CA2044183A1 - Dispersants - Google Patents
DispersantsInfo
- Publication number
- CA2044183A1 CA2044183A1 CA002044183A CA2044183A CA2044183A1 CA 2044183 A1 CA2044183 A1 CA 2044183A1 CA 002044183 A CA002044183 A CA 002044183A CA 2044183 A CA2044183 A CA 2044183A CA 2044183 A1 CA2044183 A1 CA 2044183A1
- Authority
- CA
- Canada
- Prior art keywords
- dispersant
- acid
- weight
- parts
- aromatic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Abstract
O.Z. 0050/41661 Abstract of the Disclosures Dispersants of increased bioeliminability or biodegradability for use in dye and pigment preparations, as tanning aids, in plastics production and in crop protection formulations contain from 3 to 50% by weight of one or more aromatic or long-chain aliphatic carboxylic acids, salts thereof or anhydrides thereof or a mixture thereof.
Description
21~d~ 3 O.Z. 0050/41661 Dispersants The present invention relates to novel disper-sants of increased bioeliminability or biodegradability for use in dye and pigment preparations, as tanning aids, in plastic~ production and in crop protection formula-tions.
Disper~ants used for industrial purposes, in particular in dye preparations and in dyebaths, are frequently sulfo-containing organic compounds which, however, are only incompletely bioeliminable or bio-degradable. For this reason, the use of ~uch agents can pollute surface waters.
DE-C-l 137 005 discloses a process for preparing condensation products of ~- and ~-naphthalenesulfonic acids and methylnaphthalenesulfonic acids and the corresponding naphthalenedisulfonic acids with aldehydes.
The condensation is carried out at from 100 to 200C
under superatmospheric p~essure. The condensation pro-ducts thus obtainable are used as tanning assistants, as dispersants for dyes, and in papermaking for preventing resin problems.
JP-A-82-077 061 discloses dispersants for cement which are prepared by condensing formaldehyde with naphthalenesulfonic acid, phenolsulfonic acid and an aromatic carboxylic acid andJor salts thereof.
According to JP-A-83-084 160 a dispersant for cement is obtained by cocondensation of alkylnaphthalene-sulfonic acid and an aromatic compound such as naph-thalene, anthracene, benzene, toluene, phenol, benzoic acid or sulfonates thereof and humic acid with formal-dehyde.
JP-A-76-045 123 discloses the preparation of condensat~on products of sulfonated aromatic carboxylic acids or of mixtu~e~ of sulfonated aromatic carboxylic acids with naphthalene and formaldehyde. The condensation product~ thus obtainable are added to hydraulic cement mixtures to improve the processing of the latter.
Disper~ants used for industrial purposes, in particular in dye preparations and in dyebaths, are frequently sulfo-containing organic compounds which, however, are only incompletely bioeliminable or bio-degradable. For this reason, the use of ~uch agents can pollute surface waters.
DE-C-l 137 005 discloses a process for preparing condensation products of ~- and ~-naphthalenesulfonic acids and methylnaphthalenesulfonic acids and the corresponding naphthalenedisulfonic acids with aldehydes.
The condensation is carried out at from 100 to 200C
under superatmospheric p~essure. The condensation pro-ducts thus obtainable are used as tanning assistants, as dispersants for dyes, and in papermaking for preventing resin problems.
JP-A-82-077 061 discloses dispersants for cement which are prepared by condensing formaldehyde with naphthalenesulfonic acid, phenolsulfonic acid and an aromatic carboxylic acid andJor salts thereof.
According to JP-A-83-084 160 a dispersant for cement is obtained by cocondensation of alkylnaphthalene-sulfonic acid and an aromatic compound such as naph-thalene, anthracene, benzene, toluene, phenol, benzoic acid or sulfonates thereof and humic acid with formal-dehyde.
JP-A-76-045 123 discloses the preparation of condensat~on products of sulfonated aromatic carboxylic acids or of mixtu~e~ of sulfonated aromatic carboxylic acids with naphthalene and formaldehyde. The condensation product~ thus obtainable are added to hydraulic cement mixtures to improve the processing of the latter.
- 2 - O.Z. ooso/41~6~41 83 EP-A-0 380 778 discloses the preparation of condensates of arenesul~onic acids and formaldehyde by ~ulfonation of aryl compounds which are obtainable by thermal cracking of a naphthenic residue oil and frac-S tional distillation of the cracking products of the fraction obtained at from 100 to 120C under atmospheric pressure. The sulfonatLon of this aromatics fraction with oleum at from 120 to 160C in an amount of from 0.7 to 1.2 parts by weight of oleum, based on oleum having an S03 content of 24~ by weight, per part by weight of the aromatics fraction and the subsequent condensation of the arenesulfonic acids with formaldehyde are effected in a conventional manner. The condensation products are used as dispersants, in particular as disper~ants for prepar-ing dye preparation~.
Dye preparations and dyebaths customarily contain dispersants comprising ligninsulfonates, sulfonates of phenol-formaldehyde condensates or naphthalenesulfonic acid/formaldehyde condensate~.
Even if properly used, the products mentioned pass into the wastewater in which or from which they are only partly biodegradable or bioeliminable in water treatment plants.
It i8 an ob~ect of the present invention to make available dispersants for various industrial purposes, in particular for dye preparations and dyebathsl which, compared with existing di3persants, are highly eliminable or degradable and at the same time still have good dispersing properties.
We have found that this ob~ect is achieved by dispersants of increased bioeliminability or biodegrad-ability for use in dye and pigment products, as tanning aids, in plastics production and in crop protection formulations, which contain from 3 to 50% by weight, preferably from 5 to 30% by weight, of one or more aromatic or long-chain aliphatic carboxylic acids, salts thereof or anhydrides thereof or a mixture thereof.
2 ~ 3 - 3 - O.Z. OOS0/41661 Dispersants for the purposes of the present invention are in particular sulfo-containing dispersants.
More particularly, the present invention provides dispersants which contain A) from 50 to 97~ by weight, preferably from 70 to 95~
by weight, of one or more arenesulfonic acid-formaldehyde condensates, one or more sulfonates of phenol-formaldehyde condensates, one or more lignin-sulfonates or a mixture thereof, and B) from 3 to 50~ by weight, preferably from 5 to 30~ by weight, of one or more aromatic or long-chain aliphatic carboxylic acids, salts thereof or an-hydrides thereof or a mixture thereof, the addition of component B taking place before, during or after the sulfonation step or the condensation step in the preparation of component A.
The term sulfonation step is here also to be understood as meaning the sulfite digestion of lignin to give ligninsulfonates.
Dye preparations are solid or liquid dye formula-tions and also dyebaths.
The dispersants of the present invention are suitable in particular for use as dispersants for dye formulations and in dyebaths.
Preferred disper~ants are those based on conden-sates of arenesulfonic acids and formaldehyde, obtainable by (a) sulfonating aromatic compounds to arenesulfonic acids and (b) condensing the arenesulfonic acids with formal-dehyde, the sulfonation (a) or the condensation (b) or both steps being effected in the pr~sence of from 5 to 50, prefer-ably 6 to 42, % by weight, based on the aromatic com-pounds used in the sulfonation (a), of aryl-containing or long-chain alkyl-containing carboxylic acids, or salts or anhydrides thereof.
204~3 - 4 - O.Z. 0050/41661 The preparation of ~uch dispersants according to the present invention i~ known. E~sentially it take~
place in two steps. In step (a), aromatic compounds are sulfonated. Suitable aromatic compounds for this purpose are for example naphthalene and mixtures of aromatic compounds which contain at least 103 by weight of naph-thalene. Commercial mixtures of aromatics, in addition to naphthalene, contain for example benzene, substituted benzenes, alkylnaphthalenes, such as l-methylnaphthalene and 2-methylnaphthalene, anthracenes, biphenyl, indene, acenaphthene/substituted indene or substituted acenaphthene.
Preferably, the aromatic compounds used in step (a) for preparing these dispersants are those aromatic compound3 which are obtainable by thermal cracking of a naphthenic residue oil and fractionation of the cracking products. Naphthenic residue oils are obtained for example in the cracking of light gasoline. In DE-A-29 47 005 for example they are referred to as high-boiling aromatic hydrocarbon oils. The naphthenic residue oil is preferably thermally cracked at 1400-1700C. The cracking products are then sub~ected to a fractional distillation.
The fraction which passes over at atmospheric pressure (1013 mbar) and 100-120C is collected and used as the aromatic compound in the sulfonation. Such a fraction is customarily obtained as a byproduct in the known acety-lene oil quench process, cf. Ullmann's Encyclopedia of Industrial Chemistry, VCH Verlagsgesellschaft mbH, Weinheim, 1985, Volume 71, pages 107-112.
This aromatics fraction is a mixture of many aromatic substances whose structures and amounts can in practice not be determined in detail. The following arene compounds are the chief representatives of this aromatics fractions 2 ~
Dye preparations and dyebaths customarily contain dispersants comprising ligninsulfonates, sulfonates of phenol-formaldehyde condensates or naphthalenesulfonic acid/formaldehyde condensate~.
Even if properly used, the products mentioned pass into the wastewater in which or from which they are only partly biodegradable or bioeliminable in water treatment plants.
It i8 an ob~ect of the present invention to make available dispersants for various industrial purposes, in particular for dye preparations and dyebathsl which, compared with existing di3persants, are highly eliminable or degradable and at the same time still have good dispersing properties.
We have found that this ob~ect is achieved by dispersants of increased bioeliminability or biodegrad-ability for use in dye and pigment products, as tanning aids, in plastics production and in crop protection formulations, which contain from 3 to 50% by weight, preferably from 5 to 30% by weight, of one or more aromatic or long-chain aliphatic carboxylic acids, salts thereof or anhydrides thereof or a mixture thereof.
2 ~ 3 - 3 - O.Z. OOS0/41661 Dispersants for the purposes of the present invention are in particular sulfo-containing dispersants.
