CN1439070A - Method for the use of hydrophobic bleadching systems in textile preparation - Google Patents

Method for the use of hydrophobic bleadching systems in textile preparation Download PDF

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Publication number
CN1439070A
CN1439070A CN01804820A CN01804820A CN1439070A CN 1439070 A CN1439070 A CN 1439070A CN 01804820 A CN01804820 A CN 01804820A CN 01804820 A CN01804820 A CN 01804820A CN 1439070 A CN1439070 A CN 1439070A
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fabric
bleaching
bleach
alkyl
activating
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CN1205378C (en
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王季平
诺迪埃·门罗·华盛顿
凯文·戴维·莫
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Procter and Gamble Ltd
Procter and Gamble Co
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Procter and Gamble Ltd
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/10—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen
    • D06L4/15—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen using organic agents
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/10—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen
    • D06L4/13—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen using inorganic agents

Abstract

A method for the treatment of a non-finished textile component is provided. The method comprises the steps of treating a non-finished textile component in an aqueous bleaching solution of hydrogen and a hydrophobic bleach activator or hydrophobic peracid. Preferred bleach activators include the alkanoyloxybenzene sulfonates and in particular noanoyloxybenzene sulfonate. The method provides superior fiber protection and fabric strength benefits versus conventional processing as well as significant savings in both energy and time due to the lower bleaching temperatures.

Description

In the textiles pre-treatment, use the method for hydrophobicity bleach system
The reference of related application
The application requires the priority of the U.S. Provisional Application sequence number 60/182,702 (Attorney Docket No.7961P) of submission on February 15th, 2000 according to 37 U.S.C. § 119 (e).
Technical field
The present invention relates to the application of hydrophobicity bleach system in the textiles pre-treatment, more specifically, relate to the application of crossing acid activation peroxide bleaching system by hydrophobicity activator or hydrophobicity on fiber or the yarn at woven or knitting fabric.
Background of invention
At natural fabric, in the weaving of yarn and the fabric processing, the general requirement has a preliminary treatment or pre-treatment step, is further use, prepares natural material rightly in particular for dyeing and/or the general final stage that needs of commercial load.No matter it is naturally occurring that these fabric treating steps have been removed, or is spinning and weaving impurity and the chromoplast of introducing fiber and/or fabric in the step.
Although textile treatment can comprise many different processing and stage, prevailing comprising: the flame calcination of singing-use, remove fiber loose or that mix from the surface; Destarch-remove sizing agent, for example starch with the enzyme infusion method; Flushing-remove grease, oils, wax and fat by under temperature, contacting with sodium hydroxide solution near boiling; A large amount of NaOH are handled-used to mercerising, together with the stretching, extension of fabric with stretch and increase fibre strength.
Common pre-treatment step in addition comprises blanching step, to eliminate naturally occurring chromoplast.Blanching step provides the even white appearance that the consumer accepted, and the even color basis of dyeing or stamp.Therefore, highly successful blanching step is that the consumption fabric accepted of commercialization is necessary.The routine weaving bleaching of natural fabric has related to the use of hydrogen peroxide.Hydrogen peroxide is because the flexibility of its use promptly can both be used and the feature of environmental protection and being widely accepted in high temperature, rapid bleach method or low temperature, long-time static bleaching.
Although hydrogen peroxide is widely used in textile industry, it is not effective especially bleaching agent.Hydrogen peroxide as supply of commodities is very stable compound, thereby natural fabric is had only slight discoloration.In order to overcome the weakness of poor activity, in business method, except the activation peroxide, also need very high temperature and/or very long bleaching time.That is, generally require temperature to be higher than 95 ℃.In addition, also must use alkali, sulfuric acid, the UV irradiation, hypochlorite or organic activator carry out the activation of peroxide, and wherein alkali is most preferred.These shortcomings have not only caused the extra cost of commercial textile products peroxide bleaching process, and high temperature and/or for a long time contact also caused apparent damage to fiber, and cause weakening of gained yarn and fabric intensity.
In the weaving bleach system, use the trial of organic activator nearly all to end in failure.The common hydrophily bleach-activating that tetraacetyl ethylene diamine or TAED accept extensively when being consumer's laundry bleaching is used for providing effective bleaching under lower wash temperature.TAED has been used for the hydrogen peroxide textile bleaching, particularly to regenerated cellulose, in the bleaching as artificial fibre.Yet, although TAED can use under lower bleaching temperature, verified it fine consumer is tieed up element, do not have benefit as the fibre damage and the fibre strength of artificial fibre.In addition, the low solubility of TAED in water also limited its application in textiles processing.
The hydrophobicity bleach-activating, for example nonanoyl oxygen benzene sulfonic acid sodium salt (NOBS) in consumer's washing agent is used, is used as the Tide  that is with bleaching agent, and NOBS and peroxide source provide the bleaching agent of activation together when the consumer washs clothes.Activated bleaching agent under consumer's family expenses wash conditions can be removed some dirt and stain effectively under cold water temperature.But hydrophobic systems is limited in using in the home washings environment owing to form diacyl peroxide in cleaning solution.Diacyl peroxide makes the natural rubber composition degraded of contact, and therefore, the drainpipe of washing machine, rubber washer etc. have stoped the use of this technology on certain condition.
The stringent condition that adopts in textile bleaching has up to now stoped the successful Application of laundry detergent bleaching technology in textile mills.Really, EP 584,710 discloses the use of activated bleaching method in textile mill applications, and is wherein briefly that the activator of NOBS and a large amount of other kinds and type is open together.Although disclose NOBS, this patent not successfully the using hydrophobic bleaching technology realize acceptable whiteness, the damage of fabric and fiber is minimized.In fact, EP 584,710 describes in detail in order to reach acceptable whiteness, and additional alkaline bleaching is essential, and this will increase the damage to fiber significantly.
Therefore, still need a kind of effective method for treating textile,, compare with conventional textile bleaching method especially for the improvement hydrogen peroxide bleaching method of textile treatment, under reduction bleaching temperature and the condition of time, provide good whiteness, improve the fabric intensity confining force simultaneously.
