KR20050091779A - Compositions and treated substrates having reversibly adaptable surface energy properties and method for making the same - Google Patents

Abstract

The present invention relates generally to substrates that exhibit useful, auto adaptable surface energy properties that depend on the environment of the substrate. Such surface energy properties provide relatively high advancing and receding contact angles for liquids when in contact with the target substrate surface. The substrates exhibit low surface energy quantities of at most about 20 millijoules per square meter (mJ/m2) at a temperature of about 25 degrees C and a surface energy greater than about 20 mJ/m2 at, or with exposure to, a temperature of about 40 degrees C. More specifically, encompassed within the present invention are textile substrates having this highly desirable unique surface energy modification property and which exhibit wash durable oil and water repellency and stain release features. Novel compositions and formulations that impart such surface energy modifications to substrates are also encompassed within this invention, as well as methods for producing such treated substrates.

Description

COMPOSITIONS AND TREATED SUBSTRATES HAVING REVERSIBLY ADAPTABLE SURFACE ENERGY PROPERTIES AND METHOD FOR MAKING THE SAME

In general, the present invention relates to a substrate that exhibits useful self-regulating surface energy properties depending on the environment of the substrate. This surface energy characteristic provides a relatively high advancing and retracting contact angle for the liquid upon contact with the target substrate surface. In particular, the substrate shows a low amount of surface energy of about 20 mJ / m ² or less at a temperature of about 25 ° C., measured by the angle measurement method and calculated by the Fowkes equation, and at or about 40 ° C. When exposed to temperature it shows a surface energy of greater than about 20 mJ / m ² . This unique automatic surface energy change capability then provides a surface that is water and oil repellent, exhibits some stain resistance and confers effective stain release to the target substrate. In addition, this unique surface energy profile is repetitive and reversible depending on the exposure environment. Not only are new compositions and formulations imparting such surface energy changes to the substrates are also included in the present invention, but also methods of making the substrates so treated. More specifically, textile substrates having such highly desirable unique surface energy changing properties and exhibiting laundry durable oils and water repellency and stain release are included in the present invention.

Providing substrates such as garment fabrics, such as garment fabrics exhibiting many simultaneous laundry-durables, has long been a necessity, especially in the textile industry. Most notably, water repellency, oil repellency, stain resistance and stain releaseability highly favorably wash the substrates or otherwise prevent their complete staining. Unfortunately, the provision of these simultaneous and wash-durable properties has been severely limited because it is generally difficult to meet specific surface energy requirements over the wash durability life of such substrates. In general, coatings or other treatments that can provide a substrate (or other surface) with water and oil repellency and stain release coherence based on wash durability, may require that the surface energy profile required for one of these properties be different. It is not readily available or widely known because it is completely different from the surface energy profile required to impart it at the same time.

Although there are some examples (described below) in which both properties are initially present simultaneously on a particular substrate, unfortunately, their degree of laundry durability during the long term use of the target substrate becomes unacceptable. As a result, any significant reduction in oil or water repellency results in a decrease in stain repulsion as well. Due to the reduced tendency for stain repulsion, in particular when exposed to a greater degree of staining, the surface energy profile required for proper stain release function (similar to that required for imparting the aforementioned water and oil repellency) is impaired ( Eg, no wash-durability), the ability to realize proper stain release can likewise be reduced.

Therefore, since both polar (aqueous) and non-polar (olefinic) liquids, which can withstand extended conventional washing procedures, are very difficult to penetrate at the same time to such fabric surfaces, in practice long-term stain repulsions and stains that are effectively effective No release treatment was shown. This problem of conventional oil and water repellent surface treatments is most remarkably observed on typical high stain substrates such as cotton-containing fabrics. It is generally difficult to change these surfaces to the extent necessary to impart both oil and water repellency to these fabrics and to maintain an acceptable feel. These three or more properties (stain releasing, water repellency and oil repellency) have not been used simply in the textile industry on the basis of wash-durability because of the surface energy problems described above. This technique of surface energy properties helps to better understand this phenomenon.

The basic physical property of any material is its surface energy. This property is usually expressed as mJ / m ² . Depending on the magnitude of this property, materials can be classified as having high or low surface energy. This property generally depends on the composition of the substrate. For example, substrates having a surface containing a substantial portion of polar hydrophilic groups such as hydroxyl groups, carboxyl groups, amine groups and the like generally exhibit high surface energy. Conversely, substrates having a surface containing a substantial portion of nonpolar hydrophobic groups such as silicon, fluorinated groups, and the like, generally exhibit low surface energy. It is readily understood that when a polar liquid such as water contacts the surface of the substrate, the liquid spontaneously wets the surface only if the surface tension of the liquid is lower than the surface energy of the substrate. Conversely, when a polar liquid such as water comes into contact with the surface of the substrate, if the liquid has a higher surface tension of the liquid than the surface energy of the substrate, spontaneous wetting does not readily occur, and the liquid is on the surface of the substrate. Will remain stuck.

As expected, substrate surface energy changes have long been a major research area for a variety of materials. For example, it is often desirable to increase the surface energy of a substrate to promote liquid absorption capability or to increase the adhesion between the coating and the substrate. Practical examples include corona treatment of plastics to increase adhesion between plastics and other coatings of aluminum, such as aluminum coatings of Mylar® films, in the chemical treatment and packaging applications of paper or plastics to enhance wetting with printing inks. Include. In addition, the textile substrates are modified to result in substrates with high surface energy resulting in a textile substrate that is hydrophilic and exhibits improved comfort and stain release. As an example, the detergent industry uses this technique to determine effective ways of washing various textile substrates.

In addition, surface energy changes have been used in other coating applications to create non-adhesive surfaces that exhibit low surface energy, such as through application of Teflon® to cookware and cookware. Textile substrates have also been modified with low surface energy treatments to produce hydrophobic and repellent textile substrates (eg, for water repellent raincoats).

Substrates treated with fluorinated polymers have generally been known to exhibit contact angles greater than 100 ° with water. The forward and backward contact angles are very similar. The main factor in this surface energy treatment is dispersibility. Substrates treated with dual functional repellents, such as, for example, disclosed in U.S. Patent No. 3,574,791 to Zengman et al., Generally exhibit lower contact angles with water as compared to traditional fluorochemical repellents and therefore lower repulsion. There is a tendency to see it. The measured surface energy contains significant dispersibility and polar component. The difference between the advancing and retracting contact angles can typically be measured.

In some cases, there is a measurable degree of hysteresis between the advancing and receding contact angles, which means that the surface energy has changed in the presence of the liquid. When inhibiting liquid adsorption, hysteresis indicates that the surface energy has changed (dynamically or thermodynamically) in the presence of liquid or under environmental conditions. This measurable degree of hysteresis provides further evidence that the substrate is automatically adjusted to its environment. One way of achieving ideal performance for textile applications is to provide a high forward contact angle (i.e.> 90 degrees) with non-porous properties to impart stain resistance, and a low retracting contact angle (i.e. < 90 degrees) to obtain a stain release property to the substrate. Other methods of achieving ideal performance for this use will be obtained from compositions that give high advancing and high retract angles between the staining object and the substrate and then provide low advancing and retracting contact angles during exposure to the laundry procedure.

It may be desirable for porous or stained surfaces to exhibit high contact angles for various liquids to prevent adsorption or staining. It may also be desirable for such surfaces to be adapted to changes in the environment, such as in a wash medium. Other environmental conditions that can lead to changes in the surface energy of the substrate include changes in temperature, moisture content, and other environmental factors. It is highly desirable to have a surface that is reversibly adapted to the environment so that the surface is stain resistant and washable and maintains these effects over many use cycles. For many end-use applications such as garments, carpets, upholstery, etc., maintaining the appearance of the product is very important. Although stain resistant treatments have been developed for each of these exemplary applications, very similarly to stain resistant garment treatments, these treatments adversely affect subsequent laundering. Thus, regardless of the end-use application, it is highly desirable to develop small and stain resistant textile substrates with enhanced washability using suitable cleaning techniques.

With the development of XPS, SIMS and other surface analytical techniques, it has become possible to detect specific chemical groups on the material surface. For example, concentration and depth profiles of functional groups (eg, CF ₃ residues commonly found in fluoropolymer stain resistant chemicals) can be measured. Through suitable sample preparation techniques, changes can also be observed that occur on the surface of the substrate and occur as a result of changes in the environment to which the substrate is exposed. for example,

Substrates under the first set of conditions, observed to predominantly contain low surface energy groups, such as CF ₃ groups, may appear to contain significant hydrophilic, high surface energy groups, such as hydroxyl groups, on the surfaces under different second set of conditions. This polarity change typically causes the substrate surface to wet (ie, absorbs liquid), thereby enhancing stain release. As the environment of the substrate returns to the first set of conditions, for example, since the CF ₃ group returns to the surface of the substrate, the substrate surface returns to a low surface energy stain resistant state.

Some treatment compositions (eg, polymers) have other properties such as glass transition temperatures that can affect the ultimate performance of the treated substrate. For example, hard polymers that are characterized by high glass transition temperatures can increase the protection against wetting, especially forced wetting. However, these stiff high glass transition polymers will require more work to adapt to changes in the environment because of their less intra-polymer flexibility. In addition, the addition of polymer molecular weight and comonomers can also enhance wetting, adhesion, chemical reactivity and durability to various substrates.

It is evident above that modifications that provide an appropriate surface energy profile to confer simultaneous wash-durable oil repellency, water repellency, stain resistance and stain release to the target substrate have been studied for many hours without success.

As described herein, the present invention enables the adjustment of the surface properties of a target substrate such that certain combinations of chemicals and processing conditions preferably obtain a balanced surface energy profile to impart simultaneous repulsion and stain release to the substrate. And / or promote it. In addition, the combination of these unique features has surprisingly shown considerable durability upon exposure to conventional and industrial laundry methods.

Conventional technology

All US patent documents listed are hereby incorporated by reference in their entirety.

US Patent No. 2,841,573 to Albrecht et al. And US Patent No. 3,645,990 to Reynolds disclose the use of fluoropolymers to impart oil and water resistance to substrates. While actually providing some degree of stain resistance to the substrate, this treatment tended to have limited durability in laundry. In addition, such polymers inhibited the release of stains, particularly in environments where stains are forcibly wet the substrate or dry on the substrate. Indeed, removal of stains is more difficult in such circumstances than when no substrate is treated.

In addition to fluoropolymers, silicone waxes and various other compounds have been disclosed to impart resilience to textiles and other substrates. With the exception of fluoropolymers, such polymers usually provide only water repellency and have only limited durability for washing. Such techniques are disclosed, for example, in US Pat. No. 4,421,796 to Burrell et al.

US Pat. No. 3,574,791 to Sherman et al. And US Pat. No. 3,896,088 to Reynolds disclose a fluorinated oily stain release agent that imparts some water and oil repellency to the substrate without adversely affecting stain removal during washing. It starts. Basically, these patents all disclose polymers comprising fluorinated repulsive residues and hydrophilic residues. It is claimed that such polymers exhibit a "flip-flop" mechanism that exposes fluorinated fragments in air to provide stain resistance and then expose the hydrophilic fragments to an aqueous environment to provide stain release. Typically such polymers exhibit lower repulsion, in particular lower water repellency, than conventional fluorochemicals, and they also have the disadvantage of lack of laundry durability.

U. S. Patent No. 4,624, 676 to White et al. Discloses a unique silicone compound such as organosiloxane that imparts stain release to the substrate. Durability is claimed when these compounds are crosslinked. The compounds may be self-crosslinked, in particular when suitable catalysts are used, or they may be crosslinked with the substrate. Such compounds can provide resistance to aqueous stains, but rarely to oil based stains.

US Pat. No. 4,834,764 to Diner et al. Discloses the use of crosslinking resins such as methylol containing resins or blocked diisocyanates. Indeed, such resins increase the durability of the fluoropolymers against washing. These resins can be added to aqueous treatments containing fluoropolymers. However, in practice it increases the durability of stain repulsion, but acceptable stain release does not come from this combination.

U. S. Patent No. 4,540, 765 to Coem et al. Discloses a fluorochemical repellent with greater wash durability than previously seen. Typically, such polymers contain certain crosslinkable moieties in the polymer. Such crosslinkable moieties include methylol groups, blocked diisocyanate groups, epoxy groups and the like. Indeed such crosslinkable polymers have greater durability against laundering. As in the case of Denier's US Pat. No. 4,834,764, durability is improved, but no acceptable stain release is observed.

