JP2006513332A - Composition having reversibly adaptable surface energy properties, treated substrate and method of making the same - Google Patents

Abstract

The present invention relates generally to substrates that exhibit useful, self-adaptable surface energy properties that depend on the environment of the substrate. Such surface energy characteristics provide a relatively high advancing and receding contact angle with the liquid when in contact with the target substrate surface. The substrate has a low surface of about 20 millijoules / square meter (mJ / m ² ) or less at a temperature of about 25 ° C., or greater than about 20 mJ / m ² at or when exposed to that temperature. Indicates the amount of energy. In particular, textile substrates having unique surface energy modifying properties that are highly desirable and exhibiting detergency, water and oil repellency, and soil release properties are included in the present invention. In particular, novel compositions and formulations that impart such surface energy modification to the substrate are also included in the present invention, as are methods for making such treated substrates.

Description

The present invention relates generally to substrates that exhibit useful, self-adaptable surface energy properties that depend on the environment of the substrate. Such surface energy characteristics provide a relatively high advancing and receding contact angle with the liquid when in contact with the target substrate surface. In particular, the substrate is measured by a goniometer at a temperature of about 25 ° C. and calculated by the Forks equation at a temperature of about 40 ° C. or less of about 20 millijoules per square meter (mJ / m ² ) or When exposed to that temperature, it exhibits a low amount of surface energy, exceeding about 20 mJ / m ² . This unique ability for automatic surface energy correction is in turn water and oil repellant, providing a surface that exhibits some degree of stain resistance and imparts effective soil release properties to the target substrate. In addition, this unique surface energy distribution is repeatable depending on the exposure environment and is reversible. Novel compositions and formulations that impart such surface energy modification to the substrate are also included in the present invention, as well as methods for making such treated substrates. In particular, textile substrates having unique surface energy modifying properties that are highly desirable and exhibiting detergency, water and oil repellency, and soil release properties are included in the present invention.

  As an example, there has been a long-standing need, particularly in the textile industry, to provide a substrate, such as a garment fabric, that exhibits many simultaneous wash resistance properties. Most notably, water repellency, oil repellency, stain resistance, and soil release are highly desirable to facilitate cleaning of the substrate unless it does not completely prevent the soil. Unfortunately, the provision of such simultaneous cleaning resistance has been significantly limited during the cleaning life of such substrates due to the general difficulty of meeting certain surface energy requirements. In general, the surface energy distribution required for one of these properties is distinctly different from the surface energy distribution required to impart other properties at the same time, so that the fabric (or other surface) is resistant to washing. Coatings or other treatments that can provide coexisting water and oil repellency and soil release properties to the base have not been readily available.

  There were cases where both characteristics existed simultaneously on a substrate (shown below), but unfortunately, the degree of cleaning resistance was unacceptable for long-term use of the target substrate. As a result, a decrease in water and oil repellency reduces soil release as well. The reduction in soil release includes the surface energy distribution required for proper soil release function (similar to that required to provide water and oil repellency as described above) (eg, for wash resistance) No.) The ability to produce proper soil release is lost, especially when exposed to severe soil.

  Therefore, it is highly possible to achieve simultaneous prevention of both polar (aqueous) and non-polar (olefinic) liquid penetration into such fabric surfaces that can withstand long-term general laundry operations. Due to the difficulty, truly effective cleaning resistance, long-term soil repellency and soil release treatment were unlikely to be realized. This problem with known water and oil repellant surface treatments is most notably observed in typical soiled substrates such as textiles including cotton. Such fabrics are generally difficult to modify their surfaces to the extent necessary to give them water and oil repellency and retain an acceptable texture. These at least three properties (soil release, water repellency and oil repellency) are simply not available to the textile industry on a wash-resistant basis due to the surface energy issues discussed above. Such a description of surface energy characteristics helps to allow a better understanding of such phenomena.

The basic physical property of any substance is its surface energy. This characteristic is usually expressed in mJ / m ² . Depending on the magnitude of this property, substances are classified as having a high surface energy and having a low surface energy. This property generally depends on the composition of the substrate. For example, a substrate having a surface that includes a substantial portion of polar hydrophilic groups such as hydroxyl groups, carboxylic acid groups, amine groups, etc. generally exhibits high surface energy. Conversely, a substrate having a surface that includes a significant portion of non-polar hydrophobic groups such as silicone groups, fluorinated groups, etc. generally exhibits low surface energy. When a polar liquid such as water is brought into contact with the surface of the substrate, the liquid will wet the surface only when the surface tension of the liquid is lower than the surface energy of the substrate. Conversely, if the surface tension of the liquid is higher than the surface energy of the substrate, spontaneous wetting will not easily occur and the liquid will remain on the substrate surface.

  As expected, modification of the surface energy of the substrate has long been a major area of research for a number of reasons for various materials. For example, it is often desirable to increase the surface energy of a substrate to promote the ability to absorb liquids or to increase the adhesion between the coating and the substrate. As a practical example, plastics and other materials, such as the chemical treatment of paper or plastic to promote wettability with printing inks, and Mylar® aluminum coatings in packaging applications There is a corona treatment of plastic to increase the adhesion between. The textile substrate was also modified to produce a substrate having a surface energy that is hydrophilic and produces a textile substrate that exhibits improved comfort and soil release properties. As one example, the detergent industry employs techniques to determine an effective method for cleaning various textile substrates.

  Surface energy modification has also been used for other coating applications, such as applying non-adhesive surfaces that exhibit low surface energy by applying Teflon to cooking utensils and utensils. The textile substrate is also hydrophobic and has been modified with a low surface energy treatment to produce a textile substrate that exhibits repellency properties (such as water-repellent rainwear).

  It has generally been observed that substrates treated with fluorinated polymers generally exhibit a contact angle with water of greater than 100 °. The advancing contact angle and the receding contact angle are very similar. The major component of the surface energy of such treatment is dispersibility. Substrates treated with a bifunctional repellent, as described in US Pat. No. 3,574,791 to Sherman et al., Are generally compared to traditional fluorochemical repellents, Shows a low contact angle. The measured surface energy contains significant dispersibility and polar components. The difference between the advancing and receding contact angles can usually be measured.

  In some cases, there is a measurable degree of hysteresis between the advancing and receding contact angles, indicating that the surface energy can be changed in the presence of a liquid. Except for liquid adsorption, hysteresis indicates that the surface energy has changed (kinetically or thermodynamically) in the presence of liquid or environmental conditions. This measurable degree of hysteresis provides further evidence that the substrate automatically adapts to its environment. One way to achieve ideal performance for textile applications is obtained from a composition that provides a high advancing contact angle (ie> 90 °), imparts soil resistance, and a low advancing contact angle ( That is, it exhibits non-porous behavior to provide <90 °) and non-porous behavior to impart soil resistance to the substrate. Another way to achieve ideal performance for such applications is to provide a high advancing and receding contact angle between the soil material and the substrate, and then a low advancing and retracting contact while subjected to a cleaning operation. It is obtained from a composition that imparts corners.

  In order to prevent adsorption or fouling, it is desirable for a porous or fouling surface to exhibit a high contact angle for various liquids. It is also desirable to adapt to these environmental changes, such as cleaning media, to facilitate removal of dirt and dust. Other environmental conditions that induce changes in the surface energy of the material include changes in temperature, moisture, or other environmental factors. It is highly desirable to have a surface that is compatible with the environment, so that the surface is soil resistant, can be cleaned, and retains this effect over many cycles of use. In end uses such as garments, carpets, fillings, etc., it has been found that such treatments have a negative impact on subsequent cleaning, such as stain resistant garment treatments. Thus, it is highly desirable to develop a soil resistant textile substrate.

Advances in XPS, SIMS and other surface analysis techniques have made it possible to detect chemical groups on the surface of materials. For example, it is possible to measure the concentration and depth distribution of functional groups, such as the CF ₃ moiety commonly found in soil resistant chemicals made of fluoropolymers. It is also possible to observe the changes that occur on the surface of the substrate and that appear as a result of changes in the environment to which the substrate is exposed by suitable sample manufacturing techniques. For example, a substrate that is observed to predominantly contain low surface energy groups, such as CF ₃ groups, under a first condition is like a hydroxyl group on its surface under a different second condition. It can be shown that it contains fairly hydrophilic surface energy groups. This change in polarity typically wets the surface of the substrate, thereby facilitating the release of dirt. According substrates environment returns to the first condition, for example, CF ₃ group returns to the surface of the substrate, the substrate and its low surface energy, i.e. back to the soil resistance state.

  Some treatment compositions, such as polymers, have other properties, such as glass transition point, that affect the ultimate performance of the treated substrate. For example, a hard polymer characterized by a high glass transition point provides increased protection against wetting, particularly forced wetting. However, this hard, high glass transition polymer requires more work to adapt to changes in its environment due to less in-polymer flexibility. In addition, the addition of polymer molecular weight and comonomer similarly enhances wettability, chemical reactivity, and durability for various materials.

  Obviously, modifications to provide the proper surface energy distribution have been pursued over the years to simultaneously impart cleaning resistance, oil repellency, water repellency, stain resistance, and soil release properties to the target substrate. However, it was not successful.

  The invention described herein allows the adjustment of the surface properties of the target substrate in order to obtain the desired balance of surface energy distribution for chemicals and processing conditions to simultaneously impart repellency and soil release. / Or promote. Moreover, this unique combination of properties has surprisingly been shown to be quite durable when exposed to routine and industrial cleaning methods.

DESCRIPTION OF THE PRIOR ART All US patents listed below are hereby incorporated by reference in their entirety.

  US Pat. No. 2,841,573 to Ahlbrecht et al. And US Pat. No. 3,645,990 to Raynolds describe the use of fluoropolymers to impart oil resistance and water resistance to textile substrates. Disclosure. Such a treatment does provide a certain degree of soil resistance to the substrate, but tends to have limited durability against washing. In addition, such polymers prevented the release of soil, particularly in the environment, when the soil forces the substrate to wet or when the substrate is dried. In fact, soil removal was more difficult in these environments than when the substrate was not treated.

  In addition to fluoropolymers, silicones, waxes, and various other compounds have been disclosed for imparting repellency to fabrics and other substrates. With the exception of fluoropolymers, such compounds usually only provide water repellency and have limited durability to washing. These techniques are disclosed, for example, in US Pat. No. 4,421,796 to Burrli et al.

  U.S. Pat. No. 3,574,791 to Sherman et al. And U.S. Pat. No. 3,896,088 to Raynolds et al. Provide some degree to the substrate without adversely affecting soil removal during washing. Disclosed are fluorinated, oily soil release agents that impart water and oil repellency. Basically, these patents disclose fluorinated polymers containing both repellent and hydrophilic moieties. Such polymers exhibit a “flip-flop” mechanism that exposes the fluorinated segment to air to provide soil resistance and then exposes the hydrophilic segment to an aqueous environment to provide soil release. It is claimed. Such polymers typically exhibit lower repellency, especially lower water repellency, than traditional fluorinated chemicals, and they suffer from a lack of durability to washing.

  U.S. Pat. No. 4,624,676 to White et al. Discloses a novel silicone composition, such as origanosiloxane, that imparts soil release properties to a substrate. If these compounds are cross-linked, durability is claimed. The compound is self-crosslinkable or can be crosslinked to the substrate, especially when a suitable catalyst is used. Such compounds provide resistance to aqueous soils but provide little resistance to oily soils.

  U.S. Pat. No. 4,834,764 to Deiner et al. Discloses the use of cross-linked resins such as methylol-containing resins or blocked diisocyanates to promote the durability of fluoropolymers. Such a resin increases the durability of the fluoropolymer to laundry. These resins are added to aqueous treatments containing fluoropolymers. However, while increasing the durability of the soil repellency properties, acceptable soil release does not result from this combination.

