HK40036613A - Improving the balance of durable press properties of cotton fabrics using non-formaldehyde technology - Google Patents

Description

Improving the balance of durable set properties of cotton fabrics using non-formaldehyde technology

Cross Reference to Related Applications

This application claims us provisional application No. 62/557,311, filed on 12.9.2017 and us application No. 62/699,920, filed on 18.7.2018, each of which is incorporated herein by reference in its entirety.

Background

Cotton fibers are often treated with a cross-linking resin (also referred to as a "reactant") to impart wrinkle resistance while being worn and after multiple washings. The crosslinking not only imparts durable smoothness and shape retention to the fibers, but also improves shrinkage control and inhibits pilling and fuzzing on the fiber surface. Other benefits of crosslinking include, but are not limited to, faster drying and easier ironing when needed.

However, the above-mentioned crosslinking process also has some disadvantages. There is a loss of abrasion resistance and strength which results in a reduced wear life. Over the years, several approaches have been developed to mitigate the impact of these degradative effects. Some of these techniques have been used, while others proposed are too expensive.

Many of the commercial reactants used to impart wrinkle resistance also have the disadvantage of releasing formaldehyde either when such reactants are mixed and applied in the textile mill or after they have been applied to the fibers. In recent years, formaldehyde has been classified as carcinogenic by the World Health Organization (WHO) (International cancer research organization (IRAC), News Res.: No. 153, 6/15/2004). Recently, the European chemical administration (ECHA) released the statement "Formaldehyde is classified as a class 1B carcinogen with > 0.1% CLP (Regulation (EC) No.1272/2008on classification, labeling and chemical stabilizers and chemistries) concentration limits 1. the Committee has suggested that Formaldehyde and some Formaldehyde releasing substances be included in the appendix 17 restriction list for the next revision of carcinogenic, germ cell mutagenic or germ toxic substances (CMRsustances) 1A and 1B in the appendix 28 to 30 restrictions. This will limit the formaldehyde in the mixture and the contained formaldehyde releasing material to be marketed for supply to the public, the respective concentration limits set by the CLP regulations being to be contained. ' Pai

This can be read here: www.echa.europa.eu/documents/10162/13641/formaldehydehyde _ review _ report _ en. pdf/551df4a2-28c4-2fa9-98ec-c8d53e2bf0 fc.

Over the years, reactants such as dimethylol dihydroxyethylene urea (DMDHEU) have been modified to reduce formaldehyde emissions, but these products are not completely formaldehyde free. Release behavior and kinetics evaluation of formaldehyde from cotton-clothing fibers surface treated with DMDHEU-based permanent shaping agents in water and simulated sweat solutions, found in b.li, y.dong, p.wang, g.cui, Textile Research Journal, Vo186 (16): 1738-1749, 2016.

Over time, several non-formaldehyde reactants have been developed and tested, but many have drawbacks in terms of yellowing, latent odor on the fibers, expense, or underperformance. More recently, reagents based on modified dimethyl urea/glyoxal (DMUG) chemistries have been developed and applied in a manner that achieves comparability to DMDHEU without the disadvantages of formaldehyde emission or yellowing and latent odor described above. However, the use of modified DMUG chemistry alone does not address the problem of abrasion resistance and strength loss associated with non-formaldehyde reactants.

Disclosure of Invention

In some aspects, the presently disclosed subject matter demonstrates that the strength and wear losses associated with the application of modified DMUG non-formaldehyde reactants can be mitigated with the addition of selected chemicals to the surface treatment bath. Among the compounds found to be useful are dicyandiamide, choline chloride, ethylene urea, propylene urea, urea and dimethyl urea. These compounds must be added in the correct concentrations in an optimized surface treatment formulation to achieve the desired effect.

According to some aspects, the presently disclosed subject matter provides a formulation for surface treating a cellulosic substrate or a mixture thereof in a surface treatment bath, the formulation comprising from about 3.0% to about 60.0% by weight of non-formaldehyde dimethyl urea/glyoxal (DMUG) or the like, and from about 0.1% to about 4.0% by weight of one or more additives selected from dicyandiamide, choline chloride, ethylene urea, propylene urea, dimethyl urea, and combinations thereof, wherein the weight percentages are given as weight percentages of the surface treatment bath, and wherein the formulation is substantially free of dimethylol dihydroxy ethylene urea (DMDHEU).

In other aspects, the presently disclosed subject matter provides a method of surface treating a durable press cellulosic substrate or a mixture thereof in a surface treatment bath, the method comprising applying a surface treatment formulation to the substrate at an elevated temperature for a period of time, the formulation comprising: from about 3.0% to about 60.0% by weight of non-formaldehyde dimethylurea/glyoxal (DMUG) or an analog thereof, and from about 0.1% to about 4.0% by weight of one or more additives selected from dicyandiamide, choline chloride, ethylene urea, propylene urea, dimethylurea and combinations thereof, wherein said weight percentages are given as weight percentages of said surface treatment bath, and wherein said formulation is substantially free of dimethylol dihydroxyethylene urea (DMDHEU).

In certain aspects, the cellulosic substrate comprises a cellulosic fiber selected from the group consisting of cotton; jute fiber; flax fibers; hemp fibers; ramie fibers; regenerated cellulose products including but not limited to rayon (rayon), lyocell and modal; and mixtures of the above. In particular aspects, the cellulosic substrate comprises cotton or a cotton blend. In other aspects, the cellulosic substrate comprises one or more fibers that are not cellulosic. In particular aspects, the non-cellulosic fiber is selected from the group consisting of a polyolefin, a polyester, nylon, vinylon, polyurethane, acetate, a mineral fiber, silk, wool, polylactic acid (PLA), polytrimethylene terephthalate (PTT), and combinations thereof.

In certain aspects, the cellulosic substrate comprises an article selected from the group consisting of a woven fabric, a knitted fabric, a non-woven fabric, a multi-layer fabric, a garment, and a yarn.

While certain aspects of the presently disclosed subject matter have been set forth above, in whole or in part, these aspects are provided by the presently disclosed subject matter, and other aspects will become apparent as the description proceeds when taken in connection with the accompanying examples as best described below.

Detailed Description

The presently disclosed subject matter may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein; rather, these embodiments are provided so that this disclosure will satisfy applicable legal requirements. Indeed, many modifications and other embodiments of the presently disclosed subject matter set forth herein will come to mind to one skilled in the art to which the presently disclosed subject matter pertains having the benefit of the teachings presented in the following descriptions and examples. Therefore, it is to be understood that the presently disclosed subject matter is not to be limited to the specific embodiments disclosed and that modifications and other embodiments are intended to be included within the scope of the appended claims.

A. Overview of Cotton-containing durable set garments

For cotton-containing durable set garments, several variables need to be taken into account in order to obtain acceptable performance properties. The structure, mechanics, chemistry, aesthetics, cost, and marketing of the product require significant considerations. In part, the presently disclosed subject matter takes into account factors important to the appearance and wear life of cotton-containing durable press garments.

Before a fiber can be considered for durable setting, it must be properly constructed to tolerate the expected loss of strength while still meeting end use requirements. The selected cotton fibers must be acceptable in terms of strength, fiber length, and the value of the microphone (a measure of the air permeability of the cotton fibers). The strength of the yarn made of the selected cotton will be influenced by the spinning method, degree and size. For the fabric itself, the strength will depend on the density and distribution of the yarns in the structure.

The auxiliaries exert a significant influence on the final properties of the cotton-containing durable-setting product. Open width processing is preferred to avoid placing permanent wrinkles in the fabric. Care must be taken in bleaching to avoid weakening by over-oxidation and pinholes due to local activation of bleaching water by iron oxide and other metal compounds. Lye treatments are often performed to obtain coverage of the green cotton during dyeing, to increase fiber strength, and to increase gloss. However, some laboratory experiments show that a very high degree of lye treatment may have a negative effect on the abrasion resistance, most likely due to the increased hardness of the fibers.

Further, in dyeing, it is important to obtain good colorant penetration. Otherwise, the decrease in wear resistance will become more pronounced. Some important considerations include dye selection and methods of dyeing. The cloth dyeing process allows better penetration than the continuous dyeing process. Bath padding is sometimes carried out to avoid ring-dyeing of the cotton.

Various pretreatments on cotton fibers prior to chemical surface treatments have been explored to improve the balance of physical properties on the final product. Some of these techniques involve the grafting of various monomers onto cotton and the wet fixing of formaldehyde-containing resins. Such methods are expensive and minimally successful. The most dramatic improvement was achieved by pretreatment with anhydrous liquid ammonia. Although expensive and requiring special equipment, the above process not only improves the abrasion resistance but also improves the aesthetic properties of the surface-treated cotton, such as hand and drape.

Mechanical methods are also effective in improving the strength retention of cotton-containing durable set products. One such process is the micro-stretching technique. In the micro-stretching technique, the fibers are stretched in the width direction and held there until crosslinking occurs. There is an increase in weft strength, but not warp strength. This increase may be due to a better arrangement of the structural elements of the weft yarns. However, the wear resistance is not improved by this process. Some disadvantages of this approach also include loss of crimp in the weft direction, reduced coverage of the fibers, and additional care in the process.

A common method of applying the durable press surface treatment to cotton fibers is pad-bake-cure, in which a soak amount of between about 60 percent to about 100 percent is obtained depending on the fiber. The curing process may be performed simultaneously with the pad-and-bake process (i.e., "pre-cure" or "fast cure") or may be performed after the fabric is cut and seamed into a garment form and then set to form creases or wrinkles (i.e., "post-cure" or "delayed cure"). If the amount of imbibition is reduced to about 35%, there may be a small, but significant increase in abrasion resistance. Some of the methods described have been found to be useful for this purpose, and also for energy saving, these being foam, vacuum, grooved roll and spray methods. By placing more of the resin used in these ways on the back of the fabric, further benefits in abrasion resistance have been realized.

In addition to the pad-and-bake process, another method of durable press surface treatment of cotton fabrics is known as "moisture cure" or "moisture crosslinking" (which process will be referred to herein as "moisture cure"), in which a durable press surface treatment comprising a crosslinking agent, such as DMDHEU, and a highly acidic catalyst (typically based on hydrochloric acid or sulfuric acid) is applied at very low pH values (typically in the range of 1.0 to 2.0), at a soak level of between 60 percent and 100 percent. The fabric is then carefully dried to a residual moisture content typically in the range of 6 to 12 percent. The fabric is then rolled onto an a-frame or similar device, which is then stored at a constant temperature of about 30 to 35 degrees for 16 to 24 hours. The fabric is then neutralized and washed to remove acidity, followed by dyeing. The treatment bath may contain a lubricant such as a polyethylene or silicone emulsion (carefully selected for a highly acidic environment). The fabric is often pre-or post-softened to improve handling or fabric aesthetics (e.g., hand).

In the durable press surface treatment itself, considerable attention has been directed over the years to the crosslinking agent. A compound that meets most of the requirements for performance, safety, availability, and cost is dimethylol dihydroxy ethylene urea (DMDHEU).

DMDHEU is most commonly used in the etherified state to control the free formaldehyde. It may also be buffered or unbuffered.

Alternatives to DMDHEU include selected polycarboxylic acids that are completely formaldehyde free, but such polycarboxylic acids lack the performance and cost advantages of DMDHEU. They also require the use of sodium hypophosphite as a catalyst, which can cause excessive discoloration and fading of specific dye types, is expensive, and is strictly regulated by the government as it is a raw material for certain illegal drugs. Another type of non-formaldehyde resin is the reaction product of dimethyl urea with glyoxal (DMUG).

Historically, DMUG has lacked the performance of DMDHEU, but recently chemical modifications of DMUG and other process changes have led to better performance.

Over the years, a number of catalysts have been used. Magnesium chloride or magnesium chloride activated with citric acid, acetic acid or glycolic acid is mainly used today in terms of performance and safety. Other catalysts include aluminum chloride, magnesium sulfate and other similar salts, with or without an organic acid incorporated in the formulation. As mentioned hereinbefore, for moisture curing, catalysts based on strong mineral acids, such as hydrochloric acid or sulfuric acid, may be used in special cases. Sodium hypophosphite is often recommended for the selected polycarboxylic acid cross-linking agent.

The concentration of the resin and catalyst and the temperature and time of reaction with the cotton-containing fibers play a great role in the durable setting, strength and abrasion resistance of the finished product. Sufficient resin and catalyst are necessary for adequate durable set, but too much resin and/or catalyst will cause excessive loss of strength and abrasion resistance. In the same way, too high a temperature and/or too much curing time will result in excessive loss of strength and abrasion resistance. These parameters must be optimized to achieve maximum performance from a particular surface treatment.

Softeners are an essential part of each durable press surface treatment. They play an important role in hand, needle cut resistance and abrasion resistance. While softeners improve tear strength, they reduce tensile strength because they allow slippage of fibers and yarns. Polyethylene is particularly useful for improving abrasion resistance. This property is due to the lubricity of the polymer and its resistance to washing. The resistance can be further enhanced by the addition of a low level of a surface cross-linking agent, such as a polyfunctional blocked isocyanate.

B. Improved durable set property balance of cotton fabric using non-formaldehyde technology

The presently disclosed subject matter, in part, demonstrates that other additives can be used in the surface treatment formulation, such as a surface treatment formulation comprising DMUG, to improve the strength and abrasion resistance of cotton-containing durable press products. As provided below, it is critical that the additives be used at a correct concentration in an optimized surface treatment. If the concentration of a particular additive is too low, it will not be effective. If the concentration of a particular additive is too high, it will adversely affect the durable set performance. Representative additives include dicyandiamide, choline chloride, ethylene urea, propylene urea, and dimethyl urea. The concentration of each additive, depending on the surface treatment bath and the particular additive, may vary from about 0.1% to about 4.0% by weight of the surface treatment bath.

