GB1563599A - Stable aqueous formulations of disperse dyes - Google Patents
Stable aqueous formulations of disperse dyes Download PDFInfo
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- GB1563599A GB1563599A GB5272976A GB5272976A GB1563599A GB 1563599 A GB1563599 A GB 1563599A GB 5272976 A GB5272976 A GB 5272976A GB 5272976 A GB5272976 A GB 5272976A GB 1563599 A GB1563599 A GB 1563599A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
- C09B67/0084—Dispersions of dyes
- C09B67/0085—Non common dispersing agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2618—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen
- C08G65/2621—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups
- C08G65/2624—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups containing aliphatic amine groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/334—Polymers modified by chemical after-treatment with organic compounds containing sulfur
- C08G65/3344—Polymers modified by chemical after-treatment with organic compounds containing sulfur containing oxygen in addition to sulfur
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/60—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing polyethers
- D06P1/607—Nitrogen-containing polyethers or their quaternary derivatives
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/60—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing polyethers
- D06P1/607—Nitrogen-containing polyethers or their quaternary derivatives
- D06P1/6076—Nitrogen-containing polyethers or their quaternary derivatives addition products of amines and alkylene oxides or oxiranes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/34—Material containing ester groups
- D06P3/36—Material containing ester groups using dispersed dyestuffs
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
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Description
(54) STABLE AQUEOUS FORMULATIONS OF DISPERSE DYES
(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 formulations of disperse dyes which are free-flowing and pourable, and to their use for dyeing synthetic fiber material.
The development and acceptance of short-cycle dyeing processes in recent years has substantially raised the standards required in respect of the finishing of disperse dyes. Cheese dyeing at from 120 to 1400C (referred to as high-temperature dyeing) makes particularly high demands in respect of the state of subdivision of the dyes and the stability of the disperse dyes in the dye liquor.
Hitherto, satisfactory level dyeings of cheeses, without a filtration effect on the dye, have only been achieved by using formulations containing lignin sulfonates.
Since the individual dyes differ substantially in properties such as particle size, particle size distribution, hydrophilic character, tendency to crystallize and solubility in water, the effect of lignin sulfonates is limited to some dyes.
A further disadvantage of the lignin sulfonates is that the impurities which they contain stain, for example, linear polyester fibers, which is objectionable particularly where light shades or brilliant hues are concerned.
Furthermore, lignin sulfonates may act as reducing agents under the dyeing conditions, thereby destroying sensitive azo dyes and giving a greater or lesser diminution of the dye yields.
Because of their adverse properties under high-temperature dyeing conditions, dispersing agents from the group of the condensation products of naphthalenesulfonic acid and formaldehyde, cresol or phenol and/or phenolsulfonic acids and formaldehyde, or their sulfomethylation products (FIAT
Report 1013, pages 1-3; German Laid-Open Applications DOS 2,032,926 and 2,301,638) cannot be used for such formulations.
The present invention seeks to provide stable aqueous finely divided formulations of disperse dyes which do not exhibit the adverse properties of the aqueous formulations of the prior art in cheese dyeing by the high-temperature process.
We have found that good results, especially level dyeings of cheeses without dye filtration by the high-temperature process, may be obtained by preparing the dye liquors from aqueous formulations of disperse dyes which comprise
(a) from 5 to 55 per cent by weight -- based on (a + c) - of one or more finely divided disperse dyes,
(b) from 10 to 200 per cent by weight, based on (a), of one or more watersoluble surfactants obtained by reacting (cur) a polyamine of the general formula
where R is linear or branched saturated alkylene of 2 to 12 carbon atoms, optionally interrupted by one or two oxygen atoms, R' is hydrogen, alkyl of I to 6 carbon atoms, hydroxyalkyl of 2 to 4 carbon atoms or cyclohexyl, n is a number from 1 to 5 and if n > I R and R' are identical or different from sub-unit to sub-unit, (ss) a diamine of the general formula
where X is methylenecyclopentylene, 1,3-phenylene or 1 ,4-phenylene or a group of the formula
where the rings A are benzene or cyclohexane rings each of which is unsubstituted or substituted by methyl, and R3 and R4 are hydrogen, methyl or ethyl, or the group
is a cyclohexane radical, and R2 is hydrogen or alkyl of 1 to 4 carbon atoms,
(y) polyethyleneimine or polypropyleneimine having a degree of polymerization of from 5 to 50 or (a) N,N-bis-(3 '-aminopropyl)-propylene- 1,3-diamine, with from 8 to 480 moles, preferably from 8 to 350 moles, of propylene oxide, butylene oxide or a mixture of these per mole of amine, and subsequently with sufficient ethylene oxide that the reaction product contains from 20 to 80 per cent by weight, based on the total molecular weight, of polyethylene oxide blocks, followed by reaction of the oxyalkylation product with from 0.16 to 1 mole of sulfur trioxide, chlorosulfonic acid or sulfopropionic anhydride per mole equivalent of hydroxyl group, and neutralization of the product, and
(c) from 45 to 95 per cent by weight (based on (a) + (c)) of water or of a mixture of water and one or more humectants.
If desired, the formulations according to the invention may contain one or more further additives conventionally used in aqueous dispersions.
The formulations according to the invention are dispersions of low viscosity which remain stable, and retain their low viscosity, both on extended storage at from 25 to 300C and on several days' storage at 600C. The finely divided state of the dye remains virtually unchanged on storage.
