KR100761646B1 - Wavelength-selective absorption filter - Google Patents

Abstract

The present invention provides a selective absorption optical filter having a large, broad absorption in the near-infrared region, absorbing neon light, and having high light transmittance in another visible light region, wherein the optical characteristic has little change over time and excellent wavelength selective absorption with excellent durability. Provide a filter.

Furthermore, this invention is obtained by laminating | stacking the wavelength selective absorption layer of the single | mono layer or multilayer which contains resin, a near-infrared absorbing pigment (A), and a pigment (B) on a transparent base material, and is wavelength 800-1200 nm and wavelength 550-620 nm. A wavelength selective absorption filter having maximum absorption, wherein one of the near-infrared absorbing dyes (A) is an aromatic dimonium pigment (a) having bis (trifluoromethanesulfonyl) imide acid as a counter ion, and the dye (B (A) is a porphyrin type pigment | dye or aza porphyrin type pigment | dye (b), It is a wavelength selective absorption filter characterized by the above-mentioned.

Optical filters, absorption filters, wavelength selection, diimnium, porphyrin

Description

Wavelength Selective Absorption Filter {WAVELENGTH-SELECTIVE ABSORPTION FILTER}

The present invention relates to an optical filter that absorbs near-infrared and neon light, and in particular, has a broadly large absorption in the near-infrared region, further absorbs neon light, has a high light transmittance in other visible light regions, and is stored under high temperature and high humidity. The present invention relates to a wavelength selective absorption filter excellent in durability with little change in the optical properties over time.

An optical filter having near infrared absorptivity has a property of blocking near infrared rays and allowing visible light to pass through, and is used in various applications.

In recent years, plasma displays have attracted attention as thin large-screen displays. However, near-infrared rays emitted from plasma displays cause malfunctions of electronic devices using the near-infrared remote control, and a near-infrared absorption filter is provided on the front of the plasma display.

As a near-infrared absorption filter, (1) the filter containing metal ions, such as copper and iron, in phosphate glass, (2) the interference filter which transmits a specific wavelength by laminating | stacking the layer from which refractive index differs, and interfering transmitted light, (3) An acrylic resin filter containing copper ions in a copolymer and a filter in which a layer obtained by dispersing or dissolving an infrared absorbing dye in (4) resin are laminated.

Among these, the filter of (4) has good workability and productivity, and the degree of freedom of optical design is also relatively large. Therefore, various methods of manufacturing the filter have been proposed (Japanese Patent Laid-Open No. 2002-82219, Japanese Patent Laid-Open No. 2002). -214427, Japanese Patent Laid-Open No. 2002-303720, Japanese Patent Laid-Open No. 2002-333517, Japanese Patent Laid-Open No. 2003-82302, Japanese Patent Laid-Open No. 2003-96040, Japanese Patent Laid-Open 11-305033, Japanese Patent Laid-Open No. 11-326629, Japanese Patent Laid-Open No. 11-326631, Japanese Patent Laid-Open No. 2000-227515, Japanese Patent Laid-Open No. 2002-264278 , International Publication No. 97/38855, Japanese Patent Publication No. 2003-114323 and Japanese Patent Publication No. 2002-138203.

Some of these methods have the ability to sufficiently block the near infrared rays emitted from the plasma display, but when used for a long time under high temperature and high humidity, the stability over time of the optical characteristics is insufficient.

As a method of suppressing the temporal stability of optical characteristics when used for a long time under high temperature and high humidity, the method of making the glass transition temperature of the resin constituting the near infrared absorbing layer to be equal to or higher than the guaranteed temperature of the device using the near infrared absorbing filter (for example, Japan Japanese Patent Laid-Open No. 11-305033, Japanese Patent Laid-Open No. 11-326629, Japanese Patent Laid-Open No. 11-326631, and Japanese Patent Laid-Open No. 2000-227515), and a near infrared absorbing layer A method of reducing the amount of residual solvent (see, for example, Japanese Patent Laid-Open No. 2000-227515 and Japanese Patent Laid-Open No. 2002-264278) has been proposed.

Moreover, it is known that the aromatic dimonium compound type pigment | dye used as a near-infrared absorbing dye is generally weak to heat (for example, refer to page 17 of International Publication No. 97/38855).

Therefore, in the near-infrared absorbing layer containing a diimmonium compound, as a technique of suppressing deterioration of the pigment | dye by heat, the diimnium compound is refine | purified and the specific dimonium type compound which has an endothermic peak at the temperature of 220 degreeC or more in DSC measurement. To a near infrared absorbing layer (for example, see Japanese Patent Laid-Open No. 2003-114323), a method for containing a diimnium compound having a melting point of 190 ° C. or higher in the near infrared shielding layer (for example, 2002-138203).

In addition, since the plasma display also emits neon orange light (near the wavelength of 600 nm), there is a problem that vivid color rendering of the display and image sharpness are impaired only by maintaining the stability of the near-infrared absorbing layer over time.

An object of the present invention is a selective absorption optical filter having a large, wide absorption in the near infrared region, absorbing neon light, and having a high light transmittance in another visible light region, with a small change in optical characteristics over time, and excellent in wavelength. It is to provide a selective absorption filter.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching in order to solve the said subject, the present inventors finally came to complete this invention. That is, this invention is as follows.

The first invention is obtained by laminating a single or multiple wavelength selective absorption layer containing a resin, a near infrared absorbing dye (A) and a dye (B) on a transparent substrate, and having a wavelength of 800 to 1200 nm and a wavelength of 550 to 620 nm. It is a wavelength selective absorption filter having maximum absorption,

One of the near-infrared absorbing dyes (A) is an aromatic dimonium pigment (a) having bis (trifluoromethanesulfonyl) imide acid as a counter ion,

One of the said dyes (B) is a porphyrin type pigment | dye or an aza porphyrin type pigment | dye (b), It is a wavelength selective absorption filter characterized by the above-mentioned.

According to a second aspect of the present invention, in the first aspect of the invention, the near-infrared absorbing layer in which the multilayer selective absorbing layer contains a resin and a near infrared absorbing dye (A), and the neon cut layer containing the resin and the dye (B) are transparent in this order. It is formed on the base material, It is a wavelength selective absorption filter characterized by the above-mentioned.

According to a third aspect of the invention, in the first aspect of the invention, the wavelength selective absorbing layer is 5 to 100 parts by mass of the porphyrin dye or azaporphyrin dye (b) based on 100 parts by mass of the aromatic diimmonium dye (a). Mass ratio).

In 4th invention, resin which comprises a wavelength selective absorption layer in said 1st invention is acrylic resin, It is a wavelength selective absorption filter characterized by the above-mentioned.

In 5th invention, in the said 1st invention, the wavelength selective absorption layer of a single | mono layer has the organic solvent, resin, aromatic dimonium pigment | dye (a), porphyrin pigment | dye, or azaporphyrin pigment | dye on the said transparent base material (b) It is a wavelength selective absorption filter characterized by apply | coating and drying coating liquid A containing containing.

6th invention is formed by apply | coating and drying the coating liquid B containing the organic solvent, resin, and an aromatic diimmonium pigment | dye (a) on the said transparent base material in the wavelength selective absorption layer of a multilayer in the said 1st invention. And a neon cut layer formed by applying and drying the formed near-infrared absorbing layer and a coating solution C containing an organic solvent and a resin, a porphyrin-based dye or an azaporphyrin-based dye (b) immediately above the near-infrared absorbing layer. It is a wavelength selective absorption filter.

7th invention is the wavelength selective absorption filter which the coating liquid A or B further contains surfactant whose HLB is 2-12 in the said 5th or 6th invention.

