JP2010060617A - Near-infrared absorption filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To stably maintain a dye having the maximum absorption wavelength in 800 to 1,100 nm, 640 to 700 nm, or 570 to 600 nm with the lapse of time and to maintain the shield effect for a long period of time, in a liquid crystal display. <P>SOLUTION: A near-infrared absorption filter is provided, in which at least one of a hard coat layer and a pressure sensitive adhesive layer includes resin particulate, and the resin particulate includes at least one type of dye selected from a group consisting of: a near-infrared absorption dye having the maximum absorption wavelength in 800 to 1,100 nm; a dye having the maximum absorption wavelength in 640 to 750 nm; and a dye having the maximum absorption wavelength in 570 to 600 nm. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a near infrared absorption filter. Specifically, the present invention relates to a near-infrared absorption filter in which resin fine particles contain a dye having a maximum absorption wavelength in a specific wavelength range.

  In recent years, flat panel displays have attracted attention as displays that can be made thin and have a large screen. Among them, a plasma display panel (PDP), a liquid crystal display (LCD), and the like are widely spread in the market and attract attention. However, these flat panel displays generate near-infrared light, and this near-infrared light can cause malfunctions in peripheral electronic devices such as remote controls such as televisions for home appliances, coolers, and video decks, as well as transmission optical communication. It is necessary to install an infrared absorption filter that cuts off this near infrared ray. In the case of a liquid crystal display, near-infrared rays of about 800 to 1100 nm, specifically 880 and 1100 nm, are particularly likely to be generated at the time of startup, and the near-infrared rays in these ranges are likely to cause malfunction of peripheral devices. The filter which cuts off near infrared rays is required.

  For the above purpose, various filters have been proposed in which a dye that absorbs wavelengths in the near infrared region is blended in a resin. For example, in Patent Document 1, a near-infrared absorbing layer formed of a near-infrared-absorbing composition in which a diimonium compound having a specific structure and a phthalocyanine compound having a specific structure are mixed in an acrylic resin is used as a transparent group. A near infrared absorption filter provided on one surface of a material has been proposed. Patent Document 2 discloses an infrared absorption filter containing a diimonium salt-based compound, a phthalocyanine-based compound and a nickel complex-based compound as a near-infrared absorbing dye, and a polyester resin. The filter has a high visible light transmittance and efficiently blocks near infrared rays of 800 to 1200 nm.

  Further, since the wavelength of 570 to 600 nm is orange light that blurs the image, it is necessary to install a filter that cuts such a wavelength range. For example, Patent Document 3 proposes a filter in which a resin layer containing a dye having a maximum absorption wavelength at 570 to 600 nm is formed on a transparent substrate (see, for example, Patent Document 3).

  On the other hand, in recent years, the flow of increase in information amount has become very rapid, and for example, the recording wavelength has been required to be shortened so that a CD-R is changing to a DVD ± R as a large capacity optical disk. For this reason, it is considered that the optical communication system currently used in the same manner at a wavelength of 800 to 900 nm used for mobile phones and game machines will be shortened to a wavelength of around 700 nm in the future. However, although the current flat panel display has extra light emission at a wavelength of 700 to 750 nm, there is no one that cuts the wavelength of 700 to 750 nm, and there is a possibility of inducing a malfunction of transmission optical communication. It is considered that it will be necessary in the future to cut light in this wavelength range.

  At the same time, light with a wavelength of 640 to 700 nm may be used for some LCDs that have a weak red color. However, unlike pure red with a wavelength range of 610 to 635 nm, the color tone is called “crimson”. Therefore, in the field of flat panel displays, it is not necessarily a preferable color tone, and in order to reproduce pure red, it is necessary to cut light in this wavelength range.

  As described above, a conventional filter having a dye that removes light of an appropriate wavelength contains a dye having a wavelength to be cut in the resin at the maximum absorption wavelength, and is applied to a substrate. However, since the pigment is directly mixed and kneaded in the resin, there is a case where the pigment has low durability.

In order to solve such a problem, Patent Document 4 proposes a resin molded product containing a near infrared absorber in the hard coat layer.
JP 2007-121578 A JP 2001-264532 A JP 2002-200711 A Japanese Patent Laid-Open No. 10-193522

  However, even if the near-infrared absorber is included in the hard coat layer, it has been difficult to say that the near-infrared absorber has sufficient durability, particularly heat resistance and light resistance.

  Therefore, in flat panel displays, there has been a demand for a form in which a dye having a maximum absorption wavelength at 800 to 1100 nm, 640 to 700 nm, or 570 to 600 nm is stably maintained over time, and the blocking effect is maintained for a long time. .

  As a result of intensive investigations in view of the above circumstances, the inventors of the present invention have a long-term blocking effect by including resin fine particles in the hard coat layer or the pressure-sensitive adhesive layer, and by incorporating a dye that absorbs a specific wavelength into the fine particles. As a result, the present invention was completed.

  That is, in the present invention, at least one of the hard coat layer or the pressure-sensitive adhesive layer has resin fine particles, and the resin fine particles have a near-infrared absorbing dye having a maximum absorption wavelength at 800 to 1100 nm; a maximum absorption wavelength at 640 to 750 nm. And a near-infrared absorption filter containing at least one dye selected from the group consisting of a dye having a maximum absorption wavelength at 570 to 600 nm.

  Since the near-infrared absorption filter of the present invention has high durability of the contained pigment, for example, the effect of preventing malfunction of the optical communication system is exhibited for a long time.

  The present invention has a hard coat layer having resin fine particles or an adhesive layer having resin fine particles, and the resin fine particles have a near infrared absorption dye having a maximum absorption wavelength at 800 to 1100 nm; a maximum absorption wavelength at 640 to 750 nm. And a near-infrared absorption filter containing at least one dye selected from the group consisting of a dye having a maximum absorption wavelength at 570 to 600 nm (hereinafter also referred to as a specific wavelength absorption dye).

  FIG. 1 shows an antiglare film for a flat panel display which is an embodiment of the near-infrared absorption filter of the present invention (hereinafter also referred to as a first embodiment). As shown in FIG. 1, in the antiglare film 10 of the first embodiment, an antiglare layer 4 that is a hard coat layer is laminated on a transparent substrate 1. The antiglare layer 4 includes a transparent resin 2 and resin fine particles 3. The resin fine particles 3 form irregularities on the surface of the antiglare layer 4, and the irregularities scatter reflected light from outside light (light from a fluorescent lamp or the like), and also cause internal scattering of the transparent resin and the particles. , Reflection can be prevented. The anti-glare layer has fine irregularities formed on the surface thereof, and the reflected light of external light (light from a fluorescent lamp or the like) is scattered by such irregularities, and reflection on the screen is suppressed. The antiglare film is usually disposed in the outermost layer of the flat panel display.

  The specific wavelength absorbing dye is mixed in the resin fine particles 3. By containing the pigment in the resin fine particles 3, the pigment is less likely to come into direct contact with moisture, ions, oxygen, and the like, so that degradation of the pigment is reduced. Therefore, the durability of the pigment is improved and the blocking effect for a long time is maintained.

  In order to form the unevenness on the antiglare layer, it is not limited to the form formed by the resin fine particles, and other methods include sandblasting, etching, and a method of transferring the unevenness. The irregularities may be formed by inorganic fine particles other than the resin fine particles. As the inorganic fine particles, titanium oxide, silica or the like is used. Only one kind of inorganic fine particles may be used, or two or more kinds may be mixed and used.

  The fine irregularities on the surface of the antiglare layer preferably have a ten-point average roughness (Rz) of about 0.1 to 2 μm. The ten-point average roughness Rz is, for example, 3 mm in a certain direction on the concavo-convex structure surface through a measuring needle having a diameter of 1 mm with a tip portion made of diamond having a conical shape with an apex angle of 55 degrees in accordance with JIS B0601-1994. Is calculated from a surface roughness curve in which the change in the vertical direction of the measuring needle is measured and recorded.

  Although the thickness of an anti-glare layer is not specifically limited, It is preferable that it is 1-50 micrometers. Such a range is preferable because the antiglare effect is appropriate.

  The content of the resin fine particles in the antiglare layer (in the case where the specific wavelength absorbing dye is included, the whole resin fine particles including the specific wavelength absorbing dye) is obtained from the effect of the fine particles, so the transparent resin constituting the antiglare layer It is preferable that it is 5-50 mass% with respect to 100 mass%, and it is more preferable that it is 10-30 mass%.

  The antiglare film contains various improvements and modifications in addition to the first embodiment as long as it is a film having antiglare properties. For example, the form in which another layer exists between a transparent base material and a glare-proof layer is also contained. Examples of the other layers include a light diffusion layer (light diffusible hard coat layer), an electromagnetic wave shielding layer, a color adjustment layer, and an impact absorption layer described in detail below.

  The electromagnetic wave shielding layer is a film in which a metal mesh is patterned on a film by etching, printing, etc., or a film in which a metal is deposited on a fiber mesh and embedded in a resin. used.

  The shock absorbing layer is for protecting the display device from external impact. It is preferably used in an optical filter that does not use a support. As the shock absorber, ethylene-vinyl acetate copolymer, acrylic polymer, polyvinyl chloride, urethane-based, silicon-based resin as disclosed in JP-A-2004-246365 and JP-A-2004-264416 However, it is not limited to these.

