JPH06191906A - Laminated glass - Google Patents

Abstract

PURPOSE:To provide a laminated glass having improved selective light- transmittance compared with conventional laminated glass having selective light-transmittance. CONSTITUTION:This laminated glass has a visible light transmittance of >=70% and is provided with a 1st selection layer composed of a selective light- transmission film having a heat-ray reflecting function and a light transmittance of <=40% at 1,000nm wavelength and a 2nd selection layer having an absorption peak within a wavelength range of >=650nm and <800nm.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminated glass for automobiles having a selective light transmittance for the purpose of energy saving. More specifically, the present invention relates to a laminated glass that has both a heat ray reflecting function and a heat ray absorbing function to effectively reduce the solar radiation transmittance without losing transparency. The laminated glass according to the present invention can be used not only as an automobile but also as a window glass for vehicles such as trains, buildings, and household electric appliances.

[0002]

2. Description of the Related Art Laminated glass having a function of controlling light transmittance has been studied as vehicles such as automobiles and trains, and window glass for construction, and some of them have already been put into practical use. In addition, this laminated glass is a material that has been drawing attention in recent years from the viewpoint of energy saving.

[0003] Conventionally, as an attempt to add a selective light transmittance having a high visible light transmittance and a low heat ray transmittance to a laminated glass for automobiles, one having a structure in which a selective light transmitting film is directly laminated on a glass plate, and a glass There is a structure in which a plastic film in which a selective light transmission film is laminated is sandwiched between plates.

The basic structure of the latter laminated glass is one in which a plastic film laminated with a functional film is sandwiched between two glass plates using a polyvinyl butyral film as a bonding agent and bonded, and a selective light transmission film is directly attached to the glass plate. Compared with the laminated glass laminated with, it has excellent physical properties such as workability, impact resistance, and uniformity, in addition to the productivity that continuous production can be performed, and has been particularly attracting attention in recent years.

These laminated glass have a function of transmitting visible rays out of all rays and reflecting heat rays (infrared rays) due to the selective ray transmitting film, and it is possible to reflect only heat rays out of sunlight rays. it can. Therefore, when used as window glass, in the summer when the sun's rays are strong,
It is possible to suppress the temperature rise in the room due to the incidence of heat rays,
The indoor cooling efficiency can be improved. Therefore, it is important to suppress the transmission of heat rays as much as possible in order to save energy. However, conventional products are insufficient for automobiles.

As a conventional technique, for example, Japanese Patent Application Laid-Open No. 56-3
As 2352, a film having a heat ray reflecting function is used which is obtained by laminating a laminated thin film having a three-layer structure of tungsten oxide / silver / tungsten oxide of a specific film thickness on the surface of a polyester film, and having this film as an intermediate layer. Laminated glass has been proposed. However, a heat ray reflective film having a three-layer structure cannot sufficiently reflect heat rays.

Further, in Japanese Patent Laid-Open No. 63-134332, a film having a heat ray reflecting function is formed on a plastic film with a specific thickness of oxide / silver / oxide / silver / oxide 5.
Proposals have been made to form a laminated thin film of layers to improve the characteristics of a selective light transmitting film having a three-layer structure, but the heat ray reflection effect was slightly better than that of the three-layer structure, but was insufficient.

Therefore, in order to improve the selective light transmittance, JP-A-60-127152 discloses a selective light transmitting film,
Attempts have been made to combine a laminate of silver alloy / organic polymer having a refractive index of 1.35 or more / silver alloy with a selective layer containing a near-infrared absorber having an absorption peak in the wavelength range of 800 to 1200 nm. However, since the laminated body of the silver alloy of this patent has a poor heat ray reflection efficiency at a wavelength of 800 to 1200 nm, particularly at 1000 nm, 800 to 120 is required to compensate for it.
Only a selective layer containing a near-infrared absorber having a peak at 0 nm is laminated, and even with this, a sufficient effect was not obtained.

[0009]

DISCLOSURE OF THE INVENTION An object of the present invention is to provide an energy-saving glass having a visible light transmittance of 70% or more, which is sufficient as a laminated glass for automobiles, and has an excellent selective light transmittance which is a low solar radiation transmittance. It aims to provide laminated glass for automobiles.