In 8th invention, in said 7th invention, surfactant is a silicone type surfactant or a fluorine-type surfactant, It is a wavelength selective absorption filter characterized by the above-mentioned.

Effect of the Invention

When the wavelength selective absorption filter according to the present invention is installed on the front surface of the plasma display, like the conventional wavelength selective absorption filter, unnecessary near-infrared rays emitted from the display can be absorbed to prevent malfunction of precision instruments and unnecessary neon light can be prevented. Because of the absorption, the sharpness of the image is high, the change due to temperature and humidity is small, and the change over time of the high quality of the plasma display can be reduced.

Best Mode for Carrying Out the Invention

The wavelength selective absorption filter of the present invention is obtained by laminating a single or multiple wavelength selective absorption layer containing a resin, a near infrared absorbing dye (A) and a dye (B) on a transparent substrate, and having a wavelength of 800 to 1200 nm and a wavelength of 550. A wavelength selective absorption filter having a maximum absorption at 620 nm, wherein one of the near infrared absorbing dyes (A) is an aromatic dimonium pigment (a) having bis (trifluoromethanesulfonyl) imide acid as a counter ion, One of the pigments (B) is characterized in that it is a porphyrin-based dye or azaporphyrin-based dye (b).

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

(Transparent mention)

In this invention, although a transparent base material is not specifically limited, It is preferable that total light transmittance is 80% or more, and 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 films, sheets, such as polyester type, acrylic type, cellulose type, polyethylene type, polypropylene type, polyolefin type, polyvinyl chloride type, polycarbonate, phenol type, urethane type, glass, and the like; The thing which joined any 2 or more types of these is mentioned. It is preferably a polyester film having 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 aromatic dicarboxylic acid or its ester, such as terephthalic acid, isophthalic acid, and naphthalene dicarboxylic acid as a dicarboxylic acid component, and ethylene glycol and di as a glycol component. The esterification reaction or the transesterification reaction is performed using ethylene glycol, 1,4-butanediol, neopentyl glycol, etc., and then the polyester chip obtained by polycondensation reaction is dried, melted with an extruder, and is melt | dissolved in the sheet form from T die | dye. It is a film manufactured by extending | stretching the unstretched sheet obtained by extrusion in at least one axial direction, and then performing a heat setting process and a relaxation process.

The film is particularly preferably a biaxially stretched film in terms of strength and the like. Examples of the stretching method include a tubular stretching method, a simultaneous biaxial stretching method, a sequential biaxial stretching method, and the like, but a sequential biaxial stretching method is preferable from the planarity, dimensional stability, and thickness nonuniformity. A sequential biaxially stretched film is roll-drawn in the longitudinal direction by the magnification of 2.0 times or more and 5.0 times or less, for example at the temperature of glass transition temperature (Tg) or more (Tg + 30 degreeC or less) of polyester in a longitudinal direction. Subsequently, after preheating with a tenter, it extends | stretches in the width direction by 1.2 times or more and 5.0 times or less at the temperature of 120 degreeC or more and 150 degrees C or less. In addition, the biaxially stretched film is subjected to a heat fixation treatment at a temperature of 220 ° C. or higher (melting point −10 ° C. or lower). Next, the polyester film suitable as a transparent base material used by this invention can be manufactured by relaxing 3%-8% in a width direction. Moreover, in order to further improve the dimensional stability of the longitudinal direction of a film, 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. . It is preferable that there are few content of particle | grains in a film from a transparency point, For example, it is preferable that they are 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, a film can also be made to contain a light resistant agent (ultraviolet-proof agent), a pigment | dye, an antistatic agent, etc. in order to provide various functions as needed.

The transparent base material used by this invention may be a single | mono layer film, and 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 in that the functions of the surface layer and the center layer can be designed independently. For example, transparency can be further improved as a whole of the composite film by containing particles only in the thin surface layer to form irregularities on the surface, while maintaining handling properties while substantially not including particles in the thick center layer. The method for producing the composite film is not particularly limited, but considering the productivity, the raw materials of the surface layer and the center layer are extruded from separate extruders, guided by one die to obtain an unstretched sheet, and then oriented in at least one axial direction. It is especially preferable to manufacture by the so-called coextrusion method.

Although the thickness of a transparent base material changes with a raw material, when using a polyester film, 35 micrometers or more are preferable and 50 micrometers or more are more preferable. On the other hand, 260 micrometers or less are preferable and 200 micrometers or less are more preferable. When the thickness is thin, not only the handling property is poor, but when heated at the time of drying to reduce the amount of residual solvent in the wavelength selective absorbing layer, thermal wrinkles occur in the film, and the planarity is likely to be poor. On the other hand, when the thickness is thick, not only is there a problem in terms of cost, but when it is wound and stored in a roll shape, poor planarity due to winding marks is likely to occur.

(Middle floor)

Although the wavelength selective absorption filter of this invention has the structure which laminated | stacked the wavelength selective absorption layer of a single layer or multiple layers on the transparent base material, an intermediate | middle layer can also be provided for the purpose of improving the adhesiveness of a transparent base material and a wavelength selective absorption layer, or the transparency of a transparent base material. have. 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 at the time of film manufacture simultaneously.

Examples of the resin constituting the intermediate layer include polyester resins, polyurethane resins, polyester urethane resins, acrylic resins, melamine resins, and the like, but it is important to select such resins to have good adhesion with the substrate and the wavelength selective absorbing layer. For example, when resin which comprises a base material and a wavelength selective absorption layer is ester type, it is preferable to select polyester type and polyester urethane type which have a similar structure.

The said intermediate | middle layer can also contain a crosslinking agent in order to improve adhesiveness and water resistance, and can form a crosslinked structure. Examples of the crosslinking agent include urea, epoxy, melamine and isocyanate. In particular, when the resin causes whitening or a decrease in strength under high temperature and high humidity, the effect of the crosslinking agent is remarkable. Instead of using a crosslinking agent, a graft copolymer resin having self crosslinking property may be used as the resin.

The intermediate layer may contain various particles for the purpose of forming irregularities on the surface to improve lubricity. 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. 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, it is difficult to express the function as an intermediate layer. On the contrary, when the thickness is thick, transparency tends to be poor.

It is preferable to provide an intermediate | middle layer by the apply | coating method. As a coating method, it is applied in the manufacturing process of a film using well-known coating methods, such as gravure coating method, kiss coating method, immersion method, spray coating method, curtain coating method, air knife coating method, blade coating method, reverse roll coating method. An inline coating method for providing a layer, an offline coating method for installing an application layer after film production, and the like can be employed. Among these methods, the in-line coating method is preferable because it is not only excellent in cost but also includes particles in the coating layer so that the particles are not included in the transparent substrate, and thus transparency can be highly improved.

(Wavelength selective absorption layer)

The wavelength selective absorption filter of this invention laminate | stacks the wavelength selective absorption layer which consists of a single layer or multilayer laminated constitution which contains the pigment | dye which has near-infrared absorptive ability on a transparent base material directly or through an intermediate | middle layer.

