KR20080097429A - Near-infrared absorbing film - Google Patents

Abstract

Disclosed is a near-infrared absorbing film which absorbs light over a wide range of near-infrared wavelengths, while being highly excellent in durability, especially in wet heat resistance and heat resistance. Specifically disclosed is a near-infrared absorbing film wherein a near-infrared absorbing layer composed of a composition mainly containing a near-infrared absorbing dye and a resin is formed on a transparent base. This near-infrared absorbing film is characterized in that the composition contains either a trifluoromethanesulfonic acid compound or a bis(trifluoromethansulfonyl)imide compound.

Description

Near-infrared absorbing film

The present invention relates to an optical film that absorbs near infrared rays, and more particularly, to a near infrared absorbing film which is less in color tone change at high temperatures and has excellent durability.

The optical film which has the near-infrared absorption ability has the property to block | block near-infrared and let visible light pass, and is used for various uses.

In recent years, plasma displays have attracted attention as thin large-screen displays, but there is a problem that electronic devices using the near-infrared remote control cause malfunction due to near-infrared radiation emitted from the plasma display, and the near-infrared absorption ability is applied to the front surface of the plasma display. The film which has is used.

As a film having a near-infrared absorptive capacity, (1) an interference filter containing metal ions such as copper or iron in a phosphate-based glass, and (2) laminating layers having different refractive indices and interfering transmitted light, ( 3) The acrylic resin film containing copper ion in a copolymer, and the film which laminated | stacked the layer which disperse | distributed or melt | dissolved the pigment in (4) resin are proposed.

In these, the film of (4) has good workability and productivity, the degree of freedom of optical design is also comparatively large, and the various methods are proposed (refer patent document 1-9).

Patent Document 1: Japanese Patent Application Laid-Open No. 2002-82219

Patent Document 2: Japanese Patent Application Laid-Open No. 2002-138203

Patent Document 3: Japanese Patent Application Laid-Open No. 2002-214427

Patent Document 4: Japanese Patent Application Laid-Open No. 2002-264278

Patent Document 5: Japanese Patent Application Laid-Open No. 2002-303720

Patent Document 6: Japanese Patent Application Laid-Open No. 2002-333517

Patent Document 7: Japanese Patent Application Laid-Open No. 2003-82302

Patent Document 8: Japanese Unexamined Patent Publication No. 2003-96040

Patent Document 9: Japanese Patent Application Laid-Open No. 2003-114323

Some of these methods have the capability of sufficiently blocking the near infrared rays emitted from the plasma display, and there is little change over time even for long time use.

On the other hand, in order to reduce the weight and quality of a display, the method of bonding together the optical filter containing a near-infrared absorbing film to the panel of a plasma display without using glass is proposed. In this system, heat of a display is easily transmitted to a near-infrared absorbing film, and the near-infrared absorbing film excellent in moisture heat resistance and heat resistance is desired.

Disclosure of the Invention

Problems to be Solved by the Invention

SUMMARY OF THE INVENTION An object of the present invention is to provide a near-infrared absorbing film which is designed to solve the above-mentioned problems of the prior art and absorbs the near-infrared region largely and broadly, and is highly excellent in durability, in particular, moist heat resistance and heat resistance.

Means to solve the problem

The near-infrared absorption film of this invention which could solve the said subject becomes the following structures.

1st invention is a near-infrared absorption film which provided the near-infrared absorption layer which consists of a composition comprised mainly from a near-infrared absorption pigment | dye and resin on a transparent base material, In a said composition, a trifluoromethanesulfonic acid compound or bis (trifluoromethane) It is a near-infrared absorptive film containing any one of the sulfonyl) imide acid compounds.

2nd invention is a near-infrared absorbing film of 1st invention characterized by the near-infrared absorption pigment | dye containing a dimonium salt compound.

The third invention is a near-infrared absorbing film according to the second invention, wherein the diimmonium salt compound is a diimmonium salt compound having bis (trifluoromethanesulfonyl) imide acid as a counter ion.

In a fourth aspect of the present invention, a trifluoromethanesulfonic acid compound or a bis (trifluoromethanesulfonyl) imide acid compound is contained as an ionic liquid in an amount of 0.1% by mass or more and 10.0% by mass or less in the near infrared absorbing layer. It is a near-infrared absorption film in any one of 1-3 invention.

In the fifth invention, a cyanine dye having a trifluoromethanesulfonic acid compound or a bis (trifluoromethanesulfonyl) imide acid compound as a counterion as a near infrared absorbing dye is 0.1% by mass or more and 10.0% by mass or less in the near infrared absorbing layer. It is the near-infrared absorption film in any one of the 1st-3rd invention characterized by containing.

Resin which comprises a near-infrared absorption layer is acrylic resin, 6th invention is the near-infrared absorption film in any one of the 1st-5th invention characterized by the above-mentioned.

Effects of the Invention

When the near-infrared absorbing film of the present invention is installed on the front side of a plasma display as a near-infrared absorbing filter, like the conventional near-infrared absorbing filter, it absorbs unnecessary near-infrared rays emitted from the display, thereby preventing malfunction of precision instruments. Since the change in color tone due to heat can be greatly reduced, there is an advantage that it can contribute to the high quality of the plasma display and the design freedom of the optical filter is increased.

Implement the invention  Best form for

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

(Transparent material)

In the present invention, the transparent substrate is not particularly limited, but it is preferable that the total light transmittance is 80% or more, and the haze is 5% or less. When the substrate is poor in transparency, not only the brightness of the display is lowered, but also the sharpness of the image is poor.

As such a transparent base material, For example, plastic film, sheet, glass, etc. of polyester type, acryl type, cellulose type, polyethylene type, polypropylene type, polyolefin type, polyvinyl chloride type, polycarbonate, phenol type, urethane type, etc. The thing which bonded two or more arbitrary types of is mentioned. Preferably, it is a polyester film with a good balance of heat resistance and flexibility, and more preferably a polyethylene terephthalate film.

The polyester film suitable as a transparent base material used by this invention is an aromatic dicarboxylic acid or ester thereof, such as terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, as a dicarboxylic acid component, ethylene glycol as a glycol component, Polyester chip obtained by esterification or transesterification of diethylene glycol, 1,4-butanediol, neopentylglycol and the like, followed by polycondensation reaction is dried, melted with an extruder and extruded into a sheet form from a T die. It is a film manufactured by extending | stretching the unstretched sheet | seat obtained by extending | stretching at least in 1 axial direction, and then performing heat setting process and a relaxation process.

The biaxially oriented film is particularly preferable for the above film in terms of strength and the like. Examples of the stretching method include a tubular stretching method, simultaneous biaxial stretching method, and successive biaxial stretching method, and the like, and the sequential biaxial stretching method is preferable because of planarity, dimensional stability, and thickness nonuniformity. The sequential biaxially oriented film is, for example, roll drawn in the longitudinal direction at a glass transition temperature (Tg) of the polyester (Tg) to (Tg + 30 ° C) at 2.0 to 5.0 times, and then preheated with a tenter, followed by 1.2 at 120 to 150 ° C. Stretch in the width direction at ˜5.0 times. Moreover, it can manufacture by performing heat-setting process at the temperature of 220 degreeC or more (melting point-10 degreeC) or less after biaxial stretching, and then relaxing 3 to 8% in the width direction. Moreover, in order to further improve the dimensional stability of a film longitudinal direction, you may use together a longitudinal relaxation process.

In order to provide handling property (for example, winding property after lamination) to a film, it is preferable to contain particle | grains and to form a processus | protrusion on the film surface. Examples of the particles to be contained in the film include inorganic particles such as silica, kaolinite, talc, calcium carbonate, zeolite, and alumina, and heat resistant polymer particles such as acrylic, PMMA, nylon, polystyrene, polyester, and benzoguanamine formalin condensate. . In terms of transparency, the content of particles in the film is preferably small, for example, preferably 1 ppm or more and 1000 ppm or less. Moreover, it is preferable to select the particle | grains whose refractive index and the resin used for transparency are close. Moreover, in order to provide various functions to a film as needed, you may contain a light resistant agent (ultraviolet-proof agent), a pigment | dye, an antistatic agent, etc.

In the present invention, when the anti-reflection layer is provided on the surface opposite to the surface on which the near-infrared absorbing layer is laminated, the near-infrared absorbing pigment due to the ultraviolet light incident from the outside tends to deteriorate, so that the ultraviolet ray absorbent is contained in the transparent substrate. It is preferable.

As a ultraviolet absorber, although it is classified roughly into organic type ultraviolet absorber and inorganic type ultraviolet absorber, use of organic type ultraviolet absorber (low molecular type, high molecular type) is preferable from a viewpoint of transparency. Although it does not specifically limit as an organic type ultraviolet absorber (low molecular type), For example, a benzotriazole type, a benzophenone type, a cyclic imino ester type, etc., and a combination thereof are mentioned. Among them, from the viewpoint of durability, a benzotriazole type and a cyclic imino ester type are preferable, and in order to withstand the temperature at the time of production of the substrate, it is preferable to use an ultraviolet absorber having a decomposition temperature of 290 ° C or higher.

It is preferable to adjust content of a ultraviolet absorber so that the transmittance | permeability in the wavelength of 380 nm or less may be 10% or less so that photodeterioration of a near-infrared absorption layer can be suppressed. Specifically, the content of the ultraviolet absorber is preferably 0.1 to 4% by mass, more preferably 0.3 to 2% by mass in the transparent substrate. If the amount of the ultraviolet absorber is too small, the ultraviolet absorbing ability is small. If the amount of the ultraviolet absorber is too large, yellowing of the film or deterioration of the film forming property of the film may be undesirable.

The transparent base material used by this invention may be a single | mono layer film, or the composite film of two or more layers which laminated | stacked the surface layer and the center layer may be sufficient. In the case of a composite film, there is an advantage that the functions of the surface layer and the center layer can be designed independently. For example, it is possible to further improve transparency as a whole composite film by containing particles only in a thin surface layer and forming irregularities on the surface, while maintaining handling properties while substantially not including particles in a thick center layer. have. In addition, in the case of providing the ultraviolet absorbing ability, by containing the ultraviolet absorbent only in the center layer, the precipitation of the ultraviolet absorbent on the film surface during film production or over time can be reduced, so that adverse effects such as deterioration of heat resistance to the near infrared absorbing layer can be reduced. It can be suppressed. Although the manufacturing method of the said composite film is not specifically limited, Taking productivity into consideration, the raw material of a surface layer and a center layer is extruded from each extruder, and it introduce | transduces into one die, and obtains an unstretched sheet, at least in 1 axial direction. Lamination | stacking by what is called co-extrusion method to orientate is especially preferable.

Although the thickness of a transparent base material changes with raw materials, when using a polyester film, a minimum is 35 micrometers or more, More preferably, it is 50 micrometers or more. On the other hand, the upper limit of the thickness is preferably 260 µm or less, and more preferably 200 µm or less. In the case where the thickness is thin, not only the handling property is poor, but when the heating is performed at a time such that the residual solvent of the near-infrared absorbing layer is reduced, heat wrinkles occur in the film, and the planarity tends to be poor. On the other hand, when the thickness is thick, not only is there a problem in terms of cost, but also poor planarity due to the wound wound is likely to occur in the case of winding up and storing in roll shape.

