JP4647188B2 - Improved polymer-grafted cotton fibers and products - Google Patents

Description

Detailed Description of the Invention

  The present invention relates to the field of graft polymer coatings, particularly applied to cotton and cotton polyester fibers and fabrics, with respect to clocking, color fastness, shrinkage, abrasion resistance, antifouling, and hand properties. In certain embodiments, the present invention also relates to adding stretch recovery properties to cotton and cotton polyester fibers and fabrics.

  Textiles used for children's clothing must have characteristics such as softness, excellent colorability, color fastness, and acceptable clocking. Furthermore, it is effective that the clothes are not easily soiled to some extent. Many consumers prefer cotton because it is a natural fiber and is usually soft. Fabrics used in children's apparel and similar applications, however, usually show poor performance with respect to clocking, abrasion resistance, color fastness, antifouling, and shrinkage.

  Cost is an important factor in children's clothing. The material processing and dyeing processes used in the manufacture of children's clothing are different from those used for applications such as adult clothing. For example, children's clothing may be printed with a combination of pigment and adhesive rubber, as opposed to the more expensive reactive dyes used in adult clothing. Since colored pigments do not easily transfer to cellulose fibers and do not fix to them, a sticking agent is usually used to improve fastness. A soft polymer adhesive binder or resin is used as the fixing agent. Other useful stickers include alum, casein, starch, acrylic, rosin size, polyvinyl alcohol, and cationic colored fixatives. They improve durability by confining and bonding the pigment to the fiber surface. Binders and resins only provide a modest increase in durability because they are surface treatments and generally have only moderate toughness. Binders or resins can make fabric-like beauty stiff, while often having a negative impact on liquid distribution and absorbent properties.

Clocking is the transfer of color from the surface of a colored fabric, mainly by frictional action, to an adjacent region of the same fabric or to another surface. Clock robustness is frictional robustness. Darker colors require an excess of pigments and binders or resins that are easily peeled off or rubbed off. Using this dyeing process to obtain a dark blue color with acceptable clocking produces an unacceptably hard garment. Improving the clock fastness / color fastness of dyed fabrics has been a continuing problem in the fabric industry.
Current techniques for improving one or more features, such as clocking, for example, result in reduced performance at least with respect to the hand and usually also with respect to shrinkage. Furthermore, the treatment exhibits inferior fastness to the fabric during washing.

  It is known to graft certain chemicals onto cotton fibers. US Pat. No. 2,789,030 discusses a method for modifying cellulosic fabrics modified with glyoxal and modified with acrylic monomers. US Pat. No. 3,989,454 teaches grafting acrylates, particularly ethyl acrylate monomers, onto cotton and mercerized cotton using high energy gamma radiation as an initiator and water / methanol as a solvent. U.S. Pat. No. 4,901,389 teaches the grafting reaction on fiber materials from which free radicals are formed, and then adding a fluoromonomer, especially a grafted fluoroacrylate. The grafting is aided by adding a graftable derivative of morpholine, ie morpholinoethyl acrylate. US Pat. No. 4,737,156 discloses the use of cationic cellulose graft copolymers to improve dyefastness to dyed textile substrates by post-dye application (additional). U.S. Pat. No. 4,524,093 discloses a latex coating composition of an emulsion of an acrylate monomer and a glyoxal cured resin.

One way to improve the feel is to treat the fabric with a softening agent. The use of silicone to soften fabrics, i.e. to provide lubrication between fibers and yarns so that they move more easily relative to each other, has been well known for a long time. In addition, the use of organically modified silicon for fabric treatment has also been well documented over the years (US Pat. Nos. 4,620,878; 4,705,704; 4,800,026; 4, 824, 877; 4,824, 890; and 5,173, 201. Each of the aforementioned patents is hereby incorporated by reference, and this type of silicone is usually applied to the dough in the form of an aqueous emulsion.
Other silicone fluids, such as polydimethylsiloxane, provide additional benefits such as improved fabric feel. Examples of these pre-emulsified silicones are a 60% emulsion of polydimethylsiloxane (350 cs) sold by Dow Corning under the trade name Dow Corning 1157 (TM) fluid, and General Electric SM2140 (TM) Silicon Is a 50% emulsion of polydimethylsiloxane (10,000 cs) sold by General Electric under the trade name. Such a composition is usually added to either the cleaning or rinsing water of the cleaning operation. They are water-dispersible microemulsions that are usually aqueous and contain from about 0.1% to about 15% microemulsified functional silicone. The composition is diluted in washing or rinsing.

US Pat. No. 5,616,758 describes a cationic silicone composition that can be used as a lubricant for fibers such as polyester, nylon, acrylic, aramid, cotton, wool, and mixtures thereof. The use of silicon compounds in the processing of synthetic fibers is well known in the art. See, for example, the description of epoxy silicon in US Pat. No. 2,947,771. Such silicon compounds are effective in providing both increased lubricity of the fibers and improved softness with respect to fabrics made from these fibers. However, epoxy silicones suffer from the disadvantage that they have limited durability when used with synthetic fibers.
The industry is also interested in certain aminosilicones in fiber processing. Since these silicons do not have a net charge, they cannot generally adhere effectively to cellulose or proteinaceous materials by electric attraction. Indeed, when used in the context of a conventional polyester fiber / cotton blend, aminosilicon adheres only to the polyester in the blend. In an effort to overcome these problems, it is known to use cationic compounds that adhere to cellulosic materials. Certain cationic compounds, such as certain specific cationic polyorganosiloxanes (see, eg, US Pat. No. 4,472,566) and quaternary nitrogen derivatives of organosiloxanes (see US Pat. No. 4,185,087). Etc.) are known in the art. Other suitable fabric softening compounds are non-quaternary amides and non-quaternary amines. Commonly cited materials are the reaction products of hydroxyalkylalkylene diamines with higher fatty acids. See U.S. Pat. Nos. 4,460,485; 4,421,792; and 4,327,133.

U.S. Pat. No. 2,952,892 describes a method for modifying cellulose fibers with a composition comprising an acrylic prepolymer and a silicone resin, such as an alkylpolysiloxane. US Pat. No. 5,951,719, the disclosure of which is incorporated by reference, treats cellulosic fabrics with a composition comprising acrylates, glyoxal, and silicone fabric softener to improve color fastness to dyed cotton A method is disclosed.
US Pat. No. 5,741,548, the disclosure of which is incorporated by reference, describes a process for chemically bonding polymer coatings, ie acrylic prepolymers, urethane prepolymers, and acrylic urethanes to many fibers including cellulose cotton. Teach. This patent describes the use of graft initiators such as iron salts and peroxides such as urea peroxide. The purpose of grafting is to provide a surface that can be combined with ink jet printing for high resolution images.

US Pat. No. 5,552,472, the disclosure of which is incorporated by reference, teaches a solution for forming a grafted material comprising an initiator, a catalyst, a water dispersible prepolymer, and a monomer. The graft is useful to control fabric porosity and to control airbag permeability. One composition includes a graft initiator such as a metal ion; a solvent such as a peroxide, peracid, or perbenzoate; a graft prepolymer such as a water dispersible urethane; and a monomer such as an acrylic.
US Pat. No. 5,763,557, the disclosure of which is incorporated by reference, is a polymer composition applied by chemical grafting with the use of monomers / prepolymers, catalysts, graft initiators, and other components of the composition. Teach. The coating is advantageously applied to remay and the satin acetate fabric can undergo graft polymerization, thereby forming a polymer film that is chemically bonded to the fabric substrate with strong adhesion. Preferred compositions include graft initiators such as metal ions; catalysts such as peroxides; graft prepolymers such as urethanes and / or acrylics; monomers such as sodium salts of acrylic and AMPS monomers.

US Pat. No. 6,165,919 discloses that a cellulosic material, such as cotton fabric and paper, is a polymer of (A) an ethylenically unsaturated polycarboxylic acid monomer or salt thereof, wherein the monomer is a carbon atom adjacent to a carboxyl group. The polymer having one or more dicarboxyl groups in; and (B) a saturated alpha-hydroxypolycarboxylic acid or salt thereof; and (C) a composition comprising one or more curing catalysts; and Heated to create cellulose esterification and cross-linking by reaction of carboxyl groups and cellulose hydroxyl groups in the reaction products of (A) and (B).
Treatment of paper with formaldehyde-based reactants such as dimethylol dihydroxylethylene urea, urea formaldehyde, and melamine-formaldehyde has been used as a wet strength agent to give these valuable characteristics to cellulose fibers . However, formaldehyde is an irritant and is a known carcinogen. In addition, cellulosic fabrics treated with formaldehyde-based reagents suffer from severe strength loss. As a result, there are strict limits on formaldehyde production from fabric garments. Glyoxylic acid polyacrylamide-diallyldimethylammonium chloride copolymer resins are also known for use as paper dry strength and temporary wet strength resins.

  The technique teaches many formulations to increase color fastness, improve touch, and reduce shrinkage. What is needed is that fabrics, especially cotton and cotton-poly mixed fabrics, can be easily processed to reduce clocking, increase color fastness and reduce shrinkage, An inexpensive composition and process such that such treatment does not adversely affect the hand. Preferably, the treatment can withstand at least 20 wash cycles with little degradation in performance. Preferably, the treatment can be applied to the fabric without any additional processing steps. The treatment is advantageously a single stable composition with a lifetime of at least 2 months. The composition of the present invention solves these needs.

The present invention is directed to compositions and methods that improve the antifouling, color fastness, clock fastness, shrinkage, and abrasion resistance of fabric fibers while not adversely affecting the feel of fabric products. The composition comprises a specific mixture of monomers in a specific formulation (here they are used as prepolymers), prepolymers, catalysts, initiators, crosslinkers, and silicone softeners in a specific formulation. It is a prescription. When applied to a fabric, preferably a cotton fabric, the composition develops graft polymerization, thereby forming a polymer film on at least a portion of the fibers that are covalently bonded to the fibers.
The composition can be applied to fibers, fabrics, fabrics, etc. by dipping, spraying, roller coating, and the like. The composition is advantageously polymerized during conventional heating and drying processes.
One embodiment of the present invention includes a graft initiator for activating a site on a substrate having active hydrogen; for grafting a first component thereto and an activation site for the first component. The first component comprising a functional group for reaction with an activation site on the substrate to form; and for reaction with the activation site of the substrate or the first component; and The present invention relates to a solution for forming a graft substrate containing the second component containing a functional group for forming an activation site in the second component. The first and second components are grafted onto the substrate upon contact with the solution to form a grafted substrate; and one of the first and second components is grafted Including a structure that imparts improved softness and antifouling properties to the finished substrate, and the other of the first and second components improves the flexibility of the graft.
The present invention generally involves contacting a composition comprising an activated graft initiator, a polymerisable softener, and a polymerisable prepolymer onto a fiber, fabric, fabric, etc., to provide a polymer layer grafted to the fiber surface. It is a method of forming.

In one embodiment, the present invention provides a sufficient amount of the selected monomer or prepolymer to adhere the fabric softener to the fabric by polymerizing a polymer that includes the fabric softener and is grafted to the substrate fiber. Treat cotton, or cotton-polymer fibers, such as cotton / polyester, with a stable liquid composition containing an activator, catalyst, and at least 5%, more preferably at least 7% polymerisable softener, as well as the polymer. It involves doing.
In another embodiment, the invention relates to a stable formulation of the treatment composition. The formulation comprises an activator, a catalyst, and at least 5%, more preferably at least 7%, as well as sufficient selected monomers to polymerize the softener-containing polymer by polymerizing the softener-containing polymer. % Polymerisable softener. Stable means that the composition remains fluid and self-polymerizes, i.e. a non-dissolvable / non-suspendable polymer, from approximately 15.55556 degrees Celsius (60 degrees Fahrenheit) to approximately 32 degrees Celsius for at least two months. During storage at a temperature between 22222 degrees (90 degrees Fahrenheit), it means having less than about 5%, preferably less than about 2% prepolymer formed in the composition. The fluid includes activators and catalysts, which are not active to a significant extent until the fluid is exposed to elevated temperatures during the drying and activation process.

