AU2006272435B2 - Paint composition - Google Patents

Description

WO 2007/009161 PCT/AU2006/000989 1 Paint Composition Field of the Invention This invention relates to water based artists' paints and more particularly to 5 improved water based artists' paint compositions. Background to the Invention Acrylic paints dry as water leaves the paint. As water evaporates or is absorbed by the substrate to which the paint is applied, acrylic polymer particles coalesce into a 10 continuous adhesive film. Within a relatively short period of time, approximately 10 to 15 minutes, a skin forms over the outer surface of the paint film. At this stage the paint film is said to be "dry to the touch". The thicker films continue to dry over time, the length of time varying with the thickness of the film. For very thin films this may be a few minutes, while films half a centimetre in thickness or more may take weeks or 15 months. Once the skin has formed over the paint film, the film can no longer be worked. The artist is not able to change and adapt what is taking place on the canvas using traditional techniques. Although the touch dry film could be painted over, the "wet in wet" painting techniques are severely curtailed. The term "wet in wet" is used by 20 persons skilled in the art to refer to painting techniques by which the artist creatively works and develops the wet paint on the substrate, adding, blending and altering the appearance over time to achieve the desired artistic result. Temperature, humidity and air flow are environmental factors that influence the drying times of acrylic paint compositions. The time taken for a paint film to skin over 25 can be extended somewhat by reducing air-flow, lowering temperature and increasing humidity. Manipulating such environmental factors may not always be possible or practical. Low temperatures (below about 9"C) may interfere with coalescence of the polymer particles resulting in paint film cracking, becoming powdery or failing to adhere to the substrate. Optimum humidity miy be difficult to determine and maintain. 30 The nature of the substrate also influences the drying time of acrylic paint compositions. An absorbent substrate will draw moisture out of the paint composition and speed drying time. Sealing the substrate to reduce absorbency or selecting a nonabsorbent substrate such as metal or masonite will reduce the moisture lost through the substrate. Using a moist substrate can also reduce moisture lost through the 35 substrate and increase humidity in the environment of the paint. -By soaking the back of a canvas with water or attaching wet rags or sponges to the back of a canvas, for 2 example, the rate of drying of the paint film can be reduced. This technique has limitations and the water may also wash impurities out of the canvas into the paint film causing discoloration. Humectants, such as glycerin or propylene glycol may be used as paint additives 5 to extend the time taken for a paint film to skin over. As paint additives however, humectants tend to linger in the paint film. They can remain tacky and adversely affect outer coat adhesion. Most importantly they do not prevent fast drying of thin films of paint. Any discussion of documents, acts, materials, devices, articles or the like which 10 has been included in the present specification is not to be taken as an admission that any or all of these matters form part of the prior art base or were common general knowledge in the field relevant to the present invention as it existed before the priority date of each claim of this application. Disclosure of the Invention 15 The invention relates to a water-based paint containing at least one water dispersible acrylic polymer, the improvement comprising including in the composition at least one alkali soluble polymer in an amount effective to increase the open time of the composition and at least one substituted amine in an amount effective to adjust the pH to about 7 to about 11. 20 In one aspect, the present invention relates to a water-based artists' paint composition consisting essentially of: at least one pigment in an effective amount to provide the desired pigmentation; at least one alkali soluble polymer in an amount effective to increase the open time of the composition so that the paint composition remains workable and may be 25 blended and altered, said polymer being selected from the group consisting of polymers soluble at ambient temperature and pressure in an aqueous solution having a pH of from about 7 to l1; at least one substituted amine in an amount effective to adjust the pH to about 7 to about 11, said amine selected from the group consisting of C 1

-

6 alcohol amines, C 1 -6 30 alkyl CI.

6 alcohol amines and mixtures thereof, a binding effective amount of at least one water dispersible acrylic polymer; and an effective amount of at least one alkali soluble or alkali swellable thickener. The composition also optionally includes one or more conventional additives such as dispersants, theology modifiers, defoamers, coalescents and preservatives. 35 The term "open time" as used herein means the time during which the paint composition remains workable such that it may be blended and altered.

3 The term "consisting essentially of' as used herein is intended to exclude elements that would materially affect the properties of the claimed composition or steps of the claimed method. Throughout this specification the word "comprise", or variations such as 5 "comprises" or "comprising", will be understood to imply the inclusion of a stated element, integer or step, or group of elements, integers or steps, but not the exclusion of any other element, integer or step, or group of elements, integers or steps. The present inventor has surprisingly found that the period during which a water-based acrylic paint composition remains workable, i.e. the open time of the paint, 10 can be significantly extended to free the artist to develop the artistic work over many hours. Rather than developing a paint skin in the normal way, within about 10 minutes, the composition sets gradually over time. Wet paint may therefore be applied over paint already on a substrate and may be blended with it and into it, giving artists time to create complex paintings while working at their own pace and with ample opportunity 15 to revise and alter their work before it becomes fixed. The open time can be extended for several hours and for as long as a day by using the composition of the invention and by periodically applying water to the paint film for example by sprinkling or spraying. The conventional acrylic binder, namely a water dispersible polymer, is prevented from forming a skin as the water evaporates. Whilst not wishing to be bound by theory, it is 20 believed that the alkali soluble polymer forms a coating around the dispersion polymer particles preventing coalescence of those particles. A water resistant film is formed only when the amine evaporates and the alkali soluble polymers themselves become water resistant. Also disclosed herein is a method of extending the open time of a water-based 25 acrylic artists' paint composition, the composition comprising at least one pigment in an effective amount to provide the desired pigmentation, a binding effective amount of at least one dispersible acrylic polymer and an effective amount of at least one alkali soluble or alkali swellable thickener, the method comprising including in the composition at least one alkali soluble polymer in an amount of effective to increase 30 the open time of the composition said polymer being selected from the group consisting of polymers soluble at ambient temperature and pressure in an aqueous solution having a pH of from about 7 to about 11; and at least one substituted amine in an amount effective to adjust the pH to about 7 to about 11 and optionally, periodically applying water to the composition. 35 In another aspect, the present invention relates to a method of extending the open time of a conventional water-based acrylic artists' paint composition not including 4 an alkali soluble polymer, the method consisting essentially of including in the conventional composition at least one alkali soluble polymer in an amount effective to increase the open time of the composition so that the paint composition remains workable and may be blended and altered, said polymer being selected from the group 5 consisting of polymers soluble at ambient temperature and pressure in an aqueous solution having a pH of from about 7 to about I1; and at least one substituted amine selected from the group consisting of C 1

