JPS5827225B2 - fireproof composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a refractory composition comprising a phosphate binder, a specific curing agent for the phosphate binder, and an alkali metal titanate.

The phosphate binder has the general formula MmOn-XP205.

YH20 (where M is a metal such as sodium, potassium, calcium, magnesium, zinc, aluminum, etc., m and n are positive real numbers that vary depending on the valence of the metal, and X and Y are positive real numbers.

), and because of its excellent water resistance and heat resistance, it is used in the production of construction materials as a binder for fillers such as aggregate and asbestos, and is well known for its use as adhesives and paints. , this binding material alone can be used at room temperature or 100%
It does not harden at low temperatures around 0C, and only hardens when heated to 5000C or higher (30000C or higher depending on the type of phosphate).

Therefore, methods of adding metal salts such as oxides, hydroxides, and chlorides of various metals to phosphate binders have been studied in order to cure the phosphate binders at room temperature or relatively low temperatures. However, these metal salts are rarely applicable alone, and it is common to mix several types of metal salts and add this to the phosphate binder (Japanese Patent Publication No. 48-3197).
(See Japanese Patent Publication No. 49-19690).

By the way, when mixing several types of metal salts and adding this to the phosphate binder, the phosphate binder and the metal salt should be mixed together so that the phosphate binder is uniformly cured without being partially cured. Although uniform mixing with the salts cannot be achieved within the desired time, it is possible that several metal salts act on the phosphate binder at each curing site at the same mixing ratio as originally done. desired.

However, when using several types of metal salts together, each metal salt naturally differs in particle size, specific gravity, and other properties, so after simply mixing the metal salts, this mixture is combined with phosphate. Even if they are added to the phosphate binder and stirred, some metal salts will not necessarily act on the phosphate binder at the original mixing ratio. When using several types in combination, it was necessary to strictly limit the compounding conditions of the metal salts and even the conditions of the aggregate, which is an additive other than the hardening agent.

Under the above circumstances, the present inventors have conducted research with the aim of providing a curing agent for phosphate binders that exhibits various characteristics when applied to phosphate binders by a simple manufacturing method, We have already succeeded in providing the desired curing agent and have filed an application.

The present invention was achieved as a result of research aimed at further improving the heat insulation performance and fire resistance of the fireproof composition containing the specific curing agent obtained above.

That is, the present invention includes a phosphate binder and: P2O5°MgO,
It contains a solid solution mainly composed of CaO and SiO□ as a curing active ingredient, and the weight ratio is 7 to 5 as MgO/P2O54, -7 to 8 as 3CaO/P205.
The present invention provides a refractory composition comprising: a curing agent for the phosphate binder having a SiO2/P2O5 of T~8; and an alkali metal titanate.

Here, the phosphate binder is as described above, but more specifically, monophosphoric acid, diphosphoric acid, metaphosphoric acid, double phosphoric acid, condensed phosphoric acid, sodium, potassium, etc. Examples include salts of calcium, magnesium, and aluminum, hydrates, aqueous solutions, and dehydrates thereof.

The curing agent that is a component of the present invention is a molten phosphorus fertilizer and includes a well-known substance. Therefore, it is natural that the hardening agent is a molten phosphorus fertilizer, and it can be prepared by using, for example, phosphate rock [3Ca (P
O4)3・CaF2], serpentine [3Mgo・2S i
02.2H20], ferronickel slag and other raw materials are ground and mixed, melted to 1300° C. or higher, and then rapidly cooled.

Generally, in the production method of dissolved phosphorus fertilizer, the phosphorus concentration, especially the phosphoric acid content that is soluble in a dilute solution of citric acid (martyrogenicity), is
While adjusting the blending ratio of phosphate rock, serpentine, ferronickel slag, etc. to keep it within the appropriate range as a fertilizer, it is believed that the melt (solid solution) of these raw material mixtures at high temperatures is the cause of a decrease in martyrdom. To avoid crystallization,
Manufacturing conditions are strictly controlled.

In the manufacturing method of the curing agent, which is a component of the present invention, if the crystalline content is increased by slow cooling the raw material mixture without rapidly cooling it after melting, the curing active ingredient will decrease by that amount. However, even with such a hardening agent, if it is mixed with phosphate, the crystalline components in the hardening agent may remain like aggregate, but other amorphous components hardens the phosphate.

Therefore, in obtaining the curing agent that is a component of the present invention, it is not necessary to determine the manufacturing conditions as strictly as in the case of melted phosphorous fertilizer, and it is not necessary to mix elements other than P t Mg tCa and Si into the raw materials. can also be tolerated more than in the case of dissolved phosphorous fertilizers.

The curing agent, which is a component of the present invention, can be produced in powder form, by appropriately changing the cooling mode of the melt during the manufacturing process.
It can be obtained in either granular or fibrous form, and can also be obtained as foamed granules by using a blowing agent in combination.

Powdered hardeners are advantageous if you want the entire amount to be consumed for hardening the phosphate, while granular hardeners allow only the surface of the hardener particles to be consumed for hardening the phosphate, leaving the remaining portion to be consumed. This is advantageous when it is desired to function as an aggregate.

Similarly, fibrous curing agents and foamed granular curing agents are also advantageous when it is desired to function not only as a curing agent but also as a reinforcing material or lightweight aggregate, as can be easily inferred from their forms.

The above-mentioned range indicating the weight ratio of MgO, etc. to P2O5 indicates a range that can practically function as a curing agent which is a component of the present invention, but does not necessarily indicate a critical value. do not have.

The range in which it can practically function as a curing agent varies depending on the amount of curing agent used with respect to the phosphate binder, the temperature conditions for curing, and the manner in which the fireproof composition, which is the object of the present invention, is used. , because it is difficult to clarify.

Therefore, it is difficult to specify a particularly suitable weight ratio of MgO, etc. to P2O5, but it is practically desirable to have a range in which a high solid solution ratio can be achieved on an industrial scale with good reproducibility, that is, a range in which the weight ratio is as follows. I can say that.

The alkali metal titanate salt, which is a component of the present invention, has the general formula do.

) and includes compounds in appropriate shapes such as fibrous crystals, powders, crushed products of melts, and powders.

Among these, whisker-like potassium tetratitanate or potassium hexatitanate is particularly preferred.

This alkali metal titanate salt greatly improves the heat insulation performance and fire resistance performance of the fireproof composition according to the present invention - and by extension, the cured product of the fireproof composition - but it is used only for the purpose of improving the heat insulation performance and fire resistance performance. If so, other filling materials may be considered.

However, the reason why it is particularly desirable to add an alkali metal titanate in the present invention is as follows.

That is, (1) When a fireproof composition is prepared only from a phosphate binder and the specific curing agent of the present invention, the cured product will be colored green in most cases due to the curing agent. However, when an alkali metal titanate salt is added, a white cured product can be obtained.

Therefore, if you want a white cured product with high reflective effect,
There is no particular need to add a pigment, and even if a cured product of a desired color is desired, the purpose of coloring can be effectively achieved by adding a pigment.

■Alkali metal titanates have good dispersibility in phosphate binders (for example, they have extremely good dispersibility compared to titanium white), and when used alone, they do not have the ability to harden phosphate binders. I don't have it.

Therefore, when preparing the composition according to the present invention, it is sufficient to first mix the phosphate binder and the alkali metal titanate until they become uniform, and then mix the curing agent, thereby ensuring good workability. can be achieved.

The appropriate composition ratio of each of the above-mentioned components in the fire-resistant composition according to the present invention cannot be unambiguously specified because it varies depending on the type and combination of each component, but the hardening agent is 100 parts of the phosphate binder. 2 to 300 parts, preferably 2
The alkali metal titanate is used in an amount of 2 to 200 parts, preferably 5 to 100 parts, based on the total of 100 parts of the phosphate binder and curing agent (the composition ratio may vary depending on the composition). is also expressed in weight ratio, and the same applies below).

If the ratio of the curing agent to the phosphate binder is less than the above range, curing may take a long time, or curing may be insufficient, resulting in poor water resistance, heat insulation performance, fire resistance, etc. of the cured product. On the other hand, if it is too large, the ratio of the excess curing agent remaining in the cured product becomes too large, resulting in a brittle refractory with weak bonding strength, which is not preferable.

In addition, if the proportion of the alkali metal titanate is smaller than the above range, the heat insulation performance and fire resistance of the cured product will decrease, and if it is too large, it will result in a brittle refractory with weak bonding strength, so both are preferable. It's not right.

In addition, when preparing the fireproof composition according to the present invention, if the total amount of the curing agent and the alkali metal titanate is kept constant and the addition ratio of the curing agent is increased, the amount of the alkali metal titanate will theoretically decrease. However, in reality, there is not such a clear difference.

This is thought to be because the hardening agent that remains in the refractory has excellent heat insulation performance and fire resistance performance (incidentally, the solid solution in the hardening agent in the present invention is
The refractive index is 1.55 or more, and the specific gravity is 2.20 or more, and these numbers support this assumption).

The essential components of the fire-resistant composition according to the present invention have been described above, but pigments, fire-resistant light reinforcement materials such as zirconium silicate, mica, etc. can be added to the fire-resistant composition according to this other invention.

In particular, water-soluble polyhydric alcohols such as glycerin, ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, oxyethylene/oxypropylene copolymer, methyl cellosolve, ethyl cellosolve, butyl cellosolve; methyl cellulose,
Water-soluble resin solutions such as hydroxyethyl cellulose and polyvinyl alcohol Nidiglycerol borate, diglycerol borate/oleate, diglycerol borate/
diglycerol borates such as laurate or modified diglycerol borates obtained by addition polymerization or copolymerization of ethylene oxide or propylene oxide; It can be said to be a useful filler because it prevents easy cracking and also functions effectively in adjusting the consistency and drying of the refractory composition.

These fillers usually have a content of 0.1 to
10% can be added.

The fire-resistant composition according to the present invention can be used for manufacturing molded products and forming coatings, and can be used to provide 1-hour, 2-hour, and 3-hour fire resistance for fire-resistant structures based on the provisions of Article 107, Item 1 of the Construction Order of the Building Standards Act. It is a suitable material for providing building materials and similar fire protection materials that are compatible with.

In addition, when using the fireproof composition according to the present invention for film formation,
It is possible to apply it directly to the object to be coated, but if necessary, it is also possible to apply it through a base material such as an inorganic adhesive, mortar, or concrete.

The main features of the fire-resistant composition according to the present invention other than those already mentioned are listed below. Even in this case, a good refractory can be obtained with good reproducibility.

(2) The curing agent, which is a component of the present invention, can be obtained from inexpensive natural sources and by a method established in the smelting phosphorus fertilizer industry, so it can be applied to the needs of the fireproof composition as a whole. The curing agent, which is a component of the present invention, can be formed into various forms as required, and other fillers may not be added to it. Even if there is no refractory, the surface condition of the final target refractory can be changed to some extent if desired.

The present invention will be further explained below with reference to Examples.

Reference example 1 Phosphate rock (burning loss 6.14 weight, Si028.80
Weight: Ca045.71 weight, Mg00.39 weight, P2O531.26 weight, others 7.7% by weight) 1
000 parts by weight, serpentine (burning loss 10.86 parts by weight, 5
i0239.81 weight rice cake, Ca0O, 85 weight rice cake, Mg
435 parts by weight, ferronickel slag (5i0253.71 weight, Ca04.88 weight, Mg029.92 weight%, 11.5 weight% of its content) Grind and mix,
It was supplied to the open hearth.

Next, the heated molten material discharged from the open hearth at approximately 1400°C is poured into water to be rapidly cooled, pulverized, and passed through a 0.5 sieve 98
% curing agent was obtained.

This curing agent was of the same quality as powdered phosphorous fertilizer manufactured by Hinode Chemical Industry Co., Ltd., and the results of its component analysis were as follows.

P2O521 weight ratio, M weight 16 weight rice cake, Ca032 weight%, 5i0225 weight rice cake, and other 6 weight ratio, and the mortality rate of this curing agent was 99.

Reference Example 2 670 parts by weight of phosphorous ore and 500 parts by weight of serpentine are crushed and mixed, and after being supplied to an electric furnace, the heated molten material discharged from the electric furnace at approximately 1400'C is injected together with high-pressure air. was quenched with spray water to obtain a granular curing agent in which more than 80 particles had a particle diameter of 0.1 to 0.5 m.

The results of component analysis of this curing agent were as follows.

P2O520.4 weight cake, Mg019.1 weight%, Ca
O30.3 weight ratio, S i0225.2 weight ratio, other 5 weight ratio, and the mortality rate of this curing agent was 99%.

Reference Examples 3 to 8 The curing agents obtained according to Reference Examples 1 and 2 are shown in Table 1 below.
(Note that slag in Table 1 means ferronickel slag).

Example 1 Immediately before use, 20 parts of the curing agent of Reference Example 1 was mixed and dispersed in a mixture of 100 parts of monobasic aluminum phosphate and 25 parts of potassium titanate fiber (manufactured by Otsuka Chemical Co., Ltd.), and immediately poured into a molding frame. 30
It was molded at room temperature under a pressure of Kf f /cm, and then cured at room temperature for 7 days to obtain a cured product with a thickness of 5 mm.

When this cured product was heated for 3 hours in accordance with the fire resistance test method of JISA1304, the temperature on the opposite side of the cured product showed a maximum temperature of 385°C as shown in the drawing (heating temperature curve 1 in the figure). It was found to pass the time fire resistance test.

Comparative Example 1 A cured product was produced in the same manner as in Example 1, except that potassium titanate was not used for comparison.

When this cured product was also subjected to the same test as in Example 1, as shown in the drawing (heating temperature curve 2 in the figure), the temperature on the opposite side of the cured product showed a maximum temperature of 620'C, and the fire resistance was 1 hour. I found out that I would pass.

Comparative Example 2 For comparison, a cured product was produced in the same manner as in Example 1, except that a hardening agent consisting of 10 parts of calcium hydroxide and 20 parts of zinc oxide was used.

When this cured product was subjected to the same test as in Example 1, as shown in the drawing (heating temperature curve 3 in the figure), the temperature on the opposite side of the refractory showed a maximum temperature of 620 ° C.
It was found that it passed the 2-hour fire resistance test.

Examples 2 to 11 Table 2 shows a group of examples conducted in the same manner as Example 1.

[Brief explanation of the drawing]

The drawing is a graph showing the fire resistance test results. In the figure, 1 is in Example 1, 2 is in Comparative Example 1,
3 shows the fire resistance test curves in Comparative Example 2, and 4 in the figure shows the heating temperature curve.

Claims (1)

[Scope of Claims] 1. A phosphate binder; The phosphate binder contains a solid solution mainly composed of P205, MgO, CaO, and Si02 as a curing active ingredient, and has a weight ratio of A refractory composition comprising: a curing agent for use in the industry; and an alkali metal titanate salt.