  U.S. Pat. No. 4,540,765 to Koemm et al. Discloses that a fluorine-based chemical repellent has a greater wash durability than that shown by the above attempts. . Typically, such polymers contain certain crosslinkable moieties within the polymer. Examples of such crosslinkable moieties include methylol groups, blocked isocyanate groups, epoxy groups and the like. Such crosslinkable polymers do have great laundry durability. Durability is improved as in US Pat. No. 4,834,764 to Deiner et al., But no acceptable soil release is seen.

  US Pat. No. RE 28,914, granted to Marco, describes carboxylated acrylic soil release polymers, fluoropolymers, and aminoplasts to produce cellulose-containing fabrics with good soil repellency and improved soil release. The use of a resin is disclosed. However, this treatment only works for cellulose-containing fabrics, with the exception of many rigid fibers.

  U.S. Pat. No. 4,695,488 to Hisamoto et al. Discloses a soil release composition comprising a polymer containing fluoroalkyl and alkoxy groups, a hydrophilic resin, and optionally water and oil repellents. . This composition is required to impart permanent antifouling and soil release properties to the substrate. However, the disclosed levels of water and oil repellency are rather low, and the disclosed antifouling test shows soil resistance rather than soil release.

  Even with so many attempts within this crowded field to provide the desired properties described above, certain surfaces, especially fibers, and most notably, disclosed and used within this industry, There was also no wash-resistant treatment that simultaneously imparted acceptable levels of water repellency, oil repellency, and soil release properties to the suggested cotton-containing fabric. Market and customer requirements are to make various materials as resistant as possible to contamination by many common contaminants, while at the same time having the substrate have improved soil removal characteristics by using routine cleaning procedures appropriate to the substrate. showed that. These cleaning procedures include cleaning as in home or industrial washing machines, or spot cleaning procedures as used in deuterons. In addition, various other routine cleaning procedures such as carpet cleaning and dry cleaning are included. Thus, despite the longstanding need and customer demand for substrates with durable repellency and soil release properties, prior attempts have not reached such goals.

  Therefore, one object of the present invention is to provide a novel composition that simultaneously imparts water / oil repellency, water repellency, stain resistance, and soil release properties to a substrate. It is also an object of the present invention to provide high performance during standard laundry procedures, such as household and industrial cleaning of surface and / or substrate cleaning, dry cleaning, or other typical methods. It is to disclose a substrate that exhibits a level of water and oil repellency and an acceptable level of soil release. Yet another object of the present invention is to disclose a method of treating a substrate to obtain a continuously high level of water and oil repellency and acceptable soil release properties. Other objects of the invention include, but are not limited to, specific textile substrates, either by typical dipping, padding, evacuation, or other similar application procedures, or domestic dryer application procedures. Including the application of such novel compositions to impart such detergency properties.

  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, including a high surface energy component, a low surface energy component, and a hydrophobic crosslinking component. In particular, the present invention relates to persistent soil repellent on a substrate comprising at least one hydrophilic soil release agent, the product of at least one hydrophobic soil repellent crosslinked by at least one hydrophobic crosslinker, and A composition that imparts soil release is included. The present invention further includes a textile surface treatment composition comprising at least one fluorinated polymer component. This composition provides the desired repellency and soil release characteristics to test polyester or cotton substrates in a wash resistance, high oil repellency rating, water repellency rating, spray rating, soil release rating, as described below. Give. In such a state, the composition is defined by the properties imparted to such a specific test fabric, and the invention states that such a fabric exists as part of the composition of the present invention. It will be clear that it is not necessary.

  Another part of the present invention comprises a specific textile substrate, such as a textile substrate comprising at least 20% cotton fibers of the total weight of the substrate, said substrate being tested according to AATCC test method 118-2000. An oil repellency rating of at least 4.0, a water repellency rating of at least 4.0 when tested by 3M water repellency test II (May 1992), at least 70 when tested by AATCC test method 22-2000 Spray grade and a soil release rating of corn and mineral oil of at least 4.0 when tested according to AATCC test method 130-2000, wherein the properties are determined by the AATCC test method after the test fabric has been washed 20 times Shown after being washed and dried according to 130-2000, the substrate is exposed to a temperature of about 25 ° C. When the measured surface energy less than about 20 millijoules / square meter, when exposed to a temperature of about 40 ° C., measured surface energy exceeds about 20 millijoules / square meter.

  While preferred are textile substrates comprising polyester fibers, other textile substrates are similarly provided within the present invention, without limitation. Therein, the substrate has an oil repellency rating of at least 3.0 when tested by AATCC test method 118-2000 and at least 3.0 when tested by 3M water repellency test II (May 1992). Water repellency rating, at least 50 spray rating when tested according to AATCC test method 22-2000, and soil release rating of at least 3.5 corn and mineral oil when tested according to AATCC test method 130-2000 The properties shown are shown after the test fabric has been washed and dried according to AATCC test method 130-2000 after 20 washes, and show the same surface energy modification as described above belonging to the cotton fabric. .

A method of imparting sustained repellency and soil release to a substrate is additionally included in the present invention, which includes:
(A) providing a substrate;
(B) coating a substrate with a composition comprising a hydrophilic soil release agent, a hydrophobic soil repellent, and a hydrophobic crosslinking agent;
(C) heating the substrate to remove substantially all excess liquid from the coated substrate;
(D) optionally further comprising the step of heating the coated substrate.

Definitions The terms “water repellency” and “oil repellency” are defined as the ability of a substrate to block water and oil from penetrating the substrate, respectively. For example, the substrate can be a fabric substrate that can block water and oil from penetrating the fibers of the fabric substrate.

  “Soil release” is generally defined as the degree to which a soiled substrate approaches its original soilless appearance as a result of the protective treatment. As defined herein, high levels of soil resistance are tested by at least 3.0 oil repellency rating, 3M water repellency test II (May 1992) when tested according to AATCC test method 118-2000. Means a water repellency rating of at least 1.0 when tested, and a spray rating of at least 50 when tested according to AATCC test method 22-2000. As described herein, acceptable soil release means a corn and mineral oil soil release rating of at least 3.0 as tested by AATCC test method 130-2000.

  “Wash durability” is generally defined as the ability to hold an acceptable level of a desired function to a substrate through an appropriate number of standard wash cycles. More particularly, the durability described herein is determined according to AATCC test method 130-2000 after a minimum of 10 wash cycles, more preferably after 20 wash cycles, most preferably after 50 wash cycles. It is intended to describe a substrate that maintains sufficient properties of soil resistance, water repellency, oil repellency, and spray grade. This substrate is, for example, a fabric substrate such as a polyester fabric fiber.

  The terms “fluorocarbon”, “fluoropolymer”, and “fluorochemical” are used interchangeably and each indicates a polymeric material that includes at least one fluorinated segment.

  The term “padded” indicates that the substrate is liquid coated by passing the substrate through a bath and then through a squeeze roller.

  The term “hydrophilic” is defined as having a strong affinity for water or the ability to absorb water.

  The term “hydrophobic” is defined as an affinity for water or a lack of ability to absorb water.

The term “high surface energy” is defined as a surface energy of about 25 mJ / m ² or more at about 25 ° C. calculated from Forks' two-component method to solid surface energy (as additional information in the Forks equation) , Industrial and Enginnering Chemistry, 1964, Chapters 12, 40, and 56 by FMFowkes).

The term “low surface energy” is defined as a surface energy of less than about 25 mJ / m ² at about 25 ° C., calculated from Forks's two-component method to solid surface energy.

  High surface energy surfaces are described for cotton-like surfaces that can spontaneously wet (with 90 ° contact angle) with lower surface tension liquids such as water.

  A low surface energy surface such as Teflon® does not get wet spontaneously by water and maintains a contact angle of> 90 ° with a liquid containing higher surface tension (approximately> 25 mN / m).

Compositions Useful for imparting soil resistance and soil release to substrates are typically hydrophilic soil release agents, hydrophobic soil repellents, and hydrophobic crosslinkers, and optionally to substrates. Other additives that give the desired contribution. Within the scope of the present invention, a novel chemical composition is contemplated, in which the relative amounts and chain lengths of each of the chemicals described above are desired for various target substrates within a single chemical composition. Optimized to achieve a level of performance.

  Hydrophilic soil release agents include ethoxylated polyesters, sulfonated polyesters, ethoxylated nylons, carboxylated acrylics, cellulose ethers or esters, hydrolyzed polymaleic anhydride polymers, polyvinyl alcohol There are polymers, polyacrylamide polymers, hydrophilic fluorinated soil release polymers, ethoxylated silicone polymers, polyoxyethylene polymers, polyoxyethylene-polyoxypropylene copolymers, and the like, or combinations thereof. A hydrophilic soil release agent is a preferred soil release agent. A potentially preferred non-limiting compound of this type is UNIDYNE® TG-2, commercially available from Daikin, REPEARL® SR1100, commercially available from Mitsubishi, and commercially available from DuPont. ZONYL® 7910. Treatment of the substrate with a hydrophilic soil release agent generally produces a surface that exhibits high surface energy.

  Examples of the hydrophobic stain repellency include wax, silicone, predetermined hydrophobic resin, fluoropolymer, and the like, or a combination thereof. Fluoropolymers are preferred soil repellency. Potentially preferred non-limiting compounds of this type are REPEARL® F8025, REPEARL® F-89, commercially available from Mitsubishi, and ZONYL® 7713, commercially available from DuPont. is there. Treatment of the substrate with a hydrophobic stain repellent generally produces a surface that exhibits a low surface energy.

  Hydrophobic crosslinking agents include water-insoluble crosslinking agents. In particular, hydrophobic crosslinkers include monomers containing blocked isocyanates (such as blocked diisocyanates), polymers containing blocked isocyanates (such as blocked diisocyanates), or epoxy-containing compounds, etc. There is a combination. Diisocyanate-containing monomers or diisocyanate-containing polymers are preferred crosslinkers. However, two or more blocked isocyanate compounds are the most preferred crosslinking agents. One potentially preferred cross-linking agent is REPEARL® MF, also commercially available from Mitsubishi. Other crosslinking agents include ARKOPHOB (registered trademark) DAN commercially available from Clariant, EPI-REZ (registered trademark) 5003W55 commercially available from Shell, and HYDROPHOBOL (registered trademark) commercially available from DuPont. ) There is XAN.

  The total amount of chemical composition applied to the substrate, as well as the respective proportions of chemical agents including the chemical composition, varies 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 application, and the cost of the chemical composition. As a general guideline, the total amount of chemical solids applied to the substrate will be found in the range of about 0.25% to about 10.0% of the substrate weight. More preferably, the total amount of chemical solids applied to the substrate is found in the range of about 0.5% to about 5.0% of the substrate weight. Typical solids ratios and concentration ratios of soil repellent, soil release agent and crosslinker are found in the range of about 10: 1: 0.1 and about 1: 10: 5, all ratios and ratios being Seen within this range. Preferably, the solids ratio and concentration ratio of the soil repellent, soil release agent and crosslinker is found in the range of about 5: 1: 0.1 and about 1: 5: 2. Most preferably, the solids ratio and concentration ratio of the soil repellent, soil release agent, and crosslinker is about 1: 2: 1.

  The ratio of soil release agent, soil repellent and crosslinker can be similarly varied based on the relative importance of each respective property being modified. For example, a higher level of soil repellency may be required for a given end use application. As a result, the amount of stain repellent with respect to the amount of stain release agent is increased. Alternatively, a high level of soil release agent may be more important than a high level of soil repellent. In this case, the amount of the soil release agent is increased with respect to the amount of the soil repellent.

  For the purpose of producing more economical chemical compositions, the type of soil release agent, soil repellent and crosslinker can be varied based on the end use of the substrate treated with the chemical composition. For example, a treated substrate is produced that is expected not to encounter oily soils. Therefore, more economical stains such as silicone can be used as one component of the chemical composition.

  The substrate of the present invention includes glass, fiberglass, metal, film, paper, plastic, stone, brick, woven fabric, or a combination thereof. In addition, metal products such as bridges or automobile bodies can benefit from the present invention. Such items are resistant to general dirt and are cleaned by rain or the like. The film can be a thermoplastic material, a thermosetting material, or a combination thereof. Suitable thermoplastic or thermosetting materials include polyolefin, polyester, polyamide, polyurethane, acrylic, silicone, melamine compound, polyvinyl acetate, polyvinyl alcohol, nitrile rubber, ionomer, polyvinyl chloride, polyvinylidene chloride, chloroisoprene, or the like. There are combinations. Polyolefins include polyethylene, polypropylene, ethyl vinyl acetate, ethyl methyl acetate, or combinations thereof.

  The textile substrate includes one potentially preferred, non-limiting aspect of the present invention. The woven substrate may be any known structure, including knitted structures, woven structures, non-woven structures, etc., or combinations thereof. The textile substrate has a weight of about 1-55 ounces / square yard, more preferably 2-12 ounces / square yard.

  The material of the woven substrate can be synthetic fiber, natural fiber, man-made fiber using natural ingredients, inorganic fiber, glass fiber, or a blend thereof. As an example only, examples of synthetic fibers include polyester, acrylic, polyamide, polyolefin, polyaramid, polyurethane, and blends thereof. In particular, the polyester includes polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polylactic acid, or a combination thereof. Polyamide includes nylon 6, nylon 6,6, or a combination thereof. Polyolefins include polypropylene, polyethylene, or combinations thereof. Polyaramids include poly-p-phenylene terephthalamide (ie, Kelar®), poly-m-phenylene terephthalamide (ie, Nomex®), or combinations thereof. Examples of natural fibers include wool, cotton, linen, ramie, jute, flax, silk, cannabis, or blends thereof. Examples of artificial fibers using natural ingredients include regenerated cellulose (ie, rayon), lyocell, or a blend thereof.

  The textile substrate is formed from staple fibers, filament fibers, slit film fibers, or combinations thereof. This fiber is subjected to one or more yarn processing processes. This fiber is spun or bonded by, for example, ring spinning, open-end spinning, air jet spinning, vortex spinning, or a combination thereof to form a yarn.

  The textile substrate comprises any size fiber or yarn, including microdenier fibers or yarns (fibers or yarns less than 1 denier per filament). The fiber or yarn has a denier ranging from less than 1 denier per filament to about 2000 denier, more preferably from less than 1 denier to about 500 denier per filament.

  In addition, the textile substrate may include, in part or in whole, multicomponent or bicomponent fibers or yarns in various forms such as, for example, underwater islands, cores and sheaths, side-by-side, or pie shapes. . Depending on the form of the bicomponent or multicomponent fiber or yarn, the fiber or yarn can be split along its length by chemical or mechanical action.

  The textile substrate can be printed or dyed to create an aesthetically pleasing decorative design on the substrate or to print an informational message on the substrate. Textile substrates are used in this field for traditional products corresponding to high temperature jet dyeing with disperse dyes, thermosol dyeing, pad dyeing, transfer dyeing, screen printing, digital printing, ink jet printing, flexographic printing, or comparable. Colored by various dyeing and / or printing techniques, such as other common techniques. In addition, the fibers or yarns comprising the textile substrate of the present invention may be dyed by an appropriate method such as package dyeing, solution dyeing, or beam dyeing, or left undyed, prior to substrate formation. The In one embodiment, the textile substrate is printed with a solvent-based dye rather than a water-based dye. Solvent-based dyes tend to wet the hydrophobic surface of the present invention uniformly.

  It is contemplated that a textile substrate composite material is formed by bonding one or more layers of a textile substrate. For example, it may be desirable to combine several layers of open woven fabric to form a woven substrate composite. The composite material also includes an adhesive material or a film of one or more layers. The composite material is then treated with the chemical composition of the present invention to obtain a material that exhibits sustained soil repellency and soil release performance. Alternatively, in yet another aspect of the invention, the textile substrate comprising the composite material is treated with a chemical composition before being bonded to the composite material form.

  In one potentially preferred embodiment of the present invention, daily necessities with a limited useful life are treated with a minimal amount of chemicals to obtain the required properties. In particular, substrates such as lightweight polyester disposable laboratory jackets have only about 0.25% to about 1.5% of a chemical solid applied to the substrate. Conversely, in another potentially preferred embodiment of the present invention, a premium product with a longer useful life is treated with approximately the maximum amount of chemical to achieve the desired level of durability. In particular, substrates such as high grade cotton apparel products or polyester / cotton blend work clothes have about 1.0% to about 10.0% chemical solids applied to the substrate.

  The application of the soil repellent, soil release agent and crosslinker to the textile substrate may involve dip coating, padding, spraying, foam coating, evacuation techniques, or a controlled amount of liquid suspension applied to the textile substrate. This can be done by various application methods including any other technique that can be done. Employing one or more of these coating techniques can uniformly apply chemicals to the textile substrate.

  What are chemical substances? It is applied simultaneously or sequentially to the textile substrate. For example, the soil release agent, soil repellent and hydrophobic crosslinker are mixed in one solution and then applied simultaneously to the textile substrate by padding. After application of the chemical agent to the textile substrate, the treated substrate is generally subjected to a drying process to evaporate excess liquid, leaving a solid active ingredient on the surface of the treated substrate. Drying can be done by techniques typically used in manufacturing operations, such as drying heat from a tenter, microwave energy, infrared heating, steam, superheated steam, autoclave, etc., or combinations thereof. In yet another aspect, a soil release agent is applied to the textile substrate, the substrate is allowed to dry or remain wet, and then a soil repellent and a hydrophobic crosslinker are applied over the soil release agent, Layered exclusive chemical treatment is performed on the surface of the substrate.

  In order to further enhance the performance or durability of the chemical agent, it is desirable to subject the treated substrate to an additional heating step. This process is called a curing process. As an example, additional heating (a) melts and flows the individual particles of the active agent of the chemical agent together to produce a uniform agglomerated film layer, and (b) induces preferred orientation of a given segment of the chemical agent (C) induces a cross-linking reaction between chemical agents or between a chemical agent and a substrate, or (d) a combination thereof.

  In many cases, properties other than persistent soil resistance and soil release are desirable for satisfactory performance for a textile substrate, regardless of its end use. Examples of such properties include antistatic, wrinkle resistance, shrinkage reduction or removal, desirable feel (feel) requirements, dyeing durability, odor control, flammability requirements, dry dirt resistance, and the like. Unexpectedly, the textile substrate treated according to the present invention actually exhibits anti-sticking and anti-static properties, which are desirable properties of the substrate, for example during garment cutting and sewing processes.

  Thus, finishes containing chemicals such as antimicrobial agents, antibacterial agents, antibacterial agents, flame retardants, UV inhibitors, antioxidants, colorants, lubricants, antistatic agents, fragrances, etc., or combinations thereof It is desirable to treat the textile substrate with an agent. Application of the chemical is done by dip coating, padding, spraying, foam coating, or any other technique that can apply a controlled amount of liquid suspension to the textile substrate. Employing one or more of these coating techniques can uniformly apply chemicals to the textile substrate. Many such chemical treatments are performed concurrently with the treatment with the chemical composition of the present invention, or such treatment is performed prior to the treatment with the chemical composition of the present invention. Many such chemical treatments can also be performed after treatment with the chemical composition of the present invention using suitable techniques.

  Note that the textile substrate is also processed by mechanical finishing techniques. For example, fabric substrates can be calendered, embossed, etched, rainbow or hologram embossed, film or metal foil hologram embossed, fabric metallization, heat-cured, hydroentangled with water or air, sunholized, shrined, Such as suede processing, sanding, emorizing, napping, hair processing, tigering, decating, fabric patterning with water, air, laser, or pattern roll, etc., or combinations thereof It is desirable to be subjected to mechanical treatment. These mechanical treatments that affect properties such as the appearance, strength, and / or feel of the fabric typically provide the desired effect on the fabric substrate. Where mechanical processing is used, advantages may be gained by either processing before or after the chemicals of the present invention are applied. Examples include benefits from sanding before chemical treatment and calendering after chemical treatment.

  Within the scope of the present invention, it is envisaged that an asymmetric textile substrate with a surface having two functional properties is produced. For example, a textile substrate having a first and second surface is produced, which has a first hydrophobic surface and a second hydrophilic surface. Such dual function fabric substrates are made, for example, by coating a hydrophilic soil release agent on both sides of the fabric substrate and then coating a hydrophobic soil repellent and hydrophobic crosslinker on the first surface of the substrate. It is done. Examples of the method for applying the chemical substance include those described above such as spray coating and foam coating. As a result, the garment thus made provides increased protection from environmental or chemical attack by repelling liquid on the first side of the garment and sweat on the second side of the garment. Absorbing such moisture provides increased user comfort.

Treatment composition and its application to a textile substrate A) Textile application procedure All examples given below are treated according to one of the following procedures and written down accordingly.

I) One-step coating procedure Approximately 14 "x 18" pieces of fabric were immersed in a bath containing a chemical containing the desired chemical agent.

    2. Unless otherwise noted, the percentage (%) of all chemicals is weight percent based on the total weight of the bath prepared, and the balance when given chemical percentages or grams is water. In addition, if the composition contains 30% active ingredient, the% composition is based on chemicals obtained from the manufacturer so that X% of this 30% composition is used. .

    3. After the fabric was completely wetted, the fabric was removed from the treatment bath and passed through a squeeze roller at about 40 psls, generally yielding a uniform water absorption of about 50 to about 90%.

    4). The fabric was pulled taut and secured to the frame to maintain the desired dimensions.

    5). The pin frame was placed in a Despatch oven at about 300-400 ° F. for about 0.5 to about 5 minutes to heat cure the fabric and to cure the final product.

    6). Once removed from the oven, the fabric was removed from the pin frame and homogenized at room temperature prior to testing.

II) Two-step application procedure 1. Rather than adding all chemical agents to one chemical bath, one or more chemical agents containing the chemical composition are applied separately to the fabric as described below. The one-step coating procedure was repeated except that

    2. The fabric was immersed in a bath containing one or more chemical agents of chemical composition.

    3. After the fabric was completely wetted, the fabric was removed from the treatment bath and passed between the squeeze rollers as described in the one-step application procedure.

    4). The fabric was dried in a Despatch oven at about 300 ° F. for about 5 minutes.

    5). The fabric was then immersed in a new bath containing the remaining desired chemical agent consisting of the chemical composition.

    6). The fabric was then dried and cured as described in the one-step application procedure.

III) Another two-step application procedure Approximately 100 grams of fabric was placed in a Werner-Mathis laboratory dryer.

    2. Approximately 2 liters of water containing the desired chemical was added to the jet dryer.

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

    4). The dryer was cooled to about 70 ° C. and the treatment bath was drained.

    5). The fabric was subjected to centrifugation in a dryer to remove excess liquid.

    6). While wet, the fabric was immersed in a treatment bath containing the desired chemical agent. Typically, the fabric was soaked for about 1 to about 10 seconds.

    7). Once removed from the bath, the fabric was squeezed between rolls, placed on a pin frame and dried, similar to the one-step application procedure described above.

IV) Post cure application procedure 1. Rather than curing the hydrophobic crosslinker during one drying step, the one step application procedure was repeated except that the fabric was dried and the chemical was cured as follows: It was.

    (A) The fabric was cured in a first stage in a Despatch oven at 300 ° F. for about 5 minutes.

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

i) High pressure for 5 seconds
ii) 10 second head steam
iii) 5 second buck steam
iv) 5 second buck vacuum (c) The fabric was then cured at 310 ° F. for 10 minutes (to simulate the process in garment manufacturing and to cure the permanent press post-cure resin).

V) Household dryer application procedure A 1.8 inch x 9 inch piece of fabric was cut according to the procedure to make a 4.5 inch x 6 inch template and placed on top of the fabric.

