DE60107626T2 - Shrink-resistant animal fibers - Google Patents

Description

BACKGROUND THE INVENTION

1st area the invention

The The present invention relates to an animal fiber comprising a shrink-proofing equipment and pilling resistance and a method of manufacturing the same. Especially The present invention relates to an animal fiber comprising a Shrink proofing and pill resistance be awarded without the superior water-repellent Property that animal fibers originally possess worsen, and a process for the preparation thereof.

2. Description of the state of the technique

The Animal fiber is a special natural fiber that is used when feeling with the hand has a special texture dependent on the sheep breeds, biological degradable, various excellent properties such as hygroscopicity, moisture-releasability, heat retention, flame retardancy and dyeability and still water repellent. It is about a special fiber, which is a suitable fiber strength and Elongation, wear and tear a higher one Allow abrasion resistance, also from the point of view of mechanical properties, and since long appreciated becomes. The filter property when washing in water and the pill property when wearing, in the structure of the cuticle tissue of the animal Fiber justified are, however, like the wear of clothing undesirable peculiarities. Therefore, for a long time investigations to improve the surface with regard to shrinking, and together with The work has also been carried out on pilling resistance. However, with any animal fiber, that is improved by such an improving process is obtained, the water repellency, a specific peculiarity the animal fiber is sacrificed. A water-repellent membrane from animal fiber is an arrangement that has an influence on the hygroscopicity and the moisturizing ability exerts and to control the heat transfer in connection with adsorption and desorption of water Influence on the heat retention and exercise the comfort. In other words, a conventional shrinking product shrinking through watery Prevent washing, but it lacks the heat retention and comfort.

When conventional, typical shrinking work there is a shrinking Method in which a chlorine agent is used, and in particular one called the shrink-hardening Chlorine-Hercosett process in which a cuticle tissue is hydrophilized from animal fiber, the fabric is softened or removed to shrink Lend property, and continue the cuticular tissue with a Polyamide-epichlorohydrin resin (Hercosett resin, manufactured by Dick Hercules) for reinforcement the resistance across from an aqueous one Washing is coated. Currently this method is distributed worldwide and provisionally as complete Wool shrinking procedure recognized.

from Position of the present worldwide environmental protection is shrinking doing work involving a chlorine agent and a chlorine-containing resin used, but the problem of the amount to be disposed of adsorbable organic halides (AOX) causes, and a new shrinkage process for animal fiber without use of a chlorine agent is becoming current examined. A satisfactory method of replacing the shrink However, the chloro-Hercosett process has not yet been developed Service.

Japanese Kokai Patent No. 126997/1975 discloses a method in which the dyeing property and the shrinkability of wool and the pilling resistance of a wool-synthetic fiber blended product are improved without deteriorating the feel and fiber strength of wool, according to the method Wool tape is impregnated with an aqueous solution of acids or acid salts and dewatered by squeeze rolls and placed in a sealed chamber previously filled with an ozone-containing gas having an ozone concentration of 35.5 ml / l, and further for 10 minutes at 50 ° C is treated while new ozone-containing gas is supplied. However, in this method, only oxidation to a cystine bridged bond (-SS-) is performed, which plays a major role in the shrinkage of wool, and no reduction treatment is carried out. In the case of wool, a -SS bond is not split until this reduction treatment, and this splitting gives wool a satisfactory shrinkproofing, thus providing a sufficient shrinkage resistance and a high shrinkage resistance sufficient pill resistance can not be obtained by the disclosed method. Further, the above-mentioned processes are carried out in a sealed system because the treatment should be carried out in an ozone gas atmosphere, and the action is effected by the aid of molecular movement of ozone gas, therefore, if the amount of wool treatment is increased, unevenness is exhibited the effect of ozone gas can not be avoided, thereby directly causing uneven processing, and uniform shrink-proofing and uniform dyeing of wool can not be obtained. At the same time, in the above-mentioned method, the productivity due to the treatment in the sealed system is low, and when ozone gas leaks directly out of the treatment apparatus, the deterioration of the working environment and the environmental burden are great, and industrialization is difficult.

The Japanese Kokai Patent No. 142759/1980 discloses a method and a device in which a fiber with a Ozone vapor mixed material is treated. In this method is Worsted knitwear made of animal keratin fiber on one piece conveyor belt suspended in a special, with an outlet device equipped treatment device circulates, steam is in introduced this device around the temperature to 79 ° C to increase, a fan begins with the introduction an ozone-air-gas mixture (ozone introduction amount: 3.4 g / min), and this gas mixture is used for Held for 8.25 minutes in the device to provide shrink-resistant equipment Mistake. Also in this process is only an ozone oxidation carried out, and no reduction treatment is effected. Therefore, the lent Shrink proofing unsatisfactory, and continues to point an ozone tank due a defective construction of the device tends to leak on, causing a deterioration of the working environment.

The Japanese Kokai Patent No. 19961/1991 discloses a method for Shrinking an animal fiber using Ozone as oxidant. It describes that ozone gas passes through in a water bath a glass filter is passed, whereby fine bubbles are obtained, and these bubbles are brought into contact with animal fiber. Bubbles that are produced by means of a glass filter or the like are but too big than that ozone gas bubbles could reach fine areas in a fiber, and treat only those surface the fiber. From experience, it is well known that a wool product, about 90% of shrink-resistant wool fiber and about 10% contains a non-shrunk wool fiber in mixture, if it is washed in water to the same extent as a non-shrink made wool product shrinks, whereas in the above-mentioned process an uneven action of an ozone gas on wool produces an uneven treatment, and because of this unevenness insufficient shrinkage is achieved.

The Japanese Kokai Patent No. 72762/1998 discloses a method in which a fiber in the form of a tow, thread, textile material, Gewirks and the like is immersed in ozone, which is dissolved in water and is made by adding an ozone-containing gas that consists of ozone and air in the form of bubbles with a diameter of 0.08 mm or less, in water atomized becomes. It describes a process in which an ozone-containing gas with the formation of bubbles introduced in water will, taking these bubbles atomized by placing them against small walls in a tap mixer bounces, causing fine bubbles obtained with a diameter of 0.08 mm or less, the one increased solubility in water, whereby ozone is obtained, which with a high Concentration dissolved in water is. This is just a procedure for treating rayon and other fibers using ozone dissolved in water.

SUMMARY THE INVENTION

The The present invention provides an animal fiber which a high shrink-proof equipment and pill resistance be lent at the same time without worsening their water repellency. About that In addition, the present invention also provides a method of preparation animal fiber available, in terms of environmental protection, no toxic chlorine containing chemical is used.

The The present invention relates to an animal fiber which, in terms of the shrink-proof equipment and superior to pill resistance is and a water repellency maintains, the animal fibers originally exhibit.

More particularly, the present invention relates to an animal fiber in which the shrinkproofing equipment is reduced to a surface shrinkage rate of not more than 8% for a three hour aqueous Washing is measured when measured as felt shrinkage speed according to Wool Mark Test Method 31.

More particularly, the present invention relates to an animal fiber having a value determined by the difference (μ _a -μ _w ) between the friction coefficient in the direction from the tip to the root (μ _a ) and the friction coefficient in the direction from the root to the tip ( μ _w ) with respect to a fiber direction and measured by the method JIS L-1015, compared to the difference (μ _a - μ _w ) of an untreated animal fiber with respect to the coefficient of static friction or the coefficient of dynamic friction by not less than 30%, μ _{a being} about the same value as that in the case of untreated animal fiber, and μ _w μm being increased by not less than 30% as compared with the value in the case of untreated animal fiber.

The The present invention also relates to an animal fiber in which the pill resistance not lower than the third class according to JIS method L-1076.6.1A is.

In particular, the present invention relates to an animal fiber, wherein it is assumed that the absorbance of an absorption band corresponding to the amide I is set to 1 in a reflection FT-IR measurement method, the degree of oxidation of an -SS bond (cystine bond) in an epidermal Cell of animal fiber having a relative extinction of not less than 0.1 in an absorption band of an -SO ₃ H group (sulfonic acid group) and / or a relative absorbance of not less than 0.08 in an absorption band of an -S-SO ₃ Na Group (Bunte salts) corresponds.

• a) einen ersten Schritt, bei dem eine -S-S--Bindung (Cystinbindung) in der Cuticulazelle einer tierischen Faser durch eine primäre Oxidation so behandelt wird, dass sie in einen niedrigeren oxidierten Zustand übergeht,
• b) einen zweiten Schritt, bei dem die primär oxidierte -S-S--Bindung durch eine Oxidation so behandelt wird, dass sie in einen oder mehrere der höher oxidierten Zustände des zweifach, dreifach oder vierfach oxidierten Zustands übergeht, und
• c) einen dritten Schritt, bei dem die -S-S--Bindung im höher oxidierten Zustand mit einer reduzierenden Spaltung behandelt wird.

