WO2001081481A1 - Revetements inorganiques modifies par des polymeres - Google Patents

Revetements inorganiques modifies par des polymeres Download PDF

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Publication number
WO2001081481A1
WO2001081481A1 PCT/AU2001/000377 AU0100377W WO0181481A1 WO 2001081481 A1 WO2001081481 A1 WO 2001081481A1 AU 0100377 W AU0100377 W AU 0100377W WO 0181481 A1 WO0181481 A1 WO 0181481A1
Authority
WO
WIPO (PCT)
Prior art keywords
range
anhydrous
coating composition
particles
polymer
Prior art date
Application number
PCT/AU2001/000377
Other languages
English (en)
Inventor
Robert Frederick Barber
Original Assignee
Australian Oxides Pty 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 Australian Oxides Pty Ltd filed Critical Australian Oxides Pty Ltd
Priority to CA002405462A priority Critical patent/CA2405462A1/fr
Priority to NZ521791A priority patent/NZ521791A/en
Priority to AU2001243960A priority patent/AU2001243960B2/en
Priority to AU4396001A priority patent/AU4396001A/xx
Priority to GB0223342A priority patent/GB2378439B/en
Publication of WO2001081481A1 publication Critical patent/WO2001081481A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • C09D1/06—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances cement
    • C09D1/08—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances cement with organic additives