-

6 alcohol amines, C1.

6 alkyl C1.

6 alcohol amines and mixtures thereof in an amount effective to adjust the pH to about 7 to about 11. In another aspect, the present invention relates to a method of controlling the 10 open time of a water-based acrylic artists' paint composition consisting essentially of at least one alkali soluble polymer in an amount effective to increase the open time of the composition so that the paint remains workable and may be blended and altered, and at least one substituted amine selected from the group consisting of C,- 6 alcohol amines,

C,.

6 alkyl C1.

6 alcohol amines and mixtures thereof in an amount effective to adjust the 15 pH to about 7 to about 11, the method comprising periodically applying to the composition one or more of: (a) water; (b) a first medium comprising at least one alkali soluble polymer and at least one substituted amine selected from the group consisting of C1.

6 alcohol amines, C1.

6 alkyl 20 C,.

6 alcohol amines and mixtures thereof in an amount effective to adjust the pH to about 7 to about I1; and (c) a second medium comprising at least one water dispersible acrylic polymer. In yet a further aspect, the present invention is directed to a process of making a water-based artists' paint composition consisting essentially of at least one alkali 25 soluble polymer, at least one substituted amine, at least one water dispersible acrylic polymer, and at least one alkali soluble or alkali swellable thickener, the process comprising adding the at least one alkali soluble polymer in an effective amount to increase the open time of the composition so that the paint composition remains workable and may be blended or altered, said polymer being selected from polymers 30 soluble at ambient temperature and pressure in an aqueous solution having a pH of about 7-11; and at least one substituted amine in an amount effective to adjust the pH to about 7 11, said amine selected from C1.

6 alcohol amines, CI- 6 alkylCI-6 alcohol amines and mixtures thereof; 35 a binding effective amount of at least one water dispersible acrylic polymer; and an effective amount of at least one alkali soluble or alkali swellable thickener.

4A Alkali Soluble Polymer As used herein, the term "alkali soluble polymer" means a polymer which is capable of being solubilized at ambient temperature and pressure in an aqueous 5 solution where the pH is alkaline. The solubilization pH of the alkali-soluble polymer is generally in the order of from about 7 to about 11. Preferably the solubilisation pH is in the order of from about 7.5 to about 10, more preferably about 7.5 to about 9.5. An alkali soluble polymer has at least one acidic or anion producing group. Examples of anion producing groups include but are not limited to carboxylic hydroxyl, phenolic 10 hydroxyl, active imido and sulfonamide. The alkali soluble polymer is made to serve as an auxiliary binder and is not a conventional ingredient in acrylic paints. The proportion of alkali soluble polymer can be varied to manipulate the drying time of the paint composition. The higher the ratio of alkali soluble polymer to water 15 dispersible acrylic polymer, the longer the drying time as long as a slow-evaporating amine is also present (as discussed below). For a paint composition with a feel similar to a conventional acrylic artists' paint the ratio of alkali soluble polymer to water dispersible acrylic polymer may range from about 1:4 to 1:20, preferably from about 1:5 to 1:10. In a 200L batch of paint for 20 example where 80kg/200L of water dispersible acrylic binder is used and about 10kg/200L of alkali soluble or alkali swellable thickener, the amount of alkali soluble polymer may be in the range of about 4-20 kg/200L, preferably 8-15 kg/200L, more preferably 8-12 kg/200L and most preferably 8-10kg/200L. This equates to ratios of alkali soluble polymer to water dispersible acrylic polymer of from about 1:4 to 1:20, 25 preferably from about 1:5.33 to 1:10, more preferably from about 1:6.66 to 1:10 and most preferably from about 1:8 to 1:10. For a paint composition with a feel more like a traditional gouache a ratio of alkali soluble polymer to water dispersible acrylic polymer may range from about 1:1 to 1:3, preferably about about 3:4. This ratio gives a tough paint film which is less 30 brittle and more flexibile than a conventional guache but can still be applied thickly if desired. Artists may wish to use paints in several different ways or techniques in the same painting and the paint is usually applied in successive layers. An artist may sometimes want a layer of paint to dry quickly, but more often wants to extend the open 35 time, and being able to control what is happening is desirable.

4B A paint as described above with 80kg water dispersible acrylic binder per 200L and 8-12kg of alkali soluble binder does not form a skin and can be kept "open" by spraying with a water atomiser from time to time as water evaporates and the paint 5 becomes tacky. Mediums can also be used to give the artists even more control. For faster drying, a medium made from water dispersible acrylic polymer applied to a paint film will swing the balance towards fast film formation, while for a slower drying paint, a medium made from alkali soluble polymer/ substituted amine swings the balance in the opposite direction. 10 In another embodiment, the invention provides a method of controlling the open time of a water-based acrylic artists' paint composition, the composition comprising at least one pigment in an effective amount to provide the desired pigmentation, a binding effective amount of at least one dispersible acrylic polymer and an effective amount of at least one alkali soluble or alkali swellable thickener, the method comprising 15 including in the composition at least one alkali soluble polymer in an amount effective to increase the open time of the composition and at least one substituted amine in an amount effective to adjust the pH to about 7-11 and periodically applying to the composition one or more of: (a) water; 20 (b) a medium comprising at least one alkali soluble polymer and at least one substituted amine in an amount effective to adjust the pH to about 7-11; and (c) a medium comprising at least one water dispersible acrylic polymer. Suitable commercially available alkali soluble polymers are flexographic ink polymers such as those manufactured by Rohm & Haas under the names Lucidene WO 2007/009161 PCT/AU2006/000989 5 .361 and Lucidene TM 602 LS, and Acrysol 1-62. Also suitable are GlascolTM LS16, and the LE 500 series - LE 510, LE 520 and LE 530 manufactured by Ciba Specialty Chemicals and Joncryl 142 TM manufactured by Johnson Wax Co. 5 Substituted Amine Substituted amines are included in amounts sufficient to neutralise the composition to a pH in the range of about 7 to about 11. Preferably the pH is in the range of from about 7.5 to 10, more preferably about 7.5 to 9.5. Suitable amines include C,. alcohol amines . and C1.

6 alkyl C 1 6 alcohol amines such as 10 aminomethylpropanol (AMP), monoethanolamine (MBA), diethanolamine (DEA) and triethanolamine (TEA) and mixtures thereof. AMP and TEA and mixtures thereof are preferred. Substituted amines are selected so as to slow the evaporation of the amines thereby extending the time in which the binders and thickeners (those which are water soluble or swellable under alkali conditions) may remain in solution, 15 Dispersible Acrylic Polymer The present invention includes at least one water dispersible acrylic polymer. These polymers are conventional binders for acrylic paints, well known to those skilled in the art. Suitable polymers include water dispersible polymers containing one or 20 more monomers selected from styrene, acrylates, alkylarylates and dienes. Polymers including acrylate, methacrylate and methyl methacrylate monomers are common. The selection of water dipersible acrylic binder and the quantity to be used for the composition of the present invention is within- the skill of the person skilled in the art using routine trial and experimentation. 25 Examples of suitable commercially available water dispersible acrylic polymers are PR 3230, ac 2235, ACI-1955 and Primal SF-017 manufactured by Rohm & Haas. Also suitable is Acronal 290D manufactured by BASF. The water dispersible acrylic polymer is present in the composition of the invention in a binding effective amount. A "binding effective amount" of at least one 30 water dispersible acrylic polymer will be understood to mean that the at least one water dispersible polymer is present in an amount so that in combination with the at least one alkali polymer discussed above, it will bind the pigment particles together into a cohesive paint film upon drying.