The new formulations are exceptionally suitable for dyeing textile material of synthetic fibers, especially of cellulose ester fibers and very particularly of linear polyester fibers or of mixtures of such fibers with cellulose fibers, at up to 1400C.
Using the novel dye formulations dyeing liquors are obtained in which the dye is in stable dispersion and does not flocculate at up to 140cC, even in the presence of conventionally used dyeing assistants.
Examples of suitable disperse dyes (a) are water-insoluble or sparingly watersoluble azo dyes, dyes from the quinophthalone series and their water-insoluble derivatives, anthraquinone dyes and dyes from other categories of compounds, which are sparingly water-soluble and are absorbed on synthetic fibers from aqueous liquors, or mixtures of such dyes.
The dispersing agents present in the novel formulations of the invention are water-soluble surfactants (b) which are obtained by reacting initially polyoxypropylated and/or polyoxybutylated and subsequently polyoxyethylated diamines and polyamines of the above type with sulfur trioxide, chlorosulfonic acid or sulfopropionic anhydride, followed by neutralization of the products. In the case of sulfur trioxide or chlorosulfonic acid, the corresponding half-esters of sulfuric acid are obtained, whilst in the case of sulfopropionic anhydride esters with a sulfonic acid group in the propionyl radical are obtained.
From 0.16 to I mole of sulfur trioxide, chlorosulfonic acid or sulfopropionic anhydride is employed per mole equivalent of free hydroxyl group in the oxyalkylation product. Since reaction products in which at least 50% of the free hydroxyl groups are esterified have a particularly high stabilizing action, preferred surfactants (b) are those obtained by reacting the oxyalkylation products with from 0.5 to I mole of chlorosulfonic acid, sulfur trioxide or sulfopropionic anhydride per mole equivalent of free hydroxyl group.
The reaction of the olyoxyalkylation products with sulfur trioxide, chlorosulfonic acid or sulfopropionic anhydride may be carried out by conventional methods. The reaction can be carried out without solvents, but preferably is carried out in the presence of an inert solvent, for example anhydrous dioxane, dimethylformamide or an aliphatic chlorohydrocarbons, e.g. chloroform, carbon tetrachloride or methylene chloride. The reaction with sulfur trioxide or chlorosulfonic acid as a rule takes place very rapidly even at from 0 to 25"C. The reaction with sulfopropionic anhydride is advantageously carried out at from 50 to 900 C, preferably from 60 to 800C. In general, the reactions have ended after from 0.5 to 5 hours.
The reaction mixture obtained may be introduced into an aqueous base in order to neutralize it, i.e. to produce the salts of the sulfuric acid half-esters or of the propionylsulfonic acids. Preferably per mole of chlorosulfonic acid or sulfopropionic anhydride employed, about 2 moles of base are employed, whilst in the case of sulfur trioxide about I mole of base is employed. Preferred bases are the alkali metal hydroxides, e.g. sodium hydroxide and/or potassium hydroxide, but also organic bases, e.g. aliphatic amines, or other bases which give water-soluble salts with the sulfuric acid half-ester or propionylsulfonic acids.During neutralization, the temperature should not exceed from 35 to 400 C. To isdlate the salts, the neutralization batch may be concentrated under reduced pressure, whereupon the organic solvent or solvents is distilled off first, followed by a part of the water. The residue is then advantageously brought to a given content of active compound (i.e. surfactant), for example by adding water.
The amount of component (b) required for optimum results depends on the one hand on the dye and the concentration of the dye in the formulation and on the other hand on the actual surfactant (b). The minimum amount of (b) is 10 per cent by weight, based on the dye (a). Preferably from 20 to 100 per cent by weight of (b), based on (a), are employed. In formulations having a low content of disperse dye, a somewhat greater amount of (b), based on (a), will in general be used than in formulations with a high dye content. In the case of dyes which are difficult to disperse, larger amounts of (b), e.g. from 60 to 100 or even to 200% by weight, based on (a), will in general be used. The use of larger amounts of (b) than 200% by weight offers no further advantages.
The polyoxyalkylation products required for the manufacture of the surfactants (b) are obtained by stepwise reaction of the amines (a), ('3), (V) and/or (6), first with from 8 to 480, preferably from 8 to 350, moles of propylene oxide or 1,2-butylene oxide per mole of amine and then with ethylene oxide. The amount oi ethylene oxide used in the reaction is chosen so that after the oxyethylation the product contains from 20 to 80, preferably from 40 to 70, per cent by weight of polyethylene oxide blocks. Oxyalkylation products which contain from 40 to 70 per cent by weight of polyethylene oxide blocks and from 29.7 to 59.8 per cent by weight of polypropylene oxide blocks, based on the oxyalkylation product, are preferred.
The molecular weight of the adducts are as a rule from 1,000 to 65,000, preferably from 5,000 to 25,000. Since particularly effective surfactants are obtained from reaction products of the amines which have this molecular weight are very particularly preferred.
Oxyalkylation products in which the content of polyoxyethylene oxide blocks is less than 20 or greater than 80 per cent by weight do not give surfactants which are effective for the purpose of the invention, i.e. a dye dispersion containing such surfactants (b) is no longer adequately stabilized under high-temperature dyeing conditions.
Preferred amines of the formula
are those where R5 is -CH2-CH2-., CH2)3- or
R is hydrogen, methyl, ethyl or A-hydroxyethyl and n' is 1, 2 or 3, and where, if n' > 1, the R5,s are identical or different.
Specific examples of amines of the formulae I and II are ethylenediamine, 1,2propylenediamine, 1 ,3-diaminopropane, 1 ,4-diaminobutane, 3methylaminopropylamine, 3-cyclohexylaminopropylamine, hexamethylenediamine, 2,5-dimethylhexane-2,5-diamine, 4,9-dioxadodecane- 1,1 2-diamine, octamethylene-l ,8-diamine, 6,6-dimethyl-4,8-dioxaundecane- 1,11 -diamine, bis-(3aminopropyl)-methylamine, diethylenetriamine, dipropylenetriamine, triethylenetetramine, tripropylenetetramine, tetraethylenepentamine, tetra propylenepetitamine, I ,2-bis-(3'-amino-propylamino)-ethane, N-(2'-aminoethyl) ethanolamine, dihexamethylenetriamine, 2-aminomethylcyclopentylamine, 1,1 -bis- (4'-aminophenyl)-cyclohexane, 4,4'-diaminodicyclohexylmethane, 3 ,3'-dimethyl- 4,4'-diaminodicyclohexylmethane, 2,2-bis-(4-aminocyclohexylpropane), 4,4'diaminodiphenylmethane, N,N'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'dimethyl-4,4'-diaminodiphenylmethane and m- and p-phenylenediamine.
The polyethyleneimines or polypropyleneimines (y) used are those having a degree of polymerization of from 5 to 50, preferably from 10 to 30. Preferred compounds (y) are polyethyleneimines with a degree of polymerization of from 5 to 50, preferably from 10 to 30. Amongst these, products with a degree of polymerization of from 10 to 20 are particularly preferred. These products are preferably oxypropylated and oxyethylated to provide the oxyalkylation product, which is reacted with sulfur trioxide, chlorosulfonic acid or sulfopropionic anhydride and neutralized to form the surfactant (b).
Preferred amines (at-(S) ) to use are ethylenediamine, diethylenetriamine, triethylenetetramine, propylene-I ,2-diamine, propylene-l ,3-diamine, dipropylenetetramine, N,N-bis-(3 '-aminopropyl)-propylene- 1,3-diamine, 4,4'diaminodiphenylmethane or a polyethyleneimine with a degree of polymerization of from 10 to 20, since the alkylene oxide adducts of these amines, especially those obtained by oxypropylation and subsequent oxyethylation, give particularly effective surfactants (b) when reacted wth sulfur trioxide, chlorosulfonic acid or sulfopropionic anhydride and neutralized.
The process for the manufacture of the polyoxyalkylation products is disclosed, for example, in U.S. Patent 2,979,528; alternatively, the products may be manufactured by a polyoxyalkylation process similar to that described in the said
U.S. Patent.
The formation of the alkylene oxide adducts is advantageously carried out in the presence of acid or, preferably, alkaline catalysts, in the presence or absence of solvents. Examples of suitable solvents are dioxane or dimethylformamide. The adduct formation is preferably carried out under pressure at from 110 to 1 500 C.
The disperse dye formulations of the invention may be produced by conventional methods, by dispersing or homogenizing the disperse dye (a) in the presence of the water-soluble surfactant (b) in an aqueous or aqueous/organic phase (c). The disperse dyes may be used in the form of a powder or preferably in the form of the press cake as obtained from the synthesis reaction.
Dispersion may be effected in conventional comminution equipment, e.g.
kneaders, ball mills, dispersers, sand mills, bead mills or attrition mills. The dispersion process is stopped when the dye has the desired state of subdivision. The latter is tested by means of the filter test or preferably by the centrifugal sedimentation test (Richter and Vescia, Melliand Textilberichte, 1965, No. 6, pages 622 et seq.).
During manufacture or after dispersion, humectants, e.g. ethylene glycol, diethylene glycol, propylene glycol and dipropylene glycol, and also assistants or adjuvants conventionally employed in dispersions, e.g. disinfectants, may be added.
The amount of assistants and adjuvants is from 0 to 5 per cent by weight, based on the formulation.
The Examples which follow illustrate the invention. Parts and percentages are by weight.
A. Manufacture of the water-soluble surfactants (b)
(I) The alkylene oxide adducts of the amines were prepared by conventional methods (U.S. Patent 2,979,528), by reaction with propylene oxide or butylene oxide, followed by reaction with ethylene oxide in the presence of basic compounds as catalysts.
Per mole of amine, from 8 to 350 moles of propylene oxide/butylene oxide are used, followed by sufficient ethylene oxide to give a reaction product containing from 20 to 80 per cent by weight, based on the total molecular weight, of ethylene oxide blocks. This product constitutes the adduct.
(2) The adduct is then converted to the water-soluble surfactant (b).
2.1. Half-esters of sulfuric acid:
I mole of adduct from (1) is dissolved in half its amount by weight of anhydrous dioxane. The solutioii is cooled to 100C and at from 10 to 150C the calculated amount of chlorosulfonic acid is added dropwise, whilst stirring, or the calculated amount of sulfur trioxide is passed in as a gas. After completion of the addition, the reaction mixture is stirred for a further hour at room temperature. It is then slowly introduced, at from 20 to 400 C, into 25 per cent strength sodium hydroxide solution, under conditions such that the pH of the neutralization solution is always greater than 7.5.
For the above reason, about 2 moles of sodium hydroxide solution are used per mole of chlorosulfonic acid when carrying out the esterification with the latter; in the case of sulfur trioxide, one mole per mole of sulfur trioxide suffices. The solvent and a part of the water are then distilled from the reaction mixture under reduced pressure at from 70 to 800C and the residue is brought to an active compound content of from 30 to 40%. Instead of dioxane, dimethylformamide, chloroform, methylene chloride or carbon tetrachloride may also be used, equally successfully, as the solvent.
2.2 Sulfopropionic acid ester
I mole of adduct from (1), in half its amount by weight of chloroform or carbon tetrachloride, is heated, with the calculated amount of sulfopropionic anhydride, to 600C under an inert gas atmosphere and is kept at from 60 to 800C for from 2 to 4 hours. After it has cooled to room temperature, the reaction mixture is neutralized as stated under 2.1. and the solvent and a part of the water are removed.
The water-soluble surfactants (b) produced are listed in the Tables which follow. They are characterized by the amine on which they are based, by the amount of propylene oxide or butylene oxide, and of ethylene oxide, used, per mole of amine, to form the adduct, by the proportion of ethylene oxide, which has undergone adduct formation, in the total molecular weight of the polyoxyalkylation product, and by the amount of chlorosulfonic acid, sulfur trioxide or sulfopropionic anhydride employed per mole of amine originally used. TABLE A
Chlorosulfonic acid/ sulfur trioxide
Propylene oxide Ethylene oxide Total Mole per Mole per mole
Mole/mole Proportion Proportion % molecular mole of equivalent
No.Amine base material of amine of MW+ of MW+ of MW+ weight adduct of OH 1 N,N-Bis-(3'-amino- 64 3,770 14,785 78.5 18,738 1 0.167 propyl)-propylene1,3-diamine 2 " " " " " " 3 0.5 3 " " " " " " 6 1.0 4 " " " " " " 4 0.667 5 " 81 4,815 11.575 70 16,578 1 0.167 6 " " " " " " 3 0.5 7 " " " " " " 6 1.0 8 " " " " " " 4 0.667 9 " 98 5.800 14,000 70 19,988 1 0.167 10 " " " " " " 3 0.5 11 " " " " " " 6 1.0 12 " " " " " " 4 0.667 13 " 108 6,380 17,340 72.5 23,908 1 0.166 14 " " " " " " 3 0.5 15 " " " " " " 6 1.0 16 " 47 2,784 7,000 70 9.972 6 1.0 17 " 88 5,220 6,600 54.7 12.008 6 1.0 18 " 105 6,194 6.402 50 12,784 6 1.0 19 " 101 5.974 4,796 43.7 10,958 6 1.0 20 " 68 4,013 7,801 65 12,002 6 1.0 21 " 106 6,264 17,336 72.8 23,788 4 0.667 22 " 106 6,264 20,504 76 26,956 6 1.0 23 " 303 17,890 42,350 70 60,428 6 1.0 24 Triethylenetetramine 59 3,526 14,520 80 18,192 6 1.0 25 " 84 4,960 11,730 70 16,836 6 1.0 26 Ethylenediamine 61 3,600 8,400 70 12,060 1 0.25 27 " " " " " " 4 1.0 28 " " " " " " 2 0.5 + MW = Total molecular weight.
TABLE A (continuation)
Chlorosulfonic acid/ sulfur trioxide
Propylene oxide Ethylene oxide Total Mole per Mole per mole
Mole/mole Proportion Proportion % molecular mole of equivalent
No. Amine base material of amine of MW+ of MW+ of MW+ weight of adduct of OH 29 Ethylenediamine 74 4,350 10,150 70 14,560 1 0.25 30 " " " " " " 4 1.0 31 " " " " " " 2 0.5 32 " 95 5,580 13,020 70 18,660 1 0.25 33 " " " " " 18,660 4 1.0 34 " 127 7,500 5,000 40 12,560 1 0.25 35 " " " " 40 12,560 4 1.0 36 " 56 3,300 2,200 40 5,560 4 1.0 37 " 76 4,500 3,000 40 7,560 4 1.0 38 " 84 4,980 3.320 40 8,360 4 1.0 39 " 186 10,815 3,625 25 14,500 4 1.0 40 Hexamethylenediamine 127 7,384 5,000 40 12,500 4 1.0 41 2-Aminomethylcyclopentylamine 127 " " " " 4 1.0 42 4,4'-Diaminodicyclohexylmethane 126 7,290 " " " 4 1.0 43 4,4'-diaminodiphenylmethane 126 7,302 " " " 4 1.0 44 Ethylenediamine 10 580 528 45 1,168 4 1.0 45 Polyethyleneimine degree of 102 5,916 13.992 70 19,950 4 0.33 polymerization 10 46 " " " " " " 8 0.66 47 " 205 11,890 8,008 40 19,941 4 0,33 48 " " " " " " 8 0.66 49 " 256 14,848 9,898 " 24,746 3 0.25 50 " " " " " " 8 0.66 51 Polyethyleneimine degree of 103 5,974 13,992 70 20,009 4 0.18 polymerization 20 52 " " " " " " 8 0.36 53 " 480 27,840 18,560 40 46,400 5 0.23 54 " " " " " " 8 0.36 55 " " " " " " 15 0.68 TABLE B
Sulfopropionic acid esters
Sulfopropionic anhydride
Propylene oxide Ethylene oxide Mole per Mole per mole
Mole/mole Proportion proportion Adduct mole equivalent
No.Amine base material of amine of MW+ of MW+ of MW+ MW+ of adduct of OH 101 N,N-Bis-(3'amino- 146 8,500 5,792 40 14,480 6 1.0 propyl)-propylene1,3-diamine 102 " " " " " " 4 0.667 103 " 120 7,000 7,188 50 14,376 6 1.0 104 " 120 " 3,080 30 10,268 6 1.0 105 Triethylenetetramine 103 6,000 2,634 30 8,780 6 1.0 106 112 6,500 4,430 40 11,076 4 0.667 107 diethylenetriamine 86 5,000 2,187 30 7,290 5 1.0 108 Ethylenediamine 86 " 3,373 40 8,433 4 1.0 109 " 86 " " 40 " 3 0.75 110 " 120 7,000 7,060 50 14,120 2 0.5 111 " 74 4,290 10,150 70 14,500 4 1.0 + Total molecular weight.