[0010]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a wavelength band of 650 nm or more, which is a large wavelength band of solar radiation energy, has a high selective light transmitting function. Blocking light, especially 6
Focusing on the fact that it is effective to block wavelengths of 50 nm or more and less than 800 nm, it selectively reflects wavelengths of 800 nm or more and has a transmittance of 4 at a wavelength of 1000 nm.
0% or less of a selective light-reflecting film of a dielectric-metal laminate,
The present invention has been completed by discovering that a base material containing a near-infrared absorber having a maximum absorption peak at a wavelength of 650 nm or more and less than 800 nm is laminated to have a selective light transmitting function synergistically.

That is, the gist of the present invention is that the wavelength is 1000
a first selection layer comprising a selection light transmission film having a heat ray reflection function of having a light transmittance of 40% or less in nm, and a wavelength of 650.
Second peak with a maximum absorption in the wavelength range from ≥nm to less than 800nm
And a visible light transmittance of 70% or more.

In the present invention, as shown in FIG. 1, a plastic film (1) containing a near-infrared absorber and a transparent plastic film (2) laminated with a selective light transmitting film are bonded together via an adhesive (3). A laminated glass for automobiles, which is produced by preparing a laminated film and sandwiching the laminated film with two butyric plates (5) using polyvinyl butyral as a bonding agent (4), and having a visible light transmittance of 70% or more and low. It is a laminated glass having a solar radiation transmittance.

The method for producing the selective layer containing the near infrared absorbing agent is not limited to the method of incorporating it into the plastic film, and the following methods can be used as other methods. As one of them, it is possible to use a method of coating a resin containing a near-infrared absorber on one side or both sides of a film laminated with a selective light-transmitting film, and the near-infrared absorber on a highly transparent plastic film. It is also possible to use a method in which the resin-coated product is laminated with a plastic film laminated with a selective light transmission film. Further, it is possible to include a near infrared ray absorbing agent in the adhesive agent for bonding the selective light transmitting film and the plastic film.

Examples of the plastic film (1) substrate containing a near infrared ray absorbent used in the present invention include polyethylene terephthalate, polyether sulfone, polypropylene, polyether ether ketone,
Homopolymers such as polyester, polyamide, polyvinyl chloride, polyvinyl fluoride, polyacrylate, and polycarbonate, or films made of monomers and copolymers copolymerizable with the monomers of these resins can be selected and used appropriately. The thickness of the plastic film is not particularly limited, but is preferably in the range of 10 to 200 μm in consideration of workability.

The near-infrared absorbing agent used in the present invention is not particularly limited as long as it is a dye having an absorption peak at a wavelength of 650 nm or more and less than 800 nm. For example, JP-A-61-1154888 and JP-A-61-15888. -197281, JP 61-246091, JP 63-37991, JP 63-39388, JP 62-233288, JP 63-312889, JP 2-43269, JP 2-138382, JP-A-2-296885, JP-A-3-43461, JP-A-3-77840, JP-A3-1
[00066] Japanese Patent Application Laid-Open No. 3-62878, Japanese Patent Application No. 3-338
557, Japanese Patent Application No. 3-99730, Japanese Patent Application No. 3-25324
14 disclosed in JP-A No. 61-291651, JP-A No. 61-291652, JP-A No. 62-132963, JP-A No. 1-129068, and JP-A No. 12-172458. Anthraquinones are preferred.

The transparent plastic film laminated with the selective light transmitting film used in the present invention is formed on the transparent plastic film (7) by a commonly used method such as sputtering, vacuum deposition, ion plating or the like. It is obtained by doing. The selective ray transmitting film is a thin film having a function of selectively controlling the transmittance of visible rays and heat rays, and is known per se. For example, a metal layer appropriately selected from metals such as gold, silver, copper, platinum, aluminum, nickel, palladium, iridium, tin, chromium and zinc, and alloys or mixtures containing these metals as a main component, and indium- Tin oxide (IT
O), indium oxide, tin oxide, silicon oxide, aluminum oxide, zinc oxide, tungsten oxide, and the like.
Examples of the thin film include 5 layers or 5 layers. Usually, the metal layer has a thickness of 50 to 500Å, and the metal oxide layer has a thickness of 100 to 2
It is about 000Å.

