JP2525200B2 - Glass plate having transparent porous composite metal film - Google Patents

Description

TECHNICAL FIELD The present invention relates to a glass plate having a transparent porous composite metal film capable of adsorbing various substances.

The glass plate having a transparent porous composite metal film obtained by the present invention is a decorative plate, a catalyst supporting plate, a pH buffer plate, a sensor by adsorbing a dye, a catalyst, an enzyme, a metal, a metal compound, an inorganic compound, or the like. It is used as such.

<Prior Art> Conventionally, as a glass plate having transparent porosity of this kind, there has been one in which a coating film containing a dehydrated product of aluminum oxide hydrate as a main component is formed on the glass plate. This transparent porous glass plate was formed by applying a dispersion containing aluminum oxide hydrate as a main component onto a glass plate, then drying and further dehydrating.

In addition, as other transparent porous glass plates, there is one in which a coating film containing, as a main component, dehydration product of silicon, titanium, zirconium, magnesium or the like alone or a mixture thereof is formed on the glass plate. This transparent porous glass plate is manufactured by a method such as immersing the glass plate in an alkoxide solution of silicon, titanium, zirconium, magnesium or the like or a mixture thereof and then drying and further dehydrating. It was

<Problems to be Solved by the Invention> However, all of the above-mentioned conventional transparent porous glass plates have the following problems.

(1) The problem of poor film forming property. That is, a conventional dispersion liquid of aluminum oxide hydrate or a solution of an organic compound containing silicon, titanium, zirconium, magnesium or the like alone or a mixture thereof as a main component or a hydrolysis dispersion liquid of the organic compound is generally Since the film-forming property was inferior, the film obtained by dehydrating the film had poor adhesion to the glass plate and poor bonding force between the molecules constituting the film. As a result, it was difficult to obtain a homogenized and smooth film, and cracks and film peeling occurred in the film. In particular, when silicon, titanium, zirconium, and magnesium were used, it was remarkable, and it was extremely difficult to form a film having a film thickness of 0.5 μm or more.

(2) The problem that the substance to be adsorbed is limited. In other words, a film mainly composed of dehydrated aluminum oxide hydrate and a film mainly composed of dehydrated product of silicon, titanium, zirconium, magnesium, etc., or their mixture has unique isoelectric point / activity. Since it has a point / surface pH, depending on the substance to be adsorbed, the decomposing action by heat or light may be promoted, which may have an adverse effect. As a result, the substance adsorbed on the obtained transparent porous glass plate is limited, and its use range is limited.

An object of the present invention is to solve the above problems and to provide a glass plate having a transparent porous composite metal film capable of adsorbing various substances without cracks or film peeling in the film. is there.

<Means for Solving the Problems> In order to solve the above problems, the present inventors have proposed a dehydrated film of a dispersion of aluminum oxide hydrate or an organic film of silicon / titanium / zirconium / magnesium. As a result of repeated research and analysis of the dehydrated film of the compound solution or the hydrolyzed dispersion liquid of the organic compound, the dispersion liquid of aluminum oxide hydrate to be applied / formed on the glass plate was appropriately selected, and further Unique isoelectric points each of which uses a mixture of a dispersion of aluminum oxide hydrate and a solution of an organic compound of silicon / titanium / zirconium / magnesium or a hydrolyzed dispersion of the organic compound
It has been found that the above problems can be solved by adjusting the active sites / surface pH. That is, the present invention provides the following (a) a solution of an organic compound of at least one element selected from the group consisting of silicon and titanium / zirconium / magnesium or a hydrolyzed dispersion of the organic compound of the element: 1380 to 1440 cm ^-1 and 1500 to 1550 cm ^-1 , 1610 to 16 by light transmission infrared spectrum analysis
A dehydrated film of a mixture of a dispersion liquid of aluminum oxide hydrate and a dehydrated film having at least two characteristic absorption peaks selected from the characteristic absorption peak group of 50 cm ⁻¹ was formed on a glass plate. It is a glass plate having a transparent porous composite metal film.

 The present invention will be described in more detail.

First, the silicon or titanium required for this invention
A solution of an organic compound containing zirconium / magnesium or a hydrolyzed dispersion of the organic compound and a dispersion of aluminum oxide hydrate are prepared.

