JP2007272197A - Optical film, coating composition, polarizing plate and image display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an optical film excellent in stainproofness and dustproofness. <P>SOLUTION: An optical film, which comprises: a support; and a layer containing an electrically-conductive particulate material, in which an interior of the electrically-conductive particulate material is porous or hollow, wherein the optical film comprises a fluorine-containing silane compound. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an optical film, particularly an antireflection film, a coating composition, a polarizing plate and an image display device.

  In recent years, display devices have been used at home and demanded toughness for handling of general users. For example, in various image display devices such as a liquid crystal display device (LCD), a plasma display panel (PDP), an electroluminescence display (ELD), a cathode ray tube display device (CRT), and a surface-conduction electron-emitter display (SED). The optical film used on the surface is required to have high physical strength (such as scratch resistance), transparency, chemical resistance, and weather resistance (such as moist heat resistance and light resistance). Further, in order to prevent a decrease in contrast due to reflection of external light or reflection of an image, antiglare performance and antireflection performance are required. Furthermore, measures are required to prevent dust (such as dust) that reduces the visibility of the display from adhering to the surface of the optical film.

From the viewpoint of preventing the adhesion of dirt, it is effective to reduce the surface free energy of the optical film, and the use of a fluorine-containing antifouling agent is disclosed (for example, see Patent Document 1).
On the other hand, it is known to provide an antistatic layer containing conductive particles from the viewpoint of preventing dust adhesion (for example, Patent Document 2).
From the viewpoint of lowering the refractive index of conductive particles, particles in which the surface of silica particles is coated with antimony oxide have been proposed (see, for example, Patent Document 3).

JP-A-9-127305 JP 2005-196122 A JP 2005-119909 A

However, the fluorine-containing antifouling agent described in Patent Document 1 and the like is easily charged, and dust tends to adhere to the optical film surface when the amount of use increases. It is desired to provide sufficient antifouling properties without limiting the amount of fluorine-containing antifouling agent used.
In addition, the method described in Patent Document 2 requires a new layer, which causes a time and economical burden in production. In addition, conductive particles that have been used in the past often have a refractive index of about 1.6 to 2.2, and the refractive index of the antistatic layer containing the particles may be high. When the refractive index of the antistatic layer is high, unintentional interference unevenness and the color of the reflected color may become strong due to the difference in refractive index between adjacent layers in the optical film, and these improvements are desired. .
Further improvement is demanded from the viewpoint of antifouling property for the particles of Patent Document 3, etc.

  Conventionally, since the fluorine-containing antifouling agent is easily charged, the amount of use cannot be increased, or it is used in combination with an antistatic layer. If the fluorine-containing antifouling agent and the conductive particles can be introduced (for example, a low refractive index layer), the antifouling property and the antistatic property can be compatible with a simple layer structure. Therefore, the subject of this invention is providing the optical film which is excellent in antifouling property and dustproof property.

  In light of the above problems, the present inventors have conducted extensive research and found an optical film having a specific structure defined by the present invention, and unexpectedly found to have exceptional performance as an optical film, The present invention has been completed.

(1)
An optical film having a layer containing conductive particles having a porous or hollow particle inside on a support, wherein the optical film contains a fluorine-containing silane compound.
(2)
The optical film as described in (1) which has an antifouling layer containing a fluorine-containing silane compound on an upper layer of the layer containing the conductive particles.
(3)
(1) or (2) in which the layer containing the conductive particles in which the inside of the particles is porous or hollow contains at least one kind of cured product of organosilane hydrolyzate and / or condensation reaction product The optical film as described.
(4)
The optical film according to (1) or (3), wherein the layer containing conductive particles in which the particle interior is porous or hollow contains a fluorine-containing silane compound, and the layer is the outermost surface layer.
(5)
The optical film according to any one of (1) to (4), wherein the fluorine-containing silane compound is a compound represented by the following general formula [1].
Formula _{[1] (Rf-L 1} ) n -Si (R 11) 4-n
(In the formula, Rf represents a linear, branched or cyclic fluorinated alkyl group having 1 to 20 carbon atoms or a fluorinated aromatic group having 6 to 14 carbon atoms. L ₁ is a divalent divalent having 10 or less carbon atoms. Represents a linking group, R ¹¹ represents an alkyl group, a hydroxyl group or a hydrolyzable group, and n represents an integer of 1 to 3.)
(6)
The optical film according to (5), wherein the fluorine-containing silane compound represented by the general formula [1] is represented by the following general formula [2].
Formula _{[2] C n F 2n +} 1 - (CH 2) m -Si (R) 3
(In the formula, n represents an integer of 10 or more, m represents an integer of 1 to 5. R represents an alkoxy group having 1 to 5 carbon atoms or a halogen atom.)
(7)
The optical film according to any one of (1) to (4), wherein the fluorine-containing silane compound contains a perfluoropolyether group.
(8)
The optical film according to (7), wherein the fluorine-containing silane compound is a compound represented by the following general formula [3].
General formula [3]

Wherein R _f is a linear or branched perfluoroalkyl group having 1 to 16 carbon atoms, X is an iodine atom or a hydrogen atom, Y is a hydrogen atom or a lower alkyl group, Z is a fluorine atom or a trifluoromethyl group. , R ¹ is a hydrolyzable group, R ² is hydrogen or an inert monovalent organic group, a, b, c, d are integers of 0 to 200, e is 0 or 1, and m and n are 0 to 0. (The integer of 2 and p represent the integer of 1-10.)
(9)
The optical film according to (8), wherein the fluorine-containing silane compound represented by the general formula [3] is a compound represented by the following general formula [4].
General formula [4]

(In the formula, Y represents a hydrogen atom or a lower alkyl group, R ¹ represents a hydrolyzable group, q represents an integer of 1 to 50, m represents an integer of 0 to 2, and p represents an integer of 2 to 10.)
(10)
The optical film according to any one of (1) to (4), wherein the fluorine-containing silane compound is a compound represented by the following general formula [5].
General formula [5]
_{^{Rf 5 [- (L 5)}} n -X-R 51 -Si (OR ⁵² ) ₃ ] _m
(Wherein Rf ⁵ represents a perfluoropolyether group, R ⁵¹ Is an alkylene group, R ⁵² is an alkyl group, L ₅ is —CO—, X is —O—, —NR ⁵³ —, —S—, —SO ₂ —, —SO ₂ NR ⁵³ —, —NR ^53. In the group selected from CO-, n represents 0 or 1, and m represents a natural number of 2 or less. R ⁵³ represents a hydrogen atom or an alkyl group having 3 or less carbon atoms. )
(11)
The optical film according to any one of (1) to (10), wherein the layer containing the fluorine-containing silane compound further contains a compound represented by the following general formula [7].
General formula [7]
R ⁷¹ -Si (OR ⁷² ₃
(Where R ⁷¹ Represents a long-chain hydrocarbon group having 10 or more carbon atoms, and R ⁷² represents an alkyl group. )
(12)
Silicon atoms (Si2p) and fluorine atoms (on the film surface) measured by X-ray photoelectron spectroscopy
(1) to (11), wherein the peak area ratio (Si2p / F1s) of F1s) is 0.0 or more and 0.4 or less.
(13)
The optical film as described in (1)-(12) whose dynamic friction coefficient is 0.02 or more and 0.30 or less.
(14)
The optical film as described in (1)-(13) whose contact angle of water is 95 degree | times or more.
(15)
The optical film as described in (1)-(14) whose value when the surface resistance of an optical film is represented by log (SR) is 12 or less.
(16)
The layer containing the said electroconductive particle is a low refractive index layer, The optical film as described in (1)-(15) whose film thickness is 130 to 500 nm.
(17)
A coating composition containing the following components (A), (B), and (C).
(A) Conductive particles having a porous or hollow particle interior. (B) At least one of organosilane and / or its hydrolyzate and / or its condensation reaction product.
(C) At least one of a fluorine-containing silane compound and / or a hydrolyzate thereof and / or a condensation reaction product thereof.
(18)
The coating composition according to (17), wherein the fluorine-containing silane compound as the component (C) is represented by any one of the general formulas [1] to [5].
(19)
A polarizing plate having the optical film according to any one of (1) to (16).
(20)
The image display apparatus which has an optical film in any one of (1)-(16).

  The optical film of the present invention has excellent antifouling properties and dustproof properties, and particularly excellent antifouling durability. In addition, the optical film of the present invention is an optical film that has excellent scratch resistance, reduced coating unevenness, and high productivity. Moreover, the structure which can provide electroconductivity to a surface layer has the effect that surface electroconductivity is improved even if there is little quantity of an antistatic agent, and it is advantageous also in cost. Furthermore, since the optical film of the present invention uses conductive particles in which the particle interior is porous or hollow, the reflectance is low. A polarizing plate or a display device using the optical film of the present invention is excellent in handleability, has little reflection of external light and background, and has high visibility.

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

The optical film of the present invention is an optical film containing conductive particles having a porous or hollow particle interior and a fluorine-containing silane compound. Preferably, the layer containing the particles contains a cured product of at least one of hydrolyzate of organosilane and / or condensation reaction product. The layer containing the conductive particles in the optical film is not particularly limited in its function, and can have functions such as a conductive layer, a hard coat layer, an antiglare layer, and a low refractive index layer. The low refractive index layer is particularly preferable, and the embodiment of the present invention is most effective when the conductive particle-containing layer itself and / or the adjacent upper antifouling layer contains a fluorine-containing organosilane compound. In the present invention, the combination of the conductive particles having a porous or hollow particle inside and the fluorine-containing silane compound can not only provide conductivity and antifouling property but also improve antifouling durability. It was outside. Conductive particles with porous or hollow particles may have some influence on the reactivity and fixability of the fluorine-containing silane compound on the film, which will become clear in future analysis.
Below, the component of this invention is demonstrated in detail.

<Conductive particles whose inside is porous or hollow>
The conductive particles in which the inside of the particles used in the present invention is porous or hollow will be described. The conductive fine particles of the invention may be fine particles having any composition and structure as long as the inside of the particles is porous or hollow and has conductivity. Preferred conductive fine particles of the present invention are core / shell type composite fine particles having a high porosity (high porosity) fine particle as a core and a shell layer of a conductive material provided on the outside, and soluble in acids, alkalis or organic solvents. After forming a composite fine particle by providing a shell layer of a conductive material on the outside with the fine particle of the core as a nucleus, the core particle is removed by treatment with an acid, alkali or organic solvent to form an internal void. And void-type hollow fine particles.
In any case, the core particle may be conductive or non-conductive.

In the case of the former, that is, the core / shell type composite fine particle, the core particle is not limited as long as it is a high-porosity fine particle and can be shelled. And porous titanium oxide. Silica gel is particularly preferable.
In the case of the latter, that is, in the case of internal enveloping hollow fine particles, the core particles used in the production process are not limited as long as they can be dissolved and washed away through the shell layer by treatment with an acid, alkali or organic solvent, but preferred core particles are Metal oxide fine particles of a metal selected from Group 2A, 2B, 3A and 5B elements of the periodic table, among which ZnO, Y ₂ O ₃ and Sb ₂ O ₅ fine particles are preferable.

In the case of core / shell type composite fine particles, examples of the shell attaching method include a sol-gel conversion method using a metal alkoxide, a metal ultrafine particle addition method via a coupling agent or a hydrolyzate thereof, and a conductive material doping method. Can do.
For example, the inorganic fine particles may be directly formed on the surface of SiO ₂ particles produced by the methods described in JP-A-7-133105 and JP-A-2001-233611 by using a sol-gel method using an alkoxide of these metals.
Further, in the case of the inner void type hollow fine particles, as a combination of the core particles and the shell material, the surface of the fine particles such as ZnO, Y ₂ O ₃ , Sb ₂ O ₅ is made ultra fine particles such as ATO, ITO, SnO ₂ or these A method of forming hollow conductive inorganic fine particles by eluting the fine particles inside with an acid or alkaline aqueous solution after coating with the above thin film can be used. The particle | grains which coat | covered the surface of the silica particle with the antimony oxide are described in Unexamined-Japanese-Patent No. 2005-119909.
On the other hand, metals such as Au, Ag, Cu, Sn, Al, Ni, Fe, and Rh and alloys such as Al—Cu and Cu—Ni are colored, but have a relatively low refractive index of 1.7 or less. In addition, it is known to exhibit high conductivity. Therefore, even when these metal (alloy) ultrafine particles are used in a small amount as a shell of conductive fine particles, conductive fine particles having substantially high transparency and a low refractive index can be formed.

Next, the core / shell type composite fine particles by shelling with a coupling agent, which is a preferred form of the hollow conductive fine particles of the present invention, will be further described.
The conductive fine particles have semiconductor particles or insulator fine particles having an average particle diameter of 2 to 100 nm as core particles, and have an average particle diameter of 1 to 1 on the surface via at least one coupling agent or a hydrolyzate thereof. Composite fine particles in which 20 nm ultrafine metal particle fillers are bonded. In the present invention, the core particles of the semiconductor fine particles or insulator fine particles are preferably transparent and have a refractive index of 1.70 or less. Examples of such compounds include Al ₂ O ₃ and SiO ₂ . The coupling agent has two or more reactive groups in the molecule, and at least one of them is bonded to the semiconductor or insulator fine particles, and at least one of the remaining is bonded to the metal ultrafine particles, whereby the semiconductor or insulator It is a bridge between fine particles and ultrafine metal particles. The coupling agent may be one in which the hydrolyzate cross-links the semiconductor or insulator fine particles and the metal ultrafine particles. A preferred coupling agent is a compound represented by the following general formula [A].

Formula [A] M- (R) _n
In the general formula [A], M represents Si or Al, and n represents an integer corresponding to the valence of M. R represents an organic group, and the n Rs may be the same or different, and at least two of the n Rs are groups having reactivity with semiconductor fine particles, insulator fine particles or metal ultrafine particles. .

Among the organic groups represented by R, examples of the group having reactivity with semiconductor fine particles, insulator fine particles or metal ultrafine particles include (1) vinyl group, allyloxy group, acryloxy group, methacryloxy group, isocyanato group, formyl. group, an epoxy group, a styryl group, a ureido group, a reactive group such as a halogen, or an alkyl group having them end, (2) _{-SH terminated, -CN, -NH 2, -SO 2} OH, -SOOH, An alkyl group having an adsorptive group such as -OPO (OH) ₂ or -COOH; (3) an alkoxy group such as a methoxy group, an ethoxy group, an isopropoxy group, an n-propoxy group, a t-butoxy group, or an n-butoxy group. And (4) a phenoxy group. As these alkyl group, alkoxy group and phenoxy group, those having 8 or less carbon atoms are desirable. Further, these alkyl group, alkoxy group and phenoxy group may further have a substituent. The remaining organic group represented by R may be any group, but preferably has 8 or less carbon atoms.

