JP2007238675A - Curable composition, method for producing curable composition, optical film, antireflection film, polarizing plate and image display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable composition giving a cured material having low refractive index, high hardness and excellent scratch resistance and stain-proofness after curing, provide a film having low reflectivity and excellent scratch resistance and stain-proofness and produced by using the curable composition, and provide a polarizing plate and an image display device produced by using the film. <P>SOLUTION: The curable composition contains (A) a fluorine-containing compound having a specific structure and containing a crosslinking agent reactive with hydroxy group and (B) a fluorine-containing polymer binder containing at least one each of a fluorine-containing vinyl monomer polymerization unit and a hydroxy-containing vinyl monomer polymerization unit. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

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

  In general, an antireflection film is used for an image display device such as a cathode ray tube display (CRT), a plasma display (PDP), an electroluminescence display (ELD), and a liquid crystal display (LCD). To prevent image reflection, it is placed on the top surface of the display to reduce reflectivity using the principle of optical interference. For this reason, high scratch resistance is required. In order to achieve high scratch resistance in a thin film having a thickness of about 100 nm, a technique such as improving the strength of the thin film itself and the adhesion to the lower layer can be employed.

  In general, the antireflection film can be produced by forming a low refractive index layer having an appropriate film thickness, which is lower than that of the support, on the support. In order to realize a low reflectance, it is desirable to use a material having a refractive index as low as possible for the low refractive index layer.

  A method using a melamine compound as a curing agent is described (see Patent Documents 1 and 2). As the melamine compound is used in a large amount, a higher scratch resistance is obtained, but at the same time, the reflectance is increased, so that the amount of use is limited.

For the purpose of increasing the film strength, a method using particles such as silica is described (see Patent Document 3). However, the use of the particles tends to cause an increase in reflectance, deterioration of the coated surface state, and the like.
JP 2003-277418 A JP 2004-269644 A JP 2003-26732 A

The present invention solves the above-mentioned problems, and provides a curable composition suitable for a film (optical film, antireflection film, polarizing plate, etc.) having high hardness (high scratch resistance, etc.) and a method for producing the same. To do.
Further, the present invention is excellent in at least one of high scratch resistance, antifouling property, and uniform coated surface by using such a curable composition, an optical film, an antireflection film, a polarizing plate, and an image. A display device is provided.

  As a result of various studies under the viewpoint that it is important to sufficiently advance the curing reaction of the curable composition in order to achieve high hardness (high scratch resistance and the like) in the optical film, The present invention has been achieved. That is, the inventors have found that the following configuration can solve the above-mentioned problems and achieve the object, and the present invention has been completed.

(1) Curing containing (A) inorganic particles having a crosslinkable group capable of reacting with a hydroxyl group, and (B) a fluorine-containing polymer having at least one kind of a fluorine-containing vinyl monomer polymerized unit and a hydroxyl group-containing vinyl monomer polymerized unit. Sex composition.
(2) The curable composition according to the above (1), further comprising (C) an organic base having a pKa of the conjugate acid of 5.0 to 10.5, or an organic base having a boiling point of 35 ° C to 85 ° C. .
(3) The curable composition according to the above (1) or (2), wherein the inorganic particles are previously mixed with a crosslinking agent capable of reacting with a hydroxyl group in the presence of an acid catalyst.
(4) The curable composition according to any one of (1) to (3), wherein the inorganic particles are silica particles.
(5) The curable composition according to (4), wherein the silica particles have a hollow structure and a refractive index is in the range of 1.15 to 1.40.

(6) The curable composition according to any one of (1) to (5), wherein the fluorine-containing polymer further has a polysiloxane polymer unit.
(7) The curable composition according to any one of (1) to (6), further comprising (D) an organosilane compound, or a hydrolyzate of the organosilane compound and / or a partial condensate thereof. .
(8) The curable composition according to any one of (1) to (7), further comprising (E) a compound having two or more (meth) acryloyl groups in one molecule.
(9) The above (1) to (8) further comprising (F) a polysiloxane structure represented by the following general formula (10), and a hydroxyl group or a compound having a structure capable of reacting with a hydroxyl group to form a bond. ). The curable composition as described in any one of.

In General Formula (10), R ¹ and R ² may be the same or different and each represents an alkyl group or an aryl group. p represents an integer of 2 to 500.

(10) (A) Inorganic particles mixed with a crosslinking agent capable of reacting with a hydroxyl group in the presence of an acid catalyst, and (B) a fluorine-containing vinyl monomer polymerized unit and a hydroxyl group-containing vinyl monomer polymerized unit. The manufacturing method of the curable composition which mixes a fluoropolymer.
(11) Before mixing (B), (C) an organic base having a pKa of a conjugate acid of 5.0 to 10.5 or an organic base having a boiling point of 35 ° C. or more and 85 ° C. or less is mixed (10 ). The manufacturing method of curable composition as described in.

(12) An optical film comprising at least one layer formed from the curable composition according to any one of (1) to (9).
(13) An antireflection film having the optical film according to (12) on a support.
(14) A polarizing plate in which at least one of the two protective films of the polarizing film in the polarizing plate is the optical film described in (12) above or the antireflection film described in (13) above.
(15) The image display apparatus which has the optical film as described in said (12), the antireflection film as described in said (13), or the polarizing plate as described in said (14) on the outermost surface of a display.

  According to the present invention, a curable composition suitable for a film (optical film, antireflection film, polarizing plate, etc.) having high hardness (high scratch resistance, etc.) can be obtained. In addition, in addition to high hardness, the present invention can provide a curable composition that, surprisingly, the cured film is excellent in at least one of antifouling property and uniform coated surface shape. Since the antifouling component such as the fluorine-containing polymer contained in the film has high scratch resistance, it is excellent in antifouling property because it is well held in the film. In addition, since inorganic particles having a crosslinkable group capable of reacting with a hydroxyl group are excellent in crosslinkability, a small amount of inorganic particles need be added. Therefore, the curable composition of the present invention can control the refractive index to be low, and can be suitably used as a material for forming the low refractive index layer.

  Therefore, the antireflection film obtained by using the curable composition of the present invention is excellent in scratch resistance, antifouling property and coated surface shape while having sufficient antireflection properties. In addition, the image display device provided with the antireflection film of the present invention and the image display device provided with the polarizing plate using the antireflection film of the present invention have little reflection of external light and reflection of the background, and are extremely visible. High nature. In addition, anti-reflection films are usually used on the outermost surface of display devices, so they are resistant to various stains such as fingerprints in exhibitions and daily use, even if they have adhesion resistance and stains ( Hereinafter, both are referred to as antifouling properties).

  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.

1. Components of the Present Invention First, the components of the present invention will be described.

1- (1) Component (A) of the present invention [inorganic particles previously mixed with a crosslinking agent capable of reacting with a hydroxyl group in the presence of an acid catalyst]
The curable composition of the present invention contains inorganic particles having a crosslinkable group capable of reacting with a hydroxyl group. The inorganic particles can be produced by mixing in advance with a crosslinking agent capable of reacting with a hydroxyl group in the presence of an acid catalyst.

  In the present invention, the crosslinkable group of the crosslinking agent (for example, methylol group of methylolmelamine) is presumed to react with the OH group of the inorganic particles and the OH group of the fluoropolymer. However, the reaction with the OH group of the inorganic particles is slower than the reaction with the OH group of the fluoropolymer, and it is assumed that the reaction hardly occurs under the thermosetting conditions (for example, 100 ° C. for 8 minutes). Therefore, it is preferable in the present invention that the crosslinking agent and the inorganic particles are premixed.

1- (1) -1. Inorganic Particles As inorganic particles, an oxide of at least one metal selected from silicon, zirconium, titanium, aluminum, indium, zinc, tin, and antimony is preferably used. 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 are included.

  The particle diameter of the inorganic particles used in the present invention is preferably as fine as possible in the dispersion medium, and preferably has a mass average diameter of 1 to 200 nm. More 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 as a dispersion in the dispersion medium to the coating solution for the layer to be used.
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-methoate) Shi-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 preferably 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 formed by the curable composition of the present invention, a composition in which inorganic particles having a high refractive index are dispersed in a monomer and an initiator, an organically substituted silicon compound, etc. A cured product is preferably used.
In this case, ZrO ₂ and TiO ₂ are particularly preferably used from the viewpoint of refractive index. For example, ZrO ₂ is most preferable for increasing the refractive index of the hard coat layer described below, and TiO ₂ fine particles are most preferable as particles for the high refractive index layer and medium refractive index layer described later.

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 mass average diameter of primary particles of TiO ₂ as a main component 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 the 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 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 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>
On the other hand, when forming a low refractive index layer with the curable composition of this invention, the inorganic particle contained in a low refractive index layer desirably has 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.

  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 represented by the following formula (X) is preferably 10 to 60%, more preferably 20 to 60. %, Most preferably 30-60%.

Formula (X)
^{x = (4πa 3/3)} / (4πb 3/3) × 100

  If hollow silica particles are made to have a lower refractive index and a higher porosity, the thickness of the outer shell becomes thinner and the strength of the particles becomes weaker. From the viewpoint of scratch resistance, the low refractive index is less than 1.15. Rate particles are not preferred.

  The method for producing hollow silica is described in, for example, JP-A 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 No. 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- (1) -2. Crosslinking agent capable of reacting with a hydroxyl group The crosslinking agent capable of reacting with a hydroxyl group used in the production of inorganic particles is not particularly limited as long as it has the above-mentioned number of functional groups capable of reacting with a hydroxyl group. Partial condensates of compounds, multimers, adducts with polyhydric alcohols, low molecular weight polyester films, blocked polyisocyanate compounds in which isocyanate groups are blocked with a blocking agent such as phenol, aminoplasts, polybasic acids or their An anhydride etc. can be mentioned. The crosslinkable group capable of reacting with a hydroxyl group is derived from the crosslinking agent.

  Among them, in the present invention, aminoplasts that undergo a crosslinking reaction with a hydroxyl group-containing compound under acidic conditions are preferable from the viewpoints of both the stability during storage and the activity of the crosslinking reaction, and the strength of the formed film. Aminoplasts contain an amino group capable of reacting with a hydroxyl group present in the fluorine-containing polymer, that is, a hydroxyalkylamino group or an alkoxyalkylamino group, or a carbon atom adjacent to a nitrogen atom and substituted with an alkoxy group. A compound. Specific examples include melamine compounds, urea compounds, benzoguanamine compounds, and the like.

  The 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, and alkoxylated methyl melamine. . In particular, methylolated melamine and alkoxylated methyl melamine obtained by reacting melamine and formaldehyde under basic conditions and derivatives thereof are preferable, and alkoxylated methyl melamine is particularly preferable in view of storage stability. There are no particular restrictions on methylolated melamine and alkoxylated methylmelamine. For example, use of various resins obtained by the method described in “Plastic Materials Course [8] Urea Melamine Resin” (Nikkan Kogyo Shimbun) Is also possible.

  As the urea compound, in addition to urea, an alkoxylated methylurea which is a polymethylolated urea derivative thereof, and a compound having a glycoluril skeleton or a 2-imidazolidinone skeleton having a cyclic urea structure are also preferable. As for the amino compounds such as the urea derivatives, various resins described in the above-mentioned “Yurea / Melamine resin” can be used.

  As the compound suitably used as the crosslinking agent in the present invention, a melamine compound or a glycoluril compound is particularly preferable from the viewpoint of compatibility with the fluorine-containing copolymer, and among these, from the viewpoint of reactivity, the crosslinking agent is in the molecule. The compound preferably contains a nitrogen atom and contains two or more carbon atoms substituted with an alkoxy group adjacent to the nitrogen atom. Particularly preferred compounds are compounds having structures represented by the following H-1 and H-2, and partial condensates thereof. In the formula, R represents an alkyl group having 1 to 6 carbon atoms or a hydroxyl group.

  As addition amount of aminoplast with respect to a fluorine-containing polymer, it is 1-50 mass parts per 100 mass parts of copolymers, Preferably it is 3-40 mass parts, More preferably, it is 5-30 mass parts. If it is 1 part by mass or more, the durability as a thin film that is a feature of the present invention can be sufficiently exhibited, and if it is 50 parts by mass or less, the low refractive index layer in the present invention when used for optical applications. This is preferable because the low refractive index, which is a characteristic of the above, can be maintained. From the viewpoint of keeping the refractive index low even when a curing agent is added, a curing agent that has a small increase in refractive index even when added is preferable, and from this viewpoint, the above compound has a skeleton represented by H-2. Compounds are more preferred.

1- (1) -3. Acid catalyst Regarding the acid catalyst mixed in advance with inorganic particles, organic acids such as sulfonic acid, phosphonic acid and carboxylic acid, and inorganic acids such as sulfuric acid and phosphoric acid can be mentioned. Preferably, sulfonic acid and phosphonic acid are more preferable, and sulfonic acid is most preferable. Preferred sulfonic acids include p-toluenesulfonic acid (PTS), benzenesulfonic acid (BS), p-dodecylbenzenesulfonic acid (DBS), p-chlorobenzenesulfonic acid (CBS), 1,4-naphthalenedisulfonic acid (NDS). ), Methanesulfonic acid (MsOH), nonafluorobutane-1-sulfonic acid (NFBS), etc., and any of them can be preferably used (the abbreviations in () are abbreviated).

  The use ratio of the acid catalyst is preferably 0.05 to 50 parts by mass, more preferably 0.5 to 25 parts by mass, and further preferably 1 to 15 parts by mass with respect to 100 parts by mass of the crosslinking agent capable of reacting with the hydroxyl group. Part.

1- (2) Component (B) of the present invention [fluorinated polymer]
The composition of the present invention contains a fluorine-containing polymer having at least one of a fluorine-containing vinyl monomer polymerization unit and a hydroxyl group-containing vinyl monomer polymerization unit.