WO 2007/009161 PCT/AU2006/000989 6 Thickener One or more alkali soluble or alkali swellable thickeners are included in the composition of the present invention. Such thickeners typically comprise the aqueous emulsion reaction product of an unsaturated carboxylic acid monomer, e.g., 5 methacrylic acid; a monoethylenically unsaturated monomer different from the carboxylic acid monomer, e.g. ethyl acrylate; a macromonomer comprising a hydrophobic portion and an alkoxylated portion which is polymerizable with the other monomers; and a monomer having latent crosslinking fimtionality. Suitable thickeners include UCAR 146 and UCAR Polyphobe TR115, manufactured by Union 10 Carbide and Acrysol DR-1, Acrysol DR-73, Acrysol ASE 60 manufactured by Rohm & Haas. The thickeners may be varied depending on the main pigments being used in order to get a uniform viscosity. The selection of alkali soluble or alkali swellable thickener and the quantity to be used for the composition of the present invention is 15 within the skill of the person skilled in the art using routine trial and experimentation. Pigment One or more pigments may be included in the composition. Pigmentation provides colour and opacity and may contribute to other properties of the paint 20 composition. A person skilled in the art will be aware that pigment particle size and shape, ease of wettability or properties relating to specific density contribute to the viscosity and application characteristics of the wet paint composition and ultimately properties of the dried paint coatings. A person skilled. in the art will therefore appreciate that the choice of pigment will have an effect on the choice of other 25 ingredients such as thickeners. It is well within the skill of the addressee to determine the appropriate selection of pigment and the quantity to be used using routine trial and experimentation. Colour pigments may be organic or inorganic compounds, natural or synthetic and these may be used separately or in combination. Titanium dioxide is a common 30 white pigment with a high refractive index and excellent hiding power (the ability to render a paint opaque). It is frequently used with both coloured organic and inorganic pigments. Iron oxides range in colour from yellow and red to brown and black. Azo pigments are a common class of organic colour pigments. Pigments called "extender" pigments may be used in conjunction with other pigments. The use of extender 35 pigments reduces shrinkage stresses within the paint film and increases the pigment volume content at relatively low cost. Extender pigments include those based on WO 2007/009161 PCT/AU2006/000989 7 carbonates, silicates, sulfates, barytes and mica. The use of extender pigments aids in viscosity and flow control and reinforces the dry film strength, Dispersant 5 . The composition of the present invention may include one or more dispersants. These are conventional ingredients used to enhance pigment loading and dispersion stability. The dispersant may be nonionic or anionic surfactants. Anionic surfactants are preferred. Examples of suitable anionic emulsifiers include sodium lauryl sulfate, sodium dodecyl benzene sulfonate, dioctylsulfosuccinate, sodium polyoxyethylene 10 lauryl ether sulfate, sodium dodecyl diphenyloxide disulfonate and other diphenylsulfonate derivatives, and sodium salt of tert-octylphenoxyethoxypoly(39) ethoxyethyl sulfate. Suitable anionic surfactants are manufactured by Rohm & Haas under the trade marks Orotan 1124, Orotan 1288, Orotan 731 DP and Orotan 850. 15 The skilled addressee is able to determine the appropriate selection of dispersants and the quantity to be used using routine trial and experimentation. Other Additives The composition also optionally includes one or more conventional additives 20 such as rheology modifiers, defoamers, coalescents and preservatives. Best Modes for Performing the Invention The invention will now be further discussed with reference to the following examples. It is to be understood that these examples are illustrative and not restrictive. 25 Example 1. Ingredient Function Quantity (k) Quinacridone Magenta Pigment 20kg Orotan 1124 (Rohm & Haas) Dispersant 4kg Functionalised polyacrylate copolymer (Anionic Dispersant) Surfynol CT-171 (Air Products & Chemicals Dispersant 4kg Inc) Anionic Dispersant Acrysol 162 (Rohm & Haas) Auxiliary 8kg WO 2007/009161 PCT/AU2006/000989 8 Alkali Soluble Ink Polymer Binder Calcium Carbonate Extender 50kg PR3230 (Rohm & Haas) Binder 80kg Acrylic Dispersion Propylene Glycol Freeze/thaw 6 kg stability TT615 (Rohm & Haas) Rheology 2kg Alkali Swellable Rheology Modifier Modifier Acrysol DRl (Rohm & Haas) Rheology 2kg Alkali Swellable Rheology Modifier Modifier Acrysol ASE 60 (Rohm & Haas) Thickener 8-10kg Acrylic polymer containing carboxylic acid groups (Alkali Swellable Thickener) AMP or MEA to pH 9.3 Neutraliser Water q.s. 200L Example 2 Ingredient Function Quantity (kg) Perinone Orange