JP2003107206A - Resin composition for optical functional film, optical functional film and antireflection film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition suitable to form a light transmitting layer which can constitute various kinds of optical functional films, particularly to form a low refractive index layer of an antireflection film and to provide an antireflection film having a low refractive index layer formed by using the above resin composition. SOLUTION: The resin composition for an optical functional film comprises at least (1) acicular fine particles and (2) a binder system containing a binder component having the molecular structure containing fluorine and/or silicon. A low refractive index layer 5 of an antireflection film 101 is formed by a coating method using this resin composition.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition for forming an optical thin film having a light transmittance and a controlled refractive index, and a light composition having a predetermined refractive index using the resin composition. Regarding the optical functional film provided with a transmission layer, in particular,
The present invention relates to a resin composition suitable for forming a low refractive index layer of an antireflection film, and an antireflection film provided with a low refractive index layer using the resin composition.

[0002]

2. Description of the Related Art The display surface of an image display device such as a liquid crystal display (LCD) or a cathode ray tube display device (CRT) is provided with a reflection of a light beam emitted from an external light source such as a fluorescent lamp in order to enhance its visibility. It is required to be small.

It has been known that the reflectance is reduced by coating the surface of a transparent object with a transparent film having a small refractive index. An antireflection film utilizing such a phenomenon is displayed on an image display device. It can be provided on the surface to improve the visibility. The antireflection film is a layer structure in which a low refractive index layer having a smaller refractive index than the coating surface is provided on the outermost surface of an object to be antireflection or a transparent substrate film, or to further improve the antireflection effect. On the coated surface medium to
It has a layer structure in which one to a plurality of high refractive index layers are provided, and a low refractive index layer for reducing the refractive index of the outermost surface is provided on the middle to high refractive index layers. In addition, for the purpose of imparting sufficient hardness to the antireflection film, a hard coat may be first provided on the coated surface, and then a medium to high refractive index layer or a low refractive index layer may be provided thereon.

The method of forming such a low refractive index layer of an antireflection film is generally roughly classified into a vapor phase method and a coating method. The vapor phase method includes physical methods such as a vacuum vapor deposition method and a sputtering method.
There is a chemical method such as a CVD method, and the coating method includes a roll coating method, a gravure coating method, a slide coating method, a spray method, a dipping method, a screen printing method and the like.

In the case of the vapor phase method, it is possible to form a high-performance and high-quality thin film low refractive index layer, but it is necessary to precisely control the atmosphere in a high vacuum system, and a special A heating device or an ion generation accelerating device is required, and thus the manufacturing device is complicated and large in size, which inevitably raises the manufacturing cost. Further, it is difficult to increase the area of the thin film of the low refractive index layer or to form the thin film with a uniform thickness on the surface of a film having a complicated shape.

On the other hand, in the case of using the spray method among the coating methods, there are problems that the utilization efficiency of the coating liquid is poor and it is difficult to control the film forming conditions. When the roll coating method, the gravure coating method, the slide coating method, the dipping method, the screen printing method and the like are used, the film forming raw materials are efficiently used and are advantageous in terms of mass production and equipment cost. The low refractive index layer obtained by the coating method has a problem that the function and quality are inferior to those obtained by the vapor phase method.

In recent years, as a coating method capable of forming a thin film of a low refractive index layer having excellent quality, a fluorine-containing or fluorine- and silicon-containing UV-curable resin composition is coated to form a coating film. A method has been proposed. It is possible to reduce the refractive index of the thin film by increasing the fluorine and silicon contents in this ultraviolet curable resin composition, but the thin film becomes softer as the fluorine and silicon contents increase, and it is necessary as a product. The desired film strength cannot be obtained. Considering the balance with the film strength, at present, the limit is to reduce the refractive index to about 1.38.

The antireflection film can realize an excellent antireflection effect as the refractive index of the low refractive index layer is lower, but in the conventional vapor phase method and coating method, a refractive index of 1.38 or less is obtained for the above reason. Is very difficult.

In Japanese Patent Laid-Open Nos. 7-168006 and 7-198904, only one layer of ultrafine particles having a low refractive index is formed on the surface to be antireflection, that is, with a film thickness about the same as the particle diameter of the ultrafine particles. By forming a densely packed coating film that is regularly arranged at high density, the outermost surface of the unevenness in which air and ultrafine particles are mixed is formed on the surface of the coating film,
It is described that the apparent refractive index of the outermost surface layer is brought close to that of air to obtain an outermost surface having a low refractive index. But,
It is very difficult to close-pack the spherical particles, and it is necessary to slow down the evaporation rate of the solvent so that the solvent convection does not occur during the drying in the coating film, and the drying time is very long.

[0010]

The present invention has been accomplished in view of the above circumstances, and a first object thereof is to provide various optical functional films having optical transparency and a predetermined refractive index. Another object of the present invention is to provide a resin composition used for forming a possible optical thin film.

A second object of the present invention is to form a light-transmitting layer having a relatively low refractive index among light-transmitting layers capable of forming various optical functional films, and in particular, it is used for reflection. It is to provide a resin composition suitable for forming a low refractive index layer of an anti-reflection film.

A third object of the present invention is to provide various optical functional films having a light-transmitting layer formed of the above resin composition and having a predetermined refractive index, particularly a low refractive index layer formed of the above resin composition. It is to provide an antireflection film formed with.

[0013]

A resin composition for an optical functional film according to the present invention for solving the above-mentioned problems comprises at least (1) acicular fine particles and (2) fluorine and / or silicon. It is characterized by comprising a binder system containing a binder component having a contained molecular structure.

When the resin composition for an optical functional film of the present invention is applied to the surface to be coated to form an optical thin film (a layer containing acicular fine particles) having optical transparency, acicular fine particles are stacked in the optical thin film. It has a different structure, and many fine holes are formed. The apparent refractive index of the thin film can be reduced by allowing air having a refractive index of 1.0 to enter the fine pores. Then, the refractive index of the thin film formed using the binder component containing fluorine and / or silicon and having a low refractive index is apparently further reduced by the action of the air that has entered the fine pores. Is obtained.

The acicular fine particles contained in the resin composition for optical functional film have a diameter of 1 to 30 nm and a length of 30.
It is preferably in the range of ˜500 nm. If the size of the needle-shaped particles is too small, it becomes difficult to form a large number of fine pores of an appropriate size, and the effect of lowering the apparent refractive index becomes weaker.If the size of the needle-shaped particles is too large, the transparency of the thin film is reduced. It is easy to damage

As the acicular fine particles, fine particles selected from the group consisting of fine particles having a pseudo-boehmite structure and fine particles in which silica sol is chain-bonded are preferably used.

