JPH08133790A - Ultraviolet rays and infrared rays absorbing transparent body - Google Patents

Abstract

PURPOSE: To shield UV rays without damaging an optical characteristic and a heat rays and IR rays shielding performance and to remarkably increase wear resistance, scuffing resistance and durability while keeping the characteristic and the performance by sufficiently shielding near 400nm especially and to produce the subject body usable for a long time as a window material for an automobile, not to mention for a building. CONSTITUTION: In the UV rays and IR rays absorbing transparent body, a polysilazane based mixture soln. is applied to form film on a surface of a hard coat type UV rays and IR rays absorbable film obtained by applying in order a synthetic resin based primer coating soln. in which a fluorescent brightener, an UV rays absorber and an IR rays absorber are dissolved on the surface of a transparent base material and heat-curing to form an UV rays and an IR rays absorbable thin film, then a silicone based hard coating soln. obtained by dissolving siloxane pre-polymer in an org. solvent thereon and heat-curing to form a protective thin film.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is a transparent body coated with a coating film having excellent absorption of ultraviolet rays and infrared rays, and has more abrasion resistance, scratch resistance and durability while maintaining excellent characteristics. In particular, the present invention relates to an ultraviolet-infrared ray absorbing transparent body which becomes more prominent when used in a single plate.

These are ultraviolet / infrared absorbing transparent materials which are useful as window / infrared ray blocking filter members, for example, in window materials for buildings, houses, vehicles, automobiles, ships, aircrafts, and various display devices.

[0003]

2. Description of the Related Art Conventionally, treatment methods for imparting ultraviolet and infrared absorption to a transparent body such as a glass substrate have generally been roughly classified into the following three types.

First, (1) a method of mixing and blending an ultraviolet and infrared ray absorbing compound in the transparent body itself. For example, various glass compositions in which a metal compound is melt-added into glass (for example, JP-A-4-224133), and then (2) a method of laminating an ultraviolet and infrared ray absorbing transparent film on the surface of a transparent body. For example, a laminated glass sandwiched by a polyvinyl butyral interlayer film containing an ultraviolet and infrared absorber (see, for example, JP-A-59).
-152249 gazette) etc. Furthermore, (3) a method of laminating and forming an ultraviolet and infrared ray absorbing transparent film on the surface of the transparent body. For example,
A material in which zinc oxide and aluminum-containing zinc oxide are laminated on a transparent base material by a vapor phase film forming method such as sputtering (for example, Japanese Patent Publication No. 44721/1992 and Japanese Patent Publication No. 133004/1992) or ultraviolet and infrared absorption Liquid phase film formation method using a resin solution in which the agent is dissolved (for example, Japanese Patent Application Laid-Open Nos. 4-160037 and 5-42622) or a liquid phase film formation method using a resin solution in which an ultraviolet and infrared absorber is dispersed (for example, JP-A-2-
No. 75683 gazette).

On the other hand, various types of silazanes have been conventionally used for various purposes. Among them, the followings are related to so-called surface modification of articles. For example, JP-A-1-138107 discloses a modified polysilazane, a method for producing the modified polysilazane, a raw material polysilazane having perhydropolysilazane as a starting material, orthoxylene as a solvent, and carbonization as a filler. It describes that a solution consisting of silicon was prepared and applied on a SUS substrate to form a film.

Further, for example, in Japanese Patent Laid-Open No. 5-311120,
Disclosed are a composition for forming an ultraviolet-shielding glass protective film and an ultraviolet-shielding glass, and the surface of the glass coated with an ultraviolet-shielding film such as ZnO or TiO ₂ (SiH ₂ -based Si-H
The number of bonds) / (the number of all Si—H bonds) = 0.13 to 0.45, and the polysilazane having a number average molecular weight of 200 to 100,000 is contained as an essential component and diluted with a solvent such as xylene. An ultraviolet-shielding glass coated with a protective film-forming composition is described.

Further, for example, Japanese Patent Laid-Open No. 5-310444 discloses a water repellent article and a method for producing the same,
A base material, a silicon dioxide-containing coating formed by reacting, for example, SiH ₄ gas, N ₂ gas for separation, and O ₂ gas on the surface of the base material, and poly-silicon such as hexamethyldisilazane formed on the surface of this coating. A water repellent layer composed of a nitrogen analog of siloxane or an organic silazane compound which is a fluorine-containing disilazane system is described.