A solution of an organic compound of silicon or an element of titanium / zirconium / magnesium or a hydrolyzed dispersion of the organic compound is obtained as follows.

Obtained by dissolving at least one element selected from the group consisting of silicon and titanium / zirconium / magnesium, for example, an alcoholate compound or an acetylacetonate compound in an organic solvent, or by hydrolyzing the compound with an acidic aqueous solution. To be

Examples of the alcoholate compound include methyl silicate, ethyl silicate, n-propyl silicate, n-butyl silicate, titanium tetramethoxide, titanium tetraethoxide, titanium tetraisopropoxide, titanium tetrabutoxide, methyl zirconate, and ethyl zirconate. There are n-propyl zirconate, isopropyl zirconate, n-butyl zirconate, magnesium dimethoxide, magnesium diisopropoxide, and the like, and examples of the acetylacetonate compound include titanium acetylacetonate, zirconium acetylacetonate, and magnesium. Acetylacetonate etc. The organic solvent includes isopropyl alcohol and ethyl alcohol, and the acidic aqueous solution includes acetic acid aqueous solution.

On the other hand, a dispersion of aluminum oxide hydrate is obtained as follows.

(A) After sufficiently dissolving metallic aluminum in isopropyl alcohol, it is hydrolyzed with an acid, or (b) aluminum isopropoxide is dissolved in isopropyl alcohol and then hydrolyzed with an acid, (c) an aluminum salt. Is dissolved in water and hydrolyzed with an acid, and the like. This aluminum oxide hydrate dispersion has a specific absorption peak after dehydration, that is, 1380 to 1440 by a light transmission infrared spectrum analysis method.
cm ^-1 and 1500~1550cm ^-1, selects used which have at least two characteristic absorption peaks selected from characteristic absorption peaks of 1610~1650cm ^-1. To do this,
It is advisable to appropriately select the reaction starting materials and reaction conditions, and change the type of acid used during the reaction, the pH value, the solid content, and the temperature.

Alternatively, with a dispersion of this aluminum oxide hydrate,
A solution of an organic compound of the elements of silicon and titanium / zirconium / magnesium or a hydrolyzed dispersion of the organic compound is mixed. By this mixing, the isoelectric point, active point, and surface pH of each can be adjusted.

The mixing ratio of the solution of the organic compound or the hydrolytic dispersion of the organic compound and the dispersion of the aluminum oxide hydrate is at least one element selected from the group consisting of silicon and titanium-zirconium-magnesium. The atomic ratio with aluminum is preferably 100: 100 to 1: 199. This is because when the content of at least one element selected from the group consisting of silicon and titanium / zirconium / magnesium is more than 100: 100, the film-forming property and transparency are poor, and the content is less than 1: 199. This is because it is insufficient to control the isoelectric point, active point, surface pH, etc. of the dehydrated film to be obtained.

Further, the solution of the organic compound is preferably a solution of the alcoholate compound or the acetyl acetate compound of the element. This is because the structure of this compound is easily dissolved in an organic solvent or an acidic aqueous solution. Further, it is preferable that the hydrolyzed dispersion liquid of the organic compound of the element is an acetic acid acid hydrate of the element.
This is because the use of acetic acid acid hydrate can provide a colloid having a good film-forming property and forming a film having excellent transparency.

 Next, this mixed solution is applied onto a glass plate.

As the glass plate, glass plates of lead potassium soda, soda lime, alkali zinc borosilicate, aluminosilicic acid, borosilicate, barium borosilicate, soda barium silicic acid, quartz, etc. are used.

Examples of the coating method include a spinner method, a roll coating method, a gravure coating method, a gravure printing method, a dipping method, and a spray method.

Next, the glass plate coated with the mixed liquid is dried and then dehydrated. The conditions at this time are 70 to 130 ° C, 5 to 60
After heating and drying for minutes, 250 to 550 ° C, particularly preferably 300
It is recommended to heat carefully at ~ 500 ° C for 10-120 minutes.

By doing so, a transparent porous composite metal film capable of adsorbing various substances is formed on the glass plate.

The film thickness of the coating is 0.5 to 50 μm, preferably 1.0 to 5.
0 μm is preferable. If the film thickness becomes thicker, for example, if it exceeds 50 μm, the transparent coating tends to crack, and if the film thickness becomes thinner, on the other hand, if it is less than 0.5 μm, the amount of dyes, catalysts, metals, etc., tends to decrease. .

