JPS5952641A - Laminated intermediate membrane - Google Patents

Abstract

(57) [Abstract] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention]

The present invention relates to a light-transmitting sheet that transmits visible light and reflects infrared rays. More specifically, the present invention relates to a selective light-transmitting laminated interlayer film that transmits visible light but does not transmit near-infrared light to infrared light. In general, conductive thin films such as gold, silver, copper, and various alloys containing these as main components are sandwiched between transparent high refractive index dielectric layers.
It is known that, in Ij, by appropriately controlling the thickness of each grooved thin film layer, it is possible to obtain a material that selectively transmits light in a specific wavelength range. In particular, the laminate, which is transparent in the visible region and selectively reflects light from the near infrared to the infrared #lj, is used as a thermal reflective film for buildings,
This is effective from the point of view of energy saving for houses, vehicles, etc. However, in order to further improve the efficiency of energy use in buildings, houses and other buildings, and vehicles, it is necessary to
It is more effective for Fr heat to further reduce the transmission characteristics of the near-infrared region, which accounts for about 50% of the solar irradiation energy, and to further improve the transmission characteristics of the visible light region. Ink that improves these properties improves heat resistance during high-temperature work,
buildings, containers. It is expected that the cooling and heating effects will be further improved by improving the ability to block solar energy that enters through the windows of vehicles, and that the cold storage effect of frozen and refrigerated showcases will be further improved. The object of the present invention is to provide a laminated interlayer film that is easy to apply and apply to windows, etc., by applying the structure to a thermoplastic resin layer. As an optical interference filter having selective light transmittance, a Fapry-Bello filter is well known. This is known as an interference filter in which a transparent tritium having a specific optical thickness is sandwiched between opposing translucent boundaries, and allows only light of a specific wavelength to pass through. U.S. Pat. No. 3,684,528 reveals that by applying this Fapley-Bekou filter, a selective light transmitting sheet with crystalline transmission characteristics in the visible region and high reflection characteristics in the near-infrared region can be obtained.
is shown. According to this, for example, the structure of substrate/metal 1t4/dielectric/metal layer/dielectric is gas/Ni/Ag/kl, 0s/
400 n in the composition Ni/Ag/A408
The transmittance from m to 700 nm is 70% or more and the reflectance is about 10%, and from 700 nm to 25 Q Ofim
Transmittance is 10% or less and reflectance is approximately 90%
]'I! 1 Selective light transmissive wood 1 Wounded body can be obtained 5
In the Fabry 1 Page filter, the transmission wavelength width can be expanded by thinning 1g of the metal film that is the semi-transparent reflector, and the transmission wavelength width can be increased by lowering the refractive index of the important dielectric material that improves transmittance. It is known theoretically that it will become narrower. By choosing the refractive index and thickness of the dielectric material so that a 500 nm C transmission peak can be obtained by calculation, and making the metal film sufficiently thin, a filter with high transmission characteristics in the visible region and good blocking characteristics in the near-infrared region can be constructed. I can do it. Conventional filters are mainly used for precision optical applications, and from that point of view, metal compounds such as oxides with stable optical glare and low absorption have been used as transparent dielectrics.

