Durable waterproof treatment agent for synthetic fibers and natural fibers

Abstract

A water-based coating composition includes a drying oil, a fatty acid or alkylamine fatty acid and an alkylamine, 50%-90% of water, and one or more waxes. When applied to a fabric and cured in air, the composition forms a laundry durable waterproof coating. The coating composition may include a dye; in such cases, a durable waterproof coating is applied to the fabric in a single curing step and the fabric is dyed.

Description

[0001] Textiles are typically finished at the mill with dyes and various polymeric treatments to obtain color, improved durability, comfort, and hand, and to provide water repellency for outdoor and sportswear. One such finishing step is the addition of a durable water repellent (DWR) treatment. For many years, polymeric treatments of perfluorinated compounds have been applied to dyed fabrics using water baths and continuous curing ovens. This finishing process provides water repellency and limited stain resistance to the fabric before it is sewn into a garment.

[0002] Since the 2012 ban by the U.S. EPA of certain long-chain perfluoroalkyl substances (PFAS), there has been a sharp increase in consumer preference for safe chemical ingredients applied to the surface of garments, carpets, medical personal protective equipment (PPE), and other textiles, and the industry has been searching for alternatives to the banned PFAS-based chemicals. Some shorter-chain PFAS chemicals are still allowed in certain jurisdictions, although these chemicals have not been proven to be effective in water repellency, laundry durability, or stain resistance. New, non-fluorinated compound DWR treatments have also become similarly deficient.

[0003] Most commonly, the DWR finishing step is performed as a second finishing process after dyeing, because the chemicals required for dyeing and DWR are incompatible in many cases, and because the DWR treatment interferes with any subsequent water-based dyeing of the fabric. Dyeing and DWR fabric treatment are always performed as separate steps, even though the two finishing processes affect the properties of the other on the fabric. For example, DWR treatment often changes the shade or color of dyed fabric. In addition, to make the dyeing process more effective, hydrophilic chemicals are often added to the dye bath to improve the uptake of the dye. These dye additives affect the water repellency of any subsequent DWR treatment.

[0004] Fabric dyeing is a major aspect of textile and garment production, and is one of the key steps required in any garment manufacturing process. Fabric dyeing is one of the most demanding processes in textile production, as brands and customers want to have bright colors that are not only uniform across the entire width of the fabric (which can be 1.2 to 1.8 meters), but also uniform over lengths of hundreds or even thousands of meters.

[0005] Many commercial dyes are specific to certain fabrics. For example, disperse dyes are exclusively used for polyester fabrics, acid dyes are typically used for polyamides, and reactive dyes are used for cotton and certain other natural fibers.

[0006] Traditionally, dyeing processes are carried out using aqueous solutions. One common fabric dyeing process is “beck” dyeing, which is a batch process where a large volume of full-width fabric is internally circulated in superheated pressurized water containing dissolved dyes and various dye-enhancing chemicals for 6 to 8 hours, followed by rinsing, neutralization, drying, and curing.

[0007] Another common dyeing process is hot-melt dyeing, which is a continuous process, also requiring several hours, and involves steaming the fabric in various hot stages, followed by several rinsing and neutralization processes.

[0008] Cotton dyeing also involves soaping, high-temperature washing, followed by rinsing, neutralization, drying, and curing.

[0009] All of these conventional dyeing processes involve large volumes of water and consume several hours of processing time. The majority of water pollution generated by a mill comes from the dyeing process, as water is circulated through the fabric and requires multiple rinsing steps to clear excess dye and any residual soap or dye additives. Additionally, the majority of energy consumption by a mill comes from heating all of the water required for dyeing. Reducing the energy budget for water heating is necessary for the industry to meet its greenhouse gas reduction targets.

[0010] A high-performance DWR fabric treatment process that avoids PFAS chemicals and is easy to apply and cure, using reduced amounts of energy, is highly desirable. It is further desirable if such a coating composition used in such a process consists primarily of products obtained from renewable resources, particularly agrochemicals derived from plants or trees.

[0011] Additionally, a process that allows for simultaneous DWR treatment and fabric dyeing in a single coating and curing step would be of great value to the industry and would reduce energy usage and costs as well as operational complexity for textile mills. Furthermore, by eliminating dye additives used to improve dye uptake by the fabric, the amount of wasted water can be greatly reduced. For use in garments, the DWR and fabric dyeing process must also be durable to withstand multiple wash cycles.

[0012] The present invention is a coating composition in the form of an emulsion. The coating composition comprises, based on the total weight of the composition,

[0013] a) 5 wt-% to 35 wt-% of a drying oil;

[0014] b) 0.25 wt.-% to 5 wt.-% of a fatty acid or fatty alcohol component selected from the group consisting of (i) a fatty acid having at least 12 carbon atoms and 0 to 2 non-conjugated carbon-carbon double bonds, (ii) an alkyl amine fatty acid having at least 12 carbon atoms and 0 to 2 non-conjugated carbon-carbon double bonds in the fatty acid moiety, and (iii) a fatty alcohol having at least 12 carbon atoms and 0 to 2 non-conjugated carbon-carbon double bonds;

[0015] c) 2 wt.-% to 10 wt.-% of an alkyl amine having a boiling point temperature of 75 °C to 160 °C, provided that the amount of alkyl amine is 0.2 to 1.25 parts by weight per part by weight of the drying oil;

[0016] d) 50 wt.-% to 90 wt.-% of water; and

[0017] e) 0.25 wt.-% to 7.5 wt.-% of a wax or mixture of waxes, the melting temperature of the wax or mixture of waxes being at least 60 °C.

[0018] The present invention is also a method for applying a DWR finish to a fabric comprising the steps of:

[0019] (a) applying the coating composition of the present invention to a fabric, and

[0020] (b) curing the applied coating composition in air at a temperature of 100 °C to 160 °C to produce a DWR finish.

[0021] The coating composition is used to apply a DWR finish to a wide range of fabrics, including cotton, wool, bamboo, linen, silk, polyester, precipitated cellulose (Lyocell, Tencel®), polyolefins, polyamides, acrylics (Orlon™), polylactic acid, aromatic polyamides, and polyether-polyurea (e.g. Elastane®, Spandex, Lycra®), as well as blends of two or more of these fibers and synthetic derivatives of natural biological fibers (e.g. banana stem, wheat and straw, hemp, jute, manila hemp, corn and pineapple). The coating composition is typically in the form of an oil-in-water emulsion, although a water-in-oil emulsion is also possible. The fabric can be immersed in the emulsion or pulled through the emulsion, then squeezed between rollers to remove excess liquid (a process known in the industry as “padding”), and continuously dried and cured in an oven or other heater. At the end of the curing process, the DWR treatment is complete and no additional treatment or rinsing is required. The curing step is carried out in air and is distinctly different from certain free radical polymerization processes that must be carried out in an oxygen-free environment. Thus, the coating and curing steps do not require specialized capital equipment or any industrial gases. It uses equipment of the type already present in most textile mills. Many of the components of the coating composition can be agrochemicals, such as natural plant products (e.g. drying oils and waxes) or derivatives of natural plant or animal products (e.g. fatty acid or fatty alcohol components and many waxes). These agrochemicals are also biodegradable, which meets another sustainability development goal of the textile industry.

[0022] The coating composition of the present invention does not require fluorocarbons, so the adhesion of the icon and film to the treated fabric is simple. The treated fabric has a pleasant, dry hand feel. The DWR treatment generally improves the durability of the product by minimizing fiber breakage and microfiber release during use and washing.