(Middle floor)

Although the near-infrared absorption filter of this invention is a structure which laminated | stacked the near-infrared absorption layer on the transparent base material, it is preferable to provide an intermediate | middle layer for the purpose of improving the adhesiveness of a transparent base material and a near-infrared absorption layer, or the transparency of a transparent base material. Moreover, when particle | grains are not contained in a film, high transparency can be obtained, maintaining handling property by providing the intermediate | middle layer containing particle | grains simultaneously at the time of film manufacture.

Examples of the resin constituting the intermediate layer include polyester resins, polyurethane resins, polyester urethane resins, acrylic resins, melamine resins, and the like, and it is important to select such resins to have good adhesion with the substrate and the near infrared absorbing layer. If the resin constituting the base material and the near-infrared absorbing layer is an acrylic, it is preferable to select an acrylic, a co-polyester type, and a polyester urethane type.

You may form a crosslinked structure by including a crosslinking agent in the said intermediate | middle layer for the purpose of improving adhesiveness and water resistance. Examples of the crosslinking agent include urea, epoxy, melamine and isocyanate. In particular, the effect of the crosslinking agent is remarkable when the whitening or strength of the resin decreases under high temperature and high humidity. In addition, you may use the graft copolymer resin which has self crosslinking property as resin, without using a crosslinking agent.

The intermediate layer may contain various particles for the purpose of improving the activity by forming irregularities on the surface. Examples of the particles to be contained in the intermediate layer include inorganic particles such as silica, kaolinite, talc, calcium carbonate, zeolite and alumina, and organic particles such as acrylic, PMMA, nylon, styrene, polyester, and benzoguanamine formalin condensate. Can be mentioned. Moreover, it is preferable to select the particle | grains whose refractive index and the resin used for transparency are close.

Moreover, in order to provide various functions to an intermediate | middle layer, you may contain surfactant, an antistatic agent, a pigment | dye, a ultraviolet absorber, etc.

Although the intermediate | middle layer may be a single | mono layer, when it has a target function, you may laminate | stack two or more layers as needed.

Although the thickness of an intermediate | middle layer will not be specifically limited if it has a target function, 0.01 micrometer or more and 5 micrometers or less are preferable. When the thickness is thin, the function is less likely to be expressed even as the intermediate layer. On the contrary, when the thickness is thick, transparency tends to be poor.

As a method of providing the intermediate layer, a coating method is preferable. As a coating method, it is a manufacturing process of a film using well-known coating methods, such as a gravure coat system, a kiss coat system, a dip system, a spray coat system, a curtain coat system, an air knife coat system, a blade coat system, a reverse roll coat system. Can be installed by an inline coat method for installing the coating layer, or an offline coat method for installing the coating layer after film production. Among these methods, the inline coating method is not only excellent in terms of cost, but also by including particles in the coating layer, there is no need to include particles in the transparent base material, and therefore, transparency can be highly improved, which is preferable.

(Near infrared absorption layer)

The near-infrared absorption filter of this invention is provided with the near-infrared absorption layer which consists of a composition which mainly contains a near-infrared absorbing dye and resin on a transparent base material directly or via an intermediate | middle layer. Said "mainly containing a near-infrared absorbing dye and resin" means containing 80 mass% or more of a near-infrared absorbing dye and resin in the said composition.

The near-infrared absorbing dye is a dye having a maximum absorption in the near-infrared region having a wavelength of 800 to 1200 nm and includes a diimmonium, phthalocyanine, dithiol metal complex, naphthalocyanine, azo, polymethine, anthraquinone and naph. Compounds, such as a toquinone type, a pyryllium type, a thiopyryllium type, a squarylium type, a croconium type, a tetrahydrocholine type, a triphenylmethane type, a cyanine type, an azo type, and an aluminum type, are mentioned. Although these compounds are used individually or in mixture of 2 or more types, they contain the diimmonium salt compound represented by following General formula (1) which has large absorption of a near-infrared region, wide absorption range, and high transmittance of visible region. It is preferable.

As a specific example of R <_1> -R <_8> in said Formula (1), (a) methyl group, an ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, ter-butyl group, n-amyl group , n-hexyl group, n-octyl group, 2-hydroxyethyl group, 2-cyanoethyl group, 3-hydroxypropyl group, 3-cyanopropyl group, methoxyethyl group, ethoxyethyl group, butoxyethyl group, etc. Aryl groups such as alkyl groups, (b) phenyl groups, fluorophenyl groups, chlorophenyl groups, tolyl groups, diethylaminophenyl groups, naphthyl groups, (c) alkenyl groups such as vinyl groups, propenyl groups, butenyl groups, pentenyl groups, and (d ) Allylalkyl groups such as benzyl group, p-fluorobenzyl group, p-chlorophenyl group, phenylpropyl group and naphthylethyl group.

R ₉ to R ₁₂ include hydrogen, fluorine, chlorine, bromine, diethylamino group, dimethylamino group, cyano group, nitro group, methyl group, ethyl group, propyl group, trifluoromethyl group, methoxy group, ethoxy group and propoxy group Etc. can be mentioned.

X ^- is fluorine, chlorine, bromine, iodine, perchlorate, hexafluoroantimonate, hexafluorophosphate, tetrafluoroborate, bis (trifluoromethanesulfonyl) Deacid ions, and the like.

This diimmonium salt compound can be obtained as a commercial item, For example, Kayasorb IRG-022, IRG-023, IRG-024, IRG-068 by Nippon Kayaku, CIR-1080, CIR-1081, CIR-1083, CIR-1085, CIR-1085F, CIR-RL, etc. are suitable.

Among them, the bis (trifluoromethanesulfonyl) imide is already in view of improving the heat resistance and the heat resistance by containing a trifluoromethanesulfonic acid compound or a bis (trifluoromethanesulfonyl) imide acid compound in the near infrared absorbing layer. The diimmonium salt compound which makes deacid ion a counter ion is preferable.

As a diimmonium salt compound having bis (trifluoromethanesulfonyl) imide acid ion as a counter ion, among commercially available diimmonium salt compounds, Kayasorb IRG-068 manufactured by Nippon Kayaku Co., CIR-1085, CIR-1085F manufactured by Nippon Kaliton , CIR-RL is illustrated.

In the near-infrared absorbing film of the present invention, other near-infrared absorbing dyes may be added for the purpose of expanding the absorption range of the near-infrared region and adjusting the color tone, in addition to the diimmonium salt compound represented by the formula (1).

As another near-infrared absorbing dye which can be used together with the said diimmonium salt type compound, a phthalocyanine type compound, a dithiol metal complex system compound, a cyanine type compound, a naphthalocyanine type compound, a squarylium salt type compound, a pyryllium salt type compound, thi Operyllium compounds, croconium compounds, inaniline chelate dyes, innaphthol chelate dyes, azo dyes, azochelate dyes, aluminium salt dyes, quinone dyes, anthraquinone dyes, polymethine dyes, Triphenylmethane type pigment | dye etc. are mentioned. Among them, phthalocyanine-based compounds and dithiol-based metal complex-based compounds with less deterioration under the high temperature and high humidity of the dye itself are preferred. When the pigment | dye which tends to deteriorate is used, not only stability of the transmittance | permeability of the near-infrared region becomes poor, a dimonium salt type compound acts as a quencher, deteriorates, and a near-infrared absorbing film discolors yellow.

Some of these can be obtained as a commercial item, for example, the phthalocyanine pigment | dye (IR-1, IR-2, IR-3, IR-4, IR-10, IR-10A, IR-12, made from Nippon Shokubai) IR-14), cyanine dyes (TZ-111, 114, 119, 121, 123) made by Asahi Denka, nickel complex dyes (MIR-101, MIR-111, MIR-121, MIR-102) , MIR-1011, MIR-1021), cyanine pigments (IR-301) made by Yamada Kagaku, cyanine pigments (YKR-2900) made by Yamamoto Chemicals, phthalocyanine pigments (YKR-3070, YKR-3081) Can be.

Among the near-infrared absorbing dyes described above, cyanine-based dyes containing a trifluoromethanesulfonic acid compound or a bis (trifluoromethanesulfonyl) imide acid compound as counter ions are preferable from the viewpoint of moisture-heat resistance and heat resistance improvement. For example, CY-40MC (F), CYP4646 (F) by Nippon Kayaku, or TZ-109D by Asahi Denka Co., Ltd. is mentioned as a commercial item.

In the present invention, in order to control the absorption of the near-infrared region of interest and the transmittance in the visible region, the amount of the near-infrared absorbing dye is 0.01 g / m 2 or more and 1.0 g / m 2 in any aspect in the thickness direction of the near-infrared absorbing layer. It is preferable to adjust so that it exists below. When the amount of the near infrared absorbing dye is small, the absorption ability in the near infrared region is insufficient. On the contrary, in many cases, there is a problem that the brightness of the display is lowered due to the lack of transparency in the visible region.

In the present invention, a method of laminating a near infrared absorbing layer on a transparent substrate includes a method of melting a near infrared absorbing dye and a resin by heating to install on a transparent substrate, and dissolving the near infrared absorbing dye and a resin in an organic solvent on a transparent substrate. The coating method of apply | coating, drying, and laminating is mentioned. The coating method in which the uniformity of the width direction and the flow direction of a near-infrared absorption layer is easy to be obtained is preferable.

In the present invention, the resin used for the near infrared absorbing layer is not particularly limited as long as it can dissolve or disperse the near infrared absorbing dye uniformly, but is not limited to polyester, acrylic, polyamide, polyurethane, polyolefin, and polycarbonate. Resin can be used suitably. Especially, acrylic resin which is excellent in heat resistance is preferable. Moreover, it is preferable that the glass transition temperature of resin is more than the usage guarantee temperature of the apparatus to be used.

When the glass transition temperature is equal to or lower than the device use temperature, the pigments dispersed in the resin react, or the resin absorbs moisture in the outside air and the like, and the deterioration of the dye and the binder resin increases. In the present invention, the glass transition temperature of the resin is not particularly limited as long as the glass transition temperature of the resin is higher than or equal to the apparatus use temperature, and particularly preferably 85 ° C. or higher and 160 ° C. or lower.

In addition, glass transition temperature is performed using differential scanning calorimetry (DSC) based on JISK7112, and glass transition temperature uses extrapolation glass transition start temperature. The measurement procedure was as follows.

About 5 mg of sample was enclosed in a measuring aluminum pan, mounted on a differential calorimeter (MAC Science DSC3100S), and heated up from 30 ° C. to 200 ° C. at a rate of 10 ° C./min under a nitrogen atmosphere. After reaching 200 ° C, the sample is taken out and immediately quenched. This pan is again mounted on a differential calorimeter, and the glass transition temperature (Tg: degreeC) is measured by heating at 30 degreeC at the speed of 10 degree-C / min.

