Water-only colorant composition

Abstract

A point-of-sale order color system for tinting waterborne architectural base paints and stains includes an array of at least white, green, blue, and red low volatile organic compound water-only liquid colorants, each containing at least a three-component surfactant package, a pigment, and a vehicle. The surfactant package disperses the colorant compatibly and homogeneously throughout the waterborne base paints and stains, but does not disperse the colorant compatibly and homogeneously throughout the solventborne base paints and stains unless the colorant is used in combination with a synergist that contains one or more components that disperse the water-only colorant in the solventborne base paint or stain.

Description

[Technical field]

[0001] The present invention relates to colorants, and associated methods and surfactant packages, for point-of-sale customized color architectural paint and stain tinting systems, such as those used in retail paint stores to create custom tinted paints or stains. [Background technology]

[0002] Architectural paint and stain manufacturers typically distribute premixed paints and stains in a small number of popular colors. To accommodate consumer demand and allow color matching with existing painted or stained surfaces, manufacturers typically also distribute a tintable base paint or stain and a set of several liquid colorants. These are combined in stores at the point of sale using volumetric colorant dispensing equipment and shaker mixing equipment to create small batch lots of custom tinted paints or stains in a much larger array of colors than the limited array of colors available in the premixed products.

[0003] Due in part to industry practices and available colorant dispensing equipment, custom color systems from different paint or stain manufacturers tend to have somewhat similar components. For example, a typical custom color paint system may employ several (e.g., 2-4) tintable base paints, ranging from clear color bases that already contain a white pigment, such as titanium dioxide, and are intended to accept a relatively small amount of added colorant at the point of sale, to relatively unpigmented transparent bases that are intended to accept a much larger amount of added colorant at the point of sale. The base paints and stains may employ a variety of binders (e.g., natural or synthetic resins), binder forms (e.g., solution or latex polymers), and vehicles (e.g., solvent- or water-based versions), and may provide a variety of dry surface finishes (e.g., matte, semi-gloss, or gloss finishes). Some manufacturers also sell tinted base paints (e.g., red, blue, and yellow bases) that are intended to be combined with additional colorants at the point of sale when a strongly tinted, custom-tailored paint shade with hiding power in one application is desired. The colorants in a custom color paint or stain system may, for example, be volumetrically metered from a multiple colorant dispensing station, which for the U.S. market typically employs 12-20 paint or stain colorants, and other markets may employ more (e.g., 16 or 24 colorants).

[0004] A few years ago, paints and stains were virtually all solvent-based. Currently, over 80 percent of architectural paints and a significant percentage of stains are water-based, although solvent-based paints and stains continue to be used. The overall share of water-based paints and stains as a percentage of total sales is expected to continue to increase. Nevertheless, some workers or consumers continue to prefer solvent-based paints (e.g., alkyd paints) or solvent-based stains for some end-use applications, and they may continue to be sold in large quantities in the future.

[0005] Universal stains have been developed for use in point-of-sale tinting equipment. Universal stains are typically formulated by modifying water-based stain formulations to include appropriate surfactants and, optionally, appropriate dispersants or co-solvents, so that the stains can be used to tint either water-based or solvent-based base paints or stains using the same tinting equipment. Unfortunately, the use of universal stains requires compromises in paint performance to effectively bridge the gap in colorant compatibility between water-based and solvent-based systems. For example, in water-based paints tinted with universal stains, the compromised performance factors may include one or more of higher volatile organic compound (VOC) content, surfactant leaching, increased tack, reduced hardness, reduced blocking resistance, and reduced viscosity. For solvent-based paints tinted with such universal stains, the compromised performance factors may include one or more of longer drying times, reduced film hardness, or changes in gloss. Some point-of-sale paint stores employ separate tinting machines that use water-based colorants to tint water-based paints and stains and contain solvent-based colorants optimized for use with solvent-based paints and stains. However, this solution is not ideal because it requires the investment and maintenance of two separate tinting machines, requires the sale, storage, and inventory of extra stock-keeping units (SKUs) that represent the solvent-based paint colorants, and can result in colorant shelf-life expiration or dispenser clogging issues for less frequently used water-based or solvent-based colorants.

[0006] U.S. Patent Nos. 10,933,389(B2) (Ellsworth et al., '389) and 10,934,151(B2) (Ellsworth et al., '151) describe tinting systems that use water-only colorants to tint water-based paints and stains and water-only colorants with synergists to tint solvent-based paints and stains. WO 2022 / 011012(A1) (Donlon et al.) describes tinting systems that use water-only colorants to tint water-based paints and stains and water-only colorants with synergists and drying agents to tint solvent-based paints and stains. Summary of the Invention

[0007] Although the above-mentioned synergists can be used with various water-only colorants to tint solvent-based paints and stains, improved performance can be obtained by recognizing that synergist optimization may not be sufficient. The inventors have obtained further performance improvements by optimizing water-only colorants that can be used to tint solvent-based paints or stains with synergists so that the colorants work better to tint water-based paints and stains when the synergist is not used. The inventors have developed an array of three-component (or more) surfactant packages for use in making water-only colorants, and water-only colorants containing the disclosed surfactant packages. Compared to the general-purpose colorants, the water-only colorants containing the disclosed surfactant packages can provide equal or better compatibility and better resistance to viscosity loss of the tinted paint when used to tint water-based paints and stains. However, the disclosed water-only colorants do not provide a universal colorant array, since at least the white, green, blue, and red water-only colorants containing the disclosed surfactant packages do not compatibilize tinting solvent-based paints and stains unless a synergist is also used to provide the missing compatibility.

[0008] Thus, the present disclosure provides, in one aspect, a point-of-sale custom color system for tinting waterborne architectural base paints and stains, the system comprising an array of low volatile organic compound water-only liquid colorants including at least white, green, blue, and red colorants, each including at least a three-component surfactant package, a pigment (i.e., a colored dispersible solid particulate material, or a colored dispersible or soluble dye material), and a vehicle, that disperses the colorant compatibly and homogeneously throughout the waterborne base paints and stains, but not compatibly and homogeneously throughout the solvent-borne base paints or stains unless a synergist is used in combination with the colorant that contains one or more components that disperse the water-only colorant in the solvent-borne base paint or stain.

[0009] The disclosure provides, in another aspect, a method of tinting a point-of-sale order paint or stain comprising dispensing, using an automatic or manual colorant dispenser, at a retail, wholesale, or combined retail / wholesale storefront, into a water-based paint or stain one or more water-only liquid colorants selected from an array of colorants including at least white, green, blue, and red colorants, each including at least a three-component surfactant package, a pigment, and a vehicle that causes the colorant to be compatible and homogeneously dispersed throughout the water-based paint or stain, but not compatible and homogeneously dispersed throughout the solvent-based paint or stain unless a synergist is used in combination with the colorant that contains one or more components that cause the water-only colorant to be dispersed in the solvent-based paint or stain.

[0010] In another embodiment, the present disclosure provides a point-of-sale custom color system for tinting waterborne architectural base paints and stains, the system comprising an array of low volatile organic compound water-only liquid colorants including at least white, green, blue, and red colorants, each of which comprises at least a three-component surfactant package, a pigment, and a vehicle that, when used in combination with the colorant, a synergist containing one or more components that disperse the colorant compatible and homogeneous throughout the waterborne base paint or stain and disperse the water-only colorant in the solvent-borne base paint or stain, disperses the colorant compatible and homogeneous throughout the solvent-borne base paint or stain.

[0011] In another embodiment, the disclosure provides a method of tinting point-of-sale custom paint or stain comprising dispensing, at a retail, wholesale, or combined retail / wholesale store using an automatic or manual colorant dispenser, into a water-based paint or stain one or more water-only liquid colorants selected from an array of colorants including at least white, green, blue, and red colorants, each of which includes at least a three-component surfactant package, a pigment, and a vehicle that, when used in combination with the colorant, includes a synergist that contains one or more components that cause the water-only colorant to be compatible and homogeneously dispersed throughout the water-based paint or stain and disperse the colorant in the solvent-based paint or stain.

[0012] In an additional embodiment, the method comprises: One or more water-only colorants are dispensed into water-based paints and stains to tint the water-based paint or stain; or To tint solvent-based paints or stains, a) dispensing one or more water-only colorants and synergists into a solvent-based paint or stain; or b) dispensing one or more water-only colorants into a solvent-based paint or stain containing a synergist; Further includes.

[0013] In yet another aspect, the present disclosure provides a packaged colorant comprising a low volatile organic compound water-only liquid colorant including at least a three-component surfactant package, a pigment, and a vehicle that causes the colorant to be compatible and homogeneously dispersible throughout water-based base paints and stains, but not compatible and homogeneously dispersible throughout solvent-based base paints and stains unless a synergist containing one or more components that cause the water-only colorant to disperse in solvent-based base paints or stains is used in combination with the colorant, the synergist comprising at least one component that causes the water-only colorant to disperse in solvent-based base paints or stains, packaged in a container having a volume of about 0.5 to about 5 L.

[0014] In some embodiments, the colorant in the above systems, methods, and packaged colorants is packaged in a container from which the colorant is gravimetrically or volumetrically dispensed via an automated or manual colorant dispenser into a base paint or stain in the container having a volume of about 0.2-20 L.

[0015] In some embodiments, the point-of-sale custom color systems and methods described above also include at least one water-based base paint or stain packaged in a mostly-filled, but not completely-filled point-of-sale container with an openable and resealable lid, cap, or other closure for an opening through which water-only liquid colorant may be dispensed from an automatic or manual colorant dispenser into the base paint or stain.

[0016] In further embodiments, the point-of-sale custom color system and method described above also includes at least one solvent-based paint or stain packaged in a mostly filled, but not completely filled, point-of-sale container with an openable and resealable lid, cap, or other closure for an opening through which the water-only liquid colorant may be dispensed from an automatic or manual colorant dispenser into the solvent-based paint or stain, and the synergist described above (containing one or more components that disperse the water-only colorant in the solvent-based paint or stain) is included in the solvent-based paint or stain or is added to the solvent-based paint or stain prior to, simultaneously with, or (less preferably) after dispensing the water-only liquid colorant into the solvent-based paint or stain. In additional embodiments, the point-of-sale custom color system includes an air-oxidizable solvent-based paint or stain and a drier that accelerates the cure time of the air-oxidizable (e.g., alkyd) material contained within the base paint or stain.

[0017] The present disclosure, in another aspect, provides an at least three component surfactant package for use in making water-only liquid colorants for tinting water-based paints and stains, comprising at least one surfactant selected from the group consisting of aryl, ...

