FI127636B

FI127636B - An aqueous universal colourant composition and a method for tinting a base paint

Info

Publication number: FI127636B
Application number: FI20175348A
Authority: FI
Inventors: Juha Taivainen; Asya Yurchenko; Olga Yurchenko; Oleg KUZMIN
Original assignee: Tikkurila Oyj
Priority date: 2017-04-13
Filing date: 2017-04-13
Publication date: 2018-11-15
Also published as: WO2018189426A1; CN110494515A; EA039547B1; EA201992458A1; EP3609963A1; EP3609963A4

Abstract

The present disclosure provides an aqueous universal colourant composition comprising water in the range of 20–65% (w/w), pigment(s) in the range of 1.8–60% (w/w), dispersing system in the range of 2–30% (w/w), one or more polymeric OH-functional humectant(s) in the range of 3–12% (w/w), optionally inorganic filler(s) in the range of 1–43% (w/w), wherein the composition contains 0.5% or less of semi-volatile organic compounds (SVOC), preferably 0.35% or less and wherein the polymeric OH-functional humectant is a polyether humectant having a mean average molecular weight of about 1500 g/mol. The present disclosure also provides a method for tinting a base paint.

Description

AN AQUEOUS UNIVERSAL COLOURANT COMPOSITION AND A METHOD FOR TINTING A BASE PAINT

Field of the application

The present application relates to aqueous universal colourant compositions and to a method for tinting a base paint.

Background

Colourant compositions, such as colourant pastes or colourants, are stable, liquid concentrates, in which the colour and colour strength are controlled. To produce a tinted paint, colourants are added to a base paint according to a previously determined formula. This is normally a task for a volumetric dispensing machine, which may be operated manually or automatically. Once the colourant has been added, the mixture is blended in a mixer, after which the paint is ready for use. The whole process takes only a few minutes. The tinting may be carried out for example in a tinting machine at a retail store, wherein a base paint is tinted into a desired colour, hue, tint or shade. The term “tint” specifically refers to a colour which is obtained when a small amount of colourant is added to a base paint, such as a white base paint. The colourants usually comprise one or more pigments, a solvent, and one or more additives such as dispersing agents, wetting agents, defoamers, biocides, fillers and the like. Universal colourants refer to such colourants which may be used for both solvent and waterborne paints and coatings, such as alkyd and latex paints and coatings.

Some volatile organic compounds (VOC) are harmful to human health and environment and are not desired in colourants and paints. They also impact the indoor air quality which may cause human health effects like irritation in eyes, throat and nose and nausea among others. A specific group of volatile organic compounds are semivolatile organic compounds (SVOC), which include compounds with broad chemical properties and structural features. SVOCs tend to have a higher molecular weight and higher boiling point temperature than other VOCs. Examples of semivolatile organic compounds include hydrocarbons, aldehydes, ethers, esters, phenols, organic acids, ketones, amines, amides, nitroaromatics, PCBs, PAHs, phthalate esters, nitrosamines, haloethers and trihalomethanes. The health effect of a specific SVOC depends on its chemical nature and on the degree of exposure,

20175348 prh 06 -09- 2018 which can occur through different routes such as oral, inhalation, or dermal, or a combination thereof.

Harmful compounds providing VOCs or SVOCs have been used in colourant compositions, for example in the additives or other agents present in the compositions, such as agents affecting to the rheological properties such as viscosity, drying or other properties of the colourant compositions. There exists a need to obtain colourant compositions having a very low VOC, and especially a very low SVOC content to improve indoor air quality and health and safety for humans 10 and environment. However, at the same time there exists a need to maintain or improve the physical properties of the compositions, such as rheological properties, drying properties or other properties.

WO 2017/029290 A1 discloses aqueous, low-VOC/SVOC universal pigment 15 preparations comprising a pigment component; a water-soluble, nonionic, surfaceactive additive comprising a copolymer formed from a vinyl monomer and from an ethylenically unsaturated monomer selected from the group consisting of monocarboxylic esters, dicarboxylic esters, monocarboxamides, and dicarboxamides, the vinyl monomer and/or the ethylenically unsaturated monomer 20 containing an N-containing group with pigment affinity; a phosphoric or phosphonic ester, and optionally customary additives. The preparations may comprise humectants, such as glycerol ethoxylates having a molecular weight of about 200 to about 1 000 g/mol.

US 2013/0338253 A1 discloses aqueous copolymer dispersions for a variety of uses, including coating compositions or binders for plasters and paints. US 2013/0338253 A1 is silent about colourants.

Summary

The present application provides an aqueous universal colourant composition comprising

-water in the range of 20-65% (w/w),

-one or more pigment(s) in the range of 1.8-70% (w/w),

-dispersing system in the range of 2-30% (w/w),

-one or more polymeric OH-functional humectant(s) in the range of 3-12% (w/w), -optionally one or more inorganic filler(s) in the range of 1-43% (w/w),

20175348 prh 06 -09- 2018 wherein the composition contains 0.5% or less of semi-volatile organic compounds (SVOC), preferably 0.35% or less and wherein the polymeric OH-functional humectant is a polyether humectant having a mean average molecular weight of about 1500 g/mol.

The present application provides a method for tinting a base paint, the method comprising

-providing a base paint,

-providing the aqueous universal colourant composition,

-adding an amount of the aqueous universal colourant composition to the base paint, and

-mixing to obtain a tinted paint.

One example provides a paint or a coating obtained by tinting a base paint with the 15 aqueous universal colourant composition.

The main embodiments are characterized in the independent claims. Various embodiments are disclosed in the dependent claims. The embodiments recited in dependent claims and in the specification are mutually freely combinable unless 20 otherwise explicitly stated.

In the embodiments a unique set of dispersing and wetting agents or combinations thereof or one or more dispersing and wetting additives, herein called as dispersing system, are used to give the colourants the best colour strength, good compatibility 25 with various paint types and a long term stability. Wetting and dispersing additives as used in the embodiments combine both mechanisms of action in one product, i.e. they are both wetting and stabilizing agents.

In addition the raw materials of the dispersing system are chosen to give a low 30 SVOC content to improve the indoor air quality and health and safety for humans and environment.

The dispersing system used in the colourants was chosen so that compatibility with both solventborne and waterborne basepaints was achieved and no flocculation of 35 pigment does occur. This was tested with a rub-out test and measuring the difference in the dry film from the rubbed-out surface and from the not rubbed out surface. The dispersing system also keeps the colourant viscosities stable and

20175348 prh 06 -09- 2018 ensures the excellent behaviour in tinting machines. The settling or sedimentation of the composition is decreased.

The rheology of the obtained colourant composition is suitable for point of sale 5 dispensers as well as for in-plant use. Unique rheology of the colourants was formed by the combination of the specific thickener and inorganic rheology modifier in combination with the dispersing system selected so that colourants maintain stable rheology and show improved stability during storage and during use in tinting equipment.

Further, components most affecting the SVOC content of the colourants, such as the dispersing and wetting additives and the humectant, used in the embodiments were chosen to provide a minimum amount of SVOC. As the SVOC amount is very low in colourants, for example 0.35% or 6 g/l according to the measurements, the 15 colourants do not add the amount of SVOC of the base paints in significant amounts.

For example when 10% (v/v) of colourant according to the embodiments including maximum of 6 g/l of SVOC is added to a base paint with SVOC of 2.5 g/l, it increases the SVOC only by about 0.3 g/l. Especially the dispersing and wetting additives do not substantially contain SVOC or a source of SVOC.

As the VOC and SVOC contents are very low, it means that the solvent of the colourant composition is mainly or only water, which will evaporate quickly from the paint film. If SVOCs were present, they would evaporate slower thus slowing down the film formation of the paint, especially with solventborne alkyd paints.

A noticeable difference, in addition to the low SVOC content, between the embodiments and the universal colourants used as a comparison, was the better drying, especially in alkyd paints. For example many universal colourants include low molecular weight glycols, such as ethylene glycols or propylene glycols and 30 derivatives thereof, which reduce drying. Additives, such as dispersing and wetting agents, and humectants, used in the embodiments do not preferably contain any such glycols which are known to reduce drying. The selected components, including the dispersing and wetting system, humectants, thickeners and rheology modifiers, were selected to be compatible with each other.

