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WO1995035363A1 - Method of creating a stonewashed appearance in wet-processed fabrics - Google Patents

Method of creating a stonewashed appearance in wet-processed fabrics Download PDF

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Publication number
WO1995035363A1
WO1995035363A1 PCT/US1995/006578 US9506578W WO9535363A1 WO 1995035363 A1 WO1995035363 A1 WO 1995035363A1 US 9506578 W US9506578 W US 9506578W WO 9535363 A1 WO9535363 A1 WO 9535363A1
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WIPO (PCT)
Prior art keywords
fabric
dye
natural
group
synthetic
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Application number
PCT/US1995/006578
Other languages
French (fr)
Inventor
Michael Paul Wiley
David Meredith Shank
David John Milora
Original Assignee
Ivax Industries, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ivax Industries, Inc. filed Critical Ivax Industries, Inc.
Priority to AU26028/95A priority Critical patent/AU2602895A/en
Priority to JP08502190A priority patent/JP3128136B2/en
Publication of WO1995035363A1 publication Critical patent/WO1995035363A1/en

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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
    • D06M16/003—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic with enzymes or microorganisms
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38645—Preparations containing enzymes, e.g. protease or amylase containing cellulase
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/15—Locally discharging the dyes
    • D06P5/158—Locally discharging the dyes with other compounds

