Note: Descriptions are shown in the official language in which they were submitted.
' '94/00546 '.i I 3 8 9 4 ~ PC~r/US93/05551
Concentrated aqueous liquid detergent compositions
comprising polyvinylpyrrolidone and a terephthalate-based
soil release polymer
Technical field
The present invention relates to concentrated aqueous
liquid detergent compositions. The compositions
according to the present invention comprise
polyvinylpyrrolidone and a terephthalate-~ased soil
release polymer.
Backqround of the invention
It is widely known in the art to use various polymers in
liquid detergent compositions. The use of polyvinyl
pyrrolidone in detergent compositions, mainly for fabric
care properties, has been described for instance in EP
262 897, EP 327 927 and EP 203 486. These documents
Pnco~p~s the use of polyvinylpyrrolidone in liquid
detergent compositions.
Terephthalate-based soil release polymers have also been
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. These documents also encompass liquid detergent
compositions.
A new trend in the field of detergent compositions is the
formulation of so-called concentrated detergents. In the
context of liquid aqueous detergents, this refers to
products comprising less water and a higher total amount
of active ingredients. The formulation of such
W094/00~46 ~ 3 ~ 9 ~ ~ PCT/US93/05~'
concentrated detergent compositions raises specific
problems.
In particular, formulating concentrated a~ueous liquid
detergent compositions comprising Polyvinylpyrrolidone
raises a problem in that polyvinylpyrrolidone becomes
less soluble in such concentrated detergent matrixes as
their water content drops. The same problem occurs with
terephthalate-based soil release polymers. These
problems result in products which have a hazy appearance
and present physical stability issues.
It has now surprisingly been found that both
polyvinylpyrrolidone and terephthalate-based soil release
polymers can improve each others' solubility in said
concentrated aqueous liquid detergent matrix. Thus,
physically stable aqueous liquid detergent compositions
can be formulated which comprise both said polymers
whereas they would be less stable if they only contained
either one.
Combinations of polyvinylpyrrolidone and terephthalate-
based soil release polymers have been disclosed in GB 2
137 221 in the context of granular detergent
compositions. In this context, the polyvinylpyrrolidone
is said to protect the terephthalate soil release polymer
against attack by alkaline builders.
SummarY of the invention
The compositions according to the present invention are
liquid detergent compositions comprising conventional
detergency ingredients, from 2 % to 35 % by weight of the
total composition of water, from 0.05 ~ to 5 % by weight
of the total composition of polyvinylpyrrolidone and from
0.05 % to 2 % of a terephthalate-based polymer.
~94/00546 ~1 3 8 9 ~ S PCT/US93/05551
Detailed des~riPtion of the invention
The present invention comprises polyvinylpyrrolidone (A),
a terephthalate-based soil release polymer (B) and
conventional detergency Lngredients (C).
(A) PolvvinYlPYrrolidone
The composition according to the invention comprises from
0.05 % to 5 ~ by ~cight of polyvinylpyrrolidone,
preferably from 0.25 % to 2 %. Preferred
polyvinylpyrrolidone for use herein have a molecular
weight of from 1000 to 100 000, preferably from 1500 to
20000, most preferably from 2500 to 15000.
(B) TereDhthalate-based soil release ~ol~mer
The compositions according to the present invention
comprise from 0.05 % to 2 % ~y weight of the total
composition, preferably from 0.1 % to 0.5 % 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.
Sultable poly~ers for use herein include polymers of the
f~r::~ula: X ~ ~oCH2CH(Y~)n(o~5)m~E(A-Rl-A-R2)U(A-R3-A-R2)
- A-R~ (R50)~!CH(Y)~H20)nl X
In this formul2, the moiety t(A-Rl-A-R2)U(A-R -A-R2)V~ A-R4-A-
foms the ol igomer or polymer ~ackbone of the compounds.
It is 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.
~ 1 3 ~ 9 ~ 5 PCI/US93/055.
WO 94/00546
- 4 -
O O
~ Il 11
The linking A moieties are essentially - CO - or -OC- moi-
eties, i.e. the compounds of the present invention are polyesters.