Pigment 10kg Remainder as for Example 1 except no Quinacridone I Magenta pigment Example 3 3. Terre Verte Pthalo Blue Pigment: 4 kg Raw Sienna Pigment: 68.25kg Remainder as for Example 1 except no Quinacridone Magenta. pigment or calcium carbonate Example 4 4. Blue Black Pthalo Blue 10kg Carbon Black 2.5kg Remainder as per Example 1 except no Quinacridone Magenta pigment WO 2007/009161 PCT/AU2006/000989 9 Example 5 5. Ultramarine Blue Pigment 100kg Remainder as for Example 1 except no Quinacridone Magenta pigment or calcium carbonate The thickeners may be varied depending on the main pigments being used in order to get a uniform viscosity. The alkali swellable thickener in the examples may be substituted with other conventional alkali swellable thickeners as discussed above. 6 The amount of Alkali Soluble Ink polymer may be varied to control the rate of drying. For Acrysol 1-62 in the examples above amounts may be varied from about 4kg to about,20kg/200L. Preferred amounts are from 8-15 kg/200L more preferably 8 12 kg/200L. Less than 4kg does not achieve the desired effect. 10 The paint making process is the same for any colour and is the conventional procedure which may be summarised as follows. Stage 1: Load: Add water, dispersants, some defoamer as required to control against foam and alkali soluble ink polymer and under agitation using a cavitation mixer such 15 as a TORRACE mixer, add enough substituted amine, such as MEA or TEA, to neutralize this mixture to desired pH, add the coalescent if used. A suitable defoamer is manufactured by Henkel under the trade mark Foamaster NS-1. Stage 2: At this point the pigment (and extender if used) is added, either in powder 20 form, or possibly as a pre-dispersed liquid which has already been processed in a bead mill Stage 3: Add a portion of the thickener and disperse. 25 Stage 4: Let down: Add the acrylic binder dispersion, the rheology modifiers and remainder of the thickener and the propylene glycol. Stage 5: Add sufficient water to make 200L and stir until the batch is uniform- WO 2007/009161 PCT/AU2006/000989 10 Example 6 Ingredient Function Quantity (kg) Quinacridone Magenta Pigment Pigment 20kg Calcium Carbonate Extender 50kg Orotan 1124 (Rohm & Haas) Dispersant 4kg Functionalised polyacrylate copolymer (Anionic Dispersant) Surfynol CT-171 (Air Products & Chemicals Dispersant 4kg Inc),.Anionic Dispersant AC 2235 (Rohm & Haas] Binder 80kg Acrylic Dispersion Texanol (Eastman Chemical Company) - Coalescent 2kg Ester alcohol TT615 (Rohm & Haas) Rheology Modifier 1.5kg Alkali Swellable Rheology Modifier Acrysol ASE 60 (Rohrn & Haas) Thickener' 10kg Acrylic polymer containing carboxylic acid groups (Alkali Swellable Thickener) Acrysol DR72 (Robm & Haas) Rheology Modifier 2kg Alkali Swellable Rheology Modifier Propylene Glycol Freeze/thaw stabilizer 4kg Joncryl 142 (Johnson Wax Co) Auxiliary Binder 10kg Alkali Soluble Ink Polymer AMP or MEA to pH 9.3 Neutraliser Water q_.s. 200 L WO 2007/009161 PCT/AU2006/000989 11 Example 7 Ingredient Function Quany Arylamide Yellow Pigment 2G X 70 Pigment 20kg Orotan 1124 (Rohm & Haas) Dispersant 4kg Functionalised polyacrylate copolymer (Anionic Dispersant) Surfynol CT-171 (Air Products & Dispersant 4kg Chemicals Inc).Anionic Dispersant AC 1-1955 Binder 80kg (Rohm & Haas) Alkali Soluble Acrylic Dispersion Texanol (Eastman Chemical Co) Coalescent 2kg Ester alcohol TT615 (Rohm & Haas) Rheology Modifier 2kg Alkali Swellable Rheology Modifier Acrysol ASE 60 (Rohm & Haas) Thickener 10kg Acrylic polymer containing carboxylic acid groups (Alkali Swellable Thickener) Lucidene 361 (Rohm & Haas) Auxiliary Binder 10kg water-based polystyrene/acrylic emulsion (Alkali Soluble Ink Polymer) AMP or MEA to pH 9.3 Neutraliser Water q.s. 200L WO 2007/009161 PCT/AU2006/000989 12 Example 8 Ingredient Function Quantity (k Pthalo Green Pigment Pigment 20kg Calcium Carbonate Extender 50kg Orotan 1124 (Rohm & Haas) Dispersant 4kg Functionalised polyacrylate copolymer (Anionic Dispersant) Surfynol CT-171 (Air Products & Dispersant 4kg Chemicals Inc) Anionic Dispersant Acronal 290D (BASF) Binder 80kg Styrene/acrylic copolymer dispersion Texanol (Eastman Chemical Co) Coalescent 2kg Ester alcohol Acrysol DR72 (Rohm & Haas) Rheology Modifier 2kg Alkali Swellable Rheology Modifier Acrysol ASE 60 (Rohma & Haas) Thickener 10kg Acrylic polymer containing carboxylic acid groups (Alkali Swellable Thickener) Polyphobe TRl 17 (Union Carbide) Thickener 1kg Joncryl 142 (Johnson Wax Co) Auxiliary Binder 10kg Alkali Soluble Ink Polymer AMP or MEA to pH 9.3 Neutraliser Water q.s. 200L Compositions were prepared according to examples I to 8 and used under studio 5 conditions and outdoors to prepare artworks on conventional substrates using conventional palettes and brushes. It was found that "wet in wet" painting techniques could be exercised for a full day and in some portions of the artworks on a second day, provided that water sprays were used.