The near-infrared absorbing dye is a dye having a maximum absorption in the near-infrared region having a wavelength of 800 nm or more and 1200 nm or less, and is a diimium-based, phthalocyanine-based, dithiol metal complex, naphthalocyanine-based, azo-based, polymethine-based, anthraquinone-based And compounds such as naphthoquinone series, pyryllium series, thiopyryllium series, squarylium series, croconium series, tetradehydrocholine series, triphenylmethane series, cyanine series, azo series and aluminum series. Although these compounds are used individually or in mixture of 2 or more types, in this invention, they contain the diimmonium salt compound represented by following formula (I) which has a large absorption of a near-infrared region, a wide absorption region, and also has a high transmittance of a visible region. It is necessary to do

In the formulas, specific examples of R ¹ to R ⁸ include (1) methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, n-amyl and n- Alkyl groups, such as a hexyl group, n-octyl group, 2-hydroxyethyl group, 2-cyanoethyl group, 3-hydroxypropyl group, 3-cyanopropyl group, methoxyethyl group, ethoxyethyl group, butoxyethyl group, ( 2) aryl groups such as phenyl group, fluorophenyl group, chlorophenyl group, tolyl group, diethylaminophenyl, naphthyl group, (3) alkenyl groups such as vinyl group, propenyl group, butenyl group, pentenyl group, and (4) benzyl group and aralkyl groups such as p-fluorobenzyl group, p-chlorophenyl group, phenylpropyl group and naphthylethyl group.

As R ⁹ to R ¹² , 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.

In the formula (I), X ⁻ represents fluorine ion, chlorine ion, bromine ion, iodine ion, perchlorate ion, hexafluoro antimonate ion, hexafluoro phosphate ion, tetrafluoroborate ion, bis (trifluoromethanesulfonyl ) Imide acid ion, etc. are mentioned. In addition, in this invention, since an azaporphyrin type pigment | dye etc. are used as a neon cut pigment | dye (it mentions later), it is necessary to include the near-infrared absorption pigment | dye which is said X ^- bis (trifluoromethanesulfonyl) imide acid ion. This compound can be obtained as a commercial item, For example, CIR-1085, CIR-RL by Nippon Carit, and IRG-068 by Nippon Kayaku are mentioned.

The wavelength selective absorption filter of the present invention may add another near infrared absorbing dye for the purpose of expanding and adjusting the absorption region of the near infrared region in addition to the diimmonium salt compound represented by the above formula (I). It is preferable not to accelerate deterioration of a diimmonium salt type pigment | dye, Preferably, the phthalocyanine type | system | group, the cyanine pigment | dye, and the dithiol metal complex system which have an absorption peak in 800 nm or more and 1200 nm or less are mentioned.

In the present invention, in order to control the absorption of the near-infrared region of interest and the transmittance in the visible-light region, the amount of the near-infrared absorbing dye is 0.01 g / m ² or more in any aspect in the thickness direction of the wavelength selective absorbing layer 1.0 g / It is preferable to adjust so that it may be m <^2> or less. 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 this invention, it is necessary to contain a neon cut pigment | dye in a wavelength selective absorption layer. Plasma displays emit a so-called neon-orange light centered around 600 nm, and there is a drawback in that red is mixed with orange to obtain a clear red color. By containing a neon cut pigment | dye, the said problem can be solved.

In the present invention, the neon cut dye is a dye having a maximum absorption in the wavelength range of 550 nm or more and 620 nm or less, and specifically, a cyanine-based, squarylium-based, azomethine-based, xanthene-based, oxonol-based, azo-based or phthalocyanine And quinones, azeleniums, pyrylliums, croconiums, dithiol metal complexes, pyrromethenes, and azaporphyrins. Although these pigment | dyes can be used individually or in mixture of 2 or more types, in this invention, it is necessary to use a porphyrin type pigment | dye or an aza porphyrin type pigment | dye.

Porphyrin dyes or azaporphyrin dyes are dyes represented by the following formulas (II) and (III). Specific examples of R ¹¹ to R ¹⁴ and R ¹⁵ to R ^{22 in} the formulas (II) and (III) include a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amino group, a carboxyl group, a sulfonic acid group, an alkyl group having 1 to 20 carbon atoms, and halo. A genoalkyl group, an alkoxy group, an alkoxyalkoxy group, an aryloxy group, a monoalkylamino group, a dialkylamino group, an aralkyl group, an aryl group, a heteroaryl group, an alkylthio group or an arylthio group, each of which is independently a linking group You may form a ring except an aromatic ring through. Examples of M include two hydrogen atoms, a divalent metal atom, a trivalent monosubstituted metal atom, a tetravalent disubstituted metal atom, or an oxy metal atom.

This compound is available as a commercial item, for example, TAP-2, TAP-5, TAP-9, TAP-10, TAP-12, and Mitsui Chemicals, PD-319, PD-311 by Yamada Chemical Industries, Ltd. Can be mentioned.

It is preferable to adjust content of the neon cut pigment | dye so that the obtained wavelength selective absorption filter may have clear absorption in the wavelength range of 550 nm or more and 62O nm or less, and the transmittance | permeability in a maximum absorption wavelength is 30% or less. Specifically, it is preferable to make a neon cut pigment exist in 0.001 g / m <^2> or more and 0.1 g / m <^2> or less on a transparent base material.

In the present invention, the wavelength selective absorbing layer is composed of a single layer or a multilayer structure. As a wavelength selective absorption layer, two pigment | dyes of the aromatic dimonium pigment | dye (a) which uses bis (trifluoromethanesulfonyl) imide acid as a counter ion, and a porphyrin pigment | dye or an azaporphyrin pigment | dye (b) are the same coating layer. It is preferable to set it as the single layer structure mixed in the inside.

In the present invention, an aromatic diimmonium dye having bis (trifluoromethanesulfonyl) imide acid as a counter ion as a near-infrared absorbing dye in a monolayer wavelength selective absorbing layer, and a porphyrin dye or azaporphyrin dye as a neon cut dye. It is necessary to employ the above because the effect of improving the durability of the wavelength selective absorbing layer is obtained by mixing these two pigments in the same coating layer. In addition, although the mechanism for improving durability is not clear, bis (trifluoromethanesulfonyl) imide acid, which is a counter ion of the diimmonium pigment, and azaporphyrin pigment (or porphyrin pigment) cause some interactions, thereby causing humidity and It is estimated that pigment | dye deterioration by temperature is suppressed.

In addition, in this invention, the near-infrared absorbing layer containing resin and a near-infrared absorbing dye (A) as a wavelength selective absorbing layer, and the neon cut layer containing resin and a dye (B) are formed in this order of the multilayer. The wavelength selective absorption layer which consists of a structure can be used. A multilayer layer in which a layer containing an aromatic dimonium pigment (a) having a bis (trifluorometansulfonyl) imide acid as a counter ion and a porphyrin dye or an azaporphyrin dye (b) alone as a wavelength selective absorption layer is laminated. By making it a structure, the improvement effect of durability is acquired similarly to the wavelength selective absorption layer of a single layer. Although the reason is not clear, at the interface between the near-infrared absorbing layer and the neon cut layer, interaction between the dye (a) and the dye (b) occurs, and at the same time, the movement of the dye occurs at the interface, so that the dye (a) and The same effects as in the case where the dye (b) is present are obtained.

It is preferable to contain 5 mass parts or more with respect to 100 mass parts of diimmonium pigments, and, as for an azaporphyrin type pigment (or porphyrin type pigment), 10 mass parts or more are more preferable. It is preferable that it is 100 mass parts, and, as for an upper limit, it is more preferable that it is 50 mass parts or less. When the ratio of an azaporphyrin type pigment | dye etc. with respect to an aromatic dimonium pigment | dye is not in a preferable range, the above-mentioned interaction does not occur and it may be difficult to improve durability.