When the glass transition temperature of resin used for a near-infrared absorption layer is less than 85 degreeC, interaction of a pigment | dye and resin, interaction of a pigment | dye, etc. arise, and a pigment | dye of a pigment becomes easy to generate | occur | produce. In addition, when the glass transition temperature exceeds 160 ° C., the resin should be heated to a high temperature to dissolve the resin in a solvent and to be sufficiently dried to apply it on a transparent substrate. Deterioration of the pigment occurs. In addition, when drying at low temperatures, the drying time is long, resulting in poor productivity and poor productivity. In addition, sufficient drying may not be possible, and a solvent remains in the coating film, and the glass transition temperature of the external appearance of a resin falls as mentioned above, and it becomes easy to generate | occur | produce a denaturation of a pigment similarly.

In addition, the acrylic resin having a high glass transition temperature is insufficient in flexibility, and the near-infrared absorbing layer has a problem that cracks are likely to occur due to impact or bending. As described later, flexibility can be imparted by containing the ionic liquid in the near infrared absorbing layer.

It is preferable that the quantity of a near-infrared absorbing dye in a near-infrared absorbing layer is 1 mass% or more and 10 mass% or less with respect to resin. When the amount of near-infrared absorbing dye in resin is small, it is necessary to increase the coating amount of a near-infrared absorbing layer in order to achieve the target near-infrared absorbing ability, and to make it dry enough, it is necessary to make it high temperature and / or long time, Deterioration, poor planarity of the substrate, and the like tend to occur. On the contrary, in the case where the amount of the near-infrared absorbing dye in the resin is large, the interaction between the dyes becomes strong, and even if the amount of the residual solvent in the near-infrared absorbing layer is reduced, the dye tends to change over time.

In the present invention, the near infrared absorbing layer is formed by applying and drying a coating liquid containing a near infrared absorbing dye, a resin, and an organic solvent on a transparent substrate. At this time, it is important to contain a surfactant in the coating liquid. By containing surfactant, the coating appearance of a near-infrared absorption layer, especially the removal by the micro bubble, the dent by adhesion of a foreign material, etc., and splashing in a drying process are improved. Further, the surfactant is bleeded to the surface by application drying and localized, so that the addition of a low surfactant of HLB not only improves durability, but also gives activity, so that the near infrared absorbing layer or / and vice versa. Even if surface unevenness is not provided in a surface, handling property becomes favorable and it becomes easy to wind up in roll shape.

Although surfactant can use suitably well-known thing of a cationic system, an anionic system, and a nonionic system, The nonionic system which does not have a polar group from the problem, such as deterioration with a near-infrared absorbing dye, is preferable, Furthermore, surfactant activity Silicone or fluorine-based surfactants having excellent performance are preferred.

Silicone surfactants include dimethylsilicone, aminosilane, acrylicsilane, vinylbenzylsilane, vinylbenzylaminosilane, glycidsilane, mercaptosilane, dimethylsilane, polydimethylsiloxane, polyalkoxysiloxane, hydrogen-modified siloxane, vinyl-modified siloxane , Hydroxy modified siloxane, amino modified siloxane, carboxyl modified siloxane, halogenated modified siloxane, epoxy modified siloxane, methacryloxy modified siloxane, mercapto modified siloxane, fluorine modified siloxane, alkyl group modified siloxane, phenyl modified siloxane, alkylene oxide modified Siloxane and the like.

Examples of fluorine-based surfactants include ethylene tetrafluoride, perfluoroalkyl ammonium salts, perfluoroalkyl sulfonate amides, sodium perfluoroalkyl sulfonates, perfluoroalkyl potassium salts, perfluoroalkyl carboxylates, and perfluoro Roalkylsulfonic acid salts, perfluoroalkylethylene oxide adducts, perfluoroalkyltrimethylammonium salts, perfluoroalkylaminosulfonates, perfluoroalkyl phosphate esters, perfluoroalkylalkyl compounds, perfluoroalkylalkylbeta Phosphorus, perfluoroalkyl halide, etc. are mentioned.

It is preferable that content of surfactant is 0.01 mass% or more and 2.00 mass% or less with respect to resin which comprises a near-infrared absorption layer. When there is little content of surfactant, the effect of the improvement of coating appearance and the provision of activity are lacking, On the contrary, in many cases, a near-infrared absorbing layer becomes easy to absorb water and the deterioration of a pigment may be accelerated.

In the present invention, the HLB of the surfactant is preferably 2 or more and 12 or less. The lower limit of the HLB is preferably 3, particularly preferably 4. On the other hand, the upper limit of the HLB is preferably 11, and particularly preferably 10. When the HLB is low, the surface is water-repellent and the deterioration of the pigment due to moisture-resistant heat can be suppressed, and it is easy to impart diactivation. However, when the HLB is too low, the leveling is caused by the lack of surfactant activity. Gender tends to be insufficient. On the contrary, when the HLB is high, not only the activity is insufficient, but the near-infrared absorbing layer tends to absorb moisture, and the color stability of the pigment tends to be poor.

In addition, HLB is WC Griffin of Atlas Powder of the United States named Hydorophil Lyophile Balance and indexed the balance between hydrophilic and lipophilic groups contained in the molecule of surfactant as a characteristic value. The higher the hydrophilicity.

The localization of the surfactant to the surface of the near-infrared absorbing layer differs depending on the type of resin and the solvent, but the HLB value is most likely to occur around 7, and the initial drying tends to occur more slowly. The degree of localization can be evaluated by comparing the amount of the surfactant in the vicinity of the surface of the near infrared absorbing layer measured using ESCA with the amount of the surfactant in the near infrared absorbing layer measured by chemical analysis.

In the present invention, it is important to contain either a trifluoromethanesulfonic acid compound or a bis (trifluoromethanesulfonyl) imide acid compound in the near infrared absorbing layer. By containing the said compound, it becomes possible to reduce the deterioration by the heat of a near-infrared absorbing dye, especially a diimmonium salt compound. Although the mechanism of action is not clear, it is presumed that the above-mentioned compound is ion-exchanged in the coating liquid or after drying with the counterion of the diimmonium salt compound to stabilize the dimonium salt compound. When the counterion of the diimmonium salt compound is a trifluoromethanesulfonic acid compound or a bis (trifluoromethanesulfonyl) imide acid compound, the low-molecular weight counterion contained in another dye or resin is the diimmonium salt compound. Since the ion exchange with the counterion of is suppressed, it is thought that the heat and moisture resistance and the heat resistance are improved.

In this invention, a well-known thing can be used as a trifluoromethanesulfonic acid compound, and lithium trifluoromethanesulfonic acid, potassium trifluoromethanesulfonic acid, and trifluoromethanesulfonic acid are trifluoromethanesulfonic anhydrides. Zinc trifluoromethanesulfonic acid, ammonium trifluoromethanesulfonic acid, yttrium trifluoromethanesulfonic acid, gadolinium trifluoromethanesulfonic acid, potassium trifluoromethanesulfonic acid, trifluoromethanesulfonic acid 3,5 -Dichloro-1-fluoropyridinium, trifluoromethanesulfonic acid 2,2,2-trifluoroethyl, trifluoromethanesulfonic acid trimethylsilyl, and sodium trifluoromethanesulfonic acid are mentioned. As the bis (trifluoromethanesulfonyl) imide acid compound, bis (trifluoromethanesulfonyl) imide acid lithium and bis (trifluoromethanesulfonyl) imide acid are already bis (trifluoromethanesulfonyl) imides Sodium Date, Bis (trifluoromethanesulfonyl) imide acid potassium, Bis (trifluoromethanesulfonyl) imide acid cesium, Bis (trifluoromethanesulfonyl) imide acid tetramethylammonium, Bis (trifluoromethane Sulfonyl) imide acid ethyltrimethylammonium, diethyldimethylammonium, bis (trifluoromethanesulfonyl) imide acid triethylmethylammonium, bis (trifluoromethanesulfonyl) imide acid tetraethylammonium, tetrabutylammonium, bis (Trifluoromethanesulfonyl) imide acid N, N-dimethylpyrrolidinium, bis (trifluoromethanesulfonyl) imide acid N-ethyl-N-methylpyrrolidinium, bis (trifluoromethanesulfonyl) Imide acid N, N-dimethyl Ferridinium, bis (trifluoromethanesulfonyl) imide acid N-ethyl-N-methylpiperidinium, bis (trifluoromethanesulfonyl) imide acid tetramethylphosphonium, tetraethylphosphonium, bis (tri Fluoromethanesulfonyl) imide acid 1-ethyl-2-methylimidazolium, bis (trifluoromethanesulfonyl) imide acid 1-ethyl-2,3-dimethylimidazolinium, bis (trifluoromethane Sulfonyl) imide acid 1,2,3,4-tetramethylimidazolinium.

In the present invention, as a structure similar to the bis (trifluoromethanesulfonyl) imide acid compound, bis (perfluoroalkanesulfonyl) imide acids and tris (perfluoroalkanesulfonyl) methides are also industrially It is available if it is available.

In the present invention, the near-infrared absorbing dyes other than the diimmonium salt compound may be any of the trifluoromethanesulfonic acid compound or the bis (trifluoromethanesulfonyl) imide acid as the counterion. In that case, although content is restrict | limited from an optical characteristic, what is necessary is just to contain either another trifluoromethanesulfonic acid compound or bis (trifluoromethanesulfonyl) imide acid compound separately as needed.

In the present invention, it is preferable to contain at least 0.1% by mass or more and 10.0% by mass or less of the trifluoromethanesulfonic acid compound or the bis (trifluoromethanesulfonyl) imide acid compound in the near infrared absorbing layer. If the said compound is less than 0.1 mass%, the improvement effect of heat resistance will become difficult to be acquired. On the contrary, when said compound exceeds 10 mass%, the problem that a haze becomes high by poor solubility arises.

In addition, when the trifluoromethanesulfonic acid compound or the bis (trifluoromethanesulfonyl) imide acid compound is an ionic liquid, by containing the ionic liquid in the near infrared absorption layer, not only the flexibility of the near infrared absorption layer is improved, but also the near infrared ray It becomes possible to reduce deterioration due to heat of the absorbing dye, especially the diimmonium salt compound. By containing a large amount of ions in the near-infrared absorbing layer, it can act as a plasticizer to impart flexibility, and is also stabilized by ion exchange with a counterion of the diimmonium salt compound. When the counterion of the diimmonium salt compound and the ionic liquid are the same, low molecular weight counterions contained in other dyes or resins interfere with ion exchange with the counterion of the diimnium salt compound, thereby improving heat resistance.

Said ionic liquid is a liquid salt consisting only of ions of an anion and a cation.

Examples of anionic species that make up the ionic liquid, for example, ^{Cl -, Br -, I -} , AlCl 4 -, Al 2 Cl 7 -, BF 4 -, PF 6 -, ClO 4 -, NO 3 -, CH 3 _{^{COO -, CF 3 COO -,}} CH 3 SO 3 -, CF 3 SO 3 -, (CF 3 SO 2) 2 N -, (CF 3 SO 2) 3 C -, AsF 6 -, SbF 6 -, NbF 6 _{^{-, TaF 6 -, F (}} HF) n -, (CN) 2 N -, C 4 F 9 SO 3 -, (C 2 F 5 SO 2) 2 N -, C 3 F 7 COO -, (CF 3 SO ₂ ) (CF ₃ CO) N ⁻ and the like. Among these, an anion component containing a fluorine-containing atom easily obtains an ionic compound having a low melting point, and easily provides flexibility of the near infrared absorbing layer. In the case where the counterion of the diimmonium salt compound is bis (trifluoromethanesulfonyl) imide acid, by using the same counterion, the effect of improving moisture resistance and heat resistance is obtained.

