JP2000121806A - Antireflection film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an antireflection film having an adequate color correction function in addition to an antireflection function by disposing a primer coat layer containing a polymer of a specific glass transition temperature or below or a primer coat layer of which the filter layer side have a rough surface between a filter layer and a transparent base. SOLUTION: The antireflection film is constituted by laminating the filter layer 3 containing dyes and a polymer binder, the transparent base 1 and a low-refractive index layer 4 having the refractive index lower than the refractive index of the transparent base 1 in this order. The antireflection film is provided with the primer coat layer 2 containing the polymer having a glass transition temperature of <=25 deg.C or the primer coat layer 2 of which the filter layer 3 side has a rough surface between the filter layer 3 and the transparent base 1. The thickness of the primer coat layer 2 is preferably 20 to 100 nm. The primer coat layer 2 containing the polymer having a glass transition temperature of >=25 deg.C adheres the transparent base 1 and the filter layer 3 by the tacky adhesiveness of the polymer. The average grain size of the latex of the primer coating layer 2 of which the surface is rough is preferably 0.02 to 3 μm.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an antireflection film having a transparent support, a low refractive index layer and a filter layer. In particular, the present invention relates to a liquid crystal display (LCD), a plasma display panel (PDP), an electroluminescence display (ELD), a cathode ray tube display (CR)
T) relates to an antireflection film attached to the surface of an image display device such as a fluorescent display tube or a field emission display for antireflection and improving color reproducibility.

[0002]

2. Description of the Related Art A liquid crystal display (LCD), a plasma display panel (PDP), an electroluminescence display (ELD), a cathode ray tube display (CRT),
An image display device such as a fluorescent display tube or a field emission display has a problem that the contrast is reduced due to the background being reflected on the display. As means for solving this problem, various antireflection films have been proposed. The antireflection functional layers of the antireflection films proposed so far can be classified into vapor deposition layers and coating layers. Although the vapor deposition layer is superior from the viewpoint of optical functions, the coating layer has an advantage that it is easy to manufacture. The vapor deposition layer has been used for a long time as an antireflection film for lenses such as glasses and cameras. The deposition layer is formed by a vacuum deposition method, a sputtering method, an ion plating method, a CVD method, or a PVD method. The coating layer is generally formed by applying fine particles and a binder. The coating layer is described in JP-A-59-49501.
And JP-A-59-50401, JP-A-60-59250 and JP-A-7-48527.

[0003] In addition to anti-reflection, the image display device also requires color correction. In image display devices, in principle,
A color image is displayed using a combination of the three primary colors of red, blue and green. However, it is very difficult (practically impossible) to make light for display ideal three primary colors.
For example, in a plasma display panel (PDP),
It is known that light emitted from the three primary color phosphors contains extra light (wavelength in the range of 560 to 620 nm). Therefore, it has been proposed to perform color correction using a filter that absorbs light of a specific wavelength in order to correct the color balance of display colors. Japanese Patent Application Laid-Open Nos. 58-153904 and 61-1885 disclose color correction using a filter.
No. 01, JP-A-3-231988, JP-A-5-20564
No. 3, 9-145918, 9-306366,
It is described in each publication of JP-A-10-26704. It is also conceivable to incorporate a filter function into the antireflection film. JP-A-61-188501 and JP-A-5-25-2 described above.
No. 05643, No. 9-145918, No. 9-3063
Nos. 66 and 10-26704 each disclose an antireflection film having a built-in filter function. In the antireflection films described in JP-A-61-188501, JP-A-5-205643, JP-A-9-145918 and JP-A-9-306366, a dye or pigment is added to the transparent support of the antireflection film. Thus, the support functions as a filter. In the anti-reflection film described in JP-A-10-26704, the hard coat layer (surface hardened layer) provided between the transparent support and the anti-reflection layer is colored so that the hard coat layer functions as a filter.

[0004]

If the transparent support or the hard coat layer of the antireflection film is colored, the transparent support or the hard coat layer functions as a filter. However, the types of dyes and pigments that can be added to the transparent support and the hard coat layer are very limited. The transparent support is made from plastic or glass (usually plastic). Dyes and pigments to be added to the transparent support are required to have extremely high heat resistance enough to withstand the temperature during the production of the support. The hard coat layer is generally a layer containing a crosslinked polymer. The crosslinking reaction of the polymer is carried out after the application of the layer. Under the reaction conditions for crosslinking, there are many dyes and pigments that fade. Dyes or pigments used for color correction are required to have various absorption spectrum characteristics depending on the type of image display device. If the types of dyes and pigments used for color correction are limited, it is difficult to perform appropriate correction.

The present inventor has proposed that a dye be added to a polymer layer that can be formed under mild conditions, instead of a transparent support or a hard coat layer, which has many restrictions on the types of dyes that can be used, so that the polymer layer functions as a filter layer. It was investigated. Due to the optical properties of the anti-reflective coating, the filter layer must be provided adjacent to the transparent support. However, the affinity between the dye-containing polymer layer and the transparent support (plastic or glass) is low, and the dye-containing polymer layer is easily separated from the transparent support. It is considered that the reason why the conventional technique allows the transparent support or the hard coat layer to function as a filter is that a problem occurs in adhesion between the filter layer and the transparent support. An object of the present invention is to provide an antireflection film having an appropriate color correction function in addition to an antireflection function.

