TWI896646B - Water-free fabric dyeing process and dye compositions - Google Patents

Abstract

A non-aqueous fabric dyeing method used a non-aqueous dyeing composition. The dyeing composition is a fluid at room temperature; contains no more than 5% water and no more than 5% VOCs. The dye composition includes an organic dye that is solid at temperatures up to 130°C and which sublimes or boils at 130 to 220°C, and further includes a carrier phase that is a liquid in the temperature range of 130 to 220°C.

Description

Waterless fabric dyeing method and dye composition

The present invention relates to a method for dyeing textiles, a dye composition and a method for applying a hydrophobic coating to dyed textiles.

Applying a hydrophobic treatment to fabrics is often beneficial. Athletic clothing, rain gear, tents, tarpaulins, and other fabrics that are frequently exposed to rain, snow, and/or ice, or otherwise need to be water-repellent, are among the many examples of textile products that benefit from a hydrophobic treatment. A hydrophobic treatment helps the fabric shed or repel water and water-based contaminants.

WO 2015/127479 and WO 2017/020018 describe certain hydrophobic treatments and methods for applying them to fabrics or other objects. These hydrophobic treatments have been found to be highly effective, imparting excellent hydrophobic (and sometimes oleophobic) properties while maintaining breathability. The applied hydrophobic treatments are also highly resistant to repeated washing cycles.

Despite this, it has been found that hydrophobic fabric treatments, including those described in WO 2015/127479 and WO 2017/020018, among others, often perform inconsistently when applied to fabrics dyed with conventional water-based dyes. In particular, conventionally dyed fabrics require subsequent rinse cycles to remove the chemical ingredients required for water-based dyeing, such as emulsifiers, pH adjusters, humectants, and fixing chemicals. Because these auxiliary additives are formulated to function in a water bath, they are hydrophilic in nature. If the dyeing process or rinsing steps are simplified to save water or process time, traces of these hydrophilic chemicals may remain in the dyed fabric (once it has dried). This residue can impair the subsequent hydrophobicization chemistry applied to repel water, resulting in a poor water-repellent treatment. While WO 2015/127479 and WO 2017/020018 mention that dyes can be added to their respective hydrophobic fabric treatments as a one-step process, poor color saturation has been found to result. Dyed fabrics have a light or faded appearance.

Dyeing plants are often reluctant to perform very thorough washing steps, partly due to cost and equipment limitations, and because they generate large aqueous waste streams that must be cleaned or disposed of. Additionally, wastewater containing dyes is difficult to remediate and can present a health hazard if it contaminates community drinking water.

In fact, waste generation and disposal is a very important issue in the commercial textile dyeing industry and for the entire textile industry. Large amounts of aqueous waste streams are generated not only in the washing steps after dyeing but also during the dyeing process itself.

Fabrics are conventionally dyed using a process in which the fabric is immersed in an aqueous dye bath. Dyes are mostly solid materials that are insoluble in water. As such, they exhibit a strong tendency to settle out of the aqueous dye bath. This problem is mitigated by adding various chemicals to the dye bath, such as surfactants, emulsifiers, and thickeners, to keep the dye particles suspended. Other chemicals are typically added, including various hydrophilic polymers (to make hotsols for hotsol dyeing), chelating agents, leveling agents, pH control agents, defoaming agents, color fixatives, and reducing agents. Many of these are water-soluble, water-dispersible, or otherwise hydrophilic.

Conventional water-based dyeing, therefore, generates large amounts of hazardous wastewater and is most often performed as a batch process. When the dyeing process is complete, or when switching to a different dye, the dyebath is discarded, and the dye container must then be cleaned to remove residual dye from the container's internal surfaces. Cleaning water-based dyebaths is highly labor-intensive. Additional wastewater is generated during dyebath cleaning and from the fabric rinsing step.

Furthermore, the inventors have recognized that, even when performed correctly, a post-dyeing rinsing step can have a detrimental effect on the subsequent hydrophobic finish if the rinse water contains a high content of dissolved minerals. Drying the fabric after exposure to "hard" water results in water-soluble mineral residues remaining on the fabric, which can damage the hydrophobic finish of the overcoat. Therefore, a dyeing process that can be performed without rinsing would be of great value.

The need to discharge large amounts of wastewater in the textile dyeing industry is a significant problem. Over time, this problem has become more pronounced as governments and non-governmental organizations continue to push the industry toward low- or zero-emission manufacturing processes. Consequently, the textile industry has identified waterless dyeing as a long-term goal.

Water-based dyeing methods have other serious disadvantages. The dyebath regularly becomes depleted of dye and must therefore be replenished from time to time, especially if the dyebath is used to dye multiple batches of fabric. This must be done carefully, as variations in the dyebath's properties (such as changes in dye concentration or pH) can affect the method and result in inconsistent coloration. Because the mineral content and pH of water vary from location to location, each dyeing plant needs to adjust its method to accommodate differences in water quality.

Extended batch times are often required, especially when dyeing certain synthetic fabrics such as nylon or polyester. It is often necessary to carry out the dyeing step at elevated temperatures, such as 80°C or, in some cases, even 100°C to 125°C. Because large quantities of water must be heated, the need to use high temperatures significantly increases the energy requirements of the process. In cases where the temperature is at or above the atmospheric boiling temperature of water, it becomes necessary to pressurize the dye vat. This requires specialized equipment. Furthermore, the dyed wet fabric then needs to be dried, which requires even more energy to accomplish on an industrial scale.

CN 104278576 A describes a hot melt dyeing method using a decamethylcyclopentasiloxane medium, wherein a polyester fabric is immersed in the dye, then soaked in water, the fabric is removed, dried, a pure disperse dye is added to the medium and the fabric is placed in the dye bath.

References such as US Pat. No. 3,504,996, US Pat. No. 3,957,427, US Pat. No. 4,132,522, US Pat. No. 4,448,582, GB Pat. No. 1,270,886, and GB Pat. No. 1,274,601 describe various hot-sol dyeing methods. Hot-sol dyeing is an aqueous emulsion bath process in which the batch material contains a small amount of an emulsified organic phase. The organic phase may contain, for example, a water-soluble organic polymer such as a urea-formaldehyde resin, a melamine-formaldehyde resin, a poly(vinyl methyl ether/maleic anhydride amide derivative), or a water-soluble polyglycol. A reducing agent such as methyl hydropolysiloxane may also be present. The thermosol dyeing process can be operated continuously by passing the fabric through a sequence of "dip stations" (where it is immersed in a thermosol dye bath) and then through various heating stations to first dry the wet fabric to remove the water and then "cure" the dye. After dipping in the bath, the fabric is squeezed (dip) to remove excess liquid. Despite the advantage of being able to operate continuously, the thermosol dyeing process has many of the same disadvantages as aqueous batch dyeing. The dye bath must be replenished; unused bath liquid must be discarded; a large amount of waste is generated when cleaning the equipment; energy is required to remove water from the fabric; and post-dyeing fabric treatment is required to remove residual chemicals and surface dye.

Alternative methods to waterbath or hot-sol dyeing exist. For example, US Pat. No. 7,731,763 describes a supercritical _CO₂ dyeing process. Equipment for practicing this technique is commercially available from DYCOO of Weesp, the Netherlands. This method avoids many of the problems associated with using a waterbath, as no water or surfactants are required, and the dyed fabric does not need to be dried. However, it requires extremely expensive high-pressure equipment to handle the necessary operating pressures (up to 3,000 psi), and water-based, post-dyeing fabric cleaning or rinsing is necessary. This is also essentially a batch process and still produces wastewater contaminated with dye.

An alternative to waterbath dyeing is the transfer method. Transfer is a dry process that avoids the need for a dye bath. Instead, the dye is first applied to a transfer paper. This can be done, for example, using inkjet printing or other digital printing methods. The transfer paper is then placed in contact with the fabric. The dye is transferred to the fabric under conditions of heat and mechanical pressure. Under these conditions, the dye sublimates, transferring the color to the fabric.

The continuous transfer method is described, for example, in US Pat. No. 8,870,972. A sublimation dye is applied to each of two transfer sheets. The textile to be colored is sandwiched between the transfer sheets. The sandwich assembly is then subjected to conditions of heat and mechanical pressure, as in a hot press. The dye sublimates, coloring the fabric.

As US Pat. No. 8,870,972 demonstrates, transfer printing is very different from bath dyeing. The dye does not uniformly color the fabric. Instead, the dye remains on the surface of the fabric that contacts the transfer sheet and colors it. When the dye is applied to one side of the fabric, only that side becomes colored. Therefore, the method of US Pat. No. 8,870,972 allows for, and is particularly suitable for, producing fabrics with different colors and/or patterns on opposite sides or with single-sided coloring.

Alternatively, printing is performed using water-based dyes or inks. This is because the use of water-insoluble dyes complicates subsequent finishing steps (e.g., the application of a water-repellent finish): the dyes interfere with the subsequent water-based finishing step. Essentially, textile finishing can be accomplished using either water-compatible or water-incompatible chemistries. There is a strong desire to move away from water-compatible chemistries, which consist of dyeing and water-repellent finishing, toward water-incompatible chemistries, in order to achieve highly water-repellent and wash-resistant finishes. Furthermore, a secondary goal is to eliminate wastewater from dyeing operations without generating any secondary pollution.

When dye is applied only to the surface of the fabric, the color or pattern becomes easily worn off, unlike when the fabric is dyed in a bath. The hydrophobicity of many synthetic fabrics means that water-based dyes or inks do not penetrate into the yarn, and therefore only surface coloring is produced. In addition, as described in US 8,870,972, the transfer printing method requires the use of a transfer sheet, which increases complexity and cost, especially when attempting to operate the transfer printing method continuously. Therefore, transfer printing is not a suitable alternative to waterbath dyeing and is not commercially useful for dyeing roll items or for use in other large-scale fabric dyeing operations. Alternatively, transfer printing is mainly limited to producing images (patterns, printing, logos, photos and other artworks) on fabrics that have already been colored in the bath dyeing process or on undyed white or natural color backgrounds.

Research into the problem of applying hydrophobic coatings to conventionally dyed fabrics revealed to the inventors that it was related to residual chemicals used in water-based dyeing processes. Surfactants and other additives in the dyebath tend to deposit on and remain on the dyed fabric if the fabric is not adequately washed. These chemicals, which are typically hydrophilic in nature, appear to interfere with the application or performance of the hydrophobic treatment.