More particularly, the present invention provides dispersants which contain A) from 50 to 97~ by weight, preferably from 70 to 95~
by weight, of one or more arenesulfonic acid-formaldehyde condensates, one or more sulfonates of phenol-formaldehyde condensates, one or more lignin-sulfonates or a mixture thereof, and B) from 3 to 50~ by weight, preferably from 5 to 30~ by weight, of one or more aromatic or long-chain aliphatic carboxylic acids, salts thereof or an-hydrides thereof or a mixture thereof, the addition of component B taking place before, during or after the sulfonation step or the condensation step in the preparation of component A.
The term sulfonation step is here also to be understood as meaning the sulfite digestion of lignin to give ligninsulfonates.
Dye preparations are solid or liquid dye formula-tions and also dyebaths.
The dispersants of the present invention are suitable in particular for use as dispersants for dye formulations and in dyebaths.
Preferred disper~ants are those based on conden-sates of arenesulfonic acids and formaldehyde, obtainable by (a) sulfonating aromatic compounds to arenesulfonic acids and (b) condensing the arenesulfonic acids with formal-dehyde, the sulfonation (a) or the condensation (b) or both steps being effected in the pr~sence of from 5 to 50, prefer-ably 6 to 42, % by weight, based on the aromatic com-pounds used in the sulfonation (a), of aryl-containing or long-chain alkyl-containing carboxylic acids, or salts or anhydrides thereof.
204~3 - 4 - O.Z. 0050/41661 The preparation of ~uch dispersants according to the present invention i~ known. E~sentially it take~
place in two steps. In step (a), aromatic compounds are sulfonated. Suitable aromatic compounds for this purpose are for example naphthalene and mixtures of aromatic compounds which contain at least 103 by weight of naph-thalene. Commercial mixtures of aromatics, in addition to naphthalene, contain for example benzene, substituted benzenes, alkylnaphthalenes, such as l-methylnaphthalene and 2-methylnaphthalene, anthracenes, biphenyl, indene, acenaphthene/substituted indene or substituted acenaphthene.
Preferably, the aromatic compounds used in step (a) for preparing these dispersants are those aromatic compound3 which are obtainable by thermal cracking of a naphthenic residue oil and fractionation of the cracking products. Naphthenic residue oils are obtained for example in the cracking of light gasoline. In DE-A-29 47 005 for example they are referred to as high-boiling aromatic hydrocarbon oils. The naphthenic residue oil is preferably thermally cracked at 1400-1700C. The cracking products are then sub~ected to a fractional distillation.
The fraction which passes over at atmospheric pressure (1013 mbar) and 100-120C is collected and used as the aromatic compound in the sulfonation. Such a fraction is customarily obtained as a byproduct in the known acety-lene oil quench process, cf. Ullmann's Encyclopedia of Industrial Chemistry, VCH Verlagsgesellschaft mbH, Weinheim, 1985, Volume 71, pages 107-112.
This aromatics fraction is a mixture of many aromatic substances whose structures and amounts can in practice not be determined in detail. The following arene compounds are the chief representatives of this aromatics fractions 2 ~
- 5 - O.Z. 0050/41661 % by weight of aromatics fraction ~aphthalene 30-55 2-Methylnaphthalene 5-15 1-Methylnaphthalene 4-10 Indene 3-10 ~iphenyl 1- 5 Methylindene 1- 5 Acenaphthene 1- 4 ~
The aromatics fraction also contains as iden-tified constituents in amounts of from 0.1 to about 2% by weight the following arene compounds: fluorene, indane, methyl~tyrene, phenanthrene, methylindane, dimethylnaph-15thalene, ethylnaphthalene, xylenes, tetralin, styrene, methylethylbenzene, anthracene, fluoranthrene, pyrene, acetnaphthylene and toluene. The sulfonation i9 prefer-ably performed on an aromatics fraction containing from 40 to 45% by weight of naphthalene.
20The aromatic compound~ are sulfonated in step (a) with oleum at 120-160C, preferably at 135-145C. Higher temperatures require shorter reaction times than lower temperatures. For example, the sulfonation takes from 1.6 to 2.6 hours at 145C, while from 2.25 to 4 hours are 25required at 140C and from 3.25 to 6 hours at 135C.
The aromatic compound3 are sulfonated per part by weight with from 0.7 to l.S part3 by weight of oleum, based on a fuming sulfuric acid having an S03 content of 65% by weight. The sulfonation of the aromatic compounds 30may of course also be effected with concentrated ~ulfuric acid or with a sulfuric acid which ha~ an S03 content of for example from 10 to 60% by weight. The amount of oleum used in the sulfonation step (a) depends on the S03 content of the fuming sulfuric acid. If the above-3peci-35fied temperature range i8 maintained during the sulfona-tion and the above-described amounts of oleum are used, then the naphthalene, or the naphthalene-containing .
2~1g3 - 6 - O.Z. 0050/41661 mlxture of aromatic compounds, will contain sulfonation product~ which contain ~- and ~-naphthalenesulfonic acid in a ratio of from 20:1 to 1:8, preferably from 10:1 to 1:5.
The sulfonation itself and/or the subsequent condensation as per step (b) are performed in the pre-sence of carboxylic acids which contain an aromatic group or a long-chain aliphatic radical or in the presence of salts or anhydrides thereof, aromatic carboxylic acids and derivatives thereof being preferred.
Suitable exa~ples of these preferred compounds are naphthalenecarboxylic acid, naphthalic acid, tereph-thalic acid, isophthalic acid, benzoic acid, trimellitic acid, phenylacetic acid, phenoxyacetic acid, salicylic acid, p-hydroxybenzoic acid, diphenylacetic acid, m-hydroxybenzoic acid, benzenetetracarboxylic acid and anhydrides of acids, for example phthalic anhydride, trimellitic anhydride, benzene-l,2,4,5-tetracarboxylic dianhydride or naphthalic anhydride.
Suitable long-chain aliphatic carboxylic acids are in particular saturated or olefinically unsaturated, linear or branched aliphatic monocarboxylic acids of from 8 to 22, preferably from 8 to 18, carbon atoms of natural or synthetic origin, ie. for example higher fatty acids such as caprylic acid, capric acid, lauric acid, myri~tic acid, palmitic acid, stearic acid, oleic acid, linoleic acid or linolenic acid or synthetically prepared car-boxylic acids such as 2-ethylhexanoic acid, isononanoic acid and isotridecanoic acid.
It is also possible to use mixtures of anhy-drides, mixtures of carboxylic acids, mixtures of salts of suitable carboxylic acids and also mixtures of car-boxylic acids and anhydrides. Suitable salts of the stated carboxylic acids are the alkali metal, ammonium and alkaline earth metal salt~, which are obtainable for example by neutralizing these carboxylic acids with sodium hydroxide, potassium hydroxide, lithium hydroxide, 2 ~
The aromatics fraction also contains as iden-tified constituents in amounts of from 0.1 to about 2% by weight the following arene compounds: fluorene, indane, methyl~tyrene, phenanthrene, methylindane, dimethylnaph-15thalene, ethylnaphthalene, xylenes, tetralin, styrene, methylethylbenzene, anthracene, fluoranthrene, pyrene, acetnaphthylene and toluene. The sulfonation i9 prefer-ably performed on an aromatics fraction containing from 40 to 45% by weight of naphthalene.
20The aromatic compound~ are sulfonated in step (a) with oleum at 120-160C, preferably at 135-145C. Higher temperatures require shorter reaction times than lower temperatures. For example, the sulfonation takes from 1.6 to 2.6 hours at 145C, while from 2.25 to 4 hours are 25required at 140C and from 3.25 to 6 hours at 135C.
The aromatic compound3 are sulfonated per part by weight with from 0.7 to l.S part3 by weight of oleum, based on a fuming sulfuric acid having an S03 content of 65% by weight. The sulfonation of the aromatic compounds 30may of course also be effected with concentrated ~ulfuric acid or with a sulfuric acid which ha~ an S03 content of for example from 10 to 60% by weight. The amount of oleum used in the sulfonation step (a) depends on the S03 content of the fuming sulfuric acid. If the above-3peci-35fied temperature range i8 maintained during the sulfona-tion and the above-described amounts of oleum are used, then the naphthalene, or the naphthalene-containing .
2~1g3 - 6 - O.Z. 0050/41661 mlxture of aromatic compounds, will contain sulfonation product~ which contain ~- and ~-naphthalenesulfonic acid in a ratio of from 20:1 to 1:8, preferably from 10:1 to 1:5.
The sulfonation itself and/or the subsequent condensation as per step (b) are performed in the pre-sence of carboxylic acids which contain an aromatic group or a long-chain aliphatic radical or in the presence of salts or anhydrides thereof, aromatic carboxylic acids and derivatives thereof being preferred.
Suitable exa~ples of these preferred compounds are naphthalenecarboxylic acid, naphthalic acid, tereph-thalic acid, isophthalic acid, benzoic acid, trimellitic acid, phenylacetic acid, phenoxyacetic acid, salicylic acid, p-hydroxybenzoic acid, diphenylacetic acid, m-hydroxybenzoic acid, benzenetetracarboxylic acid and anhydrides of acids, for example phthalic anhydride, trimellitic anhydride, benzene-l,2,4,5-tetracarboxylic dianhydride or naphthalic anhydride.
Suitable long-chain aliphatic carboxylic acids are in particular saturated or olefinically unsaturated, linear or branched aliphatic monocarboxylic acids of from 8 to 22, preferably from 8 to 18, carbon atoms of natural or synthetic origin, ie. for example higher fatty acids such as caprylic acid, capric acid, lauric acid, myri~tic acid, palmitic acid, stearic acid, oleic acid, linoleic acid or linolenic acid or synthetically prepared car-boxylic acids such as 2-ethylhexanoic acid, isononanoic acid and isotridecanoic acid.
