DE1469316A1 - Process for modifying the characteristic properties of keratin fibers - Google Patents

Description

Method aur Mbdifjgieruan der oharakteriatisohen Properties of teratinous asarp.

The present invention relates to new methods on modification of the characteristic league-like τοη Xeratin fibers. Znnnbe special admit "ie" I old new methods of pre-enactment τοη keratin fiber-containing tissues in the Hlnbllok on a permanent fixation of the same. The presence is made in such a way that dsJ the fabric can be given a desired finish can. The present invention particularly relates to solhe Milling initiation procedures in which the final Fixing the Sewebe, which is about in the form of it Clothes are present under normal humidity conditions

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can take place, i.e. without supply of moisture via the Amount of moisture reuse of the fibers.

Not long ago, methods of presensitizing fabrics containing keratin fibers, in particular of woolen fabrics, in which the final fixing of the fabric, for example in the form of it made clothes is available without supplying a larger amount of water, as is the case in the earlier state of the

W Technique Happened, Can Be Carried Out Such procedures are described in U.S. Patent Application 11144-7, and particularly in U.S. Patent Application 167,420. These methods have become known as "dry folding" -Präseneitivierungverfahren, based on the Tateaohe that the design in the form of clay, for example, permanent folds, folds and the like can be achieved by simple ironing, for example with a Hoffman press can without it being required as in the past

that is lioh, old water »u spray. Do this * procedure thus the need for a spray device and a large number of undesirable operations on a wet tissue are superfluous, as they are due to the "HsJ" -preservations the necessary addition of water to the tissue before the Ironing are own.

The above mentioned new "trooken folds" sensitization methods are strongly welcomed and widely accepted been. In the early stages of developing this new one

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However, some problems have occurred with the type of presensitization. For example, according to the US patent application 167 420 Wool fabric by impregnation with an aqueous solution of a reducing agent and a low molecular weight Polyhydrocyan compound, made from ethylene glycol, for example, is presensitized. However, the dried fabric has no particular one pleasing appearance, so that it is necessary to subject the fabrics thus treated to mild, known finishing operations.

Typical finishing operations include full decating, whereby the fabric is rolled up and in contact with a special accompanying sheet for several minutes steamed under pressure in an autoclave and then subjected to vacuum conditions. An alternative, The operation called half-decating is full decating although similar, the difference is that steam at atmospheric pressure is forced through the rolled web will. These finishing measures are, however, to a certain extent the conditions necessary for the fixation of a tissue similar, wherein the fabric is present, for example, in the form of a dress with a view to a desired configuration thereof. For example, the full decating operation essentially destroys the presensitization in the tissue. For this reason, the process is a little milder of half-decating has been applied. Jedooh can get through too the mild finishing operation, a loss of presensitization to a substantial degree occurs, if none

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special precautionary measures are taken.

Another difficulty stems from the fact that the fabric changes from the beginning of the finishing operation is in a reduced state and is consequently more sensitive to stresses which the fabric assumes a stronger residual relaxation shrinkage. Normal tissues have a certain residual relaxation shrinkage. This difficulty becomes. however, overcome by the fact that the fabric prior to its cutting is completely moistened and dried in the dress form in a relaxed state. This procedure cannot be applied to presensitized tissues because of the chemical substances used for presensitization can essentially be removed by wetting · It was therefore necessary to use this new presensitization method to be carried out under the highest control so that no high residual relaxation shrinkage occurred in the tissues «

^ It is true that an excellent Presensitized tissue can be obtained, however, the cost of such tissue increases because of the required strong control during the sizing to avoid destroying the presensitization as well as one too strong residual relaxation shrinkage significantly increased.

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According to the invention, these difficulties can be overcome in that, after the desired Finishing operations a reducing agent is formed in situ on the fabric. This procedure will be implemented on most effectively carried out in such a way that the tissue is brought into contact with the precursor of a reducing agent is, after which the desired finishing operations are carried out, and the fabric is then exposed to a gaseous activating agent of the reducing agent. In this way all wet operations are carried out before the desired finishing. The finish obtained essentially remains as it is not destroyed by the gaseous activator

Furthermore, there are the keratin fibers of the tissue only in a reduced state after all finishing operations have been completed. That way don't need any exceptional precautionary measures to avoid the development of high residual relaxation shrinkage in the Tissue getting hit.

Since the tissue continues to presensitize only after the action of the gaseous chemical activating agent all finishing operations can be carried out to achieve a high quality finish in the fabric, without affecting the degree of presensitization in any way will.

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A reducing agent preliminary stage * as used here is to be understood as a chemical compound which, through reaction with another chemical compound, forms a reducing agent for keratin fibers. The compound precursor should generally have a pH of preferably about 7 or more when in the form of a 1 ^ aqueous solution. Particularly suitable compounds in this context include lower alkanolamines, such as monoethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, N-ethylethanolamine, N, H-dimethylethanolamine, Ν, Ν-diethylethanolamine, N, ff-diisopropylethanolamine, N-aminoethylethane -Methyl diethanolamine, n-propanolamine, isopropanolamine, triisopropanolamine, n-butanolamine, dimethy lbutanolamine, dimethy lhexanolamine, polyglycolamine of the general formula HO (C ₂ HiO) _x RHH ₂ * in which χ is a positive whole number and R is an alkyl radical, for example the compound in which χ has the value 2 and R is a C ^ Hg radical and the like. Under the action of gaseous SO2 and other activating agents, these compounds readily form reducing agents.

Although the above alkanolamines can preferably be used as reducing agent precursors, these compounds also include other amines, for example those of the formula R (NH ₂ ) _χ , in which χ is a positive integer from 1 to approximately 4 and R is an alkyl radical, such as ethylamine, hexylamine and the like; or an aryl radical, such as, for example, aniline, the toluidines, benzidine

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and similar; or an R ¹ COMH radical in which X has the value 1 and R * is an alkyl or aryl radical, "for example hydrazides, such as acetoylhydrazide H, C-CONH-NH ₂ > butyrohydrazide, benzoylhydrazide, and the like; hydrazines of the formula R ¹¹ NHNH ₂ I in which R ″ can be, inter alia, hydrogen, an alkyl radical, aryl radical and the like, such as, for example, hydrazine, methylhydrazine, phenylhydrazine and the like; Piperazine compounds such as piperazine, homopiperazine, N-methylpiperazine, N-hydroxyethylpiperazine, N-aminoethylpiperazine, N-phenylpiperazine and the like.

Further suitable basic precursors are the alkalis, such as compounds of the alkali and alkaline earth metals, including the hydroxides, carbonates, borates, phosphates, ZeB. Sodium Hydroxide, Ealium Hydroxide, Lithium Hydroxide, Strontium hydroxide, barium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium carbonate, sodium borate, Potassium borate, sodium perborate, disodium monohydrogen phosphate and the like.

Further chemical reducing agent precursors are aldehydes, in particular formaldehyde and glyoxal. But also other aldehydes are suitable, for example saturated aliphatic aldehydes with up to about 18 carbon atoms, such as acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, caproaldehyde, enanthaldehyde, nonaldehyde, palmitinaldehyde and similar; unsaturated aliphatic aldehydes such as acrolein, crotonaldehyde, tiglinaldehyde, citral, propiolaldehyde

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and similar; alicyollic monofunctional aldehydes, such as Pormylcyclohexane and the like; aliphatic dialdehydes such as glyoxal, pyruvic aldehyde, malonaldehyde, amber aldehyde, Glutaraldehyde, adipaldehyde and the like; aromatic aldehydes such as benzaldehyde, tolualdehyde, α-tolualdehyde, cinnamaldehyde, Salioylaldehyde, anisaldehyde, phenylaoetaldehyde, a-naphthaldehyde, anthraldehyde, pyrocateohualdehyde, veratrumaldehyde and similar; heterocyclic aldehydes, such as cc-formylthiophene, a-formylfuran and similar, dialdehyde starch, as well as other aldehyde carbohydrates and aldehydic cellulose products

It has also been shown that ammonia as such can also be used as a reducing agent _{precursor, for example in conjunction with SO 2} or N ₂ O, as an activating gas. In this context, ammonia can be present as a gas, preferably in an anhydrous state or also as ammonium hydroxide, methylammonium hydroxide, ethylammonium hydroxide or any similar compound. If ammonia is used as a gas, this can be done before, after or during the usual finishing.