[0018] [ka] where R is a straight or branched chain alkyl group or mixture of groups having 1 to 20 carbons, and n is the number of moles of ethylene oxide and is at least 7 and at most 50;

[0019] [ka] wherein m is the number of moles of ethylene oxide and is at least 5 and at most 25, in some embodiments at least 10 and at most 20; and R1, R2, R3, R4, and R5 are independently hydrogen or a straight or branched chain aliphatic or aromatic hydrocarbon group containing at least 4 and at most 10 carbon atoms; and

[0020] [ka] wherein R6 is hydrogen or an ethylene oxide chain containing at least 5 and at most 15 moles EO and a terminal hydrogen atom, a nitrogen group, an alkyl group, or an alkaryl group; and R7 and R8 are independently hydrogen, sodium, potassium, a counterion, or an ethylene oxide chain containing at least 5 and at most 15 moles EO and a terminal hydrogen atom, an alkyl group, or an alkaryl group.

[0021] In some embodiments, the disclosed surfactant package is a mixture of: a) alcohol ethoxylates having a hydrophilic-lipophilic balance (HLB value) of 12 to 20; b) tristyrylphenol ethoxylates having 5 to 15 moles of ethylene oxide, and c) Aliphatic phosphate esters having 5 to 15 moles of ethylene oxide.

[0022] The disclosed systems, methods, and surfactant packages enable both water-based and solvent-based, custom-tinted paints and stains to be formulated and sold at the point of sale using a single tinting machine and a single colorant array, while avoiding or minimizing additional inventory, dedicated dispensers, or dedicated floor space. [Brief description of the drawings]

[0023] [Figure 1]FIG. 1 is a perspective view of an embodiment of the disclosed paint or stain tinting system. [Diagram 2] FIG. 1 is a perspective view of an embodiment of the disclosed paint or stain tinting system. [Diagram 3] FIG. 1 is a schematic diagram of an embodiment of the disclosed colorant array and the disclosed synergist.

[0024] Like reference symbols in the various figures of the drawings indicate like elements. Elements in the drawings are not drawn to scale. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0025] Unless the context indicates otherwise, the following terms shall have the following meanings and are applicable to both the singular and plural forms:

[0026] The terms "a," "an," "the," "at least one," and "one or more" are used interchangeably. Thus, for example, a system or method that includes "a" pigment means that the system or method can include "one or more" pigments.

[0027] The terms "architectural coatings" and "architectural stains" refer to paints and stains, respectively, for use on interior or exterior surfaces of buildings or structures, such as walls, trim, floors, decks, railings, ceilings, roofs (including metal roofs, shingles, and tile), roads, sidewalks, and the like.

[0028] The term "array" when used with respect to colorants means an assortment of colorants intended to be used individually or in suitable combination to tint a base paint or stain to provide a user-customized color in a wide range of hues. A typical array usually contains at least white, green, blue, and red colorants, and usually also contains one or more black colorants, one or more yellow colorants, and one or more oxide colorants such as red oxide or yellow oxide. The individual colorants in a typical array are usually supplied by a single manufacturer, packaged in similar containers, each with a similar label with a distinct SKU identifier, and may have a unified trademark for the array or for the brand of paint or stain for which the array is intended to be used.

[0029] The term "automated colorant dispenser" means a dispenser for paint or stain colorants that is controlled or controllable via an electronically regulated precision gravimetric or volumetric metering device to dispense a controlled amount of one or more colorants (e.g., a water-only colorant) into a base paint or stain container, thereby facilitating the preparation of a tinted paint or stain, the tint of which is selected from an array of tints. The type and amount of colorant selected by such an automatic colorant dispenser is optionally and preferably controlled using software and a suitable database.

[0030] The term "base paint or stain" means a water- or solvent-based paint or stain product packaged in a mostly, but not completely, filled point-of-sale container having a volume of about 0.2 to 20 L with an openable and resealable lid, cap, or other closure, which may be used as is, but typically can be tinted at the point of sale by adding one or more colorants to the paint or stain product in the container and stirring, shaking, or otherwise mixing the contents of the container to cause the colorants to be compatible and homogeneously distributed throughout the base paint or stain product.

[0031] The term "binder" means a film-forming natural or synthetic polymer suitable for use in a paint or stain.

[0032] The term "colorant" means a composition that can be added (e.g., dispensed) to a point-of-sale container having a majority of its internal volume (e.g., two-thirds or more of the volume of the container) filled with such base paint or stain, but not completely pre-filled, and containing pigment and vehicle, but substantially free of binder, to change the hue or shade of the base paint or stain.

[0033] The terms "compatible" and "compatible," when used in reference to a colorant, mean that when 4 fluid ounces of the colorant is added to a nominal (128 fluid ounce) gallon of base paint or stain and shaken for 5 minutes with a standard paint shaker, the colorant disperses throughout the base paint or stain and undergoes no visually discernible separation when allowed to stand at room temperature for 1 week.

[0034] The term "custom tinted" when used in reference to a system or method for tinting a base paint or stain means that one or more colorants can be dispensed and mixed into the base paint or stain to provide a finished paint or stain that matches a wide variety (e.g., more than 100, or even more than 1000) of preselected formula colors, or, if desired, a randomly selected color. The colors of the preselected formulas are typically viewed by a potential end user using a printed color chart or a displayed computer image.

[0035] The term "headspace" when used with respect to a base paint or stain in an openable container refers to the small unfilled portion of the total container volume that is available for and intended to be used for the addition of colorant (e.g., from about 1% to about 33%, and in some embodiments from about 1% to about 15% of the total container volume).

[0036] The terms "homogeneous" and "homogeneously" when used in reference to a colorant mean that when 4 fluid ounces of the colorant are added to a nominal (128 fluid ounce) gallon of base paint or stain and shaken for 5 minutes in a standard paint shaker, the colorant is uniformly dispersed throughout the base paint or stain without any visually discernible separation.

[0037] The term "liquid" when used to describe a material that can exist in several different phases refers to the phase occupied by the material at room temperature (23° C.) and 1 atm.

[0038] The terms "low volatile organic compounds" and "low VOC" when used in reference to a stain, paint, or stain mean that the stain, paint, or stain, when in liquid form, contains less than 50 grams of carbon per liter (g / L) of volatile compounds in accordance with California South Coast Air Quality Management District Rules 102 and 113 (amended February 2016).

[0039] The term "manual colorant dispenser" means a non-automatic dispenser for paint or stain colorants having a manually movable piston whose stroke is indexed to manually meter an amount of one or more colorants into a base paint or stain container, thereby facilitating the preparation of a tinted paint or stain whose tint is selected from an array of tints.

[0040] The term "molecular weight" when used in reference to polymeric materials means number average molecular weight as determined using gel permeation chromatography and polystyrene standards.

[0041] The term "NVM" is an abbreviation for nonvolatile material and refers to materials that do not significantly evaporate at standard temperature and pressure. NVM content can be evaluated using ASTM D1353-13.

[0042] The term "paint" means a coating composition comprising a pigment and a binder which, when applied to form a thin (e.g. 100 μm) wet thickness film on a smooth, freshly sanded wood surface, when dried hides or substantially hides the grain of the wood and presents a new surface having the appearance of its own.

[0043] The term "pigment" refers to both colored dispersible solid particulate materials and (for brevity) colored dispersible or soluble dye materials which impart a visually noticeable color to a base paint or stain when 5% by weight (for colored dispersible solid particulates) or 0.05% by weight (for colored dispersible or soluble dyes) of the material is added to (e.g., distributed within) the base paint or stain. The presence or absence of visually noticeable color can be evaluated by preparing drawdown samples of the base paint or stain both with and without the pigment, casting such samples as 25 μm dry thickness coatings on the white portion of a BYK-Gardner No. PA-2811 Opacity Drawdown Chart (manufactured by BYK-Gardner USA) or an equivalent chart, and inspecting the coatings under normal overhead room lighting.

[0044] The term "pigment volume concentration" when used in reference to a paint, stain, or colorant means the total percentage of the dry coating volume occupied by all pigment species in the coating.

[0045] The terms "point of sale" and "retail store" when used with respect to a job site, storage area, warehouse, or other establishment means a location where custom mixed paint or stain is colored and mixed in small batch lots (e.g., 1 / 2 pint, 1 pint, 1 quart, 1 liter, 1 gallon, 4 liter, 5 gallon, or 20 liter containers, equivalent to approximately 0.2 to 20 L containers) for sale to end users (e.g., painters, builders, and homeowners). Exemplary point of sale retail, wholesale, or combination retail / wholesale establishments include paint stores, hardware stores, building supply stores (including warehouses), and distribution centers.

[0046] The terms "preferred" and "preferably" refer to embodiments of the invention that may provide certain benefits, under certain circumstances. However, other embodiments may also be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, and is not intended to exclude other embodiments from the scope of the invention.

[0047] The term "predominantly or exclusively" when used in reference to the amount of a component in a synergist means that the named component represents at least 50% by weight of the components in such synergist, excluding any solvent or other carrier (e.g., water) that may be present in the synergist. In some embodiments, the named component may represent at least 60%, at least 70%, at least 80%, or at least 90% by weight of the components in such synergist, excluding such solvent or other carrier. The term "exclusively" means that the synergist consists essentially of or consists of such named component, excluding such solvent or other carrier.

[0048] The term "drier" refers to an additive dispersible in an air-oxidizable solvent-borne base paint or stain that accelerates the cure time of air-oxidizable (e.g., alkyd) materials contained therein. Without wishing to be bound by theory, it is believed that such driers accelerate such cure times by catalyzing the free radical autoxidation of conjugated double bonds contained therein when exposed to air.

[0049] The term "drier-free" when used with respect to a drier-free synergist or base paint or stain means that the representative components are formulated without the inclusion of a drier. In some embodiments, a drier-free composition may be the same as a composition that is substantially free of drier materials.

[0050] The term "solid" when used to describe a material that can exist in several different phases refers to the phase occupied by the material at room temperature (23° C.) and 1 atm.

[0051] The term "solvent" when used in reference to a paint, stain, or colorant means an organic liquid that dissolves or disperses other materials in the paint, stain, or colorant, and is considered to include both volatile and nonvolatile and both reactive and nonreactive materials.

[0052] The term "solvent-based" when used in reference to a paint, stain, or colorant means that the primary liquid vehicle or carrier of the paint, stain, or colorant is a non-aqueous solvent or mixture of non-aqueous solvents.

[0053] The term "stain" refers to a coating composition, including a binder, which, when applied to a freshly sanded smooth wood surface to form a thin (e.g., 100 μm) wet thickness film, when dried, does not hide both the grain and the texture of the wood. When a translucent stain is applied to wood, the grain and the texture usually both remain visible, whereas when a solid (i.e., opaque) stain is applied, the grain is usually hidden, but the texture usually remains visible. Stains typically penetrate into wood or other porous substrates (e.g., concrete) to a much greater extent than paints.

[0054] The term "substantially free" when used with respect to a component or composition means that the referenced component or composition contains less than 0.1% by weight of the recited component. The term "completely free" of a particular compound means that the recited material or composition contains less than 100 parts per million (ppm) of the compound.