As the transparent plastic film (7) on which the selective light transmitting film is laminated, polyethylene terephthalate, polyether sulfone, polypropylene, polyether ether ketone, polyester, polyamide,
Examples thereof include homopolymers such as polyvinyl chloride, polyvinyl fluoride, polyacrylate, and polycarbonate, and films made of monomers and copolymers copolymerizable with the monomers of these resins, which can be appropriately selected and used. The thickness of the plastic film is not particularly limited, but is 10 to 20 in consideration of workability.
The range of 0 μm is preferable. Adhesive for bonding the film having a heat ray reflection function and the film containing a near infrared ray absorbent is a known transparent material such as silicon-based, urethane-based, acrylic-based, etc. as appropriate, and the visible light transmittance of the adhesive layer alone. Is not particularly limited as long as it is 70% or more. Usually, the thickness is 1 to 100 μm.

As the bonding agent (4) for glass, a known bonding agent such as polyvinyl butyral resin can be appropriately selected and used. Usually, its thickness is 0.1 to 1 mm. Further, an ultraviolet absorber or the like may be added to the bonding agent to such an extent that the selective light transmittance is not affected.

The material and thickness of the glass plate (5) used in the present invention are not particularly limited, and a plurality of glass plates for vehicles such as automobiles and for construction can be appropriately selected according to the application. Used in pieces.

[0020]

The present invention will be described in detail below with reference to examples. Example 1 Polyethylene terephthalate pellets 120 manufactured by Unitika
3 and an anthraquinone-based near-infrared absorber (SIR-114 manufactured by Mitsui Toatsu Dye Co., Ltd .: maximum absorption wavelength 765 nm) were mixed at a weight ratio of 1: 0.0032, and a film having a thickness of 100 μm was produced by an extruder. The film was biaxially stretched to prepare a polyethylene terephthalate film containing a near-infrared absorber having a thickness of 25 μm. Also, indium oxide (300Å) / silver (100Å) / indium oxide (600Å) / silver (100Å) / indium oxide (30
A thin film having a composition of 0Å) was deposited on a 25 μm-thick Toray Co., Ltd. Lumirror by a magnetron sputtering method to prepare a transparent plastic film (hereinafter referred to as a heat ray reflective film) in which a selective light transmission film was laminated. The infrared ray absorbent-containing polyethylene terephthalate film and the heat ray reflective film were bonded together by using a urethane adhesive to prepare a laminated transparent body. This laminated transparent body was sandwiched between polyvinyl butyral as a bonding agent between molten glass sheets having a thickness of 2 mm and pressure-bonded with a heating press machine at 130 ° C. and 6.5 kg / m ² to produce a laminated glass. The light transmittance of this laminated glass was measured by Hitachi Ltd. spectrophotometer U.
When the visible light transmittance and the solar radiation transmittance were calculated according to JIS-R-3106, the visible light transmittance was 73% and the solar radiation transmittance was 41%.

Example 2 A liquid obtained by mixing Uban 20SE-60 manufactured by Mitsui Toatsu Chemicals, Inc. and Almatex 748-5M manufactured by the same at a weight ratio of 3: 7, and an infrared absorbent manufactured by Mitsui Toatsu Dyes Co., Ltd. SIR-
Toluene in which 0.3% by weight of 114 was dissolved at a ratio of 2: 1 by weight was mixed and coated on a polyethylene terephthalate film having a thickness of 75 μm at 130 ° C.
Allowed to dry for 5 minutes. The coating thickness after drying was 40 μm. This film was laminated with the heat ray reflective film used in Example 1 and a urethane adhesive to prepare a laminated transparent body. This laminated transparent body was sandwiched between polyvinyl butyral as a bonding agent between molten glass sheets having a thickness of 2 mm, and 1
A laminated glass was produced by pressure bonding with a heating press machine at 30 ° C. and 6.5 kg / m ² . The light transmittance of this laminated transparent body was measured using a spectrophotometer U-3400 manufactured by Hitachi, Ltd., and the visible light transmittance was measured according to JIS-R-3106.
When the solar radiation transmittance was calculated, the visible light transmittance was 73.
%, And the solar radiation transmittance was 42%.

Example 3 Uban 20SE-60 manufactured by Mitsui Toatsu Chemicals, Inc. and Almatex 748-5M manufactured by the same were mixed at a weight ratio of 3: 7, and an infrared absorbent manufactured by Mitsui Toatsu Dyes Co., Ltd. SIR-
Toluene in which 114% by weight of 0.3% was mixed at a weight ratio of 2: 1 was coated on the selective light reflection film of the heat ray reflection film used in Example 1, and 130
It was dried at ℃ for 15 minutes. The coating thickness after drying was 4 μm. This film was sandwiched between 2 mm thick fused sheet glass using polyvinyl butyral as a bonding agent,
The laminated glass was manufactured by pressure bonding with a heating press machine at 6.5 ° C. and 6.5 kg / m ² . The light transmittance of this laminated transparent body was measured using a spectrophotometer U-3400 manufactured by Hitachi, Ltd., and the visible light transmittance was measured according to JIS-R-3106.
When the solar radiation transmittance was calculated, the visible light transmittance was 73.
%, And the solar radiation transmittance was 42%.

Example 4 A liquid obtained by mixing Uban 20SE-60 manufactured by Mitsui Toatsu Chemicals, Inc. and Almatex 748-5M manufactured by the same at a weight ratio of 3: 7, and the following structural formula (1) [Chemical formula 1]

[0024]

[Chemical 1] Phthalocyanine-based near-infrared absorber (maximum absorption wavelength 74
Toluene in which 0.3% by weight of (2 nm) is dissolved at a ratio of 2: 1 by weight, and the mixture is coated on a polyethylene terephthalate film having a thickness of 75 μm at 130 ° C.
Allowed to dry for 5 minutes. The coating thickness after drying was 35 μm. This film was laminated with the heat ray reflective film used in Example 1 and a urethane adhesive to prepare a laminated transparent body. This laminated transparent body was sandwiched between polyvinyl butyral as a bonding agent between molten glass sheets having a thickness of 2 mm, and 1
A laminated glass was produced by pressure bonding with a heating press machine at 30 ° C. and 6.5 kg / m ² . The light transmittance of this laminated transparent body was measured using a spectrophotometer U-3400 manufactured by Hitachi, Ltd., and the visible light transmittance was measured according to JIS-R-3106.
When the solar radiation transmittance was calculated, the visible light transmittance was 73.
%, And the solar radiation transmittance was 40%.

Comparative Example 1 A heat ray reflective film having the same structure as in Example 1 is
Nylbutyral is used as a bonding agent and has a thickness of 2 mm.
Sandwiched between the shoes, 130 ℃, 6.5kg / m ²Heating
It pressure-bonded with the press machine and produced the laminated glass. This combination
Light transmittance of glass is spectrophotometer manufactured by Hitachi, Ltd.
Measured using U-3400, JIS-R-3106
Therefore, when calculating the visible light transmittance and solar radiation transmittance,
The visible light transmittance is 79% and the solar radiation transmittance is 51%.
It was

Comparative Example 2 A heat ray reflective film having the same structure as in Example 1 and a polyethylene terephthalate film having a thickness of 75 μm and containing no infrared absorber were laminated using an acrylic adhesive to prepare a laminated film. This laminated film was sandwiched between molten plate glass with a thickness of 2 mm using polyvinyl butyral as a bonding agent, and the temperature was 130 ° C. and 6.5 kg / m.
^The laminated glass was manufactured by press-bonding with the heating press machine of No. ² .
The light transmittance of this laminated glass was measured using a spectrophotometer U-3400 manufactured by Hitachi Ltd., and JIS-R-3
When the visible light transmittance and the solar radiation transmittance were calculated according to 106, the visible light transmittance was 77%, and the solar radiation transmittance was 50%.
Met.

Comparative Example 3 Uban 20SE-60 manufactured by Mitsui Toatsu Chemical Co., Inc. and Almatex 748-5M manufactured by the same company were mixed at a weight ratio of 3: 7, and a near infrared absorption by Mitsui Toatsu Dye Co., Ltd. Agent SIR
Toluene in which 0.3% by weight of -114 was dissolved at a weight ratio of 2: 1 was mixed and coated on a polyethylene terephthalate film having a thickness of 75 μm at 130 ° C.
Allowed to dry for 5 minutes. The coating thickness after drying was 40 μm. This film was sandwiched between 2 mm thick fused sheet glass using polyvinyl butyral as a bonding agent,
The laminated glass was manufactured by pressure bonding with a heating press machine at 6.5 ° C. and 6.5 kg / m ² . The light transmittance of this laminated transparent body was measured using a spectrophotometer U-3400 manufactured by Hitachi, Ltd., and the visible light transmittance was measured according to JIS-R-3106.
When the solar radiation transmittance was calculated, the visible light transmittance was 80.
%, And the solar radiation transmittance was 75%.

Comparative Example 4 Uban 20SE-60 manufactured by Mitsui Toatsu Chemicals, Inc. and Almatex 748-5M manufactured by the same were mixed at a weight ratio of 3: 7, and a near infrared absorption by Mitsui Toatsu Fine Co., Ltd. Agent I
Toluene in which 0.3% by weight of R-ABSORBER PA-1001 (maximum absorption wavelength 1110 nm) was dissolved was mixed in a weight ratio of 2: 1 and the heat ray reflective film used in Example 1 was subjected to selective light reflection film. Coated on
It was dried at 130 ° C. for 15 minutes. The coating thickness after drying is 40
was μm. This film was sandwiched between polyvinyl butyral as a bonding agent between molten glass sheets having a thickness of 2 mm, and pressure-bonded with a heating press machine at 130 ° C. and 6.5 kg / m ² to produce a laminated glass. The light transmittance of this laminated transparent body was measured using a spectrophotometer U-3400 manufactured by Hitachi Ltd., and the visible light transmittance and the solar radiation transmittance were calculated according to JIS-R-3106. Was 73% and the solar radiation transmittance was 47%.

[0029]

The laminated glass having the constitution of the present invention is
Compared with a laminated glass that does not use a selective layer containing a near-infrared absorber having a maximum absorption peak at a wavelength of 650 nm or more and less than 800 nm, the solar radiation transmittance is significantly reduced, and the selective light transmittance is improved. Specifically, the laminated transparent body having the constitution of the present invention has a visible light transmittance of 70% or more and a solar radiation transmittance of 45% or less, while the wavelength of 650 nm.
The heat ray reflector which does not use the near-infrared absorber having a maximum absorption peak at less than 800 nm has a visible light transmittance of 70% or more, but a solar radiation transmittance of 45% or more.

[0030]

[Brief description of drawings]

FIG. 1 is a schematic view of a laminated glass of Example 1.

FIG. 2 is a schematic view of a laminated glass of Example 2.

FIG. 3 is a schematic view of a laminated glass of Example 3.

FIG. 4 is a schematic view of an example of a laminated glass other than the example.

[Explanation of symbols]

1 Plastic Film Containing Near Infrared Absorber 2 Transparent Plastic Film Laminated with Selective Light Transmitting Film 3 Adhesive 4 Bonding Agent 5 Glass 6 Near Infrared Absorber Coating Layer 7 Transparent Plastic Film 8 Adhesive Containing Near Infrared Absorber layer

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

Claims (5)

[Claims] 1. A light transmittance of 40 at a wavelength of 1000 nm.
% Or less, a first selective layer made of a selective light transmitting film having a heat ray reflecting function and a second selective layer having a peak of maximum absorption at a wavelength of 650 nm or more and less than 800 nm, and a visible light transmittance of 70% or more. Laminated glass characterized by being. 2. The laminated glass according to claim 1, wherein the second selective layer is a combination of a near infrared absorbing agent. 3. The laminated glass according to claim 1, wherein the first selection layer is a transparent plastic film laminated with a dielectric and a metal. 4. The laminated glass according to claim 1, wherein the first selective layer is a transparent plastic film on which dielectric-silver-dielectric-silver-dielectric is laminated. 5. The laminated glass of claim 1, wherein the first selective layer is a transparent plastic film of indium oxide-silver-indium oxide-silver-indium oxide.