The binder system contained in the resin composition for an optical functional film preferably has curing reactivity. When the binder system has curability of some reaction type such as ionizing radiation curability, heat curability, and hydrolysis polycondensation, it is possible to impart sufficient film strength to the optical thin film.

In a preferred embodiment of the present invention, the binder system of the resin composition for an optical functional film is an ionizing radiation curable binder containing an ionizing radiation curable monomer and / or oligomer having a hydrogen bond forming group. Systems can be used.

The ionizing radiation-curable monomer and / or oligomer having a hydrogen bond-forming group has a high affinity for the acicular fine particles and makes the acicular fine particles well dispersible in the resin composition for an optical functional film. be able to.

Next, the optical functional film according to the present invention has a single-layer structure comprising a light-transmitting light-transmitting layer, or a multilayer structure having one or more light-transmitting light-transmitting layers. A functional film, which is at least one of the light transmitting layers.
The layer is characterized by being a needle-shaped fine particle-containing layer formed by mixing needle-shaped fine particles in a binder containing fluorine and / or silicon.

The above-mentioned resin composition for an optical functional film according to the present invention is applied directly or through another layer to the surface of an object or a support to which some optical function is desired to be applied, dried, and optionally chemically. When cured by a reaction, it is possible to form a needle-shaped fine particle-containing layer having a light-transmitting property and a low refractive index, and having a single-layer structure exhibiting an optical function by the needle-shaped fine particle-containing layer alone, or, It is possible to form an optical functional film having a multilayer structure that exhibits an optical function by the interaction between the layer containing the acicular fine particles and another layer.

In the acicular fine particle-containing layer, the fine pores have a pore size distribution in the range of 1 to 300 nm, and the total pore volume of the fine pores is 10 to 80% of the volume of the acicular fine particle-containing layer. It is preferable to occupy

When the lower limit of the pore size distribution is less than 1 nm, the effect of lowering the refractive index is weakened, and the upper limit of the pore size distribution is 300 n.
When it is more than m, the layer containing the acicular fine particles becomes cloudy. Further, when the total pore volume of the fine pores is less than 10% of the volume of the acicular fine particle-containing layer, the refractive index lowering action becomes weak, while when it exceeds 80%, the strength of the acicular fine particle-containing layer is high. Becomes extremely weak.

In a preferred embodiment, the optical functional film according to the present invention is used as an antireflection film having a low refractive index layer formed of the needle-shaped fine particle-containing layer.

[0025]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below. The resin composition for an optical functional film according to the present invention comprises at least (1) acicular fine particles, and (2) fluorine and / or
Alternatively, it is composed of a binder system containing a binder component having a molecular structure containing silicon, and may optionally contain other components.

When the resin composition for an optical functional film of the present invention is applied to a surface to be coated to form an optical thin film (a layer containing acicular fine particles) having optical transparency, acicular fine particles are stacked in the optical thin film. It has a different structure, and many fine holes are formed. The apparent refractive index of the thin film can be reduced by allowing air having a refractive index of 1.0 to enter the fine pores.

The refractive index of the optical thin film (layer containing acicular fine particles) formed by the resin composition for an optical functional film of the present invention is determined by the acicular fine particles, the binder component, and the components other than the binder component. It depends on the refractive index and amount,
The apparent refractive index varies depending on the amount of micropores having a certain size range. As will be described later, the size of micropores is also important, and micropores of a certain size range can reduce the apparent refractive index, but if the pores are too large or too small, the Has no effect.

The acicular fine particles have a acicular structure,
Fine particles that are colloidally dispersed are preferably used. Examples of the fine particles that satisfy this condition include fine particles having a needle-like structure obtained by crystal growth of pseudo-boehmite or a needle-like structure equivalent thereto (pseudo-boehmite structure fine particles). The pseudo-boehmite structure fine particles include pseudo-boehmite needle-like fine particles themselves and alumina fine particles having a pseudo-boehmite structure.

While boehmite has a chemical structure represented by AlO (OH), in pseudo-boehmite, part of boehmite (AlO (OH)) becomes aluminum hydroxide (aluminum oxide trihydrate). And has a chemical structure that is amorphized.

As one method for preparing the pseudo-boehmite fine particles, an aluminum compound represented by the following formula 1, an oligomer derived from the aluminum compound, a complex, a salt of an inorganic acid or an organic acid, and two or more of them are used. There is a method of hydrolyzing the mixture.

Formula 1: AlR ₃ (In the above formula, the residues R may be the same or different and are halogen, alkyl having 10 or less carbon atoms, preferably 4 or less carbon atoms, alkoxyl or acyloxy,
Or it is hydroxyl. All or some of these groups may be replaced by chelating ligands. ) Specific examples of the aluminum compound represented by the above formula 1 include aluminum alkoxides such as aluminum-sec-butoxide and aluminum-iso-propoxide. Furthermore, complexes of these aluminum alkoxides with acetylacetone, ethyl acetoacetate, alkanolamines, glycols, or their derivatives can be exemplified.

Pseudo-boehmite fine particles can be obtained by dissolving the above aluminum compound in a suitable solvent and adding an appropriate amount of water for hydrolysis. Examples of the solvent for hydrolysis include ketones such as methyl ethyl ketone and methyl isobutyl ketone; alcohols such as isopropyl alcohol, methanol and ethanol; esters such as ethyl acetate and butyl acetate; halogenated hydrocarbons; toluene, xylene and the like. Aromatic hydrocarbons; and mixtures of two or more of these.

The amount of water added for hydrolysis is preferably about equimolar to the hydrolyzable groups contained in the aluminum compound. Hydrolysis is 15-3
It is carried out at a temperature of 5 ° C, preferably 22 to 28 ° C, with stirring for 5 to 30 hours, preferably 12 to 16 hours. It is preferable to use a catalyst for the hydrolysis. The catalyst is preferably an acid such as hydrochloric acid, nitric acid, sulfuric acid, acetic acid, etc.
01 to 20.0N, preferably 0.005 to 5.0
By preparing an aqueous solution of about N and using it, the water content in the aqueous solution can be utilized as the water content for hydrolysis.

On the other hand, alumina fine particles having a pseudo-boehmite structure can be obtained by firing pseudo-boehmite needle-shaped fine particles, and commercially available products (for example, Nano Whiskers A series manufactured by Daiichi Rare Element Industry Co., Ltd., Nissan Chemical Industries Ltd. ) Alumina sol etc.).

From the viewpoint of transparency and affinity with the binder component, it is preferable to use the quasi-boehmite structure fine particles in the form of a solution in the form of a sol, but powdery particles may also be used.

Further, as the fine particles having a needle-like structure and capable of being dispersed in a colloidal form, fine particles in which silica sol is bound in a chain can be used, and the same effect as that of the above-mentioned pseudo-boehmite structure fine particles can be obtained. Such acicular silica sol fine particles can also be obtained as a commercial product (for example, Snowtex-ST manufactured by Nissan Chemical Industries, Ltd.).

