NZ564136A - Colourant compositions - Google Patents

Abstract

Disclosed is a water based colouring composition adapted to be used with a material having substantially porous surface, which composition comprises a emulsion or solution of (a) at least one pigment; (b) at least one acrylate polymer or copolymer; (c) at least one silane-type binding agent; and the remainder being water; wherein the composition penetrates the substantially porous surface of the material, forming a physiochemical bond therewith.

Description

New Zealand Paient Spedficaiion for Paient Number 564136 Received at IPONZ on 4 November 2010 mcinnes patents PATENTS FORM NO. 5 NEW ZEALAND PATENTS ACT 1953 COMPLETE SPECIFICATION Colourant Compositions Applicant: We, Packaging Inks (NSW) Pty Ltd, a company incorporated under the laws of Australia of 159 Darley Street, Mona Vale NSW 2103, Australia Address for Service: Invention Title: Details of Priority Application: HODGKINSON McINNES PATENTS Patent & Trade Mark Attorneys Levels 21, 201 Elizabeth Street Sydney NSW 2000 HMcIP Ref: P20604NZ00 Colourant Compositions 2006906996 Australia 14 December 2006 hereby declare the invention for which I (or we) pray that a patent may be granted to me (or us) and the method by which it is to be performed, and particularly described in and by the following statement: /12 2007 15:04 FAX +61 2 9264 5154 Hodgkinson Mclnnes Pat. @1007/027 Received at IPONZ on 10 December 2007 COLOURANT COMPOSITIONS TECHNICAL FIELD The present invention relates to a colouring composition for various materials that s have some surface porosity, particularly granular materials such as landscaping materials. The composition is particularly useful for colouring quaitz or silica containing substances, such as stones, gravel and pebbles for example, the colouring of which are normally difficult to change. The colouring composition is a low viscosity, water based emulsion or solution containing a colourant pigment, a si lane-type binding to agent and an acrylate-type copolymer or polymer, such as a styrene-acrylate copolymer, as well as other optional ingredients.

BACKGROUND ART Garden landscapers and gardeners like to use a wide variety of materials to create new and interesting features in outdoor areas. Coloured landscaping materials, is especially stones, gravel, pebbles, and sand, for instance, can provide a complimentary backdrop or visual highlight.

In the past efforts have been made to make landscaping material available in a range of colours. For example, US patent application 2002/0006481 discloses a method for the surface coating of landscaping stones using a clear base solution of acrylic 20 copolymer and an organic solvent (such as toluene), that is coloured with an organic-soluble colourant. Also, UV stabilisers and mica/titanium dioxide gloss improvers can be included in the mixture. The coating is of a thick consistency that covers cipenings and blocks the pores in the stones, so that they must be heated prior to the application of the coating mixture in order to first drive moisture out of their pores. The coating as mixtures described also require special handling due to the unpleasant nature of the chemicals used and their noxious fumes.

Another approach, in US patent 6.338,871 describes a method of colouring silica sand, firstly by applying an air dried acrylic and vinyl emulsion, followed by spraying-on a coloured phenolic, polyester or epoxy coating at about 100 to 150 C. The colourant ■\ 0 DEC 2007 DFP.FIVED /12 2007 15:05 FAX +61 2 9264 5154 Hodgklnson Mclnnes Pat. @008/027 Received at IPONZ on 10 December 2007 •*> - J ~ is typically a soluble silicate dye. The coloured sand can then be applied as a coating to a surface. Titanium dioxide may be added to the mixture to alter the gloss of the coating.

US patent application 2004/0214000 relates to a special turf filler consisting of s rounded particles of crushed silica mixed with a colourant and with an acrylic based sealant. Organic solvents such as mineral spirits, ethylbenzene and xylene are used in the mixture. The coating is viscous and applied thickly enough so as to cover and remove any rough edges. The resulting coloured aggregate may be used on artificial playing surfaces or landscaped surfaces. xo US patent 3,099,574 relates to a method of coating crushed stones; and other mineral aggregates using a coloured epoxy or polyester resin that includes a promoter. Typically the coating is applied using a heated drum. The coloured stone can be used for stucco, plaster and asphalt facings and coatings.

US patent 2,934,455 relates to a process for colouring coarse aggregate using a is binder slurry consisting of sodium silicate, water, kaolin and colourant. Once; the coarse aggregate is coated with the slurry, it must be fired in a rotary kiln at 1000 ( F to dry and cure the binder.