As the aluminum oxide hydrate dispersion according to the present invention, the dehydrated film is 1380 to 1440 cm ^-1 and 1500 to 1550.
cm ^-1, reason for using one having at least two characteristic absorption peaks selected from characteristic absorption peaks of 1610～1650Cm ^-1 are as follows. That is, this aluminum oxide hydrate dispersion is particularly excellent in transparency and film-forming property as compared with general aluminum oxide hydrate dispersions. In other words, this allows other elements, that is, silicon.
A large amount of titanium, zirconium, and magnesium can be mixed in, and the film thickness necessary for adsorbing various substances can be secured.

In addition, 1380-1440 cm ^-1, and 1500-1550 cm ^-1 , 1610-
At least 2 out of 3 characteristic absorption peaks at 1650 cm ^-1
At present, it is not easy to elucidate the reason why a film having excellent transparency and film-forming property can be obtained with a film having one characteristic absorption peak. However, regardless of the reason, the dehydrated aluminum oxide film having the characteristic absorption peak specified in the present invention is said to have excellent transparency and film-forming property which could never be obtained by the conventional porous glass plate. It was found from many experimental examples.

Furthermore, a detailed examination of this experimental example revealed that
80～1440Cm ^-1 and 1500～1550Cm ^-1, having all three characteristic absorption peak of 1610～1650Cm ^-1 is excellent in transparency and film forming properties, also the characteristic absorption peak at 1610～1650Cm ^-1 Strength of 1380 ~ 1440cm ^-1 and 1500 ~ 1550cm
It was also found that when the intensity of the characteristic absorption peak at ^-1 is stronger, the transparency and film-forming property are more excellent.

Conversely, 1380-1440 cm ^-1 and 1500-1550 cm ^-1 , 1610-
When at least two characteristic absorption peaks cannot be confirmed from the characteristic absorption peak group at 1650 cm ^-1 , the transparency and film-forming property are lacking. Further, even if there is a characteristic absorption peak only in the neighboring band position different from the characteristic absorption peak,
Its transparency and film-forming property were extremely poor.

The light transmission infrared spectrum analysis method in the present invention means that a sample is dried from a dehydrated film of aluminum oxide hydrate formed on a glass plate, or a dispersion containing aluminum oxide hydrate as a main component is dried. It is preferably obtained from dehydrated products, and is measured according to the conventional potassium bromide method. Examples of analyzers that can be used in the light transmission type infrared spectrum analysis method include those of various companies such as JASCO A-202 in a dispersion type infrared spectrophotometer, and a Fourier transform infrared spectrophotometer. Here, you can use those from other companies such as Nicolet Japan 5DX.

Incidentally, the surface reflection infrared spectrum analysis method, since the above-mentioned characteristic absorption peaks tend not to appear clearly, in the present invention, the aluminum oxide hydrate dehydrated film of the aluminum oxide hydrate using the light transmission infrared spectrum analysis method. It is recommended to measure the characteristic absorption peak.

The glass plate having the composite metal film of the present invention must of course be guaranteed to be transparent and smooth without optical impurities. Moreover, it is necessary that the surface has a high adsorption ability, that is, a large number of microscopic adsorption holes are formed. However, since these fine holes are not of a size that can be optically detected, and the average pore size is 0.1 μm or less, most of them are 0.05 μm or less, which adversely affects transparency and smoothness. There is no such thing.

This point will be described in more detail. As the transparency required for the glass plate having the composite metal film of the present invention, the one in which the dehydrated film is formed in a thickness of 2 μm on the glass plate is It is desirable that the glass plate has a wavelength of 400 to 700 nm as a reference and a transmittance of 85% or more.

As for smoothness, the unevenness of the surface is 0.4 mm within a width of 1 mm.
It is desirable that the thickness is μm or less.

Further, as the adsorptive property, the specific surface area of the dehydrated film is 100 m ² / g or more by the BET method, and particularly preferably 200 to 7
00m ² / g is desirable.

A glass plate having such a composite metal film has a strong ability to adsorb a dye, a catalyst, an enzyme, a metal, a metal compound, an inorganic compound, and the like, and many uses of these properties have been found.

