Note: Descriptions are shown in the official language in which they were submitted.
10490~'~
An object of the present invention is the development
of an ethoxylation product having the formula
R~l
R-CH-CH2-N-X
0-(CH2-CH2-0)n~H
wherein R is an aliphatic hydrocarbon group having from 6 to 20
; carbon atoms selected from the group consisting of alkyl and
alkenyl, Rl is an alkyl having from 1 to 4 carbon atoms, X is a
member selected from the group consisting of Rl and -(CH2-CH2-0~-H~
and n and m are integ~rs, the sum of which being from 2 to 20.
~ Another object of the present invention is the develop-
10 ment of a process for the production of the above ethyloxylation
product comprising the steps of reacting a 1,2-epoxy compound of
the formula
R-CH _ CH2
~O
whereln R ls an allphatlc hydrocarbon group having from 6 to 20
carbon atoms selected from the group consisting of alkyl and
alkenyl, with at least an equimolar amount of an amine having the
formula
R
H-N
, R
~` wherein Rl is an alkyl having from 1 to 4 carbon atoms and R2 ls
a member selected from the group consisting of hydrogen and Rl, at
a temperature of from 20C to 150C for a time sufficient to ef-
~` fect condensation, dehydrating the reaction product, reacting the
dehydrated reaction product with from 2 to 20 mols of ethylene
oxide in the presence of an alkaline ethoxylation catalyst under
ethoxylation conditions, and recovering said ethoxylation product.
A further object of the present invention is the devel-
opment of a process for washing textiles employing from 0.05
-1-
~04904Z
to 12 gm/liter of the above ethoxylated product.
A yet further ob~ect of the present lnventlon ls the
obtalnlng of washlng agent compositions partlcularly for wash-
lng textiles containlng from 0.5% to 40% by weight of the
above ethoxylated product.
These and other ob~ects of the present invention will
become more apparent as the description thereo~ proceeds.
The above ob~ects have been achleved by the develop-
ment Or novel lnterface-active ethoxylatlon products, a
method for their productlon, and thelr use in washing and
cleansing agents.
The new ethoxylation products are compounds havlng
formula I;
1 . .
R-fH-CH2-N-X
0-(CH2-CH2-0) -H (I)
whereln R represents an allphatic hydrocarbon group having 6
to 20, preferably 10 to 18 carbon atoms~ Rl represents an
alkyl group havlng 1 to 4 carbon atoms, preferably the methyl
or ethyl group, X represents an alkyl group Rl or the group
-(CH2-CH2-0) -H, and the numbers n and m represent whole
numbers, the sum of whlch are from 2 to 20, preferably 6 to
~, 12.
~, The product of the lnventlon possess surface-actlve
properties; they are sultable as wettlng agents, corroslon
lnhlbltors, bitumen ad~uvants, emulsifiers and especlally
sur~ace-active compounds or tensldes for washlng and cleans-
lng agents.
.
-
104904Z
More particularly, the invention lnvolves an ethoxy-
latlon product having the formula
1 1
R-IH-CH2-N-X -
O-(CH2-CH2-O)n-H
whereln R is an aliphatic hydrocarbon group having from 6 to
20 carbon atoms selected from the group consisting of alkyl
and alkenyl, Rl is an alkyl having from l to 4 carbon atoms,
:X ls a member selected from the group conslstlng of Rl and
-(CH2-CH2-O)m-H, and n and m are integers, the sum of whlch
belng from 2 to 20; as well as the process of producing the
ethoxylation product comprising the steps of reactlng a 1,2-
epoxy compound having the formula
:~; R-CH CH2
! \ /
whereln R ls an aliphatlc hydrocarbon group havlng from 6 to
20 carbon atoms selected ~rom the group conslsting of alkyl
and alkenyl, wlth at least an equlmolar amount of an amlne
havlng the formula R
H-N
R2
whereln Rl ls an alkyl havlng from l to 4 carbon atoms and
R2 ls a member selected from the group consistlng of hydrogen
and Rl, at a temperature of from 20C to 150C for a tlme
~,, sufflclent to effect condensatlon, dehydratlng the reaction
~" product, reactlng the dehydrated reactlon product wlth from
2 to 20 mols of ethylene oxlde in the presence of an alkaline
:'
104904Z
ethoxylatlon catalyst under ethoxylatlon condltlons, and
recovering said ethoxylatlon product.
Partlcularly suitable as allphatic hydr~carbon groups
R ln the formula are alkyl groups, which are preferably
stralght-chaln. Especlally preferable are compounds Or
rormula I where R is straight-chaln alkyl and the sum of the
carbon atoms is R in the range of from 10 to 18.
The compounds of formula I are ethoxylation products of
secondary or tertiary 2-hydroxy-alkylamines, possessing non-
lonic water-solubilizing polyoxyethyleneglycol ether groups.
The degree of ethoxylation of the products is expreased by
the sum of the numbers n ~ m. In practice the products ob-
talned by ethoxylatlon are mixtures, i.e. the numbers given
for the degree of ethoxylatlon of the above-described products
; o~ rormula I slgnlfy the average degree of ethoxylation for
the products mlxture, and are used as such.
In a further aspect this invention provides a process
~or produclng the new substances of formula I, which con~prises
~eacting a 1,2-epoxyalkane of formula II
R-CH-CH2 (II)
` O
wherein R has the signification as given in formula I, at 20
to 150C, with at least an equimolar amount of an amine Or
rormula III
R
s \ R (III)
.
4-- .
.
~049~4Z
wherein Rl has the same signiflcance as ln formula I, and R2
represents hydrogen or the group Rl, rollowing this reaction
separating off the surplus amine, addlng to the product thus
obtalned, which may be dried, catalytlc amounts of an al~alin~
ethoxylatlon catalyst such as an alkali metal alcoholate, pre-
ferably elther an alkali metal alcoholate of the previous re-
actlon product or a lower alkanolate, such as the methylate,
and reactlng under pressure wlth ethylene oxide preferably in
an lnert gas atmosphere, untll the calculated amount of ethy-
lene oxlde (2 to 20 mols) has been reacted.
