EP1297214A2 - Method for oxidising or activating a textile mass with a gas mixture containing ozone - Google Patents

Method for oxidising or activating a textile mass with a gas mixture containing ozone

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Publication number
EP1297214A2
EP1297214A2 EP20010919591 EP01919591A EP1297214A2 EP 1297214 A2 EP1297214 A2 EP 1297214A2 EP 20010919591 EP20010919591 EP 20010919591 EP 01919591 A EP01919591 A EP 01919591A EP 1297214 A2 EP1297214 A2 EP 1297214A2
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EP
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Application
Patent type
Prior art keywords
fibers
wool
ozone
mass
characterized
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.)
Withdrawn
Application number
EP20010919591
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German (de)
French (fr)
Inventor
Luc Choisnard
Didier Guillochon
Bernard Leman
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chargeurs Wool (Eurasia)
CHARGEURS WOOL EURASIA
Original Assignee
CHARGEURS WOOL (EURASIA)
CHARGEURS WOOL EURASIA
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Classifications

    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS, OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M16/00Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
    • D06M16/003Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic with enzymes or microorganisms
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS, OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00Treating 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
    • D06M11/32Treating 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
    • D06M11/34Treating 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 m3, 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

A method of oxidation or activation of a fibrous mass with a gas mixture containing ozone

The invention relates generally to the oxidizing treatment of any fibrous mass which can be formed into a sheet adapted to be homogeneously traversed and completed by a gas.

Here, the term fibrous mass, any mass of fibers of animal origin, vegetable or synthetic origin.

The oxidative treatment of textile fibers, especially protein, is particularly concerned and especially that of wool in the broad sense of the term (sheep wool, goat, llama etc ...). More specifically, the invention relates to an oxidative treatment, in particular non-polluting, non-destructive, a fibrous mass as defined above, in order to impart particular qualities such as, for wool, 1 ' infeutrabilité and wool and various other fibers, the non-narrowing or ability to fix dyes, for example.

Regarding particularly wool, it is recalled following. Wool fiber is a fiber of animal origin, protein 97%. Morphologically, the fiber is in the form of a cylinder whose diameter ranges from 15 to 40 micrometers for a length of 20 to 150 millimeters. Fiber comprises two distinct parts: the center of the fiber referred to as the cortex name and scales covering the cortex. The set of scales is designated by the term cuticle. The peeling is attached to the cortex by a cement but only two thirds of its length. Thereby the end portion is free and can be lifted depending on the state of the fiber. This lifting phenomenon occurs when the moisture content of the fiber varies and that the fiber is moving, allowing it to meet other fibers. The scales then being apart of the cortex, there is a phenomenon ratchet that becomes irreversible due to the closing of the scales. This phenomenon is commonly referred to as felting.

Felting is a major drawback for wool maintenance. Indeed, as explained previously, felting is linked to the movement of the fibers and their water content. This is why washing a woolen article must be done with great care. It is particularly recommended to wash by hand and dry it flat, which is particularly restrictive and limit, to some extent, the development of woolen items that need to be washed often, particularly clothing.

There is therefore, a very long time, a need for treatments that prevent, at least to a large extent, felting wool when washed and, more recently, with the release of washing machines, that allow its washing machine.

There is also a need for ever more effective treatments for other applications, especially for dyeing wool.

The peeling is an important part of the wool as it is home to many chemical reactions involved in the wool processing, that is to say, the dye, the addition of auxiliaries (eg bactericidal) of waterproofing agents, resins preventing felting. Moreover, worsted present naturally a shade that, according to quality varies from white to straw yellow. Different bleaching agents are used in the wool industry, mostly chlorinated derivatives whose use is increasingly restricted due to the toxicity of their waste.

The reactivity of wool scales can be increased with the aim of improving the effectiveness of these treatments, or reduce the duration or cost. As examples, two treatments widely used in the wool industry can be cited. The first in the field of dyes. To obtain the desired coloring, it is necessary to the wool in a dye bath to be heated to boiling in order to allow opening the pores of the flake, which allows the diffusion of the dye inside the 'peeling and for times of the order of the day. Any treatment to change one tortoiseshell facilitate dyeing.

Moreover, many treatments have been proposed in order to make the machine washable wool. The most effective treatment to obtain certification "machine washable" is to coat the wool fiber with a resin, which has the effect of preventing the felting wool. In this treatment, it is necessary to oxidize prior wool scales to enable the attachment of the resin. Different methods use oxidizing chemical, mainly made of chlorine. These products are the source of pollution that eventually condemn their use.