[0023] The DWR process can be used on pre-dyed or undyed fabrics. However, another important advantage of the present invention is that dyes or pigments can be included in the coating composition; doing so allows dyeing and applying a DWR finish to be performed simultaneously in a single processing operation, thereby reducing the operating costs and energy costs of the mill. It is believed that the oil and fatty acid or fatty alcohol components improve the penetration of the emulsion chemistry into both synthetic and natural fibers, bring the dye into the fiber, and anchor the dye into the fiber upon curing and reduce the number of hours of operation. Any number of dye types can be used: acid dyes, pigment dyes, reactive dyes, or disperse dyes; and in most cases, the fabric will be permanently colored accordingly, while also having the desired DWR attributes. This is very attractive because it reduces the operating complexity of the dye house, because it allows a wider range of dyes to be used to treat a particular fabric, and it simplifies the dyeing of fabrics having blended fibers such as cotton / polyester or polyester / spandex blends. For example, reactive dyes that are typically used on cotton can be used instead of only disperse dyes on polyester to obtain a non-fading dye. Acid or direct dyes that are typically used on polyamide fabrics can also be used on cotton or linen, and one type of dye can be mixed with other types of dyes.

[0024] Component a) of the coating composition is a drying oil. By "drying oil" is meant a fatty acid triglyceride that crosslinks upon exposure to air over a period of time. At least one of the constituent fatty acids of the fatty acid triglyceride has at least one, preferably at least two, carbon-carbon double bonds. In some embodiments, at least one of the constituent fatty acids has at least three carbon-carbon double bonds. The drying oil preferably has an iodine value greater than 130.

[0025] The multiple carbon-carbon double bonds of such constituent fatty acids can be conjugated or unconjugated; however, drying oils having at least one constituent fatty acid comprising at least 2 (e.g., as in linoleic acid), preferably 3, conjugated carbon-carbon double bonds are particularly useful. In some particularly useful embodiments, at least 40 wt% of the constituent fatty acids of the drying oil comprise at least 3 conjugated carbon-carbon double bonds. Examples of constituent fatty acids having at least 3 conjugated carbon-carbon double bonds include a-eleostearic acid and calendic acid. The drying oil can be a raw oil, i.e., an oil that has not been purified to remove free fatty acids or other organic components. In fact, the use of raw drying oils can be a proof of safety and sustainability of the process.

[0026] Examples of drying oils include flaxseed oil, sunflower oil, safflower oil, perilla oil, and walnut oil. Particularly preferred examples of drying oils include tung oil, balsam pear oil, and calendula seed oil, as a-eleostearic acid and / or calendic acid comprise more than 40 wt% of the constituent fatty acids of those particularly preferred drying oils.

[0027] The coating composition comprises 5 wt.% to 35 wt.% of a drying oil, based on the weight of the coating composition. Preferred amounts are at least 6 wt.-% or at least 7 wt.-% and at most 30 wt.-%, at most 25 wt.-% or at most 20 wt.-% on the same basis. All weight percentages of the coating compositions reported herein are "wet weights", i.e. the total weight of the coating composition, including the weight of water and other volatiles which are removed during curing and do not remain in the cured coating.

[0028] The fatty acid or fatty alcohol component (component b) is (i) one or more fatty acids having at least 12 carbon atoms, preferably 12 to 24 carbon atoms, and 0 to 2 non- conjugated carbon-carbon double bonds, (ii) one or more alkyl amine fatty acids having at least 12, preferably 12 to 24 carbon atoms, and 0 to 2 non-conjugated carbon-carbon double bonds in the fatty acid moiety, and / or (iii) one or more fatty alcohols having at least 12 carbon atoms, preferably 12 to 24 carbon atoms, and 0 to 2 non-conjugated carbon-carbon double bonds. Examples of suitable fatty acids include lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearic acid, myristoleic acid, palmitoleic acid, vaccenic acid, oleic acid, and elaidic acid. Examples of fatty alcohols include cetyl alcohol and stearyl alcohol.

[0029] The alkyl amine fatty acid is a compound having either of the following structures:

[0030] NR3 HOOC-R 1 or NR3H + - OOC-R 1

[0031] wherein each R is hydrogen or alkyl, with the proviso that at least one R is alkyl, and R 1 is a linear hydrocarbon group having at least 11 carbon atoms, preferably 11 to 23 carbon atoms, and 0, 1 or 2 non-conjugated carbon-carbon double bonds. Each R is preferably alkyl, and more preferably C1-C4 alkyl. When alkyl, the R groups can all be the same, or can differ from one another.

[0032] Examples of alkyl amine fatty acids are alkyl amine compounds of any one or more of the foregoing fatty acids. The alkyl amine moiety of the alkyl amine fatty acid can be, for example, methylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, tri-n-propylamine, tri-i-propylamine, di-i-propylamine, di-n-propylamine, mono-n-butylamine, di-n-butylamine, tri-n-butylamine, mono-t-butylamine, di-t-butylamine, or tri-t-butylamine, mono-cyclohexylamine, di-cyclohexylamine, and tri-cyclohexylamine. Preferably, the alkyl amine moiety of the alkyl amine is the same alkyl amine as component c). In preparing the coating composition of the present invention, the alkyl amine fatty acid can be produced in situ when the fatty acid is combined with the alkyl amine component c).

[0033] The fatty acid or fatty alcohol component constitutes 0.25 wt.-% to 5 wt.-% by weight of the coating composition. Preferred amounts are at least 0.5 wt.-% or at least 0.75 wt.-% and at most 3 wt.-% or at most 2 wt.-%. In the case of alkyl amine fatty acids, only the weight of the fatty acid moiety (i.e. HOOC-R 1 ) counts towards the weight of the fatty acid component; when the alkyl amine moiety (NR3) falls within the description of component (c), its weight counts towards the weight of component c).

[0034] Component c) is an alkyl amine having a boiling point temperature of 75 °C to 160 °C. Examples of suitable such alkyl amines include triethylamine, diisopropylamine, triisopropylamine, tri-n-propylamine, mono-n-butylamine, di-n-butylamine and monocyclohexylamine. The coating composition comprises 2 wt.-% to 10 wt.-% of alkyl amine, preferably at least 3 wt.-% or at least 4 wt.-% and preferably at most 7 wt.-% of alkyl amine, provided that the amount of alkyl amine is 0.2 to 1.25 parts by weight per part by weight of drying oil.

[0035] Water (component d)) preferably constitutes at least 55 wt.-% or at least 58 wt.-% of the coating composition and preferably at most 85 wt.-% or at most 82 wt.-% of the coating composition.

[0036] Component e) is a wax or mixture of waxes, the melting temperature of the wax or mixture of waxes being at least 60 °C. The melting temperature is preferably at most 120 °C, at most 100 °C or at most 90 °C. The wax can include, for example, a hydrocarbon wax (e.g. an alkane or mixture of alkanes), a R 2 ester compound of the form COOCR 3 wherein R 2 and R 3each is a straight chain hydrocarbon chain having, for example, 12 to 50 carbon atoms, or a mixture of any two or more of the foregoing. The wax can be a natural wax from a plant and / or animal source, and / or a hydrogenated triglyceride from a plant and / or animal source. Examples of suitable plant and / or animal waxes include beeswax, carnauba wax, paraffin wax, rice bran wax, soy wax, emulsified wax, a mixture of soy wax and carnauba wax, or a mixture of any two or more thereof. The wax can be a mixture of waxes including a mixture of preferably carnauba wax and beeswax. The wax or mixture of waxes constitutes 0.25 wt.-% to 7.5 wt.-% of the coating composition. In certain embodiments, it constitutes at least 0.5 wt.-% or at least 0.75 wt.-% of the coating composition, and in some embodiments, up to 6 wt.-%, up to 5 wt.-%, up to 4 wt.-%, or up to 3 wt.-% of the coating composition. The coating composition of the present application for applying a DWR coating to a pre-dyed fabric preferably comprises the wax or mixture of waxes in an amount at the higher end of these ranges, for example, 3.5 wt.-% to 7.5 wt.-%, in particular 4 wt.-% to 6 wt.-%, and the like.