Therefore, the problem can be partially solved by thoroughly washing the dyed fabric before applying the hydrophobic treatment. However, this solution only increases the amount of waste generated. It also increases costs and occupies cleaning equipment, reducing its productivity. Therefore, this solution is unpopular.

Instead, alternatives to waterbath dyeing are needed. These alternatives should be efficient from an energy and raw material perspective; be capable of dyeing webs or other large quantities of fabric at high rates; dye the fabric uniformly and consistently; and avoid the use of large quantities of liquids that must be disposed of or cleaned up after use. When seeking an environmentally friendly method, the method should not involve photochemical activity and/or volatile organic compounds (VOCs).

The method should produce dyed fabrics that can be easily and consistently coated with a hydrophobic treatment without having to wash the dyed fabric before applying the DWR coating. The non-polar nature of the hydrophobic treatments described in WO 2015/127479 and WO 2017/020018 makes it easier for them to penetrate synthetic fiber yarns, as the fibers themselves are non-polar. This observation leads to better abrasion and laundry resistance in WO 2015/127479 and WO 2017/020018 compared to other water-based finishing methods. However, using water-based dyeing methods compromises the properties of those hydrophobic treatments. It is desirable to develop dyeing methods that precede the hydrophobic treatment process without compromising the performance of the subsequently applied hydrophobic treatment.

In one aspect, the present invention is a method for dyeing a textile, comprising the following steps: A. applying a fluid dye composition to at least one surface of the textile at a temperature of 10°C to 100°C using a non-immersion method at an application weight of 2.5 to 250 grams per square meter of textile, wherein the dye composition comprises a) a carrier phase that is liquid in the temperature range of 20°C to 220°C; the carrier phase having dissolved or suspended therein b) 2.5 to 300 grams per liter of the dye composition of at least one organic dye that is solid at a temperature below 130°C and has a sublimation or melting temperature of 130°C to 220°C, and B. Curing the dye composition by heating the fabric having the applied dye composition to a temperature at least equal to the boiling or sublimation temperature of the at least one organic dye for a period of at least 30 seconds, such that the dye boils or sublimates and at least a portion thereof is absorbed by, diffuses into, and/or chemically bonds to the fabric, wherein the dye composition contains no more than 5% by weight of water and no more than 5% by weight of volatile organic compounds, and the dye composition has a kinematic viscosity of at least 10 centistokes and at most 5000 centistokes at 25°C.

The present invention offers numerous advantages. Both the dye application step (step A) and the curing step (step B) can be performed continuously, although, as explained below, in some embodiments of the invention, the curing step can also be performed in batches. When both steps A and B are performed continuously, the process is rapid and requires only short residence times in the operating equipment. In some embodiments, the operating equipment itself is non-specialized, inexpensive, and readily available.

The process is essentially non-aqueous, thus avoiding the drawbacks of using aqueous dye compositions – the large amount of waste, the need to renew the bath by adding dye and other chemicals, the need to dry the fabric, and the associated energy costs. Essentially all of the dye composition remains in the fabric, so the process produces very little waste.

Equipment cleaning is easy, and little waste is generated. The coating weight is low, and due to this and the viscosity of the dye composition, the coated fabric exiting step A of the process is damp, but there is little, if any, excess dye composition that drips from the fabric or transfers onto the processing equipment. Any small amount of dye composition that remains on the coating equipment can be easily washed or wiped off. In some cases, equipment used in the curing step may become contaminated with small amounts of organic dye due to sublimation or volatilization of the dye during the curing step. In most cases, this can be removed thermally.

Even if the dye composition remains in the fabric, it is generally not necessary to wash the fabric after dyeing to remove residual surface chemicals. Similarly, "reduction cleaning" (an aqueous process used to remove residual uncured dye) is not required. Instead, residual surface dye can be removed as part of the curing process or by a second or subsequent heat treatment. This is an important advantage, particularly in situations where subsequent finishing is to be applied to the fabric. For example, the dyed fabric can subsequently be treated to make it water- or oil-repellent. Fabrics dyed in this method generally do not require prior cleaning or rinsing before applying such treatments.

Unlike transfer printing, this method is a true dyeing process, in which the organic dye penetrates the fibers of the fabric, not just as a surface treatment. The color is rich, vibrant, and uniform; the dyed fabric exhibits excellent color fastness, resistance to bleeding, and minimal wet or dry rubbing (crocking). The dyed fabric is highly resistant to fading after repeated washings. The dyed fabric has a pleasant "hand" and other tactile properties.

Quite surprisingly, even dyeing is often seen even when the dye composition is applied to only one side of the fabric.

In addition to these other advantages, the method is versatile. It easily allows multiple colors to be applied to a single length of fabric simply by changing the dye composition. Dyes of different colors can be applied to the fabric to form a color blend.

In another aspect, the present invention is a fluid dye composition comprising: a) a carrier phase that is liquid within a temperature range of 20°C to 220°C; the carrier phase having dissolved or suspended therein b) 2.5 to 300 grams per liter of the dye composition of at least one organic dye that is solid at 23°C and sublimes and/or boils at a temperature of 130°C to 210°C; wherein the dye composition contains no more than 5% by weight of water and no more than 5% by weight of volatile organic compounds, and the dye composition has a viscosity at 25°C of at least 10 centistokes and no more than 5,000 centistokes.

In step A of the method of the present invention, the fluid dye composition is applied to the fabric using a non-immersion method. A "non-immersion" method means that the fabric is not immersed in a bath of the dye composition during the dye composition application step. This allows the dye composition to be applied to the fabric without the need to remove excess material by, for example, dipping, extrusion, vacuuming, or drying. Additionally, there is no need to remove or distill liquefied gases, such as _CO2 , some of which invariably escapes into the atmosphere.

Examples of non-immersion application methods include, for example, spraying, brushing, roll coating, slot die coating, and doctor blade coating. Roll coating, including direct and/or gravure coating, and doctor blade coating (including air knife coating) are particularly suitable.

Roll coating is performed by applying a fluid dye composition to the surface of a roll, such as a gravure roll. The fabric is then brought into contact with the roll surface, transferring the fluid dye composition to the fabric surface. Gravure roll coating is a type of roll coating that uses an engraved roll to facilitate dye transfer. The engraving controls the coating weight and also provides optimal application uniformity.

When carrying out step A in the gravure roller coating method, direct, reverse or offset printing methods can be used. In direct gravure coating, the fluid dye composition is introduced into the surface of a rotating engraving roller, as by a pan, wherein the roller is partially immersed in the fluid dye composition, or by some other accessories by which the fluid dye composition is kept against the roller. The roller is rotated in the same direction as the fabric movement by the application station usually. Before the dye composition is applied to the fabric, a blade is typically applied against the gravure roller to wipe off any excess dye composition. As the roller continues to rotate, the fluid dye composition on the roller surface is introduced into the fabric at the roller gap point. The roller gap point is typically formed between the engraving roller and a support roller or other fixed elements. The dye composition is transferred to the fabric by the roller gap force and is also partially "pushed" into the fabric by the roller tension force.

Reverse gravure coating is similar, except that the gravure rolls rotate in the opposite direction.

In the gravure coating process, an intermediate roll (the "offset roll") is used to transfer the dye composition from the gravure roll to the fabric. The dye composition is transferred from the rotating gravure roll to the rotating offset roll, and from there to the fabric, by passing the fabric through a nip formed by the offset roll and a support roll or other fixed element.

In the blade coating process, a puddle of dye composition is applied to the surface of the substrate. The fabric is passed through a coating station where the dye composition is deposited on its top surface, and the fabric with the applied dye composition is conveyed under a knife that mechanically or pneumatically meters the dye composition to the desired coating weight. Floating knives, knife-over-roll, knife-over-fixed-table, and knife-over-conveyor configurations, as well as various air knives, are suitable. Typically, an excess of dye composition (sometimes referred to as a "puddle") accumulates on the top surface of the fabric, upstream of the knife.

Equipment for gravure coating and doctor blade coating is well known and available from many sources, such as Innovative Machine Corporation (Birmingham, Alabama), Pyradia Corporation (Saint-Hubert, Ontario), IMC Corporation (Fairfield, New Jersey), Retroflex Co., Ltd. (Wrightstown, Wisconsin), Yessing Machine Corporation (Taiwan), and Zimmer Klagenfurt (Austria).

The dye composition is applied to the fabric at a temperature of 10°C to 100°C. Preferably, the temperature is 10°C to 50°C or 20°C to 40°C. Particularly preferably, the temperature is 20°C to 35°C. An advantage of the present invention is that the application step can be carried out in a factory environment under ambient conditions.

The dye composition is applied at an application weight of 2.5 to 250 grams of dye composition per square meter of fabric (gsm). In some embodiments, the application weight can be at least 5 gsm, at least 10 gsm, at least 20 gsm, and in some embodiments can be up to 200 gsm, up to 150 gsm, up to 100 gsm, up to 75 gsm, up to 60 gsm, or up to 50 gsm.

The application weight and concentration of the one or more organic dyes in the dye composition can be selected together so that at least 0.25 gsm, at least 0.5 gsm, or at least 0.75 gsm of organic dye is applied. In some embodiments, the amount of the one or more organic dyes is up to 5 gsm, up to 2.5 gsm, up to 1.5 gsm, or up to 1.25 gsm.

The application of the dye composition is preferably carried out continuously by moving the fabric continuously through a dye application station where the dye is applied. This can be done by pulling the fabric through the dye application station using a device such as a tenter frame, one or more drive rolls, an endless belt or the like.

A curing step is performed on the fabric having the applied dye composition. Curing is performed by heating the fabric having the applied dye composition to a temperature at least equal to the boiling or sublimation temperature of the one or more organic dyes for a period of at least 30 seconds.

In some embodiments, the curing temperature is at least 140° C., at least 150° C., at least 160° C., or at least 170° C., and in some embodiments is up to 210° C., up to 200° C., or up to 195° C. In some embodiments, the curing temperature is up to 200° C., and the curing step is followed by a subsequent step in which the fabric with the cured dye composition is heated to an even higher temperature, such as 210° C. to 250° C. In this final step, residual dye remaining on the fabric surface is removed thermally or “burned off” by thermal decomposition and/or evaporation.

Under the temperature conditions just described, the curing time is at least 30 seconds. The curing time can be at least 1 minute, at least 2 minutes, or at least 3 minutes, and can be, for example, up to 1 hour, up to 30 minutes, up to 15 minutes, up to 10 minutes, up to 8 minutes, or up to 6 minutes.

