JP2007163971A - Antireflection film, and polarizing plate and liquid crystal display device using the same - Google Patents

Abstract

An object of the present invention is to provide an antireflection film having both high antiglare property and improvement of image blur and white blur and a polarizing plate using the antireflection film with high productivity. In addition, the present invention provides a high-quality display that exhibits stable display performance with respect to ambient brightness by using the antireflection film and the polarizing plate.
An antireflection film having at least an antiglare layer and a low refractive index layer on a transparent support, and having a specific reflection intensity profile caused by surface irregularities of the film with respect to incident light on the film surface An antireflection film having
[Selection] Figure 2

Description

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

  In general, an antireflection film is used in a display device such as a CRT, a plasma display (PDP), an electroluminescence display (ELD), or a liquid crystal display (LCD) to prevent reflection of an image due to reflection of external light. Arranged on the top surface of the display.

  In order to reduce the influence of external light reflection, there are a method of lowering the reflectance of the display device surface and a method of scattering reflected light by surface irregularities.

  Anti-glare films having a scattering property of reflected light are roughly classified into an anti-glare film having substantially only surface scattering property and an anti-glare film having both surface scattering property and internal scattering property. be able to.

  In addition, in recent years, with the increase in the definition of display devices, as a means of improving minute luminance unevenness (called glare) with an anti-glare film, anti-glare property having higher internal scattering than surface scattering in addition to surface scattering. The technique regarding a film is disclosed (patent documents 1-4).

In order to prevent the reflection of an image due to reflection of external light, a means for making the film surface uneven and blurring the outline of the reflected image is generally used, and visibility from the regular reflection direction of external light is improved. On the other hand, since scattered light travels in a direction other than regular reflection, black appears white in that direction (referred to as white blur). In response to this problem, a proposal (Patent Document 5) has been made to control the scattering distribution (profile) of reflected light by irradiating the film surface with light rays. Here, in the reflected light profile for incident light of −10 °, An antiglare film having a value width of 7 ° or more and a reflection intensity ratio of 30 ° direction and regular reflection direction (10 °) of 0.2 or less is disclosed.
JP 2000-304648 A Japanese Patent No. 3507719 Japanese Patent No. 3515401 Japanese Patent No. 3515426 JP 2002-365410 A JP 2003-121606 A JP 2003-270409 A

  As described above, in order to reduce the influence of external light reflection, there are a method of reducing the reflectance of the display device surface and a method of scattering the reflected light by surface irregularities, etc., but only one of these methods is considered. Then, it is difficult to further improve the visibility. For example, if the surface has no anti-glare property even if the reflectance is significantly reduced from the current common sense, it can be easily guessed that the shape of the reflector is still recognized and looks unsightly. Patent Documents 6 and 7 describe that when a light-scattering film is used on the outermost surface of a display device, a film having an antireflection function having an effect of suppressing surface reflection of external light in a bright room is preferable. Has been. Patent Document 7 discloses a technique related to a scattering film that improves the viewing angle characteristics of an LCD by controlling internal scattering.

  Furthermore, in view of the viewing angle dependency of the display device itself such as a liquid crystal display device, optimizing the performance of the antireflection film is extremely important for improving the total performance of the display device.

  However, the present situation is that no antireflection film satisfying both the antiglare property and the improvement of image blur and white blur has not been proposed.

  Accordingly, an object of the present invention is to provide an antireflection film that achieves both high antiglare properties and improvement in image blur and white blur and a polarizing plate using the antireflection film with high productivity. Furthermore, it is providing the high quality display which shows the stable display performance with respect to ambient brightness by using this antireflection film and a polarizing plate.

  As a result of intensive studies to solve the above-described problems, the present inventors have found that the above-described problems can be solved and the object can be achieved, and the present invention has been completed.

  That is, the present invention achieves the object by the following configuration.

1. An antireflection film having at least an antiglare layer and a low refractive index layer on a transparent support, wherein substantially parallel light is incident on the film surface, and the film includes a normal line and an incident direction, When the reflection intensity due to the surface unevenness of the film is measured, the maximum value of the change amount of reflectance | dR (θ) / dθ | with respect to the reflection angle θ is 0.005 or more and less than 0.03. Antireflection film.
[Where R (θ) is the reflectance at the reflection angle θ. ]
2. An antireflection film having at least an antiglare layer and a low refractive index layer on a transparent support, wherein substantially parallel light is incident on the film surface, and the film includes a normal line and an incident direction, When the reflection intensity due to the surface irregularities of the film was measured, the maximum amount of change of relative reflectance R _rel (θ) with respect to the reflection angle θ | dR _rel (θ) / dθ | An antireflective film characterized by being
[Where R _rel (θ) is the relative reflectance normalized by the reflectance R _s in the regular reflection direction, R _rel (θ) = R (θ) / R _s , and R (θ) is the reflection It is a reflectance at an angle θ. ]
3. 3. The antireflection film as described in 1 or 2 above, wherein the specular reflectance at 5 ° incidence is 0.5% or more and less than 3%.
4). 4. The antireflection film according to any one of 1 to 3, wherein the antireflection film has a haze value of 0 to 35% due to internal scattering and a haze value of 5 to 15% due to surface scattering.
5. 5. The antireflection film as described in any one of 1 to 4 above, wherein the antireflection film has a center line average roughness Ra of 0.08 to 0.30 μm.
6). 6. The antireflection film according to any one of 1 to 5 above, wherein the image clarity of the antireflection film according to JIS K-7105 is 5 to 60% when measured at an optical comb width of 0.5 mm.
7). 7. The antireflection film according to any one of 1 to 6, wherein the antiglare layer contains at least a translucent resin and translucent particles.
8). The above-mentioned 7 wherein the translucent resin is a crosslinked poly (meth) acrylate-based polymer particle comprising a (meth) acrylate monomer having at least trifunctional or higher functionality and the translucent particle having an acrylic content of 50 to 100% by mass. The antireflection film according to Item.
9. Cross-linked polyacrylic (-styrene) (co) polymer particles in which the translucent resin contains at least a trifunctional or higher functional (meth) acrylate monomer as the main component, and the translucent particles have an acrylic content of 50 to 100% by mass. Item 9. The antireflection film according to Item 7 or Item 8.
10. In the polarizing plate having a polarizing film and protective films provided on both sides of the polarizing film, at least one of the protective films is the antireflection film according to any one of 1 to 9 above. Polarizing plate.
11. 11. The polarizing plate according to 10 above, wherein at least one of the two protective films is an optical compensation film having optical anisotropy.
12 Item 10 or Item 11 above, wherein the protective film disposed opposite to the antireflection film among the two protective films is an optical compensation film having at least an optically anisotropic layer in which the orientation of the liquid crystal compound is fixed. The polarizing plate as described in.
13. Of the two protective films, an optical anisotropic film comprising a compound having a discotic structural unit on the surface opposite to the surface to be bonded to the polarizing film, the protective film disposed opposite to the antireflection film 13. The polarizing plate as described in any one of 10 to 12 above, which is an optical compensation film having a functional layer.
14 A laminated polarizing plate comprising at least one optical compensation film and a polarizing plate bonded via an adhesive layer, wherein the polarizing plate is the polarizing plate according to any one of 10 to 13 above. .
15. 15. A liquid crystal display device comprising at least one polarizing plate according to any one of items 10 to 14.
16. It includes at least a polarizing plate, a liquid crystal cell for display, and a backlight. The maximum luminance is 300 cd / m ² or more, and the darkroom contrast ratio in white / black display is 500 or more in the normal direction of the liquid crystal cell, 30 ° to the normal. A liquid crystal display device having an angle range of 150 or more and an angle range of 60 ° or less with respect to the normal line of 15 or more, wherein the polarizing plate according to any one of 10 to 15 above is a display device. A liquid crystal display device arranged on the outermost surface of the observer side.
17. Item 17. The liquid crystal display device according to Item 15 or 16, wherein the diagonal of the display screen is 20 inches or more.

  With the film of the present invention, it was possible to provide an antireflection film that achieves both high antiglare property and improvement in image blur and white blur, a polarizing plate using the antireflection film, and a liquid crystal display device.

  Hereinafter, the present invention will be described in more detail. In the present specification, when a numerical value represents a physical property value, a characteristic value, etc., the description “(numerical value 1) to (numerical value 2)” means “(numerical value 1) or more and (numerical value 2) or less”. . In the present specification, the description “(meth) acrylate” means “at least one of acrylate and methacrylate”. The same applies to “(meth) acrylic acid” and the like. Furthermore, the term “on the support” in the present invention includes both the case where the surface directly refers to the support and the case where the surface includes a layer (film) provided on the support. is there. The same applies to “on the hard coat layer” and the like.

0. Angle dependency of reflection intensity The antireflection film of the present invention has a fine concavo-convex structure on at least the surface, and the anti-glare property is obtained by scattering the reflected image due to light scattering caused by the concavo-convex structure and blurring the outline. Demonstrate. When the angle dependency of the reflection intensity due to the surface irregularities when light is incident on the film surface at a certain angle satisfies the numerical range in the specific relational expression of the present invention, the preferred antireflection performance in the present invention can be obtained. .

  Specifically, it is shown in FIG. (A) of FIG. 1 is a schematic diagram showing a method of measuring the angle dependency of the reflected light intensity due to surface irregularities of the antireflection film of the present invention. FIG. 1B is a schematic diagram showing a surface C including the normal direction D of the film and the incident direction E of light. As shown in FIGS. 1 (a) and 1 (b), light substantially parallel from the light source F is incident on the surface B of the antireflection film A having irregularities on the surface, and the normal direction D of the film and the incidence of light. In the plane C including the direction E, the angle of the light receiving part G is continuously changed, and the intensity of the reflected light at each reflection angle, for example, the reflection angle θ, is measured. The reflection angle dependency (hereinafter also referred to as reflected light intensity profile) is measured.

The light incident on the film is preferably substantially parallel light. Specifically, it is preferable to collimate a white light source and set the diffusion or convergence angle to within 1 °. Although it depends on the size of the surface irregularities, the measurement range is preferably 1 mm ² or more. Although the incident angle is not particularly limited, the purpose is to measure the angular dependence near specular reflection, and incidence from around 0 ° where specular reflection cannot be observed or from a wide angle where both sides of the profile cannot be observed is not preferable. . A range of approximately 5 ° to 45 ° is preferred. As a measuring method, for example, by using an automatic variable angle photometer “GP-5 type” manufactured by Murakami Color Research Laboratory Co., Ltd., the sample surface is irradiated with white parallel light of about 5 mmφ, and the incident light direction and The angle dependency of the reflected light intensity in the plane including the normal line direction of the film can be continuously measured at a reflection angle unit of 0.1 °.

  When used in an actual display, the surface (referred to as the back surface) opposite to the surface provided with the antiglare antireflection layer of the antireflection film is closely bonded to the polarizing film or the display surface. For this reason, the influence of back surface reflection becomes so small that it can be ignored. It is desirable to consider the reflected light intensity profile handled in the present invention in a state in which the influence of the back surface reflection is eliminated so as to be closer to the actual state. Specifically, the back surface of the antireflection film is painted black during the measurement, or an adhesive. It can measure by sticking and sticking to a black resin film or a polarizing plate with a crossed Nicol arrangement. As used herein, “reflection intensity due to surface irregularities” means the reflection intensity measured using these methods, and includes not only the effects of interface reflection between coating layers and scattering by internal particles. It is out. That is, it is not limited only to the reflection intensity resulting from the interface between the film outermost surface and air.

If the blur of the reflected image that does not depend on the amount of light is assumed to be anti-glare, the anti-glare can be considered in direct correlation with the angle dependence of the reflected light profile. On a smooth surface having no antiglare property, the strength rapidly decreases when the angle is changed from regular reflection, and the maximum value of | dR _rel (θ) / dθ | Conversely, if the maximum value of | dR _rel (θ) / dθ | is reduced, it means that light is diffused at all angles and the reflected image is more blurred and anti-glare. d is a differential symbol, and dR _rel (θ) / dθ represents the slope of the tangent line of the function R _rel (θ). Experimentally, it is only necessary to obtain a change in the light amount when the measurement step of the observation angle θ is reduced. In the present invention, the measurement step of θ is measured at 0.1 °. If the step value of θ exceeds 1 °, an error from the reflected light profile (which should be originally) increases, and there is a possibility of deviation from the specified range of the present invention. As a measuring means, for example, it can be measured with a general commercially available apparatus as described above.

The reflection image actually recognized by a person can be said to be a physical quantity obtained by multiplying the anti-glare property by the absolute value of the reflection intensity, that is, if the reflection image has a large blur even if the reflectance of the surface is high, It can be considered that the same visibility as a smooth surface with low reflectance is exhibited.
However, if the antiglare property is increased while the surface reflectance is high, the reflected light is scattered over a wide angle range, which causes a problem called “white blur”. The present inventors considered that it is very important to control the reflected light profile to an appropriate value in order to reduce the reflection of the reflected image without such a harmful effect. Thus, by satisfying the relationship of the reflection profile of the present invention, a high-quality antireflection film free from image blur and white blur can be obtained without using an expensive multilayer antireflection film.

An example of the angle dependence of the reflected light intensity is shown in FIG. The horizontal axis is the reflection angle relative to the film normal (
Angle θ) of the light receiving portion, and the normal direction of the film is 0 °. Parallel light is incident from the direction of −5 °, and therefore has a peak at 5 °, which is the regular reflection direction. The vertical axis represents the relative reflection intensity R _rel (θ) normalized by the peak intensity.

The maximum change amount | dR _rel (θ) / dθ | of the relative reflectance R (θ) with respect to the reflection angle θ can be expressed as the slope of the broken line A in the figure. The greater the inclination, the smaller the antiglare property, and the smaller, the greater the antiglare property. In the present invention, when | dR _rel (θ) / dθ | is 0.35 or more and less than 1.0, preferably 0.40 or more and less than 0.85, the antiglare property, the image blur and the white blur are improved at the same time. A satisfactory antireflection film can be obtained. Further, in the present invention, the maximum change amount of reflectivity with respect to the reflection angle θ | dR (θ) / dθ | (which can be considered as the total performance of antiglare property and reflectivity) is 0.005 or more and less than 0.03. An antireflection film that satisfies both the antiglare property and the improvement of image blur and white blur can be obtained also by setting the content to preferably 0.008 or more and less than 0.025.
By selecting the amount and size of the light-transmitting particles so as to obtain a desired profile and changing the drying and curing conditions of the coating film, the degree of aggregation of the particles in the film and the distribution of the aggregated particles To change.
Further, in the antireflection film satisfying any one of the above relational expressions, the specular reflectance at 5 ° incidence is preferably 0.5% or more and less than 3%, and more preferably 0.5% or more and less than 2%.

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

1- (1) Binder The antireflection film of the present invention can comprise at least one layer formed by a crosslinking reaction or a polymerization reaction of an ionizing radiation curable compound. That is, a coating composition containing an ionizing radiation-curable polyfunctional monomer or polyfunctional oligomer as a binder (hereinafter also referred to as a curable composition) is coated on a transparent support, and the polyfunctional monomer or polyfunctional oligomer is crosslinked. Alternatively, at least one functional layer contributing to the antireflection function can be formed on the support by a polymerization reaction.

  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.

[Photopolymerizable polyfunctional monomer]
Specific examples of the photopolymerizable polyfunctional monomer having a photopolymerizable functional group include (meth) alkylene glycols such as neopentyl glycol acrylate, 1,6-hexanediol (meth) acrylate, and propylene glycol di (meth) acrylate. Acrylic acid diesters; (Meth) acrylic acid 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 Diesters; (meth) acrylic acid diesters of polyhydric alcohols such as pentaerythritol di (meth) acrylate; 2,2-bis {4- (acryloxy-diethoxy) phenyl} propane, 2--2-bi {4- (acryloxy · polypropoxy) phenyl} (meth) diesters acrylate of ethylene oxide or propylene oxide adducts such as propane; and the like.

  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.

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 performed 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.

[Polymer binder]
In the present invention, an uncrosslinked polymer or a crosslinked polymer can be used as the binder. The crosslinked polymer preferably has an anionic group. The polymer having a crosslinked anionic group has a structure in which the main chain of the polymer having an anionic group is crosslinked.

  Examples of the polymer main chain include polyolefin (saturated hydrocarbon), polyether, polyurea, polyurethane, polyester, polyamine, polyamide and melamine resin. A polyolefin main chain, a polyether main chain and a polyurea main chain are preferable, a polyolefin main chain and a polyether main chain are more preferable, and a polyolefin main chain is most preferable.

  The polyolefin main chain consists of saturated hydrocarbons. The polyolefin main chain is obtained, for example, by an addition polymerization reaction of an unsaturated polymerizable group. The polyether main chain has repeating units bonded by an ether bond (—O—). The polyether main chain is obtained, for example, by a ring-opening polymerization reaction of an epoxy group. In the polyurea main chain, repeating units are bonded by a urea bond (—NH—CO—NH—). The polyurea main chain is obtained, for example, by a condensation polymerization reaction between an isocyanate group and an amino group. The polyurethane main chain has repeating units bonded by urethane bonds (—NH—CO—O—). The polyurethane main chain is obtained, for example, by a polycondensation reaction between an isocyanate group and a hydroxyl group (including an N-methylol group).

  The polyester main chain has repeating units bonded by an ester bond (—CO—O—). The polyester main chain is obtained, for example, by a 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 condensation polymerization reaction between a triazine group (for example, melamine) and an aldehyde (for example, 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 group), a sulfonic acid group (sulfo group), and a phosphoric acid group (phosphono group), 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 crosslinked 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 quaternary ammonium group has a function of maintaining the dispersed state of the inorganic particles in the same manner as the anionic group. In addition, even if the amino group, the quaternary ammonium group and the benzene ring are contained in a repeating unit having an anionic group or a repeating unit having a crosslinked structure, the same effect can be obtained.

In a repeating unit having an amino group or a quaternary ammonium group, the amino group or quaternary ammonium group is bonded directly to the main chain of the polymer or bonded to the main chain via 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, and 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, and 1 carbon atom. More preferably, it is an alkyl group of ˜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.

[Fluoropolymer]
Of the polymer binders in the present invention, a fluorine-containing polymer can be preferably used particularly for the low refractive index layer.

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

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

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

Specific methods for preparing the photopolymerizable group-containing copolymer include, but are not limited to, the following methods.
a. A method of esterifying by reacting a (meth) acrylic acid chloride with a crosslinkable functional group-containing copolymer containing a hydroxyl group,
b. A method of urethanization by reacting an isocyanate group-containing (meth) acrylic ester with a crosslinkable functional group-containing copolymer containing a hydroxyl group,
c. A method of reacting (meth) acrylic acid with a crosslinkable functional group-containing copolymer containing an epoxy group,
d. A method in which a crosslinkable functional group-containing copolymer containing a carboxyl group is reacted with a containing (meth) acrylic acid ester containing an epoxy group for esterification.

  The amount of the photopolymerizable group introduced can be arbitrarily adjusted, and the carboxyl group, hydroxyl group, etc. can be controlled from the viewpoints of surface stability of the coating film, reduction of surface failure when coexisting with inorganic particles, and improvement of film strength. It is also preferable to leave a certain amount.

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

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

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

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

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

  As described in JP-A-10-25388 and JP-A-2000-17028, a curing agent having a polymerizable unsaturated group may be used in combination with the above polymer. Further, as described in JP-A-2002-145952, combined use with a compound having a fluorine-containing polyfunctional polymerizable unsaturated group is also preferable. Examples of the compound having a polyfunctional polymerizable unsaturated group include the polyfunctional monomers described in the hard coat layer. These compounds are particularly preferred because they have a large combined effect for improving scratch resistance, particularly when a compound having a polymerizable unsaturated group is used in the polymer body.

[Organosilane compound]
The functional layer in the antireflection film of the present invention contains a hydrolyzate of an organosilane compound and / or a partial condensate thereof (hereinafter, the obtained reaction solution is also referred to as “sol component”). It is preferable in terms of scratch resistance.

  This sol component functions as a binder by applying the curable composition and then condensing in a drying and heating process to form a cured product. Moreover, when it has a polyfunctional acrylate polymer, the binder which has a three-dimensional structure is formed by irradiation of actinic light.

The organosilane compound is preferably represented by the following general formula (1).
Formula _{^{(1) :( R 10) m1}} -Si (X 11) 4-m1
In the general formula (1), R ¹⁰ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, hexyl, decyl, hexadecyl and the like. The alkyl group is preferably an alkyl group having 1 to 30 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 6 carbon atoms. Examples of the aryl group include phenyl and naphthyl, and a phenyl group is preferable.

