JP2007102208A - Optical film, anti-reflection film, and polarizing plate and image display device using the optical film and the anti-reflection film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an optical film which has satisfactory conductivity and superior antistatic performance, can avoid white powder staining and dust sticking due to peeling of layer and disconnection of antistatic agent in a manufacturing step and handling (coating, conveyance, etc.) and can avoid repelling fault accompanied by the white powder staining and dust sticking, and to provide a polarizing plate and an image display device that has been subjected to anti-reflection treatment using such an optical film. <P>SOLUTION: The optical film comprises an antistatic layer, a protective layer and a light scattering layer made of a resin layer with fine particles dispersed therein, in the order on a transparent film, wherein acicular metal oxide particles, having the ratio of major axis to minor axis of 3 to 50, are contained in the antistatic layer. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an optical film, an antireflection film, and a polarizing plate and a liquid crystal display device using the same.

  In general, the antireflection film is used in a display device such as a cathode ray tube display (CRT), a plasma display (PDP), an electroluminescence display (ELD), or a liquid crystal display (LCD), and a contrast reduction or image due to reflection of external light. In order to prevent reflection of light, it is arranged on the outermost surface of the display so as to reduce the reflectance by using the principle of optical interference. In addition, dust tends to adhere to the display panel, and there is a high possibility of scratching when the attached dust is wiped.

  Therefore, an antireflection material provided with an antireflection function and a conductive function on a transparent film is arranged on the front surface of the display to prevent scratches, prevent charging, and prevent reflection.

  For example, an antireflection layer in which a conductive layer in which transparent conductive ultrafine particles of metal oxide are dispersed on a transparent substrate and a low reflection layer having a refractive index lower than that of the conductive layer is laminated (patent) Reference 1).

  However, when conductive fine particles are used as described above, so-called white powder stains that fall off the surface of the layer and adhere to the surface of the transport roll due to contact friction with the transport roll during the manufacturing process occur. There is a concern that it is easy. That is, particles detached from the layer and adhering to the transport roll or the like may re-adhere on the substrate during the manufacturing process and cause coating defects, foreign matter defects, and scratches. Is significantly reduced.

If the conductive fine particles are reduced in order to avoid such a desorption phenomenon, the white powder stain due to the desorption of the fine particles is certainly improved, but it is difficult to say that the antistatic layer has sufficient conductivity. The adhesion of dust and the like cannot be completely avoided. On the contrary, when the amount of the conductive fine particles is increased, the number of particles detached from the layer is increased, so that white powder dirt and dust adhesion are deteriorated, and in addition, the haze value is increased due to the increase.
JP 2003-294904 A

An object of the present invention is to solve the conventional manufacturing problems and achieve the following objects. In other words, the present invention has good electrical conductivity and excellent antistatic performance, and prevents white powder contamination and dust adhesion due to peeling of the layer and desorption of the antistatic agent during the manufacturing process and handling (during application, transportation, etc.). It is an object of the present invention to provide an optical film that can be avoided and that can prevent cissing failure associated with the white powder stain and dust adhesion.
Another object of the present invention is to provide an optical film having strong film properties, excellent transparency and scratch resistance in addition to the above properties.
Furthermore, this invention is obtaining the antireflection film excellent in antireflection and other optical performance in addition to electroconductivity.
Another object of the present invention is to provide a high-quality polarizing plate and an image display device provided with the above-described optical film, particularly an antireflection film.

As a result of intensive investigations, the present inventors have sequentially laminated an antistatic layer, a protective layer, and a light scattering layer composed of a resin layer in which fine particles are dispersed to achieve both conductivity and antireflection, and a well-balanced antireflection. It was found that a film was obtained.
According to the present invention, an optical film, an antireflection film, a polarizing plate and an image display device having the following constitution are provided, and the above object is achieved.
(1) On a transparent film, an antistatic layer, a protective layer, and a light scattering layer composed of a resin layer in which fine particles are dispersed are sequentially provided. The antistatic layer has a ratio of a major axis to a minor axis (major axis / An optical film comprising acicular metal oxide particles having a minor axis ratio of 3 to 50.
(2) A reaction product of (1) a resin having a plurality of carboxylic acid groups in the molecule and a weight average molecular weight of 2000 or more and (2) a compound having a plurality of carbodiimide structures in the molecule in the antistatic layer. The optical film as described in (1) above, which is contained.
(3) The optical film according to the above (1) or (2), wherein the haze value when only an antistatic layer and a protective layer are provided on a transparent film is 1.0% or less.
(4) The optical film according to any one of (1) to (3) above, wherein the surface resistance value logSR at 25 ° C. and 55% RH of the optical film is 12Ω / sq or less.

(5) The optical film as described in any one of (1) to (4) above, wherein the protective layer has a thickness of 0.01 μm to 0.5 μm.
(6) The optical film according to any one of (1) to (5), wherein the light scattering layer contains fine particles whose surfaces are coated with a conductive material.
(7) The antireflection according to any one of (1) to (6), wherein a low refractive index layer having a refractive index lower than that of the light scattering layer is provided on the light scattering layer. the film.
(8) The antireflection film as described in (7) above, wherein the low refractive index layer contains hollow silica particles.
(9) The above (7) or (8), wherein any layer on the transparent film contains at least one of an organosilane compound represented by the following general formula [A] and a derivative thereof. ) Antireflection film as described.
Formula _{^{[A] (R 10) m}} -Si (X) 4-m
[In the general formula [A], R ¹⁰ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. X represents a hydroxyl group or a hydrolyzable group. m represents an integer of 1 to 3. ]

(10) The optical film or antireflection film as described in any one of (1) to (9) above, wherein a haze value of the optical film or the antireflection film is 0 to 90%.
(11) Any one of (1) to (10) above, wherein a haze value resulting from surface scattering of the optical film or the antireflection film is 0 to 15%, and an internal haze is 0 to 90%. The optical film or antireflection film described in 1.
(12) In the polarizing plate having a polarizing film and protective films provided on both sides of the polarizing film, at least one of the protective films is the optical film or the antireflection according to any one of (1) to (11) above. A polarizing plate characterized by being a film.

(13) An image in which the optical film or antireflection film according to any one of (1) to (11) above, or the polarizing plate according to (12) above is disposed on an image display surface. Display device.
(14) The image display device according to (13), wherein the image display device is a TN, STN, IPS, VA, or OCB mode transmissive, reflective, or transflective liquid crystal display device. .

  By forming an antireflection film using the optical film according to the present invention, an antireflection film excellent in antireflection and other optical performances can be obtained. The polarizing plate and image display device of the present invention, which has been subjected to antireflection treatment with such a film, were able to obtain high-quality images with excellent visibility. Furthermore, when it is arranged on the outermost surface of the display, dust is difficult to adhere.

  Hereinafter, the present invention will be described in more detail. In the present specification, when a numerical value represents a physical property value, a characteristic value, etc., the description “(numerical value 1) to (numerical value 2)” means “(numerical value 1) or more and (numerical value 2) or less”. . In the present specification, the description “(meth) acrylate” means “at least one of acrylate and methacrylate”. The same applies to “(meth) acrylic acid” and the like.

The optical film of the present invention has an antistatic layer containing acicular metal oxide particles that exhibit electrical conductivity by electronic conduction, and the antistatic layer further has (1) a plurality of carboxylic acid groups in the molecule, Moreover, it is preferable to contain a reaction product of a resin having a weight average molecular weight of 2000 or more and (2) a compound having a plurality of carbodiimide structures in the molecule.
Hereinafter, it explains with the component of the coating liquid for antistatic layer formation used for manufacture of this invention, and its manufacturing method.

[(1) Acicular metal oxide particles that exhibit electrical conductivity by electronic conduction]
Specific examples of the acicular metal oxide particles (hereinafter referred to as a conductive compound as appropriate) that exhibit conductivity by electronic conduction used in the coating solution for forming an antistatic layer of the present invention include, for example, tin oxide. Indium oxide, zinc oxide, titanium oxide, magnesium oxide, aluminum oxide, antimony oxide, and the like can be used. In particular, tin oxide and indium oxide are preferable, and among these, tin oxide doped with antimony exhibits good conductivity and transparency and can be suitably used.

  The primary particle diameter of the metal oxide is preferably 0.3 μm or less, particularly preferably 0.2 μm or less, from the viewpoint of the planarity of the antistatic layer. More preferably, it is 0.01-0.1 micrometer. When the particle size is increased, it is necessary to increase the coating film thickness to improve the flatness, but even if the antistatic layer is increased, the high conductivity corresponding to that is not obtained, and on the contrary the transparency is increased. There is a possibility that problems such as lowering may occur.

In general, in the coating process of the antistatic layer, metal (oxide) particles fall off from the film surface due to contact friction with a transport roll, etc., adhere to the roll, and there is a problem of causing scratches and poor coating. By using acicular particles, the amount of conductive metal (oxide) added can be reduced without degrading the charging performance, and the above-described advantage of effectively preventing the particles from dropping off can be obtained. It is what you have.
The average major axis length of the metal oxide in the case of using acicular particles is preferably 0.01 to 0.5 μm or less, particularly preferably 0.02 to 0.4 μm or less, from the viewpoint of the flatness of the antistatic layer. . More preferably, it is 0.02-0.3 micrometer. Further, in the particle structure, those having an acicular structure in which the ratio of the major axis to the minor axis is in the range of 3 to 50 are preferable, and in particular, the acicular structure in which the ratio is in the range of 4 to 40 is preferable. When such needle-like structured particles are used, when the ratio of the major axis to the minor axis is less than 3, there is a concern that the contact probability between the particles when applied in the form of a thin film is lowered and the conductivity is lowered. There is.
The particle shape of the conductive material can be confirmed by taking an image of 100,000 times or more with an electron microscope. In particular, the aggregate state of the particles in the film can be observed with a transmission electron microscope.

Among these conductive materials, a particularly preferable material that can be used in the present invention is tin oxide having a needle-like structure.
The amount of these conductive materials added to the coating solution for forming the antistatic layer is preferably in the range of 10 to 95% by mass, more preferably in the range of 20 to 90% by mass in terms of solid content. .

[(1) Reaction product of a resin having a plurality of carboxylic acid groups in the molecule and a weight average molecular weight of 2000 or more and (2) a compound having a plurality of carbodiimide structures in the molecule]
The “(1) resin having a plurality of carboxylic acid groups in the molecule and having a weight average molecular weight of 2000 or more” (hereinafter, referred to as “carboxylic acid group-containing resin” as appropriate) used in the present invention is a weight average molecular weight of 2000 or more. Any resin can be used as long as it has two or more carboxylic acid groups introduced therein. The carboxylic acid group may be introduced after the resin is synthesized, or may be introduced by copolymerizing a structural unit having a carboxylic acid group, but the latter is preferred from the viewpoint of synthesis suitability.
Examples of carboxylic acid group-containing resins that can be used in the present invention include polyacrylic acid esters, polymethacrylic acid esters, polyester resins, polyurethane resins, polystyrene, polyacrylonitrile, polyvinyl acetate, polyvinyl alcohol, styrene-butadiene resins, and vinylidene chloride. A resin obtained by copolymerizing a monomer having a carboxylic acid group during synthesis of a resin such as a resin, a vinyl chloride resin, or an ethylene-vinyl acetate resin is preferred.
Among them, one or more monomers selected from the group consisting of acrylic acid and methacrylic acid and one or more monomers having a double bond capable of polymerization reaction, specifically, for example, methyl (meth) acrylate , (Meth) acrylate esters such as ethyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate Preferred are resins obtained by copolymerization with monomers such as styrene, divinylbenzene, acrylamide, acrylonitrile, vinyl acetate, vinyl chloride, vinylidene chloride, ethylene, propylene, butadiene, and isoprene.
Other examples of the carboxylic acid group-containing resin preferably include those obtained by introducing a carboxylic acid group into a hydrophilic polymer such as gelatin, polyvinyl alcohol, celluloses, styrene-maleic acid resin, phenol resin, and polyvinylpyrrolidone.

  The carboxylic acid group contained in the carboxylic acid group-containing resin may be introduced as it is as an acid group (carboxylic acid group), but it may be added by a base such as ammonia, amines, alkali metals, alkaline earth metals, etc. The functional group in a neutralized state may be introduced in a hydrated state, and is also included in the carboxylic acid group in the present invention.

When preparing an antistatic layer coating solution containing these resins, an aqueous coating solution is preferable from the viewpoint of stability over time. In the case of an aqueous conductive coating solution, these resins can be blended as an emulsion obtained by emulsion polymerization, an emulsion obtained by solution polymerization, neutralized with a base, and the solvent is replaced with water to emulsify. Also. If the resin itself is a water-soluble resin, it can be used as an aqueous solution as it is.
In consideration of the viscosity of the coating solution, an aqueous coating solution containing the resin in an emulsion state is preferable.

The weight average molecular weight of the carboxylic acid group-containing resin used in the present invention is preferably 2000 or more from the viewpoint of the strength of the formed film. In addition, although there is no restriction | limiting in particular in the upper limit of molecular weight, From a viewpoint of synthetic suitability, specifically molecular weight control and its reproducibility, it is preferable that it is 150,000 or less, and 3000-100000 are especially preferable.
The carboxylic acid group-containing resin has a plurality of carboxylic acid groups in the molecule. The amount of carboxylic acid groups introduced per molecule of the resin can be detected by the acid value, but the acid value of the resin is preferably in the range of 5 to 400, particularly preferably 10 to 300. Here, the acid value of the resin is represented by the weight (mg) of potassium hydroxide required to neutralize 100 g of the resin.
When obtaining by neutralization titration, the acid values of all acids including carboxylic acid are obtained, but when the copolymerization ratio is known in advance, the equivalent of carboxylic acid can be calculated by the molar ratio. .

  The “(2) compound having a plurality of carbodiimide structures in the molecule” (hereinafter appropriately referred to as a carbodiimide compound) used in the present invention is not particularly limited as long as it is a compound having a plurality of carbodiimide groups in the molecule. Can be used.

Polycarbodiimide is usually synthesized by a condensation reaction of organic diisocyanate. In the present invention, as described above, it is preferable to use an aqueous coating liquid as the coating liquid for forming an antistatic layer. However, when a compound having a plurality of carbodiimide structures is blended in such an aqueous coating liquid, the terminal isocyanate is mixed with On the other hand, it is preferable to impart hydrophilicity by reacting a compound having a hydrophilic group together with a functional group having reactivity with an isocyanate group.
Here, (2) the organic group of the organic diisocyanate used for the synthesis of the compound having a plurality of carbodiimide structures in the molecule is not particularly limited, and either an aromatic group or an aliphatic group or a mixture thereof can be used. However, aliphatic systems are particularly preferable from the viewpoint of reactivity.
As the synthetic raw material, organic isocyanate, organic diisocyanate, organic triisocyanate and the like are used.
As examples of organic isocyanates, aromatic isocyanates, aliphatic isocyanates, and mixtures thereof can be used.
Specifically, 4,4′-diphenylmethane diisocyanate, 4,4-diphenyldimethylmethane diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, cyclohexane Diisocyanate, xylylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 1,3-phenylene diisocyanate, etc. are used. As organic monoisocyanates, isophorone isocyanate, phenyl isocyanate are used. Cyclohexyl isocyanate, butyl isocyanate, naphthyl isocyanate and the like are used.
Moreover, the carbodiimide type compound that can be used in the present invention is also available as a commercial product such as Carbodilite V-02-L2 (trade name: manufactured by Nisshinbo Co., Ltd.).

The reaction product that contributes to improving the film strength in the antistatic layer of the present invention has a cross-linked structure formed by the addition reaction of carboxylic acid and carbodiimide. That is, the reaction product has a structure in which the oxygen atom of the carboxylic acid is nucleophilically added to the carbon atom of the carbodiimide functional group, and such a crosslinked structure is heated at about 30 to 140 ° C. during drying of the film, particularly for a short time. In the case of heating at a temperature of 60 to 140 ° C., it is preferably formed without heating at a high temperature that adversely affects the support substrate, such as heating at 150 ° C. or higher.
The suitable mixing ratio of (1) carboxylic acid group-containing resin and (2) carbodiimide compound can be calculated from the acid value of the resin and the carbodiimide equivalent of the carbodiimide compound. From the viewpoint of improving the film strength due to the formation of a crosslinked structure and the flexibility of the formed film, the ratio of the number of moles of carbodiimide groups to the number of moles of carboxylic acid groups is preferably 1:20 to 10: 1. 1:10 to 5: 1 is particularly preferable, and 1: 5 to 3: 1 is more preferable.

In preparing the coating solution for forming the antistatic layer, the sum of solid content concentrations of (1) carboxylic acid group-containing resin and (2) carbodiimide compound is 10% by mass or less. From the viewpoint of sex. When the total solid content concentration of both is higher than 10% by mass, the intermolecular distance between the carboxylic acid group and the carbodiimide functional group is shortened and the collision probability is increased. It tends to occur, and as a result, the pot life is shortened, which is not preferable in terms of production suitability. The particularly preferred solid content concentration is 0.1 to 8% by mass, and more preferably 0.3 to 6% by mass.
Moreover, it is preferable that the solid content concentration of the reaction product of (1) carboxylic acid group-containing resin and (2) carbodiimide-based compound in the formed film (conductive film) is 5 to 90% by mass, More preferably, it is the range of 10-80 mass%, Most preferably, it is the range of 15-60 mass%.

[Other additives]
The antistatic layer of the present invention can contain various additives as necessary as long as the effects of the present invention are not impaired.
For example, a matting agent or wax may be used to adjust the surface characteristics of the antistatic layer, particularly the friction coefficient.
As the matting agent, organic and inorganic materials such as silica, calcium carbonate, magnesium carbonate, barium sulfate, polystyrene, polystyrene-divinylbenzene copolymer, polymethyl methacrylate, melamine, and benzoguanamine can be used.
Examples of waxes that can be used include paraffin wax, microwax, polyethylene wax, polyester wax, carnauba wax, fatty acid, fatty acid amide, and metal soap.
In order to improve the coating property, a surfactant may be added to the coating solution for forming the antistatic layer. The surfactant is not particularly limited, and any of aliphatic, aromatic, and fluorine surfactants may be used, and nonionic, anionic, and cationic surfactants may be used.

[Formation of antistatic layer]
The antistatic layer according to the present invention can be formed by dissolving these materials for forming an antistatic layer in an appropriate solvent, and applying and drying on a support described later.
The antistatic layer is formed by preparing a coating solution containing a conductive compound that exhibits conductivity by electronic conduction, coating the coating solution on at least one side of the support, and drying.
More preferable antistatic layers include: a conductive compound that exhibits electrical conductivity by electronic conduction; (1) a resin having a plurality of carboxylic acid groups in the molecule and having an average molecular weight of 2000 or more; and (2) an intramolecular A compound having a plurality of carbodiimide structures, (1) a resin having a plurality of carboxylic acid groups in the molecule and having an average molecular weight of 2000 or more, and (2) a compound having a plurality of carbodiimide structures in the molecule Are prepared by preparing an aqueous coating solution having a solid content concentration of 10% by mass or less, applying the aqueous coating solution to at least one surface of the support, and drying.

As a solvent used for forming the antistatic layer, for example, water is a main component, and a water-soluble organic solvent that can be mixed with water as required, such as lower alcohols such as methanol, ethanol, isopropyl alcohol, acetone, methyl ethyl ketone, etc. An aqueous solvent partially containing
Moreover, as an organic solvent, solvents such as lower alcohols such as methanol, ethanol and isopropyl alcohol, acetone, methyl ethyl ketone, ethyl acetate, propylene glycol monoacetate, toluene, xylene, petroleum ether and the like can be used.
In the production method of the present invention, from the viewpoint of environmental protection and explosion protection, the solvent of the coating solution is preferably an aqueous solvent, and in particular, the organic solvent other than water is preferably 3% by mass or less in the total solvent, It is preferable that it is 1 mass% or less.
As a coating method, for example, a known method such as dip coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating, and extrusion coating can be used.
Moreover, it is preferable to dry the antistatic layer after coating at a temperature of 30 to 140 ° C. for 10 seconds to 15 minutes. In the present invention, crosslinking is carried out by the reaction between the carboxylic acid group in the (1) carboxylic acid group-containing resin and the carbodiimide structure in the carbodiimide-based compound as described above without using a crosslinking agent that is crosslinked under high temperature conditions that are generally used. Since the structure is formed, it is possible to form an antistatic layer having sufficient film strength even under such mild drying conditions that do not affect the support.

  The film thickness after coating and drying of the antistatic layer of the present invention is not particularly limited, and may be appropriately determined depending on the use of the optical film and the type of the conductive material to be used. The film thickness is preferably 3 μm or less, particularly preferably 0.01 to 2 μm. When the average film thickness of the antistatic layer exceeds 3 μm, there is a concern that problems such as a decrease in transparency and coloring may occur. In applications where transparency is not required, the thickness is preferably about 0.03 to 5 μm from the viewpoint of film properties and antistatic effects.

The antistatic layer is preferably substantially transparent. Specifically, the haze of the antistatic layer is preferably 10% or less, more preferably 5% or less, further preferably 3% or less, and most preferably 1% or less. . Further, the transmittance of light having a wavelength of 550 nm is preferably 50% or more, more preferably 60% or more, further preferably 65% or more, and most preferably 70% or more.
The antistatic layer of the present invention has excellent strength, and the specific strength of the antistatic layer is preferably 1 H or higher pencil hardness (as defined in JIS-K-5400), preferably H or higher. Is more preferably 3H or more, and most preferably 4H or more.

  Further, when only the antistatic layer and the protective layer are provided on the transparent film, the haze value is 10% or less, preferably 3%, more preferably 1% or less, preferably 0.8% or less. Most preferably.

[Protective layer]
In the optical film of the present invention, a protective layer is provided on the antistatic layer in order to protect the antistatic layer.
Although there is no restriction | limiting in the application method of a protective layer, It is desirable to apply | coat simultaneously with an antistatic layer.
The material used for the protective layer is not particularly limited as long as it can form a film with sufficient adhesion to the antistatic layer. For example, methacrylic resin, acrylic resin, polyester resin, polyurethane resin, SBR resin, polyamide resin, cellulose derivative, gelatin, polystyrene, polyvinyl chloride, polyvinylidene chloride, silicone resin, fluorine-containing resin, polyethylene resin, polypropylene resin Epoxy resin, styrene-maleic acid resin, phenol resin, ethylene vinyl acetate resin, polyvinyl alcohol, phenol resin and the like can be used. In particular, it is desirable to use a polyester resin.

In forming the protective layer, these resins may be dissolved in an appropriate solvent and applied on the antistatic layer. The solvent is appropriately selected depending on the characteristics of the resin used, and examples thereof include a method in which the solvent is dissolved and applied in an organic solvent, a method in which the solvent is applied as an aqueous dispersion, or an aqueous solution.
In the protective layer of the present invention, a matting agent or a wax may be used as necessary to adjust the surface characteristics, particularly the friction coefficient. As examples of the matting agent and the wax, the same materials as those mentioned in the antistatic layer can be used.
In order to improve the coating property, a surfactant may be added to the protective layer-forming coating solution. The surfactant is not particularly limited, and any of aliphatic, aromatic, and fluorine surfactants may be used, and nonionic, anionic, and cationic surfactants may be used.

Although the thickness of the protective layer depends on the characteristics of the resin used, it is generally preferably in the range of 0.01 μm to 0.5 μm, particularly preferably 0.01 μm to 0.3 μm. More preferably, it is 0.02 micrometer-0.2 micrometer.
If the film thickness is too thin, a sufficient protective effect of the antistatic layer may not be obtained, and if the film thickness is 0.5 μm or more, the surface resistance increases, and the antistatic layer originates from the antistatic layer. There is a concern to reduce the effect.

(Light scattering layer)
The optical film of the present invention is provided with a light scattering layer (also referred to as a light diffusion layer) made of a resin layer in which fine particles are dispersed on the protective layer.
The light scattering layer is a light-scattering hard coat layer and includes fine particles having a size capable of light scattering, and the fine particles are dispersed in the resin layer. The light scattering layer may have an antiglare function in addition to the light scattering property.
The light scattering layer in the present invention preferably contains translucent fine particles whose surface is coated with a conductive substance.

(Translucent fine particles whose surface is coated with a conductive material)
The material for forming the substrate fine particles may be organic or inorganic. As the organic material, various plastic materials can be used. For example, polyethylene, polypropylene, polymethylpentene, polyvinyl chloride, polytetrafluoroethylene, polystyrene, polymethyl methacrylate, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyimide, poly Linear or cross-linked polymers such as sulfone, polyphenylene oxide, and polyacetal; epoxy resin, phenol resin, melamine resin, unsaturated polyester resin, divinylbenzene polymer, divinylbenzene-styrene copolymer, divinylbenzene-acrylic acid ester And resins having a network structure such as polymers, diallyl phthalate polymers, triallyl isocyanurate polymers, and benzoguanamine polymers.

  Among these resins, particularly preferred are those having a network structure such as divinylbenzene polymer, divinylbenzene-styrene copolymer, divinylbenzene-acrylate copolymer, diallyl phthalate polymer, and benzoguanamine polymer. Resin.

The inorganic particles are not particularly limited, and conventionally known particles can be used. For example, an oxide of at least one metal selected from silicon, zirconium, titanium, aluminum, indium, zinc, tin, and antimony, and specific examples include ZrO ₂ , TiO ₂ , Al ₂ O ₃ , In ₂ O _3. ZnO, SnO ₂ , Sb ₂ O ₃ , ITO and the like. In addition, BaSO ₄ , CaCO ₃ , talc and kaolin may be used.

  As the shape of the substrate fine particles, for example, a spherical shape, an elliptical spherical shape, and a cylindrical shape are preferable. In the case of a true sphere, the diameter is preferably in the range of 0.1 to 100 μm, the particularly preferable diameter is 0.5 to 50 μm, and the more preferable diameter is 1 to 20 μm. In the case of an oval shape, the minor axis is preferably in the range of 0.1 to 1000 μm, and the preferred range is 1 to 100 μm. The ratio of the major axis to the minor axis is preferably in the range of 1 to 10, and the preferred range is 1 to 5. The base fine particles are particularly preferably spherical.

  The conductive substance that coats the substrate fine particles preferably forms a conductive metal layer or metal oxide layer. Examples of the material for forming the metal layer include gold, silver, copper, platinum, palladium, cobalt, Examples thereof include nickel, iron, indium, tin, lead, and alloys containing these as main components. Further, the metal layer may have a multilayer structure. As a material for forming the metal oxide layer, tin oxide, indium oxide, zinc oxide, titanium oxide, magnesium oxide, aluminum oxide, antimony oxide, and the like can be used. In particular, tin oxide and indium oxide are preferable, and among them, tin oxide doped with antimony exhibits good conductivity and transparency and can be suitably used.

  Examples of methods for forming a metal layer or metal oxide layer on the surface of the substrate fine particles include a coating method by precipitation, a method by electroless plating, a coating method by physical vapor deposition such as vacuum deposition, ion plating, ion sputtering, etc. There is.

The thickness of the coated metal layer or the coated metal oxide layer is preferably in the range of 0.02 to 5.0 μm. If the thickness is less than 0.02 μm, it is difficult to obtain desired conductivity. When the thickness exceeds 5.0 μm, the coating layer is easily peeled off due to a difference in thermal expansion coefficient between the substrate fine particles and the coating layer.
The translucent fine particles whose surfaces are coated with a conductive substance are preferably contained in an amount of 0.05 to 30% by mass, more preferably 0.07 to 20% by mass, based on the solid content of the layer. It is more preferable to contain 1-10 mass%.

