Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
~ 3 ~ ~ Case 150-5603
Low-foam surfactants and their use
In the treatment of fibrous material, in particular textile material, with
conventional treatment agents, in particular dyes, from aqueous liquor, it
is often necessary to add levelling agents. This is of particular impor-
tance in dyeing. Since conventional levelling agents have a more or less
pronounced surface-active character and tend to foam-formation in the aque-
ous liquor and/or the presence of e.g. a wetting agent can favour foam-
-formation and e.g. higher speeds of the substrate and/or liquor (as in the
case of high-speed conveyance of substrates or/and liquors in jet dyeing
machines or in the case of the dyeing of cross-wound bobbins) particularly
favour foam-formation, the addition of a defoamer is necessary in such
cases, as a too high proportion of foam or an uncontrolled foam-formation
during the process, in particular dyeing process, may considerably disturb
this process. With procedures that are carried out in closed vessels an
excess of foam may lead e.g. up to a stand-still of the machine and in
procedures in open vessels or when opening a foam-containing closed vessel
an excessive foam-formation may eventually cause a dangerous foam eruption.
Also with foam behaviours that are not so pronounced a too high amount of
foam may also otherwise disturb the process, e.g. insofar as certain liqour
components may float on a too stable foam blanket or the levelling activity
of a levelling agent is disturbed or further the whole apparatus is soiled
etc. Experience has, however, shown that the presence of surfactans of the
above kind, in particular of levelling agents, may impair the defoaming or
foam-inhibiting activity of defoamers. For an efficient depression or
inhibiting of foam in aqueous systems, especially in those with a consi-
derable speed of goods or/and liquor and that as a consequencey strongly
favour the formation of foam - temperature and pressure variations during
the procedure may have an additonal influence - there are, thus, often
employed the particularly efficient silicone-based defoamers. When using
such strong defoamers it may happen that these are incompatible with
certain components of the liquor and/or tend to destabilize under
treatment-conditions so that the silicones may deposit on the substrate and
there may e.g. be formed the particularly feared silicone specks on the
treated goods.
- 2 ~ 9 ~ 3 0 Case 150-5603
It has now been found that the surfactant mixtures (G) described below are
excellently suitable as low-foam assistants, in particular as low-foam
levelling agents, for treatments in aqueous liquor and that the defoaming
activity may be clearly increased by the acldition of mild defoamers, i.e.
of such that are essentially free of defoaming silicones and preferably
also free of paraffinic waxes and/or of difficultly soluble high polymers,
specifically so that even at high speeds of liquor and/or substrate, in
particular even in closed vessels, e.g. in dye-jet machines, the formation
of a disturbing extent of foam may be substantially avoided.
The invention relates to the below defined mixtures (G), their production
and their novel components, to the (G)-containing compositions (P) and to
the use of (G) resp. (P) in the treatment of substrates in aqueous medium.
The invention thus provides a mixture (G)
of (E) a compound of the general formula R - -X---N ~ Y
y J (Ie)
wherein
R is a radical of the formula R ~ -CH~--CH--CH ~ -
O--Y Y
(a)
Ri-0- or R2 C0--NH - ,
(O (r)
R~ signifies a hydrocarbon radical with 8 to 30 carbon atoms,
R2 signifies a hydrocarbon radical with 7 to 29 carbon atoms,
X signifies C2_6-alkylene,
Y signifies a radical of the general formula
~ A-0) (B-0 ~ A-0 ~ (~),
A signifies ethylene and optionally propylene with the proviso
that at least 50 % of the m radicals A are ethylene,
~ 3 ~ ~ 8 ~ ~ 9 ~ Case 150-5603
B signifies Cq_6-alkylene or/and phenylethylene,
U signifies hydrogen or an anionic radical W1
r is a number in the range of 0 to 3 if R = (a), a number in the
range of 1 to 4 if R = (~), o:r a number in the range of 1 to
3 if R = (r),
m is at least 1,
m is a number in the range of (r + p + 5) to 150,
n is 0 or 1,
n is a number in the range of 1 to (r + p + 2),
x is a number in the range of 0 to m
and
p is O or 1
or a protonation and/or quaternization product thereof or a
mixture of such compounds,
with (F) a compound of the general formula
R + X N~A-O~U ( If),
L w~o--A~m ~r
wherein
Ro signifies a radical of the formula (~) or (r) or of the for-
mula
R ~ --CH2 CH--CH2 l N
L I~A~U ~ ~A~3~U ( 1 ) ~
and the symbols R1, R2, A X. U. m, m, p and r have, indepen-
dently from (E), the significances indicated under (E),
or a protonation and/or quaternization product thereof or a mix-
ture of such compounds.
