DE1769225A1 - Process for one-bath dyeing and finishing of fiber material made of cellulose ester - Google Patents

Description

²²⁵⁰ "' ^U ■ Dr.Fa ^ HtDr.Eta« « ^D 1-2605 / Pfe 1

Dr.R.Koenigsberger - Dipl. Phya. R. Holzbauer Dr. F. Zumstein jun. Patent attorneys

⁸ Mönchen 2, Bräuhousstraße 4 / III

New complete registration documents Process for one-bath dyeing and finishing of fiber material

from cellulose ester

The present invention relates to a process for the one-bath dyeing and finishing of fiber material made from zeus ester, the treatment liquor used for this, and the zeus ester fiber material dyed and finished according to this process. %

It is known that Ze ^ u ^ seester fabric dyed with disperse dyes in an aqueous liquor and the dyed Fabric can then be provided with a finish suitable for the intended purpose, also in an aqueous liquor. the However, treatment in water has various disadvantages. So will for example, the structure of the goods adversely affected, and one obtains tissue with an undesirable, fluffy feel. The extensive The handle can be defaced later by using it can no longer be completely corrected by grip enhancers. It has therefore already been proposed to carry out the dyeing in organic solvents and after the heat-setting of the Dye the finishing agent in a second bath of organic ^ Apply solvents to the tissue. This two-bath treatment However, it still has various disadvantages. To e.g. wet and To get dyeings that are fast to rub, such large hip center quantities are required. used that often have an adverse effect on the desired finish results. Subsequent application can also be used of finishing agents on the dyed fabric from one organic bath, depending on the agent used, cause a change in nuance, which makes the reproduction more faithful to the pattern Staining made considerably more difficult. In addition, the structure of the fiber can be improved by the required double heat treatment

.109-83071964- ''

Documents (Art 7 i 1 Para. 2 No. 1 Sstac 3 of the amendment of 4.9.1967)

be harmed.

It has now been found that the disadvantages mentioned are avoided when cellulose ester fiber material is dyed and finished from a single bath at the same time. The present The invention therefore relates to a method for one-bath dyeing and finishing of fiber material made of cellulose ester by this material with a solution, the organic dye and finishing agent and optionally other auxiliaries in one Contains solvent mixture, which consists essentially of

a) at least 50 percent by weight optionally halogenated, between. 70 and 150 ° C boiling hydrocarbon and

b) there is a maximum of 50 percent by weight of water-miscible organic ^{solvent boiling below 210 °} C., impregnated and then the excess treatment liquor is removed from the fiber material or printed and the dyeing or print is fixed by heat setting at temperatures below the softening point of the fiber material.

The impregnation of the fiber material can be carried out by known methods, e.g. padding or printing.

The dyeings on cellulose ester fibers obtained by the process according to the invention have unexpectedly high wet fastness properties, E.g. washing, alkaline fulling, perspiration and sea water fastness as well as high rub fastness and dry cleaning fastness, whereby often an addition of auxiliaries which increase these fastness properties is not necessary or only much smaller amounts of it such aids are required as in the known two-bath treatment.

At the moment, no explanation can be given for this unexpected result that can be obtained when using the inventive Receives single bath process.

Suitable hydrocarbons boiling between 70 and 150 ^° C. which can be used as component a) in solvent mixtures which can be used according to the invention are, for example, aromatic hydrocarbons, such as toluene or xylene; In particular, however, the solvent mixtures according to the definition contain at least 50

109830/1964 * '/

Percentage by weight of halogenated, in particular chlorinated, hydrocarbons, such as chlorobenzene, and preferably lower aliphatic ones Halogenated hydrocarbons, namely chlorinated hydrocarbons, e.g. carbon tetrachloride and tetrachloroethane, or brominated Hydrocarbons such as dibromoethylene; Tri- or tetrachlorethylene are preferred. Mixtures of such solvents can also be used as component a) of the treatment liquid.

Miscible with water, below 210 ⁰ G-boiling organic solvents of the present invention useful solvent mixture can be used as component b) are, for example, monovalent aliphatic alcohols such as n-.or Isopropanolj Alkylenglykolmonoalkylather such as ethylene glycol monomethyl or -monoäthylather; likewise furfuryl or tetrahydrofurfuryl alcohol, or dihydric aliphatic alcohols such as ethylene glycol or 1,2-propylene glycol and lower aliphatic ketones such as acetone; cyclic ethers, such as dioxane or tetrahydrofuran, and amides of lower fatty acids, such as dimethylformamide or dimethylacetamide; Amides of carbonic acid, such as tetramethylurea, * or, finally, tertiary organic amines, such as pyridine, mixtures of such solvents can also be used as component b) of the treatment liquor. The amides of lower fatty acids, in particular dimethylacetamide, are preferred as component b) of the solvent mixture.

The composition of the solvent mixture depends on the solubility of the dyes and finishing agents used. Should be such that a homogeneous, clear or opalescent solution exists ä. Solvent mixtures are preferably used which consist of 85 to 99.5 percent by weight of halogenated hydrocarbons with a boiling point between 70 and 150 ^° C. and 15 to 0.5 percent by weight of an amide, monoalkylamide or dialkyl amide of a lower fatty acid.

Organic dyes which can be used according to the invention are water-soluble dyes and color salts, but especially disperse dyes. They can belong to any class of dye. For example, it can be metal-free or heavy-metal-containing

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Azo dyes, including the formazan dyes, as well as anthraquinone, nitro, methine, especially styryl, Azostyryl, naphthoperinone, quinophthalone, oxazine, 5-amino-8-hydroxy-1,4-naphthoquinone or phthalocyanine dyes.

The so-called acidic wool dyes of the azo and anthraquinone series, containing a sulfonic acid or carboxylic acid group are as water-soluble dyes for use in particularly suitable according to the invention. As azo dyes acidic, metal-free and heavy metal-containing mono- or disazo dyes are possible, · as heavy metal-containing azo dyes can in particular chromium or cobalt-containing monoazo dyes, which contain no acidic or basic water-solubilizing groups and the 2 molecules of azo dye bound to a metal atom included. As anthraquinone dyes, l-amino-4-arylamino-anthraquinone-2-sulfonic acids in particular are to be used mention.

The disperse dyes are metal-free azo, styryl, Naphthoperinone, quinophthalone, nitro and anthraquinone dyes which do not contain acidic, salt-forming groups are preferred.

The soluble color salts are salts with colored organic cations and colorless organic anions, salts with colorless organic ones Cation and colored organic anion and salts with colored organic cation and colored organic anion in question. Of the colored part of these colored salts can be made from any of the above Dye classes are taken. Preferred colored cations include e.g. the di- and triphenylmethane, rhodamine, oxazine and Thiazine series, it can also be quaternary ammonium, in particular act azo dyes containing cyclammonium groups. The colored anions of such color salts are, for example, the ions of dye carboxylic acids or, more advantageously, of dye sulfonic acids or of metal complex dyes, which are derived from one equivalent of a trivalent, coordinatively hexavalent heavy metal, such as chromium or cobalt, and two equivalents of bicyclic, metal complex-forming Dyes, e.g. from the class of the o, o'-dihydroxyoder ö-hydroxy-o'-carboxy-azo or -azomethine dyes exist.

1Q9820 / 1954

For example, precipitation products of di- or triphenylmethane or rhodamir dyes with optionally sulfated chromium or Cobalt complexes of 0,0'-dihydroxy or o-llydroxy-o'-carboxyazo dyes can be used as such color salts. Suitable colorless cations in these salts are, for example, those of primary, secondary or tertiary organic amines of the aliphatic, cycloaliphatic ^ araliphatic, aromatic or heterocyclic series or of cyclic amines. The main colorless anions in salts with colored cations are those Residues of organic acids, especially aromatic sulfonic acids, e.g., anions of the alkylalkoxybenzenesulfonic acids.

The treatment liquor to be used contains depending on the ge ■ * ■ desired depth of color e.g. 0.1 to 10 percent by weight of one or more different of the mentioned dyes.

Finishing agents which can be used according to the invention include e.g. consider those that have an oil and water-repellent effect, which improve the grip of the treated fiber material, make it slip-proof or give it antistatic properties, also flame retardants and agents with a bacteriostatic effect or those that prevent infestation by microorganisms, e.g. fungi (Fungistatica). With a suitable selection With a finishing agent, several of these finishing effects can be achieved at the same time, e.g. a simultaneous repulsion of OeI and water, or water repellency, combined with a full, ^ soft grip. On the other hand, different finishing agents can also be combined with one another to create the desired one To achieve effects.

The prerequisite for the usability of the finishing agent is, that they, or optionally their mixtures, in the according to the invention solvent mixtures used are soluble. It is therefore advantageous to use the finishing agents in liquid form, i.e. dissolved in any organic solvent or mixture of solvents To give treatment liquor,

100830/19

Finishing agents suitable for the above-mentioned one-bath coloring and finishing process are, for example, the following:

a) A condensation product of formaldehyde and either urea or melamine in a molar ratio of about 1.5 to 4.5 of the first-mentioned reactant per amino group in the urea or melamine, with at least one of the methylolamino groups formed in the condensation product (1) having an aliphatic carboxyl radical of 8 to 22 carbon atoms esterified, or (2) with an aliphatic hydrocarbon radical of 8 to 22 carbon atoms or (3) with a radical of the formula R-CO-NH-CH _? - etherified, wherein R represents an aliphatic hydrocarbon residue of 7 to 21 carbon atoms, and w infrequent least a portion of remaining methylol groups with lower alkyl groups is etherified.