  Moreover, the form of FIG. 2 is mentioned as a modification of the first embodiment. The antiglare film 20 of FIG. 2 has an antireflection layer 6 on the antiglare layer 4. The antireflection layer has the effect of suppressing surface reflection and reflection of the screen by utilizing optical interference. 2 that have the same reference numerals as those in FIG. 1 have the same functions, and a description thereof will be omitted.

Examples of the antireflection layer include a single layer of a low refractive index layer (LR), and a case in which a high refractive index layer and a low refractive index layer are stacked in this order on a hard coat layer (AR). Preferably, it is LR consisting of a single layer having a low refractive index. Conventionally known low refractive index layers and high refractive index layers are used. Specifically, the antireflection layer includes a thin film of an inorganic material such as a metal oxide, fluoride, silicide, boride, carbide, nitride, sulfide, and a refractive index of an acrylic resin, a fluorine resin, or the like. In the case of the former, there is a method of forming a single layer or a multilayer on a transparent substrate using vapor deposition or sputtering. is there. In the latter case, the surface of the transparent substrate is reflected on a transparent film using a knife coater such as a comma coater, a fountain coater such as a slot coater or a lip coater, a gravure coater, a flow coater, a spray coater or a bar coater. There are methods of applying a protective coating. As the low refractive index layer, silica, magnesium fluoride, fluorine-based resin or the like is preferably used, and as the high refractive index layer, TiO ₂ , Y ₂ O ₃ , La ₂ O ₃ , ZrO ₂ , Al ₂ O _{3 are used.} Etc. are preferably used.

  Another preferred embodiment of the present invention is the antiglare film for flat panel display shown in FIG. 3 (hereinafter also referred to as the second embodiment). The antiglare film in FIG. 3 has a form in which a light diffusible hard coat layer 5 is laminated on a transparent substrate 1 and an antiglare layer 7 is laminated thereon. The light diffusing hard coat layer 5 is formed by dispersing resin fine particles 3 in a transparent resin 2 ′. In the present embodiment, the resin fine particle 3 contains a specific wavelength absorbing dye. The antiglare layer 7 includes fine particles 11 for forming irregularities. The fine particles 11 may be resin fine particles or inorganic fine particles. Details of the resin fine particles and inorganic fine particles will be described in the column of resin fine particles below. As an anti-glare layer, it is not limited to the said form, As long as it has anti-glare property, a conventionally well-known anti-glare layer can be used. For example, you may use the glare-proof layer 4 containing the specific wavelength absorption pigment | dye used in 1st Embodiment. 3 that have the same reference numerals as those in FIG. 1 have the same functions, and a description thereof will be omitted. The transparent resin 2 in the antiglare layer and the transparent resin 2 'in the light diffusion layer may be the same type of resin or different types of resins.

  The light diffusing hard coat layer 5 is also the one in which the resin fine particles 3 are dispersed in the transparent resin 2 ′. The light diffusing hard coat layer diffuses the light from the display within the layer, thereby reducing the proportion of light rays that are emitted in the normal direction out of the light emitted from the concavo-convex portion of the antiglare layer 7. It functions to increase the proportion of light rays that are emitted in directions other than the line direction.

  In the light diffusing hard coat layer, the difference in refractive index between the resin fine particles and the translucent resin is preferably 0.01 to 0.5. The thickness of the light diffusing hard coat layer is preferably 1 to 50 μm although it depends on the resolution of the display. Such a range is preferable because the light diffusion effect is appropriate. Other points and matters relating to the formation of the layer are the same as those already described as relating to the antiglare layer 4.

  The light diffusing hard coat layer 5 needs to be applied flat so as not to form particularly fine irregularities on the upper surface. The lower the degree of flatness, the lower the coating suitability of the antiglare layer on the light diffusing hard coat layer. In order to obtain more effective light diffusibility, the upper surface of the light diffusible hard coat layer is preferably flat. In addition, the light diffusible hard coat layer preferably has an internal haze of 8 to 50, more preferably 15 to 30. If the upper limit is exceeded, when the antiglare film is applied to the display, the image appears whitened, and if it is less than the lower limit, the effect of preventing scintillation is reduced.

  Another preferred embodiment of the present invention is the antiglare film for flat panel display shown in FIG. 4 (hereinafter also referred to as the third embodiment). The anti-glare film 40 of FIG. 4 is a form which has the anti-glare layer 7 laminated | stacked on the transparent base material 1, and has the adhesive layer 8 in the side facing the anti-glare layer of a transparent base material. The antiglare layer 7 is formed by dispersing fine particles 11 for forming irregularities in the transparent substrate 2. The fine particles 11 may be resin fine particles or inorganic fine particles. The antiglare layer 7 is not limited to the above-described form, and a conventionally known antiglare layer can be used as long as it has antiglare properties. The pressure-sensitive adhesive layer 8 is provided to adhere an antiglare film and a polarizer when used in another member, for example, a liquid crystal display. The pressure-sensitive adhesive layer 8 includes resin fine particles 3 containing a specific wavelength absorbing dye. By including the dye in the resin fine particles, it is difficult for the dye to come into direct contact with moisture, ions, oxygen, etc., so that the deterioration of the dye is reduced, the durability of the dye is improved, and the blocking effect is maintained for a long time. As described above. Since the resin fine particles can be easily and stably contained in the pressure-sensitive adhesive layer, even if the pressure-sensitive adhesive layer has the resin fine particles, the effect of the present invention is significantly obtained.

  As other suitable embodiment of the near-infrared absorption filter of this invention, the polarizing plate which has an anti-glare film, a polarizer, and an adhesive layer is mentioned. FIG. 5 shows an embodiment of a polarizing plate (hereinafter also referred to as a fourth embodiment). The polarizing plate 60 in FIG. 5 is formed by laminating an adhesive layer 8 ′, a protective film 9, a polarizer 12, and an antiglare film 50 in this order. The pressure-sensitive adhesive layer 8 ′ includes resin fine particles 3 containing a specific wavelength absorbing dye. By including the dye in the resin fine particles, it is difficult for the dye to come into direct contact with moisture, ions, oxygen, etc., so that the deterioration of the dye is reduced, the durability of the dye is improved, and the blocking effect is maintained for a long time. As described above. Since the resin fine particles can be easily and stably contained in the pressure-sensitive adhesive layer, even if the pressure-sensitive adhesive layer has the resin fine particles, the effect of the present invention is significantly obtained. The pressure-sensitive adhesive layer 8 ′ is provided for bonding a polarizing plate and a liquid crystal cell (or a glass substrate in the liquid crystal cell) when used for another member, for example, a liquid crystal display.

  As a polarizer, for example, a film made of a suitable vinyl alcohol-based polymer according to the prior art such as polyvinyl alcohol or partially formalized polyvinyl alcohol, a dyeing treatment with a dichroic substance made of iodine or a dichroic dye, a stretching treatment In addition, an appropriate treatment such as a crosslinking treatment can be performed in an appropriate order and method, and an appropriate material that transmits linearly polarized light when natural light is incident can be used. In particular, those excellent in light transmittance and degree of polarization are preferable. The thickness of the polarizer is generally 5 to 80 μm, but is not limited thereto. Examples of the protective film include a film made of a cellulose resin such as triacetyl cellulose or a polymer resin having an alicyclic structure. However, the alicyclic resin is excellent in terms of transparency, low birefringence, dimensional stability, and the like. Polymer resins having the formula structure are preferred. Examples of the polymer resin having an alicyclic structure include those described in the column of the transparent substrate used in the antiglare film of the present invention described later.

  In 4th Embodiment, the anti-glare film 50 may use the anti-glare film of the said 1st-3rd embodiment and this deformation | transformation, and may use a conventionally well-known anti-glare film. Since the transparent base material in the anti-glare film 50 is arrange | positioned so that the polarizer 12 may be contact | connected, a transparent base material plays the role which protects the surface of the polarizer on the opposite side to a protective film. The arrangement of the pressure-sensitive adhesive layer 8 ′ in the laminate is not limited to the above form, and may be arranged between the polarizer and the protective film, and the pressure-sensitive adhesive layer may be formed on both sides of the protective film. .

  The first to fourth embodiments, which are preferred embodiments of the present invention, have been described above. However, the present invention is not limited to the above-described embodiments, and the fine particles containing a specific wavelength absorbing dye are hard coat layers or adhesives. As long as it is contained in the agent layer, it is included in the present invention.

  In the present invention, since the resin fine particles contain near-infrared absorbing dyes, various laminate forms can be used in the near-infrared absorbing filter of the present invention as long as the resin fine particles are present in the hard coat layer or the pressure-sensitive adhesive layer. Is included. In 1st-4th embodiment, although demonstrated using the anti-glare film or the polarizing plate, the near-infrared absorption filter is not restrained by the name, The resin fine particle containing a pigment | dye is a hard-coat layer or adhesion. It suffices if it is present in the drug layer.

  Hereinafter, each member demonstrated above is demonstrated.

