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GB2329895A - Adhesive containing calcium sulphate - Google Patents

Adhesive containing calcium sulphate Download PDF

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Publication number
GB2329895A
GB2329895A GB9720960A GB9720960A GB2329895A GB 2329895 A GB2329895 A GB 2329895A GB 9720960 A GB9720960 A GB 9720960A GB 9720960 A GB9720960 A GB 9720960A GB 2329895 A GB2329895 A GB 2329895A
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GB
United Kingdom
Prior art keywords
water
composition according
composition
component
vinyl
Prior art date
Legal status (The legal status 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 status listed.)
Granted
Application number
GB9720960A
Other versions
GB9720960D0 (en
GB2329895B (en
Inventor
Brian J Taylor
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NICOBOND INTERNATIONAL Ltd
Original Assignee
NICOBOND INTERNATIONAL 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 NICOBOND INTERNATIONAL Ltd filed Critical NICOBOND INTERNATIONAL Ltd
Priority to GB9720960A priority Critical patent/GB2329895B/en
Publication of GB9720960D0 publication Critical patent/GB9720960D0/en
Publication of GB2329895A publication Critical patent/GB2329895A/en
Application granted granted Critical
Publication of GB2329895B publication Critical patent/GB2329895B/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/14Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00663Uses not provided for elsewhere in C04B2111/00 as filling material for cavities or the like
    • C04B2111/00672Pointing or jointing materials

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

A composition for admixing with water to form an adhesive, comprises: (A) anhydrous and/or partially hydrated calcium sulphate; (B) a hardening-rate modifier to regulate the rate of setting of the composition when admixed with water; (C) a water-retention aid; (D) a rheology modifier; and (E) a water-soluble or redispersible polymer resin. A cellulose ether, starch ether or gum may constitute both (C) and (D) and (D) may also be a bentonite clay, wollastonite or attapulgite. The compositions may be used for adhering ceramic tiles to a substrate.