[0037] In certain embodiments, the coating composition further comprises f) 0.25 wt.-% to 10 wt.-% of the coating composition of a crosslinking monomer that is not a fatty acid or an alkyl amine fatty acid. When cured, coating compositions comprising a crosslinking monomer tend to exhibit increased laundry durability, color fastness, and / or anti-fading and abrasion resistance compared to other similar cases where the crosslinking monomer is not present. The crosslinking monomer comprises at least two carbon-carbon double bonds and has up to 20 carbon atoms, preferably up to 13 carbon atoms. The crosslinking monomer preferably does not contain a fluorine atom. The crosslinking monomer comprises at least two free-radically curable groups per molecule, and can have 2 to 20, 2 to 8, or 2 to 6 such groups. The free-radically curable groups are preferably acrylate or methacrylate groups. Specific examples of crosslinking monomers include 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,8-octanediol diacrylate, cyclohexanedimethanol diacrylate, trimethylolpropane triacrylate, glyceryl triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, or a mixture of any two or more thereof. In particular embodiments, the coating composition comprises at least 0.75 wt.-% or at least 1 wt.-% of the crosslinking monomer, and can comprise up to 7.5 wt.-% or up to 5 wt.-% of the crosslinking monomer.

[0038] The coating composition can comprise g) at least one oxidizing agent selected from the group consisting of peroxide compounds, azo compounds, perborate compounds, persulfate compounds and perchlorate compounds. Examples of such oxidizing agents include, for example, 1) acyl peroxides such as acetyl peroxide or benzoyl peroxide, 2) alkyl peroxides such as cumyl peroxide, dicumyl peroxide, lauryl peroxide or tert-butyl peroxide, 3) hydroperoxides such as tert-butyl hydroperoxide or cumyl hydroperoxide, 4) peresters such as tert-butyl perbenzoate, 5) other organic peroxides including acyl alkyl sulfonyl peroxides, dialkyl peroxydicarbonates, diperoxyketals or ketone peroxides, 6) azo compounds such as 2,2'-azobis(isobutyronitrile) (AIBN) or 2,2'-azobis(2,4-dimethylpentanenitrile), 4,4'-azobis(4-cyanopentanoic acid) or 1,1'-azobis(cyclohexanecarbonitrile), 7) ammonium perborate compounds and alkali metal perborate compounds, 8) various persulfate compounds such as ammonium persulfate and alkali metal persulfate compounds, 9) ammonium perchlorate and alkali metal perchlorate and 10) hydrogen peroxide (H2O2). Hydrogen peroxide has the particular advantage of being very inexpensive, and is often readily available at fabric plants for bleaching cotton. In the case of types (1) to (9), the amount of oxidizing agent can be 0.1 wt.-% to 2 wt.-%, based on the weight of the coating composition. Hydrogen peroxide can be present in greater amounts, for example up to 20 wt-%, up to 10% wt-% or up to 5% wt-%, based on the weight of the coating composition.

[0039] The coating composition can comprise h) fumed silica, carbon, graphite or candle soot particles, colored or uncolored mica, chitosan, diatomaceous earth or a mixture of any two or more thereof, when present, which can constitute 0.1 wt.-% to 3 wt.-% of the coating composition. The presence of fumed silica, chitosan and / or diatomaceous earth or mixtures thereof has been found to improve the laundry durability of the cured coating and can also provide effective moth proofing for wool and other protein-based fabrics. These can also provide resistance to insect or fungal infestation of cotton fabrics.

[0040] Particularly interesting coating compositions comprise i) an organic dye. Such coating compositions allow for simultaneous dyeing and application of a DWR finish. The organic dye can be water-soluble. The organic can be, for example, a reactive dye comprising a chromophore and a reactive substituent that binds to the fibers of the fabric, a water-soluble anionic dye (acid dye), a water-soluble cationic dye (basic dye), a water-insoluble disperse dye, a sulfur dye, or a mixture of any two or more thereof. Examples of suitable dyes include acridine dyes, anthraquinone dyes, arylmethane dyes, azo dyes, phthalocyanine dyes, quinone-imine dyes, thiazole dyes, safranine dyes, and xanthene dyes. In some embodiments, the organic dye comprises indigo, white indigo, indigo carmine, or a mixture of any two or more thereof.

[0041] When present, the organic dye can comprise, for example, 0.1% to 5% of the total weight of the coating composition. A preferred upper limit is at most 1.5% or at most 3% of the total weight of the coating composition.

[0042] The coating composition can comprise j) a silicone oil. When present, the silicone oil can comprise 0.1% to 2% of the total weight of the coating composition. The silicone oil can be or include a linear, branched, or cyclic polysiloxane. Examples of polysiloxanes include poly(dimethylsiloxane) (PDMS) and copolymers thereof and siloxane-poly(alkylene glycol) copolymers such as poly(dimethylsiloxane-poly(ethylene glycol) copolymers.

[0043] The coating composition can further comprise, based on the weight of the coating composition, k) 0.1 wt.-% to 5 wt.-%, in particular 0.1 wt.-% to 2.5 wt.-% of at least one terpene and / or terpenoid having 10 to 20 carbon atoms, preferably 15 to 20 carbon atoms. Such terpenes can be provided in the form of a plant essential oil comprising at least 25% by weight or at least 50% by weight of one or more terpenes and / or terpenoids having 10 to 20 carbon atoms. Examples of such plant essential oils include cedarwood oil, eucalyptus oil, pine oil, borage seed oil, rosemary oil, citronella oil, lemon eucalyptus oil, lemongrass oil, thyme oil, or a mixture of any two or more thereof. Steam-distilled or chemically extracted plant essential oils are particularly useful.

[0044] The coating composition can further comprise l) one or more of tannic acid, oxalic acid, alum (potassium alum), ammonium alum, sodium (soda) alum, chrome alum, and sodium chloride. Such compounds have been found to be useful as mordants in the dyeing operations of conventional fabrics; when used in the present application, their presence has been found to improve the laundry durability of the applied coating, whether or not a dye is present in the coating composition. When present, the amount of component l) can be, for example, 0.01 wt.-% to 2 wt.-% based on the total weight of the coating composition.

[0045] In some embodiments, the coating composition has a basic pH of 7.5 to 11, in particular 8.5 to 11; however, for coatings of fabrics comprising wool, a lower pH is preferred as solutions with a pH above 8.0 have a detrimental effect on wool. When coating cellulosic fabrics such as cotton, a coating composition with a basic pH is preferred as better laundry durability is generally seen when the coating composition is basic. The pH can be adjusted into the basic range by including a water-soluble base in the coating composition. Examples of such bases include alkali metal and alkaline earth metal hydroxides. A preferred base is ammonium hydroxide, which is typically provided as an aqueous solution. Ammonium hydroxide can also improve the solubility of the wax. When heated during the curing step, ammonium hydroxide releases ammonia vapour, thereby lowering the pH, which is advantageous as multiple post-dyeing rinses and "reduction cleaning" to remove residual base from the cured coating are not required. This allows the treated fabric to meet the industrial pH specifications for garments with skin contact. In some embodiments, ammonium hydroxide constitutes 0.25 wt.-% to 25 wt.-% of the coating composition. In particular embodiments, ammonium hydroxide can constitute at least 1 wt.-% or at least 2 wt.-% of the coating composition, and at most 15 wt.-%, at most 12 wt.-%, at most 10 wt.-%, at most 8 wt.-%, or at most 6 wt.-% of the coating composition.