Further, for example, Japanese Patent Application Laid-Open No. 5-163174 filed by the applicant of the present invention discloses an ultraviolet shielding glass for vehicles. At least one ultraviolet shielding film is formed on the glass, and for example, it is formed on the outside. It describes that a layer containing silicon is formed, such as by coating and forming a compound having at least CH ₃ —Si bond and / or a compound having Si—N bond.

[0009]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention As described above, for example, none of the ones described in Japanese Patent Laid-Open No. 4-224133 is not suitable for high-mix low-volume production.
Absorption is also insufficient.

Further, the one described in JP-A-59-152249 has improved chemical resistance, scratch resistance and durability as compared with the case of the resin film alone, but it uses two or more plate glasses. It has poor shape conformability, and it is difficult to reduce its weight because it is quite thick.

Further, those disclosed in Japanese Patent Publication No. 4-44721 or Japanese Unexamined Patent Publication No. 4-133004 are ZnO.
Since it becomes an absorption base, there is concern about moisture resistance, chemical resistance, and durability, and UVA yield is insufficient.

Further, in the conventional method using an organic compound-based coating agent described in JP-A-2-75683 and JP-A-4-160037, it is necessary to add a large amount of an ultraviolet / infrared absorber, and the matrix resin layer If it is used alone, the chemical resistance, scratch resistance, and durability will be considerably inferior.

On the other hand, for example, in the ultraviolet blocking glass for vehicles described in the above-mentioned Japanese Patent Laid-Open No. 5-163174, it is sure that the ultraviolet blocking property is excellent, or that it has excellent scratch resistance or weather resistance against window up / down movement, scratching and rubbing. However, when adopting a relatively low temperature curing type ultraviolet absorbing thin film as shown in the ultraviolet absorbing transparent body described in JP-A-6-145387, it is not always immediately adopted. is there.

Similarly, for example, the above-mentioned JP-A-1-138107.
In the modified polysilazane described in Japanese Patent Laid-Open No. JP-A No. 6-145387, it is difficult to say that the modified polysilazane, the method for producing the same, and the use thereof are relatively low-temperature curable types. In addition, it cannot be used for a transparent body that requires sufficient transparency.

Further, for example, in the composition for forming an ultraviolet-shielding glass protective film and the ultraviolet-shielding glass described in JP-A-5-311120, a relatively low temperature curing type described in JP-A-6-145387 is disclosed. Are likewise unacceptable.

Furthermore, in the water repellent article and the method for producing the same described in, for example, Japanese Patent Laid-Open No. 5-310444, a silicon dioxide coating is used as an underlayer on the glass surface, and an organic silazane compound is added to the silazane water repellent. However, it cannot be used at all in the case where the relatively low temperature curing type ultraviolet absorbing thin film described in JP-A-6-145387 is used as the undercoating layer and the hard coating is carried out.

[0017]

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and it is an optical brightener for shielding UVA extremely sharply to the boundary of the visible region, and an infrared absorbing agent. While applying the agent to the coating agent composition, it is dissolved and added to a synthetic resin primer that has good adhesion to various substrates, especially transparent substrate surface, especially acrylic primer coating solution, and it absorbs UV and infrared rays. A hard coat type that absorbs fluorescence and improves light resistance by coexisting with an agent, forms a coating film in which fluorescence is inconspicuous at a relatively low temperature, and further protects this with a silicone-based hard coating film as a top coat. By applying a solution of a polysilazane-based mixture on the ultraviolet and infrared absorbing film to form a film, damage to the underlayer due to cure etc. By coating with a low temperature curing type treatment without the above, there is a protective effect that an excellent product having significantly improved durability such as chemical resistance, scratch resistance and abrasion resistance, which are the above problems, can be obtained. It can be used as a plate or an exterior, and it is transparent to UV absorption, which does not provide sufficient performance with each structure alone, sharply shields UVA, and simultaneously exhibits and maintains the heat ray absorption performance. It is assumed that it is equipped with, and is extremely excellent in chemical resistance, abrasion resistance, scratch resistance and durability, not only in veneer construction and vehicular window materials, but also especially under various severe conditions. It is intended to provide a useful ultraviolet and infrared ray absorbing transparent material which can be used for a long period of time.