The surface resistance value (log SR) at 25 ° C. and 55% RH of the optical film of the present invention is preferably 12 Ω / sq or less, and more preferably 10 Ω / sq or less. Further, the surface resistance value is preferably 5 Ω / sq or more in order to be compatible with the transparency of the coating film. Accordingly, the surface resistance value of the optical film of the present invention at 25 ° C. and 55% RH is preferably 5 to 12 Ω / sq, more preferably 5 to 9 Ω / sq, and 5 to 8 Ω / sq. Most preferably it is. The surface resistance value at 25 ° C. and 10% RH is preferably 14 Ω / sq or less, more preferably 12 Ω / sq or less.
The surface resistance of the antistatic layer can be measured by a four probe method.

  The optical film of the present invention preferably has a center line average roughness (Ra) in the range of 0.03 to 0.40 μm. If it exceeds 0.40 μm, problems such as glare and whitening of the surface when external light is reflected occur. The optical film of the present invention preferably has a haze of 0 to 90%, more preferably 10 to 85%, and most preferably 15 to 80%. The haze resulting from internal scattering (hereinafter referred to as internal haze) is preferably 0% to 90%, more preferably 10% to 85%, and still more preferably 15% to 80%. Further, haze caused by surface scattering (hereinafter referred to as surface haze) is preferably 0 to 15%, and preferably 0 to 10%. Further, the value of image definition is preferably 5 to 90%, more preferably 15 to 90%. .

  Next, various compounds that can be used in addition to the antistatic layer and protective layer of the present invention will be described.

1- (1) Binder The film of the present invention can be formed by a crosslinking reaction or a polymerization reaction of an ionizing radiation curable compound. That is, a coating composition containing an ionizing radiation-curable polyfunctional monomer or polyfunctional oligomer as a binder is coated on a transparent support, and the polyfunctional monomer or polyfunctional oligomer is formed by a crosslinking reaction or a polymerization reaction. be able to.
The functional group of the ionizing radiation curable polyfunctional monomer or polyfunctional oligomer is preferably a light, electron beam, or radiation polymerizable group, and among them, a photopolymerizable functional group is preferable.
Examples of the photopolymerizable functional group include unsaturated polymerizable functional groups such as a (meth) acryloyl group, a vinyl group, a styryl group, and an allyl group. Among them, a (meth) acryloyl group is preferable.

As a specific example of a photopolymerizable polyfunctional monomer having a photopolymerizable functional group,
(Meth) acrylic acid diesters of alkylene glycol such as neopentyl glycol acrylate, 1,6-hexanediol (meth) acrylate, propylene glycol di (meth) acrylate;
(Meth) acrylic acid diesters of polyoxyalkylene glycols such as triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate;
(Meth) acrylic acid diesters of polyhydric alcohols such as pentaerythritol di (meth) acrylate;
(Meth) acrylic acid diesters of ethylene oxide or propylene oxide adducts such as 2,2-bis {4- (acryloxy · diethoxy) phenyl} propane and 2-bis {4- (acryloxy · polypropoxy) phenyl} propane ;
Etc.

  Furthermore, epoxy (meth) acrylates, urethane (meth) acrylates, and polyester (meth) acrylates are also preferably used as the photopolymerizable polyfunctional monomer.

  Among these, esters of polyhydric alcohol and (meth) acrylic acid are preferable. More preferably, a polyfunctional monomer having 3 or more (meth) acryloyl groups in one molecule is preferable. Specifically, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, 1,2,4-cyclohexanetetra (meth) acrylate, pentaglycerol triacrylate, pentaerythritol tetra (meth) acrylate, penta Erythritol tri (meth) acrylate, (di) pentaerythritol triacrylate, (di) pentaerythritol pentaacrylate, (di) pentaerythritol tetra (meth) acrylate, (di) pentaerythritol hexa (meth) acrylate, tripentaerythritol triacrylate , Tripentaerythritol hexatriacrylate and the like. In the present specification, “(meth) acrylate”, “(meth) acrylic acid”, and “(meth) acryloyl” represent “acrylate or methacrylate”, “acrylic acid or methacrylic acid”, and “acryloyl or methacryloyl”, respectively. .

As the monomer binder, monomers having different refractive indexes can be used to control the refractive index of each layer. Examples of particularly high refractive index monomers include bis (4-methacryloylthiophenyl) sulfide, vinyl naphthalene, vinyl phenyl sulfide, 4-methacryloxyphenyl-4′-methoxyphenyl thioether, and the like.
Further, for example, dendrimers described in JP-A-2005-76005 and JP-A-2005-36105, and norbornene ring-containing monomers as described in JP-A-2005-60425 can also be used.

Two or more polyfunctional monomers may be used in combination.
Polymerization of these monomers having an ethylenically unsaturated group can be carried out by irradiation with ionizing radiation or heating in the presence of a photo radical initiator or a thermal radical initiator.
It is preferable to use a photopolymerization initiator for the polymerization reaction of the photopolymerizable polyfunctional monomer. As the photopolymerization initiator, a photoradical polymerization initiator and a photocationic polymerization initiator are preferable, and a photoradical polymerization initiator is particularly preferable.

1- (2) Polymer Binder In the present invention, a polymer or a crosslinked polymer can be used as the binder. The crosslinked polymer preferably has an anionic group. The polymer having a crosslinked anionic group has a structure in which the main chain of the polymer having an anionic group is crosslinked.

Examples of the polymer main chain include polyolefin (saturated hydrocarbon), polyether, polyurea, polyurethane, polyester, polyamine, polyamide and melamine resin. A polyolefin main chain, a polyether main chain and a polyurea main chain are preferable, a polyolefin main chain and a polyether main chain are more preferable, and a polyolefin main chain is most preferable.
The polyolefin main chain consists of saturated hydrocarbons. The polyolefin main chain is obtained, for example, by an addition polymerization reaction of an unsaturated polymerizable group. The polyether main chain has repeating units bonded by an ether bond (—O—). The polyether main chain is obtained, for example, by a ring-opening polymerization reaction of an epoxy group. In the polyurea main chain, repeating units are bonded by a urea bond (—NH—CO—NH—). The polyurea main chain is obtained, for example, by a condensation polymerization reaction between an isocyanate group and an amino group. In the polyurethane main chain, repeating units are bonded by a urethane bond (—NH—CO—O—). The polyurethane main chain is obtained, for example, by a polycondensation reaction between an isocyanate group and a hydroxyl group (including an N-methylol group). The polyester main chain has repeating units bonded by an ester bond (—CO—O—). The polyester main chain is obtained, for example, by a polycondensation reaction between a carboxyl group (including an acid halide group) and a hydroxyl group (including an N-methylol group). The polyamine main chain has repeating units bonded by imino bonds (—NH—). The polyamine main chain is obtained, for example, by a ring-opening polymerization reaction of an ethyleneimine group. The polyamide main chain has repeating units bonded by an amide bond (—NH—CO—). The polyamide main chain is obtained, for example, by a reaction between an isocyanate group and a carboxyl group (including an acid halide group). The melamine resin main chain is obtained, for example, by a polycondensation reaction between a triazine group (eg, melamine) and an aldehyde (eg, formaldehyde). In the melamine resin, the main chain itself has a crosslinked structure.

The anionic group is bonded directly to the main chain of the polymer or bonded to the main chain via a linking group. The anionic group is preferably bonded to the main chain as a side chain via a linking group.
Examples of the anionic group include a carboxylic acid group (carboxyl), a sulfonic acid group (sulfo), and a phosphoric acid group (phosphono), and a sulfonic acid group and a phosphoric acid group are preferable.
The anionic group may be in a salt state. The cation that forms a salt with the anionic group is preferably an alkali metal ion. Moreover, the proton of the anionic group may be dissociated.
The linking group that binds the anionic group and the polymer main chain is preferably a divalent group selected from —CO—, O—, an alkylene group, an arylene group, and combinations thereof.

  The crosslinked structure is a structure in which two or more main chains are chemically bonded (preferably covalent bonds), but it is preferable to covalently bond three or more main chains. The cross-linked structure is preferably composed of a divalent or higher valent group selected from —CO—, —O—, —S—, a nitrogen atom, a phosphorus atom, an aliphatic residue, an aromatic residue, and combinations thereof.

  The crosslinked polymer having an anionic group is preferably a copolymer having a repeating unit having an anionic group and a repeating unit having a crosslinked structure. The proportion of the repeating unit having an anionic group in the copolymer is preferably 2 to 96% by mass, more preferably 4 to 94% by mass, and most preferably 6 to 92% by mass. The repeating unit may have two or more anionic groups. The proportion of the repeating unit having a crosslinked structure in the copolymer is preferably 4 to 98% by mass, more preferably 6 to 96% by mass, and most preferably 8 to 94% by mass.

The repeating unit of the polymer having a crosslinked anionic group may have both an anionic group and a crosslinked structure. Further, other repeating units (repeating units having neither an anionic group nor a crosslinked structure) may be contained.
Other repeating units are preferably a repeating unit having an amino group or a quaternary ammonium group and a repeating unit having a benzene ring. The amino group or the quaternary ammonium group has a function of maintaining the dispersed state of the inorganic particles, like the anionic group. The same effect can be obtained even when the amino group, quaternary ammonium group and benzene ring are contained in a repeating unit having an anionic group or a repeating unit having a crosslinked structure.
In a repeating unit having an amino group or a quaternary ammonium group, the amino group or quaternary ammonium group is directly bonded to the main chain of the polymer or bonded to the main chain through a linking group. The amino group or quaternary ammonium group is preferably bonded to the main chain as a side chain via a linking group. The amino group or quaternary ammonium group is preferably a secondary amino group, a tertiary amino group or a quaternary ammonium group, more preferably a tertiary amino group or a quaternary ammonium group. The group bonded to the nitrogen atom of the secondary amino group, tertiary amino group or quaternary ammonium group is preferably an alkyl group, preferably an alkyl group having 1 to 12 carbon atoms, Is more preferably an alkyl group of 1 to 6. The counter ion of the quaternary ammonium group is preferably a halide ion. The linking group that connects the amino group or quaternary ammonium group to the polymer main chain is a divalent group selected from -CO-, -NH-, -O-, an alkylene group, an arylene group, and combinations thereof. Preferably there is. When the polymer having a crosslinked anionic group contains a repeating unit having an amino group or a quaternary ammonium group, the ratio is preferably 0.06 to 32% by mass, and 0.08 to 30% by mass. It is more preferable that it is 0.1 to 28% by mass.

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

Examples of the structural unit for imparting crosslinking reactivity include units represented by the following (A), (B), and (C).
(A): a structural unit obtained by polymerization of a monomer having a self-crosslinkable functional group in the molecule in advance such as glycidyl (meth) acrylate and glycidyl vinyl ether,
(B): a monomer having a carboxyl group, a hydroxy group, an amino group, a sulfo group, etc. (for example, (meth) acrylic acid, methylol (meth) acrylate, hydroxyalkyl (meth) acrylate, allyl acrylate, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether) , Maleic acid, crotonic acid, etc.)
(C): a group having a crosslinkable functional group separately from a group that reacts with the functional group of (A) or (B) in the molecule and a structural unit of (A) or (B) above. Examples of the structural unit to be obtained include (for example, a structural unit that can be synthesized by a technique such as allowing acrylic acid chloride to act on a hydroxyl group).

  In the structural unit (C), the crosslinkable functional group is preferably a photopolymerizable group. Examples of the photopolymerizable group include (meth) acryloyl group, alkenyl group, cinnamoyl group, cinnamylideneacetyl group, benzalacetophenone group, styrylpyridine group, α-phenylmaleimide group, phenylazide group, sulfonylazide. Group, carbonyl azide group, diazo group, o-quinonediazide group, furylacryloyl group, coumarin group, pyrone group, anthracene group, benzophenone group, stilbene group, dithiocarbamate group, xanthate group, 1,2,3-thiadiazole group, cyclo A propene group, an azadioxabicyclo group, etc. can be mentioned, These may be not only 1 type but 2 or more types. Of these, a (meth) acryloyl group and a cinnamoyl group are preferable, and a (meth) acryloyl group is particularly preferable.

Specific methods for preparing the photopolymerizable group-containing copolymer include, but are not limited to, the following methods.
a. A method of esterifying by reacting a (meth) acrylic acid chloride with a crosslinkable functional group-containing copolymer containing a hydroxyl group,
b. A method of urethanization by reacting an isocyanate group-containing (meth) acrylic ester with a crosslinkable functional group-containing copolymer containing a hydroxyl group,
c. A method of reacting (meth) acrylic acid with a crosslinkable functional group-containing copolymer containing an epoxy group,
d. A method in which a crosslinkable functional group-containing copolymer containing a carboxyl group is reacted with a containing (meth) acrylic acid ester containing an epoxy group for esterification.
The amount of the photopolymerizable group introduced can be arbitrarily adjusted. From the viewpoints of surface stability of the coating film, reduction of surface failure when coexisting with inorganic particles, and improvement of film strength, carboxyl groups, hydroxyl groups, etc. It is also preferable to leave a certain amount.

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

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

  The fluorine-containing polymer particularly useful in the present invention is a random copolymer of perfluoroolefin and vinyl ethers or vinyl esters. In particular, it preferably has a group capable of undergoing a crosslinking reaction alone (a radical reactive group such as a (meth) acryloyl group, a ring-opening polymerizable group such as an epoxy group or an oxetanyl group). These crosslinkable group-containing polymerized units preferably occupy 5 to 70 mol% of the total polymerized units of the polymer, particularly preferably 30 to 60 mol%. Regarding preferred polymers, JP-A-2002-243907, JP-A-2002-372601, JP-A-2003-26732, JP-A-2003-222702, JP-A-2003-294911, JP-A-2003-329804, JP-A-2004. -4444 and JP, 2004-45462, A can be mentioned.

  Moreover, it is preferable that the polysiloxane structure is introduce | transduced in the fluorine-containing polymer of this invention in order to provide antifouling property. There is no limitation on the method of introducing the polysiloxane structure, but for example, as described in JP-A-6-93100, JP-A-11-189621, JP-A-11-228631 and JP-A-2000-313709, the initiation of silicone macroazo A method of introducing a polysiloxane block copolymer component using an agent, and a method of introducing a polysiloxane graft copolymer component using a silicone macromer as described in JP-A-2-251555 and JP-A-2-308806. preferable. Particularly preferred compounds include the polymers of Examples 1, 2, and 3 of JP-A-11-189621, and the copolymers A-2 and A-3 of JP-A-2-251555. These polysiloxane components are preferably 0.5 to 10% by mass in the polymer, and particularly preferably 1 to 5% by mass.

  The preferred molecular weight of the polymer that can be preferably used in the present invention is a mass average molecular weight of 5,000 or more, preferably 10,000 to 500,000, most preferably 15,000 to 200,000. By using polymers having different average molecular weights in combination, it is possible to improve the surface state of the coating film and the scratch resistance.

  As described in JP-A-10-25388 and JP-A-2000-17028, a curing agent having a polymerizable unsaturated group may be used in combination with the above polymer. Moreover, combined use with the compound which has a fluorine-containing polyfunctional polymerizable unsaturated group as described in Unexamined-Japanese-Patent No. 2002-145952 is also preferable. Examples of the compound having a polyfunctional polymerizable unsaturated group include the polyfunctional monomers described in the hard coat layer. These compounds are particularly preferred because they have a large combined effect for improving scratch resistance, particularly when a compound having a polymerizable unsaturated group is used in the polymer body.

1- (4) Organosilane Compound In the film of the present invention, at least one layer formed on the transparent support has a hydrolyzate of organosilane compound and / or a partial condensate thereof (hereinafter obtained). The reaction solution is also referred to as a “sol component”) from the viewpoint of scratch resistance.
This sol component functions as a binder by applying a curable composition containing the sol component and then condensing in a drying and heating step to form a cured product. Moreover, when it has a polyfunctional acrylate polymer, the binder which has a three-dimensional structure is formed by irradiation of actinic light.

The organosilane compound is preferably represented by the following general formula [A].
Formula [A]
(R ¹⁰ ) _m -Si (X) _4-m
In the general formula [A], R ¹⁰ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, hexyl, decyl, hexadecyl and the like. The alkyl group is preferably an alkyl group having 1 to 30 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 6 carbon atoms. Examples of the aryl group include phenyl and naphthyl, and a phenyl group is preferable.
X represents a hydroxyl group or a hydrolyzable group, for example, an alkoxy group (preferably an alkoxy group having 1 to 5 carbon atoms, such as a methoxy group or an ethoxy group), a halogen atom (for example, Cl, Br, I or the like). ), And R ² COO (R ² is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, such as CH ₃ COO, C ₂ H ₅ COO, etc.), preferably An alkoxy group, particularly preferably a methoxy group or an ethoxy group.
m represents an integer of 1 to 3, preferably 1 or 2, and particularly preferably 1.

When R ¹⁰ or X there are a plurality, a plurality of R ¹⁰ or X groups may be different, even the same, respectively.
The substituent contained in R ¹⁰ is not particularly limited, but a halogen atom (fluorine, chlorine, bromine, etc.), hydroxyl group, mercapto group, carboxyl group, epoxy group, alkyl group (methyl, ethyl, i-propyl, propyl, t-butyl etc.), aryl groups (phenyl, naphthyl etc.), aromatic heterocyclic groups (furyl, pyrazolyl, pyridyl etc.), alkoxy groups (methoxy, ethoxy, i-propoxy, hexyloxy etc.), aryloxy (phenoxy etc.) ), Alkylthio groups (methylthio, ethylthio, etc.), arylthio groups (phenylthio, etc.), alkenyl groups (vinyl, 1-propenyl, etc.), acyloxy groups (acetoxy, acryloyloxy, methacryloyloxy, etc.), alkoxycarbonyl groups (methoxycarbonyl, ethoxy) Carbonyl, etc.), aryloxy Carbonyl groups (phenoxycarbonyl, etc.), carbamoyl groups (carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N-methyl-N-octylcarbamoyl, etc.), acylamino groups (acetylamino, benzoylamino, acrylicamino, methacrylamino) Etc.), and these substituents may be further substituted.

When there are a plurality of R ^{10 s} , at least one is preferably a substituted alkyl group or a substituted aryl group.
Among the organosilane compounds represented by the general formula [A], an organosilane compound having a vinyl polymerizable substituent represented by the following general formula [B] is preferable.

General formula [B]

In the general formula [B], R ¹ represents a hydrogen atom, a methyl group, a methoxy group, an alkoxycarbonyl group, a cyano group, a fluorine atom, or a chlorine atom. Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group. A hydrogen atom, a methyl group, a methoxy group, a methoxycarbonyl group, a cyano group, a fluorine atom, and a chlorine atom are preferable, a hydrogen atom, a methyl group, a methoxycarbonyl group, a fluorine atom, and a chlorine atom are more preferable, and a hydrogen atom and a methyl group Is particularly preferred.
Y represents a single bond or * -COO-**, * -CONH-** or * -O-**, preferably a single bond, * -COO-** or * -CONH-**, * -COO-** is more preferable, and * -COO-** is particularly preferable. * Represents a position bonded to ═C (R ¹ ) —, and ** represents a position bonded to L.

  L represents a divalent linking chain. Specifically, a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted alkylene group having a linking group (for example, ether, ester, amide, etc.) inside, and a linking group inside. A substituted or unsubstituted arylene group, a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, an alkylene group having a linking group therein is preferred, an unsubstituted alkylene group, an unsubstituted arylene group Further, an alkylene group having an ether or ester linking group inside is more preferable, an unsubstituted alkylene group, and an alkylene group having an ether or ester linking group inside is particularly preferable. Examples of the substituent include a halogen, a hydroxyl group, a mercapto group, a carboxyl group, an epoxy group, an alkyl group, and an aryl group, and these substituents may be further substituted.

n represents 0 or 1. When there are a plurality of Xs, the plurality of Xs may be the same or different. n is preferably 0.
R ¹⁰ has the same meaning as in formula [A], preferably a substituted or unsubstituted alkyl group or an unsubstituted aryl group, and more preferably an unsubstituted alkyl group or an unsubstituted aryl group.
X has the same meaning as in the general formula [A], preferably a halogen atom, a hydroxyl group or an unsubstituted alkoxy group, more preferably a chlorine atom, a hydroxyl group or an unsubstituted alkoxy group having 1 to 6 carbon atoms, a hydroxyl group or a carbon number of 1 -3 alkoxy groups are more preferred, and methoxy groups are particularly preferred.

  Two or more compounds of the general formula [A] and general formula [B] may be used in combination. Although the specific example of a compound represented by general formula [A] and general formula [B] is shown below, it is not limited.

  Of these, (M-1), (M-2), and (M-5) are particularly preferable.

  The hydrolyzate and / or partial condensate of the organosilane compound is generally produced by treating the organosilane compound in the presence of a catalyst. Catalysts include inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid; organic acids such as oxalic acid, acetic acid, formic acid, methanesulfonic acid and toluenesulfonic acid; inorganic bases such as sodium hydroxide, potassium hydroxide and ammonia; triethylamine, Examples thereof include organic bases such as pyridine; metal alkoxides such as triisopropoxyaluminum and tetrabutoxyzirconium; metal chelate compounds having a metal such as Zr, Ti or Al as a central metal. In the present invention, it is preferable to use a metal chelate compound, an acid catalyst of inorganic acids and organic acids. Inorganic acids are preferably hydrochloric acid and sulfuric acid, and organic acids are preferably those having an acid dissociation constant (pKa value (25 ° C.)) of 4.5 or less in water, and further, acid dissociation constants in hydrochloric acid, sulfuric acid and water. Is preferably an organic acid having an acid dissociation constant of 2.5 or less in hydrochloric acid, sulfuric acid or water, more preferably an organic acid having an acid dissociation constant of 2.5 or less in water. Specifically, methanesulfonic acid, oxalic acid, phthalic acid, and malonic acid are more preferable, and oxalic acid is particularly preferable.

As the metal chelate compound, (wherein, R ³ represents an alkyl group having 1 to 10 carbon atoms) Formula R ³ OH alcohol and R ⁴ COCH ₂ COR ⁵ (formula represented by, R ⁴ is the number of carbon atoms 1 to 10 alkyl groups, R ⁵ represents an alkyl group having 1 to 10 carbon atoms or a compound represented by an alkoxy group having 1 to 10 carbon atoms), and is selected from Zr, Ti, and Al. Any metal having a central metal as the metal can be used without any particular limitation. Within this category, two or more metal chelate compounds may be used in combination. The metal chelate compound used in the present invention has the general formula Zr (OR ³ ) _p1 (R ⁴ COCHCOR ⁵ ) _p2 , Ti (OR ³ ) _q1 (R ⁴ COCHCOR ⁵ ) _q2 , and Al (OR ³ ) _r1 (R ⁴ Those selected from the group of compounds represented by COCHCOR ⁵ ) _r2 are preferred and serve to promote the condensation reaction of the hydrolyzate and / or partial condensate of the organosilane compound.
R ³ and R ⁴ in the metal chelate compound may be the same or different and each is an alkyl group having 1 to 10 carbon atoms, specifically, an ethyl group, n-propyl group, i-propyl group, n-butyl group, sec -Butyl group, t-butyl group, n-pentyl group, phenyl group and the like. R ⁵ represents an alkyl group having 1 to 10 carbon atoms as described above, or an alkoxy group having 1 to 10 carbon atoms such as a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, and n-butoxy. Group, sec-butoxy group, t-butoxy group and the like. Moreover, p1, p2, q1, q2, r1, and r2 in the metal chelate compound represent integers determined so as to be p1 + p2 = 4, q1 + q2 = 4, and r1 + r2 = 3, respectively.

Specific examples of these metal chelate compounds include tri-n-butoxyethylacetoacetate zirconium, di-n-butoxybis (ethylacetoacetate) zirconium, n-butoxytris (ethylacetoacetate) zirconium, tetrakis (n-propylacetate). Zirconium chelate compounds such as acetate) zirconium, tetrakis (acetylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium; diisopropoxy bis (ethylacetoacetate) titanium, diisopropoxy bis (acetylacetate) titanium, diiso Titanium chelate compounds such as propoxy bis (acetylacetone) titanium; diisopropoxyethyl acetoacetate aluminum, diisopropyl Poxyacetylacetonate aluminum, isopropoxybis (ethylacetoacetate) aluminum, isopropoxybis (acetylacetonate) aluminum, tris (ethylacetoacetate) aluminum, tris (acetylacetonate) aluminum, monoacetylacetonate bis (ethyl) An aluminum chelate compound such as acetoacetate) aluminum.
Among these metal chelate compounds, tri-n-butoxyethyl acetoacetate zirconium, diisopropoxy bis (acetylacetonate) titanium, diisopropoxyethyl acetoacetate aluminum, and tris (ethyl acetoacetate) aluminum are preferable. . These metal chelate compounds can be used individually by 1 type or in mixture of 2 or more types. Moreover, the partial hydrolyzate of these metal chelate compounds can also be used.

  In the present invention, it is preferable that a β-diketone compound and / or a β-ketoester compound is further added to the curable composition. This will be further described below.

The β-diketone compound and / or β-ketoester compound represented by the general formula R ⁴ COCH ₂ COR ⁵ is used in the present invention, and is used as a stability improver for the curable composition used in the present invention. It works. Here, R ⁴ represents an alkyl group having 1 to 10 carbon atoms, and R ⁵ represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. That is, by coordinating with a metal atom in the metal chelate compound (zirconium, titanium and / or aluminum compound), the condensation reaction of the hydrolyzate and / or partial condensate of the organosilane compound by these metal chelate compounds is performed. It is considered that the promoting action is suppressed and the storage stability of the resulting composition is improved. R ⁴ and R ⁵ constituting the β- diketone compound and / or β- ketoester compound are the same as R ⁴ and R ⁵ constituting the metal chelate compound.

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

The compounding amount of the organosilane compound is preferably 0.1 to 50% by mass, more preferably 0.5 to 20% by mass when the total solid content of the low refractive index layer is introduced into the low refractive index layer. 10% by mass is most preferred.
The organosilane compound may be added directly to the curable composition (a coating solution for forming any layer of an optical film, preferably a coating solution for a hard coat layer or a low refractive index layer). A silane compound is pretreated in the presence of a catalyst to prepare a hydrolyzate and / or partial condensate of the organosilane compound, and the curable composition is prepared using the resulting reaction solution (sol solution). In the present invention, first, a composition containing a hydrolyzate and / or partial condensate of the organosilane compound and a metal chelate compound is prepared, and a β-diketone compound and / or a β-ketoester compound is added thereto. It is preferable that the added liquid is coated by being contained in at least one coating liquid of a hard coat layer or a low refractive index layer.
In the present invention, the following organosilane compounds can also be preferably used.

a, silicon alkoxide A compound represented by RmSi (OR ′) n, wherein R and R ′ represent an alkyl group having 1 to 10 carbon atoms, and m and n are integers such that m + n = 4, respectively. For example, tetramethoxysilane, tetraethoxysilane, tetra-iso-propoxysilane, tetra-n-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, tetrapentaethoxysilane, Tetrapenta-iso-propoxysilane, tetrapenta-n-proxysilane, tetrapenta-n-butoxysilane, tetrapenta-sec-butoxysilane, tetrapenta-tert-butoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, Methyl tributoxy silane, dimethyl dimethoxy silane, dimethyl diethoxy silane, dimethyl ethoxy silane, dimethyl methoxy silane, dimethyl propoxy silane, dimethyl butyl Kishishiran, methyldimethoxysilane, methyldiethoxysilane, hexyl trimethoxysilane.

b. Silane coupling agents For example, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ Aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropylmethoxysilane hydrochloride, γ-glycidoxypropyltrimethoxysilane, aminosilane , Methyltrimethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilazane, vinyltris (β-methoxyethoxy) silane, octadecyldimethyl [3- (to Trimethoxysilyl) propyl] ammonium chloride, methyl trichlorosilane, dimethyl dichlorosilane, and the like.

c. Ionizing radiation curable silicon compound A plurality of groups that undergo reactive crosslinking by ionizing radiation, for example, an organosilicon compound having a polymerizable double bond group and having a molecular weight of 5,000 or less. Such reactive organosilicon compounds may be one end vinyl functional polysilane, both end vinyl functional polysilane, one end vinyl functional polysiloxane, both end vinyl functional polysiloxane, or a vinyl functionality obtained by reacting these compounds. Examples include polysilane, vinyl functional polysiloxane, and the like.