X ¹¹ represents a hydroxyl group or a hydrolyzable group, for example, an alkoxy group (preferably an alkoxy group having 1 to 5 carbon atoms, such as a methoxy group or an ethoxy group), a halogen atom (for example, Cl, Br, I Etc.), and R ¹¹ COO (R ¹¹ is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, such as CH ₃ COO, C ₂ H ₅ COO, etc.). Is an alkoxy group, particularly preferably a methoxy group or an ethoxy group.
m1 represents an integer of 1 to 3, preferably 1 or 2, and particularly preferably 1.

When R ¹⁰ or the X ¹¹ there are a plurality, even more R ¹⁰ or X ¹¹ is the same, respectively, may be different.

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

When there are a plurality of R ^{10 s} , at least one is preferably a substituted alkyl group or a substituted aryl group.

Among the organosilane compounds represented by the general formula (1), an organosilane compound having a vinyl polymerizable substituent represented by the following general formula (1-1) is preferable.
General formula (1-1):

In the general formula (1-1), R ¹² represents a hydrogen atom, a methyl group, a methoxy group, an alkoxycarbonyl group, a cyano group, a fluorine atom, or a chlorine atom. Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group. A hydrogen atom, a methyl group, a methoxy group, a methoxycarbonyl group, a cyano group, a fluorine atom, and a chlorine atom are preferable, a hydrogen atom, a methyl group, a methoxycarbonyl group, a fluorine atom, and a chlorine atom are more preferable, and a hydrogen atom and a methyl group Is particularly preferred.

Y ¹¹ represents a single bond or * -COO-**, * -CONH-** or * -O-**, preferably a single bond, * -COO-** or * -CONH-**. Bonds and * -COO-** are more preferred, and * -COO-** is particularly preferred. * Represents a position bonded to ═C (R ¹² ) —, and ** represents a position bonded to L ¹¹ .

L ¹¹ represents a divalent linking chain. Specifically, a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted alkylene group having a linking group (for example, ether, ester, amide, etc.) inside, and a linking group inside. A substituted or unsubstituted arylene group, a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, an alkylene group having a linking group therein is preferred, an unsubstituted alkylene group, an unsubstituted arylene group Further, an alkylene group having an ether or ester linking group inside is more preferred, an unsubstituted alkylene group, and an alkylene group having an ether or ester linking group inside is particularly preferred. Examples of the substituent include a halogen, a hydroxyl group, a mercapto group, a carboxyl group, an epoxy group, an alkyl group, and an aryl group, and these substituents may be further substituted.

m2 represents 0 or 1, and is preferably 0.
R ¹⁰ has the same meaning as R ¹⁰ in formula (1), and is preferably a substituted or unsubstituted alkyl group or an unsubstituted aryl group, more preferably an unsubstituted alkyl group or an unsubstituted aryl group.

X ¹¹ has the same meaning as X ¹¹ in formula (1), preferably a halogen atom, a hydroxyl group or an unsubstituted alkoxy group, more preferably a chlorine atom, a hydroxyl group or an unsubstituted alkoxy group having 1 to 6 carbon atoms. Further, an alkoxy group having 1 to 3 carbon atoms is more preferable, and a methoxy group is particularly preferable. When X ¹¹ there are a plurality, it may be different even multiple X ¹¹ is the same, respectively.

  Two or more compounds of the general formula (1) and the general formula (1-1) may be used in combination.

  Although the specific example of a compound represented by General formula (1) and General formula (1-1) below is shown, it is not limited.

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

[catalyst]
The hydrolyzate and / or partial condensate of the organosilane compound is generally produced by treating the organosilane compound in the presence of a catalyst.

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

(Metal chelate compound)
Examples of the metal chelate compound include an alcohol represented by a general formula R ⁰¹ OH (where R ⁰¹ represents an alkyl group having 1 to 10 carbon atoms), and R ⁰² COCH ₂ COR ⁰³ (where R ⁰² represents carbon. From Zr, Ti, and Al having a ligand represented by a compound represented by an alkyl group having 1 to 10 carbon atoms, R ⁰³ represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms) Any metal having a selected metal as a central metal can be suitably used without particular limitation. Within this category, two or more metal chelate compounds may be used in combination.

The metal chelate compound used in the present invention is represented by the general formula Zr (OR ⁰¹ ) _p1 (R ⁰² COCHCOR ⁰³ ) _p2 , Ti (OR ⁰¹ ) _q1 (R ⁰² COCHCOR ⁰³ ) _q2 , and Al (OR ⁰¹ ) _r1 (R ⁰² Those selected from the group of compounds represented by COCHCOR ⁰³ ) _r2 are preferred, and they serve to promote the condensation reaction of the hydrolyzate and / or partial condensate of the organosilane compound.

R ⁰¹ and R ⁰² in the metal chelate compound may be the same or different, and an alkyl group having 1 to 10 carbon atoms, specifically, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, An s-butyl group, a t-butyl group, an n-pentyl group, or a phenyl group. R ⁰³ represents an alkyl group having 1 to 10 carbon atoms as described above, or an alkoxy group having 1 to 10 carbon atoms such as a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, and n-butoxy. Group, s-butoxy group, t-butoxy group and the like. Moreover, p1, p2, q1, q2, r1, and r2 in the metal chelate compound represent integers determined so as to be p1 + p2 = 4, q1 + q2 = 4, and r1 + r2 = 3, respectively.

  Specific examples of these metal chelate compounds include tri-n-butoxyethylacetoacetate zirconium, di-n-butoxybis (ethylacetoacetate) zirconium, n-butoxytris (ethylacetoacetate) zirconium, tetrakis (n-propylacetate). Zirconium chelate compounds such as acetate) zirconium, tetrakis (acetylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium; diisopropoxy bis (ethylacetoacetate) titanium, diisopropoxy bis (acetylacetate) titanium, diiso Titanium chelate compounds such as propoxy bis (acetylacetonate) titanium; diisopropoxyethyl acetoacetate aluminum, dii Propoxyacetylacetonate aluminum, isopropoxybis (ethylacetoacetate) aluminum, isopropoxybis (acetylacetonate) aluminum, tris (ethylacetoacetate) aluminum, tris (acetylacetonate) aluminum, monoacetylacetonate bis (ethyl) An aluminum chelate compound such as acetoacetate) aluminum.

  Among these metal chelate compounds, tri-n-butoxyethyl acetoacetate zirconium, diisopropoxy bis (acetylacetonate) titanium, diisopropoxyethyl acetoacetate aluminum, and tris (ethyl acetoacetate) aluminum are preferable. . These metal chelate compounds can be used individually by 1 type or in mixture of 2 or more types. Moreover, the partial hydrolyzate of these metal chelate compounds can also be used.

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

The β-diketone compound and / or β-ketoester compound represented by the general formula R ⁰² COCH ₂ COR ⁰³ is used in the present invention, and is used as a stability improver for the curable composition used in the present invention. It works. Here, R ⁰² represents an alkyl group having 1 to 10 carbon atoms, and R ⁰³ represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. That is, by coordinating with the metal atom in the metal chelate compound (zirconium, titanium and / or aluminum compound), the condensation reaction of the hydrolyzate and / or partial condensate of the organosilane compound by these metal chelate compounds is performed. It is considered that the promoting action is suppressed and the storage stability of the resulting composition is improved. R ⁰² and R ⁰³ constitute a β- diketone compound and / or β- ketoester compound are the same as R ⁰² and R ⁰³ constituting the metal chelate compound.

Specific examples of the β-diketone compound and / or β-ketoester compound include acetylacetone, methyl acetoacetate, ethyl acetoacetate, acetoacetate-n-propyl, acetoacetate-i-propyl, acetoacetate-n-butyl, acetoacetate. Acetic acid-s-butyl, acetoacetic acid-
t-butyl, 2,4-hexane-dione, 2,4-heptane-dione, 3,5-heptane-dione, 2,4-octane-dione, 2,4-nonane-dione, 5-methylhexane-dione And so on. Of these, ethyl acetoacetate and acetylacetone are preferred, and acetylacetone is particularly preferred. These β-diketone compounds and / or β-ketoester compounds may be used alone or in combination of two or more. In the present invention, the β-diketone compound and / or β-ketoester compound is preferably used in an amount of 2 mol or more, more preferably 3 to 20 mol, per 1 mol of the metal chelate compound. The use of 2 mol or more is preferable because it can prevent a decrease in storage stability of the resulting composition.

  The compounding amount of the organosilane compound is preferably 0.1 to 50% by mass, more preferably 0.5 to 20% by mass, and most preferably 1 to 10% by mass based on the total solid content of the low refractive index layer.

  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. It is preferable to prepare a hydrolyzate and / or partial condensate of the organosilane compound and prepare the curable composition using the resulting reaction solution (sol solution). In the present invention, first, the organosilane is prepared. A composition containing a hydrolyzate and / or partial condensate of a compound and a metal chelate compound, and a liquid obtained by adding a β-diketone compound and / or a β-ketoester compound thereto, an antiglare layer or a low refractive index It is preferable that the coating liquid is contained in at least one layer of the coating solution.

[Other binder compounds]
For the curable resin composition of the present invention, for example, the following reactive organosilicon compounds described in JP-A No. 2003-39586 can be used in combination. The reactive organosilicon compound is used in the range of 10 to 100% by mass with respect to the total of the ionizing radiation curable compound and the reactive organosilicon compound. In particular, when the following ionizing radiation curable organosilicon compound is used, it is possible to form a curable resin composition using only this as a resin component.

[Reactive organosilicon compounds]
(Silicon alkoxide)
Silicon alkoxide corresponds to the compound represented by the general formula (1), wherein X ¹¹ is an alkoxy group (OR ¹³ ), and R ¹⁰ and R ¹³ represent an alkyl group having 1 to 10 carbon atoms. To do. Examples of these compounds include tetramethoxysilane, tetraethoxysilane, tetra-i-propoxysilane, tetra-n-propoxysilane, tetra-n-butoxysilane, tetra-s-butoxysilane, and tetra-t-butoxysilane. Tetrapentaethoxysilane, tetrapenta-i-propoxysilane, tetrapenta-n-proxysilane, tetrapenta-n-butoxysilane, tetrapenta-s-butoxysilane, tetrapenta-t-butoxysilane, methyltrimethoxysilane, methyltriethoxysilane , Methyltripropoxysilane, methyltributoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethylethoxysilane, dimethylmethoxysilane, dimethylpropoxysilane, dimethylbutoxy Silane, methyl dimethoxy silane, methyl diethoxy silane, hexyl trimethoxy silane and the like.

(Silane coupling agent)
Examples of the silane coupling agent include γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxy. Silane, γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropylmethoxysilane hydrochloride, γ-glycidoxypropyltrimethoxy Silane, aminosilane, methyltrimethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilazane, vinyltris (β-methoxyethoxy) silane, octadecyldimethyl [ 3- (trimethoxysilyl) propyl] ammonium chloride, methyltrichlorosilane, dimethyldichlorosilane and the like.

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

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

1- (2) Radical Polymerization Initiator Polymerization of various monomers having an ethylenically unsaturated group used in the present invention is performed by irradiation with ionizing radiation or heating in the presence of a photo radical polymerization initiator or a thermal radical polymerization initiator. be able to. In producing the antireflection film of the present invention, a photoradical polymerization initiator and a thermal radical polymerization initiator can be used in combination.

[Photo radical polymerization initiator]
Photo radical polymerization initiators include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides (such as those described in JP-A-2001-139663) 2,3-dialkyldione compounds, disulfide compounds, fluoroamine compounds, aromatic sulfoniums, lophine dimers, onium salts, borate salts, active esters, active halogens, inorganic complexes, coumarins, etc. It is done.

  Examples of acetophenones include 2,2-dimethoxyacetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, 1-hydroxy-dimethylphenylketone, 1-hydroxydimethyl-p-isopropylphenylketone, 1-hydroxycyclohexyl Phenylketone, 2-methyl-4-methylthio-2-morpholinopropiophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, 4-phenoxydichloroacetophenone, 4-t-butyl- Examples include dichloroacetophenone.

  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. included.

Examples of benzophenones include benzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 2,4-dichlorobenzophenone, 4,4-dichlorobenzophenone and p-chlorobenzophenone, 4,4'-dimethylaminobenzophenone (Michler ketone), 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone and the like are included.

  Examples of the borate salt are described in Japanese Patent Nos. 2764769 and 2002-116539, and in 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-trimethylbenzoyl diphenylphosphine 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, compounds described in Examples in JP-A No. 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, and JP-A-5-27830. No., M.C. P. The compounds described in Hutt's “Journal of Heterocyclic Chemistry”, Vol. 1 (No. 3), (1970), and the like, particularly, an oxazole compound substituted with a trihalomethyl group: an s-triazine compound. More preferred are s-triazine derivatives in which at least one mono-, di- or tri-halogen 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-methoxy). Phenyl) -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, Nos. In p14 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, U.S. Pat. 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.

As the photo radical polymerization initiator, in addition to the above, “Latest UV Curing Technology” {Technical Information Association, Inc.} (1991), p. 159 and Kiyotsugu Kato, “Ultraviolet Curing System” {published by General Technology Center} (1989), p. Various examples are also described in 65-148 and are useful in the present invention.

  Commercially available photo radical polymerization initiators include “Kaya Cure DETX-S”, “Kaya Cure BP-100”, “Kaya Cure BDK”, “Kaya Cure CTX”, “Kaya Cure BMS”, “Kaya Cure 2” manufactured by Nippon Kayaku Co., Ltd. -EAQ "," Kaya Cure ABQ "," Kaya Cure CPTX "," Kaya Cure EPD "," Kaya Cure ITX "," Kaya Cure QTX "," Kaya Cure BTC "," Kaya Cure MCA ", etc .; manufactured by Ciba Specialty Chemicals Co., Ltd. "Irgacure 651", "Irgacure 184", "Irgacure 500", "Irgacure 819", "Irgacure 907", "Irgacure 369", "Irgacure 1173", "Irgacure 1870", "Irgacure 2959", "Irgacure 4265 "," IRGACURE 4263 ", and the like; Sartomer Co." Esacure (KIP100F, KB1, EB3, BP, X33, KTO46, KT37, KIP150, TZT) "or the like, and combinations thereof Preferred examples.

  The radical photopolymerization initiator is preferably used in the range of 0.1 to 15 parts by mass, more preferably in the range of 1 to 10 parts by mass with respect to 100 parts by mass of the polyfunctional monomer.

[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 “Kaya Cure (DMBI, EPA)” manufactured by Nippon Kayaku Co., Ltd.

[Thermal radical polymerization 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 2,2′-azobis (isobutyronitrile), 2,2′-azobis (propionitrile), 1,1′-azobis (cyclohexanecarbonitrile) as azo compounds such as ammonium sulfate and potassium persulfate And diazoaminobenzene, p-nitrobenzenediazonium and the like.

1- (3) Crosslinkable compound When the monomer or polymer binder constituting the present invention alone does not have sufficient curability, the necessary curability may be imparted by blending the crosslinkable compound. it can.

[Amino compound]
For example, when the polymer main body contains a hydroxyl group, various amino compounds are preferably used as the crosslinkable compound. The amino compound used as the crosslinkable compound is, for example, a compound containing a total of two or more of any one or both of a hydroxyalkylamino group and an alkoxyalkylamino group. Specifically, for example, a melamine compound, Examples include urea compounds, benzoguanamine compounds, glycoluril compounds, and the like.

  Melamine compounds are generally known as compounds having a skeleton in which a nitrogen atom is bonded to a triazine ring, and specific examples include melamine, alkylated melamine, methylol melamine, and alkoxylated methyl melamine. However, those having one or both of a methylol group and an alkoxylated methyl group in one molecule in total are preferably 2 or more. Specifically, methylolated melamine, alkoxylated methylmelamine, or a derivative thereof obtained by reacting melamine and formaldehyde under basic conditions is preferable, and good storage stability is obtained particularly for the curable resin composition. Alkoxylated methyl melamine is preferable in that it can be obtained and good reactivity can be obtained. There are no particular restrictions on the methylolated melamine and the alkoxylated methylmelamine used as the crosslinkable compound. For example, the methylolated melamine and the alkoxylated methylmelamine can be obtained by the method described in the document “Plastic Materials Course [8] Urea Melamine Resin” (Nikkan Kogyo Shimbun). Various resinous materials can be used.

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

[Curing catalyst]
In the antireflection film of the present invention, a compound capable of generating radicals and acids upon irradiation with ionizing radiation or heat can be used as a curing catalyst for promoting curing.

[Thermal acid generator]
Specific examples of the thermal acid generator include various aliphatic sulfonic acids and salts thereof, various aliphatic carboxylic acids and salts thereof such as citric acid, acetic acid and maleic acid, and various aromatic carboxylic acids such as benzoic acid and phthalic acid. Examples thereof include acids and salts thereof, alkylbenzenesulfonic acids and ammonium salts thereof, amine salts, various metal salts, phosphoric acid and phosphoric acid esters of organic acids, and the like.

  Commercially available materials include “Catalyst 4040”, “Catalyst 4050”, “Catalyst 600”, “Catalyst 602”, “Catalyst 500”, “Catalyst 296-9” {and above, Nippon Cytec Industries Co., Ltd.}, “NACURE series 155, 1051, 5076, 4054J” and its block type “NACURE series 2500, 5225, X49-110, 3525, 4167” {manufactured by King, Inc.} and the like. .

  The use ratio of the thermal 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. When the addition amount is within this range, the storage stability of the curable resin composition is good and the scratch resistance of the coating film is also good.

[Photosensitive acid generator, photoacid generator]
Furthermore, the photosensitive acid generator which can be used as a photoinitiator is explained in full detail.
Photosensitive acid generators include known compounds such as photoinitiators for photocationic polymerization, photodecolorants for dyes, photochromic agents, known acid generators used in microresists, and the like, and their compounds. A mixture etc. are mentioned. This will be further described below.

Examples of the photosensitive acid generator include (1) various onium salts such as iodonium salts, sulfonium salts, phosphonium salts, diazonium salts, ammonium salts, pyridinium salts; (2) β-ketoesters, β-sulfonylsulfones and these. sulfone compounds such as α-diazo compounds; (3) sulfonic acid esters such as alkyl sulfonic acid esters, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, and imino sulfonates; (4) sulfonimide compounds; and (5) diazomethane compounds. Can be mentioned.

  Examples of the onium compounds include diazonium salts, ammonium salts, iminium salts, phosphonium salts, iodonium salts, sulfonium salts, arsonium salts, and selenonium salts. Of these, diazonium salts, iodonium salts, sulfonium salts, and iminium salts are preferable from the viewpoint of photosensitivity at the start of photopolymerization, material stability of the compound, and the like. Examples thereof include compounds described in paragraph numbers [0058] to [0059] of JP-A-2002-29162.

The use ratio of the photosensitive acid generator is preferably 0.01 to 10 parts by 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- (4) Translucent Particles Various translucent particles can be used for the antireflection film of the present invention, particularly the antiglare layer, in order to impart surface scattering properties and internal scattering properties.
These translucent particles can also be used for the hard coat layer.

  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 having a refractive index difference from the binder within a numerical range as described below 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. 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.

  Among these, crosslinked polystyrene particles, crosslinked poly ((meth) acrylate) particles, and crosslinked polyacrylic (-styrene) (co) polymer particles are preferably used, and refraction of each light-transmitting particle selected from these particles is used. By adjusting the refractive index of the binder in accordance with the rate, the internal haze, surface haze, and centerline average roughness in the present invention can be achieved.

Furthermore, in the present invention, the antiglare layer preferably contains a translucent resin and translucent particles, and a binder mainly composed of a tri- or higher functional (meth) acrylate monomer and an acrylic content of 50 to 100 mass. It is preferably formed using a combination of light-transmitting particles composed of a cross-linked poly (meth) acrylate polymer that is a percentage, and in particular, the cross-linked polyacryl (-styrene) having the binder and an acrylic content of 50 to 100 mass percent A combination with translucent particles comprising a (co) polymer is preferred. The acrylic content is more preferably 60 to 100% by mass, still more preferably 100% by mass of acrylic or 60 to 95% by mass of acrylic. Particles of 100% by mass of acrylic or particles having an acrylic content of 60 to 95% by mass may be used alone, or both may be used in combination. The compounding rate in the case of using together can be adjusted so that it may become a desired refractive index.
Moreover, it is preferable that the refractive index after hardening is the range of 1.50-1.53 as a binder which has a trifunctional or more than trifunctional (meth) acrylate monomer as a main component. The translucent particles made of a crosslinked polyacrylic (-styrene) (co) polymer preferably have a refractive index in the range of 1.48 to 1.54.

  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 make the refractive index within the above range, the type and amount ratio of the binder and translucent particles may be appropriately selected. How to select can be easily known experimentally in advance.

  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 is 0.030 or less, problems such as film character blurring, dark room contrast reduction, and surface turbidity do not occur, which is preferable.