(Hard coat layer)
The transparent resin constituting the hard coat layer is not particularly limited as long as it has properties as a binder, has sufficient strength as a film after the hard coat layer is formed, and is transparent. Specific examples include thermosetting resins, thermoplastic resins, and active energy ray curable resins (such as ultraviolet ray curable resins and electron beam curable resins). In terms of film strength and workability, active energy is used. A linear curable resin is preferred. For example, transparent resins described in JP-A Nos. 2003-302506 and 2007-062102 can be used.

  Among these, a thermosetting resin or a radiation curable resin having a refractive index of 1.40 to 1.70 is desirable because it can improve the hardness and scratch resistance of the hard coat layer. In particular, the use of an ultraviolet curable resin as the radiation curable resin is desirable because a hard coat layer can be easily and efficiently formed by a curing treatment by irradiation with ultraviolet rays.

  The active energy ray-curable resin is a resin composed of a polyfunctional monomer and / or a monofunctional monomer that forms a cured film or the like by being polymerized by irradiation with active energy rays such as ultraviolet rays and electron beams. Point to. 1 type (s) or 2 or more types can be used for a polyfunctional monomer and a monofunctional monomer, respectively.

  Active energy ray curable resins include acrylic resins, polyether resins, epoxy resins, alkyd resins, spiroacetal resins, polybutadiene resins, polythiol polyene resins, polyester resins, urethane resins, amide resins. There are various types such as oligomers or prepolymers such as (meth) acrylates of polyfunctional compounds such as resins, silicone resins, epoxy resins, and polyhydric alcohols.

  For example, an acrylic ultraviolet curable resin having an ultraviolet polymerizable functional group (for example, vinyl group), in particular, an acrylic monomer or oligomer having 2 or more, more preferably 3 to 6, the above functional groups What added the polymer to this and mix | blended the ultraviolet-ray polymerization initiator are used. Specifically, examples of the acrylic monomer having a polyfunctional vinyl group include ethylene glycol di (meth) acrylate; di (meth) acrylate of polyethylene glycol such as diethylene glycol or triethylene glycol; propylene glycol di (meth) ) Acrylate; di (meth) acrylate of polypropylene glycol such as dipropylene glycol or tripropylene glycol; neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol or (Meth) acrylate of a dihydric alcohol such as 1,4-dimethylolbenzene; di (meth) of a dihydric alcohol obtained by reacting the dihydric alcohol with ethylene oxide and / or propylene oxide Trimethylolpropane tri (meth) acrylate; trimethylolpropane di (meth) acrylate; glycerin di (meth) acrylate; glycerin tri (meth) acrylate; reaction of ethylene oxide and / or propylene oxide with trimethylolpropane or glycerin Di (meth) acrylate and tri (meth) acrylate of trihydric alcohol obtained in this way; pentaerythritol tri (meth) acrylate; pentaerythritol tetra (meth) acrylate; obtained by reacting pentaerythritol with ethylene oxide and / or propylene oxide Polyfunctional (meth) acrylates such as tri (meth) acrylates and tetra (meth) acrylates of tetrahydric alcohols; (meth) acrylic in the same molecule It may be mentioned 2-vinyloxyethyl (meth) acrylate and a vinyl ether group, a 2- (2-vinyloxy) ethyl (meth) heterologous polymerizable compounds such acrylate.

  The active energy ray-curable resin preferably has a weight average molecular weight of 5,000 to 200,000, more preferably 10,000 to 100,000, from the viewpoint of strength and transparency as a hard coat layer. preferable. In addition, the value measured on condition of the following using a gel permeation chromatograph (GPC) is employ | adopted for a weight average molecular weight.

  A known initiator may be used for the active energy ray curable resin as necessary. Examples of the initiator include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone, 2-hydroxy- Acetophenones such as 2-methyl-1- [4- (1-methylvinyl) phenyl] propanone oligomer; benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; benzophenone, -Methyl benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, 3,3 ', 4,4'-tetra (t-butylperoxylcarbonyl) benzophenone, 2,4,6- Benzophenones such as trimethylbenzophenone, 4-benzoyl-N, N-dimethyl-N- [2- (1-oxo-2-propenyloxy) ethyl] benzenemethananium bromide, (4-benzoylbenzyl) trimethylammonium chloride; 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2- (3-dimethylamino-2-hydroxy) -3,4- Dimethyl-9H-thio Thioxanthones such as xanthone-9-Onmesokurorido and the like. Among these, acetophenones and benzophenones are preferable. Of these, 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one are preferable. As the initiator, a commercially available product such as Irgacure 184 (manufactured by Ciba Specialty Chemicals) can be used.

  The thermosetting resin or reactive resin is capable of forming a crosslinked structure resulting from addition reaction, condensation reaction, etc. by heating, active energy ray irradiation, drying or other means after the film formation process or film formation, Specifically, for example, phenolic resins such as novolak resins and resol resins, amino resins such as urea resins, melamine resins, and benzoguanamine resins, various alkyd resins, unsaturated polyester resins, curable acrylic resins, isocyanate group-containing polyesters And urethane-modified resins such as isocyanate group-containing polyethers, polyamine resins, and epoxy resins. The thermosetting resin preferably has a weight average molecular weight of 5,000 to 200,000, more preferably 10,000 to 100,000, from the viewpoint of strength and transparency as a hard coat layer.

  As the thermoplastic resin, those having a weight average molecular weight of about 10,000 to 100,000 are preferably used. Specific examples thereof include vinyl chloride polymers such as vinyl chloride polymers and vinyl chloride-vinylidene chloride copolymers. Resin, vinyl acetate polymer, vinyl acetate-ethylene copolymer, vinyl acetate-based resin such as vinyl acetate-methyl methacrylate copolymer, (meth) acrylate ester (co) polymer, (meth) acrylate ester- Acrylonitrile copolymer, (meth) acrylic ester resin such as (meth) acrylic ester-styrene copolymer, styrene resin such as styrene-butadiene-acrylonitrile copolymer, poly (ε-caprolactam), adipine Polyamide resins such as condensates of acid and hexamethylene diamine, terephthalic acid and ethylene glycol Polyester resins such as condensates with alcohol, condensates of adipic acid and ethylene glycol, polyolefin resins such as polyethylene, chlorinated polypropylene, carboxyl-modified polyethylene, polyisobutylene, polybutadiene, cellulose acetate, cellulose propionate, Examples thereof include cellulose derivatives such as nitrocellulose and other butyral resins. As these resins, commercially available products may be used as they are, or those synthesized by a generally known method may be used.

  The thickness of the hard coat layer is not particularly limited, but is preferably 0.1 to 30 μm, more preferably 0.5 to 20 μm, in order to sufficiently exhibit the function as the hard coat layer.

  In addition, the hard coat layer of the present invention preferably exhibits a hardness of HB or higher in a pencil hardness test (test plate is a glass plate) represented by JIS K5600-5-4, and more preferably exhibits a hardness of H or higher. More preferably, it exhibits a hardness of 4H or more.

  The hard coat layer may contain inorganic fine particles in addition to the following resin fine particles. As the inorganic fine particles, titanium oxide, silica and the like are used. Only one kind of inorganic fine particles may be used, or two or more kinds may be mixed and used. The content of the inorganic fine particles in the hard coat layer is preferably 5 to 50% by mass and more preferably 10 to 30% by mass with respect to 100% by mass of the hard coat layer. The average particle size of the inorganic fine particles is preferably from 0.1 to 15 μm, and more preferably from 0.5 to 5 μm.

  Moreover, you may add another additive suitably to a hard-coat layer.

(Resin fine particles)
As resin fine particles, styrene resin, acrylic resin, acrylic-styrene copolymer resin, formaldehyde resin, amino resin, urea resin, phenol resin, melamine resin, benzoguanamine resin, xylene resin, polycarbonate Fine particles made of a resin such as a polyethylene resin, a polyethylene resin, or a polyvinyl chloride resin are preferred. From the viewpoint of transparency, fine particles made of acrylic resin, acrylic-styrene copolymer resin, and polystyrene resin are preferable, and fine particles made of acrylic resin, acrylic-styrene copolymer resin, and polystyrene resin are more preferable. . The resin fine particles may be used alone or in combination of two or more. The resin used for the resin fine particles may be obtained by synthesis or a commercially available product.

  Examples of the styrene resin include polystyrene resins and other copolymers of styrene and other monomers. The polystyrene-based resin is obtained by polymerizing a styrene-based monomer as a main component, and may contain another monomer copolymerizable with styrene. Styrene monomers include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-methoxystyrene, p-tert-butylstyrene, p-phenylstyrene, o- Examples include chlorostyrene, m-chlorostyrene, and p-chlorostyrene. These styrene monomers may be used alone or in combination of two or more. In the present invention, the main component refers to those containing 70 to 100% by mass in all monomers, preferably 85 to 100% by mass or more, more preferably 95 to 100% by mass. . Examples of other monomers copolymerizable with styrene include the following (meth) acrylic monomers. In addition, it is preferable that the weight average molecular weight of the microparticles | fine-particles which consist of a polystyrene-type resin is 10,000-1,000,000, and it is more preferable that it is 50,000-500,000.

  Other monomers used in the copolymer of styrene and other monomers include divinylbenzene, divinylnaphthalene, aromatic divinyl compounds such as derivatives thereof, N, N-divinylaniline, divinyl ether, divinyl. It is also possible to use a crosslinking agent such as sulfide and divinylsulfonic acid. Among these, a styrene-divinylbenzene copolymer is preferable.