[0055] The terms "specific color strength" and "color strength" refer to values ​​obtained using a spectrophotometric instrument such as, but not limited to, a Datacolor DC500, DC800, or similar spectrophotometer, D65 illuminant, CIE 1964 10° standard observer angle, and reflectance mode.

[0056] The term "uncolored" when used in reference to a synergist means that the synergist does not contain a visually noticeable amount of pigment. However, the synergist may have its own inherent color, such as the yellow color sometimes found in amine group-containing surfactants or provided by certain drying agents.

[0057] The term "water-based" when used in reference to a paint, stain, or colorant means that the primary liquid vehicle or carrier of the paint, stain, or colorant is water.

[0058] The term "water-only" when used in reference to a liquid colorant means that the colorant can be used to tint a water-based base paint or stain, but exhibits poor rub-up (i.e., poor compatibility and homogeneity) when added alone in an attempt to tint a conventional solvent-based paint (e.g., SWP™ Exterior Oil Base Paint Tinting White, Product No. A02W00528) or a conventional solvent-based stain (e.g., Cabot™ Semi-Transparent Deck & Siding Stain Neutral Base No. 306). Rub-up can be evaluated using the rub-up test set forth below in the Examples section. Poor rub-up corresponds to a moderate or severe rating in the rub-up test. A skilled paint tinter would consider a water-only colorant to be a "non-general purpose" colorant and a general purpose colorant to be a non-water-only colorant.

[0059] The recitation of numerical ranges using endpoints includes all numbers subsumed within that range (eg, 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, 5, etc.).

[0060] The disclosed surfactant package comprises at least three surfactants. The inventors have found that when using water-only colorants to tint water-based paints and stains, surfactant packages containing three or more surfactants can provide better tinted paint and stain performance compared to water-only colorants that contain only one or two surfactants. Typically, water-only colorants only require a single surfactant to be compatible mixed into water-based paints or stains.Exemplary surfactants that may be used in the disclosed surfactant packages include anionic, amphoteric, and nonionic materials available from a variety of suppliers, including 3M, Air Products and Chemicals, Inc., Akzo Nobel, Ashland, BASF, Dow Chemical Co., EI DuPont de Nemours and Co., Elementis Specialties, Inc., Harcros Chemicals, Rhodia, and Solvay, such as the TAMOL™ series from Dow Chemical Co., nonyl and octyl phenol ethoxylates from Dow Chemical Co. (e.g., TRITON™ X-45, TRITON X-100, TRITON X-114, TRITON X-165, TRITON X-305, and TRITON X-405) and other suppliers (e.g., the T-DET N series from Harcros Chemicals), alkylphenol ethoxylate (APE) replacements from Dow Chemical Co., Elementis Specialties, Inc., and the like, Air Products and and various members of the SURFYNOL™ series manufactured by Chemicals, Inc. (e.g., SURFYNOL 104, SURFYNOL 104A, SURFYNOL 104 BC, SURFYNOL 104 DPM, SURFYNOL 104E, SURFYNOL 104H, SURFYNOL 104 PA, SURFYNOL 104PG50, SURFYNOL 104S, SURFYNOL 2502, SURFYNOL 420, SURFYNOL 440, SURFYNOL 465, SURFYNOL 485).Examples of surfactants include SURFYNOL 485W, SURFYNOL 82, SURFYNOL CT-211, SURFYNOL CT-221, SURFYNOL OP-340, SURFYNOL PSA204, SURFYNOL PSA216, SURFYNOL PSA336, SURFYNOL SE, and SURFYNOL SE-F), various fluorocarbon surfactants from 3M, EI DuPont de Nemours and Co., and other suppliers, and phosphate esters from Ashland, Rhodia, and other suppliers. The individual types and amounts of these and other surfactants are typically selected empirically for each colorant in the array based on colorant performance factors including storage stability, compatibility and ease of use with water-based paints and stains, and performance of the desired tinted water-based paint or stain after addition of the colorant.

[0061] In some embodiments, the disclosed surfactant package includes at least two nonionic surfactants and at least one anionic surfactant. The nonionic surfactant desirably includes a hydrophilic alkylene oxide portion (e.g., an ethylene oxide portion containing multiple -CH2CHO- groups) and a hydrophobic portion, where at least one of the hydrophobic portions of the nonionic surfactant contains a straight or branched chain aliphatic group (e.g., an alkyl group or mixture of alkyl groups having 1 to 20 carbons) and at least one other of the hydrophobic portions of the nonionic surfactant contains one or more aromatic rings (e.g., 1, 2, 3, 4, or more six-carbon aromatic rings). In some embodiments, all three of the at least three surfactants have a number average molecular weight of less than 2,000 g / mol. The anionic surfactant desirably includes a hydrophilic alkylene oxide portion (e.g., an ethylene oxide portion containing multiple -CH2CHO- groups) and a hydrophobic portion, where the hydrophobic portion desirably includes a phosphorus group (e.g., a phosphate ester group) or a sulfur group (e.g., a sulfate or sulfonate group). In some embodiments, the disclosed surfactant packages comprise the following formulas I, II, and III:

[0062] [ka] where R is a straight or branched chain alkyl group or mixture of groups having 1 to 20 carbons, and n is the number of moles of ethylene oxide and is at least 7 and at most 50;

[0063] [ka] wherein m is the number of moles of ethylene oxide and is at least 5 and at most 25, in some embodiments at least 10 and at most 20; and R1, R2, R3, R4, and R5 are independently hydrogen or a straight or branched chain aliphatic or aromatic hydrocarbon group containing at least 4 and at most 10 carbon atoms; and

[0064] [ka] where R6 is hydrogen or an ethylene oxide chain containing at least 5 and at most 15 moles EO and a terminal hydrogen atom, a nitrogen group, an alkyl group, or an alkaryl group; and R7 and R8 are independently hydrogen, sodium, potassium, a counterion, or an ethylene oxide chain containing at least 5 and at most 15 moles EO and a terminal hydrogen atom, an alkyl group, or an alkaryl group.

[0065] In some embodiments, the disclosed surfactant package includes an alcohol ethoxylate having a hydrophilic-lipophilic balance (HLB value) of 12 to 20, a tristyrylphenol ethoxylate having 5 to 15 moles of ethylene oxide, and an aliphatic phosphate ester having 5 to 15 moles of ethylene oxide.

[0066] Table I below provides a list of commercially available surfactants that can be used in the disclosed surfactant packages.

[0067] [Table 1-1]

[0068] [Table 1-2]

[0069] Table II below provides a list of additional commercially available surfactants that can be used in the disclosed colorants.

[0070] [Table 2-1]

[0071] [Table 2-2]

[0072] The colorant may contain, for example, at least about 0.5, at least about 1, or at least about 2 wt. % and up to about 20, up to about 15, or up to about 10 wt. % of the disclosed surfactant package based on the total weight of the colorant. Different colorants may contain different total amounts of the surfactant package, as well as different amounts or relative ratios of each individual surfactant. For example, in an array containing white, green, blue, red, yellow, and black colorants and using surfactant packages containing surfactants of formula I, formula II, and formula III, improved performance can be obtained when the yellow and black colorants contain a higher amount of the surfactant package compared to the other colorants. Also, improved performance can be obtained when the white, green, blue, yellow, and black colorants contain a higher amount of the surfactant of formula I relative to the amount of the surfactant of formula II or formula III, and when the red colorant contains a higher amount of the surfactant of formula III relative to the amount of the surfactant of formula I or formula II.

[0073] A variety of water-only stains can be used in the disclosed systems and methods. Water-only stains will typically contain the disclosed surfactant package, one or more pigments, one or more vehicles or carriers, one or more pigment dispersants, and optional adjuvants, and are in the form of a pourable liquid. The stains typically do not contain a film-forming binder and must be combined with a base paint or stain to provide a durable dried or cured finish.

[0074] A variety of pigments may be used in the disclosed colorants (as well as the base paint or stain), which are well known to those skilled in the art. It is desirable that the pigments form a stable dispersion that does not require stirring before use. In some examples, suitable pigments may also or alternatively be commercially referred to as dyes. Exemplary pigments include treated or untreated inorganic pigments and mixtures thereof, such as metal oxides including titanium dioxide, iron oxides of various colors (including black), and zinc oxide; and metal flakes such as aluminum flakes, pearlescent flakes, and the like. Exemplary pigments include treated or untreated organic pigments and mixtures thereof, such as carbon black, azo pigments, benzimidazolinones, carbazoles such as carbazole violet, diketopyrrolopyrroles, indanthrones, isoindolinones, isoindolones, perylenes, phthalocyanines, quinacridones, and thioindiio reds. Suitable pigments are commercially available from a variety of commercial sources, including BASF Colors & Effects GmbH, LANXESS, Cabot Corp, Ciba Specialty Chemicals, Clariant, Ferro Corporation, Shepherd Color Company, Sun Chemical and Tomatec America, Inc. Other exemplary pigments are described, for example, in U.S. Pat. Nos. 8,141,599 (B2) (Korenkiewicz et al.), 8,746,291 (B2) (Hertz et al.), and 8,748,550 (B2) (Cavallin et al.). When a custom-tinted paint or stain with maximum exterior durability is desired, a colorant or colorant array containing only inorganic pigments or pigment mixtures may be preferred. In some embodiments, the colorant array includes a non-infrared absorbing pigment for tinting dark exterior paints and an infrared absorbing pigment for tinting dark interior paints, as described in U.S. Patent No. 8,752,594 (B2) (Gebhard et al.). The colorant may contain, for example, at least about 2, at least about 3, or at least about 5% by weight pigment and up to about 90, up to about 80, or up to about 70% by weight pigment.

[0075] Pigments include extenders, inert pigments, or fillers, such as talc, china clay, barite, carbonates, silicates, and mixtures thereof, such as magnesium silicate, calcium carbonate, aluminosilicates, silica, and various clays; plastic beads (e.g., polystyrene or polyvinyl chloride beads), microspherical materials containing one or more voids, and vesiculated polymer particles (e.g., U.S. Pat. No. 4,427,633). ,835, 4,920,160, 4,594,363, 4,469,825, 4,468,498, 4,880,842, 4,985,064, 5,5157,084, 5,041,464, 5,036,109, 5,409,776, and 5,510,422). Other exemplary extenders, inert pigments, or fillers include EXPANCEL™ 551DE20 acrylonitrile / vinyl chloride foam particles (manufactured by Expancel Inc.), SIL-CEL™ 43 glass microporous filler (manufactured by Silbrico Corporation), FILLITE™ 100 ceramic spherical particles (manufactured by Trelleborg Fillite Inc.), SPHERICEL™ hollow glass spheres (manufactured by Potter Industries Inc.), 3M ceramic microspheres including grades G-200, G-400, G-600, G-800, W-210, W-410, and W-610 (manufactured by 3M), 3M hollow microspheres including 3M Performance Additives iM30K (also manufactured by 3M), INHANCE™ UH 1900 polyethylene particles (manufactured by Fluoro-Seal Inc.), and BIPHOR aluminum phosphate (manufactured by Bunge Fertilizantes SA, Brazil). The colorant may contain, for example, at least about 0.5, at least about 1, or at least about 2% by weight of the combined weight of pigments, extenders, inert pigments, and fillers, and up to about 80, up to about 70, or up to about 60% by weight of the combined weight of pigments, extenders, inert pigments, and fillers.