20175348 prh 06 -09- 2018

Detailed description

In this specification, percentage values, unless specifically indicated otherwise, are based on weight (w/w). If any numerical ranges are provided, the ranges include 5 also the upper and lower values. The percentages of the ingredients disclosed herein are percentages of the total composition.

The universal colourant composition disclosed in the embodiments is provided as a product, more particularly as a dispersion, which is used for tinting a base paint to 10 a desired colour, usually as desired by a customer at a retail store or the like. A predetermined amount of one or more colourant compositions is/are dosed into an amount of base paint, and the colourant composition is mixed with the base paint, for example in a dispenser or a shaker, to obtain a tinted paint having a desired colour, shade, hue or tint.

The colourants can be added to waterborne and solvenborne paints, for example to acrylic, alkyd, vinyl-acrylic paints or vinylacetate/ethylene (VAE) emulsion paints. The universal colourant composition is suitable for use in indoor and outdoor paints.

The base paints are products generally provided at a retail store. A base paint may contain polymeric binder(s), pigment(s), filler(s), solvent(s) and additive(s). The pigment may be included to provide a general base colour range, such as white, semi-white or clear. For example a white base paint may contain titanium dioxide as a pigment, and a clear base paint may not contain any pigment at all. This base 25 paint is then tinted into a desired colour. The base paints may be waterborne or solventborne, and a universal colourant composition is compatible with the both base paint types, so there is no need to provide separate colourant compositions for different types of base paints.

Generally a colourant is added to a base paint from a dispenser, which may be a device arranged to dose the colourants to the base paint. In the dispenser a colourant may stay from few weeks to several months or even longer periods, depending on how often paint is tinted with dispenser and which colours are made. In dispensers there is a mechanical mixing to keep colourant homogenized in the 35 canisters in order to achieve repeatable colours. However, one problem with the existing colourants is that their viscosity, colour shade and strength may change during the stay in the dispenser due to mixing of colourant in the canister.

20175348 prh 06 -09- 2018

One example provides an aqueous universal colourant composition comprising -water in the range of 20-65% (w/w),

-one or more pigment(s) in the range of 1.8-70% (w/w),

-one or more dispersing agent(s) and optionally one or more wetting agent(s), or a 5 dispersing system, in the range of 2-30% (w/w),

-one or more polymeric humectant(s),

-optionally one or more antifoaming agent(s),

-optionally one or more inorganic filler(s), wherein the composition contains 1% or less of semi-volatile organic compounds 10 (SVOC), preferably 0.5% or less.

-one or more pigment(s) in the range of 1.8-70% (w/w),

-one or more dispersing agent(s) and optionally one or more wetting agent(s), or a dispersing system in the range of 2-30% (w/w),

-one or more organic thickener(s) in the range of 0.1-3.0% (w/w),

-optionally one or more antifoaming agent(s),

-optionally one or more inorganic filler(s), wherein the composition contains 1% or less of semi-volatile organic compounds (SVOC), preferably 0.5% or less.

-one or more pigment(s) in the range of 1.8-70% (w/w),

-one or more inorganic and/or particulate rheology modifier(s) in the range of 0.11.5% (w/w),

-optionally one or more antifoaming agent(s),

-one or more pigment(s) in the range of 1.8-70% (w/w),

20175348 prh 06 -09- 2018

-optionally one or more dispersing agent(s) and optionally one or more wetting agent(s), or a dispersing system, in the range of 2-30% (w/w),

-optionally one or more polymeric humectant(s),

-one or more organic thickener(s) in the range of 0.1-3.0% (w/w), and/or

-optionally one or more antifoaming agent(s),

The compositions recited in previous, or other compositions recited in this disclosure, may be combined, and the compositions may contain other additional substances or features disclosed herein. In general the compositions disclosed herein, and the combinations thereof, may contain further additives customary of colourant compositions, for example in an amount in the range of 0-20% (w/w), 010% (w/w), or 1-20% (w/w), or 1-10% (w/w) or 1-5% (w/w). The sum of the percentages of the substances makes 100% (w/w). A substance may refer to an agent or an additive, or a combination of such agents and/or additives.

The colourant composition is aqueous, which means that it contains water as a solvent. In general the water content of the composition may be at least 10% (w/w), more particularly at least 15% (w/w) or at least 20% (w/w). The water content of the composition is in the range of 20-65% (w/w), such as in the range of 20-60% (w/w), 23-61% (w/w), or 25-60% (w/w). The aqueous colourant composition does not contain substantial amounts of organic solvents, such as less than 1 % (w/w), or less than 0.5% (w/w), or even less than 0.1% (w/w), or it does not contain any organic solvents. Preferably water is the only solvent in the colourant composition.

The colourant composition contains one or more pigment(s). The amount of the pigment(s) in the composition may be in the range of 1-70% (w/w), or 1-60% (w/w), such as in the range of 1.8-70% (w/w), 1.8-60% (w/w), for example in the range of 1-50% (w/w), 1-40% (w/w), 1-30% (w/w), 1-20% (w/w), 10-70% (w/w), 10-60% (w/w), 10-50% (w/w), 10-40% (w/w) or 10-30% (w/w). In one example the pigment comprises one or more organic pigment(s), one or more inorganic pigment(s) or a combination thereof. In one example the pigment comprises at least one organic pigment and at least one inorganic pigment. The organic pigment may be selected for example from monoazo pigments, diazo pigments, diazo condensation

20175348 prh 06 -09- 2018 pigments, anthanthrone pigments, anthraquinone pigments, anthrapyhmidine pigments, quinachdone pigments, quinophthalone pigments, diketopyrrolopyrrole pigments, dioxazine pigments, isoindoline pigments, isoindolinone pigments, isoviolanthrone pigments, metal complex pigments, perinone pigments, perylene 5 pigments, phthalocyanine pigments, pyranthrone pigments, pyrazoloquinazolone pigments, thio indigo pigments, and tharylcarbonium pigments. The inorganic pigment may be selected for example from white pigments, such as titanium dioxide, zinc white, pigment grade zinc oxide; zinc sulphide, lithopone; black pigments such as iron oxide black, iron manganese black, spinel black, carbon black; chromatic 10 pigments such as chromium oxide, chromium oxide hydrate green; chrome green, cobalt green, ultramarine green, cobalt blue, ultramarine blue, manganese blue, ultramarine violet, cobalt violet, manganese violet, red iron oxide, cadmium sulfoselenide, cerium sulphide, molybdate red, ultramarine red, brown iron oxide, mixed brown, spinel phases and corundum phases, chromium titanium yellow, 15 chrome orange, cerium sulphide, yellow iron oxide, nickel titanium yellow, chrome yellow and bismuth vanidate. Examples of suitable commercial pigments by their Color Index Generic names include PW6, PBk7, PR101, PR254, PY42, PO73, PR122, PY74, PY138, PB15:3, PG7, PG17, and PV23.

In general the preparation of a pigment dispersion proceeds in steps such as pigment wetting, grinding of pigment particles and stabilization of the pigment particles. Wetting agents are substances which decrease surface or interfacial tension and improve the wetting of solids, thereby acting as surfactants. Dispersing agents prevent particles flocculating by various mechanisms. Wetting and 25 dispersing additives as used in the embodiments combine both mechanisms of action in one product, i.e. they are both wetting and stabilizing agents.

The colourant composition contains a dispersing system which contains one or more dispersing agent(s) and/or one or more wetting agent(s). In one example the 30 dispersing system contains one or more dispersing agent(s) and one or more wetting agent(s). In one embodiment the dispersing system contains one or more dispersing and wetting additive(s). The amount of the dispersing system in the composition may be in the range of 2-30%, more generally in the range of 3-28%. In one example the composition contains dispersing system in the range of 8.535 22% (w/w). In one example the composition contains dispersing system in the range of 3-15% (w/w). In one example the composition contains dispersing system in the range of 3.4-5% (w/w).