These methods used in the prior art for colouring aggregate and the like have a number of disadvantages. A major problem is that they all form a continuous 'coating' 20 on the surface of the aggregate that is not closely bound to the surface, and over time this coating can flake or chip off'. Coatings used in the past typically need to include a UV stabilizer to minimise degradation of the coating by sunlight, which can otherwise cause the coating to separate from the substrate. The compositions used in these previously known methods also often include organic solvents which require special 25 handling due to their hazardous chemical properties, such as a tendency to generate noxious fumes. Some of the compositions also incorporate phenolic, polyester, epoxy or vinyl emulsions that require heating to cross-link and cure them, which increases the processing steps involved, and adds to their production costs. /12 2007 15:05 FAX +61 2 9264 5154 Hodgklnson Hclnnes Pat. @009/027 Received at IPONZ on 10 December 2007 DISCLOSURE OF THE INVENTION The present invention in one form concerns a water based colouring composition adapted for use on materials having some surface porosity, which composition comprises a emulsion or solution oft (a) at least one pigment; (b) at least one acrylate s polymer or copolymer; (c) at least one silane-type binding agent; and the remainder being water. Preferably the water based colouring composition also includes: (d) at least one coalescing agent The water based colouring composition may preferably be used on si ica or quartz containing materials, such as stones, gravel, pebbles, or sand, for example. It may also io be used to colour landscaping materials, such as woodchips, timber, concrete and pavers.

The acrylate polymer or copolymer may be an acrylate-styrene copolymer. The binding agent may be a silane-type binding agent selected from silanes or siloxanes. The coalescing agent may be a glycol ether compound. The colouring composition may is also contain a biocide. It may also contain any one or more of a defoamer, surfactant, suspension additive, or a neutraliser.

The water based colouring composition may preferably contains (a) at least one pigment in an amount of from 0.1 to 30% by weight; (b) at least one acrylate polymer or copolymer in an amount of from 1 to 50% by weight; (c) at least one si'&ne binding 2o agent in an amount of from 1 to 20% by weight; and the remainder being water, in an amount of from 30 to 90% by weight, whereby the amounts are selected u> add up to 100%. Preferably it also contains (d) at least one coalescing agent, in an amount of from 0.1 to 10 % by weight.

It may more preferably contain (a) at least one pigment in an amount of from 1 to 25 20% by weight; (b) at least one acrylate polymer or copolymer in an amount of from 4 to ! 5% by weight; (c) at least one si-lane binding agent in an amount of frorr 2 to 9% by-weight; and the remainder being water, in an amount of from 30 to 90% by weight, whereby the amounts are selected to add up to 100%. It may more preferably also contain (d) at least one coalescing agent, in an amount of from 2 to 6 % by w eight. /12 2007 15:06 FAX +61 2 9264 5154 Hodgklnson Mclnnes Pat. @010/027 Received at IPONZ on 10 December 2007 Most preferably, the water based colouring composition may contain (a) at least one pigment in an amount of from 2 to 5 % by weight; (b) at least one acrylate polymer or copolymer in an amount of from 4 to 9% by weight; (c) at least one silane binding agent in an amount of from 3 to 7% by weight; and the remainder being water, in an 5 amount of from 30 to 90% by weight, whereby the amounts are selected- to add up to 3 00%. Most preferably it also contains (d) at least one coalescing agent, in an amount of from 4 to 5 % by weight. Preferably, the water based colouring composition may have from 5% to 12% solids present by weight.

BEST MODES FOR CARRYING OUT THE INVENTION io In one broad form the invention concerns a water based colouring composition adapted for use on materials having some surface porosity, which comprises a emulsion or solution of: (a) at least one pigment; (b) at least one acrylate polymer or copolymer; (c) at least one silane-type binding or coupling agent; (d) preferably, at least one coalescing agent, and the remainder being water. is Preferably, the composition for use in the present invention has from 0.1 to 30 wt% of a pigment colourant present, and more preferably from 1 to 20 wt%, and most preferably from 2 to 5 wt%. This may be any pigment, or other type of, preferably insoluble, colourant that disperses in an aqueous solvent. Typically, the colourant may be chosen from the group comprising one or more of: azo pigments such as azo lake, 20 insoluble azo pigments, condensed azo pigments and chelate azo pigments; polvcyclic pigments such as phthalocvanine pigments, perylene pigments, perynone pigments anlhraquinone pigments, quinacridone pigments, dioxazine pigments, thioindigo pigments, isoindolinone pigments and quinopththalone pigments: dye lakes such as basic dye type lakse and acid dye type lakes; nitro pigments, nitroso pigments and 25 aniline black daylight fluorescent pigments.

