Note: Descriptions are shown in the official language in which they were submitted.
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LAUNDRY DETERGENT COMPOSITION COMPRISING HYDROPHOBIC SOLVENT AND HYDROPHILIC
SOLVENT
15
2o Technical Field
The present invention relates to liquid compositions and processes for
laundering fabrics therewith.
Background of the invention
A great variety of liquid laundering compositions have been described in the
art, such as liquid compositions comprising enzymes and surfactants which
3o deliver mast of the cleaning performance. However, a problem associated
with such common liquid cleaning compositions, when used in a laundry
application to treat different kinds of fabrics, including cotton and
synthetic
fabrics such as polyesters, polyamides and the like, is that they do not
deliver
an effective performance satisfactorily meeting consumer's needs, on all
types of stains including greasy stains, enzymatic stains, mud/clay stains,
bleachable stains and the like.
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It is thus an object of the present invention to provide overall improved
stain
removal performance on a wide range of stains.
It has now been found that this object can be met by cleaning fabrics with a
liquid composition comprising from 0.0001 % to 5% by weight of the total
composition of an enzyme, a surfactant and a solvent system comprising a
hydrophobic solvent, i.e., a solvent having a hydrophilic index of less than
15, and a hydrophilic solvent, i.e., a solvent having a hydrophilic index of
more than 15, at a weight ratio of said hydrophilic solvent to said
hydrophobic solvent of 10:1 to 2:1.
The hydrophilic index is defined by the following equation:
i 5 molecular weight of the hydrophilic part of the solvent
100.
total molecular weight of the solvent
20 Indeed, it has been found that such liquid compositions comprising an
enzyme, a surfactant and a solvent system as defined herein, when used in a
laundry operation, boost the removal of various types of stains including
greasy stains, mud/clay-containing stains, enzymatic stains, as well as
bleachable stains.
An advantage of the present invention is that excellent performance is
provided in a variety of laundry applications, e.g., laundry detergent, or
laundry additive, and preferably laundry pretreater.
3o Another advantage of the present invention is that when such a solvent
system, as described herein, is added in a liquid composition of the present
invention, the viscosity of said composition is reduced, whatever the
viscosity was before the addition of said solvent system. Thus, the present
invention also provides liquid compositions, as described herein, wherein the
viscosity can be conveniently controlled while maintaining adequate physical
stability, without the need to add any viscosity control agent which would
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raise the formula cost, and add bulk to the compositions without contributing
to the cleaning performance of said compositions. Thus the solvent system
herein has a dual function, i.e., stain removing agent and viscosity
controlling
agent.
Background art
EP-A-137616 discloses laundry liquid compositions formulated in the form of
an emulsion having a pH of 6.5 or above and comprising at least 5 % by
weight of solvents. Such solvents include terpene and terpenoid solvents
(e.g., pinene, d-limonene) as well as other solvents like benzyl alcohol,
paraffins. Pretreating of fabrics and through the wash treatment with such
compositions are disclosed. However, none of these compositions comprise a
solvent system with a hydrophilic solvent and a hydrophobic solvent at a
weight ratio of the hydrophilic solvent to the hydrophobic solvent of 10:1 to
~5 2:1.
Summary of the invention
The present invention encompasses a liquid composition suitable for cleaning
2o fabrics, comprising:
- a surfactant,
- from 0.0001 % to 5% by weight of the total composition of an enzyme,
- and a solvent system comprising a hydrophilic solvent having a
hydrophilic index of more than 15, and a hydrophobic solvent having a
25 hydrophilic index of less than 15, at a weight ratio of said hydrophilic
solvent to said hydrophobic solvent of 10:1 to 2:1,
wherein the hydrophilic index is defined by the equation
molecular weight of the hydrophilic part of the solvent
30 ~ 100 .
total molecular weight of the solvent
The present invention also encompasses a process of cleaning a fabric with a
liquid composition as described herein, said process comprising the steps of
35 applying said composition in its neat form onto said fabric, preferably
only
soiled portions thereof, before rinsing, or washing then rinsing said fabric.
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The present invention further encompasses a process of cleaning fabrics
which includes the steps of diluting in an aqueous bath a liquid composition
in its neat form, as described herein, contacting said fabrics with said
aqueous bath comprising said liquid composition, and subsequently rinsing, or
washing then rinsing said fabrics.
