DE1769068A1 - Process for treating animal protein fibers in order to increase their shrink strength - Google Patents

Description

DR. Ί. i '~ \ ί: ώ

KiI. Γ I,. '- _L.

«? - (iidiiii - Street 38
Telephone 443755

Walter Joseph Thorsen, »355 Terrace Drive, El Cerrito, California (V, St, A.)

Process for the treatment of animal protein fibers to increase their shrinkage resistance

The present invention; concerns new procedures for Shrink-proofing animal protein fibers such as Wool * mohair and the like. Further objects of the present invention are apparent from the description below visible in the all parts parts by weight and all proxies are percentages by weight, unless otherwise indicated.

The accompanying drawing illustrates an apparatus for carrying out an inspected embodiment of the method according to the invention.

In the pending patent application T 30 711 IVc / 8 k of the inventor, which on Ιδ. ΜΚτζ Filed in 1966, it has been revealed that wool and other animal paeerti

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can be made shrink resistant by placing the fibers in an area where ozone is generated. Typically, this is done in such a way that aan brings the fibers for a short period of time into an electrical high-voltage discharge zone, which is under normal atmospheric pressure and in contact with the outside atmosphere. While the parsers are located in the zone where they are brought mi I ozone and other gaseous substances generated by the electric discharge into contact, and this has the consequence that the shrink properties of the fibers are substantially improved. As further set out in the aforementioned pending patent application, this mode of operation has numerous advantages, for example the fact that only a short treatment time of about 2 to 20 seconds is required; that because of the short duration of treatment, it can be used continuously; and that the apparatus required to carry out the process is simple and in no way expensive because it is not necessary to use a separate ozone generator and apparatus for fiber treatment, as are required in known systems in which the fibers are treated with preformed ozone he follows.

The teachings of the present invention are followed the way of working of the patent application cited above the modification that chlorine and also air in the elec-

• ■ *

Trlsche discharge zone is introduced. How was found the addition of chlorine gas causes a surprising brhötourv

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the shrinkage resistance of the product. For example, two attempts, the one with wool under otherwise identical loading ~ conditions were carried out and with air alone in one experiment and air plus chlorine (14 volumes to 1 volume) were used, the following results were obtained: the product of the first attempt (Air alone) had a shrinkage time of 22 minutes, whereas the product of the second experiment (air plus Chlorine) had a shrink time of 92 minutes. (The Shrinkage was determined with the help of the ball shrinkage test, which is described in the examples below).

In-one typical of the practice of the invention Case is the electrical discharge system with a Gas inlet device and a stream of air and chlorine is fed into the system through this gas inlet. For best results, the stream should contain approximately 14 volumes of air to 1 volume of chlorine. It however, it was found that improved results - compared to treatment with air alone - with proportions which are about 5 to about 30 volumes of air to 1 volume of chlorine.

The method according to the invention not only allows one to achieve a high degree of shrinkage resistance, but allows at the same time maintaining the numerous advantages obtained with the procedures of application T ^ O 711 IVc / 8k are connected anyway, including the following: * ■ ·

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A main advantage is that the desired result is received very quickly, for example in a period of 1 to 20 seconds, which in a blatant This is in contrast to a treatment duration of at least one minute, preferably about 3 minutes, as in the case known working methods required. in which Method of the inventor's United States Patent 3,149,906, according to which the oas emerging from an ozone generator together with mixed in water vapor takes one to ten minutes long blown against the fiber material to achieve the desired Achieve result.

Since the method according to the invention is very easy to use Treatment time is sufficient, it is particularly suitable for use in a continuous operation especially for the treatment of long webs of the fiber meter, s. Because of the short duration of the treatment, a continuous process does not take place in the regular transport of the Fasaroaterlallen through the numerous steps leading to the overpass the raw original fibers into the finished ones Textiles are required. .