Definitions

  • This invention relates to inorganic coatings and in particular to polymer modified inorganic coatings.
  • Background to the Invention Coatings have been used for many years to enhance the appearance and provide protection for substrates.
  • coating compositions are widely used as architectural and house paints.
  • the substrates to which these coatings are applied include timber, unreinforced and steel reinforced concrete and bricks as well as previously coated substrates.
  • the coating compositions consist of a film forming binder in which are dispersed pigments or colorants that provide opacity and/or colour to the coating.
  • the binders are generally either oil based where the binder is usually an alkyd resin or water based where the binder is a film forming latex. In more recent times latex based coatings have become the predominant type of coating for residential and commercial structures as they do not have high levels of organic solvent present. They are thus safer to use and less polluting to the environment.
  • This render coat is usually of a composition similar to brick laying mortar and consists of sand, lime and Portland cement as well as optional colourants.
  • This render coat is trowel applied after mixing the ingredients with water and normally a three coat system is used to provide a trowel applied coating having a total thickness of typically at least 10mm.
  • These latex based render coats have achieved wide- spread acceptance. However, they are relatively expensive.
  • the binder in these coatings is usually an acrylic latex. While these render coats are able to provide the desired decorative appearance to the substrate they also lack some of the long-term protective properties desired of such coatings.
  • Polymer or latex modified cementitious (containing cement) trowel applied mortars have been proposed to improve the performance of such mortars.
  • the mix proportions of most latex modified mortars are in the range of cement to fine aggregate (sand) ratio of 1:2 to 1:3 (by weight), polymer to cement ratio of 1:5 to 1:20 and water to cement ratio of 1:3 to 2:3.
  • US 5,806,609 (BASF) relates to adding alkyl phenol ethylene oxide surfactants to a cementitious composition to improve the adhesion of the composition to polystyrene foams.
  • the cementitious compositions contain polymer powder but it is typically present at very low levels such as 3% in Example 1.
  • US 5,753,036 Air Products & Chemicals Inc discloses mortar compositions that involve the use of acrylic latexes stabilised with partially hydrolysed poly(vinyl alcohol).
  • the powdered polymer content is preferably in the range 1-20% and more preferably in the range 2-12%.
  • This invention provides in one form an anhydrous cementitious coating composition
  • an anhydrous cementitious coating composition comprising: hydraulic cement in the range 30-70% w/w polymeric particles having a Tg less than 25°C, preferably less than 15°C in the range 5-25% w/w, and more preferably in the range 8-20% w/w; mineral extender particles in the range 5-50% w/w and; wherein the cement to mineral extender particles are in the weight ratio 5:1 to 1:1.
  • the hydraulic cement percentage is 40-65% w/w and more preferably 50-60% w/w.
  • the polymeric particles are meth(acrylic) polymers.
  • the mineral extender includes ceramic microspheres and more preferably the major proportion of the mineral extender consists of ceramic microspheres.
  • this invention provides anhydrous cementitious coating compositions as defined above wherein up to 100% of the polymeric particles are replaced with a natural polymer.
  • natural polymer means that the polymer is a natural product or derived from a natural product. Examples are casein and cellulosic polymers.
  • the anhydrous cementitious compositions of the present invention are described as anhydrous in that they are intended to be free flowing powders and require the addition of water before application and use. Minor amounts of water may be present, for example water of crystallisation associated with the mineral extenders. However, provided the minor amount of water does not adversely effect the storage stability or final properties of the composition such compositions are regarded as anhydrous.
  • the coatings are described as inorganic in that a substantial amount of the binder is inorganic. However it will be appreciated that the coatings are mixed with significant amounts of organic polymer and such hybrid coatings are described as polymer modified inorganic coatings.
  • compositions of the present invention are prepared for use by mixing the anhydrous blend of dry ingredients with potable water to form a slurry suitable for application.
  • the products are conveniently applied in a similar fashion to latex paints using either a brush, spray equipment or paint roller. They thus differ from conventional render compositions that are trowel applied.
  • the compositions of the present invention do require the addition of water for application they do not require the addition of other resin or latex components.
  • the amount of water may thus be varied without the cement to latex proportions being changed . It will be appreciated that the amount of water added not only effects the application properties of the composition but also the chemical and physical properties of the final cured coating.
  • the amount of water that is added to the composition is usually in the range of anhydrous composition to water of 1:0.2 to 1 :0.5 and more preferably 1 :0.2 to 1 :0.4.
  • Tg glass transition temperatures
  • the term glass transition temperature is well known in the art and generally defines the onset of long range molecular motion wherein the polymer preserves the outward appearance of a solid but becomes rubbery and then tacky with increasing temperature and undergoes plastic flow and elastic deformation.
  • Tg can be measured in accordance with the differential thermal analysis method set out in the Journal of Paint Technology, Volume 41, pages 167-168 (1969) or by testing of softening points or thermomechanical analysis (TMA). In practice we find in most cases that the Tg as determined by the various available methods is close to the theoretical Fox Tg.
