GB1572360A

GB1572360A - Dye formultations for cellulosic fibrous materials

Info

Publication number: GB1572360A
Application number: GB1679977A
Authority: GB
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 1976-04-24
Filing date: 1977-04-22
Publication date: 1980-07-30
Also published as: CH599287A5; FR2348996B1; DE2618032A1; IT1075306B; JPS52132182A; FR2348996A1

Description

(54) DYE FORMULATIONS FOR CELLULOSIC FIBROUS MATERIALS (71) We, BASF AKTIENGESELLSCHAFT, a German Joint Stock Company of 6700 Ludwigshafen, Federal Republic of Germany, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- The present invention relates to aqueous dye formulations for dyeing cellulosic fibrous materials.

According to the invention such a dye formulation contains one or more dyes of the general formula (I)

where R and R' are each independently alkyl of 1 to 4 carbon atoms, chlorine, bromine, alkoxy of 1 to 4 carbon atoms, phenoxy, methylphenoxy or chlorophenoxy and n and n' are each independently 0, 1, 2 or 3 (i.e. R and R' are identical or different and n and n' are identical or different), together with one or more dispersants and one or more water-retaining agents and with or without a disinfectant.

Examples of specific meanings of R and R' in formula (I), in addition to chlorine and bromine, are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, isobutyl and tert.-butyl (if R and R' are alkyl of 1 to 4 carbon atoms), methoxy, ethoxy, propoxy, butoxy and isobutoxy (if R and R' are alkoxy of 1 to 4 carbon atoms), phenoxy, pmethylphenoxy and p-chlorophenoxy.

Accordingly, the dyes (I) may contain, for example, the following radicals as groups

phenyl, 0-tolyl, p-tolyl, m-tolyl, o-chlorophenyl, p-chlorophenyl, p-bromophenyl, pethylphenyl, p-isopropylphenyl, p-tert.-butylphenyl, p-sec.-butylphenyl, 2,4-dimethylphenyl, 3,5-dimethylphenyl, 2,4,6-trimethylphenyl, 2-methyl-4-chlorophenyl, 2-chloro4-methylphenyl, 2,4-dichlorophenyl, 3,5-dichlorophenyl, p-methoxyphenyl, p-ethoxyphenyl, 2-chloro-4-methoxyphenyl, 2,4-dimethoxyphenyl, 3,4-dimethoxyphenyl, 4phenoxyphenyl, 4- (4'-methylphenoxy) -phenyl and 4- ( 4'-chlorophenoxy) -phenyl. The radicals (IIa) and (IIb) may be different, but are preferably identical.

For tinctorial and technological reasons, formulations which contain dyes of the formula (I), where n and n' are each independently 0 or 1, are preferred. Particularly preferred dyes of the formula (I) are those where the radicals of the formulae

are each independently phenyl, p-tolyl, o-tolyl, m-tolyl, o-chlorophenyl, p-chlorophenyl, m-chlorophenyl, p-methoxyphenyl, p-ethoxyphenyl, p-ethylphenyl, p-tert. -butylphenyl, 4-phenoxyphenyl or 4-(4'-chlorophenoxy)-phenyl. Dyes (I) in which the groups (IIa) and (IIb) are identical are particularly preferred.

The formulations according to the invention in general contain from 5 to 40C,'a by weight, preferably from 20 to 35% by weight, based on the formulation, of dye (I), from 4 to 10% by weight of dispersant(s), from 5 to 15% by weight of water retaining agent(s) and, if desired, from 0.5 to 1.5% by weight of disinfectanr(s), water-accounting for the remaining amount of from 85.5 to 33.5% by weight in the presence of disinfectant and from 86 to 35% in the absence of disinfectant.

The formulations according to the invention are advantageously manufactured by milling a suspension of from 1S to 40, preferably from 20 to 35, parts of dye (I), from 4 to 10 parts of dispersants, from 5 to 15 parts of water-retaining agents and, if desired, from about 0.5 to 1.5 parts of disinfectant in from 75.5 to 33.5, preferably from 70.5 to 38.5, parts of water in a stirred ball mill, a bead mill or a sand mill, until the particle size is about 0.5 ,um or less. This gives dye dispersions having a good shelf life.

Examples of the dispersants are the anionic and non-ionic dispersants conventionally used for the manufacture of finely divided formulations of disperse dyes.

Examples of anionic dispersants are ligninsulfonates, salts of phenol/formaldehyde/ sodium sulfite condensation products (German Laid-Open Application 2,301,638), salts of 2-naphthalenesulfonic acid/formaldehyde condensation products, salts of phenolsulfonic acid/urea/formaldehyde condensation products, and salts of condensation products of- phenolsulfonic acid/urea/formaldehyde which have been subjected to post-condensation with phenol and formaldehyde.

Examples of non-ionic dispersants are, above all, ethylene oxide adducts and propylene oxide/ethylene oxide adducts. These are described, for example, in U.S.

Patents 2,979,538 and 3,841,888 and German Patent 1,081,226.

The amount of dispersant depends on the dye and on its concentration in the dispersion; as a rule, the amount of dispersant is from 4 to 10% by weight, based on the formulation.

Examples of the water-retaining agents are above all glycols, e.g. ethylene glycol, propylene glycol, diethylene glycol and preferably dipropylene glycol. The amount is in general from 5 to 15% by weight, preferably from 8 to 12% by weight, based on the formulation.

The dyes of the general formula (I) may be manufactured by reacting 1,8-dinitro4,5-dihydroxyanthraquinone with the appropriate aniline derivatives by the process described in German Patent 1,277,475.

The dyes of the formula (I) can, from the point of view of their structure, be described as disperse dyes. They differ from vat dyes by their significantly higher solubility in organic solvents.

German Patent 1,811,796 describes a process which permits printing water insoluble dyes onto cellulose or cellulose-containing textile material and can be used for the dye formulations of the present invention. According to the procedure disclosed there, the cellulose or cellulose-containing textile material is contacted with water and an epoxyethylene or oxypropylene compound to swell the fibers and, simultaneously or subsequently while the fibers are still swollen, with the dye formulation. The data on process conditions given in the said patent also apply in general terms to the dye formulations according to the present invention.

In addition, German Laid-Open Applications 2,524,243 and 2,528,743 disclose further processes by means of which the dye formulations of the invention can be applied. Amongst these, printing processes are preferred.

The dye formulations of the invention give dyes and prints having very good fastness properties, amongst which wet fastnesss, fastness to crocking, fastness to dry cleaning, and light fastness, should be singled out. In printing, no staining of such white ground as may be present occurs on washing.

In the Examples which follow, parts and percentages are by weight, unless stated otherwise.

EXAMPLE 1.

a) A cotton fabric is printed by rotary screen printing with an ink which comprises 10 parts of the dye of the formula

in the form of a 30% strength aqueous formulation (see b)), 100 parts of polyethylene oxide of molecular weight 300 and 890 parts of a 3% strength alginate thickener, and the print is dried at 100"C. It is then treated for 1 minute with hot air at 200"C, rinsed cold, soaped at the boil, again rinsed cold and dried.

A wash-fast print in a clear green hue on a white ground is obtained.

b) 30 parts of the dye referred to under a), 6 parts of ligninsulfonate and 10 parts of dipropylene glycol are stirred in 50 parts of water and the suspension is milled in a sand mill until the particle size is 0.5 Lam or less. 1 part of pentachlorophenol is added and the dye content is brought to 30% by adding water. A formation having a good shelf life is obtained.

EXAMPLES 2 TO 5.

The method described in Example 1 is followed by instead of the above dye those mentioned in the Table are used. Prints in the hues shown in the Table are obtained. The dye formulations are prepared as described in Example 1 b).

Example No. -X Hue of the print

bluish green olive green olive EXAMPLE 6.

A union fabric of polyester/cotton (in the weight ratio of 67:33) is printed with a paste which consists of 10 parts of the dye of the formula

in the form of a 35% strength aqueous formulation, 120 parts of the reaction product of a polyethylene oxide of molecular weight 300 with boric acid in the molar ratio of 3:1 and 860 parts of a 10% strength alginate thickener. The print is dried at 105 C and treated wth live steam at 1800C for 6 minutes. It is then rinsed with cold water, soaped at 80"C, again rinsed with cold water and dried.

A wash-fast print having a clear green hue is obtained.

The formulation was prepared as described in Example lb).

EXAMPLES 7 TO 12.

The procedure described in Example 6 is followed, but dyes where X has the meaning shown in the Table which follows are used.

After fixing and rinsing, wash-fast prints having the hues shown in the Table are obtained.

Example No. -X Hue

green clear green green clear green olive bluish grey

Claims

WHAT WE CLAIM IS:

1. An aqueous dye formulation for cellulosic textile material which contams one or more dyes of the general formula

where R and R' are each independently alkyl of 1 to 4 carbon atoms, chlorine, bromine, alkoxy of 1 to 4 carbon atoms, phenoxy, methylphenoxy or chlorophenoxy and n and n' are each independently 0, 1, 2 or 3, together with one or more dispersants and one more water-retaining agents and with or without a disinfectant.

2. Dye formulations as claimed in claim 1, where n and n' are each independently 0 or 1.

3. Dye formulations as claimed in claim 1 or claim 2, wherein the radicals of the formulae

are each independently phenyl, p-tolyl, m-tolyl, o-tolyl, o-chlorophenyl, m-chlorophenyl, p-chlorophenyl, p-methoxyphenyl, p-ethoxyphenyl, p-ethylphenyl, p-tert.-butylphenyl, 4-phenoxyphenyl or 4-(4'-chlorophenoxy)-phenyl and may be identical or different.

4. Dye formulations as claimed in claim 3, where the radicals of the formulae set forth are identical.

5. Dye formulations as claimed in any preceding claim which contain-based on the formulation-from 5 to 40C, by weight of dye, from 4 to 10% by weight of dispersant, from 5 to 15% by weight of water-retaining agent and from 86 to 35% by weight of water.

6. Dye formulations as claimed in any preceding claim which contain from 20 ro 35% by weight of dye.

7. Dye formulations as claimed in any preceding claim which contain from 0-5 /O to 1.5% by weight of disinfectant

8. Dye formulations as claimed in any one of claims 1 to 4 which contain 20 to 35% by weight of dye, 4 to 10% by weight of dispersant, 5 to 15% by weight of water-retaining agent, from 0.5 to 1.5% by weight of disinfectant, and 70.5 to 38.5% by weight of water.

9. Dye formulations as claimed in any preceding claim wherein the dye is one hereinbefore identified specifically.

10. Dye formulations as claimed in claim 1 and substantially as hereinbefore described in any one of the foregoing specific Examples.

11. A cellulosic textile material whenever dyed with a dye of the general formula defined in claim I

12. A dyed textile material as claimed in claim 11 wherein the dyeing has been carried out by a process according to German patent 1,811,796 or German laid-open application 2.24,243 or 1,528,743.