[It was used. However, when used in energy-saving applications such as building windows, it is essential to apply it to a large area, and production on an industrial scale is impossible using conventional metal compounds as transparent dielectrics. This means that the technology of uniformly covering a large area of the surface of a thin metal i-layer with metal oxide at equal pressure is still an incomplete technology. If the thickness of the metal oxide film is thin < so It can be said that it is impossible to uniformly coat a large area with a film thickness of about .000χ on an industrial scale. We are applying this structure to a wide range of energy-saving applications →
As a result of extensive research, we have successfully created a light selective transmission film that is optically transparent and has uniform optical properties by applying a transparent dielectric layer made of a Fabry-Perot-filter organic compound. The present inventors have discovered that it is possible to do this, and that it is much easier to use in actual engineering than by contacting at least one side of the 15?1 unit with a layer made of thermoplastic resin. 1- That is, the present invention provides a laminate in which at least one side of a structure having light selective transmittance or transparent conductivity is in contact with a layer made of a thermoplastic resin. At least one surface of the monopolymer film (A) is coated with a metal thin film layer (B), a transparent dielectric layer (O) made of an organic compound, and a transparent dielectric layer (O, which is optionally present). Consists of 0 vague layers, (A) / (Bl / (C
1/ (Bl or (At / (81/ (C1/(B
This is a laminated interlayer film characterized in that the layers are laminated in the order of l/(IJ).The organic polymer film (A) in the present invention does not need to be particularly limited, but the laminated interlayer film of the present invention can be used as a transparent film. For the purpose of pasting it on windows, etc., it is necessary to have transparency with a transmittance of at least 50% or more, preferably 75% or more at 500 mμ, and an organic polymer film that satisfies this condition. In the case of (2), any conventionally known film may be used, but among these, polyethylene terephthalate film, polycarbonate film, polypropylene film, polyethylene film, polyethylene naphthalate, polysulfone film, polyethersulfone film, nylon film, etc. are preferably used. Furthermore, it is also possible to use in the present invention even if these organic polymer films contain a coloring agent of 8 degrees, an ultraviolet absorber 1 dye, etc., which do not impair the geometric properties and optical properties of the organic polymer film. The thermoplastic resin layer in the present invention is not particularly limited as long as it is a layer formed from a transparent thermoplastic resin. The thermoplastic resin layer having a transmittance of at least 80% or more at a wavelength of 5()011 m is in contact with at least one surface of the In composite having selective light transmission or transparent conductivity as referred to in the present invention. This means that the construct covering the sheet-like thermoplastic resin layer may be pressure-bonded, or the thermoplastic resin layer may be provided on the grafted body by means of a cloth. The resin layer has the function of protecting the front or back surface of the structure and/or acting as a contact layer or adhesive layer when attaching the structure to an actual window, etc. Thermoplastic material suitable for this purpose Examples of thermoplastic resins that can form the resin layer include polyvinyl butyl, polyacrylic acid ester, polyvinyl acetate, and polyvinyl ether.
Poly(vinyl pyrolyte, H5 polyethylene propylene copolymer, polyester copolymer, etc.) are generally mixed with tackifiers to improve their adhesive properties.Selective light transmittance or transparent conductivity In the case of using a structural body having properties for laminated windows etc., polyvinyl butyral is preferable as the thermoplastic resin.The material for the metal thin film M181 used in the laminate of the present invention is a material with low absorption loss in the visible light region. (Any metal or alloy with high electrical conductivity may be used, but it is particularly preferable that the main component is scissors. Other metals to be included are preferably gold, steel, aluminum, nickel, etc.) It doesn't matter what kind of metal it contains as long as it does not detract from the properties of silver.The silver content is a factor that controls the optical properties of the resulting Jj1 layered body. At least 40%, preferably 5Oy loss%.
It is preferable that the content is above. In addition, in order to obtain a thin layered body with particularly high infrared reflectivity, gold, (4
, a metal thin film layer (B) of an alloy consisting of 2 fl or 3 metals selected from the three elements of the body (B) a single metal thin film layer (preferably a ~1° metal thin film layer) The film thickness of (13) is not particularly limited as long as it satisfies the required characteristics of the obtained product j integral σ) optical zero property, but it is It is necessary for the film to have continuity as a film in at least a certain area. In order to increase the visible light transmission characteristics, which is the objective of the present invention, a 500A laminate is sufficient as a film thickness of approximately 30λ or more as a 5-layer film thickness from J, B-shaped 4D construction to continuous construction. In order to have sufficient visible light transmittance and sufficient infrared light reflectance, it is particularly preferable that the thickness of the metal thin film layer (13) σ) is about 40× or more and about 120× or less. Gold Ir4M, Fa layer (R) forming step 1 Method 42.