TABLE C
Sulfuric acid half-esters
Chlorosulfonic acid
Butylene oxide Ethylene oxide Mole per Mole per mole
Mole/mole Proportions Proportions % Total mole equivalent
No. Amine base material of amine of MW+ of MW+ of MW+ MW+ of adduct of OH 201 Ethylenediamine 30.4 2,190 5,250 70 7,500 4 1.0 202 " 103 7,440 5,000 40 12,500 4 1.0 203 " 59.6 4,290 10,150 70 14,500 4 1.0 204 Triethylenetetramine 28.6 2,062 5,250 70 7,500 6 1.0 205 N,N-Bis(3'-amino- 60 4,312 3,000 40 7,500 6 1.0 propyl)-propylene-1,3-diamine + Total moleculat weight.
B. Aqueous formulations of disperse dyes
EXAMPLES 1 TO 35.
20 parts of the dye
in the form of the aqueous press cake are milled with 10 parts of the surfactant shown in Table I and 60 parts of water until the particle size is less than 1 ,um. The milling time and milling equipment used are shown in Table I. A further 10 parts of the same surfactant are then added. The formulations contain the dye in a very finely divided form. The degree of fine division is shown in Table I in terms of the
Richter and Vescia centrifugal sedimentation value (Melliand Textilberichte 1965,
No. 6, pages 622 et seq.). The formulations are mobile and stable on storage.
Cheeses dyed with the formulations show level dyeing throughout, without dye filtration.
TABLE I state of
Example Surfactant Milling equipment Milling time subdivision +)
1 Table A No. 1 Ball mill 200 hours 4 10 25 61
2 3 ,, ,, 6 8 20 66
Stirred ball mill
3 7 (glass spheres) 24 hours 3 7 19 71
4 10 Attrition mill 30 hours 5 16 28 51
5 18 Sand mill 4 passes 2 10 29 59
6 19 Sand mill 4 passes 2 5 18 75
7 24 ,, ,, 2 5 31 62
8 25 ,, ,, 2 3 25 70
9 30 Sanilmill ,, 3 2 23 72
10 34 Bead mill 15 hours 14 16 31 39
11 35 ,, ,, 2 2 13 83
12 37 ,, " 1 6 22 71
13 38 ,, 4 8 24 64
14 39 ,, ,, 10 16 31 43
15 41 ,, ,, 8 13 26 53
16 42 " " 6 18 35 41
17 43 " " 9 14 21 56
18 44 " " 12 18 37 33
19 45 " " 7 17 25 51
20 46 " " 7 12 36 45
21 48 " " 9 17 25 49
22 49 " " 11 20 31 38
23 51 " " 8 15 24 53 24 53 " " 11 18 29 47 25 55 " " 6 10 17 67
26 Table B No.101 " " 9 19 27 45
27 103 " " 7 20 29 44
28 106 " " 11 15 31 43
+) Centrifugal sedimentation values determined by the method of Richter and Vescia,
Melliand Textilberichte 1965, pages 622 et seq.
TABLE I (continuation)
State of
Example Surfactant Milling equipment Milling time subdivision+)
29 Table B No.108 Bead mill 15 hours 8 11 14 67
30 111 ,, ,, 13 23 24 40
31 Table C No.201 ,, ,, 7 12 28 53 32 202 ,, ,, 11 18 21 50
33 203 ,, ,, 10 19 27 44
34 204 ,, ,, 9 17 25 49
35 205 ,, ,, 12 20 32 36 Centrifugal sedimentation values determined by the method of Richter and Vescia,
Melliand Textilberichte 1965, pages 622 et seq.
EXAMPLES 36 TO 37.
20 parts of the dye of the formula
in the form of the moist press cake are milled with 10 parts of one of the surfactants (dispersing agents) shown in Table II and 60 parts of water until the particle size is less than 1 m. The milling time and milling equipment used are shown in Table II.
A further 10 parts of the particular surfactant are added to the milled samples.
The dispersions obtained are mobile and storage-stable, and give level dyeings, without filtration, when used to dye cheeses of texturized polyester fibers.
The formulations obtained contain the dye in a very finely divided form, as may be seen from the centrifugal sedimentation values.