As used herein, the term "the A moieties are
O O
Il 11
essentially - OC - or - CO - moieties" refers to compounds where
O O
Il 11
the A moieties consist entirely of moieties - OC - or - CO -, or
R
are partially substituted with linking moieties such as - NC - or
O O O
CN - (amide), and - OYN - or - NCO - (urethane). The degree of
~ 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~ntirely of (i.e., comprise 100X) moieties - OC - or -CO -, i.e.,
O O
each A is either - Oe - or - CO -
The R1 moieties are essentially 1,4-phenylene moieties. As
used herein, the term "the Rl moieties are essentially 1,4-
phenylene moieties" refers to compounds where the Fl moieties
consist entirely of 1,4-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 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,
1,5-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 1,4-phenylene should be such that the soil
release properties of the compound are not adversely affected to
~94/00546 ~ 3 8 9 4 5 PC~r/US93/05551
~ny 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 Rl comprise from about 50 to 100~ 1,4-phenylene moieties (from
0 to about ~0~ moieties other than 1,4-phenylene) have adequate
soil ,elease activity. For example, polyesters made according to
the present invention with a 40:60 mole ratio of isophthalic
(1,3-phenylene) to terephthalic (1,4-phenylene) acid have adequate
soi1 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
nloieties other than l,4-phenylene for best soil release activity.
Preferably, the Rl moieties consist entirely of (i.e., comprise
100~) 1,4-phenylene moieties, i.e. each Rl moiety is 1,4-phenyl-
ene.
The R2 ~oieties are essentially ethylene moieties, or sub-
stituted ethylene moieties having Cl-C4 alkyl or alkoxy sub-
stitutents. As used herein, the tenm "the R moieties are essen-
tially ethylene moieties, or substituted ethylene moieties having
Cl-C4 alkyl or alkoxy substituents" refers to compounds of the
present invention where the R moieties consist entirely of
ethylene, or substituted ethylene moieties, or are partially
substituted with other compatible moieties. Examples of these
other moieties include linear C3-C6 alkylene moieties such as
1,3-propylene, 1,4-butylene, l,~-pentylene or 1,6-hexamethylene,
1,2-cycloalkylene moieties 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
~ CH2-0 ( CH2CH20 ) p- X
-cH2cH2ocH2cH2ocH2cH2- or -CH2CH20CH2CH2-.
For the R2 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
WO 94/00546 3'~J 1 3 8 9 ~ 5 PCI/US93/055'-
extent. Generally, the degree of partial substitution which can
be tolerated will depend ~pon the backbone length of the compound,
i.e., longer backbones can have greater partial substitution.
Usually, compounds where the R comprise from about 20 to 100
ethylene, or substituted ethylene moieties (from ~ 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 moieties (as
dialkylene glycols) are typically formed from glycols in side
reactions and are then incorporated into the polyester). Prefer-
ably, R comprises from about 80 to 100X ethylene, or substituted
ethylene moieties, and from 0 to about 20X other compatible
moieties.
For the R2 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 thereof.
Preferably, the R2 moieties are essentially ethylene moieties,
1,2-propylene moieties or mixtures thereof. Inclusion of a
greater percentage of ethylene moieties tends to impro~e 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 linear, 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 R moieties are
those which are substituted 1,3-phenylene moieties.
4 ~ 3~945
' 94/00546 PCI/US93/05551
- 7
he substituted R moieties preferabl~ have only one - S03M,
-COOM, -0-~-(R O)m(CH(Y)CH20)n - X or
-A-~(R -A-R4-A) ~ (R50)m(CH(Y)CH2o)n~ X su2stituent. M can be H
or any compatible water-soluble cation. ~uitable 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 - R
R3
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
Cl-C20 hydrocarbyl group; and R is H (ammonium) or a C1-C20
hydrocarbyl group (quat amine). Typical substituted ammonium
cationic groups are those where R4 is H (ammonium) or C1-C4 alkyl,
especially methyl (quat amine); R is C10-Cl8 alky , p y
C12-C14 alkyl; and R and R are each C1-C4 alkyl, especially
methyl.
