BE634259A - - Google Patents

Description

       

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  "Process for improving the fastness to washing or the like
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 aaracterial of a textile material dyed with cellulose acetate * #
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 The present invention relates to cellulose acetate textile materials having a very high acetyl number and more particularly relates to dyed cellulose acetate textile materials having very good wash fastness.



   As is known, the cellulose acetate textile materials conventionally used are made of acetone-soluble cellulose acetates, having

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 acetyl numbers of between about 53.0 and 55.5% calculated as combined acetic acid. These materials can be dyed very easily with the aid of the well known "cellse acetate disperse dyestuff" and a wide range of uniform shades is obtained including shades having very good lightfastness. The fastness to washing is generally moderate% usai good or better than that which can pull obtained by simple dyeing of cotton or of cellulose regenerated by direct dyeing of cotton.



  However, in general, the shades obtained with dyes dispersed on cellulose acetate soluble in acetone, in particular particularly intense shades, such as those obtained on cotton or on cellulose regenerated with direct dyes from cotton, are not sufficiently washing strength to meet the conditions of the American Association of Textile Chemists and Colorist No.3 Wash Fastness Test (see Techinical Manual and Year Book of the AATCC 1953 pages 91 and 92) .



  This applies even when the dyes are made with disperse dyes of the "high temperature slow dye" type. Dyed textile materials, which are capable of withstanding this test, are required for many applications. This test involves washing a sample of the dyed material at 71 C for 45 minutes under certain normal conditions and observing the change, if any, in the color of the dyed material and the coloration caused by the colorant removed from said material.

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  This test 3 is so rigorous that in general only a very limited group of dyed material, for example ooton or regenerating cellulose in the tank, undergoes it successfully.



   The present invention proposes to provide: - a novel dyed cellulose acetate textile material having extremely good wash fastness, for example sufficient wash fastness to successfully pass the wash fastness test N 3 AAT0.0 . above-mentioned;

   - new dyed cellulose acetate textile materials, having better properties, such as better wash fastness, better resistance to perspiration, greater resistance to wear and wet spillage, more high resistance to discoloration and sublimation, better resistance to polishing, higher safe ironing temperatures, the ability to form creases which are permanent in laundering, greater resistance to creasing during washing and less shrinkage when the fabric is pressed in the presence of water vapor.



     Other advantages and characteristics of the invention will emerge from the detailed description which follows.



   In accordance with the present invention, a cellulose acetate textile material having an acetyl content of at least 59% is dyed. oaloulé as acid

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 acetic, preferably in an aqueous bath with a disperse dye of cellulose acetate, preferably of the high temperature slow dyeing type, and the dyed material is subjected to heat treatment.



  By using this method, one can obtain textile fabrics of cellulose acetate dyed in intense shades, which can be washed a very large number of livers under the conditions of the wash fastness test AATCC N 3 without affecting. they show an appreciable change in color or coloration. In addition, the heating makes it possible to obtain a very marked increase in the temperature of ironing without risk of the textile fabric, an improvement in its resistance to polishing, an improvement in its resistance to wiping and to creasing during laundering, a to be permanently wrinkled and a marked decrease in the degree to which the fabric shrinks when pressed with water vapor. The treatment does not modify the hand or significantly decrease the mechanical strength of the fabric.



  The heat treatment of cellulose acetate textile materials having an acetyl number of at least 59% calculated as acetic acid is the subject of United States Patent Application No. 758,449
The dyeing of cellulose acetate having a very high acetyl number can be carried out in a heated aqueous bath containing a slow dyeing type cellulose acetate disperse dye at high temperature.

   This class of dyes is well known

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 in practice and is represented by compounds like
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 2-nitro-4-aulfo-anilido-diphenylaaine! 4'-ethoxy-2-nitro d1pb'laa1n.-b8t.-b1droz, -proP11aultonaa14e ° -nitro-2-aa6tBoxdr-phérl.sso- ° '-bia (bita-4ydroxy ithyl) acalno-2-a4etylamino-beasne; f 4-nitro-2-ttethylsultonephtnyl-aao- ° - (N-bta-3Aroxy-ethyl-N-ditlaoroethyl) -aminob4nzene; ° -nitrp-2-ohlorophisrl-aao ° 'b1a.



  (bita-hydroqréthyljacino-2'-taitbylbensine; 1: ° -di (ir- droth, y1.am1no) -'a 8-dlh, ydrox; r anthraquinont t 4-nitro- phen, rl-aso-4'-di (bta-hyd roqr-stbyl) -amino-2'-aoitaaino benzene 1 adlangt of 1s ° -di (hydraxyithylaAina-5s8- dihydroxy anthraquinone and 1-aolno-4-anilido- thra- quinone 1sg-dihJdroxy-8 -aitro- ° - (mita-alpha h1droX1éth1l) -ah1lldo-anthraqulnont, l! 6-dihydroxy-4- (pa - a-beta-hydroxyethyl) -anilido-5-nitro-anth quinon4, 1- amino-4- anilido-anthraq, uinone;

   and 2t4-dinitro-6- chloroph <! ayl-azo-4'-bie- (hydro] <yethyl) - <nalno-2'-tc <tyl-amino-51-methoxybenzene-Ces dye, such as sold are a mixed form of a 418- pereion agent as sodium lignosulphonate or sodium salt of a formaldehyde condensation product
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 and naphthalene sulfonic acid with the actual coloring matter and usually contain 30
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 to about 45 of the actual coloring matter.

   Of
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 commercial colourants of this type include those sold
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 praised the trademarks t "blue G 8étaoyl"; "blue GLY Batman"; "EU-40 Interohemioal blue" (Pr.227); A7 Celliton blue (Pr.227), "red Y"; Green blue BA Celliton 0 (Pr.229) "red 2B-GLP Ia8tOD ..

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 -red 2B Aaaoel8 1 * yellow CI 1 0010 "red OR Ja8tone '" rabis Il Amaoel "(Pr.239), * scarlet III" (Pr.2 ..),' blue Bols-40 Interohem1oal '% green blue H1Il. -d0 Interohemical "(Pr.229) and -blue violet? 31 Amaosl".



  All these coloring * are characterized by the fact that
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 when applied to textile materials of ordinary cellulose aodtate having an acetyl number between 53 and 55.5 under certain normal conditions
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 at 80 ° C. and it * color the textile materials in Intense shades # but when applying the dyestuffs to the same textile materials in the, said. normal conditions at a temperature below # i.e. 6000. # Textile materials are dyed only to a small extent, for example in shades the intensity of which only corresponds to 65 or less of the Intensities of Intense shades, Normal conditions.

     aforementioned involve treating one part by weight of the fabric in 50 parts by weight of an aqueous dye bath comprising 0.5 grams per liter
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 of soap, for example sodium oldate and 1 t (based on the weight of the fabric) of the dye, for one hour.



   It turned out that cellulose triacetate
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 and other cellulose acetates having a very high acityl number generally resist dyeing with
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 the above-described cellulose acetate disperse dyes of the high temperature slow dyeing type. For example, when using AF Celliton "blue which is of the high temperature type, as a dye for both ordinary cellulose acetate

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 and cellulose triaoetate at 80 F under identical conditions, the depth of the shade of the trianoetate after two hours of dyeing is only 20% or 25% of the depth of the shade obtained on the same. ordinary cellulose acetate after one hour of dyeing.

