JP2010079145A - Infrared absorbing laminate and optical filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an infrared absorbing laminate which substantially avoids a spectral characteristic change due to the deterioration of a light absorbent even after long-time use particularly at high temperature and high humidity, and an optical filter including the infrared absorbing laminate. <P>SOLUTION: In the infrared absorbing laminate, an infrared absorbing film containing composite tungsten oxide fine particles, a substituted benzenedithiol metal-complex having a specific structure and a resin is laid on one surface of a transparent base. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an infrared absorption laminate that is disposed on the front surface of a display device and has a function of absorbing infrared rays generated from the display device, and an optical filter including the infrared absorption laminate.

In recent years, display devices such as CRT (CRT), LCD (Liquid Crystal Display), plasma display panel (also called PDP), organic / inorganic EL display, FED (Field Emission Display), etc. have been used as display devices for various electronic devices. ing.
A filter is installed on the front surface of such an electronic display in order to remove unnecessary light-emitting components and make the display color clear. For example, in a plasma display, near infrared rays of about 800 to 1100 nm are generated by plasma discharge of a mixed gas of xenon and neon, and the generated near infrared rays cause peripheral devices to malfunction. For this reason, in the plasma display, a filter (near infrared absorption filter) that has a function of absorbing and removing near infrared rays, with a near infrared absorption layer laminated on the base film, is installed on the front of the image display device (hereinafter also referred to as display). is doing. The near-infrared absorption and removal function is often expressed by a near-infrared absorption layer containing a near-infrared absorber in a resin.

Conventionally, as a near-infrared absorber, an organic near-infrared absorber (pigment) in which a phthalocyanine compound and a diimonium compound are combined has been studied.
Since the phthalocyanine compound is excellent in heat resistance and heat-and-moisture resistance, by using the organic near-infrared absorber (pigment) in which the phthalocyanine compound and a diimonium compound are combined, it can be used for a long time, particularly at high temperature and high humidity. It is possible to make it difficult to cause changes in spectral characteristics due to deterioration of the light absorber. However, the organic near-infrared absorber (pigment) has a problem that it is easily deteriorated by ultraviolet rays derived from sunlight or the like.

On the other hand, Patent Document 1 describes a near-infrared absorption filter for PDP using composite tungsten oxide fine particles.
Such composite tungsten oxide fine particles are excellent in UV resistance and weather resistance as compared with organic near-infrared absorbers (pigments), but are insufficient in heat resistance and moist heat resistance. Therefore, the spectral characteristics change due to deterioration is likely to occur during long-time use, particularly under high temperature and high humidity, and the absorption of near infrared rays is insufficient.

JP 2006-154516 A

  The present invention has been made to solve the above-mentioned problems, and even when composite tungsten oxide fine particles are used as a near-infrared absorber, the light absorber is deteriorated even when used for a long time, particularly under high temperature and high humidity. It is an object of the present invention to provide an infrared absorbing laminate that is unlikely to cause a change in spectral characteristics, and an optical filter including the infrared absorbing laminate.

As a result of intensive studies, the inventors have found that the above problem can be solved by including a substituted benzenedithiol metal complex having a specific structure together with the composite tungsten oxide fine particles in the infrared absorption film, The present invention has been completed.
That is, the infrared-absorbing laminate according to the present invention has a general formula MxWyOz (where M element is H, He, alkali metal, alkaline earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, One or more elements selected from F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, and I, W is tungsten, O Is oxygen, 0.001 ≦ x / y ≦ 1.1, 2.2 ≦ z / y ≦ 3.0), composite tungsten oxide fine particles, substituted benzenedithiol metal represented by the following chemical formula (1) An infrared absorption film containing a complex and a resin is provided. And wherein the door.

（化学式（１）中、Ａは遷移金属であり、Ｒは下記化学式（２）に示す、いずれかの基である。Ｂ^＋は第４級アンモニウム基である。）

(In chemical formula (1), A is a transition metal, R is any group shown in chemical formula (2) below, and B ⁺ is a quaternary ammonium group.)

  According to the present invention, the inclusion of the substituted benzenedithiol metal complex having a specific structure together with the composite tungsten oxide fine particles in the infrared absorption film suppresses the deterioration of the composite tungsten oxide fine particles, and the long-term use. In particular, it is possible to make it difficult to cause changes in spectral characteristics due to deterioration of the light absorber even under high temperature and high humidity.

  In the infrared absorption laminate according to the present invention, the substituted benzenedithiol metal complex is bis [4-piperidinosulfonyl-1,2-benzenedithiolate-S, S ′] copper tetra-n-butylammonium, bis. (4-morpholinosulfonyl-1,2-benzenethiolate-S, S ′) nickel-tetra-n-butylammonium and bis (4-morpholinosulfonyl-1,2-dithiophenolate) copper tetra-n-butylammonium One or more metal complexes selected from the group consisting of these are preferable from the viewpoint of suppressing deterioration of the composite tungsten oxide fine particles.

  In the infrared absorbing laminate according to the present invention, the amount of the substituted benzenedithiol metal complex is in the range of 0.1 to 20 parts by weight with respect to 100 parts by weight of the composite tungsten oxide fine particles. It is preferable from the viewpoints of the change in the color of the absorption film and the change in film properties, and the prevention of precipitation of the substituted benzenedithiol metal complex.