It is also possible to use mixtures of anhy-drides, mixtures of carboxylic acids, mixtures of salts of suitable carboxylic acids and also mixtures of car-boxylic acids and anhydrides. Suitable salts of the stated carboxylic acids are the alkali metal, ammonium and alkaline earth metal salt~, which are obtainable for example by neutralizing these carboxylic acids with sodium hydroxide, potassium hydroxide, lithium hydroxide, 2 ~
- 7 - O.Z. 0050/41661 sodium carbonate, magnesium carbonate, calcium oxide, calcium hydroxide, ammoni~ or alkanolamines, such a~
ethanolamine, diethanolamine or triethanolamine.
Particular preference i9 given to using sodium benzoate, sodium phenylacetate, sodium salicylate, sodium 4-hydroxybenzoate, sodium terephthalate, sodium 2-hydroxy-3-naphthalenecarboxylate, naphthalene-l-car-boxylic acid, phthalic anhydride and benzoic acid.
The aryl-containing or long-chain alkyl-containing carboxylic acids are used in amounts of from5 to 50, preferably from 6 to 42, in particular from 10 to 30, % by weight, based on the aromatic compounds used in the sulfonation (a). The abo~ementioned carboxylic acids and their salts or anhydrides may be added before, during or after the sulfonation step (a) or else in the course of the condensation as per step (b). It is simi-larly possible to add these compounds to modify the arenesulfonic acid/formaldehyde condensation products for both the sulfonation step (a) and the condensation step (b)-The sulfonated product mixtures are then con-densed with formaldehyde in a conventional manner. This may be done by starting directly from the sulfonation mixture, diluting it with water and condensing it by adding formaldehyde, for example within the temperature range from 90 to 105C. The condensation may of course also be carrisd out under superatmospheric pressure at 105-150C. The condensation reaction requires about 4-12, preferably 7-9, hours. The amount of formaldehyde required in the condensation per part by weight of aromatic compound used in the sulfonation (a) is about 0.05-0.20, preferably from 0.07 to 0.17, part by weight of formaldehyde (calculated at 100% strength). The formaldehyde is preferably used in the condensation as a 10-50% strength by weight aqueous solution.
After the condensation has ended, the reaction mixture is neutralized. This may be done with sodium .
2 ~
ethanolamine, diethanolamine or triethanolamine.
Particular preference i9 given to using sodium benzoate, sodium phenylacetate, sodium salicylate, sodium 4-hydroxybenzoate, sodium terephthalate, sodium 2-hydroxy-3-naphthalenecarboxylate, naphthalene-l-car-boxylic acid, phthalic anhydride and benzoic acid.
The aryl-containing or long-chain alkyl-containing carboxylic acids are used in amounts of from5 to 50, preferably from 6 to 42, in particular from 10 to 30, % by weight, based on the aromatic compounds used in the sulfonation (a). The abo~ementioned carboxylic acids and their salts or anhydrides may be added before, during or after the sulfonation step (a) or else in the course of the condensation as per step (b). It is simi-larly possible to add these compounds to modify the arenesulfonic acid/formaldehyde condensation products for both the sulfonation step (a) and the condensation step (b)-The sulfonated product mixtures are then con-densed with formaldehyde in a conventional manner. This may be done by starting directly from the sulfonation mixture, diluting it with water and condensing it by adding formaldehyde, for example within the temperature range from 90 to 105C. The condensation may of course also be carrisd out under superatmospheric pressure at 105-150C. The condensation reaction requires about 4-12, preferably 7-9, hours. The amount of formaldehyde required in the condensation per part by weight of aromatic compound used in the sulfonation (a) is about 0.05-0.20, preferably from 0.07 to 0.17, part by weight of formaldehyde (calculated at 100% strength). The formaldehyde is preferably used in the condensation as a 10-50% strength by weight aqueous solution.
After the condensation has ended, the reaction mixture is neutralized. This may be done with sodium .
2 ~
- 8 - O.Z. 0050/gl661 hydroxide, potas~ium hydroxide, calcium hydroxide, sodium carbonate or sodium bicarbonate. It is also possible to use an excess of the neutralizing agent and bring the pH
back down to the desired value by adding customary mineral acids such as sulfuric acid or the abovementioned aromatic or long-chain aliphatic carboxylic acids. The pH
of the aqueous solution which contains the condensate in solution is customarily ad~usted to 6-11. However, it is also possible to isolate the condensation product from the solution in a solid form by spray drying.
The arenesulfonic acid/formaldehyde condensation products preparable in the presence of aryl-containing or long-chain alkyl-containing carboxylic acids are readily soluble in water and are suitable, as are the other lS dispersants according to the invention, for use as dispersant~ in dye formulations and in textile dyeing dyebaths. Dyes which are formulated in water with the use of dispersants are those which are insoluble or only sparingly soluble in water, for example vat dyes, dis-perse dyes and water-insoluble or only sparingly water-soluble fluorescent whitening agents. Disperse dyes are for example water-insoluble or only sparingly water-soluble azo dyes, dyes of the class of the quinophtha-lones and their water-insoluble derivatives, anthra-quinone dyes and dyes of other classes which are sparing-ly soluble or insoluble in water and go on to synthetic fiber material such as linear polyesters from an aqueous bath. In dye formulations the dispersant according to the present invention is required in amounts of from 8 to 500, preferably from 25 to 400, parts by weight per 100 parts by weight of dye. If used as a dyeing assistant in dyebaths for dyeing textiles, the dispersants according to the pre~ent invention are conventionally employed in amounts of from O.S to S g/l, based on the dyebath. The dye formulations obtainable in this way have long shelf lives, permit satisfactory level package dyeings without dye deposits, and are highly degradable or at least 2i~ J~3 - 9 - O.Z. 0050/41661 eliminable.
Further preferred disper~ant~ are tho~e which a~e obtainable by subsequently mixing the aromatic or long-chain aliphatic carboxylic acidc B or salts and an-hydrides thereof into customary dispersants, in part-icular into compounds A. Thi~ mixing in takes place after the customary dispersant~ or the compounds A have been prepared.
It was to be expected that in mixtures of customary dispersants with readily bioeliminable or bio-degradable productq the bioeliminability or biodegrad-ability would increase. However, the measured values surprisingly exceed the calculated values by fr~m about 10 to about 30%. This shows that in these mixtures synergisms are at work in respect of bioeliminability and biodegradability which leave the dispersing properties virtually unchanged.
The ligninsulfonates used are in particular those sulfonates, especially the alkali metal salts, whose sulfo group content does not exceed 25~ by weight.
Particular preference is given to ligninsulfonates containing from 5 to 15% by weight of sulfo groups.
The arenesulfonic acid-formaldehyde condensates and sulfonates of phenol-formaldehyde condensates used are in particular those having a maximum sulfo group content of 40% by weight.
Suitable arenesulfonic acid-formaldehyde con-densates are based for example on naphthalene or on the abovementioned mixtures of aromatic compounds which contain at least 10~ by weight of naphthalene and which can be sulfonated to give arenesulfonic acid components.
Particular preference is given to condensates which are based on the above-described aromatics mixtures obtain-able by thermal cracking of a naphthenic residue oil and fractional distillation of the cracking products.
The naphthalenesulfonic acid components used here are in general iso~er mixtures in which the ratio of the - 10 - O.Z. 0050/41661 ~- to the ~-isomer is within the range from 20:1 to 1:8, in particular from lO:l to 1:5.
As aromatic or long-chain aliphatic carboxylic acidq B it is possible in principle to use the same compounds as mentioned above.
Particularly suitable carboxylic acids B here are for example naphthalenecarboxylic acids, hydroxynaphtha-lenecarboxylic acids, o-, m- and p-benzenedicarboxylic acid, o-, m- and p-hydroxybenzoic acid, benzoic acid, phenylacetic acid, diphenylacetic acid, benzenetricar-boxylic acids and benzenetetracarboxylic acids, also oleic acid and isononanoic acid.
These compounds are mixed in either a-q the free acid and/or as the salt andJor as the anhydride. Prefer-ence is given to using salt~ which can be obtained byneutralization with sodium hydroxide or potas3ium hydroxide solution, with ammonia or with alkanolammonium compounds.
The dispersants of the prèsent invention, in addition to customary dispersants or sulfo-containing compounds A and the aromatic carboxylic acid~ B, may further contain customary assistants C in an amount of up to about 5~ by weight, for example other dispersants, surfactants, defoamers, hydrotropes, standardizing agents, complexing agents or biocides.
The disper~ants of the present invention can further be used with good results in pigment prepara-tions. Such pigment preparations can then be used for example for coloring carpets, paper materials, crop protection agents, building materials, detergents or paintbox colors.
The dispersants of the present invention are also highly suitable for use as tanning aids, ie. aids used in the production of leathers and furs, for example as dispersants in the coloring of leathers and furs.
The dispersants of the present invention can also be used with great advantage in plastics production, for 2 0 ~ r3 ~ 11 ~ O~Z~ 0050/41661 example as dispersant~ or emulsifiers in latex production.
The di~persants of the present invention can also be used to good effect in crop protection formulations.
5Examples thereof are the use as dispersants or emulsi-fiers in powder or liquid formulations of herbicides, fungicides or insecticides.
The bioeliminability or biodegradability was determined by the Zahn-Wellens test (R. Zahn, H. Wellens, Chem. Zeitung 90 (1974), 228; OECD 302 B corresponds to DIN 38412, Part 25). This test makes use of an activated sludge which contains a mixture of various microorganisms and mineral nutrients. ~n aqueous solution of this activated sludge i8 kept together with an aqueous solu-15tion of the test substance substantially in the dark at a constant temperature of about 22C for a set period (up to 28 days) while being aerated. The decrease in the concentration of the test substance is determined by determining the chemical oxygen demand (COD) or the 20dissolved organic carbon (DOC). Good biodegradability or bioeliminability requires a COD or DOC value of > 70%;
cf. U. Pagga, Umweltschutz-Umweltanalytik 4 (1984), 9.
The arylcarboxyl-containing axenesulfonic acid/formaldehyde condensation products to be used 25according to the present invention are in general more than 55% and in particular more than 70% degradable or at least eliminable, while commercial naphthalenesulfonic acid/formaldehyde condensates are only 30% eliminable under the same conditions and ligninsulfonates only about 3033%.
EXAMPLES
In the Examples, the parts and percentages are by weight. The dispersantq were prepared using, unless otherwise stated, aryl compounds obtained by fractional 35distillation of the cracking products of a naphthenic residue oil in accordance with EP-A-0 380 778. Speci-fically, the fraction passing over at 100-120C under 2a~0~
- 12 - O.z. 0050/41661 atmospheric pressure (1013 mbar) was used. The thermal cracking of the naphthenlc residue oil was carried out at 1400-1700C.
Specifically the followLng substances were identified in the mixtures of aryl compounds obtained by fractional distillation of the cracking products:
Compound %
Naphthalene 44.60 2-Methylnaphthalene 10.00 l-Methylnaphthalene 6.20 Indene 7.40 Biphenyl 2.20 Methylindene 1.95 Acenaphthene 1.70 Fluorene 1.30 Indane 1.22 Phenanthrene 1.10 Methylindane 1.10 Dimethylnaphthalene 1.13 Ethylnaphthalene 0.82 p- and m-Xylene 0.80 Tetralin 0.80 Styrene 0.60 The eliminability of the disper~ant was deter-mined by the Zahn-Wellen~ test as per German Standard Specification DIN 38412, Part 25.
Dispersant 1 128 parts of the mixture of the above-described aryl compounds and 29 parts of phthalic anhydride were introduced into a heatable reaction vessel, equipped with stirrer, and heated to 60C with stirring. Then 107 parts of oleum containing 65% of S03 were added over 4 hours while ensuring that the temperature did not rise above 70C. After the oleum had been added, the reaction mixture was stirred at 60C for 4 hours and at 135C for 5 hours. It was then cooled back to 70C, 150 parts of water were added, followed by 50 parts of 30% strength - 13 - o.z. 0050/41661 aqueous formaldehyde, and the mixture was then conden~ed by heating at 100C for 8 hour~. Then 500 parts of water and 125 part~ of 50% strength aqueous ~odium hydroxide solution were added. The pH was found to be 11.2. The mixture was then ~tirred at 90C for one hour and admixed with 15 parts of 20~ strength aqueou~ sulfuric acid to ad~ust to pH 8.4.
The solution had a solids content of 27.1%.
In the sulfonated product the ratio of ~- to ~-naphthalenesulfonic acid was 2.3:1.
The condensation product was 72~ eliminable.Dispersant 2 The preparation of dispersant 1 was repeated, except that the 29 parts of phthalic anhydride were replaced by 52 parts of naphthalene-l-carboxylic acid.
The aqueous solution of the dispersant had a pH of 8.1 and a solids content of 28.1%. The ratio of ~- to ~-naphthalenesulfonic acid was 1.7:1. The bioelimin-ability/degradability of the spray-dried product was > 70~-Dispersant 3 The procedure used in the preparation of disper-sant 1 was repeated, except that instead of the 29 parts of phthalic anhydride 25 parts of benzoic acid were added to the mixture of the above-described aryl compounds. The ratio of ~- to ~-naphthalenesulfonic acids was 1.2:1. The aqueous solution of the dispersant had a solids content of 25.83. The bioeliminability~degradability of the spray-dried product in the Zahn-Wellen~ test wa~ 75~.
Dispersant 4 128 part~ of pure (96 - 98%~ naphthalene and 25 parts of benzoic acid were introduced into a vessel as described for dispersant 1 and heated to 90C with stirring. Then 107 parts of oleum containing 65~ of S03 were added over 2 hours while ensuring that the temper-ature did not rise above 95C. After the oleum had been added, the reaction mixture was heated to 140C and 2~4~ ~3 - 14 - o.Z. 0050/41661 stirred at that temperature for 3.5 hours. It was then cooled back to 80aC, 150 parts of water were added, followed by 50 parts of 30~ strength aqueous formal-dehyde, and the mixture was condensed at 100C for 8 hours.
Then 500 parts of water and 131 part~ of S0 strength aqueous sodium hydroxide solution were added.
The mixture was stirred at 90C and pH lO.S for one hour.
Then 365 part~ of water and 12 parts of 20% strength aqueous sulfuric acid were added to obtain a solution having a pH of 8.4 and a solids content of 20%. In the sulfonated product, the ratio of ~- to ~-naphthalene-sulfonic acid was 1:4.6.
The bioeliminability of the spray-dried product in the Zahn-Wellens test was 70%.
Dispersant 5 The procedure for dispersant 3 was repeated, except that the amount of oleum containing 65% of S03 used was increased from 107 parts to 115 parts.
The ratio of ~- to ~-naphthalenesulfonic acid was 1:1.5. The aqueous solution of the dispersant had a solids content of 25.6~. The condensation product was > 70~ eliminable.
Dispersant 6 The procedure used in the prepration of disper-sant 1 was repeated, except that instead of the 29 parts of phthalic anhydride 56 parts of oleic acid were added to the mixture of the above-described aryl compounds. The ratio of ~- to ~-naphthalenesulfonic acids was 2.01:1.
The aqueou~ solution of the dispersant had a pH of 8.2 and a solids content of 28.3%. The spray-dried product had a bioeliminability/degradability of 86%.
Dispersants 7 to 24 Dispersants 7 to 24 were prepared by subsequently mixing sodium salt~ of aromatic carboxylic acids into dispersant~ of a comparatively low bioeliminability or biodegradability. The starting dispersants used for this - 15 - O.Z. 0050/41661 purpose were as follows:
(I) the above-~escribed mixture used for the prepara-tion of dispersant 1 of aryl compounds obtained in the fractional distillation of the cracking products of a naphthenic residue oil;
(II) a commercial naphthalenesulfonic acid-formal-dehyde condensate having a sulfo group content of 30%, prepared by condensation of naphthalenesul-fonic acid (~- to ~-isomer ratio 1:4.5) with formaldehyde;
(III) commercial sodium ligninsulfonate having a sulfo group content of 7%;
(IV) commercial sodium ligninsulfonate having a sulfo group content of 14~;
(V) commercial sodium ligninsulfonate having a sulfo group content of 22%.
As sodium salts of aromatic carboxylic acids were used sodium benzoate, sodium 4-hydroxybenzoate, sodium phenylacetate, sodium salicylate and sodium terephtha-late. For this purpose the sodium salicylate and the sodium terephthalate were each prepared by neutralization of the free acids with sodium h~droxide solution to pH 9.5 and subsequent evaporation.
The following table shows the measured bioelimin-abilities/degradabilities EOLO f the prepared mixtures.
Example Dispersant Eo1O
No. ~%l Mixtures according to the present invention:
7 95% of I + 5% of sodium benzoate 70 8 85% of I + 15% of sodium benzoate 70 9 90% of I + 10~ of sodium phenylacetate 77 70% of I ~ 30% of sodium phenylacetate 81 11 90% of I + 10% of sodium salicylate 75 12 70% of I + 30% of sodium salicylate 75 13 90% of II + 10% of sodium benzoate 56 14 70% of II + 30% of sodium benzoate 65 70% of II + 30% of sodium 4-hydroxy-2 ~ J v - 16 -O.Z. 0050/41661 TABLE (continued) Example Di~per~ant EbiO
No. ~ %]
Mixtures according to the present invention:
S benzoate 57 16 90% of II + 10% of sodium phenylacetate 58 17 70~ of II + 30~ of sodium phenylacetate 73 18 90% of III + 10% of sodium benzoate 57 19 70% of III + 304 of sodium benzoate 60 70% of III + 30% of sodium 4-hydroxy-benzoate 74 21 90% of III + 10% of sodium terephthalate 68 22 70% of III ~ 30% of sodium terephthalate 74 23 70% of IV + 30% of sodium benzoate 59 24 70% of V + 30~ of sodium benzoate 63 For comparison:
100% of I 45 100% of II 30 100% of III 30 100% of IV 27 100% of V 14 100% of sodium benzoate 99 100% of sodium phenylacetate 99 100% of sodium salicylate 99 100~ of sodium 4-hydroxybenzoate 99 100% of sodium terephthalate 99 The measurements were carried out in accordance with OECD guideline~ 302 B (Zahn-Wellens test) at a sludge concentration of 1 g of dry matter/l and a test concentration of about 400 mg of COD/l.
Application examples The state of fine division in the dye prepara-tion~ was characterized by the centrifuge test of Richter and Vescia, Melliand Textilberichte 196S, 621-625 (No.6).
- 17 - O.Z. 0050/41661 The numerical values correspond to the ~ of dye which on centrifuging at lO00, 2000 and 4000 revolutions per minute sediments within S minutes (values 1-3) and which at the end still remains in dispersion (value 4).
Dye preparations which give a small sedimentation value and high fLnal value are particularly finely divided.
2~ parts of the blue disperse dye of C.I. number 11345 (calculated dry) in the form of the aqueous press cake was pasted up with 18 parts of the dispersant l, lO parts of sorbitol in the form of a 70% strength aqueous solution, 5 parts of propylene glycol, 1 part of a commercial aqueous ~iocide (1,2-benziso-thiazolin-3-one as a 9.5% strength solution in propylene glycol) and water to 100 parts by weight by means of a high-speed stirrer and ground in a stir~ed ball mill with glass ball~ until very finely divided. The pH was 8.5. The centrifuge test gaYe the following values: 2/3/23~72.
The dye preparation was liquid and storable and very highly suitable for dyeing polyester fibers and fabrics by any of the dyeing proce~ses widely used for this purpose. In particular, when dyeing polyester/cotton blend fabrics by the thermosol method the dye preparation showed a high cotton reserve. Dyed packages of textured polyester fiber were found to be free of dye deposits.
16 parts of the red disperse dye C.I. Disperse Red 167:1 (calculated dry) in the form of the water-moist press cake were pasted up with 16 parts of dispersant 2, 15 parts o~ glycerol, 1 part of the biocide mentioned in Example 25 and water to a total weight of 100 parts, adjusted to pH 7.5 and gro-~nd in a stirred ball mill 2 ~ ~
- 18 - O.Z. 0050/41661 until very finely divided. The centrifuge te~t gave the following v~lues: 5/7/19/69.