The animal fiber is obtainable by a process comprising:

• a) a first step in which an -SS - bond (cystine bond) in the cuticle cell of an animal fiber is treated by a primary oxidation so that it changes into a lower oxidized state,
• b) a second step in which the primary oxidized -SS bond is treated by oxidation to transform into one or more of the more highly oxidized states of the double, triple or quadruple oxidized state, and
• c) a third step, in which the -SS - bond is treated in the higher oxidized state with a reducing cleavage.

• a) einen ersten Schritt, bei dem eine -S-S--Bindung in der Cuticulazelle einer tierischen Faser durch eine primäre Oxidation mit einem Oxidans mit der Fähigkeit zur Oxidation einer Cystin--S-S--Bindung in einer tierischen Faser behandelt wird,
• b) einen zweiten Schritt, bei dem die primär oxidierte -S-S--Bindung durch eine Oxidation mit Ozon so behandelt wird, dass sie in einen oder mehrere der höher oxidierten Zustände des zweifach, dreifach oder vierfach oxidierten Zustands übergeht, und
• c) einen dritten Schritt, bei dem die -S-S--Bindung im höher oxidierten Zustand mit einer reduzierenden Spaltung behandelt wird.

In particular, the method comprises:

• a) a first step, in which an -SS bond in the cuticle cell of an animal fiber is treated by a primary oxidation with an oxidant capable of oxidizing a cystine - SS bond in an animal fiber,
• b) a second step in which the primary oxidized -SS bond is treated by oxidation with ozone to transform into one or more of the more highly oxidized states of the double, triple or quadruple oxidized state, and
• c) a third step, in which the -SS - bond is treated in the higher oxidized state with a reducing cleavage.

The The present invention relates to an animal fiber which, in terms of Shrink-resistant and pill-resistance property, which by superior to one of the methods described above is.

Moreover, in the above description, supposing that the absorbance of an absorption band corresponding to the amide I is set to 1 in a reflection FT-IR measurement method, the oxidation degree of a -SS bond (cystine bond) refers to a relative absorbance of not less than 0.1 in an absorption band of an -SO ₃ H group (sulfonic acid group) and / or a relative absorbance of not less than 0.08 in an absorption band of an -S-SO ₃ Na group (Bunte salts) ",""the relative absorbance of an absorption band of -SO ₃ H group (sulfonic acid group)" in particular to a -SO ₃ H group (sulfonic acid group) corresponding relative absorbance of 1040 cm ^-1 , by the reflection FT-IR Measuring method (ATR method) in the case where the absorption band of 1650 cm ^-1 corresponding to the amide I is set to 1. In addition, "a relative absorbance in an absorption band of a -S-SO ₃ Na group (Bunte salts)" refers to a relative absorbance of the relative absorbance of 1024 corresponding to the -S-SO ₃ Na group (Bunte salts) cm ^-1 measured by the reflection FT-IR measuring method (ATR method) in the case where the absorption band corresponding to the amide I is set to 1 by 1650 cm ^-1 .

SUMMARY THE DRAWINGS

1 is a schematic longitudinal section illustrating an animal fiber.

2 are photographs of a Scanning Electron Microscope showing the surface of an untreated wool fiber and various shrink-treated fiber treated fibers.
(A) Untreated wool fiber,
(B) wool treated with chlorine,
(C) Wool fiber treated by the Chloro-Hercosett process,
(D) Wool fiber of the present invention.

3 Fig. 10 is a side view illustrating a processing apparatus used for the method of the present invention.

4 is a drawing that explains an ozone treatment method.

5 Fig. 15 is a drawing showing a state in which various wool fibers of Example 3 were macroscopically observed in terms of water repellency.

6 are light-microscopic photographs showing conditions of untreated wool fiber and various shrink-proof treated wool fibers in an all-word reaction.
(A) Untreated wool fiber,
(B) wool treated with chlorine,
(C) Wool fiber treated by the Chloro-Hercosett process,
(D) Wool fiber of the present invention.

DETAILED DESCRIPTION OF THE INVENTION

The Animal fiber of the present invention is characterized that they have superior shrink-resistant equipment and pilling resistance while, while they have a water repellency maintains, the animal fibers originally exhibit.

The Shrink proofing The animal fiber of the present invention is by use the felt shrinkage speed or the difference of the friction coefficient a single fiber marked as a measure.

If the shrink-proof equipment of the animal fiber of the present invention by the felt shrinking speed represents is, is she at a three-hour aqueous Do not wash more than 8%. Even more preferably, it is not more than 5%.

In the case where it is represented by the friction coefficient of a single fiber with respect to a value represented by the difference (μ _a -μ _w ) between the friction coefficient in the direction from the tip to the root (μ _a ) and the friction coefficient in Direction from the root to the tip (μ _w ) with respect to the fiber direction, it has a reduction of not less than 30% in terms of the static friction coefficient or the dynamic friction coefficient compared to that of an untreated animal fiber. Even more preferably, it has a reduction of not less than 40%. Moreover, the value of μ _{a is} about the same as the value in the case of untreated animal fiber, and the value of μ _w has an increase of not less than 30% as compared with the value in the case of untreated animal fiber.

Here, in the present invention, the felt shrinking speed becomes according to the method WM TM31 (Wool Mark Test Method 31), and a tissue that measured with a coverage factor C.F. of 0.41, with one strand of 14 Gage is used as a sample. Here, "according to the procedure WM TM31 "on the Fact that the measurements according to the test procedure of method WM TM31 based on ISO 6330 method carried out were, the test washing machine changed to a Cubex shrink test machine.

In the present invention, the friction coefficient of a single fiber is measured according to JIS L 1015, and the following conditions are used:
Test machine: Radar-type test machine for the friction coefficient
Load applied to the suspension cord: 200 mg
Peripheral speed of the cylinder: 90 cm / min.

In this case, μ _{a is} a friction coefficient in the direction from the tip to the root with respect to a fiber direction, and μ _w is a friction coefficient in the direction from the root to the tip with respect to a fiber direction.

The pilling resistance The animal fiber of the present invention is obtained by means of a Pill test method according to JIS L 1076.6 1A is represented quantitatively and is not lower than the third class of pill resistance.

Based on the above reference, the pilling test is carried out under the following conditions:
Test machine: Pill housing testing machine of the ICI type.
Knitted fabric: A fabric knitted using an IP18G is used.

The water repellency is determined by applying a water droplet to a knit consisting of the fibers to be tested and observing the penetration of the water droplet into the knit. The evaluation criteria are as follows:
O: A water droplet remains on the tissue for a period of 30 minutes (equivalent to natural animal fibers, etc.).
Δ: Practically all the water droplets penetrate into the tissue after a period of 2 to 30 minutes.
X: Practically all the water droplets penetrate into the tissue in less than 2 minutes.

Here the evaluation of water repellency can be done by adding a sample placed in the form of a sliver on the water surface and the period is measured, in which the sliver absorbed water and in the Water is sinking. In the animal fiber according to the present invention remains water droplets for one 30 minutes in the same way as natural animal fibers.

Furthermore the presence of a surface layer of epicuticle, which supplements the animal fiber by the water-repellent property the omnivorous reaction (Wool Science Review, Vol. 63 (1986)) Fiber into a saturated one Bleach solution or a saturated one Bromwasserlösung is dipped to determine the formation of bubbles on its surface.

The superior Properties of the fiber of the present invention are achieved by changing the conformation of the scale structure, and by means of a Illustration of the surface structure of Wool becomes the mechanism of the superior shrink-resistant equipment and the pill resistance is exercised, which inventors, etc. of the present invention have found explained below.

1 (from Wool Science Review, Vol. 63 (1986)) is a schematic longitudinal section showing the surface part of a wool fiber. A part of the epidermis tissue called the cuticle (cuticle) consists of an epicuticular layer ( 21 ), an Exocuticula A layer ( 22 ), an exocuticula B layer ( 23 ) and an endocuticle layer ( 24 ) as the innermost layer layered on top of each other in this order. In addition, the outer surface of the epicuticular layer is combined with a layer of about 0.9 nm in thickness consisting of a higher fatty acid (mainly eicosanoic acid) attached via a thioester bond to an -SH residue of a polypeptide chain in the epicutylic layer and the alkyl group of this eicosanoic acid allows the animal fiber to form a superior water-repellent property.

Farther have higher fatty acids, the outermost surface of the Represent fiber, in particular eicosanoic acid, which has a Thioesterbindung with an epicuticular layer (cysteine content: 12%) Water repellency on, and continue to form the epicuticular layer and an exocuticle A layer (Cystine content: 35%) next to the underside of the epicuticular layer an integrated structure that accounts for about 20% of the total thickness of the cuticle and cystine bonds are in an amount of about 70% on the total cystine content of the cuticle, concentric in this tissue distributed. It is known that the remaining approximately 30% off an exocuticula B layer (cysteine content: 15%) and an endocuticle (cystine content: 3%).