Some examples of pigments that may be used include, for example, Carbon Black (Pigment Black 7, CI77266, such as "Printex 25" from the Degussa company), Phthalocvanine Blue (Pigment Blue 15:4, C174160, such as "Irgalite Blue GLVO" from the Ciba company), Cobalt Blue {Pigment Blue 28, CI77346, such as "Colanvl Oxide ao Blue "from the Clariant company), Phthalocyanine Green (Pigment Green 7. CI74260, such as "Hostaperm Green GNX" from the Clariant company), Quinacridone Red /12 2007 15:06 FAX +61 2 9264 5154 Hodgklnson Mclnnes Pat. @011/027 Received at IPONZ on 10 December 2007 (Pigment Red 122. CI73915. such as "Hostaperm Pink E" from the Clariant company), Diketopyrrolopyrrol Red (Pigment Red 254, such as "Hostaperm Red DPP'" from the Clariant company), Quinacridone Violet (Pigment Violet 19, CI73900, such as "Hostaperm red' E5B" from the Clariant company), Titanium Dioxide (Pigment White s 6, CI77891, such as "Tronox CR828" from the APS company), Iron Oxide Yellow (Pigment Yellow 42, CI77492, such as "Colanyl Oxide Yellow" from the Clariant company). Iron Oxide Red (Pigment Red 101 CI77491, such as "Colanyl Oxide Red" from the Clariant company), Bismuth Vanadate Yellow (Pigment Yellow j 84, such as "Colanyl Oxide Yellow" from the Clariant company), Dioxazine Violet (Pigment Violet io 23, CI51319. such as "Hostaperm Violet RL" from the Clariant company), or combinations of two or more of these pigments.

It is also preferred that the colourant selected for use in the invention is weatherproof and colour-fast, especially for use in colouring any landscaping materials to be used outdoors. This can be ascertained by simple trial and error. Combinations and i5 mixtures of two or more of these pigments may also be used to provide a Rail range of colours. Preferably a commercially available colourant is selected for use in the invention.

These commercial pigments will often contain additional ingredients, particularly a surfactant for instance, which acts as a dispersing agent for the colourant. Commonly, 20 the surfactant, if present, will comprise from 0.001 to 5 % by weight of the colourant composition in this situation. When this amount of surfactant is mixed into the composition of the invention in combination with the colourant, the proportion of other surfactant to be used in the composition of the invention can be reduced by a corresponding amount. ss The composition for colouring materials having some surface porosity, such as landscaping and other materials, according to the present invention will preferably comprise 1 to 50 wt%. or more preferably from 4 to 15 wt%, or most preferably from 4 to 9 wt% of an acrylate-type polymer or copolymer. Preferably the acrylate-type (co)polymer is a styrene-acrylate copolymer.

The (co)polymer may be chosen from any of those well known in the colourant, concrete coating, or printing, industries and are generally polymers or copolymers :07 FAX +61 2 9264 5154 Hodgklnson Mclnnes Pat. @012/027 Received at IPONZ on 10 December 2007 involving acrylic acid, or derivatives of acrylic acid. These include for example, alkylacrylate copolymers such as methacrylate copolymers. Further examples of some suitable copolymers include polyacrylic acids, and acrylic acid copolymers . Some other examples of suitable copolymers include, for instance, a (meth)acrylic acid copolymer such as styrene-acrylic acid copolymer, styrene-methylstyrene-acrylic acid copolymer, styrene-acrylic acid-(meth)acrylic acid ester copolymer ("ester" preferably denotes a lower alkyl ester where the number of carbon atom of an aikyl group is about I to 4,), styrene-methacrylic acid copolymer, styrene-methacrylic acid-(meth)acrylic acid ester copolymer, acrylic acid-(meth)acrylic acid ester copolymer or methacrylic acid-(meth)acrylic acid ester copolymer; a styrene copolymer such as styrene-acrylic acid, ester-styrene sulphonic acid copolymer, styrene-methacrylsulphonic acid copolymer or styrene-acrylic acid ester-allylsulphonic acid copolymer; and the like, These can be used alone or in mixtures.

One particularly preferred such polymer is a styrene-acrylate-methacrylate copolymer, obtained from the Rhodia PPMC Australia Pty Ltd company of Box Hill Victoria Australia, (or from Hexion Specialty Chemicals Australia Pty Ltd of Laverton Victoria Australia), under the brand name "Duramul DPI701" which an emulsion in water of a styrene-acrylate-methacrylate copolymer present in an amount of 30-60%, with minor amounts of benzyl alcohol (1-5%), ammonia (<1%) and remainder being water (30-60%).

The composition of the present invention preferably comprises 1 to 20 wt%, or more preferably from 2 to 9 wt%, or more preferably from 3 to 7 wt.%, of one or more silane-type binding or coupling agents. Typically these are chosen from the group generally comprising organo-silanes, or organo-siloxanes, their derivatives and combinations thereof, which function as water repellants, binding or coupling agents. Especially, those that bind other compounds to silica are preferred. The tenn '"binding agent" as used herein, also includes coupling agents.

The silane-type binding or coupling agents may be chosen from the group comprising aminoalkyl-functional organo-silanes, aminoalkyl-functional organo-siloxanes, alkenyl-functional organo-silanes, alkenyl-functional organo-siloxanes, epoxy alkyl-functional organo-silanes, epoxy alkyl-functional organo-siloxanes. /12 2007 15:07 FAX +61 2 9264 5154 Hodgklnson Mclnnes Pat. 0013/027 Received at IPONZ on 10 December 2007 methacryloyloxyalkyl-functional organo-silanes, methacryloyloxyalkvl-functional organo-siloxanes, hydroxy-functional organo-silanes, hydroxy-functional organo-siloxanes, alkoxy-functional organo-silanes, alkoxy-functional organo-siloxanes, acryloyl-functional organo-silanes, acryloxyl-functionai organo-siloxiines, alkyl-s functional organo-silanes, and alkyl-functional organo-siloxanes, for example.