20175348 prh 06 -09- 2018

The dispersing system refers to additives which are used in the dispersion process of the composition, in which solid particles, such as pigment and/or filler particles, are distributed and stabilized in a liquid. The dispersing system contains preferably at least one dispersing and wetting additive. A “dispersing and wetting additive” 5 comprises both wetting and dispersing functionalities in one substance or product, such as in one molecule. Such additives are amphiphilic compounds, i.e. they are both hydrophilic and lipophilic. Their structure allows them to enable or facilitate dispersion of pigments and fillers in the solvent. The dispersing and wetting additives may be categorized according to the head group as anionic, cationic, 10 amphoteric and non-ionic types. A dispersing and wetting additive contains one or more adhesion group(s), which have an effect to the dispersing and wetting effectiveness. Adhesion groups, also called as pigment affinic groups, are functional groups which have a special affinity for pigment surfaces. The pigment affinic groups cause adsorption of the additives upon the pigment surface. A pigment affinic group 15 may comprise carboxylic acid, amine, such as tertiary amine, isocyanate or derivatives thereof, or a salt structure which is produced by neutralisation of amine moieties with a mixture of acid-functional polymers. The dispersing and wetting additives may be high molecular weight polymeric dispersing and wetting additives, which contain a considerably large number of pigment affinic groups.

Such additives provide complete deflocculation and differ from the conventional low molecular weight analogs through molecular weight sufficiently high to allow the attainment of resin-like character.

In the dispersion process the solid particles are first wetted. To lower the surface or 25 interfacial tension of the liquid to enhance the wetting, a wetting functionality is required. A wetting agent in general contains a hydrophobic tail and a hydrophilic head. As the solid particles attract each other, energy is needed to separate the particles from each other in the next step of the dispersion process to prevent flocculation. Dispersing functionality is required to prevent the flocculation and to 30 stabilize the particles by various mechanisms, such as electrostatically or sterically.

In one example the colourant composition contains at least two different dispersing and wetting additives.

The dispersing and wetting additive may be an oligomer or a polymer. In one 35 example the dispersing and wetting additive is a polymeric dispersing and wetting additive. Such products generally have a greater molecular weight than conventional wetting or dispersing agents, such as a molecular weight of 1500 g/mol or more, or 2000 g/mol or more. They are suitable for both organic and inorganic

20175348 prh 06 -09- 2018 pigments. In one example the dispersing and wetting additive comprises a copolymer containing pigment-affinic blocks and binder-compatible blocks, such as block copolymer or a gradient copolymer. In one example the dispersing and wetting additive comprises lecithin. Lecithins are usually phospholipids, composed of 5 phosphoric acid with choline, glycerol or other fatty acids usually glycolipids or triglyceride. Glycerophospholipids in lecithin include phosphatidylcholine, phosphatidylethanolamine, phosphatidylinositol, phosphatidylserine, and phosphatidic acid. Lecithins are amphoteric.

In one example the dispersing and wetting additive comprises phenyl polymer with epoxy monoalkyl esters. Such a dispersing and wetting additive is especially compatible with organic pigments. In one example the dispersing and wetting additive comprises a (block) copolymer with pigmentic affinic groups. Such a dispersing and wetting additive is especially compatible with inorganic pigments.

In one example the dispersing and wetting additive comprises lecithin, such as soy lecithin. In one example the dispersing and wetting additive comprises ethoxylated fatty acid. In one example the dispersing agent comprises 1-propanaminium, 3amino-N-(carboxymethyl)-N,N-dimethyl, N-C8-18(even numbered) acyl 20 derivatives, such as C8-18(even numbered) alkylamidopropyl betain.

In one embodiment the dispersing system comprises one or more dispersing and wetting additive(s) selected from a modified (e.g. OH modified) polyether or polyester with pigment affinic group(s), such as hydroxyl functional carboxylic acid 25 ester or ether with pigment affinic group(s), polyether phosphate or phenylpolymer with epoxy, monoalkyl esters; copolymer with pigment-affinic group(s); block copolymer with pigment affinic group(s); poly(oxy-1,2-ethanediyl), alpha-isotridecylomega-hydroxy-, phosphate; ethoxylated fatty acid (non-ionic), such as hcinoleic acid polyglycol ester; 1-propanaminium, 3-amino-N-(carboxymethyl)-N,N-dimethyl30 , N-C8-18(even numbered) acyl derivatives (amphoteric); and lecithin, such as soy lecithin. The soy lecithin may be also defined as a combination of diglycerides of fatty acids linked to choline ester of phosphoric acid.

In one example the dispersing system comprises one or more dispersing and 35 wetting additive(s) selected from a copolymer with acidic groups (such as having acidic value of about 101 mg KOH/g); a block copolymer with pigment affinic groups (such as having amine value of about 3 mg KOH/g); phenyl polymers with epoxy, monoalkyl esters; lecitins; ethoxylated fatty acids; 1-propanaminium, 3-amino-N

20175348 prh 06 -09- 2018 (carboxymethyl)-N,N-dimethyl- N-(C8-18 even numbered) acyl derivatives, such as alkylamidopropyl betaine; a modified polyether.

Examples of suitable commercial dispersing and/or wetting additives include 5 Dispersogen LFH, Disperbyk 102, Disperbyk 2060, Disperbyk 2061, Tego Dispers

653, soy lecithin, Rewopal M 365, VP-D 262. These may be used also or as a combination, such as a combination of Tego Dispers 653 and Disperbyk 102, a combination of soy lecithin and Rewopal M 365, a combination of soy lecithin and Tego Dispers 653, a combination of soy lecithin, Tego Dispers 653 and VP-D 262, 10 a combination of Tego Dispers 653 and VP-D 262, a combination of Disperbyk 2060,

VP-D 262 and Disperbyk 102, and a combination of Disperbyk 2060 and Disperbyk 2061.

Humectants are hygroscopic materials that are used to promote the retention of 15 moisture. Humectants have an effect to the drying time and they help to prevent the drying out of pigment concentrates during manufacture and also prevent the drying out of paint or coating formulations, for example during storage within a can. Humectants also reduce the viscosity to help increase the pigment loadings for pigment concentrates thereby acting as a process aid. They may also have an effect 20 to the wet-edge time during the application of the paint or coating. The drying time correlates with open time, which is a period in which irregularities in a freshly applied coating can be repaired without resulting in brush marks. On the other hand the period in which a coating can be applied over an existing paint film without leaving lap marks is called as wet edge time. Therefore the use of the humectants described 25 herein may increase the open time and the wet edge time of the final tinted paint.

The colourant composition comprises one or more polymeric OH-functional humectant(s), more particularly polymeric OH-functional humectants having a high molecular weight. The polymeric OH-functional humectant comprises or consists of 30 high molecular weight polyether humectants. The polymeric OH-functional humectant comprises one or more polymer(s) having OH-functionalities. In one embodiment the polyether humectant is a high molecular weight polyglycol humectant. In a general example a polymeric OH-functional humectant has a mean average molecular weight in the range of 500-10000 g/mol, 700-10000 g/mol, 35 1000-10000 g/mol, 500-3000 g/mol, 700-3000 g/mol, 500-2000 g/mol, 700-2000 g/mol, 1000-3000 g/mol, or 1000-2000 g/mol.

20175348 prh 06 -09- 2018

In general the mean average molecular weight of a polyether may vary and it may be for example in the range of 200-50 000 g/mol, such as 500-10000 g/mol, or more particularly 700-10000 g/mol. In one example a polyether humectant has a mean average molecular weight of at least 500 g/mol, at least 700 g/mol, or 1000 5 g/mol, such as at least 2000 g/mol, or at least 3000 g/mol, such as in the range of 500-5000 g/mol, 700-5000 g/mol, 500-3000 g/mol, 700-3000 g/mol, 500-2000 g/mol, 700-2000 g/mol, or 1000-3000 g/mol, or 1000-2000 g/mol. One exemplary polyether humectant used in the tests had a mean average molecular weight of about 1500 g/mol.

The amount of the OH-functional humectants, preferably polyether humectants, in the composition may be in the range of 3-12% (w/w), such as 3.75-10% (w/w), or 4-10% (w/w). In certain cases, as noticed in the tests, a higher amount of the humectant is required, such as in the range of 9-12% (w/w). Polyether humectants 15 are used preferably instead of humectants containing mono or oligomeric glycols having a low molecular mass less than 1000 g/mol, less than 700 g/mol, or less than 500 g/mol, or even less than 400 g/mol or less than 200 g/mol. Therefore the humectants preferably do not contain mono or oligomeric glycols, such as ethylene glycol, propylene glycol or butyl glycol. Ethylene glycol has a molecular mass of 20 about 62 g/mol and propylene glycol of about 76 g/mol. Examples of such glycols include glycol ethers, such as ethylene glycol butyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ether, and triethylene glycol dimethyl ether.

In one example the composition does not contain mono or oligomeric glycols, as discussed in previous. The mono or oligomeric glycols will slow down the drying of the tinted paint, especially alkyd based paints. On the contrary longer polyethers do not have such an effect. At the same time high molecular weight polyethers keep 30 the colourants flowable and prevent drying and caking of the colourants in the tinting equipment. In one example the humectant does not contain compounds based on phosphoric esters and/or phosphonic esters.

The polyether in the humectant may be for example polymeric glycol, 35 polyhydroxyether, polysaccharide, modified polyurea, or polyalkylene oxide. A polymeric humectant may be a homopolymer or a copolymer of one or more monomers.

20175348 prh 06 -09- 2018

Polyether glycols, or polyglycols or polyols, are aliphatic polyethers with the general formula HO[-(CH2)mO-]_nOH. Examples of polyether glycols include polyacetal and paraformaldehyde (repeating unit -CH2O-; polyethylene glycol, polyoxyethylene, polyoxyethylene (releating unit - CH2CH2O-; polypropylene glycol, polypropylene 5 oxide, polyoxypropylene (repeating unit -CH2CH(CH3)O-; polytetramethylene glycol, polytetramethylene ether glycol and polytetrahydrofuran (repeating unit -CH2CH2CH2CH2, or a copolymer thereof.

The use of polymeric OH-functional humectants, such as polyether humectants, 10 enables decreasing the amount of VOC and SVOC emissions. Low molecular weight polyglycols, such as propylene glycol, dipropylene glycol, and derivatives thereof, such as glycol derivatives and phenylglycol derivatives, are prone to provide especially VOC or SVOC emissions.

Other types of humectants include modified urea, trimethyl polyol, such as trimethylolpropane (propylidynethmethanol), non-ionic dispersant, and betaine.

Non-ionic dispersants may be provided as a mixture with polyols, especially low molecular weight polyols.

The colourant composition preferably does not contain certain harmful compounds, such as compounds recognized by EU Ecolabel. The colourant composition does not contain alkylphenol ethoxylates (APEO). The colourant composition does not contain added folmaldehyde, phthalates, heavy metals, such as lead, cadmium chromium (VI), mercury, arsenic, barium, selenium or antimony other than trace levels (less than 100 ppm), organotin compounds, phthalates, halogenated organic substances and isocyanates.

With the selected compounds the VOC and SVOC content of the colourant composition can be kept at very low level. In general, the colourant composition 30 contains 5 g/l or less of volatile organic compounds (VOC), such as 3.5 g/l or less, g/l or less, 2 g/l or less, or 1 g/l or less, more particularly 0.5 g or less. In examples the colourant composition contains 0.25% (w/w) or less of volatile organic compounds (VOC), 0.20% (w/w) or less, more particularly 0.15% (w/w) or less, or even 0.005% (w/w) or 0.002% (w/w) or less, calculated from the total weight of the 35 composition. The VOC content may be determined according to DIN EN ISO

11890/2. In the compositions of the examples the VOC content was below 0.20% (w/w), such as 0.18% (w/w), and in some cases even below 0.002% (w/w), such as 0.0015% (w/w).

20175348 prh 06 -09- 2018

In one example the colourant composition contains 6 g/l or less of semi-volatile compounds (SVOC), such as 5 g/l or less. In one example the colourant composition contains 3 g/l or less of semi-volatile compounds (SVOC), or 2 g/l or less, more particularly 1 g/l or less. In one example the colourant composition contains 1.0% or less or less of semi-volatile compounds (SVOC), preferably 0.5% or less, or more preferably 0.35% or less, preferably 0.25% (w/w) or less, for example 0.20% or less, 0.15% or less, or more preferably 0.1% (w/w) or less, for example 0.05% (w/w) or less. In other units, the SVOC content may be 30 g/l or less, 20 g/l or less, 10 g/l or 10 less, 6 g/l or less, 5 g/l or less or 2 g/l or less, or even 0 g/l. In one example the colourant composition contains no semi-volatile compounds, or substantially no semi-volatile compounds, meaning that only insignificant amounts, such as 0.1 g/l or less, or 0.05% (w/w) or less may be present. The SVOC content may be determined according to DIN EN ISO 11890/2. In the compositions of the examples 15 the measured SVOC content was below 0.35% (w/w), even below 0.20% (w/w).

However, as the scope of ISO 11890-2 does not properly cover SVOC measurement, another method for determining the SVOC content may be used. ISO 11890-2 is currently being proposed to be amended for its scope by ISO/TC 35 to 20 include SVOC determination. However, until it is amended, a guidance for the paint industry on the determination of Semi-Volatile Organic Compounds (SVOC) using ISO 11890-2 (2013) (extending its scope) is provided by the CEPE (European Council of the Paint, Printing Ink and Artists' Colours Industry).

The guidance document interprets the specifications of ISO 11890-2 to allow the running of a test to quantify paint SVOC content, either alone or in one run together with an ISO 11890-2 VOC test, so as to evaluate compliance with the requirements of the Ell Ecolabel. The guidance should therefore be read alongside ISO 11890-2, but with the modified sample preparation method, apparatus and parameters 30 specified taking precedence. The procedure is explained in detail at the Examples section of this application. Preferably the SVOC content is measured according to this procedure.

In one embodiment the colourant composition does not contain a binder, such as a 35 ketone aldehyde resin or acrylate binder. Especially binders commonly used in paints cannot be usually used in colourants because they are not readily compatible with other binders, and they often have too high viscosities and poor pigment dispersing and/or wetting properties. If binders would be used, they should be

20175348 prh 06 -09- 2018 specific colourant binders having better properties with respect to polarity and/or solubility. However, in the present embodiments it was possible to obtain a binderfree combination of dispersing and wetting additives and humectant and water as diluent which could be used as a medium as such.

The colourant composition may contain one or more antifoaming agent(s), which may be also called defoamers. The amount of the antifoaming agent(s) is in the range of 0.1-1.0% (w/w), such as in the range of 0.6-1% (w/w), or 0.7-1% (w/w). In one example the antifoaming agent is an emulsion comprising foam-destroying 10 polysiloxanes, hydrophobic solids and emulsifiers; or a mixture comprising foamdestroying polysiloxanes and hydrophobic solids. Examples of commercial antifoaming agents include BYK-023 silicone defoamer and BYK-017 silicone defoamer.

The colourant composition may contain one or more inorganic filler(s). The amount of the inorganic filler(s) may be in the range of 0-43% (w/w), and if present, the amount of the inorganic filler(s) may be in the range of 1-43% (w/w), such as 540% (w/w), or 10-35% (w/w). The inorganic filler may comprise calcium carbonate, calcium sulphate, such as gypsum and anhydrite, barium sulphate, clay minerals 20 such as talc, mica, kaolin/kaolinite, silicon dioxide (silica), diatomaceous silica, dolomite, synthetic silicate fibers or a combination thereof. Fillers are used to optimize the dispersing phase to give it a suitable consistency. Optimizing the filler package also gives significant saves in the more expensive components like pigments. Clay minerals, in general hydrous aluminium phyllosilicates, may be used 25 because they have a relatively small particle size, which may have an effect to rheological properties, such as viscosity. Talc is a clay mineral comprising hydrated magnesium silicate with the chemical formula H2Mg3(SiO3)4 or Mg3Si40io(OH)2. Kaolin may be used in paint especially to extend the titanium dioxide (T1O2) white pigment and modify gloss levels. In general kaolin refers to rocks that are rich in 30 kaolinite (aluminium silicate dehydrate), which is a clay mineral, with the chemical composition Al2Si2Os(OH)4. One specific example of kaolin is calcined kaolin, which is raw kaolin that has been fired (in a rotary calcining kiln) high enough to remove the about 12% crystal water, i.e anhydrous aluminium silicate Al2O3'2SiO2. Also other aluminium silicates may be used as fillers. Dolomite is an anhydrous 35 carbonate mineral comprising calcium magnesium carbonate, ideally CaMg(CO3)2, with rhombohedral shaped crystals.