The existing fire enables a more effective use dee ozone, i.e. it requires less ozone per person of the treated fiber material lala · Os the fibers Are localized in the zone in which the ozone is formed « the ozone can come into direct contact with the fibers, and there is hardly any

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losses. This beneficial result stands in sharp In contrast to the systems * where an ozone-containing Gas flow is blown through a textile material; in such a case, a large part of the ozone has no way of contacting the fibers and leaves so lost.

To carry out the method according to the invention The apparatus used is simple and by no means expensive. Although a suitable one for handling the gases Apparatus equipment is required, but it is not in the least complicated, and of course there is none Apparatus for generating overpressure or vacuum is required, i.e. the system according to the invention is used in operated at essentially normal (atmospheric) pressure.

The dyeing capacity of the fibers is made possible by the invention Procedure Essentially unchanged. This means that the products with the usual coloring preparations and can be colored according to the known coloring methods. Therefore, the method according to the invention can be used in the usual Processing stage of the textile material · to be installed; without the dyeing processes as they normally · In the factory be applied ^ to disturb. -

A further advantage of the method according to the invention «, b · -

φ *

stands in the fact that the properties inherent in the fibers, such as their acid solubility, alkali solubility, tensile strength

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- 6 and abrasion resistance, are not affected.

Another advantage is the, dft. £ neither pressure-resistant (nor vacuum-tight} device elements are required; the entire procedure is carried out at normal atmospheric pressure carried out.

Another point is that wool yarns which have been treated in accordance with the teaching of the invention have higher tensile strength when compared to untreated Comparing yarns.

As has also been found, particularly good results are obtained if the fiber material is at least partially dried before it is introduced into the discharge zone, and if the oas stream which is introduced into said zone contains moisture. In practicing such an embodiment of the invention, the fiber material to be treated is subjected to a conventional drying operation so that its moisture content is less than about 5 % before it is introduced into the electrical discharge zone. As far as the gas flow introduced into the discharge zone is concerned, the normal atmospheric air contains sufficient moisture to achieve the desired effect. . Saturate bs advantageous 1st However, in the Hegel, for Kv livering b "," ter "results with the air humidity below. This can be done in a calibration customary manner, for example by means of passing the air stream by water ··

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or through a chamber filled with chunks of quartz, Berlsehen Saddle bodies, pearled filler material and the like is filled and sprayed with water. Even if optimal results are obtained when the fiber material has been dried before the treatment and the incoming gas has been humidified, so the invention can of course can also be carried out without applying these measures, whereby one then gets the improved results achieved which the basic process described above can be achieved allowed.

One for carrying out the method according to the invention suitable form of the device is in the attached Drawing illustrates. This embodiment of the device Is suitable for the continuous treatment of long tracts of the Faeermaterlala, and it also points those necessary for the implementation of the eventual measure Device elements for drying the Paserramaterials before treatment and to moisten the entering Omsstroee. The following is now the construction and the mode of operation of the device will be explained.

The device for generating the silent electrical discharge or the glow discharge line ·, which is very general denoted by 1, consists of the plates 2 and 5 of sinsm dielectric material, such as glass, which are at a very short distance - from about 4 to 10 mm - opposite-

stand. In contact with the plate 2 or 3 is located One electrode each 4 and 5, which are made of aluminum, copper or another electrically conductive metal. The electrodes are provided with pipes 6 and 7, through which a heat exchange fluid circulates, with which the discharge device can be cooled (or heated) to bring it to the particular temperature desired keep.

The energy supply to the internal discharge cell 1 is on Step-up transformer 8 is provided. The secondary winding of the transformer is connected to electrodes 4 and 5. (The symbols x, x illustrate an electrical connection that is not shown in the drawing, impure «to avoid confusion with other parts of the device) The primary winding 10 is connected to an alternating current source tied together. The line 11 that has sagged in the middle the secondary winding is, as shown, preferably grounded. The parameters of the power supply system and the power source are matched so that the electrodes 4 and 5 an electromotive force of about 10,000 to 25,000 volts at a frequency of around 60 to 3000 Herta available 1st. In general, better results are obtained with the higher prequenas in this area. PUhrt one assigns an energy in the specified order of magnitude, so finds a glow discharge in the space between plates 2 and 3 instead of. The room therefore radiates a diffuse purple Glimmlicht aus / das as a series of "bushel discharges

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- 9 appears.

