JPS6226309B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a coated selective light transmitting laminate, and more particularly to a selective light transmitting laminate having high visible light transmittance and infrared reflectance and excellent abrasion resistance. 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 in solar energy collectors, water heaters,
Possible uses include greenhouses, building windows, frozen and refrigerated cases, vehicle and aircraft windows, etc.
The function of transparent insulating windows that utilize solar energy and prevent energy dissipation will become increasingly important in the future. In order to achieve this objective, it is strongly desired that homogeneous, high-performance selective light transmitting laminates be industrially available at low cost and in large quantities. Conventionally, films (laminates) having the above-mentioned properties include: 1. Metal thin films such as gold, copper, silver, and palladium; 2. Compound semiconductor films such as indium oxide, tin oxide, and copper iodide; 3. Gold, copper, It is known that the transparency in a certain wavelength range is improved by a combination of a metal thin film such as silver or palladium and other elements. In particular, a typical structure of the above 3 is a laminate in which a metal thin film layer is sandwiched between transparent high refractive index thin film layers, such as Bi formed by vacuum evaporation, reactive evaporation, chemical coating method or sputtering method. ₂ O ₃ /Au/Bi ₂ O ₃ , ZnS/Ag/
Laminated bodies such as ZnS or 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 having selective light transmittance as a transparent heat insulating window, it is necessary to have not only the inherent performance such as visible light transmittance and infrared light reflectance, but also its abrasion resistance and durability (light resistance, Practical performance such as heat resistance) is also required. However, in general, laminated extremely thin metal films or metal oxide thin films as described above often have insufficient abrasion resistance.For example, when used inside double-glazed glass, there are few problems, but when used directly When exposed to the outside, it is necessary to provide a protective layer. The present inventors investigated various protective coating agents in order to improve the practicality of the laminate and found that many protective coating agents can improve wear resistance, but at the same time, they have a high ability to reflect infrared rays, that is, heat ray reflection. It was discovered that this significantly reduced performance. 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 becomes high, and therefore the reflectivity for infrared light is significantly reduced. When a general protective coating agent is used, when the thickness of the protective layer is 1.5 to 2.0 μm, a considerable decrease in infrared reflectivity cannot be avoided. A protective layer 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, coatings for general paints cannot be expected to have a sufficient function as a protective layer if the film thickness is less than 0.3 μm to avoid interference. As a result of intensive research in order to solve such problems, the inventors of the present invention have developed a highly wear-resistant protective layer,
It has been discovered that such problems can be solved at once by using a protective layer with a low infrared absorption rate, and the present invention has been achieved. That is, the invention is based on the following: 1. On a selective light transmitting laminate formed by laminating a high refractive index dielectric thin film layer and a metal thin film layer on at least one side of a transparent molded substrate, a film thickness of 2 μm measured by reflected infrared light is obtained. A transparent protective layer (A) with an average infrared absorption rate of 35% or less in the wavelength range of 3 to 25 μm, and a wear-resistant transparent layer with a haze value of 15% or less when tested with 500 g of sand on top of the protective layer (A). A laminate in which protective layers (B) are sequentially laminated, wherein (a) the sum of the thickness of the protective layer (A) and the thickness of the protective layer (B) is greater than the upper limit of the interference film thickness; and (b) a coated laminate characterized in that the film thickness of the protective layer (B) is less than or equal to the upper limit of the interference film thickness; The coated laminate according to item 1 above, which is a three-dimensional polymer coating layer mainly composed of a meth)acryloyl compound. The advantages brought about by coating two layers to a specific thickness as in the present invention will be explained in detail in comparison with the case where each layer is coated alone. (1) If the protective layer (B) is provided alone with a thickness greater than the upper limit of the interference film thickness, the infrared absorption rate will be extremely high and the heat ray reflection ability will be reduced even if sufficient wear resistance is achieved. It will drop significantly. (2) When the protective layer (B) is provided alone with a thickness of less than the lower limit of the interference film thickness, for example, about 0.1 to 0.2 μm, the heat ray reflecting ability will not be reduced. However, when using a normal protective coating agent, it will not function as a protective layer unless the film thickness is at least 1.5 to 2 μm, and even if the coating agent has a high degree of wear resistance (AR coating agent), it will not function as a protective layer. A thickness of about 0.1 to 0.2 μm is not sufficient for harsh usage environments. (3) When the protective layer (A) is provided alone, wear resistance is insufficient not only when the film thickness is below the lower limit of the interference film thickness, but even when it is above the upper limit, and it cannot be used under severe usage conditions. It's unbearable. (4) In contrast, according to the two-layer structure of the present invention,
It is possible to set a film thickness that suppresses absorption in the infrared region and exhibits wear resistance without causing interference. For example, by setting the thickness of the transparent protective layer (A) to 1.4 μm and the thickness of the wear-resistant protective layer (B) to 0.7 μm, the total thickness of the protective layer will be 2.1 μm, without causing any interference. , and wear-resistant protective layer (B)
The film thickness can also be set to a film thickness that sufficiently exhibits abrasion resistance, and therefore a laminate with improved abrasion resistance can be obtained without sacrificing heat ray reflective ability. The transparent molded substrate serving as the base of the selectively transparent laminate used in the present invention may be either an organic-based inorganic molded product or a composite molded product thereof. Examples of organic molded products include polyethylene terephthalate resin, polyethylene naphthalate resin, polybutylene terephthalate resin,
Examples include molded products of polycarbonate resin, polyvinyl chloride resin, acrylic resin, polyamide 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. Examples of the high refractive index dielectric thin film layer used in the present invention include thin film layers made of titanium dioxide, titanium oxide, bismuth oxide, zinc sulfide, tin oxide, indium oxide, and the like. It is effective for the high refractive index dielectric thin film layer to have a refractive index of 1.6 or more, preferably 1.8 or more for visible light, and a visible light transmittance of 80% or more, preferably 90% or more. The film thickness is 50 to 600 Å, preferably 120 to 400 Å. These thin film layers can also be applied by sputtering, ion plating, vacuum deposition or chemical coating. As an example of a chemical coating, a thin layer of titanium oxide can be provided, for example by applying an organic solution of a solute based on an alkyl titanate. By adjusting the conditions for alkyl titanate film formation, those in which 0.1 to 10% by weight of alkyl groups remain in the thin film layer have improved adhesion with metal layers or organic films, and can be used in a wide wavelength range. It is a selective light transmitting film with excellent transparency throughout the film, and is particularly preferred. Materials for the metal thin film layer constituting the selectively transparent film used in the present invention include silver, gold, copper,
Aluminum, nickel, palladium, tin and alloys or mixtures thereof are used. In particular, silver, gold, copper, and alloys or mixtures thereof are preferably used. The film thickness is 30 to 500 Å, preferably 50 to 200 Å, because this range is suitable when both the transparency and heat insulation of the window are taken into consideration. Examples of methods for forming the metal thin film layer include vacuum evaporation, cathode sputtering, plasma spraying, vapor phase plating, chemical plating, electroplating, and combinations thereof. The vacuum evaporation method is advantageous in that vapor deposition is performed efficiently, and the sputtering method is advantageous in that temporal fluctuations in the composition of the metal thin film can be reduced. 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 100 to 200
Metal thin film 100-200 Å, which is a silver and copper alloy layer with a copper content of 0.5-15% by weight in the alloy.
It is a metal thin film consisting of two layers: a silver layer of 100 Å and a copper layer of 5 to 50 Å. The transparent protective layer (A) in the present invention is a transparent material with a low infrared absorption rate, with an average infrared absorption rate of 35% or less, preferably 30% or less, in the range of 3 to 25 μm when measured with a film thickness of 2 μm. It is a protective layer. Here, the average infrared absorption rate is 300〓(27℃) for a protective layer with a thickness of 2μm.
When irradiated with infrared rays emitted from a black body,
It is defined as the proportion of radiant energy in the wavelength range of 3 to 25 μm that is absorbed by the protective layer. The measurement method will be described later, but the wavelength dependence of the absorbance is measured using reflected infrared light using a test piece in which a 2 μm thick protective layer is provided on a deposited silver film. The absorption rate obtained and 300〓(27
3 to 25, taking into account the radiant energy intensity at
It is obtained by integrating in the μm wavelength range. Materials used for such transparent protective layers include, for example, poly(meth)acrylate paints; saturated polyester paints; ethylene-vinyl acetate copolymer paints; polystyrene paints; polyvinyl formal or polyvinyl butyral paints; polyvinyl chloride, vinyl acetate. -Vinyl chloride-based paints such as vinyl chloride copolymer or vinyl chloride-vinylidene chloride; alcohol-soluble nylon; and polyolefins such as polyethylene or polypropylene. In particular, poly(meth)acrylate paints mainly composed of (meth)acrylic acid esters of higher aliphatic alcohols such as 2-ethylhexyl alcohol and butyl alcohol; linear or branched paints such as ethylene glycol, tetramethylene glycol, neopentyl glycol, etc. Mainly from aliphatic diols such as adipic acid, aliphatic dicarboxylic acids such as sebacic acid, or ε-oxycaproic acid, certain saturated polyester resin paints; ethylene-vinyl acetate copolymer paints; acrylonitrile-
Alcohol-soluble nylon made of styrene copolymer; polystyrene; aliphatic polyamide copolymer and the like are preferred because they have low absorption in the infrared region.
Although polyethylene and polypropylene require special techniques such as plasma coating to form a thin film coating, they are preferably used because of their low infrared absorption. There are no particular limitations on the coating method for these protective layers;
For example, a solution diluted with a solvent may be applied, or a general coating method such as a dipping method, a spray method, a spinner method, or a machine coating method such as gravure coating can be applied as is. Wear-resistant transparent protective layer (B) used in the present invention
has a haze value of 15% or less, preferably 10% or less in a sand drop test using 500 g of carborundum. However, the haze value in this case is a value measured with a sufficiently thick film so that changes in film thickness do not affect the haze value. Such wear-resistant transparent protective layers include three-dimensional crosslinked films such as polyfunctional poly(meth)acrylate paints and diethylene glycol bisallyl carbonate; three-dimensional crosslinked films obtained by heating and curing thermosetting resin paints such as melamine resin paints; Crosslinked film: Examples include films formed by three-dimensionally crosslinking silicon compounds such as polysilicic acid and organopolysiloxane, and vapor deposits of inorganic glass and SiO ₂ . Many of these wear-resistant protective layers are three-dimensionally crosslinked, and the method of forming the film is not particularly limited, but generally a monomer is applied and then a polymerization reaction is carried out to form the film. These coating methods are not particularly limited; for example, a solution diluted with a solvent may be applied, or a general coating method such as a dipping method, a spray method, a spinner method, or a machine coating method such as gravure coating can be directly applied. Furthermore, the method for carrying out the polymerization reaction differs depending on the monomer. For example, in the case of polyfunctional vinyl-based monomers, thermal polymerization initiators or photopolymerization initiators are added and the polymerization is performed by heating or photopolymerization, and thermosetting resin paints, polysilicic acid, organopolysiloxane, etc. Three-dimensional crosslinked films of condensation systems such as
Forms a film. Inorganic glass, SiO ₂ deposits, etc. are formed into a film by a method such as a vapor deposition method, an ion plating method, or a sputtering method. As such a wear-resistant coating agent, a polyfunctional (meth)acrylate having a functional group number of 3 to 6 (i.e.,
A three-dimensional polymer coating layer mainly composed of (a compound having a large number of (meth)acryloyl groups) is particularly preferably used for the following reasons. (a) It exhibits high hardness because it forms a high-order network structure based on a polyfunctional acrylate polymer.
Therefore, it functions as a protective layer even if the film thickness is made sufficiently thin without reducing the heat ray reflecting ability. (b) Because it uses radical reactions, the reaction is fast and it can be cured at low temperatures. Therefore, the process can be easily made continuous, which is advantageous for long products. (c) Since it is an acrylate type, thermal polymerization using a radical initiator or photopolymerization using a sensitizer is also possible. Since the functional number thereof is increased, it is advantageous in many cases because it has air curability, that is, polymerizability in the presence of air. Such polyfunctional (meth)acrylates include (a) polyfunctional (meth)acrylates obtained by reacting polyfunctional polyols such as trimethylolpropane, tromethylolethane, and pentaerythritol with (meth)acrylic acid; and (b) trimellitic acid. , trimesic acid, pyromellitic acid, and 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate (iii) Polyfunctional (meth)acrylate obtained by the reaction of hexahydroxyether of hexamethylolmelamine, hydroxypropyl Cyanuric ring, isocyanuric ring obtained by reaction of ether, trishydroxyethyl isocyanurate, trishydroxypropyl isocyanurate, hydroxyethyl cyanurate, hydroxypropyl cyanurate, hexahydroxyethylmelamine, hexahydroxypropylmelamine, etc. and (meth)acrylate, etc. , (meth)acrylate containing a melamine ring, etc. are preferably used. Polymerization initiators used for such polyfunctional (meth)acrylates vary depending on the curing method; in the case of ultraviolet curing, benzoin ethers such as benzophenone, benzoin, benzoin methyl ether, and benzoin ethyl ether; benzyl, benzyl dimethyl ketal, and benzyl diethyl; Benzyl ketals such as ketal; 2-alkylanthraquinones; diacetyl, etc.; in the case of heat curing, azo compounds such as azobisisobutyronitrile; benzoyl peroxide, lauryl peroxide,
Examples include peroxides such as di-tert-butyl peroxide, dicumyl peroxide, and cumene hydroperoxide. When ultraviolet rays and heat are used together, polymerization initiators can also be used in combination. The amount used is usually based on the (meth)acrylic ester.
It ranges from 0.01 to 10% by weight. Furthermore, when using gamma rays, electron beams, or the like as a curing means, it is not necessarily necessary to add a polymerization initiator. Polymerization inhibitors as storage stabilizers are not necessarily required, but include, for example, hydroquinone, hydroquinone monomethyl ether, catechol, 2.6
-di-tert-butylphenol, N-nitrodiphenylamine, phenothiazine, etc., and usually 10 to 10% of the (meth)acrylic acid ester
1000ppm used. Further, the coating liquid may contain an ordinary vinyl monomer to the extent that it does not impair the abrasion resistance of the cured product of the (meth)acrylic acid ester represented by the above general formula and the excellent adhesion to the molded product. can. When the coating liquid is diluted with a solvent, the polyester molded article coated with the coating liquid can be polymerized by first removing the solvent by heating or the like, and if it does not contain a solvent, it can be directly polymerized. Polymerization is carried out using ultraviolet rays, gamma rays, heat, electron beams, or a combination thereof, preferably ultraviolet rays,
heat or a combination thereof. Most esters are air-curable (curing is not inhibited by oxygen in the air), so during polymerization, inert gas such as nitrogen is used, pressure is reduced, or air is cured using a film or glass. In many cases, there is no need to shut it off. Furthermore, when selecting the two types of protective layers (A) and (B), it is generally better that the layers (A) and (B) have a lower layer capacity.
In other words, it is generally better to have a larger difference in solubility parameters between (A) and (B). The reason is that when coating the (B) layer on the (A) layer, if the (B) layer is compatible with the (A) layer, this will lead to a decrease in abrasion resistance. Therefore, a suitable combination is, for example, using a polyfunctional acrylate three-dimensional polymer coating layer for the (B) layer and polystyrene for the (A) layer.
Examples include cases where acrylonitrile-styrene copolymer, polyester resin, polyethylene, polypropylene, polyamide, etc. are used. For the same reason, the coating solvent used when forming the layer (B) is preferably one that does not easily dissolve the layer (A). The thickness of the transparent protective layer (A) and wear-resistant transparent protective layer (B) used in the present invention is such that the sum of the thickness of (A) and the thickness of (B) is greater than the interference thickness limit; And the film thickness of (B) is less than or equal to the upper limit of the interference film thickness. Here, the interference film thickness is the film thickness that produces a rainbow-colored interference pattern when exposed to visible light, and 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.
That's about it. However, the interference effect does not change rapidly at 0.3 μm, but gradually becomes darker as the film thickness increases, and as the film thickness further increases, the interference effect appears. Therefore, if the sum of the film thicknesses of (A) and (B) is within the interference film thickness limit, interference will occur, which is not preferable. Also (A)
The upper limit of the sum of the film thicknesses (B) and (B) should be determined by considering the intended use, scratch resistance, infrared reflectance, etc., but if it is too large, the infrared absorption will be too high, so it should be set at 5 μm. , generally used in a range of 4 μm or less. Next, the film thickness of layer (B) is below the upper limit of the interference film thickness, but if it is too thick, the infrared absorption rate will generally be too high, so it is preferably 1.0 μm or less, particularly preferably 0.8 μm.
A range of m or less is used. (B) Layer thickness is 1.0μ
m or more, the difference between the infrared absorption of the two layers together with the (A) layer and the infrared absorption when the (B) layer is provided alone at the same thickness becomes small. The advantage of having two layers is reduced. The thickness of layer (B) is 0.05 μm or more, preferably 0.1 μm or more, and more preferably 0.2 μm.
It is used in the above range. If it is less than that, the (B) layer has no meaning as a wear-resistant protective layer. Further, in order to further enhance the effects of the present invention, the surface of the transparent high refractive index dielectric thin film layer may be treated with a silane coupling agent, coated with an adhesive layer, etc. Furthermore, it is not at all prohibited to use surface treatments such as coloring agents and ultraviolet absorbers in combination within a range that does not impair the effects of the present invention. When the laminate of the present invention is used as a heat ray reflective material, if water droplets adhere to the surface of the laminate, the effect will be significantly impaired, so in order to reduce this, the surface should be made hydrophilic or water repellent. There is no problem with processing such as oil treatment. By providing the above-mentioned protective layer, not only the scratch resistance can be significantly improved without impairing the heat ray reflection ability, but also the light resistance can be improved by blocking moisture and ultraviolet rays. In addition to being used as a transparent heat insulating film, the thus obtained laminate can be used for applications utilizing its conductivity, such as electrodes for liquid crystal displays, electrodes for electroluminescent materials, electrodes for photoconductive photoreceptors, 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. 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 EPI-type infrared spectrometer and measuring the reflectance of a slide glass with sufficiently thick (approx. 3000 Å) vacuum-deposited silver.
Unless otherwise specified, measurements were taken at 10μ 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). In addition, the sand drop test was performed on a transparent film with a film thickness of 3 μm or more.
A protective layer of 5 μm was provided and 500 g of carborantum was used, and the difference in haze value before and after the test was determined. For the clock meter test, a clock meter manufactured by Toyo Seiki was used. Using commercially available gauze, the sample surface was abraded back and forth under a load of 500 g/cm ² , and the number of back and forth movements until the metal layer began to wear was determined. The film thickness was measured using a digital electronic micrometer (model K351A) 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 dielectric thin film layer and a metal thin film layer, and its infrared reflectance is adjusted to a wavelength range of 3 to 25μ. Measure with. On the other hand, 300〓(27
0.2 μm of the energy radiated from a black body at
The product of the radiant energy and the infrared reflectance according to each wavelength is calculated every 0.2 μm, and the sum is determined in the wavelength range of 3 to 25 μm. 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 represents the total percentage of energy radiated from 300〓 (in the 3 to 25 μm range) that is reflected. If the metal layer is thicker than a certain thickness, it can be assumed that there is almost no infrared transmittance, so finding the difference in this normalized reflectance from 100 will represent the infrared absorbing ability of the protective layer used at that time.
This value is defined as the average infrared absorption rate. 3~25μm
The radiant energy in this region corresponds to about 85% of the total blackbody radiant energy of 300〓. The heat transmission coefficient was measured using HFM-MU model manufactured by Showa Denko. In addition, all "parts" in the examples are based on polymerization. Next, methods for synthesizing substances that are raw materials for the abrasion-resistant transparent protective layer (B) are illustrated below as synthesis methods A to E. Synthesis method A 82 g of 2-hydroxyethyl acrylate, 51 g of triethylamine and 25 mg of N-nitrosodiphenylamine are dissolved in 130 ml of dioxane. After dropping 37.1 g of trimellitic acid chloride in 40 ml of dioxane under stirring while keeping the temperature at 20-35°C,
React for 2 hours at room temperature. After separating the precipitated triethylamine hydrochloride, dioxane is distilled off under reduced pressure. The residue is extracted with ether, washed with a 0.5N aqueous HCl solution, and further washed with water. The ether layer was dried over magnesium sulfate and further concentrated to obtain a liquid acrylic ester (referred to as A-1). The infrared absorption spectrum of this product has the characteristic absorption of ester at 1730 cm ^-1 .
It showed C=C characteristic absorption at 1640 cm ^-1 and 1620 cm ^-1 . Similarly, acrylic acid ester (A-
2) was obtained. Synthesis method B Tris (2-hydroxyethyl) isocyanurate 522g, methacrylic acid 56.8g, concentrated sulfuric acid 0.6g,
Add 16 mg of phenothiazine and 120 ml of toluene to a stirrer.
The mixture was charged into a flask equipped with a water separator and reacted under reflux. The water produced by the reaction flowed into the system as an azeotrope with toluene. After 4 hours, almost the theoretical amount of water had flowed out, so the reaction system was cooled. After washing the reaction solution with an aqueous solution containing 2 wt% ammonia and 20 wt% ammonium sulfate, and then with an aqueous solution containing only 20 wt% ammonium sulfate,
Hytroquinone monomethyl ether in toluene layer
25 mg was added and the toluene was removed under reduced pressure. The obtained methacrylic ester (referred to as (B-1)) was crystallized after cooling. The yield was 72g. Infrared absorption spectrum is 1460cm ^-1 and 1690cm
Isocyanurate-based absorption near ^-1 , 1720cm
Absorption based on carbonyl of methacroyl group near ^-1 , absorption based on vinyl group near 1635 cm ^-1 , 1165
Absorption based on C-O-C near cm ^-1 was observed. 56.8g of the above methacrylic acid to 48.6g of acrylic acid
Acrylic ester (B-
2) was obtained. Synthesis method C 2-hydroxylethyl acrylate 125.4g
To a slurry mixture obtained by adding 55.3 g of cyanuric chloride to a solution consisting of 25 mg of N-nitrosodiphenylamine and 25 mg of N-nitrosodiphenylamine, 95.4 g of fine particles of soda carbonate were added with stirring at room temperature. Although the system immediately generated heat, it was stirred for 1 hour while being cooled to below 80°C. The reaction temperature was then raised to 95°C and stirring was continued at that temperature for 2 hours. After cooling, add 200ml of ethyl ether to the reaction mixture and separate the precipitate.
Washed 5 times with 100 ml of water. Magnesium sulfate 20
After dehydration, ether ether was distilled off. 105 g of a pale yellow liquid was obtained. This includes liquid chromatography, mass spelling,
Infrared absorption spectrum (IR) and elemental analysis revealed that tris(acroyloxyethyl)cyanurate (C-
1) was obtained. Synthesis method D 45.3 g of hexamethylolmelamine, 200 g of 2-hydroxyethyl acrylate, 500 mg of p-methoxyphenol and 8 g of concentrated sulfuric acid were stirred at 30°C for 10 hours. The resulting mixture was extracted with ethyl acetate/n-hexane, washed with saturated aqueous sodium bicarbonate solution, washed with water, and the organic layer was concentrated to obtain acrylic acid ester ((D-1). Synthesis method E: 184.4 parts of cyanuric chloride, 413 parts of dioxane A slurry was obtained by pouring the solution consisting of 1.0 parts into 600 parts of ice water with vigorous stirring. 316.2 g of diethanolamine was added dropwise into the slurry while externally cooling the reaction system to a temperature of 30°C or less. After the dropwise addition, Add several drops of phenolphthalein solution, gradually heat the reaction system to reflux temperature, and further reflux for 2 hours.
Time was maintained. During the heating and refluxing period, a solution consisting of 120 g of sodium hydroxide and 300 g of water was added dropwise while paying attention to coloration of phenolphthalein in the reaction system. The reaction mixture was then cooled and the solvent was removed to dryness. The reaction mixture was extracted with n-butanol and directly recrystallized to obtain 240 g of hexa(hydroxyethyl)melamine in the form of needles. Hexakis (hydroxyethyl) melamine 39.1
0.03 g of g and p-methoxyphenol were dissolved in 100 g of acrylic acid, 80 parts of acrylic anhydride was added dropwise to the solution at room temperature while stirring, and then 40 g of p-methoxyphenol was dissolved in 100 g of acrylic acid.
The reaction was carried out at 50°C to 50°C for 5 hours. The reaction mass was poured into 1200 g of water under vigorous stirring and the organic layer was separated. Add 200 g of ethyl acetate to the organic layer, wash twice with aqueous sodium carbonate solution, and then wash with water 3 times.
The organic layer was separated several times, 30 g of magnesium sulfate was added to the organic layer, and after drying, the solvent was distilled off under reduced pressure to obtain a viscous liquid of hexakis(acryloyloxyethyl)melamine (E-1). Hexakis(2-acryloyloxypropyl)melamine (E-2) was obtained in the same manner using 400 g of diisopropanolamine instead of 316.2 g of diethanolamine. Example 1 A biaxially stretched polyethylene terephthalate film with a light transmittance of 86% and a film thickness of 50 μm, a titanium oxide thin film layer with a thickness of 300 Å, and a thin film layer of a silver and copper alloy with a thickness of 170 Å (92% by weight of silver, 8% by weight of copper) %) and 280 Å titanium oxide thin film layers were sequentially laminated to obtain a laminate having selective light transmittance. The titanium oxide thin film layer is made of 3 parts of tetrabutyl titanate and 97 parts of isopropyl alcohol.
Apply a solution consisting of
Heat and set for 3 minutes. The metal thin film layer was formed using a silver-copper alloy (70% silver, 30% copper) and was vacuum deposited using a resistance heating method. A coating liquid consisting of 8 parts of SAN-H (Mitsubishi Monsanto chemical styrene-acrylonitrile copolymer) and 92 parts of methyl ethyl ketone was applied onto this laminate having selective light transmittance (laminated body ○A) using Percoater No. 20. coating at 120℃
A transparent protective layer with a thickness of 2.0 μm was obtained by drying for 3 minutes. Calculating the average infrared absorption rate of this protective layer is 21
A value of % was obtained. Next, apply the same coating liquid to Bar Coater No.12.
Coat the laminate ○a using
A protective layer (A) with a film thickness of 1.5 μm was obtained by drying for 30 minutes.
On top of this laminate, 10 parts of A-TMMT (tetramethylolmethane tetraacrylate) (haze value 1.2% by sand drop test at a film thickness of 3 μm) and ethylene glycol monoethyl ether (ethyl celsonbu) were added.
A coating solution consisting of 90 parts and 0.15 parts of benzyl dimethyl ketal was applied using a spinner, and 120 parts of
After the solvent was evaporated for 3 minutes at °C, ultraviolet rays were irradiated for 1 minute under a 2KW high-pressure mercury lamp 20cm long to obtain an abrasion-resistant transparent protective layer (B) made of A-TMMT with a thickness of 0.5μ. This laminate ○I/SAN-H (1.5μ)/A-
When a laminate made of TMMT (0.5μ) was subjected to a clock meter test, the metal layer still showed high scratch resistance even after 15,000 cycles. On the other hand, in the case of the laminate (○) without a protective layer, most of the metal layer was worn out after one or two times. Furthermore, the average infrared absorption rate of the laminate with this protective layer was 27%, and the heat transmission coefficient was 1.60, making it possible to obtain a laminate with low infrared absorption and high heat insulation performance. The transmittance at 500 mμ was 72%, showing excellent visible light transmission, and no interference was observed. Comparative Examples 1 to 5 The following various protective layers were provided on the laminate ○A with selective light transmission without a protective layer used in Example 1, and the average infrared absorption coefficient and heat transmission coefficient were measured as heat insulation performance. A clock meter test was also conducted to determine scratch resistance.

[Table] Transparent protective layer as shown in Comparative Example 1
SAN-H alone has excellent heat insulation performance but poor scratch resistance. On the other hand, as shown in Comparative Example 2, A-TMMT alone, which is an abrasion-resistant transparent protective layer, has excellent scratch resistance, but has a high average infrared absorption rate and poor heat insulation performance. Comparative Example 3 shows an example of A-TMMT 0.8μ, which has excellent scratch resistance and decent heat insulation performance, but the film thickness interferes with visible light, so interference fringes are not visible. It will be done. The film thickness is the point at which interference fringes appear.
A coating of 0.1 μm was applied to SAN-H and A-TMMT, and the results are shown in Comparative Examples 4 and 5.
Both have very good insulation performance, but the scratch resistance of SAN-H is very poor, and A-
In the case of TMMT, this cannot be said to be sufficient. Example 2 A biaxially stretched polyethylene terephthalate film with a transmittance of 86% and a thickness of 50 μm, a titanium oxide thin film layer with a thickness of 300 Å, and a thin film layer of silver and copper with a thickness of 170 Å (8% by weight of copper, 92% by weight of silver). and a titanium oxide thin film layer with a thickness of 300 Å were sequentially laminated to form a transparent laminate having selective light transmittance on the film. The titanium oxide layer was formed by low-temperature sputtering using a target formed from commercially available high-purity titanium oxide powder. The sputtering conditions are as follows: After the vacuum chamber is sufficiently evacuated to high vacuum (5×10 ^-6 Torr), Ar
Gas was introduced until the pressure reached 5×10 ⁻³ torr, and a titanium oxide thin film layer was formed using a high frequency electric field. The high frequency sputtering output was 500 W, the distance between the sputtered part and the target was 10 cm, and a titanium oxide thin film layer with a thickness of 300 Å was obtained in a sputtering time of 20 minutes. A thin film layer of silver and copper was provided in the same manner as in Example 1. On this laminate (laminated body ○○), as layer A, 1.5μ of polystyrene (Styron 666, K-27 manufactured by Asahi Dow) with an average infrared absorption rate of 20% was coated using toluene as a solvent. On top of that, hexakis (2-
acryloyloxypropyl) melamine (E-
2) (Sand falling test 1.0) was coated with ethyl cellosolve as a solvent, and A-TMMT of Example 1 was coated.
Dry in the same manner as above, and cure by irradiating with ultraviolet rays.
A protective layer with a film thickness of 0.5μ was obtained. This laminate has an average infrared absorption rate of 28%, a heat transmission coefficient of 1.61, and has excellent insulation performance.It has also been tested over 15,000 times on a clock meter, and has very high scratch resistance. The visible light transmittance was also excellent at 72%, and no interference fringes were observed. Example 3 Instead of the 170 Å silver and copper alloy of Example 1, a 170 Å thin film layer (silver) made of a 170 Å silver and gold alloy was used.
95% by weight and 5% by weight of gold), a laminate ○c was formed instead. A thin film layer made of an alloy of silver and gold was provided by a sputtering method. On top of this laminate ○C, 1.5μ of SAN-H described in Example 1 was coated as layer A, and on top of this, tris(acroyloxyethyl) cyanurate (C-1) described in synthesis method C was coated as layer B. ) (Sand Drop Test 1.5) was coated with isopropyl alcohol as a solvent and cured by UV irradiation in the same manner as in Example 1 to obtain a film thickness of 0.5μ. This laminate has an average infrared absorption rate of 28%, a heat transmission coefficient of 1.60, and has excellent heat insulation performance.It has also been tested over 13,000 times on a clock meter, resulting in a protective layer with extremely high scratch resistance. Also 500mμ
The visible light transmittance was 71%, and no interference fringes were observed. Examples 4 to 12 Laminated bodies having various selective light transmittances were prepared and their scratch resistance and heat insulation performance were measured. In all cases, excellent scratch resistance and heat insulation performance were exhibited. Unless otherwise specified, benzyl dimethyl ketal was added to the wear-resistant protective layer (B) in an amount of 2 wt % based on the resin content, and the layer was cured in the same manner as in Example 1.

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Claims (1)

[Scope of Claims] 1. On a selective light transmitting laminate formed by laminating a high refractive index dielectric thin film layer and a metal thin film layer on at least one side of a transparent molded substrate, a film thickness of 2
A transparent protective layer (A) having an average infrared absorption rate of 35% or less in the wavelength range of 3 to 25 μm when measured in μm;
Furthermore, a laminate in which a wear-resistant transparent protective layer (B) having a haze value of 15% or less as determined by a 500 g falling sand test is successively laminated on the protective layer (A), wherein (a) the protective layer (A) The sum of the film thickness and the film thickness of the protective layer (B) is thicker than the upper limit of the interference film thickness, and (b) the film thickness of the protective layer (B) is less than or equal to the upper limit of the interference film thickness. coated laminate. 2. The coated laminate according to claim 1, wherein the wear-resistant transparent protective layer (B) is a three-dimensional polymer coating layer mainly composed of a poly(meth)acryloyl compound.