The dye preparation had the properties described under Example ~5.
40 parts of the red disperse dye C.I. Disperse Red 277 in the form of the water-moist press cake (calculated dry) were ad~usted with 60 parts of dispersant 3 and water to a solids content of 40%, pasted up and sand-milled until very finely divided. The centrifuge test gave the following values: 4t5/12/79.
The dispersion was spray-dried at a gas inlet temperature of 120C and diluted to the final color strength with 100 parts of dispersant ~. The resulting dye powder showed the state of fine division obtained in the wet-grinding stage.
~tirred into water, it produced a stable dyeing li~uor which did not give any dye deposits even under HT
dyeing conditions and was very highly suitable not only for dyeing textured polyester fiber packages but also for thermosoling polyester/cotton blend fabrics. In par-ticular, this preparation produced very little staining of cotton fibers. The disperse dye was very easy to wash off the cotton.
25 parts of Fluorescent Brightener 199 in the form of a water-moist press cake were pasted up with the dispersants mentioned in the Table, 15 parts of glycerol, 15 parts of triethanolamine and water to 100 parts total and bead-milled until very finely divided, as measured by the centrifuge test. The pH was 10.0-11.0 and stayad at that level during the grinding. The preparation obtained was liquid and stable. It was highly suitable for the fluorescent whitening of polyester fibers and fabrics by the HT and thermosol processes and did not give any unlevelness or dye deposits even on dyeing packages of 2 ~ 'J,i~
- 19 - O.Z. 0050/41661 textile polyester fiber.
Example Disper~ant Grinding time Fine division No. centrifuge value 28 4 16 h bead 10, 15, 36, 39 milling 291' 4 14 h bead 13, 17, 35, 35 milling "Instead af 15 parts of glycerol, 15 parts of a 2:1 mixture of glycerol/sorbitol were used.
40 parts of the dye of C.I. number 69825 in the form of the aqueous press cake were bead-milled with 40 parts of dispersant 2 and an amount of water required to adjust the dry content to 20-25% at pH lO-11 until very finely divided. The centrifuge value was 3/8/10/79.
After the grinding medium had been sieved off, a further 18 parts of dispersant 2 and 1 part of di-2-ethylhexyl sulfosuccinate and 1 part of di-C10-alkyldisulfonimide were stirred in, and the mixture was filtered at a dry content of about 25% through a 3 ~m filter plug and then spray-dried at an air inlet temperature of 130C.
The dye powder obtained was readily redispersible in water, had a long shelf life and was suitable for all conventional dyeing processe~.
23 parts of the dye of C.I. number 59825 in the form of the aqueous press cake were pasted up with 7 parts of dispersant 3, 15 parts of a 70% strength aqueous ~orbitol solution and 1 part of commercial biocide as described in Example 25 and water to 100% and bead-milled at pH 10-11 until very finely divided. The centrifuge value was 5/16/31/48.
The dye preparation obtained was liquid, had a long shelf life a,nd was suitable for all widely used dyeing processes.
_ 20 - O.Z. 0050/4~ 3 50 parts of textured polye~ter yarn on packages were dyed in 1000 part~ of an aqueous liquor containing 2 parts of the yellow disperse dye of Colour Index No.
547023, 1 part of the dispersant from Example 4 and 1 part by weight of 30% strength acetic acid. The pH of the liquor was 4.5. The dyeing was carried out in a closed dyeing apparatus with liquor recirculation by pumping the liquor through the package in alternating directions. The 10liquor was heated from 60 to 130C in the course of 30 minutes. It was maintained at 130C for 60 minutes, then cooled back to 90C and finally dropped. The textile material was then reduction cleared at 70C with a fresh liquor containing 0.5 g~l of caustic soda, 2 g/l of 15sodium dithionite and 0.5 g/l of a nonionic detergent (condensation product of 1 mol of oleylamine and 12 mol of ethylene oxide) for about 20 minutes and then rinsed once with hot and once with cold water. The result obtained was a level wash- and crock-fast yellow dyeing.
Example 32 was repeated, except that the dye used was 2 parts of the disperse dye of Colour Index No.
60756. The result obtained was a level, wash- and crock-fast red dyeing.
22 parts of the blue disperse dye C.I. Di~perse Blue 60 (calculated dry) in the form of the water-moist press cake were p~sted up with 12 parts of the dispersant of Exampla 20, 3010 parts of sorbitol in the form of a 70% strength aqueous solution, 1 part of a commercially available biocide (l~2-benzisothiazolin-3-one in the form of a 9.5% strength solution in propylene glycol) and 35water to 100 parts of total weight by means of a high-speed stirrer and milled in a stirred ball mill with ~lass media to obtain a state of fine division. The pH
'J 3 - 21 - O.Z. 0050/41661 was 8.7. Centrifuge test: 3/4/24/69.
The dye formulation obtained was thln-bodied and storable and was very highly suitable for dyeing yarn~
and fabrics made of polyester fibers by any conventional dyeing process. When packages of textured polyester fibers were dyed, completely level dyeings were obtained which were completely free of filtered-out dye deposits.
25 parts of the red disperse dye C.I. Disperse Red 91 (calculated dry) in the form of the water-moist press cake were pasted up with 11 parts of the dispersant of Example 22, 12 parts of sorbitol in the form of a 70% strength aqueous solution, 1 part of the biocide mentioned in Example 34 and water to 100 parts of total weight, adjusted to pH 8.5 and milled in a stirred ball mill until a satisfactory state of fine division was obtained.
Centrifuge test: 7/9/21/63.
The dye formulation obtained has the properties described under Example 34.
Similar results were obtained with the dispersant of Example 19.
40 parts of the red disperse dye C.I. Disperse Red 167:1 ~calculated dry), in the form of an aqueous press cake, were pasted up with 60 parts of the dispersant of Example 19 and : water to a suspension having a solids content of about 40%, brought to pH 7.5 with sulfuric acid (20% strength) and milled in a stirred ball mill until a satisfactory state of fine division was obtained.
Centrifuge test: 9/13/32/46.
The dispersion was dried in a spray dryer at a gas inlet temperature of 120C and reduced in a blender to the final color strength by addi~ion of 25 parts of the dispersant of Example 23.
~ J
- 22 - O.Z. 0050/41661 The dye powder obtained had the ~tate of fine division achieved in the wet milling ~tage. Stirring into water produced a stable dyeing liquor which had the good dyeing properties described in Example 34.
40 parts of the violet vat dye C.I. Vat Red 91 in the form of the water-moist press cake were pasted up with 60 parts of the dispersant of Example 23 and water to give a suspension having a solids content of 38%
and milled in a stirred ball mill until a satisfactory state of fine division was achieved.
Centrifuge te~t: 2/4/7/87.
After drying in a spray dryer at a gas inlet tempera~ure of 130C, 20 parts of the abovementioned dispersant were added to adjust to the final color strength.
The dye powder thus obtained had the state of fine division achieved in the wet milling stage. It had a long shelf life, was very readily dispersible in dyeing liquors and was highly suitable for dyeing cotton fibers by any conventional dyeing proces 23 parts of the vat dye Vat Green 1 (C.I. 59825) in the form of the aqueous press cake were pasted up with 10 parts of the dispersant of Example 11, 15 parts of a 70% strength aqueous sorbitol solution, 1 part of a commercial biocide (1,2-benzi~othiazolin-3-one in the form of a 9.5% strength solution in propylene glycol) and water to 100 parts of ~otal weight and bead-milled at pH 10-11 until a satisfactory state of fine division had been achieved. The centrifuge value was 4/14/29/53.
The dye formulation obtained was thin-bodied, storable and suitable for any conventional dyeing process.
40 parts of the vat dye Vat Blue 6 (C.I. 69825) - 23 - O.Z. 0050/~16~
in the form of the aqueous press cake were milled with 60 parts of the dispersant of Example 11 and the amount of water required to set a dry matter content of from 20 to 25% in a stirred ball mill at pH 10 and 11 until a satisfactory state of fine division had been achieved.
The centrifuge value was 5/10/12/73.
After milling, the dry matter content was ad-~usted to about 25~, 1 part of di-2-ethylhexyl sulfo-succinate and 1 part of di-C10-alkyldisulfonimide were added, and the suspension was filtered through 3 ~m filter plugs as often as required until it was speckle-free. This was followed by spray drying at an air inlet temperature of about 150C.
The dye powder obtained was readily dispersible in water, storable and suitable for any conventional dyeing process.
The same result as in Example 39 above was obtained when the dispersant of Example 11 W~8 replaced by the mixture of Example 12.
20 parts of the blue azo disperse dye C.I. 11345 (cal-culated dry) in the form of the water-moist press cake were pasted up with 18 parts of the dispersant of Example 6, 15 parts of sorbitol in the form of a 70~ strength aqueous solution, 1 part of a commercially available biocide, and water to 100 parts of total weight by means of a high-speed stirrer and milled in a stirred ball mill with glass media until a satisfactory state of fine division had been achieved. The pH was 8.3.
Centrifuge test: 3/3~18/76.
The dye formulation was thin-bodied and storable and was very highly suitable for dyeing polyester fibers and fabrics by any conventional dyeing process. The formulation was notable in particular for a high cotton 2 ~
- 24 - o.z. 00SO/41661 reserve in the dyeing of polyester/cotton blend fabric~
by the thermo~ol process. When packages of textured polyester fibers were d-yed, there were no filtered-out dye deposit~.
back down to the desired value by adding customary mineral acids such as sulfuric acid or the abovementioned aromatic or long-chain aliphatic carboxylic acids. The pH
of the aqueous solution which contains the condensate in solution is customarily ad~usted to 6-11. However, it is also possible to isolate the condensation product from the solution in a solid form by spray drying.
