JPH06316451A - Admixture for hydraulic inorganic composition - Google Patents

Abstract

(57) [Summary] [Purpose] To obtain a hydraulic inorganic composition having improved workability and quality by improving water retention, shape retention, plasticity, extrusion lubricity, etc., and improvement of curing delay. Provide an admixture. [Structure] Polysaccharide containing glucose, fucose, rhamnose, glucuronic acid as a constituent monosaccharide, or mannose, a polysaccharide containing one or both of polysaccharides in which fucose is a constituent monosaccharide, and particularly, Alcaligenes reitus B-16
An admixture for a hydraulic inorganic composition containing a strain bacterial culture or a treated product as a main component.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention uses a hydraulic inorganic material such as cement, gypsum, lime, calcium silicate, calcium carbonate, and the like to prepare a hydraulic inorganic composition of mortar,
In the production of various concretes, water retention, shape retention,
It is an admixture for a hydraulic inorganic composition which improves plasticity, extrusion lubricity, curing delay, etc., and improves workability and quality. The admixture for a hydraulic inorganic composition of the present invention is useful for producing building materials, civil engineering materials, heat insulating materials, industrial pipes and the like.

[0002]

2. Description of the Related Art A hydraulic inorganic composition obtained by using a hydraulic inorganic substance such as cement, gypsum, lime, calcium silicate and calcium carbonate is a mortar for plaster, a fiber reinforced concrete, an asbestos slate board, There are various types of concrete such as gypsum board, calcium silicate board, and tile, and they have a wide range of uses such as building materials, roads, bridges, utility poles, piping, exposed surface treatment materials for tunnels and grounds. These hydraulic inorganic compositions are manufactured by adding various aggregates and water to a hydraulic inorganic material, kneading the mixture, molding it by pouring it into a mold, extruding, coating and spraying, and then curing it. When the hydraulic inorganic substance and water are kneaded in this way, various molding aids such as a plasticizer are added to adjust the properties of the kneaded product. The hydraulic inorganic composition differs in composition and required properties of the uncured hydraulic inorganic composition at the time of molding depending on the application, but the uniformity of the composition, water retention, shape retention, plasticity, extrusion lubricity, etc. A variety of admixtures for hydraulic inorganic compositions have been used to improve cure, improve retardation, and improve workability and quality.

However, even if the admixture is used, there are still many improvements in the molding of the hydraulic inorganic composition, and specific examples are as follows. Mortar mainly composed of cement, sand, and water is generally applied to a flat surface, especially to a wall surface, using a trowel, so the mortar has an appropriate viscosity and adhesiveness, and the mortar stretches and trowels during installation. It is required that the mortar is well separated, water does not seep over the surface of the mortar after construction, has surface smoothness, and does not drip (hangs down or deforms after construction) before hardening.
Various admixtures are used to satisfy this condition. It is preferable to use a large amount of admixture to prevent water from seeping out onto the surface of the mortar after mortar construction, maintain surface smoothness, and prevent dripping. However, it may be unfavorable because the mortar becomes undesirably stretched or the trowel may be difficult to separate from the mortar, and its blending amount is generally adjusted in consideration of the application and workability of the mortar and requires skill.

The fiber reinforced concrete (hereinafter referred to as FRC) is a concrete reinforced with 0.1 to 30% by weight (with respect to FRC) of the reinforcing fiber to improve its concrete strength. It is used in a wide variety of areas, especially in parts that particularly require strength in timber, exterior panels, curtain walls, flooring, buildings, bridges, tunnels, roads, and structures. The production is roughly classified into a casting method and an extrusion method. In FRC, it is important that the fibers are dispersed in the concrete as uniformly as possible in order to sufficiently exert the reinforcing effect. However, the thinner the reinforcing fibers are, the more fiber bundles or pills called fiber balls are generated in the concrete, resulting in lower strength. It is necessary to take measures to prevent such problems. Conventionally, asbestos has been widely used as a reinforcing fiber, but as it is suspected that asbestos is carcinogenic, it is not generally used today. Carbon fibers, glass fibers, steel fibers, aromatic polyamide fibers, polypropylene fibers, polyethylene fibers, pulp and the like have already been put into practical use as alternative fibers. However, the alternative fiber has a problem that it is not easily dispersed uniformly in concrete as compared with asbestos, and it is necessary to add an admixture to obtain an appropriate viscosity in order to enhance the dispersion effect of the fiber.

In the concrete spraying method, cement, water and other kneaded materials are pressure-fed using compressed air, and mortar and concrete are directly sprayed on the construction surface such as the exposed surface of the excavated ground to instantaneously set and harden. This method is used when excavating tunnels and mountain slopes. A wet method in which a slurry in which all materials such as cement, aggregate, admixture, and water are kneaded is pressure-fed, and a quick-setting agent is mixed and sprayed before the spray nozzle, if necessary, and materials other than water are separated from water. There is a method called a dry method in which a system is pressure-fed, the mixture is joined before the spray nozzle, and the mixture is sprayed. In these spraying methods, a large amount of dust is generated in the dry type during spraying, and rebound (reband) occurs in the dry type and wet type, which not only deteriorates the work environment but also causes a large amount of concrete loss. become. Underwater concrete is a concrete composition that is a mixture of cement, aggregate, water, and various admixtures, and is poured into water using a tremie pipe or bucket. High fluidity and self-leveling property to improve workability, high breathability after casting, high inseparability in water to prevent outflow of components into water (prevention of contamination of surrounding water), shape retention Excellent shape retention and rapid onset of curing are required. Therefore, when pouring underwater concrete, a fluidizing agent for obtaining fluidity, a self-leveling property during pouring and an admixture for the inseparability of concrete after pouring, and for accelerating the development of hardening. The coagulation accelerators, etc. are used.

Centrifugal molded concrete is used for manufacturing poles, piles, fume pipes and the like, and these are widely used in the field of civil engineering and construction. These concrete products are
Cement, aggregate, water, and various admixtures are mixed in advance and kneaded, put into a cylindrical form and molded by applying centrifugal force, and then subjected to underwater curing, autoclave curing, etc. There is. When centrifuging concrete, a large amount of slag or paste is generated on the inner surface of the pipe due to centrifugal force. Therefore, a large amount of concrete is placed in the cylinder form in advance in anticipation of the amount of paste and paste. Conventionally, such a slag or a paste-like material is discharged out of the pipe by inclining the mold after molding or scraped off. Also, if there is a large amount of glue or paste, the surface of the inner wall of the centrifugally molded concrete becomes uneven, so it must be mechanically shaved off. This paste or paste has self-hardening property and its composition is not constant, so that it is difficult to reuse and it is generally solidified and disposed of. Furthermore, since it is strongly alkaline, the disposal site is limited from the viewpoint of environmental protection. In order to suppress the generation of slag and paste-like substances, it is necessary to reduce the slump value of concrete. The slump value is a measure of the softness of concrete that has not yet set,
Those with a small slump value have low fluidity and high shape retention. Therefore, kneading a low slump concrete composition,
There is a method of compacting with a relatively small centrifugal force, but this reduces the effect of centrifugal molding and is not very preferable. So admixtures are being dealt with.

As described above, the hydraulic inorganic composition varies depending on its purpose, usage, etc., but the components of the hydraulic inorganic composition are not separated during the curing process and are always kept uniform. What is required is excellent water retention, shape retention, plasticity, extrusion lubricity, etc. from molding to curing. In particular, it is required to have fluidity in mortar, dispersibility of reinforcing fiber in FRC, adjustment of viscosity in sprayed concrete, inseparability in water in underwater concrete, and reduction of slag or paste in centrifugally molded concrete. ing. These requirements have been addressed by adding various admixtures.

As the admixture, polyvinyl alcohol (PVA) (JP-A-57-123850 and JP-A-61-50900), polyacrylamide (JP-A-61-260453), polyethylene oxide ( PEO) (Japanese Patent Publication No. 1-58141), synthetic polymer-based compounds, alginates (JP-A-3-22)
No. 8857), guar gum, xanthan gum (Japanese Patent Laid-Open No. 2-217345),
Furthermore, HPMC, ethyl cellulose (EC), hydroxyethyl cellulose (HEC), hydroxyethyl methyl cellulose (HEMC), hydroxypropyl cellulose (HPC), carboxymethyl cellulose (CM)
C) (JP-A-57-123850 and JP-A-61-7)
2664) and the like, and water-soluble cellulose-based materials and derivatives thereof (Japanese Patent Laid-Open No. 61-21948).

However, the hardening of the hydraulic inorganic material is a hydration reaction of the inorganic calcium salt, and polyacrylamides, alginates, guar gum, xanthan gum, CM.
C or the like easily forms a water-insoluble salt with calcium, and as a result, changes in viscosity over time, composition separation, reduction in water retention (water separation), and reduction in shape retention (deformation) are likely to occur. Is limited. Further, when calcium and a water-insoluble salt are formed, it is difficult to obtain a stable thickening effect. Polyethylene oxide (PEO) has a small amount of foaming, but has a drawback that it is difficult to dissolve in water, and there is a drawback that it remains as it is, depending on the hydraulic inorganic composition to be blended. In addition, since the formed saw-like material has a spinnability, it is a great obstacle to work. Generally widely used is the use of a water-soluble cellulosic admixture, or the combined use of alginate, guar gum, xanthan gum, CMC and a water-soluble cellulosic admixture.

Natural polymer-based admixtures and water-soluble cellulose-based admixtures include water retention, shape retention, plasticity, extrusion lubricity,
Further, when reinforcing fibers are added, it is effective to disperse the reinforcing fibers uniformly, but as the compounding amount increases, the viscosity of the hydraulic inorganic composition increases, the fluidity decreases, and the strength increases due to the increase in the amount of air inclusions. This leads to disadvantages such as a decrease and an increase in curing delay. The inclusion of air impairs the uniformity of strength due to the formation of bubbles in the hydraulic inorganic composition, and even if an antifoaming agent is added, it is not possible to completely eliminate the inclusion of air, but it is also hydrophobic. When a large amount of the defoaming agent is added, the strength of the hydraulic inorganic composition decreases. In addition, the hardening of the hydraulic inorganic substance is usually expressed in 2 to 4 hours only with cement. If the time required for the onset of curing becomes long, the molded product will gradually deform before the curing begins, which will reduce the shape and dimensional stability of the product. Damage during molding, cracks during high temperature and high pressure curing,
It will cause damage to manufacturing, such as damage.

[0011]

DISCLOSURE OF THE INVENTION The present invention overcomes the above drawbacks of the prior art and improves workability by improving water retention, shape retention, plasticity, extrusion lubricity, etc. and curing delay.
The present invention provides an admixture for obtaining a hydraulic inorganic composition having improved quality.

[0012]

Means for Solving the Problems As a result of intensive studies to improve such conventional drawbacks, the present inventors have found that a blending agent for hydraulic inorganic substances containing a specific polysaccharide is blended. According to the present invention, it was found that the water-holding property, shape-retaining property, plasticity, extrusion lubricity of the hydraulic inorganic composition is improved, further curing delay is improved, and workability and product quality are improved. Has been completed.

That is, the present invention provides a hydraulic composition containing, as a main component, one or both of a polysaccharide having glucose, fucose, rhamnose, and glucuronic acid as constituent monosaccharides, mannose, and a polysaccharide containing fucose as a constituent monosaccharide. It is an admixture for inorganic substances.

In the admixture of the present invention, the constituent ratios of glucose, fucose, rhamnose and glucuronic acid are (1-8) :( 1-4) :( 1-4) :( 1-
The polysaccharide, mannose, or fucose, which is 4), may contain, as a main component, either one or both of the polysaccharides having a molar ratio of (1 to 4) :( 1 to 4). .

As the polysaccharide of the present invention, Alcaligenes latus, particularly Alcaligenes latus.
tus) B-16 strain (FERM BP-2015)
It includes the bacterial culture of JP-A-2-291292 or a processed product thereof. The Alcaligenes reitus bacterium and the Alcaligenes reitus B-16 strain therein are strains having a polysaccharide-producing ability. As carbon sources of such strains, fructose, glucose, monosaccharides such as sucrose, in addition to oligosaccharides, hemicellulose, starch, natural polymers such as corn starch, and oil carbon sources such as olive oil are preferably used. . In addition, urea, ammonium chloride, ammonium nitrate, ammonium sulfate and other inorganic nitrogen sources, tryptone, yeast extract, meat extract, peptone, malt extract and other organic nitrogen sources, other inorganic salts such as potassium phosphate, magnesium sulfate, salt, etc. Used as a constituent. The culture may be liquid culture. The initial pH of the culture is 4-1
0, temperature 15 to 40 ° C., and usually aeration and agitation culture. The culturing is carried out for 1 to 10 days, although it varies depending on the conditions such as the type of carbon source. For the treatment of the culture, for example, adding twice the amount of ethanol to the culture medium
The precipitate formed by standing overnight at ℃ Collected by filtering with 2 filter paper, then washed with 70% ethanol 3 times, and further with distilled water 3 times on filter paper, and then the aggregated substance whose water is removed by freeze-drying etc. can be recovered as a culture-treated product. . In the present invention, the separated and purified culture can be used as it is, or the culture can be treated and used.
The present invention is not limited to such culture method and treatment method.

The admixture for a hydraulic inorganic composition of the present invention also includes an admixture containing, as a main component, a mixture of the above polysaccharide and at least one water-soluble cellulose derivative selected from HPMC and HEC. By mixing the two, the performance that makes the best use of the respective characteristics of both is exhibited. Polysaccharides and HP
When mixed with at least one selected from water-soluble cellulose derivatives of MC and HEC and added to the hydraulic inorganic material, the mixing ratio is 95: 5 to 5:95 (weight ratio). Outside this range, the effect of substantially mixing cannot be obtained. The addition amount of the admixture for a hydraulic inorganic composition of the present invention is 0.001 to 5.0% by weight based on the hydraulic inorganic material. The optimum amount of this addition amount is the composition of the hydraulic inorganic composition,
Although it varies depending on the purpose of use, conditions of use, etc., it is usually preferably added in an amount of 0.01 to 2.0% by weight. If it exceeds 5.0% by weight (hydraulic inorganic substance), the viscosity is increased and the workability is deteriorated, which is not preferable. On the other hand, if the amount is less than 0.001% by weight (hydraulic inorganic substance), no sufficient effect can be expected.

Although it is difficult to obtain a polysaccharide having a substantially 100% purity, the weight as a standard for the amount of addition is usually obtained from the content of saccharide in the polysaccharide. In the case of the polysaccharide obtained from Alcaligenes reitus strain B-16 in a specific liquid medium, 19% of the polysaccharide is exemplified in this polysaccharide by the carbazole sulfate reaction (Japanese Patent Application No. 3-316391). No.), the substantial amount of the polysaccharide from Alcaligenes reitus strain B-16 can be determined from this analysis value. When cultured with a different culture method from the above,
Alternatively, in the case of other polysaccharides, it is necessary to prepare a highly purified sample once and measure the saccharides by the carbazole sulfate method.

The hydraulic inorganic substances are cement, gypsum, lime, calcium silicate and the like. The cement includes various kinds of commonly used normal / early-strength / ultra-early-strength portland cement, blast furnace slag, various mixed cement mixed with fly ash, expanded cement, and special cement such as alumina cement. In the production of the hydraulic inorganic composition, the hydraulic inorganic material and water, an aggregate, a reinforcing fiber, various admixtures for the hydraulic inorganic material, etc. are added depending on the purpose. As the aggregate, silica sand, natural sand, gravel, shirasu balloon, etc. are used. When it is used in the production of fiber reinforced concrete, carbon fiber, glass fiber, steel fiber, aromatic polyamide fiber, polypropylene fiber, pulp, etc. are used as the reinforcing fiber. 30 wt% (vs. FRC) is compounded. The hydraulic inorganic material admixture of the present invention effectively acts to disperse these reinforcing fibers, and is therefore suitable for the production of fiber-reinforced concrete.

The polysaccharide of the present invention is i) good in water retention and
i) The aqueous solution has a large thickening effect and a small temperature dependence of viscosity as compared with the conventionally used thickeners, and has a substantially constant viscosity between 2 and 80 ° C. which can stably exist as an aqueous solution. Iii) This aqueous solution has a pseudoplastic property, and even a low-concentration aqueous solution of 0.01% by weight or less has a low viscosity when a shearing force is applied, but at the moment when the application of force is stopped , The viscosity increases significantly,
iv) The effect of inorganic salts such as calcium is small, and v) These characteristics are exhibited even in the highly alkaline region of cement slurry (Japanese Patent Laid-Open No. 4-200389).
issue). When this polysaccharide is applied to a hydraulic inorganic composition, this unique property is utilized and the following advantages are brought out.

As an advantage over the hydraulic inorganic composition in general, * wettability on the surface can be maintained for a long time, drying on the surface can be suppressed * surface smoothness can be improved * air entrainment is low, and bubbles are contained Since there is no inclusion, strength is improved * Sufficient viscosity can be obtained with a small blending amount * Maintenance of composition uniformity (prevention of component separation) * Bleeding can be prevented * Shape retention is improved * Plasticity * Short curing delay * Improved workability due to improved fluidity during molding

In particular, in the case of mortar, * When the material is kneaded, the viscosity is lowered and stirring can be done quickly, and the workability is improved. * When the material is applied with a trowel, the viscosity is lowered, and the spread of the trowel and the spread of the trowel are extremely difficult. Good and the surface is finely and smoothly finished. * After application, the viscosity increases rapidly, so that the mortar does not drip or drip, and the state when applied is maintained. Possible * The tiles will not be displaced and the adhesiveness will be improved * Because there is a large difference between the viscosity when the shearing force is applied and when the force is stopped and when the product is at rest,
Excellent workability can be obtained even if the amount added increases or decreases.

In particular, in fiber-reinforced concrete, the dispersibility of reinforcing fibers is improved. In particular, in sprayed concrete, the viscosity becomes low during pumping by a spraying machine, resulting in very high fluidity and the moment of spraying. Rebound is greatly reduced due to increased viscosity. * Viscosity characteristics do not change with temperature, so even if the temperature rises due to heat of hydration, sprayed concrete and mortar fluidity do not change. And no deviation occurs

In particular, in the underwater concrete, it is possible to improve the workability by increasing the fluidity when pouring concrete to enable pumping and pumping. * The self-leveling property is improved. * The concrete after pouring. Prevents outflow and contamination of the composition by increasing the inseparability of the composition in water. Especially in centrifugal molding concrete, * to reduce slag during centrifugal molding, to reduce paste-like substances and to improve internal smoothness. Become

Other water-soluble cellulosic admixtures that have been used conventionally, such as ethyl cellulose (E
C), hydroxyethyl methylcellulose (HEM
C), hydroxypropyl cellulose (HPC), carboxymethyl cellulose (CMC) and the like can also be used together. When used in combination, the properties of the conventional admixture can be utilized, new properties can be imparted, and the cost can be reduced. Thus, in the present invention, the combined use with other admixture does not hinder the present invention.

In the present invention, the admixture for hydraulic inorganic substances according to the present invention and various other admixtures such as superplasticizer,
The combined use of the AE agent, the rust preventive agent, the defoaming agent and the like is not limited at all. The mixing method of the admixture of the present invention and the hydraulic inorganic material is not particularly limited, but in use, a culture or a treated product thereof is dispersed in water as a liquid, and a method of kneading by mixing with cement, or , There is a method of using it by premixing it with cement after powderizing it. For mixing with cement, a general tilting cylinder mixer, an omni mixer, a V-type mixer, a Henschel mixer, a Nauta mixer, etc. are used and are arbitrarily selected.

[0026]

The present invention will be described below with reference to examples.
The present invention is not limited to these examples.

(Preparation of Alkaline Genes Reitas B-16 Cultured Polysaccharide) B-16 Polysaccharide I: Fucose 15
g, KH ₂ PO ₄ 6.8 g, K ₂ HPO ₄ 8.8 g, M
gSO ₄ .7H ₂ O 0.2 g, NaCl 0.1 g, N
0.5 g of aNO _{3 and} 0.5 g of meat extract were added to deionized water 1
It was dissolved in 1 and the pH was adjusted to 7.4. This medium 150
ml was transferred to a 500 ml Erlenmeyer flask and sterilized in an autoclave at 120 ° C. for 15 minutes, and one platinum loop amount of Alcaligenes retus B-16 strain was added, followed by rotary rotation (180 rpm) at 30 ° C. After culturing for 6 days, twice the amount of ethanol was added and the mixture was left at 5 ° C. overnight to obtain a precipitate. The precipitate was filtered through No. 2 filter paper, washed twice with ethanol, and further washed 3 times with distilled water. After mixing with dry ice and cooling, it was crushed in a mortar and further pulverized with a homogenizer. The polysaccharide I thus obtained contains a high-molecular component, a low-molecular component, and some impurities. B-16 Polysaccharide II: Glucose 10 g, KH ₂ PO ₄ 4.5 g, K ₂ HPO _{4
1.5g, MgSO 4 · 7H 2 O0.2g} , NaCl
0.1 g, NaNO ₃ 0.1 g, glycine 0.1
g, FeSO ₄ .7H ₂ O 0.01 g, deionized water 1 liter
And was adjusted to pH 7.0. This medium 150m
1 was placed in a 500 ml Erlenmeyer flask and sterilized in an autoclave at 120 ° C. for 15 minutes, and then one generous amount of one platinum loop of Alcaligenes retus B-16 strain was added, followed by shaking culture at 30 ° C. for 10 days. After culturing, the polysaccharide was obtained by the ethanol precipitation method in the same manner as the above B-16 polysaccharide I. This polysaccharide
II contains a high-molecular component, a low-molecular component, and some impurities.

B-16 Polysaccharide III: B-16 Polysaccharide I
Same as shoe shoe 15g, KH ₂ PO ₄ 6.8
g, K ₂ HPO ₄ 8.8 g, MgSO ₄ .7H ₂ O 0.
2 g, NaCl 0.1 g, NaNO ₃ 0.5 g, and meat extract 0.5 g were dissolved in distilled water 1 liter, and the pH was 7.4.
Adjusted to. 150 ml of this medium was placed in a 500 ml Erlenmeyer flask and sterilized in an autoclave at 120 ° C. for 15 minutes, and then an amount of 1 platinum loop of Alcaligenes retus B-16 strain was added, followed by rotary rotation (180 rp at 30 ° C.).
m) Cultured. After culturing for 6 days, about 4 times the amount of water was added and the pH was adjusted to 12 with NaOH. This liquid was passed through a column of 1000 ml of ion exchange resin Diaion HPA-75 (OH ⁻ ) (manufactured by Nippon Nermizu Co., Ltd.) to remove proteins, nucleic acids and low molecular components. Next, the filter aid RL700 (Radiolite) was mixed and applied to a 5 μm membrane filter. The mixture was neutralized with hydrochloric acid and concentrated, and twice the amount of acetone was added to the mixture to cause precipitation. The polymer was filtered and washed with acetone to obtain a purified polymer component of B-16 polysaccharide.

(Raw material for hydraulic composition) (1) Cement: ordinary Portland cement (manufactured by Ube Industries, Ltd.) (2) Fine aggregate: Kawasago I: Specific gravity = 2.57, maximum particle size 5 mm, coarse particle Diameter =
2.81 Kawasuna II: Specific gravity = 2.58, maximum particle size 5 mm, coarse particle size =
2.807 No. 7 silica sand No. 8 silica sand (3) Coarse aggregate: Crushed stone I: Specific gravity = 2.61, maximum particle size 20 mm, coarse particle size =
6.62 Crushed stone II: Specific gravity = 2.63, maximum particle size 25 mm, coarse particle size =
6.81 (4) Light weight aggregate: Shirasu balloon (Sankilite Y-04 (trade name) manufactured by Sanki Industry Co., Ltd.) (5) Reinforcing fiber: Pulp: Bleached hardwood pulp Carbon fiber: Pitch-based carbon fiber, Length 10 mm, direct line 15
μ (manufactured by Kureha Chemical Industry Co., Ltd.) (6) Water: Yokkaichi, Mie

(7) Hydroxypropyl methylcellulose
(HPMC): (manufactured by Shin-Etsu Chemical Co., Ltd., hi-Metroses 90SH-15000 (trade name)) (8) Hydroxyethyl cellulose (HEC): (manufactured by Daicel Chemical Industries, Ltd., HEC Daicel) SP-800
(Trade name) (9) Polyethylene oxide (PEO): (Sumitomo Seika
PEO-18 (trade name) manufactured by (Inc.) (10) Polyvinyl alcohol (PVA): (Denka PVAB-17 (trade name) manufactured by Denki Kagaku Co., Ltd.) (11) Curdlan: (Wako Jun Yakusan Co., Ltd./reagent) (12) Zansan gum: (Kelco / KELZA
NZN (trade name)) (13) Ethylene-vinyl acetate-acrylic acid copolymer: ethylene: vinyl acetate: acrylic acid = 20: 78: 2
(Molar ratio), molecular weight = 100,000.
Obtained as described in No. 847.

(14) Polyacrylamide: [η] =
8.5 Obtained as described in JP-A-60-260453. (15) Polyacrylamide propane sulfonic acid:
[Η] = 3.0 Obtained according to the description in JP-A-60-260453. (16) Fast-setting agent: Pozoris Bussan Co., Ltd. QP-55
(Trade name) (17) Water reducing agent: manufactured by Kao, Mighty 150 (Trade name) (18) Fluidizing agent: manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., Seroflow 1
10P (trade name) (19) antifoaming agent: hydrophobic silica, manufactured by Hakuto Co., Ltd.

(Production Example of Hydraulic Inorganic Composition) (1) Mortar Example A mortar composition was blended as shown in Table 1-3, and 50
1 A cement mixer was used for kneading, and a part of the kneaded material was subjected to a slump test and a flow test. In addition, a part of which is vertically placed on a concrete board is 300 mm long and 550 m wide.
m and a thickness of 15 mm were coated with a trowel, and a flat plate tile of 50 mm square was stuck on this. The physical properties of this mortar, the peelability of tiles, and the degree of tile displacement were evaluated. Further, put the remaining mortar in the formwork and make a plate-like object (40 mm x 160 m
m × 10 mm) 6 sheets were prepared, allowed to stand for 24 hours, then demolded and cured in water. The one that was aged in water was used as a specimen at 28 days of age, and a bending strength test was performed. The results are shown in Tables 1-3. In Tables 1 to 3, the following criteria were used for evaluation.

"Slump": Japanese Industrial Standard JIS A
It was measured according to 1101. Smaller slump shows higher viscosity and higher mortar shape retention. "Flow": Measured according to Japanese Industrial Standard JIS R5201. A large flow indicates that the mortar has high fluidity and high pseudoplasticity. "Mortar extension": The condition when the mortar was spread with a trowel was observed. a: The mortar does not break off and spreads well,
b: The mortar does not break, c: the mortar breaks. "Mortar's iron separation": After extending the mortar with the iron, the state of the iron separation was observed. a ': the mortar does not stick to the iron, b': the mortar sticks to the iron.

"Peeling off tile": The presence or absence of tiles dropped from the concrete board was checked. "Tile offset": The downward offset of tiles was measured until the mortar was cured. "Dispersibility of pulp": The dispersion state of pulp in concrete was observed. a ': good dispersion, b': pulp binding and poor dispersion. "Bending strength of mortar": Japanese Industrial Standard JIS R5
201. "Density": determined from weight and apparent volume. "Comprehensive evaluation": The above results were comprehensively evaluated as follows. A: Particularly excellent and improved, B: Slightly improved, C: Not improved or unusable,
Indicates.

From these results, by using the admixture of the present invention, the spread of the mortar, the separation from the iron, the improvement of the fluidity, and the application of the mortar were facilitated. Furthermore, since a mortar with a small slump and high shape retention can be obtained, there is no change in the shape of the mortar after application, and the displacement of the tiles that have been applied and the peeling of the tiles have been eliminated. Further, since the admixture of the present invention has no foaming property, it has no air entrainment to the mortar and a mortar having a high bending strength was obtained.

(2) Example of fiber-reinforced concrete cast molding Each raw material of concrete was mixed with an omni mixer (Chiyoda Industry Co., Ltd.).
OM-5 (trade name) manufactured by K.K. is well kneaded to make a carbon fiber reinforced concrete (CFRC) paste,
Pour into a mold (40 mm × 160 mm × 10 mm),
It was put in a humidity control box at 20 ° C. and left standing for 12 hours to cure. After demolding, autoclave curing (180 ° C, 10 kg / cm
² , 5 hours) to obtain a molded body. Properties of the obtained fiber-reinforced concrete molded body are shown in Table 4-5. In Table 4-5, the following criteria were evaluated.

"Flow": Japanese Industrial Standard JIS R5
201. "Dispersion degree of carbon fibers": The dispersion state of fibers in concrete was visually judged. a ': uniformly dispersed, b': there is a bundle of fibers. “Presence or absence of cured body / defective part at demolding”: presence / absence of defective part was checked. "Bending strength": measured according to Japanese Industrial Standard JIS R5201. "Density": determined from weight and apparent volume. "Comprehensive evaluation": The above results were comprehensively evaluated as follows. A ': improved, B': not improved. By incorporating the admixture of the present invention, the dispersibility of the reinforcing fiber is improved, the amount of air mixed into the concrete is reduced,
The curing delay was reduced. As a result, demolding was facilitated and the strength of the molded body after curing in the autoclave was improved.

(3) Example of Fiber Reinforced Concrete Extrusion Molding Each raw material of concrete is mixed with an omni mixer (Chiyoda Industry Co., Ltd.).
Well kneaded with OM-5 (trade name) manufactured by KK, and further uniaxial screw type kneader (MH-10 manufactured by Miyazaki Tekko KK)
After kneading with 0 type, three pieces of flat plates (80 mm × 20 mm in cross section) having a length of 600 mm were prepared with a small vacuum extrusion molding machine (DE-50 type manufactured by Honda Iron Works Co., Ltd.). This piece was placed on a table about 50 cm in length and about 20 cm in height and placed in a humidity control box at 20 ° C., and the extruded body was placed from the end of the table 6
The amount of downward deformation due to gravity (referred to as "drip amount") was measured until 0 mm was set and the mixture was cured, and used as a measure of the degree of curing delay due to the admixture. The remaining two extruded bodies are 20
After placing in a humidity control box at ℃ for 12 hours, steam curing (180 ℃, 10 kg / cm ² , 5
After that, a CFRC cured product was obtained, and the other was put in water at 20 ° C. and aged for 28 days. The state and properties of these molded products are shown in Table 6-7. In Tables 6-7, the following criteria were evaluated.

"Dispersion degree of carbon fibers": The dispersion state of fibers in concrete was visually judged. a ': uniformly dispersed, b': there is a bundle of fibers. "Extrudability": a ': Extrudable,
b ': indicates that the material cannot be molded due to blockage and a die-shaped molded product cannot be obtained. "Surface smoothness of molded product": a ': a smooth surface, b': uneven or rough surface. "Dag amount": The amount of downward deformation due to gravity was measured. "Bending strength": measured according to Japanese Industrial Standard JIS R5201. "Density": determined from weight and apparent volume. "Comprehensive evaluation": The above results were comprehensively evaluated as follows. A ': improved, B': not improved. By adding the admixture of the present invention, the curing delay was reduced, the sagging (deformation) of the molded product was improved, and the density was increased to improve the bending strength.

(4) Example of Centrifugal Molded Concrete After mixing each raw material of concrete with a 50 l cement mixer, diameter 20 cm × height 30 cm × thickness 4 cm
2 minutes for 3G and 2 minutes for 10G for 2 minutes
Centrifuged at 5 G for 2 minutes. The amount of slag at this time was measured. The obtained molded body is heated at 20 ° C. for 4 hours and then at 65 ° C.
Was steam-cured for 4 hours, naturally cooled, and the compressive strength was measured 7 days after the material age. The results are shown in Table 8. In Table 8, the following criteria were evaluated.

"Slump": Japanese Industrial Standard JIS A
It was measured according to 1101. “Amount of discharged paste”: The amount of discharged paste was measured. "Inside condition": a ': inner surface is smooth by visual judgment
b ': indicates that the inner surface has irregularities. "Compressive strength": Measured in accordance with Japanese Industrial Standard JIS A1108. "Comprehensive evaluation": The above results were comprehensively evaluated as follows. A ': improved, B': not improved. From the results, the admixture of the present invention reduced the slag in the centrifugal molding method, improved the inner surface smoothness, and did not have air entrainment, so that the compressive strength was increased.

(5) Example of sprayed concrete After each raw material of concrete was dry-blended with a 200 l tilting mixer (compound A), 3.0-3.5 kg was sprayed with a spraying machine (lead gun manufactured by PRIPLECO Co., Ltd.). / Cm
Pumped at ² . Separately, a quick-setting agent, a water-reducing agent, an admixture (ethylene-vinyl acetate-acrylic acid copolymer, polyvinyl alcohol) and water were mixed (formulation B), and the mixture was pumped by another high-pressure pump. Both were blended in front of the nozzle and sprayed onto a vertically standing concrete wall. At the time of spraying, at a position about 5 m from the concrete wall surface, the dust amount from the start of spraying to 5 minutes after the end is taken, and the concrete sprayed on the wall surface is immediately taken, and the slump, flow, air entrainment amount, 1 day The cylindrical core was cut out every 7 days and 28 days, and the compressive strength was measured. The results are shown in Table 9. In Table 9, the following criteria were evaluated.

"Slump": Japanese Industrial Standard JIS A
The slump value (cm) was measured according to 1101. "Flow": The flow value (mm) was measured according to Japanese Industrial Standard JIS R5201. "Air entrainment amount": Japanese Industrial Standard JIS A 1128
The air entrainment amount (%) was measured in accordance with. "Dust amount": Dust meter (Shibata Scientific Instruments Co., Ltd. P-5
Type (trade name)). "Rebound rate": A vinyl sheet was laid under the concrete wall, the rebound concrete was collected, the rebound (rebound) amount was measured, and the rebound rate (%) amount to the sprayed concrete amount was obtained. "Compressive strength": Cylindrical cores were cut out every 1, 7, and 28 days of age, and measured according to Japanese Industrial Standards JIS A1108. "Comprehensive evaluation": The above results were comprehensively evaluated as follows. A: Particularly excellent and improved, B: Slightly improved, C: Not improved or unusable,
Indicates. From this result, with the admixture of the present invention, the amount of mixed air is small, high compressive strength is obtained, pumping is easy, and the loss of sprayed concrete is small,
Shotcrete with high shape retention was obtained.

(6) Example of underwater concrete Table 6 shows the results obtained in the examples of underwater concrete. Each raw material of concrete was kneaded using a 50 l cement mixer. The slump flow and the air amount of this concrete paste were measured. 1 liter of this concrete paste with an outer diameter of 110 mm and a height of 150 mm
In a beaker, put 800 ml of water (20 ° C) and gently drop 500 g of this concrete paste from the water surface.
After allowing it to stand for 3 minutes, the water in the beaker was sampled, and the clarity and pH of the water were measured. Also, the fluidity of the concrete in water 10 minutes after the injection was observed, and the amount of air entrained in the concrete was measured.

Further, length 50 cm × width 40 cm × height 40
Water was put in a cm water tank to a depth of 35 cm, and a cylindrical mold having a diameter of 10 cm and a height of 20 cm was put in this water tank, and the concrete paste was gently dropped and put in the mold. 1
Leave it for 5 minutes, take it out, and cure it in water.
The compressive strength was measured for 28 days. The results are shown in Table 10. In Table 10, the following criteria were evaluated.

"Slump flow": According to the slump test method (Japanese Industrial Standard JIS A1101), a slump cone (20 cm) was filled with concrete, and the spread of the concrete produced when the slump cone was immediately pulled up was measured. "PH": pH meter for measuring water in the water tank (manufactured by HORIBA, Ltd., p
It was measured with an H meter D-14). "Clarity of water": The water in the water tank is sampled and the Japanese Industrial Standard J
The amount of suspended solids was measured according to the “Factory drainage test method” described in ISK0102, and a ′: suspended solids 50 pp.
The state is clear when less than m and b ': turbid when the amount of suspended matter is 50 ppm or more. "Air amount entrainment amount": Japanese Industrial Standard JIS A1118
The air content of the concrete was measured in accordance with. "Flowability": Visual observation of the spread of concrete in water, a: Spread is good and flat, b: Spread is slightly insufficient but almost flat, c: Spread is insufficient and flat. , Is shown. "Compressive strength": Measured in accordance with Japanese Industrial Standard JIS A1108. "Comprehensive evaluation": The above results were comprehensively evaluated as follows. A ': improved, B': not improved.

[0047]

[0048]

[0049]

[0050]

[0051]

[0052]

[0053]

[0054]

[0055]

[0056]

[0057]

As described above, according to the present invention, one or both of a polysaccharide containing glucose, fucose, rhamnose, and glucuronic acid as constituent monosaccharides, mannose, and a polysaccharide in which fucose is a constituent monosaccharide. A polysaccharide containing,
In particular, by using an admixture for a hydraulic inorganic composition containing an Alcaligenes reitus B-16 strain bacterial culture or a treated product thereof, the water retention, shape retention, plasticity, extrusion lubricity, etc. are improved, and By improving the setting delay, a hydraulic inorganic composition having improved workability and quality can be obtained.

Front page continuation (72) Inventor Ryuichiro Kurane 1-3 Higashi 1-chome, Tsukuba, Ibaraki Prefectural Institute of Biotechnology, Industrial Technology Institute (72) Zenji Yamaguchi Yokkaichi, Mie 6-6-9 Hakuto Co., Ltd. Yokkaichi Research Institute (72) Inventor Hisatomi Muraki Yokkaichi City, Mie Prefecture 6-6-9 Hakuto Co., Ltd. Yokkaichi Research Institute (72) Inventor Yasuhiro Nobata Yokkaichi City, Mie Prefecture 6-6-9 Hakuto shares Company Yokkaichi Laboratory (72) Inventor Shuji Anazawa 4-19-18 Minamioizumi, Nerima-ku, Tokyo

Claims (12)

[Claims] 1. Glucose, fucose, rhamnose,
An admixture for a hydraulic inorganic composition containing, as a main component, one or both of a polysaccharide containing glucuronic acid as a constituent monosaccharide, mannose, and a polysaccharide in which fucose is a constituent monosaccharide. 2. The composition ratio of glucose, fucose, rhamnose, and glucuronic acid components is a molar ratio of each (1 to 8):
(1 to 4): (1 to 4): (1 to 4) polysaccharide, mannose, and fucose each have a molar ratio of (1).
-4): The admixture for a hydraulic inorganic composition according to claim 1, wherein one or both of the polysaccharides (1-4) are contained as a main component. 3. The polysaccharide is Alcaligenes lettas (Alc).
aigenes latus) bacterial culture or a processed product thereof, the admixture for a hydraulic inorganic composition according to claim 1 or 2. 4. Alcalig
The admixture for hydraulic inorganic compositions according to claim 3, wherein the bacterium is an Alcaligenes latus B-16 strain (FERM BP-2015). 5. The polysaccharide according to any one of claims 1 to 4 and hydroxypropylmethyl cellulose (HPMC)
And at least one selected from water-soluble cellulose derivatives of hydroxyethyl cellulose (HEC) are 95:
An admixture for a hydraulic inorganic composition containing a mixture in the range of 5 to 5:95 (weight ratio) as a main component. 6. The admixture for a hydraulic inorganic composition according to any one of claims 1 to 5, wherein the hydraulic inorganic composition is a mortar. 7. The admixture for a hydraulic inorganic composition according to claim 1, wherein the hydraulic inorganic composition is concrete. 8. The admixture for a hydraulic inorganic composition according to claim 7, wherein the concrete is fiber reinforced concrete. 9. The admixture for a hydraulic inorganic composition according to claim 7, wherein the concrete is a centrifugal molding concrete. 10. The admixture for a hydraulic inorganic composition according to claim 7, wherein the concrete is a spray concrete. 11. The admixture for a hydraulic inorganic composition according to claim 7, wherein the concrete is underwater concrete. 12. The polysaccharide according to claim 1, or a mixture of the polysaccharide according to claim 5 and a water-soluble cellulose derivative is added to a hydraulic inorganic composition in an amount of 0.0
The admixture for hydraulic inorganic compositions according to any one of claims 1 to 9, which contains 01 to 5.0% by weight.