[0046] Similarly, some dye processes, such as those using acid dyes, work best under acidic conditions. For these cases, a protonic acid, in particular a carboxylic acid, can be used to adjust the pH into the acidic range, for example 3.0 to 5.5. Acetic acid is particularly suitable for this purpose as it evaporates at the curing temperature, so there is no hydrophilic residue left on the fabric, and thus no need for a post-curing rinse.

[0047] The coating composition can further comprise functional materials, such as oleophobic and lipophobic treatments, i.e., substances that make the treated substrate less receptive to or repel fats and oils; superhydrophobic agents, i.e., substances that impart very high (>130°) contact angles of water droplets to the treated substrate surface; antimicrobial treatments, i.e., substances that inhibit the growth of and / or kill microorganisms, including Cu, Zn, Ag compounds, and chitosan or diatomaceous earth particles; anti-wrinkle agents, such as melamine-formaldehyde resins and urea-formaldehyde resins; fabric softening and anti-chafing agents, such as polydimethylsiloxanes and polymethylhydrogensilane; emollients that produce, for example, softness, wear comfort, and / or moisturizing properties; solid or liquid flame retardants, including various organic phosphorus-, phosphorus-, bromine-, and boron-containing compounds, including sodium tetraborate and boric acid; and trace forensic chemical markers added to the formulation to aid in the detection of counterfeit goods or counterfeit finishing treatments.

[0048] The coating composition can further comprise one or more other finely divided particulate solids that do not melt, thermally degrade, dissolve, or decompose or react with other components of the coating composition at temperatures below 150°C. The d50 particle size, as measured by dynamic light scattering, can be, for example, less than 100 pm, less than 10 pm, less than 1 pm, less than 500 nm, or less than 100 nm. The d50 particle size can be at least 5 nm, at least 10 nm, or at least 20 nm. Examples of such finely divided particles include fumed silica; cellulose nanocrystals; perlite and expanded perlite, chitosan, and diatomaceous earth; plant products such as corn starch and wheat, corn, rice, or wood flour; various metals; various metal oxides such as titanium dioxide, zirconium oxide, and aluminum oxide; ceramic or inorganic particles such as talc, saponite, iron carbonate, calcium carbonate, aluminum hydroxide, magnesium hydroxide, various borate salts, boron and / or phosphorus compounds, titanium carbide, tungsten carbide, pumice, and silicon carbide; thermoset polymers; thermoplastic polymers such as polylactic acid, polyethylene, polypropylene, polystyrene, polytetrafluoroethylene, poly(vinyl fluoride), poly(vinylidene fluoride), poly(hexafluoropropylene), poly(perfluoropropyl vinyl ether), poly(perfluoromethyl vinyl ether), poly(fluorotrichloroethylene); and glass microspheres, among others. The finely divided particulate solids can constitute from 0.1 wt.-% to 3 wt.-% by weight of the coating composition.

[0049] The coating composition can be prepared by forming separate organic and aqueous phases, then combining them under vigorous agitation to disperse the organic phase into the aqueous phase (or vice versa) to produce an emulsion. The emulsion includes a liquid (at 23°C) aqueous phase and a liquid (at 23°C) organic phase, either of which can be the continuous phase. Most typically, the emulsion has a continuous aqueous phase and a dispersed liquid organic phase, but in some embodiments the aqueous phase can form the dispersed phase. Solid components, if any, can be dispersed in either or both of the aqueous and organic phases.

[0050] In a particular process, the drying oil and alkyl amine are first combined and allowed to dissolve in one another. The fatty acid component, crosslinking monomer if used, oil-soluble oxidant, and terpene, terpenoid, and / or plant essential oil containing terpene or terpenoid if used are then added and blended. The waxes are then added and the mixture heated to a temperature sufficient to melt them. This produces the organic phase. Alternatively, the waxes can be combined in their solid form, then melted together, then the liquid waxes are added to the other oil-based components. This approach is advantageous to avoid evaporative loss of the alkyl amine emulsifier.

[0051] Separately, the water is combined with the water-soluble or water-dispersible ingredients, such as the organic dye if used, and the water-soluble oxidant to produce the aqueous phase. The organic and aqueous phases are then combined under vigorous agitation to disperse the organic phase into the aqueous phase (or vice versa), and an at least temporarily stable (as defined below) emulsion is produced. This can be done at any convenient temperature, such as 10°C to 80°C. It is often convenient to add the particulate solid, if used, to either or both of the aqueous or organic phases prior to formation of the emulsion.

[0052] The resulting emulsion has some resistance to phase separation. Preferably, in the absence of agitation, it does not undergo phase separation at 23°C for at least 15 minutes, preferably at least 30 minutes, at least 1 hour, or at least several hours, and especially for at least 1 or 2 days after production. This allows the coating composition to be produced and stored for different periods of time prior to application. It is often convenient, as part of the coating process, to produce the emulsion continuously, whereby the separate organic and aqueous phases are combined and emulsified, then immediately applied to a substrate to produce a coating. In some cases, it can optionally be desirable to add an emulsion stabilizer, such as xanthan gum, polysorbate 20, 60, or 80, lecithin, corn starch, psyllium husks, or guar gum, to stabilize the emulsion's lifetime by inhibiting phase separation.

[0053] The coating composition can be applied to the fabric or other substrate by spraying, rolling, brushing, pouring, dipping, or other method that can be suitable for coating the particular substrate. The coating composition can be applied at a temperature of, for example, 10°C to 70°C, in particular 15°C to 50°C. If desired, excess coating composition can be removed by "dip padding", wringing, rolling with a nip roller, or similar method. Suitable application weights are at least 3, at least 20, or at least 40 grams per square meter (gsm) and up to 500, up to 300, or up to 200 gsm. Preferably, the cured coating can weigh, for example, 4 to 70 gsm.

[0054] The coating composition is cured in air, preferably at a temperature of 100°C to 160°C, to produce a coating. Curing can be achieved by first heating the coated substrate to a temperature of 100°C to 125°C to remove water, and then to a higher temperature or gradually higher temperatures in the range of 126°C to 160°C, in particular 126°C to 150°C.

[0055] The coating composition is conveniently applied and cured in a continuous process in which the substrate is moved through successive stations in which the coating composition is applied, optionally "dip padded" or wrung to remove excess liquid, and then cured at elevated temperature. The fabric substrate can be drawn through a tenter frame frame, for example, for transport through various operations. Alternatively or additionally, one or more drive rollers can move the fabric through various operations.

[0056] The coating composition can also be cured by pulling the coated fabric over a plurality of heated metal drums, during which process the coating is exposed to ambient air.

[0057] The substrate can be any fibrous material capable of being transported through the coating process and the polymerization process. By "fibrous" is meant that the surface of the substrate to which the chemical treatment mixture is applied is composed of or includes at least one type of fiber, and the substrate includes spaces between the fibers that the applied chemical treatment mixture can penetrate. The fibers can be, for example, woven, knitted, twisted, knotted, felted, glued, or otherwise formed into a fabric having sufficient mechanical integrity (i.e., a flat material that can be subsequently sewn or otherwise manufactured into a garment or other article) to perform the method of the present invention. Such fabrics include fibers that can be, for example, natural fibers such as cotton, hemp, wool, flax, silk, lyocell (e.g., Tencel®), rayon, bamboo, and cellulose, etc.; or synthetic fibers such as nylon, aramid, acrylic, polyolefin (e.g., ultra-high molecular weight polyethylene), polypropylene, polyester, polyacetate, polylactic acid, cellulose ester, polyether polyurea, or other synthetic fibers; and blends of any two or more of the foregoing. It can be a smooth, textured, or fleeced fabric.

