JPH07178861A - Near infrared-absorbing panel - Google Patents

Abstract

PURPOSE:To obtain a near infrared absorbing panel having excellent light fastness and simple to produce by laminating an ethylene/vinyl acetate(EVA) adhesive polymer containing a near infrared absorbing dye and an ultraviolet absorber having the max. absorbing wavelength within a specific wavelength region and a glass or resin panel. CONSTITUTION:An EVA polymer containing a near infrared absorbing dye and an ultraviolet absorber having the max. absorbing wavelength within a wavelength region of 250-400nm and a glass or resin panel are laminated. As the dye, for example, there are a metal complex compd., phthalocyanine, naphthalocyanine, aluminum salt, anthraquinone or naphthoquinone. Glass is inorg. glass and the resin panel has high transparency and, for example, a rigid panel or film composed of an acrylic resin, polycarbonate or polyethylene terephthalate is utilized.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a near infrared ray absorbing plate having excellent light resistance. The main fields of use are indoors,
A near-infrared absorbing plate having a heat ray blocking effect, which is useful for controlling the temperature inside the vehicle, can be mentioned. Further, it can be used as a film for selective use of light quality for controlling plant growth, an infrared cut filter of a semiconductor light receiving element, eyeglasses for protecting human eyes from rays containing harmful infrared rays, and the like.

[0002]

2. Description of the Related Art In recent years, particularly from the viewpoint of energy saving, attention has been paid to combining a near infrared ray absorbing plate with a building material such as a building or a house or a window of an automobile, a train, an airplane or the like for the purpose of blocking heat rays. In some, near-infrared absorbing plates have been commercialized. As a method of combining a near-infrared absorbing plate and a window glass for building materials and vehicles such as automobiles and trains, a method of directly attaching a near-infrared absorbing film to the window glass, or a method of sandwiching the laminated glass between two glass plates However, in any case, the near-infrared absorbing film is required to have high light resistance because it is used for outdoor use. Further, in order to reduce the cost, it is important to establish a simple manufacturing method for the near infrared ray absorbing plate.

JP-A-3-62878 describes that a phthalocyanine compound having a substituent on the phthalocyanine ring has good phase solubility in a resin and is excellent as a near infrared absorbing dye for a near infrared absorbing film or a filter. Has been done. Further, polyethylene terephthalate or polycarbonate is usually used as the substrate film of the near-infrared absorbing film, but the near-infrared absorbing film made of those plastics does not have sufficient light resistance of the near-infrared absorbing agent contained therein. However, the pigment is gradually decomposed by sunlight, and the function as a heat ray blocking film is largely deteriorated. There is no report on the light resistance of the near-infrared absorbing film. Furthermore, when an adhesive is applied to both sides of a plastic film to produce a laminated glass, a problem such as wrinkling of the plastic film occurs, and thus a special technique is required. In particular, it is difficult to manufacture a laminated glass having a curved surface.

JP-A-59-152249 discloses a method in which a polyvinyl butyral resin containing a near-infrared absorber and an ultraviolet absorber is used as an intermediate film and sandwiched between rigid transparent plates such as glass and plastic. Not only is the resin hygroscopic and complicated to handle,
The bonding temperature is high when making laminated glass or plywood, and the near-infrared absorbing dye contained during bonding sometimes decomposes. It is important that the near-infrared absorbing plate has a large visible transmittance (T _V ) when it is used for building materials or windows of automobiles, trains and the like. For example, in the case of automobile windshields, T _V is 70% or more from the viewpoint of safety.
It is defined by the IS standard. Also, the index of the low emissivity for sunlight can be represented by the solar transmittance (T _E), but higher T _E is less high performance low emissivity is, T _E
It is important to keep the value as small as possible in order to save energy.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a near-infrared absorbing plate which has a small deterioration of its near-infrared absorbing ability due to light and is easy to manufacture.

[0006]

DISCLOSURE OF THE INVENTION As a result of earnest studies for solving the above-mentioned problems, the present inventors have found that wavelengths of 250 to 40
It has been found that the near-infrared absorbing dye is decomposed by 0 nm light, and the light fastness of the near-infrared absorbing plate is significantly improved by using an ultraviolet absorber capable of absorbing light of that wavelength. Furthermore, by dissolving the near-infrared absorbing dye and the ultraviolet absorber in an ethylene-vinyl acetate (EVA) -based adhesive polymer to prepare an adhesive film having a near-infrared absorbing function, and easily bonding a glass or resin plate It was found that a laminated glass or a composite plate having a near-infrared absorbing function can be produced, and the present invention has been completed. That is, the present invention relates to ethylene-containing a near infrared absorbing dye and an ultraviolet absorber having a maximum absorption wavelength in the wavelength range of 250 to 400 nm.
The present invention relates to a near-infrared absorbing plate obtained by laminating a vinyl acetate (EVA) adhesive polymer and a glass or resin plate.