That is, according to the present invention, the surface of the transparent substrate is
A synthetic resin-based primer coating solution prepared by dissolving and adding a fluorescent whitening agent, an ultraviolet absorber and an infrared absorber is applied and cured by heating to form an ultraviolet and infrared absorbing thin film, and then the siloxane prepolymer is dissolved in an organic solvent. A silicone-based hard coating solution is applied and heat-cured to form a protective thin film, which is sequentially coated to form a hard coat type ultraviolet / infrared absorbing thin film. An ultraviolet and infrared absorption transparent body characterized by the following.

The above-mentioned ultraviolet and infrared ray absorbing transparent body, wherein the synthetic resin-based primer coating solution is an acrylic primer coating solution. Further, the polysilazane-based mixture is a low-temperature-curable polysilazane-based mixture, which is the above-mentioned ultraviolet-infrared-absorbing transparent body.

Furthermore, the above-mentioned UV-infrared absorbing transparent body is provided, wherein the low temperature-curable polysilazane-based mixture is mainly composed of poly (perhydrosilazane) -based mixture.

Here, as mentioned above, the fluorescent whitening agent absorbs in the ultraviolet region and emits fluorescence in the visible region,
Synthetic resin type primer, especially acrylic type primer, which can be melt-added and can be any type as long as the coating film does not denature by heat curing at a relatively low temperature, and also has a suitable heat resistance. The absorption wavelength is in the ultraviolet / visible region boundary (around 400 nm), for example,
Uvitex-OB (Ciba Geigy, 2,5 bis (5'-tertiarybutylbenzoxazolyl) thiophene) or EB-501 (Mitsui Toatsu Dyes), and Nikkafluor SB
, KB, EFS, OB (manufactured by Nippon Chemical Industry Co., Ltd.) and the like.

Examples of the ultraviolet absorbers that can coexist include benzophenone-based, benzotriazole-based, cyanoacrylate-based, salicylate-based, and indole-based compounds.

Examples of the infrared absorbers that can coexist include polymethylene type (cyanine, pyrylium,
Squarylium, croconium, azurenium, etc.),
Examples thereof include phthalocyanine-based, dithiol metal complex-based, naphthoquinone-based, anthraquinone-based, indole phenol-based, azo-based, triallylmethane-based, immonium-based, diimonium-based compounds.

The ratio of the fluorescent whitening agent, the ultraviolet absorber and the infrared absorber used is 1: 0.5: 0.3 by weight.
To about 1:10:10, and a preferable range for ensuring more stability is about 1: 3: 0.5 to 1: 6: 6. When the amount of the optical brightener increases, the transparency deteriorates due to fluorescence. ,
If it is too small, the desired UVA absorption capacity will not be obtained. These are 0.1-10% by weight of the primer coating solution as a total.
However, it is uneconomical to add more than necessary even if there is a margin in solubility.

Further, regarding the synthetic resin primer, especially the acrylic primer, it is necessary to sufficiently dissolve the fluorescent whitening agent, the ultraviolet absorber and the ultraviolet absorber described above, and therefore, in an ether alcohol solvent such as ethyl cellosolve. It is preferable to use a ketone alcohol-based solvent such as diacetone alcohol or a mixed solvent prepared by combining a ketone, an ether or an aromatic solvent so as not to attack the transparent substrate. Especially when the transparent substrate is a glass plate or the like, a ketone solvent such as cyclohexanone or an aromatic solvent such as toluene which has a dissolving power is preferable.

Furthermore, as the synthetic resin, for example, acrylic resin, urethane resin, fluorine resin,
Polyester resin or silicone resin,
Among them, as the acrylic resin, for example, a commercially available acrylic BR resin (manufactured by Mitsubishi Rayon) may be used to prepare the acrylic resin in accordance with the concentration, viscosity or film thickness.
Resin concentration is about 1 ~ 15wt%, viscosity is 10
~ 1000 cP, primer film thickness of 0.5 ~ 10μ is preferable, and top film thickness is 1 ~
Since about 5 μ is preferable, about 2 to 15 μ is preferable as the total film thickness.

When the transparent base material is made of glass, a silane coupling agent is often used in order to further improve the adhesiveness. For example, OS808A (a silicone modified acrylic by Daihachi Chemical Co., Ltd.) is used as a primer solution. About 0.25 to 60% by weight and about 1/4 to 4 of the resin concentration are added, but if too little, there is no effect, and if too much, it becomes uneconomical.

Furthermore, the ultraviolet absorbing synthetic resin primer prepared as described above, particularly the ultraviolet absorbing acrylic primer, has a uniform film thickness,
For example, it is applied by a dipping method, a spray method, a flow coating method, a printing method or the like to form a film, which is heated and dried at about 80 ° C. or higher for about 1 hour. If the heating is insufficient, a silicone hard coat is used. The primer component is likely to elute into the protective film to cause, for example, clouding or cracks, and when the heating is excessive, the adhesion of the protective film, which is a silicone-based hard coat, deteriorates.

The silicone hard coating solution is preferably based on an alcohol solution of a siloxane prepolymer, which is basically obtained by hydrolyzing an organoalkoxysilane. For example, the applicant of the present invention has already proposed it. Those containing colloidal silica such as the coating composition described in JP-A No. 62-220531 are more preferable because of excellent abrasion resistance. In the case of commercial products, for example, Tosgard 510 (made by Toshiba Silicone) or Si coat 2
(Manufactured by Daihachi Chemical Co., Ltd.) can be used.

Further, the coating environment is, for example, a temperature of about
About 15 to 25 ° C, a humidity of about 40 to 50 RH%, and a cleanliness of about 10,000 or less are preferable from the viewpoint of preventing coating film defects. Further, as the coating method, similar to the ultraviolet and infrared ray absorbing synthetic resin primer, especially the ultraviolet and infrared ray absorbing acrylic primer, a dipping method, a spray method, a flow coating method or a printing method can be used so as to obtain a uniform film thickness. Available. The film thickness is preferably about 1 to 5 μm, and when it is thin, the effect of the surface protective film is lost, and when it is thick, cracks are likely to appear during heat-drying and curing. Further, a temperature of about 80 ° C. or higher is preferable for the heat-drying and curing, and particularly when the transparent substrate is a glass plate or the like, a temperature of about 150 ° C. and a treatment for about 2 hours are preferable for increasing the surface hardness.

Needless to say, a flow improver, a rheology control agent or the like may be appropriately added in order to improve the coating performance of the above-mentioned ultraviolet absorbing acrylic primer or silicone hard coating solution.

Further, as the polysilazane-based mixture,
A low temperature-curable polysilazane-based mixture is preferable, and specifically a poly (perhydrosilazane) -based mixture (for example, manufactured by Tonensha Co., Ltd.), in which the solid content concentration of the mixture is 5 to 5 It is about 40 wt% (the rest is, for example, xylene and a curing catalyst).

The coating film of the mixture can be formed by, for example, a dipping method, a spray method, a flow coating method, a spin coating method or a printing method so as to obtain a uniform film thickness. ~ 3μ,
It is preferably about 1.0 to 2.0 μ, and when it is thin, the effect of strengthening the surface protection is reduced, and when it is thick, cracks are likely to appear during heat-drying and curing, and it is not economical. Furthermore, since the first layer contains an organic UV absorber, a fluorescent whitening agent and a resin for heat-drying and curing, it is about 100 ° C or more and about 250 ° C or more.
It is necessary to perform the treatment at a temperature not higher than about 60 ° C., preferably about 150 to 220 ° C. when the transparent substrate is a glass plate or the like, and the treatment for about 10 to 60 minutes, preferably about 30 minutes. It is preferable for increasing the surface hardness.

The application environment is, for example, a room temperature of about 25 ° C. and a relative humidity of about 20 to 50% RH, preferably about 40% RH. Needless to say, even better if it is a clean room.

Regarding the diluting solvent in the solution of the polysilazane mixture, the aromatic compound is, for example, benzene, toluene, xylene, and the ether compound is, for example, ethyl ether, tetrahydrofuran (THF).
The chlorine compound is, for example, methylene chloride, carbon tetrachloride, and the ketone compound is, for example, butyl carbitol acetate.

Further, the transparent substrate may be any one having a heat resistance of about 80 ° C. or higher, and is preferably an inorganic glass such as a float glass or a resin such as PC, PMMA, PET or the like. Glass or the like, regardless of whether it is inorganic or organic, is not particularly limited to the shape and the like, and has various shapes, and of size or configuration, for example, as bent plate glass,
It is needless to say that it can be used as various tempered glass, strength-up glass, flat plate or single plate, and can be applied as multi-layer glass or laminated glass.

[0037]

As described above, according to the present invention, a coating solution having a unique constitution and excellent in ultraviolet and infrared ray shielding property, which is a primer solution in which a fluorescent whitening agent, an ultraviolet absorber and an infrared absorber coexist, and a sufficient amount The surface of the hard coat type ultraviolet / infrared ray shielding film, which is a protective film formed by a silicone hard coating, is a transparent body which is further coated with a solution of a polysilazane-based mixture. Fluorescence can also be formed at a relatively low temperature as a coating that is inconspicuous, and a unique silica-based film obtained by low-temperature curing treatment from the solution of the specified hard coat and polysilazane-based mixture (for example, by surface analysis such as SIMS, Part of the film, for example, N remains at the adhesion part of the coating, etc.) and becomes a double protective film, and UVA is extremely sharp. Can be shielded to the boundary of the visible region, and in addition to having excellent infrared absorption performance, it also has excellent adhesion, chemical resistance, scratch resistance or durability, and in addition to the above-mentioned peculiarity of a relatively thick film thickness. Even if it is a silica-based film, cracks do not appear, and low-temperature curing treatment can increase the adhesion to the hard coat film, and it becomes dense even in the amorphous form, and has a pencil hardness of 9H or higher, and film strength and smoothness. In particular, the conventional wear resistance, scratch resistance, or durability has been further improved, the field of view can be secured sufficiently, and livability is greatly improved. Of course, it can be used as a plate or exterior, especially for the more severe of windshields of automobile windows, rear glass and side door glass that moves up and down, sunroof glass, etc. Transparent UV-IR absorption that can be used for a long time even under usage conditions and environments, and has a glare due to reflection of visible light and radio waves and a useful UV-IR shielding window that does not have radio wave shielding properties. The transparent body can be easily and inexpensively obtained and provided by a simple coating process.

[0038]

The present invention will be described below in detail with reference to examples. However, the present invention is not limited to the embodiment. Solution A (Preparation of UV absorbing acrylic primer) [For glass coating] Cyclohexanone and propylene glycol monomethyl ether as solvents are put into a round bottom flask equipped with a stirrer and a circulator and stirred at room temperature as an acrylic resin dialnal BR. -88 or BR-85 (both manufactured by Mitsubishi Rayon) are introduced. UVITEX-OB (manufactured by Ciba Geigy) as a fluorescent whitening agent, TINUVIN327 (manufactured by Ciba Geigy) as an ultraviolet absorber, and SIR 159 (manufactured by Mitsui Toatsu Fine Co., Ltd.) as an infrared absorber while continuing stirring.
1 (manufactured by Teikoku Kagaku Sangyo Co., Ltd.) was added at the ratio shown in Table 1, and the temperature was raised to about 95 ° C over about 30 minutes in an oil bath, then about 30
Hold for about a minute to dissolve completely. Then stop heating,
After the temperature was lowered to room temperature, a silicone modified acrylic resin OS-808A as an adhesion improver was added and dissolved by stirring to obtain an ultraviolet absorbing acrylic primer for glass coating.

The ultraviolet / infrared absorbing acrylic primer solution is transparent and has a solid content of about 8-11% and a viscosity of about 250-.
It was about 350cP (25 ℃). Solution B (Preparation of UV-infrared absorbing acrylic primer) [For resin coating] Cyclohexanone, diacetone alcohol, and propylene glycol monomethyl ether as solvents are put into a round-bottomed flask equipped with a stirrer and a circulator, and acrylic is stirred at room temperature. BR-85 resin (made by Mitsubishi Rayon) is introduced. UVITEX-OB optical brightener while continuing to stir
(Manufactured by Ciba-Geigy), UV absorber TINUVIN327 (manufactured by Ciba-Geigy) and infrared absorbers PA1001 and SIR103 (manufactured by Mitsui Toatsu Fine Co., Ltd.) are added at the ratios shown in Table 1, and about 95 ° C over about 30 minutes in an oil bath. After the temperature was raised to about 30 minutes, it was kept for about 30 minutes to be completely dissolved to obtain an ultraviolet and infrared absorbing acrylic primer for resin application.

The ultraviolet and infrared absorbing acrylic primer solution is transparent and has a solid content of about 3-5% and a viscosity of about 180-.
It was about 250cP (25 ℃). Liquid C (preparation of silicone-based hard coating solution) 100 g of methyltriethoxysilane and 10 g of 3-glycidoxypropyltrimethoxysilane were placed in a 500 ml round bottom flask equipped with a stirrer and a circulator, and 0.04 g of phthalic anhydride was added.
Is added and heated in a hot water bath to about 40 ° C to dissolve it, and then
Weakly basic colloidal silica aqueous solution Snowtex C (manufactured by Nissan Chemical Co., average particle size of about 15 μm, SiO ₂ content of about 20%) 100 g was added and reacted at about 40 ° C. for about 5 days, and GPC ( ULC802A manufactured by Tosoh Co., Ltd. was used to obtain a composition having a number average molecular weight of about 1100 and a solid content of about 29%. to this
145 g of isopropyl alcohol was added, and the molecular weight cut-off was 10
The mixture was concentrated with an 00 ultrafilter (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 20%. About 0.1% of dicyandiamide was added to the composition as a curing catalyst.
About 1 part was added to obtain a silicone-based hard coating solution. Liquid D (Preparation of polysilazane-based mixture solution) A curing catalyst or the like was added mainly based on poly (perhydrosilazane), and xylene was used as a diluting solvent to obtain a solution having a solid content concentration of about 20 wt%. [Used by Tonensha Co., Ltd.] (Performance evaluation method) Ultraviolet and infrared absorptivity: Absorption spectrum pattern was measured with a spectrophotometer. (For example, Hitachi-U4000 type) Fluorescence: Visual observation under outdoor natural sunlight. (There is no emission of light and no cloudiness.) Abrasion resistance: Conforms to JIS R 3221, wear wheel CS-10F, load 500g, ΔH (haze) value (%) after 1000 rotations.

Surface hardness: Pencil hardness. Adhesion: In accordance with JIS K5400, the cross-cut (1mm mouth) tape peeling remaining number is displayed as / 100.

Chemical resistance: Acid resistance --------- 3 wt% Dilute H ₂ SO ₄ immersion test for 24 hours. Alkali resistance --- 24wt% in 5wt% NaOH dip test. Solvent resistance ------ 100% ethanol 4 hours by drip test.

Weather resistance: According to JIS D0205, the time until visual abnormality (film crack, peeling, noticeable yellowing) is observed with a sunshine carbon weather meter. (However, irradiation on the glass surface) Example 1 A clear float glass substrate having a size of about 300 mm x 300 mm and a thickness of about 3 mm was sequentially washed with a neutral detergent, water rinse, alcohol, dried, and then wiped with acetone to form a film. A glass substrate was used.

One side of the glass substrate for coating was film-masked and dipped in the prepared UV coating infrared ray absorbing acrylic primer solution for glass coating shown in Table 1 to give a thickness of about 0.1 cm.
Pull up at a speed of about / sec and about 0 at about 120 ° C.
After drying for about 5 hours, an ultraviolet / infrared ray absorbing film having a thickness of about 6 μm was formed.

Then, the glass substrate with the ultraviolet absorbing film is dipped in the prepared silicone-based hard coating solution and pulled up at a speed of about 1 cm / sec to about 12 cm.
The film was dried and hardened at about 0 ° C. for about 0.5 hours and at about 150 ° C. for about 0.5 hours to form a protective film having a thickness of about 3 μm.

Then, the glass substrate with a laminated film coated with the hard coat protective film was prepared as a polysilazane-based mixture solution D prepared above in a clean room condition of about 25 ° C. and about 40% RH in an air-conditioned clean room. After being dipped in the liquid and applied only on the hard coat surface, it was air-dried for about 10 minutes and then placed in a hot air circulation dryer at about 170 ° C. for about 30 minutes to cure, and a silica-based film was obtained. The film was colorless and transparent and had no crack, and the film thickness was about 1.2 μm. During the drying process in the far-infrared furnace, it could be cured at about 200 ° C in about 15 minutes.

The obtained ultraviolet / infrared absorbing glass substrate, which is an ultraviolet / infrared absorbing transparent body, was evaluated according to the above-described performance evaluation method. As a result, as shown in Fig. 1, even if a specific silica-based thin film is further coated, it is slightly greenish, but it blocks almost 100% of UVA, and the solar radiation transmittance is 50% or less. In this state, the heat ray is sufficiently shielded, and the emission of light can be prevented and the cloudiness can be prevented. The surface hardness is 9H or more and the pencil hardness is hard, and the haze value (ΔH) after the Taber test is high. As a result, an ultraviolet-infrared absorbing glass plate having a scratch resistance of 3.7, weather resistance of 3000 hours or more, no visual abnormality, no abnormal chemical resistance, and excellent durability was obtained.

Examples 2 to 3 A glass substrate similar to that used in Example 1 was prepared with the same primer solution as shown in Table 1, and the same film formation as in Example 1 was performed.
An ultraviolet and infrared absorption film having a film thickness of about 6 to 7 μm was formed.

Next, the glass substrate provided with the ultraviolet and infrared ray absorbing film is dipped in Tosugato 510 (manufactured by Toshiba Silicone), which is a commercially available silicone-based hard coating solution, to obtain a solution of about 1 cm.
It was pulled up at a speed of / sec and dried and cured at about 120 ° C. for about 3 hours to form a protective film with a thickness of about 3 μm.

Next, only the drying temperature of the coating film of the liquid D was changed to about 200 ° C. in Example 2 and about 170 ° C. in Example 3, and the film thickness was changed to about 1.2 μ in Example 2. Example 3 is about 1.5
A silica-based film of about μ was obtained.

The ultraviolet / infrared shielding glass substrate which is the obtained ultraviolet / infrared absorbing transparent body was evaluated in the same manner as in Example 1. As a result, for example, the haze value after the Taber test (△
H) is 2.8 in Example 2 and 3.2 in Example 3, and the abrasion resistance is remarkably excellent. Other evaluations are similar to those in Example 1, and the desired excellent ultraviolet / infrared absorption as in Example 1 is obtained. It was a transparent body.

Examples 4 to 5 A PC plate having a thickness of about 3 mm was dipped in a UV-absorbing acrylic primer solution for resin coating shown in Table 1 to give a thickness of about 0.1 cm / cm 2.
Pull up at a speed of about sec, about 0.5 at about 120 ℃
After drying for about an hour, an ultraviolet / infrared absorbing film having a film thickness of about 4 or 6 μm was formed.

Then, the film with an ultraviolet absorbing film is dipped in the above-prepared silicone-based hard coating solution and pulled up at a speed of about 1 cm / sec to about 120 cm.
The film was dried and hardened at about 0.5 ° C. for about 0.5 hours and at about 150 ° C. for about 0.5 hours to form a protective film with a thickness of about 3 μm.

Next, only the drying temperature of the coating film of the liquid D was changed to about 200 ° C. in Example 4 and about 170 ° C. in Example 5, and the film thickness in Example 2 was about 1.5 μm. Example 3 is about 2.1
A silica-based film of about μ was obtained.

The obtained ultraviolet / infrared ray absorbing transparent film was evaluated in the same manner as in Example 1.
As a result, for example, haze value (ΔH) after Taber test
However, Example 4 was 3.8, and Example 5 was 4.2, and the abrasion resistance was remarkably excellent. Other evaluations were the same as those of Example 1, and the desired excellent ultraviolet-infrared-absorbing transparent body as in Example 1 was obtained. Met.

Comparative Example 1 As shown in Table 1, as in Example 1 except that a UV brightening agent UVITEX-0B (manufactured by Ciba Geigy) and an ultraviolet absorbent TINUVIN327 (manufactured by Ciba Geigy) were used. Similarly, an ultraviolet absorbing glass substrate was obtained.

The obtained ultraviolet absorbing glass substrate was good in appearance, but could not shield 100% of UVA, had a solar radiation transmittance of 90% or more, and had a haze value after the Taber test. (ΔH) was 24.1, so it was hard to say that it was an expected ultraviolet and infrared absorbing glass plate.

COMPARATIVE EXAMPLE 2 As shown in Table 1, except that a UV-absorbing acrylic primer prepared with a fluorescent whitening agent UVITEX-OB (manufactured by Ciba Geigy) and an infrared absorbent NIR-AM1 (manufactured by Teikoku Chemical Industry) was used. An ultraviolet / infrared absorbing glass substrate was obtained in the same manner as in Example 1.

The obtained ultraviolet-infrared-absorptive glass substrate felt a slight blue fluorescence in appearance and partially shielded the visible region near ultraviolet, but had a UVA up to that time.
Is not shielded, the weather resistance is about 500 hours, and the haze value (△ H) after the Taber test is 23.
It was hard to say that it was a glass plate for absorbing ultraviolet rays and infrared rays at the very beginning.

Comparative Example 3 As shown in Table 1, Example 1 was repeated except that an ultraviolet absorbent TINUVIN327 (manufactured by Ciba Geigy) and an infrared absorbent NIR-AM1 (manufactured by Teikoku Kagaku Sangyo) were used.
An ultraviolet and infrared absorbing glass substrate was obtained in the same manner as in.

Regarding the obtained ultraviolet and infrared ray absorbing glass substrate, the shielding in the vicinity of 400 nm was insufficient and the weather resistance was 12
It was about 00 hours, and the haze value (ΔH) after the Taber test was 23.4, so it was hard to say that it was a UV / infrared absorbing glass plate at the very beginning.

Comparative Example 4 As shown in Table 1, an infrared absorbing glass substrate was prepared in the same manner as in Example 1 except that the infrared absorbing primer prepared only with the infrared absorbing agent NIR-AM1 (manufactured by Teikoku Kagaku Sangyo) was used. Obtained.

With respect to the obtained infrared absorbing glass substrate, there was no ultraviolet ray cutting performance, the weather resistance was about 600 hours, and the haze value (ΔH) after the Taber test was 22.2. It was hard to say that it was an ultraviolet and infrared absorbing glass plate at the very beginning.

[0064]

[Table 1]

In Table 1, (a) Dialnal BR88,
(A ') Diinal BR85 (both made by Mitsubishi Rayon). (B) UVITEX-OB (manufactured by Ciba Geigy).
(C) TINUVIN327 (manufactured by Ciba Geigy).
(D) NIR-AM1 (manufactured by Teikoku Chemical Industry), (d ') S
IR159 (Mitsui Toatsu Fine), (d '') PA10
01 (manufactured by Mitsui Toatsu Fine), (d ''') SIR103
(Mitsui Toatsu Fine). (E) cyclohexanone,
(E ') propylene glycol monomethyl ether,
(E '') diacetone alcohol. (F) Silicone modified acrylic resin: OS808A (manufactured by Daihachi Chemical Co., Ltd.) is shown.

[0066]

As described above, according to the present invention,
It is transparent and can block UV and infrared rays without impairing the optical properties, especially UVA almost completely.
It also has good heat ray absorption performance, has significantly improved habitability, and has dramatically improved adhesiveness, chemical resistance, scratch resistance, and durability, and is a single plate for windows of buildings, houses, vehicles, etc. Of course, it can also be used as an exterior,
In particular, it is possible to impart various functionalities such as long-term use even under severe operating conditions and environments such as windshields of automobile window glass, rear glass, side door glass that moves up and down, and sunroof glass. It is possible to easily and inexpensively provide a useful ultraviolet / infrared ray absorbing transparent body which can be widely adopted in various fields.

[Brief description of drawings]

FIG. 1 shows the transmittance of an ultraviolet-infrared ray absorbing transparent body of Example 1 of the present invention and a normal glass substrate (thickness of float glass 3 mm).

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location B32B 27/18 Z 9349-4F B60J 1/00 G C08J 7/04 Z (72) Inventor Noboru Murata 1510 Oguchi-cho, Matsusaka-shi, Mie Central Glass Co., Ltd. Glass Research Institute

Claims (4)

[Claims] 1. An ultraviolet and infrared absorbing thin film is formed by applying a synthetic resin-based primer coating solution obtained by dissolving and adding a fluorescent brightening agent, an ultraviolet absorbing agent and an infrared absorbing agent onto the surface of a transparent substrate and heating and curing it. After that, a siloxane prepolymer is applied to a silicone-based hard coating solution that is dissolved in an organic solvent and heat-cured to form a protective thin film. An ultraviolet-infrared absorbing transparent body, which is obtained by applying a solution of a polysilazane-based mixture to form a coating film. 2. The ultraviolet / infrared absorbing transparent body according to claim 1, wherein the synthetic resin-based primer coating solution is an acrylic primer coating solution. 3. The ultraviolet / infrared absorbing transparent body according to claim 1, wherein the polysilazane-based mixture is a low temperature curable polysilazane-based mixture. 4. The ultraviolet / infrared absorbing transparent body according to claim 3, wherein the low-temperature curable polysilazane-based mixture is mainly composed of poly (perhydrosilazane).