Note: Descriptions are shown in the official language in which they were submitted.
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.
- 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 ~
- 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 ~
- 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 ~
- 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.
EXAMPLE 25
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.
EXAMPLE 26
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.
EXAMPLE 27
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.
EXAMPLES 28 AND 29
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.
EXAMPLE 30
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~.
EXAMPLE 31
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
EXAMPLE 32
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.
20EXAMPLE 33
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.
25EXAMPLE 34
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.
EXAMPLE 35
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.
EXAMPLE 36
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.
EXAMPLE 37
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
EXAMPLE 38
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.
EXAMPLE 39
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.
EXAMPLE 40
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.
EXANPLE 41
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~.