The curing step can be carried out in air or an inert atmosphere such as nitrogen, argon, helium, etc. (or any mixture of any two or more thereof). When the curing step is carried out in air, the fluid dye composition of the present invention preferably has a flash point of at least 220°C as measured by the ASTM D92 open cup method.

It is preferred to apply heat using non-contact methods, that is , methods in which heat is supplied by a heated, non-liquefied gas or by radiation rather than by contacting the fabric with a heated solid that transfers the heat to the fabric.

In some embodiments, the curing step is performed at approximately atmospheric pressure or slightly below atmospheric pressure (e.g., at least 90 kPa absolute to up to 202 kPa or up to 125 kPa absolute). In other embodiments, the curing step is performed under elevated pressure. The elevated pressure can be, for example, at least 202 kPa, at least 500 kPa, or at least 700 kPa, and can be, for example, up to 10,000 kPa, up to 5000 kPa, or up to 3500 kPa, all of which are absolute. When the curing step is performed under elevated pressure of 202 kPa absolute or higher, it is preferably performed under an inert atmosphere, as described above. In any superatmospheric curing step, the inert gas should not liquefy (i.e., be in a gaseous state and not in a liquid or supercritical state) at the process pressure used.

In some embodiments, the curing step (B) is performed continuously. This can be accomplished by moving the fabric through the curing station using the apparatus described above for the dye application step.

The coating method of the present invention can be carried out in an integrated process in which the application of the dye composition (step A) and step B are both carried out continuously, wherein the fabric is continuously moved through a dye application station where the dye composition is applied, and then continuously moved through a curing station where the fabric and the applied dye composition are subjected to curing conditions as just described. This can be done by moving the fabric through the dye application and curing stations using suitable equipment as described with respect to the dye application step.

In some embodiments, curing step B is performed in an oven. In such embodiments, the fabric with the applied dye composition is preferably moved continuously through the oven, with the oven length and line speed (the speed at which the fabric moves through the oven) selected so that the fabric's residence time in the oven is as described above for the curing step. The fabric with the applied dye is heated in the oven to the curing temperature described above. The type of oven is not particularly critical. The required heat can be supplied, for example, by heated gas, heated hot fluid, radiation (e.g., by infrared light or other electromagnetic energy source), or other suitable means.

The oven is preferably operated at approximately atmospheric pressure, such as 90 kPa to 125 kPa absolute, although higher or lower pressures may be used. During the curing step, the fabric is preferably subjected to little or no mechanical pressure while in the oven. The mechanical pressure on the fabric may, for example, not exceed 70 kPa, not exceed 35 kPa, or not exceed 15 kPa at any point in the oven. In some embodiments, the fabric may also be unsupported from below during the curing step in the oven, such as when the fabric is attached to a tenter frame by its edges.

In other embodiments, curing step B is performed under excessive atmospheric pressure, preferably in a sealed container under an inert atmosphere, as described above. A suitable container is an autoclave or other vessel capable of handling pressure. The container may have one or more gas ports through which gas may be introduced for pressurization. A specific container useful for performing step B is described in Figures 1, 2, and 3 of WO 2017/020018 (incorporated herein by reference). The fabric after application of the dye composition can be rolled or braided for insertion into such a reaction vessel. The fabric can be positioned on a spinning hammer within the reaction vessel, as described in WO 2017/020018.

In a preferred method, no steps of washing, removing excess fluid (e.g., by wringing, rolling, or pressing the fabric), or drying the fabric are performed between the dye application step A and the curing step B. An advantage of the present invention is that such steps are generally unnecessary due to the properties of the dye composition and the weight applied.

Under curing conditions, the organic dye boils or sublimates and at least a portion of it is absorbed by the fabric and/or the fibers comprising the fabric, diffuses into and/or chemically bonds to the fabric and/or fibers, thereby producing the desired coloration. Thus, the method of the present invention is a true dyeing method, rather than a coating method, in which the colorant is present in a binder that forms a surface layer on the outer surface of the fabric and/or the fibers comprising the fabric. Typically, the carrier phase of the dye composition has at least partial solubility in the yarn. Compared to water-based surface treatments, this is believed to allow the dye to be more thoroughly diffused into the yarn, achieving true dyeing. Another beneficial effect is that the applied and cured dye does not interfere with the subsequent application of a hydrophobic coating.

It is believed that at least a portion and in most cases substantially all of the carrier phase is also absorbed by the fabric and/or the fibers of which the fabric is composed, diffuses into and/or chemically bonds to the fabric and/or fibers. Like this, little or no waste liquid or solid stream is generated during or due to the curing step. When cleaning the application equipment (rollers, pots, blades, etc.), a small amount of waste may be generated. This waste can usually be recycled for subsequent use in the method, particularly when cleaning the application equipment with the carrier phase of the dye composition or its components. In addition, very little (if any) of the carrier phase evaporates or is discharged into the atmosphere. Dye that evaporates and coats the interior of the equipment used for the curing step can be easily removed by a high-temperature "flash-off" process or by wiping.

When curing is performed in a sealed container, it is advantageous to enclose the fabric with the applied dye composition in a wrapper to minimize the formation of dye residues on the inner surface of the container, thereby reducing the need for subsequent cleaning. The wrapper can be a length of undyed guide fabric, a bag or other attachment, which can be deformable and preferably permeable to air. When the fabric is rolled up, the wrapper can be or include one or more outer circles of undyed fabric, which is generally sufficient to reduce or eliminate the escape of volatile dyes from the fabric roll.

When curing is performed in a sealed container, even fabrics coated with different dye compositions, or even fabrics with different coloring dyes, can be cured simultaneously. In the event that multiple portions of fabric to which different coloring dyes have been applied are cured simultaneously in a single sealed container, it is preferred to wrap each such portion individually as just described to prevent color contamination.

In some embodiments, the fabric of single length is dyed with two or more different colors sequentially along the length of fabric.Can be as mentioned above by for example changing the dye composition used in single application station or by making fabric pass through the first application station (only the first colored dye composition is applied to the part of fabric length at the first application station) and then by the second application (wherein the second colored dye composition is applied to the second part of fabric length) continuously apply the dye composition of different colors.Can fabric be fed into the curing oven continuously and solidify as mentioned above.When fabric will be solidified in airtight container, advantageously a part of fabric length (center of adjacent part (corresponding dye composition has been applied thereto)) is kept as undyed. Lengths of fabric may be rolled up and cured in a sealed container, with the undyed portion forming one or more loops of fabric that separate adjacent dyed portions of the roll, thereby preventing color contamination during the curing step.

The coating method of the present invention can be used to dye fabrics to produce solid colors. It is also useful for producing color blends, patterns and other designs, logos, and uneven coloring in various ways.

Can make color blend in different ways according to method.In some embodiments, two or more different dye compositions (it produces different dye colors after solidification separately) can be applied to fabric and solidify fabric as mentioned above simultaneously or continuously.In such embodiment, one or more dye compositions can be applied to one side of fabric, and one or more remaining dye compositions can be applied to the opposite side of fabric.Yet, also all dye compositions can be applied to the same side of fabric.When forming blend, the special useful mode of solidifying dye composition is to roll up the fabric with the dye composition applied, and then make the fabric rolled up stand curing conditions, particularly in airtight container.

Another way to create a color blend is to coat two or more fabrics with different dye compositions that produce different colors upon curing. The curing step is then performed with the coated major surfaces of the fabrics in contact with each other. This can be accomplished, for example, by stacking the fabrics and/or rolling or folding them together to form a roll or stack with alternating layers of different fabrics. As previously described, upon curing, a color blend forms on both fabrics.

A method for producing uneven coloring in a fabric is a variation of the color blending method just described. As previously mentioned, a first dye composition is applied to the fabric. If the fabric itself is to be cured, this dye composition can be evenly applied to the fabric to produce a solid color. A second dye composition producing a different color is applied to a second fabric. The second fabric has openings on its main surface. The openings can define a pattern, design, or logo (arranged randomly or otherwise). The second fabric can be, for example, lace or a net. Then, as described in the preceding paragraph, the two fabrics with the applied dye compositions are cured simultaneously, with their main surfaces in contact with each other. The color blend forms at the contact point between the two fabrics, but not elsewhere, creating the desired uneven coloration.

Dye compositions include an organic dye and a carrier phase. The dye is dispersed and/or dissolved in the carrier phase (and may be partially dispersed and partially dissolved). "Dye" refers to any solid colorant having the thermal properties described herein. The dye may be soluble, partially soluble, or insoluble in the carrier phase. As used in this specification, no distinction is made between "dye" and "pigment," both of which are intended to be encompassed by the term "dye."

The dye can be present in an amount of, for example, 2.5 to 300 grams per liter of fluid dye composition. A preferred lower limit is at least 10 grams per liter or at least 20 grams per liter. A preferred upper limit is up to 150 grams per liter, up to 100 grams per liter, or up to 80 grams per liter.

Organic dyes are characterized as being solid at temperatures below 130°C, meaning they do not melt, degrade, boil, or sublime at such temperatures, and are solid at all lower temperatures and 1 atmosphere (101 kPa). Organic dyes sublime and/or boil at temperatures between 130°C and 210°C, preferably between 140°C and 190°C. Organic dyes may or may not have a melting temperature below the sublimation or boiling temperature. So-called "sublimation dyes" are generally considered to not exhibit any such melting temperature; such dyes are fully useful in the present invention.

In some embodiments, the organic dye has a molecular weight of 300 to 800, specifically 350 to 700 or 400 to 600.

Suitable organic dyes include preferably anthraquinone dyes, azo dyes, diphenylamine dyes, nitroarylamine dyes, coumarin dyes, methane dyes, naphthostyryl dyes, quinophthalone dyes, formazan dyes and benzodifuranone disperse dyes, which have the aforementioned thermal characteristics.

Quinone dyes are characterized by having at least one quinone unit in their molecular structure, i.e., a unit having structure I: (I);

Anthraquinone dyes are characterized by including at least one anthraquinone unit in their molecular structure, i.e., a unit having structure I: (II) In each case, one or more of carbon atoms 1-8 and (in the case of quinone dyes) 10 are substituted with a heteroatom-containing substituent, wherein the heteroatom is bonded to the indicated carbon atom of the anthraquinone unit. The heteroatom-containing substituents may be the same or different (if there is more than one). The oxygen bonded to carbon atom 10 in Structure II may be replaced by nitrogen, which may be further substituted. A variety of such anthraquinone dyes are known; those having the thermal properties described above are suitable for use in the present invention. Among the useful quinone and anthraquinone dyes are alizarin (1,2-dihydroxyanthraquinone), oxalool blue, CI Reactive Blue 19, indanthraquinone (CI Vat Blue 4), Acid Blue 25, Alizarin Red S, antrapurpurin, carminic acid, 1,4-diamino-2,3-dihydroanthraquinone, 7,14-dibenzopyrenequinone, dibromoanthathrone, 1,3-dihydroxyanthraquinone, 1,4-dihydroxyanthraquinone, CI Disperse Red 9, CI Disperse Red 11, CI Disperse Red 15, CI Disperse Red 60 Kuwanon, Oil Blue 35, Oil Blue A, physcion, quinizarin Green SS, remazol Brilliant Blue R, CI Disperse Violet 4, CI Disperse Violet 26, Solvent Violet 13, 1,2,4-trihydroxyanthraquinone, Vat Orange 1, and Vat Yellow 1.