Marco's US Patent RE28,194 discloses the use of carboxylated acrylic stain release polymers, fluoropolymers and aminoplast resins for the preparation of cellulose-containing textiles with good stain repellency and improved stain release. . However, this treatment can only work on cellulose-containing textile substrates, except for most synthetic fibers.

US Pat. No. 4,695,488 to Hisamoto et al. Discloses a stain release composition comprising a fluoroalkyl group and an alkoxy group, a hydrophilic resin and a polymer optionally containing water and oil repellents. This composition claims to impart durable stain prevention and stain release to the substrate. However, the water and oil repellency levels are lower, and the disclosed anti-stain test shows more stain resistance than stain release.

While many attempts have been made to provide the desirable properties described above in these various fields, at the same time water repellency, oil repellency, and stain release are acceptable levels of specific substrates, especially fabrics, disclosed, or proposed in this industry, and Most notably there was no wash-durable treatment imparting to the cotton-containing fabric. Accordingly, none of the references cited above adequately discloses a surface having a durable high level of water and oil repellency and an acceptable level of stain release on various substrates and / or on the substrate. The market and consumer demand is that it is desirable for the various substrates to be resistant to staining by as many common staining materials as possible, while at the same time having the substrates with improved stain removal properties by using conventional laundry procedures suitable for the substrates. Has been shown. Such laundry procedures may include methods used in laundry, such as domestic or industrial washing machines or spot laundry procedures, such as furniture fabrics. In addition, various other conventional laundry procedures are contemplated, such as those used in carpet laundry and dry cleaning, for example. Thus, despite the long lasting need and consumer demand for substrates with durable repulsion and stain release properties, prior attempts have been insufficient to achieve this goal.

Summary of the Invention

Therefore, one object of the present invention is to provide a novel composition which simultaneously imparts washing-durable oil repellency, water repellency, stain resistance and stain release to the substrate. It is also an object of the present invention to provide durable high levels of water and oil repellency and acceptable levels during and after standard laundry procedures such as household and industrial laundry, dry cleaning, or other typical surface and / or substrate cleaning methods. Disclosed is a substrate showing stain release properties. Another object of the present invention is to disclose a method of treating a substrate to have a durable high level of oil and water repellency and acceptable stain release. It is another object of the present invention to apply such a novel composition to a particular fabric substrate so that such wash-durable properties can be applied to the substrate through typical immersion, padding, exhaustion or other application procedures or through a method of applying a domestic dryer. It includes without limitation.

Accordingly, the present invention includes a composition that changes the surface energy of a substrate in response to changes in the environment of the substrate, the composition comprising a high surface energy component, a low surface energy component, and a hydrophobic crosslinking component. More specifically, the present invention provides durable substrate and stain release properties comprising a product of at least one hydrophilic stain release agent, at least one hydrophobic stain repellent crosslinked by at least one hydrophobic crosslinker. Composition. In addition, the present invention is directed to polyester or cotton fabric substrates for testing specific resilience and stain release properties in terms of wash-durable and high oil repellency rating, water repellency rating, spray rating, and stain release rating. Fabric surface treatment compositions comprising at least one fluorinated polymer component. In this situation, the composition is defined as above in terms of the properties imparted to this particular test fabric, so the present invention does not require that such fabric be present as part of the composition of the present invention.

Other portions of the present invention include certain woven substrates consisting of at least 20% by weight cotton fibers based on the total weight of the substrate, wherein the substrates have an oil repellency rating of 4.0 or greater as measured by AATCC test method 118-2000; A water repellency rating of 4.0 or higher as measured by the 3M Water Repellency Test II (May 1992); Spray rating of 70 or higher as measured by AATCC Test Method 22-2000; A stain release rating of 4.0 or higher for corn oil and mineral oil as measured by AATCC test method 130-2000; After 20 washes, the test fabrics were washed and dried by AATCC test method 130-2000 and the above characteristics were shown. Alternatively, we include herein a textile substrate consisting of at least 20% by weight cotton fibers based on the total weight of the substrate, the substrate measured upon exposure to a temperature of about 25 ° C. in response to changes in the environment of the substrate. The surface energy is less than about 20 mJ / m ² , and the surface energy measured upon exposure to a temperature of about 40 ° C. shows a change in surface energy in the range of more than about 20 mJ / m ² .

Also provided are other textile substrates including, but not limited to, a textile substrate comprising a potentially preferred, polyester fiber, which is encompassed within the present invention, wherein the substrate has an oil repellency of at least 3.0 as measured by AATCC test method 118-2000. Rating; A water repellency rating of 3.0 or higher as measured by the 3M Water Repellency Test II (May 1992); Spray rating of 50 or higher as measured by AATCC Test Method 22-2000; Shows a stain release rating of at least 3.5 for corn oil and mineral oil as measured by AATCC test method 130-2000; After washing and drying the test fabric by AATCC Test Method 130-2000 after 20 washes, the test fabrics not only exhibited the above properties, but also exhibited the same surface energy change characteristics as described above for cotton fiber fabrics.

Also within the scope of the present invention,

(a) providing a substrate;

(b) coating the substrate with a composition consisting of a hydrophilic stain release agent, a hydrophobic stain repellent and a hydrophobic crosslinker;

(c) heating the substrate to remove substantially all of the excess liquid from the coated substrate; And

(d) optionally, further heating the coated substrate

Included are methods of imparting durable repellency and stain release to a substrate.

Such compositions, fabrics, and methods of the present invention are discussed in greater detail below.

1 is a graph of XPS surface chemical analysis for microdenier polyester textile substrates treated with the novel chemical composition of the present invention and several microdenier polyester textil substrates treated with various competitive chemical compositions.

FIG. 2, except that the graph shows surface chemical analysis of fluorine, carbon and oxygen before (ie, as received) the substrate and after washing and drying the substrate 10 times. Is a graph similar to FIG. 1.

Justice

"Water repellency" and "oil repulsion" are generally defined as the ability of a substrate to block water and oil from penetrating into the substrate, respectively. For example, the substrate can be a textile substrate that can block the penetration of water and oil into the fibers of the textile substrate.

"Stain release" is generally defined as the extent to which the stained substrate approaches the original unstained appearance as a result of the care procedure. As defined herein, high levels of stain resistance can be determined by an oil repellency grade of at least 3.0 as measured by AATCC test method 118-2000; A water repellency rating of at least 1.0 as measured by the 3M Water Repellency Test II (May 1992); Means a spray grade of 50 or greater as measured by AATCC Test Method 22-2000, as defined herein, an acceptable stain release is at least 3.0 for corn oil and mineral oil release as measured by AATCC Test Method 130-2000. Means rating.

"Laundry durability" is generally defined as the ability of a substrate to retain an acceptable level of desirable functionality through a reasonable number of standard wash cycles. More specifically, the durability used herein is a stain resistance, number after at least 10 wash cycles, more preferably after 20 wash cycles, most preferably after 50 wash cycles, according to AATCC test method 130-2000. It is intended to describe a substrate that retains the proper properties of repellency, oil repellency, and spray grade. Such substrate may be a textile substrate, such as a polyester textile fabric.

The terms "fluorocarbon", "fluoropolymer" and "fluorochemical" are used interchangeably herein and refer to polymeric materials, each containing one or more fluorinated fragments.

The term "padded" means that the liquid coating is applied to the substrate by passing through a bath and then through a squeeze roller.

"Hydrophilicity" is defined as having a strong affinity for water or the ability to absorb water.

"Hydrophobic" is defined as lacking affinity for water or the ability to absorb water.

“High surface energy” is defined as the surface energy of at least about 25 mJ / m ² at about 25 ° C., calculated from the Poux 2 component approach to solid surface energy (for further information on the Poux equation, see Foxx Industrial and Engineering Chemistry, 1964, Chapters 12, 40, and 56).

“Low surface energy” is defined as surface energy of less than about 25 mJ / m ² at 25 ° C., calculated from the Pooxes two component approach to solid surface energy.

High surface energy surfaces describe surfaces (eg, faces) that can be spontaneously moistened (<90 ° contact angle) by low surface tension liquids such as water.

Surfaces of low surface energy (e.g. Teflon®) do not spontaneously get wet by water, but maintain a contact angle of> 90 ° with a liquid containing a higher surface tension (about> 25 mN / m). to be.

Composition :

Compositions useful for making a substrate durable and stain resistant and stain release typically consist of a hydrophilic stain release agent, a hydrophobic stain repellent, a hydrophobic crosslinker, and optionally other additives that impart desirable properties to the substrate. Within the scope of the present invention, novel chemical compositions are contemplated in which the relative amounts and chain lengths of each of the aforementioned chemical agents can be optimized to achieve the desired level of performance for different target substrates within a single chemical composition.

Hydrophilic stain release agents include ethoxylated polyesters, sulfonated polyesters, ethoxylated nylons, carboxylated acrylics, cellulose ethers or esters, hydrolyzed polymaleic anhydrides, polyvinylalcohol polymers, polyacrylamide polymers, hydrophilic fluorinated stains Release polymers, ethoxylated silicone polymers, polyoxyethylene polymers, polyoxyethylene-polyoxypropylene copolymers, and the like, or combinations thereof. Hydrophilic fluorinated stain releasing polymers may be preferred stain releasing agents. Potentially preferred compounds of this type are UNIDYNE® TG-922 (available from Daikin Corporation), REPEARL® SR1100 (available from Mitsubishi Corporation), and ZONYL® 7910 (from DuPont) Available), but is not limited to such. Treatment of substrates with hydrophilic stain emitters generally results in surfaces showing high surface energy.

Hydrophobic stain repellents include waxes, silicones, certain hydrophobic resins, fluoropolymers, and the like, or combinations thereof. The fluoropolymer may be the preferred stain repellent. Potentially preferred compounds of this type include REPEARL® F8025 and REPEARL® F-89 (all of which are available from Mitsubishi Corporation) and ZONYL® 7713 (available from Dupont) It is not limited to this. Treatment of the substrate with a hydrophobic stain release agent generally results in a surface showing low surface energy.

Hydrophobic crosslinkers include those that are crosslinkers that are insoluble in water. More specifically, hydrophobic crosslinkers include blocked isocyanate-containing monomers (eg, blocked diisocyanates), blocked isocyanate-containing polymers (eg, blocked diisocyanates), epoxy Containing compounds and the like or combinations thereof. Diisocyanate containing monomers or diisocyanate containing polymers may be preferred crosslinkers. However, monomers or polymers containing two or more blocked isocyanate compounds may be the most preferred crosslinkers. One potentially preferred crosslinker is REPEARL® MF (also available from Mitsubishi Corporation). Others include ARKOPHOB® DAN (available from Client), EPI-REZ® 5003 W55 (available from Shell) and HYDROPHOBOL® XAN (available from DuPont).

The total amount of chemical composition applied to the substrate and the proportion of each chemical agent comprising the chemical composition can vary widely. The total amount of chemical composition applied to the substrate will generally depend on the composition of the substrate, the level of durability required for a given end-use application, and the cost of the chemical composition. As a general guideline, the total amount of chemical solids applied to the substrate will range from about 0.25% to about 10.0% of the weight of the substrate. More preferably, the total amount of chemical solids applied to the substrate will be in the range of about 0.5% to about 5.0% of the weight of the substrate. Typical solid ratios and concentration ratios of stain repellent to stain releaser to crosslinker may be from about 10: 1: 0.1 to about 1: 10: 5 (including all ratios and ratios that may be within this range). Preferably, typical solid ratios and concentration ratios of stain repellent to stain releaser to crosslinker may be from about 5: 1: 0.1 to about 1: 5: 2. Most preferably, the typical solid ratio and concentration ratio of stain repellent to stain releaser to crosslinker may be about 1: 2: 1.

The ratio of stain release agent to stain repellent to crosslinker may likewise vary based on the relative importance of each property being changed. For example, higher levels of outbreaks may be required for a given end use application. As a result, the amount of repellent relative to the amount of stain release agent can be increased. Alternatively, higher levels of stain release may be seen as more important than higher levels of stain resilience.

For the production of more economical chemical compositions, the types of stain release agents, stain repellents and crosslinkers may vary based on the end use application of the substrate treated with the chemical composition. For example, the treated substrate can be prepared without anticipating the encounter with oil-based stains. Thus, more economical repellents (eg silicone) can be used as one component of the chemical composition.

Substrates of the invention may include glass, fiberglass, metals, films, paper, plastics, stones, bricks, textiles, or combinations thereof. Glass, such as window glass in buildings or automobiles, may be useful from the present invention. In addition, metal products such as, for example, bridges or automobile bodies may be useful from the present invention. Such items may resist staining by conventional soiling and may be cleaned by rain or the like. The film may comprise a thermoplastic, a thermoset or a combination thereof. Suitable thermoplastic or thermoset materials include polyolefins, polyesters, polyamides, polyurethanes, acrylics, silicones, melamine compounds, polyvinyl acetates, polyvinyl alcohols, nitrile rubbers, ionomers, polyvinyl chlorides, polyvinylidene chlorides, chloroisoprene Or combinations thereof. The polyolefin can be polyethylene, polypropylene, ethylvinyl acetate, ethylmethyl acetate or combinations thereof.

Textile substrates include one non-limiting embodiment of the invention that is potentially preferred. The textile substrate can be any known structure, including knit structures, woven structures, nonwoven structures, and the like, or combinations thereof. The textile substrate may have a fabric weight of about 1 to about 55 ounces / yard ² , more preferably about 2 to about 12 ounces / yard ² .

The textile based material may be synthetic fibers, natural fibers, artificial fibers using natural ingredients, inorganic fibers, glass fibers or any blend thereof. By way of example only, synthetic fibers may comprise polyesters, acrylics, polyamides, polyolefins, polyaramids, polyurethanes or blends thereof. More specifically, the polyester may comprise polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polylactic acid or combinations thereof. Polyamides may include nylon 6, nylon 6,6 or combinations thereof. The polyolefin may comprise polypropylene, polyethylene or combinations thereof. Polyaramids may include poly-p-phenyleneterephthalaramid (ie, Kevlar®), poly-m-phenyleneterephthalaramid (ie, Nomex®), or combinations thereof. . Exemplary natural fibers may include wool, cotton, linen, ramie, jute, flax, silk, hemp or combinations thereof. Exemplary artificial materials using natural ingredients include regenerated cellulose (ie, rayon), lyocells, or mixtures thereof.

The textile substrate may be formed from staple fibers, filament fibers, slit film fibers or combinations thereof. The fiber can be exposed to one or more texturing processes. The fibers may then be spun into yarn or otherwise combined, for example by ring spinning, open-end spinning, air jet spinning or a combination thereof. Thus, the textile substrate will generally consist of interlaced fibers, interlaced yarns, loops or combinations thereof.

The textile substrate may be comprised of fibers or yarns of any size, including microdenier fibers or yarns (fibers or yarns having less than 1 denier per filament). The fibers or yarns may have deniers ranging from less than about 1 denier per filament to about 2000 denier per filament, more preferably less than about 1 denier per filament to about 500 denier per filament.

In addition, textile substrates may be partially or wholly in various shapes, such as islands-in-the-sea, core and sheath, side-by-side. Or pie-shaped multi-component or bi-component fibers or yarns. Depending on the shape of the bi- or multi-component fibers or yarns, the fibers or yarns can be split along the length by chemical or mechanical action.

Textile substrates may, for example, be printed or dyed to create an aesthetically pleasing decorative design on the substrate or to print an information message on the substrate. Textile substrates can be subjected to a variety of dyeing and / or printing techniques, such as high temperature jet dyeing using disperse dyes, thermosol dyeing, pad dyeing, transfer printing, screen printing, digital printing, ink jet printing, flexographic printing or comparable. It may be colored by any other technique common in the art for equivalent traditional textile products. In addition, fibers or yarns comprising the textile substrates of the present invention may be dyed by suitable methods such as via package dyeing, solution dyeing, or beam dyeing prior to substrate formation, or they may be left undyed. Can be. In one embodiment, the textile substrate can be printed with a solvent-based dye rather than an aqueous dye. Solvent-based dyes may make the hydrophobic surface of the present invention more homogeneous.

It is also contemplated that the textile substrate composite material may be formed by combining one or more textile substrate layers together. For example, it may be desirable to combine several open weave textile substrate layers together to form a textile substrate composite material. In addition, the composite material may include an adhesive material or one or more film layers. The composite material can then be treated with the chemical composition of the present invention to achieve a material that exhibits durable stain repellency and stain release. Alternatively, in another embodiment of the present invention, a textile substrate comprising a composite material may be treated with a chemical composition prior to being combined into the composite material.

In one potentially preferred embodiment of the present invention, daily necessities having a limited useful life can be treated with a minimum amount of chemicals to achieve the required properties. More specifically, the substrate, such as a lightweight polyester disposable wrap coat, may have only about 0.25% to about 1.5% of the chemical solids applied to the substrate. Conversely, in another potential preferred embodiment of the present invention, a high quality product with a longer useful life can be treated with almost the maximum amount of chemicals to achieve the desired level of durability. More specifically, the substrate, such as a high quality cotton apparel product or a polyester / cotton blend coverall uniform, may have from about 1.0% to about 10.0% of the chemical solids applied to the substrate.

The application of stain release agents, stain repellents and crosslinkers to textile substrates can be accomplished by various application methods, including impregnating coatings, padding, spraying, foam coatings, consuming techniques, or by those skilled in the art applying a limited amount of suspension to textile substrates. It can be accomplished by any other technique that can. One or more of these application techniques may be used to apply the chemicals to the textile substrate in a homogeneous manner.

The chemical agent may be applied to the textile substrate simultaneously or sequentially. For example, the stain release agent, the stain repellent and the hydrophobic crosslinker can be mixed together in one solution and then simultaneously applied to the textile substrate by padding. After applying the chemical to the textile substrate, the treated substrate is generally exposed to a drying step to evaporate excess liquid leaving a solvent active ingredient on the treated substrate. Drying can be accomplished by any technique typically used in the manufacturing process, such as dry heating from the tenter frame, microwave energy, infrared heating, steam, superheated steam, autoclaving, or any combination thereof. . In another embodiment, a stain release agent can be applied to the textile substrate, the substrate can remain dry or wet, and then a stain repellent and a hydrophobic crosslinker are applied on top of the stain release agent to the textile substrate. It is possible to create a sequential chemical treatment deposited on the surface of the.

It may be desirable to expose the treated substrate to an additional heating step to further enhance the performance or durability of the chemical formulation. This step may be referred to as a curing step. For example, additional heating (a) melt-flows the individual particles of the active ingredient of the chemical agent together, resulting in a homogeneous cohesive film layer; (b) derive the desired arrangement of the particular fragment of the chemical agent; (c) induce a crosslinking reaction between the chemical agent or between the chemical agent and the substrate; Or (d) allow a combination of these.

In many instances, despite the end use, it is desirable for textile substrates to satisfactorily exhibit properties other than durable stain resistance and stain release. Examples of these properties include static protection, wrinkle resistance, shrinkage reduction or removal, desirable hand (or tactile) requirements, dye fastness requirements, odor removal, flammability requirements, and resistance to dry soiling. Include. Unexpectedly, textile substrates treated in accordance with the present invention actually exhibit certain desirable anti-cling and antistatic properties of the substrate, such as during garment cutting and sewing processes.

Thus, it may be desirable to treat textile substrates with chemical containing finishes such as antimicrobials, antibiotics, antimicrobials, flame retardants, UV inhibitors, antioxidants, colorants, lubricants, antistatic agents, fragrances, and the like, or combinations thereof. Chemical application can be accomplished by various application methods, including impregnating coating, padding, spraying, foam coating, consuming techniques, or by any other technique in which a person skilled in the art can apply a limited amount of suspension to a textile substrate. . One or more of these application techniques may be used to apply the chemicals to the textile substrate in a homogeneous manner. Many such chemical treatments may be incorporated simultaneously with the chemical composition of the invention, or such treatment may be carried out prior to treatment with the chemical composition of the invention. It is also possible to apply many of these chemical treatments using appropriate techniques after treatment with the chemical composition of the present invention.

In addition, textile substrates can be processed by mechanical finishing techniques. For example, calendaring, embossing, etching, rainbow or hologram embossing, film or metal foil hologram embossing, fabric metallization, heat curing, hydroentanglement with water or air, sanding, gloss, schrininering ), Sueding, sanding, emorizing, napping, shearing, tigering, deciding, water, air, laser or patterning It may be desirable to expose the textile substrate to fabric patterning through a rolled roll, or the like, or a combination thereof. Such mechanical treatment typically provides the textile substrate with a desirable effect that affects properties such as the appearance, strength, and / or feel of the fabric. Depending on which mechanical treatment is used, the benefits may be obtained by treatment before or after the application of the chemicals of the invention. For example, benefits from sanding before chemical treatment and calendaring after chemical treatment can be expected.

Within the scope of the present invention, it is also contemplated that asymmetrical textile substrates may be produced using surfaces having dual functional properties. For example, a textile substrate having a first and a second surface can be made to have a first hydrophobic surface and a second hydrophilic surface. Such dual functional textile substrates can be prepared, for example, by coating both surfaces of a textile substrate with a hydrophilic stain release agent and then coating the first side of the substrate with a hydrophobic stain release agent and a hydrophobic crosslinker. Chemical applications include any of the foregoing, such as spray coating, foam coating, and the like. As a result, a garment made in this manner increases protection from environmental or chemical attack by repelling liquid on the first surface of the garment, while absorbing moisture, such as sweat, on the second surface of the garment. Can increase the wearer's comfort.

Description of the Preferred Embodiments

Treatment Compositions and Their Application to Textile Substrates

A) Fabric application procedure:

It should be noted that all the examples that follow are handled according to one of the following procedures.

I) One Step Application Procedure:

1. A piece of fabric about 14 inches by 18 inches was immersed in a bath containing a chemical composition of the desired chemical formulation.

2. Unless stated otherwise, all percentages of chemicals are% by weight based on the total weight of the bath produced, with the remainder consisting of water given% or grams of chemical. In addition, the% chemicals were based on the chemicals obtained from the manufacturer (eg, for compositions containing 30% active ingredient, X% of this 30% composition is used).

3. After the fabric is fully wetted, the fabric is removed from the treatment bath and run between squeeze rolls of about 40 psi, generally yielding a homogeneous pickup of about 50 to about 90%.

4. Pull the fabric as directed and plug it into the frame to maintain the desired dimensions.

5. The pin frame was placed in a dispatch oven at a temperature of about 300 to about 400 ° F. for about 0.5 to about 5 minutes to dry, and the fabric was heat cured to cure the final product.

6. Once removed from the oven, the fabric is removed from the pin frame and allowed to equilibrate at room temperature prior to testing.

II) Two steps application procedure:

1. The one step application procedure was repeated except that one or more chemical agents comprising the chemical composition were individually applied to the fabric in a specific order, rather than adding all chemical agents to one chemical bath.

2. The fabric was impregnated in a bath containing at least one chemical agent comprising the chemical composition.

3. After the fabric was fully wet, the fabric was removed from the treatment bath as described in the one step application procedure and the fabric was moved between squeeze rolls.

4. The fabric was dried in a dispatch oven at a temperature of about 300 ° F. for about 5 minutes.

5. The fabric was then impregnated with a new bath containing the residual desired chemical agent comprising the chemical composition.

6. The fabric was then dried and cured as in one step application procedure.

III) Other Two Steps Application Procedures:

1. Approximately 100 g of fabric was placed in a Warner-Matis laboratory dyeing apparatus.

2. About 2 liters of water containing the desired chemical were added to the jet dyeing apparatus.

3. The dyeing apparatus was closed, heated to about 130 ° C. and held at this temperature for about 30 minutes. As the water was heated the pressure was increased to about 3 bar.

4. The dyeing apparatus was cooled to about 70 ° C. and the treatment bath was drained.

5. The fabric was centrifuged in a dyeing apparatus to remove excess liquor.

6. While still wet, the fabric was impregnated into the treatment bath containing the desired chemical agent. Typically, the fabric was impregnated for about 1 to 10 seconds.

7. Once removed from this bath, the fabric was squeezed through a pad roll, placed on a pin frame, dried and cured as described in the one step application procedure described above.

IV) Post-curing application procedure:

1. The one step application procedure is repeated except that the fabric is dried and the chemical formulation is cured as follows, rather than curing the plasticizing crosslinker during one drying step:

(a) The fabric was dried in a dispatch oven at a temperature of about 300 ° F. for about 5 minutes.