The amlne Or formula III can be used ln gaseous phase
or ln an aqueous solutlon. An excess amount Or amlne, whlch
may be up to 10 tlmes the molar amount, based on one mol Or
the epoxide of formula II, is recommended, especially when a
prlmary amlne is used (R2 s H in formùla ~II). As the excess
amount Or a primary amine increases~the rormatlon Or the
adduct, comprislng 2 mols of epoxlde and 1 mol of prlmary
amlne, ls suppressed to a greater and greater extent. or
course, lt has been round that the presence Or thls by-product
is ln no way dlsadvantageous, and that technlcal ethoxylation
; products, up to 20% Or whlch comprise ethoxylatlon derlvatives
Or thls by-product, have the same valuable properties as the
purlPled ethoxylatlon product accordlng to formula I. Thls
by-product of 2 mols Or epoxlde and 1 mol o~ primary amine
ls belleved to have the formula
Rl
R-CH-CH2-N-CH2-fH-R
OH OH
_5_
.
104904;~
nd both s~condary hydroxyls would undergo ethoxylation in
the ethoxylation step.
The 1,2-epoxy alkanes of formula II, which can be
used in accordance with the invention, can be obtained in a
known manner by epoxidation of the corresponding terminal
olefins. Examples of epoxides which are preferably used are
the compounds: 1,2-epoxy-octane, 1,2-epoxydecane, 1,2-epoxy-
dodecane, 1,2-epoxytetradecane, 1,2-epoxyhexadecane, 1,2-
epoxyoctadecane, 1,2-epoxyeicosane and the epoxide mixtures
which can be obtained from olefins produced by cracking,
h C to C -1,2-epoxide, Cll to C15
Cl5 to Cl8-1,2-epoxide.
Examples of suitable primary and secondary amines
of formula III are the compounds: methylamine, ethylamine,
propylamine, isopropylamine, butylamine, isobutylamine, dimethyl-
amine, diethylamine and diisopropylamine.
The invention further relates to the use of the ethoxy-
lation products of formula I in washing and cleansing agent com-
positions which are present in solid form, as pastes, or as
dispersions or solutions and comprise a content of at least one
other active washing agent component from the group of the anionic
and non-ionic surface-active agents and/or the organic and
inorganic builder salts. These washing and cleansing agent
compositions are characterized in that they contain the ethoxy-
lation products of formula I in quantities of from 0.5% to 40%
by weight.
If the washing agent compositions of the invention
are solid, they are usually present as fine or granular powders,
as agglomerates or granulates. Such preparations can be
.~ , .
~ - 6 -
. . .
~04904Z
practically anhydrous, or they may contain water of crystal-
llzatlon or hydration. The preparations of the invention can
be used also in pastes, dispersions, or solutions. These
then contain smaller or larger amounts of solvents, such as
water or water-soluble organic solvents, in which the other
constituents are dissolved partially or completely. Thus,
for certainclean~n-g purposes, solutions can be used which
contain up to 1%, preferably up to 4%, by weight of the solid
composition.
The lnventlon therefore also relates to an improve-
ment ln the process for washing of textiles which comprises
contacting soiled textiles with an aqueous solution containin-~
surface-active compounds, builder salts and soil suspension
agents for a time and at a temperature sufficient to disperse
or dissolve said soil from sald soiled textiles ln said
aqueous solution, separating said textiles, rinslng and dry-
ing sald textiles and recovering cleaned textiles,thelmprove-
ment consisting of employlng from 0.05 to 12 gm/liter of the
secondary alcoholamlne ethoxylates of the invention, in said
aqueous solution as part of said surface-active compounds and
soil suspension agents.
Solid washing agents in which the ethoxylation product
of formula I can be used together with anionic surface-active
compounds of the sulfonate and sulfate type, according to the
invention are characterized by the following composition:
1% to 12% by weight of ethoxylation products of formula I,
0 to 12% preferably 3% to 10%, by weight of at least one
anionic surface-active compound of the sulfonate
and/or sulfate type, and possibly of at least one
,
--7--
.~
i
1049042
non-ionic surface-a.ctive compound which differs from
the products of formula I,
0 to 6% by welght of a foam-inhibiting soap and/or non-sur-
face-active foam inhibitor,
40% to 88% by weight of an organic and/or inorganic builder
salts and optionally, a bleaching component, and
0 to 20% preferably 0.5% to 10%, by weight Or other common
washing agent composition constituents such as
optical brighteners, foam regulators, enzymes, soil
suspension agents, textile softeners, antimicrobial
agents, dyes, perfume and water.
In order to obtain readily pourable, powdery prepara-
tions, the new ethoxylation products, which at room tempera-
ture are fluid or paste-like, are advantageously applied to
the powder particles of the other constituents of the prepara-
.,
tlon, for example by spraylng onto some of the builder salts,
such as sodlum tripolyphosphate and sodium sulfate types with
bulk densltles of 200 to 500 gm/liter, which are particularly
: suitable for this purpose or onto the sodium perborate of the
preparations containing bleaching agent.
The use according to invention of the secondary alco-
holamine ethoxylates of formula I in liquid cleansing agents .-
is preferably in preparations of the following composition:
5% to 40% by weight of the secondary alcoholamine ethoxylates
. of formula I,
~i. 0.5% to 40% by weight of at least one other organic or inor-
ganic substance having a cleansing effect, in parti-
cular
. 0.5% to 15% by weight of at least one anionic surface--active
,;
--8--
104904Z
compound of the sulfonate and/or sulfate type or
soap and/or
0.5% to 25% by weight of at least one organic and/or lnorganlc
builder salt,
40% to 94.5% by weight of water and possibly water-soluble
organic solvents,
0 to 10% by weight of other common liquid washing agent con-
stituents, such as solution aids, optical brightener~
fat restoring agents, soil suspension agents, opacl-
flers, antimicroblal agents, enzymes, perfume and
dyes.