1- (2) -1. Fluorinated vinyl monomer polymerization unit The structure of the fluorinated vinyl monomer polymerization unit constituting the fluorinated polymer of the present invention is not particularly limited, and examples thereof include fluorinated olefins, perfluoroalkyl vinyl ethers, vinyl ethers having a fluorinated alkyl group and (meta ) Polymerized units based on acrylates can be mentioned. The fluorine-containing polymer is preferably a copolymer of a fluorine-containing olefin and a vinyl ether because of suitability for production and properties required for a low refractive index layer such as a refractive index and film strength. More preferably, it is a copolymer. Further, as a copolymer component, perfluoroalkyl vinyl ether, vinyl ether having a fluorine-containing alkyl group, (meth) acrylate, or the like may be included for the purpose of reducing the refractive index.

  As the perfluoroolefin, those having 3 to 7 carbon atoms are preferable, perfluoropropylene or perfluorobutylene is preferable from the viewpoint of polymerization reactivity, and perfluoropropylene is particularly preferable from the viewpoint of availability.

  The content of perfluoroolefin in the polymer is preferably 25 to 75 mol%. In order to reduce the refractive index of the material, it is desired to increase the introduction rate of the perfluoroolefin, but in the general solution-based radical polymerization reaction, introduction of about 50 to 70 mol% is preferable in terms of polymerization reactivity. In the present invention, the content is more preferably 30% to 70 mol%, further preferably 30% to 60 mol%, particularly preferably 35% to 60 mol%, 60 mol% is particularly preferred.

  As the fluorine-containing vinyl monomer polymerization unit, a vinyl ether having a fluorine-containing alkyl group represented by the following M1 is also preferably used. The copolymer component may be introduced into the polymer in a co-range of preferably 0 to 40 mol%, more preferably 0 to 30 mol%, particularly preferably 0 to 20 mol%. is there.

In M1, R _f ¹¹¹ represents a fluorinated alkyl group having 1 to 30 carbon atoms, preferably a fluorinated alkyl group having 1 to 20 carbon atoms, particularly preferably 1 to 15 carbon atoms, and a straight chain {for example, —CF ₂ CF ₃ , —CH ₂ (CF ₂ ) _a H, —CH ₂ CH ₂ (CF ₂ ) _a F (a: an integer of 2 to 12), etc.}, but a branched structure {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.}, and alicyclic It may have a structure (preferably a 5- or 6-membered ring such as a perfluorocyclohexyl group, a perfluorocyclopentyl group or an alkyl group substituted with these), and an ether bond (for example, —CH ₂ OCH ₂ CF ₂ CF _3, - _{H 2 CH 2 OCH 2 (CF} 2) b H, -CH 2 CH 2 OCH 2 (CF 2) b F (b: 2~12 _{integer), CH 2 CH 2 OCF 2} CF 2 OCF 2 CF 2 H , etc. ). Note that the substituent represented by R _f ¹¹¹ is not limited to the substituent described here.

  Examples of the monomer represented by M1 include “Macromolecules”, Vol. 32 (21), p. 7122 (1999), a method in which a fluorine-containing alcohol is allowed to act on a leaving group-substituted alkyl vinyl ether such as vinyloxyalkyl sulfonate and vinyloxyalkyl chloride as described in JP-A-2-721. A method of exchanging vinyl groups by mixing a fluorine-containing alcohol and a vinyl ether such as butyl vinyl ether in the presence of a palladium catalyst as described in International Patent Application No. 92/05135; as described in US Pat. No. 3,420,793. , A method in which a fluorine-containing ketone and dibromoethane are reacted in the presence of a potassium fluoride catalyst, followed by a de-HBr reaction with an alkali catalyst;

  Although the preferable example of the structural component represented by M1 below is shown, it is not limited to these.

  Moreover, as a fluorine-containing vinyl monomer polymerization unit, the perfluoroalkyl vinyl ether represented by the following M2 is also preferably used. The copolymer component may be introduced into the polymer preferably in the range of 0 to 40 mol%, more preferably 0 to 30 mol%, still more preferably 0 to 20 mol%.

In M2, R _f ¹¹² represents a fluorinated alkyl group having 1 to 30 carbon atoms, preferably a fluorinated alkyl group having 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms, and 1 to 10 carbon atoms. More preferred is a perfluoroalkyl group. The fluorinated alkyl group may have a substituent. Specific examples of R _f ¹¹² include —CF ₃ {M2- (1)}, —CF ₂ CF ₃ {M2- (2)}, —CF ₂ CF ₂ CF ₃ {M2- (3)}, —CF ₂ CF (OCF ₂ CF ₂ CF ₃ ) CF ₃ {M2- (4)} and the like.

1- (2) -2. Next, the hydroxyl group-containing vinyl monomer polymerization unit constituting the fluorine-containing polymer of the present invention will be described.
As the hydroxyl group-containing vinyl monomer, any vinyl ethers, (meth) acrylates, styrenes and the like can be used as long as they are copolymerizable with the above-described fluorine-containing vinyl monomer polymerization unit. For example, when perfluoroolefin (such as hexafluoropropylene) is used as the fluorine-containing vinyl monomer, a hydroxyl group-containing vinyl ether having good copolymerization and a vinyl ether not containing a hydroxyl group are used in combination in order to control the hydroxyl group content. It is preferable. Specific examples of the hydroxyl group-containing vinyl ether include 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, 6-hydroxyhexyl vinyl ether, 8-hydroxyoctyl vinyl ether, diethylene glycol vinyl ether, triethylene glycol vinyl ether, 4- (hydroxymethyl) cyclohexyl methyl vinyl ether. However, it is not limited to these.

1- (2) -3. Polymerized unit having polysiloxane structure The fluoropolymer of the present invention preferably has a polymer unit having a polysiloxane structure in its partial structure, for example, in order to impart antifouling properties. The copolymerization site of the polysiloxane structure may be either the side chain or the main chain of the fluorine-containing polymer. A preferred polysiloxane structure is represented by the following general formula 1.

In General Formula 1, R ¹ and R ² may be the same or different and each represents an alkyl group or an aryl group. As an alkyl group, C1-C4 is preferable and a methyl group, a trifluoromethyl group, an ethyl group etc. are mentioned as an example. The aryl group preferably has 6 to 20 carbon atoms, and examples thereof include a phenyl group and a naphthyl group. Among these, a methyl group and a phenyl group are preferable, and a methyl group is particularly preferable. p represents an integer of 2 to 500, preferably 5 to 350, and particularly preferably 8 to 250.

  The polymer having a polysiloxane structure represented by the general formula 1 in the side chain is, for example, an epoxy group as described in J. Appl. Polym. Sci. 2000, 78, 1955, JP-A-56-28219, etc. Reactive groups (eg, amino groups, mercapto groups, carboxyl groups, hydroxyl groups, etc. with respect to epoxy groups and acid anhydride groups) with respect to polymers having reactive groups such as hydroxyl groups, carboxyl groups, and acid anhydride groups Can be synthesized by a method of introducing a polysiloxane having a terminal at one end (for example, Silaplane series (manufactured by Chisso Corporation)) by a polymer reaction or a method of polymerizing a polysiloxane-containing silicon macromer, and both methods are preferred. Can be used. In the present invention, a method of introducing by polymerization of silicon macromer is more preferable.

  Any silicon macromer may be used as long as it has a polymerizable group capable of copolymerization with a fluorine-containing olefin, and preferably has a structure represented by any one of formulas 2 to 5.

In General Formulas 2 to 5, R ¹ , R ² and p represent the same meaning as in General Formula 1, and preferred ranges are also the same. R ^{3 to} R ⁵ each independently represents a substituted or unsubstituted monovalent organic group or a hydrogen atom, an alkyl group having 1 to 10 carbon atoms (for example, a methyl group, an ethyl group, an octyl group, etc.), a carbon number of 1 10 to 10 alkoxy groups (for example, methoxy group, ethoxy group, propyloxy group and the like), aryl groups having 6 to 20 carbon atoms (for example, phenyl group, naphthyl group and the like) are preferable, and alkyl groups having 1 to 5 carbon atoms are particularly preferable. . R ⁶ represents a hydrogen atom or a methyl group. L ₁ represents an arbitrary linking group having 1 to 20 carbon atoms, and examples thereof include a substituted or unsubstituted linear, branched or alicyclic alkylene group, or a substituted or unsubstituted arylene group. It is an unsubstituted linear alkylene group of 1 to 20, particularly preferably an ethylene group or a propylene group. These compounds are synthesized, for example, by the method described in JP-A-6-322053.

  Any of the compounds represented by the general formulas 2 to 5 can be preferably used in the present invention, but among these, a structure represented by the general formula 2, 3 or 4 from the viewpoint of copolymerizability with a fluorine-containing olefin. Are preferred. The polysiloxane moiety preferably occupies 0.01 to 20% by mass of the graft copolymer, more preferably 0.05 to 15% by mass, and particularly preferably 0.5 to 10%. Is the case.

  Although the preferable example of the polymer unit of the polymer graft part which contains a polysiloxane part in a side chain useful for this invention below is shown, this invention is not limited to these.

S- (36) Silaplane FM-0711 (manufactured by Chisso Corporation)
S- (37) Silaplane FM-0721 (same as above)
S- (38) Silaplane FM-0725 (same as above)

  By introducing the polysiloxane structure, the film is imparted with antifouling property and dustproof property, and the film surface is provided with slipperiness, which is advantageous for scratch resistance.

  The copolymer component that forms a polymer unit other than the above can be appropriately selected from various viewpoints such as hardness, adhesion to a substrate, solubility in a solvent, transparency, and the like. For example, methyl vinyl ether, ethyl vinyl ether Examples thereof include vinyl ethers such as t-butyl vinyl ether, n-butyl vinyl ether, cyclohexyl vinyl ether and isopropyl vinyl ether, and vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl cyclohexanecarboxylate. The introduction amount of these copolymer components is preferably in the range of 0 to 40 mol%, more preferably in the range of 0 to 30 mol%, and particularly preferably in the range of 0 to 20 mol%.

  A particularly preferred form of the fluorine-containing polymer in the present invention is a form represented by the general formula 7.

In General Formula 7, R _f ¹¹ represents a C 1-5 perfluoroalkyl group. With _respect to the monomer constituting the moiety represented by —CF ₂ CF (R _f ¹¹ ) —, the above description applies as an example of perfluoroolefin. In the general formula 7, R _f ¹² is the same as the definition described in the fluorine-containing vinyl ether (R _f ¹¹² in the compound represented by the formula M2), and the preferred range is also the same. A ¹¹ and B ¹¹ each represent a hydroxyl group-containing vinyl monomer polymerization unit and an arbitrary constituent unit. A ¹¹ is the same as the definition of the hydroxyl group-containing vinyl monomer polymerization unit described above, and B ¹¹ is not particularly limited, but vinyl ethers and vinyl esters are more preferable from the viewpoint of copolymerization. Specific examples include the monomers exemplified in the above (other polymerization units) and the monomer represented by the formula M1.

Y ¹¹ represents a structural unit having a polysiloxane structure, and the form thereof may be a polymer unit having a graft site comprising a polysiloxane repeating unit represented by the general formula 1 in the side chain. Their definitions and preferred ranges are the same as those described above (constituent units having a polysiloxane structure).

  a to d each represent a mole fraction (%) of each constituent component, and a + b + c + d = 100. Preferably, each is 30 ≦ a ≦ 70 (more preferably 30 ≦ a ≦ 60, more preferably 35 ≦ a ≦ 60), 0 ≦ b ≦ 40 (more preferably 0 ≦ b ≦ 30, still more preferably 0 ≦ b). ≦ 20), 20 ≦ c ≦ 70 (more preferably 20 <c ≦ 60, still more preferably 25 ≦ c ≦ 55), and 0 ≦ d ≦ 40 (more preferably 0 ≦ d ≦ 30).

  y represents the mass fraction (%) of the structural unit containing polysiloxane with respect to the whole fluorine-containing polymer, preferably 0.01 ≦ y ≦ 20 (more preferably 0.05 ≦ y ≦ 15, still more preferably 0). .5 ≦ y ≦ 10).

  The number average molecular weight of the fluoropolymer in the present invention is preferably 5,000 to 1,000,000, more preferably 8,000 to 500,000, and particularly preferably 10,000 to 100,000.

  Here, the number average molecular weight is 10,000 to 100,000 for TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G. The molecular weight is expressed in terms of polystyrene by solvent THF and differential refractometer detection using a GPC analyzer using a column of 2000HxL (both trade names manufactured by Tosoh Corporation).

  Although the specific example of the fluorine-containing polymer of this invention is shown in Table 1 and Table 2, this invention is not limited to these.

Regarding the polymer constituents in the table, the molar ratio of each component is shown. The abbreviations are as follows.
HEVE: 2-hydroxyethyl vinyl ether,
HBVE: 4-hydroxybutyl vinyl ether,
HOVE: 8-hydroxyoctyl vinyl ether,
DEGVE: Diethylene glycol vinyl ether,
HMcHVE: 4- (hydroxymethyl) cyclohexylmethyl vinyl ether,
EVE: ethyl vinyl ether,
cHVE: cyclohexyl vinyl ether,
tBuVE: t-butyl vinyl ether,
VAc: vinyl acetate,

Although the specific example of the fluorine-containing polymer binder of this invention is shown in Table 3-Table 6, this invention is not limited to these.
In Tables 3 to 6, they are expressed as combinations of polymerization units.

Regarding the polymer constituents in the table, the molar ratio of each component is shown. The abbreviations are the same as in Tables 1 and 2 or as follows.
VPS-0501: an azo group-containing polydimethylsiloxane (made by Wako Pure Chemical Industries, Ltd.) represented by the following general formula (SI), having a number average molecular weight of 3 to 40,000 and a polysiloxane moiety having a molecular weight of about 5000,
VPS-1001: azo group-containing polydimethylsiloxane (manufactured by Wako Pure Chemical Industries, Ltd.) represented by the following general formula (SI), having a number average molecular weight of 70 to 90,000 and a polysiloxane moiety having a molecular weight of about 10,000.

  NE-30: a nonionic reactive emulsifier represented by the following general formula (SII), wherein n is 9, m is 1, u is 30, and Z is 7 to 9, manufactured by Asahi Denka Kogyo Co., Ltd.