In aqueous conditions, the organo-silane is normally present together with the equivalent organo-siloxanes, caused by hydrolysis of the silane. In particular, alkoxysilanes are hydrolysed to form silanol containing species, which ccridense with other such silanols to form siloxanes. io When a organo-silane is used it may, for example, be selected Iron the group consisting of 3-aminopropyl-trimethoxysilane, 3-aminopropyl-triethoxysilane, 3-amino-propylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, N-(2-amiiioethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyl-triethoxysilane, N-(2~aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethv])-3-arnino-' is propylmethyldiethoxysilane, N,N-di(2-aminoethyl)-3-aminopropyltrimethoxysilane, N,N-di(2-aniinoethyl)-3-am.inopropyltriethoxysilane, N,N-di(2-aminoethyi)-3-amino-propylmethvldimethoxysilane, N,N-di(2-aminoethyl)-3-aminopropylmethyIdiethoxy-silane, N-(2-aminoethyl)-N'-(2-aniinoethyl)-3-aininopropyltrimethoxysilane, N-(2-an:inoethyl)-N,-(2-aminoethyl)-3-aininopropy]trieihoxy.silane, N-(2-aminoc1hyl)-N'-(2-20 aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-N'-(2-amino-ethyl)-3-aminopropylrnethyldiethoxysilane, bis(triethoxysilylpropyl)ami ne, 3-(2-aminoethylamino)-propyltrimethoxysilane, bisOrimethoxysilylpropyl)amine, N-(2-aminobutyl)-3-aminopropyltriethoxysilane, N-(2-aminobutyl)-3-a]rinopropyi- triinethoxysilane, triethoxy(2,4,4-trimethylpentyl) silane and mixtures thereof.

Some preferred organo-silane binders are general alkylalkoxy-silanos: and their siloxane hydration derivatives where "alky!" and "alkoxy" generally have up to 10, or preferably up to 5 carbon atoms, especially, triethoxy(2,4,4-trimethy!pentyl) silane and its siloxane hydration derivatives.

Other organo-silane binder or coupling agents that may be selected for the 3c invention, are compounds commonly understood to act as silane coupling agents (see a booklet entitled "Silane Coupling Agents" by Gelest Inc of Morrisville PA USA (http:// /12 2007 15:08 FAX +61 2 9264 5154 Hodgklnson Mclnnes Pat. ®°J-nV°27 Received at IPONZ on 10 December 2007 . 9. www.gelest.com/ company/ InfoRequest.asp), 2006. Such coupling agents can form durable bonds between organic and inorganic materials, and have a general formula of R-{CH2)n-Si-X3 where R is an organofunctional group, (CH^n is a linker, Si is silicon, and X is a s hydrolysable group. X is typically, alkoxy, acyloxy. halogen, or amine. R is; normally a nonhydrolyzable organic radical.

One preferred organo-silane coupling agent is 3-(2-aminoethylamino)-propyI-trimethoxy-silane. Other coupling agents, especially amino-substituted alkyl tri-alkoxy silanes, may be used. As well, other coupling agents may be utilized, such as those 10 described in the Gelest booklet above.

It is preferred to use a combination of an alkylalkoxy-silane and its siloxane hydration derivatives, together with a minor proportion of an organo-silane coupling agent being 3-(2-aminoethylamino)-propyl-tri.methoxy-silane, or a similar such compound. is One particularly preferred silane compound binding agent is provided under the trade name "S1LRES BS 1001", which can be obtained from the Amtrade International coinpany, of Melbourne, Victoria, Australia. A similar product can also be obtained from the Wacker Company of the United States, under a similar trade name. This product is a silane/siloxane emulsion in water. It contains trietho>;y(2,4,4-20 frimethylpentyl) silane (CAS 35435-21-3) 25-50 wt%, and alkylalkoxysiloxarie 25-50 wt%, and 3-(2-aminoethylamino)-propyl-trimethoxy-silane 0.1-1 wt%, and o-i-tridecyl-o)-hydroxy-polyglycolether (CAS 9043-30-5) <5 wt%, (these ingredients comprising 45-55% of the emulsion), as well as water about 50%, and some ethanol arising from hydrolysis.

The composition may also contain a coalescing agent, especially one that is composed of a glycol compound. The coalescing agent appears to help with the penetration of the pigment mixture into the substrate, and to help improve the film forming ability of the acrylate polymer.

