JP2882725B2 - UV absorbing thermal insulation glass - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coated heat ray shielding glass mainly used for a window glass of a vehicle such as an automobile, a building or the like, which shields the direct sunlight and reduces glare of the direct sunlight. The present invention relates to a useful ultraviolet-absorbing heat-insulating glass capable of improving the comfortability and having an ultraviolet-shielding property, thereby preventing deterioration of an interior material due to ultraviolet rays.

[0002]

2. Description of the Related Art As a heat ray reflective glass used for the purpose of cutting off solar energy and mainly reducing a cooling load, and a low radiation glass for improving a heating efficiency, it has a high transmittance in a visible region and a high transmittance in an infrared region. As an article having high reflection, a structure of dielectric / silver / dielectric has been proposed. For example, in Japanese Patent Application Laid-Open No. 63-239043, ZnO / Ag / ZnO
/ Ag / ZnO, an infrared reflective article having a visible light transmittance of 60% or more has been proposed. Also, JP-A-2-111644 discloses an IT
Insulated laminated glass with a neutral color of O / Ag / ITO / Ag / ITO has been proposed.

[0003] For example, as a method of shielding ultraviolet rays, a method of coating ZnO on a substrate is common, and an ultraviolet absorbing substrate in which an ultraviolet absorbent is mixed with the substrate has also been proposed.

[0004]

Problems to be Solved by the Invention As described above, since the heat ray shielding article and the infrared reflecting article containing a silver-based film reflect solar energy and radiant energy, the cooling load and the heating load can be reduced. Is very effective, but the silver-based film is particularly susceptible to deterioration due to moisture and moisture, and due to the moisture and moisture, the silver is aggregated and the shielding performance is not sufficiently exhibited, and the adhesion strength is reduced. Therefore, it cannot be used as a veneer and must be combined or processed into multiple layers. Further, since the shielding effect against ultraviolet rays is not sufficient, it is necessary to use a laminated glass to provide an ultraviolet shielding effect.

Further, since the ultraviolet ray absorbing substrate has no effect of heat ray reflection or infrared ray reflection, it is necessary to laminate the above-mentioned reflection film on the substrate in order to provide the effect, and it cannot be used as a single plate. . Furthermore, recently, the influence of ultraviolet rays due to the ozone layer destruction is becoming important together with the effective use of solar energy. From this point, ultraviolet shielding is also important in addition to conventional solar control, which is effective use of solar energy.

As the solar control, the above-mentioned silver-based multilayer structure has a high visible light transmittance while maintaining high heat rays,
Because of its high infrared reflection performance, it is often used for architectural and heat insulating glass for vehicles, low radiation glass, transparent heating elements, electromagnetic wave shielding, etc., but since the silver-based film is significantly deteriorated by moisture such as humidity, There is a problem that even if a protective film having a considerable thickness is laminated, sufficient durability cannot be obtained. In addition, it cannot be used as a veneer from the viewpoint of adhesion, and must be treated in a combined or multilayered manner.From the viewpoint of durability, the time required to perform these treatments must be as short as possible, and the humidity, It was difficult to handle, requiring strict control of moisture.

As an ultraviolet shielding film, a ZnO film is generally used and commercialized. However, when the ultraviolet shielding performance is improved, the ZnO film is oriented in a columnar shape and is very easily ionized. Because the durability is extremely weak,
The place where it was used was very limited. For this reason, there has been a problem that it cannot be used for architectural purposes and vehicles unless it is combined or processed into multiple layers.

[0008]

SUMMARY OF THE INVENTION The present invention has been made in view of the above points, and uses at least a noble metal-based thin film, for example, a silver-based film having sufficient heat ray shielding performance and infrared reflection performance. By skillfully laminating and combining, for example, an acrylic resin and a silicone-based hard coating resin having ultraviolet shielding performance on the laminated body, the above-mentioned problems such as low durability and abrasion resistance can be significantly improved. Although it is a multilayer film containing at least a noble metal-based thin film, it can be used as a single plate, and the functions of ultraviolet shielding, heat shielding, and infrared reflection, which could not obtain sufficient performance with each structure alone, simultaneously and sufficiently An object of the present invention is to provide a single-panel, highly durable ultraviolet-absorbing heat-insulating glass useful for architecture and vehicles that can be developed.