The method of applying ammonia to the fabric after sizing and before or after applying the activating gauze is highly preferred because of its simplicity and the old recorded results obtained, without the need for barrel sizing and without the additional cost of padding and drying occur

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Ammonia can also be used in conjunction with other reducing agent precursors. For example, a wool fabric can be impregnated with an alkanolamine and then treated and then exposed to the action of both ammonia and SO ₂ in a gaseous state. than better gaps or other forms of greater durability can be obtained in this way.

On the other hand, ammonia can also act as a reducing agent activator as such be used, especially in connection with nitrites with the formation of ammonium nitrites, Ammonium complex compounds and the like.

As stated above, is the reducing agent precursor With the exception of gaseous ammonia, it is preferably applied to the fabric before sizing, since these compounds are best applied in a liquid medium, which essentially destroys the finish of the fabric would be. Most reducing agent precursors are water soluble and can be used as an aqueous solution, however can also be applied to the fabric in the form of a dispersion, emulsion and other suitable systems. The even one The fabric can be impregnated in a known manner, for example by padding, spraying and the like. In In this context, however, it must be noted that the chemical reducing agent precursor in the gaseous state before or

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after finishing, the normally liquid precursor system can be used if those skilled in the art prefer to evaporate.

Under the designation used here "reducing agent activator" is to be understood as a chemical compound that is preferably present in a gaseous state and with one of the above reducing agent precursors can react to form another chemical compound which is a * Represents reducing agents for keratin fibers and thus the Break disulfide bonds of the molecular keratin fiber structure able.

It is not known with certainty whether there is a reducing agent as such on the treated keratin fibers arises in situ, but such formation is highly likely.

₍ Most of the preferred activating gases are reducing agents for keratin fibers. Thus, it is possible that the fibers are simply sensitized by the pretreatment with a chemical reducing agent precursor, so that the keratin fibers then react more effectively with the gaseous reducing agent, thereby making the fibers present in view of a later permanent pixellation is achieved.

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Independent of the mechanism of presensitization however, the chemical reducing agent precursors and the reducing agent activating gases can also be used in the absence of keratin fibers react with one another to form various reducing agent compounds. According to the invention, there is also a presensitization when the treatment with a reducing agent as such for this Purpose is essentially ineffective. For example, an excellent presence of Keratin fibers with a view to permanent fixation in the absence of a larger amount of water, if that Fabric is first impregnated with monoisopropanolamine and then finished as desired, after which it is exposed to SO2, possibly forming monoisopropanolamine sulfite in situ on the fabric. On the other hand, if monoisopropanolamine sulfite is used as a solohes, no such presentation occurs, and a permanent crease can only be obtained by ironing the fabric after the same with a strong amount Water in the order of, for example, 40 wt.-j ( or more has been moistened. Treatment with gaseous SO2 alone is generally in the same way with regard to the presence of a tissue with regard to a later permanent fixation with or without Using a larger amount of water is ineffective.

Since sulfites are generally excellent reducing agents for keratin fibers, SO _{2 is} an often preferred

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Additional suitable activating gases include hydrogen sulfide, the mercaptans, such as methyl mercaptan with a boiling point of 6 ⁰ C, ethyl mercaptan with a boiling point of 37 ⁰ O and similar, mercaptan alcohols such as 2-mercaptoethanol with a boiling point of 50 to 52 ⁰ C at 10 mm Hg and the like, nitrogen oxides such as N ₃ O ₅ and the like, phosphorus-containing oases such as phosphine and the like, nitrosating agents such as HOCl, NOBr and the like.

The amount of reducing agent precursor required and of the activation gas can easily be done by a person skilled in the art determine and depends on the treated tissue and the desired degree of presence.

The preferred chemical precursors are fairly strong bases. Keratin fibers remain for a long time If exposed to basic conditions, a tendency to severe degradation occurs in them. Therefore, the reducing agent activating gas, which is usually acidic, should preferably used in sufficient amount to allow essentially complete conversion with the precursor and a substantially neutral fabric is obtained. It is true that the tissue can be shipped under slightly acidic or basic conditions, even under strongly acidic or basic conditions. You best physical However, properties related to the presensitizing properties are achieved when the fabric is shipped in a substantially neutral state.

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H69316

In this context, a fabric treated according to the invention has a higher folding capacity after a longer period of time Storage time as a tissue treated according to known methods. In reality, the design of the Tissue is generally better after it has been stored than immediately after exposure to the gas. As a result, means the usual retention period is more of an asset than a necessity for the present invention.

The tissue containing the chemical precursor can be subjected to the gaseous activator in an ordinary device get abandoned. For example, steam boxes, decating devices, warp beam and pack dyeing machines, Drying ovens and similar devices can be used.

Somewhat better results, albeit at increased costs, are obtained when a swelling agent or a "low molecular weight polyhydroxy compound" in connection with the reducing agent precursor is applied to the tissue.

Under the designation "low molecular weight polyhydroxy compound" is to be understood as a compound which contains more than one hydroxyl group and a molecular weight of not more than about 4,000. Among the most readily available and most in this regard Desired compounds include those comprising ethylene glycol because of their ease of use. Too special preferred glycols include the poly-

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functional glycols with terminal hydroxyl groups which are separated by 2 to 10 methylene groups, such as among other things, of course, the preferred ethylene glycol, as well as trimethylene glycol, tetramethylene glycol, pentamethylene glycol, Hexamethylene glycol, heptamethylene glycol, ootamethylene glycol, nonamethylene glycol and decamethylene glycol or such glycols as 1,2-propylene glycol, dipropylene glycol, 1,3-butylene glycol, diethylene glycol, polyethylene glycol or similar.

The polyfunctional compounds also belong to polyfunctional compounds with more than 2 hydroxyl groups Alcohol glycerols, such as glycerine, quintenyl glycerine, diethyl glycerine and mesicerin, as well as trimethylol ethane, Trimethylolbutane, tris (hydroxymethyl) aminomethane and others. Glycol ethers, such as the water-soluble or dispersible polyethylene glycols or polypropylene glycols with a Molecular weights of no more than about 4,000 also give satisfactory results in their invention Use.

The urea is the most readily available and most desirable swelling agent, albeit different Substances that are able to swell wool fibers in an aqueous medium are also suitable. For example are guanidine compounds, such as the hydrochloride, formamide, Ν, ΙΓ-dimethylformamide, acetamide, thiourea, phenol, Lithium salts, such as chloride, bromide and iodide, as well as similar

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borrowed compounds equally suitable.

The swelling agent or the low molecular weight polyhydroxy compound can be used in the desired amount, depending on the requirements of the particular tissue. For example, as little as about 0.5 to 1 jL of additives, based on the weight of the fabric, gives some compensation, although in general a larger amount, for example about 3 to 10% by weight, gives remarkable compensation . Of course, a higher amount, up to about 50 % or more, can be used if the particular end use justifies the increased chemical cost of using these additives.

Sa the application of the swelling agent and / or the polyhydroxy compound in general by a wet process takes place, this is preferably done before finishing.

"Finishing ¹ *" in this context is to be understood as a mechanical work step, in which at least one surface of the fabric is treated in order to give it a glossier appearance and / or a pleasing feel.

It is true that the sizing can be carried out in a desired manner, for example in a trough press and the like. Ss

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however, vapor deposition methods such as Halb decating are becoming increasingly popular and full decating preferred. After these procedures, the tissue experiences little or no Stress, which results in minimal residual relaxation shrinkage. When fully decating that becomes Tissue rolled up on a perforated drum which is housed in a pressure autoclave. There is steam through the drum and web under constant pressure generally up to about 2.1 atmospheres (30 psig) during pressed for several minutes, for example for about 1 to 5 minutes, then for several minutes, for example vacuum conditions are maintained in the tissue for 2 to 20 minutes.

In the half-decating procedure, there is steam pressed under atmospheric pressure through a perforated drum and the fabric rolled up on it until it emerges from the outer Layer emerges again. If the steam "breakthrough" occurs, steam will continue to be used for a few minutes, for example passed through the tissue for 2 minutes or more. The extent of decating can help maintain a desired one The gloss of the final finish can be modified accordingly.

The treatment of fabrics according to the invention can, if desired, be carried out under atmospheric conditions. In general however, the treatment is preferably carried out under conditions of elevated temperature and pressure. Better ones Results are obtained when this is a chemical precursor

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containing tissues before, after or during treatment is heated with the activation gas leioht.

Even if the reason for the emergence of better properties cannot be fully explained, it is assumed that that the likely reaction that occurs between the chemical precursor, the activation gas and possibly the keratin fibers run off, more effectively at elevated temperatures runs.

The temperature is preferably lower than the volatilization temperature of the chemical precursor and the decomposition temperature of the desired reaction product. For most of the preferred combinations of precursor and Aktivierungsgae this temperature is less than about 100 ⁰ C (212 ⁰ P), and preferably less than 82 ⁰ C (18O ⁰ P).

By evacuating the container in which the treated tissue is contained, an extremely effective Impregnation of the fabric can be achieved with the activation gas. For example, vacuum conditions in the container be generated. If the activation gas is introduced into the container, the vacuum can be broken and the gas due the pressure increase are effectively pressed into the interstices of the tissue.

Since the keratin fibers are treated according to the invention Do not load tissue until after the gassing in a reduced state

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find, the fabric can be dried after its padding with the chemical precursor at a temperature as it normally occurs during fulling, for example at about 93 ⁰ C (200 ⁰ P) and usually at a temperature of no more than 121 ⁰ C (250 ⁰ P). If the fabric is essentially in a relaxed state during drying, then it is characterized by even less surface shrinkage than an untreated fabric. In this state, the fabric can be sent to the clothing manufacturer who will receive the fabric in the

I can tailor the state without decating

or shrinkage needs to be done, as is required with ordinary fabrics. This earlier way of working is particularly undesirable for the clothing manufacturer, as he not only soaks the fabric obtained, but that The fabric must also be allowed to dry in a relaxed state to ensure that the fabric is more likely to be untrimmed Condition shrinks than later in the form of wet clothes. This decat or shrink process was up

L now an essential step in the production of

Garments made from fabrics finished in a known manner, even if they are a great nuisance for the clothing manufacturer mean.

Regardless of the drying process, the fabric treated according to the invention, on the other hand, has a low residual De-tensioning as it is not in damp and reduced state is processed. The clothes manufacturer

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can the fabric according to the invention in the desired, for the Cut the required shape to manufacture the garment! Sew and iron the dress without adding an extra Treatment step is required. In the process, a piece of clothing is obtained, which is made possible by permanent cracks and splits, depending on the pail at hand. Furthermore, the flat surface areas of the item of clothing made from the fabric according to the invention are distinguished by the tendency to maintain the desired flat shape even in hot, humid conditions.

It can thus be readily seen that the process of the invention is not only an extremely desirable one Supplies dress for the wearer, but that it continues many of the undesirable and additional ways in which how they had to be done by the clothing manufacturer until now, completely eliminates them.

The method according to the invention is particularly suitable for tissue that consists essentially of keratin fibers exist, especially for those made entirely of wool fibers, but can also be applied to fabrics, in which synthetic, natural or other keratin fibers are mixed with the wool component. To other keratin fibers in this context mohair, alpaca, cashmere, vicuna, guanaco, camel hair, lama and the like. Preferred synthetic fibers for blending with wool fibers include polyamides such as polyhexamethylene adipamidej

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Polyester, such as polyethylene terephthalatej acrylic fibers, such as acrylonitrile homopolymers or copolymers that contain at least about 85 # bonded acrylonitrile, such as acrylonitrile / ethyl acrylate (85/15) and Celluloses such as cellulose acetate and viscose rayon. Of the natural fibers that can be mixed with Eeratin fibers, cotton is preferred.

The pasers continue to need during their treatment not to be in the form of a tissue. The process can also be used, for example, on pulling, tow, roving, Use sliver and thread goods and similar goods.

The inventive method can be applied to woven Apply to goods, to nonwovens, to knitwear of any kind and to dyed or undyed goods, provided, of course, that the dyes are resistant to the chemical precursor and the activating agent. In this In connection with this, the dyes are far less sensitive to the chemical precursor than they are to the earlier processes used reducing agents.

Another advantage of the method according to the invention is that the tissue can be treated over a wide pH range. With ordinary finishing for example concentrated sulfuric acid Applied wool fabric in order to carbonize the cellulosic impurities present in the fabric. After this

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treatment often remains 2-3 wt .- # sulfuric acid on the Tissue back. An advantage of the invention is that the fabric treated in this way without prior Neutralization can be treated according to the invention, although the tissue can of course be neutralized for some reason if this is preferred by those skilled in the art will. As stated above, the preferred reducing agent precursors are basic. For example Woolen fabrics suffer degradation if they are exposed to alkaline conditions for too long a period. As a result, the gas reaction is preferably carried out to a sufficient extent for shipping a substantially neutral fabric is obtained.

In the accompanying drawing, a typical device for carrying out the invention is shown schematically Procedure shown. The device has a reaction space 1, which is partially surrounded by an envelope 2 which is used to warm up or cool down the reaction space and its contents. Through the inlet valve 3 Steam or some other heating or cooling fluid can be fed in and discharged through the outlet valve 4 will. In the reaction space 1, a perforated spindle 6 is installed, which flows with the line communicates. Above the perforated spindle 6, on a perforated warp beam 8, a tissue 7 is full Width applied. In the recirculation system there is a 4-way check valve 9 for changing the direction of flow

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of the gas or gases used during the procedure "attached, the valves 10 and 11 are used to control the flow. Purely the manual operation of the valve is a Hand lever 12 is provided, although an automatic control can easily be installed.

That associated with the 4-way valve 9 The recirculation system has the recirculation lines 13 and 14, an air pump 15 driven by a motor (the motor cannot be seen from the drawing), one with the steam or water line 17 connected heat exchanger 16 and a return line 18, as well as a Gas supply line 19, which has an automatic valve and a heat exchanger 21 is connected to the pressurized gas container 22, which is mounted on the balance 23, the is electrically connected to the valve 20 for automatic control. The heat exchanger 21 has a steam or Water line 24 and a return line 25.

A similar system for another gas supply is with the recirculation system via the line 26, the automatic valve 27, the heat exchanger 28 with the steam or Water line 29 and the return line 30, as well as with connected to the gas pressure container 31, which is mounted on the balance 32, which is electrically connected to the automatic control the valve 27 is connected.

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Sur control of the gas or liquid flow, cer

is introduced into the heat exchanger 21 and 28, oind the valves 33 and 34 are also provided.

In the recirculation system there is an exhaust disc and a similar disc 36 in the ventilation flue of the Reaction chamber 1 present «In 37 is in the recirculation system an air inlet valve and in the reaction space in 33 a vent valve available.

When this task is put into operation, the G-weave tree is in the reaction space 1 on the perforated Spindle 6 mounted, the flow in connection with the Line 14 of the recirculation system is up. If desired, the fabric can be preheated by introducing steam into the envelope 2 will.

Ammonia gas is passed from the container 22 into the heat exchanger 21 and through the automatic valve 20 forwarded into lines 19 and 14, up to the scales 23 a predetermined amount is registered, after which the associated automatic valve 20 closes. This gas is then passed through the line 14 into the perforated spindle 6, the perforated warp beam and passed through the tissue 7 and then passed back into the line 13 of the recirculation system, from where it continues to flow through the heat exchanger 16 to maintain the desired gas temperature. This flow

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direction is called "inside-outside flow".

After a predetermined period of time, the flow is turned by setting the valve 9 in the reversed position indicated by the dotted lines in 9 '. In this position the dasstrom turns through the

Valve 9 back so that the gas

surrounds the tissue tree where it is pressed by the tissue 7

enters the space that

and through the holed tree

8 and who were drowsy

Spindle 9 back into line 14 of the recirculation system is directed. This flow direction is "outside-inside flow" called.

This procedure is repeated continuously so that if desired Oy el en an inside-outside and outside-inside flow which will normally be continued throughout treatment.