The coalescing agents used may be any that are well known in the ink manufacture industry. Some suitable examples include glycol ethers, such as- cx-tridecyl- :08 FAX +61 2 9264 5154 Hodgklnson Mclnnes Pat. 0015/027 Received at IPONZ on 10 December 2007 omega-hydroxy-polyglycol-ether, or ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether, and propylene glycol ri-butyl ether, and similar compounds; or nitrogen containing heterocyclic compounds, such as N-methyl-2-pyrrolidone; or alkanol amines. The coalescing agent may be used singly, or two or more may be used in combination. When used they preferably shouid comprise from 0.1 to 10 wt%, or more preferably from 2 to 6 wt%, and most preferably about 4 to 5 wt% of the composition.

Some suitable glycol ethers for use as coalescing agents, may be obtained under the trade names, "Celiosolve" for ethyl glycol ethers and ether acetates, "Carbitol" diethyl glycol ethers and ether acetates, "Arcosolv PTB" propylene glycol lertiary butyl ether. "Dowanol" (di)propylene glycol n-butyl ether, or "Rosstech Formula I19EC" glycol ethers and alkanolamines.

The composition may include a surfactant or dispersing agent, which may often be made available, at least partly, from the commercially available pigment component used in the composition. If present, then from 0.001 to 2 wt% surfactant, more typically about 0.1 wt% of surfactant, may be present in the total composition.

Examples of suitable non-ionic surfactants include polyoxyalkylene higher fatty acid esters, higher fatty acid esters of polyhydric alcohols and derivatives thereof, and higher fatty acid esters of sugars. More specific examples include glycerin fatty acid esters, polyglycerin fatty acid esters, propylene glycol fatty acid esters, pentaerythritol fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatly acid esters, polyoxyethylene glycerin fatty acid esters, polyethylene glycol fatty-acid esters, polyoxyethylene alkyl ethers, polyoxyethylene phytosterols, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene alkylphenyi ethers, polyoxyethylene castor oil, polyoxyethylene lanolin, polyoxyethylene lanolin alcohols, polyoxyethylene alkylamines, polyoxyethylene fatty acid amides and polyoxyethylene alkylphenyi formaldehyde condensation products. In a particularly preferred embodiment surfactant is polyoxyethylene lauryl ether, and polyalkykne oxide modified siloxanes. One or more than one such surfactant may be used. /12 2007 15:09 FAX +61 2 9264 5154 Hodgklnson Mclnnes Pat. iir^ki^ ®°1®/027 Received at IPONZ on 10 December 2007 Optionally, the composition may include further components. Typically the further components are chosen from the group comprising suspension additives, neutralizes, biocides, defbamers and combinations thereof.

Typically the composition may include some additional components that are sourced from the commercial pigment dispersions, which can include suspension additives, present in an amount of typically from 0.001 to 1 wt%, more commonly 0.001 to 0.1 wt% of the total composition. Some examples of suspension agents include Tego "Dispers 750W" (from the Tego company). "Bentone AD" (from the Elementis company), and "Rheolate 2001" (Elementis), and these are all additives used for suspension of pigments in water based compositions.

Typically the composition may also includes a neutralizer, often sourced from the pigment formulation, such as a basic or alkaline neutralizer, typically present from 0.001 to ! wt%. Usually, the neutralizer is an amine neutralizer such as ammonia or ammonium hydroxide.

The pigment formulation, and consequently the composition of the invention may additionally include from 0.001 to 1 wt% biocide, more typically 0.01 to 0.3 wt% and most preferably about 0.2 wt% of biocide. Examples of some suitable bioc>des include, "Nuosept 95", a bicyclic oxazolidine solution from Creanova Inc. or "Acticide RS" from Thorchem, which has the active ingredients of 2-Methyl-3(2H)-isothiazolone (0.37 %) and 5-Chloro-2-methyl-3(2H)-isothiazolone (1.11%). Other biocides may be used. The biocide may be added to the formulation of the invention so as to help prevent bacterial or other contamination of the formulation, and to help extend its shelf-life.

The pigment formulation, and consequently the composition of the invention may include from 0.001 to 2 wt% of defoamer, more preferably from 0.5 to 1 wt% of defoamer, Examples of antifoaming agents include "Tego Foamex 810" ( Goldsmith Chemical Co.), "Dapro Df 1161" (Elementis Specialty Chemicals). "Surfynol Df 75" (Air Products Inc.) , or "Toammaster" ( a hydrocarbon defoamer from ihe Cognis company), or mixtures thereof. Other defbamers may be used. Additional amounts, or a different defoamer, may be added to the formulation of the invention, to help prevent frothing and foaming, which can cause uneven colour distribution. /12 2007 15:09 FAX +61 2 9264 5154 Hodgklnson Mclnnes Pat. 0017/027 Received at IPONZ on 10 December 2007 In the composition of the present invention water may be present in an amount of from 30 to 95 wt%, or more preferably from 75 to 90 wt%, and most preferably from 80 to 90 wt%. The formulat ion may be produced and sold with 80 to 90% of water present ready for immediate use, or in another alternative, the formulation may be produced and 5 sold in a more concentrated form, and then diluted to the preferred proportion of water, prior to application to a substrate. The water may be normal tap water.