The near-infrared absorbing dye used in the present invention is not particularly limited as long as it has absorption in the near-infrared region (700 to 1800 nm), but may be in the visible region (400 to 700 nm) depending on the application. Little coloring,
Those having a large molar extinction coefficient are desirable, and these dyes can be used alone or in combination. Further, depending on the use, it is possible to adjust the color in the visible region or to contain a dye having absorption in the visible region in order to color the target color. The amount of near-infrared absorbing dye used depends on the purpose of use, the difference in molar absorption coefficient of the dyes used, the combination of dyes
Although it is not uniformly determined by the above, the total amount of the near-infrared absorbing dye is usually added to the produced ethylene-vinyl acetate (EVA) adhesive polymer film.
It is preferably 0.01 g to 50 g / m ² . A particularly preferred amount is 0.1 g to 20 g / m ² .

Examples of desirable dyes include metal complex compounds, phthalocyanines, naphthalocyanines, aminium salts, anthraquinones and naphthoquinones. Particularly desirable dyes are metal complex compounds represented by the general formula (1) (Chemical formula 7) or general formulas (2) (Chemical formula 8), phthalocyanine compounds represented by the general formula (3) (Chemical formula 9), A naphthalosinin compound represented by the formula (4) (formula 10), an aminium salt compound represented by the general formula (5) (formula 11), or an anthraquinone compound represented by the general formula (6) (formula 12) Etc.

[0009]

[Chemical 7] [Wherein, A ^{1 to} A ⁸ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, a thiocyanate group, a cyanate group, an acyl group, a carbamoyl group, an alkylaminocarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group. Group, substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted alkoxy group,
A substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted alkylamino group, or a substituted or unsubstituted arylamino group, and Two matching substituents may be connected via a linking group.
R ^{1 to} R ⁴ are each independently a substituted or unsubstituted alkyl group,
It represents a substituted or unsubstituted aryl group. M represents a divalent metal atom, a trivalent or tetravalent substituted metal atom, or an oxymetal. ]

[0010]

[Chemical 8] [Wherein B ^{1 to} B ⁴ are each independently a hydrogen atom, a cyano group, an acyl group, a carbamoyl group, an alkylaminocarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a substituted or unsubstituted alkyl group, a substituted or It represents an unsubstituted aryl group, and two adjacent substituents may be connected via a linking group. M represents a divalent metal atom, a trivalent or tetravalent substituted metal atom, or an oxymetal. ]

[0011]

[Chemical 9] [In the formula, C ^{1 to} C ¹⁶ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl An oxy group, a substituted or unsubstituted alkylthio group, or a substituted or unsubstituted arylthio group, and C ¹ , C ² , C ³ , C ⁴ , C ⁵ and C ⁶ , C ⁷
And in each combination of C ^8, C ⁹ and C ¹⁰ and C ¹¹ and C ^12, C ¹³ and C ¹⁴ and C ¹⁵ and C ^16, does not become a combination of hydrogen atom at the same time. M represents a divalent metal atom, a trivalent or tetravalent substituted metal atom, or an oxymetal. ]

[0012]

[Chemical 10] [Wherein, D ^{1 to} D ²⁴ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group] An oxy group, a substituted or unsubstituted alkylthio group, or a substituted or unsubstituted arylthio group, and D ¹ , D ² , D ³ , D ⁴ , D ⁵ , D ⁶ , D ⁷
And D ⁸ and D ⁹ and D ¹⁰ and D ¹¹ and D ¹² , D ¹³ and D ¹⁴ , D ¹⁵ and D ¹⁶ , D ¹⁷ and D ¹⁸ , D ¹⁹ and D ²⁰ , D ²¹ and D ²² , D ²³ and D.
^In each of the ²⁴ combinations, no combination is simultaneously a hydrogen atom. M represents a divalent metal atom, a trivalent or tetravalent substituted metal atom, or an oxymetal. ]

[0013]

[Chemical 11] [Wherein, E ^{1 to} E ⁸ are hydrogen atoms, a substituted or unsubstituted alkyl group, Y is a halogen atom, SbF ₆ , ClO ₄ , BF
₄ , NO ₃ and n represent 1 or 2. ]

[0014]

[Chemical 12] [In the formula, the benzene rings a, b, c and d are the same or each independently, a substituted or unsubstituted alkyl group having a prime number of 1 to 20, a cycloalkyl group, a carbon number of 1 to 20 or an unsubstituted group. May be substituted with an alkyl group, a trifluoromethyl group or a halogen atom. ]