Summary of the invention
The present invention has satisfied this demand, and the activation hydrogen peroxide bleaching method that wherein provides a kind of usefulness to contain the hydrophobic bleach system is handled the method for textiles.This method comprises the use of hydrogen peroxide and hydrophobicity bleach-activating or hydrophobicity peracid.The use of hydrophobicity bleaching agent provides the good whiteness and the benefit of fabric intensity and fibre damage, promptly keeps fiber, and the intensity of yarn and fabric and minimizing are to the damage of fiber.In addition, method of the present invention can reduce the operating cost of textile bleaching processing by using than much lower bleaching temperature of conventional peroxide bleaching process and the processing time that shortens greatly, particularly during batch processing.
Although be reluctant to arrest in theory, it is believed that hydrophobicity bleaching agent of the present invention provides better fabric and yarn absorbability than conventional peroxide bleaching technology or hydrophily activator, and fiber surface better " wettability ".The hydrophobicity bleach-activating forms active bleaching kind---peracid at fabric face, can be detained the longer time at fabric face.And the hydrophily activator forms peracid in solution, and the fabric solution that must experience a poor efficiency subsequently interacts.Therefore, hydrophobic bleach agent of the present invention provides remarkable bleaching and whiteness, and damage and the intensity reduction with fiber simultaneously minimizes.
According to the first embodiment of the present invention, provide a kind of method of handling non-finished product textiles component.This method comprises the steps: to provide non-finished product textiles component, fiber for example, yarn or fabric; With comprising hydrogen peroxide and hydrophobicity bleaching agent, soak into the textiles component as the water-based bleaching liquid of hydrophobicity activator or preformed hydrophobicity peracid; Make this bleaching liquid contact the sufficiently long time, be at least 70 with bleaching textiles component to CIE whiteness with the textiles component.
Preferably, bleaching liquid comprises hydrogen peroxide and hydrophobicity bleach-activating, and this activator is selected from:
A) the following bleach-activating of general formula:
Figure A0180482000071
Wherein R contains about 5～about 17 carbon atoms, preferably contains the alkyl of about 7～about 11 carbon atoms, and L is a leaving group;
B) the following bleach-activating of general formula:
Figure A0180482000081
Or their mixture, wherein R 1Be the alkyl that contains about 1～about 14 carbon atoms, aryl or alkaryl, R 2Be the alkylidene that contains about 1～about 14 carbon atoms, arlydene or alkarylene, R 5Be H or the alkyl that contains about 1～about 10 carbon atoms, aryl or alkaryl, and L is a leaving group;
C) the following benzo oxazinyl bleach-activating of chemical formula: R wherein 1Be H, alkyl, alkaryl, aryl, aralkyl, R 2, R 3, R 4And R 5Can be to be selected from H, halogen, alkyl, alkenyl, aryl, hydroxyl, alkoxyl, amino, alkyl amino ,-COOR 6With the identical or different substituting group of carbonyl functional group, wherein R 6Be H or alkyl;
D) the following N-acyl caprolactam bleach-activating of chemical formula:
Figure A0180482000083
R wherein 6Be H or the alkyl that contains 1～12 carbon, aryl, alkoxy aromatic yl or alkaryl; And a, b, the alkyloyloxyethyl benzene sulfonate that c and d and chemical formula are following:
Figure A0180482000084
R wherein 1Be the alkyl that contains about 7～11 carbon atoms, M becomes the most preferably suitable CATION of hydrophobicity activator.
In optional embodiments, bleaching liquid also comprises and is selected from wetting agent, chelating agent, stabilizing agent, desizing agent, abrasive cleaner, a kind of composition of washing agent and composition thereof.The concentration range of preferred peroxide and activator is about 1g/L～about 20g/L hydrogen peroxide, and the mol ratio of hydrophobicity bleach-activating and hydrogen peroxide is about 1: 1～1: 50.
At about 20～about 80 ℃, under preferred about 50 ℃～about 80 ℃, the textiles component keeps contacting one suitable period with bleaching textiles component, generally at least about 15 minutes with liquid lime chloride, more generally be about 15 minutes～about 180 minutes, in addition more typical be about 30～about 60 minutes.In preferred operations, it is about 10% that the fabric intensity that the textiles component causes owing to bleaching of the present invention is lower than, more preferably less than about 5%.In other words, it is about 25% that the flowability increase of textiles component is lower than, and shows the obvious fibre damage that improved.
Second embodiment according to the present invention provides the method for the woven product of the non-finished product textiles of a kind of batch processing.The step that this method comprises has: the non-finished product machine fabric that introducing is provided; Woven product are put into comprise the water-based bleaching liquid that hydrogen peroxide and hydrophobicity bleach-activating or preformed hydrophobicity are crossed acid blend, the heating bleaching liquid is to about 20～about 90 ℃, and makes the bleaching liquid contact fabric about 15～about 180 minutes.
Therefore, an object of the present invention is to provide a kind of processing textiles component, fiber for example, the method of yarn and fabric, this method provides good whiteness for textiles, and there is not significantly to reduce fabric intensity and to the potential damage of fiber, these are the problems that run into usually in the pre-treating method of routine.Another object of the present invention provides a kind of method that adopts hydrophobicity bleach-activating or preformed peracid to handle the textiles component together with hydrogen peroxide.These and other purpose of the present invention, feature and advantage will be below detailed description and accompanying Claim in show.
All percentages of the present invention, ratio and ratio, unless otherwise indicated, all in 100% weight.All documents of quoting are incorporated herein by reference.
DESCRIPTION OF THE PREFERRED
The invention provides a kind of good method for treating textile, be used to handle knitting and woven fiber, yarn and fabric.But in commercialization textiles component, yarn for example, fabric, in the manufacturing of clothes etc., the textiles component, as fiber, the suitable pre-treatment of yarn or fabric is further to handle successful key.These treatment steps comprise dyeing, and durable shaping finishing is for example used in stamp and/or textile finishing.Uneven color outward appearance or at the impurity of textile surface has hindered the even utilization of many processing as wax or oil.Existing commercial textile products pre-treating method, textile bleaching method particularly, because infringement to the fiber and the fabric of processing textiles, what essential high temperature interrelated with driving bleaching is expensive, expensive owing to separately destarch, washing and the necessary extra equipment of bleaching treatment step, the environmental pollution that excessive poisonous salt causes in the waste material, and still can not be satisfactory.
The invention provides a kind of saving cost and high performance alternative processed conventionally method.The present invention includes the hydrophobicity bleaching agent, for example activator or peracid and peroxide unite use, to bleach non-finished product textiles component.These hydrophobicity bleaching species are providing remarkable result aspect textiles whiteness and the maintenance fabric intensity.When conventional textile bleaching method need surpass 950 ℃ high temperature reach satisfied, during greater than the whiteness of CIE whiteness coefficient 70, consequently fabric intensity reduces by 15% or more than initial fabric intensity, and fiber degradation 50% or more, method of the present invention provides the gratifying whiteness that surpasses 70CIE whiteness coefficient, fabric intensity is reduced less than about 10% than green strength, be more preferably less than approximately 5%,, thereby provide remarkable fabric intensity confining force most preferably less than about 3%.In addition, method of the present invention provides the degradation of fiber degree to be lower than 25%, more preferably less than 15%, even more preferably less than 10%, and the increase of fibre damage is represented in the increase of degree of degradation.Therefore, use method of the present invention to compare the obvious fibre damage that reduced with the peroxide bleaching technology of routine, the latter causes tangible height degree of degradation under surpassing 95 ℃.Finishing of these unique achievements owing to passing through possible low bleaching temperature and the surface-activity of the inventive method.
In addition, the inventive method is used low bleaching temperature, has significant cost advantage.Particularly, the present invention has saved cost significantly at the energy of batch processing with on the time.Conventional batch processing comprises immerses non-finished product fabric in the bleaching liquid, and the heating bleaching liquid is to the effective temperature that surpasses 95 ℃.For heating so for a large amount of (article), fabric and solution are heated to so high temperature are all taking great amount of investment aspect fund and time.Yet because the present invention can use the reduction process temperature, for example about 50 ℃～about 80 ℃, the energy and time that the present invention needs aspect heating will obviously reduce.
The present invention includes the use of the water-based liquid lime chloride of hydrogen peroxide and the hydrophobicity bleaching species such as hydrophobicity activator or preformed hydrophobicity peracid.Hydrogen peroxide or the concentration of preformed peracid in bleaching liquid of the present invention are about 1～about 20g/L, and more preferably about 1～about 10g/ most preferably is about 1.5～about 5g/L.The mol ratio of hydrophobicity activator of Cai Yonging and peroxide is about 1: 1～about 1: 50 then, more preferably about 1: 2～about 1: 30, and more more preferably about 1: 5～about 1: 20.Simultaneously, the ratio of liquid lime chloride or liquid and fabric quantity is about 5: 1～about 100: 1, more preferably about 5: 1～about 40: 1, most preferably is about 8: 1～about 20: 1.
The combination of hydrogen peroxide and hydrophobicity bleach-activating is particularly useful and preferred, particularly the following chain alkyloyloxyethyl class bleach-activating of general formula: Wherein R be contain about 5～about 17, the alkyl chain of preferred about 7～about 11 carbon atoms, L can be any suitable leaving group basically.Leaving group is any group of being replaced from the bleach-activating, consequently crosses the nucleophillic attack of hydroxide radical anion to bleach-activating.This crosses the formation that hydrolysis causes peroxycarboxylic acid.Generally speaking, the group that becomes suitable leaving group must have the electrophilic effect.It also should form stable entity, to such an extent as to can ignore the speed of back reaction.This was convenient to the nucleophillic attack of hydroxide radical anion.
The L group must have enough activity so that be reflected at (for example wash cycle) generation in the optimum time.But if L is too active, activator will be difficult to stable application in bleaching composition.These characteristics generally parallel with the pKa of leaving group conjugate acid, although the exception of known this convention of existence.Usually, the leaving group that shows this behavior be those its grip acid altogether pKa be about 4～about 13, preferred about 6～about 11,8～about 11 group most preferably from about.The L that is suitable for the object of the invention is selected from: And composition thereof, R wherein 1Be the alkyl that contains about 1～about 14 carbon atoms, aryl or alkaryl, R 3Be the alkyl chain that contains 1～about 8 carbon atoms, R 4Be H or R 3, and Y is H or solubilizing group.
Preferred solubilizing group is-SO 3 -M +,-CO 2 -M +,-SO 4 -M +,-N +(R 3) 4X -And O＜--N (R 3) 3, most preferably-SO 3 -M +With-CO 2-M +, R wherein 3Be the alkyl chain that contains about 1～about 4 carbon atoms, M is for bleach-activating provides deliquescent CATION, and X provides deliquescent anion for bleach-activating.Preferably, M is an alkali metal, the ammonium ion of ammonium or replacement, and wherein sodium and potassium are most preferred, and X is a halogen, hydroxide, dimethyl suflfate or acetate anion.The bleach-activating that should be understood that those band leaving groups but do not contain solubilizing group should be scatter in liquid lime chloride well, to help its dissolving.
Preferred bleach-activating is the compound with above-mentioned general formula, and wherein L is selected from:
Figure A0180482000122
R wherein 3Define as above, Y is-SO 3 -M +Or-CO 2 -M +, wherein the M definition as above.
The most preferred bleach-activating of the present invention is the following chain alkyloyloxyethyl benzene sulfonate of chemical formula: R wherein 1Contain about 7～about 12, preferred about 8～about 11 carbon atoms, M is suitable CATION, alkali metal for example, the ammonium ion of ammonium or replacement, most preferably sodium and potassium.
Highly preferred hydrophobic chain alkyloyloxyethyl benzene sulfonate is selected from nonanoyl oxygen benzene sulfonate, and 3,5,5-trimethyl acetyl oxygen benzene sulfonate, 2-ethyl hexanoyl oxygen benzene sulfonate, decoyl oxygen benzene sulfonate, caprinoyl oxygen benzene sulfonate, dodecane acyl-oxygen benzene sulfonate and composition thereof.
In addition, the present invention can adopt the bleach-activating that acid amides is derived.These activators are compounds that the following acid amides of general formula replaces:
Figure A0180482000131
Or its mixture, wherein R 1Be the alkyl that contains about 1～about 14 carbon atoms, aryl or alkaryl, R 2Be the alkylidene that contains about 1～about 14 carbon atoms, arlydene or alkarylene, R 5Be H or the alkyl that contains about 1～about 10 carbon atoms, aryl or alkaryl, L are leaving groups as defined above.
Preferred bleach-activating is R in the above-mentioned general formula 1For containing the alkyl of about 6～about 12 carbon atoms, R 2Contain about 1～about 8 carbon atoms, and R 5It is the compound of H or methyl.Particularly preferred bleach-activating is R in the above-mentioned general formula 1For containing the alkyl of about 7～about 10 carbon atoms, R 2Contain about 4～about 5 carbon atoms, and L is selected from:
Figure A0180482000132
R wherein 3Define as above, Y is-SO 3 -M +Or-CO 2 -M +, wherein the M definition as above.
Another kind of important bleach-activating provided organic peracid described herein by using hydroxide radical anion that the carbonyl carbon of ring is carried out the ring-opening reaction that nucleophillic attack causes.For example, the ring-opening reaction of this caprolactam activators comprises the attack to the caprolactam cyclocarbonyl of hydrogen peroxide or its anion.Because hydrogen peroxide or its anion preferentially occur in the outer carbonyl of ring to the attack of acyl caprolactam, may need catalyst for obtaining effective open loop fragment.The example of another open loop bleach-activating can be found in the benzo oxazinyl activator.
The chemical formula of this benzo oxazinyl activator compound is: The replacement benzoxazine that comprises following type: R wherein 1Be H, alkyl, alkaryl, aryl, aralkyl, R 2, R 3, R 4And R 5Can be to be selected from H, halogen, alkyl, alkenyl, aryl, hydroxyl, alkoxyl, amino, alkyl amino ,-COOR 6(R wherein 6Be H or alkyl) and the identical or different substituting group of carbonyl functional group.
Preferred benzo oxazinyl activator is:
When using activator, cleaning solution obtains best superficial bleaching performance, and wherein the pH of solution is about 8.5～10.5, and is preferred 9.5～10.5, so that cross the carrying out of hydrolysis.
The present invention can adopt N-acyl caprolactam bleach-activating.The chemical formula of these activators is: R wherein 6Be H or alkyl, aryl, alkoxy aromatic yl or the alkaryl that contains 1～12 carbon atom.As mentioned above, R wherein 6Part contains at least about 6, and the caprolactam activators of preferred 6～about 12 carbon atoms provides the hydrophobicity bleaching, and this method provides nucleophilicity and body dirt cleaning function.
Highly preferred hydrophobicity N-acyl caprolactam is selected from benzoyl caprolactam, caprylyl caprolactam, pelargonyl group caprolactam, capryl caprolactam, endecatylene acyl caprolactam, 3,5,5-trimethyl acetyl base caprolactam and composition thereof.
In addition, can adopt preformed acid substitution peroxide and the activator crossed.Preformed hydrophobicity peracid is preferably selected from percarboxylic acids and salt, and percarbonic acid and salt are crossed imidic acid and salt, permonosulphuric acid and salt, and composition thereof.The example is disclosed in the U.S.P 5,576,282 of Miracle etc.
The general formula of the organic peroxy carboxylic acid that one class is suitable is as follows:
Figure A0180482000151
Wherein R contains the 1～alkylidene of about 22 carbon atoms or the alkylidene of replacement, or the phenylene of phenylene or replacement, and Y is H, halogen, alkyl, aryl ,-C (O) OH or-C (O) OOH.
Being applicable to that organic peracid of the present invention can comprise one or two peroxy, both can be aliphatic, also can be armaticity.When organic percarboxylic acids is aliphatic, the general formula of unsubstituted peracid is:
Figure A0180482000152
Wherein Y can be, for example, and H, CH 3, CH 2Cl, C (O) OH or C (O) OOH; N is 0～20 integer.When organic percarboxylic acids was aromatic series, unsubstituted peracid general formula was:
Figure A0180482000153
Wherein Y can be, for example, and H, alkyl, alkyl halide, halogen, C (O) OH or C (O) OOH.
Can be used for a typical peroxy acid of the present invention and comprise alkyl and aryl peroxy acids, for example:
(i) benzylhydroperoxide and cyclosubstituted benzylhydroperoxide, peroxide-a-naphthoic acid for example, a peroxide phthalic acid (six hydration magnesium salts), and neighbour-carboxyl benzamide is crossed caproic acid (sodium salt);
(ii) aliphatic, the aliphatic of replacement and aralkyl one peroxy acid are for example crossed laurate, perstearic acid, amino caproic acid (NAPCA), the N of crossing of N-nonanoyl, amino caproic acid (SAPA) and the N of crossing of N-(3-octyl group amber one acyl group), N-O-phthalic acylamino-is crossed caproic acid (PAP);
(iii) acyl ammonia peroxy acid is for example crossed butanedioic acid one pelargonamide (NAPSA) or is crossed adipic acid one pelargonamide (NAPAA).
The typical two peroxy acids that can be used for this comprise two peroxy acids of alkyl and the two peroxy acids of aryl, for example:
(iv) 1, the two peroxide dodecanedioic acids of 12-;
(v) 1, the two peroxide azelaic acids of 9-;
(vi) two peroxide brassylic acids; Two peroxide decanedioic acid and two peroxide isophthalic acid;
(vii) two peroxide butane-1 of 2-decyl, 4-diacid;
4, the two benzylhydroperoxide of 4 '-sulfonyl.
These bleaching agents are disclosed in the U.S.P4 of the Hartman that published on November 20th, 1984,483,781, the U.S.P 4 of Burns etc., 634, the european patent application 0,133 of the Banks that on February 20th, 551,1985 published etc., 354, with the U.S.P4 of the Chung that publishes November 1 nineteen eighty-three etc., 412,934.The source also comprises the U.S.P4 that is disclosed in the Burns that published on January 6th, 1987 etc. in detail, and 6-amino in the ninth of the ten Heavenly Stems-6-oxo in 634,551 is crossed caproic acid.Persulfate compounds, OXONE is for example commercially produced by the E.I.DuPont de Nemours of German Wilmington, also can be used as suitable permonosulphuric acid source and is used.
Liquid lime chloride of the present invention can also comprise various auxiliary elements.These auxiliary elements comprise chelating agent, wetting agent, pH controlling agent, bleaching catalyst, stabilizing agent, washing agent and composition thereof.Used wetting agent generally is selected from surfactant, particularly non-ionic surface active agent.When using wetting agent, its content is generally about 0.1～about 10g/L, 0.1～about 5g/L more preferably from about, and most preferably 0.2～about 1g/L embathes liquid.The use of stabilizing agent is for a variety of reasons, comprises buffer capacity, chelating ability, and dispersion force strengthens the performance of surfactant in addition.Stabilizing agent, inorganic still organically all is well-known, is the most widely used and silicate closes organic phosphate, when using stabilizing agent, its content is about 0～about 10g/L, 0.1～about 5g/L more preferably from about, and most preferably from about 0.1～about 3g/L embathes liquid.In the preferred optional embodiment of the present invention, comprise NaOH in the liquid lime chloride, its content is about 0.5～about 20g/L, more preferably from about 1～about 10g/L, most preferably from about 1.5～about 5g/L.
Also can adopt chelating agent, chelating agent can be selected from aminocarboxylate, amino phosphonates do, and fragrant chelating agent of multi-functional replacement and composition thereof, all are all as following definition.
The aminocarboxylate that can be used as optional chelating agent comprises edetate, the N-hydroxyethyl-ethylenediamine triacetate, nitrilotriacetic acid(NTA) salt, ethylenediamine tetraproprionates, triethylenetetraaminehexaacetic acid salt does not contain above the alkyl of about 6 carbon atoms or the phosphonate of alkenyl.
The armaticity chelating agent of multi-functional replacement also can be used for the present composition.U.S.P 3,812,044 referring to the Connor that published on May 21st, 1974 etc.The compound of preferred the type acid form is the dihydroxy disulfobenzene, for example 1, and 2-dihydroxy-3,5-disulfobenzene diethylenetriamines penta acetate and ethanol Diglycocol, alkali metal, ammonium and substituted ammonium salt and composition thereof.
When allow using a small amount of at least total phosphorus, amino phosphonates do also is suitable as the chelating agent of the present composition.
Being used for preferred biodegradable cheating agent of the present invention is ethylenediamine disuccinate (EDDS), and particularly [S, S] isomers is disclosed among the U.S.P 4,704,233 as on November 3rd, 1987 (publication) Hartman and Perkins.
When existing, the consumption of chelating agent is about 0.01～about 10g/L, more preferably from about 0.1～about 5g/L, most preferably from about 0.2～about 2g/L.
Also can adopt bleaching catalyst in the liquid lime chloride of the present invention.A kind of metallic bleaching catalyst is a kind of catalyst system, comprises the transition-metal cation of decision bleach catalyst activity, for example copper, iron, titanium, ruthenium, tungsten, molybdenum, or manganese CATION, weak or do not have an assistant metal CATION of bleach catalyst activity, for example zinc or aluminium cations, with the chelating agent, particularly ethylenediamine tetra-acetic acid of decision catalysis and assistant metal cationic stabilized constant, ethylenediamine tetraacetic (methylene phosphonic acid) and water soluble salt thereof.Such catalyst is disclosed in U.S.P 4,430,243.
The bleaching catalyst of other types comprises and is disclosed in U.S.P 5,246,621 and 5,244,594 manganese basigamy compound.The preferred embodiment of these catalyst comprises Mn IV 2(u-O) 3(1,4,7-trimethyl-1,4,7-7-triazacyclononane) 2-(PF 6) 2(" MnTACN "), Mn III 2(u-O) 1(u-OAc) 2(1,4,7-trimethyl-1,4,7-7-triazacyclononane) 2-(ClO 4) 2, Mn IV 4(u-O) 6(1,4, the 7-7-triazacyclononane) 4-(ClO 4) 4, Mn IIIMn IV 4(u-O) 1(u-OAc) 2-(1,4,7-trimethyl-1,4,7-7-triazacyclononane) 2-(ClO 4) 3And composition thereof.Also referring to European patent application publication No. 549,272.Be applicable to that other ligands of the present invention comprise 1,5,9-trimethyl-1,5, the 9-triazododecane, the 2-methyl isophthalic acid, 4, the 7-7-triazacyclononane, the 2-methyl isophthalic acid, 4, the 7-7-triazacyclononane, and composition thereof.The example of other suitable bleaching catalysts is referring to U.S.P 4,246,612 herein, and U.S.P 5,227, and 084 and the WO95/34628 in December 21 nineteen ninety-five, the latter relates to the specific type of iron catalyst.
Also referring to U.S.P 5,194,416, this patent disclosure monokaryon manganese (IV) complex, Mn (1,4,7-trimethyl-1,4,7-7-triazacyclononane) (OCH for example 3) 3-(PF 6).
Also have a class bleaching catalyst, be disclosed in U.S.P 5,114,606, be manganese (II), (III) and/or (IV) and contain the water-soluble complexes of the non-carboxylate polyol part of at least three consecutive C-OH bases.Preferred part comprises D-sorbite, iditol, galactitol (dulsitol), mannitol, xylitol, arabitol, adonitol, meso-erythrite, meso-inositol, lactose, and compound.
U.S.P 5,114, and 611 disclose another kind of useful bleaching catalyst, comprise the complex of transition metal and non-(greatly) ring part, and described transition metal comprises Mn, Co, Fe or Cu.Preferred part comprises pyridine, pyridazine, pyrimidine, pyrazine, imidazoles, pyrazoles and triazole ring.Randomly, this ring can be substituted base, alkyl for example, and aryl, alkoxyl, halogen and nitro replace.Particularly preferably be 2,2 '-two pyridine amine ligands.Preferred bleaching catalyst comprises Co-, Cu-, Mn-or Fe-two pyridine methane and two pyridine amine complexes.Highly preferred catalyst comprises Co (2,2 '-two pyridine amine) Cl 2, two (isothiocyanato) two pyridine amine-Co (II), three couples of pyridine amine-Co (II) perchlorate, Co (2,2-two pyridine amine) 2O 2ClO 4, two-(2,2 '-two pyridine amine) Cu (II) perchlorate, three (two-2-pyridine amine) Fe (II) perchlorate, and composition thereof.
Other bleaching catalyst example comprises managanese gluconate, Mn (CF 3SO 3) 2, Co (NH 3) 5The binuclear complex that Cl and Mn and four-N-tooth and two-N-tooth part form comprises N 4Mn III(u-O) 2Mn IVN 4)+and [two pyridines 2Mn III(u-O) 2Mn IVTwo pyridines 2]-(ClO 4) 3
Be used for particularly preferred Mn catalyst of the present invention and be those full disclosures in WO 98/23249, WO 98/39098, the Mn catalyst of WO 98/39406 and WO 98/39405, and its disclosure is incorporated herein by reference.
Other bleaching catalysts are disclosed in, for example, and European patent application publication No. 408,131 (cobalt complex catalyst), European patent application publication No. 384,503 and 306,089 (catalysis of metalloporphyrin agent), U.S.4,728,455 (manganese/multidentate ligand catalyst), U.S.4,711,748 and European patent application publication No. 224,952 (alumino-silicate absorption Mn catalyst), U.S.4,601,845 (alumino-silicates that manganese and zinc or magnesium salts support), U.S.4,626,373 (manganese/ligand catalysts), U.S.4,119,557 (ferric iron composition catalysts), German patent specification 2,054,019 (cobalt chelating agent catalyst), Canada 866,191 (containing transition metal salt), U.S.4,430,243 (with the chelating agent of manganese CATION and on-catalytic metal cation), and U.S.4,728,455 (managanese gluconate catalyst).
Preferred following cobalt (III) catalyst of chemical formula:
Co[(NH 3) nM ' mB ' bT ' tQ qP p] Y yWherein cobalt is in+3 oxidation state; N is 0～5 integer (preferred 4 or 5; Most preferably 5); M ' represents monodentate ligand; M is 0～5 integer (preferred 1 or 2; Most preferably 1); B ' represents bidentate ligand; B is 0～2 integer; T ' represents tridentate ligand; T is 0 or 1; Q is a tetradentate ligands; Q is 0 or 1; P is five tooth parts; P is 0 or 1; And n+m+2b+3t+4q+5p=6; Y is that the quantity of one or more appropriate selections is the counter anion of y, and wherein y is 1～3 integer (preferred 2～3; When Y is-1 valency anion, most preferably 2), to obtain charge balance salt, preferred Y is selected from chloride, nitrate, and nitrite, sulfate, citrate, acetate, carbonate, and composition thereof; And wherein also to have a coordination site that contacts with cobalt at least be to be unsettled under the automatic bowl service condition, and all the other coordination sites make cobalt stable under the automatic bowl condition, thus make cobalt (III) to the reduction potential of cobalt (II) under alkali condition with respect to standard hydrogen electrode less than about 0.4 volt (preferably less than about 0.2 volt).Some preferred catalyst are that chemical formula is [Co (NH 3) 5Cl] Y y, [Co (NH particularly 3) 5Cl] Cl 2Chloride salt.
Composition more preferably of the present invention, said composition utilize the following cobalt of chemical formula (III) bleaching catalyst:
[Co (NH 3) n(M) m(B) b] T yWherein cobalt is in+3 oxidation state; N is 4 or 5 (preferred 5); M is one or more parts that pass through a site and cobalt coordination; M is 0,1 or 2 (preferred 1); B is the part by two sites and cobalt coordination; B is 0 or 1 (preferred 0), and when b=0, m+n=6, when b=1, m=0, n=4; T is that the quantity of one or more appropriate selections is the counter anion of y, and to obtain charge balance salt, wherein y is that (preferred y is 1～3 to integer; When Y is-1 valency anion, most preferably 2); And wherein the basic hydrolysis speed constant of this catalyst less than 0.23M -1s -1(25 ℃).These raw materials more completely are disclosed in U.S.P 5,559, and 261,5,597,936,5,705,464,5,703,030 and 5,962,386, its disclosure is incorporated herein by reference.
As a kind of practical ways, but not be confined to this, can regulate solution of the present invention and to aqueous medium, contain 100,000,000/a active bleaching catalyst species at least, and about 0.01ppm～about 25ppm will be contained in the preferred liquid, more preferably from about 0.05ppm～about 10ppm, most preferably from about the bleaching catalyst species of 0.1ppm～about 5ppm.
Any known organic bleaching catalyst, oxygen-transfer agent or its precursor also can be used for the present invention, comprise compound itself and/or its precursor, for example any suitable being used to produces the ketone of bisoxirane, and/or any analog that contains heteroatomic bisoxirane precursor or bisoxirane, for example sulfo group imines R 1R 2C=NSO 2R 3, referring to EP 446 982 A of publication in 1991, and sulfonyloxaziridines, for example: EP 446,981 A referring to publication in 1991.The preferred embodiment of this raw material comprises hydrophily or hydrophobicity ketone, particularly generates bisoxirane on the spot with a peroxysulphate logotype, and/or U.S.5,576,282 and institute's quoted passage offer in disclosed imines.The oxygen bleaching method preferably with this oxygen-transfer agent or precursor logotype, comprise percarboxylic acids and salt thereof, percarbonic acid and salt thereof, permonosulphuric acid and salt thereof, and composition thereof.Also referring to U.S.5,360,568, U.S.5,360,569 and U.S.5,370,826.In highly preferred embodiment, the present invention relates to a kind of detergent compositions, said composition combines with transition metal bleach catalyst of the present invention with such as organic bleaching catalyst of a kind of compound of above-mentioned appointment.
The inventive method comprises provides a kind of non-finished product textiles component, puts into described liquid lime chloride.This textiles component can comprise fiber, and yarn and fabric comprise woven fabric, non-woven fabric and knitted fabric.Non-finished product textiles component is meant also not dyeing, stamp or enter material such as the final step of durable shaping finishing.Certainly, those of ordinary skill in the art knows that textiles component of the present invention is that those also do not comprise the processed material of cutting and sewing through clothes or other.
This method can be used for most of arbitrary natural materials, comprise fibrinous, for example cottonizing, the cellulose of flax and regeneration, for example artificial fibre and Lu Saier (lyocell).100% natural fabric, yarn and fabric, or and the melange of synthetic material can be used.For purposes of the present invention, natural fabric can comprise cellulose described herein, pure and the wool that mixes, silk, sisal hemp, flax and jute.
Method of the present invention can comprise further singes, destarch, and flushing and mercerising are handled, together with bleaching step together.These steps can be carried out with different combinations and order, and those of ordinary skill in the art will know that various combinations all are possible.Destarch step of the present invention comprises removes sizing agent, starch that for example adds and polyvinyl alcohol in spinning process.The destarch step comprises uses the amylase aqueous solution and general wetting agent, soaks or the sufficiently long time of contact fabric with enzyme solutions, to remove sizing agent.
Rinsing step of the present invention comprises the natural or synthetic impurity of removing, for example wax and oil from textiles.Rinsing step comprises the use of aqueous base solution, is generally the NaOH under the high temperature.Optional member in the alkali lye comprises wetting agent and chelating agent.
Mercerising treatment step of the present invention comprises applying high density alkali, and NaOH for example together with the stretching, extension of fabric with stretch and recover fibre strength and improve gloss, is singed simultaneously---with textiles by naked light to remove loose fibres or thread.Destarch, flushing, mercerising is handled and singed is that those skilled in the art are well-known, is that the technical staff knows and in its skill.
Certain method of the present invention is included in the inventive method washing or a series of washing step afterwards in preferred application scheme.The textiles of carrying out washing treatment is well-known, and in technical staff's skill.When existing, the washing stage,, carry out after flushing and the mercerising treatment step, equally also after blanching step of the present invention generally in each destarch.In addition, when there being bleaching, destarch when flushing or mercerising treatment step, in preferred embodiments, can comprise that one soaks or pre-wetting step, with guarantee the textiles component evenly or the humidity of homogeneous.
The inventive method provides excellent wetting capacity for the textiles component that adopts this method to handle.The wettability of textiles is all very important to any dyeing and the arrangement of textiles.Wettability causes dyestuff or the finishing agent good permeability to textiles, and produces good dyeing and/or arrangement result.Therefore, the wettability of textiles is an index of processing method validity.Wettability is high more, and promptly wetting time is short more, represents effective and good more processing method.Verified, conventional textiles hydrogen peroxide bleaching method is only just having qualified wetting distribution above under 95 ℃ the temperature, and low temperature (70 ℃) bleaching causes wetting distribution to surpass about 40%.But, use method of the present invention, then the increase of wetting property of the fabric index is lower than approximately 10%, and preferably less than about 5%, its wettability index is defined as follows:
[(70 ℃ degree of wettings)-(95 ℃ degree of wettings)]/(95 ℃ degree of wettings) * 100%.
For purposes of the present invention, degradation of fiber or damage are the mobilities measured based on AATCC method of testing 82-1996, and this method comprises the dispersion of fiber in cupri ethylene diamine (CP).The increase of fibre damage quantity is represented in the increase of mobility between fiber of handling and the untreatment fiber.The method that is adopted outlines as follows.The representative sample of 1.5mm fiber sheared and be dissolved among the CP in the sample bottle that has several glass marbles, CP measures as equation CP=120 * example weight * 0.98 qualification, is placed under the nitrogen.Shook this bottle about 2 hours.Press equation CP=80 * example weight * 0.98 and add additional C P, shook under the nitrogen subsequently 3 hours.After waiting to dissolve, solution is placed under constant agitation, to prevent the separation of dispersion.In 25 ℃ thermostatic bath, measure the delivery time of solution then with the Oswald Canon Fenske viscosimeter of proofreading and correct.Delivery time is by being drawn onto fluid 2 mark between the ball, and measures the marked flows of liquid meniscus between two balls and spend below the lower ball the required time of mark and determine.What adopt is the mean value of twice time.Calculate mobility according to formula F=100/ctd then, c=viscometer constant wherein, t=delivery time, and d=solution density 1.052.
Following non-limiting example has further been illustrated the present invention.Embodiment 1
The present invention's bleaching and pretreated method can be implemented according to following mode.This method can be carried out on dyeing instrument in the automatic laboratory that has the infrared heating system (Labmat) that Mathis Co. makes.Prepare bleaching liquid in the deionized water by descending the chemicals of listing in the tabulation 1 to join.Addition sequence is as follows: wetting agent-chelating agent-activator-H 2O 2-NaOH-fabric.Fabric is destarch 122g/m that clean, plain weave 2100% heavy kissuto.The whiteness of original fabrics is CIE32.58.Be under 15: 1 the situation, fabric to be put into solution in liquid/fabric ratio.In about 10 minutes, solution is heated to required bleaching temperature each hurdle of table 1 from about 20 ℃,, is cooled to room temperature then temperature required maintenance 50 minutes.From bleaching liquid, pull fabric out, and with hot water and the thorough laundering of textile fabrics of warm water, to guarantee no longer including residual alkali in the fabric.Fabric is dry and arrangement under 70 and 65% relative humidity, to carry out wetting and whiteness is measured.The Miniscan XE Plus that uses HunterLab to make measures CIE whiteness coefficient.Use Instron to estimate fibre strength by following ASTM D 5035 methods.Wetting property of the fabric is measured with AATCC method of testing 79-1995.Wetting time is short more, and wettability of fabrics or absorbability are good more.
Table 1
A ?B ?C ?D
Temperature (℃) 70 ?70 ?70 ?95
?NaOH(g/l) 3.5 ?3.5 ?3.5 ?3.5
?H 2O 2(g/l) 2 ?2 ?2 ?2
Activator Do not have Hydrophobicity 1 Hydrophobicity 2 Do not have
Mol ratio (activator/H 2O 2) - ?1∶10 ?1∶10 ?-
Stabilizing agent (g/l) - ?- ?- ?-
Wetting agent 3(g/l) 0.7 ?0.7 ?0.7 ?0.7
Chelating agent 4(g/l) 0.3 ?0.3 ?0.3 ?0.3
Time (minute) 50 ?50 ?50 ?50
Liquid/fabric ratio 15∶1 ?15∶1 ?15∶1 ?15∶1
Wettability (second) 1.92 ?1.42 ?1.47 ?1.34
The CIE whiteness 64.4 ?73.7 ?68.5 ?75.8
Fabric intensity (newton) 232.1 ?248.6 ?220.2 ?211.6
Intensity reduces (%) 7.5 ?0.9 ?12.2 ?15.3
1Nonanoyl oxygen benzene sulfonic acid sodium salt, NOBS.
2Tetra acetyl ethylene diamine, TAED.
3The Silvatrol SL of Ciba Geigy.
4The Invatek DTPA-41 of Ciba Geigy.

Claims (10)

1. the method for non-finished product textiles component pre-treatment, it is characterized in that following steps: provide non-finished product textiles component, described textiles component use liquid lime chloride is soaked into, this liquid lime chloride is a feature with hydrogen peroxide and hydrophobicity bleaching agent, allow this liquid lime chloride keep contacting the sufficiently long time with described textiles component, with bleaching textiles component, the whiteness value of wherein resulting treated textiles component is at least 70 CIE coefficients, or the increase of fiber degradation degree is less than 25%.
2. the process of claim 1 wherein that described liquid lime chloride is characterised in that hydrogen peroxide and hydrophobicity bleach-activating, this activator is selected from:
A) the following bleach-activating of general formula:
Figure A0180482000021
Wherein R is the alkyl that contains 5～17 carbon atoms, and L is a leaving group;
B) the following bleach-activating of general formula: Or its mixture, wherein R 1Be the alkyl that contains 1～14 carbon atom, aryl or alkaryl, R 2Be the alkylidene that contains 1～14 carbon atom, arlydene or alkarylene, R 5Be H or the alkyl that contains 1～10 carbon atom, aryl or alkaryl, and L is a leaving group;
C) the following benzo oxazinyl bleach-activating of chemical formula: R wherein 1Be H, alkyl, alkaryl, aryl, aralkyl, R 2, R 3, R 4And R 5Can be to be selected from H, halogen, alkyl, alkenyl, aryl, hydroxyl, alkoxyl, amino, alkyl amino ,-COOR 6With the identical or different substituting group of carbonyl functional group, wherein R 6Be H or alkyl;
D) the following N-acyl caprolactam bleach-activating of chemical formula: R wherein 6Be H or the alkyl that contains 1～12 carbon atom, aryl, alkoxy aromatic yl or alkaryl; And
E) a, b, the mixture of c and d.
3. each method among the claim 1-2, the reduction of the fabric intensity of wherein said textiles component in described method is lower than 10%.
4. each method among the claim 1-3, the increase of the textiles component fibers degree of degradation of wherein said processing is lower than 25%.
5. the woven textile fabric method of pre-treatment in batch is characterized in that following steps:
A) provide the non-finished product machine woven fabric of introducing;
B) with described fabric process water-based liquid lime chloride, described liquid lime chloride is a feature with the mixture of hydrogen peroxide and hydrophobicity bleach-activating or preformed hydrophobicity activator, described liquid lime chloride is heated to 90 ℃ from 20 ℃, and makes described liquid lime chloride contact fabric 15～180 minutes.
6. a matrix is characterized in that the collection of the textiles component of non-finished product bleaching, and the whiteness value of wherein said matrix is greater than the 70CIE coefficient, and the reduction of fabric intensity is lower than 10%.
7. each matrix among the claim 1-6, the increase of the textiles component fibers degree of degradation of wherein said processing is lower than 25%.
8. each matrix among the claim 1-5, the wettability index of wherein said matrix is less than 10%.
9. one kind is improved the method that textiles component wettability is lost, and it is characterized in that following steps:
A) provide the non-finished product machine woven fabric of introducing;
B) with described fabric process water-based liquid lime chloride, this liquid lime chloride is a feature with the mixture of hydrogen peroxide and hydrophobicity bleach-activating or preformed hydrophobicity activator, described liquid lime chloride is heated to 90 ℃ from 20 ℃, and makes described liquid lime chloride contact fabric 15～180 minutes.
10. each method among the claim 1-9, the whiteness value of the textiles component of the wherein said processing that obtains is greater than the 70CIE coefficient.
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CN1302095C (en) * 2001-06-29 2007-02-28 宝洁公司 Stability enhanced hydrophobic peracid bleaching systems for textile applications and methods for using same
CN102844491A (en) * 2010-03-26 2012-12-26 丹尼斯科美国公司 Treatment of keratinous fibers with an enzyme having perhydrolase activity
CN107109771A (en) * 2014-04-24 2017-08-29 Cthr.拜特利希有限公司 Method for brightening dyed fabric
CN107419511A (en) * 2017-09-11 2017-12-01 广东溢达纺织有限公司 The method for bleaching and textile product of textile material
CN110042647A (en) * 2019-04-02 2019-07-23 嘉兴学院 A kind of high whiteness cold bleaching method of cashmere or wool
CN112482014A (en) * 2020-12-04 2021-03-12 东华大学 Room-temperature bleaching method for cashmere loose fibers

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EP0584710A3 (en) * 1992-08-22 1995-02-01 Hoechst Ag Method for the bleaching of textiles.
ATE170552T1 (en) * 1993-05-20 1998-09-15 Procter & Gamble BLEACHING METHODS USING PEROXY ACID ACTIVATORS ALONG WITH ENZYMES
WO1995021283A1 (en) * 1994-02-07 1995-08-10 Warwick International Group Limited Process for bleaching textiles

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1302095C (en) * 2001-06-29 2007-02-28 宝洁公司 Stability enhanced hydrophobic peracid bleaching systems for textile applications and methods for using same
CN102844491A (en) * 2010-03-26 2012-12-26 丹尼斯科美国公司 Treatment of keratinous fibers with an enzyme having perhydrolase activity
CN102844491B (en) * 2010-03-26 2016-03-09 丹尼斯科美国公司 Use the ferment treatment cutin fiber with perhydrolase activity
CN107109771A (en) * 2014-04-24 2017-08-29 Cthr.拜特利希有限公司 Method for brightening dyed fabric
CN107109771B (en) * 2014-04-24 2020-04-21 Cthr.拜特利希有限公司 Method for whitening dyed fabrics
CN107419511A (en) * 2017-09-11 2017-12-01 广东溢达纺织有限公司 The method for bleaching and textile product of textile material
CN110042647A (en) * 2019-04-02 2019-07-23 嘉兴学院 A kind of high whiteness cold bleaching method of cashmere or wool
CN110042647B (en) * 2019-04-02 2022-02-18 嘉兴学院 High-whiteness low-temperature bleaching method for cashmere or wool
CN112482014A (en) * 2020-12-04 2021-03-12 东华大学 Room-temperature bleaching method for cashmere loose fibers

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