The proportions and amounts specified herein, apply to the commercially available constituents, which may contain added water.

Preferably, the amounts of total solids present in the ready-to-use formulation may io ideally be about 5% to 12%. However, a higher solids content may be used with concentrated formulations, which are intended to be further diluted before application. Lower solids content solutions are also possible, which tend to give lower colour intensities. The colouring effect of the specific pigments used will also have an impact of the proportion of solids present and dilution to be applied; some pigments are is naturally more intense than others. Generally the formulation should be applied in an aqueous solution of at least 1% or 2%, to obtain a reasonable colouring effec t, although "in some circumstances more dilute formulations may have a useful result. With concentrated formulations, intended for further dilution before use, a maximum of 25% or 30% of solids present in the concentrated mixture is preferred.

The colourant forms a special "physiochemical" type of bond with the material it is colouring, in the like manner of a stain. That is, the bond between the colourant and the landscaping material depends on both the physical and chemical interaction between the colourant and the substrate. Unlike coatings such as paints, stains tend not to flake or chip off a substrate. Furthermore there may often be no need for a UV stabiliser or 25 the like to avoid the tendency of chipping or flaking occurring under the influence of UV radiation. The present invention thus provides an integrated colour finish that is durable and protective whilst maintaining the natural texture of the substrate such as landscaping material. The compositions of the present invention have good penetration of the substrate, and better than with paints or the like, which reiy for then- colouring so effect on creating a surface coating around the substrate. /12 2007 15:10 FAX +61 2 9264 5154 Hodgklnson Mclnnes Pat. 0O18/O27 Received at IPONZ on 10 December 2007 The substrate, or material to be coloured, which has some surface porosity may be any natural or synthetic material, especially that which is for use in indoor or outdoor landscaping. Any material that contains silica, or similar material, is ideal for use with the invention.

The water based colouring compositions may be especially used on silica or quartz containing materials, such as on rocks, stones, gravel, pebbles or sand, or on materials that include these, such as concrete, pavers, or the like. These materials may be used as they are found, such as on river pebbles or sand, or these materials m&y be processed further, such as by crushing, cutting or with other treatments, or by sieving or to grading to create specific sizes and shapes for this material. These materials may have their surfaces be roughened to increase their porosity, if necessary, but generally, the natural surface, containing natural imperfections, will normally take well the colouring stains according to the invention. For example, natural materials such as quart?; pebbles may appear smooth to the naked eye, but as natural stones they actual!)' contain may is surface imperfections and microscopic pits and ridges which function well with the colourant compositions of the present invention.

The material to be coloured may form part of an existing building. Additionally, the material to be coloured may be any landscaping materials. Typically such landscaping materials may be particulate inorganic matter such as aggregate, pebbles or 20 sand, or particulate organic matter such as woodchips, bark or leaves, or other organic materials such as timber, either natural, or cut, or treated. Many natural organic materials have some silica within their structure, which allows them to work well with the present invention. It is an unexpected advantage of the invention that a whole range of distinct landscaping materials such as gravel, sand, woodchips and concrete pavers 25 may all be coloured a similar colour, or else according to a coordinated colour scheme, for use in gardens, or as decorative features in buildings or houses. Landscaping materials are intended in this document to refer to all materials that may be used in this industry, and include materials intended for outdoor use in gardens and the countryside, but also inside buildings, such as in or around pools, as decorative features, in indoor 30 gardens, and pots, or as floor or ground covering such as in garages. The coloured materials may also be used as roof covering such as on flat rooves to provide insulation and protection for roofing membranes. :10 FAX +61 2 9264 5154 Hodgklnson Mclnnes Pat. 0019/027 Received at IPONZ on 10 December 2007 Alternatively the material may be a continuous expanse of landscaping material such as a feature wall or path or the like. That is, the colourant may bo applied to concrete or concrete products such as Besser blocks, concrete pavers, mortar or render. Generally, it can be applied to the finished product, and give a good result. The colouring compositions have good water resistance, and may be used in swimming pools, water features, fountains, or the like, or as part of the surrounds for these.

Once the composition is applied to the landscaping materials, the water present can be driven off using applied heat, or just allowed to dry naturally, as the colourant forms a bond with the substrate or silica containing material. The special bond is sufficiently strong that subsequent applications of water by rain, washing, flooding, etc, does not appreciably dissolve the colourant or wash it off the substrate material, The composition may be applied by any convenient process such as spraying, dipping or brushing the colourant onto on to the substrate, such as of landscaping materials. The best method of application will depend on the nature of ihe substrate itself, and with landscaping material, an appropriate method that can be used with the quantities involved, and in the situation of the application, will be chosen. For example, loose particulate material such as aggregate could either be put in a net or sack and dipped in the colourant, or spread on screens in an auger screw or trammel system and sprayed, or placed in concrete mixers or agitators and sprayed, for instance.