TABLE II State of
Example Surfactant Milling equipment Milling time subdivision+)
36 Table A No. 1 Sand mill 6 passes 5 14 30 51
37 4 ,, ,, 4 21 45 30
38 5 ,, ,, 1 8 24 67
39 9 Bead mill 30 hours 5 16 28 51
40 12 ,, ,, 11 24 30 35
41 13 ,, ,, 12 23 32 33
42 14 ,, ,, 10 25 31 34
43 21 ,, ,, 8 12 30 50
44 22 ,, ,, 9 13 31 47
45 25 ,, ,, 10 23 33 44
46 31 " " 8 15 34 43
47 36 " " 11 18 31 40
48 39 " " 12 19 24 45
49 40 " " 11 17 29 43
50 41 " " 9 21 30 40
51 43 " " 11 19 29 41
52 44 " " 12 22 35 31
53 47 " " 8 12 18 62
54 48 " " 9 13 21 57
55 50 " " 10 16 25 49
56 52 " " 11 18. 29 42
57 53 " " 10 17 21 52
58 54 " " 12 14 22 52
59 Table B No.102 " " 6 11 18 65
60 105 " " 9 14 23 54
61 107 " " 12 20 29 39
62 109 " " 11 16 31 42
63 110 " " 8 11 33 48
64 111 " " 7 10 26 57
+) Centrifugal sedimentation values determined by the method of Richter and Vescia,
Melliand Textilberichte 1965, pages 622 et seq.
TABLE II (continuation)
State of
Example Surfactant Milling equipment Milling time subdivision+)
65 Table C No. 202 Bead mill 30 hours 8 19 27 46
66 204 ,, ,, 8 17 24 51
67 205 ,, ,, 9 22 36 33
+) Centrifugal sedimentation values determined by the method of Richter and Vescia,
Melliand Textilberichte 1965, pages 622 et seq
EXAMPLES 68 TO 101.
25 parts of the dye of the formula
in the form of the aqueous press cake are milled with 15 parts of the surfactant shown in Table III, 10 parts of ethylene glycol and 50 parts of water until the dispersion contains the dye in a very finely divided form (with a particle size of less than l yam). The milling equipment, milling time and degree of fine division are shown in Table III.
The formulations obtained are mobile and storage-stable, and are very suitable for dyeing polyester fiber cheeses by the high temperature process.
TABLE III
State of
Example Surfactant Milling equipment Milling time subdivision +)
68 Table A No. 1 Sand mill 6 passes 4 15 30 51
69 6 ,, ,, 6 18 25 50
70 8 ,, ,, 5 13 35 47
71 15 ,, ,, 7 16 30 47
72 16 ,, ,, 3 11 41 45
73 17 ,, ,, 6 14 33 47
74 18 ,, ,, 5 17 34 44
Stirred ball mill
75 19 (glass spheres) 15 hours 8 18 38 36
76 20 ,, ,, 10 11 30 44
77 22 ,, ,, 11 18 33 38
78 23 ,, ,, 9 17 29 45
79 24 ,, ,, 10 19 31 40
80 25 ,, ,, 7 15 30 48
81 27 ,, ,, 9 19 32 40
82 30 Attrition mill 30 hours 10 18 35 37
83 33 ,, ,, 12 21 33 34
84 35 ,, ,, 9 20 35 36
85 37 " " 11 17 34 38
86 38 " " 10 21 31 38
- 87 39 Bead mill 15 hours 8 14 25 53
88 41 " " 9 19 27 45
89 44 " " 12 23 34 41
90 45 " " 7 15 26 52
91 46 " " 6 15 24 55
92 50 " " 5 12 29 54
93 53 " " 10 18 27 45
94 55 " " 6 11 22 61
95 Table B No.103 " " 8 20 31 41
96 104 " " 10 23 36 31
97 107 " " 9 19 32 40
98 111 " " 12 19 33 36
99 Table C No. 201 " " 10 17 25 48
100 203 " " 7 13 21 59
101 205 " " 8 19 30 43
+) Centrifugal sedimentation values determined by the method of Richter and Vescia.
Melliand Textilberichte 1965, pages 622 et seq.
WHAT WE CLAIM IS:
1. A stable aqueous disperse dye formulation comprising:
(a) from 5 to 55 per cent by weight - based on (a + c)-of one or more finely divided disperse dyes,
(b) from 10 to 200 per cent by weight, based on(a), of one or more watersoluble surfactants obtained by reacting (α) a polyamine of the general formula:
**WARNING** end of DESC field may overlap start of CLMS **.
Claims (14)
- **WARNING** start of CLMS field may overlap end of DESC **.TABLE III State of Example Surfactant Milling equipment Milling time subdivision +)68 Table A No. 1 Sand mill 6 passes 4 15 30 5169 6 ,, ,, 6 18 25 5070 8 ,, ,, 5 13 35 4771 15 ,, ,, 7 16 30 4772 16 ,, ,, 3 11 41 4573 17 ,, ,, 6 14 33 4774 18 ,, ,, 5 17 34 44 Stirred ball mill75 19 (glass spheres) 15 hours 8 18 38 3676 20 ,, ,, 10 11 30 4477 22 ,, ,, 11 18 33 3878 23 ,, ,, 9 17 29 4579 24 ,, ,, 10 19 31 4080 25 ,, ,, 7 15 30 4881 27 ,, ,, 9 19 32 4082 30 Attrition mill 30 hours 10 18 35 3783 33 ,, ,, 12 21 33 3484 35 ,, ,,9 20 35 3685 37 " " 11 17 34 3886 38 " " 10 21 31 38 - 87 39 Bead mill 15 hours 8 14 25 5388 41 " " 9 19 27 4589 44 " " 12 23 34 4190 45 " " 7 15 26 5291 46 " " 6 15 24 5592 50 " " 5 12 29 5493 53 " " 10 18 27 4594 55 " " 6 11 22 6195 Table B No.103 " " 8 20 31 4196 104 " " 10 23 36 3197 107 " " 9 19 32 4098 111 " " 12 19 33 3699 Table C No. 201 " " 10 17 25 48100 203 " " 7 13 21 59101 205 " " 8 19 30 43 +) Centrifugal sedimentation values determined by the method of Richter and Vescia.Melliand Textilberichte 1965, pages 622 et seq.WHAT WE CLAIM IS: 1. A stable aqueous disperse dye formulation comprising: (a) from 5 to 55 per cent by weight - based on (a + c)-of one or more finely divided disperse dyes, (b) from 10 to 200 per cent by weight, based on(a), of one or more watersoluble surfactants obtained by reacting (α) a polyamine of the general formula:where R is linear or branched saturated alkylene of 2 to 12 carbon atoms optionally interrupted by one or two oxygen atoms, R' is hydrogen, alkyl of 1 to 6 carbon atoms, hydroxyalkyl of 2 to 4 carbon atoms or cyclohexyl, n is a number from 1 to 5 and, if n > 1, R and R1 are identical or different from sub-unit to sub-unit, ('3) a diamine of the general formula:where X is methylenecyclopentylene, 1,3-phenylene or 1 ,4-phenylene or a group of the formula::where the rings A are benzene or cyclohexane rings, each of which is unsubstituted or substituted by methyl, and R3 and R4 are hydrogen, methyl or ethyl, or the groupis a cyclohexane radical, and R2 is hydrogen or alkyl of 1 to 4 carbon atoms (y) polyethyleneimine or polypropyleneimine having a degree of polymerization of from 5 to 50, or (a) N,N-bis-(3'-aminopropyl)-propylene-l,3-diamine, with from 8 to 480 moles of propylene oxide, butylene oxide or a mixture of these per mole of amine, and subsequently with sufficient ethylene oxide that the reaction product contains from 20 to 80 per cent by weight, based on the total molecular weight, of polyethylene oxide blocks, followed by reaction of the oxyalkylation product with from 0.16 to l mole of sulfur oxide, chlorosulfonic acid or sulfopropionic anhydride per mole equivalent of hydroxyl group, and neutralization of the product, and (c) from 45 to 95 per cent by weight (based on a + c) of water or of a mixture of water and one or more humectants.
- 2. A formulation as claimed in claim 1, wherein component (b) has been prepared by reaction with sulfur trioxide, chlorosulfonic acid or sulfopropionic anhydride of the oxyalkylation product obtained by oxypropylation or oxybutylation and subsequent oxyethylation of an amine of the formulain which R5 is -CH2-CH2-, CH2)3- orRss is hydrogen, methyl, ethyl, or p-hydroxy-ethyl and n' is 1, 2 or 3, provided that if n' is greater than 1, the R5,s are identical or different.
- 3. A formulation as claimed in claim 1, wherein component (b) has been prepared by oxypropylation and subsequent oxyethylation of polyethyleneimine or polypropyleneimine which has a degree of polymerization of from 10 to 30, followed by reaction with sulfur trioxide, chlorosulfonic acid or sulfopropionic anhydride and neutralization.
- 4. A formulation as claimed in any of claims 1 to 3, wherein from 8 to 350 moles of propylene oxide and/or butylene oxide per mole of amine are used for the oxypropylation and/or oxybutylation.
- 5. A formulation as claimed in any of claims 1 to 4, wherein component (b) is based on an oxyalkylation product which contains from 29.7 to 59.8 per cent by weight of polypropylene oxide blocks and from 40 to 70 per cent by weight of polyethylene oxide blocks, based on the total molecular weight of the oxyalkylation product.
- 6. A formulation as claimed in any of claims 1 to 5, wherein component (b) is prepared by reaction of from 0.5 to 1 mole of sulfur trioxide, chlorosulfonic acid or sulfopropionic anhydride per mole equivalent of hydroxyl group in the oxyalkylation product, followed by neutralization.
- 7. A formulation as claimed in any of claims 1 to 6, which contains from 20 to 100 per cent by weight of component (b), based on (a).
- 8. A formulation as claimed in any of claims 1 to 7, wherein component (b) is a sulfuric acid half-ester or sulfopropionic acid ester of an oxyalkylation product obtained by oxypropylation and subsequent oxyethylation of ethylenediamine, diethylenetriamine, triethylenetetramine, propylene- 1 ,2-diamine, propylene-1,3diamine, dipropylenetriamine, N,N-bis-(3 '-aminopropyl)-propylene- 1, 3-diamine, 4,4'-diaminodiphenylmethane or a polyethyleneimine with a degree of polymerization of from 10 to 20.
- 9. A formulation as claimed in any of claims 1 to 8, wherein component (a) is a disperse dye from the series of the azo dyes, the quinophthalone dyes or in the anthraquinone dyes, or is a mixture of such dyes.
- 10. A formulation as claimed in claim I and substantially as described in any of the foregoing Examples.
- 11. A process for the manufacture of an aqueous disperse dye formulation as claimed in any of claims 1 to 10 comprising dispersing one or more disperse dyes (a) in the presence of a dispersing agent in an aqueous or aqueous/organic phase (c), wherein the dispersing agent used is a water-soluble surfactant or surfactant mixture as defined under (b) in claim 1.
