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Title:
STABLE AQUEOUS LIQUID COMPOSITION OF REACTIVE DYES CONTAINING beta-SULFATOETHYLSULFONYL GROUPS
Document Type and Number:
WIPO Patent Application WO/1984/003312
Kind Code:
A1
Abstract:
An aqueous, liquid fiber-reactive dye composition which is stable to decomposition. The composition consists essentially of 5 to 45 % by weight of a water-soluble, fiber-reactive dyestuff having from 1 to 3 beta-sulfatoethylsulfonyl (-SO2CH2CH2OSO3H) groups, or a mixture of such dyestuffs; 0 to 10 % by weight of water-soluble inert inorganic salt; and 45 to 95 % by weight of water. Said liquid dye composition must have a pH of about 2.5 to about 4.5 and must be substantially free of buffer substances. The liquid dye composition may be stored for long periods of time at 0o to 50oC with substantially reduced decomposition to the vinylsulfonyl dye form.

Inventors:
CORSO ANTHONY J (US)
Application Number:
PCT/US1984/000230
Publication Date:
August 30, 1984
Filing Date:
February 21, 1984
Export Citation:
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Assignee:
HOECHST CO AMERICAN (US)
International Classes:
C09B62/505; C09B62/51; C09B62/507; C09B62/513; C09B62/515; C09B62/517; C09B67/26; (IPC1-7): D06P1/38; C09B62/00
Foreign References:
US4118184A1978-10-03
US4349349A1982-09-14
US4149850A1979-04-17
US4078884A1978-03-14
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Claims:
CIAIMSWhat is claimed is:
1. An aqueous, liquid fiberreactive dye composition which is stable to decαrposition consisting essentially of 5 to 45% by weight of a watersoluble, fiberreactive dyestuff having frαn 1 to 3 S02CH2(H20S03H groups, or a mixture of such dyestuffs; 0 to 10% by weight of watersoluble inert inorganic salt; and 45 to 95% by weight of water; said liquid dye composition having a pH of about 2.5 to about 4.5 and being substantially free of buffer substances.
2. A composition according to claim 1 wherein said inert inorganic salt is selected from alkali metal or airmonium chlorides or sulfates or mixtures thereof.
3. A composition according to claim 2 which contains 0 to 6% inert inorganic salt.
4. A composition according to claim 3 wherein said watersoluble, fiberreactive dyestuff has, in its free acid form, the formula (H0,S) F(30(_HCH<SO,H) wherein F is the chomophoric radical o m 2 ^ _z J n of a monoazo, disazo, anthraquinone, or phthalocyanine dyestuff, or a copper, nickel, chromium or cobalt metal complex thereof, m is an integer from 1 to 4 and n is an integer frαn 1 to 3.
5. A cαrposition according to claim 4 wherein m is 1 and n is 1. OMPI .
6. A composition according to claim 1 wherein said dyestuff, in its free acid form, has a formula selected from the group consisting of 0 0 (G) / \ R A N= NB N= N D wherein and wherein Rf is S02CH2CH2OS03H; R is independently selected frαn lower alkyl, lower alkoxy, brcmo, chloro, nitro, trifluorαmethyl, lower alkylamino, carboxy and sulfo; Ε is independently selected from amino, lower alkylamino, lower alkanoyl amino, benzoyl amino, and benzoyl amino substituted by chloro, brαπo, nitro, trifluoromεthyl, lower alkyl or lower alkoxy; R_ is independently selected from R and R.; 2, ; R. is lower alkyl, carboxy, lower alkoxy carbonyl, or carbamoyl; R, is H or OH; Me is Cu, Ni, Co, or Cr; m is independently 0, 1 or 2; n is independently 0, 1 or 2; p is independently 0 or 1; q is independently 0 or 1, provided that at least one q in a given structure is 1; and x and y are independently 1 or 2, and z is 0, 1 or 2, provided that x + y + z = 3 or 4.
7. The composition of claim 6 wherein Me is Cu.
8. A cαrposition according to claim 1 wherein said dyestuff, in its free acid form, has a formula selected frαn the group consisting of III HO '..SOCH.CHSO.' !© °> N (Claim 8 cαntd) VIII H03SOCH2CH2S (Claim 8 contd) 20 XEII _OMPI__ (Claim 8 contd) 21 * θY S02CH2CH20S03H XV R* H XVI R ■ OCH, XVIII Me « Cu y* z 2»o (Claim XXIII .
9. A composition according to claim 8 which contains 10 to 20% of said dyestuff, 0 to 6% of said inert inorganic salt, and 75 to 90% water.
10. A composition according to clain 8 which contains 30 to 40% of said dyestuff, 0 to 6% of said inert inorganic salt, and 5570% water.
11. A irethod of stablizing an aqueous, liquid fiberreactive dye composition against decomposition during storage, wherein said dye composition contains from 5 to 45% of a watersoluble, fiberreactive dyestuff having from 1 to 3 S02CH2CH2OS03H groups, which method comprises adjusting the pi of said dye composition to about 2.5 to about 4.5 and maintaining it at about 0 to 50° C.
12. A method of storing an aqueous, liquid fiberreactive dye composition for periods in excess of thirty days with iriinimum decomposition, wherein said dye ccrposition contains from 5 to 45%,of a water soluble, fiberreactive dyestuff having from 1 to 3 SC CRCHOSOH groups, which method comprises adjusting the pH of said dye composition to about 2.5 to about 4.5 and storing said composition at 0 to 50° C.
Description:
STABLE AQUEOUS LIζ?JID COMPOSITION OF REACTIVE DYES CONTAINING &-_ ^AT0-_T-βLSlI__P0NΪ GROUPS

The present invention relates to an aqueous, liquid fiber- reactive dye cαmpositicn which is stable to decomposition.

There are several patents which describe liquid reactive dye preparations. Most notably are U.S.4,072,463, U.S.4,078,884,

U.S.4,118,184 and U.S.4,149,850, which, in essence, describe aqueous preparations ccnt-iining 5.to 35% (45% in one instance) reactive dyestuff of the formula <HOj,S)m-F-Zn. where F is the dirαrrcp ^horic radical and Z is the fiber-reactive group, 1 to 5% (or 6%) buffer substances,_. and having a pH of 3 to 7. The preferred pH for the liquid preparations is stated to be 5.5 to 6.8 in each patent and most of the exaπples illustrate buffered liqui preparations having a pH in that range.

In U.S. 4,349,349 there is disclosed liquid preparations of C.I. Reactive Blue 19 which contain 10 to 50 parts dyestuff, 1 to 40 parts formaldehyde/naphthalene sulfonic acid condensation product, and 0.1 to 10 parts noniαnic surfactant. All the exaπples illustrate dye ccppositions adusted to pH 5.5 with the cαrpositiαn of Exaπple 1 also containing sodium acetate buffer.

Applicant has found that liquid preparations of reactive dyestuffs which contain the fiber-reactive group β-sulfatoethylsulfcsψl (-SO-CΗ j C-H-OSOJH) , when prepared according to the preferred conditions of the above-described patents, are subject to decαtpositica during long-term storage. That is, the 6-sulfatcethylsulfonyl group of said dyestuffs will decompose to the vinylsulfonyl form (-SO-CH^CH-). While the vinylsulfonyl form of the dyestuff is an active dye form and will react with the fiber, applicant has found it to be disadvantageous to have significant portions of the dyestuff in this form prior to the actual dyeing application.

Since the vinylsulfonyl form is much less soluble than the β-sulfatoethylsulfαnyl form, dyestuff may precipitate out of liquid concentrates as deccnpositiαn to the vinylsulfonyl form proceeds, thus reducing dyestuff (tinctorial) strength. This is particularly a problem where the dyestuff involved is a monosulfonic acid or where a highly concentrated dyestuff solution is desired. In either situation the liquid cαrposition may be very close to the saturation point and any shift to the less-soluble dyestuff form may not be tolerated.

Applicant has also found that liquid dyestuff preparations which, through decomposition, contain significant portions of dyestuff in the vinylsulfonyl form are undesirable with respect to subsequent dyeing operations. Such preparations may produce uneven dyeings or superficial surface dyeings due to premature fixing of the active vinylsulfonyl form onto the fiber. Also, excess alkali will remain uncσnsumed in the dyeing solution since there is less sulfate ester to be hydrolized than expected. This excess alkali can reverse the dyeing process through hydrolysis of the dyestuff-fiber band.

SUMMARY OF THE INVENTION

Applicant has discovered an aqueous, liquid fiber-reactive dye cαrrposition which is stable to decomposition. Applicant's composition consists essentially of 5 to 45% by weight of a water-soluble, fiber-reactiv dyestuff having frαn 1 to 3 3-sulfatoethylsulfonyl (-SO-CH-QI-OSO^) groups, or a mixture of such dyestuffs; 0 to 10% by weight of water-soluble inert inorganic salt; and 45 to 95% by weight of water. Said liquid dye cαrrposition must have a pH of about 2.5 to about 4.5 and must be substantially free of buffer substances. Applicant's liquid dye cαrposition may be stored for long periods of time, for exaπple, in excess of thirty days, at 0° to 50°C with substantially reduced decαrposition to the vinylsulfonyl dye form.

DESCRIPTION OF THE PKEF HRED __MBCPIME->7rS

ϋhe reactive dyes which may be utilized in the cαrpositiα of the present invention nay be any of those known in the art, provided that frαn 1 to 3 β-sulfatoethylsulfonyl groups are present. Such dyes are well-known and are described, for exanple, in U.S 4,072,463, U.S. 4,078,884, U.S. 4,088,441, U.S. 4,118,184, U.S. 4,149,850 and U.S. 4,271,072, the disclosures of which are incorporated herein by reference.

More particularly, suitable fiber-reactive dyestuffs may, in their free acid form, correspond to the formula (HO.S) m -F- S0 2 CH 2 CH2θS0 3 H) n wherein F is the chrcrnophoric radical of a mαnoazo, disazo, anthraquinαne or phtϊialocyanine dyestuff, or a copper, nickel, chrαnium or ccbalt metal cαπplex thereof, is an integer frαn 1 to 4, and n is an integer from 1 to 3. Of course, any of the water-soluble metal salts of these dyestuffs iray be utilized, particularly the lithium, sodium and potassium salts.

Fiber-reactive dyestuffs found to be especially useful in the composition of the present invention correspond to the following formulae (in their free acid form) :

(C) ■■• ψ (SO^J) .

Me / N

O O

/ \

CG) R f -A- N* N- B - N N- D wherein

<R>_. ( (SSOO^-H)--. R,

wherein

R f is -S0 2 CH 2 CH 2 OS0 3 H

R is independently selected from lower alkyl, lower alkoxy, brαno, chloro, nitro, trifluorαmethyl, lower alkylamino, carboxy and sulfo;

R, is independently selected frαn amino, lower alkylamino, lower alkanoyl amino, benzoyl amino, and benzoyl amino substituted by chloro, brcmo, nitro, trifluorαrethyl, lα^er alkyl or lower alkoxy;

R- is

3 is

R. is lower alkyl, carboxy, lower alkoxy carbonyl, or carbamoyl;

R_ is H or OH; b

Me is Cu, Ni, Co, or Cr;

m is independently 0, 1 or 2; n is independently 0, 1 or 2; p is independently 0 or 1; q is independently 0 or 1, provided that at least one q in a given structure is 1; and x and y are independently 1 or 2, and z is 0, 1 or 2, provided that x + y+ z = 3 or 4.

Dyestuffs which are most especially preferred for use in the present invention are those which in their f ee acid form have the following formulae:

VII

X HO D3,SSOOCCHH 2 , EE_2.SS0C 2 - θ r

.Cu

XEII HO.SOCHJCHJSO, 2> ,' "sTo fio ^ ^To1of

*Λ O > so ; .CH-C-l j OSO.B

XV R« H XVI R-OCH,

XVCII Me « Cu y«z z-o

XIX Me « Ni Y" 8 * * °

XX Hs-Cu y« l z" 1

XXIII

OMPI

The composition of the present invention is particularly advantageous for liquid preparations of fber-reactive dyestuffs which are πonosulfonic acids, that is dyestuffs of the formula (H0 3 S) -F-(SO-CH-CH j OSO-H) wherein F is as previously defined and m is 1, most particularly n also being 1. Such πonosulfonic acids have borderline solubility and partial decomposition to the less soluble vinylsulfonyl form could cause precipitation of the dyestuff. Applicant's composition avoids or substantially reduces the decαπposition of such dyestuffs so that they nay be kept in solution over long periods of time.

The cαrpositiσn of the present invention also finds particular advantage where highly concentrated liquid preparations are desired. For example, a liquid preparation containing 30 to 40% by weight of dyestuff may be close to the saturation point. In such a case partial decomposition to the less soluble vinylsulfonyl form could cause dyestuff precipitation. Applicant's composition, being more stable to such decomposition, may accordingly be stored safely for a long period of time.

The ccpositiαn of the present invention may contain from 0 to 10% water-soluble, inert inorganic salt. Preferably, it will contain no more than 6% of such salt. Typical of such salts are the alkali metal (lithium, sodium, potassium) or ai ioni n chlorides or sulfates or mixtures thereof.

The composition of the present invention may also optionally contain agents normally utilized to aid dyestuff solubility or subsequent processing. Typically, these may include caprolactam, surfactants, naphthalene sulfonic acid/formaldehyde condensation product, anthraquinone-2-sulfonic acid, etc.

The invention may be further illustrated by the following example in which the parts and percentages are be weight.

EXAMPIE

Aqueous liquid dyestuff compositions were tested for stability in the following manner. Aqueous solutions of the dyestuffs having the structural foπrulae previously identified as I toB were placed in a covered glass container, adjusted to an initial pi as indicated in the Table, and stored in an oven at 40 C. These aqueous dyestuff solutions ware made up to 25% standard dyestuff strength and contained about 14-18% dyestuff, 0 to 6% inorganic salt, and in seme instances (as indicated in the Table) 2 or 3% buffer (phosphate salts) . Each aqueous dyestuff saπple was analyzed for vinylsulfone content prior to the storage test and from time to time thereafter. The net increase in vinylsulfone content for various storage periods is shown in the Table. As can be seen frαn the Table, the liquid dyestuff cαrrpositiαns maintained at pi 4.5 or lower and containing no buffer showed dramatically less vinylsulfone foπratiαn during storage " than the corresponding compositions maintained at higher pi or containing buffer.

T BLE

Dyestuff Initial Buffer Vinylsulfone formation (final % minus initial %)

No. pH Content 7 days 14 days ' 28 days 35 days 56 days 105 days

I €.0 2% 6.0 9.0 10.0 10.5

4.5 2% 0.5 0.5 2.5 2.5

II 5.5 2% 14.5 . 17.0 .

4.5 2% 4.5 β 6.0 — — —

III 6.0 3% 16.5 >20 (ppt] > - -

6.0 0 9.5 - 13.0 - - _

4.5 3% 1.5 - 3.5 _

4.5 0 0.5 — 2.5

IV 6.0 0 3.3 4.6 6.6 8.9

4.5 0 0 0 0 0.3

JΕEXfi*

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