The composltlon of the washlng agents with a content of
- ethoxylation products of formula I depends largely on the pur-
pose of their use. Preparations whlch are used preferably as
prewashlng agent composltlon, as also the bolllng or full
washlng agent composltlons, have a pH of between 9.5 and 11 in
1% aqueous solution. Thls is usually obtalned by a hlgher
oontent of basic reacting bullder salts. The preparations
suitable as fine washing agent composltions are usually neu-
~i
tral to weakly alkaline (pH 7 to 9.5) ln lZ aqueous solutlon,
but sometlmes weakly acid (pH 6 to 7). The boillng or full
washing agent compositions differ from the other preparations
`` also by their content of a bleaching component, which conslsts
of a peroxy-compound as active oxygen carrier, in particular
sodium perborate, stabilizersandpossibly activators for the
peroxy-compound, and which may amount to 10% to 40%, prefera-
bly 15% to 35g, by weight of the total washing agent. The
stabilizers are employed in amounts of from 0 to 30% byweight
-~ of the bleaching component and the activators for the peroxy-
_ g_
1049042
compound are employed in amounts of from 0 to 40% by welght
of the bleaching components.
In the following, the other constituents contained in
the washing andcleansing agent compositions besides the active
substances according to the invention will be described in
greater detail, arranged by substance class.
The anionic and non-ianic surface-active compounds or
tensides contain in the molecule at least one hydrophobic
organic moiety and one water-solubilizing, anionic or non-
lonlc group. the hydrophobic molety ls mostly an allphatic
hydrocarbon radlcal with 8 to 26, pre~erably 10 to 22 and
particularly 12 to 18 carbon atoms or an alkyl aromatlc radl-
cal, such as alkylphenyl, with 6 to 18,preferably 8 to 16
aliphatlc carbon atoms.
Among the anionic surface-active compounds are, ~or
example, soaps of natural or synthetic, preferably saturated,
~; fatty acids, optlonally, also, soaps of resinic or naphthenlc
acld~. Sultable synthetic anionic tensides are those of the
type of the sul~onates, sulfates and synthetic carboxylates.
Suitable anionic tensides of the sulfonate type are
alkylbenzene sul~onates (C9_15 alkyl), mixtures of alkene-
sul~onates and hydroxyalkanesul~onates, as well as alkane-
dlsul~onates, as they are obtained, ~or example, from mono-
` ole~lns wlth termlnal or non-termlnal double bonds by sulfon-
ation wlth gaseous sul~ur trloxide and subsequent alkaline or
acld hydrolysis of the sulfonation products. Also suitable
are alkanesulfonates whlch are obtained from alkanes by sul-
fochlorination or sul~oxidation and subsequent hydrolysls or
neutralization or by bisulfite addition to ole~ins. Other
--10--
-
1049042
suitable tensides of the sulfonate type are the esters of
~-sulfofatty acids, ror example, the ~-sulfonic acids of
hydrogenated methyl or ethyl esters of coconut, palmkernel or
tallow fatty acids.
Suitable tensides of the sulfate type are the sulfuric
acid monoesters of primary alcohols (e.g. from coconut fatty
alcohols, tallow fatty alcohols or oleyl alcohol) and those
of secondary alcohols. Also suitable are sulfated fatty acid
alkanolamides, sulfated fatty acid monoglycerides or sulfated
reaction products of 1 to 4 mols of ethylene oxide with prim-
ary or secondary fatty alcohols or alkylphenols.
Other suitable anionic tensides are the fatty acid
esters or amides of hydroxy- or amino-carboxyllc acids or sul-
fonic acids, such as the fatty acid sarcosides, fatty acid
glycolates, fatty acid lactates, fatty acid taurides or fatty
`~ acid isoethionates.
The anionic tensides can be present in the form of the
alkali metal salts, such as the sodium or potassium salts,the
ammonium salts, as well as soluble salts of organic bases,such
; 20 as the lower alkylolamines, for example, mono-, di- or tri-
ethanol amine.
Suitable non-ionic surface-active compounds or tenside
are the addition products of 4 to 40, preferably 4 to 20 mols
of ethylene oxide to 1 mol of a fatty alcohol, alkylphenol,
fatty acid, fatty amine, fatty acid amide or alkane-sulfon-
amide. Partlcularly important are the addition products of
; 5 to 16 mols of ethylene oxide to coconut fatty alcohols or
tallow fatty alcohols, to oleyl alcohol or to secondary alk-
anols with 8 to 18, preferably 12 to 18 carbon atoms, as well
--11--
104904Z
as mono-alkylphenols or dialkylphenols with 6 to 14 carbon
atoms in the alkyls. In addition to these water-soluble non-
lonics, polyglycol ethers with 1 to 4 ethylene glycol ether
radlcals in the molecule, which are insoluble or not complete-
ly water-soluble, are also of interest, particularly if they
are used together with water-soluble non-ionic or anionic
tensides.
Furthermore, the water-soluble addition products of
20 to 250 mols of ethylene-oxide to polyoxypropylene glycol
contalnlng 10 to 100 propylene glycol ether groups (Pluronics
), to alkylenediamine-polyoxypropylene glycol (Tetronics
Q, and to alkylpolyoxypropylene glycols wlth 1 to 10
carbon atoms in the alkyl chain, can also be used where the
polyoxypropylene glycol chain acts as a hydrophobic radical.
Non-lonlc tensldes of the type of the amine oxides or
sulfoxides can also be used.