In addition to the 911 *, &f j"t ? vapor deposition method, the cut-F snow ξ spooling method, the inflation method, etc., the conventionally known σ)
In order to form a stable film with a thickness of 2 (l A or less σ), a film forming method using high-energy particles such as cathode snobbing, ion plate tying, etc. is preferable. When obtaining a thin film, the cathode sputtering method is preferable from the viewpoints of uniformity of the alloy composition σ) of the formed thin film and uniformity σ) of the thickness of the formed thin film. Further, when forming the metal thin film layer (B), in order to stabilize the metal layer which is a thin Btj, a pretreatment can be applied to the material where ik=plate by a known method. These methods are
For example, a surface cleaning treated organic silicate such as Ion Bonnocudment. Organic titanate, organic zirconate compound σ) Undercoating treatment such as coating and/or metal Ni + T + , Sl 2 . There is a nucleation stable habitat 9# in which Zr, V, TFL, etc. and oxides of these metals are formed in advance by sputtering etc., and these should be appropriately selected and used within a range that does not adversely affect the optical properties of the laminate. Good. If these pre-treatments involve an increase in thickness, the thickness is 1.
It is preferable that it is 00A or less. Fourth, the bond provided with the metal thin film II (B) may be subjected to a post-treatment similar to the pre-treatment described above. The transparent dielectric layer (C) used in the present invention is an organic compound with a refractive index between 1.35 and 650, and which is optically transparent and can be coated uniformly (also used in "J"). However, since it is used for optical filters, when a layer with a thickness of 1μ is formed, the
A homogeneous/travel dielectric material that transmits 85% or more of 0 mμ light, has few surface irregularities, and has no local turbidity) tli (an organic compound that can form O) is preferable. Examples of organic compounds include vinyl heptafluoride hexafluoropropylene copolymer, vinylidene fluoride tetrafluoroethylene copolymer, polytrifluoropoethylene vinyl fluoride copolymer, vinylidene fluoride chlorotrifluoroethylene copolymer, etc. Fluorine-41 fat, etc., acrylic resins such as acrylonitrile, polymethacrylonitrile, polymethylmethacrylate, acrylate resins and their mixtures or copolymers, polystyrene resins, vinyl chloride resins. Vinyl acetate resins, polyvinyl alcohol resins. Polyvinyl butyral resins. , phenoxy resin/polyester resin, polyurethane resin, etc., and mixture copolymers thereof are preferably used. In particular, if a fluororesin with a low refractive index is used, it is possible to screen with a high blocking rate of near-infrared light. The film thickness of the transparent!ll1lt body layer (O) is determined by the relationship between the selectively transmitted waves and the refractive index of the obtained transparent dielectric layer (Q). 65σ] 1 River K Aru I1 Reimon Ihi Sake Shizuku J σ) Ba Dai
, 1400A to 1400A to 11FIOA, it becomes an A'R layer body with visible so on nm KJ & large transmittance. In this way, the thickness of the transparent dielectric layer (0) can be appropriately determined depending on the desired optical properties and the refractive index of the 11 bright dielectric layer (C). , Dissolve the resin at an appropriate concentration in a solvent that can dissolve the selected resin, and spin coating if the area is small.Can be obtained by coating with a bar coater, doctor knife, etc. and drying.For large areas. By drying the coated buds using a machine such as a gravure roll coater or reverse roll coater,
It is possible to form a transparent dielectric layer (C) as thick as a grain of rice. The drying temperature depends on the resin used. Although it varies depending on the solvent, it is usually 80°C to 150°C. When an organic compound is used for optical purposes like the laminate of the present invention, the physical properties of the coated film govern the optical properties of the laminate, so the purity is 1. In addition, it is necessary to use a tank 11 that has excellent coating thickness and uniformity, and it is also necessary to appropriately select a coating method that can achieve a uniform film thickness. Preferably, it is necessary to keep the film thickness within ±5% of the set film thickness. The laminate of the present invention has a laminate having an optical function! structure(
A) / (Bl / (C') / (For the purpose of protecting Bl, an outermost layer 0 can be formed. Such a protective layer ([Mechanical damage compared to the one-layer structure of the old invention)] , chemical substances, etc.) It has the role of protecting against the infiltration of contaminants, moisture, etc. In order to achieve this objective and not adversely affect the optical properties of the laminate, Cτ is preferably a material that is optically transparent and has excellent strength and protection ability as the material for the protective layer 0. Si I kl @ Ti. A film made of an inorganic compound such as an oxide such as Zr or Ta or a mixed oxide of two or three kinds of gold (4f), or an acrylic resin such as acrylonitrile, polymethacrylonitrile, polymethylmethacrylate, etc. comonomer of t et al., polystyrene resin,
Vinyl acetate resin. Resins such as phenoxy resins, polyester resins, and polyurethane resins, and f) mixtures and copolymers thereof; destressing agents made of organic compounds; preferably used. This Hosun 1@ is not limited to thermoplastic resins, and thermosetting resins such as 4111 can also be used. In addition, when the IL1 layer interlayer film of the present invention is subjected to FCT in a harsh usage environment, polyethylene film, PO II propylene film, nylon film, polyester film, polycarbonate sheet, etc. having a thickness of 45 mm are used. Laminate the protective layer (1) using the method below.