   Some improvement can be achieved by increasing the temperature of the dye bath to the boiling point. Thus when the temperature of the dye bath is brought to 95 C., the depth of the shade of the cellulose triacetate is increased to 30% in comparison with the 20 or 25% obtained at 80 C.
The rate of dyeing of cellulose triacetate and other cellulose acetates having a very high aoetyl number can be greatly increased by carrying out the dyeing with the aqueous dye bath in the presence of certain adjuvants which work in such a manner. substantive with regard to cellulose acetates * This dyeing process using certain adjuvants is the subject of United States Patent Application No. 791,392. Using these adjuvants,

   Very high aoetyl number cellulose acetates can be dyed in deep shades and in commercially acceptable time periods using cellulose acetate disperse dyes of the high temperature slow dye type. These deep shades can be obtained at temperatures well below the boiling point of the dye bath at atmospheric pressure.

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   The adjuvants used, as mentioned, have a substantive action with regard to cellulose acetate having a very high aoetyl number. Thus, when the fibers of said cellulose acetate having a very high acetyl number are placed in an aqueous bath containing the adjuvant in a uniformly dispersed state, for example in an aqueous bath containing from 0.05 to 0.2 of the adjuvant relative to the weight of the bath and having a temperature of 65 C to 90 C the adjuvant is absorbed by the fibers in an amount which is large, usually several times greater than the amount which would be absorbed by the fiber by simple mibtinodu aqueous bath, so that the concentration of said adjuvant in the aqueous bath is reduced.



  The adjuvant should also be a good solvent for the dye and should preferably have limited solubility in water. For example, one of the preferred adjuvants of the present invention, tripropyl phosphate, has a solubility in water of less than 0.9 at 25 C and of about 0.5% at temperatures between 50 and 95. C while the other adjuvants mentioned are generally even less soluble.



   Remarkable results have been obtained by using as dyeing aids such materials as terpene alcohols, for example pine oil and their ethers, for example the terpene ether glyool known as "Terposol N 8". , ethers such as tripropyl phosphate, tributyl phosphate, triamyl phosphate, trihexyl phosphate, diootyl acid phosphate, dimethyl phthalate,

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 diethyl phthalate and dipropyl phthalate, diallyl phthalate, triallyl citrate,
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 ..1ioll.t.

   ethyl, aethyl bentoate and * IiN-dihydroxy-6tthyl amides of higher fatty acids, such as capriqut and lauriquop NtN-dihydroxy acids
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 <tbyl amides which can be prepared by reacting
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 the d1 & hanola = 1ne with the fatty acid at an elevated temperature @ while removing the water.

   As other materials which and have been found to be effective as an adjuvant, mention may be made of aroaatic hydrocarbons, halo-Senated compounds, hydroxar compounds, arboJ11iqu acids, glycol ethers, lactones and others such as oumene, diphenyl, naphthalene titra hydronaphthalene trionlorobensene, 0101oh.1 phenol, o-phenyl-phenolp salicylic acid #
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 benzoic acid, ethylene mono-phenyl ether
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 glyool, ethylene glycol mono-dichlorophenyl ether and mono-p-ohloroph'D11 ether. ethylene
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 glycol, mono-phenyl diethylene ether glyool
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 and acetophenone; the alkylic enterera or other esters of mono-and-pol1-oarbox, lique acids. aromatics, such as dibutyl phthalate; 2¯methyl-Wthyl¯
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 pyridine;

   set superior aliphatic alcohols, such as
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 deoanol, alkyl phosphates such as tx, oaty, iquee phosphates, for example tri-n- phosphate
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 ootyl, dipropyl acid phosphate 1 phosphate
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 dibutyl acid, diamyl acid phosphate, dideoylo acid phosphate and dilauryl acid phosphate; dibutyl- ettanolamiae! 1e 4ii, obut, l oarbinol le "Maypon Kw (a product of oondonsation

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 a product separated from protein and a fatty acid);

   alkamine N-30 "(a condensate of anine crass); the" CR140229-G215 (an ester obtained by condensation of lauric acid and 8 to 10 percent of ethylene oxide) and the known aryl amine under the name of Kar-In "However, these latter materials are not considered to be as generally useful as the adjuvants uttered previously mentioned., that is to say terpene alcohols and their ethers, phosphate tripropyl, triamyl, trihexyl and tributyl phthalates of idmethyl, diethyl, diallyl and dipropyl, diootyl acid phosphate, triallyl citrate, methyl salicylate,

   methyl benzoate, and the condensation products of fatty acids and amino diethanol, since in many cases the materials are toxic or are too volatile or do not readily solubilize some of the disperse acetate dyes of the high type. temperature, or exhibit some tendency to stain unless additional dispersants are available, or do not increase the dye rate to the same extent as the preferred adjuvant, or are sometimes detrimental to mechanical properties and the dimensions of the fabric.



  The adjuvant is preferably capable of dissolving the pure dye up to the content of 0.1% by weight or more, for example 0.5 to 1% by weight or more.



   Mixtures of the dyeing aids can be used if desired. For example, excellent results have been obtained using a mixture of

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 tributyl phosphate and the condensation product of diethanolamine and capric acid, for example N: N-di (hydroxyethyl) capramide, said mixtures containing for example 20% at least, for example 50% by weight of each of these adjuvants Other mixtures of the dyeing aids which have given excellent results are, for example, a mixture of equal parts of pine oil and the aforementioned condensation product of diethanolamine and capric acid;

   a mixture of 40% by weight of tributyl phosphate, 40% by weight of pine oil and 20% by weight of the above-mentioned condensation product of diethanolamine and capric acid; a mixture of 40% by weight of tripropyl phosphate, 40% by weight of tributyl phosphate and 20% by weight of the aforementioned condensation product of diethanolamine and oapric acid.



   In general, the dye hain must contain a dispersing agent in order to guarantee the correct dispersion of the dye. As previously indicated, the commercially available cellulose acetate disperse dyes are preparations containing these dispersants in intimate admixture with the actual colorant. In practice, it is customary for the dyeing of ordinary acetone-soluble cellulose acetate to incorporate into the dye bath additional amounts of a dispersing agent beyond those present in the commercial dye.

   However, the Applicant has found that for the dyeing of cellulose triacetate

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 and other cellulose acetates having a very high acetyl number in the presence of the builders, the presence of an excessive amount of the dispersing agent generally causes a decrease in the dye level. Therefore, it is usually desirable to maintain the amount of the dispersing agent in the dye bath to a minimum value commensurate with the particular conditions of the dye and dye.



  On the other hand, certain dispersing agents having a substantive action with respect to the fibers can be used to promote the action of the dyeing aid. Thus, the condensation product of diethanolamine and capric acid, which has certain dispersing properties and deterging action, can be used to promote the dispersion of tributyl phosphate or tributyl phosphate. pin, for example.



   When the amount of the dispersing agent is too small, the material may be unevenly colored. For example, dyed fabric may exhibit more strongly dyed round spots when the adjuvant used is not automatically dispersible in water and there is an insufficient amount of dispersing agent. Therefore, when such an adjuvant is used, there must be a sufficient amount of dispersing agent to ensure even dyeing under the particular dyeing conditions used.

   Thus, in many cases a higher ratio of dispersant to adjuvant should be used, for example up to about 1: 5.

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 when a more concentrated dye bath is used, such as in wool dyeing, than when a relatively dilute dye bath is used as in reel dyeing. If we want it, we can
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 treat the fabric having the au4-noutonnée stains to remove them by degreasing the fabric at a high temperature @ for example at 95 * 0.

     in the presence of a potent * of which '# ullioDD & Dt oamoa the nonionic reaction product of rioin oil and th11nt oxide sold to the state.-U'D1. dtmdrique all the name -I # ulphor SUL-719 "\ the degreased fabric can then be repainted free of stain # The word" Eauxphor "is a * trademark
The coloring adjuvant can be added directly
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 in an aqueous dye bath with the odorant or it can be applied to the surfaces of the textile material having to bring the textile material into contact with the bath of
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 dyeing.