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

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

  The average particle size of the translucent particles is preferably 0.5 to 10 μm, more preferably 2.0 to 6.0 μm. If the average particle size is 0.5 μm or more, the light scattering angle distribution does not spread over a wide angle, which is preferable without causing character blur on the display. On the other hand, the thickness of 10 μm or less is preferable because it is not necessary to increase the thickness of the layer to which the light-transmitting particles are added, and problems such as curling and cost increase do not occur.

  Further, the translucent particles may be used in combination of two or more kinds having different particle diameters. Accordingly, it is possible to impart an antiglare property with the light-transmitting particles having a larger particle diameter, and to reduce the roughness of the surface with the light-transmitting particles having a smaller particle diameter.

  The translucent particles are preferably blended so as to be contained in an amount of 3 to 30% by mass in the total solid content of the layer to which they are added. More preferably, it is 5-20 mass%. By containing 3% by mass or more, a sufficient addition effect can be exhibited. If it is 30% by mass or less, problems such as image blurring, surface turbidity and glare do not occur.

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

[Translucent particle preparation, classification method]
Examples of the method for producing translucent particles according to the present invention include suspension polymerization method, emulsion polymerization method, soap-free emulsion polymerization method, dispersion polymerization method, seed polymerization method and the like. Good. These production methods are described in, for example, “Experimental Methods for Polymer Synthesis” (Takayuki Otsu and Masaaki Kinoshita, Kagaku Dojinsha), pages 130 and 146 to 147, “Synthetic Polymers” Vol. 1, p. 246-2
90, 3 volumes, p. 1 to 108, etc., and Japanese Patent Nos. 2543503, 3508304, 2746275, 3521560, 3580320, Japanese Patent Laid-Open No. 10-1561. Reference can be made to methods described in JP-A No. 7-2908, JP-A No. 5-297506, JP-A No. 2002-145919, and the like.

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

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

  The particle diameter of the inorganic particles used in the present invention is preferably as fine as possible in the dispersion medium, and the 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 such dispersion media include water, alcohols (eg, methanol, ethanol, isopropanol, butanol, benzyl alcohol, etc.), ketones (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), esters (eg, acetic acid). Methyl, ethyl acetate, propyl acetate, butyl acetate, methyl formate, ethyl formate, propyl formate, butyl formate, etc.), aliphatic hydrocarbons (eg, hexane, cyclohexane, etc.), halogenated hydrocarbons (eg, methylene chloride, chloroform, Carbon tetrachloride etc.), aromatic hydrocarbons (eg benzene, toluene, xylene etc.), amides (eg dimethylformamide, dimethylacetamide, N-methylpyrrolidone etc.), ethers (eg diethyl ether, dioxane, Tiger hydrofuran, etc.), ether alcohols (e.g., 1-methoxy-2-propanol, etc.). Toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and butanol are more preferred, and methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone are particularly preferred.

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

[High refractive index particles]
For the purpose of increasing the refractive index of the layer constituting the present invention, a cured product of a composition in which inorganic particles having a high refractive index are dispersed in a monomer, an initiator, and an organically substituted silicon compound is preferably used.

As the inorganic particles in this case, ZrO ₂ and TiO _{2 are} particularly preferably used from the viewpoint of refractive index. ZrO ₂ is most preferable for increasing the refractive index of the hard coat layer, and TiO ₂ fine particles are most preferable as the particles for the high refractive index layer and the medium refractive index layer.

As the TiO ₂ particles, inorganic particles mainly containing TiO ₂ containing at least one element selected from cobalt, aluminum, and zirconium are particularly preferable. The main component means a component having the largest content (mass%) among the components constituting the particles.

The particles mainly composed of TiO ₂ in the present invention preferably have a refractive index of 1.90 to 2.80, more preferably 2.10 to 2.80, and 2.20 to 2.80. Most preferably.

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

By containing at least one element selected from Co (cobalt), Al (aluminum) and Zr (zirconium) in the particles containing TiO ₂ as a main component, the photocatalytic activity of TiO ₂ can be suppressed. The weather resistance of the antireflection film of the invention 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 used in the present invention may have a core / shell structure as described in JP-A-2001-166104 by surface treatment.

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

[Low refractive index particles]
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, they are 35% or more and 80% or less, More preferably, they are 40% or more and 60% or less. That is, when the thickness of the low refractive index layer is 100 nm, the particle diameter of the silica fine particles is preferably 30 nm to 150 nm, more preferably 35 nm to 80 nm, and still more preferably 40 nm to 60 nm.
Here, the average particle diameter of the inorganic particles is measured by a Coulter counter.

  If the particle size of the silica fine particles is not less than the above lower limit, the effect of improving the scratch resistance is increased, and if it is not more than the above upper limit, the appearance of fine irregularities on the surface of the low refractive index layer and black tightening, This is preferable because there is no inconvenience such as deterioration of the integrated reflectance. 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.

(Silica fine particles with small size)
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 coated amount of the silica fine particles having a low refractive index is preferably from ^{1mg / m 2 ~100mg / m 2} , more preferably ^{5mg / m 2 ~80mg / m 2} , further preferably 10mg / m ² ~60mg / m ² is there. If it is at least the lower limit value, a good effect of improving scratch resistance can be exhibited. If it is not more than the upper limit value, fine irregularities are formed on the surface of the low refractive index layer, and the appearance such as black tightening and the integrated reflectance This is preferable because there is no inconvenience such as deterioration.

(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, the radius of the cavity inside the particle r _i, if the radius of the outer shell of the particle r _o, the porosity x (%) is expressed by the following equation (1). The porosity x of the hollow silica particles is preferably 10 to 60%, more preferably 20 to 60%, and most preferably 30 to 60%.
Equation (1): x = {( 4πr i 3/3) / (4πr o 3/3)} × 100

  If hollow silica particles are made to have a lower refractive index and a higher porosity, the thickness of the outer shell becomes thinner and the strength of the particles becomes weaker. From the viewpoint of scratch resistance, the refractive index of hollow silica particles The rate is usually 1.15 or higher.

A method for producing hollow silica particles is described in, for example, Japanese Patent Application Laid-Open Nos. 2001-233611 and 2002-79616. The hollow silica particles that are preferably used in the present invention are particularly preferably particles that have cavities inside the outer shell and in which the pores of the outer shell are closed. The refractive index of these hollow silica particles can be calculated by the method described in JP-A No. 2002-79616.

The coating amount of the hollow silica particles is preferably from ^{1mg / m 2 ~100mg / m 2} , more preferably ^{5mg / m 2 ~80mg / m 2} , more preferably from ^{10mg / m 2 ~60mg / m 2} . If the coating amount is not less than the lower limit value, it is preferable because a good effect of lowering the refractive index and an effect of improving scratch resistance are exhibited. If the coating amount is not more than the upper limit value, fine irregularities are formed on the surface of the low refractive index layer. This is preferable because there is no inconvenience such as black appearance and deterioration of the integrated reflectance.

  The average particle diameter of the hollow silica particles is preferably 30% or more and 150% or less of the thickness of the low refractive index layer, more preferably 35% or more and 80% or less, and further preferably 40% or more and 60% or less. 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 hollow silica particles is equal to or greater than the lower limit, the ratio of the cavities is sufficient and a decrease in the refractive index can be expected, and if it is equal to or less than the upper limit, fine irregularities are formed on the surface of the low refractive index layer. This is preferable because there is no inconvenience such as an appearance such as black tightening and deterioration of the integrated reflectance. The hollow silica 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.

  Moreover, two or more types of hollow silica particles having different particle average particle sizes can be used in combination. Here, the average particle diameter of the hollow silica particles can be determined from an electron micrograph.

The specific surface area of the hollow silica particles 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 determined by the BET method using nitrogen.

1- (6) Conductive Particles Various conductive particles can be used for imparting conductivity to the antireflection film of the present invention. The conductive particles are preferably formed from a metal oxide or nitride. Examples of metal oxides or nitrides include tin oxide, indium oxide, zinc oxide and titanium nitride. Tin oxide and indium oxide are particularly preferred.

  The conductive inorganic particles are mainly composed of these metal oxides or nitrides, and may further contain other elements. The main component means a component having the largest content (mass%) among the components constituting the particles. Examples of other elements include Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P, S, B, Nb, In, V and halogen atoms are included. In order to increase the conductivity of tin oxide and indium oxide, it is preferable to add Sb, P, B, Nb, In, V and a halogen atom. Particularly preferred are tin oxide (ATO) containing Sb and indium oxide (ITO) containing Sn. The ratio of Sb in ATO is preferably 3 to 20% by mass. The ratio of Sn in ITO is preferably 5 to 20% by mass.

The average particle diameter of the primary particles of the conductive inorganic particles used for the antistatic layer is preferably 1 to 150 nm, more preferably 5 to 100 nm, and most preferably 5 to 70 nm. The average particle diameter of the conductive inorganic particles in the antistatic layer to be formed is 1 to 200 nm, preferably 5 to 150 nm, more preferably 10 to 100 nm, and more preferably 10 to 80 nm. Most preferred. The average particle diameter of the conductive inorganic particles is an average diameter weighted by the mass of the particles and can be measured by a light scattering method or an electron micrograph.

The specific surface area of the conductive 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 conductive inorganic particles may be surface treated. The surface treatment is performed using an inorganic compound or an organic compound. Examples of inorganic compounds used for the surface treatment include alumina and silica. Silica treatment is particularly preferred. Examples of the organic compound used for the surface treatment include polyols, alkanolamines, stearic acid, silane coupling agents, and titanate coupling agents. Silane coupling agents are most preferred. Two or more types of surface treatments may be combined.

  The shape of the conductive inorganic particles is preferably a rice grain shape, a spherical shape, a cubic shape, a spindle shape, or an indefinite shape.

  Two or more types of conductive inorganic particles may be used in combination in a specific layer, and different types of conductive inorganic particles may be used for a plurality of layers of the antireflection film.

  The proportion of the conductive inorganic particles in the antistatic layer is preferably 20 to 90% by mass, preferably 25 to 85% by mass, and more preferably 30 to 80% by mass.

  The conductive inorganic particles can be used for forming an antistatic layer in the form of a dispersion.

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

The surface treatment can be carried out using a surface treatment agent of an inorganic compound or an organic compound. Examples of inorganic compounds used for the surface treatment include inorganic compounds containing cobalt (CoO ₂ , Co ₂ O ₃ , Co ₃ O _4, etc.), inorganic compounds containing aluminum {Al ₂ O ₃ , Al (OH) ₃ }, Inorganic compounds containing zirconium (such as ZrO ₂ and Zr (OH) ₄ ), inorganic compounds containing silicon (such as SiO ₂ ), inorganic compounds containing iron (such as Fe ₂ O ₃ ), etc. .

Inorganic compounds containing cobalt, inorganic compounds containing aluminum, and inorganic compounds containing zirconium are particularly preferred, and inorganic compounds containing cobalt, Al (OH) ₃ , and Zr (OH) ₄ are most preferred.

  Examples of organic compounds used for the surface treatment include polyols, alkanolamines, organic compounds having an anionic group (preferably organic compounds having a carboxyl group, a sulfonic acid group, or a phosphoric acid group, stearic acid, lauric acid Oleic acid, linoleic acid, linolenic acid, etc. are particularly preferred), silane coupling agents and titanate coupling agents. Of these, silane coupling agents are most preferred. In particular, the surface treatment is preferably performed with at least one of a silane coupling agent (organosilane compound), a partial hydrolyzate thereof, and a condensate thereof.

Examples of titanate coupling agents include metal alkoxides such as tetramethoxytitanium, tetraethoxytitanium, and tetraisopropoxytitanium, “preneact (KR-TTS, KR-46B, KR-55, KR-41B)”, etc. {Ajinomoto ( Etc.}.

  The organic compound used for the surface treatment preferably further has a crosslinkable or polymerizable functional group. Examples of the crosslinkable or polymerizable functional group include an ethylenically unsaturated group {for example, a (meth) acryl group, an allyl group, a styryl group, a vinyloxy group, etc.} capable of an addition reaction / polymerization reaction with a radical species, a cationic polymerizable group ( For example, an epoxy group, an oxatanyl group, a vinyloxy group, etc.), a polycondensation reactive group (for example, a hydrolyzable silyl group, an N-methylol group, etc.) etc. are mentioned, Preferably it is group which has an ethylenically unsaturated group.

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

  When the inorganic particles are silica, the use of a coupling agent is particularly preferred. As the coupling agent, an alkoxy metal compound (for example, a titanium coupling agent, a silane coupling agent, etc.) is preferably used. Of these, silane coupling treatment is particularly effective.

  The above coupling agent is used, for example, as a surface treatment agent for an inorganic filler of a low refractive index layer in advance for surface treatment prior to the preparation of the layer coating solution, but is further added as an additive during the preparation of the layer coating solution. It is preferably contained in the layer. In particular, the silica fine particles are preferably dispersed in the medium before the surface treatment in order to reduce the load of the surface treatment.

  Specific examples of the surface treatment agent and the surface treatment catalyst that can be preferably used in the present invention include organosilane compounds and catalysts described in International Publication No. 2004/017105 pamphlet.

1- (8) Dispersant Various dispersants can be used for dispersing the particles used in the present invention.
The dispersant preferably further contains a crosslinkable or polymerizable functional group. Examples of the crosslinkable or polymerizable functional group include an ethylenically unsaturated group {for example, a (meth) acryloyl group, an allyl group, a styryl group, a vinyloxy group, etc.} capable of an addition reaction / polymerization reaction with a radical species, a cationic polymerizable group (epoxy Groups, oxatanyl groups, vinyloxy groups, etc.), polycondensation reactive groups (hydrolyzable silyl groups, etc., N-methylol groups), and the like. Preferred are functional groups having an ethylenically unsaturated group.

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

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

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

  The dispersant preferably further contains a crosslinkable or polymerizable functional group. Examples of the crosslinkable or polymerizable functional group include an ethylenically unsaturated group {for example, a (meth) acryloyl group, an allyl group, a styryl group, a vinyloxy group, etc.} capable of an addition reaction / polymerization reaction with a radical species, a cationic polymerizable group (epoxy Groups, oxatanyl groups, vinyloxy groups, etc.), polycondensation reactive groups (hydrolyzable silyl groups, etc., N-methylol groups) and the like, and functional groups having an ethylenically unsaturated group are preferred.

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

In the preferred dispersant used in the present invention, examples of the repeating unit having an ethylenically unsaturated group in the side chain include poly-1,2-butadiene and poly-1,2-isoprene structures, or (meth) acrylic acid. An ester or amide repeating unit to which a specific residue (the R ⁰⁴ group of —COOR ⁰⁴ or CONHR ⁰⁴ ) is bonded can be used.

Examples of the specific residue (R ⁰⁴ group) include — (CH ₂ ) n—CR ⁰⁵ ═CR ⁰⁶ R ⁰⁷ , — (CH ₂ O) n—CH ₂ CR ⁰⁵ ═CR ⁰⁶ R ⁰⁷ , — ( _{CH 2 CH 2 O) n-} CH 2 CR 05 = CR 06 R 07, - (CH 2) n-NH-CO-O-CH 2 CR 05 = CR 06 R 07, - (CH 2) n-O- ^{CO-CR 05 = CR 06 R} 07 and _{(CH 2 CH 2 O) 2} -X 01) can be cited, wherein, R ⁰⁵ to R ⁰⁷ are each a hydrogen atom, a halogen atom, a carbon number 1 to 20 alkyl groups, aryl groups, alkoxy groups, aryloxy groups, R ⁰⁵ and R ⁰⁶ or R ⁰⁷ may be bonded to each other to form a ring, n is an integer of 1 to 10, and X ⁰¹ is a dicyclopentadienyl residue.

Specific examples of R ⁰⁴ of the ester residue include —CH ₂ CH═CH ₂ (corresponding to an allyl (meth) acrylate polymer described in JP-A No. 64-17047), —CH ₂ CH ₂ O—CH _{2. CH = CH 2, -CH 2 CH} 2 OCOCH = CH 2, -CH 2 CH 2 OCOC (CH 3) = CH 2, -CH 2 C (CH 3) = CH 2, -CH 2 CH = CH-C 6 _{H 5, -CH 2 CH 2 OCOCH} = CH-C 6 H 5, -CH 2 CH 2 -NHCOO-CH 2 CH = CH 2 and ^{_{CH 2 CH 2 O-X 01}} (X 01 is dicyclopentadienyl residue Group). Specific examples of the amide residue R ⁰⁴ include —CH ₂ CH═CH ₂ , —CH ₂ CH ₂ —X ⁰² (X ⁰² is a 1-cyclohexenyl residue) and CH ₂ CH ₂ —OCO—CH═CH. _{2, -CH 2 CH 2 -OCO-} C (CH 3) = CH 2 are included.

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

  The weight average molecular weight (Mw) of the dispersant having an anionic group and a crosslinkable or polymerizable functional group and having the crosslinkable or polymerizable functional group in the side chain is not particularly limited but is preferably 1000 or more. . The more preferable mass average molecular weight (Mw) of the dispersant is 2000 to 1000000, more preferably 5000 to 200000, and particularly preferably 10000 to 100000.

  The cross-linked or polymerizable functional group-containing unit may constitute all repeating units other than the anionic group-containing repeating unit, preferably 5 to 50 mol% of all the crosslinking or repeating units, Most preferably, it is 5-30 mol%.

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

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

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

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

1- (9) Antifouling agent For the purpose of imparting antifouling properties, water resistance, chemical resistance, slipping properties and the like to the antireflection film of the present invention, particularly the uppermost layer thereof, known silicone type or fluorine type It is preferable to add an antifouling agent, a slip agent and the like as appropriate.

  When these additives are added, it is preferably added in the range of 0.01 to 20% by mass of the total solid content of the low refractive index layer, more preferably in the range of 0.05 to 10% by mass. Particularly preferred is 0.1 to 5% by mass.

  Preferable examples of the silicone compound include those having a substituent at the end of the compound chain and / or the side chain, containing a plurality of dimethylsilyloxy units as repeating units. The compound chain containing dimethylsilyloxy as a repeating unit may contain a structural unit other than dimethylsilyloxy.

  The substituents may be the same or different, and a plurality of substituents are preferable. Examples of preferred substituents include acryloyl group, methacryloyl group, vinyl group, aryl group, cinnamoyl group, epoxy group, oxetanyl group, hydroxyl group, fluoroalkyl group, polyoxyalkylene group, carboxyl group, amino group and the like. It is done.

  Although there is no restriction | limiting in particular in the molecular weight of a silicone type compound, It is preferable that it is 100,000 or less, It is more preferable that it is 50,000 or less, It is especially preferable that it is 3000-30000, It is most preferable that it is 10,000-20000. .

  Moreover, although there is no restriction | limiting in particular in silicon atom content of a silicone type compound, it is preferable that it is 18.0 mass% or more, it is especially preferable that it is 25.0-37.8 mass%, and 30.0-37. Most preferably, it is 0 mass%.

  Examples of preferable silicone compounds include “X-22-174DX”, “X-22-2426”, “X-22-164B”, “X22-164C”, “X-” manufactured by Shin-Etsu Chemical Co., Ltd. “22-170DX”, “X-22-176D”, “X-22-1821” (named above); “Silaplane FM-0725”, “Silaplane FM-7725”, “Sila” manufactured by Chisso Corporation "Plain FM-4421", "Silaplane FM-5521", "Silaplane FM-6621", "Silaplane FM-1121"; "DMS-U22", "RMS-033", "RMS-083" manufactured by Gelest "," UMS-182 "," DMS-H21 "," DMS-H31 "," HMS-301 "," FMS121 "," FMS123 "," FM 131 "," FMS141 "," FMS221 "(trade names), but the like, but is not limited thereto.

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

  The fluorine-based compound preferably further has a substituent that contributes to the formation of a bond with the low refractive index layer film or compatibility. The substituents may be the same or different, and a plurality of substituents are preferable. Examples of preferred substituents include acryloyl group, methacryloyl group, vinyl group, aryl group, cinnamoyl group, epoxy group, oxetanyl group, hydroxyl group, polyoxyalkylene group, carboxyl group, amino group and the like.

  The fluorine-based compound may be a copolymer with a compound containing no fluorine atom or a co-oligomer, and the molecular weight is not particularly limited.

  Although there is no restriction | limiting in particular in fluorine atom content of a fluorine-type compound, It is preferable that it is 20 mass% or more, It is especially preferable that it is 30-70 mass%, It is most preferable that it is 40-70 mass%.

  Examples of preferred fluorine-based compounds include “R-2020”, “M-2020”, “R-3833”, “M-3833” (all trade names) manufactured by Daikin Chemical Industries, Ltd .; "Megafuck F-171", "Megafuck F-172", "Megafuck F-179A", "Defenser MCF-300" (above product names), etc. manufactured by Co., Ltd., etc. are mentioned, but are not limited to these is not.