The process for preparing such condensation products is described in British patent specification 726,661, in German Auslegeschrift 1,233,874 and in the German interpretative document 1,044,402 described.

These condensation products give the fiber material treated with them a certain hydrophobic effect and a pleasant one Handle, which by the additional use of fatty compounds such as paraffin, fats, i.e. glycerol esters of higher fatty acids, or waxes, e.g. higher myristyl or cetyl esters , Fatty acids, can be varied.

"b) A condensation product as defined under a) etherified with (2) and at the same time condensed with about 0.5 to 10 moles of a free aliphatic or aromatic dicarboxylic acid with 4 to 12 carbon atoms, especially maleic or phthalic * acid, or the anhydride of such an acid. A process for the production of these condensation products is in the Swiss 388,901.

About 0.2 to 0.6 mol of an aliphatic monocarboxylic acid having 8 to 22 carbon atoms can also be condensed onto this product per mole of melamine, as is described in Example 2 of the Swiss patent mentioned .

These condensation products make the fiber treated with it material well water repellent and give it a pleasant Handle that can be varied with the above-mentioned fat-like compounds.

If the fiber material is treated with condensation products, as defined above under (a) or (b), with or without fatty products Compounds, together with an alcoholate of a lower alkanol or lower alkanediol and a trivalent or tetravalent igen metal of the III. or IV. Mendeleev's group Periodic table, in particular aluminum, titanium or zirconium, so the water-repellent effect is further improved.

The production of such alcoholates is e.g. in the German Patent application C 1891 IVd / 12 ο or in the German Auslegeschriften 1 116 412ί 1 114 176 and 1 076 110.

c) Organopolysiloxanes used as textile finishing agents in the invention Process are used and the treated cellulose ester fibers have a soft feel and a water-repellent Give effect; such polysiloxanes are, in particular, methyl hydrogen polysiloxanes, dimethyl polysiloxanes or Mixtures of both types of polysiloxane.

Such organopolysiloxanes are produced by known methods, e.g. according to German patents 925 225 or 864 152.

The water repellency that the fiber material using This organopolysiloxane can be bestowed through common Use of known curing catalysts can be significantly improved, e.g. by

(α) an alcoholate of a lower alkanol or a lower one Alkanediol and a trivalent or tetravalent metal the III. or IV. group of the Mendeleev periodic table, in particular aluminum, titanium or zirconium, its production above is specified,

(ß) an alcoholate, as indicated in (α), in which at least one alkoxy group has been replaced by an acyloxy group of a fatty acid having 6 to 22 carbon atoms.

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The production of such curing catalysts is e.g. in the German patent application F 10 490 IVc / 8k, in the German Auslegeschrift 1 123 308, in the German patent specification 1 041 942 or in German patent specification 880 292.

(7) A condensation product of (1) alcoholates three- or tetravalent metals, in particular aluminum, zirconium or titanium and alkanols or alkanediols with 2 to 6 carbon atoms, or mono-lower alkyl ethers of the above alkanediols, and (2) formaldehyde in a molar ratio of (1) :( 2) in the range of 1: 1 to 1:10.

These condensation products can be stabilized against precipitation caused by moisture by adding a metal soap of a fatty acid with at least 5 and preferably 6 to 18 carbon atoms and a Z-, 3- or 4-valent metal such as magnesium, calcium, strontium, Barium, zinc, aluminum, titanium, tin, lead or manganese, in particular aluminum octoate, barium octoate, magnesium octoate, lead octoate, tin octoate, zinc octoate, barium oleate, calcium oleate, manganoleate, calcium laurate, zinc laurate, aluminum stearate, magnesium stearate, and zinc stearate 0.06 to 1 mole of this metal soap is added to one mole of the aforementioned condensation product.

The preparation of such condensation products was described in German patent applications C 41 896 IVc / 8k and C 42 529 IVa / 12 g described.

(S) Organotin compounds, such as diorganotin diacylate, described in German Auslegeschrift 1 225 640.

(C) zinc salts of organic fatty acids containing 6 to 12 carbon atoms.

d) fatty compounds such as paraffins, oils, waxes, Fats or esters of higher fatty acids with lower alcohols and their mixtures. They are used to improve the grip of the Suitable for fiber material.

e) Condensation products of alcoholates, as defined under (c), with formaldehyde, with and without stabilization

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" ⁹ - T769225

Addition or cocondensation of metal soaps, as mentioned above under ( ^c ) (7). Used alone, they improve the sliding resistance. Together with the fatty compounds defined under (d), the handle of the fiber material can be varied.

f) Polymers or mixtures of polymers, such as those made from ethylene and propylene (described in German Auslegeschrift 1 090 628), from acrylic or methacrylic acid esters or from esters of vinyl alcohols with lower fatty acids (described in German Patent 626 920) or their copolymers with acrylonitrile (described in German Patent 653 084), from methacrylic acid esters of higher alcohols (described in German Auslegeschrift 1 002 281), from styrene or its derivatives (described in German Patent % 534 636 and German Auslegeschrift 1 088 019), Copolymers of styrene and styrene derivatives with, for example, butadiene, copolymers of monoesters of α, ß-ethylenedicarboxylic acid with copolymerizable monomers (described in German patent 1,077,631), terpene (described in French patent 1,185,745), and other polymers and copolymers, for example of vinyl chloride and vinyl isobutyl ether insofar as they are soluble in organic solvents. These polymers are used to give the fiber material a fuller feel.

g) Organic compounds that have a perfluorinated carbon chain containing 4 to 12 perfluorinated carbon atoms, " such as copolymers of acrylic and methacrylic esters of Perfluoroalkanesulfonamidoalkanols with other copolymerizable monomers as described in US Pat. No. 2,803,615. the Copolymers obtained are coagulated and dried and dissolved in a carboxylic acid ester mixture, e.g. in butyl acetate and halogenate hydrocarbons. These compounds are suitable to give the fiber material oil and water-repellent properties.

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Other suitable oil and water repellent finishing agents are addition products of perfluoroalkanesulfonamidoalkanols with a perfluorocarbon chain with 4 to 12 perfluorinated carbon atoms on mono-, di- or polyisocyanates of the aliphatic, aromatic or araliphatic series. The resulting water shock can be improved by using these fluorine compounds and di- or polyisocyanates with a higher aliphatic Converts alcohol. Such fluorine compounds are described in British patent specification 999 795 and in Austrian patent 254 128. Furthermore, such finishing agents are polymers of acrylic or methacrylic esters with lower fluorinated ones Alkanols, such as hexafluoroisopropanol, are suitable.

h) Esters of higher fatty acids with pentachlorophenol, the so treated fiber material give fungistatic properties.

I) Neutralized or acidified condensation products of polyglycidyl ethers with polyamines. The manufacture of these products, which give the fiber material antistatic properties is described in German patent application F 42 554 IVc / 8k. These Condensation products are brought to a high solids content and mixed with a suitable emulsifying agent, e.g. with the salt of an organic amine with an organic sulfonic acid.

j) Organic phosphorus compounds, e.g. polymerized allyl bis (dibromopropyl) phosphate or diallyl dibromopropyl phosphate, copolymers of these compounds or their mixtures. Such Finishing agents are suitable for making the fiber material flame-resistant.

k) 1,3-Dipheny / urea derivatives (described in the US patent 2,745,874); they are in the process according to the invention used as a finishing agent to make the fiber material bacteriostatic To give properties.

Depending on the desired effect, those according to the invention contain Treatment liquors, e.g. 0.1 to 10 percent by weight of one or more finishing agents.

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If necessary, the treatment liquor can also contain thickeners contain, advantageously those in the defined solvent mixture are soluble, e.g. thickeners based on cellulose esters or polyvinyl esters ^ and / or small amounts other auxiliaries, such as surface-active agents (surfactants), the perfect rubbing fastness properties of the dyeings or prints to guarantee. In particular, nonionic surfactants, especially ethers and esters of polyethylene glycol, consisting of a higher one aliphatic hydrocarbon radical or the acyl radical of a higher fatty acid with a carbon chain of 8 to 20 carbon atoms or an alkyl / substituted phenyl radical, its alkyl chain Has 6 to 12 carbon atoms, and a polyether chain from about 2 to 20 ethyleneoxy groups have been found to be effective proven. There are preferred condensation products of one mole of one higher fatty alcohol or a higher fatty acid with 10 to 18 carbon atoms with 4 to 10 moles of ethylene oxide, such as penta, Hepta- or decaethylene glycol monolauryl or monostearyl or monooleyl ethers, or the monoesters of stearic or oleic acid with penta-, hepta- or decaethylene glycol. Also other polyglycol ethers with emulsifier properties, such as higher Al phenol polyglycol ethers, e.g. pentaethylene glycol monononylphenol ether or Tri- (1,2-propylene glycol) -inonononylphenolether, or polyglycolether with basic nitrogen, e.g. also polyglycol ethers of aliphatic, higher alkylated or higher acylated di- and polyamines are suitable surfactants. As such, amides can also be aliphatic, at least one monocarboxylic acid having a lipophilic radical with f primary or secondary amines which have at least one lower hydroxyalkyl group, especially coconut fatty acid mono- or -di-hydroxyäthylainide, optionally in a mixture with the mentioned Polyglycol ethers, can be used. '

Polyethylene glycol monooleyl ether with 4 to 10 ethyleneoxy groups are preferred.