   In the latter case # this is carried out having.- geuaement the process by padding a * tail * dispersion of the toînturop adjuvant, for example an * 'aqueous mulsion containing the adjuvant and a disportionp agent on the surfaces of a fabric comprising cellulose acetate fibers having an acetyl indicator plus iloydr and then introducing the wet fabric thus obtained into the bath of dyes in the mine in operation of the prevents i.

   # * t. the aqueous dye bath is preferably kept at an elevated temperature, the best results
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 being obtained at temperatures * of at least 6500, approximately *

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 Temperatures up to the boiling point of the dye bath can be used, and in fact the dye bath can be maintained at a pressure above atmospheric pressure so that it can be heated to temperatures three times above the point d. The dye bath boils normally, but this has not been found to be essential from a practical point of view.



   The amount of the adjuvant the pH of the dye bath the proportion of the dye in the dye bath and the ratio of the liquor, that is to say the ratio of the weight of the dye bath to the weight of the fabric which can vary within a large Moor. So. excellent results have been obtained with an amount of adjuvant in the dye bath of between about 5 and 20 (relative to the weight of the fabric) and when the pH of the bath is between about 6 and 9 * Natural leaent, it is preferable to use tincture baths containing minimum amounts of the adjuvant.



  As regards the amount of the dye, it is of the same order as that generally used in dye baths containing dispersed dye of cellulose acetate, for example from 0.1% to 4.0% approximately (based on the weight tissue) * For best results the liquor ratio should not be too high, for example it should not be more than about 80, preferably about 50 or less, for example between 50 and 30 when the dyeing is carried out on a reel, since at higher liquor ratios the dye bath is generally too diluted.

   when processes other than reel dyeing are used to set the

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 dyeing bath in contact with the material to be dyed, the liquor ratio is much lower, for example about 10 in the case of pack dyeing and about 5 in the area of wool dye.



   When the adjuvant is applied to the textile material before bringing the textile material into contact with the dye bath, the total amount of the dyeing aid used can be significantly reduced, particularly in the case of dyeing aids such as for example tripropyl phosphate, tributyl phosphate, dimethyl phthalate and dibutyl phtate, which are not easily removed from the surfaces of the textile material by the dye bath.



  Thus, an emulsion having a concentration of about 1 to 5% of the dyeing aid can be applied to the fabric in an amount substantially equal to the weight of the fabric (eg, 75 to 100% of the emulsion based on the weight of the fabric. weight of the fabric) at a temperature of for example between 20 and 60 ° C. before introducing the fabric into the dye bath which does not contain additional dyeing adjuvant. Although the total amount of dyeing aid used is only about 1 to 5% based on the weight of the fabric, the results * are equal to or better than those obtained using larger amounts, for example 5 to 20% adjuvant in the dye bath.

   In fact, when this process is used, instead of the process in which the adjuvant is added directly to the dye bath, the dye rate is generally higher, so

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 that the dyeing period is considerably reduced.



  With adjuvants which are more easily removed from the surface of the fabric by the action of the coloring bath, such as the condensation product of diethanolamine and capric acid, it is preferable to use dispersions containing a higher concentration of the adjuvant, for example from 5 to 10%, when the dispersions are applied to the fabric before bringing the latter into contact with the dye bath.



   After dyeing the textile material made of cellulose triacetate or other cellulose acetate having a very high acetyl number, it is rinsed in a manner well known in the dyeing field to remove other dye bath components. than the dye and subjected to a heat treatment according to the present invention. The heat treatment has the effect of improving the wash fastness, the perspiration fastness and other coloring properties and, as already indicated, it can improve still other properties of the textile material, for example the temperature of the textile material. safe ironing, the ability to take permanent creases, resistance to polishing and shrinkage by pressing with damp steam.



   The temperature at which the heat treatment is carried out and the duration of the treatment will depend to some extent on the heat treatment medium. Thus, when hot air is used as the heating medium, an improvement in the properties of the textile material can be obtained by using

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 air temperatures of about 190 C, although optimum results are obtained at much higher temperatures, for example at air temperatures of about 250 C.

   Thus, heat treatment of a staple fiber of a yarn or woven fabric of cellulose triacetate dyed in hot air at a temperature of 190 C for 20 minutes greatly improves the wash fastness of the material and the Safe ironing temperature of the fabric, hand only improves the polishing resistance and the resistance to shrinkage by pressing with moist steam only to a relatively small extent, although heat treatment of the same fabric with hot air at a temperature of 250 C. for a few seconds ensures a very marked improvement in all these properties * In addition,

   As can be seen from the results described in the preceding sentence, the desired improvement in the properties of the textile material can be achieved much more rapidly when the higher temperatures are used. To obtain the best results, the heat treatment should not be carried out at temperatures and for prolonged periods of time so as to seriously alter the color, tensile strength and elongation at break or other mechanical properties of the material. the textile material.



   Heat treatment has a dynamic process and involves heating the textile material to the high temperature. In reality, it is believed that the textile material should be at this high temperature only

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 for a very short time and most of the time is spent heating the tissue to that temperature * However, the use of heat sources with very high temperatures * to decrease the treatment time is not very convenient,

   since the outer surface of the fibers or fabric can then reach a temperature high enough to cause damage before the inside of the fibers * or fabric has reached the correct temperature. In addition, it is very difficult to detect the exact temperatures * actually reached by the fabric during heat treatment.
Therefore, it is evident that for commercial heat treatment of any particular fabric and with any particular apparatus it is preferable to carry out simple tests in order to determine the best heat treatment conditions.

   These tests or trials are carried out in an easy and rapid manner by exposing samples of the tissue to heat in the apparatus to be used, using various conditions of time and temperature and observing the characteristics of the samples processed. such as the safe ironing point and the degree of degradation, if any.



  The textile material can be heat treated in a relaxed state or while it is kept under tension. The heat treatment can be carried out while keeping the dimensions of the textile material substantially constant, for example by using an expander. Heat treatment in the relaxed state provides some shrinkage in the textile material,

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 This shrinkage is very low in the case of acetates
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 of celluloses-an! aoetyl numbers greater than 61%.



  Thus, when heating a cellulose acetate yarn having an aoetyl number of 61.3% in the relaxed state, at a temperature of 250 ° C. for 30 seconds and then cooling it, the yarn will not only shrinks by about 4%. Shrinkage is normally less when thermally heating a woven fabric. instead of wire.



   The heat treatment in the relaxed state, with the associated shrinkage, is often advantageous when it is necessary to avoid the elimination of creping of the fibers constituting the textile material and to avoid flattening of the fabric.



   The optimum heat treatment times will depend to some extent on the weight and construction of the fabric, since for example a longer period of time is required to bring the fabric to the desired elevated temperature in the case of 'a heavier or tighter woven fabric than in the case of a lighter or looser woven fabric * Thus, a relatively light woven fabric weighing approximately 136 grams per square meter, described in more detail below, is advantageously heated. in hot air at a temperature of about 230 ° C. for about 5 seconds at the raine, but not more than one minute in order to avoid damage to the tissue, preferably for a period of slightly less than 1 minute .

   For the same fabric at temperatures of 25000 and 270 C., the corresponding temples are at least about 5 seconds and

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 at least about 2 seconds respectively and not longer than about 30 seconds and not longer than
About 15 seconds, respectively. When using a relatively heavy fabric weighing 221 to 238 g per square meter and consisting of staple fibers, described in more detail below, the corresponding maximum times are twice as long as those indicated above, it is i.e. approximately two minutes, one minute and 30 seconds at temperatures between 230 and 250 C and 270 0 respectively, while the minimum times correspond to double or a little more than double the minimum times indicated for the relatively light fabric.

   When it is desired to obtain maximum improvement in the resistance to polishing and shrinkage upon pressing with wet steam, the heat treatment should be continued for as long a time as possible to achieve this without severely damaging the fabric. Thus, by suitable heat treatment of a fabric of cellulose acetate having an aoetyl number of 61.3, shrinkage on repeated wet steam pressing can be decreased to less than 4. % and the tendency of the fabric to shine during pressing and ironing can be practically eliminated.