WO 2007/009161 PCT/AU2006/000989 13 Key to examples 9 - 31 Ingredient Manufacturer Quantity (kg) Surfynol CT-171 Air Products & Chemicals Dispersant (anionic dispersant) Inc Orotan 1124 Rohm & Haas Dispersant (anionic dispersant) Mergal K1 ON Troy Corporation Biocide Polyphase AF3 Troy Corporation Fungicide Foamaster NS-1 Henkel Defoamer Propylene glycol Shell Petroleum Freeze/thaw stability AMP-95 Dow Chemicals Neutraliser Primal SF-017 Rohin & Haas Binder Water dispersible acrylic polymer Acrysol TT-615 Rohm & Haas Rheology modifier (alkali swellable theology modifier) Acrysol DR-I Rohm & Haas Rheology modifier (alkali swellable rheology modifier) Viscalex HV-30 Ciba Specialty Chemicals Thickener Acrysol 1-62 Rohm & Haas Auxiliary binder (alkali soluble polymer) Omycarb-2 Omya-Southern Chemicals Extender (calcium carbonate) Air Products & Chemicals Non-foaming wetting agent Envirogen AD Surfactant Inc WO 2007/009161 PCT/AU2006/000989 14 EIxample 9 Ingredient Quantity Surfynol CT-171 1 Orotan 1124 1.5 Propylene Glycol 6 Mergal K1ON 0.3 Polyphase AF3 0.3 Foamaster NS- 1 0.5 AMP-95 4 Primal SF-017 85 Acrysol TT-615 1 Acrysol DR-i I Viscalex HV-30 8 Acrysol 1-62 10 Pigment: Merlin Super Coper 50 Water q.s. 200L Example 10 5 Ingredient Quantity (kg) Surfynol CT-171 2 Orotan 1124 3 Propylene Glycol 6 Mergal K1 ON 0.3 Polyphase AF3 0.3 Foamaster NS-1 0.5 AMP-95 5 Primal SF-017 85 Acrysol TT-615 1 Acrysol DR-1 1 Viscalex H-V-30 10 Acrysol 1-62 10 Pigment: Shepherd Green 260 100 Water g.s. 200L WO 2007/009161 PCT/AU2006/000989 15 Example 11 Ingredient Quantity (kg) Surfynol CT-171 0.5 Orotan 1124 1.5 Propylene Glycol 6 Mergal KION 0.3 Polyphase AF3 0.3 Foamaster NS-1 0.5 Omyacarb-2 50 AMP-95 5 Primal SF-017 85 Acrysol TT-61'5 1 Acrysol DR-i 1 Viscalex HV-30 12 Acrysol 1-62 10 Pigment: Red 3705 50 Water g.s. 200L Example 12 Ingredient Quantity (kg) Surfynol CT-171 0.5 Orotan 1124 1.5 Propylene Glycol 6 Mergal KI ON 0.3 Polyphase AF3 0.3 Foamaster NS-1 0.5 Omyacarb-2 50 AMP-95 . 5 Primal SF-017 85 Acrysol TT-615 1 Acrysol DR-I 1 Viscalex HV-30 12 Acrysol 1-62 10 WO 2007/009161 PCT/AU2006/000989 16 Pigment: Pink 304/80 17.5 Pigment: Red HFT 20 Water g.s. 200L Example 13 Ingredient Quantiy Surfynol CT-171 0.5 Orotan 1124 1.5 Propylene Glycol 6 Merga1K1ON 0.3 Polyphase AF3 0.3 Foamaster NS-1 0.5 Omyacarb-2 50 AMP-95 5 Primal SF-017 85 Acrysol TT-615 1 Acrysol DR-I 1 Viscalex HV-30 12 Acrysol 1-62 10 Pigment: RCL 595 36 Pigment: Pink 304/80 30 Water . q.s. 200L 5 Example 14 Ingredient Quantity (kg) Surfynol CT-171 0.5 Orotan 1124 1.5 Propylene Glycol 6 Mergal KION 0.3 Polyphase AF3 0.3 Foamaster NS-1 0.5 Omyacarb--2 50 AMP-95 4 Primal SF-017 85 WO 2007/009161 PCT/AU2006/000989 17 Acrysol TT-615 I Acrysol DR-i 1 Viscalex HV-30 8 Acrysol 1-62 10 Pigment: RCL 595 36 Pigment: Violet C10 6.2 Water g.s. 200L Example 15 Ingredient Quantity (kg) Surfynol CT-171 0.5 Orotan 1124 1.5 Propylene Glycol 6 Mergal Ki ON 0.3 Polyphase AF3 0.3 Foamaster NS- 1 0.5 Omyacarb-2 50 AMP-95 5 Primal SF-017 85 Acrysol TT-615 1 Acrysol DR-1 1 Viscalex HV-30 11 Acrysol 1-62 10 Pigment: Red Fbe 60 Water q.s. 200L 5 Example 16 Ingredient Quantity (kg) Surfynol CT-171 0.25 Orotan 1'124 0.75 Propylene Glycol 6 Mergal KI ON 0.3 Polyphase AF3 0.3 Foamaster NS- 1 0.5 WO 2007/009161 PCT/AU2006/000989 18 Omyacarb-2 25 AMP-95 5 Primal SF-017 85 Acrysol TT-615 1 Acrysol DR-1 1 Viscalex HV-30 10 Acrysol 1-62 10 Pigment: RCL 595 60 Pigment: Blue 2gax 6.5 Pigment Green 1211/79 10.5 Water q.s. 200L Example 17 Ingredient Quantity (kg) Surfynol CT-171 0.5 Orotan 1124 1.5 Propylene Glycol 6 Mergal KION 0.3 Polyphase AF3 0.3 Foamaster NS-1 0.5 Omyacarb-2 50 AMP-95 5 Primal SF-017 85 Acrysol TT-615 1 Acrysol DR-1 1 Viscalex HV-30 10 Acrysol 1-62 10 Pigment: RCL 595 75 Pigment: Yellow 1811/82 2 Pigment: Yellow C16 10 Water g.s. 200L WO 2007/009161 PCT/AU2006/000989 19 Example 18 Ingredient Quanty (kg) Surfynol CT-171 1.5 Orotan 1124 2.25 Propylene Glycol 6 Mergal KION 0.3 Polyphase AF3 0.3 Foamaster NS-1 0.5 AMP-95 4 Primal SF-017 85 Acrysol TT-615 1 Acrysol DR-I 1 Viscalex HV-30 11 Acrysol 1-62 10 Pigment: Black Oxide 318 70 Water g.s. 200L Example 19 5 Ingredient anti Surfynol CT-171 0.25 Orotan 1124 0.75 Propylene Glycol 6 MergalKION 0.3 Polyphase AF3 0.3 Foamaster NS-1 0.5 Omyacarb-2 25 AMP-95 4 Primal SF-017 85 Acrysol TT-615 1 Acrysol DR-1 I Viscalex HV-30 8 Acrysol 1-62 10 Pigment: RCL 595 150 Water q.s. 200L WO 2007/009161 PCT/AU2006/000989 20 Example 20 Ingredient Quantity (kg) Surfynol CT-171 1.5 Orotan 1124 2.25 Propylene Glycol 6 Merga K0N 0 .3 Polyphase AF3 0.3 Foamaster