A representative formulation for improving the balance of durable press properties may comprise the following composition (given as a weight percentage of the surface treatment bath as received commercial product, noting that the percentages provided herein are based on a received commercial product comprising about 40% modified DMUG reactant, e.g., 3.0% DMUG, as enumerated herein representing about 1.2% active DMUG, and similarly, 40.0% DMUG as enumerated herein representing about 16% active DMUG): from about 3.0% to about 40.0% non-formaldehyde dimethylurea/glyoxal (DMUG) and the like, including about 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, and 60% non-formaldehyde dimethylurea/glyoxal (DMUG), wherein the formulation is essentially free of dimethylol dihydroxyethylene urea (DMDHEU); from about 0.1% to about 4.0% dicyandiamide, choline chloride, ethylene urea, propylene urea, dimethyl urea and combinations thereof, including from about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5 and 4.0% dicyandiamide, choline chloride, ethylene urea, propylene urea, dimethyl urea and combinations thereof; from about 0.5% to about 8.0% of a polyethylene softener (which type may comprise medium density polyethylene softeners, high density polyethylene softeners, nonionic polyethylene softeners, and/or cationic polyethylene softeners), including about 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, and 8.0% of a polyethylene softener (note that the percentages of a polyethylene softener recited herein are based on a as-received formulation comprising about 35% active polyethylene plus emulsifier, e.g., 0.5% polyethylene softener represents about 0.175% active polyethylene, and similarly, 8.0% polyethylene softener represents about 2.8% active polyethylene softener); from about 0.0% to about 6.0% of an aminopolysiloxane softener, including about 0.0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5 and 6.0% of an aminopolysiloxane softener (note that the percentages of the monomeric aminopolysiloxane softener listed herein are based on an as received formulation comprising about 25% active aminopolysiloxane plus emulsifier, e.g., 0.1% aminopolysiloxane softener represents about 0.025% active aminopolysiloxane and, similarly, 6.0% aminopolysiloxane softener represents about 1.5% active aminopolysiloxane); and from about 0.0% to about 10.0% of an acidic catalyst, including from about 0.0% to about 10.0% of a lewis acid catalyst (e.g., magnesium chloride, aluminum chloride, or magnesium sulfate) including from about 0.0, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5, and 10% of a lewis acid catalyst, or from about 0.0% to about 10.0% of a bronsted acid catalyst (e.g., citric acid, acetic acid, or glycolic acid), including from about 0.0, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5, 6.5, 6.0, 5, 0.5, 9.5, and 10% of a lewis acid catalyst, including from about 0, 0.0% of the total of the lewis acid catalyst. The amount of catalyst must be appropriate to adequately crosslink the DMUG resin and the additives used. For most curing, a catalyst containing a strong mineral acid, such as hydrochloric acid or sulfuric acid, is added at a concentration specified to achieve a pH value typically in the range of 1.0 to 2.0. A small amount of a wetting agent may also be used to aid penetration of the surface treatment. Other adjuvants, including but not limited to fluorochemical water repellents, hand modifying finishes, and the like, may be added to the above formulations if additional performance properties are to be provided. The particular amount of chemical used in the surface treatment formulation should be balanced with the amount of said soaking of the fabric or substrate, which may range from about 30% to about 120%, including about 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115 and 120%, depending on the method of application, but for conventional pad-bake-curing processes typically from about 60% to about 100%, including about 60, 65, 70, 75, 80, 85, 90, 95 and 100%. At low imbibition (e.g., foam surface treatment at about 30% imbibition), the above-mentioned concentrations may have to be increased to reach the same final addition.

As mentioned above, the ingredients of the presently disclosed formulations, such as DMUG, softeners and the like, are provided as aqueous solutions that are in a diluted state and do not represent 100% active ingredient. Therefore, the percentages listed for such components need to be adjusted accordingly. Compositions having different percentages of active ingredients are also suitable for use in the presently disclosed formulations and methods. In such embodiments, one of ordinary skill in the art will recognize that the concentration of the formulation may be adjusted to compensate for differences in activity. Further, as used herein, the phrase "essentially free of dimethylol dihydroxyethylene urea (DMDHEU)" means that the formulation contains less than a trace amount of DMDHEU, which in some embodiments is less than about 0.1% or less of DMDHEU.

The presently disclosed formulations can be added in a number of application methods, including, but not limited to, pre-cure and post-cure conditions of fabrics, and garment treatments such as garment laundering and dosing, and the like. The matrix must be cured at an elevated temperature for a sufficient time to achieve sufficient crosslinking. Since commercial curing equipment may vary from manufacturer to manufacturer, the curing time and temperature must be optimized for the particular equipment, application method, and substrate used. The temperature range for curing may be from about 140 degrees to 200 degrees, including about 140 degrees, 145 degrees, 150 degrees, 155 degrees, 160 degrees, 165 degrees, 170 degrees, 175 degrees, 180 degrees, 185 degrees, 190 degrees, 195 degrees, and 200 degrees, and the curing time may range from about 10 seconds to about 10 minutes, including about 10 seconds, 30 seconds, 1 minute, 2 minutes, 3 minutes, 4 minutes, 5 minutes, 6 minutes, 7 minutes, 8 minutes, 9 minutes, and 10 minutes. In order to achieve the best improvement in the durable press properties with the above formulations, it is recommended to use the lowest curing temperature that achieves sufficient crosslinking and is appropriate for the application method and the substrate used. At higher curing temperatures, the improvement in performance of the optimized surface treatment compared to a standard durable-setting surface treatment will still be observable; however, the improvement may not be as significant as the samples cured at lower temperatures. In some embodiments, the drying may be performed simultaneously with the curing, e.g., so-called "fast cure", and the total time in the oven will be extended to include both drying and curing. Alternatively, for the moisture curing process, the fabric is then carefully dried to a residual moisture content typically in the range of 6 to 12 percent. The fabric is then rolled onto an a-frame or similar device, which is then stored at a constant temperature of about 30 to 35 degrees for 16 to 24 hours. The fabric is then neutralized and washed to remove acidity, followed by dyeing.

The presently disclosed subject matter relates to cellulosic fibers and blends thereof, preferably cotton and cotton blends, and may include cellulosic fibers, yarns, fabrics, garments and other articles having cellulosic fibers. The term "cellulosic substrate" as used herein means a substrate comprising cellulosic fibers, such as cotton; jute fiber; flax fibers; hemp fibers; ramie fibers; regenerated cellulose products (including but not limited to rayon, lyocell and modal), mixtures of the above; and blends with other fibrous materials (e.g., synthetic fibers), in which blends, in some embodiments, at least about 25 percent, in other embodiments at least about 40 percent, including about 25, 30, 35, and 40 percent of the fibers are cellulosic materials. The cellulosic fibers preferably comprise cotton fibers. The cellulosic substrate may include non-cellulosic fibers (e.g., synthetic fibers and non-cellulosic natural fibers) including, for example, a polyalkylene such as polypropylene or polyethylene, polyester, nylon, vinylon, polyurethane, acetate fibers, mineral fibers, silk, wool, polylactic acid (PLA) or polytrimethylene terephthalate (PTT), and mixtures thereof. In a particular embodiment, the cellulosic matrix consists entirely of cellulosic fibers, such as cotton. The substrate can be any article containing the requisite amount of cellulosic fibers and includes, for example, woven, knitted, non-woven, multi-layered, garments, yarns, and the like.

More specifically, one embodiment of the presently disclosed surface treatment includes the following chemicals (given as weight percentages of the commercial product as received in the surface treatment bath): about 10% to 30.0% of a modified DMUG reagent (a suitable example is Arkofix NZF from Archroma); about 0.1% to 4.0%, depending on the particular additive, of one of the additives listed above; about 1% to 5.0% polyethylene (high density, 35%) softener (a suitable example is Turpex ACN New from Huntsman Textile Effects, inc); from about 1.0% to 5.0% of an aminopolysiloxane (20%) softener (a suitable example is marsil gss from Marlin Chemical); and about 1.0% to 4.0% of an activated magnesium chloride catalyst (a suitable example is catalyst NKD from ango corporation). In some embodiments, a small amount of a wetting agent (a suitable example is FluowetUD from Onga) may also be added to the formulation.

In particular embodiments, this representative durable press surface treatment is applied as a pre-cure surface treatment to 100% cotton 3/1 twill fabric (7.3 ounces per square yard), 100% cotton shirt fabric 80/2 fine oxford (3.9 ounces per square yard), and 100% cotton 24 cut duplex (5.8 ounces per square yard). The twill fabric was prepared commercially (desized, scoured, bleached and lye-treated) and dyed to an vat cal shade. For the twill fabric, the surface treatment is pad applied at a soak level of about 60% to about 65%, and the fabric is then dried/cured in a continuous laboratory oven at about 160 degrees for about 105 seconds. The shirt fabric is prepared commercially (desizing, scouring and bleaching) and then treated with (a) a lye treatment followed by a liquid ammonia pretreatment, (B) a lye treatment only, or (C) a liquid ammonia pretreatment only. The shirt fabric was then surface treated on a pilot scale tenter frame by pad application of the surface treatment solution at 55 to 60% pick-up, followed by drying/curing at 160 degrees for 70 to 90 seconds. The knitted double-sided fabric was prepared and reactive dyed in a sample jet to a medium blue shade. For the knit reversible fabric, fabric samples were pre-marked to the size of the needle plate frame, the surface treatment was pad applied at a soak level of about 115 to about 130%, the fabric was pinned to the needle plate frame along the marked edge, and the fabric was dried/cured at about 160 degrees for about 90 seconds to about 120 seconds.