<Example> Example 1 1 kg of aluminum isopropoxide is added to 7 kg of water and stirred and mixed. Next, 1 kg of an acetic acid aqueous solution having a pH of 3.2 was added, and the mixture was further heated for 1 hour to prepare a dispersion liquid of aluminum oxide hydrate. This is 1400cm ^-1 , 1510cm ^-1 , 1640cm ^-1 3 after dehydration by light transmission infrared spectrum analysis method.
This is a dehydrated film having two characteristic absorption peaks. 5 kg of this aluminum oxide hydrate dispersion (solid content of 6% at the time of firing at 500 ° C.) was added to 0.3 kg of ethyl silicate dissolved in 5 kg of ethyl alcohol, and the mixture was stirred to prepare a semitransparent sol liquid. (Si: Al = 14: 86) This sol solution is uniformly applied on one surface of a transparent glass plate by a roll coating method, and is first gently dried at room temperature to 100 ° C. After confirming that the gel was uniformly and beautifully adhered to the glass plate surface, the gel was placed in a baking furnace kept at about 400 ° C. and heated for about 80 minutes.

Then, a glass plate having a composite metal film having a film thickness of 5 μm and excellent in activity on the surface was obtained.

On the other hand, red disperse dye CIDisperse Red 60, blue disperse dye CIDisperse Blue 56, yellow disperse dye CIDisperse
For each of Yellow 54, we made three color offset inks of red, blue and yellow using alkyd resin as a binder,
These inks were sequentially printed with a pattern of each color on a coated paper by an offset printing method to prepare a transfer paper having a landscape picture pattern.

Next, after superposing this transfer paper and the glass plate having the composite metal film, 180 ° C. under reduced pressure for 30 seconds, 1 kg / cm ²
The above pattern was sublimated and transferred by applying heat and pressure. After coating the melamine resin on the coating of the glass plate transferred in this way to form an overcoat layer, heat treatment was performed at 160 ° C for 30 minutes, and it was a stained glass style with excellent transparency and good physical properties. A glass plate was obtained.

This stained glass-like glass plate did not accelerate the decomposition of fuel in the light resistance / heat resistance test.

Example 2 1 kg of aluminum isopropoxide is added to 5 kg of water and stirred and mixed. Next, 1 kg of an aqueous acetic acid solution having a pH of 3.0 was added, and the mixture was further heated for 1 hour to prepare a dispersion liquid of aluminum oxide hydrate. This 3 dehydration ^{after, 1400cm -1 · 1500cm -1 · 1640cm} -1 by an optical transmission type infrared spectroscopy
This is a dehydrated film having two characteristic absorption peaks. Add 6.3 kg of this dispersion of aluminum oxide hydrate (6% solid content at 500 ° C firing) to a solution of tetra-n-butyl titanate 0.37 kg dissolved in isopropyl alcohol 3.7 kg, and stir to make it semi-transparent Was prepared. (Ti: A
l = 13: 87) This sol solution was applied uniformly on one surface of a transparent glass plate by a spinner method.

Then, after drying the glass plate at 120 ° C for 30 minutes, 300
After dehydration at 2 ° C. for 2 hours, a glass plate having a uniform thickness of 5 μm and a composite metal film having excellent transparency was obtained.

On the other hand, an aqueous screen ink was prepared using the red disperse dye CIDisperse Red 127 and the blue disperse dye CIDisperse Blue 26 as sodium alginate as a binder.

Using this ink, a floral pattern was printed by a screen printing method on a glass plate having a composite metal film, and then high-pressure and high-temperature steaming was performed. Then, it was cooled and washed with water to remove the binder, and a glass plate with a beautiful floral pattern was obtained. This glass plate was extremely beautiful as a vase or interior goods, advertisement, and signboard.

When a heat and light resistance test was conducted in the same manner as in Example 1, the decomposition of the dye was not accelerated.