20175348 prh 06 -09- 2018

The colourant composition may contain one or more thickener(s). A thickener is used to adjust the overall viscosity of the composition, such as to increase the overall viscosity. The thickener may be inorganic or organic, synthetic or nonsynthetic. A thickener may have an effect to rheology, but is not considered an actual 5 rheology modifier in this context. Rheologically active additives, i.e. rheology modifiers, differ from thickeners. Rheology modifiers effect changes in viscosity over a specific range of shear rate, which leads to non-Newtonian flow. In contrast, thickeners effect an increase in viscosity over the whole range of shear rate by increasing only the viscosity of the liquid phase (liquid phase thickeners). The 10 thickeners usually do not change the flow (or the rheology), at least in substantial amounts.

In one embodiment the thickener is organic thickener, such as polymeric thickener, for example a synthetic organic thickener. Thickeners may be classified as 15 associative and non-associative thickeners. Associative thickening involves nonspecific interactions of hydrophobic end groups of a thickener molecule both with themselves and with the other components of the composition. The thickener produces a reversible, dynamic network of thickener molecules and the other components.

Non-associative thickening is thickening by an entanglement of water-soluble, high molecular weight polymer chains. The effectiveness of a non-associative thickener is mainly determined by the molecular weight of the polymer. Formulations thickened non-associatively have pseudoplastic rheology with highly elastic 25 properties. However, such systems may have a limited flowability and because of the high molecular weight, also compatibility problems such as flocculation.

A preferred type of thickener is associative thickener, which offers properties including improved flow and leveling. So far associative thickeners were only used 30 in waterborne paints and coatings. The associative thickener may be selected from styrene-maleic anhydride terpolymers (SMAT), hydrophobically modified alkaliswellable emulsions (HASE), hydrophobically modified polyether thickeners (HMPE), hydrophobically modified cellulose ethers (HMHEC), and hydrophobically modified ethoxylated urethanes (HEIIR), also known as PUR (polyurethane) 35 associative thickeners. In one embodiment the associative thickener is hydrophobically modified ethoxylated urethane. In one example the associative thickener is hydrophobically modified polyacetal polyether (HM-PAPE).

20175348 prh 06 -09- 2018

The polyurethane associative thickeners are synthetic thickeners and may have a molecular weight in the range of 10000-100000 g/mol, such as 15000-100000 g/mol. They usually comprise nonionic hydrophobic polymers, which are available either in liquid form (for example as a 50% solution in water and/or organic solvents) 5 or in powder form. The PUR polymers are obtained by reacting diisocyanates with diols and hydrophobic blocking components. Such molecules may contain hydrophobic terminal segments (end-groups), several hydrophilic segments and urethane groups. The polymer is end-capped with hydrophobic segments. The linking of the middle segments with each other and with the terminal segments 10 occurs mainly via free hydroxyl groups of the segments with mono- or polyisocyanates forming the urethane structures which give their name to this class of products. Examples of hydrophobic segments include oleyl, stearyl, and dodecylphenyl. The hydrophilic segments may comprise polyethers or polyesters, for example polyesters of maleic acid and ethylene glycol and polyethers, such as 15 polyethylene glycol or polyethylene glycol derivatives. However, polyethers are the preferred hydrophilic segments, as these polymers offer the best chemical resistance and hence the best viscosity stability during storage of the paint. The polymer chain may be extended by polyisocyanates. Examples of possible isocyanates include isophorone diisocyanate (IPDI), toluene diisocyanate (TDI) and 20 hexamethylene diisocyanate (HMDI). The PUR associative thickeners function only through interactions with other components of the composition, such as the colourant composition or the paint or coating.

The presence of hydrophobic and hydrophilic groups in the same PUR thickener 25 molecule indicates a certain surface activity. On solution in water, formation of micelles does in fact occur above a characteristic concentration. In contrast to monomeric surfactants, the same PUR associative thickener molecule may be present in more than one micelle. This results in the formation of structures that reduce the mobility of the water molecules and in an increase of the viscosity, which 30 may result in the formation of a gel structure. The extent to which association takes place with the polymer particle depends on the properties of the hydrophobic group and on emulsion particle surface properties. The strength of the structure build-up between the PUR associative thickener and the dispersion particle depends on the strength of the association of the PUR thickener to the dispersion particle surface. 35 Associative thickeners with multiple hydrophobic functionalities are very effective high-shear thickeners.

20175348 prh 06 -09- 2018

Conventionally formulated solvent borne paints usually show an almost Newtonian flow behaviour and differ considerably in this respect from dispersion paint systems. Contrary to waterborne coatings, the solventborne coatings are characterized by dissolved resin molecules, rather than dispersed polymeric particles. Therefore any 5 similar kind of association thickening as seen for associative thickeners with binder particles in waterborne coatings seems to be unlikely in solventborne coatings. However, dispersed pigment particles in solventborne coatings offer adsorptive sites for association interactions, which is used for associative thickeners for use in solventborne coatings (solventborne associative thickeners, SBAT), which belong 10 to the polyurethane class of polymers.

In one embodiment the colourant composition comprises one or more liquid associative polymeric thickener(s) in the range of 0.1-3.0% (w/w), such as 0.2-2.0% (w/w), for example 0.2-1.8% (w/w).

In one embodiment the colourant composition comprises one or more non-ionic liquid associative polymeric thickener(s), such as one or more polyurethane-based non-ionic liquid associative polymeric thickener(s), for example hydrophobically modified polyurethane. In one example the polyurethane-based non-ionic liquid 20 associative polymeric thickener is a solution of polyether urethane.

In one embodiment the colourant composition comprises one or more liquid associative polymeric thickener(s) comprising glycerides, such as C8-10 mono, di and th ethoxylated glycerides; and an oxirane compound, such as phenyl oxirane, 25 polymer with oxirane, or mono (3,5,5-thmethylhexyl) ether.

In one example the colourant composition has a pH in the range of 7-9.5, such as in the range of 9-9.5 or in the range of 7-8.5. The pH may have been adjusted by adding a pH adjusting agent. The colourant composition may comprise a pH 30 adjustment agent, for example less than 1% (w/w) of the composition, such as in the range of 0-1% (w/w), or 0-0.57% (w/w) for adjusting the pH to the range of 79.5, such as (earth) alkaline metal hydroxide, such as NaOH, or other pH adjusting agent.

In one example the colourant composition comprises one or more rheology modifier(s). Rheology modifiers may be classified in two groups: particulate (dispersed) and polymeric (dissolved) types. In one embodiment the rheology modifier is a particulate rheology modifier, for example comprising layered

20175348 prh 06 -09- 2018 silicate(s), such as synthetic lattice-layer silicate, or fumed silica or a rheology modifying clay, such as attapulgite, bentonite, or laponite. In one embodiment the rheology modifier is an inorganic rheology modifier. In one embodiment the rheology modifier is a particulate inorganic rheology modifier. In one example the composition 5 does not contain polymeric and/or organic rheology modifiers, which are not associative thickeners, such as acrylates or cellulose ethers.

