JPS6225097B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a selective light transmitting laminate with improved spot resistance, more specifically, it has high visible light transmittance and infrared reflectance, excellent abrasion resistance, and is resistant to spots caused by moisture, rainwater, etc. The present invention relates to a selective light transmitting laminate having excellent properties. As the selective light transmitting laminate, for example, one that is transparent to visible light and reflective to infrared light is used as a transparent heat insulating film. Laminated bodies with such performance can be used as windows in buildings, refrigerated/refrigerated cases, vehicles, aircraft windows, etc.
The function of transparent insulating windows that utilize solar energy and prevent energy dissipation will become increasingly important in the future. A selective light transmitting laminate that achieves this purpose is a laminate in which a metal thin film layer is sandwiched between transparent high refractive index thin film layers, such as vacuum evaporation, reactive evaporation,
Bi ₂ O ₃ /Au/Bi ₂ O ₃ , ZnS/Ag/ZnS or
Laminated bodies such as TiO ₂ /Ag/TiO ₂ have been proposed.
Those using silver as the metal layer have particularly excellent transparency in the visible light region and reflective ability for infrared light due to the optical properties of silver itself. However, when using a laminate with selective light transmittance as a transparent heat insulating window, it is necessary to improve not only the original performance such as visible light transmittance and infrared light reflectance, but also the durability against abrasion and staining. Practical performance is also required. However, in general, laminated extremely thin metal films or metal oxide thin films as described above often have insufficient abrasion resistance and stain (spot) resistance, for example when used in double-glazed glass. However, if it is directly exposed to the outside, it is necessary to provide a protective layer. The present inventors previously investigated various protective coating agents in order to improve the practicality of the laminate and found that many protective coating agents could improve wear resistance, but at the same time, the infrared reflective ability, i.e. It was discovered that the ability to reflect heat rays was significantly reduced. As a result of tracing the cause of this, it was found that the protective layer absorbs most of the infrared rays, and that the absorbed infrared energy is re-radiated as heat rays and at the same time is transmitted to the surroundings by conduction and convection. Therefore, when actually applying a protective layer to a selectively transparent laminate, the following problems exist. If the protective layer is too thick, the protective function will increase, but the absorption rate in the infrared region will increase, and therefore the ability to reflect infrared light will decrease significantly. When using a general protective coating agent, the thickness of the protective layer
If the thickness is 1.5 μm or more, a considerable decrease in infrared reflectivity cannot be avoided. A protective film thickness of about 0.3 μm to 1.5 μm is suitable for the purpose of the present invention in that it does not reduce infrared reflective ability. However, with this film thickness, rainbow-colored interference patterns occur when exposed to visible light, so it cannot be used for normal purposes. If the film thickness is further reduced, the absorption in the infrared region will further decrease and the generation of interference marks can be avoided, but on the contrary, the wear resistance will be significantly reduced. For example, in most cases, with coatings for general paints, it is difficult to expect a sufficient function as a protective layer if the film thickness is less than 0.3 μm to avoid interference. The present inventors have discovered that by using a polymer mainly composed of (meth)acrylonitrile as a protective layer, it is possible to resolve the above contradiction and maintain excellent selective light transmittance while improving abrasion resistance. Already suggested. There are few problems when using a selective light transmitting laminate having such a protective layer laminated thereon at a relatively low temperature, such as in a frozen or refrigerated case. However, if the film is to be used for a long period of time in a place where it is directly exposed to wind and rain under high temperature, high humidity, severe temperature differences, etc., for example as a film for controlling sunlight, a protective layer and a selective light transmitting laminate are required. In between, minute flakes occur and spots are unavoidable. In such a situation, the excellent performance of poly(meth)acrylonitrile, such as low infrared absorption, high abrasion resistance, heat resistance, and high durability such as light resistance, can be preserved.
Moreover, it is strongly desired to suppress the occurrence of spots. As a result of intensive research, the present inventors have developed a linear polyurethane layer between poly(meth)acrylonitrile and a protective layer that can suppress the occurrence of spots while maintaining the above-mentioned excellent performance of poly(meth)acrylonitrile. The inventors have discovered that the above object can be achieved by providing the above-described structure, and have arrived at the present invention. That is, the present invention provides a structure in which a metal thin film layer and/or a metal oxide thin film layer is laminated on at least one side of a transparent molded substrate, optionally in combination with a high refractive index thin film layer; In a permselective laminate in which layers are sequentially laminated, the first layer of the protective layer is made of linear polyurethane, and the second layer has the following general formula [] The present invention is a selective light-transmitting laminate characterized by being made of a polymer whose main structural unit is a structural unit represented by the following formula: [wherein R represents a hydrogen atom or a methyl group]. The first polyurethane layer in the protective layer used in the present invention includes (a) a metal thin film layer constituting the selective light transmitting laminate;
High adhesion to metal oxide thin film layers and high refractive index thin film layers. (b) High adhesion to the second poly(meth)acrylonitrile protective layer. It shows excellent features such as The polyurethane layer used as the first protective layer in the present invention is formed by an addition reaction between a diisocyanate and a diol. The diisocyanate may be aliphatic, alicyclic or aromatic polyisocyanate.