Although the specific example of a coupling agent is enumerated below, it is not limited to these compounds.
N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminophenoxydimethylvinylsilane, aminophenyltrimethoxysilane, 3-amino Propyltriethoxysilane, bis (trimethoxysilylpropyl) amine, (p-chloromethyl) phenyltrimethoxysilane, (3-glycidoxypropyl) trimethoxysilane, 3-mercaptopropyltrimethoxysilane, (3-glycid Xylpropyl) -3-mercaptopropyldimethoxysilane, vinyltrichlorosilane, tetraethoxysilane, aminophenylaluminum dimethoxide, aluminum isopropoxide and the like.

The ultrafine metal particles are preferably made of a metal or alloy (composite metal) having a specific resistance at 20 ° C. of 20 μΩ · cm or less (preferably 10 μΩ · cm or less, more preferably 6 μΩ · cm or less). In general, it is known that the physical property value of a metal or an alloy is different between the bulk and the particle, but the specific resistance range refers to the bulk value of the metal or the alloy. Therefore, such physical property values are described in documents such as “Chemical Handbook (Edited by the Chemical Society of Japan)”, “Analytical Chemical Handbook (Edited by the Chemical Society of Japan)” and the like.
Examples of the metal that satisfies the above conditions include Au, Ag, Cu, Zn, Cd, Al, In, Tl, Sn, Co, Ni, Fe, Pd, Ir, Mo, Pt, Ru, Rh, and W. . Among these, Au, Ag, Cu, Pt, Pd, Ni, Ru, and Sn are preferable because of their low specific resistance and resistance to oxidation. When the ultrafine metal particles are made of an alloy, it is preferable to use an alloy containing at least one of Au, Ag, Cu, Pt, Pd, Ni, Ru, and Sn. Such alloys include Cu—Zn, Cu—Sn, Al—Cu, Cu—Sn—P, Cu—Ni, Au—Ag—Cu, Au—Zn, Au—Ni, Ag—Cu—Zn, and Ag—Cu. -Zn-Sn, Sn-Pb, Ag-In, Cu-Ag-Ni, Ag-Pd and the like can be mentioned, but are not limited thereto. There is no restriction | limiting in particular about the composition ratio of each metal in an alloy, and it can select variously. The metal and alloy may contain an impurity element, but the amount is preferably less than 1%. Examples of the impurity element include metals such as Cr, Sb, Bi, and Rh, and non-metals such as P, B, C, N, and S, alkali metals such as Na and K, and Mg and Ca. Examples include alkaline earth metals. One or more of these impurity elements may be contained.

In the core / shell type composite fine particles, it is preferable that the ultrafine metal particles are bonded at least 1/10 times the mass and more preferably 1/5 times the mass bonded per mass of the core particles.
In the present invention, the conductive fine particles preferably have a refractive index of 1.20 to 2.00, more preferably 1.30 to 1.80, and particularly preferably 1.30 to 1.70. Preferably, it is 1.35 to 1.65.
The powder resistance of the conductive fine particles is preferably as low as possible, preferably 1 × 10 ⁵ Ω · cm or less, more preferably 1 × 10 ⁴ Ω · cm or less, further preferably 1 × 10 ³ Ω · cm or less, particularly preferably. 1 × 10 ² Ω · cm or less. The powder resistance can be obtained, for example, by molding a sample powder at a pressure of 9.8 MPa (100 kg / cm ² ) to form a green compact, and measuring the direct current resistance. For example, it is described in JP-A-6-92636.
The average particle diameter of the primary particles of the conductive fine particles is preferably not more than the visible light wavelength region (that is, not more than 400 nm), more preferably 1 to 200 nm, still more preferably 1 to 100 nm, particularly preferably 1 to 1. 80 nm. In the case where the particles are internally enveloping particles, the thickness of the shell part forming the outer shell of the particles is preferably 1 to 100 nm, more preferably 1 to 50 nm, and most preferably 1 to 20 nm. The shape of the conductive fine particles may be any of a rice granular shape, a spherical shape, a cubic shape, a spindle shape, a rod shape, an indefinite shape, or a mixed shape thereof. The average particle diameter here is represented by the average value of the maximum diameters of the respective fine particles. For example, in the case of a spindle shape, the average value of the major axis diameters of the respective fine particles is defined as the average particle diameter. The particle diameter of the conductive fine particles is defined by an average particle diameter measured for at least 1000 particles by an electron micrograph.

<Organosilane compound used for layer containing conductive particles of the present invention>
The organosilane compound used in the present invention will be described in detail. This compound can be used as a binder of a layer containing the conductive particles of the present invention as it is or as a hydrolyzate or a condensate. The general formula is shown below.
Formula _{^{(B) :( R 10) m}} -Si (X) 4-m
In the general formula (B), R ¹⁰ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, hexyl group, t-butyl group, sec-butyl group, hexyl group, decyl group, hexadecyl group and the like. The alkyl group preferably has 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 a phenyl group and a naphthyl group, and a phenyl group is preferable.

X represents a hydroxyl group or a hydrolyzable group. Examples of the hydrolyzable group include an alkoxy group (an alkoxy group having 1 to 5 carbon atoms, such as a methoxy group and an ethoxy group), a halogen atom (for example, Cl, Br, I, etc.), and R ^2. COO groups (R ² is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Examples include CH ₃ COO groups and C ₂ H ₅ COO groups), preferably alkoxy groups, particularly preferably. Is a methoxy group or an ethoxy group.
m represents an integer of 0 to 3. When R ¹⁰ or X there are a plurality, a plurality of R ¹⁰ or X groups may be different, even the same, respectively. m is preferably 0, 1 or 2.

The substituent contained in R ¹⁰ is not particularly limited, but is a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), hydroxyl group, mercapto group, carboxyl group, epoxy group, alkyl group (methyl group, ethyl group, i -Propyl group, propyl group, t-butyl group etc.), aryl group (phenyl group, naphthyl group etc.), aromatic heterocyclic group (furyl group, pyrazolyl group, pyridyl group etc.), alkoxy group (methoxy group, ethoxy group) , I-propoxy group, hexyloxy group etc.), aryloxy group (phenoxy group etc.), alkylthio group (methylthio group, ethylthio group etc.), arylthio group (phenylthio group etc.), alkenyl group (vinyl group, 1-propenyl group) Etc.), acyloxy groups (acetoxy group, acryloyloxy group, methacryloyloxy group, etc.), alkoxycarbonyl groups (me Toxylcarbonyl group, ethoxycarbonyl group, etc.), aryloxycarbonyl group (phenoxycarbonyl group, etc.), carbamoyl group (carbamoyl group, N-methylcarbamoyl group, N, N-dimethylcarbamoyl group, N-methyl-N-octylcarbamoyl group) Etc.), acylamino groups (acetylamino group, benzoylamino group, acrylamino group, methacrylamino group, etc.) and the like, and these substituents may be further substituted. In the present specification, even if a hydrogen atom is replaced by a single atom, it is treated as a substituent for convenience.
When there are a plurality of R ¹⁰ , at least one is preferably a substituted alkyl group or a substituted aryl group. Of these, the substituted alkyl group or substituted aryl group preferably further has a vinyl polymerizable group.

  Preferred compounds in the present invention are tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane; methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltri Methoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, pentyltrimethoxysilane, pentyltriethoxysilane, heptyltrimethoxysilane, heptyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, dodecyltri Methoxysilane, dodecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, octadecyltrimethyl Xysilane, octadecyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ- Trialkoxysilanes such as glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane; dimethyl Examples thereof include dialkoxysilanes such as dimethoxysilane and dimethyldiethoxysilane. Among these, tetramethoxysilane, tetraethoxysilane, and γ-acryloxypropyltrimethoxysilane are preferable from the viewpoints of dispersion stability of the inorganic particles in the cured composition and scratch resistance.

(Hydrolysis and condensation reaction of organosilane)
In the present invention, the organosilane compound can be used in the coating composition after hydrolysis or partial condensation thereof. It is preferable that at least one of hydrolysis and condensation reaction of organosilane is performed 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 include organic bases such as pyridine; metal alkoxides such as triisopropoxyaluminum and tetrabutoxyzirconium. From the viewpoint of production stability and storage stability of the inorganic oxide fine particle liquid, an acid catalyst is used in the present invention. At least one of (inorganic acids, organic acids) and a metal chelate compound is used. Among inorganic acids, hydrochloric acid, sulfuric acid, nitric acid, and organic acids preferably have an acid dissociation constant (pKa value (25 ° C.)) of 4.5 or less in water. Among organic acids, methanesulfonic acid, oxalic acid, phthalic acid, and malonic acid are preferable, and oxalic acid is particularly preferable.

In the present invention, the metal chelate compound used for the formation of the hydrolyzate of organosilane and the condensation reaction is represented by the general formula R ³ OH (wherein R ³ represents an alkyl group having 1 to 10 carbon atoms). alcohol of the general formula R ⁴ COCH ₂ COR ⁵ (wherein, the R ⁴ is an alkyl group having 1 to 10 carbon atoms, R ⁵ represents an alkyl group or an alkoxy group having 1 to 10 carbon atoms having 1 to 10 carbon atoms. And at least one metal chelate compound having a metal selected from Zr, Ti and Al as a central metal.

  The metal chelate compound can be suitably used without particular limitation as long as it has a metal selected from Zr, Ti or Al as a central metal. Within this category, two or more metal chelate compounds may be used in combination. Specific examples of the metal chelate compound used in the present invention include tri-n-butoxyethyl acetoacetate zirconium, di-n-butoxybis (ethylacetoacetate) zirconium, n-butoxytris (ethylacetoacetate) zirconium, tetrakis (n Zirconium chelate compounds such as propylacetoacetate) zirconium, tetrakis (acetylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium; diisopropoxy bis (ethylacetoacetate) titanium, diisopropoxy bis (acetylacetate) titanium , Titanium chelate compounds such as diisopropoxy bis (acetylacetone) titanium; diisopropoxyethyl acetoacetate aluminum Diisopropoxyacetylacetonate aluminum, isopropoxybis (ethylacetoacetate) aluminum, isopropoxybis (acetylacetonate) aluminum, tris (ethylacetoacetate) aluminum, tris (acetylacetonato) aluminum, monoacetylacetonate bis (Ethyl acetoacetate) Aluminum chelate compounds such as aluminum can be mentioned.

  Among these metal chelate compounds, tri-n-butoxyethyl acetoacetate zirconium, diisopropoxybis (acetylacetonato) 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.

  The hydrolysis and condensation reaction of the organosilane can be performed without a solvent or in a solvent. By this reaction, the curable composition of the present invention can be produced. When a solvent is used, the concentration of the hydrolyzate of organosilane and its partial condensate can be appropriately determined. As the solvent, an organic solvent is preferably used in order to uniformly mix the components. For example, alcohols, aromatic hydrocarbons, ethers, ketones, esters and the like are preferable. The solvent preferably dissolves the organosilane and the catalyst. In addition, it is preferable in the process that an organic solvent is used as a coating solution or a part of the coating solution, and those that do not impair the solubility or dispersibility when mixed with other materials such as a fluorine-containing polymer are preferable.

  Among these, examples of the alcohols include monohydric alcohols and dihydric alcohols. Among these, monohydric alcohols are preferably saturated aliphatic alcohols having 1 to 8 carbon atoms. Specific examples of these alcohols include methanol, ethanol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol. Examples thereof include monobutyl ether and ethylene glycol monoethyl ether acetate.

  Specific examples of aromatic hydrocarbons include benzene, toluene, xylene and the like. Specific examples of ethers include tetrahydrofuran and dioxane. Specific examples of ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, Specific examples of esters such as diisobutyl ketone include ethyl acetate, propyl acetate, butyl acetate, and propylene carbonate. These organic solvents can be used alone or in combination of two or more. The concentration of the solid content relative to the solvent in the reaction is not particularly limited, but is usually in the range of 1% by mass to 90% by mass, and preferably in the range of 20% by mass to 70% by mass.

  In the hydrolysis and condensation reaction, usually 0.3 to 2 mol, preferably 0.5 to 1 mol of water is added to 1 mol of the hydrolyzable group of the organosilane, and in the presence or absence of the solvent. Under stirring and in the presence of an acid catalyst at 25-100 ° C. When the hydrolyzable group is an alkoxy group and the acid catalyst is an organic acid, since the carboxyl group or sulfo group of the organic acid supplies protons, the amount of water added can be reduced, such as the alkoxy group of organosilane. The amount of water added to 1 mol of the hydrolyzable group is 0 to 2 mol, preferably 0 to 1.5 mol, more preferably 0 to 1 mol, and particularly preferably 0 to 0.5 mol. When alcohol is used as the solvent, it is also preferred that substantially no water is added.

  The amount of the acid catalyst used is 0.01 to 10 mol%, preferably 0.1 to 5 mol%, based on the hydrolyzable group when the acid catalyst is an inorganic acid, and the acid catalyst is an organic acid. However, when water is added, the optimal amount of use is 0.01 to 10 mol%, preferably 0.1 to 5 mol%, based on the hydrolyzable group. When substantially no water is added, it is 1 to 500 mol%, preferably 10 to 200 mol%, more preferably 20 to 200 mol%, still more preferably 50 to 50 mol% with respect to the hydrolyzable group. 150 mol%, particularly preferably 50 to 120 mol%. The reaction is carried out by stirring at 25 to 100 ° C., but is preferably controlled by the reactivity of organosilane.

(Shape and molecular weight of organosilane hydrolyzate and condensation reaction product)
The organosilane hydrolyzate and condensation reaction product used in the present invention may have a chain or a three-dimensional network structure. Moreover, as for the mass average molecular weight of these compounds, it is preferable that the mass average molecular weight by conversion of ethylene glycol is 300-10000. When the mass average molecular weight is in the above range, the coating and storage stability of the curable composition are good, and the scratch resistance of the cured film can be sufficiently secured, which is preferable. The mass average molecular weight in terms of ethylene glycol is more preferably 300 to 9000, and particularly preferably 300 to 8000.
The mass average molecular weight is a molecular weight expressed in terms of ethylene glycol by DMF and differential refractometer detection using a GPC analyzer using columns of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (both trade names manufactured by Tosoh Corporation). It is.

<Fluorine-containing organosilane compound contained on the surface of the optical film of the present invention>
Hereinafter, the fluorine-containing organosilane compound contained on the surface of the optical film of the present invention will be described. The compound is not limited as long as it is an organosilane compound containing a fluorine atom, but compounds represented by the following general formulas [1] to [4] are preferable. This will be sequentially described below.