  The fluorine-containing polymer binder used in the present invention can be synthesized by various polymerization methods such as solution polymerization, precipitation polymerization, suspension polymerization, precipitation polymerization, bulk polymerization, and emulsion polymerization. Moreover, it is compoundable by well-known operations, such as a batch type, a semi-continuous type, and a continuous type.

  The polymerization initiation method includes a method using a radical initiator, a method of irradiating light or radiation, and the like. These polymerization methods and polymerization initiation methods are, for example, the revised version of Tsuruta Junji “Polymer Synthesis Method” (published by Nikkan Kogyo Shimbun, 1971), Takatsu Otsu, Masato Kinoshita, “Experimental Methods for Polymer Synthesis” It is described in pp. 47-154 published in 1972.

  Among the above polymerization methods, a solution polymerization method using a radical initiator is particularly preferable. Solvents used in the solution polymerization method are, for example, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, tetrahydrofuran, dioxane, N, N-dimethylformamide, N, N-dimethylacetamide, benzene, toluene, acetonitrile, A single organic solvent such as methylene chloride, chloroform, dichloroethane, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, or a mixture of two or more thereof may be used, or a mixed solvent with water may be used.

  The polymerization temperature needs to be set in relation to the molecular weight of the polymer to be produced, the type of initiator, etc., and can be from 0 ° C. or lower to 100 ° C. or higher, but it is preferable to perform polymerization in the range of 40 to 100 ° C. .

  The reaction pressure can be appropriately selected, but is usually 0.01 to 10 MPa, preferably 0.05 to 5 MPa, more preferably about 0.1 to 2 MPa. The reaction time is preferably about 5 to 30 hours.

The obtained polymer can be used as it is for the application of the present invention, or can be purified by reprecipitation or liquid separation operation.
For example, in the case of a low refractive index layer to be described later, the amount of the fluorine-containing polymer is preferably 20 to 99.5% by mass, more preferably 30 to 90% by mass, and most preferably 40 to 80% by mass.

1- (3) Preferred Component (C) [Organic Base] of the Present Invention
It is preferable that the composition of this invention contains the organic base whose pKa of (C) conjugate acid is 5.0-10.5, or the organic base whose boiling point is 35 degreeC or more and 85 degrees C or less. Inorganic particles of the present invention are mixed with a crosslinking agent capable of reacting with a hydroxyl group in the presence of an acid catalyst, and before mixing with a fluorine-containing polymer, an organic base having a pKa of a conjugate acid of 5.0 to 10.5, or It is preferable to mix an organic base having a boiling point of 35 ° C. or higher and 85 ° C. or lower. By adding an organic base before mixing with the fluorine-containing polymer, the crosslinking agent capable of reacting with a hydroxyl group and the hydroxyl-containing fluorine-containing polymer are prevented from cross-linking reaction before coating the composition, resulting in coating failure (unevenness). , Repelling, etc.) can be prevented. After coating the composition, it is necessary to cure the film by a crosslinking reaction between the hydroxyl group of the fluorine-containing polymer and the crosslinking agent by heating. Therefore, it is preferable to use an organic base having an appropriate basicity. When expressed using pKa of a conjugate acid as a basic index, the pKa of the organic base used in the present invention is preferably 5.0 to 10.5, more preferably 6.0 to 10.0, and 6. More preferably, it is 5-10.0. The value of pKa of organic base in aqueous solution is described in Chemistry Handbook Basic Edition (5th revised edition, edited by The Chemical Society of Japan, Maruzen, 2004) Volume II, pages II-334-340. An organic base having an appropriate pKa can be selected. In addition, a compound that can be presumed to have an appropriate pKa in terms of structure even if not described in this document can be preferably used. Table 7 shows compounds having an appropriate pKa described in the literature, but compounds that can be preferably used in the present invention are not limited thereto.

  From the viewpoints of coatability and crosslinking reaction, the boiling point of the organic base is preferably 120 ° C. or lower, more preferably 80 ° C. or lower, and further preferably 70 ° C. or lower.

Examples of the organic base that can be preferably used in the present invention include, but are not limited to, the following compounds. Figures in parentheses indicate boiling points.
b-3: pyridine (115 ° C), b-14: 4-methylmorpholine (115 ° C), b-20: diallylmethylamine (111 ° C), b-19: triethylamine (88.8 ° C), b-21 : T-butylmethylamine (67-69 ° C), b-22: dimethylisopropylamine (66 ° C), b-23: diethylmethylamine (63-65 ° C), b-24: dimethylethylamine (36-38 ° C) ), B-18: trimethylamine (3-5 ° C.).

  The preferred amount of the organic base is preferably mixed so that the equivalent ratio of the acid to the organic base is 1: 0.9 to 1.5, more preferably 1: 0.95 to 1.3. 1: 1.0 to 1.1 is preferable.

1- (4) Preferred component (D) of the present invention [organosilane compound]
The composition of the present invention may contain an organosilane compound, a hydrolyzate of the organosilane compound and / or a partial condensate thereof (hereinafter, the obtained reaction solution is also referred to as “sol component”). preferable.
These compounds function as a binder by applying the composition and then condensing in a drying and heating process 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}} 1) 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 ¹ 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 And R′COO (R ′ 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.). Is 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 1} there are a plurality, it may be different even or ^{X 1} more ^{R 10} is the same, respectively.
The substituent contained in R ¹⁰ is not particularly limited, but a halogen atom (fluorine, chlorine, bromine, etc.), a hydroxyl group, a mercapto group, a carboxyl group, an epoxy group, an 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), arylo Xyloxycarbonyl group (phenoxycarbonyl, etc.), carbamoyl group (carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N-methyl-N-octylcarbamoyl, etc.), acylamino group (acetylamino, benzoylamino, acrylamino, methacryl) Amino) and the like, and these substituents may be further substituted.

When there are a plurality of R ^{10 s} , at least one of them 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.

In the general formula [B], R ²¹ 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 ¹ represents a single bond or * -COO-**, * -CONH-** or * -O-**, preferably a single bond, * -COO-** or * -CONH-**, a single bond And * -COO-** is more preferable, and * -COO-** is particularly preferable. * Represents a position bonded to ═C (R ²¹ ) —, 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.

s represents 0 or 1. When X ¹ there are a plurality, it may be different even multiple of X ¹ is the same, respectively. s 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 ¹ is synonymous with 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. 1-3 alkoxy groups are more preferable, and a methoxy group is particularly preferable.

  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.

(M-11) Methyltrimethoxysilane (M-12) Trimethylmethoxysilane (M-13) Triethylmethoxysilane

Of these compounds, (M-1), (M-2), (M-5), (M-11), and (M-12) are preferably used.
When two types are used in combination, (M-1) or (M-2) is selected as a compound having a polymerizable group, and (M-11) or (M-12) is selected as a compound having no polymerizable group. It is preferable to select and use together. It is also preferable to use an oligomer obtained by condensing and condensing the above compound having a polymerizable group and a compound having no polymerizable group.
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 33} represents an alkyl group having 1 to 10 carbon atoms) Formula ^R 33 OH alcohol and ^R 34 COCH ₂ COR ³⁵ (wherein represented ^{by, R 34} is the number of carbon atoms 1 to 10 alkyl groups, R ³⁵ 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 a 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 a general formula of Zr (OR ³³ ) _p1 (R ³⁴ COCHCOR ³⁵ ) _p2 , Ti (OR ³³ ) _q1 (R ³⁴ COCHCOR ³⁵ ) _q2 , and Al (OR ³³ ) _r1 (R ³⁴ ). Those selected from the group of compounds represented by COCHCOR ³⁵ ) _r2 are preferred and serve to promote the condensation reaction of the hydrolyzate and / or partial condensate of the organosilane compound.

R ³³ and R ³⁴ in the metal chelate compound may be the same or different and each has an alkyl group having 1 to 10 carbon atoms, specifically, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, sec -Butyl group, t-butyl group, n-pentyl group, phenyl group and the like. R ³⁵ 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, diisopropoxybis (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 ³⁴ COCH ₂ COR ³⁵ 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 ³⁴ represents an alkyl group having 1 to 10 carbon atoms, and R ³⁵ 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 34} and ^{R 35} constitute a β- diketone compound and / or β- ketoester compound are the same as ^{R 34} and ^{R 35} 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 amount of the organosilane compound or the hydrolyzate and / or partial condensate thereof is preferably 0.1 to 50% by mass of the total solid content in the case of a low refractive index layer, for example, 30 mass% is more preferable, and 1-20 mass% is the most preferable.
The organosilane compound may be added directly to the composition, but is obtained by treating the organosilane compound in the presence of a catalyst beforehand to prepare a hydrolyzate and / or partial condensate of the organosilane compound. It is preferable to adjust the composition using a reaction solution (sol solution) prepared. 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. In addition, it is preferable to apply a liquid obtained by adding a β-diketone compound and / or a β-ketoester compound to the composition.

1- (5) Preferred component (E) of the present invention [compound containing two or more (meth) acryloyl groups in one molecule]
In the curable composition of the present invention, a compound containing two or more (meth) acryloyl groups in one molecule as described below can be used.

(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.

  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. .

1- (6) Preferred component (F) of the present invention [compound having a polysiloxane structure]
In the present invention, for the purpose of improving scratch resistance by imparting slipperiness and imparting antifouling property, it is represented by the general formula (10) separately from the polymerization unit of the component (B) fluoropolymer binder of the present invention. It is preferable to use a compound having a polysiloxane structure and having a structure capable of forming a bond by reacting with a hydroxyl group or a hydroxyl group.

In General Formula (10), R ¹ and R ² may be the same or different and each represents an alkyl group or an aryl group. As an alkyl group, C1-C4 is preferable and a methyl group, a trifluoromethyl group, an ethyl group etc. are mentioned as an example. The aryl group preferably has 6 to 20 carbon atoms, and examples thereof include a phenyl group and a naphthyl group. Among these, a methyl group and a phenyl group are preferable, and a methyl group is particularly preferable. p represents an integer of 2 to 500, preferably 5 to 350, and particularly preferably 8 to 250.

  Examples of the structure of the compound include those having a substituent at the terminal and / or side chain of the compound chain, which includes 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.

  Although there is no restriction | limiting in particular in the molecular weight of the compound which has the said polysiloxane structure, It is preferable that it is 100,000 or less, It is especially preferable that it is 50,000 or less, It is most preferable that it is 3000-30000.

  From the viewpoint of preventing transcription, it preferably contains a hydroxyl group or a functional group that reacts with the hydroxyl group to form a bond. This bond formation reaction preferably proceeds rapidly under heating conditions and / or in the presence of a catalyst. Examples of such a substituent include an epoxy group and a carboxyl group. Although the following are mentioned as an example of a preferable compound, It is not limited to these.

(Including hydroxyl group)
“X-22-160AS”, “KF-6001”, “KF-6002”, “KF-6003”, “X-22-170DX”, “X-22-176DX”, “X-22-176D”, “X-22-176F” {manufactured by Shin-Etsu Chemical Co., Ltd.}; “FM-4411”, “FM-4421”, “FM-4425”, “FM-0411”, “FM-0421”, “ "FM-0425", "FM-DA11", "FM-DA21", "FM-DA25" {above, manufactured by Chisso Corp.}; "CMS-626", "CMS-222" {above, manufactured by Gelest} .

(Containing functional groups that react with hydroxyl groups)
"X-22-162C", "KF-105" {manufactured by Shin-Etsu Chemical Co., Ltd.}; "FM-5511", "FM-5521", "FM-5525", "FM-6611", " FM-6621 "," FM-6625 "{above, manufactured by Chisso Corporation}.
The compounding amount of the compound having a polysiloxane structure is preferably 0 to 30% by mass, more preferably 0.5 to 20% by mass, and most preferably 1 to 10% by mass based on the total solid content of the low refractive index layer.

  In addition to the polysiloxane compound, another polysiloxane compound may be used in combination. Preferable examples 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 groups containing acryloyl group, methacryloyl group, vinyl group, aryl group, cinnamoyl group, oxetanyl group, fluoroalkyl group, polyoxyalkylene group, carboxyl group, amino group and the like. 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 25.0-37.0 mass%, and 30.0-37.0. Most preferably, it is mass%. Examples of preferred silicone compounds include X-22-174DX, X-22-2426, X-22-164B, X22-164C, X-22-1821 (above trade names) and Chisso (manufactured by Shin-Etsu Chemical Co., Ltd.). Co., Ltd., FM-0725, FM-7725, FM6621, FM-1121 and Gelest DMS-U22, RMS-033, RMS-083, UMS-182, DMS-H21, DMS-H31, HMS-301, FMS121, Examples thereof include, but are not limited to, FMS123, FMS131, FMS141, FMS221 (named above).

2. Various compounds that can be used in the present invention Next, various compounds that can be used in the curable composition and the film of the present invention are described below, but the present invention is not limited thereto.

2- (1) Binder The film obtained in the present invention can be formed by a crosslinking reaction or a polymerization reaction of an ionizing radiation curable compound. That is, a coating solution 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. Can do.
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.

  Specific examples of the photopolymerizable polyfunctional monomer having a photopolymerizable functional group include the compounds described in the preferred component (F) of the present invention.

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.

2- (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. The polyurethane main chain has repeating units bonded by urethane bonds (—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 condensation polymerization 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 connects 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 main chain of the polymer 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.

2- (3) Fluorine-containing polymer binder The fluorine-containing polymer described in the component (B) of the present invention is used in the composition of the present invention.

2- (4) Organosilane compound In the composition of the present invention, the organosilane compound described in the preferred component (D) of the present invention, a hydrolyzate of the organosilane compound and / or a partial condensate thereof, etc. Hereinafter, the obtained reaction solution is preferably also referred to as “sol component”).

2- (5) Initiator Polymerization of various monomers, for example, 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.
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's 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 Kiyomi Kato, 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.

2- (6) Crosslinking agent capable of reacting with hydroxyl group The cured composition of the present invention contains a crosslinking agent capable of reacting with the hydroxyl group described in the component (A) of the present invention.

2- (7) Thermal acid generator The hardening composition of this invention contains the acid catalyst described in the structural component (A) of the said this invention.