In another embodiment, the present invention relates to a stable thickener that can be diluted with water or other solvents to form the stable formulations described above.
Preferred softeners are aqueous emulsions of silicone oil for cotton fibers and modified or unmodified organopolysiloxanes for cotton / polyester fibers. Special case of printed cotton containing pigment adhering to the cotton fibers of rubber or other adhesives, preferably softeners, modified or unmodified organopolysiloxane is a compound of high density polyethylene, and polyamide.
The terms fiber, yarn, filament, staple, and fabric are well known to those skilled in the fabric industry. The finishing and processing operations referred to are also well known. However, as used herein, the term “fiber” refers to individual fibers, yarns, staples, and filaments, and also refers to both woven and non-woven fabrics and products made from fibers and / or woven fabrics. To do.

Both natural and synthetic fibers are known in the art to be used in the formation of textile materials. Cellulosic fabric fibers are derived from natural resources such as cotton, flax, African hanegaya, milkweed, straw, jute hemp, and bagasse. The composition of the present invention is useful for all natural fibers. Mixtures such as cotton / polyester are well known to those skilled in the fabric industry.
The terms “color fastness” and / or “fastness” mean the degree to which the color fades or changes when exposed to causative agents such as sunlight, reactive gases, chemicals, solvents, and the like. Color fastness or fastness can be measured by standard test methods such as AATCC test method 3-1989.
As used herein, the term “clock” or “clock resistant” refers to the degree to which color may transfer from one surface of a dyed fabric to another due to friction. Clock testing is performed using standard test procedures and equipment such as the AATCC Clock Meter Model CM.M, available from Atlas Electric Devices, Inc., Chicago, Illinois. 5 may be used.

As used herein, the terms “dyed cotton” and “dyed cotton / polyester” mean fibers that have been exposed to and contain at least one reactive dye. Dispersible dyes are used to dye polyester. As used herein, the term “reactive dye” means an acidic, basic or mordant dye with attached reactive groups that can be covalently attached to the cellulose fiber. While it is clear that reactive dyes, vat dyes, and sulfur dyes are desirable for use with cellulose fibers, the application of these dyes requires more than one process step and sufficient reaction time. Is often disturbed by the slow line speeds necessary to achieve this.
As used herein, the terms “printed cotton” and “printed cotton / polyester” mean fibers that have been exposed to pigments and adhesives that help the pigments bind to the fibers. . Such an adhesive, also referred to as an adhesive rubber, is carboxylated butadiene acrylonitrile.

As used herein, the term “catalyst” usually does not necessarily mean by dissolving in water, but an approximately 0.01N to approximately 1N solution of an active ingredient, such as peroxide or metabisulfite, preferably Means a prescription solution containing a 0.1N solution. Effectively, the catalyst is added to the composition as a solution.
As used herein, the term “graft initiator” is usually not necessarily dissolved in water, but an approximately 0.01N to approximately 1N solution of an active ingredient, eg, an iron salt, preferably 0.1N. The formulation liquid containing a solution is meant. Effectively, the graft initiator is added to the composition as a solution.
As used herein, the composition is described in weight percent unless otherwise indicated.

  The present invention provides polymerizable monomers such as: vinylidene chloride, chloroprene, isoprene, dimethylaminoethyl methacrylate, styrene, 1,3-butylene dimethyl acrylate, hydroxyethyl methacrylate, isobutyl vinyl ether, acrylonitrile, acrylamide, N-vinyl pyridine Glycidyl methacrylate; N-vinylcaprolactam, N-vinylpyrrolidone, N-vinylcarbazole, acrylic acid, methacrylic acid, ethyl acrylate, ethyl methacrylate, itaconic acid, isobutyl methacrylate, methyl acrylate, sodium styrenesulfonate, Sodium vinyl ether, ethylene glycol divinyl ether, butanediol divinyl ether, vinyl toluene, vinyl acetate, octadecyl vinyl ether As, mixtures and can be applied to use of the prepolymer. However, certain combinations of monomers and prepolymers have been found to create fabrics with very nice characteristics, including antifouling, clock fastness, and feel.

In addition, the components of the composition comprising acrylic, elastomer latex, urethane, silicone oil, polyamide, urethane acrylate, polyethylene glycol diacrylate, high density polyethylene, and sodium vinyl sulfonate are more specific to the monomer and / or prepolymer composition. In particular, it means monomer and prepolymer formulations when they are commercially available. As used herein, the term “prepolymer” is commonly used to form monomers, oligomers, short chain pseudostable polymer chains, and other polymerizable monomers or oligomers that can be included in a polymerized polymer. Includes formulations that may react with the compound.
The prepolymer (polymer material) is chemically grafted to the fiber polysaccharide, and the grafting is initiated with a graft initiator. The graft polymer effectively comprises a silicon-based softener and at least two selected prepolymers.
Thus, the present invention is specifically a method of making a fiber with a soft hand and good clock fastness, color fastness, abrasion resistance, and antifouling:
Contacting the cellulose fiber with the activated graft initiator to form a location on the fiber where the polymer can adhere and polymerize; and at least 5 weights selected from organopolysiloxanes, polymerizable silicone oils, or mixtures thereof % of polymerisable silica-containing compound, and an acrylic prepolymer, glyoxal prepolymer, elastomer latex prepolymer, polyamide prepolymer, the urethane prepolymer, at least two polymerisable selected from acrylonitrile prepolymer and high density polyethylene prepolymer Contacting the composition comprising a prepolymer with the cellulose fiber under conditions to form a copolymer grafted to the cellulose fiber, and the activated graft initiator is in the composition;
The composition comprises about 5 polymerizable materials that self-polymerize at a temperature between approximately 15.55556 degrees Celsius (60 degrees Fahrenheit) and 32.22222 degrees Celsius (90 degrees Fahrenheit) during storage for a period of at least 2 months. %, Stable,
The present invention is directed to a method of forming a graft copolymer on a cellulose fiber, the graft copolymer comprising at least about 5% by weight of a silica-containing compound.
Composition used in the present invention include acrylic prepolymer, glyoxal prepolymer, elastomer latex prepolymer, polyamide prepolymer, the urethane prepolymer, at least two polymerisable selected from acrylonitrile prepolymer and high density polyethylene prepolymer pre Contains polymer.
The term “acrylic prepolymer” as used herein means a low molecular weight polymer chain of 6000 molecular weight or less, and preferably approximately 200 to 1200 molecular weight. Particularly suitable monomers for the practice of the present invention are hydroxyl, carboxyl, epoxy, amino, hydride, and glycidyl functional groups, ie hydroxyethyl or propyl methacrylate, dimethyl and diethylaminoethyl acrylate and methacrylate, methyl, ethyl, butyl and other alkyls Includes acrylates and methacrylates, glycidyl methacrylate or mixtures thereof.
Diacrylates and triacrylates are present in minimal amounts because they may cause undesirable crosslinking.

For example, preferred acrylic prepolymers are available from Wilmington Leather Co., Newcastle, Del., HELASTIC WO-8001 (TM), HELASTIC WO-8041 (TM), and HELASTIC. Including WO-8061. They are characterized by gentle tensile strength, adhesion, and color stability. Others include ECCO-REZ907 available from Advanced Polymer, Saddlebrook, NY. It has been found that different acrylic prepolymers give different results and that the most preferred formulations contain a predetermined amount of several acrylic prepolymers.
Glyoxal resin prepolymer is a prescription commercially available from Eastern Color & Chemical as ECCORE GB404 (TM). More preferred is RESIN KLF (TM), which is a low formaldehyde-producing glyoxal resin.

Polyamide prepolymer is a dispersant available as MICROMID 632 HPL ™ from Union Camp, Jacksonville, FL. A preferred urethane prepolymer is SR9035 (TM), a preferred urethane acrylate is SR9035 (TM), and a preferred polyethylene glycol diacrylate prepolymer is SR344 (TM), each available from Sartomer, Pennsylvania. is there. Another urethane prepolymer emulsion is RESAMINE UMT171 (TM).
  The anti-clocking non-ionic dispersant is CROCKFAST2 (TM) available from AM Technology, Oxford, NY.
  A preferred elastomer latex prepolymer is HISTRETCH V-43 available from BF Goodrich, Cleveland, Ohio. These are highly elastic polymers with memory that can recover their shape after being stretched. The polyethylene prepolymer emulsion is available as MYKON HD from Gen Corp, Chester, SC.
  Carboxylated butadiene acrylonitrile prepolymers are available from Reichhold Chemical Company, Research Triangle, North Carolina.
  Graft polymer chains are formed from monomers and prepolymers containing suitable polymerizable functional groups such as hydroxyl, carboxyl, epoxy, amide, amine, hydride and the like. The amount of triacrylate is kept low to reduce unwanted cross-linking.
  As used herein, water is usually non-ionized water. Other components such as alcohols, alkyl glycols, and other organic solvents may be used.

[Polymerizable silica-containing compound]
Formulations according to the present invention utilize polymerizable silicone oil, preferably in the form of an aqueous emulsion or microemulsion of silicone oil. Silicone oil softeners are specified by the amount of aqueous silicone oil emulsion required in the formulation. Silicone oils and organopolysiloxanes provide a better feel and also increase durability against wear, chemicals and dirt.
Non-functional and functional siloxanes characterized as described above may be either monomeric (low molecular weight) or oligomer or polymer (high molecular weight) and linear, branched, or cyclic. Examples of polymeric siloxane compounds include dimethylpolysiloxane, methylhydrogen polysiloxane, methylalkylpolysiloxane, methylallylpolysiloxane, methylfluoroalkylpolysiloxane, and organofunctional methylpolysiloxanes such as aminoalkylmethylpolysiloxane, cyanoalkylmethyl Non-functional and organofunctional polysiloxanes including polysiloxanes, haloalkylmethyl polysiloxanes, and vinylmethyl polysiloxanes. Examples of monomeric or oligomeric siloxanes are MeOSi (Me) ₂ -OMe, Me ₃ SiOMe, Me ₃ Si (OMe) ₂ , Si (OMe) ₄ , Si (OEt) ₄ , MeSi (Me) ₂ -OSi (Me ) ₂ -Me, HOOC - containing _{(CH 2) 3 --COOH - (} CH 2) 3 -Si (Me) 2 -O-Si (Me) 2. Examples of cyclic siloxane oligomers include octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane.
A preferred silicone oil emulsion is SEQUASOFT 69 (TM), available from Gen Corp., Chester, SC. A preferred high molecular weight silicon is HELASTIC WO-8026 (TM), available from Wilmington Leather Company, Newcastle, Delaware.
A preferred modified organopolysiloxane emulsion is APS V-SOFT (TM), available from Advanced Polymer Co., Saddle Brook, NY.

Composition used in the present invention may further comprise at least one polymerisable prepolymer selected either et polyethylene glycol diacrylate and urethane acrylate prepolymer over.
The above-mentioned composition may also contain surfactant monomers, examples of such monomers include sulfonic acid group-containing compounds such as sodium vinyl sulfonate, sodium p-styrene sulfonate, sodium methallyl sulfonate, methallyl ether. Examples include sodium p-sulfophenyl or sodium 2-methyl-2-acrylamidopropane sulfonate. Such groups are known to increase hydrophilicity. Also, carboxylate-containing comonomers, for example itaconic acid also surfactant monomers. A preferred surfactant monomer is sodium vinyl sulfonate.

