JPH06194517A - Heat ray shielding sheet - Google Patents

Abstract

PURPOSE:To obtain a heat ray shielding sheet having excellent shielding capacity without losing its transparency by incorporating a near IR absorbing dyestuff having a specified maximum absorption peak. CONSTITUTION:An IR reflecting laminate capable of reflecting a heat ray is combined with a near IR absorbing dyestuff capable of absorbing a heat ray and having the maximum absorption peak in 650-800nm wavelengths. Since the light transmittance of the laminate is high in 700-800nm wavelengths, the solar radiation transmittance TE is not reduced. Further a heat ray shielding sheet capable of effectively reducing the TE is obtained without significantly lowering the visible light transmittance TV because the light of 650-700nm wavelengths in the visible lights low in visibility and having a large solar radiation energy is absorbed. In this case, the laminate is obtained by alternately laminating a metal oxide layer and a metallic layer starting with the metal oxide layer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sheet having high transparency and an excellent heat ray shielding effect for the purpose of energy saving. The highly transparent heat ray-shielding sheet, when combined with the window glass of a building or a house, restricts the inflow of solar energy into the room, suppresses the indoor temperature rise in the summer, and contributes to energy saving during cooling. Also, by incorporating it into the windows of automobiles, trains, etc., the temperature rise inside the car in hot weather can be suppressed, cooling efficiency can be improved, and the load on the engine can be reduced by saving energy.

[0002]

2. Description of the Related Art When an excellent heat ray-shielding sheet for actually incorporating a heat ray-shielding sheet into a building material such as a building or a house or a window of an automobile, a train, etc. is used, the visible light transmittance (T _V ) Is important. For example, in the case of an automobile windshield, T _V is 7 from the viewpoint of safety.
It is specified by the JIS standard that it is 0% or more. Further, an index of heat ray interception for sunlight can be expressed by the solar radiation transmittance (T _E ), and the smaller T _E is, the higher the heat ray interception performance is, and it is important to suppress T _E as small as possible for energy saving. As described in detail below,
Conventionally, when the heat ray blocking film is increased in T _V , T _E is also increased and the heat ray blocking efficiency is deteriorated. Further, if T _E is made smaller, T _V also becomes lower, and the JIS standard T _V does not satisfy the standard of 70% or more. Especially difficult is _TV
Is a technique for reducing T _E to about 40 to 44% while maintaining 70% or more. Some of the heat ray absorbing sheets and heat ray reflecting sheets having T _V of 70% or more have already been put into practical use and are on the market, but all have a wavelength of 700.
The heat ray has not been completely cut over the entire infrared region above nm. Especially as a drawback of them, 7
The light transmittance in the vicinity of 00 to 800 nm is large, which is an obstacle to reducing T _E.

As a prior art, Japanese Patent Laid-Open No. 56-32352
As a film having a heat ray reflection function, a polyester film surface with a specific thickness of tungsten oxide / silver /
There is proposed a stack of stacked thin films of a three-layer structure of tungsten oxide. However, in the case of the three-layer structure, T _E cannot be made sufficiently small because the rise of reflection in the near infrared region is slow. In addition, JP-A-63-1343
As the film 32 having a heat ray reflecting function, a laminated thin film of 5 layers of oxide / silver / oxide / silver / oxide having a specific film thickness is formed on the substrate 32 to show the characteristics of the heat ray reflecting film having a three-layer structure. Suggestions for improvement have been made. However, even in the five-layer structure, compared with the three-layer structure, although the rise of reflection in the near infrared region is sharpened and T _E is improved,
The light transmittance is large in the wavelength range of 800 nm.

Further, in JP-A-60-127152, a laminated body of silver alloy / organic polymer having a refractive index of 1.35 or more / silver alloy is used as a selective light transmitting film, and a wavelength of 800 to 1200 n.
Attempts have been made to combine selective layers containing a near infrared absorber having an absorption peak between m. But T
_In order to reduce _E , it is a wavelength band in which the heat ray transmittance of the selective light transmitting film is large and the solar energy is large.
It is effective to cut heat rays of 00 nm or more, but a near-infrared absorber having an absorption peak in the range of 800 to 1200 nm cannot efficiently absorb the wavelength range of 700 to 800 nm. In particular, it is difficult to produce a heat ray-shielding sheet that meets the criteria of T _V of 70% or more and T _E of 44% or less on an industrial scale by the conventional technique of sputtering metals on a plastic film.

[0005]

The object of the present invention is to have an excellent heat ray ability without losing transparency by combining the heat ray reflecting function of the infrared ray reflective laminate and the heat ray absorbing function of the near infrared ray absorbing dye. It is to provide a heat ray shielding sheet.

[0006]

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have found that an infrared reflective laminate having a heat ray reflecting function and a wavelength of 650 nm having a heat ray absorbing function.
By combining a near-infrared absorbing dye having a maximum absorption peak between 800 nm and less than 800 nm, the infrared reflective laminate has a large light transmittance in the wavelength range of 700 to 800 nm, thereby compensating for the drawback that T _E is prevented from being reduced, Furthermore, an epoch-making heat ray-shielding sheet that effectively reduces T _E without significantly lowering T _V by absorbing light in the wavelength range of 650 to 700 nm, which has a low luminosity factor but has a low luminosity factor in visible light. The inventors have found that they can be obtained and completed the present invention. That is, the present invention is a heat ray-shielding sheet comprising an infrared reflective laminate, which has a wavelength of 650 nm or more and 8
The present invention relates to a heat ray-shielding sheet containing a near-infrared absorbing dye having a maximum absorption peak in the range of less than 00 nm.

The infrared reflective laminate used in the present invention is a laminate in which a metal oxide layer and a metal layer are alternately laminated in order from the metal oxide layer. The thickness of each layer is 50 metal layers.
~ 500Å, metal oxide is 100 ~ 2000Å.
The conditions for creating each layer are 10 on the plastic film substrate.
^The film is carried at ^-1 to 10 ^-7 torr by a method such as sputtering, vacuum deposition, ion plating, etc. to prepare an infrared reflective laminate supporting film. Examples of the material for the metal oxide layer include highly transparent indium-tin oxide (ITO), indium oxide, tin oxide, silicon oxide, aluminum oxide, zinc oxide, and tungsten oxide. Examples include metals such as gold, silver, copper, platinum, aluminum, nickel, palladium, iridium, tin, chromium, and zinc, and alloys or mixtures containing these metals as main components.

The substrate plastic film used for laminating the infrared reflective laminate is a polyethylene terephthalate film, a polymethylmethacrylate film, a polycarbonate film, a polyethylene film, a polysulfone film, a polyethersulfone film, a nylon film, a polyamide film, a polyacrylate. Films, polyvinyl chloride films, polyvinyl fluoride films and the like having high transparency can be mentioned. Particularly preferred substrate plastic film, polyethylene terephthalate film, polymethylmethacrylate film, polycarbonate film,
Is mentioned. As a particularly preferable infrared reflective laminate supporting film, a film prepared by sputtering indium oxide / silver on indium oxide / silver / indium / silver / indium oxide in five layers alternately on a polyethylene terephthalate film can be mentioned.