  Examples of other compounds include (meth) acryloxysilane compounds such as 3- (meth) acryloxypropyltrimethoxysilane and 3- (meth) acryloxypropylmethyldimethoxysilane.

  For example, the following reactive organosilicon compound described in JP-A-2003-39586, publicly disclosed, may be used in combination with the binder. The reactive organosilicon compound is used in the range of 10 to 100% by weight with respect to the total of the ionizing radiation curable resin and the reactive organosilicon compound. In particular, when the ionizing radiation curable organosilicon compound of c is used, it is possible to form a conductive layer using only this as a resin component.

1- (5) Initiator Polymerization of monomers having various ethylenically unsaturated groups can be carried out by irradiation with ionizing radiation or heating in the presence of a photo radical initiator or a thermal radical initiator.
In preparing the film of the present invention, a photoinitiator or a thermal initiator can be used in combination.

<Photoinitiator>
Examples of photo radical polymerization initiators include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides (JP-A No. 2001-139663, etc.), 2, 3 -Dialkyldione compounds, disulfide compounds, fluoroamine compounds, aromatic sulfoniums, lophine dimers, onium salts, borate salts, active esters, active halogens, inorganic complexes, coumarins and the like.
Examples of acetophenones include 2,2-dimethoxyacetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, 1-hydroxy-dimethylphenylketone, 1-hydroxy-dimethyl-p-isopropylphenylketone, 1-hydroxy Cyclohexyl phenyl ketone, 2-methyl-4-methylthio-2-morpholinopropiophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, 4-phenoxydichloroacetophenone, 4-t- Butyl-dichloroacetophenone is included.

  Examples of benzoins include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyl dimethyl ketal, benzoin benzene sulfonate, benzoin toluene sulfonate, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether It is. Examples of benzophenones include benzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 2,4-dichlorobenzophenone, 4,4-dichlorobenzophenone and p-chlorobenzophenone, 4,4'-dimethylaminobenzophenone (Michler ketone), 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone and the like are included.

  Examples of the borate salt are described in Japanese Patent Nos. 2764769 and 2002-116539, and Kunz, Martin “Rad Tech'98. Proceeding April 19-22, 1998, Chicago”. And the organic borate compounds described. For example, the compounds described in JP-A-2002-116539, paragraph numbers [0022] to [0027] can be mentioned. Examples of other organic boron compounds include JP-A-6-348011, JP-A-7-128785, JP-A-7-140589, JP-A-7-306527, and JP-A-7-292014. Specific examples include organoboron transition metal coordination complexes and the like, and specific examples include ion complexes with cationic dyes.

Examples of phosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
Examples of active esters include 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], sulfonic acid esters, cyclic active ester compounds, and the like.
Specifically, Examples 1 to 21 described in JP-A 2000-80068 are particularly preferable.
Examples of the onium salts include aromatic diazonium salts, aromatic iodonium salts, and aromatic sulfonium salts.

Specific examples of the active halogens include Wakabayashi et al., “Bull Chem. Soc Japan” 42, 2924 (1969), US Pat. No. 3,905,815, JP-A-5-27830, M.M. P. Examples include compounds described in Hutt “Journal of Heterocyclic Chemistry”, Vol. 1 (No. 3), (1970), and in particular, oxazole compounds substituted with a trihalomethyl group: s-triazine compounds. More preferred are s-triazine derivatives in which at least one mono-, di- or trihalogen-substituted methyl group is bonded to the s-triazine ring. Specific examples include S-triazine and oxathiazole compounds, such as 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl). -4,6-bis (trichloromethyl) -s-triazine, 2- (p-styrylphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3-Br-4-di (ethyl) Acetate) amino) phenyl) -4,6-bis (trichloromethyl) -s-triazine, 2-trihalomethyl-5- (p-methoxyphenyl) -1,3,4-oxadiazole. Specifically, p.14 to p30 in JP-A-58-15503, p6-p10 in JP-A-55-77742, and p287 in JP-B-60-27673. 1-No. 8, No. pp. 443 to p444 of JP-A-60-239736. 1-No. 17, No. 4,701,399. Compounds such as 1-19 are particularly preferred.
Examples of inorganic complexes include bis (η ⁵ -2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium.
Examples of coumarins include 3-ketocoumarin.

These initiators may be used alone or in combination.
“Latest UV Curing Technology”, Technical Information Association, 1991, p. 159, and “UV curing system” written by Kayo Kiyomi, 1989, General Technology Center, p. Various examples are also described in 65-148 and are useful in the present invention.

  Commercially available radical photopolymerization initiators include KAYACURE (DETX-S, BP-100, BDKM, CTX, BMS, 2-EAQ, ABQ, CPTX, EPD, ITX, QTX, BTC, manufactured by Nippon Kayaku Co., Ltd. MCA, etc.), Irgacure (651, 184, 500, 819, 907, 369, 1173, 1870, 2959, 4265, 4263, etc.) manufactured by Ciba Specialty Chemicals, Ltd., Esacure (KIP100F, KB1, manufactured by Sartomer) EB3, BP, X33, KT046, KT37, KIP150, TZT) and the like and combinations thereof are preferred examples.

  It is preferable to use a photoinitiator in the range of 0.1-15 mass parts with respect to 100 mass parts of polyfunctional monomers, More preferably, it is the range of 1-10 mass parts.

<Photosensitizer>
In addition to the photopolymerization initiator, a photosensitizer may be used. Specific examples of the photosensitizer include n-butylamine, triethylamine, tri-n-butylphosphine, Michler's ketone and thioxanthone.
Further, one or more auxiliary agents such as an azide compound, a thiourea compound, and a mercapto compound may be used in combination.
Examples of commercially available photosensitizers include KAYACURE (DMBI, EPA) manufactured by Nippon Kayaku Co., Ltd.

<Thermal initiator>
As the thermal radical initiator, organic or inorganic peroxides, organic azo, diazo compounds, and the like can be used.
Specifically, benzoyl peroxide, halogen benzoyl peroxide, lauroyl peroxide, acetyl peroxide, dibutyl peroxide, cumene hydroperoxide, butyl hydroperoxide as organic peroxides, hydrogen peroxide, peroxides as inorganic peroxides. Diazo compounds such as ammonium sulfate, potassium persulfate and the like, 2,2′-azobis (isobutyronitrile), 2,2′-azobis (propionitrile), 1,1′-azobis (cyclohexanecarbonitrile), etc. And diazoaminobenzene, p-nitrobenzenediazonium and the like.

1- (6) Crosslinkable compound When the monomer or polymer binder constituting the present invention alone does not have sufficient curability, the necessary curability may be imparted by blending the crosslinkable compound. it can.
For example, when the polymer body contains a hydroxyl group, various amino compounds are preferably used as the curing agent. The amino compound used as the crosslinkable compound is, for example, a compound containing a total of two or more of any one or both of a hydroxyalkylamino group and an alkoxyalkylamino group. Specifically, for example, a melamine compound, Examples include urea compounds, benzoguanamine compounds, glycoluril compounds, and the like.

  Melamine compounds are generally known as compounds having a skeleton in which a nitrogen atom is bonded to a triazine ring, and specific examples include melamine, alkylated melamine, methylol melamine, alkoxylated methyl melamine, and the like. However, it is preferable to have one or both of a methylol group and an alkoxylated methyl group in one molecule in total. Specifically, methylolated melamine, alkoxylated methylmelamine, or a derivative thereof obtained by reacting melamine and formaldehyde under basic conditions is preferable, and good storage stability is obtained particularly for the curable resin composition. Alkoxylated methyl melamine is preferable in that it can be obtained and good reactivity can be obtained. There are no particular restrictions on the methylolated melamine and the alkoxylated methylmelamine used as the crosslinkable compound. For example, the methylolated melamine and the alkoxylated methylmelamine can be obtained by the method described in the document “Plastic Materials Course [8] Urea Melamine Resin” (Nikkan Kogyo Shimbun). Various resinous materials can be used.

  In addition to urea, examples of the urea compound include polymethylolated urea, alkoxylated methylurea which is a derivative thereof, methylolated uron having a uron ring, and alkoxylated methyluron. And also about compounds, such as a urea derivative, the use of the various resinous materials described in said literature is possible.

1- (7) Curing Catalyst For the layer formation of the film of the present invention, radicals and acids generated by irradiation with ionizing radiation or heat can be used as a curing catalyst for promoting curing.

<Heat acid generator>
Specific examples of the thermal acid generator include various aliphatic sulfonic acids and salts thereof, various aliphatic carboxylic acids and salts thereof such as citric acid, acetic acid and maleic acid, and various aromatic carboxylic acids such as benzoic acid and phthalic acid. Examples thereof include acids and salts thereof, alkylbenzenesulfonic acids and ammonium salts thereof, amine salts, various metal salts, phosphoric acid and phosphoric acid esters of organic acids, and the like.
Examples of commercially available materials include catalyst 4040, catalyst 4050, catalyst 600, catalyst 602, catalyst 500, catalyst 296-9, and more made by Nippon Cytec Industries, Inc., and NACURE series 155, 1051, 5076, 4054J and its block type NACURE series 2500, 5225, X49-110, 3525, 4167 or more manufactured by King Corporation, and the like.
The use ratio of the thermal acid generator is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the curable resin composition. When the addition amount is within this range, the storage stability of the curable resin composition is good and the scratch resistance of the coating film is also good.

<Photosensitive acid generator, photoacid generator>
Furthermore, the photo-acid generator which can be used as a photoinitiator is explained in full detail.
Examples of the acid generator include a photoinitiator for photocationic polymerization, a photodecolorant for dyes, a photochromic agent, a known acid generator used in a microresist, and the like, a known compound, and a mixture thereof. Is mentioned. Examples of the acid generator include organic halogenated compounds, disulfone compounds, onium compounds, etc. Among these, specific examples of organic halogen compounds and disulfone compounds are the same as those described for the compound that generates radicals. Things.
Examples of the photosensitive acid generator include (1) various onium salts such as iodonium salts, sulfonium salts, phosphonium salts, diazonium salts, ammonium salts, pyridinium salts; (2) β-ketoesters, β-sulfonylsulfones and these. sulfone compounds such as α-diazo compounds; (3) sulfonic acid esters such as alkyl sulfonic acid esters, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, and imino sulfonates; (4) sulfonimide compounds; and (5) diazomethane compounds. Can be mentioned.
Examples of the onium compounds include diazonium salts, ammonium salts, iminium salts, phosphonium salts, iodonium salts, sulfonium salts, arsonium salts, and selenonium salts. Of these, diazonium salts, iodonium salts, sulfonium salts, and iminium salts are preferable from the viewpoint of photosensitivity at the start of photopolymerization, material stability of the compound, and the like. Examples thereof include compounds described in paragraph numbers [0058] to [0059] of JP-A-2002-29162.

The use ratio of the photosensitive acid generator is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the curable resin composition.
In addition, as specific compounds and methods of use, for example, the contents described in JP-A-2005-43876 can be used.

1- (8) Translucent Particles In order to impart antiglare property (surface scattering property) and internal scattering property to the film of the present invention, particularly the antiglare hard coat layer and hard coat layer described later, Light particles can be used.

The translucent particles may be organic particles or inorganic particles. As the particle size is not varied, the scattering characteristics are less varied, and the design of the haze value is facilitated. As the translucent particles, plastic beads are preferable, and those having particularly high transparency and a difference in refractive index with the binder are preferable.
As organic particles, polymethyl methacrylate particles (refractive index 1.49), crosslinked poly (acryl-styrene) copolymer particles (refractive index 1.54), melamine resin particles (refractive index 1.57), polycarbonate particles ( Refractive index 1.57), polystyrene particles (refractive index 1.60), crosslinked polystyrene particles (refractive index 1.61), polyvinyl chloride particles (refractive index 1.60), benzoguanamine-melamine formaldehyde particles (refractive index 1. 68) etc. are used.
Examples of the inorganic particles include silica particles (refractive index: 1.44), alumina particles (refractive index: 1.63), zirconia particles, titania particles, and inorganic particles having hollows and pores.

Of these, cross-linked polystyrene particles, cross-linked poly ((meth) acrylate) particles, and cross-linked poly (acryl-styrene) particles are preferably used, and a binder is selected according to the refractive index of each light-transmitting particle selected from these particles. By adjusting the refractive index, the internal haze, surface haze, and centerline average roughness of the present invention can be achieved.
Furthermore, a binder (having a refractive index of 1.50 to 1.53 after curing) containing a tri- or higher functional (meth) acrylate monomer as a main component and a crosslinked poly (meth) acrylate weight having an acrylic content of 50 to 100 weight percent. It is preferable to use a combination of translucent particles composed of a combination, and in particular, a combination of a binder and translucent particles composed of a crosslinked poly (styrene-acrylic) copolymer (with a refractive index of 1.48 to 1.54). preferable.

The refractive index of the binder (translucent resin) and translucent particles in the present invention is preferably 1.45 to 1.70, more preferably 1.48 to 1.65. In order to set the refractive index within the above range, the type and amount ratio of the binder and the light-transmitting particles may be appropriately selected. How to select can be easily known experimentally in advance.
In the present invention, the difference in refractive index between the binder and the translucent particles (the refractive index of the translucent particles−the refractive index of the binder) is preferably 0.001 to 0.130 as an absolute value, More preferably, it is 0.001-0.120, More preferably, it is 0.001-0.115. If this difference exceeds 0.130, problems such as film character blur, a decrease in dark room contrast, and surface turbidity occur.

  Here, the refractive index of the binder can be quantitatively evaluated by directly measuring it with an Abbe refractometer or by measuring a spectral reflection spectrum or a spectral ellipsometry. The refractive index of the translucent particles is measured by measuring the turbidity by dispersing an equal amount of the translucent particles in the solvent in which the refractive index is changed by changing the mixing ratio of two types of solvents having different refractive indexes. It is measured by measuring the refractive index of the solvent when the turbidity is minimized with an Abbe refractometer.

  In the case of the above translucent particles, the translucent particles easily settle in the binder, and therefore an inorganic filler such as silica may be added to prevent sedimentation. As the amount of the inorganic filler added increases, it is more effective in preventing the translucent particles from settling, but adversely affects the transparency of the coating film. Therefore, preferably, an inorganic filler having a particle size of 0.5 μm or less is contained in an amount of less than 0.1% by mass so as not to impair the transparency of the coating film with respect to the binder.

  The average particle size of the translucent particles is preferably 0.5 to 10 μm, more preferably 2.0 to 6.0 μm. If the average particle size is less than 0.5 μm, the light scattering angle distribution spreads to a wide angle, which may cause blurring of characters on the display. On the other hand, if it exceeds 10 μm, it is necessary to increase the thickness of the layer to be added, which causes problems such as curling and cost increase.

  Moreover, you may use together and use 2 or more types of translucent particle | grains from which a particle diameter differs. It is possible to impart an antiglare property with a light-transmitting particle having a larger particle diameter, and to reduce the surface roughness with a light-transmitting particle having a smaller particle diameter.

  The translucent particles are preferably blended so that 3 to 30% by mass is contained in the total solid content of the additive layer. More preferably, it is 5-20 mass%. If it is less than 3% by mass, the effect of addition is insufficient, and if it exceeds 30% by mass, problems such as image blur, surface turbidity and glare occur.

Moreover, the density of the translucent particles is preferably 10 to 1000 mg / m ² , more preferably 100 to 700 mg / m ² .

<Translucent particle preparation, classification method>
Examples of the method for producing translucent particles according to the present invention include suspension polymerization method, emulsion polymerization method, soap-free emulsion polymerization method, dispersion polymerization method, seed polymerization method and the like. Good. These production methods are described in, for example, “Experimental Methods for Polymer Synthesis” (Takayuki Otsu and Masaaki Kinoshita, Kagaku Dojinsha), pages 130 and 146 to 147, “Synthetic Polymers” Vol. 1, p. 246-290, 3rd volume, p. 1 to 108, etc., and Japanese Patent Nos. 2543503, 3508304, 2746275, 3521560, 3580320, Japanese Patent Laid-Open No. 10-1561. Reference can be made to methods described in JP-A No. 7-2908, JP-A No. 5-297506, JP-A No. 2002-145919, and the like.

The particle size distribution of the translucent particles is preferably monodisperse particles in terms of haze value and control of diffusibility, and uniformity of the coated surface. For example, when particles having a particle size of 20% or more than the average particle size are defined as coarse particles, the proportion of the coarse particles is preferably 1% or less of the total number of particles, more preferably 0.1% or less. Yes, more preferably 0.01% or less. Particles having such a particle size distribution are also effective means of classification after preparation or synthesis reaction, and particles having a desired distribution can be obtained by increasing the number of classifications or increasing the degree of classification. .
It is preferable to use a method such as an air classification method, a centrifugal classification method, a sedimentation classification method, a filtration classification method, or an electrostatic classification method for classification.

1- (9) Inorganic particles Various inorganic particles can be used in the present invention in order to improve physical properties such as hardness, optical properties such as reflectance, and scattering properties.
As the inorganic particles, an oxide of at least one metal selected from silicon, zirconium, titanium, aluminum, indium, zinc, tin, and antimony, specific examples include ZrO ₂ , TiO ₂ , Al ₂ O ₃ , In ₂ O ₃ , ZnO, SnO ₂ , Sb ₂ O ₃ , ITO and the like can be mentioned. Others include BaSO ₄ , CaCO ₃ , talc and kaolin.

  The particle diameter of the inorganic particles used in the present invention is preferably as fine as possible in the dispersion medium, and the weight average diameter is 1 to 200 nm. Preferably it is 5-150 nm, More preferably, it is 10-100 nm, Most preferably, it is 10-80 nm. A film that does not impair the transparency can be formed by refining the inorganic particles to 100 nm or less. The particle diameter of the inorganic particles can be measured by a light scattering method or an electron micrograph.

The specific surface area of the inorganic particles is preferably from 10 to 400 m ² / g, more preferably from 20 to 200 m ² / g, and most preferably from 30 to 150 m ² / g.

The inorganic particles used in the present invention are preferably added to a coating solution for a layer used as a dispersion in a dispersion medium.
As the dispersion medium for the inorganic particles, a liquid having a boiling point of 60 to 170 ° C. is preferably used. Examples of dispersion media include water, alcohol (eg, methanol, ethanol, isopropanol, butanol, benzyl alcohol), ketone (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone), ester (eg, methyl acetate, ethyl acetate, Propyl acetate, butyl acetate, methyl formate, ethyl formate, propyl formate, butyl formate), aliphatic hydrocarbons (eg, hexane, cyclohexane), halogenated hydrocarbons (eg, methylene chloride, chloroform, carbon tetrachloride), aromatic Hydrocarbon (eg, benzene, toluene, xylene), amide (eg, dimethylformamide, dimethylacetamide, n-methylpyrrolidone), ether (eg, diethyl ether, dioxane, tetrahydrofuran), ether alcohol (eg, 1-methyl) Carboxymethyl-2-propanol) are included. Toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and butanol are particularly preferred.
Particularly preferred dispersion media are methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.

  The inorganic particles are dispersed using a disperser. Examples of dispersers include sand grinder mills (eg, pinned bead mills), high speed impeller mills, pebble mills, roller mills, attritors and colloid mills. A sand grinder mill and a high-speed impeller mill are particularly preferred. Further, preliminary dispersion processing may be performed. Examples of the disperser used for the preliminary dispersion treatment include a ball mill, a three-roll mill, a kneader, and an extruder.

<High refractive index particles>
For the purpose of increasing the refractive index of the layer constituting the present invention, a cured product of a composition in which inorganic particles having a high refractive index are dispersed in a monomer, an initiator, and an organically substituted silicon compound is preferably used.
As the inorganic particles in this case, ZrO ₂ and TiO _{2 are} particularly preferably used from the viewpoint of refractive index. ZrO ₂ is most preferable for increasing the refractive index of the hard coat layer, and TiO ₂ fine particles are most preferable as the particles for the high refractive index layer and the medium refractive index layer.

As the TiO ₂ particles, inorganic particles mainly containing TiO ₂ containing at least one element selected from cobalt, aluminum, and zirconium are particularly preferable. The main component means a component having the largest content (mass%) among the components constituting the particles.
The particles mainly composed of TiO ₂ in the present invention preferably have a refractive index of 1.90 to 2.80, more preferably 2.10 to 2.80, and 2.20 to 2.80. Most preferably.
The weight average diameter of the primary particles of particles mainly composed of TiO ₂ is preferably 1 to 200 nm, more preferably 1 to 150 nm, still more preferably 1 to 100 nm, and particularly preferably 1 to 80 nm.

The crystal structure of the particles containing TiO ₂ as a main component is preferably a rutile, rutile / anatase mixed crystal, anatase or amorphous structure, and particularly preferably a rutile structure. The main component means a component having the largest content (mass%) among the components constituting the particles.

By containing at least one element selected from Co (cobalt), Al (aluminum) and Zr (zirconium) in the particles containing TiO ₂ as a main component, the photocatalytic activity of TiO ₂ can be suppressed. The weather resistance of the inventive film can be improved.
A particularly preferable element is Co (cobalt). It is also preferable to use two or more types in combination.
The inorganic particles mainly composed of TiO ₂ of the present invention may have a core / shell structure by surface treatment as described in JP-A No. 2001-166104.

  The addition amount of the monomer and inorganic particles in the layer is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, based on the total mass of the binder. Two or more kinds of inorganic particles may be used in the layer.

<Low refractive index particles>
The inorganic particles contained in the low refractive index layer desirably have a low refractive index, and examples thereof include fine particles of magnesium fluoride and silica. In particular, silica fine particles are preferable in terms of refractive index, dispersion stability, and cost.
The average particle diameter of the silica fine particles is preferably 30% to 150% of the thickness of the low refractive index layer, more preferably 35% to 80%, and still more preferably 40% to 60%. That is, when the thickness of the low refractive index layer is 100 nm, the particle diameter of the silica fine particles is preferably 30 nm to 150 nm, more preferably 35 nm to 80 nm, and still more preferably 40 nm to 60 nm.
Here, the average particle diameter of the inorganic particles is measured by a Coulter counter.

  If the particle size of the silica fine particles is too small, the effect of improving the scratch resistance is reduced. If it is too large, fine irregularities are formed on the surface of the low refractive index layer, and the appearance such as black tightening and the integrated reflectance are deteriorated. The silica fine particles may be either crystalline or amorphous, and may be monodispersed particles or aggregated particles as long as a predetermined particle size is satisfied. The shape is most preferably a spherical diameter, but there is no problem even if the shape is indefinite.

Further, at least one kind of silica fine particles having an average particle size of less than 25% of the thickness of the low refractive index layer (referred to as “small size particle size silica particles”) is used as silica fine particles having the above particle size (“large size particles”). It is preferably used in combination with “silica fine particles having a diameter”.
Since the fine silica particles having a small particle size can exist in the gaps between the fine silica particles having a large particle size, they can contribute as a retaining agent for the fine silica particles having a large particle size.
When the low refractive index layer is 100 nm, the average particle size of the silica fine particles having a small size is preferably from 1 nm to 20 nm, more preferably from 5 nm to 15 nm, and particularly preferably from 10 nm to 15 nm. Use of such silica fine particles is preferable in terms of raw material costs and a retaining agent effect.

The coating amount of the low refractive index particles is preferably ^{1mg / m 2 ~100mg / m 2} , more preferably ^{5mg / m 2 ~80mg / m 2} , more preferably from ^{10mg / m 2 ~60mg / m 2} . If the amount is too small, the effect of improving the scratch resistance is reduced. If the amount is too large, fine irregularities are formed on the surface of the low refractive index layer, and the appearance such as black tightening and the integrated reflectance are deteriorated.

<Hollow silica particles>
For the purpose of further reducing the refractive index, it is preferable to use hollow silica fine particles.

The hollow silica fine particles preferably have a refractive index of 1.15 to 1.40, more preferably 1.17 to 1.35, and most preferably 1.17 to 1.30. The refractive index here represents the refractive index of the entire particle, and does not represent the refractive index of only the outer shell silica forming the hollow silica particles. At this time, when the radius of the cavity in the particle is a and the radius of the particle outer shell is b, the porosity x expressed by the following formula (VIII) is (formula VIII)
^{x = (4πa 3/3)} / (4πb 3/3) × 100
Preferably it is 10-60%, More preferably, it is 20-60%, Most preferably, it is 30-60%. If the hollow silica particles are made to have a lower refractive index and a higher porosity, the thickness of the outer shell becomes thinner and the strength of the particles becomes weaker. From the viewpoint of scratch resistance, the low refractive index is less than 1.15. Rate particles are not preferred.

  A method for producing hollow silica is described in, for example, Japanese Patent Application Laid-Open Nos. 2001-233611 and 2002-79616. In particular, particles having cavities inside the shell and having fine pores in the shell are particularly preferred. The refractive index of these hollow silica particles can be calculated by the method described in JP-A-2002-79616.

The coating amount of the hollow silica is preferably from ^{1mg / m 2 ~100mg / m 2} , more preferably ^{5mg / m 2 ~80mg / m 2} , more preferably from ^{10mg / m 2 ~60mg / m 2} . If the amount is too small, the effect of lowering the refractive index and the effect of improving the scratch resistance will be reduced.
The average particle diameter of the hollow silica is preferably 30% to 150% of the thickness of the low refractive index layer, more preferably 35% to 80%, and still more preferably 40% to 60%. That is, if the thickness of the low refractive index layer is 100 nm, the particle size of the hollow silica is preferably 30 nm to 150 nm, more preferably 35 nm to 100 nm, and still more preferably 40 nm to 65 nm.
If the particle size of the silica particles is too small, the proportion of cavities will decrease and a decrease in refractive index cannot be expected. Getting worse. The silica fine particles may be either crystalline or amorphous, and monodisperse particles are preferred. The shape is most preferably a spherical diameter, but there is no problem even if the shape is indefinite.
Further, two or more kinds of hollow silica having different particle average particle sizes can be used in combination. Here, the average particle diameter of the hollow silica can be determined from an electron micrograph.
The specific surface area of the hollow silica in the present invention is preferably from 20 to 300 m ² / g, more preferably 30~120m ² / g, most preferably 40~90m ² / g. The surface area can be obtained by the BET method using nitrogen.

  In the present invention, silica particles having no voids can be used in combination with hollow silica. The preferred particle size of silica without voids is 30 nm to 150 nm, more preferably 35 nm to 100 nm, and most preferably 40 nm to 80 nm.

1- (9) Surface Treatment Agent Inorganic particles used in the present invention are plasma in order to stabilize dispersion in a dispersion or coating solution, or to increase affinity and binding properties with a binder component. A physical surface treatment such as a discharge treatment or a corona discharge treatment, or a chemical surface treatment with a surfactant or a coupling agent may be performed.

The surface treatment can be performed using a surface treatment agent of an inorganic compound or an organic compound. Examples of inorganic compounds used for the surface treatment include inorganic compounds containing cobalt (CoO ₂ , Co ₂ O ₃ , Co ₃ O _4, etc.), inorganic compounds containing aluminum (Al ₂ O ₃ , Al (OH) _{3, etc.} Etc.), inorganic compounds containing zirconium (ZrO ₂ , Zr (OH) ₄ etc.), inorganic compounds containing silicon (SiO ₂ etc.), inorganic compounds containing iron (Fe ₂ O ₃ etc.), etc. .
Inorganic compounds containing cobalt, inorganic compounds containing aluminum, and inorganic compounds containing zirconium are particularly preferred, and inorganic compounds containing cobalt, Al (OH) ₃ , and Zr (OH) ₄ are most preferred.
Examples of organic compounds used for the surface treatment include polyols, alkanolamines, stearic acid, silane coupling agents, and titanate coupling agents. Silane coupling agents are most preferred. In particular, the surface treatment is preferably performed with at least one of a silane coupling agent (organosilane compound), a partial hydrolyzate thereof, and a condensate thereof.

Examples of titanate coupling agents include metal alkoxides such as tetramethoxy titanium, tetraethoxy titanium, and throat tetraisopropoxy titanium, and preneact (KR-TTS, KR-46B, KR-55, KR-41B, etc .; Ajinomoto Co., Inc. ))).
Examples of the organic compound used for the surface treatment include polyols, alkanolamines, and other organic compounds having an anionic group, and particularly preferable are organic compounds having a carboxyl group, a sulfonic acid group, or a phosphoric acid group. is there. Stearic acid, lauric acid, oleic acid, linoleic acid, linolenic acid and the like can be preferably used.
The organic compound used for the surface treatment preferably further has a crosslinked or polymerizable functional group. Crosslinkable or polymerizable functional groups include ethylenically unsaturated groups (for example, (meth) acrylic groups, allyl groups, styryl groups, vinyloxy groups, etc.) that can undergo addition reactions and polymerization reactions with radical species, cationic polymerizable groups (Epoxy groups, oxatanyl groups, vinyloxy groups, etc.), polycondensation reactive groups (hydrolyzable silyl groups, etc., N-methylol groups) and the like can be mentioned, and groups having an ethylenically unsaturated group are preferred.

  Two or more kinds of these surface treatments can be used in combination, and it is particularly preferable to use an inorganic compound containing aluminum and an inorganic compound containing zirconium.

When the inorganic particles are silica, the use of a coupling agent is particularly preferred. As the coupling agent, an alkoxy metal compound (eg, titanium coupling agent, silane coupling agent) is preferably used. Of these, silane coupling treatment is particularly effective.
The above coupling agent is used as a surface treatment agent for the inorganic filler of the low refractive index layer in advance for surface treatment prior to the preparation of the layer coating solution, and is added as an additive during the preparation of the layer coating solution. It is preferable to make it contain in a layer.
The silica fine particles are preferably dispersed in the medium in advance before the surface treatment in order to reduce the load of the surface treatment.
Specific examples of the surface treatment agent and the surface treatment catalyst that can be preferably used in the present invention include organosilane compounds and catalysts described in WO 2004/017105.

1- (10) Dispersant Various dispersants can be used for dispersing the particles used in the present invention.
The dispersant preferably further contains a crosslinkable or polymerizable functional group. Crosslinkable or polymerizable functional groups include ethylenically unsaturated groups (for example, (meth) acryloyl groups, allyl groups, styryl groups, vinyloxy groups, etc.) that can undergo addition reactions and polymerization reactions with radical species, and cationic polymerizable groups (epoxies). Groups, oxatanyl groups, vinyloxy groups, etc.), polycondensation reactive groups (hydrolyzable silyl groups, etc., N-methylol groups) and the like, and functional groups having an ethylenically unsaturated group are preferred.

It is preferable to use a dispersant having an anionic group for the dispersion of inorganic particles, particularly for the dispersion of inorganic particles containing TiO ₂ as a main component, more preferably having an anionic group and a crosslinkable or polymerizable functional group, It is particularly preferable that the dispersant has the cross-linked or polymerizable functional group in the side chain.

  As the anionic group, a group having an acidic proton such as a carboxyl group, a sulfonic acid group (sulfo), a phosphoric acid group (phosphono), a sulfonamide group, or a salt thereof is effective, and in particular, a carboxyl group, a sulfonic acid group, A phosphoric acid group or a salt thereof is preferable, and a carboxyl group and a phosphoric acid group are particularly preferable. The number of anionic groups contained in the dispersing agent per molecule may be plural, but is preferably 2 or more on average, more preferably 5 or more, Particularly preferred is 10 or more. Moreover, the anionic group contained in a dispersing agent may contain multiple types in 1 molecule.

In the dispersant having an anionic group in the side chain, the composition of the anionic group-containing repeating unit is in the range of 10 ^{−4 to} 100 mol%, preferably 1 to 50 mol%, particularly preferably 5 in the total repeating units. ˜20 mol%.

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

  The average number of cross-linkable or polymerizable functional groups contained in the dispersant per molecule is preferably 2 or more, more preferably 5 or more, and particularly preferably 10 or more. Moreover, the crosslinking or polymerizable functional group contained in the dispersant may contain a plurality of types in one molecule.

In the preferred dispersant for use in the present invention, examples of the repeating unit having an ethylenically unsaturated group in the side chain include poly-1,2-butadiene and poly-1,2-isoprene structures or (meth) acrylic acid. An ester or amide repeating unit to which a specific residue (the R group of —COOR or —CONHR) is bonded can be used. Examples of the specific residue (R _{group), - (CH 2) n} -CR 21 = CR 22 R 23, - (CH 2 O) n-CH 2 CR 21 = CR 22 R 23, - (CH _{2 CH 2 O) n-CH} 2 CR 21 = CR 22 R 23, - (CH 2) n-NH-CO-O-CH 2 CR 21 = CR 22 R 23, - (CH 2) n-O-CO —CR ²¹ ═CR ²² R ²³ and — (CH ₂ CH ₂ O) ₂ —X (R ^{21 to} R ²³ are each a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, or an alkoxy group. R ²¹ and R ²² or R ²³ may be bonded to each other to form a ring, n is an integer of 1 to 10, and X is a dicyclopentadienyl residue. There are). Specific examples of R of the ester residue include —CH ₂ CH═CH ₂ (corresponding to an allyl (meth) acrylate polymer described in JP-A No. 64-17047), —CH ₂ CH ₂ O—CH ₂ CH _{= CH 2, -CH 2 CH 2} OCOCH = CH 2, -CH 2 CH 2 OCOC (CH 3) = CH 2, -CH 2 C (CH 3) = CH 2, -CH 2 CH = CH-C 6 H ₅ , —CH ₂ CH ₂ OCOCH═CH—C ₆ H ₅ , —CH ₂ CH ₂ —NHCOO—CH ₂ CH═CH ₂ and —CH ₂ CH ₂ O—X (X is a dicyclopentadienyl residue) Is included. Specific examples of R of the amide residue include —CH ₂ CH═CH ₂ , —CH ₂ CH ₂ —Y (Y is a 1-cyclohexenyl residue) and —CH ₂ CH ₂ —OCO—CH═CH ₂ , _{-CH 2 CH 2 -OCO-C (} CH 3) = CH 2 are included.

  In the dispersant having an ethylenically unsaturated group, a free radical (a polymerization initiation radical or a growth radical of a polymerization process of a polymerizable compound) is added to the unsaturated bond group, and the polymer compound is directly or between molecules. Addition polymerization is carried out through the polymerization chain, and a crosslink is formed between the molecules to cure. Alternatively, atoms in the molecule (for example, hydrogen atoms on carbon atoms adjacent to the unsaturated bond group) are extracted by free radicals to form polymer radicals that are bonded together to form a bridge between the molecules. Harden.

  The weight average molecular weight (Mw) of the dispersant having an anionic group and a crosslinkable or polymerizable functional group and having the crosslinkable or polymerizable functional group in the side chain is not particularly limited, but is preferably 1000 or more. . The more preferred weight average molecular weight (Mw) of the dispersant is 2,000 to 1,000,000, more preferably 5,000 to 200,000, and particularly preferably 10,000 to 100,000.

  The cross-linkable or polymerizable functional group-containing unit may constitute all repeating units other than the anionic group-containing repeating unit, preferably 5 to 50 mol% of the total cross-linking or repeating unit, particularly Preferably it is 5-30 mol%.

  The dispersant may be a copolymer with an appropriate monomer other than a monomer having a crosslinking or polymerizable functional group or an anionic group. Although it does not specifically limit regarding a copolymerization component, It selects from various viewpoints, such as dispersion stability, compatibility with another monomer component, and the intensity | strength of a formed film. Preferable examples include methyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, styrene and the like.

  The form of the dispersant is not particularly limited, but is preferably a block copolymer or a random copolymer, and particularly preferably a random copolymer from the viewpoint of cost and ease of synthesis.

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

  Specific examples of the dispersant preferably used in the present invention are shown below, but the dispersant for the present invention is not limited thereto. Unless otherwise specified, it represents a random copolymer.

1- (11) Antifouling agent For the purpose of imparting antifouling properties, water resistance, chemical resistance, slipping properties and the like to the film of the present invention, particularly the uppermost layer of the film, known silicone type or fluorine type It is preferable to add an antifouling agent, a slip agent and the like as appropriate.
When these additives are added to the low refractive index layer, it is preferably added in the range of 0.01 to 20% by mass of the total solid content of the low refractive index layer, more preferably 0.05 to 10% by mass. It is a case where it adds in the range of 0.1-5 mass% especially preferably.

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

As the fluorine compound, a compound having a fluoroalkyl group is preferable. The fluoroalkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and a straight chain (for example, —CF ₂ CF ₃ , —CH ₂ (CF ₂ ) ₄ H, —CH ₂ (CF ₂ ) ₈ CF ₃ , —CH ₂ CH ₂ (CF ₂ ) ₄ H, etc.), even branched structures (eg, CH (CF ₃ ) ₂ , CH ₂ CF (CF ₃ ) ₂ , CH (CH ₃ ) CF ₂ CF ₃ , CH (CH ₃ ) (CF ₂ ) ₅ CF ₂ H, etc.), alicyclic structures (preferably 5-membered or 6-membered rings such as perfluorocyclohexyl group, perfluorocyclopentyl, etc. Group or an alkyl group substituted with these, and may have an ether bond (for example, CH ₂ OCH ₂ CF ₂ CF ₃ , CH ₂ CH ₂ OCH ₂ C ₄ F ₈ H, CH ₂ CH ₂ OCH ₂ CH ₂ C ₈ F ₁₇ , CH ₂ CH ₂ OCF ₂ CF ₂ OCF ₂ CF ₂ H, etc.). A plurality of the fluoroalkyl groups may be contained in the same molecule.

  It is preferable that the fluorine-based compound further has a substituent that contributes to bond formation or compatibility with the low refractive index layer film. The substituents may be the same or different, and a plurality of substituents are preferable. Examples of preferred substituents include acryloyl group, methacryloyl group, vinyl group, aryl group, cinnamoyl group, epoxy group, oxetanyl group, hydroxyl group, polyoxyalkylene group, carboxyl group, amino group and the like. The fluorine-based compound may be a polymer or an oligomer with a compound not containing a fluorine atom, and the molecular weight is not particularly limited. Although there is no restriction | limiting in particular in fluorine atom content of a fluorine-type compound, It is preferable that it is 20 mass% or more, It is especially preferable that it is 30-70 mass%, It is most preferable that it is 40-70 mass%. Examples of preferred fluorine-based compounds include Daikin Chemical Industries, Ltd., R-2020, M-2020, R-3833, M-3833 (named above), Dainippon Ink Co., Ltd., Megafac F-171. , F-172, F-179A, defender MCF-300 (trade name) and the like, but are not limited thereto.

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

1- (12) Surfactant In the film of the present invention, in order to ensure surface uniformity such as coating unevenness, drying unevenness, point defect, etc., any fluorine-based or silicone-based surfactant, or Both of them are preferably contained in the coating composition for forming the hard coat layer. In particular, a fluorine-based surfactant can be preferably used because an effect of improving surface defects such as coating unevenness, drying unevenness, and point defects appears at a smaller addition amount. Productivity can be improved by giving high-speed coating suitability while improving surface uniformity.

  Preferable examples of the fluorosurfactant include a fluoroaliphatic group-containing copolymer (sometimes abbreviated as “fluorine polymer”), and the fluoropolymer includes the following monomer (i): A copolymer of an acrylic resin or a methacrylic resin containing a corresponding repeating unit and a vinyl monomer copolymerizable therewith (for example, a monomer represented by the following (ii)) is useful.

(I) Fluoroaliphatic group-containing monomer represented by the following general formula

General formula

In the general formula A, R ¹¹ represents a hydrogen atom or a methyl group, X represents an oxygen atom, a sulfur atom or —N (R ¹² ) —, m is an integer of 1-6, and n is an integer of 2-4. To express. R ¹² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, specifically a methyl group, an ethyl group, a propyl group, or a butyl group, preferably a hydrogen atom or a methyl group. X is preferably an oxygen atom.

(Ii) Monomer represented by the following general formula (b) copolymerizable with (i)

General formula

In the general formula B, R ¹³ represents a hydrogen atom or a methyl group, Y represents an oxygen atom, a sulfur atom or —N (R ¹⁵ ) —, R ¹⁵ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, specifically Specifically, it represents a methyl group, an ethyl group, a propyl group, or a butyl group, preferably a hydrogen atom or a methyl group. Y is an oxygen atom, -N (H) -, and -N (CH ₃₎ - are preferred.
R ¹⁴ represents a linear, branched or cyclic alkyl group having 4 to 20 carbon atoms which may have a substituent. Examples of the substituent for the alkyl group of R ¹⁴ include a hydroxyl group, an alkylcarbonyl group, an arylcarbonyl group, a carboxyl group, an alkyl ether group, an aryl ether group, a halogen atom such as a fluorine atom, a chlorine atom, and a bromine atom, a nitro group, and a cyano group. , Amino groups and the like, but not limited thereto. Examples of the linear, branched or cyclic alkyl group having 4 to 20 carbon atoms include a butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group and undecyl group which may be linear or branched. , Dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, octadecyl group, eicosanyl group, etc., and monocyclic cycloalkyl groups such as cyclohexyl group, cycloheptyl group and bicycloheptyl group, bicyclodecyl group, tricycloundecyl group, A polycyclic cycloalkyl group such as a tetracyclododecyl group, an adamantyl group, a norbornyl group, a tetracyclodecyl group, or the like is preferably used.

  The amount of the fluoroaliphatic group-containing monomer represented by the general formula (a) used in the fluoropolymer used in the present invention is 10 mol% or more based on each monomer of the fluoropolymer, preferably Is 15 to 70 mol%, more preferably in the range of 20 to 60 mol%.

The preferred weight average molecular weight of the fluoropolymer used in the present invention is preferably 3000 to 100,000, more preferably 5,000 to 80,000.
Furthermore, the preferable addition amount of the fluoropolymer used in the present invention is in the range of 0.001 to 5% by mass, preferably in the range of 0.005 to 3% by mass, and more preferably, with respect to the coating solution. It is the range of 0.01-1 mass%. If the addition amount of the fluorine-based polymer is less than 0.001% by mass, the effect is insufficient, and if it exceeds 5% by mass, the coating film may not be sufficiently dried or the performance as a coating film (for example, reflectance) Adversely affect the scratch resistance).

  Examples of the specific structure of the fluoropolymer composed of the fluoroaliphatic group-containing monomer represented by the general formula (i) are shown below, but this is not restrictive. In addition, the number in a formula shows the molar ratio of each monomer component. Mw represents a mass average molecular weight.

However, by using such a fluorine-based polymer, the functional group containing F atoms is segregated on the surface of the hard coat layer, so that the surface energy of the hard coat layer is lowered and the hard coat layer has a low refractive index. When the rate layer is overcoated, there arises a problem that the antireflection performance deteriorates. This is presumably because minute unevenness that cannot be visually detected in the low refractive index layer deteriorates because the wettability of the curable composition used for forming the low refractive index layer deteriorates. To solve such problems, by adjusting the structure and amount of the fluorine-based polymer, the surface energy of the hard coat layer preferably in ^{20mN · m -1 ~50mN · m -1} , more preferably it was found that it is effective to control the ^{30mN · m -1 ~40mN · m -1} . In order to realize the surface energy as described above, F / C, which is a ratio of a peak derived from a fluorine atom and a peak derived from a carbon atom, measured by X-ray photoelectron spectroscopy is 0.1 to 1.5. is required.

  Alternatively, by selecting a fluorine-based polymer that is extracted by the solvent that forms the upper layer when the upper layer is applied, it is not unevenly distributed on the lower layer surface (= interface), so that the adhesion between the upper layer and the lower layer is provided. The surface energy of the hard coat layer before application of the low refractive index layer can be reduced by preventing the reduction of surface free energy that can provide an antireflection film having high surface resistance even in high-speed application and having high scratch resistance. The purpose can also be achieved by controlling the range. Examples of such materials include acrylic resins or methacrylic resins containing a repeating unit corresponding to a fluoroaliphatic group-containing monomer represented by the following general formula c, and vinyl monomers copolymerizable therewith (for example, (iv And a monomer represented by ()).

(Iii) Fluoroaliphatic group-containing monomer represented by the following general formula C

General formula C

In the general formula C, R ²¹ represents a hydrogen atom, a halogen atom or a methyl group, and more preferably a hydrogen atom or a methyl group. X ² represents an oxygen atom, a sulfur atom or —N (R ²² ) —, more preferably an oxygen atom or —N (R ²² ) —, and still more preferably an oxygen atom. m is an integer from 1 to 6 (more preferably from 1 to 3, more preferably 1), and n is an integer from 1 to 18 (more preferably from 4 to 12, and even more preferably from 6 to 8). Represents. R ²² represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms which may have a substituent, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and further preferably a hydrogen atom or a methyl group. X is preferably an oxygen atom.
In addition, two or more kinds of fluoroaliphatic group-containing monomers represented by the general formula C may be contained in the fluorine-based polymer as constituent components.

(Iv) A monomer represented by the following general formula (D) that can be copolymerized with the above (iii)

General formula D

In the general formula D, R ²³ represents a hydrogen atom, a halogen atom or a methyl group, more preferably a hydrogen atom or a methyl group. Y ² represents an oxygen atom, a sulfur atom or —N (R ²⁵ ) —, more preferably an oxygen atom or —N (R ²⁵ ) —, and still more preferably an oxygen atom. R ²⁵ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and still more preferably a hydrogen atom or a methyl group.
R ²⁴ is an optionally substituted linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, an alkyl group containing a poly (alkyleneoxy) group, and an optionally substituted aromatic group. (For example, a phenyl group or a naphthyl group). A linear, branched or cyclic alkyl group having 1 to 12 carbon atoms or an aromatic group having 6 to 18 carbon atoms is more preferable, and a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms is more preferable. .

  Hereinafter, examples of specific structures of fluoropolymers containing a repeating unit corresponding to the fluoroaliphatic group-containing monomer represented by formula (c) are shown, but the present invention is not limited thereto. In addition, the number in a formula shows the molar ratio of each monomer component. Mw represents a mass average molecular weight.

1- (13) Thickener

In the formation of the film of the present invention, a thickener may be used to adjust the viscosity of the coating solution.
The term “thickener” as used herein means that the viscosity of the liquid is increased by adding it, and is preferably 0.05 to 50 cP as the magnitude of increase in the viscosity of the coating liquid by adding it. More preferably, it is 0.10-20 cP, Most preferably, it is 0.10-10 cP.

Examples of such thickeners include, but are not limited to:
Poly-ε-caprolactone poly-ε-caprolactone diol poly-ε-caprolactone triol polyvinyl acetate poly (ethylene adipate)
Poly (1,4-butylene adipate)
Poly (1,4-butylene glutarate)
Poly (1,4-butylene succinate)
Poly (1,4-butylene terephthalate)
polyethylene terephthalate)
Poly (2-methyl-1,3-propylene adipate)
Poly (2-methyl-1,3-propylene glutarate)
Poly (neopentyl glycol adipate)
Poly (neopentyl glycol sebacate)
Poly (1,3-propylene adipate)
Poly (1,3-propylene glutarate)
Polyvinyl butyral Polyvinyl formal Polyvinyl acetal Polyvinyl propanal Polyvinyl hexanal Polyvinyl pyrrolidone Polyacrylic acid ester Polymethacrylic acid ester Cellulose acetate Cellulose propionate Cellulose acetate butyrate

  Other known viscosity modifiers such as smectite, tetrasilica mica, bentonite, silica, montmorillonite and sodium polyacrylate, JP-A-10-219136, ethyl cellulose, polyacrylic acid, and organic clay described in JP-A-8-325491. Or a thixotropic agent can be used.

1- (14) Coating solvent As a solvent used in the coating composition for forming each layer of the present invention, each component can be dissolved or dispersed, and a uniform surface is easily formed in the coating process and the drying process. Various solvents selected from the viewpoints of ensuring liquid storage stability and having an appropriate saturated vapor pressure can be used.
Two or more kinds of solvents can be mixed and used. In particular, from the viewpoint of drying load, it is preferable that a solvent having a boiling point of 100 ° C. or lower at normal pressure and room temperature as a main component and a small amount of solvent having a boiling point of 100 ° C. or higher for adjusting the drying speed.

  Examples of the solvent having a boiling point of 100 ° C. or lower include hydrocarbons such as hexane (boiling point 68.7 ° C.), heptane (98.4 ° C.), cyclohexane (80.7 ° C.), benzene (80.1 ° C.), Halogenated carbonization such as dichloromethane (39.8 ° C), chloroform (61.2 ° C), carbon tetrachloride (76.8 ° C), 1,2-dichloroethane (83.5 ° C), trichloroethylene (87.2 ° C) Hydrogens, diethyl ether (34.6 ° C), diisopropyl ether (68.5 ° C), dipropyl ether (90.5 ° C), tetrahydrofuran (66 ° C) and other ethers, ethyl formate (54.2 ° C), Esters such as methyl acetate (57.8 ° C.), ethyl acetate (77.1 ° C.), isopropyl acetate (89 ° C.), acetone (56.1 ° C.), 2-butanone (methyl ethyl) Ketones such as 79.6 ° C, the same as ketone, methanol (64.5 ° C), ethanol (78.3 ° C), 2-propanol (82.4 ° C), 1-propanol (97.2 ° C), etc. Alcohols, cyano compounds such as acetonitrile (81.6 ° C.), propionitrile (97.4 ° C.), carbon disulfide (46.2 ° C.), and the like. Of these, ketones and esters are preferable, and ketones are particularly preferable. Among the ketones, 2-butanone is particularly preferable.

  Examples of the solvent having a boiling point of 100 ° C. or more include, for example, octane (125.7 ° C.), toluene (110.6 ° C.), xylene (138 ° C.), tetrachloroethylene (121.2 ° C.), and chlorobenzene (131.7 ° C.). , Dioxane (101.3 ° C), dibutyl ether (142.4 ° C), isobutyl acetate (118 ° C), cyclohexanone (155.7 ° C), 2-methyl-4-pentanone (same as MIBK, 115.9 ° C) 1-butanol (117.7 ° C.), N, N-dimethylformamide (153 ° C.), N, N-dimethylacetamide (166 ° C.), dimethyl sulfoxide (189 ° C.) and the like. Cyclohexanone and 2-methyl-4-pentanone are preferable.

1- (15) Others In addition to the above-described components, the film of the present invention includes a resin, a coupling agent, a coloring inhibitor, a coloring agent (pigment, dye), an antifoaming agent, a leveling agent, a flame retardant, and an ultraviolet absorber. , Infrared absorbers, adhesion-imparting agents, polymerization inhibitors, antioxidants, surface modifiers, and the like can also be added.

1- (16) Support The support for the film of the present invention is not particularly limited, such as a transparent resin film, a transparent resin plate, a transparent resin sheet, and transparent glass. Transparent resin films include cellulose acylate films (for example, cellulose triacetate film (refractive index 1.48), cellulose diacetate film, cellulose acetate butyrate film, cellulose acetate propionate film), polyethylene terephthalate film, polyethersulfone. Film, polyacrylic resin film, polyurethane resin film, polyester film, polycarbonate film, polysulfone film, polyether film, polymethylpentene film, polyetherketone film, (meth) acrylonitrile film, heavy with alicyclic structure A united resin film or the like can be used.

  Specific examples of the alicyclic structure-containing polymer include (i) a norbornene polymer, (ii) a monocyclic olefin polymer, (iii) a cyclic conjugated diene polymer, and (iv) a vinyl alicyclic polymer. Examples include hydrocarbon polymers and their hydrides. Among these, norbornene-based polymers are preferable from the viewpoints of transparency and moldability.

  Examples of the norbornene-based resin include those manufactured by ZEON Corporation, trade names “ZEONOR” and “ZEONEX”; manufactured by JSR Corporation, trade names “ARTON”; The trade name “APEL” is commercially available.

<Cellulose acylate film>
Among them, a cellulose acylate film having high transparency, optically low birefringence, easy production, and generally used as a protective film for a polarizing plate is preferable, and a cellulose triacetate film is particularly preferable. The thickness of the transparent support is usually about 25 μm to 1000 μm.

In the present invention, it is preferable to use cellulose acetate having an acetylation degree of 59.0 to 61.5% for the cellulose acylate film.
The degree of acetylation means the amount of bound acetic acid per unit mass of cellulose. The degree of acetylation follows the measurement and calculation of the degree of acetylation in ASTM: D-817-91 (test method for cellulose acetate and the like).
The viscosity average degree of polymerization (DP) of cellulose acylate is preferably 250 or more, and more preferably 290 or more.
In addition, the cellulose acylate used in the present invention has a Mw / Mn (Mw is mass average molecular weight, Mn is number average molecular weight) value by gel permeation chromatography close to 1.0, in other words, a molecular weight distribution. Narrow is preferred. The specific value of Mw / Mn is preferably 1.0 to 1.7, more preferably 1.3 to 1.65, and most preferably 1.4 to 1.6. preferable.

In general, the 2, 3, and 6 hydroxyl groups of cellulose acylate are not evenly distributed by 1/3 of the total substitution degree, and the substitution degree of the 6-position hydroxyl group tends to be small. In the present invention, it is preferable that the substitution degree of the 6-position hydroxyl group of cellulose acylate is larger than that of the 2- and 3-positions.
The hydroxyl group at the 6-position with respect to the total degree of substitution is preferably substituted with an acyl group of 32% or more, more preferably 33% or more, and particularly preferably 34% or more. Furthermore, the substitution degree of the 6-position acyl group of cellulose acylate is preferably 0.88 or more. The 6-position hydroxyl group may be substituted with a propionyl group, butyroyl group, valeroyl group, benzoyl group, acryloyl group or the like, which is an acyl group having 3 or more carbon atoms, in addition to the acetyl group. The degree of substitution at each position can be determined by NMR.
In the present invention, as cellulose acylate, paragraphs “0043” to “0044” [Example] [Synthesis Example 1], paragraphs “0048” to “0049” [Synthesis Example 2], paragraph “ Cellulose acetate obtained by the method described in “0051” to “0052” [Synthesis Example 3] can be used.

<Manufacture of cellulose acylate film>
The cellulose acylate film used in the present invention can be produced by a solution casting method (solvent casting method). In the solvent cast method, a film is produced using a solution (dope) in which cellulose acylate is dissolved in an organic solvent.

  The organic solvent is a solvent selected from ethers having 3 to 12 carbon atoms, ketones having 3 to 12 carbon atoms, esters having 3 to 12 carbon atoms, and halogenated hydrocarbons having 1 to 6 carbon atoms. It is preferable to contain. Two or more organic solvents may be mixed and used.

  The ether, ketone and ester may have a cyclic structure. A compound having two or more functional groups of ether, ketone and ester (that is, —O—, —CO— and —COO—) can also be used as the organic solvent. The organic solvent may have another functional group such as an alcoholic hydroxyl group. In the case of an organic solvent having two or more types of functional groups, the preferred number of carbon atoms may be within the range of the preferred number of carbon atoms specified above for the compound having any functional group.

Examples of the ether having 3 to 12 carbon atoms include diisopropyl ether, dimethoxymethane, dimethoxyethane, 1,4-dioxane, 1,3-dioxolane, tetrahydrofuran, anisole and phenetole.
Examples of ketones having 3 to 12 carbon atoms include acetone, methyl ethyl ketone, diethyl ketone, diisobutyl ketone, cyclohexanone and methylcyclohexanone.
Examples of the esters having 3 to 12 carbon atoms include ethyl formate, propyl formate, pentyl formate, methyl acetate, ethyl acetate and pentyl acetate.