The primary object of the present invention is to provide fibers and fabric materials having a coating of a polymer material that is chemically, ie covalently bonded to the fabric. The present invention is applicable to any suitable textile material including acetate, polyester, polypropylene fabric, nylon, polyester, fiberglass, acrylic, cellulose, polyethylene, polyvinyl chloride, polycarbonate, and the like. The present invention is particularly applicable to cotton and cotton-containing fabrics.
Cotton is the main fabric fiber. Usually it is made from approximately 88% to 96% cellulose. Cellulose is a natural hydrocarbon high polymer, a polysaccharide that contains anhydroglucose units joined together by oxygen bonds that basically form a linear molecular chain.
This grafting of the polymer material to the fiber is accomplished by chemical bonding of the polymer to the textile substrate molecule through a covalent bond. Grafting the cotton fabric surface with the polymer layer can be described as a process that involves activating cellulose molecules, attaching monomers to reactive sites, and then chain growth with attached monomers.

Chemical grafting is believed to involve activation of the substrate, ie the fabric to be treated, as a first step. Free radicals initiate the process of chemically grafting the polymer layer onto the fabric surface. Acidic protons from the monomer or substrate are removed by the graft initiator, thereby forming a radical. In particular, the process of chemically grafting the polymer layer onto the cotton fabric surface involves the separation of (acidic) hydrogen atoms from the hydroxy groups of the cellulose molecules that form free radicals. The radical then initiates the formation of polymer chains.
Graft initiators are used to activate the fabric surface and initiate the polymerization reaction. The graft initiator is selected to separate active hydrogen from the substrate filament or yarn to which the graft polymer is bound. The initiator is preferably a metal ion provided by ionization of a metal salt. Ferrous ions extracted from ferrous ammonium sulfate and other metal ions such as Ag ⁺ , Co ⁺² , and Cu ⁺² extracted from the respective saline remove active hydrogen and are active Has the ability to concomitantly initiate polymer chain growth at sites where hydrogen has been removed. Silver ions and ferrous and ferric ions are preferred, but other metal salts may also be utilized effectively.

The graft initiator advantageously comprises an effective concentration of metal ions selected from Fe ⁺³ , Fe ⁺² , Ag ⁺ , Co ⁺² and Cu ⁺² . When a site is activated, the amount does not need to be large because growth continues substantially like an autocatalytic process at the site. 1 to 1000 ppm, preferably 10 to 100 ppm of graft initiator is usually sufficient. When ferrous ammonium sulfate is utilized as the graft initiator, such salts are preferably from about 0.001% to about 0.2%, more preferably about 0.01% by weight of the composition. % To 0.1% by weight present in the graft composition. Certain iron salts function very well, but they contribute to yellowing and may not be preferred in certain applications.
In one embodiment of the invention, chemical grafting of natural or polymer filaments or yarn substrates begins with the reaction of the substrate's “active hydrogen” with a graft initiator with metal ions. Other methods of initiating grafting, including radiation, high or low pH, plasma treatment, or framing, are included in certain embodiments of the invention and reduce the amount of graft initiator in the treatment composition, or Makes it possible to eliminate. The initiator may be ozone or other known free radical former in one other embodiment. However, in these cases, the composition will not be a self-contained single formulation composition that can be easily applied and cured using equipment and processes at the appropriate location in the yarn and fabric manufacturing plant.

Active hydrogen is hydrogen that is relatively easily removed from the substrate by the graft initiator. For example, a tertiary carbon maintains a weaker covalent bond with a hydrogen atom than a secondary carbon, and the hydrogen atom would be a type of active hydrogen. Other types include NH, -OH, -COOH, -COOR-H, and the like. With respect to the cellulose structure, the graft initiator is believed to remove active hydrogen from cellulose-CH ₂ OH to form cellulose-CH ₂ O. Graft initiators are: only active hydrogen that results in the formation of cation positions; active hydrogen with one electron that results in substrate free radical positions; or the removal of active hydrogen and both electrons that result in the formation of anion positions in the substrate it can.
Hydrogen separation produces an activated position on the substrate that binds to the monomer or prepolymer, particularly the vinyl-based monomer. The free radical carbonyl group then reacts with either the first component or the second component (eg, CH2 = CH-X) and grafts the component as a free radical on the polyester chain. The grafted free radical component may now be covalently bonded to an additional component of the same or another species, thereby activating the additional component to a free radical state or to terminate the polymerization process May react with another free radical. All cellulose -CH ₂ OH in polysaccharide chain is recognized that it is not necessary to be activated. Growth continues until it is terminated, for example, by radical synthesis.

In order to ionize the metal salt to provide activated metal ions, the graft solution contains a catalyst. As used herein, the term catalyst refers to a material that converts the used graft initiator into an entity capable of initiating another graft site. A wide range of catalysts may be utilized in the process of the present invention. Among the catalysts that can be used, ammonium persulfate, hydrogen peroxide, tert-butyl hydroperoxide, di-tertbutyl peroxide, benzoyl peroxide, sodium disulfide, dicumyl peroxide, lauryl peroxide, tert-butyl perbenzoic acid, And peracetic acid. Other strong oxidants including periodate can also be used. Peroxides, peracids, or perbenzoates are preferred catalysts. Water-soluble peroxide catalysts of urea peroxide and / or hydrogen peroxide are preferred, as are ammonium persulfate and / or potassium persulfate. Benzoyl peroxide, peracetic acid, or tertiary butyl perbenzoic acid are also useful. Certain peroxides, such as urea peroxide, exhibit excellent stability during storage and excellent activity during use. In order to provide silver and iron ion graft initiators, the catalyst functions to ionize metal salts, such as the silver or iron salts described above.
The catalyst can be present in any effective amount. When peroxide is utilized to activate the graft initiator, such compounds are preferably from about 0.001% to 0.2% by weight of the composition, more preferably about 0.01% of the composition. It is present in the graft composition at from about 0.1% to about 0.1% by weight.

The fabric according to the present invention has a grafted polymer layer made by a process comprising treating the fabric surface with a graft initiator effective to chemically activate the fabric surface. The chemically activated surface then comprises (or at the same time) polymerizable monomers and prepolymers that react with the activated textile surface to form a polymer layer grafted, ie chemically bonded, to the textile surface. Contact with reagents.
It is believed that not all of the polymerizable material in the treatment composition will form a graft on the substrate fiber. Preferably, at least about 20% of the polymerizable material, more preferably at least about 50%, is grafted to the substrate fiber. Evidence of grafting is seen when the fiber does not impair more than 50% of the treatment after at least 15 washes with normal detergent.
Of course, the grafted polymer may also be crosslinked to other grafted or non-grafted polymers. At least some of the polymerizable prepolymers preferably have functional side chains such as hydroxyl groups, carboxyl groups, and secondary or tertiary amino groups. The described formulation was selected to provide a graft product that improves the feel, shrinkage, antifouling, color fastness, and clock fastness of the treated fibers.

Where possible, the reactions of the present invention utilize emulsions or aqueous solutions to minimize environmental release of organic solvents. To this end, methods have been developed to increase the solubility of required organic substances in water and to maintain a stable fluid composition. In addition, the reaction typically drains organic reactants, leaving little or no organic waste.
The present invention relates to forming a graft polymer on a fiber comprising cotton. The method provided by the present invention for chemically grafting a polymeric material to a fabric surface includes: (a) treating the fabric surface with an effective graft initiator to create a chemically activated fabric surface; b) contacting the activated fabric surface with a reagent comprising a polymerizable monomer or prepolymer to create a fabric surface grafted with the polymer layer; and (c) after the polymer layer is grafted to the fabric surface. Termination of chemical grafting by radical synthesis or other mechanisms.

Accordingly, the present invention provides compositions and methods for making fabric surfaces to provide improved clocking, color fastness, rub resistance, antifouling, and hand properties and to provide reduced shrinkage to the fabric. I will provide a. The polymeric material is chemically grafted to the woven polysaccharide to form a durable process. The graft polymer effectively comprises a silicon-based softener and at least two selected prepolymers. Grafting is initiated with a graft initiator.
Another advantage of the present invention is that the formulation is stable at room temperature, is available in a thickener, and in a preferred embodiment has all the necessary components in a single fluid composition. The graft initiator and catalyst are activated by heat, for example by exposure to approximately 340 degrees for 1 minute. It is effective in dough making that the treatment recipe is self-sufficient but not necessarily so. Activation of cotton fibers before or simultaneously with wet pick-up, for example with ozone or irradiation, is also conceivable as an embodiment of the reaction. In such cases, the formulation without activator and catalyst is more stable against temperature changes.

One important feature of the present invention is to provide a stable thickener for use in treating fibers. A stable one-composition thickener is particularly useful because all of the components except the solvent are present. The thickener premix allows for better measurement and control of the resulting treatment recipe. Applicants have found that certain ratios of certain treatment compounds are important, as is the concentration of some treatment compositions. In addition, the thickener reduces the cost of loading and handling the processing chemicals.
The particular monomers and prepolymers used in the present invention and the amount used will depend, in part, on the properties of the cotton. The properties of cotton depend on whether it is dyed and pigmented by printing, whether the cotton has other adjuvants, such as cotton-poly compositions known in the art, and so on.
The absolute amount of chemical is not as important as the ratio of components in the composition. Certain compounds that provide cross-linking with multiple bonding sites, such as diacrylates, triacrylates, and urethane acrylates, are in very small amounts, typically less than 1%, and preferably less than 0.4%. Included in low polymerisable compositions. Silicone based softeners, on the other hand, provide at least 20% polymerisable material, preferably at least 30%, and in most cases preferably at least 40%.

Dyed and undyed cotton As used herein, “dyed cotton” is cotton that has reacted with a reactive dye. Thus, dyed cotton requires less protection to maintain anti-clocking and color fastness properties. In addition, reactive dyes change the fibers, and the specially made processing composition is an excellent combination of a very soft hand, sufficient clock and color fastness, and sufficient antifouling and anti-friction properties. I will provide a.
One feature of the present invention is about 0.4% to about 5% glyoxal prepolymer; about 0.1% to about 3% elastomer latex prepolymer; about 6% to about 35% aqueous silicone oil emulsion; A stable composition comprising about 0.2% to about 5% urethane prepolymer emulsion; about 0.002% to about 0.3% catalyst; and 0.002% to about 0.3% graft initiator. A method of treating cotton fibers, comprising a first step of providing Effectively, the formulation described above further comprises from about 0.02% to about 2% high molecular weight silicone; from about 0.002% to about 0.15% urethane acrylate prepolymer; from about 0.002% to about 0. 15% polyethylene glycol diacrylate; and approximately 0.004% to approximately 2% polyethylene glycol.

