Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
WO94~10277 l 2 1 ~ 8 0 0 S PCT/US~3/~W36
DETERGENT COMPOSITIONS INHIBITING
DYE TRANSFER
Field of the Invention
The present invention relates to a composition and a process
for inhibiting dye transfer between fabrics during washing.
Background of the Invention
One of the most persistent and troublesome problems arising
during modern fabric laundering operations is the tendency of
some colored fabrics to release dye into the laundering
solutions. The dye is then transferred onto other fabrics
being washed therewith.
~_ 2
One way of overcoming this problem would be to complex or
absorb the fugitive dyes washed out of dyed fabrics before they
have the opportunity to become attached to other articles in the
wash. Polymers have been used within detergent compositions to
inhibit dye transfer, such as EP-A-O 102 923, DE-A-2 814 329,
FR-A-2 144 721 and EP-265 257.
United States Patent No. 5,478,489 describes dye transfer
inhibiting compositions comprising polyamine N-oxides containing
polymers.
In addition to dye binding, it is also important to prevent
the tendency of some coloured fabrics to release dyes into the
wash solution. It has now been found that terephthalate-based
soil release polymers when added to said polyamine N-oxide dye
transfer inhibiting compositions enhance the overall dye transfer
inhibiting performance.
This finding allows the formulation of detergent
compositions which are very efficient in preventing colour-
bleeding and in eliminating transfer of solubilized or suspended
dyes.
According to another embodiment of this invention a process
is also provided for laundering operations involving colored
fabrics.
Terephthalate-based soil release polymers have also been
described in the art, for instance in GB 2 137 221, US 4,116,885,
US ,132,680, EP 185 427, EP 199 403, EP 241 985 and EP 241 984.
Summary of the Invention
The present invention relates to inhibiting dye transfer
composltlons comprlslng
A) polyamine N-oxide polymers.
B) terephthalate-based polymers.
~2 ~
WO94/10277 2 1 4 8' ~ ~ 5 PCT/US93/09936
Detailed description of the invention
The compositions of the present invention comprise as
essential elements polyamine N-oxide polymers (A) and a
- terephtalate-based polymer (B).
tA) Polyamine N-oxide polymers
The polyamine N-oxide polymers contain units having the
following structure formula :
Ax
I
R
~herein P is a polymerisable unit, whereto the N-O group
can be attached to or wherein the N-O group forms
part of the polymerisable unit or a combination of
both.
O O O
A is NC, CO, C, -O-,-S-, -N- ; x is or O or 1;
R arè aliphatic, ethoxylated aliphatics, aromatic,
heterocyclic or alicyclic groups or any combination
thereof whereto the nitrogen of the N-O group can be
attached or wherein the nitrogen of the N-O group is
part of these groups
The N-O group can be represented by the following general
structures :
O O
I
(Rl)x -N- (R2)y =N- (Rl)x
I
(R3)z
W094/10277~ $~ PCT/US93/09936
wherein Rl, R2, R3 are aliphatic groups, aromatic,
heterocyclic or alicyclic groups or combinations
thereof, x or/and y or/and z is 0 or l and wherein
the nitrogen of the N-O group can be attached or
wherein the nitrogen of the N-O group forms part of
these groups.
The N-O group can be part of the polymerisable unit (P) or
can be attached to the polymeric backbone or a combination of
both.
Suitable polyamine N-oxides wherein the N-O group forms part
of the polymerisable unit comprise polyamine N-oxides wherein
R is selected from aliphatic, aromatic, alicyclic or
heterocyclic groups.
One class of said polyamine N-oxides comprises the group of
polyamine N-oxides wherein the nitrogen of the N-O group forms
part of the R-group. Preferred polyamine N-oxides are those
wherein R is a heterocyclic group such as pyrridine, pyrrole,
imidazole, pyrrolidine, piperidine and derivatives thereof.
Another class of said polyamine N-oxides comprises the group
of polyamine N-oxides wherein the nitrogen of the N-O group is
attached to the R-group.
Other suitable polyamine N-oxides are the polyamine oxides
whereto the N-O group is attached to the polymerisable unit.
Preferred class of these polyamine N-oxides are the polyamine
N-oxides having the general formula (I) wherein R is an
aromatic, heterocyclic or alicyclic groups wherein the
nitrogen of the N-0 functional group is part of said R group.
Examples of these classes are polyamine oxides wherein R
is a heterocyclic compound such as pyrridine, pyrrole,
imidazole and derivatives thereof.
Another preferred class of polyamine N-oxides are the
polyamine oxides having the general formula (I) wherein R
are aromatic, heterocyclic or alicyclic groups wherein the
nitrogen of the N-0 functional group is attached to said R
groups.
WO94/10277 2 1 ~ ~ ~ O S PCT/US93/~9~
_ 5
Examples of these classes are polyamine oxides wherein R
groups can be aromatic such as phenyl.
Any polymer backbone can be used as long as the amine oxide
polymer formed is water-soluble and has dye transfer
inhibiting properties. Examples of suitable polymeric
- backbones are polyvinyls, polyalkylenes, polyesters,
polyethers, polyamide, polyimides, polyacrylates and mixtures
thereof.
The amine N-oxide polymers of the present invention
typically have a ratio of amine to the amine N-oxide of 10 : 1
to 1: 1000000. However the amount of amine oxide groups
present in the polyamine oxide polymer can be varied by
appropriate copolymerization or by appropriate degree of N-
oxidation . Preferably, the ratio of amine to amine N-oxide is
from 3:1 to 1:1000000. The polymers of the present invention
actually encompass random or block copolymers where one
monomer type is an amine N-oxide and the other monomer type is
an N-oxide or not.
The amine oxide unit of the polyamine N-oxides has a PKa <
10, preferably PKa < 7, more preferred PKa < 6.
The polyamine oxides can be obtained in almost any degree of
polymerisation. The degree of polymerisation is not critical
provided the material has the desired water-solubility and
dye-suspending power.
Typically, the average molecular weight is within the range
of 500 to 1000,000 ; more preferred 1000 to 500,000 ; most
preferred 5000 to 100,000.
The polyamine N-oxides of the present invention are
typically present from 0.01 to 10% , more preferably from 0.05
to 1%, most preferred from 0.05 to 0.5 % by weight of the dye
transfer inhibiting composition.
WOg4/10277 ~ PCT/US93/~36
a~ 6
(B) Terephthalate-based soil release polymers
It has now surprisingly been found that the overall dye
transfer inhibiting performance of detergent compositions
comprising polyamine N-oxide polymers can be improved by
adding terephtalate-based soil release polymers.
It is believed that the adsorption capa~ity of terephtalate-
based soil release polymers onto the fabrics is improved by
the polyamine N-oxide polymers. As a result, the soil release
polymer adsorbs better onto the surface of the fabrics
immersed in the wash solution. It is also believed that the
backbone structure is important to the adsorption of the
polymers on the fabrics while the end groups confer the soil
release properties. The adsorbed polyester then forms a film
onto the fabrics which prevents the fabric from bleeding. The
said combination of terephthalate-base polymers and polyamine
N-oxide containing polymers allows us to formulate dye
transfer inhibiting compositions which are very efficient in
preventing colour-bleeding and in eliminating transfer of
solubilized or suspended dyes.
The compositions according to the present invention comprise
from 0.01 % to 10 % by weight of the total dye transfer
inhibiting composition, preferably from 0.05 % to 5 ~ of a
terephthalate-based soil release polymer. Such soil release
polymers have been extensively described in the art , for
instance in US 4,116,885, US 4,132,680, EP 185 427, EP 199
403, EP 241 985 and EP 241 984.
Suitable polymers for use herein include polymers of the
formula :
X -[(oCH2CH(Y))n(oR5)m H A-Rl-A-R2)u(A-R3-A-R2)v1-
- A - R4 - A ~(R50)m(CH(Y)CH20)n~ X
In this formula, the moiety ~(A-R1-A-R2)U(A-R3-A-R2)v~ A-R4-A
forms the oligomer or polymer backbone of the compounds.
W O 94/10277 2 1 ~ PC~r/US93/09g36
~ 7
O O
The linking A moieties are essentially - C0 - or -OC- moi-
eties, i.e. the compounds of the present invention are polyesters.
As used herein, the term "the A moieties are
essentially - OC - or - C0 - moieties" refers to compounds where
O O
the A moieties consist entirely of moieties - OC - or - C0 -, or
o
are partially substituted with linking moieties such as - N~ - or
0 0 0 H
CN - (amide), and - OCN - or - N~0 - (urethane). The degree of
H H H
partial substitution with these other linking moieties should be
such that the soil release properties are not adversely affected
to any great extent. Preferably, linking moteties A consist
O O
entirely of (i.e., comprise lOOX) moieties - OC - or -C0 -, l.e.,
o e
each A is either - OC - or - C0 -
The Rl moieties are essentially 1,4-phenylene mo~eties. As
used herein, the term "the Rl moieties are essentially 1,4-
phenylene moieties" refers to compounds where the Rl moieties
consist entirely of 1,4-phenylene moiet~es, or are part~ally
substituted with other ary~ene or alkar~lene moieties, alkylene
moieties, alkenylene moieties, or mixt~res the.c~f. Arylene and
alkarylene moieties which can be partially subst~tuted for 1,4-
phenylene include 1,3-phenylene, 1,2-phenylene, 1,8-naphthylene,
1,4-naphthylene, 2,2-biphenylene, 4,4'-biphenylene and mixtures
thereof. Alkylene and alkenylene moieties which can be partially
substituted include ethylene, 1,2-propylene, 1,4-butylene,
l,S-pentylene, 1,6-hexamethylene, 1,7-heptamethylene, 1,8-octa-
methylene, l,4-cyclohexylene, and mixtures thereof.
For the Rl moieties, the degree of partial substitution with
moieties other than l,4-phenylene should be such that the soil
release properties of the compound are not adversely affected to
WO 94/10277 ~ rv' PCI~/US93/09936
any great extent. Generally, the degree of partial substitution
which can be tolerated will depend upon the backbone length of the
compound, i.e., longer backbones can have greater partial sub-
stitution for l,4-phenylene moieties. Usually, compounds where
the Rl comprise from about 50 to 100~ 1,4-phenylene moieties (from
0 to about 50X moieties other than 1,4-phenylene) have adequate
soil release activity. For example, polyesters made accordlng to
the present invention with a 40:60 mole ratio of ~sophthalic
(1,3-phenylene) to terephthalic (1,4-phenylene) acid ha~e adequate
soil release activity. However, because most polyesters used in
fiber making comprise ethylene terephthalate units, it is usually
desirable to minimize the degree of partial substitution w~th
moieties other than 1,4-phenylene for best soil release activity.
Preferably, the Rl moieties consist entirely of (~.e., compr~se
100~) 1,4-phenylene moieties, i.e. each Rl mo~ety is 1,4-phenyl-
ene.
The R2 moieties are essent~ally ethylene mote ff es, or sub-
stituted ethylene mo~eties having Cl-C4 alkyl or alkoxy sub-
stitutents. As used herein, the tenm ~the R2 mo~et~es are essen-
tially ethylene moieties, or subst~tuted ethylene moiet~es hav~ng
Cl-C4 alkyl or alkoxy subst~tuents~ refers to compounds of the
present invention where the ~2 mo~eties cons~st ent1rely of
ethylene, or substituted ethylene mo~et~es, or are partially
substituted with other compatible moiet~es. Examples of these
other moieties include linear C3-C6 alkylene motet~es such as
1,3-propylene, 1,4-butylene, 1,5-pentylene or 1,6-hexamethylene,
1,2-cycloalkylene mo~eties such as 1,2-cyclohexylene, 1,4-cyclo-
alkylene moieties such as 1,4-cyclohexylene and 1,4-dimethylene-
cyclohexylene, polyoxyalkylated 1,2-hydroxyalkylenes such as
-CH2-CH- , and oxyalkylene moieties such as
CH2 ~(CH2CH2~)p X
-CH2CH20CH2CH20CH2CH2- or -CH2cH2~c 2 2
For the R moieties, the degree of partial substitution with
these other moieties should be such that the soil release pro-
perties of the compounds are not adversely affected to any great
W O 94/10277 2 I ~ ~ O OS PC~r/US~3/09936
_ 9
extent. Generally, the degree of partial substitution which can
be tolerated will depend upon the backbone length of the compound,
i.e., longer backbones can have greater partial substitution.
Usually, compounds where the R2 comprise from about 20 to 100X
ethylene, or substituted ethylene moieties (from 0 to about 80
other compatible moieties) have adequate soil release activity.
For example, polyesters made according to the present invention
with a 75:25 mole ratio of diethylene glycol (-CH2CH20CH2CH2-) to
ethylene glycol (ethylene) have adequate soil release activity.
However, it is desirable to minimize such partial substitution,
especially with oxyalkylene moieties, for best soil release
activity. (During the making of polyesters according to the
present invention, small amounts of these oxyalkylene moiettes (as
dialkylene glycols) are typically formed from glycols in side
reactions and are then incorporated into the polyester). Prefer-
ably, R2 comprises from about 80 to 100X ethylene, or substituted
ethylene moieties, and from 0 to about 20X other compatible
moieties.
For the R moieties, suitable ethylene or substituted ethyl-
ene moieties include ethylene, 1,2-propylene, 1,2-butylene,
1,2-hexylene, 3-methoxy-1,2-propylene and mixtures theleof.
Preferably, the R moieties are essentially ethylene moieties,
1,2-propylene moieties or mixtures thereof. Inclusion of a
greater percentage of ethylene moieties tends to improve the soil
release activity of the compounds. Surprisingly, inclusion of a
greater percentage of 1,2-propylene moieties tends to improve the
water solubility of the compounds.
For the R3 moieties, suitable substituted C2-C18 hydro-
carbylene moieties can include substituted C2-C12 alkylene,
alkenylene, arylene, alkarylene and like moieties. The substitut-
ed alkylene or alkenylene moieties can be l~near, branched, or
cyclic. Also, the R3 moieties can be all the same (e.g. all
substituted arylene) or a mixture (e.g. a mixture of substituted
arylenes and substituted alkylenes). Preferred R3 moieties are
those which are substituted 1,3-phenylene moieties.
WO 94/10277 PCI'/US93/09936
The substituted R3 moieties preferably have only one - S03M,
-COOM, -o-~-(R50)m(CH(Y)cH2o)n-~-x or
-A-~(R2-A-R4-A) ~ (R50)m(CH(Y)CH20)n~t X substituent. M can be H
or any compatible water-soluble cation. Suitable water soluble
cations include the water soluble alkali metals such as potassium
(K ) and especially sodium (Na ), as well as ammonium (NH4 ).
Also suitable are substituted ammonium cations having the fonmula:
Rl
R2 N - R4
R3
where R1 and R2 are each a Cl-C20 hydrocarbyl group (e.g. alkyl,
hydroxyalkyl) or together form a cyclic or heterocyclic ring of
from 4 to 6 carbon atoms (e.g. piperidine, morpholine); R3 is a
C1-C20 hydrocarbyl group; and R4 is H (ammonium) or a C1-C20
hydrocarbyl group (quat amine). Typical substituted ammonium
cationic groups are those where R4 is H (ammonium) or Cl-C4 alkyl,
especially methyl (quat amine); Rl is C10-Cl8 alkyl, espec~ally
C12-C14 alkyl; and R2 and R3 are each C1-C4 alkyl, especially
methyl.
The R3 moieties haYing -A-~(R2-A-R4A)-3-W
-~-(RS0)m(CH(Y)CH20)n-~-X substituents provide branched backbone
compounds. R moieties having -A{ (R2-A-R4-A) ~ R -A moieties
provide crosslinked backbone compounds. Indeed, syntheses used to
make the branched backbone compounds typically provide at least
some crosslinked backbone compounds.
The moieties -(RS0)- and -(CH(Y)CH20)- of the moieties
-~-(R50)m(CH(Y)CH20)n-~- and -~-(oCH(Y)CH2)~(0R5)m-3- can be mixed
together or preferably form blocks of -(R 0)- and -(CH(Y)CH20)-
moieties. Preferably, the blocks of -(R50)- moieties are located
next to the backbone of the compound. When R5 is the moiety
-R2-A-R6-, m is 1; also, the moiety -R2.A-R6- is preferably
located next to the backbone of the compound. For R5, the pre-
ferred C3-C4 alkylene is C3H6 (propylene); when RS is C3-C4
alkylene, m is preferably from 0 to about S and is most preferably
0. R6 is preferably methylene or 1,4-phenylene. The moiety
-(CH(Y)CH20)- preferably comprises at least about 75X by weight of
W O 94/10277
2 1 ~ PCr/US93/09936
11
the moiety -~-(RSo)m(CH(Y)CH20)n-3- and most preferably 100X by
weight (m is 0).
The Y substituents of each moiety -~(R50)m(CH(Y)CH20)n-~ are
the ether moiety -CH2(0CH2CH2)pO-X, or are, more typically, a
mixture of this ether moiety and H; p can range from 0 to 100, but
is typically 0. When the Y substituents are a mixture, moiety
-(CH(Y)CH20)n - can be represented by the following moiety:
~(CHCH20)n(CH2CH20)
CH2(0CH2CH2)pO-X
wherein n1 is at least 1 and the sum of n1 + n2 is the value for
n. Typically, n1 has an average value of from about 1 to about
10. The moieties
-(CHCH20)n - and
- (CH2CH20)n-
CH2(0CH2CH2)pO x 2
can be mixed together, but typically form blocks of
-(C~CH20)n - and -(CH2CH20)n - moieties.
CH2 ( 0CH2CH2 ) pO-X
X can be H, C1-C4 alkyl or -eR7, wherein R7 is C1-C4 alky1. X is
preferably methyl or ethyl, and most preferably m~thyl. The value
for each n is at least about 6, but is preferably at least about
10. The value for each n usually ranges from about 12 to about
113. Typically, the value for each n is in the range of from
about 12 to about 43.
~ he backbone moieties -~-A-Rl-A-R2-~- and -(-A-R3-A-R2-~- can
be mixed together or can form blocks of -~-A-Rl-A-R2~L and
-~-A-R3-A-R2-~ moieties. It has been found that the value of u + v
needs to be at least about 3 in order for the compounds of the
present invention to have significant soil release activity. The
maximum value for u ~ v is generally determined by the process by
which the compound is made, but can range up to about 25, i.e. the
WO 94~10277 - ~ PCI'/US93/09936
12 '~
compounds of the present invention are oligomers or low molecular
weight polymers. By comparison, polyesters used in fiber making
typically have d much higher mo~ecular weight, e.g. have from
about ~0 to about 250 ethylene terephthalate units. Typically,
the sum of u ~ v ranges from about 3 to about 10 for the compounds
of the present invention.
Generally, the larger the u + v value, the less soluble is
the compound, especially when the R3 moieties do not have the
substituents -COOM or -S03M. Also, as the value for n increases,
the value for u + v should be increased so that the compound will
deposit better on the fabric during laundering. ~hen the R3
moieties have the substituent -A-~_(R2_
A-R -A) 3w E (RSO)m(CH(Y)CH20)n_~_X (branched backbone compounds)
or -A-~-(R2-A-R4-A) ~ R2_A_ (crosslinked backbone compounds), the
value for w is typically at least 1 and is determined by the
process by which the compound is made. For these branched and
crosslinked backbone compounds the value for u + v ~ w is from
about 3 to about 25.
Preferred compounds in this class of polymers are block
polyesters having the formula:
O O O
{ ( 2CH2)n20cH2FH)nl] t (OC- R1 -CO-R2)u(_~ - R3 -
CH20X
O O O
co R2) ~ oc-~4-co{(IHcH2o)nl(cH2cH2o)
CH20X
wherein the Rl moieties are all 1,4-phenylene moieties; the R2
moieties are essentially ethylene moieties, 1,2-propylene moieties
or mixtures thereof; the R3 moieties are all potassium or pre-
ferrably sodium 5-sulfo-1,3-phenylene moieties or substituted
1,3-phenylene moieties having the substituent
WO 94/10277 PCI/USg3/09g36
- 2~4~QO~
13
O O O
) i W~~(IHCH2~)n1(CH2CH20)n-~-X at the 5
CH20X
position; the R moieties are Rl or R3 moieties, or mixtures
thereof; each X is ethyl or preferably methyl; each nl is from 1
to about S; the sum of each nl + n2 is from about 12 to about 43;
when w is O, u + v is from about 3 to about 10; when w is at least
1, u + v + w is from about 3 to about 10.
Particularly preferred block polyesters are those hhere v is
O, i.e. the linear block polyesters. for these most preferred
linear block polyesters, u typically ranges from about 3 to about
8. The most water soluble of these linear block polyesters are
those where u is from about 3 to about 5.
Other suitable polymers for use herein include polymers of the
formula :
X-E(OCH2CH(Y))n(oR4)m ~ E(A-Rl-A-R2)u(A-Rl-A-R3)
- A-Rl-A~(R40~m(CH(Y)CH20)n~ X
In this formula, the moiety -~(A-Rl-A-R2)U(A-Rl-A-R3)V~ A-Rl-A-
forms the oligomer or polymer backbone of the compounds. Groups
X-~(oCH2CH(Y))n(oR4)m~ and -~(R40)m(CH(Y)CH20)n~}-X are generally
connected at the ends of the oligomer/polymer backbone.
O O
Il ~I
The linkins A moieties are essentially - CO - or -OC- moi-
eties, i.e. the compounds of the present invention are polyesters.
As used herein, the tenm "the A moieties are
O O
essentially - OC - or - CO - moieties" refers to compounds where
O O
the A moieties consist entirely of moieties - OC - or - CO -, or
WO 94/l~77 Q~ PCI/US93/09936
14
are partially substituted with linking moieties such as - NC - or
O O O H
CN - (amide), and - OYN - or - NCO - (urethane). The degree of
H H H
partial substitution with these other linking moieties should be
such that the soil release properties are not adversely affected
to any great extent. Preferably, linking moieties A consist
O O
entirely of ~i.e., comprise 100~) moieties - OC - or -CO -, i.e.,
O O
each A is either - OC - or - CO -
The Rl moieties are essentially 1,4-phenylene moieties. As
used herein, the term ~the Rl moiet~es are essentially 1,4-
phenylene moieties" refers to compounds where the Rl moieties
consist entirely of 1,4-phenylene mo~eties, or are partially
substituted with other arylene or alkarylene moiet~es, alkylene
moieties, alkenylene moieties, or mixtures thereof. Arylene and
alkarylene moieties which can be part~ally substituted for 1,4-
phenylene include 1,3-phenylene, 1,2-phenylene, 1,8-naphthylene,
1,4-naphthylene, 2,2-biphenylene, 4,4~-biphenylene and mixtures
thereof. Alkylene and alkenylene moiet~es which can be partially
substituted include ethylene, 1,2-propylene, 1,4-butylene,
1,5-pentylene, 1,6-hexamethylene, 1,7-heptamethylene, 1,8-octa-
methylene, 1,4-cyclohexylene, and mixtures thereof.
These other arylene, alkarylene, alkylene and alkenylene
moieties can be unsubstituted or can have at least one -S03M,-COOM
or -A-R~ A-Rl-A-R7-o ~ X substituent or at least one moiety
-A-R -~A-Rl-A-R -3--A- cross-linked to another R moiety, wherein
R7 is the moiety R~ or R3; and w is O or at least 1. Preferably,
these substituted Rl moieties have only one -S03M, -COOM or -A-R7
{ A-R1-A-R7-o ~ X substituent. M can be H or any compatible
water-soluble cation. Suitable water-soluble cations include the
water-soluble alkali metals such as potassium (K ) and especiatly
sodium (Na ), as well as ammonium (NH4 ). Also suitable are
substituted ammonium cations having the formula:
W O 94/10277 P(~r/US93/Og936
15 ~ 0 S
R2 N+ R4
l3
where R1 and R2 are each a C1-C20 hydrocarbyl group (e.g. alkyl,
hydroxyalkyl) or together form a cyclic or heterocyclic ring of
from 4 to 6 carbon atoms (e.g. piperidine, morpholine); R3 is a
C1-C20 hydrocarbyl group; and R4 is H (ammonium) or a C1-C20
hydrocarbyl group (quat amine). Typical substituted ammonium
cationic groups are those where R4 is H (ammonium) or Cl-C4 alkyl,
especially methyl (quat amine); R1 is C10-Cl8 alkyl, especially
C12-C14 alkyl; and R and R are each C1-C4 alkyl, especially
methyl.
The R1 moieties having -A-R7-~- A-R1-A-R7-o ~ X substituents
provide branched backbone compounds. ~he R1 moieties having
-A-R7{ A-R1-A-R7 ~ A- moieties provide cross-linked backbone
compounds. Indeed, syntheses used to make the branched bac~bone
compounds typically provide at least some cross-linked backbone
compounds.
For the R1 moieties, the degree of partial substitution with
moieties other than 1,4-phenylene should be such that the soil
release properties of the compound are not adversely affected to
any great extent. Generally, the degree of partial substitution
which can be tolerated will depend upon the backbone length of the
compound, i.e., longer backbones can have greater partial sub-
stitution for 1,4-phenylene moieties. Usually, compounds where
the R comprise from about 50 to 100X 1,4-phenylene moieties (from
0 to about 50X moieties other than 1,4-phenylene) have adequate
soil release activity. However, because most polyesters used in
fiber making comprise ethylene terephthalate units, it is usually
desirable to minimize the degree of partial substitution with
moieties other than 1,4-phenylene for best soil release activity.
Preferably, the R1 moieties consist entirely of (i.e., comprise
100g) 1,4-phenylene moieties, i.e. each R1 moiety is 1,4-phenyl-
ene.
WO 94/10277
PCI'/US93/09936
Q~ 16 '-
The R2 moieties are essentially substituted ethy1ene moieties
having Cl-C~ alkyl or alkoxy substitutents. As used herein, the
term "the R moieties are essentially substituted ethylene moie-
ties having C1-C4 alkyl or alkoxy substituents" refers to
compounds of the present invention where the R2 moieties consist
entirely of substituted ethylene moieties, or are partially
replaced with other compatible moieties. Examples of these other
moieties include linear C2-C6 alkylene moieties such as ethylene,
1,3-propylene, 1,4-butylene, l,S-pentylene or 1,6-hexamethylene,
1,2-cycloalkylene moieties such as 1,2-cyclohexylene, 1,4-
cycloalkylene moieties such as 1,4-cyclohexylene and 1,4-
dimethylene-cyclohexylene, polyoxyalkylated 1,2-hydroxyalkylenes
such as -CH2-C~- , and oxyalkylene moieties such as
CH2 0 ( CH2CH20 ) p X
-CH2CH20CH2CH2-.
For the R moieties~ the degree of partial replacement with
these other moieties should be such that the soil release and
solubility properties of the compounds are not adversely affected
to any great extent. Generally, the degree of part1al replacement
which can be tolerated will depend upon the soil release and
solubility properties desired, the backbone length of the com-
pound, (i.e., longer backbones generally can have greater partial
replacement), and the type of moiety involved (e.g., greater
partial substitution with ethylene moieties generally decreases
solubility). Usually, compounds where the R2 com~rise from about
20 to 100~ substituted ethylene moieties (from 0 to about 80X
other compatible moieties) have adequate soil release activity.
However, it is generally desirable to minimize such partial
replacement for best soil release activity and solubility
properties. (During the making of polyesters according to the
present invention, small amounts of oxyalkylene moieties (as
dialkylene glycols) can be formed from glycols in side reactions
and then incorporated into the polyester). Preferably, R2 com-
prises from about 80 to 100~ substituted ethylene moieties, and
from 0 to about 20X other compatible moieties. For the R2
W O 94/10277 2 1 ~ P(~r/USg3/09936 17
moieties, suitable substituted ethylene moieties include
1,2-propylene, 1,2-butylene, 3-methoxy-1,2-propylene and mixtures
thereof. Preferably, the R2 moieties are essentially 1,2-
propylene moieties.
The R moieties are essentially the polyoxyethylene moiety
~(CH2CH20)q~CH2CH2~~ As used herein, the term "the R3 moieties
are essentially the polyoxyethylene moiety ~(CH2CH20)q~H2CH2~n
refers to compounds of the present invention in which the R
moieties consist entirely of this polyoxyethylene moiety, or
further include other compatible moieties. Examples of these
other moieties incluce C3-C6 oxyalkylene moieties such as oxy-
propylene and oxybutylene, polyoxyalkylene moieties such as
polyoxypropylene and polyoxybutylene, and polyoxyalkylated 1,2-
hydroxyalkylene oxides such as -OCH2CH-
CH20(CH2CH20)p-X .
The degree of inclusion of these other moieties should be such
that the soil release properties of the compounds are not ad-
versely affected to any great extent. Usually, in compounds of
the present invention, the polyoxyethylene moiety comprises from
about 50 to 100~ of each R3 moiety. Preferably, the
polyoxyethylene moiety comprises from about 90 to lOOX of each R3
moiety. (During the making of polyesters according to the present
invention, very small amounts of oxyalkylene mo~eties may be
attached to the polyoxyethylene moiety in side reactions and thus
incorporated into the R3 moieties).
For the polyoxyethylene moiety, the value fo: q is at least
about 9, and is preferably at least about 12. The value for q
usually ranges from about 12 to about 180. Typically, the value
for q is in the range of from about 12 to about 90.
The moieties -tR40)- and -(CH(Y)CH20)- of the moieties
-~-(R O)m(CH(Y)CH2G)n-~- and -~-(oCH(Y)CH2)r(0R4)m-~- can be mixed
together or preferably form blocks of -(R 0)- and -(CH(Y)CH20)-
moieties. Preferably, the blocks of -(R40)- moieties are located
next to the backbone of the compound. ~hen R4 is the moiety
-R2-A-R5-, m is 1; also, the moiety -R2-A-R5- is preferably
located next to the backbone of the compound. For R4, the
WO 94/102~ PCI/US93/09936
18
preferred C3-C4 a1kylene is C3H6 (propylene); when R4 is C3-C4
alkylene, m is preferably from O to about 10 and is most pre-
ferably 0. R5 is preferably methylene or 1,4-phenylene. The
moiety -(CH(Y)CH20)- preferably comprises at least about 75~ by
weight of the moiety -~-(R40)m(CH(Y)CH20)n-~- and most preferably
lOOX by weight (m is 0).
The Y substituents of each moiety [(R50)m(CH(Y)CH20)n] are H,
the ether moiety -CH2(0CH2CH2)pO-X, or a mixture of this ether
moiety and H; p can range from O to lOO, but is typically 0.
Typically, the Y substituents are all H. ~hen the Y substituents
are a mixture of the ether moiety and H, the moiety -(CH(Y)CH20)n-
can be represented by the following moiety:
-{(jHCH20)n(CH2CH20)n~-
CH2 ( 0CH2CH2 ) pO-X
wherein nl is at least 1 and the sum of nl I n2 is the value for
n. Typically, n1 has an average value of from about 1 to about
10. The moieties
-(CHCH20)n - and
~(CH2CH2~)n-
CH2(0CH2CH2)pO_X
can be mixed together, but typically form blocks of
-(fHCH20)n - and ~(CH2CH2~)n2 moieties.
CH2(0CH2CH2 ) pO-X
X can be H, C1-C4 alkyl or -CR7, wherein R7 is Cl-C4 alkyl. X is
preferably methyl or ethyl, and most preferably methyl. The value
for each n is at least about 6, but is preferably at least about
10. The value for each n usually ranges from about 12 to about
113. Typically, the value for each n is in the range of from
about 12 to about 45.
The backbone moieties -~-A-Rl-A-R2-~- and
WO 94/10277
~ ~ ~ 8 Q ~ 5 PCr/US93/09g36
19
-~-A-Rl-A-R3-~- can form blocks of -~-A-Rl-A-R ~ and
-~-A-RI-A-R3~- moieties but are more typically randomly mixed
together. For these backbone moieties, the average value of u can
range from about 2 to about 50; the average value of v can range
from about 1 to about 20; and the average value of u + v can range
from about 3 to about 70. The average values for u, v and u + v
are generally determined by the process by which the compound is
made. Generally, the larger the average value for v or the
smaller the average ~alue for u + v, the more soluble is the
compound. Typically, the average value for u is from about 5 to
about 20; the average value for v is from about 1 to about 10; and
the average value for u + v is from about 6 to about 30. Géner-
ally, the ratio of u to v is at least about 1 and is typically
from about 1 to about 6.