Formula _{[1] (Rf-L 1} ) n -Si (R 11) 4-n
In the above formula, Rf represents a linear, branched or cyclic fluorinated alkyl group having 1 to 20 carbon atoms or a fluorinated aromatic group having 6 to 14 carbon atoms. Rf may be further substituted with another substituent. Rf is preferably a linear, branched or cyclic fluoroalkyl group having 3 to 14 carbon atoms, and more preferably a linear fluoroalkyl group having 4 to 14 carbon atoms. L ₁ represents a divalent linking group having 10 or less carbon atoms, preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms. The alkylene group is a linear or branched, substituted or unsubstituted alkylene group which may have a linking group (for example, ether, ester, amide) inside. The alkylene group may have a substituent, and preferable substituents in that case include a halogen atom, a hydroxyl group, a mercapto group, a carboxyl group, an epoxy group, an alkyl group, and an aryl group. R ¹¹ represents an alkyl group, a hydroxyl group or a hydrolyzable group, preferably an alkoxy group having 1 to 5 carbon atoms or a halogen atom, more preferably a methoxy group, an ethoxy group, or a chlorine atom. When there are a plurality of Rf, L ₁ and R ^11, each may be the same or different. n represents an integer of 1 to 3.

Among the fluorine-containing silane compounds represented by the general formula [1], a fluorine-containing silane compound represented by the following general formula [2] is preferable.
Formula _{[2] C n F 2n +} 1 - (CH 2) m -Si (R) 3
In the above formula, n represents an integer of 10 or more, and m represents an integer of 1 to 5. R represents an alkoxy group having 1 to 5 carbon atoms or a halogen atom. n is preferably 10 to 14, m is preferably 1 to 3, and R is preferably a methoxy group, an ethoxy group, or a chlorine atom. By using the compound represented by the general formula [2], the antifouling durability is improved. In particular, it is excellent in antifouling durability after being rubbed with a cloth containing a weak alkaline detergent that may be used in daily cleaning. This is presumed to be because the fluorine-containing compound does not fall off even when rubbed under alkalinity because the surface is covered with fluorine atoms and the fixability of the fluorine-containing compound is high.

  Specific examples of the fluorine-containing silane coupling agent represented by the general formula [1] or [2] are shown below, but are not limited thereto.

_{C 3 F 7 CH 2 CH 2} Si (OC 2 H 5) 3 A-41
_{C 8 F 17 CH 2 CH 2} Si (CH 3) (OCH 3) 2 A-42
_{C 10 F 21 CH 2 CH 2} Si (OCH 3) 3 A-43
_{C 10 F 21 CH 2 CH 2} Si (OC 2 H 5) 3 A-44
_{C 12 F 24 CH 2 CH 2} Si (OCH 3) 3 A-45
_{C 14 F 29 CH 2 CH 2} Si (OCH 3) 3 A-46

  Among these specific examples, (A-43), (A-45), and (A-46) are preferable, and (A-43) is particularly preferable. These compounds can be synthesized, for example, by the method described in JP-A-11-189599.

In addition, in the present invention, a fluorine-containing silane compound containing a perfluoropolyether group is preferable from the viewpoint of improving surface lubricity in addition to antifouling properties. The compounds having preferred structures will be sequentially described below.
General formula [3]

Wherein R _f is a linear or branched perfluoroalkyl group having 1 to 16 carbon atoms, X is an iodine atom or a hydrogen atom, Y is a hydrogen atom or a lower alkyl group, Z is a fluorine atom or a trifluoromethyl group. , R ¹ is a hydrolyzable group, R ² is hydrogen or an inert monovalent organic group, a, b, c, d are integers of 0 to 200, e is 0 or 1, and m and n are 0 to 0. (The integer of 2 and p represent the integer of 1-10.)
R _f in the general formula [3] is usually a linear or branched perfluoroalkyl group having 1 to 16 carbon atoms, preferably a CF ₃ group, a C ₂ F ₅ group, or a C ₃ F ₇ group. is there. Examples of the lower alkyl group for Y usually include those having 1 to 5 carbon atoms. Examples of the hydrolyzable group for R ¹ include halogen atoms such as chlorine atom, bromine atom and iodine atom, R ³ O group, R ³ COO group, (R ⁴ ) ₂ C═C (R ³ ) CO group, ( R ³ ) ₂ C═NO group, R ⁵ C═NO group, (R ⁴ ) ₂ N group, and R ³ CONR ⁴ group are preferred. (Wherein, R ³ is usually generally aromatic hydrocarbon group having 6 to 20 carbon atoms and an aliphatic hydrocarbon group or a phenyl group having 1 to 10 carbon atoms such as an alkyl group, R ⁴ is a hydrogen atom or an alkyl Group is usually a lower aliphatic hydrocarbon group having 1 to 5 carbon atoms, and R ⁵ is usually a divalent aliphatic hydrocarbon group having 3 to 6 carbon atoms such as an alkylidene group.) More preferably, chlorine An atom, a CH ₃ O group, and a C ₂ H ₅ O group. R ² is a hydrogen atom or an inert monovalent organic group, and is preferably a monovalent hydrocarbon group usually having 1 to 4 carbon atoms such as an alkyl group. a, b, c and d are integers of 0 to 200, preferably 1 to 50. m and n are integers of 0 to 2, preferably 0. p is an integer of 1 or 2 or more, preferably an integer of 1 to 10, and more preferably an integer of 1 to 5. The number average molecular weight is preferably 5 × 10 ² to 1 × 10 ^5, more preferably 1 × 10 ³ to 1 × 10 ⁴ .

Further, as a preferable structure of the fluorine-containing silane compound represented by the general formula [3], R _f is C ₃ F ₇ group, a is an integer of 1 to 50, b, c and d Is 0, e is 1, Z is a fluorine atom, n is 0, and p is 2 to 10, that is, a compound represented by the following general formula [4].
General formula [4]

(In the formula, Y, m and R ¹ represent the same meaning as described above, q represents an integer of 1 to 50, and p represents an integer of 2 to 10).
In the present invention, in order to improve antifouling durability, particularly antifouling durability after rubbing with an alkaline detergent, p is preferably 2 or more, and most preferably 3 or more. It is presumed that the durability is improved when the fluorine-containing ether compound is bonded to the matrix body by a plurality of bonding groups having p of 2 or more.

  These fluorine-containing silane compounds can be obtained by treating a commercially available perfluoropolyether with silane. For example, as disclosed in JP-A-1-294709.

A compound having a perfluoropolyether group represented by the following general formula is also preferable because of its excellent antifouling property.
General formula [5]
_{^{Rf 5 [- (L 5)}} n -X-R 51 -Si (OR ⁵² ) ₃ ] _m
(Wherein Rf ⁵ represents a perfluoropolyether group, R ⁵¹ The alkylene group, the R ⁵² is an alkyl group, L ₅ is a -CO-, X is ^{-O -, - NR 53 -,} - S -, - SO 2 -, - SO 2 NR 53 over, -NR ⁵³ In the group selected from CO-, n represents 0 or 1, and m represents a natural number of 2 or less. R ⁵³ represents a hydrogen atom or an alkyl group having 3 or less carbon atoms. )
Of the perfluoropolyether groups Rf ^{5 in} the general formula [5], examples of monovalent ones include the following general formulas [51], [52], and [53]. There is no limit. Moreover, a bivalent thing may be sufficient. In this case, an alkoxysilane compound is bonded to both ends of the Rf ⁵ group. The molecular weight of the perfluoropolyether group is not particularly limited, but from the viewpoint of stability and ease of handling, a number average molecular weight of 500 to 10,000, more preferably 500 to 2,000 is used. .
Formula [51] F (CF ₂ CF ₂ CF ₂ O) _j −
Formula [52] CF ₃ (OCF (CF ₃ ) CF ₂ ) _m (OCF ₂ ) _l −
Formula [53] F (CF (CF ₃ ) CF ₂ O) _k −
Here, j, k, l and m in the general formula [51], [52] or [53] represent a natural number of 1 or more.
Specific examples of preferred compounds are described in, for example, JP-A-10-148701.

Moreover, the compound of the following general formula is mentioned as an organosilazane compound with high reactivity in the case of hardening.
General formula [6]
_{[C n F 2n + 1 C} m H 2m Si (CH 3) 2] 2 -NH
In the formula, n is an integer of 4 or more, and m is 2 or 3. Examples of such a disilazane compound include the following.
_{[C 4 F 9 C 2 H 4} (CH 3) 2 Si ] ₂ NH
_{[C 4 F 9 C 3 H 6} (CH 3) 2 Si ] ₂ NH
[C ₈ F ₁₇ C ₂ H ₄ (CH ₃ ) ₂ Si] ₂ NH
[C ₈ F ₁₇ C ₃ H ₆ (CH ₃ ) ₂ Si] ₂ NH
_{[C 8 F 17 C 3 H 6} (CH 3) (C 2 H 5) Si ] ₂ NH
_{[C 10 F 21 C 3 H 6} (CH 3) 2 Si ] ₂ NH
These compounds are used alone or in combination. These are disclosed in JP-A-10-26703.

  In the present invention, as the fluorine compound to be used, the alkoxysilane compound having a perfluoropolyether group represented by the above general formulas [3] to [5] is more resistant to abrasion than a compound having a simple perfluoroalkyl group. From the viewpoint of properties and water repellency. The reason for this is not necessarily clear, but it is conceivable that there is a considerable interaction between fluorine compound groups, or that the interaction between the alkoxysilane compound group, which is a polar group, and the underlying layer changes.

  Further, it is preferable to use the compounds described in JP 2000-191977 A, JP 2000-204319 A, JP 2000-328001 A, etc. as the high-molecular fluorine-containing silane compound since there are few coating failures.

(Method of placing a fluorine-containing silane compound on an optical film)
The fluorine-containing silane compound of the present invention may be contained in the same coating composition together with the above-described conductive particles of the present invention and the organosilane compound, hydrolyzate, or condensate to form a coating film. You may provide as another antifouling layer on the layer containing the electroconductive particle of invention. Moreover, both methods can also be used together. The method of containing in the same coating composition has high productivity because it is not necessary to provide a new antifouling layer. Moreover, when providing as a new antifouling layer, even if it uses a slightly soluble fluorine-containing silane compound, it can be used by methods, such as a vacuum evaporation without a solvent, using a solvent for exclusive use. In terms of improving antifouling durability, it is preferable to add to the antifouling layer.

The fluorine-containing silane compound is preferably excellent in the stability of the coated surface because it is partially condensed in advance with the organosilane compound of the present invention. In addition, it is particularly preferable from the viewpoint of antifouling durability to use an organosilane compound represented by the following general formula [7] in the fluorine-containing organosilane compound-containing layer.
General formula [7]
R ⁷¹ -Si (OR ⁷² ₃
(Where R ⁷¹ Represents a long-chain hydrocarbon group having 10 or more carbon atoms, and R ⁷² represents an alkyl group. Long chain hydrocarbon group R ⁷¹ Are preferably those having 10 or more carbon atoms, whether linear or branched. Further, it may contain an unsaturated bond or a cyclic structure such as an aromatic ring. However, a straight chain is preferably selected in the range of 12 to 20 carbon atoms. With this molecular design, the alkoxysilano group portion of the general formula (7) can interact with the SiO _{2 of the} antireflection layer and the long chain hydrocarbon group R71. The water repellency of the part is increased, and the intermolecular interaction between the water-repellent groups, that is, the van der Waals force is increased. By using this together with the alkoxysilane compound having a perfluoropolyether group represented by the general formulas [3] to [5], these effects are synergized, and the solvent resistance, water repellency and wear resistance are large. Improved.

When the fluorine-containing silane compound is used for the antifouling layer, the ratio of the fluorine-free organosilane to 100 parts by mass of the fluorine-containing organosilane compound is preferably 1 part by mass or more and 150 parts by mass or less, more preferably 1 part by mass or more. 50 parts by mass. By setting it within this range, antifouling properties and scratch resistance are excellent.
In the optical film of the present invention, it is also preferred that the layer containing conductive particles whose inside is porous or hollow contains a fluorine-containing silane compound and that the layer is the outermost layer.

<Coating composition of layer containing conductive particles of the present invention>
The layer containing the conductive particles of the present invention is preferably formed using a coating composition containing the particles, the organosilane compound of the present invention, and optionally the fluorine-containing silane compound of the present invention. Specific film forming methods include spin coating, dip coating, roll coating coating, gravure coating coating, curtain flow coating, and die coating coating.

(Surface modification of conductive particles)
The conductive particles of the present invention can be subjected to surface treatment as necessary from the viewpoints of stability in a coating solution, improvement in conductivity of a coating film, and improvement in coating film strength. In the present invention, there are roughly classified a method of treating with a compound that forms a covalent bond with the particle surface and a method of treating with a compound that does not form a covalent bond.

The compound that does not form a covalent bond is not particularly limited, but preferably includes a nonionic surfactant having an HLB value of 4 or less or 10 or more, a cationic surfactant having a linear alkyl group, and the like. .
Basic low molecular amines are also preferred dispersants because of their high conductivity of the coating film.

The compound that forms a covalent bond with the particle surface preferably includes a silane coupling agent and a titanate coupling agent. 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.
Specific examples of the compound include the fluorine-free or fluorine-containing organosilane compound of the present invention described above. In the present invention, an organosilane compound having a (meth) acryloyl group, an epoxy group, an oxetanyl group, or a fluorine-substituted alkyl group is particularly preferable. Although there is no restriction | limiting in particular in the usage-amount of a silane coupling agent, 1 mass%-300 mass% per electroconductive particle are preferable, More preferably, they are 1 mass%-100 mass%, Most preferably, they are 3 mass%-50 mass%. is there.
When the amount of the organosilane compound used is in the above range, a sufficient stabilizing effect of the dispersion can be obtained, and the strength of the coating film can be increased and high conductivity can be obtained.

(Solvent for coating composition)
The conductive particles according to the present invention described above can be combined with a binder and, if necessary, a diluent solvent to form a coating composition, and each layer of the optical film can be formed from this composition. Although there is no restriction | limiting in the solvent of a coating composition, It is preferable to contain at least 2 type of volatile solvent. For example, it is preferable to use a combination of at least two selected from alcohol and derivatives thereof, ethers, ketones, hydrocarbons, and esters. A solvent can be selected from the viewpoint of the solubility of the binder component, the stability of the inorganic fine particles, and the adjustment of the viscosity of the coating liquid. The boiling point of the solvent used in the present invention is preferably 50 ° C. or higher and 250 ° C. or lower, more preferably 65 ° C. or higher and 200 ° C. or lower. Further, the preferable dielectric constant is preferably 1 or more and 50 or less, more preferably 5 or more and 30 or less at 20 ° C. It is preferable in view of dispersion stability that a solvent having a dielectric constant of 10 or more is contained in an amount of 10% by mass or more based on the conductive fine particles.