   The aforementioned "relatively light fabric" consists of 150 denier yarns, each yarn being 40 continuous filaments of cellulose triacetate. The fabric is a 2 by 1 twill fabric and has 120 ends and 72 picks per 2.5 centimeter unit.

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   The above * relatively heavy fabric consists of 3 denier staple fibers, with a * 5 cm length, threads in 20a two-ply yarn (cotton count) with 15% twist in the strands * individual and 14s in the yarn, and woven with 44 ends and 42 picks per unit of 2.5 or in a suitable fabric to be worn in the tropics *
When using saturated water vapor as a heating medium,

   the heat treatment can be carried out at lower temperatures *. However, a significant improvement in the properties of the fabric can be obtained by treating it with saturated steam under a pressure of 1.4 kg / oa2 at a pressure gauge for 5 minutes, although a treatment period of 30 minutes gives the best results at this pressure * Steam can also be used at higher pressures, for example 2.1 to 3.5 kg / cm2 at manometer. When treating with water vapor, it is desirable to prevent the condensate droplets from contacting the material being processed, since such droplets sometimes stain the dyed material.



   If desired, other heat treatment media can be used, for example superheated steam, hot oil, or sheared metal, or the textile material can be heated by subjecting it to a high frequency electric field. or to infrared radiation or the textile material can be heated by bringing it into contact with hot rollers or hot plates. We can perform the treatment

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 thermal at atmospheric pressure at a pressure greater than atmospheric pressure or even at a pressure if greater than atmospheric pressure.



   Heat treatment tends to stiffen the fabric slightly. This stiffness can be eliminated by subjecting the fabric to mechanical treatment, for example to operations known as "button breaking" or cold-spreading or to a wet treatment, for example washing or deweaving. The tendency to stiffen can be eliminated by applying a very finely divided solid material to the textile material before heat treatment; for example, a dispersion of elioe such as the anionic dispersions of one micron particles of silica known as Ludox or "Syton W-20 or DS" can be applied to the fabric for this purpose. The words "Ludox" and "Syton" are trademarks.

   The least stiffening of the fabric has been observed when the heat treatment is carried out using pressurized steam, for example in an autoclave.



   As indicated, the safe ironing temperature of the textile material is improved significantly by the heat treatment of the present invention. For example, the safe ironing temperature of fabrics made from fibers (directly from spinning) of cellulose triaoetate or of a cellulose acetate having an acetyl number of 59.5 calculated, as acetic acid combined, is not more than 190 C., for example about 180 C. By thermally treating these fabrics

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 according to the present invention, the safe ironing temperature is increased by more than 2000, about to a value greater than about 220 C or 230 C, usually greater than about 240.



   The effect of heat treatment is most pronounced in the case of cellulose acetates with the highest acetyl numbers. Thus, for example, cellulose acetates having acetyl numbers of 61 or 62% or more, calculated as combined acetic acid, show the greatest improvements in heat treatment in terms of polish resistance, resistance. to shrinkage by pressing with wet steam and ironing temperature without risk compared to cellulose acetate with an index of 59.5%, calculated as combined acetic acid. On the contrary, when a fabric of ordinary cellulose acetate, for example having an acetyl number of 54.5%, is subjected to the heat treatment of the present invention, the fabric is severely damaged.

   To obtain optimum properties for fabrics sold on a commercial scale, the acetyl number should be at least 60 and preferably at least 61%.
In accordance with one aspect of the present invention, the heat treatment can be applied to dyed textile materials in which most of the dye has been absorbed only on the surface of the fibers. Thus, when certain dyeing aids are used, for example esters of polyacids such as tributyl phosphate,

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 Dimethyl phthalate and diethyl phthalate, it is noted that even at temperatures as low as 65 ° C there is application of the dye to the fibers to provide a peripherally dyed or "surface dyed" material at the start of dyeing. .



  The fiber is truly dyed as shown by examination of cross sections of the fibers revealing that the dye is inside the fiber and by the fact that the dye is not washed away. When this material is subjected to heat treatment in accordance with the present invention, the dyed material becomes very solid on washing and does not spoil in part due to further diffusion of the dye into the cross section of the fiber.



   The heat treatment according to the present invention may have the additional effect of removing a large part of the dyeing aid from the textile material. Since the dyeing aids have a substantive action against cellulose acetate having a very high acetyl number, an appreciable proportion of these aids remains in the textile material after dyeing, even after rinsing and rinsing. degreased the textile material.



  For example two parts of a cellulose acetate fabric having an acetyl number of 61.3 parts which have been dyed, one in the presence of tributyl phosphate as an adjuvant and the other in the presence of tripropyl phosphate have been dyed. proven, after degreasing at 49 C to have a PO4 content, resulting from

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 the presence of the above phosphates, 1.64% and 1.44% respectively.

   After heating the parts of the fabric for 31 seconds by subjecting them to infrared radiation so that their surface reaches a temperature between 245 and 255 C their PO4 content has been reduced to 0.12 and 0.08% respectively. due to the evaporation of the phosphates. Similar results are obtained with other adjuvants which are volatile at the temperature of the heat treatment, for example pine oil. However, the high temperature slow dyeing cellulose acetate dyes used in the present invention do not evaporate or decompose to any appreciable extent during heat treatment and remain substantially all in the textile material.



   In some cases, it is advantageous to degrease the textile material after the heat treatment. This degreasing has been found to decrease the tendency of the material to color the water used for the first household wash or laundering, possibly by removing a very small amount of the weakly adhering dye. This degreasing treatment can be carried out, for example at a temperature between 49 and 66 ° C., using an aqueous degreasing bath containing from 0.5 to 2 grams per liter of a nonionic or anionic detergent after the "Emulphor ELA". -719 "or" Duponol RA "
Either of the common sizing agents can be applied to textile materials produced in accordance with the present invention.

   For example, we can apply

 <Desc / Clms Page number 26>

 to the textile material a silicone binder comprising a polysiooxane containing methyl or other groups. hydrocarbon groups and preferably also hydrogen atoms attached directly to the silicon atoms. Other sizing agents which can be applied include waxy polyethylene; waxy sulfonated fats 1 black cationic long chain amino compounds of the finely divided alloy; finely divided titanium dioxide and a resinous or resin-forming condensation product, such as the reaction products of melamine, stearamide and formaldehyde.



  Other resinous or resin-forming condensation products which can be applied include the reaction products of formaldehyde with urea or thiourea or substituted or cyclic ureas such as urea ethylene or melamine, alkylation products of these reaction products, for example di- (methoxy-methyl) urea, tri-methoxymethyl) melamine or N: N'-di-methoxymeth) ethylene urea.

   The amount of the sizing agent applied is relatively small, for example about 0.25 to 2%, and the sizing agent is used very conveniently by applying to the textile material an aqueous dispersion of said sizing agent. sizing, after which the textile material is dried and when it is necessary to cure the sizing agent as in the case of silcones and resinous condensation products, it is then baked at an elevated temperature.

   Suitable finishing agents are sold under the names "De Cetex 102"

 <Desc / Clms Page number 27>

 
 EMI27.1
 "DeOetex 104nit" De Cetex 108 * t Waydropruto; "R <p $ llwtM P '0", "Ahoo 111", "Ahoovel E", "Ahoovel Ont" Ahoovtl 90%,
 EMI27.2
 14 "Ahoovel nftt" Aquex 15 "p" Aquex 16x "," Pormelwt * Aorotox AHC0V61 A "Ahoove7,", aqueous 1 "," Aauex 16x "," pirmil, "AAratlx softener H", "Paropon R" "Silicone 81386 from General Eleotrio, "Syton W-20", "Dullatone", "Aerotex Resin 801" Aerotex cream 450 "," Rhonite R-1 and "Rhonite N-5".