The majority of the cuticle tissue consists of exocuticula A and B layers and an endo cuticle layer, and the exocuticula A layer forms an integrated tissue structure with the epicuticular layer, and the phenomenon of felting substantially depends on the exocuticula B layer and the endocuticle layer.

If An animal fiber immersed in water absorbs each layer Water more or less and swells. But of course the extent of the swelling with water the lower the more the cystine crosslinking is formed is. And therefore, the endocuticle layer swells at which it is is the innermost layer, with a lower cystine crosslink density, when an animal fiber is immersed in water, sprinkle with water and expands, whereas, in contrast, the outer layer, the exocuticle layer with a higher one Cystine crosslink density, to a lesser extent with water, and therefore, the extent of the Expansion in the exocuticle layer lower. Such a difference of expansion by a difference of Quellens leads cause the scale to straighten up, causing mutual entanglement of fibers, whereby a felting is effected.

Especially entangles fibers with each other, and on the tangled parts are other fibers by an external force, at the time of the aqueous Wash on the fabric, entangled, so that all fibers be pulled into the tangled parts, causing a shrinking over the Length of the entire piece of fiber effecting felting, thus felping leads to another Shrink.

The animal fiber of the present invention, with respect to the Shrink proofing and pill resistance superior is, becomes mainly obtained by a chemical modification of the epidermis tissue, and the swelling properties of the exocuticula B layer and the endocuticle layer are practically matched to each other, with the water-repellent Property of eicosanoic acid on the top surface is maintained so that the erection of the scales even then, When the fiber is immersed in water, it is virtually eliminated.

In other words, while the integral structural body the epicuticular layer and the exocuticula A layer, in which it is a hard structure in terms of organized structure act, maintain, d. h., while the repellency causing eicosanoic acid is obtained, only the exocuticula B layer is selectively attacked, so that their cystine binding, i. H. their network structure, broken becomes. Only those parts of the fiber surface, especially those which concern the swelling and shrinking become the modification whereby the inside of the fiber is protected, whereby the resulting Feature is that the water-repellent property of entire fiber is retained and the strength of the fiber as well is maintained.

The above-mentioned structural change by the treatment of the present invention is confirmed by a reflection FT-IR measuring method (ATR method). The structure within 1 μm of the surface is reflected in the reflection FT-IR measurements, and this is equivalent to the thickness of the epidermis tissue of the animal fiber, which is about 1 μm. With regard to the FT-IR extinction of the animal fiber subjected to the modifying treatment, both the relative absorbance in the absorption band of 1040 cm ^-1 corresponding to the -SO ₃ H group (sulfonic acid group) and the absorption band of 1024 cm ^-1 corresponding to the -S-SO ₃ Na group (Bunte salts) obtained in the case where the absorption band corresponding to amide I (1650 cm ^-1 ) is set to 1, a gain compared to the relative extinction of untreated animal fibers, suggesting that the cross-linking bond of the exocuticula B bond has been broken.

in the Contrary to this, in the case of an animal fiber, by a Chlorine treatment process or a Chlorine-Hercosett process etc., which is a typical conventional method, is obtained, the integral structural body of the epicuticle layer and the Exocuticula-A layer directly attacked, and in particular the epicuticular layer is severely damaged with the consequence that the water-repellent layer is destroyed, rendering it water-repellent Property that originally had the animal fiber loses. About that comes it leads to a deterioration of the strength, because of the oxidation process applied to the entire fiber becomes. About that In addition, the conventional Shrink-resistant Animal fiber has a smoother flake surface, so in comparison to the animal fiber of the present invention wherein the dandruff are maintained, a reduction in stretch-resistance to abrasion a single fiber, resulting in sufficient pilling resistance not received.

2 FIG. 12 shows the results of surface observation of the animal fiber of the present invention, the shrink-treated fiber treated by the conventional method, and FIG natural, untreated animal fiber under an electron microscope. In 2 shows (A) an untreated wool fiber, shows (B) a chlorine-treated wool fiber shows (C) a wool fiber treated by the Chloro-Hercosett method and shows (D) a wool fiber of the present invention. It is confirmed that the animal fiber of the present invention maintains a surface state which is practically the same as in the natural state, as compared with the conventional shrink-finished animal fiber having a relatively smooth surface with hardly any dandruff observed.

Here the animal fiber of the present invention comprises wool, mohair, Alpaca, cashmere, llama, vicuna, camel and angora.

A Animal fiber with a relatively poor utility in terms of pill characteristic, the feature described above can by the manufacturing method described below according to the present Invention are produced.

The A method of making an animal fiber of the present invention Namely, the invention comprises that an animal fiber sliver first with a Oxidant, the ability for the oxidation of a cystine S - S bond of the animal fiber, primary is oxidized and then to ultrafine an ozone-oxygen gas mixture vesicle of 5 μm or less in water is made by adding a tap mixer is used, and then present in this state gas for a given period against the previously primarily oxidized animal fiber is collapsed, causing a gas phase reaction in the liquid causing the oxidation of the cystine bond of the wool to one higher oxidized Condition leads. Then it becomes a higher one Stage oxidized animal fiber carried out a reduction treatment, thereby cystine crosslinking (-S-S-) is cleaved.

And The method of the present invention also has the feature that it the sliver of animal fiber, the combined effect of Shrink proofing and the pill resistance can lend continuously.

Namely, in the present invention, the primary oxidized state of a cystine bond (-SS-) means the state oxidized to a lower order, the mono-oxidized state (-SO-S-), the dioxygenated state (-SO ₂ -S-) or a mixed one Condition of it. In particular, it means the state rich in the mono-oxidized state. In contrast, the state oxidized to a higher order means the dioxygenated state and the trioxide state (-SO ₂ -SO-), the tetra-oxidized state (-SO ₂ -SO ₂ -), or a mixed state thereof.

It is known that, although a cleavage of a -S-S bond by a reducing agent is not easy in the case of the mono-oxidized state is and longer lasts, the cleavage in the di-, tri- and tetra-oxidized state relative is easily effected.

The The present invention is characteristic in that it effects a two-stage oxidation, comprising a first stage, in which an animal fiber by block fumes with an oxidant with the ability for the oxidation of a cystine S - S group of animal fiber primary Oxidation treatment is subjected, and a second stage, at the one oxidation to a higher one Order performed is made by an aqueous Treatment liquid, the ozone in the form of ultrafine bubbles of 5 μm or less in the aqueous treatment solution contains for effectively splitting a cystine bond only in the cuticle areas animal fiber, namely in a short period of time without any unevenness of treatment, injected becomes.

Then is a gas mixture of ozone and oxygen, which with an ozone generating device is generated in a liquid circulation pump blown in, furthermore an aqueous ozone treatment liquid, the ozone in the form of ultrafine bubbles of 5 microns or less contains made by means of a line mixer, this liquid is injected in water onto a previously oxidized animal fiber, causing quickly and preferably an exocuticula B layer, in a cystine S - S bond was previously oxidized to give an oxidation state with higher Order in the B-layer is oxidized with ozone.

Then becomes a cystine (- S-S) bond by a reduction treatment with a reducing agent, for example a sulphite, split, thereby reducing the cystine crosslink density of the exocuticle B layer which, as a consequence, causes swelling, fluidization and the solubilization promoted with water become, and you leave pour a portion of the protein out of the fiber.

According to the present Invention will undergo the cystine crosslink density of this exocuticle B layer the implementation a pre-oxidation, an oxidation by ozone and a reduction treatment is reduced with a sulphite, and as a result of this becomes a swelling in water of about the same order of magnitude obtained at the endocuticle, and the bilateral function of the exocuticula B layer and the endocuticle is made to disappear. And therefore judges the edge of the dandruff even when the animal fiber is dipped in water, not on, and a shrinkage in the aqueous Washing is not done. At the same time, a higher level of shrink-resistant equipment is obtained, without the water repellency is deteriorated, because the epicuticular layer and the thioester of eicosanoic acid, the their surface covered, remain. And continues, because the dandruff in the fiber held, the extraction force when pulling out a fiber the fiber arrangement higher, and a fiber movement in the fiber assembly is suppressed, which compared to a shrinking process, in which the scale peeled off or removed, or a process of shrinking, where the surface the scale is coated with a resin, corresponding to one Antipilling leads.

The Method for producing the animal fiber of the present invention Invention is characterized by a two-stage oxidation comprising a first stage where animal fiber is primarily oxidized, and a second stage Stage at which the primary oxidized animal fiber is oxidized to a higher order, and comprising a subsequent reduction step to a higher one Order to split oxidized cystine bond.

The Method for producing the animal fiber of the present invention Invention is described in more detail below.

Of the The first step in this process is a pretreatment step for the oxidation of a cystine bond with ozone, and it is one step at which there is a cystine bond in the cuticular tissue the fiber with an oxidant with the ability to oxidize a -S-S - binding of an animal fiber is primarily oxidized, creating a essentially mono-oxidized state is obtained.