  In the infrared-absorbing laminate according to the present invention, the average dispersed particle size of the composite tungsten oxide fine particles is preferably 800 nm or less from the viewpoint of increasing the transmittance in the visible region.

  In the infrared absorbing laminate according to the present invention, the composite tungsten oxide fine particles include one or more crystal structures of hexagonal, tetragonal, and cubic crystals from the viewpoint of improving the durability of optical characteristics. preferable.

  In the infrared absorption laminate according to the present invention, in the general formula MxWyOz representing the composite tungsten oxide fine particles, the M element is Cs (cesium), and the composite tungsten oxide fine particles have a hexagonal crystal structure. From the viewpoint of improving the durability of the optical characteristics.

  In the infrared absorbing laminate according to the present invention, the surface of the composite tungsten oxide fine particles is coated with an oxide containing one or more elements selected from Si, Ti, Zr, and Al. It is preferable from the viewpoint of improving the durability of optical characteristics.

  The optical filter according to the present invention is characterized in that a functional layer is laminated on the surface of the infrared absorbing laminate on the transparent substrate side and / or on the infrared absorbing film side. Such an optical filter can be used as an optical filter to which various functions are added in addition to the infrared absorption function.

The infrared absorbing laminate of the present invention contains a substituted benzenedithiol metal complex having a specific structure together with the composite tungsten oxide fine particles in the infrared absorbing film, thereby suppressing deterioration of the composite tungsten oxide fine particles. Spectral characteristic changes due to deterioration of the light absorber can be made difficult to occur even when used for time, particularly under high temperature and high humidity.
The optical filter of the present invention can be used as an optical filter to which various functions are added in addition to the infrared absorption function.

  The present invention includes an infrared absorption laminate and an optical filter including the infrared absorption laminate. Each will be described in detail below. In addition, in this invention, infrared rays are electromagnetic waves with a wavelength range of 780 nm-4 micrometers, and electromagnetic waves with a wavelength range of 780 nm-1,100 nm are also called near infrared rays.

I. Infrared absorbing laminate The infrared absorbing laminate according to the present invention has a general formula MxWyOz (where M element is H, He, alkali metal, alkaline earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, One or more elements selected from B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, I, W is tungsten , O is oxygen, composite tungsten oxide fine particles represented by 0.001 ≦ x / y ≦ 1.1, 2.2 ≦ z / y ≦ 3.0), substituted benzene represented by the following chemical formula (1) An infrared absorbing film containing a dithiol metal complex and a resin is provided. It is characterized by.

（化学式（１）中、Ａは遷移金属であり、Ｒは下記化学式（２）に示すいずれかの基である。Ｂ^＋は第４級アンモニウム基である。）

(In chemical formula (1), A is a transition metal, R is any group shown in chemical formula (2) below, and B ⁺ is a quaternary ammonium group.)

  According to the present invention, the inclusion of the substituted benzenedithiol metal complex having a specific structure together with the composite tungsten oxide fine particles in the infrared absorbing film suppresses the deterioration of the composite tungsten oxide fine particles, and the Even when used, particularly under high temperature and high humidity, it is possible to make it difficult to cause changes in spectral characteristics due to deterioration of the light absorber.

It has not been clarified that heat resistance and heat-and-moisture resistance have been improved by using a combined benzenedithiol metal complex having a specific structure together with composite tungsten oxide fine particles, but it is thought to be due to the following reasons. .
In the composite tungsten oxide fine particles represented by the general formula MxWyOz in which the element M is added to the tungsten oxide, there are many structural units in which the element M is arranged in the voids formed in the aggregate of the tungsten oxide. Aggregates to form a crystal structure. The composite tungsten oxide fine particles are considered to be easily deteriorated because the element M is released from the crystal structure by heat or the like. In contrast, the combined use of the substituted tungsten benzenedithiol metal complex having a specific structure together with the composite tungsten oxide fine particles suppresses the release of the element M from the crystal structure of the composite tungsten oxide fine particles, thereby improving the heat resistance and moisture resistance. It is thought that thermal properties are improved.

The layer configuration of the infrared absorption laminate according to the present invention will be described with reference to the drawings.
A cross-sectional view of an example of an infrared absorbing laminate according to the present invention is conceptually shown in FIG. In the cross-sectional views shown in FIGS. 1 to 3, the scale in the thickness direction (vertical direction in the drawing) is greatly exaggerated from the scale in the plane direction (horizontal direction in the drawing) for ease of explanation. It is shown. FIG. 1 is a first embodiment among preferred embodiments of an infrared absorption laminate 1 according to the present invention, and an infrared absorption film 11 is provided on one surface of a transparent substrate 10. Provided here means that the infrared absorption film 11 is laminated on the surface of the transparent substrate 10, but the infrared absorption film 11 is formed on the surface of the transparent substrate 10. May be attached so as to be peelable.
Moreover, FIG. 2 is 2nd embodiment among the suitable embodiment of the infrared rays absorption laminated body 1 which concerns on this invention, and the ultraviolet-ray absorption layer 12 and the infrared rays absorption film on one surface of the transparent base material 10 are shown. 11 are provided in this order. As described above, another functional layer may be provided between the transparent substrate 10 and the infrared absorption film 11.

FIG. 3 is a cross-sectional view showing an example of the optical filter 20 according to the present invention. The anti-glare layer 13 is laminated | stacked on the surface on the opposite side to the transparent base material 10 side of the infrared rays absorption film 11 of the infrared rays absorption laminated body 1 which concerns on this invention. Moreover, the said infrared absorption film 11 serves as the function as an adhesive layer with an infrared absorption function.
The infrared absorption film 11 of the present invention may be provided as a coating film on the surface of a transparent substrate or another layer, or may be laminated as an infrared absorption layer that also serves as an adhesive layer.
Hereinafter, the infrared absorption laminate of the present invention will be described in order from a transparent substrate.

1. Transparent base material As long as it has mechanical strength and light transmittance, a transparent base material that appropriately considers performance such as heat resistance may be selected according to the intended use. As such a transparent substrate, a polymer film (or polymer sheet) can be used.

  Examples of the transparent resin used as the polymer film material include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, terephthalic acid-isophthalic acid-ethylene glycol copolymer, terephthalic acid-cyclohexanedimethanol-ethylene glycol copolymer, and the like. Polyester resins such as nylon 6, polyamide resins such as nylon 6, polyolefin resins such as polypropylene, polymethylpentene and cycloolefin polymers, acrylic resins such as polymethyl methacrylate, styrenes such as polystyrene and styrene-acrylonitrile copolymers Examples thereof include resins, cellulose resins such as triacetyl cellulose, and polycarbonate resins.

  These resins are used alone or as a plurality of types of mixed resins (including polymer alloys), and the layer structure of the transparent substrate is used as a single layer or a laminate of two or more layers. In the case of a resin film, a uniaxially stretched or biaxially stretched film is more preferable in terms of mechanical strength.

The thickness of the transparent substrate may be basically selected according to the use and is not particularly limited, but is usually 12 to 1000 μm, preferably 20 to 500 μm, more preferably 50 to 200 μm. Within such a thickness range, the mechanical strength is sufficient, warping, loosening, breakage, etc. are prevented, and it is easy to supply and process in a continuous belt shape.
In the present invention, the transparent substrate is referred to as including a resin plate in addition to a polymer film (including a polymer sheet). However, a thin transparent substrate is preferable from the viewpoint of reducing the thickness of the optical filter by avoiding an increase in the total thickness.

  In this respect, the transparent substrate is preferably a polymer film rather than a resin plate. Among the polymer films, polyester resin films such as polyethylene terephthalate and polyethylene naphthalate are preferable in terms of transparency, heat resistance, cost, and the like, and more preferably a biaxially stretched polyethylene terephthalate film. In addition, although the transparency of a transparent base film is so good that it is high, Preferably the light transmissive film which becomes 80% or more by visible light transmittance | permeability is good.

Further, a known additive such as a filler, a plasticizer, an antistatic agent and the like can be appropriately added to the resin of the transparent base material as necessary without departing from the spirit of the present invention. .
In addition, the transparent substrate may be appropriately subjected to known easy adhesion treatment such as corona discharge treatment, plasma treatment, ozone treatment, flame treatment, primer treatment, alkali treatment, etc. on the surface.

2. Infrared absorbing film The infrared absorbing film of the present invention has a general formula MxWyOz (where M element is H, He, alkali metal, alkaline earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, One or more elements selected from Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, I, W is tungsten, O is oxygen, 0.001 ≦ x / y ≦ 1.1, 2.2 ≦ z / y ≦ 3.0), a substituted benzenedithiol metal complex having a specific structure, and a resin, and further containing other components. It is good.
In the infrared absorbing film of the present invention, composite tungsten oxide fine particles and a substituted benzenedithiol metal complex having a specific structure are dispersed in the resin to ensure the transparency required for the infrared absorbing laminate and the infrared absorbing function. is doing.

(1) Composite tungsten oxide fine particles The general formula MxWyOz (wherein M element is H, He, alkali metal, alkaline earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, One or more elements selected from Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, and I, W is tungsten, O is oxygen, 0.001 ≦ x / y ≦ 1 .1, 2.2 ≦ z / y ≦ 3.0), which absorbs a wavelength region of 800 nm to 1,100 nm and functions as an infrared absorber in the present invention.

  The composite tungsten oxide fine particles represented by the general formula MxWyOz are selected from the hexagonal, tetragonal, and cubic crystals because they have excellent durability when they have a hexagonal, tetragonal, or cubic crystal structure. Preferably it contains more than one crystal structure. For example, in the case of composite tungsten oxide fine particles having a hexagonal crystal structure, preferable M elements include Cs, Rb, K, Tl, In, Ba, Li, Ca, Sr, Fe, and Sn. Examples thereof include composite tungsten oxide fine particles containing one or more selected elements. Among them, the M element is preferably Cs (cesium) from the viewpoint of durability.

At this time, the addition amount x of the added M element is preferably 0.001 or more and 1.0 or less, and more preferably around 0.33. This is because the value of x calculated theoretically from the hexagonal crystal structure is 0.33, and preferable optical characteristics can be obtained with the addition amount before and after this. On the other hand, the abundance z of oxygen is preferably 2.2 or more and 3.0 or less. For example, Cs _0.33 WO ₃ , Rb _0.33 WO ₃ , K _0.33 WO ₃ , Ba _0.33 WO _{3 and the} like can be mentioned as long as x and z fall within the above ranges. Useful infrared absorption characteristics can be obtained.

Such composite tungsten oxide fine particles may be used alone or in combination.
In addition, it is preferable that the surface of the composite tungsten oxide fine particles is coated with an oxide containing one or more elements of Si, Ti, Zr, and Al from the viewpoint of further improving weather resistance. .

  The average dispersed particle size of the composite tungsten oxide fine particles is preferably 800 nm or less, more preferably 200 nm or less, particularly preferably 100 nm or less, from the viewpoint of the transparency of the infrared absorption film. The average dispersed particle size here refers to the volume average particle size, and can be measured using a particle size distribution / particle size distribution measuring device (for example, Nanotrack particle size distribution measuring device manufactured by Nikkiso Co., Ltd.). .

  The content of the composite tungsten oxide fine particles is preferably 1 to 25% by weight in the infrared absorbing film. If the content is more than 1% by weight, a sufficient infrared absorption function can be exhibited, and if it is 25% by weight or less, a sufficient amount of visible light can be transmitted.

(2) Substituted benzenedithiol metal complex represented by chemical formula (1) The infrared absorbing film of the present invention contains a substituted benzenedithiol metal complex represented by the following chemical formula (1).

（化学式（１）中、Ａは遷移金属であり、Ｒは下記化学式（２）に示すいずれかの基である。Ｂ^＋は第４級アンモニウム基である。）

(In chemical formula (1), A is a transition metal, R is any group shown in chemical formula (2) below, and B ⁺ is a quaternary ammonium group.)

In the chemical formula (1), A represents a transition metal and is not particularly limited, and examples thereof include copper, cobalt, and nickel. Of these, copper and nickel are preferable.
B ⁺ represents a quaternary ammonium group, and specific examples include a tetra-n-butylammonium group, a tetraethylammonium group, a tetraphenylammonium group, a tetrabenzylammonium group, and a trimethylbenzylammonium group. . Of these, a tetra-n-butylammonium group is preferable.

  The substituted benzenedithiol metal complex represented by the chemical formula (1) is bis [4-piperidinosulfonyl-1 represented by the following chemical formula (3) from the viewpoint of suppressing deterioration of the composite tungsten oxide fine particles. , 2-Benzenedithiolate-S, S ′] copper tetra-n-butylammonium, bis (4-morpholinosulfonyl-1,2-benzenethiolate-S, S ′) nickel- represented by the following chemical formula (4) One or more metals selected from the group consisting of tetra-n-butylammonium and bis (4-morpholinosulfonyl-1,2-dithiophenolate) copper tetra-n-butylammonium represented by the following chemical formula (5) A complex is preferred.

  The amount of the substituted benzenedithiol metal complex is preferably in the range of 0.1 to 20 parts by weight, more preferably 0.2 to 10 parts by weight, with respect to 100 parts by weight of the composite tungsten oxide fine particles. A range is preferable. If the amount is less than 0.1 part by weight, the deterioration suppressing effect of the composite tungsten oxide fine particles may not be sufficiently obtained. If the amount exceeds 20 parts by weight, the chromaticity change of the entire infrared absorbing film and the hardness change of the film , And the substituted benzenedithiol metal complex may be precipitated.

(3) Resin The resin contained in the infrared absorbing film functions as a binder resin that uniformly disperses the composite tungsten oxide fine particles and the substituted benzenedithiol metal complex and gives the infrared absorbing film a film forming property. The resin is not particularly limited as long as it achieves film formability and transparency, and can be appropriately selected and used depending on the layer configuration adjacent to the infrared absorption film. The higher the transparency as the infrared absorbing film, the better. When a film is formed with the resin used, the resin should be used in such a resin and film thickness that can provide a light transmittance of 70% or more, more preferably 80% or more in the visible light region of 380 to 780 nm. Is preferred.
Examples of the resin include resins such as a polyester resin, a polyurethane resin, an acrylic resin, and an epoxy resin.

Moreover, it is preferable that resin used for this invention can disperse | distribute the said composite tungsten oxide microparticles | fine-particles and the said substituted benzenedithiol metal complex favorably.
Specifically, when the composite tungsten oxide fine particles and the substituted benzenedithiol metal complex are dispersed in a resin to form a coating film having a film thickness of 25 μm, and a haze value in accordance with JIS K7105-1981 is measured. It is preferable that a resin having a haze value of 15 or less is selected and used at a mixing ratio at which the haze value is 15 or less. The haze value is more preferably 10 or less, and particularly preferably 5 or less. When using an additive for improving dispersion when dispersing the composite tungsten oxide fine particles and the substituted benzenedithiol metal complex, the resin is added at a mixing ratio so that the additive also has the above haze value. An agent is preferably used.

The infrared absorbing film can also function as a pressure-sensitive adhesive layer for bonding the transparent substrate and a functional layer described later.
An adhesive refers to a type of adhesive. Of the adhesives, only moderate pressure is applied at room temperature, usually just lightly pressed by hand, and only the adhesiveness of the surface. It can be bonded. In order to develop the adhesive strength of the pressure-sensitive adhesive, usually, physical energy or action such as heating, humidification, radiation (ultraviolet ray, electron beam, etc.) irradiation is unnecessary, and chemical reaction such as polymerization reaction is also unnecessary. In addition, the pressure-sensitive adhesive can maintain the adhesive strength to the extent that it can be re-peeled after bonding. In the present invention, it has moderate tackiness (adhesive force), transparency, dispersibility, and coating suitability among those commonly used as known pressure-sensitive adhesives, and substantially changes the transmission spectrum of the optical filter. Those that are not allowed to be selected can be appropriately selected and used.

  Examples of the pressure-sensitive adhesive include natural rubber, synthetic rubber, acrylic resin (hereinafter also abbreviated as acrylic), polyvinyl ether, urethane resin, and silicone resin. Specific examples of synthetic rubbers include styrene-butadiene rubber, acrylonitrile-butadiene rubber, polyisobutylene rubber, isobutylene-isoprene rubber, styrene-isoprene block copolymer, styrene-butadiene block copolymer, styrene-ethylene-butylene block. A copolymer is mentioned. Specific examples of the silicone resin system include dimethylpolysiloxane. These pressure-sensitive adhesives can be used alone or in combination of two or more.

  An acrylic adhesive is mentioned as an adhesive suitably used. The acrylic pressure-sensitive adhesive is a polymer containing at least a (meth) acrylic acid alkyl ester monomer. A copolymer of a (meth) acrylic acid alkyl ester monomer having an alkyl group having about 1 to 18 carbon atoms and a monomer having a carboxyl group, or (meth) acrylic acid having an alkyl group having about 1 to 18 carbon atoms A copolymer using two or more kinds of alkyl ester monomers is generally used. In the present invention, (meth) acrylic acid means acrylic acid and / or methacrylic acid.

Examples of (meth) acrylic acid alkyl ester monomers used here include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, sec-propyl (meth) acrylate, N-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, isoamyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, Examples thereof include n-octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, undecyl (meth) acrylate, and lauryl (meth) acrylate.
Moreover, it is preferable that the said (meth) acrylic-acid alkylester is copolymerized in the quantity of 30-99.5 weight part in the acrylic adhesive.

Moreover, as a monomer which has a carboxyl group which forms an acrylic adhesive, monomers containing a carboxyl group such as (meth) acrylic acid, itaconic acid, crotonic acid, maleic acid, monobutyl maleate and β-carboxyethyl acrylate are used. Can be mentioned.
Furthermore, in addition to the above, the acrylic pressure-sensitive adhesive used in the present invention may be copolymerized with a monomer having another functional group within a range that does not impair the characteristics of the acrylic pressure-sensitive adhesive. Examples of monomers having other functional groups include monomers containing hydroxyl groups such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and allyl alcohol; (meth) acrylamide, N-methyl Monomers containing an amide group of (meth) acrylamide and N-ethyl (meth) acrylamide; Monomers containing an amide group and a methylol group such as N-methylol (meth) acrylamide and dimethylol (meth) acrylamide; ) Monomers having functional groups such as monomers containing amino groups such as acrylate, dimethylaminoethyl (meth) acrylate and vinylpyridine; and epoxy group-containing monomers such as allyl glycidyl ether and (meth) acrylic acid glycidyl ether. It is. In addition to these, fluorine-substituted (meth) acrylic acid alkyl ester, (meth) acrylonitrile, and the like, vinyl group-containing aromatic compounds such as styrene and methylstyrene, vinyl acetate, and vinyl halide compounds can be used.

Furthermore, in the acrylic pressure-sensitive adhesive used in the present invention, in addition to the monomer having other functional groups as described above, another monomer having an ethylenic double bond can be used. Examples of monomers having an ethylenic double bond include diesters of α, β-unsaturated dibasic acids such as dibutyl maleate, dioctyl maleate and dibutyl fumarate; vinyl esters such as vinyl acetate and vinyl propionate. Vinyl ether; vinyl aromatic compounds such as styrene, α-methyl styrene and vinyl toluene; (meth) acrylonitrile and the like.
In addition to the monomer having an ethylenic double bond as described above, a compound having two or more ethylenic double bonds may be used in combination. Examples of such compounds include divinylbenzene, diallyl malate, diallyl phthalate, ethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, methylenebis (meth) acrylamide, and the like.

  Furthermore, in addition to the above-described monomers, monomers having an alkoxyalkyl chain can be used. Examples of (meth) acrylic acid alkoxyalkyl esters include 2-methoxyethyl (meth) acrylate, methoxyethyl (meth) acrylate, 2-methoxypropyl (meth) acrylate, and 3-methoxypropyl (meth) acrylate. , 2-methoxybutyl (meth) acrylate, 4-methoxybutyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 3-ethoxypropyl (meth) acrylate, 4-ethoxybutyl (meth) acrylate And so on.

  As a commercial item of an acrylic adhesive, for example, trade name: TU-41A (manufactured by Yodogawa Paper Mill), trade name: No. 591, no. 5915, no. 5919M, CS9621, LA-50, LA-100, HJ-9210, No. 595B (manufactured by Nitto Denko Corporation), trade name: SK Dyne SK2094 (manufactured by Soken Chemical Co., Ltd.) and the like are suitably used from the viewpoint of low haze and adhesive strength.

(4) Other components Other components that may be further contained in the infrared absorbing film include neon light absorbers and color correction dyes.

(Neon light absorber)
The neon light absorption function is contained to absorb neon light emitted from the plasma display panel, that is, the emission spectrum of neon atoms. Since the emission spectrum band of neon light has a wavelength of 550 to 640 nm, it is preferable that the spectral transmittance when functioning as a neon light absorbing layer is designed to be 50% or less and further 40% or less at a wavelength of 550 nm. As the neon light absorber, a dye having an absorption maximum in a wavelength region of at least 550 to 640 nm can be used. Specific examples of the dye include cyanine, oxonol, methine, subphthalocyanine or porphyrin. Of these, porphyrins are preferred. Among them, a tetraazaporphyrin-based dye as disclosed in Japanese Patent No. 3834479 is particularly preferable from the viewpoint of good dispersibility even in a pressure-sensitive adhesive and good heat resistance, moisture resistance, and light resistance.
Although content of a neon light absorber is not specifically limited, It is preferable that it is 0.05 to 5 weight% in a film | membrane. If the content is more than 0.05% by weight, a sufficient neon light absorbing function can be exhibited, and if it is 5% by weight or less, a sufficient amount of visible light can be transmitted.

(Color correction dye)
The color correction function is included to adjust the color of the display filter in order to improve the color purity of the light emitted from the panel, the color reproduction range, the display color when the power is turned off, and the like.
Examples of known dyes that can be used as color correction dyes include the dyes described in JP 2000-275432 A, JP 2001-188121 A, JP 2001-350013 A, JP 2002-131530 A, and the like. Can be suitably used. In addition, other dyes such as anthraquinone, naphthalene, azo, phthalocyanine, pyromethene, tetraazaporphyrin, squarylium, and cyanine that absorb visible light such as yellow light, red light, and blue light. Can be used.
The content of the color correction dye is appropriately adjusted according to the color to be corrected and is not particularly limited. Usually, it contains about 0.01 to 10% by weight in the film.

(Other ingredients)
Moreover, unless the effect of this invention is impaired, infrared absorbers other than composite tungsten oxide microparticles | fine-particles may be included. The infrared absorber other than the composite tungsten oxide fine particles is appropriately selected from inorganic infrared absorbers such as tungsten oxides other than those represented by the above general formula, and organic infrared absorbers such as phthalocyanine compounds and diimonium compounds. Used.
Furthermore, the infrared absorbing film may contain a crosslinking agent such as an isocyanate compound, a tackifier, and the like as desired.
In addition, the infrared absorbing film may contain various dispersants for improving the dispersibility of the composite tungsten oxide fine particles and the substituted benzenedithiol metal complex, various surfactants, silane coupling agents, and the like.

3. Characteristics of infrared absorbing laminate (infrared absorptivity)
In the infrared absorbing laminate according to the present invention, the infrared transmittance in the wavelength range of 800 nm to 1,100 nm (near infrared region) is preferably 20% or less, and more preferably 15% or less.
In addition, the light transmittance in this invention can be measured with a spectrophotometer (for example, product number: UV-3100PC, company name: Shimadzu Corporation) based on JIS-Z8701.

(durability)
The infrared-absorbing laminate of the present invention has excellent durability, and even when used for a long time under high temperature and high humidity, changes in spectral characteristics attributable to deterioration of the light absorber are unlikely to occur. Specifically, the difference ΔT in transmittance T at a wavelength of 300 nm to 1300 nm after the passage of 3 days under the condition of heat and humidity resistance (80 ° C., humidity 95% RH) is 10% or less, more preferably 6% or less. It is desirable that

II. Optical filter The optical filter according to the present invention is characterized in that a functional layer is laminated on the surface of the infrared absorbing laminate on the transparent substrate side and / or on the infrared absorbing film side. Such an optical filter can be used as an optical filter to which various functions are added in addition to the infrared absorption function.

  As the functional layer used in the present invention, an optical functional layer having optical functions such as an anti-scratch function, an antiglare function and an antireflection function, and a functional layer having functions other than the optical functions such as an electromagnetic wave shielding function and an antifouling function Is mentioned. The functional layer may be formed as a multilayer in addition to a single layer. As the functional layer, a known optical filter may be used.

Hereinafter, each functional layer will be described in order.
(1) Optical functional layer <Abrasion resistant functional layer>
The scratch-resistant (hard coat) layer preferably exhibits a hardness of “H” or higher in a pencil hardness test defined by JISK5600-5-4 (1999). The material is not particularly limited as long as the same transparency can be realized.
The scratch-resistant layer (hard coat) layer is, for example, a polyfunctional (meth) acrylate prepolymer such as polyester (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, or trimethylolpropane tri (meth) acrylate. , Pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and other polyfunctional (meth) acrylate monomers such as tri- or more functional compounds, either alone or in combination of two or more of these It can be formed as a coating film using a curable resin. Further, when the ionizing radiation curable resin is used as an ultraviolet curable resin, a sensitizer can be added as a photopolymerization initiator or a photopolymerization accelerator. Here, (meth) acrylate is a composite notation meaning acrylate or methacrylate. The scratch resistance function (hard coat) can be formed by a wet film formation method such as coating on the transparent substrate by diluting the material with a solvent as necessary.

<Anti-glare layer>
The antiglare layer (Anti Glare layer, abbreviated as AG layer) is formed on the surface of the layer by forming a coating with an inorganic filler such as silica added to the resin binder or by forming using a shaping plate. It can be formed as a layer provided with fine irregularities for irregularly reflecting light. As the resin of the resin binder, a curable acrylic resin, an ionizing radiation curable resin, or the like is preferably used in the same manner as the scratch-resistant (hard coat) layer because the surface layer is desired to have surface strength.

<Antireflection layer>
The antireflection layer (Anti Reflection layer, abbreviated as AR layer) is a single layer of a low refractive index layer, or a low refractive index layer and a high refractive index layer, and the low refractive index layer is positioned in the uppermost layer. A multilayer structure in which the layers are alternately laminated is generally used, and can be formed by a dry film formation method such as vapor deposition or sputtering, or by using a wet film formation method such as coating. Note that silicon oxide, magnesium fluoride, fluorine-containing resin, or the like is used for the low refractive index layer, and titanium oxide, zinc sulfide, zirconium oxide, niobium oxide, or the like is used for the high refractive index layer. Here, the high (low) refractive index layer means that the refractive index of the layer is relatively high (low) compared to a layer adjacent to the layer (for example, a low (high) refractive index layer). Meaning.
When the antireflection layer is further provided with a scratch resistance function, the antireflection layer is appropriately formed using a material having high hardness described in the section of the scratch resistance function (hard coat) layer.

<Other optical functional layers>
Examples of other optical functional layers include a neon light absorption layer, a color correction layer, and an ultraviolet absorption layer. However, from the viewpoint of production efficiency, the neon light absorbing layer and the color correction layer are not formed as a single layer, but, as described above, the neon light absorbing layer or the color correcting layer is formed on another film (layer) such as an infrared absorbing film. It is preferable that a correction dye is contained so as to serve as a neon light absorption layer and a color correction layer. Even when it is formed as a single layer, the neon light absorber and the color correction dye described in the above “2. Infrared absorbing film” can be used.
The ultraviolet absorbing layer may be an independent layer, or may be a layer that functions as an ultraviolet absorbing layer, in which another functional layer contains an ultraviolet absorber. Examples of the transparent substrate containing an ultraviolet absorber include “Tetron Film HB Type” (trade name) manufactured by Teijin Limited.
Examples of the ultraviolet absorber include organic compounds such as benzotriazole-based compounds and benzophenone-based compounds, and inorganic compounds composed of particulate zinc oxide, cerium oxide, and the like. Examples of the binder resin used for the independent layer include resins such as a polyester resin, a polyurethane resin, an acrylic resin, and an epoxy resin.

(2) Other functional layers <electromagnetic wave shielding layer>
The electromagnetic wave shielding layer is a layer having both electromagnetic wave shielding performance and visible light transmission performance. Here, the term “transparent” refers not only to the case of a coating film of a continuous continuum having optical transparency to visible light (also simply referred to as light), but also by meshing the material itself even if it is opaque, The total light transmittance may be 50% or more, more preferably 80% or more.

The material and shape of the electromagnetic wave shielding layer are not particularly limited, and various conductor layers in a conventionally known light-transmitting electromagnetic wave shielding filter can be appropriately employed. The electromagnetic wave shielding layer is typically a mesh-like layer formed by etching a metal foil. For example, the electromagnetic wave is formed in a mesh-like shape on a polyester film from the beginning by using a printing method, a plating method, or the like. One or two or more physical or chemical forming methods such as vapor deposition, sputtering, plating, etc. are used on the entire surface of a polyester film formed with a shielding layer (hereinafter referred to as a conductor mesh layer) or initially on a polyester film. Then, after the electromagnetic wave shielding layer is formed, a conductor mesh layer is formed by etching or the like. It is also possible to form a conductor mesh layer by patterning a single metal foil before lamination on a polyester film sheet by etching. The conductor mesh layer of this single layer is laminated on the polyester film sheet with an adhesive or the like.
Moreover, as an electromagnetic wave shielding layer which is a whole surface film which has a light transmittance, what formed the whole surface film of the transparent conductor layer by vapor deposition of silver, ITO (indium tin oxide), etc. on the polyester film is mentioned, for example.

The electromagnetic wave shielding layer is not particularly limited as long as it is a substance having sufficient conductivity to express electromagnetic wave shielding performance, but usually a metal layer is preferable in terms of good conductivity, and the metal layer is as described above. It can be formed by vapor deposition, plating, metal foil lamination, or the like. Examples of the metal material for the metal layer include gold, silver, copper, iron, nickel, chromium, and aluminum. The metal of the metal layer may be an alloy, and the metal layer may be a single layer or multiple layers.
When the electromagnetic shielding layer is a conductor mesh layer, the blackened surface can be formed by a conventionally known method for the purpose of preventing light reflection on the surface of the electromagnetic shielding layer. Furthermore, you may provide a conventionally well-known rust prevention layer in a conductor mesh layer or a blackening process surface as needed.

<Anti-fouling layer>
The antifouling layer is generally a water-repellent or oil-repellent coat, and a siloxane-based, fluorinated alkylsilyl compound or the like can be applied. A fluorine-based or silicone-based resin used as a water-repellent paint can be preferably used. For example, when the low refractive index layer of the antireflection layer is formed of SiO ₂ , a fluorosilicate water-repellent paint is preferably used.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has any configuration that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits the same effects. Are included in the technical scope.

  Hereinafter, the present invention will be described more specifically with reference to examples. These descriptions do not limit the present invention.

Example 1
To 100 parts by weight of acrylic resin (manufactured by Soken Chemical Co., Ltd., SK Dyne 2094), 0.25 parts by weight of curing agent (manufactured by Soken Chemical Co., Ltd., E-5XM), cesium-containing tungsten oxide as an infrared absorber (Cs _0.33 WO ₃₎ content of 18.5 wt.% suspension (Sumitomo Metal Mining Co., YMF-02; average dispersion particle size 50 nm) 10 parts by weight, and methyl isobutyl ketone (MIBK) 40 wt In addition, 0.05 parts by weight of bis (4-morpholinosulfonyl-1,2-benzenethiolate-S, S ′) nickel-tetra-n-butylammonium is added and mixed to absorb infrared rays. A sex composition was prepared.
Next, the infrared-absorbing composition is dried on a continuous strip-shaped uncolored transparent biaxially stretched polyethylene terephthalate (PET) film (A4300: trade name, manufactured by Toyobo Co., Ltd.) having a thickness of 100 μm. After coating with an applicator to a thickness of 25 μm and drying at 70 ° C. for 3 minutes, a 75 μm-thick release-treated PET was laminated from above to obtain an infrared-absorbing laminate.

(Evaluation)
The transmittance T at a wavelength of 300 nm to 1300 nm after the passage of 3 days under the conditions of the initial state of the produced infrared absorbing laminate and the heat and humidity resistant environment (80 ° C., humidity 95% RH) of the infrared absorbing laminate was measured. Measurement was performed using a photometer (manufactured by Shimadzu Corporation, UV-3100PC). The transmittance change ΔT was determined from the measured value of the transmittance T after the passage of 3 days under the conditions of the initial state and the humidity and heat resistant environment (80 ° C., humidity 95% RH).
As a result, the transmittance change ΔT was less than 7% in comparison between the initial state and after 3 days.

(Comparative Example 1)
An infrared-absorbing laminate was prepared in the same manner as in Example 1 except that bis (4-morpholinosulfonyl-1,2-benzenethiolate-S, S ′) nickel-tetra-n-butylammonium was not used. did.
[Evaluation results]
When evaluated in the same manner as in Example 1, the difference ΔT in the transmittance T at wavelengths of 300 nm to 1300 nm before and after the passage of 3 days exceeded 10%, and the light absorber deteriorated in the infrared region.

FIG. 1 is a schematic cross-sectional view of an example of an infrared absorption laminate according to the present invention. FIG. 2 is a schematic cross-sectional view of an example of an infrared absorption laminate according to the present invention. FIG. 3 is a schematic cross-sectional view of an example of an optical filter according to the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Infrared absorption laminated body 10 Transparent base material 11 Infrared absorption film 12 Ultraviolet absorption layer 13 Anti-glare layer 20 Optical filter

Claims (8)

On one side of the transparent substrate, a general formula MxWyOz (where M element is H, He, alkali metal, alkaline earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, One or more elements selected from Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, and I, W is tungsten, O is oxygen, 0.001 ≦ x / y ≦ 1 .1, 2.2 ≦ z / y ≦ 3.0), an infrared absorption film containing a substituted benzenedithiol metal complex represented by the following chemical formula (1), and a resin An infrared-absorbing laminate, characterized in that

(In chemical formula (1), A is a transition metal, R is any group shown in chemical formula (2) below, and B ⁺ is a quaternary ammonium group.)

  The substituted benzenedithiol metal complex is bis [4-piperidinosulfonyl-1,2-benzenedithiolate-S, S ′] copper tetra-n-butylammonium, bis (4-morpholinosulfonyl-1,2-benzene. One or more metals selected from the group consisting of thiolate-S, S ′) nickel-tetra-n-butylammonium and bis (4-morpholinosulfonyl-1,2-dithiophenolate) copper tetra-n-butylammonium The infrared-absorbing laminate according to claim 1, which is a complex.   The infrared ray according to claim 1 or 2, wherein the amount of the substituted benzenedithiol metal complex is in the range of 0.1 to 20 parts by weight with respect to 100 parts by weight of the composite tungsten oxide fine particles. Absorbent laminate.   The infrared-absorbing laminate according to any one of claims 1 to 3, wherein the composite tungsten oxide fine particles have an average dispersed particle size of 800 nm or less.   The infrared-absorbing laminate according to any one of claims 1 to 4, wherein the composite tungsten oxide fine particles include one or more crystal structures of hexagonal, tetragonal, and cubic crystals. .   6. The general formula MxWyOz representing the composite tungsten oxide fine particles, wherein the M element is Cs (cesium), and the composite tungsten oxide fine particles have a hexagonal crystal structure. An infrared-absorbing laminate according to claim 1.   The surface of the composite tungsten oxide fine particles is coated with an oxide containing one or more elements selected from Si, Ti, Zr, and Al. The infrared absorption laminate according to one item.   A functional layer is laminated on the transparent substrate side surface and / or the infrared absorption film side surface of the infrared absorption laminate according to any one of claims 1 to 7, filter.

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