Preferred compounds in this class of polymers are polyesters
having the formula:
O O O O
X-(OCH2CH2)n ~(-OC-Rl-CO-R2-)U (-~-Rl-Co-R3-)
O O
-OC-R-CO-~CH2CH20)n-X
wherein each R1 is a 1,4-phenylene moiety; the R2 are essentially
1,2-propyle~e moieties; the R3 are essentially the polyoxyethylene
moiety ~(CH2H20)q~CH2CH2~; each X is ethyl or preferably methyl;
each n is from about 12 to about 45; q is from about 12 to about
90; the average value of u is from about 5 to about 20; the
average value of v is from about 1 to about 10; the average value
of u + v is from about 6 to about 30; the ratio u to v is from
about 1 to about 6.
WO 94/10277 PCI~/US93/09936
~ighly ~referred Dolymers for use ~erein are Dolymers of the
formula :
O O
X tOCH2CH2tn tO - C - R1 _ ~ - OR2t
O O
~ 0 - C - R1 _ C - Ot ta~2CH2 n
in which X can be any suitable capping group, wit~ each X being
selected frorn the group consisting of H, and alkyl or acyl groups
containing from 1 to about 4 carbon atoms, preferably 1 to 2
carbon atoms, most preferably alkyl. n is sel~ted for water
solubility and is a range of values which generally averages from
about 10 to about 50, preferably from about 10 to about 25. The
selection of u is critical to formùlation in a liquid detergent
having a relatively high ionic strength. Tl~ere should be very
little material, preferably less than about 10 mol ~, more
preferably less than S mol %, most preferably Icss than 1 mol %,
in which u is greater than 5. Furtt.&r~.~re there should be at
least 20 mol %, preferably at least 40 mol %, of material in which
u ranges from 3 to 5.
The R1 moieties are essentially 1,4-phenylene ~ieties. As
used herein, the term "the Rl moieties are essentially 1, 4-
phenylene moieties" refers to CDm pounds where the Rl moieties
consist entirely of t,4-phenylene moieties, or are partially
substituted with other arylene or alkarylene moieties, alkylene
moieties, alkenylene moieties, or mixtures thereof. Arylene and
alkarylene moieties which can be partially substituted for t,4-
phenylene include 1,3-phenylene, 1,2-phenylene,
WO94/10277 Z ~ 8~ PCI/US~3/09936
-- 21
1, 8-naphthylene, 1, 4-naphthylene, 2, 2-biphenylene,
4, 4'-biphenylene and mixtures thereof. Alkylene and alkenylene
moieties which can be partially substituted include ethylene,
1,2-propylene, 1,4-butylene, 1,5-pentylene, 1,6-hexamethylene,
1,7-heptamethylene, 1,8-octamethylene, '1,4-cyclohexylene, and
mixtures thereof.
For the R1 moieties, the degree of partial substitution with
moieties other than 1 ,4-phenylene should be such that the soil
release properties of the compovrd are not adversely afrecled to
any great extent. Generally, the degree of partial substitution
which can be tolerated will depend upon the ' ackbone length of
the compound, i . e ., longer baci~bones can have greater partial
substitution for 1, 4 ~ enylene moieties. Usually, compound
where the Rl comprise from about 509~ to 100~ enylene
moieties (from 0 to about S0~ moieties other than 1,~ ~he.-ylene)
have adequate soil release activity. For example, ~oly~sters made
according to the present i..~ent;~ with a 40:60 mole ratio of
isophthalic (1,3-phenylene) to terepl.tha~ic (1,4-phenylene) acid
have adequate soil ~el~ase activity. Il~ e~er, because most
polyesters used in fiber making comprise ethylene terephthalate
units, it is usually desirable to minimizc the degree of partial
substitution with moieties other than 1,~ ~he.~ylene for best soil
release activity. Preferably, the Rl moieties consist entirely of
(i.e., comprise 100~) l,q phenylene moieties, i.e. each Rl moiety
is 1, 4-phenylene.
For the R2 m~ieties, suit~ble ethylene or substituted ethyl-
ene moieties include ethylene, 1, 2-propylene, 1, 2-butylene,
1, 2-hexylene, 3-methoxy-1 ,2-propylene and mixtures thereof.
Preferably, the R2 moieties are essentially ethylene moieties,
- or, preferably, 1, 2-propylene moietieS or mixtures thereof .
Although inclusion of a greater percentage of ethylene moieties
tends to improve the soil release activity of the compounds, the
percentage included is limited by water so!ubility. Surprisingly,
inclusion of a greater percentage of 1,2-propylene moieties tends
to improve the water solubility of the c~ ~unds and consequently
~ ~ ~8~
22
the ability to formulate isotropic aqueous detergent compositions
without significantly harming soil release activity.
For this invention, the use of 1,2-propylene moieties or a
similar branched equivalent is extremely important for maximizing
incorporation of a substantial percentage of the soil release
component in the heavy duty liquid detergent compositions.
Preferably, from about 75% to about 100~, more preferably
from about 90% to about 100% of the R2 moieties are 1,2-propylene
molet ies .
In general, soil release components which are soluble in
cool (15~C) ethanol are also useful in compositions of the
invention.
The value for n averages at least about 10, but a
distribution of n values is present. The value for each n
usually ranges from about 10 to about 50. Preferably, the value
for each n averages in the range of from about 10 to about 25.
A preferred process for making the soil release component
comprises the step of extracting a polymer having a typical
distribution in which a substantial portion comprises a material
in which u is equal to or greater than 6 with essentially
anhydrous ethanol at low temperatures, e.g. from about 10~C to
about 15~C, preferably less than about 13~C. The ethanol soluble
fraction is substantially free of the longer polymers and is much
easier to incorporate into isotropic heavy duty liquids,
especially those with higher builder levels. Although the
polymers wherein u is less than about 3 are essentially of no
value in providing soil release effects, they can be more easily
incorporated than higher u values.
A more preferred process for making the soil release
component is by direct synthesis.
A more comprehensive disclosure of the soil release
component and methods for making it can be found in Canadian
Patent No. 1,315,286, issued March 30, 1993.
~B~
wo g4/10277 2 I ~ 8 Q o 5 pcr/us93/o9936
23
The most prefe~red polymers for use herein are polymers
according to the formula :
O O
X (OCH2CH2)n (O - C - R1 - C - oR2)U
~
(o - C - R1 - C - O) (cH2cH2o)n X
wherein X is methyl, n is 16, R1 is 1,4-phenylene moiety, R2
is 1,2-propylene moiety and u is essentially between 3 and 5.
DETERGENT ADJUNCTS
The present compositions are conveniently used as additives
to conventional detergent compositions for use in laundry
operations. The present invention also encompasses dye
transfer inhibiting compositions which will contain detergent
ingredients and thus serve as detergent compositions.
A wide range of surfactants can be used in the detergent
compositions. A typical listing of anionic, nonionic,
ampholytic and zwitterionic classes, and species of these
surfactants, is given in US Patent 3,664,961 issued to Norris
on May 23, 1972.
Mixtures of anionic surfactants are particularly suitable
herein, especially mixtures of sulphonate and sulphate
surfactants in a weight ratio of from 5:1 to 1:2, preferably
from 3:1 to 2:3, more preferably from 3:1 to 1:1. Preferred
sulphonates include alkyl benzene sulphonates having from 9 to
15, especially 11 to 13 carbon atoms in the alkyl radical, and
alpha-sulphonated methyl fatty acid esters in which the fatty
acid is derived from a C12-C1g fatty source preferably from a
C16-C18 fatty source. In each instance the cation is an
alkali metal, preferably sodium. Preferred sulphate
surfactants are alkyl sulphates having from 12 to 18 carbon
atoms in the alkyl radical, optionally in admixture with
ethoxy sulphates having from 10 to 20, preferably 10 to 16
r'
WO94/102~ PCT/US93/09936
24
carbon atoms ln the alkyl radical and an average degree of
ethoxylation of 1 to 6. Examples of preferred alkyl sulphates
herein are tallow alkyl sulphate, coconut alkyl sulphate, and
C14_1s alkyl sulphates. The cation in each instance is again
an alkali metal cation, preferably sodium.
One class of nonionic surfactants useful in the present
invention are condensates of ethylene oxide with a hydrophobic
moiety to provide a surfactant having an average hydrophilic-
lipophilic balance (HLB) in the range from 8 to 17, preferably
from 9.5 to 13.5, more preferably from 10 to 12.5. The
hydrophobic ~lipophilic) moiety may be aliphatic or aromatic
in nature and the length of the polyoxyethylene group which is
condensed with any particular hydrophobic group can be readily
adjusted to yield a water-soluble compound having the desired
degree of balance between hydrophilic and hydrophobic
elements.
Especially preferred nonionic surfactants of this type are
the Cg-C1s primary alcohol ethoxylates containing 3-8 moles of
ethylene oxide per mole of alcohol, particularly the C14-C1s
primary alcohols containing 6-8 moles of ethylene oxide per
mole of alcohol and the C12-C14 primary alcohols containing 3-
5 moles of ethylene oxide per mole of alcohol.
Another class of nonionic surfactants comprises alkyl
polyglucoside compounds of general formula
RO (cnH2no)tzx
wherein Z is a moiety derived from glucose; R is a saturated
hydrophobic alkyl group that contains from 12 to 18 carbon
atoms; t is from 0 to 10 and n is 2 or 3; x is from 1.3 to 4,
the compounds including less than 10~ unreacted fatty alcohol
and less than 50% short chain alkyl polyglucosides. Compounds
of this type and their use in detergent are disclosed in EP-B
0 070 077, 0 075 996 and 0 094 118.
WO94/10277 ~ t~ 8~ q5 PCT~US93/0~36
Also suitable as nonionic surfactants are poly hydroxy fatty
acid amide surfactants of the formula
R2 - C - N - Z,
Il I
O Rl
wherein R1 is H, or R1 is C1_4 hydrocarbyl, 2-hydroxy ethyl,
2-hydroxy propyl or a mixture thereof, R2 is Cs_31
hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a linear
hydrocarbyl chain with at least 3 hydroxyls directly connected
to the chain, or an alkoxylated derivative thereof.
Preferably, R1 is methyl, R2 is a straight C11_1s alkyl or
alkenyl chain such as coconut alkyl or mixtures thereof, and Z
is derived from a reducing sugar such as glucose, fructose,
maltose, lactose, in a reductive amination reaction.
The compositions according to the present invention may
further comprise a builder system. Any conventional builder
system is suitable for use herein including aluminosilicate
materials, silicates, polycarboxylates and fatty acids,
materials such as ethylenediamine tetraacetate, metal ion
sequestrants such as aminopolyphosphonates, particularly
ethylenediamine tetramethylene phosphonic acid and diethylene
triamine pentamethylenephosphonic acid. Though less preferred
for obvious environmental reasons, phosphate builders can also
be used herein.
Suitable builders can be an inorganic ion exchange material,
commonly an inorganic hydrated aluminosilicate material, more
particularly a hydrated synthetic zeolite such as hydrated
zeolite A, X, B or HS.
Another suitable inorganic builder material is layered
silicate, e.g. SKS-6 (Hoechst). SKS-6 is a crystalline
layered silicate consisting of sodium silicate (Na2Si2Os).
Suitable polycarboxylates builders for use herein include
citric acid, preferably in the form of a water-soluble salt,
derivatives of succinic acid of the formula R-
CH(COOH)CH2(COOH) wherein R is C10-20 alkyl or alkenyl,
WO ~/10~77 Z ~ 26 PCT/US93/~gg~
preferably C12-16, or wherein R can be substituted with
hydroxyl, sulfo sulfoxyl or sulfone substituents. Specific
examples include lauryl succinate , myristyl succinate,
palmityl succinate2-dodecenylsuccinate, 2-tetradecenyl
succinate. Succinate builders are preferably used in the form
of their water-soluble salts, including sodium, potassium,
ammonium and alkanolammonium salts.
Other suitable polycarboxylates are oxodisuccinates and
mixtures of tartrate monosuccinic and tartrate disuccinic acid
such as described in US 4,663,071.
Especially for the liquid execution herein, suitable fatty
acid builders for use herein are saturated or unsaturated C10-
18 fatty acids, as well as well as the corresponding soaps.
Preferred saturated species have from 12 to 16 carbon atoms in
the alkyl chain. The preferred unsaturated fatty acid is
oleic acid.
Preferred builder systems for use in granular compositions
include a mixture of a water-insoluble aluminosilicate builder
such as zeolite A, and a watersoluble carboxylate chelating
agent such as citric acid.