Detailed description of the Invention
Li4uid compositions
The present invention is based on the finding that by adding a solvent system
comprising a hydrophilic solvent having a hydrophilic index of more than 15,
and a hydrophobic solvent having a hydrophilic index of less than 15, at a
weight ratio of said hydrophilic solvent to said hydrophobic solvent of 10:1
to 2:1, in a liquid composition comprising an enzyme (0.0001 %-5%) and a
~ 5 surfactant, improved stain removal performance is obtained with said
composition when used to treat a soiled fabric, especially in pretreatment
application, as compared to the stain removal performance delivered with the
same composition without said solvent system, or comprising only one type
of solvent, i.e., a hydrophilic solvent or a hydrophobic solvent as defined
20 herein, or comprising both a hydrophilic solvent and a hydrophobic solvent
but not at the specific weight ratios from one to the other as defined herein.
By "stain removal performance" it is meant herein stain removal performance
on a variety of stains/soils such as greasy/oily stains, and/or enzymatic
stains
25 and/or mud/clay stains and/or bleachable stains.
By "greasy/oily stains" it is meant herein any soil and stain of greasy nature
that can be found on a fabric like dirty motor oil, mineral oil, make-up,
lipstick
vegetal oil, spaghetti sauce, mayonnaise and the like. Indeed, the liquid
3o compositions herein have been found to be particularly effective on make-up
and spaghetti sauce.
Examples of enzymatic stains include grass, chocolate and blood. Examples
of bleachable stains include tea, coffee, wine and the like.
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The stain removal performance of a given composition on a soiled fabric, for
example under pretreatment conditions, may be evaluated by the following
test method. A composition according to the present invention is first
applied neat on the stained portion of a fabric, left to act thereon from
about
5 1 to about 10 minutes, preferably 5 minutes, after which the pretreated
fabric is washed according to common washing conditions with a
conventional detergent composition, at a temperature of from 30~C to 70~C
for a period of time sufficient to bleach said fabric. For example, typical
soiled fabrics to be used in this stain removal performance test method may
be commercially available from EMC (Empirical Manufacturing Company)
Cincinnati, Ohio, USA, such as clay, grass, spaghetti sauce, gravy, dirty
motor oil, make-up, barbecue sauce, tea, on two different substrates: cotton
(CW120) and polycotton (PCW281.
~ 5 The stain removal performance may be evaluated by comparing side by side
the soiled fabrics pretreated with the composition according to the present
invention with those pretreated with the reference, e.g. the same
composition without such a solvent system according to the present
invention. A visual grading scale may be used to assign differences in panel
2o score units (psu), in a range from 0 to 4.
As a first essential element, the liquid compositions according to the present
invention comprise a solvent system comprising a hydrophobic solvent, as
defined herein, and a hydrophilic solvent, as defined herein, at a weight
ratio
25 of said hydrophilic solvent to said hydrophobic solvent of 10:1 to 2:1.
By "solvent" it is meant herein any hydrocarbon including aliphatic saturated
or unsaturated hydrocarbons or aromatic hydrocarbons that contain or not,
one or more alcoholic groups, one or more ether groups and/or one or more
3o ketone groups.
To define the hydrophilic or hydrophobic character of a solvent herein, the
following hydrophilic index (H11 is used:
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molecular weight of the hydrophilic part of the solvent
total molecular weight of the solvent
100
By "hydrophilic part" of a given solvent it is meant herein all the groups O,
CO, OH, of a given solvent.
By "molecular weight of the hydrophilic part of a solvent" it is meant herein
the total molecular weight of all the hydrophilic parts of a given solvent.
The hydrophilic solvents to be used herein have a hydrophilic index of more
than 15, preferably more than 18, more preferably more than 25 and most
preferably more than 30, and the hydrophobic solvents to the used herein
have a hydrophilic index of less than 15, preferably 14 or less and more
preferably 13 or less.
It is essential that these solvents are present in the liquid compositions
herein
at a weight ratio of said hydrophilic solvent to said hydrophobic solvent of
10:1 to 2:1, preferably 7:1 to 3:1, more preferably 6:1 to 4:1 and most
2o preferably about 5:1. Indeed, such a solvent system provides improved
overall stain removal performance when added in a liquid composition
comprising an enzyme and a surfactant, on various type of stains like greasy
stains (e.g. dirty motor oil), enzymatic stains (e.g. blood) and clay stains
as
well as on bleachable stains (e.g. teal. It is speculated that said solvents
can
be a vehicle to the other active ingredients present in said liquid
compositions, helping them to penetrate the stains.