The composition is stable with less than 5% prepolymer that self-polymerizes at a temperature between approximately 15.55556 degrees Celsius and 32.22222 degrees Celsius (60 degrees Celsius to 90 degrees Fahrenheit) during storage for a period of at least 2 months. ing. The solids content of the stable composition when dried is at least approximately 5% by weight.
This formulation in the second step contacts the cotton fibers to pick up approximately 40 grams to approximately 120 grams of the stable composition onto approximately 100 grams of cotton fibers. The method of contacting and controlling the wet pickup may be any known method in the art. The cotton fiber is in a third step at a temperature sufficient to polymerize at least 20%, preferably at least 50%, more preferably at least 80% of the prepolymer and silicone oil into a polymer grafted to the cotton fiber. It is dried by being exposed. It has been recognized that some prepolymers may self-polymerize during the drying step, and these polymers may advantageously be loosely bonded to the fibers. This is a form of prior art—it is known to cross-link processing chemicals to themselves. This treatment is less effective when the processing chemicals are removed. A significant proportion of the processing chemical of the present invention is grafted onto the fiber, but is therefore less likely to be removed by friction or washing.
One effect of this process is typically 148.8889 degrees Celsius (300 degrees Fahrenheit) to 204.4444 degrees Celsius (400 degrees Fahrenheit), where the coating with the treatment chemical prior to drying is periodically e.g. during stretching It is to be implemented with a tenter frame.
In one embodiment, the treatment composition is a stable single contact formulation and the activator and catalyst coexist in the stable formulation with the prepolymer. The formulation can be stored and used at normal ambient temperatures without solidification or polymerization.

In a more preferred embodiment, the cotton fibers comprise about 0.8% to about 3.5% glyoxal prepolymer; about 0.2% to about 2% elastomer latex prepolymer; about 8% to 30% aqueous silicone. Oil emulsion; including approximately 0.8% to approximately 4% urethane prepolymer emulsion; approximately 0.006% to approximately 0.2% catalyst; and approximately 0.006% to approximately 0.2% graft initiator Coated with a stable composition. The stable composition is more effectively about 0.1% to about 1.5% high molecular weight silicon; about 0.004% to about 0.08% urethane acrylate prepolymer; about 0.004% to about 0.08% polyethylene glycol diacrylate; and approximately 0.1% to approximately 1% polyethylene glycol.
Concentration and wet pickup are at some price, but certain effects are inherent in more concentrated formulations, including less solvent evaporating. In one embodiment, the contact picks up approximately 60 grams to approximately 100 grams of the stable composition onto approximately 100 grams of cotton fiber.
The drying temperature ranges from approximately 43.33333 degrees Celsius (110 degrees Fahrenheit) to approximately 226.6667 degrees Celsius (440 degrees Fahrenheit), preferably approximately 121.1111 degrees Celsius (250 degrees Fahrenheit) to approximately 204.4444 degrees Celsius (Fahrenheit). 400 degrees), for example approximately 171.1111 degrees Celsius (340 degrees Fahrenheit), and the drying time is approximately 10 seconds to approximately 10 minutes, for example approximately 1 minute. Without being bound by theory, it is believed that both water loss from drying and elevated temperatures contribute to effective grafting and polymerization.

  One preferred treatment formulation is: approximately 1% to approximately 3% glyoxal prepolymer; approximately 0.4% to approximately 1.5% elastomer latex prepolymer; approximately 10% to approximately 30% aqueous silicone oil emulsion; approximately 1% to approximately 3.5% urethane prepolymer emulsion; approximately 0.2% to approximately 1% high molecular weight silicone; approximately 0.01% to approximately 0.05% urethane acrylate prepolymer; approximately 0.01% From about 0.05% polyethylene glycol diacrylate; from about 0.01% to about 0.05% catalyst; from about 0.01% to about 0.05% graft initiator; and from about 0.16% to about . Contains 8% polyethylene glycol. Treatment of cotton, especially dyed cotton, with this formulation results in a fabric having a good touch and a clock factor of approximately 4 to 4.5 based on a standard scale of 1 (bad) to 5 (very good). Fabrics so treated may have excellent color fastness and low shrinkage, for example, as much as approximately 3.55 to 4%, and untreated cotton may exhibit approximately 8% shrinkage.

  In one embodiment, a stable treatment composition is provided by mixing a stable concentrated composition with water or other solvent. The thickener comprises approximately 2% to 10% glyoxal prepolymer; approximately 0.5% to approximately 6% elastomer latex prepolymer; approximately 30% to approximately 70% aqueous silicone oil emulsion; approximately 1% to approximately 10%. % Urethane prepolymer emulsion; about 0.01% to about 0.6% catalyst; and about 0.01% to about 0.6% graft initiator. Preferred formulations are further: about 0.1% to about 4% high molecular weight silicone; about 0.01% to about 0.3% urethane acrylate prepolymer; about 0.2% to about 4% polyethylene glycol; and Contains about 0.01% to about 0.3% polyethylene glycol diacrylate. The concentrated composition can be, for example, from about concentrate 2: water 100 to about concentrate 100: water 100, preferably about concentrate 4: water 100, about concentrate 50: water 100, more preferably about concentrated. Agent 10: water 100 is diluted with water added at a weight ratio of concentrate 25: water 100 approximately. In one preferred embodiment, the treatment composition is formed by adding the thickener 1 to water or other solvent 2-4. Again, the concentrated solution is effective and stable under normal storage conditions, for example, the concentrated composition is approximately 15.55556 degrees Celsius (60 degrees Fahrenheit) to about Celsius during storage for a period of at least 2 months. A fluid with less than 5% prepolymer that self-polymerizes at a temperature between 32.22222 degrees (90 degrees Fahrenheit). A stable concentrated composition typically contains about 10% to about 35% solids upon drying.

  In one embodiment, the stable concentrated composition is: about 4% to about 7%, such as about 5.6% glyoxal prepolymer; about 1% to about 4%, such as about 2.8% elastomer latex pre. Polymer; approximately 40% to approximately 60%, such as approximately 56.1% of an aqueous silicone oil emulsion; approximately 4% to approximately 8%, such as approximately 5.6%, urethane prepolymer emulsion; approximately 0.03% to approximately 0 0.2%, such as approximately 0.06% of the catalyst; and approximately 0.03% to approximately 0.2%, such as approximately 0.06% of the graft initiator. The formulation is effectively about 0.5% to about 3%, such as about 1.6% high molecular weight silicone; about 0.02% to about 0.15%, such as about 5.6% urethane acrylate prepolymer. About 0.5% to about 2%, for example about 1% polyethylene glycol (preferably diethylene glycol); and about 0.02% to about 0.15%, for example about 0.06% polyethylene glycol diacrylate. Including. This stable concentrated composition contains about 20% to about 32% solids upon drying.

  In a further embodiment, the stable concentrate composition is: about 4% to about 7% glyoxal prepolymer; about 1% to about 4% elastomer latex prepolymer; about 40% to about 60% aqueous silicone oil About 4% to about 8% urethane prepolymer emulsion; about 0.5% to about 3% high molecular weight silicone; about 0.02% to about 0.15% urethane acrylate prepolymer; % To about 2% polyethylene glycol (preferably diethylene glycol); and about 0.02% to about 0.15% polyethylene glycol diacrylate. In this embodiment, the catalyst and graft initiator are added separately, or else a method of initiating and growing ozone and / or irradiation and / or graft polymer is used.

In another embodiment, the stable concentrated composition comprises: about 5% to about 6% glyoxal prepolymer; about 2% to about 3% elastomer latex prepolymer; about 52% to about 60% aqueous silicone oil emulsion Approximately 5% to approximately 7% urethane prepolymer emulsion; approximately 0.03% to approximately 0.1% catalyst; approximately 0.03% to approximately 0.1% graft initiator; approximately 1% to approximately 2; % High molecular weight silicon; about 0.04% to about 0.1% urethane acrylate prepolymer; about 0.04% to about 0.1% polyethylene glycol diacrylate; and 0.6% to about 1.6 % Polyethylene glycol. This stable concentrated composition, when dried, contains approximately 25% to approximately 30% solids.
The graft initiator may comprise Fe, Ag, Co, Cu salts, or mixtures thereof. These metal salts are effectively used with a catalyst to activate the graft initiator. The catalyst comprises a strong oxidant such as a peroxide, peracid, perbenzoate, or a mixture thereof. Since glyoxal prepolymer is a low formaldehyde prepolymer, it produces less than 30 ppm formaldehyde in the treated fiber.
When the cotton fibers comprise non-dyed cotton, the above-described stabilizing treatment composition effectively further increases from about 0.4% to about 8%, preferably from about 0.8% to about 6%, more preferably about 1 Further comprising 2% to approximately 4.5% fluoroalkyl acrylate.
The concentrated stable composition described above effectively further comprises from about 2% to about 16%, preferably from about 4% to about 12%, more preferably from about 6% to about 9% fluoroalkyl acrylate.

The treatment composition is added to the fiber, such as a fabric, by any method, and the polymer is then typically but not exclusively for approximately 30 seconds to approximately 5 minutes, heat, for example approximately 171.1111 degrees Celsius (Fahrenheit). 340 degrees) is applied to the fiber and is also crosslinked. The application may be performed, for example, by padding, infiltration, spraying, etc. For example, the cellulose fabric may be dipped in a bath of treatment solution. The treatment composition may be an emulsified nonionic or ionic material.
Thicker fabrics may require longer heating at higher temperatures. The thick fabric may preferably be oven cured at approximately 160 degrees Celsius (320 degrees Fahrenheit) to 190.5556 degrees Celsius (375 degrees Fahrenheit) for approximately 1 to 15 minutes.
The present invention includes both treatment compositions and methods of treatment.
The present invention also includes the product of a process for treating cotton fibers and / or fabrics with the treatment composition described above. Fabrics made of treated cotton effectively have a shrinkage of less than about 4.5%, preferably less than about 4%, at least 4 clock fastness in the standard test described below, and good hand .

Dyed cotton / polyester and non-dyed cotton / polyester The compositions described for dyed cotton and non-dyed cotton work well with cotton / polyester blends, while different formulations provide even better cotton / polyester blend properties To do.
One embodiment of the present invention is about 1.6% to about 18% acrylic prepolymer, about 0.1% to about 3% elastomer latex prepolymer, about 6% to about 35% organopolysiloxane emulsion. About 0.1% to about 3% urethane prepolymer emulsion, about 0.002% to about 0.3% catalyst, and about 0.002% to about 0.3% graft initiator It relates to a method of treating cotton / polyester fibers comprising providing a fluid composition. Advantageously, the processing fluid also comprises approximately 0.002% to approximately 0.2% polyethylene glycol diacrylate. In another embodiment, the composition also includes from about 0.002% to about 0.2% surfactant monomer. Again, it is important that the treatment composition be stable for at least two months at ambient storage conditions. Again, stable refers to 5 prepolymers that self-polymerize at temperatures between approximately 15.55556 degrees Celsius (60 degrees Fahrenheit) and 32.22222 degrees Celsius (90 degrees Fahrenheit) during storage for a period of at least 2 months. % And the solids content of the stable composition when dried is at least approximately 5% by weight.

The processing fluid is contacted with cotton / polyester fibers to pick up a stable composition of about 40 grams to about 120 grams, for example about 60 grams to about 100 grams, onto about 100 grams of cotton / polyester fibers. The amount of fluid remaining after contacting the fluid and after any fluid removal is known as the percent wet pickup.
The polymerisable component of the processing fluid is then made to form a graft onto cotton / polyester fibers. In one embodiment, the polymerization comprises drying the cotton fibers by exposing the prepolymer and the organopolysiloxane to a temperature that is sufficient to polymerize the polymer grafted to the cotton fibers. Is achieved. The drying temperature in one embodiment is approximately 121.1111 degrees Celsius (250 degrees Fahrenheit) to 204.4444 degrees Celsius (400 degrees Fahrenheit), and the drying time is approximately 10 seconds to 10 minutes.
In another embodiment, the stable composition is: about 3.2% to about 15% acrylic prepolymer; about 0.2% to about 2% elastomer latex prepolymer; about 8% to about 30% organic polypolymer Including about 0.2% to about 2% urethane prepolymer emulsion; about 0.004% to about 0.1% catalyst; and about 0.004% to about 0.1% graft initiator. . The stable composition advantageously further comprises about 0.004% to about 0.1% polyethylene glycol diacrylate; and about 0.002% to about 0.2% surfactant monomer.

In one preferred embodiment for treating cotton / polyester fibers, the stable composition is: about 4% to about 12% acrylic prepolymer; about 0.4% to about 1.5% elastomer latex prepolymer. Approximately 9% to approximately 26% organopolysiloxane emulsion; approximately 0.4% to approximately 1.5% urethane prepolymer emulsion; approximately 0.006% to approximately 0.05% catalyst; approximately 0.006% About 0.05% graft initiator; about 0.006% to about 0.05% polyethylene glycol diacrylate; and about 0.006% to about 0.05% surfactant monomer.
The treatment composition is advantageously provided by one composition fluid concentrate. Such fluid thickeners include approximately 8% to approximately 35% acrylic prepolymer; approximately 0.5% to approximately 6% elastomer latex prepolymer; approximately 30% to approximately 70% organopolysiloxane emulsion; approximately 0 .5% to about 6% urethane prepolymer emulsion; about 0.01% to about 0.4% catalyst; about 0.01% to about 0.4% graft initiator. The treatment provides an excellent product when it also includes approximately 0.01% to approximately 0.4% polyethylene glycol diacrylate and approximately 0.01% to approximately 0.4% surfactant monomer. Again, the concentrated composition self-polymerizes at a temperature of approximately 15.55556 degrees Celsius (60 degrees Fahrenheit) to 32.22222 degrees Celsius (90 degrees Fahrenheit) during storage for a period of at least 2 months, 5% Stable with less prepolymer, and stable concentrated compositions contain about 10% to about 35% fixation when dried.

The fluid concentrate is diluted using the same dilution factor as described above, ie, approximately concentrate 2: from water 100, approximately concentrate 100: water 100, preferably approximately concentrate 4: water 100 to approximately concentrate. Agent 50: water 100, more preferably about 10% thickener to about 100 concentrated agent 25: water 100 may be added. In one preferred embodiment, the treatment composition is formed by adding one thickener to 2 to 4 water or other solvent.
The stable concentrated composition in one embodiment is: about 16% to about 30% acrylic prepolymer; about 1% to about 4% elastomer latex prepolymer; about 38% to about 60% organopolysiloxane emulsion; Approximately 1% to approximately 4% urethane prepolymer emulsion; approximately 0.02% to approximately 0.2% solvent; approximately 0.02% to approximately 0.2% graft initiator. The concentration agent may also include from about 0.02% to about 0.2% polyethylene glycol diacrylate and from about 0.02% to about 0.2% surfactant monomer.

In another embodiment, the stable concentrated composition comprises about 20% to about 24% acrylic prepolymer; about 2% to about 3% elastomer latex prepolymer; about 46% to about 52% organopolysiloxane emulsion. Approximately 2% to approximately 3% urethane prepolymer emulsion; approximately 0.03% to approximately 0.1% catalyst; approximately 0.03% to approximately 0.1% polyethylene glycol diacrylate; approximately 0.03% From about 0.1% surfactant monomer; and from about 0.03% to about 0.1% graft initiator.
The thickener advantageously has approximately 25% to approximately 32% solids, preferably approximately 25% to approximately 30% solids when dried.
The surfactant monomer can be any surfactant monomer, also referred to as an ionic monomer. Such monomers contain sulfonic acid groups such as sodium vinyl sulfonate, sodium p-styrene sulfonate, sodium methallyl sulfonate, sodium methallyl ether p-sulfophenyl sodium, or sodium 2-methyl-2-acrylamidopropane sulfonate. But you can. Such groups are known to increase hydrophilicity. Carboxylate-containing comonomers such as itaconic acid are also surfactant monomers. A preferred surfactant monomer is sodium vinyl sulfonate.

As described above, the graft initiator may be one or more salts of Fe, Ag, Co, Cu, or a mixture thereof. Similarly, the catalyst may be a peroxide, peracid, perbenzoate, and mixtures thereof.
When the cotton / polyester fibers comprise undyed cotton / polyester fibers, the stable composition is advantageously further about 0.4% to about 8% fluoroalkyl acrylate, such as about 0.8% to about 6% fluoro. Alkyl acrylate, preferably from about 1.2% to about 4.5% fluoroalkyl acrylate.
The concentrated stable composition providing the preferred treated non-dyed cotton / polyester fibers further comprises from about 2% to about 16% fluoroalkyl acrylate, such as from about 4% to about 12% fluoroalkyl acrylate, preferably From about 6% to about 9% fluoroalkyl acrylate.
Again, the invention relates to treated products as well as products comprising treated fibers, fabrics, yarns and staples.
The present invention also relates to a stable treatment fluid and a stable concentrated composition for treating cotton / polyester fibers.

Printed Cotton The method of treating pre-printed cotton fibers with dyes is: approximately 1% to approximately 12% acrylic prepolymer; approximately 0.08% to approximately 2% elastomer latex prepolymer; approximately 3% to approximately 25% of the organic polysiloxane emulsion; about 0.08% from about 2% urethane prepolymer emulsion; from about 1.4% about 11.5% of high density polyethylene prepolymer; approximately 0.8% approximately 9% Providing a stable fluid composition comprising about 0.0004% to about 0.15% catalyst; and about 0.0004% to about 0.15% graft initiator. Preferably, about 0.08% to about 2% nonionic dispersant; about 0.0004% to about 0.15% polyethylene glycol diacrylate; and about 0.0004% to about 0.15% urethane acrylate. Is also included. Again, the treatment composition self-polymerizes at a temperature of approximately 15.55556 degrees Celsius (60 degrees Fahrenheit) to 32.22222 degrees Celsius (90 degrees Fahrenheit) during storage for a period of at least 2 months, less than 5% Stable with prepolymer. When dried, the solid content of the stable composition is at least approximately 5% by weight.
This processing fluid picks up about 40 grams to about 120 grams of the stable composition, about 100 grams of cotton fiber, preferably about 60 grams to about 100 grams of stable composition into about 100 grams of printed cotton fiber. To make contact with the printed cotton fiber.

Finally, the method includes forming a graft polymer. In one embodiment, this results from drying the cotton fibers by exposing the prepolymer and at least half of the silicone oil to a temperature sufficient to polymerize into a polymer grafted to the printed cotton fibers. Arises as For example, the drying temperature may be approximately 121.1111 degrees Celsius (250 degrees Fahrenheit) to 204.4444 degrees Celsius (400 degrees Fahrenheit), and the drying time is approximately 10 seconds to 10 minutes.
In one embodiment, the stable composition is: approximately 1.6% to approximately 10% acrylic prepolymer; approximately 0.2% to approximately 1.5% elastomer latex prepolymer; approximately 5% to approximately 23%. approximately 0.2 about 1.5% of% of the urethane prepolymer emulsion; high density polyethylene prepolymer from approximately 2% of about 10%; about 1.4% from about 7.5% polyamide organopolysiloxane emulsion From about 0.002% to about 0.1% catalyst; and from about 0.002% to about 0.1% graft initiator. Again, from about 0.2% to about 1.5% nonionic dispersant; from about 0.002% to about 0.1% polyethylene glycol diacrylate; and from about 0.002% to about 0.1% The presence of urethane acrylate provides a preferred product. The fluid must of course be stable.

In one embodiment, the stable composition for treating printed cotton comprises from about 2.4% to about 8% acrylic prepolymer; from about 0.3% to about 1% elastomer latex prepolymer; approximately 6 approximately 20% percent of the organopolysiloxane emulsion; from about 2%; approximately 0.3% approximately 1% of the urethane prepolymer emulsion; about 2.6 about 8.5% of% of high density polyethylene prepolymer Approximately 6% polyamide prepolymer; approximately 0.006% to approximately 0.05% catalyst; approximately 0.006% to approximately 0.05% graft initiator; approximately 0.3% to approximately 1% nonionic About 0.006% to about 0.05% polyethylene glycol diacrylate; and about 0 Containing from 006% approximately 0.05% of the urethane acrylate.
In yet another embodiment, the stable composition comprises about 5% to about 24% acrylic prepolymer; about 0.4% to about 4% elastomer latex prepolymer; about 15% to about 50% organic polypolymer. siloxane emulsion; approximately 0.4% of the approximately 4% urethane Rimmer emulsion; high density polyethylene prepolymer approximately 7% about 23%; about 4% to about 18% of a polyamide prepolymer; from about 0.002% A stable concentrated composition comprising about 0.3% catalyst; and about 0.002% to about 0.3% graft initiator is provided by mixing with water or other solvent. The concentrated composition further comprises approximately 0.4% to approximately 4% nonionic dispersant; approximately 0.002% to approximately 0.3% polyethylene glycol diacrylate; and approximately 0.002% to approximately 0.3%. The urethane acrylate may be included. The stable concentrate dilution is the same as previously described for the other stable concentrates.

The concentrated composition is less than 5% prepolymer that self-polymerizes at a temperature of approximately 15.55556 degrees Celsius (60 degrees Fahrenheit) to 32.22222 degrees Celsius (90 degrees Fahrenheit) during storage for a period of at least 2 months. Stabilize.
A stable concentrated composition, when dried, comprises about 10% to about 35% solids, preferably about 25% to about 32% solids. The concentrate is effectively diluted with water before use.
The thickener is from about concentrate 2: water 100 to about concentrate 100: water 100, preferably about concentrate 4: water 100 to about concentrate 50: water 100, more preferably about concentrate 10: It can be diluted with water added in a mass ratio from water 100 to approximately the concentration agent 25: water 100.

In one embodiment, the stable concentrated composition is: about 8% to about 20% acrylic prepolymer; about 1% to about 3% elastomer latex prepolymer; about 25% to about 46% organopolysiloxane emulsion. ; about 1 about 3% to% of the urethane prepolymer emulsion; high density polyethylene prepolymer from approximately 10% of the approximately 20%; approximately 7% from about 15% polyamide prepolymer; from about 0.01% about 0.2 % Catalyst; and about 0.01% to about 0.2% graft initiator. The concentration agent is about 1% to about 3% nonionic dispersant; about 0.01% to about 0.2% polyethylene glycol diacrylate; and about 0.01% to about 0.2% urethane acrylate. It is further improved by including.
In yet another preferred embodiment, the stable concentrated composition comprises: about 12% to about 16% acrylic prepolymer; about 1.5% to about 2% elastomer latex prepolymer; about 30% to about 40% organic polysiloxane emulsion; approximately 1.5% of the approximately 2% urethane prepolymer emulsion; high density polyethylene prepolymer from approximately 13% of the approximately 17%; about 10 approximately 12% from the% polyamide prepolymer; approximately 0.03 % To approximately 0.1% catalyst; approximately 0.03% to approximately 0.1% graft initiator; approximately 1.5% to approximately 2% nonionic dispersant; approximately 0.03% to approximately 0. 1% polyethylene glycol diacrylate; and approximately 0.03% to approximately 0 Containing 1% of the urethane acrylate. This stable concentrated composition, when dried, contains approximately 25% to approximately 30% solids.

Again, the graft initiator effectively comprises a salt of Fe, Ag, Co, Cu or a plurality of salts or mixtures thereof. The initiator may include a magnesium salt. The catalyst includes a strong oxidant, such as a peroxide, peracid, perbenzoate, or a mixture thereof. Most preferred is urea peroxide.
Again, the present invention relates to treated products as well as goods, fabrics, yarns and staples comprising treated fibers.
The present invention also relates to both a stable processing fluid and a stable concentrated composition for processing cotton / polyester fibers.

