JPS593958B2 - Method for producing flexible inorganic noncombustible molded body - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION Conventionally, synthetic resin sheets, foam sheets, mats, etc. have flexibility but lack nonflammability.

On the other hand, inorganic molded objects such as tiles, slate, concrete plates, and cement mortar plates are nonflammable, but they have no or almost no flexibility, and combustible furniture such as buildings, synthetic resin, and wood are nonflammable. It is not possible to coat the curved surfaces of everyday objects or other items to make them nonflammable.

The present invention eliminates the drawbacks of both of the above, and provides coating materials for the floors, roofing materials, ceiling materials, wall materials, pillars, etc. of buildings that are highly flexible and have not only flat surfaces but also curved surfaces, as well as furniture, etc. Experimental research was conducted to obtain an inorganic nonflammable molded product that can be used in a wide range of areas.

In this case, for example, a metal phosphate salt is used as an inorganic film-forming agent, and an aqueous slurry mixture containing enough magnesium oxide to cure this is applied to a glass fiber woven fabric to impregnate it, and then heated and cured. Although a flexible molded product was obtained, cracks occurred during the manufacturing process and a good product could not be obtained.

The present invention provides a method for producing a good flexible inorganic noncombustible molded article that does not cause cracks even when cured by heating. An aqueous slurry mixture containing an appropriate amount of a relatively fast-acting curing agent and a relatively slow-acting curing agent,
After creating a molded article by impregnating and coating a shaped fiber base material such as paper, woven fabric, non-woven fabric, mat, etc. and integrally covering and bonding the shaped fiber base material, the inorganic film-forming agent is coated with a fast-acting curing agent.
It is characterized in that one part is cured, and the remaining part is then cured with a slow-acting curing agent.

Furthermore, the present invention relates to the above-mentioned manufacturing method, and also provides a manufacturing method that provides a product molded object with a large curvature. It is characterized by curing the film forming agent in two stages using each curing agent.

Next, the present invention will be explained in detail.

Examples of the inorganic film forming agent include alkali metal silicates such as sodium silicate, silica-based materials such as colloidal silica,
Phosphate metal salts such as aluminum phosphate and aluminum polyphosphate are used.

As a hardening agent, mica powder, metal oxides such as zinc oxide, calcium hydroxide, calcium silicate, etc., and various other hardening agents are used, and for the film forming agent used, magnesium oxide, zinc oxide, etc. are relatively fast-acting. curing agent and a relatively slow-acting curing agent such as aluminum hydroxide, one part of the film-forming agent is first cured with the fast-acting curing agent, and then the remainder is cured with the slow-acting curing agent. Mix appropriate amounts of each.

Organic binders added to further increase curvature include chloroprene latex, SBR latex, acrylic resin, melamine resin, urea resin and other water-soluble water-resistant synthetic resins, polyester emulsions, epoxy resin emulsions, vinyl chloride emulsions, and chloride. These include synthetic resin emulsions such as vinylidene emulsions.

When such an organic binder is added, it is preferable to use a flame retardant or flame retardant such as halogen acid, antimony oxide, aluminum hydroxide, halogen type, or condensed ammonium phosphate type.

Furthermore, if necessary, a small amount of inorganic mineral powder or inorganic fiber powder can be mixed.

Even if this mixture is molded, heated or cured at room temperature, a flexible inorganic molded body cannot be obtained.

The present invention utilizes such an inorganic slurry mixture for paper, woven fabric,
As a result of many experimental studies, it has been found that by impregnating and coating a regular fiber base material such as a non-woven fabric mat, and forming a molded body by integrally covering and binding the regular fiber base material, it is possible to obtain an inorganic molded body that is highly curved. I found it.

Since this molded body is both nonflammable and waterproof, it can be used as an advantageous inorganic material that can be used as a covering material even on curved surfaces in place of conventional waterproofing materials and noncombustible materials of this type. Extremely advantageous.

The fibers of this fiber base material may be of vegetable, animal, mineral, or metallic type, and it does not matter whether they are long fibers or short fibers.

A part of the inorganic film-forming agent is cured using a fast-acting curing agent, and then the remaining part is cured using a slow-acting curing agent to form a flexible molded body having a water-resistant cured inorganic film. In order to obtain a non-combustible molded article, it is generally heat treated after that, but by then a part of it is cured at room temperature by the fast-acting curing agent, and then the rest is cured by the slow-acting curing agent by the heat treatment. At the same time, the molded body is dried.

To give a more specific example, each slurry-like nonflammable mixture of the following formulation examples was stirred and kneaded using a mixer.

The blending ratio is in parts by weight. Formulation example Aluminum phosphate 30 parts Zinc oxide
10 parts aluminum hydroxide 20 parts titanium oxide 15 parts glass fiber (10im length) 5 parts titanium oxide
15 parts Water 15 parts The slurry-like mixture of the above example was impregnated and coated on an asbestos fiber woven fabric to create a thin coating film on both sides, and heated at 80°C for 10 minutes to produce a sheet-shaped molded product (Sample AI). I got it.

