CN1408665A - Fire-proof glass constructed by glass plate and gel layer in laminated layer mode - Google Patents

Abstract

The invention relates to fire-resistant glass consisting of a glass pane and a gel layer in a sandwich structure, wherein the gel layer is an aqueous solution of an amine salt and an acidic metal phosphate or an aqueous solution of an amine salt, an acidic metal phosphate and boric acid The reaction product of the gel component, which is filled into the gaps between the glass plates of the composite panel and gelled by heating. The fire-resistant glass has high stability to ultraviolet rays and temperature under the condition of long-term clarity through simple manufacture. The mixture of gel components is added to the colloidal silicic acid hydrosol solution and gelled.

Description

Fire-resistant glass composed of glass plates and gel layers in a laminated manner

field of invention

What the present invention relates to is to be made of glass plate and gel body layer with sandwich mode, and here gel layer is the reaction product of gel component, and it is made of amine salt and acidic metal phosphate or is made of amine salt, Composed of an aqueous solution of acidic metal phosphate and boric acid, it fills the gaps between the glass panes of a composite panel and gels by heating.

current technology

By DE 4236936A1 known a kind of fireproof glass that makes sandwich structure with this gel component. This known fire-resistant glass is different from the fire-resistant glass of the present invention in that it does not use a real gel layer, but a high-viscosity solution layer to make fire-resistant glass, as described in DE 3 729 867 A1. The fire-resistant glass made of gel in this way is simple in manufacture and has good fire-proof performance, but it shows that its processability and stability are poor in practical applications.

Fire-resistant glasses in this regard are described in EP 0 732 388 B1, EP 0 582 168 B1 and EP 0596 324 B1 and are based on the introduction of gel components with water as the aqueous medium.

The manufacture of fire-resistant glass based on alumino-phosphate-amine salts is very difficult. In particular, the pretreatment time for degassing the gel component is very long due to its high viscosity and makes it difficult to fill it into the sandwich structure. Such long, variable gel times require considerable expense to maintain consistent product quality and predictable production cycles. It has good stability to UV light and temperature in principle, material defects (gel cracks) due to defects in its post-processing.

Another known fire-resistant glass that is already on the market is based on water glass gels modified with organic additives. This kind of fireproof glass has high fireproof performance, but it also has poor stability. In addition, the fireproof glass containing water glass will form bubbles under the continuous action of ultraviolet rays and temperature, which will substantially deteriorate the optical properties of the composite board after some time. Fire-resistant glass with such an influence gel layer must therefore have additional protective measures, such as a UV protection film, especially on the front side.

There is also fire-resistant glass that uses hydrogel as a fire-resistant material. Due to the large thickness of the gel layer, the surface weight of the fire-resistant glass is significant, so only standard-sized fire-resistant glass can be provided. Because its weight is too big, this fireproof glass can not be generally applicable and can only be used in specific occasions.

A kind of bonding material and coating material disclosed from DE 4401636C2, this is a kind of mixture that is formed by aluminum-phosphate-amine salt and silica sol. Although it has intumescent properties, this mixture cannot be applied to fire-resistant glass due to its lack of transparency. The use of such coatings is limited by their high layer thicknesses and the overall system must have very good light transmission and no light scattering.

Contents of the invention

The object of the present invention is to provide a fireproof glass which remains transparent for a long time under standard conditions, has a high stability to UV rays and temperature and is easy to handle during production.

This object is solved according to the invention in that the gel component mixture is added to a hydrosol of silicic acid colloids and gelled.

In this case, the aqueous medium substantially gels the gel component in a short time and can reasonably produce fireproof glass. The processability of the overall system is significantly improved due to the greatly reduced output viscosity and unexpectedly a hard gel. The slight shrinkage during gelation greatly simplifies production. A gel layer of high transparency was unexpectedly obtained, making it possible to use a given mixture for the first time in the manufacture of fire-resistant glass.

Commercially used silicic acid sols can be used as the silicic acid sol. It is usually made by ion-exchanging dilute solutions of alkali metal silicates. According to one embodiment, the silicic acid sols used have particles with a specific surface area in the range from 50 to 500 m ² /g. The silicic acid sol has a solid content of 10 to 50% by weight and a pH value of 7 to 8.

Mixtures of acidic metal phosphates and amine salts of boric acid are preferably used as gel components. The acidic metal phosphate is preferably prepared by the reaction of aluminum hydroxide and orthophosphoric acid, but may also be the reaction product of a mixture of phosphate and phosphoric acid with addition of additional metal compounds. A very suitable mixture is prepared, for example, by reacting 1 mol of aluminum hydroxide with a multiequivalent of orthophosphoric acid, preferably 3 to 5 mol of orthophosphoric acid. Ammonium salts of boric acid are prepared by reacting a water-soluble, preferably aliphatic, amine with boric acid. A preferred ratio of boric acid to aliphatic amine is 1:2 to 1:4. The amines may be primary, secondary or tertiary amines or mixtures thereof, wherein the primary amine used is preferably monoethanolamine.

For the composition of the mixture the aluminum-phosphate-amine salt solution is pregelled at a temperature between 10 and 75°C, preferably between 20 and 60°C. The pH of the solution before gelling is adjusted to pH 5.8 to 6.5 or 8 to 10 with an alkaline solution. Especially suitable are aqueous solutions of sodium hydroxide or potassium hydroxide. Water-soluble amines can be added especially in the pH range of 5.8 to 6.5. The silica sol should be added under vigorous stirring. The ratio of the mixture can be between 1 to 0.005 to 1 to 0.25. The solution thus formed was almost clear and transparent.