Description

ADHESIVE This invention relates to adhesive compositions, particularly but not exclusively for adhering ceramic tiles or the like to a substrate.
It is often desired to adhere ceramic tiles directly to gypsum-based substrates, such as floors and walls. The use of adhesives based on portland cement for this purpose has not hitherto been successfiil due to reaction of tricalcium aluminate in the portland cement with water soluble salts in the substrate to form ettringite in the adhesive layer. This causes weakness of the adhesive/substrate interface and leads to failure in bonding the tiles to the substrate. In order to solve this problem it has hitherto been proposed to apply a primer layer to the substrate before application of the adhesive in order to form a chemical barrier to prevent ettringite formation. The application of such a barrier layer is, however, laborious and increases expense, as well as sometimes decreasing the strength of the bond between the tile and the substrate.
EP-A-O 320 982 describes tile adhesives and grouts containing calcium sulphate and an aluminate-free cement.
Tile adhesives are generally used in two types of application. Thin-bed applications are usually used for applying tiles to substantially uniform surfaces, such as walls, and in this application the thickness of the adhesive layer is up to 3 mm.
Thick-bed applications, where the thickness of the adhesive layer is greater than 3 mm, are used where the surface of the substrate is uneven, such as on floors or poorly finished walls.
We have now found it possible to formulate a calcium sulphate-based adhesive, e.g. for bonding a ceramic tile in thin- or thick-bed applications, that does not suffer from the above mentioned disadvantages when used with a gypsum-based substrate.
References to "ceramic tiles" herein are intended to encompass not only ceramic tiles per se but also other hard surface coverings such as natural or reconstituted stones and mosaics.
According to one aspect, the invention provides a composition for admixing with water to form an adhesive, comprising: (A) anhydrous and/or partially hydrated calcium sulphate; (B) a hardening-rate modifier to regulate the rate of setting of the composition when admixed with water; (C) a water-retention aid; (D) a rheology modifier; and (E) a water-soluble or redispersible polymer resin.
Various preferred features and embodiments of the invention are described below by way of non-lirniting illustration.
The compositions of the invention are generally in the form of dry powders that are admixed with water immediately prior to use to form an adhesive paste that can be used in thick- or thin-bed applications. The amount of water added to the composition of the invention is therefore generally chosen to enable the adhesive to be readily applied uniformly to the substrate with little or no slippage of the ceramic tile before hardening of the adhesive occurs. The compositions of the invention form adhesives that avoid ettringite formation when applied to a gypsum-base substrate and therefore have high bond strengths.
Component (A) of the compositions of the invention is anhydrous or partially hydrated calcium sulphate, e.g. calcium sulphate hemihydrate in a- or ss- form. For reasons of cost and ready availability, it is preferred to use calcium sulphate hemihydrate (ss- form) as a fine powders The compositions of the invention contain (B) a hardening-rate modifier to regulate the rate of setting of the composition when admixed with water. Without such a hardening-rate modifier, compositions containing anhydrous calcium sulphate set too slowly when admixed with water, and compositions containing partially hydrated calcium sulphate set too quickly. Materials that can be used for this purpose include: alkali metal salts to accelerate the rate of setting when the compositions contain anhydrous calcium sulphate; and/or organic acids and/or salts thereof to retard the rate of setting when the compositions contain a partially hydrated calciurn sulphate. Examples of organic acids that may be used include citric acid and other carboxylic acids such as tartaric acid, and their salts. In some circumstances, the resin component (E) ofthe compositions may comprise a material that acts as a hardening retarder, e.g. where component (E) contains an organic acid or salt, and in these cases component (E) may have a dual function and it may not be necessary to add additional component (B).
Other materials that serve to regulate the rate of setting of calcium sulphatecontaining compositions are known to those skilled in the art.
The compositions of the invention include (C) a water retention aid.
Materials that can be used for this purpose include cellulose ethers, starch ethers, natural or synthetic gums and the like. Examples of cellulose ethers include: hydroxypropyl methyl cellulose, commercially available as Methocels (Dow Chemical Company) or Walocels (Wolff Walstrode AG); carboxymethyl celluose ethers, commercially available from Courtaulds Chemicals and Wolff Walstrode AG; and methyl hydroxyethyl cellulose ethers, commercially available as Tylose (Hoechst) or Culminal (Aqualon).
The compositions also include (D) a rheology modifier to allow the compositions to be readily applied to a substrate when admixed with water in use and which help to prevent slippage of the tiles while the adhesive is setting. Materials that can be used for this purpose include the above-mentioned cellulose ethers, starch ethers and natural or synthetic gums, as well as inorganic materials such as bentonite clays, wollastonites, attapulgites and the like. Bentonite clays are commercially available in the Bentone range from Redland Minerals, and attapulgites are commercially available in the Attagel range from Lawrence Industries. It will be appreciated that when the compositions of the invention contain cellulose ethers, starch ethers and/or natural or synthetic gums, these may serve as both waterretention aids (C) and rheology modifiers (D).