Although the solvent which can be used for this invention below is mentioned, it is not limited to these.
Alcohol and its derivatives (methanol, ethanol, n-propanol, isopropyl alcohol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-amyl alcohol, isoamyl alcohol, sec amyl alcohol, 3-pentanol , Tertiary amyl alcohol, n-hexanol, methyl amyl alcohol, 2-ethylbutanol, n-heptanol, 2-heptanol, 3-heptanol, n-octanol, 2-octanol, 2-ethylhexanol, 3,5,5- Trimethylhexanol, nonanol, benzyl alcohol, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether, ethylene glycol Diethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol isopropyl ether, ethylene glycol monobutyl ether, ethylene glycol dibutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol isoamyl ether, methoxymethoxyethanol, methoxypropanol, butoxyethanol, ethylene glycol Monoacetate, ethylene glycol diacetate, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol Mono butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether)

・ Ethers (isopropyl ether, n-butyl ether, diisoamyl ether, methylphenyl ether, ethylphenyl ether)
Ketones (acetone, methylacetone, methylethylketone, methyl-n-propylketone, methyl-n-butyl, methylisobutylketone, methyl-n-amylketone, methyl-n-hexylketone, diethylketone, ethyl-n-butylketone, Di-n-propyl ketone, diisobutyl ketone, acetonyl acetone, diacetone alcohol, cyclohexanone, methylcyclohexanone)

Hydrocarbons (n-hexane, isohexane, n-heptane, n-octane, isooctane, n-decane, toluene, xylene, ethylbenzene, diethylbenzene, isopropylbenzene, amylbenzene)
Esters (propyl formate, n-butyl formate, isobutyl formate, amyl formate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, n-amyl acetate) , Isoamyl acetate, methyl isoamyl acetate, methoxybutyl acetate, secondary hexyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, cyclohexyl acetate, methyl cyclohexyl acetate, benzyl acetate, methyl propionate, ethyl propionate , N-butyl propionate, isoamyl propionate, methyl butyrate, ethyl butyrate, n-butyl butyrate, isoamyl butyrate, ethyl oxyisobutyrate, methyl acetoacetate, ethyl acetoacetate, isoamyl isovalerate, methyl lactate, ethyl lactate, Lactic acid-n-butyl, isobutyl lactate, milk -n- amyl lactate, isoamyl, methyl benzoate, diethyl oxalate)

  A particularly preferred combination is the use of at least two, more preferably three, of alcohol and its derivatives, ketones and esters. As a preferable example, for example, two or three of methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, butyl acetate, 2-methoxypropanol, 2-butoxyethanol, isopropyl alcohol, methyl alcohol, and ethyl alcohol are used in combination. Can do.

<Stain of antifouling layer>
The fluorine-containing silane compound of the present invention can also be contained in an antifouling layer that can be provided on the layer containing the conductive particles of the present invention. When the antifouling layer is formed by coating, it is preferable to dilute with a solvent from the viewpoint of controlling the thickness of the layer comprising the fluorine silane compound and from the viewpoint of workability. Examples of the solvent include perfluoroaliphatic hydrocarbons usually having 5 to 12 carbon atoms such as perfluorohexane, perfluoromethylcyclohexane, perfluoro-1,3-dimethylcyclohexane, and bis (trifluoromethyl) benzene. Examples thereof include polyfluorinated aromatic hydrocarbons and polyfluorinated aliphatic hydrocarbons. The concentration of the fluorine silane compound in the coating solution is preferably 0.05 to 0.5% by mass.

<Coating method of coating film>
The layer containing the conductive particles of the present invention is formed by applying a coating composition on a support and then evaporating and curing the solvent. The curing conditions vary depending on the organosilane compound and catalyst used, but a range of 20 ° C to 200 ° C is usually preferable. More preferably, it is 60 degreeC-140 degreeC, Most preferably, it is 80 degreeC-110 degreeC. By setting it in the above range, a sufficient curing rate can be obtained and damage to the support can be reduced. The curing time is not particularly limited, but for example, it is usually preferably 1 hour to 50 hours at 60 ° C, and preferably 1 minute to 30 minutes at 140 ° C. As the curing catalyst, it is preferable to use the acid described in the above-mentioned catalyst for hydrolysis of organosilane.
The curing conditions for the antifouling layer are the same as above. The antifouling layer may be applied and cured after the adjacent lower layer has been cured, but it can also be applied and cured after it has been cured or partially cured, thereby improving the fixing property of the fluorine-containing silane compound and thus preventing the antifouling property. Improved and preferred.
Moreover, when the radically polymerizable compound represented by polyfunctional acrylate is contained in the lower surface of the layer containing electroconductive particle, it can also irradiate with ionizing radiation before the said thermosetting. The interface bond between both layers is strengthened, and the scratch resistance of the coating film is improved. The materials that can be used for the lower layer will be described later on page 1- (1) Binder.

<Composition / physical properties of coating film>
In the layer containing the conductive particles of the present invention, the volume fraction occupied by the conductive particles is preferably 15% or more and 90% or less, more preferably 30% or more and 80% or less, and most preferably 40% or more and 70%. It is as follows. By setting the content in the above range, the conductivity and scratch resistance can be set in a preferable range.
In the layer containing the conductive particles, the volume fraction of the component obtained by curing the hydrolyzate and / or condensation reaction product of the organosilane compound of the present invention among components other than the conductive particles is 5%. It is preferably 100% or less and more preferably 10% or more and 100% or less.
When the fluorine-containing silane compound of the present invention is used in the same layer as the conductive particles of the present invention and the organosilane compound of the present invention, the fluorine-containing silane compound is in an amount of 0. It is preferably used in an amount of from 01% by mass to 50% by mass, more preferably from 0.1% by mass to 20% by mass, and most preferably from 0.2% by mass to 10% by mass.
Moreover, another inorganic fine particle can also be used together for the layer containing the electroconductive particle of this invention. For example, the refractive index can be lowered by using porous or hollow particles which do not contain a conductive component, which will be described later, and the scratch resistance of the coating film can be increased by using general-purpose silica particles having a dense inside. Can be improved. Specific materials will be described later in the <low refractive index particles> page.

  The composition of the coating composition can be used by mixing each component so that the above composition is obtained after the film is cured. The solid content concentration of the coating composition is preferably 1% by mass or more and 10% by mass, and more preferably 1% by mass or more and 5% by mass or less.

  There is no restriction | limiting in particular in the thickness of the layer containing the electroconductive particle of this invention, When using for a hard-coat layer, 0.1 to 50 micrometer is preferable, More preferably, it is 1.0 to 20 micrometer. When used for the low refractive index layer, the thickness is preferably from 30 nm to 500 nm, more preferably from 70 nm to 500 nm. From the viewpoint of increasing conductivity, the thickness of the low refractive index layer is preferably 130 nm or more and 500 nm or less, and most preferably 230 nm or more and 330 nm or less.

  The refractive index of the layer using the conductive particles of the present invention is not particularly limited, and can be a refractive index required for the layer to be used. When used for the low refractive index layer, it is preferably 1.30 or more and 1.48 or less, more preferably 1.35 or more and 1.46 or less, and most preferably 1.35 or more and 1.45 or less. By making the refractive index within this range, it is possible to achieve both reduction in reflectance and conductivity.

  When the antifouling layer containing the fluorine-containing silane compound of the present invention is provided, the thickness of the layer is preferably from 0.5 nm to 150 nm, and more preferably from 1.0 nm to 10 nm. When the layer immediately below the antifouling layer contains a compound containing a fluorine atom, the antifouling layer may be able to impart the antifouling property that is the object of the present invention without necessarily forming a uniform layer.

(Elemental composition of the surface of the optical film)
The elemental composition of the surface of the optical film of the present invention is such that the peak area ratio (Si2p / F1s) of silicon atoms (Si2p) and fluorine atoms (F1s) on the surface measured by X-ray photoelectron spectroscopy described below is 0.0. It is preferable that it is 0.4 or more. More preferably, it is 0.0 or more and 0.3 or less, and most preferably 0.05 or more and 0.15 or less. The smaller this ratio, the greater the ratio of fluorine atoms to silicone atoms on the film surface, and a reduction in surface free energy is expected.
In the present invention, the peak area ratio was measured with “ESCA-3400” manufactured by Shimadzu Corporation (vacuum degree 1 × 10 ⁻⁵ Pa, X-ray source; target Mg, voltage 12 kV, current 20 mA). It is defined as that calculated using the area of the photoelectron spectrum of the surface Si2p and F1s.

(Surface resistance of optical film)
The surface resistance of the optical film is preferably 10 ⁵ to 10 ¹² Ω / sq, more preferably 10 ⁶ to 10 ¹¹ Ω / sq, and most preferably 10 ⁷ to 10 ¹⁰ Ω / sq. . The surface resistance of the antistatic layer can be measured by a four-probe method at 25 ° C. and 60% RH.

(Contact angle of optical film)
The contact angle of the film of the present invention is preferably 95 degrees or more with respect to pure water. The angle is more preferably 100 degrees or more, and most preferably 105 degrees or more. For example, it can be measured as follows.
Using a contact angle meter ['CA-V' type contact angle meter, manufactured by Kyowa Interface Science Co., Ltd.], in a dry state (25 ° C./60% RH), using pure water as the liquid, 2 μl droplets were Made on the surface of 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.

(Surface free energy of optical film)
The surface energy can be obtained by a contact angle method, a wet heat method, and an adsorption method as described in “Basics and Applications of Wetting”, Realize, Inc., 1989.12.10. In the case of the film of the present invention, it is preferable to use a contact angle method.
Specifically, two types of solutions with known surface energies are dropped, and at the intersection of the droplet surface and the film surface, the tangent drawn to the droplet and the angle formed by the film surface contain the droplet. Is defined as the contact angle, and the surface energy of the film can be calculated by calculation.

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. , Referring to 13,1741 (1969), the value represented by the sum of gamma] s ^d and gamma] s ^h determined from the respective contact angles of pure water H2O and methylene iodide CH2I2 determined experimentally on the optical film gamma] s ^v It represents the surface tension defined by (= γs ^d + 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.
The contact angle was measured at 25 ° C. and 60% RH for 30 seconds after a 2 μl droplet was dropped on the film using an automatic contact angle meter CA-V type manufactured by Kyowa Interface Science Co., Ltd. Later, the contact angle was determined.
The surface free energy of the optical film of the present invention is preferably 25 mN / m or less, more preferably 20 mN / m.

(Dynamic friction coefficient of optical film)
A dynamic friction coefficient can be used as an index of surface slipperiness. The optical film of the present invention is preferably 0.02 or more and 0.30 or less, more preferably 0.02 or more and 0.25 or less, and most preferably 0.05 or more and 0.20 or less. By setting it within the above range, the antifouling property and scratch resistance can be kept good.
As the dynamic friction coefficient, a sample was conditioned at 25 ° C. and 60% RH for 24 hours, and then a value measured with a HEIDON-14 dynamic friction measuring machine at a 5 mmφ stainless steel ball, a load of 100 g, and a speed of 60 cm / min was used.

1. First, the various compounds that can be used in the film of the present invention will be described.

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

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

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

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

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

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

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

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

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

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

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

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

1- (3) Organosilane Compound The film of the present invention contains an organosilane compound, a hydrolyzate of the organosilane compound and / or a partial condensate thereof (hereinafter referred to as “sol component”). From the viewpoint of scratch resistance.
These compounds function as a binder by applying a curable composition and then condensing in a drying and heating process to form a cured product. Specific compounds that can be used in the conductive particle-containing layer of the present invention are represented by the compound represented by the general formula (B).

In this invention, the usage-amount of the organosilane compound represented by general formula (B) is demonstrated.
(A) When used for surface treatment of inorganic fine particles Although there is no particular limitation, it is preferably 1% by mass to 300% by mass, more preferably 3% by mass to 100% by mass, and most preferably 5% by mass per inorganic oxide fine particle. -50 mass%. It is preferably 1 to 300 mol%, more preferably 5 to 300 mol%, and most preferably 10 to 200 mol% per normal concentration (Formol) based on hydroxyl groups on the surface of the inorganic oxide.
When the amount of the organosilane compound used is in the above range, a sufficient stabilizing effect of the dispersion can be obtained, and the film strength is also increased during coating film formation. It is also preferable to use a plurality of types of organosilane compounds in combination, and a plurality of types of compounds can be added at the same time, or the reaction can be carried out by shifting the addition time. Also, it is preferable to add a plurality of kinds of compounds in the form of partial condensates in advance because the reaction control is easy.
(B) When used for the constituent layer of the optical film 0.1 to 90% by mass of the total solid content of the constituent layer of the optical film is preferable, 0.5 to 30% by mass is more preferable, and 1 to 20% by mass is the most. preferable.
The organosilane compound may be added directly to the curable composition (coating liquid for antiglare layer, low refractive index layer, etc.), but the organosilane compound is treated in the presence of a catalyst in advance to prepare the organosilane compound. It is preferable to prepare a hydrolyzate and / or partial condensate of a silane compound and prepare the curable composition using the obtained reaction solution (sol solution). In the present invention, first, the organosilane compound A composition containing a hydrolyzate and / or a partial condensate and a metal chelate compound is prepared, and a liquid obtained by adding a β-diketone compound and / or a β-ketoester compound thereto is added to at least an antiglare layer or a low refractive index layer. It is preferable to coat it in a single layer coating solution.

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

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

  Examples of benzoins include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyl dimethyl ketal, benzoin benzene sulfonate, benzoin toluene sulfonate, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether It is. Examples of benzophenones include benzophenone, hydroxybenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 2,4-dichlorobenzophenone, 4,4-dichlorobenzophenone and p-chlorobenzophenone, 4,4′-dimethylaminobenzophenone (Michler'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 Kayo Kiyomi, 1989, General Technology Center, p. Various examples are also described in 65-148 and are useful in the present invention.

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

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

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

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

  In the present invention, in addition to the thermal acid generator 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 sulfonic acid esters, haloalkyl sulfonic acid esters, aryl sulfonic acid esters and imino sulfonates; (4) sulfonimide compounds; (5) diazomethane compounds Others can be mentioned and can be used as appropriate.

  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.

The use ratio of the photosensitive acid generator 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 resin composition.
In addition, as specific compounds and methods of use, for example, the contents described in JP-A-2005-43876 can be used.

1- (5) Translucent Particles Various translucent particles are used for imparting antiglare properties (surface scattering properties) and internal scattering properties to the film of the present invention, particularly the antiglare layer and the hard coat layer. I can do it.

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) and translucent particles in the present invention is preferably 1.45 to 1.70, more preferably 1.48 to 1.65. In order to set the refractive index within the above range, the type and amount ratio of the binder and the light-transmitting particles may be appropriately selected. How to select can be easily known experimentally in advance.
In the present invention, the difference in refractive index between the binder and the translucent particles (the refractive index of the translucent particles−the refractive index of the binder) is preferably 0.001 to 0.030 as an absolute value, More preferably, it is 0.001-0.020, More preferably, it is 0.001-0.015. 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 diameter of the translucent particles is preferably 0.5 to 20 μm, more preferably 2.0 to 15.0 μm. When the average particle size is 0.5 μm or more, the scattering angle distribution of light does not spread to a wide angle, which is preferable because character blur of the display is not caused. On the other hand, when the thickness is 20 μm or less, it is not necessary to increase the thickness of the layer to be added, which is preferable in terms of curling and cost.

  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.

  It is preferable from the viewpoints of image blur, surface turbidity, glare and the like that the translucent particles are blended so as to be 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%.

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, emulsion polymerization, soap-free emulsion polymerization, dispersion polymerization, seed polymerization, 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. 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.

1- (6) Inorganic particles Various inorganic particles can be used in the present invention in order to improve physical properties such as hardness, optical properties such as reflectance, and scattering properties.
As the inorganic particles, an oxide of at least one metal selected from silicon, zirconium, titanium, aluminum, indium, zinc, tin, and antimony, specific examples include ZrO ₂ , TiO ₂ , Al ₂ O ₃ , In ₂ O ₃ , ZnO, SnO ₂ , Sb ₂ O ₃ , ITO and the like can be mentioned. 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 the mass average diameter is 1 to 200 nm. Preferably it is 5-150 nm, More preferably, it is 10-100 nm, Most preferably, it is 10-80 nm. A film that does not impair the transparency can be formed by refining the inorganic particles to 100 nm or less. The particle diameter of the inorganic particles can be measured by a light scattering method or an electron micrograph.

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

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

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

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

As the TiO ₂ particles, inorganic particles mainly containing TiO ₂ containing at least one element selected from cobalt, aluminum, and zirconium are particularly preferable. The main component means a component having the largest content (mass%) among the components constituting the particles.
The particles mainly composed of TiO ₂ in the present invention preferably have a refractive index of 1.90 to 2.80, more preferably 2.10 to 2.80, and 2.20 to 2.80. Most preferably.
The 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 the particles containing TiO ₂ as a main component, the photocatalytic activity of TiO 2 can be suppressed, and the present invention. The weather resistance of the film can be improved.
A particularly preferable element is Co (cobalt). It is also preferable to use two or more types in combination.
The inorganic particles mainly composed of TiO ₂ of the present invention may have a core / shell structure by surface treatment as described in JP-A No. 2001-166104.

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

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

  It is preferable to make the average particle diameter of the silica fine particles in the above range from the viewpoint of the effect of improving the scratch resistance, the fine irregularities on the surface of the low refractive index layer, the appearance such as black tightening, the integrated reflectance, and the like. 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} . The above range is preferable from the viewpoints of the effect of improving the scratch resistance, the fine irregularities on the surface of the low refractive index layer, the appearance of black tightening, the integrated reflectance, and the like.

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

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

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

The coating amount of the hollow silica is ^preferably from ^{1mg / m 2 ~100mg / m 2} , more preferably ^{5mg / m 2 ~80mg / m 2} , more preferably from ^{10mg / m 2 ~60mg / m 2} . The above range is preferable from the viewpoints of the effect of improving the scratch resistance, the fine irregularities on the surface of the low refractive index layer, the appearance of black tightening, the integrated reflectance, and the like.
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- (7) Conductive Particles Various conductive particles can be used for imparting conductivity to the film of the present invention. The usable particles are described in, for example, JP-A-2005-196122.

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

  Preferable examples of the fluorosurfactant include a fluoroaliphatic group-containing copolymer (sometimes abbreviated as “fluorine polymer”), and the fluoropolymer includes the following monomer (i): An acrylic resin, a methacrylic resin, and a vinyl monomer copolymerizable with the acrylic resin, the methacrylic resin characterized by containing a corresponding repeating unit, or a repeating unit corresponding to the monomer (ii) below: Copolymers are useful.

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

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) a monomer represented by the following general formula (b) copolymerizable with the above (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 groups such as cyclohexyl group, cycloheptyl group and bicycloheptyl group, bicyclodecyl group, tricycloundecyl group, A polycyclic cycloalkyl group such as a tetracyclododecyl group, an adamantyl group, a norbornyl group, a tetracyclodecyl group, or the like is preferably used.

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

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

1- (9) Thickener

The film of the present invention may use a thickener to adjust the viscosity of the coating solution.
The term “thickener” as used herein means that the viscosity of the liquid is increased by adding it, and preferably 0.05 to 50 cP (0. 05 to 50 mPa.s), more preferably 0.10 to 20 cP (0.1 to 20 mPa.s), and most preferably 0.10 to 10 cP (0.10 to 10 mPa.s).

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

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

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

  Examples of the solvent having a boiling point of 100 ° C. or lower include hydrocarbons such as hexane (boiling point 68.7 ° C.), heptane (98.4 ° C.), cyclohexane (80.7 ° C.), benzene (80.1 ° C.), Halogenated carbonization such as dichloromethane (39.8 ° C), chloroform (61.2 ° C), carbon tetrachloride (76.8 ° C), 1,2-dichloroethane (83.5 ° C), trichloroethylene (87.2 ° C) Hydrogens, diethyl ether (34.6 ° C), diisopropyl ether (68.5 ° C), dipropyl ether (90.5 ° C), 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.

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

1- (12) 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 hydroxyl groups at 2, 3, and 6 positions 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.

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

2- (1) Antiglare Layer The antiglare layer is formed for the purpose of contributing to the film antiglare properties due to surface scattering and preferably hard coat properties 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 preferably contains a binder capable of imparting hard coat properties, translucent particles for imparting antiglare properties, and a solvent as essential components. It is preferable that irregularities on the surface be formed by the protrusions of the protrusions themselves or protrusions formed by an aggregate of a plurality of particles.
The antiglare layer formed by dispersing the matte particles 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.

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 matte particles is measured by a Coulter counter method, and the measured distribution is converted into a particle number distribution.

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

The translucent particles may be blended in the formed anti-glare layer so as to be contained in an amount of 3 to 30% by mass in the total solid content of the anti-glare layer. From the viewpoint of the above. More preferably, it is 5-20 mass%. If it is less than 3% by mass, the antiglare property is insufficient, and if it exceeds 30% by mass, problems such as image blur, surface turbidity and glare occur.
The density of the translucent particles is preferably 10 to 1000 mg / m ² , more preferably 1
It is a 00~700mg / 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. If this difference exceeds 0.040, problems such as film character blur, dark room contrast reduction, and surface turbidity occur.
Here, the refractive index of the translucent resin 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 light-transmitting particles is measured by measuring the turbidity by equally dispersing the light-transmitting particles in the solvent in which the refractive index is changed by changing the mixing ratio of two kinds 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 pixels are enlarged or reduced due to unevenness present on the surface of the antiglare and antireflection antireflection film, resulting in loss of luminance uniformity, but particles smaller than mat particles that impart antiglare properties. It can be greatly improved by using mat particles having a diameter different from that of the binder.

  The 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. If it exceeds 0.40 μm, problems such as glare and whitening of the surface when external light is reflected occur. 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.

2- (2) Hard Coat Layer In addition to the antiglare layer, the film of the present invention can be provided with a hard coat layer in order to impart the physical strength of the film.
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, since 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 the reflected light tends to be strong. is there.

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

  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.

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

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

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

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

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

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

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

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

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

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

2- (4) Low Refractive Index Layer In order to reduce the reflectance of the film of the present invention, a low refractive index layer can be used. 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 30 to 500 nm, and more preferably 70 to 500 nm. In order to impart conductivity, it is preferable that the low refractive index layer has a thickness of 130 to 500 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.

2- (5) Antistatic layer, conductive layer In the present invention, in addition to a layer containing conductive particles in which the inside of the particle is porous or hollow, an antistatic layer may be provided to prevent static electricity on the film surface. This is preferable. 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 and a conductive polymer such as polythiophene or polyaniline can be mentioned. 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.

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.

2- (6) 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 layer 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.

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

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

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

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

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

2- (8) Anti-curl Layer The film of the present invention can be subjected to anti-curl processing. The anti-curl processing is to give the function of trying to curl with the surface to which it is applied inside, but by applying this processing, some surface processing is performed on one side of the transparent resin film and both sides are processed. When surface treatments of different degrees and types are applied, it functions to prevent curling with the surface facing inward.
The anti-curl layer may be provided on the side opposite to the side having the anti-glare 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.

2- (9) 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, similarly to the barrier layer, or nanoparticles may be prepared by various methods. The thickness of the layer is preferably 1 to 100 nm, and more preferably 1 to 10 nm. The layer containing the water absorbent is between the support and the laminate (a laminate of the barrier layer and the organic layer), between the uppermost layer of the laminate, between the laminates, or in the organic layer or barrier layer in the laminate. It may be added. When added to the barrier layer, a co-evaporation method is preferably used.

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

3. Layer structure of film About the film of this invention, a well-known layer structure can be used using the above layers. For example, the following are typical examples.
a. Support / 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)

As shown in b (FIG. 1), when a hard coat layer is applied on a support and a low refractive index layer is laminated, it can be suitably used as an antireflection film. By forming the low refractive index layer on the hard coat layer with a film thickness of about 1/4 of the wavelength of light, surface reflection can be reduced by the principle of thin film interference.
Moreover, even if a high-refractive index layer and a low-refractive index layer are laminated after applying a hard coat layer on a support as shown in FIG. 2 (c), it can be suitably used as an antireflection film. Further, by installing a layer structure in the order of a support, a hard coat layer, a medium refractive index layer, a high refractive index layer, and a low refractive index layer as shown in d (FIG. 3), the reflectance is 1% or less. can do.

  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 dispersion of matte particles 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 dispersing the matte particles 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, interference unevenness (rainbow unevenness) prevention layer, antistatic layer (reduction of surface resistance value from the display side, etc.) may be provided between the support and the surface layer or the outermost layer. , If there is a problem with dust on the surface, etc.), another hard coat layer (when 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

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

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

<Physical properties of coating solution>
In the coating method of the present invention, the upper limit speed at which coating is possible is greatly affected by the liquid physical properties, so it is necessary to control the liquid physical 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 transparent support body also affects the upper limit speed | rate which can be apply | coated. The amount of the coating solution applied to the transparent support is 2.0 to 5.0 [cm ³
/ M ² ]. Increasing the amount of the coating liquid applied to the transparent support is preferable because the upper limit of the application rate can be increased, but if the amount of the coating liquid applied to the transparent support is increased too much, the load on drying increases. It is preferable to determine the optimal amount of coating liquid to be applied to the transparent support depending on the liquid formulation and process conditions.
The surface tension is preferably in the range of 15 to 36 [mN / m]. It is preferable to reduce the surface tension by adding a leveling agent or the like because unevenness during drying is suppressed. On the other hand, if the surface tension is too low, the upper limit speed at which coating can be performed is reduced. Therefore, a range of 17 [mN / m] to 32 [mN / m] is more preferable, and 19 [mN / m] to 26 [mN / m]. mN / m] is more preferable.

<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 is mentioned.
It is also preferable to ultrasonically disperse the filtered coating solution immediately before coating to assist defoaming and dispersion holding of the dispersion.

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

Furthermore, as a dust removing method used in the dust removing step as a pre-process for application, a method of pressing a nonwoven fabric, a blade or the like on the film surface described in JP-A-59-150571, JP-A-10-309553 A method of blowing the air with high cleanliness described at a high speed to peel off the deposits from the film surface and sucking it with a suction port close to it, blowing compressed air that is ultrasonically vibrated as described in JP-A-7-333613 Examples thereof include a dry dust removing method such as a method for peeling and sucking adhered substances (manufactured by Shinkosha, New Ultra Cleaner, etc.).
In addition, a method of introducing a film into a cleaning tank and peeling off deposits with an ultrasonic vibrator, supplying a cleaning liquid to the film described in Japanese Patent Publication No. 49-13020, and then blowing and sucking high-speed air As described in JP-A-2001-38306, a wet dust removal method such as a method in which a web is continuously rubbed with a roll wetted with 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 support (preferably a cellulose acylate film) in these treatments is preferably Tg or less, specifically 150 ° C. or less.
When the cellulose acylate film is adhered to the polarizing film as in the case of using the film of the present invention as a protective film for a polarizing plate, from the viewpoint of adhesiveness to the polarizing film, acid treatment or alkali treatment, that is, cellulose acylate. It is particularly preferred to carry out a saponification treatment on the rate.
From the viewpoint of adhesiveness and the like, the surface energy of the cellulose acylate film is preferably 55 mN / m or more, more preferably 60 mN / m or more and 75 mN / m or less, and it can be adjusted by the surface treatment. .

4- (3) Coating Each layer of the film of the present invention can be formed by the following coating method, but is not limited to this method.
Dip coating method, air knife coating method, curtain coating method, roller coating method, wire bar coating method, gravure coating method and extrusion coating method (die coating method) (see US Pat. No. 2,681,294), 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 layer of at least one of a hard coat layer or a low refractive index layer containing a fluorine-containing olefin-based polymer is formed on one side of the unwound support. It can be applied by a gravure coating method.

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

In order to supply the film of the present invention with high productivity, an extrusion method (die coating method) is preferably used. In particular, it can be preferably used in a region with a small wet coating amount (20 cm ³ / m ² or less) such as a hard coat layer or an antireflection layer.

4- (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.

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

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

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

Irradiation conditions vary depending on each lamp, but the 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 a low refractive index layer having a small 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. By setting it as 0.7 second or more, the curing reaction is completed and sufficient curing can be performed. Moreover, since it is not necessary to maintain low-oxygen conditions for a long time by setting it as 60 seconds or less, it is excellent in the viewpoint that the enlargement of an installation can be avoided and a lot of inert gas is unnecessary.

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

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

By supplying inert gas to the ionizing radiation irradiation chamber and making it slightly blown out to the web entrance side of the irradiation chamber, it is possible to effectively reduce the oxygen concentration in the reaction chamber by eliminating the carry air accompanying the web transfer, It is possible to efficiently reduce the substantial oxygen concentration on the pole surface where the inhibition of curing by oxygen is large. 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.

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

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

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

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

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

b. Method of applying alkaline solution As a means of avoiding damage to each film in the above-mentioned immersion method, an alkali solution is applied, heated, washed with water, and dried only on the surface opposite to the surface having the coating layer under appropriate conditions. A liquid coating method is preferably used. The application in this case means that an alkaline solution or the like is brought into contact only with the surface to be saponified, and in addition to the application, it may be carried out by spraying or contacting a belt containing the solution. Including. By adopting these methods, a separate facility and process for applying an alkaline solution are required, which is inferior to the immersion method a. 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 a. And b., The saponification method can be carried out after the film is unwound from the roll-shaped support and the respective layers are formed. Furthermore, the polarizing plate can be produced more efficiently than the same operation with a single wafer by continuously performing the pasting step with the polarizing plate made of the unwound support.

c. Method of saponification by protecting with a laminate film As in the case of b. Above, when the coating layer has insufficient resistance to an alkaline solution, the laminate film is bonded to the surface on which the final layer is formed after the final layer is formed. Then, by immersing in an alkaline solution, only the surface of the triacetyl cellulose opposite to the surface on which the final layer is formed can be made hydrophilic, and then the laminate film can be peeled off. Even in this method, the hydrophilic treatment necessary for the polarizing plate protective film can be applied only to the surface opposite to the surface on which the final layer of the triacetyl cellulose film is formed without damaging the coating layer. Compared with the method b. Above, the laminate film is generated as waste, but there is an advantage that a device for applying a special alkaline solution is unnecessary.

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

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

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

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

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

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

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

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 according to the present invention can be used on a known display such as a plasma display panel (PDP) or a cathode ray tube display (CRT).

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

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

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

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

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

6). Various characteristic values Various measurement methods related to the present invention and preferable characteristic values are shown below.
6- (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 reflectance at the outgoing angle of -5 ° at the incident angle of 5 °, calculate the luminous reflectance, and evaluate the antireflection property.
The antiglare antireflection film of the present invention preferably has a specular reflectance of 2.5% 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 described in 3-d.

6- (2) color antireflection performance polarizing plate of 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 from the a ^* and 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 b ^* 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.

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

6- (4) Surface roughness Centerline average roughness (Ra) can be measured in accordance with JIS-B0601.
The optical film of the present invention has a surface roughness of 0.001 to 0.30 μm in the center line average roughness, 10 points or less of the average roughness Rz of 10 or less, and an average mountain valley distance Sm of 1 to 100 μm. preferable. Further, in the embodiment in which the porous or hollow conductive particles of the present invention are used for the low refractive index layer of the optical film, compared with the conventional embodiment including the conductive layer containing conductive particles having a high refractive index, the antiglare property is improved. Since the occurrence of interference unevenness is reduced even in a low region, Ra is 0.001 to 0.15 μm, and the effect of the present invention is particularly remarkable.

6- (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.

6- (7) 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., gelled 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 (dragonfly pencil-like MONO)
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.

6- (8) 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 ). Indentation area for each load F when the conical diamond indenter is pushed in by increasing the load continuously from 0 to 4 mN for each film and making the film thickness of 1/10 that is not affected by the glass plate hardness of the base material maximum 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.

6- (9) Antifouling test <Magic wiping>
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. .

6- (10) Evaluation of adhesion 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.

6- (11) 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.

6- (12) Dust Removability The film of the present invention can be attached to a monitor, dust (futon, fiber waste from clothes) 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.

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

[Example of particle synthesis]
Synthesis example 1
[Synthesis of hollow conductive fine particles A-1 in which Au ultrafine particles are bonded to SiO ₂ fine particles]
IPA (isopropyl alcohol) dispersion of hollow silica fine particles (prepared according to Preparation Example 4 of JP-A-2002-79616; average particle diameter of about 40 nm, shell thickness of about 10 nm, silica particle refractive index of 1.31, silica concentration of 20 mass %) 39 g, 3-mercaptopropyltrimethoxysilane 3 ml, and aluminum isopropoxide 15 mg were added to MEK (ethyl methyl ketone) 200 ml and mixed. Further, 3 ml of water was added, the temperature was raised to 60 ° C., and the mixture was stirred for 4 hours for reaction. Thereafter, 8.4 g of gold chloride (III) acid tetrahydrate was dissolved in 80 ml of MEK and added, and further 15 ml of hydroxyacetone was added and stirred for 30 minutes. When the dispersion obtained by lowering the liquid temperature to room temperature was analyzed by TEM and XRD, it was observed that Au ultrafine particles having a particle diameter of 3 to 5 nm were bonded to the entire surface of the hollow silica fine particles.
The mass ratio of Au to silica (SiO ₂ ) was 0.62. The powder specific resistance of the conductive fine particles was 90 Ω · cm.
The powder specific resistance is obtained by molding a sample powder at a pressure of 9.8 MPa (100 kg / cm ² ) into a cylindrical powder molded product (diameter 18 mm, thickness 3 mm), and measuring the direct current resistance. The powder specific resistance (Ω · cm) was determined by the following formula.
Powder specific resistance (Ω · cm) = measured value (Ω) × [2.54 (cm ² ) /0.3 (cm)]

Synthesis example 2
[Synthesis of hollow conductive fine particles A-2 in which SiO ₂ fine particles are coated with antimony oxide]
[Preparation of hollow silica fine particles (C-1)]
A mixture of 100 g of silica sol having an average particle diameter of 5 nm and a SiO ₂ concentration of 20% by mass and 1900 g of pure water was heated to 80 ° C. The pH of this reaction mother liquor was 10.5, and 9000 g of a 1.17 mass% sodium silicate aqueous solution as SiO ₂ and 9000 g of a 0.83 mass% sodium aluminate aqueous solution as Al ₂ O ₃ were simultaneously added to the mother liquor. . Meanwhile, the temperature of the reaction solution was kept at 80 ° C. The pH of the reaction solution rose to 12.5 immediately after the addition, and hardly changed thereafter. After completion of the addition, the reaction solution was cooled to room temperature and washed with an ultrafiltration membrane to prepare a SiO ₂ .Al ₂ O ₃ primary particle dispersion having a solid content concentration of 20% by mass.

1,700 g of pure water was added to 500 g of this primary particle dispersion and heated to 98 ° C. While maintaining this temperature, 53,200 g of ammonium sulfate having a concentration of 0.5% by mass was added, and then the concentration of SiO ₂ was 1 A dispersion of composite oxide fine particles (1) was obtained by adding 3,000 g of a .17% by mass sodium silicate aqueous solution and 9,000 g of a 0.5% by mass sodium aluminate aqueous solution as Al ₂ O ₃ .
Next, 1,125 g of pure water was added to 500 g of the dispersion of the composite oxide fine particles (1) having a solid concentration of 13% by washing with an ultrafiltration membrane, and concentrated hydrochloric acid (concentration 35.5% by mass). Was dropped to pH 1.0, and dealumination was performed. Next, the aluminum salt dissolved in the ultrafiltration membrane was separated while adding 10 L of hydrochloric acid aqueous solution of pH 3 and 5 L of pure water to obtain a hollow silica fine particle (C-1) dispersion having a solid content concentration of 20% by mass.
The silica-based fine particles (C-1) had an average particle size of 58 nm, MO _x / SiO ₂ (molar ratio) of 0.0001, and a refractive index of 1.30.

[Preparation of antimonic acid]
111 g of antimony trioxide (Sumitomo Metal Mining Co., Ltd .: KN purity 98.5% by mass) was suspended in a solution of 57 g of caustic potash (Asahi Glass Co., Ltd .: 85% by mass) dissolved in 1800 g of pure water. . This suspension was heated to 95 ° C., and then an aqueous solution obtained by diluting 32.8 g of hydrogen peroxide water (produced by Hayashi Junyaku Co., Ltd .: special grade, purity 35% by mass) with 110.7 g of pure water was added in 9 hours. It was added (0.1 mole / hr) to dissolve antimony trioxide, and then aged for 11 hours. After cooling, 1000 g was taken from the resulting solution, and this solution was diluted with 6000 g of pure water, and then passed through a cation exchange resin (Mitsubishi Chemical Corporation: pk-216) for deionization treatment. The pH at this time was 2.1, and the conductivity was 2.4 mS / cm.

Next, 40 g of antimonic acid having a solid concentration of 1% by mass was added to 400 g of the dispersion prepared by diluting the hollow silica-based fine particle (C-1) dispersion prepared above to a solid content of 1% by mass, and the mixture was stirred at 70 ° C. for 11 hours. Then, it was concentrated with an ultrafiltration membrane to prepare a dispersion of antimony oxide-coated silica-based fine particles (P-1) having a solid concentration of 20% by mass. The average particle size of the antimony oxide-coated silica-based fine particles was 60 nm, and the thickness of the antimony oxide coating layer was about 2 nm.
To 100 g of this antimony oxide-coated silica-based fine particle dispersion, 300 g of pure water and 400 g of methanol are added, mixed with 3.57 g of normal ethyl silicate (SiO ₂ concentration 28 mass%), and heated and stirred at 50 ° C. for 15 hours to prepare silica. An antimony oxide-coated silica-based fine particle (A-2) dispersion having a coating layer was prepared. This dispersion was subjected to solvent replacement with methanol using an ultrafiltration membrane and concentrated to a solid content concentration of 20% by mass. Subsequently, the solvent was replaced with isopropyl alcohol by a rotary evaporator to obtain an isopropyl alcohol dispersion of silica-based fine particles having a concentration of 20% by mass.

Next, 0.73 g of a methacrylic silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-503) was added to 100 g of an isopropyl alcohol dispersion of the antimony oxide-coated silica-based fine particles on which the silica coating layer was formed, A silica coating layer was formed by heating and stirring for a time to prepare a surface-treated antimony oxide-coated silica-based fine particle (A-2) dispersion.
The mass ratio of antimony oxide to silica (SiO ₂ ) was 0.11. The powder specific resistance of the conductive fine particles was 1600 Ω · cm and the refractive index was 1.41.

Synthesis example 3
[Synthesis of hollow conductive fine particles A-3 in which SiO ₂ fine particles are coated with antimony oxide]
The conditions for preparing the hollow silica-based particles (C-1) of Synthesis Example 2 were changed to obtain particles having an average particle diameter of 76 nm and a refractive index of 1.26. An antimony oxide coating layer having a thickness of about 4 nm was formed on the particles to form antimony oxide-coated silica-based fine particles having an average particle diameter of 78 nm, thereby obtaining an isopropyl alcohol dispersion of silica-based fine particles having a concentration of 20% by mass.
Next, a surface treatment was performed according to Synthesis Example 2 to prepare a surface-treated antimony oxide-coated silica-based fine particle (A-3) dispersion.
The mass ratio of antimony oxide to silica (SiO ₂ ) was 0.20. The powder specific resistance of the conductive fine particles was 600 Ω · cm and the refractive index was 1.41.

Synthesis example 4 (for comparison)
[Preparation of silica-based fine particles (B-1)]
The silica-based fine particles (C-1) used in Synthesis Example 2 are used as an aqueous dispersion having a solid concentration of 20% by mass, and 300 g of pure water and 400 g of methanol are added to 100 g of the aqueous dispersion, and then added to normal ethyl silicate (SiO _2). A silica-based fine particle aqueous dispersion in which 3.57 g (concentration 28% by mass) was mixed and heated and stirred at 50 ° C. for 15 hours to form a silica coating layer was prepared. This dispersion was subjected to solvent replacement with methanol using an ultrafiltration membrane and concentrated to a solid content concentration of 20% by mass. Subsequently, the solvent was replaced with isopropyl alcohol by a rotary evaporator to obtain an isopropyl alcohol dispersion of silica-based fine particles having a concentration of 20% by mass.
Next, 0.73 g of a methacrylic silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-503) is added to 100 g of this silica-based fine particle isopropyl alcohol dispersion, and the silica coating layer is heated and stirred at 50 ° C. for 15 hours. Silica-based fine particles (B-1) that were formed and surface-treated were prepared. The average particle diameter of the silica-based fine particles (B-1) on which the silica coating layer was formed and surface-treated was 58 nm. The fine particle powder was an insulator.

Synthesis Example 5 (for comparison)
[Preparation of antimony oxide fine particles (B-2)]
111 g of antimony trioxide (manufactured by Sumitomo Metal Mining Co., Ltd .: KN purity 98.5 mass%) was suspended in a solution of 57 g of caustic potash (Asahi Glass Co., Ltd .: purity 85 mass%) dissolved in 1800 g of pure water. . This suspension was heated to 95 ° C., and then an aqueous solution obtained by diluting 59.2 g of hydrogen peroxide water (manufactured by Hayashi Junyaku Co., Ltd .: special grade, purity 35% by mass) with 194.9 g of pure water was obtained in 6 hours. It was added (0.27 mole / hr) to dissolve antimony trioxide, and then aged for 14 hours. After cooling, 1000 g was taken from the resulting solution, and this solution was diluted with 6000 g of pure water, and then passed through a cation exchange resin (Mitsubishi Chemical Corporation: pk-216) for deionization treatment. The pH at this time was 2.0, and the conductivity was 3.1 mS / cm.
Then, after aging for 10 hours at a temperature of 70 ° C., an antimony oxide fine particle dispersion having a solid content of 14% by mass was prepared by concentrating with an ultra-thin film. The obtained antimony oxide fine particle dispersion (R-1) had a pH of 2.1 and an electric conductivity of 1.2 mS / cm.

The antimony oxide fine particle dispersion (R-1) was diluted to a dispersion having a solid concentration of 5% by mass, 100 g of methanol was added to 100 g of this dispersion, and normal ethyl silicate (SiO ₂ concentration 28% by mass) was added to the dispersion. 79 g was mixed and heated and stirred at 50 ° C. for 15 hours to prepare an antimony oxide fine particle dispersion liquid in which a silica coating layer was formed. This dispersion was subjected to solvent replacement with methanol using an ultrafiltration membrane and concentrated to a solid content concentration of 20% by mass. Subsequently, the solvent was replaced with isopropyl alcohol by a rotary evaporator to obtain an isopropyl alcohol dispersion of antimony oxide fine particles having a concentration of 20% by mass.
Next, 1.5 g of a methacrylic silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-503) is added to 100 g of the isopropyl alcohol dispersion of antimony oxide fine particles on which the silica coating layer is formed, and the mixture is heated and stirred at 50 ° C. for 15 hours. Thus, a silica coating layer was formed, and a surface-treated antimony oxide fine particle (B-2) dispersion was prepared.
The average particle size was 20 nm, the powder specific resistance of the conductive fine particles was 500 Ω · cm, and the refractive index was 1.63.

Example of optical film creation
[Example 1]
Hard coat layer coating solutions (HC-1) to (HC-6) shown in Table 1 were prepared.

The constituents in the table are expressed as mass percentages of solids. Details of the compounds used are shown below.
PETA: (A mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate manufactured by Nippon Kayaku Co., Ltd.)
DPHA: (mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate manufactured by Nippon Kayaku Co., Ltd.)
Organosilane compound: (3-acryloyloxypropyltrimethoxysilane, KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.)
Polymerization initiator: (Irgacure 184 manufactured by Nippon Ciba-Geigy Co., Ltd.)
Cross-linked styrene particles: (3.5 μm cross-linked polystyrene particles, SX-350, manufactured by Soken Chemical Co., Ltd.)
Crosslinked acrylic-styrene particles: (3.5 μm crosslinked acrylic-styrene particles,
(Made by Soken Chemical Co., Ltd.)
Crosslinked acrylic particles: (3 μm crosslinked PMMA particles, MXS-300,
(Made by Soken Chemical Co., Ltd.)
Silica particles: (1.5 μm silica particles, KE-P150, manufactured by Nippon Shokubai Co., Ltd.)
MIBK: (Methyl isobutyl ketone)
IPA: (Isopropyl alcohol)
MEK: (Methyl ethyl ketone)

A coating solution for the low refractive index layer was prepared as follows.
(Preparation of coating solution for low refractive index layer (LL-1))
A mixture of 32.1 g of normal ethyl silicate (SiO ₂ concentration 28 mass%) and 1.22 g of heicosafluorododecyltrimethoxysilane with 55.0 g of isopropyl alcohol, 10 g of pure water and 1.69 g of nitric acid with a concentration of 61 mass%. And stirred at 50 ° C. for 1 hour to prepare a matrix-forming component liquid (M-1) having a solid concentration of 10% by mass.

Next, 1.65 g of the antimony oxide-coated silica fine particle (A-2) dispersion prepared above was mixed with 6.7 g of the matrix-forming component liquid (M-1), diluted with isopropyl alcohol, and the solid content concentration was 1 A 0.0% by mass coating solution for low refractive index layer (LL-1) was prepared.

(Preparation of coating solution for low refractive index layer (LL-2))
(LL) except that the comparative silica-based particles (B-1) were used in place of the antimony oxide-coated silica-based fine particles (A-2) in the preparation of the low refractive index layer coating solution (LL-1). In the same manner as in -1), a coating solution for low refractive index layer (LL-2) having a solid content concentration of 1.0% by mass was prepared.

(Preparation of coating solution for low refractive index layer (LL-3))
36.5 g of normal ethyl silicate (SiO ₂ concentration: 28% by mass) was mixed with a mixture of 51.8 g of isopropyl alcohol, 10 g of pure water and 1.69 g of nitric acid having a concentration of 61% by mass, and stirred at 50 ° C. for 1 hour. A matrix-forming component liquid (M-2) having a solid content concentration of 10% by mass was prepared.

  Next, 1.5 g of the antimony oxide-coated silica fine particle (A-2) dispersion prepared above was mixed with 7 g of the matrix-forming component liquid (M-2), diluted with isopropyl alcohol, and a solid content concentration of 1.0. A coating solution for low refractive index layer (LL-3) of mass% was prepared.

(Preparation of coating solution for low refractive index layer (LL-4))
A mixture of 34.3 g of normal ethyl silicate (SiO ₂ concentration 28 mass%), 0.61 g of helicosafluorododecyltrimethoxysilane, 55.0 g of isopropyl alcohol, 10 g of pure water, and 1.69 g of nitric acid with a concentration of 61 mass%. And stirred at 50 ° C. for 1 hour to prepare a matrix-forming component liquid (M-3) having a solid concentration of 10% by mass.

  Next, 1.65 g of the comparative silica particle (B-1) dispersion prepared above was mixed with 6.7 g of the matrix-forming component liquid (M-3), diluted with isopropyl alcohol, and a solid content concentration of 1.0. A coating solution for low refractive index layer (LL-4) of mass% was prepared.

(Preparation of coating solution for low refractive index layer (LL-7))
The coating solution for low refractive index layer (LL-7) was the same as in the coating solution for low refractive index layer (LL-1) except that the fluorine-containing organosilane compound was changed to the same amount of heptadecafluorodecyltrimethoxysilane. ) Was produced.

(Preparation of antifouling layer coating solution (OC-1))
Henicosafluorododecyltrimethoxysilane was dissolved in isopropyl alcohol to prepare a 0.1% by mass antifouling layer coating solution (OC-1).

  The following optical films were produced using the coating solution obtained as described above.

(Preparation of optical film (101))
On the triacetyl cellulose film “TAC-TD80U” {manufactured by FUJIFILM Corporation) with a film thickness of 80 μm and a width of 1340 mm, a hard coat layer coating (HC-1) is applied by a micro gravure coating method at a conveyance speed of 30 m / min. After applying for 150 seconds and drying at 60 ° C. for 150 seconds, using a 160 W / cm air-cooled metal halide lamp {manufactured by Eye Graphics Co., Ltd.) while purging with nitrogen (oxygen concentration 0.05% or less), radiation The coating layer was cured by irradiating with ultraviolet rays having an illuminance of 400 mW / cm ² and an irradiation energy amount of 100 mJ / cm ² to prepare a hard coat layer having a thickness of 4 μm. The optical film with a hard coat layer thus obtained is referred to as (HC-1A).

On the above (HC-1A), the low refractive index layer coating solution (LL-1) is coated by the macro gravure method, and the low refractive index layer thickness after curing is adjusted to 95 nm. Thus, sample 101 was manufactured. Immediately before the application of the low refractive index layer, 1.5% by mass of 3-isocyanatopropyltriethoxysilane was added to the coating solution for the low refractive index layer with respect to the total solid content. After coating, the solvent was evaporated at 90 ° C. for 150 seconds, and thermosetting was performed at 120 ° C. for 10 minutes. Then, using a 240 W / cm air-cooled metal halide lamp (made by Eye Graphics Co., Ltd.) while purging with nitrogen so that the atmosphere has an oxygen concentration of 0.01% by volume or less, an irradiance of 120 mW / cm ² , irradiation energy Ultraviolet rays were irradiated at a dose of 240 mJ / cm ² . The refractive index of the low refractive index layer after curing was 1.43. Thus, an optical film (101) was produced.

(Preparation of optical film (102))
On the triacetyl cellulose film “TAC-TD80U” {manufactured by FUJIFILM Corporation) with a film thickness of 80 μm and a width of 1340 mm, a hard coat layer coating (HC-1) is applied by a micro gravure coating method at a conveyance speed of 30 m / min. After applying for 150 seconds and drying at 60 ° C. for 150 seconds, using a 160 W / cm air-cooled metal halide lamp {manufactured by Eye Graphics Co., Ltd.) while purging with nitrogen (oxygen concentration 0.05% or less), radiation The coating layer was cured by irradiating with ultraviolet rays having an illuminance of 400 mW / cm ² and an irradiation energy amount of 100 mJ / cm ² to prepare a hard coat layer (HC-2A) having a thickness of 3.7 μm.

On the above (HC-2A), the coating speed for hard coat layer (HC-2) is adjusted by a micro gravure coating method so that the film thickness after curing is 0.3 μm, while the conveyance speed is 30 m / After applying for 150 minutes and drying at 60 ° C. for 150 seconds, using a 160 W / cm air-cooled metal halide lamp {manufactured by Eye Graphics Co., Ltd.) while purging with nitrogen (oxygen concentration 0.05% or less), The coating layer was cured by irradiating with ultraviolet rays having an irradiance of 400 mW / cm ² and an irradiation energy amount of 100 mJ / cm ² . The optical film with a hard coat layer thus obtained is designated as (HC-2B).

The coating liquid for low refractive index layer (LL-2) is applied on the hard coat layer of (HC-2B) by the macro gravure method, and the thickness of the low refractive index layer after curing becomes 95 nm. The sample 102 was manufactured by adjusting as described above. Immediately before the application of the low refractive index layer, 1.5% by mass of 3-isocyanatopropyltriethoxysilane was added to the coating solution for the low refractive index layer with respect to the total solid content. After coating, the solvent was evaporated at 90 ° C. for 150 seconds, and thermosetting was performed at 120 ° C. for 10 minutes. Then, using a 240 W / cm air-cooled metal halide lamp (made by Eye Graphics Co., Ltd.) while purging with nitrogen so that the atmosphere has an oxygen concentration of 0.01% by volume or less, an irradiance of 120 mW / cm ² , irradiation energy Ultraviolet rays were irradiated at a dose of 240 mJ / cm ² . Thus, an optical film (102) was produced.

(Production of optical films (103) to (105))
In the production of the optical film (101), the antireflective films (103) to (105) were the same as (101) except that the coating solution for the low refractive index layer was changed to (LL-2) to (LL-4)). ) Was produced.

(Preparation of optical film (106))
The antifouling layer coating solution (OC-1) was applied on the optical film ((103) and cured at 110 ° C. for 10 minutes to form an antifouling layer. The antifouling layer had a thickness of 2 nm. It was.
Table 2 shows the structures of the optical films (101) to (106). As a result of measuring the surface roughness (Ra) of these films, it was in the range of 0.03 to 0.05 and exhibited a clear surface shape.

(Evaluation of optical film)
About the obtained film, the following items were evaluated after putting a sample on 25 degreeC60% RH conditions for 24 hours.
(Evaluation 1) Surface resistance value (LogSR)
The surface resistance value (SR) was measured by the circular electrode method. The log (SR) was calculated by taking the common logarithm of the surface resistance value. The charge on the surface leaks and the reduction in dust adhesion is remarkable at log (SR) of 12 or less, and 10 or less is particularly preferable.

(Evaluation 2) Contact angle A contact angle was determined 30 seconds after a 2 μl drop of pure water was dropped on the film using an automatic contact angle meter CA-V manufactured by Kyowa Interface Science Co., Ltd. The contact angle of the film of the present invention is preferably 95 degrees or more, and most preferably 105 degrees or more with respect to pure water.

(Evaluation 3) A dynamic friction coefficient HEIDON-14 was measured with a dynamic friction measuring machine at a 5 mmφ stainless steel ball, a load of 100 g, and a speed of 60 cm / min. It is preferably 0.30 or less, and most preferably 0.20.

(Evaluation 4) (Si2p / F1s)
The photoelectron spectra of Si2p and F1s on the outermost surface of the optical film measured with “ESCA-3400” manufactured by Shimadzu Corporation (vacuum degree 1 × 10 ⁻⁵ Pa, X-ray source; target Mg, voltage 12 kV, current 20 mA) Using the area, the peak area ratio (Si2p / F1s) of silicon atoms (Si2p) and fluorine atoms (F1s) on the surface was calculated. The smaller this ratio, the greater the ratio of fluorine atoms to silicon atoms on the film surface, and a reduction in surface free energy is expected.

(Evaluation 5) Antifouling and antifouling durability An optical film is fixed on a glass surface with an adhesive, and a black magic "Mackey extra fine (trade name: made by ZEBRA)" nib (25 ° C, 60RH%) Write a circle with a diameter of 5 mm for 3 rounds, and wipe it back and forth 20 times with a load that dents the bundle of Bencot (Brand name, Asahi Kasei Co., Ltd.) after 5 seconds. The above writing and wiping were repeated under the above conditions until after the magic did not disappear by wiping, and the antifouling property was evaluated by the number of times of wiping. The number of times until disappearance is preferably 15 times or more, and more preferably 50 times or more.
Moreover, after rubbing an optical film on the following conditions with a rubbing tester, antifouling durability evaluation was performed by performing the same operation as said antifouling evaluation.
Rub material: Bencot M-3 (manufactured by Asahi Kasei Co., Ltd.) was wound around the rubbing tip (1 cm × 1 cm) of a tester that was in contact with the sample, and the band was fixed so as not to move. 1.0 g of a weak alkaline household detergent (Glass Mypet Kao Co., Ltd.) was impregnated into the rubbing tip of the becot.
Moving distance (one way): 13 cm, rubbing speed: 13 cm / second,
Load: 200 g / cm ³ , tip contact area: 1 cm × 1 cm,
Number of rubs: 10 round trips.

(Evaluation 6) Dustproofness The transparent support side of each antireflection film sample was attached to the surface of the CRT, and the dust and tissue paper waste of 0.5 μm or more were present in a room having 1 to ² million per 1 ft ³ (cubic feet) for 24 hours. used. When the number of adhering dust and tissue paper waste is measured per 100 cm ^{2 of the} antireflection film, the average value of each result is less than 20, A is 20 to 49, B is 50 to 199 Was evaluated as C, and the case of 200 or more was evaluated as D.

(Evaluation 7) Steel wool scratch resistance evaluation (SW)
A rubbing test was conducted using a rubbing tester under the following conditions.
Evaluation environmental conditions: 25 ° C., 60% RH
Rub material: Steel wool (No. 0000, manufactured by Nippon Steel Wool Co., Ltd.) was wound around the rubbing tip (1 cm × 1 cm) of a tester in contact with the sample, and the band was fixed so as not to move. Then, the reciprocating rubbing motion under the following conditions was given.
Moving distance (one way): 13 cm, rubbing speed: 13 cm / second,
Load: 200 g / cm ³ , tip contact area: 1 cm × 1 cm,
Number of rubs: 10 round trips.
An oil-based black ink was applied to the back side of the rubbed sample and visually observed with reflected light, and scratches on the rubbed portion were evaluated according to the following criteria.
○: Even when viewed very carefully, no scratches are visible.
○ △: Slightly weak scratches are visible when viewed very carefully.
Δ: A weak scratch is visible.
Δ ×: moderate scratches are visible.
X: There are scratches that can be seen at first glance.

(Evaluation 8) Evaluation of coating unevenness The optical film was cut into a sheet having a size of A4, a PET film with a black adhesive was pasted on the back surface, and visually evaluated under the three-wavelength fluorescent lamp 1000 lux according to the following criteria. Five A4 sheets were observed to evaluate the frequency of occurrence of unevenness.
A: Unevenness is not recognized.
○: 1 or less unevenness is observed. Satisfactory with normal use.
Δ: 1 to 3 irregularities are observed.
X: Three or more unevenness is recognized.
The evaluation results are shown in Table 3.

In accordance with the present invention, an optical film having a layer containing conductive particles that are porous or hollow inside and containing a fluorine-containing silane compound has a low surface resistance, a high contact angle, a low coefficient of dynamic friction, and an optical film. It can be seen that the film is excellent in antifouling property and antifouling durability without deteriorating the dust resistance and scratch resistance of the film. Further, in the configuration of the present invention, the low refractive index layer also serves as an antistatic layer for imparting dust resistance, and it is not necessary to install a new layer for antistatic, and a high refractive index is provided. Since there is no installation of an antistatic layer, the occurrence of coating unevenness is suppressed. Furthermore, the absolute amount of conductive particles necessary for lowering the surface resistance of the outermost surface of the optical film is small, which is advantageous in terms of cost (comparison between samples 101 and 102). In addition, the sample of the present invention containing a fluorine-containing organosilane compound in a layer containing conductive particles in which the inside of the present invention is porous or hollow, or an adjacent layer thereof, has the same proportion of fluorine atoms on the surface. It turns out that it is excellent in stain | pollution | contamination durability (comparison of sample 101, 102,104). Moreover, the antifouling durability after rubbing with a nonwoven fabric containing detergent weak alkali is more than 10 fluoroalkyl group having carbon atoms (C ₁₀ F ₂₁ -) is less deteriorated and using a fluorine silane compound having, further It can be seen that the effect is high when used for the antifouling layer (comparison of samples 101, 105, and 107). In addition, the optical films (101) and (106) of the present invention had a luminous reflectance as low as 2.1 and excellent antireflection performance.

[Example 2]
(Preparation of coating solution for low refractive index layer (LL-5))
In the same manner as in the coating solution for low refractive index layer (LL-1), except that the fluorine-containing organosilane compound was changed to the same amount of the following compound (21), the coating solution for low refractive index layer (LL-5) was used. Produced.

Compound (21)
(C ₂ H ₅ O) ₃ SiC ₃ H ₆ NHCOCF ₂ O (CF ₂ O) _b —
_{- (CF 2 CF 2 O)} c CF 2 CONHC 3 H 6 Si (OC 2 H 5) 3
(Wherein b and c each represent a natural number of 2 <b <16, 3 <c <14,
It is 1/2 <= b / c <= 2. )

(Preparation of coating solution for low refractive index layer (LL-6))
In the same manner as in the coating solution for low refractive index layer (LL-1), except that the fluorine-containing organosilane compound was changed to the same amount of the following compound (22), the coating solution for low refractive index layer (LL-6) was used. Produced.

Compound (22)

_{[C 10 F 21 C 3 H 6} (CH 3) 2 Si ] ₂ NH

(Preparation of antifouling coating solution (OC-2))
Heptadecafluorodecyltrimethoxysilane was dissolved in isopropyl alcohol to prepare a 0.1% by mass antifouling layer coating solution (OC-2).

(Preparation of antifouling coating solution (OC-3))
A fluorine-containing silane compound represented by the following compound (23) (a mixture having a molecular weight of about 5000 and p = 2 to 10, manufactured by Daikin Industries, Ltd.) is diluted with perfluorohexane to give 0.1 mass% A soil layer coating solution (OC-3) was prepared.
Compound (23)

(Preparation of antifouling coating solution (OC-4))
4 parts by mass of a fluorine-containing silane compound represented by the following compound (24) and 1 part by mass of an alkoxysilane having a long chain hydrocarbon group represented by the following compound (25) were dissolved in 200 parts by mass of ethyl alcohol. Further, 1 part by mass of acetylacetone and 0.001 part by mass of concentrated hydrochloric acid were added to obtain a uniform solution, and then diluted with ethyl alcohol to prepare a coating solution for antifouling layer (OC-4) having a concentration of 0.1%.

Compound (24)
CF ₃ O (CF (CF ₃ ) CF ₂ O) _a CF ₂ CONHC ₃ H ₆ Si (OC ₂ H ₅ ) ₃
(Wherein, a represents 3 ≦ a <12)
Compound (25)
C ₁₈ H ₃₇ Si (OC ₂ H ₅ ) ₃

(Preparation of antifouling coating solution (OC-5))
DSX manufactured by Daikin Industries, Ltd., which is a fluoropolyether group-containing organosilane compound, is diluted with Fluorinert FC-77 (manufactured by Sumitomo 3M Co., Ltd.) to give a 0.1% by mass antifouling layer coating solution (OC- 5) was prepared.

(Preparation of optical film (201))
In the optical film with a hard coat layer (HC-1A) of Example 1, the optical film with a hard coat layer (HC-5A) was similarly prepared except that the coating liquid for hard coat layer was changed to (HC-5). Produced.
An optical film (201) was produced by applying and curing a coating solution for low refractive index layer (LL-1) on (HC-5A) in accordance with the sample (101) of Example 1.

(Production of optical film (202 to 203))
In the production of the optical film (201), the coating liquid type for the low refractive index layer was changed as shown in Table 4 to produce optical films (202 to 203).

(Production of optical film (204))
On the optical film with a hard coat layer (HC-5A), the coating solution for low refractive index layer (LL-3) was applied and cured according to the sample (103) of Example 1 and applied to the low refractive index layer. An optical film (204) was obtained. Further, the antifouling layer coating solution (OC-2) was applied to the upper layer and cured at 110 ° C. for 10 minutes to form an antifouling layer. The thickness of the antifouling layer was 2 nm.

(Production of optical film (205-208))
In the production of the optical film (204), the antifouling layer coating solution was changed as shown in Table 4 to produce optical films (205 to 208).
Table 4 shows the configurations of the optical films (201) to (208).

  These optical films were evaluated according to Example 1. The results are shown in Table 5.

  From Table 5, it can be seen that according to the present invention, the surface resistance is low, the high contact angle and the coefficient of dynamic friction are low, and the optical film is excellent in antifouling property and antifouling durability without deteriorating the dust resistance and scratch resistance. . In particular, when a fluoroether compound is used, it can be seen that the coefficient of dynamic friction is low and the antifouling property and antifouling durability are excellent.

[Example 3]
(Preparation of optical film (301))
An optical film (301) was produced in the same manner as in the optical film (206) of Example 2, except that the thickness of the low refractive index layer was changed to 280 nm.

(Preparation of optical film (302))
An optical film (302) was produced in the same manner as in the optical film (206) of Example 2, except that the conductive particles of the low refractive index layer were changed from (A-2) to (A-3).

(Production of optical film (303))
An optical film (303) was produced in the same manner as in the optical film (206) of Example 2, except that the conductive particles of the low refractive index layer were changed from (A-2) to (A-1).
These optical films were evaluated according to Example 1. In addition, regarding the dustproof property, the evaluation of the conditions under which the relative humidity was reduced to 40% was additionally performed. The results are shown in Table 6.

From Table 6, by increasing the film thickness of the low refractive index layer containing conductive particles or by reducing the resistance of the conductive particles themselves, the surface resistance of the optical film is reduced, and the dust resistance under low humidity is reduced. It can be seen that it is improved.
Both the optical films (206) and (301) had a luminous reflectance of 1.9. It can be seen that the dustproof improvement can be achieved without substantially increasing the luminous reflectance by setting the film thickness of the layer containing conductive particles to the optimum condition of optical interference.

[Example 5]
Samples 501 to 504 in which the composition of the hard coat layer in the optical film (206) of Example 1 was changed as shown in Table 7 were prepared.

As a result of measuring the surface roughness, surface haze, and internal haze of each sample, the following values were shown.
Sample 501 (Ra = 0.19 μm, internal haze 35%, surface haze 6%)
Sample 502 (Ra = 0.06 μm, internal haze 15%, surface haze 1%)
Sample 503 (Ra = 0.10 μm, internal haze 20%, surface haze 3%)
Sample 504 (Ra = 0.10 μm, internal haze 2%, surface haze 8%)

  As a result of evaluation according to Example 2, it was found that each sample had a low surface resistance and excellent dust resistance and antifouling durability, similar to Sample 206 of Example 2.

[Example 6]
[Saponification of optical film]
The back surface of the optical film of Example 2 was saponified under the following 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

[Production of polarizing plate with optical film]
A polarizing film was prepared by adsorbing iodine to a stretched polyvinyl alcohol film. A saponification-treated antireflection film of Example 2 was attached to one side of the polarizing film using a polyvinyl alcohol-based 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 evaluating a TN mode transmissive liquid crystal display device equipped with the produced polarizing plate of the present invention, it was confirmed that a display device excellent in visibility, dust resistance, scratch resistance and antifouling property could be produced.

[Example 7]
When the optical film sample of Example 2 was bonded to the glass plate on the surface of the organic EL display device via an adhesive, a display device having excellent antifouling property, low reflection, and high visibility was obtained.

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

Explanation of symbols

(1) Support (2) Hard coat layer (3) Medium refractive index layer (4) High refractive index layer (5) Low refractive index layer

Claims (20)

  An optical film having a layer containing conductive particles having a porous or hollow particle inside on a support, wherein the optical film contains a fluorine-containing silane compound.   The optical film according to claim 1, further comprising an antifouling layer containing a fluorine-containing silane compound on an upper layer of the layer containing the conductive particles.   The layer containing conductive particles in which the inside of the particles is porous or hollow contains at least one kind of cured product of organosilane hydrolyzate and / or condensation reaction product according to claim 1 or 2. Optical film.   The optical film according to claim 1 or 3, wherein the layer containing conductive particles in which the inside of the particle is porous or hollow contains a fluorine-containing silane compound, and the layer is the outermost surface layer. The optical film according to claim 1, wherein the fluorine-containing silane compound is a compound represented by the following general formula [1].
Formula _{[1] (Rf-L 1} ) n -Si (R 11) 4-n
(In the formula, Rf represents a linear, branched or cyclic fluorinated alkyl group having 1 to 20 carbon atoms or a fluorinated aromatic group having 6 to 14 carbon atoms. L ₁ is a divalent divalent having 10 or less carbon atoms. Represents a linking group, R ¹¹ represents an alkyl group, a hydroxyl group or a hydrolyzable group, and n represents an integer of 1 to 3.) The optical film according to claim 5, wherein the fluorine-containing silane compound represented by the general formula [1] is a compound represented by the following general formula [2].
Formula _{[2] C n F 2n +} 1 - (CH 2) m -Si (R) 3
(In the formula, n represents an integer of 10 or more, m represents an integer of 1 to 5. R represents an alkoxy group having 1 to 5 carbon atoms or a halogen atom.)   The optical film according to claim 1, wherein the fluorine-containing silane compound contains a perfluoropolyether group. The optical film according to claim 7, wherein the fluorine-containing silane compound is a compound represented by the following general formula [3].
General formula [3]

Wherein R _f is a linear or branched perfluoroalkyl group having 1 to 16 carbon atoms, X is an iodine atom or a hydrogen atom, Y is a hydrogen atom or a lower alkyl group, Z is a fluorine atom or a trifluoromethyl group. , R ¹ is a hydrolyzable group, R ² is hydrogen or an inert monovalent organic group, a, b, c, d are integers of 0 to 200, e is 0 or 1, and m and n are 0 to 0. (The integer of 2 and p represent the integer of 1-10.) The optical film according to claim 8, wherein the fluorine-containing silane compound represented by the general formula [3] is a compound represented by the following general formula [4].
General formula [4]

(In the formula, Y represents a hydrogen atom or a lower alkyl group, R ¹ represents a hydrolyzable group, q represents an integer of 1 to 50, m represents an integer of 0 to 2, and p represents an integer of 2 to 10.) The optical film according to claim 1, wherein the fluorine-containing silane compound is a compound represented by the following general formula [5].
General formula [5]
_{^{Rf 5 [- (L 5)}} n -X-R 51 -Si (OR ⁵² ) ₃ ] _m
(Wherein Rf ⁵ represents a perfluoropolyether group, R ⁵¹ Is an alkylene group, R ⁵² is an alkyl group, L ₅ is —CO—, X is —O—, —NR ⁵³ —, —S—, —SO ₂ —, —SO _2.
In the group selected from NR ⁵³ — and —NR ⁵³ CO—, n represents 0 or 1, and m represents a natural number of 2 or less. R ⁵³ represents a hydrogen atom or an alkyl group having 3 or less carbon atoms. ) The optical film according to claim 1, wherein the layer containing the fluorine-containing silane compound further contains a compound represented by the following general formula [7].
General formula [7]
R ⁷¹ -Si (OR ⁷² ₃
(Where R ⁷¹ Represents a long-chain hydrocarbon group having 10 or more carbon atoms, and R ⁷² represents an alkyl group. ) Silicon atoms (Si2p) and fluorine atoms (on the film surface) measured by X-ray photoelectron spectroscopy
The peak area ratio (Si2p / F1s) of F1s) is 0.0 or more and 0.4 or less, The optical film according to claim 1-11.   The optical film according to claim 1, wherein the dynamic friction coefficient is 0.02 or more and 0.30 or less.   The optical film according to claim 1, wherein a contact angle of water is 95 degrees or more.   The optical film according to any one of claims 1 to 14, which has a value of 12 or less when the surface resistance of the optical film is expressed by log (SR).   The optical film according to claim 1, wherein the layer containing the conductive particles is a low refractive index layer and has a thickness of 130 nm to 500 nm. A coating composition containing the following components (A), (B), and (C).
(A) Conductive particles having a porous or hollow particle interior.
(B) At least one of organosilane and / or its hydrolyzate and / or its condensation reaction product.
(C) At least one of a fluorine-containing silane compound and / or a hydrolyzate thereof and / or a condensation reaction product thereof. The coating composition according to claim 17, wherein the fluorine-containing silane compound as the component (C) is a compound represented by any one of the following general formulas [1] to [5].
Formula _{[1] (Rf-L 1} ) n -Si (R 11) 4-n
(In the formula, Rf represents a linear, branched or cyclic fluorinated alkyl group having 1 to 20 carbon atoms or a fluorinated aromatic group having 6 to 14 carbon atoms. L ₁ is a divalent divalent having 10 or less carbon atoms. Represents a linking group, R ¹¹ represents an alkyl group, a hydroxyl group or a hydrolyzable group, and n represents an integer of 1 to 3.)
Formula _{[2] C n F 2n +} 1 - (CH 2) m -Si (R) 3
(In the formula, n represents an integer of 10 or more, m represents an integer of 1 to 5. R represents an alkoxy group having 1 to 5 carbon atoms or a halogen atom.)
General formula [3]

Wherein R _f is a linear or branched perfluoroalkyl group having 1 to 16 carbon atoms, X is an iodine atom or a hydrogen atom, Y is a hydrogen atom or a lower alkyl group, Z is a fluorine atom or a trifluoromethyl group. , R ¹ is a hydrolyzable group, R ² is hydrogen or an inert monovalent organic group, a, b, c, d are integers of 0 to 200, e is 0 or 1, and m and n are 0 to 0. (The integer of 2 and p represent the integer of 1-10.)
General formula [4]

(In the formula, Y represents a hydrogen atom or a lower alkyl group, R ¹ represents a hydrolyzable group, q represents an integer of 1 to 50, m represents an integer of 0 to 2, and p represents an integer of 2 to 10.)
General formula [5]
_{^{Rf 5 [- (L 5)}} n -X-R 51 -Si (OR ⁵² ) ₃ ] _m
(Wherein Rf ⁵ represents a perfluoropolyether group, R ⁵¹ Is an alkylene group, R ⁵² is an alkyl group, L ₅ is —CO—, X is —O—, —NR ⁵³ —, —S—, —SO ₂ —, —SO _2.
In the group selected from NR ⁵³ — and —NR ⁵³ CO—, n represents 0 or 1, and m represents a natural number of 2 or less. R ⁵³ represents a hydrogen atom or an alkyl group having 3 or less carbon atoms. )   A polarizing plate comprising the optical film according to claim 1.   The image display apparatus which has an optical film in any one of Claims 1-16.

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