Specific examples of the cationic species include imidazolium and pyridinium. By using nitrogen-containing onium, sulfur-containing onium and phosphorus-containing onium, it is possible to impart an antistatic effect to the near infrared absorbing layer, which is preferable.

Although a commercial item may be used for the above ionic liquid, it is also possible to synthesize | combine as follows. The method for synthesizing the ionic liquid is not particularly limited as long as the target ionic liquid is obtained, but is generally described in the document "Ionic Liquid-Forefront and Future of Development" published by CMC Corporation. As the halide method, the hydroxide method, the acid ester method, the complexing method, the neutralization method, and the like are used.

It is preferable to make content of an ionic compound contain 0.1 mass% or more and 10.0 mass% or less in a near-infrared absorption layer. If it is less than 0.1 mass%, the effect of the improvement of heat resistance and flexibility provision by ionic liquid containing becomes difficult to be expressed. On the contrary, when it exceeds 10 mass%, it will precipitate on the surface of a near-infrared absorption layer, and adhesiveness with an adhesive will fall easily.

In this invention, it is preferable to laminate | stack a near-infrared absorption layer by apply | coating and drying a coating liquid containing resin, a near-infrared absorbing dye, and surfactant on a transparent base material. It is necessary to dilute this coating liquid with an organic solvent from coating property.

Examples of the organic solvent include (1) alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, tridecyl alcohol, cyclohexyl alcohol, and 2-methylcyclohexyl alcohol, and (2) Glycols such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, glycerin, etc. (3) Ethylene glycol monomethyl ether, ethylene glycol monoethylene ether, ethylene glycol monobutyl ether, di Ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol butyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl acetate, ethylene glycol monobutyl acetate, diethylene glycol monomethyl acetate, diethylene glycol monoethyl Glycol ethers such as acetate and diethylene glycol monobutyl acetate (4) esters such as ethyl acetate, isopropylene acetate, n-butyl acetate, (5) acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, isophorone, diacetone alcohol, etc. Ketones may be exemplified, and these may be used alone or in combination of two or more thereof.

Preferably, 30 mass% or more and 80 mass% or less of ketones excellent in the solubility of a pigment | dye are contained with respect to the all organic solvent used for a coating liquid. It is preferable to select other organic solvents in consideration of leveling properties and drying properties. Moreover, as for the boiling point of an organic solvent, 60 degreeC or more and 180 degrees C or less are preferable. When boiling point is low, solid content concentration of a coating liquid changes during coating, and coating thickness is hard to stabilize. On the contrary, when the boiling point is high, the amount of the organic solvent remaining in the coating film increases, resulting in poor stability over time.

As a method of dissolving or dispersing a near-infrared absorbing dye and resin in an organic solvent, the method of stirring, dispersion, and grinding | pulverization under heating is mentioned. By heating, the solubility of a pigment | dye and resin can be improved, and the defect to coating appearance by undissolved matter etc. is hindered. Moreover, it becomes possible to form a layer excellent in transparency by disperse | distributing and pulverizing and disperse | distributing resin and a pigment in a coating liquid in 0.3 micrometer or less fine particle state. As the disperser and the pulverizer, known ones can be used, and specifically, ball mills, sand mills, attritors, roll mills, agitators, colloid mills, ultrasonic homogenizers, homomixers, pearl mills, wet jet mills, paint shakers, A butterfly mixer, a planetary mixer, a Henschel mixer, etc. are mentioned.

In the case where the contamination or undissolved lysate of 1 µm or more is present in the coating liquid, since the appearance after application becomes poor, it is necessary to remove it with a filter or the like before applying. Although various things can be used suitably as a filter, It is preferable to use 99% or more of things of 1 micrometer size removal. In the case of applying and drying a coating liquid containing 1 µm or more of contaminants or unsealed products, dents or the like may occur around it, resulting in a defect of a size of 100 to 1000 µm.

As for solid content concentration, such as resin and pigment | dye contained in a coating liquid, 10 mass% or more and 30 mass% are preferable. When the solid content concentration is low, drying after application takes time, not only the productivity decreases, but also the amount of solvent remaining in the coating film increases, resulting in poor stability over time. On the contrary, when solid content concentration is high, the viscosity of a coating liquid will become high, and leveling property will become inferior and coating appearance will be bad. As for the viscosity of a coating liquid, 10 cps or more and 300 cps or less are preferable at the point of coating appearance, and it is preferable to adjust solid content concentration, an organic solvent, etc. so that it may become this range.

In the present invention, as a method of laminating the near-infrared absorbing layer on the transparent substrate by a coating method, a gravure coat method, a kiss coat method, a dip method, a spray coat method, a curtain coat method, an air knife coat method, a blade coat method, a reverse roll The method normally used, such as a coat system, a bar coat system, and a lip coat system, can be applied. Among these, the gravure coat method which can apply | coat uniformly, especially the reverse gravure method are preferable. Moreover, it is preferable that the diameter of gravure is 80 mm or less. Larger diameters increase the frequency of serpentine lines in the flow direction.

Although the coating amount after drying of a near-infrared absorption layer is not specifically limited, 1 g / m <2> is preferable for a minimum, More preferably, it is 3 g / m <2>, 50 g / m <2> is preferable and more preferably 30 g / m <2>. M 2. When the application amount after drying is small, the absorption power of near-infrared rays will tend to run short. Therefore, when the amount of the near-infrared absorbing dye in resin is increased, the distance between the dyes becomes shorter, so that the interaction between the dyes becomes stronger. As a result, deterioration of a dye tends to occur, and stability with time becomes poor. On the contrary, when the application amount after drying is large, the absorption ability of near-infrared rays is sufficient, but transparency in the visible light region is lowered and the brightness of the display is lowered. For this reason, when the amount of the near-infrared absorbing dye in the resin is reduced, the optical characteristics can be adjusted, but the drying tends to be insufficient. As a result, stability with time of a pigment | dye becomes poor with the residual solvent in a coating film. On the other hand, when dry enough, the planarity of a base material will become inferior.

Although a well-known hot air drying, an infrared heater, etc. are mentioned as a method of apply | coating a coating liquid on a transparent base material, and drying, hot air drying with a quick drying speed is preferable.

It is preferable to dry using hot air of 2 m / sec or more and 30 m / sec at 20 degreeC or more and 80 degrees C or less in the stage of initial stage drying after application | coating. When the initial drying is performed strongly (hot wind temperature is high and the amount of hot air is large), localization to the surface of the surfactant is difficult to occur, and the effect of improving the durability and imparting activity is hardly obtained. It is easy to produce minute defects in coating films such as missing coats, minute cracks, and cracks. On the contrary, in the case of weakening the initial drying (low hot air temperature and small amount of hot air), the appearance is good, but the drying time is not only troublesome in terms of cost, but also causes problems such as brushing. When surfactant is not added to a coating liquid, said small fault arises easily and it is necessary to make initial drying very weak.

In the reduction rate drying step, the solvent in the coating film needs to be reduced to a higher temperature than the initial drying, and the preferred temperature is 120 ° C or more and 180 ° C or less. Especially preferably, a lower limit is 140 degreeC and an upper limit is 170 degreeC. When the temperature is low, the solvent in the coating film is less likely to decrease, becoming a residual solvent and insufficient stability of the dye over time. On the contrary, in the case of high temperature, not only the planarity of a base material becomes poor by heat wrinkle, but a near-infrared absorbing dye deteriorates by heat. Moreover, as passage time, it is preferable that they are 5 second or more and 180 second or less. If the time is short, the amount of solvent remaining in the coating film increases, resulting in poor temporal stability. On the contrary, in the case of long time, not only the productivity is poor, but also heat wrinkles occur on the substrate, resulting in poor planarity. The upper limit of the passage time is particularly preferably 30 seconds in terms of productivity and planarity.

In the end of drying, it is preferable to make hot air temperature below the glass transition temperature of resin, and to make room temperature of a base material below the glass transition temperature of resin in a flat state. In the case of leaving the drying furnace in a high temperature state, when the coated surface comes into contact with the roll surface, slippage becomes poor, not only scratches occur, but also curls may occur.

(Near infrared absorption film)

In this invention, a near-infrared absorption film means the film with the low transmittance | permeability of the near infrared region of 800-1200 nm, and the high transmittance | permeability of the visible light region of 400 nm-800 nm. The lower the transmittance of the near infrared region, the more preferable. Specifically, the transmittance is 40% or less, and more preferably 30% or less. When the transmittance is high, absorption of near infrared rays emitted from the plasma display is insufficient, and malfunction of the electronic apparatus using the near infrared remote controller cannot be prevented.

As adjustment of a transmittance | permeability, it can change according to the kind of above-mentioned near-infrared absorbing dye and the amount of presence of a near-infrared absorbing dye per unit area.

As a hue of a near-infrared absorbing film, when expressing with a Lab colorimeter, it is preferable that a value is -10.0-+10.0, and b value is -10.0-+10.0. If it is this range, it becomes a natural color also when it is provided in the front surface of a plasma display, and it is preferable.

As a method of adjusting a color tone, it can achieve by mixing with the kind of above-mentioned near-infrared absorbing dye, the amount of a near-infrared absorbing dye per unit area, and further mixing with other pigment | dye. In addition, when bonding together with other members, such as an electromagnetic wave prevention film, an antireflection film, and glass, using the adhesive layer colored on the front surface or the back surface of the near-infrared absorption film mentioned later, adjusting a color tone so that it may become a natural color as an optical filter. desirable.

As a coating appearance of a near-infrared absorption layer, it should be made to avoid the fault of the size of 300 micrometers or more, More preferably, 100 micrometers in diameter. The defect of 300 micrometers or more becomes like a bright spot when installed in front of a plasma display, and a defect becomes remarkable. The defect of 100 micrometers or more and less than 300 micrometers may be emphasized by the lens effect etc. by the bonding of adhesive processing, etc., and it should not exist as much as possible. In addition, thin lines, unevenness, and the like of the coating layer also become prominent on the front of the display and become a problem.

Even when the near-infrared absorbing film is left for a long time under high temperature and high humidity, it is preferable that the transmittance of the near infrared ray and the transmittance of the visible light do not change. When the stability over time under high temperature and high humidity is poor, not only the color tone of the display image changes, but also the effect of the present invention which prevents malfunction of the electronic device using the near infrared remote controller may be lost.

In order to improve the stability over time, the amount of solvent or solvent in the near-infrared absorbing layer is reduced by controlling the type of organic solvent used in the coating liquid, the thickness of the coating layer, and the drying conditions. It can be made favorable by adjusting content of the thing or the pigment in resin. The smaller the amount of the residual solvent in the near infrared absorbing layer, the better. The lower the amount of the residual solvent, the better. When it becomes 3 mass% or less, there will be no difference in stability with time substantially. However, in order to further reduce the amount of residual solvent, for example, if drying is made in an excessive condition, adverse effects such as poor flatness of the filter are generated, and productivity is lowered in a method such as vacuum drying.