The R3 moieties having -A-~(R2-A-R4A)~~w
-~-(RS0)m(CH(Y)CH20)n-~-X substituents provide branched backbone
compounds. R3 moieties having -A-~(R -A-R4-A) ~ R2-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)~(0RS)m-~- can be mixed
together or preferably form blocks of -(R 0)- and -(CHtY)CH20)-
moieties. Preferably, the blocks of -(R50)- moieties are located
next to the backbone of the compound. When R is the moiety
-R2-A-R -, m is l; also, the moiety -R2-A-R6- is preferably
located next to the backbone of the compound. For R , the pre-
ferred C3-C4 alkylene is C3H6 (propylene); when R is C3-C4
alkylene, m is preferably from 0 to about 5 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 94/00546 ~ 3 8 ~ ~ ~ PCT/US93/055C-
the moiety -~-(R50)m(CH(Y)CH20)n 1 and most preferably 100~ by
weight (m is 0).
The Y substituents of each moiety -~(R O)m(CH(r)CH20) ~ 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(CH2CH2~)n~~ -
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
can be mixed together, but typically form blocks of
-(CHCH20)n - and 2 2 n2
CH2(0CH2CH2 )pO-X
X can be H, C1-C4 alkyl or -eR7, wherein R is C1-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 43.
The backbone moieties -~-A-Rl-A-R2-~- and -(-A-R3-A-R2_~_ can
be mixed together or can form blocks of -~-A-Rl-A-R2~ and
-~-A-R3-A-R2-t 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
~ 1 3 8 9 4 5
~ 94/00546 PCI'/US93/05~51
_~ _ g _
comDounds of the present invention are oligomers or low molecular
weight polymers. By comDarison, polyesters used in fiber making
typically have a much higher molecular weight, e.g. have from
about 50 ~o 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. When the R3
moieties have the substituent -A-~-(R2-
A-R4-A) ~w r (R50)m(CH(Y)CH20)n-~-X (branched backbone compounds)
or -A-~-(R~-A-R4-A) ~ R2-A- (crosslinked backbone compounds), the
value for w is typically at least 1 and is detenmined 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 ~olymers are block
polyesters having the formula:
O O O
( 2CH2)n20CH2CIH)n ] t (OC- R1 -C0-R2) (-0~l- R3
CH20X
O O O
co_R2) 3 oC ~4 co{(CHCH20)n (CH2CH20)n2~X
CH20X
wherein the R1 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-
ferra~ly sodium 5-sulfo-1,3-phenylene moieties or substituted
1,3-phenylene moieties having the substituent
WO 94/00546 ~ 1 3 8 ~ ~ ~ PCr/US93/05'-
- 10 -
O O O .
) - w ( HCH2~~n ~ ~2CH20)n .' X at the 5
rH2OX
position; the R ~oieties are R or D' moieties, or mixtures
thereof; each X is ethyl or preferably methyl; each n1 is from 1
to about S; the sum of each n1 + n2 is from about 12 to about 43;
when w is 0, u + v is from about 3 to about 10; when w is at least
1, u + v + w is from about ~ to about 10.
Particularly preferred block polyesters are those hhere v is
0, 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 ~(OCH2CH(Y))n(oR4)m ~ (A-Rl-A-R2)U(A-Rl-A-R3)
- A-Rl-A-E(R40)m(CH(Y )CH20)n~ X
In this formula, the moiety -~(A-Rl-A-R2)U(A-R1-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
The linking A moieties are essentially - CO - or -OC- moi-
eties, i.e. the compounds of the present invention are polyesters.