  The words "De Oetex" "Achovel" and "Paropon" are trademarks. The finishing agents can be applied to the dyed material before the heat treatment, but preferably afterwards.
 EMI27.3
 applying certain finishing agents, such as silioones, for example "De Cetex 104" to the textile material and they can be cured even before dyeing without appreciably affecting the dye rate.

     Sizing agents which act as a surface lubricant, for example silicones, waxy polyethylene and other waxy softening agents, and condensation products of melamine, formaldehyde and stearamide, greatly increase the resistance of the coating. abrasion-dyed textile material, abrasion which sometimes causes the detachment of fragments of fibers and thus gives a tortoiseshell appearance.



  These sizing agents also improve the tear resistance of the material. Combinations of the sizing agents, for example combinations of silicones or waxy polyethylene with products, can be used.
 EMI27.4
 condensation of urea and formaldehyde or melamine and formaldehyde to combinations of finely divided dispersed silica and silioones, if desired, with condensation products of urea or melanin and formaldehyde.

 <Desc / Clms Page number 28>

 



   Cellulose acetate having a very high acetyl number dyed with certain dispersed cellulose acetate dyes tends to be discolored upon exposure to acidic vapors such as combustion gases and in some cases during combustion. exposure to ozone. To reduce this tendency, it is often desirable to apply an appropriate inhibitor to the textile material. The inhibitor can be applied, for example, by incorporating it into the dye bath, spraying a solution or dispersion of the inhibitor before or after dyeing or by applying the inhibitor after the heat treatment. It is generally desirable to apply the inhibitor prior to heat treatment.

   As examples of suitable inhibitors, there may be mentioned those conventionally used for ordinary cellulose acetate soluble in acetone,
 EMI28.1
 such as diphenylimidazolidine, NiNI-diphenylethylenediamine, NiNI-dibenzylethylenediamine and methyl substitution products or other alkyl substitution products thereof, diphenyl-
 EMI28.2
 benzamidine, dipridny, aaétamid.ne, benzylethyl-aniline, sodium formate or "Meleine" (melamine which has been partially dissolved in water by reaction with a small amount of formaldehyde).



  To prevent the alteration of the color by ozone, anti-oxidants can be used, for example tertiary butyl hydroquinone, alkylated phenols, such as
 EMI28.3
 "lonol" and ..... "inhibitor 162" and many of the nitrogen inhibitors mentioned above. The word "lonol"

 <Desc / Clms Page number 29>

 is a trade mark. The amount of the Inhibitor is generally low, for example 0.5 to 3% based on the weight of the textile material.



   It has been found that even without the use of an inhibitor, the attractant dyed textile of cellulose acetate having a very high acetyl number which has been thermally treated according to the present invention exhibits a much lower tendency to undergo. alteration of the cculeur by being exposed to the ozone that the same fabric dyed before the heat treatment,
As indicated, the heat-treated fabrics of the present invention can be permanently pleated. Thus, in one example,

   a thermally treated fabric of cellulose acetate having an Acetyl Number of 61.3% and accordion pleated on a steamed prose using a pressure of 227 kg while vaporizing for 10 seconds with steam of water having a gauge pressure of 3.5 kg / ca2 the plies remain in the washing.



  Permanent plies can also be obtained by creasing the fabric arcrnt or during heat treatment: for example, a wire that has not been heat treated can be pleated between metal rolls @ at a temperature of 177 * 0., Then it can then be thermally treated, for example with water vapor under a gauge pressure of 1.4 kg / cu 2 in an autoclave.



   If desired, the very high aoetyl number cellulose acetate textile material can be embossed or raised to form any suitable pattern before, during or after.

 <Desc / Clms Page number 30>

 heat treatment.

   For example, a woven fabric of cellulose acetate having a very high acetyl number can be applied a surface pattern which is wash-smooth by the application of a metal embossing roller at a temperature of 204 ° C.
Although the process of the present invention has been described with particular reference to textile materials consisting entirely of cellulose chippings fibers having a high-grade acetyl number, it is also applicable to other materials. textiles comprising such fibers,

   for example materials constituted by mixtures of these fibers with other fibrous materials, such as wool, cotton, rayon, glass fibers and asbestos. These mixtures can be dyed under conditions such that all types of fibers of the melagna are dyed at the same time or they can be dyed in stages so as to color the different types of fibers successively. The fiber blends can be successively dyed or dyed together. The process of the present invention is applicable to textile materials consisting of discontinuous fibers of cellulose acetate having a very high acetyl number, as well as those formed by fibers. continuous filament * of said cellulose acetate.



   Although the heat treatment of the present invention is the most valuable and gives optimum results when used with cellulose acetate textile materials having a very high acetyl number dyed with acetate dyes. slow dyeing type cellulose to high

 <Desc / Clms Page number 31>

 temperature, it can also be applied to textile materials of cellulose acetate having a high aceyl number dyed with other dyestuffs, for example with dispersed cellulose acetate dyes of the low temperature or high temperature type medium, such as 2-nitro-4-sulfonamido diphenyl amine,

   p-nitro-phenyl-azo-diethyl aniline or 1-amine-4-hydroxy-anthraquinone. In these cases, the safe ironing temperature, the polishing resistance, the resistance to shrinkage during steam pressing and the ability to exhibit permanent creases are improved, as well as the washing fastness of the fabric. material, but the improvement is not sufficient for the latter property to allow the material to pass the A.TA.TCC N 3 wash fastness test successfully. Further, materials dyed with high temperature slow dyeing type dyes generally exhibit superior resistance to gas discoloration, light discoloration and sublimation.



   The following examples are given by way of illustration and without limitation of the invention, EXAMPLE 1 (A) (a) A woven fabric comprising fibers of cellulose acetate having an acetyl number of 62 is dyed according to the present invention, 0% to 62.5% calculated as combined acetic acid, the fibers having been obtained by spinning a solution of cellulose aoetate; in a mixture of 90% methylene chloride and

 <Desc / Clms Page number 32>

 of 10% ethanol in an evaporating atmosphere.



  The fabric used is a two-on-one twill fabric, weighing approximately 136 grams per square meter and having
120 ends and 72 picks per unit of 2.5 cm, each yarn of both the weft and the warp being 150 denier and comprising 40 continuous filaments. The dyeing is carried out for one hour in an aqueous dye bath maintained at a temperature of 85 ° C. and containing 2% (based on the weight of the fabric) of the "GLF Eastman blue" dye (containing about 40% of the coloring matter. active) 10% (based on the weight of the fabric) of tri-n-propyl phosphate and 1% (based on the weight of the fabric) of the product sold in the United States of America under the name "Igepon T Gel% un dispersing agent which comprises as active ingredient 16% of the sodium salt of oleylin taurine.

   The word "Igepon" is a trademark. The liquor ratio, i.e. the ratio of the weight of the dye bath to the weight of the fabric, is 50. After dyeing, the wet fabric is rinsed for 15 minutes at 35 ° C in a bath containing 2 grams per liter of soap and dried.



   Four other parts are dyed with the same fabric.



  The dyeing conditions which are different in each case are identical to the dyeing conditions indicated in paragraph (a) above with the following exceptions: (b) An equal weight of pine oil is substituted for the tripropyl phosphate.



   (c)! 0% tripropylphosphate 10% (based on tissue weight) is substituted for "Alrosol C"

 <Desc / Clms Page number 33>

 a condensation product obtained by heating two moles of diethanolamine with one mole of capric acid while removing the water from the reaction said condensation product comprising N:

  N-di- (hydroxyethyl) capramdie This product of condenation is a liquid soluble in water and in organic solvents Its solutions in water are dilute liumides and slightly mlcaens do not gel on dilution with water and tolerate electrolyte @ * (d) The dye bath does not contain additional admixture or “Igepon T.” but simply “GLF Sastman blue” and water.