  Examples of the organic solvent having two or more kinds of functional groups include 2-ethoxyethyl acetate, 2-methoxyethanol and 2-butoxyethanol.

  The number of carbon atoms of the halogenated hydrocarbon is preferably 1 or 2, and most preferably 1. The halogen of the halogenated hydrocarbon is preferably chlorine. The proportion of halogenated hydrocarbon hydrogen atoms replaced with halogen is preferably 25 to 75 mol%, more preferably 30 to 70 mol%, and more preferably 35 to 65 mol%. More preferably, it is most preferable that it is 40-60 mol%. Methylene chloride is a representative halogenated hydrocarbon.

The cellulose acylate solution (dope) can be adjusted by a general method. A general method means processing at a temperature of 0 ° C. or higher (room temperature or high temperature). The solution can be prepared by using a dope preparation method and apparatus in a normal solvent cast method. In the case of a general method, it is preferable to use a halogenated hydrocarbon (particularly methylene chloride) as the organic solvent. A non-chlorinated solvent can also be used, and examples thereof include those described in JIII Journal of Technical Disclosure No. 2001-1745.
The amount of cellulose acylate is adjusted so as to be contained in the obtained solution in an amount of 10 to 40% by mass. The amount of cellulose acylate is more preferably 10 to 30% by mass. Arbitrary additives described later may be added to the organic solvent (main solvent).
The solution can be prepared by stirring cellulose acylate and an organic solvent at room temperature (0 to 40 ° C.). High concentration solutions may be stirred under pressure and heating conditions. Specifically, cellulose acylate and an organic solvent are placed in a pressure vessel and sealed, and stirred while being heated to a temperature equal to or higher than the boiling point of the solvent at normal temperature and in a range where the solvent does not boil. The heating temperature is usually 40 ° C. or higher, preferably 60 to 200 ° C., more preferably 80 to 110 ° C.

Each component may be coarsely mixed in advance and then placed in a container. Moreover, you may put into a container sequentially.
The container needs to be configured so that it can be stirred. The container can be pressurized by injecting an inert gas such as nitrogen gas. Moreover, you may utilize the raise of the vapor pressure of the solvent by heating. Or after sealing a container, you may add each component under pressure.
When heating, it is preferable to heat from the outside of the container. For example, a jacket type heating device can be used. The entire container can also be heated by providing a plate heater outside the container and piping to circulate the liquid.
It is preferable to provide a stirring blade inside the container and stir using this. The stirring blade preferably has a length that reaches the vicinity of the wall of the container. A scraping blade is preferably provided at the end of the stirring blade in order to renew the liquid film on the vessel wall.
Instruments such as a pressure gauge and a thermometer may be installed in the container. Each component is dissolved in a solvent in the container. The prepared dope is taken out of the container after cooling, or taken out and then cooled using a heat exchanger or the like.

A solution can also be prepared by a cooling dissolution method. In the cooling dissolution method, cellulose acylate can be dissolved in an organic solvent that is difficult to dissolve by a normal dissolution method. In addition, even if it is a solvent which can melt | dissolve a cellulose acetate with a normal melt | dissolution method, there exists an effect that a uniform solution can be obtained rapidly according to a cooling melt | dissolution method.
In the cooling dissolution method, first, cellulose acylate is gradually added to an organic solvent at room temperature while stirring.
The amount of cellulose acylate is preferably adjusted so as to be contained in the mixture at 10 to 40% by mass. The amount of cellulose acylate is more preferably 10 to 30% by mass. Furthermore, you may add the arbitrary additive mentioned later in a mixture.

The mixture is then cooled to -100 to -10 ° C (preferably -80 to -10 ° C, more preferably -50 to -20 ° C, most preferably -50 to -30 ° C). The cooling can be performed, for example, in a dry ice / methanol bath (−75 ° C.) or a cooled diethylene glycol solution (−30 to −20 ° C.). When cooled in this way, the mixture of cellulose acetate and organic solvent solidifies.
The cooling rate is preferably 4 ° C./min or more, more preferably 8 ° C./min or more, and most preferably 12 ° C./min or more. The faster the cooling rate, the better. However, 10,000 ° C./second is the theoretical upper limit, 1000 ° C./second is the technical upper limit, and 100 ° C./second is the practical upper limit. The cooling rate is a value obtained by dividing the difference between the temperature at the start of cooling and the final cooling temperature by the time from the start of cooling to the final cooling temperature.

Further, when this is heated to 0 to 200 ° C. (preferably 0 to 150 ° C., more preferably 0 to 120 ° C., most preferably 0 to 50 ° C.), cellulose acetate is dissolved in the organic solvent. The temperature can be raised by simply leaving it at room temperature or in a warm bath.
The heating rate is preferably 4 ° C./min or more, more preferably 8 ° C./min or more, and most preferably 12 ° C./min or more. The higher the heating rate, the better. However, 10,000 ° C./second is the theoretical upper limit, 1000 ° C./second is the technical upper limit, and 100 ° C./second is the practical upper limit. The heating rate is a value obtained by dividing the difference between the temperature at the start of heating and the final heating temperature by the time from the start of heating until the final heating temperature is reached. .
A uniform solution is obtained as described above. If the dissolution is insufficient, the cooling and heating operations may be repeated. Whether or not the dissolution is sufficient can be determined by merely observing the appearance of the solution with the naked eye.

In the cooling dissolution method, it is desirable to use a sealed container in order to avoid moisture mixing due to condensation during cooling. In the cooling and heating operation, when the pressure is applied during cooling and the pressure is reduced during heating, the dissolution time can be shortened. In order to perform pressurization and decompression, it is desirable to use a pressure-resistant container.
In addition, according to differential scanning calorimetry (DSC), a 20 mass% solution obtained by dissolving cellulose acetate (acetylation degree: 60.9%, viscosity average polymerization degree: 299) in methyl acetate by a cooling dissolution method was 33. There exists a quasi-phase transition point between a sol state and a gel state in the vicinity of ° C., and a uniform gel state is obtained below this temperature. Therefore, this solution needs to be maintained at a temperature equal to or higher than the pseudo phase transition temperature, preferably about the gel phase transition temperature plus about 10 ° C. However, this pseudo phase transition temperature varies depending on the degree of acetylation of cellulose acetate, the degree of viscosity average polymerization, the concentration of the solution, and the organic solvent used.

A cellulose acylate film is produced from the prepared cellulose acylate solution (dope) by a solvent cast method.
The dope is cast on a drum or band and the solvent is evaporated to form a film. The concentration of the dope before casting is preferably adjusted so that the solid content is 18 to 35%.
The surface of the drum or band is preferably finished in a mirror state. The casting and drying methods in the solvent casting method are described in U.S. Pat. No. 7,736892, JP-B Nos. 45-4554, 49-5614, and 62-1115035.
The dope is preferably cast on a drum or band having a surface temperature of 10 ° C. or less.
After casting, it is preferable to dry it by applying air for 2 seconds or more. The obtained film can be peeled off from the drum or band, and further dried by high-temperature air whose temperature is successively changed from 100 to 160 ° C. to evaporate the residual solvent. The above method is described in Japanese Patent Publication No. 5-17844. According to this method, it is possible to shorten the time from casting to stripping. In order to carry out this method, it is necessary for the dope to gel at the surface temperature of the drum or band during casting.

  A film can also be produced by casting two or more layers by a solvent casting method using a plurality of prepared cellulose acylate solutions (dope). In this case, the dope is cast on a drum or band and the solvent is evaporated to form a film. It is preferable to adjust the concentration of the dope before casting so that the solid content is 10 to 40% by mass. The surface of the drum or band is preferably finished in a mirror state.

  When casting a plurality of cellulose acylate liquids of two or more layers, it is possible to cast a plurality of cellulose acylate solutions, and cellulose is supplied from a plurality of casting openings provided at intervals in the traveling direction of the support. A film may be produced while casting and laminating a solution containing an acylate. For example, in each publication such as JP-A Nos. 61-158414, 1-122419, 11-198285, etc. The described method is applicable. Further, it may be formed into a film by casting a cellulose acylate solution from two casting ports. For example, JP-B-60-27562, JP-A-61-94724, JP-A-61-104813, It can be carried out by the methods described in JP-A Nos. 61-158413 and 6-134933. Further, a cellulose acylate film in which a flow of a high-viscosity cellulose acylate solution described in JP-A-56-162617 is wrapped with a low-viscosity cellulose acylate solution and the high-low viscosity cellulose acylate solution is simultaneously extruded. A casting method may be used.

  Alternatively, by using two casting ports, the film cast on the support by the first casting port is peeled off, and the second casting is performed on the side that is in contact with the support surface, thereby the film. For example, it is a method described in Japanese Patent Publication No. 44-20235. The cellulose acylate solutions to be cast may be the same solution or different cellulose acylate solutions, and are not particularly limited. In order to give a function to a plurality of cellulose acylate layers, a cellulose acylate solution corresponding to the function may be extruded from each casting port.

  Furthermore, in the present invention, the cellulose acylate solution is cast simultaneously with a solution for forming other functional layers (for example, an adhesive layer, a dye layer, an antistatic layer, an antihalation layer, a UV absorbing layer, a polarizing layer, etc.) Simultaneous formation of the layer and film formation can also be carried out.

  In the case of a single-layer solution, it is necessary to extrude a high-concentration and high-viscosity cellulose acylate solution to obtain the required film thickness. In this case, the stability of the cellulose acylate solution is poor and solids are generated. In many cases, however, it becomes a problem due to a failure or a poor flatness. As this solution, a plurality of cellulose acylate solutions are cast from a casting port. As a result, it is possible to extrude a highly viscous solution onto the support at the same time, not only can the flatness be improved and an excellent planar film can be produced, but also a concentrated cellulose acylate solution can be used to reduce the drying load. Reduction can be achieved and film production speed can be increased.

A plasticizer can be added to the cellulose acylate film in order to improve the mechanical properties or to improve the drying rate after casting during film production. As the plasticizer, phosphoric acid ester or carboxylic acid ester is used. Examples of phosphate esters include triphenyl phosphate (TPP), diphenyl biphenyl phosphate, and tricresyl phosphate (TCP). Representative examples of the carboxylic acid ester include phthalic acid esters and citric acid esters. Examples of phthalic acid esters include dimethyl phthalate (DMP), diethyl phthalate (DEP), dibutyl phthalate (DBP), dioctyl phthalate (DOP), diphenyl phthalate (DPP) and diethyl hexyl phthalate (DEHP). Examples of citrate esters include triethyl O-acetylcitrate (OACTE) and tributyl O-acetylcitrate (OACTB). Examples of other carboxylic acid esters include butyl oleate, methylacetyl ricinoleate, dibutyl sebacate, and various trimellitic acid esters. Phthalate plasticizers (DMP, DEP, DBP, DOP, DPP, DEHP) are preferably used. DEP and DPP are particularly preferred.
The addition amount of the plasticizer is preferably 0.1 to 25% by mass of the amount of cellulose acylate, more preferably 1 to 20% by mass, and most preferably 3 to 15% by mass.

  A degradation inhibitor (eg, antioxidant, peroxide decomposer, radical inhibitor, metal deactivator, acid scavenger, amine) may be added to the cellulose acylate film. The deterioration inhibitors are described in JP-A-3-199201, JP-A-597073, JP-A-5-194789, JP-A-5-271471, and JP-A-6-107854. The addition amount of the deterioration preventing agent is preferably 0.01 to 1% by mass of the solution (dope) to be prepared in consideration of the effect of the deterioration preventing agent and bleeding out (bleeding out) to the film surface. More preferably, the content is 0.01 to 0.2% by mass. Examples of particularly preferred deterioration inhibitors include butylated hydroxytoluene (BHT) and tribenzylamine (TBA).

In the cellulose acylate film, a retardation increasing agent can be used as necessary in order to adjust the retardation of the film. The retardation of the film is preferably 0 to 300 nm in the film thickness direction and 0 to 1000 nm in the in-plane direction.
An aromatic compound having at least two aromatic rings is preferable as the retardation increasing agent, and the aromatic compound is used in an amount of 0.01 to 20 parts by mass with respect to 100 parts by mass of cellulose acylate. The aromatic compound is preferably used in the range of 0.05 to 15 parts by mass, and more preferably in the range of 0.1 to 10 parts by mass with respect to 100 parts by mass of cellulose acetate. Two or more aromatic compounds may be used in combination.
Details are described in Japanese Patent Application Laid-Open Nos. 2000-1111914, 2000-275434, 2002-236215, and International Publication No. 00/065384.

<Stretching treatment of cellulose acylate film>
The produced cellulose acylate film can further improve drying unevenness, film thickness unevenness caused by drying shrinkage, and surface unevenness by stretching treatment. The stretching treatment is also used for adjusting the retardation.
Although there is no limitation in particular in the method of the width direction extending | stretching process, the extending | stretching method by a tenter is mentioned as the example.
More preferably, the longitudinal stretching is performed in the longitudinal direction of the roll, and the longitudinal stretching is performed by adjusting the draw ratio of each pass roll (rotational ratio between the pass rolls) between the pass rolls that transport the roll film. Is possible.

<Polyethylene terephthalate film>
In the present invention, the polyethylene terephthalate film is also preferably used because it is excellent in transparency, mechanical strength, flatness, chemical resistance and moisture resistance, and is inexpensive.
In order to further improve the adhesion strength between the transparent plastic film and the hard coat layer provided thereon, the transparent plastic film is more preferably subjected to an easy adhesion treatment.
Examples of commercially available PET films with an easily adhesive layer for optics include Toyobo Co., Ltd. Cosmo Shine A4100 and A4300.

2. The layer which comprises a film Although the film of this invention is obtained by mixing and coating said various compounds, it describes about the layer which comprises the film of this invention next.

2- (1) Hard Coat Layer The optical film of the present invention is preferably provided with a hard coat layer on one surface of the transparent support in order to impart physical strength of the film. The hard coat layer imparts light scattering properties and preferably functions as a light scattering layer in the optical film of the present invention.
Preferably, a low refractive index layer is provided on the hard coat layer, and more preferably an intermediate refractive index layer and a high refractive index layer are provided between the hard coat layer and the low refractive index layer to constitute an antireflection film. The hard coat layer may be composed of two or more layers. The hard coat layer may have antiglare properties

  The refractive index of the hard coat layer in the present invention is preferably in the range of 1.48 to 2.00, more preferably 1.50 to 1, from the optical design for obtaining an antireflection film. .90, more preferably 1.52-1.80. In the case of an antireflection film in which a low refractive index layer is laminated on a hard coat layer, since there is at least one low refractive index layer on the hard coat layer, if the refractive index is too smaller than this range, the antireflection property is lowered. However, if it is too large, the color of the reflected light tends to become strong.

From the viewpoint of imparting sufficient durability and impact resistance to the film, the thickness of the hard coat layer is usually about 0.5 μm to 50 μm, preferably 1 μm to 20 μm, more preferably 2 μm. 10 μm, most preferably 3 μm to 7 μm.
Further, the strength of the hard coat layer is preferably H or more, more preferably 2H or more, and most preferably 3H or more in a pencil hardness test.
Furthermore, in the Taber test according to JIS K5400, the smaller the wear amount of the test piece before and after the test, the better.

The hard coat layer is preferably formed by a crosslinking reaction or a polymerization reaction of an ionizing radiation curable compound. For example, it may be formed by coating a coating composition containing an ionizing radiation-curable polyfunctional monomer or polyfunctional oligomer on a transparent support and subjecting the polyfunctional monomer or polyfunctional oligomer to a crosslinking reaction or a polymerization reaction. it can.
The functional group of the ionizing radiation curable polyfunctional monomer or polyfunctional oligomer is preferably a light, electron beam, or radiation polymerizable group, and among them, a photopolymerizable functional group is preferable.
Examples of the photopolymerizable functional group include unsaturated polymerizable functional groups such as a (meth) acryloyl group, a vinyl group, a styryl group, and an allyl group. Among them, a (meth) acryloyl group is preferable.

  The hard coat layer has matte particles having an average particle diameter of 1.0 to 10.0 μm, preferably 1.5 to 7.0 μm, for example, inorganic compound particles or resin particles described later used for the purpose of imparting antiglare properties, Translucent fine particles whose surface is coated with a conductive substance are included. By containing the mat particles in the hard coat layer, light scattering properties can be imparted.

  For the purpose of controlling the refractive index of the hard coat layer, a high refractive index monomer, inorganic particles, or both can be added to the binder of the hard coat layer. In addition to the effect of controlling the refractive index, the inorganic particles also have the effect of suppressing cure shrinkage due to the crosslinking reaction. In the present invention, a polymer formed by polymerizing the polyfunctional monomer and / or the high refractive index monomer after the hard coat layer is formed, and the inorganic particles dispersed therein are referred to as a binder.

The haze of the hard coat layer varies depending on the function imparted to the antireflection film.
In the case where the sharpness of the image is maintained, the reflectance of the surface is suppressed, and the light scattering function is not imparted inside and on the surface of the hard coat layer, the haze value is preferably as low as possible, specifically 10% or less is preferable. More preferably, it is 5% or less, and most preferably 2% or less.

On the other hand, in addition to the function of suppressing the reflectance of the surface, in the case of imparting an antiglare function by surface scattering of the hard coat layer, the surface haze is preferably 5% to 15%, preferably 5% to 10%. It is more preferable that
In addition, when it is difficult to see the pattern, color unevenness, brightness unevenness, glare, etc. of the liquid crystal panel due to internal scattering of the hard coat layer, or to add the function of expanding the viewing angle by scattering, the internal haze value The value obtained by subtracting the surface haze value) is preferably 0% to 90%, more preferably 15% to 90%, and most preferably 30% to 90%.
The film of the present invention can freely set surface haze and internal haze according to the purpose.

  In addition, for the surface irregularity shape of the hard coat layer, in order to obtain a clear surface for the purpose of maintaining the sharpness of the image, among the characteristics indicating the surface roughness, for example, the centerline average roughness (Ra) is set. The thickness is preferably 0.10 μm or less. Ra is more preferably 0.09 μm or less, and still more preferably 0.08 μm or less. In a film including a hard coat layer, the surface unevenness of the hard coat layer is dominant to the surface unevenness of the film, and the center line average roughness of the antireflection film is adjusted by adjusting the center line average roughness of the hard coat layer. The thickness can be within the above range.

  In order to maintain the sharpness of the image, it is preferable to adjust the clarity of the transmitted image in addition to adjusting the uneven shape of the surface. The clearness of the transmitted image of the clear antireflection film is preferably 60% or more. The transmitted image clarity is generally an index indicating the degree of blurring of an image reflected through a film, and the larger this value, the clearer and better the image viewed through the film. The transmitted image definition is preferably 70% or more, and more preferably 80% or more.

Furthermore, as a method for forming the antiglare property on the hard coat layer, a method of laminating and forming a mat-shaped shaping film having fine irregularities on the surface as described in JP-A-6-16851, JP-A-2000- A method of forming by curing shrinkage of an ionizing radiation curable resin due to a difference in ionizing radiation dose as described in No. 206317, a weight ratio of a good solvent to a translucent resin by drying as described in JP-A No. 2000-338310 A method of forming unevenness on the surface of the coating film by solidifying the light-transmitting fine particles and the light-transmitting resin by gelation by reducing the surface unevenness by external pressure as described in JP-A-2000-275404 Methods of imparting and the like are known, and these known methods can be used.
The antiglare hard coat layer that can be used in the present invention preferably contains a binder capable of imparting hard coat properties, translucent particles for imparting antiglare properties, and a solvent as essential components. Surface irregularities are preferably formed by protrusions of the light particles themselves or protrusions formed by an aggregate of a plurality of particles.
The antiglare hard coat layer formed by dispersing the matte particles is composed of a binder and translucent particles dispersed in the binder.

As specific examples of the mat particles, inorganic particles such as silica particles and TiO ₂ particles; resin particles such as acrylic particles, crosslinked acrylic particles, polystyrene particles, crosslinked styrene particles, melamine resin particles, and benzoguanamine resin particles are preferable. Can be mentioned. Of these, crosslinked styrene particles, crosslinked acrylic particles, and silica particles are preferred.
The shape of the mat particles can be either spherical or irregular.

  Two or more kinds of mat particles having different particle diameters may be used in combination. It is possible to impart anti-glare properties with mat particles having a larger particle size and to impart other optical characteristics with mat particles having a smaller particle size. For example, when an anti-glare antireflection film is attached to a high-definition display of 133 ppi or higher, a problem in display image quality called “glare” may occur. “Glitter” is derived from the fact that pixels are enlarged or reduced due to unevenness present on the surface of the antiglare and antireflection antireflection film, resulting in loss of luminance uniformity, but particles smaller than mat particles that impart antiglare properties. It can be greatly improved by using mat particles having a diameter different from that of the binder.

The mat particles are contained in the antiglare hard coat layer so that the amount of mat particles in the formed antiglare hard coat layer is preferably 10 to 1000 mg / m ² , more preferably 100 to 700 mg / m ^2. Is done.
The particle size distribution of the mat particles is measured by a Coulter counter method, and the measured distribution is converted into a particle number distribution.

[Phase separation]
As an example of a technique for imparting anti-glare properties other than expressing anti-glare properties using translucent particles that can be used in the present invention, irregularities are formed on the surface of the coating film by spinodal decomposition of a plurality of polymers. A method is mentioned. Moreover, it becomes possible to give favorable light diffusibility by giving a difference in the refractive index of the phase isolate | separated especially. The light scattering layer prepared by spinodal decomposition is composed of a plurality of polymers having different refractive indexes, and is usually a phase having at least a co-continuous phase structure in the use atmosphere (especially at room temperature of about 10 to 30 ° C.). A separation structure is formed. The co-continuous phase structure is formed by spinodal decomposition from a liquid phase containing a plurality of polymers (a liquid phase at room temperature, for example, a mixed liquid or a solution). The co-continuous phase structure is usually formed by spinodal decomposition through evaporation of a solvent using a composition (for example, a mixed solution or a solution) containing a plurality of polymers and forming a liquid phase at room temperature. Since such a light scattering layer is formed from a liquid phase, it has a uniform and fine co-continuous phase structure. When such a transmission type optical (light scattering) film is used, incident light is scattered substantially isotropically, and directivity can be imparted to the transmission scattered light. Therefore, both high light scattering and directivity can be achieved.

  In order to enhance light scattering properties, a plurality of polymers can be used in combination so that the difference in refractive index is, for example, about 0.01 to 0.2, and preferably about 0.1 to 0.15. If the difference in refractive index is less than 0.01, the intensity of the transmitted scattered light decreases. If the difference in refractive index is greater than 0.2, high directivity cannot be imparted to the transmitted scattered light.

  The plurality of polymers include, for example, styrene resins, (meth) acrylic resins, vinyl ester resins, vinyl ether resins, halogen-containing resins, olefin resins (including alicyclic olefin resins), polycarbonate resins, and polyesters. Resin, polyamide resin, thermoplastic polyurethane resin, polysulfone resin (polyethersulfone, polysulfone, etc.), polyphenylene ether resin (2,6-xylenol polymer, etc.), cellulose derivatives (cellulose esters, cellulose carbamates) , Cellulose ethers, etc.), silicone resins (polydimethylsiloxane, polymethylphenylsiloxane, etc.), rubbers or elastomers (diene rubbers such as polybutadiene, polyisoprene, styrene-butadiene copolymers, Acrylonitrile - butadiene copolymer, acrylic rubber, urethane rubber, silicone rubber, etc.) can be chosen a suitable combination and the like.

  Preferred polymers include, for example, styrene resins, (meth) acrylic resins, vinyl ester resins, vinyl ether resins, halogen-containing resins, alicyclic olefin resins, polycarbonate resins, polyester resins, polyamide resins, Cellulose derivatives, silicone resins, rubbers or elastomers are included. As the plurality of polymers, a resin that is non-crystalline and is soluble in an organic solvent (in particular, a common solvent capable of dissolving the plurality of polymers) is usually used. In particular, resins with high moldability or film formability, transparency and weather resistance, such as styrene resins, (meth) acrylic resins, alicyclic olefin resins, polyester resins, cellulose derivatives (cellulose esters, etc.) Etc. are preferable.

  These plural polymers can be used in appropriate combinations. For example, in a combination of polymers, at least one polymer may be a cellulose derivative, particularly a cellulose ester (eg, cellulose C2-4 alkylcarboxyl such as cellulose diacetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate). Acid esters) and may be combined with other polymers.

  The glass transition temperature of the polymer can be selected from the range of, for example, −100 ° C. to 250 ° C., preferably −50 to 230 ° C., more preferably about 0 to 200 ° C. (for example, about 50 to 180 ° C.). From the viewpoint of sheet strength and rigidity, the glass transition temperature of at least one of the constituent polymers is 50 ° C. or higher (for example, about 70 to 200 ° C.), preferably 100 ° C. or higher (for example, 100 to 170 ° C.). It is advantageous that The weight average molecular weight of the polymer can be selected from the range of, for example, 1,000,000 or less (about 10,000 to 1,000,000), preferably about 10,000 to 700,000.

  In the above embodiment, a wet method is employed in which a solvent is evaporated from a liquid phase containing a plurality of polymers and spinodal decomposition is performed. Therefore, in principle, a substantially isotropic common property is used regardless of the compatibility of the plurality of polymers. A light scattering layer having a continuous phase structure can be formed. For this reason, it may be configured by combining a plurality of mutually compatible polymers. However, in order to easily control the phase separation structure by spinodal decomposition and to form a co-continuous phase structure efficiently, incompatible (phase separation) In many cases, a plurality of polymers are combined.

  The plurality of polymers can be constituted by a combination of the first polymer and the second polymer, and each of the first polymer and the second polymer may be constituted by a single resin or a plurality of resins. Also good. The combination of the first polymer and the second polymer is not particularly limited. For example, when the first polymer is a cellulose derivative (for example, cellulose esters such as cellulose acetate propionate), the second polymer is a styrene resin (polystyrene, styrene-acrylonitrile copolymer, etc.), (meta ) Acrylic resins (such as polymethyl methacrylate), alicyclic olefin resins (such as polymers containing norbornene as monomers), polycarbonate resins, polyester resins (such as poly C2-4 alkylene arylate copolyester) Or the like.

  The ratio of the first polymer to the second polymer is, for example, the former / the latter = about 10/90 to 90/10 (weight ratio), preferably about 20/80 to 80/20 (weight ratio), and more preferably Is about 30/70 to 70/30 (weight ratio), particularly about 40/60 to 60/40 (weight ratio). When the ratio of one polymer is too large, the volume ratio between the separated phases is biased, so that the intensity of scattered light decreases. In addition, when forming a sheet | seat with a 3 or more polymer, content of each polymer is 1 to 90 weight% (For example, 1 to 70 weight%, Preferably it is 5 to 70 weight%, More preferably, it is 10 (About 70% by weight).

  The light scattering layer constituting the optical (light scattering) film of the above aspect preferably has at least a bicontinuous phase structure. The co-continuous phase structure is sometimes referred to as a co-continuous structure or a three-dimensional continuous or connected structure, and means a structure in which at least two constituent polymer phases are continuous (for example, a network structure). . The light scattering layer preferably has at least a co-continuous phase structure, and may have a structure in which a co-continuous phase structure and a droplet phase structure (independent or isolated phase structure) are mixed. In spinodal decomposition, a co-continuous phase structure is formed as the phase separation progresses, and when the phase separation is further advanced, the continuous phase becomes discontinuous due to its surface tension, and the droplet phase structure (spherical, true spherical) Sea island structure of independent phase). Therefore, depending on the degree of phase separation, an intermediate structure between the co-continuous phase structure and the droplet phase structure, that is, a phase structure in the process of shifting from the co-continuous phase to the droplet phase can be formed. In the present specification, the intermediate structure is also referred to as a co-continuous phase structure. When the phase separation structure is a mixed structure of a co-continuous phase structure and a droplet structure, the ratio of the droplet phase (independent polymer phase) is, for example, 30% or less (volume ratio), preferably 10% or less ( Volume ratio). The shape of the co-continuous phase structure is not particularly limited, and may be a network shape, particularly a random network shape.