Regarding the size of the needle-shaped fine particles, if the needle-shaped fine particles are too small, it becomes close to the shape of the spherical fine particles, and it becomes difficult to form a large number of fine pores of an appropriate size. On the other hand, if the acicular fine particles are too large, the transparency of the thin film will be impaired. Therefore, as the acicular fine particles, those having an appropriate size should be selected so as not to cause these disadvantages, and it is preferable to use those having a diameter of 1 to 30 nm and a length of 30 to 500 nm.

The binder system (2) of the resin composition for an optical functional film contains a binder component having a molecular structure containing fluorine and / or silicon as an essential component and, if necessary, other binder component or binder. It may contain components other than the components. That is, in the resin composition for an optical functional film of the present invention, in order to reduce the refractive index of the optical thin film, a binder component having a molecular structure containing fluorine and / or silicon as a binder component that constitutes the matrix structure of the thin film. However, other binder components containing no fluorine or silicon, and components other than the binder component may be blended, depending on the physical properties required for the thin film to be formed. As components other than the binder component,
For example, compounds such as photopolymerization initiators for ionizing radiation curing, curing accelerators for thermal curing, and catalysts for hydrolysis polycondensation, which assist the curing reaction of the binder component, may be exemplified. it can.

As the binder component having a molecular structure containing fluorine and / or silicon, a compound containing fluorine and / or silicon, functioning as a binder, and capable of forming an optical thin film having optical transparency is widely used. be able to.

Specific examples of the fluorine-based binder component include polyvinylidene fluoride, polytetrafluoroethylene, 4-fluoroethylene-6-fluoropropylene copolymer, 4-fluoroethylene-perfluoroalkyl vinyl ether copolymer, 4 -Fluoroethylene-ethylene copolymer, polyvinyl fluoride, polyvinylidene fluoride, fluoroethylene-hydrocarbon-based vinyl ether copolymer, fluorine-containing monomer having an ethylenically unsaturated bond represented by the following formula 2 or formula 3 The homopolymers or copolymers thereof can be mentioned.

[0041]

[Chemical 1]

(In the formula, R ¹ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a halogen atom. Rf represents a completely or partially fluorinated alkyl group, alkenyl group,
Represents a heterocycle or aryl group. R ² and R ³ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, a heterocycle, an aryl group or a group defined by Rf above. Each of R ¹ , R ² , R ³ and Rf may have a substituent other than a fluorine atom. Further, any two or more groups of R ² , R ³ and Rf may be bonded to each other to form a ring structure. )

[0043]

[Chemical 2]

(In the formula, A represents a completely or partially fluorinated n-valent organic group. R ⁴ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a halogen atom. R ⁴ is other than a fluorine atom. And n represents an integer of 2 to 8.) As the fluorine-based binder component, a fluorine-modified product of each resin such as epoxy, polyurethane, cellulose, phenol, polyimide and silicone. In addition, other commercially available fluorine-containing polymers such as "Cytop" manufactured by Asahi Glass Co., Ltd. may be mentioned.

On the other hand, specific examples of the silicon-based binder component include polydimethylsiloxane and its derivatives, polycissesquioxane and its derivatives, polysilazane and its derivatives, and vinyl groups and (meth) acryloyl groups. -A silane coupling agent having an ethylenically unsaturated bond may be mentioned.

As the silicon-based binder component,
A polymer having a dimethylpolysiloxane structure as a basic skeleton and at least a part thereof containing a hydroxyl group, a carboxyl group, an epoxy group, a glycidyl group, an amide group or the like can be given as an example.

In order to impart sufficient film strength to the optical thin film, a binder system (2) for the resin composition for optical functional film
Preferably has an ionizing radiation curability, a thermosetting property, a hydrolysis polycondensation property, or other reaction type curability. To prepare a binder system with curing reactivity,
A binder component containing fluorine and / or silicon and having curability of some reaction type is used, or a first binder component containing fluorine and / or silicon but having no curing reactivity and fluorine and / or A second binder component which does not contain silicon but has some reaction type curability is used in combination. Further, the first binder component containing fluorine and / or silicon and having curability of some reaction type has the same reaction type curability as that of the first binder component without containing fluorine and / or silicon. A second binder component may be combined.

For example, in the case of preparing an ionizing radiation-curable binder system, a binder component containing fluorine and / or silicon and having ionizing radiation curability is used, or fluorine and / or silicon is contained. Is used in combination with a first binder component having no curing reactivity and a second binder component containing no fluorine and / or silicon but having ionizing radiation curability, or using fluorine and / or silicon. A first binder component which is contained and is curable by ionizing radiation is used in combination with a second binder component which is free of fluorine and / or silicon but is curable by ionizing radiation.

Here, as the binder component which does not contain fluorine and / or silicon but has some reaction type curability, the following compounds can be used depending on the reaction type.

Examples of the ionizing radiation-curable binder component containing no fluorine and / or silicon include monofunctional or polyfunctional monomers and oligomers having an ethylenically unsaturated bond, and more specifically, 2 -Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hydroxybutyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, carboxypolycaprolactone acrylate,
Monofunctional (meth) acrylates such as acrylic acid, methacrylic acid, acrylamide; diacrylates such as pentaerythritol triacrylate, ethylene glycol diacrylate, pentaerythritol diacrylate monostearate; trimethylolpropane triacrylate, pentaerythritol triacrylate, etc. Examples thereof include poly (meth) acrylates such as tri (meth) acrylate, pentaerythritol tetraacrylate derivatives and dipentaerythritol pentaacrylate, or oligomers obtained by polymerizing these monomers. Here, “(meth) acrylate” means acrylate and / or methacrylate.

As the thermosetting binder component containing no fluorine and / or silicon, a monofunctional or polyfunctional monomer having an epoxy group, an oligomer and an epoxy resin (polymer) can be exemplified, and more specifically, ,
As the bifunctional to trifunctional epoxy group-containing monomer,
Polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, trimethylolpropane polyglycidyl ether, 2,3-diglycidyloxystyrene, 3,4-diglycidyloxystyrene,
2,4-diglycidyloxystyrene, 3,5-diglycidyloxystyrene, 2,6-diglycidyloxystyrene, 5-vinylpyrogallol triglycidyl ether, 4-vinylpyrogallol triglycidyl ether,
Vinyl phloroglycinol triglycidyl ether,
2,3-dihydroxymethylstyrene diglycidyl ether, 3,4-dihydroxymethylstyrene diglycidyl ether, 2,4-dihydroxymethylstyrene diglycidyl ether, 3,5-dihydroxymethylstyrene diglycidyl ether, 2,6-dihydroxymethyl Styrene diglycidyl ether, 2,3,4-trihydroxymethylstyrene triglycidyl ether, 1,
3,5-trihydroxymethylstyrene triglycidyl ether and the like can be mentioned.

