Cement composition

Abstract: A cement composition comprising a cement base and hemicellulose. The cement composition produces reduced efforescence and less bleeding. Self-leveling materials containing the cement composition also produce reduced efforescence and less bleeding and exhibit improved surface adhesion strength.

Description: BACKGROUND OF THE INVENTION Field of the Invention : The present invention relates to a cement composition which produces reduced efflorescence and less bleeding, as well as to a self-levelling material which contains the cement composition. Background Art : Efflorescence is white powder of CaCO 3 , Na 2 CO 3 , etc. deposited on the surface of a cement composition after the composition is set. Efflorescence is formed by the following mechanism: When the composition solidifies, soluble components (a variety of salts such as Ca, Na, K, etc.) of a cement composition which have been dissolved in a kneading water entrapped in the composition transfer to the surface of the composition, and as the moisture in the surface evaporates, the components react with CO 2 in the air to form white powder of CaCO 3 , Na 2 CO 3 , etc. It has been indicated that efflorescence readily occurs particularly in winter seasons, when temperature is low. Also, when a self-levelling material (hereinafter referred to as an SL material) is used in a self-levelling construction method (in which a slurry of a cement composition having self-smoothing properties (SL material) is simply poured onto a floor to freely flow thereon, thereby forming a precise horizontal plane; it is a usual practice when employing this method to apply a finishing material onto the surface of the SL material after installation), presence of efflorescence hinders adhesion between the SL material and the finishing material. Therefore, additional work such as polishing is needed in order to remove efflorescence. In the meantime, generation of laitance is prompted by bleeding, and if new concrete is installed on the concrete which has laitance thereon, the new and old concretes do not sufficiently bond to each other, and do not become satisfactorily united. As a result, cracks may generate from such ununited portions, water may leak, or interior reinforcements may become rusted. Hitherto, in an attempt to prevent production of efflorescence, a number of methods have been proposed including a method in which kneading water is reduced via co-use of a cement base and a water reducing agent, a method in which powders of inert substances which are finer than cement particles are added, a method in which capillary tubes are embedded, and a method in which oils and fats or synthetic resins are added. Even though efflorescence may be reduced to some extent via these methods, no conventional method has been completely successful in preventing production of efflorescence. In order to prevent solidified SL materials from forming efflorescence, the following methods have been proposed among others: in one method, ultra-fine silica particles are contained in SL materials, and in another method, the setting process is controlled. These methods also do not readily or sufficiently prevent production of efflorescence. To reduce bleeding, there are methods in which clay minerals such as bentonite are incorporated, or alternatively, water reducing agents for cements or AE agents are used. However, none of these methods provided satisfactory results. SL materials are primarily used as level adjusters for P tiles, elongated sheets, and other thin articles to be affixed to objects, or for floor-finishing materials such as flooring materials. When SL materials are used for these purposes, they must exhibit tenable adhesion strength between the SL material and the floor-finishing material. Although the minimum strength standard is designated as 49 N/mm 2 (5.0 kgf/cm 2 ), surface adhesion strength of SL materials varies depending on environmental conditions. Particularly in summers, separation of materials often occurs to reduce surface adhesion strength of SL materials, and therefore, the above-mentioned minimum strength standard may sometimes