As hydrocarbon radicals R1 come into consideration conventional alkylaro-
matic or purely aliphatic hydrocarbon radicals, as can occur in surface
active compounds; they may be saturated or unsaturated. There may, in
particular, be mentioned the following fatty radicals: capryl, caprinyl,
lauryl, myristyl, cetyl, stearyl, arachidyl, behenyl, lignoceryl, cerotyl,
- 4 ~ 9 0 Case 150-5603
oleyl, elaidoyl, linoleyl, linolenyl, gadoleyl, arachidonyl and docosenyl
(brassidyl or the erucahydrocarbon fatty radical) and also technical
hydrocarbon radical mixtures containing such fatty radicals, in particular
coconut fat, tallow fat, tallow alkyl, technical oleyl, arachidyl/behenyl,
arachidyl/behenyl/stearyl, stearyl/cetyl and oleyl/cetyl. As R2-C0- come
in general into consideration conventional acyl radicals, in particular
fatty acid radicals of conventional fatty acids with 8 to 30 carbon atoms,
especially those corresponding to the above listed fatty radicals, parti-
cularly caproyl, caprinoyl, lauroyl, myristoyl, palmitoyl, stearoyl, ara-
chidoyl, behenoyl, lignoceroyl, cerotoyl, oleoyl, elaidoyl, linoleoyl,
linolenoyl, gadoleoyl, arachidoyl and the radical of erucic acid and tech-
nical mixtures, in particular the acyl radicals of technical, optionally
hydrogenated fatty acids, especially of coconut fatty acid, tallow fatty
acid, tallow alkyl fatty acid, technical oleic acid and technical palmit-
oleic acid. Among the mentioned radicals are preferred those with 12 to 24
carbon atoms, in particular with 16 to 24, especially 18 to 22 carbon
atoms. Among the saturated and the non-saturated fatty radicals the satu-
rated ones are preferred. Among the technical mixtures are preferred those
that are predominantly saturated tadvantageously 2 80 % by weight, prefer-
ably > 90 % by weight saturated). Among the radicals R2-C0- and Rl in the
significance of R R1 is preferred.
X may be any bivalent C2_6-alkane radical as occurring in alkylene diamines
and polyalkylenepolyamines, advantageously ethylene, propylene or hexameth-
ylene, wherein, if r > 1, X preferably signifies ethylene and/or propylene
and the r radicals X may have the same significance or different signifi-
cances. Preferably X signifies ethylene, propylene-1,3 or hexamethylene,
in particular propylene-1,3 if r = 1, ethylene and/or propylene-1,3 if
r = 2, or ethylene if r = 3.
Advantageously r signifies 0 to 2, in particular 0 or 1.
The index p signifies preferably 0.
Of the total radicals -A-0- in formula (Ie), preferably at leat 80 % are
ethyleneoxy groups. More preferably all radicals -A-0- in formula (Ie)
signify ethylenoxy groups. Also in formula (If) advantageoulsly at least
80 % of the total radicals -A-0- are ethylenoxy groups, preferably all of
- 5 - Case 150-5603
the radicals -A-0- in formula (If) are ethylenoxy groups.
As C4_6-alkylene in the significance of B come in general into conside-ration conventional radicals as can be introduced into the molecule by
addition of the respective cyclic oxides, especially oxiranes, preferably
butylene, in particular butylene-1,2, -2,3 or -1,4. Preferably B signifies
phenylethylene or/and in particular butylene, before all butylene-1,2.
The sum of the total of the groups -A-0- in (E), i.e. m, is advantageously
(r + p + 6) to 70 [resp. if p , 0, (r + 6) to 70], preferably 10 to 70, in
particular 30 to 70, and in (F) preferably 30 to 70. The sum of the total
of the groups -B-0- in (E), i.e. n, is advantageously in the range of 1 to
(r + p + 1), and is advantageously < 3, in particular 1 to 2, before all 1
to 1.5.
Of the n groups -B- in (E) advantageously at least one half, preferably
0.5 to 2, in particular 1 to 2, on average are C4_6-alkylene, more prefe-
rably butylene, whereas preferably at most 0.5, i.e. 0 to 0.5, on average,
are phenylethylene groups. With particular preference -B- signifies
exclusively butylene.