Further, as the high molecular weight epoxy resin,
Bisphenol A type epoxy resin, bisphenol F type epoxy resin, brominated bisphenol A type epoxy resin, bisphenol S type epoxy resin, diphenyl ether type epoxy resin, hydroquinone type epoxy resin,
Naphthalene type epoxy resin, biphenyl type epoxy resin, fluorene type epoxy resin, phenol novolac type epoxy resin, orthocresol novolac type epoxy resin, trishydroxyphenylmethane type epoxy resin, trifunctional epoxy resin, tetraphenylolethane type epoxy resin, Dicyclopentadiene phenol type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol A nucleus-containing polyol type epoxy resin, polypropylene glycol type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin,
Glyoxal type epoxy resin, alicyclic type epoxy resin, heterocyclic type epoxy resin, etc. can be mentioned.

Examples of the hydrolytic polycondensable binder component containing no fluorine and / or silicon include titanate coupling agents. Specifically, as titanate coupling agents, product names Planeact KR-TTS and KR-46, which are commercially available from Ajinomoto Co., Inc.
B, KR-55, KR-41B, KR-38S, KR-
138S, KR-238S, 338X, KR-44, K
R-9SA, KR-ET and the like can be mentioned, and further,
Tetramethoxy titanium, tetraethoxy titanium, tetraisopropoxy titanium, tetra n-propoxy titanium,
Metal alkoxides such as tetra n-butoxy titanium, tetra sec-butoxy titanium, and tetra tert-butoxy titanium can also be mentioned.

The curing-reactive binder component as described above is a polyfunctional polymerizable compound capable of forming a network structure by a crosslinking reaction regardless of whether it contains fluorine and / or silicon. preferable.

Further, in order to disperse the acicular fine particles in the resin composition for an optical functional film well, it is preferable that the binder component used in the binder system has a high affinity with the acicular fine particles. From such a viewpoint, when a binder component having a functional group capable of forming a hydrogen bond with acicular fine particles (hydrogen bond forming group) such as a hydroxyl group is used, the binder component may or may not contain fluorine and / or silicon. Regardless, it contributes to the dispersibility of the acicular fine particles, which is preferable.

As the binder component having a hydroxyl group in the molecule, among those having ionizing radiation curability, pentaerythritol polyfunctional (meth) acrylate or dipentaerythritol polyfunctional (meth) acrylate, which is a hydroxyl group in the molecule, Examples thereof include those which are not esterified and remain, for example, pentaerythritol triacrylate and the like.

As the binder component having a hydrogen bond-forming group, polyamide resin, polyester resin, alkyd resin, unsaturated polyester resin, polycarbonate resin, silicone resin, polyphenylene oxide resin, phenol resin, xylene resin, amino resin may be used. ,
Examples include resins with essentially polar groups such as melamine resins, urea resins, polyether resins, epoxy resins, penton resins, urethane resins, and resins with monomers containing hydrogen bond-forming groups introduced by a copolymerization method. can do.

In the case of preparing a binder system having some curing reactivity, components for assisting the reaction may be blended as necessary according to the reaction mode. For example, when preparing an ionizing radiation-curable binder system, a photopolymerization initiator is usually added together with an ionizing radiation-curable binder component. When preparing a thermosetting binder system, a curing accelerator is usually added together with the thermosetting binder component. When preparing a hydrolytic polycondensable binder system, a hydrolysis catalyst is usually added together with a hydrolytic polycondensable binder component.

Examples of the photopolymerization initiator used together with the ionizing radiation-curable binder component include acetophenones, benzophenones, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, and 2.
3-Dialkyldione compounds, disulfide compounds, thiuram compounds, fluoroamine compounds and the like are used. More specifically, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropane-1
-One, benzyl dimethyl ketone, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropane-1
-One, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl)
Examples thereof include 2-hydroxy-2-methylpropan-1-one and benzophenone. Of these, 1-
Hydroxy-cyclohexyl-phenyl-ketone and 2-methyl-1- [4- (methylthio) phenyl]
Since 2-morpholinopropan-1-one initiates and accelerates the polymerization reaction upon irradiation with ionizing radiation even in a small amount,
It is preferably used in the present invention. These can be used alone or in combination of both. These also exist in commercial products, for example 1-hydroxy-cyclohexyl-phenyl-ketone is available from Ciba Geigy under the trade name Irgacure 184 (Irgacure 184).

As the curing accelerator used together with the thermosetting binder component, for example, when an epoxy resin is used, polycarboxylic acid anhydride or polycarboxylic acid can be exemplified.

Specific examples of the polycarboxylic acid anhydride include:
Phthalic anhydride, itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarballylic anhydride, maleic anhydride, hexahydrophthalic anhydride,
Aliphatic or alicyclic dicarboxylic acid anhydrides such as dimethyltetrahydrophthalic anhydride, hymic acid anhydride, and nazic anhydride; 1,2,3,4-butanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride Aliphatic polycarboxylic acid dianhydrides such as; aromatic polycarboxylic acid anhydrides such as pyromellitic anhydride, trimellitic anhydride, and benzophenone tetracarboxylic anhydride; ethylene glycol bis trimellitate, glycerin tris trimellitate, etc. Of the ester group-containing acid anhydrides, and particularly preferably, aromatic polyvalent carboxylic acid anhydrides. Further, a commercially available epoxy resin curing agent composed of carboxylic acid anhydride can also be suitably used.

Specific examples of the polycarboxylic acid include:
Aliphatic polycarboxylic acids such as succinic acid, glutaric acid, adipic acid, butanetetracarboxylic acid, maleic acid and itaconic acid; hexahydrophthalic acid, 1,2-cyclohexanedicarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid , Aliphatic polycarboxylic acids such as cyclopentane tetracarboxylic acid, and phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, trimellitic acid, 1, 4,
Aromatic polycarboxylic acids such as 5,8-naphthalene tetracarboxylic acid and benzophenone tetracarboxylic acid can be mentioned, and aromatic polycarboxylic acids are preferable.

Examples of the hydrolysis catalyst used together with the hydrolytic polycondensable binder component include inorganic acids such as hydrochloric acid, nitric acid and sulfuric acid, and organic acids such as acetic acid.

The organic solvent for dissolving and dispersing the solid component of the resin composition for an optical functional film of the present invention is not particularly limited,
Various substances, for example, alcohols such as isopropyl alcohol, methanol and ethanol; ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; esters such as ethyl acetate and butyl acetate; halogenated hydrocarbons; aromatics such as toluene and xylene Group hydrocarbons; or mixtures thereof can be used.