Specific examples include tetramethylene diisocyanate, hexamethylene diisocyanate, 2.2.
Aliphatic systems such as 4-trimethylhexamethylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate; m-, p-cyclohexylene diisocyanate, 4-methyl-m-cyclohexylene diisocyanate,

【formula】

【formula】

【formula】

【formula】

Alicyclic systems such as [Formula]: Aromatic diisocyanates such as m-, p-phenylene isocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, diphenyl ether diisocyanate, m-, p-xylylene diisocyanate are preferred. used. On the other hand, diols include ethylene glycol,
Propylene glycol, tetramethylene glycol, neopentylene glycol, cyclohexanedimethanol, xylylene glycol; Aliphatic and alicyclic diols such as N-alkyl substituted diethanolamines such as N-methyldiethanolamine and N-ethyldiethanolamine; Hydroxyl groups at both ends Polyethylene glycol, polypropylene glycol, polytetramethylene glycol or copolymers thereof; polyethylene adipate, polyethylene sebacate, having hydroxyl groups at both ends;
Aliphatic polyesters such as polytetramethylene adipate, polytetramethylene sebacate, or copolymers thereof; Polydienes having hydroxyl groups at both ends such as 1,2-polybutadiene diol, 1,4-polybutadiene diol, etc. are preferably used. used. The proportion of urethane bonds in the polyurethane layer is usually 0.2 to 12 mmol/g, preferably 0.2 to 12 mmol/g, expressed as the equivalent of urethane bonds per 1 g of polyurethane resin.
It is 0.5-10 mmol/g. The second protective layer used in the present invention has the following general formula [] It consists of a polymer whose main constituent unit is a constituent unit represented by [wherein R represents a hydrogen atom or a methyl group]. Examples of polymerization types include radical polymerization and anionic polymerization, and examples of polymerization methods include bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization.
Further, the molecular weight of these polymers used is such that the intrinsic viscosity measured in dimethylformamide at 20° C. is 0.5 to 15.0, preferably 0.7 to 10.0. If it is less than that, a decrease in scratch resistance is observed, and if it is more than that, no improvement in scratch resistance is observed as the molecular weight increases, and the viscosity of the coating liquid becomes high, resulting in poor coating properties, which is not preferable. In addition, other structural units may be included as long as the features of the protective film layer of the present invention are not impaired. Such a structural unit is formed from a vinyl monomer that can be copolymerized with (meth)acrylonitrile. For example, styrene, styrene monomers such as α-methylstyrene, (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, n-butoxyethyl (meth)acrylate, glycidyl (meth)acrylate, glycidyl (meth)acrylate n - (Meth)acrylate monomers such as butanol, phenol, diethanolamine adducts; (meth)acrylamide monomers such as (meth)acrylamide, N-methylolacrylamide, diacetone acrylamide, vinyl acetate, butadiene, isoprene, ethylene, propylene, etc. Can be mentioned. These copolymerizable structural units may be of one type, or two or more types may be mixed. The thickness of the protective film layer is between the upper limit of the interference film thickness and 20 μm or less, preferably between the upper limit of the interference film thickness and 10 μm in total for the first layer and the second layer. Interference film thickness is the film thickness that produces a rainbow-colored interference pattern when exposed to visible light.
Although it cannot be said to be exact because it varies slightly depending on the refractive index, etc., it is usually about 0.3 μm to 1.5 μm. Therefore, the lower limit of the thickness of the protective film in the present invention is determined depending on the material.