Where in the concerned polyglycol chains (~) in (E) n = 1, the radical
-B-0- may be in any position of the respective chain, i.e. if x = m, B is
bound directly to N [or if in the radical () p . 1, it may also be direct-
ly linked to the CH-bound oxygenl or, if x - 0, B is bound directly to
-0-U, or, if 0 < x < m -B-0- is inserted between two groups -A-0- e.g. as
an intermediate element of a block-polymeric polyglycolether chain. With
particular preferen~e x = 0 and the group -B-0- is placed at the end of the
added chain and is bound to U as -B-0-U.
If U represents an anionic radical Ul this may be any anionic radical as
conventionally employed for the anionic modification of polyglycol
radicals, principally a sulphuric acid ester or phosphoric acid ester group
or a dicarboxylic acid monoester group as may be formed by esterification
of the respective terminal hydroxy groups, or a carboxy-(Cl_3-alkyl) group
(especially carboxymethyl) as may be formed by carboxyalkylation, in parti-
cular carboxymethylation, of the hydroxy group. These anionic groups Ul
may be in the form of salts, for which conventional cations come into con-
- 6 - Case 150-5603
sideration for salt-formation, principally alkali metal cations (lithium,
sodium, potassium) or optionally substituted ammonium cations [unsubstitu-
ted ammonium or mono-, di- oder tri-(C1_3-alkyl)- or -(C2_3-hydroxyalkyl)-
-ammonium], or may form inner salts with basic amine groups of the molecule
or further, especially at lower pH-values, may even be in the form of free
acid, advantageously at least a part of the symbols U signifies hydrogen.
Advantageously the molecule contains on average not more than 1.5, prefer-
ably not more than one anionic substituent W1. With particular preference
all symbols W signify hydrogen.
Preferred mixtures (G) are those in which
A signifies ethylene,
R signifies a radical of formaula (a),
r signifies a number from 0 to 2,
p signifies zero,
~m signifies (r + 6) to 70
and in (E) ~n signifies 1 to (r + 1),
provided that at most one of the n radical -B- is phenylethylene,
especially those in which
R1 signifies an aliphatic hydrocarbon radical with 12 to 24 carbon
atoms,
X signifies propylene,
x signifies zero
and W signifies hydrogen
and of the ~n radicals -B- in (E) 0 to 0.5 signify phenylethylene and the
remaining, in particular 0.5 to (r + 1) signify butylene.
The compounds (F) are known or may be produced analogously to known method
and serve as assistants for the treatment of substrates, in particular as
levelling agents or the dyeing of fibrous material. The compounds (E) have
also a levelling effect and their tendency to foaming is minimal. If (F)
is blended with (E) the joined effect of the mixture is not worse than the
one of (F) alone and the tendency to foaming is surprisingly clearly redu-
7 h ~ 8 ~ ~ 9 Case 150-5603
ced. The relative amounts of (E) and (F) may vary in a broad range and are
suitably chosen so that both effects, i.e. the own (before all levelling)
effect of (F) and the diminished tendency to foaming are efficiently dis-
played. The weight ratio (E)/(F) is advantageously in the range of 10/90
to 90/10, preferably 30/70 to 70/30, especially 1/2 to 2/1.
The invention further provides the new products (E1), i.e. products (E)which are as defined above and in which -B- signifies C4_6-alkylene and
x = O.
Compounds (E) and (F) may be produced in a manner known per se by oxyalkyl-
ation of the respective starting amines and optionally further reaction of
the product by introduction of anionic radicals Wl and/or protonation and/-
or quaternization.
The process for the production of compounds of formula (E) is in particular
characterized in that a compound of formula
R ~ X--NH ~ H (IIa),
in which Rx signifies a radical of the formula (~), (r) or
R ~ -CH2 CHOH - CH ~ H - (a2)
or a mixture of such compounds
is reacted with the corresponding cyclic oxides (A) and (OB), optionally at
least one anionic radical Ul is introduced and the product is optionally
protonated and/or quaternized.
The compounds (F) may be produced in an analogous way by oxyalkylating a
compound of formula (IIa) or a mixture of such compounds with the corre-
sponding A-oxide or oxides, optionally introducing at least one anionic
radical Ul and optionally protonating and/or quaternizing the product.
According to a particularly advantageous procedure the mixtures (G) of (E)
and (F) are produced directly by reacting at least one amine of formula
(IIa) with A-oxide and B-oxide, where the quantity of B-oxide is chosen so
that the corresponding mixtures can result. It is, however, also possible
to produce the components (E) and (F) separately and then to mix them whith
- 8 ~ Case 150-5603
each other in the suitable quantitative ratio, or also to produce (F) in
admixture with a part of (E) by mixed oxyalkylation and optional further
reaction and then to add further component (E) up to the desired mixture
ratio. Of course the production of (G) in admixture is indicated if in
components (E) and (F) the symbols W, A and X and the indexes r and p as
well as the sum ~m have the same significances and if R derives from the
same radical Rx. By subsequent blending with further same of different
component (F) the properties of the final mixture may be specifically ad-
justed. The separate production of (E) and (F) is especially suited, if in
(E) n > 1 (especially if n on average is > 1.5) whereas the production in
admixture is especially indicated if in compounds (E) n is predominantly
= 1 (especially if ~n on average is 1 to 1.5).
The reaction of compounds of formula (IIa) with the respective cyclic
oxides, principally oxiranes (A-oxide: ethylene oxide, propylene oxide;
B-oxide: butylene oxide, pentylene oxide, hexylene oxide, styrene oxide),
to introduce the respective radicals -A-0- and -B-0- may be carried out in
any desired sequence. For the production of compounds (E) it is preferred
to first react with A-oxide and then with B-oxide. The reaction may be
carried out under reaction conditions conventional per se, principally at
elevated temperature, in particular in the temperature range of 100 to
180C, preferably 140 to 170C, and in the presence of a suitable catalyst,
in particular an alkali metal hydroxide (sodium hydroxide, potassium hydr-
oxide, lithium hydroxide). The reaction may take place in an inert organic
solvent or in the absence of any solvents, advantageously under displace-
ment of air oxygen. The reaction with B-oxide is carried out advantage-
ously as the last oxyalkylation.
The introduction of an anionic radical Wl may be carried out in a manner
known per se and takes place advantageously by reaction with a suitable
acid or a functional derivative thereof, e.g. with a C3_8-dicarboxylic acid
or a functional derivative thereof, preferably the anhydride (with parti-
cular preference the cyclic anhydride, e.g. maleic, succinic or phthalic
acid anhydride), with a C2 4-chloroalkane carboxylic acid, in particular
chloroacetic acid, with phosphoric acid anhydride, with polyphosphoric acid
or with sulphuric acid (optionally S03-containing) or a functional deriva-
tive thereof (e.g. chlorosulphonic acid or aminosulphonic acid) and, if
required, with a base for salt formation. The reaction with a cyclic
- 9 - ~ ~ ~ 9 5 ~ Case 150-5603
anhydride takes place e.g. at 0 to 80C, optionally in the presence of a
catalyst, if desired with subsequent addition of a base for salt formation.
The reaction with chloroacetic acid takes place suitably under dehydrohalo-
genating conditions, e.g. at 45 to 80C, suitably with addition of an
alkali metal hydroxide. The reaction with P20s takes place advantageously
at 30 to 80C, if desired with subsequent addition of water and/or a base
for salt formation. The reaction with aminosulphonic acid takes place
advantageously in the presence of urea, suitably 10 to 200 ~ by weight of
the used quantity of aminosulphonic acid, advantageously at temperatures
between 75 and 130C. The reaction with sulphuric acid takes place advan-
tageously in a similar temperature range, if desired with subsequent
addition of a base for salt formation. The reaction with chlorosulphonic
acid takes place suitably under dehydrohalogenating conditions, e.g. at 45
to 80C, and with addition of alkali metal hydroxide.
For protonation there may be employed conventional acids, in particularmineral acids (sulphuric acid, phosphoric acid or preferably hydrochloric
acid) or low molecular aliphatic carboxylic acids (e.g. with 1 to 4 carbon
atoms, in particular formic, acetic, oxalic, lactic, tartaric or citric
acid).
By quaternization there may be introduced conventional quaternizing radi-
cals, in particular Cl_4-alkyl, aryl-(Cl_3-alkyl) or -CH2-C0-NH2. For
quaternization there may be employed conventional quaternizing agents, in
particular aryl-(Cl_3-alkyl)-halides (especially benzylchloride) C1_4-alkyl
halides (preferably chlorides or bromides) or sulphates (e.g. dimethylsul-
phate or diethylsulphate) or chloroacetic acid amide. The quaternization
may take place under conventional reaction conditions, e.g. in the tempe-
rature range of 40 to 120, preferably 60 to 100C. Quaternization may be
carried out exhaustively or partially, e.g. so that on average 0.5 to 1
basic nitrogen per molecule is quaternated. Preferably neither (E) nor (F)
are quaternated.