This is why alternative processes to facilitate attachment of the resin were studied. Some consist of replacing the chlorine with less polluting oxidants such as permanganate, persulfates or hydrogen peroxide. Other methods aim to replace the use of the resin by reducing the thickness of the flake or totally eliminate the scales of the fiber. These methods also require a pretreatment of the fiber by oxidation, which is followed by treatment with a protease, in order to detach or totally destroy the scales. The latter method allows a smooth fiber which is not only infeutrable but finer than the natural fiber or the fiber treated by other methods, which is a commercial advantage.

It seems now acquired a pre-treatment, especially oxidation, before a possible treatment with a protease, is qualitatively and economically necessary to obtain a good quality fiber, ready for further processing in particular to make it machine washable and / or dye satisfying current requirements. However, as explained above, oxidizing treatments currently available, including those that do not use chlorine compounds, are pollutants.

According to the present invention, had the idea of ​​using ozone to perform the oxidative treatment. Ozone has in the past been proposed several times to make animal fibers such as wool in particular, shrink resistant.

Thus, patent US-A-4 189 303 discloses a process for making shrink resistant materials based proteinaceous animal fibers, which method comprises putting these materials in contact, for about 2 to 6 minutes, with an aqueous solution of ozone containing about 1 to 20 mg / 1 of ozone, at neutral pH and at a temperature of about 20 to 30 ° C. The description of the prior art of US-A-

4,189,303 summarizes and comments on three prior patents, namely GB-242 patents, 027, US-A-3, 149, 906 and US Patent 3,404,942.

GB-A-242.027 proposes to impregnate the wool for a few minutes with a 5% ammonia solution, to extract the excess liquid and exposing, in the wet state, to the air containing ozone at a concentration of 1 to 1,000.

According to US-A-3, 149, 906, a stream consisting of ozone and steam is blown through the textile to be treated. The ozone content in the stream is about 10 to 50 mg / 1. The treatment is carried out at a temperature of about 60 to 95 ° C for 1 to 10 minutes.

According to US-A-3, 404, 942, a wet proteinaceous tissue is heated on one side at a temperature of 80 to 170 ° C, while an ozone containing gas stream passes on the opposite side.

The referenced article: Textile Research Journal, Vol. 35 (7), 1965, pages 638-647, discloses the use of a gaseous mixture ozone / oxygen, among others, for treating wet wool fabrics at room temperature. Nothing in this document allows to see how the treatment he described, realized laboratory scale, could be transposed to an industrial scale to efficiently process large fibrous masses. None of these treatments appears to have been used industrially for a wool infeutrable much less a machine washable wool, presumably because of disappointing results that led researchers to explore other avenues that treatment with ozone, there including to perform pretreatment of the wool fiber scales.

It has now been found that it is possible to obtain a good quality wool fiber, ready for further processing, to perform a pretreatment in which the oxidizing pollutants used so far are replaced by a mixture oxidant containing a defined proportion of ozone in specific conditions.

According to one of its aspects, the invention relates to a method of oxidizing a fibrous mass for modifying the surface of the fiber component, which process essentially comprises: a) transforming said fibrous mass in a fibrous mass containing 12.5 to 60% (g / g) of water and having a structure such that gas can pass through regularly and completely; and b) passing through said mass, for 5 to 20 minutes at room temperature, a gaseous mixture containing 20 to 150 g of ozone per m.3, which is continuously injected through said mass during that it runs on a carrier system, being sent alternately on both sides of said mass.

Here, the term "surface modification of fibers composing the" the treatment is essentially limited to the surface and does not affect the core of the fibers.

The modification in question is in particular to enable or facilitate subsequent processing such as in particular dyeing or enzymatic treatment. This modification may also, in some instances impart directly to the fibrous mass of a certain quality, e.g., 1 'infeutrabi ity (non-shrinkage) of the wool in the presence of water when it is not subjected to a temperature high and / or vigorous stirring, or a bleach. By varying the different parameters of the process according to the invention (especially water content, duration of treatment and the concentration of ozone in the gas mixture), it is possible to modify a given type of fibers to obtain the desired reactivity or respectively the particular desired quality. The parameters can be defined by preliminary tests.

Here, the term "a structure such that a gas can pass through regularly and completely" a structure such that the gas that passes through is in contact with every fiber and whole surface. A "veil" fiber usually respond to this definition.

The term "room temperature" a temperature of the order of 15 to 30 ° C. The mixed gas used can be any mixture containing 20 to 150 g of ozone per rr in the presence of one or more other gases which do not affect adversely the fibers, especially their central part. Typically, this mixture consists in mixture of ozone with oxygen or air, preferably oxygen. The oxidation process of a fibrous mass according to the invention is carried out continuously. More specifically, the gas mixture containing ozone is injected continuously through the fibrous mass of step a) as it travels on a carrier system, particularly a porous web or perforated cylinders, being alternatively sent on both sides of the fibrous mass.