When preferred, to primary Oxides oxidans used are persulfuric acid, peracetic acid, performic acid, peracids and neutral salts or acid salts of these peracids or potassium permanganate, Hydrogen peroxide and the like are exemplified, and these can used alone or in admixture of two or more. A particularly preferred oxidant is potassium hydrogen persulfate.

The primary Oxidation takes place by the pre-oxidation by means of a pad (impregnation) damping (reaction) process, in some cases by pad storage (reaction at room temperature). Usually, if Potassium persulfate is used, a dipping method is used, and in this case, a treatment reagent penetrates into the inner Parts of the fiber, and the fiber or the entire fiber is oxidized and hydrolyzed, whereby a cystine bond is cleaved, thereby a deterioration of mechanical properties such as strength, the stretching and the like is effected. Nevertheless, a shrinking did not get the making effect. Furthermore, in a method, in the potassium hydrogen persulfate padded (impregnated) and stored (at room temperature left), no reaction with the fiber, and cuticle is not sufficiently oxidized, provided that the reaction temperature is not or exceeds room temperature (essentially 32 ° C). In According to the present invention, the treatment condition should be dependent on the type of oxidant used and its reactivity towards the fiber and in the case of using potassium hydrogen persulfate oxidizes the block (impregnation) steam (reaction in the heat) procedure a cystine bond only in cuticular areas, while it inhibits the oxidation of prevents internal areas of the fiber, reducing the subsequent oxidation from cuticle areas to a higher one Order with ozone is facilitated.

at this primary Oxidation stage, a Exocuticula B layer is first primarily oxidized (first stage). Compared to an exocuticula B layer is in Tissue of the epicuticular layer and the exocuticula A layer, the in contact with it, the cystine S-S crosslink density very high, and as a result, the fabric has a very high hardness and has a chemical resistance and abrasion resistance (The tissue of this epicuticle part is eventually replaced by a Hydrolysis with 6 N hydrochloric acid decomposed. Therefore, the epicuticle in histology as resistant Treated membrane). Accordingly, the Exocuticula B layer compared to the epicuticular layer and the Exocuticle A layer relatively more sensitive to oxidation.

Namely, in the first step, a wetting agent is placed in a bath containing an aqueous Oxidation solution is filled, the bath temperature is controlled to a temperature as possible below room temperature, the padding (impregnation) is carried out so that the liquid contact time with the animal fiber is several seconds (about 2 to 3 s), the fiber is at a Step where the aqueous oxidant solution has not reached the inner parts of the fiber and sufficiently penetrated into the cuticle, removed from the pad bath and immediately expressed with a defect, so that the added amount of the aqueous oxidant solution remains constant. The fiber thus containing a given amount of the aqueous oxidant solution is then treated at temperatures of about 95 ° C in a steaming apparatus to promote the primary oxidation reaction while avoiding drying of the fiber.

Here The term "padding" does not mean impregnation the fiber with a liquid by mere Placing the fiber in a bath, but an impregnation, with it in the dipping bath with regard to the chemical reactivity of with the animal fiber used Oxidans no reaction is effected. It means poor reaction conditions, namely a selection of a wetting agent with a high permeability, that is not decomposed by an oxidant in a bath, the regulation the temperature in a bath so that it is as low as possible so that a reaction with the fiber is suppressed, and one for a short Period as several seconds of immersion and immediately then a phrase.

Of the second step in the treatment process is a stage in which an animal fiber that primarily oxidizes by means of an oxidant was, with ozone to a higher Order is oxidized. Usually is a long period of time required for oxidation with ozone and the formation of an oxidation step leading to cleavage of a cystine bond is sufficient, is difficult. That means that if it is an animal Fiber is oxidized with ozone, which is required animal fiber with ozone gas or ozone dissolved in water at a high concentration for 10 to treat for 30 min, and under such conditions was one continuous treatment impossible. In the present invention, one with ozone becomes a higher order successful oxidation in a short period of time by carrying out the primary Oxidation in the first stage as a pretreatment process and the Provision of ozone in a special condition and simultaneous Achieving the contact process with the fiber with ease allows and thus a continuous treatment step has become possible.

The Namely, the present invention is characteristic in that ozone with a high concentration in the form of ultrafine bubbles of 5 μm or less is dispersed in water and further this aqueous treatment liquid, which contains ozone in such a state, blown on an animal fiber which causes a gas-solid reaction with ozone as a gas phase is effected.

The Development of a bursting ultrafine bubbles preventing Device, the ultrafine bubbles of 5 μm or less, which consists of a line mixer on the surface of a perforated suction drum are discharged, and increasing the Number of collisions of ultrafine bubbles with the fiber also contributed to completion of the present invention.

at the oxidation treatment with ozone in the form of finely divided in water vesicle prevents the presence of bubbles in water in general a wetting of the fiber with liquid and practice an adverse effect on the wetting ability of the liquid out. In the present invention, as a means for solving this Disadvantage has been applied to a means in which first the fiber an upper sliver of animal fiber by means of a rotary gill sufficiently open will, making a thin Fleece is formed as a belt, which on the surface of a perforated suction drum is wound, and an ozone-oxygen gas mixture becomes ultrafine bubbles of 5 μm or smaller using a line mixer made, and the liquid is sucked in to increase the number of collisions with the fiber increase, allowing penetration of these ultrafine bubbles between the fibers, which in turn promotes oxidation by ozone.

The present invention will be described with reference to FIG 3 described method described in detail. For example, the sliver of animal fiber is a sliver of about 25 g / m, and the fibers on the nine yarns of the slabs are opened by means of a pacemaker, thereby forming a belt, and the draw ratio is about 1.4 times up to 4 times, preferably 1.66 times, although it varies depending on the fineness of the wool. The feed rate of the wool-combing train is 0.2 m / min to 4 m / min, preferably 0.5 m / min to 2 m / min.

The wool-combed train formed into a belt shape is immersed in an aqueous solution containing an oxidant and a wetting agent and expressed with a squeeze-out defect. Examples of the oxidant include persulfonic acid, persulfates or acid persulfates such as potassium hydrogen persulfate, sodium hy drug persulfate, ammonium persulfate, potassium persulfate and sodium persulfate, potassium permanganate, hydrogen peroxide, performic acid or salts thereof, peracetic acid or salts thereof and the like. Particularly preferred is potassium hydrogen persulfate [trade name: "Oxone" (2KHSO ₅ · KHSO ₄ · K ₂ SO ₄ , the active composition as KHSO ₅ content represents 42.8%) manufactured by EI du Pont de Nemours and Company] because it is in the form of a grain, readily dissolves and an aqueous solution containing the dissolved oxidizing agent is storage stable at a temperature of 32 ° C or less. As the wetting agent, "Alcopol 650" (manufactured by Chiba Specialty Chemicals KK) is preferable because it is stable to an oxidizing agent. The concentration of the oxidant in the case of the potassium hydrogen persulfate "oxone" is 10 g / L to 50 g / L, preferably 20 g / L to 40 g / L when the squeezing ratio is 100% although it varies depending on the kind of the oxidant , The concentration of the wetting agent is suitably about 2 g / l in the case of "Alcopol 650". The temperature of the padding liquid is preferably as low as possible so that no reaction is effected in the liquid. It is more preferably from 15 ° C to 25 ° C. It is preferable that the pH of the liquid is on the acidic side. Even more preferably, the pH is 2.0.

To the expressions in a lack of expression an oxidant will react with the sliver of animal fiber left, and the treatment conditions vary depending of the type of oxidant. For example, in the case of potassium permanganate, Hydrogen peroxide, performic acid or peracetic acid a method recommended in which an aqueous solution of these compounds padded and then is recommended to be kept at room temperature. The exposure time can be advantageously 2 to 10 minutes, although they dependent on varies depending on the type and concentration of the oxidant. In case of Potassium persulfate, potassium persulfate, sodium persulfate or Ammonium persulfate can be a primary Oxidation reaction advantageous after padding an aqueous solution this compound by means of a taking place under atmospheric pressure steaming treatment carried out become. With regard to the damping conditions are a temperature of 95 ° C and a period of 5 to 15 minutes, preferably about 10 minutes, to carry out the primary Oxidation sufficient.

A characteristic of animal fiber is that the cystine (- SS) content varies depending on the tissues making up the cuticle and cortex. Specifically, in the present invention, to provide shrink-proofing equipment and pilling resistance, modification of the cuticle tissue is performed. The oxidation of a cystine bond, -SS-, then proceeds as described below, and the -SS bond is cleaved after the hydrolysis and the reducing treatment, and finally sulfonic acid (-SO ₃ H) is obtained.

The The present invention has the feature that a reaction by means of a pad damping method with an oxidant, for example potassium hydrogen persulfate, is carried out wherein the reaction of the -S-S bond is substantially mono-oxidized Condition is stopped and in the subsequent step with ozone too a higher one Order is oxidized.