Definitions

  • the invention relates to methods for producing a stonewashed effect in fabrics and garments while reducing redeposition of dye on the treated materials.
  • stonewashing is considered a process whereby color is removed from a cellulosic garment or fabric by the mechanical abrasion of pumice stones or other abrasive materials, usually in a water bath in a tumbler or washer, such that localized abrasion creates lighter spots or areas on the surface of said fabric or garment leaving a relatively untouched background.
  • processes which produce a similar appearance to said abraded fabric or garments by chemical or enzymatic means, or combinations of the above with or without mechanical abrasion are included in the definition of stonewashing as it is accepted in the industry.
  • cellulase enzymes are typically divided into two groups: those with greatest activity at a neutral pH range (pH about 6 to 8), and those with greatest activity in the acid pH range (pH about 4 to 6). These ranges represent the pH values of optimum performance, even though each type of enzyme has some activity outside its stated pH range. Both types are commonly used to impart the "stonewashed" appearance and both have advantages and disadvantages.
  • neutral cellulase treatments are that only a moderate amount of indigo dye removed during the washing process is redeposited onto the white portions of the fabric, thus producing stonewashed denim garments that have bright, clean appearing highlighted areas.
  • the major disadvantage is that, typically, a neutral cellulase enzyme will react somewhat slower than an acid cellulase enzyme, thus lengthening processing times.
  • a major advantage of the acid cellulase treatments is that the reaction on fabric is much faster than a neutral cellulase enzyme. A reaction time of two to five times faster than a similar treatment with a neutral cellulase enzyme is not uncommon.
  • the major disadvantage is that a greater amount of dye is redeposited onto the garments due in part to the lower solubility of indigo at the lower pH.
  • compositions for chemically stonewashing fabrics or garments generally are set forth in, for example, U.S. Patent Nos. 4,832,864, 4,912,056, 5,006,126 and 5,122,159. Improved compositions and techniques are required, however, for processing dyed material with fast-acting acid cellulase enzyme treatments while reducing the quantity of redeposited dye, thus rapidly yielding garments with areas of bright, clean contrast and an attractive stonewashed appearance.
  • Still another object of the present invention is to provide a method as aforesaid which is particularly well-adapted for processing indigo dyed denim fabrics or garments.
  • the present invention resides in an improved method for treating dyed fabric, either in unsewn form or in the form of a garment, to produce a stonewashed effect by treating said fabric with a water-based composition having an acidic pH and including at least one acid cellulase enzyme and a dye redeposition inhibiting additive selected from the group consisting of natural and synthetic inorganic silicates, polyalkylene oxide polymers, acrylic polymers (homopolymers and copolymers) and natural, synthetic and semisynthetic polysaccharides, including natural and synthetic gums.
  • novel method utilizing the foregoing additives enables the use of fast- acting acid cellulase enzymes to remove dye and cause the desired localized variations in color density while substantially preventing "backstaining", the redeposition of dye (particularly indigo dye) from the low pH wash water onto the treated fabric.
  • the improved wet-processing method of the invention involves contacting dyed cellulosic fabrics, principally cotton denim fabrics, with an aqueous or water-based solution containing (a) a cellulase enzyme having greatest activity in the acid pH range, and (b) a dye redeposition inhibiting additive, as well as optionally other conventional additives such as buffers, surfactants, enzyme activators, solubilizing agents and the like.
  • a cellulase enzyme having greatest activity in the acid pH range
  • a dye redeposition inhibiting additive as well as optionally other conventional additives such as buffers, surfactants, enzyme activators, solubilizing agents and the like.
  • the fabric treated in accordance with the invention may be in unsewn form or sewn in the form of a garment or other article composed of sewn fabric, preferably a new (unworn) garment or article
  • stonewashed appearance refers to an appearance including local areas of variation in color density on the surface of dyed cellulosic fabrics, resembling the appearance created by mechanical abrasion of the fabric with pumice or other "stones".
  • Stonewashing is normally carried out in commercial washing machines, cylindrical tumblers, converted dryers or similar pieces of equipment.
  • the necessary parameters for practice of the subject method are that there must be a means to contain the wash liquor during the process, along with the garments, fabric, or items being stonewashed, such that they and the enzymes and other processing chemicals can make constant or intermittent contact.
  • there must be a means of introducing mechanical energy into the system allowing the surfaces of the items to be stonewashed to rub against other surfaces, including other fabrics or items being stonewashed. This, in the case of a washing machine or tumbler, is accomplished by rotating the cylinder containing the garments, etc. at such a speed as to allow the garments to move about inside and rub against each other.
  • the stonewash process typically consists of several *steps, rather than a single exposure to cellulase enzyme and/or pumice stones.
  • the garments are first typically desized using (a) amylase enzymes and surfactants, (b) oxidizers, alkalis, and surfactants, (c) solvents and surfactants or (d) hot water. This is frequently, but not necessarily, followed by one or more rinses.
  • the abrasion step normally follows, where the cellulase enzyme and other auxiliary chemicals are used to create the abraded appearance. This is the step during which the dye redeposition preventing additives would normally be present according to the invention.
  • a bleach step (only if the overall color is to be lightened), an antichlor step (only if a bleach step is used), a clean-up step where detergents and brighteners are frequently added to wash away excess loose dye, one or more rinses, and a final softener application. Subsequently, the garments are extracted to remove excess water, then dried and pressed.
  • the additives may provide some benefit if added to the desize operation, the rinses before or after the abrasion, in the cleanup step, or in multiple steps.
  • indigo dye is by far the most common dye used on stonewashed fabrics and garments
  • the stonewash concept applies to any fabric, garment, or article which is made from cellulosic fibers, yarns, or threads, in whole or in part, and is dyed, pigmented, or otherwise colored in such a way as to have a differential of color between the surface and the center of said fibers, threads or yarns, whether the colorant is a vat dye (such as indigo), a pigment (or pigment dye), a sulfur dye, or another classification of dyestuff.
  • vat dye such as indigo
  • a pigment or pigment dye
  • sulfur dye or another classification of dyestuff
  • the key concept is that the fibers or yarns are "ring dyed", named for the resulting appearance of a cross-section of the dyed fiber, being more heavily dyed on the outermost ring of the fiber, less heavily dyed (or not dyed at all) at the center core.