The thickness is preferably 1.5 μm or more. Moreover, if the film thickness exceeds 20 μm, the infrared absorption rate becomes high, which is not preferable. However, since the first polyurethane layer exhibits stronger absorption in the infrared region based on urethane bonds than the second (meth)acrylonitrile layer, increasing the film thickness lowers the heat ray reflective ability. Therefore, the thickness of the first layer should be kept to the minimum thickness necessary to provide adhesion between the selective light transmitting functional layer and the second protective layer. The specific range is 0.01μ~
0.8μ, preferably 0.05-0.5μ, more preferably
0.1-0.3μ is used. If it is more than that, it is not preferable because the heat ray reflective ability will decrease, and if it is less than that, it will not be possible to impart an adhesive effect and it will not be able to contribute to the spot resistance, so it is not preferable. In the present invention, a laminate (hereinafter referred to as laminate) having selective light transmittance to be provided on the protective film as described above is used.
(B)) is a permselective functional layer, that is, a metal thin film layer and/or a metal oxide thin film layer (if necessary, laminated in combination with a high refractive index thin film layer) on at least one side of a transparent molded substrate. ) are laminated. Selective light transmitting laminate (B) used in the present invention
The base transparent molded substrate may be either an organic or inorganic molded product or a composite molded product thereof. Examples of organic molded products include molded products of polyethylene terephthalate resin, polyethylene naphthalate resin, polybutylene terephthalate resin, polycarbonate resin, polyvinyl chloride resin, acrylic resin, polyamide resin, polypropylene resin, and other resins. On the other hand, examples of inorganic molded products include molded products of metal oxides such as soda glass, borosilicate glass, alumina, magnesia, zirconia, and silica. These molded products can be molded into any shape such as a plate, sheet, or film, and colored or uncolored transparent ones are selected depending on the purpose. However, sheet-like, film-like, and plate-like materials are preferable from the viewpoint of processability, and among them, film-like materials are particularly preferable from the viewpoint of productivity. Further, a biaxially oriented polyethylene terephthalate film is preferable from the viewpoints of the strength of the transparent film, dimensional stability, adhesiveness with the laminate, and the like. The film may be pretreated with corona discharge treatment, claw discharge treatment, flame treatment, ultraviolet or electron beam treatment, ozone oxidation treatment, hydrolysis treatment, etc. in order to improve adhesive properties, or may be precoated with an adhesive layer. Also good. The high refractive index thin film layer used in the present invention includes:
Examples include a thin film layer made of one or more compounds selected from the group consisting of titanium dioxide, titanium oxide, bismuth oxide, zinc sulfide, tin oxide, zirconium oxide, indium oxide, silicon oxide, and the like. The high refractive index thin film layer has a high refractive index for visible light, usually 1.4 or more, preferably 1.6.
or more, preferably has a refractive index of 1.8 or more,
It is effective that the visible light transmittance is 80% or more, preferably 90% or more, and the film thickness is 10 to 600 Å, preferably 20 to 400 Å. As the material for the metal thin film layer, silver, gold, copper, aluminum, nickel, palladium, tin, and alloys or mixtures thereof are used. Especially,
Silver, gold, copper, alloys or mixtures thereof are preferably used. The film thickness is 30 to 500 Å, preferably 50 to 200 Å, and a thickness within this range is preferred from the viewpoint of both transparency and heat insulation. The metal thin film layer may be a single layer, or may be a multilayer combination of different metals. A particularly preferable metal thin film layer is 80 to 200
A thin metal film consisting of a silver layer or an alloy layer of silver and copper with a thickness of 80 to 200 Å, and in which the proportion of copper in the alloy layer is 5 to 15% by weight, a thin metal film consisting of an alloy layer of silver and gold of 80 to 200 Å. It is a layer. Indium oxide, tin oxide, tin cadmium oxide, and mixtures thereof are used as the material for the metal oxide layer. Therefore, specific examples of the selective light transmitting laminate (B) before the protective film is laminated in the present invention include the following. A more preferred embodiment is one in which an extremely thin layer of Ni, Co, Cr, etc. is provided. (a) PET/TiO _x /Ag/TiO _x (b) PET/TiO _x /Ag−Cu/TiO _x (c) PET/TiO _x /Ag−Au/TiO _x (d) PET/TiO _x /Ag− Au−Cu/TiO _x (E) PET/ZnS/Ag/ZnS (F) PET/SnO ₂ /Ag−Cu/SnO ₂ (G) PET/TiO _x ／Ag−Au−Cu/ZnS (H) PET/ Bi ₂ O ₃ /Ag-Au/Bi ₂ O ₃ (li) PET/Ni/Au/SiO ₂ (nu) PET/Ni/Au (ru) PET/Au/TiO _x (wo) PET/In ₂ O ₃ (W) PET/Al (F) PET/In ₂ O ₃ −SnO ₂ (Y) PET/Ni−Cr (T) PET/ZrOx/Ag・Cu/ZrOx (R) PET/Ag・Cu/ZrOx Here x takes a value between 1 and 2. However, the present invention is not limited thereto. In the laminate (A) of the present invention, the surface of the selectively transparent laminate (B) having the above-mentioned structure is coated with a polymer mainly composed of the structural units of the formula () next to the above-mentioned linear polyurethane. It can be obtained by forcing. In obtaining the laminate (B), the method of laminating the metal thin film layer and/or metal oxide thin film layer, and furthermore the high refractive index thin film layer on the transparent substrate is not particularly limited.
