JP3335397B2 - Heat shielding sheet - Google Patents

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 restricts the inflow of solar energy into the room by combining with a window glass of a building or a house, suppresses a rise in the room temperature in summer, and contributes to energy saving during cooling. In addition, by incorporating it into windows of automobiles and trains, it is possible to suppress a rise in the temperature inside the vehicle under hot weather, improve cooling efficiency, and reduce the load on the engine due to energy saving.

[0002]

BACKGROUND ART heat ray shielding sheet actually building, building material product or automobile such as a house, excellent heat ray cutoff for incorporation into the window, such as a train sheet - when trying to create the door, visible light transmittance (T _V It is important that) is large. For example, if the front glass of an automobile, is T _V from the viewpoint of safety 7
It is specified by JIS standard that it is 0% or more. The index of the low emissivity can be a represented in solar transmittance (T _E) for the sunlight, T _E is important for that energy saving can be kept as small as can the smaller the performance is high T _E of the low emissivity. As detailed below,
Conventionally, heat ray blocking film becomes poor high becomes low emissivity efficiency at the same time T _E raising the T _V. Further, T _V is also lowered Smaller T _E, does not satisfy the T _V reference of 70% or more is JIS standard. Particularly difficult is T _V
This is a technique for reducing TE to about 40 to 44% while maintaining the _E to 70% or more. T _V is heat absorbing sheet and heat-reflecting sheet is 70% or more has been already some are practically marketed, also the wavelength that of any 700
It has not been possible to completely cut off heat rays over the entire infrared region of nm or more. Especially their disadvantages are 7
Light transmittance in the vicinity of 00~800nm large, are preventing to reduce T _E.

The prior art is disclosed in Japanese Patent Application Laid-Open No. 56-32352.
As a film having a heat ray reflection function, a specific thickness of tungsten oxide / silver /
A stack of stacked thin films of tungsten oxide having a three-layer structure has been proposed. However, the case of a three-layer structure, it is impossible to sufficiently reduce the T _E for dull rise of reflection in the near infrared region. Also, JP-A-63-1343
Reference numeral 32 denotes a film having a heat ray reflection function, in which a laminated thin film of five layers of oxide / silver / oxide / silver / oxide having a specific thickness is formed on a substrate, and the characteristics of the heat ray reflection film having a three-layer structure are determined. Suggestions for improvement have been made. But although the rising of the reflection in the near infrared region compared to that of three-layer structure has improved sharply becomes T _E even five layers, 700
High light transmittance in the wavelength range of 800 nm.

Japanese Patent Application Laid-Open No. 60-127152 discloses a selective light transmitting film comprising a laminate of silver alloy / organic polymer having a refractive index of 1.35 or more / silver alloy, a wavelength of 800 to 1200 nm.
Attempts have been made to combine selective layers containing near infrared absorbers with absorption peaks between m. But T
_In order to reduce _E , it is necessary to select a wavelength band where the selective light transmitting film has a high heat ray transmittance and a large solar radiation energy.
It is effective to cut out heat rays of 00 nm or more, but a near-infrared absorbent having an absorption peak between 800 and 1200 nm cannot efficiently absorb the wavelength range of 700 to 800 nm. Especially the technique of sputtering the metals on a plastic film in the prior art it has been difficult to make the heat ray shielding sheet meet industrial scale T _V is the reference of 70% or more and T _E is 44% or less.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide an excellent heat ray ability without losing transparency by combining the heat ray reflection function of the infrared ray reflection laminate and the heat ray absorption function of the near infrared ray absorbing dye. It is to provide a heat ray shielding sheet.

[0006]

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that an infrared reflecting laminate having a heat ray reflecting function and a wavelength of 650 nm having a heat ray absorbing function.
Above maximum absorption peak in less than 800nm by combining near infrared absorbing dye having compensates the disadvantage of infrared reflective laminate reduction of T _E is prevented because the light transmittance is large in the wavelength region 700 to 800 nm, Although even lower the visibility in the visible light innovative heat ray shielding sheet to effectively reduce the T _E without much lowering the T _V by absorbing light near a wavelength range 650~700nm large solar energy It was found that the present invention was obtained, and the present invention was completed. That is, the present invention relates to a heat ray shielding sheet provided with an infrared reflective laminate, and further has a wavelength of 650 nm or more,
The present invention relates to a heat ray shielding sheet containing a near infrared absorbing dye having a maximum absorption peak within less than 00 nm.

