JPS58199761A - Alkali silicate composition, heat solidified matter and manufacture - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION This invention relates to compounds and their preparation. More specifically, an alkali silicate composition/A) containing an alkali silicate, 7 lithium, and a condensed phosphate having thermal assimilation properties, or an alkali silicate composition (B) obtained by removing the condensed phosphate from this composition (B) ), an elastic body, a coating or a molded body obtained by heating these compositions, and a method for producing the same.

In recent years, the use of petroleum-free materials for various materials has become an important technical issue in industry from the viewpoint of resource and energy conservation.

Incidentally, silicates have been attracting attention from the above-mentioned viewpoint as an abundant material that is inexpensive and easily available, and its effective utilization is desired. However, quartz salt has poor water resistance and chemical resistance, and it is difficult to put it into practical use because it causes shrinkage cracks and the F-0 phenomenon (whitening or deterioration due to the action of charcoal gas or moisture in the air). , and its practical application requires the skills of an expert.

Some of the present inventors have already proposed a curing agent that effectively utilizes alkali silicate (Japanese Patent Publication No. 16106/1986).
are doing. The present inventors have conducted intensive research to further increase the utilization of alkali silicate in industry, and have arrived at the present invention. The present invention provides an alkali silicate composition that is a base material for the assimilate, and a method for producing the assimilate.

That is, the present invention provides (1) a heat-curable alkali silicate composition (4) containing an alkali silicate, 7 watts, and a condensed phosphate; an alkali silicate molded product and a method for producing the molded product, characterized in that the composition (4) is molded and solidified under heating; (3) a coated product coated with a heat-solidified product of the composition (4); , and (4) alkali silicate and 7 lithium as constituent components.
The present invention provides an alkali silicate composition FB) which forms an elastic body upon heating, and an alkali silicate elastic body obtained by reacting this composition under heating.

Examples of the alkali silicate used in the present invention include sodium silicate, potassium silicate, and lithium silicate, and may be either an ortho compound or a meta compound. These alkali silicates may be used alone or in combination of two or more. In addition, alkali silicates are in the form of solids, hydrates, or aqueous solutions, but
In the present invention, any of these forms can be used. In particular, the alkali silicate used in the composition (A) of the present invention is preferably in a liquid form, and if it is solid at room temperature, it is desirable to make it into a liquid form by dispersing or dissolving it in an appropriate amount of water. . On the other hand, the alkali silicate used in the composition (B) of the present invention is an aqueous solution;
A fine powder is preferable in order to smoothly react with 7lift.

The 7 liter used in the present invention refers to a low melting point solid solution generally used as a flux in the kiln industry, and its chemical composition is considered to be a solid solution consisting of 21111 or more of a metal compound. In the present invention, 1 type or a mixture of 2 or more types of 7 liters is used, especially 10)-9A
M (trade name, manufactured by Nippon 7 Yellow ■) is preferably used because it does not contain lead and has low toxicity. The 7 liter used in the composition (B) of the present invention is preferably in the form of fine powder in order to allow the reaction to proceed smoothly.

20. -nH
2O (in the formula, y is a positive number of 6 or less, n is a positive number of 6 or less)
Examples include condensed phosphorus aluminums represented by the following formulas, and those in which X is 0.5 to 1, y is 1.5 to 3, m is 4 or less, and <0.1 to 3 are preferable. Condensed phosphates are usually provided as an aqueous solution or concentrated dehydrate, but in the composition rA) of the present invention, the content of the phosphorus compound or phosphate anhydride is 50% or more in terms of anhydride, especially 70% or more are preferably used, and these are usually provided in the form of powder. The reason why the condensed phosphate having the above-mentioned composition and properties is suitably used in the composition fA) of the present invention is that when the condensed phosphate is in an aqueous solution, the rapid reaction with the alkali silicate causes the alkali silicate to react with the alkali silicate. This is because the alkali silicate does not harden before the reaction with 7 liters is substantially completed, making it difficult to obtain a solidified product having the desired strength.

The blending proportions of the alkali silicate, 7-Lit, and condensed phosphate in the composition (A) of the present invention are appropriately selected depending on the type of each component and the intended use of the composition (A), but usually 100 parts (by weight) of the alkali silicate ), frit 0.1
~50 parts, preferably 0.5 to 20 parts, and 0.5 to 20 parts of condensed phosphorus salt.
Selected within the range of 1 to 50 parts, preferably 0.5 to 50 parts. If the mixture is too warm, the assimilate will lack sufficient strength and water resistance, and on the other hand, if it is too warm, the solidified product will become brittle, which is undesirable. In addition, if the amount of condensed phosphoric acid salt is too small, the solidified product may not have sufficient strength, water resistance, or fire resistance, while if it is too large, the solidified product may be brittle.
This is not preferred because the stability of the alkali silicate in composition (A) is reduced and the workability thereof is poor.

The composition (A) of the present invention may be prepared by mixing only the alkali silicate, 7 lithium salt, and condensed phosphate, or water may be added to adjust the workability. Ingredients, plasters, embellishments, fillers, etc., as well as co-hydrogen, alumina sol, Ia! fat emulsion,
! An aqueous fI fat solution may also be added.

The blending ratio of alkali silicate and 7L in the composition (n) of the present invention depends on the type of each component, the desired properties of the elastic body,
Although it is appropriately determined depending on the intended use of the elastic body, it is usually selected within the range of 0.1 to 50 parts, preferably 0.5 to 26 parts, per 100 parts of alkali silicate. If the blending ratio of 7 liters is too low, the elasticity of the elastic body will be insufficient and the assimilation process will take a long time, while if it is too high, the cohesive force will decrease and the resulting elastic body will become brittle and elastic. This is undesirable because the reaction rate decreases or, furthermore, the reaction occurs rapidly and its control becomes difficult.

The composition tB) can be prepared by heating an aqueous solution of alkali silicate using a mixer such as a stirrer together with finely powdered alkali silicate, or by heating it with stirring while using a mixer such as a stirrer. This can be carried out by heating the alkali silicate and 7 liters while mixing them in a powder mixer or the like. Particularly in the latter case, it is desirable to add an appropriate amount of water to the mixture and heat it while kneading.

Compositions (A) and rn) of the present invention may contain commonly used alkali silicate stabilizers such as glycerin, glycerin borate, and derivatives thereof, pH adjusters, surfactants, and the like.

The molded article of the present invention is made by casting the composition (mu) into a desired mold and heating it under normal pressure or pressure at 40 to 400 oO for 10 minutes to 24 hours, preferably 60 to 200%. So 6
This is carried out by heat treatment for 0 minutes to 2 hours. At this time, if the heating temperature is less than 40°A, it will take a long time to complete the reaction, while if it exceeds 400°A, the bite-shaped material may shrink or abnormal foaming may occur due to rapid vaporization of the water content. This will reduce the homogeneity of the quality of the resulting molded product.
Undesirable.

In this way, the alkali silicate molded product of the present invention, that is, the solidified product of composition rA), can be easily produced using inexpensive raw materials. It has excellent water resistance, anti-F-4 properties (no E-F4 phenomenon), anti-crack properties, heat resistance, and thermal shock resistance, and has high industrial applicability.

The composition (A) of the present invention can also be suitably used as a coating material for metal materials such as slate plates, calcium silicate plates, or steel plates. The coating is manufactured by applying the composition (A) to the material to be coated to a desired thickness, usually from 0.1 to 30 I! ! l! This can be done by coating the molded product by a known coating method such as a brush coating method, a spray coating method, a border coating method, or a dip coating method so that the molded article has a color I, and then heat-treating it in the same manner as in the production of the molded article.

By using the composition rA) of the present invention as a coating material, a coating can be easily applied using inexpensive raw materials, and the coating has excellent water resistance, anti-effrostatic properties, anti-cracking properties, heat resistance, and thermal shock resistance. It has the advantage of suppressing the occurrence of cracks that occur with conventional inorganic compositions, especially when you want to express cosmetic appearance by changing the thickness, such as in uneven patterns. There are some things that are extremely expensive.

The elastic body of the present invention can be changed into a solid or viscous substance that is easily powdered by heat-treating the composition (B). At this time, since the heat treatment does not become an elastic body if the composition (B) is substantially solidified, it is necessary to stop the heat treatment at stage 111 (B stage) where it can be redissolved in water, and the heating treatment is performed at 40 to 200 oO.

Preferably under heating at 60 to 100°a for 5 minutes to 6 hours,
Preferably, this can be carried out by reacting for 10 minutes to 2 hours. If the heating temperature is less than 4000°C, it will take a long time for the reaction to complete, while if it exceeds 200°0, the reaction will proceed rapidly and the reaction will not be controlled, and the dehydration reaction will proceed at the same time. This is undesirable because it makes it difficult to remove a homogeneous and stable elastic body. More specifically, 100oo or more,
In particular, when heated for more than 2 hours at 120 parts 0 or more, it becomes a white solid with poor cohesive force and easily powdered, and even if water is added to the solid powder obtained from this, it has poor affinity with water and poor solubility in water. Even when mixed with water, the aggregate remains homogeneous<<
, this one shows no elasticity. Therefore, the heating conditions for preparing the elastic body of the present invention are desirably 2 hours or less, particularly 1 hour or less at temperatures exceeding 100QO.

On the other hand, at temperatures below 100°O, the elastic body of the present invention can flow even when heat-treated for a long time; for example, when heat-treated at 100°O for 6 hours, the reaction product is a white solid that easily solidifies, When water is added to this, it becomes sticky and coagulates to form a semi-transparent elastic body.As described above, according to the composition (B) of the present invention, it has been known that it takes 6 days to 1 week to form an elastic body. Compared to the conventional technology, which takes a long time and requires highly skilled skills to manage fR manufacturing conditions and stabilize quality, it is possible to easily manufacture an elastic square body.

In the present invention, prior to the heat treatment of the composition (B), a colorant, a filler, a resin emulsion, an aqueous titanium liquid, and an alumina sol are added to the composition (B) or to the elastic body obtained by the heat treatment. , colloidal silica, alkali silicate stabilizers, etc. may be added or mixed.

The elastic body of the present invention can be reversibly dissolved in water or volatilized from the dissolved substance, and the elastic body can be made thinner and thinner.
Physical properties such as hardness and elasticity can be adjusted arbitrarily, and it has excellent workability, and it can be encapsulated in rubber elastic materials, rigid materials such as metals and ceramics, and plastic materials such as plastics to increase S impact force. Less shape deformation compared to
This makes it possible to develop an elastic material with a high recoil coefficient, which can be used, for example, as a material for golf balls, soft baseballs, and other materials.

In addition, the elastic body of the present invention can be suitably used as a binder, and by using a curing agent such as a bound phosphorus salt, it can be used as a molded body, sheet, or coating composition, and has excellent adhesive properties and water resistance. It can be used as an inexpensive material that exhibits heat resistance and fire resistance, making it highly usable in industry.

Next, the present invention will be described in detail with reference to examples. A composition was obtained by mixing 5 parts of 9AM (manufactured by Nippon 7 Yellow Co., Ltd., the same hereinafter) and 10 parts of condensed phosphorus aluminum (manufactured by Fanehosaku Yoneyama Chemical Industry Co., Ltd.) using a Purpera type stirrer.

Examples 2 to 9 (Composition rA)) In the same manner as in Example 1, compositions having the following compositions were prepared.

(Example 2) Sodium silicate 1oO1,s7
Lit
4
titanium oxide 6s glycerin
1 part (Example 6) Sodium silicate 100 parts 7 parts
T
10
Total magnesium phosphate (Mg-100) 1
00 parts Titanium oxide 2 parts (Example 4) Frit
10 part condensed aluminum phosphate (MAR) 1g part titanium
1 part mica powder 6 parts glycerin, 1:1
False Ion Water 15 parts (Example 5) 7 liters

4 Partially condensed aluminum (MAII)
1os condensed phosphorous magnesium (Mg-100)
5 g titanium oxide 6 parts glycerin
1 part (Example 6) Sodium silica 100 parts 7 liters
3.5
Partly condensed aluminum 10 parts Condensed magnesium phosphate (Mg-100) 5 g Titanium oxide 5 parts Glycerin
1 part (Example 7) Composition of Example 6 1 part Mouth Silica Sand No. 4
200 parts (Example 8) Silica sodium 100 parts 7 liters
10 parts condensed aluminum phosphate (MAR)
5 g condensed magnesium phosphate (Mg-100)
10 g Titanium oxide 2 parts Glycerin porate 1 part (Example 9) Powdered sodium orzosilicate 100 parts
Lit
10 parts condensed aluminum (MAR) 10 parts titanium oxide
Part 1! squid powder 3 parts glycerin
1 Myth Ionized Water
20 parts Example 10 (Molded body) The composition obtained in Example 1 was mixed to a depth of 10! ! 1111 was poured into a wooden formwork with 10 molds on each side and heated at 80°0 for 1 hour to obtain a molded plate with a thickness of 10 cm. This molded body has a specific gravity of 1
．． 45, compressive strength is 200 Vc- or more, 50 aO
There was no change even after 24 hours of immersion in irrigation water.

Example 11 (Molded body) A molded body having a specific gravity of 1.48, a compressive strength of 200, and m- or more was obtained in the same manner as in Example 10, except that the composition obtained in Example 2 was heated at 90 aO for 30 minutes. This product was subjected to the same underwater immersion test as in Example 10, but no abnormalities were observed.

Example 12 (Molded body) The composition obtained in Example 3 was used in the same manner as in Example 1 to obtain a molded body having a specific gravity of 1.49 and a compressive strength of 2DOky'awP or more. This product was subjected to the same underwater immersion test as in Example 10, but no abnormalities were observed.

Example 13 (Molded body) Using the composition obtained in Example 4, a molded article was prepared in the same manner as in Example 10, with a specific gravity of 1.47 and a compressive strength of 200 kfaw? As described above, a molded article was obtained in which no abnormalities were observed even when subjected to an underwater immersion test.

Example 14 (Molded body) Using the composition obtained in Example 5, a molded body was obtained in the same manner as in Example 11, with a specific gravity of 1.48, a compressive strength of 200≠- or more, and no abnormalities observed in the underwater immersion test. .

Example 15 (Coated material) Using the composition obtained in Example 1 (milky white paste paint), it was applied to a slate board (J Kosm 5405 asbestos slate board) and a mild steel board (J Kos 8 G 3141 cold rolled The coating was applied to the surface of each steel plate with a brush to a thickness of 3 mm, and then baked and cured for 60 minutes in a drying oven at 80°O to obtain a milky white translucent coating. The resulting coating was allowed to stand at room temperature for 24 hours, and then immersed in water at 60°A for 24 hours, but no change was observed.

7. Comparative Example From the composition of Example 1. A coated plate was prepared in the same manner as in Example 15 using the composition except for the phosphorus or condensed aluminum. In all of the obtained coated mild steel plates, the coating film was softened by an underwater immersion test (50°C, 24 hours) when the plate was left standing at room temperature for 24 hours.

Example 16 (Coated material) Using the composition obtained in Example 6, the heating conditions were 90 oa, 60 oa
A coating was obtained in the same manner as in Example 15, except that the immersion test was conducted in water for a few minutes, and no abnormality was observed at all in the underwater immersion test.

Example 17 (Coating) The composition obtained in Example 7 was applied to a slate board to a thickness of 5 m, and was cured by heating at 95 oO for 20 minutes to obtain a sand wall-like coating.

The obtained coating was subjected to an underwater immersion test in the same manner as in Example 15, but no abnormality was observed.
No change in appearance was observed in accelerated weathering tests (Weatherometer: manufactured by Suga Test Instruments) over time.

Examples 18 and 19 (Coated material) A coated material was prepared in the same manner as in Example 15 using the composition obtained in Example 8 or 9, and an abnormal underwater immersion test was performed, but no abnormality was observed in either case.

Example 20 (Composition (B) and elastomer) 100 parts of sodium silicate and 5 parts of 7 liters (XD-9AP manufactured by Nippon Hue 4) were placed in a 300 mj capacity container and stirred with a puller type stirrer. Heat to 60-90
% temperature range for 20 minutes, the stirring was stopped and the temperature was allowed to cool at room temperature.
A slightly sticky elastic body containing 8% was obtained.

Next, the obtained elastic body was molded using a spherical mold with an inner diameter of 10 mm, and when it was naturally dropped from a height of 1 fold onto a glass plate surface, it did not deform and fell 60 mm from the glass surface.
It was repulsed to the height of weight.

In addition, the results of infrared absorption spectrum analysis of the obtained elastic body (
KBr tablet method) is shown in FIG.

Also, dilute the custom-made elastic body with water and measure it with a B-type viscometer (
■Tokyo Keiki Co., Ltd.) No. 3 → -15Q r, p, m
The viscosity at 20°0 was measured and the results shown in Table 1 were obtained.

Table 1 Examples 21 to 24 (Elastic bodies) Four types of elastic bodies and two types of comparative examples were prepared in the same manner as in Example 20 except that the heating conditions were changed. The results are shown in Table 2.

Examples 25 to 66 (Composition (B) and elastic body) Compositions shown in Table 3 were prepared in the same manner as in Example 20,
The recoil height of the obtained elastic body was measured. The results are shown in Table 3.

[Brief explanation of the drawing]

FIG. 1 is an infrared absorption spectrum diagram of the elastic body obtained in Example 20.

Claims (1)

[Scope of Claims] 1. A heat-curable alkali silicate composition comprising an alkali silicate, a 7-lithium salt, and a condensed phosphorous salt. 2. The composition according to claim 1, which is subjected to mts for thermoforming. 3. The composition according to claim 1 prepared for use as a dressing. 4. An alkali silicate molded article obtained by heat molding an alkali silicate composition containing an alkali silicate, 7 liters, and condensed phosphorous acetate. 5. A method for producing an alkali silicate molded article, which comprises solidifying an alkali silicate composition containing an alkali silicate, a frit, and a condensed phosphorous ceramic salt under heating. 6. An alkali silicate coating obtained by covering a material with an alkali silicate composition containing an alkali silicate, 7 lithium chloride, and condensed phosphate and heat-treating the material. 7. An alkali silicate composition which forms an elastic body by heating and contains an alkali silicate and a fritted material. 8. An Fi-acid alkali-based elastomer obtained by reacting an alkali-silicate composition containing an alkali silicate and 7 lithium under heating.