A gas stream - air, chlorine and water vapor (which latter either coincidentally or deliberately exposed) - is indicated by the line 18 between the Plates 2 and j5 located space supplied. The glow discharge acts on these gaseous materials in the mentioned room. As a result, in addition to the substances introduced - oxygen, nitrogen, chlorine, and water vapor in their normal state - the following Components available:

monatomic oxygen (O);

monatomic chlorine (Cl);

monatomic oxygen in both negatively and positively charged states;

monoatomic chlorine in both negatively and positively charged states;

molecular oxygen (O ₂ ), excited to vibrate by visible light; .

molecular oxygen in both negatively and positively charged states; Ozone (0 · -);
Chlorine dioxide (CIO »);

Ozone, excited to vibrate by ultraviolet light;

Ozone in both negatively and positively charged states;

Oxides of nitrogen, including nitrogen pentoxide, nitrogen dioxide and nitrous oxide; Hydrogen peroxide;
Hydroxy groups as free radicals

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- IC-

From the above let it be seen that in the ollament loading zone Oxygen, nitrogen and chlorine are present in manifold reactive states. Many of the extremely reactive species - x.B. the Artan traps excited and charged to vibrations quickly and cannot get out of the discharge zone into one Gas stream can be removed. As a result, the fact that the fiber material causes the GlImmentiadungazone to be exposed directly will. Reactions and window modifications that are different from those obtained when the gaseous products of the discharge zone are removed here and only then to act on a fiber material to be brought.

In operation, the ion discharge cell 1 is under voltage set, and the textile material is taken from the supply roll 1) continuously derived and through the * Antrisbswalsensltse 1% and 15 through the Svste *. part Ifeterlal first of all passes a dryer 16 in which "# a Jeuehtigkeltswoche" to under 5 yrs. # relMej | #tAt becomes. Dmnite ^ will

■ · ■■ '■ ■■■■■. ■ ■■■■ {:, ■''■■ \ W V ". ^V · ^." ^^ i ^ ii · ". ^"; »· - iii -'- '.,

that material passed through cell 1 and treated that Material 17 can then be wound up on a "roll" and in can be processed in any desired way. The turning

^r ■ * · ·

The speed of the rollers Xk and Idm is adjusted in such a way that the fee surface remains in the loading zone until the desired improvement in the scuffing ability has occurred, but no problem has occurred. This period of time is usually around 2 to 20 seconds

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announce. Curr «nd of the operation is allowed to further the Wärmeaustauschflüasigkeit (for example, a known silicone oil) through the pipelines 6 and 7 circulate in order to keep the Glimmentladungszelle 1 at a temperature of about 80 to preferably about 90 to 100 ⁰ C. Usually, this heat exchange fluid is used during the operation of the system to keep the temperature at the desired level by dissipating the heat that is released in the glow discharge cell when the gaseous substances are formed in the discharge zone, and also the heat that is released arises when these substances react with the Pasermaterlal to be treated. On the other hand, the system is cold at the start of operation, and in this phase the liquid serves as a heating medium to warm up the cell to the desired temperature.

To introduce the gases into the glow discharge cell 1 is a pipe 18 made of polytetrafluoroethylene or a other insulating, chlorine-resistant material is provided. The pump 19, which can be designed as a metering pump, sucks in atmospheric outside air from the open end 18a of the line and presses it through the humidifying device 20 into cell 1. At the same time, a Gaseous chlorine originating from the chlorine gas source 21 is fed into the line 18 via the supply line 22. That Appropriate ratio of air to chlorine is achieved by setting the valve 23 in coordination nlt

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the dosing quantity «that pump 19 delivers. Xn usually will the chlorine / air mixture enters the cell in such an amount introduced »that ec in a great excess over the There is enough for the implementation with the fiber material is actually needed; this excess emerges clearly recognizable from the discharge zone, since this after all seldom let open. In operation, the Pump 19 to deliver only a slight overpressure, nXmllch only as much as is required to reduce the flow resistance to overcome the gases; the pressure in the discharge zone corresponds to the attnosphere pressure. The moistening device 20 can, for example, have the shape of a chamber equipped with water spray nozzles, among other things «11«: air flowing through is loaded with moisture.