Azo dyes are characterized by having at least one RN=NR or R=N-NH-R unit in their molecular structure. The R group is preferably phenyl, naphthalene, anthracene, ,or wherein any carbon atom of any such R group may be substituted or unsubstituted. Examples of azo dyes include Acid Orange 7, Acid Red 13, Acid Red 88, Alcine Yellow, Allure Red AC, Biebrich Scarlet, Bismarck Brown Y, Brown HT, D&C Red 33, Direct Blue 1, Direct Blue 15, Disperse Orange 1, Lithol Red BK, Metamine Yellow, Mordant Brown 33, Mordant Red 19, Oil Red O, Orange, Orange G, Orange GGN, Pigment Yellow 10, Azosulfonamide, Red 2G, Crimson GN, Solvent Red 26, Solvent Yellow 124, Sudan Black B, Sudan 1, Sudan II, Sudan III, Sudan IV, Sudan Red 7B, Sudan Red G, Sudan Dye, Sudan Yellow 3G, Sunset Yellow FCF, Tartrazine, Nasturtium Orange, Coneworm Blue, and Yellow 2G.

One or more organic dyes are dispersed and/or dissolved in the carrier phase.The carrier phase is made up of one or more constituent materials, and these constituent materials form the liquid phase with some characteristics when combined.Except any dissolved dye, for the purpose of the present invention, all components of the dye composition liquid phase are considered to be the part of carrier.It is liquid in the temperature range of 20 ℃ to 220 ℃.The carrier phase does not contain water, or if there is water, then water constitutes the dye composition weight and is not more than 5 % by weight.The carrier phase does not contain volatile organic compounds (VOC) as defined below, or, if there is any VOC, then VOC constitutes the dye composition and is not more than 5 % by weight.Dye composition has a viscosity of at least 50 centistokes to a maximum of 5000 centistokes at 25 ℃.

In some embodiments, the carrier phase includes at least one polydimethylsiloxane having a kinematic viscosity of at least 10 centistokes at 25°C, as measured by dynamic rotational rheology using a TA Instruments AR Series rheometer or equivalent. The polydimethylsiloxane can be linear, cyclic, branched, or some combination thereof. It can have various end groups, such as alkyl groups (methyl or other alkyl groups, phenyl groups, etc.) or functional end groups. The polydimethylsiloxane can have a kinematic viscosity of at least 25 centistokes (cst), at least 50 cst, at least 90 cst, at least 300 cst, or at least 350 cst, and, for example, up to 5,000 cst, up to 2,000 cst, or up to 1250 cst. Different polymer chain lengths in silicone chemistry result in different viscosities. Water-immiscible polysiloxanes are preferred. As used herein, a material is "water-miscible" if it does not visibly phase separate from the water when mixed with water in a 1:1 volume ratio at 25°C and then left at that temperature without agitation for at least 30 seconds.

In some embodiments, the polydimethylsiloxane comprises at least 5% of the fluid dye composition weight. In some embodiments, the polydimethylsiloxane comprises at least 7.5%, at least 10%, at least 60% or at least 75% of the fluid dye composition weight. It can constitute up to 98%, up to 96%, up to 95% or up to 93% of its weight. In some embodiments, the polydimethylsiloxane comprises 50% to 95% or 60% to 93% of the dye composition weight in the absence of an ethylenically unsaturated free radical polymerizable monomer or the monomer constituting the dye composition weight. In some embodiments, the polydimethylsiloxane comprises 15% or more of the dye composition weight in the presence of an ethylenically unsaturated free radical polymerizable monomer, and the polydimethylsiloxane comprises 5% to 30% or 7% to 20% of the dye composition weight.

In some embodiments, the carrier phase includes at least one ethylenically unsaturated free radical polymerizable monomer ( i.e., a vinyl monomer having a -CR= _CH2 group, where R is hydrogen or a group bonded to the indicated carbon atom through another carbon atom to form a carbon-carbon bond). In such embodiments, the vinyl monomer can comprise, for example, at least 2.5%, at least 5%, at least 15%, or at least 20% by weight of the dye composition, and can comprise, for example, up to 60%, up to 50%, up to 40%, or up to 30% thereof.

Vinyl monomers include, for example, vinyl aromatic compounds, α-olefins, acrylate monomers, methacrylate monomers, acrylamide, vinyl alcohol, vinyl halides, and vinyl esters.

In some embodiments, all or some of the vinyl monomers are hydrophobic monomers having a linear or branched aliphatic, alicyclic, aromatic, or group containing at least 8, at least 10, or at least 12 carbon atoms. The alkyl group may contain, for example, 8 to 24 carbon atoms, or 10 to 20 carbon atoms, or 12 to 18 carbon atoms. In some embodiments, the alkyl group is a linear alkyl or alkenyl group having 8 to 24, 10 to 20, or 12 to 18 carbon atoms. In some embodiments, the alkyl group is partially or fully fluorinated and contains 8 to 24, preferably 10 to 20, carbon atoms.

The one or more hydrophobic monomers preferably have a solubility in water of not more than 2 parts by weight, more preferably not more than 1 part by weight, and even more preferably not more than 0.25 parts by weight per 100 parts by weight of water at 30°C. It is preferred that water is soluble in the one or more hydrophobic monomers to an extent of not more than 2 parts by weight, more preferably not more than 1 part by weight, and even more preferably not more than 0.25 parts by weight per 100 parts by weight of the one or more monomers at 30°C.

Examples of hydrophobic monomers include, but are not limited to, one or more of the following: octyl acrylate, octyl methacrylate, decyl acrylate, decyl methacrylate, lauryl acrylate, lauryl methacrylate, octadecyl acrylate, octadecyl methacrylate, 2-(perfluorohexyl)ethyl acrylate, 2-(perfluorooctyl)ethyl acrylate, 2-(perfluorodecyl)ethyl acrylate, 2-(perfluorohexyl)ethyl methacrylate, 2-(perfluorooctyl)ethyl methacrylate, lauryl methacrylate, stearyl methacrylate, 2-(perfluorodecyl)ethyl methacrylate, 2-(perfluorooctyl)ethyltrichlorosilane, and vinylnaphthalene.

If present, the hydrophobic monomer preferably constitutes no more than 10%, no more than 5%, or no more than 1% of the total weight of the dye composition.

Preferably, at least a portion or all of the vinyl monomers are crosslinking monomers containing two or more free radical polymerizable ethylenically unsaturated groups. The ethylenically unsaturated groups of such crosslinking monomers may be acrylate and/or methacrylate groups. Specific examples of crosslinking monomers include acrylates and/or methacrylates of polyols having 2 to 50, 2 to 20, or 4 to 12 carbon atoms, such as 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,8-octanediol diacrylate, cyclohexanedimethanol diacrylate, trihydroxymethylpropane triacrylate, glycerol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, and corresponding methacrylates.

The fluid dye composition may contain a free radical initiator, which is preferably a free radical initiator when the fluid dye composition is a vinyl monomer. The free radical initiator is preferably heat- and/or UV-activated. Suitable free radical initiators include, for example, 1) acyl peroxides, such as acetyl or benzoyl peroxide, 2) alkyl peroxides, such as cumyl, dicumyl, lauryl, or tertiary butyl peroxide, 3) hydroperoxides, such as tertiary butyl or cumyl hydroperoxide, 4) peresters, such as tertiary butyl perbenzoate, 5) other organic peroxides, including acyl alkyl sulfonyl peroxides, dialkyl peroxydicarbonates, esters, diperoxyketal, ketone peroxide, or 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane; 6) azo compounds such as 2,2'-azobisisobutyronitrile (AIBN) or 2,2'-azobis(2,4-dimethylvaleronitrile), 4,4'-azobis(4-cyanovaleric acid), or 1,1'-azobis(cyclohexanecarbonitrile); 7) various tetrakis(aluminum); and 8) various persulfate compounds such as potassium persulfate. Preferred free radical initiators are solid at 22°C, such as those with a half-life of 10 hours at 60°C or higher. Those with a half-life of 1 minute at a temperature of at least 100°C are particularly preferred. In some embodiments, the free radical initiator may also have a half-life of at least one minute at 100° C. or a half-life of at least 6 minutes at 100° C. A useful amount of the free radical initiator is 0.1% to 5% by weight of the total weight of the fluid dye composition.

In alternative embodiments, the carrier phase is free of ethylenically unsaturated free radical polymerizable monomers, or, if such monomers are present, they constitute less than 2.5% by weight of the dye composition. In such embodiments, the fluid dye composition preferably contains no more than 0.1% by weight of a free radical initiator and may be free of a free radical initiator.

In some embodiments, the carrier phase includes one or more aliphatic polyols having a formula weight (in the case of pure compounds) or a weight-average molecular weight (in the case of polymers) of up to 1500, up to 1200, up to 1000, up to 600, up to 500, and/or up to 250 g/mol. For the purposes of the present invention, a polyol is a compound having at least two hydroxyl groups. The polyol may have up to 8, up to 6, up to 4, or up to 3 hydroxyl groups. The polyol is preferably liquid at 23°C. Examples of such polyols include glycerol, ethylene glycol and oligomers and polymers thereof (e.g., diethylene glycol, triethylene glycol, and higher polyethylene glycols having a weight average molecular weight of 150 to 1500, especially 150 to 1000, 150 to 600, or 150 to 250 g/mol), propylene glycol and oligomers and polymers thereof (e.g., dipropylene glycol, tripropylene glycol, and higher polypropylene glycols having a weight average molecular weight of 200 to 1500, especially 200 to 1200, 200 to 600, or 200 to 350 g/mol), 1,4-butanediol, trihydroxymethylethane, trihydroxymethylpropane, etc. Polyethylene, polyethylene oligomers, and especially poly(ethylene glycol) having the above-mentioned molecular weights are preferred aliphatic polyols, as are mixtures thereof with propylene glycol and/or propylene glycol oligomers or polymers (having the above-mentioned molecular weights).

