JP2005121870A - Antireflective laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antireflective laminate which decreases scratches, blocking, failure due to foreign matters and coating failure even when an antireflection layer containing fine particles is applied. <P>SOLUTION: The antireflective laminate has at least one antireflection layer containing fine particles on one surface of a supporting body, and has at least a conductive layer and an overcoat layer on the opposite face of the supporting body to the face where the antireflection layer is formed. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an antireflection laminate, and more particularly to an antireflection laminate having reduced flaws, blocking, foreign matter failure, and coating failure.

  The display surface of various image display devices such as a liquid crystal display device (LCD), a plasma display panel (PDP), an electroluminescence display (ELD), and a cathode ray tube display device (CRT) is fluorescent to increase its visibility. There is a demand for less reflection of light emitted from an external light source such as a lamp. Such reflection of light rays can be reduced by providing an antireflection film on the surface of the image display device. As the antireflection film, a single layer structure in which a low refractive index layer having a low refractive index is provided on a display surface or a multilayer film in which a transparent thin film of metal oxide is laminated has been conventionally used. When a plurality of transparent thin films are used, reflection of light having various wavelengths can be prevented. Therefore, the visibility can be further improved by forming the antireflection film in a multilayer structure (antireflection laminate).

  As the antireflection film used for the antireflection laminate, a multilayer film in which transparent thin films of metal oxide are laminated is generally used, and a plurality of transparent thin films are used in order to lower the reflectance in a wide wavelength range. It is known that a transparent thin film of metal oxide is formed by a physical vapor deposition (PVD) method or chemical vapor deposition (CVD). A transparent thin film of metal oxide has excellent optical properties as an antireflection film, but the formation method by vapor deposition has low productivity and is not suitable for mass production. Instead of the vapor deposition method, a method of manufacturing an antireflection film by forming an optical functional layer on a transparent support by coating has also been proposed. In this case, it is common to form a metal oxide thin film by a sol-gel method, but there is also a method of forming a thin film by dispersing metal oxide fine particles in a binder solution in view of ease of adjusting the refractive index and stability. Be taken.

  On the other hand, in the antireflection laminate, dust is easily attached due to static electricity or the like at the time of film production, a step of bonding to a polarizing plate or a display device, or panel production, and failure often occurs. Therefore, for the purpose of improving the conductivity, a conductive layer containing an ionic polymer compound or conductive fine particles (also referred to as an antistatic layer) may be provided on one surface of the support. The conductive layer is provided at a position closer to the substrate than the hard coat layer with a film thickness of about 0.2 μm, a method for imparting conductivity to the hard coat layer, and the medium refractive index of the antireflection laminate. A method of imparting conductivity to a layer or a high refractive index layer is known. However, if a conductive layer is provided closer to the substrate than the hard coat layer, there is a distance between the conductive layer and the outermost surface of the film, so surface resistance is difficult to occur, and a conductive agent is added to the hard coat layer. As a result, haze, scratch resistance, etc. deteriorate, and when the middle refractive index layer or the high refractive index layer is made conductive, the film thickness becomes thin, so that there is a problem that it is difficult to obtain sufficient surface resistance.

  For this reason, a technique is disclosed in which an antistatic layer is provided on the opposite surface of a substrate having an antireflection layer (see, for example, Patent Document 1), but when the antireflection layer is provided by a sol-gel method, the antireflection layer is provided. Since the film strength of the film is relatively high, scratches do not occur even when contacting with the conductive layer on the opposite surface at the time of winding, and there is little occurrence of failure such as scratches or blocking.

However, when the antireflection layer is a layer containing fine particles, the film strength of the layer is relatively lower than the film strength obtained by the sol-gel method. I understood. In particular, the conductive layer tends to be a layer containing a large amount of a polymer compound or a fine particle dispersion in order to obtain conductivity, and the antireflection layer may contain a large amount of fine particles for adjusting the refractive index. In this case, the fine particles are easily contacted with each other and easily damaged. Furthermore, the fine particles that have been peeled off may become foreign matter and cause a failure of the antireflection layer. In addition, since the particles are in strong contact with each other, a part of the components of the conductive layer is transferred to the antireflection layer, and when the antireflection layer is laminated, the coating properties may deteriorate due to this transfer component, and the coating may not be performed well. It was. In order to lower the reflectance of the antireflection film, it is effective to lower the refractive index of the outermost low refractive index layer. There are several means for lowering the refractive index. Among these hollow particles, which are hollow, the hollow portion becomes the refractive index of air, and the refractive index can be relatively easily lowered. However, the layer using the hollow particles is more likely to have a failure such as a scratch than the layer containing general fine particles.
JP 2002-343137 A

  In view of the above problems, an object of the present invention is to provide an antireflection laminate in which scratches, blocking, foreign matter failures, and coating failures are reduced even when an antireflection layer containing fine particles is applied.

The above object of the present invention is achieved by the following configurations.
(Claim 1)
An antireflection layer containing at least one layer of fine particles is provided on one side of the support, and at least a conductive layer and an overcoat layer are provided on the side opposite to the side on which the antireflection layer is provided. Antireflection laminate.
(Claim 2)
The antireflection laminate according to claim 1, wherein the antireflection layer comprises at least a high refractive index layer and a low refractive index layer.
(Claim 3)
The antireflection laminate according to claim 1, wherein the antireflection layer is provided in the order of a medium refractive index layer, a high refractive index layer, and a low refractive index layer from the support side.
(Claim 4)
The antireflection laminate according to claim 2 or 3, wherein the low refractive index layer contains SiO ₂ fine particles or MgF ₂ fine particles.
(Claim 5)
The antireflection laminate according to claim 4, wherein the SiO ₂ fine particles are hollow.
(Claim 6)
The medium refractive index layer and the high refractive index layer are selected from the group consisting of Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P, and S. The antireflection laminate according to any one of claims 3 to 5, comprising fine particles of a metal oxide having at least one element selected.
(Claim 7)
2. The antireflection laminate according to claim 1, wherein a surface specific resistance of the surface provided with the conductive layer and the overcoat layer is 10 ¹¹ Ω / □ (25 ° C., 55% RH) or less.
(Claim 8)
The antireflection laminate according to claim 1, wherein the conductive layer contains an ionic polymer compound.
(Claim 9)
The antireflective laminate according to claim 8, wherein the ionic polymer compound is a quaternary ammonium cationic polymer having molecular crosslinking.
(Claim 10)
The conductive material of the conductive layer contains as a main component at least one element selected from the group consisting of Sn, Ti, In, Al, Zn, Si, Mg, Ba, Mo, W, and V, The volume resistivity is 10 ⁷ Ω · cm (25 ° C., 55% RH) or less, and the antireflection laminate according to any one of claims 1, 7, and 8.
(Claim 11)
The said electroconductive layer contains a cellulose ester resin or an acrylic resin, The antireflection laminated body of any one of Claims 1 and 7-10 characterized by the above-mentioned.
(Claim 12)
The antireflection laminate according to claim 1, wherein the overcoat layer contains at least a cellulose ester resin or an acrylic resin.
(Claim 13)
The antireflection laminate according to claim 12, wherein the overcoat layer contains a hydrophilic polymer compound.
(Claim 14)
The antireflection laminate according to claim 12 or 13, wherein the overcoat layer contains at least one of gelatin or a gelatin derivative and a cellulose ester resin.
(Claim 15)
The amount of the conductive layer after drying is 0.05 to 1.0 g / m ² , and the amount of the overcoat layer after drying is 0.05 to 1.0 g / m ^2. The antireflection laminate according to any one of claims 1 and 7 to 14.

  According to the present invention, even when an antireflection layer containing fine particles is applied, an antireflection laminate having reduced scratches, blocking, foreign matter failure, and coating failure can be provided.

  The best mode for carrying out the present invention will be described in detail below, but the present invention is not limited thereto.

  In the present invention, an antireflection layer containing at least one fine particle is provided on one surface of a support, and at least a conductive layer and an overcoat layer are provided on the surface opposite to the side on which the antireflection layer is provided. It is characterized by.

  That is, when an overcoat layer mainly composed of a resin is provided on the conductive layer, it has been found that even when fine particles are used in the antireflection layer, a particularly remarkable effect can be obtained with respect to the above problems. It came to make.

  The overcoat layer may be provided before the antireflection layer is provided, but is preferably provided before the antireflection layer having a low film strength is provided. In addition, after the uppermost antireflection layer is provided, the antireflection laminate is designed so that sufficient film strength can be obtained. In order to further improve the film strength, the film roll may be aged. In this case, depending on the aging temperature, so-called film roll winding and blocking may occur, which may damage the antireflection layer or the conductive layer. If an overcoat layer is provided on the conductive layer, this scratch can be prevented, and this effect is also remarkable when fine particles are used in the antireflection layer.

  Hereinafter, the present invention will be described in detail.

(Conductive layer)
The conductive layer according to the present invention may be provided on the surface opposite to the side on which the antireflection layer is provided by providing an antireflection layer containing at least one layer of fine particles on one surface of the support described later. It is a feature.

  The conductive layer imparts a function of preventing the resin film from being charged when the support (resin film, etc.) is handled. Specifically, the conductive layer contains an ion conductive substance or conductive fine particles. This is done by providing a layer to be used. Here, the ion conductive substance is a substance that shows electric conductivity and contains ions that are carriers for carrying electricity, and examples include ionic polymer compounds.

The surface specific resistance of the conductive layer according to the present invention is preferably adjusted to 10 ¹¹ Ω / □ (25 ° C., 55% RH) or less, more preferably 10 ¹⁰ Ω / □ (25 ° C., 55% RH). ) Or less, particularly preferably 10 ⁹ Ω / □ (25 ° C., 55% RH) or less.

  Here, although details of the measurement of the surface specific resistance value are described in the examples, the sample was conditioned for 24 hours under the conditions of 25 ° C. and 55% RH, and a terraohm meter model VE-30 manufactured by Kawaguchi Electric Co. Use to measure.

  Further, on the conductive layer according to the present invention, an overcoat layer is further provided as the outermost surface layer. The surface specific resistance value is measured by measuring the surface specific resistance of the outermost surface layer on the side where the conductive layer is provided. The value is substantially defined as the surface resistivity value of the conductive layer.

  In order to adjust the surface specific resistance value of the conductive layer according to the present invention within the above-described range, conductive materials as shown below are preferably used.

  As the conductive material according to the present invention, an ionic polymer compound, a metal oxide or the like is preferably used.

  Examples of the ionic polymer compound include anionic polymer compounds such as those described in JP-B-49-23828, JP-A-49-23827, and JP-A-47-28937; JP-B-55-734, JP-A-50-54672 Ionene type polymers having a dissociating group in the main chain, as seen in JP-B Nos. 59-14735, 57-18175, 57-18176, 57-56059, etc .; No. 57-15376, No. 53-45231, No. 55-145783, No. 55-65950, No. 55-67746, No. 57-11342, No. 57-19735, No. 58-56858. No., JP-A 61-27853, 62-9346, and a cationic pendant type poly having a cationic dissociation group in the side chain. Over; and the like can be mentioned.

  Particularly preferred ionic polymer compounds include polymers having units of the following general formulas [1], [1a] and [1b].

In the formula, R ₃ , R ₄ , R ₅ and R ₆ each represent a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, and R ₃ and R ₄ and / or R ₅ and R ₆ are bonded to each other such as piperazine. A nitrogen-containing heterocycle may be formed. A, B and D are each a substituted or unsubstituted alkylene group having 2 to 10 carbon atoms, an arylene group, an alkenylene group, an arylenealkylene _{group, -R 7 COR 8 -, -} R 9 COOR 10 OCOR 11 -, - R 12 _{OCR 13 COOR 14 -, - R} 15 - (oR 16) m -, - R 17 CONHR 18 NHCOR 19 -, - R 20 OCONHR 21 NHCOR 22 - or -R ₂₅ NHCONHR ₂₄ NHCONHR ₂₅ - represents a. R ₇ , R ₈ , R ₉ , R ₁₁ , R ₁₂ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₁₉ , R ₂₀ , R ₂₂ , R ₂₃ and R ₂₅ are alkylene groups, R ₁₀ , R ₁₃ , R ₁₈ , R ₂₁ and R ₂₄ are each a linking group selected from a substituted or unsubstituted alkylene group, alkenylene group, arylene group, arylene alkylene group and alkylene arylene group, m represents a positive integer of 1 to 4, X ⁻ represents an anion.

  However, when A is an alkylene group, a hydroxyalkylene group or an arylenealkylene group, it is preferable that B is not an alkylene group, a hydroxylalkylene group or an arylenealkylene group.

E represents a group selected from a simple bond, —NHCOR ₂₆ CONH— or D. R ₂₆ represents a substituted or unsubstituted alkylene group, alkenylene group, arylene group, arylene alkylene group, or alkylene arylene group.

Z ₁ and Z ₂ are linked to E in the form of a quaternary salt of a group of nonmetallic atoms (≡N ⁺ [X ⁻ ] — necessary for forming a 5-membered or 6-membered ring together with —N═C— group. May be).

  n represents an integer of 5 to 300.

  Among them, a quaternary ammonium cationic polymer having molecular crosslinking is particularly preferable, and a quaternary ammonium cationic polymer not containing chlorine ions and having molecular crosslinking is particularly preferably used from the viewpoint of environmental safety such as prevention of dioxin generation.

  Specific examples of the ionic polymer compound according to the present invention are given below, but the present invention is not limited thereto.

The ionic polymer compound according to the present invention may be used alone or in combination of several kinds of ionic polymer compounds. The content of the ionic polymer compound according to the present invention in the resin film is preferably 0.02 g to 1.0 g / m ² , particularly preferably 0.02 g to 0.5 g / m ² .

The conductive material contains at least one element selected from the group consisting of Sn, Ti, In, Al, Zn, Si, Mg, Ba, Mo, W and V as a main component, and has a volume. A conductive material having a resistivity of 10 ⁷ Ω · cm or less is preferably used.

  Examples of the conductive material include metal oxides and composite oxides having the above elements.

As an example of the metal oxide, ZnO, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , SiO ₂ , MgO, BaO, MoO ₂ , V ₂ O ₅ , or a composite oxide thereof is preferable. In particular, ZnO, TiO ₂ and SnO ₂ are preferred. Examples of containing different atoms include, for example, addition of Al and In to ZnO, addition of Nb and Ta to TiO ₂ , and addition of Sb, Nb and halogen elements to SnO ₂ . Addition is effective. The amount of these different atoms added is preferably in the range of 0.01 to 25 mol%, particularly preferably in the range of 0.1 to 15 mol%.

In addition, the volume resistivity of these metal oxide powders having conductivity is 10 ⁷ Ω · cm or less, particularly 10 ⁵ Ω · cm or less.

  Furthermore, in the present invention, fine particles may be added to the conductive layer, and examples thereof include fine particles containing silica, colloidal silica, alumina, alumina sol, kaolin, talc, mica, calcium carbonate or the like as a constituent component. I can do it.

  The average particle diameter of the fine particles described above is preferably 0.01 μm to 10 μm, more preferably 0.01 μm to 5 μm, and the addition amount is 0.05 part to 10 parts by mass with respect to the solid content in the coating agent. Parts are preferred, with 0.1 to 5 parts being particularly preferred.

  Moreover, in order for the electroconductive layer which concerns on this invention to show sufficient antistatic effect and to maintain easy-adhesiveness with an overcoat layer, it is preferable to contain a cellulose ester resin or an acrylic resin.

  Examples of the cellulose ester resin include cellulose derivatives such as cellulose diacetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate phthalate, and cellulose nitrate.

  Examples of the acrylic resin include Acrypet MD, VH, MF, V (Mitsubishi Rayon Co., Ltd.), Hyperl M4003, M-4005, M-4006, M-4202, M-5000, M -5001, M-4501 (manufactured by Negami Kogyo Co., Ltd.), Dialnal BR-50, BR-52, BR-53, BR-60, BR-64, BR-73, BR-75, BR-77, BR- 79, BR-80, BR-82, BR-83, BR-85, BR-87, BR-88, BR-90, BR-93, BR-95, BR-100, BR-101, BR-102, BR-105, BR-106, BR-107, BR-108, BR-112, BR-113, BR-115, BR-116, BR-117, BR-118, etc. (Mitsubishi Rayon Co., Ltd.) Various homopolymers and copolymers to produce Le and methacrylic monomer as a raw material is preferably used.

  The resin used here is preferably 60% by mass or more, more preferably 80% by mass or more of the total resin used in the conductive layer, and an actinic radiation curable resin or a thermosetting resin is used as necessary. It can also be added. These resins are coated as a binder in a state dissolved in the following solvent.

  The following solvents are preferably used in the coating composition for coating the antistatic layer. As the solvent, hydrocarbons, alcohols, ketones, esters, glycol ethers, and other solvents (methylene chloride) can be appropriately mixed and used, but are not particularly limited thereto.