The process is based on animal fibers ir5.all, such as full, mohair, cashmere wool, alpaca wool, Vlkunja wool, camel hair, horse hair and other profcein fibers which are of animal origin »applicable. Oils materials can be in any physical For: »present, e.g. as slips, rovings, yarns, fiber bundles, Felts, woven or knitted fabrics and the like. It is usually beneficial to use the fiber material of the treatment to be subjected to before it becomes a textile fabric is processed. The treatment is particularly beneficial ωη thin fiber webs - see B. Krempelvllesen - what after the treated material is then processed into yarns and then into textiles. Oa the invented gesture

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Process the desirable properties of the fibers not adversely affected, the materials treated in accordance with the teachings of the present invention can be used for all common uses that fiber materials would normally have are supplied, are used, see B. for the production of all kinds of clothing.

The invention will now be elucidated by means of the following examples explained.

Example X

In the tests of this example, the oil 1 -nt 1 charging chamber 1 used was constructed as shown in the drawing. The dielectric plate 3 ta "stood" from borosilicate glass (CPyrex * -Olas) and was 5.17 aa 0/8 ") thick. 25 * sa (XO") wide and 234 bsi (XO ") long dielectric · plate 3 consisted of a * SiXikonglas bonded 01 laaerflocken (Trp · "Mleaa * t") and wlea • in «thickness of 0.38 en (0.015 *) and a width of 254 sst (XO") and a · Length of 254 au (10 *). The $ paXJi "wlsehen the plates was 6.35» n (X? ") Diethylene Olisisentl · -. Duigsxelle was old operated Herts a current of 18,200 VoXt and 41 <and kept at 98 ⁰ C?.

The velocity of the flow of the chlorine gas lake in the OXlaaen ^ charge selXe was constant at 137 ov? per minute (0-00484 cubic feet per minute) under standard conditions (hereinafter referred to as "ecftn"). The structure

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through air (which comes from the Auasenateosphar was removed and therefore inevitably contained about a moisture, but without additional moistening) was varied during the experiment in the catfish given below.

Each attempt included the treatment of dried wool State. Each wool nuster weighed 1 g and was su a thin strip of ulner area of about 6 * 5 approx (100 sq. Inches) spread out. The Duration Each · Trust ·· was 5 seconds. In a control experiment, no chlorine was added, rather air alone was in the discharge point introduced"

The strength of the hull of the treated woolly owls and tines fluster the untreated full was based on the Loose fiber entanglement (or shrinkage · -) 1 ·· ί ·· betU «Mt. At dl ·. ·. Test is 1 g dea mieriai in * in Oeft Wt a «VatHm ^ v ·» «« · «'^^ au * a Α, -value YoH t, 0 set A fcl-ICl-Fuf ^ er

uM ds · MfSi wlr # o ^ n ¹ ^ "* '- * - ^ -' ■ '

StODfen spoiled · «! and placed on a SehUttelMMohin · (type r ^ saga), on which the oefli · per Nlnut · 175 »al c'uroh were shaken. The shaking is continued until the material forms a ball. The tent, which is needed to achieve this effect, is a hat for the shrink wings of the fibers.

■ · · Sine longer indicates that the fibers are in a small

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- it? -

filter and cut corners. In other words, a I Less time required to form a sphere from the Fibers shows an improvement in resistance to one Schruaperung on.

