DE2842187A1 - Phthalocyanine dyes contg. substd. sulphonamide gps. - for use on cellulose fibres and blends with synthetic fibres. - Google Patents

Abstract

Dyeing or printing of cellulose fibres swollen with water-miscible swelling agents or mixts. contg. these, uses dyes of formula (I). Pc is the gp. of a Cu, Ni or Co phthalocyanine molecule; R is H or opt. substd. alkyl; A is arylene; Q is -O-, -S-, -NH- or a direct bond; B is opt. substd. (cyclo) alkylene; R1 and R2 are H, opt. substd. alkyl or cyclo-alkyl; R1 may also be NR3R4 or with R2 form with N a satd. 5- or 6-member ring; R3 and R4 are H or alkyl; Z+ is H, alkali metal, NH4 or a quaternised amine RNH-(AQ)n-B-NR1-R2 (where Hal is Cl or Br; n = 0 or 1; x = 2-4; y =0-1 and z = 0-4). Esp. used for dyeing blends of cellulose and synthetic fibres, in partic. cotton/polyester blends, in turquoise to green shades. Tone-on-tone shades are obtd. as blends of fibres by a single-stage process, with very good fastness, esp. to sublimation, washing, light and dry-cleaning.

Description

Process for dyeing and printing cellulose fibers

The invention relates to a method for dyeing and printing cellulose fibers swollen with water-miscible swelling agents or containing them Mixed fibers.

The method is characterized in that the fibers with a dye of the general formula where Pc is the radical of a Cu, Ni or Co phthalocyanine molecule, R is hydrogen, optionally substituted alkyl, A is arylene, Q is -0-, -S-, -Nil- or a direct bond, B is optionally substituted alkylene or cycloalkylene , R1 and R2 are hydrogen, optionally substituted alkyl or cycloalkyl or R1 is the group or R1 and R2 together with N form a saturated 5- or 6-membered ring, R3 and R4 hydrogen or alkyl, a hydrogen ion, an alkali metal ion, NH4 (or an ammonium ion which is different from the amine derives, Hal is chlorine or bromine, n is 0 or 1, x is 2 to 4 y is 0 to 1 and z is 0 to 4, are treated and the dye is fixed by heat treatment.

The invention also relates to dye preparations for dyeing and printing of cellulose and cellulose-containing fiber material which contains a dye of the formula I.

The dyes of the formula (I) are in the neutral range Dyes that are sparingly soluble to insoluble in water.

Preference is given to dyes of the formula (I) in which Pc represents the remainder of Cu or Ni phthalocyanine.

The number of sulfonic acid groups adhering to the Pc residue is im Mean less than 1, preferably less than 0.5.

Preferred alkyl radicals are those having 1-6, in particular 1-4, carbon atoms and preferred alkylene radicals are those with 2-6, especially 2-4, carbon atoms.

Cycloalkyl or cycloalkylene is preferably cyclohexyl or Cyclohexylene.

Preferred arylene are the isomeric phenylene radicals which are substituted could be.

Examples of saturated 5- or 6-membered rings are pyrrolidine, Morpholine, piperidine and N-methyl- or N-ethylpiperazine should be mentioned.

Particularly suitable substituents are hydroxy, C1-C4-alkoxy, chlorine or bromine and, for the cyclic radicals, also C1-C4-alkyl.

Examples for R are, besides hydrogen, methyl, ethyl, n- and iso-propyl, Methoxyethyl, ethoxyethyl, methoxypropyl or ethoxypropyl.

Examples of A are o-, m- and p-phenylene, 2-chloro-1,4-phenylene, 5-methyl-1,3-phenylene, 4-methyl-1,2-phenylene and 2,5-dimethyl-1,4-phenylene.

Preferred radicals B are ethylene, 1,3-propylene, 1,2-propylene, 1,4-butylene, 1,3-butylene and 1,4-cyclohexylene are suitable.

R1 and R2 can be the same or different and, for example, for Methyl, ethyl, n- and iso-propyl, butyl, ß-hydroxyethyl, ß-methoxyethyl or ß-ethoxypropyl stand.

Preferred dyes are those of the formula in which Pc, Q, n, x, y and z have the meaning given in formula (I) and R 'is hydrogen or C1-C4-alkyl optionally substituted by C1-C4-alkoxy, A' optionally by C1-C4-alkyl, C1-C4-alkoxy, chlorine or bromine-substituted o-, m- or p-phenylene, B 'C2-C6-alkylene or o-, m- or p-cyclohexylene 1 and R'2 which are optionally substituted by C1-C4-alkyl Hydrogen, C1-C6-alkyl optionally substituted by hydroxy or C1-C4-alkoxy or o-, m- or p-cyclohexylene optionally substituted by C1-C4-alkyl, or R'1 is the group or R'1 and R'2 together with N are a pyrrolidine, morpholine, piperidine, N-methylpiperazine or N-ethylpiperazine radical optionally substituted by C1-C4-alkyl, R'3 and R'4 are hydrogen or C1-C4-alkyl, Z '(+) H (+), Na (+), K (+), NH4 (+) or an ammonium ion that is different from the amine derives, mean.

Of the dyes of the formulas (I) and (II), the dyes are with R or R '= hydrogen to be emphasized; and of these, in turn, there are those with n = 0 and or B '= C2-C4-alkylene preferred.

From this group are the dyes with R1 or R'1 and R2 or R'2 = C1-C3-alkyl of particular interest.

The dyes of the formula (I) are prepared in a customary manner by reacting phthalocycanine sulfonic acid chlorides of the formula Pc- (SO2C1) x + y (III) with at least x moles of amine of the formula carried out with the addition of an acid-binding agent, preferably working in an aqueous medium and at temperatures of OOC-30 ° C.

In this reaction, a minor side reaction takes place Hydrolysis of SO2Cl groups takes place.

However, the number of sulfonic acid groups formed is on average less than 0.5 per phthalocyanine molecule.

The phthalocyaninesulfonic acid chlorides of the formula (III) are known in Way by treating phthalocyanines or phthalocyaninesulfonic acids with chlorosulfonic acid or chlorosulfonic acid and thionyl chloride or phosphorus pentachloride. Dyes of the formula (I) and their preparation are, for example, from DE-AS 1 061 010 known.

The water-soluble dyes to be used according to the invention differ from the phthalocyanine pigments in that they are due to their substituted sulfonamide group have a certain hydrophilicity and in organic Media such as dimethylformamide, chloroform, dichlorobenzene or nitrobenzene to a certain extent Scope are soluble.

It has now been found that the dyes of the formula (I) are free of fiber-reactive groups are excellent for dyeing and printing of water-swellable cellulose fibers and mixed fibers containing them, if they are applied according to the method known from DE-AS 1,811,796.

In this process, the fibers are in front of or at the same time as the Dye treatment with an amount sufficient to swell the cellulose water and in contact with a water-miscible swelling agent brought. The swelling agent must be able to maintain the swelling of the cellulose when the water is removed and the dye, if necessary with the help of a to solve additional solubilizer at the dyeing temperature. The swelling agent is generally in a diene of 10 to 30 wt .-%, based on. the cellulose fibers, added. Suitable swelling agents have a boiling point of over 100C.

Dye and swelling agent can be applied to the fiber at the same time or the fiber can first be mixed with the soaking agent and then with the aqueous one Dye dispersion are treated.

The dye is finally treated with Ilitz, in particular Fixed at 150 - 2300C.

The process is suitable for dyeing and printing both from native Cellulose as well as regenerated cellulose.

The process is of particular interest for dyeing and printing of mixed fibers made of cellulose and synthetic fibers such as polyamide and polyester fibers, especially cotton-polyester mixed fibers, as there is a tone-on-tone dyeing or printing made possible in a single-stage mode of operation.

Procedures of this type and other aids that take the place of the of DE-AS 1 811 796 known products used can be are for example from the German Offenlegungsschriften 2 524 243, 2 528 743, 2,636,427, 2,643,804 and 2,751,830 are known.

The dyes (I) give dyeings and prints, their color shades lie between turquoise blue and green and match well on the mixed fibers. They are distinguished by very good fastness properties, in addition to being washable Above all, the fastness to sublimation, light and dry cleaning should be emphasized.

In addition to water, the dye preparations according to the invention can be customary Components such as dispersants, e.g. nonionic and / or anionic and / or cationic dispersants, thickeners and / or those mentioned above Contain dye solvents.

The parts mentioned in the following examples are parts by weight and the degrees Celsius degrees.

Example 1 a> 200-300 parts of the dye of the formula are combined with 60 to 90 parts of a non-ionic dispersant (emulsifier U), made up to 1000 parts with water and dispersed in a ball mill or other suitable device. To prevent the dyestuff powder from drying out too quickly, a little preservative and glycols or glycerine can be added to the dough.

b) A fabric made of PESICO 50:50 is made up of a printing paste from 1 to 50 parts of the dyestuff powder from paragraph a) 100 parts of polyethylene glycol (Molar weight about 400) 399-350 parts of water and 500 parts of a 10% guar flour thickener 1000 parts are printed using a rotary film printing machine or film printing tables used. (Using a Rouleaux printing press must ever Depending on the engraving depth, the amount of polyethylene glycol can be increased to 150-200 parts.) Then it is dried, fixed for 1 minute at 2100 with dry heat, rinsed, soaped, rinsed again and dried.