The produced mixtures may be diluted directly with water to reach the
desired solid substance content. The invention, thus, further provides
compositions (P) comprising a mixture (G) which is as defined above.
The compositions (P) advantageously further contain
10 - iJ ~ ~ ~ 3 3 Case 150-5603
(H) at least one non-ionic, cationic or weakly anionic antifoaming
additive, which is essentially free of silicone-based defoamers and
preferably also of defoaming paraffinic waxes and/or difficultly
soluble high polymers.
As (H) come, in general, into consideration low foam compounds and foam in-
hibiting compounds, specifically low-foam surfactants as may conventionally
be employed as dyeing assistants, e.g. low-foam wetting agents (e.g. fatty
acid oligoethyleneglycol-monoesters or addition products of propylene oxide
and ethylene oxide to fatty alcohols or to alkylphenols, e.g. uith 12 to 24
carbon atoms in the lipophilic radical) or low-foam dyeing assistants that
influence the affinity of the dye for the substrate (e.g. reaction products
of fatty acids - e.g. such with 16 to 22 carbon atoms - with alkanolamines
or aminoalkylalkanolamines, which are optionally oxyethylated and may be in
protonated form), as well as typically defoaming additives, e.g. of the
kind of the low alkyl esters of higher fatty acids, of the fatty acid
a]kylene bisamides, of the non-esterified fatty acids, of the higher
molecular in particular also branched fatty alcohols, of the phosphoric
acid trialkylesters, of the glycerine dialkyl ethers, or further of the
emulsified oils, such as occur also as fat-liquors, especially if they are
emulsified with weakly anionic emulsifiers (e.g. of the kind of the fatty
acids and of the carboxymethylated derivatives of oxyalkylated high fatty
alcohols). The choice and amount of the additives (H) is dictated essen-
tially by the proposed field of use of the product. In general the rela-
tive quantities of (G) and (H) are chosen so that the reciprocal sustaining
of the foam inhibiting effect is as pronounced as possible and at the same
time the functional effect of the product (G) (in particular as levelling
agent) may be efficiently displayed. The weight ratio (G)/(H) is advan-
tageously 1/10 to 50/1, preferably 1.5/1 to 25/1.
Since some foam hemming additives that may be employed as (H) may have an
insufficient hydrosolubility and/or their solubility might, in some cases,
be insufficient for the production of compositions of higher concentration,
it is in such cases of advantage to add
(L) at least one solubilizer and/or hydrotrope.
~ g j 3 ~ ~ Case 150-5603
As solubilizers and/or hydrotropes there may be employed conventional hy-
drosoluble low molecular compounds, e.g. polyols, etheralcohols or amides,
e.g. mono- oder diethyleneglycol and C1_4-monoalkylethers thereof, propyl-
eneglycol and/or urea.
The quantity and choice of the respective solubilizer andJor hydrotropedepends essentially on the constitution of the other components and their
quantities. The weight ratio (L)/[(G) + (H)]) is in particular in the
range of 1/1 to 1/20.
The suitable amounts of (H) and also of (L) may be assessed by means of a
few preliminary tests.
The mixtures (G) are advantageously formulated to aqueous compositions,preferably together with (H) and if required also together with (L), the
dry substance content of which is in particular in the range of 5 to 80 %
by weight, preferably 20 to 75 ~ by weight. The (G)-content of the aqueous
compositions (P) is advantageously in the range of 5 to 60 % by weight,
preferably 15 to 50 % by weight. They are distinguished by their storage
stability.
The mixtures (G) according to the invention, preferably in the form of the
above-defined aqueous compositions (P), serve as assistants, in particular
as levelling agents, in the treatment, especially in the dyeing, of sub-
strates from aqueous medium. As substrates come into consideration, prin-
cipally fibrous materials, in particular textile material, which may be of
synthetic, animal or vegetable origin, preferably of natural and/or synthe-
tic polyamides (wool, silk, synthetic polyamides) and mixtures thereof with
other materials, e.g. with cotton, polyesters, polyurethanes or polyacryl-
nitril fibres. The mixtures (G) serve in particular as levelling agents
for the dyeing of the mentioned substrates with corresponding anionic dyes,
as they are conventionally employed for the dyeing of wool, silk and/or
synthetic polyamides, especially acid dyes, metal complex dyes, direct
dyes, vat dyes, sulphur dyes and mordant dyes, and include as well the so-
-called milling dyes as the so-called neutral build-up dyes. The substrate
may be in any processing form as conventionally employed for the respective
dyeing processes, e.g. as loose fibres, filaments, yarns, strains, bobbins
(also cross-wound bobbins), woven goods, knitted goods, carpets, tuftings,
- 12 ~ Case 150-5603
felts, non-wovens or velvet or also as half-ready-made or ready-made goods.