As used herein, the term "the A moieties are
O O
essentidlly - OC - or - CO - moieties" refers to compounds where
O O
Il 11
the A moieties consist entirely of moieties - OC - or - CO -, or
94/00546 f ~ 3 ~ 9 4 5 PCr/US93/05551
are partially substituted with linking moieties such as - NC - or
O O O H
Il 11 11
CN - (amide), and - OCN - or - NCO - (urethane). The degree of
H H H
partial substitution with tnese 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
1~ 11
~ach A is either - OC - or - CO -
The R1 moieties are essentially 1,4-phenylene moieties. As
usea herein, the term "the R moieties are essentially 1,4-
phenylene moieties" refers to compounds where the Rl moieties
consist entirely of 1,4-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 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, l,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-R7 1 A-Rl-A-R7-o ~ X substituent or at least one moiety
-A-R7-~A-Rl-A-R7-~--A- cross-linked to another R1 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-Rl-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 especially
sodium (Na ), as well as ammonium (NH4 ). Also suitable are
substituted ammonium cations havin~ the formula:
W O 94/00546 ~ 1 3 8 ~ ~ 5 - 12 - PCT/US93/05~
R2 ~+ R4
l3
where ~1 and R2 are each a C1-C20 hydrocarbyl group (e.g. alkyl,
hydroxyalkyl) or together form a cyclic or heterocyclic ring of
~rom 4 to 6 carbon atoms (e.g. piperidine, morpholine); R3 is a
Cl-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-C18 alkyl, especially
C12-C14 alkvl; 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. The R1 moieties having
-A-Ri-~A-Rl-A-R7 ~ A- moieties provide cross-linked backbone
compounds. Indeed, syntheses used to make the branched backbone
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-phenyl2ne should be such that the soil
release properties of the compclnd 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
comDound, i.e., longer backbones can have greater partial sub-
stitution for 1,4-phenylene moieties. Usually, compounds where
the R1 comprise from about 50 to 100X 1,4-phenylene moieties (from
0 to about 50~ 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 p1 moieties consist entirely of (i.e., comprise
100~) i,4-phenylene moieties, i.e. each R1 moiety is 1,4-phenyl-
ene.
' ~ 94/00546 ,1 1 ~ ~ 9 ~ ~~ PCI/US93/05551
The R2 moieties 2re essentially substituted ethylene moieties
havina C1-C~ alkyl or alkoxy substititents. As used herein, the
term "the R moieties are essentially substituted ethylene moie-
ties having Cl-C4 alkyl or alkoxy substituents" refers to
compounds of the present invention where the R 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, 1,5-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 l,2-hydroxyalkylenes
such as -CH2-CH- , and oxyalkylene moieties such as
CH2 0 ( CH2CH20 ) p X
-CH2CH20CH2CH2-.
For the R moieties, the degree of partial replacement with
these other moieties shou]d be such that the soil release and
solubility properties of the compounds are not adversely affected
to any great extent. Generally, the degree of partial 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 R cor~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
propertjes. (During the making of polyesters according to the
present invention, smal1 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 20~ other compatible moieties. For the R2
W 0 94/00546 ~ 3 ~ - PC~r/US93tO55'-
moieties, suitable ~!~bstituted ethylene moieties nclude
1,2-pro~ylene, l,~-butylene, ~-methoxv-1,2-propylene and mixtures
thereof. Preferably, the R mcieties are essentially 1,~-
propylene moieties.
he R3 moieties are essentially the polyoxyethylene moiety
~(CH2CH20)q~CH2CH2~. As used herein, the term "the R moieties
are essentially the colyoxyethylene moiety -(CH2CH20)q~H2CH2-
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 .
,he 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 R moiety. Prefe~ably, the
polyoxyethylene moiety comprises from about 90 to 100~ of each R3
moiety. (During the making of polyesters according to the present
invention, very small amounts of oxyalkylene moieties may be
attached to the polyoxyethylene moiety in side reactions and thus
incorporated into the R3 moieties).
For the polyoxyethylene moiety, the value ~o:~ 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 ranqe of from about 12 to about 9C.
~ hQ moieties -(p 0)- and -(CH(Y)CH20)- of the moie~t~s
_ (R40)m(CH(Y)CH20)n - and A--(OCH(Y)CH2)~(52 )m~~~ can be mixed
together or preferably form ~locks of -(R 0)- and -(CH(Y)CH20)-
moieties. Preferably, the blocks of -(R 0)- moieties are located
next to the backbone of the compound. When R 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
~ ~ 94/00546 ~; ~ 3 ~ 9 '1 S PCI'/US93/05551
~.~
preferred C3-C4 d lkylene is C3H6 (proDyle~e); when R is C3-C4
alkylene, m is preferablv 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 comDrises at least about 75g by
weight of the moiety -r-(R40)m(CH(Y)CH20)n and most preferably
100~ 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 100, but is typically 0.
Typical ly, the Y substituents are all H. When 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:
~(CHCH20)n(CH2C~20)
CH2 ( 0CH2CH2 ) pO-X
wherein nl is at least 1 and the sum of nl + n2 is the value for
n. Typically, nl has an average value of from about 1 to about
10. The moieties
-(CHCH20)n - and
-(CH2CH20)n-
CH2(0CH2CH2)pO_X
can be mixed together, but typically form blocks of
-(CHCH20)n - and (CH2cH20)n2 moieties-
CH2(0CH2CH2) pO-X
O
X can be H, Cl-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 lZ to about 45.
The backbone moieties ' A-Rl-A-R2 ' and
WO 94/00546 ~J 1 3 ~ 9 ~ S PCr/US93/0555
- 16 -
-~-A Rl A R3 T can form blocks of -~-A-Rl-A-R2~- ana
1 A Rl A R3~- moieties but are more typically randomly mixea
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 value 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. Gener-
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 (-oC-Rl-Co-R3-)
O O
Il 11
-OC-R-CO-(CH2CH20)n-X
wherein each Rl is a 1,4-phenylene moiety; the R2 are essentially
1,2-propylene 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.
~- 13~ PCT/US93/0~5~1
' ~ 94/00546
- 17 -
Highly preferred polymers for use herein re Folymers of the
formula :
O O
X tOCH2CH2tn tO - C - Rl - ~ - oR2~u
O O
tO - C - Rl - C - Ot tCH2C~20tn X
in which X can be any suitable capping group, with 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 selected for water
solubility anc is a range of values which generally averages from
about 10 to about S0, preferably from about 10 to about 25. The
selection of u is critical to formulation in a liquid detergent
having a relatively high ionic strength. There should be very
little material, preferably less than about 10 mol %, more
preferably less than 5 mol ~, most preferably less than 1 mol ~,
in which u is greater than 5. Furthermore there should be at
least 20 mol ~, preferably at least 40 mol %, of material in which
u ranges from 3 to 5.
The R moieties are essentially 1,4-phenylene moieties. As
used herein, the term "the R moieties are essentially 1, 4-
phenylene moieties" refers to compounds ~here the R moieties
consist entirely of 1, 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 1,4-
phenylene include 1,3-phenylene, 1,2-phenylene,
WO 94/00546 ~ PCr/US93/055'
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-bu ty lene, 1, 5 -penty lene, 1, 6-hexamethylene,
1,7-heptamethylene, l,B-octamethylene, 1,4-cyclohexylene, and
mixtures thereof.
For the Rl 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 r.ot 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 partiai
substitution for 1, 4-phenylene moieties. Usually, compo-Jnds
where the R comprise from about 50% to 100% 1,4-phenylene
moieties (from 0 to about 50% moieties other than 1,4-phenylene)
have adequate soil release activity. For example, polyesters made
according to the present invention with a 40:60 mole ratio of
isophtha I ic ( 1, 3-pheny lene ) to terephthalic ( 1, 4-phenylene 3 acid
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,~-phenylene for best soil
release activity. Preferably, the R moieties consist entirely of
(i.e., comprise 100%) 1,4-phenylene moieties, i.e. each R1 moiety
is 1, 4-phenylene.
For the R ml,ieties, 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 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 solubility. Surprisingly,
inclusion of a greater percentage of 1,2-propylene moietieS tends
to improve the water solubility of the compounds and consequently
19 - 21 38945
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 100X
of the R2 moieties are 1,2-propylene moieties.
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 copending Canadian Patent
Application, CA 1,315,286, by Eugene P. Gosselink.
~D
'~ 1 3 ~ PCr/US93/055~
W094/OOS46
- 20 -
The most preferred polymers for use herein are polymers
acco,~ding to the formula:
O O
X tOCH2CH2tn tO - C - Rl - C - OR2t
O O
~0 - C - R - C - ~t tCH2CH2Otn X
wherein X is methyl, n is 16, Rl is 1,4-phenylene moiety,
R2 is 1,2-prop~-lene moiety and u is essentially between 3
and 5.
(C) Common detergencv inqredients
The compositions according to the present invention are
concentrated liquid detergents which comprise from 2 % to
35 % by weight of the total composition of water.
Preferred compositions according to the present invention
comprise from 5 % to 25 % by weight of the total
composition of water.
The compositions according to the present invention
further comprise conventional detergency ingredients.
Such ingredients are selected from surfactants and
builder and mixtures thereof.
Suitable surfactant materials for use herein include
organic surface-active agent selected from nonionic,
anionic, cationic and zwitterionic surface-active agents
and mixtures thereof.
Suitable anionic surface-active salts are selected from
the group of sulfonates and sulfates. The like anionic
surfactants are well-known in the detergent art and have
found wide application in commercial detergents.
~ 1 3 8 ~ ~ ~ Pcr/usg3/05~l
~ ~94/00546
- 21 -
Preferred anionic water-soluble sulfonate or sulfate
salts have in their molecular structure an alkyl radical
containing from about 8 to about 22 carbon atoms.
Examples of such preferred anionic surfactant salts are
the reaction products obtained by sulfating Cg-C18 fatty
alcohols derived from e.g. tallow oil, palm oil, palm
kernel oil and coconut oil; alkylbenzene sulfonates
wherein the alkyl group contains from about 9 to about 15
carbon atoms; sodium alkylglyceryl ether sulfonates:
ether sulfates of fatty alcohols derived from tallow and
coconut oils; coconut fatty acid monoglyceride sulfates
and sulfonates; and water-soluble salts of paraffin
sulfonates having from about 8 to about 22 carbon atoms
in the alkyl chain. Sulfonated olefin surfactants as
more fully described in e.g. U.S. Patent Specification
3,332,880 can also be used. The neutralizing cation for
the anionic synthetic sulfonates and/or sulfates is
represented by conventional cations which are widely used
in detergent technology such as sodium, potassium or
alkanolammonium.
A suitable anionic synthetic surfactant component herein
is represented by the water-soluble salts of an
alkylbenzene sulfonic acid, preferably sodium
alkylbenzene sulfonates, preferably sodium alkylbenzene
sulfonates having from about lO to 13 carbon atoms in the
alkyl group. Another preferred anionic surfactant
component herein is sodium alkyl sulfates having from
about 10 to 15 carbon atoms in the alkyl group.
The nonionic surfactants suitable for use herein include
those produced by condensing ethylene oxide with a
hydrocarbon having a reactive hydrogen atom, e.g., a
hydroxyl, carboxyl, or amido group, in the presence of an
acidic or basic catalyst, and include compounds having
the general formula RA(CH2CH2O)nH wherein R represents
the hydrophobic moiety, A represents the group carrying
the reactive hydrogen atom and n represents the average
~ S PCT/US93/055'-
W094/00546
- 22 -
number of ethylene oxide moieties. R typically contains
from about 8 to 22 carbon atoms They can also be formed
by the condensation of propylene oxide with a lower
molecular weight compound. n usually varies from about 2
to about 24.
A preferred class of nonionic ethoxylates is represented
by the condensation product of a fatty alcohol having
from 12 to 15 carbon atoms and from about 4 to 10 moles
of ethylene oxide per mole or fatty alcohol. Suitable
species of this class of ethoxylates include : the
condensation product of C12-Cls oxo-alcohols and 3 to 9
moles of ethylene oxide per mole of alcohol; the
condensation product or narrow cut C14-C15 oxo-alcohols
and 3 to 9 moles of ethylene oxide per mole of
fatty(oxo)alcohol; the condensation product of a narrow
cut C12-C13 fatty(oxo)alcohol and 6,5 moles of ethylene
oxide per mole of fatty alcohol; and the condensation
products of a C10-Cl4 coconut fatty alcohol with a degree
of ethoxylation (moles EO/mole fatty alcohol) in the
range from 4 to 8. The fatty oxo alcohols while mainly
linear can have, depending upon the processing conditions
and raw material olefins, a certain degree of branching,
particularly short chain such as methyl branching. A
degree of branching in the range from 15% to 50%
(weight%) is frequently found in commercial oxo alcohols.
Suitable cationic surfactants include quaternary ammonium
compounds of the formula R1R2R3R4N+ where Rl,R2 and R3
are methyl groups, and R4 is a C12_1s alkyl group, or
where Rl is an ethyl or hydroxy ethyl group, R2 and R3
are methyl groups and R4 is a C12_1s alkyl group.
ZwitterioniC surfactants include derivatives of aliphatic
quaternary ammonium, phosphonium, and sulfonium compounds
in which the aliphatic moiety can be straight or branched
chain and wherein one of the aliphatic substituents
contains from about 8 to about 24 carbon atoms and
f~ I 3 ~ PCT/US93/0~551
~94/00546
~3
another substituent contains, at least, an anionic water-
solubilizing group. Particularly preferred zwitterionic
materials are the ethoxylated ammonium sulfonates and
sulfates disclosed in U.S. Patents 3,925,262, Laughlin et
al., issued December 9, 1975 and 3,929,678, Laughlin et
al., issued December 30, 1975.
Semi-polar nonionic surfactants include water-soluble
amine oxides containing one alkyl or hydroxy alkyl moiety
of from about 8 to about 28 carbon atoms and two moieties
selected from the group consisting of alkyl groups and
hydroxy alkyl groups, containing from 1 to about 3 carbon
atoms which can optionally be joined into ring
structures.
Also suitable are Poly hydroxy fatty acid amide
surfactants of the formula R2-C-N-Z, wherein Rl is H,
Cl_4hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a
mixture thereof, R2 is C5_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,
Rl is methyl, R2 is a straight Cll_1s alkyl or alkenyl
chain 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
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
~) 1 3 ~ 9 4 5 PCT/US93/055~
W094/00546
- 24 -
obvious environmental reasons, phosphate builders can
also be used herein.
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,
preferably C12_16, or wherein R can be substituted with
hydroxyl, sulfo sulfoxyl or sulfone substituents.
Specific examples include lauryl succinate, myristyl
succinate, palmityl succinate, 2-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
Suitable fatty acid builders for use herein are saturated
or unsaturated C10-l8 fatty acids, 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.
A preferred builder system for use herein consists of a
mixture of citric acid, fatty acids and succinic acid
derivatives described herein above. The builder system
according to the present invention preferably represents
from 5% to 35% by weight of the total composition.
The compositions according to the invention preferably
comprise enzymes. Suitable enzymes for use herein are
protease, lipases, cellulases and amylases and mixtures
thereof. The compositions according to the present
invention may also comprise an enzyme stabilizing system.
Any conventional enzyme stabilizing system is suitable
~ 1 3 ~ Pcr/usg3/0555l
~94/00546
- 25 -
for use herein, and preferred enzyme stabilizing systems
are based on boric acid or derivatives thereof, 1,2-
propanediol, carboxylic acids, and mixtures thereof.
The compositions herein can contain a series of further,
optional ingredients. Examples of the like additives
include solvents, alkanolamines, pH adjusting agents,
suds regulants, opacifiers, agents to improve the machine
compatibility in relation to enamel-coated surfaces,
perfumes, dyes, bactericides, brighteners, softening
agents and the like.
The present invention is further illustrated in the
following examples.
PC~r/US93/055~
W O 94/00546 ~ 1 3 ~ g ~ ~ 26 -
Examples
Weight %
I II
Alkyl benzene sulfonate 18 6
C13-15 Alkyl 3 ethoxylate sulfate - 12
C13-15 alcohol 7 ethoxylate 13 5
Cl2-14 N-methyl glucosamide - 9
Topped palm kernel fatty acid 11 ll
Dodecyl succinic acid anhydride 4.2
Citric acid 1.8 5
Di-ethylene triamine pentamethylene
phosphonic acid
Ethanol 1 2
Propane diol ll 9.8
Sodium hydroxide 0.6
Potassium hydroxide 2.2
Monoethanolamine 9 12.6
Enzymes 0.7 1.5
Boric acid 1.2 2
Calcium chloride 0.02
Ethoxylated tetraethylene pentamine 0.5 0.5
Perfume 0.6 0.5
PVP 0.5 l.0
Terephthalate-based polymer 0.46 0.46
Water 23 l9
Minors up to lO0 %
~4t00546 ' ~ PCT/US93/05551
- 27 - ~ .
The PVP used in both examples is Luviskol R Kl2, from
BASF (MW 2500). The terephthalate polymer used in both
examples is the preferred polymer described in page 17
hereinbefore, where X is Me, n is 16, Rl is l,4-
phenylene, R2 is l,2-propylene, and u is essentially
between 3 and 5.
Similar compositions were also made, comprising either no
terephthalate-based soil release polymer, or neither PVP
nor terephthalate-based soil release polymer. All the
compositions were then put on storage at room temperature
(about 20~c). Compositions freshly made all had the same
appearance. After 2 weeks storage, it was observed that
compositions comprising neither polymers were clear,
compositions comprising no terephthalate-based soil
release polymer were hazy, and compositions I and II were
clear.