NS-1 '0.5 Eamp-95 4.5 Primal SF-0 17 85 Acrysol TT-615 l Acrysol DR-1 -I Viscalex HV--30 10 Acrysol I-62 10 Pigment: RS 2 10 68 |W4ater q.s. 200L 5 Examples 21-31 exemplify paint compositions of the invention that are more like a traditional gouaache. Example 21 Absolute matte: ultramarine blue Ingredient -Quantity (kg) Surfynol CT- 171 5.5 Orotan 1124 2.25 Propylene glycol 12 _ Mergal K10ON 0.2 Foamaster NS- 1 0.5 Envirogen ad surfactant 0.2 AMP-95 4 Primal SF-017 40 Acrysol TT-615 I WO 2007/009161 PCT/AU2006/000989 21 Acrysol DR-1 1 Viscalex HV-30 8 Acrysol 1-62 10.5 Pigment:-ultra blue premier RX 75 Water q.s. 200L Example 22 Absolute matte: napthol red light Ingredient Quantity (kg) Surfynol CT-171' 4.4 Orotan 1124 1.2 Propylene glycol 12 Mergal K1ON 0.2 Foamaster NS- 1 0.5 Envirogen AD surfactant 0.2 Omyacarb 2 60 AMP-95 4 Primal SF-017 40 Acrysol TT-615 1 Acrysol DR-1 I Viscalex HIV-30 6 Acrysol 1-62 10 Pigment: red fri1 50 Water g.s. 200L 5 Example 23 Absolute matte: cobalt turquoise Lht Ingredient Quantity (kg) Surfynol CT- 171 6 Orotan 1124 3 Propylene glycol 12 Mergal KION 0.2 Foamaster NS-1 0.5 Envirogen AD surfactant 10.2 WO 2007/009161 PCT/AU2006/000989 22 AMP-95 4 Primal SF-017 40 Acrysol TT-615 1 Acrysol DR-I 1 Viscalex HV-30 8 Acrysol 1-62 9 Pigment:irgacolor turquoise 22-5500p 100 Water q.s. 200L Example 24 Absolute matte: titanium white Ingredient Quantity (kg) Surfynol CT-171 4.4 Orotan 1124 1.2 Propylene glycol 12 Mergal KON 0.2 Foamaster NS- 1 0.5 Envirogen AD surfactant 0.2 Omyacarb 2 60 AMP-95 4 Primal SF-017 40 Acrysol TT-615 1 Acrysol ACRYSOL DR-1 1 Viscalex HV-30 8 Acrysol 1-62 10 Pigment: RCL 595 150 Water q.s. 200L 5 Example 25 Absolute matte: chromium green oxide Ingredient Quantity (kg) Surfynol CT-171 5.8 Orotan 1124 3.6 Propylene glycol 12 WO 2007/009161 PCT/AU2006/000989 23 Mergal K10ON 0.2 Foamaster NS-1 0.5 Envirogen AD surfactant 0.2 Omnyacarb 2 40 AMP-95 4 Primal SF-017 40 Acrysol TT-615 1 Acrysol ACRYSOL DR-1 1 Viscalex HV-30 8 Acrysol 1-62 10 Pigment: green oxide g6099 80 Water q.s. 200L Example 26 Absolute matte: pthalo blue (red shade) Ingredient Quantit ) Surfynol CT-171 4.5 Orotan 1124 1.2 Propylene glycol 12 Mergal K1ON 0.2 Foamaster NS-1 0.5 Envirogen AD surfactant - 0.2 Omyacarb 2 70 AMP-95 4 Primal SF-017 45 Acrysol TT-615 1 Acrysol DR-I 1 Viscalex HAV-30 6 Acrysol 1-62 10 Pigment: blue 303/81 30 Water q.s. 200L WO 2007/009161 PCT/AU2006/000989 24 Example 27 Absolute matte: pthalo green Ingredient Quantity (kg) Surfynol CT-171 4.5 Orotan 1124 1.5 Propylene glycol 12 Mergal KION 0.2 Foamaster NS- 1 0.5 Envirogen AD surfactant 0.2 Omyacarb 2 -70 AMP-95 4 Primal SF-017 40 Acrysol TT-615 1 Acrysol DR-I 1 Viscalex HV-30 6 Acrysol 1-62 10 Pigment: green 1211179 30 Water g.s. 200L Example 28 5 Absolute matte: burnt umber Ingredient Quantity (kg) Surfynol CT-171 5.6 Orotan 1124 2.4 Propylene glycol 12 Mergal.KION 0.2 Foamaster NS- 1 0.5 Envirogen AD surfactant 0.2 AMP-95 4 Primal SF-017 40 Acrysol TT-615 1 Acrysol DR-1 1 Viscalex HV-30 6 WO 2007/009161 PCT/AU2006/000989 25 Acrysol 1-62 8 Pigment: BU 524 80 Water q.s. 200L Example 29 Absolute matte: carbon black Ingredient Quantity (kg) Surfynol CT-171 4.3 Orotan 1124 0.9 Propylene glycol 12 Mergal K1ON 0.2 Foamaster NS-1 0.5 Envirogen AD surfactant 0.2 Omyacarb 2 50 AMP-95 4 Primal SF-017 40 Acrysol TT-615 1 Acrysol DR-i 1 Viscalex*HV-30 6 Acrysol 1-62 6.6 Pigment: black 43/77vb 30 Water g.s. 200L 5 Example 30 Absolute matte: burnt sienna Ingredient Quantity (kg) Surfynol CT-171 5.6 Orotan 1124 2.4 Propylene glycol 12 Mergal K1 ON 0.2 Foamaster NS-1 0.5 Envirogen AD surfactant 0.2 AMP-95 4 Primal SF-017 40 WO 2007/009161 PCT/AU2006/000989 26 Acrysol TT-615 1 Acrysol DR-1 1 Viscalex HV-30 7 Acrysol 1-62 10 Pigment: BS 310 80 Water g.s. 200L Example 31 Absolute matte: cobalt blue hue Ingredient Quantity (kg) Surfynol CT-171 4.5 Orotan 1124 1.5 Propylene glycol 12 Mergal K1ON 0.2 Foamaster NS-1 0.5 Envirogen AD surfactant 0.2 Omyacarb 2 70 AMP-95 4 Primal SF-017 45 Acrysol TT-615 1 Acrysof DR-I 1 Viscalex HV-30 8 Acrysol I-62 11.5 Pigment: RCL 595 9 Water q.s. 200L 5 . The present invention gives an artist considerably more time to develop an artistic piece while still retaining the benefits of using water-based acrylic paints (such as low amounts of volatile organic compounds, excellent colour retention and brushes being able to be washed out in water). The invention provides paint compositions with increased open time without loss of appropriate viscosity and with desirable final film 10 properties once the amine has evaporated.