  Examples of the hydrocarbons include benzene, toluene, xylene, hexane, cyclohexane and the like, and examples of alcohols include methanol, ethanol, n-propyl alcohol, iso-propyl alcohol, n-butanol, 2-butanol, tert- Examples include butanol, pentanol, 2-methyl-2-butanol, and cyclohexanol. Examples of ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Examples of esters include methyl formate, ethyl formate, Examples thereof include methyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, ethyl lactate, and methyl lactate. Examples of glycol ethers (C1 to C4) include methyl cellosolve, ethyl cellosolve, propylene glycol monomethyl ester. As terrestrial (PGME), propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol monoisopropyl ether, propylene glycol monobutyl ether, or propylene glycol mono (C1-C4) alkyl ether esters, propylene glycol monomethyl Examples of ether acetate, propylene glycol monoethyl ether acetate, and other solvents include methylene chloride and N-methylpyrrolidone. Although not particularly limited to these, a solvent in which these are appropriately mixed is also preferably used.

  As a coating method of the conductive layer coating composition, using a gravure coater, dip coater, wire bar coater, reverse coater, extrusion coater, etc., the coating solution film thickness (sometimes referred to as wet film thickness) is 1 to 100 μm. In particular, 5 to 30 μm is preferable.

(Overcoat layer)
In the antireflection laminate according to the present invention, an overcoat layer is provided on the conductive layer. Providing an overcoat layer as described above is essential for obtaining the effects of the present invention.

  The overcoat layer according to the present invention preferably contains a resin. Examples of the resin used include vinyl chloride / vinyl acetate copolymer, vinyl chloride resin, vinyl acetate resin, copolymer of vinyl acetate and vinyl alcohol, partial Hydrolyzed vinyl chloride / vinyl acetate copolymer, vinyl chloride / vinylidene chloride copolymer, vinyl chloride / acrylonitrile copolymer, ethylene / vinyl alcohol copolymer, chlorinated polyvinyl chloride, ethylene / vinyl chloride copolymer, ethylene / vinyl acetate copolymer, etc. Cellulose such as homopolymer or copolymer, cellulose nitrate, cellulose acetate propionate, cellulose diacetate, cellulose triacetate, cellulose acetate phthalate, cellulose acetate butyrate resin Sester resin, copolymer of maleic acid and / or acrylic acid, acrylic acid ester copolymer, acrylonitrile / styrene copolymer, chlorinated polyethylene, acrylonitrile / chlorinated polyethylene / styrene copolymer, methyl methacrylate / butadiene / styrene copolymer, acrylic resin, polyvinyl acetal Resin, polyvinyl butyral resin, polyester polyurethane resin, polyether polyurethane resin, polycarbonate polyurethane resin, polyester resin, polyether resin, polyamide resin, amino resin, styrene / butadiene resin, butadiene / acrylonitrile resin rubber resin, silicone resin , Fluorine resin, polymethyl methacrylate, polymethyl methacrylate and polymethyl acrylate It can be mentioned bets copolymers, but is not limited thereto. A cellulose ester resin or an acrylic resin is preferable, and a cellulose ester resin is particularly preferable. Among them, cellulose diacetate and cellulose acetate propionate are preferable.

In order to improve the effect of the present invention, it is preferable to contain at least one hydrophilic polymer compound (a) or gelatin or a gelatin derivative. As the hydrophilic polymer compound (a) used in the present invention, Preferably, hydrophilic cellulose derivatives (for example, methyl cellulose, carboxymethyl cellulose, hydroxy cellulose, etc.), polyvinyl alcohol derivatives (for example, polyvinyl alcohol, vinyl acetate-vinyl alcohol copolymer, polyvinyl acetal, polyvinyl formal, polyvinyl benzal, etc.), Natural polymer compounds (for example, gelatin, casein, gum arabic, etc.), hydrophilic polyester derivatives (for example, partially sulfonated polyethylene terephthalate), hydrophilic polyvinyl derivatives (for example, poly-N- Vinylpyrrolidone, polyacrylamide, polyvinylindazole, polyvinylpyrazole and the like), among others, hydrophilic cellulose derivatives, polyvinyl alcohol derivatives, natural polymer compounds (gelatin or gelatin derivatives) and the like are more preferably used. Of course, the above derivatives can be used alone or in combination of two or more.

  The overcoat layer according to the present invention may contain fine particles.

  Examples of the fine particles contained in the overcoat layer useful in the present invention include inorganic compound fine particles and organic compound fine particles.

  The amount of fine particles added to the binder of the overcoat layer is preferably 0.01 parts by weight to 1 part by weight, more preferably 0.05 parts by weight to 0.5 parts by weight, with respect to 100 parts by weight of the resin. Most preferred is 08 to 0.2 parts by weight. The larger the addition amount, the lower the dynamic friction coefficient, and the smaller the addition amount, the lower the haze and the fewer the aggregates.

  The organic solvent used in the overcoat layer is not particularly limited, but since the anti-curl function can be imparted to the overcoat layer, the organic solvent for dissolving the cellulose ester film and the resin of the cellulose ester film material or the organic solvent for swelling Solvents are useful. These may be appropriately selected depending on the curl degree of the cellulose ester film, the type of resin, the mixing ratio, the coating amount, and the like.

  Examples of the organic solvent that can be used for the overcoat layer include benzene, toluene, xylene, dioxane, acetone, methyl ethyl ketone, N, N-dimethylformamide, methyl acetate, ethyl acetate, N-methylpyrrolidone, 1,3-dimethyl- 2-Imidazolidinone. Further, there are methanol, ethanol, n-propyl alcohol, i-propyl alcohol, n-butanol and the like, but the organic solvent is not particularly limited thereto.

  As a coating method of the overcoat layer coating composition, using a gravure coater, dip coater, wire bar coater, reverse coater, extrusion coater, etc., the coating solution film thickness (sometimes referred to as wet film thickness) is 1 to 100 μm. In particular, 5 to 30 μm is preferable.

Moreover, it is preferable that the adhesion amount after drying of the said electroconductive layer is 0.05-1.0 g / m < ² >, and the adhesion amount after drying of an overcoat layer is 0.05-1.0 g / m < ² >.

(Antireflection layer)
In the antireflection laminate according to the present invention, the metal oxide layer may be directly formed on the transparent base film described later, but at least one other coating layer is provided, and the long base film having an uneven surface It may be formed on the top. The other coating layer is preferably an actinic radiation curable resin layer described later having a centerline average surface roughness (Ra) defined by JIS B 0601 of 0.01 to 1 μm. These are resin layers that are cured by active rays such as ultraviolet rays. By coating the metal oxide layer on the resin layer cured with such ultraviolet rays, an excellent antireflection laminate with reduced generation of transport scratches and cracks can be obtained.

  The basic structure of the antireflection laminate of the present invention will be described. For example, the antireflection laminate includes a transparent support / hard coat layer / low refractive index layer, a transparent support / hard coat layer / high refractive index layer / low refractive index layer, and a transparent support / hard coat layer / medium refractive index. Layer / high refractive index layer / low refractive index layer in order, transparent support / hard coat layer / high refractive index layer / low refractive index layer, transparent support / hard coat layer / medium refractive index layer / High refractive index layer / Low refractive index layer is preferable. The transparent support, the middle refractive index layer, the high refractive index layer, and the low refractive index layer have a refractive index that satisfies the following relationship.

  The refractive index of the low refractive index layer <the refractive index of the transparent support <the refractive index of the medium refractive index layer <the refractive index of the high refractive index layer.

  In an antireflection laminate having a medium refractive index layer, a high refractive index layer, and a low refractive index layer, as described in JP-A-59-50401, the medium refractive index layer has the following formula (1): When the refractive index layer satisfies the following mathematical formula (2) and the low refractive index layer satisfies the following mathematical formula (3), the average reflectance of the antireflection laminate can be further reduced, which is preferable.

(Hλ / 4) × 0.7 <n ₃ d ₃ <(hλ / 4) × 1.3 (1)
In formula (1), h is a positive integer (generally 1, 2 or 3), n ₃ is the refractive index of the medium refractive index layer, and d ₃ is the film thickness (nm) of the medium refractive index layer. It is. Further, λ is a wavelength, which is a value in the range of 350 to 800 (nm).

(Jλ / 4) × 0.7 <n ₄ d ₄ <(jλ / 4) × 1.3 (2)
In formula (2), j is a positive integer (generally 1, 2 or 3), n ₄ is the refractive index of the high refractive index layer, and d ₄ is the film thickness (nm) of the high refractive index layer. It is. Further, λ is a wavelength, which is a value in the range of 350 to 800 (nm).

(Kλ / 4) × 0.7 <n ₅ d ₅ <(kλ / 4) × 1.3 (3)
In Equation (3), k is a positive odd number (generally 1), n ₅ is the refractive index of the low refractive index layer, and d ₅ is the film thickness (nm) of the low refractive index layer. Further, λ is a wavelength, which is a value in the range of 350 to 800 (nm).

  Moreover, in this invention, it is also preferable to give an unevenness | corrugation to a hard-coat layer or a high refractive index layer, and to set it as an anti-glare antireflection laminated body.

  In addition, a layer structure in the order of a transparent support, a hard coat layer (antiglare layer), a high refractive index layer, a low refractive index layer, a high refractive index layer, and a low refractive index layer is also a preferable configuration. An antiglare property can be imparted to the low refractive index layer on the surface, and an antiglare layer may be provided on the surface.

<High refractive index layer and medium refractive index>
In the present invention, in order to reduce the reflectance, it is preferable to provide a high refractive index layer between the transparent support or the transparent support provided with the hard coat layer and the low refractive index layer. In addition, it is more preferable to provide a middle refractive index layer between the transparent support and the high refractive index layer in order to reduce the reflectance. The refractive index of the high refractive index layer is preferably 1.55 to 2.30, and more preferably 1.57 to 2.20. The refractive index of the medium refractive index layer is adjusted to be an intermediate value between the refractive index of the transparent support 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 thickness of the high refractive index layer and the medium refractive index layer is preferably 5 nm to 1 μm, more preferably 10 nm to 0.2 μm, and most preferably 30 nm to 0.1 μm. The haze of the high refractive index layer and the medium refractive index layer is preferably 5% or less, more preferably 3% or less, and most preferably 1% or less. The strength of the high refractive index layer and the medium refractive index layer is preferably H or higher, more preferably 2H or higher, and most preferably 3H or higher, with a pencil hardness of 1 kg.

  In the present invention, the high refractive index layer is formed by applying and drying a coating liquid containing a monomer, oligomer or hydrolyzate of an organic titanium compound represented by the following general formula (1). A layer of 1.55 to 2.5 is preferred.

General formula (1)
Ti (OR ¹ ) ₄
In the formula, R ¹ is preferably an aliphatic hydrocarbon group having 1 to 8 carbon atoms, preferably an aliphatic hydrocarbon group having 1 to 4 carbon atoms. Moreover, the monomer, oligomer, or hydrolyzate thereof of an organic titanium compound reacts like -Ti-O-Ti- when an alkoxide group is hydrolyzed to form a crosslinked structure, thereby forming a cured layer.

Examples of the monomer or oligomer of the organic titanium compound used in the present invention include Ti (OCH ₃ ) ₄ , Ti (OC ₂ H ₅ ) ₄ , Ti (On-C ₃ H ₇ ) ₄ , Ti (O-i- _{C 3 H 7) 4, Ti} (O-n-C 4 H 9) 4, Ti (O-n-C 3 H 7) 4 2-10 mer, Ti (O-i-C 3 H 7) Preferred examples include ₄ to 10 mer of ₄ and 2 to 10 mer of Ti (On-C ₄ H ₉ ) ₄ . These may be used alone or in combination of two or more. Of these _{Ti (O-n-C 3} H 7) 4, Ti (O-i-C 3 H 7) 4, Ti (O-n-C 4 H 9) 4, Ti (O-n-C 3 H 7 ) ₄ to 10-mer and Ti (On-C ₄ H ₉ ) ₄ to 10-mer are particularly preferable.

  In the present invention, it is preferable that the organic titanium compound is added to a solution in which water and an organic solvent described later are sequentially added to the coating solution for the high refractive index layer. When water is added later, hydrolysis / polymerization does not proceed uniformly, and white turbidity occurs or film strength decreases. After the water and the organic solvent are added, it is preferable that they are stirred and mixed and dissolved in order to mix well.

  Further, as another method, it is also a preferred embodiment that an organic titanium compound and an organic solvent are mixed and this mixed solution is added to the mixed and stirred solution of water and the organic solvent.

Moreover, it is preferable that the quantity of water is the range of 0.25-3 mol with respect to 1 mol of organic titanium compounds. When the amount is less than 0.25 mol, hydrolysis and polymerization are not sufficiently progressed and the film strength is lowered. If it exceeds 3 moles, hydrolysis and polymerization will proceed excessively, resulting in generation of coarse TiO ₂ particles and white turbidity. Therefore, the amount of water needs to be adjusted within the above range.

  Moreover, it is preferable that the content rate of water is less than 10 mass% with respect to the coating liquid total amount. If the water content is 10% by mass or more with respect to the total amount of the coating solution, it is not preferable because the stability of the coating solution with time deteriorates and white turbidity occurs.

  The organic solvent according to the present invention is preferably a water-miscible organic solvent. Examples of the water-miscible organic solvent include alcohols (eg, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, secondary butanol, tertiary butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol, etc.), many Monohydric alcohols (for example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol, etc.), polyvalent Alcohol ethers (eg, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether) , Ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, ethylene glycol mono Phenyl ether, propylene glycol monophenyl ether, etc.), amines (eg, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenediamine) , Triethylenetetramine, tetraethylenepentamine, polyethyleneimine, pentamethyldiethylenetriamine, tetramethylpropylenediamine, etc.), amides (eg, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, etc.), heterocyclic rings (For example, 2-pyrrolidone, N-methyl-2-pyrrolidone, cyclohexyl pyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone, etc.), sulfoxides (for example, dimethyl sulfoxide, etc.), sulfones (for example, , Sulfolane and the like), urea, acetonitrile, acetone and the like, and alcohols, polyhydric alcohols, and polyhydric alcohol ethers are particularly preferable. The amount of these organic solvents used may be adjusted as described above so that the water content is less than 10% by mass with respect to the total amount of the coating solution.

  The monomer, oligomer or hydrolyzate of the organic titanium compound used in the present invention preferably occupies 50.0% by mass to 98.0% by mass in the solid content contained in the coating solution. The solid content ratio is more preferably 50% by mass to 90% by mass, and further preferably 55% by mass to 90% by mass. In addition, it is also preferable to add to the coating composition a polymer of an organic titanium compound (a product obtained by crosslinking the organic titanium compound in advance by hydrolysis) or titanium oxide fine particles.

  The high refractive index layer and the medium refractive index layer according to the present invention contain metal oxide particles as fine particles, and further contain a binder polymer.

  When the organic titanium compound hydrolyzed / polymerized by the coating liquid preparation method and the metal oxide particles are combined, the metal oxide particles and the hydrolyzed / polymerized organic titanium compound are firmly bonded, and the hardness and uniform film of the particles It is possible to obtain a strong coating film having both flexibility.

The metal oxide particles used for the high refractive index layer and the medium refractive index layer preferably have a refractive index of 1.80 to 2.80, and more preferably 1.90 to 2.80. The weight average diameter of the primary particles of the metal oxide particles is preferably 1 to 150 nm, more preferably 1 to 100 nm, and most preferably 1 to 80 nm. The weight average diameter of the metal oxide particles in the layer is preferably 1 to 200 nm, more preferably 5 to 150 nm, still more preferably 10 to 100 nm, and more preferably 10 to 80 nm. Most preferred. The average particle diameter of the metal oxide particles is measured by a light scattering method if it is 20-30 nm or more, and by an electron micrograph if it is 20-30 nm or less. The specific surface area of metal oxide particles, as measured values by the BET method is preferably from 10 to 400 m ² / g, more preferably from 20 to 200 m ² / g, with 30 to 150 m ² / g Most preferably it is.

  Examples of the metal oxide particles include at least one selected from Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P, and S. Specific examples of the metal oxide include titanium dioxide (eg, rutile, rutile / anatase mixed crystal, anatase, amorphous structure), tin oxide, indium oxide, zinc oxide, and zirconium oxide. Of these, titanium oxide, tin oxide, and indium oxide are particularly preferable. The metal oxide particles are mainly composed of oxides of these metals and can further contain other elements. The main component means a component having the largest content (mass%) among the components constituting the particles. Examples of other elements include Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P, and S.

  The metal oxide particles are preferably surface-treated. The surface treatment can be performed using an inorganic compound or an organic compound. Examples of inorganic compounds used for the surface treatment include alumina, silica, zirconium oxide and iron oxide. Of these, alumina and silica are preferable. Examples of the organic compound used for the surface treatment include polyols, alkanolamines, stearic acid, silane coupling agents, and titanate coupling agents. Of these, a silane coupling agent is most preferable.