; The foamlng power of the tenslde can be lncreased or
reduced by combination of suitable tenslde types. A reduc-
tlon can also be achieved by additions of non-surface-active
organic substances.
Suitable foam stabilizers, particularly ln tensides of
the sulfonate or sulfate type, are surface-active carboxy or
sulfobetaines, as well as the above-named non-lonlcs of the
alkylolamide type. Moreover, fatty alcohols or higher termin-
al diols have been suggested for this purpose.
A reduced foaming power, that is desirable for the use
in washing machines, is often attained by combination of dif-
ferent-tenside types, such as of sulfate and/or sulfonates
with non-ionics, and/or with soaps. In soaps, the foam lnhi-
-12-
104904Z
bition increases with the degree of saturation and the number
of carbons in the fatty acid residue. Soaps derived from sat-
urated C20 24 fatty acids have been proven good as foam ln-
hlbltors.
The non-tenslde foam lnhibitors include N-alkylated
amlnotrlazines, optlonally containing chlorine, whlch are
obtalned by the reaction of l mol of cyanuric acid chloride
wlth 2 to 3 mols of a mono- and/or dialkylamlne with 6 to 20,
preferably 8 to 18 carbon atoms in the alkyl radicals. Slml-
larly effectlve are propoxylated and/or butoxylated amlno-
trlazines, such as, products that are obtalned by the addl-
tlon of from 5 to lO mols of propylene oxlde to l mol of
; melamine and further additlon of from lO to 50 mols of buty-
lene oxide to this propylene-oxlde derivatlve.
Likewise sultable as non-tenslde foam lnhibltors are
water-insoluble organic compounds, llke paraffin~, or halogen
ated paraffins wlth meltlng polnts below 100C, aliphatic
Cl8 to C40 ketones, as well as allphatlc carboxylic acld
esters whlch contain ln the acid or alcohol residue, optional-
ly, also ln both of these resldes, at least 18 carbon atoms
(such as trlglycerldes or fatty acld fatty alcohol esters).
A These compounds can be used to rceiduc foamlng, partlcularly
ln combinatlons of tensldes of the sulfate and/or sulfonate
type wlth soaps.
Partlcularly low-foamlng non-lonlcs, whlch can be used
elther alone or ln comblnation wlth anionlc, amphoterlc and
non-ionlc tensides, and which reduce the foamlng power of high
foamlng tensldes, are the addltlon products of propylene oxide
on the above-described surface-actlve polyoxyethyleneglycol
:`
, ~
.. . - ;. -
1049042
ethers as well as the likewise described addition products of
ethylene oxide to polyoxypropylene glycols and to alkylene-
diamlne polyoxypropylene glycols or to alkyl polyoxypropylene
glycols having l to lO carbonsin the alkyl.
Weakly acid, neutral or alkaline-reacting inorganic
or organic salts can be used as builder salts. The builder
salts are salts capable of complexing calcium ions or preci-
pitating them, preferably the salts are the alkali metal
salts.
Of special importance are the lnorganlc salts capable
of complexing or sequestering calcium, such as the water-sQlu-
ble alkali metal condensed phosphates, such as the alkali
~A metal ~ç~Y}phosphates or alkali metal polyphosphates, in
particular pentasodium tripolyphosphate. These phosphates~ag
be replaced wholly or partially by organic builder salts cap-
able of complexing calcium ions, preferably the alkali metal
salts. These organlc sequesterlng agents lnclude compounds
of the following classes:
l. The aminopolycarboxylic acids, such as amino-lower-
alkanolc acids and polyamino-lower-alkane-poly-lower-alkanoic
aclds, for example, nitriloacetic acid, ethylenediaminetetra-
acetic acid, diethylenetriaminepentaacetic acid, as well as
higher homologs.
2. The lower alkane polyphosphonic acids, such as
methane diphosphonic acid.
3. The amino- and hydroxy-substituted alkane poly-
phosphonic acids, having l to 9 carbon atoms, such as l-amino-
ethane-l,l-dlphosphonic acid, amino-tri-methylene-phosphonic
~` acid, methylamino- or ethylamino-di-methylene-phosphonic acid,
; 3 ethylene diaminetetra-methylenephosphonic acid, dimethylamino-
ethane-l,~diphosphonic acid, l-hydroxy-ethane-l,l-diphosphonic
acid, etc.
-14-
104904Z
4. The phosphonoalkane polycarboxylic acids with 1 and
2 phosphono and 2 and 3 carboxyl groups and 4 to 9 carbon atoms,
such as l-phosphonoethane-1,2-dicarboxylic acid, 2-phosphonopro-
pane-2,3-dicarboxyllc acid, 1,1-diphosphonopropane-2,3-dicarboxy-
lic acld, 2-phosphonobutane-1,2,4-tricarboxylic acid, 2-phosphono-
butane-2,3,4-tricarboxylic acid, etc.
Of special importance are the nitrogen-free and phos-
phorus-free polycarboxylic acids forming complex salts with cal-
cium ions, which include also carboxyl group-containing polymers.
These organic sequestering agents, particularly in the form of
their alkali metal salts include compounds of the following
classes:
5. Hydroxyalkanepolycarboxylic acids having from 4 to
12 carbon atoms and cyclic polycarboxylic acids having from 4 to
12 carbon atoms, such as citrlc acid, tartaric acid, benzenehex-
acarboxylic acid and tetrahydrofurantetracarboxylic acid.
o~y~56~CC;n~`~
6. 2,2'-hy~r~ diauooln~c acid and carboxymethyloxy-
succlnlc acld.