After exposure to the ammonia gas for a predetermined period of time, the machine will run through Closing the valve 10, opening the inlet valve 37 and the ventilation valve 38 ventilated the reaction space 1, wherein the cyclic procedure is continued. After a few minutes, the valve 10 is opened and the valves 37 and 38 are closed.

From the container 31 is then liquid sulfur dioxide passed into the heat exchanger 28, the steam is

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is called. The liquid immediately evaporates and becomes then supplied via the valve 27, since it is calibrated automatically at the instruction of the scales 32 closes, which indicates that a predetermined amount of liquid has been used.

After recirculation has taken place during the desired As before, the machine will run at atmospheric pressure ventilated, after which additional β ammonia in the system is initiated

The cyolische working method is then interrupted and the reaction chamber 1 is ventilated again to atmospheric pressure, with air in the inside-outside flow duroh the tissue will. After this ventilation, the liasohine is opened and the tissue tree taken out.

This device can be used for any desired implementation method according to the invention, for example, when the tissue has been pretreated with a chemical reducing agent precursor, whereby one or more oasis to be used.

In the following examples, various properties of fabrics treated according to the invention are measured. The tongue tear strength is determined according to A.S.T.M. test for Woven fabrics (Designation 39), Tongue Method, the flex wear according to A.S.T.M. Test for Abrasion of Textile Pabrics (Designation 1175),

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Flexing and Abrasion Method, and the tensile strength according to A.S.T.M. test for Woven Fabrics (Designation 39)> Grab method measured. The pH values are determined by the accepted procedure for determining the pH value of a aqueous wool extract as determined by the international Wool Textile Organization Teohnical Committee in Kay, 1960.

The heduction capacity, expressed in $ SO ₂ , is determined by extracting a sample of 50 g of a presensitized wool fabric in a Soxhlet extractor with methanol for 4 hours under a stioketoff atmosphere diluted. An amount corresponding to 10 ml of extract is filled into a 125 ml Brlenmeyer flask together with 50 ml of water, 10 drops of _{6N H 2} BOj and 1 ml of strength indicator solution. The system _{obtained is titrated with O 1} 1 η KI, solution until the first blue change, which remains for 10 seconds.

ürooken fold assessments were made on presensitized Tissue samples were taken which had a dimension of 11.4 om (4-1 / 2 inches) in the direction of the breast and in the direction of the bed 15.2 cm (6 in.). These samples were folded in half, with the fold parallel to the warp yarns proceeded. The samples were then brewed on a Hoffman press, the deodorant closed and sealed, and the Samples treated with steam under pressure for 30 seconds

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and then heated for 30 seconds, after which it was heated for 10 seconds were kept under vacuum.

They were then opened and folded samples getauoht in a water bath containing a wetting agent and had been heated to 77 ⁰ O (17O ⁰ P). After 30 minutes, the samples were removed, folded along the original fold line, and allowed to air dry. After drying, the creases remaining in the samples were subjectively evaluated by at least 3 observers, the crease rating being evaluated from 1, which does not correspond to a substantial palette, to 5 »which corresponds to a very sharp palette.

According to the Aufhängetest (12O ⁰ F hanging test) were in a manner similar samples of 11.4 cm om (4-1 / 2 to 12 inoh.) Ironed at 49 ⁰ C to 30.5. In this test, the samples were opened, however, by a Elemmgestell hang down left and lowered in a similar bath at 49 ⁰ C (12O ⁰ P). After 30 minutes, the samples were pulled up from the bath and allowed to hang on the rack until dry.

Wet wrinkles were measured by any of the above procedures, including the präeensitlvierten tissue samples were moistened with water to a moisture regain of 40 f> before they were ironed on the Hoffman press.

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example 1

A very consisting of wool fabric, Style 8012 Deering Milliken - worsted fabric was treated with an aqueous solution having a content of 5.5 i "monoethanolamine and from 0.1 # Surfonio N-95, a non-ionic Äthylenoxydkondensationsprodukt as a wetting agent , impregnated. After drying, the fabric was steamed on a Hoffman press to give it the desired finish. The finished tissue was then rolled up on a perforated spindle and SO ₂ gas in an amount of 3 l / Win. pressed through the spindle and tissue for 3 minutes.

After a storage period of 24 hours, the tissue was folded without the addition of water and as above for the determination examined its wrinkle rating, which was 3.0.

This procedure was repeated with the difference that various reducing agent precursors were in solution were used, as shown in Table 1.

Table 1

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Table 1 Treatment before finishing Wrinkle evaluation (dry)

Control 1.0

No pretreatment (only SO ₂ -SaS) 1.0

5.5 * monoethanolamine 3.0

965t monoethanolamine carbonate (pH 8.0) 2.5

6.25t monolsopropanolamine 3.0

11 5 < Honoieopropanol amino carbonate (pH 8.0) 2.5

7.75 * trie (hydroxymethyl) aminomethane 3.5 13 * tris (hydroxymethyl) ainomethanocarbonate

(pH 8.0) 3.0

20 * ethylene glycol 1.3

5.5 * monoethanolemine + 20 * ethylene glycol 3.5

9.6 * monoethanol amino carbonate + 20 * ethylene

glycol 3.0

6.2 * monoisopropanolamine + 20 * ethylene glycol 3.5

11 * monoieopropanol amino carbonate + 20 *

Ethylene glycol 3.0

7.7 * trie (bydroxyraethyl) aminomethane + 20 *

Ethylene glycol 4.0

13 * trie (hydroxymethyl) aminomethane + 20 *

Ethylene glycol 3.5 Example 2

A sample of a Kaimngarn-Öewebee Style 8012 was padded with an aqueous solution of 6.0 * monoisopropanolamine and 0.1 * Syn-fae 905, that is a non-ionic ethylene oxide condensation product with crosslinking agent properties, up to an absorption of 80 *. The temperature of the Klotzbadee was 24 ⁰ C (75 ⁰ P). The impregnated fabric was then stress-free at 102 ⁰ O in a drying device

809817/068 1

- 30 - 1A-27 794

(215 ⁰ P) dried to a moisture content of $ 10>. After drying, the fabric was semi-decated using a cycle of steam breakthrough + 1-1 / 4 min. Steam at 7 Atu (100 psig), followed by a pump vacuum of 500 mm. Mercury for 3 min was created.

After half-decating, the tissue was rolled up onto a perforated spindle of a full-decating autoclave. The spindle was placed in the autoclave, the sealed unit, and heats the tissue at 60 ⁰ C (I40 ⁰ f). Sulfur dioxide gas was then introduced into the system in an amount stoichiometric to the amount of monoisopropanolamine padded onto the fabric. After introducing the sulfur dioxide into the closed system, the tissue remained exposed to the sulfur dioxide vapors for a further 10 minutes. Then air was forced through the fabric and the autoclave was then ventilated so that residual and / or unconverted tungsten dioxide could be removed.

After folding and testing as above, a Taltengtite of 2.4 was measured.

Example 3

The procedure according to Example 2 was repeated with the difference that a ·

»09817/06 8 1

- 31 - 1A-27 794

Gaston County (Theis) drying machine was used. In this machine, the SO ₂ gas is passed through the fabric in a forward and backward flow until all of the amine has theoretically been converted. Fabric treated in this way has a wrinkle rating of 2.5.

Example 4

The process according to Example 2 was repeated with the difference that the half-decatation cycle had vapor deposition for 5 seconds after the vapor breakthrough, after which a vacuum was applied by pumping for 2 minutes. The tissue was further put into a dyeing machine Burlington and preheated prior to the gas treatment 26.7 ⁰ C (80 ⁰ P). In this way, a column rating of 2.0 was achieved. After a storage period of one week, this value rose to 2.5.

Example 5

The method according to Example 2 was repeated with the difference that the pad bath 5 $> ethylene glycol was added. The wrinkle rating was 2.3 after 24 hours and 2.5 after one week.

909817/0681

- 32 - ■ 1A-27 794

Example 6

Samples of the worsted fabric from Example 1 were padded to a moisture absorption of $ 70> each of two pad solutions

(1) 6.196 monoisopropanolamine + O.I96 Syn-Fac 905 Wetting agent?