In the present invention, the near-infrared absorbing dye or neon cut dye is laminated on the transparent substrate by the coating method in a state dispersed or dissolved in the resin. The resin is not particularly limited as long as it can uniformly dissolve or disperse a near infrared absorbing dye or a neon cut dye, but polyester, acrylic, polyamide, polyurethane, polyolefin, and polycarbonate resins are preferably used. Can be. Especially, acrylic resin which is excellent in transparency, heat resistance, and solvent resistance at the time of dye mixing is preferable, and especially when using the diimmonium pigment | dye which has bis (trifluoromethanesulfonyl) imide acid as a counter ion, It is preferable to employ | adopt acrylic resin from a viewpoint of adhesiveness and affinity with a pigment | dye.

In addition, it is preferable that the glass transition temperature of said resin is more than the guaranteed temperature of the apparatus in which a wavelength selective absorption filter is used. When the glass transition temperature of the resin is equal to or lower than the use temperature of the device in which the wavelength selective absorption filter is used, the pigments dispersed in the resin are easily reacted, and the resin absorbs moisture in the outside air and the like and deteriorates the pigment or the resin. Becomes large. In addition, in this invention, if the glass transition temperature of resin is more than the use temperature of the apparatus in which a wavelength selective absorption filter is used, it will not specifically limit, It is especially preferable that they are 85 degreeC or more and 160 degrees C or less.

When the glass transition temperature of said resin is less than 85 degreeC, interaction of a pigment | dye and resin, interaction of a pigment | dye, etc. arise, and a pigment | dye is modified. In addition, when the glass transition temperature exceeds 160 ° C., if the resin is to be dissolved in a solvent and sufficiently dried when coated on a transparent substrate, the resin should be heated to a high temperature. Deterioration occurs. Moreover, when drying at low temperature, since it takes a long time to dry, productivity becomes poor. In addition, sufficient drying may not be possible, and in the case where a large amount of solvent remains in the coating film, dimmium salt-based pigments having poor durability as in the case where the above-described glass transition temperature is below the use temperature of the device in which the wavelength selective absorption filter is used. Causes degeneration

In the case of using a wavelength selective absorbing layer composed of a multilayer structure, the resin used for the neon cut layer is different from the diimnium salt dye, and the porphyrin dye or the aza porphyrin dye (b) itself is excellent in durability. Less influence of glass transition temperature or drying conditions. However, when a strong resin such as an amine is used as the resin used for the neon cut layer, the durability of the diimnium salt dye may be deteriorated at the interface between the neon cut layer and the near-infrared absorbing layer containing the diimium salt dye. have.

As resin used for the neon cut layer which does not contain a dimonium salt type pigment | dye, resin of polyester type, acryl type, polyamide type, polyurethane type, polyolefin type, and polycarbonate type can be used preferably. Among these resins, acrylic resins excellent in transparency at the time of dye mixing and heat resistance are preferable. Moreover, when bonding with an antireflection film, glass, and an electromagnetic wave prevention film, an adhesive can also be used as resin.

Examples of the pressure-sensitive adhesives include known acrylic adhesives, silicone adhesives, urethane adhesives, polyvinyl butyral adhesives (PVB), ethylene-vinyl acetate adhesives (EVA), polyvinyl ethers, saturated amorphous polyesters, melamine resins, and the like. Among these pressure-sensitive adhesives, acrylic pressure-sensitive adhesives are preferable in terms of transparency and the like.

An acrylic adhesive contains resin which has an acrylic ester, methacrylic acid ester, etc. as a main component, for example. In addition, an adhesive can be used as a hardening | curing agent as needed, for example, a metal chelate type, an isocyanate type, and an epoxy type crosslinking agent mixed with the said adhesive resin.

It is preferable that the quantity of a near-infrared absorbing dye in a wavelength selective absorption 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 wavelength selective absorbing layer in order to achieve the target near-infrared absorbing ability, and high temperature and / or long time are required for sufficient drying accordingly. Deterioration of the dye, 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 residual solvent is reduced, the dye tends to occur over time.

In this invention, the wavelength selective absorption layer which consists of a single-layer laminated structure is a transparent base material which contains the coating liquid A containing an organic solvent, resin, an aromatic diimmonium pigment | dye (a), a porphyrin pigment | dye, or an azaporphyrin pigment | dye (b). It is formed by applying and drying on the phase. Moreover, the wavelength selective absorbing layer which consists of a multilayer structure of the multiple layer is a near-infrared absorption layer formed by apply | coating and drying the coating liquid B containing the organic solvent, resin, and aromatic diimmonium pigment | dye (a) on a transparent base material, and this near-infrared absorption layer The neon cut layer formed by apply | coating and drying the coating liquid C containing an organic solvent and resin, a porphyrin type pigment | dye, or an azaporphyrin type pigment | dye (b) directly above is formed.

At this time, it is preferable to contain surfactant in the said coating liquid A or B. Moreover, although surfactant can also be contained also in the coating liquid C, when using an adhesive as resin, you may not contain surfactant.

By containing a surfactant in the coating liquid used for formation of a wavelength selective absorbing layer, the coating appearance of a wavelength selective absorbing layer, especially the omission by a micro bubble, the dent by adhesion of a foreign material, etc., and the cratering in a drying process are improved. Furthermore, the surfactant in the wavelength selective absorption layer (coating layer) is bleeded to the surface by heat treatment at the time of drying the coating layer. As a result, lubricity can be provided to the surface of an application layer. Moreover, even if it contains the particle | grains which cause deterioration of transparency in a wavelength selective absorption layer and / or an opposite surface, and does not form surface irregularities, handling property becomes favorable and it becomes easy to wind up in roll shape.

In this invention, it is important that HLB of surfactant is 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 leveling property is insufficient due to the lack of surface active ability. On the contrary, when the HLB is high, not only the lubricity is deficient, but also the wavelength selective absorbing layer tends to absorb moisture, and the time-lapse stability of the diimnium pigment is poor.

In addition, HLB is a value obtained by indexing hydrophilic and lipophilic groups contained in a molecule of a surfactant as a characteristic value by Griffin (WCGriffin) of Atlas Powder of the United States named hydrophilic lipophilic balance. The lower this value, the higher the lipophilicity. On the contrary, the higher the value, the higher the hydrophilicity.

It is important that content of surfactant is 0.01 mass% or more and 2 mass% or less with respect to resin which comprises a wavelength selective absorption layer. When the amount of the surfactant is small, the effect of improving the coating appearance and imparting lubricity is insufficient. On the contrary, in many cases, the wavelength selective absorbing layer tends to absorb moisture, thereby facilitating deterioration of the dye.

The surfactant may be preferably a cationic, anionic or nonionic, but is preferably a nonionic which does not have a polar group from problems such as deterioration with a near infrared absorbing dye. Or fluorine-based surfactants.

Silicone surfactants include dimethylsilicone, aminosilane, acrylicsilane, vinylbenzylsilane, vinylbenzylaminosilane, glycidosilane, mercaptosilane, dimethylsilane, polydimethylsiloxane, polyalkoxysiloxane, hydrodiene-modified siloxane, vinyl-modified siloxane, and hydroxide. Roxy modified siloxane, amino modified siloxane, carboxy 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, etc. Can be mentioned.

Examples of the fluorine-based surfactants include ethylene tetrafluoride, perfluoroalkyl ammonium salt, perfluoroalkyl sulfonate amide, sodium perfluoroalkyl sulfonate, perfluoroalkyl potassium salt, perfluoroalkyl carboxylate, perfluoroalkyl sulfonate, Perfluoroalkyl ethylene oxide adducts, perfluoroalkyl trimethylammonium salts, perfluoroalkyl aminosulfonates, perfluoroalkyl phosphate esters, perfluoroalkyl alkyl compounds, perfluoroalkyl alkylbetaines, perfluoro Alkyl halides; and the like.