The arenesulfonic acid/formaldehyde condensation products preparable in the presence of aryl-containing or long-chain alkyl-containing carboxylic acids are readily soluble in water and are suitable, as are the other lS dispersants according to the invention, for use as dispersant~ in dye formulations and in textile dyeing dyebaths. Dyes which are formulated in water with the use of dispersants are those which are insoluble or only sparingly soluble in water, for example vat dyes, dis-perse dyes and water-insoluble or only sparingly water-soluble fluorescent whitening agents. Disperse dyes are for example water-insoluble or only sparingly water-soluble azo dyes, dyes of the class of the quinophtha-lones and their water-insoluble derivatives, anthra-quinone dyes and dyes of other classes which are sparing-ly soluble or insoluble in water and go on to synthetic fiber material such as linear polyesters from an aqueous bath. In dye formulations the dispersant according to the present invention is required in amounts of from 8 to 500, preferably from 25 to 400, parts by weight per 100 parts by weight of dye. If used as a dyeing assistant in dyebaths for dyeing textiles, the dispersants according to the pre~ent invention are conventionally employed in amounts of from O.S to S g/l, based on the dyebath. The dye formulations obtainable in this way have long shelf lives, permit satisfactory level package dyeings without dye deposits, and are highly degradable or at least 2i~ J~3 - 9 - O.Z. 0050/41661 eliminable.
Further preferred disper~ant~ are tho~e which a~e obtainable by subsequently mixing the aromatic or long-chain aliphatic carboxylic acidc B or salts and an-hydrides thereof into customary dispersants, in part-icular into compounds A. Thi~ mixing in takes place after the customary dispersant~ or the compounds A have been prepared.
It was to be expected that in mixtures of customary dispersants with readily bioeliminable or bio-degradable productq the bioeliminability or biodegrad-ability would increase. However, the measured values surprisingly exceed the calculated values by fr~m about 10 to about 30%. This shows that in these mixtures synergisms are at work in respect of bioeliminability and biodegradability which leave the dispersing properties virtually unchanged.
The ligninsulfonates used are in particular those sulfonates, especially the alkali metal salts, whose sulfo group content does not exceed 25~ by weight.
Particular preference is given to ligninsulfonates containing from 5 to 15% by weight of sulfo groups.
The arenesulfonic acid-formaldehyde condensates and sulfonates of phenol-formaldehyde condensates used are in particular those having a maximum sulfo group content of 40% by weight.
Suitable arenesulfonic acid-formaldehyde con-densates are based for example on naphthalene or on the abovementioned mixtures of aromatic compounds which contain at least 10~ by weight of naphthalene and which can be sulfonated to give arenesulfonic acid components.
Particular preference is given to condensates which are based on the above-described aromatics mixtures obtain-able by thermal cracking of a naphthenic residue oil and fractional distillation of the cracking products.
The naphthalenesulfonic acid components used here are in general iso~er mixtures in which the ratio of the - 10 - O.Z. 0050/41661 ~- to the ~-isomer is within the range from 20:1 to 1:8, in particular from lO:l to 1:5.
As aromatic or long-chain aliphatic carboxylic acidq B it is possible in principle to use the same compounds as mentioned above.
Particularly suitable carboxylic acids B here are for example naphthalenecarboxylic acids, hydroxynaphtha-lenecarboxylic acids, o-, m- and p-benzenedicarboxylic acid, o-, m- and p-hydroxybenzoic acid, benzoic acid, phenylacetic acid, diphenylacetic acid, benzenetricar-boxylic acids and benzenetetracarboxylic acids, also oleic acid and isononanoic acid.
These compounds are mixed in either a-q the free acid and/or as the salt andJor as the anhydride. Prefer-ence is given to using salt~ which can be obtained byneutralization with sodium hydroxide or potas3ium hydroxide solution, with ammonia or with alkanolammonium compounds.
The dispersants of the prèsent invention, in addition to customary dispersants or sulfo-containing compounds A and the aromatic carboxylic acid~ B, may further contain customary assistants C in an amount of up to about 5~ by weight, for example other dispersants, surfactants, defoamers, hydrotropes, standardizing agents, complexing agents or biocides.
The disper~ants of the present invention can further be used with good results in pigment prepara-tions. Such pigment preparations can then be used for example for coloring carpets, paper materials, crop protection agents, building materials, detergents or paintbox colors.
The dispersants of the present invention are also highly suitable for use as tanning aids, ie. aids used in the production of leathers and furs, for example as dispersants in the coloring of leathers and furs.
The dispersants of the present invention can also be used with great advantage in plastics production, for 2 0 ~ r3 ~ 11 ~ O~Z~ 0050/41661 example as dispersant~ or emulsifiers in latex production.
The di~persants of the present invention can also be used to good effect in crop protection formulations.
5Examples thereof are the use as dispersants or emulsi-fiers in powder or liquid formulations of herbicides, fungicides or insecticides.
The bioeliminability or biodegradability was determined by the Zahn-Wellens test (R. Zahn, H. Wellens, Chem. Zeitung 90 (1974), 228; OECD 302 B corresponds to DIN 38412, Part 25). This test makes use of an activated sludge which contains a mixture of various microorganisms and mineral nutrients. ~n aqueous solution of this activated sludge i8 kept together with an aqueous solu-15tion of the test substance substantially in the dark at a constant temperature of about 22C for a set period (up to 28 days) while being aerated. The decrease in the concentration of the test substance is determined by determining the chemical oxygen demand (COD) or the 20dissolved organic carbon (DOC). Good biodegradability or bioeliminability requires a COD or DOC value of > 70%;
cf. U. Pagga, Umweltschutz-Umweltanalytik 4 (1984), 9.
The arylcarboxyl-containing axenesulfonic acid/formaldehyde condensation products to be used 25according to the present invention are in general more than 55% and in particular more than 70% degradable or at least eliminable, while commercial naphthalenesulfonic acid/formaldehyde condensates are only 30% eliminable under the same conditions and ligninsulfonates only about 3033%.
EXAMPLES
In the Examples, the parts and percentages are by weight. The dispersantq were prepared using, unless otherwise stated, aryl compounds obtained by fractional 35distillation of the cracking products of a naphthenic residue oil in accordance with EP-A-0 380 778. Speci-fically, the fraction passing over at 100-120C under 2a~0~
- 12 - O.z. 0050/41661 atmospheric pressure (1013 mbar) was used. The thermal cracking of the naphthenlc residue oil was carried out at 1400-1700C.
Specifically the followLng substances were identified in the mixtures of aryl compounds obtained by fractional distillation of the cracking products:
Compound %
Naphthalene 44.60 2-Methylnaphthalene 10.00 l-Methylnaphthalene 6.20 Indene 7.40 Biphenyl 2.20 Methylindene 1.95 Acenaphthene 1.70 Fluorene 1.30 Indane 1.22 Phenanthrene 1.10 Methylindane 1.10 Dimethylnaphthalene 1.13 Ethylnaphthalene 0.82 p- and m-Xylene 0.80 Tetralin 0.80 Styrene 0.60 The eliminability of the disper~ant was deter-mined by the Zahn-Wellen~ test as per German Standard Specification DIN 38412, Part 25.
Dispersant 1 128 parts of the mixture of the above-described aryl compounds and 29 parts of phthalic anhydride were introduced into a heatable reaction vessel, equipped with stirrer, and heated to 60C with stirring. Then 107 parts of oleum containing 65% of S03 were added over 4 hours while ensuring that the temperature did not rise above 70C. After the oleum had been added, the reaction mixture was stirred at 60C for 4 hours and at 135C for 5 hours. It was then cooled back to 70C, 150 parts of water were added, followed by 50 parts of 30% strength - 13 - o.z. 0050/41661 aqueous formaldehyde, and the mixture was then conden~ed by heating at 100C for 8 hour~. Then 500 parts of water and 125 part~ of 50% strength aqueous ~odium hydroxide solution were added. The pH was found to be 11.2. The mixture was then ~tirred at 90C for one hour and admixed with 15 parts of 20~ strength aqueou~ sulfuric acid to ad~ust to pH 8.4.
The solution had a solids content of 27.1%.
In the sulfonated product the ratio of ~- to ~-naphthalenesulfonic acid was 2.3:1.
The condensation product was 72~ eliminable.Dispersant 2 The preparation of dispersant 1 was repeated, except that the 29 parts of phthalic anhydride were replaced by 52 parts of naphthalene-l-carboxylic acid.
The aqueous solution of the dispersant had a pH of 8.1 and a solids content of 28.1%. The ratio of ~- to ~-naphthalenesulfonic acid was 1.7:1. The bioelimin-ability/degradability of the spray-dried product was > 70~-Dispersant 3 The procedure used in the preparation of disper-sant 1 was repeated, except that instead of the 29 parts of phthalic anhydride 25 parts of benzoic acid were added to the mixture of the above-described aryl compounds. The ratio of ~- to ~-naphthalenesulfonic acids was 1.2:1. The aqueous solution of the dispersant had a solids content of 25.83. The bioeliminability~degradability of the spray-dried product in the Zahn-Wellen~ test wa~ 75~.
Dispersant 4 128 part~ of pure (96 - 98%~ naphthalene and 25 parts of benzoic acid were introduced into a vessel as described for dispersant 1 and heated to 90C with stirring. Then 107 parts of oleum containing 65~ of S03 were added over 2 hours while ensuring that the temper-ature did not rise above 95C. After the oleum had been added, the reaction mixture was heated to 140C and 2~4~ ~3 - 14 - o.Z. 0050/41661 stirred at that temperature for 3.5 hours. It was then cooled back to 80aC, 150 parts of water were added, followed by 50 parts of 30~ strength aqueous formal-dehyde, and the mixture was condensed at 100C for 8 hours.
Then 500 parts of water and 131 part~ of S0 strength aqueous sodium hydroxide solution were added.
The mixture was stirred at 90C and pH lO.S for one hour.
Then 365 part~ of water and 12 parts of 20% strength aqueous sulfuric acid were added to obtain a solution having a pH of 8.4 and a solids content of 20%. In the sulfonated product, the ratio of ~- to ~-naphthalene-sulfonic acid was 1:4.6.
The bioeliminability of the spray-dried product in the Zahn-Wellens test was 70%.