  The bicontinuous phase structure is generally isotropic with reduced anisotropy in the layer or film plane. Note that isotropic means that the average interphase distance of the co-continuous phase structure is substantially equal in any direction in the film plane.

  The bicontinuous phase structure usually has regularity in the interphase distance (distance between the same phases). For this reason, the light incident on the film is transmitted scattered light directed in a specific direction by Bragg reflection. Therefore, even if it is mounted on a reflective liquid crystal display device, the transmitted scattered light can be directed in a certain direction, the display screen can be made highly bright, and conventional particle-dispersed transmissive optics (light A problem that cannot be solved by the (scattering) film, that is, reflection of a light source (for example, a fluorescent lamp) on the panel can be avoided.

  In the optical (light scattering) film, the average interphase distance between the co-continuous phases is, for example, about 0.5 to 20 μm (for example, 1 to 20 μm), preferably about 1 to 15 μm (for example, 1 to 10 μm). If the average interphase distance is too small, it is difficult to obtain high scattered light intensity, and if the average interphase distance is too large, the directivity of transmitted scattered light decreases.

  The average interphase distance of the co-continuous layer can be calculated from a photomicrograph (such as a transmission microscope, a phase contrast microscope, or a confocal laser microscope) of the light scattering layer or light scattering film. In addition, the scattering angle θ at which the scattered light intensity is maximized is measured by a method similar to the scattered light directivity evaluation method described later, and the average interphase distance d of the co-continuous phase is calculated from the following Bragg reflection condition equation. May be.

2d · sin (θ / 2) = λ
(Where d is the average interphase distance of co-continuous phases, θ is the scattering angle, and λ is the wavelength of light)

[Emboss]
An example of a method for creating a light scattering layer is a method for creating a light scattering layer by an embossing method as an example of a method other than the use of translucent particles to exhibit antiglare properties.
The light scattering layer produced by the embossing method is an ionizing radiation curable resin composition or a thermosetting resin composition formed on a transparent substrate with a mat-shaped molding film having fine irregularities on the surface. A light diffusion layer consisting essentially of is formed.
When the resin is an ionizing radiation curable resin composition, the light scattering layer is produced by coating the ionizing radiation curable resin composition on a transparent substrate and then applying the ionizing radiation curable resin. By laminating a mat-shaped shaped film having fine irregularities on the surface of the uncured coating film of the composition, and then irradiating ionizing radiation on the coated film on which the shaped film is laminated, It is preferable to manufacture the coating film of the ionizing radiation curable resin composition by a manufacturing method in which the forming film is peeled from the cured coating film of the ionizing radiation curable resin.
When the resin is a thermosetting resin composition, the thermosetting resin composition is applied onto a transparent substrate, and then the uncured coating film of the applied thermosetting resin composition is applied. A mat-like shaped film having fine irregularities on the surface is laminated, and then the coating film laminated with the shaped film is heated and cured, and then the cured thermosetting resin composition is applied. It is preferable to manufacture by the manufacturing method which peels a shaping film from a film | membrane.

  When laminating the shaping film on the coating film of the uncured ionizing radiation curable resin composition, if the coated resin is of a solvent dilution type, the solvent is dried and then laminating, If the applied resin is solventless, lamination is performed as it is. The film forming component of the ionizing radiation curable resin composition used for the light diffusing layer of the embossing method is preferably one having an acrylate functional group, such as a polyester resin, polyether resin, acrylic resin having a relatively low molecular weight. , Epoxy or urethane resins, alkyd resins, spiroacetal resins, polybutadiene resins, polythiol polyene resins, oligomers or prepolymers of polyfunctional compounds such as polyhydric alcohols or prepolymers and ethyl (meth) as a reactive diluent Monofunctional monomers such as acrylate, ethylhexyl (meth) acrylate, styrene, methylstyrene, N-vinylpyrrolidone and polyfunctional monomers such as trimethylolpropane tri (meth) acrylate, hexanediol (meth) acrylate, tri Lopylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) ) Those containing a relatively large amount of acrylate or the like can be used.

  Particularly preferably, a mixture of polyester acrylate and polyurethane acrylate is used. The reason is that polyester acrylate is very hard and suitable for obtaining a hard coat, but polyester acrylate alone has low impact and is brittle. In order to give the properties, polyurethane acrylate is used in combination. The blending ratio of polyurethane acrylate with respect to 100 parts by weight of polyester acrylate is 30 parts by weight or less. If this value is exceeded, the coating film is too soft and the hardness is lost.

  Further, in order to make the ionizing radiation curable resin composition into an ultraviolet curable resin composition, acetophenones, benzophenones, Michler benzoyl benzoate, α-amyloxime ester, tetra Methyl thiuram monosulfide, thioxanthones, and n-butylamine, triethylamine, tri-n-butylphosphine, and the like can be used as a photosensitizer. In particular, in the present invention, it is preferable to mix urethane acrylate as an oligomer and dipentaerythritol hexa (meth) acrylate as a monomer.

2- (3) High Refractive Index Layer, Medium Refractive Index Layer The film of the present invention can be provided with a high refractive index layer and a medium refractive index layer to enhance antireflection properties.
In the following specification, the high refractive index layer and the medium refractive index layer may be collectively referred to as a high refractive index layer. In the present invention, “high”, “medium”, and “low” in the high refractive index layer, the medium refractive index layer, and the low refractive index layer represent the relative refractive index relationship between the layers. In terms of the relationship with the transparent support, the refractive index preferably satisfies the relationship of transparent support> low refractive index layer, high refractive index layer> transparent support.
In the present specification, the high refractive index layer, the middle refractive index layer, and the low refractive index layer may be collectively referred to as an antireflection layer.

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

  When an antireflective film is prepared by coating a medium refractive index layer, a high refractive index layer, and a low refractive index layer in order from the support, the refractive index of the high refractive index layer is 1.65 to 2.40. Preferably, it is 1.70 to 2.20. The refractive index of the middle refractive index layer is adjusted to be a value between the refractive index of the low refractive index layer and the refractive index of the high refractive index layer. The refractive index of the middle refractive index layer is preferably 1.55 to 1.80.

The inorganic particles mainly composed of TiO ₂ used for the high refractive index layer and the medium refractive index layer are used for forming the high refractive index layer and the medium refractive index layer in the state of dispersion.
In the dispersion of the inorganic particles, the inorganic particles are dispersed in a dispersion medium in the presence of a dispersant.

  The high refractive index layer and the medium refractive index layer used in the present invention are preferably used in a dispersion liquid in which inorganic particles are dispersed in a dispersion medium, preferably a binder precursor necessary for matrix formation (for example, an ionizing radiation curable composition described later). Polyfunctional monomer, polyfunctional oligomer, etc.), photopolymerization initiator, etc. are added to form a coating composition for forming a high refractive index layer and a medium refractive index layer, and a high refractive index layer and a medium refractive index layer are formed on a transparent support. It is preferable that the coating composition is applied and cured by a crosslinking reaction or a polymerization reaction of an ionizing radiation curable compound (for example, a polyfunctional monomer or a polyfunctional oligomer).

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

  The binder of the high refractive index layer is added in an amount of 5 to 80% by mass based on the solid content of the coating composition of the layer.

The content of the inorganic particles in the high refractive index layer is preferably 10 to 90% by mass, more preferably 15 to 80% by mass, and particularly preferably 15 to 75% by mass with respect to the mass of the high refractive index layer. . Two or more inorganic particles may be used in combination in the high refractive index layer.
When the low refractive index layer is provided on the high refractive index layer, the refractive index of the high refractive index layer is preferably higher than the refractive index of the transparent support.
The high refractive index layer contains an ionizing radiation curable compound containing an aromatic ring, an ionizing radiation curable compound containing a halogenated element other than fluorine (for example, Br, I, Cl, etc.), and atoms such as S, N, P, etc. A binder obtained by a crosslinking or polymerization reaction such as an ionizing radiation curable compound can also be preferably used.

  The film thickness of the high refractive index layer can be appropriately designed depending on the application. When using a high refractive index layer as an optical interference layer described later, the thickness is preferably 30 to 200 nm, more preferably 50 to 170 nm, and particularly preferably 60 to 150 nm.

The haze of the high refractive index layer is preferably as low as possible when it does not contain particles that impart an antiglare function. It is preferably 5% or less, more preferably 3% or less, and particularly preferably 1% or less.
The high refractive index layer is preferably constructed directly on the transparent support or via another layer.

2- (4) Low Refractive Index Layer In order to reduce the reflectance of the film of the present invention, it is preferable to use a low refractive index layer.

The refractive index of the low refractive index layer is preferably 1.20 to 1.46, more preferably 1.25 to 1.46, and particularly preferably 1.30 to 1.46.
The thickness of the low refractive index layer is preferably 50 to 200 nm, and more preferably 70 to 100 nm. The haze of the low refractive index layer is preferably 3% or less, more preferably 2% or less, and most preferably 1% or less. The specific strength of the low refractive index layer is preferably H or higher, more preferably 2H or higher, and most preferably 3H or higher in a pencil hardness test under a 500 g load.
In order to improve the antifouling performance of the optical film, it is preferable that the contact angle of the surface with respect to water is 90 degrees or more. More preferably, it is 95 degrees or more, and particularly preferably 100 degrees or more.

  The curable composition preferably contains (A) the fluoropolymer, (B) inorganic particles, and (C) an organosilane compound.

  In the low refractive index layer, a binder is used for dispersing and fixing the fine particles of the present invention. As the binder, the binder described in the hard coat layer can be used, but it is preferable to use a fluorine-containing polymer having a low refractive index or a fluorine-containing sol-gel material. The fluorine-containing polymer or fluorine-containing sol-gel is a material that has a dynamic friction coefficient of 0.03 to 0.30 on the surface of the low refractive index layer formed by crosslinking by heat or ionizing radiation and a contact angle of 85 to 120 ° with water. Is preferred.

2- (6) Antifouling layer An antifouling layer can be provided on the outermost surface of the present invention. The antifouling layer lowers the surface energy of the antireflection layer and makes it difficult to attach hydrophilic or lipophilic stains.
The antifouling layer can be formed using a fluorine-containing polymer or an antifouling agent.
The thickness of the antifouling layer is preferably 2 to 100 nm, and more preferably 5 to 30 nm.

2- (7) Interference unevenness (rainbow unevenness) prevention layer There is a substantial refractive index difference (refractive index difference of 0.03 or more) between the transparent support and the hard coat layer, or between the transparent support and the antiglare hard coat layer. In some cases, reflected light is generated at the transparent support / hard coat layer or at the transparent support / antiglare interface. This reflected light interferes with the reflected light on the surface of the antireflection layer, and may cause interference unevenness due to fine film thickness unevenness of the hard coat layer (or antiglare hard coat layer). In order to prevent such interference unevenness, for example, an intermediate refractive index n _P is provided between the transparent support and the hard coat layer (or antiglare hard coat layer), and the film thickness d _P satisfies the following formula: Such an interference non-uniformity prevention layer can also be provided.

Formula (I)
d _P = (2N−1) × λ / (4n _P )
Where λ is the wavelength of visible light and any value in the range of 450 to 650 nm, and N is a natural number.

  Moreover, when bonding an antireflection film to an image display etc., an adhesive layer (or adhesive layer) may be laminated | stacked on the side which has not laminated | stacked the antireflection layer of a transparent support body. In such an embodiment, when there is a substantial refractive index difference (0.03 or more) between the transparent support and the pressure-sensitive adhesive layer (or adhesive layer), the transparent support / pressure-sensitive adhesive layer (or adhesive layer) The reflected light interferes with the reflected light on the surface of the antireflection layer, and the interference unevenness due to the film thickness unevenness of the support or the hard coat layer may occur as described above. For the purpose of preventing such interference unevenness, an interference unevenness preventing layer similar to the above can be provided on the side of the transparent support on which the antireflection layer is not laminated.

  Such an interference non-uniformity prevention layer is described in detail in Japanese Patent Application Laid-Open No. 2004-345333, and the interference non-uniformity prevention layer introduced here can also be used in the present invention.

2- (8) Easy-Adhesion Layer An easy-adhesion layer can be applied to the film of the present invention. An easy-adhesion layer means the layer which provides the function which makes it easy to adhere | attach a protective film for polarizing plates, its adjacent layer, or a hard-coat layer and a support body, for example.
Examples of the easy adhesion treatment include a treatment of providing an easy adhesion layer on a transparent plastic film with an easy adhesive composed of polyester, acrylic acid ester, polyurethane, polyethyleneimine, silane coupling agent and the like.
Examples of the easy-adhesion layer preferably used in the present invention include a layer containing a polymer compound having a -COOM (M represents a hydrogen atom or a cation) group, and a more preferable embodiment is a film substrate. A layer containing a polymer compound having a —COOM group is provided on the side, and a layer containing a hydrophilic polymer compound as a main component is provided on the polarizing film side adjacent to the layer. Examples of the polymer compound having -COOM group herein include styrene-maleic acid copolymer having -COOM group, vinyl acetate-maleic acid copolymer having -COOM group, and vinyl acetate-maleic acid-maleic anhydride. For example, it is preferable to use a vinyl acetate-maleic acid copolymer having a —COOM group. These polymer compounds are used alone or in combination of two or more, and the preferred weight average molecular weight is preferably about 500 to 500,000. Particularly preferred examples of the polymer compound having a —COOM group include those described in JP-A-6-094915 and JP-A-7-333436.

The hydrophilic polymer compound is preferably a hydrophilic cellulose derivative (eg, methyl cellulose, carboxymethyl cellulose, hydroxy cellulose, etc.), a polyvinyl alcohol derivative (eg, polyvinyl alcohol, vinyl acetate-vinyl alcohol copolymer, polyvinyl acetal, polyvinyl formal). , Polyvinyl benzal, etc.), natural polymer compounds (eg, gelatin, casein, gum arabic, etc.), hydrophilic polyester derivatives (eg, partially sulfonated polyethylene terephthalate), hydrophilic polyvinyl derivatives (eg, poly -N-vinylpyrrolidone, polyacrylamide, polyvinylindazole, polyvinylpyrazole and the like), and may be used alone or in combination of two or more.
The thickness of the easy adhesion layer is preferably in the range of 0.05 to 1.0 μm. If it is thinner than 0.05 μm, it is difficult to obtain sufficient adhesiveness, and if it is thicker than 1.0 μm, the effect of adhesiveness is saturated.

2- (9) Anti-curl Layer The film of the present invention can be subjected to anti-curl processing. The anti-curl processing is to give the function of trying to curl with the surface to which it is applied inside, but by applying this processing, some surface processing is performed on one side of the transparent resin film and both sides are processed. When surface treatments of different degrees and types are applied, it functions to prevent curling with the surface facing inward.
The anti-curl layer may be provided on the side opposite to the side having the anti-glare hard coat layer or anti-reflection layer of the substrate, or for example, an easy-adhesion layer may be coated on one side of the transparent resin film, An embodiment in which anti-curl processing is applied is exemplified.

  Specific examples of the anti-curl processing include solvent coating, and a method of applying a solvent and a transparent resin layer such as cellulose triacetate, cellulose diacetate, and cellulose acetate propionate. The method using a solvent is specifically performed by applying a composition containing a solvent for dissolving or swelling a cellulose acylate film used as a protective film for a polarizing plate. Accordingly, the coating solution for the layer having a function of preventing curling preferably contains a ketone-based or ester-based organic solvent. Examples of preferred ketone-based organic solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl lactate, acetyl acetone, diacetone alcohol, isophorone, ethyl-n-butyl ketone, diisopropyl ketone, diethyl ketone, di-n-propyl ketone, Examples thereof include methylcyclohexanone, methyl-n-butyl ketone, methyl-n-propyl ketone, methyl-n-hexyl ketone, methyl-n-heptyl ketone, etc. Examples of preferable ester organic solvents include methyl acetate, ethyl acetate, acetic acid Examples include butyl, methyl lactate, and ethyl lactate. However, as a solvent to be used, in addition to a solvent mixture to be dissolved and / or a solvent to be swollen, it may further contain a solvent that does not dissolve, and a composition in which these are mixed at an appropriate ratio depending on the degree of curl of the transparent resin film and the type of resin. This is done using the product and the coating amount. In addition, the anti-curl function is exhibited even if transparent hard processing or antistatic processing is applied.

2- (10) Water Absorbing Layer A water absorbent can be used in the film of the present invention. The water absorbent can be selected from compounds having a water absorption function, mainly alkaline earth metals. Examples thereof include BaO, SrO, CaO, and MgO. Further, it can be selected from metal elements such as Ti, Mg, Ba, and Ca. The particle size of these absorbent particles is preferably 100 nm or less, and more preferably 50 nm or less.
The layer containing these water absorbents may be prepared by using a vacuum deposition method or the like as in the above-described barrier layer, or nanoparticles may be prepared by various methods. The thickness of the layer is preferably 1 to 100 nm, and more preferably 1 to 10 nm. The layer containing the water absorbent is between the support and the laminate (a laminate of the barrier layer and the organic layer), between the uppermost layer of the laminate, between the laminates, or in the organic layer or barrier layer in the laminate. It may be added. When added to the barrier layer, a co-evaporation method is preferably used.

2- (11) Primer Layer / Inorganic Thin Film Layer In the film of the present invention, gas barrier properties can be enhanced by installing a known primer layer or inorganic thin film layer between the support and the laminate. .
As the primer layer, for example, an acrylic resin, an epoxy resin, a urethane resin, a silicone resin or the like can be used. In the present invention, an organic-inorganic hybrid layer is used as the primer layer, an inorganic vapor deposition layer or a sol-gel is used as the inorganic thin film layer. A dense inorganic coating thin film by the method is preferred. As an inorganic vapor deposition layer, vapor deposition layers, such as a silica, a zirconia, an alumina, are preferable. The inorganic vapor deposition layer can be formed by a vacuum vapor deposition method, a sputtering method, or the like.

3. Layer structure of film About the film of this invention, a well-known layer structure can be used using the above layers. For example, the following are typical examples.
a. Support / Antistatic layer / Protective layer / Light scattering hard coat layer b. Support (1) / Antistatic layer (7) / Protective layer (6) / Light scattering hard coat layer (2) / Low refractive index layer (FIG. 1)
c. Support (1) / Antistatic layer (7) / Protective layer (6) / Light scattering hard coat layer (2) / High refractive index layer / Low refractive index layer (FIG. 2)
d. Support (1) / Antistatic layer (7) / Protective layer (6) / Light scattering hard coat layer (2) / Medium refractive index layer (3) / High refractive index layer (4) / Low refractive index layer ( 5) (Fig. 3)
As shown in FIG. 1B, when a light-reflective hard coat layer is applied and a low refractive index layer is laminated, it can be suitably used as an antireflection film. By forming the low refractive index layer on the light scattering hard coat layer with a film thickness of about ¼ of the wavelength of light, surface reflection can be reduced by the principle of thin film interference.
Moreover, even if a high refractive index layer and a low refractive index layer are laminated after applying a light scattering hard coat layer as shown in c (FIG. 2), it can be suitably used as an antireflection film. Further, as shown in d (FIG. 3), by providing a layer structure in the order of a support, a light-scattering hard coat layer, a medium refractive index layer, a high refractive index layer, and a low refractive index layer, the reflectance becomes 1 % Or less.

  The light-scattering hard coat layer (2) may be an anti-glare hard coat layer having anti-glare properties as shown in FIGS. 1 to 3, and the anti-glare manifestation means may be based on dispersion of mat particles, embossing, etc. It may be formed by surface shaping according to the method. The antiglare hard coat layer formed by dispersing the matte particles is composed of a binder and translucent particles dispersed in the binder. The antiglare hard coat layer having antiglare properties may be composed of a plurality of layers, for example, 2 to 4 layers.

In addition, as a layer that may be provided between the support and the layer on the surface side or the outermost layer, an interference unevenness (rainbow unevenness) prevention layer, another antistatic layer (only one antistatic layer is used from the display side) If the surface resistance of the material is high or if dust is a problem on the surface, etc.), another hard coat layer (if the hardness is insufficient with only one hard coat layer or antiglare hard coat layer), gas Examples thereof include a barrier layer, a water absorption layer (moisture-proof layer), an adhesion improving layer, an antifouling layer (a contamination-preventing layer), and the like.
The refractive index of each layer constituting the antireflection film in the present invention preferably satisfies the following relationship.
Refractive index of light scattering hard coat layer> Refractive index of transparent support> Refractive index of low refractive index layer

4). Manufacturing Method The film of the present invention can be formed by the following method, but is not limited to this method.
4- (1) Adjustment of coating solution

<Preparation>
First, a coating solution containing components for forming each layer is prepared. In that case, the raise of the moisture content in a coating liquid can be suppressed by suppressing the volatilization amount of a solvent to the minimum. The moisture content in the coating solution is preferably 5% or less, more preferably 2% or less. The suppression of the volatilization amount of the solvent is achieved by improving the sealing property at the time of stirring after putting each material into the tank, minimizing the air contact area of the coating liquid at the time of liquid transfer operation, and the like. Moreover, you may provide the means to reduce the moisture content in a coating liquid during application | coating, or before and behind that.

<Physical properties of coating solution>
For coating liquids with a dry film thickness of 200 nm or less such as low refractive index layer, medium refractive index layer, high refractive index layer, antifouling layer, etc., the upper limit speed that can be applied is greatly affected by the liquid properties. It is necessary to control the liquid physical properties, particularly the viscosity and the surface tension, at the moment.
The viscosity is preferably 2.0 [mPa · sec] or less, more preferably 1.5 [mPa · sec] or less, and most preferably 1.0 [mPa · sec] or less. Since there are some coating solutions whose viscosity changes depending on the shear rate, the above value indicates the viscosity at the shear rate at the moment of coating. When a thixotropic agent is added to the coating solution and the coating solution is subjected to high shear, the viscosity is low, and when the coating solution is hardly sheared, if the viscosity is high, unevenness during drying is less likely to occur.
Moreover, although it is not a liquid physical property, the quantity of the coating liquid apply | coated to a transparent support body also affects the upper limit speed | rate which can be apply | coated. The amount of the coating solution applied to the transparent support is preferably 2.0 to 5.0 [cc / m ² ]. Increasing the amount of the coating liquid applied to the transparent support is preferable because the upper limit of the application rate can be increased, but if the amount of the coating liquid applied to the transparent support is increased too much, the load on drying increases. It is preferable to determine the optimal amount of coating liquid to be applied to the transparent support depending on the liquid formulation and process conditions.
The surface tension is preferably in the range of 15 to 36 [mN / m]. It is preferable to reduce the surface tension by adding a leveling agent or the like because unevenness during drying is suppressed. On the other hand, if the surface tension is too low, the upper limit speed at which coating can be performed is reduced. Therefore, a range of 17 [mN / m] to 32 [mN / m] is more preferable, and 19 [mN / m] to 26 [mN / m]. mN / m] is more preferable.
In the antiglare hard coat layer containing translucent particles, the viscosity is preferably 5 cp or more, and more preferably 7 cp or more, from the viewpoint of preventing sedimentation of the particles.

<Filtration>
The coating solution used for coating is preferably filtered before coating. As the filter for filtration, it is preferable to use a filter having a pore diameter as small as possible within the range in which the components in the coating solution are not removed. For the filtration, a filter having an absolute filtration accuracy of 0.1 to 50 μm is used, and a filter having an absolute filtration accuracy of 0.1 to 30 μm is preferably used. The thickness of the filter is preferably 0.1 to 10 mm, and more preferably 0.2 to 2 mm. In that case, the filtration pressure is preferably 1.5 MPa or less, more preferably 1.0 MPa or less, and further preferably 0.2 MPa or less.
The filtration filter member is not particularly limited as long as it does not affect the coating solution. Specifically, the same thing as the filter member of the wet dispersion of an inorganic compound mentioned above is mentioned.
It is also preferable to ultrasonically disperse the filtered coating solution immediately before coating to assist defoaming and dispersion holding of the dispersion.

4- (2) Treatment before coating The support used in the present invention is preferably subjected to a surface treatment before coating. Specific examples include corona discharge treatment, glow discharge treatment, flame treatment, acid treatment, alkali treatment, and ultraviolet irradiation treatment. In addition, as described in JP-A-7-333433, it is preferable to provide an undercoat layer.

Furthermore, as a dust removing method used in the dust removing step as a pre-process for application, a method of pressing a nonwoven fabric, a blade or the like on the film surface described in JP-A-59-150571, JP-A-10-309553 A method of blowing the air with high cleanliness described at a high speed to peel off the deposits from the film surface and sucking it with a suction port close to it, blowing compressed air that is ultrasonically vibrated as described in JP-A-7-333613 Examples thereof include a dry dust removing method such as a method for peeling and sucking adhered substances (manufactured by Shinkosha, New Ultra Cleaner, etc.).
In addition, a method of introducing a film into a cleaning tank and peeling off deposits with an ultrasonic vibrator, supplying a cleaning liquid to the film described in Japanese Patent Publication No. 49-13020, and then blowing and sucking high-speed air As described in JP-A-2001-38306, a wet dust removal method such as a method in which a web is continuously rubbed with a roll wetted with liquid and then the liquid is sprayed onto the rubbed surface for cleaning. Can do. Among such dust removal methods, a method using ultrasonic dust removal or a method using wet dust removal is particularly preferable in terms of dust removal effect.
In addition, it is particularly preferable to remove static electricity on the film support before performing such a dust removal step from the viewpoint of increasing dust removal efficiency and suppressing adhesion of dust. As such a static elimination method, a corona discharge ionizer, a light irradiation ionizer such as UV or soft X-ray, or the like can be used. The charged voltage of the film support before and after dust removal and coating is desirably 1000 V or less, preferably 300 V or less, and particularly preferably 100 V or less.

From the viewpoint of maintaining the flatness of the film, the temperature of the cellulose acylate film in these treatments is preferably Tg or less, specifically 150 ° C. or less.
When the cellulose acylate film is adhered to the polarizing film as in the case of using the film of the present invention as a protective film for a polarizing plate, from the viewpoint of adhesiveness to the polarizing film, acid treatment or alkali treatment, that is, cellulose acylate. It is particularly preferred to carry out a saponification treatment on the rate.
From the viewpoint of adhesiveness and the like, the surface energy of the cellulose acylate film is preferably 55 mN / m or more, more preferably 60 mN / m or more and 75 mN / m or less, and it can be adjusted by the surface treatment. .

4- (3) Coating Each layer of the film of the present invention can be formed by the following coating method, but is not limited to this method.
Dip coating method, air knife coating method, curtain coating method, roller coating method, wire bar coating method, gravure coating method and extrusion coating method (die coating method) (see US Pat. No. 2,681,294, specification WO 2005/123274), Known methods such as a micro gravure coating method are used, and among them, a micro gravure coating method and a die coating method are preferable.

  The micro gravure coating method used in the present invention is a gravure roll having a diameter of about 10 to 100 mm, preferably about 20 to 50 mm and engraved with a gravure pattern on the entire circumference, below the support and in the transport direction of the support. The gravure roll is rotated in reverse with respect to the gravure roll, the excess coating liquid is scraped off from the surface of the gravure roll by a doctor blade, and a fixed amount of the coating liquid is removed from the support in a position where the upper surface of the support is in a free state. The coating method is characterized in that the coating liquid is transferred onto the lower surface for coating. A roll-shaped transparent support is continuously unwound, and at least one layer of at least one of a hard coat layer or a low refractive index layer containing a fluorine-containing olefin-based polymer is formed on one side of the unwound support. It can be applied by a gravure coating method.