Other builder materials that can form part of the builder
system for use in granular compositions the purposes of the
invention include inorganic materials such as alkali metal
carbonates, bicarbonates, silicates, and organic materials
such as the organic phosphonates, amiono polyalkylene
phosphonates and amino polycarboxylates.
Other suitable water-soluble organic salts are the homo- or
co-polymeric acids or their salts, in which the polycarboxylic
acid comprises at least two carboxyl radicals separated from
each other by not more than two carbon atoms.
Polymers of this type are disclosed in GB-A-1,596,756.
Examples of such salts are polyacrylates of MW 2000-5000 and
their copolymers with maleic anhydride, such copolymers having
a molecular weight of from 20,000 to 70,000, especially about
40,000.
WO94/10277 21~ ~ ~ 0 5 PCT/US93/09936
_ 27
Detergency builder salts are normally included in amounts
of from 10% to 80% by weight of the composition preferably
from 20% to 70% and most usually from 30% to 60% by weight.
Other components used in detergent compositions may be
employed, such as bleaches, suds boosting or depressing
agents, enzymes and stabilizers or activators therefor, soil-
suspending agents soil-release agents, optical brighteners,
abrasives, bactericides, tarnish inhibitors, coloring agents,
and perfumes.
Especially preferred are combinations with technologies which
also provide a type of color care benefit. Examples of these
technologies are polyvinylpyrrolidone polymers and other
polymers which have dye transfer inhibiting properties.
Another example of said technologies are cellulase for color
maintenance/ rejuvenation.
The detergent compositions according to the invention can
be in liquid, paste or granular forms. Granular compositions
according to the present invention can also be in "compact
form", i.e. they may have a relatively higher density than
conventional granular detergents, i.e. from 550 to 950 g/l; in
such case, the granular detergent compositions according to
the present invention will contain a lower amount of
"inorganic filler salt", compared to conventional granular
detergents; typical filler salts are alkaline earth metal
salts of sulphates and chlorides, typically sodium sulphate;
"compact" detergents typically comprise nst more than 10%
filler salt. The liquid~compositions according to the present
invention can also be in "compact form", in such case, the
liquid detergent compositions according to the present
invention will contain a lower amount of water,compared to
conventional liquid detergents.
The present invention also relates to a process for
inhibiting dye transfer from one fabric to another of
solubilized and suspended dyes encountered during fabric
laundering operations involving colored fabrics.
The process comprises contacting fabrics with a laundering
solution as hereinbefore described.
w094/to277 ~4~~~ PCT/US93/~9~
28
The process of the invention is conveniently carried out in
the course of the washing process. The washing process is
preferably carried out at 5 ~C to 75 ~C, especially 20 to 60,
but the polymers are effective at up to 95 ~C. The pH of the
treatment solution is preferably from 7 to 11, especially from
7.5 to 10.5.
The process and compositions of the invention can also be
used as additive during laundry operations.
The following examples are meant to exemplify compositions
of the present invention , but are not necessarily meant to
limit or otherwise define the scope of the invention, said
scope being determined according to claims which follow.
Example I :
A liquid detergent composition according to the present
invention is prepared, having the following composition :
Linear alkylbenzene sulfonate 10
Alkyl sulphate 4
Fatty alcohol (C12-Cls) ethoxylate 12
Fatty acid 10
Oleic acid 4
Citric acid
NaOH 3 4
Propanediol 1.5
Ethanol 10
Poly(4-vinylpyridine)-N-oxide 0.3
Therephtalate-based polymer 0.4
Minors up to 100
Example II :
A compact granular detergent composition according to the
present invention is prepared, having the following
formulation:
WO94/10277 2 1 ~ 5 PCT/US93/0~36
29
Linear alkyl benzene sulphonate 11.40
Tallow alkyl sulphate 1.80
C4s alkyl sulphate 3.00
C4s alcohol 7 times ethoxylated 4.00
Tallow alcohol 11 times ethoxylated 1.80
Dispersant 0.07
Silicone fluid 0.80
Trisodium citrate 14.00
Citric acid 3.00
Zeolite 32.50
Maleic acid actylic acid copolymer 5.00
DETMPA 1.00
Cellulase ~active protein) 0.03
Alkalase/BAN 0.60
Lipase 0.36
Sodium silicate 2.00
Sodium sulphate 3.50
Glucose 10.00
Poly(4-vinylpyridine)-N-oxide 0.3
Terephtalate-based polymer 0.4
Minors up to 100
Examples III-VI :
The compositions according to the present invention will
be further illustrated by the following examples. The
following liquid detergent compositions are made by mixing the
listed ingredients in the listed proportions (weight %).
These compositions comprise a pH-jump system which consists of
polyhydroxy fatty acid amide surfactants and borate and/or
propanediol. The compositions are formulated at a pH below 7,
preferably at a pH of 6.5. Upon dilution, these formulations
..
provide a wash pH of at least 7.4. This pH-jump allows
compositions which are unstable at a certain pH to be
formulated at a lower pH. Examples of such compositions are
polymer-containing compositions which have a better stability
of the polymers at a lower pH. Other advantages of the pH-jump
WO94/10277 ~ PCT/US93/ffl 36
system include the improved bleachable stain removal upon
pretreatment and lower formulation cost, in that less
neutralizing agent is required to obtain a higher pH.
III IV V VI
C12-C1s Alkyl sulfate - 19.0 21.0
C12-C1s Alkyl ethoxylated sulfate23.04.0 4.025.0
C12-C14 N-methyl glucamide 9.0g 0 g og o
C12-C14 fatty alcohol ethoxylate 6.06.0 6.06.0
C12-Cl6 Fatty acid 9.06.8 14.014.0
citric acid anhydrous 6.04.5 3.53.5
Diethylene triamine penta methylene
phosphonic acid 1.01.0 2.02.0
Monoethanolamine 13.212.7 12.811.0
Propanediol 12.714.5 13.110.0
Ethanol 1.81.8 4.75.4
Enzymes 2.42.4 2.02.0
Terephtalate-based polymer 0.50.5 0.50.5
Polyvinyl pyrrolidone 1.0 1.0
Poly(4-vinylpyridine)-N-oxide 0.5 0.5
Boric acid 2.42.4 2.8 2.8
2-butyl-Octanol 2.02.0 2.0 2.0
DC 3421 R (1) 0.30.4 0.3 0.4
FF 400 R (2)
Water & Minors ------up to 100%------
(1) DC 3421 is a silicone oil commercially available from Dow
Corning. (2) is a silicone glycol emulsifier available from
Dow Corning.