By the application of this process increases the speed the oxidation reaction compared to that oxidation rate, when ozone alone or potassium hydrogen persulfate are used alone, remarkable, and a continuous treatment of a sliver From animal fiber becomes possible for the first time, which is a success leading to industrialization, if an -S-S bond is primarily oxidized first and then by ozone is oxidized as illustrated in the following formula:

The present invention is characteristic in that an ozone-oxygen gas mixture is bounced against an animal fiber sliver by bubbling the gas in the form of ultrafine bubbles of 5 μm or less in water, thereby causing higher-order oxidation by means of a gas-phase reaction. With regard to the apparatus for producing ozone, an ozonating apparatus having a generating capacity of about 250 g / h (for example, one manufactured by Chlorine Engineering KK) can sufficiently effect a continuous treatment of an animal fiber sliver, and Example has an ozone gas generated by feeding oxygen gas into the ozonating apparatus at a rate of 40 l / min, a weight concentration of 6.5% by weight and a volume concentration of 0.1 g / l in the gas mixture, and in FIG For example, treatment with an ozone-oxygen gas mixture of 4 g / min was an optimal condition, although it depends on the extent of primary oxidation and other conditions. The amount supplied to impart shrinkage resistance and pilling resistance to wool fiber is 6% by weight or less, preferably 1.5 to 5% by weight, based on the weight of the wool, though it varies depending on the quality of the wool fiber.

One Feature of the present invention is that the ozone gas for one efficient implementation with wool is formed into bubbles in Water as fine as possible are the bubbles bounced against wool and at the collision point an oxidation is effected. Therefore, too, because the solubility ozone in water is extremely low, hence only cuticula fabric of wool oxidized, and cuticula tissue, which is internal tissue is protected, protected which further enhances the Effect of modifying the Wolloberfläche leads. As a method of preparation of an ozone-oxygen gas mixture as ultrafine bubbles of 5 μm or less a method is preferred in which the gas mixture in a Water jet pump introduced and by an increase of the water pressure against small walls in a cylinder bounce is left, whereby ultrafine bubbles are obtained.

A feature of the present invention is also that a special, in 4 as shown, apparatus for collecting ultrafine bubbles produced in a line mixer was used and the bubbles were blown onto a wool fiber belt in the form of a belt. Woolen fiber tape ( 2 ) in the form of a primary oxidized belt is placed between power belts ( 1 ) and ( 3 ) and placed in an ozone treatment basin ( 9 ) transferred with a suction drum ( 5 ), where the ultrafine bubbles through a nozzle ( 6 ) from a line mixer ( 13 ) are blown on the present in the form of a belt wool fiber tape. And for collecting these ultrafine bubbles on the wool-fiber ribbon present in the form of a belt, a device ( 4 ) for collecting ultrafine bubbles at the edge of a suction drum, and further the ultrafine bubbles containing liquid from the middle part ( 7 ) sucked the suction drum, whereby the ultrafine bubbles can bounce against the present in the form of a belt Wollfaserband. An ozone-oxygen gas mixture that is used in an ozonizer ( 11 ) is introduced into a water jet pump ( 12 ) to cause the mixing of the gas with the liquid, and the mixture is increased by increasing the pressure of the line mixer ( 13 ), thereby producing ultra-fine bubbles which are blown onto the belt-shaped wool-fiber ribbon sandwiched between stainless steel sieve belts. Furthermore, the surface oxidation of the wool fiber by the use of a through a suction port ( 7 ) sucking device completes.

Although ozone is said to be strong and fluoride the strongest oxidant, its reactivity on the acidic and alkaline sides is different. On the acid side, namely: O ₃ + 2H ⁺ + 2e ^- = O ₂ + H ₂ OE _o = 2.07V while on the alkaline side: O ₃ + H ₂ O + 2e ^- = O ₂ + 2OH ^- E _o = 1.24 V and, on the acid side, the standard oxidation potential is higher, and the solubility of ozone in water is greater and the half-life much longer. (The half-life is 1 s at a pH of 10.5 and at a pH of 2.0 to 105 s.)

The ozone oxidation is carried out on the acid side at a pH of 1.5 to a pH of 2.5, preferably at a pH of 1.7 to a pH of 2.0. Ozone has a higher solubility in cold water but lower reactivity. To increase the reactivity, the treatment temperature must be increased and the treatment temperature may advantageously be 30 ° C to 50 ° C, and if it is too high, an ozone-oxygen gas mixture has a higher molecular motion and splatter from a treatment basin. A particularly preferred temperature is 40 ° C. The reaction can be controlled by the reaction time, the feed rate of the wool fiber tape, namely the contact time with the liquid in the ozone treatment tank. When the feeding speed of the sliver is 0.5 m / min, the contact time is 2 min, and when it is 2 m / min, the contact time is 33 sec, and the shrink-proof control and the pill-resistance control are by controlling the reaction time possible.

The in the ozone treatment by ozone oxidized wool fiber tape is with a reducing agent is treated, and only then is an -S-S bond according to the illustration split in the following formula.

at In particular, this method is characterized by the cuticula tissues Exocuticula B layer attacked, and thus the cystine S-S crosslink density decreases and the source property with water increases to the same water source grade like that of the endocuticle too, and consequently the bilateral property of the dandruff of the animal fiber, thereby a raising of the scale edge in water is prevented. Therefore does not do the water-repellent function, a feature of wool lost, and a higher one Degree of shrink-proof equipment and pill resistance can be lent while the water repellency preserved.

The reducing agent is not particularly limited, and sulfites are suitable. Of the sulfites, sodium sulfite, Na ₂ SO ₃ (pH 9.7), more than acid sodium sulfite, NaHSO ₃ (pH 5.5), is preferred. Because the primary oxidation and the ozone oxidation are performed on the acidic side, the reduction treatment on the alkaline side is also preferable from the standpoint of the neutralization treatment. The concentration of sodium sulfite is preferably 10 g / l to 40 g / l, and more preferably about 20 g / l. The temperature is preferably 35 ° C to 40 ° C, and more preferably about 40 ° C.

It is preferred, the rinsing in water in two stages while overflowing is carried out, both to remove the remaining sulfite and dissolved protein to remove from the treated wool. The temperature can be beneficial about 40 ° C be.

After rinsing with water, a softening agent and spinning oil agent may be added to the last basin in view of the handle and spider nature of the woolen fiber tape. For example, the treatment may also be carried out at 40 ° C by:
1 g / l Alcamine CA New (manufactured by Chiba Specialty Chemicals KK) and
1 g / l Croslube GCL (manufactured by CTC Textiles Ltd./Miki KK)
be added.

The Drying is preferably carried out at relatively lower temperatures from about 80 ° C in a suction-type dryer to prevent yellowing in the heat.

• A) im Fall der Oxidation nur durch eine Ozonbehandlung:
• 1) Ozon hat eine extrem niedrige Löslichkeit in Wasser, die 39,4 mg/l bei 0°C, 13,9 mg/l bei 25°C und 0 mg/l bei 60°C beträgt, und vom Standpunkt einer kontinuierlichen Behandlung von Faserband aus tierischer Faser aus wird die Behandlungsdauer aufgrund der niedrigen Konzentration zu lang, um für eine kontinuierliche Behandlung geeignet zu sein. 2) Eine große Menge an wässriger, gelöstes Ozon enthaltender Lösung ist erforderlich. 3) Eine Vorrichtung, die Ozon in hoher Konzentration erzeugt, ist notwendig, wodurch die Gerätekosten erhöht werden. 4) Wenn Ozongas mit einer hohen Konzentration verwendet wird, sind ein vorsichtiger Umgang mit dem Abgas und der Arbeitsumgebung an dieser Stelle erforderlich.
• B) Im Fall des Vergleichs eines Tauchverfahrens mit einem Klotzdämpfverfahren hinsichtlich der Oxidation von Kaliumhydrogenpersulfat und dergleichen:
• 1) Eine ionische Bindung (-NH₃ ^+–OOC-) ist eine derjenigen Seitenketten, die in die Stabilisierung von Polymerketten in tierischer Faser eingebunden sind, und als Folge davon, dass Chemikalien wie Kaliumhydrogenpersulfat bei einer höheren Temperatur für einen längeren Zeitraum in einem diskontinuierlichen Tauchverfahren umgesetzt werden, werden das Kalium(+)-Ion, das Wasserstoff-(+)-Ion oder das Persulfat(–)-Ion von -NH₃ ⁺ oder ^–OOC- angezogen und die ionische Bindung zerstört und weiterhin die -S-S--Bindung gespalten. Dies führt zu einer Erniedrigung der Festigkeit, der Dehnung und dergleichen der Faser, und die Wirkung der Schrumpfechtmachung kann nicht erhalten werden.
• 2) Andererseits wird bei demjenigen Verfahren, bei dem tierische Faser nur mittels Klotzdämpfen unter Verwendung von Kaliumhydrogenpersulfat oxidiert wird, der Schritt des Klotzverfahrens mit der Absicht verwendet, unter derjenigen Bedingung zu tauchen, bei der tierische Faser und Kaliumhydrogenpersulfat nicht reagieren. Daher wird die Temperatur einer wässrigen Lösung von Kaliumhydrogenpersulfat (Stabilisierungstemperatur der wässrigen Lösung, 20°C oder niedriger) erniedrigt, das Tauchen in dieser wässrigen Lösung wird für einen kurzen Zeitraum (2 bis 3 s) bewerkstelligt, und die tierische Faser wird durch Ausdrücken mit einer Mangel sofort mit einer bestimmten Menge an Kaliumhydrogenpersulfat imprägniert. Und dann wird dies durch Dämpfen erwärmt, und anschließend kann eine Reaktion nur in denjenigen Bereichen erfolgen, in denen die tierische Faser sich in Kontakt mit dem Reagens befindet. Bei diesem Verfahren dringt das Reagens nicht in innere Bereiche der Faser ein, sondern führt nur zur Oxidation der Oberflächenschicht, und das innere Gewebe wird geschützt, was zur Schrumpfechtmachung und der Pillbeständigkeit beiträgt, was auf eine Modifizierung des Oberflächengewebes hin deutet, die der Aufgabe der vorliegenden Erfindung entspricht.
• C) Im Fall einer Ozonbehandlung nach der Vorbehandlung mit einem Oxidans wie Kaliumhydrogenpersulfat und dergleichen:
• 1) Sobald die tierische Faser primär oxidiert ist, wird sie schnell mit Ozon oxidiert, wobei die Oxidation einer tierischen Faser in einem kurzen Zeitraum abgeschlossen ist und eine kontinuierliche Behandlung ermöglicht wird. 2) Aufgrund der vorherigen primären Oxidation wird eine Oxidationsreaktion mit Ozon mit niedriger Konzentration ausreichend gefördert, und folglich wird eine kontinuierliche Behandlung eines Faserbandes aus tierischer Faser mittels einer Vorrichtung, die Ozon mit einer niedrigeren Konzentration erzeugt, möglich. 3) Aufgrund der Ozon mit einer niedrigeren Konzentration erzeugenden Vorrichtung wird die Arbeitsumgebung nicht beeinträchtigt. 4) Aufgrund der Ozon mit einer niedrigeren Konzentration erzeugenden Vorrichtung kann die Investition in die Vorrichtung klein sein.