It can be carried out individually or in combination as appropriate from among conventionally known vacuum evaporation methods, cauldron sputtering methods, plasma spraying methods, vapor phase plating methods, chemical plating methods, electroplating methods, chemical coating methods, and the like. In addition, when using titanium oxide or zirconium oxide as a high refractive index thin film layer, an industrially advantageous method is to wet-coat a solution of an alkyl metal compound such as tetrabutyl titanate or tetrabutyl zirconate, and then apply this to a solvent. There is a method of evaporation-hydrolysis, but in addition to the cost advantage, this method allows the titanium oxide or zirconium oxide layer to contain a small amount of organic matter, which improves adhesion with other layers. It is also possible to exhibit effects. In this case, the performance of the laminate can be improved by processing the layer under even higher temperature and humidity conditions (for example, 80° C., RH 100%). Further, the same effect can be obtained even if such treatment is performed after providing the protective layer. If a titanium oxide layer etc. is provided by the above method, a laminate (B') having the above-mentioned advantages can be obtained, but depending on the usage conditions, oxidation may be performed by physical means such as sputtering method. In many cases, the durability is inferior to the laminate (B″) provided with a titanium layer, etc. However, even such a laminate (B′) can be made into the laminate (A) of the present invention to prevent oxidation. It has extremely excellent durability regardless of the method of forming titanium, etc. Therefore, the structure of the laminate (B') in which the effect of the protective layer of the present invention can be even more excellently exhibited is the above-mentioned chemical Titanium oxide, zirconium oxide, etc. formed by
Expressed in terms of TiO ₂ (TBT), (a) PET/TiO ₂ (TBT)/Ag/TiO ₂ (TBT) (b) PET/TiO ₂ (TBT)/Ag and Au and/or
Examples include Cu alloy/TiO ₂ (TBT) (c) PET/Au/TiO ₂ (TBT) (d) PET/TiO ₂ (TBT)/Au/TiO ₂ (TBT). In order to provide the first layer of the protective film on the surface of the laminate (B), a solution containing the raw material of the crosslinked polymer is usually coated or dipped, by a spraying method, a spinner method, a gravure coating method, etc. This is achieved by forming a solution layer using a general method and then carrying out a crosslinking reaction. After coating, the first protective layer is polymerized by a urethanization reaction of diol and diisocyanate.
Therefore, the solvent to be used is not particularly limited as long as it is insoluble in isocyanate, dissolves diol and diisocyanate, and can be removed by evaporation, but examples include dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and tetramethyl. Polar solvents such as urea, dimethyl sulfoxide, and tetramethylene sulfone; Ketone solvents such as cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, and acetone; Ester solvents such as ethyl acetate, butyl acetate, and isobutyl acetate;
Other solvents used include ethyl acetoacetate, methyl acetoacetate, and acetylacetone. However, in order to sufficiently remove the solvent and perform the urethanization reaction, drying is generally carried out at 70°C or higher.
Preferably it is carried out at 100°C or higher. The upper limit of drying temperature depends on the heat resistance of the base material and drying time.
200℃ is sufficient. Further, in order to promote the urethanization reaction, a tertiary amine such as triethylenediamine or tri-N-butylamine or a urethanization catalyst such as dibutyltin dilaurate may be used in combination. Further, the second protective layer does not need to undergo a chemical reaction after coating, but can be easily obtained by coating and drying a solution containing the polymer in the same manner as the first layer. At this time, in addition to the polymer, additives such as ultraviolet absorbers or other polymers may be used in combination as long as they do not impair the performance of the present invention, that is, selective light transmittance and abrasion resistance. good. In addition to being used as a transparent heat-insulating laminate, the laminate thus obtained can be used for applications utilizing its conductivity, such as electrodes for liquid crystal displays, electrodes for electroluminescent materials, electrodes for photoconductive photoreceptors, and antistatic layers. It is also used in fields such as electronics, such as surface heating elements. Hereinafter, a more specific explanation of the present invention will be shown in Examples. Note that in the examples, unless otherwise specified, the light transmittance is a value at a wavelength of 500 nm. Infrared reflectance is measured by attaching a reflectance measurement device to a Hitachi EP-type infrared spectrometer and measuring the reflectance of a slide glass with sufficiently thick (approx. 3000 Å) vacuum-deposited silver.