The dyeing may take place according to conventional impregnation or exhaust
processes, e.g. by padding, dipping, spraying, foam application or prefer-
ably by exhaust process in short or long liquors, of which there are espe-
cially to be mentioned the processes involving considerable speed of the
goods or/and the liquor (e.g. as the dyeing of cross-wound bobbins or in
jet-dyeing machines) and those in which the substrate tends particularly to
entrap air (e.g. the dyeing of skeins and looped substrates) since with
these the effect of the compositions of the invention is displayed particu-
larly clearly, as they not only inhibit the formation of foam, but favour
also the deaeration of the substrate (e.g. in terry-cloth or where air-
-channels are formed in the skeins). The dyeing processes may be carried
out under temperatures, pH-values and liquor-to-goods ratios, conventional
per se and as suitable for the relative substrate [for natural polyamides
advantageously at temperatures from room temperature t= 20C) to 115C,
e.g. 20 to 100C, and pH-values in the range of 1.5 to 7.0, e.g. 3.5 to
6.5, and for synthetic polyamides, advantageously at temperatures in the
range of 30 to 150C and pH-values in the range of 2 to 9, e.g. 4.5 to 7.5;
the liquor-to-goods ratios for exhaust process are advantageously in the
range of 2:1 to 120:1, preferably 5:1 to 60:1].
The concentration of the products of the invention is chosen depending on
the desired effect, especially levelling effect, in particular depending on
the employed dye and liquor-to-goods ratio as well as on the substrate and
special application method; it is, e.g. in the range of 0.1 to 5 g, prefe-
rably 0.2 to 2 g (G) per liter of aqueous liquor.
By the process of the invention and using the compositions of the invention
there may be achieved excellent levelling effects, whilst the addition of
strong defoamers may be avoided, especially of such that may tend to desta-
bilization and/or may leave on the substrate disturbing deposits (e.g. of
silicones, of paraffinic waxes or of high polymers), which lead then to
specks that are very difficult to eliminate or may even not be eliminated
without damaging the substrate. The further properties, in particular in-
tensity and fastnesses of the dyeings, as well as the physical properties
of the treated substrates are substantially not impaired.
- 13 - ~ Case 150-5603
In the following examples parts and percentages are by weight and the tem-
peratures are indicated in degrees Celsius. In the Application Examples
the percentages are referred to the weight of the substrate.
Example 1
To 1 mole of N-(y-aminopropyl)-fatty amine are added, in conventional way,
after addition of 1 % of sodium hydroxide, referred to the amine, 35 moles
of ethylene oxide during 4 to 5 hours at 150-165C; subsequently there are
further added 0.5 moles of butylene oxide (~8 %) and the addition reaction
is carried out at the same temperature. There is obtained a brown pasty
substance.
The employed N-(r-aminopropyl)-fatty amine (DINORAM 42, of the firm PROCHI-
NOR) is a technical mixture of molecular weight 420, the fatty radical of
which consists mainly of the following components: stearyl about 25 ~;
arachidyl about 25-35 %; behenyl about 30-40 ~; C20_22-unsaturated about
2-5 %.
Example 2
The procedure is carried out as in Example 1 usingt however, in place of
the there employed N-(r-aminopropyl)-fatty amine, the equimolar amount of
N-(y-aminopropyl)-tallow fatty smine.
Example 3
The procedure is carried out as described in Example 1, with the difference
that in place of the there employed N-(r-aminopropyl)-fatty amine there is
employed the equimolar amount of tallow fatty amine.
Example 4
The procedure is carried out as described in Example 3, with the difference
that in place of the tallow fatty amine, there is employed equimolar amount
of a technical fatty amine mixture, consisting essentially of behenylamine
and arachidylamine.
- 14 ~ Case 150-5603
Example 5
The procedure is carried out as in Example 1, with the difference that in
place of 0.5 moles of butylene oxide, there is added 1 mole of butylene
oxide.
Example 6
The procedure is carried out as described in Example 1, with the difference
that in place of 0,5 moles of butylene oxide, there is added 1 mole of
styrene oxide.
Example 7
The procedure is carried out as in Example 6, with the difference, that in
place of 1 mole of styrene oxide, there are added 1.5 moles of styrene
oxide.