2- (8) Photosensitive acid generator In the present invention, in addition to the thermal acid catalyst described above, a compound that generates an acid upon irradiation with light, that is, a photosensitive acid generator may be further added. The photosensitive acid generator is a substance that imparts photosensitivity to the coating film of the curable resin composition and enables the coating film to be photocured by, for example, irradiation with radiation such as light. Examples of the photosensitive acid generator include (1) various onium salts such as iodonium salt, sulfonium salt, phosphonium salt, diazonium salt, ammonium salt, pyridinium salt; (2) β-ketoester, β-sulfonylsulfone and these Sulfone compounds such as α-diazo compounds; (3) sulfonic acid esters such as alkyl sulfonate esters, haloalkyl sulfonate esters, aryl sulfonate esters, and imino sulfonates; (4) sulfonimide compounds; and (5) diazomethane compounds. Others can be mentioned and can be used as appropriate. 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 photosensitive acid generator can be used alone or in combination of two or more, and can also be used in combination with the thermal acid generator. The use ratio of the photosensitive acid generator is preferably 0 to 20 parts by mass, more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the fluoropolymer in the curable resin composition. If the ratio of the photosensitive acid generator is less than or equal to the upper limit, it is preferable because the resulting cured film has excellent strength and good transparency.

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

2- (9) Translucent particles Among the compositions of the present invention, antiglare properties (surface scattering properties) and internal scattering properties are imparted to the compositions used for the antiglare layers and hard coat layers described below. Therefore, various translucent 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.

  Further, a binder (having a refractive index after curing of 1.50 to 1.53) composed mainly of a trifunctional or higher functional (meth) acrylate monomer and a crosslinked poly (meth) acrylate weight having an acrylic content of 50 to 100 mass 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) used for the antiglare layer or the hard coat layer and the translucent particles is preferably 1.45 to 1.70, more preferably 1.48 to 1.70. 65. In order to make the refractive index within the above range, the type and amount ratio of the binder and translucent particles may be appropriately selected. How to select can be easily known experimentally in advance.
Further, the difference in refractive index between the binder used for the antiglare layer and the hard coat layer and the translucent particles (the refractive index of the translucent particles−the refractive index of the binder) is preferably 0.001 to 0 as an absolute value. 0.030, more preferably 0.001 to 0.020, and still more preferably 0.001 to 0.015. If this difference exceeds 0.030, 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.

  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 blended so as to be preferably contained in an amount of 3 to 30% by mass 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, Chemical 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, and 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.

2- (10) Inorganic Particles The cured composition of the present invention contains inorganic particles described in the component (A) of the present invention.

2- (11) Conductive Particles In order to impart conductivity to the composition of the present invention, various conductive particles can be used.
The conductive particles are preferably formed from a metal oxide or nitride. Examples of metal oxides or nitrides include tin oxide, indium oxide, zinc oxide and titanium nitride. Tin oxide and indium oxide are particularly preferred. The conductive inorganic particles are mainly composed of oxides or nitrides of these metals, and can further contain other elements. The main component means a component having the largest content (mass%) among the components constituting the particles. Examples of other elements include Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P, S, B, Nb, In, V and halogen atoms are included. In order to increase the conductivity of tin oxide and indium oxide, it is preferable to add Sb, P, B, Nb, In, V and a halogen atom. Particularly preferred are tin oxide containing Sb (ATO) and indium oxide containing Sn (ITO). The ratio of Sb in ATO is preferably 3 to 20% by mass. The ratio of Sn in ITO is preferably 5 to 20% by mass.

2- (12) Surface Treatment Agent The inorganic particles of the present invention are plasma-discharge treated in order to stabilize dispersion in a dispersion or coating solution, or to increase affinity and binding properties with a binder component. Further, physical surface treatment such as corona discharge treatment, or 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.) and inorganic compounds containing aluminum (Al ₂ O ₃ , Al (OH) ₃ 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. .
An inorganic compound containing cobalt, an inorganic compound containing aluminum, and an inorganic compound containing zirconium are particularly preferable, and an inorganic compound containing cobalt, Al (OH) ₃ , and Zr (OH) ₄ are most preferable.
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 crosslinkable 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.), cationic polymerizable groups capable of addition and polymerization reactions with radical species. (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.

2- (13) 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 group, allyl group, styryl group, vinyloxy group, etc.) capable of addition reaction / polymerization reaction 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, and functional groups having an ethylenically unsaturated group are preferred.

2- (14) Antifouling agent The composition of the present invention, particularly the composition used for the uppermost layer of the film, is known for the purpose of imparting antifouling properties, water resistance, chemical resistance, slipping properties and the like. It is preferable to add a polysiloxane-based or fluorine-based antifouling agent, slipping agent or the like as appropriate.
In the case of adding these additives, for example, in the case of a low refractive index layer, it is preferably added in the range of 0.01 to 20% by mass, more preferably in the range of 0.05 to 10% by mass. And is particularly preferably 0.1 to 5% by mass.

As the fluorine compound used as an antifouling agent, a compound having a fluoroalkyl group is preferred. 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 ) 8CF 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.), but alicyclic structures (preferably 5-membered or 6-membered rings such as perfluorocyclohexyl group and perfluorocyclopentyl 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 O _{H 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, 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 in the range of 0.05 to 10% by mass. Particularly preferred is 0.1 to 5% by mass. 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.

2- (15) Compound having polysiloxane structure The present invention has a polysiloxane structure described in the preferred component (F) of the present invention for the purpose of improving scratch resistance by imparting slipperiness and imparting antifouling property. It is preferable to use a hydroxyl group or a compound having a structure capable of reacting with a hydroxyl group to form a bond.

2- (16) Surfactant In the composition of the present invention, in order to ensure surface uniformity such as coating unevenness, drying unevenness, point defect, etc., any one of fluorine-based and silicone-based surfactants, Or it is preferable to contain both in a coating composition. 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 fluoroaliphatic group-containing copolymers (sometimes abbreviated as “surfactant fluoropolymer”), and the surfactant fluoropolymer includes the following (i And a copolymer of an acrylic resin, a methacrylic resin, and a vinyl monomer copolymerizable therewith (for example, the monomer (ii) below) characterized by containing a repeating unit corresponding to the monomer of is there.

(I) Fluoroaliphatic group-containing monomer represented by the following 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 to 6 and n is an integer of 2 to 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)

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 represented by 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 group 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 surface-active fluoropolymer used in the present invention is preferably 10 mol based on each monomer of the surface-active fluoropolymer. % Or more, more preferably 15 to 70 mol%, and still more preferably 20 to 60 mol%.

The preferred mass average molecular weight of the surface-active fluoropolymer used in the present invention is preferably from 3,000 to 100,000, more preferably from 5,000 to 80,000.
Furthermore, the preferable addition amount in the case of adding the surface-active 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 with respect to the composition. More preferably, it is the range of 0.01-1 mass%.

2- (17) Thickener In the composition of the present invention, a thickener may be used to adjust the viscosity of the coating composition.
The term “thickener” as used herein means that the viscosity of the liquid is increased by adding it, and the amount by which the viscosity of the coating composition increases by addition is preferably 0.05 to 50 cP. More preferably, it is 0.10-20 cP, Most preferably, it is 0.10-10 cP.

2- (18) Coating solvent As a solvent used in the coating composition for forming each layer according to the present invention, each component can be dissolved or dispersed, and a uniform surface shape is likely to be formed in the coating process and the drying process. In addition, 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), ethers such as tetrahydrofuran (66 ° C), 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 ether) Ketones such as Luketone, 79.6 ° C, 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.

2- (19) Others In addition to the components described above, the composition of the present invention includes a resin, a coupling agent, an anti-coloring agent, a coloring agent (pigment, dye), an antifoaming agent, a leveling agent, a flame retardant, and an ultraviolet absorber. An agent, an infrared absorber, an adhesion-imparting agent, a polymerization inhibitor, an antioxidant, a surface modifier, and the like can also be added.

2- (20) Support The support of 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. Films, polyacrylic resin films, polyurethane resin films, polyester films, polycarbonate films, polysulfone films, polyether films, polymethylpentene films, polyetherketone films, (meth) acrylonitrile films, and the like can be used.

<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.

<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.

3. Layers constituting the film The film of the present invention is obtained by, for example, mixing and coating the above-mentioned various compounds. Next, preferred examples of the film of the present invention and preferred for constituting the same Describe the layer.

3- (1) Antiglare layer The antiglare layer is usually formed for the purpose of contributing to the film an antiglare property due to surface scattering and preferably a hard coat property for improving the scratch resistance of the film.

  As a method of forming the antiglare property, a method of laminating and forming a mat-shaped shaping film having fine irregularities on the surface as described in JP-A-6-16851, as described in JP-A-2000-206317 A method of forming by curing shrinkage of an ionizing radiation curable resin due to a difference in the amount of ionizing radiation applied, and by reducing the mass ratio of a good solvent to a light transmitting resin by drying as described in JP-A No. 2000-338310. A method of solidifying the light-sensitive fine particles and the translucent resin while gelling to form unevenness on the coating film surface, a method of imparting surface unevenness by external pressure as described in JP-A-2000-275404, etc. These known methods can be used.

The antiglare layer that can be used in the present invention usually contains a binder capable of imparting hard coat properties, translucent particles for imparting antiglare properties, and a solvent, and the translucent particles themselves. It is preferable that surface irregularities are formed by the protrusions or protrusions formed by an aggregate of a plurality of particles.
The antiglare layer formed by dispersing the matte particles contains a binder and translucent particles dispersed in the binder. The antiglare layer having antiglare properties preferably has both antiglare properties and hard coat properties.

As specific examples of the mat particles, particles of inorganic compounds 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.

  The particle size distribution of the mat particles can be measured by a Coulter counter method, and the measured distribution can be converted into a particle number distribution.

  By adjusting the refractive index of the translucent resin in accordance with the refractive index of each translucent particle selected from these particles, desired internal haze and surface haze can be achieved. Specifically, a translucent resin (having a refractive index after curing of 1.55 to 1.70) mainly composed of a tri- or higher functional (meth) acrylate monomer preferably used in the antiglare layer according to the present invention described later. ) And a translucent particle and / or benzoguanamine particle composed of a crosslinked poly (meth) acrylate polymer having a styrene content of 50 to 100% by mass, particularly preferably the translucent resin and the styrene content of 50 to 50. A combination with translucent particles (refractive index of 1.54 to 1.59) made of a crosslinked poly (styrene-acrylate) copolymer of 100% by mass is particularly preferred.

The translucent particles are preferably blended in the formed antiglare layer so as to be contained in an amount of 3 to 30% by mass in the total solid content of the antiglare layer. More preferably, it is 5-20 mass%.
Moreover, the density of the translucent particles is preferably 10 to 1000 mg / m ² , more preferably 100 to 700 mg / m ² .

  The absolute value of the difference between the refractive index of the translucent resin and the refractive index of the translucent particles is preferably 0.04 or less. The absolute value of the difference between the refractive index of the translucent resin and the refractive index of the translucent particles is preferably 0.001 to 0.030, more preferably 0.001 to 0.020, and still more preferably 0.001. ~ 0.015. Here, the refractive index of the translucent resin can be quantitatively evaluated by directly measuring the refractive index 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.

  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 the pixels are enlarged or reduced due to the unevenness present on the surface of the antiglare and antireflection film, resulting in loss of brightness uniformity, but the particle size is smaller than the matte particles that impart antiglare properties. Thus, the use of mat particles different from the refractive index of the binder can greatly improve the performance.

  The film thickness of the antiglare layer is preferably 1 to 10 μm, and more preferably 1.2 to 8 μm. If it is too thin, the hard property is insufficient, and if it is too thick, curling and brittleness may be deteriorated and workability may be lowered.

  On the other hand, the center line average roughness (Ra) of the antiglare layer is preferably in the range of 0.10 to 0.40 μm. Further, it is preferable that the value of the transmitted image definition is 5 to 60%.

  The strength of the antiglare layer is preferably H or more, more preferably 2H or more, and most preferably 3H or more in a pencil hardness test.

3- (2) Hard Coat Layer In order to impart the physical strength of the film to the film of the present invention, a hard coat layer can be provided in addition to the antiglare layer.
Preferably, a low refractive index layer is provided thereon, 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 refractive index of the hard coat layer in the present invention is preferably in the range of 1.48 to 2.00, more preferably 1.52 to 1, from the optical design for obtaining an antireflection film. .90, more preferably 1.55 to 1.80. In the present invention, it is preferable that there is at least one low refractive index layer on the hard coat layer. If the refractive index is too small, the antireflection property is lowered, and if it is too large, the color of reflected light becomes strong. Tend.

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 contains matte particles having an average particle diameter of 1.0 to 10.0 μm, preferably 1.5 to 7.0 μm, such as inorganic compound particles or resin particles, for the purpose of imparting internal scattering properties. May be.

  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, after the formation of the hard coat layer, a polymer formed by polymerizing the polyfunctional monomer and / or the high refractive index monomer and the like and inorganic particles dispersed therein are referred to as a binder.

  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.

3- (3) High Refractive Index Layer, Medium Refractive Index Layer As a preferred example of the film of the present invention, a high refractive index layer and a medium refractive index layer can be provided to improve 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 preferably used for forming the high refractive index layer and the medium refractive index layer in a dispersion state.
In the dispersion of the inorganic particles, it is preferable to disperse in the 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 thus prepared is, for example, a binder or ionizing radiation curable polyfunctional monomer or polyfunctional oligomer cross-linked 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 middle refractive index layer has a function of maintaining the dispersion state of the inorganic particles in the anionic group, 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 preferably 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.

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

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 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 of the present invention can be preferably used as a composition for forming a low refractive index layer.