If the use of such aids is necessary, what of depends on the type of finishing agent, are generally sufficient Quantities up to 0.5 percent by weight, calculated on the total weight of the treatment liquor.

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A preferred embodiment of the present method includes the use of the following measures and substances;

a) Impregnating the fiber material with an essentially non-aqueous, clear or opalescent solution

(α) organic dye »of which at least 0.5 g in solve every kg of the fiber material in an amount »sufficient to dye the fiber material in the desired depth,

(ß) Sizing agent in sufficient quantity to protect the fiber material to give the desired finishing effect, in

(7) a solvent mixture consisting essentially of (1) 50 to 99.5 percent by weight of non-halogenated or halogenated hydrocarbons with a boiling point between 70 and 150 ^° C.

^ (2) from 50 to 0.5 percent by weight water-miscible organic solvent having a boiling point above 100 ⁰ C and below 210 ° C,

(S) 0 to 1 percent by weight water,

(B) 0 to 0.5 percent by weight of other auxiliaries

b) mechanical removal of excess solution, and

c) Heat setting of the dye on or in the impregnated fiber material at a temperature below the softening point of the material, the organic dye and the sizing agent not interfering with each other and at least colloidal in are soluble in the solvent mixture.

A fiber material that can be dyed or printed and finished in a single bath according to the invention is such fc from cellulose esters, preferably cellulose tri- and in particular Cellulose-2-2-acetate in question. Said fiber material can be dyed and finished in any desired shape, such as e.g. in the form of flakes, tops, yarn or - preferably fabric, also in the form of blended fabrics.

Cellulose ester fiber material is impregnated, for example, by printing or spraying, but preferably by padding. in the In the latter case, the fiber material is advantageously continuous guided through the treatment liquor at room temperature and then reduced to the desired treatment liquor content

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squeezes, which is around 40 to 120 percent by weight (calculated on the weight of the goods). The main part of the solvent mixture remaining in the fiber material is then advantageously removed by mild drying at 40 to 100 ° C, preferably in a warm, dry air stream. After this During the drying process, the finishing agents can already be completely fixed while the dye is not yet fixed. this can easily be determined from the insufficient dry cleaning or rub fastness of the dummy dye.

The dye is on the fiber material, from which the excess treatment liquor has already been removed if desired, and this is already dried, by heat-setting at temperatures of at least 170 ⁰ C, preferably from 185 to 210 ⁰ G, | but below the softening point of the fiber material, fixed. Hot air, contact heat, treatment with high-frequency alternating current or irradiation with infrared (IR irradiation) are suitable for heat setting.

The residence time of the fiber material to be dyed in the treatment liquor, the type of drying of the impregnated material and the duration and temperature of the heat setting are dependent on the composition of the treatment liquor, in particular from Solvent mixture. All measures and conditions should, so be coordinated so that while maintaining the fiber structure, fiber swelling sufficient for the dye to take up is achieved. The most favorable conditions for a given device can easily be determined by a preliminary test.

If a preferred treatment liquor is used, which contains e.g. 85 to 95 percent by weight of trichlorethylene as a solvent mixture. and 15 to 5 weight percent methanol, or 95 to 99.5 weight percent Tetrachlorethylene and 5 to 0.5 percent by weight dimethylacetamide contains, is the residence time of the cellulose ester fiber material in the treatment liquor about 0.1 to 20 seconds and preferably 0.1 to 2 seconds, for example, the duration of the dry heat treatment in an air stream of 170 to 220 ° C is preferably 10 to 120 seconds.

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Solvent mixtures, which color and finish sensitive cellulose-22-acetate and cellulose triacetate in a way that is gentle on the fibers allow and which deliver consistently good rub fastness, while the supple and voluminous handle is retained from a mixture of 95 to 99.5 percent by weight of chlorinated lower aliphatic hydrocarbons, such as tetrachlorethylene or trichlorethylene and 5 to 0.5 percent by weight of an amide, monoalkylamide or dialkylamide of a lower fatty acid, in particular e.g. dimethylacetamide, it being possible for the mixture to contain up to 0.5 percent by weight of one of the surfactants mentioned.

The inventive method allows Zelluloseester fiber material, especially that of cellulose-2 _'2' acetate to color in ρ uniform colors and simultaneously equip. Thanks to the single bath work in organic solvent mixtures, the original voluminous, full feel of the textile material is retained. Although some of the same solvents are used in the process according to the invention as are used for dry cleaning of these textiles, these are colored. good fastness to dry cleaning. But the other fastness properties, such as wet fastness, light fastness and rub fastness, are also good. The dyeings are distinguished by excellent uniformity and great color strength, which is surprising since the finishing agents are for the most part fully fixed after the drying process. In addition, in the one-bath process it is generally not necessary to add an auxiliary to W in order to achieve optimum rubbing fastness, and it is possible to reproduce a given color shade in a faithful manner. The shades obtained are practically identical to those obtained without additional finishing.

Compared with previously used methods, this is according to the invention Single bath process more economical. It also has the important advantage that the solvents used almost completely recovered and can be used again in the dyeing process, so that in contrast to previously known processes the problem of wastewater treatment does not pose a problem. Also flush baths are-not necessary.

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The following examples illustrate the invention. the Temperatures are given in degrees Celsius.

example 1

5 g of the dye of the formula

N = N

CH ₂ CH ₂ OH

are dissolved in about 800 g of a solvent mixture which consists of 767 g of tetrachlorethylene and 30 g of dimethylacetamide and contains 3g of a condensation product of oleic acid and ethylene oxide (molar ratio about 1: 7.5). A solution of 19 g of a paraffin-free condensation product λ obtained by the method described in Swiss Patient 388 901, Example 2, of melamine, paraformaldehyde, phthalic anhydride, stearic acid and, instead of octanol, twice the amount of octadecyl alcohol in about 100 g of tetrachlorethylene is added to bring the weight of the liquor thus obtained to 1000 g. Tissue made of cellulose-2'2-acetate is impregnated with the clarified dye liquor at room temperature, squeezed off to a liquid content of about 100% of the dry weight and then dried in a stream of air at 40 to 80 °. The dyeing is then heat-set for 100 seconds by IR irradiation at 190 to 210 °. , "

A strongly colored, level and well-developed red dyeing with good fastness to dry cleaning and perspiration is obtained. The Λ fabric has a soft, supple feel and a certain water-repellent effect. At the same time, the fabric has good fungicidal properties if 20 g of lauric acid pentachlorophenol ester are added to the liquor.

If, in this example, instead of 30 g of dimethylacetamide, one of those mentioned in Table I, column 2 below, is used Water-miscible solvent in the amount specified in column 3 is used and otherwise applies the procedure described in this example, one obtains level and well-developed scarlet fever

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red stains on cellulose-2'2-acetate tissue that are similarly good Have fastnesses and finishing effects.

Table I.

Example no. water-miscible solvents Quantity (in g) 2 Isopropanol 100 3 Benzyl alcohol 100 4th n-butanol 80 5 Ethylene glycol monomethyl ether 90 6th Tetrahydrofurfuryl alcohol 90 7th Ethylene glycol 50 8th 1,2 propylene glycol 60 9 Dioxane 100 10 Diethylformamide 100 11 Dimethylformamide 30th 12th Pyridine 50

If in Examples 1 to 12 instead of tetrachlorethylene the the same amount of one of the hydrocarbons or chlorinated hydrocarbons given in Table II, column 2 below used and otherwise the procedure described in Example 1 is followed, one also obtains level and well developed red colorations with a corresponding handle on cellulose-2 ^ - acetate tissue.

Table II

Example no. Hydrocarbon or chlorinated hydrocarbon
material 13th
14th
15th
16 toluene
Xylene
Trichlorethylene
Carbon tetrachloride

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If in Examples 1 to 16 cellulose triacetate instead of Cellulose-2'2-acetate is used and the rest of the specified If the procedure is followed, well-developed and strongly colored red dyeings are obtained on the fiber material mentioned, the analogous ones Possess equipment effects.

example 17th Dye the formula C. - C
Il - CH 5 g of C ₉ HcSO ₉ - K-N = N-

-C

are dissolved in about 800 g of a solvent mixture which consists of 767 g of tetrachlorethylene and 30 g of dimethylacetamide and contains 3 g of a condensation product of oleic acid and ethylene oxide (molar ratio about 1: 7.5). A solution of 9 g of a paraffin-free condensation product of melamine, paraformaldehyde, phthalic anhydride, ■ stearic acid and, instead of octanol, twice the amount of octadecyl alcohol in about 100 g of tetrachlorethylene is added, as described in Swiss Patent 388 901, Example 2, to bring the weight of the resulting liquor to 1000 g. The tissue made of cellulose 2 ^ acetate is impregnated with the clarified dye liquor at room temperature, squeezed off to a liquid content of about 100% of the dry weight and then dried in a stream of air at 40 to 80 °. The dyeing is then heat-set for 100 seconds IR irradiation at 190 to 210 ⁰ C.