[0076] A variety of vehicles or carriers may be used in the disclosed colorants and are well known to those skilled in the art. A preferred vehicle or carrier is water, which may be, for example, tap water, deionized water, demineralized water (e.g., by reverse osmosis), or distilled water. The co-solvent may help disperse the pigment in the colorant or in the base paint or stain, may accelerate, retard, or otherwise change the time or release associated with drying, may improve wet edge or overlap properties, may improve freeze-thaw protection, or may provide or improve other characteristics, and is generally not retained in the dried, cured, or otherwise solidified paint or stain coating. The selected co-solvent may be a hazardous air pollutant solvent (HAPS material), but is preferably a non-HAPS material or substantially free of HAPS materials. Exemplary cosolvents typically have low molecular weights (e.g., up to about 700, up to about 600, up to about 500, or up to about 400 g / mol) and include, for example, glycols (e.g., ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, and propylene glycol), glycol ethers (e.g., DOWANOL™ DPM and Butyl CELLOSOLVE™ from Dow Chemical Co.), alcohols (e.g., methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, 2-methylbutanol, isoamyl alcohol, and other primary amyl alcohol isomers, n-pentanol, 2-ethylhexanol, 4-hydroxy-2,6,8-trimethylnonane, and diisobutylcarbinol), esters and ester alcohols (e.g., isopropyl acetate, n-butyl acetate, isobutyl acetate, n-propyl acetate, primary amyl acetate mixed isomers, and UCAR™ Ester from Dow Chemical Co.). EEP), ketones (e.g., diisobutyl ketone and ECOSOFT™ Solvent IK from Dow Chemical Co.), CARBOWAX 300 and CARBOWAX 600 polyethylene from Dow Chemical Co., mixtures thereof, and the like.The colorant may contain, for example, at least about 8, at least about 10, or at least about 12% by weight of the vehicle or carrier, and up to about 70, up to about 60, or up to about 50% by weight of the vehicle or carrier.

[0077] Various pigment dispersants may be used in the disclosed colorants, and such pigment dispersants are well known to those skilled in the art. Exemplary pigment dispersants include anionic polyelectrolyte dispersants such as maleic acid copolymers, acrylic acid copolymers, including methacrylic acid copolymers, and carboxylic acids such as tartaric acid, succinic acid, citric acid, itaconic acid, and mixtures thereof, as well as other materials well known to those skilled in the art. Some colorants in the array may not require a pigment dispersant. Colorants that use them may contain, for example, at least about 0.1, at least about 0.5, or at least about 1 weight percent pigment dispersant, and up to about 5, up to about 3, or up to about 2 weight percent pigment dispersant.

[0078] The disclosed surfactants are suitable for inclusion in one or more water-only colorants in a colorant array. The disclosed colorant array can also be prepared in some cases by adding suitable additional surfactants to existing water-only fluid colorants manufactured by manufacturers such as Akzo Nobel, BASF, Behr Paint Company, Clariant, Color Corporation of America (a subsidiary of the assignee), CPS Color, Inc., Evonik Industries, ICI, PPG, and Sherwin-Williams, such as the NOVOCOLOR HPII 8600 and NOVOCOLOR HP 8900 colorant lines from Color Corporation of America, the GENNEX colorant line from Benjamin Moore, and the ECOTONER colorant line from Sherwin-Williams. Such modified colorants can be all or part of a particular product array. For example, an array of water-only colorants including at least white, green, blue, and red colorants may be selected from the NOVOCOLOR HP 8900 product line described above by selecting White #8900, either or both Phthalo Green #8920 or #8921, either or both Phthalo Blue #8930 or #8932, and either or both Interior Red #8942 or Exterior Red #8951. Additional colorants may be added to the array as needed, depending on the availability of suitable dispenser slots. Exemplary such additional colorants include one or more yellow, orange, magenta, brown, or black colorants from the colorant manufacturers described above.

[0079] The disclosed systems and methods may use, for example, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 colorants, but may use as few as 4 colorants if only a limited (i.e., relatively few hues and relatively narrow gamut) color space is acceptable. The disclosed systems and methods may use more than 15 colorants if sufficient dispenser slots are available and additional colorant SKUs are acceptable. For example, the disclosed systems and methods may use 16, 17, 18, 19, 20, 21, 22, 23, or 24 colorants.

[0080] When the available number of colorant dispenser canisters is limited (e.g., when using 12 or fewer canister dispensers), the number of colorant SKUs can be reduced by recognizing that some individual colorants are themselves mixtures of pigments that can be replaced with precisely metered blends of the individual colorants. For example, many custom color paint systems use one or more earth tone colorants that are variously referred to using names such as brown oxide, raw umber, or umber. Brown oxide colorants are sometimes referred to as being made from a single pigment (e.g., PBr7 natural iron oxide), but may actually be made using a blend of red oxide and yellow oxide (e.g., PR101 red iron oxide and PY42 yellow iron oxide) tinted with carbon black (e.g., PBk7 carbon black) to meet a particular color goal. Similarly, raw umber or umber earth tone colorants (sometimes collectively referred to as "raw umber" colorants) may be made from a blend of colored oxides and carbon black. These blends can also be replaced by adding colorants made entirely (or substantially entirely) of the appropriate individual pigments to provide a paint or stain whose coloration is similar to that which would be obtained using conventional blended pigment colorants. This can be done by using an automated colorant dispenser that has a suitably small minimum fluid volume (e.g., a minimum fluid dispensing volume of less than 0.01 fluid ounces (<0.3 mL)) to allow for the dispensing of small amounts of the individual colorants. Further details regarding the manner in which such blends can be dispensed can be found in the aforementioned U.S. Pat. No. 8,141,599(B2). For example, whenever a paint or stain tinted with a brown oxide or low umber shade is required, a blend made using small, precisely metered amounts of yellow oxide pigment, red oxide pigment, and black pigment can be dispensed into the base paint or stain.

[0081] The colorant may optionally contain various adjuvants well known to those skilled in the art. Representative adjuvants are described in Koleske et al., Paint and Coatings Industry, April, 2003, pages 12-86. Exemplary adjuvants and their commercially available examples include biocides, bactericides, fungicides, and preservatives (e.g., BUSAN™ 1292 from Buckman Laboratories, Inc., NOPCOCIDE™ N-40D from Cognis, KATHON™ LX from Rohm & Haas, and POLYPHASE™ 663, POLYPHASE™ 678, and POLYPHASE PW-40 from Troy Corporation); buffers and pH adjusters; defoamers; humectants; light stabilizers (e.g., hindered amine light stabilizers such as TINUVIN™ 123-DW and TINUVIN 292 HP from Ciba Specialty Chemicals); optical brighteners; thickeners; ultraviolet light absorbers (e.g., TINUVIN 234 and TINUVIN 1130 from Ciba Specialty Chemicals); wetting agents (e.g., BYK™ 346 and BYK™ 1130 from Altana). 348, PENTEX™ 99 from Rhodia, and TROYSOL LAC™ from Troy Corporation. The amount and type of such adjuvants are typically selected empirically, keeping in mind that the colorants are preferably non-settling and low VOC, and these goals may be affected by the choice and amount of any adjuvant.

[0082] The disclosed colorants desirably have a PVC value of at least about 0.1% by volume, at least about 0.5% by volume, or at least about 1% by volume and up to about 25% by volume. The amount of colorant dispensed into a 1 gallon (3.78 L) nominal container of base paint or stain will vary depending in part on the PVC value of the base paint, stain, or colorant, and may range, for example, from about 0.00065 fluid ounces (0.19 mL) to about 16 fluid ounces (473 mL) of colorant addition, with larger amounts typically being used with clear base paints or stains or in larger base paint or stain containers, and smaller amounts typically being used with white base paints or stains or in smaller base paint or stain containers. The finished tinted paint or stain may have a PVC value of, for example, at least about 0.5 or at least about 1% by volume, and may have a PVC value of, for example, up to about 85% by volume, or up to about 50% by volume.

[0083] The colorant array may contain one or more solvent-based colorants, if desired. However, preferably, all of the colorants in the array and in the colorant dispenser are water-based colorants. In some embodiments, most or even all of the colorants in the array and in the colorant dispenser are water-only fluid colorants. In other embodiments, fewer than two, fewer than one, or none of the colorants in the array and in the colorant dispenser are compatible with alkyd paints and stains, and the remaining colorants in the array, when added in a representative tinting amount of about 1 to about 15% of the alkyd paint or stain container volume, exhibit visually objectionable rub-up or insufficient tint strength when dispensed into such alkyd paints and stains without the synergist described above.

[0084] The disclosed colorants (and optionally, synergists, desiccants, or mixtures thereof described above) are typically packaged in containers suitable for use in a selected colorant dispenser and sold to the owner or operator of the dispenser at a custom tint facility at the point of sale, rather than to the end user of the custom tinted paint or stain. Exemplary small batch lot container sizes are about 0.5, 1, 2, or 3 quarts, about 1 gallon, or about 0.5, 1, 2, 3, 4, or 5 liters, which correspond to containers of about 0.5 to about 5 L. Exemplary containers include boxes, cans, cartridges, jars, pouches (e.g., sealed pouches made of metal or plastic), squeeze bottles, syringes, tubes (e.g., collapsible tubes such as metal or plastic toothpaste-type tubes, and more rigid tubes with movable pistons or plungers such as metal, plastic, or paper caulking-type tubes), and other containers in which the colorants, synergists, and desiccants can be sealed for storage, transport, and use. The colorant, synergist, and desiccant may be provided to the dispenser owner or operator in a can or other sealed container designed to be opened, for example, using a can opener or other can piercing device. The container may also or alternatively have a manually openable closure, such as a resealable and resealable cap, or an irreversibly openable closure, such as a peel seal or a breakable septum. When provided to the dispenser owner or operator, the colorant container typically contains little or no headspace.

[0085] To replace an empty container in the stain dispenser, a new stain container may be placed in an appropriate slot or other receptacle, or may be poured into an appropriate hopper or other container in the stain dispenser, so that the desired stain is dispensed in a controlled amount. In either case, once the container is opened, the stain may be dispensed via the stain dispenser into the available headspace of the base paint or stain container. Desirably, the stain container, the stain dispenser, or both have a nozzle, adapter orifice, or other design that facilitates clean entry of the stain, drying agent, or synergist into the stain dispenser while minimizing spillage or waste before or after use.