   (e) The dye bath contains no additional adjuvant but simply "GLF Eaatman Blue", water and 1% (based on fabric weight) of "Igepon T".



   The following table compares the results obtained during the above dyes:
 EMI33.1
 
<tb> Type <SEP> of <SEP> bath <SEP> of <SEP> dye <SEP> Color <SEP> of <SEP> fabric
<tb>
<tb>
<tb>
<tb> (a) <SEP> Tripropyl <SEP> phosphate,
<tb>
<tb> "Igepon <SEP> T" <SEP> and <SEP> water <SEP> Shade <SEP> blue <SEP> deep.
<tb>
<tb>
<tb>
<tb>



  (b) <SEP> Oil <SEP> from <SEP> pin, <SEP> "Igepon <SEP> T" <SEP> Shade <SEP> almost <SEP> also <SEP> Intense
<tb>
<tb>
<tb> and <SEP> water <SEP> than <SEP> (a)
<tb>
<tb>
<tb>
<tb> (c) <SEP> "Alrosol <SEP> C" <SEP> and <SEP> water <SEP> Shade <SEP> slightly <SEP> plus <SEP> clear
<tb>
<tb> than <SEP> (b)
<tb>
<tb>
<tb>
<tb>
<tb> (d) <SEP> Water <SEP> Shade <SEP> very <SEP> pale * <SEP> a lot
<tb>
<tb> clearer <SEP> <SEP> than <SEP> (c)
<tb>
<tb>
<tb>
<tb>
<tb> (e) <SEP> "Igepon'T" <SEP> and <SEP> water <SEP> More pale <SEP> <SEP> than <SEP> (d)
<tb>
 

 <Desc / Clms Page number 34>

 
We repeat the Processes (a) (b), (cz) (d) and (e) described $ Or $ paragraph (A) above,

     except that the dye * AF Celliton blue "(containing about 40% of otitis dye) is substituted for" GLF Eastman blue "the results are shown below:
 EMI34.1
 
<tb> Type <SEP> of <SEP> bath <SEP> of <SEP> tantur <SEP> Color <SEP> of <SEP> fabric
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> (a) <SEP> Tripropyl Phosphate <SEP>, <SEP> Deep blue <SEP> <SEP> shade
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> "Igepon <SEP> T" <SEP> and <SEP> water
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> (b) <SEP> Oil <SEP> from <SEP> pin, <SEP> "Igepon <SEP> T" <SEP> Grade <SEP> almost <SEP> too
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> and <SEP> water <SEP> deep <SEP> than <SEP> (a)
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> (0)

   <SEP> "Alrosol <SEP> C" <SEP> and <SEP> water <SEP> Grade <SEP> slightly <SEP> more
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> clear <SEP> than <SEP> (b)
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> (d) <SEP> Water <SEP> Grade <SEP> very <SEP> pays,
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> a lot <SEP> more <SEP> clear
<tb>
<tb>
<tb>
<tb>
<tb> than <SEP> (c)
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> (e) <SEP> "Igepon <SEP> T" <SEP> and <SEP> water <SEP> Shade <SEP> substantially
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> identical <SEP> to <SEP> (d)
<tb>
 (0) (a) A woven fabric comprising cellulose acetate fibers having an acetyl number of 62.0% to 62.5% calculated as combined acetic acid is dyed,

   said fibers having been obtained by spinning a solution of cellulose acetate in an organic solvent for the latter in an evaporating atmosphere for one hour in a dye bath maintained at a temperature of 85 ° C. and containing 1% (based on fabric weight) of "GLF Eaatone Red" dye, 10 "(based on fabric weight) pine oil and 1% (based on fabric weight) of an agent dispersion comprising equal proportions by weight of the dispersing agents known under the names of "Emulphor ELA-719 (a nonionic product of the reaction

 <Desc / Clms Page number 35>

 (castor oil and ethylene oxide) and "Quadronate" (a "mahogany soap" that is, a low molecular weight petroleum sodium sulfonate).

   The liquor ratio is 50 and the fabric is washed after dyeing in a manner analogous to that described in paragraph (A) above and dried.



   Two other parts of the same fabric are dyed.



  The dyeing processes, which are different for each of the parts, are identical to those described in the previous paragraph, with the following exceptions: (b) 10% pine oil is substituted for 10% (based on the weight of the fabric ) "from Alrosol C and the dispersant is removed.



   (c) Pine oil and dispersing agent are removed.



   The results are shown in the following table
 EMI35.1
 
<tb> Type <SEP> of <SEP> bath <SEP> of <SEP> dyeing <SEP> Color <SEP> of <SEP> fabric
<tb>
<tb> (a) <SEP> Oil <SEP> from <SEP> pin, <SEP> agent <SEP> from <SEP> Shade <SEP> red <SEP> deep
<tb> dispersion <SEP> and <SEP> water
<tb>
<tb> (b) <SEP> "Alrosol <SEP> C" <SEP> and <SEP> water <SEP> slightly <SEP> plus <SEP> clear
<tb> than <SEP> (a)
<tb>
<tb> (c) <SEP> Water <SEP> Shade <SEP> red <SEP> pale <SEP> much <SEP> more <SEP> clear <SEP> than <SEP> (b),
<tb>
 
The dyed fabrics prepared as described in paragraphs (A), (B) and (C) above are heat treated in an oven in hot circulating air having a temperature of 230 0 for 60 seconds,

   while maintaining the fabrics in expanders to keep their dimensions substantially constant throughout the heat treatment.

 <Desc / Clms Page number 36>

 



  Heat treated fabrics are subjected to the A.A.T.C.C. N 3 and it is found that they retain their color, without appreciable change in color or coloration, even after three repetitions of said test. The heat treatment increases the safe ironing temperature of the dyed fabric by 6000., that is, from 180 to 240 C., improves the shine resistance of the fabric and decreases the degree of wrinkling that occurs during laundering.



  Heat treated fabric shrinks 9 of its surface after 12 wet steam pressing, compared to 155 shrinkage for fabric that has not been heat treated. The heat-treated fabric can be pleated in a steam press using a damp fabric and strong mechanical pressure, and the pleats thus obtained are permanent and remain after repeated washing at 71 ° C. The hand and the mechanical strength of the fabric. fabric are substantially the same before and after the heat treatment.



   The aforementioned "safe ironing temperature" is determined using a conventional hand iron weighing 2.27 kg and having a sole area of 145 cm 2. The test is carried out by heating the iron until a selected area of 5 cm per side of the sole plate in the vicinity of the tip of the iron has reached the desired temperature.

   A 5 cm side part of the fabric to be tested is placed on an ironing surface comprising a flat board covered with 2.5 cm foam rubber on which are four oouohes of cotton flannel and

 <Desc / Clms Page number 37>

 the iron is then placed on the fabric so that the above-mentioned selected area of the sole coincides with the fabric, The dwarf iron is placed without lateral movement of the iron on the fabric and without applying pressure to the fabric. iron on the fabric.

   After the iron has remained on the fabric for 10 seconds exactly the iron is lifted directly away from the fabric. The test is repeated increasing the heat of the iron by 10 C for each test, until A sign of damage to the fabric is obtained, for example until the fabric sticks to the iron becomes harder or changes color.

   The maximum safe ironing temperature corresponds to the temperature which is 10 C below the temperature at which the first sign of damage to the fabric occurs,
EXAMPLE 2
The procedure of Example 1 (A) (a) is repeated, except that tri-n-butyl phosphate is used in an amount of 5 (based on the weight of the fabric) in place of the tripropyl phosphate;

   the dispersant is a mixture of 0.25 (based on tissue weight) "Emulphor ELA-719" and 0.25 (based on tissue weight) "Quadronate"; the dye is "Ruby IX Amacel" and is used in an amount of 2% based on the weight of the fabric and the dyeing is carried out at 80 ° C. The fabric is dyed an intense red shade and is then heat treated as described in example 1.