[0006]

The object of the present invention has been attained by the following antireflection films (1) to (8). Are as follows. (1) An antireflection film in which a filter layer containing a dye and a polymer binder, a transparent support, and a low refractive index layer having a refractive index lower than that of the transparent support are laminated in this order, An antireflection film, comprising an undercoat layer containing a polymer having a glass transition temperature of 25 ° C. or lower or an undercoat layer having a rough surface on the filter layer side between the layer and the transparent support. (2) The antireflection film according to (1), wherein the filter layer has an absorption maximum in a wavelength range of 560 to 620 nm. (3) The antireflection film according to (1), wherein a hard coat layer having a hardness higher than the hardness of the transparent support is provided between the transparent support and the low refractive index layer. (4) The antireflection film according to (3), wherein the hard coat layer contains a crosslinked polymer. (5) An antireflection film in which a transparent support, a filter layer containing a dye and a polymer binder, and a low refractive index layer having a refractive index lower than the refractive index of the transparent support are laminated in this order. An antireflection film, wherein an undercoat layer containing a polymer having a glass transition temperature of 25 ° C. or lower or an undercoat layer having a rough surface on the filter layer side is provided between the support and the filter layer. (6) The antireflection film according to (5), wherein the filter layer has an absorption maximum in a wavelength range of 560 to 620 nm. (7) The antireflection film according to (5), wherein a hard coat layer having a hardness higher than the hardness of the transparent support is provided between the filter layer and the low refractive index layer. (8) The antireflection film according to (7), wherein the hard coat layer contains a crosslinked polymer.

[0007]

The present inventor has proceeded with the study and studied to provide an undercoat layer between the transparent support and the filter layer to enhance the adhesive strength between the transparent support and the filter layer. However, the optical function of the antireflection film must not be impaired by providing the undercoat layer. As a result of further research conducted by the present inventors, the use of an undercoat layer containing a polymer having a glass transition temperature of 25 ° C. or lower or an undercoat layer having a rough surface on the filter layer side enables the optical function of the antireflection film to be improved. Without affecting, it succeeded in enhancing the adhesive strength between the transparent support and the filter layer. As a result of eliminating the problem of adhesion between the transparent support and the filter layer, various kinds of dyes can be used for the filter layer. For example, in the field of silver halide photography, various photographic dyes have been developed. The absorption spectral properties of photographic dyes have also been studied in detail. It has been difficult to add a photographic dye to a transparent support or a hard coat layer by a conventional method. According to the present invention, various photographic dyes can be used for the antireflection film. As a result, in the antireflection film of the present invention, in addition to the antireflection function, it is possible to obtain an appropriate color correction function according to the type of the image display device.

[0008]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS A typical layer structure of an antireflection film is as follows.
This will be described with reference to the drawings. FIG. 1 is a schematic cross-sectional view showing a layer configuration of an antireflection film in which a filter layer is provided on the side opposite to the transparent support from the antireflection layer. The embodiment shown in FIG. 1A has a layer structure in the order of a filter layer (3), an undercoat layer (2), a transparent support (1), and a low refractive index layer (4). The transparent support (1) and the low refractive index layer (4) have a refractive index satisfying the following relationship. Refractive index of low refractive index layer <refractive index of transparent support In the embodiment shown in FIG. 1B, the filter layer (3), the undercoat layer (2), the transparent support (1), and the hard coat layer (5) , Low refractive index layer (4). The embodiment shown in FIG. 1C includes a filter layer (3), an undercoat layer (2), a transparent support (1), a hard coat layer (5),
It has a layer configuration in the order of a high refractive index layer (6) and a low refractive index layer (4). The transparent support (1), the low refractive index layer (4) and the high refractive index layer (6) have a refractive index satisfying the following relationship. The refractive index of the low refractive index layer <the refractive index of the transparent support <the refractive index of the high refractive index layer In the embodiment shown in FIG. 1 (d), the filter layer (3), the undercoat layer (2), the transparent support (1) ), A hard coat layer (5), a medium refractive index layer (7), a high refractive index layer (6), and a low refractive index layer (4). The transparent support (1), the low-refractive-index layer (4), the high-refractive-index layer (6) and the middle-refractive-index layer (7) have a refractive index satisfying the following relationship. Refractive index of low refractive index layer <refractive index of transparent support <refractive index of medium refractive index layer <refractive index of high refractive index layer

FIG. 2 is a schematic sectional view showing a layer structure of an antireflection film in which a filter layer and an antireflection layer are provided on the same side of a transparent support. The embodiment shown in FIG. 2A has a layer structure of a transparent support (1), an undercoat layer (2), a filter layer (3), and a low refractive index layer (4) in this order. The relationship between the refractive index of the transparent support (1) and the refractive index of the low refractive index layer (4) is the same as that of FIG. The embodiment shown in FIG. 2B includes a transparent support (1), an undercoat layer (2), a filter layer (3),
It has a layer structure in the order of the hard coat layer (5) and the low refractive index layer (4). The embodiment shown in FIG. 2C includes a transparent support (1), an undercoat layer (2), a filter layer (3), a hard coat layer (5), a high refractive index layer (6), and a low refractive index layer ( 4)
In the following order. The relationship between the refractive indices of the transparent support (1), the low refractive index layer (4) and the high refractive index layer (6) is the same as that in FIG. The mode shown in FIG.
A transparent support (1), an undercoat layer (2), a filter layer (3), a hard coat layer (5), a medium refractive index layer (7), a high refractive index layer (6), and a low refractive index layer (4). It has an orderly layer configuration. The relationship among the refractive indices of the transparent support (1), the low refractive index layer (4), the high refractive index layer (6) and the middle refractive index layer (7) is the same as that in FIG.

(Transparent support) Examples of the material forming the transparent support include cellulose esters (eg, diacetyl cellulose, triacetyl cellulose (TAC), propionyl cellulose, butyryl cellulose, acetyl propionyl cellulose, nitrocellulose). Polyamide, polycarbonate, polyester (eg, polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, poly-1,4-cyclohexane dimethylene terephthalate, polyethylene-1,2-diphenoxyethane-4,4'-dicarboxylate, poly Butylene terephthalate), polystyrene (eg, syndiotactic polystyrene), polyolefin (eg, polyethylene, polypropylene, polymethylpentene), polymethylmethacrylate , Syndiotactic polystyrene, polysulfone, polyethersulfone, polyetherketone, polyetherimide and polyoxyethylene. Triacetyl cellulose, polycarbonate and polyethylene terephthalate are preferred. The transmittance of the transparent support is preferably 80% or more,
More preferably, it is 86% or more. Haze is 2
%, More preferably 1% or less. The refractive index is preferably from 1.45 to 1.70. An infrared absorber or an ultraviolet absorber may be added to the transparent support. The amount of the infrared absorber added is preferably 0.01 to 20% by weight of the transparent support, more preferably 0.05 to 10% by weight. Further, as a slipping agent, particles of an inert inorganic compound may be added to the transparent support. Examples of the inorganic _{compound, SiO 2, TiO 2, BaSO} 4, CaCO 3, talc and kaolin. The transparent support may be subjected to a surface treatment. Examples of surface treatment include chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency treatment, glow discharge treatment, active plasma treatment,
Laser treatment, mixed acid treatment and ozone oxidation treatment are included. Glow discharge treatment, ultraviolet irradiation treatment, corona discharge treatment and flame treatment are preferred, and glow discharge treatment and ultraviolet treatment are more preferred. Further, an undercoat layer for strengthening the adhesion with the upper layer may be provided.

(Anti-reflection layer) As the anti-reflection layer, a low refractive index layer is essential. The refractive index of the low refractive index layer is lower than the refractive index of the transparent support. The refractive index of the low refractive index layer is
1.20 to 1.55, preferably 1.30
It is more preferably from 1.55 to 1.55. The thickness of the low refractive index layer is preferably 50 to 400 nm,
More preferably, it is 50 to 200 nm. The low refractive index layer is a layer made of a fluoropolymer having a low refractive index (JP-A-57-34526, JP-A-3-130103).
, JP-A-6-115023, JP-A-8-313702, and JP-A-7-168004), and a layer obtained by a sol-gel method (JP-A-5-208811, JP-A-6-299).
Nos. 091 and 7-168003) or a layer containing fine particles (JP-B-60-59250, JP-A-5-13021, JP-A-6-56478 and JP-A-7-923).
No. 06 and No. 9-288201). In the layer containing fine particles, voids can be formed in the low refractive index layer as microvoids between the fine particles or in the fine particles. The layer containing fine particles preferably has a porosity of 3 to 50% by volume, and 5 to 3% by volume.
More preferably, it has a porosity of 5% by volume.

In order to prevent reflection in a wide wavelength range,
It is preferable that a layer having a high refractive index (medium / high refractive index layer) is laminated on the low refractive index layer. The refractive index of the high refractive index layer is 1.6
It is preferably 5 to 2.40, and more preferably 1.70 to 2.20. The refractive index of the middle refractive index layer is adjusted to be an intermediate value between the refractive index of the low refractive index layer and the refractive index of the high refractive index layer. The refractive index of the middle refractive index layer is preferably from 1.55 to 1.70. During·
The thickness of the high refractive index layer is preferably from 5 nm to 100 μm, more preferably from 10 nm to 10 μm, and most preferably from 30 nm to 1 μm. The haze of the middle / high refractive index layer is preferably 5% or less, more preferably 3% or less, and more preferably 1%.
It is most preferred that: The middle / high refractive index layer can be formed using a polymer binder having a relatively high refractive index. Examples of high refractive index polymers include:
Polystyrene, styrene copolymer, polycarbonate,
Included are melamine resins, phenolic resins, epoxy resins and polyurethanes obtained by reacting cyclic (alicyclic or aromatic) isocyanates with polyols. Other polymers having a cyclic (aromatic, heterocyclic, alicyclic) group and polymers having a halogen atom other than fluorine as a substituent also have a high refractive index. A polymer may be formed by a polymerization reaction of a monomer capable of radical curing by introducing a double bond.