[0086] Various synergists may be used in the disclosed systems and methods, for example, as described in the above-mentioned U.S. Pat. Nos. 10,933,389 (B2), 10,934,151, and WO 2022 / 011012 (A1). The synergists may contain various surfactants (e.g., nonionic, anionic, cationic, or amphoteric surfactants), optional dispersants, and optional cosolvents. Exemplary dispersants and cosolvents include the dispersants and cosolvents discussed above. Exemplary synergists also include some of the components used or recommended for use in general-purpose paint colorants, such as those described in U.S. Pat. No. 2,878,135 (Willis), U.S. Pat. No. 6,287,377 (B1) (Binns et al.), U.S. Pat. No. 7,659,350 (B2) (Coward et al.), U.S. Pat. No. 9,080,030 (B2) (Amiel et al.), U.S. Patent Application Publication No. 2016 / 0333213 (A1) (Zhou et al.), and WO 2016040641 (A1) (Donlon et al.). The synergist is preferably a low-VOC material, although low-VOC properties are not required given the intended use in solvent-based paints and stains. In some embodiments, the synergist includes one or more surfactants, and the surfactants are selected to provide improved colorant compatibility across the full range of solvent-based paint or stain binders. In some embodiments, the synergist may optionally include one or more dispersants, one or more co-solvents, or one or more dispersants and one or more co-solvents. The surfactant and optional dispersant may be solid or liquid. As will be understood by those skilled in the art, the optional co-solvent is liquid, preferably a low-VOC liquid. When solid surfactants or solid optional dispersants are used, they may be combined with liquid surfactants, dispersants, co-solvents, or conventional carriers or solvents (preferably low-VOC carriers or solvents) to provide liquid synergists, if desired.

[0087] Suitable synergists may be selected in a variety of ways, for example, by selecting ingredients previously used in generic colorants used in the paint and stain industry in empirical testing to identify surfactants, driers, dispersants, or co-solvents that make individual members of the desired water-only colorant array compatible with the desired base paints and stains, or by selecting surfactants, driers, dispersants, or co-solvents based on structural considerations such as hydrophilicity, oleophilicity, and the synergist's ability to draw the water-only colorant into the solvent phase. In some embodiments, the disclosed systems and methods may employ at least two synergists, one configured for use in light-colored paints or stains (e.g., shades of white, pastels, etc.) and one configured for use in dark-colored paints or stains. Additionally or alternatively, the disclosed systems and methods may employ more than one different synergist, each optimized for use with a paint or stain, or each optimized for use with different commercially available base paints or stains (e.g., different branded product lines of base paints or stains).

[0088] The synergist may optionally include one or more additional adjuvants, such as one or more rheology modifiers or thickeners. Other optional adjuvants include, but are not limited to, adhesion promoters, antioxidants, biocides, buffers, coalescing aids, defoamers, dispersants, dyes, extenders, fillers, humectants, leveling agents, neutralizers, optical brighteners, pearlescent agents, plasticizers, polymer additives, preservatives, reactive diluents, tackifiers, UV stabilizers (e.g., hindered amine light stabilizers), and waxes. In some embodiments, the synergist consists essentially of or consists of surfactants, optional dispersants, optional cosolvents, and optional rheology modifiers or thickeners. For example, the synergist may contain less than 5% by weight or less than 1% by weight of any other component.

[0089] Sufficient synergist should be used to achieve the desired degree of dispersion of colorant in the solvent-based base paint or stain to be tinted, while leaving sufficient residual head space in the base paint or stain container to allow for the addition of the desired amount of colorant. Expressed on a volumetric basis, exemplary amounts of synergist may be, for example, at least about 2, at least about 4, at least about 6, at least about 8, or at least about 10 mL of synergist per liter of solvent-based base paint or stain to be tinted, and up to about 60, up to about 50, up to about 40, up to about 30, or up to about 20 mL of synergist per liter of solvent-based base paint or stain to be tinted. When made to contain a combination of components, the synergist preferably provides a stable, homogenous, non-settling composition that can be mixed into the base paint or stain in such exemplary amounts using a conventional paint stirrer or shaker without forming visible lumps after mixing.

[0090] A variety of desiccants may be used in the disclosed systems and methods, such as those described in WO 2022 / 011012 A1, cited above. Exemplary desiccants include metal organic compounds that catalyze the solidification of air-oxidizable solvent-based paints and stains. In some embodiments, the desiccants may include metal carboxylate driers, such as organometallic salts derived from salts or coordination compounds of hydrocarbon carboxylates and metal ions. The metal source and one or more organic acids may be dissolved in a diluent to produce the organometallic salts. Exemplary organic acids may be natural or synthetic. Natural organic acids may include, but are not limited to, naphthenates (e.g., petroleum-based derivatives), fatty acids (e.g., unsaturated oleates), tallates, and the like. Synthetic organic acids may include, but are not limited to, 2-ethylhexanoate, neodecanoate, isononanoate, and the like. In some instances, the drying agent may be characterized as an oil drying agent or a Japan drier because it serves to reduce the drying or curing time of solvent-based paints or stains.

[0091] The desiccant may include one or more auxiliary, primary, or through drier materials. A primary drier functions primarily by drying the surface of the coating composition (e.g., skinning), while the coating underneath remains wet. A through drier may help ensure that the coating dries at a uniform rate throughout the body of the film, not just the surface, by, for example, linking fatty acid chains in the composition via oxygen-metal-oxygen bridges to provide cross-linked connections in the coating. Auxiliary driers are useful for modifying the effect of other drier materials. Examples of primary drier metals that can be used as desiccants include, but are not limited to, cobalt, manganese, iron, and vanadium. Examples of through drier metals that can be used as desiccant materials include, but are not limited to, aluminum, cesium, lithium, neodymium, potassium, strontium, and zirconium. Examples of auxiliary drier metals that can be used as desiccant materials include, but are not limited to, calcium, barium, and zinc. In a preferred example, the desiccant may include one or more cobalt or iron based desiccants.

[0092] Additionally or alternatively, it may be desirable to select a drier that exhibits reduced color properties, so that the inclusion of the drier does not alter the color performance of the base paint or stain or added colorants. Iron-based driers may be particularly preferred for light-colored paints or stains due to their compatibility or unobtrusive color properties and robust drying properties. Other driers, such as cobalt-based driers, may have a slightly colored (e.g., non-white) appearance and may be more suitable in darker colored paints or stains.

[0093] In some embodiments, the synergist and the drier may be combined together as a premixed mixture. For example, the synergist and the drier may be combined with each other and used in an amount sufficient to provide a desired drying time (e.g., about 1 to about 12 hours) in the solvent-based base paint or stain to which the combination is added. The amount of synergist and drier desired may depend, for example, on whether the base paint or stain is a fast drying product or a conventional drying product. In some embodiments, the synergist and drier mixture may include at least about 0.01 wt.%, at least about 0.5 wt.%, or at least about 1 wt.% drier, and up to about 20 wt.%, up to about 10 wt.%, or up to about 5 wt.% drier. In some embodiments, after the drier is added or dispersed in the tinted base paint or stain, the paint or stain may contain from about 0.5 wt.% to about 10 wt.% total drier on a dry solids basis.

[0094] The synergist, desiccant, or mixtures thereof may be packaged and shipped in a variety of containers, including those described above with respect to the colorants. In some embodiments, the containers for the synergist, desiccant, or mixtures thereof are similar to those used for the colorants and may be placed into and dispensed from available slots in a colorant dispenser. In other embodiments, the synergist, desiccant, or mixtures thereof are packaged and shipped in containers that allow manual dispensing of the respective components, such as squeeze bottles, or any of a number of other convenient packaging and dispensing containers familiar to those skilled in the art.

[0095] A variety of liquid-based paints and stains may be used in the disclosed systems and methods, which are well known to those skilled in the art. Suitable base paints or stains are described, for example, in the above-mentioned U.S. Pat. Nos. 10,933,389 (B2), 10,934,151 (B2), and WO 2022 / 011012 (A1), the disclosures of which are incorporated herein by reference.

[0096] Exemplary commercially available water-based paints and stains that can be used in the disclosed system include ARMSTEAD™, CORAL™, DULUX™ TRADE™, and FLEXA™ emulsion paints from Akzo Nobel; BEHR™, BEHR MARQUEE™, and BEHR PREMIUM™, PREMIUM PLUS™, and PREMIUM PLUS ULTRA™ latex paints from Behr Paint Company; BENJAMIN MOORE™, BENJAMIN MOORE ADVANCE™, BENJAMIN MOORE AURA™, BENJAMIN MOORE BEN™, BENJAMIN MOORE NATURA™, and BENJAMIN MOORE SELECT™ latex paints from Benjamin Moore & Co.; GENERATION™, GENERATION LX™, INTERLOK™, MATCH™, and INTERLOK™ latex paints from McCormick Paints. POINT™, RENEWXC™, REVO™, STATE HOUSE™, TOTAL ADVANTAGE™, and 360 COMPLETE COVERAGE™ latex or low-VOC paints; PPG Industries, Inc.Made by GLIDDEN(TM), GLIDDEN PREMIUM(TM), GLIDDEN HIGH ENDURANCE(TM), GLIDDEN SPRED(TM), GLIDDEN DIAMOND(TM), MANOR HALL™, PORTER™, REGENCY™, WONDER-PURE™, and WONDER-TONES™ latex paints; and A-100™, DURATION™, DURAMAX™, EMERALD™, INFINITY™, MEDALLION, OPTIMUS™, OVATION™, PRISTINE™, RESERVE™, RESILIENCE™, SHERWIN-WILLIAMS™, SHOWCASE™, SUPERPAINT™, SIGNATURE™, ULTRA™, and VALSPAR™ latex paints, and MINWAX™ water-based wood stains from Sherwin-Williams.

[0097] Exemplary commercially available solvent-based paints and stains that can be used in the disclosed system include GREAT FINISHES™ stains from Ace Hardware Corporation; DULUX™ and (outside the U.S.) GIDDEN™ alkyd paints from Akzo Nobel; BEHR™ alkyd paints from Behr Paint Company; oil-based stains from McCormick Paints; MOORE SATIN IMPERVO™ alkyd paints from Benjamin Moore & Co.; WEATHER-SHIELD™ alkyd paints from Kelly-Moore Co., alkyd paints from Huarun Paints (China); BAR-OX™, VELOUR™, and (outside the U.S.) GLIDDEN™ alkyd paints from PPG Industries, Inc.; SHERWIN-WILLIAMS PROCLASSIC™, PROMAR™, and VALSPAR ULTRA from Sherwin-Williams. 4000™ alkyd paint, as well as CABOT™, MINWAX, and MINWAX WOOD FINISH™ paints; and PERMO-PAVE™ alkyd paints manufactured by Wattyl Australia Pty. Ltd.

[0098] A variety of manual or automatic colorant dispensers can be used in the disclosed systems and methods, including the COROB™ D50 manual colorant dispenser manufactured by CPS Color Equipment, Inc., having a minimum dispensing capacity of 1 / 48 fluid ounce (0.62 mL), the ACCUTINTER™ 1500, 2000, 7000, and 8000 series automatic colorant dispensers manufactured by Fluid Management, Inc., having a minimum dispensing volume of 1 / 384 fluid ounce (0.077 mL), and the Sample Dispensing System automatic colorant dispenser manufactured by Fluid Management, Inc., having a minimum dispensing volume of 1 / 1024 fluid ounce (0.029 mL). Additional automatic paint or stain colorant dispensers include the COROB MODULA HF™ machine, which has a minimum dispense volume of 1 / 192 fluid ounce (0.153 mL), manufactured by CPS Color Equipment, Inc., and the TATOCOLOR™ machine, which has a minimum dispense volume of 1 / 384 fluid ounce (0.077 mL), manufactured by CPS Color Equipment, Inc. The dispenser selected may have a minimum fluid dispense volume of, for example, less than 0.01 fluid ounce (<0.3 mL), preferably less than 0.007 fluid ounce (<0.2 mL), and more preferably less than 0.005 fluid ounce (<0.15 mL). Dispensers with smaller minimum dispense volumes, for example less than 0.001 fluid ounces (<0.03 mL) or less than 0.0002 (<0.014 mL), may be used, but such dispensers may also require longer times to prepare dark colors in larger containers.

[0099] The disclosed custom pigmented architectural paints and stains may be applied to a variety of substrates, such as asphalt (including shingles and membranes of asphalt compositions), cement, cement fiberboard and roof tiles, ceramic, concrete, textiles, glass, metal, paper, plastic, wallboard and wood (including monolithic wood, engineered wood, and veneered plywood), as well as other substrates that will be apparent to one of ordinary skill in the art.

[0100] Referring now to the drawings, FIG. 1 shows a perspective view of an embodiment 100 of the disclosed paint and stain mixing system. A container 102 holds a liquid water-based base paint or stain 104. A top surface 106 (also shown in partial perspective) of the base paint or stain 104 is located a sufficient distance D1 below a container lid 108 such that a headspace 110 is available for adding one or more colorants to prepare a custom tinted water-based paint or stain having a custom hue. A handle 111 can be used to carry the container 102. A container 112 holds a liquid solvent-based base paint or stain 114. A top surface 116 (also shown in partial perspective) of the base paint or stain 114 is located a sufficient distance D2 below a container lid 118 such that a headspace 120 is available for adding one or more colorants to prepare a custom tinted water-based paint or stain having a custom hue. Distance D2 may be greater than, less than, or the same as distance D1, depending on the amount of colorant pre-present in the base paint or stain 104 and 114, and the anticipated amount of colorant that may need to be dispensed into the base paint or stain 104 and 114 to obtain a satisfactory final hue. Handle 121 may be used to carry container 112. The disclosed systems and methods may optionally use an additional base (not shown in FIG. 1), for example, a clear water-based or solvent-based base paint or stain for custom tinting of dark colors.

[0101] The containers 102 and 112 of base paint or stain may be combined with one or more colorants, for example, using a manual colorant dispenser 130. The dispenser 130 includes a cabinet 132 with attached shelves 134 on which the containers 102 or 112 may be positioned for addition of colorant and, if desired, other ingredients such as synergists, desiccants, or combinations thereof. A turntable 136 contains a series of refillable dispenser canisters (in this case twelve, four of which are numbered 138a, 138b, 138c, and 138d) that contain a point-of-sale array of liquid colorant in most or all of the canisters, and optionally a synergist, a desiccant, or a synergist and a desiccant combined together as a mixture in one or more remaining canisters. In some embodiments, for example when it is desirable to use all or nearly all of the available turntable positions for colorant addition, one or more separate bolt dispensers or a combination of a bolt-on dispenser and a canister, such as canister 138a, may be used to dispense optional synergists, drying agents, or both into the solvent-based paint or stain 114. An exemplary such dispenser is represented by a reservoir 152 that may contain contents 154 (shown in local perspective) representing a synergist, a drying agent, or a mixture thereof. The reservoir 152 may be sealed by a removable cap 156 or other suitable closure and may be refilled by removing such closure and injecting additional contents 154 into the reservoir 152. An outlet conduit 158, a manually operated valve 160, and a dispensing inlet 162 may be used to dispense the contents 154 from an inlet 164 into the container 112. The amount of contents 154 added to the container 112 can be estimated using the index mark 166 or by noting the change in the level of the contents 154 in the container 112 during addition.The amount of contents 154 added can also be metered by the valve 160, for example, by providing a hollow chamber (not shown in FIG. 1) within the valve 160 that holds a specified amount of contents 154 (e.g., 0.5 fluid ounces or 14.8 mL) and configuring the valve 160 such that the entire contents 154 within such chamber is dispensed from the inlet 164 when the handle on the valve 160 rotates completely. Additional rotations can be used to dispense additional contents 154. A typical addition of a synergist or drying agent mixture to a one gallon (3.78 L) container of base paint or stain can be, for example, from about 1 to about 5 fluid ounces (about 30 to 150 mL) of contents 154 and does not need to be measured as precisely as adding a colorant. Thus, with a valve 160 configured as described above, one revolution of the valve handle can be used to dispense sufficient contents 154 for a 1 quart (0.946 L) container holding a solvent-based paint or stain, and four full revolutions can be used to dispense sufficient contents 154 for a 1 gallon (3.78 L) container holding such a paint or stain. In some embodiments, the tinted paint or stain can include from about 1 to about 4 fluid ounces per gallon of synergist and from about 0.01 to about 0.25 fluid ounces per gallon of drying agent.

[0102] When tinting a water-based base paint or stain, such as base paint or stain 104, synergists and driers are preferably not used. When tinting a solvent-based base paint or stain, such as base paint or stain 114, synergists (and often driers as well) are typically used with one or more colorants and may be omitted only if the volume or type of colorant is such that compatibility issues are not expected to arise. By way of example, canister 138d includes a dispensing cylinder 140d including a piston and connecting link (neither shown in FIG. 1 ) joined to a movable handle 142d whose position can be adjusted vertically along cylinder 140d to provide metered delivery of colorant, synergist, or drier from canister 138d through dispensing outlet 144d to a container, such as base paint or stain container 102 or 112, located on shelf 134. The remaining canisters include similar, but unnumbered, dispensing cylinders, pistons, connecting links, handles, and dispensing outlets. A release lever 150 allows the turntable 136 to rotate as needed to align each stain, synergist, or desiccant canister above the shelf 134 and lock into place while the stain, synergist, or desiccant is metered and dispensed into the base paint or stain container. The amount and type of synergist and desiccant dispensed into the solvent-based base paint or stain may be the same for simplicity whenever the solvent-based base paint or stain is tinted. In other embodiments, the amount or type of synergist or desiccant may vary depending on the amount of stain added (i.e., a particular desiccant may be used when preparing a dark or deep shade and a different desiccant may be used when preparing a light pastel shade), the type of stain added (i.e., more synergist or a different synergist may be used when preparing a green or blue shade and less synergist or none at all when preparing a black or yellow shade), or both the amount and type of stain added. The amount or type of synergist and drier may also vary depending on the solvent-based paint or stain selected. Preferably, the synergist and drier are added prior to the addition of the colorant, although this is not required.

[0103] FIG. 2 shows a perspective view of an embodiment 200 of the disclosed paint and stain mixing system. The base paint or stain containers 102 and 112 are similar to FIG. 1. The containers 102 and 112 may be combined with one or more colorants, for example, using an automated colorant dispenser 202. The dispenser 202 includes a shelf 204 on which the containers 102 or 112 may be positioned for the addition of colorants and, if desired, other ingredients such as synergists, desiccants, or combinations thereof. A cabinet 206 holds a series of interchangeable dispenser canisters (in this case 16, four of which are numbered 208a, 208b, 208c, and 208d) that contain a point-of-sale array of liquid colorants in most or all of the canisters, and optionally a synergist, a desiccant, or a synergist and a desiccant combined together as a mixture in one or more remaining canisters. The colorant, synergist, desiccant, or a mixture of synergist and desiccant may be dispensed from an appropriate canister through suitable internal plumbing (not shown in FIG. 2) in the cabinet 206 and suitable dispensing nozzles (not shown in FIG. 2) located in the dispensing head 210 and then dispensed into the base paint or stain container. In some embodiments, the synergist, desiccant, or mixtures thereof may be dispensed into the solvent-based base paint or stain 114 from a separate bolt-on dispenser. An exemplary such separate dispenser is represented by a reservoir 252 containing contents 254 (shown in local perspective) representing the synergist, desiccant, or mixtures thereof. The reservoir 252 may include a removable cover 256 or other suitable closure to allow for refilling of the reservoir 252. An outlet conduit 258, a motorized metering valve 260, and a dispensing inlet 262 may be used to dispense the contents 254 from an inlet outlet 264 into the container 122. A microprocessor or other control device (not shown in FIG. 2) may be used to meter the amount of contents 254 added to the container 112. The monitor 212 and keyboard 214 allow information and commands to be entered into the dispenser 202.A barcode reader (not shown in FIG. 2) can be used to read information from the paint or stain sample cards or base paint or stain container to assist in controlling the system. A power button 216 and an emergency off button 220 can be used to start and stop the dispenser 202 and valve 260. As in the embodiment shown in FIG. 1, the amount or type of synergist and drier can vary depending on the amount or type of colorant added. Additionally, as in the embodiment shown in FIG. 1, the amount or type of synergist and drier can also vary depending on the solvent-based base paint or stain selected. Such changes in the amount or type of synergist and drier are generally much easier and more reliably accomplished with an automated stain dispenser such as shown in FIG. 2 than with a manual stain dispenser such as shown in FIG. 1.

[0104] FIG. 3 is a perspective view of a point-of-sale colorant array 300 having thirteen containers 302-326 containing water-only fluid colorants of different hues. In the center of FIG. 3 is a fourteenth container, designated 328, which contains a synergist and, optionally, a desiccant. In some embodiments, a desiccant may be provided in one of the containers 302-326 and a synergist may be provided in container 328, or vice versa. Although not shown in FIG. 3, the corresponding point-of-sale custom color system also desirably includes one or more water-based paint or stain bases, such as base 102 in FIGS. 1 and 2, and one or more solvent-based paint or stain bases, such as base 112 in FIGS. 1 and 2. Container 302 (representative of the other containers in FIG. 3) includes sides 330, bottom 332, top 334, and label 336, and may contain a water-only liquid colorant, such as a carbon black dispersion for use in interior paint tinting, for example. Top 334 is preferably pierceable, shearable, or otherwise penetrable and may be similar to tops used on soup cans. Container 304 contains different water-only liquid colorants, such as a dispersion of a non-infrared absorbing black colorant for use in tinting exterior paints. Containers 306-326 preferably contain additional water-only fluid colorants, which in the embodiment shown in FIG. 3 are white, green, blue, red, magenta, red oxide, yellow oxide, medium yellow, yellow, transparent yellow, and transparent red colorants, respectively. The colorants in containers 302-322 include embodiments of the disclosed surfactant packages optimized for use of the colorants in water-based paints and stains, and the colorants in containers 324 and 326 include embodiments of the disclosed surfactant packages optimized for use of the colorants in water-based stains. Many of the colorants in containers 302-326 exhibit unacceptable compatibility when added alone to a solvent-based paint or stain. However, not all such colorants exhibit unacceptable compatibility.For example, the medium yellow colorant in container 320 and the yellow colorant in container 322, due to the nature of these colorants, may exhibit acceptable compatibility with both water- and solvent-based paints and stains even in the absence of a synergist in container 328. Nevertheless, these latter colorants will be referred to as "water-only" colorants for simplicity.

[0105] When at least each of the colorants 306-312, and more preferably each of the colorants 302-318 and 324-326, are dispensed into a solvent-based paint or stain, the synergists (and optional drying agents, if used) in array 300 are preferably optimized to provide improved compatibility, a homogenous mixture, reduced rub-up, and faster drying times.

[0106] Test Method Rub-up Test: Shake the tinted paint or stain on a RED-DEVIL cradle-type paint shaker for 1 minute, then remove a small aliquot of tinted paint. Shake the remaining sample for an additional 14 minutes, for a total of 15 minutes. Make a drawdown using a BIRD™ film applicator onto a white LENETA™ card and compare samples shaken for 1 and 15 minutes. Use the index finger and gentle pressure to create a uniform circular "rub-up" pattern on the top outer edge of each coating, applying shear to the applied area without rubbing through the film, typically using at least 5 rubs and a maximum of 25 rubs on each coating. Rub-up is visually rated on a scale of none, slight, slight, moderate, or severe, with moderate or severe ratings being visually objectionable.

[0107] Colorimeter Test: Allow the film to air dry. Upon drying, use a spectrophotometer to measure the tint strength and CIELAB delta E color difference between samples shaken for 1 minute and 15 minutes, with a tint strength ratio of 90%-110% for 15 minutes vs. 1 minute shaking time indicating acceptable compatibility, and a ratio of 95%-105% indicating very acceptable compatibility.

[0108] Viscosity Loss Test: A 1 / 2 pint (8 fluid ounce) sample of water-based latex paint is tinted at the maximum recommended colorant loading level and shaken for 1 minute on a RED-DEVIL cradle-type paint shaker, followed by measuring the Stromer KU viscosity of the shaken paint sample in Krebs units. Improved performance is indicated if the viscosity loss of the tinted paint is less than the viscosity loss observed with a water-only or all-purpose colorant having the same color.

[0109] The disclosed systems, methods, and surfactant packages are further described in the following examples, in which all parts and percentages are by weight unless otherwise specified. EXAMPLES

[0110] White, green, blue, and red colorants were prepared by mixing the ingredients shown in Table III below.

[0111] [Table 3]

[0112] All the colorants exhibited good compatibility, homogeneity, and flowability. EXAMPLES

[0113] Using the method of Example 1, yellow, medium yellow, red oxide, yellow oxide, magenta, and amber colorants were prepared by mixing the ingredients shown in Table IV below.

[0114] [Table 4]

[0115] All the colorants exhibited good compatibility, homogeneity, and flowability. EXAMPLES

[0116] Using the method of Example 1, an infrared absorbing black colorant was prepared by mixing the ingredients shown in the center column of Table V below.

[0117] [Table 5]

[0118] The black infrared absorbing colorant exhibited good compatibility, homogeneity, and flowability. A non-infrared absorbing black colorant having good compatibility, homogeneity, and flowability can be prepared by mixing the components shown in the right column of Table V. EXAMPLES

[0119] The colorants of Example 1, Example 2, and the infrared absorbing Example 3 were added to the base paints listed in Table VI below from McCormick Paints, applied as 6 mil (0.15 mm) thick films on unsealed LENETA charts, and evaluated using rub-up and colorimeter tests in comparison to NOVOCOLOR II™ general purpose colorants from Color Corp. of America, which are described in the aforementioned U.S. Patent No. 7,659,350 (B2) (Coward et al.).

[0120] [Table 6]

[0121] Rub-up test results were the same or better in all cases for comparing the non-infrared absorbing black colorants from Example 1, Example 2, and Example 3 with the corresponding NOVOCOLOR II colorants, and were all acceptable. Colorimeter test results showed that acceptable compatibility was obtained for all bases using these colorants from Examples 1, 2, and 3, and very acceptable compatibility was obtained for all bases using almost all of the colorants from Examples 1, 2, and 3. For example, very acceptable compatibility was obtained using the green colorant from Example 1 in the REVO LOW VOC Flat Clear (Deep) tint base, but not using the NOVOCOLOR II green colorant (e.g., ΔE ratio of 101.83 for the green of Example 1 vs. 105.70 for the NOVOCOLOR II green). Also, the use of the blue colorant of Example 1 in the TOTAL ADVANTAGE Eggshell Medium base resulted in very acceptable compatibility, whereas the use of the NOVOCOLOR II green colorant did not (e.g., ΔE ratio of 97.35 for Example 1 blue vs. 140.98 for NOVOCOLOR II blue).

[0122] The results of the viscosity reduction tests were very favorable. Viscosity reduction test results comparing the pigmented (i.e., non-white) colorants from Examples 1 and 2 and the non-infrared absorbing black colorant from Example 3 with the corresponding NOVOCOLOR II colorants when added to three different INTERLOK Indoor / Outdoor Latex Urethane Direct-to-Metal Bases are shown in Table VII below. For all shades, reduced viscosity reduction was observed using the colorants of Examples 1, 2, and 3. These results are particularly important for use in point-of-sale paint and stain tinting systems, as they allow the user to have better brush and edge control throughout the shade after stirring or other agitation.

[0123] [Table 7] EXAMPLES

[0124] Two oil-based paints (SWP™ Exterior Gloss Oil-Based Paint and PROMAR™ 200 Interior Alkyd Eggshell, both from The Sherwin-Williams Company) and two oil-based stains (Semi-Solid Deck and Siding Stain Neutral Base and Semi-Transparent Stain Neutral Base, both from The Sherwin-Williams Company) were mixed with several of the colorants from Examples 1-3 and evaluated using rub-up and colorimeter tests both with and without the addition of a synergist. The synergist was made with 76.68% by weight isopropylamine salt of linear alkylbenzene sulfonic acid, 16.82% by weight propylene glycol, 2.24% by weight liquid thixotropic additive, and 4.26% by weight iron-based drying agent catalyst. The colorants were added to the oil-based paints at 4 oz / gal (31.25 mL / L). The colorants were added to the oil stain at 10 oz / gal (78.125 mL / L) along with 2 oz / gal (15.625 mL / L) of the white colorant of Example 1. The synergists were added in the amounts shown in Table VIII below.

[0125] [Table 8-1]

[0126] [Table 8-2]

[0127] [Table 8-3]

[0128] The results in Table VIII show that in almost every instance, the use of synergist resulted in significant improvements in tint stability, and rub-up performance results were at least as good, and in many cases significantly improved, compared to using the colorants without synergist.

[0129] Having thus described a preferred embodiment of the present invention, one of ordinary skill in the art will readily appreciate that the teachings found herein may be applied to still other embodiments within the scope of the appended claims. The complete disclosures of all patents, patent documents, and publications are incorporated herein by reference as if individually incorporated.

[0130] Embodiment 1: An embodiment of a point-of-sale custom color system for tinting waterborne architectural base paints and stains, the system comprising an array of low volatile organic compound water-only liquid colorants including at least white, green, blue, and red colorants, each of which comprises at least a three-component surfactant package, a pigment, and a vehicle that causes the colorant to be compatible and homogeneously dispersed throughout the waterborne base paint or stain, but not compatible and homogeneously dispersed throughout the solvent-based base paint or stain unless the colorant is used in combination with a synergist that contains one or more components that cause the water-only colorant to be dispersed in the solvent-based base paint or stain.

[0131] Embodiment 2: An embodiment of a method for tinting point-of-sale ordered paints or stains, the method comprising dispensing, at a retail, wholesale, or combined retail / wholesale store using an automatic or manual colorant dispenser, into a water-based paint or stain one or more water-only liquid colorants selected from an array of colorants including at least white, green, blue, and red colorants, each including at least a three-component surfactant package, a pigment, and a vehicle, that causes the colorant to be compatible and homogeneously dispersed throughout the water-based paint or stain, but not compatible and homogeneously dispersed throughout the solvent-based paint or stain unless a synergist is used in combination with the colorant that contains one or more components that cause the water-only colorant to be dispersed in the solvent-based paint or stain.

[0132] Embodiment 3: An embodiment of a point-of-sale custom color system for tinting waterborne architectural base paints and stains, the system comprising an array of low volatile organic compound water-only liquid colorants including at least white, green, blue, and red colorants, each of which comprises at least a three-component surfactant package, a pigment, and a vehicle that, when used in combination with the colorant, a synergist containing one or more components that disperse the water-only colorant in the solvent-borne base paint or stain, disperses the colorant compatible and homogeneous throughout the water-borne base paint or stain.

[0133]

[0023] Embodiment 4: An embodiment of a method for tinting point-of-sale ordered paints or stains, the method comprising dispensing, at a retail, wholesale, or combined retail / wholesale store using an automatic or manual colorant dispenser, into the water-based paints or stains one or more water-only liquid colorants selected from an array of colorants including at least white, green, blue, and red colorants, each including at least a three-component surfactant package, a pigment, and a vehicle that, when used in combination with the colorant, a synergist containing one or more components that disperse the water-only colorant in the solvent-based paints or stains, disperses the colorant compatible and homogeneous throughout the water-based paints and stains.

[0134] Embodiment 5: The method comprises distributing a water-only colorant into water-based paints and stains to tint the water-based paints or stains, or To tint solvent-based paints or stains, a) dispensing one or more water-only colorants and synergists into a solvent-based paint or stain; or b) dispensing one or more water-only colorants into a solvent-based paint or stain containing a synergist; 5. An embodiment of the method of any one of embodiments 2 or 4, further comprising:

[0135] Embodiment 6: A packaged staining embodiment comprising a low volatile organic compound water-only liquid staining agent, the embodiment comprising at least a three-component surfactant package that disperses the staining agent compatibly and homogeneously throughout the water-based paint or stain, but not compatibly and homogeneously throughout the solvent-based paint or stain, unless a synergist is used in combination with the staining agent, the synergist containing one or more components that disperse the water-only liquid staining agent in a solvent-based paint or stain, packaged in a container having a volume of about 0.5 to about 5 L, the pigment, and a vehicle.

[0136] Embodiment 7: An embodiment of the system, method, or packaged stain of any one of the preceding embodiments, wherein the stain is packaged in a container from which it is gravimetrically or volumetrically dispensed via an automatic or manual stain dispenser into a base paint or stain in the container having a volume of about 0.2-20 L.

[0137] Embodiment 8: An embodiment of the system, method, or packaged colorant according to any one of the preceding embodiments, further comprising at least one water-based base paint or stain and at least one solvent-based base paint or stain, the base paint or stain being packaged in a mostly filled, but not completely filled, point-of-sale container having a volume of about 0.2 to 20 L with an openable and resealable lid, cap, or other closure for an opening through which colorant may be dispensed from an automatic or manual colorant dispenser into the base paint or stain.

[0138] Embodiment 9: A system, method, or packaged colorant embodiment of any one of the preceding embodiments, further comprising red, yellow, and black colorants.

[0139] Embodiment 10: An embodiment of the system, method, or packaged colorant of any one of the preceding embodiments, further comprising medium yellow, red oxide, yellow oxide, magenta, and amber colorants.

[0140] Embodiment 11: An embodiment of the system, method, or packaged colorant according to any one of the preceding embodiments, wherein the surfactant package comprises at least two nonionic surfactants and at least one anionic surfactant.

[0141] Embodiment 12: An embodiment of the system, method, or packaged colorant of embodiment 11, wherein the nonionic surfactant comprises a hydrophilic alkylene oxide portion and a hydrophobic portion, and at least one hydrophobic portion of the nonionic surfactant contains a straight or branched chain aliphatic group, and at least another hydrophobic portion of the nonionic surfactant contains one or more aromatic rings.

[0142] Embodiment 13: An embodiment of the system, method, or packaged colorant of embodiment 12, wherein the hydrophilic alkylene oxide portion of the nonionic surfactant contains a plurality of -CH2CH2O- groups.

[0143] Embodiment 14: An embodiment of the system, method, or packaged colorant of embodiment 12 or embodiment 13, wherein the linear or branched chain aliphatic group comprises an alkyl group or mixture of alkyl groups having 1 to 20 carbons.

[0144] Embodiment 15: An embodiment of the system, method, or packaged colorant of any one of embodiments 12-14, wherein the aromatic ring is one, two, three, or four six-carbon aromatic rings.

[0145] Embodiment 16: An embodiment of the system, method, or packaged colorant described in any one of embodiments 11 to 15, wherein at least one anionic surfactant comprises a hydrophilic alkylene oxide portion and a hydrophobic portion that includes a phosphorus or sulfur group.

[0146] Embodiment 17: An embodiment of the system, method, or packaged colorant described in embodiment 16, wherein the hydrophilic alkylene oxide portion of the anionic surfactant comprises a plurality of -CH2CH2O- groups.

[0147] Embodiment 18: An embodiment of the system, method, or packaged colorant of embodiment 16 or embodiment 17, wherein the hydrophobic portion of the anionic surfactant comprises a phosphate ester group.

[0148] Embodiment 19: An embodiment of the system, method, or packaged colorant of embodiment 16 or embodiment 17, wherein the hydrophobic portion of the anionic surfactant comprises a sulfate or sulfonate group.

[0149] Embodiment 20: A system, method, or packaged colorant embodiment of any one of the preceding embodiments, wherein the surfactants in the surfactant package each have a number average molecular weight of less than 2,000 g / mol.

[0150] Embodiment 21: An embodiment of the system or method according to any one of the preceding embodiments, wherein the colorants in the array each contain at least about 0.5 and up to about 20% by weight of the surfactant package.

[0151] Embodiment 22: An embodiment of the system or method according to any one of the preceding embodiments, wherein different colorants in the array contain different total amounts of surfactant packages.

[0152] Embodiment 23: An embodiment of the system or method according to any one of the preceding embodiments, wherein different colorants in the array contain different amounts or different relative ratios of each surfactant.

[0153] Embodiment 24: An embodiment of the system or method according to any one of the preceding embodiments, wherein the array contains yellow and black colorants that contain a higher amount of surfactant package compared to the other colorants.

[0154] Embodiment 25: An embodiment of the system, method, or packaged colorant of any one of the preceding embodiments, wherein the colorant contains at least about 2 and up to about 90% by weight of pigment.

[0155] Embodiment 26: An embodiment of the system, method, or packaged colorant of any one of the preceding embodiments, wherein the colorant contains at least about 0.5 and up to about 80% by weight of the combined weight of pigments, extenders, inert pigments, and fillers.

[0156] Embodiment 27: An embodiment of the system, method, or packaged colorant of any one of the preceding embodiments, wherein the one or more colorants contain at least about 0.1 and up to about 5% by weight of a pigment dispersant.

[0157] Embodiment 28: An embodiment of the system or method according to any one of the preceding embodiments, wherein all of the colorants in the array are water-only colorants.

[0158] Embodiment 29: An embodiment of the system or method according to any one of the preceding embodiments, further comprising a synergist.

[0159] Embodiment 30: An embodiment of the system or method according to any one of the preceding embodiments, further comprising a desiccant.

[0160] Embodiment 31: An embodiment of an at least three component surfactant package for use in making water-only liquid colorants for tinting water-based paints and stains, the package comprising at least three surfactants represented by the following formulae I, II, and III:

[0161] [ka] where R is a straight or branched chain alkyl group or mixture of groups having 1 to 20 carbons, and n is the number of moles of ethylene oxide and is at least 7 and at most 50;

[0162] [ka] wherein m is the number of moles of ethylene oxide and is at least 5 and at most 25, in some embodiments at least 10 and at most 20; and R1, R2, R3, R4, and R5 are independently hydrogen or a straight or branched chain aliphatic or aromatic hydrocarbon group containing at least 4 and at most 10 carbon atoms; and

[0163] [ka] wherein R6 is hydrogen or an ethylene oxide chain containing at least 5, and at most 15 moles, and a terminal hydrogen atom, a nitrogen group, an alkyl group, or an alkaryl group; and R7 and R8 are independently hydrogen, sodium, potassium, a counterion, or an ethylene oxide chain containing at least 5, and at most 15 moles, of EO, and a terminal hydrogen atom, an alkyl group, or an alkaryl group.

[0164] Embodiment 32: An embodiment of the surfactant package according to embodiment 29, comprising a mixture of: a) alcohol ethoxylates having a hydrophilic-lipophilic balance (HLB value) of 12 to 20; b) tristyrylphenol ethoxylates having 5 to 15 moles of ethylene oxide, and c) Aliphatic phosphate esters having 5 to 15 moles of ethylene oxide.

Claims

1. 1. A water-only liquid colorant comprising at least a three component surfactant package, said surfactant package comprising at least two nonionic surfactants and at least one anionic surfactant, said nonionic surfactants each comprising a hydrophilic alkylene oxide portion and a hydrophobic portion, said hydrophobic portion of at least one of said nonionic surfactants comprising a straight or branched chain aliphatic group and said hydrophobic portion of at least another of said nonionic surfactants comprising one or more aromatic rings, said liquid colorant being suitable for dispersion in a water-based based paint or stain without a synergist, and said liquid colorant being unsuitable for dispersion in a solvent-based based paint or stain without a synergist.

2. The hydrophilic alkylene oxide portion of the nonionic surfactant has a plurality of -CH ２ CH ２ 2. The liquid colorant of claim 1, comprising an O-group.

3. The liquid colourant according to any one of claims 1 to 2, wherein the straight or branched chain aliphatic group comprises an alkyl group.

4. 4. The liquid colourant of claim 1, wherein each non-ionic surfactant comprises a straight or branched chain alkyl group or mixture of alkyl groups having 1 to 20 carbons.

5. 5. The liquid colourant according to claim 1, wherein the aromatic ring is one, two, three or four carbon hexacyclic rings.

6. The liquid colorant according to any one of claims 1 to 5, wherein the at least one anionic surfactant comprises a hydrophilic alkylene oxide moiety and a hydrophobic moiety comprising a phosphorus or sulfur group.

7. The hydrophilic alkylene oxide portion of the anionic surfactant has a plurality of -CH ２ CH ２ A liquid colourant according to any one of claims 1 to 6, comprising an O-group.

8. The liquid colourant according to any one of claims 1 to 7, wherein the hydrophobic portion of the anionic surfactant comprises a phosphate ester group.

9. The liquid colourant according to any one of claims 1 to 8, wherein the hydrophobic portion of the anionic surfactant comprises a sulfate or sulfonate group.

10. 10. The liquid colorant according to any one of the preceding claims, wherein the surfactants in the surfactant package each have a number average molecular weight of less than 2,000 g / mol.

11. The liquid colorant of any one of claims 1 to 10, wherein the colorant contains at least about 0.5 and at most about 20% by weight of the surfactant package.

12. The liquid colorant of any one of claims 1 to 11, wherein the colorant further comprises at least about 2 and up to about 90 weight percent of one or more pigments.

13. 13. The liquid colorant of any one of claims 1 to 12, wherein the colorant contains at least about 0.5 percent by weight and up to about 80 percent by weight of the combined weight of pigments, extenders, inert pigments, and fillers.

14. The liquid colorant of any one of claims 1 to 13, wherein the one or more colorants contain at least about 0.1 weight percent and up to about 5 weight percent of the pigment dispersant.

15. 1. A liquid package for use in making water-only liquid colorants for tinting water-based paints and stains, comprising: 【Chemistry 1】 where R is a straight or branched chain alkyl group or mixture of groups having 1 to 20 carbons, and n is the number of moles of ethylene oxide and is at least 7 and at most 50. 【Chemistry 2】 where m is the number of moles of ethylene oxide and is at least 5 and at most 25, in some embodiments at least 10 and at most 20; R １ , R ２ , R ３ , R ４ , and R ５ are independently hydrogen or a straight or branched chain aliphatic or aromatic hydrocarbon group containing at least 4 and at most 10 carbon atoms; and 【Chemistry 3】 (In the formula, R ６ is hydrogen or an ethylene oxide chain containing at least 5 and at most 15 moles and a terminal hydrogen atom, nitrogen group, alkyl group, or alkaryl group; R ７ and R ８ are independently hydrogen, sodium, potassium, a counterion, or an ethylene oxide chain containing at least 5 and at most 15 moles of EO, and a terminal hydrogen atom, alkyl group, or alkaryl group.

16. d) alcohol ethoxylates having a hydrophilic-lipophilic balance (HLB value) of 12 to 20; e) tristyrylphenol ethoxylates having 5 to 15 moles of ethylene oxide, and 16. The liquid package of claim 15, further comprising: f) an aliphatic phosphate ester having 5 to 15 moles of ethylene oxide.

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