3- (5) Antistatic Layer, Conductive Layer In the present invention, it is preferable to provide an antistatic layer from the viewpoint of preventing static electricity on the film surface. The antistatic layer can be formed by, for example, applying a conductive coating solution containing conductive fine particles and a reactive curable resin, or depositing or sputtering a metal or metal oxide that forms a transparent film. Conventionally known methods such as a method of forming a conductive thin film can be listed. The conductive layer can be formed directly on the support or via a primer layer that strengthens adhesion to the support. Further, the antistatic layer can be used as a part of the antireflection film. In this case, when used in a layer close to the outermost layer, sufficient antistatic properties can be obtained even if the film is thin.

The thickness of the antistatic layer is preferably from 0.01 to 10 μm, more preferably from 0.03 to 7 μm, and even more preferably from 0.05 to 5 μm. The surface resistance of the antistatic layer is ^preferably from ¹⁰ 5 ~10 ¹² Ω / ^sq, more preferably from 10 5 ~10 ⁹ Ω / ^sq, most be 10 5 ~10 ⁸ Ω / sq preferable. The surface resistance of the antistatic layer can be measured by a four probe method.

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. . 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 antistatic layer has a pencil hardness of 1 kg, preferably H or higher, more preferably 2H or higher, more preferably 3H or higher. Is more preferable, and 4H or more is most preferable.

3- (6) Antifouling layer It is preferable to provide an antifouling layer on the outermost surface of the film. 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.

3- (7) Interference unevenness (rainbow unevenness) prevention layer When 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 layer, 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 subtle film thickness unevenness of the hard coat layer (or antiglare layer). In order to prevent such interference unevenness, for example, it has an intermediate refractive index n _P between the transparent support and the hardcoat layer (or antiglare layer), such as the film thickness d _P satisfies the following formula interference An unevenness prevention layer can also be provided.

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.

3- (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 side. A layer containing a polymer compound having a -COOM group is provided, 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, a vinyl acetate-maleic acid copolymer having a -COOM group is preferably used. These polymer compounds are used alone or in combination of two or more, and the preferred mass average molecular weight is 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.

3- (9) Anti-curl layer The film of the present invention may 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 layer or anti-reflection layer of the base material, or for example, an easy-adhesion layer may be coated on one side of the transparent resin film, and the anti-curl processing is performed on the opposite side The mode which coats is mentioned.

  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.

3- (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.

3- (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.

4). 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 / hard coat layer b. Support / hard coat layer / low refractive index layer (FIG. 1)
c. Support / hard coat layer / high refractive index layer / low refractive index layer (FIG. 2)
d. Support / hard coat layer / medium refractive index layer / high refractive index layer / low refractive index layer (FIG. 3)

When the hard coat layer (2) is applied on the support (1) and the low refractive index layer (5) is laminated as shown in FIG. 1 (b), it can be suitably used as an antireflection film. The low refractive index layer (5) is formed by forming the low refractive index layer (5) on the hard coat layer (2) with a film thickness of about 1/4 of the wavelength of light, thereby reflecting the surface reflection by the principle of thin film interference. Can be reduced.
Moreover, even if a high refractive index layer (4) and a low refractive index layer (5) are laminated after applying a hard coat layer (2) on a support (1) as shown in c (FIG. 2). It can use suitably as a prevention film. Furthermore, as shown in FIG. 3 (d), the order of the support (1), the hard coat layer (2), the middle refractive index layer (3), the high refractive index layer (4), and the low refractive index layer (5) By installing a layer structure, the reflectance can be reduced to 1% or less.

  In the constitutions a to d, the hard coat layer (2) can be an antiglare layer having antiglare properties. The antiglare property may be formed by the dispersion of mat particles (6) as shown in FIG. 4 or may be formed by surface shaping by a method such as embossing as shown in FIG. The antiglare layer formed by the dispersion of the mat particles (6) is composed of a binder and translucent particles dispersed in the binder. The antiglare layer having antiglare properties preferably has both antiglare properties and hard coat properties, and 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 surface layer or on the outermost surface, there are demands such as an interference non-uniformity (rainbow nonuniformity) prevention layer and an antistatic layer (reducing the surface resistance value from the display side). In some cases, dust on the surface becomes a problem), another hard coat layer (if one hard coat layer or antiglare layer is insufficient in hardness), gas barrier layer, water absorption layer (moisture-proof) Layer), adhesion improving layer, antifouling layer (contamination preventing layer), and the like.
The refractive index of each layer constituting the antiglare antireflection film having the antireflection layer in the invention preferably satisfies the following relationship.
Refractive index of hard coat layer> refractive index of transparent support> refractive index of low refractive index layer

5). Production method The formation of the film of the present invention, including the preparation of the curable composition of the present invention, the formation of layers using the composition, and the formation of each preferred layer of the film of the present invention, can be carried out by the following methods, It is not limited to this method.

5- (1) Preparation of coating solution <Preparation>
First, the curable composition of the present invention is prepared. In order to form the film of this invention, the coating liquid containing the component for forming each layer is prepared. When preparing the coating solution, first, a crosslinking agent capable of reacting with a hydroxyl group and inorganic particles are mixed in the presence of an acid catalyst. Thereafter, a mixed liquid of a crosslinking agent and inorganic particles and a fluorine-containing polymer are mixed. After mixing the crosslinking agent and the inorganic particles, before mixing with the fluoropolymer, an organic base having a pKa of the conjugate acid of 5.0 to 10.5 or an organic base having a boiling point of 35 ° C. or more and 85 ° C. or less is mixed. Is preferred.

  In the film of the present invention, one or more of the layers are formed by the curable composition of the present invention. 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>
Depending on the coating method, the upper limit speed at which coating can be performed is greatly affected by the liquid properties, so it is preferable to control the liquid properties, particularly the viscosity and surface tension, at the moment of coating.
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 support body also affects the upper limit speed | rate which can be apply | coated. The amount of the coating solution applied to the support is preferably 2.0 to 5.0 [cc / m ² ]. Increasing the amount of the coating solution applied to the support is preferable because the upper limit of the application rate can be increased. However, excessively increasing the amount of the coating solution applied to the support increases the load on drying, so the liquid formulation -It is preferable to determine the amount of the coating solution to be applied to the optimal support depending on the 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 decreases, so the range of 17 [mN / m] to 32 [mN / m] is more preferable, and 19 [mN / m] to 26 [ mN / m] is more preferable.

<Filtration>
The coating solution used for coating is preferably filtered before coating. As a filter for filtration, it is preferable to use a filter having a pore diameter as small as possible within a range in which components in the coating solution are not removed. For filtration, a filter having an absolute filtration accuracy of 0.1 to 10 μm is used, and a filter having an absolute filtration accuracy of 0.1 to 5 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 filtration 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.

5- (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 a liquid and then washed by spraying the liquid onto the rubbed surface is used. 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 film in these treatments is preferably Tg or less, for example, in the case of a cellulose acylate film, 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. .

5- (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), micro gravure coating method, etc. Known methods are used, and among them, the micro gravure coating method and the 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 of a hard coat layer or a low refractive index layer is applied to one side of the unwound support by a microgravure coating method. Can do.

  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, a die coater that can be preferably used in a region with a small wet coating amount (20 cc / m ² or less) such as a hard coat layer or an antireflection layer will be described below.

<Die coater configuration>
FIG. 6 is an example of a cross-sectional view of a coater using a slot die preferably used for producing the film of the present invention. The coater 10 is applied to the web W supported by the backup roll 11 and continuously applied from the slot die 13 as a bead 14a to form a coating film 14b on the web W.

  Inside the slot die 13, a pocket 15 and a slot 16 are formed. The pocket 15 has a curved section and a straight section. For example, the pocket 15 may have a substantially circular shape as shown in FIG. 5 or a semicircular shape. The pocket 15 is a liquid storage space for the coating liquid extended in the width direction of the slot die 13 with its cross-sectional shape, and the length of the effective extension is generally equal to or slightly longer than the coating width. The supply of the coating liquid 14 to the pocket 15 is performed from the side surface of the slot die 13 or from the center of the surface opposite to the slot opening 16a. The pocket 15 is provided with a stopper that prevents the coating liquid 14 from leaking out.

  The slot 16 is a flow path of the coating liquid 14 from the pocket 15 to the web W, and has a cross-sectional shape in the width direction of the slot die 13 similarly to the pocket 15, and the opening 16a located on the web side is generally Using a width regulating plate (not shown), the width is adjusted to be approximately the same as the coating width. The angle between the slot tip of the slot 16 and the tangent in the web running direction of the backup roll 11 is preferably 30 ° or more and 90 ° or less.

  The tip lip 17 of the slot die 13 where the opening 16a of the slot 16 is located is tapered, and the tip is a flat portion 18 called a land. In the land 18, the upstream side in the traveling direction of the web W with respect to the slot 16 is referred to as an upstream lip land 18 a and the downstream side is referred to as a downstream lip land 18 b.

FIG. 7 shows the cross-sectional shape of the slot die 13 in comparison with the conventional one. FIG. 7A shows an example 13 of an improved slot die, and FIG. 7B shows an example 30 of a conventional slot die. ing. Any slot die can be used in the present invention. In the conventional slot die 30, the distance between the upstream lip land 31a and the web of the downstream lip land 31b is equal. Reference numeral 32 denotes a pocket, and 33 denotes a slot. On the other hand, in the slot die 13 of the present invention, the downstream side lip land length I _LO is shortened, so that application with a wet film thickness of 20 μm or less can be performed with high accuracy.

The land length I _UP of the upstream lip land 18a is not particularly limited, but is preferably used in the range of 500 μm to 1 mm. The land length I _LO of the downstream lip land 18b is preferably 30 μm or more and 100 μm or less, more preferably 30 μm or more and 80 μm or less, and further preferably 30 μm or more and 60 μm or less. When the land length Lo of the downstream lip is shorter than 30 μm, the edge or land of the tip lip is likely to be chipped, streaks are likely to occur in the coating film, and as a result, application is impossible. In addition, it becomes difficult to set the position of the wetting line on the downstream side, and there is a problem that the coating liquid tends to spread on the downstream side. It has been conventionally known that this spreading of the coating liquid on the downstream side means non-uniform wetting lines and leads to a problem of causing a defective shape such as a streak on the coating surface. On the other hand, when the land length Lo of the downstream lip is longer than 100 μm, it is impossible to perform thin layer coating because the beat itself cannot be formed. On the other hand, the land length I _LO of the downstream lip is preferably 100 μm or less in that the bead itself can be formed and thin layer coating can be performed.

Further, the downstream lip land 18b has an overbite shape closer to the web W than the upstream lip land 18a. Therefore, the degree of decompression can be lowered, and a bead suitable for thin film coating can be formed. The difference in distance between the downstream side lip land 18b and the web W of the upstream side lip land 18a (hereinafter referred to as overbit length LO) is preferably 30 μm or more and 120 μm or less, more preferably 30 μm or more and 100 μm or less, and most preferably 30 μm. It is 80 μm or less. When the slot die 13 has an overbite shape, the gap _GL between the tip lip 17 and the web W indicates the gap between the downstream lip land 18b and the web W.

FIG. 8 is an example of a perspective view showing a slot die and its periphery in a coating process preferably used for manufacturing the film of the present invention.
On the opposite side of the web W in the direction of travel, a decompression chamber 40 is installed at a position where it does not come into contact with the bead 14a so that sufficient decompression can be adjusted. The decompression chamber 40 includes a back plate 40a and a side plate 40b for maintaining its operating efficiency, and the gaps G _B and G between the back plate 40a and the web W, and between the side plate 40b and the web W, respectively. _S exists.

5- (4) <Drying>
The film of the present invention is preferably applied on a support directly or via another layer and then conveyed by a web to a heated zone to dry 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.

5- (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.

It is preferable that the film of the present invention is first heated at a temperature of 70 ° C. or higher and 130 ° C. or lower for 5 to 20 minutes, and then cured by an active energy ray typified by ultraviolet rays.
The temperature of thermosetting is preferably 70 ° C. or higher and 120 ° C. or lower, and most preferably 80 ° C. or higher and 115 ° C. or lower.
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 amount of irradiation light 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.

  The oxygen concentration is preferably formed by a crosslinking reaction or 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.

By supplying inert gas to the ionizing radiation irradiation chamber where ionizing radiation curable compounds are cross-linked or polymerized, and by slightly blowing out to the web entrance side of the irradiation chamber, the carry air accompanying web transport is eliminated. Thus, the oxygen concentration in the reaction chamber can be effectively reduced, and the substantial oxygen concentration on 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 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 excluding oxygen on the web surface in advance, the curing can proceed more efficiently. Further, the side surface constituting the web entrance side of the ionizing radiation reaction chamber or the front chamber is preferably 0.2 to 15 mm in gap with the web surface in order to use the inert gas efficiently, more preferably, 0.1%. The thickness is preferably 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 at 170 ° C. or higher, problems such as deformation of the substrate occur. A more preferable temperature is 60 ° C to 100 ° C. 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 laminated 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.

5- (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 and drying a coating liquid, a process of curing a coating film, and curing It is preferable that the process of winding up the support body film which has the layer which carried out 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.

5- (7) Saponification Treatment When making a polarizing plate using the film of the present invention as one of two polarizing film surface protective 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.

(1) 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 requires special equipment. Therefore, it is preferable 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.

(2) Method of applying alkaline solution As means for avoiding damage to each film in the above-mentioned immersion method, the alkaline solution is applied only to the surface opposite to the surface having the coating layer under appropriate conditions, heated, washed with water, A drying alkaline solution 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.

(3) Method of saponification by protecting with a laminate film In the same manner as in (2) above, when the coating layer has insufficient resistance to an alkaline solution, it is laminated on the surface on which the final layer is formed after the final layer is formed. By laminating the films and then immersing them in an alkaline solution, only the film surface opposite to the surface on which the final layer is formed, for example, the triacetylcellulose surface can be made hydrophilic, and then the laminate film can be peeled off. Even in this method, it is possible to perform only the hydrophilic treatment necessary as a polarizing plate protective film on the surface opposite to the surface on which the final layer of the support 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.