That is, the present invention relates to a synthetic resin system in which a multilayer film containing at least one noble metal thin film is formed on a transparent glass substrate, and a fluorescent whitening agent and an ultraviolet absorber are dissolved and added. The method is characterized in that a primer liquid is applied and cured by heating, and then a silicone-based hardcoat solution in which a siloxane prepolymer is dissolved in an organic solvent is applied and cured by heating to be sequentially coated. And UV absorbing heat insulating glass.

[0010] Further, the multilayer film containing one or more noble metal-based thin films is a three to seven-layer film formed by sequentially laminating a dielectric, a noble metal or an alloy thereof, a metal, and a dielectric, or a repetitive lamination thereof. The above-mentioned ultraviolet absorbing heat insulating glass, characterized in that: Further, the noble metal-based thin film is Ag, A
The ultraviolet absorbing heat insulating glass described above, which is made of u, Cu, Pt or an alloy thereof. Further, the dielectric of the multilayer film is made of Si, Ti, Sn, Al, Cr, SUS, Ta, Zn, In, Si
The ultraviolet absorbing heat-insulating glass as described above, which is an oxide, nitride or nitrogen oxide film of C or an alloy thereof.

Further, the present invention provides the above-mentioned ultraviolet absorbing heat insulating glass, wherein the synthetic resin primer liquid is an acrylic solution containing a silicone component. Here, the heat ray shielding and the infrared reflection are made into a multilayer laminate of dielectric / silver alloy film / dielectric, for example, by laminating a five-layer system of ITO / silver / ITO / silver / ITO on a transparent substrate. This is because a heat ray shielding film and an infrared reflecting film having a high visible light transmittance and a remarkably high reflectance in a near-infrared to long wavelength infrared region can be obtained. Films and the like are also preferable because they have high transparency and excellent durability, but their properties are inferior to those of the above-mentioned silver-based films.

[0012] Further, titanium nitride or the like, which is a normal solar control film, has a low visible light transmittance. However, its characteristics are lower than those of a silver-based film, and a silver-based laminate is used for this purpose. Is the best one. In addition, an ultraviolet-ray shielding film was formed by applying an acrylic-based primer coating film containing mainly a silicone component in which a fluorescent whitening agent and an ultraviolet absorber were dissolved, and applying a silicon-based hard coat to the film as described above. By doing so, the durability of the above-mentioned silver-based noble metal-based multilayer film, in particular, the moisture resistance, chemical resistance, and abrasion resistance are greatly improved. For example, a method such as sputtering and vapor deposition of this ultraviolet shielding film is used. In the case where a ZnO film is stacked, ZnO, which is an amphoteric oxide, is used.
This is because the membrane is particularly vulnerable to acidic solutions and cannot be used as a single plate.

Further, in the present invention, preferably, a transparent dielectric material having a refractive index of about 2.0 from a transparent substrate is about 40 nm, and a silver-based film 10-15.
about 40 nm transparent dielectric with a refractive index of about 2.0 nm or about 40 nm with a refractive index of about 2.0 from a transparent substrate, about 10 to 15 nm of a silver-based film, and about 70 to 80 of a transparent dielectric with a refractive index of about 2.0
about 400 nm, a transparent dielectric with a refractive index of about 2.0 nm, an acrylic primer containing a silicone component dissolved and added with a fluorescent whitening agent and an ultraviolet absorber. The reason for the system hard coating is that the film thickness configuration of this level is the condition that the visible light transmittance becomes the highest as a result of utilizing thin-film interference for heat ray shielding and infrared reflection, This is because infrared reflection and ultraviolet shielding are sufficient, and in order to fully satisfy each shielding performance, visible light transmittance is 65% or more, solar radiation transmittance is 60% or less, emissivity is 0.15 or less, transmittance of 370nm. 10% or less is desirable, more preferably 70% or more of visible light transmittance, and 55% of solar radiation transmittance
Hereinafter, the emissivity is 0.1 or less, and the transmittance at 370 nm is 5% or less.

More recently, solar control has been used to reduce the cooling load by a method of shielding the entire solar energy with a relatively low visible light transmittance, whereas a relatively high transmittance has been used to reduce the cooling load. Doing Sunbelt Lo
w-E is mainly provided for warm regions, but in this case, the dielectric / silver double-layer glass is used, and the ultraviolet ray shielding performance is relatively low. Further, particularly in a warm region, there is a high demand for ultraviolet shielding, and there is a great demand for the above-mentioned glass having a single-plate ultraviolet shielding, and the present invention is a very effective means for these.

The substrate is not limited to inorganic matter, but may be organic or transparent, and may be colorless or colored. Needless to say, it can be used not only as a single plate, but also as various plate glass products such as double-glazed glass or laminated glass.

[0016]

As described above, the ultraviolet absorbing heat insulating glass of the present invention is a primer obtained by dissolving and adding a fluorescent whitening agent and an ultraviolet absorber to a laminated film formed of a dielectric or the like including at least one noble metal thin film. By performing a coat and further performing a silicon-based hard coat as a protective film,
A laminated film composed of a dielectric or the like containing at least one noble metal-based thin film exhibits a heat ray reflection function and an infrared ray reflection function, and is ultraviolet-shielded by an acrylic coating containing a silicone component dissolved in an ultraviolet absorbent and a silicon-based hard coat. Expresses the function and durability of the protective film. By skillfully combining these two, a single plate has sufficient durability, and especially the boundary between the ultraviolet and visible regions can be cut extremely sharply. It is a transparent UV-absorbing heat-insulating glass that satisfies the functions of blocking ultraviolet rays, blocking heat rays, and reflecting infrared rays without impairing the optical properties.It has excellent moisture resistance, abrasion resistance, chemical resistance, etc. It can be used, has a relatively high visible light transmittance, can sufficiently secure the field of view, and significantly improves the livability as a window for architecture or vehicles. That it is intended to provide a useful UV-absorbing insulating glass.

[0017]

The present invention will be described below in detail with reference to examples. However, the present invention is not limited to such an embodiment. Example 1 A float glass (FL3) having a size of about 300 mm × 300 mm and a thickness of about 3 mm was sequentially washed with a neutral detergent, water rinse, and isopropyl alcohol, dried, and then set in a vacuum chamber of a DC magnetron sputtering apparatus. The target is set so that it can reciprocate upwards, facing the target of zinc and silver. Then, the inside of the tank is evacuated to about 5 × 10 ⁻⁶ Torr or less by a vacuum pump. And oxygen gas (however, the flow ratio of oxygen gas to argon gas is from 100: 0 to 5
It only has to be in the range of 0:50. ) And reduce the vacuum to about 2
× 10 ^-3 Torr, about 1.0 kw to the zinc target
Is applied, and the sheet glass is transported at a speed of about 250 mm / min above the zinc target in the DC magnetron reaction sputtering using oxygen gas, thereby forming a ZnOx thin film having a thickness of about 40 nm as a first layer. . After the film formation is completed, the application to the zinc target and the supply of the gas are stopped.

Next, while the plate glass is kept in the vacuum chamber, 45 cc of argon gas is introduced into the vacuum layer to maintain the degree of vacuum at about 3 × 10 ⁻³ Torr, and the silver target is applied to the silver target at about 0.1 kN.
w, power was applied, and the speed was increased above the silver target in the DC magnetron sputtering with argon.
By conveying at 800 mm / min, the Zn
An Ag thin film having a thickness of about 10 nm was formed and laminated as a second layer on the Ox deposition surface. After the film formation is completed, the application to the silver target and the supply of the gas are stopped.

Next, while the plate glass is kept in the vacuum chamber, an argon gas is introduced into the vacuum layer to maintain the degree of vacuum at about 3 × 10 ⁻³ Torr, and about 0.1 kw is applied to the zinc target.
By applying a power of about 1600 mm / min above the zinc target through the DC magnetron sputtering, about 6 mm is applied to the Ag deposition surface of the sheet glass.
A Zn thin film having a thickness of nm was deposited and laminated as a third layer. After the film formation is completed, the application to zinc and the supply of gas are stopped.

Next, while the plate glass is kept in the vacuum chamber, argon gas and oxygen gas (provided that the flow ratio of oxygen gas to argon gas is in the range of 100: 0 to 50:50) in the vacuum layer. Good) to reduce the degree of vacuum to about 2 × 10 ^-3 To
rr, a power of about 1.0 kw was applied to the zinc target, and a speed of about 250 m was applied above the zinc target in the DC magnetron reaction sputtering using oxygen gas.
about 40 nm by transporting the sheet glass at m / min
A thin ZnOx thin film was formed as a fourth layer. After the film formation is completed, the application to the zinc target and the supply of the gas are stopped.

Next, after taking out the glass with the film from the vacuum chamber, the surface on which the film is not laminated is masked with a film and immersed in a UV-absorbing acrylic-based primer solution prepared in advance under the following conditions. After being pulled up at a speed of about 0.15 cm / sec, it was dried at about 120 ° C. for about 30 minutes to form an ultraviolet absorbing film (UV) having a thickness of about 8 μm. Then, it was immersed in a silicon-based hard coat solution prepared under the following two conditions and pulled up at a speed of about 1 cm / sec.
After drying at about 120 ° C. for about 30 minutes, it was further heated and cured at about 140 ° C. for about 30 minutes to form a hard coat protective film (HC) of about 5 μm.

As described above, a multilayer thin-film laminated glass as shown in Table 1 was obtained. [1, UV-absorbing acrylic-based primer solution] 350 g of cyclohexanone and 495 g of propylene glycol monomethyl ether serving as a solvent are placed in a 1000 ml round-bottom flask equipped with a stirrer and a reflux condenser, and acrylic BR-85 resin is stirred at room temperature ( 55g (Mitsubishi Rayon). Add 2g of fluorescent brightener UVITEX-OB (manufactured by Ciba-Geigy) and 9g of UV absorber TINUVIN327 (manufactured by Ciba-Geigy) while continuing stirring, raise the temperature to about 95 ° C in about 30 minutes in an oil bath, and hold for about 30 minutes To dissolve completely.

Then, the heating was stopped, and the temperature was lowered to room temperature. Then, about 100 g of an acrylic modified silicone resin OS-808A was added thereto, and the mixture was stirred and dissolved to obtain a UV-absorbing acrylic-based primer solution for glass application. The UV-absorbing acrylic primer solution was transparent and had a solid content of about 9% and a viscosity of about 600 cP. [2, Silicon Hardcoat Solution] 100 g of methyltriethoxysilane and 10 g of 3-glycidoxypropyltrimethoxysilane were put into a 500 ml round bottom flask equipped with a stirrer and a reflux condenser, and 0.04 g of phthalic anhydride was added. added, was warmed dissolved in about 40 ° C. in a water bath, then a weakly basic colloidal silica solution Sunotetsukusu C (manufactured by Nissan chemical Industries, Ltd., average particle size of about 15μm approximately, about about 20% SiO ₂ content) of 100g was added The reaction was carried out at about 40 ° C for about 5 days to obtain a composition having a number average molecular weight of about 1100 and a solid content of about 30% by GPC (manufactured by Tosoh, ULC802A).

To this, 145 g of isopropyl alcohol was added, and an ultrafilter having a molecular weight cut off of 1,000 (manufactured by Nippon Millipore)
To obtain a composition having a number average molecular weight of about 1200 by GPC and a solid content of about 22%.

About 0.1 part of dicyandiamide as a curing catalyst was added to the composition to obtain a silicone-based hard coating solution. Regarding the obtained multilayer thin film laminated glass, the visible light transmittance (380 to 780 nm) and the visible light reflectance (38
0 to 780 nm) and solar transmittance (340 to 1800 nm), 340 type self-recording spectrophotometer (manufactured by Hitachi, Ltd.) and JISZ
The optical characteristics were determined by 8722 and JISR3106, respectively. The ultraviolet absorption performance was evaluated based on the transmittance at 370 nm of a 340 type recording spectrophotometer.

Further, as for the abrasion resistance by the traverse test, six blade cloths # 40 were stacked on a cylindrical bottom surface having a load of 0.1 kg / cm ² and a diameter of 5 cm. It comes into contact with the
After reciprocating 00 times, the state of the film surface was visually evaluated. Next, the acid resistance test of chemical resistance was determined by immersing the test piece in a 1N hydrochloric acid solution at room temperature for about 6 hours and then observing the deterioration state of the film. After immersing the test piece in 1N sodium hydroxide solution for about 6 hours at room temperature,
The marks ○ indicate that the deterioration was hardly observed, and the marks X indicate that the deterioration was clearly conspicuous.

Further, regarding the humidity resistance performance, the surface condition after storage in an environmental tester at 50 ° C. 90% for 1, 2, 5, 10, 20, or 30 days was visually evaluated. No defect is seen, and the others are indicated by crosses. As is clear from Table 2 and FIG. 1, it can be used as a single plate, has a high visible light transmittance, has excellent ultraviolet shielding, heat shielding, and infrared shielding, and has excellent habitability, It has abrasion resistance, corrosion resistance, weather resistance, and durability, and can be used as window glass for automobiles, buildings, and the like.

Examples 2 to 3 In the same manner as in Example 1, the multilayer films and their respective film thicknesses shown in Table 1 were obtained, and the same evaluation means were used in the film constitution by the measuring method and the like shown in Example 1. Table 2 shows the results.
Shown in The AgCu thin film was formed by a DC magnetron sputter using argon, and the ITO thin film was formed using an ITO target by using a DC reactive magnetron sputter of argon and a trace amount of oxygen to a predetermined thickness.

Each of the obtained single-plate articles having a multilayer film was a UV-absorbing heat-insulating glass exhibiting excellent physical properties such as the desired optical properties as in Example 1.

[0030]

[Table 1]

[0031]

[Table 2]

Comparative Example 1 In the same manner as in Example 1, as shown in Table 1, the first to fourth layers were deposited and laminated. However, the ultraviolet absorbing film and the hard coat protective film are not formed. As shown in Table 2 and FIG. 1, the obtained multilayer thin film laminated glass is not preferable in absorption of ultraviolet rays, humidity resistance, abrasion resistance and chemical resistance, and is not intended.

Comparative Example 2 After a ZnOx film was laminated on a glass substrate to a thickness of 500 nm by sputtering,
An Ox film, a TiOx film, and a SiOx film were stacked. The SiOx thin film is
An RF magnetron sputter using SiO 2 as a target and argon oxygen was used, and a TiOx thin film was formed as a Ti target using a DC reactive magnetron sputter using an oxygen to obtain a predetermined film thickness. However, the ultraviolet absorbing film and the hard coat protective film are not formed.

As shown in Table 2, the obtained multilayer thin-film laminated glass has poor chemical resistance and is not intended. Comparative Example 3 A 500 nm thick ZnOx film was formed on a glass substrate by sputtering, and then Ag was
A film, a Zn film, a TiOx film, and a SiOx film were stacked and formed. However, the ultraviolet absorbing film and the hard coat protective film are not formed.

As shown in Table 2, the obtained multilayer thin-film laminated glass has poor humidity resistance, abrasion resistance and chemical resistance, and is not intended. Comparative Example 4 One surface of a glass substrate was masked with a film, immersed in an ultraviolet-absorbing acrylic primer solution prepared under the conditions described in 1 above, and pulled up at a rate of about 0.15 cm / sec. After drying for about 30 minutes, an ultraviolet absorbing film (UV) having a thickness of about 8 μm was formed. Then, it was immersed in the silicon-based hard coat solution prepared under the conditions of the above 2 and about 1 cm
After pulling up at a speed of about / sec, drying at about 120 ° C. for about 30 minutes, and then heating and curing at about 140 ° C. for about 30 minutes to form a hard coat protective film (HC) of about 4 μm. .

As shown in Table 2 and FIG. 1, the obtained multilayer thin-film laminated glass is not intended to achieve the intended purpose because it naturally has no heat insulating performance. However, it is satisfactory in terms of ultraviolet absorption, humidity resistance, abrasion resistance and chemical resistance. As described above, a laminated film as shown in Table 1 was obtained, and in the film configuration, the same measurement method and the same evaluation means as in Example 1 were used, and the results were as shown in Table 2, respectively. Insulated glass is remarkably excellent overall in various points, and each comparative example cannot fully satisfy, for example, ultraviolet ray shielding performance, heat ray shielding performance, and infrared reflection performance at the same time as compared with these examples. Therefore, it is hard to say that it is sufficient for the desired characteristics. In addition, its durability performance is not particularly preferable for at least one of humidity resistance, chemical resistance, and abrasion resistance, and is not sufficient for use as a veneer. It cannot be said that it is the desired durability performance.

[0037]

As described above, according to the present invention, a primer coat in which a fluorescent whitening agent and an ultraviolet absorber are dissolved is applied to a laminated thin film layer composed of a dielectric thin film containing at least a noble metal thin film. By applying a silicon-based hard coat as a protective film, a heat-reflection function and an infrared-reflection function are exhibited by a dielectric or a noble metal-based laminated thin film layer. By exhibiting an ultraviolet shielding function and a durable protective film function, and by combining these both skillfully, it has sufficient durability even when used as a single plate, without impairing optical characteristics, ultraviolet shielding, heat rays It can be an ultraviolet absorbing heat insulating glass that can satisfy the shielding and infrared reflecting functions, and has relatively high visible light transmittance. It can sufficiently viewing secured, window or a transparent heating element for buildings or vehicles, as such an electromagnetic wave shield, there is provided an ultraviolet absorbing insulating glass which is to significantly improve the comfort.

[Brief description of the drawings]

FIG. 1 is a diagram showing spectral transmittance curves of Example 1 of the present invention and Comparative Examples 1 and 4 which are conventional examples.

Continued on the front page (72) Inventor Haruki Kuramasu 1510 Oguchi-cho, Matsusaka-shi, Mie Central Technical Co., Ltd. Technical Center (58) Field surveyed (Int.Cl. ⁶ , DB name) C03C 17/38 B32B 15/04 B60J 1/00 C03C 17/42 E06B 5/00

Claims (5)

(57) [Claims] 1. A synthetic resin-based primer liquid obtained by laminating a multilayer film containing at least one noble metal-based thin film on the surface of a transparent glass substrate and then dissolving and adding a fluorescent whitening agent and an ultraviolet absorber. After coating and heating and curing, a silicone-based hardener in which a siloxane prepolymer is dissolved in an organic solvent.
A UV-absorbing heat-insulating glass characterized in that it is coated in sequence by applying a coating solution and curing by heating. 2. The multi-layered film containing at least one noble metal-based thin film is a three- to seven-layer film formed by sequentially laminating a dielectric, a noble metal or an alloy thereof, a metal, and a dielectric, or a repetitive lamination thereof. The ultraviolet absorbing heat insulating glass according to claim 1, wherein: 3. The ultraviolet absorbing heat insulating glass according to claim 1, wherein said noble metal based thin film is made of Ag, Au, Cu, Pt or an alloy thereof. 4. The dielectric of the multilayer film is made of Si, Ti, Sn, A
3. The ultraviolet absorbing heat-insulating glass according to claim 2, wherein the glass is an oxide, nitride, or nitrogen oxide film of l, Cr, SUS, Ta, Zn, In, SiC or an alloy thereof. 5. The ultraviolet absorbing heat insulating glass according to claim 1, wherein said synthetic resin primer liquid is an acrylic solution containing a silicone component.