JP2021008396A - Geopolymer composition and its production method, admixture for geopolymer composition, and cured geopolymer body - Google Patents

Abstract

To provide a geopolymer composition that makes it possible to obtain a cured geopolymer body having a uniform specific gravity and excellent shrinkage reduction property, and a method for producing the same; and to provide an admixture suitable for use in the production of geopolymer composition, and a cured geopolymer body, namely, a cured product of the geopolymer composition.SOLUTION: A geopolymer composition comprising a base component (A), a water-soluble cellulose ether (B), and an anionic surfactant (C), wherein the base component (A) contains coal ash and/or blast furnace slag, and wherein an aqueous 2 wt.% solution of the water-soluble cellulose ether (B) has a viscosity 100 to 50,000 mPa s at 20°C.SELECTED DRAWING: None

Description

The present invention relates to a geopolymer composition and a method for producing the same, an admixture for the geopolymer composition, and a cured geopolymer.

Hardened materials such as concrete and mortar are widely used as construction materials all over the world, and it is predicted that the production volume of cement, which is the main raw material, will continue to increase in the future. Cement is produced by the chemical decomposition of limestone, but since a large amount of carbon dioxide is emitted at that time, it may lead to global warming, and a raw material that replaces cement is required.
Among them, geopolymers using coal ash, blast furnace slag, metacaolin, etc., proposed by Davidovits et al. In France, are not only used as raw materials to replace cement, but also from the viewpoint of reducing carbon dioxide and effectively utilizing waste. It is being developed as an important technology.

Regarding the geopolymer, the dispersibility is characterized in that the water absorption rate is 30 wt% or more, the maximum pore diameter is 1 mm or less, and 40% or more of the contained pores are pores involved in water absorption. An excellent water-absorbent geopolymer material is exemplified in Patent Document 1, and a peroxide such as hydrogen peroxide solution, sodium peroxide, potassium peroxide, or sodium perborate is preferable as a foaming agent for introducing bubbles. Has been done.
Further, in Patent Document 2, a substance containing water, a chemical activator, and a cementaceous reactive material, and the chemical activator is selected from the group consisting of an alkali metal salt, an alkali metal base, and a mixture thereof. The cementitious reactive material is selected from the group consisting of thermally activated aluminosilicate minerals, calcium aluminocate cement, calcium sulfate dihydrate, calcium sulfate hemihydrate, anhydrous calcium sulfate and mixtures thereof. An aluminosilicate geopolymer composition containing calcium sulfate is exemplified, and cracks and the like occur in the cured geopolymer due to the preparation of the geo-component and the cementitious reactive material and the delay of the rapid hydration reaction and the mitigation of heat generation. It is said that it can be prevented from doing so. However, the cement-based component exemplified in Patent Document 2 is a cement that is normally distributed, and the effect of reducing carbon dioxide is low.

Japanese Unexamined Patent Publication No. 2011-219281 Special Table 2015-514675

However, in the geopolymer material of Patent Document 1, it is difficult to control the diameter of the bubbles introduced by the foaming agent, and the diameter of the bubbles inside the obtained geopolymer cured product tends to be non-uniform. In addition, it was confirmed that the bubbles inside the cured product were unevenly distributed and localized, and that the uniformity of the specific gravity of the cured product was low, and that the shrinkage reduction property was also inferior.
Further, in the geopolymer composition of Patent Document 2, the introduced bubbles are unevenly distributed, coarsened, and coalesced due to the temperature rise of the composition due to heat generation, and the bubble diameter introduced into the obtained cured geopolymer is not large. It was confirmed that the cured product became uniform and the uniformity of the specific gravity of the cured product decreased. In addition, the shrinkage reducing property of the cured product was insufficient.

As described above, there has been no geopolymer composition capable of obtaining a cured geopolymer having a uniform specific gravity and excellent shrinkage reduction property.
An object of the present invention is a geopolymer composition capable of obtaining a cured geopolymer composition having a uniform specific gravity and excellent shrinkage reduction property, a method for producing the same, and a geopolymer composition preferably used for producing the geopolymer composition. It is to provide a physical admixture and a geopolymer cured product which is a cured product of the geopolymer composition.

As a result of diligent studies to solve the above problems, the present inventors have obtained a geopolymer composition containing a specific base material component, a specific water-soluble cellulose ether, and an anionic surfactant. We have found that a cured geopolymer having a uniform specific gravity and excellent shrinkage reduction property can be obtained, and have reached the present invention.

That is, the present invention is a geopolymer composition containing a base material component (A), a water-soluble cellulose ether (B), and an anionic surfactant (C), wherein the component (A) is coal ash and / Or a geopolymer composition containing blast furnace slag and having a viscosity of an aqueous solution containing 2% by weight of the cellulose ether (B) at 20 ° C. of 100 to 50,000 mPa · s.

The pH of the aqueous dispersion having a concentration of 82.5% by weight of the water-insoluble component of the geopolymer composition at 20 ° C. is preferably 12 or more and 14 or less.
It is preferable to further contain the amphoteric surfactant (D).
It is preferable to further contain an alkali component (E) that essentially contains an alkali metal silicate.

The method for producing a geopolymer composition of the present invention is the above-mentioned method for producing a geopolymer composition, which comprises a step of mixing the base material component (A) and an admixture for a geopolymer composition. The admixture for a polymer composition contains a water-soluble cellulose ether (B) and an anionic surfactant (C), and the viscosity of an aqueous solution having a concentration of 2% by weight of the water-soluble cellulose ether (B) at 20 ° C. is 100. It is a method for producing a geopolymer composition of ~ 50,000 mPa · s.
It is preferable that the admixture further contains an amphoteric surfactant (D).

The admixture for a geopolymer composition of the present invention is an admixture for a geopolymer composition containing a water-soluble cellulose ether (B) and an anionic surfactant (C), and the cellulose ether at 20 ° C. The viscosity of the aqueous solution having a concentration of 2% by weight of B) is 100 to 50,000 mPa · s.
It is preferable to further contain the amphoteric surfactant (D).

The geopolymer cured product of the present invention is a cured product of the above geopolymer composition.

The geopolymer composition of the present invention can obtain a cured geopolymer composition having a uniform specific gravity and excellent shrinkage reduction property.
The method for producing a geopolymer composition of the present invention can efficiently produce a geopolymer composition capable of obtaining a cured geopolymer composition having a uniform specific gravity and excellent shrinkage reduction property.
The admixture for a geopolymer composition of the present invention can obtain a geopolymer composition capable of obtaining a cured geopolymer having a uniform specific gravity and excellent shrinkage reduction property.
The cured geopolymer of the present invention has a uniform specific gravity and is excellent in shrinkage reduction.

The geopolymer composition of the present invention contains a base material component (A), a water-soluble cellulose ether (B), and an anionic surfactant (C). Hereinafter, each material contained in the geopolymer composition will be described in detail.