  The acrylic resin is polymerized using a (meth) acrylic monomer as a main component, and contains other monomers copolymerizable with the (meth) acrylic monomer. Also good. Examples of (meth) acrylic monomers include acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, dodecyl acrylate, stearyl acrylate, 2-ethylhexyl acrylate, and acrylic. Tetrahydrofurfuryl acid, methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, etc. Is mentioned. These (meth) acrylic monomers may be used alone or in combination of two or more. Other monomers copolymerizable with the (meth) acrylic monomer include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-methoxystyrene, p- Styrenic monomers such as tert-butylstyrene, p-phenylstyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, ethylene, propylene, butylene, vinyl chloride, vinyl acetate, acrylonitrile, acrylamide, methacrylamide, N -Vinylpyrrolidone etc. are mentioned. In addition, it is preferable that the weight average molecular weight of the microparticles | fine-particles which consist of acrylic resins is 10,000-1,000,000, and it is more preferable that it is 50,000-500,000.

  Furthermore, when obtaining resin particles having a cross-linked structure between molecules, it is possible to copolymerize (meth) acrylic monomers having a plurality of polymerizable double bonds in the molecule with the above (meth) acrylic monomers. It is. Examples of such crosslinkable (meth) acrylic monomers include trimethylolpropane triacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, decaethylene glycol dimethacrylate, and pentamethacrylate. (Meta) such as decaethylene glycol, pentamethaethylene dimethacrylate, ethylene glycol 1,3-butylene dimethacrylate, allyl methacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate, diethylene glycol dimethacrylate Acrylic monomers can be mentioned, and a plurality of these can be used in combination. Further, within the range not inhibiting the blending ratio of (meth) acrylic monomers, aromatic divinyl compounds such as divinylbenzene, divinylnaphthalene, and derivatives thereof, N, N-divinylaniline, divinyl ether, divinyl sulfide, divinyl sulfone. Cross-linking agents such as acids, polybutadiene, polyisoprene unsaturated polyester, and JP-B-57-56,507, JP-A-59-221,304, JP-A-59-221,305, It is also possible to use reactive polymers described in Japanese Utility Model Laid-Open Nos. 59-221,306 and 59-221,307.

  The acrylic-styrene copolymer resin is polymerized using the styrene monomer and the (meth) acrylic monomer as main components, and the (meth) acrylic monomer and the styrene monomer. It may also contain other monomers copolymerizable with. The polymerization ratio of the styrene monomer to the (meth) acrylic monomer is preferably styrene monomer: (meth) acrylic monomer = 50: 100 to 500: 100 in molar ratio. 100: 100 to 300: 100 is more preferable. In addition, it is preferable that the weight average molecular weight of the microparticles | fine-particles which consist of acrylic-styrene copolymer resin is 10,000-1,000,000, and it is more preferable that it is 50,000-500,000.

  The average particle size of the resin fine particles is preferably from 0.1 to 15 μm, and more preferably from 0.5 to 5 μm. The average particle size of the fine particles is measured by a Coulter counter.

(Adhesive layer)
As the pressure-sensitive adhesive used for the pressure-sensitive adhesive layer, an ionizing radiation curable adhesive, a pressure sensitive adhesive, a heat sensitive adhesive (hot melt type) and the like can be used. Adhesives and pressure sensitive adhesives are preferred, and ionizing radiation curable adhesives are more preferred from the standpoint of adhesion retention.

  Examples of the ionizing radiation curable adhesive include (1) an adhesive containing a (meth) acrylic acid ester copolymer having an ionizing radiation crosslinkable functional group in a side chain, and a photopolymerization initiator as required. ) (Meth) acrylic acid ester-based copolymers, photopolymerizable oligomers and / or photopolymerizable monomers, and adhesives containing a photopolymerization initiator as required. On the other hand, as the pressure sensitive adhesive, those for optical use, for example, pressure sensitive adhesives such as acrylic, urethane, silicone, polyvinyl butyral (PVA), ethylene-vinyl acetate (EVA) and the like can be preferably used. However, among these, acrylic adhesives are particularly preferable because of excellent weather resistance and the like. The acrylic adhesive is usually a composition containing a (meth) acrylic acid ester copolymer and, if necessary, a crosslinking agent component.

  As the monomer used for the (meth) acrylic acid ester copolymer, various alkyl (meth) acrylates can be used, and among them, alkyl (meth) acrylates having an alkyl group having 1 to 18 carbon atoms are preferable. Examples of the alkyl (meth) acrylate having an alkyl group having 1 to 18 carbon atoms include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth). Acrylate, tert-butyl (meth) acrylate, amyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) Acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) a Relate and the like. These may be used alone or in combination of two or more.

  Moreover, you may use the other monomer copolymerizable with the said alkyl (meth) acrylate. As these other monomers, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, caprolactone-modified hydroxy (meth) acrylate, α- (hydroxymethyl) acrylic Hydroxyl group-containing (meth) acrylates such as mono (meth) acrylate of polyester diol obtained from methyl acrylate, α- (hydroxymethyl) ethyl acrylate, phthalic acid and propylene glycol; amino group, amide group, epoxy group and ether (Meth) acrylates having any of the groups, etc .; aliphatic unsaturated hydrocarbons such as ethylene and butadiene, and halogen-substituted products of aliphatic unsaturated hydrocarbons such as vinyl chloride; styrene and α-methylstyrene, etc. Aromatic unsaturated carbonization Elements; vinyl esters such as vinyl acetate; vinyl ethers; esters of allyl alcohol and various organic acids; ethers of allyl alcohol and various alcohols; unsaturated cyanide compounds such as (meth) acrylonitrile . These may be used alone or in combination of two or more. Further, in order to impart polarity to the resulting acrylic polymer, a small amount of (meth) acrylic acid may be used instead of a part of the alkyl (meth) acrylate. Moreover, the said adhesive may contain a crosslinking agent. Examples of the crosslinking agent include polyisocyanate compounds, polyamine compounds, melamine resins, urea resins, and epoxy resins. Furthermore, the pressure-sensitive adhesive may be appropriately added with a tackifier, a plasticizer, a filler, an antioxidant, an ultraviolet absorber, a silane coupling agent, and the like as necessary without departing from the object of the present invention. It can also be used.

  Moreover, as a suitable adhesive used for an adhesive layer, as disclosed by Unexamined-Japanese-Patent No. 2006-124640, 100 mass parts of acrylic adhesive polymers (A) containing an oxazoline group, and a carboxyl group are contained. The cross-linking polymer (B) is 0.01 to 10 parts by mass, and the cross-linking polymer (B) is obtained from a raw material monomer mixture having a carboxyl group-containing monomer of 30% by mass or more. A composition.

  The adhesive polymer (A) is a raw material monomer mixture comprising an oxazoline group-containing monomer (a-1), an alkyl (meth) acrylate (a-2), and other monomers (a-3) used as necessary ( It is obtained by radical polymerization of a).

  The oxazoline group-containing monomer (a-1) is represented by the following general formula (1).

(Wherein R ¹ , R ² , R ³ and R ⁴ may be the same or different, and independently represent hydrogen, halogen, alkyl group, aralkyl group, cycloalkyl group, cycloalkenyl group, aryl group, Or a substituted aryl group, and R ⁵ represents an alkenyl group).

  Specifically, 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl -4-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline, and the like, and one or more of these can be used. Of these, 2-isopropenyl-2-oxazoline, which is easily available, is preferable.

  This oxazoline group-containing monomer (a-1) is a monomer for introducing an oxazoline group serving as a crosslinking point into the adhesive polymer (A), and is 0.01% by mass in 100% by mass of the raw material monomer mixture (a). The above is preferable, and 0.05% by mass or more is more preferable. However, since the crosslinking does not proceed excessively, the oxazoline group-containing monomer (a-1) is preferably 5% by mass or less in 100% by mass of the raw material monomer mixture (a).

  The alkyl (meth) acrylate (a-2) is preferably an alkyl (meth) acrylate having an alkyl group having 4 to 18 carbon atoms, such as butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate. , Tert-butyl (meth) acrylate, amyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate , 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate It can be exemplified preferred, butyl acrylate, 2-ethylhexyl acrylate, octyl acrylate and isooctyl acrylate are more preferred. These may be used alone or in combination of two or more, and is not limited. This alkyl (meth) acrylate (a-2) is an essential monomer for developing adhesive strength, and is preferably used in an amount of 60% by mass or more in 100% by mass of the raw material monomer mixture (a). However, the alkyl (meth) acrylate (a-2) is preferably 90% by mass or less in 100% by mass of the raw material monomer mixture (a) from the balance with properties other than the expression of adhesive strength.