Measured as 100%. Further, the elemental composition in the metal thin film was determined by quantitative determination using a fluorescence X-ray analysis method (using a Rigaku Fluorescence X-ray analyzer). For the clock meter test, a clock meter manufactured by Toyo Seiki was used. Using commercially available gauze,
A load of 500 g/m ² was applied to the sample surface to wear it back and forth, and the number of times it would take to wear the metal layer back and forth was determined. The film thickness was measured using a digital electronic micrometer (model K551A) manufactured by Anritsu Electric. Next, a method for calculating the average infrared absorption rate will be shown. A protective layer (thickness: 2μ unless otherwise specified) is provided on the selectively permeable laminate formed by laminating a high refractive index thin film layer and a metal thin film layer, and its infrared reflectance is set to 3 to 25.
Measure in the μ wavelength range. On the other hand, the energy radiated from a blackbody at 300〓 (27℃) is picked up every 0.2μm, and the product of the radiant energy and infrared reflectance according to each wavelength is calculated every 0.2μm. Find the sum in the wavelength domain. Then, the sum is normalized by dividing it by the sum of the radiant energy intensity in the 3 to 25 μm region. This value is the energy radiated from 300〓 (3 to 25 μm
represents the overall percentage of the area) that is reflected. This is defined as infrared reflectance. The radiant energy in the 3 to 25 μm region corresponds to about 85% of the total black body radiant energy of 300 mm. Corrosion resistance was measured using a salt spray tester (Suga Test Instruments KK).
The selective light transmitting laminate was placed in a refrigerator whose temperature was controlled to 35°C, and salt water (concentration 5%) was sprayed onto the glass. Observe the sample every 24 hours, and check if there are 5 speckled spots within 5 x 5 ^cm2 of the sample.
Corrosion resistance was evaluated based on the number of days until corrosion occurred. In addition, all "parts" in the examples are based on weight. Example 1 A biaxially stretched polyethylene terephthalate film with a light transmittance (500 μm) of 86% and a film thickness of 50 μm, a titanium oxide layer with a thickness of 300 Å, and an alloy layer of silver and copper with a thickness of 195 Å (92 wt% silver, 8 wt% copper) ) and a titanium oxide layer of 280 Å were sequentially laminated to obtain a laminate (B-1) having selective light transmittance. For each titanium oxide layer, a solution consisting of 3 parts of tetrabutyl titanate tetramer and 97 parts of isopropyl alcohol was applied using a percoater, and heated at 120°C for 30 minutes.
It was prepared by heat treatment for a minute. The silver/copper alloy layer was formed by vacuum evaporation using a resistance heating method using an alloy containing 70 wt% silver and 30 wt% copper. On this laminate (B-1), 16.8 parts of hexamethylene diisocyanate, ethylene glycol
A coating solution consisting of 6.2 parts of cyclohexanone, 105 parts of cyclohexanone, and 105 parts of methyl ethyl ketone was coated using bar coater No. 5, and dried at 130°C for 3 minutes to form a first layer with a film thickness of 0.3μ. (ηsp/c1.0dl/g,
c=0.5g/dl, dimethylformamide solution, 30
℃), 45 parts of methyl ethyl ketone, and 45 parts of cyclohexanone were coated using a bar coater No. 16, and dried at 130℃ for 3 minutes to obtain a laminate (A) having a transparent protective layer with a film thickness of 2.0 μm. -1) was obtained. The infrared reflectance of the laminate (A-1) was 83%, and the visible light transmittance was 59%. Furthermore, the abrasion resistance according to the clock meter test was more than 3000 times, and the appearance of stains after 8 days in the salt spray test. Comparative Example 1 Polymethacrylonitrile (ηsp/C=1.0,
A coating solution consisting of 10 parts of 0.5% DMF solution (20°C), 45 parts of methyl ethyl ketone, and 45 parts of cyclohexanone was applied using bar coater No. 16 in the same manner as in Example 1 to form a transparent protective film with a thickness of 2.0 μm. A laminate (A-2) having layers was obtained. Although the laminate A-2 had an infrared reflectance of 86%, a visible light transmittance of 57%, and scratch resistance of 2,500 times or more, stains appeared in one day in the salt spray test. Example 2 A biaxially stretched polyethylene terephthalate film with a light transmittance (500 μm) of 86% and a film thickness of 25 μm, a titanium oxide layer with a thickness of 150 A, a layer of silver with a thickness of 190 A, and a layer of 250 A with a thickness of 250 A.