The metal complex compound represented by the above formula (1) or (2), the phthalocyanine represented by the formula (3), the naphthalocyanine represented by the formula (4), or the formula (5). In the aminium salt, A ^{1 to} A ⁸ , B ^{1 to} B ⁴ , R
Specific examples of the substituents represented by ^{1 to} R ⁴ , C ^{1 to} C ¹⁶ , D ^{1 to} D ²⁴ , and E ^{1 to} E ⁴ are described below. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Examples of the substituted or unsubstituted alkyl group are methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, t-butyl group. , N-pentyl group, iso-pentyl group, neo-pentyl group, 1,2-dimethyl-propyl group, n-hexyl group, cyclo-
Hexyl group, 1,3-dimethyl-butyl group, 1-iso-propylpropyl group, 1,2-dimethylbutyl group, n-heptyl group,
1,4-dimethylpentyl group, 2-methyl 1-iso-propylpropyl group, 1-ethyl-3-methylbutyl group, n-octyl group,
Carbon number 1 to 2-ethylhexyl group, 3-methyl-1-iso-propylbutyl group, 2-methyl-1-iso-propyl group, 1-t-butyl-2-methylpropyl group, n-nonyl group, etc. 20 linear or branched alkyl group, methoxymethyl group, methoxyethyl group, ethoxyethyl group, propoxyethyl group, butoxyethyl group, γ-methoxypropyl group, γ-ethoxypropyl group, methoxyethoxyethyl group, ethoxyethoxyethyl Group, dimethoxymethyl group, diethoxymethyl group, dimethoxyethyl group, alkoxyalkyl group such as diethoxyethyl group, alkoxyalkoxyalkyl group,
Alkoxyalkoxyalkoxyalkyl group, chloromethyl group, 2,2,2-trichloroethyl group, trifluoromethyl group, 2,2,2-trichloroethyl group, 1,1,1,3,3,3, -hexafluoro -2-Halogenated alkyl group such as propyl group,
Examples thereof include an alkylaminoalkyl group, a dialkylaminoalkyl group, an alkoxycarbonylalkyl group, an alkylaminocarbonylalkyl group and an alkoxysulfonylalkyl group.

Examples of the substituted or unsubstituted alkoxy group are methoxy group, ethoxy group, n-propyloxy group, iso-propyloxy group, n-butyloxy group, iso-
Butyloxy group, sec-butyloxy group, t-butyloxy group, n-pentyloxy group, iso-pentyloxy group, neo-
Pentyloxy group, 1,2-dimethyl-propyloxy group,
n-hexyloxy group, cyclo-hexyloxy group, 1,3-dimethyl-butyloxy group, 1-iso-propylpropyloxy group, 1,2-dimethylbutyloxy group, n-heptyloxy group, 1,4-dimethyl Pentyloxy group, 2-methyl-1-iso-
Propylpropyloxy group, 1-ethyl-3-methylbutyloxy group, n-octyloxy group, 2-ethylhexyloxy group, 3-methyl-1-iso-propylbutyloxy group, 2-methyl-1-iso-propyl 1 to 2 carbon atoms such as oxy group, 1-t-butyl-2-methylpropyloxy group, n-nonyloxy group
0 linear or branched alkoxy group, methoxymethoxy group, methoxyethoxy group, ethoxyethoxy group, propoxyethoxy group, butoxyethoxy group, γ-methoxypropyloxy group, γ-ethoxypropyloxy group, methoxyethoxyethoxy group, ethoxy Alkoxyalkoxy groups such as ethoxyethoxy group, dimethoxymethoxy group, diethoxymethoxy group, dimethoxyethoxy group, diethoxyethoxy group, alkoxyalkoxyalkoxy groups such as methoxyethoxyethoxy group, ethoxyethoxyethoxy group, butyloxyethoxyethoxy group, alkoxy Alkoxyalkoxyalkoxy group, chloromethoxy group, 2,2,2-trichloroethoxy group, trifluoromethoxy group, 2,2,2-trichloroethoxy group, 1,1,1,3,3,3, -hexafluoro- 2-propyloxy group And other halogenated alkoxy groups, dimethylaminoethoxy groups, diethylaminoethoxy groups and other alkylaminoalkoxy groups, dialkylaminoalkoxy groups, and the like.

Examples of the substituted or unsubstituted aryl group are halogenated phenyl groups such as phenyl group, chlorophenyl group, dichlorophenyl group, bromophenyl group, fluorinated phenyl group and iodinated phenyl group, tolyl group, xylyl group, Examples thereof include a mesityl group, an ethylphenyl group, a methoxyphenyl group, an ethoxyphenyl group and a pyridyl group. Examples of the substituted or unsubstituted aryloxy group include phenoxy group, naphthoxy group, alkylphenoxy group and the like.

The substituted or unsubstituted alkylthio group includes a methylthio group, an ethylthio group, an n-propylthio group,
iso-propylthio group, n-butylthio group, iso-butylthio group, sec-butylthio group, t-butylthio group, n-pentylthio group, iso-pentylthio group, neo-pentylthio group, 1,2-
Dimethyl-propylthio group, n-hexylthio group, cyclo-
Hexylthio group, 1,3-Dimethyl-butylthio group, 1-iso-
Propylpropylthio group, 1,2-dimethylbutylthio group,
n-heptylthio group, 1,4-dimethylpentylthio group, 2-methyl 1-iso-propylpropylthio group, 1-ethyl-3-methylbutylthio group, n-octylthio group, 2-ethylhexylthio group, 3- A straight chain having 1 to 20 carbon atoms such as methyl-1-iso-propylbutylthio group, 2-methyl-1-iso-propylthio group, 1-t-butyl-2-methylpropylthio group, n-nonylthio group or the like. Branched alkylthio group, methoxymethylthio group,
Methoxyethylthio group, ethoxyethylthio group, propoxyethylthio group, butoxyethylthio group, γ-methoxypropylthio group, γ-ethoxypropylthio group, methoxyethoxyethylthio group, ethoxyethoxyethylthio group, dimethoxymethylthio group, Alkoxyalkylthio groups such as diethoxymethylthio group, dimethoxyethylthio group, diethoxyethylthio group, alkoxyalkoxyalkylthio groups, alkoxyalkoxyalkoxyalkylthio groups, chloromethylthio group, 2,2,2-trichloroethylthio group, trifluoromethylthio group Group, 2,2,2-trichloroethylthio group, 1,1,1,3,3,3, -hexafluoro-2-
Examples thereof include halogenated alkylthio groups such as propylthio group, dimethylaminoethylcythio groups, alkylaminoalkylthio groups such as diethylaminoethylthio group, and dialkylaminoalkylthio groups.

Examples of the substituted or unsubstituted alkylthio group include methylthio group, ethylthio group, n-propylthio group,
iso-propylthio group, n-butylthio group, iso-butylthio group, sec-butylthio group, t-butylthio group, n-pentylthio group, iso-pentylthio group, neo-pentylthio group, 1,2-
Dimethyl-propylthio group, n-hexylthio group, cyclo-
Hexylthio group, 1,3-Dimethyl-butylthio group, 1-iso-
Propylpropylthio group, 1,2-dimethylbutylthio group,
n-heptylthio group, 1,4-dimethylpentylthio group, 2-methyl 1-iso-propylpropylthio group, 1-ethyl-3-methylbutylthio group, n-octylthio group, 2-ethylhexylthio group, 3- A straight chain having 1 to 20 carbon atoms such as methyl-1-iso-propylbutylthio group, 2-methyl-1-iso-propylthio group, 1-t-butyl-2-methylpropylthio group, n-nonylthio group or the like. Branched alkylthio group, methoxymethylthio group,
Methoxyethylthio group, ethoxyethylthio group, propoxyethylthio group, butoxyethylthio group, γ-methoxypropylthio group, γ-ethoxypropylthio group, methoxyethoxyethylthio group, ethoxyethoxyethylthio group, dimethoxymethylthio group, Alkoxyalkylthio groups such as diethoxymethylthio group, dimethoxyethylthio group, diethoxyethylthio group, alkoxyalkoxyalkylthio groups, alkoxyalkoxyalkoxyalkylthio groups, chloromethylthio group, 2,2,2-trichloroethylthio group, trifluoromethylthio group Group, 2,2,2-trichloroethylthio group, 1,1,1,3,3,3, -hexafluoro-2-
Examples thereof include halogenated alkylthio groups such as propylthio group, dimethylaminoethylcythio groups, alkylaminoalkylthio groups such as diethylaminoethylthio group, and dialkylaminoalkylthio groups. Examples of the substituted or unsubstituted arylthio group include phenylthio group, naphthylthio group, alkylphenylthio group and the like.

Further, examples of the divalent metal represented by M include Cu (II), Zn (II), Co (II) and Ni (I
I), Ru (II), Rh (II), Pd (II), Pt (I
I), Mn (II), Mg (II), Ti (II), Be (I
I), Ca (II), Ba (II), 1d (II), Hg (I
I), Pb (II), Sn (II) and the like. Examples of mono-substituted trivalent metals include Al-Cl, Al-Br,
Al-F, Al-I, Ga-Cl, Ga-F, Ga-
I, Ga-Br, In-Cl, In-Br, In-I,
In-F, Tl-Cl, Tl-Br, Tl-I, Tl-
_{F, Al-C 6 H 5} , Al-C 6 H 4 (CH 3), In
_{-C 6 H 5, In-C} 6 H 4 (CH 3), In-C 6 H
_{5, Mn (OH), Mn} (OC 6 H 5), Mn [OSi
(CH _{3) 3],} Fe-Cl, include Ru-Cl, etc.. Examples of the di-substituted tetravalent metal include CrCl ₂ and Si.
Cl ₂ , SiBr ₂ , SiF ₂ , SiI ₂ , ZrC
l ₂ , GeCl ₂ , GeBr ₂ , GeI ₂ , GeF ₂ ,
SnCl ₂ , SnBr ₂ , SnF ₂ , TiCl ₂ , Ti
Br ₂ , TiF ₂ , Si (OH) ₂ , Ge (OH) ₂ ,
Zr (OH) ₂ , Mn (OH) ₂ , Sn (OH) ₂ , T
iR ₂ , CrR ₂ , SiR ₂ , SnR ₂ , GeR ₂ [R
Represents an alkyl group, a phenyl group, a naphthyl group, and a derivative thereof], Si (OR ') ₂ , Sn (OR') ₂ ,
Ge (OR ') ₂ , Ti (OR') ₂ , Cr (OR ')
₂ [R ′ represents an alkyl group, a phenyl group, a naphthyl group, a trialkylsilyl group, a dialkylalkoxysilyl group and derivatives thereof], Sn (SR ″) ₂ , Ge (S
R ″) ₂ (R ″ represents an alkyl group, a phenyl group, a naphthyl group, or a derivative thereof), etc. Examples of the oxy metal include VO, MnO, and TiO.

Specific examples of the substituents on the benzene rings a, b, c and d of the anthraquinone represented by the formula (6) are described below. Substituents on the benzene rings a, b, c, d include methyl group, ethyl group, n-propyl group, iso-propyl group, n-
Butyl group, iso-butyl group, sec-butyl group, t-butyl group,
n-pentyl group, iso-pentyl group, neo-pentyl group, 1,2-
Dimethyl-propyl group, n-hexyl group, cyclo-hexyl group, 1,3-dimethyl-butyl group, 1-iso-propylpropyl group, 1,2-dimethylbutyl group, n-heptyl group, 1,4-dimethyl Pentyl group, 2-methyl 1-iso-propylpropyl group,
1-ethyl-3-methylbutyl group, n-octyl group, 2-ethylhexyl group, 3-methyl-1-iso-propylbutyl group, 2-methyl-1-iso-propyl group, 1-t-butyl-2- C1-C20 linear or branched alkyl group such as methylpropyl group, n-nonyl group, cycloalkyl group such as cyclohexyl group, cyclopentyl group, methoxy group, ethoxy group, n-propyloxy group, iso-propyl Oxy group, n-butyloxy group, iso-butyloxy group, sec-butyloxy group, t-butyloxy group, n-pentyloxy group, iso-pentyloxy group, neo-pentyloxy group, 1,2-dimethyl-propyloxy group , N-hexyloxy group, cyclo-hexyloxy group, 1,3-dimethyl-butyloxy group, 1-iso-propylpropyloxy group, 1,2-dimethylbutyloxy group, n-heptyloxy group, 1,4- Dimethylpentyloxy group, 2-methyl-1-iso -Propylpropyloxy group, 1-ethyl-3-methylbutyloxy group, n-octyloxy group, 2-ethylhexyloxy group, 3-methyl-1-iso-propylbutyloxy group, 2-methyl-1-iso- Propyloxy group, 1-t-butyl
-2-Methylpropyloxy group, n-nonyloxy group and other linear or branched alkoxy groups having 1 to 20 carbon atoms, trifluoromethyl group, halogen such as fluorine, chlorine, bromine and iodine. Further, the substitution position of these substituents is o
It may be any of-, m-, and p-, and one or more benzene rings may be substituted.

The ultraviolet absorber having a maximum absorption wavelength in the wavelength range of 250 to 400 nm of the present invention is 400 to 700.
The compound is not particularly limited as long as it has a small absorption in the visible region of nm and a large absorption in the range of 250 to 400 nm. For example, light stabilizers described in "Photopolymer deterioration and stabilization" (Zenjiro Osawa, CMC), for example, benzotriazole ultraviolet absorbers, benzophenone ultraviolet absorbers, salicylate ultraviolet absorbers, acrylates. Examples of the ultraviolet absorber include oxalic acid anilide ultraviolet absorbers. Particularly preferred compounds include benzotriazole-based UV absorbers represented by the following general formula (7) (formula 13) and the following general formula (8) (formula 1)
A benzophenone-based external ray absorbent represented by 3), a lysyl acid ester-based ultraviolet absorbent represented by the following general formula (9) (Chemical formula 13), and an arelate ultraviolet ray represented by the following general formula (10) (Chemical formula 13) Absorbent, the following general formula (11) (Chemical formula 13)
And an oxalic acid anilide-based ultraviolet absorber represented by

[0024]

[Chemical 13] [In the formula, R ⁵ to R ¹² each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, R ¹² ~
R ^49's each independently represent a hydrogen atom, a halogen atom, a hydroxy group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, X represents a hydrogen atom, a substituted or unsubstituted alkyl group, and n represents 3 to 3 Represents an integer of 20. ]

The amount used is not generally determined by the purpose of use, the difference in molar extinction coefficient of the ultraviolet absorber to be used, the combination of absorbers, etc., but usually the produced ethylene-vinyl acetate ( The total amount of the ultraviolet absorber used is 0.1) based on the EVA) adhesive polymer film.
g to 500 g / m ² is preferable. Examples of the ethylene-vinyl acetate (EVA) adhesive polymer used in the present invention include an EVA hot melt adhesive containing EVA as a main component, or a part or all of the acetic ester portion of EVA, which is hydrolyzed. Also included are modified adhesive polymers in which some or all of them are replaced with other substituents having a carboxyl group or an ester group. Commercially available EVA adhesive polymers include, for example, Diabond Industry Co., Ltd.
Merlotron O series, Hiyoshi Chemical Co., Ltd., Hiyoshi Melt, Nippon Matai Co., Ltd., Elfan OH, Yokohama Rubber Co., Ltd., Hamaite M-410, Hirodyne Industry Co., Ltd.
Hirodine, Aika Kogyo Co., Ltd., and the like. Alternatively, E manufactured by Bridgestone Co., Ltd., which is commercially available as an interlayer film (adhesive) of EVA-based glass or the like.
VASAFE, Dumilan of Takeda Co., Dumilan film, etc. can also be used. If necessary, additives such as a plasticizer, an antioxidant, a singlet oxygen quencher, and a triplet radical trapping agent can be added.

Generally, the following four methods can be used as the method for producing the near infrared ray absorbing plate of the present invention. EVA-based adhesive polymer, near-infrared absorbing dye and ultraviolet absorber are mixed and melted, coated on the glass or resin plate to be adhered, and another glass or resin plate is placed on the glass or resin plate at 50 to 200 ° C. Crimp at temperature. The thickness of the adhesive layer is usually 10 μm to 5 mm. A particularly preferred thickness is 0.1 to 1 mm. An EVA-based adhesive polymer, a near-infrared absorbing dye and an ultraviolet absorbing agent are mixed and melted, and molded by extrusion or the like to prepare a film. Using the film as an intermediate film, glass and glass, glass and resin plate, or resin plate and resin plate are pressure bonded at a temperature of 50 to 200 ° C. The thickness of the film is usually 10 μm to 5 mm. Particularly preferred thickness is 0.1
~ 1 mm. An EVA-based adhesive polymer film containing an ultraviolet absorber is prepared, a near-infrared absorbing dye is applied to the film surface or the inside of the glass or resin plate to be adhered, and the films are pasted together at a temperature of 50 to 200 ° C. Crimp with.
The near-infrared absorbing dye partially dissolves in the intermediate film during heating and pressure bonding, so that the adhesive strength and the like are not adversely affected. A solution is prepared by dissolving a near-infrared absorbing dye and an ultraviolet absorbing agent in an organic solvent such as toluene, chloroform and alcohols. Next, in the solution, separately prepared 10μ
An EVA-based adhesive polymer film having a thickness of m to 5 mm is impregnated to prepare a film coated with a near infrared absorbing dye and an ultraviolet absorber. Using the film as an intermediate film, glass and glass, glass and resin plate, or resin plate and resin plate are pressure bonded at a temperature of 50 to 200 ° C. At that time, an EVA-based adhesive polymer film containing an ultraviolet absorber may be sandwiched on both sides of a film coated with a near-infrared absorbing dye and pressure-bonded. In addition to the above methods,
A near-infrared absorbing dye, an ultraviolet absorbing agent and an EVA polymer resin may be dissolved in an organic solvent to prepare a cast film for use.

The glass used for making the near infrared absorbing plate is not particularly limited as long as it is an inorganic glass. The resin plate is not particularly limited as long as it has high transparency, but for example, a rigid plate or film of acrylic, polycarbonate, polyethylene terephthalate (PET), polysulfone, polyether sulfone, polyamide, polyimide or the like can be used. . Based on the above embodiment, an ethylene-vinyl acetate (EVA) -based adhesive polymer containing a near-infrared absorbing dye and an ultraviolet absorber having a maximum absorption wavelength in the wavelength range of 250 to 400 nm and a glass or a resin plate are produced together. The near-infrared absorbing plate has excellent light resistance and near-infrared absorbing ability, and the manufacturing method is simple, which is extremely valuable in practical use.

[0028]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited thereto. The phthalocyanine compound represented by the formulas (12) and (15) shown in the examples is a simplification of the structure represented by the formula (3) in the text. Example 1 Ethylene-vinyl acetate (EVA) -based adhesive polymer flakes (Meltron O-17 manufactured by Diabond Industry Co., Ltd.)
1) 2.0 kg, 20 g of salicylate-based ultraviolet absorber (Biosorb 130 manufactured by Kyodo Yakuhin Co., Ltd.), and 2 g of copper phthalocyanine represented by the following formula (12) (Chemical Formula 14) as a near-infrared absorbing dye were mixed. , 130-1
It was melted at 60 ° C., and a film having a thickness of 300 μm was produced with an extruder. Subsequently, the film was sandwiched between 3 mm-thick float glass and placed in an autoclave at 110 ° C.
A laminated glass was prepared by treating the laminated glass for 20 minutes at atmospheric pressure. This laminated glass is a spectrophotometer U-3 manufactured by Hitachi, Ltd.
Measured at 400, T according to JIS-R-3106
_{When V} and T _E are calculated, T _V = 76%, T _E =
It was 61%. The laminated glass was heated at 63 ° C. under
A light resistance test was performed by irradiating with a carbon arc lamp for 500 hours. When the transmittance was measured in the same manner after the test, the change in transmittance in the near infrared region was small and the decomposition of the dye by light was small. Further, when T _V and T _E are calculated in the same manner, T _V = 76% and T _E = 62%,
The changes in T _V and T _E before and after the test were small, and the light resistance was good.

[0029]

[Chemical 14]

Example 2 As a near infrared absorbing dye, 2 g of a nickel dithiol complex represented by the following formula (13) (Chemical formula 15) and the following formula (14) (Chemical formula 15) were used instead of the formula (12). A laminated glass was produced by performing the same operation as in Example 1 except that 2 g of the metal complex described above was used. When the same measurement and calculation as in Example 1 were performed, T _V = 81% and T _E = 68%
Met. The laminated glass was irradiated with a carbon arc lamp for 500 hours under the condition of 63 ° C. to perform a light resistance test.
When the transmittance was measured in the same manner after the test, the change in transmittance in the near infrared region was small and the decomposition of the dye by light was small. Further, when T _V and T _E were calculated in the same manner, T _V = 82% and T _E = 70%, and the changes in T _V and T _E before and after the test were small and the light resistance was good.

[0031]

[Chemical 15]

Example 3 10 g of a benzotriazole type ultraviolet absorber (Biosorb 583 manufactured by Kyodo Chemical Co., Ltd.) and 1 g of a phthalocyanine compound represented by the following formula (15) (Chemical Formula 16) as a near-infrared absorbing dye were added to 100 ml of toluene. A solution containing a near infrared absorbing dye was prepared by dissolving. In the solution, ethylene-
The film was impregnated with a vinyl acetate (EVA) -based adhesive polymer film (Dumilan film, which is a laminated glass interlayer film manufactured by Takeda Co., Ltd.) and then taken out, and toluene was evaporated to produce a near infrared absorbing dye-containing EVA film. A laminated glass was produced in the same manner as in Example 1. When the same measurement and calculation as in Example 1 were performed, T _V = 71% and T _E =
It was 57%. The laminated glass was heated at 63 ° C. under
A light resistance test was performed by irradiating with a carbon arc lamp for 500 hours. When the transmittance was measured in the same manner after the test, the change in transmittance in the near infrared region was small and the decomposition of the dye by light was small. Further, when T _V and T _E are calculated in the same manner, T _V = 72% and T _E = 59%,
The changes in T _V and T _E before and after the test were small, and the light resistance was good.

[0033]

[Chemical 16]

Example 4 Example 1 was prepared by sandwiching the near infrared ray absorbing dye-containing EVA film prepared in Example 3 with a polycarbonate plate having a thickness of 3 mm.
A composite plate was prepared in the same manner as in. When the same measurement and calculation as in Example 1 were performed, T _V = 70% and T _E = 55.
%Met. The laminated glass was irradiated with a carbon arc lamp for 500 hours under the condition of 63 ° C. to perform a light resistance test. When the transmittance was measured in the same manner after the test, the change in transmittance in the near infrared region was small and the decomposition of the dye by light was small. Further, when T _V and T _E were calculated in the same manner, T _V = 70% and T _E = 56%, and the changes in T _V and T _E before and after the test were small and the light resistance was good.

Comparative Example 1 A laminated glass was prepared in the same manner as in Example 1, except that the salicylic acid ester type ultraviolet absorber was not added. When the same measurement and calculation as in Example 1 were performed, T _V = 76% and T _E = 60%. The laminated glass was irradiated with a carbon arc lamp for 500 hours under the condition of 63 ° C. to perform a light resistance test. When the transmittance was measured in the same manner after the test, the change in transmittance in the near infrared region was large, and the decomposition of the dye by light was large. Further, when T _V and T _E are calculated in the same manner, T _V = 80
%, T _E = 70%, T _V and T _E before and after the test
Change was large and the light resistance was insufficient.

Comparative Example 2 Except that no benzotriazole type ultraviolet absorber was added,
The same operation as in Example 3 was performed to produce a laminated glass. When the same measurement and calculation as in Example 1 were performed,
T _V = 72% and T _E = 57%. The laminated glass was irradiated with a carbon arc lamp for 500 hours under the condition of 63 ° C. to perform a light resistance test. When the transmittance was measured in the same manner after the test, the change in transmittance in the near infrared region was large, and the decomposition of the dye by light was large. Further, when T _V and T _E are calculated in the same manner, T _V = 75%,
T _E = 65%, the changes in T _V and T _E before and after the test were large, and the light resistance was insufficient. Comparative Example 3 A laminated glass was produced by performing the same operations as in Example 1 except that the salicylic acid ester-based ultraviolet absorber and the phthalocyanine-based near infrared absorbing dye were not added. When the same measurement and calculation as in Example 1 were performed, T _V = 90%, T
_E = 90% and the heat ray blocking function was insufficient.