When present, the one or more aliphatic polyols may, for example, constitute at least 10%, at least 20%, or at least 30%, and up to 95%, up to 60%, or up to 50% of the total weight of the fluid dye composition.

In some embodiments, the carrier phase comprises a carboxylic acid ester having a molecular weight of up to 1000 and a flash point of at least 120°C as determined by the ASTM D92 open cup method. The carboxylic acid ester can be, for example, i) a _C1-4 alkyl ester of a _C12-24 linear or branched alkyl, alkenyl, or polyalkenyl mono- or polycarboxylic acid, ii) a fatty acid mono-, di-, or triglyceride, or a mixture of i) and ii). For example, the carboxylic acid ester i) can be a methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tertiary butyl ester of a saturated fatty acid (such as lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, or sebacic acid). In some embodiments, the carboxylic acid portion of the ester is linear and can be both linear and saturated. The carboxylic acid ester i) can be a methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tertiary butyl ester of myristic acid, palmitic acid, sapienic acid, oleic acid, isoleic acid, linoleic acid, trans-linoleic acid, α-linolenic acid, arachidonic acid, eicosapentaenoic acid, erucic acid, or docosahexaenoic acid. Isopropyl myristate is a particularly useful carboxylic acid i).

Carboxylic acid esters (ii) include mono-, di- or tri-glycerides of fatty acids having 8 to 24, in particular 8 to 18, carbon atoms, including glycerides of lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, myristoleic acid, palmitic acid, cis-6-hexadecenoic acid, oleic acid, isoleic acid, linoleic acid, trans-linoleic acid, α-linolenic acid, arachidonic acid, eicosapentaenoic acid, erucic acid or docosahexaenoic acid. Among the carboxylic acid esters (ii) are vegetable and animal oils, such as castor oil, canola oil, olive oil, linseed oil, corn oil, cottonseed oil, palm oil, peanut oil, safflower oil, sesame oil, soybean oil, sunflower oil, almond oil, beech nut oil, brazil nut oil, hazelnut oil, macadamia oil, pecan oil, pine nut oil, pistachio oil, walnut oil, pumpkin seed oil, grapefruit seed oil, lemon oil, avocado oil, cocoa butter, and orange oil.

The carboxylic acid ester can be a liquid or solid at room temperature (25°C); if solid, the carrier phase includes additional materials such that the mixture of materials forming the carrier phase is a fluid having the properties described herein, including restrictions on water and VOC content.

If present, the carboxylate may constitute at least 5%, at least 10% or at least 15% by weight of the fluid dye composition, and may constitute up to 80%, up to 70%, up to 60% or up to 50% by weight thereof.

In some embodiments, the carrier phase comprises an organic thickening agent. Such thickening agent should be miscible with other components of the carrier phase. The example of useful thickening agent comprises polyacrylate polymer, guar gum, cellulose gum, xanthan gum, cellulose ether, cellulose ester, polyvinyl alcohol, styrene-butadiene polymer and polyurethane oligomer. When there is, the amount of such thickening agent is to make the fluid dye composition have viscosity as described herein. When there is, the amount of thickening agent can be for example at least 1% of the fluid dye composition weight, at least 5% or at least 10% and can be for example up to 30%, up to 25% or up to 20% of its weight.

Another useful component of the carrier phase is a surfactant, which can be anionic or nonionic. Examples of non-ethoxylated surfactants include soy lecithin and sodium stearyl lactylate, as well as carboxylates such as sodium lauryl sulfate. Surfactants can be ethoxylated. Ethoxylated surfactants are characterized by having one or more poly(ethylene oxide) chains. Examples of such ethoxylated surfactants include ethylene oxide/propylene oxide block copolymers; ethylene oxide/butylene oxide block copolymers; polyoxyethylene (10-100) sorbitan monocarboxylate, in which the carboxylate group is a linear or branched, saturated or unsaturated fatty acid residue having 8 to 24 carbon atoms; and the like. If present, such surfactants may constitute up to 10% by weight of the total fluid dye composition. When present, preferred amounts are from 0.1% to 10% or from 0.1% to 8% on the same basis.

In some embodiments, the carrier phase comprises at least one aliphatic polyol as described above, at least one crosslinking monomer as described above, and at least one free radical initiator. In such embodiments, the aliphatic polyol is preferably ethylene glycol or an oligomer or polymer thereof, particularly poly(ethylene glycol) having the molecular weights described above, or a mixture thereof with at least one of propylene glycol or an oligomer or polymer of propylene glycol (again having the molecular weights described above). A specific aliphatic polyol is a mixture of poly(ethylene glycol) and propylene glycol. The crosslinking monomer preferably comprises a polyacrylate monomer. Cross-linking monomer can constitute for example at least 15% or at least 20% of the total weight of the fluid dye composition, and it is up to 60% or up to 50%; Cross-linking monomer can constitute for example at least 15% or at least 20% of the fluid dye composition weight, and can constitute it for example up to 60%, up to 50%, up to 40% or up to 30%.The amount of free radical initiator is as shown above.In such embodiment, dimethicone also can for example exist with 0% to 30%, 5% to 20% or 7% to 20% amount of the weight of the fluid dye composition.If exist, optionally surfactant can constitute 0.1 to 8 % by weight of such fluid dye composition weight.

In another specific embodiment, the fluid dye composition contains (based on total weight) 15 to 50% by weight of poly(ethylene glycol) having a molecular weight as described above and 0 to 50% of mono-, di-, or tri-propylene glycol (wherein the poly(ethylene glycol) and mono-, di-, or tri-propylene glycol together comprise 30% to 65% of the total weight of the fluid dye composition), and 20% to 60% of one or more crosslinked acrylate monomers (e.g., 1,6-hexyl diacrylate). Such a specific embodiment may contain, for example, 0 to 30%, 5 to 20%, or 7 to 20% by weight of polydimethylsiloxane. It may optionally contain, for example, 0.1 to 8% by weight of a surfactant. The amount of dye present in such a specific embodiment is as indicated above.

In alternative embodiments, the carrier phase comprises both dimethicone and a carboxylate. In such embodiments, the dimethicone may comprise, for example, 15% to 90%, 30% to 90%, or 50% to 90% by weight of the fluid dye composition, and the carboxylate may comprise 2.5% to 75%, 2.5% to 45%, or 2.5% to 35% by weight thereof.

In a particular embodiment, the carrier phase comprises polydimethylsiloxane, a carboxylic acid ester having a molecular weight of up to 1000 and a flash point of at least 120°C as determined by the ASTM D92 open cup method, and a thickener. In a particular embodiment, the polydimethylsiloxane may comprise, for example, at least 50% by weight of the fluid dye composition; the thickener may comprise 5% to 25% by weight of the fluid dye composition, and the carboxylic acid ester may comprise 1 to 25% by weight of the fluid dye composition.

Based on the gross weight of dye composition, the fluid dye composition contains no more than 5% water.On identical basis, preferred amount is no more than 1%, no more than 0.5% or no more than 0.25%, and the fluid dye composition can be water-free.

The fluid dye composition contains no more than 5 weight percent of volatile organic compounds (VOCs). "VOC" means any carbon-containing compound having a boiling temperature of 120°C or less at 1 atmosphere (101.3 kPa) and participating in atmospheric photochemical reactions, but does not mean any such compound exempted under 40 CFR §51.100 (s) (1) as of the date of this filing. The fluid dye composition preferably contains no more than 2 weight percent and more preferably no more than 1 weight percent of such compounds, and may be free of such compounds. "VOC" also does not apply to polymerizable monomers that are converted to polymers by a free radical polymerization process in this example.

The fluid dye composition preferably contains no more than 2.5% by weight of a wax (such as polyethylene wax, beeswax, lanolin, carnauba wax, candelabra wax, cocoa wax, sugarcane wax, jojoba wax, cuticle wax, coconut wax, petroleum wax, stone wax, etc.) having a melting temperature greater than 22° C., based on the weight of the fluid dye composition. On the same basis, it may contain no more than 1% by weight, or no more than 0.5% by weight, or 0.25% by weight thereof.

The fluid dye composition may include other ingredients not mentioned above, such as one or more organic compounds having a boiling temperature greater than 120°C at atmospheric pressure that are not included in any of the aforementioned categories of carrier phase ingredients; and/or one or more organic compounds that are liquid at 25°C, have a boiling temperature between 30°C and 120°C at atmospheric pressure, and are exempt as of the date of this filing under 40 CFR §51.100 (s) (1). Examples of such optional ingredients include acetone, methylene chloride, methyl formate, 2-amino-2-methyl-1-propanol; tertiary butyl acetate; propylene carbonate, dimethyl carbonate, methyl acetate. Such other ingredients may constitute, for example, up to 35%, up to 25%, up to 15%, up to 10%, up to 5%, up to 2.5% or up to 1% of the total weight of the fluid dye composition, again provided that the dye composition has the properties described herein.

The fluid dye composition has a kinematic viscosity of 10 to 5000 centistokes at 25°C. A preferred viscosity is at least 50 centistokes or at least 100 centistokes. Viscosity is conveniently measured by dynamic rotational rheology using a TA Instruments AR series rheometer or equivalent. Density is conveniently measured using a Chatelier-type pycnometer.

The fluid dye compositions of the present invention preferably have a flash point of at least 220°C as measured by the ASTM D92 open cup method.

The fabric is preferably a fibrous textile. "Fibrous" means that the surface of the textile is composed of or includes at least one type of filament or fiber. The filaments can have a denier of, for example, 0.25 to 1000, preferably 0.5 to 600 or 0.75 to 300. The filaments can be formed into yarns. The filaments or yarns of the porous substrate can be, for example, woven, knitted, entangled, knotted, felted, glued, or otherwise formed into a fabric, nonwoven, or textile having sufficient mechanical integrity to be conveyed through the method of the present invention. Such fabrics include fibers that may be, for example, natural fibers such as cotton, hemp, wool, linen, silk, Tencel, rayon, leather, bamboo, cellulose, or synthetic fibers such as nylon, para- or meta-aromatic polyamide, polypropylene, polyester (including PET), polyacetate, polyacrylic acid, polylactic acid, cellulose ester, or other fibers and blends of any two or more thereof. It may be a smooth or fleecy fabric and may contain a small amount (up to 50% by weight, preferably up to 20% by weight or up to 3% by weight) of stretchable fibers such as elastane, Lycra, or polyether-polyurea polymers such as spandex.

The present invention is particularly suitable for dyeing synthetic fabrics such as, for example, polyester fabrics, polyester blends (such as nylon/polyether-polyurea copolymer blends), polyamide (including nylon) fabrics, polyamide blends (such as nylon/polyether-polyurea copolymer blends), cotton/polyamide blends (such as cotton-nylon blends), cotton/polyamide/polyether-polyurea blends, cotton/polyester blends, and cotton/polyester/polyether-polyurea blends.

Prior to dyeing according to the present invention, the fabric may have an air permeability of at least 0.2 cubic feet per minute per square foot (0.001016 m/s) (as measured according to ASTM D737 using an SDL Atlas M021A or equivalent instrument and a 38 ^cm2 test area). More preferably, the fabric has an air permeability of at least 10 (0.0508), at least 50 (0.204), at least 75 (0.3060), or at least 130 (0.6604) feet per minute per square foot (m/s). The air permeability of porous fabrics can be any higher value, such as up to 200 cubic feet per minute per square foot (1.016 m/s).

The present invention is particularly suitable for processing textile coils.When textile is in the form of sheet or coil, it should have a thickness no more than about 12 mm and preferably have a thickness no more than 4 mm or no more than 2 mm.Textile can have any less thickness, as long as it has enough mechanical integrity implemented by the method.In some embodiments, the fluid dye composition is applied to the textile roll article, and these articles can have 100 mm or larger, as 1600 mm to 7 meters or larger width.

The method is not limited to roll fabrics. Folded or unfolded textile sheets can be used as substrates, as can finished products having textile components. The invention is useful for applying coatings to articles of clothing such as shirts, pants, sweaters, coats, jerseys, gloves, hats, scarves, leg and arm warmers and socks, as well as shoes and other footwear, curtains, bedding, and other items of textile material.

Fabrics dyed according to the present invention exhibit rich, vibrant colors and are easily color-uniform.

Dyed fabrics exhibit excellent color fastness, typically achieving a color fastness of at least 3.5, at least 4.0, or at least 4.5 on a dry rub scale (AATCC Method 8) and a wet rub scale (AATCC Method 8) of at least 3.0 and typically at least 4.0 or at least 4.5.

When tested according to ISO 105-E01, dyed fabrics normally exhibit a colorfastness (change of color) grade to water of at least 4.0 and usually at least 4.5. In the same test, dyed fabrics normally exhibit a dyefastness grade of at least 3.5, at least 4.0, or at least 4.5 relative to acetate, cotton, nylon, polyester, acrylic, and wool multifiber fabrics.

Dyed fabrics typically exhibit a colorfastness (color change) rating to washing (AATCC 61-2A) of at least 4.0 and usually at least 4.5. In the same test, dyed fabrics typically exhibit a dye rating of at least 3.5, at least 4.0, or at least 4.5 relative to acetate, cotton, nylon, polyester, acrylic, and wool multifiber fabrics.

Dyed fabrics typically exhibit a colorfastness (color change) rating to perspiration of at least 4.0 and usually at least 4.5 (ISO 105-E04 acid test). In the same test, dyed fabrics typically exhibit a dye rating of at least 3.5, at least 4.0, or at least 4.5 relative to acetate, cotton, nylon, polyester, acrylic, and wool multifiber fabrics.

Dyed fabrics typically exhibit a colorfastness (color change) rating to perspiration of at least 4.0 and usually at least 4.5 (ISO 105-E04 alkaline test). In the same test, dyed fabrics typically exhibit a dye rating of at least 3.5, at least 4.0, or at least 4.5 relative to acetate, cotton, nylon, polyester, acrylic, and wool multifiber fabrics.

The dyed fabrics typically exhibit an appearance grade (LTD-37 test) of at least 4.0 and often at least 4.0 or at least 4.5 after 10 washes, after 15 washes, after 20 washes and even after 25 washes.

The dyed fabric may then be treated with various treatments as may be desired or necessary for its intended end use. Examples of such treatments include hydrophobic treatments to impart water repellency and/or hydrophobic properties; oleophobic treatments to reduce oil absorption or staining and/or impart oil repellency; superhydrophobic treatments, which impart a very high (>130°) contact angle between a water droplet and the surface of the treated substrate; hydrophilic treatments to increase water absorption or wettability; various rubbers; flame retardant treatments; antimicrobial treatments; UV absorber and/or UV reflector treatments; anti-wrinkle agents; fabric softeners and/or anti-mar treatments; softening treatments; insecticide and/or repellent treatments; and forensic chemical marker treatments.

In particular, it has been found that fabrics dyed according to the present invention can be easily and effectively treated with a hydrophobic treatment agent. According to the method of the present invention, after the fabric has been dyed and the dye has been cured, if necessary, such a hydrophobic treatment agent is appropriately applied and cured. Particularly useful hydrophobic treating agents include those described in WO 2015/127479 and WO 2007/020018, especially hydrophobic treating agents comprising: i) a silicone oil, ii) at least one free radical curable monomer having only one polymerizable group per molecule, the free radical curable monomer having at least one alkyl group having at least eight carbon atoms directly or indirectly bonded to the polymerizable group, wherein the alkyl group may be non-fluorinated, partially fluorinated, or perfluorinated, the free radical curable monomer having a boiling temperature equal to or greater than 100°C, iii) at least one crosslinking monomer having at least two free radical curable polymerizable groups and a boiling temperature equal to or greater than 100°C, and optionally iv) at least one wax. A very significant advantage of the present invention is that a subsequent hydrophobic treatment can be applied to the dyed and cured fabric without any intermediate washing of the fabric and without the adverse effects of conventionally accomplished water-based dyeing.

The following examples are intended to illustrate the present invention without limiting its scope. Unless otherwise indicated, all parts and percentages are by weight. Example 1

A fluid dye composition was prepared by mixing 2 parts of anthraquinone dye (Red 70027 from Continental Red), 30 parts of 1000 cst polydimethylsiloxane (PDMS), 8 parts of guar gum, and 1.5 parts of isopropyl myristate in a laboratory mixer. The fluid dye composition contained approximately 5 g of dye per liter. The viscosity of the fluid dye composition ranged from 1000 to 5000 centistokes at 25°C. This fluid dye composition was then used to dye high toughness (HT) woven polyester fabric. HT fabrics are among the most difficult fabrics to dye using conventional water-based dyeing. Furthermore, it is well known in the art that red dyes tend to be the most difficult dyes to work with due to increased friction and colorfastness issues.

A polyester fabric is mounted on a tenter frame and secured on each side by pins on the tenter frame. The fabric is then drawn through a dye application station, where a fluid dye composition is poured onto the fabric just upstream of a knife-roll-type blade mechanism. The blade mechanism is adjusted to achieve a coating weight of 30 to 60 grams per square meter. Application is carried out at 25 to 3°C. An even layer of the fluid dye composition is applied across the entire width of the fabric. It is important that the fluid dye composition does not pass through the fabric and come into contact with the underlying rollers during application.

The tenter frame then transported the fabric, with the applied fluid dye composition, continuously through air into a multi-zone atmospheric drying oven without any intermediate processing steps (such as dipping, drying, washing, etc.). The zone temperature was set at 195°C, with the final zone set at 210°C. The line speed was selected so that the residence time in the 195°C zone was 4 minutes, and the residence time in the 210°C zone was 1 minute.

The fluid dye composition cures in the 195°C zone of the oven. Any residual dye remaining on the fabric surface is thermally removed in the 210°C zone. This eliminates any dry-erase issues and also eliminates the need for rinsing before applying a subsequent hydrophobic treatment. The fabric is then cooled and rolled up without further treatment (specifically, without rinsing or washing) before applying the hydrophobic treatment.

Even if the fluid dye composition does not penetrate through the fabric during the initial application step, the cured fabric is dyed on both sides with no perceptible difference in color between the front and back sides.

A hydrophobic treatment was applied to the dyed fabric. The treatment consisted of a mixture of octadecyl acrylate, 1,6-hexanediol diacrylate, dipentaerythritol penta/hexaacrylate, lauryl acrylate, and polydimethylsiloxane. The treatment was applied to each side of the fabric using a gravure roll at a coat weight of 15 grams per square meter. Following the procedure outlined in U.S. Patent 9,902,874, the coated fabric was rolled onto a beam and then cured at 100°C under 500 psi (3.447 MPa) of nitrogen pressure for 30 minutes.

The dyed fabrics were evaluated for colorfastness to rubbing (wet and dry) according to AATCC 8, colorfastness to water according to ISO 105-E01, colorfastness to washing according to AATCC 6121, colorfastness to perspiration (acid and alkali) according to ISO 105-E04, and appearance after 25 washes according to LTD-37. The results are shown in Table 1. Industry standards are listed in the "Requirements" column for reference.

The water repellency and laundering resistance of the hydrophobic treatments applied after the waterless dyeing process were also tested using the AATCC 22 spray test (scales 0 to 100) and the Bundesmann ISO 9865 water repellency test (scales 1-5). Industry "best practice" requires an ISO 9865 rating of 2.5 after three washes. There is no standard for exceeding three washes because the previous hydrophobic treatment cannot provide an ISO 9865 rating of more than 1 after three washes. The results show high performance (at least a rating of 2.5) after 10 washes and even more. All conventionally dyed fabrics with subsequent hydrophobic treatments failed the ISO 9865 test after five or more washes. [ Table 1 ] Test Standards Require Test results CF for friction (AATCC 8) Qian 4.0 4.5 wet 3.0 4.5 CF for water (ISO 105-E01) Color change 4.0 4.5 dyeing Fiber acetate 3.5 4.5 cotton 4.5 Nylon 4.5 Polyester 4.5 Acrylics 4.5 wool 4.5 CF for washing (AATCC 61-2A) Color change 4.0 4.5 dyeing Fiber acetate 3.5 4.5 cotton 4.5 Nylon 4.5 Polyester 4.5 Acrylics 4.5 wool 4.5 CF for sweat, (ISO 105-E04) acid Color change 4.0 4.5 dyeing Fiber acetate 3.5 4.5 cotton 4.5 Nylon 4.5 Polyester 4.5 Acrylics 4.5 wool 4.5 CF for sweat, (ISO 105-E04) alkaline Color change 4.0 4.5 dyeing Fiber acetate 3.5 4.5 cotton 4.5 Nylon 4.5 Polyester 4.5 Acrylics 4.5 wool 4.5 Appearance after repeated home washing and ironing (LTD-37) 5 washes 4.0 4.5 10 washes 4.0 4.0 15 washes 4.0 4.0 20 washes 4.0 4.0 25 washes 4.0 4.0

The water repellency and laundry durability of the hydrophobic treatment applied after the waterless dyeing process were also tested using the AATCC 22 Spray Test (scales 0 to 100) and the Bundesmann ISO 9865 Water Repellency Test (scales 1-5). Industry "best practice" requires an ISO 9865 rating of 2.5 after 3 washes. The results showed high performance (at least a 4.2 rating) after 10 washes based on the AATCC 22 Spray Test with a spray rating of 100, in which 12-13 mL of water was passed through the fabric. Conventionally dyed fabrics with a subsequent hydrophobic treatment did not pass the ISO 9865 test after 5 or more washes. Examples 2-17

The carrier phase of the fluid dye composition was prepared by mixing the ingredients indicated in Table 2. In each case, the dye was Red 70027 from Continental Red, described in the previous example, added to the carrier phase at a level of 30-60 grams per liter of fluid dye composition. In all cases, the viscosity ranged from 50 to 5000 centistokes at 25°C. The fluid dye composition was applied to the fabric samples and cured in the general manner described in the previous example. No hydrophobic treatment was applied.

In Table 2: PEG 200 is poly(ethylene glycol) of 200 weight average molecular weight (by GPC); HDA is a mixture of 95 parts 1,6-hexane diacrylate and 5 parts free radical initiator; LA is a mixture of 95 parts lauryl acrylate and 5 parts free radical initiator; DS is dioctyl sebacate; PG is monopropylene glycol; and PDMS is polydimethylsiloxane as described, having a viscosity of 10 centistokes at 25°C. In the following examples, when PDMS is present, an emulsifier such as sodium stearyl lactylate is also present at 10% by weight of the PDMS. [ Table 2 ] Instance Number Ingredients (parts by weight) PEG 200 HDA LA DS PG PDMS 2 0 94.3 0 0 0 0 3 94 0 0 0 0 0 4 63 31 0 0 0 0 5 47 47 0 0 0 0 6 31 63 0 0 0 0 7 28 38 0 28 0 0 8 38 19 0 0 0 38 9 28.3 47.2 0 0 18.9 0 10 28.3 28.3 28.3 0 9.4 0 11 0 47.2 0 0 47.2 0 12 37.7 28.3 0 0 28.3 0 13 28.3 28.3 0 0 37.7 0 14 18.9 37.7 0 0 37.7 0 15 23.8 23.8 0 0 31.7 7.9 16 35.1 35.1 0 0 0 17.5 17 35.4 44.2 0 0 0 8.8

The dyed fabrics were evaluated for color, dry rubbing (AATCC Method 8), wet rubbing (AATCC Method 8), and hand feel, and the color fastness according to ISO 105-E01 was also indicated. In each case, the rating was based on a scale of 1-5, with 5 being the best. The results are shown in Table 3. [ Table 3 ] Instance Number color Dry friction Wet friction feel Color fastness 2 3 4 5 4 ND ¹ 3 2 5 5 4 ND 4 4 5 5 4 ND 5 4 4.5 5 4 ND 6 5 5 5 3 ND 7 5 3.5 5 2 ND 8 5 4.5 5 3 ND 9 4 5 5 4 ND 10 4 4.5 5 3 ND 11 3 5 5 2 ND 12 4 5 5 5 5 13 5 5 5 5 5 14 4 5 5 5 5 15 5 4.5 5 4 ND 16 5 4.5 5 4 ND 17 5 5 5 5 ND ¹ ND series has not been determined.

Example 2 demonstrates the effects of using only a crosslinking monomer as the carrier phase. Dyeing was successful. Friction and feel were good to excellent, but color development was not as good as in the other examples.

Example 3 shows the effect of using only poly(ethylene glycol) as the carrier phase. Again, good friction and feel were obtained, but the color development was not very good.

Examples 4 to 17 all contain mixtures of aliphatic polyols (PEG 200 and/or monopropylene glycol) and crosslinking monomers. Dry rub performance was excellent in all but Example 7. In these formulations, the presence of dioctyl sebacate or lauryl acrylate was found to negatively impact hand feel. Similarly, when monopropylene glycol was the sole aliphatic alcohol, hand feel and color were also less favorable (Example 11).

Examples 12-17 performed best, with ratings of very good to excellent for all evaluated attributes. All of them contained PEG 200, a crosslinking monomer, and at least one of monopropylene glycol and dimethicone.

Examples 2 and 3 were repeated, this time by winding the dyed fabric onto a spinning hammer and performing the curing step at 195°C in a closed autoclave under a nitrogen pressure above atmospheric pressure. In both cases, color development and dry friction were found to be inferior to the samples cured in the oven. However, when the samples were then further heated in the oven at 210°C for an additional minute, color development and dry friction were the same as those seen in Examples 2 and 3.

Examples 12 and 13 were then further coated with a hydrophobic coating in the manner generally described in Example 1. The samples were then evaluated for water repellency according to the AATCC 22 spray test for 30 seconds and for 10 minutes in a Bundesmann water repellency tester according to ISO 9865. Duplicate samples were subjected to 10 cold water wash/machine dry cycles and then tested similarly. The results are shown in Table 4. [ Table 4 ] Instance Number AATCC 22 spray test level (30 seconds) ISO9865 level (10 minutes) ISO9865, water absorption % 12 (unwashed) 100 4.7 4.09 12 (after 10 wash/dry cycles) 100 4.3 4.15 12 (unwashed) 100 4.8 0.55 12 (after 10 wash/dry cycles) 100 4.5 6.78

As shown in the results in Table 4, a laundry-resistant hydrophobic coating was applied to the fabric dyed according to the present invention.

In a specific embodiment, the present invention is:

1. A method for dyeing a textile, comprising the following steps: A. applying a fluid dye composition to at least one surface of a textile at a temperature of 10°C to 100°C using a non-immersion method at an application weight of 2.5 to 250 grams per square meter of textile, wherein the dye composition comprises a) a carrier phase that is liquid in the temperature range of 20°C to 220°C; the carrier phase having dissolved or suspended therein b) 2.5 to 300 grams per liter of the dye composition of at least one organic dye that is solid at a temperature below 130°C and has a sublimation or boiling temperature of 130°C to 220°C; and B. Curing the dye composition by heating the fabric having the applied dye composition to a temperature at least equal to the boiling or sublimation temperature of the at least one organic dye for a period of at least 30 seconds, such that the dye boils or sublimates and at least a portion thereof penetrates the fabric, wherein the dye composition contains no more than 5% by weight of water and no more than 5% by weight of volatile organic compounds, and the dye composition has a viscosity of at least 10 centistokes and at most 5,000 centistokes at 25°C.

2. A textile dyeing method as described in embodiment 1, wherein the dye composition contains not more than 10% of a water-miscible chemical.

3. The fabric dyeing method of embodiment 1 or 2, wherein in step A, the fabric is continuously moved through a dye application station where the dye composition is applied to the fabric.

4. The textile dyeing method according to any one of embodiments 1 to 3, wherein the temperature in step B is 140°C to 220°C.

5. The textile dyeing method according to any one of embodiments 1 to 3, wherein in step B, the dye composition is first cured by heating the fabric with the applied dye composition to a temperature of 140°C to 200°C and then further heating to a temperature of 210°C to 220°C.

6. The fabric dyeing method of any one of embodiments 1 to 3, wherein in step B, the fabric is continuously moved through a heating station, in which the fabric with the applied dye composition is heated to a temperature of 140°C to 220°C for a period of at least 30 seconds.

7. The fabric dyeing method of embodiment 6, wherein in step B, the fabric is secured at opposite edges to a tenter frame that continuously moves the fabric through the heating station.

8. A method for dyeing a fabric as described in any preceding embodiment, wherein, in step B, the fabric is not supported from below and no mechanical pressure is applied to the top surface of the fabric.

9. A method for dyeing a fabric as described in any preceding embodiment, wherein in step A, the dye is applied using a gravure coater.

10. A method for dyeing a fabric as described in any one of embodiments 1 to 5, wherein the fabric with the applied dye composition is formed into a roll and step B is performed on the roll in a sealed container.

11. The textile dyeing method of embodiment 10, wherein, during at least a portion of step B, the sealed container is pressurized with a non-liquefied gas to a gauge pressure of 350 to 7,000 kPa.

12. A method for dyeing a textile as described in any preceding embodiment, wherein in step A, the dye composition is applied with a coating weight of 5 to 50 g/m2.

13. A method for dyeing a fabric as described in any of the preceding embodiments, wherein the fabric has an area weight of 50 to 250 grams per square meter before dyeing.

14. The method of any preceding embodiment, wherein the fabric has an air permeability of 0.472 to 23.6 L/s before dyeing, as measured according to ASTM D737 using an SDL Atlas M021A or equivalent instrument and a 38 ^cm2 test area.

15. A method for dyeing a fabric as described in any preceding embodiment, wherein, in step A, the dye composition is applied to only one surface of the fabric.

16. A method for dyeing a fabric as described in any preceding embodiment, wherein, in step A, a first dye composition is applied to a portion of the fabric surface and a second dye composition is applied to a different portion of the same surface of the fabric, and in step B, the first and second dye compositions are cured simultaneously.

17. A method for dyeing a fabric as described in embodiment 16, wherein, after curing, the first and second dye compositions have different colors.

18. A method for dyeing a fabric as described in any one of embodiments 1 to 14, wherein in step A, a first dye composition is applied to one surface of the fabric, a second dye composition is applied to the opposite surface of the fabric, and in step B, the first and second dye compositions are cured simultaneously.

19. A textile dyeing method as described in embodiment 18, wherein, after curing, the first and second dye compositions have different colors.

20. A method for dyeing a fabric as described in any of the preceding embodiments, wherein the fabric is a woven or knitted fabric.

21. A method for dyeing a fabric as described in any of the preceding embodiments, wherein the fabric is a polyester or polyamide fabric, or a blend of polyester or polyamide and at least one other fiber.

22. A method for dyeing a fabric as described in any of the preceding embodiments, further comprising applying a hydrophobic fabric treatment to the fabric after step B.

23. A textile dyeing method as described in any of the aforementioned embodiments, wherein the organic dye is an anthraquinone or azo dye.

24. A method for dyeing a textile as described in any of the preceding embodiments, wherein the dye composition contains 20 to 150 grams of the at least one organic dye per liter of the dye composition.