According to a preferred embodiment, the fibrous mass is in the form of a veil --continu of constant thickness over its entire width and length. The release of large amounts of ozone in the atmosphere having the effects of pollutants in a particularly preferred embodiment, the method according to the invention is carried out in a sealed chamber and ozone not consumed by the reaction of oxidation of the fibrous mass is destroyed before discharge of the other gases of the mixture.

Different-type reactors that can be used in this particularly preferred mode of carrying out the method according to 1 the invention are described in International Patent Application (PCT) deposited parallel to the name of the present Applicant and which is entitled "Reactor for treating a solid material by a gas or a harmful gas mixture and comprising the plant ".

The following describes the advantageous operating principle of a sealed reactor for the treatment of a fibrous mass with a gas mixture containing from 1 ozone according to the invention.

The exchange between the gas mixture and the fibrous mass is done in this case by passing the gas through the moving mass. Applying the principles of the countercurrent and multiple effect, which reduces the concentration of ozone in the gas mixture and thus reduce its concentration in the leak to the reactor inlet.

To do this, one introduces the gas mixture at the outlet of the fibrous mass and its ozone concentration is depleted by passing it in processing cells. Thus, the ozone concentration decreases in each cell and tends towards zero at one input of the reactor. For example, the reaction chamber is divided into cells of which the seal is obtained by means of rollers. The gaseous mixture is introduced at the output of the fiber mass passes through the fibrous mass in motion, then penetrates in the opposite direction in the next cell. The gas mixture, depleted in ozone, is extracted at the inlet of the fibrous mass.

So that the fiber mass is not entrained by the gas flow, it is held between two porous conveyor belts (upper conveyor and the lower conveyor, respectively). These two porous webs which enclose the fibrous mass moves on a porous support by creating a pressure drop which facilitates the even distribution of the gas mixture into the fibrous mass.

According to a variant based on the same principle, in the reactor cell are replaced by floors ensuring the reversal of the fibrous mass. An entry lock system and outlet can be flushed under the control of a probe which reacts to the presence of ozone at a higher threshold ppm. The principle reactors patterns which can advantageously be used for carrying out the oxidation process a gaseous mixture containing ozone according to the invention are shown in Figures 2 and 3 appended which will be described later. The method according to the invention is particularly applicable to the woolen oxidation, as shown in Examples 1 to 12 described in the experimental section which follows and the comparison of Figures 8 to 13 appended.

Example 1 shows that the wool subjected to the oxidation process with ozone according to the invention has a sensitivity to enzymatic hydrolysis comparable to that of the wool treated with chlorine.

In particular since 1 'is not consumed by the ozone oxidation can be easily converted back to oxygen by simple heat treatment, the method according

1 the invention is advantageously suitable to replace the existing oxidizing treatments which are pollutants, particularly treatments which use chlorine or compounds thereof. Furthermore, the effluent gas mixture charged with oxygen can be recycled after passage through an ozone generator.

Example 2 shows that the effectiveness of subsequent treatment with protease may be modulated by acting on the relative humidity of the fibrous mass of wool at the time of ozone treatment.

Example 3 shows that the ozone treatment is capable of reducing the average diameter of the wool fibers, that is to say to improve their smoothness, while giving them after enzymatic hydrolysis, a sufficient inf eutrabilité to obtain the label "machine washable" without using a resin application.

Example 4 shows that duration of equal treatment, the fineness of the fibers increases and the felting tendency decreases as the concentration of ozone in the gas mixture increases.

Example 5 shows that the ozone treatment is able to improve by itself, the whiteness of wool. Example 6 shows that pre-treatment with ozone is at least as effective as treatment with chlorine to sensitize the wool to the application of a resin. The method according to the invention is very advantageously applicable to the production of machine washable wool by applying a resin. Example 7 shows that the ozone treatment followed by enzymatic hydrolysis meets the highest requirements regarding obtaining a great infeutrabilité.

Examples 8 to 12 which were used in a pilot plant in which the reactor chamber had a length of 1.5 m and a width of 30 cm, confirm the results obtained in the other examples as to the fineness and 1 ' infeutrabilité.

Description of FIGS. Figure 1 shows the block diagram of the ozone treatment system used in Examples 1 to 5 and 7 below.

1 of oxygen is fed to an ozone generator thermostated with water at 10 ° C. The ozone / oxygen mixture produced is sent to the bottom of a closed reactor with a grid on which are arranged, as a veil, the wool fibers to be treated. The gaseous mixture passes through the sail upwardly and escapes in the direction of a valve which restricts the flow of 1 1 / min to the ozone sensor, within the framework of the measurement of the ozone consumption in the reactor. The total flow of gas mixture leaving the reactor is sent to a thermal ozone destroyer. The gas leaving the destroyer is oxygen which can either be released into the atmosphere or be recycled to the ozone generator.

The attached Figure 2 shows schematically a reactor for the oxidative treatment of the wool washed with a mixture of oxygen (or air) and ozone, as well as the environment in the case of obtaining washable wool machine.

The wool is transported into the reactor by a conveyor apron and enters the box sealing, it then passes between the rolls of a roll press which seals with the oxidation chamber. Inside the oxidation vessel are two drums perforated sheet counter rotating. The gas mixture is introduced into the oxidation vessel and extracted by an extractor whose inlet is located inside the drums. It therefore creates a vacuum that has the effect of forcing the gas mixture through the wool layer while pinning it on the drums. The fact that there are two drums increases the contact time. The seal at the outlet of reactor can be obtained in the same manner as its input. In a variant shown in the diagram, the wool can be output by means of a system enabling the fall of the wool in a treatment bath, for example by a protease, the sealing being provided by the bath guard found in the wool of lowering conduit.

The sealing chamber is connected to a blowing fan that establishes an overpressure in the box, compared with the pressure prevailing in the oxidation chamber.

The gas escaping as the oxidation chamber that the sealing box is sent to a thermal ozone destroyer.

Figure 3 attached shows a simplified variant of the reactor of Figure 2 and its environment. In this embodiment, the drum system is replaced by porous carrier tape decks. The reactors 2 and 3 ensure the protection of the environment as follows.

The gas mixture that passed through the wool is released into the atmosphere after passing through a destructive thermal ozone. Air ozone concentration present in the sealing box is measured continuously. When it reaches a limit value, air is blown into this chamber so that the ozone is sent to the destructive to ozone.

Figure 4 appended represents the variations of the absorbance at 280 n of the enzymatic treatment according supernatant 1 Example 1 as a function of the hydrolysis time in minutes, for a wool fiber treated with chlorine, a fiber treated with ozone and a crude fiber, respectively. Figure 5 attached shows changes of absorbance at 280 nm of the enzymatic treatment according supernatant 1 Example 2 to a wool fiber treated with ozone at a relative humidity of 5-0% to 12.5%, respectively. 6 shows schematically a continuous processing line of the scoured wool to make washable by enzymatic hydrolysis after oxidation with ozone according to the invention.

This chain comprises essentially - a feeding station

- an oxidation reactor

- a finishing treatment station.

The supply station is connected to a drum drawing device which transforms the scoured wool which is in the form of fluff, into a web of suitable thickness.

The reactor, schematically represented in Figure 6, may in particular be of the type shown in Figure 2 or, preferably, of Figure 3.

The wool thus oxidized undergoes an enzymatic treatment and then, after rinsing, it is séchéee, carded, combed and setting reels.

Figure 7 attached shows schematically a wool worsted processing chain to make washable by enzymatic hydrolysis after oxidation with ozone according to the invention.

The principle of this processing sequence is the same as in the case of Figure 6, except that the feed station comprises a creel for the passage of tapes in the roll system which has a function of rolling the web ribbons so as to feed the reactor with a thin web. It is possible to moisten the ribbons before pasage in 1 'stretcher.

Processing lines of Figures 6 and 7, to fix ideas described in the case of wool processing to make machine washable, can be easily adapted to other fibers and other treatments "finishing" after the treatment with ozone, such as for example dyeing, replacing 'the hydrolysis bath a dye bath. FIG 8 is a photograph at 2000X magnification of a fiber untreated raw sheep wool.

Figure 9 is a photograph at 2000X magnification of a crude fiber sheep wool treated with subtilisins GC 897-200 .mu.l / 1.

Figure 10 is a photograph at 2000X magnification of a fiber wool of sheep treated for 15 minutes by a flux of 2 1 / min oxygen containing 100 g of ozone / rr.3. FIG 11 is a photograph at 2000X magnification of a sheep wool fiber treated for 15 minutes by a flux of 2 1 / min oxygen containing 100 g of ozone / m ^ then by GC enzyme 897 200 .mu.l / 1. Figure 12 is a photograph at 2000X magnification of a sheep wool fiber treated with chlorine to 2%.

FIG 13 is a photograph at 2000X magnification of a sheep wool fiber treated with chlorine to 2% and then by the enzyme GC 897-200 .mu.l / 1.