Example 8
The procedure is carried out as in Example 6, with the difference that in
place of 1 mole of styrene oxide there are added 2 moles of styrene oxide.
Example 9
The procedure is carried out as described in Example 1, with the difference
that subsequently there are further added 0.5 moles of styrene oxide under
otherwise identical reaction conditions.
Example 10
The procedure is carried out as in Example 1, with the difference that in
place of 0.5 moles of butylene oxide, there are added 0.7 moles of butylene
oxide.
Example ll
The procedure is carried out as in Example 1, with the difference that in
- 15 - ~ Case 150-5603
place of 0.5 moles of butylene oxide, there are added 0.8 moles of butylene
oxide.
Example 12
The procedure is carried out as in Example 4, with the difference that in
place of 35 moles of ethylene oxide, there are added 50 moles of ethylene
oxide and in place of 0.5 moles of butylene oxide, there are added 0.8
moles of butylene oxide.
Example 13
The procedure is carried out as in Example 4, with the difference that in
place of 35 moles of ethylene oxide, there are added 55 moles of ethylene
oxide.
Example 14
The procedure is carried out as described in Example 13, with the diffe-
rence that subsequently there are further added 0.5 moles of styrene oxide
under otherwise identical reaction conditions.
Examples 15, 16 and 17
The products of Examples 5, 6 and 9 are each blended with the equimolarquantity of the non-butoxylated ethylene oxide addition product of Example
1.
Examples 18 and 19
The products of Examples 7 and 8 are each blended with the equimolar amount
of the product of Example 1 and with the sesquimolar amount of the non-bu-
toxylated ethylene oxide addition product of Example 1.
Compositi on 1
The product of Example 1 is diluted with demineralized water to a solids
- 16 ~ Case 150-5603
content of 30 % and adjusted with formic acid to pH 5.
Composition 2
400 parts of the product of Example 1 are melted in a stirrer flask at 60C
and then the following components are sequentially separately added and
stirred:
180 parts of propylene glycol,
20 parts of tetramethylnonanol,
280 parts of demineralized water
and 120 parts of urea
then cooling is allowed with stirring; when reaching 25C the pH is adjus-
ted to 7 by addition of formic acid.
Composition 3
The procedure is carried out as in Composition 2, with the difference that
to the 400 parts of the pre-melted product of Example 1 there are added
sequentially and with stirring the following components:
20 parts of the addition product of 6.5 moles of ethylene oxide to
1 mole of oleic acid
20 parts of tetramethylnonanol
140 parts of propylene glycol
320 parts of demineralized water
and 100 parts of urea
and at 25C the pH is adjusted with formic acid to 7.
Compositi on 4
The procedure is carried out as described for Composition 2, with the dif-
ference that to the 400 parts of the pre-melted product of Example 1 there
are added sequentially the following products:
60 parts of propylene glycol
- 17 ~ Case 150-5603
100 parts of butylglycol
50 parts of glycerindiisobutylether-1,3
270 parts of demineralized water
and 120 parts of urea
and at 25C the pH is adjusted to 7 with formic acid.
Composition 5
The procedure is carried out as described for Composition 2, with the dif-
ference that in place of 400 parts of the product of Example 1, 400 parts
of the product of Example 6 are pre-melted at 60C and the following pro-
ducts are added sequentially.
60 parts of a 30 % aqueous solution of the condensation product of
1 mole of oleic acid with 1 mole of N-(~-aminoethyl)-ethanolamine,
oxyethylated with 2 moles of ethylene oxide and protonated with
formic acid
20 parts of metiloil (commercially available mixture of fatty acid
methylesters)
and 520 parts of demineralized water
and then at 25C the pH is adjusted with formic acid to 7.
Composition 6
The procedure is carried out as described for Composition 5, with the dif-
ference, that to the pre-melted product of Example 6 there are added se-
quentially the following components:
80 parts of the 30 % condensation product indicated in Composition 5
240 parts of an aqueous 25 % addition product of 2 moles of ethylene
oxide and 1 mole of propylene oxide to 1 mole of oleic alcohol
and 280 parts of demineralized water
and at 25C the pH is adjusted with formic acid to 7.
- 18 - ~ 5 9 0 Case 150-5603
Composition 7
The procedure is carried out as described for Composition 2, with the dif-
ference that 380 parts of pre-melted product of Example 1 are prepared and
the following components are sequentially added with stirring:
100 parts of the 25 ~ aqueous addition product of 2 moles of ethylene
oxide and 1 mole of propylene oxide to 1 mole of oleyl alcohol
60 parts of propylene glycol
and 460 parts of demineralized water,
and at 25C the pH is adjusted to 7 with formic acid.