To prepare the resin composition for an optical functional film of the present invention, a material is selected from the above-mentioned materials according to the performance required for the optical thin film to be formed and the type of curing reaction. Then, the mixture may be mixed in any order, a medium such as beads may be added to the obtained mixture, and appropriate dispersion treatment may be performed with a paint shaker, a bead mill or the like.

When the mixing ratio of the acicular fine particles and the binder component in the resin composition for an optical functional film is changed, the amount and size of the fine pores formed in the acicular fine particle-containing layer are changed, and the fine pores are changed. Since the optical effect due to the holes fluctuates, the amounts of the acicular fine particles and the binder component also fluctuate, and the optical effects due to the respective components also fluctuate, the refractive index changes.
Therefore, in the resin composition for an optical functional film of the present invention, the refractive index can be adjusted by changing the mixing ratio of the acicular fine particles and the binder component.

The total amount of the binder component is 10
It is preferable to adjust in the range of 5 to 70 parts by weight with respect to 0 parts by weight. If the binder component is less than 5 parts by weight,
Needle-like fine particles easily fall off from the thin film, and conversely, when the amount exceeds 70 parts by weight, the fine pores are almost completely filled,
Since the amount of air entering the thin film is small, the refractive index may not be sufficiently lowered.

The amount of the organic solvent is appropriately selected so that each component can be uniformly dissolved and dispersed, no aggregation occurs during storage after preparation, and a concentration that is not too dilute during coating. Adjust. Within the range where this condition is satisfied, use a small amount of solvent to prepare a high-concentration coating liquid, store it in a state that does not take up the volume, and take out the necessary amount at the time of use to obtain a concentration suitable for coating work. It is preferably diluted. In the state immediately before coating, the solid content concentration is usually adjusted to be about 1 to 30% by weight when all the compounded materials including the liquid monomer components and the like are considered as solid content.

Preferable examples of the resin composition for an optical functional film include pseudo-boehmite fine particles as the acicular fine particles (1),
Alumina fine particles having a pseudo-boehmite structure, and one or two or more kinds of fine particles of colloidal silica having an average primary particle diameter of 10 to 20 nm, which are selected from fine particles in which five or more colloidal silicas are linked in a chain, Polyvinylidene fluoride is used as a binder component containing fluorine and / or silicon in the molecular structure, and an ethylenically unsaturated bond such as pentaerythritol triacrylate is contained as a binder component for imparting ionizing radiation curability. An example of the coating liquid is a polyfunctional monomer or oligomer having a hydroxyl group remaining, and the photopolymerization initiator as described above is used to dissolve and disperse each of these materials in a solvent.

The above-exemplified resin composition for optical functional film is
Since the ionizing radiation-curable polyfunctional monomer or oligomer is combined with the binder component containing fluorine and / or silicon in the molecular structure, the content of fluorine and / or silicon is increased to make the refractive index of the binder component very high. It can be made small, and the polyfunctional monomer or oligomer is cross-linked by irradiation of ionizing radiation to cure the entire matrix, and a coating strength that can withstand practical use is obtained.

Furthermore, the above-exemplified resin composition for an optical functional film uses an ionizing radiation-curable polyfunctional monomer or oligomer having a hydroxyl group. Such a polyfunctional monomer or oligomer and pseudo-boehmite fine particles, pseudo-boehmite particles are used. Alumina fine particles having a boehmite structure, or because they form hydrogen bonds with acicular fine particles made of colloidal silica, these acicular fine particles are uniformly dispersed in the coating liquid, and the fine pores are evenly distributed. A coated film can be formed.

Next, the optical functional film of the present invention obtained by using the above resin composition for an optical functional film will be described.

The resin composition for an optical functional film of the present invention is applied directly or through another layer to the surface of an object or a support to which some optical function is desired to be applied, followed by drying and, if necessary, a chemical reaction. When cured by, it is possible to form a needle-shaped fine particle-containing layer having a light-transmitting property and a low refractive index, and having a single-layer structure exhibiting an optical function by the needle-shaped fine particle-containing layer alone, or It is possible to form an optical functional film having a multi-layered structure that exhibits an optical function by the interaction between the acicular fine particle-containing layer and another layer.

Examples of objects to which some kind of optical function is to be given include, for example, displays for word processors, computers, televisions, polarizing plates used for liquid crystal display elements, sunglasses lenses, prescription glasses lenses, optical lenses such as finder lenses for cameras, Examples thereof include covers of various instruments, window glasses of automobiles and trains, and the like.

When it is difficult to directly form an optical thin film on the surface of an object to which an optical function is desired, an optical functional film is formed on the surface of a light transmissive support such as a transparent resin film. It is possible to prepare a sheet or unit having optical functionality and arrange it on the surface of an object to which an optical function is desired. Examples of the light-transmitting support include glass plate; acetate butyrate cellulose film, polyether sulfone film, polyacrylic resin film, polyurethane resin film, polyester film, polycarbonate film, polysulfone film, polyether film, trimethyl. Although a pentene film, a polyetherketone film, a (meth) acrylonitrile film, etc. can be used, a uniaxially stretched polyester film is particularly preferable because it is excellent in transparency and has no optical anisotropy. The thickness of these supports is usually about 8 μm to 1000 μm.

The acicular fine particle-containing layer is prepared by dissolving and dispersing the resin composition for an optical functional film of the present invention in a suitable solvent to prepare a coating solution, and applying the coating solution by spin coating, dipping, Spray method, roll coater method, meniscus coater method,
Apply on the surface to be coated by a known coating method such as flexographic printing method, screen printing method, bead coater method, etc., dry, and if necessary, cure by an appropriate method such as ionizing radiation irradiation, heating, hydrolysis polycondensation It can be formed by The resin composition for an optical functional film of the present invention can form an optical thin film by coating on the surface to be coated by a general coating method, so compared with the case of forming an optical thin film by a vapor phase method. It is advantageous in terms of control of coating atmosphere, equipment cost, and mass productivity. Moreover, the resin composition for an optical functional film of the present invention can be uniformly applied at a normal coating speed, and unlike the case of using spherical fine particles, the solvent is convected in the coating film by rapid drying. Since the micro holes can be formed without any problem, the production speed is high. Therefore, the productivity of the optical thin film is excellent.

The optical functional film thus formed has a single-layer structure composed of a light-transmitting light-transmitting layer or a multi-layer structure having one or more light-transmitting light-transmitting layers. And at least one of the light transmitting layers
The layer is a needle-shaped fine particle-containing layer obtained by mixing needle-shaped fine particles in a binder containing fluorine and / or silicon.
When a polyfunctional compound having a curing reactivity is used as a binder component of the resin composition for an optical functional film, the binder of the acicular fine particle-containing layer is cured due to cross-linking, and excellent in film strength. Therefore, it is preferable.