The amount of the particulate or inorganic rheology modifier may be in the range of 0-1.5% (w/w), more particularly in the range of 0.1-1.5% (w/w), such as 0.5-1.5% 10 (w/w). A rheology modifier, as used herein, refers to a substance which provides for example anti-settling properties. A rheology modifier therefore prevents sedimentation of the substances of the colourant composition, or the paint, but at the same time maintains the fluidity of the composition. The rheology modifier maintains low viscosity in the composition, and it is effective already in small 15 amounts. The rheology modifier may provide thixotrophy to the composition, i.e.

time-dependent shear thinning properties. Such a composition may be viscous in static conditions but becomes thin or less viscous when shaken, agitated, sheared or otherwise stressed. Such fluids may be also called as non-Newtonian pseudoplastic fluids, which show a time-dependent change in viscosity; the longer 20 the fluid undergoes shear stress, the lower its viscosity. In contrast, in a Newtonian flow the viscosity does not depend on the shear rate. In one example of nonNewtonian flow the viscosity decreases with increase in shear rate. In another example of non-Newtonian flow including thixotrophy, the viscosity decreases with increase in shear rate (gel curve) and increases with decrease in shear rate (sol 25 curve), but not to the same extent as in the case of the gel curve. If the system is allowed to stand for some time, it returns to its initial viscosity (complete reversibility). The greater the difference between the sol and gel curves, the greater is the degree of thixotropy. Unlike shear thinning, which is time-independent, thixotropy is time-dependent.

In one embodiment the particulate and/or inorganic rheology modifier is a silicabased rheology modifier, such as fumed silica, for example hydrophilic fumed silica. The fumed silica may be highly disperse, i.e. nanoparticulate, which will orientate in a fluid and forms a gel, thereby providing anti-settling properties, in both solvent 35 borne and waterborne paints. Particulate, especially nanoparticulate, rheology modifier, such as the fumed silica, was found out to provide such a low viscosity that was especially suitable for the types of universal colourants discussed herein. Therefore in one example the particulate rheology modifier is nanoparticulate. In

20175348 prh 06 -09- 2018 general nanomaterials are chemical substances or materials that are manufactured and used on a very small scale. According to a definition by European Chemicals Agency their structures range from approximately 1 to 100 nm in at least one dimension. Nanomaterials have unique and more pronounced characteristics compared to the same material without nanoscale features. Therefore, the physicochemical properties of nanomaterials may differ from those of the bulk substance or particles of a larger size.

In one example the silica-based rheology modifier comprises colloidal silica. 10 Colloidal silicas are usually present as suspensions of fine amorphous, nonporous, and typically spherical silica particles in a liquid phase. Colloidal silicas are most often prepared in a multi-step process where an alkali-silicate solution is partially neutralized, leading to the formation of silica nuclei. The subunits of colloidal silica particles are typically in the range of 1-5 nm. Whether or not these subunits are 15 joined together depends on the conditions of polymerization. Initial acidification of a water-glass (sodium silicate) solution yields Si(OH)4. Colloidal silica may be used to obtain a higher open time of the composition.

Fumed silica is also known as pyrogenic silica because it is produced in a flame, 20 and it contains microscopic droplets of amorphous silica fused into branched, chainlike, three-dimensional secondary particles which then agglomerate into tertiary particles. The resulting powder has an extremely low bulk density and high surface area. The fumed silica is hydrophobic, so it is not wetted by water but by waterborne paint resins, which makes it ideal as an additive for modifying rheology, 25 especially of waterborne paints.

In one embodiment the particulate and/or inorganic rheology modifier, such as the hydrophilic fumed silica, has a specific surface area in the range of 50-600 m²/g, 150-400 m²/g, 200-400 m²/g or 150-250 m²/g.

In one example the colourant composition comprises one or more biocide(s), preferably in an amount less than 0.2% (w/w) of the total composition, such as less than 0.16% (w/w), for example in an amount in the range of 0.05-0.2% (w/w), or 0.5-0.16% (w/w). The biocide may be any biocide or antimicrobial additive suitable 35 for colourant or paint or coating compositions, such as a bactericide, a fungicide or an algaecide. However, generally harmful biocides such as PCPs, PCBs and formaldehyde are naturally not preferred. One group of suitable biocides include isothiazolinone based biocides, such as 5-chloro-2-methyl-2H-isothiazol-3-one

20175348 prh 06 -09- 2018 (C(M)IT), 2-methyl-2H-isothiazol-3-one or 2-methylisothiazol-3(2H)-one (MIT), 1,2benzisothiazol-3(2H)-one (BIT), 2-methyl-1,2-benzisothiazol-3(2H)-one (MBIT), reaction mass of: 5-chloro-2-methyl-2H-isothiazolin-3-one and 2-methyl-2H isothiazol-3-one (3:1) (C(M)IT/MIT), 2-octyl-2H-isothiazol-3-one tai 2-octyl5 isothiazol-3(2H)-one (OIT) and 4,5-dichloro-2-octyl-2H-isothiazol-3-one, 4,5dichloro-2-octylisothiazol-3(2H)-one (DCOIT). Biocides used in the tests carried out in the embodiments include 2-methyl-2H-isothiazol-3-one and 1,2-benzisothiazol3(2H)-one.

Further examples of biocides include iodopropynylbutylcarbamate, octylisothiazolinone, dichlorooctylisothiazolinone, n-butyl-benzisothiazolinone, zinc pyrithione and sodium pyrithione.

The colourant compositions disclosed herein may contain also minor amounts of 15 other ingredients, such as in an amount of 0.1-10% (w/w), or 0.1-5% (w/w), or 0.13% (w/w), or less than 5%, less than 3% or less than 1 %.

One example provides a method for preparing the aqueous universal colourant composition disclosed herein, the method comprising providing the ingredients, 20 such as one or more pigment(s), optionally dispersing system, optionally one or more inorganic filler(s), optionally one or more polymeric OH-functional humectant(s), optionally one or more containing organic thickener(s), optionally one or more inorganic and/or particulate rheology modifier(s), and any other required components, such as one or more inorganic filler(s), one or more biocide(s), one or 25 more antifoaming agent(s), and the like, combining and dispersing said ingredients with water as solvent to obtain the aqueous universal colourant composition. The proportions and/or amounts of the ingredients may be as disclosed in the embodiments.

The aqueous universal colourant composition disclosed herein may be used in a method for tinting a base paint. In one embodiment the method comprises -providing a base paint,

-providing the aqueous universal colourant composition,

-adding an amount of the aqueous universal colourant composition to the base 35 paint, and

-mixing to obtain a tinted paint.

The base paint may be any suitable base paint known in the art. Such base paints are usually commercially available and are arranged to be tinted, for example at a retail store. Therefore it is clear that the base paint is not already tinted, but it may contain a basic type colour range, such as white, semi-white or clear. It is also clear 5 that the colourant composition is not a base paint, or a tinted paint.

A customer may select a desired colour of the final paint. The amount and type of one or more colourant composition(s) to obtain the desired colour is provided, for example by a computerized system or from a manual system, and the provided 10 type(s) and amount(s) of the colourant composition(s) are added into a container containing the base paint, for example through an aperture at the lid of the container. The aperture is closed and the container is then agitated in a mixer so the colourant(s) will be evenly mixed with the base paint and the desired colour of the paint is obtained. The universal colourant may be added to practically any kind of 15 base paints.

20175348 prh 06 -09- 2018

Examples

Methods used for testing the colourant compositions are explained herein.

Rub-Out test

The rub-out test may be used to check the stabilisation of pigment particles. It can be used to assess the compatibility of pigment concentrates, the tendency of pigment particles to flocculate or pigment flooding phenomena. Rub-out test is 10 described in “Additives for Waterborne Coatings, Wernfhed Heilen et al., Hannover:

Vincentz Network, 2009 (European Coatings Tech Files), pages 27, 34-35” as follows.

An area of the moist but partially dry paint film is rubbed with a finger or a brush. If 15 the pigments have separated or are strongly flocculated, this mechanical procedure of rubbing re-establishes a homogeneous pigment distribution. The viscosity of the dry film will already have increased strongly. The homogeneous distribution of pigment particles is stabilised this way. The colour difference relative to the unrubbed film is an indication of pigment separation or flocculation. The colour 20 difference is usually quoted as the separation of the chromaticity ΔΕ (ΔΕ is dimensionless). For ΔΕ less than 0.5, no colour difference is visible. The automotive sector requires ΔΕ <0.3. Between 0.5 and 1.0 the colour difference is only slightly visible. For architectural paints, ΔΕ of <1.0 is still adequate but ΔΕ values greater than 1 are not acceptable.