  For the purpose of imparting properties such as dust resistance and antistatic property, a known cationic surfactant or a dustproof agent such as a polyoxyalkylene compound, an antistatic agent, or the like can be appropriately added. These dustproofing agent and antistatic agent may contain the structural unit as a part of the function in the above-mentioned silicone compound or fluorine compound.

  Examples of preferred compounds include “Megafac F-150” (trade name) manufactured by Dainippon Ink and “SH-3748” (trade name) manufactured by Toray Dow Corning Co., Ltd. It is not limited to.

1- (10) Surfactant In the antireflection film of the present invention, in order to ensure surface uniformity such as coating unevenness, drying unevenness, point defect, etc., any one of fluorine-based and silicone-based surfactants may be used. It is preferable to contain both of them 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 fluoroaliphatic group-containing copolymers (sometimes abbreviated as “fluoropolymer surfactant”). An acrylic (co) polymer, a methacrylic (co) polymer containing a repeating unit corresponding to the monomer (i) below, or a repeating unit corresponding to the monomer (i) below and the following (ii) Acrylic copolymers and methacrylic copolymers containing repeating units corresponding to the monomers, and copolymers with vinyl monomers copolymerizable therewith are useful.

(I) Fluoroaliphatic group-containing monomer represented by the following general formula (2) General formula (2):

In general formula (2), R ²¹ represents a hydrogen atom or a methyl group, L ²¹ represents an oxygen atom, a sulfur atom or N (R ²²⁾ - represents a oxygen atom are preferred. s1 represents an integer of 1 to 6, and t1 represents an integer of 2 to 4. R ²² 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.

(Ii) Monomer represented by the following general formula (3) copolymerizable with the above (i) General formula (3):

In the general formula (3), R ³¹ represents a hydrogen atom or a methyl group, L ³¹ represents an oxygen atom, a sulfur atom or N (R ³³ ) —, and R ³³ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Specifically, it represents a methyl group, an ethyl group, a propyl group or a butyl group, preferably a hydrogen atom or a methyl group. L ³¹ is preferably an oxygen atom, —N (H) —, and N (CH ₃ ) —.

R ³² represents a linear, branched or cyclic alkyl group having 4 to 20 carbon atoms which may have a substituent. Examples of the substituent for the alkyl group of R ³² 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 (2) used in the fluoropolymer surfactant that can be used in the present invention is determined according to each unit of the fluoropolymer surfactant. It is 10 mol% or more based on a monomer, Preferably it is 15-70 mol%, More preferably, it is the range of 20-60 mol%.

  The preferred mass average molecular weight of the fluoropolymer surfactant 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 surfactant used in the present invention is in the range of 0.001 to 5% by mass, preferably in the range of 0.005 to 3% by mass with respect to the coating solution. More preferably, it is the range of 0.01-1 mass%. If the addition amount of the fluorine-based polymer surfactant is 0.001% by mass or more, the effect is sufficiently exhibited, which is preferable, and if it is 5% by mass or less, the coating film is not sufficiently dried. Or adverse effects on the performance as a coating film (for example, reflectivity, scratch resistance), and the like.

  Hereinafter, although the example of the specific structure of the fluoropolymer surfactant containing the repeating unit corresponding to the fluoro aliphatic group containing monomer represented by General formula (2) is shown, it is not this limitation. In addition, the number in a formula shows the molar ratio of each monomer component. Mw represents a mass average molecular weight.

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

  Alternatively, when the upper layer is applied, by selecting a fluoropolymer surfactant that can be extracted into the solvent that forms the upper layer, it is not unevenly distributed on the lower layer surface (= interface), and the upper layer and the lower layer are in close contact with each other. Thus, it is possible to provide an antireflection film that maintains surface uniformity even during high-speed application and has high scratch resistance. Further, by preventing the surface free energy from decreasing, the object can be achieved by controlling the surface energy of the antiglare layer before application of the low refractive index layer to the above range. Examples of such fluoropolymer surfactants are acrylic (co) polymers, methacrylic (co) polymers containing repeating units corresponding to the monomer (iii) below, or the following (iii) An acrylic copolymer, a methacrylic copolymer, and a copolymer of a vinyl monomer copolymerizable therewith, and a repeating unit corresponding to the monomer (iv) and a repeating unit corresponding to the monomer (iv) It is.

(Iii) Fluoroaliphatic group-containing monomer represented by the following general formula (4) General formula (4)

In the general formula (4), R ⁴¹ represents a hydrogen atom, a halogen atom or a methyl group, and more preferably a hydrogen atom or a methyl group. L ⁴¹ represents an oxygen atom, a sulfur atom or —N (R ⁴² ) —, more preferably an oxygen atom or —N (R ⁴² ) —, and still more preferably an oxygen atom. s2 represents an integer of 1 to 6 (more preferably 1 to 3, more preferably 1), and t2 represents an integer of 1 to 18 (more preferably 4 to 12 and even more preferably 6 to 8). . R ⁴² represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms which may have a substituent, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and further preferably a hydrogen atom or a methyl group.

  Further, in the fluoropolymer surfactant, two or more kinds of repeating units corresponding to the fluoroaliphatic group-containing monomer represented by the general formula (4) may be contained as a constituent component.

(Iv) Monomer represented by the following general formula (5) copolymerizable with the above (iii) General formula (5)

In the general formula (5), R ⁵¹ represents a hydrogen atom, a halogen atom or a methyl group, more preferably a hydrogen atom or a methyl group. L ⁵¹ represents an oxygen atom, a sulfur atom or —N (R ⁵³ ) —, more preferably an oxygen atom or —N (R ⁵³ ) —, and still more preferably an oxygen atom. R ⁵³ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and still more preferably a hydrogen atom or a methyl group.

R ⁵² is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkyl group containing a poly (alkyleneoxy) group, or an aromatic which may have a substituent. Represents a group (for example, a phenyl group or a naphthyl group). A linear, branched or cyclic alkyl group having 1 to 12 carbon atoms or an aromatic group having 6 to 18 carbon atoms is more preferable, and a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms is still more preferable. .

  The preferred amount of the fluoroaliphatic group-containing monomer represented by the general formula (4) used in the fluoropolymer surfactant that can be used in the present invention is each of the fluoropolymer surfactant. It is 10-100 mol% based on a monomer, Preferably it is 20-100 mol%, More preferably, it is the range of 40-100 mol%.

  Hereinafter, although the example of the specific structure of a fluoropolymer surfactant containing the repeating unit corresponding to the fluoro aliphatic group containing monomer represented by General formula (4) is shown, it is not this limitation. In addition, the number in a formula shows the molar ratio of each monomer component. Mw represents a mass average molecular weight.

1- (11) Thickener The antireflection film of the present invention may use a thickener in order to adjust the viscosity of the coating liquid for forming the functional layer.
The term “thickener” as used herein means that the viscosity of the liquid is increased by adding the thickener, and the amount by which the viscosity of the coating liquid is increased by addition is preferably 0.05 to 50 cP. More preferably, it is 0.10-20 cP, Most preferably, it is 0.10-10 cP.

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 (neopentylglycol adipate),
Poly (neopentyl glycol sebacate),
Poly (1,3-propylene adipate),
Poly (1,3-propylene glutarate),
Polyvinyl butyral,
Polyvinyl formal,
Polyvinyl acetal,
Polyvinylpropanal,
Polyvinyl hexanal,
Polyvinylpyrrolidone,
Poly (meth) acrylic acid ester,
Cellulose acetate,
Cellulose propionate,
Cellulose acetate butyrate.

  In addition, smectite, tetrasilica mica, bentonite, silica, montmorillonite and sodium polyacrylate described in JP-A-8-325491, ethylcellulose, polyacrylic acid, organic clay described in JP-A-10-219136, etc. Well-known viscosity modifiers and thixotropic agents can be used.

1- (12) Coating solvent In the present invention, as the solvent used in the coating composition for forming each layer, each component can be dissolved or dispersed, and a uniform surface is likely to be formed in the coating process and the drying process. In addition, various solvents selected from the viewpoints of ensuring liquid storage stability and having an appropriate saturated vapor pressure can be used.

  Two or more kinds of solvents can be mixed and used. In particular, from the viewpoint of drying load, it is preferable that a solvent having a boiling point of 100 ° C. or lower at normal pressure and room temperature as a main component and a small amount of solvent having a boiling point of 100 ° C. or higher for adjusting the drying speed.

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

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

1- (13) Others In addition to the above components, the antireflection 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 ray. Absorbers, infrared absorbers, adhesion-imparting agents, polymerization inhibitors, antioxidants, surface modifiers, and the like can also be added.

1- (14) Support The support for the antireflection 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, etc.), polyethylene terephthalate film, polyether Sulfone film, polyacrylic resin film, polyurethane resin film, polyester film, polycarbonate film, polysulfone film, polyether film, polymethylpentene film, polyetherketone film, (meth) acrylonitrile film, polynorbornene resin film { For example, “Arton” (trade name) manufactured by JSR Corporation, and “Zeonex” (trade name) manufactured by Nippon Zeon Co., Ltd.} There 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.

[Cellulose acetate]
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 is ASTM
It follows the measurement and calculation of the degree of acetylation in 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 value of Mw / Mn (Mw is a mass average molecular weight, Mn is a number average molecular weight) by gel permeation chromatography (GPC) close to 1.0. A narrow molecular weight distribution 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 the 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 substitution degree is preferably substituted with 32% or more of an acyl group, 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], and paragraph “ Cellulose acetate obtained by the method described in “0051” to “0052” [Synthesis Example 3] can be used.

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

  The organic solvent includes a solvent selected from ether having 3 to 12 carbon atoms, ketone having 3 to 12 carbon atoms, ester having 3 to 12 carbon atoms, and halogenated hydrocarbon having 1 to 6 carbon atoms. preferable. Two or more organic solvents may be mixed and used.

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

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

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

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

  The cellulose acylate solution (dope) can be adjusted by a general method. A general method means processing at a temperature of 0 ° C. or higher (room temperature or high temperature). The solution can be prepared by using a dope preparation method and apparatus in a normal solvent cast method. In the case of a general method, it is preferable to use a halogenated hydrocarbon (particularly methylene chloride) as the organic solvent. A non-chlorinated solvent can also be used, and examples thereof include those described in JIII Journal of Technical Disclosure No. 2001-1745.

  The amount of cellulose acylate is adjusted so as to be contained in the obtained solution in an amount of 10 to 40% by mass. The amount of cellulose acylate is more preferably 10 to 30% by mass. Arbitrary additives described later may be added to the organic solvent (main solvent).

The solution can be prepared by stirring cellulose acylate and an organic solvent at room temperature (0 to 40 ° C.). The high concentration solution may be stirred under pressure and heating conditions. Specifically, cellulose acylate and an organic solvent are placed in a pressure vessel and sealed, and stirred while heating to a temperature not lower than the boiling point of the solvent at normal temperature and in a range where the solvent does not boil. The heating temperature is usually 40 ° C. or higher, preferably 60 to 200 ° C., more preferably 80 to 110 ° C.

  Each component may be coarsely mixed in advance and then placed in a container. Moreover, you may put into a container sequentially.

  A container configured to be stirred is used. The container can be pressurized by injecting an inert gas such as nitrogen gas. Moreover, you may utilize the raise of the vapor pressure of the solvent by heating. Or after sealing a container, you may add each component under pressure. When heating, it is preferable to heat from the outside of the container. For example, a jacket type heating device can be used. The entire container can also be heated by providing a plate heater outside the container and piping to circulate the liquid.

  It is preferable to provide a stirring blade inside the container and stir using this. The stirring blade preferably has a length that reaches the vicinity of the wall of the container. A scraping blade is preferably provided at the end of the stirring blade in order to renew the liquid film on the vessel wall.

  Instruments such as a pressure gauge and a thermometer may be installed in the container. Each component is dissolved in a solvent in the container. The prepared dope is taken out of the container after cooling, or is taken out and then cooled using a heat exchanger or the like.

  A solution can also be prepared by a cooling dissolution method. In the cooling dissolution method, cellulose acylate can be dissolved in an organic solvent that is difficult to dissolve by a normal dissolution method. In addition, even if it is a solvent which can melt | dissolve a cellulose acetate with a normal melt | dissolution method, there exists an effect that a uniform solution can be obtained rapidly according to a cooling melt | dissolution method.

  In the cooling dissolution method, first, cellulose acylate is gradually added to an organic solvent at room temperature while stirring. The amount of cellulose acylate is preferably adjusted so as to be contained in the mixture in an amount of 10 to 40% by mass. The amount of cellulose acylate is more preferably 10 to 30% by mass. Furthermore, you may add the arbitrary additive mentioned later in a mixture.

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

  Further, when this is heated to 0 to 200 ° C. (preferably 0 to 150 ° C., more preferably 0 to 120 ° C., most preferably 0 to 50 ° C.), cellulose acetate is dissolved in the organic solvent. The temperature can be raised by simply leaving it at room temperature or in a warm bath. The heating rate is preferably 4 ° C./min or more, more preferably 8 ° C./min or more, and most preferably 12 ° C./min or more. The higher the heating rate, the better. However, 10,000 ° C./second is the theoretical upper limit, 1000 ° C./second is the technical upper limit, and 100 ° C./second is the practical upper limit. The heating rate is a value obtained by dividing the difference between the temperature at the start of heating and the final heating temperature by the time from the start of heating until the final heating temperature is reached. .

  A uniform solution is obtained as described above. If the dissolution is insufficient, the cooling and heating operations may be repeated. Whether or not the dissolution is sufficient can be determined by merely observing the appearance of the solution with the naked eye.

  In the cooling dissolution method, it is desirable to use a sealed container in order to avoid moisture mixing due to condensation during cooling. In the cooling and heating operation, when the pressure is applied during cooling and the pressure is reduced during heating, the dissolution time can be shortened. In order to perform pressurization and decompression, it is desirable to use a pressure-resistant container.

  In addition, according to differential scanning calorimetry (DSC), a 20% by mass solution of cellulose acetate (acetylation degree: 60.9%, viscosity average polymerization degree: 299) dissolved in methyl acetate by the cooling dissolution method is There is a quasi-phase transition point between a sol state and a gel state in the vicinity of 33 ° C., and a uniform gel state is obtained below this temperature. Therefore, this solution needs to be maintained at a temperature equal to or higher than the pseudo phase transition temperature, preferably about the gel phase transition temperature + 10 ° C. However, this pseudo phase transition temperature varies depending on the degree of acetylation of cellulose acetate, the degree of viscosity average polymerization, the concentration of the solution, and the organic solvent used.

  A cellulose acylate film is produced from the prepared cellulose acylate solution (dope) by a solvent cast method.

  The dope is cast on a drum or band and the solvent is evaporated to form a film. The concentration of the dope before casting is preferably adjusted so that the solid content is 18 to 35% by mass.

  The surface of the drum or band is preferably finished in a mirror state. The casting and drying methods in the solvent casting method are described in U.S. Pat. Nos. 736892, JP-B 45-4554, 49-5614, and 62-1115035.

  The dope is preferably cast on a drum or band having a surface temperature of 10 ° C. or less.

  After casting, it is preferable to dry it by applying air for 2 seconds or more. The obtained film can be peeled off from the drum or band, and further dried by high-temperature air whose temperature is successively changed from 100 to 160 ° C. to evaporate the residual solvent. The above method is described in Japanese Patent Publication No. 5-17844. According to this method, it is possible to shorten the time from casting to stripping. In order to carry out this method, it is necessary for the dope to gel at the surface temperature of the drum or band during casting.

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

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

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

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

  In the case of a single-layer liquid, it is necessary to extrude a cellulose acylate solution having a high concentration and a high viscosity in order to obtain a required film thickness. It often occurs and causes problems, such as a failure or flatness. As this solution, a plurality of cellulose acylate solutions are cast from a casting port. As a result, it is possible to extrude a highly viscous solution onto the support at the same time, not only can the flatness be improved and an excellent planar film can be produced, but also a concentrated cellulose acylate solution can be used to reduce the drying load. Reduction can be achieved and film production speed can be increased.

[Plasticizer]
A plasticizer can be added to the cellulose acylate film in order to improve the mechanical properties or to improve the drying speed after casting in the production of the film.

  As the plasticizer, phosphoric acid ester or carboxylic acid ester is used. Examples of phosphate esters include triphenyl phosphate (TPP), diphenyl biphenyl phosphate, and tricresyl phosphate (TCP). Representative examples of the carboxylic acid ester include phthalic acid esters and citric acid esters. Examples of phthalic acid esters include dimethyl phthalate (DMP), diethyl phthalate (DEP), dibutyl phthalate (DBP), dioctyl phthalate (DOP), diphenyl phthalate (DPP) and diethyl hexyl phthalate (DEHP). Examples of citrate esters include triethyl O-acetylcitrate (OACTE) and tributyl O-acetylcitrate (OACTB). Examples of other carboxylic acid esters include butyl oleate, methylacetyl ricinoleate, dibutyl sebacate, and various trimellitic acid esters. Phthalate plasticizers (DMP, DEP, DBP, DOP, DPP, DEHP) are preferably used. DEP and DPP are particularly preferred.

  The addition amount of the plasticizer is preferably 0.1 to 25% by mass of the amount of cellulose acylate, more preferably 1 to 20% by mass, and most preferably 3 to 15% by mass.

[Deterioration inhibitor]
A degradation inhibitor (eg, antioxidant, peroxide decomposer, radical inhibitor, metal deactivator, acid scavenger, amine) may be added to the cellulose acylate film.

  The deterioration inhibitors are described in JP-A-3-199201, JP-A-597073, JP-A-5-194789, JP-A-5-271471, and JP-A-6-107854. The addition amount of the deterioration preventing agent is preferably 0.01 to 1% by mass of the solution (dope) to be prepared in consideration of the effect of the deterioration preventing agent and bleeding out (bleeding out) to the film surface. More preferably, the content is 0.01 to 0.2% by mass. Examples of particularly preferred deterioration inhibitors include butylated hydroxytoluene (BHT) and tribenzylamine (TBA).

[Retardation adjuster]
In order to adjust the retardation of the film, a retardation adjusting agent can be used as necessary for the cellulose acylate film. The retardation of the film is preferably 0 to 300 nm in the film thickness direction and 0 to 1000 nm in the in-plane direction.

  As the retardation increasing agent, an aromatic compound having at least two aromatic rings is preferable, and the aromatic compound is used in the range of 0.01 to 20 parts by mass with respect to 100 parts by mass of cellulose acylate. The aromatic compound is preferably used in the range of 0.05 to 15 parts by mass, and more preferably in the range of 0.1 to 10 parts by mass with respect to 100 parts by mass of cellulose acetate. Two or more aromatic compounds may be used in combination.

  Details are described in JP-A Nos. 2000-1111914, 2000-275434, 2002-236215, WO 00/065384, and the like.

[Stretching treatment of cellulose acylate film]
The produced cellulose acylate film can further improve drying unevenness, film thickness unevenness caused by drying shrinkage, and surface unevenness by stretching treatment. The stretching treatment is also used for adjusting the retardation.

  Although there is no limitation in particular in the method of the width direction extending | stretching process, the extending method by a tenter is mentioned as the example. More preferably, the longitudinal stretching is performed in the longitudinal direction of the roll, and the longitudinal stretching is performed by adjusting the draw ratio of each pass roll (rotational ratio between the pass rolls) between the pass rolls that transport the roll film. Is possible.

[Polyethylene terephthalate film]
In the present invention, the polyethylene terephthalate film is also excellent in transparency, mechanical strength, planarity, chemical resistance and moisture resistance, and is preferably used because it is inexpensive.

[Easy adhesion treatment]
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 the commercially available PET film with an easily adhesive layer for optics include “Cosmo Shine A4100, A4300” manufactured by Toyobo Co., Ltd.

2. Layers Constructing Antireflection Film The antireflection film of the present invention is obtained by mixing the composition containing the various compounds described above and coating the composition on a transparent support to form various functional layers. . The antireflection film of the present invention has at least an antiglare layer and a low refractive index layer on a transparent support. Moreover, it can also have another functional layer according to the objective. Next, each functional layer constituting the antireflection film of the present invention will be described.

2- (1) Hard Coat Layer The antireflection film of the present invention is preferably provided with a hard coat layer on one surface of the transparent support in order to impart the physical strength of the film. An antiglare layer and a low refractive index layer are provided on the substrate. 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. Moreover, it is good also as a structure which reduces the number of layers by providing an anti-glare property to a hard-coat layer and setting it as an anti-glare hard-coat layer.