not be met. To solve this problem, there is proposed a method in which the amount of a thickener to be added to an SL material is increased to enhance the surface adhesion strength. However, this method is not advantageous in that an increase in the amount of a thickener causes a reduction in fluidity. From SU-A-761 436 hemicellulose is known as a cement additive for improving workability of a concrete mix. US-A-5,403,394 describes cellulose derivatives acting as water retention agents comprised in a self-levelling cement mixture. FR-A-1,562,406 proposes the utilization of chemically hydrolysed cellulose obtainable either from soft or hard wood as water retention agents in cement mixtures. BE-A-27 07 677 reports on further improvements in water retention for cement Compositions resulting by reducing the aldehyde group of hemicellulose obtainable by chemical or enzymatic hydrolysis. JP-A-4321545 suggests the treatment of cement with natural polysaccharides containing uronic acid for prevention of temperature rise of hydraulic cement compositions. SUMMARY OF THE INVENTION Under the above-mentioned Circumstances, the present inventors conducted extensive studies and found that the aforementioned problems are solved if a water-soluble hemicellulose from soybeans with a uronic acid content of 5 to 40 % by weight is incorporated into a cement base, leading to completion of the present invention. Accordingly, the present invention provides a cement composition which produces reduced efflorescence even in winters and which bleeds less while retaining its fluidity. The invention also provides an SL material which exhibits improved surface adhesion strength while retaining its fluidity. In another aspect of the present invention, there is a self-levelling material comprising a cement composition, an aggregate, a fluidizing agent, a thickener, and a defoamer; said cement composition comprising a cement base and a water-soluble hemicellulose obtained from soybeans wherein the uronic acid content in the hemicellulose is 5 to 40 % by weight. DESCRIPTION OF PREFERRED EMBODIMENTS The cement base which may be used in the present invention may be composed solely of cement or may contain inorganic materials if needed. Examples of cement include portland cements such as ordinary cement, high-early-strength cement, ultra high-early-strength cement, moderate heat cement, and sulfate resisting cement; low heat cement; and high belite cement. In the present invention, portland cements are preferably used. Examples of inorganic materials include gypsum, fly ash, and granulated blast-furnace slag powder. These inorganic materials are preferably incorporated in a cement base in amounts of not more than 30% by weight. In the present invention, hemicellulose is used as an admixture. The hemicellulose is a water-soluble hemicellulose obtained from soybeans. Generally, oils and fats, proteins, etc. are removed from soybeans and resultant residues are used. For example, tofu refuse, which is a by-product in the production of tofu, soybean milk, or separated soybean proteins, may be used. In the present invention, hemicellulose derived from soybeans is used, more preferably from cotyledons. Water-soluble hemicellulose may be obtained through extracting the above-mentioned starting materials using water, or dissolving, while applying heat, the materials under acidic or alkaline conditions when such treatment is necessary. Alternatively, it may be obtained through decomposing the starting materials using enzymes to make it soluble. Specifically, the following method may be used. Briefly, the above-mentioned starting materials are decomposed with heat (preferably between 40 and 160°C, and more preferably between 100 and 130°C) under acidic or alkaline conditions, and preferably at a pH in the vicinity of the isoelectric point of respective proteins (normally acidic pH), thereby fractionating water-soluble fractions. If an enzyme such as hemicellulase or a chelating agent such as EDTA is used during extraction, it is possible to extract a water-soluble fraction at relatively low temperatures. When the thus-obtained