  • the polymer particles suitable for the present invention are usually in the form referred to as redispersible polymer powders. These are manufactured by a two-step process. Initially polymer latices are prepared by emulsion polymerisation. Before these are spray dried the latexes are combined with bactericides, spray drying aids and antifoaming agents. Anti blocking agents such as ultrafine clays, silica and calcium carbonate are added to the polymer powders during or after spray drying to prevent caking of the powders during storage. This is necessary because the Tg of the powders is less than ambient temperature.
  • the preferred polymeric particles are prepared from acrylic and methacrylic acid alkyl esters such as methyl methacrylate and butyl acrylate.
  • monomers such as methyl methacrylate and butyl acrylate.
  • these include styrene, vinyl acetate and carboxylic acid containing monomers such as acrylic acid.
  • Ethylene and butadiene are other possible monomers.
  • Particularly suitable polymer particles are those supplied by Rohm and Haas under the trade name Drycryl DP- 2904. This is a 100% acrylic re-dispersible powder which has a Tg of 10°C and average particle size (before redispersion) of 45-75 ⁇ m.
  • compositions of the present invention are prepared as dry mixes using conventional mixing equipment.
  • the slurried coating composition may be applied at appropriate rates to give dry film builds generally in the range 100-2000 ⁇ m although preferred dry film builds are in the range 400-1000 ⁇ m.
  • the compositions of the present invention when slurried with water usually have a pot life or useable consistency of an hour or more at ambient temperature and this allows sufficient time for application. Most of the water present in the slurried composition participate in reaction with the cementitious particles leading to films that do not exhibit as much shrinkage on drying as conventional latex paints or render coats.
  • conventional concrete or mortar admixtures may be incorporated to reduce the amount of water needed for a given degree of liquid consistency and to reduce water evaporation. They also assist in consistent properties being attained under a range of application conditions.
  • wicking of water from the slurried composition into the substrate may lead to a loss of water from the coating.
  • anti-wicking agents may be used or alternatively a sealer coat may be applied to the substrate before applying the slurried coating. As the coating cures it has been found useful to apply a water spray to remove residual surfactants.
  • the mineral extenders are usually less than 100 ⁇ m in size and preferably less than 50 ⁇ m and in preferred compositions include ceramic microspheres as a major component of the mineral extenders.
  • Other suitable extenders include mica, clays, and diatomaceous earth.
  • Other extenders that may be used include fly ash, blast furnace slag and condensed silica fume and the term mineral extenders also includes mineral particles that can participate in chemical reactions. These materials are commonly referred to as Pozzalanic materials.
  • the term mineral extenders also includes inorganic pigments such as iron oxide, rutile and other opacifiers or colourants.
  • the weight ratio of hydraulic cement to mineral extender particles is important and should be in the range 5:1 to 1:1. This ratio differs from many other cementitious compositions.
  • mice Mica flakes (325 mesh) 1.450 Mica powder (53 ⁇ m) 0.600
  • Diatomaceous earth powder (5 ⁇ m) 2.700
  • Anti-foam powder 1.900 Titanium Dioxide pigment 6.000
  • Methyl cellulose powder ('Methocel' H25) 0.030
  • This example illustrates the preparation of an aqueous composition from the dry mix of Example 1.
  • dry mix of Example 1 1000 water 350
  • This example illustrates the preparation and testing of the composition of Example 2.
  • Example 2 The composition of Example 2 was applied in two coats at a nominal wet film thickness of 500 ⁇ m per coat. A recoat interval of one hour was used. Sample Preparation
  • test pieces were unglazed ceramic tiles and these were conditioned at 23 ⁇ 2°C and 50 ⁇ 20% relative humidity for 7 days prior to testing.
  • test piece was a concrete block and after coating it was conditioned at 23 ⁇ 2°C and 60 ⁇ 10% relative humidity for 9 days prior to testing.
  • test pieces were unglazed ceramic tiles and after coating these were conditioned at 23 ⁇ 2°C and 60 ⁇ 10% relative humidity for 9 days.
  • the chloride diffusion coefficient was determined at steady state condition using Ficks first law of diffusion to be 2.7 x 10 " m /sec.
  • the mean adhesion strength of the coating composition of the coating was 1.9 MPa. These results are considered to be satisfactory since the mode of failure was cohesive failure of either the coating or the substrate concrete, indicating that the strength of the adhesive bond obtained exceeded the tensile strengths of the materials.
  • the AS 1580 test method is applicable to all generic types of film-forming coatings and substrates. There is no standard minimum value as this varies with the coating system, substrate and method of surface preparation. Generally, adhesion strengths for coatings or repairs on concrete substrates rarely exceed 2 - 2.5 MPa. Specifications for concrete repair materials typically require a minimum mean adhesion strength of 1.5 MPa between the repair material and the prepared substrate. The only reference to a recommended numerical adhesion strength value was found in the following British Standard:
  • the average wear index of the coating composition was 101.3, as measured for 2 samples using the ASTM Taber abrasion test method. In isolation this value cannot be interpreted, but may provide some comparison with data for other materials tested using the same method.
  • abrasion resistance test methods are only suitable for comparative assessment of materials, as the mechanism of abrasion does not usually model the mechanisms encountered in normal service environments.
  • the Taber abrasion test method has relatively poor reproducibility.
  • numerical abrasion resistance values are to be compared they should be preferably be generated by a common laboratory.
  • the Taber abrasion test method is best suited to thin coatings, but is also used for ceramics and similar materials. It requires measurement of average weight loss over a number of wear cycles.
  • the alternative Chaplin Method which uses powered abrasive wheels for abrasion, is more aggressive and is best suited to tests of concrete substrates or relatively thick toppings on a comparative basis using the mean depth of wear.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Aftertreatments Of Artificial And Natural Stones (AREA)