- 12. A process as claimed in claim 11 carried out substantially as described in any of the foregoing Examples.
- 13. An aqueous disperse dye formulation when obtained by a process as claimed in claim 10 or claim 12.
- 14. A process for dyeing textile materials containing synthetic fibers from an aqueous liquor, wherein an aqueous disperse dye formulation -as claimed in any of claims 1 to 10 and 13 is used to provide the dye liquor.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19752557563 DE2557563A1 (en) | 1975-12-20 | 1975-12-20 | DISPERSION-STABLE AQUATIC PREPARATIONS OF DISPERSION COLORS |
Publications (1)
Publication Number | Publication Date |
---|---|
GB1563599A true GB1563599A (en) | 1980-03-26 |
Family
ID=5964990
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB5272976A Expired GB1563599A (en) | 1975-12-20 | 1976-12-17 | Stable aqueous formulations of disperse dyes |
Country Status (6)
Country | Link |
---|---|
JP (1) | JPS5277274A (en) |
BE (1) | BE849440A (en) |
DE (1) | DE2557563A1 (en) |
FR (1) | FR2335571A1 (en) |
GB (1) | GB1563599A (en) |
IT (1) | IT1064329B (en) |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4548744A (en) * | 1983-07-22 | 1985-10-22 | Connor Daniel S | Ethoxylated amine oxides having clay soil removal/anti-redeposition properties useful in detergent compositions |
US4551506A (en) | 1982-12-23 | 1985-11-05 | The Procter & Gamble Company | Cationic polymers having clay soil removal/anti-redeposition properties useful in detergent compositions |
US4597898A (en) * | 1982-12-23 | 1986-07-01 | The Proctor & Gamble Company | Detergent compositions containing ethoxylated amines having clay soil removal/anti-redeposition properties |
US4659802A (en) | 1982-12-23 | 1987-04-21 | The Procter & Gamble Company | Cationic compounds having clay soil removal/anti-redeposition properties useful in detergent compositions |
US4661288A (en) | 1982-12-23 | 1987-04-28 | The Procter & Gamble Company | Zwitterionic compounds having clay soil removal/anti/redeposition properties useful in detergent compositions |
US4664848A (en) | 1982-12-23 | 1987-05-12 | The Procter & Gamble Company | Detergent compositions containing cationic compounds having clay soil removal/anti-redeposition properties |
US4676921A (en) * | 1982-12-23 | 1987-06-30 | The Procter & Gamble Company | Detergent compositions containing ethoxylated amine polymers having clay soil removal/anti-redeposition properties |
WO2021196103A1 (en) * | 2020-04-01 | 2021-10-07 | 南通纺织丝绸产业技术研究院 | Water-based nano disperse dye useful for softening finishing and use thereof |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2812307A1 (en) | 1978-03-21 | 1979-10-04 | Basf Ag | DISPERSION COLOR PREPARATIONS |
-
1975
- 1975-12-20 DE DE19752557563 patent/DE2557563A1/en active Pending
-
1976
- 1976-11-30 IT IT2996676A patent/IT1064329B/en active
- 1976-12-14 FR FR7637591A patent/FR2335571A1/en active Granted
- 1976-12-15 BE BE173290A patent/BE849440A/en unknown
- 1976-12-17 GB GB5272976A patent/GB1563599A/en not_active Expired
- 1976-12-17 JP JP15101876A patent/JPS5277274A/en active Pending
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4551506A (en) | 1982-12-23 | 1985-11-05 | The Procter & Gamble Company | Cationic polymers having clay soil removal/anti-redeposition properties useful in detergent compositions |
US4597898A (en) * | 1982-12-23 | 1986-07-01 | The Proctor & Gamble Company | Detergent compositions containing ethoxylated amines having clay soil removal/anti-redeposition properties |
US4659802A (en) | 1982-12-23 | 1987-04-21 | The Procter & Gamble Company | Cationic compounds having clay soil removal/anti-redeposition properties useful in detergent compositions |
US4661288A (en) | 1982-12-23 | 1987-04-28 | The Procter & Gamble Company | Zwitterionic compounds having clay soil removal/anti/redeposition properties useful in detergent compositions |
US4664848A (en) | 1982-12-23 | 1987-05-12 | The Procter & Gamble Company | Detergent compositions containing cationic compounds having clay soil removal/anti-redeposition properties |
US4676921A (en) * | 1982-12-23 | 1987-06-30 | The Procter & Gamble Company | Detergent compositions containing ethoxylated amine polymers having clay soil removal/anti-redeposition properties |
US4548744A (en) * | 1983-07-22 | 1985-10-22 | Connor Daniel S | Ethoxylated amine oxides having clay soil removal/anti-redeposition properties useful in detergent compositions |
WO2021196103A1 (en) * | 2020-04-01 | 2021-10-07 | 南通纺织丝绸产业技术研究院 | Water-based nano disperse dye useful for softening finishing and use thereof |
Also Published As
Publication number | Publication date |
---|---|
FR2335571B3 (en) | 1979-08-24 |
IT1064329B (en) | 1985-02-18 |
DE2557563A1 (en) | 1977-06-30 |
BE849440A (en) | 1977-06-15 |
FR2335571A1 (en) | 1977-07-15 |
JPS5277274A (en) | 1977-06-29 |
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