Various tests were used to take the performance of durable setting surface treatments for cotton and other substrates. These tests include, but are not limited to, the protocols and methods below. Smoothness scoring (AATCC TM124) is performed by washing and drying fabric samples in a selected protocol, then comparing the washed samples to smoothness replicas. The smoothness reproduction is on a scale from 1 to 5, 1 being highly wrinkled and 5 having few wrinkles. The washing protocol used in the following examples used a top loading washing machine with a load of 4 pounds and a washing temperature of 40 degrees and AATCC standard detergent (powder), after which the samples were tumble dried under a "cotton/heavy" setting. A total of 3 home wash/tumble dry (HLTD) cycles are used in the examples below, but the wash protocol may be modified to accommodate other types of washing machines and temperature settings. Durable setting surface treatments, such as the one described in the present invention, tend to improve smoothness appearance scores on cotton and other cellulosic fabrics. Another test is dimensional change (AATCC TM135), which measures the shrinkage or increase (shrinkage is a negative value) of the fabric samples after washing and drying. The same wash protocol as used in AATCC TM125 was used for AATCC TM 135. Durable setting surface treatments tend to reduce shrinkage of cotton or other cellulosic fabrics. Tensile strength (ASTM D5034) and tear strength (ASTM D1424) were used to assess the amount of strength loss that may occur with a durable press finish. Crease recovery angle (AATCC TM6, modified to use an automatic crease recovery angle tester), sometimes used as a measure of durable set performance; this test is often used as a research tool but is not a performance criterion. Higher fold recovery angles normally indicate improved durable set performance. Flex abrasion (ASTM D3885) and martindale abrasion (ASTM D4966) were used to measure abrasion resistance; durable setting surface treatments can cause abrasion loss on cotton fabrics. Wrinkle durability (AATCC TM88C) is used to determine the durability of post-cured cotton or cellulosic garments (e.g., shorts or pants with durable wrinkles) after laundering by tucking wrinkles. The same wash protocol as used for AATCC TM124 was used for wrinkle durability in some examples below. The wrinkle durability test uses a visual replica similar to that used for the smoothness appearance at AATCC TM 124; this test is also on a scale of 1 to 5, with 5 being the highest score. Wrinkle recovery (AATCC TM128) is used to measure the "dry wrinkle recovery" of a fabric (wrinkles that may occur when actually worn); this test is also a visual test using a1 to 5 scale with 5 being the highest score. The whiteness index is performed on a spectrophotometer and the amount of yellowing/darkening of the fabric is measured; higher values are whiter or less yellow.

In the specification and claims, the terms "comprise", "comprises", "comprising" and "comprising" are used in a non-exclusive sense unless the context requires otherwise. Similarly, the term "include" and its grammatical variants are intended to be non-limiting, such that recitation of items in a list is not to the exclusion of other like items that may be substituted or added to the recited items.

For the purposes of this specification and the claims that follow, unless otherwise indicated, all numbers expressing quantities, sizes, dimensions, proportions, shapes, formulations, parameters, percentages, parameters, quantities, characteristics, and other numerical quantities used in the specification and claims are to be understood as being modified in all instances by the term "about," although the term "about" may not be expressly recited in the stated values, quantities, or ranges. Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are not and need not be exact, but may be approximate and/or larger or smaller, as desired, reflecting tolerances, conversion factors, rounding off, measurement error and the like, and other factors known to those of skill in the art to achieve the desired properties in light of the presently disclosed subject matter. For example, when referring to a value, the term "about" may, in some embodiments, be intended to encompass a difference of ± 100% from the particular value; in some embodiments, a difference of ± 50% from the particular value may be intended to be included; in some embodiments, a difference of ± 20% from the particular value may be intended to be included; in some embodiments, a difference of ± 10% from the particular value may be intended to be included; in some embodiments, a difference of ± 5% from the particular value may be intended to be included; in some embodiments, a difference of ± 1% from the particular value may be intended to be included; in some embodiments, a variation of ± 0.5% from the particular value and in some embodiments, a variation of ± 0.1% from the particular value may be intended to be included when such a variation is appropriate for performing the disclosed methods or employing the disclosed compositions.

Further, the term "about" when used in connection with one or more numbers or ranges of values should be understood to refer to all such numbers, including all numbers in a range and modified by extending the line above and below the previously stated value. The recitation of numerical ranges by endpoints includes all numbers, e.g., integers, decimal places including said integers, integers subsumed within that range (e.g., the recitation of 1 to 5 includes 1, 2, 3, 4, and 5, and decimals of 1 to 5, e.g., 1.5, 2.25, 3.75, 4.1, and the like) and any range within that range.

Example (c):

the following examples are included to provide guidance to those skilled in the art for practicing representative embodiments of the presently disclosed subject matter. In view of the present disclosure and the general level of skill in the art, those skilled in the art will recognize that the following examples are intended to be exemplary only and that many changes, modifications, and variations can be made without departing from the scope of the presently disclosed subject matter. The following description of compositions and specific examples are intended for purposes of illustration only and are not to be construed in any way as limiting the manufacture of the disclosed compounds by other methods.

Example 1

An optimized surface treatment applied to 100% denim in the pre-cured condition is provided in the table presented immediately below.

The procedure is as follows: padding: 30 psi, 1 dip and 1 pad (target soak 60 to 70%). Drying/or picking unit

And (3) curing: in a continuous laboratory oven at the indicated times/temperatures.

Word class abbreviation list: HLTD ═ home wash/tumble dry (HLTD) cycle. CRA is the wrinkle recovery angle.

With respect to the surface treatment formulations shown in table 1 and the physical test results of the treated fabric samples shown in table 2, the non-formaldehyde surface treatment (formulation 35GW-2) provided a smoothness similar to the DMDHEU control group (formulation 35 GW-1); however, the tensile/tear strength and flex wear of the non-formaldehyde surface treatment is significantly higher. The progressive addition of dicyandiamide did not improve the tensile/tear strength of the non-formaldehyde surface treatment, but did improve the flex abrasion to some extent. The flex abrasion reaches a maximum at 2 g/kg dicyandiamide (bath weight 0.2%).

The procedure is as follows: padding: 30 psi, 1 dip and 1 pad (target soak 60 to 70%). Drying/or picking unit

And (3) curing: in a continuous laboratory oven at the indicated times/temperatures.

Word class abbreviation list: HLTD ═ home wash/tumble dry (HLTD) cycle. CRA is the wrinkle recovery angle. CC ═ choline chloride. EU ═ ethylene urea.

With respect to the surface treatment formulations shown in table 3 and the physical test results of the treated fabric samples in table 4, higher amounts of dicyandiamide were added to the formaldehyde-free formulations. The smoothness results were unexpected; the smoothness score decreased at 10 g/kg dicyandiamide, but not at 20 g/kg. The CRA data also conflicts with the smoothness score as does dicyandiamide, and the amount of shrinkage increases progressively with more dicyandiamide. The increased shrinkage is suspected to occur when the dicyandiamide concentration is too high and begins to interfere with crosslinking. The tensile, tear and flex wear increase with the addition of dicyandiamide; these data show that a maximum is reached at 5 g/kg (0.5% bath weight) of dicyandiamide.

The option of adding choline chloride or ethylene urea was also explored in the 49GW series. Referring again to table 4, choline chloride appeared to have a somewhat minor effect on smoothness and tear strength compared to addition of DMUG alone (49 GW-2). Ethylene urea gave some improvement in tear strength and flex abrasion, but the smoothness score decreased at 20 g/kg. The optimum amount of ethylene urea appears to be between about 10 and about 20 grams per kilogram.

The procedure is as follows: padding: 30 psi, 1 dip and 1 pad (target soak 60 to 70%). Drying/or picking unit

And (3) curing: in a continuous laboratory oven at the indicated times/temperatures.

Word class abbreviation list: HLTD ═ home wash/tumble dry (HLTD) cycle. CRA is the wrinkle recovery angle.

With respect to the surface treatment formulations shown in table 5 and the physical test results of the treated fabric samples in table 6, two different DMUG systems were compared in the pre-cure surface treatment with and without dicyandiamide as an additive. DMUG a and catalyst a are the aforementioned Arkofix NZF and catalyst NKD from oho corporation. DMUG B and catalyst B are Reacel ZF and Catal MCA from Bozzetto, Inc. Both DUMG systems gave slightly higher smoothness scores than the DMDHEU control group surface treatment. When dicyandiamide was added to each DUMG system, there was a small shift in smoothness scores, but no significant change was noted. (the only possible exception is DMUG B, the smoothness decreases when 2 grams/liter dicyandiamide is added (2.7 versus 3.2), but the smoothness of 3 grams/liter dicyandiamide is slightly higher (2.9), so there appears to be no trend there.

The procedure is as follows: padding: 30 psi, 1 dip and 1 pad (target soak 60 to 70%). And (3) drying: 110 degrees 75 seconds in a continuous laboratory oven at the indicated times/temperatures. Light pressure for 4 seconds (to simulate stretching on a tenter. time/temperature shown in table 7 was cured in a continuous laboratory oven.

Word class abbreviation list: HLTD ═ home wash/tumble dry (HLTD) cycle. CRA is the wrinkle recovery angle.

With respect to the physical test results for the surface treatment formulations shown in table 7 and the treated fabric samples in table 8, a DMUG surface treatment was applied to cotton woven fabric in formulations with and without dicyandiamide. The treated fabric samples were dried and then cured at a temperature of 160 degrees or 170 degrees for 45 seconds or 60 seconds. Formulations without dicyandiamide all have similar smoothness under all cure conditions. The smoothness score of the dicyandiamide formula appears to have a slight trend towards increasing smoothness with higher cure temperature/longer cure time. Tensile strength is generally higher where dicyandiamide is added to the surface treatment, except for 170 degrees/60 seconds of cure, which decreases to almost the same value as a sample cured at 170 degrees/60 seconds without dicyandiamide. The tear strength was not generally affected by the addition of dicyandiamide in this experiment. The flex wear was improved under all curing conditions by the addition of dicyandiamide, except at 170 degrees/60 seconds, the improvement in flex wear was reduced as in tensile strength.

The procedure is as follows: padding: 30 psi, 1 dip and 1 pad (target soak 60 to 70%). Drying/or picking unit

And (3) curing: cured in a continuous lab oven at 160 degrees for 105 seconds.

Word class abbreviation list: HLTD ═ home wash/tumble dry (HLTD) cycle. CRA is the wrinkle recovery angle.

With respect to the surface treatment formulations shown in table 9 and the physical test results of the treated fabric samples in table 10, several additives (other than dicyandiamide) were tested on a cotton twill in a surface treatment containing DMUG. This is a subsequent experiment to the experiments shown in tables 3 and 4. It is noteworthy that some additives have an effect on the pH of the surface treatment bath; in these examples, dilute hydrochloric acid was carefully added to lower the pH of the surface treatment bath to 3.5 (which is close to the pH of a bath containing only DMUG). The results for each additive will be discussed individually:

urea: although the smoothness score appeared to decrease with the addition of 5 grams/liter of urea compared to a surface treatment containing only DMUG, the smoothness score was slightly higher than it was with 10 grams/liter of urea. Tensile, tear and flex wear values are higher with increasing amounts of urea added to the surface treatment.

Ethylene urea: smoothness scores were not affected by the addition of ethylene urea to the surface treatment. The addition of ethylene urea only results in a slight increase in tensile and tear strength; however, the flex wear is greatly improved by the ethylene urea.

Creatine: smoothness was not affected by 5 gr/l creatine, but at 10 gr/l creatine smoothness scores were reduced. The addition of creatine results in only a slight increase in tensile and tear strength compared to DMUG alone. At 5 grams/liter of creatine, the flexor abrasion is actually lower; creatine increases in flex abrasion at 10 grams/liter.

Trimethyl urea: trimethyl urea has little effect on either property at either of the two concentrations.

Guanidine: guanidine has little effect on either property at either concentration.

Summarizing the experiments with additives as shown in tables 9 and 10, urea and ethylene urea have a positive effect on wear and strength retention but not on smoothness scores. Other additions either did not improve the properties or had a negative effect on smoothness retention.

Post cure procedure: padding at 30 psi, 1 pad and 1 pad (target soak 60 to 70%). Dried in a continuous laboratory oven at 95 degrees 60 seconds dwell time. For post-cure, cut and sewn simulated trouser legs were used for wrinkle appearance test; flat cloths were used for other tests. A flat steam iron is used to iron the trouser legs or flat cloth. The samples were cured in a large oven at 150 degrees for 10 minutes.

Word class abbreviation list: HLTD ═ home wash/tumble dry (HLTD) cycle. CRA is the wrinkle recovery angle.

With respect to the surface treatment formulations shown in table 11 and the physical test results of the treated fabric samples in table 12, two different DMUG systems were compared in post-cure surface treatment with and without dicyandiamide as an additive. DMUG a and catalyst a are the Arkofix NZF and catalyst NDK from ango corporation mentioned above. DMUG B and catalyst B are Reacel ZF and Catal MCA from Bozzetto, Inc. Both DMUG systems provided a smoothness appearance score similar to each other and to the DMDHE U control group, and the addition of dicyandiamide did not detract from the smoothness score. Wrinkle retention scores were somewhat inconsistent: it was later found that the steam injection valve of a steam iron was somewhat problematic. Both non-formaldehyde systems had higher tensile and tear values than the DEDHEU control. The addition of dicyandiamide resulted in a small increase in tensile and tear in both DMUG systems.

The procedure is as follows: the tests were performed on a pilot scale tenter. Padding is performed at 65 pounds per square inch (the soak is 55 to 60%). The fabric was then dried/cured for the times and temperatures shown in table 13.

Word class abbreviation list: HLTD ═ home wash/tumble dry (HLTD) cycle. CRA is the wrinkle recovery angle. DNT ═ unripped (sample torn in the transverse direction).

With respect to the surface treatment formulations shown in table 13 and the physical test results of the treated (lye treated/liquid ammonia pretreated) fabric samples shown in table 14A, all non-formaldehyde tests using DMUG reactants had higher smoothness scores than the DMDHEU control. Adding dicyandiamide to a surface treatment with DMUG at 200 grams/liter did not change the smoothness score; however, when dicyandiamide was added, the surface treatment containing 300 g/l of DUMG had a reduction in smoothness. The tensile and tear strengths of the DMUG surface treatment were generally higher than those of the DMDHEU control group. The addition of dicyandiamide resulted in an increase in tensile and tear strength of the surface treatment with two concentrations of DMUG (200 and 300 grams per liter). Flex wear was higher in all DMUG surface treatments than in DMDHEU control groups, and the addition of dicyandiamide resulted in a further improvement in flex wear. The formaldehyde levels of all DMUG surface treatments, with or without dicyandiamide, were below detectable levels in both AATCC test method 112 and ISO 14184-1. All non-formaldehyde surface treatments were acceptable in whiteness index.

Word class abbreviation list: HLTD ═ home wash/tumble dry (HLTD) cycle. CRA is the wrinkle recovery angle. DNT ═ unripped (sample torn in the transverse direction).

With respect to the surface treatment formulations shown in table 13 and the physical test results of the treated fabric samples shown in table 14B (fabric treated with lye only), the smoothness scores for all non-formaldehyde tests using the DMUG reactant were higher than the DMDHEU control. The addition of dicyandiamide resulted in a slight reduction in smoothness scores for both DMUG concentrations (200 and 300 grams/liter). The tensile and tear strengths of the DMUG surface treatment were generally higher than those of the DMDHEU control group. The addition of dicyandiamide resulted in an increase in tensile and tear strength in the surface treatment with DUMG at both concentrations. All DMUG surface treatments had higher flex wear than DMDHEU control, and the addition of dicyandiamide resulted in a further improvement in flex wear. It is noted that the wrinkle recovery test is a very severe test for woven cotton fabrics, and therefore all results are low (2.0 or less.) the whiteness index of all non-formaldehyde surface treatments are acceptable.

Word class abbreviation list: HLTD ═ home wash/tumble dry (HLTD) cycle. CRA is the wrinkle recovery angle. DNT ═ unripped (sample torn in the transverse direction).

With respect to the surface treatment formulations shown in table 13 and the physical test results of the treated fabric samples shown in table 14C (liquid ammonia only treated fabric), the smoothness scores of all non-formaldehyde test results using the DMUG reactant were higher than the DMDHEU control group. The addition of dicyandiamide to the surface treatment with DMUG at 200 grams/liter did not change the smoothness score; however, when dicyandiamide was added, there was a small reduction in smoothness of the surface treatment containing 300 grams/liter of DUMG. The tensile and tear strengths of the DMUG surface treatment were generally higher than those of the DMDHEU control group. The addition of dicyandiamide resulted in an increase in tensile and tear strength in both surface treatments with two concentrations of DMUG (200 and 300 grams/liter). All DMUG surface treatments had higher flex wear than DMDHEU control, and the addition of dicyandiamide resulted in a further improvement in flex wear. It is noted that the wrinkle recovery test is a very severe test for woven cotton fabrics, and therefore all results are low (2.0 or less.) the whiteness index of all non-formaldehyde surface treatments are acceptable.

Summarizing the physical test results for all fabrics in the "68 KGB" test (tables 13, 14A, 14B and 14C), it should be noted that the smoothness scores for the fabric pretreated with liquid ammonia only (fabric C) were always the highest, followed by the fabric pretreated with lye/liquid ammonia (fabric a) and then the fabric pretreated with lye only (fabric B). In some cases, particularly at high DMUG concentrations (300 grams/liter), the smoothness score decreased somewhat with the addition of dicyandiamide. There are some concerns that the concentration of dicyandiamide may be too high at 5 grams/liter. In addition, the drying/curing time may be too short. It was determined that the test was repeated on fabrics B and C, with some adjustments in the formulation and drying/curing time; for subsequent testing, see tables 15, 16A and 16B, below.

The procedure is as follows: the tests were performed on a pilot scale tenter. Padding is performed at 65 pounds per square inch (the soak amount is 55 to 60 percent soak amount). The fabric was dried/cured for the times and temperatures shown in table 15.

Word class abbreviation list: HLTD ═ home wash/tumble dry (HLTD) cycle. CRA is the wrinkle recovery angle. DNT ═ unripped (sample torn in the transverse direction).

With respect to the surface treatment formulations shown in table 15 and the physical test results of the treated fabric samples shown in table 16A (fabric treated with lye only), the smoothness scores of all non-formaldehyde tests using the DMUG reactant were higher than the DMDHEU control group. The addition of dicyandiamide did not have much effect on smoothness scores at two DMUG concentrations (200 and 300 grams/liter). The tensile and tear strength of the DUMG surface treatment was generally higher than that of the DMDHEU control group. The addition of dicyandiamide resulted in an increase in tensile and tear strength in the surface treatment of both concentrations of DMUG. All DMUG surface treatments had higher flex wear than the DMDHEU control group, and the addition of dicyandiamide resulted in a further improvement in flex wear. The Martindall abrasion values for all the DMUG surface treatments were higher than the DMDHEU control group. Since the martindale test was terminated at 20000 cycles, it was not determinable whether any improvement in martindale wear was caused by dicyandiamide. A whiteness index of 200 grams/liter is acceptable; there was a reduction in whiteness at the 300 g/l DUMG group, but the degree of yellowing was not too excessive.

Word class abbreviation list: HLTD ═ home wash/tumble dry (HLTD) cycle. CRA is the wrinkle recovery angle. DNT ═ unripped (sample torn in the transverse direction).

With respect to the surface treatment formulations shown in table 15 and the physical test results of the treated fabric samples shown in table 16B (fabric treated with liquid ammonia only), the smoothness scores of all non-formaldehyde tests using the DMUG reactant were higher than the DMDHEU control group. The addition of dicyandiamide to the surface treatment with DMUG at 200 grams/liter did not change the smoothness score; however, when dicyandiamide was added, there was a small reduction in smoothness of the surface treatment containing 300 grams/liter of DMUG. When dicyandiamide was added, there was a small increase in tensile strength, tear strength and flex wear in the surface treatment of DMUG at 200 grams/liter; however, at 300 g/l of DMUG, dicyandiamide did not affect these properties to a significant extent. Since all martindale abrasion tests were terminated at 20000 cycles, no difference in results could be determined. All DMUG surface treatments were acceptable for whiteness index.

Summary as detailed in tables 15, 16A and 16B, all of the "70 KGB" tests on shirt fabric did not improve the overall results in smoothness much as the drying/curing time was adjusted compared to the "68 KGB" tests shown in tables 13, 14A, 14B and 14C.

The procedure is as follows: pre-marking the fabric sample to size on a needle board rack, padding: pinning the fabric at the mark on the fabric at 0.7 meters/min, 30 pounds per square inch, 1 dip and 1 nip (target soak amount of 110 to 120%), and drying/curing: dry/cure at 160 degrees for 90 seconds in a continuous lab oven.

Word class abbreviation list: HLTD ═ home wash/tumble dry (HLTD) cycle.

With respect to the surface treatment formulations shown in table 17 and the physical test results of the treated fabric samples in table 18, the 100 grams/liter DMUG formulation (34GW-2) had better fabric smoothness compared to the control group surface treatment. The addition of varying amounts of dicyandiamide (0.5, 1.0 and 1.5 grams/liter) to formulation 34GW-2 tended to improve burst strength. The smoothness was improved but burst strength was reduced for the formulation with DMUG at 200 g/l in the formulation (34GW-6) compared to the formulation with DMUG at 100 g/l (34 GW-2). Formulations (34GW-7, 34GW-8, and 34GW-9) that added different amounts of dicyandiamide (1, 2, and 3 grams/liter) to the 200 grams/liter DMUG tended to increase burst strength without changing the smoothness.

The procedure is as follows: pre-marking the fabric sample to size on a needle board rack, padding: the fabric was pinned at the mark on the fabric at 0.7 meters/minute, 30 pounds per square inch, 1 dip and 1 nip (target soak amount of 110 to 120%), and dried/cured at 160 degrees in a continuous laboratory oven. Sample "a" was dried/cured for 90 seconds; sample "B" was dried/cured for 60 seconds.

Word class abbreviation list: HLTD ═ home wash/tumble dry (HLTD) cycle.

With respect to the physical test results for the surface treatment formulations shown in table 19 and the treated fabric samples in table 20, the longer cure times gave only slight, if any, improvement in smoothness. However, such increased cure times tend to compromise burst strength. As observed in the "34 GW" group (tables 17 and 18), the addition of dicyandiamide tended to improve burst strength.

The procedure is as follows: pre-marking the fabric sample to size on a needle board rack, padding: the fabric was pinned at the mark on the fabric at 0.7 meters/minute, 30 pounds per square inch, 1 dip and 1 nip (target soak amount of 110 to 120%), and dried/cured in a continuous laboratory oven at 160 degrees for 90 seconds.

Word class abbreviation list: HLTD ═ home wash/tumble dry (HLTD) cycle.

With respect to the physical test results for the surface treatment formulations shown in table 21 and the treated fabric samples in table 22, it is notable that the DMDHEU control group (50GW-1) and the non-formaldehyde resin (50GW-2) provide a moderate improvement in smoothness compared to the non-surface treated samples. Both surface treatments significantly reduced shrinkage. The non-formaldehyde resin provides better smoothness and lower shrinkage than the DEDHEU control group; the burst strength of both surface treatments was nearly equal.

In the "50 GW" group (tables 21 and 22), the addition of dicyandiamide progressively improved burst strength, but the smoothness score and shrinkage control progressively worsened. The optimum amount of dicyandiamide required to increase burst strength while maintaining smoothness and shrinkage appears to be in the range of 2 to 5 grams per kilogram (0.2 to 0.5% of bath weight). Choline chloride has only a very small effect, if any, on any of the physical properties described. Ethylene urea did improve burst strength, but as the amount of ethylene urea was increased from 10 g/kg to 20 g/kg, the smoothness decreased to almost the same value as the non-surface treated fabric, and the amount of shrinkage increased.

The procedure is as follows: pre-marking the fabric sample to size on a needle board rack, padding: the fabric was pinned at the mark on the fabric at 0.7 meters/minute, 30 pounds per square inch, 1 dip and 1 nip (target soak amount of 110 to 120%), and dried/cured in a continuous laboratory oven at 160 degrees for 90 seconds.

Word class abbreviation list: HLTD ═ home wash/tumble dry (HLTD) cycle.

With respect to the surface treatment formulations shown in table 23 and the physical test results of the treated fabric samples in table 24, the non-formaldehyde surface treatment (51GW-2) provided better smoothness than its approximate set in "50 GW" because the amount of resin was doubled. Interestingly, increasing the amount of non-formaldehyde resin did not compromise burst strength. As in the "50 GW" group, the addition of dicyandiamide to the non-formaldehyde surface treatment increased burst strength, but the smoothness score and the shrinkage control were progressively impaired.

As in the 50GW group, choline chloride was less effective, and ethylene urea improved burst strength but sacrificed smoothness and shrinkage control. It is noteworthy that the bath pH increases with more ethyleneurea, which may result in less curing. The bathing pH is not affected by dicyandiamide, even at the highest concentration.

As stated at the beginning of paragraph B of the detailed description, these experiments support the following statement: "it is critical that the additive be used in the correct concentration in an optimized surface treatment". The amount of each additive required depends on the desired effect; for example, if increased strength is the desired goal and smoothness/shrinkage control is secondary, slightly higher amounts of each additive may be used in the formulation. However, if the amount of smoothness/shrinkage cannot be sacrificed, less of each additive will be needed.

Reference data

All publications, patent applications, patents, and other references mentioned in the specification are indicative of the levels of those skilled in the art to which the presently disclosed subject matter pertains. All publications, patent applications, patents, and other references mentioned in this specification (e.g., websites, databases, etc.) are herein incorporated by reference in their entirety to the same extent as if each individual publication, patent application, patent, and other reference was specifically and individually indicated to be incorporated by reference. It should be appreciated that although some patent applications, patents, and other references are referred to herein, such references do not constitute an admission that these documents form part of the common general knowledge in the art. In the event that the specification and any incorporated reference conflict, the specification (including any amendments thereto, which amendments may be based on an incorporated reference) shall prevail. Unless otherwise indicated, the standard meanings of the words accepted in the art are used. Standard abbreviations for many words are used herein.

Tomasino, c., chemistry and technology of fiber preparation and surface treatment, north carolina, roli, university of north carolina, NCSU Copy Center, copyright 1992

Vigo, t.l., fabric treatment and property preparation, dyeing, surface treatment and performance, cishere private ltd, netherlands, amsterdam, copyright 1994.

Greenson jr., h.k., Phillips, k.j., tube, j.d., "tough cotton: new attempts to durably set surface treatments, ", AATCC Review: Vo1.5Issue 3, pp.13-16, 5 months 2005.

Greenson jr, h.k., Rowe, James e., "surface treatment of tough cotton of shirt fabric", AATCC Review: Vo1.9Issue 3, pp.30-32, 5 months 2009.

Westpoint Stevens, inc., Andrews, George a., Peterson, Joseph, Hough, William, U.S. patent No. 5,707,404, a formaldehyde-free process for imparting permanent set properties to cotton and cotton blends, 1/13/1998.

Solvay(SoCIEte Anonyme)Krafft Philippe、Gilbeau Patrick、Balthasart

Dominique, Boulos Noel, U.S. patent No. 8,399,692, epichlorohydrin manufacture and use, 3 months and 19 days 2013.

BASF Wyandotte Corporation, Pai, Panemangalore s, U.S. patent No. 4,331,483, a process for scavenging free formaldehyde in fabric materials treated with dimethylol carbamate, 5 months and 25 days 1982.

BASF Aktiengesellschaft, Pai, Panemangalore S, Petersen, Harro; klippel, Friedrich, U.S. patent No. 3,957,431, ironing free surface treatment of fibrous compound processing, 5 months and 18 days 1976.

BASF AG, Hans Wilhelm, guest Lange, Hans weiding, U.S. patent No. 3,232,691, dyes and cross-links the copolymer dye with a copolymer dye, 2 months and 1 day 1966.

Clariant Intelligent LTD, Jean Kyrazis, Georg Lang, International patent No. WO 2007/042380A 1, processing of textile surface treatment, 4.19 days 2007.

ROHM & HAAS, bone Benjamin b, Nuessle Albert c, U.S. patent No. 2,886,474, combined with pigment composition, 5 months and 12 days 1959.

BASF AG, british patent No. 1142428A, surface treatment of fibrous materials comprising or consisting of cellulose, 2 months and 5 days in 1969.

ROHM & HAAS, british patent No. 769271a, aqueous tinting composition or improvements associated with aqueous tinting composition, 3/6/1957.

ROHM & HAAS, british patent No. 769255a, improvement in or relating to aqueous tinting compositions and their preparation, 3/6/1957.

ROHM & HAAS, british patent No. 769252a, fabric coloring composition or improvements related to fabric coloring composition, 3/6/1957.

ROHM & HAAS, british patent No. 768883a, fabric coloring composition or improvements related to fabric coloring composition, 2 months and 20 days 1957.

European chemical administration (ECHA), to which can be read: www.echa.europa.eu/documents/10162/13641/formaldehydereviews _ report _ en. pdf/551df4a2-28c4-2fa9-98ec-c8d53e2bf0fc (and references cited therein).