7~ The carboxymethylated, polyhydrlc C2 to C6 alcoho~s
. 20 and C3 to C6 hydroxycarboxylic acids, containing at least two
carboxyl groups in the molecule, preferably the carboxymethyl
derlvatives of alkanepolyols having 2 to 6 carbon atoms and hydr-
oxyalkane-carboxylic acids having 3 to 6 carbon atoms, such as
the ~ompounds: dicarboxymethyl-ethylene glycol and dicarboxy-
methyl-diethylene glycol, tricarboxylmethyl-glycerine, mono- and
. dlcarboxymethyl-glyceric acid, carboxymethyl-tartronic acid, car-
boxymethyl-methyl-tartronic acid, carboxymethyl-maleic acid, mono-
and di-carboxymethyl-tartaric acid, also the carboxymethylated 7
derivatives of glutaric acid~saccharic acid, mucic acid, gluconic
30 acid, the erythritols, pentaerythritol, 2,2-dihydroxymethyl-pro-
panol, sorhitol, mannitol, xylitol, etc.
104904Z
8. The polymeric carboxylic acids with molecular
welghts over 350, and at least one carboxyl group per each
molecular welght unit of 175, such as polyacrylic acid, poly
-~-hydroxyacrylic acid, the polycarboxylic acids obtained
from mixed polymerization of maleic acid anhydride with ethy-
lene or propylene, isobutylene or styrene, or with vinyl
methyl ether or furan, or with acrylic acid, as well as the
polyhydroxy-carboxylic acids obtained from acrolein and acry-
llc acld with H2O2 and the Cannizzaro reaction, etc.
Suitable lnorganic,non-complex-forming salts are the
dicarbonates, carbonates, borates, sulfateg or sllicates o~
the alkali metals. The most suitable of the alkali metal
silicates are the sodium sillcates with a ratio of Na20 to
S102 of 1:1 to 1:3.5.
Other builder salts, which because of their hydrotropic
properties, are usually utilized in liquid composltlons are
the alkall metal salts of organic non-surface-active sul-
fonlc aclds, carboxyllc aclds and sulfocarboxyllc acids con-
talnlng from 2 to 9 carbon atoms. These lnclude, for example,
water-soluble alkall metal salts of alkenesulfonlc acld,
benzenesulfonlc acid, toluenesulfonic acid, or xylenesulfonic
acid or cumenesulfonic acid, water soluble alkali metal
;~ salts of sulfoacetic acid, sulfobenzoic acid, sulfophthalic
acid or of succinic acid as well as the corresponding salts
of acetic acid or lactic acid. In addition, as further solu-
tion aids, acetamide and urea may be employed.
`~ In addition to the active secondary alcohol amine
ethoxylates of formula I according to the invention, addition-
al soil suspension agents or dirt carriers may be employed,
-16-
~04904Z
whlch keep the dirt released from the fibers in suspension in
the liquor and so prevent graying. Suitable compounds are water-
soluble collolds, mostly of an organic nature, such as the water-
soluble salts of polymeric carboxyllc acids, glue, gelatin, salts
of ether carboxylic acids or ether sulfonic acids of starch or
cellulose,or salts of acid sulfuric acid esters of cellulose or
starch. Water-soluble polyamides containing acid groups are also
suitable for this purpose. Furthermore, soluble starch prepara-
tions and other than the above-mentioned starch products can be
used~ for example, degraded starches, aldehyde starches, etc.
Polyvinyl pyrrolidone can also be used.
Among the compounds serving as bleaching agents and
releasing H22 in water, sodium perborate tetrahydrate (NaB02.
H203. 3 H20) and the monohydrate (NaB02. H202)are of particular
importance. But also other H202 releasing borates can also be
used, such as perborax Na2B407 . 4 H20. These compounds can be
replaced partly or completely by other carriers of active oxygen,
particularly by peroxyhydrates, such as peroxycarbonates, (Na2C03-
1.5 H202), peroxypyrophosphates, citrated perhydrates, urea-H202
compounds, as well as by H202-releasing peracid salts, such as
Caroates (XHS05), perbenzoates or peroxyphthalates.
It is recommended to incorporatewater-soluble and/or
water-insoluble stabilizers for the peroxy compounds together
with the latter in amounts of 0.25% to 10% by weight. Water-
insoluble stabilizers, which amount to 1% to 8%, preferably 2%
to 7% of the weight of the entire preparation are, for example,
silicate
the magnesium/having a MgO: SiO2 ratio of 4:1 to 1:4, prefera-
bly 2:1 to 1:2, and particularly 1:1, which are mostly obtained
` by precipitation from aqueous solutions. In their place, other
alkaline earth metal, cadmium or tin silicates of corresponding
.~ .
-17-
1049042
compositions are also usable. Also hydrous oxides of tin are
suitable as stabilizers. Water-soluble stabilizers, which can
be present together with water-insoluble stabilizers, are mostly
the organic sequestering agents which can be added in amounts of
0.25% to 5%, preferably 0.5% to 2.5% of the weight of the entire
preparation.
In order to obtain a satisfactory bleaching effect
when washing at temperatures below 80C, particularly in the
rangé of 60 to 40C, activator-containing bleaching components
are preferably incorporated in the preparations.