As is clear from the examples and comparative examples, the near-infrared absorbing plate using the near-infrared absorbing dye has a large T _V of 70% or more and a small T _E. Further, the near-infrared absorbing plate produced without using the ultraviolet absorber has a large decomposition of the dye and a large deterioration of T _{E in} the light resistance test for 500 hours, but the maximum absorption wavelength is in the wavelength range of 250 to 400 nm according to the present invention. When combined with an ultraviolet absorber having
It is clear that the change in T _E is small and that the dye in the near infrared absorbing plate has excellent light resistance.

[0038]

INDUSTRIAL APPLICABILITY The present invention makes it possible to provide a near-infrared absorbing plate which has excellent light resistance and is easy to manufacture, and is extremely valuable in practical use.

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Claims (4)

[Claims] 1. A near infrared absorbing dye and a wavelength of 250 to 40.
A near-infrared absorbing plate obtained by laminating an ethylene-vinyl acetate (EVA) adhesive polymer containing an ultraviolet absorber having a maximum absorption wavelength at 0 nm and a glass or resin plate. 2. A near-infrared absorbing dye is a metal complex compound represented by the general formula (1) (formula 1) or the general formula (2) (formula 2), or a general formula (3) (formula 3). A phthalocyanine compound represented by the general formula (4) (formula 4), an aminium salt compound represented by the general formula (5) (formula 5), or a general formula (6) (formula 6) The near infrared absorbing plate according to claim 1, which is at least one of the anthraquinone compounds represented. [Chemical 1] [Wherein, A ^{1 to} A ⁸ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, a thiocyanate group, a cyanate group, an acyl group, a carbamoyl group, an alkylaminocarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group. Group, substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted alkoxy group,
A substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted alkylamino group, or a substituted or unsubstituted arylamino group, and Two matching substituents may be connected via a linking group.
R ^{1 to} R ⁴ are each independently a substituted or unsubstituted alkyl group,
It represents a substituted or unsubstituted aryl group. Z represents a sulfur atom or an oxygen atom. M is a divalent metal atom, trivalent or 4
It represents a valent substituted metal atom or an oxy metal. ] [Chemical 2] [Wherein B ^{1 to} B ⁴ are each independently a hydrogen atom, a cyano group, an acyl group, a carbamoyl group, an alkylaminocarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a substituted or unsubstituted alkyl group, a substituted or It represents an unsubstituted aryl group, and two adjacent substituents may be connected via a linking group. M represents a divalent metal atom, a trivalent or tetravalent substituted metal atom, or an oxymetal. ] [Chemical 3] [In the formula, C ^{1 to} C ¹⁶ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl An oxy group, a substituted or unsubstituted alkylthio group, or a substituted or unsubstituted arylthio group, and C ¹ , C ² , C ³ , C ⁴ , C ⁵ and C ⁶ , C ⁷
And in each combination of C ^8, C ⁹ and C ¹⁰ and C ¹¹ and C ^12, C ¹³ and C ¹⁴ and C ¹⁵ and C ^16, does not become a combination of hydrogen atom at the same time. M represents a divalent metal atom, a trivalent or tetravalent substituted metal atom, or an oxymetal. ] [Chemical 4] [Wherein, D ^{1 to} D ²⁴ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group] An oxy group, a substituted or unsubstituted alkylthio group, or a substituted or unsubstituted arylthio group, and D ¹ , D ² , D ³ , D ⁴ , D ⁵ , D ⁶ , D ⁷
And D ⁸ and D ⁹ and D ¹⁰ and D ¹¹ and D ¹² , D ¹³ and D ¹⁴ , D ¹⁵ and D ¹⁶ , D ¹⁷ and D ¹⁸ , D ¹⁹ and D ²⁰ , D ²¹ and D ²² , D ²³ and D.
^In each of the ²⁴ combinations, no combination is simultaneously a hydrogen atom. M represents a divalent metal atom, a trivalent or tetravalent substituted metal atom, or an oxymetal. ] [Chemical 5] [Wherein, E ^{1 to} E ⁸ are hydrogen atoms, a substituted or unsubstituted alkyl group, Y is a halogen atom, SbF ₆ , ClO ₄ , BF
₄ , NO ₃ and n represent 1 or 2. ] [Chemical 6] [In the formula, the benzene rings a, b, c and d are the same or each independently, a substituted or unsubstituted alkyl group having a prime number of 1 to 20, a cycloalkyl group, a carbon number of 1 to 20 or an unsubstituted group. May be substituted with an alkyl group, a trifluoromethyl group or a halogen atom. ] 3. A near infrared absorbing dye and a wavelength of 250 to 40.
The near-infrared absorbing plate according to claim 1, which is obtained by sandwiching both sides of an ethylene-vinyl acetate (EVA) -based adhesive polymer containing an ultraviolet absorber having a maximum absorption wavelength at 0 nm with glass to prepare a laminated glass. . 4. A near infrared absorbing dye and a wavelength of 250 to 40.
The near-infrared absorption according to claim 1, which is obtained by sandwiching both sides of an ethylene-vinyl acetate (EVA) adhesive polymer containing an ultraviolet absorber having a maximum absorption wavelength at 0 nm with resin plates to prepare a composite plate. Board.