One of the advantages of the composition for use in the method of the present invention is that it can be readily applied at ambient temperature and air dried. For faster production rates fan forced air or the like may be used to speed up the drying process. Typically, it is unnecessary to apply any additional heat, or radiation, or a promoter so as to initiate reaction between components in the composition or bonding between the colourant and the landscaping material or other substrate, and to dry the now coloured and bonded substrate.

The use of water as a solvent and major component of the composition also has the advantage of making the composition environmentally friendly and user friendly because it tends not to release toxic fumes, is non-flammable and has low toxicity. Furthermore water is readily driven out so as to easily dry the colourant. /12 2007 15:11 FAX +61 2 9264 5154 Hodgklnson Mclnnes Pat. 0020/027 Received at IPONZ on 10 December 2007 Another advantage of the composition of the present invention is that because of the special bonding with the substrate, the pores of the landscaping material are not blocked (as they would be by a traditional coating). Accordingly the method of the present invention provides a breathable finish that allows moisture to escape from 5 landscaping material. This means that the landscaping material does not hsve to be pre-treated to drive out moisture, and there are no freeze/thaw problems caused by trapped moisture that over time can cause degradation (for example, rotting) of organic landscaping materials, or crumbling of stone materials, for instance.

EXAMPLES io Various embodiments/aspects of the invention will now be described with reference to the following non-limiting examples.

Example 1 A composition was prepared having the following components: Component Amount (1) Pigment Composition - Aquatal Black BP 1100 7 wt% (2) Acrylate Polymer - Duramul DPI 701 wt(,/o (3) Binding Agent - Silres BS1001 3 wtc/o (4) Coalescing Agent - Butyl glycol ether 4 wt% (5) Biocide - Acticide RS 0.2 vvt % (6) Water 80.8 wt% The pigment composition component was a commercially obtained formulation, and contains minor amounts of other ingredients. /12 2007 15:11 FAX +61 2 9264 5154 Hodgklnson Mclnnes Pat. @021/027 Received at IPONZ on 10 December 2007 Examples 2 to 15 A number of colourant compositions, of differing colours and intensities were prepared in a similar manner to that of Example 1, having as the Acrylate Polymer -Duramui DP 1701 (6 wt%), the Binding Agent - Silres BS1001 (6 wt%), the Coalescing s Agent - Butyl glycol ether (4 wt%), and the Biocide - Acticide RS (0.2 wi%), but with a variation in the other components as shown in the following table: Example # Component (1) Pigment Amount of pigment Component (1) Amount of water Component (6) 2 Aquatel Process Blue BP 1400 3 wt% 8z-.8 wt% 3 Colanyl Oxide Red G500 3 wt% 84.8 wt% 4 Hostajet Magenta E-PT VP2690 2 wt% 85.8 wt% Colanyl Oxide Yellow BV500 3 wt% 84.8 wt% 6 Flexobrite Violet CI 0 3 wt% 84.8 wt% 7 Colonyl Oxide Yellow R500 3 wt% 84.8 wt% 8 Aquatal Black BP 1100 Flexobrite Violet C10 0.5 wt% 1.5 wt% 85.8 wt% 9 Aquatal Black BP 1100 1.5 wt% 86.3 wt% Colanyl Oxide Yellow BV500 Aquatel Process Blue BP1400 2.0 wt% 0.3 wt% 85.5 wt% 11 Flexobrite Green AD 3 wt% 84 .8 wt.% 12 Colanyl DPP Red GD 6 wt% 79.8 wt% 13 Colony! Oxide Blue CGR500 9 wt% 70.8 wt% 14 Colanyl Red HF35 6 wt% 7'7.8 wt% /12 2007 15:11 FAX +61 2 9264 5154 Hodgklnson Mclnnes Pat. @022/027 Received at IPONZ on 10 December 2007 Example Component (1) Amount of Amount of # Pigment pigment water Component (1) Component (6) Colanyl Oxide Red G500 9 wt% 76.8 wt% Example 16 A further example was prepared similarly to the previous ones: Component Proportion (1) Colouring agent:- Aquatal Black BP 1100'( from Taisons) wt% (2) Acrylate copolymer: -Duramul DPI701/25 (Hexion) 7 wt% (3) Silane binding agent:-Silres BS1001 (Wacker) wt% (4) Coalescing agent- Butyl glycol ether (Chemcentral) 4 wt% (5) Biocide: -Actcide RS (Thorchem) 0.2 wl% (6) Water 68.8% Preparation Examples In a commercial blender the styrene/acrylate copolymer, and silane binding agent, were mixed together with half the water. After the mixing until all the components were distributed evenly, the other half of the water was added, together with the glycol ether coalescing agent, and the resulting mixture blended at low speed for about 15 minutes.