23. A method for dyeing a fabric as described in any preceding embodiment, wherein no step of washing, removing excess fluid or drying the fabric is performed between steps A and B.

24. In the fabric dyeing method as described in embodiment 23, the dye composition is a dye composition of any of the following embodiments.

25. A fluid dye composition comprising: a) a carrier phase that is liquid within a temperature range of 20°C to 220°C; the carrier phase having dissolved or suspended therein b) 2.5 to 300 grams per liter of the dye composition of at least one organic dye that is solid at temperatures below 130°C and sublimes and/or boils at temperatures between 130°C and 210°C; wherein the dye composition contains no more than 5% by weight of water and no more than 5% by weight of volatile organic compounds, and the dye composition has a viscosity at 25°C of at least 10 centistokes and no more than 5,000 centistokes.

26. The fluid dye composition as described in embodiment 25, wherein the organic dye is an anthraquinone or azo dye.

27. The fluid dye composition of embodiment 25 or 26, wherein water constitutes no more than 1% by volume of the dye composition.

28. A fluid dye composition as described in any one of embodiments 25-27, which contains 20 to 150 grams of the at least one organic dye per liter of the dye composition.

29. A fluid dye composition as described in any of embodiments 25-28, comprising at least one polydimethylsiloxane, which is a liquid having a viscosity of at least 10 centistokes at 25°C.

30. The fluid dye composition of any one of embodiments 25-29, wherein the polydimethylsiloxane has a viscosity of at least 100 cst at 25°C.

31. A fluid dye composition as described in any of embodiments 25-30, comprising at least one aliphatic polyol having a molecular weight of up to 1000 g/mol.

32. The fluid dye composition as described in embodiment 31, wherein the aliphatic polyol is one or more of glycerol, ethylene glycol, oligomers or polymers of ethylene glycol, propylene glycol, oligomers or polymers of propylene glycol, 1,4-butanediol, trihydroxymethylethane and trihydroxymethylpropane.

33. The fluid dye composition of embodiment 32, wherein the aliphatic polyol comprises poly(ethylene glycol) having a weight average molecular weight of 150 to 600.

34. The fluid dye composition of embodiment 32 or 33, wherein the aliphatic polyol comprises one or more oligomers or polymers of propylene glycol or propylene glycol having a weight average molecular weight of 200 to 600.

35. The fluid dye composition of embodiment 32, wherein the aliphatic polyol comprises polyethylene glycol and propylene glycol having a weight average molecular weight of 150 to 600.

36. A fluid dye composition as described in any of embodiments 25-35, wherein the carrier phase includes at least one cross-linking monomer.

37. The fluid dye composition as described in embodiment 36, wherein the crosslinking monomer is one or more of 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,8-octanediol diacrylate, cyclohexanedimethanol diacrylate, trihydroxymethylpropane triacrylate, glycerol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate and any corresponding methacrylate.

38. The fluid dye composition as described in embodiment 36 or 37 further comprises a heat-activatable or UV-activatable free radical initiator.

39. The fluid dye composition as described in any one of embodiments 25-38, further comprising a surfactant.

40. The fluid dye composition as described in embodiment 39, wherein the surfactant is one or more of an ethoxylated non-ionic surfactant, sodium stearyl lactylate, or soy lecithin.

41. The fluid dye composition as described in any one of embodiments 25-40, further comprising an organic thickener.

42. The fluid dye composition as described in embodiment 41, wherein the thickener is selected from the group consisting of: polyacrylate polymer, guar gum, cellulose gum, xanthan gum, cellulose ether, cellulose ester, polyvinyl alcohol, styrene-butadiene polymer and polyurethane oligomer.

43. The fluid dye composition of any of embodiments 25-42, further comprising a carboxylic acid ester having a molecular weight of up to 1000 and a flash point of at least 120°C as determined by the ASTM D92 open cup method.

44. The fluid dye composition according to embodiment 43, wherein the carboxylic acid ester is i) a C _1-4 alkyl ester of a C _12-24 linear or branched alkyl, alkenyl or polyalkenyl carboxylic acid, ii) a fatty acid mono-, di- or tri-glyceride, or a mixture of i) and ii).

45. The fluid dye composition as described in embodiment 44, wherein the carboxylic acid ester is isopropyl myristate.

46. The fluid dye composition of embodiment 25, wherein the carrier phase comprises at least 50 wt% polydimethylsiloxane, 5 to 25 wt% thickener, and 1 to 25 wt% carboxylic acid ester having a molecular weight of up to 1000 and a flash point of at least 120°C as determined by ASTM D92 open cup method.

47. A fluid dye composition as described in embodiment 25, wherein the carrier phase comprises at least one aliphatic polyol having a molecular weight of up to 1000 g/mol, at least one crosslinking monomer and at least one thermally activatable or UV-activatable free radical initiator.

48. The fluid dye composition of embodiment 47, wherein the aliphatic polyol constitutes 30% to 75% of the total weight of the fluid dye composition and the cross-linking monomer constitutes 20% to 50% of the total weight of the fluid dye composition.

49. The fluid dye composition of embodiment 47 or 48, wherein the aliphatic polyol comprises poly(ethylene glycol) having a weight average molecular weight of 150 to 500.

50. The fluid dye composition as described in embodiment 49, wherein the aliphatic polyol further includes propylene glycol.

51. The fluid dye composition of any one of embodiments 47-50, further comprising 7% to 20% of polydimethylsiloxane, based on the weight of the fluid dye composition.

52. The fluid dye composition of any one of embodiments 25-28, comprising, based on the weight of the fluid dye composition, 15% to 50% of poly(ethylene glycol) having a weight average molecular weight of 150 to 500; 0% to 50% of propylene glycol, wherein the combined weight of the poly(ethylene glycol) and propylene glycol constitutes 30 to 65% by weight of the fluid dye composition; 20% to 60% of at least one crosslinking monomer, a heat-activatable or UV-activatable free radical initiator, and 0 to 20% by weight of polydimethylsiloxane.

53. The fluid dye composition as described in embodiment 52, wherein the fluid dye composition contains 5% to 40% propylene glycol based on the weight of the fluid dye composition.

54. The fluid dye composition of any one of embodiments 47-54, wherein the crosslinking monomer comprises 1,6-hexane diacrylate.

55. The fluid dye composition of any one of embodiments 52-54, further comprising 7% to 20% of polydimethylsiloxane, based on the weight of the fluid dye composition.

without

without

without

Claims (22)

A method for dyeing a textile comprising the following steps: A. applying a fluid dye composition to at least one surface of the textile at a temperature of 10°C to 100°C using a non-immersion method at an application weight of 2.5 to 250 grams per square meter of textile, wherein the dye composition comprises a) a carrier phase that is liquid in the temperature range of 20°C to 220°C; the carrier phase having dissolved or suspended therein b) 2.5 to 300 grams per liter of the dye composition of at least one organic dye that is solid at a temperature below 130°C and has a sublimation or boiling temperature of 130°C to 220°C, and B. Curing the dye composition by heating the fabric having the applied dye composition to a temperature at least equal to the boiling or sublimation temperature of the at least one organic dye for a period of at least 30 seconds, such that the dye boils or sublimates and at least a portion thereof penetrates into the fabric, wherein the dye composition contains no more than 5% by weight of water and no more than 5% by weight of volatile organic compounds, and the dye composition has a viscosity of at least 10 centistokes and at most 5000 centistokes at 25°C. The fabric dyeing method of claim 1, wherein in step A, the fabric is continuously moved through a dye application station where the dye composition is applied to the fabric. The method of claim 1 or 2, wherein in step A, the dye is applied using a gravure coater. A method for dyeing a fabric as claimed in claim 2, wherein in step B, the fabric is continuously moved through a heating station in which the fabric with the applied dye composition is heated to a temperature of 140°C to 220°C for a period of at least 30 seconds. The method of claim 2, wherein the fabric having the applied dye composition is formed into a roll and step B is performed on the roll in a sealed container. The method of claim 5, wherein during at least a portion of step B, the sealed container is pressurized with a non-liquefied gas to a gauge pressure of 350 to 7,000 kPa. The method of claim 2, wherein in step A, the dye composition is applied at a coating weight of 5 to 50 g/m2. The method of claim 2, wherein, in step A, a first dye composition is applied to a portion of the surface of the fabric and a second dye composition is applied to a different portion of the same surface of the fabric, and in step B, the first and second dye compositions are cured simultaneously. The method of claim 8, wherein, after curing, the first and second dye compositions have different colors. The method of claim 2, wherein in step A, a first dye composition is applied to one surface of the fabric, a second dye composition is applied to the opposite surface of the fabric, and in step B, the first and second dye compositions are cured simultaneously. The method of claim 10, wherein, after curing, the first and second dye compositions have different colors. The method of claim 2, further comprising applying a hydrophobic fabric treatment to the fabric after step B. The method of claim 2, wherein no step of washing, removing excess fluid, or drying the fabric is performed between steps A and B. The method of claim 2, wherein the carrier phase comprises polydimethylsiloxane. The method of claim 2, wherein the carrier phase comprises at least one aliphatic polyol having a molecular weight of up to 1000 g/mol. The method of claim 2, wherein the carrier phase comprises at least one crosslinking monomer and the dye composition comprises a thermally activatable or UV activatable free radical initiator. The method of claim 2, wherein the carrier phase comprises poly(ethylene glycol) having a molecular weight of 150 to 600, a crosslinking monomer, and at least one of propylene glycol and polydimethylsiloxane. A fluid dye composition comprising: a) a carrier phase that is liquid within a temperature range of 20°C to 220°C; the carrier phase having dissolved or suspended therein b) 2.5 to 300 grams per liter of the dye composition of at least one organic dye that is solid at temperatures below 130°C and sublimes and/or boils at temperatures between 130°C and 210°C; wherein the dye composition contains no more than 5% by weight of water and no more than 5% by weight of volatile organic compounds, and the dye composition has a viscosity at 25°C of at least 10 centistokes and no more than 5,000 centistokes. The dye composition of claim 18, wherein the carrier phase comprises polydimethylsiloxane. The dye composition of claim 19, wherein the carrier phase comprises at least one aliphatic polyol having a molecular weight of up to 1500 g/mol. The dye composition of claim 19, wherein the carrier phase comprises at least one crosslinking monomer and the dye composition comprises a thermally activatable or UV activatable free radical initiator. The dye composition of claim 19, wherein the carrier phase comprises poly(ethylene glycol) having a molecular weight of 150 to 600, a crosslinking monomer, and at least one of propylene glycol and polydimethylsiloxane.