 <Desc / Clms Page number 38>

 



   EXAMPLE 3
A portion of the woven fabric described in Example 1 was dyed for 30 minutes in an aqueous dye bath maintained at a temperature of 65 ° C. and containing 2% (based on the weight of the fabric) of the "Beo A? Celliton" dye ( containing 40% active coloring matter) 10 (based on the weight of the fabric) of tri-n-butyl phosphate and 0.5 (based on the weight of the fabric) of "Quadronate" and 0.3% (based on the fabric weight) "from Eaulphor ELA-719". The tributyl phosphate, which is a liquid, is first mixed with the "Emulphor ELA-1790 and the" quadrate "and the resulting pite is then mixed with the water of the dye bath. is 50.

   After dyeing, the "surface dyed" wet fabric is rinsed for 15 minutes at 350 ° C in a bath containing 1 g per liter of "Igepon T Gel *.



  The tiaau is dyed an intense blue shade. It is then subjected to the heat treatment described in Example 1, after which the dye becomes very solid on washing and does not flake.



    EXAMPLE 4
A portion of the woven fabric described in Example 1 is wrapped at a temperature of 50 ° C. with a bath comprising an emulsion containing 5% by weight of tri-n-butyl phos phate, 0.5 "of Emulphor ELA-719. ", 0.5%" Quadronate ", the remainder being water, all of which are based on the total weight of the emulsion. After crumbing the fabric in contact with the padding bath for 30 seconds, the fabric is introduced, supporting 100% of its weight of said emulsion in

 <Desc / Clms Page number 39>

 a dye bath containing 2% (based on the weight of the fabric)

   of "AF Oelliton Blue" and kept there for half an hour at 85 ° C. the liquor ratio being 50. The fabric is dyed an intense blue shade and is then heat treated as described in example 1.



    EXAMPLE 5
The procedure described in paragraph (A) of Example 1 is repeated, except that the fabric consists of cellulose acetate fibers having an acetyl number of 59.5% calculated as acetic acid.



  We obtain substantially the same results.



   The dyed fabrics are then subjected to the heat treatment described in Example 1 with regard to the fastness to washing. The temperature is increased by for 30 seconds. Ironing is safe and the fold characteristics are obtained substantially the same seed, crease resistance and encumbrance as in during laundering and shrink resistance - Example 1 sown by steam pressing wet conditions are improved, but not to such an extent as in Example 1.



   EXAMPLE 6
50 kg of cellulose acetate woven fabric having an acetyl number of 61.3% was placed on a woolen machine, fixed and dyed on the woolen machine at a liquor ratio of 4: 1 with an aqueous mixture. comprising 3000 grams of "AF Oelliton blue", 390 grams of "red and? Easton", 420 grams of "yellow OW Amaoel", 950 grams of diphenylimidazolidine, 50 grams

 <Desc / Clms Page number 40>

 of "igepon T Gel", 100 g of tetrasodium pyrophosphate and 2500 g of a mixture of 400 parts by weight of tripropyl phosphate,

   400 parts by weight of pine oil sold under the name "Yarmor 350 (a mixture of hydrocarbons and alcohols distilling between 1900 and 220 C approximately 50% distilling at 200 C, approximately at atmospheric pressure) and of 100 parts by weight of "Emulphor ELA-719". Dyeing is started at 85 C and after two hours the temperature of the dye bath is raised to 95 C. The total duration of the dyeing is 6 hours, at during which the fabric is passed from one roll of the woolen machine through the dye bath and onto the other roll of the woolen machine, then through the dye bath to the first roll, this operation being repeated several times during the dyeing period in the conventional way, after which the fabric is degreased and washed on the woolen machine.



  The fabric dyed to an intense navy blue shade was heat treated in a radiant heater for thirty seconds at which time the fabric reached a temperature of 23000., Then subjected to the A.A.T.C.O.washfastness test. No. 3 in which no appreciable change in shade occurs.



   EXAMPLE 7
A fabric comprising a blend of 50% cellulose acetate staple fibers having an acetyl number of 62.5% and 50% viscose rayon continuous fibers is dyed at a liquor ratio of 50: 1 with an aqueous bath comprising 1% of

 <Desc / Clms Page number 41>

 
 EMI41.1
 ubleu SLF? astaan ", 2% of" red GLY Santontuo 0.75 - of "yellow acetate IiDLP-40 Ittexahasnioal", 0.21 i of Ubl * U i OLN teaoil, x ", 0.45 of * yellow GL Cuprofix "and 2.59i of% rubis' DL! 1 Resotix", the last three being
 EMI41.2
 direct dye for cellulose # all proportions banded on fabric weight. The dye bath also includes 10% by weight
 EMI41.3
 of the title "d # Arosol C".

   Sodium chloride is added in portions during the dyeing process, based on the weight of the fabric. The dyeing temperature is 90 ° C. The fabric is dyed a uniform medium brown shade. It is rinsed, then heat treated by exposing it to radiant heat for 30 seconds during which the fabric reaches a temperature of 220 C and then it is padded with an aqueous mixture so as to deposit on the fabric 0.5% by weight of "Decetex 104", 0.5% by weight of "Deoetex 108"
 EMI41.4
 (the two “Deoetex” compositions being silicone learning agents), 10% by weight of a condensation product of 1.3 moles of formaldehyde and one mole of uro,

     1% by weight of "Catalyst G-8" (an acidic mixture of formaldehyde and an amine hydrochloride forming a ripening catalyst for the urea and formaldehyde product) and 2% by weight "Cuprofix 47" (a fixing agent for direct dyes on cellulose),
 EMI41.5
 all proportions to poGJ, 1 <- 'JU After drying, the fabric is heated to 155 ° C for 8 minutes to cure the finish, then hardened.



   In the following parts numbered by 1 11 III and IV, parts I, II and III describe other *

 <Desc / Clms Page number 42>

 particular means for dyeing fabrics for further heat treatment according to the invention, while part IV gives further examples of mixtures of dyeing aids and dyeing agents which may be used for dyeing cellulose acetate having a high acetyl number with slow dyeing type dyes at high temperature to obtain dyes for heat treatment according to the present invention.



   I.



   100 parts by weight of a fabric of cellulose acetate having an acetyl number of 62.5% are immersed and stirred for one hour in a bath at a temperature of 85 ° C. and comprising 4000 parts by weight. of water, 2 parts by weight of the "blue green BA celiton" dye containing about 40% by weight of active coloring material and the remainder being a dispersing agent, and 5 parts by weight of tri-n-butyl phosphate. The fabric is then rinsed in water and dried.



   The dyed fabric thus obtained is analyzed to determine its content of tri-n-butyl phosphate and dye and the dye bath is analyzed to determine the concentration of tri-n-butyl phosphate,
For comparison, the dyeing is repeated under identical conditions, except that in one case the phosphate is completely removed from the dye bath and in the other cases an equal amount of triethyl or tri-n-propyl phosphate is used as instead of tributyl phosphate.