In the present invention, the wavelength selective absorbing layer is laminated by applying and drying a coating liquid containing a resin, a near infrared absorbing dye, and a surfactant on a transparent substrate, and the coating liquid needs to be diluted with an organic solvent in view of coatability. Do.

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) ethylene Glycols such as glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol and glycerin, (3) ethylene glycol monomethyl ether, ethylene glycol monoethylene ether, ethylene glycol monobutyl ether, diethylene 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 acetate, Diethylene glycol monobutyl acetate, etc. Colethers, (4) esters, such as ethyl acetate, isopropylene acetate, n-butyl acetate, (5) acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, isophorone, diacetone Ketones, such as alcohol, can be illustrated and these can be used individually or in mixture of 2 or more types.

Preferably, the ketones excellent in the solubility of a pigment | dye are contained 30 mass% or more and 80 mass% or less with respect to the total organic solvent used for a coating liquid, and it is preferable to select other organic solvents in consideration of leveling property and dryness. 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 difficult to stabilize. On the contrary, when boiling point is high, the amount of the organic solvent which remain | survives in a coating film increases and stability with time becomes bad.

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 the coating appearance by an undissolved thing etc. can be prevented. Furthermore, it becomes possible to form a layer excellent in transparency by dispersing and pulverizing and disperse | distributing resin and a pigment in a coating liquid in 0.3 micrometer or less fine particle state. As a disperser and a grinder, a well-known thing can be used, Specifically, a ball mill, a sand mill, an attritor, a roll mill, a stirrer, a colloid mill, an ultrasonic homogenizer, a homo mixer, a pearl mill, a wet jet mill, a paint shaker, a butterfly Mixers, planetary mixers, Henschel mixers and the like.

If a contaminant or an undissolved product 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 coating. Although various things can be used suitably as a filter, it is preferable to use what removes 99% or more of things of 1 micrometer size. When the coating liquid containing 1 micrometer or more of contaminants or undissolved matters is apply | coated and dried, dents etc. generate | occur | produce around it, and it may become a fault of the magnitude | size of 100 micrometers or more and 1000 micrometers or less.

It is preferable to make solid content concentration, such as resin and a pigment | dye contained in a coating liquid, 10 mass% or more and 30 weight% or less. 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. It is preferable to adjust the viscosity of a coating liquid to 10 cps or more and 300 cps or less from an external viewpoint of coating, and to adjust solid content concentration, an organic solvent, etc. so that it may become this range.

In the present invention, a method of applying the wavelength selective absorbing layer on the transparent substrate may include a gravure coating method, a kiss coating method, an immersion method, a spray coating method, a curtain coating method, an air knife coating method, a blade coating method, a reverse roll coating method, and a bar coating method. The method normally used, such as a system and a lip coating system, can be applied. Among these, the gravure coating method which can apply | coat uniformly, especially the reverse gravure method are preferable. In addition, it is preferable that the diameter of gravure is 80 mm or less. Larger diameters increase the frequency of creases in the flow direction.

Although the coating amount after drying of a wavelength selective absorption layer is not specifically limited, 1 g / m <^2> is preferable, as for a minimum, 3 g / m <^2> is more preferable, 50 g / m <^2> is preferable and an upper limit is 30 g / m <^2>. Is more preferable. 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 the resin is increased, the amount of the dye present at the interface between the surface and the anchor layer increases, and the influence of external air or anchor layer resin is likely to occur. 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. Therefore, although the optical characteristic can be adjusted by reducing the amount of the near-infrared absorbing dye in resin, drying becomes inadequate easily. As a result, the time-lapse stability 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.

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

It is preferable to dry using hot air of 2 m / sec-30 m / sec at 20 degreeC or more and 80 degrees C or less in the step of the initial rate drying after application | coating. When the initial drying is performed strongly (hot wind temperature is high, and the amount of hot air is large), minute defects of the coating film such as micro coating omission, micro cratering, cracking, etc. derived from foam easily occur. On the contrary, when the initial drying is weakened (the hot air temperature is low and the amount of hot air is small), the appearance becomes good, but there is a problem in terms of cost due to the drying time. When surfactant is not added to a coating liquid, the said micro fault is easy to generate | occur | produce, and it is necessary to carry out initial drying fairly weakly.

In the step of reduction rate drying, the solvent in the coating film needs to be reduced to a higher temperature than the initial drying, and preferable temperatures are 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 be reduced to become a residual solvent, resulting in 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 pigment deteriorates by heat. Moreover, as passage time, it is preferable that they are 5 second or more and 180 second or less. When the time is short, the amount of remaining solvent in the coating film increases, resulting in poor stability over time. On the contrary, when the time is long, not only the productivity is poor, but also thermal wrinkles are generated on the substrate, resulting in poor planarity. The upper limit of the elapsed time is particularly preferably 30 seconds in terms of productivity and planarity.

It is preferable to make hot air temperature below the glass transition temperature of resin at the final stage of drying, and to room temperature of a base material below the glass transition temperature of resin in a flat state. In the high temperature state, when taken out of the drying furnace, when the coated surface comes into contact with the roll surface, the lubricity is poor, not only scratches occur, but also curls may occur.

(Wavelength selection absorption filter)

In the present invention, the wavelength selective absorption filter is an optical filter having a maximum absorption at a wavelength of 800 to 1200 nm and a wavelength of 550 to 620 nm. This wavelength selective absorption filter is so preferable that the transmittance | permeability in the near infrared region of wavelength 800 nm or more and 1200 nm or less is so preferable. Specifically, the transmittance of the near infrared region is preferably 20% or less, and particularly preferably 10% or less. When the transmittance is high, absorption of near infrared rays emitted from the plasma display is insufficient, and malfunctions of electronic devices using the near infrared remote controller cannot be prevented.

In addition, the average transmittance of the visible region is higher than the average transmittance of the near-infrared region, and it is preferable to have clear absorption at a wavelength of 550 nm or more and 620 nm or less, and a wavelength of 570 nm to 600 nm. Specifically, the transmittance at the maximum absorption wavelength within the wavelength range is preferably 40% or less, and particularly preferably 30% or less. When the transmittance in this area is high, it becomes difficult to obtain the effect of absorbing neon light emitted from the plasma display to improve red color development. In addition, when the absorption of this region is large, the overall transmittance of the visible light region decreases, so that the luminance of the display tends to decrease. The higher the transmittance of the visible light region except for the wavelength of 550 nm or more and 620 nm or less, the higher the value is, and preferably 50% or more, particularly preferably 60% or more. If the transmittance is low, the color of the display is disturbed, resulting in a low luminance image.

The adjustment of the transmittance can be changed depending on the application amount of the wavelength selective absorbing layer and the amount of the near infrared absorbing dye per unit area.

As a color tone of a wavelength selective absorption filter, it is preferable that a value is -10.0-+10.0, and b value is -10.0-+10.0 when expressed with a Lab colorimeter. If it is this range, even if it is provided in the front of a plasma display, a natural color is produced and it is preferable.

As a method of adjusting a color tone, it can achieve by the application amount of a wavelength selective absorbing layer, the amount of a near-infrared absorbing dye per unit area, further mixing of other pigment | dye, or the optimization of drying conditions. In addition, when the colored adhesion layer or another optical filter exists in the front or back surface of the wavelength selective absorption filter mentioned later, it is preferable to also include it and to adjust the color tone of a wavelength selective absorption filter to a natural color.