Regarding the present invention, the following six methods can be mentioned as a method for producing a heat ray shielding sheet containing an infrared reflective laminate and a near infrared absorbing dye. The first is
First, a method of preparing a near-infrared absorbing dye-containing plastic film (A) and laminating it with an infrared reflective laminate supporting film (B) obtained by attaching an infrared reflective laminate on a substrate plastic film of 10 to 200 μm by sputtering or the like. To be The plastic pellets used as the material of the plastic film (A) containing the near infrared absorbing dye are polyethylene terephthalate, polymethylmethacrylate, polycarbonate, polyethylene, polysulfone, polyethersulfone, nylon, polyamide, polyacrylate, polyvinyl chloride, polyvinyl fluoride. , Etc., which have high transparency, are prepared by mixing plastic pellets and a near infrared absorbing dye,
It is heated to 0-350 ℃ and melted, and it is made into a film by an extruder or made into an original fabric by an extruder.
A method of forming a 10-200 μm thick film by uniaxially or biaxially stretching 2 to 5 times at ˜90 ° C., or alcohols such as the above-mentioned plastic pellets such as toluene, hexane, cyclohexane, methanol, ethanol and isopropanol , Toluene, xylene, and other aromatics, hexane, cyclohexane, ethylcyclohexane, and other aliphatic compounds, methyl cellosolve, isolopyru cellusolve and other cellosolves, etc. A method of forming a film having a thickness of up to 300 μm can be used. The adhesive used to bond (A) and (B) is a known transparent adhesive such as a silicone-based, urethane-based or acrylic-based adhesive, and the thickness of the adhesive layer is 1 to 100 μm. Secondly, there is a method in which (A) prepared in the same manner as the first method is used as a substrate plastic film, and an infrared reflective laminate is attached thereto by sputtering or the like.

Third, at least one surface of the infrared reflective laminate supporting film (B) in the first method is coated with a near infrared absorbing dye dissolved in a solvent, or the near infrared absorbing dye and a resin are dissolved in a solvent. It is a coating method. As the solvent, toluene, hexane,
Cyclohexane, methanol, ethanol, isopropanol, and other alcohols, toluene, xylene, and other aromatic compounds, hexane, cyclohexane, ethylcyclohexane, and other aliphatic compounds, methyl cellosolve, and isopyrcerosolve Cellulose is used as the resin, and the resin is a natural resin such as a cellulose acetate derivative, an acrylic resin, a phenol resin, a urea resin, a melanin resin, a vinyl resin, an alkyd resin, an epoxy resin, or a synthetic resin such as a urethane resin. Alternatively, they may be used in combination of several kinds. Examples of the coating method include a barcode method, a spin coating method, and a transfer method.

Fourth, a near-infrared absorbing dye coating film (C) is prepared by coating a near-infrared absorbing dye on at least one surface of a plastic film having a thickness of 10 to 200 μm by the same method as the third method.
As a substrate plastic film, a method of attaching an infrared reflective laminate to the near infrared absorbing dye coating surface of (C) or the surface not coated with the near infrared absorbing dye by sputtering or the like can be mentioned.

The fifth is (B) and the fourth in the first method.
There is a method of laminating (C) prepared by the method of 1) in the same manner as the first method. As a method for laminating two films, a method of aligning the infrared reflective laminate surface of (B) and the near infrared absorbing dye coating surface of (C),
(B) the plastic surface and (C) the near infrared absorbing dye coating surface are matched, (B) the plastic surface and (C) the plastic surface are matched, or (B) the infrared reflective laminate surface ( There is a method of matching the plastic surfaces of C).

Sixth, (B) and 10 in the first method
Examples include a method of mixing and dissolving a near-infrared absorbing dye in a transparent adhesive such as a silicone-based, urethane-based, or acrylic-based adhesive used when laminating a plastic film having a thickness of up to 200 μm.

The near-infrared absorbing dye used in the present invention is 6
The dye is not particularly limited as long as it has a maximum absorption peak at 50 nm or more and less than 800 nm.
JP 61-154888 A, JP 61-19728 A
1, JP-A-61-246091, JP-A-63-3799
1, JP-A-63-39388, JP-A-62-23328
8, JP-A-63-312889, JP-A-2-4326
9, JP-A-2-138382, JP-A-2-29688
5, JP-A-3-43461, JP-A-3-77840, JP-A-3-100066, JP-A-3-628878, Japanese Patent Application No. 3-338557, Japanese Patent Application No. 3-99730, Japanese Patent Application No. 3-
Phthalocyanines as disclosed in JP-A-252414, JP-A-61-291651 and JP-A-61-2916.
52, JP-A-62-1260, and JP-A-62-1329.
63, Japanese Patent Application Laid-Open No. 1-129068, Japanese Patent Application Laid-Open No. 1-17245.
The anthraquinones as disclosed in No. 8 are preferable, and the amount thereof is preferably 1 to 1000 mg / m ² with respect to the area of the heat ray shielding sheet to be prepared.