  As coating conditions by the micro gravure coating method, the number of gravure patterns imprinted on the gravure roll is preferably 50 to 800 lines / inch, more preferably 100 to 300 lines / inch, and the depth of the gravure pattern is 1 to 600 μm. Is preferable, 5 to 200 μm is more preferable, the rotation speed of the gravure roll is preferably 3 to 800 rpm, more preferably 5 to 200 rpm, and the conveyance speed of the support is 0.5 to 100 m / min. It is preferably 1 to 50 m / min.

  In order to supply the film of the present invention with high productivity, an extrusion method (die coating method) is preferably used. In particular, when two or more hard coat layers are applied simultaneously, it is preferable to apply by the coating method described in JP-A-2002-86050 and JP-A-2003-260400.

4- (4) Drying The film of the present invention is preferably applied to the support directly or via another layer, and then conveyed by a web to a heated zone for drying the solvent.
Various knowledges can be used as a method for drying the solvent. Specific examples include JP-A Nos. 2001-286817, 2001-314798, 2003-126768, 2003-315505, and 2004-34002.
The temperature of the drying zone is preferably 25 ° C. to 140 ° C., the first half of the drying zone is preferably a relatively low temperature, and the latter half is preferably a relatively high temperature. However, it is preferably below the temperature at which components other than the solvent contained in the coating composition of each layer start to volatilize. For example, some of the commercially available photo radical generators used in combination with ultraviolet curable resins volatilize around several tens of percent within a few minutes in warm air at 120 ° C. Some acrylate monomers and the like undergo volatilization in warm air at 100 ° C. In such a case, it is preferable that it is below the temperature at which components other than the solvent contained in the coating composition of each layer start to volatilize as described above.

Moreover, the dry wind after apply | coating the coating composition of each layer on a support body has the wind speed of the coating-film surface of 0.1-2 m / sec while the solid content concentration of the said coating composition is 1-50%. It is preferable to be in the range in order to prevent drying unevenness.
Moreover, after apply | coating the coating composition of each layer on a support body, the temperature difference of the conveyance roll which contacts the surface opposite to the coating surface of a support body in a drying zone, and a support body is 0 to 20 degreeC or less. Then, the drying nonuniformity by the heat transfer nonuniformity on a conveyance roll can be prevented, and it is preferable.

4- (5) Curing
After drying the solvent, the film of the present invention can be passed through a zone where the coating film is cured by ionizing radiation and / or heat on the web to cure the coating film.

The ionizing radiation species in the present invention is not particularly limited, and is appropriately selected from ultraviolet rays, electron beams, near ultraviolet rays, visible light, near infrared rays, infrared rays, X-rays and the like according to the type of curable composition forming the film. Although it can be selected, ultraviolet rays and electron beams are preferred, and ultraviolet rays are particularly preferred because they are easy to handle and high energy can be easily obtained.
As the ultraviolet light source for photopolymerizing the ultraviolet reactive compound, any light source that generates ultraviolet light can be used. For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used. An ArF excimer laser, a KrF excimer laser, an excimer lamp, synchrotron radiation, or the like can also be used. Among these, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, and a metal halide lamp can be preferably used.

  Moreover, an electron beam can be used similarly. As an electron beam, 50 to 1000 keV, preferably 100 to 100, emitted from various electron beam accelerators such as a cockroft Walton type, a bandegraph type, a resonance transformation type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type. An electron beam having an energy of 300 keV can be given.

Irradiation conditions vary depending on each lamp, but the irradiation light quantity is preferably 10 mJ / cm ² or more, more preferably 50 mJ / cm ^{2 to} 10000 mJ / cm ² , and particularly preferably 50 mJ / cm ^{2 to} 2000 mJ / cm ^2. It is. At that time, the irradiation distribution in the width direction of the web is preferably 50 to 100%, more preferably 80 to 100%, including both ends with respect to the central maximum irradiation.

In the present invention, at least one layer laminated on the support is irradiated with ionizing radiation and heated to a film surface temperature of 60 ° C. or more for 0.5 seconds or more from the start of irradiation with ionizing radiation, with an oxygen concentration of 10 volumes. It is preferable to cure by the step of irradiating ionizing radiation in an atmosphere of less than or equal to%.
It is also preferable to heat in an atmosphere having an oxygen concentration of 3% by volume or less simultaneously and / or continuously with ionizing radiation irradiation.
In particular, it is preferable that the low refractive index layer which is the outermost layer and has a small film thickness is cured by this method. The curing reaction is accelerated by heat, and a film having excellent physical strength and chemical resistance can be formed.

  The time for irradiating with ionizing radiation is preferably 0.7 seconds or longer and 60 seconds or shorter, and more preferably 0.7 seconds or longer and 10 seconds or shorter. If it is 0.5 seconds or less, the curing reaction cannot be completed, and sufficient curing cannot be performed. Also, maintaining low oxygen conditions for a long time is not preferable because the equipment becomes large and a large amount of inert gas is required.

  The oxygen concentration is preferably formed by a crosslinking reaction or a polymerization reaction of an ionizing radiation curable compound in an atmosphere of 6% by volume or less, more preferably 4% by volume or less, particularly preferably 2% by volume of oxygen. Hereinafter, it is most preferably 1% by volume or less. In order to reduce the oxygen concentration more than necessary, a large amount of inert gas such as nitrogen is required, which is not preferable from the viewpoint of production cost.

  As a method of reducing the oxygen concentration to 10% by volume or less, it is preferable to replace the atmosphere (nitrogen concentration of about 79% by volume, oxygen concentration of about 21% by volume) with another gas, particularly preferably replacement with nitrogen (nitrogen purge). It is to be.

Conveying air accompanying web transport by supplying inert gas to the ionizing radiation irradiation chamber (hereinafter also referred to as irradiation chamber or reaction chamber) and making the inert gas slightly blow out to the web entrance side of the irradiation chamber The oxygen concentration in the reaction chamber can be effectively reduced, and the substantial oxygen concentration at the extreme surface where the inhibition of curing by oxygen is large can be efficiently reduced. The direction of the inert gas flow on the web entrance side of the irradiation chamber can be controlled by adjusting the balance between the supply and exhaust of the irradiation chamber.
Direct blowing of an inert gas onto the web surface is also preferably used as a method for removing the carried air.

  Further, by providing a front chamber in front of the reaction chamber and eliminating oxygen on the web surface immediately before the web enters the reaction chamber, curing can be promoted more efficiently. The side of the ionization radiation reaction chamber or the front chamber that forms the web entrance side has a gap with the web surface (in other words, the distance between the web surface and the web entrance) in order to use inert gas efficiently. ) Is preferably 0.2 to 15 mm, more preferably 0.2 to 10 mm, and most preferably 0.2 to 5 mm. However, in order to continuously manufacture the web, it is necessary to join and connect the webs, and a method of sticking with a joining tape or the like is widely used for joining. For this reason, if the gap between the entrance surface of the ionizing radiation reaction chamber or the front chamber and the web is too narrow, there arises a problem that the joining member such as the joining tape is caught. For this reason, in order to narrow the gap, it is preferable to make at least a part of the entrance surface of the ionizing radiation reaction chamber or the front chamber movable, and to widen the gap by the junction thickness when the junction enters. In order to realize this, the entrance surface of the ionizing radiation reaction chamber or the front chamber is made movable in the forward and backward direction, and when the joint passes, the gap is moved back and forth to widen the gap, It is possible to move the chamber entrance surface vertically with respect to the web surface and move up and down to widen the gap as the joint passes.

  In curing, the film surface is preferably heated at 60 ° C. or higher and 170 ° C. or lower. Below 60 ° C., there is little curing by heating, and when it exceeds 170 ° C., problems such as deformation of the substrate occur. Furthermore, this preferable temperature is 60 degreeC-100 degreeC. The film surface refers to the film surface temperature of the layer to be cured. The time for the film to reach the temperature is preferably 0.1 second or more and 300 seconds or less from the start of UV irradiation, and more preferably 10 seconds or less. If the time for maintaining the temperature of the film surface in the above temperature range is too short, the reaction of the curable composition that forms the film cannot be accelerated, and conversely, if it is too long, the optical performance of the film deteriorates and the equipment is large. Manufacturing problems such as

  There is no particular limitation on the heating method, but a method of heating a roll to contact the film, a method of spraying heated nitrogen, irradiation with far infrared rays or infrared rays is preferable. A method of heating a rotating metal roll described in Japanese Patent No. 2523574 by flowing a medium such as hot water, steam or oil can also be used. As a heating means, a dielectric heating roll or the like may be used.

  The ultraviolet irradiation may be performed every time one layer is provided for each of a plurality of constituent layers, or may be performed after lamination. Or you may irradiate combining these. From the viewpoint of productivity, it is preferable to irradiate ultraviolet rays after laminating multiple layers.

In the present invention, at least one layer coated on the support can be cured by multiple times of ionizing radiation. In this case, it is preferable that at least two ionizing radiations are performed in a continuous reaction chamber in which the oxygen concentration does not exceed 3% by volume. By performing multiple times of ionizing radiation irradiation in the same low oxygen concentration reaction chamber, the reaction time required for curing can be effectively ensured.
In particular, when the production rate is increased for high productivity, ionizing radiation irradiation is required multiple times to ensure the energy of ionizing radiation necessary for the curing reaction.

  Further, when the curing rate (100-residual functional group content) is a certain value of less than 100%, the lower layer has a curing rate of the upper layer when a layer is provided thereon and cured by ionizing radiation and / or heat. When the height is higher than before, the adhesion between the lower layer and the upper layer is improved, which is preferable.

4- (6) Handling In order to continuously produce the film of the present invention, a process of continuously feeding a roll-shaped support film, a process of applying / drying a coating liquid, a process of curing a coating film, and curing The process of winding up the support film which has a layer is performed.
The film support is continuously sent out from the roll-shaped film support to the clean room. In the clean room, the static electricity charged on the film support is removed by an electrostatic charge-off device, and then the film support adheres on the film support. Remove the foreign material that has been removed with a dust remover. Subsequently, the coating liquid is applied onto the film support in the application section installed in the clean room, and the applied film support is sent to the drying chamber and dried.
The film support having the dried coating layer is fed from the drying chamber to the curing chamber, and the monomer contained in the coating layer is polymerized and cured. Further, the film support having the cured layer is sent to the curing unit to complete the curing, and the film support having the layer having been completely cured is wound up into a roll shape.

The above steps may be performed every time each layer is formed, or a plurality of coating parts-drying chambers-curing parts may be provided to continuously form each layer.
In order to create the film of the present invention, as described above, the coating step in the coating unit and the drying step performed in the drying chamber are performed in a highly clean air atmosphere simultaneously with the microfiltration operation of the coating solution, and It is preferable that dust and dust on the film are sufficiently removed before application. The air cleanliness of the coating process and the drying process is desirably class 10 (353 particles / 0.5 m or more / (cubic meter) or less) based on the standard of air cleanliness in the US Federal Standard 209E. Preferably it is class 1 (35.5 particles / (cubic meter) or less) having a particle size of 0.5 μm or more. Moreover, it is more preferable that the degree of air cleanliness is high also in the feeding and winding parts other than the coating-drying process.

4- (7) Saponification treatment When making a polarizing plate using the film of the present invention as one of the surface protective films of two polarizing films, the surface on the side to be bonded to the polarizing film should be hydrophilized. Thus, it is preferable to improve the adhesion on the bonding surface.

a. Method of immersing in alkaline solution This is a method of saponifying all surfaces that are reactive with alkali on the entire surface of the film by immersing the film in an alkaline solution under appropriate conditions, and no special equipment is required. From the viewpoint of cost. The alkaline liquid is preferably a sodium hydroxide aqueous solution. A preferred concentration is 0.5 to 3 mol / L, particularly preferably 1 to 2 mol / L. The liquid temperature of a preferable alkali liquid is 30-75 degreeC, Most preferably, it is 40-60 degreeC.
The combination of the saponification conditions is preferably a combination of relatively mild conditions, but can be set according to the material and composition of the film and the target contact angle.
After being immersed in the alkaline solution, it is preferable to sufficiently wash with water or neutralize the alkaline component by immersing in a dilute acid so that the alkaline component does not remain in the film.

By saponification treatment, the surface opposite to the surface having the coating layer is hydrophilized. The protective film for polarizing plate is used by adhering the hydrophilic surface of the transparent support to the polarizing film.
The hydrophilized surface is effective for improving the adhesiveness with the adhesive layer mainly composed of polyvinyl alcohol.
In the saponification treatment, the lower the contact angle with respect to the surface of the transparent support opposite to the side having the coating layer, the better from the viewpoint of adhesion to the polarizing film, while the dipping method simultaneously has the coating layer. Since it is damaged by alkali from the surface to the inside, it is important to set the minimum reaction conditions. When the contact angle to water of the transparent support on the opposite surface is used as an index of damage to each layer due to alkali, particularly when the transparent support is triacetylcellulose, preferably 10 to 50 degrees, more preferably Is 30 to 50 degrees, more preferably 40 to 50 degrees. If it is 50 degrees or more, there is a problem in the adhesion to the polarizing film, which is not preferable. On the other hand, if it is less than 10 degrees, the film suffers too much damage, which impairs physical strength and is not preferable.

b. Method of applying alkaline solution As a means of avoiding damage to each film in the above-mentioned immersion method, an alkali solution is applied, heated, washed with water, and dried only on the surface opposite to the surface having the coating layer under appropriate conditions. A liquid coating method is preferably used. The application in this case means that an alkaline solution or the like is brought into contact only with the surface to be saponified, and in addition to the application, it may be carried out by spraying or contacting a belt containing the solution. Including. By adopting these methods, a separate facility and process for applying an alkaline solution are required, which is inferior to the immersion method (1) from the viewpoint of cost. On the other hand, since the alkali solution contacts only the surface to be saponified, the opposite surface can have a layer using a material that is weak against the alkali solution. For example, vapor deposition films and sol-gel films have various effects such as corrosion, dissolution, and peeling due to alkali solution, so it is not desirable to use the immersion method. Is possible.

  In any of the saponification methods (1) and (2), since each layer can be formed by unwinding from a roll-shaped support, it may be performed by a series of operations in addition to the film manufacturing process. . Furthermore, the polarizing plate can be produced more efficiently than the same operation with a single wafer by continuously performing the pasting step with the polarizing plate made of the unwound support.

c. Method of protecting and saponifying with a laminate film As in (2) above, when the coating layer is insufficient in resistance to an alkaline solution, a laminate film is pasted on the surface on which the final layer is formed after forming the final layer. By immersing them in an alkaline solution after combining them, only the triacetyl cellulose surface opposite to the surface on which the final layer is formed can be hydrophilized, and then the laminate film can be peeled off. Even in this method, the hydrophilic treatment necessary for the polarizing plate protective film can be applied only to the surface opposite to the surface on which the final layer of the triacetyl cellulose film is formed without damaging the coating layer. Compared with the method (2), there is an advantage that a laminate film is generated as waste, but a device for applying a special alkaline solution is unnecessary.

d. Method of immersing in alkaline solution after forming up to middle layer Although resistant to alkaline solution up to lower layer, but insufficient resistance to alkaline solution of upper layer, dip into alkaline solution after forming up to lower layer to make both sides hydrophilic The upper layer can also be formed after processing. Although the manufacturing process is complicated, for example, in a film composed of an antiglare hard coat layer and a low refractive index layer of a fluorine-containing sol-gel film, when it has a hydrophilic group, the antiglare hard coat layer and the low refractive index layer There is an advantage of improving the interlayer adhesion.

e. Method of forming a coating layer on a saponified triacetyl cellulose film A saponification of a triacetyl cellulose film by immersing it in an alkaline solution in advance and applying the coating layer directly on one side or via another layer It may be formed. In the case of saponification by dipping in an alkaline solution, the interlayer adhesion with the triacetyl cellulose surface hydrophilized by saponification may deteriorate. In such a case, after saponification, only the surface on which the coating layer is to be formed is treated by corona discharge, glow discharge or the like to remove the hydrophilic surface and then form the coating layer. Further, when the coating layer has a hydrophilic group, the interlayer adhesion may be good.

4- (8) Production of Polarizing Film The film of the present invention can be used as a polarizing film and a protective film disposed on one side or both sides thereof, and can be used as a polarizing film.
As one protective film, the film of the present invention is used. The other protective film may be a normal cellulose acetate film, but is produced by the above-mentioned solution casting method and at a stretch ratio of 10 to 100%. It is preferable to use a cellulose acetate film stretched in the width direction in the form of a roll film.
Furthermore, in the polarizing plate of the present invention, it is preferable that one side is an antireflection film, whereas the other protective film is an optical compensation film having an optically anisotropic layer made of a liquid crystalline compound.

Examples of the polarizing film include an iodine polarizing film, a dye polarizing film using a dichroic dye, and a polyene polarizing film. The iodine polarizing film and the dye polarizing film are generally produced using a polyvinyl alcohol film.
The transparent support of the antireflection film and the slow axis of the cellulose acetate film and the transmission axis of the polarizing film are arranged so as to be substantially parallel.

The moisture permeability of the protective film is important for the productivity of the polarizing plate. The polarizing film and the protective film are bonded together with an aqueous adhesive, and the adhesive solvent is dried by diffusing in the protective film. The higher the moisture permeability of the protective film, the faster the drying and the higher the productivity. However, if the protective film is too high, moisture will enter the polarizing film depending on the usage environment (high humidity) of the liquid crystal display device. Polarization ability decreases.
The moisture permeability of the protective film is determined by the thickness, free volume, hydrophilicity / hydrophobicity, etc. of the transparent support or polymer film (and polymerizable liquid crystal compound).
When using the film of the present invention as a protective film of a polarizing plate, the moisture permeability is preferably from 100~1000g / m ² · 24hrs, and more preferably a 300~700g / m ² · 24hrs.
In the case of film formation, the thickness of the transparent support can be adjusted by lip flow rate and line speed, or stretching and compression. Since the moisture permeability varies depending on the main material to be used, it is possible to make a preferable range by adjusting the thickness.
In the case of film formation, the free volume of the transparent support can be adjusted by the drying temperature and time.
Also in this case, moisture permeability varies depending on the main material to be used, so that a preferable range can be obtained by adjusting the free volume.
The hydrophilicity / hydrophobicity of the transparent support can be adjusted by an additive. The moisture permeability can be increased by adding a hydrophilic additive to the free volume, and conversely, the moisture permeability can be lowered by adding a hydrophobic additive.
By independently controlling the moisture permeability, a polarizing plate having an optical compensation ability can be manufactured at low cost with high productivity.

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

The method for stretching the polymer film is described in detail in paragraphs 0020 to 0030 of JP-A-2002-86554.
Of the two protective films of the polarizer, the film other than the antireflection film is preferably an optical compensation film having an optical compensation layer comprising an optically anisotropic layer. The optical compensation film (retardation film) can improve the viewing angle characteristics of the liquid crystal display screen.
A known film can be used as the optical compensation film, but the optical compensation film described in JP-A-2001-100042 is preferable in terms of widening the viewing angle.

5. Form of use of the present invention The film of the present invention is used in image display devices such as liquid crystal display devices (LCD), plasma display panels (PDP), electroluminescence displays (ELD) and cathode ray tube display devices (CRT). The optical filter according to the present invention can be used on a known display such as a plasma display panel (PDP) or a cathode ray tube display (CRT).

5- (1) Liquid Crystal Display Device The film and polarizing plate of the present invention can be advantageously used for an image display device such as a liquid crystal display device, and is preferably used for the outermost layer of the display.
The liquid crystal display device has a liquid crystal cell and two polarizing plates arranged on both sides thereof, and the liquid crystal cell carries a liquid crystal between two electrode substrates. Furthermore, one optically anisotropic layer may be disposed between the liquid crystal cell and one polarizing plate, or two optically anisotropic layers may be disposed between the liquid crystal cell and both polarizing plates.

  The liquid crystal cell is preferably in TN mode, VA mode, OCB mode, IPS mode or ECB mode.

<TN mode>
In the TN mode liquid crystal cell, rod-like liquid crystal molecules are substantially horizontally aligned when no voltage is applied, and are twisted and aligned at 60 to 120 °.
The TN mode liquid crystal cell is most frequently used as a color TFT liquid crystal display device, and is described in many documents.

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

<OCB mode>
The OCB mode liquid crystal cell is a bend alignment mode liquid crystal cell in which rod-like liquid crystalline molecules are aligned in substantially opposite directions (symmetrically) at the upper and lower portions of the liquid crystal cell. US Pat. No. 4,583,825, No. 5,410,422. Since the rod-like liquid crystal molecules are symmetrically aligned at the upper and lower portions of the liquid crystal cell, the bend alignment mode liquid crystal cell has a self-optical compensation function. Therefore, this liquid crystal mode is called an OCB (Optically Compensatory Bend) liquid crystal mode. The bend alignment mode liquid crystal display device has an advantage of high response speed.

<IPS mode>
The IPS mode liquid crystal cell is a type in which a nematic liquid crystal is switched by applying a lateral electric field. IDRC (Asia Display '95), p. 577-580 and p. 707-710.

<ECB mode>
In the ECB mode liquid crystal cell, rod-like liquid crystalline molecules are substantially horizontally aligned when no voltage is applied. The ECB mode is one of the liquid crystal display modes having the simplest structure, and is described in detail in, for example, Japanese Patent Application Laid-Open No. 5-203946.

5- (2) Display other than liquid crystal display device <PDP>
A plasma display panel (PDP) is generally composed of a gas, a glass substrate, an electrode, an electrode lead material, a thick film printing material, and a phosphor. Two glass substrates are a front glass substrate and a rear glass substrate. An electrode and an insulating layer are formed on the two glass substrates. A phosphor layer is further formed on the rear glass substrate. Two glass substrates are assembled and gas is sealed between them.
Plasma display panels (PDP) are already commercially available. The plasma display panel is described in JP-A-5-205643 and JP-A-9-306366.

The front plate may be disposed on the front surface of the plasma display panel. The front plate preferably has sufficient strength to protect the plasma display panel. The front plate can be used with a gap from the plasma display panel, or can be used by directly pasting the front plate to the plasma display body.
In an image display device such as a plasma display panel, an optical filter can be directly attached to the display surface. When a front plate is provided in front of the display, an optical filter can be attached to the front side (outside) or the back side (display side) of the front plate.

<Touch panel>
The film of the present invention can be applied to touch panels described in JP-A-5-127822 and JP-A-2002-48913.

<Organic EL device>
The film of the present invention can be used as a substrate (base film) such as an organic EL element or a protective film.
When the film of the present invention is used for an organic EL device or the like, JP-A-11-335661, JP-A-11-335368, JP-A-2001-192651, JP-A-2001-192652, JP-A-2001-192653, JP-A-2001-335776, JP-A-2001-247859, JP-A-2001-181616, JP-A-2001-181617, JP-A-2002-181816, JP-A-2002-181617, JP-A-2002-056776, etc. The contents described in each publication can be applied. Moreover, it is preferable to use together with the content of each gazette of Unexamined-Japanese-Patent No. 2001-148291, Unexamined-Japanese-Patent No. 2001-221916, and Unexamined-Japanese-Patent No. 2001-231443.

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

(Synthesis of perfluoroolefin copolymer (1))

  Into a stainless steel autoclave with a stirrer of 100 ml, 40 ml of ethyl acetate, 14.7 g of hydroxyethyl vinyl ether and 0.55 g of dilauroyl peroxide were charged, and the inside of the system was deaerated and replaced with nitrogen gas. Furthermore, 25 g of hexafluoropropylene (HFP) was introduced into the autoclave and the temperature was raised to 65 ° C. The pressure when the temperature in the autoclave reached 65 ° C. was 0.53 MPa. The reaction was continued for 8 hours while maintaining the temperature, and when the pressure reached 0.31 MPa, the heating was stopped and the mixture was allowed to cool. When the internal temperature dropped to room temperature, unreacted monomers were driven out, the autoclave was opened, and the reaction solution was taken out. The obtained reaction solution was poured into a large excess of hexane, and the polymer was precipitated by removing the solvent by decantation. Further, this polymer was dissolved in a small amount of ethyl acetate and reprecipitated twice from hexane to completely remove the residual monomer. After drying, 28 g of polymer was obtained. Next, 20 g of the polymer was dissolved in 100 ml of N, N-dimethylacetamide, and 11.4 g of acrylic acid chloride was added dropwise under ice cooling, followed by stirring at room temperature for 10 hours. Ethyl acetate was added to the reaction solution, washed with water, the organic layer was extracted and concentrated, and the resulting polymer was reprecipitated with hexane to obtain 19 g of perfluoroolefin copolymer (1). The resulting polymer had a refractive index of 1.421.

(Preparation of sol solution a)
A stirrer, a reactor equipped with a reflux condenser, 120 parts of methyl ethyl ketone, 100 parts of acryloyloxypropyltrimethoxysilane (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.), 3 parts of diisopropoxyaluminum ethyl acetoacetate were added and mixed. Thereafter, 30 parts of ion-exchanged water was added and reacted at 60 ° C. for 4 hours, and then cooled to room temperature to obtain sol solution a. The mass average molecular weight was 1600, and among the components higher than the oligomer component, the component having a molecular weight of 1000 to 20000 was 100%. Further, from the gas chromatography analysis, the raw material acryloyloxypropyltrimethoxysilane did not remain at all.

(Preparation of sol liquid b)
After the reaction, the mixture was cooled to room temperature, and then a sol solution b was obtained in the same manner as the sol composition a except that 6 parts of acetylacetone was added.

(Synthesis of fluororesin-containing polymer (FP-132))
To a reactor equipped with a stirrer and a reflux condenser, 39.93 g of 1H, 1H, 7H-dodecafluoroheptyl acrylate, 1.1 g of dimethyl 2,2′-azobisisobutyrate and 30 g of 2-butanone were added, and a nitrogen atmosphere was added. For 6 hours at 78 ° C. to complete the reaction. The weight average molecular weight was 1.5 × 10 ⁴ .
Fluoro resin-containing polymer (FP-132)

(1) Coating of antistatic layer A triacetyl cellulose film (TD80U, manufactured by Fuji Photo Film Co., Ltd.) having a thickness of 80 μm is unwound in a roll form, and a coating liquid 1 for forming a conductive layer is applied at 130 ° C. And dried for 2 minutes to form a conductive layer having a thickness of 0.11 μm. Next, the following protective layer-forming coating solution 1 is applied on the conductive layer, dried at 130 ° C. for 2 minutes to form a protective layer having a thickness of 0.05 μm, and the antistatic layer / protective layer of Example A optical A film was obtained. Antistatic Layer / Protective Layer The haze of the optical film of Example A is 1.0% and is excellent in transparency.