The needle-shaped fine particle-containing layer formed from the resin composition for an optical functional film of the present invention has a relatively low refractive index as an optical thin film, and specifically, the needle-shaped fine particles and the binder component are By changing the blending ratio, the refractive index
It can be adjusted to a predetermined value of 1.45 or less. At present, the limit of the refractive index of the optical thin film formed by the coating method is about 1.38, but
The needle-shaped fine particle-containing layer can have a refractive index lower than the current limit while ensuring the film physical properties required for practical use.

The acicular fine particle-containing layer has a structure in which acicular fine particles are stacked in a matrix of a thin film formed by using a binder component having a relatively low refractive index, and fine voids are formed by the accumulating structure of the acicular fine particles. Are formed in large numbers, and the air having a refractive index of 1.0 is introduced into these fine pores, whereby the apparent refractive index of the needle-shaped fine particle-containing layer becomes small. Therefore, when the optical effect of the fine pores changes depending on the amount and size of the fine holes formed in the needle-shaped fine particle-containing layer, the apparent refractive index of the needle-shaped fine particle-containing layer also changes accordingly.

In the present invention, the fine pores formed in the needle-shaped fine particle-containing layer have a fine pore size distribution in the range of 1 to 300 nm, and the total pore volume of the fine pores is the needle-shaped fine particle-containing layer. It is preferable to occupy 10 to 80% of the volume.

When the lower limit of the pore size distribution is less than 1 nm,
In some cases, there are too many pores of too small size to weaken the effect of lowering the refractive index, so that the apparent refractive index cannot be reduced to a desired value. The fine pores having a too small pore size cannot form a structure in which air can penetrate into the acicular fine particle-containing layer to a depth necessary for lowering the apparent refractive index, and are substantially acicular. It does not contribute to the apparent reduction of the refractive index because it only causes air to be trapped at the interface between the fine particle-containing layer and the layer adjacent thereto. On the other hand, when the upper limit of the pore size distribution is 300 nm or more, visible light is scattered and the needle-shaped fine particle-containing layer becomes cloudy, which may be practically inconvenient.

When the total pore volume of the fine pores is less than 10% of the volume of the acicular fine particle-containing layer, the refractive index lowering action is weakened, while when it exceeds 80%, the acicular fine particle-containing layer is contained. It is not preferable because the strength of the layer becomes extremely weak.

The thickness of the acicular fine particle-containing layer varies greatly depending on the use of the acicular fine particle-containing layer and whether or not other layers are combined, but it is generally 50 to 150 n.
It is preferably within the range of m, and particularly preferably within the range of 80 to 100 nm. In particular, when used as the low refractive index layer of the antireflection film, the thickness of the acicular fine particle-containing layer is preferably 50 nm to 3 μm.

The optical functional film according to the present invention may have a single-layer structure composed of only one acicular fine particle-containing layer as long as it can exhibit the required optical function. For example, in the case of forming an antireflection film, the surface of an object or a support to which an antireflection function is to be imparted is coated with a needle-shaped fine particle-containing layer having a refractive index lower than that of the surface to prevent the reflection. The effect is obtained.

When the optical functional film according to the present invention has a multilayer structure, various layers other than the acicular fine particle-containing layer may be laminated in any order depending on the use of the optical functional film. be able to. For example, in the case of forming an antireflection film, a hard coat layer for increasing the surface hardness of the antireflection film is provided on the surface of an object or a support for which an antireflection function is desired to be provided, and a medium refractive index layer or a It is possible to provide one or more high refractive index layers, provide the above-mentioned acicular fine particle layer as a low refractive index layer thereon, and further provide an antifouling layer thereon.

Since the needle-shaped fine particle-containing layer formed from the resin composition for an optical functional film of the present invention can have a very low refractive index, it is suitable for forming a low refractive index layer of an antireflection film. Used for. Therefore, an antireflection film having a low refractive index layer formed by using the resin composition for an optical functional film of the present invention will be described below.

The antireflection film is provided on the surface of an object or a support for which reflection is to be prevented by providing only one light transmitting layer having a refractive index lower than that of the surface, or for an object or support for which reflection is to be prevented. The surface has a structure in which two or more light transmitting layers are laminated so that the magnitudes of the refractive index values alternate with each other and the light transmitting layer having the smallest refractive index is located on the outermost surface. Among the antireflection films, the layer with the highest refractive index is referred to as the high refractive index layer, the layer with the lowest refractive index is referred to as the low refractive index layer, and the other layers having intermediate refractive indices are the medium refractive index layers. Called. When the antireflection film has a single layer structure, the only light transmitting layer can be considered as the low refractive index layer.

In addition to the high, medium and low refractive index layers, the antireflection film has a hard coat layer for increasing the surface hardness of the antireflection film, and an antifouling layer for preventing the surface of the antireflection film from becoming dirty. Alternatively, other layers may be provided. The high, medium, and low refractive index layers and other layers constituting the antireflection film need to have a light-transmitting property such that the display on the coated surface can be visually recognized.

FIG. 1 shows an example (101) of an antireflection film belonging to the optical functional film according to the present invention. Antireflection film 10
Reference numeral 1 denotes an antiglare hard coat layer 2, a high refractive index layer 3, a medium refractive index layer 4, and a low refractive index on the surface of an object 1 to be coated, which is either an object for which reflection is desired to be prevented or a light transmissive support. It has a multilayer structure in which the layer 5 and the antifouling layer 6 are laminated in this order.

As an object for which reflection is desired to be prevented, for example,
Various articles such as those already mentioned, that is, displays for word processors, computers, televisions, polarizing plates used for liquid crystal display devices, sunglasses lenses, prescription eyeglass lenses, optical lenses such as camera finder lenses, covers for various instruments, automobiles. A window glass of a train or a train can be exemplified.

As the light-transmissive support, various plate-like or film-like materials as described above, that is, glass plate; acetate butyrate cellulose film, polyether sulfone film, polyacrylic resin film, Examples thereof include polyurethane resin films, polyester films, polycarbonate films, polysulfone films, polyether films, trimethylpentene films, polyetherketone films, (meth) acrylonitrile films and the like. An antireflection film or an antireflection film can be formed by providing an antireflection film on these plate-shaped or film-shaped supports. These antireflection members can be installed on the surface of an object such as a word processor, a computer, a display of a television, etc., where it is difficult to directly form an antireflection film.