Various oxidation processes for the animal fiber are compared and considered below.

• A) in the case of oxidation only by ozone treatment:
• 1) Ozone has an extremely low solubility in water, which is 39.4 mg / L at 0 ° C, 13.9 mg / L at 25 ° C and 0 mg / L at 60 ° C, and from the standpoint of continuous treatment From fiber-fiber sliver, the treatment time due to the low concentration becomes too long to be suitable for continuous treatment. 2) A large amount of aqueous solution containing dissolved ozone is required. 3) A device that generates ozone in high concentration is necessary, thereby increasing the equipment cost. 4) When using high concentration ozone gas, careful handling of the exhaust gas and working environment is required at this point.
• B) In the case of comparing a dipping method with a pad damping method with respect to the oxidation of potassium hydrogen persulfate and the like:
• 1) An ionic bond (-NH ₃ ^{+ -} OOC-) is one of those side chains involved in the stabilization of polymer chains in animal fiber, and as a result of chemicals such as potassium hydro be reacted at a higher temperature for a longer period of time in a batch dipping process, the potassium (+) - ion, the hydrogen - (+) - ion or the persulfate (-) - ion of -NH ₃ ⁺ or ^- OOC- and the ionic bond is destroyed and the -SS bond is further cleaved. This results in a lowering of the strength, elongation and the like of the fiber, and the effect of shrinking can not be obtained.
• 2) On the other hand, in the method in which animal fiber is oxidized only by means of block vapors using potassium hydrogen persulfate, the step of the padding method is used with the intention of submerging under the condition where animal fiber and potassium hydrogen persulfate do not react. Therefore, the temperature of an aqueous solution of potassium persulfate (stabilizing temperature of the aqueous solution, 20 ° C or lower) is lowered, the dipping in this aqueous solution is accomplished for a short period of time (2 to 3 sec), and the animal fiber is expressed by expressing a deficiency is immediately impregnated with a certain amount of potassium hydrogen persulfate. And then this is heated by steaming, and then a reaction can only occur in those areas where the animal fiber is in contact with the reagent. In this method, the reagent does not penetrate into internal regions of the fiber, but only leads to oxidation of the surface layer, and the inner tissue is protected, contributing to shrinkage and pilling resistance, suggesting a modification of the surface weave which is the object of the corresponds to the present invention.
• C) In the case of ozone treatment after pretreatment with an oxidant such as potassium hydrogen persulfate and the like:
• 1) Once the animal fiber is primarily oxidized, it is rapidly oxidized with ozone, whereby the oxidation of an animal fiber is completed in a short period of time and a continuous treatment is enabled. 2) Due to the previous primary oxidation, an oxidation reaction with low concentration ozone is sufficiently promoted, and hence, continuous treatment of an animal fiber sliver by means of a device producing ozone at a lower concentration becomes possible. 3) Due to the ozone with a lower concentration generating device, the working environment is not impaired. 4) Due to the ozone with a lower concentration generating device, the investment in the device can be small.

As described above allows the two-stage oxidation method used in the present invention an unexpectedly effective oxidation caused by an oxidation treatment either with an oxidant or with ozone is not obtained.

In The present invention will be described according to the above description Cystine binding by oxidation of an animal fiber to a higher Order and the subsequent reduction treatment divided evenly, and consequently, those with shrink-resistant equipment and pill-resistance Equally equipped animal fiber obtained by continuous steps. In the thus obtained treated animal fiber becomes the exocuticula B layer selectively attacked, and the integrated structure of the epicuticle and the exocuticula A layer, which is a structural hard tissue remains, and thus remains the the water repellency resulting eicosanoic acid also obtained, and the water repellency of the entire fiber and the fiber strength is also retained.

Because, in a chlorination reaction of an animal fiber, a cystine - (-S-) bond is oxidized and hydrolyzed to give sulfonic acid (-SO ₃ H), and because a peptide chain constituting the animal fiber is split in addition to cleavage of a cystine bond, the tensile strength and elongation of the fiber are lowered. Also, the bond formed by thioester bonds formed between eicosanoic acid, which is the outermost film of an animal fiber, and an -SH group in a polypeptide chain is broken, thereby converting the hydrophobicity into a hydrophilicity. Therefore, the wool disappears its own water-repellent function.

(| und – bedeuten eine Polypeptidkette.)A reaction mechanism by a chlorination reaction is shown below.

(| and - mean a polypeptide chain.)

DESCRIPTION THE PREFERRED EMBODIMENTS

Examples

example 1

Woolen fiber tape was made according to a in 3 described process diagram treated continuously. The running speed of the sliver through the processes, namely, a pad treatment deficiency, an ozone treatment tank, a water rinse treatment tank and a drying method was 2 m / min.

Padding treatment method

sliver with 9 yarn threads (25 g / m) from merino wool with 20.7 microns from Australia were put into a rotary and the fibers of the woolen fiber tape became a belt open, by having a relationship of 1.66 was stretched. The belt sliver was in a solution with the following composition and paddled by means of a defect expressed.

composition the aqueous padding solution

• Potassium hydrogen persulfate, KHSO ₅ : the concentration is 40 g / l ("Ozone", manufactured by EI du Pont de Nemours and Company)
• Wetting agent "Alcopol 650 ": the concentration is 2 g / l (manufactured by Chiba Specialty K.K.)

treatment condition

• Contact duration: 2 min
• Temperature: room temperature
• pH: 2.0
• Ausdrückgeschwindigkeit: 100%

It was expressed by a defect and then transferred to a steaming process.

Steaming process

Wool fiber tape wetted in the form of a belt was subjected to steaming on a conveyor belt under the following conditions.
95 ° C, 10 min

To In the steam treatment, the sliver became an ozone treating tank directed.

Ozone treatment process

The Steam-treated sliver became an ozone treatment tank of Suction type and under the following conditions using ozone oxidized.

One Ozonizer ("OZAT CFS-3 "manufactured from Chlorine Engineering K.K.) was used at 250 g / h, and As an oxygen source, an oxygen cylinder was used.

The oxygen feed rate to the "ozonizer OZAT CFS-3" was 40 l / min.
Ozone production, concentration by weight: 6.5% by weight
Ozone production, concentration by volume: 0.1 g / l
Ozone production, amount: 4 g / min
Apparent ozone supply to wool: 1.48 by fiber weight 25 g / m × 9 × 1 / 1.66 = 135.5 g / m wool 135.5 g / m × 2 m / min × contact time 0.55 min (33 s) = 149.05 g of wool 4 g / min (O 3 ) × 0.55 min = 2.2 g O 3 2.2 g / 149.05 × 100 = 1.48% by weight of fiber O 3

The generated ozone gas was passed through 4 pumps with a water lift amount of 80 l / min in four-pipe mixers. The ozone injection amount in each line mixer was 10 l / min, and the total amount was 40 l / min. The ultrafine bubbles were allowed to bounce against the woolen fiber tape on the suction drum by blowing the bubbles through an in 4 In addition, the spraying of ultra-fine vesicle preventing apparatus was inflated, and further, the treating liquid was sucked from the inside of the drum and circulated to the outside of the drum to increase its residence time, and the ozone treatment was carried out under the following conditions.
Ozone bubbles: ultrafine bubbles of about 5 μm
Treatment temperature: 40 ° C
pH: 1.7 (adjusted with sulfuric acid)
Contact time: 33 s

To the ozone treatment, the sliver was transported to a reducing tank.

Reduction treatment method

The ozone-treated belt-shaped sliver was treated under the following conditions in a suction-type reducing tank.
Sodium sulfite, Na ₂ SO ₃ : 20 g / l
pH value: 9.7
Temperature: 40 ° C
Contact time: 33 s

To In the reduction treatment, the sliver became a water sink transported.

Wasserspülbehandlungsbecken

The in the form of a belt, subjected to a reduction treatment Sliver was for 33 s in a water sink of the suction type treated with warm water of 40 ° C. After rinsing with Water became the sliver to another water rinse treatment tank transported further.

Wasserspülbehandlungsbecken

The in the form of a belt, subjected to a reduction treatment Sliver was for 33 s in a water sink of the suction type treated with warm water of 40 ° C. After rinsing with Water, the sliver was transported to the last basin to it with a spinning oil and a Schmälzmasse to provide for the subsequent ones Procedures were necessary.

Spinning oil and lubricating mass treatment method

The in the form of a belt present, rinsed with water sliver was for 33 s in a water sink of the suction type with warm water of 40 ° C containing the following treatment agents had been added, treated.

treatment agents

• 1 g / l "Alcamine CA New " (produced Chiba Specialty Chemicals K.K.) and
• 1 g / l "Croslube GCL " (produced CTC Textiles Ltd./Miki K.K.).

To the oil treatment The sliver was transported to a dryer.

drying process

The Drying became at 80 ° C using a hot air dryer carried out by suction.

The treated belt-shaped sliver was hackled and by turning Z500 × S300 into yarn for knitting and knitted fabric of 2/48 Nm spun, and the strength and the Elongation of the yarn was measured and it became a denier of a coverage factor C.F. of 0.41, and for 1 h and 3 h by means of a Cubex shrinkage test device washed continuously. That with a coverage factor of 0.41 knitted fabric was given a five-hour pill test subjected to an ICI Pilltesters. For further investigation The property of the treated wool fiber was the surface of the Wool with an Hitachi electron microscope S-3500 N examined. To measure the water repellency of the treated wool, the sliver was hacked, so that the fibers opened, and 1 g each of the treated sliver and untreated Sliver was sampled, 800 ml of distilled water were placed in a 1 liter beaker, and the sample was placed on the surface of the water, and the sedimentation state became observed. The results thereof are shown in Table 1.

The Wollfaserband treated was soft and had a white color on, and his shrink-proof equipment filled referring to the method WM TM31, the standard of area shrinkage percentage according to the requirement the Wool-Mark washability, and it also fulfilled that in the ICI pill test Level of the 4th degree. The observation of the sedimentation state of 1 g of the sample showed that both the untreated wool and even the ozone-treated wool does not sink even then, if you are for swim one day and one night on the water surface in the beaker were left while wool, by means of a chlorinated resin process (Hercosett chlorination process) was treated in a beaker after only 2 to 3 minutes under the water surface sank. Although one of the properties of animal fiber is that she is a natural has water-repellent function, in the present invention get a groundbreaking experimental result that a shrink-proof equipment can be awarded without the natural wool's own water-repellent function to lose. In the conventional Shrinking process is mainly a process in which the chlorine-treated wool surface with a Hercosett resin (Polyamide epichlorohydrin) is used. The water repellent Function of the thus treated wool tends to be lost to go, and the wool tends to get wetted, and consequently becomes the body temperature due to the high thermal conductivity lowered by water, causing the wearer to feel cold, though a shrink-proof equipment is obtained. The surface The treated wool was measured by means of a highly evacuated electron microscope S-3500N, manufactured by Hitachi, observed with the object can be observed in the wet state, which showed that the shed edge of the wool did not straighten up, a differential Frictional effect (D.F.) was namely not found, and on the contrary was aimed at the untreated Wool the scale of the wool due to swelling with water, what a cause for the felting represents. Therefore, the present invention is shrink-resistant making process in which the scales edges of wool are in Do not raise the water.

Comparative Example 1

One Sliver of 20.7 μm (25 g / m, 9 yarn threads, Draw ratio: 1: 66-fold) Merino wool from Australia was made according to the procedure of Example 1 treated continuously. However, the ozone treatment has subsided Use of a splashing of ultrafine bubbles preventing Device omitted. The results thereof are in Table 1 listed. Although the treated wool was bleached, the shrink resistant equipment and the pill resistance about the same amount as the untreated wool on, and it was not a treatment effect too detect.

Out Comparison of Example 1 with Comparative Example 1 showed that in wool previously treated with potassium hydrogen persulfate as a pre-treatment process had been treated, oxidation processes fast with a small Amount of ozone. The present invention illustrated by Example 1 Invention is in fact a revolutionary Method by which wool fiber can be modified so that you with a small amount of ozone a shrink-proof equipment and pilling resistance can be awarded, and consequently, the treatment effect manifests itself sufficiently with a small capacity of the ozonizer, and thus reduced the investment in equipment, and the exhaust treatment will be reduced, and a deterioration of the working environment is prevented.

Comparative Example 2

20.7 μm (25 g / m, 9 yarn, draw ratio: 1.66-fold) sliver of Australian merino wool was continuously treated according to the method of Example 1. However, pretreatment using potassium hydrogen persulfate was omitted. The results thereof are in Table 1 listed. Although the treated wool was somewhat bleached, the shrink-proof finish and the pilling resistance were completely the same level as the untreated wool.

Example 2

A 21.7 micron sliver of Australian merino wool was treated according to the procedure of Example 1. However, the transfer rate of the wool fiber ribbon was 0.55 m / min, and the contact time of the treatment liquid with the wool fiber ribbon in the ozone treatment tank and the other treatment tank was 2 min. Apparent ozone supply to wool was 5.37% by fiber weight. 25 g / m × 9 × 1 / 1.66 = 135.5 g / m wool 135.5 g / m × 0.55 m / min × contact time 2 min = 149.05 g of wool 4 g / min (O 3 ) × 2 min = 8 g (O 3 ) 8 g / 149.05 × 100 = 5.37% by fiber weight O 3

The treated woolen fiber tape was hacked and twisted from Z500 × S300 to yarn for Knitted and knitted fabrics of 2/48 Nm spun and to a density with a coverage factor C.F. of 0.41, and were continuous Washing tests for 1 h and 3 h by means of a Cubex shrinkage test device and continue a five-hour pill test performed by means of an ICI Pilltesters, and the strength and the stretching of the knotted Yarns were measured. To observe the state of modification the Wolloberfläche For example, the fibers of 1 g of the treated sliver were treated with a Clam open, 800 ml of distilled water was placed in a 1 liter beaker, and the sliver was floated on the water surface, and the sedimentation state was observed.

The Results of the tests are shown in Table 1. The treated woolen fiber band was soft and also showed wisdom on, and continued by an increase in the ozone supply about 3.6 times compared to Example 1, the shrink-resistant equipment over the Far superior to Wool Mark washability requirement, and the degree of pill resistance was so high that as a result of an ICI pill test even after 5 h the 5th degree was obtained. Because the reaction rate of ozone was increased, the strength and elongation of the knitted yarn were slightly lower and in terms of durability the water repellency in the case of chlorine-treated wool was a complete decrease under the water surface observed and treated this wool compared to natural, untreated wool slightly reduced.

Example 3

The same procedures as in Example 1 were carried out except that the contact time The ozone treatment was set to 1 min, so that a shrinkage treatment on merino wool of 20.7 microns from Australia was performed. The resulting shrink-treated wool fiber was evaluated for its properties, and the results are shown in Table 2 as compared to untreated wool, chlorine-treated wool and chlorine-Hercosett-treated wool. In addition, electron micrographs of the fiber surface in 1 and the results of the water repellency tests using a water droplet dropping method on a knit are shown in FIG 5 illustrated.

With respect to the evaluation of the above-described properties in Table 2, the felt shrinkage speed was measured according to the method of TM TM31, and the fabric was knitted at a coverage factor of 0.41 using a 14 gauge sheet as a sample. The pilling resistance was measured by a pilling test method according to JIS L 1076.6 1A, using the fabric knitted by means of an IP18G. In addition, the friction coefficient μ _a in the direction from the tip to the root of a single fiber in the direction of the scales of the single fiber and the friction coefficient μ _w in the direction from the root to the tip to the fiber direction according to JIS L 1015 under the conditions of acting on the suspension cord Load of 200 mg and a peripheral cylinder speed of 90 cm / min measured.

