JP3361176B2 - UV and infrared absorbing transparent body - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transparent body coated with a coating film having excellent ultraviolet and infrared absorption. These are ultraviolet / infrared absorbing transparent bodies useful as ultraviolet / infrared shielding filter members for various window materials such as buildings or houses, vehicles, ships, aircrafts, and various display devices.

[0002]

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).

[0004]

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 has poor shape conformability,
It is very thick and difficult to reduce in weight, and its UVA absorption is insufficient.

Further, those disclosed in Japanese Patent Publication No. 4-44721 or Japanese Patent Application Laid-Open 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.

[0008]

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. By improving the light resistance while absorbing fluorescence by coexisting with the agent, the coating film in which fluorescence is inconspicuous is formed at a relatively low temperature, and by further protecting this with a silicone-based hard coating film as a top coat,
In particular, it provides a useful UV and infrared absorbing transparent material that is transparent and sharply shields UVA, and that also has heat ray absorption performance and can be used as an exterior material with excellent chemical resistance, scratch resistance and durability. It is a thing.

That is, the present invention is characterized in that 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. An ultraviolet and infrared absorbing transparent body excellent in durability, characterized in that it is formed by applying a silicone-based hard coating solution as described above, followed by heating and curing to form a protective thin film, which is then sequentially coated.

Also, the above-mentioned synthetic resin type primer coating solution is an acrylic type primer coating solution, which provides the above-mentioned ultraviolet and infrared ray absorbing transparent body.

As described 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'-tert-butylbenzoxazolyl) thiophene), or EB-501 (Mitsui Toatsu Dyes), and Nikkafluor S
Examples include B, KB, EFS, OB (manufactured by Nippon Kagaku Kogyo Co., Ltd.).

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

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 use ratio of the fluorescent whitening agent, the ultraviolet absorber and the infrared absorber 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 infrared 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.

Further, the synthetic resin is, for example, an acrylic resin, a urethane resin, a fluorine resin or a polyester resin, and the acrylic resin is a commercially available acrylic BR resin (Mitsubishi Rayon, for example). It may be prepared according to the relationship of concentration, viscosity or film thickness, etc., resin concentration is about 1 to 15 wt%, viscosity is about 10 to 1000 cP, primer film thickness is about 0.5 to 10 μ. Since the top film thickness is preferably about 1 to 5 μ, the total film thickness is preferably about 2 to 15 μ.

When the transparent substrate is made of glass, it is preferable to use a silane coupling agent in order to further improve the adhesiveness. For example, OS808A (Daihachi Chemical Co., Ltd. acrylic modified silicone) 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.

Further, 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. For example, clouding or cracking is likely to occur due to the elution of the primer component into the protective film, and if the heating is excessive, the adhesion of the protective film, which is a silicone-based hard coat, deteriorates.

The silicone-based 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.

Furthermore, the transparent substrate may be any one having a heat resistance of, for example, about 80 ° C. or higher, and is preferably inorganic glass, PC, PMMA,
Resin glass such as PET, whether inorganic or organic, is not particularly limited in shape, etc., in various shapes, and in sizes or peculiar configurations, such as bent plate glass, of course, various strengthening It goes without saying that it can be used as glass, strength-up glass, flat plate or single plate, and can also be applied as multi-layer glass or laminated glass.

[0023]

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 Since it is a transparent body coated with a protective film made of a silicone-based hard coating, it can be formed at a relatively low temperature as a film with excellent light resistance of the infrared absorber and inconspicuous fluorescence of the fluorescent whitening agent. It can shield up to the boundary and has excellent infrared absorption performance, as well as adhesion,
It has excellent chemical resistance, scratch resistance, and durability, and also has no glare due to reflection of visible light or radio waves or radio wave shielding properties, and can be used as an exterior, and it can be a useful UV-infrared shielding window, etc. The ultraviolet and infrared ray absorbing transparent body can be easily and inexpensively obtained by a simple coating process.

[0024]

EXAMPLES The present invention will be specifically described below with reference to examples. However, the present invention is not limited to the embodiment.

(Preparation of Ultraviolet and Infrared Absorbing Acrylic Primer) [For glass coating] Cyclohexanone and propylene glycol monomethyl ether as a solvent were put in a round bottom flask equipped with a stirrer and a circulator, and an acrylic resin was used as a diamond while stirring at room temperature. Knall 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 and infrared absorbing acrylic primer for glass coating.

The ultraviolet and 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 ℃). (Preparation of ultraviolet and infrared absorbing acrylic primer)
[For resin coating] Cyclohexanone, diacetone alcohol, and propylene glycol monomethyl ether as a solvent are put into a round-bottomed flask equipped with a stirrer and a circulator, and acrylic BR-85 resin (manufactured by Mitsubishi Rayon) is charged while stirring at room temperature. 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 ray 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 ℃). (Preparation of silicone hard coating solution) 500 with stirrer and circulator
Put 100 g of methyltriethoxysilane and 10 g of 3-glycidoxypropyltrimethoxysilane in a ml round-bottomed flask, add 0.04 g of phthalic anhydride, and use an oil bath water bath to approx.
It is heated to about 40 ° C to dissolve it, then 100g of weakly basic colloidal silica aqueous solution Snowtex C (Nissan Chemical Co., average particle size of about 15 μm, SiO ₂ content of about 20%) is added to about 40 ° C. The reaction was carried out for about 5 days to obtain a composition having a number average molecular weight of about 1100 by GPC (manufactured by Tosoh, ULC802A) and a solid content of about 29%. To this, 145 g of isopropyl alcohol was added, and the mixture was concentrated with an ultrafilter having a molecular weight cut off of 1000 (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 part of dicyandiamide as a curing catalyst was added to the composition to obtain a silicone hard coating solution.