  Specific examples of the silane coupling agent include methyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxyethoxysilane, methyltriacetoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane. Methoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyltriacetoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, γ-glycidyloxypropyltrimethoxysilane, γ-glycidyloxy Propyltriethoxysilane, γ- (β-glycidyloxyethoxy) propyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, γ-acryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, Examples include N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane and β-cyanoethyltriethoxysilane.

  Examples of silane coupling agents having a disubstituted alkyl group with respect to silicon include dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldiethoxysilane, and γ-glycidyloxypropylmethyldiethoxysilane. Γ-glycidyloxypropylmethyldimethoxysilane, γ-glycidyloxypropylphenyldiethoxysilane, γ-chloropropylmethyldiethoxysilane, dimethyldiacetoxysilane, γ-acryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropylmethyldi Ethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-methacryloyloxypropylmethyldiethoxysilane, γ-mercaptopropylmethyldimeth Shishiran, .gamma.-mercaptopropyl methyl diethoxy silane, .gamma.-aminopropyl methyl dimethoxy silane, .gamma.-aminopropyl methyl diethoxy silane, methyl vinyl dimethoxy silane, and methyl vinyl diethoxy silane.

  Among these, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, γ-acryloyloxypropyltrimethoxysilane and γ-methacryloyloxypropyltrimethoxysilane having a double bond in the molecule. Γ-acryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropylmethyldiethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, and γ-methacryloyloxypropylmethyldiethoxy having a disubstituted alkyl group with respect to silicon Silane, methylvinyldimethoxysilane and methylvinyldiethoxysilane are preferred, and γ-acryloyloxypropyltrimethoxysilane and γ-methacryloyloxyp Particularly preferred are propyltrimethoxysilane, γ-acryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropylmethyldiethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane and γ-methacryloyloxypropylmethyldiethoxysilane.

  Two or more coupling agents may be used in combination. In addition to the silane coupling agents shown above, other silane coupling agents may be used. Other silane coupling agents include alkyl esters of orthosilicate (eg, methyl orthosilicate, ethyl orthosilicate, n-propyl orthosilicate, i-propyl orthosilicate, n-butyl orthosilicate, sec-butyl orthosilicate, orthosilicate). Acid t-butyl) and its hydrolyzate.

  The surface treatment with the coupling agent can be carried out by adding the coupling agent to the fine particle dispersion and allowing the dispersion to stand at a temperature from room temperature to 60 ° C. for several hours to 10 days. In order to accelerate the surface treatment reaction, inorganic acids (for example, sulfuric acid, hydrochloric acid, nitric acid, chromic acid, hypochlorous acid, boric acid, orthosilicic acid, phosphoric acid, carbonic acid), organic acids (for example, acetic acid, polyacrylic acid, Benzenesulfonic acid, phenol, polyglutamic acid), or salts thereof (eg, metal salts, ammonium salts) may be added to the dispersion.

  These silane coupling agents are preferably hydrolyzed with a necessary amount of water in advance. When the silane coupling agent is hydrolyzed, the surfaces of the organic titanium compound and the metal oxide particles described above are easy to react and a stronger film is formed. It is also preferable to add a hydrolyzed silane coupling agent to the coating solution in advance. The water used for this hydrolysis can also be used for the hydrolysis / polymerization of the organic titanium compound.

  In the present invention, the treatment may be performed by combining two or more kinds of surface treatments. The shape of the metal oxide particles is preferably a rice grain shape, a spherical shape, a cubic shape, a spindle shape or an indefinite shape. Two or more kinds of metal oxide particles may be used in combination in the high refractive index layer and the middle refractive index layer.

  The ratio of the metal oxide particles in the high refractive index layer and the medium refractive index layer is preferably 5 to 65% by volume, more preferably 10 to 60% by volume, and still more preferably 20 to 55% by volume. is there.

  The metal oxide particles are supplied to a coating solution for forming a high refractive index layer and a medium refractive index layer in a dispersion state dispersed in a medium. As a dispersion medium for metal oxide particles, it is preferable to use a liquid having a boiling point of 60 to 170 ° C. Specific examples of the dispersion solvent include water, alcohol (eg, methanol, ethanol, isopropanol, butanol, benzyl alcohol), ketone (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone), ester (eg, methyl acetate, ethyl acetate). , Propyl acetate, butyl acetate, methyl formate, ethyl formate, propyl formate, butyl formate), aliphatic hydrocarbons (eg, hexane, cyclohexane), halogenated hydrocarbons (eg, methylene chloride, chloroform, carbon tetrachloride), aromatic Group hydrocarbon (eg, benzene, toluene, xylene), amide (eg, dimethylformamide, dimethylacetamide, n-methylpyrrolidone), ether (eg, diethyl ether, dioxane, tetrahydrofuran), ether alcohol (eg, 1-methoxy-2-propanol). Of these, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and butanol are particularly preferable.

  The metal oxide particles can be dispersed in the medium using a disperser. Examples of the disperser include a sand grinder mill (eg, a bead mill with pins), a high-speed impeller mill, a pebble mill, a roller mill, an attritor, and a colloid mill. 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.

  The high refractive index layer and the medium refractive index layer according to the present invention preferably use a polymer having a crosslinked structure (hereinafter also referred to as a crosslinked polymer) as a binder polymer. Examples of the crosslinked polymer include polymers having a saturated hydrocarbon chain such as polyolefin (hereinafter collectively referred to as polyolefin), and crosslinked products such as polyether, polyurea, polyurethane, polyester, polyamine, polyamide, and melamine resin. Among them, a crosslinked product of polyolefin, polyether and polyurethane is preferred, a crosslinked product of polyolefin and polyether is more preferred, and a crosslinked product of polyolefin is most preferred. Further, it is further preferable that the crosslinked polymer has an anionic group. The anionic group has a function of maintaining the dispersion state of the inorganic fine particles, and the crosslinked structure has a function of imparting a film forming ability to the polymer and strengthening the film. The anionic group may be directly bonded to the polymer chain or may be bonded to the polymer chain via a linking group, but is bonded to the main chain as a side chain via the linking group. Is preferred.

  Examples of the anionic group include a carboxylic acid group (carboxyl), a sulfonic acid group (sulfo), and a phosphoric acid group (phosphono). Of these, sulfonic acid groups and phosphoric acid groups are preferred. Here, 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 chain is preferably a divalent group selected from —CO—, —O—, an alkylene group, an arylene group, and combinations thereof. The crosslinked polymer which is a preferable binder polymer is preferably a copolymer having a repeating unit having an anionic group and a repeating unit having a crosslinked structure. In this case, the ratio 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. preferable. The repeating unit may have two or more anionic groups.

  The crosslinked polymer having an anionic group may contain other repeating units (a repeating unit having neither an anionic group nor a crosslinked structure). 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 fine particles, like the anionic group. The benzene ring has a function of increasing the refractive index of the high refractive index layer. The amino group, the quaternary ammonium group, and the benzene ring can obtain the same effect even if they are contained in a repeating unit having an anionic group or a repeating unit having a crosslinked structure.

  In the crosslinked polymer containing a repeating unit having an amino group or a quaternary ammonium group as a constituent unit, the amino group or quaternary ammonium group may be directly bonded to the polymer chain, or may be a side chain via a linking group. May be bonded to the polymer chain, but the latter is more preferred. The amino group or quaternary ammonium group is preferably a secondary amino group, a tertiary amino group or a quaternary ammonium group, more preferably a tertiary amino group or a quaternary ammonium group. The group bonded to the nitrogen atom of the secondary amino group, tertiary amino group or quaternary ammonium group is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, still more preferably carbon number. 1 to 6 alkyl groups. 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 chain is a divalent group selected from —CO—, —NH—, —O—, an alkylene group, an arylene group, and combinations thereof. Is preferred. When the crosslinked polymer includes a repeating unit having an amino group or a quaternary ammonium group, the ratio is preferably 0.06 to 32% by mass, more preferably 0.08 to 30% by mass, Most preferably, it is 0.1-28 mass%.

  The cross-linked polymer is prepared by blending a monomer for generating a cross-linked polymer to prepare a coating solution for forming a high refractive index layer and a medium refractive index layer, and is generated by a polymerization reaction simultaneously with or after coating of the coating solution. Is preferred. Each layer is formed with the production of the crosslinked polymer. The monomer having an anionic group functions as a dispersant for inorganic fine particles in the coating solution. The monomer having an anionic group is preferably used in an amount of 1 to 50% by mass, more preferably 5 to 40% by mass, and still more preferably 10 to 30% by mass with respect to the inorganic fine particles. The monomer having an amino group or a quaternary ammonium group functions as a dispersion aid in the coating solution. The monomer having an amino group or a quaternary ammonium group is preferably used in an amount of 3 to 33% by mass based on the monomer having an anionic group. These monomers can be made to function effectively before application of the coating liquid by a method of forming a crosslinked polymer by a polymerization reaction simultaneously with or after application of the coating liquid.

  As the monomer used in the present invention, a monomer having two or more ethylenically unsaturated groups is most preferable, and examples thereof include esters of polyhydric alcohol and (meth) acrylic acid (eg, ethylene glycol di ( (Meth) acrylate, 1,4-dichlorohexanediacrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, dipentaerythritol Tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol hexa (meth) acrylate, 1,2,3-cyclohexanetetramethacrylate, polyurethane polyacrylate, polyester Terpolyacrylate), vinylbenzene and its derivatives (eg, 1,4-divinylbenzene, 4-vinylbenzoic acid-2-acryloylethyl ester, 1,4-divinylcyclohexanone), vinylsulfone (eg, divinylsulfone), acrylamide (E.g., methylenebisacrylamide) and methacrylamide. Commercially available monomers may be used as the monomer having an anionic group and the monomer having an amino group or a quaternary ammonium group. As a commercially available monomer having a commercially available anionic group, KAYAMAPMPM-21, PM-2 (manufactured by Nippon Kayaku Co., Ltd.), Antox MS-60, MS-2N, MS-NH4 (manufactured by Nippon Emulsifier Co., Ltd.) , Aronix M-5000, M-6000, M-8000 series (manufactured by Toagosei Chemical Industry Co., Ltd.), Biscote # 2000 series (manufactured by Osaka Organic Chemical Industry Co., Ltd.), New Frontier GX-8289 (Daiichi Kogyo Seiyaku) NK ester CB-1, A-SA (manufactured by Shin-Nakamura Chemical Co., Ltd.), AR-100, MR-100, MR-200 (manufactured by Eighth Chemical Industry Co., Ltd.), and the like. It is done. Examples of commercially available monomers having a commercially available amino group or quaternary ammonium group include DMAA (manufactured by Osaka Organic Chemical Industry Co., Ltd.), DMAEA, DMAPAA (manufactured by Kojin Co., Ltd.), and Bremer QA (Nippon Yushi Co., Ltd.). ) And New Frontier C-1615 (Daiichi Kogyo Seiyaku Co., Ltd.).

  For the polymerization reaction of the polymer, a photopolymerization reaction or a thermal polymerization reaction can be used. A photopolymerization reaction is particularly preferable. A polymerization initiator is preferably used for the polymerization reaction. For example, the thermal polymerization initiator mentioned later used in order to form the binder polymer of a hard-coat layer, and a photoinitiator are mentioned.

  A commercially available polymerization initiator may be used as the polymerization initiator. In addition to the polymerization initiator, a polymerization accelerator may be used. The addition amount of the polymerization initiator and the polymerization accelerator is preferably in the range of 0.2 to 10% by mass of the total amount of monomers. The coating liquid (dispersion of inorganic fine particles containing monomer) may be heated to promote polymerization of the monomer (or oligomer). Moreover, it may heat after the photopolymerization reaction after application | coating, and may additionally process the thermosetting reaction of the formed polymer.

  For the medium refractive index layer and the high refractive index layer, it is preferable to use a polymer having a relatively high refractive index. Examples of the polymer having a high refractive index include polystyrene, styrene copolymer, polycarbonate, melamine resin, phenol resin, epoxy resin, and polyurethane obtained by reaction of cyclic (alicyclic or aromatic) isocyanate and polyol. . Polymers having other cyclic (aromatic, heterocyclic, alicyclic) groups and polymers having halogen atoms other than fluorine as substituents can also be used with a high refractive index.

(Low refractive index layer)
Examples of the low refractive index layer include a low refractive index layer formed by crosslinking a fluorine-containing resin that is crosslinked by heat or ionizing radiation (hereinafter also referred to as “fluorinated resin before crosslinking”), a low refractive index layer by a sol-gel method, or fine particles. And a binder polymer, and a low refractive index layer or the like having voids between or inside the fine particles is used. The low refractive index layer according to the present invention may be a low refractive index layer mainly using fine particles and a binder polymer. preferable. In particular, a low refractive index layer having voids inside the particles (also referred to as hollow fine particles) is preferable because the refractive index can be further lowered. However, if the refractive index of the low refractive index layer is low, it is preferable because the antireflection performance is improved, but it is difficult from the viewpoint of imparting strength to the low refractive index layer. From this balance, the refractive index of the low refractive index layer is preferably 1.30 to 1.50, more preferably 1.35 to 1.49.

  Moreover, you may use combining the preparation method of the said low-refractive-index layer suitably.

  Preferred examples of the fluorine-containing resin before crosslinking include a fluorine-containing copolymer formed from a fluorine-containing vinyl monomer and a monomer for imparting a crosslinkable group. Specific examples of the fluorine-containing vinyl monomer unit include, for example, fluoroolefins (for example, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoroethylene, hexafluoropropylene, perfluoro-2,2-dimethyl-1,3 -Dioxoles, etc.), (meth) acrylic acid partial or fully fluorinated alkyl ester derivatives (for example, Biscoat 6FM (produced by Osaka Organic Chemicals) or M-2020 (produced by Daikin)), fully or partially fluorinated vinyl ethers, etc. Is mentioned. As monomers for imparting a crosslinkable group, glycidyl methacrylate, vinyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, vinyl glycidyl ether, and other vinyl monomers having a crosslinkable functional group in advance in the molecule. , Vinyl monomers having a carboxyl group, hydroxyl group, amino group, sulfonic acid group, etc. (for example, (meth) acrylic acid, methylol (meth) acrylate, hydroxyalkyl (meth) acrylate, allyl acrylate, hydroxyalkyl vinyl ether, hydroxyalkyl allyl) Ether, etc.). The latter can introduce a crosslinked structure after copolymerization by adding a compound that reacts with a functional group in the polymer and one or more reactive groups. No. 147739. Examples of the crosslinkable group include acryloyl, methacryloyl, isocyanate, epoxy, aziridine, oxazoline, aldehyde, carbonyl, hydrazine, carboxyl, methylol, and active methylene group. When the fluorine-containing copolymer is cross-linked by heating by a cross-linking group that reacts by heating, or a combination of an ethylenically unsaturated group and a thermal radical generator or an epoxy group and a thermal acid generator, the thermosetting type In the case of crosslinking by irradiation with light (preferably ultraviolet rays, electron beams, etc.) by a combination of an ethylenically unsaturated group and a photo radical generator, or an epoxy group and a photo acid generator, etc., it is an ionizing radiation curable type .

  Further, in addition to the above monomers, a fluorine-containing copolymer formed by using a monomer other than the fluorine-containing vinyl monomer and the monomer for imparting a crosslinkable group may be used as the fluorine-containing resin before crosslinking. The monomer 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, 2-acrylic acid 2- Ethyl hexyl), methacrylates (methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate, etc.), styrene derivatives (styrene, divinylbenzene, vinyl toluene, α-methylstyrene, etc.), vinyl ethers (methyl vinyl ether) Etc.), vinyl esters (vinyl acetate, vinyl propionate, vinyl cinnamate, etc.), acrylamides (N-tertbutylacrylamide, N-cyclohexylacrylamide, etc.), methacrylamides, Ronitoriru derivatives and the like can be mentioned. In addition, it is also preferable to introduce a polyorganosiloxane skeleton or a perfluoropolyether skeleton into the fluorinated copolymer in order to impart slipperiness and antifouling properties. For example, polyorganosiloxane or perfluoropolyether having an acrylic group, methacrylic group, vinyl ether group, styryl group or the like at the terminal is polymerized with the above monomer, and polyorganosiloxane or perfluoropolyester having a radical generating group at the terminal. It can be obtained by polymerization of the above monomers with ether, reaction of a polyorganosiloxane or perfluoropolyether having a functional group with a fluorine-containing copolymer, or the like.

  The proportion of each of the above monomers used to form the fluorinated copolymer before crosslinking is preferably 20 to 70 mol%, more preferably 40 to 70 mol%, more preferably 40 to 70 mol% of the fluorinated vinyl monomer. The amount of the monomer is preferably 1 to 20 mol%, more preferably 5 to 20 mol%, and the other monomer used in combination is preferably 10 to 70 mol%, more preferably 10 to 50 mol%.

  The fluorine-containing copolymer can be obtained by polymerizing these monomers in the presence of a radical polymerization initiator by means such as solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization.

  The fluorine-containing resin before crosslinking is commercially available and can be used. Examples of commercially available fluorine-containing resins before cross-linking include Cytop (Asahi Glass), Teflon (R) AF (DuPont), polyvinylidene fluoride, Lumiflon (Asahi Glass), Opstar (JSR) and the like. It is done.

  The low refractive index layer containing a cross-linked fluororesin as a constituent component preferably has a dynamic friction coefficient in the range of 0.03 to 0.15 and a contact angle with water in the range of 90 to 120 degrees.

  It is preferable from the viewpoint of refractive index adjustment that the low refractive index layer containing a crosslinked fluorine-containing resin as a constituent component contains inorganic particles described later. The inorganic fine particles are preferably used after being subjected to a surface treatment. The surface treatment method includes physical surface treatment such as plasma discharge treatment and corona discharge treatment and chemical surface treatment using a coupling agent, but the use of a coupling agent is preferred. As the coupling agent, an organoalkoxy metal compound (eg, titanium coupling agent, silane coupling agent, etc.) is preferably used. When the inorganic fine particles are silica, treatment with a silane coupling agent is particularly effective.

  Various sol-gel materials can also be used as the material for the low refractive index layer. As such a sol-gel material, metal alcoholates (alcohols such as silane, titanium, aluminum, and zirconium), organoalkoxy metal compounds, and hydrolysates thereof can be used. In particular, alkoxysilane, organoalkoxysilane and its hydrolyzate are preferable. Examples of these include tetraalkoxysilane (tetramethoxysilane, tetraethoxysilane, etc.), alkyltrialkoxysilane (methyltrimethoxysilane, ethyltrimethoxysilane, etc.), aryltrialkoxysilane (phenyltrimethoxysilane, etc.), dialkyl. Examples thereof include dialkoxysilane and diaryl dialkoxysilane. In addition, organoalkoxysilanes having various functional groups (vinyl trialkoxysilane, methylvinyl dialkoxysilane, γ-glycidyloxypropyltrialkoxysilane, γ-glycidyloxypropylmethyl dialkoxysilane, β- (3,4-epoxy) Dicyclohexyl) ethyltrialkoxysilane, γ-methacryloyloxypropyltrialkoxysilane, γ-aminopropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, γ-chloropropyltrialkoxysilane, etc.), perfluoroalkyl group-containing silane compounds ( For example, it is also preferable to use (heptadecafluoro-1,1,2,2-tetradecyl) triethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, etc.). In particular, the use of a fluorine-containing silane compound is preferable in terms of lowering the refractive index of the layer and imparting water and oil repellency.

  As the low refractive index layer, it is also preferable to use a layer formed using inorganic or organic fine particles and forming microvoids between or within the fine particles. The average particle diameter of the fine particles is preferably 0.5 to 200 nm, more preferably 1 to 100 nm, still more preferably 3 to 70 nm, and most preferably in the range of 5 to 40 nm. The particle diameter of the fine particles is preferably as uniform (monodispersed) as possible.

The inorganic fine particles are preferably amorphous. The inorganic fine particles are preferably made of a metal oxide, nitride, sulfide or halide, more preferably a metal oxide or a metal halide, and most preferably a metal oxide or a metal fluoride. . As metal atoms, Na, K, Mg, Ca, Ba, Al, Zn, Fe, Cu, Ti, Sn, In, W, Y, Sb, Mn, Ga, V, Nb, Ta, Ag, Si, B Bi, Mo, Ce, Cd, Be, Pb and Ni are preferable, and Mg, Ca, B and Si are more preferable. An inorganic compound containing two kinds of metals may be used. Specific examples of preferred inorganic compounds are SiO ₂ and MgF ₂ , and particularly preferred is SiO ₂ .

Particles having microvoids in the inorganic fine particles can be formed, for example, by crosslinking silica molecules forming the particles. Crosslinking silica molecules reduces the volume and makes the particles porous. (Porous) inorganic fine particles having microvoids are prepared by a sol-gel method (described in JP-A-53-112732 and JP-B-57-9051) or a precipitation method (described in APPLIED OPTICS, 27, 3356 (1988)). Can be directly synthesized as a dispersion. Further, the powder obtained by the drying / precipitation method can be mechanically pulverized to obtain a dispersion. Commercially available porous inorganic fine particles (for example, SiO ₂ sol) may be used.

  These inorganic fine particles are preferably used in a state of being dispersed in an appropriate medium in order to form a low refractive index layer. As the dispersion medium, water, alcohol (for example, methanol, ethanol, isopropyl alcohol) and ketone (for example, methyl ethyl ketone, methyl isobutyl ketone) are preferable.

  The organic fine particles are also preferably amorphous. The organic fine particles are preferably polymer fine particles synthesized by polymerization reaction of monomers (for example, emulsion polymerization method). The organic fine particle polymer preferably contains a fluorine atom. The proportion of fluorine atoms in the polymer is preferably 35 to 80% by mass, and more preferably 45 to 75% by mass. It is also preferable to form microvoids in the organic fine particles by, for example, cross-linking the polymer forming the particles and reducing the volume. In order to crosslink the polymer forming the particles, it is preferable to use 20 mol% or more of the monomer for synthesizing the polymer as a polyfunctional monomer. The ratio of the polyfunctional monomer is more preferably 30 to 80 mol%, and most preferably 35 to 50 mol%. Examples of the monomer used for the synthesis of the organic fine particles include fluoroolefins (for example, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene) as examples of monomers containing fluorine atoms used to synthesize fluorine-containing polymers. , Perfluoro-2,2-dimethyl-1,3-dioxole), fluorinated alkyl esters of acrylic acid or methacrylic acid, and fluorinated vinyl ethers. A copolymer of a monomer containing a fluorine atom and a monomer not containing a fluorine atom may be used. Examples of monomers that do not contain fluorine atoms include olefins (eg, ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride), acrylic esters (eg, methyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate). , Methacrylates (eg, methyl methacrylate, ethyl methacrylate, butyl methacrylate), styrenes (eg, styrene, vinyl toluene, α-methyl styrene), vinyl ethers (eg, methyl vinyl ether), vinyl esters ( Examples thereof include vinyl acetate and vinyl propionate), acrylamides (for example, N-tert-butylacrylamide, N-cyclohexylacrylamide), methacrylamides and acrylonitriles. Examples of polyfunctional monomers include dienes (eg, butadiene, pentadiene), esters of polyhydric alcohols and acrylic acid (eg, ethylene glycol diacrylate, 1,4-cyclohexane diacrylate, dipentaerythritol hexaacrylate), Esters of polyhydric alcohol and methacrylic acid (for example, ethylene glycol dimethacrylate, 1,2,4-cyclohexanetetramethacrylate, pentaerythritol tetramethacrylate), divinyl compounds (for example, divinylcyclohexane, 1,4-divinylbenzene), divinyl Examples include sulfones, bisacrylamides (eg, methylenebisacrylamide) and bismethacrylamides.

  Microvoids between particles can be formed by stacking at least two fine particles. When spherical fine particles having the same particle diameter (completely monodispersed) are closely packed, microvoids between fine particles having a porosity of 26% by volume are formed. When spherical fine particles having the same particle diameter are simply filled with cubic particles, microvoids between fine particles having a porosity of 48% by volume are formed. In an actual low-refractive index layer, the particle size distribution of fine particles and intra-particle microvoids exist, so the porosity varies considerably from the above theoretical value. When the porosity is increased, the refractive index of the low refractive index layer is lowered. When microvoids are formed by stacking fine particles, the size of the microvoids can be adjusted to an appropriate value (does not scatter light and cause no problem with the strength of the low refractive index layer) by adjusting the particle size of the fine particles. You can adjust. Furthermore, by making the particle diameters of the fine particles uniform, it is possible to obtain an optically uniform low refractive index layer in which the size of microvoids between particles is uniform. As a result, the low refractive index layer is microscopically a microvoided porous film, but can be made optically or macroscopically uniform. The interparticle microvoids are preferably closed in the low refractive index layer by fine particles and a polymer. The closed air gap also has an advantage that light scattering on the surface of the low refractive index layer is less than that of an opening opened on the surface of the low refractive index layer.

  By forming the microvoids, the macroscopic refractive index of the low refractive index layer becomes lower than the sum of the refractive indexes of the components constituting the low refractive index layer. The refractive index of the layer is the sum of the refractive indices per volume of the layer components. The refractive index of the constituent component of the low refractive index layer such as fine particles or polymer is larger than 1, whereas the refractive index of air is 1.00. Therefore, a low refractive index layer having a very low refractive index can be obtained by forming microvoids.

In the present invention, it is also a preferred embodiment to use SiO ₂ hollow fine particles.

The hollow fine particles referred to in the present invention are particles having a particle wall and a hollow inside. For example, SiO ₂ particles having microvoids inside the fine particles described above are further converted to organosilicon compounds (alkoxy such as tetraethoxysilane). These are particles formed by covering the surface with silanes and closing the pore entrance. Alternatively, the cavity inside the particle wall may be filled with a solvent or gas. For example, in the case of air, the refractive index of the hollow fine particles should be significantly lower than that of ordinary silica (refractive index = 1.46). (Refractive index = 1.44 to 1.34). By adding such hollow SiO ₂ fine particles, the refractive index of the low refractive index layer can be further reduced.

The method for preparing particles having microvoids in the inorganic fine particles may be in accordance with the methods described in JP-A Nos. 2001-167737 and 2001-233611. In the present invention, commercially available hollow SiO _Two fine particles can be used. Specific examples of commercially available particles include P-4 manufactured by Catalytic Chemical Industry Co., Ltd.

  The low refractive index layer preferably contains the polymer in an amount of 5 to 50% by mass. The polymer has a function of adhering fine particles and maintaining the structure of a low refractive index layer including voids. The amount of the polymer used is adjusted so that the strength of the low refractive index layer can be maintained without filling the voids. The amount of the polymer is preferably 10 to 30% by mass of the total amount of the low refractive index layer. In order to adhere the fine particles with the polymer, (1) the polymer is bonded to the surface treatment agent of the fine particles, (2) the fine particles are used as a core, and a polymer shell is formed around the fine particles. It is preferable to use a polymer as the binder. The polymer to be bonded to the surface treatment agent (1) is preferably the shell polymer (2) or the binder polymer (3). The polymer (2) is preferably formed around the fine particles by a polymerization reaction before preparing the coating solution for the low refractive index layer. The polymer (3) is preferably formed by adding a monomer to the coating solution for the low refractive index layer and performing a polymerization reaction simultaneously with or after the coating of the low refractive index layer. It is preferable to carry out a combination of two or all of the above (1) to (3), and to carry out a combination of (1) and (3) or (1) to (3) all of the combinations. Particularly preferred. (1) Surface treatment, (2) shell, and (3) binder will be described sequentially.

(1) Surface treatment It is preferable that the fine particles (particularly inorganic fine particles) are subjected to a surface treatment to improve the affinity with the polymer. The surface treatment can be classified into physical surface treatment such as plasma discharge treatment and corona discharge treatment, and chemical surface treatment using a coupling agent. It is preferable to carry out only chemical surface treatment or a combination of physical surface treatment and chemical surface treatment. As the coupling agent, an organoalkoxy metal compound (eg, titanium coupling agent, silane coupling agent) is preferably used. Particles when made of SiO _2, surface treatment with a silane coupling agent can be particularly effectively conducted. As a specific example of the silane coupling agent, the above-described silane coupling agent is preferably used.

  The surface treatment with the coupling agent can be carried out by adding the coupling agent to the fine particle dispersion and allowing the dispersion to stand at a temperature from room temperature to 60 ° C. for several hours to 10 days. In order to accelerate the surface treatment reaction, inorganic acids (for example, sulfuric acid, hydrochloric acid, nitric acid, chromic acid, hypochlorous acid, boric acid, orthosilicic acid, phosphoric acid, carbonic acid), organic acids (for example, acetic acid, polyacrylic acid, Benzenesulfonic acid, phenol, polyglutamic acid), or salts thereof (eg, metal salts, ammonium salts) may be added to the dispersion.

(2) Shell The polymer forming the shell is preferably a polymer having a saturated hydrocarbon as the main chain. A polymer containing a fluorine atom in the main chain or side chain is preferred, and a polymer containing a fluorine atom in the side chain is more preferred. Polyacrylic acid esters or polymethacrylic acid esters are preferred, and esters of fluorine-substituted alcohols with polyacrylic acid or polymethacrylic acid are most preferred. The refractive index of the shell polymer decreases as the content of fluorine atoms in the polymer increases. In order to lower the refractive index of the low refractive index layer, the shell polymer preferably contains 35 to 80% by mass of fluorine atoms, and more preferably contains 45 to 75% by mass of fluorine atoms. The polymer containing a fluorine atom is preferably synthesized by a polymerization reaction of an ethylenically unsaturated monomer containing a fluorine atom. Examples of ethylenically unsaturated monomers containing fluorine atoms include fluoroolefins (eg, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, perfluoro-2,2-dimethyl-1,3-dioxole), Mention may be made of esters of fluorinated vinyl ethers and fluorine-substituted alcohols with acrylic acid or methacrylic acid.

  The polymer forming the shell may be a copolymer composed of a repeating unit containing a fluorine atom and a repeating unit not containing a fluorine atom. The repeating unit containing no fluorine atom is preferably obtained by a polymerization reaction of an ethylenically unsaturated monomer containing no fluorine atom. Examples of ethylenically unsaturated monomers that do not contain fluorine atoms include olefins (eg, ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride), acrylic acid esters (eg, methyl acrylate, ethyl acrylate, acrylic acid 2- Ethyl hexyl), methacrylic acid esters (for example, methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate), styrene and its derivatives (for example, styrene, divinylbenzene, vinyltoluene, α-methylstyrene), vinyl ether ( For example, methyl vinyl ether), vinyl esters (for example, vinyl acetate, vinyl propionate, vinyl cinnamate), acrylamide (for example, N-tertbutylacrylamide, N-cyclohexylacrylic) Amides), methacrylamide and acrylonitrile.

  When the binder polymer (3) described later is used in combination, a crosslinkable functional group may be introduced into the shell polymer to chemically bond the shell polymer and the binder polymer by crosslinking. The shell polymer may have crystallinity. When the glass transition temperature (Tg) of the shell polymer is higher than the temperature at the time of forming the low refractive index layer, it is easy to maintain microvoids in the low refractive index layer. However, if Tg is higher than the temperature at which the low refractive index layer is formed, the fine particles are not fused, and the low refractive index layer may not be formed as a continuous layer (resulting in a decrease in strength). In that case, it is desirable to use a binder polymer (3) described later in combination, and form the low refractive index layer as a continuous layer with the binder polymer. By forming a polymer shell around the fine particles, core-shell fine particles are obtained. The core-shell fine particles preferably contain 5 to 90% by volume of a core composed of inorganic fine particles, and more preferably 15 to 80% by volume. Two or more kinds of core-shell fine particles may be used in combination. Further, inorganic fine particles having no shell and core-shell particles may be used in combination.

(3) Binder The binder polymer is preferably a polymer having a saturated hydrocarbon or polyether as the main chain, and more preferably a polymer having a saturated hydrocarbon as the main chain. The binder polymer is preferably crosslinked. The polymer having a saturated hydrocarbon as the main chain is preferably obtained by a polymerization reaction of an ethylenically unsaturated monomer. In order to obtain a crosslinked binder polymer, it is preferable to use a monomer having two or more ethylenically unsaturated groups. Examples of monomers having two or more ethylenically unsaturated groups include esters of polyhydric alcohols and (meth) acrylic acid (for example, ethylene glycol di (meth) acrylate, 1,4-dichlorohexane diacrylate, pentaerythritol). Tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Pentaerythritol hexa (meth) acrylate, 1,2,3-cyclohexanetetramethacrylate, polyurethane polyacrylate, polyester polyacrylate), vinylbenzene and its derivatives For example, 1,4-divinylbenzene, 4-vinylbenzoic acid-2-acryloyl ethyl ester, 1,4-divinylcyclohexanone), vinyl sulfone (eg, divinyl sulfone), acrylamide (eg, methylene bisacrylamide) and methacrylamide Can be mentioned. The polymer having a polyether as the main chain is preferably synthesized by a ring-opening polymerization reaction of a polyfunctional epoxy compound. Instead of or in addition to the monomer having two or more ethylenically unsaturated groups, a crosslinked structure may be introduced into the binder polymer by the reaction of a crosslinkable group. Examples of crosslinkable functional groups include isocyanate groups, epoxy groups, aziridine groups, oxazoline groups, aldehyde groups, carbonyl groups, hydrazine groups, carboxyl groups, methylol groups, and active methylene groups. Vinylsulfonic acid, acid anhydride, cyanoacrylate derivative, melamine, etherified methylol, ester and urethane can also be used as a monomer for introducing a crosslinked structure. A functional group that exhibits crosslinkability as a result of the decomposition reaction, such as a block isocyanate group, may be used. The cross-linking group is not limited to the above compound, and may be one that exhibits reactivity as a result of decomposition of the functional group. As the polymerization initiator used for the polymerization reaction and the crosslinking reaction of the binder polymer, a thermal polymerization initiator or a photopolymerization initiator is used, and the photopolymerization initiator is more preferable. Examples of photopolymerization initiators include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkyldione compounds, disulfide compounds , Fluoroamine compounds and aromatic sulfoniums. Examples of acetophenones include 2,2-diethoxyacetophenone, p-dimethylacetophenone, 1-hydroxydimethylphenyl ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-4-methylthio-2-morpholinopropiophenone and 2 -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone. Examples of benzoins include benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether. Examples of benzophenones include benzophenone, 2,4-dichlorobenzophenone, 4,4-dichlorobenzophenone and p-chlorobenzophenone. Examples of phosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

  The binder polymer is preferably formed by adding a monomer to the coating solution for the low refractive index layer, and at the same time as or after the coating of the low refractive index layer, by a polymerization reaction (further crosslinking reaction if necessary). Even if a small amount of polymer (for example, polyvinyl alcohol, polyoxyethylene, polymethyl methacrylate, polymethyl acrylate, diacetyl cellulose, triacetyl cellulose, nitrocellulose, polyester, alkyd resin) is added to the coating solution for the low refractive index layer Good.

  Moreover, it is preferable to add a slipping agent to the low refractive index layer or other refractive index layers of the present invention, and scratch resistance can be improved by imparting slipperiness. As the slip agent, silicon oil or a wax-like substance is preferably used. For example, a compound represented by the following general formula is preferable.

General formula R ₁ COR ₂
In the formula, R ₁ represents a saturated or unsaturated aliphatic hydrocarbon group having 12 or more carbon atoms. An alkyl group or an alkenyl group is preferable, and an alkyl group or alkenyl group having 16 or more carbon atoms is more preferable. R ₂ represents —OM ₁ group (M ₁ represents an alkali metal such as Na or K), —OH group, —NH ₂ group, or —OR ₃ group (R ₃ represents a saturated or unsaturated group having 12 or more carbon atoms. R ₂ represents a saturated aliphatic hydrocarbon group, preferably an alkyl group or an alkenyl group, and R ₂ is preferably an —OH group, —NH ₂ group, or —OR ₃ group. Specifically, higher fatty acids such as behenic acid, stearamide, and pentacoic acid, or derivatives thereof, and carnauba wax, beeswax, and montan wax containing many of these components as natural products can also be preferably used. Polyorganosiloxane as disclosed in JP-B-53-292, higher fatty acid amide as disclosed in US Pat. No. 4,275,146, JP-B 58-33541, British patent No. 927,446 or JP-A-55-126238 and 58-90633, higher fatty acid esters (fatty acids having 10 to 24 carbon atoms and 10 to 24 carbon atoms). Esters of alcohols), and higher fatty acid metal salts as disclosed in U.S. Pat. No. 3,933,516, dicarboxylic acids having up to 10 carbon atoms as disclosed in JP-A-51-37217 A polyester compound comprising an acid and an aliphatic or cycloaliphatic diol, a dicarboxylic acid disclosed in JP-A-7-13292, It can be mentioned oligo polyester or the like from the Le.

For example, the amount of slip agent to be used in the low refractive index layer is preferably ^{0.01mg / m 2 ~10mg / m 2} .

  In addition to the above-described components (metal oxide particles, polymer, dispersion medium, polymerization initiator, polymerization accelerator), each layer of the antireflection laminate or coating liquid thereof is a polymerization inhibitor, leveling agent, thickener, coloring. An inhibitor, an ultraviolet absorber, a silane coupling agent, an antistatic agent or an adhesion promoter may be added.

  Each layer of the antireflection laminate is formed by coating by a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, a gravure coating method or an extrusion coating method (US Pat. No. 2,681,294). I can do it. Two or more layers may be applied simultaneously. For the method of simultaneous application, US Pat. Nos. 2,761,791, 2,941,898, 3,508,947, 3,526,528 and Yuji Harasaki, Coating Engineering, page 253, It is described in Asakura Shoten (1973).

  In the present invention, in the method for producing a low reflection laminate, when the prepared coating solution is applied to a support and then dried, it is preferably dried at 60 ° C. or higher, and may be dried at 80 ° C. or higher. Further preferred. Further, drying at a dew point of 20 ° C. or lower is preferable, and drying at 15 ° C. or lower is more preferable. Furthermore, drying is preferably started within 10 seconds after coating on the support, and combining with the above conditions is a preferable production method for obtaining the effects of the present invention.

(Transparent substrate film)
Next, the transparent substrate film that can be used in the present invention will be described.

  The transparent substrate film used in the present invention is easy to manufacture, has good adhesion to the actinic radiation curable resin layer, is optically isotropic, and is optically transparent. Etc. are mentioned as preferable requirements.

  The term “transparent” as used in the present invention means that the visible light transmittance is 60% or more, preferably 80% or more, and particularly preferably 90% or more.

  Although it will not specifically limit if it has said property, For example, a cellulose-ester type film, a polyester-type film, a polycarbonate-type film, a polyarylate-type film, a polysulfone (a polyether sulfone is also included) type film, a polyethylene terephthalate, polyethylene Polyester film such as naphthalate, polyethylene film, polypropylene film, cellophane, cellulose diacetate film, cellulose triacetate, cellulose acetate butyrate film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene vinyl alcohol film, syndiotactic polystyrene film, Polycarbonate film, cycloolefin polymer film (Arton (manufactured by JSR), Onex, Zeonea (above, ZEON Corporation), polymethylpentene film, polyetherketone film, polyetherketoneimide film, polyamide film, fluororesin film, nylon film, polymethylmethacrylate film, acrylic film, glass plate, etc. Can be mentioned. Among them, a cellulose triacetate film, a polycarbonate film, and a polysulfone (including polyethersulfone) are preferable. In the present invention, a cellulose ester film (for example, Konicattak product names KC8UX2MW, KC4UX2MW, KC8UY, KC4UY, KC5UN, KC12UR (Konica ( From the viewpoint of production, cost, transparency, isotropy, adhesiveness and the like. These films may be films produced by melt casting film formation or films produced by solution casting film formation.

The optical properties of the substrate film thickness direction retardation R _t is 0Nm～300nm, retardation R ₀ in the plane direction those 0nm~1000nm is preferably used.

  In the present invention, it is preferable to use a cellulose ester film as the substrate film. As the cellulose ester, cellulose acetate, cellulose acetate butyrate, and cellulose acetate propionate are preferable. Among them, cellulose acetate butyrate, cellulose acetate phthalate, and cellulose acetate propionate are preferably used.

  In particular, when the substitution degree of acetyl group is X and the substitution degree of propionyl group or butyryl group is Y, X and Y are active ray curable resin layers on a base film having a mixed fatty acid ester of cellulose in the following range And an antireflection laminate provided with an antireflection layer is preferably used.

2.3 ≦ X + Y ≦ 3.0
0.1 ≦ Y ≦ 1.2
In particular, 2.5 ≦ X + Y ≦ 2.85
It is preferable that 0.3 ≦ Y ≦ 1.2.

  When cellulose ester is used as the base film according to the present invention, the cellulose used as a raw material for the cellulose ester is not particularly limited, and examples thereof include cotton linter, wood pulp (derived from coniferous tree, derived from broadleaf tree), kenaf and the like. . Moreover, the cellulose ester obtained from them can be mixed and used in arbitrary ratios, respectively. When the acylating agent is an acid anhydride (acetic anhydride, propionic anhydride, butyric anhydride), these cellulose esters use an organic solvent such as acetic acid or an organic solvent such as methylene chloride, and It can be obtained by reacting with a cellulose raw material using a protic catalyst.

When the acylating agent is acid chloride (CH ₃ COCl, C ₂ H ₅ COCl, C ₃ H ₇ COCl), the reaction is carried out using a basic compound such as an amine as a catalyst. Specifically, it can be synthesized with reference to the method described in JP-A-10-45804. In addition, the cellulose ester used in the present invention is obtained by mixing and reacting the amount of the acylating agent in accordance with the degree of substitution. In the cellulose ester, these acylating agents react with hydroxyl groups of cellulose molecules. Cellulose molecules are composed of many glucose units linked together, and the glucose unit has three hydroxyl groups. The number of acyl groups derived from these three hydroxyl groups is called the degree of substitution (mol%). For example, cellulose triacetate has acetyl groups bonded to all three hydroxyl groups of the glucose unit (actually 2.6 to 3.0).

  The cellulose ester used in the present invention is a mixed fatty acid ester of cellulose in which a propionate group or a butyrate group is bonded in addition to an acetyl group such as cellulose acetate propionate, cellulose acetate butyrate, or cellulose acetate propionate butyrate. Is particularly preferably used. The butyryl group that forms butyrate may be linear or branched.

  Cellulose acetate propionate containing a propionate group as a substituent has excellent water resistance and is useful as a film for liquid crystal image display devices.

  The measuring method of the substitution degree of an acyl group can be measured according to the provisions of ASTM-D817-96.

  The number average molecular weight of the cellulose ester is preferably 70,000 to 250,000 because the mechanical strength when molded is strong and an appropriate dope viscosity is preferable, and more preferably 80,000 to 150,000.

  These cellulose esters are pressurized by applying a cellulose ester solution (dope) generally called a solution casting film forming method onto, for example, an endless metal belt for infinite transport or a support for casting of a rotating metal drum. It is preferable to manufacture the dope from a die by casting (casting).

  The organic solvent used for the preparation of these dopes is preferably capable of dissolving the cellulose ester and having an appropriate boiling point, for example, methylene chloride, methyl acetate, ethyl acetate, amyl acetate, methyl acetoacetate, acetone, tetrahydrofuran 1,3-dioxolane, 1,4-dioxane, cyclohexanone, ethyl formate, 2,2,2-trifluoroethanol, 2,2,3,3-tetrafluoro-1-propanol, 1,3-difluoro-2 -Propanol, 1,1,1,3,3,3-hexafluoro-2-methyl-2-propanol, 1,1,1,3,3,3-hexafluoro-2-propanol, 2,2,3 , 3,3-pentafluoro-1-propanol, nitroethane, 1,3-dimethyl-2-imidazolidinone, etc. It is possible, organic halogen compounds such as methylene chloride, dioxolane derivatives, methyl acetate, ethyl acetate, acetone, methyl acetoacetate, and the like are preferable organic solvents (i.e., good solvent), and as.

  Moreover, as shown in the following film forming process, it is used from the viewpoint of preventing foaming in the web when the solvent is dried from the web (dope film) formed on the casting support in the solvent evaporation process. The boiling point of the organic solvent is preferably 30 to 80 ° C. For example, the good solvent described above has a boiling point of methylene chloride (boiling point 40.4 ° C), methyl acetate (boiling point 56.32 ° C), acetone (boiling point 56.56 ° C). 3 ° C.), ethyl acetate (boiling point 76.82 ° C.) and the like.

  Among the good solvents described above, methylene chloride or methyl acetate, which is excellent in solubility, is preferably used.

  It is preferable to contain 0.1 mass%-40 mass% of C1-C4 alcohol other than the said organic solvent. It is particularly preferable that the alcohol is contained at 5 to 30% by mass. After casting the dope described above onto a casting support, the solvent starts to evaporate and the alcohol ratio increases and the web (dope film) gels, making the web strong and peeling from the casting support. It is also used as a gelling solvent for facilitating the dissolution, and when these ratios are small, it also has a role of promoting the dissolution of the cellulose ester of the non-chlorine organic solvent.

  Examples of the alcohol having 1 to 4 carbon atoms include methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol, tert-butanol and the like.

  Of these solvents, ethanol is preferred because it has good dope stability, relatively low boiling point, good drying properties, and no toxicity. It is preferable to use a solvent containing 5% by mass to 30% by mass of ethanol with respect to 70% by mass to 95% by mass of methylene chloride. Methyl acetate can be used in place of methylene chloride. At this time, the dope may be prepared by a cooling dissolution method.

  The cellulose ester film used in the present invention is preferably at least stretched in the width direction, and is 1.01 times to the width direction when the residual solvent amount is 3% by mass to 40% by mass in the solution casting process. The film is preferably stretched 1.5 times. More preferably, biaxial stretching is performed in the width direction and the longitudinal direction, and when the residual solvent is 3% by mass to 40% by mass, the width direction and the longitudinal direction are 1.01 times to 1.5 times, respectively. It is desirable to be stretched. By doing in this way, the light diffusable film excellent in planarity and light diffusibility can be obtained.

  The residual solvent amount is represented by the following formula.

Residual solvent amount (% by mass) = {(MN) / N} × 100
Here, M is the mass of the web (cellulose ester film containing the solvent) at an arbitrary point in time, and N is the mass when the web of M is dried at 110 ° C. for 3 hours.

  Furthermore, by carrying out biaxial stretching and performing the knurling described above, it is possible to remarkably improve the deterioration of the winding shape during storage of the long optical film in the form of a roll.

  In the present invention, the biaxially stretched cellulose ester film is preferably a transparent support having a light transmittance of 90% or more, more preferably 93% or more.

The cellulose ester film support according to the present invention preferably has a thickness of 10 μm to 100 μm, more preferably 40 μm to 80 μm, and moisture permeability conforms to JIS Z 0208 (25 ° C., 90% RH). The measured value is preferably 200 g / m ² · 24 hours or less, more preferably 10 to 180 g / m ² · 24 hours or less, and particularly preferably 160 g / m ² · 24 hours or less. . In particular, it is preferable that the film thickness is 10 μm to 80 μm and the moisture permeability is within the above range.

  In the present invention, it is preferable to use a long film, and specifically, a film having a length of about 100 m to 5000 m is shown, which is usually provided in a roll shape. Moreover, it is preferable that the width | variety of a base film is 1.3-4 m.

  When a cellulose ester film is used for the antireflection laminate of the present invention, it is preferable to contain the following plasticizer. Examples of plasticizers include phosphate ester plasticizers, phthalate ester plasticizers, trimellitic acid ester plasticizers, pyromellitic acid plasticizers, glycolate plasticizers, citrate ester plasticizers, and polyesters. A plasticizer or the like can be preferably used.

  For phosphate plasticizers, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, diphenylbiphenyl phosphate, trioctyl phosphate, tributyl phosphate, etc. For phthalate ester plasticizers, diethyl phthalate, dimethoxy For trimellitic acid plasticizers such as ethyl phthalate, dimethyl phthalate, dioctyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, butyl benzyl phthalate, diphenyl phthalate, dicyclohexyl phthalate, tributyl trimellitate, triphenyl trimellitate, triethyl For pyromellitic acid ester plasticizers such as trimellitate, tetrabutylpyromellitate, In the case of glycolate plasticizers such as lupyromelitate and tetraethylpyromellitate, triacetin, tributyrin, ethylphthalylethyl glycolate, methylphthalylethyl glycolate, butylphthalylbutyl glycolate, etc. Citrate, tri-n-butyl citrate, acetyl triethyl citrate, acetyl tri-n-butyl citrate, acetyl tri-n- (2-ethylhexyl) citrate and the like can be preferably used. Examples of other carboxylic acid esters include trimethylolpropane tribenzoate, butyl oleate, methylacetyl ricinoleate, dibutyl sebacate, and various trimellitic acid esters.

  As the polyester plasticizer, a copolymer of a dibasic acid such as an aliphatic dibasic acid, an alicyclic dibasic acid, or an aromatic dibasic acid and a glycol can be used. The aliphatic dibasic acid is not particularly limited, and adipic acid, sebacic acid, phthalic acid, terephthalic acid, 1,4-cyclohexyl dicarboxylic acid and the like can be used. As the glycol, ethylene glycol, diethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,4-butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol and the like can be used. These dibasic acids and glycols may be used alone or in combination of two or more.

  The amount of these plasticizers used is preferably 1% by mass to 20% by mass and particularly preferably 3% by mass to 13% by mass with respect to the cellulose ester in terms of film performance, processability and the like.

  An ultraviolet absorbent is preferably used for the long film for the antireflection laminate of the present invention.

  As the ultraviolet absorber, those excellent in the ability to absorb ultraviolet rays having a wavelength of 370 nm or less and having little absorption of visible light having a wavelength of 400 nm or more are preferably used from the viewpoint of good liquid crystal display properties.

  Specific examples of the ultraviolet absorber preferably used in the present invention include oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, nickel complex compounds, and the like. However, it is not limited to these.

  Specific examples of the benzotriazole-based ultraviolet absorbers include the following ultraviolet absorbers, but the present invention is not limited thereto.

UV-1: 2- (2'-hydroxy-5'-methylphenyl) benzotriazole UV-2: 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole UV-3 : 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) benzotriazole UV-4: 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl)- 5-Chlorobenzotriazole UV-5: 2- (2'-hydroxy-3 '-(3 ", 4", 5 ", 6" -tetrahydrophthalimidomethyl) -5'-methylphenyl) benzotriazole UV-6: 2,2-methylenebis (4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol)
UV-7: 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole UV-8: 2- (2H-benzotriazol-2-yl) -6 (Linear and side chain dodecyl) -4-methylphenol (TINUVIN171, manufactured by Ciba)
UV-9: Octyl-3- [3-tert-butyl-4-hydroxy-5- (chloro-2H-benzotriazol-2-yl) phenyl] propionate and 2-ethylhexyl-3- [3-tert-butyl- 4-Hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl] propionate (TINUVIN109, manufactured by Ciba)
Moreover, although the following specific example is shown as a benzophenone series ultraviolet absorber, this invention is not limited to these.

UV-10: 2,4-dihydroxybenzophenone UV-11: 2,2'-dihydroxy-4-methoxybenzophenone UV-12: 2-hydroxy-4-methoxy-5-sulfobenzophenone UV-13: Bis (2-methoxy -4-hydroxy-5-benzoylphenylmethane)
As the ultraviolet absorber preferably used in the present invention, a benzotriazole-based ultraviolet absorber and a benzophenone-based ultraviolet absorber that are highly transparent and excellent in preventing the deterioration of the polarizing plate and the liquid crystal are preferable, and unnecessary coloring is less. A benzotriazole-based ultraviolet absorber is particularly preferably used.

  Moreover, the ultraviolet absorber whose distribution coefficient described in Unexamined-Japanese-Patent No. 2001-187825 is 9.2 or more improves the surface quality of a long film, and is excellent also in applicability | paintability. In particular, it is preferable to use an ultraviolet absorber having a distribution coefficient of 10.1 or more.

  Further, the polymer ultraviolet absorbers described in the general formula (1) or general formula (2) described in JP-A-6-148430 and the general formulas (3), (6), and (7) of Japanese Patent Application No. 2000-156039 ( Alternatively, an ultraviolet absorbing polymer) is also preferably used. As a polymer ultraviolet absorber, PUVA-30M (manufactured by Otsuka Chemical Co., Ltd.) and the like are commercially available.

  Moreover, in order to provide slipperiness to the cellulose-ester film used for this invention, the microparticles | fine-particles similar to what is described with the coating layer containing the below-mentioned actinic radiation curable resin can be used.

  The primary average particle diameter of the fine particles added to the cellulose ester film used in the present invention is preferably 20 nm or less, more preferably 5 to 16 nm, and particularly preferably 5 to 12 nm. These fine particles preferably form secondary particles having a particle diameter of 0.1 to 5 μm and are contained in the cellulose ester film, and the preferable average particle diameter is 0.1 to 2 μm, more preferably 0.2 to 0.6 μm. Thereby, the unevenness | corrugation about 0.1-1.0 micrometer high can be formed in the film surface, and, thereby, appropriate slipperiness can be given to the film surface.

  The primary average particle diameter of the fine particles used in the present invention is measured by observing particles with a transmission electron microscope (magnification 500,000 to 2,000,000 times), observing 100 particles, and using the average value, the primary value is measured. The average particle size was taken.

  The apparent specific gravity of the fine particles is preferably 70 g / liter or more, more preferably 90 to 200 g / liter, and particularly preferably 100 to 200 g / liter. A larger apparent specific gravity makes it possible to make a high-concentration dispersion, which improves haze and agglomerates, and is preferable when preparing a dope having a high solid content concentration as in the present invention. Are particularly preferably used.

SiO ₂ fine particles having an average primary particle diameter of 20 nm or less and an apparent specific gravity of 70 g / liter or more are, for example, a mixture of vaporized silicon tetrachloride and hydrogen burned in air at 1000 to 1200 ° C. Can be obtained. For example, it is marketed by the brand name of Aerosil 200V and Aerosil R972V (above, Nippon Aerosil Co., Ltd. product), and can use them.

The apparent specific gravity described above is calculated by the following formula by measuring a weight of SiO ₂ fine particles in a graduated cylinder and measuring the weight at that time.

Apparent specific gravity (g / liter) = SiO ₂ mass (g) / SiO ₂ volume (liter)
Examples of the method for preparing the fine particle dispersion used in the present invention include the following three types.

<< Preparation Method A >>
After stirring and mixing the solvent and fine particles, dispersion is performed with a disperser. This is a fine particle dispersion. The fine particle dispersion is added to the dope solution and stirred.

<< Preparation Method B >>
After stirring and mixing the solvent and fine particles, dispersion is performed with a disperser. This is a fine particle dispersion. Separately, a small amount of cellulose triacetate is added to the solvent and dissolved by stirring. The fine particle dispersion is added to this and stirred. This is a fine particle addition solution. The fine particle additive solution is sufficiently mixed with the dope solution using an in-line mixer.

<< Preparation Method C >>
Add a small amount of cellulose triacetate to the solvent and dissolve with stirring. Fine particles are added to this and dispersed by a disperser. This is a fine particle addition solution. The fine particle additive solution is sufficiently mixed with the dope solution using an in-line mixer.

Preparation method A is excellent in the dispersibility of SiO ₂ fine particles, and preparation method C is excellent in that the SiO ₂ fine particles are difficult to re-aggregate. Among them, the preparation method B described above is a dispersion of SiO ₂ particles, a preferred preparation method SiO ₂ particles have excellent reagglomeration hardly like, both.

《Distribution method》
The concentration of SiO ₂ when the SiO ₂ fine particles are mixed with a solvent and dispersed is preferably 5 to 30% by mass, more preferably 10 to 25% by mass, and most preferably 15 to 20% by mass. A higher dispersion concentration is preferable because liquid turbidity with respect to the added amount tends to be low, and haze and aggregates are improved.

  The solvent used is preferably lower alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol and the like. Although it does not specifically limit as solvents other than a lower alcohol, It is preferable to use the solvent used at the time of film forming of a cellulose ester.

The addition amount of SiO ₂ fine particles to the cellulose ester relative to 100 parts by weight of cellulose ester, SiO ₂ fine particles is preferably 5.0 parts by 0.01 parts by weight, 0.05 parts by weight to 1.0 parts by weight is more Preferably, 0.1 mass part-0.5 mass part is the most preferable. The larger the added amount, the better the dynamic friction coefficient, and the smaller the added amount, the less aggregates.

As the disperser, a normal disperser can be used. Dispersers can be broadly divided into media dispersers and medialess dispersers. For dispersion of SiO ₂ fine particles, a medialess disperser is preferred because of low haze. Examples of the media disperser include a ball mill, a sand mill, and a dyno mill. Examples of the medialess disperser include an ultrasonic type, a centrifugal type, and a high pressure type. In the present invention, a high pressure disperser is preferable. The high pressure dispersion device is a device that creates special conditions such as high shear and high pressure by passing a composition in which fine particles and a solvent are mixed at high speed through a narrow tube. When processing with a high-pressure dispersion apparatus, for example, the maximum pressure condition inside the apparatus is preferably 9.807 MPa or more in a thin tube having a tube diameter of 1 to 2000 μm. More preferably, it is 19.613 MPa or more. Further, at that time, those having a maximum reaching speed of 100 m / second or more and those having a heat transfer speed of 420 kJ / hour or more are preferable.

  Examples of the high-pressure dispersing apparatus include an ultra-high pressure homogenizer (trade name: Microfluidizer) manufactured by Microfluidics Corporation or a nanomizer manufactured by Nanomizer, and other manton gorin type high-pressure dispersing apparatuses such as homogenizer manufactured by Izumi Food Machinery. And UHN-01 manufactured by Sanwa Machinery Co., Ltd.

  In addition, casting a dope containing fine particles so as to be in direct contact with the casting support is preferable because a film having high slip properties and low haze can be obtained.

  Moreover, after peeling and drying after casting and winding up into a roll, the optical thin film layer according to the present invention is provided. Until processing or shipment, packaging is usually performed in order to protect the product from dirt, static electricity, and the like. The packaging material is not particularly limited as long as the above purpose can be achieved, but a material that does not hinder volatilization of the residual solvent from the film is preferable. Specific examples include polyethylene, polyester, polypropylene, nylon, polystyrene, paper, various non-woven fabrics, and the like. Those in which the fibers are mesh cloth are more preferably used.

  The cellulose ester film used in the present invention may have a multilayer structure by a co-casting method using a plurality of dopes.

  Co-casting is a sequential multilayer casting method in which two or three layers are configured through different dies, and a simultaneous multilayer casting method in which two or three slits are combined in a die having two or three slits. Any of the multilayer casting methods combining sequential multilayer casting and simultaneous multilayer casting may be used.

  In addition, the cellulose ester used in the present invention is preferably used as a support having a small amount of bright spot foreign matter when formed into a film. In the present invention, the bright spot foreign material is a structure in which two polarizing plates are arranged orthogonally (crossed Nicols), a cellulose ester film is arranged between them, and light from a light source is applied from one side to the other side. When the cellulose ester film is observed, the light from the light source appears to leak.

  At this time, the polarizing plate used for the evaluation is desirably composed of a protective film having no bright spot foreign matter, and a polarizing plate using a glass plate for protecting the polarizer is preferably used. The occurrence of bright spot foreign matter is considered to be one of the causes of unacetylated cellulose contained in the cellulose ester. As countermeasures, the use of cellulose ester with a small amount of unacetylated cellulose, It can be removed and reduced by filtering the dissolved dope solution. Further, the thinner the film thickness, the smaller the number of bright spot foreign matter per unit area, and the lower the content of cellulose ester contained in the film, the fewer bright spot foreign matter.

The bright spot foreign matter having a bright spot diameter of 0.01 mm or more is preferably 200 pieces / cm ² or less, more preferably 100 pieces / cm ² or less, 50 pieces / cm ² or less, 30 pieces / cm. ² or less, preferably 10 pieces / cm ² or less, but it is particularly preferred that a 0.

The number of bright spots of 0.005 mm to 0.01 mm is preferably 200 / cm ² or less, more preferably 100 / cm ² or less, 50 / cm ² or less, 30 / cm ² or less. The number is preferably 10 / cm ² or less, but particularly preferred is the case where the bright spot is zero. A thing with few also about a bright spot of 0.005 mm or less is preferable.

  When removing bright spot foreign matter by filtration, it is preferable to filter the composition in which a plasticizer is added and mixed, rather than filtering a cellulose ester dissolved alone, because the bright spot foreign matter removal efficiency is high. As the filter medium, conventionally known materials such as glass fibers, cellulose fibers, filter paper, and fluororesins such as tetrafluoroethylene resin are preferably used, but ceramics, metals and the like are also preferably used. The absolute filtration accuracy is preferably 50 μm or less, more preferably 30 μm or less, and 10 μm or less, and particularly preferably 5 μm or less.

  These can also be used in combination as appropriate. The filter medium can be either a surface type or a depth type, but the depth type is preferably used because it is relatively less clogged.

  Next, a coating layer useful for the antireflection laminate of the present invention will be described.

  The antireflection layer or other thin film of the present invention may be directly formed on the film-like or sheet-like substrate, but may be formed thereon via another layer.

  In the present invention, examples of the coating layer applied to the surface of the substrate on which the antireflection layer is formed include a clear hard coat layer, an antiglare layer, and an adhesive layer. In particular, in the case of an antireflection laminate, the clear hard coat layer is particularly preferably provided as “another layer” in order to increase the surface hardness of the antireflection laminate. Further, as described above, a conductive layer and an overcoat layer are provided on the side on which the antireflection layer or other thin film is formed and the side opposite to the substrate.

  Here, the clear hard coat layer used for the antireflection laminate is described as a coating layer as an “other layer” useful in the present invention.

  The clear hard coat layer is preferably a layer containing an ultraviolet curable compound (resin) that is cured by ultraviolet rays, and an antireflection laminate excellent in scratch resistance can be obtained.

  The ultraviolet curable resin layer of the clear hard coat layer is preferably a resin layer formed by polymerizing a component containing an ethylenically unsaturated monomer. Here, the ultraviolet curable resin layer refers to a layer mainly composed of a resin which is cured through a crosslinking reaction or the like by irradiation with an active ray such as an electron beam in addition to ultraviolet rays. Typical examples of the ultraviolet curable resin include an ultraviolet curable resin and an electron beam curable resin. However, a resin that is cured by irradiation with active rays other than ultraviolet rays and electron beams may be used. Examples of the ultraviolet curable resin include an ultraviolet curable acrylic urethane resin, an ultraviolet curable polyester acrylate resin, an ultraviolet curable epoxy acrylate resin, an ultraviolet curable polyol acrylate resin, and an ultraviolet curable epoxy resin. I can do it.

  In general, UV-curable acrylic urethane-based resins are obtained by further reacting 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate (hereinafter referred to as acrylate, methacrylate) with a product obtained by reacting a polyester polyol with an isocyanate monomer or a prepolymer. Can be easily obtained by reacting an acrylate monomer having a hydroxyl group such as 2-hydroxypropyl acrylate (for example, see JP-A-59-151110).

  The UV curable polyester acrylate resin can be easily obtained by reacting polyester polyol with 2-hydroxyethyl acrylate or 2-hydroxy acrylate monomer (see, for example, JP-A-59-151112). .

  Specific examples of the ultraviolet curable epoxy acrylate resin include those obtained by reacting epoxy acrylate with an oligomer, a reactive diluent and a photoinitiator added thereto (for example, JP-A-1- No. 105738). As this photoreaction initiator, one or more kinds selected from benzoin derivatives, oxime ketone derivatives, benzophenone derivatives, thioxanthone derivatives and the like can be selected and used.

  Specific examples of ultraviolet curable polyol acrylate resins include trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, alkyl-modified dipentaerythritol pentaacrylate. Etc. can be mentioned.

  These resins are usually used together with known photosensitizers. Moreover, the said photoinitiator can also be used as a photosensitizer. Specific examples include acetophenone, benzophenone, hydroxybenzophenone, Michler's ketone, α-amyloxime ester, thioxanthone, and the like. Further, when using an epoxy acrylate photoreactant, a sensitizer such as n-butylamine, triethylamine, or tri-n-butylphosphine can be used. The photoreaction initiator or photosensitizer contained in the ultraviolet curable resin composition excluding the solvent component that volatilizes after coating and drying can be added in an amount of usually 1 to 10% by mass of the composition, and 2.5 to 6 It is preferable that it is mass%.

  Examples of the resin monomer include general monomers such as methyl acrylate, ethyl acrylate, butyl acrylate, vinyl acetate, benzyl acrylate, cyclohexyl acrylate, and styrene as monomers having one unsaturated double bond. In addition, monomers having two or more unsaturated double bonds include ethylene glycol diacrylate, propylene glycol diacrylate, divinylbenzene, 1,4-cyclohexane diacrylate, 1,4-cyclohexyldimethyl adiacrylate, and the above trimethylolpropane. Examples thereof include triacrylate and pentaerythritol tetraacryl ester.

  For example, as an ultraviolet curable resin, Adekaoptomer KR / BY series: KR-400, KR-410, KR-550, KR-566, KR-567, BY-320B (above, manufactured by Asahi Denka Kogyo Co., Ltd.) Or KOHEI HARD A-101-KK, A-101-WS, C-302, C-401-N, C-501, M-101, M-102, T-102, D-102, NS-101, FT -102Q8, MAG-1-P20, AG-106, M-101-C (manufactured by Guangei Chemical Industry Co., Ltd.), or Seika Beam PHC2210 (S), PHC X-9 (K-3), PHC2213, DP- 10, DP-20, DP-30, P1000, P1100, P1200, P1300, P1400, P1500, P1600, SCR900 (above, large Manufactured by Seika Kogyo Co., Ltd.), or KRM7033, KRM7039, KRM7130, KRM7131, UVECRYL29201, UVECRYL29202 (above, Daicel UCB Corporation), or RC-5015, RC-5016, RC-5020, RC-5031, RC- 5100, RC-5102, RC-5120, RC-5122, RC-5152, RC-5171, RC-5180, RC-5181 (manufactured by Dainippon Ink & Chemicals, Inc.) or Aulex No. 340 clear (manufactured by China Paint Co., Ltd.), Sunrad H-601 (manufactured by Sanyo Chemical Industries, Ltd.), SP-1509, SP-1507 (manufactured by Showa Polymer Co., Ltd.), or RCC-15C (Grace Japan Co., Ltd.) (Manufactured by company), Aronix M-6100, M-8030, M-8060 (above, manufactured by Toagosei Co., Ltd.) or other commercially available ones can be used.