(b) The fabric was then exposed to steam in a hot head press set set at 320 ° F. as follows:

i) 5 seconds at high pressure

ii) 10 seconds in head steam

iii) 5 seconds in buck steam

iv) 5 seconds at buck vacuum; And

(c) The fabric was then cured at a temperature of about 300 ° F. for 10 minutes (simulating the process to cure the permanent post-cured resin at the garment manufacturer).

V) Application Procedures for Household Dryers:

1. An 8 x 9 inch piece of fabric was cut for this procedure, a 4.5 inch x 6 inch mold was made and placed on top of the fabric.

2. The chemical composition was placed in a spray bottle and 2.5 g of solution was sprayed onto the fabric through the mold opening.

3. The treated fabrics were placed in a Dryel® home dry laundry bag obtained from a Dryel® home dry laundry kit and placed in a home dryer for about 30 minutes at a high set point.

4. The fabric sample was removed from the dryer and conditioned at room temperature for about 15 to about 45 minutes before testing.

B) Treatment Compositions Used herein

Example 1:

A 200 g bath containing the following chemicals was prepared:

1. 9 g Unidyne TG-992 (fluorinated hydrophilic stain release agent available from Daikin Corporation);

2. 3 g Repearl F8025 (fluorinated stain repellent available from Mitsubishi Corporation); And

3. 3.6 g of Repearl MF (blocked hydrophobic diisocyanate crosslinker available from Mitsubishi Corporation).

The 100% microdenier polyester fabric was treated with this chemical composition according to the one step application procedure described above. The wet pickup of the chemical composition on the fabric was about 60%.

Polyester fabrics were obtained from Milliken & Campani, Spartanburg, South Carolina. The fabric is textured filament polyester 1/40/200 denier warp yarns and textured filament polyester woven together in a 2 x 2 right hand twill pattern with 175 warp yarns and 80 fill yarns per inch of fabric. Made of 1/150/100 denier peel yarns (hereinafter referred to as "test polyester fabric"). The fabric was treated with a face finishing process that included sanding the fabric surface lightly, followed by jet dyeing. The finished fabric had a weight of about 6 ounces per square yard.

0 household washing ("AR" means "as received"), 10 household washings, 20 household washings, 30 household washings, 40 household washings and 50 household washings Fabrics treated by the method were tested for water and oil repellency, spray grade and corn oil and mineral oil stain release. The test results are shown in FIG. IA.

Example 2:

Example 1 was repeated except that the concentration of the chemical agent was changed as follows:

Example 2A: 8.0 g Unidyne TG-992, 2.4 g Repearl F8025, 3.0 g Repearl MF;

Example 2B: 4.0 g Unidyne TG-992, 6 g Repearl F8025, 3.0 g Repearl MF; And

Example 2C: 2.0 g Unidyne TG-992, 6 g Repearl F8025, 3.0 g Repearl MF.

The results are shown in Table IA.

Example 3 (comparative example):

Example 1 was repeated except that one chemical agent of the chemical composition was omitted from the bath as follows:

Example 3A: Not using Unidyne TG-992;

Example 3B: without using Repearl F8025; And

Example 3C: No Repearl MF.

The results are shown in Table IA.

Example 4:

Example 1 was repeated except that some chemical formulations of the chemical composition were replaced with alternative chemicals available from various manufacturers, including:

Example 4A: Repearl F8025 was replaced with 1% Unidyne TG-571 available from Daikin Corporation;

Example 4B: Repearl F8025 was replaced with 2% Zonyl 7713 available from Dupont;

Example 4C: Repearl F8025 was replaced with 3% Zonyl 7713 available from Dupont and 4.5% Unidyne TG-992 was replaced with 1% Zonyl 7910 available from Dupont.

The wet pickup degree of the chemical composition on the fabric was about 60%. Test results are shown in Table IA.

Example 5:

Two polyester fabrics useful for bedspreads were prepared in Milliken and Campani and treated as the following chemicals following the one step application procedure described above:

1.4.5% Unidyne TG-992;

2. 1% Repearl F8025; And

3. 1.8% Arkophob DAN (hydrophobic crosslinker available from Client).

The wet pickup degree of the chemical composition on the fabric was about 75%.

Example 5A has a flat-spun polyester 56T DB 1/200/136 denier warp yarn and a flat-spun polyester 56T DB 2/150/68 denier fill available from Dupont with linen weave fill) treated one polyester bedspread fabric consisting of yarn. The fabric is further comprised of 61 warp ends per inch of fabric and 45 fill yarns per inch of fabric and has a final fabric weight of about 8.75 ounces / yard ² .

Example 5B was identical to Example 5A except that the polyester bedspread fabric was transferred to print after treatment with the chemical of the present invention.

Example 5C is a flat-spun polyester T-121 8 / with a flat-spun polyester fb3 SDY 75/36 denier warp yarn available from Nanya, with a faille weave The treatment of another polyester bedspread fabric consisting of one denier fill yarn was included. The fabric further consists of 164 warp ends per inch of fabric and 37 fill yarns per inch of fabric and has a final fabric weight of about 10.5 ounces / yard ² .

Example 5D was identical to Example 5C except that the polyester bedspread fabric was transferred to print after treatment with the chemical of the present invention.

Fabrics treated by the above-described method after zero industrial laundering (“AR” means “as received”) and five industrial laundering can be subjected to water and oil repellency, spray grade and corn oil and minerals. Tested for oil stain release. The test results are shown in FIG. IB.

Example 6 (comparative)

Example 1 was repeated except that each chemical formulation of the present chemical composition was replaced with various competing stain release and / or stain repellent chemicals. Examples G and H were purchased garments (pants) tested with the following treated fabrics. The chemicals used are:

Example 6A: 5.0% Scotchgard FC-5120 (stain repellent available from 3M)

Example 6B: 5.0% Zonyl 7040 (stain repellent available from Dupont)

Example 6C: 8.0% Scotchgard L-18542 (stain repellent available from 3M)

Example 6D: 5.0% Scotchgard FC-248 (fluorinated stain releasing agent available from 3M)

Example 6E: 5.0% Zonyl 7910 (Fluorinated Stain Release Agent available from Dupont)

Example 6F: 5.0% Scotchgard L-18369 (PM 490) (fluorinated stain release agent available from 3M)

Example 6G: Stain Defender Pants (DuPont Teflon® in Polyester / Cotton Blends)

Example 6H NanoCare Pants (100% cotton believed to be treated according to US Pat. No. 6,379,753 assigned to Nanotex)

Example 6I:

2.5% Unidyne TG-992

0.5% Reactant 901

0.25% Zinc Nitrate Hydrate

0.35% Unidyne TG-571 (Example 11 of Daikin's U.S. Patent No. 4,695,488)

Example 6J:

3.0% Repearl F8025

2.0% Repearl SR-1100 (Stain Release Agent available from Mitsubishi Corporation).

The test results are shown in Table II.

Example 7 (comparative)

Example 1 was repeated except that the polyester fabric was treated according to the two step application procedure described above. In the first step of the procedure, 6.0 g of PD-75 (carboxylated acrylic stain release agent available from Milliken & Co.) and 0.5 g of calcium acetate were applied to the fabric. In the second step of the procedure, 6 g of Repearl F8025, fluorinated stain repellent and 3.0 g of Repearl MF were applied to the fabric.

After zero household washings (“AR” means “as received”), five household washings and thirty household washings, the fabric treated by the method described above was subjected to water and oil repellency, spray grade. And corn oil and mineral oil stain release. The test results are shown in FIG.

Example 8:

Example 1 was repeated except that the polyester fabric was treated according to the alternative two step application procedure described above. In the first step of the procedure, 2% Unidyne TG-992 for the fabric weight and 1.0% acetic acid for the fabric weight were applied to the fabric in the dyeing apparatus. In the second step of the procedure, 8.0% Repearl F8025 and 9.6% Repearl MF were applied to the fabric sequentially.

After zero household washings (“AR” means “as received”), five household washings and thirty household washings, the fabric treated by the method described above was subjected to water and oil repellency, spray grade. And corn oil and mineral oil stain release. The test results are shown in FIG.

Example 9:

A 200 g bath containing the following chemicals was prepared:

a. 12g Unidyne TG-992;

b. 4g Repearl F8025;

c. 4g Repearl MF;

d. 16g Freerez PFK (permanent press resin available from Noveon Inc.);

e. 4 g of Catalyst 531 (catalyst available from Omninova Solutions); And

f. 4 g of Atebin 1062 (emollient available from Boehm Filatex).

100% cotton fabric was treated as this chemical composition according to the one step application procedure described above. The wet pickup degree of the chemical composition on the fabric was about 60%.

The fabric was obtained from Milliken & Campani, Spartanburg, South Carolina. The fabric is a 20/1 denier ring spun yarn and 11/1 denier open end spinned fill that are woven together in a 3 x 1 left hand twill pattern with 118 warp yarns and 54 fill yarns per inch of fabric. Made of yarn. The fabric is then dyed through a continuous dyeing process, sanitized and then treated with the chemical composition. The finished fabric has a weight of about 8 oz / yard ² (hereinafter, specifically referred to herein as "test cotton fabric").

After 0 times household washing (“AR” means “as received”), 10 times household washing, 20 times household washing and 30 times household washing, the fabric treated by the method described above can be water and oil. Resilience, spray grades and corn oil and mineral oil stain release were tested. The test results are shown in FIG.

Example 10:

Example 9 was repeated except that Repearl F8025 was replaced with Zonyl 7713 and Repearl MF was replaced with Hydrophobol XAN with the concentrations changed as follows:

Example 10A:

8.0 g Unidyne TG-992,

4.0 g of Zonyl 7713,

4.0 g Hydrophobol XAN (hydrophobic crosslinker available from Dupont);

Example 10B:

6.0 g of Unidyne TG-992,

6.0 g of Zonyl 7713,

4.0 g of Hydrophobol XAN; And

Example 10C:

4.0 g Unidyne TG-992,

8.0 g of Zonyl 7713,

4.0 g of Hydrophobol XAN.

Test results are shown in Table IV.

Example 11 (comparative)

Example 9 was repeated except that one chemical agent in the chemical composition was removed from the bath as follows:

Example 11A: Unidyne TG-992 not used;

Example 11B: no stain repellent; And

Example 11C: No hydrophobic crosslinker used.

The results are shown in Table IV.

Example 12 (comparative)

Example 9 was repeated except that each chemical formulation of the present chemical composition was replaced with various competing stain release and / or stain repellent chemicals (the same amounts of chemicals and chemicals used in Example 6). Examples G and H were purchased garments (pants) tested with the following treated fabrics. The chemicals used are:

Example 12A: 5.0% Scotchgard FC-5120;

Example 12B: 5.0% Zonyl 7040;

Example 12C: 8.0% Scotchgard L-18542;

Example 12D: 5.0% Scotchgard FC-248;

Example 12E: 5.0% Zonyl 7910;

Example 12F: 5.0% Scotchgard L-18369 (PM 490);

Example 12G: Stain Defender Pants (DuPont Teflon ™ of Polyester / Cotton Blend Apparel);

Example 12H: Nanocare Pants (100% cotton believed to be treated according to US Pat. No. 6,379,753 assigned to Nanotex);

Example 12I:

2.5% Unidyne TG-992

0.5% Reactant 901

0.25% Zinc Nitrate Hydrate

0.35% Unidyne TG-571 (Example 11 of Daikin's U.S. Patent No. 4,695,488)

Example 12J:

3.0% Repearl F8025

2.0% Repearl SR-1100.

The test results are shown in Table V.

Example 13:

The polyester and cotton blended fabrics were treated as novel chemicals of the present invention following the one step application procedure and the post application curing procedure described above. The fabric was obtained from Milliken & Campani, Spartanburg, South Carolina. The fabric consisted of about 65% polyester yarns and about 35% cotton yarns. The warp yarns consisted of 14.0 / 1 open end spinning 65/35 polyester / cotton staple fibers with 3.30 twist multiflow. Polyester staple fibers for both warp and peel yarn had about 1.2 denier. The warp and peel yarns were woven together in a 3 × 1 left twill pattern with 100 warps and 47 fill yarns per inch of fabric. The fabric was then dyed through a continuous dyeing process and treated with the chemicals of the present invention. The finished fabric had a weight of about 8.5 ounces / yard ² .

The chemicals of the present invention included the following formulations:

Example 13A: Prepared using a one step application procedure,

3.75% Unidyne TG-992

1.25% Zonyl 7713 (repellant available from Dupont)

1.25% Arkophob DAN

10% Permafresh MFX (permanent press resin available from Omninova)

2.5% Catalyst KR (catalyst available from Omninova)

0.25% Tebefoam (defoamer available from Boem Pilatex)

0.5% Mykon XLT (softener available from Omninova)

Example 13B: made using a one step application procedure,

5.4% Unidyne TG-992

1.75% Zonyl 7713

2% Arkophob DAN

10% Permafresh MFX

2.5% Catalyst EN

0.25% Tebefoam

0.5% Mykon XLT

Example 13C: prepared using a one step application procedure,

0.32% Unidyne TG-992

1.76% Arkophob DAN

3.87% Zonyl 7910

1.55% Repearl F8025

10% Permafresh MFX

2.5% Catalyst EN

0.25% Tebefoam

0.5% Mykon XLT

Example 13D: prepared using a one step application procedure,

5% Unidyne TG-992

1% Repearl F-89

3% Epi-Rez 5003 W55 (hydrophobic crosslinker available from Shell)

Example 13E: Prepared using a one step application procedure,

5% Unidyne TG-992

1% Repearl F-89

2% Witcobond W-293 (hydrophobic crosslinker available from Chromton)

Example 13F: Prepared using the application procedure after curing,

5% Unidyne TG-992

1% Repearl F-89

3% Epi-Rez 5003 W55

5% Permafresh MFX

1.25% Catalyst EN

0.25% Tebefoam

0.5% Mykon XLT

Example 13G: Prepared using an application procedure after curing,

5% Unidyne TG-992

1% Repearl F-89

2% Witcobond W-293

5% Permafresh MFX

1.25% Catalyst EN

0.25% Tebefoam

0.5% Mykon XLT

Example 13H Same as 13F, but with 1% Pluronic F-68 (Stain Release Agent available from BASF).

Example 13I: Same as 13G, but with 1% Pluronic F-68 added.

Example 13F is the same as used in Example 13D, except that the permanent press resin is used with other adjuvants and the composition does not fully cure, allowing permanent crease to be induced into the fabric. Chemical compositions were included. However, the fabrics were fully cured prior to testing and processed at the garment manufacturing facility. Similarly, Example 13G is an example, except that permanent press resins are used with other auxiliaries and the composition is not fully cured so that the permanent wrinkles can be induced into the fabric using resin treatment after curing. The same chemical composition as used in 13E was included.

Example 13H includes the addition of a polyoxyethylene-polypropylene copolymer (Pluronic F-68 from BASF) to the same chemical composition as used for 13F. This was applied as a post cure application method. Example 13I includes the addition of a polyoxyethylene-polypropylene copolymer (Pluronic F-68 from BASF) in the same chemical composition as used for 13F. This was also applied as a method of application after curing.

Fabrics treated by the method described above after zero household washing ("AR" means "as received"), five household laundry, ten household, 20 household laundry and 30 household laundry Were tested for water and oil repellency, spray grade and corn oil and mineral oil stain release. The test results are shown in FIG. VI.

Example 14 (comparative)

Example 13 was repeated except that each chemical formulation of the chemical composition was replaced with various competing stain release agents and / or stain repellents.

In addition, the fabric used in Example 14D is slightly different in structure from the fabric described in Example 13. The 14D fabric is also a 65/35 polyester / cotton blend fabric. However, the warp yarns consisted of 16/1 open end spinning 65/35 polyester / cotton staple fibers with 3.3 twist multiples. Peel yarn is a 12.0 / 1 open end spun 65/35 polyester / cotton staple fiber. Polyester staple fibers for both warp and peel yarn had a denier of about 1.2. The warp and fill yarns were woven together in a 2 × 1 left hand twill pattern with 88 warp yarns and 46 fill yarns per inch of fabric. The fabric was then dyed through a continuous dyeing process and treated with the chemicals of the present invention. The finished fabric had a weight of about 7.2 ounces / yard ² .

The chemical composition is as follows:

Example 14A: Prepared using a one step application procedure,

1.5% Zonyl 7910

18% Permafresh MFX

4.5% Catalyst US

1.25% Mykon XLT

0.5% Tebefoam 1868

0.35% Progapol DAP-9

Example 14B: prepared using a one step application procedure,

11.1% Scotchgard L-18369

2.2% Hydrophobol XAN

9% Permafresh MFX

2.2% Catalyst 531

1% Mykon NRW3

Example 14C: prepared using a one step application procedure,

6% Zonyl 7713

6% Zonyl 7714

2% Hipochem CSA

3% Ultratex REP

1.5% Hydrophobol XAN

13% Freerez PFK

2.9% Catalyst US

Example 14D: prepared using a one step application procedure,

10% Zonyl S410

1% Atebin 1062

3% Ultratex REP

1% Hydrophobol XAN

15% Permafresh MFX

3.75% Catalyst 531

Example 14E: Stain Defender Pants (DuPont Teflon ™ of Polyester / Cotton Blend Apparel);

Example 14F: Nanocare Pants (100% cotton believed to be treated according to US Pat. No. 6,379,753 assigned to Nanotex);

Example 14G: prepared using an application procedure after curing,

8% Scotchgard L-18542

10% Permafresh MFX

2.5% Catalyst EN

0.25% Tebefoam

0.5% Mykon XLT

Example 14H: prepared using an application procedure after curing,

4% Scotchgard L-18542

10% Permafresh MFX

2.5% Catalyst EN

0.25% Tebefoam

0.5% Mykon XLT

The test results are shown in Table VII.

Example 15:

The fabric of Example 13 was treated using the following inventive chemical composition:

Example 15A: Prepared using a one step application procedure,

3.75% Unidyne TG-992

1.25% Zonyl 7713

1.25% Arkophob DAN

10% Permafresh MFX

2.5% Catalyst EN

0.25% Tebefoam

0.5% Mykon XLT

Example 15B: made using a one step application procedure,

5.4% Unidyne TG-992

1.75% Zonyl 7713

2% Arkophob DAN

10% Permafresh MFX

2.5% Catalyst EN

0.25% Tebefoam

0.5% Mykon XLT

Example 15C: prepared using an application procedure after curing,

0.32% Unidyne TG-992

1.76% Arkophob DAN

3.87% Zonyl 7910

1.55% Repearl F8025

10% Permafresh MFX

2.5% Catalyst EN

0.25% Tebefoam

0.5% Mykon XLT

Example 15D: prepared using an application procedure after curing,

5% Unidyne TG-992

1% Repearl F-89

3% Epi-Rez 5003 W55

Example 15E: prepared using an application procedure after curing,

5% Unidyne TG-992

1% Repearl F-89

0.5% Epi-Rez 5003 W55

5% Permafresh MFX

2% Witcobond W-293

1.25% Catalyst EN

0.25% Tebefoam

0.5% Mykon XLT

Fabrics treated by the methods described above after 0 industrial washes, 5 industrial washes, 10 industrial washes, 20 industrial washes and 30 industrial washes are subjected to water and oil repellency, spray grade and corn oil and mineral oil stain release. Was tested. The test results are shown in FIG. VIII.

Example 16 (comparative)

Example 16A: The fabric of Example 13 was treated with the post-curing application procedure described above using the following competing chemicals:

4% Scotchgard L-18542

10% Permafresh MFX

2.5% Catalyst EN

0.25% Tebefoam

0.5% Mykon XLT

Example 16B: Treated with the one step application procedure described above using the following competing chemicals:

10% Zonyl 7040

2.0% Reactant 901

1% Free Cat (available from Noveon Inc.)

0.4% Alkanol 6112 (wetting agent)

The fabrics were tested after 0 industrial washes, 5 industrial washes, 10 industrial washes, 20 industrial washes and 30 industrial washes. The test results are shown in FIG. VIII.

Example 17:

The piece of nylon fabric was treated with the chemical of the present invention according to the one step application procedure described above. The fabric was obtained from Milliken & Campani, Spartanburg, South Carolina. Warp yarns consisted of 70/34 denier filament nylon 6,6 fibers. Fill yarns consisted of 2/070/66 denier filament nylon 6,6 fibers. The fiber was purchased from Dupont. Warp and peel yarns were woven together in a plain weave pattern with 106 warp yarns and 68 fill yarns per inch of fabric. The fabric was then jet dyed and face finished by light exposure with mechanical sanding. The finished fabric had a width of about 60 inches and a weight of about 4.8 ounces per yard.

The chemicals of the present invention included the following formulations (wt% in bath):

1.2% Zonyl 7910

2. 2% Repearl F8025

3. 1.5% Arkophob DAN.

The wet pickup of the chemical bath on the fabric was about 52%.

After zero household washings (“AR” means “as received”), five household washings and ten household washings, the fabric treated by the method described above was subjected to water and oil repellency, spray grade. And corn oil and mineral oil stain release. Test results are shown in FIG. IX.

Example 18 (comparative)

Example 17 was repeated except that each chemical formulation of the chemical composition was replaced with various competing stain release and / or stain repellent chemicals. The chemicals used are:

Example 18A: 3.0% Zonyl 7713 and 1% Repearl MF;

Example 18B: 3.0% Scotchgard L-18369 and 1% Hydrophobol XAN; And

Example 18C: 6.0% Scotchgard L-18542 and 1.5% Repearl MF.

The test results are also shown in test table IX.

Example 19:

Nomex® fabric pieces were treated with the chemicals of the present invention according to the one step application procedure described above. The fabric was obtained from Milliken & Campani, Spartanburg, South Carolina. Warp and peel yarn consisted of 38/2 denier staple T-462 Nomex® fibers. Warp and fill yarns were woven together in a plain weave pattern with 67 warp yarns and 43 fill yarns per inch of fabric. The fabric was then dyed in pieces and then finished by conventional techniques. The finished fabric had a width of about 60 inches and a weight of about 4.5 ounces per yard.

The chemicals of the present invention included the following formulations:

Example 19A:

2% Unidyne TG-992

1% Zonyl 7713

1.5% Arkophob DAN

Example 19B:

0.25% Unidyne TG-992

1.75% Zonyl 7910

2% Repearl F8025

1.5% Arkophob DAN

Example 19C: Untreated Fabric (Control).

The wet pickup of the chemical bath on the fabric was about 93%.

Fabrics treated by the methods described above after zero household washes (“AR” means “as received”) and five household washes were subjected to water and oil repellency, spray grades and corn oils and minerals. Tested for oil stain release. Test results are shown in FIG.

Each of these exemplified substrates was then tested for various surface properties.

C) Fabric surface analysis procedure and test results:

I) Description of the subsequent test method:

a) Household laundry procedures, which are subsequently undertaken to test for laundry durability, are performed in accordance with AATCC Test Method 130-2000, Washing Procedure 1 (105 ° F washing) and Tide Quick Dissolving Powder detergents. Was carried out using.

Industrial laundry procedures were carried out in accordance with standard procedures used by many large industrial laundry facilities. The procedure is used for colored blends of textile substrates and utilizes the following procedural steps:

The load magnitude for the industrial laundry procedure was measured at 80% of the device capacity (28 lb load of 35 lb device). The total wash cycle time was about 33 minutes. For example, the time indicated by "16/1" indicates that the washing time is 16 minutes and the draining time is 1 minute. Chemicals were Choice MP (concentrated nonionic surfactant), Horizon (silicate phosphate enhancer), Express (alkali compound) and Sour (acidic compound). The pH range of the wash cycle remained in the range of about 10.2 to 10.8.

b) The spray grade test was conducted according to AATCC (American Textile Chemists and Colorists Association) Test Method 22-2000. The rating scale is as follows:

100-no stickiness or dampness on the top surface

90-randomly slight stickiness or dampness on the upper surface

80-damp at the spray point of the entire upper surface

70-only part of the upper surface is damp

50-The entire upper surface is completely damp

0-The entire upper and lower surface is completely moist.

c) Stain release was measured using AATCC test method 130-2000. The staining agents used in stain release were corn oil (CO) and mineral oil (MI). The rating scale is 1 to 5, where "1" means the lowest degree of stain release and "5" means the highest degree of stain release. Generally about 3.0 is the minimum stain level that is acceptable in normal wear and use.

d) Water repellency was tested according to the 3M Water Repellency Test II (May 1992). The rating scale is 0 to 10, where "0" means the lowest degree of rebound (substrate has a higher surface energy), and "10" means the highest degree of rebound (substrate has a lower surface energy). . The 3M repulsive test scale is:

0 is 0% isopropanol (IPA), 100% water (by weight)

1 is 10% isopropanol, 90% water

2 is 20% isopropanol, 80% water

3 is 30% isopropanol, 70% water

4 is 40% isopropanol, 60% water

5 is 50% isopropanol, 50% water

6 is 60% isopropanol, 40% water

7 is 70% isopropanol, 30% water

8 is 80% isopropanol, 20% water

9 is 90% isopropanol, 10% water

10 is 100% isopropanol

e) Oil repellency is tested according to AATCC Test Method 118-2000. The rating scale is 0 to 8, where "0" means the lowest degree of repulsion (substrate has higher surface energy), and "8" means the highest degree of repulsion (substrate has lower surface energy). . Oil repulsion test scale is:

0 is Nujol (TM) mineral oil (substrate soaked in oil)

1 is Nujol (TM) mineral oil

2 is 65/35 Nujol / n-hexadecane (by volume)

3 is n-hexadecane

4 is n-tetradecane

5 is n-dodecane

6 is n-decane

7 is n-octane

8 is n-heptane

f) Kawabata hand test

Various properties were measured using the Kawabata evaluation system ("Kawabata System"). The Kawabata System, developed by Dr. Sue Kawabata (Professor of the Department of Polymer Chemistry, Kyoto University, Japan), is a scientific technique for measuring the "feel" of textile fabrics in an objective and renewable manner. It was developed specifically for use in Kawabata systems with basic mechanical properties (e.g., softness, fullness, stiffness, softness, flexibility and crispness) that relate to aesthetics regarding touch. This is accomplished by measuring using four sets of highly specialized measuring devices. These devices are as follows:

Kawabata Tensile and Shear Tester (KES FB1)

Kawabata Pure Flexural Testing Machine (KES FB2)

Kawabata Compression Tester (KES FB3)

Kawabata Surface Tester (KES FB4)

KES FB1 to 3 were prepared by Kato Iron Walk Call, Limited, Division of Instrumentation, Kyoto, Japan. KES FB4 (Kawabata Surface Tester) was manufactured by Kato Decco Co., Limited, Division of Instrumentation. In each case, measurements were performed using 8 inch by 8 inch samples of each of the four fabric types tested in accordance with standard Kawabata test procedures and averaged results. Care has been taken to prevent the sample from being handled in such a way that the sample is folded, wrinkled, stressed or otherwise deformed. The fabric was tested as it was made (ie, not washed afterwards). The die used to cut each sample was aligned with the yarn of the fabric to improve the accuracy of the measurement.

i) shear measurement

Test equipment was set up according to the instructions in the Kawabata manual. The Kawabata shear tester (KES FB1) was warmed up for at least 15 minutes before calculation. The tester was set up as follows:

Sensitivity: 2 and X5

Sample Width: 20cm

Shear weight: 195g

Tensile Speed: 0.2mm / s

Elongation Sensitivity: 25mm

The shear test measures the resistance to applying a constant tensile force to the fabric and to shear deformation in the vertical direction.

Mean shear stiffness (G) [gf / (cm-deg)]. Average shear stiffness was measured in the warp and peel directions, respectively. Lower values for shear stiffness indicate a more flexible hand.

Four samples are taken respectively in the warp and peeling directions and listed below.

ii) bending measurement

A value lower than the flexural stiffness (B)-means the fabric is less stiff. Four samples were taken in the warp and peeling directions, respectively.

iii) compression analysis

Test equipment was set up according to the instructions in the Kawabata manual. The Kawabata shear tester (KES FB3) was warmed up for at least 15 minutes before calculation. The tester was set up as follows:

Sensitivity: 2 and X5

Stroke: 5mm

Compression Speed: 1mm / 50s

Sample size: 20 x 20cm

A compression test is a measure of the resistance experienced by a plunger with a certain surface area when moving in a direction away from and perpendicular to the fabric sample in alternating directions. Ultimately, the test measures the work performed when compressing the fabric (forward direction) with a predetermined maximum force and the work performed during decompression (reverse direction) of the fabric.

% Compression at 0.5 g (COMP05): The higher the measured value, the more compressible the fabric.

Maximum thickness (TMAX): Thickness in mm at maximum pressure (nominal 50 gf / cm ² ). Higher TMAX means loftier fabric.

Minimum Thickness (TMIN): Thickness at 0.5 g / cm ² . In general, higher values are considered to be better. Higher TMIN means higher quality fabrics.

Minimum Density (TMIN): Density at TMIN (DMIN). Lower values are generally considered to be better. T _min [g / cm ³ ]

Maximum Density (TMAX): Density at TMAX (DMAX), T _max [g / cm ³ ]. Lower values are generally considered to be better.

Compression work per unit area (WC): The energy to compress the fabric to 50 gf / cm ² [gf-cm / cm ² ]. In general, larger is considered to be better.

Decompression work per unit area (WC '): This means the recoverability of the fabric. Larger values mean greater resiliency (ie, more elastic feel) and are generally considered to be better.

iv) surface analysis

Test equipment was set up according to the instructions in the Kawabata manual. The Kawabata Surface Tester (KES FB4) was warmed up for at least 15 minutes before calculation. The tester was set up as follows:

Sensitivity 1: 2 and X5

Sensitivity 2: 2 and X5

Tensile Weight: 480g

Surface Roughness Weight: 10g

Sample size: 20 x 20cm

Surface testing measures the frictional properties and geometrical roughness of the fabric surface.

Coefficient of friction (MIU): Average coefficient of friction [no units]. This was tested in each of the warp and peeling directions. Higher values consist of more fiber ends and loops, which means that the fabric is provided with a soft and fluffy touch. Four samples in each warp and peeling direction are taken and listed below.

Surface Roughness (SMD): Average displacement deviation [μ] of the contactor perpendicular to the surface. This means the roughness of the fabric surface. Lower values mean that the fabric surface has more fiber ends and loops to give the fabric a softer, more comfortable feel. Four samples in each warp and peeling direction are taken and listed below.

g) Dry Cleaning Test Method: This was done by putting about 6 inches by 6 inches fabric pieces in a 1 quart jar containing 250 ml perchloroethylene. The man was shaken vigorously for 5 minutes. The fabric was then removed and air dried for at least 8 hours. This method is hereinafter referred to as "dry cleaning method".

h) Static Test Method: This was done by placing about 3 inches by 8 inches of fabric pieces on a laboratory bench. The sample was rubbed 20 times (with one direction) with a new paper towel. The Simco FM300 electrostatic fieldmeter was placed approximately 1 inch from the fabric and measured at the push of a button. The results obtained were reported in kilovolts. To obtain results after conditioning of the fabric, the fabric sample was placed overnight in an environmentally controlled space at 70 ° F. and 65% relative humidity. The measurement was repeated on the conditioned sample.

i) Forward and Retracted Contact Angles: These were measured using the following two instruments and procedures.

i ) Tension meter test method: The tension measurement method used herein includes a gravimetric measurement of the interaction force when a solid is in contact with a test liquid (Wilhelmy method). These interaction forces are dynamic measurements and reflect the interaction of the entire impregnated article (wet length). The force is measured by advancing and retracting the article with the test liquid. From this measurement, both forward and backward contact angles can be measured in an indirect manner, respectively (Wilhelmie's equation).

ii ) Angle Test Method: The angle method used herein includes the optical observation of adherent droplets of test liquid on a solid substrate. The tangent angle was measured for each test liquid providing a direct measurement of the "advanced" (static) contact angle. These angles only reflect the average force imparted from the area under the drop (dropping point), not the bulk article. Each of these calculations can be used to determine surface energy and corresponding components.

Both the goniometer and tension meter test methods show similar results for the goniometer, which is a narrow area and static measurement.

j) X-ray photoelectron spectroscopy (XPS) was used to perform the surface chemical analysis shown in Example 28 and FIGS. 1 and 2.

XPS is described as follows:

XPS was first used to test polymer surfaces as described in DT Clark and HR Thomsa, The Journal of Polymer Science and Polymer Chemistry Ed. (1977, vol. 15, p. 2843). As used, this is the standard quantitative method for their characterization. The energy-analyzed electrons emitted during irradiation of the solid sample by monochromatic X-rays show sharp peaks corresponding to the binding energy of the core-level electrons in the sample. These binding energy peaks can be used to identify the chemical components in the sample.

The average free path in the solid is very short (λ-2.3 nm). See W. S. Bhatiam, D. H. Pan and J. T. Koberstein, Macromolecules (1988, vol. 21, p2166). The effective sampling depth Z of the XPS can be calculated by Z = 3λcosθ, where θ is the angle between the surface normal and the electron path emitted to the analyzer. The maximum depth that can be irradiated is about 7 nm at θ = 0. In the typical atomic components of the polymer, C, N and O, the optimized XPS can detect 0.2 atomic% of the composition. XPS is also very sensitive to F and Si. This quantitative information is very useful for understanding polymer surface properties.

X-ray photoelectron spectroscopy (XPS) is used herein to investigate the chemical composition of modified textile surfaces and also to evaluate surface chemical composition changes under different environmental circumstances. XPS Spectrum was obtained using a Perkin-Elmer Model 5400 XPS spectrometer with a Mg Kα X-ray light source (1253.6 eV) operating at 300 W and 14 kV DC and at 25 mA emission current. The spot size was 1.0 x 3.0 mm. Photoelectrons were analyzed on a hemisphere analyzer using a position-sensitive detector.

II) Analysis results:

"N / A" or "NA" listed in the table means that the test data is not available in that section.

Test results for Examples 1-4 are shown in Table IA. Example 1 demonstrates the durability of the chemical of the present invention in polyester fabrics in that it maintains a high level of water and oil repellency through at least 30 household washing cycles while maintaining an acceptable level of stain release. give.

The results of Example 2 resulted in maximizing stain repellency (ie, reducing the Unidyne TG-992 content) at the expense of stain release (ie, reducing mineral oil release with less Unidyne TG-992). Improvement) and, conversely, at the expense of stain repulsion (ie, lowering the spray grade to higher Unidyne TG-992), maximizing stain release performance (i.e., higher amounts of Unidyne TG-992 The diversity of the chemicals of the invention is described in terms of its ability to increase release). This variety allows the compositions of the present invention to be tailored to specific end use applications such as raincoats where water repellency may be more desirable or workwear where stain release may be more desirable.

The results of Example 3, a comparative example, show the excellent performance obtained by the unique combination of chemical agents disclosed by the present invention. Without this unique combination, as described in Comparative Examples 3A-3C, repellency, spray grade and stain releaseability are not optimized.

The results of Example 4 show that the fluorinated stain repellent provides durable durability, spray grade and stain release over 30 or more household laundry cycles when the alternative chemical is properly combined with other chemical formulations of the chemical composition. And stain release agents.

Table IA continued

Test results for Example 5 are shown in Table IB. The results show the durability and versatility of the chemicals of the present invention on substrates such as polyester bedspread fabrics having various structures and fiber deniers. The results also show the durability and variety of textile substrates made of flat (rather than texturing) polyester and textile substrates that have not been treated with a face finish sanding process.

Test results for Example 6 are shown in Table II. The result is that the chemical of the present invention described in Example 1 is subjected to at least 30 household washes for competing chemicals as described in Examples 6A-6J provided herein for comparison to the same microdenier polyester substrate. It provides durability through the cycle, spray grade and stain release.

Table II Continued

The results for Examples 7 (comparative) and 8 (examples of the invention) are shown in Table III. The results for Example 7 demonstrate that the chemicals of the present invention on polyester fabrics in that they maintain an acceptable level of stain release through at least five household laundry cycles while maintaining high levels of water and oil repellency. Shows durability. The results also show the diversity of the chemicals of the present invention in the use of various chemical application techniques and procedures.

The results of Example 8 demonstrate the durability of the chemicals of the present invention on polyester fabrics in that they maintain an acceptable level of stain release through at least 30 household laundry cycles while maintaining high levels of water and oil repellency. Shows. The results also show the diversity of the chemicals of the present invention in the use of various chemical application techniques and procedures. The results also show that alternative two-stage application procedures can provide higher spray grade results while maintaining a higher level of repellency and corn oil release than one-stage application procedures.

The test results of Example 9, Example 10 and Comparative Example 11 are shown in Table IV. The results of Example 9 demonstrate that the present invention on cotton fabrics in that it maintains a high level of water and oil repellency while maintaining an acceptable level of stain release through at least 30 household laundry cycles as noted below. It shows the durability of chemicals.

The results of Example 10 resulted in maximizing stain repellency (ie, reducing the Unidyne TG-992 content) at the expense of stain release (ie, reducing mineral oil release with less Unidyne TG-992). Improvement) and, conversely, at the expense of stain repulsion (ie, lowering the spray grade to higher Unidyne TG-992), maximizing stain release performance (i.e., higher amounts of Unidyne TG-992 The diversity of the chemicals of the invention is described in terms of its ability to increase release). This variety allows the compositions of the present invention to be tailored to specific end use applications such as raincoats where water repellency may be more desirable or workwear where stain release may be more desirable.

The results of Example 11 show the excellent performance obtained by the unique combination of chemical agents disclosed by the present invention. Without such a unique combination, as described in Comparative Examples 10A-10C, repellency, spray grade and stain releaseability are not optimized.

Test results for Comparative Example 12 and Example 9 of the present invention are shown in Table V. The results show that the chemicals of the present invention provide durable resilience, spray grade, and stain release over 30 or more household laundry cycles for competing chemicals provided herein for comparison using the same substrate.

Table V Continue

Test results for Example 13 are shown in Table VI. The result is the durability of the chemicals of the present invention on polyester and cotton blend fabrics in that they maintain an acceptable level of stain release through at least 30 household wash cycles while maintaining a high level of water and oil repellency. Shows. The result is an application in which the permanent press resin is fully cured during the textile finishing step or in which the resin is partially cured during the textile finishing step and then fully cured after garment manufacturing to obtain a durable garment crease (ie, curing). Later also shows the diversity of the chemicals of the invention. Both processes provide high levels of water and oil repellency, acceptable levels of stain release and acceptable levels of spray grade.

Table VI Continue

Test results for Example 14 are shown in Table VII. The result is at least 30 household wash cycles for the competing chemicals shown herein as Examples 14A-14H provided herein for comparison on the same polyester cotton blend substrate where the chemicals of the invention shown as Examples 13A-13J. To provide durable resilience, spray grade and stain release.

Table VII Continued

Table VII Continued

Test results for Examples 15 and Comparative Examples 16-18 of the present invention are shown in Tables VIII and IX. The results for Example 15 show that the present invention on polyester and cotton blend fabrics in that it maintains an acceptable level of stain release through at least 30 industrial laundry cycles while maintaining a high level of water and oil repellency It shows the durability of chemicals. The results also show the diversity of the chemicals of the invention in the addition of permanent press resins to the fabric before the chemicals of the invention are fully cured or after the chemicals of the invention are fully cured (ie, after curing). Both processes provide high levels of water and oil repellency, acceptable levels of stain release and acceptable levels of spray grade. The results also show the durability and effectiveness of the chemicals of the invention used in Examples 15A and 15B for tanned motor oil (“BMO”) stain release on polyester and cotton blend substrates after 30 or more industrial washes.

The results of Comparative Example 16 show that the chemicals of the invention shown as Examples 15A-15E are 30 compared to the competing chemicals shown as Examples 16A and 16B provided herein for comparison to the same polyester cotton blend substrate. It has also been shown to provide durable resilience, spray grade and stain release through more than one industrial wash.

The results of Example 17 show the durability of the chemicals of the present invention on nylon textile substrates over 10 household wash cycles when tested for spray grade and oil releaseability by the methods described above.

The results of Comparative Example 18 show the superior performance of the chemicals of the present invention on nylon textile substrates relative to competing chemicals for spray grade and corn oil and mineral oil release over 10 or more household laundry cycles.

Table VIII continued

The test results of Example 19 are shown in Table X. The results show improved corn oil and mineral oil release compared to untreated Nomex® fabrics. The results also show the durability of the chemicals of the present invention on Nomex® fabric through five household laundry cycles when tested for repellency, stain release and spray grade by the method described above.

III) Further analysis by changing the test method

Example 20:

Some other textile substrates are described using a one step application procedure to demonstrate that the chemicals of the present invention further provide improved oil and water repellency, improved stain release and improved spray grades on various textile substrates. Treated with a chemical and compared to the same textile substrate in an untreated state.

The chemical compositions used for these textile substrates are as follows:

1% Repearl F89, Repellent;

5% Unidyne TG-992, stain release agent; And

2% Witcobond W-293, crosslinker.

Example 20A:

A 100% acetate textile substrate made by Milliken & Campani was used to test oil and water repellency, spray grade and corn oil and mineral oil stain release by the method described above. The acetate textile substrate consisted of a 191 × 50 satin weave pattern and consisted of 75/19 denier bright (opposite of the dull) acetate warp yarns and 150/38 denier bright peel yarns. Acetate textile substrates had a wet pickup of the chemical composition on the substrate of about 80%.

Example 20B:

100% acrylic textile substrates were purchased from a fabric store to test oil and water repellency, spray grade and corn oil and mineral oil stain releaseability by the methods described above. Acetate textile substrates have a felt structure and exhibited wet pickup of the chemical composition on the substrate of about 250%.

Example 20C:

100% wool textile substrates were purchased from a fabric store to test oil and water repellency, spray grade and corn oil and mineral oil stain releaseability by the methods described above. Wool textile substrates had a plain weave structure and exhibited wet pick up of the chemical composition on the substrate of about 80%.

Example 20D:

100% silk textile substrates were purchased from a fabric store to test oil and water repellency, spray grade and corn oil and mineral oil stain releaseability by the methods described above. The silk textile substrate was a raw silk with a woven structure similar to a taffeta fabric. The wet pickup degree of the chemical composition on the substrate was about 100%.

Test results are shown in Table XI. The results for Example 20A show that the treated acetate textile substrates show improved oil and water repellency compared to the untreated acetate textile substrates. The results for Example 20B show that the treated acrylic textile substrate shows improved oil repellency compared to the untreated acrylic textile substrate. The results for Example 20C show that the treated wool textile substrate shows improved oil repellency and improved corn oil and mineral oil stain release compared to the untreated wool textile substrate. The results for Example 20D show that the treated silk textile substrates show improved oil and water repellency and improved spray grades as compared to the untreated silk textile substrates.

Example 21:

Example 1 was repeated except that some other conventional laundry detergent was used instead of the Quick Dissolving Tide®. Detergents used were:

Example 21A: Mountain Spring Tide (registered trademark)

Example 21B: Cheer®

Example 21C: Tide Free Liquid®

Example 21D: Era®

Example 21E: All®

Example 21F: Downy® (in washing machine) and Quick Dissolving Tide®

Example 21G: Bounce® (in dryer) and Quick Dissolving Tide®.

Test results are shown in Table XII. The results show that using a variety of different detergents and fabric softeners on polyester substrates results in good stain release and acceptable levels of repellency and spray grades.

Example 22:

In order to determine how the chemicals of the present invention affect the feel of the textile substrate, several textile substrates were treated as described below and then tested using a Kawabata evaluation system. The substrates tested and the chemical compositions used were as follows:

Example 22A: Example 1 was repeated.

Example 22B: Example 6B was repeated.

Example 22C: The textile substrate described in Example 1 was untreated as a control.

Test results are shown in Table XIII. Lower values for flexural stiffness mean a more flexible hand. The results show that the chemicals of the present invention do not adversely affect the feel of the polyester fabric, but actually slightly improve the feel when tested by Kawabata measurement.

Example 23:

The durability to dry cleaning was tested on microdenier polyester fabrics treated with the inventive chemical composition and several competing chemical compositions according to the dry cleaning procedure described above. Fabrics treated for oil and water repellency and spray grades prior to any dry cleaning cycle (“as received”), after one dry cleaning cycle, after five dry cleaning cycles, and after five dry cleaning cycles and ironing Was tested. The substrates tested were as follows:

Example 23A: Example 1 was repeated.

Example 23B: Example 6B was repeated.

Example 23C: Example 6C was repeated.

Test results are shown in Table XIV. The result is

It is shown that the chemicals of the present invention can withstand dry cleaning processes and dry cleaning and ironing processes and still maintain some level of durability through five or more dry cleaning cycles.

Example 24:

Other tests were conducted to determine the air permeability of the microdenier polyester textile substrate treated with the chemical of the present invention. Treated polyester fabrics were compared to untreated polyester fabrics and also to the same substrate with the competing chemical composition applied thereto. The test was conducted in accordance with ASTM test method D737-96 with an air pressure of 125 Pa (Pascals) and the results are expressed in units of “cfm” (feet ³ / minute). The textile substrates tested and the chemicals used were:

Example 24A: Example 1 was repeated.

Example 24B: Example 6B was repeated.

Example 24C The textile substrate described in Example 1 was untreated as a control.

The test results are shown in Table XV. The results show that treatment with the chemicals of the present invention does not significantly affect air permeability. The results further show that the air permeability is better for the chemicals of the present invention compared to the same fabrics treated with competing chemicals.

Example 25:

Other tests were conducted to determine the effect on the electrostatic charge of the chemicals of the present invention on microdenier polyester textile substrates. Treated polyester fabrics were compared to untreated polyester fabrics and also to the same substrate with the competing chemical composition applied thereto. The test was carried out following the procedure described above. Before household washing ("AR" means Grorow obtained), after one household washing cycle, after five household washing cycles, and washing five household washing cycles and substrates at 70 ° F and 65% relative humidity ("RH"). The results after conditioning in) are expressed as "kV" (kilovolts). "NR" means that the electrostatic charge exceeds the meter capacity for charge measurement. The textile substrates tested and the chemicals used were:

Example 25A: Example 1 was repeated.

Example 25B: Example 6B was repeated.

Example 25C The textile substrate described in Example 1 was untreated as a control.

Test results are shown in Table XVI. The results show that the electrostatic charge on the substrate is actually reduced after washing and conditioning the polyester substrate treated with the chemical of the present invention five times. The results further show that the substrate treated with the chemical of the present invention produces less electrostatic charge than the same fabric treated with the competing chemical without any washing after five washes and conditioning. It is further shown that the polyester substrate treated with the chemical of the present invention produces less electrostatic charge than the untreated polyester substrate after 1 wash and 5 washes.

In addition, to all results except for the substrate treated with the chemical of the present invention after five washes and conditioning, some degree of electrostatic charge was measured, which means that the substrate exhibited undesirable electrostatic fixation properties. The only sample that did not exhibit any electrostatic sticking properties was the substrate treated with the chemical of the present invention after five washes and conditioning. Since durable antistatic and anti-sticking protection is difficult to achieve on polyester substrates (particularly microdenier polyester substrates), these results show another advantage of using the chemicals of the present invention on various substrates.

Example 26:

The advancing and retracting contact angles were measured for the polyester substrates treated with the present invention and the competitive chemical composition using the aforementioned goniometer and tension meter test methods. The chemical composition is as follows:

Example 26A: Example 1 was repeated on a polyester film and on the polyester / cotton blend fabric described in Example 13 and the contact angle was measured.

Example 26B Example 26A was repeated on a polyester film using only 4.5% Unidyne TG-992, a stain release agent, and the contact angle was measured.

Example 26C: Example 26A was repeated on a polyester film using only 1.5% Repearl F8025, a stain repellent, and the contact angle was measured.

Example 26D Example 6B was repeated on a microdenier polyester fabric and the contact angle was measured.

Example 26E: Example 6C was repeated on a polyester film and on the polyester / cotton blend fabric described in Example 13 and the contact angle was measured.

Example 26F: The substrate (polyester film) described in Example 26A was left untreated as a control and the contact angle was measured.

Test results are shown in Table XVII. The results show that improved stain resistance and improved stain release are expected for the chemical compositions of the present invention as compared to conventional fluorochemical repellents (Example 26B). The results also show that improved aqueous stain resistance is expected when compared to newer repellents (Example 26C). In addition, the advancing contact angle is dominated by Repearl F8025 (stained repellent) and the retraction angle is dominated by Unidyne TG-992 (release agent), further supporting the chemical composition which is automatically adapted to changes in the environment. Shows. The results, in turn, show that the compositions of the present invention yield similar results both on natural and synthetic fibers and on films other than textile substrates.

Example 27:

Using the forward contact and retract angle data shown in Example 26, surface energies were calculated for the microdenier polyester substrates treated with the various inventive and competitive chemical compositions at both 25 ° C and 40 ° C. The results are expressed in units of milli joules (MJ) / M ² . The surface energy at 40 ° C. was measured using the same measurement technique except that the sample was immersed in water at 40 ° C. for 1 hour before testing and vacuum dried.

Example 27A: Example 1 was repeated and surface energy was measured.