Table 1 shows results from a test wherein 2 ml of a colourant of the embodiments was added into 90 ml of white base paint

Table 1.

Colourant	ΔΕ rubout in waterborne paint	ΔΕ rubout in solventborne paint
PY42 Yellow Iron Oxide	0.05	0.07
PY138 Quinophthalone Yellow	0.68	0.43

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Determination of Semi-Volatile Organic Compounds (SVOC) using ISO 118902(2013) (CEPE)

Sample preparation:

An organic solvent suitable for diluting the sample shall be used. It shall have a purity of at least 99% by mass. The recommended dilution solvent is methanol 100%. If necessary, the sample can be stirred during 30 minutes with application of ultrasound in order to achieve a homogenous liquid phase, or by mechanically 10 stirring during two hours followed by centrifugation or a filtration step using a PTFE filter type for paints containing large, undissolved particles. In the case that a homogenous liquid phase cannot be achieved using methanol 100% then another suitable dilution solvent, such as acetonitrile or tetrahydrofuran, shall be used.

Note: The marker compounds to be used are n-tetradecane (n-C14) and nDocosane (n-C22). It may be necessary to prepare a marker solution containing these compounds in acetone due to the limited solubility of n-Docosane in acetonitrile.

Capillary column:

The preferred choice of column shall be one made of fused silica coated with 5% phenyl 195% dimethyl polysiloxane (slightly polar type, DB5 or equivalent).

A column coated with 100% dimethyl polysiloxane (non-polar type, DB1 or equivalent) may be used if it can be shown to perform better for predominantly nonpolar paint ingredients.

Note: A suitable combination of column length (30m or 60m), diameter and 30 temperature programme shall be selected such that compounds in the sample and the markers elute in the order of their increasing boiling points. A column length of 60m may be used to improve the elution order for the slightly polar column type.

Oven:

- Oven initial temperature: 40-100°C

- Isothermal holding time: 2-5 min

- Heating rate: 3-20°C/min

- Oven final temperature: 280-325°C

20175348 prh 06 -09- 2018

- Isothermal holding time: >2min

- Flow in the column: 1-2 ml/min

Detector:

- Identification by mass spectrometer

- Quantification by flame ionization detector (FID)

- FID detector temperature: Final oven temperature or higher

Carrier gas:

- helium

Hot injection system:

- injector temperature : 250-280°C

- injection volume: 1-2 pl

Calibration:

The preferred internal standard for quantification of SVOC peaks shall be ntetradecane (n-C14). An alternative internal standard, 1,2-diethoxyethane (also named ethylene glycol diethyl ether) can be used in order to achieve improved recovery values when analysing water-based paints.

Note: If the calibration procedures are run in an appropriate manner the selection of the internal standard should have no impact on the test result. However, it is important to ensure that the internal standard does not overlap or hide any peaks arising from the sample itself. It must therefore show a complete separation from other peaks in the chromatogram. A large choice of internal standards is thus possible but internal standards having very low boiling points (e.g. acetone...) or very high boiling points (C22 and more) must be excluded to avoid any discriminatory phenomenon in the injector.

All SVOCs shall be identified as far as achievable, and then quantification shall be performed with their authentic calibration standards, as specified for VOCs in ISO 11890-2, or via their relative response factors. Remaining unknown SVOC peaks shall be quantified using the response factor of diethyl adipate, expressed in diethyl adipate equivalents.

20175348 prh 06 -09- 2018

SVOCs were measured for colourants of the embodiments. For example a colourant containing diketopyrrolo pyrrole, Pigment PR254, exhibited a SVOC value of 1.9 g/l, and a colourant containing synthetic hydrated ferric oxide, Pigment yellow PY42, exhibited a SVOC value of 6.0 g/l, corresponding to 0.15% (w/w) and 0.34% (w/w).

Stability of a colourant in a dispenser

It was noticed that the viscosity of the test colourant compositions increased less during mixing when compared to reference samples. Also the colour strength and 10 shade remained stable while in the references they changed remarkably.

As already discussed, one problem with existing colourants is that their viscosity, colour shade and strength may change during stay in dispenser due to mixing of colourant in the canister. To evaluate the stability of a colourant against mixing a 15 method called “Roller bench test” was used in the tests.

1. Roller bench test of a colourant

Equipment and material

-a roller bench

-a jar+lid (for example height 90 mm, diameter 70 mm)

-KU viscometer

-a colourant of an embodiment

-a reference colourant

Test procedure

The colourant (about 250 ml) is filled into jar and the jar was closed. Colourant 30 amount has to be enough, that KU viscosity can be measured, but the jar should not be filled to the top.

The speed of roller bench is adjusted so, that rolling speed of jar is 30 rpm.

The jar is placed on the roller bench for 1 week. After 1 week the jar is taken from the roller bench and the lid is opened. The appearance of colourant is evaluated. Features such as if the colourant is on the walls and if there is a hole on the centre of the colourant, are monitored.

After visual evaluation, the colourant is mixed homogenous with a spatula and the KU viscosity is checked.

Colour strength and shade is checked after roller bench by adding colourant (2% v/v) into a white base paint and by shaking 2 minutes in shaker. A draw-down is made on draw-down paper with a 150 pm applicator, and let dry at room temperature until dry. The colour shade and strength are measured against a sample of the same colourant, which has not been on the roller bench.

The test results and one example are evaluated and shown in Table 2.

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Table 2

Test	Result	Judgement
Visual observation	homogenous hole in the center	acceptable (homogeneous) not acceptable (not homogeneous)
KU (ASTM D 5895 - 03) viscosity change	less than +15KU compared to original >+15KU compared to original	acceptable not acceptable
ΔΕ (Cielab, D65)	ΔΕ<1.5 ΔΕ>1.5	acceptable not acceptable
colour strength change (AStrength, %)	<+5% >+5%	acceptable not acceptable
Example of results
Colourant	Colourant PO73	Colourant PO73 reference
Roller bench test Visual observation KU viscosity change AE(Cielab, D65) AStrength%	result homogenous -2 (acceptable) 0.3 (acceptable) -0.7 (acceptable)	result acceptable (homogenous) +37 (not acceptable) 2.3 (not acceptable) -13.2 (not acceptable)

2. The effect of the colourant to drying time of tinted alkyd paint

Test method use was according to standard ASTM D 5895 - 03 Standard Test Methods for Evaluating Drying or Curing During Film Formation of Organic Coatings 5 Using Mechanical Recorders.

Test conditions:

Wet film thickness 300 pm (drying conditions: 25°C, RH=50%, 24h). Test paint: 10 Panssarimaali C-base (Solvent borne alkyd paint, clear base paint). Test shade: colourants of the embodiments added by vol-% to test paint:

Lamp black (Pbk7) 1.91%

Synthetic Iron Oxide Red (PR101) 1.18%

Quinophthalone Yellow (PY138) 2.26%

Yellow Iron Oxide, Pigment yellow (PY42) 1.38%

As a reference a very low VOC commercial universal colourant with the same colour as the colorants of the embodiments was used.

Results are shown in Table 3:

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Table 3

Results:	flowing	dust-dry	touch-dry	throughdry
test shade	9 min	37 min	3 h	8 h
reference	23 min	3 h 25 min	11 h 45 min	>24 h

It was noticed that the colourants of the embodiments containing polymeric OHfunctional humectant provided a remarkably shorter drying time of a tinted alkyd paint compared to a reference colourant. This was probably mostly due to a high molecular weight polyether used in the embodiments.

3. Effect of the colourant to the KU viscosity of tinted waterborne paints

Test procedure

10% (v/v) colourant was added to paint and shaked for 2 minutes. KU viscosity was measured according to ASTM D562-01 one day after tinting. Testbase was Euro 20 C-base. The results are shown in Table 4.

Table 4.

Paint	Colourant	KU viscosity
Euro 20 C-base (waterborne styrene acrylate paint)	-	120
PY74, Arylide yellow	120
PY74 reference	83
PY138, Quinophthalone Yellow	111
PY138 reference	92
PW6, Titanium white	107
PW6 reference	90

It was noticed that the colourants of the embodiments reduced the viscosity of the tinted waterborne paint less than the reference colourant.

As a reference a very low VOC commercial universal colourant with the same colour 15 as the colorants of the embodiments was used. Table 5 shows the compositions of the test colourants.

20175348 prh 06 -09- 2018 able 5.

Colourant	PY42	PBk7	PO73	PR254	PY74
Raw material	%	%	%	%	%
Water	32.78	32.78	39.53	26.40	36.78
Dispersing additive 1		22.13	1.53	21.91	16.98
Dispersing additive 2	4.28		2.95
Dispersing additive 3			3.93
Dispersing additive 4		1.60
Lecithin		4.39
Polymeric OH-functional humectant	5.97	4.28	8.51	9.96	7.63
Defoamer	0.80	0.84	1.06	1.00	1.04
NaOH. 19%	0.50	0.44	0.68		0.22
Associative polymeric thickener	0.28	0.09	1.04	0.60	1.90
Biocide	0.13	0.14	0.15	0.13	0.14
Inorganic filler kaolin		4.70	32.50		5.16
Silica based rheology modifier		0.07	0.12		0.07
Inorganic filler talc		9.51
Pigment PY42 Yellow Iron Oxide	55.27
Pigment PO73 Pyrrole orange			8.00
Pigment PBk7 Lamp black		19.03
Pigment PY74 Arylide yellow					30.08
Pigment PR254 Pyrrole red				40.00
	100.00	100.00	100.00	100.00	100.00

20175348 prh 06 -09- 2018

The dispersing additive 1 was a modified polyether with groups of high pigment affinity (polyether phosphate). The dispersing additive 2 was a copolymer with 5 pigment affinic groups having an acid value of 5 mg KOH/g. The dispersing additive was a block copolymer with pigment affinic groups having an acid value of 3 mg KOH/g. The dispersing additive 4 was N-C8-18(even numbered) alkylamidopropyl betain.

The polymeric OH-functional humectant was a polyether humectant having a mean average molecular weight of about 1500 g/mol. The associative polymeric thickener was a polyurethane associative thickener.

Drying of the colourant

Colourants are added to paints through a dispenser nozzle. It is important, that they do not dry fast in the nozzles of the dispenser in order that the colorants can be dispensed out right amounts to achieve the desired tint for the paint.

This test was developed to check how fast colourant dries in an open nozzle. If this happens, problems for accurate colourant addition to paint through the dispenser will follow. This test can also be used to evaluate the effect of humectant for drying of colorant.

Equipment and material ml plastic syringe, nozzle’s inner diameter 1 mm

Rack to keep syringe at right position (nozzle down)

Colorant under development

Reference colorant (VOC free universal commercial colorant with same color)

Description of test

Draw in 5 ml of colorant into a 10 ml syringe. Wipe the outside of nozzle clean of colorant. Place the syringe on rack so that the nozzle points down.

Make 2 parallel samples of colorant and of corresponding reference colorants. Let the syringes stay for 24 hours and 48 hours on rack at conditions 23°C/50%RH 20 (RH= relative air humidity). After 24 hours and 48 hours, inject the colorants out of syringes.

Table 6 shows a judgement scale used for evaluating the results.

20175348 prh 06 -09- 2018

Table 6.

Observation	result	judgement
Colorant comes out easily, no drying on the nozzle	1	works in the dispenser
Colorant comes out, but some drying on the nozzle	2	does not work good enough in the dispenser
Colorant comes out, but severe drying on the nozzle	3	does not work in the dispenser
Colorant does not come out, nozzle is blocked	4	does not work in the dispenser

The results are shown in Table 7.

Table 7.

Colourant	result 24 hours	results 48 hours
PR254 (containing 8% of humectant)	4	4
PR254 (containing 10% of humectant)	1	1
PR254 reference	1	2

20175348 prh 06 -09- 2018

This result shows, that humectant addition increases drying time of colorant and that drying can be adjusted on the same level or better compared to a reference colorant from market, where it is used in a dispenser. The effect of the humectant may be 10 pigment-dependent.

Claims

The claims

A water-based general tinting composition, such as a paste, comprising 20-65% by weight of water,

5 -one or more pigments 1.8-70 wt%

-dispersing system 2-30% by weight,

-one or more polymeric OH-functional humectants 3-12% by weight, -optably one or more inorganic fillers 1-43% by weight, the composition containing 0.5% by weight or less of semi-volatile organic compounds

(SVOC), preferably 0.35% by weight or less, characterized in that the polymeric OH-functional humectant is a polyether humectant having an average molecular weight of about 1500 g / mol.

The aqueous general tinting composition of claim 1, wherein the composition contains 0.2% by weight or less of volatile organic compounds (VOC).

The aqueous general tinting composition of claim 1 or 2, wherein the dispersing system comprises one or more dispersing and wetting agents, such as at least two different dispersing and wetting agents.

The aqueous general tinting composition of claim 3, wherein the dispersing and wetting agent comprises both wetting and dispersing functionalities in a single molecule.

An aqueous general tinting composition according to any preceding claim, wherein the dispersing system comprises one or more dispersing and wetting agents selected from: a modified (e.g. OH-modified) polyether or polyester having a pigment affinity group or groups such as a hydroxyl functional carboxyl functional or carboxyl functional affine

30 group or groups, polyether phosphate or phenyl polymer with epoxy, monoalkyl esters; a copolymer having a pigment affinity group or groups; a block copolymer having a pigment affinity group or groups; poly (oxy-1,2-ethanediyl), alpha-isotridecyl omegahydroxy, phosphate; ethoxylated fatty acid (nonionic) such as polyglycol ester of xynoleic acid; 1-propanaminium, 3-amino-N35 (carboxymethyl) -N, N-dimethyl, N-C8-18 (even) acyl derivatives (amphoteric); and lecithin such as soy lecithin.

20175348 prh 06 -09- 2018

An aqueous general tinting composition according to any one of the preceding claims, comprising a polymeric OH-functional humectant of 2.75 to 10% by weight.

A water-based general tinting composition according to any one of the preceding claims.

5 wherein the composition comprises one or more organic thickeners comprising a liquid associative polymeric thickener, such as one or more liquid associative polymeric thickeners comprising glycerides, such as C8-10 mono-, di- and tri-ethoxylated glycerides; and an oxirane compound such as phenyloxirane, oxirane polymer, or mono (3,5,5, -thmethyl-10-hexyl) ether in an amount of 0.1 to 3.0% by weight, such as 0.28 to 1.9% by weight.

The aqueous general tinting composition of claim 7, wherein the composition comprises one or more nonionic liquid associative polymeric thickeners, such as a polyurethane-based nonionic liquid thickener.

15 associative polymeric thickeners.

The aqueous general tinting composition of any one of claims 7 to 8, wherein the composition comprises one or more liquid associative polymeric thickeners selected from styrene-maleic anhydride terpolymers.

20 (SMAT), hydrophobically modified alkaline swelling emulsions (HASE), hydrophobically modified polyether thickeners (HMPE), hydrophobically modified cellulose ethers (HMHEC) and hydrophobically modified ethoxylated urethanes (HEIIR).

Wherein the composition does not contain low molecular weight glycols, such as glycols having a molecular weight of less than 700 g / mol, or less than 500 g / mol or less than 200 g / mol.

An aqueous general tinting composition according to any preceding claim, wherein the composition does not contain a binder such as a ketone aldehyde resin or an acrylic

30 tile binders.

Aqueous general tinting composition according to any one of the preceding claims, wherein the composition comprises one or more inorganic and / or particulate rheology modifiers comprising a silica-based rheology modifier.

35 in an amount of 0.1 to 1.5% by weight of hydrophilic fumed silica, for example one having a specific surface area of 50 to 600 m ² / g.

Aqueous general tinting composition according to any one of the preceding claims, wherein the composition comprises 4.7 to 32.5% by weight of kaolin.

A method of tinting a base paint, the method comprising

Providing 5 primers,

- providing an aqueous general tinting composition according to any preceding claim,

-addition of the water-based general tinting composition to the base paint, -mixing to obtain a tinted paint.