  The other monomer (a-3) is a monomer other than these which can be copolymerized with the oxazoline group-containing monomer (a-1) and the alkyl (meth) acrylate (a-2). However, it is desirable not to use a carboxyl group-containing monomer. It is because there exists a possibility of reacting with an oxazoline group containing monomer (a-1) during superposition | polymerization and gelatinizing. Specific examples of the other monomer (a-3) include alkyl (meth) acrylates other than the alkyl (meth) acrylate (a-2) such as methyl (meth) acrylate and ethyl (meth) acrylate; 2-hydroxyethyl (Meth) acrylate, hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, caprolactone-modified hydroxy (meth) acrylate, methyl α- (hydroxymethyl) acrylate, ethyl α- (hydroxymethyl) acrylate, phthalate Hydroxyl group-containing (meth) acrylates such as mono (meth) acrylate of polyester diol obtained from acid and propylene glycol; (meth) acrylates having any of amino group, amide group, epoxy group and ether group; ethylene And And halogen-substituted products of aliphatic unsaturated hydrocarbons such as butadiene and aliphatic unsaturated hydrocarbons such as vinyl chloride; aromatic unsaturated hydrocarbons such as styrene and α-methylstyrene; vinyl esters such as vinyl acetate Vinyl ethers; esters of allyl alcohol and various organic acids; ethers of allyl alcohol and various alcohols; unsaturated cyanide compounds such as (meth) acrylonitrile; These may be used alone or in combination of two or more, and is not limited. The other monomer (a-3) is preferably 0 to 30% by mass in 100% by mass of the raw material monomer mixture (a).

  Since the crosslinking polymer (B) is a crosslinking reaction partner of the oxazoline group of the above-mentioned adhesive polymer (A), the crosslinking polymer (B) does not need to exhibit adhesiveness alone. This crosslinking polymer (B) can be obtained by radical polymerization of a raw material monomer mixture (b) comprising a carboxyl group-containing monomer (b-1) and other monomers (b-2) used as necessary. it can. Examples of the carboxyl group-containing monomer (b-1) include unsaturated monocarboxylic acids such as (meth) acrylic acid, cinnamic acid and crotonic acid; unsaturated dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid and citraconic acid; Examples thereof include monoesters of these unsaturated dicarboxylic acids, and one or more of these can be used. Of these, (meth) acrylic acid and itaconic acid are preferred.

  The carboxyl group-containing monomer (b-1) needs to be 30% by mass or more in 100% by mass of the raw material monomer mixture (b). However, from the balance with other raw materials, the carboxyl group-containing monomer (b-1) is preferably 90% by mass or less in 100% by mass of the raw material monomer mixture (b). Moreover, the carboxyl group-containing monomer (b-1) and the other monomer (b-2) may be copolymerized to obtain a crosslinking polymer (B). As the other monomer (b-2), any one or more of the alkyl (meth) acrylate (a-2) and the other monomer (a-3) can be used. Moreover, you may use polyfunctional monomers, such as ethylene (glycol) di (meth) acrylate, in part.

  Although the thickness of an adhesive layer can be suitably adjusted with the location used, it is about 1-50 micrometers normally.

  When the resin layer contains resin fine particles, the content of the resin fine particles is preferably 1 to 30% by mass and more preferably 5 to 15% by mass with respect to 100% by mass of the adhesive layer. . If it is such a range, since the effect of this invention can be acquired appropriately, it is preferable.

  In addition to the pressure-sensitive adhesive and resin fine particles, other conventionally known additives may be added to the pressure-sensitive adhesive layer.

(Dye)
The present invention provides at least one of a near-infrared absorbing dye having a maximum absorption wavelength in a region of 800 to 1100 nm; a dye having a maximum absorption wavelength at 640 to 750 nm; and a dye having a maximum absorption wavelength at 570 to 600 nm. Contains one species. Conventionally, various liquid crystal displays in which a dye that absorbs wavelengths in the near infrared region is blended in an adhesive have been proposed. As in the present invention, by incorporating a specific wavelength absorbing dye into the fine particles, the durability of the dye is remarkably improved.

  The content of the specific wavelength absorbing dye in the fine particles is not particularly limited. When the fine particles are resin fine particles, the amount is preferably 0.1 to 10% by mass and more preferably 0.5 to 5% by mass with respect to 100% by mass of the resin fine particles (including the pigment).

  The specific wavelength absorbing dye used in the present invention is at least one of a near infrared absorbing dye having a wavelength range of 800 to 1100 nm; a dye having a maximum absorption wavelength at 640 to 750 nm; and a dye having a maximum absorption wavelength at 570 to 600 nm. is there. These dyes are appropriately selected according to the purpose, but preferably include a near-infrared absorbing dye having at least a region of 800 to 1100 nm, and a near-infrared absorbing dye having a region of 800 to 1100 nm and a maximum absorption at 640 to 750 nm. It is more preferable to have a dye having a wavelength or a dye having a maximum absorption wavelength at 570 to 600 nm, a near-infrared absorbing dye having a wavelength of 800 to 1100 nm; a dye having a maximum absorption wavelength at 640 to 750 nm; and 570 to 600 nm It is particularly preferable to include all three types of dyes having the maximum absorption wavelength.

  In flat panel display applications, near-infrared light generated from plasma display panels and liquid crystal displays can cause malfunctions in peripheral electronic devices such as remote controls such as televisions for home appliances, coolers, and video decks, as well as transmission optical communications. In addition, it is necessary to install an infrared absorption filter for cutting near infrared rays on the front surface. For this purpose, a near-infrared absorbing dye having a range of 800 to 1100 nm or a dye having a maximum absorption wavelength at 640 to 750 nm is used. In addition, light having a wavelength of 640 to 700 nm may be used for some LCDs that have a weak red color. However, unlike pure red having a wavelength range of 610 to 635 nm, it has a color tone called “crimson”. For this reason, in the field of flat panel displays and liquid crystal displays, it cannot necessarily be said that the light has a preferable color tone, and therefore a dye may be blended for the purpose of cutting this wavelength range. Furthermore, since the region of 570 to 600 nm corresponds to orange light derived from neon light emission in which an image is unclear, a dye having a maximum absorption wavelength at 570 to 600 nm is used.

Examples of the near-infrared absorbing dye having a maximum absorption wavelength at 800 to 1100 nm used in the present invention include cyanine dyes, phthalocyanine dyes, nickel complex dyes, and diimonium dyes. Among these, as the phthalocyanine dyes, phthalocyanine dyes described in JP-A No. 2001-106869, particularly phthalocyanine [CuPc (2,5-Cl ₂₎ produced in Example 8 of JP-A No. 2001-106689. PhO) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ (PhCH ₂ NH) ₄ ] (λmax: 807 nm), phthalocyanine [VOPc (2,5-Cl ₂ PhO) produced in Example 7 of the publication ) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ (PhCH ₂ NH) ₄ ] (λmax: 870 nm), phthalocyanine [VOPc (PhS) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ (PhCH ₂ NH) ₄ ] (λmax: 912 nm); manufactured in Example 2 of JP-A-2007-56105 Phthalocyanine [CuPc (PhS) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ {CH ₃ (CH ₂ ) ₃ CH (C ₂ H ₅ ) CH ₂ NH} ₄ ] (λmax: 903 nm); The phthalocyanine dyes described in JP-A-2004-18561, particularly the phthalocyanine [VOPc (PhS) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ {produced in Example 8 of JP-A-2004-18561 CH ₃ CH ₂ O (CH ₂ ) ₃ NH} ₄ ] (λmax: 928 nm), phthalocyanine [VOPc (4- (4)) produced in Example 17 of the publication (or Synthesis Example 1 of JP-A-2005-344021). (CH ₃ O) PhS) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ {CH ₃ (CH ₂ ) ₃ CH (C ₂ H ₅ ) CH ₂ NH} ₄ ] (λma x: 962 nm);

A phthalocyanine compound [hereinafter also referred to as {CuPc (3-methoxycarbonylphenoxy) ₈ (2-chlorobenzylamino) ₇ F}] (λmax: 916 nm), represented by the following formula:

A phthalocyanine compound [hereinafter also referred to as {CuPc (3-methoxycarbonylphenoxy) ₈ (2-ethylhexylamino) ₈ }] (λmax: 963 nm) or the like is preferably used. In this case, in consideration of durability and weather resistance, it is particularly preferable that the central metal of the phthalocyanine skeleton of the phthalocyanine dye having a wavelength of 800 to 1100 nm is copper. Examples of the diimonium dye include (N, N, N ′, N′-tetrakis (p-diethylaminophenyl) -p-benzoquinone-bis (imonium) · hexafluoroantimonate (λmax: 1090 nm), N, N. , N ′, N′-tetrakis (p-dibutylaminophenyl) -p-phenylenediamine-bis (bis (trifluoromethanesulfonyl) imidic acid) imonium salt (commercially available from Nippon Carlit Co., Ltd., trademark: CIR -1085), N, N, N ′, N′-tetrakis (p-dibutylaminophenyl) -p-phenylenediamine-bis (hexafluoroantimonic acid) imonium salt (commercially available from Nippon Carlit Co., Ltd.) Trademark: CIR-1081), diimonium cation and bis (trifluoromethanesulfone) imide anion ( As commercial products, CIR-RL (manufactured by Nippon Carlit) is preferably used, and as the nickel complex dye, Bis (1,2-diphenylene-1,2-dithiol) nickel is preferably used. As the cyanine dye, a stabilized cyanine dye is preferable, and the stabilized cyanine dye removes a cyanine cation and a quencher anion (an active molecule in an excited state (eg, singlet oxygen ( ¹ O ₂ )). An anion having a function to be excited (quenched)) As the cyanine cation or quencher anion, the compounds described in JP-A-2007-163644 can be used. Is a cation N represented by the following formula as a cyanine cation .1 or cationic No.2 are preferably used, and the quencher anion, anion No.11 or anion No.22 is preferably used.