In order to obtain a higher refractive index, inorganic fine particles may be dispersed in a polymer binder. The refractive index of the inorganic fine particles is preferably from 1.80 to 2.80. The inorganic fine particles are preferably formed from a metal oxide or sulfide. Examples of metal oxides or sulfides include titanium dioxide (eg, rutile, rutile / anatase mixed crystals, anatase, amorphous structure), tin oxide, indium oxide, zinc oxide, zirconium oxide, and zinc sulfide. Titanium oxide, tin oxide and indium oxide are particularly preferred. The inorganic fine particles contain oxides or sulfides of these metals as main components and may further contain other elements. The main component means a component having the largest content (% by weight) of 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, S
i, P and S are included. Inorganic materials that are film-forming and can be dispersed in solvents or are themselves liquid, such as alkoxides of various elements, salts of organic acids, coordination compounds (eg, chelate compounds) combined with coordination compounds, activity The middle / high refractive index layer can be formed using an inorganic polymer.

The anti-reflection layer can provide the surface with an anti-glare function (a function of scattering incident light on the surface to prevent a scene around the film from shifting to the film surface). For example, by forming fine irregularities on the surface of a transparent film, and forming an antireflection layer on the surface, or after forming the antireflection layer, by forming irregularities on the surface with an embossing roll, an anti-glare function is obtained. be able to.
An antireflection layer having an antiglare function generally has a haze of 3 to 30%.

(Filter layer) The thickness of the filter layer is 1
It is preferably from 15 to 15 μm. The dye used in the filter layer preferably has an absorption maximum in a wavelength range of 560 to 620 nm (between green and red). Two or more dyes may be used as a mixture. The absorption spectrum of the dye is preferably sharp. Specifically, the half width value (the width of the wavelength region showing half the absorbance of the absorbance at the maximum absorption wavelength of the dye in the solution) is preferably 10 to 100 nm, more preferably 20 to 70 nm, Most preferably, it is 20 to 50 nm. As the dye, imidazoquinoxaline-based, squarylium-based, indolenine trimethylene-based, azomethine-based, xanthene-based, cyanine-based or oxonol-based compounds are particularly preferably used. These dyes are
It is known as a photographic dye, and its absorption spectral properties are well studied. The dye may be added to the filter layer as a particulate dispersion. The filter layer further includes a polymer binder. Natural polymer (eg, gelatin, cellulose derivative, alginic acid) or synthetic polymer (eg, polymethyl methacrylate, polyvinyl butyral, polyvinyl pyrrolidone, polyvinyl alcohol, polyvinyl chloride, styrene-butadiene copolymer, polystyrene, polycarbonate, water-soluble polyamide) It can be used as a polymer binder. Particularly preferred are hydrophilic polymers (the above-mentioned natural polymers, polyvinyl butyral, polyvinyl pyrrolidone, polyvinyl alcohol, and water-soluble polyamide).

An anti-fading agent may be added to the filter layer. Examples of anti-fading agents that function as dye stabilizers include hydroquinone derivatives (US Pat. No. 3,935,016).
Nos. 3,982,944), hydroquinone diether derivatives (described in U.S. Pat. No. 4,254,216 and JP-A-55-21004), phenol derivatives (described in JP-A-54-145530),
Derivatives of spiroindane or methylenedioxybenzene (UK Patent Publications Nos. 2077455 and 2062888)
And the derivatives of chroman, spirochroman or coumaran (U.S. Pat. Nos. 3,432,300 and 3,573,050).
Nos. 3574627 and 3764337 and JP-A Nos. 52-152225 and 53-20327.
Nos. 53-17729 and 61-90156), hydroquinone monoether or paraaminophenol derivatives (UK Patent 1347556,
Nos. 2066975 and JP-B-54-12
337, JP-A-55-6321) and bisphenol derivatives (described in US Pat. No. 3,700,455 and JP-B-48-31625).

In order to improve the stability of the dye to light or heat, a metal complex (described in US Pat. No. 4,245,018 and JP-A-60-97353) may be used as an anti-fading agent. In order to further improve the light fastness of the dye, a singlet oxygen quencher may be used as an anti-fading agent. Examples of the singlet oxygen quencher include a nitroso compound (described in JP-A-2-300288), a diimmonium compound (described in US Pat. No. 4,656,612), a nickel complex (described in JP-A-4-146189), and antioxidant. Agent (European Patent Publication 820057A1)
Description).

