JPH08119709A - Water-hardening composition, hardened article and its production - Google Patents

Abstract

PURPOSE: To obtain a water-hardening composition having excellent fluidity by compounding a specific component containing a latent water-hardening material and to obtain a hardened material having high strength, durability and water resistance by kneading the composition with water followed by forming and hardening CONSTITUTION: This water hardened composition is obtained by compounding (A) 100 pts.wt. of a latent water-hardening material such as water granulated slag from a blast furnace having Blain's specific surface area of >=2000cm<2> /g or converter slag with (B) 2-50 pts.wt. of superfine powder having an average particle diameter of <=10μm, (C) 2-50 pts.wt. of needle-shaped inorganic powder and/or 1-20 pts.wt. of fibrous material, (D) 0.1-10 pts.wt. of a high polymeric dispersant having a molecular weight of 1000-200000 based on 100 pts.wt. of the components A+B, (E) 0.2-20 pts.wt. of a hardening stimulating agent based on 100 pts.wt. of the components A+B, (F) 10-200 pts.wt. of water based on 100 pts.wt. of the components A+B, and optionally (G) 0.001-5 pts.wt. of a thickener consisting of an hydrophilic polymer having a molecular weight of >=20000 based on 100 pts.wt. of the components A+B.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a hydraulic composition, a cured product and a method for producing the same.

[0002]

2. Description of the Related Art Latent hydraulic materials represented by granulated blast furnace slag, converter slag, etc. are mainly by-produced in large quantities during the production of pig iron, and the amount reaches tens of millions of tons per year. However, various effective use of this has been studied. Among them, there is a method in which the latent hydraulic property of the latent hydraulic substance is used to add several% to several tens% to the cement, and this is a method of using the latent hydraulic substance as an additive material. Hard materials based on hard materials have been rarely developed.

It is known that the latent hydraulic property is exhibited by the addition of water and an alkaline agent or the addition of a sulfate to the latent hydraulic substance, and the composition is gradually hardened. Is very brittle and has poor water resistance, which is problematic in terms of practicality.

[0004]

In recent years, attempts have been made to use this latent hydraulic substance for casting, centrifugal molding and the like similarly to cement, but the obtained cured product has a weak strength and is not practical yet. There is no product that satisfies us. In order to effectively use a large amount of latent hydraulic substances,
Development of a technique for producing a cured product having high strength physical properties is required.

[0005]

[Means for Solving the Problems] The present inventors can cast a latent hydraulic substance in the same manner as cement without adding cement, and the cured product has physical properties of higher strength than cement. As a result of intensive studies to obtain a cured product, the present invention has been completed. That is, the present invention

(1) Hydraulic composition containing the following (a) to (e) (a) Latent hydraulic material (b) Ultra fine powder (c) Inorganic inorganic powder and / or fibrous material (d) ) Dispersant (e) Curing stimulant (2) The hydraulic composition according to (1) above, which contains (f) water as a component other than (a) to (e), (3) (a) to (e). Or (a) to (f) as a component other than (g) a thickening agent containing a thickener, (4) latent hydraulic substance is blast furnace granulated slag and And / or a hydraulic composition according to the above (1), (2) or (3) which is a converter slag, (5) (c) component is wollastonite, sepiolite,
The hydraulic composition according to any one of (1) to (4) above, which is one or more selected from the group consisting of chrysotile, amosite, tremolite, zeolite, glass fiber and alumina fiber, (6) curing stimulus The agent is an alkali metal hydroxide, carbonate,
The hydraulic composition according to any one of (1) to (5) above, which is one or more selected from the group consisting of bicarbonates and silicates. (7) The hardening stimulant is caustic soda, caustic potash, carbonic acid. Any of the above (1) to (7), wherein the hydraulic composition according to the above (6) is soda or sodium silicate, and (8) the dispersant is a polymer having a carboxylic acid group and / or a salt thereof in the molecule. The hydraulic composition according to claim 1, (9) A kneaded product obtained by kneading the hydraulic composition according to any one of (1) to (8) above with water as necessary is molded and cured. A method for producing a cured product, which is characterized by curing. (10) A cured product produced by the method described in (9) above.

Hereinafter, the present invention will be described in detail. The latent hydraulic material used in the present invention is not particularly limited as long as it exhibits curability when mixed with a curing stimulant, but granulated blast furnace slag and converter slag are preferable. These latent hydraulic substances preferably have a Blaine specific surface area of 2000 cm ² / g or more, and particularly preferably 3000 cm ² / g or more.

The ultrafine powder used in the present invention has an average particle size smaller than that of the latent hydraulic substance, preferably one order or more smaller than that of the latent hydraulic substance, and more preferably. Use one that is smaller than two orders of magnitude. The average particle size of the ultrafine powder is 10 μm or less, and preferably 0.01 to 2 μm.

Specific examples of the ultrafine powder that can be used include silica fume, fly ash, silica sand, silica stone powder, clay,
Examples include talc, kaolin, calcium carbonate, ground ceramics, ground blast furnace slag, titania, zirconia, alumina, and Aerosil. It is particularly preferable to use silica fume because the effects such as improvement of the properties are remarkable. The amount of the ultrafine powder used varies depending on the size (particle size) and type of the latent hydraulic substance, and the type and amount of other various admixtures added as necessary, but usually,
The amount is preferably 2 to 50 parts by weight, and particularly preferably 5 to 25 parts by weight, based on 100 parts by weight of the latent hydraulic substance.

Specific examples of the acicular inorganic powder that can be used in the present invention include wollastonite, sepiolite, chrysotile, amosite, tremolite, zeolite, etc., but the cured product has improved strength, durability and water resistance. Wollastonite is preferred from the standpoint of improving the effect of the above. Usually, the amount of the acicular inorganic powder used is preferably 2 to 50 parts by weight, and particularly preferably 5 to 25 parts by weight, based on 100 parts by weight of the latent hydraulic substance.

Specific examples of the fibrous substance that can be used in the present invention include glass fiber, carbon fiber, vinylon, nylon, aramid, polypropylene, acrylic, polyester and other fibers, cellulose fiber, steel, alumina fiber and the like. Of these, glass fibers and alumina fibers are preferable. The amount of the fibrous substance used is usually 0.1 to 20 parts by weight, preferably 0.1% by weight, relative to 100 parts by weight of the latent hydraulic substance.
2 to 5 parts by weight.

The dispersant used in the present invention is preferably a polymer having a carboxylic acid group and / or its salt in the molecule,
Specifically, poly (meth) acrylic acid salts, acrylic acid / maleic acid copolymers, acrylic acid / maleic acid / isobutyl vinyl ether copolymers, acrylic acid / itaconic acid /
Styrene copolymer, acrylic acid / itaconic acid / methacrylic acid / styrene copolymer, maleic anhydride / C _{5 to} C ₈
It is an olefin copolymer or the like. Examples of the salt include alkali metal salts such as lithium, sodium and potassium salts, and further ammonium salts and amine salts.

The dispersant used in the present invention includes (meth) acrylic acid, maleic acid, itaconic acid, styrene,
It may be a copolymer of vinyl ethers and a copolymerizable monomer. Copolymerizable monomers include hydroxyethyl (meth) acrylate, N-vinylpyrrolidone, sodium styrenesulfonate, sodium allylsulfonate, sodium methacrylsulfonate, vinyl acetate, methyl acrylate, ethyl acrylate, butyl acrylate. , Acrylonitrile, methyl methacrylate, acrylate, methacrylamide, ethylene, propylene, isobutylene and the like.

The dispersant used in the present invention is not limited to the above-mentioned copolymers. In the present invention, formalin condensate of naphthalene sulfonic acid, melamine sulfonic acid formalin condensate, lignin sulfonic acid condensate, etc., which are known as water-reducing agents for cement and concrete, can be used in combination with the above dispersant. These water reducing agents may be used alone or in combination of two or more. When these water reducing agents are used in combination with the above dispersant (polymer having a carboxylic acid group and / or its salt in the molecule), the proportion of the above dispersant in the total dispersant is 10 parts by weight or more. Preferably. In the following, the above dispersant and water reducing agent are collectively referred to as a dispersant and the like.

The molecular weight of the dispersant and the like is preferably 100
0 to less than 200,000, more preferably 3,000 to
It is 100,000. The molecular weight is 1,000 or less,
When it is 200,000 or more, the fluidity of the hydraulic composition is poor,
The strength of the cured product also tends to be weak.

The amount of these dispersants used varies depending on the required characteristics of the cured product, etc., but is usually 0.1 to 10 parts by weight, preferably 0 to 100 parts by weight of the total amount of the latent hydraulic substance and ultrafine powder. 0.3 to 6 parts by weight, particularly preferably 0.5 to 3
Parts by weight. If the amount of the dispersant used is less than 0.1 part by weight, the kneading may be difficult or the fluidity of the kneaded product may be reduced, depending on the amount of water added.

Specific examples of the thickener that can be used in the present invention include polyacrylic acid salts, polyacrylamides, acrylic acid-acrylamide copolymer salts, cellulose derivatives such as methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxyethyl cellulose, and the like. Polyethylene oxide, polypropylene oxide, polyvinylpyrrolidone, polyvinyl alcohol,
Examples thereof include relatively high molecular weight hydrophilic polymers such as xanthan gum and curdlan.

The molecular weight of the thickener is preferably 20,000 or more, particularly preferably 30,000 or more. Further, the thickener is used in an amount of 0.001 to 5 parts by weight, if necessary, per 100 parts by weight of the total amount of the latent hydraulic substance and ultrafine powder.

The hydraulic composition of the present invention may further contain various admixtures other than those mentioned above, if necessary. As the admixture, for example, pulverized slowly cooled slag,
Examples include inorganic fillers such as ferrochrome slag, silica, alumina, talc, silica sand, silica powder, clay, kaolin, calcium carbonate, ground ceramics, titania, zirconia, and gravel. Further, a setting retarder such as sugar or glucose, a surface treating agent such as a silane coupling agent, a pigment or the like may be used.

When using these various admixtures, the amount used is usually 10 to 300 parts by weight per 100 parts by weight of the latent hydraulic substance in the case of an inorganic filler, and a curing retarder,
In the case of surface treatment agents, pigments, etc., it is usually 0.1 to 20 parts by weight with respect to 100 parts by weight of the latent hydraulic substance.

The curing stimulant used in the present invention is not particularly limited as long as it stimulates the latent hydraulic substance to promote the hydration reaction, and examples thereof include various alkaline substances. Specific examples of the curing stimulant that can be used include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide, alkali metal carbonates such as sodium carbonate, potassium carbonate and lithium carbonate, sodium bicarbonate and bicarbonate. Alkali metal bicarbonate such as potassium carbonate lithium bicarbonate, hydroxide of alkaline earth metal such as calcium hydroxide and magnesium hydroxide, sodium pyrophosphate, potassium pyrophosphate, dipotassium phosphate, tripotassium phosphate, phosphoric acid Examples thereof include phosphates such as trisodium, and silicates such as sodium (meth) silicate and potassium (meth) silicate.

Of these curing stimulants, alkali metal hydroxides are preferable, and sodium hydroxide is particularly preferable.

The amount of the curing stimulant used depends on its basicity (alkaline strength), the particle size of the latent hydraulic substance, the type and amount of various ultrafine powders to be added, and the amount of water. Generally, 0.2 to 20 parts by weight is preferable, and particularly preferably 2 to 10 parts by weight, based on 100 parts by weight of the total amount of the latent hydraulic substance and the ultrafine powder.

If the amount of the curing stimulant is too small, the cured product does not exhibit sufficient strength, and it takes a long time to cure, which is economically disadvantageous.

The amount of water used may be determined so that the type and amount of latent hydraulic substance and ultrafine powder used, the kneaded product show good fluidity, and the cured product shows high strength and high durability. Although important, 10 to 200 parts by weight, preferably 20 to 15 parts by weight, based on 100 parts by weight of the total amount of the latent hydraulic substance and the ultrafine powder.
It is 0 part by weight, more preferably 30 to 100 parts by weight.

The hydraulic composition of the present invention can be obtained by mixing the above-mentioned components other than water in a predetermined proportion as solid or kneading each component with water.

Next, the method for producing the cured product of the present invention will be described. A mixture of a latent hydraulic substance and ultrafine powder, latent hydraulic substance, ultrafine powder, needle-like inorganic powder and / or fibrous substance and, if necessary, various admixtures insoluble in water (a),
Dispersing agents, hardening stimulants, and if necessary thickeners, various water-soluble admixtures dissolved in water to form an aqueous solution (b)
And are kneaded with a kneader to obtain a kneaded product. These operations may be carried out as described above up to (a), and then (b) may be mixed and kneaded, or the respective components may be simultaneously mixed and kneaded. In order to obtain a uniform cured product, it is preferable to add a water-soluble substance after dissolving it in water. Next, if necessary, the kneaded product is poured into an appropriate mold and the like, and cured to obtain the cured product of the present invention.

The curing for curing is usually carried out at room temperature, but it may be carried out at a temperature of room temperature to 100 ° C. under a saturated vapor pressure, or under heating with a lid so that water does not fly off. In the present invention, the higher the curing temperature, the faster the curing tends to be, but generally, the curing temperature is from room temperature to 60 ° C, and the curing time is from 1 day to 1 month.

[0028]

EXAMPLES The present invention will now be described in more detail by way of examples. In addition, the flow value in the examples was measured according to JIS R5201 for the kneaded product after kneading.

The compressive strength in the examples is 5c in diameter.
A cylindrical test piece with a height of 10 m and a height of 10 cm
This is the strength (kgf / cm ² ) when the material is compressed and broken at a loading speed of 0.2 mm / min using Orientec).

In the examples, parts or% are based on weight unless otherwise specified.

Example 1 Brane specific surface area 4000 cm in a concrete mixer
² / g granulated blast furnace slag (Nippon Steel Essent) 900
Parts, 100 parts of silica fume (manufactured by Nippon Heavy Chemical Industry Co., Ltd.), and 50 parts of sepiolite were added and stirred and mixed for 90 seconds. Subsequently, 15 parts of sodium polyacrylate (weight average molecular weight: 25,000) as a dispersant, 20 parts of sodium hydroxide and 240 parts of water as a curing stimulant were added, and the mixture was further kneaded for 5 minutes.

The flow value of the pasty composition obtained by kneading was 270 mm. Next, the kneaded product was put in a mold for compression test, and the cured product of the present invention obtained by steam curing for 1 day under an atmosphere of saturated vapor pressure of 90 ° C. had a compressive strength of 1050 kgf / cm ² . .

Example 2 Brane specific surface area 4000 cm in a planetary mixer
² / g granulated blast furnace slag (Nippon Steel Essent) 900
Parts, 100 parts of silica fume (manufactured by Nippon Heavy Chemical Industry Co., Ltd.), and 100 parts of wollastonite were added and stirred and mixed for 90 seconds. Subsequently, 15 parts of a sodium salt of acrylic acid / maleic acid (9: 1) copolymer (weight average molecular weight: 35,000) as a dispersant, 25 parts of sodium hydroxide and 270 parts of water as a curing stimulant were further added. Kneading for 5 minutes. The flow value of the pasty composition obtained by kneading is 2
It was 50 mm.

Next, the kneaded product was poured into a mold for compression test, and the cured product of the present invention obtained by steam curing for 1 day under an atmosphere of saturated vapor pressure of 60 ° C. had a compressive strength of 820 kgf /.
cm ² .

Example 3 Brane specific surface area 4000 cm in a planetary mixer
² / g granulated blast furnace slag (Nippon Steel Essent) 900
Part, silica fume (manufactured by Nippon Heavy Industries, Ltd.) 100 parts, polypropylene short fiber (Taflite, manufactured by Tesac Co., Ltd.)
20 parts was added and mixed by stirring for 90 seconds. Then, 15 parts of a sodium salt of acrylic acid / maleic acid (9: 1) copolymer (weight average molecular weight: 35,000) as a dispersant,
20 parts of sodium hydroxide and 280 parts of water were added as a hardening stimulant and kneaded for 5 minutes. The flow value of the pasty composition obtained by kneading was 260 mm.

Next, the kneaded product was poured into a mold for compression test, and the cured product of the present invention obtained by steam curing for 1 day at room temperature and saturated vapor pressure had a compressive strength of 650 kgf / c.
m ² .

Test Example The cured product of the present invention obtained in Examples 1 to 3 (hereinafter referred to as cured product-
1-cured product-3) and the cured product (cured product-4) obtained in the same manner as in Example 1 except that sepiolite was not added in Example 1 as a comparison. did. Test conditions: cylindrical cured product having a diameter of 5 cm and a height of 10 cm-
Tests were carried out by completely immersing 1 to cured product-4 in 10 times the volume of pure water. Test result: one month after the start of the test, cured product-1 to cured product-3
There was no change in appearance (cracks, cracks) and the like, but in the cured product-4, cracks were observed.

The hydraulic composition of the present invention has excellent fluidity, and the cured product obtained by curing the composition has high strength, high durability and high water resistance, and can be widely used as a building / construction material. .

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location C04B 18:14 Z 14:10 B 24:26 E 22:06) Z 103: 14 103: 40 111 : 00 (72) Inventor Katsuhiko Kurabayashi 1-6-23 Annaka, Annaka City, Gunma Prefecture

Claims (10)

[Claims] 1. A hydraulic composition containing the following (a) to (e). (A) latent hydraulic substance (b) ultrafine powder (c) needle-like inorganic powder and / or fibrous substance (d) dispersant (e) hardening stimulant 2. The hydraulic composition according to claim 1, which further comprises (f) water as an additional component other than (a) to (e). 3. The hydraulic composition according to claim 1, which further comprises (g) a thickener as an additional component other than (a) to (e) or (a) to (f). 4. The hydraulic composition according to claim 1, 2 or 3, wherein the latent hydraulic substance is granulated blast furnace slag and / or converter slag. 5. The component (c) is one or more selected from the group consisting of wollastonite, sepiolite, chrysotile, amosite, tremolite, zeolite, glass fiber and alumina fiber. The hydraulic composition according to. 6. The water according to claim 1, wherein the curing stimulant is one or more selected from the group consisting of alkali metal hydroxides, carbonates, bicarbonates and silicates. Hard composition. 7. The hydraulic composition according to claim 6, wherein the curing stimulant is sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate. 8. The hydraulic composition according to claim 1, wherein the dispersant is a polymer having a carboxylic acid group and / or a salt thereof in the molecule. 9. A process for producing a cured product, which comprises molding and curing the kneaded product obtained by kneading the hydraulic composition according to any one of claims 1 to 8 with water if necessary. 10. A cured product produced by the production method according to claim 9.