(Performance Evaluation Method) Ultraviolet and Infrared Absorption: The absorption spectrum pattern was measured with a spectrophotometer. Fluorescence: Visual observation under natural sunlight outdoors. (There is no annoying luminescence or cloudiness.) Surface hardness: According to ASTM D1044, wear wheel CS-10F, 50
0 ΔH (haze) value (%) after rotation.

Adhesion: In accordance with JIS K5400, the cross-cut (1 mm mouth) tape peeling remaining number is displayed as / 100. Chemical resistance: acid ---- 24hr at 25wt% H ₂ SO ₄ infusion test.

Base --- 5 wt% NaOH 4 hours in drip test. Solvent --- 100% ethanol 4 hours by drip test. Weather resistance: In accordance with JIS D0205, the time until visual abnormality (film crack, peeling, noticeable yellowing) is observed with a sunshine carbon weather meter.

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 glass substrate for coating. .

One side of the glass substrate for coating was film-masked and dipped in the prepared UV-ray-absorptive acrylic primer solution for glass coating shown in Table 1 to 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.

Next, the glass substrate with the 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 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.

The obtained ultraviolet / infrared absorbing transparent glass substrate, which was an ultraviolet / infrared shielding glass substrate, was evaluated according to the above-described performance evaluation method. As a result, as shown in Fig. 1, although it has a slightly greenish color, it shields almost 100% of UVA, and the solar radiation transmittance is 50% or less. It can prevent appearance and haze, has excellent haze value (△ H) of 5 after the Taber test and has excellent scratch resistance, weather resistance of 3000 hours or more, no visible abnormality, no chemical resistance, and excellent durability. An ultraviolet and infrared absorbing glass plate having properties was obtained.

Examples 2 to 3 A glass substrate similar to that used in Example 1 was coated with a 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 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 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.

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. Similar to Example 1, it was a desired excellent ultraviolet and infrared ray absorbing transparent body.

Examples 4 to 5 A PC plate having a thickness of about 3 mm was dipped in an ultraviolet 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.

Next, 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.

The ultraviolet / infrared shielding film, which is the obtained ultraviolet / infrared absorbing transparent body, was evaluated in the same manner as in Example 1.
Similar to Example 1, it was a desired excellent ultraviolet and infrared ray absorbing transparent body.

Comparative Example 1 As in Table 1, as shown in Table 1, except that a UV whitening 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 and had a solar radiation transmittance of 90% or more. It was hard to call a glass plate.

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

With respect to the obtained ultraviolet and infrared ray absorbing glass substrate, only a slight amount of blue fluorescence was visually perceived, and a part of the visible region near ultraviolet was blocked, but the UVA up to that point was used.
However, the weather resistance was about 300 hours, and it was hard to say that it was a UV / infrared absorbing glass plate at the very beginning.

Comparative Example 3 As shown in Table 1, Example 1 was repeated except that an ultraviolet absorbing primer prepared with an ultraviolet absorbing agent TINUVIN327 (manufactured by Ciba Geigy) and an infrared absorbing agent NIR-AM1 (manufactured by Teikoku Kagaku Sangyo) was 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 is insufficient and the weather resistance is 10
It was about 00 hours, and it was hard to say that it was an expected ultraviolet and infrared absorbing glass plate.

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 an infrared absorbing primer prepared only with the infrared absorbing agent NIR-AM1 (manufactured by Teikoku Kagaku Sangyo) was used. Obtained.

The obtained infrared absorbing glass substrate had no ultraviolet ray cutting performance and a weather resistance of about 500 hours, and it was hard to say that it was an expected ultraviolet ray infrared absorbing glass plate. .

[0049]

[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.

[0051]

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.
Good heat ray absorption performance, excellent adhesion, chemical resistance, scratch resistance or durability, can be used as an exterior, and can be given various functionalities, such as buildings, houses, vehicles It is possible to easily and inexpensively provide a useful ultraviolet / infrared ray absorbing transparent body that 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 the front page (72) Inventor Koichi Yamamoto 1510 Oguchi-cho, Matsusaka-shi, Mie Central Glass Co., Ltd. Glass Research Laboratory (56) References JP-A-6-145387 (JP, A) JP-A-6- 316443 (JP, A) JP-A-6-316444 (JP, A) JP-A-7-187717 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C03C 17/34

Claims (2)

(57) [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 dissolved in an organic solvent to apply a silicone-based hard coating solution, which is cured by heating to form a protective thin 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.