  • the stonewashing process damages the outermost portion of the cellulosic fibers, exposing the undyed (or lighter-dyed) centers of the fibers.
  • the dye redeposition or backstaining preventing additives to be used in the novel methods are selected from the group consisting of natural and synthetic inorganic silicates, such as zeolites, kaolin and bentonite clays; polyalkylene oxide polymers, including polyalkylene oxide polyamine copolymers; acrylic homopolymers and copolymers; and natural, synthetic and semisynthetic polysaccharides, such as natural and synthetic gums and cellulosic polymers.
  • natural and synthetic inorganic silicates such as zeolites, kaolin and bentonite clays
  • polyalkylene oxide polymers including polyalkylene oxide polyamine copolymers
  • acrylic homopolymers and copolymers acrylic homopolymers and copolymers
  • natural, synthetic and semisynthetic polysaccharides such as natural and synthetic gums and cellulosic polymers.
  • Representative generic structures for several categories of dye redeposition preventing additives to be used in the methods of the invention include but are not limited to, the following:
  • Locust Bean gum (principally, galactomannan)
  • KELACIDTM Alginic acid polymannuronic (Merck & Co.) acid + polyguluronic acid
  • VALFORTM 150 Na 2 O ⁇ Al 2 O 3 ⁇ (SiO 2 ) x ⁇ (H 2 O) y
  • montmorillonite Al 2 O 3 ⁇ 4SiO 2 ⁇ H 2 O
  • CARBOPOLTM 613,1622 Crosslinked acrylic copolymers (The B.F. Goodrich Co.)
  • Suitable cellulase enzymes for use in the novel stonewashing method include any cellulases, including those produced from fungal or bacterial sources that are optimally active in acidic solutions in degrading cellulosic fibers.
  • the invention is not limited to any particular cellulase enzymes or any particular sources for such enzymes, but instead comprehends the use of any enzymes with cellulose degrading activity maximized in an acidic medium, which may be defined as a medium with a pH less than 7.0, but preferably within a pH range of about 4 to about 6.
  • the dye redeposition or backstaining inhibiting additives be present in the fabric treatment solution in a weight (w/w) concentration not less than about 0.005%.
  • This minimum level may vary depending on the class of additives utilized. For example, the following are representative concentration ranges for the various classes of redeposition preventing additives, based on experimental test results:
  • Natural/synthetic inorganic silicates .025 - 5.0%
  • Polyalkyleneoxide polymers .025 - 2.5%
  • Polysaccharide polymers .005 - 5.0%
  • Acrylic homopolymers and copolymers .005 - 8.0% It should be stressed that the above weight concentration ranges are based on the total weight of wash liquor in which the fabric is immersed and/or tumbled.
  • the invention is not limited, however, to any specific method, sequence or formulation for adding the essential components of the invention, i.e. the acid cellulase enzymes and anti-redeposition additives to the wash liquor.
  • the enzymes and anti- redeposition additives can first be blended with suitable solvents and other optional ingredients, with the resultant formulation (in liquid, concentrate, gel or other form) being added to the wash water, or the individual components can be separately added in dry or fluid form to the wash water.
  • the water-based compositions used in the novel method of the invention may include not merely appropriate weight concentrations of acid cellulase enzymes and anti-backstaining additives but also optional additional ingredients such as buffers to maintain the pH of the composition at a fairly stable level, surfactants to increase the wettability of the aqueous solution, promoting the activity of the enzyme in the treated fabric; solvents to help dissolve or disperse the enzymes and surfactants; cellulase activators; antioxidants; solubilizers; and builder components such as divalent sequestering agents.
  • optional ingredients include the following:
  • Cellulase enzyme activators - proteins cobalt and its salts, magnesium and its salts, calcium and its salts, potassium and its salts, sodium and its salts or monosaccharides such as mannose and xylose.
  • Solubilizers - lower alcohols such as ethanol, benzenesulfonate salts, lower alkylbenzenesulfonate salts such as p-toluenesulfonate salts, glycols such as propylene glycol, acetylbenzenesulfonate salts, acetamides, pyridinedicarboxylic acid amides, benzoate salts and urea.
  • Builders organic phosphates, phosphonates, phosphonocarboxylates, amino-polyacetates, polyacrylic acids; non-dissociating polymers such as polyethylene glycol, polyvinyl alcohol and polyvinyl pyrrolidone, and salts of dicarboxylic, diglycolic and sulfonated carboxylic acids, borates, citrates and mixtures thereof.
  • the enzyme compositions used in the novel methods may be in any conventional form, including liquids, thickened liquids, concentrates, gels or solids.
  • Various such compositions have been disclosed in the prior art and are known to those of skill in the formulation of textile treatment and processing products.
  • compositions according to the present invention for use in the novel method of treating dyed fabric or garments to produce a stonewashed appearance while substantially preventing redeposition of dye onto the treated material. These examples are not intended, however, to limit the invention in any way or to set forth ingredients, materials or concentration ranges which must be used exclusively to practice the invention.
  • Examples 1-7 define compositions for use in the present invention which contain an acid cellulase enzyme derived from T. longibrachiatum, a buffer comprising 31.2% sodium acetate, 23.3% acetic acid and 45.5% water, the specified dye redeposition preventing additive and water, quantity sufficient to 100% by weight.
  • EXAMPLE 8 Laboratory testing was performed utilizing the compositions of Examples 1-7 in the wet processing of indigo dyed denim fabric to quantify the anti-backstaining benefit of each additive.
  • ⁇ E is calculated by the following formula:
  • Launder-Ometer available from Atlas Electric Devices Co., Chicago, IL.
  • the Launder-Ometer is an AATCC-approved standard laboratory washing machine which rotates (at 40 ⁇ 2 rpm) up to 20 - 3 in. X 8 in. stainless steel cannisters (1.2 liter capacity) in a thermostatically controlled water bath.
  • Each canister contained 200g. of one test solution of Examples 1-9, one - 4 in. X 4 in. white cotton swatch, one - 4 in. X 4 in. desized 14 oz. indigo denim swatch, and 45 - .25 in. stainless steel balls.
  • each test solution was adjusted to 5.0 ⁇ 0.1 units.
  • Each canister was sealed and rotated in the Launder- Ometer at 132 ⁇ 2°F for 60 or 75 minutes.
  • the fabric swatches were removed and rinsed in a Kenmore (Series 60) home washer at a low water level for a six minute cycle.
  • all test swatches were dried in a conventional domestic dryer.
  • Final L,A,b readings were taken and the Total Color Difference ( ⁇ E) was calculated for the white test swatches.
  • Percent improvement (%I) in ⁇ E for each test solution in comparison with control solution was calculated as follows:
  • Table A lists percentage improvement values for the various backstaining inhibiting additives used in Examples 1-7.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
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Abstract