(2) 6,196 monoisopropanolamito. + 20 # ethylene glycol and 0.19i Syn-Fac 905. j

After drying at 93 ⁰ O (200 ^ P) and semi-decatizing according to a Cyklus of vapor deposition for 5 seconds, followed by vacuum for 2 min, the tissues were kg in an amount of 31.8 (70 lbs) on the warp beam a Rolled up Burlington dyeing machine. The unit was then sealed and SO ₂ was forced through the warp beam at a rate of 15 l / min., Converted to atmospheric pressure, for a period of 0.6 minutes (0.28 minutes per lbs) per kg of fabric. This amount of SO ₂ provides the stoichiometric amount required for binding with the amine. The treatment with gas was continued for 20 minutes, after which the fabric was left in the SO2-laden atmosphere inside the machine for a further 20 minutes. Compressed air was then fed into the beam feed to expel excess SOg from the fabric before the beam was removed from the machine.

After decating and being treated with SO « Samples of the tissue for their reducing power, (percent

•• 09017/0681

BATH ORIGINAL

- 35 - / U-27 794

extractable β SOg) analyzed their free amine content, pH, folding capacity and their physical properties. These samples were compared with an untreated control sample compared.

After the Amin-Kloteen · Gate of the S02 treatment

τ _ö _ Daetrön test crease

_eung Grirr { GraftTensile; . 'ti * i * -r »** i» irmi * usage

-, ι -π "■, L * w ** ftH ^ * ^ c ** y (cycles to

"fSSP" ^g ! S) ¹¹¹¹ * ygrammj jg * gSi tögung)

Con
trolls (77 * 5) 55, 1 60 .5 1926 1
2 (70 .; 4)
2) 52. I IO O 50
55 .6
.0 1841
1698 741
925

Table 3 Naoh eOg treatment and aging for 4 days

Instrftat KnltteralH

Tension- (Jrirr (Grab HeiereetigKeit Nutzbi- «» «» Shrink Tensile). (Tongue Tear) resistance ^^ _. W _ Strength (cycles up to

Chain Schufl (lbs) kg (ji) (gr) eur destruction)

Control (77.5) 55.1 60.5 1926

1 1.45 3.03 (72.7) 32.8 51.6 1851 803

2 1.70 3.17 (80.4) 36.5 58.7 1878 938

»09817/0601 ^{8AD 0R} ' ^Q INAL

Table 4 Reducing Power and Dry Wrinkle Rating

solution * SO ₂ Troak fold assessment according to 4 days control O 1. 1 0.24 3. 2 0.23 2. , 0 ,1 .5

Example 7

Samples of the fabric * from Example 1 were up to one Recorded ion 100 * padded with each of the following solutions »

▲ · 6.1 * Monoisopropanola »in + 20 * ethylene glycol + 0.1 * Syn-? Ao $ 90

B. 6.1 * monoisopropanolein + 0.1 * 8yn-Jao 905

0.1.15 * monoieopropanolaiiin + 20 * ethylene glycol + 0.1 * Byn-Pao 905

D. 9 * 15 * ^ »noiaopropanolamine + 0.1 * 8yn-? Ao 905

1. 12.2 * lonoieopropanolamine + 20 * ethylene glycol + 0.1 * Byn-Pao 905

f.12.2 * Monoieopropanolamine + 0.1 * 3yn-Fao 905 *

laughing their Trootaien at 93 ⁰ O (20O ⁰ F) in a mechanisohen Konrektionsofen the tissues was rerliehen a GHanzappretur. For this purpose, they were placed on a Hoffman press between 2 pieces of a cotton conductive cloth and steam was pressed through them for 15 seconds, after which they were pressed for 60

909817/0681

BATH ORIGINAL

1A-27 794

Seconds were exposed to the vacuum conditions. Some samples were used to measure pH, amine and taken for physical investigations.

The remaining samples were _{exposed to the action of SO 2} until a clear excess could be detected by a moist indicator paper on the outside of the fabric roll. Investigations were carried out with these samples to determine the Falteri resistance and an extraction was carried out to determine the reducing power and to carry out physical investigations.

Table 5

Reducing power and dry wrinkle rating after 1 day

solution

SO

Dry wrinkle evaluation at 77 ^° C

A. 0.79 B. 0.46 σ 0.42 D. 0.65 E. 1.27 F. 0.47 control 0.0

4.9 4.4 4.0 4.5 5.0 4.8 1.0

909817/0681

BATH ORIGINAL Table 6

pH of the tissue

1A-27

Solution After the amine puke After the SC ^ treatment Before the SOp treatment

5.3 7.5 7.7 7.4 5.4 8.9

control 5.4 (no amine) A. 8.1 B. 9.2 σ 9.5 D. 9.5 Έ 9.6 9.6

Tabel

$ 09817/0681 BAD ORIGINAL

Table 7

ghyaikalieoher read

solution

Tear resistance (tongue tear)

(gr)

According to amine
treatment
and finishing (71.1) 32.2 44.0 • 1719 Before the
SO ₂ -Bt- (77.6) 35.2 62.3 1678 plot (71.7) 32.5 55; 3 1633 Xontroll (74.6) 33.8 64.1 1524 A. (75.1) 34.0 60.6 1615 B. (75.9) 34.4 61.3 1551 C. (71.0) 32.2 5 M 1488 D. E. V (81.6) 37.0 73.0 1696 ! «Oh SO ₂ - (85.0) 38.6 65.3 1814 B »action (81.5) 36.9 68.6 1583 A. (83.9) 38.0 70.6 1864 B. (83.3) 37.8 71.1 1696 σ (83.9) 38.0 74.3 1746 D. 1 J

• 09817 / U681

ORIGINAL INSPECTED Example 8

As in Example 7, the various fabric samples in this example were pretreated with solution B from Example 7, dried and finished on a Hoffman press. The fabric was then rolled up tightly on the spindle of a Baok dyeing machine, the dimensions closed and 80 g fed into the spindle under various pressure conditions. Duron by flowing 8O _{2 fc} into an evacuated autoclave, the fabric was more thoroughly impregnated with the gas. As the Druok continues during the If reaction with UO ₂ decreases, the person skilled in the art has a method for controlling the amount of _{80 2 used during the measurement of the pressure drop.}

In Table 8, veffohiedeae treatments are listed, what an evacuated Paokflrbemaeohin · used and the wrinkle rating was determined. The letters MZPA mean monieopropaaolaain.

. Act 8

Treatment- Description of treatment folds & b ·· number rating

1 treatment with 6.0 * MZPAf Halb-Dekatieren on a Hoffman-Pressef vacuum of 71 cm _{break with BO 2} (5 times) 3 x 7

909817/0681 * orte.tzua «

BATH ORIGINAL

- 39 - 1A-27 794

Table 8 (continued)

Treatment Description of the treatment. Wrinkle number Rating

Treat with 6.0 # MIPA; Halb decating in a dyeing machine; SO ₂ under (10 psi) pressure of

0.7 atm 2.3

Treat with 6.0 # MIPA; Halb decating in a dyeing machine; Break vacuum of 70 cm with SO ₂ (1 time)

Treat with 6.0 # MIPA; Halb decating in a dyeing machine; Vacuum of 30 cm with SO ₂

break (1 time) 3 * 7

Treat with 6.0 # MIPA; Halb decating in a dyeing machine; Break vacuum of 20 cm with SO ₂ (once)

Treat with 6.0ji MIPA; Halb decating in a dyeing machine; Break vacuum of 10 cm with SO ₂ (once)

Treat with 6.OjG MIPA; Half-decating in a dyeing machine; Break the vacuum of 71 cm with SO _2; Let pressure rise; Break the vacuum from 47 cm to 0 with NH

Treat with 6.0 # MIPA; Half-decating on Hoffman press; Break the vacuum of 71 cm with SO _2; Let pressure rise; Break the vacuum from 46 cm to 0 with NH ₅

949 817/0681 continued ^

- 40 - * 1A-27 794

Table 8 (continued)

Treatment rubbing of the treatment FaIten number evaluation

9 Treat with 6.0 ^ .MIPAj none

Half-decating; Blow SO ₂ through the tissue (2 literat.) For 5 min.} Pumps for 10 min. At 40 om vacuum to flush 4.0