Claims (19)

10/12 2007 15:12 FAX +61 2 9264 5154 Hodgklnson Mclnnes Pat. @023/027 Received at IPONZ on 10 December 2007 -18- With continuous stirring, one third of the aqueous solution from the: previous step was added portion-wise to the carbon black in a blender. Another third of the aqueous solution was added and blended at low speed for about 5 minutes. After any resulting foaming subsides, the biocide and the remaining third of the aqueous solution was 5 added and stirred at low speed for about another 5 minutes. The solution from this step can be applied to a substrate, such as to a quantity of quartz aggregate. One method of application can involve spreading the substrate on a moving bed. The solution can be applied at ambient temperature from fixed spray nozzles located above the moving bed. The coloured aggregate can then be allowed to io air dry. For faster production rates drying can be accelerated by fan forced air. An alternative application method involves dipping quantities of the substrate, such as of quartz aggregate, into the colourant composition. The stained aggregate is then allowed to air dry, or may be forced using hot air. Note that the word 'comprising' and its variants as used in this description is to be i s interpreted to allow additional ingredients, unless specifically indicated otherwise. It will be apparent that obvious variations or modifications may be made in accordance with the spirit of the invention that are intended to be part of the invention, and any such obvious variations or modification are therefore within the scope of the invention. INDUSTRIAL APPLICABILITY so The covering composition is useful for creating a colourful bonded layer around porous materials, especially landscaping materials, and most preferably to stones, or quartz containing materials, to provide coloured materials, which have decorative and aesthetic utility. Received at IPONZ on 4 November 2010 - 19 - CLAIMS:

1. A water based colouring composition when used with a material having substantially porous surface, which composition comprises a emulsion or solution of: (a) at least one pigment; (b) at least one acrylate polymer or copolymer; (c) at least one silane-type binding agent; and the remainder being water; wherein the composition penetrates the substantially porous surface of the material, forming a physiochemical bond therewith, thereby providing the material with an integrated colour finish without altering any surface properties of the material.

2. The water based colouring composition of claim 1, which also includes: (d) at least one coalescing agent

3. The water based colouring composition of claim 1, which is adapted for use on silica or quartz containing materials.

4. The water based colouring composition of claim 3, which is adapted for use on stones, gravel, pebbles or sand.

5. The water based colouring composition of claim 1, which is adapted for use on landscaping materials.

6. The water based colouring composition of claim 5, which is adapted for use on woodchips, timber, concrete, or pavers.

7. The water based colouring composition of claim 1, wherein the acrylate polymer or copolymer is an acrylate-styrene copolymer.

8. The water based colouring composition of claim 1, wherein the binding agent is a silane-type binding agent selected from silanes or siloxanes.

9. The water based colouring composition of claim 2, wherein the coalescing agent is a glycol ether compound.

10. The water based colouring composition of claim 1, which also contains a biocide. Received at IPONZ on 4 November 2010 -20 -

11. The water based colouring composition of claim 1, which also contains any one or more of: a defoamer, surfactant, suspension additive, or a neutraliser.

12. The water based colouring composition of claim 1, which contains (a) at least one pigment in an amount of from 0.1 to 30% by weight; (b) at least one acrylate polymer or copolymer in an amount of from 1 weight; (c) at least one silane binding agent in an amount of from 1 to 20% and the remainder being water, in an amount of from 30 to 90% by weight, whereby the amounts are selected to add up to 100%>.

13. The water based colouring composition of claim 12, which also contains : (d) at least one coalescing agent, in an amount of from 0.1 to 10 % by weight

14. The water based colouring composition of claim 12, which contains (a) at least one pigment in an amount of from 1 to 20%> by weight; (b) at least one acrylate polymer or copolymer in an amount of from 4 to 15% by weight; (c) at least one silane binding agent in an amount of from 2 to 9% by weight; and the remainder being water, in an amount of from 30 to 90% by weight, whereby the amounts are selected to add up to 100%.

15. The water based colouring composition of claim 14, which also contains : (d) at least one coalescing agent, in an amount of from 2 to 6 % by weight

16. The water based colouring composition of claim 14, which contains (a) at least one pigment in an amount of from 2 to 5 % by weight; (b) at least one acrylate polymer or copolymer in an amount of from 4 to 9% by weight; (c) at least one silane binding agent in an amount of from 3 to 7% by weight; and the remainder being water, in an amount of from 30 to 90% by weight, whereby the amounts are selected to add up to 100%.

17. The water based colouring composition of claim 16, which also contains : (d) at least one coalescing agent, in an amount of from 4 to 5 % by weight to 50%) by by weight; Received at IPONZ on 4 November 2010 -21 -

18. The water based colouring composition of claim 1, which has from 5% to 12% solids present by weight.

19. A water based colouring composition, substantially as herein described with reference to any one of the Examples.