The infrared reflecting 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
Å500 ° and the metal oxide is 100１００2000 °.
The conditions for forming each layer are as follows.
^The films are laminated by a method such as sputtering, vacuum deposition, or ion plating at ^-1 to 10 ^-7 torr, and an infrared reflective laminated body supporting film is prepared. Examples of the material of 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.

[0008] Substrate plastic films used for laminating the infrared reflective laminate include polyethylene terephthalate film, polymethyl methacrylate film, polycarbonate film, polyethylene film, polysulfone film, polyethersulfone film, nylon film, polyamide film, polyacrylate. Films having high transparency such as films, polyvinyl chloride films, polyvinyl fluoride films and the like can be mentioned. Particularly preferred substrate plastic film, polyethylene terephthalate film, polymethyl methacrylate film, polycarbonate film,
Is mentioned. As a particularly preferred film for supporting an infrared reflective laminate, a film formed by alternately sputtering five layers of indium oxide and silver with indium oxide / silver / indium / silver / indium oxide on a polyethylene terephthalate film is exemplified.

According to the present invention, the following six methods are available for producing a heat ray shielding sheet containing an infrared reflecting laminate and a near infrared absorbing dye. The first is
First, a plastic film (A) containing a near-infrared absorbing dye is prepared, and then bonded to an infrared-reflective laminate-supporting film (B) in which an infrared-reflective laminate is applied on a substrate plastic film of 10 to 200 μm by sputtering or the like. Can be The plastic pellets used as the material of the plastic film (A) containing a near infrared absorbing dye are polyethylene terephthalate, polymethyl methacrylate, polycarbonate, polyethylene, polysulfone, polyethersulfone, nylon, polyamide, polyacrylate, polyvinyl chloride, polyvinyl fluoride. , Etc., and a method of producing the same is to mix a plastic pellet and a near-infrared absorbing dye,
Heated and melted at 0-350 ° C, formed into a film with an extruder, or made a raw material with an extruder,
A method of forming a film having a thickness of 10 to 200 μm by stretching uniaxially or biaxially 2 to 5 times at 90 ° C. or alcohols such as toluene, hexane, cyclohexane, methanol, ethanol, isopropanol, etc. Solvent such as aromatics such as toluene, xylene, aliphatics such as hexane, cyclohexane and ethylcyclohexane, and cellsolves such as methylcellosolve and isopropylcellosolve, and cast on a glass plate. A method of forming a film having a thickness of about 300 μm is exemplified. The adhesive used for bonding (A) and (B) is a known transparent adhesive such as a silicon-based, urethane-based, or acrylic-based adhesive, and the thickness of the adhesive layer is 1 to 100 μm. Secondly, a method in which (A) prepared in the same manner as in the first method is used as a substrate plastic film, and an infrared reflective laminate is attached thereon by sputtering or the like.

Third, at least one surface of the infrared-reflective laminated body supporting film (B) in the first method is coated by dissolving a near-infrared absorbing dye in a solvent, or by dissolving a near-infrared absorbing dye and a resin in a solvent. It is a method of coating. Solvents such as toluene, hexane,
Alcohols such as cyclohexane, methanol, ethanol and isopropanol, aromatics such as toluene and xylene, aliphatics such as hexane, cyclohexane and ethylcyclohexane, methylcellosolve, isopropylcellosolve Cellsolves such as cellulose acetate derivatives are used as the resin, and synthetic resins such as acrylic resins, phenol resins, urea resins, melanin resins, vinyl resins, alkyd resins, epoxy resins, and urethane resins are used. Alternatively, several types are used in combination. Examples of the coating method include a method of coating using a barcode method, a spin coating method, a transfer method, or the like.

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

Fifth, (B) in the first method and the fourth
(C) prepared by the above method is bonded by the same method as the first method. A method of bonding the infrared-reflective laminate surface of (B) and the coating surface of the near-infrared absorbing dye of (C) as a method of bonding the two films,
The method of matching the plastic surface of (B) with the coating surface of the near infrared absorbing dye of (C), the method of matching the plastic surface of (B) and the plastic surface of (C), or the method of (B) C) There is a method of matching plastic surfaces.

Sixth, (B) in the first method and 10
A method of mixing and dissolving a near-infrared absorbing dye in a silicone-based, urethane-based, acrylic-based, or other transparent adhesive used for bonding a plastic film having a thickness of about 200 μm is used.

The near infrared absorbing dye used in the present invention is 6
It is not particularly limited as long as it is a dye having a maximum absorption peak at 50 nm or more and less than 800 nm.
JP-A-61-154888, JP-A-61-19728
1, JP-A-61-246091, JP-A-63-3799
1, JP-A-63-39388, JP-A-62-23328
8, JP-A-63-31889, 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-3-62878, Japanese Patent Application No. 3-338557, Japanese Patent Application No. 3-99730, Japanese Patent Application No. 3-3793.
Phthalocyanines as disclosed in JP-A-252414, JP-A-61-291651, JP-A-61-2916
52, JP-A-62-15260, JP-A-62-1329
63, JP-A-1-129068, JP-A-1-17245
Anthraquinones as disclosed in No. 8 are preferable, and the amount of the anthraquinone 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 2).

[0016]

Embedded image [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 ,
In each combination of A ³ and A ⁴ , A ⁵ and A ⁶ , and A ⁷ and A ⁸ , there is no possibility that the combination is a hydrogen atom at the same time. On the other hand, B ^{1 to} B ⁸ each independently represent a hydrogen atom,
A halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group,
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 oxymetal. ]

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) include a methyl group, an ethyl group, an n-propyl group and an 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, n-hexyl, cyclo-hexyl, 1,3-dimethyl-butyl, 1-iso-propylpropyl, 1,2-dimethylbutyl, n-heptyl, 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 Propyl group, n-nonyl group, a linear or branched alkyl group having 1 to 20 carbon atoms such as 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-propyl group, such as a halogenated alkyl group, an alkylaminoalkyl group, a dialkylaminoalkyl group,
Alkoxycarbonylalkyl group, alkylaminocarbonylalkyl group, alkoxysulfonylalkyl group,
And an alkylsulfonyl group.

Examples of the substituted or unsubstituted alkoxy group include a methoxy group, an ethoxy group, an 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, linear or branched alkoxy group having 1 to 20 carbon atoms, methoxymethoxy group, methoxyethoxy group, ethoxy Ethoxy, propoxyethoxy, butoxyethoxy, γ-methoxypropyloxy, γ-ethoxypropyloxy, methoxyethoxyethoxy, ethoxyethoxyethoxy, dimethoxymethoxy, diethoxymethoxy, dimethoxyethoxy, 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,
Alkyl halides such as 2,2,2-trichloroethoxy group, 1,1,1,3,3,3, -hexafluoro-2-propyloxy group, alkyl groups such as dimethylaminoethoxy group and diethylaminoethoxy group Examples include an aminoalkoxy group and a dialkylaminoalkoxy group. Examples of the substituted or unsubstituted aryl group include a phenyl group, a chlorophenyl group, a dichlorophenyl group, a bromophenyl group, a fluorinated phenyl group, a halogenated phenyl group such as an iodinated phenyl group, a tolyl group, a xylyl group, a mesityl group, Examples 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.As the substituted or unsubstituted alkylthio group, 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, 2-ethylhexylthio, 3-methyl-1
-iso-propylbutylthio group, 2-methyl-1-iso-propylthio group, 1-t-butyl-2-methylpropylthio group, n-nonylthio group, etc. Alkylthio, methoxymethylthio, methoxyethylthio, ethoxyethylthio, propoxyethylthio, butoxyethylthio, γ-methoxypropylthio, γ-ethoxypropylthio, methoxyethoxyethylthio, ethoxyethoxyethyl A thio group, a dimethoxymethylthio group, a diethoxymethylthio group, a dimethoxyethylthio group, an alkoxyalkylthio group such as a diethoxyethylthio group, an alkoxyalkoxyalkylthio group, an alkoxyalkoxyalkoxyalkylthio group,
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, and dimethylaminoethylthio group And an alkylaminoalkylthio group such as a diethylaminoethylthio group and a dialkylaminoalkylthio group. Examples of the substituted or unsubstituted arylthio group include a phenylthio group, a naphthylthio group, an alkylphenylthio group, and the like.

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), Cd (II), Hg (I
I), Pb (II), Sn (II) and the like. Examples of monosubstituted 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 , 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 represents an alkyl group, a phenyl group, a naphthyl group, and 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 derivatives thereof). Examples of oxymetals include VO, MnO, and TiO.