 <Desc / Clms Page number 43>

 the results are shown in the table below:

   
 EMI43.1
 
<tb> Phosphate <SEP> Content <SEP> in <SEP> Concentration <SEP> Content <SEP> in
<tb>
<tb>
<tb> trialky- <SEP> phosphate <SEP> from <SEP> phosphate <SEP> dye <SEP> from
<tb>
<tb>
<tb> lique <SEP> trialkyli- <SEP> trialkylic <SEP> fabric <SEP> dyed <SEP> *
<tb>
<tb>
<tb> that <SEP> of the <SEP> fabric <SEP> in <SEP> the <SEP> bath <SEP> of
<tb>
<tb>
<tb>
<tb> dye <SEP> * <SEP> dye <SEP> at the <SEP> end
<tb>
<tb>
<tb> of <SEP> time <SEP> of
<tb>
<tb>
<tb>
<tb> dye <SEP> **
<tb>
<tb>
<tb>
<tb>
<tb> None <SEP> 0.00 <SEP> 0.00 <SEP> 0.22
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Triethyl- <SEP> 0.32 <SEP> 0.060 <SEP> 0.23
<tb>
<tb>
<tb> lique
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Tripropy- <SEP> 0.81 <SEP> 0.045 <SEP> 0.28
<tb>
<tb>
<tb> lique
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Tributy- <SEP> 1.35 <SEP> 0.008 <SEP> 0,

  43
<tb>
<tb>
<tb>
<tb> lique
<tb>
 * relative to the weight of the dyed fabric ** relative to the weight of the dye bath
II
A cellulose acetate fabric having an aoetyl number of 62.5 is padded with an emulsion prepared by vigorously mixing 99% water and 1% tri-n-butyl phosphate. During padding, the fabric is first immersed in the emulsion for 2 minutes at 25 ° C. and then passed between padding rolls under pressure. The scarf fabric is then dyed with an amount of emulsion equal to approximately 90% of its own weight at 8500, for one hour with an aqueous dispersion of 2%, relative to the weight of the fabric, before padding, of "green blue BA Celliton "to a liquor ratio of 40.



  The fabric is then rinsed and dried. The resulting dyed fabric was analyzed to determine its content of tri-n-butyl phosphate and dye.

 <Desc / Clms Page number 44>

 



   For comparison, the operations of the procedure described above were repeated without using phosphate in the forming bath or by using triethyl phosphate or tri-n-propyl phosphate in place of. tri-n-butyl phosphate, all other conditions being the same. The results are shown in the following table
 EMI44.1
 
<tb> Phosphate <SEP> Content <SEP> in <SEP> phosphate <SEP> Content <SEP> in <SEP> colorant
<tb> trialkyl <SEP> trialkyl <SEP> from <SEP> fabric <SEP> * <SEP> from <SEP> fabric <SEP> * <SEP>
<tb>
<tb> None <SEP> 0, <SEP> 0 <SEP> 0, <SEP> 22 <SEP>
<tb>
<tb> Triethylic <SEP> 0.10 <SEP> 0.24
<tb>
<tb> Tripropyl <SEP> 0.57 <SEP> 0.32
<tb>
<tb> Tributylic <SEP> 3.24 <SEP> 0.76
<tb>
   * Relative to the weight of the dyed fabric.



   III
100 parts by weight of a cellulose acetate textile fabric having an acetyl number of 61.3 are immersed and stirred in a dye bath containing 5000 parts by weight of water, 3 parts by weight of solid blue. AF Celliton ", 12.5 parts by weight of diethyl phthalate and 2.5 parts by weight of" Tween 85 "(a polyoxyethylene-sorbitan trioleate). The word "Tween" is a trademark. The dyeing is started with the dye bath at a temperature of 60 ° C. which is brought to 900 ° C. as the dyeing progresses. The fabric is dyed a very uniform intense blue shade.

 <Desc / Clms Page number 45>

 



    Else. examples of coloring adjuvant * and
 EMI45.1
 Acid dispersion suitable for use with slow, high temperature dye type cellulose dyestuffs are
 EMI45.2
 
<tb> (a) <SEP> 4 <SEP> will start <SEP> in <SEP> weight <SEP> of <SEP> phosphate <SEP> tributyl
<tb>
<tb> 4 <SEP> "<SEP>" Yarmor <SEP> 350 "
<tb>
<tb>
<tb> @ <SEP> "<SEP>" Emulphor <SEP> EU-7190
<tb>
 
 EMI45.3
 (b) 3 "" tributyl phosphate 3 "tripropyl phosphate 1 m" E8ulphor EU-7190
 EMI45.4
 
<tb> (o) <SEP> 3 <SEP> "<SEP> tributyl phosphate <SEP>
<tb>
<tb> 2 <SEP> "<SEP>" Yarmor <SEP> 350 "
<tb>
<tb> 2 <SEP> "<SEP>" Alroaol <SEP> C "
<tb>
<tb> 1 <SEP> "<SEP>" Emulphor <SEP> ni-719
<tb>
 
 EMI45.5
 (d)

   ° "" dlethylt phthalate
 EMI45.6
 
<tb> 4 <SEP> "<SEP> tripropyl phosphate <SEP>
<tb>
 
 EMI45.7
 \ "" Tween 80 "
 EMI45.8
 
<tb> "<SEP> (e) 4 <SEP>" <SEP> ethylene <SEP> phenyl <SEP> <SEP>
<tb>
<tb> glyool
<tb>
 
 EMI45.9
 4 "d1eth7- phenyl ether
 EMI45.10
 
<tb> lene <SEP> glycol
<tb>
<tb> 0.5 <SEP> "<SEP>" <SEP> "Span <SEP> 20"
<tb>
 
 EMI45.11
 0.5 "* Tween 20'm
The word "Span" is a trademark.



  The product "Span 20" is that designated in the
 EMI45.12
 "Techn1oal Manual and Year Book" of A.A.T.O.Q.1, page 396


    

Claims (1)

EMI46.1 ae 3 umka Method for improving the wash fastness and other characteristics of a textile material dyed with cellulose acetate having an acetyl number of 59% at the monk calculated as acetic acid, method characterized by the tips following separately or in combinations: 1 It consists in subjecting the dyed material to a heat treatment. 2 The dye of the material is a high temperature slow dyeing type disperse dye. 3 To obtain shades having good wash fastness, the material is first dyed from an aqueous medium with a disperse dye of the slow dyeing type at high temperature, and the material is then subjected to heat treatment to that the washing fastness is significantly improved, 4 The heat treatment is such that the dyed material satisfies the conditions of the EMI46.2 wash fastness A, A..C.O, N 3. The heat treatment is carried out at a sufficiently high temperature and for a sufficient time to substantially improve the temperature of safely ironing the material. 6 The material is a fabric and it may shrink during heat treatment. 7 The material is a fabric and its dimensions are kept substantially constant during heat treatment. <Desc / Clms Page number 47> 8 - The temperature and duration of the heat treatment are such that the safe ironing temperature is raised to at least 230 C. The heat treatment is carried out in substantially saturated steam under pressure. The dyeing of the material is carried out from an aqueous medium in the presence of an adjuvant which increases the dye rate of cellulose acetate, which is a solvent for the dye and which has substantive power. regard to cellulose acetate. Dyeing is carried out from an aqueous dye bath containing adjuvant in a dispersed state. 12 - The material is impregnated with an aqueous dispersion of the adjuvant and then dyed in an aqueous dye bath. The adjuvant is a terpene alcohol or an ether thereof. 14 - The adjuvant is an (alkyl phosphate. The adjuvant is an alkyl ester of an aromatic carboxylic acid. 16 - The adjuvant is tripropyl phosphate or tributyl phosphate. 17 The adjuvant is triamyl phosphate or trihexyl phosphate. 18 - The adjuvant is dimethyl phthalate or dithyl phthalate <Desc / Clms Page number 48> 19 - The adjuvant is dipropyl phthalate or diallyl phthalate, The adjuvant is a condensation product of diethanolamine with a long chain fatty acid. 21 The adjuvant is a condensation product of two molecular proportions of diethanolamine with one molecular proportion of oapric acid. B - Textile products dyed with cellulose acetate having an acetyl number of at least 59% calculated as acetic acid, obtained by a process according to paragraph A or any other equivalent process.