Certain N-acyl and/or 0-acyl compounds forming, with
H202, organic per acids serve as activators for per compounds
releasing H202 in water. Particularly to be mentioned are
acetyl, propionyl or benzoyl compounds, as well as carbonic acid
or pyrocarbonic acid esters. Suitable compounds are among others:
the N-diacylated and N,N'-tetraacylated amines, such as N,N,N'N'-
tetraacetyl-methylenediamine, N,N,N',N'-tetraacetyl-ethylene-
diamlne, N,N-diacetyl-anlline and N,N-diacetyl-p-toluidine, or
the 1,3-diacylated hydantoins and alkyl-N-sulfonyl-carbonamides,
such as N-methyl-N-mesyl-acetamide, N-methyl-N-mesyl-benzamide,
N-methyl-N-mesyl-p-nitrobenzamide, and N-methyl-N-mesyl-p-methoxy
benzamide, the N-acylated cyclic hydrazides, acylated triazoles
or urazoles, such as monoacetyl maleic acid hydrazide, the 0,N,N
-trisubstituted hydroxylamines, such as 0-benzoyl-N,N-succinyl-
hydroxylamine, 0-acetyl-N,N-succinyl-hydroxylamine, 0-p-methoxy-
benzoyl-N,N-succinyl-hydroxylamine, 0-p-nitrobenzoyl-N,N-succinyl-
hydroxylamine and 0,N,N-triacetyl-hydroxylamine, the N,N'-diacyl-
sulfuryl-amides, auch as N,N-dimethyl-N,N'-diacetyl-sulfurylamide,
and N,N'-diethyl-N,N'-diethyl-N,N'-dipropionyl-sulfuryl amide,
the triacyl cyanurates, such as triacetyl cyanurate or tribenzoyl
.
-18-
~049042
cyanurate, the carboxylic acid anhydrides, such as benzoic acid
anhydride, m-chlorobenzoic acid anhydride, phthalic acid anhyd-
ride, 4-chlorophthalic acid anhydride, the sugar esters, such as
glucose pentaacetate, the 1,3-diasyl-4,5-diacyloxyimidazolidines,
for example the compounds 1,3-diformyl-4,5-diacetoxy-imidazoli-
dine, 1,3-diacetyl-4,5-diacetoxy-imidazolidine, 1,3-diacetyl-
4,5-dipropionyloxy-imidazolidine, the acylated glycolurils, such
as tetrapropionyl glycoluril or diacetyl-dibenzoyl glycoluril,
the diacylated 2,5-diketopiperazines, such as 1,4-diacetyl-2,5-
diketopiperazine, 1,4-dipropionyl-2,5- diketopiperazine, 1,4-
dipropionyl-3,6-dimethyl-2,5-diketopiperazine, the acetylated or
benzoylated products of propylene-diurea or 2,2-dimethyl-propyl-
~ ene diurea [2,4,6,8-tetraazabicyclo-(3,3,1)-nonane-3,7-dione or
;~ its 9,9 dimethyl derivatives], and the sodium salts of p-ethoxy-
carbonyloxy)-benzoic acid and p-(propoxycarbonyloxy)-benzene sul-
fonic acid.
The actlvated chlorine compounds servlng as bleachlng
agents can be of an lnorganlc or organic nature.
The lnorganic active chlorine compounds include alka-
line metal hypochlorites, which can be used particularly in theform of their mixed salts or addition compounds with orthophos-
phates or on condensed phosphates such as with alkali metal
pyrophosphates and polyphosphates, or with alkali metal silic-
ates. If the washing agents and washing assistant compositions
contain mono-persulfates and chlorides, active chlorine is formed
in aqueous solution.
The organic active-chlorine compounds which can be
used are particularly the N-chloro compounds, where one or two
chlorine atoms ar linked to a nitrogen atom, the third valence
of the nitrogen atoms leading preferably to a negative group,
. ~
-19-
. ~ ~
104904Z
particularly to a C0- or SO2-group. These compounds lnclude
dichlorocyanuric acid and trichlorocyanuric acid or thelr salts,
chlorlnated alkylguanldes or alkylbiguanides, chlorinated hydan-
toins and chlorlnated melamines.
The washing agents can contain optical brighteners
such as those for cotton, particularly derivatives of diamino-
stilbenedisulfonic acid or its alkali metal salts. Suitable
are, for example, salts of 4,4'-bis-(2-anilino-4-morpholino-1,
3,5-triazin-6-yl-amino)-stilbene-2,2'-disulfonic acid or simllar-
ly compounds which have instead of the morpholino group, a dieth-
anolamino group, a methylamino group or a 2-methoxy-ethylamino
- group. Brighteners for polyamide fibers which can be used are
those of the type of the 1,3-diaryl-2-pyrazolines, for example,
the compound l-(p-sulfamoylphenyl)-3-(p-chlorophenyl)-2-pyrazo-
line, as well as compounds of similar composition which have in-
stead of the sulfamoyl group, for example, the methoxycarbonyl
group, the 2-methoxyethoxycarbonyl group, the acetylamino group
or the vinylsulfonyl group. Sultable polyamide brighteners are
also the substltuted aminocumarins, for example, 4-methyl-7-
dimethylamino-cumarin or 4-methyl-7-diethylaminocumarin. Further-
more, the compounds 1-(2-benzimidazolyl)-2-(1-hydroxyethyl-2-ben-
zimidazolyl)-ethylene and l-ethyl-3-phenyl-7-diethylamino-carbo-
styril can also be used as polyamide brighteners. Brighteners
for polyester and polyamide fibers which can be used are the
i compounds 2,5-di-(2-benzoxazolyl)-thiophene,2-(2-benzoxazolyl)-
naphtho-[2,3-b]-thiophene and 1,2-di-(5-methyl-2-benzoxazolyl)-
ethylene. Furthermore, brighteners of the type of the substitu-
ted 4,4'-distyryl-diphenyls can be utilized,for example, the com-
pound 4,4'-bis-(4-chloro-3-sulfostyryl)-diphenyl. Mixtures of
the above-mentioned brighteners can likewise be used.
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~04904Z
The enzyme preparations to be used are mostly a mix-
ture of enzymes with different effects, such as proteases, car-
bohydrases, esterases, lipases, oxidoreductases, catalases,
peroxidases, ureases, isomerases, lyases, transferases, desmol-
ases, or nucleases. Of particular interest are the enzymes,
obtained from bacteria strains or from fungi, such as Bacillus
subtilis or Streptomyces griseus, particularly proteases and amy-
lases, which are relatively stable towards alkalis, percompounds,
and anionic tensides and are still effective at temperatures up
to 70C.