The compositions ofthe invention include (E) a water-soluble or redispersible polymer resin. The resin generally serves to improve the cohesive and adhesive strength of the compositions when admixed with water in use. Examples or resins that may be utilised in the compositions of the invention include water-soluble resins, such as polyvinyl alcohol, and preferably redispersable polymer powder resins, e.g. derived from dispersions of: vinyl resins; styrene resins; copolymers of vinyl laurate, vinyl chloride and/or vinyl acetate and ethylene; vinyl acetate; copolymers of vinyl
acetate and vinyl versatatet styrene/acrylic copolymers; or resins derived from dispersions of styrene and butyl acetate or styrene and butadiene. The resins may optionally be silanated, e.g. silane groups may be added during polymerisation, since this has been found to increase the water resistance ofthe composition.
Suitable resins include: Goshenol water-soluble polyvinyl alcohol polymers; and redispersible polymer powders such as Rhophlex resins from Rohm and Haas, particularly Rhophlex DP 2605; Elotex resins from Elotex AG, particularly Elotex 1080, Elotex 50V/906, Elotex WS45 or WS73, Elotex AP200, Elotex BN0107 and Elotex WSlOlE; Vinnapas resins from Wacker Chemicals, particularly Vinnapas RI 532Z, Vinnapas RE5452, 546Z and 547Z, Vinnapas RI 538Z; Mowilith powder resins from Hoechst Limited, particularly Mowilith LDM 2072P, LDM 20700, DM117P and LDM 2040P; Acronal DS6200 from BASF (UK) Limited; PAV 27, PAV 29 and Rhodopas PSB 54 from Rhone-Poulenc; and DLP 110 and DLP 120 from Dow Europe.
The compositions of the invention may optionally further include calcium hydroxide, usually in powder form, in order to improve workability of the compositions when admixed with water for use. The incorporation of calcium hydroxide also serves as a pH increaser and rapidly activates resin component (E).
It is also sometimes convenient to optionally add fibres, fillers, antifoaming agents and/or wetting agents to the compositions of the invention. The presence of fibres serves to improve the coherence and resistance to slippage of the adhesive before it hardens and sets. Examples of fibres that may be used include natural or synthetic organic materials such as cotton, wool, nylon, polyethylene or polypropylene fibres, as well as inorganic fibres such as glass fibres.
Fillers that may be incorporated into the compositions ofthe invention include fine particle size inorganic materials such as silica sand, calcium carbonate (e.g. in the Fillers that may be incorporated into the compositions ofthe invention include fine particle size inorganic materials such as silica sand, calcium carbonate (e.g. in the form of ground limestone or calcite) or calcium magnesium carbonates (dolomites).
The use of fillers is particularly preferred where the compositions are to be used in thick-bed applications since they help to reduce cost and enhance the workability of the adhesive.
Component (A) is conveniently present in an amount of 10-80% by weight of the dry composition of the invention. Component (B) is conveniently present in an amount of 0.01 to 2% by weight. Component (C) is conveniently present in an amount of from 0.05 to 3% by weight. Component (D) is conveniently present in an amount up to 5% by weight. Component (E) is conveniently present in an amount of 0.5 to 10% by weight.
When present, calcium hydroxide is conveniently present in an amount up to 10% by weight of the composition. Optional fillers may conveniently be present in an amount of from 10 to 50% by weight. Fibres may optionally be present in an amount of from 0.1 to 2% by weight.
Shortly before use, the compositions ofthe invention are mixed with sufficient water to form a smooth, firm adhesive paste which may be applied to a substrate before tiles are applied thereto. The adhesive of the invention allows sufficient working time before hardening and setting, and during this period little or no slippage of the tiles occurs. The ability to provide little slippage is especially advantageous when tiles are to be applied to walls. The adhesive provides a high bond strength, and may be applied to a gypsum-based substrate without first applying a primer layer.
In some cases, however, it may be desirable first to apply a primer layer, e.g. to stabilise a cracked or crumbling substrate, but this is not necessary to prevent ettringite formation.
The following non-limiting examples serve to illustrate the invention.
FORMULATION 1 2 3 4 5 comparison comparison alpha CaSO4.H2O 80 80 50 beta CaSO4.H2O 40 35 Fine silica sand 20 20 20 Ground limestone 18 18 20 20 25 Calcium hydroxide 2.4 10 5 Redispersible resin-1 ditto-2 2 ditto - a blend 5 5 3 Cellulose ethers 2.5 3 1.5 Clay 1.5 9.0 Organic acid 0.1 0.5 1.0 Cellulose fibres 0.5 Water 22 23 27 27 26 RESULTS All tested and stored at 23 C/50% RH.
Setting time over 5 days 11 mins 19 mins 41 minus 60 mins Open time 2 mins 11 mins 19 minus 22 mins Workability Poor Good Good V. good Slip 1 mm 1 mm 0.5 mm Bond Stengths: (a) Tensile to CEN pr EN 1348 in N/mm2 0.7 0.72 0.7 (b) Shear to BS 5980 @ 14 days 9.5 > 20 > 20 18.0 @24 hours in kN 10.00 For further comparison, an adhesive was prepared containing: a-CaSO4.t/2 H20 - 100 gms (Calcium sulphate alpha hemihydrate) Water - 24 gms.
This set hard in 5 mins. and was difficult to make up for shear test samples. It was tested after 14 days in air to the shear-test requirements of British standard 5980, and gave only 2 kN (Minimum pass level 8.9 kN).