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

  3. The treated fabric was placed in a Dryel® home dry cleaning bag obtained from a Dryel® home dry cleaning kit and subjected to the home dryer at high settings for about 30 minutes.

  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 composition used Example 1
A 200 g bath was prepared containing the following chemicals:

1. Unidyne TG-992, a 9g fluorinated hydrophilic soil release agent, commercially available from Daikin
2. Repearl® F8025, a 3 g fluorinated stain repellent, commercially available from Mitsubishi.
3. 3.6 g of hydrophobic block diisocyanate crosslinker Repearl® MF, commercially available from Mitsubishi Corporation
A 100% microdenier polyester fabric was treated with this chemical composition by the one-step coating procedure described above. The moisture absorption of the chemical composition on the fabric was about 60%.

  This polyester fabric was obtained from Milliken & Company of Spartanburg, South Carolina. This fabric is a 1/140/200 denier warp of polyester processed filaments and polyester processed filaments woven together in a 2x2 right hand twill pattern with 175 warps and 80 wefts per inch of fabric. It consists of 1/150/100 denier weft (hereinafter referred to as a “test polyester fabric” special to the present invention). This fabric was subjected to a surface finishing process in which the surface of the fabric was gently sanded and then jet-dried. The finished fabric had a weight of about 6 ounces / square yard.

  Treated fabrics have 0 home washes (“AR” indicates “accepted”), 10 home washes, 20 home washes, 30 home washes, 40 home washes After home cleaning and 50 home cleanings, the above methods were tested for water and oil repellency, spray grade, and soil release of corn and mineral oils. The test results are shown in Table IA.

Example 2
Example 1 was repeated except that the concentration of 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
Example 2C: 2.0 g Unidyne TG-992, 6 g Repearl F8025, 3.0 g Repearl MF
The test results are shown in Table IA.

Example 3 (comparative example)
Example 1 was repeated, except that some of the chemical agent of the chemical composition was removed from the bath as follows.

  Example 3A: Unidyne TG-992 was not used.

  Example 3B: Repearl F8025 was not used.

  Example 3C: Repearl MF was not used.

    The test results are shown in Table IA.

Example 4
Example 1 was repeated, except that some of the chemical agents in the chemical composition were replaced with other chemicals commercially available from various manufacturers as follows.

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

  Example 4B: Repearl F8025 was replaced with 2% Zonyl 7713 commercially available from DuPont.

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

  The moisture absorption of the chemical composition on the fabric was about 60%. The test results are shown in Table IA.

Example 5
Two polyester fabrics useful for bed covers were manufactured from Milliken & Company and treated with the following chemicals according to the one-step coating procedure described above.

1.4.5% Unidyne TG-992
2.1% Repearl F8025 and 3.1.8% Arkophob DAN (hydrophobic crosslinker commercially available from Clariant)
The moisture absorption of the chemical composition on the fabric was about 75%.

  Example 5A is a flat spun polyester 56T DB 1/200/136 denier warp and a flat spun polyester 2/150/68 denier weft having a linen weave and commercially available from DuPont. Including. The fabric further contained 61 warps per inch of fabric and 45 wefts per inch of fabric and had a final fabric weight of about 8.75 ounces per square yard.

  Example 5B was similar to Example 5A except that the polyester bed cover was treated with the chemicals of the present invention and then transfer printed.

  Example 5C is a flat spun polyester fb3 SDY 75/36 denier warp having a faille weave and commercially available from Nanya, and a flat spun polyester T-121 8 / commercially available from DuPont. It included the treatment of a second polyester bedspread fabric containing 1 denier weft. The fabric contained 164 warps per inch of fabric and 37 wefts per inch of fabric and had a final fabric weight of about 10.5 ounces per square yard.

  Example 5D was similar to Example 5C except that a polyester bed cover fabric was treated with the chemicals of the present invention and then transfer printed.

  Treated fabrics are treated with water and oil repellency, spray grade, and corn after 0 home cleanings (“AR” indicates “accepted”) and 5 industrial cleanings, as described above. Oil and mineral oil were tested for soil release. The test results are shown in Table IB.

Example 6 (comparative example)
Example 1 was repeated, except that each of the chemical agents in the chemical composition was replaced with various comparative soil release agents and / or soil repellents as follows. Examples G and H were purchased garments (pants) tested with the following treated fabrics. The chemicals used are as follows.

Example 6A: 5.0% Scotchgard FC-5102 (stain repellent commercially available from 3M)
Example 6B: 5.0% Zoyl 7040 (stain repellent commercially available from DuPont)
Example 6C: 8.0% Scotchgard L-18542 (stain repellent commercially available from 3M)
Example 6D: 5.0% Scotchgard FC-248 (a fluorinated soil release agent commercially available from 3M)
Example 6E: 5.0% Zoyl 7910 (a fluorinated soil release agent commercially available from DuPont)
Example 6F: 5.0% Scotchgard L-18369 (a fluorinated soil release agent commercially available from 3M)
Example 6G: Dirt Protective Pants (DuPont Teflon on Polyester / Cotton Blend Garment)
Example 6H: NanoCare pants (100% cotton considered to be treated according to US Pat. No. 6,379,753 to Nanotex)
Example 6I: 2.5% Unidyne TG-992
0.5% Reactant 901
0.25% hydrated zinc nitrate
0.35% Unidyne TG-571 (Example 11 of US Pat. No. 4,695,488 to Daikin)
Example 6J: 3.0% Repearl F8025
2.0% Repearl SR-1100 (a soil release agent commercially available from Mitsubishi)
The test results are shown in Table II.

Example 7 (comparative example)
Example 1 was repeated except that the polyester fabric was treated according to the two-step coating procedure described above. In the first stage of this procedure, 6.0 g PD-75, a carboxylated acrylic soil release agent commercially available from Milliken & Company, and 0.5 g calcium acetate were applied to the fabric.

  The treated fabric was treated with water repellent and water after 0 home washes (“AR” indicates “accepted”), 5 home washes, and 30 home washes. Tested for oil repellency, spray grade, and soil release of corn and mineral oils. The test results are shown in Table III.

Example 8
Example 1 was repeated except that the polyester fabric was treated according to another two-step application procedure described above. In the first stage of the procedure, Unidyne TG-992 of 2% by weight of fabric and 1.0% acetic acid by weight of fabric were applied to the fabric in the dryer. In the second stage of the procedure, 8.0% Repearl F8025 and 9.6%% Repearl MF were then applied to the fabric.

  The treated fabric was treated with water repellent and water after 0 home washes (“AR” indicates “accepted”), 5 home washes, and 30 home washes. Tested for oil repellency, spray grade, and soil release of corn and mineral oils. The test results are shown in Table III.

Example 9
200 g bath containing the following chemicals a. 12g Unidyne TG-992
b. 4g Repearl F8025
c. 4g Repearl MF
d. 16 g of Freeze PFK, a permanent press resin available from Noveon, Inc.
e. 4 g of Catalyst 531, a catalyst commercially available from Omnova Solutions
f. 4 g of Atebin 1062, a softener commercially available from Boehme Filatex
A 100% cotton fabric was treated with the chemical composition according to the one-step application procedure described above. The moisture absorption of the chemical composition on the fabric was about 60%.

  The fabric was obtained from Milliken & Company, Spartanburg, South Carolina. This fabric is a 20/1 denier ring spun warp and 11/1 denier open, woven together in a 3x1 left hand twill pattern with 118 warps and 54 wefts per inch Consists of end-spun wefts. The fabric was dried by a continuous drying process, sanforized and then treated with a chemical composition. The finished fabric had a weight of about 8 ounces per square yard (hereinafter referred to as the “test cotton fabric” special to the present invention).

  Treated fabrics are treated as described above after 0 home cleanings (“AR” indicates “accepted”), 10 home cleanings, 20 home cleanings, 30 home cleanings. The method was tested for water and oil repellency, spray grade, and soil release of corn and mineral oils. The test results are shown in Table IV.

Example 10
Example 9 was repeated except that Repearl F8025 was replaced with Zoyl 7713 and Repearl MF was replaced with Hydrophobol XAN at varying concentrations as follows.

Example 10A: 8.0 g of Unidyne TG-992
4.0 g of Zoyl 7713
4.0 g Hydrophobol XAN (hydrophobic crosslinking agent commercially available from DuPont)
Example 10B: 6.0 g of Unidyne TG-992
6.0 g of Zoyl 7713
4.0g Hydrophobol XAN
Example 10C: 4.0 g of Unidyne TG-992
8.0 g of Zoyl 7713
4.0g Hydrophobol XAN
The test results are shown in Table IV.

Example 11 (comparative example)
Example 9 was repeated except that one chemical agent of the chemical composition was removed from the bath as follows.

  Example 11A: Unidyne TG-992 was not used.

  Example 11B: No soil repellent was used.

  Example 11C: No hydrophobic crosslinker was used.

    The test results are shown in Table IV.

Example 12 (comparative example)
Example 9 was repeated except that each chemical agent in the chemical composition was replaced with various comparative soil release agents and / or soil repellent chemicals. (These are the same and the same amount as the chemicals used in Example 6.) Examples G and H were purchased garments (pants) that were tested by others shown below. The chemicals used are as follows.

Example 12A: 5.0% Scotchgard FC-5102
Example 12B: 5.0% Zoyl 7040
Example 12C: 8.0% Scotchgard L-18542
Example 12D: 5.0% Scotchgard FC-248
Example 12E: 5.0% Zoyl 7910
Example 12F: 5.0% Scotchgard L-18369
Example 12G: Dirt Protective Pants (DuPont Teflon on Polyester / Cotton Blend Garment)
Example 12H: NanoCare pants (100% cotton considered to be treated according to US Pat. No. 6,379,753 to Nanotex)
Example 12I: 2.5% Unidyne TG-992
0.5% Reactant 901
0.25% hydrated zinc nitrate
0.35% Unidyne TG-571 (Example 11 of US Pat. No. 4,695,488 to Daikin)
Example 12J: 3.0% Repearl F8025
2.0% Repearl SR-1100 (a soil release agent commercially available from Mitsubishi)
The test results are shown in Table V.

Example 13
Polyester and cotton blend fabrics were treated with the chemicals of the present invention according to the one-step application procedure and post-cure application procedure described above. The fabric was obtained from Milliken & Company, Spartanburg, South Carolina. The fabric contained approximately 65% polyester yarn and about 35% cotton yarn. The warp consisted of 65/35 polyester / cotton staple fiber spun at 14.0 / 1 open end with 3.30 multiple twist. The wefts consisted of 65/35 polyester / cotton staple fibers spun at 12.0 / 1 open end with 3.25 multiple twists. Both warp and weft polyester staple fibers had a denier of about 1.2. The warp and weft were woven together in a 3 × 1 left hand twill pattern with 100 warps and 47 wefts per inch of fabric. The fabric was dried by a continuous drying process and treated with the chemicals of the present invention. The finished fabric had a weight of about 8.5 ounces / square yard.

  The chemical substance of the present invention contained the following composition.