In addition, the fiber itself was measured by FT-IR according to a reflection method (ATR method). The numerical values are listed as relative absorbances of the absorption band corresponding to the -SO ₃ H group and the -S-SO ₃ Na group in the case where the absorbance of the absorption band corresponding to the amide I is set to 1.

In Table 2 are the results of the evaluation of the dyeing property through the use of a basic dye, which is a measure of the presence of sulfonic acid groups represents listed.

In addition, an evaluation was made using the Allwörden reaction to confirm the presence of the epicuticular layer. The results are in 6 shown.

As clearly shown by these data, the shrink-treated wool fiber of the present invention, unlike the conventional shrink-proofed fibers, allows scales to remain the same amount as that of the natural, untreated wool ( 1 ), whereby a better water-repellent property is maintained ( 5 ).

Furthermore is the pill-resistance compared to the traditional ones Treated fibers with only minor improvements, extraordinarily improved.

Furthermore, the felt shrinkage speed is greatly improved, and the difference between the friction coefficients (static friction and dynamic friction) of the single fiber, which is a measure of the felt shrinking speed, ie the difference "μ _a -μ _w " between the coefficients of friction in the direction of the Tip to the root and in the direction from the root to the tip with respect to the fiber direction, becomes smaller, whereby the anisotropy is reduced.

The FT-IR data shows that, compared to other fibers, the shrinkage-resistant improved fiber of the present invention has many more sulfonic acid groups (-SO ₃ H) and Bunte salts (-S-SO ₃ Na), indicating a higher degree of oxidation indicates that are formed on its surface, indicating that the surface oxidation was efficient.

As in 6 In the animal fiber of the present invention, the generation of bubbles in the all-word reaction was observed in the same manner as in the untreated animal fiber, indicating that the epicuticular layer sufficiently existed. In contrast, in the case of the "chlorine-treated wool" and the "chlorine-Hercosett-treated wool", no bubbles were produced, indicating that the epicuticular layer had been degraded.

The "chlorine-treated Wool "and the" with chlorine-Hercosett treated wool ", which were evaluated for comparative purposes were as described made below:

Production of chlorine treated wool

Wool fiber tape was sequentially immersed in a chlorine treatment bath with a press roll pressed, then immersed in a Antichloro treatment bath, squeezed with a press roll, washed with water and dried.

Chlorine treatment: Chlorine gas was blown into water so that the amount of active Chlorine in the range of 1.8% to 2.0% by weight in terms of fiber weight the weight of the wool was, and the treatment was at one pH of 2.0 carried out in cold water for several tens of seconds.

Anti-chlorine treatment: Sodium sulfite (40 g / L) was added to sodium bicarbonate with sodium bicarbonate pH adjusted to 0.9, and the treatment was several 10 s long at 30 ° C carried out.

Washing treatment: The resulting fibers were placed in a wash bath for several tens of seconds dipped at 40 ° C and then expressed with a press roller.

Dry treatment: The resulting fibers were fed with a suction-type dryer dried.

Production of Chlorine-Hercosett treated wool

To the above mentioned Chlorine treatment, anti-chlorine treatment and water washing treatment was the resulting woolen fiber tape dipped in a processing bath, in the Hercosett resin WT-570 (manufactured by Dick Hercules Co., Ltd.) had been and expressed and then into an emollient and spinel containing oil Treatment bath immersed, expressed and then dried.

treatment with Hercosett resin: The concentration of resin bath was reduced to 2% adjusted by fiber weight, based on the weight of the wool, wherein the pH of the bath with sodium bicarbonate to a pH was adjusted to 7.5, and treatment was included 35 ° C several Carried out for 10 s, and the resultant wool was squeezed with a press roll.

softening: The bath temperature was adjusted to give Alcamine CA-New (manufactured by Chiba Specialty Chemicals K.K.), used as a softening agent Served, to 0.5% by fiber weight, based on the weight of Wool, was discontinued, and Croslube GCL (manufactured by CTC Textiles Ltd./Miki K.K.), which served as spinning oil, decreased to 1.35% Fiber weight, based on the weight of the wool, adjusted, and the treatment was at 30 ° C carried out for several tens of seconds, and the resultant wool was squeezed with a press roll.

Drying treatment: The resulting wool was dried with a suction-type dryer.

Table 2

Note: One minus (-) in the table means shrinking.

With Reference to the evaluation points of Table 2 become the evaluation points those points, from the already mentioned, the felt shrinkage speed, the coefficient of friction of a single fiber, the pilling resistance and the water-repellent property, described below.

Confirmation of the presence of Epicuticle layer

Allwörden reaction: Several individual wool fibers were placed on a glass plate, and several drops of saturated Bromine water was sprinkled on it, and immediately thereafter, the state of the surface of each fiber became submerged observed in an optical microscope. In the presence of an epicuticular layer be on the surface the fiber bubbles generated. Therefore, the presence of an epicuticular layer dependent on from the generation of bubbles approved.

Presence of dandruff

to Observation of scales served an electron microscope.

Property of dyeability by basic dye

In a water solution containing 1 g / l of Astrazon Blue 3RL (manufactured by Bayer Corp.) and 1 ml / l of a nonionic wetting agent, at 20 ° C, wool fibers having a bath ratio of 1: 100 for Immersed for 5 minutes and then washed with water to examine their colored state.

ever darker the coloration state was, the more sulfonates were formed by oxidation.

The present invention enables the provision of an animal fiber with superior shrinkproofing equipment and pilling resistance, without the water-repellent property, the animal fibers originally as superior Feature, deteriorates, and without causing deterioration the mechanical properties of the fiber is effected. Furthermore The present invention also provides a method of manufacture the animal fiber with the above-mentioned features available, without that a toxic chemical such as chlorine, etc. is used.

Furthermore allows the method used in the present invention, the implementation of a continuous process and therefore - from the industrial point of view From the Providing a useful method.

Claims (8)

Animal fiber with scales in original forms on the surface portion of the fiber, resulting in an oxidation degree of -SS - binding in an epidermal cell of the animal fiber of not less than 0.1 of the relative absorbance of an absorption band of -SO ₃ H group and not less than 0.08 of the relative absorbance of an absorption band of an -S-SO ₃ Na group (Bunte salts) is oxidized, wherein the absorbance of an absorption band corresponds to amide-I, which is 1 in a reflection FT-IR measurement method when it is measured as a felt shrinkage speed according to the Wool Mark Test Method 31, and a pilling resistance of not less than the third class in the JIS-L method; 1076.6.1A in addition to the water-repellent property originally exhibited by the animal fiber, the fiber being obtained by a process that is, a) a first step of treating a -SS - bond in a cuticle cell by a primary oxidation to change to a lower oxidized state, b) a second step, wherein the primary oxidized -SS bond is treated by oxidation to transition into one or more of the more highly oxidized states of the double, triple or quadruple oxidized state, and c) a third step wherein the -SS bond in the higher oxidized state is treated with a reducing cleavage. The animal fiber of claim 1, wherein as a measure of shrinkage prevention, the value determined by the difference (μ _a -μ _w ) between the friction coefficient in the direction from the tip to the root (μ _a ) and the friction coefficient in the direction from the root to the tip ( μ _w ) with respect to a fiber direction and measured by the method JIS L-1015, in comparison to the difference (μ _a - μ _w ) of an untreated animal fiber with respect to the coefficient of static friction or the coefficient of dynamic friction by 30 % or more is decreased, wherein the value μ _{a is} about the same value as that in the case of the untreated animal fiber and the value μ _{w is} increased by 30% or more as compared with the value in the case of the untreated animal fiber. Animal fiber according to claim 1 or 2, wherein the animal fiber made of wool, mohair wool, alpaca wool, cashmere wool, Llama wool, vicuna wool, camel hair and angora wool existing group selected is. Animal fiber according to claim 1, wherein in the first Step (a) an -S-S bond by a primary oxidation with an oxidizing agent that's the ability to handle that has to oxidize a cysteine - S - S bond in an animal fiber, and in the second step (b) the primary oxidized -S-S bond an oxidation is treated with ozone. Animal fiber according to claim 4, wherein the oxidizing agent an oxidizing agent or a mixture of two or more oxidizing agents is that of the from persulfuric acid, peracetic acid, performic acid, neutral salts and acidic salts of these peracids, Potassium permanganate and hydrogen peroxide existing group are selected. Animal fiber according to claim 4 or 5, wherein the first step is by means of a pad-steam method of animal fiber in an aqueous solution of oxidizing agents. An animal fiber according to claim 4, wherein the oxidation treatment carried out with ozone is made by an aqueous Ozone treatment liquid which contains ozone in the form of ultrafine bubbles of 5 μm or less animal fiber is blown in this ozone treatment fluid. The animal fiber of claim 4, wherein the animal Fiber as one mainly fabric or fiber composite consisting of animal fibers becomes.