Dispersant 5 The procedure for dispersant 3 was repeated, except that the amount of oleum containing 65% of S03 used was increased from 107 parts to 115 parts.
The ratio of ~- to ~-naphthalenesulfonic acid was 1:1.5. The aqueous solution of the dispersant had a solids content of 25.6~. The condensation product was > 70~ eliminable.
Dispersant 6 The procedure used in the prepration of disper-sant 1 was repeated, except that instead of the 29 parts of phthalic anhydride 56 parts of oleic acid were added to the mixture of the above-described aryl compounds. The ratio of ~- to ~-naphthalenesulfonic acids was 2.01:1.
The aqueou~ solution of the dispersant had a pH of 8.2 and a solids content of 28.3%. The spray-dried product had a bioeliminability/degradability of 86%.
Dispersants 7 to 24 Dispersants 7 to 24 were prepared by subsequently mixing sodium salt~ of aromatic carboxylic acids into dispersant~ of a comparatively low bioeliminability or biodegradability. The starting dispersants used for this - 15 - O.Z. 0050/41661 purpose were as follows:
(I) the above-~escribed mixture used for the prepara-tion of dispersant 1 of aryl compounds obtained in the fractional distillation of the cracking products of a naphthenic residue oil;
(II) a commercial naphthalenesulfonic acid-formal-dehyde condensate having a sulfo group content of 30%, prepared by condensation of naphthalenesul-fonic acid (~- to ~-isomer ratio 1:4.5) with formaldehyde;
(III) commercial sodium ligninsulfonate having a sulfo group content of 7%;
(IV) commercial sodium ligninsulfonate having a sulfo group content of 14~;
(V) commercial sodium ligninsulfonate having a sulfo group content of 22%.
As sodium salts of aromatic carboxylic acids were used sodium benzoate, sodium 4-hydroxybenzoate, sodium phenylacetate, sodium salicylate and sodium terephtha-late. For this purpose the sodium salicylate and the sodium terephthalate were each prepared by neutralization of the free acids with sodium h~droxide solution to pH 9.5 and subsequent evaporation.
The following table shows the measured bioelimin-abilities/degradabilities EOLO f the prepared mixtures.
Example Dispersant Eo1O
No. ~%l Mixtures according to the present invention:
7 95% of I + 5% of sodium benzoate 70 8 85% of I + 15% of sodium benzoate 70 9 90% of I + 10~ of sodium phenylacetate 77 70% of I ~ 30% of sodium phenylacetate 81 11 90% of I + 10% of sodium salicylate 75 12 70% of I + 30% of sodium salicylate 75 13 90% of II + 10% of sodium benzoate 56 14 70% of II + 30% of sodium benzoate 65 70% of II + 30% of sodium 4-hydroxy-2 ~ J v - 16 -O.Z. 0050/41661 TABLE (continued) Example Di~per~ant EbiO
No. ~ %]
Mixtures according to the present invention:
S benzoate 57 16 90% of II + 10% of sodium phenylacetate 58 17 70~ of II + 30~ of sodium phenylacetate 73 18 90% of III + 10% of sodium benzoate 57 19 70% of III + 304 of sodium benzoate 60 70% of III + 30% of sodium 4-hydroxy-benzoate 74 21 90% of III + 10% of sodium terephthalate 68 22 70% of III ~ 30% of sodium terephthalate 74 23 70% of IV + 30% of sodium benzoate 59 24 70% of V + 30~ of sodium benzoate 63 For comparison:
100% of I 45 100% of II 30 100% of III 30 100% of IV 27 100% of V 14 100% of sodium benzoate 99 100% of sodium phenylacetate 99 100% of sodium salicylate 99 100~ of sodium 4-hydroxybenzoate 99 100% of sodium terephthalate 99 The measurements were carried out in accordance with OECD guideline~ 302 B (Zahn-Wellens test) at a sludge concentration of 1 g of dry matter/l and a test concentration of about 400 mg of COD/l.
Application examples The state of fine division in the dye prepara-tion~ was characterized by the centrifuge test of Richter and Vescia, Melliand Textilberichte 196S, 621-625 (No.6).
- 17 - O.Z. 0050/41661 The numerical values correspond to the ~ of dye which on centrifuging at lO00, 2000 and 4000 revolutions per minute sediments within S minutes (values 1-3) and which at the end still remains in dispersion (value 4).
Dye preparations which give a small sedimentation value and high fLnal value are particularly finely divided.
2~ parts of the blue disperse dye of C.I. number 11345 (calculated dry) in the form of the aqueous press cake was pasted up with 18 parts of the dispersant l, lO parts of sorbitol in the form of a 70% strength aqueous solution, 5 parts of propylene glycol, 1 part of a commercial aqueous ~iocide (1,2-benziso-thiazolin-3-one as a 9.5% strength solution in propylene glycol) and water to 100 parts by weight by means of a high-speed stirrer and ground in a stir~ed ball mill with glass ball~ until very finely divided. The pH was 8.5. The centrifuge test gaYe the following values: 2/3/23~72.
The dye preparation was liquid and storable and very highly suitable for dyeing polyester fibers and fabrics by any of the dyeing proce~ses widely used for this purpose. In particular, when dyeing polyester/cotton blend fabrics by the thermosol method the dye preparation showed a high cotton reserve. Dyed packages of textured polyester fiber were found to be free of dye deposits.
16 parts of the red disperse dye C.I. Disperse Red 167:1 (calculated dry) in the form of the water-moist press cake were pasted up with 16 parts of dispersant 2, 15 parts o~ glycerol, 1 part of the biocide mentioned in Example 25 and water to a total weight of 100 parts, adjusted to pH 7.5 and gro-~nd in a stirred ball mill 2 ~ ~
- 18 - O.Z. 0050/41661 until very finely divided. The centrifuge te~t gave the following v~lues: 5/7/19/69.
The dye preparation had the properties described under Example ~5.
40 parts of the red disperse dye C.I. Disperse Red 277 in the form of the water-moist press cake (calculated dry) were ad~usted with 60 parts of dispersant 3 and water to a solids content of 40%, pasted up and sand-milled until very finely divided. The centrifuge test gave the following values: 4t5/12/79.
The dispersion was spray-dried at a gas inlet temperature of 120C and diluted to the final color strength with 100 parts of dispersant ~. The resulting dye powder showed the state of fine division obtained in the wet-grinding stage.
~tirred into water, it produced a stable dyeing li~uor which did not give any dye deposits even under HT
dyeing conditions and was very highly suitable not only for dyeing textured polyester fiber packages but also for thermosoling polyester/cotton blend fabrics. In par-ticular, this preparation produced very little staining of cotton fibers. The disperse dye was very easy to wash off the cotton.
25 parts of Fluorescent Brightener 199 in the form of a water-moist press cake were pasted up with the dispersants mentioned in the Table, 15 parts of glycerol, 15 parts of triethanolamine and water to 100 parts total and bead-milled until very finely divided, as measured by the centrifuge test. The pH was 10.0-11.0 and stayad at that level during the grinding. The preparation obtained was liquid and stable. It was highly suitable for the fluorescent whitening of polyester fibers and fabrics by the HT and thermosol processes and did not give any unlevelness or dye deposits even on dyeing packages of 2 ~ 'J,i~
- 19 - O.Z. 0050/41661 textile polyester fiber.
Example Disper~ant Grinding time Fine division No. centrifuge value 28 4 16 h bead 10, 15, 36, 39 milling 291' 4 14 h bead 13, 17, 35, 35 milling "Instead af 15 parts of glycerol, 15 parts of a 2:1 mixture of glycerol/sorbitol were used.
40 parts of the dye of C.I. number 69825 in the form of the aqueous press cake were bead-milled with 40 parts of dispersant 2 and an amount of water required to adjust the dry content to 20-25% at pH lO-11 until very finely divided. The centrifuge value was 3/8/10/79.
After the grinding medium had been sieved off, a further 18 parts of dispersant 2 and 1 part of di-2-ethylhexyl sulfosuccinate and 1 part of di-C10-alkyldisulfonimide were stirred in, and the mixture was filtered at a dry content of about 25% through a 3 ~m filter plug and then spray-dried at an air inlet temperature of 130C.
The dye powder obtained was readily redispersible in water, had a long shelf life and was suitable for all conventional dyeing processe~.
23 parts of the dye of C.I. number 59825 in the form of the aqueous press cake were pasted up with 7 parts of dispersant 3, 15 parts of a 70% strength aqueous ~orbitol solution and 1 part of commercial biocide as described in Example 25 and water to 100% and bead-milled at pH 10-11 until very finely divided. The centrifuge value was 5/16/31/48.
The dye preparation obtained was liquid, had a long shelf life a,nd was suitable for all widely used dyeing processes.
_ 20 - O.Z. 0050/4~ 3 50 parts of textured polye~ter yarn on packages were dyed in 1000 part~ of an aqueous liquor containing 2 parts of the yellow disperse dye of Colour Index No.
547023, 1 part of the dispersant from Example 4 and 1 part by weight of 30% strength acetic acid. The pH of the liquor was 4.5. The dyeing was carried out in a closed dyeing apparatus with liquor recirculation by pumping the liquor through the package in alternating directions. The 10liquor was heated from 60 to 130C in the course of 30 minutes. It was maintained at 130C for 60 minutes, then cooled back to 90C and finally dropped. The textile material was then reduction cleared at 70C with a fresh liquor containing 0.5 g~l of caustic soda, 2 g/l of 15sodium dithionite and 0.5 g/l of a nonionic detergent (condensation product of 1 mol of oleylamine and 12 mol of ethylene oxide) for about 20 minutes and then rinsed once with hot and once with cold water. The result obtained was a level wash- and crock-fast yellow dyeing.
Example 32 was repeated, except that the dye used was 2 parts of the disperse dye of Colour Index No.