Example 27B Example 1 was repeated with only 4.5% Unidyne TG-992, a stain release agent, and surface energy was measured.

Example 27C Example 1 was repeated using only 1.5% Repearl F8025, a stain repellent, and surface energy was measured.

Example 27D Example 6D was repeated and surface energy was measured.

Example 27E Example 6E was repeated and surface energy was measured.

Example 27F Example 6I was repeated and surface energy was measured.

The test results are shown in Table XVIII. The results reflect the unique surface energy changes obtained from the compositions of the present invention as a result of environmental changes. The chemical composition of the present invention is the only composition that shows a change from a low energy surface to a high energy surface as a result of environmental effects. This surface energy change is a representative requirement of durable stain repellent and stain releasing compositions or treated surfaces.

Example 28:

Surface chemical analysis of fluorine, carbon and oxygen using XPS analysis techniques was performed on microdenier polyester fabrics treated with the chemicals of this invention and various competing chemicals. The chemical composition applied to the fabric is as follows:

Example 28A: Example 6C was repeated.

Example 28B: Example 1 was repeated.

Example 28C: Example 6I was repeated.

Example 28D: Example 6D was repeated.

Example 28E: Example 6B was repeated.

Test results for Example 28 are shown in Table XIX and FIGS.

Detailed description of the drawings:

As shown in Table XIX and FIG. 1, the fluorine-containing fragment and the oxygen-containing fragment at the surface remain relatively constant for the treatment used in Example 28A, despite the sample being exposed to water or heat. However, if the sample is exposed to water and the sample is returned to essentially the original value after heating, the fluorine decreases and the oxygen increases when treated with Example 28B (chemical of the present invention). Without wishing to be bound by theory, this may mean that in the presence of water, especially at 40 ° C., the ethylene oxide fragment of Unidyne TG-992 is hydrated and fully expanded predominantly over the fluorinated fragment. This can explain not only the surface energy changes that have been produced, but also the excellent stain repellency and stain release properties of the chemical compositions of the present invention. Upon subsequent heating, the polymer returns to its original shape.

1 also shows that Examples 28A and 28B do not show an environmental response to water at 40 ° C. as shown in Example 28B. Examples 28C and 28D show a similar environmental response to Example 28B (chemical of the present invention). However, as shown in Figure 2, more fluorine is lost from Examples 28C and 28D than Example 28B (chemical of the present invention) after 10 household washings. This is particularly well suited for Example 28D and means a lack of durability for these treatments.

IV) further analysis of different fabric types

Example 29:

Suit fabrics consisting of about 65% polyester fibers and about 35% wool fibers were tested according to the above-described home dryer application procedures using the chemicals and competitive chemicals of the present invention. Treated fabrics were tested for corn oil stain release, water repellency and oil repellency as described above. Untreated control fabrics were also tested. The chemical composition used for the treatment is as follows:

Example 29A: Untreated Fabric Pieces (Control)

Example 29B: 5% Unidyne TG-992

Example 29C: 5% Unidyne TG-992

1% Repearl F-89

Test results are shown in Table XX. The results show that stain release agents and stain repellents can be added to textile substrates using domestic dryer application procedures to provide corn oil stain release and water and oil repellency. The results also show the versatility and ease with which such chemicals can be applied to substrates to obtain such stain release and repellency.

Thus, while it is known to use fluorocarbon polymers and hydrophilic stain release polymers together or separately, these properties can be used simultaneously and in repeated household and industrial laundry cycles to obtain water and oil repellency and stain release on the substrate. It has proven difficult to obtain with durability lasting after exposure. Since the polymers each tend to act opposite to each other and are washed out of the substrate during washing, a stain repellent, a stain release agent and a hydrophobic crosslinker that work well together as described in Examples 1-18 It was surprisingly found. The concentrations of the individual chemical agents, including the chemical compositions used to treat the substrate, the unique ratios of the chemical agents to each other in combination with each other, and the careful selection of the chemical agents, all of which are particularly important for the manufacture and product success of durability. It seems to play an important role in determining this.

In one or more preferred embodiments of the present invention, the chemical composition may be applied to the substrate in a one step application process, a two step application process or an alternative two step application process as described above. Indeed, as described in the Examples, polyamides, polyaramids, polyesters, cotton and polyester and cotton blend substrates upon treatment in accordance with the present invention have an improvement on durable water and oil repellency and durable stain release properties. All the obtained performance was obtained.

Thus, treated substrates of the present invention can be used in garment products such as outdoor wear (eg, raincoats), workwear (eg, uniforms), fashion clothes (eg, shirts, pants and other garments); Drapery; Napery (eg, table linen and nepkin); Residential furniture; Car upholstery fabrics; Carpeting; Many applicable uses are incorporated into outdoor fabrics (e.g., outdoor furniture, tents, boat covers and grill covers), and any other product desirable for producing substrates having durable water and oil repellency and durable stain release properties. Have

These and other changes and modifications to the invention can be made by those skilled in the art without departing from the spirit and scope of the invention. It will also be understood by those skilled in the art that the above description is illustrative only and is not intended to limit the scope of the invention described in the appended claims.

Claims (34)

(a) a stain release agent; (b) stain repellents; And (c) hydrophobic crosslinking species A composition for imparting durable resilience and stain release to a substrate, comprising a combination of: The method of claim 1, and wherein the concentration ratio of (a) :( b) :( c) ranges from about 10: 1: 0.1 parts by weight to about 1: 10: 5 parts by weight. The method of claim 2, And wherein the concentration ratio is from about 5: 1: 0.1 parts by weight to about 1: 5: 2 parts by weight. The method of claim 3, wherein And wherein the concentration ratio is about 1: 2: 1 parts by weight. (a) a stain release agent; (b) stain repellents; And (c) isocyanate-containing hydrophobic crosslinking species A composition for imparting durable resilience and stain release to a substrate comprising a mixture of. The method of claim 5, and wherein the concentration ratio of (a) :( b) :( c) is about 1: 2: 1 parts by weight. Stain release agents; Repellents; And Isocyanate-containing hydrophobic crosslinking species As a composition prepared by combining The stain release agent is ethoxylated polyester, sulfonated polyester, ethoxylated nylon, carboxylated acrylic, cellulose ether, ester, hydrolyzed polymaleic anhydride, polyvinyl alcohol polymer, polyacrylamide polymer, hydrophilic fluorinated polymer , Ethoxylated silicone polymer, polyoxyethylene polymer and polyoxyethylene-polyoxypropylene copolymer. (a) fluorinated stain release polymers; (b) stain repellents; And (c) hydrophobic crosslinking species A composition for imparting durable resilience and stain release to a substrate comprising a. (a) a stain release agent; (b) stain repellents; And (c) epoxy-containing hydrophobic crosslinking species A composition for imparting durable resilience and stain release to a substrate comprising a. (a) fluorinated stain release polymers; (b) stain repellents; And (c) isocyanate-containing hydrophobic crosslinking species Composition comprising a. (a) fluorinated stain release polymers; (b) fluorinated stain repellents; And (c) isocyanate-containing hydrophobic crosslinking species A composition for imparting durable resilience and stain release to a substrate, comprising a combination of: (a) fluorinated acrylate-containing polymers; (b) fluorinated urethane-containing polymers; And (c) isocyanate-containing crosslinked species A composition for imparting durable resilience and stain release to a substrate comprising a. (a) a stain release agent; (b) stain repellents; (c) hydrophobic crosslinking species; And (d) flame retardant compositions Composition comprising a. (a) a stain release agent; (b) stain repellents; (c) hydrophobic crosslinking species; And (d) antimicrobial compounds A composition for imparting durable resilience and stain release to a substrate comprising a. (a) a fluorocarbon-containing polymer having a non-esterified primary chain suitable for imparting stain release to the substrate; (b) stain repellents; And (c) hydrophobic crosslinking species A composition for imparting durable repellency and stain release to a substrate, comprising a mixture prepared by combining the same. Stain release agents; Fluorocarbon-containing repellents; And Blocked hydrophobic isocyanate crosslinked species As a composition prepared by combining The stain release agent is ethoxylated polyester, sulfonated polyester, ethoxylated nylon, carboxylated acrylic, cellulose ether, ester, hydrolyzed polymaleic anhydride, polyvinyl alcohol polymer, polyacrylamide polymer, hydrophilic fluorinated polymer , An ethoxylated silicone polymer, a polyoxyethylene polymer and a polyoxyethylene-polyoxypropylene copolymer. The method of claim 16, A composition further comprising a flame retardant. The method of claim 16, A composition further comprising an antimicrobial compound. (a) a fluorocarbon-containing copolymer having a non-esterified primary polymer chain, suitable for imparting stain release to the substrate; (b) stain repellents; And (c) hydrophobic crosslinkers A composition for imparting durable resilience and stain release to a substrate, comprising: Wherein said fluorocarbon-containing copolymer is selected from the group consisting of fluoroalkyl acrylates, fluoroarylates and fluorinated substituted urethanes. The method of claim 19, Wherein said hydrophobic crosslinker comprises an isocyanate-containing species. The method of claim 20, Wherein the source of isocyanate-containing species is blocked isocyanate. A first fluorocarbon-containing species suitable for imparting stain release to the substrate; Second fluorocarbon-containing species suitable for imparting durable resilience to the substrate; And Cross-linked species As the composition consisting essentially of, The first fluorocarbon-containing species is ethoxylated polyester, sulfonated polyester, ethoxylated nylon, carboxylated acrylic, cellulose ether, ester, hydrolyzed polymaleic anhydride, polyvinyl alcohol polymer, polyacrylamide polymer , Hydrophilic fluorinated polymer, ethoxylated silicone polymer, polyoxyethylene polymer and polyoxyethylene-polyoxypropylene copolymer, The second fluorocarbon-containing species is selected from the group consisting of waxes, silicones, hydrophobic resins and fluoropolymers, The crosslinked species may be monomers having blocked isocyanates, aromatic diisocyanates, blocked diisocyanates, blocked isocyanate-containing polymers, epoxy-containing compounds, epoxide resins, dia A composition selected from the group consisting of isocyanate-containing monomers and diisocyanate-containing polymers. The method of claim 22, And said first fluorocarbon-containing paper acrylate. The method of claim 22, Said second fluorocarbon-containing species comprising a fluorinated substituted urethane. The method of claim 22, Wherein said crosslinked species comprises aromatic diisocyanate. The method of claim 22, The crosslinked paper composition comprising an epoxy resin. A first fluorocarbon acrylate polymer species having an attached ethylene oxide group suitable for imparting stain release to the substrate; Second fluorinated urethane-containing species suitable for imparting durable resilience to the substrate; And Isocyanate-containing species A composition adapted for application to a textile substrate comprising a. A first fluorocarbon-containing species suitable for imparting stain release to the substrate; Second fluorocarbon-containing species suitable for imparting durable resilience to the substrate; And Cross-linked species As the composition consisting essentially of, The first fluorocarbon-containing species is ethoxylated polyester, sulfonated polyester, ethoxylated nylon, carboxylated acrylic, cellulose ether, ester, hydrolyzed polymaleic anhydride, polyvinyl alcohol polymer, polyacrylamide polymer , Hydrophilic fluorinated polymer, ethoxylated silicone polymer, polyoxyethylene polymer and polyoxyethylene-polyoxypropylene copolymer, The second fluorocarbon-containing species is selected from the group consisting of waxes, silicones, hydrophobic resins and fluoropolymers, The crosslinked species may be monomers having blocked isocyanates, aromatic diisocyanates, blocked diisocyanates, blocked isocyanate-containing polymers, epoxy-containing compounds, epoxide resins, dia A composition selected from the group consisting of isocyanate-containing monomers and diisocyanate-containing polymers. The method of claim 28, And said first fluorocarbon-containing paper acrylate. The method of claim 28, Said second fluorocarbon-containing species comprising a fluorinated substituted urethane. The method of claim 28, Wherein said crosslinked species comprises aromatic diisocyanate. The method of claim 28, The crosslinked paper comprises a epoxide resin. A first fluorocarbon acrylate polymer species having an attached ethylene oxide group suitable for imparting stain release to the substrate; Second fluorinated urethane-containing species suitable for imparting durable resilience to the substrate; And Isocyanate-containing species A composition adapted for application to a textile substrate comprising a. (a) a stain release agent; (b) stain repellents; (c) hydrophobic crosslinkers; And (d) flame retardant compositions A composition for imparting stain release, durable repellency, and flame retardancy to a substrate, comprising a combination of: