US3623834A

US3623834A - Dye solution or print paste containing chlorinated hydrocarbon with an alcohol ketone dioxane alkanoic acid amide tetramethyl urea or pyridine and polyamide dyeing therewith

Info

Publication number: US3623834A
Application number: US606553A
Authority: US
Inventors: Marcel Seuret; Willi Leutenegger; Hans E Wegmuller
Original assignee: Ciba Geigy AG
Current assignee: Novartis AG
Priority date: 1966-01-05
Filing date: 1967-01-03
Publication date: 1971-11-30
Anticipated expiration: 1988-11-30
Also published as: GB1153221A; BE692183A; DE1619565A1; AT273872B; FR1507460A; NL6700129A; ES335268A1; CH454084A

Abstract

SYNTHETIC LINEAR POLYAMIDES ARE DYED OR PRINTED WITH A SHORT CHAIN CHLORINATED ALKANE SOLUTION CONTAINING ANY ONE OF AN ALKANOL, CYCLOALKANOLS, ARALKANOLS, ALKANONE, CYCLOALKANONE, ALKYLENE GLYCOL MONOALKYETHER, FURFURYL ALCOHOL, TETRAHYDROFURFURYL ALCOHOL, ALKANEDIOLS, DIOXANE, N,N-DIALKYLAMIDES OF SHORT CHAIN ALKANOIC ACIDS, N,N,N''TETRAMETHYL UREA, PYRIDINE OR MIXTURES THEREOF.

Description

United States Patent G US. Cl. 8-l72 9 Claims ABSTRACT OF THE DISCLOSURE Synthetic linear polyamides are dyed or printed with a short chain chlorinated alkane solution containing any one of an alkanol, cycloalkanols, aralkanols, alkanone, cycloalkanone, alkylene glycol monoalkyether, furfuryl alcohol, tetrahydrofurfuryl alcohol, alkanediols, dioxane, N,N-dialky1amides of short chain alkanoic acids, N,N,N'- tetramethyl urea, pyridine or mixtures thereof.

The present invention concerns a process for the continuous dyeing and printing of synthetic polyamide fibre material, the dye liquor used for this purpose and also the fibre material dyed or printed by this process.

It is known that synthetic polyamide fibre material is dyed both from an aqueous solution with water soluble dyestuffs and from an aqueous dispersion with dispersion dyestuffs, the dyeing being performed either at the boiling point of the Water or at temperatures of 100 to 130 C. under pressure. These dyeing processes, however, often lead to uneven (stripy) dyeings, particularly if texturized synthetic polyamide, Banlon, is used as fibre material and heavy metal containing dyestuffs are used as dyestuffs.

Moreover, these dyeing processes have several disadvantages: on the one hand, the dispersion dyestulfs have to be brought into a finely dispersed form which necessitates lengthy time-consuming milling operations with suitable dispersing agents and, on the other hand, large amounts of waste Water occur requiring extensive cleansing thereof.

Therefore, attempts have been made to dye the abovementioned material by means of organic dyestuff solutions. Thus, it has been suggested to impregnate synthetic polyamide fibre material with solutions of dyestulfs in certain organic solvents, such as ethylene glycol or polyethylene glycol, and, if polyethylene glycol is used, to subsequently subject the material to a wet heat treatment. However, these processes have proved to be unsatisfactory in various respects: in some cases the desired colour strength could not be attained according to these processes, while the fastness properties, especially the fastness to rubbing, of the dyeings obtained therewith did not satisfy present-day requirements. Further these processes require after-treatments, such as washing out of unfixed dyestuffs.