Titanium oxide layers were sequentially laminated to obtain a laminate (B-2) having selective light transmittance. The titanium oxide layer was provided by reactive sputtering of titanium. A coating liquid consisting of 18.8 parts of xylylene diisocyanate, 11.9 parts of N-methyldiethanolamine, 300 parts of cyclohexanone, and 300 parts of methyl ethyl ketone was coated on this laminate (B-2) using a bar coater No. 5, and the temperature was 130°C. 3
A first layer with a film thickness of 0.2μ was applied by drying for 10 minutes, and then the methacrylonitrile polymer 10 used in Example 1 was applied.
parts, 45 parts of methyl ethyl ketone, cyclohexanone
Coating liquid consisting of 45 parts is applied to bar coater No.16.
A laminate (A
-3) was obtained. The infrared reflectance of the laminate A-3 was 84%, and the visible light transmittance was 60%. In addition, the wear resistance measured by clock meter was over 3000 times, and there were no problems in practical use. When evaluated using a salt spray tester, spot-like stains appeared after 25 days, and a marked improvement in stain resistance was observed. Comparative Example 2 Polymethacrylonitrile was coated on the laminate B-2 under the same conditions as in Comparative Example 1 to obtain a laminate (A-4) having a transparent protection with a film thickness of 2 μm. The infrared reflectance of the laminate (A-4) was 82%,
The visible light transmittance was 63%. However, in the salt spray tester, stains appeared within one day. Example 3 A titanium oxide layer with a thickness of 150A, gold with a thickness of 90A, and a titanium oxide layer with a thickness of 250A were sequentially laminated on a biaxially stretched polyethylene terephthalate film with a light transmittance of 86% and a film thickness of 25μm to achieve selective light transmittance. A laminate (B-3) was obtained. The titanium oxide layer was applied by reactive sputtering of titanium, and the gold was applied by conventional sputtering methods. This laminate (B-3) was coated with a coating liquid consisting of 19.4 parts of hexahydroxylylene diisocyanate, 10.6 parts of diethylene glycol, 150 parts of cyclohexanone, and 150 parts of methyl ethyl ketone using Percoater No. 5.
℃ for 3 minutes to form a first layer with a thickness of 0.3μ.
Next, the coating liquid consisting of 10 parts of methacrylonitrile polymer used in Example 1, 45 parts of methyl ethyl ketone, and 45 parts of cyclohexanone was coated using Percoater No. 16, and dried at 130°C for 3 minutes to form a transparent film with a thickness of 2.0 μm. A laminate (A-5) having a protective layer was obtained. The infrared reflectance of the laminate A-5 was 74%, and the visible light transmittance was 71%. In addition, the wear resistance measured by clock meter was over 3000 times, and there were no problems in practical use. When evaluated using a salt spray tester, no spot-like stains appeared even after 40 days. Comparative Example 3 A protective film of polymethacrylonitrile having a thickness of 2 μm was provided on the laminate B-3 under the same conditions as in Comparative Example 1. When the sample was subjected to a salt spray test, 30 days later, part of the sample had turned reddish-purple. Example 4 A biaxially stretched polyethylene terephthalate film with a light transmittance (500 nm) of 86% and a film thickness of 25 μm, a titanium oxide layer with a thickness of 150 Å, a titanium layer with a thickness of 40 A,
160 Å thick silver and copper alloy layer (silver to copper weight ratio
A selective light transmitting laminate (B
-4) was obtained. As in Example 1, the titanium oxide layer was provided by the hydrolysis method of tetrabutyl titanate. Further, the metal layer was obtained by a sputtering method. On this laminate (B-4), 22.2 parts of isophorone diisocyanate, 20.0 parts of polyethylene glycol (average molecular weight 200), 300 parts of cyclohexanone
A coating solution consisting of 300 parts of methyl ethyl ketone was coated using Percoater No. 5, and dried at 130°C for 3 minutes to form a first layer with a film thickness of 0.3 μm. A coating solution consisting of 10 parts of methyl ethyl ketone, 50 parts of cyclohexanone, and 40 parts of cyclohexanone was coated using bar coater No. 16, and heated at 130°C.
After drying for 3 minutes, a laminate (A-6) having a transparent protective layer with a thickness of 2.0 μm was obtained. The infrared reflectance was 78% and the visible light transmittance was 63%. In the salt spray test, stains appeared after 7 days,
A significant effect was observed. Example 5 A biaxially stretched polyethylene terephthalate film with a light transmittance (500 μm) of 86% and a film thickness of 50 μm, a titanium oxide layer with a thickness of 300 Å, and an alloy layer of silver and copper with a thickness of 195 Å (92 wt% silver, 8 wt% copper) ) and a titanium oxide layer of 280 Å were sequentially laminated to obtain a laminate (B-1) having selective light transmittance. Each titanium oxide layer was coated with a solution consisting of 3 parts of tetrabutyl titanate tetramer and 97 parts of isopropyl alcohol using a bar coater, and heated at 120°C for 30 minutes.
It was prepared by heat treatment for a minute. The silver/copper alloy layer was formed by vacuum evaporation using a resistance heating method using an alloy containing 70 wt% silver and 30 wt% copper. A coating liquid consisting of 25 parts of diphenylmethane diisocyanate, 85.0 parts of polyethylene adipate sebacate (average molecular weight 85) having hydroxyl groups at both ends (average molecular weight 85), and 2800 parts of toluene was applied onto this laminate (B-1) using bar coater No. 5. The first layer was coated with a methacrylonitrile/n-butoxyethyl methacrylate (90/10 weight ratio) copolymer (ηsp/C1.84dl) and dried at 130°C for 3 minutes to form a first layer with a film thickness of 0.3μ. /g, C=0.5g/dl, dimethylformamide solution, 30°C) 10 parts, 45 parts of methyl ethyl ketone, and 45 parts of cyclohexanone were coated using a bar coater No. 16, and dried by heating at 130°C for 3 minutes. and film thickness 2.0
A laminate (A-7) having a transparent protective layer of μm was obtained. The visible light transmittance of this laminate (A-7) is 56%
The infrared reflectance was 82%. In addition, the wear resistance according to the clock meter test is over 3000 times.
In the salt spray test, stains appeared after 28 days. Comparative Example 4 Polymethacrylonitrile (ηsp/C=1.0,
A coating solution consisting of 10 parts of 0.5% DMF solution (20°C), 45 parts of methyl ethyl ketone, and 45 parts of cyclohexanone was applied using bar coater No. 16 in the same manner as in Example 1 to form a transparent protective film with a thickness of 2.0 μm. A laminate (A-8) having layers was obtained. Although the laminate A-8 had an infrared reflectance of 86%, a visible light transmittance of 57%, and scratch resistance of more than 2,500 times, stains appeared in one day in the salt spray test. Example 6 10 parts of polybutadiene diol (Nisso PB-G1000 (manufactured by Nippon Soda KK)) was placed on the laminate (B-2) used in Example 2, 2.2.4-/2.2.4-
A coating solution consisting of 2.1 parts of trimethylhexamethylene diisocyanate (50/50) and 80 parts of toluene was coated using bar coater No. 5, and dried at 130°C for 3 minutes to form a first layer with a film thickness of 0.3μ. Acrylonitrile polymer (ηsp/C1.95
dl/g, C = 0.5 g/dl, 10 parts of dimethylformamide solution (30°C) and 90 parts of dimethylformamide were coated using a bar coater No. 16, and dried by heating at 180°C for 3 minutes to form a film. Laminated body (A-
9) was obtained. The infrared reflectance of the laminate A-9 was 86%, and the visible light transmittance was 63%. Furthermore, the wear resistance measured by clock meter was more than 3800 times, and there were no problems in practical use. In the salt spray test, stains appeared after 13 days and a significant improvement in stain resistance was observed. Example 7 Biaxially stretched polyethylene terephthalate film with light transmittance (500 μm) of 86% and film thickness of 50 μm
A laminate (B-4) having selective light transmittance was obtained by laminating aluminum layers of 100 Å. The aluminum layer was provided by vacuum deposition using a resistance heating method. This laminate was coated with a coating liquid consisting of 26.2 parts of 4,4'-dicyclohexylmethane diisocyanate, 6.7 parts of N-ethyldiethanolamine, 3.1 parts of ethylene glycol, 50 parts of cyclohexanone, and 50 parts of methyl ethyl ketone using a bar coater No. 10. Dry at 130℃ for 3 minutes, film thickness 0.3
A coating solution consisting of 10 parts of methacrylonitrile polymer (ηsp/C1.0dl/g, C=0.5g/dl, dimethylformamide solution, 30°C), 45 parts of methyl ethyl ketone, and 45 parts of cyclohexanone is applied. was coated using bar coater No. 16 and dried at 130° C. for 3 minutes to obtain a laminate having a transparent protective layer with a thickness of 2.0 μm. The laminate had an abrasion resistance of more than 3000 cycles in a Crotchmeter test, and stains appeared after 11 days in a salt spray test. Comparative Example 5 A coating solution consisting of 10 parts of polymethacrylonitrile (ηsp/C=1.0, 0.5% dimethylformamide solution, 30°C), 45 parts of methyl ethyl ketone, and 45 parts of cyclohexanone was applied to the laminate (B-4) obtained in Example 13. was coated using bar coater No. 16 in the same manner as in Example 1 to obtain a laminate having a transparent protective layer with a thickness of 2.0 μm. This laminate had abrasion resistance of more than 2,500 cycles, but stains appeared in one day in the salt spray test. Example 8 A biaxially stretched polyethylene terephthalate film with a light transmittance (500 μm) of 86% and a film thickness of 50 μm, a zirconium oxide layer with a thickness of 300 Å, and an alloy layer of silver and copper with a thickness of 195 Å (92 wt% silver, 8 wt% copper) ) and 280Å
zirconium oxide layers were sequentially laminated to obtain a laminate (B-5) having selective light transmittance. Both zirconium oxide layers were coated with a solution consisting of 3 parts of tetrabutyl zirconate and 97 parts of isopropyl alcohol using a bar coater, and heated at 120°C.
It was provided by heat treatment for 3 minutes. The silver/copper alloy layer was formed by vacuum evaporation using a resistance heating method using an alloy containing 70 wt% silver and 30 wt% copper. On this laminate (B-5), 16.8 parts of hexamethylene diisocyanate, ethylene glycol
A coating solution consisting of 6.2 parts of cyclohexanone, 105 parts of cyclohexanone, and 105 parts of methyl ethyl ketone was coated using bar coater No. 5, and dried at 130°C for 3 minutes to form a first layer with a film thickness of 0.3μ. (ηsp/C1.0dl/
A coating solution consisting of 10 parts of dimethylformamide solution, 45 parts of methyl ethyl ketone, and 45 parts of cyclohexanone was coated using a bar coater No. 16, and the temperature was 130 °C.
After drying for 3 minutes, a laminate (A-10) having a transparent protective layer with a thickness of 2.0 μm was obtained. The infrared reflectance of the laminate was 84%, and the visible light transmittance was 54%. In addition, the abrasion resistance was measured using a clock meter over 3,000 cycles, and stains appeared after 10 days in a salt spray test. Example 9 A 150A thick zirconium oxide layer, a 190A thick silver layer, and a 250A thick zirconium oxide layer were sequentially laminated on a biaxially stretched polyethylene terephthalate film with a light transmittance (500μm) of 86% and a film thickness of 25μm, and selective light was applied. A transparent laminate (B-6) was obtained. The zirconium oxide layer was provided by reactive sputtering of zirconium. A coating liquid consisting of 18.8 parts of xylylene diisocyanate, 11.9 parts of N-methyldiethanolamine, 300 parts of cyclohexanone, and 300 parts of methyl ethyl ketone was coated on this laminate (B-2) using a bar coater No. 5, and the temperature was 130°C. 3
A first layer with a film thickness of 0.2μ was applied by drying for 10 minutes, and then the methacrylonitrile polymer 10 used in Example 1 was applied.
parts, 45 parts of methyl ethyl ketone, cyclohexanone
Coating liquid consisting of 45 parts is applied to bar coater No.16.
A laminate (A
−11) was obtained. The infrared reflectance of the laminate A-3 was 84%, and the visible light transmittance was 53%. In addition, the wear resistance measured by clock meter was over 3000 times, and there was no problem in practical use. When evaluated using a salt spray tester, spot-like stains appeared after 25 days, and a marked improvement in stain resistance was observed. Comparative Example 6 Laminate B-6 was coated with polymethacrylonitrile under the same conditions as Comparative Example 1 to obtain a laminate (A-11) with transparent protection having a thickness of 2 μm. The infrared reflectance of the laminate (A-11) was 82%,
The visible light transmittance was 52%. However, in the salt spray tester, stains appeared within one day.

Claims (1)

[Claims] 1. A metal thin film layer and/or a metal oxide thin film layer is laminated on at least one side of a transparent molded substrate, optionally in combination with a high refractive index thin film layer, and further two layers In a selective light transmitting laminate in which protective layers are sequentially laminated, the first layer of the protective layer is made of linear polyurethane, and the second layer is made of the following general formula [] [In the formula, R represents a hydrogen atom or a methyl group] A selective light-transmitting laminate comprising a polymer whose main structural unit is a structural unit represented by the following.