[Base material component (A)]
The base material component (A) (hereinafter, may be simply referred to as the component (A)) is a material that contains SiO ₂ and Al ₂ O ₃ and is cured, and essentially contains coal ash and / or blast furnace slag. When the component (A) contains coal ash and / or blast furnace slag, a geopolymer cured product having a uniform specific gravity and excellent shrinkage reduction property (hereinafter, may be simply referred to as a cured product) can be obtained.
Examples of the coal ash include liquid bed coal ash, fly ash, clinker ash and the like. Blast furnace slag is a residue produced as a by-product when iron is refined in a blast furnace.

Component (A) may include anything other than coal ash and / or blast furnace slag. Examples of other than coal ash and / or blast furnace slag include municipal waste incineration ash molten slag, sewage sludge incineration ash molten slag, metakaolin, steelmaking slag and the like.
The weight ratio of coal ash and / or blast furnace slag to the component (A) is not particularly limited, but is preferably 35 to 100% by weight, more preferably 40 to 100% by weight, still more preferably 45 to 100% by weight, and particularly. It is preferably 47.5 to 100% by weight, most preferably 50 to 100% by weight. When the weight ratio of coal ash and / or blast furnace slag to the component (A) is less than 35% by weight, poor curing of the cured product may occur, and the appearance may be impaired by powder blowing.

[Water-soluble cellulose ether (B)]
The water-soluble cellulose ether (B) (hereinafter, may be referred to as cellulose ether (B)) is a nonionic cellulose derivative. By containing the cellulose ether (B), an appropriate viscosity can be imparted to the geopolymer composition, and the material inseparability of the material contained in the geopolymer composition is improved. In addition, the stability of the bubbles introduced into the geopolymer composition is also improved, and a cured geopolymer product having a uniform specific gravity and excellent shrinkage reduction property can be obtained.
Cellulose ether (B) is preferable in that the effect of the present application can be obtained when the aqueous solution shows a gel point of 40 ° C. or higher and lower than 90 ° C. At the gelling point of the aqueous solution of cellulose ether (B) in the present invention, an aqueous solution having a concentration of 2% by weight of cellulose ether (B) is heated at a constant heating rate by using a visible light transmittance measuring device. The transmittance of visible light with a wavelength of 650 nm at a cell length of 10 mm was measured, and the temperature indicating 50% transmittance when the transmittance at 20 ° C. was 100% and the transmittance at 90 ° C. was 0% was gelled. It was a point.

Examples of the cellulose ether (B) include alkyl cellulose such as methyl cellulose; hydroxyalkyl cellulose such as hydroxyethyl cellulose and hydroxypropyl cellulose; and hydroxyalkyl alkyl cellulose such as hydroxyethyl methyl cellulose and hydroxypropyl methyl cellulose. Alternatively, two or more types may be used in combination.
The cellulose ether (B) preferably has a hydroxyl group in that it exhibits the effects of the present application.

In the cellulose ether (B), the viscosity of the aqueous solution having a concentration of the cellulose ether (B) of 2% by weight at 20 ° C. is 100 to 50,000 mPa · s. If the viscosity of the aqueous solution having a concentration of 2% by weight is less than 100 mPa · s, the material inseparability is lowered, and a cured product having a uniform specific gravity and excellent shrinkage reduction property cannot be obtained. On the other hand, if it exceeds 50,000 mPa · s, uniform bubbles cannot be introduced, and the specific gravity of the obtained cured product becomes non-uniform. Further, if the viscosity of the aqueous solution having a concentration of 2% by weight of the cellulose ether (B) is out of the above range, the production efficiency of the cured product is lowered.
The viscosity of the aqueous solution having a concentration of cellulose ether (B) of 2% by weight at 20 ° C. is preferably 150 mP to 45,000 mPa · s, more preferably 200 to 40,000 mPa · s, still more preferably 250 to 35,000 mPa · s, and particularly preferably 300 to 300. It is 30,000 mPa · s, most preferably 350 to 25,000 mPa · s. The viscosity of the aqueous solution having a concentration of cellulose ether (B) of 2% by weight at 20 ° C. was measured using a B-type viscometer.

In the geopolymer composition, the content of the cellulose ether (B) is not particularly limited, but is preferably 0.10 to 2.5 parts by weight with respect to 100 parts by weight of the component (A). If the content of cellulose ether (B) is less than 0.10 parts by weight, the material non-separability may decrease. On the other hand, if the content of the cellulose ether (B) is more than 2.5 parts by weight, uniform bubbles cannot be introduced, and the specific gravity of the obtained cured product may be non-uniform. In addition, the production efficiency of the cured product may decrease.
The content of the cellulose ether (B) is more preferably 0.125 to 2.25 parts by weight, further preferably 0.15 to 2.0 parts by weight, and particularly preferably 0.175 to 1.75 parts by weight. It is preferably 0.2 to 1.50 parts by weight.

[Anionic surfactant (C)]
The anionic surfactant (C) (hereinafter, may be simply referred to as the activator (C)) is a material capable of introducing uniform bubbles into the geopolymer composition. As a result, the obtained cured geopolymer is lightweight and has a uniform specific gravity. In addition, the obtained cured product can suppress cracking due to frost damage.
Furthermore, by containing the activator (C) in the geopolymer composition, the cellulose ether (B) and the activator (C) interact with each other, the cellulose ether (B) is protected by the activator (C), and the geopolymer is formed. It is considered that the stability of the cellulose ether (B) can be improved in the composition, and the stability of the introduced bubbles is improved.

Examples of the activator (C) include carboxylates, sulfonates, sulfates, phosphates and the like.
The carboxylate is not particularly limited, but is preferably one having 8 to 22 carbon atoms in terms of exhibiting the effects of the present application. The number of carbon atoms contained in the carboxylate is more preferably 10 to 20, and most preferably 12 to 18. Examples of the carboxylate include fatty acid salts such as sodium oleate and potassium palmitate; and acyl amino acid salts such as N-lauroyl glutamate monosodium and N-stearoyl-L-glutamic acid disodium.

The sulfonate is not particularly limited, but is preferably one having 8 to 20 carbon atoms in terms of exhibiting the effects of the present application. The number of carbon atoms contained in the sulfonate is more preferably 8 to 18, particularly preferably 10 to 16. Examples of the sulfonate include alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate; α-sulfonates such as 2-sulfotetradecanoic acid-1-methyl ester sodium salt and 2-sulfohexadecanoic acid-1-methyl ester sodium salt. Fatty acid ester salt; α-olefin sulfonate such as sodium tetradecene sulfonate and the like can be mentioned.

The sulfate ester salt is not particularly limited, but is preferably one having 8 to 20 carbon atoms in terms of exhibiting the effects of the present application. The number of carbon atoms contained in the sulfate ester salt is more preferably 10 to 18, particularly preferably 11 to 17. Examples of the sulfate ester salt include sodium lauryl sulfate, ammonium lauryl sulfate, sodium stearyl sulfate, and alkyl sulfates of sodium cetyl sulfate.
The phosphoric acid ester salt is not particularly limited, but is preferably one having 8 to 20 carbon atoms in terms of exhibiting the effects of the present application. The number of carbon atoms contained in the phosphoric acid ester salt is more preferably 8 to 18, particularly preferably 10 to 16. Examples of the phosphoric acid ester salt include higher alcohol phosphate ester salts such as sodium lauryl phosphate salt and potassium lauryl phosphate salt, and alkylene oxide adducts thereof.