After degassing, the solution is injected into a multilayer composite board and gelled at a temperature of 50 to 120° C. in a drying oven. The gelling process can be done in one step or in multiple steps, so that the resulting gel is clear and transparent.

The composite pane can consist of sodium silicate glass and/or borosilicate glass. This constitutes a sub-system for use in compounds with UV-sensitive internal compositions as UV or temperature protection.

After gelling, the fireproof glass frit can be cut to the required size, and the edge of the composite board is broken and closed.

The fireproofing material is injected between the 3 x 1.5 mm interstices of the composite panels, eg standard 4 x 3 mm sodium silicate glass panels. Here the composite panels are sealed under hydrostatic pressure and subsequently heated in a drying cabinet at 90° C. After 2 to 8 hours the fireproof mass gelled to a hard gel. At this point there is no longer hydrostatic pressure. After being cut to the required size of the composite panel, its sides are closed and sealed.

The composite panels produced in this way represent high-quality fire-resistant glass with high mechanical strength and high weather stability. The composite panel can be used in combination with functional glass.

Example

The gel composition used is described for the embodiment of the fire-resistant glass according to the invention.

The first step is to dissolve 100g of Al(OH) ₃ in 445g of 65% phosphoric acid solution, which is stirred at 90°C for 1 hour.

The second step is to dissolve _{125g H3BO3} in 260g 98% H2 _- N- _CH2 - _CH2OH and heat at 90°C for 1 hour.

Mix the aqueous solutions obtained in the above two steps and add 50% NaOH to adjust the pH value to 6.5. Then add 10 g of 30% silicic acid sol (220 m ² /g) to the prepared above solution at 65°C.

The fireproof substance (gel component) thus obtained is degassed before being injected into the composite panel. The gel component is pretreated at a temperature of 20 to 60° C. before being injected into the composite plate.

The gelation process is carried out one or more times at a temperature of 50°C to 120°C for 1 hour to 24 hours.

The amounts of the individual components of the mixture given as examples above are also given in relation to each other. Mix the corresponding multiples of each component according to the amount of the required gel component.

The composite sheet may comprise n glass sheets and (n-1) gel layers, where n≥2, such as n=4.

Claims (11)

1. Fireproof glass composed of a glass plate and a gel layer with a sandwich structure, wherein the gel layer is the reaction product of the gel component, which is made of amine salt and acid metal phosphate or is made of amine salt, acid metal phosphate It is composed of an aqueous solution of salt and boric acid, which is filled in the gap between glass plates and gelled by heating. It is characterized in that the mixture of gel is added to the aqueous solution of colloidal silicic acid and gelled. 2. Fire-resistant glass according to claim 1, characterized in that the silicic acid particles of the gel component have a specific surface area of 50 to 500 m ² /g as measured by the BET method. 3. Fireproof glass according to claim 1 or 2, characterized in that the solid content of the silicic acid is 10 to 55% by weight, and the gel composition contains 25 to 85% by weight of amine salts and metal phosphates or amine salts, metal An aqueous solution of phosphate and boric acid and a mixture of gel components having a solids content of 30 to 75% by weight. 4. Fire-resistant glass according to claims 1 to 3, characterized in that the pH of the gel composition is adjusted to 5.8 to 6.5 or 8 to 10. 5. Fire-resistant glass according to claim 4, characterized in that the pH value is adjusted by adding aqueous sodium hydroxide or potassium hydroxide solutions or water-soluble amines. 6. Fireproof glass according to claims 1 to 5, characterized in that the ratio of amine salt and metal phosphate or an aqueous mixture of amine salt, metal phosphate and boric acid to silica sol is 1:0.005 to 1:0.25. 7. Fireproof glass according to claims 1 to 6, characterized in that, in the mixture formed by amine salt and metal phosphate or by the aqueous solution of amine salt, metal phosphate and boric acid, can add such as antioxidant, bonding agent, Additives for silicic acid sols such as reducing agents, UV-stabilizers and blowing agents. 8. The method for producing fire-resistant glass according to claims 1 to 7, wherein a gel component is injected into the composite panel, and its edges are sealed due to hydrostatic action, wherein the gel component is filled into the composite panel and It is gelled by heating and the composite board thus produced is cut into the desired size, sealed and closed at its edge, and it is characterized in that, before filling the gel component into the composite board, the first step is to 100g Al(OH) ₃ is put into 445g 65% phosphoric acid and stirred at 90°C for 1 hour to make an aqueous solution and the second step is to add 125g HBO ₃ to 250g 98% H ₂ N-CH ₂ -CH ₂ OH and stirred at a temperature of 90°C for 1 hour to make an aqueous solution, the two aqueous solutions were mixed and the pH value was adjusted to about 6.5 with 50% NaOH, and the aqueous solution thus prepared was added at a temperature of 55°C with 10 g of 30 % of the silicic acid sol and make the gel component constitute and fill the composite board in a given proportion of the corresponding components necessary for use. 9. The method according to claim 8, characterized in that the gel component is filled directly into the composite panel at a temperature of 20 to 60° C. after pretreatment. 10. The method according to claim 8 or 9, characterized in that the gelling process is carried out directly or in several steps at a temperature between 50 and 120° C. over a period of 1 to 24 hours. 11. The method according to claims 8 to 10, characterized in that the silicic acid sol is added to the pH-adjusted aqueous solution under vigorous stirring, wherein the ratio of the aqueous solution to the silicic acid sol is 1:0.005 to 1: 0.25.