  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 aspect of the present invention, since there is at least one low refractive index layer on the hard coat layer, if the refractive index of the hard coat layer is equal to or higher than the lower limit value, the antireflection property becomes good, and the lower limit value or lower. If it exists, since the tendency that the color of reflected light becomes strong too much does not arise, it is preferable.

  The thickness of the hard coat layer is usually about 0.5 to 50 μm, preferably 1 to 20 μm, more preferably 2 from the viewpoint of imparting sufficient durability and impact resistance to the film. 10 μm, most preferably 3 to 7 μm.

Further, the hardness of the hard coat layer is preferably H or more, more preferably 2H or more, and most preferably 3H or more in the pencil hardness test.
Furthermore, in the Taber test according to JIS K-5400, 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 applying 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 is provided with translucent 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. You may contain.

  For the purpose of controlling the refractive index of the hard coat layer, a high refractive index monomer and / or inorganic particles 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 formation of the hard coat layer, and the inorganic particles dispersed therein are referred to as a binder.

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

  As a method for 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; JP-A 2000-206317 A method of forming by curing shrinkage of an ionizing radiation curable resin due to a difference in ionizing radiation dose as described in the gazette; a good solvent for the translucent resin by drying as described in JP-A-2000-338310 A method in which the light-transmitting fine particles and the light-transmitting resin are solidified while being gelled to reduce the mass ratio, thereby forming irregularities on the surface of the coating film; as described in JP-A-2000-275404, And the like are known, and these known methods can also be used in the present invention.

  The antiglare layer that can be used in the present invention contains a translucent resin and translucent particles for imparting antiglare properties. The antiglare layer is preferably formed using a coating solution containing a binder polymer capable of imparting hard coat properties, translucent particles and a solvent, and the projections of the translucent particles themselves or an aggregate of a plurality of particles It is preferable that irregularities on the surface be formed by the protrusions formed in step (b).

  The antiglare layer formed by the dispersion of the translucent particles contains a translucent resin and the translucent particles dispersed in the translucent resin. The antiglare layer having antiglare properties preferably has both antiglare properties and hard coat properties. The translucent resin is preferably formed by using the compound described in the section 1- (1) Binder, and among them, the compound listed in the section [Photopolymerizable polyfunctional monomer] is preferably used. Most preferably, the main component is a tri- or higher functional (meth) acrylate monomer. Here, the main component means that the translucent resin occupies a majority of the weight fraction, and specifically, the weight fraction of the trifunctional or higher functional (meth) acrylate monomer contained in the translucent resin. It is preferable that the sum exceeds 50%.

Specific examples of the translucent particles include inorganic compound particles such as silica particles and TiO ₂ particles; resin particles such as acrylic particles, crosslinked acrylic particles, polystyrene particles, crosslinked styrene particles, melamine resin particles, and benzoguanamine resin particles. Is preferred. Of these, crosslinked poly (meth) acrylic particles and crosslinked polyacrylic (-styrene) (co) polymer particles are preferred.

Either a spherical shape or an indefinite shape can be used as the shape of the translucent particles.
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 size and to impart another optical characteristic with a light-transmitting particle having a smaller particle size. For example, when an anti-glare antireflection film is attached to a high-definition display of 133 ppi or higher, a problem in display image quality called “glare” may occur. “Glitter” is derived from the fact that the unevenness existing on the surface of the antiglare and antireflection film causes the pixels to be enlarged or reduced and loses uniformity of brightness, but is smaller than the light-transmitting particles that impart antiglare properties. The particle diameter can be greatly improved by using light-transmitting particles having a different refractive index from that of the binder.

The translucent particles are contained in the antiglare layer so that the amount of the translucent particles in the formed antiglare layer is preferably 10 to 1000 mg / m ² , more preferably 100 to 700 mg / m ^2. .

  The particle size distribution of the translucent particles is measured by a Coulter counter method, and the measured distribution is converted into a particle number distribution.

The film thickness of the antiglare layer is preferably in the range of 1 to 15 μm, and more preferably in the range of 1.2 to 8 μm. If it is not less than the lower limit, the hard property will not be insufficient, and if it is not more than the upper limit, problems such as curling and deterioration of workability due to a decrease in brittleness will not occur. It is preferable to do this.

  On the other hand, the center line average roughness (Ra) of the antiglare layer is preferably in the range of 0.08 to 0.30 μm. If Ra is less than or equal to the upper limit, problems such as glare and whitening of the surface when external light is reflected do not occur. Further, the value of the transmitted image definition is preferably 5 to 60%.

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

2- (3) High Refractive Index Layer, Medium Refractive Index Layer The antireflective film of the present invention is more preferably provided with a high refractive index layer and a medium refractive index layer to further improve the antireflection property.

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 1.70-2.20. 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 1.55-1.80.

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.
The inorganic particles are preferably dispersed in the dispersion medium in the presence of a dispersant.

  The high refractive index layer and 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, the ionizing radiation curable composition described above). 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. It is preferable that the coating composition is applied and cured by a crosslinking reaction or a polymerization reaction of an ionizing radiation curable compound (for example, a polyfunctional monomer or a polyfunctional oligomer).

  Furthermore, it is preferable to cause the binder of the high refractive index layer and the medium refractive index layer to undergo a crosslinking reaction or a polymerization reaction with the dispersant simultaneously with or after the coating of the layer.

The binder of the high refractive index layer and the medium refractive index layer thus prepared is, for example, a binder or ionizing radiation curable polyfunctional monomer or polyfunctional oligomer cross-linked or polymerized to form a binder. The anionic group of the dispersant is incorporated. Furthermore, the binder of the high refractive index layer and the medium refractive index layer has a function of maintaining the dispersion state of the inorganic particles by the anionic group, and the crosslinked or polymerized structure imparts a film forming ability to the binder and contains inorganic particles. To improve the physical strength, chemical resistance and weather resistance of the high refractive index layer and medium refractive index layer.

  The binder of the high refractive index layer is 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 kinds of 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 5% or less, more preferably 3% or less, and particularly preferably 1% or less.

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

  The refractive index of the low refractive index layer is preferably 1.20 to 1.46, more preferably 1.25 to 1.46, and particularly preferably 1.30 to 1.46.

  The thickness of the low refractive index layer is preferably 50 to 200 nm, and more preferably 70 to 100 nm. The haze of the low refractive index layer is preferably 3% or less, more preferably 2% or less, and most preferably 1% or less. The specific hardness of the low refractive index layer is preferably H or more, more preferably 2H or more, and most preferably 3H or more in a pencil hardness test under a 500 g load.

  In order to improve the antifouling performance of the antireflection film, it is preferable that the contact angle of the surface with respect to water is 90 ° or more. More preferably, it is 95 ° or more, and particularly preferably 100 ° or more.

  The curable composition particularly preferably used for forming the low refractive index layer preferably comprises (A) the fluoropolymer, (B) inorganic particles, and (C) an organosilane compound.

In the low refractive index layer, a binder is used for dispersing and fixing the fine particles in the present invention. As the binder, those described in the section 1- (1) Binder can be used, and it is preferable to use the above-mentioned fluoropolymer having a low refractive index of the binder itself or a fluorosol / gel material. The fluorine-containing polymer or fluorine-containing sol / gel is crosslinked by heat or ionizing radiation, has a dynamic friction coefficient of 0.03 to 0.30 on the surface of the formed low refractive index layer, and has a contact angle with water of 85 to 120 °. The material which becomes is preferable.

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

The thickness of the antistatic layer is preferably from 0.01 to 10 μm, more preferably from 0.03 to 7 μm, and even more preferably from 0.05 to 5 μm. The surface resistance of the antistatic layer is preferably from 10 ⁵ to 10 is ¹² Omega / □, more preferably 10 ⁵ to 10 ⁹ Omega / □ is the most be 10 ⁵ to 10 ⁸ Omega / □ is 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. Further, the transmittance of light having a wavelength of 550 nm is preferably 50% or more, more preferably 60% or more, further preferably 65% or more, and most preferably 70% or more.

  The antistatic layer in the present invention preferably has excellent hardness, and the specific antistatic layer has a pencil hardness of 1 kg load, preferably H or higher, more preferably 2H or higher. Preferably, it is 3H or more, more preferably 4H or more.

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

2- (7) Interference nonuniformity (rainbow nonuniformity) prevention layer A substantial refractive index difference (refractive index difference is 0. 0) between the transparent support and the hard coat layer or the transparent support and the antiglare layer in the antireflection film of the present invention. 03 or more), reflected light is generated at the transparent support / hard coat layer or 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, an intermediate refractive index n _P is provided between the transparent support and the hard coat layer (or antiglare layer), and the film thickness d _P satisfies the following formula (2). Such an interference non-uniformity prevention layer can also be provided.
Formula (2): d _P = (2N−1) × λ / (4n _P )
Where λ is the wavelength of visible light and any value in the range of 450 to 650 nm, and N is a natural number.

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

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

2- (8) Easy-Adhesion Layer An easy-adhesion layer can be applied to the antireflection film of the present invention. The easy-adhesion layer, for example, provides a function that facilitates adhesion of the protective film and its adjacent layer, or the hard coat layer and the support when the antireflection film of the present invention is used as a protective film for polarizing plates. It refers to the layer.

  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 an antireflection film. A layer containing a polymer compound having a -COOM group is provided on the support 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, a vinyl acetate-maleic acid copolymer having a -COOM group is preferably used. Such polymer compounds can be used alone or in combination of two or more.

  A preferable mass average molecular weight of the polymer compound is about 500 to 500,000. Particularly preferred examples of the polymer compound having a —COOM group include those described in JP-A-6-094915 and JP-A-7-333436.

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

  The thickness of the easy adhesion layer is preferably in the range of 0.05 to 1.0 μm. If it is 0.05 μm or more, sufficient adhesiveness can be obtained, and even if it is thicker than 1.0 μm, the effect of adhesiveness is not improved so much. Therefore, it is preferable that the easy-adhesion layer is in this thickness range.

2- (9) Anti-curl Layer The anti-reflection film of the present invention can be subjected to anti-curl processing. The anti-curl process is a process for imparting a function of curling with the surface to which the anti-curl process is applied, and specifically includes an anti-curl layer. When the above-mentioned various functional layers are formed only on one side of a transparent resin film such as an antireflection film, there is a tendency to curl with the surface on which the various functional layers are formed inside. The curl prevention layer functions to prevent the occurrence of such curling.

  The anti-curl layer can include an embodiment provided on the back surface of the anti-reflection film, that is, on the surface of the support opposite to the side having the anti-glare layer or the anti-reflection layer. In some cases, an easy-adhesion layer is coated on the back surface, and depending on the state of curling, an aspect in which an anti-curl layer is coated on the opposite side, that is, the side having the antiglare layer or the antireflection layer may be mentioned. it can.

  Specific examples of the anti-curl processing include solvent coating, and a method of coating a solvent and a transparent resin layer such as cellulose triacetate, cellulose diacetate, and cellulose acetate propionate.

  Specifically, the solvent coating method is performed by coating a solvent that dissolves a cellulose acylate film used as a support for an antireflection film or a composition containing a solvent that swells. 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 preferable ketone-based organic solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetyl acetone, diacetone alcohol, isophorone, ethyl-n-butyl ketone, diisopropyl ketone, diethyl ketone, di-n-propyl ketone, methylcyclohexanone, Methyl-n-butylketone, methyl-n-propylketone, methyl-n-hexylketone, methyl-n-heptylketone, and the like. Examples of preferable ester organic solvents include methyl acetate, ethyl acetate, butyl acetate, and lactic acid. Examples include methyl and ethyl lactate.

  However, the solvent to be used may include a solvent that dissolves the cellulose acylate film and / or a solvent that swells, and further includes a solvent that does not dissolve the film, depending on the curl degree of the transparent resin film and the type of resin. The composition and the coating amount mixed at an appropriate ratio are used. In addition, the anti-curl function is exhibited even if transparent hard processing or antistatic processing is applied.

2- (10) Water Absorption Layer The antireflection film of the present invention can be provided with a layer containing a water absorbent. The water absorbent can be selected from compounds having a water absorption function, mainly alkaline earth metals. For example, BaO, SrO, CaO, MgO, etc. are mentioned. 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 using a vacuum deposition method or the like as in the antistatic 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 may be provided between the support and the laminate (various functional layers including the antireflection layer), the uppermost layer of the laminate, or between the laminates, or the organic in the laminate A water absorbent may be added to the layer or the antistatic layer. When added to the antistatic layer, it is preferable to use a co-evaporation method.

2- (11) Primer layer / inorganic thin film layer In the antireflection film of the present invention, a known primer layer or inorganic thin film layer is placed between the support and the laminate to enhance gas barrier properties. be able to.

  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, these primer layers and inorganic thin film layers are combined as the primer layer. It is preferable to provide an organic / inorganic hybrid layer. As the inorganic thin film layer, an inorganic vapor deposition layer or a dense inorganic coating thin film by a sol-gel method is preferable. 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 antireflection film About the antireflection film of this invention, the above layers can be used and a well-known layer structure can be used. For example, the following are typical examples.
a. Support / hard coat layer b. Support / hard coat layer / low refractive index layer (FIG. 3)
c. Support / hard coat layer / high refractive index layer / low refractive index layer (FIG. 4)
d. Support / hard coat layer / medium refractive index layer / high refractive index layer / low refractive index layer (FIG. 5)

  As shown in the above b (FIG. 3), 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. The low refractive index layer can reduce surface reflection by the principle of thin film interference by forming the low refractive index layer 4 on the hard coat layer with a film thickness of about 1/4 of the wavelength of light.

  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. 4 (c), it can be suitably used as an antireflection film. Furthermore, 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. 5), the reflectance is 1% or less. can do.

  In the layer configuration of the antireflection films 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 translucent particles as shown in FIG. 6 or may be formed by surface shaping by a method such as embossing as shown in FIG. The antiglare layer formed by the dispersion of the translucent particles contains a translucent resin and the translucent particles dispersed in the translucent resin. 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 side layer or the outermost layer. If there is a dust on the surface, there is a problem), another hard coat layer (if one hard coat layer or antiglare layer is insufficient in hardness), gas barrier layer, water absorption layer ( Moisture-proof layer), adhesion improving layer, antifouling layer (contamination preventing layer), and the like.

The refractive index of each layer constituting the antiglare antireflection film having the antireflection layer in the invention preferably satisfies the following relationship.
Refractive index of hard coat layer> refractive index of transparent support> refractive index of low refractive index layer

4). Method for Producing Antireflection Film The antireflection film of the present invention can be formed by the following method, but is not limited to this method.

4- (1) Preparation of coating solution [Preparation of coating solution for forming each layer]
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 water content in the coating solution is preferably 5% by mass or less, and more preferably 2% by mass 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 after that.

[Physical properties of coating solution]
In the coating method of the present invention, the upper limit speed at which coating can be performed 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 some coating solutions change in viscosity depending on the shear rate, the above values indicate the viscosity at the shear rate at the moment of application. When a thixotropic agent is added to the coating solution and the application is highly sheared, the viscosity is low, and when the coating solution is hardly sheared, if the viscosity is high, unevenness during drying is less likely to occur.

Moreover, although it is not a liquid physical property, the quantity of the coating liquid apply | coated to a transparent support body also affects the upper limit speed | rate which can be apply | coated. The amount of the coating solution applied to the transparent support is preferably in the range of 2.0 to 5.0 cc / m ² . Increasing the amount of the coating liquid applied to the transparent support is preferable because the upper limit of the application rate can be increased, but if the amount of the coating liquid applied to the transparent support is increased too much, the load on drying increases. It is preferable to determine the optimal amount of coating liquid to be applied to the transparent support depending on the liquid formulation and process conditions.

  The surface tension is preferably in the range of 15 to 36 mN / m. It is preferable to reduce the surface tension by adding a leveling agent or the like because unevenness during drying is suppressed. On the other hand, if the surface tension is too low, the upper limit speed at which application is possible is reduced, and therefore the range of 17 mN / m to 32 mN / m is more preferable, and the range of 19 mN / m to 26 mN / m is more preferable.

[filtration]
The coating solution used for coating is preferably filtered before coating. As a filter for filtration, it is preferable to use a filter having a pore diameter as small as possible within a range in which components in the coating solution are not removed. For filtration, a filter having an absolute filtration accuracy of 0.1 to 10 μm is used, and a filter having an absolute filtration accuracy of 0.1 to 5 μm is preferably used. The thickness of the filter is preferably 0.1 to 10 mm, and more preferably 0.2 to 2 mm. In that case, the filtration pressure is preferably 1.5 MPa or less, more preferably 1.0 MPa or less, and further preferably 0.2 MPa or less.

  The filtration filter member is not particularly limited as long as it does not affect the coating solution. Specifically, the same thing as the filtration member of the wet dispersion of an inorganic compound mentioned above is mentioned. Further, it is also preferable that the filtered coating solution is ultrasonically dispersed 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.

  Further, as a dust removing method used in the dust removing process as a pre-process for coating, a method of pressing a nonwoven fabric, a blade or the like against the film surface described in JP-A-59-150571; JP-A-10-309553 A method in which air with high cleanliness is blown at a high speed to peel off deposits from the film surface and sucked by a close suction port; compressed air which is ultrasonically vibrated as described in JP-A-7-333613 is blown Examples thereof include dry dust removal methods such as a method of peeling off and adhering deposits (manufactured by Shinkosha, “New Ultra Cleaner”, etc.).

  In addition, a method of introducing a film into a cleaning tank and peeling off the deposits with an ultrasonic vibrator; after supplying a cleaning solution to the film described in Japanese Patent Publication No. 49-13020, spraying and sucking high-speed air Method to perform; as described in JP-A-2001-38306, use a wet dust removing method such as a method in which a web is continuously rubbed with a roll wetted with a liquid and then the liquid is sprayed onto the rubbed surface for cleaning. Can do. Among such dust removal methods, a method using ultrasonic dust removal or a method using wet dust removal is particularly preferable in terms of dust removal effect.

  In addition, it is particularly preferable to remove static electricity on the film support before performing such a dust removal step from the viewpoint of increasing dust removal efficiency and suppressing adhesion of dust. As such a static elimination method, a corona discharge ionizer, a light irradiation ionizer such as UV or soft X-ray, or the like can be used. The charged voltage of the film support before and after dust removal and coating is desirably 1000 V or less, preferably 300 V or less, and particularly preferably 100 V or less.

  From the viewpoint of maintaining the flatness of the film, the temperature of the cellulose acylate film in these treatments is preferably Tg or less, specifically 150 ° C. or less.

  As in the case of using the antireflection film of the present invention as a protective film for a polarizing plate, when adhering a cellulose acylate film to a polarizing film, from the viewpoint of adhesiveness with the polarizing film, acid treatment or alkali treatment, That is, it is particularly preferable to carry out a saponification treatment on cellulose acylate.

  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 antireflection 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. The known methods are used, and among them, the microgravure 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 having a gravure pattern engraved 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 antireflection film including an antiglare layer and a low refractive index layer is applied to one side of the unwound support by a microgravure coating method. Can be crafted.

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

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

[Configuration of die coater]
FIG. 8 is a cross-sectional view of the coater when the slot die used in the practice of the present invention is used. The coater 10 is applied to the web W supported by the backup roll 11 and continuously applied from the slot die 13 as a bead 14a to form a coating film 14b on the web W.

  Inside the slot die 13, a pocket 15 and a slot 16 are formed. The pocket 15 has a curved section and a straight section, and may be substantially circular as shown in FIG. 9A or semicircular. The pocket 15 is a liquid storage space for the coating liquid extended in the width direction of the slot die 13 with its cross-sectional shape, and the length of the effective extension is generally equal to or slightly longer than the coating width. The supply of the coating liquid 14 to the pocket 15 is performed from the side surface of the slot die 13 or from the center of the surface opposite to the slot opening 16a. The pocket 15 is provided with a stopper that prevents the coating liquid 14 from leaking out.

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

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

FIG. 9 shows the cross-sectional shape of the slot die 13 in comparison with the conventional one, (A) shows the slot die 13 used in the present invention, and (B) shows the conventional slot die 30. In the conventional slot die 30, the distance between the upstream lip land 31a and the web of the downstream lip land 31b is equal. Reference numeral 32 denotes a pocket, and 33 denotes a slot. On the other hand, in the slot die 13 used in the present invention, the downstream side lip land length I _LO is shortened, whereby the application with a wet film thickness of 20 μm or less can be performed with high accuracy.