No significant difference is observable between FIGS photographs 8 and 9. This result illustrates the inefficiency of a single enzyme treatment by subtilisins GC 897 (200 .mu.l of GC 897, 1 liter of borate buffer, pH 9, 5/0, 25M / 55 ° C / 5 min). The photographs of Figures 10 and 12 show that the treatments with ozone (100 g / ir, 21 / min, 15 min) and by chlorination of 2% of chlorine, respectively erode the surface of the fibers whose edges are noticeably cuticle less prominent. The photograph of Figure 13 shows that treatment with chlorination to 2% of chlorine followed by enzymatic hydrolysis (GC 897-200 .mu.l / 1, 1 liter of borate buffer, pH 9, 5/0, 25M / 55 ° C / 5 min) is actually destructive party: fragments fibers begin to peel away from the cortex.

The photograph of Figure 11 illustrates the mean fiber type obtained by treatment with one ozone according to the invention (100 g / m.3, 21 / min, 15 min), followed by enzymatic hydrolysis (GC 897 200 .mu.l / 1, 1 liter of borate buffer, pH 9.5 / 0.25 M / 55 ° C / 5 min). The fiber obtained is perfectly sanded. She has neither scales nor damage. EXPERIMENTAL EXAMPLE 1: Improved sensitivity to wool

1 enzymatic attack.

This example shows the need to pre-treat the fibers by oxidation to sensitize them to enzymatic attack. The enzymatic attack is performed on three batches of fiber obtained as follows:

1. Fiber treated by chlorine: 300 g of carded sheep's wool fibers, combed are introduced into 6 liters of acetate buffer 0, lM / pH 4 and incubated 5 min at 20 ° C. 4% (v / v) Basolant DC® (chlorocyanurate to 62-64% available chlorine), marketed by BASF are added and the preparation was incubated 45 min at 20 ° C. The free radicals formed are neutralized by reduction with sodium metabisulphite 0.3% (w / v) at 20 ° C for 15 min. The fiber sample is rinsed with distilled water, drained manually and dried 24 hours at room temperature.

2. Fibers treated with ozone:

Ozone is generated by an ozone generator Ozat-IA ™ of Ozonia company, from pure oxygen at greater than 90%. The nominal output of the apparatus is approximately 80 g of

03 / h, for a 6% production yield (g / g). The exact concentration of ozone in oxygen is measured by UV photometry at 254 nm, using an online analyzer BMT 963 of Ozonia Company. 10.05 ± 0.05 g of dry sheep wool are immersed in 1 liter of distilled water, optionally containing hydrogen peroxide and / or sodium hydroxide. After filtering, the fibers are placed on the gate of a reactor as shown in the block diagram of Figure 1 attached.

The gaseous mixture based on oxygen to 100 g / πβ ozone passes through the grid for 15 minutes.

3. Crude fiber (sheep wool)

The enzymatic attack fiber 1., 2. and 3. is carried out according to a protocol inspired Peters work

DE, JH Bradbury, Material digest by trypsin from fibers and cortical cells, Aust. J. Biol. Sci.25. , 1225-1234

(1972). 1.05 ± 0.05 g of dry fiber 1., 2. or 3., respectively (relative humidity: 12.5%) is introduced in 100 ml of 0.25M borate buffer / pH 9.0 at 60 ° C . After 5 min pre-incubation, 140 .mu.l of BACTOSOL WO (CLARIAN®, ref.

2900098) and lOμl of GC 897 (GENECOR®) are introduced into the reaction medium. At different time intervals, 2 ml of the reaction supernatant is removed and introduced into a hemolysis tube containing 0.5 ml of HCl 0, 1M to stop the reaction. The contents of the tube is filtered (filter of cellulose acetate AIT CHROMATO, diameter 13 mm, porosity 0.22 .mu.m) and the absorbance of the filtrate is measured

280 nm using a spectrophotometer Perkin Elmer LAMBDA.

The absorbance at 280 nm is a function of the amount of peptide released by the wool during the enzymatic hydrolysis. The higher it is, the more the yarn is susceptible to enzymatic hydrolysis.

The results obtained with the three samples of fibers subjected to this hydrolysis are summarized in Table I below.

TABLE I

These results are shown graphically in f igure 4 which shows, for each fiber sample, changes in absorbance of the supernatant at 280 nm as a function of the duration of the hydrolysis.

This example highlights the fai t the ozonated wool has a sensitivity comparable to that enzymatic hydrolysis of the chlorinated wool, while wool has not been subjected to oxidative pre-treatment has virtually no sensitivity.