Based on the above embodiment, the heat reflection function of the infrared reflective laminate and λ _max of 650 nm to 800 nm
By combining less than near-infrared absorbing dyes, a heat-shielding sheet with high transparency and a high heat-shielding effect, which was the initial object, was completed. In particular, as seen in the examples, _TV was 70% or more and _TE was 44% or less.

[0021]

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

[0022]

Embedded image

Example 2 As a near infrared absorbing dye, the following formula (III) was used instead of (II):
Except that a 25 μm-thick polyethylene terephthalate film containing a near infrared absorbing dye having a thickness of 25 μm was prepared using copper phthalocyanine having λ _max = 742 nm represented by Chemical Formula 4, the same operation as in Example 1 was performed, and the heat ray shielding sheet was used. It was created. When the same measurement and calculation as in Example 1 were performed, T _V = 72% and T _E = 37%.

[0024]

Embedded image

Example 3 As a near infrared absorbing dye, the following formula (IV) was used instead of (II)
Except that a 25 μm-thick polyethylene terephthalate film containing a near-infrared absorbing dye having a thickness of 25 μm was prepared using copper phthalocyanine having λ _max = 781 nm represented by (Chemical Formula 5), a heat ray blocking sheet was prepared in the same manner as in Example 1. Created. When the same measurement and calculation as in Example 1 were performed, T _V = 72% and T _E = 40%.

[0026]

Embedded image

Example 4 Using the same method as in Example 1, λ represented by the following formula (V) (Chemical Formula 6) was used instead of (II) as a near-infrared absorbing dye.
_max = 754 nm VO phthalocyanine, thickness 2
Except that a polyethylene terephthalate film containing a 5 μm near-infrared absorbing dye was prepared, the same operation 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%,
T _E = 38%.

[0028]

Embedded image

Comparative Example 1 The infrared-reflective laminate-supporting film used in Example 1 was laminated with a 25 μm-thick Lumirror manufactured by Toray Co., Ltd., containing no near-infrared absorbing dye, using a urethane-based adhesive.
The sheet was measured and calculated in the same manner as in Example 1. As a result, T _V = 79% and T _E = 52%.

Comparative Example 2 As a near infrared absorbing dye, λ _max = 85 instead of (II)
The same operation as in Example 1 except that a polyethylene terephthalate film containing a 25 μm-thick near-infrared absorbing dye was prepared using a 4 nm Mitsui Toatsu Fine metal complex-based near-infrared absorbing agent PA-1001 manufactured by Mitsui Toatsu Fine Co., Ltd. Was performed to prepare a heat ray shielding sheet. The same measurements and calculations as in Example 1 yielded T _V = 72% and T _E = 47%.

Example 5 Using a polyethylene terephthalate film containing a near-infrared absorbing dye used in Example 1 as a substrate plastic film, the same sputtering as in Example 1 was performed to produce 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 6 A liquid obtained by mixing Uvan 20SE-60 manufactured by Mitsui Toatsu Chemicals Co., Ltd. and Armatex 748-5M manufactured by the company at a ratio of 3: 7, and λ represented by the following formula (VI) (Formula 7) _max = 743n
m VO phthalocyanine dissolved in 0.3% toluene was mixed at a ratio of 2: 1 and coated on a 75 μm-thick polyethylene terephthalate film.
For 15 minutes. The coating thickness after drying was 40 μm. This film was laminated with the infrared reflective laminated body supporting film used in Example 1 with a urethane-based adhesive,
A heat shield sheet was prepared. When the same measurement and calculation as in Example 1 were performed, T _V = 73% and T _E = 39%.

[0033]

Embedded image

Examples 7 to 9 and Comparative Examples 3 to 5 Heat ray blocking films were prepared in the same manner as in Example 6, except that the compounds shown in Table 1 were used instead of (IV) as the near infrared absorbing dye. did. The T _V and T _E are shown in Table 1.

Table 1 近 Near-infrared absorbing dye λ _max (nm) Heat ray blocking film (chloroform solvent) T _V T _E ────────────────────────────────── example 7 (II) 713 73 40 Example 8 (III) 742 72 38 Example 9 (IV) 781 72 40 Comparative Example 3 PA-1001 1110 73 47 Comparative Example 4 PA-1005 850 69 46 Comparative Example 5 PA-1006 870 70 46 ──────────────── Note) In the comparative example, a near infrared absorbing dye of Mitsui Toatsu Fine Co., Ltd. was used.

[0036]

Heat ray shielding sheet according to the present invention according to the present invention compensates the disadvantage of reduced T _E infrared reflective laminate to light transmittance is large in the wavelength range of 700~800nm is prevented, so the T _V without lowering, improvement of T _E has been carried out. As apparent from Examples and Comparative Examples, the present invention due to the wavelength 650nm or more, the heat ray shielding sheet containing near infrared absorbing dye having a maximum absorption peak in less than 800nm is, T _V is 70% or more, and T _E While but at most 44%, the infrared reflective laminate film containing no near infrared absorbing dye, T _V is less than 70%, T _E 5
0%.
52 using a near-infrared absorbing dye having the same absorption peak at a wavelength of 800 nm or more as used in
_E less than 45% was not obtained.

────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Naoto Ito 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture Examiner, Mitsui Toatsu Chemicals Co., Ltd. Yoshiko Moriguchi (56) References JP-A-59-151108 (JP, A) JP-A-2-138382 (JP, A) JP-A-62-903 (JP, A) JP-A-57-105748 (JP, U) (58) Fields investigated (Int. Cl. ⁷ , DB name) G02B 5/22 G02B 5/26 G02B 5/28

Claims (8)

(57) [Claims] 1. A heat ray shielding sheet comprising an infrared reflecting laminate, further comprising a wavelength of 650 nm or more and 800 nm.
The following general formula (I) having a maximum absorption peak within less than m
Containing a near-infrared absorbing dye represented by the formula (1), and
Visible light transmittance calculated by IS-R-3106
(T _V) is 70% or more, a solar radiation transmittance (T _E) is 44% or less
A heat ray shielding sheet , characterized in that: Embedded image [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 , A ³ and A ⁴ , A ⁵ and A ⁶ , and A ⁷ and A
^In each of the combinations of ⁸ , there is no simultaneous combination of hydrogen atoms. On the other hand, B ^{1 to} B ⁸ each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, Represents 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 oxymetal. ] 2. The method according to claim 1, wherein the infrared reflecting laminate comprises a metal oxide / metal /
Claim consists five layers of metal oxide / metal / metal oxide 1
The heat ray shielding sheet as described . 3. A heat-shielding sheet comprising an infrared-reflective laminate containing a near-infrared absorbing dye, forming a near-infrared-absorbing dye-containing plastic film from plastic and the near-infrared absorbing dye and bonding the film to the infrared-reflective laminate-bearing film. The heat ray shielding sheet according to claim 1 or 2, wherein: 4. A heat ray shielding sheet comprising an infrared reflecting laminate and a near infrared absorbing dye, wherein the substrate plastic film of the infrared reflecting laminate contains a near infrared absorbing dye . 3. The heat ray shielding sheet according to 3 . 5. A heat-shielding sheet comprising an infrared-reflective laminate and a near-infrared absorbing dye, wherein the surface of the infrared-reflective laminate-supporting film is coated by dissolving the near-infrared absorbing dye in a solvent, or claims 1-4 Symbol of the near infrared absorptive dye and resin bearing film surface, wherein the coating is dissolved in a solvent
Mounting heat ray shielding sheet of. 6. A heat ray shielding sheet comprising an infrared reflective laminate containing a near infrared absorbing dye, wherein the surface of the plastic film is coated by dissolving the near infrared absorbing dye in a solvent, or the surface of the plastic film is coated with a near infrared absorbing dye. The heat ray shielding sheet according to any one of claims 1 to 5 , wherein a dye and a resin are dissolved in a solvent and coated, and an infrared reflective laminate is laminated thereon. 7. A heat ray shielding sheet comprising an infrared reflective laminate containing a near infrared absorbing dye, wherein the surface of the plastic film is coated by dissolving the near infrared absorbing dye in a solvent, or the surface of the plastic film is absorbed by a near infrared absorbing dye. The heat ray shielding sheet according to any one of claims 1 to 6 , wherein a coating obtained by dissolving a dye and a resin in a solvent is bonded to an infrared-reflective laminated body supporting film. 8. A heat-shielding sheet comprising an infrared-reflective laminate containing a near-infrared absorbing dye, wherein a near-infrared-absorbing dye is charged into an 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: