JPH09268046A - Hydraulic composition having high fluidity - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a hydraulic composition, little in temperature dependency and excellent in fluidity by compounding a hydraulic substance with a nonionic water-soluble cellulose ether and a water-soluble polysaccharide. SOLUTION: This hydraulic composition is obtained by compounding a hydraulic substance with (A) a nonionic water-soluble cellulose ether and (B) a water- soluble polysaccharide as essential components, and exhibits fluidity of >=150mm when determined according to a flow test in conformity to JIS-R5201 in the absence of falling motion. Preferably, the component A is at least one kind selected from hydroxyalkylcellulose, hydroxyalkylalkylcellulose, etc., and the component B is at least one kind selected from a sphingan gum group expressed by the formula [Glu is D-glucose; GluA is D-glucuronic acid; Rha is L-rhamnose; X is L-mannose (Man) or L-rhamnose (Rha)], and the ratio of the component A to the component B is 95:5 to 20:80.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention is applied to self-leveling materials, grout materials, soil cement, etc., which require high fluidity, and can obtain stable fluidity with little temperature dependence from low temperature to high temperature. It relates to a high flow hydraulic composition.

[0002]

2. Description of the Related Art Cement mortar compositions and gypsum compositions, which are hydraulic compositions, harden with water and can be widely used as main structural materials, interior materials or fillers for buildings. Also,
It is also possible to combine water and a water-reducing agent so as to have high fluidity, and for example, they are used as grout materials, self-leveling materials, soil cement, and the like. Flow 1
In order to obtain a high fluidity of 50 mm or more, it is important to add water, a water reducing agent, etc., but when trying to obtain a high fluidity, aggregates separate and settle, and a uniform hardened product cannot be obtained. There is. To solve this, in general, Japanese Patent Laid-Open No.
As seen in JP-A-187745, a nonionic water-soluble cellulose ether such as hydroxypropylmethyl cellulose is used as a separation preventing agent. This is because the water-soluble cellulose ether can enhance the material separation preventing effect without impairing the fluidity and can be used in combination with the water reducing agent. However, the aqueous solution of water-soluble cellulose ether has temperature dependence, and has a property that it has high viscosity at low temperature and low viscosity at high temperature. Further, the water reducing agent also has a temperature dependency, and generally has a property that the dispersion effect is enhanced at a high temperature, but is reduced at a low temperature.

Since ordinary high fluidity hydraulic compositions use these separation reducing agents and water reducing agents in combination, the temperature dependence is further increased and the viscosity is increased at low temperatures.
There was a problem that the fluidity was lowered, the viscosity was lowered at high temperature, and the fluidity was increased, but the material separation was increased. JP-A-63-315547 introduces an example in which welan gum is used as an additive, and it is stated that when welan gum is added to a cement composition, cement particles are easily suspended. Further, Japanese Patent Application Laid-Open No. 5-139806 finds application to high-fluidity concrete, and suggests that an aqueous solution of welan gum has little temperature dependence. However, welan gum has a cohesive property with respect to cement, and there is a drawback in that the fluidity is hindered if the addition amount is increased to prevent the separation of aggregates. Incidentally, JP-A-4-36754
Application to a cement mortar composition is disclosed in Japanese Patent Publication No. 9, which utilizes the above-mentioned cohesiveness.

[0004]

As described above, there is virtually no high fluidity hydraulic composition which has little temperature dependency and is excellent in fluidity, and such a high fluidity hydraulic composition is practically nonexistent. The realization of things was awaited strongly. It is an object of the present invention to provide a hydraulic composition which has little temperature dependency and excellent fluidity in view of the above circumstances.

[0005]

In order to achieve the above object, the invention of claim 1 is a high fluidity hydraulic composition comprising a hydraulic substance, a nonionic water-soluble cellulose ether and a water-soluble composition. Polysaccharide as an essential component, JIS R 52
15 if there is no drop motion in the flow test specified in 01.
It has a flow of 0 mm or more. According to the invention of claim 2, in the high fluidity hydraulic composition of claim 1, the nonionic water-soluble cellulose ether is at least selected from the group consisting of alkyl cellulose, hydroxyalkyl cellulose and hydroxyalkylalkyl cellulose. 1
And the water-soluble polysaccharide is at least one selected from the group of the sphingan gum group represented by the following structural formula, the ratio of which is 95: 5 to 20:
It is 80.

Embedded image [In the formula, Glu represents D-glucose, GluA represents D-glucuronic acid, Rha represents L-rhamnose, and X represents L-mannose (Man) or L-rhamnose (Rha). ]

The water-soluble cellulose ether is a thickener having a water-retaining property. When a suitable amount of cellulose ether is added and associated with water, it becomes a viscous liquid, and when solid particles are dispersed in this liquid, it has an effect of preventing suspension, dispersion and sedimentation, and prevents material separation. Further, its water retention property prevents bleeding, and since it has lubricity, it does not hinder fluidity. Water-soluble polysaccharides exhibit unique thixotropic properties when dissolved in water. A small amount of a polysaccharide is added together with water, cement or calcined gypsum, and shearing force is applied to the mixture, so that the whole mixture becomes easy to flow. Further, since it has a unique helical structure, the temperature dependence of the aqueous solution is small. When these two water-soluble substances are used together in a certain specific ratio, the temperature dependence as in the present invention is small, and
A hydraulic composition having excellent fluidity can be obtained. The highly fluid hydraulic composition of the present invention is obtained by adding a water-soluble cellulose ether and a water-soluble polysaccharide to a hydraulic substance such as cement or gypsum.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION As the cement that can be used in the present invention, for example, Portland cement (ordinary Portland cement, early strength Portland cement, moderate heat Portland cement, white Portland cement,
Ultra early strength Portland cement) can be mentioned. In addition to these, mixed cement (blast furnace cement, silica cement, fly ash cement), special cement (alumina cement, expanded cement) and the like can be mentioned, and one kind or a mixture of two or more kinds selected from these can be used. As gypsum, calcined gypsum obtained by firing natural gypsum or the like can be used.

Examples of the nonionic water-soluble cellulose ether used with the above cement include, for example,
Methyl cellulose (MC), ethyl cellulose (EC)
And the like. In addition to these, there can be mentioned hydroxyalkyl celluloses such as hydroxyethyl cellulose (HEC) and hydroxypropyl cellulose (HPC), and also hydroxyethyl methyl cellulose (HEMC), hydroxypropyl methyl cellulose (HPMC), hydroxyethyl ethyl cellulose (HEEC). Mention may also be made of hydroxyalkylalkylcelluloses such as Particularly, hydroxyalkyl cellulose and hydroxyalkylalkyl cellulose are preferred. This is because these are excellent in viscosity development in a cement system and therefore excellent in water retention in cement mortar. These can be used alone or as a mixture of two or more. The viscosity is not particularly limited, but 1% viscosity is 10 to 50000.
It is preferably 0 cP. If the viscosity is 10 cP or less, necessary rheological properties cannot be obtained. Also, 50,00
If it is 0 cP or more, industrial production is economically difficult. The amount of such water-soluble cellulose ether used varies depending on the fluidity, degree of prevention of material separation, application, climate, etc.
Usually, it is 0. 0 per 100 parts by weight of hydraulic material such as cement.
01 parts by weight to 10 parts by weight, preferably 0.05 parts by weight to
5 parts by weight is desirable.

These nonionic cellulose ethers have air entrainment properties, and when it is necessary to control the amount of air, tributyl phosphate (C ₁₂ H ₂₇ ), which is an antifoaming agent used in concrete and mortar, is used. O
₄ P), Pluronic antifoaming agent [Pluronic L61
(Manufactured by Asahi Denka Kogyo Co., Ltd.)], silicone-based antifoaming agent [KM73
(Manufactured by Shin-Etsu Chemical Co., Ltd.), and acetylene glycol derivatives [Surfinol (manufactured by Nissin Chemical Co., Ltd.)] can be used.

In the present invention, along with the above-mentioned cement, hydraulic substances such as gypsum and water-soluble cellulose ether,
Use water-soluble polysaccharides. Water-soluble polysaccharides include Welan gum and Rhamzan gum (Rha).
mslan gum) or gellan gum (Gellan)
Gum) and other sphingans represented by the following structural formula:
Gum Group (Sphingan Gum Grou
p) is preferred.

Embedded image [In the formula, Glu represents D-glucose, GluA represents D-glucuronic acid, Rha represents L-rhamnose, and X represents L-mannose (Man) or L-rhamnose (Rha). ] Welan gum is a bacterial ATCC bacterium of the genus Alcaligenes that produces heteropolysaccharides.
31555 bacterial species (bacterial number Alcaligenes
It may be manufactured according to ATCC 31555). For example, it can be obtained as a gum produced outside the cells of bacteria by sprinkling it on a medium containing a carbohydrate, a nitrogen source and other appropriate nutrients and subjecting to complete culture fermentation.
Ramzan gum is a similar bacterium with cell number Al.
caligenes ATCC 31961, gellan gum is microbial cell number Pseudomonas ATC
It can be obtained using C 31461 in the same manner as welan gum. The amount of such a water-soluble polysaccharide to be used depends on the expected degree of temperature dependence, but is usually 0.0005 parts by weight to 8 parts by weight, preferably 100 parts by weight per 100 parts by weight of a hydraulic substance such as cement. , 0.0025 to 4 parts by weight is desirable.

If the proportion of the water-soluble cellulose ether used is too large, the fluidity will not be a problem, but the temperature dependency will be large. On the other hand, if the proportion of water-soluble polysaccharide used is too large, there is no problem in temperature dependence, but the fluidity is poor, and as a result the amount of water that must be added during construction increases, resulting in reduced strength, cracking, etc. This is not preferable because it may cause the above problem.
The ratio of the nonionic water-soluble cellulose ether and the water-soluble polysaccharide is (nonionic water-soluble cellulose ether:
The water-soluble polysaccharide) is preferably in a weight ratio of 95: 5 to 20:80. If the ratio of the nonionic water-soluble cellulose ether is larger than 95: 5 (weight ratio), there is a drawback that the temperature dependence becomes large. Further, when the ratio of the water-soluble polysaccharide is larger than 20:80 (weight ratio), there is a drawback that fluidity is poor.

In addition to the above, in the hydraulic composition of the present invention, it is generally preferable to use river sand, mountain sand, silica sand, cold water sand, lightweight aggregate or the like as the aggregate. In addition to the aggregate, hemihydrate gypsum, slaked lime, calcium carbonate, dolomite plaster, clay and the like are preferably used in combination. In addition, powder emulsions, fiber substances, etc. may be added. In addition, water-soluble polyvinyl alcohol may be used in combination in order to enhance the adhesiveness.

Further, a water reducing agent (high-performance water reducing agent, high-performance AE) generally used for concrete, mortar and the like.
Water reducing agents, AE water reducing agents, etc.) can also be used as necessary. As the water reducing agent, a highly condensed triazine compound, a formalin condensate of melamine sulfonate, a polycarboxylic acid salt derivative, a modified lignin sulfonate compound, an amino sulfonic acid polymer compound, a naphthalene sulfonate formalin. Examples thereof include condensates and isoprene-based compounds. When nonionic cellulose ethers are used, among these, highly condensed triazine compounds [NL-4000 (manufactured by Pozzolis Co., Ltd.)], formalin condensates of melamine sulfonates [Melment F10M]
(Manufactured by SKW), SMF (manufactured by Nissan Chemical Industries, etc.), polycarboxylic acid salt derivative [SP-8S (manufactured by Pozoris)
Etc.] and isoprene-based compounds [Dynaflow (manufactured by Japan Synthetic Rubber), etc.] are preferred. Curing modifiers such as setting retarders and setting accelerators can also be used as required.

The highly fluid hydraulic composition of the present invention is added to the above composition with water, kneaded, fluidized, and cast in a required state in a fluidized state. When fluidizing, the amount of water to be added may be determined by gradually adding and adjusting until the hydraulic composition is soft enough to be placed, but usually, per 100 parts by weight of the hydraulic material. , 40
Preference is given to parts by weight to 300 parts by weight. When kneading,
All components including water may be kneaded using, for example, a mortar mixer. The water-soluble polymer substance may be added as powder into cement etc. and mixed, but in the case where it partially solidifies into particles due to the influence of water and becomes non-uniform, glyoxal etc. is used as an inhibitor. You may add.

[0015]

Embodiments of the present invention will be described below. In the present application, Examples and Comparative Examples of the present invention were obtained for grout materials and self-leveling materials as follows. 1. Examples relating to grout materials (Example 1 to 1 to 6 and Comparative example I to 1 to 6) (1) Water-soluble cellulose ether: hydroxypropyl methylcellulose, viscosity 6,300 cP [concentration 1%]
(Product name: Metroses, manufactured by Shin-Etsu Chemical Co., Ltd., below "HPM
(2) Water-soluble polysaccharides: (a) Welan gum (manufactured by Monsanto Kelco Division, hereinafter abbreviated as "WG") (b) Ramzan gum (Monsanto Kelco Division, hereinafter "RG") (3) Fine aggregate: River sand from Shinanogawa (4) Cement: Blast furnace cement type B (manufactured by Nippon Cement) (5) Fly ash: Asano fly ash (manufactured by Nippon Cement) (6) Defoaming agent: tributyl Phosphate (reagent grade 1) (7) compounding cement 300 kg / m ³ fly ash 100 kg / m ³ fine aggregate 476 kg / m ³ water 600 kg / m ³ HPMC 3 kg / m ³ (1 of Example I) To 6) WG or RG 1 kg / m ³ (1 to 6 of Example I) Defoamer 0.8 kg / m ³

(8) Kneading Using the mortar mixer in accordance with JIS R 5201, the substances specified in the above formulation are kneaded with powder only 1
After mixing for 3 minutes after pouring water, a predetermined grout material was obtained. (9) Measurement-Flow test In the flow test of JIS R 5201, the spread in the case of naturally flowing (0 hit flow) without giving a drop motion was measured by the diameter in the perpendicular direction, and the averaged value was obtained. Breathing test The values were measured according to the standards of the Japan Society of Civil Engineers, breathing rate and expansion rate test method of injected mortar of prepacked concrete, and the values after 3 hours are shown in Tables 1 and 2. Kneading temperature Measured with an alcohol thermometer.

[0017]

[Table 1]

[0018]

[Table 2]

Table 1 shows Examples 1 to 1 to 6 of Examples I and Examples 1 to 1 of Example I are at a kneading temperature of 20 ° C., and all formulations were water-soluble cellulose ether and water-soluble at the ratio of the present invention. Since it also uses a soluble polysaccharide, it exhibits high fluidity, and has a breathing rate of 0, which is excellent in preventing material separation. In Examples I, 4 to 6 are low temperature (10 ° C.) and high temperature (40 ° C.).
In the case of (° C.), the substance added in the proportion of the present invention has little change in fluidity at low temperature and high temperature, and is excellent in preventing material separation. Table 2 shows a comparative example, 1 to 3 of Comparative Example I.
Indicates the case where each compounding material is used alone. Comparative Examples I, 1, 4 and 5 are cases where the water-soluble cellulose ether was used alone, and there was no particular problem at 20 ° C., but the fluidity decreased at low temperature, the fluidity increased at high temperature, and the material separation tendency was increased. There is a drawback because it has a large temperature dependency. Comparative Examples I, 2, 3, and 6 are the cases where the water-soluble polysaccharide was used alone, and the temperature dependency was small, but there was a defect that the fluidity was poor. In Comparative Example I-7, (nonionic water-soluble cellulose ether: water-soluble polysaccharide) is 95: 5 (weight ratio).
Is over 97: 3 (weight ratio), and the temperature dependence is large. In Comparative Example I, 8 is (nonionic water-soluble cellulose ether: water-soluble polysaccharide) smaller than 20:80 (weight ratio) and 15:85 (weight ratio), and the fluidity is poor.

2. Examples relating to self-leveling materials (Example II 1 to II 6 and Comparative Example II 1 to II 6) (1) Water reducing agent: Melment F10M (manufactured by SKW) (2) Defoaming agent: SN deformer 14HP ( (3) Expanding material: Denka CSA (manufactured by Denki Kagaku Kogyo Co., Ltd.) In addition, the same water-soluble cellulose ethers, water-soluble polysaccharides, fine aggregates and cements as those used in the examples of the grout materials were used. (4) Preparation Cement 100 parts by weight Fine aggregate 250 parts by weight Water reducing agent 2 parts by weight HPMC 0.25 parts by weight (1 to 6 of Example II) WG or RG 0.15 parts by weight (1 to 6 of Example II) ) Defoaming agent 0.08 parts by weight Expansive material 5 parts by weight Water 70 parts by weight (5) Kneading The substance specified in the formulation of (4) above is added to JIS R 52.
Using a mortar mixer in accordance with No. 01, the powder was kneaded for 1 minute with the powder alone, and after mixing with water for 3 minutes to obtain a predetermined self-leveling material. (6) Measurement The same measurement as in the examples and comparative examples of the grout material was performed.

[0021]

[Table 3]

[0022]

[Table 4]

Table 3 shows Examples 1 to 6 of Example II, and Examples 1 to 2 of Example II have a kneading temperature of 20 ° C., and in any of the formulations, a water-soluble cellulose ether and a water-soluble poly (ether) were used in the ratio of the present invention. Since it uses saccharides in combination, it exhibits high fluidity, and has a breathing rate of 0, which is excellent in preventing material separation. In Examples II, 3 to 6 are low temperature (10 ° C.) and high temperature (40 ° C.).
In the case of (° C.), the substance added in the proportion of the present invention has little change in fluidity at low temperature and high temperature, and is excellent in preventing material separation.

Table 4 is a comparative example, and Comparative Examples II to 1 to 6 are the cases where the blended materials were used alone. Comparative Examples II 1, 4 and 5 are the cases where the water-soluble cellulose ether is used alone, and there is no particular problem at 20 ° C., but the fluidity decreases at low temperature, the fluidity increases at high temperature, and the material separation tendency is increased. There is a drawback because it has a large temperature dependency. Comparative Examples II, 2, 3 and 6 are cases where the water-soluble polysaccharide was used alone, and the temperature dependency was small, but there was a drawback that the fluidity was poor. In addition, both the grout material and the self-leveling material exhibited good pumping and pumping properties.

[0025]

As is apparent from the above, the high fluidity hydraulic composition of the present invention has the constitution as described above, and therefore has the excellent strength that conventional hydraulic compositions have. It has the same characteristics, and on top of that, it has the high fluidity necessary for construction. Also, since there is little change in viscosity with temperature, there is no need to change the composition throughout the year,
Stable fluidity and material separation suppression effect can be maintained.

Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display area C04B 103: 32 103: 50 111: 62 111: 70

Claims (2)

[Claims] 1. A hydraulic substance, a nonionic water-soluble cellulose ether, and a water-soluble polysaccharide are used as essential components in accordance with JIS.
A high-fluidity hydraulic composition having a flow of 150 mm or more in the case where there is no drop motion in the flow test specified in R 5201. 2. The nonionic water-soluble cellulose ether is at least one selected from the group consisting of alkyl cellulose, hydroxyalkyl cellulose and hydroxyalkylalkyl cellulose, and the water-soluble polysaccharide has the following structure: The high-fluidity water according to claim 1, which is at least one selected from the group of the sphingan gum group represented by the formula, and the ratio thereof is 95: 5 to 20:80. Hard composition. Embedded image [In the formula, Glu represents D-glucose, GluA represents D-glucuronic acid, Rha represents L-rhamnose, and X represents L-mannose (Man) or L-rhamnose (Rha). ]