The results obtained are the following:

Ver
search Flow velocity
diness of the air
, in
cm ^ / 'Mln. cu.ft./min. 0.072 Volume-
relative
nls of
Air chlorine For shaping
a 25mm ball
required
Tent in minutes Xontroll « »2039 0.024 (Air alone) 22nd 1 680 0.01.8 5: 1 50 2 1359 0.067 10: 1 70 3 1897 0.088 14: 1 92 4th 2492 0.11 16: 1 84 5 3115 0.15 23: 1 65 6th 4248 - 31 ι 1 * 5 Blind-
attempt
(ui treated - 16

Your experiments were carried out as in Example 1, Jedoph The following modifications were made: The ratio of air to chlorine was adjusted to 14: 1. The wool was dried before the treatment so that

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their moisture content was below 5 % . The oasatro (air and chlorine) was humidified or dehumidified in various auamafi as indicated in the table below. The results obtained are the following:

sv ß t

Humidity of the air / chlorine oastromes. expressed int

Water pressure mn mercury column

relative humidity
activity in %

For forming a 25mn ball. required tent in minutes

1 18th

2 9

3 *

k COl

control

(untreated

Wool)

82

18 0.05

80 62 50 35

15th

Belnplel 3

The experiments were carried out as in Example 1. However, the following modifications were made: The gas flow applied to the glow discharge cell was varied to obtain mixtures of chlorine with (1) air, (2) nitrogen and (3) oxygen. In a fourth experiment, air was used alone. In all cases the flow rate of the chlorine was 623 cnr ⁵ per minute (0.022 sofa.). The flow velocities of the other gases were approximately seven times that of chlorine «. The results are summarized below:

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- it -

Attempt gas mixture, for forming Volume ratio of a 25> mm ball

required tent in minutes.

1 air and chlorine, 7: 1 70

2 nitrogen and chlorine, 7: 1 yj

3 oxygen and chlorine, 7: 1 yj

4 air alone 18

Blind.

attempt

(untreated

Wool) - 14

An unusual property of the, according to the teacher Fibers treated in the present invention have their resistance to shrinkage negated and then by applying certain

Old treatments can be restored. The technical significance of this property lies in the following «: In the manufacture of textiles from wool or other ^ animal fibers (both woven and knitted) th goods) it is customary to carry out a fulling treatment - i.e. the cloth is mechanically in a warm aqueous liquor worked through, which contains various additives such as alkaline agents or acids, soaps and the like. This makes the tissue fuller. Usually the fabric is as it is from the loom or from the knitting machine comes, a flimsy look. Through the fulling process the fabric shrinks to a controlled extent, so that the

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Openings between adjacent yarns are reduced, and the fabric itself becomes denser and develops the desired body, texture and appearance. It is of course evident that in the paper ₄ Irc <* & a fiber has been made shrink-proof, a fabric made from it cannot be milled for the real sense *. The products treated according to the teaching of the present invention can, however, be freed from their shrinkage resistance at long waves, and by treatment with a cationic surfactant, such as qua-Cernary ammonium salts, which contain long-chain alkyl groups, methylol derivatives of long-chain fatty acids and amides of fatty acids, which are more than Have 8 carbon atoms. If the fiber ice has been treated with this, it can be milled in a weighing liquor with a py below 7 in order to achieve the desired fulling effect. The fulling process is extremely expediently carried out in an aqueous liquor which contains a cationic detergent substance with acid (eg, hydrochloric acid or sulfuric acid), which makes the liquor acidic. Once the flexing process has ended, the shrinkage strength of the bevel material is restored by removing the remaining cationic detergent. This can be done in various ways, for example by extracting the fiber material with an organic solvent such as 1,1,1-trichloroethane or with its acetone / water solutions or by washing in a washer {; en Mediuu, which is a common anlonischee or nloht-

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- 19 Ionic a Contains detergent.

Let us point out that - even if that Disability in the manner described above aries can be produced - this effect is difficult occurs unintentionally during normal use of the treated fiber "teri" is. That's because dl ·? Leather production of feltability the application el i «r. cationic detergent and, at the same time, acidic treatment conditions, whereas normal Use - e.g. when washing - generally alkaline conditions are observed, and under these The shrinkage resistance of the treated Maintain fibers.