Example 3 10 kg of aluminum secondary butyrate was dropped into 80 kg of water, stirred and heated, 3 kg of a nitric acid aqueous solution having a pH of 3.5 was added, and the mixture was further heated for 3 hours to prepare a dispersion liquid of aluminum oxide hydrate. did. This is what the optical transmission type infrared spectrometry the dehydrate having two characteristic absorption peak of 1420cm ^-1 · 1650cm ^-1. Dispersion of this aluminum oxide hydrate (solid content 6% at 500 ° C) 5
0.3 kg of tetrabutylzirconium was dissolved in 5 kg of ethyl alcohol, and the mixture was stirred to prepare a semitransparent sol solution. (Zr: Al = 12: 88) This sol solution was bar-coated on a glass plate. The glass plate was dried at 80 ° C. for 1 hour and then dehydrated at 500 ° C. for 30 minutes to obtain a glass plate having a uniform composite metal film with a thickness of 3 μm.

This substrate is immersed in a 0.5% aqueous solution of acid dye CI Acid Red 32 (80 ° C), left for 10 minutes, pulled up, washed with water, dried and vacuum dehydrated at 100 ° C. I got.

When a heat and light resistance test was conducted in the same manner as in Example 1, the decomposition of the dye was not accelerated.

Example 4 10 kg of aluminum secondary butyrate was dropped into 85 kg of a nitric acid aqueous solution having a pH of 3.6, stirred and heated, and further heated for 3 hours to prepare a dispersion liquid of aluminum oxide hydrate. This is a light transmission infrared spectrum analysis method
The dehydration product has two characteristic absorption peaks of 1510 cm ^-1 and 1640 cm ^-1 . 5 kg of this aluminum oxide hydrate dispersion (6% solid content at 500 ° C. firing) was dissolved in 0.47 kg of magnesium acetylacetonate in 5 kg of 10% acetic acid aqueous solution and stirred to form a semi-transparent sol solution. Prepared.
(Mg: Al = 26: 74) This sol solution was bar-coated on a glass plate. The glass plate was dried at 100 ° C. for 1 hour and dehydrated at 450 ° C. for 1 hour to obtain a glass plate having a composite metal film with a thickness of 4 μm.

Next, a spray ink was prepared by dissolving 1% of the cationic dye CI Basic Green 4 in a solution of methyl alcohol: water = 1: 1.

This ink was spray-coated on a glass plate with gradation. Then, after steaming at 100 ° C. for 15 minutes, a glass plate having a beautiful green gradation pattern was obtained.

When a heat and light resistance test was conducted in the same manner as in Example 1, the decomposition of the dye was not accelerated.

<Effects of the Invention> The glass plate having the composite metal film of the present invention is transparent and
A dispersion of an aluminum oxide hydrate having excellent film forming properties, and a solution of an organic compound of at least one element selected from the group consisting of silicon and titanium-zirconium-magnesium or a hydrolyzed dispersion of the organic compound. Since the mixture has a dehydrated film, it has the following effects. That is, the dehydrated film formed on the glass plate is excellent in film forming property. Therefore, the film does not have cracks or film peeling, and has excellent adsorption ability. Further, there is no limitation on the substance adsorbed on the dehydrated film. Therefore, various substances can be adsorbed and can be used for various purposes.

Claims (4)

(57) [Claims] 1. A glass plate having a transparent porous composite metal film, wherein a dehydrated film of the following mixed solution of (a) and (b) is formed on the glass plate. (A) A solution of an organic compound of at least one element selected from the group consisting of silicon and titanium-zirconium-magnesium or a hydrolyzed dispersion of the organic compound of the element. (B) 1380-14 by light transmission infrared spectrum analysis method
40 cm ^-1 and 1500~1550cm ^-1, a dispersion of aluminum oxide hydrate which is a dehydrated coating film having at least two characteristic absorption peaks selected from characteristic absorption peaks of 1610~1650cm ^-1. 2. The atomic ratio of aluminum to at least one element selected from the group consisting of silicon, titanium, zirconium, and magnesium in the dehydrated film is 10.
The glass plate having the transparent porous composite metal film according to claim 1, which is 0: 100 to 1: 199. 3. Silicon and titanium zirconium
The transparent porous composite metal according to claim 1, wherein the solution of the organic compound of at least one element selected from the group consisting of magnesium is a solution of the alcoholate compound or acetylacetonate compound of the element. A glass plate with a membrane. 4. Silicon and titanium zirconium
The transparent porous composite metal film according to claim 1, wherein the hydrolyzed dispersion of an organic compound of at least one element selected from the group consisting of magnesium is an acetic acid acid hydrate of the element. Having a glass plate.