water-soluble fraction is dried, water-soluble hemicellulose is obtained. Before drying, the water-soluble fraction may be subjected to treatment with activated carbon, adsorption onto resins, or precipitation in ethanol to remove hydrophobic substances and low molecular weight substances. The molecular weight of the thus-obtained water-soluble hemicellulose is not particularly limited. In order to obtain sufficient effects of reducing efforescence and bleeding, average molecular weight is preferably between 10,000 and 1,000,000, and more preferably between 50,000 and 500,000. The hemicellulose which is used in the present invention may take the form of sugar or a sugar derivative, and it encompasses rhamnose, fucose, arabinose, xylose, galactose, glucose, uronic acid, mannose, lactose, etc. Uronic acid encompasses galacturonic acid, glucuronic acid, mannuronic acid, etc. The composition of uronic acid is not particularly limited. However, the presence of uronic acid is important in order to reduce efflorescence and bleeding. Methyl esters of uronic acid are preferably demethoxylated. Thus, esterfication degree is preferably 50% or less, and more preferably 20% or less. Demethoxylation may be performed using an acid, an alkali, or an enzyme such as pectin esterase. The uronic acid content in hemicellulose which is used in the present invention is 5-40% by weight, in order to sufficiently reduce efflorescence and bleeding. With respect to 100 parts of the cement base, the amount of hemicellulose is preferably 0.01-1 part by weight, more preferably 0.01-0.5 parts by weight, and particularly preferably 0.1-0.3 parts by weight. Amounts less than 0.01 parts by weight provide only small effects, whereas amounts in excess of 1 part by weight no longer enhance the effects. Since cement compositions comprising hemicellulose exhibit excellent dispersing effects, coagulation of cement particles is suppressed, and as a result, generation of bleeding is prevented. This is considered to be the mechanism through which generation of weak portions in the surface area is reduced, and thus strengthening the surface. Consequently, SL materials comprising the cement composition of the present invention have improved surface adhesion strength. Moreover, since less water is bled, smaller amounts of efflorescence are formed. The SL materials of the present invention comprise, in addition to the aforementioned cement composition, an aggregate, a fluidizing agent, a thickener, and a defoamer. As the aggregate, river sand, sea sand, land sand, crushed sand, silica sand, etc. may be used. Fluidizing agents are broadly categorized as naphthalene-type, melamin-type, polycarboxylic acid-type, and aminosulfonic acid-type. In the present invention, fluidizing agents of a polycarboxylic acid-type are preferred because they have enhanced fluidity retention effects. Thickeners are used for the purpose of preventing separation of the components of an SL composition. As the thickener of the present invention, a water-soluble polymer such as methylcellulose, hydroxyethylcellulose, and carboxymethylcellulose is preferably used. Defoamers are used for the purpose of preventing swelling or depression caused by bubbles. Generally, nonionic surfactants such as polydimethylsiloxane and polyoxyalkylene ether are used as defoamers. When needed, water may also be incorporated. The amount of water is generally determined such that it is adapted to the quality requirements described in JASS15M-103 "Quality Standards for Self-levelling Materials" by the Architectural Institute of Japan. According to the present invention, cement compositions causing reduced efflorescence and less bleeding can be obtained. Moreover, self-levelling materials containing the cement compositions of the invention not only cause reduced efflorescence and less bleeding, but also have improved surface adhesion strength. Examples: The present invention will be described by way of examples, which should not be construed as limiting the invention. Examples 1-6 and Comparative Examples 1-2: The cement compositions shown in Table 2 which were formulated in accordance with JIS mortars, in which the ratio (by weight) of cement base to standard sand was 1:2 and water/cement ratio was 65/100, were tested via the following methods and evaluated. The results are also shown in Table 2. Test Methods : (1) Method for mixing: Mixing was performed in accordance with JIS R5201 "Physical test method for cement." (2) Fluidity test: Fluidity tests were performed in accordance with JIS R5201 "Physical test method for cement." (3) Method for measuring amounts of water bleeding: A cement composition was charged into a plastic box measuring 20 cm x 15 cm to a height of 15 mm. The amount of water bleeding was measured using a measuring cylinder after 20 hours after charging. This test was performed in a 5°C thermostatic chamber. Mixing and fluidity tests were also performed in the same chamber. (4) Efflorescence formation test: A cement composition was charged into a plastic box measuring 20 cm x 15 cm to a height of 15 mm. The charged composition was cured for 5 days under the below-described environmental conditions (Table 1). Subsequently, efflorescence powder formed on the surface was collected using a brush. The amount of the powder was converted to g/m 2 for making comparison. Temperature of air in the chamber 7°C (for 1 day, sealed curing), and 5°C (day 2 and subsequent days) Humidity of air in the chamber not less than 90% (for 1 day, sealed curing), and 70% (day 2 and subsequent days) Velocity of air in the chamber 0.1-0.2 m/sec (day 2 and subsequent days) CO 2 concentration 5% (day 2 and subsequent days) Period of curing 5 days (parts by weight) Examples of Invention Comparative Ex. 1 2 3 4 5 6 1 2 Base materials Cement 100 100 100 100 100 85 100 85 Fly ash - - - - - 15 - 15 Hemicellulose 0.05 0.2 0.5 0.8 1.0 0.5 - - Aggregate 200 200 200 200 200 200 200 200 Water 65 65 65 65 65 65 65 65 Amount of efflorescence (g/m 2 ) 1.25 0.70 0.35 0.03 0 0.50 2.05 3.20 Amount of water bleeding (ml) 2.5 0.3 0 0 0 0 7.2 9.7 Fluidity test (mm) 219 233 223 221 217 227 220 232 From the above test results, it was discovered that, in the cement compositions in which 0.01-1 part by weight of hemicellulose was added to 100 parts by weight of the cement base, efflorescence and water bleeding were both reduced as the amount of hemicellulose increased, and in addition, this increase in amounts added did not reduce the fluidity of the compositions. It was also found that when hemicellulose was added in amounts of 0.2-0.5 parts by weight, amounts of water bleeding were satisfactorily reduced. Examples 7-16 and Comparative Examples 3-8: The SL materials having compositions in Tables 4 and 5 and containing hemicelluloses shown in Table 3 (all produced by Fuji Seiyu K.K.) were tested via the following methods and evaluated. The results are shown in Table 6. Test Methods : (1) Method for mixing: All the components in amounts shown in Tables 3 and 4 and water were placed in the mixing bowl of a Hobart mixer. SL materials were prepared through mixing at a low speed for 1 minute and then at a medium speed for 2 minutes. (2) Flow test: In accordance with the method described in JASS15M-103 "Quality Standards for Self-levelling Materials" by the Architectural Institute of Japan, a slurry obtained via mixing was poured into a flow cone placed at the center of a flow plate. The flow cone was removed upward in a vertical direction, and the amount of flow of the slurry (flow value) was measured. (3) Surface adhesion strength: A primer was applied to a polished surface of a mortar plate having a size of 300 mm x 300 mm x 10 mm. After the primer was dried for 24 hours, a sample (i.e., an SL material) was poured thereon. The sample was cured for 48 hours in the presence of moisture and air, and then cured until day 14 in a curing chamber. A steel plate having a size of 40 mm x 40 mm was affixed onto the surface of the solidified SL material using an epoxy resin. The steel plate was pulled using a hydraulic jack until exfoliated. The maximum tensile force during pulling was measured. The test for measuring surface adhesion strength was performed in a 30°C thermostatic chamber to simulate a summer environment. Mixing and fluidity tests were also performed in the same chamber. (4) Efflorescence formation test: The above-described method for cement compositions was repeated. To simulate a winter environment, the test was performed in a 5°C thermostatic chamber. 〈Composition analysis of hemicelluloses〉 Soya-Five S-DN Hemicellulose X Hemicellulose Y Starting material Soybeans Beats Corn Water (wt%) 5.2 8.6 2.3 Crude protein (wt%) 7.8 2.6 6.6 Crude ash (wt%) 8.2 11.0 1.7 Av. molecular weight 142,000 342,000 156,000 Uronic acid (wt%) 18.1 34.7 5.5 Esterification degree (%) 0 5.2 10.2 (parts by weight) Examples of Invention 7 8 9 10 11 12 13 14 15 16 Base materials Cement 100 100 100 100 100 100 100 70 70 85 Gypsum - - - - - - - 30 30 - Fly ash - - - - - - - - - 15 Soya-Five S-DN 0.03 0.06 0.1 0.3 0.5 - - 0.1 0.3 0.3 Hemicellulose X - - - - - 0.3 - - - - Hemicellulose Y - - - - - - 0.3 - - - Thickener 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Defoamer 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Aggregate 100 100 100 100 100 100 100 100 100 100 Fluidizing agent 1.0 1.0 1.0 1.2 1.4 1.0 1.0 1.0 1.0 1.0 Water 48 48 48 48 48 48 48 48 48 48 Comparative Examples 3 4 5 6 7 8 Base materials Cement 100 100 100 70 70 85 Gypsum - - - 30 30 - Fly ash - - - - - 15 Soya-Five S-DN - 0.008 0.6 - 0.008 - Hemicellulose X - - - - - - Hemicellulose Y - - - - - - Thickener 0.2 0.2 0.2 0.2 0.2 0.2 Defoamer 0.2 0.2 0.2 0.2 0.2 0.2 Aggregate 100 100 100 100 100 100 Fluidizing agent 1.0 1.0 1.4 1.0 1.0 1.0 Water 48 48 48 48 48 48 〈Test results〉 30°C thermostatic chamber 5°C thermostatic chamber Flow value after mixed (mm) Flow value after 6 hrs (mm) Surface strength on day 28 (kg/cm 2 ) Amounts of efflorescence (g/m 2 ) Examples of the Invention Ex. 7 220 216 8.7 1.36 Ex. 8 222 217 17.8 0.45 Ex. 9 223 219 23.0 0.28 Ex.10 215 210 25.2 0.10 Ex.11 212 204 26.0 0.05 Ex.12 224 220 19.4 0.16 Ex.13 214 212 13.8 0.39 Ex.14 223 218 14.3 0.67 Ex.15 224 219 19.6 0.48 Ex.16 221 215 20.4 0.54 Comparative Examples Com.Ex. 3 221 214 5.6 2.50 Com.Ex. 4 221 215 6.0 2.32 Com.Ex. 5 200 182 26.2 0.05 Com.Ex. 6 223 216 4.5 3.38 Com.Ex. 7 222 215 4.6 3.62 Com.Ex. 8 220 213 5.2 3.20 From the above test results, it was discovered that, in the SL materials in which 0.01-0.5 parts by weight of hemicellulose was added to 100 parts by weight of the cement base, efflorescence and water bleeding were both reduced, and in addition, surface adhesion strength was enhanced. Moreover, when hemicellulose in the above range was added, it is possible to obtain sustained fluidity (enhanced working efficiency) which is essential in SL materials. In other words, it is possible to secure the minimum flow value after 6 hours of not less than 200. It was also found that when hemicellulose was added in amounts of 0.05-0.1 parts by weight, excellent SL materials were obtained, exhibiting good fluidity and suppressing separation of components.

Claims: A cement composition comprising a cement base and a water-soluble hemicellulose obtained from soybeans wherein the uronic acid content in the hemicellulose is 5 to 40 % by weight. The cement composition according to claim 1, wherein the esterification degree of the uronic acid is not more than 50 %. The cement composition according to any one of claims 1 or 2, wherein 0.01-1 part by weight of hemicellulose is incorporated in 100 parts by weight of the cement base. A self-levelling material comprising a cement composition, an aggregate, a fluidizing agent, a thickener, and a defoamer; said cement composition comprising a cement base and a water-soluble hemicellulose obtained from soybeans wherein the uronic acid content in the hemicellulose is 5 to 40 % by weight.

Inventors: ASHIYAHARA SATORU, FURUTA HITOSHI, HATTORI MITSUO, HAYASHI HIROSHI, HOSONO KATSUO, MAEDA HIROKAZU, MATSUHISA MAKOTO, SOEDA KOICHI, YAMADA KAZUO, ASHIYAHARA, SATORU, FURUTA, HITOSHI, HATTORI, MITSUO, HAYASHI, HIROSHI, HOSONO, KATSUO, MAEDA, HIROKAZU, MATSUHISA, MAKOTO, SOEDA, KOICHI, YAMADA, KAZUO
Applicants: FUJI OIL CO LTD, FUJI OIL COMPANY, LIMITED
Application year: 1996
Main classification: C04B24
IPC codes: C04B24, C04B28, C04B111