  The ultraviolet curable resin layer can be applied by a known method.

  As a solvent for coating the ultraviolet curable resin layer, for example, it can be appropriately selected from hydrocarbons, alcohols, ketones, esters, glycol ethers, and other solvents, or a mixture thereof can be used. . Preferably, propylene glycol mono (alkyl group having 1 to 4 carbon atoms) alkyl ether is prepared, and propylene glycol mono (alkyl group having 1 to 4 carbon atoms) alkyl ether ester is 5% by mass or more, more preferably 5 to 80% by mass. The solvent contained above is used.

As the light source for forming the cured film layer by photocuring reaction of the ultraviolet curable resin, any light source that generates ultraviolet rays 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. The irradiation conditions vary depending on individual lamps, but the amount of light irradiated may be any degree 20~10000mJ / cm ^2, preferably from 50~2000mJ / cm ^2. It can be used by using a sensitizer having an absorption maximum in the near ultraviolet region to the visible light region.

  The UV curable resin composition is applied and dried, and then irradiated with UV light from a light source. The irradiation time is preferably 0.5 seconds to 5 minutes, and 3 seconds to 2 from the curing efficiency and work efficiency of the UV curable resin. Minutes are more preferred.

  It is preferable to add inorganic or organic fine particles to the cured film layer thus obtained in order to prevent blocking and to improve scratch resistance. Examples of inorganic fine particles include silicon oxide, titanium oxide, aluminum oxide, tin oxide, zinc oxide, calcium carbonate, barium sulfate, talc, kaolin, calcium sulfate, and the like, and examples of organic fine particles include polymethacrylic acid. Methyl acrylate resin powder, acrylic styrene resin powder, polymethyl methacrylate resin powder, silicon resin powder, polystyrene resin powder, polycarbonate resin powder, benzoguanamine resin powder, melamine resin powder, polyolefin resin powder, polyester resin powder Polyamide-based resin powder, polyimide-based resin powder, polyfluorinated ethylene-based resin powder, and the like can be mentioned and added to the ultraviolet curable resin composition. The average particle diameter of these fine particle powders is preferably 0.005 μm to 1 μm, and particularly preferably 0.01 to 0.1 μm.

  The proportion of the ultraviolet curable resin composition and the fine particle powder is desirably blended so as to be 0.1 to 10 parts by mass with respect to 100 parts by mass of the resin composition.

  The layer formed by curing the ultraviolet curable resin thus formed is a clear hard coat layer having a center line average roughness Ra of 1 to 50 nm as defined in JIS B 0601. An antiglare layer of about 1 μm may be used.

  As a method for applying the clear hard coat layer or the antiglare layer to the substrate, a known method such as a gravure coater, a spinner coater, a wire bar coater, a roll coater, a reverse coater, an extrusion coater or an air doctor coater can be used. The liquid film thickness (also referred to as wet film thickness) at the time of application is about 1 to 100 μm, preferably 0.1 to 30 μm, and more preferably 0.5 to 15 μm.

(Polarizer)
The antireflection laminate according to the present invention is extremely excellent as a polarizing plate protective film. The polarizing plate can be produced by a general method. Similarly, in the present invention, a completely saponified polyvinyl alcohol aqueous solution is used on both surfaces of a polarizing film prepared by immersing and stretching a protective film for a polarizing plate obtained by subjecting the antireflection laminate of the present invention to an alkali saponification treatment in an iodine solution. And paste them together. After making the antireflection laminate of the present invention, one side of the cellulose ester film may be saponified.

  The polarizing film, which is the main component of the polarizing plate, is an element that transmits only light having a polarization plane in a certain direction. A typical polarizing film known at present is a polyvinyl alcohol polarizing film, which is a polyvinyl alcohol film. There are one in which iodine is dyed on a system film and one in which dichroic dye is dyed. As the polarizing film, a polyvinyl alcohol aqueous solution is formed and dyed by uniaxially stretching or dyed, or uniaxially stretched after dyeing, and then preferably subjected to a durability treatment with a boron compound. On the surface of the polarizing film, one side of the cellulose ester film having a multilayer structure according to the present invention is bonded to form a polarizing plate. The antireflection laminate according to the present invention is low in moisture permeability and excellent in durability, although it is preferably bonded with a water-based adhesive mainly composed of completely saponified polyvinyl alcohol.

  The image display device using the polarizing plate of the present invention is excellent in durability and can display with high contrast over a long period of time.

(Image display device)
Various image display devices can be produced by incorporating the antireflection laminate of the present invention or a polarizing plate using the same into an image display device. Examples of the image display device include a liquid crystal image display device (reflective type, transflective type, transmissive type), an organic electroluminescence element, a plasma display, and the like. For example, in the forced deterioration treatment under high temperature and high humidity conditions, the antireflection laminate of the present invention or the polarizing plate using the same for the image display device is excellent in visibility and problems caused by the antireflection laminate are recognized. There wasn't.

  Hereinafter, the present invention will be described more specifically by way of examples. However, the embodiments of the present invention are not limited to these examples.

  First, each coating liquid (composition) for producing the antireflection laminate was produced by the following materials and preparation methods.

<< Preparation of Medium Refractive Index Layer, High Refractive Index Layer, Low Refractive Index Layer Coating Liquid >>
(Medium refractive index layer coating solution)
<Medium refractive index layer coating solution A: sol-gel>
First, a mixed solvent was prepared in the container at the following ratio.

Propylene glycol monomethyl ether 4900 parts by mass Isopropyl alcohol 4840 parts by mass The following were sequentially added to the mixed solvent and mixed to obtain a medium refractive index layer composition.

Tetra (n) butoxytitanium 250 parts by mass Terminal reactive dimethyl silicone oil (L-9000, manufactured by Nippon Unicar Co., Ltd.)
0.48 parts by mass Aminopropyltrimethoxysilane (KBE903 manufactured by Shin-Etsu Chemical Co., Ltd.)
22 parts by mass UV curable resin (KR-500: manufactured by Asahi Denka Kogyo Co., Ltd.) 21 parts by mass <Medium refractive index layer coating solution B: Fine particles>
First, a mixed solvent was prepared in the container at the following ratio.

Propylene glycol monomethyl ether 2598 parts by weight Methyl ethyl ketone 866 parts by weight Isopropyl alcohol 5197 parts by weight To this mixed solvent, 30 parts by weight of di-i-propoxy bis (acetylacetonato) titanium (OrgaTix TC100, Matsumoto Pharmaceutical Co., Ltd.) was slowly added. And mixed. After mixing and stirring
KBM503 (Silane coupling agent, manufactured by Shin-Etsu Chemical Co., Ltd.) 19 parts by mass was slowly added and mixed. After mixing and stirring
399 parts by mass of titanium oxide fine particle dispersion (solid content: 15% by mass) (RTSPNB15WT% -G0, manufactured by CI Kasei Kogyo Co., Ltd.) was slowly added and mixed. After mixing and stirring
Dipentaerythritol hexaacrylate (KAYARAD DPHA Nippon Kayaku Co., Ltd.) 10% methyl ethyl ketone solution 534 parts by mass Irgacure 184 (Ciba Specialty Chemicals) 10% methyl ethyl ketone solution 178 parts by mass Acrylic resin (Dianar BR102, manufactured by Mitsubishi Rayon Co., Ltd.) 5% Propylene glycol monomethyl ether solution 162 parts by weight Linear dimethyl silicone-EO block copolymer (FZ-2207 Nihoncar Co., Ltd.) 10% propylene glycol monomethyl ether solution 16 parts by weight were added and mixed in order, and the medium refractive index layer composition did.

<Medium refractive index layer coating solution C: Fine particles>
First, a mixed solvent was prepared in the container at the following ratio.

Propylene glycol monomethyl ether 2624 parts by weight Methyl ethyl ketone 874 parts by weight Isopropyl alcohol 5248 parts by weight The following proportion of water was added and stirred.

1 part by mass of water 21 parts by mass of n-tetrabutoxytitanium was slowly added to and mixed with this mixed solvent. After mixing and stirring
KBM503 (silane coupling agent, manufactured by Shin-Etsu Chemical Co., Ltd.) 24 parts by mass was slowly added and mixed. After mixing and stirring
399 parts by mass of titanium oxide fine particle dispersion (solid content: 15% by mass) (RTSPNB15WT% -G0, manufactured by CI Kasei Kogyo Co., Ltd.) was slowly added and mixed. After mixing and stirring
Dipentaerythritol hexaacrylate (KAYARAD DPHA Nippon Kayaku Co., Ltd.) 10% methyl ethyl ketone solution 534 parts by mass Irgacure 184 (Ciba Specialty Chemicals) 10% methyl ethyl ketone solution 178 parts by mass Acrylic resin (Dianar BR102, manufactured by Mitsubishi Rayon Co., Ltd.) 5% Propylene glycol monomethyl ether solution 81 parts by mass Linear dimethyl silicone-EO block copolymer (FZ-2207, manufactured by Nippon Yuker Co., Ltd.) 10% propylene glycol monomethyl ether solution 16 parts by mass were sequentially added and mixed with the medium refractive index layer composition. did.

<Medium refractive index layer coating solution D: conductive fine particles>
First, a mixed solvent was prepared in the container at the following ratio.

Propylene glycol monomethyl ether 2652 parts by mass Methyl ethyl ketone 884 parts by mass Isopropyl alcohol 5304 parts by mass The following proportion of water was added and stirred.

1 part by mass of water 21 parts by mass of n-tetrabutoxytitanium was slowly added to and mixed with this mixed solvent. After mixing and stirring
863 parts by mass of ITO fine particle dispersion (solid content: 15% by mass) (IRTANB15WT%, manufactured by CI Kasei Kogyo Co., Ltd.) was slowly added and mixed. After mixing and stirring
Dipentaerythritol hexaacrylate (KAYARAD DPHA Nippon Kayaku Co., Ltd.) 10% methyl ethyl ketone solution 194 parts by mass Irgacure 184 (manufactured by Ciba Specialty Chemicals) 10% methyl ethyl ketone solution 65 parts by mass Linear dimethyl silicone-EO block copolymer (FZ-2207 Nippon Nyuka 16 parts by mass of a 10% propylene glycol monomethyl ether solution were sequentially added and mixed to obtain a medium refractive index layer composition.

(High refractive index layer coating solution)
<High refractive index layer coating solution a: sol-gel>
First, a mixed solvent was prepared in the container at the following ratio.

Propylene glycol monomethyl ether 4900 parts by mass Isopropyl alcohol 8900 parts by mass The following was sequentially added to the mixed solvent and mixed to obtain a high refractive index layer composition.

Tetra (n) butoxytitanium 310 parts by mass Terminal reactive dimethyl silicone oil (L-9000, manufactured by Nippon Unicar Co., Ltd.)
0.4 parts by mass Aminopropyltrimethoxysilane (KBE903 manufactured by Shin-Etsu Chemical Co., Ltd.)
4.8 parts by mass Ultraviolet curable resin (Asahi Denka Kogyo Co., Ltd .: KR-500) 4.6 parts by mass <High refractive index layer coating solution b: fine particles>
First, a mixed solvent was prepared in the container at the following ratio.

Propylene glycol monomethyl ether 2792 parts by mass Isopropyl alcohol 5581 parts by mass Methyl ethyl ketone 931 parts by mass The following proportion of water was added and stirred.

Water 2 parts by mass To this mixed solvent, 55 parts by mass of n-tetrabutoxytitanium was slowly added and mixed. After mixing and stirring
KBM503 (silane coupling agent, manufactured by Shin-Etsu Chemical Co., Ltd.) 29 parts by mass was slowly added and mixed. After mixing and stirring
598 parts by mass of titanium oxide fine particle dispersion (solid content 15% by mass) (RTSPNB15WT% -G0, manufactured by CI Kasei Kogyo Co., Ltd.) was slowly added and mixed. After mixing and stirring
13 parts by mass of a 10% propylene glycol monomethyl ether solution of a linear dimethyl silicone-EO block copolymer (FZ-2207, manufactured by Nippon Yuker Co., Ltd.) was slowly added and mixed to obtain a high refractive index layer composition.

(Low refractive index layer coating solution)
<Low refractive index layer coating solution α: sol-gel>
(Preparation of tetraethoxysilane hydrolyzate)
29 g of tetraethoxysilane and 55 g of ethanol were mixed, and after adding 16 g of a 1.6 mass% aqueous solution of acetic acid thereto, a tetraethoxysilane hydrolyzate was prepared by stirring at 25 ° C. for 20 hours.

  First, a mixed solvent was prepared in the container at the following ratio.

Propylene glycol monomethyl ether 382 parts by mass Isopropyl alcohol 384 parts by mass To this mixed solvent, 226 parts by mass of tetraethoxysilane hydrolyzate was slowly added and mixed. After mixing and stirring, KBM503 (silane coupling agent, manufactured by Shin-Etsu Chemical) 6 parts by mass was slowly added and mixed. After mixing and stirring, 2 parts by mass of a 10% propylene glycol monomethyl ether solution of linear dimethyl silicone-EO block copolymer (FZ-2207: Nippon Unicar Co., Ltd.) was slowly added and mixed to obtain a low refractive index layer composition.

<Low refractive index layer coating solution β: fine particles>
The tetraethoxysilane hydrolyzate was prepared as described above.

  First, a mixed solvent was prepared in the container at the following ratio.

Propylene glycol monomethyl ether 387 parts by mass Isopropyl alcohol 390 parts by mass To this mixed solvent, 198 parts by mass of tetraethoxysilane hydrolyzate was slowly added and mixed. After mixing and stirring, KBM503 (silane coupling agent, manufactured by Shin-Etsu Chemical) 6 parts by mass was slowly added and mixed. After mixing and stirring, magnesium fluoride fine particle dispersion (solid content 15% by mass) (MFDNB manufactured by CI Kasei Kogyo Co., Ltd.) 16 parts by mass 10% propylene glycol of linear dimethyl silicone-EO block copolymer (FZ-2207: manufactured by Nihon Unicar Company) 2 parts by mass of monomethyl ether solution was slowly added and mixed to obtain a low refractive index layer composition <Low refractive index layer coating solution γ: hollow fine particles>
The tetraethoxysilane hydrolyzate was prepared as described above.

  First, a mixed solvent was prepared in the container at the following ratio.

Propylene glycol monomethyl ether 377 parts by mass Isopropyl alcohol 379 parts by mass To this mixed solvent, 226 parts by mass of tetraethoxysilane hydrolyzate was slowly added and mixed. After mixing and stirring, 3 parts by mass of KBM503 (silane coupling agent, manufactured by Shin-Etsu Chemical Co., Ltd.) was slowly added and mixed. After mixing and stirring SiO ₂ fine particle dispersion (solid content: 20% by mass) (P-4 manufactured by Catalytic Chemical Industry Co., Ltd.)
12 parts by mass A 10% propylene glycol monomethyl ether solution of a linear dimethyl silicone-EO block copolymer (FZ-2207: manufactured by Nihon Unicar) was slowly added and mixed to obtain a low refractive index layer composition.

<< Preparation of hard coat layer coating liquid >>
A hard coat layer coating solution was prepared in the following configuration.

  First, a mixed solvent was prepared in the container at the following ratio.

Propylene glycol monomethyl ether 300 parts by weight Ethyl acetate 300 parts by weight Dipentaerythritol hexaacrylate monomer 120 parts by weight Dimer 40 parts by weight A component of 40 parts by weight or more of the trimer was slowly added and mixed. After mixing and stirring, 20 parts by mass of Irgacure 184 (manufactured by Ciba Specialty Chemicals) was slowly added and mixed. After mixing and stirring, linear dimethyl silicone-EO block copolymer (FZ-2207, manufactured by Nippon Unicar Co., Ltd.) 1 part by mass was slowly added and mixed to obtain a hard coat layer composition.

<< Preparation of conductive layer coating liquid >>
A conductive layer coating solution was prepared in the following configuration.

<Coating layer coating solution: Cationic polymer>
Conductive fine particle dispersion (5% methanol dispersion of exemplary compound IP-24, average particle size 0.2 μm) 10 parts by mass Cellulose diacetate resin (trade name: Acetate Flakes L-AC, manufactured by Daicel Chemical Industries, Ltd.) 0.2 parts by mass Methanol 20 parts by mass Acetone 40 parts by mass Ethyl acetate 25 parts by mass Isopropyl alcohol 5 parts by mass <Electroconductive layer coating liquid: metal oxide particles>
Conductive fine particle dispersion composition (The preparation method is shown below) 7 parts by weight Nitrocellulose 1 part by weight Acetone 58 parts by weight Methanol 30 parts by weight Ethyl lactate 5 parts by weight (Conductive fine particle dispersion composition)
Conductive SnO ₂ , antimony composite fine particles (manufactured by Mitsubishi Materials Corporation: primary particle diameter 0.015 nm) 200 parts by mass Nitrocellulose 5 parts by mass Acetone 150 parts by mass The above composition is dispersed for 2 hours using a sand mill disperser, A conductive fine particle dispersion composition was prepared.

<< Preparation of overcoat layer coating liquid >>
An overcoat layer coating solution was prepared in the following configuration.

<Overcoat layer coating solution A: DAC>
Cellulose diacetate resin (trade name: Acetate Flakes L-AC, manufactured by Daicel Chemical Industries, Ltd.) 1.0 part by mass 1% acetone-dispersed fine particle silica (trade name: Aerosil 200V, manufactured by Nippon Aerosil Co., Ltd.) 0.05 Part by mass Methyl ethyl ketone 40 parts by mass Ethyl acetate 30 parts by mass Methyl propylene glycol 30 parts by mass <Overcoat layer coating solution A: Acrylic>
Acrylic resin (Dianar BR-108: manufactured by Mitsubishi Rayon Co., Ltd.)
0.5 parts by mass Methyl propylene glycol 65 parts by mass Methyl ethyl ketone 20 parts by mass Ethyl lactate 5 parts by mass <Overcoat layer coating solution C: PVA>
Polyvinyl alcohol (PVA (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name: Gohsenol NH-26)) 0.1 part by mass Saponin (manufactured by Merck Co., Ltd., surfactant) 0.03 part by mass Cross-linking agent (glyoxal) 0.025 parts by mass Pure water 55 parts by mass Methanol 40 parts by mass Isopropyl alcohol 5 parts by mass Using the above coating solutions, samples of the following examples and comparative examples were prepared.

[Example 1]
(Preparation of conductive layer)
Uncoated base unwinding-coating-drying-UV irradiation-in a test plant where continuous coating of the coated base can be performed continuously, using an extrusion coater, a cellulose triacetate film with a film thickness of 80 μm (Konica Corporation Konicattak KC8UX2MW) A conductive layer coating solution (cationic polymer) was used as a coating solution on one side having a refractive index of 1.49 and an acetyl group substitution degree of 2.88.

・ Base width 180mm, coating width 150mm
・ Coating speed 10m / min
・ Drying zone 1: 1m, drying temperature 80 ℃
・ Drying zone 2: 2m, drying temperature 90 ℃
-Drying zone 3: 2m, drying temperature 100 ° C
・ Drying zone 4: 2m, drying temperature 80 ℃
The flow rate of the winding in-winding tension 8kg a 6-inch paper core coating solution amount per after drying was adjusted to 0.2 g / m ^2.

  The base coated with the conductive layer was wound up 100 m.

(Preparation of overcoat layer)
An overcoat layer coating solution (DAC) was used as a coating solution on the base conductive layer coated with the conductive layer in the same test plant as described above, and was prepared under the following conditions.

・ Base width 180mm, coating width 150mm
・ Coating speed 10m / min
・ Drying zone 1: 1m, drying temperature 80 ℃
・ Drying zone 2: 2m, drying temperature 90 ℃
-Drying zone 3: 2m, drying temperature 100 ° C
・ Drying zone 4: 2m, drying temperature 80 ℃
The flow rate of the winding in-winding tension 8kg a 6-inch paper core coating solution amount per after drying was adjusted to 0.2 g / m ^2.

  The base coated with the overcoat layer on the conductive layer was wound up 100 m.

(Preparation of hard coat layer)
In the same test plant as described above, a hard coat layer coating solution was used as the coating solution on the opposite side of the base overcoat layer coated with the overcoat layer, and the coating solution was prepared under the following conditions.

・ Base width 180mm, coating width 150mm
・ Coating speed 10m / min
・ Drying zone 1: 1m, drying temperature 80 ℃
・ Drying zone 2: 2m, drying temperature 90 ℃
-Drying zone 3: 2m, drying temperature 100 ° C
・ Drying zone 4: 2m, drying temperature 80 ℃
And drying after irradiation with UV (so as to be 120 mJ / cm ^2, adjusts the output of the UV lamp)
-Winding up on a 6-inch paper core with a winding tension of 8 kg-The flow rate of the coating solution was adjusted so that the film thickness after drying was 7.0 µm.

  The base coated with a hard coat layer on the opposite surface of the overcoat layer was wound up 100 m.

(Preparation of medium refractive index layer)
A medium refractive index layer coating solution B (fine particles) was used as a coating solution on a base hard coat layer coated with a hard coat layer in the same test plant as described above, and was prepared under the following conditions.

・ Base width 180mm, coating width 150mm
・ Coating speed 10m / min
・ Drying zone 1: 1m, drying temperature 80 ℃
・ Drying zone 2: 2m, drying temperature 90 ℃
-Drying zone 3: 2m, drying temperature 100 ° C
・ Drying zone 4: 2m, drying temperature 80 ℃
And drying after irradiation with UV (so as to be 120 mJ / cm ^2, adjusts the output of the UV lamp)
-Winding up on a 6-inch paper core with a winding tension of 8 kg-The flow rate of the coating solution was adjusted so that the film thickness after drying was 89 nm.

  The base coated with a medium refractive index layer on the hard coat layer was wound up by 100 m.

  The film thickness was obtained from the measurement result of the spectral reflectance of the spectrophotometer for the sample coated under the above coating conditions.

  The spectrophotometer uses U-3310 type (manufactured by Hitachi, Ltd.) to roughen the back side of the measurement side of the sample and then apply light absorption treatment with black spray to prevent light reflection on the back side. The reflectance in the visible light region (400 nm to 700 nm) was measured under the condition of regular reflection at 5 degrees.

(Preparation of high refractive index layer)
A high refractive index layer coating solution b (fine particles) was used as a coating solution on the middle refractive index layer coated base in the same test plant as described above.

・ Base width 180mm, coating width 150mm
・ Coating speed 10m / min
・ Drying zone 1: 1m, drying temperature 80 ℃
・ Drying zone 2: 2m, drying temperature 90 ℃
-Drying zone 3: 2m, drying temperature 100 ° C
・ Drying zone 4: 2m, drying temperature 80 ℃
-UV irradiation after drying (adjust the UV lamp output to 120mJ / cm ² )
-Winding on a 6 inch paper core with a winding tension of 8 kg-The flow rate of the coating solution was adjusted so that the film thickness after drying was 60 nm.

  The base in which the high refractive index layer was coated on the opposite surface on the middle refractive index layer was wound up by 100 m.

  The film thickness was determined from the measurement result of the spectral reflectance of the spectrophotometer in the same manner as described above by preparing a sample in which a single layer was directly coated on the hard coat under the same conditions as the above coating conditions.

(Preparation of low refractive index layer)
A low refractive index layer coating liquid α (sol gel) was used as a coating liquid on a base high refractive index layer coated with a high refractive index layer in the same test plant as described above, and was prepared under the following conditions.

・ Base width 180mm, coating width 150mm
・ Coating speed 10m / min
・ Drying zone 1: 1m, drying temperature 80 ℃
・ Drying zone 2: 2m, drying temperature 90 ℃
-Drying zone 3: 2m, drying temperature 100 ° C
・ Drying zone 4: 2m, drying temperature 80 ℃
And drying after irradiation with UV (so as to be 120 mJ / cm ^2, adjusts the output of the UV lamp)
-Winding up on a 6-inch paper core with a winding tension of 8 kg-The flow rate of the coating solution was adjusted so that the film thickness after drying would be 103 nm.

  The base coated with the low refractive index layer on the high refractive index layer was wound up 100 m.

  The film thickness was measured by the same method as that for the high refractive index layer.

[Example 2]
This was prepared in the same manner as in Example 1 except that the overcoat layer coating solution A was changed to the overcoat layer coating solution A in Example 1.

Example 3
This was prepared in the same manner as in Example 1 except that the overcoat layer coating solution A was changed to the overcoat layer coating solution C in Example 1.

Example 4
A conductive layer coating solution was prepared in the same manner as in Example 1 except that the conductive layer coating solution was changed to a conductive layer coating solution.

[Comparative Example 1]
The conductive layer was produced in the same manner as in Example 1, but no overcoat layer was provided. The hard coat layer was produced in the same manner as in Example 1.

  The medium refractive index layer was prepared in the same manner as in Example 1 except that the medium refractive index layer coating liquid B in Example 1 was changed to the medium refractive index layer coating liquid A. The high refractive index layer was prepared in the same manner as in Example 1 except that the high refractive index layer coating liquid b in Example 1 was changed to the high refractive index layer coating liquid a. The low refractive index layer was produced in the same manner as in Example 1.

[Comparative Example 2]
A comparative example 1 was prepared in the same manner as in comparative example 1 except that the same overcoat layer as in example 1 was provided.

[Comparative Example 3]
It was produced in the same manner as in Example 1 except that the overcoat layer was not provided in Example 1.

Example 5
It was produced in the same manner as in Example 1 except that the medium refractive index layer coating solution B was changed to the medium refractive index layer coating solution C in Example 1.

Example 6
It was produced in the same manner as in Example 1 except that the medium refractive index layer coating solution B was changed to the medium refractive index layer coating solution D in Example 1.

[Comparative Example 5]
It was produced in the same manner as in Example 5 except that no overcoat layer was provided in Example 5.

[Comparative Example 6]
It was produced in the same manner as in Example 6 except that no overcoat layer was provided in Example 6.

Example 7
It was produced in the same manner as in Example 1 except that the low refractive index layer coating solution α was changed to the low refractive index layer coating solution β in Example 1.

Example 8
It was produced in the same manner as in Example 1 except that the low refractive index layer coating solution α was changed to the low refractive index layer coating solution γ in Example 1.

[Comparative Example 7]
It was produced in the same manner as in Example 7 except that no overcoat layer was provided in Example 7.

[Comparative Example 8]
It was produced in the same manner as in Example 8 except that no overcoat layer was provided in Example 8.

Example 9
In Example 1, except that the medium refractive index layer coating liquid B was changed to the medium refractive index layer coating liquid D, and the low refractive index layer coating liquid α was further changed to the low refractive index layer coating liquid γ, the same as in Example 1. Produced.

[Comparative Example 9]
It was produced in the same manner as in Example 9 except that no overcoat layer was provided in Example 9.

  Details of the above samples are summarized in Table 1 below.

  The following evaluation was performed about the obtained sample.

<Scratch, blocking, foreign matter, coating failure (repellency) evaluation>
The sample coated up to the high refractive index layer and wound around the core was unwound, a 10-20 m portion was sampled from the core, and the occurrence of scratches was evaluated visually.

  In addition, after aging at 70 ° C. for 1 week on the sample coated up to the low refractive index layer and wound on the core, the winding was unwound and a portion of 10 to 20 m was sampled from the winding core to check whether there was blocking, how the scratches occurred, The degree of occurrence of foreign matter and the degree of application failure (repellency) were evaluated.

<Evaluation criteria>
(Scratches on medium / high refractive index layer laminate sample)
○: The number of scratches per 10 m of the sample is 5 or less ○ △: The number of scratches per 10 m of the sample is 6 to 10 Δ: The number of scratches per 10 m of the sample is 11 to 50 Δ ×: Scratches per 10 m of the sample 51 to 100 pieces ×: The number of scratches per 10 m of the sample is 101 to 200 pieces XX: The number of scratches per 10 m of the sample is 201 or more (middle / high / low refractive index layer laminate after aging blocking)
○: No blocking ○ △: There is no trace or deformation in the sample to the extent that a light peeling sound is made △: There is no deformation, but a trace remains in the sample △ ×: There is no deformation but a trace remains clearly ×: There is deformation Unevenness remains in the sample XX: Strong resistance when loosening the sample (medium / high / low refractive index layer laminate aging sample scratches)
○: The number of scratches per 10 m of the sample is 10 or less. ○ △: The number of scratches per 10 m of the sample is 11-50. Δ: The number of scratches per 10 m of the sample is 51-100. Δ ×: Scratches per 10 m of the sample. Of 101 to 200 pieces ×: The number of scratches per 10 m of the sample is 201 to 500 pieces XX: The number of scratches per 10 m of the sample is 501 or more (middle / high / low refractive index layer laminate after aging Foreign body)
○: The number of scratches per 10 m of the sample is 5 or less ○ △: The number of scratches per 10 m of the sample is 6 to 10 Δ: The number of scratches per 10 m of the sample is 11 to 50 Δ ×: Scratches per 10 m of the sample 51 to 100 pieces ×: The number of scratches per 10 m of the sample is 101 to 200 pieces XX: The number of scratches per 10 m of the sample is 201 or more (middle / high / low refractive index layer laminate after aging Application failure (repellency))
○: The number of scratches per 10 m of the sample is 5 or less ○ △: The number of scratches per 10 m of the sample is 6 to 10 Δ: The number of scratches per 10 m of the sample is 11 to 50 Δ ×: Scratches per 10 m of the sample The number of scratches is 51 to 100 ×: The number of scratches per 10 m of the sample is 101 to 200 ××: The number of scratches per 10 m of the sample is 201 or more << Surface specific resistance value >>
Each of the above samples was conditioned at 25 ° C. and 55% RH for 24 hours, and measured using a Teraohm Meter Model VE-30 manufactured by Kawaguchi Electric Co., Ltd. The electrodes used for the measurement were measured by placing two electrodes (parts in contact with the sample at 1 cm × 5 cm) in parallel with an interval of 1 cm, contacting the sample with the electrodes, and multiplying the measured value by five times. The value was defined as the surface specific resistance value Ω / □. In the present invention, the surface specific resistance represents the value of the surface of the conductive layer, and when the overcoat layer is on the conductive layer, the measured value of the outermost layer is the surface specific resistance value.

<Reflectance>
Using a spectrophotometer (U-3310, manufactured by Hitachi, Ltd.), after roughening the back side of the measurement side of the sample, light absorption treatment is performed with a black spray to prevent reflection of light on the back side. The reflection spectrum in the visible light region (400 nm to 700 nm) was measured under conditions of regular reflection at 5 degrees.

  From the measurement result of this reflection spectrum, based on JIS-Z-8701 and CIE1931, the Y value in a C light source and a 2 degree visual field was made into the reflectance.

  The evaluation results of the above samples are shown in Table 2 below.

  From the above table, the overcoat layer of the present invention was provided for a sample of a comparative example having an antireflection layer containing fine particles and providing a conductive layer on the opposite side of the substrate but not an overcoat layer. It is clear that the sample is not easily scratched and has significantly less blocking and coating failure.

  In addition, the sample of the present invention has a low surface specific resistance value and sufficient anti-static performance, and the sample using hollow fine particles in the low refractive index layer has low reflectivity and good anti-reflection performance. I understood.

Claims (15)

An antireflection layer containing at least one layer of fine particles is provided on one side of the support, and at least a conductive layer and an overcoat layer are provided on the side opposite to the side on which the antireflection layer is provided. Antireflection laminate. The antireflection laminate according to claim 1, wherein the antireflection layer comprises at least a high refractive index layer and a low refractive index layer. The antireflection laminate according to claim 1, wherein the antireflection layer is provided in the order of a medium refractive index layer, a high refractive index layer, and a low refractive index layer from the support side. The antireflection laminate according to claim 2 or 3, wherein the low refractive index layer contains SiO ₂ fine particles or MgF ₂ fine particles. The antireflection laminate according to claim 4, wherein the SiO ₂ fine particles are hollow. The medium refractive index layer and the high refractive index layer are selected from the group consisting of Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P, and S. The antireflection laminate according to any one of claims 3 to 5, comprising fine particles of a metal oxide having at least one element selected. 2. The antireflection laminate according to claim 1, wherein a surface specific resistance of the surface provided with the conductive layer and the overcoat layer is 10 ¹¹ Ω / □ (25 ° C., 55% RH) or less. The antireflection laminate according to claim 1, wherein the conductive layer contains an ionic polymer compound. The antireflective laminate according to claim 8, wherein the ionic polymer compound is a quaternary ammonium cationic polymer having molecular crosslinking. The conductive material of the conductive layer contains as a main component at least one element selected from the group consisting of Sn, Ti, In, Al, Zn, Si, Mg, Ba, Mo, W, and V, The volume resistivity is 10 ⁷ Ω · cm (25 ° C., 55% RH) or less, and the antireflection laminate according to any one of claims 1, 7, and 8. The said electroconductive layer contains a cellulose ester resin or an acrylic resin, The antireflection laminated body of any one of Claims 1 and 7-10 characterized by the above-mentioned. The antireflection laminate according to claim 1, wherein the overcoat layer contains at least a cellulose ester resin or an acrylic resin. The antireflection laminate according to claim 12, wherein the overcoat layer contains a hydrophilic polymer compound. The antireflection laminate according to claim 12 or 13, wherein the overcoat layer contains at least one of gelatin or a gelatin derivative and a cellulose ester resin. The amount of the conductive layer after drying is 0.05 to 1.0 g / m ² , and the amount of the overcoat layer after drying is 0.05 to 1.0 g / m ^2. The antireflection laminate according to any one of claims 1 and 7 to 14.