As the coating appearance of the wavelength selective absorbing layer, it is necessary to ensure that there are no defects having a maximum diameter of 300 µm or more, more preferably of 100 µm. The defects of 300 µm or more are formed on the front surface of the plasma display and become like bright spots, which makes the defects remarkable. In addition, the thin streaks, nonuniformities, etc. of the coating layer also become prominent on the front of the display and become a problem.

It is preferable that the transmittance of near infrared rays and the transmittance of visible light do not change even if the wavelength selective absorption filter is left for a long time under high temperature and high humidity. When the stability over time under high temperature and high humidity is poor, not only the image color tone of the display 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.

The stability over time is improved by mixing an aromatic dimonium pigment (a) having a bis (trifluoromethanesulfonyl) imide acid as a counter ion with a porphyrin dye or an azaporphyrin dye (b), but in addition, the coating liquid By controlling the type of organic solvent used, the thickness of the coating layer, the drying conditions and the like, the amount of residual solvent in the wavelength selective absorbing layer can be reduced, or the content of the dye in the resin can be further improved.

In addition, as described above, a near-infrared absorbing layer containing a resin and an aromatic diimmonium dye (a) having bis (trifluoromethanesulfonyl) imide acid as a counter ion, a resin, a porphyrin dye, or an azaporphyrin dye The use of the wavelength selective absorption layer which consists of the structure of the multilayered layer in which the neon cut layer containing (b) is formed on a transparent base material in this order is also preferable from a point of stability with time.

The smaller the amount of the residual solvent in the wavelength selective absorbing layer, the better. The lower the amount of the residual solvent, the more preferably 3% by mass or less. When it is 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 performed under severe conditions, adverse effects such as poor flatness of the filter are generated, and productivity is reduced in a method such as vacuum drying.

In the present invention, for the purpose of blocking harmful electromagnetic waves emitted from the display, the conductive layer may be provided directly or via an adhesive on the same or opposite side as the infrared absorbing layer. Any of a metal mesh and a conductive thin film can be used for the said conductive layer, 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, the electromagnetic shielding property is improved, but there is a problem that the light transmittance is lowered. Therefore, in order to obtain a favorable light transmittance, an opening ratio of 50% or more is required. As the metal mesh used in the present invention, a metal foil having high electrical conductivity is etched to form a mesh, and a metal mesh is attached to the surface of a woven mesh using metal fibers or the surface of a polymer fiber by a method such as plating. Fibers can also be used. The metal used in 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 in view of processability and cost.

In the case where a conductive thin film is used, the transparent conductive layer may be any conductive film, but is preferably a metal oxide. Thereby, higher visible light transmittance can be obtained. Moreover, in order to improve the electrical conductivity of a transparent conductive layer in this invention, it is preferable that it is a repeating structure of three or more layers of a 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. Moreover, as for the metal layer used for this invention, gold, silver, and the compound containing these are preferable from a conductive viewpoint.

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 kPa to 200 kPa, more preferably 50 kPa to 100 kPa. In the case where the film thickness is thicker than this, the light transmittance decreases, and in the case where the film thickness is thin, the resistance increases. The thickness of the metal oxide layer is preferably 100 kPa to 1000 kPa, more preferably 100 kPa to 500 kPa. If it is thicker than this thickness, the color tone changes, and if thin, the resistance value increases. 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 the other metal oxide layers. desirable. By doing in this way, the light transmittance of the whole multilayer film improves.

In the present invention, an anti-reflection layer and an anti-glare layer may be provided on the same or opposite side of the wavelength selective absorbing layer of the wavelength selective absorbing filter directly or through an adhesive. Moreover, in the wavelength selective absorption layer which consists of several laminated constitution, the neon cut layer can be made to adhere to a glass plate and a resin sheet by giving a function of an adhesion layer to a neon cut layer using adhesive resin, and can also be bonded directly to a display. Moreover, an adhesive layer can also be formed in the surface of the wavelength selective absorption layer of a single layer.

In the wavelength selective absorption filter of this invention, you may provide the layer which has an ultraviolet absorption ability for the purpose of improving light resistance. In order to provide an ultraviolet absorbing power, it is preferable to add a ultraviolet absorber to any one of a wavelength selective absorbing layer, a transparent base material, an adhesive layer, an antireflection layer, and an anti-glare layer. A ultraviolet absorber can use well-known things, such as an organic type sunscreen agent and an inorganic type sunscreen agent.

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.

<Viscosity of Coating Liquid>

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

<Total light transmittance, haze>

The total light transmittance and the haze were measured using a haze meter (Nippon Denshoku Kogyo Co., Ltd., NDH2000).

<Light transmittance>

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

<Tint>

Light was irradiated to the wavelength selective absorption layer side using the color difference meter (ZE-2000 by Nippon Denshoku Kogyo Co., Ltd.), and the a value and the b value of the Lab colorimeter were measured as a C light source and a 2 degree viewing angle as standard light.

<Stability over time>

After leaving for 48 hours in a temperature of 80 ° C. and a humidity of 95%, the above-mentioned transmittance and color tone were measured. ΔE was calculated from the following equation (1) as the amount of change in color tone. In addition, ΔE indicates that the smaller the value, the smaller the change in color tone.

ΔE = √ ((a value before processing-a value after processing) ² + (b value before processing-b value after processing) ² )

Subsequently, the amount of change ΔT before and after the time course of the transmittance was calculated from the following equation (2). ΔT indicates that the smaller the value, the smaller the change amount.

% Change = (transmittance after treatment-transmittance before treatment | / transmittance before treatment) x 100

<Appearance of coating>

(1) micro defect

The filter after wavelength selective absorption layer formation was put on the white film, visually observed under fluorescent lamp of 3 wavelengths, and the following evaluation was performed. In addition, the micro fault was measured the number of defects of the size of 300 micrometers or more per 100 m <^2> , and was ranked according to the following judgment criteria.

◎: less than 1 minute defect

○: 1 or more minute defects less than 5

(Triangle | delta): Five or more micro defects are less than ten

×: 10 or more minute defects

(2) Poor coating

For the presence or absence of coating defects such as coating unevenness and stripes, the wavelength selective absorption filter was placed on a white film, and the wavelength selective absorption layer surface was visually observed under a fluorescent lamp having three wavelengths, and ranked according to the following criteria.

(Double-circle): A coating defect is not seen even if it observes and moves a wavelength selective absorption filter.

(Circle): When it moves and observes a wavelength selective absorption filter, a little coating defect can be seen.

(Triangle | delta): Coating defect can be seen when moving a wavelength selective absorption filter and observing.

X: Coating defect is understood even when the wavelength selective absorption filter is stopped.

<Adhesiveness>

The adhesiveness was measured by the test method based on 8.5.1 of JISK5400. Specifically, 100 scale-shaped cut scratches were made from the side of the wavelength selective absorbing layer laminated using a cutter guide with a gap of 2 mm, and the cellophane adhesive tape ("No. 405" manufactured by Nichibansa Co., Ltd., 24 mm width) was scaled. After adhere | attached on the cut | disconnected flaw surface of a and rubbed it completely by the acrylic plate ("Semipex" by Sumitomo Chemicals, Inc.), the situation when it peeled vertically was observed visually.

○: no scale peeled off

(Triangle | delta): Although the peeling scale exists, less than 10 peeled scales

×: 10 or more scales peel off

<Example 1>

(Production of base material)

A polyethylene terephthalate resin having an intrinsic viscosity of 0.62 dl / g was introduced into a twin screw extruder, melt extruded from a T-dice at 290 ° C, and solidified by tight application while applying electrostatic application on a cold rotating metal roll to obtain an unstretched sheet.

Subsequently, after the said unstretched sheet was heated at 90 degreeC with a roll stretcher, and longitudinally stretched by 3.5 times, both sides of the said longitudinally stretched film became 0.5 g / m <^2> after drying the following coating liquid A on a longitudinally stretched film. Was applied, and the intermediate coating layer was formed by passing it for 20 seconds under a wind speed of 10 m / sec and a hot air at 120 ° C. Furthermore, after heating to 140 degreeC with a tenter and extending 3.7 times horizontally, it heat-processed at 235 degreeC in 5% of width (horizontal) directions, and obtained the biaxially stretched polyethylene terephthalate film which has an intermediate coating layer on both surfaces. The film obtained was 100 µm thick, 90.2% total light transmittance, and 0.5% haze.

(Composition of Coating Liquid A for Intermediate Coating Layer)

ㆍ 50.0% by mass of ion exchange water

Isopropyl alcohol 28.9 mass%

ㆍ 10.0% by mass of acrylic melamine resin

(Nipbon Carbide High Bridge Co., Ltd. make, A-08, solid content concentration: 46 mass%)

ㆍ 10.0 mass% of polyester resin

(Toyo Bonde Co., Vironal MD-1250, solid content concentration: 30% by mass)

ㆍ 1.0 mass% of polymethyl methacrylate crosslinked particles

(Nippon Shokubai, Eposuta MA1001)

ㆍ 0.1 mass% of silicone surfactant

(Dow Corning, Painted 32)

(Adjustment of Coating Liquid B for Wavelength Selection Absorption Layer)

Toluene, methyl ethyl ketone, and resin were mixed at the following mass ratio, and the mixture was stirred under heating to dissolve the resin, followed by addition of a dye and a surfactant, followed by stirring for 30 minutes or more. Next, the undissolved matter was removed with the filter of 1 micrometer of nominal filtration accuracy, and the coating liquid B was adjusted.

Toluene 39.995 mass%

40.000 mass% of methyl ethyl ketone

ㆍ 18.776 mass% of acrylic resin

(Mitsubishi Rayon, BR-80, Tg = 105 ° C)

ㆍ Aromatic Diimmonium Dye 0.695 Mass%

(Nippon Carit, CIR1085, counter ion: bis (trifluoromethanesulfonyl) imide acid)

Phthalocyanine-based dye 0.357 mass%

(Made by Nippon Shokubai, IR-10A)

ㆍ Azaporphyrin Dye 0.118% by Mass

(Yamada Kasei, TAP-2)

ㆍ 0.059% by mass of silicon-based surfactant

(Dow Corning, Paint 57, HLB = 6.7)

(Manufacture of wavelength selective absorption filter)

60 cm in diameter so that the transmittance of 950 nm after drying the said coating liquid B (solid content concentration: 20 mass%, viscosity: 40 cps) will be 4.3% (8.0 g / m <^{2> in the} coating amount after drying) on one side of the said intermediate | middle application layer. Reverse coating using diagonal gravure, and dried for 20 seconds with hot air of 5 m / sec at 40 ° C, 20 seconds with hot air of 20 m / sec at 150 ° C, and 10 seconds with hot air of 20 m / sec at 90 ° C. To obtain a wavelength selective absorption filter. In addition, the mass ratio of the aromatic dimonium pigment | dye (a) and the azaporphyrin type pigment | dye (b) in the wavelength selective absorption layer was (a) / (b) = 100/17.

The obtained wavelength selective absorption filter had strong absorption in the near infrared region, high transmittance in the visible light region, and had clear absorption in the vicinity of 590 nm. Moreover, stability with time and an appearance of coating were also favorable.

The physical properties of the wavelength selective absorption filter obtained in Table 1 below are shown in Tables 2 and 3 below.

<Example 2>

A wavelength selective absorption filter was obtained in the same manner as in Example 1 except that the following coating solution C was used. In addition, the mass ratio of the aromatic dimonium pigment | dye (a) and the azaporphyrin type pigment | dye (b) in the wavelength selective absorption layer was (a) / (b) = 100/17.

(Adjustment of coating liquid C for wavelength selective absorption layer)

Toluene, cyclopentanone, and resin were mixed at the following mass ratio, and the mixture was stirred under heating to dissolve the resin, followed by addition of a dye and a surfactant, followed by stirring for 30 minutes or more. Subsequently, the undissolved matter was removed with a filter having a nominal filtration accuracy of 1 µm to prepare a coating solution C.

Toluene 40.088 mass%

Cyclopentanone 40.088 mass%

18.776 mass% of copolymerized polyester resin having a fluorene skeleton

(Manufactured by Kanebo, O-PET, Tg = 150 ° C)

ㆍ Aromatic Diimmonium Dye 0.695 Mass%

(Nippon Carit, CIR1085, counter ion: bis (trifluoromethanesulfonyl) imide acid)

Phthalocyanine-based dye 0.176% by mass

(Made by Nippon Shokubai, IR-12)

ㆍ Azaporphyrin Dye 0.118% by Mass

(Yamada Kasei, TAP-2)

ㆍ 0.059% by mass of silicon-based surfactant

(Dow Corning, Paint 57, HLB = 6.7)

Similarly to Example 1, the obtained wavelength selective absorption filter had strong absorption in the near infrared region, high transmittance in the visible light region, and had a clear absorption near 590 nm. Moreover, stability with time and an appearance of coating were also favorable. However, the adhesion with the substrate was slightly poor.

In Table 1, the physical properties of the obtained wavelength selective absorption filter are shown in Table 2 and Table 3 for the kind of dye used in the wavelength selective absorption layer.

Comparative Example 1

Except having used the following coating liquid D, it carried out similarly to Example 1, and obtained the wavelength selective absorption filter.

(Adjustment of Coating Liquid D for Wavelength Selection Absorption Layer)

Toluene, methyl ethyl ketone, and resin were mixed at the following mass ratio, and the mixture was stirred under heating to dissolve the resin, followed by addition of a dye and a surfactant, followed by stirring for 30 minutes or more. Subsequently, the undissolved matter was removed with a filter having a nominal filtration accuracy of 1 µm to prepare a coating solution D.

Toluene 39.998 mass%

Methyl ethyl ketone 39.998 mass%

ㆍ 18.825% by mass of acrylic resin

(Mitsubishi Rayon, BR-80)

Aromatic diimmonium pigment 0.697 mass%

(Made by Nippon Carit, CIR1085, counter ion: bis (trifluoromethanesulfonyl) imide acid)

Phthalocyanine-based dye 0.358 mass%

(Made by Nippon Shokubai, IR-10A)

ㆍ Squarylium pigment 0.065 mass%

(Manufactured by Kyowa Hakko, SD184)

ㆍ 0.059% by mass of silicon-based surfactant

(Dow Corning, Paint 57, HLB = 6.7)

Similarly to Example 1, the obtained wavelength selective absorption filter had strong absorption in the near infrared region, high transmittance in the visible light region, and had a clear absorption near 590 nm. However, the stability over time was poor.

In Table 1, the physical properties of the obtained wavelength selective absorption filter are shown in Table 2 and Table 3 for the kind of dye used in the wavelength selective absorption layer.

Comparative Example 2

A wavelength selective absorption filter was obtained in the same manner as in Example 1 except that the following coating liquid E was used. In addition, the mass ratio of the aromatic dimonium pigment | dye (a) and azaporphyrin type pigment | dye (b) in the wavelength selective absorption layer was (a) / (b) = 100/19.

(Adjustment of Coating Liquid E for Wavelength Selection Absorption Layer)

Toluene, methyl ethyl ketone, and resin were mixed at the following mass ratio, and the mixture was stirred under heating to dissolve the resin, followed by addition of a dye and a surfactant, followed by stirring for 30 minutes or more. Subsequently, the undissolved matter was removed with a filter having a nominal filtration accuracy of 1 µm to prepare a coating solution E.

ㆍ 40.002 mass% of toluene

ㆍ Methyl ethyl ketone 40.002 mass%

ㆍ 18.839 mass% of acrylic resin

(Mitsubishi Rayon, BR-80)

ㆍ Aromatic Diimmonium Dye 0.622 Mass%

(Made by Nippon Shokubai, IRG022, counter ion: hexafluoroantimonic acid)

Phthalocyanine-based dye 0.358 mass%

(Made by Nippon Shokubai, IR-10A)

ㆍ Azaporphyrin Dye 0.118% by Mass

(Yamada Kasei, TAP-2)

ㆍ 0.059% by mass of silicon-based surfactant

(Dow Corning, Paint 57, HLB = 6.7)

Similarly to Example 1, the obtained wavelength selective absorption filter had strong absorption in the near infrared region, high transmittance in the visible light region, and had a clear absorption near 590 nm. However, the stability over time was poor.

In Table 1, the physical properties of the obtained wavelength selective absorption filter are shown in Table 2 and Table 3 for the kind of dye used in the wavelength selective absorption layer.

<Example 3>

(Adjustment of Coating Liquid F for Near-Infrared Absorption Layer in Wavelength Selective Absorption Layer)

Toluene, methyl ethyl ketone, and resin were mixed at the following mass ratio, and the mixture was stirred under heating to dissolve the resin, followed by addition of a dye and a surfactant, followed by stirring for 30 minutes or more. Subsequently, the undissolved matter was removed by the filter of 1 micrometer of nominal filtration accuracy, and the coating liquid F was adjusted.

Toluene 40.056 mass%

ㆍ Methyl ethyl ketone 40.057 mass%

ㆍ 18.776 mass% of acrylic resin

(Mitsubishi Rayon, BR-80, Tg = 105 ° C)

ㆍ Aromatic Diimmonium Dye 0.695 Mass%

(Nippon Carit, CIR1085, counter ion: bis (trifluoromethanesulfonyl) imide acid)

Phthalocyanine-based dye 0.357 mass%

(Made by Nippon Shokubai, IR-10A)

ㆍ 0.059% by mass of silicon-based surfactant

(Dow Corning, Paint 57, HLB = 6.7)

(Adjustment of Coating Liquid G for Neon Cut in the Wavelength Selection Absorption Layer)

After mixing by the following mass ratio, it stirred for 30 minutes or more. Subsequently, the undissolved matter was removed by the filter of 1 micrometer of nominal filtration accuracy, and the coating liquid G was adjusted.

ㆍ Methyl ethyl ketone 49.808 mass%

ㆍ 49.847 mass% of acrylic pressure sensitive adhesive

(Soy Kagoku Co., SK Dyne 1435, solid content 30% by weight)

ㆍ Azaporphyrin pigment 0.045 mass%

(Yamada Kasei, TAP-2)

ㆍ 0.150 mass% of hardener

(Sokusaku Kagaku, L-45)

ㆍ 0.150 mass% of hardener

(Soku Kagaku Co., Ltd., TD-75)

(Manufacture of wavelength selective absorption filter)

Diagonal gravure with a diameter of 60 cm is applied to the intermediate coating layer forming surface obtained in the same manner as in Example 1 so that the transmittance at 950 nm after drying of the coating liquid F is 4.3% (8.0 g / m ^{2 in the} coating amount after drying). Coated in reverse, and dried for 20 seconds with hot air of 5 m / sec at 40 ° C., 20 seconds with hot air of 20 m / sec at 150 ° C., and 10 seconds with hot air of 20 m / sec at 90 ° C. to dry the near-infrared absorbing layer. Formed. Subsequently, the coating liquid G was coated on the near infrared absorbing layer using a lip coater so that the coating amount after drying was 16 g / m ² , and hot air at 20 ° C. for 20 seconds with hot air at 5 ° C. at 40 ° C. for 20 seconds. 20 seconds, and then passed through a hot air of 20 m / second at 90 ℃ for 10 seconds to dry to form a neon cut layer. That is, the wavelength selective absorption filter which has a wavelength selective absorption layer which consists of two layers of a near-infrared absorption layer and a neon cut layer was obtained. In addition, the mass ratio of the aromatic dimonium pigment | dye (a) and the azaporphyrin type pigment | dye (b) in the wavelength selective absorption layer was (a) / (b) = 100/17.

The obtained wavelength selective absorption filter had strong absorption in the near infrared region, high transmittance in the visible light region, and had clear absorption in the vicinity of 590 nm. Moreover, stability with time and an appearance of coating were also favorable.

In Table 1, the physical properties of the obtained wavelength selective absorption filter are shown in Table 2 and Table 3 for the kind of dye used in the wavelength selective absorption layer.

The wavelength selective absorption filter of the present invention has a low transmittance in the near infrared region and a neon light region, a high transmittance in the visible region, a small change in optical characteristics over time, and excellent durability. Can be expressed stably, and by using a near-infrared remote control to prevent malfunction of precision equipment, it can greatly contribute to the industry.

Claims (9)

A wavelength selective absorption layer comprising a composition containing a resin, a near infrared absorbing dye (A) and a dye (B), is laminated on a transparent substrate and has a maximum absorption at a wavelength of 800 to 1200 nm and a wavelength of 550 to 620 nm. Is an optional absorption filter, One of the near-infrared absorbing dyes (A) is an aromatic dimonium pigment (a) having bis (trifluoromethanesulfonyl) imide acid as a counter ion, One of the dyes (B) is a porphyrin-based dye or azaporphyrin-based dye (b), 5-100 mass parts of dyes (b) are contained with respect to 100 mass parts of dyes (a) in the said wavelength selective absorption layer, The wavelength selective absorption filter characterized by the above-mentioned. The wavelength selective absorbing layer according to claim 1, wherein the wavelength selective absorbing layer comprises a multilayer of a near infrared absorbing layer containing a resin and a near infrared absorbing dye (A) and a neon cut layer containing a resin and a dye (B), and a near infrared absorbing layer and a neon on a transparent substrate. The wavelength selective absorption filter characterized by the cut layer being formed in order. delete The wavelength selective absorption filter of Claim 1 or 2 whose resin which comprises a wavelength selective absorption layer is acrylic resin. The coating solution A according to claim 1, wherein the wavelength selective absorbing layer contains an organic solvent, a resin, an aromatic dimonium pigment (a), a porphyrin dye or an azaporphyrin dye (b) on the transparent substrate. And dried to form a wavelength selective absorption filter. The near-infrared absorbing layer of Claim 2 in which the wavelength selective absorption layer apply | coated the coating liquid B containing the organic solvent, resin, and aromatic diimmonium pigment | dye (a) on the said transparent base material, and was formed by drying, this near-infrared ray A wavelength selective absorption filter comprising a neon cut layer formed by applying a coating solution C containing an organic solvent and a resin, a porphyrin dye or an azaporphyrin dye (b) directly above the absorber layer, and drying. The wavelength selective absorption filter according to claim 5 or 6, wherein the coating liquid A or B further contains a surfactant having an HLB of 2 to 12. The wavelength selective absorption filter according to claim 7, wherein the surfactant is a silicone surfactant or a fluorine surfactant. The wavelength selective absorption filter of Claim 1 or 2 whose transparent base material is a polyester film.