A level and well-developed, strongly reddish-tinged color is obtained yellow color with good fastness to dry cleaning and perspiration, · fastness to dry cleaning when assessed according to SNV test no. 95825/1957 is at least about 20% better than the one obtained by the two-bath process. The fabric owns a soft, supple handle and a certain water-

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repulsive effect. At the same time it shows good fungicidal properties, if 20 g of pentachlorophenyl laurate are added to the liquor.

Comparing the above-obtained equipped dyeings having equipped dyeings on cellulose-2 _'2' -acetatgewebe that was first stained with the above dye and subsequently fitted in an organic solvent bath with the above sizing agent, then the Hydrophobierwert the after the one-bath method of the above The dyeings obtained in the example are about 40% better than that of the dyeings obtained by the two-bath process (according to AATCC test No. 22-1952).

Example 18

Example 17 is repeated, but with 3 g of the dye

Formula _r "_

/ 7 ~ ^ \ y CH ₂ CH ₂ CN

^v CH ₂ CH ₂ OH Br

instead of 5 g of the dye of Example 17, red dyeings are obtained on cellulose-2'2-acetate fabric with better dry cleaning, Sweat and wash fastness (soapy water 40 °) and especially about 100% better light fastness than dyeings, using the same dye and finishing agent, but were obtained in two steps from separate organic solutions.

Example 19

Example 17 was repeated, but with 2 g of a mixture of Colorants of the formulas

9 OH • H ₀ N 0 OH

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in a weight ratio of about 1: 1, resulting in blue dyeings on cellulose-Za-acetate fabric that have better perspiration fastness, are more hydrophobic and especially 50% better wash fastness (evaluated according to SNV test no. 95811/1961) have as dyeings that were obtained after a two-step dyeing and finishing process.

If Examples 1 to 19 are repeated, but using the dyes listed in Table III, column 2 below, instead of the dyes previously mentioned in the examples, following the procedure given in the example, one obtains _: likewise level and well-developed, strongly colored Cellulose 2% acetate dyeings with the shades indicated in column 3 of the table and similarly good fastness properties. The fabrics are pleasant to the touch.

Table III

example

dye

Color shade on cellulose 2% acetate

CHoCONH

NH-COCH,

greenish yellow

yellowish orange

orange scarlet

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example

Dye shade on cellulose 2 ^ acetate

CH,

ON- / V-N = N- /

Cl

/ a_ _{n = n} - ff V_N = N- / V-OH

CH,

NH-f V-SO ₂ NH- ^

nC ₃ H ₇ -CO

3 / CN H = C

rub in

reddish yellow

yellow

greenish yellow

yellow

greenish yellow

blue

10983 0/1954

Example 31

5 g of the same reddish yellow dye as used in ' Example 17 was used, are dissolved in about 800 g of a solvent mixture consisting of 767 g of tetrachlorethylene and 30 g Dimethylacetamide and 3 g of a condensation product of oleic acid and ethylene oxide (molar ratio about 1: 7.5) contains. Then 150 g of a solution are added, which consists of 100 g of tetrachlorethylene and 50 g of a mixture of (α) a condensation product, as used in Example 17, (β) paraffin and (7) tetranopropyl titanate (16.5% Ti content), in a weight ratio of (α.): (Ss); (7) of 1: 2: 1.5.

Tissue made of cellulose-2-2-acetate becomes cleared, intense yellow colored dye liquor soaked at room temperature. | The excess treatment liquor is squeezed off to 100% of the dry weight of the goods, and the impregnated fabric is dried in a 40 to 80 ° hot air stream. The coloring will then for 60 seconds by IR irradiation at 180 Heat set to 210 °.

A level and well-developed reddish yellow ■ is obtained Dye with good fastness to dry cleaning and perspiration. That Fabric is very good water-repellent and has a pleasant, soft grip.

Same good results are obtained when the used in the above Example 31 Tetra-n-propyl titanate replaced by an equivalent amount of zirconium and the remainder for Example ~ \ prescribed loading process followed.

If the method described in the example is used, where however, the coloring and finishing are not done at the same time, if carried out separately in two different baths, then the colorations are not genuine, especially not rub and dry cleaning fast. About dyeings with good wet and rub fastness To obtain an aid, e.g. a condensation ■ product of oleic acid and ethylene oxide (molar ratio about 1: 7.5) are added to the first bath. However, this tool confers wetting properties of the tissue that are not fully carried out

109830/1954

Corresponding equipment of the colored material can be compensated in a second bath, so that colorations with considerably poorer water repellency can be obtained.

Example 32

Used instead of the FarV used in Example 31 scoffs 3 g of the red dye used in Example 18 and otherwise follows the procedure of Example 31 to give a red color with very good water repellency and a pleasant, soft handle.

Example 33

fc is used instead of the dye used in Example 31 3 g of the dye mixture used in Example 19 and otherwise following the procedure of Example 31 are obtained a blue color with very good water repellency and a pleasant, soft handle.

Example 34

5 g of the same yellow dye as used in Example 17 was used, are dissolved in 800 g of a solvent mixture consisting of 767 g of tetrachlorethylene and 30 g of dimethylacetamide and 3 g of a condensation product of oleic acid and ethylene oxide (molar ratio about 1: 7.5) contains. In addition one gives ^ 150 g of a solution consisting of 100 g of tetrachlorethylene and 50 g of a Mixture of (α) a condensation product according to Example 17, (ß) paraffin and (7) tetra-n-propyl titanate (about 16.5% Ti content) in the weight ratio of (α): (ß): (7) of 1: 2: 1.5, and 50 g of a 30% solution of a vinyl chloride / vinyl isobutyl ether copolymer, dissolved in a solvent mixture consisting of 1 part by volume of butyl acetate and 1 part by volume of 1,1,1-trichloroethane.

Tissue made of cellulose-2'2-acetate becomes cleared, intense yellow colored dye solution impregnated at room temperature. Excess treatment liquid is squeezed off to 100% of the dry weight of the goods, and the impregnated fabric

109830 / 195A

is dried in a 40 to 80 ° hot air stream. Afterward the staining is done for 60 seconds by IR irradiation Heat set at 180 to 210 °.

The dyed fabric obtained in this way has a 307 _° improvement. Rubbing fastness (SNV test No. 95831/1957), sweat fastness improved by 30% (SNV test No. 95824/1961) and washing fastness improved by 40 to 50% (SNV test No. 95811/1961) compared with dyed Fabric obtained by padding with an organic dye liquor and subsequent finishing from an organic finishing bath.

Example 35

Example 34 is repeated, but 3 g of the red dye used in Example 18 are used instead of the yellow dye | used. Red-dyed fabrics with properties that are just as good as the reddish-tinged yellow dyeings of Example 34 are obtained. Those red colorations have an approximately 20% improved fastness to perspiration. (SNV test no. 95824/1961) against red colorations obtained after a two-stage coloration and finishing treatment became. .

example 36 Dye the formula "V -ν ' ^H 5 5 g of O ₂ N- / " V-N = Ν— < = / ₂ GH ₂ OH L γ ... ^V CH

are dissolved in 888 g of a solvent mixture consisting of 90 percent by weight of trichlorethylene and 10 percent by weight of 2-methoxyethanol consists. 80 g of a 25% strength solution of a condensation product of stearic acid, paraformaldehyde and melamine are then added (produced according to example 1 of German Auslegeschrift 1 044 402 or, without the use of triethanolamine, according to Example 1 of Swiss Patent 374 830), mixed with paraffin (melting point 52 up to 54 °) in a ratio ^ of 1: 1 in trichlorethylene and 20 g a 50% solution of zirconium isopropylate in isopropanol as. Hardening agent added. With the clarified, intensely red in color

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Dye solution is impregnated tissue made of cellulose triacetate (squeeze effect about 80%) and as described in Example 1, dried. The impregnated and dried fabric is then heat-set for 90 seconds in a stream of hot air at 220 °.

A level and well-developed scarlet dyeing with good fastness to dry cleaning is obtained. In addition to good water repellency the fabric is characterized by a pleasant, full handle.

It is used instead of 20 g of a 50% strength zirconium isopropoxide solution 20 g of a 25% solution of maleic acid in isopropanol as hardening agent, and follows that described in this example Method, one obtains finished dyeings with similarly valuable properties.

Example 37

3 g of the same red dye as used in Example 18 are dissolved in 877 g of a solvent mixture which consists of 847 g of tetrachlorethylene and 30 g of dimethylacetamide. 100 g of a 25% strength solution of a condensation product of stearic acid, paraformaldehyde and melamine (prepared according to German Auslegeschrift 1 044 402, Example 1), mixed with paraffin (melting point 52 to 54 °) in a ratio of 1: 1 in Trichlorethylene, and 20 g of a 50% solution of zirconium isopropylate in isopropanol as hardening agent. Tissue made of cellulose triacetate W is impregnated with the clarified, intensely red colored dye solution (squeezing effect about 80%) and dried as described in Example 1. The impregnated and dried fabric is then heat-set for 90 seconds in a stream of hot air at 220 °.

A level and well-developed red coloration is obtained good fastness properties, especially good fastness to perspiration. Except The fabric is also characterized by good water repellency a comfortable, full grip.

If instead of the 20 g of a 50% solution of zirconium isopropylate, 20 g of a 25% solution of maleic acid in isopropanol and following the procedure described in this example, so

109830/1954

one obtains finished dyeings with correspondingly valuable properties.

In the present example, 37 g are used instead of 30 g Dimethylacetamide the same amount of any of the water-miscible Solvents listed in Table IV, column 2 below and if the procedure described in this example is followed, the result will also be level and well-developed scarlet stains on cellulose triacetate fabric with corresponding ^ good fastness to dry cleaning. The fabric is very good water-repellent and has a pleasant, full grip.

Table IV

Example no. water-miscible solvents 38 n-propanol 39 Isopropanol 40 n-butanol 41 Ethylene glycol monomethyl ether 42 Tetrahydrofurfury! Alcohol 43 Ethylene glycol 44 1,2 propylene glycol 45 Dioxane 46. Diethy! Formamid 47 Dimethylformamide. 48 Pyridine

Is used in Examples 37 to 48 instead of "847 g Tetrachlorethylene is the same amount of one of the hydrocarbons or chlorinated hydrocarbons, which are given in the following Table V, column 2, and the rest of the example is followed method described, one also obtains level and well-developed red dyeings on cellulose triacetate fabric.

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- 26 Table V

Example no. Hydrocarbon or chlorinated coals
hydrogen 49.
50
51
52 toluene
Xylene
Trichlorethylene
Carbon tetrachloride

Cellulose-2'2-acetate is used in Examples 37 to 52 instead of cellulose triacetate using otherwise the same process as indicated, the fiber material mentioned is also obtained well-developed and strongly colored red colorations, which show good water repellency and a pleasant, full handle.

Example 53

6 g of the dye of the formula

CH ₃ CONH

are dissolved in 800 g of a solvent mixture consisting of 99 percent by weight of trichlorethylene and 1 percent by weight of dimethylformamide and a solution of 10 g of a condensation product of melamine, paraformaldehyde, phthalic anhydride is added and octadecyl alcohol (obtained according to Swiss Patent 388 901, Example 1), 25 g of paraffin (melting point 52 to 54 °) and Add 10 g of zirconium isopropylate in about 100 g of trichlorethylene. The weight of the liquor is then brought to 1000 g with trichlorethylene. The yellow solution is clarified and tissue made of cellulose 2'2-acetate is impregnated with it, as described in Example 31. the The dyeing is then heat-set for 90 seconds in a stream of hot air at 190 °.

A level and well-developed yellow coloration is obtained on the specified material, which at the same time shows good water repellency.

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If the heat setting is carried out by treatment with high-frequency alternating current, IR irradiation or by contact heat instead a hot air stream carried out and the rest of the example If the specified procedure is followed, level and well-developed yellow colorations are also obtained, combined with good water repellency of said material.

Example 54

Example 53 is repeated, but the dye used therein is replaced by 5g of the yellow dye used in example 17 was used. 70 g of a solution of 10 g of the same condensation product as described in Example 53 are obtained is, 25 g paraffin and 10 g zirconium propylate in 25 g trichlorethylene and 927 g solvent mixture, consisting of 897 g tetrachlorethylene and 30 g of dimethylformamide used. ·

The yellow cellulose acetate fabric obtained is similarly good water-repellent and has better fastness to rubbing and dry cleaning as a fabric that is in a two-step dyeing and Treatment was colored.

Example 55

10 g of the 1: 2 chromium complex of the azo dyes of the formula

are dissolved in 910 g of a solvent mixture that consists of 90 Weight percent trichlorethylene and 10 weight percent isopropanol. To this solution are added 60 g of a 50% solution of Methyl hydrogen polysiloxane (viscosity about 30 cP at 25 °) in Trichlorethylene and 20 g of a 50% solution of titanium tetrabutoxide in butyl alcohol. Cellurose-2'2-acetate is used, as in example 31, treated with the red, clarified dye solution,

109830/1964

After drying, the dyeing is heat-set for 90 seconds in a stream of hot air at 200 °.

A strong, level and well-developed red dyeing with good fastness to perspiration is obtained. The fabric is good water repellent and has a soft, very pleasant feel.

Use the same amount instead of trichlorethylene a mixture of triethylethylene and xylene (weight ratio 1: 1), or the same amount is used instead of isopropanol a mixture of isopropanol and dimethylformamide (weight ratio 9: 1) and if the rest of the procedure is as indicated in the example, similar results are obtained.

Used instead of the one mentioned in the present example Dye one of the dyes listed in the following Table VI, "Column 2, are mentioned, and the rest of the procedure is followed by In the present example, strong, level and well-developed cellulose-2% acetate colorations in those indicated in column 3 are obtained Shades. The fabric is also very water-repellent and has a soft, soapy feel.

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Table VI

example

Dye shade on cellulose 2% acetate

1: 2 cobalt complex of the compound

N- N

H(

1: 2 chromium complex of the compound

; 0OH H ₉ N-SO ^ ~ f VN * N

HO- ^ N

Cl

1: 2 chromium complex of the compound OH

GH

yellow-brown

yellow

brownish Red

109830/1964

Is used in Examples 55 to 58 instead of cellulose-2'2-acetate Cellulose triacetate, and if you work the same way as indicated, you get on the fiber material mentioned well developed and strong colorations. The material has both the same hydrophobic properties and the designated characteristic handle.

Example 59

0.1 g of the same yellow dye as used in Example was used, are dissolved in 927 g of a solvent mixture composed of 897 g of tetrachlorethylene and 30 g of dimethy! acetamide consists. 50 g of a 60% strength solution of methyl hydrogen polysiloxane (viscosity about 30 cP at 25 °) are added to this solution Tetrachlorethylene and 20 g of a 50% solution of titanium tetrabutoxide in butyl alcohol. Cellulose-2 ^ -acetate is, as in example 31 labeled, treated with the yellow, cleared dye solution. After drying, the staining takes 90 seconds in one Hot air stream thermoset at 200 °.

A level and well-developed, light, yellow dyeing with good fastness to perspiration and dry cleaning is obtained. That Fabric is well water-repellent and has a soft, full texture Handle.

The dyed fabric thus obtained has better fastness to dry cleaning and has a water repellency value (determined according to the AATCC test No. 22-1952), which is about 50% better than that of a fabric that was treated accordingly in a two-stage treatment was colored and equipped.

Example 60

2 g of the dye of the formula

0 NH ₂

O NH

CH, 10 9830/19 54 *

are dissolved in 942 g of a solvent mixture which consists of 90 percent by weight trichlorethylene and 10 percent by weight dioxane and which also contains 2 g of a condensation product of oleic acid and ethylene oxide (molar ratio about 1; 7.5). To this are added 50 g of a 107 _o solution, obtained by precipitation of an in-US Patent 2,803,615 fluorinated resin described (by addition of ethanol, drying and dissolving the precipitate in a solvent mixture of butyl acetate and trichlorethylene volume ratio 2 :1). With this intense blue colored clear Farbstofflösüng web of cellulosic-2 is impregnated ⁱ iacetat and as described in Example 31, squeezed to a liquid content of approximately 807 _o and then dried. The dried fabric is then heat-set in a hot air stream A at 200 ° for 90 seconds.

A strongly colored, level and well developed blue color with good dry cleaning six the it. In addition, the fabric is extremely oil-repellent and good water repellency.

The above-mentioned fluorine-containing copolymer is replaced by the same amount of an adduct of 2 moles of N-ß-hydroxyethyl-N-propylperfluorooctanesulfonic acid amide to 1 mole Toluylene diisocyanate, a finished, colored one is obtained Fabrics with similar properties.

Example 61 ■ - "

■ 1 g of the blue dye mixture used in Example 19 is dissolved in 950 g of a solvent mixture consisting of 920 g of tetrachlorethylene and 30 g of dimethylacetamide and an additional 2 g of a condensation product of oleic acid.und. Contains ethylene oxide (molar ratio about 1: 7.5). To this are added 40 g of a 107 _o solution, obtained by precipitation of a fluorinated resin described in US Patent 2,803,615, by the addition of ethanol ·, drying and dissolving the precipitate in a solvent mixture of butyl acetate and trichlorethylene. (Volume ratio 1: 2). With this intense blue colored clear

_N 1 0 98 3 0/1 9.S4

BAD ORIGINAL

Dye solution is used to impregnate tissue made of cellulose-2'2-acetate and as described in Example 31, squeezed off to a liquid content of about 80% and then dried. That dried fabric is then heat-set in a stream of hot air at 200 ° for 90 seconds.

A strong, level and well-developed blue coloration is obtained on the fiber material mentioned, which is easy to dry clean. and is fast to sweat. The fabric is good oil and ■ water repellent. Its water repellency (according to the AATCC test No. 22-1952) is about 45% better than that of a fabric dyed and finished accordingly in a two-stage treatment.

Example 62

"'Example 61 is repeated, but with 5 g of that in example used yellow dye. A yellow fabric is obtained with the same good properties as in Example 61. The water repellency of the fabric (according to AATCC test no. 22-1952) is about 25% better than that of a similar fabric, which in a two-stage Treatment was established.

Example 63

Example 61 is repeated, but with 3 g of the red dye used in example; you get a red fabric with the same good properties as in Example 61. The water repellency of the fabric (according to AATCC test No. 22-1952) is about 100% better than a similar fabric made in a two-step treatment.

Example 64

10 g of the dye of the formula

N = N -C-C-CH

1 0 9 8 3 0/1 9 5.4

are dissolved in 97Og of a solvent mixture which consists of 95 percent by weight of tetrachlorethylene and 3 percent by weight of dimethylacetamide and contains 2 percent by weight of oleic acid-ethylene oxide condensation product according to Example 1. To this are added 20 g of a solution which contains 30 % of a vinyl chloride / vinyl isobutyl ether copolymer (weight ratio about 3: 1) in a mixture of!,!, L-trichloroethane / butyl acetate (volume ratio 1: 1). As described in Example 1, tissue made of cellulose 2% acetate is impregnated with the cleared yellow dye solution obtained and then dried. The impregnated and dried fabric is then heat-set for 120 seconds in a stream of hot air at 190 °.

Obtained on the said material is a strong, level, {and well-developed yellow color with good rub, washing and perspiration. The fabric has a voluminous handle. The filling effect of the finish can be increased by adding 5 g of butyl polyacrylate to the impregnation liquor (German Patent 626 930, Example 1).

Example 65

3 g of the same dye as used in Example 18 are dissolved in 942 g of a solvent mixture which consists of 912 g of tetrachlorethylene and 30 g of dimethylacetamide and contains 5 g of an oleic acid-ethylene oxide condensation product according to Example 1. Add 50 g of a solution that contains 30 %

a vinyl chloride / vinyl isobutyl ether copolymer (weight ratio about 3: 1) in a mixture of 1,1,1-trichloroethane / Contains butyl acetate (volume ratio 1: 1). With the clarified, red dye solution is, as described in Example 1, tissue Impregnated from cellulose-2 ^ acetate and then dried. The impregnated and dried fabric is then for 120 Heat-set for seconds in a stream of hot air at 190 °.

A strong, level and well-developed red coloration is obtained on the material mentioned, which is good for dry cleaning, Has fastness to washing and perspiration. The lightfastness of the coloring is more than 1007 »better than that on a corresponding one

10983-0 / 1 964

Fabric that was first dyed in a two-stage treatment and then finished in a second bath. The fabric owns a voluminous handle. The filling effect of the finish can be increased by adding 5 g of butyl polyacrylate to the impregnation liquor (German Patent 626 920, Example 1) can be increased further.

Example 66

Similar satisfactory reddish yellow colorations with similarly good properties and also a strong, voluminous one Handles are obtained if the above Example 64 is repeated, but 5 g of the dye. formula

^{N =} N- ^ V " ^{N =}

used instead of 10 g of the dye mentioned in Example 64 in 1000 g of dye liquor.

If Examples 64 to 66 are repeated, but instead of dimethylacetamide, one of the water-miscible types is used Solvents which are mentioned in table I, column 2, in the amounts mentioned in column 3 of the same table, are obtained in this way one also uses level and well-developed colorations on cellulose-2 ^ - acetate fabric with similarly good fastness properties and a voluminous handle.

In Example 64, instead of 95 percent by weight of tetrachlorethylene, the same amount of one of the hydrocarbons is used or chlorinated hydrocarbons, which are given in Table II, are also obtained level and well-developed yellow stains on cellulose-2 ^ -acetate and cellulose triacetate fabric. The fabrics have a voluminous handle.

Example 67

10 g of the dye of the formula

CH _n CH ₀ OH

0 "N - / __

N0 _o CH,

109 8 30/1954

are dissolved at room temperature in a solvent mixture consisting of 933 g of tetrachlorethylene and 30 g of dimethylacetamide and 2 g of the same oleic acid-ethylene oxide condensation product, as used in Example 1 contains. Then 25 g a 10% solution of a butadiene / styrene copolymer in tetrachlorethylene added. With this purple colored dye solution, tissue made of cellulose-2'2-acetate is impregnated. the Excess dye liquid will be up to 100% of the dry weight squeezed off the goods and the impregnated fabric is dried at 40 to 80 ° in a stream of air. After all, the Staining for 120 seconds in a stream of hot air at 190 ° thermoset.

In this way you get a level, violet coloration good fastness to rubbing, sweat and dry cleaning. The fabric has a voluminous handle,

By replacing the butadiene / styrene copolymer with 25 g of a 407 _o solution of a polyterpene resin (described in French Patent No. 1,185,745) in perchlorethylene, so as to obtain a fabric with a full, supple feel that the specified otherwise above Possesses properties.

Example 68

3 g of the same red dye as used in Example 18 was dissolved at room temperature in a solvent mixture consisting of 915 g of tetrachlorethylene and 30 g of dimethylacetamide and 2 g of the same oleic acid-ethylene oxide ' Contains condensation product, as used in Example 1. 50 g of a solution containing 20 percent by weight of paraffin oil and 40 percent by weight of a polyterpene resin in a mixed solvent made of gasoline and tetrachlorethylene are added. With this dye solution, tissue is made from cellulose 2% acetate impregnated. The excess liquor will be up to one Liquid absorption of 100% of the dry weight of the goods is squeezed out, and the impregnated fabric is at 40 to 80 ° im Airflow dried. The staining will then last for 120 seconds Heat-set in a stream of hot air at 190 °.

109830/19 54

In this way, a level, red dyeing with good fastness to washing, perspiration and dry cleaning is obtained. The fabric owns a voluminous handle. The fastness to washing (SNV test No. 95811/1961) and the fastness to perspiration (SNV test No. 95824/1961) are about 20% better and the lightfastness is more than 100% better than the corresponding colorations obtained in a two-stage treatment.

If, instead of the dye mentioned in Example 68 above, one uses those which are listed in the following Table VII, column 2, are given, and if the rest of the procedure is as described in the example, then one also obtains strong, level dyeings with similar good properties. Their color tones are given in the last column of the table. In all cases, the fabric possesses a voluminous handle.

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E.g., no.

Table VII

dye

0-NH-COOCH ₉ CH ₉ .

CH,

CH = C

CN

CN

° 2 ^N ~ W ~ " ^N

N - C-C- CH,

O ₂ N

-COCH, / CH ₂ CH ₂ OCOCH ₃
^ CH ₂ CH ₂ OCOCH ₃

0 NHCH (CH ₃ )

0 NH

0 NH

OSO ₂ CH ₃

0 NH- / V-CH

'Xt

N N

N N

Cl

Hue on

Cellulose-

2-2 acetate

greenish yellow

yellowish orange

Scarlet fever

blue

blue

blue

1098 30/195

1763225

example 75 Dye the formula ^ CH ₂ CH ₂ CN 5 g of ^ CH ₂ CH ₂ OCOCH ₃

are dissolved in 935 g of a solvent mixture which consists of 903 g of tetrachlorethylene and 30 g of dimethylacetamide and contains 2 g of a stearyl alcohol / ethylene oxide condensation product (molar ratio 1: 5). Then, 50 g are added to a solution of 507 _o dimethylpolysiloxane in tetrachlorethylene.

| After filtering the solution, cellulose-2-i-acetate is added impregnated the resulting filtrate at room temperature. Excess The liquor is squeezed off to about 80% of the dry weight of the goods. The impregnated fabric is then at 40 to 50 ° and dried for 90 seconds in a stream of hot air heat set at 200 °.

This gives a rubbing, strongly colored, level orange Coloring. The fabric has a voluminous handle.

If in this example the 2 g of the condensation product of stearyl alcohol and ethylene oxide are replaced (Mo! Ratio 1: 5) by

a) 2 g of a condensation product of stearyl alcohol and P ethylene oxide (molar ratio 1:10),

b) 4 g of a condensation product of oleyl alcohol and ethylene oxide (Molar ratio 1: 5),

c) 2g of a condensation product from oleylic alcohol and ethylene oxide (Molar ratio 1:10),

d) 3 g of a condensation product of lauryl alcohol and ethylene oxide (Molar ratio 1: 5),

e) 2 g of a condensation product of lauryl alcohol and ethylene oxide (Molar ratio 1:10),

f) 3 g of a condensation product of ρ-nonylphenol and Ethylene oxide (molar ratio 1: 9),

109 8 30/1954

g) 2 g of a condensation product of oleic acid and ethylene oxide (Molar ratio 1:10), or

h) 4 g of a condensation product of stearic acid and ethylene oxide (Molar ratio 1: 7),

and if the rest of the procedure is as indicated in the example, one obtains orange colorations with similarly good properties.

Example 76

0.2 g of the same yellow dye as used in Example 17 is dissolved in 970 g of a solvent mixture, that from 940 g of tetrachlorethylene and 30 g of dimethylacetarnide and 2 g of a stearyl alcohol / ethylene oxide condensation product (Molar ratio 1: 5) contains. Then 25 g of an ι 607oigen solution of a mixture of methyl hydrogen polysiloxane (Viscosity at 20 ° approx. 25 cP) and dimethylpolysiloxane (viscosity at 25 ° approx. 750 centistokes) in a weight ratio of 1: 1 added in tetrachlorethylene *

Cellulose ^ -a-acetate is mixed with the solution at room temperature impregnated. The excess dye solution is reduced to about 80% the dry weight of the goods squeezed. The impregnated fabric is then dried at 40 to 50 ° and during Thermally fixed for 90 seconds in a stream of hot air at 200 °.

In this way, a level, reddish-tinged yellow coloration that is fast to rub and dry cleaning is obtained. The fabric has a voluminous handle. Ä

Example 77

Example 76 is repeated - but instead of the mentioned dye 3 g of the red dye used in Example 18 was applied. The tissue obtained is different differs from the corresponding fabric, which was obtained in a two-step process, through better rubbing fastness, one around 50% better lightfastness and a softer handle.

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Example 78

Example 76 is repeated, but instead of the dye mentioned therein, 2 g of the blue dye mixture are used, that was used in Example 19. The resulting tissue differs from the corresponding tissue, which in a two-stage Process was obtained through better rubbing fastness, about 50% better light fastness and a softer handle.

Example 79

5 g of the same yellow dye as used in Example 17 was used, are dissolved in 977 g of a solvent mixture consisting of 943 g of tetrachlorethylene and 30 g of dimethylacetamide consists. 20 g of a perchlorethylene solution are added to this solution, which contains 10 g of butyl stearate and 4 g of paraffin oil are added.

Cellulose-2 ^ acetate is made with this dye solution at room temperature impregnated. The excess liquor is squeezed off to about 80% of the dry weight of the goods. The impregnated Tissue is then dried at 40 to 50 ° and heat-set for 90 seconds in a stream of hot air at 200 °.

In this way, a strongly colored, evenly yellow-dyed fabric with better rub and dry cleaning fastness and a softer one is obtained Handle as a suitably dyed and finished fabric obtained in a two-stage treatment.

Example 80

3 g of the same red dye as used in Example 18 are dissolved in 977 g of a solvent mixture, which consists of 943 g of tetrachlorethylene and 30 g of dimethylacetamide. Then you give 20 g of a perchlorethylene solution, the 10 g Contains butyl stearate and 4 g of paraffin oil.

Cellulose-2 ^ acetate is made with this solution at room temperature impregnated. The excess dye liquid will be up on about 80% of the dry weight of the goods squeezed off. The impregnated Tissue is then dried at 40 to 50 ° and heat-set for 90 seconds in a stream of air at 200 °. In this way, a strongly colored, equally red-dyed fabric is obtained

109830/1954

better rub and dry cleaning fastness and a softer one Handle as a suitably colored and finished fabric, which is produced in two separate treatments.

Example 81 .

2 g of the same blue dye mixture as in example 19 was used, are dissolved in 977 g of a solvent mixture consisting of 943 g of tetrachlorethylene and 30 g of dimethylacetamide consists. Then you give 20 g of a perchlorethylene solution, the 10 g Butyl stearate and 4 g paraffin oil.

Cellulose-2 ^ acetate is made with this solution at room temperature impregnated. The excess dye liquid will be up on about 80% of the dry weight of the goods squeezed. The impregnated fabric is then dried at 40 to 50 ° and heat-set for 90 seconds in a stream of hot air at 200 °.

A strongly colored fabric with a uniform blue color is obtained better fastness to rubbing and dry cleaning and a softer feel than a correspondingly dyed and finished fabric that is produced in two separate treatments.

Example 82 · - ■

10 g of the color salt of the formula

are dissolved in 950 g of a solvent mixture consisting of 850 g Trichlorethylene and 100 g of methyl alcohol. It will be 40 g added to a trichlorethylene solution containing 15 g of paraffin oil and 5 g of glycerol trioleate. With the clear blue dye solution If cellulose-2 ^ acetate fabric is impregnated, the excess dye liquor is squeezed to about 80% of the dry weight

109830/1: 9.0 ^

the goods and dries the fabric at 60 to 80 ° in an air stream. The coloration is then carried out for 100 seconds by IR irradiation Heat set at 190 to 220 °.

A deep, level, blue dyeing with good fastness to dry cleaning and excellent fastness to rubbing is obtained. That Fabric has a soft and supple feel. If the 15 g of paraffin oil is replaced by an equivalent amount of butyl stearate, this gives a fabric with a particularly pleasant feel.

If, with otherwise the same procedure, in this example, the 10 g of the colored salt are replaced by 0.5 g of the colored salt that is produced by Precipitation from an aqueous solution of the sodium salt of the dye the formula

N = N

CH ₃ SO ₃ H

was obtained with the appropriate amount of dicyclohexylamine, so a level, orange coloration is obtained. If the 10 g of the colored salt of Example 82 are replaced by 2.0 g, otherwise the procedure being the same of the color salt, which is obtained by precipitation from an aqueous solution of the sodium salt of the 1: 2 chromium complex of the compound of the formula

HCC- CH " ^C 2 ^H 5 ..

with the dye of the formula

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N (C ₂ H ₅ ),

0OH

Cl

was obtained, a level, bluish red coloration is obtained. In both cases the dyeings show equally good properties, as mentioned above.

Example 83

10 g of the dye of the formula

Λ CH ₂ CH ₂ OH

are dissolved in about 733 g of a solvent mixture which consists of 700 g of tetrachlorethylene and 30 g of dimethylacetamide and contains 3 g of a condensation product of oleic acid and ethylene oxide (mol ratio about 1: 7.5). A solution of 80 g of a polymer of brominated triallyl phosphate, which contains about 3.6 bromine atoms per monomer unit, in 200 g of benzene is added and the weight of the dye liquor with tetrachlorethylene is brought to 1000 g. Cellulose 2 ^I 2 acetate tissue is treated with this liquor as described in Example 1. In this way, a strong, level and well-developed red coloration is obtained. The dyed fabric is also flame-resistant.

This polymerized brominated TrialIylphosphate be prepared by polymerization of triallyl in benzene in the presence of benzoyl peroxide, have responded to about 1/3 to one half of the double bonds, are brominated followed by the remaining double bonds by the addition of bromine.

109830/1954

example 84 Dye the formula C -
Il
N CH ₃ 5 g of SO ₂ -O- N = N-
H ₉ N -
) ^C 2 ^H 5 • C -
Il
■ C
\ .
N

are dissolved in about 733 g of a solvent mixture consisting of 700 g of tetrachlorethylene and 30 g of dimethylacetamide and 3 g of a condensation product of oleic acid and ethylene oxide (molar ratio about 1: 7.5). A solution of 80 g of a polymer of brominated triallyl phosphate, which has about 3.6 bromine atoms contains per monomer unit, in 200 g of benzene, is added, and the weight of the dye liquor is increased to 1000 g with tetrachlorethylene brought. Cellulose acetate tissue is made as in Example 1 described, treated with this fleet. In this way, a strong, level and well developed, reddish yellow color is obtained Coloring. The dyed fabric is also excellent flame retardant.

Example 85

3 g of the dye of the formula

/ CH ₉ CH ₉ CN -N ^L

are dissolved in about 733 g of a solvent mixture consisting of 700 g of tetrachlorethylene and 30 g of dimethylacetamide and 3 g a condensation product of oleic acid and ethylene oxide (molar ratio about 1: 7.5). A solution of 80 g of a polymer of brominated triallyl phosphate containing about 3.6 bromine atoms per monomer unit in 200 g of benzene is added, and the weight of the dye liquor is brought to 1000 g with tetrachlorethylene.

109830/19 54

Tissue made of cellulose 2% acetate is, as described in Example 1, treated with this fleet. In this way, a strong, level and well-developed red coloration is obtained. That At the same time, dyed fabric has good flame resistance.

Example 86

2g of a mixture of the dyes of the formulas

and
HO ⁿ NH HO

in a weight ratio of about 1: 1, will be about 733 g dissolved a solvent mixture consisting of 700 g of tetrachlorethylene and 30 g of dimethylacetamide and 3 g of a condensation product of oleic acid and ethylene oxide (molar ratio about 1: 7.5) contains. A solution of 80 g of a polymer brominated triallyl phosphate, which contains about 3.6 bromine atoms per monomer unit contains, in 200 g of benzene, is added and the weight of the dye liquor is brought to 1000 g with tetrachlorethylene. Tissue made of cellulose 2% acetate is> as described in Example 1, treated with this fleet. This is how you get one strong, level and well-developed blue coloration. The dyed fabric is also excellent flame-resistant,

Example 87

3 g of the same blue dye mixture as in example 19 was used in 962 g of a mixed solvent dissolved from 932 g of tetrachlorethylene and 30 g of dimethylacetamide, the 2 g of the oleic acid-ethylene oxide condensation product according to example 1 contains. To this are added 30 g of a mixture of equal parts (a) of a condensation product of polyglycidyl ether with hexamethylenediamine, obtained according to Example 1 of Swiss patent application 3702/65, wherein after increasing the Viscosity to 30 cP at 25 ° the further condensation by adding

109830 / 19SA

of 36 g of acetic acid in 100 ml of water had been interrupted, and the solution obtained by distilling off water under reduced Pressure had been brought to 80% solids, and (b) an organic amine salt of dodecylbenzenesulfonate in a weight ratio of (a) :( b) of 1: 1. With the clarified dye solution, tissue is made of cellulose-2 ^ -acetate at room temperature impregnated. The excess liquor is squeezed off to about 100% of the dry weight of the goods. One dries the impregnated fabric at 40 to. 80 ° in a stream of air and then heat-set the dye for 100 seconds by IR irradiation at 190 to 210 °.

The blue dyeing obtained has a much better welding ψ fastness than the corresponding tissue that was first padded with an organic liquid containing the same dye mixture, and was then fitted in a separate organ bath with the same sizing agent.

Example 88

3 g of the same reddish yellow dye as used in Example 17 had been used, are dissolved in 957 g of a solvent mixture consisting of 927 g of tetrachlorethylene and 30 g Dime thy lace tamid consists. 40 g of a solution that contains 33% of a reaction product of 2.5 parts of zirconium n-propoxide and 1 part of paraformaldehyde in a mixture of n-propanol and tetra-P contains chlorethylene (volume ratio 1: 1) and 5% zinc octoate, these percentages being calculated on the total weight of the solution are. With the clarified dye solution obtained, tissue made of cellulose-2 ^ acetate is impregnated at room temperature, squeezed, the goods down to a liquor content of about 100% of their dry weight and the impregnated fabric dries at 40 to 80 ° in the air stream. The dyeing is finally heat-set for 100 seconds by IR irradiation at 190 to 210 °.

109830/1954

The yellow-colored fabric obtained has very good slip resistance. Its rubbing fastness is better than that of a corresponding dye obtained in a two-stage treatment,

Example 89

3. g of the same reddish yellow dye as used in Example 17 was mentioned, in 950 g of a solvent mixture consisting of 920 g of tetrachlorethylene and 30 g of dimethylacetamide exists, solved. To this are added 2 g of the oleic acid-ethylene oxide condensation product according to Example 1 and 0.5 g of the bacteriostatic Using the formula ■

CF ₃

Cl - / "^ - NH - CO - NH

dissolved in 50 g of tetrachlorethylene. With the clarified dye solution if tissue made of cellulose-2 ^ -acetate is impregnated at room temperature, then squeezes the goods down to a liquid content of about 1007o of its dry weight and dries the impregnated fabric at 40 to 80 ° in the air flow. The dyeing is then heat-set for 100 seconds by IR irradiation at 190 to 210 °.

The resulting red-tinged yellow-colored fabric is characterized by better bacteriostatic properties than a corresponding one Fabric that has been dyed and finished in two separate treatments and also has a much better rub, dry cleaning and wash fastness.

Example 90

3 g of the same red dye as used in Example 18 was used, are dissolved in 950 g of a solvent mixture composed of 920 g of tetrachlorethylene and 30 g of dimethy! acetamide consists. To this are added 2 g of the oleic acid-ethylene oxide condensation product according to Example 1 and 0.5 g of the bacteriostatic agent of the formula

NH - CO - NHhQ - Cl 109830/1954

dissolved in 50 g of tetrachlorethylene. With the clarified dye solution if tissue made of cellulose-2-2-acetate is impregnated at room temperature, then squeezes the goods down to a liquid content from about 1007o of their dry weight and dries the impregnated fabric at 40 to 80 ° in a stream of air. The coloring will then for 100 seconds by IR irradiation at 190 Heat set to 210 °.

The red-dyed fabric obtained is better bacteriostatic Properties characterized as a corresponding fabric that is dyed and finished in two separate treatments and also has a much better rubbing, dry cleaning and wash fastness.

Example 91

2 g of the same blue dye mixture as in example 19 was used, are dissolved in 950 g of a solvent mixture consisting of 920 g of tetrachlorethylene and 30 g of dimethylacetamide consists. To this are added 2 g of the oleic acid-ethylene oxide condensation product according to Example 1 and 0.5 g of the bacteriostatic Using the formula

Cl -f V-NH-CO-NH

dissolved in 50 g of tetrachlorethylene. Tissue made of cellulose acetate is impregnated with the clarified dye solution at room temperature, the goods are then squeezed to a liquid content of about 1007 _{o of} their dry weight and the impregnated tissue is dried at 40 to 80 ° in a stream of air. The dyeing is then heat-set for 100 seconds by IR irradiation at 190 to 210 °.

The blue-colored fabric obtained has better bacteriostatic properties Properties compared to a corresponding fabric dyed and finished in two separate treatments, as well as better rubbing, dry cleaning and washing fastness.

109830/1954

Claims (20)

Claims 1. A method for one-bath dyeing and finishing of fiber material made of cellulose ester, characterized in that one ^; this material with a solution which contains organic dye and finishing agent and optionally other auxiliaries combined in a solvent mixture which essentially consists of a) at least 50 percent by weight of optionally halogenated, boiling between 70 and 15O ⁰ C hydrocarbon and b) at most 50 weight percent water-miscible organic ■ schem, below 210 ⁰ C boiling solvent is, impregnated, and subsequently the excess treatment liquor from the Fasermafcerial removed or printed and the dyeing or printing by thermal fixing at temperatures below the softening point of the fiber material fixed. ™ 2. The method according to claim 1, characterized in that a Solvent mixture is used, which consists of 85 to 99.5 percent by weight of a halogenated hydrocarbon with a boiling point between 70 and 150 ^° C. and 15 to 0.5 percent by weight of an amide, monoalkylamide or dialkylamide of a lower fatty acid. 3. The method according to claim 1 and 2, characterized in that a water repellent is used as a finishing agent. - 4. The method according to claim 1 and 2, characterized in that an oil repellent is used as a finishing agent. 5. The method according to claim 1 and 2, characterized in that a finishing agent is used, which gives the handle of the fiber ' materials improved. 6. The method according to claim 1 and 2, characterized in that a flame retardant is used as a finishing agent. . 7. The method according to claim 1 and 2, characterized in that a bacteriostatic agent is used as the sizing agent. 10 9 8 3 0/1954, NoUfc »documents (Art. 7 Si I Fig. 2 No. l 3aU 3 of the amendment of 4.9.19b7) 8. The method according to claim 1 and 2, characterized in that a fungistatic agent is used as the finishing agent. 9. The method according to claim 1 and 2, characterized in that a non-slip means is used as finishing means. 10. The method according to claim 1 and 2, characterized in that an antistatic agent is used as the finishing agent. 11. The method according to claim 1 to 10, characterized in that a mixture of different finishing agents is used. 12. The method according to claim 1 to 11, characterized in that As a further aid, an ether or an ester of polyethylene glycol is used, which consists of a higher aliphatic hydrocarbon radical or the acyl radical of a higher fatty acid having a carbon chain of 8 to 20 carbon atoms or one alkyl-substituted phenyl radical, the alkyl chain of which is 6 to 12 carbon has atoms, and consists of a polyether chain of about 2 to 20 ethyleneoxy groups. 13. The method according to claim 12, characterized in that a polyethylene glycol monooleyl ether with 4 to as a further aid 10 ethyleneoxy groups is used. 14. The method according to claim 1 to 13, characterized in that a chlorinated, lower, aliphatic hydrocarbon is used as component a). 15. The method according to claim 14, characterized in that tetrachlorethylene or trichlorethylene is used as component a) will. 16. The method according to claim 1 to 13, characterized in that as component b) dimethylacetamide is used. 109830/1954 17. The method according to claim 1 to 16, characterized in that metal-free disperse dyes are used. 18. The method according to claim 1 to 17-, characterized in that cellulose acetate is used as the fiber material. 19. Treatment liquor for single-bath dyeing and finishing of fiber material made of cellulose ester is suitable, whereby the fabric is impregnated or printed and then heat-set, thereby characterized in that it consists of a solution, which in combination organic dye, finishing agent and optionally contains other auxiliaries in a solvent mixture that essentially consists of a) at least 50 percent by weight of optionally halogenated hydrocarbon boiling ^{between 70 and 150 0 C and} b) at most 50 percent by weight miscible with water, organic below 210 ⁰ C boiling solvent. 20. Cellulose ester fiber material, which according to the method according to the claims 1 to 18 was colored or printed and finished or treated with the treatment liquid according to claim 19 became. / ■ "109830/1954