The antiglare hard coat layer 2 provided first on the surface of the article 1 is formed of a transparent resin such as an ionizing radiation-curable polyfunctional (meth) acrylate monomer and / or oligomer, which provides sufficient hardness. This is a layer in which an inorganic or organic filler 7 is dispersed inside the formed thin film. The hard coat layer 2 has a mat-shaped surface unevenness and scatters transmitted light and reflected light, and therefore functions as a hard coat layer for improving surface hardness and an antiglare layer (anti-glare layer) that suppresses glare on the surface. Exert its function as. The hard coat layer 2 can be formed by applying a coating liquid, in which a transparent resin and a filler are dissolved and dispersed, onto the surface of the object to be coated 1, drying the liquid, and curing the liquid by a chemical reaction if necessary. The thickness of the hard coat layer 2 is usually about 0.5 nm to 20 μm.

The medium refractive index layer 3 and the high refractive index layer 4 which are sequentially provided on the antiglare hard coat layer 2 can be formed by a coating method or a vapor phase method. When the coating method is used, for example, a transparent resin having a relatively high refractive index such as polyimide, poly-N-vinylcarbazole, and a phenol resin, and transparent fine particles having a relatively high refractive index such as titania, zirconia, and zinc oxide are dissolved. It can be formed by applying the dispersed coating liquid on the surface to be coated, drying, and if necessary, curing by a chemical reaction. When the coating method is used, the thickness of the medium to high refractive index layer is usually 50
nm to about 300 nm. Further, in the case of the vapor phase method, the thickness 50 made of a material having a relatively high refractive index such as titanium oxide (TiOx), zinc sulfide, or zinc oxide is used.
A vapor-deposited film or a sputtered film having a thickness of about nm to 300 nm is formed as a medium to high refractive index layer. The refractive index of the medium to high refractive index layer is usually adjusted to about 1.65 to 2.3.

The low refractive index layer 5 provided on the high refractive index layer 4 is formed by a coating method using the resin composition for an optical functional film of the present invention and has a thickness of about 50 nm to 3 μm. It is a layer containing fine particles. The refractive index of the low refractive index layer is usually adjusted to about 1.10 to 1.40.

Antifouling layer 6 provided on the low refractive index layer 5
Can be formed by applying a coating liquid in which a fluorine-based antifouling material or the like is dissolved and dispersed to the surface to be coated, drying the liquid, and curing the liquid by a chemical reaction, if necessary. The thickness of the antifouling layer is usually about 5 nm to 50 nm.

The multi-layered antireflection film 101 thus formed exerts not only an excellent antireflection effect but also an antiglare effect for suppressing glare on the surface, so that very excellent visibility is obtained. .

[0097]

(Example) (1) Preparation of pseudo-boehmite A flask (with stirring blades and thermometer) was charged with ion-exchanged water 9
00 g and 676 g of isopropyl alcohol were charged, and the liquid temperature was heated to 80 ° C. While stirring, 306 g of aluminum isopropoxide was added, and the liquid temperature was kept at 80 ° C. to carry out hydrolysis reaction for 5 hours. Next, set the liquid temperature to 95 ° C.
The temperature was raised to 4.5 and acetic acid (4.5 g) was added, followed by 48 hours at 50 ° C.
Hold on and solve. Then, the solution was concentrated until the liquid amount became 900 g to obtain a white sol. The solid obtained by drying this sol was pseudo-boehmite according to powder X-ray diffraction.

Further, the sol was coated on a glass plate, the solvent was dried, and the particle size was measured by observation with an electron microscope. The average diameter was 10 nm, and the length was 170 nm.
It was needle-shaped.

(2) Preparation of coating liquid 1.0 g of the obtained dry sol was added to a solution containing a fluorine-containing binder component (trade name: OPSTAR JM5010, manufactured by JSR Co., Ltd., solid content 10% by weight, refractive index 1). .41, a methyl isobutyl ketone solution, and an initiator mixed) (3.0 g) to obtain a coating solution.

Example 2 10.0 g of sol particles obtained by drying an aqueous solution of alumina sol (trade name: Alumina sol-100, manufactured by Nissan Chemical Industries, Ltd., solid content: 10% by weight)
Is a UV-curable silicone hard coat paint containing a silicon-containing binder component (trade name: X-12-240
0, manufactured by Shin-Etsu Chemical Co., Ltd., solid content 30% by weight, and dissolved in 10.0 g of methyl ethyl ketone solution, and 0.15 g of a photopolymerization initiator (trade name Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) Dissolve the
A coating solution was obtained.

Example 3 10.0 g of a chain-like colloidal silica dispersion liquid (trade name: Organosilica sol IPA-ST-UP, manufactured by Nissan Chemical Industries, Ltd., solid content 10% by weight, isopropyl alcohol solution) was contained in silicon. The same UV-curable silicone hard coat paint (Brand name X-12-2400) used in Example 2 containing a binder component.
1.0 g of the same photopolymerization initiator (trade name Irgacure 184) as used in Example 2 was dispersed in 1.0 g.
5 g was dissolved to obtain a coating solution.

Example 4 10.0 g of the same chain colloidal silica dispersion (trade name Organosilica sol IPA-ST-UP) used in Example 3 was used in Example 1 containing a fluorine-containing binder component. A coating solution was obtained by dispersing in 3.0 g of the same solution (trade name: OPSTAR JM5010) used.

(Comparative Example 1) The same solution (trade name: OPSTAR JM5010) used in Example 1 containing a fluorine-containing binder component was used as it was as a coating solution.

Comparative Example 2 The same UV-curable silicone hard coat coating composition (trade name X-12-2400) used in Example 2 containing a silicon-containing binder component was prepared.
It was used as it was as a coating solution.

Comparative Example 3 3.0 g of the same solution containing the fluorine-containing binder component used in Example 1 (trade name Opstar JM5010) was added to spherical colloidal silica (trade name Organosilica Sol IPA-ST, Nissan). 10.0 g of a solid content of 30% by weight, isopropyl alcohol solution manufactured by Kagaku Kogyo Co., Ltd. was dispersed to obtain a coating solution.

(Example 5: Preparation of single-layer type antireflection film) (5-a) Formation of transparent hard coat layer A 88 μm-thick PET base material (A-4350, Toyobo Co., Ltd.) having one surface treated to improve the adhesiveness. )) Is prepared, and the coating liquid for hard coat (1) having the following composition is applied to the surface for easy adhesion treatment by a bar coater, the solvent is dried, and then a UV irradiation device (Fusion UV Systems Japan KK)
(Manufactured by Hamamatsu Co., Ltd.) was used as a light source to cure the H bulb at an irradiation dose of 500 mJ to form a transparent hard coat layer having a film thickness of 10 μm to obtain a hard coat substrate 5-a. <Hard coat coating liquid (1)> Dipentaerythritol pentaacrylate: 7.0
Parts by weight-Colloidal silica dispersion (trade name MEK-ST, Nissan Chemical Industries, Ltd., solid content 25% by weight): 12 parts by weight-photopolymerization initiator (trade name IRGACURE 184; Ciba Specialty Chemicals Co., Ltd.) (Manufactured): 0.3 parts by weight, methyl isobutyl ketone: 0.3 parts by weight (5-b) Formation of low refractive index layer The coating liquids of Examples 1 to 4 and Comparative Examples 1 to 3 were prepared in the above process. After coating with a bar coater on the hard coat layer of the hard coat base material 5-a and drying the solvent,
An H bulb of a UV irradiation device (manufactured by Fusion UV Systems Japan Co., Ltd.) was used as a light source and cured at an irradiation amount of 300 mJ to form a low refractive index layer, and an antireflection film 5-
b was obtained. The film thickness of the low refractive index layer was set so that the minimum reflectance was around 550 nm when the reflectance was measured with a spectrophotometer (manufactured by Shimadzu Corporation).

(Evaluation Method) The following evaluations were performed.
The evaluation results are shown in Table 1.

(1) The coating liquid for the refractive index of the coating film was applied onto a silicon wafer by a spin coater, the solvent was dried, and the H bulb of a UV irradiation device (Fusion UV Systems Japan KK) was used as a light source. The film thickness is 0.1μ when cured with an irradiation dose of 500 mJ.
m coating film was obtained. The refractive index of this coating film was measured using a spectroscopic ellipsometer (UVISEL; manufactured by Jobin Evon Co., Ltd.) at a wavelength of helium ion laser light of 633 nm.

(2) Reflectance The reflectance of the antireflection film 5-b was measured with a spectrophotometer (manufactured by Shimadzu Corporation) at an incident angle of 7 ° and a reflection angle of 7 °. It was determined.

(3) Coating film hardness For the antireflection film 5-b, JIS K5600-5-
A pencil hardness test based on No. 4 was conducted, and a portion where no scratch could be visually confirmed under a load of 1 kg was marked with the corresponding pencil type.

(4) Adhesion Test Regarding the antireflection film 5-b, JIS K5600-5-
A cellophane tape peeling test (cross-cut method) based on the cross-cut method based on No. 6 was performed to confirm the presence or absence of peeling.

[0112]

[Table 1]

[0113]

As described above, the acicular fine particle-containing layer formed of the resin composition for an optical functional film according to the present invention has a structure in which acicular fine particles are stacked in a thinned matrix. The apparent refractive index is reduced by the air having the refractive index of 1.0 entering a large number of fine holes formed by the accumulating structure of the acicular fine particles. Then, the refractive index of the thin film formed by using the low-refractive index binder component containing fluorine and / or silicon is apparently further reduced by the action of the air entering the fine pores. Is obtained.

Therefore, when the above-mentioned acicular fine particle-containing layer is formed directly on the surface of an object or a support to which some optical function is desired or through another layer, the acicular fine particle-containing layer alone exhibits an optical function. Thus, an optically functional film having a single layer structure or a multilayer structure exhibiting an optical function by the interaction between the acicular fine particle-containing layer and another layer can be obtained.

The resin composition for an optical functional film according to the present invention can be applied to the surface to be coated by a general coating method to form an optical thin film, and can be applied uniformly at a normal coating speed. It is also excellent in productivity of the optical thin film, since it can be applied to the substrate and fine pores can be formed without any problem even if it is dried relatively quickly.

The resin composition for an optical functional film according to the present invention is particularly suitable for forming a low refractive index layer of an antireflection film, and an antireflection film having excellent antireflection performance can be obtained. Also, the productivity of the antireflection film is high.

[Brief description of drawings]

FIG. 1 is a view schematically showing a cross section of an example of an antireflection film according to the present invention.

[Explanation of symbols]

101 ... Antireflection film 1 ... Object to be coated 2 ... Hard coat layer 3 ... Medium refractive index layer 4 ... High refractive index layer 5 ... Low refractive index layer 6 ... Antifouling layer 7 ... Filler

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08L 83/04 G02B 5/02 C G02B 5/02 1/10 AF term (reference) 2H042 BA04 BA12 BA15 BA20 2K009 AA06 AA15 BB02 BB14 BB24 BB28 CC03 CC06 CC09 CC14 CC21 CC26 CC42 DD02 DD03 DD06 EE05 4F071 AA26 AA67 AB18 AD01 AD02 AF29 AF30 AF31 AG12 AH12 AH16 BC01 BC02 4J002 BD121 BD131 BD141 BG0876 GP36 FA DE FA1 CP031 DE031

Claims (11)

[Claims] 1. At least (1) acicular fine particles, and
(2) A resin composition for an optical functional film, comprising a binder system containing a binder component having a molecular structure containing fluorine and / or silicon. 2. The acicular fine particles have a diameter of 1 to 30 nm,
The resin composition for an optical functional film according to claim 2, which has a length of 30 to 500 nm. 3. The optical element according to claim 1, wherein the acicular fine particles are fine particles selected from the group consisting of pseudo-boehmite structure fine particles and fine particles in which silica sol is bound in a chain. A resin composition for a functional film. 4. The resin composition for an optical functional film according to claim 1, wherein the binder system has curing reactivity. 5. Optical according to claim 4, characterized in that the binder system is an ionizing radiation-curable binder system containing ionizing radiation-curable monomers and / or oligomers having hydrogen bond-forming groups. A resin composition for a functional film. 6. An optical functional film having a single-layer structure composed of a light-transmitting light-transmitting layer or a multilayer structure having one or more light-transmitting light-transmitting layers, the light-transmitting layer At least one of the layers is an acicular fine particle-containing layer obtained by mixing acicular fine particles in a binder containing fluorine and / or silicon. 7. The acicular fine particles have a diameter of 1 to 30 nm,
The optical functional film according to claim 6, which has a length of 30 to 500 nm. 8. The optical according to claim 6, wherein the acicular fine particles are fine particles selected from the group consisting of pseudo-boehmite structure fine particles and fine particles in which silica sol is bound in a chain. Functional membrane. 9. The optical functional film according to claim 6, wherein the binder of the layer containing the acicular fine particles is crosslinked and hardened. 10. The acicular fine particle-containing layer has fine pores having pore diameters distributed in the range of 1 to 300 nm, and the total pore volume of the fine pores is 10 times the volume of the acicular fine particle-containing layer.
The optical functional film according to any one of claims 6 to 9, wherein the optical functional film occupies -80%. 11. An antireflection film comprising the optically functional film according to any one of claims 6 to 10, wherein the antireflection film comprises a single layer structure comprising the light transmitting layer or a multilayer structure comprising two or more light transmitting layers laminated. And an antireflection film having one of the layers is a low refractive index layer formed of the acicular fine particle-containing layer.