Particularly preferred dyes include phthalocyanines represented by the following general formula (I) (formula 1).

[0016]

[Chemical 1] [In the formula (I), A ^{1 to} A ⁸ each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkoxy group, and A ¹ and A ² ,
Each combination of A ³ and A ⁴ , A ⁵ and A ⁶ , and A ⁷ and A ⁸ is not a combination of simultaneously hydrogen atoms. On the other hand, B ^{1 to} B ⁸ are each independently a hydrogen atom,
Halogen atom, substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted alkoxy group,
It represents a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio group, or a substituted or unsubstituted arylthio group. M represents a divalent metal atom, a divalent or tetravalent substituted metal atom, or an oxy metal. ]

Examples of the substituted or unsubstituted alkyl group represented by A ^{1 to} A ⁸ or B ^{1 to} B ⁸ in the formula (I) are methyl group, ethyl group, n-propyl group and 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-methyl group Propyl group, n-nonyl group, straight-chain or branched alkyl group having 1 to 20 carbon atoms, 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, diethoxyethyl group and other alkoxyalkyl groups, alkoxyalkoxyalkyl groups, alkoxyalkoxyalkoxyalkyl groups, Chloromethyl group,
2,2,2-trichloroethyl group, trifluoromethyl group, 2,
2,2-trichloroethyl group, 1,1,1,3,3,3, -hexafluoro-2-propyl group, and other halogenated alkyl groups, alkylaminoalkyl groups, dialkylaminoalkyl groups,
Alkoxycarbonylalkyl group, alkylaminocarbonylalkyl group, alkoxysulfonylalkyl group,
Examples thereof include an alkylsulfonyl 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-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, etc., a linear or branched alkoxy group having 1 to 20 carbon atoms, methoxymethoxy group, methoxyethoxy group, ethoxy Ethoxy group, propoxyethoxy group, butoxyethoxy group, γ-methoxypropyloxy group, γ-ethoxypropyloxy group, methoxyethoxyethoxy group, ethoxyethoxyethoxy group, dimethoxymethoxy group, diethoxymethoxy group, dimethoxyethoxy group, diethoxy Alkoxyalkoxy groups such as ethoxy groups, methoxyethoxyethoxy groups, ethoxyethoxyethoxy groups, alkoxyalkoxyalkoxy groups such as butyloxyethoxyethoxy groups, alkoxyalkoxyalkoxyalkoxy groups, chloromethoxy groups, 2,
2,2-trichloroethoxy group, trifluoromethoxy group,
Halogenated alkoxy groups such as 2,2,2-trichloroethoxy group, 1,1,1,3,3,3, -hexafluoro-2-propyloxy group, alkyl such as dimethylaminoethoxy group and diethylaminoethoxy group Examples thereof include an aminoalkoxy group and a dialkylaminoalkoxy group. Examples of the substituted or unsubstituted aryl group are phenyl group, chlorophenyl group, dichlorophenyl group, bromophenyl group, fluorinated phenyl group, halogenated phenyl group such as iodinated phenyl group, tolyl group, xylyl group, mesityl group, Examples thereof include an ethylphenyl group, a methoxyphenyl group, an ethoxyphenyl group and a pyridyl group. Examples of the substituted or unsubstituted aryloxy group include a phenoxy group, a naphthoxy group, an alkylphenoxy group, and the like, and the substituted or unsubstituted alkylthio group includes a methylthio group, an ethylthio group, an n-propylthio group, and 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-methyl-1
-iso-propylbutylthio group, 2-methyl-1-iso-propylthio group, 1-t-butyl-2-methylpropylthio group, n-nonylthio group, etc. having a straight or branched chain of 1 to 20 carbon atoms Alkylthio group, methoxymethylthio group, methoxyethylthio group, ethoxyethylthio group, propoxyethylthio group, butoxyethylthio group, γ-methoxypropylthio group, γ-ethoxypropylthio group, methoxyethoxyethylthio group, ethoxyethoxyethyl Alkoxyalkylthio groups such as thio group, dimethoxymethylthio group, diethoxymethylthio group, dimethoxyethylthio group, diethoxyethylthio group, alkoxyalkoxyalkylthio groups, alkoxyalkoxyalkoxyalkylthio groups,
Chloromethylthio group, 2,2,2-trichloroethylthio group,
Halogenated alkylthio groups such as trifluoromethylthio group, 2,2,2-trichloroethylthio group, 1,1,1,3,3,3, -hexafluoro-2-propylthio group, dimethylaminoethylcythio group , An alkylaminoalkylthio group such as a diethylaminoethylthio group, a dialkylaminoalkylthio group, and the like. Examples of the substituted or unsubstituted arylthio group include a phenylthio group, a naphthylthio group, an alkylphenylthio group, and the like.

As examples of the divalent metal represented by M, Cu (II), Zn (II), Co (II), 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), Cd (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 disubstituted tetravalent metals include CrCl ₂ and SiC.
l ₂ , SiBr ₂ , SiF ₂ , SiI ₂ , ZrCl ₂ ,
_{GeCl 2, GeBr 2, GeI 2} , GeF 2, SnC
l ₂ , SnBr ₂ , SnF ₂ , TiCl ₂ , TiB
r ₂ , TiF ₂ , Si (OH) ₂ , Ge (OH) ₂ , Z
r (OH) ₂ , Mn (OH) ₂ , Sn (OH) ₂ , Ti
_{R 2, CrR 2, SiR 2} , SnR 2, GeR 2 [R is an alkyl group, a phenyl group, a naphthyl group, and represent derivatives _{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, and a derivative thereof), and the like. Examples of the oxy metal include VO, MnO, and TiO.

Based on the above embodiment, the infrared ray reflective laminate has a heat ray reflecting function and λ _max of 650 nm to 800 nm.
By combining the near-infrared absorbing dyes of less than the above, a heat ray-shielding sheet having high transparency and a high heat ray-shielding effect, which is an initial purpose, was completed. Particularly, as seen in the examples, T _V was 70% or more and T _E was 44% or less.

[0021]

EXAMPLES The present invention will now be described in more detail by way of examples. The phthalocyanine compounds represented by the formulas (II) to (VI) shown in the examples are a simplified version of the structure represented by the formula (I). Example 1 Polyethylene terephthalate pellets 120 manufactured by Unitika
3 and λ _max = 713 represented by the following formula (II) (Formula 2)
nm copper phthalocyanine, weight ratio 1: 0.0032
After mixing at a ratio of 1 to prepare a film having a thickness of 100 μm by an extruder, the film was biaxially stretched to prepare a polyethylene terephthalate film containing a near infrared absorbing dye having a thickness of 25 μm. In addition, indium oxide (300
Å) / Silver (100 Å) / Indium oxide (600 Å) /
A laminated body having a composition of silver (100 Å) / indium oxide (300 Å) was deposited on a 25 μm-thick Toray Co., Ltd. Lumirror by a magnetron sputtering method to prepare an infrared reflective laminated body supporting film. A polyethylene terephthalate film containing the above near-infrared absorbing dye and an infrared reflective laminate supporting film were laminated with a urethane adhesive to prepare a heat ray shielding sheet. T _V and T _E of this sheet are spectrophotometer U-34 manufactured by Hitachi, Ltd.
00, and T _V according to JIS-R-3106
And T _E were calculated, T _V = 72%, T _E = 39
%Met.

[0022]

[Chemical 2]

Example 2 Instead of (II) as the near infrared absorbing dye, the following formula (III) was used.
Λ represented by _max= 742 nm copper phthalocyanine
Contains near-infrared absorbing dye with a thickness of 25 μm using nin
Created a polyethylene terephthalate film
Except for and, perform the same work as in Example 1
Created. The same measurement and calculation as in Example 1 were performed.
Around T_V= 72%, T_E= 37%.

[0024]

[Chemical 3]

Example 3 λ _max = 76 as a near infrared absorbing dye instead of (II)
The same operation as in Example 1 was performed except that a polyethylene terephthalate film containing a near-infrared absorbing dye having a thickness of 25 μm was prepared using the anthraquinone-based near-infrared absorbing agent SIR-114 of 5 nm of Mitsui Toatsu Dye Co., Ltd. A heat ray shielding sheet was created. When the same measurement and calculation as in Example 1 were performed, T _V = 74% and T _E = 42%.

Example 4 Instead of (II) as the near infrared absorbing dye, the following formula (IV) was used.
Λ represented by _max= 781 nm copper phthalocyanine
Containing a near-infrared absorbing dye with a thickness of 25 μm using nin
Made a polyethylene terephthalate film
Except for the above, perform the same operation as in Example 1 to produce a heat ray shielding sheet.
I made it. The same measurement and calculation as in Example 1 were performed.
Ro T_V= 72%, T_E= 40%.

[0027]

[Chemical 4]

Example 5 Using the same method as in Example 1, instead of (II) as the near infrared absorbing dye, λ represented by the following formula (V)
2 using VO phthalocyanine with _max = 754 nm
A heat ray-shielding sheet was prepared in the same manner as in Example 1 except that a polyethylene terephthalate film containing a near-infrared absorbing dye of 5 μm was prepared. When the same measurement and calculation as in Example 1 were performed, T _V = 72%,
T _E = 38%.

[0029]

[Chemical 5]

Comparative Example 1 The infrared reflective laminate-carrying film used in Example 1 and a 25 μm-thick Lumirror manufactured by Toray Industries, Inc. containing no near-infrared absorbing dye were laminated using a urethane adhesive.
When the sheet was subjected to the same measurements and calculations as in Example 1, T _V = 79% and T _E = 52%.

Comparative Example 2 λ _max = 85 as a near infrared absorbing dye instead of (II)
The same operation as in Example 1 except that a polyethylene terephthalate film containing a near-infrared absorbing dye having a thickness of 25 μm was prepared using a metal complex-based near-infrared absorbing agent PA-1001 of 4 nm of Mitsui Toatsu Fine Co., Ltd. Then, a heat ray shielding sheet was prepared. When the same measurement and calculation as in Example 1 were performed, T _V = 72% and T _E = 47%.

Example 6 Using the polyethylene terephthalate film containing the near-infrared absorbing dye used in Example 1 as a substrate plastic film, the same sputtering as in Example 1 was performed to prepare a heat ray shielding sheet. When the same measurement and calculation as in Example 1 were performed, T _V = 72% and T _E = 40.
%Met.

Example 7 A liquid obtained by mixing Uban 20SE-60 manufactured by Mitsui Toatsu Chemicals, Inc. and Almatex 748-5M manufactured by the same at 3: 7, and λ represented by the following formula (VI) _max = 743n
Toluene in which 0.3% of VO phthalocyanine was dissolved at a ratio of 2: 1 and coated on a polyethylene terephthalate film having a thickness of 75 μm at 130 ° C.
And dried for 15 minutes. The coating thickness after drying was 40 μm. This film was laminated with the infrared reflective laminate supporting film used in Example 1 with a urethane adhesive,
A heat ray shielding sheet was created. When the same measurement and calculation as in Example 1 were performed, T _V = 73% and T _E = 39%.

[0034]

[Chemical 6]

Examples 8 to 910, Comparative Examples 3 to 5 Heat rays were produced in the same manner as in Example 7 except that the compounds shown in Table 1 (Table 1) were used as the near infrared absorbing dye instead of (IV). A barrier film was created. Table 1 shows T _V and T _E.