It can also be used as l. A polyvinyl butyral sheet, a polycarbonate sheet, etc. can also be laminated by a known method and used as the protective layer 1rJ. When a film made of an inorganic compound is used as the protection 114 (I), sputtering, real g! Although physical forming methods such as vapor deposition and ion blasting are preferably used, the known gold J11! coating method involves diluting and coating a metal alkoxide compound in an appropriate solvent. The protective layer +Im made of a metal oxide can also be obtained by the oxide thin film formation method. A film made of organic compounds is dissolved in a suitable solvent to form a protective layer (when used as I, the above-mentioned resin is dissolved), and the film is coated and dried to form a protective layer made of organic compounds.
) of i can be obtained. The crushing layer in the present invention is not limited to a single layer, and may have a laminated structure of two or three layers. This is a mutually laminated structure of inorganic and organic compounds. It may also be a layered structure of inorganic compounds. These product 1
By forming the protective layer (D) with a structure, it is possible to obtain the protective layer (I) of the laminate of the present invention having a more favorable protective function. Thermoposable #JI Ie!
E Even when the resin layers are in contact, the retention time is 1M (Dr
The effect of this method is not reduced, and the characteristics of the structure having selective light transmission or transparent conductivity that is in contact with the thermoplastic resin layer 5 in the present invention are not impaired in any way. The thickness of the protective layer 0 of the present invention is not limited as long as it has the ability to protect the aluminum, but from the point of view of the protective ability.
'1. As mentioned above, in order not to deteriorate the optical properties of the laminate, the thickness is preferably 50 μm or less, particularly preferably 35 μm or less. A detailed explanation of the present invention will be given below with practical examples. Example 2 A Nissdell film with a thickness of 75 μm was used as a substrate, and a #11 layer of vinyl fluoride → trifluoropropylene copolymer was formed on it as a #11 layer.
Rikimei 1g? A trowel thin film layer with a thickness of 80 A was formed as the electric layer and the third layer. Steel thin! The first layer was formed using an oc magnetron sputtering cylinder using silver-gold paulownia as a target at an Ar gas pressure of s+10 TorrK. The input power is IW/a for the target single vertical plane! Met. Lu Ming X n! The body layer was prepared by dissolving vinyl fluoride hexafluoropropylene copolymer in a solvent consisting of 2 parts of methyl ethyl ketone and 2 parts of methyl imbutyl ketone IF+Bl acetic acid Celsolve, and applying the solution using a bar coater.
It was obtained by drying at 100°C for 3 minutes. The refractive index of the obtained transparent galvanic material layer was 1.41. Such fAr
(A layer made of polyvinyl butyral resin was formed on the polyester film surface of the four substrates. The layer made of polyvinyl butyral was prepared by dissolving the polyvinyl butyral resin in 10 wt% of a solvent K consisting of 2 parts of toluene and 1 part of ethyl acetate, and using a bar coater. 10 after coating
It was dried for 2 minutes at 0°C and served. The film thickness was 10 μm. The transmittance of the obtained laminated interlayer film at 500 mμ was 74%.
The infrared light reflectance at 10μ was 81%. In addition, when we calculated the integrated visible light transmittance (from 400 nm to 700 nm) and the integrated near-infrared light transmittance (from 700 ron or more to 2100 nffl) normalized by the intensity distribution of solar energy, the integrated visible light transmittance was 72%. The integrated near-infrared light transmittance was 28%. Example 2 A silver ring thin film layer having a thickness of 90A and containing 10 wt% of copper was formed as the first layer on the polyester film used in Example;
#Therefore, a transparent dielectric layer made of polymethacrylonitrile with a thickness of 1,000A, a thin layer of silver copper containing 1 (lyt%) with a thickness of 90A as the third layer, and a thin layer of silver copper with a thickness of 1% as the fourth layer. After forming a protective layer made of 7 acrylate resin with a thickness of 2 μm, a sheet made of polyvinyl butyral resin with a thickness of 380 μm was bonded.
The sputtering conditions were the same as in Example 1, in which sputtering was performed using a silver-copper alloy target containing 10 wt% copper. The transparent dielectric In made of polymeth7crylonitrile is
A solution consisting of 1 part of cyclohexanone and 2 parts of methyl ethyl ketone containing awt% of polymetha-7crylonitrile resin was coated with a bar coater and dried at 120° C. for 2 minutes. The protective layer made of acrylate resin contains 10wt of acrylate resin (Mitsubishi Rayon Dianal LR574).
A solution consisting of 1 part of toluene and 2 parts of methyl imbutyl ketone containing 5% was applied using a bar coater and dried at 120° C. for 2 minutes. After that, the obtained f# layer body was sandwiched between polyvinyl butyral sheets with a thickness of 380μ, and then
℃IIJIML, 1 by applying a pressure of 9/cd. The transmittance of the obtained laminated interlayer film at 500 tHμ is 72%.
The integrated visible light transmittance was 70% and the integrated near-infrared light transmittance was 28%. 'Example 3 A film with a thickness of 2 on a biaxially stretched polyester film with a thickness of 50
0A titanium oxide layer, 90A thick silver-gold thin film layer containing 15% gold (20K thickness) (n titanium oxide layer, 1,100A thick transparent dielectric layer formed from polystyrene resin,
Thickness: 20 A17) A laminate consisting of a 1114 vc layer of an IW titanium layer, a 90H thick silver-gold thin film layer containing 15 weight of gold, and a 20A thick titanium oxide layer σ) Made of polyvinyl butyral resin on both sides. j (j was formed to obtain a laminated interlayer film. ~ The silver-gold thin film layer with a thickness of 90 A containing gold y13<rH% was gold f5
A thin titanium oxide B'A layer with a thickness of 20A was formed by the DC madanetroso sputtering method using an alloy of gold and silver containing 3% of 51i as a target.
It was formed by DC madanetron sputtering under a pressure of 5X 10-3 Torr (7) while reacting '1'i with oxygen gas while using MRL. The transparent Pyj electric layer made of polystyrene resin contains 3wt% polystyrene resin.
Contains 5 parts of toluene. A solution consisting of 1 part of ethyl acetate was coated with a bar coater, and 1 part of ethyl acetate was applied.
It was obtained by drying at 10°C for 3 minutes. A layer made of polyvinyl butyral resin was obtained by applying a solution containing 20 wt % polyvinyl butyral, consisting of 2 parts of toluene and 1 part of ethyl acetate, using a bar coater to obtain a layer having a thickness of 30 μm. The transmittance of the obtained laminated interlayer film at 50f31nμ is 72%.
, +jl + "J visual transmittance was 70%, and near-infrared light transmittance was 72%. Example 4 On the silver thin film layer which is the third layer of the laminated interlayer film obtained in Example 1. A titanium oxide layer formed from butrabutyl titanate of K PJ 3 OA was formed 17'), thickness 27
A protective layer made of a polymethacrylonitrile layer of J was formed, and then the surface of the obtained laminated structure made of polymethacrylonitrile was pressed against a polyvinyl butyral sheet having a thickness of 3 B Opi to obtain a laminated interlayer film. A titanium oxide layer formed from tetra-7tyl titanate was obtained by applying a solution of 3 parts of butanol containing 0.8 wj% of tetrabutyl titanate and 2M of Improper Tool using a bar coater and drying to obtain 1. The drying temperature was 120°C and the drying time was 3 minutes. The protective layer consisting of polymethacrylonitrile layer was coated with a solution consisting of 2 parts of cyclohexanone and 1 part of methyl ethyl ketone containing 10% by weight of polymethacrylonitrile using a bar coater, dried at 120°C for 2 minutes, and shaded at 120°C. Crimping hook for polyvinyl butyral sheet 2 21 M
Thickness 3 B O on the polymethacrylonitrile surface of the IN body
Combine the Ir polyvinyl butyral sheets, 1. OO
℃+'kp/d, temperature fψ, 1 hour under pressure) and crimping. The resulting laminated interlayer film had a transmittance of 72% at 5001, an integral visible transmittance of 72%, and an integral near-infrared transmittance of 2.
It was 6%. Procedural amendment dated September 9, 1980, to the Commissioner of the Japan Patent Office 1, Indication of the case, Patent Application No. 125113, No. 1987, 2, Name of the invention, Stacking Intermediate 1φ 3, Person making the amendment, Relationship with the case, Patent applicant, Minamihonmachi, Higashi-ku, Osaka City 1-11 (300) Teijin Ltd. Representative Sashibe Okamoto (1) Passed away! In the 8th line from the bottom of page 12, ``1 mixture conjugated polymer'' is corrected to 1 mixture, copolymer, and cross-persimmon mixture of the above. (2) No. 23; Add the following below line 1410. [Example 5 2411+ 1; Φ pressed polyester film with a thickness of 75 μm was used as a substrate, Kf (1 part layer, 80× thick steel thin side layer, 2nd layer with methacrylonitrile (90 parts) and 2 -ethylhexyl methacrylate (
A transparent dielectric layer with a thickness of 800X from a crosslinked copolymer with 10 parts), and a third layer of 1Jl with a thickness of 80χ! The silver thin film layers in the 1st and 31st fields were formed using Ar gas pressure of 5 X l O” T with steel metal as the target.
It was formed by DC magnetron sputtering under orr. Input power is 2W per target bank No. 1 bond.
/ crd. The second transparent dielectric layer is made of metaacrylonitrile 9
1 part of a copolymer formed from 0 parts of 2-ethylhexyl methacrylate and 10 parts of 2-ethylhexyl methacrylate; A solution prepared by dissolving 0.4 parts of the N-copolymer (manufactured by the company) in a mixed solvent of cyclohexanone, acetone, and methyl ethyl ketone (mixing ratio 5:2:I) in a manner similar to that of a double-coated copolymer. was coated with a bar coater and dried at 120° C. for 2 minutes to form a thin layer of the copolymer crosslinked with the isocyanate compound. The visible light transmittance of the obtained laminate at a wavelength of 50 fl mμ was 77 cm, and the infrared reflectance at a wavelength of 10 μm was 82 cm.
It was Chi. Further, the integrated near-infrared light transmittance of the laminate normalized by the intensity distribution of solar energy was 72 yen, which was 30% compared to the same integral near-infrared light transmittance ¥-V. After inserting Hl into the above laminate from both sides with polyvinyl butyral sheets having a thickness of 380 μm, + to
℃K 7! IIm and crimped by applying a pressure of 1 kg/c+d. The visible light transmittance of the obtained laminated interlayer film at a wavelength of 500t+tμ is 72, and the integral visible light transmittance is 72.
1%, and the integrated near-infrared light transmittance was 26 cm. ” or later
Appeals Procedures Page JF-January 1982/1980 To the Commissioner of the Japan Patent Office 1, Indication of the case Patent Application No. 125113/1987 2, Name of the invention Laminated interlayer film (300) Teijin Ltd. Representative Okamoto 4th Division 4, Agent 2-1-1 Uchisaiwai-cho, Chiyo, Tokyo [1] Ward (Iino Building) - (1) Akira I ■ Page 23, under line 10 Showa:) 1
September 9, 1999 (=Supplemented in J procedural amendment. [2-Ethylhexyl methacrylate-1.] in Example 5 (page 2, lines 9-10 of the same procedural amendment) 2-Human L1-1shi1
Corrected as Dermetacryle-1-,1. that's all

Claims (1)

[Claims] In a laminate in which at least one side of a structure having selective light transmission or transparent conductivity is in contact with a layer made of a thermoplastic resin, the structure having selective light transmission or transparent conductivity is an organic polymer film. At least one surface of the prisoner is made of a metal thin film layer (B), a transparent dielectric layer (O) made of an organic compound, and a protective layer (O) present as necessary.
Al / (B) / C) / Q31 or C (Al / (B
)/C')/(B)/(In)IllKff1 layer tL
A laminated interlayer film that is characterized by its porosity.