A method of treating dyed cellulosic fabric to create a stonewashed appearance by contacting the fabric with a water-based composition having an acidic pH and including at least one cellulase enzyme having optimum activity in an acidic medium and a dye redeposition inhibiting additive selected from the group consisting of natural and synthetic inorganic silicates, polyalkylene oxide polymers, acrylic polymers, and natural, synthetic and semisynthetic polysaccharides. The fabric is preferably indigo-dyed and may be in unsewn form or in the form of a garment or other article composed of sewn fabric.

Description

METHOD OF CREATING A STONEWASHED APPEARANCE IN WET-PROCESSED FABRICS.
The invention relates to methods for producing a stonewashed effect in fabrics and garments while reducing redeposition of dye on the treated materials.
Wet-processing of fabrics and garments to produce a variety of visual effects enhancing the appeal of the treated materials is a well known practice. This practice is particularly popular when the garments are indigo dyed and/or the garments are constructed from denim fabric, as with jeans, jackets, skirts, etc., as well as certain accessories and various non-garment items similarly constructed.
Of the more popular wet-processing procedures, abrasion of indigo dyed garments or "stonewashing" has become commercially widespread. For purposes of clarity, and to be consistent with industry terminology, "stonewashing" is considered a process whereby color is removed from a cellulosic garment or fabric by the mechanical abrasion of pumice stones or other abrasive materials, usually in a water bath in a tumbler or washer, such that localized abrasion creates lighter spots or areas on the surface of said fabric or garment leaving a relatively untouched background. Further, processes which produce a similar appearance to said abraded fabric or garments by chemical or enzymatic means, or combinations of the above with or without mechanical abrasion, are included in the definition of stonewashing as it is accepted in the industry.
The most common class of enzyme used to impart the modified appearance is cellulase. Cellulase enzymes are typically divided into two groups: those with greatest activity at a neutral pH range (pH about 6 to 8), and those with greatest activity in the acid pH range (pH about 4 to 6). These ranges represent the pH values of optimum performance, even though each type of enzyme has some activity outside its stated pH range. Both types are commonly used to impart the "stonewashed" appearance and both have advantages and disadvantages.
One of the advantages of the neutral cellulase treatments is that only a moderate amount of indigo dye removed during the washing process is redeposited onto the white portions of the fabric, thus producing stonewashed denim garments that have bright, clean appearing highlighted areas. The major disadvantage is that, typically, a neutral cellulase enzyme will react somewhat slower than an acid cellulase enzyme, thus lengthening processing times.
A major advantage of the acid cellulase treatments is that the reaction on fabric is much faster than a neutral cellulase enzyme. A reaction time of two to five times faster than a similar treatment with a neutral cellulase enzyme is not uncommon. The major disadvantage is that a greater amount of dye is redeposited onto the garments due in part to the lower solubility of indigo at the lower pH.
Methods and compositions for chemically stonewashing fabrics or garments generally are set forth in, for example, U.S. Patent Nos. 4,832,864, 4,912,056, 5,006,126 and 5,122,159. Improved compositions and techniques are required, however, for processing dyed material with fast-acting acid cellulase enzyme treatments while reducing the quantity of redeposited dye, thus rapidly yielding garments with areas of bright, clean contrast and an attractive stonewashed appearance.
It is the object of the present invention to provide a method of wet-processing dyed cellulosic fabrics and garments to chemically create a stonewashed appearance in a rapid and effective manner.
It is a further object of the present invention to provide a method as aforesaid which yields fabrics and garments having bright and clean appearing highlighted areas of color variation where dye has been removed.
It is yet a further object of the present invention to provide a method as aforesaid wherein fast-acting acid cellulase enzymes can be utilized as the principal dye-removing agents and yet redeposition of dye on the treated material is substantially avoided.
Still another object of the present invention is to provide a method as aforesaid which is particularly well-adapted for processing indigo dyed denim fabrics or garments.
In keeping with these objects and others which will become apparent hereinafter, the present invention resides in an improved method for treating dyed fabric, either in unsewn form or in the form of a garment, to produce a stonewashed effect by treating said fabric with a water-based composition having an acidic pH and including at least one acid cellulase enzyme and a dye redeposition inhibiting additive selected from the group consisting of natural and synthetic inorganic silicates, polyalkylene oxide polymers, acrylic polymers (homopolymers and copolymers) and natural, synthetic and semisynthetic polysaccharides, including natural and synthetic gums. The novel method utilizing the foregoing additives enables the use of fast- acting acid cellulase enzymes to remove dye and cause the desired localized variations in color density while substantially preventing "backstaining", the redeposition of dye (particularly indigo dye) from the low pH wash water onto the treated fabric.
The improved wet-processing method of the invention involves contacting dyed cellulosic fabrics, principally cotton denim fabrics, with an aqueous or water-based solution containing (a) a cellulase enzyme having greatest activity in the acid pH range, and (b) a dye redeposition inhibiting additive, as well as optionally other conventional additives such as buffers, surfactants, enzyme activators, solubilizing agents and the like. The fabric is tumbled or agitated together with the aqueous solution.
The fabric treated in accordance with the invention may be in unsewn form or sewn in the form of a garment or other article composed of sewn fabric, preferably a new (unworn) garment or article
The term "stonewashed appearance" as used herein refers to an appearance including local areas of variation in color density on the surface of dyed cellulosic fabrics, resembling the appearance created by mechanical abrasion of the fabric with pumice or other "stones".
Stonewashing is normally carried out in commercial washing machines, cylindrical tumblers, converted dryers or similar pieces of equipment. The necessary parameters for practice of the subject method are that there must be a means to contain the wash liquor during the process, along with the garments, fabric, or items being stonewashed, such that they and the enzymes and other processing chemicals can make constant or intermittent contact. Further, there must be a means of introducing mechanical energy into the system, allowing the surfaces of the items to be stonewashed to rub against other surfaces, including other fabrics or items being stonewashed. This, in the case of a washing machine or tumbler, is accomplished by rotating the cylinder containing the garments, etc. at such a speed as to allow the garments to move about inside and rub against each other. In the case of a paddle dye machine, this is accomplished by an external paddle wheel mounted at or near the surface of the process liquor. The paddle turns and creates a circulating current. The current and/or the paddle catches the garments and forces them along in such a way as to rub over other garments and the paddle, creating the necessary mechanical action on the goods.
The stonewash process typically consists of several *steps, rather than a single exposure to cellulase enzyme and/or pumice stones. The garments are first typically desized using (a) amylase enzymes and surfactants, (b) oxidizers, alkalis, and surfactants, (c) solvents and surfactants or (d) hot water. This is frequently, but not necessarily, followed by one or more rinses. The abrasion step normally follows, where the cellulase enzyme and other auxiliary chemicals are used to create the abraded appearance. This is the step during which the dye redeposition preventing additives would normally be present according to the invention. Following abrasion there is sometimes a bleach step (only if the overall color is to be lightened), an antichlor step (only if a bleach step is used), a clean-up step where detergents and brighteners are frequently added to wash away excess loose dye, one or more rinses, and a final softener application. Subsequently, the garments are extracted to remove excess water, then dried and pressed. Although the preferred point to introduce the additives to prevent dye redeposition is with the cellulase enzyme, the additives may provide some benefit if added to the desize operation, the rinses before or after the abrasion, in the cleanup step, or in multiple steps.
While indigo dye is by far the most common dye used on stonewashed fabrics and garments, the stonewash concept applies to any fabric, garment, or article which is made from cellulosic fibers, yarns, or threads, in whole or in part, and is dyed, pigmented, or otherwise colored in such a way as to have a differential of color between the surface and the center of said fibers, threads or yarns, whether the colorant is a vat dye (such as indigo), a pigment (or pigment dye), a sulfur dye, or another classification of dyestuff. The key concept is that the fibers or yarns are "ring dyed", named for the resulting appearance of a cross-section of the dyed fiber, being more heavily dyed on the outermost ring of the fiber, less heavily dyed (or not dyed at all) at the center core. The stonewashing process damages the outermost portion of the cellulosic fibers, exposing the undyed (or lighter-dyed) centers of the fibers.
The dye redeposition or backstaining preventing additives to be used in the novel methods are selected from the group consisting of natural and synthetic inorganic silicates, such as zeolites, kaolin and bentonite clays; polyalkylene oxide polymers, including polyalkylene oxide polyamine copolymers; acrylic homopolymers and copolymers; and natural, synthetic and semisynthetic polysaccharides, such as natural and synthetic gums and cellulosic polymers.
Representative generic structures for several categories of dye redeposition preventing additives to be used in the methods of the invention include but are not limited to, the following:
Natural/Synthetic Inorganic Silicates
Al2O3·4SiO2·H2O, R+ n(Al,Mg)nSi4O10(OH)n·H2O n≥O
H2Al2Si2O8·H 2O
Na2O·Al2O3·(SiO2)·(H2O)y
[Al2O3·4SiO2·Η2O]R+ where R is an organo group.
Polyalkyleneoxide Polymers
Polyaminoethoxylates
Figure imgf000009_0001
Polyethylene Oxide Polymers
-(CH2CH2O)-n
Polyethylene Glycol Polymers
HO(CH2CH2O)nH
Figure imgf000010_0001
Figure imgf000011_0001
Acrylic Homopolymers and Copolymers
Figure imgf000012_0001
The following are illustrative examples of compounds or materials identified by brand name, supplier and/or chemical name or structure, which have been found effective as additives to stonewashing solutions in preventing the redeposition even of dyes, such as indigo, which are poorly soluble in acidic solutions: Product Names Structural Information
Natural and Semisynthetic
Polysaccharides
KELZAN™ Xanthan gum
(Merck & Co., Rahway, N.J.)
Rhamsan gum
WeIan gum
Guar gum
Locust Bean gum (principally, galactomannan)
KELGIN™ MV, KELGIN™ LV Sodium Alginate
(Merck & Co.)
Other alginic acid metal salts
KELACID™ Alginic acid (polymannuronic (Merck & Co.) acid + polyguluronic acid)
NATROSOL™ 250 HR Hydroxyethylcellulose
(Aqualon Co., Wilmington, DE)
METHOCEL™ E5, E4M Hydroxypropylmethylcellulose (The Dow Chemical Co.,
Midland, MI)
METHOCEL™ HB-100 Hydroxybutylmethylcellulose (The Dow Chemical Co.)
Gelatin
Casein
Natural/Synthetic Inorganic Silicates
Kaolin H2Al2Si2O8·H2O
Fullers Earth Colloidal Aluminum Silicate
VALFOR™ 150 Na2O·Al2O3·(SiO2)x·(H2O)y
(PQ Corp.
Valley Forge, Pa.)
BENTONE™ 34, 38, SD-1, SD-2 Organically modified
(Rheox-, Inc., Hightstown, NJ) montmorillonite where
montmorillonite = Al2O3·4SiO2·H2O
Bentonites Al2O3·4SiO2·H2O,
R+.33 (Al,Mg)2Si4O10(OH) 2·nH2O HECTALITE™ 200 Smectite clay (Magnesium- (American Colloid Co., aluminum-silicate mineral) Arlington Heights, IL)
ZEOSYL™ 110SD, DIAFIL™ 810 Hydrated amorphous SiO2
(J.M. Huber Corp., Borger, TX)
HYDRITE™ R
(Dry Branch Kaolin Co.,
Dry Branch, GA)
Montmorillonites
Polyalkylene Oxide Polymers
TETRONIC™ 908, O O
1508
(BASF Corp.)
Figure imgf000014_0001
POLYOX™ WSR N-10, WSR N-3000 (CH2CH2O)n
WSR N-750
(Union Carbide Corp.
Danbury, Conn.)
CARBOWAX™ 400, 4600, 20M HO-(CH2CH2O)nH
(Union Carbide Chemicals
& Plastics)
Acrylic Polymers
CARBOPOL™ 907,910 Acrylic acid, homopolymer
(The B.F. Goodrich Co., [ (CH2CHCOOH)n ]
Akron, OH)
CARBOPOL™ 614,615 High MW Polyacrylic acid
(The B.F. Goodrich Co.) crosslinked w/polyalkenylpolyether
CARBOPOL™ 613,1622 Crosslinked acrylic copolymers (The B.F. Goodrich Co.)
CARBOPOL™ 681 X-1 Acrylic polymer: ethyl
(The B.F. Goodrich Co.) acrylate (formulated)
SOKALAN™ PA 70-PN, 110S Linear Polyacrylic acid,
(BASF AG, (MW: 70,000 & 250,000) Ludwigshaten, Germany)
SOKALAN™ HP-22 CAS #25820-49-9 (copolymer)
(BASF AG)
COLLOID 117/50,207
COLLOID X-0125-KN 706 GOODRITE™ K-7600 N Linear polyacrylic acid,
(B.F. Goodrich Co.) sodium salt (MW:60,000)
PARAGUM™ 511
(Para-Chem Southern, Inc.
Simpsonville, S.C.)
ALCOGUM™ L-11, L-15, L-27 Ethyl acrylate:methacrylic acid
L-37
(National Starch and Chemical
Corp., Bridgewater, NJ)
ALCOGUM™ L-83 Ethyl acrylate:methyl methacrylate: (National Starch and Chemical methacrylic acid terpolymer
Corp.)
ACUSOL™ 842 Ethyl acrylate.methacrylic acid
(Rohm and Haas Co.,
Philadelphia, PA)
ACUMER™ 8100
(Rohm and Haas Co.)
UCAR™ 102, 104, 107 Dinonylphenolethoxylate/
(Union Carbide Corp., TMN adduct, + ethyl acrylate, + Danbury, CT) methacrylic acid polymer (components)
UCAR™ 146 Butyl acrylate + styrene
(Union Carbide Corp.) methacrylic acid polymer (components)
UCAR™ 106 HE Acrylic polymer - (trade secret)
(Union Carbide Corp.)
TAMOL™ 731-D & 850 Acrylic acid polymer
(Rohm and Haas Co.)
MEROPAN™ VD Acetic acid ethenyl ester polymer with oxirane (C4H6O2·C2H4O)x
Suitable cellulase enzymes for use in the novel stonewashing method include any cellulases, including those produced from fungal or bacterial sources that are optimally active in acidic solutions in degrading cellulosic fibers.
Illustrative examples of such acid cellulase enzymes include
CYTOLASE™ and IndiAge™ enzymes (produced by Genencor, Inc.,
South San Francisco, California) and CELLUSOFT™ and DENIMAX™
(produced by Novo Nordisk, Danbury, Conn.) which are derived from a strain of Trichoderma longibrachiatum (formerly T,. reesei). It is to be understood, however, that the invention is not limited to any particular cellulase enzymes or any particular sources for such enzymes, but instead comprehends the use of any enzymes with cellulose degrading activity maximized in an acidic medium, which may be defined as a medium with a pH less than 7.0, but preferably within a pH range of about 4 to about 6.
To achieve the objects of the invention, it is necessary that the dye redeposition or backstaining inhibiting additives be present in the fabric treatment solution in a weight (w/w) concentration not less than about 0.005%. This minimum level may vary depending on the class of additives utilized. For example, the following are representative concentration ranges for the various classes of redeposition preventing additives, based on experimental test results:
Natural/synthetic inorganic silicates: .025 - 5.0% Polyalkyleneoxide polymers: .025 - 2.5%
Polysaccharide polymers: .005 - 5.0%
Acrylic homopolymers and copolymers: .005 - 8.0% It should be stressed that the above weight concentration ranges are based on the total weight of wash liquor in which the fabric is immersed and/or tumbled. The invention is not limited, however, to any specific method, sequence or formulation for adding the essential components of the invention, i.e. the acid cellulase enzymes and anti-redeposition additives to the wash liquor. For example, the enzymes and anti- redeposition additives can first be blended with suitable solvents and other optional ingredients, with the resultant formulation (in liquid, concentrate, gel or other form) being added to the wash water, or the individual components can be separately added in dry or fluid form to the wash water.
The water-based compositions used in the novel method of the invention may include not merely appropriate weight concentrations of acid cellulase enzymes and anti-backstaining additives but also optional additional ingredients such as buffers to maintain the pH of the composition at a fairly stable level, surfactants to increase the wettability of the aqueous solution, promoting the activity of the enzyme in the treated fabric; solvents to help dissolve or disperse the enzymes and surfactants; cellulase activators; antioxidants; solubilizers; and builder components such as divalent sequestering agents. Representative examples of these optional ingredients include the following:
Surfactants - polyethylene oxide polymers, polyproplene oxide polymers, ethylene oxide-propylene oxide block copolymers, ethoxylated C1-18 alkyl phenols and ethoxylated C1-18 aliphatic alcohols.
Solvents - ethylene glycol, propylene glycol, and oligomers and higher polymers of ethylene or propylene glycol in the form of polyethylene or polypropylene glycols, alcohols, terpenes, and aliphatic, aromatic and naphthenic hydrocarbons.
Cellulase enzyme activators - proteins, cobalt and its salts, magnesium and its salts, calcium and its salts, potassium and its salts, sodium and its salts or monosaccharides such as mannose and xylose.
Antioxidants - tert-butylhydroxytoluene, 4,4'- butylidenebis(6-tert-butyl-3-methylphenol), 2,2'-butylidenebis(6- tert-butyl-4-methylphenol), monostyrenated cresol, distyrenated cresol, monostyrenated phenol, distyrenated phenol and 1,1-bis(4- hydroxyphenyl)cyclohexane.
Solubilizers - lower alcohols such as ethanol, benzenesulfonate salts, lower alkylbenzenesulfonate salts such as p-toluenesulfonate salts, glycols such as propylene glycol, acetylbenzenesulfonate salts, acetamides, pyridinedicarboxylic acid amides, benzoate salts and urea.
Builders - organic phosphates, phosphonates, phosphonocarboxylates, amino-polyacetates, polyacrylic acids; non-dissociating polymers such as polyethylene glycol, polyvinyl alcohol and polyvinyl pyrrolidone, and salts of dicarboxylic, diglycolic and sulfonated carboxylic acids, borates, citrates and mixtures thereof.
The enzyme compositions used in the novel methods may be in any conventional form, including liquids, thickened liquids, concentrates, gels or solids. Various such compositions have been disclosed in the prior art and are known to those of skill in the formulation of textile treatment and processing products.
The following are representative examples of water- based compositions according to the present invention for use in the novel method of treating dyed fabric or garments to produce a stonewashed appearance while substantially preventing redeposition of dye onto the treated material. These examples are not intended, however, to limit the invention in any way or to set forth ingredients, materials or concentration ranges which must be used exclusively to practice the invention.
Examples 1-7 define compositions for use in the present invention which contain an acid cellulase enzyme derived from T. longibrachiatum, a buffer comprising 31.2% sodium acetate, 23.3% acetic acid and 45.5% water, the specified dye redeposition preventing additive and water, quantity sufficient to 100% by weight.
Figure imgf000019_0001
EXAMPLE 8 Laboratory testing was performed utilizing the compositions of Examples 1-7 in the wet processing of indigo dyed denim fabric to quantify the anti-backstaining benefit of each additive. The method used to determine changes in antibackstaining characteristics was to measure the Total Color Difference (ΔE) on a HunterLab 0/45 D25-PC2 Colorimeter, available from Hunter Associates Laboratory, Inc., Reston, VA. This instrument reads three opponent-color scales, where L represents black → white (where black=0 and white=100), a represents red → green (where +a = red, and -a = green), and b represents yellow→ blue (where +b = yellow, and -b = blue). ΔE is calculated by the following formula:
ΔE = [(ΔL)2 + (Δa)2 (Δb)2]1/2
Initial and final L,a,b readings are performed at the same location on individual test swatches.
Testing was performed in a Launder-Ometer, available from Atlas Electric Devices Co., Chicago, IL. The Launder-Ometer is an AATCC-approved standard laboratory washing machine which rotates (at 40 ± 2 rpm) up to 20 - 3 in. X 8 in. stainless steel cannisters (1.2 liter capacity) in a thermostatically controlled water bath. Each canister contained 200g. of one test solution of Examples 1-9, one - 4 in. X 4 in. white cotton swatch, one - 4 in. X 4 in. desized 14 oz. indigo denim swatch, and 45 - .25 in. stainless steel balls.
The pH of each test solution was adjusted to 5.0 ± 0.1 units. Each canister was sealed and rotated in the Launder- Ometer at 132 ± 2°F for 60 or 75 minutes. At the conclusion of the test, the fabric swatches were removed and rinsed in a Kenmore (Series 60) home washer at a low water level for a six minute cycle. At the completion of the spin cycle, all test swatches were dried in a conventional domestic dryer. Final L,A,b readings were taken and the Total Color Difference (ΔE) was calculated for the white test swatches. Percent improvement (%I) in ΔE for each test solution in comparison with control solution (the same concentrations of enzyme and buffer without the antibackstaining additives) was calculated as follows:
Figure imgf000021_0001
Using the above described test method, Table A lists percentage improvement values for the various backstaining inhibiting additives used in Examples 1-7.
Figure imgf000021_0002
EXAMPLE 9
Twenty four pounds (24 1b.) of previously desized denim jeans plus a white cotton test swatch were placed in a 125 lb. capacity Milnor open-pocket washer-extractor. The machine was filled with 35 gallons of water and heated to 138ºF (59°C). The specified antibackstaining additive and 21.7 ml. of acid cellulase enzyme per kg. of denim were then added to the washer and tumbled for twenty five minutes. An acetate buffer was also included to control the pH at 5.1 ± 0.1 units. The wash liquor was dumped and the contents of the washer were rinsed at 140°F (60°C) then 110°F (43°C) in 37 gallons of water. The garments and test swatches were then dried and final L,a,b readings were taken. Table B indicates the additive doses and the respective ΔE values.
Figure imgf000022_0001
EXAMPLE 10
Twenty one pounds (21 1b.) of denim jeans plus a white cotton test swatch were placed in an 85 lb. capacity Unimac open- pocket washer-extractor. The machine was filled with 38 gallons of 140ºF (60°C) water containing an amylase enzyme desizing stripper. After 12 minutes, the desizing solution was drained. The machine was filled with 42 gallons of 120°F (49°C) water for a 2 minute rinse. The washer was again filled with 42 gallons of 140ºF (60°C) water. The antibackstaining additive and 18.6 ml. of acid cellulase enzyme per kg. of denim were then added to the washer and tumbled for twenty minutes. An acetate buffer was also included to control the pH to 5.1. The wash liquor was then dumped and the contents of the washer were rinsed three successive times at 120°F (49°C) in 68 gallons of water. The garments and test swatches were then dried and final L,a,b reading were taken. Table C indicates the additive doses and the respective ΔE values.
Figure imgf000023_0001
It has thus been shown that there are provided methods which achieve the various objects of the invention and which are well adapted to meet the conditions of practical use.
As various possible embodiments might be made of the above invention, and as various changes might be made in the embodiments set forth above, it is to be understood that all matters herein described are to be interpreted as illustrative and not in a limiting sense.
What is claimed as new and desired to be protected by Letters Patent is set forth in the following claims.

Claims

1. A method of treating dyed cellulosic fabric, in unsewn form or in the form of a garment or other article composed of sewn fabric, to produce a stonewashed effect in said fabric comprising contacting said fabric with a water-based composition having an acidic pH and including (a) at least one cellulase enzyme having optimum cellulose degrading activity in an acidic medium and (b) a dye redeposition inhibiting additive selected from the group consisting of natural and synthetic inorganic silicates, polyalkylene oxide polymers, acrylic polymers, and natural, synthetic and semisynthetic polysaccharides.
2. A method according to claim 1 wherein said composition comprises from about .025 to about 5.0% by weight of natural or synthetic inorganic silicates.
3. A method according to claim 2 wherein said inorganic silicates are selected from the group consisting of kaolin clays, fullers earth, zeolites, bentonites, smectite clays and hydrated amorphous silicon dioxide.
4. A method according to claim 1 wherein said composition comprises from about .025 to about 2.5% by weight of polyalkylene oxide polymers.
5. A method according to claim 4 wherein said polyalkylene oxide polymers are selected from the group consisting of polyalkylene oxide polyamine copolymers, polyethylene oxides and polyethylene glycols.
6. A method according to claim 1 wherein said composition comprises from about .005 to about 5.0 % by weight of acrylic polymers.
7. A method according to claim 6 wherein said acrylic polymers are selected from the group consisting of homopolymers of acrylic acid or methacylic acid and copolymers of said acids with esters of said acids, polyalkenyl polyether or styrene.
8. A method according to claim 1 wherein said composition comprises from about .005 to about 8.0% by weight of natural, synthetic or semisynthetic polysaccharides.
9. A method according to claim 8 wherein said natural, synthetic or semisynthetic polysaccharides are selected from the group consisting of natural and synthetic gums and thickeners, hydroxylated cellulose materials, gelatin and casein.
10. A method according to claim 9 wherein said gums are selected from the group consisting of xanthan, rhamsan, welan, guar and locust bean gums.
11. A method according to claim 9 wherein said thickeners are selected from the group consisting of alginic acid, sodium alginate and other alginic acid metallic salts.
12. A method according to claim 9 wherein said cellulosic materials are selected from the group consisting of hydroxyethylcellulose, hydroxypropylmethylcellulose and hydroxybutylmethylcellulose.
13. A method according to claim 1 wherein said composition has a pH of about 4 to 6.
14. A method according to claim 1 wherein said enzyme is derived from a strain of Trichoderma longibrachiatum.
15. A method according to claim 1 wherein said composition additionally includes a buffer.
16. A method according to claim 1 wherein said composition additionally includes surfactants, solvents, enzyme activators, antioxidants, solubulizers or builders.
17. A method according to claim 1 wherein said fabric is tumbled or agitated with said composition.
18. A method accoding to claim 17 wherein said fabric is tumbled or agitated in a washing machine, tumbler, converted dryer or dye paddle machine.
19. A method according to claim 1 wherein said fabric is in unsewn form.
20. A method according to claim 1 wherein said fabric is in the form of a garment.
21. A method according to claim 20 wherein said garment is a new garment.
22. A method according to claim 1 wherein said fabric is dyed with a vat dye, a pigment dye, a sulfur dye, or other dye wherein the dye resides primarily on the surface of the fibers of the fabric.
23. A method according to claim 22 wherein said fabric is dyed with indigo dye.
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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997031089A1 (en) * 1996-02-22 1997-08-28 Henkel Kommanditgesellschaft Auf Aktien Solid, virtually waterless preparatios
DE19636531C1 (en) * 1996-09-09 1997-12-11 Henkel Kgaa Stone-wash effect production on cotton fabric using ground glass instead of pumice
WO1998010136A1 (en) * 1996-09-09 1998-03-12 Henkel Kommanditgesellschaft Auf Aktien Process for generating a structure effect on textile fabrics
WO1998017770A1 (en) * 1996-10-18 1998-04-30 Novo Nordisk Biochem North America, Inc. Color clarification methods
DE19738625C1 (en) * 1997-09-04 1999-02-04 Henkel Kgaa Texturising and softening knitwear, especially cotton knitwear to give used look
WO2001057173A1 (en) * 2000-02-04 2001-08-09 Bayer Aktiengesellschaft Two-component system for the production of a stone-wash effect on dyed cotton fabrics or fabrics containing cotton
WO2008071710A1 (en) * 2006-12-15 2008-06-19 Dow Corning Corporation Granular materials for textile treatment
EP2009087A2 (en) 2003-12-10 2008-12-31 SASOL Germany GmbH Process for preventing or minimizing dye redeposition using polyester
WO2010115664A3 (en) * 2009-03-30 2010-12-29 Unilever Nv Fabric conditioning composition and process
WO2013130429A1 (en) * 2012-02-29 2013-09-06 Celanese International Corporation Production of dyed cotton fibers
CN111519455A (en) * 2020-04-17 2020-08-11 广州科丰达新材料科技有限公司 Anti-ballistic and anti-dyeing powder and preparation method thereof
WO2021247339A1 (en) * 2020-06-02 2021-12-09 Dow Global Technologies Llc Aqueous liquid laundry formulation
WO2021247340A1 (en) * 2020-06-02 2021-12-09 Dow Global Technologies Llc Method of making and using an aqueous cotton renewing composition
WO2022106072A1 (en) 2020-11-18 2022-05-27 Aplicacion Y Suministros Textiles, S.A.U. Textile stone washing process

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0642230A (en) * 1992-07-24 1994-02-15 Keiichiro Yamazaki Connecting structure of crosspiece connected article for civil engineering and construction
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CN114775314B (en) * 2022-04-22 2024-08-13 广东职业技术学院 Treatment method for removing reactive dye from fiber fabric

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1990002790A1 (en) * 1988-09-15 1990-03-22 Ecolab Inc. Compositions and methods to vary color density
WO1991019794A1 (en) * 1990-06-14 1991-12-26 Novo Nordisk A/S Activation of polysaccharide hydrolase
WO1993025655A1 (en) * 1992-06-12 1993-12-23 Genencor International, Inc. Enzymatic compositions and methods for producing stonewashed look on indigo-dyed denim fabric
WO1994007983A1 (en) * 1992-09-30 1994-04-14 Genencor International, Inc. Methods for stonewashing fabrics using endoglucanases
EP0634486A1 (en) * 1993-07-12 1995-01-18 Rohm And Haas Company Prevention of dye deposition in fabric finishing processes
EP0665322A2 (en) * 1994-02-01 1995-08-02 Meiji Seika Kaisha Ltd. Dye antiredeposition agent and treatment method for pre-dyed fabrics or garments using this agent

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1990002790A1 (en) * 1988-09-15 1990-03-22 Ecolab Inc. Compositions and methods to vary color density
WO1991019794A1 (en) * 1990-06-14 1991-12-26 Novo Nordisk A/S Activation of polysaccharide hydrolase
WO1993025655A1 (en) * 1992-06-12 1993-12-23 Genencor International, Inc. Enzymatic compositions and methods for producing stonewashed look on indigo-dyed denim fabric
WO1994007983A1 (en) * 1992-09-30 1994-04-14 Genencor International, Inc. Methods for stonewashing fabrics using endoglucanases
EP0634486A1 (en) * 1993-07-12 1995-01-18 Rohm And Haas Company Prevention of dye deposition in fabric finishing processes
EP0665322A2 (en) * 1994-02-01 1995-08-02 Meiji Seika Kaisha Ltd. Dye antiredeposition agent and treatment method for pre-dyed fabrics or garments using this agent

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997031089A1 (en) * 1996-02-22 1997-08-28 Henkel Kommanditgesellschaft Auf Aktien Solid, virtually waterless preparatios
DE19636531C1 (en) * 1996-09-09 1997-12-11 Henkel Kgaa Stone-wash effect production on cotton fabric using ground glass instead of pumice
WO1998010136A1 (en) * 1996-09-09 1998-03-12 Henkel Kommanditgesellschaft Auf Aktien Process for generating a structure effect on textile fabrics
WO1998017770A1 (en) * 1996-10-18 1998-04-30 Novo Nordisk Biochem North America, Inc. Color clarification methods
US5919697A (en) * 1996-10-18 1999-07-06 Novo Nordisk A/S Color clarification methods
DE19738625C1 (en) * 1997-09-04 1999-02-04 Henkel Kgaa Texturising and softening knitwear, especially cotton knitwear to give used look
WO1999011747A1 (en) * 1997-09-04 1999-03-11 Cognis Deutschland Gmbh Wash process for textiles
WO2001057173A1 (en) * 2000-02-04 2001-08-09 Bayer Aktiengesellschaft Two-component system for the production of a stone-wash effect on dyed cotton fabrics or fabrics containing cotton
EP2009087A2 (en) 2003-12-10 2008-12-31 SASOL Germany GmbH Process for preventing or minimizing dye redeposition using polyester
WO2008071710A1 (en) * 2006-12-15 2008-06-19 Dow Corning Corporation Granular materials for textile treatment
US8618039B2 (en) 2006-12-15 2013-12-31 Dow Corning India Granular materials for finishing denim
WO2010115664A3 (en) * 2009-03-30 2010-12-29 Unilever Nv Fabric conditioning composition and process
WO2013130429A1 (en) * 2012-02-29 2013-09-06 Celanese International Corporation Production of dyed cotton fibers
CN111519455A (en) * 2020-04-17 2020-08-11 广州科丰达新材料科技有限公司 Anti-ballistic and anti-dyeing powder and preparation method thereof
WO2021247339A1 (en) * 2020-06-02 2021-12-09 Dow Global Technologies Llc Aqueous liquid laundry formulation
WO2021247340A1 (en) * 2020-06-02 2021-12-09 Dow Global Technologies Llc Method of making and using an aqueous cotton renewing composition
CN115667482A (en) * 2020-06-02 2023-01-31 陶氏环球技术有限责任公司 Aqueous Liquid Laundry Detergent Preparations
CN115667481A (en) * 2020-06-02 2023-01-31 陶氏环球技术有限责任公司 Methods of making and using aqueous cotton refreshing compositions
WO2022106072A1 (en) 2020-11-18 2022-05-27 Aplicacion Y Suministros Textiles, S.A.U. Textile stone washing process

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