[0036]

[Table 1] Table-1 ────────────────────────────────── Near infrared absorbing dye λ _max (nm) the low emissivity film (chloroform solvent) T _V T _E ────────────────────────────────── example 8 (II ) 713 73 40 Example 9 (III) 742 72 38 Example 10 (IV) 781 72 40 ───────────────────────────── Comparative Example 3 PA-1001 1110 73 47 Comparative Example 4 PA-1005 850 69 46 46 Comparative Example 5 PA-1006 870 70 70 46 ───────────────── ───────────────── Note) In the comparative example, a near infrared absorbing dye from Mitsui Toatsu Fine Co., Ltd. was used.

[0037]

The heat ray-shielding sheet according to the present invention compensates for the drawback that the reduction of T _E is hindered because the infrared ray reflective laminate has a large light transmittance in the wavelength range of 700 to 800 nm, and T _V is lessened. Improvements in T _E were made without lowering. As is clear from Examples and Comparative Examples, the heat ray-shielding sheet containing a near infrared absorbing dye having a maximum absorption peak in the wavelength range of 650 nm or more and less than 800 nm according to the present invention has T _V of 70% or more and T _E Is 44% or less, whereas the infrared reflective laminate film containing no near-infrared absorbing dye has T _V of 70% or more, but T _E of 5
It is as large as 0%, and is disclosed in JP-A-60-1271.
In the case of using a near infrared absorbing dye having an absorption peak at a wavelength of 800 nm or more, which is the same as that used in No. 52, T
_E could not be less than 45%.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Naoto Ito 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd.

Claims (9)

[Claims] 1. A heat ray shielding sheet comprising an infrared reflective laminate, which further has a wavelength of 650 nm or more and 800 n.
A heat ray-shielding sheet containing a near-infrared absorbing dye having a maximum absorption peak in a range of less than m. 2. The infrared reflective laminate is a metal oxide / metal /
2. A layer comprising 5 layers of metal oxide / metal / metal oxide.
The heat ray shielding sheet described. 3. The heat ray shielding sheet is JIS-R-3106.
The heat ray-shielding sheet according to claim 1, wherein the visible light transmittance (T _V ) calculated by the method is 70% or more, and the substrate of the infrared reflective laminate is plastic. 4. A heat ray shielding sheet comprising an infrared reflective laminate containing a near infrared absorbing dye, wherein a plastic film containing a near infrared absorbing dye is prepared from plastic and the near infrared absorbing dye and laminated with the infrared reflective laminate supporting film. The heat ray shielding sheet according to claim 1, wherein 5. A heat ray shielding sheet comprising an infrared reflective laminate and a near infrared absorbing dye, wherein the substrate plastic film of the infrared reflective laminate contains the near infrared absorbing dye. Heat ray shielding sheet. 6. A heat ray shielding sheet comprising an infrared reflective laminate and a near infrared absorbing dye, wherein the near infrared absorbing dye is dissolved in a solvent and coated on the surface of the infrared reflective laminate supporting film, or the infrared reflective laminate. The heat ray shielding sheet according to claim 1, wherein the surface of the supporting film is coated with a near infrared ray absorbing dye and a resin dissolved in a solvent. 7. A heat ray-shielding sheet comprising an infrared reflective laminate containing a near-infrared absorbing dye, the surface of a plastic film being coated with the near-infrared absorbing dye dissolved in a solvent, or the surface of the plastic film being absorbed by the near-infrared light. The heat ray shielding sheet according to claim 1, wherein the dye and the resin are dissolved in a solvent to be coated, and the infrared ray reflective laminate is laminated thereon. 8. A heat ray shielding sheet comprising a near-infrared absorbing dye in an infrared reflective laminate, wherein the surface of the plastic film is coated with the near-infrared absorbing dye dissolved in a solvent, or the surface of the plastic film is near-infrared absorbing. The heat ray-shielding sheet according to claim 1, wherein a coating prepared by dissolving a dye and a resin in a solvent is laminated with the infrared reflective laminate supporting film. 9. A heat ray-shielding sheet comprising an infrared reflective laminate containing a near infrared absorbing dye, wherein the near infrared absorbing dye is charged in the adhesive when the plastic film and the infrared reflective laminate supporting film are bonded together. The heat ray shielding sheet according to claim 1, wherein: