melting and kneading the shaft extruder.

Commercially available products can also be used for the acrylic particles. For example, METABLEN W-341 (C2) (manufactured by Mitsubishi Rayon Co., Ltd.), CHEMISNOW MR-2G (C3), MS-300X (C4) (manufactured by Soken Chemical Co., Ltd.), and the like can be cited.

The acrylic particles preferably contain 0.5 to 45% by mass of acrylic particles based on the total amount of the cellulose ester resin and the acrylic resin.

Further, a film composed of a cellulose ester resin and an acrylic resin (hereinafter also referred to as a cellulose ester resin/acrylic resin film) is preferably a film having a tensile softening point of 105 to 145 ° C and which does not cause ductile damage. The so-called ductile failure system is defined as being produced under the action of a stress greater than the strength of the material, and is accompanied by damage caused by significant stretching or contraction of the material before the final fracture. The specific measurement method of the tension softening point temperature is to cut a film containing an acrylic resin into 120 mm (length) × 10 mm (width) using a Tensilon tester (RTC-1225A, manufactured by ORIENTEC Co., Ltd.), and stretch at a tension of 10 N. The temperature was continuously raised at a temperature increase rate of 30 ° C / min, and the temperature at the time point of 9 N was measured three times, and the average value was obtained.

Further, the glass transition temperature (Tg) of the film composed of the cellulose ester resin and the acrylic resin is preferably at least 110 °C. More preferably 120 ° C or more. It is preferably 150 ° C or more.

The glass transition temperature is measured by a differential scanning calorimeter (DSC-7 type manufactured by Perkin Elmer Co., Ltd.) at a temperature rising rate of 20 ° C /min, and an intermediate point glass transition temperature (Tmg) obtained in accordance with JIS K7121 (1987).

The film composed of the cellulose ester resin and the acrylic resin is preferably measured in accordance with JIS-K7127-1999, and the elongation at break in at least one direction is preferably 10% or more, more preferably 20% or more. Although the upper limit of the elongation at break is not particularly limited, it is actually about 250%. Increasing the elongation at break can effectively suppress defects in the film caused by foreign matter or foaming. The thickness of the film composed of the cellulose ester resin and the acrylic resin is preferably 20 μm or more.

More preferably 30 μm or more. The upper limit of the thickness is not particularly limited, but when the film is formed by a solution film forming method, the upper limit is about 250 μm from the viewpoints of coatability, foaming, solvent drying, and the like. Further, the thickness of the film can be appropriately selected depending on the use.

The film composed of the cellulose ester resin and the acrylic resin preferably contains an acrylic resin and a cellulose ester resin in a mass ratio of 95:5 to 30:70 from the viewpoint of both workability and heat resistance. The total substitution degree (T) of the mercapto group of the ester resin is preferably from 2.00 to 3.00, the degree of substitution of the ethyl indenyl group (ac) is preferably from 0 to 1.89, and the carbon number of the mercapto group other than the ethyl indenyl group is preferably from 3 to 3. 7. The weight average molecular weight (Mw) is preferably from 75,000 to 280,000. Further, the total mass of the acrylic resin and the cellulose ester resin is 55 to 100% by mass, preferably 60 to 99% by mass, based on the film containing the acrylic resin.

The film composed of the cellulose ester resin and the acrylic resin may be composed of other acrylic resin.

The cellulose ester film or the film composed of the cellulose ester resin and the acrylic resin may be produced by a solution casting method, or may be produced by a melt casting method, but it is preferably at least in the width direction. It is preferable to use a solution casting step in which the amount of the residual solvent is from 3 to 40% by mass in the width direction of 1.01 to 1.5 times. More preferably, it is preferably biaxially stretched in the width direction and the longitudinal direction, and is preferably extended in the width direction and the length direction by 1.01 to 1.5 times when the amount of the residual solvent is 3 to 40% by mass. The stretching ratio at this time is preferably 1.03 to 1.45 times. Further, the length of the transparent film substrate is preferably from 100 m to 5000 m, and the width is preferably from 1.2 m or more, more preferably from 1.4 to 4 m. When the length and width of the transparent film substrate are within the above range, workability and productivity are excellent.

The cellulose ester film is preferably a transparent support having a light transmittance of 90% or more, more preferably 93% or more.

(plasticizer)

The cellulose ester film or the cellulose ester resin ‧ acrylic resin film preferably contains a plasticizer as described below. As the plasticizer, for example, a phosphate ester plasticizer, a phthalate plasticizer, a benzotricarboxylate plasticizer, a pyromellitic acid plasticizer, a glycolate plasticizer, or a citric acid ester is preferably used. A plasticizer, a polyester-based plasticizer, a polyol ester-based plasticizer, and the like.

The phosphate ester plasticizer preferably uses triphenyl phosphate, tricresyl phosphate, diphenyl phosphate, diphenyl phosphate, diphenyl phosphate, trioctyl phosphate, and tributyl phosphate. Ester, etc., phthalate-based plasticizers preferably use diethyl phthalate, dimethoxyethyl phthalate, dimethyl phthalate, dioctyl phthalate, dibutyl phthalate Ester, di-2-ethylhexyl phthalate, butyl benzyl phthalate, diphenyl phthalate, dicyclohexyl phthalate, etc., benzene trimellitate plasticizer is preferably used benzene Tributyl phthalate, triphenyl benzoate, triethyl benzoate, etc., pyromellitate plasticizer is preferably tetrabutyl pyromelliate, tetraphenyl pyromellitic acid Ester, tetraethyl pyromelliate, etc., glycolate plasticizers preferably use triacetin, tributyrin, ethyl phthalic acid ethyl glycolate, methyl phthalic acid Ethyl ethyl glycolate, butyl phthalic acid butyl glycolate, etc., citric acid ester plasticizer is preferably used triethyl citrate, lemon Tri-n-butyl citrate acetyl triethyl citrate, acetyl tri-n-butyl citrate, citric acid-n-acetyl - (2-ethyl hexyl acrylate) and the like. Examples of other carboxylic acid esters include butyl oleate, methyl ethionate, dibutyl sebacate, and various trimellitic acid esters.

As the polyester-based plasticizer, a copolymerized polymer of a dibasic acid such as an aliphatic dibasic acid, an alicyclic dibasic acid or an aromatic dibasic acid and a diol can be used. The aliphatic dibasic acid is not particularly limited, and adipic acid, sebacic acid, phthalic acid, terephthalic acid, 1,4-cyclohexanedicarboxylic acid, or the like can be used. As the diol, ethylene glycol, diethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol or the like can be used. These dibasic acids and diols may be used alone or in combination of two 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. 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-propylene glycol, 1,3-propanediol, dipropylene glycol, tripropylene glycol, 1, 2 -butanediol, 1,3-butanediol, 1,4-butanediol, dibutylene glycol, 1,2,4-butanetriol, 1,5-pentanediol, 1,6-hexane Alcohol, hexanetriol, 2-n-butyl-2-ethyl-1,3-propanediol, galactitol, mannitol, 3-methylpentane-1,3,5-triol, frequency Alcohol, sorbitol, trimethylolpropane, trimethylolethane, xylitol, and the like. Most preferred are triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, sorbitol, trimethylolpropane, xylitol. The monocarboxylic acid to be used in 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, it is preferable in terms of improving moisture permeability and retention. Examples of preferred monocarboxylic acids include the following, but are not limited thereto. As the aliphatic monocarboxylic acid, a fatty acid having a linear or side chain having 1 to 32 carbon atoms can be suitably used. The carbon number is 1 to 20, and the 1 to 10 is the best. If acetic acid is contained, the compatibility with the cellulose ester is increased, and it is preferred to use acetic acid in combination with other monocarboxylic acids. Preferred aliphatic monocarboxylic acids include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, capric acid, capric acid, 2-ethyl-hexanecarboxylic acid, and undecanoic acid. , dodecanoic acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, octadecanoic acid, nonadecanoic acid, eicosanoic acid, behenic acid Saturated fatty acids such as acid, tetracosanoic acid, hexadecanoic acid, heptacosanoic acid, octadecanoic acid, triacontanic acid, and tridecanoic acid, undecylenic acid, oleic acid, and sorbus Unsaturated fatty acids such as acid, linoleic acid, linolenic acid, and arachidonic acid. As preferred examples of the alicyclic monocarboxylic acid, cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, cyclooctanecarboxylic acid or the like can be exemplified. Examples of the preferred aromatic monocarboxylic acid include those in which a benzene ring such as benzoic acid or toluic acid is introduced into an alkyl group, a biphenylcarboxylic acid, a naphthalenecarboxylic acid or a tetrahydronaphthalenecarboxylic acid. More than one aromatic carboxylic acid of a benzene ring, or a derivative thereof. The best is benzoic acid. The molecular weight of the polyol ester is not particularly limited, but is preferably in the range of 300 to 1,500, more preferably in the range of 350 to 750. The greater the improvement in retention, the better the moisture permeability and the compatibility with the 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 group in the polyol may be completely esterified with a carboxylic acid, or a part of the OH group may be directly left. These plasticizers are preferably used singly or in combination. The amount of the plasticizer to be used is preferably from 1 to 20% by mass, more preferably from 3 to 13% by mass, based on the cellulose ester, in terms of film properties and workability.

(UV absorber)

The transparent film substrate preferably contains an ultraviolet absorber. The ultraviolet absorber will be described below.

As for the ultraviolet absorber, from the viewpoint of excellent ultraviolet absorption energy at a wavelength of 370 nm or less and good liquid crystal display properties, it is preferred to use a light absorption having a wavelength of 400 nm or more. Specific examples thereof include an oxybenzophenone-based compound, a benzotriazole-based compound, a salicylate-based compound, a benzophenone-based compound, a cyanoacrylate-based compound, a triazine-based compound, and a nickel-stack salt. A compound or the like, but is not limited thereto.

The benzotriazole-based ultraviolet absorber is exemplified by the following specific examples, but is not limited thereto.

UV-1: 2-(2'-hydroxy-5'-methylphenyl)benzotriazole UV-2: 2-(2'-hydroxy-3',5'-di-t-butylphenyl Benzotriazole UV-3: 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)benzotriazole UV-4: 2-(2'-hydroxy-3 ',5'-di-t-butylphenyl)-5-chlorobenzotriazole UV-5: 2-(2'-hydroxy-3'-(3",4",5",6"- Tetrahydrobenzidine imine methyl)-5'-methylphenyl)benzotriazole UV-6:2,2-extended methyl bis(4-(1,1,3,3-tetramethyl) Benzyl)-6-(2H-benzotriazol-2-yl)phenol) UV-7: 2-(2'-hydroxy-3'-t-butyl-5'-methylphenyl)- 5-Chlorobenzotriazole UV-8: 2-(2H-benzotriazol-2-yl)-6-(linear and side chain dodecyl)-4-methylphenol (TINUVIN171' Ciba . Japan (Ciba Japan) company UV-9: Octyl-3-[3-t-butyl-4-hydroxy-5-(chloro-2H-benzotriazol-2-yl)phenyl]propene a mixture of an acid ester and 2-ethylhexyl-3-[3-t-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate ( TINUVIN 109, manufactured by Ciba ‧ Japan Co., Ltd.) Further, the benzophenone-based ultraviolet absorber lists the following specific examples, but 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-benzimidylphenylmethane) as the above ultraviolet absorber, preferably having high transparency and preventing polarizing plates or The benzotriazole-based ultraviolet absorber or the benzophenone-based ultraviolet absorber which is excellent in the effect of the deterioration of the liquid crystal is preferably a benzotriazole-based ultraviolet absorber which is less colored with an undesirable color.

Further, in order to maintain the surface quality surface of the transparent film substrate satisfactorily, it is preferred to use an ultraviolet absorber having a partition coefficient of 9.2 or more, particularly an ultraviolet absorber having a partition coefficient of 10.1 or more. Moreover, the ultraviolet absorber having a distribution coefficient of 9.2 or more can be used by a conventional one, and an example thereof is described in JP-A-2001-187825.

Further, a polymer ultraviolet absorber (or a UV-absorbing polymer) is also preferably used. As for the polymer ultraviolet absorber, PUVA-30M (manufactured by Otsuka Chemical Co., Ltd.) is commercially available. As for the polymer ultraviolet ray absorbing agent, a general formula (1), a general formula (2), or a general formula of the Japanese Patent Publication No. 2000-156039 can be cited as an example. (3), (6), (7).

Further, the transparent film substrate can also impart internal turbidity.

(particle)

The internal turbidity may be, for example, a particle having a refractive index different from that of the transparent film substrate added to the transparent film substrate, and the turbidity due to internal scattering may be generated by controlling the amount of addition or the particle diameter of the particles, and the adjustment may be achieved. . As for the particles, they can be distinguished into inorganic particles and organic particles. The inorganic particles are not particularly limited, and examples thereof include cerium oxide, titanium oxide, aluminum oxide, zinc oxide, tin oxide, calcium carbonate, barium sulfate, talc, kaolin, and calcium sulfate. Further, the organic particles are not particularly limited, and examples thereof include fluorinated acrylic resin powder, polystyrene resin powder, polymethyl methacrylate resin powder, polyfluorene-based resin powder, polycarbonate resin powder, and acrylic styrene. Resin powder, benzoquinone resin powder, melamine resin powder, and other examples are polyolefin resin powder, polyester resin powder, polyamide resin powder, polyamidene resin powder, and polyvinyl fluoride resin powder. Wait. These inorganic particles and organic particles may be used in combination of two or more types and average particle diameters, and it is also preferred to use a surface of the particles to be surface-treated with an organic material.

The most preferred inorganic particles are the cerium oxides in these classes. Specific examples of cerium oxide are preferably AEROSIL 200V, AEROSIL R972V, AEROSIL R972, R974, R812, 200, 300, R202, OX50, TT600 (above is Japan AEROSIL), SEAHOSTER KE-P10, SEAHOSTER KE-P30, SEAHOSTER KE-P50 (above is manufactured by Nippon Shokubai Co., Ltd.), SYLOPHOBIC 100 (made by Fuji-Silysia), NIPSIL E220A (made by Japan Silica Industries), ADMAFINE SO (made by Admatechs), etc. Sales, etc. The shape of the particles is not particularly limited, and an amorphous shape, a needle shape, a flat shape, a spherical shape, or the like can be used. In particular, it is preferable to use spherical particles to adjust the turbidity.

As the organic particles, fluorine-containing acrylic resin particles are preferably used.

The fluorine-containing acrylic resin particles are, 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 are 1H, 1H, 3H-tetrafluoropropyl (meth)acrylate, 1H, 1H, 5H-octafluoropentyl (meth)acrylate, (methyl) )1H,1H,7H-dodecylheptyl acrylate, 1H,1H,9H-hexadecafluorodecyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, (methyl) 2,2,3,3,3-pentafluoropropyl acrylate, 2-(perfluorobutyl)ethyl (meth)acrylate, 2-(perfluorohexyl)ethyl (meth)acrylate, (a) 2-(perfluorooctyl)ethyl acrylate, 2-perfluorodecylethyl (meth)acrylate, 3-perfluorobutyl-2-hydroxypropyl (meth)acrylate, (methyl) 3-perfluorohexyl-2-hydroxypropyl acrylate, 3-perfluorooctyl-2-hydroxypropyl (meth)acrylate, 2-(perfluoro-3-methylbutyl)(meth)acrylate Ester, 2-(perfluoro-5-methylhexyl)ethyl (meth)acrylate, 2-(perfluoro-7-methyloctyl)ethyl (meth)acrylate, 3-(meth)acrylate (Perfluoro-3-methylbutyl)-2-hydroxypropyl ester, 3-(perfluoro-5-methylhexyl)-2-hydroxypropyl (meth)acrylate, 3-(meth)acrylate Perfluoro-7-methyloctyl)-2-hydroxypropyl ester, 1H-1-(trifluoromethyl)(meth)acrylate Fluoroethyl ester, 1H, 1H, 3H-hexafluorobutyl (meth)acrylate, trifluoroethyl methacrylate, tetrafluoropropyl methacrylate, perfluorooctyl acrylate, α-fluoroacrylic acid 2- (Perfluorobutyl)ethyl ester. Further, among the fluorine-containing acrylic resin particles, particles composed of 2-(perfluorobutyl)ethyl α-fluoroacrylate and fluorine-containing polymethyl methacrylate particles are preferably used in the presence of a crosslinking agent. The particles obtained by copolymerizing fluorine-containing methacrylic acid with a vinyl monomer are more preferably fluorine-containing polymethyl methacrylate particles.

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

Further, the polymerization reaction for producing the fluorine-containing polymethyl methacrylate particles may be any of random copolymerization and block copolymerization. An example of the polymerization method is a method described in JP-A-2000-169658.

Commercially available products are listed as commercially available products such as MF-0043. Further, the fluorine-containing acrylic resin particles may be used singly or in combination of two or more. Further, the state of the fluorine-containing acrylic resin particles may be a powder, an emulsion or the like, and may be added in any state.

Further, fluorine-containing crosslinked particles can also be used. Further, as the fluorine-containing crosslinked particles, those skilled in the art can be used, and examples thereof include those described in paragraphs 0028 to 0055 of JP-A-2004-83707.

The polystyrene particles are exemplified by, for example, the SBX series (SBX-6, SBX-8) manufactured by Sekisei Chemical Co., Ltd., SX-130H, SX-200H, and SX-350H).

The melamine-based particles are exemplified by, for example, Japanese catalyst: benzoquinone melamine ‧ formaldehyde condensate (trade name: EPOSTAR, grade; M30, trade name: EPOSTAR GP, grade; H40 to H110), Japanese catalyst: melamine ‧ formaldehyde Commercial products such as condensate (trade name: EPOSTAR, grade; S12, S6, S, SC4). Further, examples are a core-shell-shaped spherical composite hardened melamine resin particle which is composed of a melamine resin and a shell filled with ruthenium oxide. The spherical composite hardened melamine resin particles are commercially available from Nissan Chemical Industries Co., Ltd.: melamine resin ‧ cerium oxide composite particles (trade name: OBUTO BEAD). In the case of the method described in JP-A-2006-171033, the poly((meth)acrylate) particles and the cross-linked poly((meth)acrylate) particles are listed, for example, in the comprehensive research. :MX150, MX300, Japan Catalyst; EPOSTAR MA, grade; MA1002, MA1004, MA1006, MA1010, EPOSTAR MX (emulsion), grade; MX020W, MX030W, MX050W, MX100W, Sekisui Chemical Co., Ltd.: MBX series (MBX-8 , MBX-12) and other commercial products.

Specific examples of the cross-linked poly(acrylic acid-styrene) particles are, for example, commercially available products such as FS-201 and MG-351 manufactured by Nippon Paint Co., Ltd. The benzoquinone-based fine particles are exemplified by, for example, a Japanese catalyst: benzoquinone aldehyde condensation product (trade name: EPOSTAR, grade; L15, M05, MS, SC25).

The average particle diameter of the particles added to the support is preferably from 0.3 to 1 μm, more preferably from 0.4 to 0.7 μm.

The above average particle diameter can be obtained by visually observing the image of the secondary electrons emitted from 500 particles by a scanning electron microscope (SEM) or by using an image, or by using a dynamic light scattering method or a static light scattering method. It is measured by a particle size distribution meter or the like. The average particle diameter herein refers to the number average particle diameter. Further, the average particle diameter means an average particle diameter of the aggregate when the particles are aggregates of primary particles. Further, when the particles are not spherical, they mean the diameter of a circle corresponding to the projected area.

Further, the refractive index of the particles is preferably from 1.45 to 1.70, more preferably from 1.45 to 1.65. Further, the refractive index of the particles can be measured by dispersing the particles in an equal amount by changing the mixing ratio of the two solvents having different refractive indices to change the refractive index of the solvent, and measuring the refractive index of the solvent having a very low turbidity by the Abbe refractometer. Determined by rate.

Further, it is preferable that the difference in refractive index between the resin used in the support and the particles is 0.02 or more and 0.20 or less, and the internal turbidity is improved by the light scattering effect. The range in which the refractive index difference is more preferable is 0.05 or more and 0.15 or less.

The content of the inorganic or organic particles is preferably from 1 part by mass to 30 parts by mass based on 100 parts by mass of the resin for film substrate production, and more preferably from 5 parts by mass to 25 parts by mass in terms of internal turbidity.

The particles may be contained and dispersed together with a cellulose ester, other additives, and an organic solvent in the preparation of a composition (dopant) for preparing a transparent film substrate, or may be separately dispersed in a solution. The dispersion method of the particles is preferably finely dispersed in a dispersing machine (high-pressure dispersing device) having a high shearing force after being immersed in an organic solvent in advance.

The method for preparing the dopant is preferably to disperse the particles in a large amount of an organic solvent, join the cellulose ester solution, and mix them into a dopant by a wire kneading machine. At this time, an ultraviolet absorber may be added to the particle dispersion liquid to become a UV absorber liquid.

Further, the deterioration inhibitor and the ultraviolet absorber may be added together with a cellulose ester, a cellulose ester resin, an acrylic resin, and a solvent when preparing a solution of a cellulose ester or a cellulose ester resin and an acrylic resin. It is added during solution preparation or after preparation.

(Organic solvents)

The dopant preferably contains an organic solvent from the viewpoint of film formability or productivity. The organic solvent is not particularly limited as long as it can dissolve cellulose ester and other additives at the same time. For example, dichloromethane, methyl acetate, ethyl acetate, amyl acetate, acetone, tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, cyclohexanone, ethyl formate can be mentioned. , 2,2,2-trifluoroethanol, 2,2,3,3-hexafluoro-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 Alcohol, nitroethane, and the like. Among these organic solvents, dichloromethane, methyl acetate, ethyl acetate, and acetone are preferably used.

The dopant preferably contains 1 to 40% by mass of an alcohol having 1 to 4 carbon atoms in addition to the above organic solvent. When the ratio of the alcohol in the dopant is high, the sheet is gelatinized, and it is easy to be peeled off from the metal support. Further, when the ratio of the alcohol is small, the effect of promoting the dissolution of the cellulose ester in the non-chlorine-based organic solvent is also exhibited. Examples of the alcohol having 1 to 4 carbon atoms include methanol, ethanol, n-propanol, isopropanol, n-butanol, second butanol, and third butanol. Among these, ethanol is preferred from the viewpoints of stability of the dopant, low boiling point, good drying property, and no toxicity.

The concentration of the cellulose ester in the dopant is adjusted to 15 to 40% by mass, and the viscosity of the dopant is adjusted to a range of 100 to 500 poise (P), which is preferable in terms of obtaining a good film quality.

(solution casting method)

The cellulose ester film produced by the solution casting method, and the cellulose ester resin ‧ acrylic resin film are carried out by dissolving the cellulose ester or the cellulose ester resin ‧ acrylic resin and the additive in a solvent to prepare the dopant a step of casting a dopant on a strip or a cylindrical metal support, a step of drying the cast dopant into a sheet, a step of stripping from the metal support, a step of stretching or maintaining the width, and further drying Step, the step of crimping the finished film.

The concentration of cellulose ester and cellulose ester resin ‧ acrylic resin in the dopant, when the concentration is high, the drying load after casting on the metal support is reduced, but the concentration of the cellulose ester is too high, so that the filtration time The load increases and the filtration accuracy deteriorates. The concentration at which the two are coexisted is preferably from 10 to 35% by mass, more preferably from 15 to 25% by mass.

The metal support in the casting step is preferably a mirror-finished surface, and the metal support is preferably a stainless steel strip or a cylindrical surface of a cast material which is electroplated. The width of the casting can be 1~4m. The surface temperature of the metal support of the casting step is set to be -50 ° C to a temperature below which the solvent does not boil. When the temperature is high, it is preferable because the drying speed of the sheet can be accelerated, but if it is too high, the sheet is foamed and the flatness is deteriorated. The preferred support temperature is suitably determined between 0 and 100 ° C, preferably 5 to 30 ° C. Further, it is preferable to gel the sheet by cooling and peeling it off from the tube in a state containing a large amount of residual solvent. The method of controlling the temperature of the metal support is not particularly limited, and may be a method of blowing warm air or cold air, or a method of bringing warm water into contact with the inner side of the metal support. When warm water is used, since the heat conduction is performed efficiently, the time until the temperature of the metal support reaches a certain temperature is short and preferable. When the warm air is used, the temperature of the sheet is lowered due to the latent heat of vaporization of the solvent, and although a warm air having a boiling point or higher is used, there is also a case where a wind which prevents foaming and has a higher temperature than the target temperature is used. In particular, it is preferred to change the temperature of the support between the casting and the peeling and the temperature of the drying air, and to dry efficiently.

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

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

Residual solvent amount (% by mass) = {(M-N)/N}x100

Further, M is the weight of the sample sampled at any time during or after the production of the sheet or film, and N is the mass after heating M at 115 ° C for 1 hour.

Further, in the drying step of the cellulose ester film or the film composed of the cellulose ester resin or the acrylic resin, after the sheet is peeled off from the metal support and dried, the amount of the residual solvent is preferably 1% by mass or less, more preferably 0.1% by mass. % or less, preferably 0 to 0.01% by mass or less.

The film drying step is usually carried out by a roll drying method (drying of a plurality of rolls by alternately arranging the sheets) or by drying the sheets while being conveyed.

(melt film forming method)

The cellulose ester film, the cellulose ester resin, and the acrylic acid film are preferably formed by a melt film formation method. The melt film forming method refers to heating and melting a composition containing an additive of a cellulose ester, a cellulose ester resin, an acrylic resin, and a plasticizer to a temperature at which fluidity is exhibited, followed by casting a melt containing a fluid cellulose ester.

The molding method of heating and melting can be further classified into a melt extrusion molding method, a press molding method, a blowing method, an injection molding method, a blow molding method, an extension molding method, and the like. Among these, in order to obtain a cellulose ester film excellent in mechanical strength and surface precision, and a film of a cellulose ester resin and an acrylic number, it is excellent in a melt extrusion method.

The plurality of raw materials used in the melt extrusion are usually preferably pre-kneaded and pelletized.

The granulation may be a conventional method, for example, a feeder may be used to supply dry cellulose ester or a plasticizer, other additives to an extruder, and kneaded using a uniaxial or biaxial extruder, and extruded from a die into a strand. , cooled by water or air, and cut.

The additives may be mixed prior to being supplied to the extruder, or may each be supplied by an individual feeder. For uniform mixing, a small amount of additives such as particles or antioxidants are preferably premixed.

The extruder is preferably processed at a low temperature which can suppress the shearing force and can be granulated without deteriorating the resin (molecular weight reduction, coloration, gel formation, etc.). For example, in the case of a two-axis extruder, it is preferred to use a deep groove type spiral to rotate in the same direction. In terms of the uniformity of the kneading, it is preferred to use an intermeshing type.

Film formation was carried out using the granules obtained as above. However, without the granulation, the raw material powder is directly supplied to the extruder by a feeder, and direct film formation is also possible.

The granules are uniaxially or biaxially extruded, and the melting temperature at the time of extrusion is set to about 200 to 300 ° C, and the foreign matter is filtered by a leaf disk filter or the like, and then cast from a T-die. Film-formed and cured on a chill roll.

When the feed pump is introduced into the extruder, it is preferably under vacuum or reduced pressure or in an inert gas atmosphere to prevent oxidative decomposition or the like.

The extrusion flow rate is preferably carried out by introducing the pump into the gear or the like. Further, the filter for removing foreign matter is preferably a stainless steel fiber sintered filter. The stainless steel fiber sintered filter makes the stainless steel fiber body complicated and entangled, so that the compression contact position is sintered and integrated, and the density is changed according to the fiber thickness and the compression amount, and the filtration precision can be adjusted.

Additives such as plasticizers or particles may be pre-mixed with the resin or may be stirred in the middle of the extruder. In order to uniformly add, a mixing device such as a static kneader is preferably used.

The film temperature on the side of the contact roll when the film is pinched by the cooling roll and the elastic contact roll is preferably Tg or more and Tg+110 ° C or less of the film. Conventional rolls can be used for the rolls having elastomeric surfaces for such purposes.

The elastic contact roller is also referred to as a rolling rotating body. As the elastic contact roller, a conventional elastic contact roller, that is, a commercially available one can be used. For example, a contact roll disclosed in Japanese Laid-Open Patent Publication No. Hei. No. 2002-36333, No. 2002-36333, and the like. When the film is peeled off from the cooling roll, it is preferred to control the tension to prevent deformation of the film.

Further, the film obtained as described above is preferably extended by the above-described stretching operation after the step of contacting the cooling roll.

The stretching method can preferably use a conventional roll stretching machine or a cloth stretching machine or the like. The stretching temperature is preferably carried out in a temperature range of usually from Tg to Tg + 60 ° C of the resin constituting the film. Before the winding, the end portion of the width of the product is cut longitudinally, and in order to prevent sticking during the winding, nodular processing (embossing) can be applied to both ends. The method of nodular processing can be processed by heating or pressurizing a metal ring having a concave-convex pattern on the side. Further, the gripping portion of the gripper at both ends of the film is usually removed and reused because the film is not deformed as a product.

(polarized protective film)

When the antireflection film of the present embodiment is used as a polarizing protective film, the thickness of the protective film is preferably from 10 to 500 μm. In particular, it is 20 μm or more, more preferably 35 μm or more. Further, it is preferably 150 μm or less, more preferably 120 μm or less. It is preferably 25 μm or more to 90 μm. When the antireflection film is thicker than the above range, the polarizing plate after the processing of the polarizing plate is too thick, and it is particularly difficult to conform to the thin and light weight in the liquid crystal display of a notebook computer or a mobile electronic device. On the other hand, when it is thinner than the above range, the moisture permeability of the film is high, and the ability to protect the polarizer from moisture is less preferable.

(polarizer)

A polarizing plate using the antireflection film of the present embodiment will be described. The polarizing plate can be produced by a general method. It is preferred that the back side of the antireflection film of the present embodiment is alkalized with an alkali to treat the treated antireflection film, and the fully alkalized polyvinyl alcohol aqueous solution is applied to the polarized light prepared by immersing and stretching in an iodine solution. On at least one side of the membrane. The antireflection film can be used on the other side, and other polarizing plates can be used to protect the film. For the antireflection film of the present embodiment, the polarizing plate protective film used on the other surface is preferably an optical compensation film having a phase difference of an in-plane retardation Ro of 20 to 70 nm at 590 nm and a phase difference of Rt of 70 to 400 nm (phase difference). film). These can be made by conventional methods. An example of the method described in JP-A-2002-71957 and JP-A-2003-170492 is exemplified. Further, it is preferable to use a polarizing plate protective film having an optical compensation film having an optical anisotropic layer formed by aligning a liquid crystal compound such as a discotic liquid crystal. As for the method of forming the optically anisotropic layer, a liquid crystal compound can be formed by a conventional method, and an optically anisotropic layer can be formed by a method described in JP-A-2003-98348. Alternatively, it is also preferred to use an aligning film in which the quiescent phase Ro is 0 to 5 nm at 590 nm and the Rt is -20 to +20 nm. The unaligned film may be a conventionally exemplified one, and an example of an unaligned film in which the in-plane phase retardation Ro is 0 to 5 nm at 590 nm and Rt is -20 to +20 nm is exemplified in JP-A-2003-12859.

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

The polarizing plate protective film used on the back side is preferably a commercially available cellulose ester film of KC8UX2MW, KC4UX, KC5UX, KC4UY, KC8UY, KC12UR, KC4UEW, KC8UCR-3, KC8UCR-4, KC8UCR-5, KC4FR-1. , KC4FR-2, KC8UE, KC4UE (KONICA MINOLTA OPTO (share) system).

The polarizing film which is a main component of the polarizing plate is a light that passes only a polarizing surface in a certain direction. A typical polarizing film is a polyvinyl alcohol-based polarizing film, and the polyvinyl alcohol-based film is dyed with iodine. The dichroic dye is dyed, but is not limited thereto. The polarizing film is formed by using a polyvinyl alcohol aqueous solution to form a film, and the film is uniaxially stretched and dyed, or uniaxially stretched after dyeing, and is preferably subjected to durability treatment with a boron compound. It is preferred to use a polarizing film having a film thickness of 5 to 30 μm, preferably 8 to 15 μm. A polarizing plate is formed on one surface of the antireflection film of the present embodiment on the surface of the polarizing film. It is preferred to carry out lamination with an aqueous binder containing, as a main component, a fully alkalized polyvinyl alcohol.

(image display device)

By assembling a polarizing plate using the antireflection film of the present embodiment in a display device, it is possible to produce various image display devices having excellent visibility.

The antireflection film of the present embodiment is preferably incorporated in the polarizing plate, and is a reflective, transmissive, or transflective liquid crystal display device, TN type, STN type, OCB type, HAN type, or VA type (PVA type, MVA). Type), IPS type, OCB type and other liquid crystal display devices of various driving methods are used. Further, the antireflection film of the present embodiment is preferably used in various image display devices such as a plasma display, a field emission display, an organic EL display, an inorganic EL display, and an electronic paper.

Example

The invention will be specifically described below by way of examples, but the invention is not limited thereto.

Example A

[Example 1]

<Transparent film substrate; manufacture of cellulose ester film 1>

(dopant composition)

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 and stirred for 3 hours to completely dissolve the cellulose ester. A solution dispersed in a solvent to which cerium oxide microparticles are added in advance and a small amount of cellulose ester is added. The dopant was filtered using a filter paper (manufactured by Anjun Filter Paper Co., Ltd., Angstrom Paper No. 244) to obtain a dopant composition.

Cellulose acetate (acetamyl substitution degree 2.95) 100 parts by mass

Trimethylolpropane tribenzoate 5 parts by mass

Ethyl phthalic acid ethyl glycolate 5 parts by mass

Cerium oxide microparticles (AEROSIL R972V, Japan

AEROSIL Co., Ltd.) 0.2 parts by mass

TINUVIN 109 (made by Ciba ‧ Japan) 1 part by mass

TINUVIN 171 (made by Ciba ‧ Japan) 1 part by mass

Dichloromethane 300 parts by mass

40 parts by weight of ethanol

Butanol 5 parts by mass

Next, the obtained dopant composition was cast on a support having a temperature of 35 ° C and cast at a temperature of 35 ° C made of a stainless steel endless belt to form a sheet. Next, the sheet was dried on the support, and the sheet was peeled off from the support by a peeling roller at a stage where the amount of residual solvent of the sheet was 80% by mass.

The peeled sheet was conveyed and dried by a plurality of rolls arranged one above the other, and then conveyed while drying at a drying air of 90° C., and then the both ends of the sheet were held by a spreader, and then extended at a temperature of 130° C. in the width direction. 1.1 times before the extension. After extending through the spreader, the sheet was subjected to a transport drying step of a plurality of rolls arranged up and down, and dried at 135 ° C dry air. The atmosphere replacement rate in the drying step was 15 (times/hour) and heat-treated in the atmosphere for 15 minutes, and then cooled to room temperature and wound up to prepare a strip having a width of 1.5 m, a film thickness of 80 μm, a length of 4000 m, and a refractive index of 1.49. Cellulose ester film 1. Further, the film was subjected to knurling with a width of 1 cm and an average height of 10 μm at both end portions and wound up. The stretching ratio of the sheet conveying direction immediately after peeling calculated from the rotation speed of the stainless steel belt support and the running speed of the cloth machine was 1.1 times.

The atmosphere replacement rate in the drying step is V (m ³ ) in the drying step (heat treatment chamber), and the FA (m ³ /hr) in the fresh air blowing amount is obtained per unit time in the following formula. The number of times the fresh air replaces the atmosphere in the heat treatment chamber. Fresh air means the wind that is supplied to the heat treatment chamber, the non-recycling wind, the solvent or plasticizer that does not contain volatiles, or the removal of fresh wind.

Atmosphere gas replacement rate = FA / V (time / time)

<Preparation of Anti-Reflection Film 1>

On the cellulose ester film 1 produced above, a hard coat layer and a reflection preventing layer were provided in the following order to prepare an antireflection film 1.

<Production of Hard Coatings>

Using the above cellulose ester film 1, a hard coat layer was prepared in the following order.

In the apparatus shown in Fig. 1, a resin composition for forming a hard coat layer was filtered by applying a filter made of polypropylene having a pore diameter of 0.4 μm to the cellulose ester film 1 by using an extrusion coater (in the table). The hard coat coating liquid prepared by the resin composition for forming a HC layer was dried at 80 ° C for 1 minute, and then an ultraviolet lamp was used, and the illuminance of the irradiated portion was 100 mW/cm ² and the irradiation amount was 0.2 J/ The conditions of cm ² were hardened to form a hard coating having a dry film thickness of 10 μm. Next, the following back coat coating composition was applied to the surface opposite to the surface on which the hard coat layer was applied by an extrusion coater so as to have a wet film thickness of 10 μm, and dried at 50° C. to prepare. A rigid film is formed and rolled into a roll shape.

<Resin composition for forming a hard coat layer>

Pentaerythritol triacrylate 20 parts by mass

Pentaerythritol tetraacrylate 50 parts by mass

Urethane acrylate (U-4HA:

50% by mass produced by Shin-Nakamura Chemical Industry Co., Ltd.

Free radical polymerization initiator (IRGACURE 184:

Ciba ‧ made by Japan company) 5 parts by mass

A mixed solvent of ethyl acetate/propylene glycol monomethyl ether = 50 parts by mass / 50 parts by mass was added to the above composition to obtain a solid content of 50% by weight to obtain a resin composition for forming a hard coat layer.

<Backcoat coating composition>

Diethyl fluorenyl cellulose 0.6 parts by mass

Acetone 35 parts by mass

Methyl ethyl ketone 35 parts by mass

Methanol 35 parts by mass

2% methanol dispersion of cerium oxide particles 16 parts by mass

(KE-P30, manufactured by Nippon Shokubai Co., Ltd.)

<Production of Low Refractive Index Layer>

The resin composition 1 for forming a low refractive index layer as described below was applied onto the hard coat layer prepared above to prepare an antireflection film 1.

<Resin composition for forming a low refractive index layer 1>

2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane

A-1 55 parts by mass

Illustrative compound S-1 5 parts by mass of hydrazine salt acid generator

Cerium oxide microparticles C-1 (isopropyl alcohol dispersion)

Hollow cerium oxide microparticles) 45 parts by mass

Isopropyl alcohol 450 parts by mass

Methyl ethyl ketone 450 parts by mass

In the resin composition 1 for forming a low refractive index layer, a compound other than the hollow cerium oxide fine particles C-1 dispersed in isopropyl alcohol is added to the isopropanol and methyl ethyl ketone at the above-mentioned mixing ratio, and then dissolved. The above-mentioned blending ratio was added with isopropyl alcohol dispersed hollow cerium oxide microparticles C-1.

(Modulation of hollow cerium oxide microparticle dispersion C-1)

A mixture of 100 g of cerium oxide alumina sol having an average particle diameter of 25 nm and a concentration of SiO ₂ ‧ Al ₂ O _{3 of} 20% by mass and 3900 g of pure water was heated to 98 °C. While maintaining this temperature, 1750 g of an aqueous solution of sodium citrate having a SiO _{2 content} of 1.5% by mass and 1750 g of an aqueous solution of sodium aluminate having a content of 0.5% by mass in terms of Al ₂ O ₃ were added to obtain SiO ₂ ·Al ₂ O ₃ once. Particle dispersion. The pH of the reaction solution was 12.0 (step a).

Next, 3300 g of a concentration of 1.5% by mass of sodium sulfate was added, and 6300 g of an aqueous solution of sodium citrate having a SiO _{2 content} of 1.5% by mass and 2,100 g of an aqueous solution of sodium aluminate having a content of 0.5% by mass of Al ₂ O ₃ were added to obtain a composite. Oxide fine particle dispersion. The pH of the reaction solution was 12.0 (step b).

Then, 1500 g of pure water, 100 g of 0.5% by mass of sodium sulfate, and then concentrated hydrochloric acid (concentration 35.5 mass) were added to 500 g of the composite oxide fine particle dispersion having a solid content concentration of 13% by mass. %), made to pH 1.0, and subjected to dealumination treatment.

Then, while dissolving 10 L of a hydrochloric acid aqueous solution of pH 3 and 5 L of pure water, the dissolved aluminum salt was separated by an ultrafiltration membrane to obtain an aqueous dispersion of cerium oxide-based fine particles having a solid concentration of 20% by mass (step c).

150 g of the aqueous dispersion of the cerium oxide-based fine particles, and a mixture of 500 g of pure water, 1750 g of ethanol, and 626 g of 28% aqueous ammonia were heated to 35 ° C, and then 140 g of ethyl decanoate (SiO ₂ 28% by mass) was added to form The cerium oxide coating layer was washed with an ultrafiltration membrane while adding 5 L of pure water to obtain an aqueous dispersion of cerium oxide-based fine particles forming a cerium oxide coating layer having a solid concentration of 20% by mass (step d).

Next, ammonia water is added to the cerium oxide-based fine particle dispersion liquid forming the cerium oxide coating layer, the pH is adjusted to 10.5, the mixture is aged at 150 ° C for 11 hours, and then cooled to room temperature, and ion exchange with a cation exchange resin is repeated, and an anion is repeatedly performed. Ion exchange was carried out, and then the solvent was replaced with ethanol using an ultrafiltration membrane to prepare a hollow cerium oxide fine particle dispersion 1 having a solid concentration of 20% by mass.

The outer layer of the hollow cerium oxide microparticles had a thickness of 10 nn, an average particle diameter of 55 nm, a MO _x /SiO ₂ (mole ratio) of 0.0019, and a refractive index of 1.24. Among them, the average particle diameter is measured by a dynamic light scattering method.

(Preparation of low refractive index layer)

The resin composition 1 for forming a low refractive index layer was applied onto the surface of the hard coat layer prepared above by using an apparatus shown in FIG. 1 in an extrusion coater so that the film thickness after drying was 85 nm. The film was dried at a temperature of 80 ° C for 1 minute, and then cured under the conditions of an illuminance of 200 mW/cm ² and an irradiation amount of 0.35 J/cm ² using an ultraviolet lamp to form a low refractive index layer, thereby preparing an antireflection film 1.

[Embodiment 2]

A resin composition 2 for forming a low refractive index layer is used instead of the resin composition 1 for forming a low refractive index layer, and a low refractive index layer is formed on a transparent film substrate, except that a hard coat layer is not formed. In the same manner as in Example 1, the antireflection film 2 was prepared.

<Resin composition for forming a low refractive index layer 2>

2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane

A-1 47 parts by mass

10 parts by mass of the compound S-1 exemplified by the hydrazine salt acid generator

Cerium oxide microparticle C-2 (SiLiNax) 43 parts by mass

Isopropyl alcohol 450 parts by mass

Methyl ethyl ketone 450 parts by mass

In the resin composition 2 for forming a low refractive index layer, a compound other than the cerium oxide fine particles C-2 is added to the isopropyl alcohol and the methyl ethyl ketone at the above-mentioned mixing ratio, and then dissolved, and then the cerium oxide fine particles are added in the above-mentioned mixing ratio. C-2, a resin composition 2 for forming a low refractive index layer having a solid content of 10% was obtained. Further, the cerium oxide microparticle C-2 is SiLiNax manufactured by Nippon Mining Co., Ltd., and has a primary particle diameter of 80 to 130 nm and a cerium oxide shell thickness of 5 to 15 nm.

[Example 3]

The antireflection film 3 was prepared as in Example 2 except that the resin composition 3 for forming a low refractive index layer was used instead of the resin composition 2 for forming a low refractive index layer in the formation of the low refractive index layer.

<Resin composition for forming a low refractive index layer 3>

2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane

A-1 54 parts by mass

6 parts by mass of the compound S-6 exemplified by the hydrazine salt acid generator

Cerium oxide microparticles C-1 (isopropyl alcohol dispersion

Empty cerium oxide microparticles) 50 parts by mass

Isopropyl alcohol 450 parts by mass

Methyl ethyl ketone 450 parts by mass

In the resin composition 3 for forming a low refractive index layer, a compound other than the oxidized cerium oxide fine particles C-1 dispersed in isopropyl alcohol is added to the isopropyl alcohol and methyl ethyl ketone at the above-mentioned mixing ratio, and then dissolved. Into the blending ratio, hollow cerium oxide fine particles C-1 dispersed in isopropyl alcohol were added to obtain a resin composition 3 for forming a low refractive index layer having a solid content of 10%.

[Example 4]

The antireflection film 4 was prepared in the same manner as in Example 1 except that the resin composition 4 for forming a low refractive index layer was used instead of the resin composition 1 for forming a low refractive index layer in the formation of the low refractive index layer.

<Resin composition for forming a low refractive index layer 4>

2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane

A-1 45 parts by mass

Illustrative compound S-1 5 parts by mass of hydrazine salt acid generator

Cerium oxide microparticles C-1 (isopropyl alcohol dispersion

Empty cerium oxide microparticles) 50 parts by mass

Isopropyl alcohol 450 parts by mass

Methyl ethyl ketone 450 parts by mass

In the resin composition 4 for forming a low refractive index layer, a compound other than the oxidized cerium oxide fine particles C-1 dispersed in isopropyl alcohol is added to the isopropyl alcohol and methyl ethyl ketone at the above-mentioned mixing ratio, and then dissolved. Into the blending ratio, hollow cerium oxide fine particles C-1 dispersed in isopropyl alcohol were added to obtain a resin composition 4 for forming a low refractive index layer having a solid content of 10%.

[Example 5]

The antireflection film 5 was prepared in the same manner as in Example 1 except that the resin composition 5 for forming a low refractive index layer was used instead of the resin composition 1 for forming a low refractive index layer.

<Resin composition for forming a low refractive index layer 5>

2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane

A-1 52 parts by mass

10 parts by mass of the compound S-1 exemplified by the hydrazine salt acid generator

Cerium oxide microparticle C-2 (SiLiNax) 38 parts by mass

Isopropyl alcohol 450 parts by mass

Methyl ethyl ketone 450 parts by mass

In the resin composition 5 for forming a low refractive index layer, a compound other than the cerium oxide fine particles C-2 is added to the isopropyl alcohol and the methyl ethyl ketone in the above-described mixing ratio, and then dissolved, and then the cerium oxide fine particles are added in the above-mentioned mixing ratio. C-2, a resin composition 5 for forming a low refractive index layer having a solid content of 10% was obtained. Further, the cerium oxide microparticle C-2 is SiLiNax manufactured by Nippon Mining Co., Ltd., and has a primary particle diameter of 80 to 130 nm and a cerium oxide shell thickness of 5 to 15 nm.

[Embodiment 6]

The antireflection film 6 was prepared in the same manner as in Example 1 except that the resin composition 6 for forming a low refractive index layer was used instead of the resin composition 1 for forming a low refractive index layer in the formation of the low refractive index layer.

<Resin composition for forming a low refractive index layer 6>

2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane

A-1 36 parts by mass

Illustrative compound S-1 7 parts by mass of hydrazine salt acid generator

Cerium oxide microparticles C-1 (isopropyl alcohol dispersion)

Hollow cerium oxide microparticles) 57 parts by mass

Isopropyl alcohol 450 parts by mass

Methyl ethyl ketone 450 parts by mass

In the resin composition 6 for forming a low refractive index layer, a compound other than the hollow cerium oxide fine particles C-1 dispersed in isopropyl alcohol is added to the isopropanol and methyl ethyl ketone at the above-mentioned mixing ratio, and then dissolved. Into the blending ratio, hollow cerium oxide fine particles C-1 dispersed in isopropyl alcohol were added to obtain a resin composition 6 for forming a low refractive index layer having a solid content of 10%.

[Embodiment 7]

The antireflection film 7 was prepared in the same manner as in Example 1 except that the resin composition 7 for forming a low refractive index layer was used instead of the resin composition 1 for forming a low refractive index layer in the formation of the low refractive index layer.

<Resin composition for forming a low refractive index layer 7>

2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane

A-1 43 parts by mass

Illustrative compound S-1 5 parts by mass of hydrazine salt acid generator

Cerium oxide microparticles C-1 (isopropyl alcohol dispersion)

Hollow cerium oxide microparticles) 52 parts by mass

Isopropyl alcohol 450 parts by mass

Methyl ethyl ketone 450 parts by mass

In the resin composition 7 for forming a low refractive index layer, a compound other than the hollow cerium oxide fine particles C-1 dispersed in isopropyl alcohol is added to the isopropanol and methyl ethyl ketone at the above-mentioned mixing ratio, and then dissolved. To the blending ratio, hollow cerium oxide fine particles C-1 dispersed in isopropyl alcohol were added to obtain a resin composition 7 for forming a low refractive index layer having a solid content of 10%.

[Embodiment 8]

The antireflection film 8 was prepared as in Example 1 except that the resin composition 8 for forming a low refractive index layer was used instead of the resin composition 1 for forming a low refractive index layer in the formation of the low refractive index layer.

<Resin composition for forming a low refractive index layer 8>

1,4-cyclohexanedimethanol divinyl ether A-1 54 parts by mass

4 parts by mass of the compound S-1 exemplified by the hydrazine salt acid generator

Cerium oxide microparticles C-1 (isopropyl alcohol dispersion)

Hollow cerium oxide microparticles) 42 parts by mass

Isopropyl alcohol 450 parts by mass

Methyl ethyl ketone 450 parts by mass

In the resin composition 8 for forming a low refractive index layer, a compound other than the hollow cerium oxide fine particles C-1 dispersed in isopropyl alcohol is added to the isopropyl alcohol and methyl ethyl ketone at the above-mentioned mixing ratio, and then dissolved. Into the blending ratio, hollow cerium oxide fine particles C-1 dispersed in isopropyl alcohol were added to obtain a resin composition 8 for forming a low refractive index layer having a solid content of 10%.

[Comparative Example 1]

The antireflection film 9 was prepared in the same manner as in Example 1 except that the resin composition 9 for forming a low refractive index layer was used instead of the resin composition 1 for forming a low refractive index layer in the formation of the low refractive index layer.

<Resin composition for forming a low refractive index layer 9>

Pentaerythritol acrylate B-1 49 parts by mass

IRGACURE250 (manufactured by Ciba ‧ Japan) 5 parts by mass

Cerium oxide microparticle C-2 (SiLiNax) 46 parts by mass

Isopropyl alcohol 450 parts by mass

Methyl ethyl ketone 450 parts by mass

In the resin composition 9 for forming a low refractive index layer, a compound other than the cerium oxide fine particles C-2 is added to the isopropyl alcohol and the methyl ethyl ketone at the above-mentioned mixing ratio, and then dissolved, and then the cerium oxide fine particles are added in the above-mentioned mixing ratio. C-2, a resin composition 9 for forming a low refractive index layer having a solid content of 10% was obtained. [Comparative Example 2]

The antireflection film 10 was prepared in the same manner as in Example 2 except that the resin composition 10 for forming a low refractive index layer was used instead of the resin composition 2 for forming a low refractive index layer in the formation of the low refractive index layer.

<Resin composition for forming a low refractive index layer 10>

Pentaerythritol acrylate B-1 51 parts by mass

IRGACURE250 (manufactured by Ciba ‧ Japan) 5 parts by mass

Cerium oxide microparticles C-1 (isopropyl alcohol dispersion)

Hollow cerium oxide microparticles) 44 parts by mass

Isopropyl alcohol 450 parts by mass

Methyl ethyl ketone 450 parts by mass

In the resin composition 10 for forming a low refractive index layer, a compound other than the hollow cerium oxide fine particles C-1 dispersed in isopropyl alcohol is added to the isopropanol and methyl ethyl ketone at the above-mentioned mixing ratio, and then dissolved. Into the blending ratio, hollow cerium oxide fine particles C-1 dispersed in isopropyl alcohol were added to obtain a resin composition 10 for forming a low refractive index layer having a solid content of 10%.

[Comparative Example 3]

The antireflection film 11 was prepared in the same manner as in Example 2 except that the resin composition for forming a low refractive index layer was used instead of the resin composition 2 for forming the low refractive index layer in the formation of the low refractive index layer.

<Resin composition for forming a low refractive index layer 11>

2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane

A-1 48 parts by mass

S salt acid generator exemplified compound S-6 3 parts by mass

Cerium oxide microparticle D-1 (IPA-ST-UP) 49 parts by mass

Isopropyl alcohol 450 parts by mass

Methyl ethyl ketone 450 parts by mass

In the resin composition 11 for forming a low refractive index layer, a compound other than the cerium oxide microparticle D-1 is added to the isopropyl alcohol and the methyl ethyl ketone at the above-mentioned mixing ratio, and then dissolved, and then the cerium oxide microparticles are added in the above-mentioned mixing ratio. D-1, a resin composition 11 for forming a low refractive index layer having a solid content of 10% was obtained. Further, the cerium oxide microparticle D-1 is IPA-ST-UP manufactured by Nissan Chemical Industries Co., Ltd., and is a solid cerium oxide microparticle.

[Comparative Example 4]

The antireflection film 12 was prepared as in Example 2 except that the resin composition 12 for forming a low refractive index layer was used instead of the resin composition 2 for forming a low refractive index layer in the formation of the low refractive index layer.

<Resin composition for forming a low refractive index layer 12>

2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane

A-1 45 parts by mass

Illustrative compound S-1 5 parts by mass of hydrazine salt acid generator

Cerium oxide microparticle D-2 (OX50) 50 parts by mass

Isopropyl alcohol 450 parts by mass

Methyl ethyl ketone 450 parts by mass

In the resin composition 12 for forming a low refractive index layer, a compound other than the cerium oxide microparticle D-2 is added to the isopropanol and the methyl ethyl ketone at the above-described mixing ratio, and then dissolved, and then the cerium oxide microparticles are added in the above-mentioned mixing ratio. D-2, a resin composition 12 for forming a low refractive index layer having a solid content of 10% was obtained. Further, the cerium oxide microparticle D-2 is OX50 manufactured by Japan AEROSIL Co., Ltd., and is a solid cerium oxide microparticle.

[Comparative Example 5]

The antireflection film 13 was prepared in the same manner as in Example 2 except that the resin composition 13 for forming a low refractive index layer was used in place of the resin composition 2 for forming a low refractive index layer in the formation of the low refractive index layer.

<Resin composition for forming a low refractive index layer 13>

2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane

A-1 81 parts by mass

4 parts by mass of the compound S-1 exemplified by the hydrazine salt acid generator

Cerium oxide microparticles C-1 (isopropyl alcohol dispersion)

Hollow cerium oxide microparticles) 15 parts by mass

Isopropyl alcohol 450 parts by mass

Methyl ethyl ketone 450 parts by mass

In the resin composition 13 for forming a low refractive index layer, a compound other than the cerium oxide fine particles C-1 is added to the isopropyl alcohol and the methyl ethyl ketone at the above-mentioned mixing ratio, and then dissolved, and then the cerium oxide fine particles are added in the above-mentioned mixing ratio. C-1, a resin composition 13 for forming a low refractive index layer having a solid content of 10% was obtained.

[Comparative Example 6]

The antireflection film 14 was prepared in the same manner as in Example 2 except that the resin composition for forming a low refractive index layer was used instead of the resin composition 2 for forming the low refractive index layer in the formation of the low refractive index layer.

<Resin composition for forming a low refractive index layer 14>

2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane

A-1 74 parts by mass

6 parts by mass of the compound S-1 exemplified by the hydrazine salt acid generator

Cerium oxide microparticle C-2 (SiLiNax) 20 parts by mass

Isopropyl alcohol 450 parts by mass

Methyl ethyl ketone 450 parts by mass

In the resin composition 14 for forming a low refractive index layer, a compound other than the cerium oxide fine particles C-2 is added to the isopropyl alcohol and the methyl ethyl ketone at the above-mentioned mixing ratio, and then dissolved, and then the cerium oxide fine particles are added in the above-mentioned mixing ratio. C-2, a resin composition 14 for forming a low refractive index layer having a solid content of 10% was obtained.

[Comparative Example 7]

The antireflection film 15 was prepared as in Example 2 except that the resin composition 15 for forming a low refractive index layer was used instead of the resin composition 2 for forming a low refractive index layer in the formation of the low refractive index layer.

<Resin composition for forming a low refractive index layer 15>

2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane

A-1 43 parts by mass

Illustrative compound S-6 5 parts by mass of hydrazine salt acid generator

Cerium oxide microparticle C-2 (SiLiNax) 52 parts by mass

Isopropyl alcohol 450 parts by mass

Methyl ethyl ketone 450 parts by mass

In the resin composition 15 for forming a low refractive index layer, a compound other than the cerium oxide fine particles C-2 is added to the isopropyl alcohol and the methyl ethyl ketone at the above-mentioned mixing ratio, and then dissolved, and then the cerium oxide fine particles are added in the above-mentioned mixing ratio. C-2, a resin composition 15 for forming a low refractive index layer having a solid content of 10% was obtained.

[Comparative Example 8]

The antireflection film 16 was prepared as in the first embodiment except that the resin composition 16 for forming a low refractive index layer was used instead of the resin composition 1 for forming a low refractive index layer in the formation of the low refractive index layer.

<Resin composition for forming a low refractive index layer 16>

2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane

A-1 40 parts by mass

Illustrative compound S-1 5 parts by mass of hydrazine salt acid generator

Cerium oxide microparticles C-1 (isopropyl alcohol dispersion)

Hollow cerium oxide microparticles) 55 parts by mass

Isopropyl alcohol 450 parts by mass

Methyl ethyl ketone 450 parts by mass

In the resin composition 16 for forming a low refractive index layer, a compound other than the hollow cerium oxide fine particles C-1 dispersed in isopropyl alcohol is added to the isopropanol and methyl ethyl ketone at the above-mentioned mixing ratio, and then dissolved. Into the blending ratio, hollow cerium oxide fine particles C-1 dispersed in isopropyl alcohol were added to obtain a resin composition 16 for forming a low refractive index layer having a solid content of 10%.

[Comparative Example 9]

The antireflection film 17 was prepared in the same manner as in Example 1 except that the resin composition for forming a low refractive index layer was used instead of the resin composition 1 for forming a low refractive index layer in the formation of the low refractive index layer.

<Resin composition for forming a low refractive index layer 17>

2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane

A-1 34 parts by mass

6 parts by mass of the compound S-6 exemplified by the hydrazine salt acid generator

Cerium oxide microparticles C-1 (isopropyl alcohol dispersion)

Hollow cerium oxide microparticles) 60 parts by mass

Isopropyl alcohol 450 parts by mass

Methyl ethyl ketone 450 parts by mass

In the resin composition 17 for forming a low refractive index layer, a compound other than the hollow cerium oxide fine particles C-1 dispersed in isopropyl alcohol is added to the isopropyl alcohol and methyl ethyl ketone at the above-mentioned mixing ratio, and then dissolved. Into the blending ratio, hollow cerium oxide fine particles C-1 dispersed in isopropyl alcohol were added to obtain a resin composition 17 for forming a low refractive index layer having a solid content of 10%.

The above conditions are summarized in Table 1. In Table 1, those not included are indicated by "-".

Next, with respect to the antireflection films 1 to 17 of the above-prepared Examples 1 to 8 and Comparative Examples 1 to 9, the thickness of the low refractive index layer and the thickness of the low refractive index layer were measured for the average particle diameter of the cerium oxide microparticles by the following method. Ratio (low refractive index layer thickness / average particle diameter of cerium oxide microparticles), and surface roughness Ra of the low refractive index layer. The results obtained are shown in Table 1.

(thickness of low refractive index layer)

After embedding the obtained antireflection film with an epoxy resin, an ultrathin section of about 10 nm thick was produced by an ultramicrotome, and a transmission electron microscope (TEM) (HF-3300 manufactured by Hitachi, Ltd.) was used to photograph 800,000 times. TEM portrait. The thickness (μm) of the low refractive index layer of the antireflection film was measured.

(The ratio of the thickness of the low refractive index layer to the average particle diameter of the cerium oxide microparticles)

The ratio of the low refractive index layer thickness to the average particle diameter of the cerium oxide microparticles was calculated by dividing the thickness of the low refractive index layer measured as described above by the average particle diameter of the cerium oxide microparticles used.

(surface roughness Ra of the low refractive index layer)

The surface roughness Ra (nm) of the low refractive index layer was measured by measuring the surface of the low refractive index layer side of the obtained antireflection film by AFM (Atomic Force Microscopy) (Dimension 3100, manufactured by VEECO, Japan).

"Evaluation"

The antireflection films 1 to 17 of the above-prepared Examples 1 to 8 and Comparative Examples 1 to 9 were evaluated by the following methods. The results obtained are shown in Table 2.

(Reflectivity)

The reflectance of each of the antireflection films was measured as follows.

First, the back surface of each of the antireflection films (the surface opposite to the side on which the low refractive index layer is formed) was roughened, and then subjected to light absorption treatment using a black spray. Next, the antireflection film subjected to the light absorption treatment was irradiated with light in the visible light range (400 to 700 nm), and the reflectance was measured using a spectrophotometer (U-4100, manufactured by Hitachi HiTech Co., Ltd.).

(light resistance test)

Using a Super xenon weather meter (SX120, manufactured by Suga Tester), with a light quantity of 100 W/m ² ; 300 to 400 nm, a black panel temperature of 50 ° C, a humidity of 65%, and a test time of 2000 hours. Conditions The UV irradiation test (light resistance test) was performed on the surface of each of the antireflection films. Subsequently, the adhesion test and the scratch resistance test before and after the light resistance test were carried out by the following methods.

(adhesion test)

Each of the antireflection films before and after the light resistance test was cut into a size of 10 cm on each side, and immersed in ethanol, methyl ethyl ketone, pH 4 buffer, pH 9 buffer for 1 hour, and then washed with pure water.

Next, a checkerboard tape peeling test was carried out in accordance with JIS K 5600. 100 meshes were cut out on the surface of each of the antireflection films by a dicing blade, and the adhesive tape (No. 31B manufactured by Nitto Denko Corporation) was pressed at the same position, peeled off, and repeated three times. Subsequently, the surface of the sample after peeling off the tape was visually observed and evaluated on the following basis.

Adhesion evaluation benchmark

◎: Confirm that all are not stripped

○: Almost no peeling was confirmed, but it was confirmed that some of the mesh edges were defective.

△: Although the whole surface was peeled off, peeling was confirmed.

×: The entire surface peeling can be confirmed

Moreover, if the evaluation point is ○~◎, there is no problem in practical use.

(scratch resistance test)

Each of the antireflection films before and after the light resistance test was cut into a size of 5 cm × 10 cm on each side, and immersed in ethanol, methyl ethyl ketone, pH 4 buffer, pH 9 buffer for 1 hour, and then washed with pure water.

Next, the number of scratches per 1 cm width at a time of back and forth 10 times with a load of 300 g/cm ^{2 was} measured by a steel wool (SW) of BONSTAR #0000 manufactured by Japan Steelwool Co., Ltd., and evaluated on the following basis. Further, the number of scratches was measured at the position where the number of scratches was the largest in the portion where the load was applied.

◎: The number of scratches is 0~3 pieces/cm

○: The number of scratches is 4~7 pieces/cm

○’: The number of scratches is 8~10 pieces/cm

△: The number of scratches is 11~20 pieces/cm

×: The number of scratches is 21 pieces/cm or more

As is clear from the results of Table 2, the antireflection film of the present embodiment has a low reflectance, and is excellent not only in the sample immediately after the film formation but also in adhesion and scratch resistance after the light resistance test.

Example B

[Examples 9 to 16 and Comparative Examples 10 to 18] Each of the anti-reflection films 1 to 17 and the cellulose ester-based optical compensation film KC8UCR5 (manufactured by KONICA MINOLTA OPTO Co., Ltd.) was used as a polarizing light according to the following method. The protective film of the board is thin, and a polarizing plate is separately prepared.

(a) Production of polarizing film

100 parts by mass of a polyvinyl alcohol having a degree of saponification of 99.95 mol% and a degree of polymerization of 2400 (hereinafter referred to as PVA) are impregnated with 10 parts by mass of glycerin and 170 parts by mass of water, and after defoaming, The T-die is melt extruded on a metal roll and formed into a film. Subsequently, after drying and heat treatment, a PVA film was obtained. The obtained PVA film had an average thickness of 40 μm, a moisture content of 4.4%, and a film width of 3 m.

Next, the obtained PVA film was subjected to continuous treatment in the order of pre-swelling, dyeing, wet uniaxial stretching, fixing treatment, drying, and heat treatment to prepare a polarizing film. That is, the PVA film was immersed in water at 30 ° C for 30 seconds to be pre-swelled, and immersed in an aqueous solution having an iodine concentration of 0.4 g/L and a potassium iodide concentration of 40 g/L at a temperature of 35 ° C for 3 minutes. Next, 6 times of uniaxial stretching was carried out in a 50 ° C aqueous solution having a boric acid concentration of 4% under a tension of 700 N/m, and immersed in a potassium iodide concentration of 40 g/L, a boric acid concentration of 40 g/L, and a zinc chloride concentration of 10 g/ The temperature of L was fixed in an aqueous solution of 30 ° C for 5 minutes. Subsequently, 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 film thickness of 13 μm, a polarizing property of 43.0%, a degree of polarization of 99.5%, and a dichroic ratio of 40.1.

(b) Production of polarizing plate

Then, according to the following steps 1 to 5, the polarizing film and the protective film for a polarizing plate are bonded together to form polarizing plates 101 to 117 corresponding to the antireflection films 1 to 17 of Examples 1 to 8 and Comparative Examples 1 to 9. .

Step 1: An optical compensation film (KONICA MINOLTA TECH KCUCR-5 manufactured by KONICA MINOLTA OPTO Co., Ltd.) and an antireflection film were immersed in a 2 mol/L sodium hydroxide solution at a temperature of 60 ° C for 90 seconds, followed by washing with water. dry. A pre-detachable protective film (made of PET) is attached to the surface of each of the antireflection films on which the low refractive index layer is provided to protect the film. Similarly, the optical compensation film was immersed in a 2 mol/L sodium hydroxide solution at a temperature of 60 ° C for 90 seconds, washed with water, and dried.

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: The excess adhesive attached to the polarizing film of the step 2 is gently removed, and the polarizing film is sandwiched between the alkali-treated optical compensation film of Step 1 and the antireflection film to perform a lamination configuration.

Step 4: The laminate was laminated between two rotating rolls at a pressure of 20 to 30 N/cm ² and a speed of about 2 m/min. At this point, it must be carried out carefully without letting the bubbles enter.

Step 5: The sample prepared in the step 4 was dried in a dryer at a temperature of 80 ° C for 2 minutes to prepare polarizing plates 101 to 133.

Next, the polarizing plate on the outermost surface of the commercially available liquid crystal display panel (VA type) was carefully peeled off, and the polarizing plates 101 to 117 were bonded thereto in the polarizing direction. Thus, each of the polarizing plates 101 to 117 was prepared, and the liquid crystal panels 101 to 117 of Examples 9 to 16 and Comparative Examples 10 to 18 were evaluated as follows.

[identification]

The visibility of each of the liquid crystal panels 101 to 117 was evaluated as follows.

The liquid crystal panels 101 to 117 are placed on a table 80 cm high from the floor, and a fluorescent lamp (FLR40S‧D/MX, manufactured by Matsushita Electric Industrial Co., Ltd.) 40W × 2 is mounted on the ceiling 3 m above the floor. For a group, 10 groups are arranged at a distance of 1.5 m. At this time, the evaluator faces the front surface of the display surface of the liquid crystal panel, and the fluorescent lamp is placed on the ceiling from the back of the evaluator head. Each of the liquid crystal panels is inclined at 25° with respect to the vertical direction of the table top, and the fluorescent lamp is irradiated thereon to distinguish and evaluate the visual difficulty (identification) of the screen as follows.

A: There is no interference fringe. Since the recent fluorescent light is completely influential, the text with a font size of 8 or less can be clearly read.

B: There is no interference fringe. The nearer fluorescent light has a slight influence, but the farther one has no effect. The text with the font size below 8 is barely read.

C: The interference fringes are slightly observed, and the fluorescent lamps that are far away have an influence. The characters with a font size of 8 or less are difficult to read.

D: The interference fringes are clearly recognized, and the fluorescent light has a considerable influence. The characters that are reflected in the printed font size below 8 cannot be read.

As a result of the evaluation, each of the liquid crystal panels 109 to 117 of Comparative Examples 10 to 18 using the polarizing plates corresponding to the respective antireflection films 9 to 17 was evaluated as C or less, and the respective antireflection films 1 to 1 were used. Each of the liquid crystal panels 101 to 108 of Examples 9 to 16 of the polarizing plate of 8 was evaluated as B or more, and it was confirmed that there was no interference fringe and the visibility was good.

Although the present specification discloses various techniques as described above, the main techniques are summarized as follows.

The low-reflection member in the same state of the present invention is characterized in that (a) a cationically polymerizable binder resin, (b) a phosphonium-based acid generator, and (c) an outer shell layer are provided on at least one side of the support substrate, and a low refractive index layer of porous or voided cerium oxide microparticles, wherein the thickness of the low refractive index layer is more than one time and less than three times the average particle diameter of the cerium oxide microparticles, and the surface roughness of the low refractive index layer Ra is less than 5 nm.

According to the above configuration, it is possible to provide a low-reflection member which is excellent in scratch resistance and adhesion, and particularly excellent in scratch resistance and adhesion after the light resistance test, and which can suppress the occurrence of cerium oxide fine particles from falling off. A reflection preventing film comprising a low reflection member, a polarizing plate using the antireflection film, and an image display device.

Further, in the above-mentioned low-reflection member, the onium salt-based acid generator is preferably an onium salt represented by any one of the following general formulae (1) to (4).

In the formula (1), R ¹ to R ³ each independently represent a hydrogen atom or a substituent, and at least one of R ¹ to R ³ represents a substituent; and in the formula (2), R ⁴ to R ⁷ each represent hydrogen. At least one or more of R ⁴ to R ⁷ represents a substituent; and in the formula (3), R ⁸ to R ¹¹ each independently represent a hydrogen atom or a substituent, and at least one of R ⁸ to R ¹¹ represents at least one of In the formula (4), R ¹² to R ¹⁷ each independently represent a hydrogen atom or a substituent, and at least one of R ¹² to R ¹⁷ represents a substituent, and X ^- each represents a non-nucleophilic anion residue] .

Further, in the low reflection member, the average particle diameter of the cerium oxide microparticles is preferably from 10 nm to 1 μm.

Further, in the low reflection member, the cationically polymerizable binder resin preferably has at least one of an epoxy group and a vinyl ether group.

Further, in the above-described low-reflection member, the cationically polymerizable binder resin is preferably one obtained by curing a cationically polymerizable monomer by ultraviolet irradiation.

Further, in the low reflection member, the low refractive index layer preferably further contains conductive fine particles.

Further, in the low reflection member, it is preferable that the antistatic layer containing the conductive fine particles and the binder resin is further provided between the support member and the low refractive index layer.

Further, another aspect of the antireflection film of the present invention is characterized in that it is composed of the aforementioned low reflection member.

Further, another embodiment of the polarizing plate of the present invention is characterized in that the polarizing plate of the antireflection film is used on at least one side.

Further, an image display device according to another aspect of the present invention is characterized in that the image display device using the antireflection film or the polarizing plate is used.

The present application is based on Japanese Patent Application No. 2009-33422, filed on Feb. 17, 2009, the content of which is incorporated herein.

The present invention has been described with respect to the embodiments of the present invention, and the embodiments of the present invention can be easily and fully modified by those skilled in the art. Therefore, it is to be understood that the modifications and variations of the invention are intended to be included within the scope of the claims.

1. . . Feed roller

2. . . Conveyor roller

3. . . Coating device

4. . . Counter roller

5. . . First drying device

6. . . Active line irradiation device

6a. . . Active line illumination lamp

6b. . . Cooling medium supply unit

6c. . . Atmosphere gas supply

7. . . Second drying device

8. . . Winding device

10. . . Warm air outlet

15. . . Take the core

Y. . . film

Fig. 1 is a schematic view showing an apparatus for manufacturing an optical film according to an embodiment of the present invention.

Claims (10)

A low-reflection member characterized by having (a) a cationically polymerizable binder resin, (b) a phosphonium-based acid generator, and (c) an outer shell layer on at least one side of a support substrate, and having a porous inner portion Or a low refractive index layer of the hollow cerium oxide microparticles, wherein the thickness of the low refractive index layer is more than one time and less than three times the average particle diameter of the cerium oxide microparticles, and the surface roughness Ra of the low refractive index layer is less than 5 nm. The onium salt acid generator is an onium salt represented by any one of the following formulae (1) to (4). In the formula (1), R ¹ to R ³ each represent a substituent; in the formula (2), R ⁴ to R ⁷ each independently represent a hydrogen atom or a substituent, and at least one of R ⁴ to R ⁷ represents a substitution. In the formula (3), R ⁸ to R ¹¹ each independently represent a hydrogen atom or a substituent, and at least one of R ⁸ to R ¹¹ represents a substituent; and in the formula (4), R ¹² to R ¹⁷ represent A hydrogen atom or a substituent, at least one of R ¹² to R ¹⁷ represents a substituent, and X ^- each represents a non-nucleophilic anion residue]. The low-reflection member according to claim 1, wherein the cerium oxide microparticles have an average particle diameter of 10 nm to 1 μm. The low-reflection member according to claim 1, wherein the cationically polymerizable binder resin has at least one of an epoxy group and a vinyl ether group. The low-reflection member according to claim 1, wherein the cationically polymerizable binder resin is obtained by curing a cationically polymerizable monomer by ultraviolet irradiation. The low-reflection member according to claim 1, wherein the low refractive index layer further contains conductive fine particles. The low-reflection member according to claim 1, wherein an antistatic layer containing conductive fine particles and a binder resin is further provided between the support member and the low refractive index layer. An antireflection film characterized by being constituted by a low reflection member as in the first aspect of the patent application. A polarizing plate characterized in that it is used on at least one side of an antireflection film as in item 7 of the patent application. An image display device characterized by using an antireflection film as in claim 7 of the patent application. An image display device characterized by using a polarizing plate as in claim 8 of the patent application.