This effect of the method according to the invention is demonstrated by the following example illustrates.

ι! game

Wool yarns treated in the manner described In which the glow discharge cells had been exposed, were woven into a fabric. The fabric was divided into several Pattern sections x-cut, and each of these patterns was made ir. treated in the following way:

Mistar 1

The shrinkage capacity was based on this sample the accelerotor method tested. In this test Sample in an "Accelerator" for 2 minutes at 40 ° C

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and J.780 revolutions per minute with a small soap solution (Natriufiioleate) through with a float wool ratio of 50: 1 is applied. After this washing process the sample is air dried and measured to determine soapy curse and shrinkage is dorch comparison with egg's original area dee Calculated the master piece. The "Accelerator" 1st in "American Dyestuff Reporter ", Volume 45 (1956), September 10, 1936 Page 635.

Must «-r , 2

This sample was immersed for 15 minutes in an aqueous solution which contains 1 % of a surfactant of the quaternary long-chain alkylamine type (stearyl-dimethylbensylamao.nlumchlorld) and is kept at a temperature above 60.degree. After this treatment, the wool was subjected to a fulling treatment. This took place in the accelerator in the catfish described above with the difference that in this case the liquor used consisted of water that had been acidified to pw. 1 with hydrochloric acid. The shrinkability was measured as an index of the efficiency of the flexing operation.

A full sample which had been subjected to a treatment to remove its shrinkage resistance (as described in connection with Sample 2) was washed with a KHßrlgen solution which was 0.05 % of a conventional

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non-ionic detergent "namely nonylphenoxypoly (ethyleneoxy) -ethanol, and containing 0.2% tetrasodium pyrophosphate" in order to restore shrinkage. It was then washed in the accelerotor in the manner described above.

Ron <roll attempt

A fabric window made from untreated solid was subjected to the test to determine the visual capacity, as explained in connection with Example 1.

The results obtained are shown below.

Patterns of treatment methods used

Area shrinkage after fulling la Accelerotor in %

Control attempt

A + B

A + B + C

no

40
10

Treatment A Treatment B Treatment C

Treatment in the glow discharge cell. Application of the quaternary ammonium salt.

Removal of the quaternary ammonium salt ^ by washing with the non-ionic one Detergent.

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Claims (1)

- 22 claims 1. Method for the treatment of animal protein fibers for the purpose of improving their shrinkage resistance, thereby characterized that nan the fibers of the action of a Glinro discharge zone exposes in which a mixture of Air and chlorine is introduced. 2. The method according to claim 1, characterized in that da0 the mixture of air and chlorine in a volume ratio of about 14: 1. 3>. Method according to claim 1, characterized in that the linear charge cell under essentially atmospheric pressure stands. 4. The method according to claim 1, characterized in that the fibers are dried before they are exposed to the Exposed to the discharge zone. 5. The method according to claim 1, characterized in that the mixture of air and chlorine gas is humidified before it is introduced into the glow discharge zone. 6. The method according to claim 1, characterized in that dlt Glliunentladungszone at a temperature of about 90 to 10O ⁰ C is kept. * 7. The method according to claim 1, characterized in that the fibers consist of wool. '· 109833/1915 BATH ORIGINAL • - 25 - θ. Method according to claim 1, characterized in that dl · duration of action in the glow discharge zone is approximately 1 to 20 seconds. 9. The method according to claim 1 «characterized in that di <? Oil discharge stone in contact with the atmosphere stands. 10. The method according to claim 1 «characterized in that the treated fiber material, in order to be able to mill it, ■ impregnated with an acidified aqueous solution of a cationic surface-active agent and the treated in this way Material then in an acidified aqueous liquor is drummed and then by removing the cationic rope more surface active; Mltttle d «n tumbled material its very high strength wi «? .d * r will rarely, O BAU ^ n .-. NAL 109833/1915 if Blank page