A treatment composition that is particularly suitable for cotton / polyester fibers preprinted with printed cotton / polyester dyes will now be described. The printed cotton / polyester fibers are: about 1% to about 20% acrylic prepolymer; about 0.08% to about 2% elastomer latex prepolymer; about 6% to about 35% organopolysiloxane emulsion; 0.08% to about 2% polyamide prepolymer; about 0.2% to about 4% adhesive rubber, such as carboxylated butadiene acrylonitrile prepolymer; about 0.001% to about 0.15% catalyst; 0.001% to about 0.15% graft initiator; and effectively about 0.001% to about 0.15% polyethylene glycol diacrylate and about 0.001% to about 0.15% surfactant. Contact with a stable fluid composition containing monomer. The composition is stable with less than 5% prepolymer that self-polymerizes at a temperature of approximately 15.55556 degrees Celsius (60 degrees Fahrenheit) to 32.22222 degrees Celsius (90 degrees Fahrenheit) during storage for at least 2 months . When dried, the solid content of the stable composition is at least approximately 5% by weight.
The contact may be by any method, preferably the printed cotton / polyester fiber is about 40 grams to about 120 grams of the stable composition to about 100 grams of cotton fibers, preferably about 60 grams to about 100 grams. Pick up the stable composition onto approximately 100 grams of printed cotton / polyester fibers.

Finally, the polymerizable material in the treatment composition is polymerized into printed cotton / polyester fibers to form a graft polymer. This formation of the graft polymer involves drying the printed cotton / polyester fiber at a temperature sufficient for at least half of the prepolymer and organopolysiloxane to polymerize into the polymer grafted to the printed cotton fiber. May be started. The drying temperature may be approximately 121.1111 degrees Celsius (250 degrees Fahrenheit) to 204.4444 degrees Celsius (400 degrees Fahrenheit), and the drying time may be approximately 10 seconds to 10 minutes.
In one embodiment, the stable composition is: about 2% to about 15% acrylic prepolymer; about 0.2% to about 1.5% elastomer latex prepolymer; about 8% to about 30% organic. About 0.2% to about 1.5% polyamide prepolymer; about 0.4% to about 3% carboxylated butadiene acrylonitrile prepolymer; about 0.002% to about 0.05% catalyst. Approximately 0.002% to approximately 0.05% graft initiator; and effectively approximately 0.002% to approximately 0.05% polyethylene glycol diacrylate and approximately 0.002% to approximately 0.05%; A surfactant monomer.

In one embodiment, the stable composition comprises about 3.6% to about 12% acrylic prepolymer; about 0.3% to about 1.25% elastomer latex prepolymer; about 9% to about 27% Organopolysiloxane emulsion; approximately 0.3% to approximately 1.25% polyamide prepolymer; approximately 0.6% to approximately 2.5% carboxylated butadiene acrylonitrile prepolymer; approximately 0.004% to approximately 0.03 About 0.004% to about 0.03% graft initiator; about 0.004% to about 0.03% polyethylene glycol diacrylate; and about 0.004% to about 0.03%. Contains a surfactant monomer.
In yet another embodiment, the stable composition comprises: about 5% to about 40% acrylic prepolymer; about 0.4% to about 4% elastomer latex prepolymer; about 30% to about 70% organic polypolymer About 0.4% to about 4% polyamide prepolymer; about 1% to about 8% carboxylated butadiene acrylonitrile prepolymer; about 0.005% to about 0.3% catalyst; A stable concentrated composition comprising 005% to approximately 0.3% graft initiator is provided by mixing with a solvent, such as water. Effectively, the thickener also comprises approximately 0.005% to approximately 0.3% polyethylene glycol diacrylate and approximately 0.005% to approximately 0.3% surfactant monomer.

The concentrated composition is stable with less than 5% prepolymer that self-polymerizes at a temperature of approximately 15.55556 degrees Celsius (60 degrees Fahrenheit) to 32.22222 degrees Celsius (90 degrees Fahrenheit) during storage for at least two months .
A stable concentrated composition, when dried, dries about 10% to about 35% solids, preferably about 25% to about 32% solids, more preferably about 25% to about 30% solids. Included.
In one embodiment, the stable concentrated composition comprises about 10% to about 30% acrylic prepolymer; about 1% to about 3% elastomer latex prepolymer; about 40% to about 60% organopolysiloxane emulsion. Approximately 1% to approximately 3% polyamide prepolymer; approximately 2% to approximately 6% carboxylated butadiene acrylonitrile prepolymer; approximately 0.01% to approximately 0.1% catalyst; and approximately 0.01% to approximately Contains 0.1% graft initiator. The stable concentrated composition effectively also includes approximately 0.01% to approximately 0.1% polyethylene glycol diacrylate and approximately 0.01% to approximately 0.1% surfactant monomer.

In a preferred embodiment, the stable concentrated composition comprises about 18% to about 24% acrylic prepolymer; about 1.5% to about 2.5% elastomer latex prepolymer; about 46% to about 54% organic. About 1.5% to about 2.5% polyamide prepolymer; about 3% to about 5% carbolated butadiene acrylonitrile prepolymer; about 0.02% to about 0.06% catalyst; From about 0.02% to about 0.06% graft initiator; from about 0.02% to about 0.06% polyethylene glycol diacrylate; and from about 0.02% to about 0.06% surfactant monomer. Including.
The method of treating printed cotton / polyester fibers can be performed when the fibers are in the form of a fabric.
In one embodiment, the graft initiator comprises a salt or salts of Fe, Ag, Co, Cu, or a mixture thereof. In another embodiment, the initiator comprises a salt of Fe, Mg, or a mixture thereof. The catalyst includes a peroxide, a peracid, a perbenzoate, or a mixture thereof.
Again, the present invention relates to treated products as well as goods, fabrics, yarns and staples comprising treated fibers.
The present invention also relates to both a stable processing fluid and a stable concentrated composition for processing printed cotton / polyester fibers.

Cotton stretch component It may be necessary to use cotton fibers in the stretch composition. Surprisingly, heavy-filled cotton fibers with certain prepolymer graft combinations not only show excellent antifouling properties, good hand feel, and excellent clock robustness, but also have excellent resilience after stretching I found out. The commercial mixture used for this purpose is a mechanical mixture of cotton (approximately 95%) and SPANDEX (TM) or LYCRA (TM). While the above-described formulations work well for treating cotton fibers intended for this purpose, special stable fluid formulations that are useful for imparting stretch and recovery properties to cotton fibers are approximately 0.8% to about 15% acrylic prepolymer; about 0.4% to about 9% high molecular weight silicone; about 6% to about 35% silicone oil emulsion; about 1.5% to about 12% urethane About 0.0004% to about 0.15% catalyst; and about 0.0004% to about 0.15% graft initiator. Effectively, the treatment composition also includes approximately 0.0004% to approximately 0.15% polyethylene glycol diacrylate and approximately 0.0004% to approximately 0.15% urethane acrylate prepolymer.

Unlike other composition treatments that fill after about 2 to about 6% grafting and polymerization, cotton filling is effectively about 3% to about 10%, such as about 5% to about 7%. is there. Such a filling is stretched to approximately 150% of its original length, held for 30 seconds, and allowed the fabric to relax for 30 seconds, after which the fabric is approximately 95% to approximately 95% of its original size. 115%, preferably about 97% to about 108%. This can be repeated at least 5 times, preferably at least 10 times on the treated fabric with substantially the same result.
Effectively, the composition self-polymerizes at a temperature of approximately 15.55556 degrees Celsius (60 degrees Fahrenheit) to 32.22222 degrees Celsius (90 degrees Fahrenheit) during storage for at least 2 months, and less than 5% pre- Stable with polymer.
Stretchable cotton fibers are contacted with this treatment composition to pick up approximately 40 grams to approximately 200 grams of a stable composition to approximately 100 grams of cotton fiber, preferably approximately 60 grams to approximately 140 grams. . Advantageously, the fibers are dried before contacting the treatment composition to facilitate fluid transfer to the fiber structure.

The prepolymer in the processing fluid can then be stretched, for example, by subjecting the prepolymer and silicone oil to a temperature that is sufficient to polymerize into a polymer that is grafted onto stretchable cotton fibers. Grafted into cotton fibers and polymerized. A drying temperature of approximately 121.1111 degrees Celsius (250 degrees Fahrenheit) to 204.4444 degrees Celsius (400 degrees Fahrenheit) with a drying time of approximately 10 seconds to 10 minutes is sufficient for most fabrics.
In one embodiment, the stable composition comprises from about 2% to about 10% acrylic prepolymer; from about 0.8% to about 7% high molecular weight silicone; from about 8% to about 30% silicone oil emulsion; About 1.2% to about 8% urethane; about 0.002% to about 0.1% catalyst; about 0.002% to about 0.1% graft initiator; and effectively about 0.002. % To approximately 0.1% polyethylene glycol diacrylate and approximately 0.002% to approximately 0.1% urethane acrylate prepolymer.

In one preferred embodiment, the stable composition comprises about 2.4% to about 8% acrylic prepolymer; about 1.2% to about 5% high molecular weight silicone; about 10% to about 27% silicone oil. From about 1.6% to about 6% urethane; from about 0.006% to about 0.05% catalyst; from about 0.006% to about 0.05% graft initiator; from about 0.006% About 0.05% polyethylene glycol diacrylate; and about 0.006% to about 0.05% urethane acrylate prepolymer.
The stable composition is about 4% to about 30% acrylic prepolymer; about 2% to about 18% high molecular weight silicone; about 30% to about 70% silicone oil emulsion; about 3% to about 24% Approximately 0.002% to approximately 0.3% catalyst; approximately 0.002% to approximately 0.3% graft initiator; and effectively approximately 0.002% to approximately 0.3% polyethylene glycol. It may be provided by mixing a stable concentrated fluid composition comprising diacrylate and approximately 0.002% to approximately 0.3% urethane acrylate prepolymer.
Again, this concentrated composition self-polymerizes at a temperature of approximately 15.55556 degrees Celsius (60 degrees Fahrenheit) to 32.22222 degrees Celsius (90 degrees Fahrenheit) during storage for at least 2 months, and less than 5% pre- Stable with polymer.
The stable concentrated composition comprises from about 10% to about 35% solids when dried, preferably from about 25% to about 32% solids when dried.

In one embodiment, the stable concentrated composition comprises about 10% to about 20% acrylic prepolymer; about 4% to about 14% high molecular weight silicone; about 40% to about 60% silicone oil emulsion; 6% to about 16% urethane; about 0.01% to about 0.2% catalyst; about 0.01% to about 0.2% graft initiator; and effectively from about 0.01% About 0.2% polyethylene glycol diacrylate; and about 0.01% to about 0.2% urethane acrylate prepolymer.
In one preferred embodiment, the stable concentrated composition comprises about 12% to about 16% acrylic prepolymer; about 6% to about 10% high molecular weight silicone; about 50% to about 55% silicone oil emulsion. Approximately 8% to approximately 12% urethane; approximately 0.03% to approximately 0.1% catalyst; approximately 0.03% to approximately 0.1% graft initiator; approximately 0.03% to approximately 0.1. 1% polyethylene glycol diacrylate; and approximately 0.03% to approximately 0.1% urethane acrylate prepolymer. This stable concentrated composition, when dried, contains approximately 25% to approximately 30% solids.

The stretchable cotton fibers are advantageously in the fabric state.
In one embodiment, the graft initiator comprises a salt or salts of Fe, Ag, Co, Cu, or a mixture thereof. In another embodiment, the initiator comprises Fe, Mg salt or salts, or mixtures thereof.
In one embodiment, the catalyst is a peroxide, peracid, perbenzoate, periodate, or a mixture thereof.
Printing of non-reactive pigments on cotton and cotton / polyester is known. One adhesive includes carboxylated butadiene acrylonitrile, but many other adhesive rubbers are known. Surprisingly, a small amount of crosslinker, specifically from about 0.01% to about 0.3%, preferably from about 0.02% to about 0.1%, more preferably from about 0.03 to about 0. It has been found that including at least one crosslinked prepolymer of 06 improves clock fastness and color fastness. Preferred compositions have both urethane acrylate and polyethylene glycol diacrylate present in the above mentioned concentration range in carboxylated butadiene acrylonitrile. It may be necessary to include a small amount of water, for example from about 0.1 to about 1%, to stabilize the polymer composition.

  A compatible adjuvant can be added to the composition for its known purposes. Such adjuvants include viscosity control agents, fragrances, emulsifiers, preservatives, UV absorbers, antioxidants, bactericides, fungicides, colorants, dyes, fluorescent dyes, brighteners, opacifiers, soil release agents. , And shrinkage control agents, but are not limited thereto. One example of a useful class of antimicrobial agents that impart antimicrobial activity to fibers is a polymerizable protonated amine. One example of a useful class of flame retardants includes polymerizable vinylidene chloride. In addition, antioxidants, antiozonants, and other stabilizers can be added to the fabric to improve its resistance to aging, high temperature induced degradation or fading. In order to extend the shelf life of the adjuvant, it is useful to bind the adjuvant to the treated fibers. The adjuvant may be copolymerized with the treatment composition under certain conditions, or may be exchanged for a receiving monomer contained in the treatment agent. These adjuvants, when used, are added at their usual levels, except for the preferred liquid composition, generally up to approximately 5% by weight of each flame retardant.

  In one embodiment, the adjuvant includes a polymerizable polymerizable monomer or prepolymer in an amount sufficient to significantly improve the hydrophobicity of the treated fiber. In some cases, the adjuvant can have more than one functional group, for example, dialkyl fatty acid amines can alter the hydrophobic properties of the fiber as well as provide antimicrobial properties. In another embodiment, a hydrophilic monomer or prepolymer is included in an amount sufficient to significantly improve the hydrophilic properties of the treated fiber. Examples include the aforementioned surfactant monomers, namely sodium p-styrene sulfonate, sodium methallyl sulfonate, sodium methallyl ether p-sulfophenyl sodium, sodium 2-methyl-2-acrylamidopropane sulfonate. Monomers such as itaconic acid. It may be advantageous to treat certain regions or sides of the fiber or fabric with certain adjuvants and treat other regions or sides with other adjuvants. For example, the bandage effectively includes antimicrobial properties, as well as hydrophobic and hydrophilic regions or sides of certain regions.

The formulations described for each of the cotton and cotton / polyester fibers described above are advantageous because they can be applied without new equipment or processing steps. The method of the present invention contemplates contacting the fibers and yarns and fabrics with the grafting solution at every stage of yarn or fabric manufacture. Thus, the graft solution may be applied to staple or filament fibers, yarns, or formed fabrics. The treatment composition may be grafted onto filaments during a spin finishing operation and then formed into a woven fabric. In addition, the yarn may be formed from grafted filaments, which are then formed into a fabric. Alternatively, the yarn may be formed from non-grafted filaments, and the treatment composition is then grafted into yarn, after which the yarn is formed into a fabric.
It is possible to fire the yarn and then graft the treatment composition onto the yarn emitted during the slashing operation, or it is possible to fire the grafted yarn before forming the fabric. In addition, the grafted yarn can be repackaged and then repackaged as warp or weft yarn during fabric formation.

The treatment composition may be grafted onto staples, and the grafted staples are then spun into yarn. The grafted filaments may be cut into staples, and the staples may be spun into yarn. The filament or yarn or fabric may be contacted with the solution of the first component by dipping, spraying, or coating operations.
It is further contemplated that the fiber or yarn may be contacted with the grafting solution either before or after chemical or mechanical manufacturing operations such as spin finishing, lubricant application, or sizing. Further, the graft solution may be applied to the yarn or fiber after formation of the fabric therefrom. The fabric may be contacted with the graft solution either before, during, or after chemical and mechanical finishing operations, such as the application of fabric softeners or calendering operations.

The presence of the treated polymer in the fabric can be inferred by certain tests described herein. As the test sample, a 45.72 cm (18 inch) x 45.72 cm (18 inch) fabric sample commonly used for shrinkage testing is used. The sample should be marked for shrinkage in the usual way as additional shrinkage data is obtained during testing of the polymer. One corner of a 45.72 cm (18 inch) by 45.72 cm (18 inch) sample, each with half a teaspoon of Heinz (TM) tomato ketchup, Hersey's (TM) chocolate syrup, and Welch's (TM ) Put the grape juice. Push dirt into the fabric and wipe off excess with a clean paper towel. Wash with warm water (40.55556 degrees Celsius (105 degrees Fahrenheit)) in a normal cycle using a detergent, such as Tide Ultra Clean ™. After washing, the sample is dried. 3 dirt should be removed completely (or almost completely). Dirt is rated on a scale of “1-5”, “5” indicates no color, “4” indicates a light color, “3” indicates a slight color, and “2” indicates a slight color. Indicates that there are many colors, and “1” indicates that there is a large amount of colors. The treated fabric will have a rating greater than 3.5, preferably a rating greater than 4. Untreated cotton has a soil value of 1-2.
The shrinkage of the treated fibers in the woven state is less than 4.5%, preferably less than 4%, most preferably less than 3.5%. The untreated fabric has a shrinkage of 7.5 to 9%.

The mass of the fiber or fabric filling depends on the desired end use and cost factors. Applicants have surprisingly found that good hand, color fastness, antifouling, shrinkage, and abrasion resistance properties are improved with the loading of the processing chemical grafted thereon. Economic concerns limit the amount generally below about 10% by weight. Excellent dough properties are observed with a filling of about 2% to about 7%, preferably about 3% to about 5%. The treatment fill should be at least half of the initial treatment after approximately 15 washes.
The formulation is made by adding a pre-calculated amount of the desired prepolymer to the container, to which monomers, prepolymer, catalyst, graft initiator, and other components of the composition are added. Each component is taken in a mass concentration ratio as shown in the composition described herein. The contents are stirred into a uniform solution.
The fabric was manufactured and processed with the formulation described below. The fabric was then tested. Softness (“feel”) is a reasonable judgment of an independent examiner when compared to 100% cotton fabric. Clocking was tested using AATCC test method B on both wet and dry clock meters. The rating is based on a scale of “1-5”, “5” indicates no color transfer, “4” indicates a light color shift, “3” indicates a slight color shift, “2” indicates that a significant amount of color has been transferred, and “1” indicates that a large amount of color has been transferred. Color fastness was tested using AATCC test method 61 11A. Shrinkage was tested using AATCC test method 135-1992-IVA 111. Abrasion resistance was tested using the test method ASTM D1376 (30 minutes).

A formulation having the composition shown in Table 1 was made. This formulation is applied to the fabric when diluted in the range of approximately Water 2 Countermeasure 1 to approximately Water 4 Countermeasure 1 and approximately 60% wet pickup, and approximately 171.1111 degrees Celsius (340 degrees Fahrenheit) ) Was found to give the fabric a good feel, a shrinkage of less than 4%, a clock fastness of at least 4, no pilling during the rub resistance test, and an antifouling of at least 3.5. . The composition was also found to be a stable fluid without visible precipitation after storage at room temperature for a period of 3 months or longer.
Table 1, Prescription for dyed cotton fabric
Mass parts glyoxal resin prepolymer, Ecco Res GB404 (TM) 5.6
Urethane prepolymer, Resamin UMT171 (TM) 5.6
High molecular weight silicone softener, Helical WO-8026 (TM) 1.63
Silicon softener, Sequasoft 69 (TM) 56.13
Elastomer latex, Hystretch V-43 (TM) 2.80
Non-ionized water 27.0
Diethylene glycol 1.0
Urethane acrylate, SR-9035 (TM) 0.06
Polyethylene glycol diacrylate, SR344 (TM) 0.06
Urea peroxide (0.1% in non-ionized water) 0.06
Ferrous ammonium sulfate (0.1N) 0.06

In another composition, diethylene glycol was replaced with additional water with little degradation of the finished fabric properties.
In another composition, the glyoxal resin prepolymer Ecco Res GB404 (TM) was replaced with the glyoxal resin prepolymer Resin KLF (TM), and the formaldehyde in the fabric was reduced below 30 ppm.

Example 2
A formulation having the composition shown in Table 2 was made. This formulation is applied to the fabric when diluted in the range of approximately Water 2 Countermeasure 1 to approximately Water 4 Countermeasure 1 and approximately 60% wet pickup, and approximately 171.1111 degrees Celsius (340 degrees Fahrenheit) ) When dried at a temperature of 4) it is found to give the fabric a good feel, shrinkage of less than 4%, clock fastness of at least 4, no pilling during rub resistance, and at least 3.5 antifouling properties. It was.
Table 2, Formulation of dyed cotton / polyester fabric
Mass parts acrylic prepolymer, Helical 8001 (TM) 4.86
Urethane prepolymer, Resamine UMT171 (TM) 2.43
Acrylic prepolymer, EccoRez907 (TM) 2.43
Softener polysiloxane, APS V-soft (TM) 48.7
Acrylic prepolymer, Helical WD8061 (TM) 14.61
Elastomer latex, Histretch V-43 (TM) 2.43
Non-ionized water 24.3
Polyethylene glycol diacrylate, SR344 (TM) 0.05
Sodium vinyl sulfonate 0.05
Urea peroxide 0.1N solution 0.05
Ferrous ammonium sulfonate 0.1N solution 0.05

Example 3
A formulation having the composition shown in Table 3 was made.
Table 3, Formulation of printed cotton fabric
Parts by mass
Polyamide prepolymer dispersant, Micromid 632 MPL (TM) 10.89
Urethane prepolymer emulsion,
ResamineUMT171 (TM) 1.80
Acrylic prepolymer, Helical WD8061 (TM) 14.52
Elastomer Latex, Histret V-43 (TM) 1.80
H. D. Polyethylene prepolymer, Mykon HD (TM) 14.52
Modified organopolysiloxane, APS V-soft (TM) 36.31
Nonionic dispersant, Clockfast 2 (TM) 1.80
Non-ionized water 18.2
Urethane acrylate, SR-9035 (TM) 0.04
Polyethylene glycol diacrylate, SR-344 (TM) 0.04
Urea peroxide 0.1N solution 0.04
Ferrous ammonium sulfonate 0.1N solution 0.04
This formulation is applied to the fabric when diluted in the range of approximately Water 2 Countermeasure 1 to approximately Water 4 Countermeasure 1 and approximately 60% wet pickup, and approximately 171.1111 degrees Celsius (340 degrees Fahrenheit) ) Gives the fabric a good hand feel, shrinkage of less than 4%, clock fastness of at least 4, no pilling during rub resistance testing, and antifouling of at least 3.5. all right.

Example 4
A formulation having the composition shown in FIG. 4 was made. This formulation is applied to the fabric when diluted in the range of approximately Water 2 Countermeasure 1 to approximately Water 4 Countermeasure 1 and with a wet pickup of approximately 60%, and 171.1111 degrees Celsius (340 degrees Fahrenheit) When dried with a fabric, the fabric is found to have a good feel, shrink less than 4%, at least 4 clock fastness, no pilling during abrasion resistance testing, and at least 3.5 antifouling properties. It was.
Table 4, Formulation of printed cotton polyester fabric
Parts by mass
Acrylic prepolymer, Helical 8001 (TM) 11.75
Acrylic prepolymer, Helical WD8061 (TM) 7.83
Acrylic prepolymer, Helical 8041 (TM) 1.96
Elastomer Latex, Histret V-43 (TM) 1.96
Non-ionized water 19.6
Polyamide prepolymer dispersant, Micromid 632 MPL (TM) 1.96
Modified organopolysiloxane, APS V-soft (TM) 50.9
Carboxylated butadiene acrylonitrile,
Tylac 68805 (TM) 3.91
Polyethylene glycol diacrylate, SR344 (TM) 0.04
Sodium vinyl sulfonate 0.04
Urea peroxide 0.1N solution 0.04
Ferrous ammonium sulfonate 0.1N solution 0.04

Example 5
A formulation having the composition shown in Table 5 was made. This formulation is applied to the fabric when diluted in a range from approximately Water 2 Countermeasure 1 to approximately Water 4 Countermeasure 1 and approximately 60% wet pickup, and approximately 171.1111 degrees Celsius (340 degrees Fahrenheit) When dried at a degree), the fabric was found to have a good feel, shrinkage of less than 4%, no pilling during the abrasion resistance test, and an antifouling property of at least 3.5.
Table 5, Formulation of cotton fabric
Parts by mass
Glyoxal resin prepolymer, Ecco ResGB404 (TM) 5.6
Urethane prepolymer, Resamin UMT171 (TM) 5.6
High molecular weight silicone softener, Helical WO-8026 (TM) 1.63
Silicon softener, Sequasoft 69 (TM) 56.13
Elastomer latex, Hystretch V-43 (TM) 2.80
Fluoroalkyl acrylate copolymer dispersant,
Texfluor UPL (TM) 8.0
Non-ionized water (DIW) 19
Urethane acrylate, SR-9035 (TM) 0.06
Polyethylene glycol diacrylate, SR344 (TM) 0.06
Urea peroxide (0.1% in non-ionized water) 0.06
Ferrous ammonium sulfonate solution (0.1N) 0.06
Diethylene glycol 1.0
In another composition, diethylene glycol was replaced with additional water with little degradation of the finished fabric properties.
In another composition, the glyoxal resin prepolymer Ecco Res GB404 (TM) was replaced with the glyoxal resin prepolymer Resin KLF (TM), and the formaldehyde in the fabric was reduced below 30 ppm.

Example 6
A formulation having the composition shown in Table 6 was made. This formulation is applied to the fabric when diluted in a range from approximately Water 2 Countermeasure 1 to approximately Water 4 Countermeasure 1 and with a wet pickup of approximately 60%, and approximately 171.1111 degrees Celsius (340 degrees Fahrenheit) When dried at a degree), it was found to have a good feel, shrinkage of less than 4%, no pilling during the abrasion resistance test, and give the fabric at least 3.5 antifouling properties.
Table 6, Formulation for cotton / polyester fabric
Mass parts acrylic prepolymer, Helical 8001 (TM) 4.86
Urethane prepolymer, Resamine UMT171 (TM) 2.43
Acrylic prepolymer, EccoRez907 (TM) 2.43
Softener polysiloxane, APS V-soft (TM) 48.7
Acrylic prepolymer, Helical WD8061 (TM) 14.61
Elastomer latex, Histretch V-43 (TM) 2.43
Fluoroalkyl acrylate copolymer dispersant,
Texfluor UPL (TM) 8.0
Non-ionized water 16.3
Polyethylene glycol diacrylate, SR344 (TM) 0.05
Sodium vinyl sulfonate 0.05
Urea peroxide 0.1N solution 0.05
Ferrous ammonium sulfonate 0.1N solution 0.05

Example 7
A formulation having the composition shown in Table 7 was made. This formulation is applied to the fabric when diluted in the range of approximately Water 2 Countermeasure 1 to approximately Water 4 Countermeasure 1 and approximately 80% wet pickup, and approximately 171.1111 degrees Celsius (340 degrees Fahrenheit) ) Gives the fabric excellent stretch and recovery properties as well as good feel, shrinkage of less than 4%, no pilling during the abrasion resistance test, and at least 3.5 antifouling properties I understood it.
Table 7, Formulation of cotton fabric
Mass parts acrylic prepolymer, Helical 8001 (TM) 13.53
Urethane prepolymer, Resamine UMT171 (TM) 10.25
High molecular weight silicone softener, Helical WO-8026 (TM) 8.12
Silicone softener, Sequasoft 69 (TM) 53.6
Non-ionized water 14.21
Polyethylene glycol diacrylate, SR344 (TM) 0.06
Urethane acrylate, SR-9035 (TM) 0.06
Urea peroxide 0.1N solution 0.06
Ferrous ammonium sulfonate 0.1N solution 0.06

Example 8
Both treated and untreated fabrics are printed with a dye composition and rubber, which is 99.5% carboxylated butadiene acrylonitrile, 0.04% urethane acrylate, and 0.04% polyethylene. It contained glycol diacrylate and a small amount of water as solvent. Fabrics treated with this composition and dried at a temperature sufficient to promote crosslinking, i.e. 171.1111 degrees Celsius (340 degrees Fahrenheit), are dyed with polyethylene glycol diacrylate alone and 171.1111 degrees Celsius. It was found to have a clocking property of at least approximately 0.5 units, at most 2 units, better on a 1 to 5 scale than a similar fabric dried at (340 degrees Fahrenheit).

Example 9
A formulation having the composition shown in Table 8 was made. This formulation is applied to the fabric when diluted in a range from approximately Water 2 Countermeasure 1 to approximately Water 4 Countermeasure 1 and approximately 80% wet pickup, and approximately 171.1111 degrees Celsius (340 degrees Fahrenheit) When dry at a degree) good touch, shrinkage less than 5%, no pilling during abrasion resistance test, good wet clock fastness and acceptable dry clock fastness, and at least 3.5 antifouling property As well as providing excellent stretch and recovery properties to the fabric.
Table 8
Parts by mass
Acrylic prepolymer, Helical 8001 (TM) 12.9
Non-ionized water 25.1
Elastomer Latex, Histret V-43 (TM) 1.29
KF (TM) 28/30% water 44.08
High molecular weight silicone softener, Helical WO-8026 (TM) 3.87
Acrylic prepolymer, Helical WD 8041 (TM) 2.15
KF874 (10% in IPA) 1.29
Aurassoft 280 8.6
Sodium vinyl sulfonate 0.04
Urea peroxide (0.1%) 0.04
Ferrous ammonium sulfonate (0.1%) 0.04

This formulation was tested with a cotton navy stain and the results are in Table 9.

^*Ｍｅｌｌｅｎのバースト試験

^* Mellen's burst test

  The Mellen burst test measures the force required to push a ball about 2.54 cm (1 inch) in diameter through the fabric, which is a measure of the tensile strength of the fabric. As used herein, the tensile strength of a fabric is defined as the force required to push the ball through the fabric according to the Mellen test procedure. The strength ratio is the ratio of the force required to push the ball through the fabric divided by the force required to push the same ball through a similar but untreated fabric. This value is related to sewing ability and wearing ability. Usually, the resin applied to cotton reduces the tensile strength of the cotton fabric. Applicants surprisingly, as indicated above, the treatment of the fibers of the fabric improves the strength ratio to 150% (100% is the same strength as the untreated fabric) with large polymer loading. I understood it. Smaller filling improves the strength ratio to 115% and preferred filling improves the strength ratio to at least 125%.

Example 10
A formulation having the composition shown in Table 10 was made. This formulation is applied to the fabric when diluted in a range from approximately Water 2 Countermeasure 1 to approximately Water 4 Countermeasure 1 and approximately 80% wet pickup, and approximately 171.1111 degrees Celsius (340 degrees Fahrenheit) The fabric has excellent stretch and recovery properties as well as good hand feel, shrinkage of less than 5.4%, no pilling during rub resistance testing, and excellent clock fastness give. Test data for cotton with dark blue stains is shown in Table 11.
Table 10
Parts by mass
Urethane prepolymer, Resamine UMT171 (TM) 15.42
Polyamide prepolymer dispersant, Micromid 632 MPL (TM) 2.57
Silicone softener, Sequasoft 69 (TM) 43.18
High molecular weight silicone softener, Helical WO-8026 (TM) 5.14
Aurassoft 280 (TM) 7.71
Non-ionized water 25.7
Aurawet 634 (TM) 0.22
Urethane acrylate, SR-9035 (TM) 0.005
Sodium vinyl sulfonate 0.005
Sodium metabisulfite (0.1N solution) 0.05

^*Ｍｅｌｌｅｎのバースト試験

^* Mellen's burst test

Examples 11-13
Three formulations having the composition shown in Table 12 were made and the test data is shown in Table 13. This example shows how sensitive the test results are to small formulation changes.

  While it will be apparent that the invention disclosed herein has been sufficiently calculated to meet the above objectives, it will be understood that many modifications and embodiments may be devised by those skilled in the art, The appended claims are intended to cover all such modifications and embodiments that fall within the true spirit and scope of the invention.

Claims (10)

A method of making fibers with a soft hand and good clock fastness, color fastness, abrasion resistance, and antifouling:
Contacting the cellulose fiber with the activated graft initiator to form a location on the fiber where the polymer can adhere and polymerize; and at least 5 weights selected from organopolysiloxanes, polymerizable silicone oils, or mixtures thereof % of polymerisable silica-containing compound, and an acrylic prepolymer, glyoxal prepolymer, elastomer latex prepolymer, polyamide prepolymer, the urethane prepolymer, at least two polymerisable selected from acrylonitrile prepolymer and high density polyethylene prepolymer Contacting the composition comprising a prepolymer with the cellulose fiber under conditions to form a copolymer grafted to the cellulose fiber, and the activated graft initiator is in the composition;
The composition comprises about 5 polymerizable materials that self-polymerize at a temperature between approximately 15.55556 degrees Celsius (60 degrees Fahrenheit) and 32.22222 degrees Celsius (90 degrees Fahrenheit) during storage for a period of at least 2 months. %, Stable,
Forming a graft copolymer on the cellulose fiber, the graft copolymer comprising at least about 5% by weight of a silica-containing compound;
The above method. It said composition further comprises at least one polymerisable prepolymer selected either et polyethylene glycol diacrylate and urethane acrylate prepolymer over method of claim 1, wherein.   The composition further comprises a surfactant monomer selected from sodium vinyl sulfonate, sodium p-styrene sulfonate, sodium methallyl sulfonate, sodium methallyl ether p-sulfophenyl sodium and sodium 2-methyl-2-acrylamidopropane sulfonate. The method according to claim 1 or 2, comprising:   4. The method of any one of claims 1-3, wherein the composition further comprises a catalyst.   The cellulosic fiber is a fiber, yarn or fabric, and contacting the fiber is achieved by dipping, spraying or coating operations. The method described in 1.   The method according to claim 1, wherein the cellulose fiber is in the form of a woven fabric.   A yarn comprising fibers produced by the method of any one of claims 1-5, wherein the graft copolymer comprises 2% to 10% by weight of the yarn.   A yarn comprising fibers produced by the method of any one of claims 1-5.   A woven fabric comprising fibers produced by the method according to any one of claims 1-5.   7. A woven fabric produced by the method of any one of claims 1-6, wherein the graft copolymer comprises 2% to 10% by weight of the yarn.