10 Treat with 6.0 # MIPA and 1 Synsoft LSι no half-decating;

k _{Blow through SO 2} (2 liters / bin.)

for 5 min .; Age 5 min., Blow air through for 30 min. 3.5

Do not treat with chemicals and do not half-decate; Blow SO ₂ through the tissue (2 liters / min.) For 5 min .; no aging) NH, and blow air through until the tissue has a pH «7 1.8

12 Do not treat with chemicals and do not half-decate; Blow in SO ₂

^ (2 liters / min.) For 3 min .; Ver

close and let age 10 min.) ventilate for 5 min.) NH, through the tissue Blow through up to pH 7 3.4

Do not treat with chemicals and do not half-decate; NH, blow through for 3 minutes; Close and let age for 5 minutes; Blow air through (3 min.); Blow in SO ₂ until the tissue has a pH of 7 4.2

909817/068

-41 - -U-27 794

Example 9

The fabric from example f was treated as in Beiipitl Ö under various pressure conditions in the faokflrbeaasohine and since the fabric is preheated to different temperatures, the corresponding working conditions are shown in Table 9, the pH of the fabric according to these Treatments, • a reduction eye, its various physical characteristics and its ability to split, both in the case of a moisture supply and also in the nature of a solo supply, are divided into table 10 40 f feuohtigkeltsaufnahil · bestiwat before ironing on the Boffman face.

! Uanilung

¹ ■ * »ewebe trades ait 4ft lloaoisepropaiiolamin,

padded to «u a» strength oniieA ·· clay 100ΐί, dried b »i 95 ^σ <> (20 ^ f). The temperature is brought to 27 ⁰ O (8i ° F) inside the web and SO _{2 are} added. Feoh 80 ₂ addition, the temperature rises to 38 ⁰ O (100 ° f) · Bruok su beginning 54 «Μ«

E (tissue treated with f £ Monoieopropmnolemin, padded to a moisture absorption of 100ji, dried at 93 ⁰ O (200 ° f). The temperature is brought to 66 ⁰ O (152 ⁰ P) inside the tissue and SO ₂ added, When S0 _{2 has been} added, the temperature rises to 82 ⁰ O (182 ⁰ P), and the pressure is 190 mm at the beginning.

- 42 - 1A-27 794

9 (continuation)

Treatment description

a «wt)> · bthandtlt with 6jl honeyeitopropanolamine, gtklotat bia BU atr leuohtigktitaufnahmeat τοη 100Ji, gttrookntt btl 93 ⁰ O (200 ⁰ V). The temperature is increased to 94 ⁶ O (202 ° y) gtbraoht in the interior dt · gtwoven and BO ₂ added. After adding τοη BO ₂ , the temperature rises to 101 ⁰ O (214 ⁰ I). Druok at the beginning 70 mn

J Tissue treated with 6% monoitopropanolamine, gtklotat up to a Teuohtigkeitsaufnähme of 100H, gttrooknet at 93 ⁰ O (200 ⁰ I). The temperature is brewed with 26.7 ⁰ O (80 ⁰ P) in the interior, the water and 0O ₂ added, followed by SO ₂ addition, the temperature is 37.2 ⁰ O (99 ⁰ I). Pressure at the beginning of 60 mm.

K Gtwtbt btbandtlt Bit IfJ Monoitppropanolaml », gt-

H »** tiftto ptuthiigktlttaufnatait τοη gttrookntt Ptl 93 ^f 0 (| 00 * t). to 5 ° Ρ ti37 ° y) gtbraoht in örntrn dt · and $ 0 _t continues. laoa «is carried out on IO _f -flugaW attests the dia {« aptratur on TJi5 ^ü O ^{0 at the} beginning of ti ■ ».

bthandtl-fc «it M monoitopropanolamine, gtbia on a PtuohtigJceiiitaufnahae τοη 100K, gttreokntt bti 93 ⁰ O (200 ⁰ F). The temperature is set to 50 ⁰ O (121 * 1) gtbrao ^ t 1 "Inntrn dta atwtttt u" d SO ₂ aagtfttgt. Vaoh follows up SOg-lttga »· confirms the temperature at 69 ⁰ O (156 ⁰ J) Druok au Jtginn 58.

009917/06 81

BADORiQiNAL

- 43 - 1A-27 794

Table 9 (port setting)

Treatment description

M fabric treated with 6% monoisopropanolamine, padded to a moisture absorption of 100j6, dried at 93 ⁰ O (200 ⁰ F). Temperature is brought to 59 ⁰ O (139 ⁰ F) inside the fabric and SO _{2 is} added. After the _{addition of SO 2 has} taken place, the temperature rises to 84 ⁰ O (183 ⁰ F) pressure at the beginning of 60 mm.

N tissue treated with 6J6 monoisopropanolamine, padded to a pickup of IOO96, dried at 93 ⁰ C (200 ⁰ F). Temperature is brought to 61 ⁰ C (142 ⁰ F) inside the fabric and SO _{2 is} added. After SO ₂ addition the temperature rises to 71 ⁰ C (160 ⁰ F) mm pressure at the beginning of the 60th

Tissue treated with 696 monoisopropanolamine, padded to a moisture absorption of 10096, dried at 93 ⁰ C (200 ⁰ F). Temperature is brought to 58 ⁰ C (137 ⁰ F) inside the fabric and SO _{2 is} added. After the SOG addition, the temperature increases to 69.5 ⁰ C (157 ⁰ F) mm pressure at the beginning of the 365th

P fabric treated with 696 monoisopropanolamine, padded to a moisture absorption of 10056, dried at 93 ⁰ C (200 ⁰ F). Temperature is brought to 59 ⁰ C (138 ⁰ F) inside the fabric and SO _{2 is} added. After the _{addition of S0 2} , the temperature rises to 75 ⁰ C (167 ⁰ F)
Print at the beginning 365 mm.

Continuation 909817/068 1

- 44 - IA-ZY

Table 9 (continued)

Treatment description

Tissue treated with 6 # monoisopropanolamine and Ethylene Glycol, padded up to

Moisture absorption, dried at 93 ⁰ O (200 ⁰ P). The temperature is brought to 63 ⁰ O (146 ⁰ P) inside the fabric and SOg is added. After the SOg addition, the temperature drops to 76 ⁰ O (168 ⁰ P).
Print at the beginning 365 mm.

E fabric treated with 6 # monoisopropanolamine and 5-6 ethylene glycol, padded up to 100% moisture, dried at 93 ⁰ C (200 ⁰ P). Temperature is brought to 66 ⁰ C (15O ⁰ F) in the interior of the fabric and Soo added. After the S0 ₂ addition, the temperature rises to 79 ⁰ C (174 ⁰ P).
Print at the beginning 365 mm.

Table 10

909817/0681

ιΛ— egg

146931C

Table 10 Partial gas process

Treatment pH

Instron Instron
(Tongue 'handle (Grab Tensile) • Tear)
i tear
! strength

Pestig elongation

leg

"~ Wrinkles Dry Wet

control

1926

65.9

47.0

G 7.2 1.68 1874 77.5 60 5 3. 6th 5.0 H 5.2 2.23 1838 70.2 45. 8th 3. 5 5.0 I. 4.6 1.68 1757 66.1 55. 0 3. 1 5.0 J 7.1 1.16 1957 70.1 45. 4th 2. 5 4.9 X 7.0 2.24 1844 75.4 50. 7th 2. 9 4.8 1 7.1 1.13 1913 78.0 54. 3 3. 8th 5.0 U 7.5 1.10 1868 78.3 52. 9 3 · 6th 4.9 H 7.5 1.78 1825 70.2 53. 2 3. 9 5.0 0 7.9 1.67 1803 64.5 48. 1 3. 8th 4.9 5.6 2.75 1752 69.6 54. 2 3. 7th 4.6 Q 6.1 2.85 1719 66.1 55. 0 3. 6th 5.0 B. 5.3 2.50 1688 67.7 62. 8th 3. 2 4.6

909817/0601

Example 10

The fabric from Example 1 was half-decated, rolled up on the perforated spindle of a pack dyeing machine and enclosed therein as in Example 8. When anhydrous ammonia gas entered the machine, the temperature of the fabric was 25 ⁰ C (77 ⁰ P). After the temperature had ^{risen to 40.5 0} O (105 ⁰ F), air was forced through the machine for 10 minutes so that the ammonia gas was purged, after which the temperature was 19 ⁰ O (66 ⁰ F). "While inside the machine a pressure of 50 mm Hg prevailed, SO ₂ gas was introduced into the machine until the temperature reached 35.6 ⁰ C (96 ⁰ F). The machine was then flushed with air as above, the spindle was removed and the tissue pH and the folding capacity were measured. The pH was 4 »9» the evaluation of the dry wrinkles was 2.6 and the evaluation of the ITaB folds was 4.7.