Claims (9)

1. A composition for admixture with water to form an adhesive, comprising: (A) anhydrous and/or partially hydrated calcium sulphate; (B) a hardening-rate modifier to regulate the rate of setting ofthe composition when admixed with water; (C) a water-retention aid; (D) a rheology modifier; and (E) a water-soluble or redispersible polymer resign.
2. A composition according to claim 1 wherein component (A) comprises calcium sulphate hemihydrate (beta form).
3. A composition according to either of claims 1 or 2 wherein component (B) comprises one or more alkali metal salts, organic acids and/or salts thereof.
4. A composition according to any preceding claim wherein component (C) comprises one or more cellulose ethers, starch ethers and/or natural or synthetic gums.
5. A composition according to any preceding claim wherein component (D) comprises one or more cellulose ethers, starch ethers, natural or synthetic gums, bentonite clays, wollastonites and/or attapulgites.
6. A composition according to any preceding claim wherein component (E) comprises one or more: polyvinyl alcohols; vinyl resins; styrene resins; copolymers of vinyl laurate, vinyl chloride and/or vinyl acetate and ethylene; vinyl acetate; copolymers of vinyl acetate and vinyl versatate; styrene/acrylic copolymers; or resins derived from dispersions of styrene and butyl acetate or styrene and butadiene; which may optionally be silanated.
7. A composition according to any preceding claim which additionally contains calcium hydroxide.
8. A composition according to any preceding claim which additionally contains fibres and/or fillers.
9. An adhesive composition comprising water in admixhrre with a composition as defined in any preceding claim.
GB9720960A 1997-10-02 1997-10-02 Method of adhering tiles using an adhesive containing calcium sulphate Expired - Fee Related GB2329895B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
GB9720960A GB2329895B (en) 1997-10-02 1997-10-02 Method of adhering tiles using an adhesive containing calcium sulphate

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB9720960A GB2329895B (en) 1997-10-02 1997-10-02 Method of adhering tiles using an adhesive containing calcium sulphate

Publications (3)

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GB9720960D0 GB9720960D0 (en) 1997-12-03
GB2329895A true GB2329895A (en) 1999-04-07
GB2329895B GB2329895B (en) 2001-07-25

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6824606B1 (en) * 1998-05-20 2004-11-30 Tolsa, S.A. Additive for special plasters and mortars, compositions containing the additive and utilization of the additive in special plasters and mortars
EP1785406A1 (en) * 2005-11-14 2007-05-16 La Chape Liquide S.A.S. Method for bonding on gypsum screeds
WO2008151879A1 (en) * 2007-06-14 2008-12-18 Construction Research & Technology Gmbh Dry construction material mixtures based on calcium sulfate
CN104072077A (en) * 2014-07-02 2014-10-01 杨连树 Special interface agent for moisture-proof water-proof gypsum blocks and preparation method of interface agent
ITMI20131323A1 (en) * 2013-08-02 2015-02-03 Gabriella Costamagna DECORATIVE ELEMENT, IN PARTICULAR FOR THE COATING OF WALLS AND FLOORS, AND ITS PREPARATION PROCEDURE
WO2017004120A1 (en) * 2015-06-30 2017-01-05 Dow Global Technologies Llc Gypsum compositions containing crosslinked cellulose ethers for mortars with reduced stickiness
WO2023277678A1 (en) * 2021-07-01 2023-01-05 Vazquez Carrera Daniel Dry-mix compositions comprising cement, esters of cellulose and ethylene-vinyl acetate copolymer with use in the production of adhesives for cement tiles, glazed ceramic floor tiles, porcelain tiles, glazed ceramic tiles, natural stone, cultured stone, quarry stone and marble
WO2023287274A1 (en) * 2021-07-16 2023-01-19 Vazquez Carrera Daniel Dry-mix compositions comprising cellulose esters, calcium sulfate dihydrate, pre-gelatinised starch ester and redispersible acrylic polymer, with use as an accelerated adhesive for joining and adhering panels of gypsum and cement

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113860842B (en) * 2021-10-28 2023-05-30 河北三棵树涂料有限公司 Inorganic single-component polymer tile back adhesive and preparation method thereof

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0094507A2 (en) * 1982-05-15 1983-11-23 Gebr. Knauf Westdeutsche Gipswerke Wall of slabs comprising a trowel joint
GB2140794A (en) * 1983-05-31 1984-12-05 United States Gypsum Co Jointing cementitous composition
EP0303071A1 (en) * 1987-08-08 1989-02-15 Rigips GmbH Joint filler
EP0320982A1 (en) * 1987-12-17 1989-06-21 PCI Augsburg GmbH Use of gypsum compositions as adhesives or as jointing materials
JPH01305389A (en) * 1988-06-03 1989-12-08 Nec Corp Detection evading system for submarine
JPH01305840A (en) * 1988-06-02 1989-12-11 Marusen Kagaku Kk Treating material for substrate joint
EP0496682A1 (en) * 1991-01-22 1992-07-29 Platres Lafarge Stucco for joints
US5277712A (en) * 1992-08-20 1994-01-11 Louisiana-Pacific Corporation Dry mix-type joint compounds, compositions therefrom and methods for filling drywall joints with same

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5653797A (en) * 1996-04-26 1997-08-05 National Gypsum Company Ready mixed setting-type joint compound and method of making same