Enzyme preparations are marketed by the manufacturers
mostly as aqueous solutions of the active substances or as
powders, granulates or as cold-sprayed products. They frequently
contain sodium sulfate, sodium chloride, alkali metal ortho-,
pyro- and polyphosphates, particularly tripolyphosphates, as
fillers. Dust-free preparations are particularly valued. These
are obtained in a known manner by incorporating of oily or pasty
Non-ionics or by granulation with the aid of melts of water-of-
crystallization-containing salts in their own water-of-crystalli-
zation.
Enzymes may be incorporated which are specific for
certain types of soil, for example, proteases or amylases or
lipases. Preferably, combinations of enzymes with different
effects are used, particularly combinations of proteases and
amylases.
The organic solvents utilized in the liquid washing
agent compositions of the invention as liquid carriers are water-
soluble or emulsifiable with water, aliphatic organic solvents
, having no more than 7 carbon atoms, particularly alkanols and
alkanediols having from l to 5 carbon atoms, esters thereof with
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104904Z
~o
A alkanoic acids having ~r more than 4 carbon atoms and ethers
thereof with hydroxyalcohols having no more than 4 carbon atoms,
ror example, methanol, ethanol, propanol, isopropanol, butanol,
amyl alcohol, ethylene glycol, diethylene glycol, triethylene
glycol, propylene glycol, butylene glycol, ethyl acetate, etc.
In addition alkanones having 3 to 7 carbon atoms may be employed,
such as acetone and methylethyl ketone. The water-soluble sol-
vents are preferred.
In addition, where required to give the desired pH of
the 1% aqueous solution of the washlng compositions of the in-
vention, water-soluble inorganic wash alkalis are employed.
These wash alkalis are the bicarbonates, carbonates, borates or
-~ silicates of the alkali metals, and alkali metal sulfates.
Suitable antimicrobial substances with a bactericidal,
bacteriostatic or fungicidal or fungistatic action and which are
water-soluble as such or in the form of their salts can be em-
ployed in the powdery compositions of the invention. Among these
are the quaternary ammonium compounds which contain in the mole-
` cule one long-chained aliphatic and two short-chained aliphatic
hydrocarbon radicals, and an aromatic organic radical linked over
an aliphatic carbon atom with the nitrogen atoms, or an aliphatic
radical with double bonds, such as dimethyl-benzyl-dodecyl ammon-
ium chloride or dibutyl-allyl-dodecyl ammonium chloride. Suit-
able active substances are also the bromo and nitro substituted
alkanols and alkanediols having 3 to 5 carbon atoms, for example,
2-bromo-2-nitropropane-1,3-diol, 1-bromo-1-nitro-3,3,3-trichloro
-2-propanol, 2-bromo-2-nitro-butanol, as well as phenolic com-
pounds of the type of the halogenated phenols, the halogenated
alkylphenols, halogenated cycloalkylphenols, halogenated aralkyl-
; 30 phenols, and halogenated phenylphenols, the halogenated alkylene
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104904Z
bisphenols, the halogenated hydroxybenzoic acid derivatives, and
the preferably halogen-substituted phenoxyphenols, such as 2-
hydroxy-2',4,4'-trichloridiphenyl ether. Suitable for preserva-
tion of the liquid preparations as antimicrobial substances are
also, for example, formaldehydes as an aqueous solution, benzoic
acid, salicylic acid and sorbic acid.
The following examples are illustrative of the pract-
ice of the invention without being limitative in any respect. In
the following examples EO stands for ethylene oxide and the number
preceeding it, the mols of ethylene oxide adducted to the second-
ary alcoholamine.
EXAMPLE 1 -
Preparation of methylamino-2-hydroxyhexadecane . 10 EO
371 gm of 1,2-epoxyhexadecane (1.5 mols) was mixed
with 1175 gm of a 40% aqueous solution of methylamine (15 mols)
and stirred for 5 hours at 130C in an autoclave. Cooling was
then effected and the crystalline methylamino-2-hydroxyhexade-
cane was filtered off. After vacuum drying the yield of this
intermediate product was 97~.
For the ethoxylation process 271 gm (1 mol) of the
dried, anhydrous intermediate product wasmixed in an autoclave
with 2.5 gm of sodium methylate and reacted at 120C in a nitro-
gen atmosphere with 440 gm of ethylene oxide (10 mols), the ethy-
lene oxide being empressed into the autoclave in portions with
nitrogen. The amount of ethylene oxide used was absorbed after
5 hours. The ethoxylation product thus obtained was in the form
of a yellow fluid having a turbidity point of 56C.
EXAMPLE 2
. .
:,
., .
.: .
1049042
Preparatlon of diethylamino-2-hydroxydodecane-tetradecane .8 E0
483 gm of a technical 1,2-C12 C14 epoxide (2.5 mols)
was stirred together with 493 gm of a 40% aqueous diethylamine
solution (2.7 mols) in an autoclave for 5 hours at 150C. When
cooling to room temperature had been effected, the aqueous phase
was separated off andtheorganic phase was purified by distilla-
tion. The epoxide amine adduct distilled at 110 to 116C and
0.04torr. Yield: 85%.
The ethoxylation with 8 mols of ethylene oxide was
carried out in accordance with the manner described in Example
l; turbidity point of the ethoxylation product 44C.
The additives of the invention listed hereinafter
in Table were produced in an analogous manner.
-24-
.,~ ~ , - .