Example 11

The procedure from Example 10 was repeated with the difference that SO 2 gas was fed in at the beginning and then anhydrous ammonia gas was fed in. Before the "SO ₂ feed, the temperature was dee tissue"'25 ⁰ C (77 ⁰ P), and ■ 33.3 ⁰ O (92 ⁰ P) ala _9, the so-called feed was terminated. Goal was the feed clay ammonia the tissue temperature 25 ⁰ C (77 ⁰ P) and the pressure of 57 mm. ITaohdem a temperature of 46 ⁰ C (115 ⁰ P) was reached, the reaction was stopped and the

009817/0681

- 47 - 1A-27

The spindle removed from the machine after it was rinsed. The fabric pH ″ was 5.91, the dry foldability 3.2 and the wet foldability 5 _f 0.

Example 12

The fabric of Example 1 was padded with various baths block to a pickup of 80 i ", starched and exposed as described in Example 1 the action of an activation gas. Table H shows the properties of the fabrics obtained in this way.

Table 11

909817/068

Composition of the dye bath

Part 11

pH of the dye bath

Gas-

loading

plot

pH before pH after drying the gas- the gas- wrinkle-hand-hand formation lung lung

hour

Dry Pal formation after 24 hours

56 SUN,

H ₂ O

6.0 MIPA

8.2 Hexylamine 4.9 HH ₄ OH (28 #) 6.0 MIPA

8.2 Hexylamine 4.9 Im ₄ OH (28 #) 6.0 MIPA

8.2 hexylamine

untreated control

3.0 SO ₂ - 4.8 5.0 ti 5.4 4.6 3.0 It 5.0 4.4 7.0 It 4.8 4.4 7.0 η 5.9 4.7 7.0 π 5.5 4.6 10.0 η 4.9 4.4 10.0 η 8.8 8.3 10.0 η 9.4 6.0 - No 4.5 - 12.5 SO ₂ 9.2 6.0 12.1 η 9.0 5.8 4.5
4.5
10.9
11.2
4.5 It
η
η
η
η 7.5
6.9
7.2
9.6
■ 4.4 3.0
5.2
5.1
6.0
4.2

1.8

2.2

2.5 2.1 1.8 2.1 2.2 2.2 2.7 1.4

1.9 1.9 2.5 2.1 2.5 1.8 2.0 2.6 2.5 1.8

0.728

0.517

1.96

0.912

1,358

1,221

0.805

0.912

2,425

5.5 Strontium hydroxide

1.6 sodium hydroxide

5.5 Pormalin

7.8 Glyoxal (5

4.9 HH4OH ($ 28) 8.2 Hexylamine 8.8 aniline sulfate 2.5 5.6

2.4 1.8 2.1 4.4 1.7

2.8 4.2

.21 1.96

2.1 .27 2.1 .45 2.5 .50 4.5 1.15 1.8 .58 3.3 .29 3.4 .29 1.8 .07

6.0 MIPA. water

10.4
9.0

'.4

10.1

8.9
5.4

274 2.6 1.5

-CD CD

6.0 MIPA

so,

.0

6.7

5.6

5.9

.83

Example 13

The fabric from Example 1 was padded to a moisture absorption of 82 fL with a solution in which 6 pounds of monoisopropanolamine, 5 pounds of ethylene glycol and 0.1 pounds of Syn-Jao 905 were contained ⁰ O (200 to 225 ⁰ I ¹ ) dried to a moisture content of about 10 pounds, semi-decated with steam for 1.25 min. And then exposed to a vacuum for 3 min. After half-decaling, the fabric was cut into strips 29.5 µm (11-5 / Ö inch) wide and 36.5 m (40 yards) long. Each tissue sample was individually wound up mechanically on the spindle of a gas treatment machine and an attempt was made to manually keep the tissue tension the same from one roll to the next. The actual gas treatment was carried out in a different way, as indicated below.

(1) Sin pretreated tissue (1869 g) was placed in the ma- ■ ohine and heated to 66 ⁰ O (150 °). Sulfur dioxide gas was fed into the machine in sufficient quantity (51 g) to titrate the imine in the tissue, and in sufficient excess to fill up empty spaces in the tissue. The gas was bubbled back and forth for 15 minutes and then ammonia gas was introduced in an amount sufficient (7 g) to titrate the excess sulfur dioxide present in the system. The ammonia was 5 minutes

909817/0681

passed back and forth, the experimental treatment terminated and the tissue removed from the machine.

(2) A pretreated fabric (1869 g) was placed in the masohine and brewed to 28 ⁰ O (85 ⁰ P). As in (1), carbohydrate dioxide gas and ammonia became in proper order and amount initiated "A very small amount of" snow ¹¹ could be observed along the edge of the fabric, which should be ammonium sulfite and / or bisulfite ·

(3) A pretreated fabric (1823 g) was placed in the Maaohine and ^{heated to 57 0} O (135 ⁰ P). A sufficient amount (41.4 g) of sulfur dioxide gas was introduced into the system to titrate the amine in the tissue, including an amount sufficient to fill in empty trees in the tissue. The gas was passed back and forth for 10 minutes and then ammonia gas was introduced into the system in sufficient quantity for 6.3 seconds to titrate the excess soybean dioxide. After another Uli line for 10 minutes

\ The Deokel was opened and the tissue beblaeen 5 minutes by air.

(4) Lin pretreated fabric (1908 g) was placed in the masohine and bohweel dioxide gas in an amount of 43 g initiated into the system that was sufficient to remove the AmIn titrate in the tissue and fill in the empty spaces in the tissue. laughed at a diversion for 10 minutes was Aaaoniakg ** in sufficient quantity (6.6 g) sur Titra-

909817/068 i

- 51 - 1A-27 794

tion of excess sulfur dioxide initiated. the Gases were bubbled back and forth for 5 minutes and then the system and tissue were blown with air for 5 minutes.

No heat was applied during this experiment. The heat generated by the compression of the air and the reaction during the acid-base titration increased the temperature of the tissue to 39 ⁰ O (102 ⁰ P) during the course of the experiment.

(5) A pre-treated fabric (1886 g) was placed in the machine and a sufficient amount of sulfur dioxide gas was placed (42.5 g) for titrating the amine in the tissue and for replenishment introduced into the system by the free spaces in it. This gas was diverted for 5 minutes and then ammonia gas is introduced in sufficient quantity (6.5 g) to titrate excess sulfur dioxide.

At this point the tissue temperature was approximately 38 ⁰ O (100 ⁰ P). ^{The tissue was then heated to 60 0} O (140 ⁰ P) with the aid of an electrical heater connected to the machine. After reaching this temperature

the fabric was blown with air for 5 minutes.

(6) a pre-treated tissue (1791 g) was placed in the machine and heated at 56.5 ⁰ C (134 ⁰ P). Sufficient sulfur dioxide gas (40.5 g) was introduced into the system to titrate the amine in the tissue and fill in any gaps therein. After

9 0 9 817/0681

- 52 - '1A-27 794

U69316

line of this gas for 5 minutes was ammonia gas in sufficient amount (6.2 g) to titrate excess sulfur dioxide. Subject diversion during further The system was opened for 5 minutes and the tissue was blown with air for 5 minutes.