WO 2007/009161 PCT/AU2006/000989 27 It will be appreciated by persons skilled in the art that numerous variations and/or modifications may be made to the invention as shown in the specific embodiments without departing from the spirit or scope of the invention as broadly described. The present embodiments are, therefore, to be considered in all respects as 5 illustrative and not restrictive.

Claims (23)

1. A water-based artists' paint composition consisting essentially of: at least one pigment in an effective amount to provide the desired pigmentation; at least one alkali soluble polymer in an amount effective to increase the open 5 time of the composition so that the paint composition remains workable and may be blended and altered, said polymer being selected from the group consisting of polymers soluble at ambient temperature and pressure in an aqueous solution having a pH of from 7 to 11; at least one substituted amine in an amount effective to adjust the pH to 7 to 11, 10 said amine selected from the group consisting of C 1 - 6 alcohol amines, C 1 - 6 alkyl C1-6 alcohol amines and mixtures thereof; a binding effective amount of at least one water dispersible acrylic polymer; and an effective amount of at least one alkali soluble or alkali swellable thickener.

2. The paint composition according to claim 1 wherein the at least one alkali 15 soluble polymer is soluble at ambient temperature and pressure in an aqueous solution having a pH of from 7.5 to 9.5.

3. The paint composition according to claim I or 2 wherein the at least one substituted amine is in an amount effective to adjust the pH to 7.5 to 9.5.

4. The paint composition according to any one of claims 1-3 wherein the weight 20 ratio of alkali soluble polymer to water dispersible acrylic polymer is in the range from 1:4 to 1:20.

5. The paint composition according to any one of claims 1-3 wherein the weight ratio of alkali soluble polymer to water dispersible acrylic polymer is in the range of 1:1 to 1:3. 25

6. The paint composition according to any one of claims 1-5 wherein the composition further comprises one or more dispersants, rheology modifiers, defoamers, coalescents or preservatives or mixtures thereof.

7. The paint composition according to any one of claims 1-6 wherein the at least one substituted amine is selected from the group consisting of aminomethylpropanol 30 (AMP), monoethanolamine (MEA), diethanolamine (DEA) and triethanolamine (TEA) and mixtures thereof.

8. A method of extending the open time of a conventional water-based acrylic artists' paint composition not including an alkali soluble polymer, the method consisting essentially of including in the conventional composition at least one alkali 35 soluble polymer in an amount effective to increase the open time of the composition so that the paint composition remains workable and may be blended and altered, said .. .... . . .. II .--. - I --- I--- ..... I' ICfA4 4 4 A~.. 29 polymer being selected from the group consisting of polymers soluble at ambient temperature and pressure in an aqueous solution having a pH of from 7 to 11; and at least one substituted amine selected from the group consisting of CI- 6 alcohol amines, CI- 6 alkyl CI-6 alcohol amines and mixtures thereof in an amount effective to adjust the 5 pH to 7 to l1.

9. A method of controlling the open time of a water-based acrylic artists' paint composition consisting essentially of at least one alkali soluble polymer in an amount effective to increase the open time of the composition so that the paint remains workable and may be blended and altered, and at least one substituted amine selected 10 from the group consisting of CI- 6 alcohol amines, CI- 6 alkyl CI- 6 alcohol amines and mixtures thereof in an amount effective to adjust the pH to 7 to 1, the method comprising periodically applying to the composition one or more of: (a) water; (b) a first medium comprising at least one alkali soluble polymer and at least one 15 substituted amine selected from the group consisting of Ci- 6 alcohol amines, CI- 6 alkyl C 1 . 6 alcohol amines and mixtures thereof in an amount effective to adjust the pH to about 7 to about I1; and (c) a second medium comprising at least one water dispersible acrylic polymer.

10. The method according to claim 9 wherein the water-based acrylic artists' paint 20 composition is as defined in any one of claims 1-7.

11. The method according to claim 8 wherein the composition further comprises one or more dispersants, rheology modifiers, defoamers, coalescents or preservatives and mixtures thereof.

12. The method according to claim 8 or I1 wherein the at least one alkali soluble 25 polymer is selected from the group consisting of polymers soluble at ambient temperature and pressure in an aqueous solution having a pH of from about 7.5 to 9.5.

13 The method according to any one of claims 8, 11 or 12 wherein the weight ratio of alkali soluble polymer to water dispersible acrylic polymer is in the range from 1:4 to 1:20. 30

14. The method according to any one of claims 8 or 1 1-13 wherein the weight ratio of alkali soluble polymer to water dispersible acrylic polymer is in the range from 1:1 to 1:3.

15. The method according to any one of claims 8 or 11-14 wherein the at least one substituted amine is selected from the group consisting of aminomethylpropanol 35 (AMP), monoethanolamine (MEA), diethanolamine (DEA) and triethanolamine (TEA) and mixtures thereof. - . I - - - - -~- -- s-" - -.-- . I A4~- 30

16. A process of making a water-based artists' paint composition consisting essentially of at least one alkali soluble polymer, at least one substituted amine, at least one water dispersible acrylic polymer, and at least one alkali soluble or alkali swellable thickener, the process comprising adding the at least one alkali soluble polymer in an 5 effective amount to increase the open time of the composition so that the paint composition remains workable and may be blended or altered, said polymer being selected from polymers soluble at ambient temperature and pressure in an aqueous solution having a pH of 7-1 1; and at least one substituted amine in an amount effective to adjust the pH to 7-l1, 10 said amine selected from CI- 6 alcohol amines, CI- 6 alkylCI- 6 alcohol amines and mixtures thereof; a binding effective amount of at least one water dispersible acrylic polymer; and an effective amount of at least one alkali soluble or alkali swellable thickener.

17. The process according to claim 16, further comprising adding at least one 15 pigment in an effective amount to provide a selected pigmentation.

18. The process according to claim 16 or 17 further comprising adding one or more dispersants, rheological modifiers, defoamers, coalescents or preservatives and mixtures thereof.

19. The process according to any one of claims 16-18 wherein the at least one alkali 20 soluble polymer is selected from polymers soluble at ambient temperature and pressure in an aqueous solution having a pH of 7.5-9.5.

20. The process according to any one of claims 16-19 wherein the weight ratio of alkali soluble polymer to water dispersible acrylic polymer is in the range from 1:4 to 1:20. 25

21. The process according to any one of claims 16-20 wherein the weight ratio of alkali soluble polymer to water dispersible acrylic polymer is in the range of 1:1 to 1:3.

22. The process according to any one of claims 16-21 wherein the at least one substituted amine is selected from the group consisting of aminomethylpropanol (AMP), monoethanolamine (MEA), diethanolamine (DEA) and triethanolamine (TEA) 30 and mixtures thereof.

23. A water based artists' paint composition substantially as herein before described with reference to any one of the foregoing Examples. I I-- - I------_--------~ '-- :- - - . - --- 4 - ; A11 C~ A I 1 A