[0058] In applying the coating, the substrate can be an article such as a garment, personal footwear, an awning, tarpaulin, umbrella, tarp, window treatment, upholstery, carpet, blanket, and bedding, etc.

[0059] In other embodiments, including but not limited to footwear, in which case the substrate can be coated on one side, such as a leather or synthetic leather product, e.g., vinyl, or for athletic shoes, polyester, polypropylene, or nylon, including blends of synthetic and natural fibers, having exposed fiber surfaces on the side to be coated.

[0060] The substrate can also be a non-woven material, or a cellulosic material such as paper or paperboard, etc.

[0061] The coated substrate prepared according to the present invention is useful in applications in which hydrophobicity is desired, such as water- or stain-resistant treatment, moisture barrier, battery and fuel cell separator, bandage, antimicrobial fabric, carpet stain and discoloration protection, wall and window covering material, protective clothing or other para-aramid for bullet or fire resistance, rain gear and outdoor furniture coverings and upholstery, leather or canvas shoe and boot treatment, athletic shoe, headwear, poncho, uniform and other apparel, leather upholstery and apparel, and other automotive and furniture upholstery, tent, sail, awning and tarpaulin, umbrella, hospital scrubs and gowns, medical drape, mattress cover, automotive nonwoven, outdoor performance and sports apparel, including but not limited to jackets and long-sleeved sweatshirts.

[0062] The following examples are intended to illustrate the application and not limit its scope. All parts and percentages are by weight unless otherwise indicated.

[0063] Example 1

[0064] A premix was prepared by mixing the following ingredients, except for the wax, heating to 82°C until a homogeneous mixture was obtained, and then melting the wax into the mixture.

[0065] Premix 1

[0066]

[0067] Additionally, an aqueous phase was prepared by combining 41 parts of water, 5 parts of a 28% aqueous ammonium hydroxide solution, 0.32 parts of benzoyl peroxide, and 0.26 parts of indigo carmine dye. The aqueous phase was then added to the oil phase and emulsified in a high speed laboratory mixer to produce an oil-in-water emulsion. Then 0.53 parts by weight of a hydrophilic fumed silica was mixed into the emulsion to produce the coating composition Example 1. Its pH was 8.5 to 11. The overall composition of Example 1 was as follows:

[0068] Example 1 Composition

[0069]

[0070] 1 Due to rounding, the sum can not add up to 100%.

[0071] A 100% cotton poplin woven fabric weighing 144 gsm was immersed in the coating composition for a few minutes at room temperature, then the wet fabric was pad mopped and wrung out to remove excess fluid. The wetted and wrung fabric was coated with approximately 134 gsm of the coating composition. The wetted fabric was then cured in air at 149°C for fifteen minutes to produce a dyed fabric. The approximate weight of the cured coating was 55 gsm. After curing, the fabric exhibited a deep blue color characteristic of the indigo dye.

[0072] The water resistance of the coated fabric was evaluated according to AATCC 22 Water Resistance Spray Test, both before washing and then after the fabric had undergone multiple home laundry / drying cycles. The results are shown in Table 1.

[0073] Table 1 AATCC 22 Spray Test Results, Example 1

[0074]

[0075] The coating composition of the present invention allows for dying and applying a hydrophobic coating in one processing step. The coated fabric exhibits excellent hydrophobicity which remains even after multiple wash / dry cycles. No rinsing or neutralization is required after the heat-based curing process.

[0076] Example 2

[0077] Coating composition Example 2 was prepared in the same general manner as described in Example 1. The overall composition was as follows:

[0078] Example 2 composition

[0079]

[0080] 1 Due to rounding, the sums can not add up to 100%.

[0081] A knitted 100% polyamide fabric of 194 gsm (grams per square meter) was immersed in the coating composition at room temperature, then the wetted fabric was pad mopped and wrung out to remove excess fluid. The wetted and wrung out fabric was coated with approximately 159 gsm of the coating composition. The wetted fabric was then cured in air at 141 °C for fifteen minutes to produce a dyed fabric. The approximate weight of the cured coating was 47 gsm. After curing, the fabric exhibited a rich blue color characteristic of the dye.

[0082] The coated fabric was evaluated using the AATCC Spray Test as previously described, the results of which are shown in Table 2.

[0083] Table 2 AATCC 22 Spray Test Results, Example 2

[0084]

[0085] The present invention achieves excellent coloration and hydrophobicity on polyamide fabrics. No rinsing or neutralization is required after the heat-based curing process.

[0086] Example 3

[0087] Coating composition Example 3 was prepared in the same general manner as described in Example 1. The overall composition was as follows:

[0088] Example 3 composition

[0089]

[0090] 1 Due to rounding, the sums can not add up to 100%.

[0091] A knitted 100% polyester fabric of 173 gsm was immersed in the coating composition at room temperature, then the wetted fabric was pad mopped and wrung out to remove excess fluid. The wetted and wrung fabric was coated with approximately 157 gsm of the coating composition. The wetted fabric was then dried in air at 107°C for 5 minutes and then cured at 138°C to produce a dyed fabric. The approximate weight of the cured coating was 35 gsm. After curing, the fabric exhibited the rich red color characteristic of the dye.

[0092] The coated fabrics were evaluated using the AATCC spray test as previously described, with the results shown in Table 3.

[0093] Table 3 AATCC 22 Spray Test Results, Example 3

[0094]

[0095] The present invention achieves excellent coloration and hydrophobicity on polyester fabrics. No rinsing or neutralization is required after the heat-based curing process.

[0096] Example 4

[0097] Coating Composition Example 4 was prepared in the same general manner as described in Example 1. The overall composition was as follows:

[0098] Example 4 Composition

[0099]

[0100] 1 Due to rounding, the sum of the percentages may not equal 100%.

[0101] A knitted 100% polyester (171 gsm) and a knitted 100% polyamide (186 gsm) fabric were each coated with Coating Composition Example 4 in the same general manner as described in Example 3. In each case, the fabric was immersed in the coating composition at room temperature, then the wetted fabric was pad mopped and wrung out to remove excess fluid. The wetted and wrung fabric was coated with approximately 162 gsm and 147 gsm of the coating composition, respectively. The wetted fabric was then dried in air at 107°C for 5 minutes and then cured at 138°C to produce a dyed fabric. The approximate weight of the cured coating was 36 gsm and 23 gsm, respectively, for the polyester and polyamide fabrics. In each case, after curing, the fabric exhibited the rich red color characteristic of the dye.

[0102] The coated fabrics were evaluated using the AATCC spray test as previously described, with the results shown in Table 4.

[0103] Table 4 AATCC 22 Spray Test Results, Example 4

[0104]

[0105] The present invention achieves excellent coloration and hydrophobicity on both polyester and polyamide fabrics. No rinsing or neutralization is required after the heat-based curing process.

[0106] Example 5

[0107] Coating composition Example 5 was prepared in the same general manner as described in Example 1. The overall composition was as follows:

[0108] Example 5 composition

[0109]

[0110] 1 Due to rounding, the sum can not add up to 100%.

[0111] Knitted 100% polyester fabric weighing 172 gsm, knitted 90% polyamide / 10% spandex fabric weighing 183 gsm, and poplin woven 100% cotton fabric weighing 147 gsm were each coated with coating composition Example 5 in the same general manner as described in Example 3. The fabrics were immersed in the coating composition at room temperature, then the wetted fabric was pad mopped and wrung out to remove excess fluid. The wetted and wrung out fabric was coated with approximately 152 gsm, 119 gsm, and 121 gsm of coating composition for the polyester, polyamide / spandex, and cotton fabrics, respectively. The wetted polyester and polyamide / spandex fabrics were then dried in air at 107°C for 5 minutes and then cured at 138°C to produce dyed fabrics. The cotton fabric was cured at 149°C for 5 minutes. The approximate weight of the cured coating was 39, 23, and 21 gsm for the polyester, polyamide blend, and cotton fabric samples, respectively, in each case. In each case, the fabric exhibited a deep red color characteristic of the dye after curing.

[0112] The coated fabrics were evaluated using the AATCC spray test as previously described, with the results shown in Table 5.

[0113] Table 5 AATCC 22 Spray Test Results, Example 5

[0114]

[0115] The present invention achieves excellent coloration and hydrophobicity on each of polyester, polyamide / spandex, and cotton fabrics. For the polyester and polyamide / spandex fabrics, these excellent properties remain for at least 30 wash / dry cycles.

[0116] Some loss of the hydrophobic properties of the cotton fabric was seen after about 15 wash / dry cycles. This result is in contrast to the results in Example 1, where excellent hydrophobicity was retained even after 30 wash cycles. The main difference between Example 1 and 5 is the presence of a base (ammonium hydroxide) in the coating composition of Example 1, which results in a higher pH. Higher pH coating compositions are preferred for treating cotton and other cellulosic fabrics. No rinsing or neutralization is required after the heat-based curing process.

[0117] Example 6

[0118] Coating composition Example 6 was prepared in the same general manner as described in Example 1. The overall composition was as follows; its pH was 8.5 to 11:

[0119] Example 6 composition

[0120]

[0121] 1 Due to rounding, the sums can not add up to 100%.

[0122] Coating composition Example 6 was sprayed onto both sides of a knitted 100% polyamide fabric weighing 209 gsm. Approximately 184 gsm of coating composition was applied. The wet fabric was then cured in air at 141 °C for fifteen minutes to produce a dyed fabric. The approximate weight of the cured coating was 36 gsm. After curing, the fabric exhibited a rich yellow color characteristic of the dye.

[0123] As before, the coated fabric was evaluated using the AATCC spray test, with the results shown in Table 6.

[0124] Table 6 AATCC 22 Spray Test Results, Example 6

[0125]

[0126] The present invention again achieved excellent colorability and durable hydrophobicity on polyamide fabrics. No rinsing or neutralization is required after the heat-based curing process.

[0127] Example 7

[0128] Coating composition Example 7 was prepared in the same general manner as described in Example 1. The overall composition was as follows:

[0129] Example 7 composition

[0130]

[0131] 1 Due to rounding, the sums can not add up to 100%.

[0132] Coating composition example 7 was sprayed onto each side of a 100% cotton poplin woven fabric weighing 149 gsm. The approximate coating weight before curing was 89 gsm. The wet fabric was then cured in air at 149°C for fifteen minutes to produce a dyed fabric. The approximate weight of the cured coating was 49 gsm. After curing, the fabric exhibited a rich yellow color characteristic of the dye.

[0133] As before, the coated fabric was evaluated using the AATCC spray test, the results of which are shown in Table 7.

[0134] Table 7 AATCC 22 Spray Test Results, Example 7

[0135]

[0136] The present invention again achieved excellent coloration and durable hydrophobicity on a cotton fabric. No rinsing or neutralization was required after the heat-based curing process.

[0137] Example 8

[0138] Coating composition example 8 was prepared in the same general manner as described in example 1. The overall composition was as follows:

[0139] Example 8 Composition

[0140]

[0141] 1 Due to rounding, the sum of the percentages may not equal 100%.

[0142] A knitted 100% polyester fabric weighing 136 gsm was immersed in the coating composition at room temperature, then the wet fabric was pad mopped and wrung out to remove excess fluid. The wet and wrung fabric was coated with approximately 123 gsm of the coating composition. The wet fabric was then cured in air at 141°C for fifteen minutes to produce a dyed fabric. The approximate weight of the cured coating was 17.5 gsm. After curing, the fabric exhibited a rich blue color characteristic of the dye.

[0143] As before, the coated fabric was evaluated using the AATCC spray test, the results of which are shown in Table 8.

[0144] Table 8 AATCC 22 Spray Test Results, Example 8

[0145]

[0146] Excellent coloration and durable hydrophobicity were achieved.

[0147] Example 9

[0148] Coating composition Example 9 was prepared in the same general manner as described in Example 1. The overall composition was as follows; the pH was 8 to 11.

[0149] Example 9 composition

[0150]

[0151] 1 Due to rounding, the sums can not add up to 100%.

[0152] Coating composition Example 9 was sprayed onto both sides of a knitted 53% polyamide / 28% cotton / 19% spandex fabric weighing 297 gsm. The wet fabric was then cured in air at 141 °C for fifteen minutes to produce dyed fabric. The approximate weight of the cured coating was 84 gsm.

[0153] The coated fabric was evaluated using the AATCC spray test as previously described, the results of which are shown in Table 9.

[0154] Table 9 AATCC 22 Spray Test Results, Example 9

[0155]

[0156] Again, excellent durable hydrophobicity was seen.

[0157] Example 10

[0158] Coating composition Example 10 was prepared in the same general manner as described in Example 1. The overall composition was as follows:

[0159] Example 10 composition

[0160]

[0161] 1 Due to rounding, the sums can not add up to 100%.

[0162] Knitted 100% polyester (170 gsm) and knitted 100% polyamide (185 gsm) fabric were coated with coating composition Example 10 in the same general manner as described in Example 3. In each case, the fabric was immersed in the coating composition at room temperature, then the wet fabric was pad mopped and wrung out to remove excess fluid. The wet fabric was then cured in air at 138 °C for 15 minutes to produce dyed fabric. The approximate weight of the cured coating was approximately 32 gsm for the polyester fabric and approximately 25 gsm for the polyamide fabric. In each case, after curing, the fabric exhibited the characteristic deep red color of the dye.

[0163] The coated fabric was evaluated using the AATCC Spray Test as previously described, with the results shown in Table 10.

[0164] Table 10 AATCC 22 Spray Test Results, Example 10

[0165]

[0166] The present invention achieves excellent coloration and hydrophobicity on both polyester and polyamide fabrics.

[0167] Example 11

[0168] Coating composition Example 11 was prepared in the same general manner as described in Example 1. The overall composition was as follows:

[0169] Example 11 Composition

[0170]

[0171] 1 Due to rounding, the sum can not add up to 100%.

[0172] Knit 90% polyamide / 10% spandex fabric of weight 209 gsm was coated with coating composition Example 11 in the same general manner as described in Example 3. The fabric was immersed in the coating composition at room temperature, then the wet fabric was padded and wrung out to remove excess fluid. The wet fabric was then cured in air at 138°C for fifteen minutes to produce a dyed fabric. The approximate weight of the cured coating was about 37 gsm. The cured fabric exhibited a rich red color characteristic of the dye.

[0173] The coated fabric was evaluated using the AATCC Spray Test as previously described, with the results shown in Table 11.

[0174] Table 11 AATCC 22 Spray Test Results, Example 11

[0175]

[0176] The present invention achieves excellent coloration and hydrophobicity on both polyester and polyamide fabrics. No rinsing or neutralization is required after the heat-based curing process.

[0177] Example 12

[0178] Coating composition Example 12 was prepared in the same general manner as described in Example 1. The overall composition was as follows; the pH was 8.5 to 11:

[0179] Example 12 Composition

[0180]

[0181] 1 Due to rounding, the sum may not equal 100%. * NH4OH is provided as a 28% aqueous solution. The amount of water shown includes water from the NH4OH solution plus any additional water added.