In the sample A1, no cracks were observed in the cured film.

This sample A1 was tested for flame retardancy, flexibility (20°C), tensile strength, elongation, and waterproofness based on JISAi321, and the results shown in Table 1 below were obtained.

For comparison, a slurry-like mixture was prepared by removing aluminum hydroxide from the above formulation example and replacing it with one containing 30 parts of zinc oxide, and was treated in the same manner as in the above specific example to obtain a molded body. Many cracks were observed in the cured film, making it unsuitable as a product.

Furthermore, for comparison, a slurry-like mixture in which zinc oxide was removed from the above formulation example and 30% aluminum hydroxide was added was treated in the same manner as in the above specific example, but the hardening treatment showed no water resistance. It was a molded product that dissolved in water with no oxidation.

When heat curing was carried out at 400°C for 10 minutes, a molded product with good water resistance was obtained. occurred.

Next, we created formulation examples in which a small amount of organic binder was added in various proportions to the same formulation ratio as the formulation example of the present invention (sample AI), and as in sample A1, the same glass fibers were mixed into a mud shape. Similar tests were conducted on product samples A2, A3, and A4 obtained by similarly impregnating and curing a base material prepared using the same method, and the following results were obtained.

In addition, from many experimental results, as long as the amount of synthetic resin added is up to about 25% by weight based on the entire molded product, a product that maintains a grade 1 flame retardant pass can be obtained; ~3
It was recognized that a product with even better flame retardancy could be obtained by adding a halogen type flame retardant, a condensed ammonium phosphate type flame retardant, etc. in a weight percent.

Next, a manufacturing example of a preferable inorganic coated cured molded product of the present invention will be explained.

Aluminum phosphate (general formula aAl□03・bP20
It is preferable to use composite aluminum phosphate obtained by reacting aluminum phosphate with polyvalent metal ions such as zinc, magnesium, calcium, chromium, iron, etc.

In this case, the atomic ratio of aluminum to phosphorus (Al/P ratio) as aluminum phosphate is 1. ．． 1.32, or as composite aluminum phosphate A l /P
, those obtained by reacting with metal ions such that the ratio is in the range of 1/3 to 1.5/3 are preferable.

These aluminum phosphates may have a moisture content of approximately 50%, but may also be used after being spray-dried into a powder form.

A metal oxide such as zinc oxide or magnesium oxide is added as a hardening agent to these aluminum phosphates as an inorganic film forming agent.

The hardening agent used should be one that has been fired at a temperature of 800°C or higher.

According to many experiments, it is not preferable to perform the curing rapidly at once, as described above, and as a curing agent,
It has been found that by using both fast-acting and slow-acting cures in combination and performing curing gradually in two stages, a crack-free and robust cured film can be obtained.

As a slow-acting curing agent, a composite hydroxide is created by reacting two or more metal hydroxides such as aluminum hydroxide with magnesium hydroxide or zinc hydroxide.
This is filtered, washed, dried, and fired at a temperature of 800°C or higher to obtain a composite metal oxide, which is pulverized to form a compound of the general formula
g0-yA1203゜XZn0-yA1□03(x, y
is an integer) that provides a slow-acting curing agent.

Also, a calcined reaction product of oxides such as aluminum phosphate and magnesium oxide can also be used as a curing agent because of its slow curing speed.

- 20 parts of fast-acting hardener per 100 parts of aluminum phosphate
A preferred blending ratio is 100 parts or less of the slow-acting curing agent.

In this way, a mixture of the above aluminum phosphate and a monoacting and slow-acting curing agent is usually used as a filler.
An appropriate amount of at least one of titanium oxide, aluminum oxide, zirconium silicate, zirconium oxide, silicon oxide, calcined metal phosphate, etc., which has extremely low reactivity with aluminum phosphate, is added and blended.

Furthermore, in this case, a small amount of an organic binder τ within the above range is added and mixed in order to reinforce the moldability of the film-forming agent and improve the bendability of the molded product.

As the organic binder, an acidic resin emulsion, a rubber latex emulsion, a water-soluble resin, a powdered resin, etc., which are adjusted to the pH of the acidic metal aluminum phosphate, are used.

The slurry-like mixture is bonded to a fiber base material, and the types of fibers include glass wool, rock wool, asbestos, potassium titanate fiber, carbon fiber, metal fiber, etc., as well as cotton, linen, etc. Organic fibers such as , pulp, nylon, polyester, and vinylon can also be used, and are used in certain shapes such as sheets and mats for paper making, woven fabrics, net fabrics, etc., and have good bending properties of the product. For smoothing, a length of 5Qii or less is usually used.

The method of binding and coating the fibers with the slurry mixture containing acidic metal phosphate as a main component is to simply mix appropriate amounts of both into the shaped fiber base material, knead the mixture, and inject the mixture into a mold. There is a method of spraying a mixture of both to form a thin layer, and when using a certain sheet-like or mat-like fiber, a method of spraying or applying a slurry-like mixture onto it is generally used. Easy to work with.

When the coated fiber sheet or mat is passed through a pressure roller whose surface has been treated with water-repellent Teflon or silicone, good impregnation with the mixture can be obtained.

The aluminum phosphate-based molded plate with a built-in fiber base material formed in this manner may be left as it is at room temperature, or immediately heated to a normal temperature of preferably about 300°C or less
The curing is performed in a heating furnace at 0 to 200°C.

In this case, the film-forming agent is partially cured in two stages, first with the fast-acting curing agent for one part, and then with the slow-acting curing agent for the remaining part. A cured molded plate that is good and robust can be obtained without cracks or rapid shrinkage.

A further advantage of this is that a layer of mineral particles such as any other flexible metal foil, roofing sheet, mat, decorative sand grains, crushed stone grains, etc., is sprinkled on the upper surface of the molded plate in the initial stage of hardening. It is possible to obtain a laminated flexible inorganic noncombustible molded body by polymerizing and pressurizing the body.

Furthermore, during the initial curing process, processing treatments such as wavy molding and embossing to create an uneven pattern can also be performed.

Also, as mentioned above, when limiting the amount of curing agent added,
It has been confirmed through experiments that a molded article with appropriate hardness and no cracks can be obtained.

Next, zinc oxide is used as the former hardening agent, aluminum hydroxide is used as the latter hardening agent, titanium oxide is mixed as the filler, and glass mat (450g/772g) is used as the core material.
''), curing tea at 130℃ for 30 minutes, product sample thickness 1m
The results of the test using m were as shown in Table 3 below.

From the above, it can be seen that from the viewpoint of water resistance, the amount of the fast-acting curing agent is preferably 20% or less, and the amount of the slow-acting curing agent is preferably 100% or less.

Next, the results of various experiments on the relationship between the amount of organic binder added and its flame retardance are shown in Table 4 below.

As can be seen from the above, the amount of synthetic resin added is preferably up to about 25% based on the mixture content from the viewpoint of flame retardancy.

It is also found that when no flame retardant is added, excellent flame retardancy is maintained even when added alone up to about 5%.

The above test method is JISA132 for combustion test.
1, the flexibility test was conducted by measuring the limit of wrapping around cylinders of different diameters until cracking occurred, and the tensile test was conducted using an Instron type tensile testing machine with a grip interval of 20 cm.
, tensile speed 100771/m.

The measurement temperature was 20°C.

The drawings show the product of the present invention based on the above-mentioned embodiments, and FIG. A sheet-like molded product A of approximately one size is shown, and the sheet A is an inorganic flame-retardant product that can be largely curved as shown by the chain line.

Figure 2 shows that the above-mentioned cured molding material is impregnated and coated on both sides of a regular base material such as a non-woven fabric made of inorganic or organic fibers having a thickness of about 1 to 3 mm, such as paper making material. This figure shows a sheet or board molded product A consisting of a cured molded product a that is coated and bonded with a coating layer having a thickness of 0.511 M or less.

This can also be obtained with a large curvature in the same manner as described above.As described above, in accordance with the present invention, an aqueous slurry mixture of an inorganic film-forming agent and a curing agent is impregnated and coated on a shaped fiber base material and subjected to a curing reaction. When producing a flexible inorganic noncombustible molded article, the curing agent is a relatively fast-acting curing agent and a relatively slow-acting curing agent. Instead of curing all of the film-forming agent at once, a part of the film-forming agent is first cured with a fast-acting curing agent, and then the rest is cured with a slow-acting curing agent. As a result, it is possible to reliably produce a good flexible inorganic noncombustible molded article that is free from cracks and has excellent water resistance.

[Brief explanation of drawings]

FIG. 1 is a cutaway side view of one embodiment of the present invention, and FIG. 2 is a partially cutaway side view of the other side. a...Inorganic nonflammable molded body, b...Fiber base material, A...Product.

Claims (1)

[Scope of Claims] 1. An aqueous slurry mixture containing an inorganic film-forming agent as the main material and an appropriate amount of a relatively fast-acting curing agent and a relatively slow-acting curing agent is mixed with paper, woven fabric, After impregnating and coating a regular fiber base material such as a non-woven fabric or mat to create a molded article that is integrally coated and bonded to the regular fiber base material, a part of the inorganic film-forming agent is cured with a fast-acting curing agent, 1. A method for producing a flexible inorganic noncombustible molded article, comprising: curing the remainder of the molded article with a slow-acting curing agent. 2. The production method according to claim 1, wherein the inorganic film forming agent is at least one metal phosphate salt type. 3. An aqueous slurry mixture containing an inorganic film-forming agent as the main material, mixed with appropriate amounts of a relatively fast-acting curing agent, a relatively slow-acting curing agent, and a small amount of an organic binder.
After creating a molded article that is integrally coated and bonded to the fiber base material by impregnating and coating it on a regular fiber base material such as paper, woven fabric, non-woven fabric, or mat, or by mixing and molding with a dispersed irregularly shaped fiber base material,
A method for producing a flexible inorganic noncombustible molded article, characterized in that a part of the inorganic film-forming agent film is cured with a fast-acting curing agent, and then the remaining part is cured with a slow-acting curing agent.