As the activator (C), one or more of the above may be used in combination. Further, the activator (C) is preferably an alkali metal salt from the viewpoint of exhibiting the effects of the present application.

The content of the activator (C) in the geopolymer composition is not particularly limited, but is preferably 0.10 to 2.5 parts by weight with respect to 100 parts by weight of the component (A). If the content of the activator (C) is less than 0.10 parts by weight, the introduced bubbles may be insufficient and the stability of the introduced bubbles may be lowered. On the other hand, if the content of the activator (C) is more than 2.5 parts by weight, the introduced bubbles may become excessive and the strength of the obtained cured product may decrease.
The content of the activator (C) is more preferably 0.125 to 2.25 parts by weight, further preferably 0.15 to 2.0 parts by weight, particularly preferably 0.175 to 1.75 parts by weight, most preferably. It is preferably 0.20 to 1.5 parts by weight.

The ratio of the content of the cellulose ether (B) to the activator (C) in the geopolymer composition (cellulose ether (B) / activator (C)) is not particularly limited, but is 30/70 to 90/10. Is preferable. If the cellulose ether (B) / activator (C) is less than 30/70, the stability of the bubbles introduced into the geopolymer composition may decrease. On the other hand, if the ratio of the contents of the cellulose ether (B) and the activator (C) exceeds 90/10, the material inseparability of the geopolymer composition may decrease. Cellulose ether (B) / (C) is more preferably 32.5 / 67.5-87.5 / 12.5, still more preferably 35 / 65-85 / 15, particularly preferably 37.5 / 62. It is 5 to 82.5 / 17.5, most preferably 40/60 to 80/20.

[Amphoteric surfactant (D)]
The geopolymer composition of the present invention may further contain an amphoteric surfactant (D) (hereinafter, may be simply referred to as an activator (D)). It is preferable that the geopolymer composition contains the activator (D) because the generation of introduced bubbles and the stability of the introduced bubbles can be further improved. This is because the activator (D) and the activator (C) interact with each other, the stability of the activator (C) is improved, and the stability of the cellulose ether (B) is further improved accordingly. Conceivable.

Examples of the activator (D) include 2-undecyl-N, N- (hydroxyethylcarboxymethyl) -2-imidazoline sodium and 2-cocoyl-2-imidazolinium hydroxide-1-carboxyethyroxy disodium salt. And other imidazoline amphoteric tensides; 2-heptadecyl-N-carboxymethyl-N-hydroxyethyl imidazolium betainee, lauryldimethylaminoacetic acid betaine, alkylbetaine, amide betaine, sulfobetaine and other betaine amphoteric tensides; Amino acid amphoteric tenside agents such as −laurylglycine, N-lauryl-β-alanine, and N-stearyl-β-alanine can be mentioned, and one or more of them may be used in combination.
The activator (D) is preferably a betaine-based amphoteric surfactant and / or an amino acid-based amphoteric surfactant from the viewpoint of exhibiting the effects of the present application.

When the geopolymer composition of the present invention contains the activator (D), the content of the activator (D) in the geopolymer composition is not particularly limited, but is 0.050 per 100 parts by weight of the component (A). It is preferably about 1.0 part by weight. If the content of the activator (D) is less than 0.050 parts by weight, the introduced bubbles may be insufficient and the stability of the introduced bubbles may be lowered. On the other hand, if the content of the activator (D) is more than 1.0 part by weight, the introduced bubbles may become excessive and the strength of the obtained cured product may decrease. The content of the activator (D) is more preferably 0.10 to 0.93 parts by weight, further preferably 0.13 to 0.85 parts by weight, particularly preferably 0.15 to 0.77 parts by weight, most preferably. It is preferably 0.17 to 0.70 parts by weight.

When the geopolymer composition of the present invention contains an activator (D), the ratio of the content of the activator (C) to the activator (D) in the geopolymer composition (activator (C) / activator (D)). ) Indicates the effects of the present application: (1) 30/70 to 70/30, (2) 32.5 / 67.5 to 67.5 / 32.5, (3) 35/65 to 65/35. , (4) 37.5 / 62.5 to 62.5 / 37.5, and (5) 40/60 to 60/40 are preferable in this order (the larger the number in parentheses, the more preferable).

[Alkaline component (E)]
When the geopolymer composition of the present invention further contains an alkali component (E) (hereinafter, may be simply referred to as a component (E)) that requires an alkali metal silicate, the obtained cured product has improved shrinkage reduction property. Therefore, it is preferable.
Examples of the alkali metal silicate include lithium silicate, sodium silicate, potassium silicate and the like, and one or more of them may be used in combination. In addition, in the component (E), examples other than the alkali metal silicate include hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide and potassium hydroxide; alkalis such as calcium hydroxide and magnesium hydroxide. Hydroxides of earth metals and the like can be mentioned, and one kind or two or more kinds may be used in combination.

The weight ratio of the alkali metal silicate to the component (E) is not particularly limited, but is preferably 20 to 100% by weight. If the weight ratio of the alkali metal silicate is less than 20% by weight, the shrinkage reducing property of the obtained cured product may be lowered. The weight ratio of the alkali metal silicate to the component (E) is more preferably 25 to 95% by weight, further preferably 30 to 90% by weight, particularly preferably 35 to 85% by weight, and most preferably 40 to 80% by weight. Is.

When the geopolymer composition of the present invention contains the component (E), the content of the component (E) in the geopolymer composition is not particularly limited, but is 5.0 to 50 with respect to 100 parts by weight of the component (A). It is preferably a part by weight. If the content of the component (E) is less than 2.5 parts by weight, the obtained cured product may be insufficiently cured, and the shrinkage reducing property of the cured product may be lowered. On the other hand, if the content of the component (E) is more than 50 parts by weight, powder blowing or salt precipitation may occur on the surface of the obtained cured product, and the appearance may be impaired. The content of the component (E) is more preferably 7.5 to 45.7 parts by weight, further preferably 10 to 45 parts by weight, particularly preferably 12.5 to 42.5 parts by weight, and most preferably 15 to 40 parts by weight. It is a part by weight.

〔water〕
The geopolymer composition of the present invention preferably contains water from the viewpoint of material dispersibility and moldability of the cured product. Examples of water include tap water, ion-exchanged water, soft water, distilled water and the like.
When the geopolymer composition of the present invention contains water, the weight ratio of water to the entire geopolymer composition is not particularly limited, but is preferably 15 to 30% by weight. If the weight ratio of water is less than 15% by weight, the viscosity of the geopolymer composition may increase and the moldability may decrease. In addition, it may not be possible to introduce uniform bubbles. On the other hand, when the weight ratio of water exceeds 30% by weight, the dimensional stability of the cured product may decrease. The weight ratio of water is more preferably 18 to 28% by weight, particularly preferably 20 to 25% by weight.

Moreover, the geopolymer composition may contain alcohol, polyalkylene glycol, polyglycerin and the like. Examples of the alcohol include methanol, ethanol, isopropanol, ethylene glycol, diethylene glycol, glycenrin and the like. Examples of the polyalkylene glycol include polyethylene glycol, polypropylene glycol, polyethylene propylene glycol and the like.

〔aggregate〕
The geopolymer composition of the present invention may further contain aggregate. As aggregates, natural aggregates such as river gravel, mountain gravel, sea gravel, crushed stone, volcanic gravel lightweight aggregate, silica sand, silica stone powder, silica fume, limestone powder; slag aggregate, artificial lightweight aggregate, heavy aggregate, etc. Artificial aggregates can be mentioned, and one or more of them may be used in combination. In addition, the particle size of the aggregate can be appropriately adjusted according to the desired cured product.
When the geopolymer composition of the present invention contains an aggregate, the content of the aggregate in the geopolymer composition is not particularly limited, but is 50 to 600 parts by weight with respect to 100 parts by mass of the component (A). It is preferably more preferably 75 to 500 parts by mass, still more preferably 100 to 400 parts by weight.

[Other ingredients]
In addition to the materials described above, the geopolymer composition of the present invention contains fibers, lightening agents, fillers, cement components, coagulation adjusters, viscosity modifiers, water retention agents, and defoamers, as long as the effects of the present application are not impaired. It may further contain an agent, a swelling agent, a waterproofing agent, a water repellent agent, a rust preventive agent, a coloring agent and the like.
Examples of the fiber include inorganic fibers such as glass fiber and carbon fiber; and organic fiber such as pulp, vinylon fiber and polypropylene fiber.
Examples of the lightening agent include an inorganic lightening agent such as pearlite; an organic foaming agent such as polystyrene; and an organic weight reducing material such as organic hollow microspheres.
Examples of the filler include an organic filler and an inorganic filler. Organic fillers include, for example, natural polymer compounds such as arabic rubber, tragant gum, guar gum, locust bean gum, karaya gum, quince seed, gelatin, cellac, rosin, casein, starch; sodium alginate, ester gum, nitrocellulose, hydroxy. Semi-synthetic polymer compounds such as propyl cellulose, crystalline cellulose, and dextrin; polyvinyl alcohol, polyvinyl pyrrolidone, sodium polyacrylate, carboxyvinyl polymer, polyvinyl methyl ether, phenol resin, epoxy resin, urea resin, polyamide resin, silicone, nylon, Examples thereof include resins such as polyacrylic acid ester, polymethacrylic acid ester, crosslinked polystyrene, urethane, polyethylene, and fluororesin. Examples of the inorganic filler include amorphous silica powder, pearlite, zeolite, diatomaceous earth, bentonite, talc, kaolin, mica, clay, hydroxyapatite, ceramic powder, metal soap, calcium carbonate, magnesium carbonate, aluminum carbonate, and oxidation. Examples thereof include titanium, calcined calcium sulfate (baked talc), calcium phosphate, iron oxide, zinc oxide, barium silicate, calcium silicate, magnesium silicate, barium sulfate and the like.
Examples of the cement component include ordinary Portland cement, early-strength Portland cement, ultra-early-strength Portland cement, moderate heat Portland cement, low heat Portland cement, sulfate-resistant Portland cement, silica cement, and the like.
Examples of the coagulation regulator include siliceous fluorides such as magnesium silicate, boric acids such as boric acid, oxycarboxylic acids such as gluconic acid, glucoheptonic acid, citric acid, and tartaric acid, and salts thereof. Examples thereof include high molecular weight organic acids such as lignin sulfonic acid, humic acid, and tannic acid, and salts thereof.
Examples of the viscosity modifier include carboxymethyl cellulose and its salt; a starch-based polymer such as hydroxypropylated starch; a water-soluble polymer such as polyvinyl alcohol, polyacrylamide, polyacrylic acid and its salt; and biotechnology such as xanthan gum and guagam. Polymers: Resin emulsions such as ethylene-vinyl acetate copolymer emulsions, polyvinyl acetate emulsions, polyvinyl acetate emulsions, and vinyl acetate-vinyl versatetate copolymer emulsions can be mentioned.

Examples of the water retention agent include alkoxypolypropylene glycol acrylate and the like.
Examples of the defoaming agent include polyoxyalkylene-based defoaming agents containing ethylene oxide and propylene oxide as main components; polypropylene glycol-based defoaming agents and mineral oil-based defoaming agents; modified silicone-based defoaming agents; dimethylpolysiloxane and the like. be able to.
As the leavening agent, aluminum powder, reactive silicone powder and the like can be blended.
As waterproofing agents and water repellents, calcium chloride; zirconium compounds; fatty acid soaps, fatty acids, fatty acid esters, or fatty acid compounds obtained by emulsifying these; silicone oils; silicone emulsions; paraffin emulsions; asphalt emulsions; oil-containing waste white clay; Examples include rubber latex.

As each of the above materials, those in a state of being dispersed in a liquid material such as water or an organic solvent or in a state of being in a solution may be used.

[Geopolymer composition, method for producing geopolymer composition]
Since the geopolymer composition of the present invention indispensably contains the above-mentioned component (A), cellulose ether (B), and activator (C), a cured geopolymer having a uniform specific gravity and excellent shrinkage reduction property can be obtained. Can be done.
Further, the geopolymer composition of the present invention can obtain a cured geopolymer having excellent freeze-thaw resistance.

The pH of the aqueous dispersion having a concentration of 82.5% by weight of the water-insoluble component of the geopolymer composition of the present invention at 20 ° C. is not particularly limited, but is preferably 12 or more and 14 or less in terms of exhibiting the effects of the present application. If the pH is less than 12, the resulting cured product may be poorly cured. The pH of the aqueous dispersion having a concentration of 82.5% by weight of the water-insoluble component of the geopolymer composition at 20 ° C. is more preferably 12.25 or more and 14 or less, and further preferably 12.5 or more and 14 or less.
The "water-insoluble content of the geopolymer composition" in the present invention means a residue when the geopolymer composition is heated at 120 ° C. to a constant weight. Further, the method for measuring the pH of the aqueous dispersion having a concentration of 82.5% by weight of the water-insoluble component of the geopolymer composition at 20 ° C. is the method measured in Examples.

Since the geopolymer composition of the present invention requires a cellulose ether (B) and an activator (C), it is considered that the activator (C) improves the stability of the cellulose ether (B) as described above. As a result, even if the geopolymer composition exhibits strong alkalinity and the pH of the water-insoluble content of the geopolymer composition is 82.5% by weight, which is 12 or more and 14 or less, the material of the material contained in the geopolymer composition. A cured product having uniform specific gravity and excellent shrinkage reduction property can be obtained without impairing the inseparability and the stability of the introduced air bubbles, and the obtained cured product can be obtained from ordinary cement concrete or mortar. It is considered that similar performance can be obtained.

The viscosity of the aqueous dispersion of the geopolymer composition of the present invention having a concentration of 82.5% by weight in water at 20 ° C. is not particularly limited, but is preferably 2000 to 40,000 mPa · s in terms of achieving the effects of the present application. .. If the viscosity is less than 2000 mPa · s, the material inseparability of the material contained in the geopolymer composition and the stability of the introduced bubbles may decrease. On the other hand, if the viscosity is more than 40,000 mPa · s, uniform bubbles cannot be introduced, the specific gravity of the obtained cured product becomes non-uniform, and the appearance may be impaired. The viscosity of the aqueous dispersion having a concentration of 82.5% by weight of the water-insoluble component of the geopolymer composition at 20 ° C. is more preferably 2500 to 35000 mPa · s, further preferably 3000 to 30000 mPa · s, and particularly preferably 3500 to 25000 mPa · s.・ S. The method for measuring the viscosity of the aqueous dispersion having a concentration of 82.5% by weight of the water-insoluble component of the geopolymer composition at 20 ° C. was measured using a B-type viscometer.

As a production method in the geopolymer composition of the present invention, a step of mixing the above-mentioned component (A), cellulose ether (B) and activator (C) as essential (component (A), cellulose ether (B) and activity). A step of obtaining a mixture in which the agent (C) is essential) is included. The mixture preferably further comprises at least one selected from the activator (D), component (E), aggregate and water described above. The mixture may also contain the other ingredients mentioned above.

Examples of the order of mixing the above-mentioned materials include a method of adding and mixing in the order of 1) to 5) below. Further, the material may be in the state of an aqueous dispersion or in the state of an aqueous solution.
1) Cellulose ether (B) and activator (C) are added to the component (A) and mixed to obtain a mixture 1.
2) The aggregate and the activator (D) are added to and mixed with the mixture 1 to obtain a mixture 2.
3) Add water to the mixture 2 so as to have a predetermined amount and mix to obtain the mixture 3.
4) An aqueous solution of the component (E) is added to and mixed with the mixture 3 to obtain a mixture 4.
5) The mixture 4 is further stirred to introduce air bubbles to obtain a geopolymer composition.

Examples of the apparatus used in the above 1) to 3) include a mixer equipped with a liquid addition mechanism. For example, a mixer having two functions of floating diffusion mixing by a main blade and high-speed shear dispersion by a chopper blade, a professional. Share mixers, Erich mixers, Reedige mixers and the like can be mentioned. Further, as the device used in the above 4) to 5), two stirring rotors are provided in parallel in the kneading tank, and each stirring rotor is rotated in relatively opposite directions to knead the contents; Examples include a formula kneader, a device that mixes with a stirring blade that rotates on the inner surface of the mixing container (a device having a planetary rotation mechanism); a mortar mixer, a hobart mixer, and the like. It is also possible to mix directly into the container containing the mixture 4 with a mortar hand mixer or the like.

In the step of mixing the component (A), the cellulose ether (B) and the activator (C) as essential, an admixture for a geopolymer composition containing the cellulose ether (B) and the activator (C) as essential, and the component The step of mixing with (A) is preferable because the dispersibility of the material can be improved.

[Manufacturing agent for geopolymer composition, admixture for geopolymer composition]
The admixture for a geopolymer composition of the present invention (hereinafter, may be simply referred to as an admixture) contains a water-soluble cellulose ether (B) and an anionic surfactant (C), and is a cellulose ether at 20 ° C. The viscosity of the aqueous solution having a concentration of 2% by weight of B) is 100 to 50,000 mPa · s.

In the admixture for the geopolymer composition of the present invention, the ratio of the content of the cellulose ether (B) to the activator (C) (cellulose ether (B) / activator (C)) is not particularly limited, but is described above. It is preferably in the range.

The admixture for a geopolymer composition of the present invention may further contain the amphoteric tenside agent (D) described above. It is preferable that the admixture contains the activator (D) because the storage stability of the geopolymer composition can be improved.
When the admixture contains the activator (D), the ratio of the content of the activator (C) to the activator (D) in the admixture (activator (C) / activator (D)) is not particularly limited. , It is preferable that it is in the above range.

The form of the admixture for the geopolymer composition of the present invention may be any of the following 6) to 8).
6) The constituent materials are mixed and integrated.
7) A kit in which a part of the constituent materials is mixed and the other materials are separately packaged.
8) A kit in which the constituent materials are separately packaged.

As the admixture for the geopolymer composition of the present invention, when at least one of the materials constituting the admixture is a liquid substance, the admixture contains a wet product which is a mixture of the liquid substance and the granular substance. It may be.
The granular material may be at least one selected from the above aggregate and the above other components, and may be the component (A). Further, as the granular material, the oil absorption amount of the refined linseed oil method based on JIS-K5101-13 is preferably 200 to 500 g / 100 g. If the oil absorption of the granules is less than 200 g / 100 g, the admixture may become sticky and may not be uniformly dispersed. On the other hand, if the oil absorption of the granules exceeds 500 g / 100 g, the production cost of the geopolymer composition may become too high. The oil absorption of the granular material is more preferably 200 to 400 g / 100 g, and particularly preferably 200 to 300 g / 100 g.

As a method for producing an admixture for a geopolymer composition of the present invention, for example, mixing is performed using a general mixer such as the apparatus used in 1) to 5) above, a Nauter mixer, and a ribbon mixer. Can be manufactured by

[Manufacturing method of cured geopolymer and cured geopolymer]
Since the cured geopolymer of the present invention is a cured product of the above-mentioned geopolymer composition, it has a uniform specific gravity and is excellent in shrinkage reduction. In addition, the cured geopolymer of the present invention has excellent freeze-thaw resistance.

The specific gravity of the cured geopolymer of the present invention is not particularly limited, but is preferably 1.0 to 1.9. If the specific gravity of the cured product is less than 1.0, the strength is remarkably insufficient, cracks and chips may occur, and the appearance may be impaired. On the other hand, if the specific gravity of the cured product is more than 1.9, the introduced air bubbles may be insufficient and the freeze-thaw resistance may be lowered. The specific gravity of the cured product is more preferably 1.05 to 1.85, further preferably 1.10 to 1.80, particularly preferably 1.15 to 1.75, and most preferably 1.20 to 1.70. is there. The method for measuring the specific gravity of the cured geopolymer is the method measured in Examples.

The content of water in the entire cured geopolymer of the present invention is not particularly limited, but is preferably 5% by weight or less. If the water content is more than 5% by weight, the curing may be insufficient and the strength may be lowered. The water content is 4.9% by weight or less, more preferably 4.8% by weight or less, particularly preferably 4.7% by weight or less, and most preferably 4.6% by weight or less. The preferable lower limit of the water content is 2.0% by weight or more. It is by the method measured in the examples.

As a method for producing a cured geopolymer, for example, a method of producing a molded body by casting or extruding a geopolymer composition by centrifugal casting or the like, and heating the prepared molded body to cure the molded body. Can be mentioned. Further, if necessary, the mold may be removed and further heated to remove water to a predetermined amount.

Examples of the device used when producing the molded body include a dispenser for casting the geopolymer composition into the mold, a constant-volume transfer pump, a tapping machine for defoaming excess air bubbles, a vibrator, a vacuum degassing device, and the like. Can be done.
The heating temperature of the molded body is not particularly limited, but is preferably 40 to 90 ° C, more preferably 42.5 to 87.5 ° C, still more preferably 45 to 85 ° C, and 47.5 to 82 ° C. It is particularly preferably .5, and most preferably 50 to 80 ° C.
The heating time of the molded product is not particularly limited, but is preferably 24 to 96 hours.
Examples of the device used for heating the molded body include an autoclave that can heat the inside of the chamber with high-temperature steam in an oven or a pressure vessel.

The geopolymer cured product of the present invention can be used as a similar product to cement / concrete and mortar products for various building materials, civil engineering materials, paved road materials and the like.

Hereinafter, examples of the geopolymer composition of the present invention will be specifically described. The present invention is not limited to these examples. In the following examples and comparative examples, unless otherwise specified, "parts" means "parts by weight" and "%" means "% by weight".

[Measurement of gel point of water-soluble cellulose ether (B)]
Using a visible light transmittance measuring device (manufactured by Nippon Kogaku Co., Ltd., model: V-750), an aqueous solution having a concentration of cellulose ether (B) of 2% by weight is heated at a heating rate of 0.5 ° C. per minute. , The transmittance of visible light with a wavelength of 650 nm at a cell length of 10 mm was measured, and the temperature indicating 50% transmittance when the transmittance at 20 ° C. was 100% and the transmittance at 90 ° C. was 0% was set to gel. It was a turning point.

[Measurement of pH]
The pH at 20 ° C. at a concentration of 82.5% by weight of the geopolymer composition / water-insoluble matter was measured using a pH meter (a tabletop pH meter F-71 manufactured by HORIBA, Ltd.).

[Measurement of viscosity]
The viscosity of an aqueous dispersion having a concentration of 82.5% by weight of a water-insoluble component of the geopolymer composition at 20 ° C. and the viscosity of an aqueous solution having a concentration of 2% by weight of cellulose ether (B) are measured by a B-type viscometer. It was measured using a TVB type manufactured by Toki Sangyo Co., Ltd.

[Measurement of water content of cured geopolymer]
The obtained cured geopolymer was heated in an oven at 120 ° C. for 24 hours, and the water content (water content) of the cured geopolymer was measured from the following formula (1).
Moisture content of the cured geopolymer (% by weight) = 100 × [(weight of the cured geopolymer before heating)-(weight of the cured geopolymer after heating)] / (weight of the cured geopolymer before heating) ) (1)

[Measurement of specific gravity of cured geopolymer]
Using an electronic hydrometer (ALFA MIRAGE MDS-3000, manufactured by Alpha Mirage Co., Ltd.), the specific gravity of the cured geopolymer obtained at 20 ° C. was measured. To start the measurement, the geopolymer cured product was immersed in water, and the measurement was started after 30 seconds had passed.

[Appearance evaluation of cured geopolymer 1]
The presence or absence of black spots on the surface of the obtained cured geopolymer was confirmed.
◯: No black spots were confirmed, and the material was well dispersed and stable.
Δ: Slight black spots were confirmed, and the dispersibility and stability of the material were slightly poor.
X: Many black spots were confirmed, and the dispersibility and stability of the material were poor.

[Appearance evaluation of cured geopolymer 2]
The presence or absence of foam on the upper surface of the obtained cured geopolymer was confirmed.
◯: There are no bubbles on the upper surface, and the stability of bubbles is good.
Δ: A thin foam was confirmed on the upper surface, and the stability of the foam was slightly poor.
X: A state in which foamy substances are layered on the upper surface is confirmed, and the stability of bubbles is poor.

[Appearance evaluation of cured geopolymer 3]
The presence or absence of gloss on the surface of the obtained cured geopolymer was confirmed.
◯: Gloss is confirmed and the material is well dispersed.
Δ: Slight gloss was confirmed, and the dispersibility of the material was slightly poor.
×: Not glossy and poor material dispersibility.

[Appearance evaluation of cured geopolymer 4]
The presence or absence of coarse bubbles of φ1 mm or more on the surface and cut surface of the obtained cured geopolymer was confirmed.
◯: Coarse bubbles of φ1 mm or more are not observed on the surface / cut surface, and the bubbles are uniform.
Δ: Coarse bubbles of φ1 mm or more were not observed on the surface, but were observed on the cut surface, and the bubbles were slightly uneven.
X: Coarse bubbles of φ1 mm or more are observed on the surface and cut surface, and the bubbles are non-uniform.

[Appearance evaluation of cured geopolymer 5]
The presence or absence of cracks and cracks on the surface of the obtained cured geopolymer was confirmed.
◯: No cracks or cracks were found on the surface of the cured product.
Δ: Slight cracks and cracks were confirmed on the surface of the cured product.
X: Cracks and cracks were confirmed on the surface of the cured product.

[Evaluation of shrinkage reduction property of cured geopolymer]
The value obtained by dividing the maximum value of the bottom diameter of the obtained geopolymer cured product by the diameter of the bottom surface of the mold using the obtained shrinkage ratio (%) was defined as the shrinkage ratio (%), and the obtained shrinkage ratio (%) was calculated according to the following criteria. The shrinkage reduction property of the cured product was evaluated.
◯: 97.5% or more Δ: 95.0% or more, less than 97.5% ×: less than 95.0%

[Evaluation of specific gravity uniformity of cured geopolymer]
The obtained cured geopolymer was divided into upper and lower parts so as to be uniform, and the uniformity of the specific gravity of the cured geopolymer was evaluated from the absolute value of the difference in specific gravity of each according to the following criteria.
◯: ｜ Difference in specific gravity ｜ ＜ 0.050
Δ: 0.050 ≦ | Difference in specific gravity | <0.10
×: | Difference in specific gravity | ≤ 0.10

[Example 1]
80 parts by weight of fly ash (Type II), 20 parts by weight of blast furnace slag fine powder, and 100 parts by weight of silica sand (weight ratio of No. 5: No. 6: 7 = 1: 1: 0.5) are put into a polydiscup. And mixed to be uniform. Subsequently, 1.0 part by weight of Marpolose 90MP-4000 (manufactured by Matsumoto Yushi Pharmaceutical Co., Ltd., hydroxypropyl methylcellulose, viscosity of 2 wt% aqueous solution at 20 ° C. is 4696 mPa · s) was added and mixed while lavanol CK (Matsumoto Yushi). 0.60 parts by weight of an aqueous solution of coconut fatty acid potash soap manufactured by Pharmaceutical Co., Ltd., concentration 40% by weight, and water content 60% by weight) was added and mixed so as to be uniform. Further, 53.2 parts by weight of water was added and mixed so as to be uniform, and then 10 parts by weight (sodium hydroxide 4.) of an aqueous solution of industrial caustic soda (an aqueous solution having a sodium hydroxide concentration of 48% by weight and a water content of 52% by weight) was added. 8 parts by weight of water, 5.2 parts by weight of water) was added, and 37.6 parts by weight (20.7 parts by weight of sodium hydroxide) of water glass (JIS-1, sodium silicate concentration 55% by weight, water content 45% by weight aqueous solution) was added. , 16.9 parts by weight of water) and mixed so as to be uniform to obtain a mixture 4-1. The materials were mixed using TK Homo Disper (TK AUTO HOMO MIXER MODEL M TYPE A, manufactured by Primix Corporation) at a rotation speed of 1000 rpm.
The obtained mixture 4-1 was stirred at 3000 rpm for 30 seconds using TK Homo Disper (TK AUTO HOMO MIXER MODEL M TYPE A, manufactured by Primix Corporation), and at that time, bubbles were introduced to geo. A polymer composition was obtained. The water content of the obtained geopolymer composition was 75.7 parts by weight, and the water content in the entire mixture 4-1 was 25.0% by weight. The viscosity of the obtained geopolymer aqueous dispersion having a concentration of 82.5% by weight of water-insoluble matter at 20 ° C. was 8000 mPa · s (NO4, 3 rpm), and the concentration of water-insoluble matter was 82.5% by weight. The pH of the aqueous dispersion at 20 ° C. was 12.6.
The obtained geopolymer composition was cast into a polycarbonate columnar mold having an inner diameter of 22 mm and a height of 35 mm, heated in an oven at 80 ° C. for 4 hours, then demolded, and subsequently in an oven at 80 ° C. The geopolymer cured product was obtained by heating in. A total of three times were cast into separate molds having the same shape to prepare a cured geopolymer by the same method as described above, and evaluation was carried out using the three cured products prepared. The water content of the cured product is the average value of the water content of the three cured products, and the absolute value of the difference between the upper and lower specific gravity of the cured product is the difference between the upper and lower specific gravity of each of the three cured products. The average value of the absolute values was used, and the shrinkage rate of the cured product was the average value of the shrinkage rates of the three cured products.
The water content of the obtained cured geopolymer was 4.6% by weight, and the specific gravity was 1.28 for the first casting, 1.30 for the second, and 1.32 for the third, reducing shrinkage. The property was good at 97.8%, and the uniformity of specific gravity was good when the absolute value of the difference in specific gravity was 0.04. In addition, no black spots were confirmed on the surface of any of the obtained cured geopolymers, gloss was confirmed, the dispersibility of the material was good, and cracks and chips were not confirmed. In addition, there were no bubbles on the upper surface of the cured product, and the stability of the bubbles was good.

[Examples 2 to 16, Comparative Examples 1 to 30]
In Examples 2 to 16 and Comparative Examples 1 to 30, the geopolymer composition and the geopolymer cured product are the same as in Example 1 except that the materials are changed as shown in Tables 1, 2, 4, 5 and 6, respectively. Was obtained, and the physical properties and the like were evaluated in the same manner as in Example 1. The results are shown in Tables 1, 2, 4, 5 and 6.

[Example 17]
A uniform mixture of 2.0 parts by weight of Lavanol CK and 2.0 parts by weight of Marpo Vista MLS (manufactured by Matsumoto Yushi Pharmaceutical Co., Ltd., an aqueous solution of lauryldimethylaminoacetic acid betaine concentration 33% by weight and water content 67% by weight). The geopolymer composition and the cured geopolymer were obtained in the same manner as in Example 1 except that the other materials were changed as shown in Table 2, and the physical properties and the like were evaluated in the same manner as in Example 1. The results are shown in Table 2.

[Examples 18 to 20]
In Examples 18 to 20, a geopolymer composition and a cured geopolymer were obtained in the same manner as in Example 17, except that the materials were changed as shown in Tables 2 and 3, respectively, and the physical properties and the like were also the same as in Example 17. Evaluated in the same way. The results are shown in Tables 2-3.

[Example 21]
A geopolymer composition admixture in which 1.0 part by weight of Marporose 90MP-4000 and 4.0 parts by weight of Lavanol CK were separately packaged was used, and other materials were changed as shown in Table 3. A geopolymer composition and a cured geopolymer were obtained in the same manner as in Example, and their physical properties were evaluated in the same manner as in Example 1. The results are shown in Table 3.

[Example 22]
4 parts by weight of Carplex # 80 (Evonik Japan, amorphous silica powder, oil absorption: 220 g / 100 g) was added to the Polydiscup, followed by TK Homo Disper (Primix Corporation, TK. While stirring at 800 rpm using AUTO HOMO MIXER MODEL M TYPE A), 4 parts by weight of lavanol CK was slowly added, followed by stirring at 3000 rpm for 30 seconds to obtain a wet powder. The obtained wet powder was used, and the geopolymer composition and the cured geopolymer were obtained in the same manner as in Example 1 except that the other materials were changed as shown in Table 3, and the physical properties were also the same as in Example 1. Evaluated in the same way. The results are shown in Table 3.

[Example 23]
4 parts by weight of Carplex # 80 was put into a polydiscup, and then Ravanol CK4 was stirred at 800 rpm using TK Homo Disper (TK AUTO HOMO MIXER MODEL M TYPE A manufactured by Primix Corporation). Add 1 part by weight slowly to confirm that it became a wet powder, then add 1 part by weight of Marporose 90MP-4000, and then stir at 3000 rpm for 30 seconds to make a wet geopolymer composition. An admixture was obtained. Using the obtained admixture for geopolymer composition, the geopolymer composition and the cured geopolymer were obtained in the same manner as in Example 1 except that the other materials were changed as shown in Table 3, and the physical properties were also carried out. Evaluation was performed in the same manner as in Example 1. The results are shown in Table 3.

[Example 24]
A mixture was prepared by uniformly mixing 2.0 parts by weight of Lavanol CK and 2.0 parts by weight of Marpo Vista MLS in advance. Next, 4 parts by weight of Carplex # 80 was put into the polydiscup, and then it was prepared using TK Homo Disper (manufactured by Primix Corporation, TK AUTO HOMO MIXER MODEL M TYPE A) while stirring at 800 rpm. The mixture was slowly added, followed by stirring at 3000 rpm for 30 seconds to give a wet powder. The same as in Example 1 except that the obtained wet powder and the admixture for a geopolymer composition in which Marpolose 90MP-4000 are separately packaged are used, and the other materials are changed as shown in Table 3. A geopolymer composition and a cured geopolymer were obtained, and their physical properties were evaluated in the same manner as in Example 1. The results are shown in Table 3.

[Example 25]
2.0 parts by weight of TAYCA Power LN2050D (manufactured by TAYCA Corporation, aqueous solution of sodium alkylbenzene sulfonate concentration 50% by weight, water 50% by weight) and 2.0 parts by weight of Marpo Vista ML are uniformly mixed in advance to prepare the mixture. Made. Next, 4 parts by weight of Carplex # 80 was put into the polydiscup, and then using TK Homo Disper (TK AUTO HOMO MIXER MODEL M TYPE A manufactured by Primix Corporation) while stirring at 800 rpm. The prepared mixture was slowly added, followed by stirring at 3000 rpm for 30 seconds to give a wet powder. The same as in Example 1 except that the obtained wet powder and the admixture for a geopolymer composition in which Marpolose 90MP-4000 are separately packaged are used, and the other materials are changed as shown in Table 3. A geopolymer composition and a cured geopolymer were obtained, and their physical properties were evaluated in the same manner as in Example 1. The results are shown in Table 3.

[Example 26]
Lavanol SF-7K (manufactured by Matsumoto Yushi Seiyaku Co., Ltd., aqueous solution of polyoxyethylene secondary alkyl ether sulfate sodium salt concentration 33% by weight, water 60% by weight) was 2.0 parts by weight and Marpo Vista ML was 2.0 parts by weight. Was uniformly mixed in advance to prepare a mixture. Next, 4 parts by weight of Carplex # 80 was put into the polydiscup, and then using TK Homo Disper (TK AUTO HOMO MIXER MODEL M TYPE A manufactured by Primix Corporation) while stirring at 800 rpm. The prepared mixture was slowly added, followed by stirring at 3000 rpm for 30 seconds to give a wet powder. The same as in Example 1 except that the obtained wet powder and the admixture for a geopolymer composition in which Marpolose 90MP-4000 are separately packaged are used, and the other materials are changed as shown in Table 3. A geopolymer composition and a cured geopolymer were obtained, and their physical properties were evaluated in the same manner as in Example 1. The results are shown in Table 3.

[Example 27]
Liporan LB-440 (manufactured by Lion Specialty Chemicals Co., Ltd., an aqueous solution of α-olefin (C14) sodium sulfonate concentration 35% by weight, water 63% by weight) was 2.0 parts by weight and Marpo Vista ML was 2.0 parts by weight. Was uniformly mixed in advance to prepare a mixture. Next, 4 parts by weight of Carplex # 80 was put into the polydiscup, and then using TK Homo Disper (TK AUTO HOMO MIXER MODEL M TYPE A manufactured by Primix Corporation) while stirring at 800 rpm. The prepared mixture was slowly added, followed by stirring at 3000 rpm for 30 seconds to give a wet powder. The same as in Example 1 except that the obtained wet powder and the admixture for a geopolymer composition in which Marpolose 90MP-4000 are separately packaged are used, and the other materials are changed as shown in Table 3. A geopolymer composition and a cured geopolymer were obtained, and their physical properties were evaluated in the same manner as in Example 1. The results are shown in Table 3.

Details of the materials used are shown in Table 7.

<Evaluation of compression strength and freeze-thaw resistance>
The geopolymer compositions obtained in Examples 1 and 20 and Comparative Examples 1 and 18 were cast into a polypropylene columnar mold having an inner diameter of 48 mm and a height of 70 mm. The geopolymer composition obtained in Comparative Example 30 was cast into a polypropylene columnar mold having an inner diameter of 48 mm and a height of 140 mm. Each cast is heated in an oven at 80 ° C. for 8 hours, then demolded, subsequently heated in an oven at 120 ° C. for 4 hours, and then further heated at 80 ° C. for 24 hours to cure the geopolymer. I got a body.
Regarding the geopolymer cured product obtained from the geopolymer composition of Comparative Example 30, 50% of the upper portion was cut out based on the height with the spout side of the geopolymer composition as the upper portion, and the remaining cured product was evaluated. ..
The compression strength of the cured geopolymer and the evaluation of shrinkage resistance were evaluated as follows, and the specific gravity of the geopolymer was also measured by the above method. Further, for the evaluation of shrinkage resistance and the measurement of compressive strength and specific gravity, three cured products were prepared in each of the above-mentioned Example and Comparative Example, each of them was evaluated and measured, and the average value thereof was adopted. The results are shown in Table 8.

[Measurement of compressive strength of cured geopolymer]
The compression strength was measured by a method conforming to JIS A1108 using an Amsler type compression tester (MIC-101-0-02 type, manufactured by Marui Co., Ltd.). As the measured test piece, the cured product obtained by the above method was aged in a thermostatic chamber at 20 ° C. and 65% for 48 hours.

[Evaluation of freeze-thaw resistance of cured geopolymer]
A constant temperature and humidity machine (PL-2 type, manufactured by Tabay Espec Co., Ltd.) was used, and the method was performed in accordance with the JIS A1148 underwater freeze-thaw test method. The test temperature range was +20 to -20 ° C., freezing and thawing was repeated up to 300 cycles, and the mass residual ratio before and after the evaluation of the cured product was calculated from the following formula (1). The larger the value of the mass residual ratio, the better the freeze-thaw resistance.
The mass residual ratio (W _n ) was calculated from the cumulative mass of the following scaling measured every 50 cycles.
Scaling of the nth cycle: The pan on which the cured product was placed was pulled up every 50 cycles, and the scale remaining on the pan and the scale that fell off from the cured product with running water were collected. The collected scales were dried in an oven at 120 ° C. for 24 hours. The mass of the obtained n-cycle scaling was measured.
Mass residual rate (%) at the nth cycle: W _n = (w ₀ −w _n ) × 100 / w ₀ (1)
w ₀ : Mass of cured product at 0th cycle (before evaluation) w _n : Cumulative mass of scaling up to nth cycle

As can be seen from Tables 1 to 27, the geopolymer compositions of Examples 1 to 27 consist of a base material component (A) essential containing coal ash and / or blast furnace slag and an aqueous solution having a concentration of 2% by weight at 20 ° C. Since it is a geopolymer composition containing a water-soluble cellulose ether (B) having a viscosity of 100 to 50,000 mPa · s and an anionic surfactant (C), the obtained cured geopolymer has a uniform specific gravity and shrinks. It was confirmed that the reduction property was excellent.
On the other hand, as can be seen from Tables 4 to 6, when the geopolymer composition does not contain the water-soluble cellulose ether (B) (Comparative Examples 1 to 2, 9 to 30), the geopolymer composition is an anionic surfactant (). When C) is not included (Comparative Examples 3 to 8), the problem of the present application has not been solved.

Claims (9)

A geopolymer composition containing a base material component (A), a water-soluble cellulose ether (B), and an anionic surfactant (C).
The base material component (A) contains coal ash and / or blast furnace slag.
The viscosity of the aqueous solution having a concentration of 2% by weight of the water-soluble cellulose ether (B) at 20 ° C. is 100 to 50,000 mPa · s.
Geopolymer composition. The geopolymer composition according to claim 1, wherein the pH of the aqueous dispersion having a concentration of 82.5% by weight of a water-insoluble component of the geopolymer composition at 20 ° C. is 12 or more and 14 or less. The geopolymer composition according to claim 1 or 2, further comprising an amphoteric surfactant (D). The geopolymer composition according to any one of claims 1 to 3, further comprising an alkaline component (E) containing an alkali metal silicate as an essential component. The method for producing a geopolymer composition according to any one of claims 1 to 4.
The step of mixing the base material component (A) and the admixture for a geopolymer composition is included.
The base material component (A) contains coal ash and / or blast furnace slag.
The admixture for a geopolymer composition contains a water-soluble cellulose ether (B) and an anionic surfactant (C).
The viscosity of the aqueous solution having a concentration of 2% by weight of the water-soluble cellulose ether (B) at 20 ° C. is 100 to 50,000 mPa · s.
A method for producing a geopolymer composition. The method for producing a geopolymer composition according to claim 5, wherein the admixture for the geopolymer composition further contains an amphoteric surfactant (D). An admixture for a geopolymer composition containing a water-soluble cellulose ether (B) and an anionic surfactant (C).
The viscosity of the aqueous solution having a concentration of 2% by weight of the water-soluble cellulose ether (B) at 20 ° C. is 100 to 50,000 mPa · s.
Admixture for geopolymer compositions. The admixture for a geopolymer composition according to claim 7, further comprising an amphoteric surfactant (D). A cured geopolymer which is a cured product of the geopolymer composition according to any one of claims 1 to 4.