In this invention, you may provide another function to the surface which does not provide a near-infrared absorption layer. Specifically, an antistatic layer, an easily bonding layer, an easily slid layer, an antireflection layer, and an electromagnetic wave prevention layer are mentioned. By providing the antireflection layer and the electromagnetic wave prevention layer, the member of the optical filter can be reduced, making it inexpensive, and reducing the interference surface of light, thereby improving the image quality of the plasma display. In the formation of the near infrared absorbing layer, the antistatic layer can reduce the adhesion of dust in a later step, thereby reducing the fine defects and improving the yield at the time of manufacture. The easily adhesive layer becomes able to improve the adhesiveness at the time of bonding together with another member with an adhesive, and an easily slid layer to improve handling property.

As an antistatic agent used for an antistatic layer, a well-known thing can be used, but when winding up on a roll at the time of manufacture of a near-infrared absorption film, when an antistatic layer contacts a near-infrared absorption layer and a near-infrared absorbing pigment, especially a diimium salt compound deteriorates, It is not preferable to use anionic or cationic surfactant types or cationic resins of quaternary ammonium salts, and it is necessary to contain π-conjugated conductive polymers. The conjugated system conductive polymer does not promote deterioration of near-infrared absorbing dyes, especially dimonium salts, and on the contrary, stability with time may be good. Examples of? conjugated conductive polymers include aniline and / or derivatives thereof, pyrrole and / or derivatives thereof, isothianaphthene and / or derivatives thereof, acetylene and / or derivatives thereof, thiophene and / or derivatives thereof and the like. . Especially, thiophene and / or its derivative which are few in coloring are preferable.

In the present invention, for the purpose of blocking harmful electromagnetic waves emitted from the display, the conductive layer may be provided directly or on the opposite side to the infrared absorbing layer via a pressure-sensitive adhesive. This conductive layer may use either a metal mesh or a conductive thin film, and when using a metal mesh, it is necessary to have a metal mesh conductive layer with an opening ratio of 50% or more. When the opening ratio of the metal mesh is low, electromagnetic shielding properties are improved, but there is a problem that the light transmittance is lowered. Therefore, an opening ratio of 50% or more is required to obtain a good light transmittance. As the metal mesh used in the present invention, a metal foil having high electrical conductivity is etched to form a mesh, or a metal mesh is fabricated using metal fibers, or a metal is attached to the surface of a polymer fiber by using a method such as plating. You may use the fiber made. The metal used for the electromagnetic wave absorbing layer may be any metal as long as it has high electrical conductivity and good stability, but is not particularly limited, but copper, nickel, tungsten, or the like is preferable from the viewpoint of workability and cost.

In addition, when a conductive thin film is used, what kind of conductive film may be sufficient as a transparent conductive layer, Preferably it is preferable that it is a metal oxide. As a result, a higher visible light transmittance can be obtained. In the present invention, when the electrical conductivity of the transparent conductive layer is to be improved, it is preferable that the structure is a repeating structure of three or more layers of metal oxide / metal / metal oxide. By multilayering the metal, conductivity can be obtained while maintaining high visible light transmittance. The metal oxide used in the present invention may be any metal oxide as long as it has conductivity and visible light transmittance. Examples include tin oxide, indium oxide, indium tin oxide, zinc oxide, titanium oxide, bismuth oxide, and the like. The above is an example and is not specifically limited. In addition, the metal layer used in the present invention is preferably gold, silver and a compound containing these from the viewpoint of conductivity.

In the case where the conductive layer is multilayered, for example, when the number of repeating layers is three, the thickness of the silver layer is preferably 50 to 200 kPa, more preferably 50 to 100 kPa. When the film thickness is thicker than this, the light transmittance decreases, and when thin, the resistance increases. Moreover, as thickness of a metal oxide layer, Preferably it is 100-1000 GPa, More preferably, it is 100-500 GPa. If it is thicker than this thickness, the color tone changes, and if thin, the resistance value rises. In the case of multilayering three or more layers, for example, in the case of five layers such as metal oxide / silver / metal oxide / silver / metal oxide, the thickness of the center metal oxide is thicker than the thickness of other metal oxide layers. desirable. By doing in this way, the light transmittance of the whole multilayer film improves.

The antireflection layer has a function of preventing surface reflection and preventing shining of a fluorescent lamp or the like. The method of imparting the antireflection function is not limited and can be arbitrarily selected. For example, a method of laminating a layer having a different refractive index on the surface of the substrate and reducing the interference by using interference of reflected light at the interface of the layer, surface The method of giving an unevenness | corrugation to is mentioned. As a method of forming the antireflection film of this method, the following two methods can be mentioned. One method is a method of forming an antireflection film on the surface of a substrate by a vapor deposition method or a sputtering method, and another method is a method of forming an antireflection film by applying an antireflection coating liquid to the surface of a substrate and drying it. to be. As a general theory, the former is said to be excellent in the antireflection characteristic, and the latter is excellent in economical efficiency. In the present invention, either method may be used.

(Optical filter)

In the present invention, the optical filter is provided on the front surface of the plasma display, and blocks the near infrared rays and electromagnetic waves generated from the display, and also functions to prevent reflection and improve color reproducibility for improving the visibility of the display. And furthermore, the display has a protective function.

An optical filter can mention the structure which bonded together an antireflection film, glass, an electromagnetic wave prevention film, and a near-infrared absorption film with an adhesive as an example, It is preferable to provide an ultraviolet-ray absorption ability, a color correction function, and the improvement function of color reproducibility to an adhesive. Moreover, since the number of members can be reduced and the weight can be reduced by using the composite film which provided each function to the same surface or the opposite surface of a film, said composite film is preferable embodiment from a cost reduction point. Furthermore, in order to reduce weight and image quality, direct connection filter which directly bonds to a panel of a plasma display without using glass is also a preferred embodiment.

By bonding an optical filter directly to a panel of a plasma display without using glass, the image quality can be improved and reduced in weight, but since heat of the panel can be easily transmitted, high heat resistance is required. However, since the near-infrared absorbing film of this invention is highly excellent in heat resistance, it is suitable also for a direct filter.

Next, the Example and comparative example of this invention are shown. In addition, the measuring method of the characteristic value used by this invention, and the evaluation method of an effect are as follows.

Coating Liquid Viscosity

The coating liquid was adjusted to 20 ° C. and measured at a rotor rotation speed of 60 rpm using a type B viscometer (manufactured by Tokyo Keiki, BL).

<Transmittance>

Using a spectrophotometer (Hitachi U-3500 type), light was irradiated to the near-infrared absorbing layer side in the range of wavelength 1100-200 nm, and the indoor air was measured as a reference of the transmittance | permeability.

<Tint>

Using a color difference meter (ZE-2000, manufactured by Nippon Denshoku Industries Co., Ltd.), light was irradiated to the near-infrared absorbing layer side and measured at a D65 light source and a viewing angle of 10 degrees.

<Heat resistance heat resistance>

The color tone after leaving for 500 hours in a 60 degreeC temperature and 95% humidity atmosphere was measured, and the change amount (DELTA) x, (DELTA) y of before and after process was calculated | required.

<Heat resistance>

The color tone after leaving for 500 hours in the atmosphere of a temperature of 90 degreeC was measured, and the change amount (DELTA) x, (DELTA) y of the color tone before and behind a process was calculated | required.

<Flexibility>

The film was cut to 10 mm in width, wrapped around the metal rod with the near infrared absorbing layer outward, and the presence or absence of cracking of the near infrared absorbing layer was confirmed. The metal rods were 1-20 mm in diameter, and 20 pieces of 1 mm intervals were used, and the minimum diameter which a crack does not produce was made into the evaluation value of flexibility.

Example 1

1. Manufacturing of transparent substrate

(1) Preparation of a masterbatch containing ultraviolet absorber

10 parts by mass of dried ultraviolet absorber (CYASORB UV-3638; 2,2 '-(1,4-phenylene) bis (4H-3,1-benzoxazin-4-one)) and particles 90 parts by mass of a polyethylene terephthalate (PET) resin (manufactured by TOYOBO-SEKI, ME553), which was not used, was mixed, and a master batch was produced using a kneading extruder. The extrusion temperature at this time was 285 degreeC, and the extrusion time was 7 minutes.

(2) Preparation of coating liquid for forming easily adhesive layer

The coating liquid for easily bonding layer formation was prepared according to the following method. 95 parts by mass of dimethyl terephthalate, 95 parts by mass of dimethyl isophthalate, 35 parts by mass of ethylene glycol, 145 parts by mass of neopentylglycol, 0.1 parts by mass of zinc acetate and 0.1 parts by mass of antimony trioxide were added to the reaction vessel and over 3 hours at 180 ° C. The transesterification reaction was performed. Next, 6.0 mass parts of 5-sodium sulfoisophthalic acid were added, and after esterifying over 240 hours at 240 degreeC, polycondensation reaction was performed and the polyester resin was obtained.

20 mass% aqueous solution of the self-crosslinking polyurethane resin containing the isocyanate group which blocked the 30 mass% aqueous dispersion of the obtained polyester resin with 6.7 mass parts and sodium bisulfite (Daiichi Kogyo Pharmaceutical Co., Elastron H-3) 40 parts by mass, 0.5 parts by mass of the catalyst for elastron (Cat 64), 47.8 parts by mass of water and 5 parts by mass of isopropyl alcohol, respectively, and anionic surfactant was added to the coating liquid by 1 mass. % And colloidal silica particles (Snowtex OL, manufactured by Nissan Chemical Co., Ltd.) were added to 5% by weight based on the solids content of the coating liquid to obtain a coating liquid.

(3) Production of base film

90 parts by mass of pellets of PET resin (ME553, manufactured by Toyoboseki Co., Ltd.) and intrinsic viscosity of 0.62 dl / g and 10 parts by mass of the above-described ultraviolet absorber-containing master batch at 135 ° C for 6 hours under reduced pressure drying (1 Torr And then fed to an extruder. The resin temperature to the melting part, the kneading part, the polymer pipe, the gear pump, and the filter of the extruder was 280 ° C, and the subsequent polymer pipe was 275 ° C, and extruded into a sheet form from the detention. These polymers were each filtered using the filter medium of a stainless sintered compact (nominal filter density: 95% cutting of 10 micrometers or more of particle | grains). In addition, the flat die was made to have a resin temperature of 275 ° C. The extruded resin was wrapped in a casting drum (roll diameter 400 °, Ra 0.1 μm or less) having a surface temperature of 30 ° C. by using an electrostatically applied cast method, cooled and solidified to produce an unstretched film. The discharge amount at this time was 48 kg / hr, and the obtained unstretched sheet was 300 mm in width and 1400 micrometers in thickness.

Next, the cast film was heated to 100 ° C using a heated roll group and an infrared heater, and then stretched 3.5 times in the longitudinal direction (running direction) with a roll group having a circumferential speed difference to obtain a uniaxially oriented film. About the whole roll used at the time of this film manufacture, the surface roughness of the roll was controlled to 0.1 micrometer or less with Ra, and the roll cleaner was installed in the preheating inlet of a longitudinal drawing process, and a cooling roll. The roll diameter of the longitudinal stretching process was 150 mm, and the film was adhere | adhered to the roll by employ | adopting the adhesion apparatus of a suction roll, electrostatic adhesion, and a part nip.

Then, the coating liquid for easily bonding layer formation was filtrated microscopically by the filter medium of 25 micrometers of filter particle size (initial filtration efficiency: 95%), and it apply | coated and dried on both surfaces by the reverse roll method. After coating, the end of the film was subsequently gripped with a clip to guide the hot air zone heated to 130 ° C., stretched to 4.0 times in the width direction after drying, and heat treated at 230 ° C. for 5 seconds, and 3% in the width direction during this heat treatment step. Was subjected to relaxation treatment to obtain a base film (B). The thickness of this film was 100 micrometers, and the coating amount of the easily bonding layer at this time was 0.01 g / m <2>. The transmittance | permeability in wavelength 380nm of the obtained film was 4%, and it had the outstanding ultraviolet absorbency. Moreover, the total light transmittance was 91% and the haze was 0.6%, and the transparency was excellent.

2. Lamination of Near Infrared Absorption Layer

The following coating liquid A (viscosity: 23 cps) was dried on the intermediate coating layer described above, and coated in reverse using diagonal gravure with a diameter of 60 cm so that the transmittance of 950 nm was 4.3%. It was made to dry by passing for 20 seconds with hot air of / sec for 20 seconds, hot air of 20 m / sec at 150 ° C for 20 seconds, and further for 10 seconds with hot air of 20 m / sec at 90 ° C, to prepare a near-infrared absorbing filter.

(Coating Liquid A for Near Infrared Absorption Layer)

The material of the coating liquid was mixed in the following mass ratio, and stirred for 30 minutes or more. Subsequently, the undissolved matter was removed with a filter having a nominal filter density of 1 µm to prepare a coating solution A.

Toluene 22.193% by mass

Methyl ethyl ketone 23.083 mass%

52.762 mass% of acrylic resin

(Soken chemicals, GS-1030, solid content concentration: 30 mass%, Tg: 115 degreeC)

Dimonium salt compound (pigment A) 0.937 mass%

(Made by Nippon Kalitz, CIR1085, counterion: bis (trifluoromethanesulfonyl) imide acid)

Cyanine pigment 0.076 mass%

(Made by Asahi Denka Kogyo, TZ-123)

0.059% by mass of silicon-based surfactant

(Dow Corning, Painted 57, HLB: 6.7)

0.890 mass% of lithium trifluoromethanesulfonate (Compound C)

Table 1 shows the kind of near-infrared absorbing dye (diimmonium salt compound), the kind of trifluoromethanesulfonic acid compound, and content which are contained in a near-infrared absorption layer. As shown in Table 2, the obtained near-infrared absorptive film was strong in absorption of a near-infrared region, the transmittance | permeability in the visible light region was high, and the heat-and-moisture resistance and heat resistance were also favorable.

Example 2

A near-infrared absorbing film was obtained in the same manner as in Example 1 except that the following coating liquid B was used.

(Coating Liquid B for Near Infrared Absorption Layer)

The material of the coating liquid was mixed in the following mass ratio, and stirred for 30 minutes or more. Subsequently, the undissolved matter was removed with a filter having a nominal filter density of 1 µm to prepare a coating solution B.

22.998 mass% of toluene

Methyl ethyl ketone 23.083 mass%

52.762 mass% of acrylic resin

(Soken chemicals, GS-1030, solid content concentration: 30 mass%, Tg: 115 degreeC)

Dimonium salt compound (pigment A) 0.937 mass%

(Made by Nippon Kalitz, CIR1085, counterion: bis (trifluoromethanesulfonyl) imide acid)

Cyanine pigment 0.076 mass%

(Made by Asahi Denka Kogyo, TZ-123)

0.059% by mass of silicon-based surfactant

(Dow Corning, Painted 57, HLB: 6.7)

0.085% by mass of lithium trifluoromethanesulfonate (Compound C)

Table 1 shows the kind of near-infrared absorbing dye (diimmonium salt compound), the kind of trifluoromethanesulfonic acid compound, and content which are contained in a near-infrared absorption layer. As shown in Table 2, the obtained near-infrared absorptive film was strong in absorption of a near-infrared region, the transmittance | permeability in the visible light region was high, and the heat-and-moisture resistance and heat resistance were also favorable.

Example 3

A near-infrared absorbing film was obtained in the same manner as in Example 1 except that the following coating liquid C was used.

(Coating Liquid C for Near Infrared Absorption Layer)

The material of the coating liquid was mixed in the following mass ratio, and stirred for 30 minutes or more. Subsequently, the undissolved matter was removed with a filter having a nominal filter density of 1 μm to prepare a coating solution C.

21.411 mass% of toluene

Methyl ethyl ketone 23.083 mass%

52.762 mass% of acrylic resin

(Soken chemicals, GS-1030, solid content concentration: 30 mass%, Tg: 115 degreeC)

Dimonium salt compound (pigment A) 0.937 mass%

(Made by Nippon Kalitz, CIR1085, counterion: bis (trifluoromethanesulfonyl) imide acid)

Cyanine pigment 0.076 mass%

(Made by Asahi Denka Kogyo, TZ-123)

0.059% by mass of silicon-based surfactant

(Dow Corning, Painted 57, HLB: 6.7)

Lithium trifluoromethanesulfonate (Compound C) 1.671 mass%

Table 1 shows the kind of near-infrared absorbing dye (diimmonium salt compound), the kind of trifluoromethanesulfonic acid compound, and content which are contained in a near-infrared absorption layer. As shown in Table 2, the obtained near-infrared absorptive film was strong in absorption of a near-infrared region, the transmittance | permeability in the visible light region was high, and the heat-and-moisture resistance and heat resistance were also favorable.

Comparative Example 1

A near-infrared absorbing film was obtained in the same manner as in Example 1 except that the following coating liquid D was used. This comparative example 1 is an example which does not contain a trifluoromethanesulfonic acid compound or a bis (trifluoromethanesulfonyl) imide acid compound in a near-infrared absorption layer.

(Coating Liquid D for Near Infrared Absorption Layer)

The material of the coating liquid was mixed in the following mass ratio, and stirred for 30 minutes or more. Subsequently, the undissolved matter was removed with a filter having a nominal filter density of 1 μm to prepare a coating solution D.

Toluene 23.083 mass%

Methyl ethyl ketone 23.083 mass%

52.762 mass% of acrylic resin

(Soken chemicals, GS-1030, solid content concentration: 30 mass%, Tg: 115 degreeC)

Dimonium salt compound (pigment A) 0.937 mass%

(Made by Nippon Kalitz, CIR1085, counterion: bis (trifluoromethanesulfonyl) imide acid)

Cyanine pigment 0.076 mass%

(Made by Asahi Denka Kogyo, TZ-123)

0.059% by mass of silicon-based surfactant

(Dow Corning, Painted 57, HLB: 6.7)

Table 1 shows the kinds of near infrared absorbing dyes (diimmonium salt compounds) contained in the near infrared absorbing layer. As shown in Table 2, the obtained near-infrared absorbing film had strong absorption of a near-infrared region. However, the transmittance in the visible light region was slightly lower than those in Examples 1 to 3 containing the trifluoromethanesulfonic acid compound (Compound C) in the near infrared absorbing layer, and the heat resistance was poor.

Example 4

In Example 1, it carried out similarly to Example 1 except having changed the lithium trifluoromethanesulfonate (compound C) contained in a near-infrared absorption layer into the bis (trifluoromethanesulfonyl) imide acid compound (compound D). To obtain a near-infrared absorbing film.

Table 1 shows the kind and content of the near-infrared absorbing dye (dimonium salt compound) and the bis (trifluoromethanesulfonyl) imide acid compound which are contained in a near-infrared absorption layer are shown in Table 1. As shown in Table 2, the obtained near-infrared absorptive film was strong in absorption of a near-infrared region, the transmittance | permeability in the visible light region was high, and the heat-and-moisture resistance and heat resistance were also favorable.

Example 5

A near-infrared absorbing film was obtained in the same manner as in Example 1 except that the following coating liquid E was used.

(Coating solution E for near infrared absorption layer)

The material of the coating liquid was mixed in the following mass ratio, and stirred for 30 minutes or more. Subsequently, the undissolved matter was removed with a filter having a nominal filter density of 1 µm to prepare a coating solution E.

Toluene 22.193% by mass

Methyl ethyl ketone 23.083 mass%

52.762 mass% of acrylic resin

(Soken chemicals, GS-1030, solid content concentration: 30 mass%, Tg: 115 degreeC)

Dimonium salt compound (pigment B) 0.937 mass%

(Made by Nippon Kalitz, CIR1081, counterion: antimony hexafluoride)

Cyanine pigment 0.076 mass%

(Made by Asahi Denka Kogyo, TZ-123)

0.059% by mass of silicon-based surfactant

(Dow Corning, Painted 57, HLB: 6.7)

0.890 mass% of lithium trifluoromethanesulfonate (Compound C)

Table 1 shows the kind of near-infrared absorbing dye (diimmonium salt compound), the kind of trifluoromethanesulfonic acid compound, and content which are contained in a near-infrared absorption layer. As shown in Table 2, the obtained near-infrared absorptive film was strong in absorption of a near-infrared region, the transmittance | permeability in the visible light region was high, and the heat-and-moisture resistance and heat resistance were also favorable.

Comparative Example 2

A near-infrared absorbing film was obtained in the same manner as in Example 1 except that the following coating liquid F was used. This comparative example 2 is an example which does not contain a trifluoromethanesulfonic acid compound or a bis (trifluoromethanesulfonyl) imide acid compound in a near-infrared absorption layer.

(Coating Liquid F for Near Infrared Absorption Layer)

The material of the coating liquid was mixed in the following mass ratio, and stirred for 30 minutes or more. Subsequently, the undissolved matter was removed with a filter having a nominal filter density of 1 µm to prepare a coating solution F.

Toluene 23.083 mass%

Methyl ethyl ketone 23.083 mass%

52.762 mass% of acrylic resin

(Soken chemicals, GS-1030, solid content concentration: 30 mass%, Tg: 115 degreeC)

Dimonium salt compound (pigment B) 0.937 mass%

(Made by Nippon Kalitz, CIR1081, counterion: antimony hexafluoride)

Cyanine pigment 0.076 mass%

(Made by Asahi Denka Kogyo, TZ-123)

0.059% by mass of silicon-based surfactant

(Dow Corning, Painted 57, HLB: 6.7)

Table 1 shows the kinds of near infrared absorbing dyes (diimmonium salt compounds) contained in the near infrared absorbing layer. As shown in Table 2, the obtained near-infrared absorbing film had strong absorption of the near-infrared region, but was inferior in moist heat resistance (particularly Δy) and heat resistance.