(7) A pretreated tissue (1920 g) was placed in the machine and ^{heated to 60 0} O (HO ⁰ P ;;. Sulfur dioxide gas was then added in sufficient quantity (38.4 g) to titrate the amine in the tissue and to use it The gas was diverted for 5 minutes and then sufficient ammonia gas (6.4 g) to titrate excess sulfur dioxide was passed in. After diversion for a further 5 minutes, the system was opened and the tissue was ventilated for 5 minutes blow.

(8) A pretreated fabric (1874 g) was placed in the machine and ^{heated to 63 0} O (145 ⁰ P). Sufficient sulfur dioxide gas (37 g) was then introduced to titrate the amine in the tissue. V ± e gases were diverted for 5 minutes and then sufficient ammonia gas (14 g) was introduced to titrate all of the sulfur dioxide previously added to the system. The gases were diverted for an additional 5 minutes, then the system was opened and the tissue was blown with air for 5 minutes.

909817/066

- 53 - ■ ■ ■ 1A-27 794

(9) A pre-treated fabric was placed in the machine

(1982 g) and ^{heated to 63 0} O (145 ^Ο ϊ). Then became

A sufficient amount (39 »5 g) of sulfur dioxide gas was introduced to titrate the amine in the tissue. After diversion this gas for 5 minutes became ammonia gas in one Amount of 10.5 g introduced, which corresponds to half the amount, which was necessary to titrate the sulfur dioxide previously added to the system. These gases were diverted for 5 minutes, the system opened and air purged for 5 minutes.

(10) A pre-treated fabric (1883 g) was inserted into the Machine placed and sulfur dioxide gas in sufficient quantity (38 g) initiated to titrate the amine in the tissue. Ifaoh By diverting this gas for 5 minutes, ammonia gas was introduced in an amount of 3.3 g, which was only sufficient to fill in the free spaces in the tissue. These gases were diverted for 5 minutes, then the system opened and blow with air for 5 minutes.

(11) A pretreated fabric (2021 g) was placed in the machine and ^{heated to 57.5 0} O (136 ⁰ F). Then a sufficient amount (40 g) of sulfur dioxide gas was introduced into the system to react with the amine in the tissue. After diversion for a further 5 minutes, the system was opened and the tissue was blown with fragrance for 5 minutes. * AD ORIGINAL

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The results obtained during these experiments are summarized in Table 12.

Table 12 (170 ⁰ F) test pH of the tissue Attempt ITo * Trooken fold evaluation " 5 days treatment 77 ⁰ C 3.3 1 day 3.0 6.6 1 2.7 3.1 6.8 2 2.4 2.3 6.5 3 3 9 2.9 6.8 4th 1.9 2.3 6.7 5 1.9 2.4 6.4 6th 2.1 3.3 6.2 7th 2.8 2.5 6.5 8th 3.0 2.8 6.5 9 2.6 2.4 6.5 10 2.3 6.9 11 1.9 Example 14

The tissue-au "In" piel 1 wurdt 4.9% Monoisopropanolamine, 0.1 j 8yn-? Ao 905 and 7.2 £ urea, based on there, "Gewioht of tissue · treated.

The tissue was dried at 93 to 107 ⁰ O (200 to 225 ⁰ I) and on a Hoffaan pressure for 15 seconds

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Half-decated with steam and then im Vacuum held between 2 pieces of decatizing tissue.

This fabric, which had g a weight of 1482, was then rolled up on the warp beam a laboratory GaebehandlungB-maschlne, put into the machine and 6O ⁰ O (140 ⁰ F) · heated Then, ammonia gas in an amount of 2.6 g initiated into the system and diverted 6 minutes. The excess ammonia was then vented to the outside. Thereafter, sulfur dioxide gas was introduced into the system in an amount of 51 »4 g and diverted therein for 6 minutes. The excess sulfur dioxide gas was then vented to the outside.

Danaoh also introduced ammonia in an amount of 1.3 g into the system and diverted it for 6 minutes. Then it was ventilated for the last time and completely for 10 minutes. The fabric was removed from the machine and examined.

The original rating of the dry foldability was 3 »5. After aging in room conditions during a Week that rating rose to 4.3.

The patent is not required

909817/0681

Claims (1)

Claims (American Version) 1. Procedure for modifying the characteristic Properties of keratin fibers, characterized in that the keratin fibers are treated with a reducing agent precursor and a chemical reducing agent activator in contact, thereby giving the fibers characteristic Properties for a later permanent fixation are given to a desired design. 2. The method according to claim 1, characterized in that "that the reducing agent activator is in gaseous form State is used. 3 ο- method according to claim 2, characterized in that the keratin fibers with the reducing agent precursor brought into contact before they are treated with the reducing agent activator. 4. The method according to claim 3, characterized in that the reducing agent precursor as 1? £ aqueous solution has a pH greater than 7. 5. The method according to claim 4, characterized in that the reducing agent activator is a reducing agent having. 90 9 817/0681 BATH ORIGINAL - 57 - / 11-27 794 6. Process according to the principle that the reducing agent activator contains _{SO 2.} 7. Method naoh Inspruch 2, characterized by the fact that the Eeduktionsmittelvoretufe is used in the gaseous state. 8. Process for pre-sensitivitization τοη keratin fibers for their later permanent fixation, daduroh known · * | Seichnets that the keratin fibers are brought into contact with a beduction agent gate step, the fibers then finished in the desired way and then the Exposure to a gaseous ohemisohen reductant activator. 9 "process me fräeeneitiTierung τοη keratinfaserhaltigen Jewel) tn for" in later permanent fix, and carrion fabric is starched in a desired manner daduroh gekennieiennet _y da · bringing the fltswebe "it sin ·» ^ leduktionsmittelTorstufe in contact, then the same on gewüneohte way finished and the sole is exposed to the action of a gaseous chemical reducing agent-activator, whereby the fabric retains the desired finish and is prepared for later permanent fixation. EtAD ORIGINAL 909817/0681 - 58 - ■ 1A-27 10. Process for the presensitization of fabrics containing keratin fibers for a later permanent fixation, wherein the fabric is finished in the desired manner, characterized in that the fabric impregnated with a reducing agent preliminary stage, trooknet, finished as desired and then subjected to the action of a gaseous chemical agent activator to give the fabric the desired finish and for a later «permanent pixellation is pre-sensitized 11. The method according to claim 10, characterized in that the fabric after its impregnation trooknet in a relaxed state 12. Method naoh JLaspruoh 11, dt you raw g e k β η m -draws that one da · tissue with an aqueous Soldering the reduction agent gate step impregnated 15. Method naoh Anapruoh 12, characterized in that the Beduktionsmittelrorstufe al 1 year aqueous solution has a pH τοη more than about 7 having. 14. The method according to claim 13, characterized in that the reducing agent activator has a reducing agent in a gaseous state. 809817/0681 BATH ORIGINAL - 59 - ¹ A-27 794 15. The method according to claim 14, characterized in that the reducing agent activator SO ^ contains. 16. The method according to claim 15, characterized in that the Heduktionsmittelvorstufe an amine having. 17. The method according to claim 16, characterized in that the amine comprises an alkanolamine. 18. The method according to claim 11, characterized in that the fabric e ~ ne desired finish is imparted by steaming. 19. The method according to claim 11, characterized in that the reducing agent activator in an amount is present which corresponds essentially to at least the amount of the reducing agent precursor. 20. The method according to claim 12, characterized in that the fabric after finishing with Ammonia gas is treated. 21. The method according to claim 20, characterized in that the G-ewebe after finishing with gaseous sulfur dioxide is treated. 909817/0681 ¹ ^ ⁰ ORIGINAL 22. Method according to claim 21, characterized in that g e k e η η draws that at least part of the ammonia gas after treatment of the tissue with gaseous Sulfur dioxide is used. 23. The method according to claim 20, characterized in that the solution of the reducing agent precursor contains an alkanolamine. 24. The method according to claim 23, characterized in that g e k e η η, that the reducing agent precursor contains ammonia gas and the reducing agent activator SOp. 25. The method according to claim 24, characterized in that the reducing agent precursor is ammonia having. 26. The method according to claim 25, characterized in that the reducing agent activator is sulfur dioxide having. 27. The method according to claim 26, characterized in that at least one! Peil of the ammonia after the tissue has been treated with sulfur dioxide. 809817/0681