Abstract

L'invention concerne une composition de revêtement à base de ciment anhydre constituée de 30 à 70 % en poids d'un ciment hydraulique, de 5 à 25 % de particules polymères possédant une Tg inférieure à 25 °C et entre 5 et 50 % de particules diluantes minérales. Le rapport ciment/particules minérales et compris entre 5/1 et 1/1. Lorsqu'on les mélange à l'eau, ces compositions constituent des compositions de revêtement décoratives ou protectrices pouvant être appliquées à plusieurs substrats.
PCT/AU2001/000377 2000-04-19 2001-04-04 Revetements inorganiques modifies par des polymeres WO2001081481A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
CA002405462A CA2405462A1 (fr) 2000-04-19 2001-04-04 Revetements inorganiques modifies par des polymeres
NZ521791A NZ521791A (en) 2000-04-19 2001-04-04 Polymer modified inorganic coatings
AU2001243960A AU2001243960B2 (en) 2000-04-19 2001-04-04 Polymer modified inorganic coatings
AU4396001A AU4396001A (en) 2000-04-19 2001-04-04 Polymer modified inorganic coatings
GB0223342A GB2378439B (en) 2000-04-19 2001-04-04 Polymer modified inorgantic coatings

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AUPQ7013 2000-04-19
AUPQ7013A AUPQ701300A0 (en) 2000-04-19 2000-04-19 Polymer modified inorganic coatings

Publications (1)

Publication Number Publication Date
WO2001081481A1 true WO2001081481A1 (fr) 2001-11-01

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/AU2001/000377 WO2001081481A1 (fr) 2000-04-19 2001-04-04 Revetements inorganiques modifies par des polymeres

Country Status (5)

Country Link
AU (1) AUPQ701300A0 (fr)
CA (1) CA2405462A1 (fr)
GB (1) GB2378439B (fr)
NZ (1) NZ521791A (fr)
WO (1) WO2001081481A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4367300A (en) * 1979-12-14 1983-01-04 Kowa Chemical Industries Co., Ltd. Synthetic resin compositions to be added to cement, an aqueous paint composition containing said compositions and a method for coating said paint composition
US5753036A (en) * 1997-04-21 1998-05-19 Air Products And Chemicals, Inc. Poly(vinyl alcohol) stabilized acrylic polymer modified hydraulic cement systems
US5807609A (en) * 1994-07-29 1998-09-15 Basf Aktiengesellschaft Mineral building materials modified with polymers and containing at least one added compound
JPH11116317A (ja) * 1997-10-20 1999-04-27 Nippon Buren Partner:Kk 耐酸複合セメント組成物
US5935699A (en) * 1996-12-20 1999-08-10 Barber; Robert Frederick Lightweight composite material comprising hollow ceramic microspheres

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4367300A (en) * 1979-12-14 1983-01-04 Kowa Chemical Industries Co., Ltd. Synthetic resin compositions to be added to cement, an aqueous paint composition containing said compositions and a method for coating said paint composition
US5807609A (en) * 1994-07-29 1998-09-15 Basf Aktiengesellschaft Mineral building materials modified with polymers and containing at least one added compound
US5935699A (en) * 1996-12-20 1999-08-10 Barber; Robert Frederick Lightweight composite material comprising hollow ceramic microspheres
US5753036A (en) * 1997-04-21 1998-05-19 Air Products And Chemicals, Inc. Poly(vinyl alcohol) stabilized acrylic polymer modified hydraulic cement systems
JPH11116317A (ja) * 1997-10-20 1999-04-27 Nippon Buren Partner:Kk 耐酸複合セメント組成物

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN *

Also Published As

Publication number Publication date
GB0223342D0 (en) 2002-11-13
GB2378439B (en) 2004-04-14
GB2378439A (en) 2003-02-12
CA2405462A1 (fr) 2001-11-01
NZ521791A (en) 2004-08-27
AUPQ701300A0 (en) 2000-05-11

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