Although the foregoing subject matter has been described in some detail by way of illustration and example for purposes of clarity of understanding, it will be apparent to those of ordinary skill in the art that certain changes and modifications may be practiced within the scope of the appended claims.

Claims (40)

1. A formulation for surface treating a cellulosic substrate or mixture thereof in a surface treatment bath, characterized by: the formulation comprises: from about 3.0% to about 60.0% by weight of non-formaldehyde dimethylurea/glyoxal (DMUG) or the like, and from about 0.1% to about 4.0% by weight of one or more additives selected from dicyandiamide, choline chloride, ethylene urea, propylene urea, dimethylurea and combinations thereof, wherein the weight percentages are given as weight percentages of the surface treatment bath, and wherein the formulation is substantially free of dimethylol dihydroxyethylene urea (DMDHEU).

2. The formulation of claim 1, wherein: the formulation further comprises from about 0.5% to about 8.0% of a polyethylene softener.

3. The formulation of claim 2, wherein: the polyethylene softener is selected from a medium density polyethylene softener, a high density polyethylene softener, a non-ionic polyethylene softener or a cationic polyethylene softener, and combinations thereof.

4. The formulation of claim 1, wherein: the formulation further comprises from about 0.0% to about 6.0% of a mono amino silicone softener.

5. The formulation of claim 1, wherein: the formulation further comprises from about 0.0% to about 10.0% of a Lewis acid catalyst, from about 0.0% to about 10.0% of a Bronsted acid catalyst, or a mixture thereof.

6. The formulation of claim 5, wherein: the Lewis acid catalyst is selected from magnesium chloride, aluminum chloride or magnesium sulfate.

7. The formulation of claim 5, wherein: the formulation further comprises a mixture of a Lewis acid catalyst and a Bronsted acid catalyst.

8. The formulation of claim 5, wherein: the bronsted acid catalyst is selected from citric acid, acetic acid or glycolic acid.

9. The formulation of claim 1, wherein: the formulation further comprises an additive selected from the group consisting of a wetting agent, a fluoride water repellent, a hand feel improving finish, and combinations thereof.

10. The formulation of claim 1, wherein: the cellulosic substrate comprises a cellulosic fiber selected from the group consisting of cotton; jute fiber; flax fibers; hemp fibers; ramie fibers; regenerated cellulose products comprising rayon (rayon), lyocell and modal; and mixtures of the above.

11. The formulation of claim 10, wherein: the cellulosic substrate comprises cotton or a blend of cotton.

12. The formulation of claim 10, wherein: the formulation further comprises one or more non-cellulosic fibers.

13. The formulation of claim 12, wherein: the one or more non-cellulosic fibers are selected from a synthetic fiber and a non-cellulosic natural fiber.

14. The formulation of claim 13, wherein: the non-cellulosic fibers are selected from the group consisting of a polyolefin, a polyester, nylon, vinylon, polyurethane, acetate, a mineral fiber, silk, wool, polylactic acid (PLA), polytrimethylene terephthalate (PTT), and combinations thereof.

15. The formulation of claim 1, wherein: the cellulosic substrate comprises an article selected from the group consisting of a woven fabric, a knitted fabric, a non-woven fabric, a multi-layer fabric, a garment, and a yarn.

16. The formulation of claim 1, wherein: the formulation comprises: from about 10.0% to 30.0% DMUG; about 0.1% to 4.0% of one or more additives selected from the group consisting of dicyandiamide, choline chloride, ethylene urea, propylene urea, dimethyl urea, and combinations thereof; about 1.0% to 5.0% of a polyethylene softener; from about 1.0% to 5.0% of an aminopolysiloxane; and about 1.0% to 4.0% activated magnesium chloride.

17. The formulation of claim 16, wherein: the formulation further comprises a wetting agent.

18. A method of surface treating a durable press cellulosic substrate or mixture thereof in a surface treatment bath, characterized by: the method comprises the following steps: applying a surface treatment formulation to the substrate at an elevated temperature for a period of time, the formulation comprising: from about 3.0% to about 60.0% by weight of non-formaldehyde dimethylurea/glyoxal (DMUG) or an analog thereof, and from about 0.1% to about 4.0% by weight of one or more additives selected from dicyandiamide, choline chloride, ethylene urea, propylene urea, dimethylurea and combinations thereof, wherein said weight percentages are given as weight percentages of said surface treatment bath, and wherein said formulation is substantially free of dimethylol dihydroxyethylene urea (DMDHEU).

19. The method of claim 18, wherein: further comprising from about 0.5% to about 8.0% of a polyethylene softener.

20. The method of claim 19, wherein: the polyethylene softener is selected from a medium density polyethylene softener, a high density polyethylene softener, a non-ionic polyethylene softener or a cationic polyethylene softener, and combinations thereof.

21. The method of claim 18, wherein: further comprising from about 0.0% to about 6.0% of a mono amino silicone softener.

22. The method of claim 18, wherein: further comprising from about 0.0% to about 10.0% of a Lewis acid catalyst, from about 0.0% to about 10.0% of a Bronsted acid catalyst, or a mixture thereof.

23. The method of claim 22, wherein: the Lewis acid catalyst is selected from magnesium chloride, aluminum chloride or magnesium sulfate.

24. The method of claim 22, wherein: further comprising a mixture of a Lewis acid catalyst and a Bronsted acid catalyst.

25. The method of claim 22, wherein: the bronsted acid catalyst is selected from citric acid, acetic acid or glycolic acid.

26. The method of claim 18, wherein: further comprising an additive selected from the group consisting of a wetting agent, a fluoride water repellent, a hand feel improving finish, and combinations thereof.

27. The method of claim 18, wherein: the cellulosic substrate comprises a cellulosic fiber selected from the group consisting of cotton, jute, flax, hemp, ramie, regenerated cellulose products including, but not limited to, rayon, lyocell and modal, and mixtures thereof.

28. The method of claim 27, wherein: the cellulosic substrate comprises cotton or a blend of cotton.

29. The method of claim 27, wherein: further comprising one or more non-cellulosic fibers.

30. The method of claim 29, wherein: the one or more non-cellulosic fibers are selected from a synthetic fiber and a non-cellulosic natural fiber.

31. The method of claim 30, wherein: the non-cellulosic fibers are selected from the group consisting of a polyolefin, a polyester, nylon, vinylon, polyurethane, acetate, a mineral fiber, silk, wool, polylactic acid (PLA), polytrimethylene terephthalate (PTT), and combinations thereof.

32. The method of claim 18, wherein: the cellulosic substrate comprises an article selected from the group consisting of a woven fabric, a knitted fabric, a non-woven fabric, a multi-layer fabric, a garment, and a yarn.

33. The method of claim 18, wherein: the method comprises the following steps: from about 10.0% to 30.0% DMUG; about 0.1% to 4.0% of one or more additives selected from the group consisting of dicyandiamide, choline chloride, ethylene urea, propylene urea, dimethyl urea, and combinations thereof; about 1.0% to 5.0% of a polyethylene softener; from about 1.0% to 5.0% of an aminopolysiloxane; and about 1.0% to 4.0% activated magnesium chloride.

34. The method of claim 33, wherein: further comprises a wetting agent.

35. The method of claim 18, wherein: the method is selected from a pre-heat setting treatment method or a post-heat setting treatment method.

36. The method of claim 18: the method is characterized in that: the method is selected from a garment dip-washing or a dosing method.

37. The method of claim 18, wherein: the temperature has a range from about 140 degrees to 200 degrees.

38. The method of claim 18, wherein: the duration has a range from about 10 seconds to about 10 minutes.

39. The method of claim 18, wherein: the method comprises a dipping method.

40. The method of claim 39, wherein: the amount of imbibition has a range from about 30% to about 120%.