Example 6

A near-infrared absorbing film was obtained in the same manner as in Example 1 except that the following coating liquid G was used.

(Coating Liquid G for Near Infrared Absorption Layer)

The material of the coating liquid was mixed in the following mass ratio, and stirred for 30 minutes or more. Subsequently, the undissolved matter was removed with a filter having a nominal filter density of 1 μm to prepare a coating solution G.

Toluene 23.083 mass%

Methyl ethyl ketone 23.083 mass%

52.762 mass% of acrylic resin

(Soken chemicals, GS-1030, solid content concentration: 30 mass%, Tg: 115 degreeC)

Dimonium salt compound (pigment A) 0.937 mass%

(Made by Nippon Kalitz, CIR1085, counterion: bis (trifluoromethanesulfonyl) imide acid)

Compound E 0.076 mass%

(Cyanine Dye with Bis (trifluoromethanesulfonyl) imide Acid as Counter Ion)

Asahi Denka Kogyo, TZ-109D)

0.059% by mass of silicon-based surfactant

(Dow Corning, Painted 57, HLB: 6.7)

Table 1 shows the kind of near-infrared absorbing dye (diimmonium salt compound), the kind of trifluoromethanesulfonic acid compound, and content which are contained in a near-infrared absorption layer. As shown in Table 2, the obtained near-infrared absorptive film was strong in absorption of a near-infrared region, the transmittance | permeability in the visible light region was high, and the heat-and-moisture resistance and heat resistance were also favorable.

Example 7

A near-infrared absorbing film was obtained in the same manner as in Example 1 except that the following coating liquid H was used.

(Coating solution H for near infrared absorption layer)

The material of the coating liquid was mixed in the following mass ratio, and stirred for 30 minutes or more. Subsequently, the undissolved matter was removed with a filter having a nominal filter density of 1 µm to prepare a coating solution H.

Toluene 23.083 mass%

Methyl ethyl ketone 23.083 mass%

52.762 mass% of acrylic resin

(Soken chemicals, GS-1030, solid content concentration: 30 mass%, Tg: 115 degreeC)

Dimonium salt compound (pigment A) 0.937 mass%

(Made by Nippon Kalitz, CIR1085, counterion: bis (trifluoromethanesulfonyl) imide acid)

Compound E 0.076 mass%

(Cyanine Dye with Bis (trifluoromethanesulfonyl) imide Acid as Counter Ion)

Nippon Kayaku Co., CY-40MC (F))

0.059% by mass of silicon-based surfactant

(Dow Corning, Painted 57, HLB: 6.7)

Comparative Example 3

A near-infrared absorbing film was obtained in the same manner as in Example 1 except that the following coating liquid I was used.

(Coating Liquid I for Near Infrared Absorption Layer)

The material of the coating liquid was mixed in the following mass ratio, and stirred for 30 minutes or more. Subsequently, the undissolved matter was removed with a filter having a nominal filter density of 1 µm to prepare a coating solution I.

Toluene 23.083 mass%

Methyl ethyl ketone 23.083 mass%

52.762 mass% of acrylic resin

(Soken chemicals, GS-1030, solid content concentration: 30 mass%, Tg: 115 degreeC)

Dimonium salt compound (pigment A) 0.937 mass%

(Made by Nippon Kalitz, CIR1085, counterion: bis (trifluoromethanesulfonyl) imide acid)

Compound F 0.076 mass%

(Cyanine pigment | dye which makes antimony hexafluoride a counter ion; Nippon Kayaku Co., CY-40MC (S))

0.059% by mass of silicon-based surfactant

(Dow Corning, Painted 57, HLB: 6.7)

In Table 1, pigment | dye A-B and compound C-F mean the following compounds.

(Color A)

N, N, N ', N'-tetrakis (p-di-n-butylaminophenyl) -p-phenylenedimonium salt having bis (trifluoromethanesulfon) imide acid as the counterion

(Color B)

N, N, N ', N'-tetrakis (p-di-n-butylaminophenyl) -p-phenylenedimonium salt having antimony hexafluoride as the counterion

(Compound C)

Lithium trifluoromethanesulfonate

(Compound D)

n-butyl-3-methylpyridinium bis (trifluoromethanesulfonyl) imide

(Compound E)

Cyanine dyes having bis (trifluoromethanesulfonyl) imide acid as the counterion

(Compound F)

Cyanine pigment with antimony hexafluoride as counterion

Example 8

1. Manufacturing of transparent substrate

(1) Preparation of a masterbatch containing ultraviolet absorber

10 parts by mass of dried ultraviolet absorber (CYASORB UV-3638; 2,2 '-(1,4-phenylene) bis (4H-3,1-benzoxazinone-4-one)) and particles 90 parts by mass of a polyethylene terephthalate (PET) resin (manufactured by TOYOBO-SEKI, ME553), which was not used, was mixed, and a master batch was produced using a kneading extruder. The extrusion temperature at this time was 285 degreeC, and the extrusion time was 7 minutes.

(2) Preparation of coating liquid for forming easily adhesive layer

The coating liquid for easily bonding layer formation was prepared according to the following method. 95 parts by mass of dimethyl terephthalate, 95 parts by mass of dimethyl isophthalate, 35 parts by mass of ethylene glycol, 145 parts by mass of neopentylglycol, 0.1 parts by mass of zinc acetate and 0.1 parts by mass of antimony trioxide were added to the reaction vessel and over 3 hours at 180 ° C. The transesterification reaction was performed. Next, 6.0 mass parts of 5-sodium sulfoisophthalic acid were added, and after esterifying over 240 hours at 240 degreeC, polycondensation reaction was performed and the polyester resin was obtained.

20 mass% aqueous solution of the self-crosslinking polyurethane resin containing the isocyanate group which blocked the 30 mass% aqueous dispersion of the obtained polyester resin with 6.7 mass parts and sodium bisulfite (Daiichi Kogyo Pharmaceutical Co., Elastron H-3) 40 parts by mass, 0.5 parts by mass of the catalyst for elastron (Cat 64), 47.8 parts by mass of water and 5 parts by mass of isopropyl alcohol, respectively, and anionic surfactant was added to the coating liquid by 1 mass. % And colloidal silica particles (Snowtex OL, manufactured by Nissan Chemical Co., Ltd.) were added to 5% by weight based on the solids content of the coating liquid to obtain a coating liquid.

(3) Production of base film

90 parts by mass of pellets of PET resin (ME553, manufactured by Toyoboseki Co., Ltd.) and intrinsic viscosity of 0.62 dl / g and 10 parts by mass of the above-described ultraviolet absorber-containing master batch at 135 ° C for 6 hours under reduced pressure drying (1 Torr And then fed to an extruder. The resin temperature to the extruder melting part, the kneading part, the polymer pipe, the gear pump, and the filter was 280 ° C, and the subsequent polymer pipe was 275 ° C. These polymers were filtered using the filter media of a stainless sintered compact (nominal filter density: 95% of 10 micrometers or more). In addition, the flat die was made to have a resin temperature of 275 ° C. The extruded resin was wound around a casting drum (roll diameter 400 °, Ra 0.1 μm or less) having a surface temperature of 30 ° C. by using an electrostatically applied cast method, and cooled to solidify, thereby forming an unstretched film. The discharge amount at this time was 48 kg / hr, and the obtained unstretched sheet was 300 mm in width and 1400 micrometers in thickness.

Next, the cast film was heated to 100 ° C using a heated roll group and an infrared heater, and then stretched 3.5 times in the longitudinal direction (running direction) with a roll group having a circumferential speed difference to obtain a uniaxially oriented film. About the whole roll used at the time of this film manufacture, the surface roughness of the roll was controlled to 0.1 micrometer or less with Ra, and the roll cleaner was installed in the preheating inlet of a longitudinal drawing process, and a cooling roll. The roll diameter of the longitudinal stretching process was 150 mm, and the film was adhere | adhered to the roll by employ | adopting the adhesion device of a suction roll, electrostatic adhesion, and a part nip.

Then, the coating liquid for easily bonding layer formation was filtrated microscopically by the filter medium of 25 micrometers of filter particle size (initial filtration efficiency: 95%), and it apply | coated and dried on both surfaces by the reverse roll method. After coating, the end of the film was subsequently gripped with a clip to guide the hot air zone heated to 130 ° C., stretched to 4.0 times in the width direction after drying, and heat treated at 230 ° C. for 5 seconds. Relaxation of% gave a base film (B). The thickness of this film was 100 micrometers, and the coating amount of the easily bonding layer at this time was 0.01 g / m <2>. The transmittance | permeability of wavelength 380nm of the obtained film was 4%, and it had the outstanding ultraviolet absorbency. Moreover, the total light transmittance was 91% and the haze was 0.6%, and the transparency was excellent.

2. Lamination of Near Infrared Absorption Layer

The following coating solution J (viscosity 23 cps) was dried on the intermediate coating layer, and then coated in reverse using diagonal gravure with a diameter of 60 cm so as to have a transmittance of 950 nm of 4.3% and 5 m / at 40 ° C. It was made to dry by passing 20 seconds with hot air of 20 seconds, 20 seconds with hot air of 20 m / sec at 150 degreeC, and 10 second with hot air of 20 m / sec at 90 degreeC, and the near-infrared absorption filter was produced.

(Coating Liquid J for Near Infrared Absorption Layer)

The material of the coating liquid was mixed in the following mass ratio, and stirred for 30 minutes or more. Subsequently, the undissolved matter was removed with a filter having a nominal filter density of 1 µm to prepare a coating solution J.

Toluene 22.193% by mass

Methyl ethyl ketone 23.083 mass%

52.762 mass% of acrylic resin

(Soken chemicals, GS-1030, solid content concentration: 30 mass%, Tg: 115 degreeC)

Dimonium salt compound (pigment A) 0.937 mass%

(Made by Nippon Kalitz, CIR1085, counterion: bis (trifluoromethanesulfonyl) imide acid)

Cyanine pigment 0.076 mass%

(Made by Asahi Denka Kogyo, TZ-123)

0.059% by mass of silicon-based surfactant

(Dow Corning, Painted 57, HLB: 6.7)

Ionic liquid D 0.890 mass%

(n-butyl-3-methylpyridinium bis (trifluoromethanesulfonyl) imide)

Table 3 shows the kind of near-infrared absorbing dye (dimonium salt compound) and the kind and content of an ionic liquid in a near-infrared absorbing layer. In addition, the physical property of the obtained near-infrared absorption film is shown in Table 4. A film with strong absorption in the near infrared region and high transmittance in the visible light region was obtained. Moreover, heat resistance and flexibility were also favorable.

Example 9

A near-infrared absorbing film was obtained in the same manner as in Example 8 except that the following coating liquid K was used.

(Coating Liquid K for Near Infrared Absorption Layer)

The material of the coating liquid was mixed in the following mass ratio, and stirred for 30 minutes or more. Subsequently, the undissolved matter was removed with a filter having a nominal filter density of 1 μm to prepare a coating solution K.

22.998 mass% of toluene

Methyl ethyl ketone 23.083 mass%

52.762 mass% of acrylic resin

(Soken chemicals, GS-1030, solid content concentration: 30 mass%, Tg: 115 degreeC)

Dimonium salt compound (pigment A) 0.937 mass%

(Made by Nippon Kalitz, CIR1085, counterion: bis (trifluoromethanesulfonyl) imide acid)

Cyanine pigment 0.076 mass%

(Made by Asahi Denka Kogyo, TZ-123)

0.059% by mass of silicon-based surfactant

(Dow Corning, Painted 57, HLB: 6.7)

Ionic liquid D 0.085 mass%

(n-butyl-3-methylpyridinium bis (trifluoromethanesulfonyl) imide)

Table 3 shows the kind of near-infrared absorbing dye (dimonium salt compound) and the kind and content of an ionic liquid in a near-infrared absorbing layer. In addition, the physical property of the obtained near-infrared absorption film is shown in Table 4. A film with strong absorption in the near infrared region and high transmittance in the visible light region was obtained. Moreover, heat resistance and flexibility were also favorable.

Example 10

A near-infrared absorbing film was obtained in the same manner as in Example 8 except that the following coating liquid L was used.

(Coating Liquid L for Near Infrared Absorption Layer)

The material of the coating liquid was mixed in the following mass ratio, and stirred for 30 minutes or more. Subsequently, the undissolved matter was removed with a filter having a nominal filter density of 1 µm to prepare a coating solution L.

21.411 mass% of toluene

Methyl ethyl ketone 23.083 mass%

52.762 mass% of acrylic resin

(Soken chemicals, GS-1030, solid content concentration: 30 mass%, Tg: 115 degreeC)

Dimonium salt compound (pigment A) 0.937 mass%

(Made by Nippon Kalitz, CIR1085, counterion: bis (trifluoromethanesulfonyl) imide acid)

Cyanine pigment 0.076 mass%

(Made by Asahi Denka Kogyo, TZ-123)

0.059% by mass of silicon-based surfactant

(Dow Corning, Painted 57, HLB: 6.7)

Ionic liquid D 1.671 mass%

(n-butyl-3-methylpyridinium bis (trifluoromethanesulfonyl) imide)

Table 3 shows the kind of near-infrared absorbing dye (dimonium salt compound) and the kind and content of an ionic liquid in a near-infrared absorbing layer. In addition, the physical property of the obtained near-infrared absorption film is shown in Table 4. A film with strong absorption in the near infrared region and high transmittance in the visible light region was obtained. Moreover, heat resistance and flexibility were also favorable.

Comparative Example 4

A near-infrared absorbing film was obtained in the same manner as in Example 8 except that the following coating liquid M was used.

(Coating Liquid M for Near Infrared Absorption Layer)

The material of the coating liquid was mixed in the following mass ratio, and stirred for 30 minutes or more. Subsequently, the undissolved matter was removed with a filter having a nominal filter density of 1 μm to prepare a coating solution M.

Toluene 23.083 mass%

Methyl ethyl ketone 23.083 mass%

52.762 mass% of acrylic resin

(Soken chemicals, GS-1030, solid content concentration: 30 mass%, Tg: 115 degreeC)

Dimonium salt compound (pigment A) 0.937 mass%

(Made by Nippon Kalitz, CIR1085, counterion: bis (trifluoromethanesulfonyl) imide acid)

Cyanine pigment 0.076 mass%

(Made by Asahi Denka Kogyo, TZ-123)

0.059% by mass of silicon-based surfactant

(Dow Corning, Painted 57, HLB: 6.7)

Table 3 shows the kind of near-infrared absorbing dye (dimonium salt compound) in the near-infrared absorbing layer. In addition, the physical property of the obtained near-infrared absorption film is shown in Table 4. A film with strong absorption in the near infrared region was obtained. Although the transmittance | permeability in visible region is a little lower than Examples 8-10 which added the ionic liquid, heat resistance and flexibility became poor.

Reference Example 1

In Example 8, the near-infrared absorbing film was obtained like Example 8 except having changed the kind of ionic liquid to the following ionic liquid G.

Ionic liquid G: n-butyl-3-methylpyridinium tetrafluoroborate

Table 3 shows the kind of near-infrared absorbing dye (dimonium salt compound) and the kind and content of an ionic liquid in a near-infrared absorbing layer. In addition, the physical property of the obtained near-infrared absorption film is shown in Table 4. A film with strong absorption in the near infrared region and high transmittance in the visible light region was obtained. Moreover, heat resistance and flexibility were also favorable.

Example 11

In Example 8, the near-infrared absorption film was obtained like Example 8 except having changed the kind of ionic liquid to the following ionic liquid H.

Ionic liquid H: N, N, N-trimethyl-N-propylammonium bis (trifluoromethanesulfonyl) imide

Table 3 shows the kind of near-infrared absorbing dye (dimonium salt compound) and the kind and content of an ionic liquid in a near-infrared absorbing layer. In addition, the physical property of the obtained near-infrared absorption film is shown in Table 4. A film with strong absorption in the near infrared region was obtained. Although heat resistance was inferior to Example 8, it was better than Comparative Example 4. In addition, the flexibility was good.

Example 12

A near-infrared absorbing film was obtained in the same manner as in Example 8 except that the following coating liquid P was used.

(Coating Liquid P for Near Infrared Absorption Layer)

The material of the coating liquid was mixed in the following mass ratio, and stirred for 30 minutes or more. Subsequently, the undissolved matter was removed with a filter having a nominal filter density of 1 μm to prepare a coating solution P.

Toluene 22.193% by mass

Methyl ethyl ketone 23.083 mass%

52.762 mass% of acrylic resin

(Soken chemicals, GS-1030, solid content concentration: 30 mass%, Tg: 115 degreeC)

Dimonium salt compound (pigment B) 0.937 mass%

(Made by Nippon Kalitz, CIR1081, counterion: antimony hexafluoride)

Cyanine pigment 0.076 mass%

(Made by Asahi Denka Kogyo, TZ-123)

0.059% by mass of silicon-based surfactant

(Dow Corning, Painted 57, HLB: 6.7)

Ionic liquid D 0.890 mass%

(n-butyl-3-methylpyridinium bis (trifluoromethanesulfonyl) imide)

Table 3 shows the kind of near-infrared absorbing dye (dimonium salt compound) and the kind and content of an ionic liquid in a near-infrared absorbing layer. In addition, the physical property of the obtained near-infrared absorption film is shown in Table 4. A film with strong absorption in the near infrared region and high transmittance in the visible light region was obtained. Moreover, heat resistance and flexibility were also favorable.

Comparative Example 5

A near-infrared absorbing film was obtained in the same manner as in Example 8 except that the following coating liquid Q was used.

(Coating Liquid Q for Near Infrared Absorption Layer)

The material of the coating liquid was mixed in the following mass ratio, and stirred for 30 minutes or more. Subsequently, the undissolved matter was removed with a filter having a nominal filter density of 1 µm to prepare a coating solution Q.

Toluene 23.083 mass%

Methyl ethyl ketone 23.083 mass%

52.762 mass% of acrylic resin

(Soken chemicals, GS-1030, solid content concentration: 30 mass%, Tg: 115 degreeC)

0.97 mass% of diimmonium pigment | dyes (pigment B)

(Made by Nippon Kalitz, CIR1081, counterion: antimony hexafluoride)

Cyanine pigment 0.076 mass%

(Made by Asahi Denka Kogyo, TZ-123)

0.059% by mass of silicon-based surfactant

(Dow Corning, Painted 57, HLB: 6.7)

Table 3 shows the kind of near-infrared absorbing dye (dimonium salt compound) and the kind and content of an ionic liquid in a near-infrared absorbing layer. In addition, the physical property of the obtained near-infrared absorption film is shown in Table 4. A film with strong absorption in the near infrared region and high transmittance in the visible light region was obtained. Moreover, heat resistance and flexibility were also favorable.

Example 13

As a transparent base material, the near-infrared absorbing film was obtained like Example 8 except having laminated | stacked the near-infrared absorbing layer on the surface opposite to an anti-reflective layer using the reflecting film (Japanese fats and oils, Liaruk 7700S).

Table 3 shows the kind of near-infrared absorbing dye (dimonium salt compound) and the kind and content of an ionic liquid in a near-infrared absorbing layer. In addition, the physical property of the obtained near-infrared absorption film is shown in Table 4. A film with strong absorption in the near infrared region and high transmittance in the visible light region was obtained. Moreover, heat resistance and flexibility were also favorable.

In Table 3, pigment | dye A, B, compound D, G, H means the following compound.

(Color A)

N, N, N ', N'-tetrakis (p-di-n-butylaminophenyl) -p-phenylenedimonium salt having bis (trifluoromethanesulfon) imide acid as counterion

(Color B)

N, N, N ', N'-tetrakis (p-di-n-butylaminophenyl) -p-phenylenedimonium salt having antimony hexafluoride as the counterion

(Ionic liquid D)

n-butyl-3-methylpyridinium bis (trifluoromethanesulfonyl) imide

(Ionic liquid G)

n-butyl-3-methylpyridinium tetrafluoroborate

(Ionic liquid H)

N, N, N-trimethyl-N-propylammonium bis (trifluoromethanesulfonyl) imide

When the near-infrared absorbing film of the present invention is installed on the front side of a plasma display as a near-infrared absorbing filter, like the conventional near-infrared absorbing filter, it absorbs unnecessary near-infrared rays emitted from the display, thereby preventing malfunction of precision instruments. Since the change in the color tone due to heat can be greatly reduced, there is an advantage that it can contribute to the high quality of the plasma display and the degree of freedom in designing the optical filter is increased, which contributes greatly to the industry.

Claims (6)

A near-infrared absorbing film having a near-infrared absorbing layer composed of a composition mainly composed of a near-infrared absorbing dye and a resin on a transparent substrate, wherein the trifluoromethanesulfonic acid compound or bis (trifluoromethanesulfonyl) imide acid is contained in the composition. The near-infrared absorption film containing any one of the compounds. The method of claim 1, The near-infrared absorbing pigment contains a dimonium salt compound, The near-infrared absorption film characterized by the above-mentioned. The method of claim 2, A near-infrared absorption film characterized in that the diimmonium salt compound is a diimmonium salt compound having bis (trifluoromethanesulfonyl) imide acid as a counterion. The method according to any one of claims 1 to 3, A near-infrared absorbing film, wherein a trifluoromethanesulfonic acid compound or a bis (trifluoromethanesulfonyl) imide acid compound is contained as an ionic liquid in an amount of 0.1 mass% or more and 10.0 mass% or less in the near infrared absorbing layer. The method according to any one of claims 1 to 3, As a near-infrared absorbing dye, the cyanine pigment | dye which makes a trifluoromethanesulfonic acid compound or a bis (trifluoromethanesulfonyl) imide acid compound the counter ion contains 0.1 mass% or more and 10.0 mass% or less in a near-infrared absorption layer, It is characterized by the above-mentioned. Near-infrared absorption film made with. The method according to any one of claims 1 to 5, Resin which comprises a near-infrared absorption layer is acrylic resin, The near-infrared absorption film characterized by the above-mentioned.