(Undercoat layer) In the present invention, an undercoat layer containing a polymer having a glass transition temperature of 25 ° C. or lower or an undercoat layer having a rough surface on the filter layer side is provided between the transparent support and the filter layer. . Thereby, the adhesive strength between the transparent support and the filter layer is improved. An undercoat layer is provided on the surface of the transparent support on which the filter layer is not provided to improve the adhesion between the transparent support and a layer provided thereon (for example, an antireflection layer or a hard coat layer). Is also good. The undercoat layer may be provided to improve the affinity between the adhesive for bonding the antireflection film and the image forming apparatus and the antireflection film. The thickness of the undercoat layer is preferably from 20 nm to 1000 nm, more preferably from 80 nm to 300 nm. An undercoat layer containing a polymer having a glass transition temperature of 25 ° C. or lower adheres the transparent support and the filter layer due to the tackiness of the polymer. Polymers having a glass transition temperature of 25 ° C. or lower can be obtained by polymerization or copolymerization of vinyl chloride, vinylidene chloride, vinyl acetate, butadiene, neoprene, styrene, chloroprene, acrylate, methacrylate, acrylonitrile or methyl vinyl ether. . The glass transition temperature is 2
The temperature is preferably 0 ° C. or lower, more preferably 15 ° C. or lower, still more preferably 10 ° C. or lower, still more preferably 5 ° C. or lower, and most preferably 0 ° C. or lower. The undercoat layer having a rough surface adheres the transparent support and the filter layer by forming a filter layer on the rough surface. The undercoat layer having a rough surface can be easily formed by applying a polymer latex. The average particle size of the latex is 0.0
It is preferably 2 to 3 μm, and 0.05 to 1 μm.
m is more preferable. Glass transition temperature is 25
An undercoat layer containing a polymer having a glass transition temperature of 25 ° C. or less and having a rough surface on the filter layer side may be formed by using a polymer latex having a temperature of 25 ° C. or less. The undercoat layer may contain a solvent for swelling the transparent support, a matting agent, a surfactant, an antistatic agent, a coating aid and a hardener.

(Second Undercoat Layer) A second undercoat layer may be provided between the undercoat layer and the filter layer. The second undercoat layer is formed using a poly (for example, acrylic resin, cellulose derivative, gelatin, casein, starch, polyvinyl alcohol, soluble nylon, or polymer latex) having a high affinity for the binder polymer of the filter layer. Is preferred. A solvent for swelling the transparent support, a matting agent, a surfactant, an antistatic agent, a coating aid, a hardening agent, and the like can be added to the second undercoat layer.

(Other Layers) The antireflection film may be provided with a hard coat layer, a lubricating layer, an antistatic layer or an intermediate layer. The hard coat layer preferably contains a cross-linked polymer. The hard coat layer can be formed using an acrylic, urethane, or epoxy polymer, oligomer, or monomer (eg, an ultraviolet curable resin). The hard coat layer can also be formed from a silica-based material. A lubrication layer may be formed on the outermost surface of the antireflection film. The lubricating layer has a function of imparting lubricity to the surface of the antireflection film and improving scratch resistance. The lubricating layer can be formed using polyorganosiloxane (eg, silicone oil), natural wax, petroleum wax, higher fatty acid metal salt, fluorine-based lubricant or a derivative thereof. The thickness of the lubricating layer is preferably 2 to 20 nm.

The anti-reflection layer (medium-refractive-index layer, high-refractive-index layer, low-refractive-index layer), filter layer, undercoat layer, hard coat layer, lubricating layer and other layers are formed by a general coating method. Can be. Examples of the coating method include 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, and an extrusion coating method using a hopper (described in US Pat. No. 2,681,294). Is included. Two or more layers may be formed by simultaneous coating. The simultaneous coating method is described in U.S. Pat.
No. 41898, No. 3508947, No. 3526528
Issue specifications and Yuji Harazaki, "Coating Engineering" 2
It is described on page 53 (published by Asakura Shoten in 1973).

(Use of antireflection film) The antireflection film is used for a liquid crystal display (LCD) or a plasma display panel (P).
DP), electroluminescent display (EL)
D) or an image display device such as a cathode ray tube display device (CRT). The surface of the antireflection film on which the low refractive index layer is not provided is arranged so as to face the image display surface of the image display device. When the antireflection film of the present invention is used as an antireflection filter of a plasma display panel (PDP), a particularly remarkable effect is obtained. A plasma display panel (PDP) includes a gas, a glass substrate, an electrode, an electrode lead material, a thick film printing material, and a phosphor. There are two glass substrates, a front glass substrate and a rear glass substrate. An electrode and an insulating layer are formed on two glass substrates. A phosphor layer is further formed on the rear glass substrate. Two glass substrates are assembled, and gas is sealed between them. Plasma display panels (PDPs) are already commercially available. Regarding the plasma display panel, JP-A-5-205643 and JP-A-9-306366.
There is a description in each gazette of the issue.

[0023]

[Example 1] (Formation of undercoat layer) After corona treatment was applied to both sides of a transparent polyethylene terephthalate film having a thickness of 100 µm,
A latex made of a styrene-butadiene copolymer was applied on one surface to a thickness of 140 nm to form an undercoat layer.

(Formation of Second Undercoat Layer) On the undercoat layer,
A gelatin aqueous solution containing acetic acid and glutaraldehyde was applied to a thickness of 40 nm to form a second undercoat layer.

(Formation of Low Refractive Index Layer) Reactive Fluoropolymer (JN-7219, manufactured by Nippon Synthetic Rubber Co., Ltd.) 2.50
1.3 g of t-butanol was added to the resulting mixture, and the mixture was stirred at room temperature for 10 minutes and filtered with a 1 μm polypropylene filter.
The obtained coating liquid for a low refractive index layer was coated on a surface opposite to the undercoat surface of the transparent support with a dry film thickness of 1 using a bar coater.
It was applied to a thickness of 10 nm, dried at 120 ° C. for 30 minutes and cured to form a low refractive index layer.

(Formation of Filter Layer) 0.05 g of the following dye was dissolved in 100 g of a 1% by weight aqueous solution of high-molecular-weight alkali-treated gelatin for photography, stirred at 40 ° C. for 30 minutes, and filtered through a 2 μm polypropylene filter. The obtained filter layer coating solution is coated on the second undercoat layer,
Coating was performed so that the dry film thickness became 3.5 μm, and dried at 120 ° C. for 10 minutes to form a filter layer, thereby forming an antireflection film.

[0027]

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Example 2 (Formation of Undercoat Layer) On one side of a transparent cellulose triacetate film having a thickness of 80 μm, a latex made of a styrene-butadiene copolymer was applied to a thickness of 140 nm to form an undercoat layer.

(Formation of Hard Coat Layer) 25 parts by weight of dipentaerythritol hexaacrylate (DPHA,
Nippon Kayaku Co., Ltd.), 25 parts by weight of a urethane acrylate oligomer (UV-6300B, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), 2 parts by weight of a photopolymerization initiator (IRGACURE-
907, Ciba-Geigy) and 0.5 parts by weight of a sensitizer (Kayacure-DETX, manufactured by Nippon Kayaku Co., Ltd.)
It was dissolved in 0 parts by weight of methyl ethyl ketone. The obtained coating solution was applied to the surface of the transparent support opposite to the undercoating surface using a bar coater, dried, and irradiated with ultraviolet rays to form a hard coat layer (layer thickness: 6 μm).

(Formation of Low Refractive Index Layer) On the hard coat layer, a coating liquid for a low refractive index layer containing the reactive fluoropolymer used in Example 1 was applied in the same manner as in Example 1 to obtain a low refractive index layer. A rate layer was formed.

(Formation of Filter Layer) On the undercoat layer,
The coating liquid for a filter layer used in Example 1 was applied in the same manner as in Example 1 to form a filter layer, and an antireflection film was formed.

Example 3 (Formation of Undercoat Layer) As in Example 1, an undercoat layer (a) and a second undercoat layer (a) were formed on one surface of the transparent support. A latex made of a styrene-butadiene copolymer is applied to a surface of the transparent support on which the undercoat layer is not provided so as to have a thickness of 110 nm, and an undercoat layer (b) is formed.
Was formed.

(Formation of Second Undercoat Layer) On the undercoat layer (b), an acrylic latex (HA16, manufactured by Nippon Acrylic Co., Ltd.) was applied to a thickness of 60 nm to form a second undercoat layer (b). Was formed.

(Formation of Antireflection Layer) Second Undercoat Layer (b)
A low refractive index layer was formed thereon in the same manner as in Example 1.

(Formation of Filter Layer) On the second undercoat layer (a), a filter layer was formed in the same manner as in Example 1 to form an antireflection film.

Example 4 (Formation of Hard Coat Layer) As in Example 3, an undercoat layer (a), a second undercoat layer (a), an undercoat layer (b) and a second undercoat layer were formed on a transparent support. An undercoat layer (b) was formed. A hard coat layer was formed on the second undercoat layer (b) in the same manner as in Example 2.

(Preparation of Titanium Dioxide Dispersion) Titanium dioxide (primary particle weight average particle diameter: 50 nm, refractive index 2.7)
0) 30 parts by weight, the following anionic monomer (1)
5 parts by weight, 0.3 parts by weight of the following cationic monomer (2), and 65.2 parts by weight of cyclohexanone were dispersed by a sand grinder to prepare a titanium dioxide dispersion.

[0038]

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[0039]

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(Preparation of Coating Solution for Medium Refractive Index Layer) To 151 g of titanium dioxide dispersion, 107.0 g of dipentaerythritol hexaacrylate, 5.13 g of photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy), photosensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.) 1.71 g,
98.45 g of methyl ethyl ketone was added, and 30
After stirring for 1 minute, the mixture was filtered through a 1 μm polypropylene filter to prepare a coating solution for a medium refractive index layer.

(Formation of Medium Refractive Index Layer) On the hard coat layer, a coating solution for the medium refractive index layer is applied by a bar coater, and cured by irradiating ultraviolet rays, and the thickness (dry film thickness) is 79 nm. A medium refractive index layer was formed.

(Preparation of Coating Solution for High Refractive Index Layer) To 246.7 g of the above titanium dioxide dispersion, 14.16 g of dipentaerythritol hexaacrylate, 1.68 g of a photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy), Photosensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.)
0.56 g and 160.82 g of methyl ethyl ketone were added, stirred at room temperature for 30 minutes, and filtered with a 1 μm polypropylene filter to prepare a coating solution for a high refractive index layer.

(Formation of High Refractive Index Layer) On the medium refractive index layer,
The coating solution for a high refractive index layer was applied with a bar coater, and the layer was cured by irradiating ultraviolet rays. Thus, a high refractive index layer having a thickness (dry film thickness) of 129 nm was formed.