(4) Method of immersing in alkaline solution after forming up to middle layer Although the layer is resistant to the alkaline solution up to the lower layer, if the resistance to the alkaline solution of the upper layer is insufficient, both sides are immersed in the alkaline solution after forming up to the lower layer Can be hydrophilized, and then an upper layer can be formed. Although the manufacturing process is complicated, for example, in a film composed of an antiglare layer and a low refractive index layer of a fluorine-containing sol-gel film, when there is a hydrophilic group, the interlayer adhesion between the antiglare layer and the low refractive index layer is improved. There are advantages to doing.

(5) Method of forming a coating layer on a saponified support in advance A support such as a triacetyl cellulose film is previously saponified by immersing it in an alkaline solution, and either directly or via another layer. A coating layer may be formed. In the case of saponification by dipping in an alkali solution, the interlaminar adhesion with the support 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.

5- (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.
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 in which the absorption axis of the polarizing film is neither parallel nor perpendicular to the longitudinal direction can be 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.

6). 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 using the film of the present invention can be used on a known display such as a plasma display panel (PDP) or a cathode ray tube display (CRT).

6- (1) Liquid Crystal Display Device The film and the polarizing plate of the present invention can be advantageously used for an image display device such as a liquid crystal display device, and are 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.

6- (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.

7). Various characteristic values Various measurement methods related to the present invention and preferable characteristic values are shown below.
7- (1) Reflectance Specular reflectance and color are measured by attaching an adapter “ARV-474” to a spectrophotometer “V-550” [manufactured by JASCO Corporation], and a wavelength of 380 to 780 nm. In the region, it is possible to measure the specular reflectivity at an exit angle of -5 ° at an incident angle of 5 °, calculate an average reflectivity of 450 to 650 nm, and evaluate the antireflection property.
It is preferable that the antiglare antireflection film according to the present invention has a specular reflectance of 2.0% or less and a transmittance of 90% or more because reflection of external light can be suppressed and visibility is improved. The specular reflectance is particularly preferably 1.5% or less, and most preferably, the reflectance is 1.0% or less by using a layer structure as shown in FIG.

7- (2) color antireflection performance polarizing plate according to the present invention, the CIE standard illuminant _{D 65,} with respect to the incident angle of 5 ° incident light at 780nm region from the wavelength 380 nm, of the specularly reflected light color That is, the color tone can be evaluated by obtaining the L ^* , a ^* , and b ^* values of the CIE 1976 L ^* a ^* b ^* color space.
The L ^* , a ^* , and b ^* values are preferably in the ranges of 3 ≦ L ^* ≦ 20, −7 ≦ a ^* ≦ 7, and −10 ≦ b ^* ≦ 10, respectively. By setting it within this range, the color of reflected light from red purple to blue purple, which has been a problem with conventional polarizing plates, is reduced, and further 3 ≦ L ^* ≦ 10, 0 ≦ a ^* ≦ 5, and − 7 ≦ b ^* ≦ 0 is greatly reduced, and when applied to a liquid crystal display device, when applied to a liquid crystal display device, such as indoor fluorescent lamps, a slight brightness of bright external light is reflected. Neutral, don't mind. Specifically, if a ^* ≦ 7, the reddish color will not be too strong, and if a ^* ≧ −7, the cyan color will not be too strong. If b ^* ≧ −7, the bluish color does not become too strong, and if b ^* ≦ 0, the yellowish color does not become too strong.

Furthermore, the color uniformity of the reflected light is determined according to the following formula 21 from the a ^* b ^* on the L ^* a ^* b ^* chromaticity diagram obtained from the reflection spectrum of the reflected light from 380 nm to 680 nm. It can be obtained as the rate of change.

Here, a ^* _max and a ^* _min are the maximum value and minimum value of the a ^* value, respectively; b ^* _max and b ^* _min are the maximum value and minimum value of the b ^* value, respectively; a ^* _av and b ^* _av ^Are average values of a ^* value and a ^* value, respectively. The color change rate is preferably 30% or less, more preferably 20% or less, and most preferably 8% or less.

The film of the present invention preferably has a Delta] E _w is 15 or less is the change in color before and after the weather resistance test, more preferably 10 or less, and most preferably 5 or less. In this range, it is possible to achieve both low reflection and reduction of the color of the reflected light. For example, when applied to the outermost surface of an image display device, there is a slight amount of high-brightness external light such as an indoor fluorescent lamp. The color tone when it is reflected is neutral, and the quality of the displayed image is good, which is preferable.

The color change ΔE _w can be obtained according to the following formula (22).
Formula (22): ΔE _w = [(ΔL _w ) ² + (Δa _w ) ² + (Δb _w ) ² ] ^1/2
Here, ΔL _w , Δa _w , and Δb _w are change amounts of the L ^* value, the a ^* value, and the b ^* value before and after the weather resistance test.

7- (3) Transmission Image Sharpness The transmission image definition is an optical comb having a slit width of 0.5 mm using an image clarity measuring instrument (ICM-2D type) manufactured by Suga Test Instruments Co., Ltd. according to JIS-K7105. Can be measured.

  The transmission image definition of the film of the present invention 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. It is preferable that the transparent image of the film of the present invention is 5% to 30%, since sufficient antiglare property and improvement in image blur and dark room contrast are compatible.

7- (4) Surface Roughness Centerline average roughness (Ra) can be measured according to JIS-B0601.
The antireflection film according to the present invention has an uneven surface shape with a center line average roughness Ra of 0.08 to 0.30 μm, a 10-point average roughness Rz of 10 times or less of Ra, and an average mountain valley distance Sm of 1 to 1. 100 μm, the standard deviation of the height of the convex part from the concavo-convex deepest part is 0.5 μm or less, the standard deviation of the average mountain-valley distance Sm with respect to the center line is 20 μm or less, and the surface with an inclination angle of 0 to 5 degrees is 10% or more It is preferable to design so that sufficient anti-glare properties and a visually uniform mat feeling can be achieved. If Ra is less than 0.08, sufficient antiglare property cannot be obtained, and if it exceeds 0.30, problems such as glare and surface whitening when external light is reflected occur.

7- (5) Haze The haze of the film of the present invention is the haze value defined in JIS-K7105. Based on the measurement method defined in JIS-K7361-1, manufactured by Nippon Denshoku Industries Co., Ltd. It is automatically measured as haze measured using a turbidimeter “NDH-1001DP” = (diffused light / total transmitted light) × 100 (%).

The surface haze and internal haze can be measured by the following procedure.
(1) The total haze value (H) of the film is measured according to JIS-K7136.
(2) A few drops of silicone oil are added to the front and back surfaces of the low refractive index layer side of the film, and sandwiched from the front and back using two 1 mm thick glass plates (micro slide glass product number S 9111, manufactured by MATSANAMI), Two glass plates and a film are optically closely adhered to each other, and the haze is measured in a state where surface haze is removed, and only the silicone oil is sandwiched between two separately measured glass plates to subtract the measured haze. The calculated value is calculated as the internal haze (Hi) of the film.
(3) A value obtained by subtracting the internal haze (Hi) calculated in (2) from the total haze (H) measured in (1) above is calculated as the surface haze (Hs) of the film.

7- (6) Scratch resistance <Steel wool scratch resistance evaluation>
By using a rubbing tester and carrying out a rubbing test under the following conditions, it can be used as an index of scratch resistance.
Evaluation environmental conditions: 25 ° C., 60% RH
Rubbing material: Steel wool (Nippon Steel Wool Co., Ltd., GELADE No. 0000)
Wrap around the tip (1cm x 1cm) of the scraper of the tester that comes into contact with the sample and fix the band.
Travel distance (one way): 13cm
Rubbing speed: 13 cm / second,
Load: 500 g / cm ² and 200 g / cm ²
Tip contact area: 1 cm × 1 cm, rubbing frequency: 10 reciprocations.
An oil-based black ink is applied to the back side of the sample that has been rubbed, and scratches on the rubbed portion are visually observed with reflected light, or evaluation is made based on the difference from the amount of reflected light other than the rubbed portion.

<Eraser scuff resistance evaluation>
By using a rubbing tester and carrying out a rubbing test under the following conditions, it can be used as an index of scratch resistance.
Evaluation environmental conditions: 25 ° C., 60% RH
Rubbing material: Plastic eraser (MONO made by Dragonfly Pencil Co., Ltd.)
Fixed to the tip (1 cm x 1 cm) of the scraper of the tester that comes into contact with the sample. Moving distance (one way): 4 cm,
Rubbing speed: 2 cm / second,
Load: 500 g / cm ²
Tip contact area: 1 cm × 1 cm,
Number of rubs: 100 round trips.
An oil-based black ink is applied to the back side of the sample that has been rubbed, and scratches on the rubbed portion are visually observed with reflected light, or evaluation is made based on the difference from the amount of reflected light other than the rubbed portion.

<Taper test>
In the Taber test according to JIS-K5400, the scratch resistance can be evaluated from the wear amount of the test piece before and after the test.
The smaller the amount of wear, the better.

7- (7) Hardness <Pencil hardness>
The strength of the film of the present invention can be evaluated by a pencil hardness test according to JIS-K5400.
The pencil hardness is preferably H or higher, more preferably 2H or higher, and most preferably 3H or higher.

<Surface elastic modulus>
The surface elastic modulus in the present invention is a value determined using a micro surface hardness tester (manufactured by Fisher Instruments: Fisherscope H100VP-HCU). Specifically, using a diamond pyramid indenter (tip-to-face angle: 136 °), the indentation depth is measured under an appropriate test load within a range where the indentation depth does not exceed 1 μm. This is the elastic modulus obtained from the change in load and displacement over time.
Further, the surface hardness can be obtained as a universal hardness by using the above-mentioned micro surface hardness tester. The universal hardness is a value obtained by measuring the indentation depth of a quadrangular pyramid indenter under a test load and dividing the test load by the surface area of the indent calculated from the geometric shape of the indent generated by the test load. It is known that there is a positive correlation between the surface elastic modulus and the universal hardness.

The universal hardness of the crosslinkable polymer defined in the present invention is determined by the following measurement procedure using a microhardness meter H100 manufactured by Fischer Instruments Co., Ltd. with respect to the crosslinkable polymer film having a thickness of about 20 to 30 μm cured on a glass plate. The universal hardness (N / mm ² ).
Appropriate bar coater is selected so that the film thickness after curing of a coating solution with a solid content of about 25% containing the necessary catalyst, crosslinking agent, polymerization initiator, etc. in addition to the crosslinkable polymer is about 20-30 μm. TOSHINRIKO. CO. Made of LTD (26 mm × 76 mm × 1.2 mm) coated on a polished glass slide plate. In the case where the crosslinkable polymer is thermosetting, a thermosetting condition for sufficiently curing the film is obtained in advance (for example, 125 ° C. for 10 minutes), and when the crosslinkable polymer is ionizing radiation curable, the film is similarly formed. The curing conditions for sufficient curing are obtained in advance (as an example, the oxygen concentration is 12 ppm, the UV irradiation amount is 750 mJ / cm ² ). Recess area for each film F when the load is continuously increased from 0 to 4 mN for each film, and the conical diamond indenter is pushed in with the maximum 1/10 film thickness not affected by the glass plate hardness of the substrate. Universal hardness is calculated from N = 6 measurement average value of F / A determined from A (mm ² ).
The surface hardness can be determined by nanoindentation described in JP-A No. 2004-354828. In this case, the hardness is preferably 2 GPa to 4 GPa, and the nanoindentation elastic modulus is preferably 10 GPa to 30 GPa.

7- (8) Antifouling test <Magic wiping property>
The film is fixed on the glass surface with an adhesive, and a circle with a diameter of 5 mm is written three times with a pen tip (thin) of black magic “Mckey extra fine (product name: made by ZEBRA)” at 25 ° C. and 60 RH%. After 5 seconds, wipe it back and forth 20 times with a load that dents the bundle of Bencot (Brand name, Asahi Kasei Co., Ltd.) folded into 10 sheets. The writing and wiping are repeated under the above conditions until after the magic does not disappear by wiping, and the antifouling property can be evaluated by the number of times of wiping.
The number of times until it no longer disappears is preferably 5 times or more, and more preferably 10 times or more.

  For Black Magic, Magic Ink No. 700 (M700-T1 black) Using an ultra-fine sample, draw a circle with a diameter of 1 cm on the sample, paint it for 24 hours, rub it with Bencott (Asahi Kasei Co., Ltd.), and evaluate whether the magic can be wiped off. .

7- (9) Contact angle Using a contact angle meter [“CA-X” type contact angle meter, manufactured by Kyowa Interface Science Co., Ltd.], using pure water as a liquid in a dry state (20 ° C./65% RH) Then, a droplet having a diameter of 1.0 mm was formed on the needle tip, and this was brought into contact with the surface of the film to form a droplet on the film. The angle formed between the tangent to the liquid surface and the film surface at the point where the film and the liquid are in contact with each other is defined as the contact angle.
The contact angle of the film of the present invention is preferably 94 degrees or more with respect to pure water. It is more preferably 97 degrees or more, and most preferably 101 degrees or more.

7- (10) Surface free energy The surface energy can be determined by the contact angle method, the wet heat method, and the adsorption method as described in “Basics and Applications of Wetting”, Realize, 1989.12.10. . In the case of the film of the present invention, it is preferable to use a contact angle method.
Specifically, two kinds of solutions having known surface energies are dropped on a film, for example, a cellulose acylate film, and the tangent line drawn on the droplet and the film surface are formed at the intersection of the surface of the droplet and the film surface. The surface angle of the film can be calculated by calculation by defining the angle containing the droplet as the contact angle.

The surface free energy (γs ^v : unit, mN / m) of the film of the present invention is D.I. K. Owens: J.M. Appl. Polym. Sci. , 13, 1741 (1969) with reference to the following simultaneous equations a and b from the contact angles θ _H2O and θ _{CH2I2 of} pure water H2O and methylene iodide CH2I2 experimentally determined on the antireflection film. It represents the surface tension of the antireflection film defined by the value γs ^v (= γs ^d + γs ^h ) represented by the sum of γs ^d and γs ^h . The gamma] s ^v is small, the more high repellency of the surface with a low surface free energy, generally excellent antifouling property.

a. 1 + cos θ _H2O =
^{_{2√γs d (√γ H2O d / γ}} H2O v) + 2√γs h (√γ H2O h / γ H2O v)
b. 1 + cos θ _CH2I2 =
^{_{2√γs d (√γ CH2I2 d / γ}} CH2I2 v) + 2√γs h (√γ CH2I2 h / γ CH2I2 v)
γ _{H 2 O} ^d = 21.8, γ _{H 2 O} ^h = 51.0, γ _{H 2 O} ^v = 72.8,
γ _CH2I2 ^d = 49.5, _γCH2I2 ^h = 1.3, _γCH2I2 ^v = 50.8
In the contact angle measurement, after the film was conditioned for 1 hour or more at 25 ° C. and 60%, 2 μl of the droplet was formed into a film using an automatic contact angle meter CA-V150 manufactured by Kyowa Interface Science Co., Ltd. The contact angle was determined 30 seconds after dropping.

  The surface free energy of the film of the present invention is preferably 25 mN / m or less, and particularly preferably 20 mN / m or less.

7- (11) Curl The curl is measured using the curl measurement template of Method A in “Measurement Method of Curling of Photographic Film” of JIS-K7619-1988.
The measurement conditions are 25 ° C., relative humidity 60%, and humidity control time 10 hours.
The film according to the present invention preferably has a value when curl is expressed by the following mathematical formula in a range of minus 15 to plus 15, more preferably in a range of minus 12 to plus 12, more preferably minus 10. ~ Plus 10. In this case, the measurement direction of the curl in the sample is measured in the conveyance direction of the base material in the case of application in a web form.

  (Formula) Curl = 1 / R R is the radius of curvature (m)

This is an important characteristic for preventing cracks and film peeling during film production, processing, and market handling. It is preferable that the curl value is in the above range and the curl is small.
Here, “curl plus” means a curl in which the coating side of the film is inside the curve, and “minus” means a curl in which the coating side is outside the curve.

  In the film according to the present invention, the absolute value of the difference between the curl values when the relative humidity is changed to 80% and 10% based on the curl measurement method is preferably 24 to 0, and preferably 15 to 0. Is more preferable, and 8 to 0 is most preferable. This is a property related to handling, peeling and cracking when films are attached under various humidity.

7- (12) Adhesion Evaluation The adhesion between the layers of the film or between the support and the coating layer can be evaluated by the following method.
Nitto Denko Co., Ltd. Polyester adhesive tape with 11 squares and 11 horizontal cuts at 1 mm intervals and a total of 100 squares on the surface of the coated layer. (NO.31B) is pressure-bonded, and the test for peeling off after leaving for 24 hours is repeated three times at the same place, and the presence or absence of peeling is visually observed.
Of 100 squares, peeling is preferably within 10 mm, and more preferably within 2 mm.

7- (13) Brittleness test (crack resistance)
Crack resistance is an important characteristic for preventing crack defects by handling such as film application, processing, cutting, adhesive application, and application to various objects.
A film sample is cut into 35 mm x 140 mm, left to stand for 2 hours at a temperature of 25 ° C and a relative humidity of 60%, and then the curvature diameter at which cracks start to occur when rolled into a cylinder is measured to evaluate surface cracks. can do.
The crack resistance of the film of the present invention is preferably 50 mm or less, more preferably 40 mm or less, and most preferably 30 mm or less, when the film is rolled with the coating layer side facing outward. About the crack of an edge part, it is preferable that there is no crack or the length of a crack is less than 1 mm on average.

7- (14) Dust Removability The film of the present invention can be attached to a monitor, dust (futon, textile waste) can be sprinkled on the monitor surface, the dust can be wiped off with a cleaning cloth, and the dust removability can be evaluated.
It is preferable to remove completely by wiping 6 times, and it is more preferable to remove dust completely by wiping within 3 times.

7- (15) Performance of liquid crystal display device Hereinafter, a method for evaluating characteristics and a preferable situation when the film of the present invention is used on a display device will be described.
The polarizing plate on the viewing side provided in the liquid crystal display device (TH-15TA2, manufactured by Matsushita Electric Industrial Co., Ltd.) using a TN type liquid crystal cell is peeled off, and the film or polarizing plate of the present invention is used instead. It sticks through an adhesive so that the transmission side of a polarizing plate may correspond with the polarizing plate stuck on the product at the visual recognition side. In a 500 lux bright room, the liquid crystal display device is displayed in black, and the following various characteristics can be evaluated visually from various viewing angles.

<Evaluation of image unevenness and color>
Using the created liquid crystal display device, unevenness and color change during black display (L1) are visually evaluated by a plurality of observers.
It is preferable that three people or less can recognize the unevenness, left-right color change, color change due to temperature and humidity, and white blur, and more preferably no one can recognize it.
In addition, reflection of external light is performed using a fluorescent lamp, and a change in reflection can be relatively evaluated visually.

<Light leakage of black display>
The light leakage rate of black display in the azimuth direction 45 ° and polar angle direction 70 ° from the front of the liquid crystal display device is measured. The light leakage rate is preferably 0.4% or less, and more preferably 0.1% or less.

<Contrast and viewing angle>
Contrast and viewing angle are measured using a measuring device ("EZ-Contrast 160D" manufactured by ELDIM). Can be checked.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited thereto. In the following examples and synthesis examples,% and parts are based on mass unless otherwise specified.

Example 1
Synthesis Example 1: Synthesis of fluorinated polymer P1 described in the specification A 40 mL stainless steel autoclave with a stirrer was charged with 40 mL of ethyl acetate, 14.7 g of hydroxyethyl vinyl ether (HEVE) and 0.55 g of dilauroyl peroxide. The inside was deaerated and replaced with nitrogen gas. Further, 25 g of hexafluoropropylene (HFP) was introduced into the autoclave and heated to 65 ° C. The pressure when the temperature in the autoclave reached 65 ° C. was 5.4 kg / cm ² . The reaction was continued for 8 hours while keeping the inside of the autoclave at 65 ° C. When the pressure reached 3.2 kg / cm ² , 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 solvent was removed by decantation, and the precipitated polymer was taken out. 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 copolymer P1 having a molar ratio of HFP: HEVE of 1: 1 was obtained. The number average molecular weight of the obtained polymer was 15,000.

Synthesis Examples 2-5
Fluorinated polymers P3, P43 and P44 described in the specification were synthesized in substantially the same manner as the synthesis of P1 in Synthesis Example 1 above. The number average molecular weights of the obtained fluoropolymers are shown in Tables 2 to 6 above.

(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. Sol solution a was adjusted with methyl ethyl ketone so that the solid content was 29%.

(Preparation of hollow silica dispersion)
In 500 parts of 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), acryloyloxypropyl After adding 30.5 parts of trimethoxysilane and 1.51 parts of diisopropoxyaluminum ethyl acetate and mixing, 9 parts of ion-exchanged water was added. After reacting at 60 ° C. for 8 hours, the mixture was cooled to room temperature, and 1.8 parts of acetylacetone was added to obtain a dispersion. Then, while adding cyclohexanone so that the silica content was substantially constant, the solvent was replaced by distillation under reduced pressure at a pressure of 30 Torr. Finally, a dispersion having a solid content concentration of 18.2% was obtained by adjusting the concentration. When the amount of IPA remaining in the obtained dispersion was analyzed by gas chromatography, it was 0.5% or less.

(Preparation of curable composition LL1)
Colloidal silica fine particles (MEK-ST-L, Nissan Chemical Industries, Ltd., average particle size 10-15 nm, silica concentration 30%) 100 parts, 0.7 parts of acid-catalyzed paratoluenesulfonic acid monohydrate, crosslinked Methylolated melamine (Nippon Cytec Industries, Ltd., Cymel 303) 10 parts, and methyl ethyl ketone was added with stirring so that the silica concentration was 15%. After stirring at 25 ° C. for 24 hours, 0.4 part of the organic base b-14 shown in Table 7 was added. Thereafter, 40 parts of fluoropolymer P1, 52 parts of sol a as organosilane, and 1 part of FM-4425 as polysiloxane are added, methyl ethyl ketone is added so that the solid content concentration is 6%, and the product is made of polypropylene having a pore diameter of 1 μm. A curable composition (LL1) was prepared by filtration through a filter.

(Preparation of curable compositions LL2 to LL18)
Curable compositions LL2 to LL18 were prepared in the same manner as in the preparation of the cross-linking agent-silica particle mixed solution A except that the types and amounts of each component were changed to the amounts shown in Table 8.

(Preparation of curable compositions LL19 to LL20)
Curable compositions LL19 and LL20 were prepared in the same manner as LL1 and LL2, except that the acid catalyst was added after the organic base.

(Preparation of curable compositions LL21 to LL22)
Curable compositions LL21 and LL22 were prepared in the same manner as LL1 and LL2, except that the addition of the fluorine-containing polymer was performed simultaneously with the crosslinking agent.

"Hollow silica": Hollow silica manufactured by Catalyst Kasei Kogyo Co., Ltd. (using hollow silica dispersion described later)
“BS”: benzenesulfonic acid monohydrate “b-23”: diethylmethylamine (* 1): 1: 1 mixture of sol solution a and DPHA (mass ratio)
“DPHA”: Nippon Kayaku Co., Ltd. UV curable resin “PTS”: p-toluenesulfonic acid “FM-4425”: Chisso Corporation “X-22-160AS”: Shin-Etsu Chemical Co., Ltd. “H-2”: Compound having the following structure

[Preparation of antireflection film]
[Preparation of coating solution for antiglare layer (HCL-1)]
"PET-30" 50.0g
"Irgacure 184" 2.0g
"SX-350" (30%) 1.5g
Cross-linked acrylic-styrene particles (30%) 13.9g
"KBM-5103" 10.0g
Toluene 38.5g

  The mixed solution was filtered through a polypropylene filter having a pore size of 30 μm to prepare a hard coat layer coating solution (HCL-1).

The compounds used are shown below.
“PET-30”: a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate {manufactured by Nippon Kayaku Co., Ltd.}
“Irgacure 184”: Polymerization initiator {Ciba Specialty Chemicals Co., Ltd.}
“SX-350”: Cross-linked polystyrene particles having an average particle size of 3.5 μm {refractive index 1.60, manufactured by Soken Chemical Co., Ltd., 30% toluene dispersion. Use after dispersion for 20 minutes at 10,000 rpm in a Polytron disperser}.
Cross-linked acrylic-styrene particles: average particle size 3.5 μm {refractive index 1.55, manufactured by Soken Chemical Co., Ltd., 30% toluene dispersion. Use after dispersion for 20 minutes at 10,000 rpm in a Polytron disperser}.
“KBM-5103”: acryloyloxypropyltrimethoxysilane {manufactured by Shin-Etsu Chemical Co., Ltd.}.

[Preparation of Antireflection Film Sample 101]
An 80 μm-thick triacetyl cellulose film “TAC-TD80U” (manufactured by Fuji Photo Film Co., Ltd.) is unwound in a roll form, and the coating solution for antiglare layer (HCL-1) is directly Using a micro gravure roll with a diameter of 50 mm having a gravure pattern of 180 lines / in and a depth of 40 μm, and a doctor blade, it was applied under the conditions of a gravure roll rotation speed of 30 rpm and a conveyance speed of 30 m / min, and dried at 60 ° C. for 150 seconds. Further, using an “air-cooled metal halide lamp” {manufactured by Eye Graphics Co., Ltd.) with an oxygen concentration of 0.1 vol% under a nitrogen purge, ultraviolet rays having an illuminance of 400 mW / cm ² and an irradiation amount of 100 mJ / cm ² are used. The coating layer was cured by irradiation to form a 6 μm thick layer and wound up. The surface roughness of the antiglare layer (HCL-1) thus obtained was Ra = 0.18 μm, Rz = 1.40 μm, the surface haze was 12%, and the internal haze was 29%. .

On the antiglare layer thus obtained, the curable composition (LL-1) was used and the film thickness was adjusted to 95 nm to prepare an antireflection film sample 101. The curable composition LL-1 is coated after mixing the respective components for 2 hours, the drying and heat curing conditions are 100 ° C. and 8 minutes, and the ultraviolet curing conditions are an atmosphere having an oxygen concentration of 0.01% by volume or less. Thus, while purging with nitrogen, a 240 W / cm “air-cooled metal halide lamp” {manufactured by Eye Graphics Co., Ltd.) was used to obtain an irradiation intensity of 120 mW / cm ² and an irradiation amount of 240 mJ / cm ² .

[Preparation of antireflection films 102 to 122]
In producing the antireflection film (101), instead of using the curable composition (LL-1), it is more reflective in the same manner as the antireflection film 101 except that (LL-2) to (LL-22) are used. The prevention films 102-122 were produced.

[Saponification treatment of antireflection film]
The obtained antireflection film was treated and dried under the following saponification standard conditions.
Alkaline bath: 1.5 mol / dm ³ sodium hydroxide aqueous solution, 55 ° C.-120 seconds.
First washing bath: tap water, 60 seconds.
Neutralization bath: 0.05 mol / dm ³ sulfuric acid, 30 ° C. for 20 seconds.
Second washing bath: tap water, 60 seconds.
Drying: 120 ° C., 60 seconds.

[Evaluation of antireflection film]
The following evaluation was performed using the saponified antireflection film thus obtained.

(Evaluation 1) Measurement of average reflectance An average reflectance of 450 to 650 nm was used by the method described in the present text. As for the sample processed into the polarizing plate, the polarizing plate type is used as it is, and in the case of a display device that does not use the film itself or the polarizing plate, the back surface of the antireflection film is roughened and then blackened. Were subjected to light absorption treatment (transmittance at 380 to 780 nm was less than 10%) and measured on a black table.

(Evaluation 2) Steel wool scratch resistance evaluation (SW resistance)
The oil-based black ink was applied to the back side of the sample which had been tested and rubbed by the above method and visually observed with reflected light, and scratches on the rubbed portion were evaluated according to the following criteria. However, the load was 500 g / cm ² and the number of rubs was 20 times.
○: Even if you look very carefully, no scratches are visible.
○ △: Slightly weak scratches are visible when viewed very carefully.
Δ: Weak scratches are visible.
Δ ×: moderate scratches are visible.
X: There is a scratch that can be seen at first glance.