[0182] The coating composition of Example 12 was sprayed onto both sides of a 297 gsm knitted 53% polyamide / 28% cotton / 19% elastane fabric. The wetted fabric was then cured in air at 141°C for 15 minutes to produce a coated fabric. The approximate weight of the cured coating was 84 gsm.

[0183] As mentioned earlier, the coated fabric was evaluated using the AATCC spray test, and the results are shown in Table 12.

[0184] Table 12 AATCC 22 spray test results, Example 12

[0185]

[0186] This invention achieves excellent hydrophobicity.

[0187] Example 13

[0188] The coating composition of Example 13 was prepared in the same general manner as described in Example 1. The overall composition is as follows:

[0189] Example 13 Composition

[0190]

[0191] 1 Due to rounding, the sum may not equal 100%. 2 Water and hydrogen peroxide are provided as a 12% aqueous solution of hydrogen peroxide.

[0192] A 188 gsm woven breathable cotton fabric was coated with the coating composition of Example 13 in the same general manner as described in Example 1. The wetted fabric was then cured in air at 149°C for 15 minutes to produce a dyed fabric. The approximate weight of the cured coating was about 36 gsm. The cured fabric exhibited the rich red characteristic of the dye.

[0193] As mentioned earlier, the coated fabric was evaluated using the AATCC spray test, and the results are shown in Table 13.

[0194] Table 13 AATCC 22 spray test results, Example 13

[0195]

[0196] The present invention achieves excellent colorability and hydrophobicity on both polyester and polyamide fabrics and on the same fibers that are stretched with spandex blended in. No rinsing or neutralization is required after the heat-based curing process.

[0197] Example 14

[0198] Coating composition Example 14 was prepared in the same general manner as described in Example 1. The overall composition was as follows:

[0199] Example 14 composition

[0200]

[0201] 1 Due to rounding, the sums can not add up to 100%. 2 Water and hydrogen peroxide were provided as a 12% aqueous hydrogen peroxide solution.

[0202] A 100% cotton poplin woven fabric of 144 gsm was immersed in the coating composition at room temperature, then the wet fabric was pad mopped and wrung out to remove excess fluid. The wetted and wrung fabric was coated with approximately 142 gsm of the coating composition. The wetted fabric was then cured in air at 149°C for fifteen minutes to produce a dyed fabric. The approximate weight of the cured coating was 62 gsm. The coated fabric was evaluated using the AATCC spray test as previously described, and the results are shown in Table 14.

[0203] Table 14 AATCC 22 Spray Test Results, Example 14

[0204]

[0205] Excellent hydrophobicity was achieved.

[0206] Example 15

[0207] Coating composition Example 15 was prepared in the same general manner as described in Example 1. The overall composition was as follows:

[0208] Example 15 composition

[0209]

[0210] 1 Due to rounding, the sums can not add up to 100%. 2 A mixture of vegetable wax, cetostearical alcohol, and non-ionic surfactant.

[0211] A knitted 66% Lyocell®, 27% wool, 7% polyamide fabric weighing 301 gsm was immersed in the coating composition at room temperature, then the wetted fabric was pad mopped and wrung out to remove excess fluid. The wetted and wrung fabric was coated with approximately 345 gsm of the coating composition. The wetted fabric was then cured in air at 149°C for fifteen minutes to produce a dyed fabric. The approximate weight of the cured coating was 82 gsm. The coated fabric was evaluated using the AATCC spray test as previously described, and the results are shown in Table 15.

[0212] Table 15 AATCC 22 Spray Test Results, Example 15

[0213]

[0214] Again, excellent hydrophobicity was obtained.

[0215] Example 16

[0216] A water phase was produced by combining 70 parts of a 3% aqueous hydrogen peroxide solution, 0.41 parts of potassium alum, and 0.91 parts of fumed silica. Separately, 7 parts of tung oil, 3 parts of triethylamine, 0.52 parts of oleic acid, 1 part of trimethylolpropane triacrylate, and 1 part of cedarwood oil were combined and heated to 75°C, then 3.8 parts of white beeswax and 0.84 parts of carnauba wax preheated to 85°C were added. The water phase and the organic phase were combined at 75°C with stirring to produce an emulsion. The overall composition was as follows:

[0217] Example 16 Composition

[0218]

[0219] 1 Due to rounding, the sum of the percentages can not add up to 100%.

[0220] A knitted grey dyed 100% polyester (53 gsm) and a knitted black dyed polyester, 100% recycled white dyed polyamide (115 gsm), and a black dyed 90% / 10% polyamide- spandex interlock knitted fabric (330 gsm) were coated with the coating composition Example 16 in the same general manner as described in Example 3. In each case, the coating composition was pad mopped onto the fabric at room temperature, then the wetted fabric was squeezed to remove excess fluid. The wetted fabric was then cured in air at 127°C for 15 minutes to produce a dyed fabric. The approximate weight of the cured coating was 24 gsm for the grey polyester fabric, 18 gsm for the black polyester fabric, 11 gsm for the white polyamide fabric, and 43 gsm for the polyamide-spandex fabric.

[0221] The coated fabrics were evaluated using the AATCC spray test as described previously, with the results shown in Table 16.

[0222] Table 16 AATCC 22 Spray Test Results, Example 16

[0223]

[0224] Again, excellent hydrophobicity was obtained on pre-dyed fabrics this time.

[0225] Example 17

[0226] Combine 65 parts of a 3% aqueous hydrogen peroxide solution, 10 parts of a 4% aqueous acetic acid solution, and 0.36 parts of potassium alum and heat to 60°C. Dissolve 0.32 parts of Best Acid Supra red-SF-P3BW red dye into the aqueous phase, then add 0.91 parts of fumed silica. Separately, combine 7.1 parts of tung oil, 4 parts of triethylamine, 0.5 parts of oleic acid, 1 part of trimethylolpropane triacrylate, and 1 part of cedarwood oil, heat to 75°C, then add 2.07 parts of white beeswax and 0.21 parts of carnauba wax preheated to 85°C. Combine the aqueous and organic phases at 75°C with stirring to produce an emulsion. The overall composition is as follows:

[0227] Example 17 Composition

[0228]

[0229] 1 Due to rounding, the sum can not add up to 100%. 2 Includes water added with the hydrogen peroxide and acetic acid solutions.

[0230] Undyed 90% / 10% polyamide-elastane interlock fabric (330 gsm), knitted 100% recycled undyed polyamide (115 gsm), and undyed 100% polyamide two-way stretch (44 gsm) fabric were coated with the coating composition Example 17 in the same general manner as described in Example 16. In each case, the coating composition was pad-dipped onto the fabric at room temperature, then the wetted fabric was squeezed to remove excess fluid. The wetted fabric was then cured in air at 127°C for 15 minutes to produce dyed fabric. The approximate weight of the cured coating was 34.4 gsm for the polyamide-elastane fabric, 9.5 gsm for the white polyamide fabric, and 5.6 gsm for the two-way stretch fabric.

[0231] The coated fabrics were evaluated using the AATCC spray test as described previously, with the results shown in Table 17.

[0232] Table 17 AATCC 22 Spray Test Results, Example 17

[0233]

Claims

1. A coating composition in the form of an emulsion comprising, based on the total weight of the liquid composition, a) 5 wt-% to 35 wt-% of a drying oil; b) 0.25 wt.-% to 5 wt.-% of a fatty acid or fatty alcohol component selected from the group consisting of a fatty acid having at least 12 carbon atoms and 0 to 2 non-conjugated carbon-carbon double bonds, an alkyl amine fatty acid having at least 12 carbon atoms and 0 to 2 non-conjugated carbon-carbon double bonds in the fatty acid moiety, and a fatty alcohol having at least 12 carbon atoms and 0 to 2 non-conjugated carbon-carbon double bonds; c) 2 wt.-% to 10 wt.-% of an alkyl amine having a boiling point temperature of 75 °C to 160 °C, with the proviso that the amount of alkyl amine is 0.2 to 1.25 parts by weight per part by weight of the drying oil; d) 50 wt.-% to 90 wt.-% of water; and e) 0.25 wt.-% to 7.5 wt.-% of a wax or mixture of waxes having a melting temperature of at least 60 °C.

2. The coating composition according to claim 1, wherein the constituent fatty acids of the drying oil comprise at least 2 conjugated carbon-carbon double bonds.

3. The coating composition according to claim 2, wherein the constituent fatty acids of the drying oil comprise at least 3 conjugated carbon-carbon double bonds.

4. The coating composition according to claim 3, wherein at least 40 wt.-% of the constituent fatty acids of the drying oil comprise at least 3 conjugated carbon-carbon double bonds.

5. The coating composition according to claim 3 or 4, wherein the constituent fatty acids of the drying oil comprising at least 3 conjugated carbon-carbon double bonds are one or more of a- eleostearic acid and calendic acid.

6. The coating composition according to any of the preceding claims, wherein the drying oil is one or more of tung oil, balsam pear oil, flaxseed oil, and calendula seed oil.

7. The coating composition according to any of the preceding claims, wherein the fatty acid or fatty alcohol component is selected from the group consisting of a fatty acid having 12 to 20 carbon atoms and 0 or 1 carbon-carbon double bond, an alkyl amine fatty acid having 12 to 20 carbon atoms and 0 or 1 carbon-carbon double bond in the fatty acid moiety, and a fatty alcohol having 12 to 20 carbon atoms and 0 or 1 carbon-carbon double bond.

8. The coating composition according to claim 7, wherein the fatty acid or fatty alcohol component is a fatty acid selected from the group consisting of lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearic acid, myristoleic acid, palmitoleic acid, vaccenic acid, oleic acid, elaidic acid, and mixtures of any two or more thereof.

9. The coating composition according to any of the preceding claims, wherein the alkyl amine is selected from the group consisting of triethylamine, diisopropylamine, triisopropylamine, tri-n-propylamine, mono-n-butylamine, di-n-butylamine, and monocyclohexylamine.

10. The coating composition according to claim 9, wherein the alkyl amine is triethylamine.

11. The coating composition according to any of the preceding claims, further comprising f) 0.25 to 10 wt.-% of a crosslinking monomer of the coating composition, which is not a fatty acid or an alkyl amine fatty acid, which comprises at least two carbon-carbon double bonds and has up to 20 carbon atoms.

12. The coating composition according to any of the preceding claims, wherein the crosslinking monomer comprises 2 or more acrylate groups.

13. The coating composition according to claim 12, wherein the crosslinking monomer is one or more of 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,8-octanediol diacrylate, cyclohexanedimethanol diacrylate, trimethylolpropane triacrylate, glyceryl triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, and dipentaerythritol hexaacrylate.

14. The coating composition according to any of the preceding claims, wherein the wax is selected from the group consisting of carnauba wax, paraffin wax, rice bran wax, soy wax, a mixture of soy wax and carnauba wax, beeswax, and a mixture of any two or more of the foregoing.

15. The coating composition according to any of the preceding claims, further comprising g) at least one oxidizing agent selected from the group consisting of peroxygen compounds, azo compounds, perborate compounds, persulfate compounds, and perchlorate compounds.

16. The coating composition according to claim 15, wherein the peroxygen compound or azo compound is a peroxide.

17. The coating composition according to claim 15, wherein the oxidizing agent is one or more of hydrogen peroxide, benzoyl peroxide, lauryl peroxide, t-butyl peroxide, ammonium perchlorate, ammonium perborate, alkali metal perchlorates, and alkali metal perborates.

18. The coating composition according to any of the preceding claims, further comprising h) 0.1 wt.-% to 3 wt.-%, based on the weight of the coating composition, of a silicon dioxide compound, chitosan, diatomaceous earth, or a mixture of any two or more thereof.

19. The coating composition according to claim 18, wherein the coating composition comprises a hydrophilic fumed silica.

20. The coating composition according to any of the preceding claims, further comprising i) an organic dye or ii) a color pigment.

21. The coating composition according to claim 20, wherein the organic dye comprises a reactive dye, an acid dye, a disperse dye, or a mixture of any two or more thereof.

22. The coating composition according to claim 20, wherein the organic dye comprises indigo blue, white indigo, indigo carmine, or a mixture of any two or more thereof.

23. The coating composition according to claim 20, wherein the organic dye or pigment is water-soluble.

24. The coating composition according to any of the preceding claims, further comprising j) a silicone oil.

25. The coating composition according to any of the preceding claims, further comprising k) 0.1 wt.-% to 5 wt.-%, based on the weight of the coating composition, of at least one terpene and / or terpenoid having 10 to 20 carbon atoms.

26. The coating composition according to any of the preceding claims, further comprising l) 0.01 wt.-% to 2 wt.-%, based on the weight of the coating composition, of one or more of tannic acid, oxalic acid, alum (potassium alum), ammonium alum, sodium (soda) alum, chrome alum, and sodium chloride.

27. The coating composition according to any of claims 1 to 26, further comprising a plant essential oil comprising at least 25 wt.-% of one or more terpenes and / or terpenoids having 10 to 20 carbon atoms.

28. The coating composition according to any of claims 1 to 26, further comprising cedarwood oil, eucalyptus oil, pine oil, or a mixture of any two or more thereof.

29. The coating composition according to any of the preceding claims, comprising: 6 wt.-% to 18 wt.-% of a); 0.75 wt.-% to 2.5 wt.-% of b); 4 wt.-% to 7 wt.-% of c); and 0.75 wt.-% to 5 wt.-% of e).

30. The coating composition according to claim 29, further comprising: 1 wt.-% to 4 wt.-% of f); 0.1 wt.-% to 2 wt.-% of g) and 0.25 wt.-% to 1.5 wt.-% of h).

31. The coating composition according to claim 29 or 30, further comprising j) 0.1 wt.-% to 2 wt.-%, based on the weight of the coating composition.

32. The coating composition according to any of claims 29 to 31, further comprising k) 0.1 wt.-% to 2.5 wt.-%, based on the weight of the coating composition.

33. The coating composition according to any of claims 29 to 32, further comprising l) 0.01 wt.-% to 2 wt.-%, based on the weight of the coating composition.

34. The coating composition according to any of the preceding claims, having a pH of 8.0 to 11 at 23 °C or a pH of 3.0 to 5.5 at 23 °C.

35. The coating composition according to any of the preceding claims, further comprising 0.25 wt.-% to 25 wt.-% of NH4OH.

36. A method for applying a durable water repellent finish to a fabric, comprising the steps of: (a) applying the coating composition according to any of claims 1 to 35 to a fabric, and (b) curing the applied coating composition in air at a temperature of 100 °C to 160 °C to produce the durable water repellent finish.

37. The method of claim 36, wherein the coating composition is applied and cured in a continuous process in which a substrate is moved through a series of stations in which the coating composition is applied, optionally "dipped" or wrung to remove excess liquid, and then cured at elevated temperature.

38. The method of claim 36 or 37, wherein the fabric is polyester and the coating composition comprises a disperse dye.

39. The method of claim 36 or 37, wherein the fabric is cotton or linen and the coating composition comprises an acid dye or a reactive dye.

40. The method of claim 36 or 37, wherein the fabric is cotton or linen and the coating composition comprises 0.25 wt% to 25 wt% NH4OH based on the weight of the coating composition.

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