1049042
TABLE 1
_......... , . _ .__._
Example Additive Turbidity
point in C
.__
3 Methylamino-2-hydroxy-
dodecane . 6 EO 27
4 Methylamino-2-hydroxy-
dodecane . 8 EO 56
: 5 Methylamino-2-hydroxy-
dodecane . 10 EO 70
6 Methylamino-2-hydroxy-
hexadecane . 8 EO 43
7 Methylamino-2-hydroxy-
: eicosane . 8 E0
: ~ 8 Methylamino-2-hydroxy- .~
; . ~ e~cloDanc . 10 EO ~o .,
, ~ e,cosa n~
9 Butylamino-2-hydroxy- :
octane . 6 EO
Methylamino-2-hydroxy-
docosane . 12 E0
.~ 11 Ethylamino-2-hydroxy-
.. octadecane . 20 EO
12 Dimethylamino-2-hydroxy-
decane . 2 E0 ~0
13 Dimethylamino-2-hydroxy-
. C15-C18 alkane . 8 EO
14 Methylamino-2-hydroxy-
C15-C16 alkane . 11 EO 68
: 15 Methylamino-2-hydroxy-
C17-C18 alkane . 15 EO
.,
:
' .
-25-
1049042
The following Examples 16 to 21 of Table 2 describe
wasn~ng and cleansingagent compositions utilizing the new active
substances of Formula I. The preparation of Examples 16 and 17
are utilized as full washing agent compositions. That of Example
18 is utilized as a fine washing agent composition. That of
Example 19 is utilized as a prewashing agent composition. That
of Example 20 is utilized as a fluid washing agent composition
and that of Example 21 is utilized as a powdery cleansing agent
composition.
In the listing of compounds in the preparations of the
Examples in Table 2, the abbreviations or designations have the
following significance. The various compounds capable of forming
salts are employed in the form of the sodium salt unless other-
wise indicated.
"ABS" - the salt of alkylbenzenesulfonic acid with 10
to 15, preferably 11 to 13 carbon atoms, in the alkyl chain,
obtained by condensation of straight-chain terminal olefins with
benzene and sulfonation of the thus-formed alkylbenzene,
"Alkanesulfonate" - a sulfonate obtained from paraf-
fins with 12 to 16 carbon atoms by sulfoxidation,
"Olefinsulfonate" - a sulfonate obtained from olefin
mixtures with 12 to 18 carbon atoms by sulfonation with SO3 and
hydrolysis of the sulfonation product with aqueous sodium hydro-
xides. The olefinsulfonate consists substantially of alkene-
sulfonate and hydroxyalkanesulfonate, and contains, however, also
a slight amount of alkanedisulfonates,
` "Fs-estersulfonate" - a sulfonate obtained from the
methyl ester of a hardened tallow fatty acid, by sulfonation
" with SO3,
"CA-EO-sulfate" - the salt of the sulfated addition
product of 2 mols of ethylene oxide to 1 mol of coconut fatty
alcohol (C12 to C14);
~26-
1049042
"Soap" - the salts derived from fatty acid mixtures of
an iodine number of 4, whose composition was 21% by weight of
C12, 8% by weight of C14, 4% by weight of C16, 22% by weight of ~:
C18, 8% by weight of C20, and 37% by weight of C22, whereby the
soap has a foam inhibiting effect due to the increased average
carbon number,
"Foam Inhibitor" - a mixture of about 45% of a N,N'-
di-(alkylamino)-chlorotriazine and about 55% of a N,N'N"-tri-
(alkylamino)-triazine, where the alkyls in their triazine deri-
~ 10 vatives are a mixture of homologs containing from 8 to 18 carbon ~ :
atoms,
"NTA" or "EDTA" - the salts of nitrilotriacetic acid
or ethylenediaminetetraacetic acid,
"Perborate" - a product of the approximate composition
NaB02.H202.3 H20, containing about 10% of active oxygen,
"CMC" - the salt of carboxymethylcellulose having a
substitution degree of 0.7 to o.8.
In place of the given compounds of formula I indicated
in Table 2, other described compounds of formula I can be employ-
ed with comparable results.
As constituents of the preparation in Table 2, theethoxylation products of the formula I have a substantially im-
proved washing out capacity for hydrophobic dirt as compared with
~ known surface-active ethoxylation products. This is demonstrat-
ed, for example, on collars and cuffs of shirts and on badly
. soiled professional garments, such as those of kitchen staff,
butchers, car mechanics etc.
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1049042
TABLE 2
ConstituentsWashing agent constituents in % by weight
__ for examples
16 17 18 19 20 21
ABS 7.0 _ 3.o _ ~5.8
FS-estersulfonate _ 6.0 _ _ _
Alkanesulfonate _ _ _ _ 6.0
Olefinsulfonate _ _ _ _ _1.0
CA-EO-sulfate _ _ 4.0 _ _1.0
Soap 3.5 3-5 3.o _ _1.2
Potassium toluene-
sulfonate _ _ _ _ 4.0
Foam inhibitor _ o.5 _ _ _
Additive No. 4 3-5 _ 1.0 _ 2.0
Additive No. 1 _ 4.0 _ 6.0 _2.0
Additive No. 2 _ _ 3~ 4.0 _
Na5P3010 45.0 20.0 40.0 40.0 _10.0
NTA _ 7.o _ _ _
K4P27 _ _ _ _ 20.0
__ . _ .
EDTA 0.2 0.25 _ 0.2 _
Perborate 24.0 28.0 _ _ _
Water glass 1:3.3 3-5 3.o 3.o 4.5 _ 5.o
Sodium Carbonate _ _ _ 5.o _39-5
Sodium sulfate 6.o 5.o 30.032.0 _26.0
MgSiO3 2.0 1.8 _ _ _
CMC 1.8 2.0 1.5 1.4 _
Ethanol _ _ _ _ 15.0
l _
Remainder- water, dyes,
perfumes, and optical
brighteners _
.
-28-
:. ' ' ' ~ . ' .,:
1049042
The preceding specific embodiments are illustrative of
the practice Or the invention. It is to be understood, however,
that other expedients known to those skilled in the art or dis-
closed herein may be employed without departing from the spirit ~:
of the invention or the scope of the appended claims.
.
:;
.
. . .
.-- .
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