(Evaluation 3) Eraser abrasion resistance evaluation (eraser abrasion resistance)
An oil-based black ink was applied to the back side of the sample which was tested by the method described in the text and rubbed, and visually observed with reflected light, and scratches on the rubbed portion were evaluated according to the following criteria. However, the load was 500 g / cm ² and the number of rubs was 200.
○: Even if you look very carefully, no scratches are visible.
○ △: Slightly weak scratches are visible when viewed very carefully.
Δ: Weak scratches are visible.
Δ ×: moderate scratches are visible.
X: There is a scratch that can be seen at first glance.
XX: Single-sided film is damaged.

(Evaluation 4) Magic wiping property Tested by the method described in the text, the number of times until the magic did not disappear was determined. The number of times until it no longer disappears is preferably 5 times or more, and more preferably 10 times or more.

(Evaluation 5) Evaluation of coated surface condition Oily black ink was applied to the back side of a sample having an A4 size, and the surface condition was evaluated according to the following criteria by visual observation with reflected light.
○: Even if looked very carefully, unevenness is not visible.
○ △: Slightly weak unevenness is seen when viewed very carefully.
Δ: Weak unevenness is visible.
Δ ×: Medium unevenness is visible.
×: Unevenness that can be seen at first glance.

  As is clear from this example, it can be seen that the antireflection film using the curable composition of the present invention is excellent in SW rubbing resistance, eraser rubbing resistance, antifouling property, and coated surface condition.

Example 2
A multilayer antireflection film shown below was prepared.
(Preparation of hard coat layer coating solution (HCL-2))
90 parts by mass of MEK, 10 parts by mass of cyclohexanone, 85 parts by mass of partially caprolactone-modified polyfunctional acrylate (DPCA-20, manufactured by Nippon Kayaku Co., Ltd.), KBM-5103 (silane coupling agent: Shin-Etsu Chemical Co., Ltd.) 10 parts by mass) and 5 parts by mass of a photopolymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) were added and stirred. It filtered with the polypropylene filter with the hole diameter of 0.4 micrometer, and prepared the coating liquid (HCL-2) for hard-coat layers.

(Preparation of antireflection film (201))
An 80 μm-thick triacetyl cellulose film “TAC-TD80U” (manufactured by Fuji Photo Film Co., Ltd.) is unwound in a roll form, and the above hard coat layer coating liquid (HCL-2) is directly Using a micro gravure roll with a diameter of 50 mm having a gravure pattern of 180 lines / in and a depth of 40 μm, and a doctor blade, it was applied under the conditions of a gravure roll rotation speed of 30 rpm and a conveyance speed of 30 m / min, and dried at 60 ° C. for 150 seconds. Further, using an “air-cooled metal halide lamp” {manufactured by Eye Graphics Co., Ltd.) with an oxygen concentration of 0.1 vol% under a nitrogen purge, ultraviolet rays having an illuminance of 400 mW / cm ² and an irradiation amount of 100 mJ / cm ² are used. The coating layer was cured by irradiation to form a 7 μm thick layer and wound up. The surface roughness of the hard coat layer (HCL-2) thus obtained was Ra = 0.005 μm and Rz = 0.01 μm.

The above-described LL-1 to LL22 were applied according to Example 1 on the hard coat layer, and antireflection films 201 to 222 were produced.
As a result of performing saponification treatment and evaluation according to Example 1, it was found that an antireflection film having low reflection, excellent scratch resistance, antifouling properties, and excellent coated surface shape was obtained as in Example 1.

Example 3
A multilayer antireflection film shown below was prepared.
(Preparation of hard coat layer coating solution (HCL-3))
The following composition was put into a mixing tank and stirred to obtain a hard coat layer coating solution.
750.0 parts by mass of trimethylolpropane triacrylate (TMPTA, Nippon Kayaku Co., Ltd.), 270.0 parts by mass of poly (glycidyl methacrylate) having a mass average molecular weight of 15000, 730.0 parts by mass of methyl ethyl ketone, 500.0 cyclohexanone Mass parts and 50.0 parts by mass of a photopolymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) were added and stirred.
The mixture was filtered through a polypropylene filter having a pore size of 0.4 μm to prepare a hard coat layer coating solution (HCL-3).

(Preparation of titanium dioxide fine particle dispersion)
As the titanium dioxide fine particles, titanium dioxide fine particles (MPT-129C, manufactured by Ishihara Sangyo Co., Ltd., TiO ₂ : Co ₃ O ₄ : containing cobalt and subjected to surface treatment using aluminum hydroxide and zirconium hydroxide: Al ₂ O ₃ : ZrO ₂ = 90.5: 3.0: 4.0: 0.5 mass ratio) was used.
The following dispersant (41.1 parts by mass) and cyclohexanone (701.8 parts by mass) were added to 257.1 parts by mass of the particles and dispersed by dynomill to prepare a titanium dioxide dispersion having a mass average diameter of 70 nm.

(Preparation of coating solution for medium refractive index layer)
In 99.1 parts by mass of the above titanium dioxide dispersion, 68.0 parts by mass of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA), 3.6 parts by mass of a photopolymerization initiator (Irgacure 907), light A sensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.) 1.2 parts by mass, 279.6 parts by mass of methyl ethyl ketone and 1049.0 parts by mass of cyclohexanone were added and stirred. After sufficiently stirring, the solution was filtered through a polypropylene filter having a pore size of 0.4 μm to prepare a coating solution for a medium refractive index layer.

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

(Preparation of antireflection film (301))
The hard coat layer coating solution was applied on a triacetyl cellulose film (TD80UF, manufactured by Fuji Photo Film Co., Ltd.) having a thickness of 80 μm using a gravure coater. After drying at 100 ° C., an irradiance of 400 mW / cm using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) of 160 W / cm while purging with nitrogen so that the oxygen concentration becomes 1.0 vol% or less. ² , the coating layer was cured by irradiating with an irradiation amount of 300 mJ / cm ² to form a hard coat layer having a thickness of 8 μm.
Using a gravure coater having three coating stations on a hard coat layer, a coating solution for a medium refractive index layer, a coating solution for a high refractive index layer, and a curable composition LL-1 (a coating solution for a low refractive index layer). Applied continuously.

The medium refractive index layer was dried at 90 ° C. for 30 seconds, and the ultraviolet curing condition was 180 W / cm air-cooled metal halide lamp (eye graphics) while purging with nitrogen so that the atmosphere had an oxygen concentration of 0.1% by volume or less. ), And the irradiation dose was 400 mW / cm ² and the irradiation dose was 400 mJ / cm ² . The medium refractive index layer after curing had a refractive index of 1.630 and a film thickness of 67 nm.

The drying condition of the high refractive index layer is 90 ° C. for 30 seconds, and the UV curing condition is 240 W / cm air-cooled metal halide lamp (eye graphics) while purging with nitrogen so that the atmosphere has an oxygen concentration of 0.1% by volume or less. ), And the irradiation dose was 600 mW / cm ² and the irradiation dose was 400 mJ / cm ² .
The cured high refractive index layer had a refractive index of 1.905 and a film thickness of 107 nm.

The low refractive index layer was dried and heat-cured under conditions of 100 ° C. and 8 minutes, and the ultraviolet curing condition was “air-cooled metal halide of 240 W / cm while purging with nitrogen so that the atmosphere had an oxygen concentration of 0.01% by volume or less. using lamp "{manufactured by eye graphics Co., Ltd.}, illuminance 120 mW / cm ^2, and the irradiation amount of dose 480 mJ / cm ^2.

  Samples 302 to 322 were prepared in the same manner as the sample 301 except that the coating solution for the low refractive index layer was changed to (LL-2) to (LL-22) for the sample 301 thus obtained. . As a result of performing the saponification treatment and evaluation according to Example 1, the reflectance of each sample was greatly reduced by providing the middle refractive index layer and the high refractive index layer. According to the present invention, it has been found that an anti-reflection film having low reflection, excellent scratch resistance, antifouling property, and coated surface can be obtained.

Example 4
A multilayer antireflection film shown below was prepared.
(Preparation of hard coat layer coating solution (HCL-4))
Desolite Z7404 (zirconia fine particle-containing hard coat composition: manufactured by JSR Corporation) 100 parts by mass, DPHA (UV curable resin: Nippon Kayaku Co., Ltd.) 31 parts by mass, KBM-5103 (silane coupling agent: Shin-Etsu) Chemical Industry Co., Ltd.) 10 parts by mass, KE-P150 (1.5 μm silica particles: Nippon Shokubai Co., Ltd.) 8.9 parts by mass, MXS-300 (3 μm cross-linked PMMA particles: manufactured by Soken Chemical Co., Ltd.) 3.4 parts by mass MEK 29 parts by mass and MIBK 13 parts by mass were charged into a mixing tank and stirred to obtain a hard coat layer coating solution.

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

  The same low refractive index layer as in Example 1 was coated on the hard coat 401, and saponification treatment was performed and evaluation according to Example 1 was performed. As a result, according to the present invention, low reflection, scratch resistance, It has been found that an antireflection film excellent in soiling and coated surface can be obtained.

Example 5
<Preparation of polarizing plate with antireflection film>
A polarizing film was prepared by adsorbing iodine to a stretched polyvinyl alcohol film. A saponified antireflection film of Example 1 was attached to one side of the polarizing film using a polyvinyl alcohol adhesive so that the support (triacetylcellulose) side of the antireflection film was the polarizing film side. . A viewing angle widening film “Wide View Film SA12B” (manufactured by Fuji Photo Film Co., Ltd.) having an optical compensation layer was saponified and attached to the other side of the polarizing film using a polyvinyl alcohol adhesive. In this way, a polarizing plate was produced. As a result of performing the evaluation according to Example 1 in this polarizing plate state, the same effect was obtained by using the low refractive index layer of the present invention.

Example 6
The TN, IPS, VA, and OCB mode transmission type liquid crystal display devices mounted on the viewing side so that the antireflection film side is the display surface side of the polarizing plate of the present invention produced in Example 5 can be viewed and resisted. It was confirmed that the scratch and antifouling properties were excellent.

Example 7
When the antireflection film sample of the present invention of Example 2 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. It was.

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. 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. 1 is an example of a cross-sectional view of a coater using a slot die that is preferably used for producing the film of the present invention. (A) shows an example of the sectional shape of the slot die, and (B) shows an example of the sectional shape of the conventional slot die. It is an example of the perspective view which shows the slot die of the coating process preferably used in order to manufacture the film of this invention, and its periphery.

Explanation of symbols

(1) Support (2) Hard coat layer (3) Medium refractive index layer (4) High refractive index layer (5) Low refractive index layer (6) Matte particle 10 Coater 11 Backup roll W Web 13 Slot die 14 Coating liquid 14a Bead 14b Coating 15 Pocket 16 Slot 16a Slot opening 17 Tip lip 18 Land 18a Upstream lip land 18b Downstream lip land I _UP Upstream lip land 18a land length I _LO Downstream lip land 18b land length LO over bit length (difference in distance between web W of downstream lip land 18b and upstream lip land 18a)
G _L Gap between the lip 17 and the web W (gap between the downstream lip land 18b and the web W)
30 the gap _{G S} side plate 40b and the web W between the conventional slot-die 31a upstream lip land 31b downstream lip land 32 pocket 33 slot 40 vacuum chamber 40a back plate 40b side plate 40c screws _{G B} back plate 40a and the web W Gap between

Claims (15)

  A curable composition containing (A) inorganic particles having a crosslinkable group capable of reacting with a hydroxyl group, and (B) a fluorine-containing polymer having at least one kind of a fluorine-containing vinyl monomer polymerization unit and a hydroxyl group-containing vinyl monomer polymerization unit. .   Furthermore, (C) The curable composition of Claim 1 containing the organic base whose pKa of conjugate acid is 5.0-10.5, or the organic base whose boiling point is 35 degreeC or more and 85 degrees C or less.   The curable composition according to claim 1 or 2, wherein the inorganic particles are previously mixed with a crosslinking agent capable of reacting with a hydroxyl group in the presence of an acid catalyst.   The curable composition according to any one of claims 1 to 3, wherein the inorganic particles are silica particles.   The curable composition according to claim 4, wherein the silica particles have a hollow structure and have a refractive index in the range of 1.15 to 1.40.   The curable composition according to any one of claims 1 to 5, wherein the fluorine-containing polymer further has a polysiloxane polymer unit.   Furthermore, (D) The curable composition as described in any one of Claims 1-6 containing the hydrolyzate of the organosilane compound or this organosilane compound, and / or its partial condensate.   Furthermore, (E) The curable composition as described in any one of Claims 1-7 containing the compound which has a 2 or more (meth) acryloyl group in 1 molecule. Furthermore, (F) It has a polysiloxane structure represented by following General formula (10), and contains the compound which has a structure which can react with a hydroxyl group or a hydroxyl group and can form a bond. The curable composition according to 1.

In General Formula (10), R ¹ and R ² may be the same or different and each represents an alkyl group or an aryl group. p represents an integer of 2 to 500.   (A) inorganic particles mixed with a crosslinking agent capable of reacting with a hydroxyl group in the presence of an acid catalyst, and (B) a fluorine-containing polymer having at least one kind of a fluorine-containing vinyl monomer polymerization unit and a hydroxyl group-containing vinyl monomer polymerization unit, The manufacturing method of the curable composition which mixes.   The organic base having (C) a conjugate acid having a pKa of 5.0 to 10.5 or an organic base having a boiling point of 35 ° C or higher and 85 ° C or lower is mixed before the mixing of (B). A method for producing a curable composition.   An optical film comprising at least one layer formed from the curable composition according to claim 1.   An antireflection film comprising the optical film according to claim 12 on a support.   The polarizing plate in which at least one of the two protective films of the polarizing film in the polarizing plate is the optical film according to claim 12 or the antireflection film according to claim 13.   The image display apparatus which has the optical film of Claim 12, the antireflection film of Claim 13, or the polarizing plate of Claim 14 in the outermost surface of a display.

Images