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0094507A2 (en) * 1982-05-15 1983-11-23 Gebr. Knauf Westdeutsche Gipswerke Wall of slabs comprising a trowel joint
GB2140794A (en) * 1983-05-31 1984-12-05 United States Gypsum Co Jointing cementitous composition
EP0303071A1 (en) * 1987-08-08 1989-02-15 Rigips GmbH Joint filler
EP0320982A1 (en) * 1987-12-17 1989-06-21 PCI Augsburg GmbH Use of gypsum compositions as adhesives or as jointing materials
JPH01305840A (en) * 1988-06-02 1989-12-11 Marusen Kagaku Kk Treating material for substrate joint
JPH01305389A (en) * 1988-06-03 1989-12-08 Nec Corp Detection evading system for submarine
EP0496682A1 (en) * 1991-01-22 1992-07-29 Platres Lafarge Stucco for joints
US5277712A (en) * 1992-08-20 1994-01-11 Louisiana-Pacific Corporation Dry mix-type joint compounds, compositions therefrom and methods for filling drywall joints with same

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
JPO & JAPIO Abstract No. 03008239 & JP 01 305 389 A *
JPO & JAPIO Abstract No. 03008240 & JP 01 305 840 A *

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6824606B1 (en) * 1998-05-20 2004-11-30 Tolsa, S.A. Additive for special plasters and mortars, compositions containing the additive and utilization of the additive in special plasters and mortars
EP1785406A1 (en) * 2005-11-14 2007-05-16 La Chape Liquide S.A.S. Method for bonding on gypsum screeds
FR2893324A1 (en) * 2005-11-14 2007-05-18 Chape Liquide Soc Par Actions METHOD FOR BONDING ON A CHAPE BASED ON CALCIUM SULPHATE.
WO2008151879A1 (en) * 2007-06-14 2008-12-18 Construction Research & Technology Gmbh Dry construction material mixtures based on calcium sulfate
JP2010529270A (en) * 2007-06-14 2010-08-26 コンストラクション リサーチ アンド テクノロジー ゲーエムベーハー Calcium sulfate dry construction material mixture
AU2008264082B2 (en) * 2007-06-14 2013-03-28 Construction Research & Technology Gmbh Dry construction material mixtures based on calcium sulfate
WO2015015450A3 (en) * 2013-08-02 2015-07-23 Costamagna Gabriella Decorative element, in particular for covering walls and floors, and relative preparation method
ITMI20131323A1 (en) * 2013-08-02 2015-02-03 Gabriella Costamagna DECORATIVE ELEMENT, IN PARTICULAR FOR THE COATING OF WALLS AND FLOORS, AND ITS PREPARATION PROCEDURE
CN104072077A (en) * 2014-07-02 2014-10-01 杨连树 Special interface agent for moisture-proof water-proof gypsum blocks and preparation method of interface agent
CN104072077B (en) * 2014-07-02 2016-02-17 杨连树 Moistureproof and waterproof gypsum block special interface agent and preparation method thereof
WO2017004120A1 (en) * 2015-06-30 2017-01-05 Dow Global Technologies Llc Gypsum compositions containing crosslinked cellulose ethers for mortars with reduced stickiness
US10494303B2 (en) 2015-06-30 2019-12-03 Dow Global Technologies Llc Gypsum compositions containing crosslinked cellulose ethers for mortars with reduced stickiness
WO2023277678A1 (en) * 2021-07-01 2023-01-05 Vazquez Carrera Daniel Dry-mix compositions comprising cement, esters of cellulose and ethylene-vinyl acetate copolymer with use in the production of adhesives for cement tiles, glazed ceramic floor tiles, porcelain tiles, glazed ceramic tiles, natural stone, cultured stone, quarry stone and marble
WO2023287274A1 (en) * 2021-07-16 2023-01-19 Vazquez Carrera Daniel Dry-mix compositions comprising cellulose esters, calcium sulfate dihydrate, pre-gelatinised starch ester and redispersible acrylic polymer, with use as an accelerated adhesive for joining and adhering panels of gypsum and cement

Also Published As

Publication number Publication date
GB9720960D0 (en) 1997-12-03
GB2329895B (en) 2001-07-25

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732E Amendments to the register in respect of changes of name or changes affecting rights (sect. 32/1977)
PCNP Patent ceased through non-payment of renewal fee

Effective date: 20081002