(Antistatic layer / protective layer Example A)
(Coating layer forming coating solution 1)
(1) Acrylic resin having a plurality of carboxylic acid groups 30.9 parts by mass (Julimer ET-410, number average molecular weight 9700,
(Weight average molecular weight 17000, solid content concentration 30%, manufactured by Nippon Pure Chemical)
(2) Carbodiimide crosslinking agent 6.4 parts by mass (Carbodilite V-02-L2, solid content concentration 40%,
Carbodiimide equivalent 385; Nisshinbo Co., Ltd.)
-(3) Tin oxide-antimony oxide needle-shaped transparent conductive material aqueous dispersion 131.1 parts by mass (FS-10D, solid content concentration 20%, major axis / minor axis ratio 20-30, manufactured by Ishihara Sangyo Co., Ltd.)
Silica fine particle dispersion 5.0 parts by mass (Seahoster KE-W30, solid content concentration 20%, manufactured by Nippon Shokubai Co., Ltd.)
・ Surfactant 0.73 parts by mass (Narrow Acty HN-100, manufactured by Sanyo Chemical Industries)
・ Surfactant 1.44 parts by mass (Sandet BL, solid content concentration 43%, manufactured by Sanyo Chemical Industries)
・ Water 824.4 parts by mass

(Protective layer forming coating solution 1)
-Polyethylene latex 17.8 parts by mass (Chemical S120, solid content concentration 27%, manufactured by Mitsui Chemicals)
・ 11.8 parts by mass of colloidal silica (Snowtex C, solid content 20%, manufactured by Nissan Chemical Co., Ltd.)
-Epoxy curing agent 1.7 parts by mass (Denacol EX-614B, manufactured by Nagase Kasei Co., Ltd.)
・ Surfactant 0.52 parts by mass (Narrow Acty HN-100, manufactured by Sanyo Chemical Industries)
・ Surfactant 0.59 parts by mass (Sandet BL, solid content concentration 43%, manufactured by Sanyo Chemical Industries)

[Antistatic layer / Protective layer Example B]
Instead of the acrylic resin having a plurality of carboxylic acid groups (Durimer ET-410) used in the coating liquid 1 for forming the conductive layer, Joncryl 70 (solid content 30%, acid value 240, weight average molecular weight) which is an acrylic resin latex 16,500) 30.9 parts by mass was used, and a conductive layer was formed on the support in exactly the same manner except that the amount of carbodiimide compound carbodilite V-02-L2 was 12.8 parts by mass. .
Next, a protective layer-forming coating solution 1 similar to that used in Example A was applied on the conductive layer, dried at 130 ° C. for 2 minutes, and a protective layer having a thickness of 0.05 μm. The antistatic layer / protective layer of Example B was obtained. Antistatic Layer / Protective Layer The haze of the optical film of Example B was 2.8%.

[Antistatic layer / protective layer Example C]
Antistatic Layer / Protective Layer Instead of the acrylic resin having a plurality of carboxylic acid groups (Jurimer ET-410) used in Example A, urethane latex: Neoreds R-967 (solid content 40%, acid value 19; Avecia A conductive layer was formed on the support in exactly the same manner except that 23.2 parts by mass of the carbodiimide compound carbodilite V-02-L2 was added to 3.2 parts by mass.
Next, the same protective layer-forming coating solution 1 as used in Example 1 was applied on the conductive layer and dried at 130 ° C. for 2 minutes to form a protective layer having a thickness of 0.05 μm to prevent static charge. Layer / Protective Layer An antistatic film of Example C was obtained. Antistatic Layer / Protective Layer The haze of the optical film of Example C is 1.5% and is excellent in transparency.

[Antistatic layer / Protective layer comparative example A]
Antistatic Layer / Protective Layer Aqueous dispersion of needle-like tin oxide-antimony oxide transparent conductive material, which is the conductive material used in Example A [FS-10D (solid content concentration 20%, manufactured by Ishihara Sangyo Co., Ltd.)] 131 Except that in place of 1 part by mass, spherical tin oxide-antimony oxide conductive dispersion TDL (solid content concentration 17%, average particle size 100 nm, manufactured by Mitsubishi Materials Corporation) 154.1 parts by mass was used. Thus, a conductive layer was formed on the support.
Next, the same protective layer-forming coating solution 1 as used in Example 1 was applied on the conductive layer and dried at 130 ° C. for 2 minutes to form a protective layer having a thickness of 0.05 μm to prevent static charge. An antistatic film of Comparative Example A for the layer / protective layer was obtained. The haze of the optical film of Comparative Example A for the antistatic layer / protective layer is 2.1%, which is excellent in transparency.

[Antistatic layer / Protective layer comparison example B]
Antistatic Layer / Protective Layer An antistatic film of Comparative Example B for antistatic layer / protective layer was prepared in exactly the same manner as in Example A, except that no protective layer was formed on the conductive layer. The haze of the optical film of Comparative Example A for the antistatic layer / protective layer is 5.8% and is excellent in transparency.
[Antistatic Layer / Protective Layer Example D]
Antistatic Layer / Protective Layer In Example A, instead of the conductive layer forming coating solution 1, the conductive layer forming coating solution 3 [weight solids concentration of (1) carboxylic acid group-containing resin and (2) carbodiimide compound Was applied in exactly the same manner except that the coating amount was reduced by 10%, and dried at 130 ° C. for 2 minutes to form a conductive layer having a thickness of 0.11 μm.

(Coating liquid 3)
(1) Resin having a plurality of carboxylic acid groups 30.9 parts by mass (Julimer ET-410, number average molecular weight 9700,
(Weight average molecular weight 17000, solid content concentration 30%, manufactured by Nippon Pure Chemical)
(2) Carbodiimide crosslinking agent 6.4 parts by mass (Carbodilite V-02-L2, solid content concentration 40%,
Carbodiimide equivalent 385; Nisshinbo Co., Ltd.)
-(3) Powder of tin oxide-antimony oxide needle-like transparent conductive material 13.1 parts by mass (solid content concentration 100%) (FS-10D, solid content concentration 20%, major axis / minor axis ratio 20-30, Ishihara (Made by Sangyo)
Silica fine particle dispersion 5.0 parts by mass (Seahoster KE-W30, solid content concentration 20%, manufactured by Nippon Shokubai Co., Ltd.)
・ Surfactant 0.73 parts by mass (Narrow Acty HN-100, manufactured by Sanyo Chemical Industries)
・ Surfactant 1.44 parts by mass (Sandet BL, solid content concentration 43%, manufactured by Sanyo Chemical Industries)
-33.4 parts by weight of water Next, a coating solution 1 for forming a protective layer similar to that used in Example A was applied on the conductive layer, dried at 130 ° C for 2 minutes, A protective layer having a thickness of 0.05 μm was formed to obtain an antistatic film of the antistatic layer / protective layer of Example D. Antistatic Layer / Protective Layer The haze of the optical film of Example D was 3.1%.

─────────────────────────────────
Composition of coating liquid A for antiglare hard coat layer ─────────────────────────────────
PET-30 50.0g
Irgacure 184 2.0g
SX-350 (30%) 1.7 g
Cross-linked acrylic-styrene particles (30%) 13.3 g
FP-132 0.75g
KBM-5103 10.0g
Toluene 38.5g
─────────────────────────────────

─────────────────────────────────
Composition of coating liquid B for light diffusion layer ─────────────────────────────────
Desolite Z7404 100g
DPHA 31g
KBM-5103 10g
KE-P150 8.9g
MXS-300 3.4g
MEK 19g
MIBK (methyl isobutyl ketone) 13g
─────────────────────────────────

─────────────────────────────────
Composition of coating solution C for antiglare hard coat layer ─────────────────────────────────
PET-30 50.0g
Irgacure 184 2.0g
SX-350 (30%) 1.7 g
Cross-linked acrylic-styrene particles (30%) 11.3 g
Bright 20GNR 4.6-EH 0.12g
FP-132 0.75g
KBM-5103 10.0g
Toluene 40.5g
─────────────────────────────────

─────────────────────────────────
Composition of coating solution D for light diffusion layer ─────────────────────────────────
Desolite Z7404 100g
DPHA 31g
KBM-5103 10g
KE-P150 17.8g
Bright 20GNR4.6-EH 0.12g
MXS-300 2.3g
MEK 11g
MIBK (methyl isobutyl ketone) 13g
─────────────────────────────────

  The coating solution was filtered through a polypropylene filter having a pore size of 30 μm to prepare a coating solution for an antiglare hard coat layer and a light diffusion layer.

──────────────────────────────────
Composition of coating solution E-1 for low refractive index layer ──────────────────────────────────
DPHA 3.3g
Hollow silica (18.2%) 40.0g
RMS-033 0.7g
Irgacure 907 0.2g
Sol liquid a 6.2g
MEK 299.6g
──────────────────────────────────

──────────────────────────────────
Composition of coating liquid E-2 for low refractive index layer ──────────────────────────────────
DPHA 1.4g
P-1 5.6g
Hollow silica (18.2%) 20.0g
RMS-033 0.7g
Irgacure 907 0.2g
Sol liquid a 6.2g
MEK 315.9g
──────────────────────────────────

──────────────────────────────────
Composition of coating liquid E-3 for low refractive index layer ──────────────────────────────────
OPSTAR JTA113 (6%) 13.0g
MEK-ST-L (30%) 1.3g
Sol liquid a 0.6g
MEK 5.0g
Cyclohexanone 0.6g
──────────────────────────────────

──────────────────────────────────
Preparation of coating solution E-4 for low refractive index layer ──────────────────────────────────
OPSTAR JN7228A (6%) 13.0g
MEK-ST (30%) 1.3g
MEK-ST-L (30%) 1.3g
Sol liquid a 0.6g
MEK 5.0g
Cyclohexanone 0.6g
──────────────────────────────────

──────────────────────────────────
Composition of coating solution E-5 for low refractive index layer ──────────────────────────────────
DPHA 1.4g
P-1 5.6g
Hollow silica (18.2%) 20.0g
RMS-033 0.7g
Irgacure 651 0.2g
Sol liquid a 6.2g
MEK 315.9g
──────────────────────────────────

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

The compounds used are shown below.
KBM-5103:
Silane coupling agent [Shin-Etsu Chemical Co., Ltd.]

PET-30:
Mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate [manufactured by Nippon Kayaku Co., Ltd.]
Irgacure 184:
Polymerization initiator [Ciba Specialty Chemicals Co., Ltd.]
SX-350:
Cross-linked polystyrene particles having an average particle size of 3.5 μm [refractive index of 1.61, manufactured by Soken Chemical Co., Ltd., 30% toluene dispersion, used after dispersion at 10,000 rpm in a Polytron disperser for 20 minutes]
Cross-linked acrylic-styrene particles:
Average particle size 3.5 μm [refractive index 1.55, manufactured by Soken Chemical Co., Ltd., 30% toluene dispersion, used after dispersion for 20 minutes at 10,000 rpm in a polytron disperser]
FP-132:
Fluoro resin-containing polymer

Desolite Z7404:
ZrO ₂ fine particle-containing hard coating agent [refractive index 1.62, solid content concentration: 60% by mass, zirconium oxide fine particle content: 70% by mass (based on solid content), average particle size of zirconium oxide fine particles: about 20 nm, solvent composition: MIBK / MEK = 9/1, manufactured by JSR Corporation]
DPHA:
Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate [refractive index 1.52, manufactured by Nippon Kayaku Co., Ltd.]
KEP-150:
Silica particles having an average particle size of 1.5 μm [refractive index: 1.46, manufactured by Nippon Shokubai Co., Ltd., 30% MEK dispersion, used after dispersion at 10,000 rpm for 20 minutes in a Polytron disperser]
MXS-300:
Average particle size of 3 μm PMMA particles [refractive index: 1.49, manufactured by Soken Chemical Co., Ltd., 30% MIBK dispersion, used after dispersion at 10,000 rpm for 20 minutes in a Polytron disperser]
Bright 20 GNR 4.6-EH:
A benzoguanamine / melamine / formaldehyde condensate spherical powder plated with nickel and gold [manufactured by Nippon Chemical Industry Co., Ltd.]

OPSTAR JN7228A: Thermally crosslinkable fluorine-containing polymer [refractive index 1.42, solid content concentration 6%, manufactured by JSR Corporation]
Opster JTA113:
Thermally crosslinkable fluorine-containing polymer [refractive index 1.44, solid content concentration 6%, manufactured by JSR Corporation]
P-1:
Perfluoroolefin copolymer (1)
MEK-ST:
Colloidal silica dispersion [average particle size 10-20 nm, solid content 30%, manufactured by Nissan Chemical Co., Ltd.]
MEK-ST-L:
Colloidal silica dispersion [MEK-ST particle size difference, average particle size 45 nm, solid content concentration 30%, manufactured by Nissan Chemical Co., Ltd.]
Hollow silica: Hollow silica fine particle dispersion prepared as follows

(Preparation of hollow silica fine particle dispersion)
Hollow silica fine particle sol (isopropyl alcohol silica sol, CS60-IPA manufactured by Catalytic Chemical Industry Co., Ltd., average particle diameter 60 nm, shell thickness 10 nm, silica concentration 20%, silica particle refractive index 1.31) in 500 parts, acryloyloxypropyl After 30 parts of trimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-5103) and 1.5 parts of diisopropoxyaluminum ethyl acetate were added and mixed, 9 parts of ion-exchanged water was added. After making it react at 60 degreeC for 8 hours, it cooled to room temperature and added 1.8 parts of acetylacetone, and obtained the hollow silica dispersion liquid. The resulting hollow silica dispersion had a solid content concentration of 18% by mass and a refractive index after solvent drying of 1.31.

RMS-033: Reactive silicone (manufactured by Gelest Co., Ltd.)
Irgacure 907: Photopolymerization initiator (manufactured by Ciba Specialty Chemicals)
Irgacure 651: Photopolymerization initiator [Ciba Specialty Chemicals Co., Ltd.]

[Example 1: Preparation and evaluation of inventive samples 1 to 13 and comparative samples 14 to 24 of an antireflection film]
(1) Coating of light scattering layer On the above-described antistatic layer or protective layer, the coating liquid for the light scattering layer (antiglare hard coat layer or light diffusion layer) shown in Table 1 is used in a number of lines of 135 / Using a microgravure roll with a diameter of 50 mm having a gravure pattern of inch and depth of 60 μm and a doctor blade, coating was performed at a conveyance speed of 10 m / min, drying at 60 ° C. for 150 seconds, and further under a nitrogen purge, 160 W / cm Using an air-cooled metal halide lamp (made by Eye Graphics Co., Ltd.), the coating layer is cured by irradiating with ultraviolet rays having an illuminance of 400 mW / cm ² and an irradiation amount of 250 mJ / cm ² , and an antiglare hard coat layer (thickness) 6 μm) or a light scattering layer (thickness 3.4 μm) was formed and wound up.

(3) Coating of low refractive index layer The triacetylcellulose film coated with the light scattering layer is unwound again, and the low refractive index layer coating solution is formed into a gravure pattern with a line number of 200 lines / inch and a depth of 30 μm. Using a microgravure roll having a diameter of 50 mm and a doctor blade, the coating was performed at a conveyance speed of 20 m / min, drying at 120 ° C. for 75 seconds, and further drying for 10 minutes, and then air cooling at 240 W / cm under nitrogen purge Using a metal halide lamp (manufactured by Eye Graphics Co., Ltd.), ultraviolet rays having an illuminance of 400 mW / cm ² and an irradiation amount of 240 mJ / cm ² were irradiated to form a low refractive index layer having a thickness of 100 nm and wound up.

(Preparation of antireflection film sample)
As shown in Table 1, an antireflection film sample was prepared by the above method.

(Saponification treatment of antireflection film)
After film formation, the sample was subjected to the following treatment. A 1.5 mol / L aqueous sodium hydroxide solution was prepared and kept at 55 ° C. A 0.01 mol / L dilute sulfuric acid aqueous solution was prepared and kept at 35 ° C. The prepared antireflection film was immersed in the aqueous sodium hydroxide solution for 2 minutes, and then immersed in water to sufficiently wash away the aqueous sodium hydroxide solution. Subsequently, after being immersed in the above-mentioned dilute sulfuric acid aqueous solution for 1 minute, it was immersed in water to sufficiently wash away the dilute sulfuric acid aqueous solution. Finally, the sample was thoroughly dried at 120 ° C.
In this way, saponification-treated antireflection films (present invention samples 1 to 13 and comparative samples 14 to 24) were produced.

(Evaluation of antireflection film)
About these obtained antireflection film samples, the following items were evaluated. The results are shown in Table 1.
(1) Average reflectance Using a spectrophotometer (manufactured by JASCO Corporation), the spectral reflectance at an incident angle of 5 ° was measured in a wavelength region of 380 to 780 nm. The average reflectance of 450-650 nm was used for the result.
(2) Surface resistance value measurement The surface resistance value of the antistatic film was measured for all the samples using a surface resistance measuring device (manufactured by Shinto Kagaku Co., Ltd.) at 25 ° C. and 55% RH. The electrode spacing was 5 mm, the electrode width was 100 mm, the applied voltage was 50 V, and the values 30 seconds after voltage application were measured.
(3) Evaluation of dustiness The transparent support side of the antireflection film was attached to the CRT surface, and used for 24 hours in a room having 1 to 2 million dust and tissue paper waste of 0.5 μm or more per 1 ft3 (cubic foot). . The number of adhering dust and tissue paper waste per 100 cm ^{2 of the} antireflection film was measured, and the average value of each result was evaluated as follows.
◎: Less than 20 ○: 20 to 49 △: 50 to 199 ×: 200 or more (4) Evaluation of white powder property at the time of application The state of white powder adhered to the roller at the time of applying the light scattering layer and the surface state of the light scattering layer Were observed and evaluated as follows.
○: No white powder and no surface defects.
Δ: White powder slightly adheres to the roller, but there is no repellency in the light scattering layer.
×: White powder adheres to the roller and repelling occurs in the light scattering layer

(5) Haze The following measurements measured the total haze (H), internal haze (Hi), and surface haze (Hs) of the obtained film.
(I) The total haze value (H) of the film obtained according to JIS-K7136 is measured.
(Ii) Cellotape (registered trademark) (manufactured by Nichiban Co., Ltd.) was applied to the surface of the obtained film on the low refractive index layer side, haze was measured in a state where surface haze was removed, and cellotape (registered trademark) separately measured ) Was calculated as the internal haze (Hi) of the film.
(Iii) A value obtained by subtracting the internal haze (Hi) calculated in (ii) from the total haze (H) measured in (i) above was calculated as the surface haze (Hs) of the film.

(6) Eraser rubbing resistance An anti-reflection film is fixed on a glass surface with an adhesive, and an anti-rubber, MONO (trade name, manufactured by Dragonfly), which is 8 mm in diameter and 4 mm thick, is used as the head of the rubbing tester. After pressing vertically from above with a load of 500 g / cm ^{2 on} the surface, rubbing 200 strokes at a stroke length of 3.5 cm and a rubbing speed of 1.8 cm / s under conditions of 25 ° C. and 60 RH%, the attached eraser After removal, the rubbing part of the sample was visually confirmed, and the degree of scratching on the surface was evaluated three times on average by repeating the above test three times.
○: Scratches are hardly recognized.
Δ: Slight scratches are observed.
X: Scratches are clearly recognized.
XX: Scratches are recognized on the entire surface after rubbing.

(7) Adhesion evaluation The surface of the antireflective film having the low refractive index layer is cut with a cutter knife in a grid pattern of 11 vertical and 11 horizontal cuts, and a total of 100 square squares are carved. Nitto A polyester adhesive tape (NO. 31B) manufactured by Denko Co., Ltd. was pressure-bonded, and the adhesion test was repeated three times at the same place. The presence or absence of peeling was visually observed, and the following four-stage evaluation was performed.
◎: No peeling was observed in 100 squares ○: No peeling was found in 100 squares within 2 squares △: No peeling was observed in 100 squares Of 3 to 10 mm ×: those in which peeling was observed in 100 cells exceeded 10 mm (8) Image sharpness Image sharpness in accordance with JIS-K7105, Suga Test Instruments Co., Ltd. Measurement was performed with an optical comb having a slit width of 0.5 mm using a manufactured image clarity measuring instrument (ICM-2D type).

From the results shown in Table 1, the following is clear.
The antireflection film of the present invention is excellent in dust resistance, does not generate white powder when coated with a light scattering layer, is excellent in adhesion and has a good balance of optical properties, and has an improved overall performance as an antireflection film. .
In addition, instead of KEP-150 used for the light diffusion layer coating solution, MXS-150H: highly crosslinked PMMA particles having an average particle diameter of 1.5 μm [refractive index: 1.49, manufactured by Soken Chemical Co., Ltd., 30% MIBK dispersion When used after dispersion for 20 minutes at 10,000 rpm with a Polytron disperser], the settling stability of the coating solution was improved and the suitability for continuous coating was increased.
Further, when the sol solution b was used in place of the organosilane sol solution a used in the low refractive index layer coating solution, the stability of the coating solution with time was improved and the suitability for continuous coating was increased.
Also, instead of the triacetyl cellulose film, on one side of the cycloolefin film (Zeonor film ZF14-100, manufactured by Nippon Zeon Co., Ltd., thickness 100 μm) (the surface that becomes the adhesive interface with the light scattering layer) immediately before coating Even when the corona discharge treatment was used, the dust resistance was excellent, white powder was not generated when the light scattering layer was applied, the adhesiveness was excellent, the optical properties were well balanced, and an antireflection film was obtained.

[Example 2]
A triacetyl cellulose film (TD80U, manufactured by Fuji Photo Film Co., Ltd.) having a thickness of 80 μm, immersed in a 1.5 mol / L, 55 ° C. NaOH aqueous solution for 2 minutes and then neutralized and washed with water. A polarizing plate was produced by adhering and protecting both sides of a polarizing film prepared by adsorbing iodine to polyvinyl alcohol and stretching it on the inventive sample (saponified). The polarizing plate produced in this way is a liquid crystal display device of a notebook personal computer equipped with a transmission type TN liquid crystal display device (Sumitomo 3M which is a polarization separation film having a polarization selection layer) so that the side having the low refractive index layer is the outermost surface. When the polarizing plate on the viewing side of D-BEF manufactured by Co., Ltd. is attached between the backlight and the liquid crystal cell), a display device with very low display quality and very high display quality is obtained. It was.

[Example 3]
The PVA film was immersed in an aqueous solution of 2.0 g / l iodine and 4.0 g / l potassium iodide at 25 ° C. for 240 seconds, and further immersed in an aqueous solution of boric acid 10 g / l at 25 ° C. for 60 seconds. It introduced into the tenter drawing machine of the form of FIG. 2 described in 2002-86554, it extended | stretched 5.3 time, the tenter was bent like FIG. 2 with respect to the extending | stretching direction, and the width | variety was kept constant hereafter. After drying in an atmosphere of 80 ° C., it was detached from the tenter. The difference in transport speed between the left and right tenter clips was less than 0.05%, and the angle formed by the center line of the introduced film and the center line of the film sent to the next process was 46 °. Here, | L1-L2 | is 0.7 m, W is 0.7 m, and | L1-L2 | = W. The substantial stretching direction Ax-Cx at the tenter outlet was inclined by 45 ° with respect to the center line 22 of the film sent to the next process. Wrinkles and film deformation at the tenter exit were not observed.
Furthermore, it was bonded to Fuji Photo Film Co., Ltd. Fujitac (cellulose triacetate, retardation value 3.0 nm), which was saponified with an aqueous solution of PVA (Pura-117H, Kuraray Co., Ltd.) 3%, and further 80 ° C. And dried to obtain a polarizing plate having an effective width of 650 mm. The absorption axis direction of the obtained polarizing plate was inclined 45 ° with respect to the longitudinal direction. The polarizing plate had a transmittance at 550 nm of 43.7% and a polarization degree of 99.97%. Further, when the substrate was cut into a size of 310 × 233 mm, a polarizing plate having a 45 ° absorption axis inclined with respect to the side with an area efficiency of 91.5% was obtained.
Next, each film of the inventive sample of Example 1 (saponified) was bonded to the above polarizing plate to produce a polarizing plate with antireflection. Using this polarizing plate, a liquid crystal display device in which the low refractive index layer was arranged as the outermost layer was produced. Had.

[Example 4]
As a protective film on the liquid crystal cell side of the polarizing plate on the viewing side of the transmission type TN liquid crystal cell to which the sample of the present invention of Example 2 is attached, and a protective film on the liquid crystal cell side of the polarizing plate on the backlight side, a discotic structural unit An optical compensation layer in which the disc surface is inclined with respect to the transparent support surface, and the angle formed by the disc surface of the discotic structural unit and the transparent support surface varies in the depth direction of the optical anisotropic layer. Using the wide viewing angle film (Wide View Film Ace, manufactured by Fuji Photo Film Co., Ltd.), it has excellent contrast in bright rooms, very wide viewing angles in the vertical and horizontal directions, and extremely excellent visibility. A high-quality liquid crystal display device was obtained. Moreover, it was difficult for dust to adhere to the display panel.
In addition, Samples 3, 4, 7, and 8 (Light Diffusion Layer Coating Solution B) of the present invention have a scattered light intensity of 30 ° with respect to an emission angle of 0 ° of 0.06%. The viewing angle in the direction was improved and the yellow color in the left and right direction was improved, and the liquid crystal display device was very good. For comparison, a film produced in the same manner as Samples 3, 4, 7, and 8 of the present invention except that the crosslinked PMMA particles and silica particles were removed from the coating solution B for the light diffusion layer was 30 ° with respect to an emission angle of 0 °. The scattered light intensity was substantially 0%, and the downward viewing angle was increased and the yellowing improvement effect was not obtained at all.

[Example 5]
When the inventive sample of Example 1 was bonded to the glass plate on the surface of the organic EL display device via an adhesive, reflection on the glass surface was suppressed, and a display device with high visibility was obtained.

[Example 6]
Using the sample of the present invention of Example 1, a polarizing plate with a single-sided antireflection film was prepared, and a λ / 4 plate was laminated on the opposite side of the polarizing plate on the side having the antireflection film, with the antireflection film side closest to the antireflection film side. When attached to the glass plate on the surface of the organic EL display device so as to be on the surface, the surface reflection and the reflection from the inside of the surface glass were cut, and a display with extremely high visibility was obtained.

It is a schematic sectional drawing which shows typically preferable embodiment of the film of this invention. It is a schematic sectional drawing which shows typically preferable embodiment of the film of this invention. It is a schematic sectional drawing which shows typically preferable embodiment of the film of this invention.

Explanation of symbols

(1) Support (2) Light scattering hard coat layer (3) Medium refractive index layer (4) High refractive index layer (5) Low refractive index layer (6) Protective layer (7) Antistatic layer

Claims (14)

  On the transparent film, an antistatic layer, a protective layer, and a light scattering layer composed of a resin layer in which fine particles are dispersed are sequentially provided. ) Contains acicular metal oxide particles in the range of 3-50.   The antistatic layer contains (1) a reaction product of a resin having a plurality of carboxylic acid groups in the molecule and having a weight average molecular weight of 2000 or more and (2) a compound having a plurality of carbodiimide structures in the molecule. The optical film according to claim 1.   The optical film according to claim 1 or 2, wherein a haze value when only an antistatic layer and a protective layer are provided on a transparent film is 1.0% or less.   The optical film according to claim 1, wherein a surface resistance value logSR at 25 ° C. and 55% RH of the optical film is 12Ω / sq or less.   The optical film according to claim 1, wherein the protective layer has a thickness of 0.01 μm to 0.5 μm.   The optical film according to claim 1, wherein the light scattering layer contains fine particles having a surface coated with a conductive substance.   The antireflective film according to any one of claims 1 to 6, wherein a low refractive index layer having a refractive index lower than that of the light scattering layer is provided on the light scattering layer.   The antireflection film according to claim 7, wherein the low refractive index layer contains hollow silica particles. The antireflection film according to claim 7 or 8, wherein any layer on the transparent film contains at least one of an organosilane compound represented by the following general formula [A] and a derivative thereof. .
Formula _{^{[A] (R 10) m}} -Si (X) 4-m
[In the general formula [A], R ¹⁰ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. X represents a hydroxyl group or a hydrolyzable group. m represents an integer of 1 to 3. ]   The optical film or the antireflection film according to claim 1, wherein the optical film or the antireflection film has a haze value of 0 to 90%.   The haze value resulting from surface scattering of the optical film or the antireflection film is 0 to 15%, and the internal haze is 0 to 90%. Antireflection film.   A polarizing plate having a polarizing film and protective films provided on both sides of the polarizing film, wherein at least one of the protective films is the optical film or the antireflection film according to claim 1. A polarizing plate.   An image display device, wherein the optical film or antireflection film according to claim 1 or the polarizing plate according to claim 12 is disposed on an image display surface.   14. The image display device according to claim 13, wherein the image display device is a TN, STN, IPS, VA, or OCB mode transmissive, reflective, or transflective liquid crystal display device.

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