It has now been found that synthetic polyamide fibre material can be continuously dyed or printed in level deep and fast shades without an after-treatment. The new process comprises impregnating or printing the material with a solution of at least one dyestuff in a solvent mixture consisting of ice (a) 50 to 99% by weight of unsubstituted or preferably halogenated hydrocarbon which boils between 50 and 150 C., the balance consisting of (b) a liquid, water soluble organic solvent boiling below 220 C. and,

preferably however, these mixtures of solvents contain 50 to 99% by weight of halogenated, particularly chlorinated, hydrocarbons, e.g. chlorobenzene; however, in view of their generally easy recovery and incombustibility, chiefly, low aliphatic halogen hydrocarbons, such as chlorinated hydrocarbons, e.g. chloroform, carbon tetrachloride, trior tetra-chlorethylene (perchlorethylene), tetrachlorethane or dibromomethylene. Also mixtures of such solvents can form the water insoluble component of mixtures of solvents usable according to the invention.

By liquid, water soluble organic solvents boiling below 220 C. (b) are meant thermostable solvents of which not only fractions of percentages are soluble in water but which are soluble up to several percentages in water. Examples thereof are alkanols such as butanols or 'amyl alcohols, cycloaliphatic alcohols e.g. cycloalkanols such as cyclohexanol, araliphatic alcohols e.g. aralkanols such as benzyl alcohol, or aliphatic, or cycloaliphatic ketones e.g. alkanones and cycloalkanones such as methylethyl ketone or cyclohexanone. However, organic solvents as defined which are miscible with water in any ratio are preferred. Examples thereof are: low monovalent aliphatic alcohols such as low alkanols, e.g. methanol, ethanol, nor iso-propanol, alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether or ethylene glycol monoethyl ether, also furfuryl or tetrahydrofurfuryl alcohol, or divalent aliphatic alcohols e.g. alkanediols such as ethylene glycol or 1,2-propylene glycol, in addition, low aliphatic ketones such as acetone, low cyclic ethers such as dioxane, also N,N-dialkyl amides of low monocarboxylic acids such as dimethyl formamide or dimethyl acetamide, amides of carbonic acid such as N,N,N',N- tetramethyl urea, or tertiary organic amines such as pyridine, as well as mixtures of such liquid organic solvents which are soluble in water.

The composition of the mixture of solvents depends on the solubility of the dyestuff or mixture of dyestuffs to be used. It should be so composed that it is in the form of a homogeneous and clear dyestufi solution.

Preferred mixtures of solvents are those which consist of to 99% by weight of chlorinated low aliphatic hydrocarbon boiling between 50 and 150 C. the balance consisting of an organic solvent boiling below 220 C. and which is miscible with water in any ratio. A mixture consisting of by weight of trior per-chlorethylene and 10% by weight of a low alkanol, or a N,N-dialkyl amide of a low monocarboxylic acid, particularly a mixture of 90% by weight of trior per-chlorethylene and 10% by weight of methanol or dimethyl formamide has proved to be especially valuable.

Dyestuffs usable according to the invention are chiefly dispersion dyestuffs and water soluble dyestuffs. These are, in particular, azo, anthraquinone, nitro, methine, styryl, naphthoperinone, quinophthalone or 5-amino-8- hydroxy-1,4-naphthoquinone-imine dyestuffs.

By water soluble dyestuffs are meant, patricularly, the so-called acid wool dyestuffs of the azo and anthraquinone 3 series. Preferred azo dyestuffs are monoazo or disazo dyestuffs. Moreover heavy metal containing azo dyestuffs such as those containing chromium or cobalt, preferably metallised monoazo dyestuffs free from acid and basic water solubilising groups, which dyestuffs contain one metal atom bound to two molecules of azo dyestuff are suitable dyestuffs in the process of the invention. l-arnino- 4-arylamino-anthraquinone-Z-sulphonic acids are mentioned in particular as anthraquinone dyestuffs. Acid metal-free azo and anthraquinone dyestuffs which contain only one sulphonic acid group or carboxylic acid group are especially preferred.

The dyestuff solution to be used according to the invention preferably contains 0.1 to by weight of one or more of the dyestuffs mentioned, depending on the desired depth of shade.

If necessary, the dye solution usable according to the invention can also contain thickeners, advantageously those which are soluble in the mixture of solvents defined, e.g. thickeners having cellulose ester, polyvinyl ester or polyvinyl alcohol as base.

These thickeners are added in sufiicient amounts to raise the viscosity of the resulting dye liquor or paste to at least 30 centipoises.

Chiefly polyhexamethylene adipamide (Polyamide 6.6, nylon), polycaprolactam (Polyamide 6, Perlon), and polyaminoundecanoic acid (Polyamide l1, Rilsan), especially in the form of filament, but also texturized synthetic polyamide fibres Banlon are used as synthetic polyamide fibre material to be dyed or printed by the process according to the invention.

The fibre material defined is impregnated, for example, by printing or spraying, preferably however, by pad dyeing in the foulard. In the latter case, the fibre material is advantageously passed continuously through the dyestutf solution at room temperature and then squeezed out to the desired content of impregnation solution, which is about 30 to 150% by weight (calculated on the dry weight of the goods). The main part of the mixture of solvents remaining in the fibre material can then be removed, advantageously under mild conditions at 4080 C., particularly in a warm, dry airstream. The dyestuif is fixed on the still wet or already dry fibre material wherefrom excess dye liquor has been removed by steaming or by a dry heat treatment below the softening point of the fibre material. These two types of heat treatment can also be combined. For a dry heat fixing, contact heat, a treatment with high frequency alternating currents or irradiation with infrared rays are suitable; however, the dyestutf is preferably dry fixed on the fibre material in a hot airstream at about 145 to about 230 C., particularly at a temperature of 150 to about 210 C., optimally at 170 to 210 C.

Dyestutf Level, strongly coloured dyeings which are fast, e.g. to dry cleaning, washing in water or alkaline media, perspiration and rubbing, are obtained on the fibre material mentioned by the process according to the invention without any after-treatment, such as rinsing in water or organic solvents.

A further advantage of the process according to the invention over previously known processes is that the solvents used can be regained and again used in the dyeing process so that the problem of cleansing waste water does not arise. In addition, rinsing baths are not necessary. When dispersion dyestuffs are used, another advantage of the new process over previously known dyeing methods is that dyestuffs as they are obtained technically can be used direct for the production of the dyestuff solutions as defined. Finally, in the process according to the invention, the fibre material is impregnated in the cold which is an advance in the state of the art over similar known processes in which the impregnation is performed while heating.

The following examples illustrate the invention. The temperatures are given therein in degrees Centigrade.

EXAMPLE 1 5 g. of the dyestufi of the formula CH CH OH are dissolved in a mixture of solvents consisting of 900 g. of trichloroethylene and 100 g. of methanol. Fabric made from polyamide 6.6-filament is impregnated with this clear red dye solution at room temperature, the impregnated fabric is squeezed out to a liquor content of about calculated on the dry weight of the goods, and then dried at 40-80 in an airstream. The dried dyeing is then thermofixed for seconds at 210.

Without any after-treatment a strongly coloured, level and well developed red dyeing is obtained which has good fastness to rubbing, water and dry cleaning.

If, instead of a fabric made from polyamide 6.6-filament, a fabric or knitted article made from polyamide 6 is used and otherwise the procedure given in the example is followed, then a strongly coloured and well developed red dyeing is also obtained which has good fastness to rubbing.

If, instead of the dyestutf mentioned in the example, a dyestuff mentioned in column 2 of the following Table I is used and otherwise the procedure given in the example is followed, then strongly coloured, level and well developed dyeings are also obtained on the polyamide fabrics mentioned. The dyeings have the shades given in column 3.

TABLE I Shade on Polyamide 6.6

Violet.

NH- 0 O C H Reddish yellow.

Table I-Cntinued No. Dyestufi Shade on Polyamlde 6.6

Yellow.

Greenish yellow.

CHs

7 N 2 Yellow.

OH 00 l -CH i 8-0 CH Greenish yellow.

1 CN (CH3)2N CH=C 9 [H Blue.

HN i) II I 1o (I? NH; Do.

SO3H

11.... Greenish yellow.

N=N-H g-CH; Ho 01 H; N

SO3H

-N=NHom I N l0 210OC HO -SO H EXAMPLE 13 of the dry weight of the fabric, and the impregnated material is dried at in an airstream. The dyeing is 8 g. of dyestufl' of the formula then thermofixed for 5 minutes at Without any after-treatment a level and Well developed red dyeing having good fastness to rubbing is obtained. 0 N@N=N N If, instead of the 800 g. of trichlorethylene, the same \CHZCH2OH 7o amount of chlorobenzene is used, or, if instead of the 200 are dissolved in a mixture consisting of 800 g. of trichlorethylene and 200 g. of benzyl alcohol. A fabric made from polyamide 6.6 is impregnated with this solution as described in Example 1, the liquor content being about g. of benzyl alcohol the same amount of ethanol or methylethyl ketone is used and otherwise the procedure given in this example is followed, then also strongly coloured, well developed, red dyeings having good fastness properties are obtained.

7 EXAMPLE 14 6 g. of the dyestulf of the formula are dissolved in a mixture of solvents of 900 g. trichlorethylene and 100 g. of dimethyl formamide. Fabric made from polyamide 6.6 is impregnated with this clear, ruby red dye solution as described in Example 1. The liquor content is about 80% calculated on the dry weight of the fabric. Without intermediate drying the dyeing is then thermofixed for 3 minutes in a hot airstream at 180.

Without any after-treatment a strongly coloured, level and well developed ruby red dyeing having good fastness to rubbing is obtained.

If instead of the 900 g. of trichlorethylene, the same amount of chloroform, perchlorethylene, carbon tetrachloride or toluene is used, and/or if, instead of the 100 g. of dimethyl formamide, the same amount of methanol, ethylene glycol monomethyl or ethylene glycol monoethyl ether, acetone, dioxane, furfuryl alcohol or tetrahydrofurfuryl alcohol is used and otherwise the procedure given in this example is followed, then also red dyeings having good fastness properties are obtained.

EXAMPLE 15 5 g. of the dyestuff of the formula 0 NH, II

-SO3H CH3 Q are dissolved in a mixture of solvents of 850 g. of trichlorethylene and 150 g. of methanol. A knitted article made of polyamide 6-filament is impregnated with this solution and squeezed out as described in Example 1. The dyeing is then steamed for 15 minutes at 100 and afterwards dried.

Without any after-treatment a strongly coloured, level and Well developed blue dyeing on the material mentioned is obtained.

If, in the above example, instead of the knitted article made from polyamide 6-filament, a fabric made of texturized synthetic polyamide is used and otherwise the procedure given in this example is followed, then a very level blue dyeing is obtained which has good fastness to rubbing.

EXAMPLE 16 4 g. of the dyestuff of the formula are dissolved in a mixture of solvents of 970 g. of trichlorethylene and 30 g. of dimethyl acet-am'ide. A fabric made from polyamide 6.6-filament is impregnated with this solution and dried as described in Example 1. The dyeing is then thermofixed for 2 minutes at 200 in a hot airstream.

Without any after-treatment a strongly coloured, level and well developed yellow dyeing is obtained on the material mentioned.

If, instead of dimethyl aeetamide, the same amount of pyridine is used, then with otherwise the same procedure as given in this example, a strongly coloured, level and well developed yellow dyeing is also obtained.

EXAMPLE 17 5 g. of the 1:2 chromium complex of the compound are dissolved in a mixture of 900 g. of trichlorethylene and g. of methanol. Texturized synthetic polyamide fabric is impregnated with the clear, dark red coloured solution, the impregnated fabric is squeezed out to 100% liquor content (calculated on the dry weight of the goods) and dried at 6080 in an airstream. The dyestufi is thermofixed for 3 minutes in a hot airstream at 200.

In this way, without any after-treatment, a level, scarlet dyeing is obtained which has good wet fastness properties.

A dyeing of equal quality is obtained if, in this example, the impregnated and dried texturized synthetic polyamide fabric is steamed for 20 minutes at 100 instead of being thermofixed.

If, instead of the above 1:2 chromium complex, one of the 1:2 metal complexes given in the following Table II is used, then with otherwise the same procedure as given, dyein'gs on the fibre material mentioned are obtained which have the shades given in this table.

TABLE II Shade on 1 2 texturized synthetic No. Dyestufi polyamide 18...- 1 :2 chromium complex of the compound: Yellow.

('3 O 0 H HZN- s OzN=N U-om N HO N 19-... 1:2 chromium complex of the compound: Orange.

TABLE II-Con tinned Shade on 1 2 texturized synthetic No. Dyestufi polyamide 20.... 1 :2 chromium complex of the compound: Yellow.

('3 O O H N=N-,-HCH3 N H L 21--. 1:2 chromium complex 01 the compound: Grey.

OH HO O 0 CH3 We claim:

1. A process for the continuous, non-aqueous dyeing or printing of synthetic polyamide fiber material, consisting essentially of the steps of:

(a) impregnating this material with a solution of at least one dyestuff in a solvent mixture which consists of:

(I) 50 to 99% by weight of halogenated hydrocarbon having a boiling point between 50 and 150 C., the balance consisting of:

(II) a liquid, water soluble organic solvent having a boiling point below 220 C., and selected from the group consisting of alkanols, cycloalkanols, aralkanols, alkanones, cycloalkanones, alkylene glycol monoalkyl ethers, furfuryl alcohol, tetrahydrofurfuryl alcohol, divalent alkanediols, dioxane, vN,N-dialkylamides of lower monocarboxylic acids, N,N,N,N-tetramethyl urea, pyridine and mixtures thereof which are soluble in water,

(b) removing a substantial part of excess solvent from the material, and

(c) fixing the resulting dyeing or print by steaming and/ or a dry heat treatment of the impregnated fiber material, the dry heat treatment being carried out at 10 temperatures of at least 145 C., thereby obtaining a finished dyeing or print on the said fiber material. 2. A process as defined in claim 1, further comprising: (III) admixing thickener with said mixture of (I) and (II).

3. A process as defined in claim 1, wherein the solvent defined under (II) is a liquid which is miscible with water in any proportion.

4. A process as defined in claim 1, wherein said mixture of (I) and (II) consists of to 99% by weight of chlorinated lower aliphatic hydrocarbon having a boiling point between 50 and 150 C., the balance consisting of a completely water-miscible organic solvent having a boiling point below 220 C.

5. A process as defined in claim 1, wherein said mixture of (I) and (II) consists of about by weight of trichloroethylene or tetrachloroethylene and the balance of a lower alkanol or the N,N-di-(lower alkyl) amide of a lower aliphatic monocarboxylic acid.

6. The process of claim 5 wherein an N,N-di-(lower alkyl) amide of a lower aliphatic monocarboxylic acid is employed.

7. The process of claim 5 wherein a lower alkanol is employed.

8. A process as defined in claim 1, wherein said mixture of (I) and (II) consists of about 90% by weight of trichloroethylene or tetrachloroethylene and the balance of methanol or dimethyl formamide.

9. A process as defined in claim 1, wherein the watersoluble organic solvent is selected from the group consisting of methanol, ethanol, n-propanol, isopropanol, butanols, pentanols, cyclohexanol, benzyl alcohol, acetone, methylethyl ketone, cyclohexanone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, furfuryl alcohol, tctrahydrofurfuryl alcohol, ethylene glycol, 1,2-propylene glycol, dioxane, dimethyl forrnarnide, dimethyl acetamide, zN,N,N',N'-tetramethyl urea, pyridine and mixtures of such solvents which are water soluble.

References Cited UNITED STATES PATENTS 2,249,756 7/1941 Finzel 8-130.1 UX 2,265,119 12/1941 Coolidge 8130.1 UX 2,323,871 6/ 1943 Kienle 8-62 2,828,180 3/1958 Sertorio 8-62 2,971,458 2/1961 Kumins et al. 8-62 3,265,461 8/1966 Luetzel et a1 8-84 3,022,356 2/1962 Vernooy 260-633 3,129,053 4/1964 Castle 8-93 3,326,846 6/1967 Pascal 8-93 DONALD LEVY, Primary Examiner U.S. Cl. X.R. 8-41, 62, 173, 176