Example 13A: Processing using one-step coating procedure
3.75% Unidyne TG-992
1.25% Zoyl 7713 (a repellent available from DuPont)
1.25% Arkophob DAN
10% Permafresh MFX (permanent press resin available from Omnova)
2.5% Catalyst KR (commercially available from Omnova)
0.25% Tebefoam (a defoamer available from Boehme Filatex)
0.5% Mykon XLT (a softener commercially available from Omnova)
Example 13B: Processing using a one-step coating procedure
5.45% of Unidyne TG-992
1.75% Zoyl 7713
2% Arkophob DAN
10% Permafresh MFX
2.5% Catalyst KR
0.25% Tebefoam
0.5% Mykon XLT
Example 13C: Processed using a one-step coating procedure
0.32% Unidyne TG-992
1.76% Arkophob DAN
3.87% Zoyl 7713
1.55% Repearl F8025
10% Permafresh MFX
2.5% Catalyst KR
0.25% Tebefoam
0.5% Mykon XLT
Example 13D: Processed using a one-step coating procedure
5% Unidyne TG-992
1% Repearl F89
3% Epl-Rez 5003 W55 (hydrophobic crosslinking agent commercially available from Shell)
Example 13E Treated using a one-step coating procedure
5% Unidyne TG-992
1% Repearl F89
2% Witcobond W-293 (hydrophobic crosslinking agent commercially available from Crompton)
Example 13F: Processed using a one-step coating procedure
5% Unidyne TG-992
1% Repearl F89
3% Epl-Rez 5003 W55
5% Permafresh MFX
1.25% Catalyst KR
0.25% Tebefoam
0.5% Mykon XLT
Example 13G: Process using one-step coating procedure
5% Unidyne TG-992
1% Repearl F89
2% Witcobond W-293
5% Permafresh MFX
1.25% Catalyst KR
0.25% Tebefoam
0.5% Mykon XLT
Example 13H: Same as Example 13F except that 1% Pluronic F-68 (a soil release agent commercially available from BASF) is added. Example 13I: Example 13G except that 1% Pluronic F-68 is added. Example 13F is the same as Example 13D, except that a permanent press resin is used with other adjuvants and the composition is not sufficiently cured to allow the permanent crease to be introduced into the fabric. It contained the same chemical composition used. This is known in the art as a post-curing process. However, the fabric was sufficiently cured to simulate processing in a garment factory prior to testing. Similarly, Example 13G shows Example 13E, except that a permanent press resin is used with other adjuvants and the composition is not sufficiently cured to allow permanent creases to be introduced into the garment. Containing the same chemical composition used in This fabric was fully cured prior to testing.

  Example 13H contained the same chemical composition used in Example 13F, except that a polyoxyethylene-polyoxypropylene copolymer (Pluronic F-68 from BASF) was added. It was applied by a post cure application method. Example 13I contained the same chemical composition used in Example 13F, except that a polyoxyethylene-polyoxypropylene copolymer (Pluronic F-68 from BASF) was added. It was applied by a post cure application method.

  Treated fabric has 0 home washes (“AR” indicates “accepted”), 5 home washes, 10 home washes, 20 home washes, 30 home washes After household cleaning, the above methods were tested for water and oil repellency, spray grade, and soil release of corn and mineral oils. The test results are shown in Table VI.

Example 14 (comparative example)
Example 13 was repeated except that each chemical agent in the chemical composition was replaced with various comparative soil release agents and / or soil repellent chemicals.

  The fabric used in Example 14D was slightly different from the fabric described in Example 13. The fabric of Example 14D was also a 65/35 polyester / cotton blend fabric. However, the warp consisted of 65/35 polyester / cotton staple fibers spun 160/1 open-end with 3.30 multiple twists. The wefts consisted of 65/35 polyester / cotton staple fibers spun 12.0 / 1 open end. Both warp and weft polyester staple fibers had a denier of about 1.2. The warp and weft were woven together in a 2 × 1 left hand twill pattern with 88 warps and 46 wefts per inch of fabric. The fabric was dried by a continuous drying process and treated with the chemicals of the present invention. The finished fabric had a weight of about 7.2 ounces / square yard.

  The chemical composition is as follows.

Example 14A: Processing using a one-step coating procedure
1.5% Zoyl 7910
18% Permafresh MFX
4.5% Catalyst KR
1.25% Mykon XLT
0.5% Tebefoam 1868
0.35% Progapal DAP-9
Example 14B: Process using one-step coating procedure
11.1% Scotchgard L-18369
2.2% Hydrophobol XAN
9% Permafresh MFX
2.2% Catalyst 531
1% Mykon NRW3
Example 14C: Process using a one-step coating procedure
6% Zoyl 7713
6% Zoyl 7714
2% Hipochem CSA
3% Ultratex REP
1.5% Hydrophobol XAN
13% Freerez PFK
2.9% Catalyst KR
Example 14D: Processed using a one-step coating procedure
10% Zoyl S410
1% Atebin 1062
3% Ultratex REP
1% Hydrophobol XAN
15% Permafresh MFX
3.75% Catalyst 531
Example 14E: Stain Protective Pants (DuPont Teflon on Polyester / Cotton Blend Garment)
Example 14F: NanoCare pants (100% cotton considered to have been treated according to US Pat. No. 6,379,753 to Nanotex)
Example 14G: Process using one-step coating procedure
8% Scotchgard L-18542
10% Permafresh MFX
2.5% Catalyst KR
0.25% Tebefoam
0.5% Mykon XLT
Example 14H: Processed using a one-step coating procedure
4% Scotchgard L-18542
10% Permafresh MFX
2.5% Catalyst KR
0.25% Tebefoam
0.5% Mykon XLT
The test results are shown in Table VII.

Example 15
The fabric of Example 13 was treated with the following chemical composition of the present invention.

Example 15A: Processing using one-step coating procedure
3.75% Unidyne TG-992
1.25% Zoyl 7713
1.25% Arkophob DAN
10% Permafresh MFX
2.5% Catalyst KR
0.25% Tebefoam
0.5% Mykon XLT
Example 15B: Process using one-step coating procedure
5.4% Unidyne TG-992
1.75% Zoyl 7713
2% Arkophob DAN
10% Permafresh MFX
2.5% Catalyst KR
0.25% Tebefoam
0.5% Mykon XLT
Example 15C: Process using one-step coating procedure
0.32% Unidyne TG-992
1.76% Arkophob DAN
3.87% Zoyl 7910
1.55% Repearl F8025
10% Permafresh MFX
2.5% Catalyst KR
0.25% Tebefoam
0.5% Mykon XLT
Example 15D Treated using a one-step coating procedure
5% Unidyne TG-992
1% Repearl F-89
3% Epi-Rez 5003 W55
Example 15E Treated using a one-step coating procedure
5% Unidyne TG-992
1% Repearl F-89
0.5% Epi-Rez 5003 W55
5% Permafresh MFX
2% Witcobond W-293
1.25% Catalyst KR
0.25% Tebefoam
0.5% Mykon XLT
This fabric is treated with water and water repellency according to the method described above after 0 home cleanings, 5 home cleanings, 10 home cleanings, 20 home cleanings, and 30 home cleanings. Oiliness, spray grade, and soil release properties of corn and mineral oils were tested. The test results are shown in Table VIII.

Example 16 (comparative example)
Example 16A: The fabric of Example 13 was treated by the post cure application procedure described above using the following comparative chemicals.

4% Scotchgard L-18542
10% Permafresh MFX
2.5% Catalyst KR
0.25% Tebefoam
0.5% Mykon XLT
Example 16B: The fabric of Example 1 was treated according to the one-step application procedure described above using the following comparative chemicals.

10% Zoyl 7040
2.0% Repearl 901
1% Free Cat (commercially available from Noveon)
0.4% Alkanol 6112 (wetting agent)
The fabric was tested after 0 home washes, 5 home washes, 10 home washes, 20 home washes, and 30 home washes. The test results are shown in Table VIII.

Example 17
Nylon 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 & Company, Spartanburg, South Carolina. The warp consisted of nylon 6,6 fibers of 70/34 denier filament. The wefts consisted of nylon 6,6 fibers of 2/070/66 denier filament. This fiber was purchased from DuPont. The fabric was woven together in a plain weave pattern having 106 warps and 68 wefts per inch of fabric. The fabric was then jet dried and then subjected to mechanical sanding and face finished. The finished fabric had a width of about 60 inches and a weight of about 4.8 ounces / square yard.

The chemical substance of the present invention had the following composition (weight% in bath)
1. 2% Zoyl 7910
2. 2% Repearl F-8025
3. 1.5% Arkophob DAN
The moisture absorption of the chemical bath on the fabric was about 52%.

  The treated fabric was treated with water repellent and water in the manner described above after 0 home cleanings (“AR” indicates “as received”), 5 home cleanings, and 10 home cleanings. Tested for oil repellency, spray grade, and soil release of corn and mineral oils. The test results are shown in Table IX.

Example 18 (comparative example)
Example 17 was repeated except that each chemical agent in the chemical composition was replaced with various comparative soil release agents and / or soil repellent chemicals. The chemical substances used are as follows.

Example 18A: 3.0% Zoyl 7713 and 1% Repearl MF
Example 18B: 3.0% Scotchgard L-18369 and 1% Hydrophobol XAN
Example 18C: 3.0% Scotchgard L-18542 and 1.5% Repearl MF
The test results are shown in Table IX.

Example 19
A piece of Nomex® fabric was treated with the inventive chemical according to the one-step application procedure described above. This fabric was obtained from Milliken & Company, Spartanburg, South Carolina. The warp and weft were woven together in a plain weave pattern having 67 warps and 43 wefts per inch of fabric. This fabric was then dried and finished by conventional means. The finished fabric had a weight of about 4.5 ounces / square yard.

  The chemical substance of the present invention contained the following composition.

Example 19A: 2% Unidyne TG-992
1% Zoyl 7713
1.5% Arkophob DAN
Example 19B: 0.25% Unidyne TG-992
1.75% Zoyl 7910
2% Repearl F8025
1.5% Arkophob DAN
Example 19C: Untreated fabric (comparative example)
The moisture absorption of the chemical bath on the fabric was about 93%.

  The treated fabric is treated with water and oil repellency, spray grade, and 0 after the home cleaning ("AR" indicates "as received") and after 5 home cleanings. Corn and mineral oils were tested for soil release. The test results are shown in Table X.

  These exemplified substrates were then tested for various surface properties.

C) Textile surface analysis procedures and test results I) Description of the following test methods a) Home cleaning procedures to test for cleaning durability as follows are cleaning procedures 1 (105 ° F cleaning) and Tide (registered) (Trademark) was performed according to AATCC test method 130-2000 using a rapid degrading power detergent.

Industrial cleaning procedures were performed according to standard procedures used by many large industrial laundry factories. This procedure was identified as being used on a colored blended textile substrate and uses the following procedure steps.

  The load size for the industrial cleaning procedure was determined to be 80% of the machine capacity (28 pounds on a 35 pound machine). The total wash cycle was about 33 minutes. For example, the time indicated as “16/1” indicates that the cleaning time is 16 minutes and the dehydration time is 1 minute. The chemicals to be cleaned were obtained from Washing Systems Inc. The chemicals were Choice MP, a concentrated nonionic surfactant, Horozon, a silylated phosphate builder, Express, an alkaline compound, and Sour, an acidic compound. The pH range of the wash cycle was maintained in the range of about 10.2 to 10.8.

    b) A spray grade test was performed according to AATCC (American Association of Textile Chemists and Colorists) test method 22-2000. The scale is as follows.

100-No top surface sticking or wetting 90-Slight random top surface sticking or wetting 80-Surface wetting at spray point 70-Partial wetting of top surface 50-Full wetting of top surface 0-Top surface And complete wetting of the entire lower surface c) Soil release was performed according to AATCC test method 130-2000. The soiling agents used in the soil release test were corn oil (CO) and mineral oil (MI). The scale is 1-5, where “1” indicates the lowest degree of dirt removal and “5” indicates the highest degree of dirt removal. In general, a rating of about 3,0 is the minimum soil level that is acceptable for normal clothing and applications.

    d) The water repellency was tested according to 3M water repellency test II (May 1992). The scale is 0-10, “0” indicates the lowest degree of water repellency (substrate having high surface energy), and “10” indicates the highest degree of water repellency (substrate having low surface energy). Indicates. The 3M water repellent test scale is as follows.

• 0 is (weight) 0% isopropanol, 100% water • 1 is 10% IPA, 90% water • 2 is 20% IPA, 80% water • 3 is 30% IPA, 70% water • 4 is 40% IPA, 60% water ・ 5 is 50% IPA, 50% water ・ 6 is 60% IPA, 40% water ・ 7 is 70% IPA, 30% water ・ 8 is 80% IPA, 20% water ・ 9 is 90% IPA, 10% water ・ 10 is 100% IPA
e) Oil repellency was performed according to AATCC test method 118-2000. The scale is 0-8, “0” indicates the lowest degree of oil repellency (substrate having high surface energy), and “8” indicates the highest degree of oil repellency (substrate having low surface energy). Indicates. The scale of oil repellency is as follows.

・ 0 is Nujol (registered trademark) mineral oil (base wetted with oil)
1 is Nujol (registered trademark) mineral oil 2 is 65/35 Nujol / n-hexadecane (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 texture test Using Kawabata evaluation system Various characteristics were measured. The Kawabata System is a scientific tool for objectively and reproducibly measuring the “texture” of fabrics. Dr. Kawabata is a polymer professor at Kyoto University in Japan. Developed by Suekawa Kawabata. It uses a set of four highly specialized measuring devices specifically developed for use in the Kawabata system, using basic mechanical properties (eg, smoothness, fullness) associated with aesthetic properties related to texture. , Rigidity, softness, flexibility, and feeling of shaving). These devices are as follows.

Kawabata pull and shear tester (KES FB1)
Kawabata Pure Bending Tester (KES FB2)
Kawabata compression tester (KES FB3)
Kawabata surface tester (KES FB4)
KES FB1 to KES FB3 were manufactured by Kato Iron Works Co, Ltd., Div. Of Instrumentation in Kyoto, Japan, and KES FB4 was manufactured by Kato Tekko Co, Ltd., Div. Of Instrumentation. In each case, the measurements were made according to a standard Kawabata test procedure in which four 8 inch x 8 inch samples were tested and the results averaged. Care was taken to avoid bending, wrinkling, stressing, or other sample deformation handling. The fabric was tested as manufactured (ie, not subsequently laundered). The dies used to cut each sample were arranged along the yarn of the fabric to improve the accuracy of the measurement.

i) Shear measurement The 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 being calibrated. The tester was set up as follows.

Sensitivity: 2 and x5
Sample width: 20cm
Shear weight: 195g
Pull speed: 2mm / s
Elongation sensitivity: 25mm
The shear test measures the resistance force when a fabric is subjected to a constant tensile force and subjected to shear deformation in a direction perpendicular to the constant tensile force.

  Average shear stiffness (G) [gf / (cm-deg.)]: The average shear stiffness was measured in each of the warp and weft directions. A value with low shear rigidity indicates a softer texture.

  Four samples were taken in each of the warp and weft directions and are shown below.

ii) Bending measurement Bending stiffness (B): A lower value means that the fabric has less stiffness. Four samples were taken in each of the warp and weft directions.

iii) Compressibility analysis The test equipment was set up according to the instructions in the Kawabata manual. The Kawabata compression tester (KES FB3) was warmed up for at least 15 minutes before being calibrated. The tester was set up as follows.

Sensitivity: 2 and x5
Stroke: 5mm
Compression speed: 1mm / 50s
Sample size: 20x20cm
The compression test measured the resistance force exerted by a plunger with a given surface area as it moved alternately in the direction perpendicular to the fabric and toward and away from the fabric sample. This test ultimately measures the work done in compressing the fabric with a pre-set force (in the forward direction) and the work done in uncompressing the fabric (in the reverse direction).

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

Maximum thickness (TMAX) —Thickness at maximum pressure (nominal 50 gf / cm ² ). A high TMAX is an excellent fabric.

Minimum thickness (TMIX) thickness at -0.5gf / cm ^2. Larger is better. A high TMIX is an excellent fabric.

Minimum density-density at minimum thickness (TMIX). In general, a lower value is better. T _min [g / cm ³ ]
Maximum density-density at maximum thickness (TMAX) -T _max [g / cm ³ ]. In general, a lower value is considered better.

Compression work per unit area (WC) - Energy to compress fabric to 50 gf / cm ² [gf-cm / cm ^2]. In general, larger is considered better.

  Reduced pressure work per unit area (WC ')-This is an indication of the elasticity of the fabric. Larger numbers are more elastic (ie, elastic texture) and are generally considered better.

iv) Surface analysis The 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 being calibrated. The tester was set up as follows.

Sensitivity 1: 2 and x5
Sensitivity 2: 2 and x5
Tension weight: 480g
Surface roughness weight: 10g
Sample size: 20x20cm
The surface test measures the friction and geometric roughness characteristics of the surface of the fabric.

  Friction Coefficient (MIU)-Average Friction Coefficient [Dimensionless]: This was tested in each direction of warp and weft. Higher values consist of more fiber ends and loops on the surface, which gives the fabric a softer, brittle texture. Four samples were taken in each direction of warp and weft, and are listed below.

  Surface Roughness (SMD): Average deviation of movement of contact perpendicular to the surface [microns] It shows how the surface of the fabric is rough. Lower values consist of fiber ends and loops with more surface, which gives the fabric a softer and more pleasant texture. Four samples were taken in each direction of warp and weft, and are listed below.

  g) The dry cleaning test method was performed by placing about 6 "x 6" pieces of fabric in a 1 quart jar containing 250ml perchlorethylene. Shake jar 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) An electrostatic test method was performed by placing a piece of fabric about 3 inches by 8 inches on a laboratory bench. The sample was rubbed vigorously 20 times (in one direction) with a new paper towel. Immediately, about 1 inch away from the fabric, the Simco FM300 Electrostatic Fieldmeter was positioned and a button was pressed to measure. The results obtained were recorded in kilovolts. To obtain the results after conditioning the fabric, the fabric sample was placed in a controlled room in an environment of 70 ° and 65% relative humidity. The measurement was repeated for the conditioned sample.

  i) Advancing and receding contact angles were measured using the following two devices and procedures.

    i) Tensiometer test method: As used herein, tension measurement refers to the gravimetric measurement of the force of interaction when a solid is in contact with a test liquid. These interaction forces are dynamic measurements and reflect the interaction of all immersed objects. The force as the object enters and exits the test liquid is measured. From these measurements, both advancing and receding contact angles, respectively, can be calculated indirectly (Wilhelmy equation).

    ii) Angle meter test method: As used herein, angle measurement refers to optical observation of fixed droplets of a test liquid on a solid substrate. For each test liquid, the tangent angle is measured, which provides a direct measurement of the “advance” (static) contact angle. These angles reflect only the average force applied from the area under the drop (footprint), not the bulk article. These angle calculations can be used to determine surface energy and corresponding components.

  Both the goniometer test method and the tensiometer test method achieve similar results, and the goniometer test method is a small area static measurement.

  j) X-ray photoelectron spectroscopy (XPS) was used to perform the surface chemistry analysis shown in Example 28 and FIGS. XPS is described as follows.

  Journal of Polymaer Science and Polymer Chemistry Ed. (1977, vol. 15, p.2843) As described in DT Clark and HR Thomas, the first use of XPS is to inspect the polymer surface. It has become the standard quantitative tool for their characterization. While the solid sample is irradiated with monochromatic X-rays, the photoelectronically emitted energy analyzed electrons show a sharp peak corresponding to the binding energy of core level electrons in the sample. These binding energy peaks can be used to identify chemical components in the sample.

  The mean free path of electrons in a solid is very short (λ˜2.3 nm). Macromolecules (1988, vol. 21, p. 2166) See W. S. Bhatia, D.H. Pan, and J. T. Koberstein. The effective sampling depth Z of XPS can be calculated by Z = 3λ cos θ, where θ is the angle between the surface normal and the emitted electron path to the analyzer. Therefore, the maximum depth to be inspected is about 7 nm when θ = 0. For the typical elemental components C, N, and O of the polymer, optimized XPS can detect a composition of 0.2 atomic percent. XPS is also very sensitive to F and Si. Such quantitative information is very useful in understanding the behavior of the polymer surface.

  X-ray photoelectron spectroscopy (XPS) was employed here to examine the chemical composition of the modified fabric surface and to evaluate changes in surface chemical composition under various environments. XPS was obtained using a Perkin-Elmer Model 5400 XPS spectrometer with a Mg Kα X-ray source (1253.6 eV) operating at 300 W, 14 kV DC, emission current 25 mA. Photoelectrons were analyzed in a hemispherical analyzer using a position detector.

II) Analysis result “N / A” or “NA” shown in the table indicates that the test data cannot be used for the item.

  The test results for Examples 1-4 are shown in Table IA. The results of Example 1 demonstrate the persistence of the chemicals of the present invention on a polymer fabric while simultaneously maintaining an acceptable level of soil release throughout at least 30 household cleaning cycles.

  The results of Example 2 show that the ability to maximize soil repellency performance (ie, spray grade is the amount of Unidyne TG-992) at the expense of soil release (ie, mineral oil release is reduced with a small amount of Unidyne TG-992). The ability to maximize soil release (i.e., mineral oil release is high) at the expense of soil repellency (i.e., spray grade is reduced with high amounts of Unidyne TG-992) The improved versatility of the chemicals of the present invention. This versatility allows the chemicals of the present invention to be tailored to specific end uses such as rainwear where water repellency is more desirable and workwear where soil release is more desirable.

  The results of Comparative Example 3 show the superior performance obtained with the novel combination of chemicals disclosed by the present invention. As shown in Comparative Examples 3A-3C, without this novel combination, repellency, spray grade, and soil release properties are not optimized.

The results of Example 4 show that when combined with other chemical agents in a chemical composition in proportion to provide repellency, spray grade, and persistence of soil release properties through at least 30 household cleaning cycles. It shows that different chemicals may be used for the fluorinated soil repellent and soil release agent.

The test results of Example 5 are shown in Table IB. This result demonstrates the persistence and versatility of the chemicals of the present invention on a substrate, such as a polyester woven bed cover, with various structures and fiber denier. This result further demonstrates the persistence and versatility of a textile substrate comprising flat polyester (rather than being processed) and a textile substrate that has not been subjected to a surface finish sanding process.

The test results of Example 6 are shown in Table II. This result shows that the inventive chemical shown in Example 1 is at least 30 household cleaning cycles relative to the comparative chemical shown in Examples 6A-6J provided for comparison on the same fine denier polyester substrate. Provides continuity of repellency, spray grade, and soil release properties through.

  The results of Example 7 (Comparative Example) and Example 8 (Example) are shown in Table III. The results of Example 7 demonstrate the persistence in water and oil repellency of the inventive chemicals on polyester fabric while simultaneously maintaining an acceptable level of soil release throughout at least 5 household cleaning cycles. This result further demonstrates the versatility of the chemicals of the present invention by various chemical application techniques and procedures.

The results of Example 8 show the persistence in water and oil repellency of the chemicals of the present invention on polyester fabric while simultaneously maintaining an acceptable level of soil release throughout at least 30 household cleaning cycles. This result further shows that another two-step application procedure provides higher spray grade results while maintaining a higher level of repellency and corn oil release than the one-step application procedure.

  The test results of Example 9, Example 10, and Comparative Example 11 are shown in Table IV. The results of Example 9 demonstrate the persistence of the chemical of the present invention on cotton fabric while simultaneously maintaining an acceptable level of soil release throughout at least 30 household cleaning cycles, as shown below.

  The results of Example 10 show that the ability to maximize soil repellency (ie, spray grade is the amount of Unidyne TG-992) at the expense of soil release (ie, mineral oil release is reduced with a small amount of Unidyne TG-992). The ability to maximize soil release (i.e., mineral oil release is high) at the expense of soil repellency (i.e., spray grade is reduced with high amounts of Unidyne TG-992) The improved versatility of the chemicals of the present invention. This versatility allows the chemicals of the present invention to be tailored to specific end uses such as rainwear where water repellency is more desirable and workwear where soil release is more desirable.

The results of Example 11 show the superior performance obtained with the novel combination of chemicals disclosed by the present invention. For example, as shown in Examples 10A-10C, without this new combination, repellency, spray grade, and soil release properties are not optimized.

The test results of Comparative Example 12 and Example 9 are shown in Table V. This result shows that the chemicals of the present invention are persistent in repellency, spray grade, and soil release characteristics over at least 30 household cleaning cycles relative to the comparative chemicals provided for comparison using the same substrate. To provide.

The results of Example 13 are shown in Table VI. This result demonstrates the persistence of the inventive chemicals on polyester and cotton blend fabrics while simultaneously maintaining an acceptable level of soil release throughout at least 30 household cleaning cycles. This result further indicates that the permanent press resin is fully cured during the fabric finishing process, or that the resin is partially cured during the fabric finishing process and after garment manufacturing to obtain a sustainable crease. The versatility of the chemicals of the invention in cured (post-curing) applications is shown. Both processes provide a high level of water and oil repellency, an acceptable level of soil release, and an acceptable level of spray rating.

The test results of Example 14 are shown in Table II. This result shows that the inventive chemicals shown in Examples 13A-13J were at least 30 domestic wash relative to the comparative chemicals shown in Examples 13A-14H provided for comparison on the same polyester and cotton blend substrate. Shows that it provides repellency, spray grade, and persistence of soil release properties throughout the cycle.

  The results of Example 15 and Comparative Examples 16 and 18 are shown in Table VIII and Table IX. The results of Example 15 demonstrate the durability in water and oil repellency of the chemicals of the present invention on polyester and cotton blend fabrics while simultaneously maintaining an acceptable level of soil release throughout at least 30 household cleaning cycles. Show. The result is further that the present invention in adding a permanent press resin to the fabric before the chemical of the present invention is fully cured or after the chemical of the present invention is fully cured (post-curing). It shows the versatility of chemical substances. Both processes provide a high level of water and oil repellency, an acceptable level of soil release, and an acceptable level of spray rating. This result further shows the persistence of the inventive chemicals used in Examples 15A and 15B for combustion motor oil (BMO) soil release on this polyester and cotton blend fabric after at least 30 industrial washes. Indicates effectiveness.

  The results of Comparative Example 16 showed that the inventive chemicals shown in Examples 15A-15E were at least 30 relative to the comparative chemicals shown in Examples 16A and 16B provided for comparison on the same polyester and cotton blend substrate. It provides repellency, spray grade, and persistence of soil release characteristics throughout the home cleaning cycle.

  The results of Example 17 demonstrate the persistence of the chemicals of the present invention on a nylon fabric substrate through at least 30 domestic wash cycles when spray grade and oil release were tested by the methods described above.

The results of Comparative Example 18 show the superior performance of the chemicals of the present invention on a nylon fabric substrate for comparison chemicals for spray grade and corn oil and mineral oil release through at least 10 domestic wash cycles.

The test results of Example 19 are shown in Table X. This result shows improved corn oil as well as mineral oil release on untreated Nomex® fabric. This result further demonstrates that the chemicals of the present invention on Nomex® fabrics through at least 15 household cleaning cycles when repellency, soil release, and spray grade were tested by the methods described above. Shows persistence.

III) Further analysis by modification of test method Example 20
To demonstrate that the chemicals of the present invention provide improved water and oil repellency for various types of textile substrates, improved other textile substrates, and improved spray grades, Other fabric substrates were treated with the chemicals of the present invention using a one-step coating procedure and compared against the same lost substrate in the untreated state.

  The chemical composition used for these textile substrates is as follows.

1% Repearl F-89, repellent 5% Unidyne TG-992, soil release agent 2% Witcobond W-293, crosslinker Example 20A
A 100% acetate textile substrate manufactured by Milliken & Company was used to test for water and oil repellency, spray grade, and corn and mineral oil soil release properties by the methods described above. The acetate consists of a 191 × 50 satin weave pattern and contains 75/19 denier glossy warp (against the blur) and 150/38 denier glossy weft. This acetate had a moisture absorption of about 80% of the chemical composition relative to the substrate.

Example 20B
A 100% acrylic textile substrate purchased from a textile store was used to test for water and oil repellency, spray grade, and corn and mineral oil soil release by the methods described above. The acrylic had a felt structure and had a moisture absorption of about 250% of the chemical composition relative to the substrate.

Example 20C
A 100% wool textile substrate purchased from a textile store was used to test for water and oil repellency, spray grade, and corn and mineral oil soil release by the methods described above. The wool had a plain weave structure and had a moisture absorption of about 80% of the chemical composition relative to the substrate.

Example 20D
A 100% silk textile substrate purchased from a textile store was used to test for water and oil repellency, spray grade, and corn and mineral oil soil release by the methods described above. This silk was raw silk having a woven fabric structure similar to a weave fabric. The moisture absorption of the chemical composition relative to the substrate was about 100%.

Test results are shown in Table XI. The results for Example 20A show that the treated acetate exhibits improved water and oil repellency when compared to untreated acetate. The results for Example 20B show that the treated acrylic exhibits improved oil repellency when compared to untreated acrylic. The results for Example 20C indicate that the treated wool exhibits improved oil repellency and improved corn oil and mineral oil soil release when compared to untreated wool. The results for Example 20D show that the treated silk exhibits improved water and oil repellency and improved spray rating when compared to untreated silk.

Example 21
Example 1 was repeated except that some other common detergent was used instead of Quick Dissilving Tide®. The cleaning agents used are as follows.

Example 21A: Mountain Spring Tide®
Example 21B: Cheer®
Example 21C: Tide Free Liquid®
Example 21D: Era®
Example 21E: All®
Example 21F: Downy® (inside the washer) and Quick Dissilving Tide®
Example 21G: Bounce® (inside the washer) and Quick Dissilving Tide®
Test results are shown in Table XII. This result is obtained with good soil release and an acceptable level of repellency and spray grade using a variety of different detergents and fabric softeners on the polyester substrate.

Example 22
In order to determine how the chemicals of the present invention affect the texture (or feel) of the fabric substrate, several fabric substrates are treated as described below, and then using the Kawabata evaluation system. Tested. The substrates tested and the chemical compositions used are as follows.

  Example 22A: Example 1 was repeated.

  Example 22B: Example 6B was repeated.

  Example 22C: The textile substrate described in Example 1 was not treated as a comparative example.

Test results are shown in Table XIII. A lower value of bending stiffness indicates a softer texture. This result shows that the chemicals of the present invention do not have a detrimental effect on the texture of the polyester fabric and actually improve the texture when tested using the Kawabata method.

Example 23
Durability to dry cleaning was tested on fine denier polyester fabric treated with the chemical composition of the present invention, along with several comparative chemical compositions, according to the dry cleaning procedure described above. The treated fabric is water and oil repellent and sprayed before dry cleaning cycle (as received), after 1 dry cleaning cycle, after 5 dry cleaning cycle, and after 5 dry cleaning cycle and ironing. Tested for grade. The tested substrates are 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. This result indicates that the chemical treatment of the present invention can withstand the dry cleaning process and the dry cleaning and ironing process and maintain some persistence during at least 5 dry cleaning cycles.

Example 24
Other tests were conducted to determine the breathability of fine denier polyester fabric substrates treated with the chemical treatment method of the present invention. The treated fabric was compared to an untreated polyester fabric and the same fabric coated with a competitive chemical composition. This test is performed according to ASTM test method D737-6 at 125 Pa (Pascal) air pressure, and the results are given in units of “cfm” (cubic feet per minute). The tested textile substrates and the chemicals used are as follows:

  Example 24A: Example 1 was repeated.

  Example 24B: Example 6B was repeated.

  Example 24C: The textile substrate described in Example 1 was not treated as a comparative example.

Test results are shown in Table XV. This result indicates that isomerism was hardly affected by the treatment with the chemical substance of the present invention. This result further indicates that the breathability of the fabric treated with the chemical of the present invention is better compared to the same fabric treated with the comparative chemical.

Example 25
Other tests were performed to determine the effect of the chemicals of the present invention on the electrostatic charge of fine denier polyester fabric substrates. The treated fabric was compared to an untreated polyester fabric and the same fabric coated with a competitive chemical composition. This test was performed according to the procedure described above. The results are as follows: 70% and 65% relative humidity before dry cleaning cycle (as received), after 1 dry cleaning cycle, after 5 dry cleaning cycle, and after 5 dry cleaning cycle and ironing. When adjusted, it is given in “kV” (kilovolts). “NR” indicates that the electrostatic charge exceeds the instrument's ability to measure charge. The tested textile substrates and the chemicals used are as follows:

  Example 25A: Example 1 was repeated.

  Example 25B: Example 6B was repeated.

  Example 25C: The textile substrate described in Example 1 was not treated as a comparative example.

  Test results are shown in Table XVI. This result shows that after 5 washes with conditioning, the polyester substrate treated with the chemicals of the present invention actually reduces the electrostatic charge on the substrate. This result further indicated that the polyester substrate treated with the chemicals of the present invention produced less static charge than the same fabric treated with the comparative chemicals without washing and after 5 washings with conditioning. Is shown. Thus, the polyester substrate treated with the chemicals of the present invention produced less electrostatic charge than the untreated polyester substrate after 1 and 5 washings with conditioning.

In addition, all results measured some static charge, except for polyester substrates treated with the chemicals of the present invention after 5 washes and conditionings, which showed that the substrates were cluttered by unwanted static electricity. It was shown to demonstrate. The only sample that did not show clutter due to static was the polyester substrate treated with the chemicals of the present invention after 5 washes and conditioning. Persistent antistatic and clinging prevention is difficult to achieve on polyester substrates, especially fine denier polyester substrates, so these results use the inventive chemicals on a variety of substrates. Shows other benefits.

Example 26
The advancing and receding contact angles were measured for polyester substrates treated with various inventive and comparative chemical compositions using the goniometer test method and the tensiometer test method described above. The chemical composition is as follows.

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

  Example 26B: Example 26A was repeated for a polyester film treated only with 4.5% Unidyne TG-992, a soil release agent, and the contact angle was measured.

  Example 26C: Example 26A was repeated for a polyester film treated only with 1.5% Repearl F-8025, a soil repellent, and the contact angle was measured.

  Example 26D: Example 6B was repeated on a fine denier polyester substrate and the contact angle was measured.

  Example 26E: Example 6C was repeated for the polyester film and for the polyester / cotton blend fabric of Example 13 and the contact angle was measured.

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

Test results are shown in Table XVII. This result shows improved soil resistance, and improved soil resistance is expected for the chemical composition of the present invention compared to a traditional fluorinated repellent (Example 26B). This result also shows that improved water resistance is expected when compared to the newer repellent (Example 26C). Furthermore, the results also show that the advancing contact angle is dominated by Repearl F-8025 (soil repellent) and the receding contact angle is dominated by Unidyne TG-992 (soil release agent), thereby Provides support for chemical compositions that automatically adapt to environmental changes. Finally, the results show that the chemical composition of the present invention gives similar results for films in addition to natural and synthetic fibers and textile substrates.

Example 27
Using the receding contact angle shown in Example 26, the surface energy was calculated at both 25 ° C. and 40 ° C. for fine denier polyester substrates treated with various inventive and comparative chemical compositions. The result is given in units of millijoules / square meter. The surface energy at 40 ° C. was determined using the same measurement technique, but the samples were soaked at 40 ° C. for 1 hour and vacuum dried before testing. The chemical composition is as follows.

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

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

  Example 27C: Treated with only 1.5% Repearl F-8025, a soil repellent, Example 1 was repeated and the surface energy was measured.

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

  Example 27E: Example 6D was repeated and the surface energy was measured.

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

Test results are shown in Table XVIII. This result reflects the novel 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 exhibits a change from low to high surface energy as a result of environmental effects. This surface energy change is representative of the demands of persistent soil repellency and soil release or treated surfaces.

Example 28
Surface chemical analysis of fluorine, carbon, and oxygen was performed on fine denier polyester fabrics treated with the present invention and comparative chemicals using XPS analysis techniques. 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.

The test results of Example 28 are shown in Table XIX and FIGS. 1-3.

Detailed Description of the Drawings As shown in Table XIX and FIGS. 1-3, the fluorine-containing and oxygen-containing segments on the surface are the same as for the treatment used in Example 28A, even though the sample was exposed to water fork or heat. , Remains relatively constant. However, when the sample is exposed to water and returns essentially to its original value after heating, the fluorine decreases and the oxygen increases due to the treatment of Example 28B (the inventive chemical). Without being based on theory, this indicates that in the presence of water at 40 ° C., the ethylene oxide segment of Unidyne TG-992 is hydrated and swells well enough to outperform the fluorinated segment. . This explains the change in surface energy that has been shown to occur, as well as the excellent soil repellency and soil release properties of the chemical compositions of the present invention. Subsequent heating restores the polymer to its original form.

  FIG. 1 further illustrates that Examples 28A and 28E do not exhibit environmental responsiveness to water at 40 ° C. as shown in Example 28B. Examples 28C and 28D show a similar environmental response to Example 28B (a chemical of the present invention). However, as shown in FIG. 2, after 10 home washes, much more fluorine is lost from Examples 28C and 28D than from Example 28B (a chemical of the present invention). This is particularly true for Example 28D, indicating the lack of persistence of these treatments.

IV) Further analysis of various types of fabrics Example 29
Suit fabrics consisting of about 65% polyester fiber and about 35% wool fiber are described above (and generally U.S. Pat. Nos. 5,630,236, 5,591,236, and / or 5,951, Tested using the inventive chemicals and comparative chemicals according to the home dryer application procedure (illustrated in No. 716). The treated fabric was tested for corn oil soil release, water repellency, and oil repellency as described above. An untreated comparative fabric was also tested. The chemical composition used for the treatment is as follows.

Example 29A: Untreated fabric piece (comparative example)
Example 29B: 5% Unidyne TG-992
Example 29C: 5% Unidyne TG-992
1% Repearl F-89
Test results are shown in Table XX. This result indicates that soil release and soil repellency are imparted to the textile substrate using a home dryer application procedure, providing corn oil soil release and water repellency, and oil repellency. This result further demonstrates the versatility and ease when such chemicals are applied to a substrate to obtain such soil release and repellency.

  Thus, it has been known to use fluorocarbon polymers and hydrophobic soil release polymers together or separately to obtain water and oil repellency and soil release properties for a substrate, but these properties can be used simultaneously. And has proved difficult to obtain with persistence after being subjected to repeated household and industrial cleaning cycles. Because these polymers have a tendency to interact and clean the substrate during cleaning, the soil repellent chemical, soil release chemical, and hydrophobic crosslinker that work together as shown in Examples 1-18. It was amazing to find. The concentration of each chemical agent, including the chemical agent used to treat the substrate, in combination with a novel ratio of chemical agents, and careful selection of the chemical agents, all depend on the effectiveness of this process and product, especially sustainability. It seems to play an important role in determining gender.

  In one or more aspects of the invention, the chemical composition is applied to the substrate in a one-step coating process, a two-step coating process, or an alternating two-step coating process, as described above. Indeed, as shown in each example, polyamides, polyaramids, polyesters, cotton, and polyester / cotton blended substrates, when treated according to the present invention, are related to water and oil repellency and soil release durability. All resulted in improved performance.

  Accordingly, the treated substrates of the present invention can be used in jackets (eg, rainwear), work clothes (eg, uniforms), fashion apparel (eg, shirts, pants, and other garments), cloths, table cloths (eg, , Table linens and napkins), residential drapes, carpets, outdoor fabrics (eg, outdoor furniture, awnings, boat covers, and grill covers), and other products, many applicable In this case, it is desirable to produce a substrate having water repellency as well as oil repellency and soil release durability.

  These and other modifications and variations of the present invention will be practiced by those skilled in the art without departing from the spirit and scope of the present invention. Furthermore, those skilled in the art will recognize that the above description is illustrative only and is not intended to limit the scope of the claims.

3 is a graph showing XPS surface chemistry analysis for microdenier polyester fabric substrates treated with the chemical composition of the present invention and several microdenier polyester fabric substrates treated with various comparative chemical compositions. Shows surface chemical analysis of fluorine, carbon, and oxygen before the substrate is subjected to environmental changes (ie, as received after being treated with chemicals) and after 10 home cleanings. Except that, the same graph as FIG.

Claims (34)

A composition that imparts persistent repellency and soil release properties to a substrate, the composition comprising:
(A) a soil release agent,
A composition comprising a combination of (b) a soil repellent and (c) a hydrophobic cross-linking species.   The composition of claim 1, wherein the concentration ratio of (a) :( b) :( c) is about 10: 1: 0.1 to 1: 10: 5 by weight.   The composition of claim 1, wherein the concentration ratio is about 5: 1: 0.1 to 1: 5: 3.   The composition of claim 1, wherein the concentration ratio is about 1: 2: 1. A composition that imparts persistent repellency and soil release properties to a substrate, the composition comprising:
(A) a soil release agent,
A composition comprising (b) a soil repellent, and (c) a mixture of isocyanate-containing hydrophobic crosslinking species.   6. The composition of claim 5, wherein the concentration ratio of (a) :( b) :( c) is about 1: 2: 1 by weight. Ethoxylated polyester, sulfonated polyester, ethoxylated nylon, carboxylated acrylic, cellulose ether or ester, hydrolyzed polymaleic anhydride polymer, polyvinyl alcohol polymer, polyacrylamide polymer, hydrophilic A soil release agent selected from the group consisting of: a fluorinated soil release polymer, an ethoxylated silicone polymer, a polyoxyethylene polymer, and a polyoxyethylene-polyoxypropylene copolymer;
A composition produced by combining a repellent and an isocyanate-containing hydrophobic crosslinking species. A composition that imparts persistent repellency and soil release properties to a substrate, the composition comprising:
(A) a fluorinated soil release agent;
A composition comprising (b) an antifouling agent, and (c) a hydrophobic crosslinking species. A composition that imparts persistent repellency and soil release properties to a substrate, the composition comprising:
(A) a soil release agent,
A composition comprising (b) an antifouling agent, and (c) an epoxy-containing hydrophobic crosslinking species. (A) a fluorinated soil release agent;
A composition comprising (b) an antifouling agent, and (c) an isocyanate-containing hydrophobic crosslinking species. A composition that imparts persistent repellency and soil release properties to a substrate, the composition comprising:
(A) a fluorinated soil release agent;
A composition comprising a combination of (b) a fluorinated soil repellent and (c) an isocyanate-containing hydrophobic crosslinking species. A composition that imparts persistent repellency and soil release properties to a substrate, the composition comprising:
(A) a fluorinated acrylate-containing polymer,
A composition comprising (b) a fluorinated urethane-containing polymer, and (c) an isocyanate-containing crosslinking species. A composition that imparts persistent repellency and soil release properties to a substrate, the composition comprising:
(A) a soil release agent,
(B) a stain repellent,
A composition comprising (c) a hydrophobic crosslinking species, and (d) a flame retardant composition. A composition that imparts persistent repellency and soil release properties to a substrate, the composition comprising:
(A) a soil release agent,
(B) a stain repellent,
A composition comprising (c) a hydrophobic cross-linking species, and (d) an antimicrobial compound. A composition that imparts persistent repellency and soil release properties to a substrate, the composition comprising:
(A) a fluorine-containing polymer having a non-esterified backbone and adapted to impart repellency and soil release durability to the substrate;
A composition comprising a mixture produced by combining (b) a soil release agent, and (c) a hydrophobic cross-linking species. Ethoxylated polyester, sulfonated polyester, ethoxylated nylon, carboxylated acrylic, cellulose ether or ester, hydrolyzed polymaleic anhydride polymer, polyvinyl alcohol polymer, polyacrylamide polymer, hydrophilic A soil release agent having an active group selected from the group consisting of: a fluorinated soil release polymer, an ethoxylated silicone polymer, a polyoxyethylene polymer, and a polyoxyethylene-polyoxypropylene copolymer;
A composition produced by combining a fluorine-containing repellent and a hydrophobic blocked isocyanate cross-linking species.   The composition of claim 16 further comprising a flame retardant composition.   The composition of claim 16 further comprising an antimicrobial compound. A composition that imparts persistent repellency and soil release properties to a substrate, the composition comprising:
(A) a fluorine-containing copolymer selected from the group consisting of fluoroalkyl acrylates, fluoroarylate, and fluorinated and substituted urethanes, adapted to impart soil release properties to the substrate;
A composition comprising (b) an antifouling agent, and (c) a hydrophobic crosslinking agent.   20. The composition of claim 19, wherein the hydrophobic crosslinking agent comprises an isocyanate containing species.   The composition of claim 19, wherein the isocyanate-containing species is a blocked isocyanate. Ethoxylated polyester, sulfonated polyester, ethoxylated nylon, carboxylated acrylic, cellulose ether or ester, hydrolyzed polymaleic anhydride polymer, polyvinyl alcohol polymer, polyacrylamide polymer, hydrophilic A fluorinated soil release polymer, an ethoxylated silicone polymer, a polyoxyethylene polymer, and a polyoxyethylene-polyoxypropylene copolymer, adapted to impart soil release properties. 1 fluorine-containing species,
A second fluorine-containing species selected from the group consisting of waxes, silicones, hydrophobic resins, and fluoropolymers, adapted to impart sustainable repellency, and monomers having blocked isocyanates, aromatics A composition consisting essentially of a cross-linking species selected from the group consisting of diisocyanates, blocked diisocyanates, polymers containing blocked isocyanates, epoxy-containing compounds, epoxy resins, diisocyanate-containing monomers, and diisocyanate-containing polymers.   23. The composition of claim 22, wherein the first fluorine-containing species includes an acrylate.   23. The composition of claim 22, wherein the second fluorine-containing species comprises a fluorinated substituted urethane.   23. The composition of claim 22, wherein the cross-linking species includes an aromatic diisocyanate.   The composition according to claim 22, wherein the cross-linking species includes an epoxy resin. A first fluorocarbon acrylate having added ethylene oxide groups and adapted to impart soil release properties;
A composition adapted to be applied to a textile substrate, comprising: a second fluorinated urethane-containing species adapted to impart sustainable repellency; and an isocyanate-containing species. Ethoxylated polyester, sulfonated polyester, ethoxylated nylon, carboxylated acrylic, cellulose ether or ester, hydrolyzed polymaleic anhydride polymer, polyvinyl alcohol polymer, polyacrylamide polymer, hydrophilic A fluorinated soil release polymer, an ethoxylated silicone polymer, a polyoxyethylene polymer, and a polyoxyethylene-polyoxypropylene copolymer, adapted to impart soil release properties. 1 fluorocarbon-containing species,
A second fluorine-containing species selected from the group consisting of waxes, silicones, hydrophobic resins, and fluoropolymers, adapted to impart sustainable repellency, and monomers having blocked isocyanates, aromatics A composition consisting essentially of a cross-linking species selected from the group consisting of diisocyanates, blocked diisocyanates, polymers containing blocked isocyanates, epoxy-containing compounds, epoxy resins, diisocyanate-containing monomers, and diisocyanate-containing polymers.   30. The composition of claim 28, wherein the first fluorine-containing species comprises an acrylate.   30. The composition of claim 28, wherein the second fluorine-containing species comprises a fluorinated substituted urethane.   30. The composition of claim 28, wherein the cross-linking species comprises an aromatic diisocyanate.   29. The composition of claim 28, wherein the cross-linking species includes an epoxy resin. A first fluorocarbon acrylate having added ethylene oxide groups and adapted to impart soil release properties;
A composition adapted to be applied to a textile substrate, comprising: a second fluorinated urethane-containing species adapted to impart sustainable repellency; and an isocyanate-containing species. A composition that imparts persistent repellency and flame retardancy to a substrate, the composition comprising:
(A) a soil release agent,
(B) a stain repellent,
A composition comprising a combination of (c) a hydrophobic cross-linking species, and (d) a flame retardant.

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