CN1420953A - Method for oxidising or activating textile mass with gas mixture contg. ozone - Google Patents
Method for oxidising or activating textile mass with gas mixture contg. ozone Download PDFInfo
- Publication number
- CN1420953A CN1420953A CN 01807495 CN01807495A CN1420953A CN 1420953 A CN1420953 A CN 1420953A CN 01807495 CN01807495 CN 01807495 CN 01807495 A CN01807495 A CN 01807495A CN 1420953 A CN1420953 A CN 1420953A
- Authority
- CN
- China
- Prior art keywords
- ozone
- wool
- fiber
- gas
- oxidation
- Prior art date
- Legal status (The legal status 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 status listed.)
- Granted
Links
Images
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
-
- 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
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/34—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxygen, ozone or ozonides
Abstract
The invention concerns a method for oxidising a textile mass, in particular woollen, to modify the surface of the fibres whereof it is formed, essentially consisting in: a) transforming said textile mass into a textile mass containing 12.5 to 60 % (g/g) of water and having a structure such that a gas can pass through it uniformly and thoroughly; and b) passing through said mass, for 5 to 20 minutes at room temperature, a gas mixture containing 20 to 150 g of ozone per m<3>, which is continuously injected through said mass while it moves along on a carrier system, being alternately directed on both surfaces of said pass. Said treatment is preferably carried out in a sealed chamber, the ozone being destroyed in output.
Description
Technical field
Present invention relates in general to the oxidation processes of fibrous matter (fibrous mass), this fibrous matter is any fibrous matter that can form the net form formula that gas can evenly fully see through.
The fibrous matter here means and comes from animal, plant or synthetic any fibrous matter.
The oxidation processes of special concern textile fabric, particularly protein fibre more, and more particularly, the oxidation processes of sensu lato wool (sheep's wool, goats hair, alpaca fibre etc.).
More accurately, the present invention relates to for example oxidation processes of the fibrous matter of above definition, particularly pollution-free and nondestructive processing, be used to give their special performances, for example concerning wool, felting performance not, and concerning the wool fiber different with other, for example, the ability of shrinkage or fixed dye not.
Background technology
Owing to more specifically relate to wool, should be understood that following content.
Wool fibre is a kind of animal sources fiber, and it contains 97% protein.On the morphology, this fiber is cylindrical, and for the length of 20-150 millimeter, its diameter changes in the 15-40 micrometer range.This fiber contains two distinct parts: be known as the fibrillar center of cortex and cover the scale of this cortex.These scales are generically and collectively referred to as epidermis.Scale is fixed on the cortex by adhesive, but only the cover scales leaf length 2/3.As a result, the end of fiber is a free end and can the napping according to the state of fiber (raise).When the humidity of fiber changes and is in the motion, this napping phenomenon takes place, thereby fiber and other fiber are collided.Because this moment, scale separated from cortex, so scuffing takes place, this phenomenon becomes irreversible because of scale is closed.This phenomenon is commonly referred to as " felting ".
Felting is the major defect in the wool maintenance.In fact, as early explain that felting is relevant with the motion and their moisture of fiber.The reason why Here it is must very wash wool product carefully.Ad hoc proposal is to its hand washing and shakeout drying, and this is quite binding, and has limited for example exploitation of clothes of woolen that needs frequent washing to a certain extent.
Therefore, very since Chang period, possible when people need to wash always, prevent the processing of wool felting at least to a great extent, and, constantly popularize the not processing of felting in the time of need machine-washing to wool along with what washing machine used recently.
For other application, particularly for the dyeing wool, also need the processing of some synergy.
Scale is the pith of wool, because it is the position of numerous chemical reactions, these chemical reactions occur in the processing wool and for example dye, add in the process of auxiliary agent (for example, bactericide), waterproofing agent or felt proofing resin.
In addition, the combing wool has a kind of color and luster naturally, and this color and luster changes between the brass in white according to its quality.Use different bleaching agents in woolen industry, the major part in these bleaching agents is the derivative of chlorine, because their waste liquid toxicity, their use more and more is restricted.
For efficient or duration that reduces these processing or the expense that increases these processing, can increase the reactivity of wool scale.For example, mention two kinds of processing widely using in the woolen industry possibly.
First example relates to dyestuff.In order to obtain required color, need wool is placed dye bath, this dye bath will be heated to boiling temperature so that open the hole of scale, along with carry out in hour a period of time, dye diffusion will be arrived in the scale.Any processing that can make scale obtain modification will help dyeing.
In addition, many machine-washable processing of wool that are intended to make have been proposed.The most effective processing that can obtain " Machine Washable " authentication is to apply wool fibre with resin, and this has prevented the wool felting effectively.In this processing, the initial oxidation wool scale need be made before resin may be fixed.The whole bag of tricks all uses the chemical type oxidant that mainly is based on chlorine.These products cause pollution, and this will finally cause them disabled.
Why Here it is helps the reason of the fixing alternative method of resin always in research.The some of them method is to substitute chlorine with the oxidant that pollutes still less, for example uses permanganate, persulfate or hydrogen peroxide.Other method is intended to by the thickness that reduces scale or removes the use that scale replaces resin fully from fiber.These methods also need through the oxidation pre-treatment fiber, are the processing of carrying out with protease subsequently, and purpose is to remove or destroy fully scale.
A kind of method in back can obtain smooth fibre, and it is felting but also than natural fabric or thinner with the fiber of other method processing, this is a kind of commercial advantage not only.
It seems that now the view of setting up is, preliminary treatment before possible Protease Treatment is especially through the preliminary treatment of oxidation, see in quality and economically, all be the fiber that obtains good quality, be the ready necessary processing of the processing of carrying out subsequently, described subsequent treatment is in particular for making its Machine Washable and/or making it can meet the existing subsequent treatment that requires dyeing.
So, as previously mentioned, the oxidation processes that proposes comprises those processing of not using chlorinated compound at present, can cause pollution.
According to the present invention, use ozone to finish the idea of oxidation processes by serendipitous.
The someone proposed use ozone and made animal fiber on some occasion past, and for example particularly wool can not contract.
Therefore, U.S. Pat-A-4189303 discloses a kind of shrinkproof method of protein animal fiber sill that makes.This method is, in pH neutral and under about 20-30 ℃ condition, makes these materials contact about 2-6 minute with the ozone water solution that contains about 1-20mg/l ozone.
The description of the Prior Art summary of U.S. Pat-A-4189303 has also been commented on 3 patents formerly, i.e. patent GB-A-242027, US-A-3149906 and US-A-3404942.
Patent GB-A-242027 proposes to flood wool number minute with 5% ammonia solution, with from wherein extracting excess liq, and is exposed under wet condition in the ozone-containing air of 1/1000 concentration.
According to patent US-A-3149906, the airflow blow of ozone and vapour composition is passed through pending textiles.The content of ozone is about 10-50mg/l in this air-flow.This processing was carried out 1-10 minute under about 60-95 ℃ temperature.
According to patent US-A-3404942, under 80-170 ℃ temperature, heat a side of moistening protein fabric, air-flow ozoniferous flows through on offside simultaneously.
Among other document, publish Journal in Textile Research, the 35th (7) volume, nineteen sixty-five, the paper of 638-647 page or leaf has been described the use of ozone/oxygen mixture, is used at room temperature handling wet wool fabric.In the document, the people may be expected, how described laboratory scale treatment conversion is become plant-scale processing, to be used for efficiently handling large-sized fibrous matter without any enlightenment.
In these are handled, as if commercial development is not carried out in any processing, to obtain not felting wool, even still less handle and be intended to obtain the Machine Washable wool, the chances are for this because disappointed result causes the researcher to explore other channel rather than comprise the pretreated ozone treatment channel that is used for finishing the wool fibre scale.
Summary of the invention
Have now found that,, might under the condition of determining, finish preliminary treatment, in this preliminary treatment, replace the contaminative oxidant of use so far with the oxidation mixture that contains regulation ratio ozone in order to obtain the wool fibre that quality is good, be easy to accept subsequent treatment.
According to one aspect of the present invention, the present invention relates to a kind of method of oxidized fibre material, this method is used for the surface that modification constitutes the fiber of this material, and described method mainly comprises:
A) described fibrous matter is changed into a kind of 12.5-60% of containing (g/g) water and have the fibrous matter that can make all even structure of passing through fully of gas; With
B) at room temperature, penetrated described material 5-20 minute with every cubic metre of admixture of gas that contains 20-150g ozone, this admixture of gas be in the process that this material is advanced with delivery system by continuous injection by described material, and alternately towards two surfaces of described material.
The meaning that statement " being used for the surface that modification constitutes the fiber of this material " is got in this manual is to handle to be limited in the surface basically, and does not influence the core of fiber.
Described modification specifically means, allows or helps subsequent treatment, and for example particularly, dyeing or enzyme are handled.In some cases, the fibrous matter special performances can also be directly given in these modifications, for example, in the presence of water, without undergoing high temperature and/or strong agitation or bleaching the time, gives not felting performance (not shrinking) of wool.
By changing machined parameters (the particularly ozone concentration in moisture, processing duration and the admixture of gas) according to the inventive method, might change fiber given type, so as to need reactive or, respectively, obtain required concrete quality.Can determine relevant parameters by preliminary test.
The meaning that statement " make gas can be evenly and the structure that therefrom sees through fully " is got in this manual is that a kind of making passed the structure that wherein gas and all fibers contacted and skimmed over their all surface.Fiber " net " is usually corresponding to this definition.
" room temperature " means the temperature of 15-30 ℃ of scope.
Used admixture of gas can be every cubic metre of any admixture of gas that contains 20-150 gram ozone, exists one or more to fiber, particularly other gas of having no adverse effects of its core.Usually, this mixture preferably is made up of with the mixture of oxygen formation ozone and oxygen or air.
Fibrous matter method for oxidation of the present invention carries out continuously.More accurately, when fibrous matter was advanced on delivery system, continuously injection was by the fibrous matter of step a) with admixture of gas ozoniferous, and this delivery system is specially porous belts or perforated cylinder, and injection is alternately towards two surfaces of this material.
According to one preferred embodiment, fibrous matter is continuously the form of net, constant thickness on its whole width and length.
Because the waste discharge of a large amount of ozone generating can be polluted in atmosphere, in an especially preferred embodiment, in closed chamber, finish method of the present invention, and, the ozone that the oxidation reaction of decomposition fibrous matter does not consume before the remaining gas in exhaust mixture.
In the international patent application (PCT) of the exercise question of submitting to simultaneously with the applicant's name, described and to be used for the dissimilar reactor that particularly preferred this embodiment of the inventive method uses for " handling the reactor of solid material and the device that comprises this reactor with pernicious gas or admixture of gas ".
Below describe the favourable operation principle of sealed reactor, it is used for handling fibrous matter according to the present invention with admixture of gas ozoniferous.
Carry out interchange between admixture of gas and the fibrous matter by the material in gas being passed move.Application countercurrent action and multiple-effect principle can reduce the ozone concentration in the admixture of gas, thereby reduce its concentration in reactor inlet place leakage thing.
In order to do like this, import this admixture of gas in the exit of fibrous matter, and by making admixture of gas pass through chambers, wherein ozone concentration is exhausted.Therefore, ozone concentration reduces in each process chamber, and is tending towards 0 in the porch of reactor.
For example, reaction hood is separated into cell, obtains the tightness of cell by using roller.Import admixture of gas in the fibrous matter exit, it passes the fibrous matter in moving, then along entering next process chamber in the other direction.The depleted admixture of gas of ozone is extracted in porch at fibrous matter.
In order to prevent that fibrous matter is subjected to carrying secretly of air-flow, it is clamped between two perforated conveyor belts (being respectively upper conveyor belt and lower conveyor belt).This two porous belts have limited fibrous matter moving on porous carrier, cause to help the pressure that admixture of gas evenly diffuses through this fibrous matter and fall.
According to a variant scheme, in reactor, with guaranteeing the multistage replacement multicell that fibrous matter is reversed based on same principle.Unimpeded (purge) of input and output locking system can be controlled by probe, and this probe is reacted to the existence of the ozone that surpasses 1 ppm critical value.
Provided the schematic diagram of reactor in accompanying drawing 2 and 3, will be described them in the back, these reactors can be advantageously used in implements the method for oxidation that usefulness of the present invention admixture of gas ozoniferous carries out.
Method of the present invention is particularly useful for the oxidation wool, as the described embodiment 1 to 12 of following experimental section and illustrational by contrast accompanying drawing 8-13 institute.
Embodiment 1 shows that the wool that stands ozone oxidation processing of the present invention has more sensitiveness than chlorinating wool to enzyme hydrolysis.
In this scope, particularly, owing to can easily the ozone of not oxidized consumption be changed into oxygen again by the simple heating processing,, particularly use the processing of chlorine or its compound so method of the present invention can advantageously substitute the existing oxidation processes that pollution is arranged.
In addition, the oxygen bearing gas mixture that is flowed out can recycling after passing through ozone generator simply.
Embodiment 2 shows, by the relative water capacity of regulating the wool fibre material when the ozone treatment, can regulate the efficient of the subsequent treatment that use protease carries out.
Embodiment 3 shows that ozone treatment can reduce the average diameter of wool fibre, that is to say, has improved their fineness, simultaneously, after enzyme hydrolysis, gives its enough not felting performance with acquisition " Machine Washable " label, and need be by means of applying resin.
Embodiment 4 shows that for the identical processing duration, when the concentration of ozone in the admixture of gas increased, fibre fineness increased while felting tendency and reduces.
Embodiment 5 shows that ozone treatment itself can improve the whiteness of wool.
Embodiment 6 shows that for making wool concerning the sensitization that applies resin, the ozone preliminary treatment is handled with chlorine and compared at least equally effectively.Therefore, can be used for by applying production of resins Machine Washable wool according to method of the present invention highly beneficially.
Embodiment 7 shows, carries out enzyme hydrolysis after the ozone treatment and has satisfied the harshest requirement, has for example obtained significant no felting performance.
Embodiment 8-12 carries out under pilot-scale, and its reative cell is 1.5 meters long and 30 centimetres wide, these experiment confirms the wool fineness that obtains among other embodiment and the result of felting aspect of performance not.
Accompanying drawing is described
Fig. 1 is the schematic diagram of the ozone treatment equipment chain of use in following examples 1 to 5 and 7.
Oxygen is fed the ozone generator of using 10 ℃ of constant temperature of water management.The ozone/oxygen mixture that is produced is transported to the bottom of closed reactor, in this reactor, grid is set, on this grid, place pending netted wool fibre.Admixture of gas passes this net from the bottom to top-direction, and flows to the valve direction, and the gas flow rate that ozone detector is led in this valve restriction is 1 liter/minute, and admixture of gas is among the framework of ozone-depleting measurement amount in the reactor.The total stream of admixture of gas that leaves reactor is transported in the ozone pyrolysis apparatus.From the gas of ozone decomposer output is oxygen, it can be discharged into the atmosphere or be recycled in the ozone generator and utilize.
Accompanying drawing 2 is roughly represented the reactor of the oxidation processes of the wool of washing being carried out by the mixture of oxygen (or air) and ozone, and at the environment that obtains under the Machine Washable wool situation.
With conveyer belt wool is transported in the reactor, and enters closed chamber, pass the roller of the roller press of guaranteeing the oxidizing chamber tightness then.In oxidizing chamber, two expanded metal rotary drums are with opposite direction rotation.Admixture of gas is introduced into oxidizing chamber and is extracted device and extracts out, and the admission of withdrawal device is positioned at the inside of rotary drum.Therefore, produced pressure and fallen, this pressure falls forcing admixture of gas to exert an influence by wool layer, simultaneously wool layer is pressed against on the rotary drum.Exist the fact of two rotary drums might increase contact time.Can be to obtain the tightness of reactor exit with the same mode in Reactor inlet place.According to the listed variant scheme of sketch, can utilize to make wool drop into system's output wool that processing is bathed, for example, use the processing of protease to bathe, guarantee tightness by the bath barrier that is arranged in wool whereabouts passage.
Closed chamber is connected with air blast, and this air blast function makes the superpressure of pressure in the relative oxidizing chamber of the indoor generation of sealing.
Be sent to the ozone thermal decomposer from oxidizing chamber and closed chamber escaping gas.
Accompanying drawing 3 shows variant and the environment thereof that Fig. 2 reactor is simplified.According to this variant, rotor system is replaced by conveyer belt with holes.
The reactor of Fig. 2 and Fig. 3 is as mentioned below has guaranteed environmental protection.
By behind the hot ozone decomposer, the admixture of gas that passes wool is discharged in the atmosphere.
The ozone concentration of the air in the continuous measurement closed chamber.When its value of reaching capacity, air is blown into this chamber, make ozone be transported in the ozone decomposer.
For the fiber and the raw fiber of chlorinating wool fibre, ozone treatment, carry out enzyme according to embodiment 1 and handle, accompanying drawing 4 show supernatant in the absorbance of 280 nanometers as in minute variation of the function of hydrolysis duration.
Accompanying drawing 5 shows with the wool fibre of ozone treatment, and relative humidity is respectively 50% and 12.5% o'clock, carries out supernatant that enzyme the handles absorbance when 280 nanometers according to embodiment 2 and changes.
The continuous processing chain of the machine-washable hand washed wool of hand washed wool represented to be used to make in Fig. 6 summary, and this processing is to carry out enzyme hydrolysis after ozone oxidation of the present invention.
This processing chain mainly comprises:
-apparatus for feeding
-oxidation reactor
-arrangement treatment facility
Apparatus for feeding is connected with the Barrate type extension apparatus, and this extension apparatus is transformed into the hand washed wool of bulk on the net of suitable thickness.
The reactor that summary is represented among Fig. 6 can specifically be Fig. 2 or Fig. 3, the type among preferred Fig. 3.
The wool of oxidation like this is carried out enzyme handles, then, after the washing with its drying, carded, combing and place on the spool.
The machine-washable treatment facility chain of combing wool represented to make in accompanying drawing 7 summarys, carries out enzyme hydrolysis after ozone oxidation of the present invention.
The principle of this processing chain is identical with the situation of Fig. 6, and difference is that apparatus for feeding comprises and can make ribbon by arriving the device in the extender system, and its function is to roll ribbon, makes it be fed to reactor with thin net form formula.Before ribbon enters extender system, may be to the ribbon humidification.
The Fig. 6 that describes and the processing chain of Fig. 7 in order to clarify the item of handling about the wool Machine Washable can be applicable to " arrangement " processing after other fiber and other are arranged in ozone treatment easily, and for example, dyeing replaces with dye bath to hydrolysis bath.
Fig. 8 is 2000 times of enlarged photographs of untreated raw material sheep wool fibre.
Fig. 9 is with the 2000 times enlarged photographs of GC 897 subtilopeptidase As with the raw material sheep wool fibre of 200 μ l/l processing.
Figure 10 is 2000 times of enlarged photographs that contain the Oxygen Flow of 100 gram ozone with 15 minutes the sheep wool fibre of flow velocity processing of 2l/min with every cubic metre.
Figure 11 handled 15 minutes with the flow velocity of 2l/min with every cubic metre of Oxygen Flow that contain 100 gram ozone, then with 2000 times of enlarged photographs of the sheep wool fibre of the GC 897 subtilopeptidase As processing of 200 μ l/l.
Figure 12 is 2000 times of enlarged photographs of the sheep wool fibre handled with 2% chlorine.
Figure 13 handles with 2% chlorine, then with 2000 times of enlarged photographs of the sheep wool fibre of the GC 897 subtilopeptidase As processing of 200 μ l/l.
Do not observe significant different to Fig. 8 with 9 photo.This result shows, uses the enzyme of GC 897 subtilopeptidase As to handle (borate buffer solution that 200 μ l GC 897,1 liters, pH value 9.5/0.25M/55 ℃/5 minutes) poor efficiency or invalid separately.
The photo of Figure 10 and Figure 12 shows respectively, ozone treatment (100 gram/rice
3, 2 liters/minute, 15 minutes) and, corroded fiber surface with the chloridized that 2% chlorine carries out, make the edge of the fibrocortex still less salient angle that becomes obviously.
The photo of Figure 13 shows that carry out chloridized with 2% chlorine and use enzyme hydrolysis (borate buffer solution that the GC of 200 μ l/l is 897,1 liters, pH value 9.5/0.25M/55 ℃/5 minutes) partly to destroy structure subsequently: the fragment of fiber begins to drop from cortex.
The photo of Figure 11 shows with ozone treatment of the present invention (100 gram/rice
3, 2 liters/minute, 15 minutes), follow general type with the fiber of enzyme hydrolysis (borate buffer solution that the GC of 200 μ l/l is 897,1 liters, pH value 9.5/0.25M/55 ℃/5 minutes) acquisition.The fiber that is obtained is very smooth, has not both had scale also not have the sign that damages.
Experimental section Embodiment 1: strengthen the sensitiveness that wool corrodes enzyme
This embodiment explanation is by the necessity of oxidation pre-treatment fiber, so that they corrode sensitivity to enzyme.
3 batches of fibers to following acquisition carry out the enzyme erosion:
1. chlorinating fiber
Sheep wool fibre 300 grams of combing, carded are imported in the acetate buffer of 6 liters of 0.1M/pH 4, and 20 ℃ of insulations 5 minutes.Add the Basolant DC (chlorocyanurate with 62-64% active chlorine) of 4%v/v, it is sold by BASF AG, then said preparation is incubated 45 minutes at 20 ℃.By the free radical of 0.3% (w/v) sodium pyrosulfite in 20 ℃ of reduction neutralization formation in 15 minutes.Wash fiber sample with distilled water, manual dehydration and drying at room temperature 24 hours.
2. use the fiber of ozone treatment
Ozat-IA with the manufacturing of Ozonia company
TMOzone generator is made ozone by the pure oxygen that surpasses 90%.The manufacturing speed of this equipment approximately be 80 the gram ozone/hour, that is, productivity ratio is 6% (g/g).Ozone this accurate concentration in oxygen is to use ultraviolet photometer in 254 nanometers, measures with BMT 963 in-line analyzers of Ozonia company manufacturing.
10.05 ± 0.05 gram dry sheep wools are immersed in 1 liter of distilled water, may contain hydrogen peroxide and/or NaOH.After the dehydration, fiber is placed on the grid of the reactor shown in accompanying drawing 1 schematic diagram for example.
Make this contain 100g/m
3The oxygen based gas mixtures of ozone passes grid, continues 15 minutes.
3. raw fiber (sheep wool)
According to Aust.J.Biol.Sci.25,1225-1234 (1972), Peters D.E., BradburyJ.H. rules that propose the works " trypsase is from fiber and cortical cell digesting material " (Material digest bytrypsin from fibres and cortical cells), finish enzyme to fiber 1., 2. and 3. erosion.(relative humidity: 12.5%) 1., 2. or 3. introduce respectively in 100 milliliters of borate buffer solutions, this solution is 0.25M/pH 9.0 with the dried fiber of 10.05 ± 0.05 grams at 60 ℃.In pre-incubation after 5 minutes, with the BACTOSOL WO of 140 μ l (CLARIAN , Ref.2900098) and the GC 897 (GENECOR ) of 10 μ l introduce in the reactant mixture.On different time interval points, 2 milliliters the reaction supernatant of taking a sample, and be introduced in the haemocylolysis pipe that contains 0.5 milliliter of 0.1M HCl to interrupt reaction.The content process screening of pipe (the AITCHROMATO cellulose acetate filter, diameter: 13 millimeters, porosity: 0.22 μ m), and in the absorbance of 280 nanometers with PERKIN ELMER LAMBDA spectrophotometer measurement filter liquor.
During the absorbance of 280 nanometers is enzyme hydrolysis, the function of the quantity of the peptide that wool salts out.This value is high more, and wool is responsive more to enzyme hydrolysis.
3 kinds of fiber samples accept this hydrolysis and obtain the results are summarized in following table I.
Table I
| The absorbance of 280 nanometers supernatants | |||
| Time (minute) | The chlorination fiber | The ozonisation fiber | Raw fiber |
| ????0 | ????0.063 | ????0.041 | ????0 |
| ????1/6 | ????0.218 | ????0.18 | ????0 |
| ????1/3 | ????0.289 | ????0.25 | ????0.005 |
| ????1/2 | ????0.338 | ????- | ????0.008 |
| ????2/3 | ????0.379 | ????0.392 | ????0.01 |
| ????5/6 | ????0.416 | ????- | ????0.015 |
| ????1 | ????0.452 | ????0.446 | ????0.019 |
| ????2 | ????0.569 | ????0.526 | ????0.042 |
| ????3 | ????0.649 | ????0.588 | ????0.0745 |
| ????4 | ????0.726 | ????0.639 | ????0.096 |
| ????5 | ????0.781 | ????0.684 | ????0.121 |
These results represent that with the curve form of Fig. 4 this figure shows that concerning each fiber sample, supernatant is functions of hydrolysis duration in the absorbance variation of 280 nanometers.
Present embodiment has been given prominence to such fact, and the wool of ozonisation has the sensitiveness to enzyme hydrolysis that can compare with the chlorination wool, and on the contrary, in fact the wool of not accepting oxidation pre-treatment does not have sensitiveness.
Embodiment 2: water capacity corrodes the influence of handling sensitization efficient to the enzyme of wool fibre
The relative humidity of two kinds of samples of sheep wool fibre is separately fixed at 12.5% and 50%.These samples are introduced the ozonation chamber of using among the embodiment 1 and accepted identical ozonation treatment (100g/m
3Ozone, continues 15 minutes by 2 liters/minute).Determine the sensitiveness that each sample corrodes enzyme according to the technology of describing among the embodiment 1.
What obtain the results are summarized in following Table II.
Table II
| The absorbance of 280 nanometers supernatants | ||
| Time (minute) | Ozonisation fiber (relative humidity=50%) | Ozonisation fiber (relative humidity=12.50%) |
| ????0 | ??0.041 | ??0 |
| ????1/6 | ??0.18 | ??0 |
| ????1/3 | ??0.25 | ??0 |
| ????1/2 | ??- | ??0.004 |
| ????2/3 | ??0.392 | ??0 |
| ????5/6 | ??- | ??0.01 |
| ????1 | ??0.446 | ??0.014 |
| ????2 | ??0.526 | ??- |
| ????3 | ??0.588 | ??0.04 |
| ????4 | ??0.639 | ??0.086 |
| ????5 | ??0.684 | ??0.092 |
These results represent that with the curve form of Fig. 5 this figure shows that concerning each fiber sample, supernatant is functions of hydrolysis duration in the absorbance variation of 280 nanometers.
Present embodiment has been given prominence to such fact, and the efficient that the protease sensitization is handled depends on the relative water capacity of fiber when carrying out oxidation pre-treatment with ozone.Its demonstration, preferably relative humidity be 50% but not 12.5% time the operation.
Embodiment 3: ozone is to fibre diameter and its felting Effect on Performance
In causing research work framework of the present invention, developed a kind of analytical method, this makes the reactive enhancing of evaluation wool become possibility.The method is, after the ozone oxidation preliminary treatment of wool, makes wool accept the hydrolysis of protein hydrolysate, measures the fineness of fiber and the felting performance of fiber then.
With moisture is that 50% carded sheep wool sample, 10.00 ± 0.05 grams are placed on the reactor used grid of embodiment 1.To pass this wool by every cubic metre of air-flow (2 liters/minute) that contains the admixture of gas formed of oxygen of 30 gram ozone.Carry out 4 experiments, change each ozone preliminary treatment duration (0-20 minute).
In the 2nd step, allow all samples accept enzyme and handle (borate buffer solution that the GC of 200 μ l/l is 897,1 liters, 9.0/0.25M/55 ℃ of pH value).Measure the variation of the felting performance and the fibre fineness (average diameter) of each sample respectively according to IWTO 20-69 and IWTO12-95 standard.
What obtain the results are summarized in following Table III.
Table III
| Ozone-depleting (mg/g wool) | Fineness (μ m) (IWTO 12-95) | Density (the g/cm of ball 3) ???(IWTO?20-69) | |
| Blank | ????0 | ????21.4 | ????0.192 |
| 5 minutes | ????4.2 | ????21.4 | ????0.125 |
| 14 minutes | ????12 | ????20.8 | ????0.053 |
| 20 minutes | ????26 | ????20.3 | ????0.053 |
This table shows that ozone treatment may reduce the average diameter (increase fineness) of fiber and reduce their felting performance (density of ball).
Embodiment 4:
Repeat the experiment of embodiment 3, but, use every cubic metre of admixture of gas that contains 100 ozone for ozone treatment.
What obtain the results are summarized in following Table IV.
Table IV
| Ozone-depleting (mg/g wool) | Fineness (μ m) (IWTO 12-95) | Density (the g/cm of ball 3) ?(IWTO?20-69) | |
| Blank | ????0 | ????21.4 | ????0.192 |
| 5 minutes | ????24 | ????20.8 | ????0.057 |
| 14 minutes | ????46 | ????18.4 | Do not detect |
| 20 minutes | ????60 | ????17.5 | Do not detect |
This table shows, for the given ozone treatment duration, the minimizing amplitude of average fibre diameter and felting performance increases as the function of ozone concentration in the admixture of gas.
Embodiment 5: bleach wool with ozone treatment
With every cubic metre of mixture that contains 30 and 100 gram oxygen of ozone and ozone 10.00 ± 0.05 gram wool samples are carried out handling in 10 minutes respectively, the flow velocity of this mixture is 2 liters/minute.
Then, handle these samples with protease (borate buffer solution that the GC of 200 μ l/l is 897,1 liters, pH value 9/0.25M, 55 ℃), or do not handle.
To every kind of situation, measure the whiteness of the wool of handling with the MICROCOLOR reflectometer.Express according to IWTO 35 methods, and represent whiteness with letter w.The value of W is low more, and wool is white more.
What obtain the results are summarized in following table V.
Table V
| Test | W (whiteness) | |
| Raw fiber | ????E1 | ????49.4 |
| Ozone fiber 30 | ????E2 | ????44.4 |
| Ozone fiber 100 | ????E3 | ????44.7 |
| Ozone fiber 30+ enzyme | ????E4 | ????44.5 |
| Ozone fiber 100+ enzyme | ????E5 | ????42.6 |
This table can illustrate that ozone treatment has improved the whiteness of wool fibre.
Improvement in test E2 to the E4 situation is similarly, and the improvement of test E5 is obviously more.
Embodiment 6: make the use sensitization of wool fibre to resin by the ozone preliminary treatment
In the present embodiment, the sample of being tested is accepted using of resin by the Hercosett 125LX resin of contaminating the manufacturing of HERCULES company.This resin is the polyamide of handling with the cation form chloropharin, and this alcohol is with respect to responding property of fiber.
Select this resin to be because in the dip-dye processing after chlorination, it can be used as wool anti-felting finish agent.Developing it is for resin is obviously reduced the influence of halogenated organic compounds content in the effluent.These given the test agent are as follows:
1.-40 the ribbon blank test material (raw fiber) of gram combing sheep wool, this wool is the wool fibre of 20 gram/rice, and average fineness is 21.5 μ m.
2.-40 restrain what is called of the present invention " ozone treatment " material, it is 4 part of 10 form (processing of 10 gram wools: flow velocity was 2 liters/minute in 15 minutes, every cubic metre of oxygen that contains 100 gram ozone) that restrains every part;
3.-75 the so-called " Cl of gram
2Handle " material, be the fiber band (2% chlorination) of combing sheep wool.
The general condition of using resin is as follows:
25 gram wools are placed in the dyeing pot of AHIBA TURBOMAT laboratory system, and this dyeing pot contains the Hercosett 125LX solution of 0.5 liter of 6 grams per liter, and its pH value obtains this pH value by adding 28% ammonia between 7.8 and 8.2.At 30 ℃ this bath was applied to wool 45 minutes.
Then, pad each part ribbon (45 kg/cm) twice, in 85 ℃ hot-air dry 15 minutes then.Then, by sample is exposed to 110 ℃ following 4 minutes, make resin generation polymerization.
After arrangement processing, each sample restrains with the hand carding number, and 1 gram combing sample is carried out the reactivity test of fiber to dyestuff Bleu Lanasol 3R, and this dyestuff is equivalent to ProcionM3 indigo plant.
This test at present is used to measure and applies the uniformity of Hercosett 125LX to carrying out the pretreated wool of chlorination.
Measure two numerical value L in this test
*And b
*, they are colorimetric parameters, its can express dyestuff Bleu lanasol 3R on dye efficient.Therefore, their Hercosett 125LX resins of the people can being measured can absorb this tone applies efficient.
b
*Corresponding Huang-blue degree component, and L
*The transparency of corresponding given the test agent.
Therefore, b
*Numerical value low more, sample is just blue more.
In addition, transparency L
*Numerical value low more, then the intensity of this color is just high more.
Particularly, it is effective more that given the test agent is applied resin, then corresponding b
*And L
*Numerical value is low more.
What obtain the results are summarized in following Table VI.
Table VI
| Sample | ????L * | ????b * |
| Raw fiber | ????75.71 | ????-3.38 |
| ???Cl 2Handle fiber | ????60.17 | ????-11.79 |
| ???O 3Handle fiber | ????54.62 | ????-16.61 |
| Raw fiber-Hercosett | ????64.35 | ????13.28 |
| ???Cl 2Handle fiber-Hercosett | ????36.75 | ????-25.53 |
| ???O 3Handle fiber-Hercosett | ????32.56 | ????-27.32 |
This table can show, with the sample of chlorine or ozone oxidation, its blue cast the darkest.
For the wool of also using resin treatment with chlorine or ozone, its depth of shade further is reinforced.
The most blue sample is the sample of putting in order with Hercosett 125LX after the ozone preliminary treatment.
Conclusion is, according to the wool of ozone method for pretreating oxidation also to resin for example Hercosett 125LX affinity is arranged, and even higher than the affinity of chloride oxidation wool.
Embodiment 7: the knitted fabric that makes for the wool fibre that carries out enzyme hydrolysis with ozone treatment then, Make its generation " Machine Washable " quality
In the framework of European standard, be applied on the footwear textiles according to the most violent contraction greatest limit of IWS TM31 test determination.Under this situation, connect 5 5A week after dates a 7A cycle, the contraction of surface area must be no more than 8%.Therefore, this shrinkage factor value correspondence boundary that must not surmount.
Test two 100cm
2The knitted fabric sample.First is finished with untreated sheep wool fibre.Second is with ozone treatment (100 gram ozone/rice
3, 2 liters/minute, 15 minutes) finish with the sheep wool fibre of enzyme GC 897 processing (200 μ l/l borate buffer solutions, 9.1/55 ℃/1 liter of 0.25M/pH value) then.
After a 7A connects 5 5A washing cycles and divides drying washing cycle, measure the change in size of these samples.Obtain a result by the area percentage of contraction that calculates the tricot de laine of being investigated.
The total shrinkage that during off-test the sample of untreatment fiber is drawn is 80%.Under the same conditions, the shrinkage that the sample of handling fiber with ozone treatment and process enzyme hydrolysis is drawn only is 4%.This result can compare with the result that obtains under the chlorination fiber situation fully.Therefore, these fibers of handling according to the present invention possess " Machine Washable " quality.Can require " machine washing " label of wool sign with the goods of these fiber manufacturings.
Embodiment 8:
With wool diameter is that 21.7 μ m and metric system weight (metric weight) are that 3 ribbons of combing wools of 48 grams are immersed in the water, and dehydration makes their contained moisture reduce to 40% then.These ribbons are extended 5.6 times machinery by making their.Make gained wool net pass through reactor, this contact time of corresponding 5 minutes with the speed of 0.3m/min.
The admixture of gas of oxygen and ozone is fed in the reactor, and its ozone concentration is 112g/m
3, and flow velocity is 3.5m
3/ h.
Dry from reactor output wool and carry out above-mentioned enzyme and handle.What obtain the results are summarized in following Table VII.
Table VII
Embodiment 9:
| Sample | Production capacity kilogram/hour (kg/h) | Fineness (μ m) (IWTO 12-95) | Density (the g/cm of ball 3) ??(IWTO?20-69) | Surface shrinkage (IWS TM 31) |
| The combing wool | ??21.7 | ???0.183 | ??60％ | |
| The ozonisation wool | ??0.4 | ??21.4 | Do not detect | Do not detect |
| Proteoclastic ozonisation wool | ??20.3 | Do not detect | ??1.9％ |
With wool diameter is that 22.1 μ m and metric system weight are that 3 ribbons of combing wools of 55 grams are by making 1.22 times machinery of their elongations.Gained wool net is immersed in the water, and being dewatered to water capacity then is 40%.Make its speed with 0.15m/min pass through reactor, this is equivalent to 10 minutes contact time.
The admixture of gas of oxygen and ozone is fed in the reactor, and its ozone concentration is 112g/m
3, and flow velocity is 1.75m
3/ h.
Dry from reactor output wool and carry out above-mentioned enzyme and handle.What obtain the results are summarized in following table VIII.
Table VIII
Embodiment 10:
| Sample | Production capacity kg/h | Fineness (μ m) (IWTO 12-95) | Density (the g/cm of ball 3) ??(IWTO?20-69) |
| The combing wool | ??22.1 | ??0.192 | |
| Proteoclastic ozonisation wool | ????0.95 | ??21.5 | Do not detect |
With wool diameter is that 22.1 μ m and metric system weight are that 3 ribbons of combing wools of 55 grams are by making 1.22 times machinery of their elongations.Gained wool net is immersed in the water, and being dewatered to water capacity then is 40%.Make its speed with 0.15m/min pass through reactor, this is equivalent to 10 minutes contact time.
The admixture of gas of oxygen and ozone is fed in the reactor, and its ozone concentration is 112g/m
3, and flow velocity is 3.5m
3/ h.
Dry from reactor output wool and carry out above-mentioned enzyme and handle.What obtain the results are summarized in following table IX.
Table I X
Embodiment 11:
| Sample | Production capacity kg/h | Fineness (μ m) (IWTO 12-95) | Density (the g/cm of ball 3) ??(IWTO?20-69) |
| The combing wool | ???22.1 | ??0.192 | |
| Proteoclastic ozonisation wool | ????0.95 | ???21.5 | Do not detect |
3 ribbons of combing wools that with wool diameter 22.1 μ m and metric system weight are 55 grams are by making the machinery of 1.22 times of their elongations.Gained wool net is immersed in the water, and being dewatered to water capacity then is 40%.Make its speed with 0.3m/min pass through reactor, this is equivalent to 5 minutes contact time.
The admixture of gas of oxygen and ozone is fed in the reactor, and the ozone concentration of mixture is 112g/m
3, and flow velocity is 3.5m
3/ h.
Dry from reactor output wool and carry out above-mentioned enzyme and handle.What obtain the results are summarized in following table X.
Table X
Embodiment 12:
| Sample | Production capacity kg/h | Fineness (μ m) (IWTO 12-95) | Density (the g/cm of ball 3) ??(IWTO?20-69) |
| The combing wool | ????22.1 | ??0.192 | |
| Proteoclastic ozonisation wool | ????1.9 | ????21.6 | Do not detect |
With wool diameter is that 22.1 μ m and metric system weight are that 3 ribbons of combing wools of 55 grams are by making 1.22 times machinery of their elongations.Gained wool net is immersed in the water, and being dewatered to water capacity then is 40%.Make its speed with 0.15m/min pass through reactor, this is equivalent to 10 minutes contact time.
The admixture of gas of oxygen and ozone is fed in the reactor, and the ozone concentration of mixture is 112g/m
3, and flow velocity is 1.05m
3/ h.
Dry from reactor output wool and carry out above-mentioned enzyme and handle.What obtain the results are summarized in following table XI.
Table X I
| Sample | Production capacity kg/h | Fineness (μ m) (IWTO 12-95) | Ball density (g/cm 3) ??(IWTO?20-69) |
| The combing wool | ??22.1 | ??0.192 | |
| Proteoclastic ozonisation wool | ????0.9 | ??21.7 | Do not detect |
Claims (13)
1. the method for oxidation of fibrous matter is used for the surface that modification constitutes its fiber, and described method mainly comprises:
A) described fibrous matter being transformed into a kind of 12.5-60%g/g of containing water and having can make gas evenly and the fibrous matter of the structure that fully sees through; With
B) at room temperature, make every cubic metre of admixture of gas that contains 20-150g ozone by described material 5-20 minute, described admixture of gas be in the process that this material is advanced with delivery system by continuous injection by described material, and alternately towards two surfaces of described material.
2. the method for claim 1 is characterized in that described fibrous matter is the textile fabric material, preferred protein fiber, more preferably wool fibre.
3. claim 1 or 2 method is characterized in that described admixture of gas by ozone and oxygen or air, preferably form with the mixture of oxygen.
4. the method for any one in the claim 1 to 3 is characterized in that described delivery system comprises conveyer belt or a plurality of perforated cylinder.
5. the method for any one in the claim 1 to 4 is characterized in that implementing this method in closed chamber, but also is, before the remaining gas in this mixture of discharging, decomposing the fibrous matter oxidation reaction does not have used up ozone.
6. the method for any one in the claim 1 to 5, it is characterized in that fibrous matter relatively this admixture of gas adverse current advance.
7. be used for implementing the reactor of any one method of claim 1 to 6, it is characterized in that this reactor is according to adverse current and the operation of multiple-effect principle.
8. reducing the method for wool fibre average diameter, it is characterized in that described method comprises a step according to the described fiber of any one method oxidation in the claim 1 to 6, is the step of handling with proteolytic enzyme subsequently.
9. the method for not destroying the wool fibre cortex and polishing wool fibre is characterized in that described method comprises the step according to the described fiber of any one method oxidation in the claim 1 to 6, is the step of handling with proteolytic enzyme subsequently.
10. the method that brightens of wool fibre is characterized in that described method comprises the step according to the described fiber of any one method oxidation in the claim 1 to 6, may be the step of handling with proteolytic enzyme subsequently.
11. increase wool fibre to the resin that applies or reactive method of dyestuff, it is characterized in that described method comprises the step according to the described fiber of any one method oxidation in the claim 1 to 6.
12. the method for " Machine Washable " type of acquisition wool fibre is characterized in that described method comprises the step according to the described fiber of any one method oxidation in the claim 1 to 6, is the step of handling with proteolytic enzyme subsequently.
13. be used for implementing claim 8 to 10 and the preparation of 12 any one method or fiber and the processing chain of subsequent treatment, it is characterized in that, it mainly comprises the equipment of reactor, the system that is used for subsequent treatment, washing equipment, drying equipment and these fibers of packing of the oxidation processing of any one in the apparatus for feeding, extension apparatus, enforcement claim 1 to 5 of fiber, preferably they is placed on the spool.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR0004033A FR2807076B1 (en) | 2000-03-30 | 2000-03-30 | PROCESS FOR OXIDATION OR ACTIVATION OF A FIBROUS MASS BY A GASEOUS MIXTURE CONTAINING OZONE |
| FR00/04033 | 2000-03-30 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1420953A true CN1420953A (en) | 2003-05-28 |
| CN1211526C CN1211526C (en) | 2005-07-20 |
Family
ID=8848662
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 01807495 Expired - Fee Related CN1211526C (en) | 2000-03-30 | 2001-03-28 | Method for oxidising or activating textile mass with gas mixture contg. ozone |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP1297214A2 (en) |
| CN (1) | CN1211526C (en) |
| AU (2) | AU2001246659B2 (en) |
| FR (1) | FR2807076B1 (en) |
| NZ (1) | NZ521591A (en) |
| WO (1) | WO2001075212A2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113474508A (en) * | 2018-12-21 | 2021-10-01 | 牛仔裤科学有限公司 | Method for processing a wool garment to inhibit subsequent bonding and shrinkage thereof, and wool garment treated using the method |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1619174A1 (en) * | 1965-03-24 | 1971-06-03 | Thorsen Walter Joseph | Method and device for the shrink-fit meshing of animal fibers |
| US3404942A (en) * | 1965-08-18 | 1968-10-08 | Agriculture Usa | Shrinkproofing of animal fibers |
| GB1154729A (en) * | 1965-09-23 | 1969-06-11 | Iws Nominee Co Ltd | Wool Processing |
| JPS58144105A (en) * | 1982-02-12 | 1983-08-27 | Kurabo Ind Ltd | Production of descaled animal fiber |
-
2000
- 2000-03-30 FR FR0004033A patent/FR2807076B1/en not_active Expired - Fee Related
-
2001
- 2001-03-28 NZ NZ521591A patent/NZ521591A/en unknown
- 2001-03-28 AU AU2001246659A patent/AU2001246659B2/en not_active Ceased
- 2001-03-28 CN CN 01807495 patent/CN1211526C/en not_active Expired - Fee Related
- 2001-03-28 AU AU4665901A patent/AU4665901A/en active Pending
- 2001-03-28 EP EP01919591A patent/EP1297214A2/en not_active Withdrawn
- 2001-03-28 WO PCT/FR2001/000941 patent/WO2001075212A2/en active IP Right Grant
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113474508A (en) * | 2018-12-21 | 2021-10-01 | 牛仔裤科学有限公司 | Method for processing a wool garment to inhibit subsequent bonding and shrinkage thereof, and wool garment treated using the method |
| CN113474508B (en) * | 2018-12-21 | 2023-10-27 | 牛仔裤科学有限公司 | Method for processing woolen garments to inhibit subsequent binding and shrinkage thereof, and woolen garments treated using the method |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2001075212A2 (en) | 2001-10-11 |
| AU4665901A (en) | 2001-10-15 |
| NZ521591A (en) | 2004-02-27 |
| AU2001246659B2 (en) | 2004-09-30 |
| CN1211526C (en) | 2005-07-20 |
| FR2807076A1 (en) | 2001-10-05 |
| WO2001075212A3 (en) | 2002-02-28 |
| FR2807076B1 (en) | 2003-03-28 |
| EP1297214A2 (en) | 2003-04-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1048533C (en) | Fibre treatment | |
| RU2102547C1 (en) | Method of preparing bleached pulp and a method for delignification and bleaching of lignocellulose material | |
| Körlü | Use of ozone in the textile industry | |
| Sargunamani et al. | A study on the effects of ozone treatment on the properties of raw and degummed mulberry silk fabrics | |
| Eren et al. | Ozone: an alternative oxidant for textile applications | |
| Kan et al. | An investigation of color fading of sulfur-dyed cotton fabric by plasma treatment | |
| CN1211526C (en) | Method for oxidising or activating textile mass with gas mixture contg. ozone | |
| CN1170032C (en) | Pollution prevention method for canvas used in paper machine | |
| CN1215218C (en) | Process for improving non-shrinkable behaviour of wool | |
| CN1174140C (en) | Textile finishing process | |
| CN101068969A (en) | Continuous textile converting method and installation therefor | |
| CN1043957A (en) | Non-pollution dual tanning technology for glutaric aldehyde pigskin leather | |
| CN1334374A (en) | Excellent shrink resistance animal fibre and method for preparing same | |
| Sargunamani et al. | Effects of ozone treatment on the properties of raw and degummed tassar silk fabrics | |
| Teklemedhin | Cationization of cotton using extracted keratin from ethiopian sheep wool waste for salt free dyeing with reactive dye | |
| EP3670737B1 (en) | A method for processing wool garments for inhibiting their subsequent felting and shrinkage | |
| Jain | Alternative to water based fabric cleaner in textile and detergent processes | |
| CN87107734A (en) | The processing of fabric | |
| Özdemir et al. | Ozone Bleaching of Denim Fabrics. | |
| Mao et al. | Investigation of a homogeneous activating ozonation method in the rinsing procedure of cotton fabric dyed with reactive dye | |
| CN1104522C (en) | Method of production of woven/knitted fabrics using sericin fixation yarn and woven/knitted fabric produced by method | |
| CN1143103A (en) | Shrink-proof anti-crease finishing liquid for garment lining and making method | |
| Saleemi et al. | A green and cost-effective approach to reutilize the effluent from bleaching process | |
| CN1730808A (en) | pretreatment cleaning continuous production process for knitted fabric | |
| CN1335425A (en) | Antishrinking method for animal fibre |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20050720 Termination date: 20110328 |