~e~
The procedure is carried out as described for Composition 7, with the dif-
ference that to the 380 parts of the pre-melted product of Example 1 there
are added sequentially the following products with stirring:
100 parts of a fat-liquor of the following composition
26 ~ of palmkernel oil
8 % of paraffin oil
3 ~ of oleic acid
12 ~ of the carboxymethylated addition product
of 12 moles of ethylene oxide to 1 mole of
oleyl alcohol as sodium salt
rest water,
60 parts of propylene glycol
and 460 parts of demineralized water
and at 25C the pH is adjusted to 7 with formic acid.
Composition 9
The procedure is carried out as described for Composition 2, with the dif-
ference that instead of the 400 parts of the product of Example 1 there are
employed 400 parts of the product of Example 4.
~ 3 ~ ~
- 19 - Case 150-5603
osition lQ
The procedure is carried out as described for Composition 4, with the dif-
ference that instead of the 400 parts of the product of Example 1 there are
employed 400 parts of the product of Example 4.
Analogously as described in Compositions 1 to 10, the other products ofExamples 1 to 19 may be employed.
Application Example A
In a laboratory-jet of the firm MATHYS uith a nozzle of 55 mm of diameter a
polyamide 6 (perlon)-tricot is dyed under maintenance of the following
parameters:
liquor volume = 6 l,
flow = 60 l/min.,
speed of the goods = 20 m/min.,
and with the following additions:
dyestuff . 0.5 % of the dye Colour Index Acid Blue 72,
levelling agent: Composltion 2, 1 g/l,
acetic acid to pH 6,
as follows: the liquor is heated during 40 minutes from 30C to 98C, then
dyeing is continued for 30 minutes at 9aoc and then it is cooled.
During the heating stage foam formation is very small and does not reach a
disturbing proportion; in the subsequent course of the dyeing at 90-98C
the little foam disappears nearly completely; in the cooling stage the foam
formation is also only minimal.
Application Example B
Machine: THEN HT Jet
Material: 7 kg of warp knit fabric of texturized polyamide 66, prewashed,
h ~ 8 ~ ~ 3 ~
- 20 - Case 150-5603
rinsed, soured and dried
Liquor: 40:1 (soft water)
Additions: 1.0 g/l ammoniumsulphate
2.0 % of Composition 2
0.1 % Lanasyn Rubine S-5BL = C.I. Acid Violet 128.
The goods are fed into the jet with water, then the ammoniumsulphate and
Composition 2 are added and the jet is operated for 5 minutes at 30C.
Only little foam is formed. Speed 150 m/min.
Subsequently the dye is added and the bath is heated by 1C/min. to 80C
and then by 2C/min. to 100C; dyeing is continued at this temperature for
15 minutes and then the jet is heated by 2C/min. to 115C, maintained
5 minutes at this temperature and then cooled and the goods are rinsed.
The little foam present at 30C diminishes clearly at 60C, does, however,
never disappear completely, i.e. during the whole dyeing process there is
always present a little foam, but no foam blow occurs even if during the
cooling of the machine, e.g. at 95C, the pressure is reduced on purpose
very quickly. The dyeing is level and speckless.
Application Example C
Machine: OBERMAIER HT dyeing machine
Material: 3 kg of texturized polyamide 66 yarn dtex 22f7 on spring
tubes, bobbin-weight about 1 kg
Liquor: 10:1 soft water
Additions: 0.2 g/l sodium carbonate
1.0 g/l of the acid-yielding agent of USP 4 568 351, Example 1,
0.8 g/1 of Composition 4
1.4 % of C.I. Acid Violet 48
1.08 X of C.I. Acid Blue 278
Liquor circulation: 1 cycle/min. in ~ out, no reversal.
The dyeing is started at 40C and the bath is heated by 2C/min. to 105C,
dyeing is continued during 15 minutes at this temperature, then the bath is
indirectly cooled to 70C and, after draining off of the well exhausted
dye-bath, the goods are rinsed once with cold water. After drying a knit-
- 21 - ~J ~ ~ 3 ~ ~ Case 150-5603
ting test sample shows a completely even dyeing.
The foam behaviour of the products can also be simulated in a PRETEMA
dyeing machine and the foam behaviour displays similarly as in the MATHYS
laboratory-jet.
Like Composition 2 or 4 also the other ones of the above Compositions may
be used in the above dyeing processes and in the PRETEMA-test.