A washfast turquoise-blue print is obtained.

c) The dye used under a) and b) is prepared as follows: In a mixture of 150 parts of water and 36 parts of 1-amino-3-dimethylamino-propane from 00, an aqueous, 0 ° - 30 cold paste of 43.5 parts of copper phthalocyanine (3) trisulfochloride stirred in.

The temperature of the reaction mixture is increased to 600 within 6 hours, suction filtered and washed with water until the run-off is almost neutral. After drying, 52 parts of a blue powder of the formula are obtained The dye obtained is easily soluble in 0.5% acetic acid.

EXAMPLES 2-23 The procedure described in Example 1 is repeated, except that the dyes of the formula described in the table below are used Washable prints with the color shades given in the table are obtained. For example, ZAR R1 R2 xy hue play E: CE: 6 3 7: 1 3 kkk FI tn 2 Cu 3 -CH2-CH2- H C2H5 C2H5 2.7 n turquoise blue tn t uz e rl H 3 Cu 3 -CH2-CH2-CH2- H CH3 CH3 3,6 .Q turquoise blue khk -CH2-CH2-CH2- H CH3 CH3 r (m 3 5 Cu 3 to CH3 at 2.7m XXW 6 Ni 3 -CH2-CH2-CH2- H CH3 CH3 2.7 0.3 turquoise 7 Ni o 0-CH2-CH2- o CH3 CH3 3.6 O bluish green 8 Ni 3 CH3-C, H-CH2-CH2-CH2- H C2H5 C2H5 2.7 0.3 bluish green 9 Cu 3 CH3-C1H-CH2-CH2-CH2- H C2H5 C2H5 3.6 0.4 turquoise blue N mmm m -CH2-CH2-CH2- m C2H5 C2H5 2.7 mm 11 u UCu m -CR2-CH2-CH2- m C2H5 C2H5 3.6 0.4 turquoise blue 12 Cu 4 -CH2-CH2-CH2- H C2H5 C2H5 2.7 0.3 turquoise blue m Ni 3 nnrrrLnu, $ cis 14 Ni uuu U uuu CH3 uuuuuu m m 1 ruru mm Co IN I UU (V 1 3: 3: 17 Cu 3 | H umx | G NNNIUU CQ NNNI CS N UUUINNUUUU CC UU IIIIIU 5: n IIIIU o1 N tEl o1 N [UU tN CS NO \ ON (N m: m OII> X UUUUU 1: 2 = UUUAAUU lllll X UU- lll? - q,? a f SNN CS N 'Y, II CS O1 N lll JN CUC Ú U mU Ú U 3) UU Ú hi 9 ç Ú C.) IIIIIUOIIIII | | > OD uuuuz æ zuuuuzzuuu c> o N nv rvr For example, ZAR R1 R2 xy hue play 7 17 7 7 m mm mm 18 Cu 3 -CH2-CH2-C2- HH 2.7 0.3 turquoise blue cc qA A r9 I11 V1 rnrn rn rn rl br (rt 19 Cu X CH2-CH2-CH2-H H3 H CH3 c, c, V + I m Cu 3 -C2-CH2- H CH2-CH2-OH CH3 3.6 m turquoise blue v O Cu o -CH2-CH2- oo O >> tD U) bb R. N e ur mm mcu m Cu 3 -CH2-CH2-CH2 Um m O nn N @ X n XQ X x Ux m 5 lll tM C> l N mmm uuu llll NNN cs NN uuuuuu llllll N cç NNNN ú u ux ú ú u llllll n XX nm v7 ao ffi ON NN cs N Example 24 a) 200-300 parts of the dye of the formula are combined with 60 to 90 parts of a non-ionic dispersant (emulsifier U), made up to 1000 parts with water and dispersed in a ball mill or other suitable device.

To prevent the dyestuff powder from drying out too quickly, you can add preservatives and glycols or glycerine to the dough.

b) A fabric made of PES / Co 65:35 is made up of a printing paste from 1 to 50 parts of the dyestuff powder from paragraph a) 100 parts of the boron ester of polyethylene glycol (molar weight. 300) 399-350 parts of water and 500 parts of a 4% alginate thickening printed lo00 parts using a rotary film printing machine or film printing tables are used Then it is dried, 1 Minute at 210 0C fixed with dry heat, rinsed, soaped, rinsed again and dried. A washfast turquoise-blue print is obtained.

c) The dye used under a) and b) is prepared as follows: In a mixture of 150 parts of water and 56 parts of 2-amino-5-diethylaminopentane at 0 °, an aqueous, cold paste of 43.5 parts of copper naphthalocyanine ( 3) -trisulfochlorid stirred in. The temperature of the reaction mixture is increased to 600 within 6 hours, suction filtered and washed with water until the run-off is almost neutral. After drying, 56 parts of a blue powder of the formula are obtained The dye obtained is easily soluble in 0.5% acetic acid.

Example 25 a) 200-300 parts of the dye of the formula are combined with 60 to 90 parts of a non-ionic dispersant (emulsifier U), made up to 1000 parts with water and dispersed in a ball mill or other suitable device. To prevent the dyestuff powder from drying out too quickly, a little preservative and glycols or glycerine can be added to the dough.

b) A fabric made of PES / CO 50:50 is mixed with a 10% solution of Polyethylene glycol (molar weight 400) padded with a squeeze effect of 100% and then with a paste of 1-750 parts of the dyestuff powder from paragraph a) 50 parts of a thickener concentrate consisting essentially of alkaline digested polyacrylic acid consists of 949 - 800 parts of water 1000 parts printed.

This is followed by drying and then fixing in HT steam for 6 minutes at 1750. Now it is rinsed, soaped, rinsed again and dried. You get a real one turquoise blue print.

The dye used under a) and b) is prepared as follows: In a mixture of 150 parts of water and 46 parts of 1-amino-3-diethylaminopropane from 0 ° is an aqueous, cold paste of 43.5 parts of copper phthalocyanine-3-trisulfochloride stirred in.

The temperature of the reaction mixture is increased to 600 within 6 hours, suction filtered and washed with water until the run-off is almost neutral. After drying, 55 parts of a blue powder of the formula are obtained The dye is easily soluble in 0.5 acetic acid above.

Claims (4)

Claims 1. A process for dyeing and printing cellulose fibers swollen with water-miscible swelling agents or mixed fibers containing them, characterized in that the fibers are treated with dyes of the general formula where Pc is the radical of a Cu, Ni or Co phthalocyanine molecule, R is hydrogen, optionally substituted alkyl, A is arylene, Q is -O-, -S-, -NH- or a direct bond, B is optionally substituted alkylene or cycloalkylene , R1 and R2 are hydrogen, optionally substituted alkyl or cycloalkyl or R1 is the group R1 and R2 together with N form a saturated 5- or 6-membered ring, R3 and R4 hydrogen or alkyl, a hydrogen ion, an alkali metal ion, NH4 or an ammonium ion which is different from the amine Derives Hal chlorine or bromine, n means 0 or 1 x 2 to 4, y means 0 to 1 and OC to 4, treated and the dye is fixed by heat treatment. 2. The method according to claim 1, characterized in that one dyes of the general formula where Pc, Q, n, x, y and z have the meanings given in formula (I), and hydrogen or C1-C4-alkyl optionally substituted by C1-C4-alkoxy, A 'optionally by C1-C4-alkyl, C1 -C4-alkoxy, chlorine or bromine-substituted o-, m- or p-phenylene, B 'C2-C6-alkylene or o-, m- or p-cyclohexylene which is optionally substituted by C1-C4-alkyl, 1 and R'2 Hydrogen, C1-C6-alkyl optionally substituted by hydroxy or C1-C4-alkoxy or o-, m- or p-cyclohexylene optionally substituted by C1-C4-alkyl, or R'1 is the group or R'1 and R'2 together with N are a pyrrolidine, morpholine, piperidine, N-methylpiperazine or N-ethylpiperazine radical which is optionally substituted by C1-C4-alkyl, R'3 and R'4 are hydrogen or C1-C4-alkyl, zI (+) H (+), Na (+), K (+), Nah, (+) or an ammonium ion that is different from the amine derives, means, used. 3. The method according to claims 1 and 2, characterized in that that one uses dyes whose Pc radical is the radical of Cu or Ni phthalocyanine and wherein y is less than 1, preferably less than 0.5. 4. Preparation for dyeing and printing cellulose fibers guollenen with water-miscible swelling agents or mixed fibers containing them, characterized in that it is a dye of the general formula where Pc is the radical of a Cu, Ni or Co phthalocyanine molecule, R is hydrogen, optionally substituted alkyl, A is arylene, Q is -0-, -S-, -NH- or a direct bond, B is optionally substituted alkylene or cycloalkylene , R1 and R2 are hydrogen, optionally substituted alkyl or cycloalkyl or R1 is the group or R1 and R2 together with N form a saturated 5- or 6-membered ring, R3 and R4 are hydrogen or alkyl, a hydrogen ion, an alkali metal ion, NH4 or an ammonium ion which is different from the amine derives, Hal is chlorine or bromine, n is 0 or 1, x is 2 to 4, YO is up to 1 and 2 is 0 to 4.