(Surface Treatment of Silica Fine Particles) A silane coupling agent (KBM-) was added to 300 g of a methanol dispersion of silica fine particles (methanol silica sol, manufactured by Nissan Chemical Industries, Ltd.).
503: 4.5 g of Shin-Etsu Chemical Co., Ltd.) and 0.1 N
3 g of hydrochloric acid was added, the mixture was stirred at room temperature for 5 hours, and then left for 5 days to obtain a dispersion of silane-coupled silica fine particles.

(Preparation of coating liquid for low refractive index layer) 16.3 g of dipentaerythritol hexaacrylate, photopolymerization initiator (Irgacure 907, Ciba-Geigy) 0.6
5 g and a photosensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.) were added to isopropyl alcohol 806.
g and 248 g of diacetone alcohol,
After adding 72.36 g of a dispersion of silica fine particles whose surface was subjected to silane coupling treatment and stirring at room temperature for 30 minutes,
The solution was filtered through a μm polypropylene filter to prepare a coating solution for a low refractive index layer.

(Formation of Low Refractive Index Layer) On the high refractive index layer,
The coating liquid for the low refractive index layer has a thickness of 95 n using a wire bar.
m, dried at 120 ° C., cross-linked by irradiating ultraviolet rays, and then allowed to cool to room temperature to form a low refractive index layer, thereby forming an antireflection film.

Example 5 (Formation of Undercoat Layer) As in Example 1, an undercoat layer (a) and a second undercoat layer (a) were formed on one surface of a transparent support. A latex made of vinylidene chloride-acrylic acid-methyl acrylate copolymer was applied to a thickness of 120 nm on the surface of the transparent support on which the undercoat layer was not provided, to form an undercoat layer (b).

(Formation of Second Undercoat Layer) On the undercoat layer (b), an acrylic latex (HA16, manufactured by Nippon Acrylic Co., Ltd.) was applied to a thickness of 50 nm to form a second undercoat layer (b). Was formed. (Formation of Filter Layer) A filter layer was formed on the second undercoat layer (b) in the same manner as in Example 1.

(Formation of Hard Coat Layer and Low Refractive Index Layer) A hard coat layer and a low refractive index layer were formed on the filter layer in the same manner as in Example 2 to form an antireflection film.

Example 6 (Formation of Undercoat Layer) After a corona discharge treatment was applied to both surfaces of a transparent polyethylene terephthalate film (transparent support) having a thickness of 100 μm, styrene was applied to one surface in the same manner as in Example 2.
A butadiene copolymer latex having a thickness of 180
The undercoat layer (b) was formed by coating to a thickness of μm.
On the surface where the undercoat layer (b) of the transparent support is not provided,
A latex comprising vinylidene chloride-acrylic acid-methyl methacrylate copolymer was applied to a thickness of 130 nm to form an undercoat layer (a). On the undercoat layer (a), an acrylic latex (HA16, manufactured by Nippon Acrylic Co., Ltd.) was applied to a thickness of 50 nm to form a second undercoat layer (a).

(Formation of Hard Coat Layer) 25 parts by weight of dipentaerythritol hexaacrylate (DPHA,
Nippon Kayaku Co., Ltd.), 25 parts by weight of a urethane acrylate oligomer (VU-6300B, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), 2 parts by weight of a photopolymerization initiator (Irgacure-
907, Ciba-Geigy) and 0.5 parts by weight of a sensitizer (Kayacure-DETX, manufactured by Nippon Kayaku Co., Ltd.)
It was dissolved in 0 parts by weight of methyl ethyl ketone. The obtained coating solution was applied onto the undercoat layer (b) using a bar coater, dried, and then irradiated with ultraviolet rays to form a hard coat layer (layer thickness: 6 μm).

(Formation of Low Refractive Index Layer) On the hard coat layer, a coating liquid for a low refractive index layer containing the reactive fluoropolymer used in Example 1 was applied in the same manner as in Example 1 to obtain a low refractive index layer. A rate layer was formed.

(Formation of Filter Layer) To 94.8 g of methyl ethyl ketone, 5.0 g of polyvinyl butyral (2000 L of Denkabutyral, manufactured by Denki Kagaku Kogyo Co., Ltd.) and 0.2 g of the following dye were added and dissolved by stirring at room temperature for 30 minutes. And filtered through a 1 μm polypropylene filter. The obtained coating liquid was turned off using a bar coater on the second undercoat layer (a), and dried at 120 ° C. for 5 minutes to form a filter layer, thereby forming an antireflection film.

[0054]

Embedded image

Comparative Example 1 An antireflection film was formed in the same manner as in Example 1 except that the undercoat layer and the second undercoat layer were not formed.

Comparative Example 2 An antireflection film was formed in the same manner as in Example 2 except that the undercoat layer was not formed.

The layer constitutions of the antireflection films prepared in Examples 1 to 6 and Comparative Examples 1 and 2 are shown below.

──────────────────────────────────── Example 1 Example 2 Example 3 Example 4 ──────────────────────────────────── Low refractive index layer High refractive index layer Medium refractive index layer Low Refractive index layer Hard coat layer Low refractive index layer Second undercoat layer b Second undercoat layer b Low refractive index layer Hard coat layer Undercoat layer b Undercoat layer b Transparent support Transparent support Transparent support Transparent support Undercoat layer Undercoat layer Undercoat Layer a Undercoat layer a Second undercoat layer Filter layer Second undercoat layer a Second undercoat layer a Filter layer Filter layer Filter layer ─────────────

５ Example 5 Example 6 Comparative Example 1 Comparative Example 2 ──────────────────────────────────── Low refractive index layer Hard coat layer Filter layer Low refractive index layer Second undercoat layer b Hard coat layer Low refractive index layer Undercoat layer b Undercoat layer b Low refractive index layer Hard coat layer Transparent support Transparent support Transparent support Transparent support Undercoat layer a Undercoat layer a Filter layer Filter layer Second undercoat Layer a Second undercoat layer a Filter layer

(Evaluation of Optical Properties of Antireflection Film)
6 and the peak absorption wavelength, half width, and average reflectance in the wavelength region of 450 to 650 nm of the antireflection films prepared in Comparative Examples 1 and 2. The results are shown in Table 1.

(Evaluation of Adhesion of Antireflection Film Constituent Layer) On the back surface of the antireflection film prepared in Examples 1 to 6 and Comparative Examples 1 and 2 (the surface on which the low refractive index layer is not provided), acrylic A system pressure-sensitive adhesive was applied to a thickness of 30 μm, the surface was adhered to glass, and the antireflection layer side was subjected to a tape peeling test by a cross-cut method. A sample adhered to glass was irradiated with visible light of 150,000 lux from the antireflection layer side by a xenon lamp for 100 hours, and then a similar tape peeling test was performed. If the area of the peeled part is 70% or more, C, 30 to 7
0% was evaluated as B, and less than 30% was evaluated as A. The results are shown in Table 1.

[0062]

[Table 1] Table 1 評 価 Evaluation of optical properties Adhesion evaluation Reflection Prevention film Absorption maximum wavelength Half width Average reflectance Before irradiation After irradiation ──────────────────────────────────── Example 1 585 nm 30 nm 1.31% A A Example 2 585 nm 30 nm 1.54% A B to A Example 3 585 nm 30 nm 1.21% A A Example 4 585 nm 30 nm 0.52% A A Example 5 585 nm 30 nm 1.25% AB -A Example 6 574 nm 38 nm 1.27% A A Comparative Example 1 585 nm 30 nm 1.28% CC Comparative Example 2 585 nm 30 nm 1.22% BC ────────────────────────── ─

(Evaluation of Filter Function) Plasma Display Panel (PDS4202J-H, Fujitsu Limited)
), The anti-reflection film (the surface on the side where the low refractive index layer is not provided) prepared in Examples 1 to 6 is attached, and the color is visually improved. It was confirmed. That is, it was confirmed that in each of the filters, the conventional orange-containing red was improved to pure red, the greenish blue to vivid blue, and the yellowish white to pure white. It was also confirmed that external light reflection by the surface was suppressed.

[Brief description of the drawings]

FIG. 1 is a schematic cross-sectional view showing a layer configuration of an antireflection film in which a filter layer is provided on a side opposite to a transparent support from an antireflection layer.

FIG. 2 is a schematic cross-sectional view showing a layer configuration of an antireflection film in which a filter layer and an antireflection layer are provided on the same side of a transparent support. DESCRIPTION OF SYMBOLS 1 Transparent support 2 Undercoat layer 3 Filter layer 4 Low refractive index layer 5 Hard coat layer 6 High refractive index layer 7 Medium refractive index layer

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2H091 FA01X FA37X FB02 FB12 FB13 FC25 FD06 FD24 GA16 KA01 2K009 AA12 AA15 BB24 BB28 CC03 CC09 CC23 CC24 CC26 EE00 EE01 4F100 GB90

Claims (8)

[Claims] 1. An antireflection film comprising: a filter layer containing a dye and a polymer binder; a transparent support; and a low refractive index layer having a refractive index lower than the refractive index of the transparent support. An anti-reflection method, wherein an undercoat layer containing a polymer having a glass transition temperature of 25 ° C. or lower or an undercoat layer having a rough surface on the filter layer side is provided between the filter layer and the transparent support. film. 2. The filter layer having a wavelength of 560 to 62.
The antireflection film according to claim 1, which has an absorption maximum in a range of 0 nm. 3. The antireflection film according to claim 1, wherein a hard coat layer having a hardness higher than the hardness of the transparent support is provided between the transparent support and the low refractive index layer. 4. The antireflection film according to claim 3, wherein the hard coat layer contains a crosslinked polymer. 5. An antireflection film comprising a transparent support, a filter layer containing a dye and a polymer binder, and a low refractive index layer having a refractive index lower than that of the transparent support, which are laminated in this order. An anti-reflection method, wherein an undercoat layer containing a polymer having a glass transition temperature of 25 ° C. or lower or an undercoat layer having a rough surface on the filter layer side is provided between the transparent support and the filter layer. film. 6. The filter layer has a wavelength of 560 to 62.
The antireflection film according to claim 5, which has an absorption maximum in a range of 0 nm. 7. The antireflection film according to claim 5, wherein a hard coat layer having a hardness higher than the hardness of the transparent support is provided between the filter layer and the low refractive index layer. 8. The antireflection film according to claim 7, wherein the hard coat layer contains a crosslinked polymer.