60756. The result obtained was a level, wash- and crock-fast red dyeing.
22 parts of the blue disperse dye C.I. Di~perse Blue 60 (calculated dry) in the form of the water-moist press cake were p~sted up with 12 parts of the dispersant of Exampla 20, 3010 parts of sorbitol in the form of a 70% strength aqueous solution, 1 part of a commercially available biocide (l~2-benzisothiazolin-3-one in the form of a 9.5% strength solution in propylene glycol) and 35water to 100 parts of total weight by means of a high-speed stirrer and milled in a stirred ball mill with ~lass media to obtain a state of fine division. The pH
'J 3 - 21 - O.Z. 0050/41661 was 8.7. Centrifuge test: 3/4/24/69.
The dye formulation obtained was thln-bodied and storable and was very highly suitable for dyeing yarn~
and fabrics made of polyester fibers by any conventional dyeing process. When packages of textured polyester fibers were dyed, completely level dyeings were obtained which were completely free of filtered-out dye deposits.
25 parts of the red disperse dye C.I. Disperse Red 91 (calculated dry) in the form of the water-moist press cake were pasted up with 11 parts of the dispersant of Example 22, 12 parts of sorbitol in the form of a 70% strength aqueous solution, 1 part of the biocide mentioned in Example 34 and water to 100 parts of total weight, adjusted to pH 8.5 and milled in a stirred ball mill until a satisfactory state of fine division was obtained.
Centrifuge test: 7/9/21/63.
The dye formulation obtained has the properties described under Example 34.
Similar results were obtained with the dispersant of Example 19.
40 parts of the red disperse dye C.I. Disperse Red 167:1 ~calculated dry), in the form of an aqueous press cake, were pasted up with 60 parts of the dispersant of Example 19 and : water to a suspension having a solids content of about 40%, brought to pH 7.5 with sulfuric acid (20% strength) and milled in a stirred ball mill until a satisfactory state of fine division was obtained.
Centrifuge test: 9/13/32/46.
The dispersion was dried in a spray dryer at a gas inlet temperature of 120C and reduced in a blender to the final color strength by addi~ion of 25 parts of the dispersant of Example 23.
~ J
- 22 - O.Z. 0050/41661 The dye powder obtained had the ~tate of fine division achieved in the wet milling ~tage. Stirring into water produced a stable dyeing liquor which had the good dyeing properties described in Example 34.
40 parts of the violet vat dye C.I. Vat Red 91 in the form of the water-moist press cake were pasted up with 60 parts of the dispersant of Example 23 and water to give a suspension having a solids content of 38%
and milled in a stirred ball mill until a satisfactory state of fine division was achieved.
Centrifuge te~t: 2/4/7/87.
After drying in a spray dryer at a gas inlet tempera~ure of 130C, 20 parts of the abovementioned dispersant were added to adjust to the final color strength.
The dye powder thus obtained had the state of fine division achieved in the wet milling stage. It had a long shelf life, was very readily dispersible in dyeing liquors and was highly suitable for dyeing cotton fibers by any conventional dyeing proces 23 parts of the vat dye Vat Green 1 (C.I. 59825) in the form of the aqueous press cake were pasted up with 10 parts of the dispersant of Example 11, 15 parts of a 70% strength aqueous sorbitol solution, 1 part of a commercial biocide (1,2-benzi~othiazolin-3-one in the form of a 9.5% strength solution in propylene glycol) and water to 100 parts of ~otal weight and bead-milled at pH 10-11 until a satisfactory state of fine division had been achieved. The centrifuge value was 4/14/29/53.
The dye formulation obtained was thin-bodied, storable and suitable for any conventional dyeing process.
40 parts of the vat dye Vat Blue 6 (C.I. 69825) - 23 - O.Z. 0050/~16~
in the form of the aqueous press cake were milled with 60 parts of the dispersant of Example 11 and the amount of water required to set a dry matter content of from 20 to 25% in a stirred ball mill at pH 10 and 11 until a satisfactory state of fine division had been achieved.
The centrifuge value was 5/10/12/73.
After milling, the dry matter content was ad-~usted to about 25~, 1 part of di-2-ethylhexyl sulfo-succinate and 1 part of di-C10-alkyldisulfonimide were added, and the suspension was filtered through 3 ~m filter plugs as often as required until it was speckle-free. This was followed by spray drying at an air inlet temperature of about 150C.
The dye powder obtained was readily dispersible in water, storable and suitable for any conventional dyeing process.
The same result as in Example 39 above was obtained when the dispersant of Example 11 W~8 replaced by the mixture of Example 12.
20 parts of the blue azo disperse dye C.I. 11345 (cal-culated dry) in the form of the water-moist press cake were pasted up with 18 parts of the dispersant of Example 6, 15 parts of sorbitol in the form of a 70~ strength aqueous solution, 1 part of a commercially available biocide, and water to 100 parts of total weight by means of a high-speed stirrer and milled in a stirred ball mill with glass media until a satisfactory state of fine division had been achieved. The pH was 8.3.
Centrifuge test: 3/3~18/76.
The dye formulation was thin-bodied and storable and was very highly suitable for dyeing polyester fibers and fabrics by any conventional dyeing process. The formulation was notable in particular for a high cotton 2 ~
- 24 - o.z. 00SO/41661 reserve in the dyeing of polyester/cotton blend fabric~
by the thermo~ol process. When packages of textured polyester fibers were d-yed, there were no filtered-out dye deposit~.
Claims (7)
1. A dispersant of increased bioeliminability or biodegradability for use in dye and pigment products, as tanning aids, in plastics production and in crop protec-tion formulations, which contains from 3 to 50% by weight, preferably from 5 to 30% by weight, of one or more aromatic or long-chain aliphatic carboxylic acids, salts thereof or anhydrides thereof or a mixture thereof.
2. A dispersant as claimed in claim 1, containing A) from 50 to 97% by weight of one or more arene-sulfonic acid-formaldehyde condensates, one or more sulfonates of phenol-formaldehyde condensates, one or more ligninsulfonates or a mixture thereof, and B) from 3 to 50% by weight of one or more aromatic or long-chain aliphatic carboxylic acids, salts thereof or anhydrides thereof or a mixture thereof, the addition of component B taking place before, during or after the sulfonation step or the condensation step in the preparation of component A.
3. A dispersant as claimed in claim 1 for use in dye formulations and dyebaths.
4. A dispersant based on a condensate of an arene-sulfonic acid and formaldehyde, obtainable by (a) sulfonating an aromatic compound to the arenesul-fonic acid and (b) condensing the arenesulfonic acid with formaldehyde, the sulfonation (a) or the condensation (b) or both steps being effected in the presence of from 5 to 50% by weight, based on the aromatic compound used in the sulfonation (a), of an aryl-containing or long-chain alkyl-containing carboxylic acid or a salt or anhydride thereof.
5. A dispersant as claimed in claim 4, wherein the condensate is obtainable by (a) sulfonating naphthalene or a mixture of aromatic compounds containing at least 10% by weight of naphthalene.
O.Z. 0050/41661
O.Z. 0050/41661
6. A dispersant as claimed in claim 4, wherein the condensate is obtainable by (a) sulfonating arene com-pounds which are preparable by the thermocracking of an naphthenic residue oil and which form the fraction which in the course of the fractional distillation of the cracking products passes over at 100-120°C and 1013 mbar.
7. A dispersant as claimed in claim 2, obtainable by subsequently mixing the aromatic or long-chain aliphatic carboxylic acids B or salts and anhydrides thereof into the compounds A.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA002044183A CA2044183A1 (en) | 1990-06-13 | 1991-06-10 | Dispersants |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4018873.6 | 1990-06-13 | ||
| CA002044183A CA2044183A1 (en) | 1990-06-13 | 1991-06-10 | Dispersants |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2044183A1 true CA2044183A1 (en) | 1991-12-14 |
Family
ID=4147767
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002044183A Abandoned CA2044183A1 (en) | 1990-06-13 | 1991-06-10 | Dispersants |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA2044183A1 (en) |
-
1991
- 1991-06-10 CA CA002044183A patent/CA2044183A1/en not_active Abandoned
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5186846A (en) | Dye dispersants: aryl sulphonic acid-formaldehyde condensate or ligninsulfonate | |
| EP0764695B1 (en) | Surfactants mixtures | |
| CN101027364B (en) | Navy blue and black mixtures, method for the production thereof, and their use for dying material containing hydroxy groups | |
| US4311480A (en) | Dyeing composition | |
| JPH0579264B2 (en) | ||
| EP0474595B1 (en) | Aqueous dispersion of low-solubility UV-absorbers | |
| EP0382138A1 (en) | Auxiliary mixture and its use in dyeing synthetic fibrous materials | |
| US3781169A (en) | Dispersing and stabilizing agents for dyestuffs | |
| US5534166A (en) | Preparation of condensates of arenesulfonic acids and formaldehyde and use thereof | |
| CA1136807A (en) | Use of oxalkylated novolaks as preparation agents for disperse dyestuffs and preparations made with said agents | |
| CA2044183A1 (en) | Dispersants | |
| US5902356A (en) | Textile dye preparations | |
| US5174792A (en) | Mixtures of monoazo dyes: dicyano-nitrobenzene azo compounds | |
| US5753775A (en) | Sulfonated and oxidized indene polymers | |
| EP0354174A1 (en) | Stable aqueous composition for modifying light fastness | |
| DE4202911A1 (en) | DYE MIXTURES FOR DYING TEXTILE HYDROPHOBIC FIBER MATERIALS | |
| CA1101155A (en) | Dispersant for textile dyeing and optical brightening | |
| US5248314A (en) | High temperature dyeing of polyester and polyester-containing textile materials with cyano group containing azo dye | |
| DE4131845A1 (en) | Benzophenone azo dye compsns. - contg. biodegradable dispersant based on sulphonate and carboxylic acid | |
| KR20030021181A (en) | Yellow dispersion dye mixture | |
| US5425785A (en) | Process for dyeing polyester and polyester-containing textile materials | |
| KR20030065596A (en) | Use of pigment dyes for dispersion dyeing from aqueous media | |
| JPS6218675B2 (en) | ||
| GB1603100A (en) | Dispersing agents based on water soluble phenolic condensates | |
| GB2041388A (en) | Sulphited polyoxyethylene esters |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |