WO2004033387A1 - Melange pour ciment ou pour mortier - Google Patents

Melange pour ciment ou pour mortier Download PDF

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Publication number
WO2004033387A1
WO2004033387A1 PCT/JP2003/004712 JP0304712W WO2004033387A1 WO 2004033387 A1 WO2004033387 A1 WO 2004033387A1 JP 0304712 W JP0304712 W JP 0304712W WO 2004033387 A1 WO2004033387 A1 WO 2004033387A1
Authority
WO
WIPO (PCT)
Prior art keywords
cement
carrageenan
admixture
mortar
cement mortar
Prior art date
Application number
PCT/JP2003/004712
Other languages
English (en)
Japanese (ja)
Inventor
Teruo Urano
Sachio Ina
Original Assignee
Murakashi Lime Industry Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Murakashi Lime Industry Co., Ltd. filed Critical Murakashi Lime Industry Co., Ltd.
Priority to AU2003227494A priority Critical patent/AU2003227494A1/en
Publication of WO2004033387A1 publication Critical patent/WO2004033387A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24—Macromolecular compounds
    • C04B24/38—Polysaccharides or derivatives thereof

Definitions

  • the present invention relates to a cement or an admixture for cement mortar used for pressure bonding of tiles, stones and the like used in exteriors and interiors of buildings, and particularly to a cement having an effect of improving workability and increasing pressure strength.
  • a ment admixture Provide a ment admixture.
  • the interior and exterior of the building are constructed by attaching tiles, natural stones, etc. to the groundwork for their functionality and appearance.
  • the base and the tile, c crimping cement using a cement-based materials such as cement or cement mortar as an adhesive used for pasting the stones is by evaporation of water from the water and surface by underlying cement Water to be added for the hydration reaction is reduced.
  • Portland cement can be used for sand, silica sand, tanker, stone powder, water-soluble resin such as methylcellulose, polyvinyl alcohol, carboxymethylcellulose, EVA, Atari.
  • Water resin emulsions such as rubber resin and rubber latex are added to improve the normal curing of cement and to improve the adhesion to the foundation such as tiles.
  • An object of the present invention is to provide an admixture for preventing a decrease in compression strength due to evaporation of water from the surface, which is a drawback of compression cements such as tiles and stones.
  • the present inventors have focused on the constituents of natural seaweed that have been conventionally used as glue for plastering materials, and have conducted intensive studies.
  • the six-membered galactose skeleton has an ester sulfate group (one OS- 3- )
  • carrageenan with equatorial conformation of hydroxyl group (-OH) do not gelate under alkaline conditions such as Portland cement, and do not inhibit the hydration of Portland cement. It can be seen that it gives viscosity and does not form a film even if the kneading water evaporates from the surface. Solved the problem.
  • the carrageenan hydroxyl (-OH) has Ekatoriaru conformation, lambda (e) color Ginan, mu (mu) carrageenan, New (V) carrageenan, xi ( ⁇ ) Carrageenan, pie ( ⁇ ) carrageenan, or theta (0) carrageenan.
  • carrageenan six-membered ring galactose skeleton sulfate group (- 0S0 3 -) and hydroxyl (- ⁇ ) 1 kind or two kinds which are selected from Ekatoriaru distribution sitting was carrageenans
  • the present invention relates to an admixture for cement or cement mortar comprising the above.
  • Claim 2 of the present invention is the admixture for cement or cement mortar according to claim 1, wherein the six-membered galactose skeleton has a sulfate group (one oso 3- ) and a hydroxyl group (one) in equatorial conformation.
  • the carrageenan is characterized in that it is a lambda (e) power raguinan, mu ( ⁇ ) carrageenan, new (V) carrageenan, kusai ( ⁇ ) carrageenan, pie ( ⁇ ) carrageenan, or theta (0) carrageenan is there.
  • Claim 3 of the present invention relates to the admixture for cement or cement mortar according to claim 1 or claim 2, wherein 0.1 to 5.0 parts by mass of a predetermined carrageenan is added to 100 parts by mass of cement or cement mortar. It is special to add It is a sign.
  • Claim 4 of the present invention relates to the admixture for cement or cement mortar according to any one of claims 1 to 3, wherein the admixture is at least one selected from hydraulic compositions, admixtures, fibers, and aggregates. Is blended.
  • Claim 5 of the present invention is characterized in that the cement or the admixture for cement mortar according to any one of claims 1 to 4 is used as a cement for pressure bonding.
  • Claim 6 of the present invention relates to a method for using the cement or cement mortar admixture according to any one of claims 1 to 5, wherein the admixture is preliminarily mixed with the cement or cement mortar powder / particle composition. Water is added and kneaded before use, or water is added to the cement or mortar powder / granule composition at the site of use and added when kneading is used.
  • Carrageenan is the molecular weight 1 0 5 about the water-soluble natural polysaccharides and galactosyl bets sulfate es ether the extracted and purified from natural seaweed as a main component, such as red algae. Due to the difference in molecular structure, kappa (K) carrageenan, iota (t) carrageenan, lambda (e) carrageenan, mu ( ⁇ ) carrageenan, new (V) carrageenan, kusai () carrageenan, pie ( ⁇ ) carrageenan It has been known. Theta ( ⁇ ) carrageenan, which does not exist in nature but can be obtained by alkali treatment of lambda (e) carrageenan.
  • the structure of carrageenan consists of) 3-D-galactose and ⁇ -D-galactose with alternating 1,4 and ⁇ -1,3 bonds.
  • the structural difference between each type is due to the difference between the six-membered ring structure of the galactose skeleton and the conformation of the sulfate group (one OSO 3- ) and the hydroxyl group (- ⁇ ) in the galactose skeleton. Les, classified by.
  • the six-membered ring structure that can be taken by the galactose skeleton in the carrageenan structure includes a chair (Ch air) type (abbreviated as C type), a boat (Boat type) (abbreviated as B type), a twist boat (Twi st boat, or There are Skew-boat type (abbreviated as S type) and half-chair type (abbreviated as H type), but all carrageenans are C type. This can be illustrated by the following formula 2 (Naomichi Kunisaki, Masao Sano: Published by Koshobo Co., Ltd. "Knowledge of Food Polysaccharide Emulsification, Thickening, and Gelation”) (Cited from page 105).
  • Carrageenan is a 6-membered ring consisting of 3D-galactose and 1D-galactose
  • the structure is a bond between CI and CI, and a bond between CI and 1C.
  • the sulfate ester group (one OSO 3- ) and the hydroxyl group (-OH) present in the galactose skeleton have three conformations, equatorial conformation and axial conformaton.
  • sulfuric es ether group (_0 S0 3 -) hydroxyl group (one OH) to say that protrude in the horizontal direction on the same Ippei surface of galactose six-membered ring skeleton, which Ekatoriaru (Equatoria 1; "equatorial "Meaning” is called conformation.
  • the axial conformation means that these functional groups protrude in the vertical direction of the six-membered galactose ring skeleton, and this is called an axial (meaning "axial") conformation.
  • Type 1 Type C
  • kappa (C) carrageenan In kappa (C) carrageenan, the hydroxyl group at the C-12 position (10 ⁇ group), which is located in the ⁇ -D-galactose suite on the right, protrudes vertically in the six-membered galactose skeleton in an axial conformation.
  • the interaction between the molecules is strong, and the polymer chains of kappa (fC) carrageenan are stabilized by entanglement with each other, forming a helical structure. Therefore, in the presence of metal ions, high molecular chains of kappa ( ⁇ ) carrageenan associate with the aqueous solution, crosslink and gel by forming a three-dimensional network structure.
  • Lambda (E) Carrageenan structure on behalf of the formula 5 (Naomichi Kunisaki, Masao Sano: Published by Koshobo Co., Ltd. “Food polysaccharide monoemulsion ⁇ ⁇ viscosity ⁇ knowledge of gelation” 2 0 0 1 1 1 1 The first edition of the 25th edition, the first print: cited from page 1 ⁇ page 3).
  • the left side of the formula is] 3-D-galactose unit, and the right side is a -D-galactose unit.
  • the six-membered ring structure of the galactose skeleton is jS-D-galactose unit, ⁇ -D-galactose unit.
  • the unit is C1 type only), and the conformation of the functional group is equatorial.
  • the galactose unit has a sulfate group at the C-2 and C-6 positions and a hydroxyl group at the C-3 position, all of which have an equatorial conformation.
  • the sulfate group hydroxyl group equatorially conformed to the galactose six-membered ring skeleton protrudes in the horizontal direction on the same plane of the six-membered ring, repels each other and stabilizes, so the interaction between molecules Is weak and does not form a helical structure. Therefore, the aqueous solution does not undergo a cross-linking reaction with metal ions, and does not gel, but exhibits a viscosity increase. For the other mu () carrageenan, new (V) carrageenan, kusai ( ⁇ ) force laginan, and pi ( ⁇ ) carrageenan, the aqueous solution does not gel by metal ions for the same reason.
  • Theta (0) carrageenan is kappa ( ⁇ ) carrageenan, iota (t) power Raginan as well as left in the formula] 3-D-galactose Interview knit six-membered ring structure type C1 ⁇ type), six-membered ring structure 1C type in the right is alpha-D-galactosamine toe scan unit (4 Ci-type ), But all conformations of functional groups are equatorial. That is, the i3-D-galactose unit of theta ( ⁇ ) carrageenan has a sulfate group at the C-12 position, a hydroxyl group at the C-4 and C-16 positions, and a D-galactose unit. Has a sulfate ester group at the C-12 position, but all of them have an equatorial conformation.