  Among the dyes listed above, diimonium dyes, phthalocyanine (II) having a maximum absorption wavelength of more than 920 nm and not more than 1100 nm, cyanine dyes, and the like are particularly inferior in light resistance. Therefore, it is preferable that these dyes are contained in the resin fine particles because the effects of the present invention are remarkably obtained.

  In addition, by including a plurality of near infrared absorbers, it is possible to absorb a wide range of unnecessary wavelengths generated from a liquid crystal display or the like. While exhibiting excellent near-infrared absorption ability and transparency, it is also excellent in various properties such as thermal stability (heat resistance), moist heat resistance and light resistance, so the near-infrared absorbing dye has a maximum absorption wavelength at 800 to 920 nm. A phthalocyanine (I) having a maximum absorption wavelength at 800 to 920 nm, and a diimonium, the phthalocyanine (I) having a maximum absorption wavelength of more than 920 nm and not more than 1100 nm It is preferable that the near-infrared absorbing dye contains a phthalocyanine (I) having a maximum absorption wavelength at 800 to 920 nm and a phthalocyanine (II) having a maximum absorption wavelength in a region exceeding 920 nm. More preferred.

  Examples of the phthalocyanine (I) having a maximum absorption wavelength at 800 to 920 nm that can be used in the present invention include phthalocyanine compounds described in JP-A No. 2001-106658 and fluorine-containing compounds described in JP-A No. 2001-133623. Phthalocyanine compounds (Nippon Shokubai Co., Ltd., “Excolor IR-1”), (Nippon Shokubai Co., Ltd., “TX-EX810K”), (Mitsui Toatsu Dye Co., Ltd., “SIR-159”), JP-A-2002-82293 Fluorine-containing phthalocyanine-based dyes (Nippon Shokubai Co., Ltd., “e-ex color 801K”), (Nippon Shokubai Co., Ltd., “e-ex color 802K”), (Nippon Shokubai Co., Ltd. 803K "), eExcolor IR-10, eExcolor IR-10A, eExcolor IR 14. Ex-color IR-12, described in JP-A No. 2004-309655, phthalocyanine dye having a maximum absorption wavelength at 800 nm or more and less than 850 nm, phthalocyanine dye having a maximum absorption wavelength at 850 to 920 nm, etc. can do.

  As the phthalocyanine (II) having a maximum absorption wavelength of more than 920 nm and not more than 1100 nm that can be used in the present invention, phthalocyanine dyes described in JP-A No. 2004-309655 can be used.

(Method for producing resin fine particles containing specific wavelength absorbing dye)
The method for producing the resin fine particles containing the specific wavelength absorbing dye is not particularly limited. For example, the method of producing the resin containing the specific wavelength absorbing dye during polymerization of the monomer forming the resin; the specific wavelength absorption in the dissolved resin A method of forming fine particles after mixing the dye can be used. Preferably, it is a method in which a specific wavelength absorbing dye is contained during polymerization of the monomer forming the resin.

  Known methods for polymerizing the monomers forming the resin include suspension polymerization and emulsion polymerization. Among them, when resin fine particles are obtained by suspension polymerization, resin particles having a desired particle diameter can be obtained relatively easily, and there are advantages such as not using a solvent and easy reaction control, which is preferable. .

  In suspension polymerization, a polymerizable monomer is polymerized in the presence of a polymerization initiator soluble in the monomer, preferably in a solvent containing water. As the polymerization initiator used, an oil-soluble peroxide-based or azo-based initiator usually used for suspension polymerization can be used as the polymerization initiator used for the polymerization. For example, for example, benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, orthochlorobenzoyl peroxide, orthomethoxybenzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxydicarbonate, cumene hydroperoxide, cyclohexanone peroxide, t -Peroxide-based initiators such as butyl hydroperoxide and diisopropylbenzene hydroperoxide, 2,2'-azobisisobutyronitrile (azoisobutyronitrile), 2,2'-azobis (2,4- Dimethylvaleronitrile), 2,2'-azobis (2,3-dimethylbutyronitrile), 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobis (2,3,3 -Trimethylbutyronitrile), 2, '-Azobis (2-isopropylbutyronitrile), 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2- ( Carbamoylazo) isobutyronitrile, 4,4′-azobis (4-cyanovaleric acid), dimethyl-2,2′-azobisisobutyrate and the like. The polymerization initiator is preferably used in an amount of 0.01 to 20% by weight, particularly 0.1 to 10% by weight, based on the polymerizable monomer.

  The solvent containing water can contain an organic solvent in addition to water. Examples of the organic solvent include alcohols such as methanol, ethanol, isopropanol, n-butanol, isobutanol, sec-butanol, t-butanol, pentanol, ethylene glycol, propylene glycol, 1,4-butanediol; acetone, Examples thereof include ketones such as methyl ethyl ketone; astels such as ethyl acetate; (cyclo) paraffins such as isooctane and cyclohexane; aromatic hydrocarbons such as benzene and toluene. These may be used alone or in combination of two or more.

  The specific wavelength absorbing dye is preferably polymerized after being mixed with a polymerizable monomer and a polymerization initiator. The order of mixing at this time is not limited.

  In suspension polymerization, a dispersion stabilizer can be added to stabilize suspended particles. Dispersion stabilizers include polyvinyl alcohol, gelatin, tragacanth, starch, methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, sodium polyacrylate, sodium polymethacrylate, and other water-soluble polymers, anionic surfactants, and cationic surfactants. , Zwitterionic surfactants, nonionic surfactants, etc. Other alginate, zein, casein, barium sulfate, calcium sulfate, barium carbonate, magnesium carbonate, calcium phosphate, talc, clay, diatomaceous earth, bentonite, hydroxylated Titanium, thorium hydroxide, metal oxide powder, etc. are used. Examples of anionic surfactants include fatty acid oils such as sodium oleate and castor oil potassium, alkyl sulfate salts such as sodium lauryl sulfate and ammonium lauryl sulfate, alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate, and alkylnaphthalene sulfonates. , Alkane sulfonate, dialkyl sulfosuccinate, alkyl phosphate ester salt, naphthalene sulfonate formalin condensate, polyoxyethylene alkylphenyl ether sulfate, polyoxyethylene alkyl sulfate, and the like. Nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxysorbitan fatty acid ester, polyoxyethylene alkylamine, glycerin fatty acid ester, oxyethylene- Examples include oxypropylene block polymers. Examples of the cationic surfactant include alkylamine salts such as laurylamine acetate and stearylamine acetate, and quaternary ammonium salts such as lauryltrimethylammonium chloride. Examples of the zwitterionic surfactant include lauryl dimethylamine oxide.

  These dispersion stabilizers have a composition such that the particle diameter of the obtained resin particles is a predetermined size, for example, 0.1 to 500 μm, preferably 0.5 to 100 μm, more preferably 0.5 to 30 μm. The amount to be used should be adjusted as appropriate. For example, it is used in an amount of 0.01 to 29% by weight, preferably 0.1 to 10% by weight, based on the polymerizable monomer.

  Furthermore, in the case of suspension polymerization, other additives may be added to the polymerizable monomer or the solvent as necessary. Examples of additives include colorants such as pigments and dyes, plasticizers, polymerization stabilizers, fluorescent brighteners, magnetic powders, ultraviolet absorbers, antistatic agents, and flame retardants. These additives may have been surface-treated by various methods.

In addition, the group consisting of —SH, —S—S—, —COOH, —NO ₂ and —OH is used for the purpose of effectively suppressing emulsion polymerization occurring at the suspension particle interface when suspension polymerization is performed. A compound having at least one structural unit selected from the group consisting of substantially insoluble in water and hardly soluble in the polymerizable monomer may be added. Specific examples of such compounds include salicylic acid, thiosalicylic acid, dithiosalicylic acid, nitrobenzoic acid, 3,4-dinitrobenzoic acid, and nitrophenol. These may be used alone or in combination of two or more.

  The suspension polymerization is usually carried out at 10 to 90 ° C, preferably 30 to 80 ° C. The regulation of the particle diameter is, for example, that a suspension in which a predetermined component is dispersed in an aqueous medium is T.D. K. Stir with a homomixer. Alternatively, it is carried out by passing it once or several times through a high-speed stirrer such as a line mixer (for example, Ebara Milder). The time for suspension polymerization is not particularly limited, but is usually 1 to 30 minutes, preferably 2 to 10 minutes.

  The mixing ratio of the polymerizable monomer and the specific wavelength absorbing dye is not particularly limited, but the dye is preferably 0.1 to 10% by mass with respect to the polymerizable monomer, More preferably, it is 0.5-5 mass%.

  After mixing the specific wavelength absorption dye into the dissolved resin, the method of making fine particles is, for example, by dissolving the resin in a solvent, then dissolving the specific wavelength absorption dye in this, and concentrating until high viscosity is obtained. Fine particles are obtained by pulverizing the obtained pellets.

The solvent used for dissolving the resin is not particularly limited, and examples thereof include tetrahydrofuran, dimethylformamide, chloroform and the like. These may be used alone or in combination of two or more. The amount of solvent is not particularly limited, but is about 5 to 20 times by mass with respect to the resin.

  Furthermore, at the time of mixing, other additives may be added to the solvent as necessary. Examples of additives include colorants such as pigments and dyes, plasticizers, polymerization stabilizers, fluorescent brighteners, magnetic powders, ultraviolet absorbers, antistatic agents, and flame retardants.

  The obtained pellets are dried and then appropriately pulverized and classified in order to obtain fine particles having a desired particle size.

(Transparent substrate)
As the transparent substrate 1, conventionally known ones can be used, and there may be a transparent resin film, a transparent resin sheet, a transparent resin plate (eg, acrylic resin plate) or transparent glass, but industrially easy to process continuously. It is preferable to use a flexible transparent resin film. Examples of transparent resin films include triacetyl cellulose (abbreviated as TAC, cellulose triacetate), polyesters such as polyethylene terephthalate (PET), diacetyl cellulose, acetate butyrate cellulose, polyethersulfone, acrylic or methacrylic, polyurethane Resin films such as polyester, polycarbonate, polysulfone, polyether, polymethylpentene, polyetherketone film and (meth) acrylonitrile can be used. Among these, TAC having no birefringence is preferable. The thickness of the transparent resin film is usually about 25 μm to 1000 μm, preferably 200 μm or less.

  The method for laminating the hard coat layer on the transparent substrate is not particularly limited. For example, transparent resin, fine particles containing a dye, and if necessary, a polymerization initiator, a sensitizer, a diluting solvent, a filler, a pigment dispersant, a conductivity imparting agent, an ultraviolet absorber, an antioxidant, an anti-drying agent, Add penetrant, pH adjuster, metal sequestering agent, antibacterial and fungicidal agent, surfactant, etc., uniformly mix and disperse to form a mixture, then spin coating method, wheeler coating method, dip coating method, Coating method such as spray coating method, slide coating method, bar coating method, roll coating method, gravure reverse coating method, meniscus coating method or bead coating method; printing method such as flexographic printing method, screen printing method or gravure printing method By applying to the surface of a transparent base material, a coating film is formed. After that, when it contains a thermosetting resin, it is heated, and when it contains an active energy ray-curable resin, it contains active energy rays (electromagnetic waves, ultraviolet rays (UV), visible rays, infrared rays, electron beams, gamma rays, etc.) To cure. If the resin that forms the hard coat layer contains pigments, transparent resin, pigments, and other necessary ingredients are mixed and dispersed uniformly to form a mixture and then applied to the surface of the transparent substrate. To form a coating film and cure.

  In the case of curing by irradiation with ultraviolet rays, it is preferable to use a light source including light having a wavelength of 150 to 450 nm. As such a light source, a solar ray, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, a gallium lamp, a xenon lamp, a carbon arc lamp, or the like is preferable. Together with these light sources, it is possible to use heat by infrared rays, far infrared rays, hot air, high-frequency heating or the like.

  In the case of curing by irradiation with an electron beam, 50 to 1000 KeV emitted from various electron beam accelerators such as a Cockloft Walton type, a bandegraph type, a resonant transformation type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type. Preferably, an electron beam having an energy of 100 to 300 KeV can be used. In addition to the electron beam, it is possible to use heat by infrared rays, far infrared rays, hot air, high frequency heating or the like.

  Since the near-infrared absorption filter of the present invention has high stability, the appearance and near-infrared absorption ability are maintained even after long-term storage and use. The near-infrared absorption filter of the present invention can be used for a display such as a liquid crystal display, a CRT display, a plasma display, an EL display, or an LED display. A liquid crystal display or a plasma display is preferable, and a liquid crystal display is more preferable.

  Hereinafter, the present invention will be described in more detail with reference to synthesis examples and examples.

Synthesis Example 1 Synthesis of Dye-Containing Fine Particle A A flask equipped with a stirrer, an inert gas introduction tube, a reflux condenser and a thermometer was added to a polyoxyethylene sulfammonium (Haitenol N-08, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.). ) 900 parts of deionized water with 0.5 parts dissolved was charged. 70 parts of styrene, 30 parts of divinylbenzene, 1 part of azoisobutyronitrile and 1 part of 3,4-dinitrobenzoic acid and phthalocyanine synthesized in the same manner as in Synthesis Example 1 of JP-A-2005-344021 [ VOPc {4- (CH ₃ O) PhS} ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ {CH ₃ (CH ₂ ) ₃ CH (C ₂ H ₅ ) CH ₂ NH} ₄ ] (λmax: 962 nm ) 1.5 parts of the mixture was charged. K. The mixture was stirred at 8000 rpm for 5 minutes with a homogenizer (manufactured by Tokushu Kika Kogyo Co., Ltd.) to obtain a uniform suspension. Next, the mixture was heated to 75 ° C. while blowing nitrogen gas, and stirred at this temperature for 5 hours to conduct a suspension polymerization reaction, followed by cooling. The suspension was filtered and dried to obtain colored resin fine particles A. The obtained pigment-containing fine particles A were measured with a Coulter counter. As a result, the average particle size was about 2 μm.

Synthesis Example 2: Production Method of Dye-Containing Fine Particle B Styrene-acrylic acid ester copolymer (trade name: Hymer TB-1000F, manufactured by Sanyo Chemical Co., Ltd.) 100 parts of a copolymer dissolved in 900 parts of tetrahydrofuran, and then a diimonium compound (N, N, N ′, N′-tetrakis (p-diethylaminophenyl) -p-benzoquinone-bis (imonium) · hexafluoroantimonate) 0.5 parts are dissolved and concentrated to a high viscosity pellet. Turned into. The obtained pellets were dried at room temperature and then vacuum dried at 60 ° C. overnight. Thereafter, it was coarsely pulverized using a hammer mill, once again vacuum dried at 60 ° C. overnight, and then finely pulverized by an air jet type fine pulverizer. The obtained fine powder was further classified to select 2 μm to obtain dye-containing fine particles B.

Example 1
On a commercially available polyethylene terephthalate film (about 50 μm), a coating composition for forming a light diffusing layer (light diffusing hard coat layer) having the following composition was formed on the film by a gravure reverse coating method, and the film thickness was 10 g / m ² . After coating, the coated film was dried at a temperature of 70 ° C. for 1 minute, and then cured by irradiating with an ultraviolet ray so that the irradiation dose was 100 mJ to form a light diffusion layer (light diffusion) Layer thickness: about 10 μm). Thereafter, an antiglare layer-forming coating composition having the following composition was applied on the light diffusion layer by a gravure reverse coating method so that the film thickness would be 3 g / m 2. And dried for 1 minute, and then cured by irradiating with ultraviolet rays so that the irradiation dose becomes 100 mJ to form an antiglare layer (film thickness of the antiglare layer: about 3 μm) to obtain an antiglare film. . The hardness of the obtained film was 2H. Moreover, haze was measured according to JIS-K7136 haze (cloudiness), and haze value was 51.6.

  However, the near-infrared absorbing dye 1 represents the following phthalocyanine compound produced in the same manner as in Example 2 of JP-A-2007-56105.

  Similarly, near-infrared absorbing dye 2 represents the following phthalocyanine compound produced in the same manner as in Example 8 of JP-A-2001-106869.

  Subsequently, 2.7 parts by mass of an ultraviolet absorber (manufactured by Ciba Specialty Chemicals Co., Ltd., TINUVIN 384) and an antioxidant (Ciba Specialty Chemicals Co., Ltd.) are formed on the base of the antiglare film thus obtained. Co., Ltd., IRGANOX-1010) 0.9 parts by mass, acrylic adhesive (manufactured by Toagosei Co., Ltd., Aron S-1601) 96.4 parts by mass was mixed to obtain a dry coating film. Coating was performed so that the thickness was 15 μm, and a transparent adhesive layer containing an ultraviolet absorber was laminated. The pressure-sensitive adhesive surface of the film containing the near-infrared absorber subjected to the pressure-sensitive adhesive process was attached to a tempered glass substrate having a thickness of 3 mm with a roll laminator to produce a near-infrared absorption filter.

(Example 2)
The near-infrared operation was carried out in the same manner as in Example 1 except that the dye-containing fine particles B were used instead of the dye-containing fine particles A in the coating composition for forming a light diffusion layer of Example 1 and methyl cellosolve was used instead of toluene. An absorption filter was manufactured. The hardness of the obtained film was 2H.

Synthesis Example 3: Polymerization of adhesive polymer emulsion 78 parts 2-ethylhexyl acrylate, 10 parts n-butyl acrylate, 5 parts ethyl acrylate, 6 parts 2-hydroxyethyl methacrylate, 1 part 2-isopropenyl-2-oxazoline, Mix 0.04 part of tert-dodecyl mercaptan (TDM) as a molecular weight regulator, 2.5 parts of “Hytenol LA-16” (Daiichi Kogyo Seiyaku Co., Ltd.) and 32 parts of deionized water as an emulsifier, and stir well. A pre-emulsion was prepared. Next, 30 parts of deionized water was charged into a flask equipped with a dropping funnel, a stirrer, a thermometer, a nitrogen gas inlet tube and a reflux condenser, and the temperature was raised to 70 ° C. by replacing with nitrogen. To this, 0.4 part of potassium persulfate and 0.015 part of sodium bisulfite were added, and then 0.29 part of the pre-emulsion was added to initiate the polymerization reaction. After 10 minutes from the start of the reaction, the rest of the pre-emulsion was continuously added dropwise over about 2.5 hours, and 0.135 parts of sodium bisulfite was added dropwise in parallel to carry out the polymerization reaction. After completion of the dropwise addition, the mixture was aged at 70 ° C. for 1.5 hours, and then cooled to room temperature to obtain an adhesive polymer emulsion E-1 (solid content 55.0%).

(Synthesis Example 4)
59.8 parts of ethyl acrylate, 40 parts of methacrylic acid, 0.2 part of ethylene (glycol) dimethacrylate, 1.5 parts of “Hytenol LA-10” (Daiichi Kogyo Seiyaku Co., Ltd.) as an emulsifier and 76 of ion-exchanged water 96 parts were mixed well and stirred well to prepare a pre-emulsion. Next, a flask equipped with a dropping funnel, a stirrer, a thermometer, a nitrogen gas inlet tube and a reflux condenser was charged with 157.16 parts of deionized water and 1.5 parts of the above-mentioned “Hitenol LA-10”, and the atmosphere was replaced with nitrogen. The temperature was raised to 68 ° C. 8.92 parts of the pre-emulsion was added thereto, and 5 minutes later, 0.012 part of ammonium persulfate and 0.02 part of sodium bisulfite were added, and the polymerization reaction was started at 72 ° C. After 20 minutes from the reaction time, the rest of the pre-emulsion was continuously dropped over about 2 hours, and 0.219 parts of ammonium persulfate was dropped in parallel to obtain a crosslinking polymer emulsion E-2 ( Solids 28.0%).

(Example 3)
100 parts (wet) of adhesive polymer emulsion E-1 is added, 1.01 part (wet) of polymer emulsion E-2 for crosslinking is added, and 5.5 parts of dye-containing fine particles A are added. 0.45 part of 1 and 0.4 part of the above near-infrared absorbing dye 2 were added and stirred well to obtain a near-infrared dye-containing pressure-sensitive adhesive emulsion. This near-infrared pigment-containing pressure-sensitive adhesive emulsion was coated on a commercially available polyethylene terephthalate film (about 50 μm) so that the film thickness after drying was 25 μm, dried for 90 seconds with a hot air dryer at 105 ° C., and then transparent. The adhesive surface of the coating film was attached to a 3 mm thick tempered glass substrate with a roll laminator to produce a near infrared absorption filter.

Example 4
A near-infrared absorption filter was produced in the same manner as in Example 3 except that 5.5 parts of dye-containing fine particles B were used in place of the dye-containing fine particles A of Example 4.

(Comparative Example 1)
Instead of 20 parts of the dye-containing fine particles B in Example 2, 20 parts of the fine particles prepared without adding the dye in Synthesis Example 2 and a diimonium compound (N, N, N ′, N′-tetrakis (p -Diethylaminophenyl) -p-benzoquinone-bis (imonium) hexafluoroantimonate) Example 2 except that the diimonium compound was added directly to the coating solution so that the amount of the dye was exactly the same as Example 2. The near-infrared absorption filter was manufactured in exactly the same manner as described above.

(Comparative Example 2)
Instead of 5.5 parts of the dye-containing fine particles B in Example 4, 5.5 parts of the fine particles prepared without adding the dye in Synthesis Example 2, and diimonium compounds (N, N, N ′, N ′ contained in the coating film) -Tetrakis (p-diethylaminophenyl) -p-benzoquinone-bis (imonium) hexafluoroantimonate) Except that the diimonium compound was added directly to the coating solution so that the amount of the dye was exactly the same as in Example 4. The near-infrared absorption filter was manufactured in exactly the same manner as in Example 4.

  The near-infrared absorption filter obtained above was evaluated for light resistance and durability by the following test methods, and the results are shown in Table 1.

(Evaluation of light resistance)
Using a xenon light resistance tester (Suntest CPS manufactured by ATLAS), irradiating 130,000 lux of light, measuring the average value of the initial absorbance up to 780 to 1000 nm and the average value of the absorbance after 1000 hours, Evaluation was made with an average residual ratio of 80% or more as ◎, 70-80% as ○, 50-60% as Δ, and 50% or less as x.

(Evaluation of heat resistance)
Using an inert oven (TABAI INSERT OVEN IPHH-200), a heat resistance test for 1000 hours was performed at a temperature of 80 ° C., and then the average value of the initial absorbance up to 780 to 1000 nm and the average value of the absorbance after 1000 hours. Was measured, and the residual ratio of the average value of the absorbance with respect to the initial stage was evaluated as ◎, 97 to 95% as ○, and less than 95% as ×.

(Examples 5 to 9)
Mount the near-infrared absorbing filter described in Examples 1 to 4 on the front of the plasma display, install an electrical device that controls the operation with a remote control at a position 2.5 m from the display, and observe whether a malfunction is induced As a result, the malfunction was induced when the filter was not attached, but when the near-infrared absorption filter described in Examples 1 to 4 was attached to the front part of the plasma display, the induction of malfunction was completely recognized. I couldn't.

  From this, it is considered that the near-infrared absorption filter according to the present invention of Examples 1 to 4 can suppress malfunction of a remote controller or the like.

(Examples 10 to 14)
As shown in FIG. 6, the filters 103 obtained in Examples 1 to 4 are vertically arranged with respect to the support column 102 adjusted to be substantially perpendicular to the direct sunlight (the incident direction of the direct sunlight). And a temperature measuring device 106 (a measurement panel is winded by a measuring filter 104 installed at the tip of the column 103 and a sample support plate 105 that can be adjusted in the vertical direction near the lower part of the column 103. The black panel 107 is set on the sample support plate 105, and the distance between the surface of the black panel 107 and the measurement filter 104 is set to 200 mm. The temperature sensor 108 was brought into contact with the surface of 107. The temperature sensor 108 is connected to a measuring device (not shown) via a lead wire 109. Using this temperature measuring device, the temperature of the portion where the light passed through the filter was exposed under direct sunlight was measured. Further, after performing a light resistance test for 50 hours at a humidity of 50%, a black panel temperature of 63 ° C., and an ultraviolet intensity of 90 mW / cm ² , the temperature was measured again in the same manner as described above. The results are shown in Table 2.

(Comparative Examples 3 and 4)
In Example 10, the temperature change was measured in the same manner as in Example 10 except that the filters obtained in Comparative Examples 1 and 2 were used.

(Comparative Example 5)
In Comparative Example 1, the temperature change was measured in the same manner as in Example 10 except that no dye compound was added.

It is a schematic diagram which shows one Embodiment of the anti-glare film of this invention. It is a schematic diagram which shows one Embodiment of the anti-glare film of this invention. It is a schematic diagram which shows one Embodiment of the anti-glare film of this invention. It is a schematic diagram which shows one Embodiment of the anti-glare film of this invention. It is a schematic diagram which shows one Embodiment of the polarizing plate of this invention. It is a figure which shows the temperature measuring apparatus used in the Example.

Explanation of symbols

1, 1 'transparent substrate,
2, 2 'transparent resin,
3 resin fine particles,
4, 7 Anti-glare layer,
5 light diffusing hard coat layer,
6 antireflection layer,
8, 8 'adhesive layer,
9 Protective film,
10, 20, 30, 40, 50 Anti-glare film,
11 fine particles,
12 Polarizer,
60 polarizing plate,
101 direct sunlight,
102 support base,
104 Filter for measurement,
106 temperature measuring device,
107 black panel,
108 Temperature sensor.

Claims (8)

  At least one of the hard coat layer or the pressure-sensitive adhesive layer has resin fine particles, and the resin fine particles have a near-infrared absorbing dye having a maximum absorption wavelength at 800 to 1100 nm; a dye having a maximum absorption wavelength at 640 to 750 nm; A near-infrared absorption filter comprising at least one dye selected from the group consisting of dyes having a maximum absorption wavelength at 600 nm.   The near-infrared absorption filter according to claim 1, wherein the hard coat layer is an antiglare layer.   The near-infrared absorption filter according to claim 1 or 2, wherein the resin fine particles are at least one selected from fine particles comprising an acrylic resin, an acrylic-styrene copolymer resin, or a styrene resin.   The resin fine particles include at least one selected from the group consisting of a cyanine dye, a phthalocyanine dye, a nickel complex dye, and a diimonium dye having a maximum absorption wavelength in a range of 800 to 1100 nm. The near-infrared absorption filter of any one of these.   The dye contained in the resin fine particles is at least one selected from the group consisting of a diimonium dye, phthalocyanine (II) having a maximum absorption wavelength of more than 920 nm and not more than 1100 nm, and a cyanine dye. Near infrared absorption filter.   Furthermore, the near-infrared absorption filter of Claim 5 containing the phthalocyanine (I) which has a maximum absorption wavelength in 800-920 nm.   The flat panel display containing the near-infrared absorption filter of any one of Claims 1-6.   The flat panel display according to claim 7, wherein the flat panel display is a liquid crystal display.

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