EXAMPLE 2

Effect of humidity on the effectiveness of the sensitization treatment of the wool fibers to enzymatic attack. The relative humidity of two samples of sheep's wool fibers is fixed at 12.5 and 50%, respectively. These samples are introduced into the enclosure ozonation used in Example 1 and 'subjected to the same treatment of ozonization (100 g of 03 / m ^ 2 1 / min, 15 minutes). Susceptibility to enzyme attack of each of the samples is determined using the technique described in Example 1.

The results are summarized in Table II below. TABLE II

These results are shown graphically in Figure 5 which shows, for each sample, changes in absorbance of the supernatant at 280 nm as a function of the duration of one hydrolysis. This example highlights the fact that the effectiveness of awareness protease treatment depends on the relative humidity of the fibers at the time of the oxidative pre-treatment by ozone. It shows that it is better to work with a relative humidity of 50%, rather than 12.5%.

Example 3

Effect of ozone on the fiber diameter and their ability to felting. As part of the research that led to the invention, it was developed an analytical method for assessing the improved responsiveness of wool. This method involves subjecting the wool, after oxidative pre-treatment with ozone, a proteolytic hydrolysis and then measuring its finesse and ability to felting.

A sample of 10.00 ± 0.05 g of sheep wool worsted whose water content is 50%, is placed on the grid of the reactor used in Example 1. A gas mixture stream (2 1 / min ) oxygen containing compound 30 g of ozone / m ^, passes through the wool. The experiment was performed 4 times with varying durations of pretreatment with ozone (0 to 20 min).

In a second step, all samples were subjected to enzymatic treatment (GC 897 200 .mu.l / l, in 1 liter of 9/0 borate pH buffer, 25M / 55 ° C). The ability to felting and evolution of the fineness (average diameter) of the fibers of each sample were determined respectively according to the standards IWTO IWTO 20-69 and 12-95. The results are summarized in Table III following. TABLE III

This table clearly shows that treatment with ozone reduces the average fiber diameter

(Increasing fineness) and their ability to felting

(Ball density).

Example 4 was repeated the experiments of Example 3 but using for the treatment with ozone, a gaseous mixture containing 100 g of ozone / m 3.

The results are summarized in Table IV below. TABLE IV

This table shows that the magnitude of the decrease in the average fiber diameter and the ability felting increases, for the ozone treatment of given duration, depending on the concentration of ozone in the gas mixture.

EXAMPLE 5

Wool bleaching by treating 1 ozone.

Samples of 10.00 ± 0.05 g of wool are treated for 10 min using a mixture of oxygen and ozone to 30 and 100 g of ozone / m 3, respectively, the flow of the mixture being 2 1 / min. These samples were then treated or not treated with protease (GC897 200 .mu.l / 1, one liter of borate buffer, pH 9 / 0.25M, 55 ° C).

The whiteness of the treated wool is, in each case measured using a reflectometer MICROCOLOR. It is expressed as the IWTO 35 method and the brightness is represented by the letter W. The higher the W value, the lower wool is white.

The results are summarized in Table V below. TABLE V

This table shows that the whiteness of the wool fibers is improved by treatment with ozone.

The improvement is comparable for test E2 E4 and E5 for significantly higher. EXAMPLE 6

Sensitization of wool fibers with the application of a resin, caused by pre-treatment with one ozone. In this example, the samples tested receive an application by Hercosett®125LX resin exhaustion of Hercules. This resin is a polyamide resin-treated cationic epichlorohydrin which is reactive vis-à-vis the fibers. This resin was chosen because it claims the primer status antifelting wool in the exhaust process after bleach. It has been developed to greatly reduce the contribution of the resin .the content of halogenated organic compounds in wastewater. The samples tested were:

1.- 40 g of a control material (crude fiber) as a sheep combed wool top at 20 g / m of average fineness of wool fibers 21.5 microns;

2. 40 g of a material called "O3 treated" according to the invention in the form of four portions of 10 g each (treatment for 10 g of wool: 15 min in a flux of 2 1 / min oxygen containing 100 g ozone / m 3); 3. 75 g of a material called "CI2 treated" in a sheep combed wool top (bleach 2%). The general conditions of application of the resin are as follows.

25 g of wool are arranged in a lab system of the dyeing pot AHIBA TURBOMAT containing 0.5 liter of a solution containing 6 g / 1 Hercosett® 125LX pH between 7.8 and 8.2 obtained by the addition of 28% ammonia. This bath is applied to wool at 30 ° C for 45 min.

ribbon sections are then foulardés (45 kg / cm) two times and then dried with hot air at 85 ° C for 15 min. Then, the resin is polymerized by exposing the sample to the températutre 110 ° C for 4 min. Few grams of each sample are carded by hand after finishing treatment and 1 g of the carded sample is tested for reactivity of the fibers Lanasol® Blue 3R dye, which is an equivalent of Procion Blue M3.

This test is currently used as an indicator of the homogeneity of Hercosett® 125LX applications on wool having undergone pretreatment bleach.

In this test, we determine both L * and b * are colorimetric parameters to account for the making efficiency Lanasol® Blue 3R. So they pemettent measure the performance of the application of Hercosett® 125LX resin capable of absorbing the coloring. b * is the yellow-blue chromatic component and J * to the clarity of the sample tested.

Thus, less than the b * value, the higher the sample exhibited a blue color.

Moreover, less the lightness L *, the higher the intensity of the color is important.

Specifically, the application of the resin on the tested sample is more effective that the values ​​b * and L * are corresponding low.

The results are summarized in Table VI below.

TABLE VI

This table shows that the blue color is darker for samples oxidized by chlorine or 1 ozone. The depth of tone is even more pronounced for wool treated with Cl2 or O3 and resin.

The most blue sample is one that is primed with 1 'Hercosett® 125LX after pretreatment 1 ozone. In conclusion, the wool oxidized by the process of pre-ozone treatment is also refines for resins such as 1 'Hercosett® 125LX and even more refined than wool oxidized by bleach.

EXAMPLE 7

Obtaining quality "machine washable" for a knit obtained from wool fibers treated with ozone and then subjected to enzymatic hydrolysis.

Under European standards, the maximum withdrawal limits measured by the IWS test the most drastic TM31 are applied to footwear textiles. In this case, the withdrawal area at the end of a cycle 7A followed by 5 cycles 5A does not exceed 8%. This value corresponds to the withdrawal limit is not exceeded. Two samples of knitting 100 cc were tested. The first was carried out with untreated sheep wool fibers. The second was made with sheep's wool fibers treated with ozone (100g of 03/3, 2 1 / min, 15 min) followed by the enzyme GC 897 (200 .mu.l / 1 borate buffer 0, 25M / pH 9.1 / 55 ° C / 1 liter).

The dimensional changes of the samples were measured after 7A wash cycle followed by 5 wash cycles 5A and a dry flat. The results are expressed by calculating the percentage of area considered withdrawal of knitted wool.

The sample untreated fibers has a total withdrawal after the 80% test. Under the same conditions, the sample fibers treated by ozone and subjected to enzymatic hydrolysis has a shrinkage of only 4%. This result is quite comparable to that obtained in the case of chlorinated fibers. The fibers treated according to the present invention therefore have the quality "machine washable". The articles made from these fibers can claim 1 obtaining WOOLMARK label "ash machine."

EXAMPLE 8

Three combed wool tops of 21.7 mm in diameter and metric weight 48 g were immersed in water and drained so as to bring their moisture to 40%. These tapes pass through a machine for stretch 5.6 times. Wool web obtained through the reactor at a rate of 0.3 m / min, which corresponds to a 5 minute contact time.

The reactor is fed with a gas mixture of oxygen and ozone with the ozone concentration is 112 g / m 3 and flow rate of 3.5 m 3 / h.

Wool at the outlet of the reactor is dried and is then subjected to the enzyme treatment described above. The results are summarized in Table VII below.

TABLE VII

EXAMPLE 9

Three combed wool tops of 22.1 mm in diameter and metric weight of 55 g passed in a machine for stretch 1.22 times. Wool web obtained is immersed in water and then dewatered to a moisture of 40%. It passes through the reactor at a rate of 0.15 m / min, which corresponds to a 10-minute contact time.

The reactor is fed with a gas mixture of oxygen and ozone with the ozone concentration is

112 g / m 3 and flow rate of 1.75 m 3 / h-

Wool at the outlet of the reactor is dried and is then subjected to the enzyme treatment described above.

The results are summarized in Table VIII below.

TABLE VIII

EXAMPLE 10

Three combed wool tops of 22.1 mm in diameter and 55 g metric weight pass through a machine for stretch 1.22 times. Wool web obtained is immersed in water and then dewatered to a moisture of 40%. It passes through the reactor at a rate of 0.15 m / min, which corresponds to a 10-minute contact time.

The reactor is fed with a gas mixture of oxygen and ozone with the ozone concentration is 112 g / m 3 and flow rate of 3, 5 m 3 / h. Wool at the outlet of the reactor is dried and is then subjected to the enzyme treatment described above. The results are summarized in Table IX below. TABLE IX

EXAMPLE 11

Three combed wool tops 22.1 mm in diameter and 55 g metric weight pass through a machine for stretch 1.22 times. Wool web obtained is immersed in water and then dewatered to a moisture of 40%. It passes through the reactor at a rate of 0.3 / min, which corresponds to a 5 minute contact time.

The reactor is fed with a gas mixture of oxygen and ozone with the ozone concentration is 112 g / m 3 and flow rate of 3.5 m 3 / h.

Wool at the outlet of the reactor is dried and is then subjected to the enzyme treatment described above. The results are summarized in Table X below.

PAINTINGS

Example 12

Three combed wool tops of 22.1 microns in diameter whose metric weight is 55 g pass through a machine for stretch 1.22 times. Wool web obtained is immersed in water and then dewatered to a moisture of 40%. It passes through the reactor at a rate of 0.15 m / min, which corresponds to a 10-minute contact time.

The reactor is fed with a gas mixture of oxygen and ozone with the ozone concentration is 112 g / m 3 and flow rate of 1.05 m 3 / h.

Wool at the outlet of the reactor is dried and is then subjected to the enzyme treatment described above. The results are summarized in Table XI below.

TABLE XI

Claims

1.- oxidation method of a fibrous mass for modifying the surface of the fibers composing the, which process essentially comprises: a) transforming said fibrous mass into a fibrous mass containing 12.5 to 60% (g / g) of water and having a structure such that gas can pass through regularly and completely; and b) passing through said mass, for 5 to 20 minutes at room temperature, a gaseous mixture containing 20 to 150 g of ozone per m 3, which is continuously injected through said mass during that it circulates on a carrier system, being sent alternately on both sides of said mass.
2. A process according to claim 1, characterized in that the fiber mass is a mass of fibers, preferably proteinaceous fibers, preferably of wool fibers.
3. A process according to claim 1 or 2, characterized in that the gas mixture comprises ozone in admixture with oxygen or air, preferably oxygen.
4. - Process according to any one of claims 1 to 3, characterized in that the carrier system consists of a tape or perforated cylinders.
5. - Method according to any one of claims 1 to 4, characterized in that it is carried out in a sealed chamber and in that one ozone not consumed by the oxidation reaction of the fibrous mass is destroyed prior to discharge from the other gases of the mixture.
6. - Process according to any one of claims 1 to 5, characterized in that the fiber mass flows against the flow of the gas mixture.
7. - A reactor for carrying out the method according to any one of claims 1 to 6, characterized in that it operates according to the principles of the against-current and the multiple effect.
8. - A method for reducing the average diameter of the wool fibers, characterized in that it comprises a step of oxidation of said fibers by the process of any one of claims 1 to 6, followed by a treatment step proteolytic enzymes.
9. - A method for polishing wool fibers without damaging their cortex, characterized in that it comprises a step of oxidation of said fibers by the process of any one of claims 1 to 6, followed by a step treatment with proteolytic enzymes.
10. - A method for increasing the whiteness of wool fibers, characterized in that it comprises a step of oxidation of said fibers by the process of any one of claims 1 to 6, optionally followed by a treatment step proteolytic enzymes.
11. - A method for increasing the reactivity of the wool fibers with the application of a resin or a dye, characterized in that it comprises a step of oxidizing said fiber according to the method of any one of claims 1 to 6.
12. - A method for obtaining wool fibers of the type "machine washable", characterized in that it comprises a step of oxidation of said fibers by the process of any one of claims 1 to 6, followed by a stage of treatment with proteolytic enzymes.
13. - processing chain for implementing the method according to any one of claims 8 to 10 and 12 or the preparation of fibers and further processing, characterized in that it essentially comprises a feeding station fibers , a stretcher, a reactor for carrying out the oxidation process according to any one of claims 1 to 5, a system for further processing, a rinsing device, a drying device and a packaging device, of Any formatting coils, fibers.
EP20010919591 2000-03-30 2001-03-28 Method for oxidising or activating a textile mass with a gas mixture containing ozone Withdrawn EP1297214A2 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
FR0004033 2000-03-30
FR0004033A FR2807076B1 (en) 2000-03-30 2000-03-30 oxidation process, or activation of a fibrous mass with a gaseous mixture containing ozone
PCT/FR2001/000941 WO2001075212A3 (en) 2000-03-30 2001-03-28 Method for oxidising or activating a textile mass with a gas mixture containing ozone

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Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1619174A1 (en) * 1965-03-24 1971-06-03 Thorsen Walter Joseph Method and apparatus for shrinkproofing meshes 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
JPH0154471B2 (en) * 1982-02-12 1989-11-20 Kurashiki Boseki Kk

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0175212A2 *

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WO2001075212A2 (en) 2001-10-11 application
WO2001075212A3 (en) 2002-02-28 application
CN1211526C (en) 2005-07-20 grant
FR2807076B1 (en) 2003-03-28 grant
FR2807076A1 (en) 2001-10-05 application
CN1420953A (en) 2003-05-28 application

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