  • the sulfate and hydroxyl groups that are equatorially conformed to the galactose six-membered ring skeleton protrude in the horizontal direction on the same plane of the six-membered ring, repel each other and stabilize, and the mutual The effect is weak, and no helical structure is formed. Therefore, the aqueous solution does not undergo a cross-linking reaction with metal ions, and does not gel, but exhibits a viscosity increase.
  • carrageenan is particularly a genus of Nommata (for example, Chondrus cri ferment, Chondrus ocellatus), a giraffe (for example, Gigartina stellata, Gigartina acicularis, Gigartina pistillata, Gigartina radula), or a genus of snow genus (for example, Eucheuma spinosum) , Eucheuraa cottoni), Chlorophyceae (eg, Iridaea), Ibaranori (eg, Hypnea musciformis), Saimi (eg, Ahnfeltia concinna), abundantly contained It has been known.
  • Nommata for example, Chondrus cri ferment, Chondrus ocellatus
  • a giraffe for example, Gigartina stellata, Gigartina acicularis, Gigartina pistillata, Gigartina rad
  • the carrageenan content in these seaweeds varies depending on the sampling location and season.For example, in the case of Chondrus crispus, the kappa is 12 to 33% for carrageenan, 7 to 21% for lambda (e) carrageenan, and a small amount for others.
  • a liquid is added, and the mixture is filtered by using a filter aid to obtain a carrageenan solution.
  • the solution is concentrated, it is gelled by separating it from the gelled insoluble matter by the alcohol precipitation method in which alcohol is added or the pressure dehydration method (gel press method) in which metal ions such as potassium ions are added.
  • Theta (0) carrageenan can be obtained by treating lambda (e) carrageenan with alkali.
  • lambda ( ⁇ ) carrageenan is preferred because it is abundant in quantity and is actively traded in commerce.
  • the cement for pressing such as tiles and stones used in the present invention is a cement containing Portland cement as a main component, and white Portland cement may be used in consideration of cosmetics, but if necessary, slaked lime or dolomite
  • a known hydraulic composition may be added in addition to the plaster.
  • the hydraulic composition include gypsum, early-strength portland cement, alumina cement, blast furnace cement, fly ash cement, and colored cement.
  • River sand, mountain sand, silica sand, cold water sand, lightweight aggregate, tanker, stone powder, etc. can be mixed with these cement-based powder mixtures to use as mortar.
  • the carrageenans of the present invention may be added to cellulose derivatives such as methylcellose, ethylcellulose, hydroxypropylcellulose, hydroxyshethylsenorellose, hydroxyshethylmethinolecellulose, hydroxypropylmethylcellulose and the like.
  • Water-soluble polymer compounds such as Bier alcohol and polyacrylamide Polymer-based emulsions, polymer-based emulsions of vinyl acetate, polymer-based emulsions of ethylene monoacetate, polymer-based emulsions of SBR, epoxy resin emulsions, etc. You may.
  • Vegetable fibers (hemp ass, jiutuss, manila hemp, Japanese paper, asparagus, wood pulp, kenaf) and inorganic fibers (asbestos, rock asbestos, glass fibers, etc.) and organic fibers (polyamide fibers, polyester fibers, polypropylene fibers) , Vinylon fiber, carbon fiber, etc.).
  • the amount of the carrageenan used in the present invention may be set to an amount sufficient to impart desired physical properties to the pressure-bonded cement such as a tile.
  • cement, cement mortar 100 parts by mass, It is used in the range of 0.1 part by mass to 5.0 parts by mass.
  • the amount used is less than 0.1 part by mass, it does not contribute to the water retention of the pressure-bonded cement such as tiles, and workability and adhesive strength may not be improved. If the amount used exceeds 5.0 parts by mass, not only is the adhesive strength reduced, but also the drying shrinkage due to the increase in the amount of water mixed becomes remarkable, and shrinkage cracks occur in the cured product, which is not preferable.
  • the admixture for cement of the present invention is preliminarily mixed with powder of granules having a composition of cement and cement mortar, and water is added and kneaded before use, or water is added to the cement mortar powder or granule composition at the site of use. May be added when adding and kneading.
  • cement for tiles and other press-fitting should be mixed well with water when used, and mortar mixed with cement or sand suitable for work should be used.
  • mortar is applied to the front surface of the base to a thickness of 5 to 1 Omm, tiles, stones, etc. are applied by crimping, and the cement and cement mortar are completed after being hardened.
  • cement or cement mortar is adhered in a dumpling shape to the surface to which tiles, stones, etc. are attached, and then pressed directly onto the substrate.
  • the cement used in the examples was prepared by mixing 50 parts by mass of Portland cement made of Sumitomo Osaka Cemente clay with 33 parts by mass of No. 6 silica sand and 17 parts by mass of No. 7 silica sand at a cement: sand ratio of 1: 1.
  • lambda carrageenan was selected from among carrageenans in which the sulfate group (-0S03-) and the hydroxyl group (-OH) were equatorially conformed to the six-membered galactose skeleton.
  • the mortar was added with fresh water so as to have a flow value of 17 Omm, and this was used as the standard softness. Is the standard water mixture (%).
  • the time from applying the mortar to pressing the tiles is called open time, and the tiles shown above were manually attached to the concrete board at three levels of open time: 0, 15 minutes, and 30 minutes.
  • Adhesive strength was measured by attaching a 4 Omm X 4 Omm steel flat metal plate to the tile surface with a quick-hardening epoxy resin, making cuts in the four corners of the tile with an electric cutter, and using a Kenken-type adhesive strength tester. To determine the adhesive strength.
  • Lambda (E) carrageenan (manufactured by Nitta Gelatin Co., Ltd., trade name: Nitta-carrageenan L_l) is mixed uniformly with 100 parts by mass of cement mortar Then, a cement mortar for tile crimping kneaded with water was obtained. The standard water mixture was 26.5%. As in Example 1, the open times were set to 0, 15 minutes, and 30 minutes, and the adhesion strength was measured after 10 days. Table 1 shows the results.
  • methylcellulose (trade name; 90SH-4000, manufactured by Shin-Etsu Chemical Co., Ltd.) were uniformly mixed to obtain a tile-pressing cement mortar kneaded with water.
  • the standard water mixing ratio was 23.7%.
  • the open times were set to 0, 15 and 30 minutes, and the adhesion strength was measured after 10 days. When the open time was 15 minutes or 30 minutes, the bond strength was extremely low. Table 1 shows the results.
  • methylcellulose trade name; 90SH-4000, manufactured by Shin-Etsu Chemical Co., Ltd.
  • the standard water mixture was 24.7% of the outside ratio.
  • the open times were set to 0, 15 and 30 minutes, and the adhesion strength was measured after 10 days. When the open time was 15 minutes or 30 minutes, the bond strength was extremely low. Table 1 shows the results.
  • methylcellulose trade name; 90SH-4000, manufactured by Shin-Etsu Chemical Co., Ltd.
  • the standard water mixture was 26.5%.
  • the open times were set to 0, 15 and 30 minutes, and the adhesion strength was measured after 10 days. Adhesion strength when open time is 15 minutes and 30 minutes was significantly lower. Table 1 shows the results.
  • Example 1 the open time was set to 0, 15 minutes, and 30 minutes for the cement mortar for crimping tiles (standard mixture water ratio 21.6%) made without using an admixture. After the elapse, the adhesion strength was measured. When the open time was 15 minutes or 30 minutes, the tiles did not adhere. Table 1 shows the results.
  • the cement admixture of the present invention is excellent in workability and exhibits excellent adhesive strength even when the open time is lengthened, so that it is excellent as a cement admixture for pressure bonding of tiles, stones and the like. is there.
  • lambda (e) carrageenan was selected and carried out from carrageenan which is not gelled by metal ions, but similar results were obtained with other types of carrageenan described in the claims.
  • cement mortar to which the carrageenan of the present invention is added in an appropriate amount is applied to the surface of the mortar after application to the base and before the tiles are crimped. Can be prevented.
  • the cement admixture of the present invention prevents a decrease in compression strength due to evaporation of water from the surface, which is a drawback of compression cements such as tiles and stones.
  • the admixture for cement or cement mortar of the present invention is a carrageenan selected from carrageenans in which a sulfate group (one OSO 3- ) and a hydroxyl group (_OH) are equatorially conformed to the carrageenan's six-membered galactose skeleton.
  • This carrageenan is characterized in that it does not gel even under alkaline conditions such as Portland cement, has excellent workability, and does not inhibit the hydration reaction of Portland cement.
  • the cement has an appropriate viscosity, and does not form a film even if the mixing water evaporates from the surface. Since it can prevent the deterioration, it has the property to be maintained as a pressed cement, and its industrial utility value is extremely large.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

L'invention concerne un mélange pour ciments ou mortiers, caractérisé en ce qu'il contient un ou plusieurs carraghénanes comprenant un squelette galactose à cycle à six membres et un groupe sulfate (-OSO3 -)et un groupe hydroxyle (-OH) qui lui sont liés en position équatoriale. Le carraghénane ne gélifie pas même en conditions alcalines, par exemple celles rencontrées avec du ciment portland, afin d'assurer une très bonne possibilité d'application. Il n'empêche pas la réalisation de la réaction hydraulique du ciment portland et confère une viscosité modérée au ciment. Même lorsque de l'eau utilisée pour le pétrissage s'évapore de la surface, le carraghénane ne forme pas de film. Le mortier possède ainsi une très bonne force d'adhésion même en cas de délai prolongé, et peut être empêché de voir sa force d'adhésion diminuer, par exemple dans le collage d'une tuile. Ce ciment possède donc les propriétés requises d'un ciment de liaison.
PCT/JP2003/004712 2002-10-11 2003-04-14 Melange pour ciment ou pour mortier WO2004033387A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2003227494A AU2003227494A1 (en) 2002-10-11 2003-04-14 Admixture for cement or cement mortar

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2002-298353 2002-10-11
JP2002298353A JP4078176B2 (ja) 2002-10-11 2002-10-11 セメント又はセメントモルタル用混和剤

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WO2004033387A1 true WO2004033387A1 (fr) 2004-04-22

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AU (1) AU2003227494A1 (fr)
WO (1) WO2004033387A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8962714B2 (en) 2011-06-30 2015-02-24 Dow Global Technologies Llc Hydraulic setting adhesive with improved open time

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009190919A (ja) * 2008-02-13 2009-08-27 Murakashi Sekkai Kogyo Kk 鏝塗材
EP2540687B1 (fr) 2011-06-29 2017-11-15 Dow Global Technologies LLC Composition cimentaire hydrophobe
JP2014129208A (ja) * 2012-12-28 2014-07-10 Taiheiyo Material Kk タイル用接着剤
CA3198470A1 (fr) * 2020-11-18 2022-05-27 Socpra Sciences Et Genie S.E.C. Utilisation de carraghenane comme adjuvant modificateur de viscosite dans des suspensions cimentaires fluides

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2293821A (en) * 1994-10-06 1996-04-10 Sandoz Ltd Admixtures for slip forming of concrete
JPH11349364A (ja) * 1998-06-05 1999-12-21 Shin Etsu Chem Co Ltd セメントモルタル用混和剤
US6173778B1 (en) * 1998-05-27 2001-01-16 Bj Services Company Storable liquid systems for use in cementing oil and gas wells

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2293821A (en) * 1994-10-06 1996-04-10 Sandoz Ltd Admixtures for slip forming of concrete
US6173778B1 (en) * 1998-05-27 2001-01-16 Bj Services Company Storable liquid systems for use in cementing oil and gas wells
JPH11349364A (ja) * 1998-06-05 1999-12-21 Shin Etsu Chem Co Ltd セメントモルタル用混和剤

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8962714B2 (en) 2011-06-30 2015-02-24 Dow Global Technologies Llc Hydraulic setting adhesive with improved open time

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JP4078176B2 (ja) 2008-04-23
JP2004131339A (ja) 2004-04-30
AU2003227494A1 (en) 2004-05-04

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