The land length I _UP of the upstream lip land 18a is not particularly limited, but is preferably used in the range of 500 μm to 1 mm. The land length I _LO of the downstream lip land 18b is not less than 30 μm and not more than 100 μm, preferably not less than 30 μm and not more than 80 μm, more preferably not less than 30 μm and not more than 60 μm. By making the land length I _LO of the downstream lip longer than 30 μm, there is no problem that the edge or land of the tip lip is easily chipped or streaks are likely to occur in the coating film, so that coating is easy. . Further, there is no problem that the setting of the wet line position on the downstream side becomes difficult or the coating liquid tends to spread on the downstream side. It has been conventionally known that this spreading of the coating liquid on the downstream side means non-uniform wetting lines and leads to a problem of causing a defective shape such as a streak on the coating surface. On the other hand, when the land length I _LO of the downstream lip is shorter than 100 μm, an appropriate bead can be formed and the thin layer coating can be easily performed.

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

FIG. 10 is a perspective view showing the slot die and its periphery in the coating process in which the present invention is implemented.
On the opposite side of the web W in the direction of travel, a decompression chamber 40 is installed at a position where it does not come into contact with the bead 14a so that sufficient decompression can be adjusted. The decompression chamber 40 includes a back plate 40a and a side plate 40b for maintaining its operating efficiency, and there are gaps G _B and G between the back plate 40a and the web W and between the side plate 40b and the web W, respectively. _S exists.

11 and 12 are cross-sectional views showing the decompression chamber 40 and the web W that are close to each other. The side plate and the back plate may be integrated with the chamber main body as shown in FIG. 11, or may be structured to be fastened to the chamber with screws 40c or the like so that the gap can be appropriately changed as shown in FIG. . In any structure, portions that are actually opened between the back plate 40a and the web W and between the side plate 40b and the web W are defined as gaps G _B and G _S , respectively. The gap G _B between the back plate 40a and the web W of the decompression chamber 40, when installed below the web W and the slot die 13 as shown in FIG. 10 the vacuum chamber 40, the uppermost end of the back plate 40a to the web W Indicates the gap.

Is preferably placed in the gap G _B between the back plate 40a and the web W is larger than the gap G _L between the end lip 17 and the web W of the slot die 13, beads vicinity due to the eccentricity of the backup roll 11 thereby The change in the degree of decompression can be suppressed. For example, when the gap G _L between the end lip 17 and the web W of the slot die 13 is 30μm or more 100μm or less, the gap G _B between the back plate 40a and the web W is preferably 100μm or 500μm or less.

[Material and accuracy]
The longer the length of the tip lip on the traveling direction side of the web in the web traveling direction, the more disadvantageous it is for bead formation.If this length varies between arbitrary locations in the slot die width direction, It becomes unstable. Therefore, it is preferable that the fluctuation width in the slot die width direction is within 20 μm.

  Further, if the material of the tip end lip of the slot die is made of a material such as stainless steel, it will sag at the stage of die processing, and the length of the slot die tip lip in the web running direction is 30 to 100 μm as described above. Even within this range, the accuracy of the tip lip cannot be satisfied. Therefore, in order to maintain high processing accuracy, it is important to use a cemented carbide material as described in Japanese Patent No. 2817053. Specifically, at least the tip lip of the slot die is preferably made of a cemented carbide formed by bonding carbide crystals having an average particle size of 5 μm or less. Examples of cemented carbide include carbide crystal particles such as tungsten carbide (hereinafter referred to as WC) bonded by a bonding metal such as cobalt, and other bonding metals include titanium, tantalum, niobium, and mixed metals thereof. Can also be used. The average particle size of the WC crystal is more preferably 3 μm or less.

  In order to realize high-precision coating, the length of the land on the web traveling direction side of the tip lip and the variation in the slot die width direction of the gap with the web are also important factors. It is desirable to achieve a combination of these two factors, that is, straightness within a range in which the fluctuation range of the gap can be suppressed to some extent. Preferably, the straightness of the tip lip and the backup roll is set so that the fluctuation width of the gap in the slot die width direction is 5 μm or less.

[Application speed]
By achieving the accuracy of the backup roll and the tip lip as described above, the coating method preferably used in the present invention has high film thickness stability during high-speed coating. Furthermore, since the coating method is a pre-weighing method, it is easy to ensure a stable film thickness even during high-speed coating. With respect to a coating solution having a low coating amount, the coating method can be applied at high speed with good film thickness stability. Although application is possible by other application methods, the dip coating method inevitably causes vibration of the application liquid in the liquid receiving tank, and stepped unevenness is likely to occur. In the reverse roll coating method, stepped unevenness is likely to occur due to eccentricity and deflection of the roll related to coating. Moreover, since these coating methods are post-measuring methods, it is difficult to ensure a stable film thickness. From the viewpoint of productivity, it is preferable to apply the die coating method at 25 m / min or more.

4- (4) Drying The antireflective 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 Japanese Patent Application Laid-Open 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 at a relatively low temperature, and the latter half is preferably at a relatively high temperature. However, it is preferably below the temperature at which components other than the solvent contained in the coating solution of each layer start to volatilize. For example, some commercially available photoradical generators used in combination with ultraviolet curable resins may volatilize around several tens of mass% within a few minutes in warm air at 120 ° C. Some functional acrylate monomers, etc., undergo volatilization in hot 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 liquid 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 liquid is 1-50 mass%. It is preferable in order to prevent drying unevenness.

  Furthermore, after coating the coating composition of each layer on the support, if the temperature difference between the transport roll contacting the surface opposite to the coating surface of the support in the drying zone and the support is 0 ° C to 20 ° C or less. Further, drying unevenness due to heat transfer unevenness on the transport roll can be prevented, which is preferable.

4- (5) Curing The antireflection film of the present invention can cure the coating film by passing through a zone for curing each coating film with ionizing radiation and / or heat on the web after drying of the solvent.

  The ionizing radiation species in the present invention is not particularly limited, and may be selected from ultraviolet rays, electron beams, near ultraviolet rays, visible light, near infrared rays, infrared rays, X-rays, and the like depending on the type of curable composition forming the film. Although it can be appropriately selected, ultraviolet rays and electron beams are preferred, and ultraviolet rays are particularly preferred because they are easy to handle and high energy can be easily obtained.

  As the ultraviolet light source for photopolymerizing the ultraviolet reactive compound, any light source that generates ultraviolet light can be used. For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used. An ArF excimer laser, a KrF excimer laser, an excimer lamp, synchrotron radiation, or the like can also be used. Among these, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, and a metal halide lamp can be preferably used.

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

Irradiation conditions vary depending on each lamp, but the irradiation light amount 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. 2} . 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 ionizing radiation irradiation, with an oxygen concentration of 10 It is preferable to harden | cure by the process of irradiating ionizing radiation in the atmosphere below volume%. It is also preferable that heating is performed in an atmosphere having an oxygen concentration of 3% by volume or less simultaneously and / or continuously with ionizing radiation irradiation. In particular, it is preferable that the low refractive index layer which is the outermost layer and has a small film thickness is cured by this method. The curing reaction is accelerated by heat, and a film having excellent physical strength and chemical resistance can be formed.

  The time for irradiating with ionizing radiation is preferably 0.7 seconds or longer and 60 seconds or shorter, and more preferably 0.7 seconds or longer and 10 seconds or shorter. If it is 0.5 second or more, the curing reaction can be completed and sufficient curing can be performed. If it is 60 seconds or less, the low oxygen condition is not maintained for a long time, and there is no inconvenience that the equipment becomes large and a large amount of inert gas is required.

The oxygen concentration is preferably formed by a crosslinking reaction or a polymerization reaction of an ionizing radiation curable compound in an atmosphere of 6% by volume or less, more preferably 4% by volume or less, particularly preferably 2% by volume. % Or less, most preferably 1% by volume or less. Unless the oxygen concentration is reduced more than necessary, the amount of inert gas such as nitrogen used is not so large, which is preferable from the viewpoint of manufacturing 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 slightly blowing it out to the web entrance side of the irradiation chamber, the carry air accompanying the web transfer can be eliminated, and the oxygen concentration in the reaction chamber can be effectively reduced. Thus, the substantial oxygen concentration on the pole surface, which is largely inhibited by curing by oxygen, can be efficiently reduced. The direction of the inert gas flow on the web entrance side of the irradiation chamber can be controlled by adjusting the balance between supply and exhaust of the irradiation chamber. Direct blowing of an inert gas onto the web surface is also preferably used as a method for removing the carried air.

  Further, by providing a front chamber in front of the reaction chamber and excluding oxygen on the web surface in advance, the curing can proceed more efficiently. Further, the side surface constituting the web entrance side of the ionizing radiation reaction chamber or the front chamber is preferably 0.2 to 15 mm in gap with the web surface in order to efficiently use an inert gas, and more preferably, 0. 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, when the gap between the entrance surface of the ionizing radiation reaction chamber or the front chamber and the web is made 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 directions, and when the joint passes, it moves forward and backward 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. If it is 60 degreeC or more, hardening of a heating will fully be performed, and if it is 170 degreeC or less, problems, such as a deformation | transformation of a base material, will not arise. 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 which the film is at this temperature is preferably 0.1 second or more and 300 seconds or less, more preferably 10 seconds or less from the start of UV irradiation. If the time for maintaining the temperature of the film surface in the above temperature range is not too short, the reaction of the curable composition forming the film can be sufficiently accelerated, and if not too long, the optical performance of the film There is no problem in manufacturing such as a decrease in size or an increase in equipment.

  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 of 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 a plurality of constituent layers are provided, 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 to perform ionizing radiation at least twice in a continuous reaction chamber that does not exceed an oxygen concentration of 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 due to high productivity, ionizing radiation irradiation is required multiple times in order to ensure the energy of ionizing radiation necessary for the curing reaction.

  In addition, when the curing rate (100-residual functional group content) is a certain value of less than 100%, when the layer is provided thereon and cured by ionizing radiation and / or heat, the lower layer has a curing rate of the upper layer. 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 antireflection film of the present invention, a step of continuously feeding a roll-shaped support film, a step of applying and drying a coating liquid, a step of curing a coating film, A step of winding up the support film having the cured layer is performed.

  The film support is continuously sent 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 removal device, and then attached to the film support. Remove foreign matter using a dust remover. Subsequently, the coating liquid is applied onto the film support in the application unit 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 produce the antireflection film of the present invention, as described above, simultaneously with the microfiltration operation of the coating liquid, the coating process in the coating unit and the drying process performed in the drying chamber are performed in a clean air atmosphere. In addition, 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 / m ³ or less of 0.5 μm or more) based on the standard of air cleanliness in US Federal Standard 209E, and more preferably. Is preferably class 1 (35.5 particles / m ³ or less of particles of 0.5 μm or more) 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 producing a polarizing plate using the antireflection film of the present invention as one of the two surface protective films of a polarizing film, the surface to be bonded to the polarizing film is hydrophilic. It is preferable to improve the adhesiveness on the adhesive surface.

a. Method of immersing in alkaline solution This is a method in which a film is immersed in an alkaline solution under appropriate conditions to saponify the part of the entire surface that is reactive with alkali, and no special equipment is required. It is preferable from the viewpoint of cost. The alkaline liquid is preferably a sodium hydroxide aqueous solution. A preferred concentration is 0.5 to 3 mol / L, particularly preferably 1 to 2 mol / L. The liquid temperature of a preferable alkali liquid is 30-75 degreeC, Most preferably, it is 40-60 degreeC. The combination of the saponification conditions is preferably a combination of relatively mild conditions, but can be set depending on the material and composition of the film and the target contact angle.

  After being immersed in the alkaline solution, it is preferable that the film is sufficiently washed with water so that the alkali component does not remain in the film, or is immersed in a dilute acid to neutralize the alkali component.

  By saponification treatment, both the surface having the coating layer and the opposite surface are hydrophilized. The protective film for polarizing plate is used by adhering the hydrophilic surface of the transparent support to the polarizing film.

  The hydrophilized surface is effective for improving the adhesiveness with the adhesive layer mainly composed of polyvinyl alcohol.

  In the saponification treatment, the lower the contact angle with water on the surface of the transparent support opposite to the side having the coating layer, the better from the viewpoint of adhesiveness to the polarizing film. Since it may be damaged by alkali from the surface to the inside, it is important to set the reaction conditions to the minimum necessary. 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 triacetyl cellulose, preferably 10 to 50 °, more preferably 30 to 50 °, more preferably 40 to 50 °. If it is 50 ° or less, there is no problem in adhesion to the polarizing film, which is preferable. On the other hand, if it is 10 ° or more, the film is not damaged so much that the physical strength is not deteriorated.

b. Method for applying alkaline solution In the above immersion method, as a means for avoiding damage to each film, the alkaline solution is applied, heated and washed only on the surface opposite to the side having the coating layer under appropriate conditions. A drying alkali solution coating method is preferably used. The application in this case means that an alkaline liquid or the like is brought into contact with only the surface to be saponified, and includes application by spraying, contact with a belt containing the liquid, or the like. By adopting these methods, a separate facility and process for applying an alkaline solution are required, which is inferior to the immersion method (a) from the viewpoint of cost. On the other hand, since the alkali solution contacts only the surface to be saponified, the opposite surface can have a layer using a material that is weak against the alkali solution. For example, vapor deposition films and sol / gel films may be affected by various effects such as corrosion, dissolution, and peeling by an alkaline solution. Therefore, it is not easy to provide these layers by the dipping method. These layers can be provided without any problem because they do not come into contact with each other.

  In any of the saponification methods (a) and (b), since each layer can be formed after being unwound from a roll-shaped support, a series of operations are performed in addition to the antireflection film manufacturing process. Also good. Furthermore, the polarizing plate can be produced more efficiently than when the same operation is performed on a single wafer by continuously performing the bonding process with the polarizing film composed 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, after the final layer is formed, the laminate film is formed on the surface on which the final layer is formed. It is possible to hydrophilize only the surface of the triacetyl cellulose opposite to the surface on which the final layer is formed by immersing the substrate in the alkaline solution. In this case, the laminate film may be peeled after the saponification treatment. 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), there is an advantage that a laminate film is generated as a waste, but a special device for applying an alkaline solution is unnecessary.

d. Method of immersing in alkaline solution after forming up to middle layer If the lower layer is resistant to alkaline solution, but the upper layer is insufficiently resistant to alkaline solution, both sides are hydrolyzed by immersing in alkaline solution after forming up to the lower layer However, the upper layer can be formed thereafter. Although the manufacturing process is complicated, for example, in an antireflection film comprising an antiglare layer and a low refractive index layer of a fluorine-containing sol / gel film, when the low refractive index layer has a hydrophilic group, the antiglare layer and the low refractive index There is an advantage that the interlayer adhesion with the rate layer is improved.

e. Method of forming a coating layer on a pre-saponified triacetyl cellulose film Triacetyl cellulose film is saponified by dipping in an alkaline solution in advance, and the coating layer is formed directly on one side or via another layer. It may be formed. In the case of saponification by dipping in an alkaline solution, the interlaminar adhesion between the triacetyl cellulose surface hydrophilized by saponification and the coating layer to be formed 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, thereby removing the hydrophilic surface and then forming 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 antireflection film of the present invention can be used as a protective film disposed on at least one side of a polarizing film to produce a polarizing plate.

  In that case, the antireflection film of the present invention can be used as one protective film, and a normal cellulose acetate film can be used as the other protective film. In addition, the cellulose acetate film produced by the solution casting method and stretched in the width direction in the roll film form at a stretch ratio of 10 to 100%, and the roll coat form film, the die coater or the like. It is preferable to use the antireflection film of the present invention having a coating layer formed thereon.

  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 solvent of this adhesive 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 moisture permeability becomes too high, moisture may enter the polarizing film depending on the usage environment (high humidity) of the liquid crystal display device. As a result, the polarization ability may decrease.

  The moisture permeability of the protective film is determined by the thickness, free volume, hydrophilicity / hydrophobicity, etc. of the polymer film (and polymerizable liquid crystal compound) which is a transparent support.

The case of using the antireflection 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 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 longitudinal movement speed difference of the holding device is within 3%, and the angle formed by the film traveling 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 °. It can be produced by a stretching method in which the traveling direction is bent with both ends of the film held. 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.

Furthermore, in the polarizing plate of the present invention, it is also a preferable aspect that one side is an antireflection film while the other protective film is an optical compensation film.
The optical compensation film is preferably an optical compensation film having an optically anisotropic layer in which the orientation of the liquid crystalline compound is fixed.
Furthermore, it is preferable that the optically anisotropic layer contains a compound having a discotic structural unit.
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.
Moreover, the composite polarizing plate which bonded together the polarizing plate which has the antireflection film of this invention, and the optical compensation film through the adhesive layer may be sufficient.

When the optical compensation film is bonded to the polarizing plate and the liquid crystal cell through the pressure-sensitive adhesive layer, unevenness caused by dimensional changes due to environmental changes may be reduced.
The pressure-sensitive adhesive is not particularly limited, and an acrylic pressure-sensitive adhesive can be used although it is generally used for LCDs. A single component or a plurality of acrylic polymers may be used for the pressure-sensitive adhesive, and the above-mentioned unevenness can be improved by adjusting the Tg of the material, the degree of crosslinking, and the thickness of the pressure-sensitive adhesive layer.

5. Forms of use of the antireflection film of the present invention The antireflection film of the present invention comprises a liquid crystal display (LCD), a plasma display panel (PDP), an electroluminescence display (ELD), and a cathode ray tube display (CR).
T). The antireflection film according to the present invention can be used on a known display such as a plasma display panel (PDP) or a cathode ray tube display (CRT).

5- (1) Liquid Crystal Display Device The antireflection film of the present invention and a polarizing plate using the same can be advantageously used for an image display device such as a liquid crystal display device, and is preferably used for the outermost layer of the display.

  The liquid crystal display device has a liquid crystal cell and two polarizing plates arranged on both sides thereof, and the liquid crystal cell carries a liquid crystal between two electrode substrates. Furthermore, one optically anisotropic layer may be disposed between the liquid crystal cell and one polarizing plate, or two optically anisotropic layers may be disposed between the liquid crystal cell and both polarizing plates.

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

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

[VA mode]
In a VA mode liquid crystal cell, rod-like liquid crystalline molecules are aligned substantially vertically when no voltage is applied.

In VA mode liquid crystal cell,
(1) In addition to a narrowly-defined VA mode liquid crystal cell (described in JP-A-2-176625) in which rod-like liquid crystalline molecules are aligned substantially vertically when no voltage is applied, and substantially horizontally when a voltage is applied. ,
(2) Liquid crystal cell ("SID97, Digest of tech. Papers" (Preliminary Collection), Vol. 28 (1997), p. 845},
(3) A liquid crystal cell of 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 Collection of Japan Liquid Crystal Society", p. 58-59 (1998) description}, and
(4) Includes 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 crystal molecules are aligned in a substantially opposite direction (symmetrically) between the upper and lower portions of the liquid crystal cell. Nos. 825 and 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. For this reason, this liquid crystal mode is also 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. For details, refer to “Proc. 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, JP-A-5-203946.

5- (2) Display other than liquid crystal display [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, the antireflection film of the present invention can be directly attached to the display surface as an optical filter. When a front plate is provided in front of the display, an antireflection film as an optical filter can be attached to the front side (outside) or the back side (display side) of the front plate.

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

[Organic EL device]
The antireflection film of the present invention can be used as a protective film for organic EL elements and the like.

  When the antireflection 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, 2001-335776, JP 2001-247859, JP 2001-181616, JP 2001-181617, JP 2002-181816, JP 2002-181617, JP 2002-056776. It is possible to apply the contents described in each publication. 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 other than the above-mentioned items 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 reflectivity at an exit angle of -5 ° at an incident angle of 5 °, calculate an average reflectivity of 450 to 650 nm, and evaluate the antireflection property.

6- (2) a polarizing plate using the antireflection film as a protective film of the color 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, a positive The color can be evaluated by determining the color of the reflected light, that is, 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 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 light, the color tone when a little bright external light is reflected. Neutral, don't mind. Specifically, if a ^* ≦ 7, the reddishness will not be too strong, and if a ^* ≧ −7, the cyanishness 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 (3) from a ^* b ^* on the L ^* a ^* b ^* chromaticity diagram obtained from the reflection spectrum of the reflected light from 380 nm to 680 nm. It can be obtained as the rate of change in taste.
Formula (3):

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

In the antireflection film of the present invention, ΔE _w which is a change in color before and after the weather resistance test is preferably 15 or less, 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 mathematical formula (4).
Formula (4): ΔE _w = [(ΔL _w ) ² + (Δa _w ) ² + (Δb _w ) ² ] ^1/2
Here, ΔL _w , Δa _w , and Δb _w are respective amounts of change in the L ^* value, the a ^* value, and the b ^* value before and after the weather resistance test.

6- (3) Transmission image definition The transmission image definition is optical in accordance with JIS K-7105, using an image clarity measuring instrument “ICM-2D type” manufactured by Suga Test Instruments Co., Ltd. with a slit width of 0.5 mm. It can be measured using a comb.

  The transmitted image definition is generally an index indicating the degree of blur of an image reflected through a film, and the larger this value, the clearer and better the image viewed through the film. On the other hand, in a film with an antiglare layer having surface irregularities, if the sharpness is high, a minute brightness unevenness called “glare” occurs due to the geometric structure. It is not necessarily good that the nature is high. The transmitted image definition of the antireflection film of the present invention is preferably 5 to 60%. More preferably, it is 20 to 60%.

6- (4) Surface Roughness Measurement of surface roughness parameters such as center line average roughness (Ra) in the antireflection film of the present invention can be performed according to JIS B-0601.

As a surface uneven | corrugated shape of this invention film, it is preferable that centerline average roughness Ra is 0.08-0.30 micrometer. More preferably, it is 0.08 to 0.15 μm.
If Ra is 0.08 or more, sufficient anti-glare property is obtained, and if it is 0.30 or less, problems such as glare and whitening of the surface when external light is reflected do not occur. It is preferable to be within this range.
In addition, 10-point average roughness Rz is 10 times or less of Ra, average mountain valley distance Sm is 1 to 100 μm, standard deviation of the height of the convex part from the deepest part of the irregularities is 0.5 μm or less, and average mountain valley based on the center line It is preferable to design the standard deviation of the distance Sm to be 20 μm or less because sufficient anti-glare properties and a visually uniform mat feeling can be achieved.

6- (5) Haze The haze of the antireflection film of the present invention is the haze value defined in JIS K-7136, based on the light transmittance measurement method defined in JIS K-7361-1. A value automatically measured as haze = (diffuse light / total transmitted light) × 100 (%) measured using a turbidimeter “NDH-1001DP” manufactured by Nippon Denshoku Industries Co., Ltd. was used.

  The antireflection film of the present invention preferably has 0% to 35%, more preferably 0% to 30%, and still more preferably haze caused by internal scattering (hereinafter referred to as internal haze). It is 0% to 10%, most preferably 0% to 5%. Further, haze caused by surface scattering (hereinafter referred to as surface haze) is preferably 5% to 15%, more preferably 5% to 10%.

  The internal haze can be measured, for example, by eliminating scattering due to surface irregularities in a medium having a refractive index substantially equal to the film surface. The surface haze can be determined as the difference between the haze of the entire film and the internal haze.

6- (7) Scratch resistance [steel wool scratch resistance evaluation]
A rubbing test using a “rubbing tester” under the following conditions can be used as an index of scratch resistance.
Evaluation environmental conditions: 25 ° C., 60% RH
Rubbing material: steel wool {made by Nippon Steel Wool Co., Ltd. 0000} is wound around the rubbing tip (1 cm × 1 cm) of a tester that comes into contact with the sample, and the band is fixed.
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,
Number of rubbing: 10 round trips.
Evaluation is performed by applying oil-based black ink to the back side of the rubbed sample, visually observing the scratch on the rubbed portion with reflected light, and observing the difference in the amount of reflected light from other than the rubbed portion.

[Eraser scuff resistance evaluation]
By using a rubbing tester and conducting 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: A plastic eraser {"MONO" manufactured by Dragonfly Pencil Co., Ltd.} is fixed to the tip (1 cm × 1 cm) of the tester that comes into contact with the sample.
Travel distance (one way): 4cm
Rubbing speed: 2 cm / second,
Load: 500 g / cm ²
Tip contact area: 1 cm × 1 cm,
Number of rubbing: 100 reciprocations.
An oil-based black ink is applied to the back side of the rubbed sample, the scratches on the rubbing portion are visually observed with reflected light, and evaluation is made based on the difference in the amount of reflected light from other than the rubbed portion.

[Taper test]
In the Taber test according to JIS K-5400, 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 hardness of the antireflection film of the present invention can be evaluated by a pencil hardness test according to JIS K-5400. 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 antireflection film of the present invention is a value determined using a micro surface hardness meter {manufactured by Fisher Instruments: “Fischer Scope 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.

[Universal hardness]
Further, the surface hardness can be obtained as a universal hardness by using the 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 a microhardness meter “H100” manufactured by Fisher Instruments Co., Ltd. It is represented by the universal hardness (N / mm ² ) determined by the measurement procedure below.

In addition to the crosslinkable polymer, apply a coating solution with a solid content concentration of about 25% by mass containing the necessary catalyst, crosslinking agent, polymerization initiator, etc. to an appropriate bar so that the film thickness after curing is about 20-30 μm. Select the coater and select TOSHINRIKO. CO. Made by LTD (26mm x 76mm x 1.2mm)
Apply onto a polished glass slide. When the crosslinkable polymer is thermosetting, the thermosetting conditions for sufficiently curing the film are obtained in advance (as an example, 125 ° C., 10 minutes), and the same applies to the case where the crosslinkable polymer is ionizing radiation curable. The curing conditions for sufficiently curing the film are determined in advance (as an example, the oxygen concentration is 12 ppm, the UV irradiation amount is 750 mJ / cm ² ). For each film, the load is continuously increased from 0 to 4 mN, the film thickness of the base plate is not affected by 1/10 film thickness, and the cone diamond indenter is pressed against each load F. Universal hardness is calculated from N = 6 measurement average value of F / A determined from the indentation area A (mm ² ).

[Surface hardness by nanoindentation]
Further, the surface hardness can be obtained by nanoindentation described in JP-A-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 property test [Magic wiping property]
An anti-reflection film is fixed on the glass surface with an adhesive, and a black “magic ink” (“Mckey extra fine”) {trade name: manufactured by Zebra Co., Ltd.} nib (narrow) under the conditions of 25 ° C. and 60 RH%. Write a circle of 5 mm in diameter 3 times, and “Bencot” {Brand name: Asahi Kasei Co., Ltd.}, which was folded 10 times after 5 seconds, and wiped it back and forth 20 times with a load enough to dent the “Bencot” bundle. This writing and wiping are repeated under the same conditions until the “magic ink” mark disappears 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 Ink”, use “Magic Ink No. 700 (M700-T1 Black) Extra Fine”, paint a circle with a diameter of 1 cm on the sample, leave it for 24 hours and rub it with “Bencott”. It can also be evaluated by whether or not "" can be wiped off.

6- (10) Surface tension The surface tension measured and evaluated in the present invention is determined by measuring the surface tension of the coating solution for forming the functional layer under the environment of a temperature of 25 ° C. (manufactured by Kyowa Interface Science Co., Ltd., “ KYOWA CBVP SURFACE TENSIOTER A3 "} can be used for measurement.

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

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

The surface free energy (γs ^v : unit, mN / m) of the antireflection film of the present invention is D
. K. Owens, “J. Appl. Polym. Sci.”, Volume 13, p. 1741 (1969), from the contact angles θ _H2O and θ _{CH2I2 of} pure water H ₂ O and methylene iodide CH ₂ I ₂ experimentally determined on the antireflection film, the following simultaneous equations a, b represents the surface tension of the antireflection film defined by the value γs ^v (= γs ^d + γs ^h ) expressed as the sum of the values γs ^d and γs ^h obtained from {Formula (5)}. The gamma] s ^v is small, as the surface of the repellent can of high a low surface free energy, generally excellent antifouling property.
Formula (5):

a. ^{_{1 + cosθ H2O = 2√γs d (}} √γ H2O d / γ H2O v) + 2√γs h (√γ H2O h / γ H2O v)
b. ^{_{1 + cosθ CH2I2 = 2√γs d (}} √γ CH2I2 d / γ CH2I2 v) + 2√γs h (√γ CH2I2 h / γ CH2I2 v)
γ _H2O ^d = 21.8, γ _H2O ^h = 51.0, γ _H2O ^v = 72.8,
γ _CH2I2 ^d = 49.5, _γCH2I2 ^h = 1.3, _γCH2I2 ^v = 50.8

  The contact angle is measured using an automatic contact angle meter “CA-V150 type” manufactured by Kyowa Interface Science Co., Ltd. after conditioning the antireflection film at 25 ° C. and 60% RH for 1 hour or more. The contact angle was determined 30 seconds after 2 μL of the droplet was dropped on the film.

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

6- (13) Curl The curl is measured using the template for curl measurement of Method A in “Measuring Method of Curling of Photographic Film” of JIS K-7619-1988.
The measurement conditions are 25 ° C., 60% RH, and a humidity control time of 10 hours.

In the antireflection film of the present invention, the value when curl is expressed by the following formula (6) is preferably in the range of −15 to +15, more preferably in the range of −12 to +12. Is -10 to +10. In this case, the measurement direction of the curl in the sample is measured in the conveyance direction of the base material in the case of application in a web form.
Formula (6): Curl = 1 / R
R is radius of curvature (m)

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

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

6- (14) Evaluation of adhesion The adhesion between the layers of the antireflection film or between the support and the coating layer can be evaluated by the following method.

On the surface having the coating layer, 11 square and 11 horizontal cuts are made at 1 mm intervals in a grid pattern with a cutter knife, and a total of 100 square squares are engraved, and polyester adhesive made by Nitto Denko Corporation. The tape “NO.31B” is pressure-bonded, and left for 24 hours and then peeled off. The test 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- (15) Brittleness test (crack resistance)
Crack resistance is an important characteristic for preventing crack defects by handling such as application of antireflection film, processing, cutting, application of pressure-sensitive adhesive, and adhesion to various objects.

  Cut the antireflection film sample to 35mm x 140mm, leave it for 2 hours under the conditions of temperature 25 ° C and 60% RH, then measure the curvature diameter at which cracking starts when rolled up into a cylinder, and check the surface crack Can be evaluated.

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

6- (17) Performance of liquid crystal display device Hereinafter, a method for evaluating characteristics and a preferable situation when the antireflection film of the present invention is used on a display device will be described.

  The polarizing plate on the viewing side provided in the liquid crystal display device is peeled off. Instead, the antireflection film or polarizing plate of the present invention is applied to the product with the coating surface on the viewing side and the transmission axis of the polarizing plate attached to the product. Affix with an adhesive to match the plate. In a 500 Lx bright room, the liquid crystal display device is displayed in black, and the following various characteristics can be evaluated visually from various viewing angles.

  As a specific commercially available liquid crystal display device, in the TN mode, for example, “Syncmaster 172X” (manufactured by Samsung), “MDT191S” {manufactured by Mitsubishi Electric Corporation}, “TH-15TA2” {manufactured by Matsushita Electric Industrial Co., Ltd.} VA mode “LC15S4” {manufactured by Sharp Corporation}; IPS mode “TH32LX-500” {Matsushita Electric Co., Ltd.}; OCB mode “VT23XD1” {manufactured by Nanao Corporation}, etc. .

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

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

[Contrast and viewing angle]
Contrast and viewing angle are measured using the measuring instrument “EZ-Contrast 160D” (manufactured by ELDIM). The contrast ratio and the viewing angle in the left-right direction (direction orthogonal to the rubbing direction of the cell) Can be checked.

  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.

<Preparation of antireflection film>
[Synthesis of fluoropolymer]
Synthesis Example 1: Synthesis of fluorinated polymer (1)

In a 100 mL stainless steel autoclave with a stirrer, 40 mL of ethyl acetate, 14.7 g of hydroxyethyl vinyl ether (HEVE) and 0.55 g of dilauroyl peroxide were charged, and the inside of the system was deaerated and replaced with nitrogen gas. Furthermore, 25 g of hexafluoropropylene (HFP) was introduced into the autoclave and the temperature was raised to 65 ° C. The pressure when the temperature in the autoclave reached 65 ° C. was 0.53 Mpa (5.4 kg / cm ² ). The reaction was continued for 8 hours while maintaining the temperature, and when the pressure reached 0.31 MPa (3.2 kg / cm ² ), the heating was stopped and the mixture was allowed to cool.

When the internal temperature dropped to room temperature, unreacted monomers were driven out, the autoclave was opened, and the reaction solution was taken out. The obtained reaction solution was poured into a large excess of hexane, and the solvent was removed by decantation to take out the precipitated polymer. Further, this polymer was dissolved in a small amount of ethyl acetate and reprecipitated twice from hexane to completely remove the residual monomer. After drying, 28 g of polymer was obtained. Next, 20 g of the polymer was dissolved in 100 mL of N, N-dimethylacetamide, and 11.4 g of acrylic acid chloride was added dropwise under ice cooling, followed by stirring at room temperature for 10 hours. Ethyl acetate was added to the reaction solution, washed with water, the organic layer was extracted and concentrated, and the resulting polymer was reprecipitated with hexane to obtain 19 g of a fluoropolymer (1) having the following structural formula. The resulting polymer had a refractive index of 1.421.
Fluorine-containing polymer (1):

[Preparation of antireflection film]
Examples 1-1 to 1-5 and Comparative Examples 1-1 to 1-7
[Preparation of Sol Solution a]
Add a stirrer, a reactor equipped with a reflux condenser, 120 parts of methyl ethyl ketone, 100 parts of acryloyloxypropyltrimethoxysilane {"KBM-5103", manufactured by Shin-Etsu Chemical Co., Ltd.}, 3 parts of diisopropoxyaluminum ethyl acetoacetate After mixing, 30 parts of ion exchange water was added and reacted at 60 ° C. for 4 hours, and then cooled to room temperature to obtain sol solution a. The mass average molecular weight was 1600, and among the components higher than the oligomer component, the component having a molecular weight of 1000 to 20000 was 100%. Further, from the gas chromatography analysis, the raw material acryloyloxypropyltrimethoxysilane did not remain at all.

[Preparation of coating solution for antiglare layer (BLA)]
31 g of a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate {“DPHA”, manufactured by Nippon Kayaku Co., Ltd.} was diluted with 38 g of methyl isobutyl ketone. Furthermore, 1.5 g of a polymerization initiator {“Irgacure 184”, manufactured by Ciba Specialty Chemicals Co., Ltd.} was added and mixed and stirred. Subsequently, 0.04 g of a fluorine-based surface modifier (FP-149) and a silane coupling agent {“KBM-5103”, manufactured by Shin-Etsu Chemical Co., Ltd.} 6.2 g were added. The refractive index of the coating film obtained by applying this solution and curing with ultraviolet rays was 1.520.

  Finally, 30 of crosslinked poly (acryl-styrene) particles having an average particle diameter of 3.5 μm (copolymerization composition ratio = 50/50, refractive index 1.540) dispersed in this solution for 20 minutes at 10,000 rpm with a Polytron disperser. 21.0 g of% cyclohexanone dispersion was added to make a finished solution. The obtained mixed solution was filtered through a polypropylene filter having a pore size of 30 μm to prepare a coating solution for antiglare layer (BLA).

[Preparation of coating solution for antiglare layer (BLB)]
In the preparation of the coating solution for antiglare layer (BLA), the coating solution for antiglare layer (except that the addition amount of the 30% cyclohexanone dispersion of crosslinked poly (acryl-styrene) particles was changed from 21.0 g to 14.0 g ( In the same manner as for BLA), an antiglare layer coating solution (BLB) was prepared.

[Preparation of coating solution for antiglare layer (BLC)]
In the preparation of the coating solution for antiglare layer (BLA), the coating solution for antiglare layer (except for the addition amount of 30% cyclohexanone dispersion of crosslinked poly (acryl-styrene) particles from 21.0 g to 10.0 g) In the same manner as for BLA), an antiglare layer coating solution (BLC) was prepared.

[Preparation of antiglare layer coating solution (BLD)]
In the preparation of the coating solution for antiglare layer (BLA), the coating solution for antiglare layer (except that the addition amount of 30% cyclohexanone dispersion of crosslinked poly (acryl-styrene) particles was changed from 21.0 g to 17.0 g ( In the same manner as in BLA), an antiglare layer coating solution (BLD) was prepared.

[Preparation of antiglare layer coating solution (BLE)]
In the preparation of the coating solution for antiglare layer (BLA), the coating solution for antiglare layer (except that the addition amount of the 30% cyclohexanone dispersion of crosslinked poly (acryl-styrene) particles was changed from 21.0 g to 28.0 g) In the same manner as in (BLA), an antiglare layer coating solution (BLE) was prepared.

[Preparation of coating solution for antiglare layer (BLF)]
30% cyclohexanone dispersion of crosslinked poly (acryl-styrene) particles (copolymerization composition ratio = 50/50, refractive index 1.540) having an average particle size of 3.5 μm in the preparation of the coating solution for antiglare layer (BLA) Except that 28.0 g of a 30% cyclohexanone dispersion of crosslinked poly (acryl-styrene) particles (copolymerization composition ratio = 50/50, refractive index 1.540) having an average particle size of 5 μm was used instead of 21.0 g of Prepared an antiglare layer coating solution (BLF) in the same manner as the antiglare layer coating solution (BLA).

[Adjustment of coating solution for low refractive index layer (LLA)]
Thermally crosslinkable fluorine-containing polymer having a refractive index of 1.44 containing polysiloxane and hydroxyl group {“JTA113”, solid content concentration 6%, manufactured by JSR Corporation} 13 g, colloidal silica dispersion “MEK-ST-L” { (Trade name), average particle size 45 nm, solid content concentration 30%, manufactured by Nissan Chemical Co., Ltd.} 1.3 g, the above sol solution a 0.6 g, methyl ethyl ketone 5 g, and cyclohexanone 0.6 g were added. The mixture was filtered through a 1 μm polypropylene filter to prepare a low refractive index layer coating solution (LLA). The refractive index of the layer formed with this coating solution was 1.45.

[Adjustment of coating solution for low refractive index layer (LLB)]
Instead of using 1.3 g of the colloidal silica dispersion “MEK-ST-L” in the coating liquid for low refractive index layer (LLA), hollow silica sol (refractive index 1.31, average particle size 60 nm, solid content concentration 20 %) Was used in the same manner as the low refractive index layer coating solution (LLA) except that 1.95 g was used. The refractive index of the layer formed by this coating solution was 1.39.

[Preparation of coating solution for low refractive index layer (LLC)]
15.2 g of the fluorinated polymer (1) produced in Synthesis Example 1 above, colloidal silica dispersion {silica, “MEK-ST” with different particle size, average particle size 45 nm, solid content concentration 30%, Nissan Chemical Industries ( 1.4 g, reactive silicone “X-22-164B” {(trade name), manufactured by Shin-Etsu Chemical Co., Ltd.} 0.3 g, sol liquid a 7.3 g, photopolymerization initiator {“Irgacure 907” (Trade name), Ciba Specialty Chemicals Co., Ltd.} 0.76 g, methyl ethyl ketone 301 g, cyclohexanone 9.0 g were added, and after stirring, filtered through a polypropylene filter having a pore size of 5 μm, for a low refractive index layer A coating solution (LLC) was prepared. The refractive index of the layer formed by this coating solution was 1.44.

[Preparation of Antireflection Film (1F) (Example 1-1)]
(1) Coating of anti-glare layer An 80 μm thick triacetyl cellulose film {“TAC-TD80U”, manufactured by Fuji Photo Film Co., Ltd.} is unwound in roll form and shown in the following apparatus configuration and coating conditions. After applying the antiglare layer coating solution (BLA) by a die coating method, drying the solvent, and further using a 160 W / cm “air-cooled metal halide lamp” {manufactured by Eye Graphics Co., Ltd.} under a nitrogen purge, The coating layer was cured by irradiating with an ultraviolet ray with an irradiation amount of 90 mJ / cm ² to form an antiglare layer having an antiglare property having a thickness of 6 μm and wound up.

Basic conditions: The slot die 13 has an upstream lip land length I _UP of 0.5 mm, a downstream lip land length I _LO of 50 μm, a length of the opening of the slot 16 in the web running direction of 150 μm, and the length of the slot 16 The one with a length of 50 mm was used. The gap between the upstream lip land 18a and the web W is 50 μm longer than the gap between the downstream lip land 18b and the web W (hereinafter referred to as an overbite length of 50 μm), and the gap between the downstream lip land 18b and the web W _GL was set to 50 μm. Further, the gap G _B between the gap G _S, and the back plate 40a and the web W between the side plate 40b and the web W in the vacuum chamber 40 were both 200 [mu] m. In accordance with the liquid physical properties of each coating solution, coating was performed at a coating speed of 50 m / min and a wet coating amount of 17 ml / m ² , and then dried at 30 ° C. for 15 seconds and 90 ° C. for 20 seconds. Further, the inter-application width was 1300 mm and the effective width was 1280 mm.

(2) Coating of low refractive index layer The triacetyl cellulose film coated with the antiglare layer coating solution (BLA) and uncoated with the antiglare layer is unwound again, and the low refractive index layer coating solution ( LLA) was applied under the above-mentioned application conditions at a coating speed of 40 m / min and a wet coating amount of 5 ml / m ² . After drying at 120 ° C. for 150 seconds and further drying at 140 ° C. for 8 minutes, an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) with 240 W / cm in an atmosphere with an oxygen concentration of 0.1% by nitrogen purge. Then, an ultraviolet ray having an irradiation amount of 900 mJ / cm ² was irradiated to form a low refractive index layer having a thickness of 100 nm, and wound to prepare an antireflection film.

(3) Saponification treatment of antireflection film After the formation of the low refractive index layer, the antireflection film sample was subjected to the following treatment.
A 1.5 mol / L aqueous sodium hydroxide solution was prepared and kept at 55 ° C. A 0.01 mol / L dilute sulfuric acid aqueous solution was prepared and kept at 35 ° C. The produced antireflection film was immersed in this aqueous sodium hydroxide solution for 2 minutes, and then immersed in water to sufficiently wash away the aqueous sodium hydroxide solution. Subsequently, after being immersed in the above-mentioned dilute sulfuric acid aqueous solution for 1 minute, it was immersed in water to sufficiently wash away the dilute sulfuric acid aqueous solution. Finally, the sample was thoroughly dried at 120 ° C.
In this manner, a saponified antiglare antireflection film (1F) was produced.

(Examples 1-2 and 1-3)
In Example 1-1, instead of using the antiglare layer coating solution (BLA), antiglare was applied in the same manner as in Example 1-1 except that the antiglare layer coating solution (BLB) or (BLC) was used. A layer was formed, and a low refractive index layer was applied and saponified in the same manner as in Example 1-1 to produce antiglare antireflection films (2F) and (3F).

(Example 1-4)
In Example 1-2, instead of using the coating solution for low refractive index (LLA), an antiglare antireflection film was prepared in the same manner as in Example 1-2 except that the coating solution for low refractive index (LLB) was used. (4F) was produced.

(Example 1-5)
In Example 1-2, instead of using the coating solution for low refractive index (LLA), the coating solution for low refractive index (LLC) was used, and the drying conditions after coating were changed to 100 ° C. for 2 minutes. An antiglare antireflection film (5F) was produced in the same manner as in Example 1-2.

(Comparative Example 1-1)
In Example 1-1, instead of using the coating solution for antiglare layer (BLA), the coating solution for antiglare layer (BLD) was used, and the wet coating amount was 10 mL / m ^2. An antiglare layer was formed in the same manner, and a low refractive index layer was applied and saponified in the same manner as in Example 1-1 to produce an antiglare antireflection film (1rF).

(Comparative Example 1-2)
Example 1-1 and Example 1-1 except that instead of using the antiglare layer coating solution (BLA), the antiglare layer coating solution (BLE) was used and the wet coating amount was 15 mL / m ^2. An antiglare layer was formed in the same manner, and a low refractive index layer was applied and saponified in the same manner as in Example 1-1 to produce an antiglare antireflection film (2rF).

(Comparative Example 1-3)
Example 1-1 is different from Example 1-1 except that the coating liquid for antiglare layer (BLF) is used instead of the coating liquid for antiglare layer (BLA) and the wet coating amount is 15 mL / m ^2. Similarly, an antiglare layer is formed, and the low refractive index is the same as in Example 1-1 except that the low refractive index coating liquid (LLB) is used instead of using the low refractive index coating liquid (LLA). The rate layer was coated and saponified to produce an antiglare antireflection film (3rF).

(Comparative Example 1-4)
In Example 1-2, an antiglare antireflection film was prepared in the same manner as in Example 1-2 except that the low refractive index layer was not applied, and further saponified in the same manner as in Example 1-1. Processing was performed to produce an antiglare antireflection film (4rF).

(Comparative Examples 1-5 and 1-6)
A commercially available antireflection film {“CVL02” manufactured by Fuji Photo Film Co., Ltd.} was used as the antireflection film (5F) of Comparative Example 1-5, and a wide viewing angle antireflection film {“CVU01”, Fuji Photo Film Co., Ltd. The product was evaluated as an antireflection film (6F) of Comparative Example 1-6.

(Comparative Example 1-7)
Furthermore, the polarizing plate on the surface was peeled off from a commercially available liquid crystal display device using “Clear AR” having a multilayer structure, and this was evaluated as a polarizing plate sample (7rP) of Comparative Example 1-7.

[Evaluation of antiglare antireflection film]
About the obtained film sample, the following items were evaluated. The results are shown in Tables 1 and 2.

(1) Reflection intensity measurement As shown in FIGS. 1A and 1B, white parallel light of about 5 mmφ is applied to the surface of the antireflection film sample A, and the incident light direction E and the normal direction D of the film The angle dependence of the reflected light intensity was measured by continuously changing the angle of the light-receiving portion G in increments of 0.1 ° within the in-plane C including. As a measuring device, an automatic variable angle photometer “GP-5 type” manufactured by Murakami Color Research Laboratory Co., Ltd. was used.

An example of the measurement result is shown in FIG. The horizontal axis represents the angle θ of the light receiving portion with respect to the film normal, and the vertical axis represents the relative reflection intensity R _rel (θ) normalized by the peak intensity. When calculating the reflectance, the light source quantity I ₀ when the incident light was directly measured in the absence of the sample was set to 100% intensity. Accordingly, when the reflection intensity at each reflection angle is I (θ), the reflectance R (θ) can be calculated as I (θ) / I ₀ . The rate of change in reflection intensity with respect to the reflection angle θ, | dR (θ) / dθ |, was calculated as the absolute value of the slope a from the average value of 10 points on both sides of the data measured in increments of 0.1 °. Further, the relative reflectivity R _rel (θ) is the reflectivity R _{s at the} reflection angle at which regular reflection occurs (in FIG. 2, the regular reflection angle is 5 °, and R _s = R (5)}. Calculated as the ratio of the reflectance at R _i , ie R _rel = R (θ) / R _s . In addition, | dR (θ) / dθ | of the light source used was 1.2.

(2) Average reflectance After the back surface of the film is sandpapered, it is treated with black ink, and the surface side is removed using a spectrophotometer (manufactured by JASCO Corporation) with the back surface reflection eliminated. , The specular spectral reflectance at an incident angle of 5 ° was measured in the wavelength region of 380 to 780 nm. The arithmetic average value of the specular reflectance of 450-650 nm was used for the result.

(3) Haze following measurement, the total haze of the obtained film (H), internal haze (H _i), and measuring the surface haze (H _s).
(I) The total haze value (H) of the film obtained according to JIS K-7136 is measured. (Ii) A value measured in a state where the surface on the low refractive index layer side of the obtained film is immersed in a medium having the same refractive index as that of the low refractive index layer, and a cover glass is further placed thereon, and the influence of surface haze is eliminated. The internal haze ( _Hi ) of the film was used.
(Iii) The value obtained by subtracting the internal haze (H _i ) calculated in (ii) from the total haze (H) measured in (i) above was calculated as the surface haze (H _s ) of the film.

(4) Transmission image definition In accordance with JIS K-7105, the transmission image definition was measured with an optical comb having a slit width of 0.5 mm using an image clarity measuring device “ICM-2D type” manufactured by Suga Test Instruments Co., Ltd. And measured.

(5) Centerline average roughness The centerline average roughness Ra of the obtained antireflection film was measured according to JIS B-0601.

(6) Anti-glare property The degree of blurring of the reflected image when an exposed anti-louvered fluorescent lamp (8000 cd / m ² ) is projected from a 45 ° angle on the obtained anti-reflection film and observed from the −45 ° direction. Was evaluated according to the following criteria.
I do not know the outline of the fluorescent lamp at all: ◎
Slightly understand the outline of the fluorescent lamp: ○
The fluorescent lamp is blurred, but the outline can be identified: △
Fluorescent lamp is hardly blurred: ×

(7) Whiteness The surface of the obtained antireflection film opposite to the surface coated with the antiglare antireflection layer is attached to a black acrylic resin board with an adhesive, and a 500 Lx bright room The degree to which black appears black at the bottom (whether it looks neat black or looks gray due to scattered light) was visually observed. For the samples of Examples and Comparative Examples, 10 points of relative evaluation were performed with 1 point being the whitest and 10 points being the black acrylic plate.

  The evaluation results of the obtained antiglare antireflection film are shown in Tables 10 and 11 together with the structure of each antireflection film.

<Preparation of polarizing plate>
Examples 2-1 to 2-5 and comparative examples 2-1 to 2-6
An 80 μm-thick triacetyl cellulose film {“TAC-TD80U”, manufactured by Fuji Photo Film Co., Ltd.) was immersed in a 1.5 mol / L, 55 ° C. NaOH aqueous solution for 2 minutes, and then neutralized and washed with water. And antiglare antireflection film prepared in Example 1 {saponified: antireflection film samples (1F to 5F) of Examples 1-1 to 1-5 and Comparative Examples 1-1 to 1-6 The antireflective film sample (1rF-6rF)} was bonded to and protected on both surfaces of a polarizing film prepared by adsorbing iodine to polyvinyl alcohol and stretching it to prepare a polarizing plate. These are respectively Example 2-1 {polarizing plate sample (1P)} to Example 2-5 {polarizing plate sample (5P)} and comparative example 2-1 {polarizing plate sample (1rP)} to comparative example 2. It was set to -6 {polarizing plate sample (6rP)}.

Comparative Example 2-7
The polarizing plate on the surface was peeled off from a commercially available liquid crystal display device using “Clear AR” having a multilayer structure, and this was evaluated as a polarizing plate sample (7rP) of Comparative Example 2-7.

Comparative Example 2-8
Further, a polarizing plate was prepared using the saponified triacetyl cellulose film as a protective film on both sides, and used as a comparative polarizing plate sample (8rP).

[Evaluation of polarizing plate]
Part of the polarizing plate on the viewing side of the liquid crystal television {“LC20S4”, manufactured by Sharp Corporation} was peeled off, and then produced in Examples 2-1 to 2-5 and Comparative Examples 2-1 to 2-6, respectively. Polarizing plates (1P) to (5P) and (1rP) to (6rP), (7rP), and (8rP) were prepared by replacing each of the polarizing plates as a peeled polarizing plate. About the obtained display apparatus, the following items were evaluated. Is shown in Table 12.

Further, the polarizing plate on the viewing side of the liquid crystal television was replaced with a polarizing plate having no anti-glare function, and the display characteristics in the dark room were evaluated. The front luminance was 500 cd / m ² , the front contrast was 550, and the polar angle. The contrast at 30 ° and polar angle 60 ° was 180 or more and 25 or more in all directions, respectively.

(1) Image blur A non-glare-proofing polarizing plate is displayed on a white background of the LCD panel, with a 10-point size Ming Dynasty “rose” in 25 lines per line and 10 lines in a row. The degree of blur of the outline of the character (image blur) when compared with the case where the same display was used was visually evaluated according to the following criteria.
Bokeh is not worried at all and is preferable: ◎
Bokeh is slightly worrisome, but relatively preferable: ○
I am a little worried about the blur: △
Blur is conspicuous and undesirable: ×

(2) Reflection On the liquid crystal televisions obtained in Example 2 and Comparative Example 2, an exposed fluorescent lamp (8000 cd / m ² ) without a louver was projected from an angle of 45 ° and observed from a direction of −45 °. The degree of reflection of the fluorescent lamp was evaluated according to the following criteria.
Not reflected so much that the outline of the fluorescent lamp is not understood: ◎
The outline of the fluorescent lamp is slightly understood, but it is hardly reflected: ○
Fluorescent light is blurred but slightly reflected: △
Fluorescent light is completely reflected: ×

(3) White blur The liquid crystal TV obtained in Example 2 and Comparative Example 2 is installed in a 500 Lx bright room with a fluorescent lamp on the ceiling, and a moving image including a black display and a low gradation image is displayed. Evaluation of white blur was performed. In the case of black display, the degree of black looks black, and in the case of moving image display, whether the image is clearly visible (light room contrast) was visually observed according to the following criteria.
The black display looks black and the video looks clear: ◎
Both black display and video look a little sweet: ○
The whiteness in black display is conspicuous, and the moving image is not refreshing.
The sharpness of the video image is not clear: ×

  Similar samples for commercially available 32 inch diagonal LCD TV {"W32-L7000", manufactured by Hitachi, Ltd.} and 37 inch diagonal LCD television {"LC-37AD5", manufactured by Sharp Corporation} When the visibility was evaluated, the same results as those in the liquid crystal display device with a diagonal of 20 inches shown in Table 12 were obtained.

From the results shown in Table 12, the following is clear.
The antiglare antireflection film of the present invention can achieve both high antiglare property and improvement of image blur and white blur when applied to a liquid crystal television of 20 inches or more.

<Evaluation of anti-glare antireflection film in liquid crystal display>
Example 3-1.
As a polarizing plate on the backlight side of the liquid crystal cell of the transmission type TN liquid crystal cell (“Syncmster 172X”, manufactured by Samsung), a plain tack {“TD-80UL”, manufactured by FUJIFILM Corporation) is used as a protective film on the backlight side. Is applied to the protective film on the viewing side as the polarizing plate on the viewing side, using a viewing angle widening film {"Wide View Film SA 128" manufactured by Fuji Photo Film Co., Ltd.} When the anti-glare antireflection film (2F) produced in 1-2 is used as a protective film on the liquid crystal cell side, a viewing angle widening film {“Wide View Film SA 128”, manufactured by Fuji Photo Film Co., Ltd.} is used. Thus, a liquid crystal display device having a very wide viewing angle in the vertical and horizontal directions, extremely excellent visibility, and high display quality was obtained.

Example 3-2
As a polarizing plate on the backlight side of the liquid crystal cell of the transmissive TN liquid crystal cell {“RDT191S”, manufactured by Mitsubishi Electric Corporation}, a plain tack {“TD-80UL”, FUJIFILM Corporation )} Is used as a protective film on the liquid crystal cell side, and a viewing angle widening film {“Wide View Film SA 128”, manufactured by Fuji Photo Film Co., Ltd.} is used as a polarizing plate on the viewing side, and the protective film on the outermost surface on the viewing side The anti-glare antireflection film (2F) produced in Example 1-2 was used as a protective film on the liquid crystal cell side, and a viewing angle widening film {“Wide View Film SA 128”, manufactured by Fuji Photo Film Co., Ltd.}. When used, the vertical and horizontal viewing angles are very wide, and the brightness from the front is high and a vivid display is obtained. High a contrast, extremely excellent in visibility, liquid crystal display device with high display quality was obtained.

Fig.1 (a) is a schematic diagram which shows the method of measuring the angle dependence of the reflected light intensity by surface unevenness | corrugation of the antireflection film of this invention. FIG. 1B is a schematic diagram showing a surface C including a normal direction D of the film and an incident direction E of light. FIG. 2 is an example of the measurement result of the angle dependence of the reflected light intensity. FIG. 3 is a schematic cross-sectional view schematically showing a preferred embodiment of the antireflection film of the present invention. FIG. 4 is a schematic cross-sectional view schematically showing another preferred embodiment of the antireflection film of the present invention. FIG. 5 is a schematic sectional view schematically showing still another preferred embodiment of the antireflection film of the present invention. FIG. 6 is a schematic cross-sectional view schematically showing a preferred embodiment of an antiglare antireflection film using translucent particles according to the present invention. FIG. 7 is a schematic cross-sectional view schematically showing a preferred embodiment of an antiglare antireflection film which has been surface-shaped by embossing or the like according to the present invention. FIG. 8 is a sectional view of the coater 10 using the slot die 13 embodying the present invention. FIG. 9A shows the cross-sectional shape of the slot die 13 of the present invention, and FIG. 9B shows the cross-sectional shape of the conventional slot die 30. FIG. 10 is a perspective view showing the slot die 13 and its periphery in the coating process in which the present invention is implemented. FIG. 11 is a cross-sectional view showing the vacuum chamber 40 and the web W that are close to each other. (The back plate 40a is integrated with the main body of the chamber 40) FIG. 12 is a cross-sectional view showing another embodiment of the vacuum chamber 40 and the web W that are close to each other. (The back plate 40a is fastened to the chamber 40 with screws 40c)

Explanation of symbols

A: Antireflection film A
B: Surface of the antireflection film A C: Surface including the normal direction D of the antireflection film and the light incident direction E D: Normal direction of the antireflection film E: Light incident direction F: Light source G: Detector light reception Part

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

10: Coater 11: Backup roll W: Web 13: Slot die 14: Coating liquid 14a: Bead 14b: Coating film 15: Pocket 16: Slot 16a: Slot opening 17: Tip lip 18: Land 18a: Upstream lip land 18b : Downstream lip land I _UP : land length of upstream lip land 18a I _LO : land length of downstream lip land 18b L _O : over bite length (web of downstream lip land 18b and upstream lip land 18a Difference in distance from W)
G _L : gap between the tip lip 17 and the web W (gap between the downstream lip land 18b and the web W)

30: Conventional slot die 31a: Upstream lip land 31b: Downstream lip land 32: Pocket 33: Slot 40: Decompression chamber 40a: Back plate 40b: Side plate 40c: Screw

G _B : Gap between the back plate 40 a and the web W G _S : Gap between the side plate 40 _b and the web W

Claims (17)

An antireflection film having at least an antiglare layer and a low refractive index layer on a transparent support, wherein substantially parallel light is incident on the film surface, and the film includes a normal line and an incident direction, When the reflection intensity due to the surface unevenness of the film is measured, the maximum value of the change amount of reflectance | dR (θ) / dθ | with respect to the reflection angle θ is 0.005 or more and less than 0.03. Antireflection film.
[Where R (θ) is the reflectance at the reflection angle θ. ] An antireflection film having at least an antiglare layer and a low refractive index layer on a transparent support, wherein substantially parallel light is incident on the film surface, and the film includes a normal line and an incident direction, When the reflection intensity due to the surface irregularities of the film was measured, the maximum amount of change of relative reflectance R _rel (θ) with respect to the reflection angle θ | dR _rel (θ) / dθ | An antireflective film characterized by being
[Where R _rel (θ) is the relative reflectance normalized by the reflectance R _s in the regular reflection direction, R _rel (θ) = R (θ) / R _s , and R (θ) is the reflection It is a reflectance at an angle θ. ]   The antireflection film according to claim 1 or 2, wherein the specular reflectance at 5 ° incidence is 0.5% or more and less than 3%.   The antireflection film according to any one of claims 1 to 3, wherein a haze value resulting from internal scattering of the antireflection film is from 0 to 35%, and a haze value resulting from surface scattering is from 5 to 15%.   The antireflection film according to any one of claims 1 to 4, wherein the antireflection film has a center line average roughness Ra of 0.08 to 0.30 µm.   The antireflection film according to any one of claims 1 to 5, wherein the image clarity of the antireflection film according to JIS K-7105 is 5 to 60% when measured at an optical comb width of 0.5 mm.   The antireflection film according to any one of claims 1 to 6, wherein the antiglare layer contains at least a translucent resin and translucent particles.   The translucent resin is a cross-linked poly (meth) acrylate-based polymer particle comprising a (meth) acrylate monomer having at least trifunctional or higher functionality as a main component and the translucent particle having an acrylic content of 50 to 100% by mass. 7. The antireflection film according to 7.   Cross-linked polyacrylic (-styrene) (co) polymer particles in which the translucent resin contains at least a trifunctional or higher functional (meth) acrylate monomer as the main component, and the translucent particles have an acrylic content of 50 to 100% by mass. The antireflection film according to claim 7 or 8.   A polarizing plate having a polarizing film and protective films provided on both sides of the polarizing film, wherein at least one of the protective films is the antireflection film according to any one of claims 1 to 9. Polarizing plate.   The polarizing plate according to claim 10, wherein at least one of the two protective films is an optical compensation film having optical anisotropy. The protective film arranged opposite to the antireflection film among the two protective films is an optical compensation film having at least an optically anisotropic layer in which the orientation of the liquid crystalline compound is fixed. The polarizing plate as described in.   Of the two protective films, an optical anisotropic film comprising a compound having a discotic structural unit on the surface opposite to the surface to be bonded to the polarizing film, the protective film disposed opposite to the antireflection film The polarizing plate according to claim 10, which is an optical compensation film having a functional layer.   A laminated polarizing plate, wherein the polarizing plate is a polarizing plate according to any one of claims 10 to 13, comprising at least one optical compensation film and a polarizing plate bonded together through an adhesive layer. .   A liquid crystal display device comprising at least one polarizing plate according to claim 10. It includes at least a polarizing plate, a liquid crystal cell for display, and a backlight. The maximum luminance is 300 cd / m ² or more, and the darkroom contrast ratio in white / black display is 500 or more in the normal direction of the liquid crystal cell, 30 ° to the normal. A liquid crystal display device having an angle range of 150 or more and an angle range of 60 ° or less with respect to the normal line of 15 or more, wherein the polarizing plate according to claim 10 is a display device. A liquid crystal display device arranged on the outermost surface of the observer side.   The liquid crystal display device according to claim 15 or 16, wherein a diagonal of the display screen is 20 inches or more.

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