Typically, the liquid compositions herein comprise from 0.1 % to 20% by
weight of the total composition of said solvent system, preferably from 0.1
3o to 10%, more preferably from 0.2% to 4%, and most preferably from 0.5%
to 3.5%.
Suitable hydrophobic solvents to be used herein include paraffins, terpenes or
terpene derivatives, as well as alkoxylated aliphatic or aromatic alcohofs,
aliphatic or aromatic alcohols, glycols or alkoxylated glycols, and mixtures
thereof, all these solvents have a hydrophilic index of less than 15.
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Suitable terpenes (hydrophilic index of 0) are mono-and bicyclic
monoterpenes, especially those of the hydrocarbon class, which include the
terpinenes, terpinolenes, limonenes and pinenes and mixtures thereof. Highly
preferred materials of this type are d-limonene, dipentene, alpha-pinene
and/or beta-pinene. For example, pinene is commercially available form SCM
Glidco (Jacksonville) under the name Alpha Pinene P&F~.
Terpene derivatives such as alcohols, aldehydes, esters, and ketones which
1o have a hydrophilic index of less than 15 can also be used herein. Such
materials are commercially available as, for example, the a and ~3 isomers of
terpineol and linalool.
All type of paraffins (hydrophilic index of 0) can be used herein, both linear
and not, containing from 2 to 20 carbons, preferably from 4 to 10, more
preferably from 6 to 8. Preferred herein is octane. Octane is commercially
available for example from BASF.
Suitable hydrophobic alkoxylated aliphatic or aromatic alcohols to be used
herein are according to the formula R (A)n-OH wherein R is a linear or
branched saturated or unsaturated alkyl group of from 1 to 20 carbon atoms,
preferably from 2 to 15 and more preferably from 2 to 10, or an alkyl
substituted or non-alkyl substituted aryl group of from 1 to 20 carbon atoms,
preferably from 2 to 15 and more preferably from 2 to 10, wherein A is an
alkoxy group preferably butoxy, propoxy and/or ethoxy, and n is an integer of
from 1 to 5, preferably 1 to 2. Suitable hydrophobic alkoxylated alcohol to be
used herein is 1-methoxy-11-dodecanol (HI =14).
Suitable hydrophobic aliphatic or aromatic alcohols to be used herein are
according to the formula R-OH wherein R is a linear or branched saturated or
3o unsaturated alkyl group of from 1 to 20 carbon atoms, preferably from 2 to
15 and more preferably from 2 to 10, or an alkyl substituted or non-alkyl
substituted aryl group of from 1 to 20 carbon atoms, preferably from 2 to 15
and more preferably from 2 to 10. Suitable aliphatic alcohols to be used
herein include linear alcohols like decanol (HI = 7). Suitable aromatic
alcohol
to be used herein is 3-phenyl-1-butanol (HI= 13).
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Suitable hydrophobic glycols to be used herein are according to the formula
HO-CR1 R2-OH wherein R1 and R2 are independently H or a C2-C10
saturated or unsaturated aliphatic hydrocarbon chain and/or cyclic. Suitable
glycol to be used herein is octadecaneglycol (HI =12).
Suitable hydrophobic alkoxylated glycols to be used herein are according to
the formula R-(A)n-R 1-OH wherein R is H, OH, a linear saturated or
unsaturated alkyl of from 1 to 20 carbon atoms, preferably from 2 to 15 and
more preferably from 2 to 10, wherein R1 is H or a linear saturated or
unsaturated alkyl of from 1 to 20 carbon atoms, preferably from 2 to 15 and
more preferably from 2 to 10, and A is an alkoxy group preferably ethoxy,
methoxy, and/or propoxy and n is from 1 to 5, preferably 1 to 2. Suitable
alkoxylated glycol to be used herein is methoxy octadecanol (HI =11 ).
Particularly preferred hydrophobic solvents to be used herein include d-
~ 5 limonene, dipentene, alpha-pinene, beta-pinene, octane or mixtures
thereof.
Suitable hydrophilic solvents to be used herein include alkoxylated aliphatic
or
aromatic alcohols, aliphatic or aromatic alcohols, glycols or alkoxylated
glycols, and mixtures thereof, all these solvents having a hydrophilic index
of
2o more than 15.
Suitable hydrophilic alkoxylated aliphatic or aromatic alcohois to be used
herein are according to the formula R (A)n-OH wherein R is a linear or
branched saturated or unsaturated alkyl group of from 1 to 20 carbon atoms,
25 preferably from 2 to 15 and more preferably from 2 to 10, or an alkyl
substituted or non-alkyl substituted aryl group of from 1 to 20 carbon atoms,
preferably from 2 to 15 and more preferably from 2 to 10, wherein A is an
alkoxy group preferably butoxy, propoxy and/or ethoxy, and n is an integer of
from 1 to 5, preferably 1 to 2. Particularly suitable alkoxylated aliphatic
3o alcohols to be used herein include methoxy propanol (HI = 37), ethoxy
propanol (HI = 32), propoxy propanol (HI = 28) and/or buthoxy propanol (HI =
27). Particularly suitable alkoxylated aromatic alcohol to be used herein
include 1-methoxy-2-phenyl-1-ethanol (HI = 23).
35 Suitable hydrophilic aliphatic or aromatic alcohols to be used herein are
according to the formula R-OH wherein R is a linear or branched saturated or
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unsaturated alkyl group of from 1 to 20 carbon atoms, preferably from 2 to
15 and more preferably from 2 to 10, or an alkyl substituted or non-alkyl
substituted aryl group of from 1 to 20 carbon atoms, preferably from 2 to 15
and more preferably from 2 to 10. Particularly suitable aliphatic alcohols to
be
used herein include linear alcohols like ethanol (HI = 371 and/or propanol
(HI=281. Particularly suitable aromatic alcohol to be used herein is benzyl
alcohol (HI = 16).
Suitable hydrophilic glycols to be used herein are according to the formula
HO-CR1 R2-OH wherein R1 and R2 are independently H or a C2-C10
saturated or unsaturated aliphatic hydrocarbon chain and/or cyclic.
Particularly suitable glycol to be used herein are propanediol (HI =45) and/or
dodecaneglycol (HI =161.
~ 5 Suitable hydrophilic alkoxylated glycols to be used herein are according
to
the formula R-(Aln-R1-OH wherein R is H, OH, a linear saturated or
unsaturated alkyl group of from 1 to 20 carbon atoms, preferably from 2 to
and more preferably from 2 to 10, wherein R 1 is H or a linear saturated or
unsaturated alkyl group of from 1 to 20 carbon atoms, preferably from 2 to
15 and more preferably from 2 to 10, and A is an alkoxy group preferably
ethoxy, methoxy, and/or propoxy and n is from 1 to 5, preferably 1 to 2.
Particularly suitable alkoxylated glycols to be used herein is
ethoxyethoxyethanol (HI = 371.
Particularly preferred hydrophilic solvents to be used herein are benzyl
alcohol
and/or 1-methoxy-2-propanol.
As a second essential element, the liquid compositions according to the
present invention comprise an enzyme or mixtures thereof at a level of active
3o enzyme of from 0.0001 % to 5% by weight of the total composition,
preferably from 0.001 % to 2%, and more preferably from 0.01 % to 1 %. The
enzymes are desirable herein as they contribute to the stain removal
performance of the liquid compositions.
Suitable enzymes to be used herein include any enzyme known to those
skilled in the art. Particularly suitable enzymes to be used herein include
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those selected from the group consisting of cellulases, hemicellulases,
peroxidases, proteases, gluco-amylases, amylases, lipases, cutinases,
pectinases, xylanases, reductases, oxidases, phenoloxidases, lipoxygenases,
ligninases, pullulanases, tannases, pentosanases, malanases, f3-glucanases,
5 arabinosidases and mixtures thereof.
A preferred combination of enzymes is for example protease, amylase, lipase,
cutinase and/or cellulase. More preferably protease and/or amylase are used
in combination with the lipolytic enzyme variant D96L, as the lipase.
The cellulases usable in the present invention include both bacterial or
fungal
cellulase. Preferably, they will have a pH optimum of between 5 and 9.5.
Suitable cellulases are disclosed in U.S. Patent 4,435,307, Barbesgoard et al,
which discloses fungal cellulase produced from Humicola insolens. Suitable
~ 5 cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-
OS-2.247.832.
Examples of such cellulases are cellulases produced by a strain of Humicola
insolens (Humicola grisea var. thermoidea), particularly the Humicola strain
DSM 1800.
Other suitable cellulases are cellulases originated from Humicola insolens
having a molecular weight of about 50KDa, an isoelectric point of 5.5 and
containing 415 amino acids. Especially suitable cellulases are the cellulases
having color care benefits. Examples of such cellulases are cellulases
described in European patent application No. 91202879.2, filed November 6,
1991 (Novol.
Preferred commercially available protease enzymes include those sold under
the tradenames Alcalase~) SavinaseO, Primase~, Durazym~, and Esperase~
3o by Novo Nordisk A/S (Denmark), those sold under the tradename Maxatase~,
Maxacal~ and Maxapem~ by Gist-Brocades, those sold by Genencor
International, and those sotd under the tradename Opticlean~ and Optimase~
by Solvay Enzymes. Also proteases described in our co-pending application
USSN 08/136,797 can be included in the liquid composition of the invention.
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A preferred protease herein referred to as "Protease D" is a carbonyl
hydrolase variant having an amino acid sequence not found in nature, which
is derived from a precursor carbonyl hydrolase by substituting a different
amino acid for the amino acid residue at a position in said carbonyl hydrolase
equivalent to position + 76, preferably also in combination with one or more
amino acid residue positions equivalent to those selected from the group
consisting of + 99, + 101, + 103, + 104, + 107, + 123, + 27, + 105,
+ 109, + 126, + 128, + 135, + 156, + 166, + 195, + 197, + 204, + 206,
+ 210, + 216, + 217, + 218, + 222, + 260, + 265, and/or + 274 according
to the numbering of Bacillus amyloliquefaciens subtilisin, as described in the
concurrently filed patent application of A. Baeck et al. entitled "Protease-
Containing Cleaning Compositions" having U.S. Serial No. 08/322,676, filed
October 13, 1994, which is incorporated herein by reference in its entirety.
Highly preferred enzymes that can be included in the compositions of the
present invention include lipases. It has been found that the cleaning
performance on greasy soils is synergistically improved by using lipases.
Suitable lipase enzymes include those produced by microorganisms of the
Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as
2o disclosed in British Patent 1,372,034. Suitable lipases include those which
show a positive immunological cross-reaction with the antibody of the lipase,
produced by the microorganism Pseudomonas fluorescens IAM 1057. This
lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan,
under the trade name Lipase P~ "Amano" hereinafter referred to as "Amano-
P". Further suitable lipases are lipases such as M 1 Lipase~ and Lipomax~
(Gist-Brocades). Highly preferred lipases are the D96L lipolytic enzyme
variant
of the native lipase derived from Humicola lanuginosa as described in US
Serial No. 08/341 (826. Preferably the Humicola lanuginosa strain DSM 4106
is used. This enzyme is incorporated into the composition in accordance with
3o the invention at a level of from 50 LU to 8500 LU per liter wash solution.
Preferably the variant D96L is present at a level of from 100 LU to 7500 LU
per liter of wash solution. More preferably at a level of from 150 LU to 5000
LU per liter of wash solution.
By D96L lipolytic enzyme variant is meant the lipase variant as described in
patent application WO 92/05249 viz. wherein the native lipase ex Humicola
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lanuginosa aspartic acid (D) residue at position 96 is changed to Leucine (L).
According to this nomenclature said substitution of aspartic acid to Leucine
in
position 96 is shown as : D96L.
Also suitable are cutinases [EC 3.1.1.50) which can be considered as a
special kind of lipase, namely iipases which do not require interfacial
activation. Addition of cutinases to detergent compositions have been
described in, e.g. WO-A-88/09367 (Genencor).
Amylases (& and/or f3) can be included for removal of carbohydrate-based
stains. Suitable amylases are Termamyl~ (Novo Nordisk), Fungamyl~ and
BAN~ (Novo Nordisk).
The above-mentioned enzymes may be of any suitable origin, such as
~ 5 vegetable, animal, bacterial, fungal and yeast origin.
As a third essential element, the liquid compositions according to the present
invention comprise a surfactant or mixtures thereof.
2o Any surfactant known to those skilled in the art may be suitable herein
including nonionic, anionic, cationic, zwitter~ionic, and/or amphoteric
surfactants. Such surfactants contribute to the stain removal properties of
the compositions according to the present invention.
25 The liquid compositions herein comprise from 0.1 % to 50% by weight of the
total composition of a surfactant or mixtures thereof, preferably from 5 % to
30% and more preferably from 8% to 20%.
Nonionic surfactants are highly preferred herein for performance reasons.
3o Suitable nonionic surfactants to be used herein are fatty alcohol
ethoxylates
and/or propoxylates which are commercially available with a variety of fatty
alcohol chain lengths and a variety of ethoxylation degrees. Indeed, the HLB
values of such alkoxylated nonionic surfactants depend essentially on the
chain length of the fatty alcohol, the nature of the alkoxylation and the
35 degree of alkoxylation. Surfactant catalogues are available which list a
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number of surfactants, including nonionics, together with their respective
HLB values.
Suitable chemical processes for preparing the nonionic surfactants for use
herein include condensation of corresponding alcohols with alkylene oxide, in
the desired proportions. Such processes are well-known to the man skilled in
the art and have been extensively described in the art. As an alternative, a
great variety of alkoxylated alcohols suitable for use herein is commercially
available from various suppliers.
Particularly suitable to be used herein as nonionic surfactants are
hydrophobic nonionic surfactants having an HLB (hydrophilic-lipophilic
balance) below 16, preferably below 15, more preferably below 12, and
most preferably below 10. Those hydrophobic nonionic surfactants have
~ 5 been found to provide good grease cutting properties.
Preferred hydrophobic nonionic surfactants to be used in the compositions
according to the present invention are surfactants having an HLB below 16
and being according to the formula RO-(C2H40)n(C3Hg0),~,-,H, wherein R is a
2o Cg to C22 alkyl chain or a Cg to C2g alkyl benzene chain, and wherein n+m
is from 0 to 20 and n is from 0 to 15 and m is from 0 to 20, preferably n + m
is from 1 to 15 and, n and m are from 0.5 to 15, more preferably n + m is
from 1 to 10 and, n and m are from 0 to 10. The preferred R chains for use
herein are the Cg to C22 alkyl chains. Accordingly, suitable hydrophobic
25 nonionic surfactants for use herein are Dobanol~ 91-2.5 (HLB = 8.1; R is a
mixture of C9 and C11 alkyl chains, n is 2.5 and m is 01, or Lutensal~ T03
(HLB=8; R is a C13 alkyl chains, n is 3 and m is 0), or Lutensol~ A03
(HLB = 8; R is a mixture of C 13 and C 15 alkyl chains, n is 3 and m is 0), or
Tergitol~ 25L3 (HLB = 7.7; R is in the range of C 12 to C 15 alkyl chain
30 length, n is 3 and m is 0), or Dobanol~ 23-3 (HLB = 8.1; R is a mixture of
C 12 and C 13 alkyl chains, n is 3 and m is 0), or Dobanolo 23-2 (HLB = 6.2;
R is a mixture of C 12 and C 13 alkyl chains, n is 2 and m is 0), or Dobanol~
45-7 (HLB=1 1.6; R is a mixture of C14 and C15 alkyl chains, n is 7 and m is
0) Dobanol~ 23-6.5 (HLB=1 1.9; R is a mixture of C12 and C13 alkyl chains,
35 n is 6.5 and m is 0), or Dobanol~ 25-7 (HLB=12; R is a mixture of C12 and
C 15 alkyl chains, n is 7 and m is 0), or Dobanol~ 91-5 (HLB =1 1.6; R is a
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mixture of Cg and C11 alkyl chains, n is 5 and m is 0), or Dobanol~ 91-6
(HLB=12.5 ; R is a mixture of Cg and C1 1 alkyl chains, n is 6 and m is 0), or
Dobanol~ 91-8 (HLB = 13.7 ; R is a mixture of Cg and C 1 1 alkyl chains, n is
8 and m is 0), Dobanol~ 91-10 (HLB = 14.2 ; R is a mixture of Cg to C1 1
alkyl chains, n is 10 and m is 0), or mixtures thereof. Preferred herein are
Dobanol~ 91-2.5 , or Lutensol~ T03, or Lutensol~ A03, or Tergitol~ R 25L3,
or Dabanol~ 23-3, or Dobanol~ 23-2) or mixtures thereof. These Dobanol~
surfactants are commercially available from SHELL. These Lutensol~
surfactants are commercially available from BASF and these Tergitol~
7 o surfactants are commercially available from UNION CARBIDE. Nonionic
surfactants may also be available from Hoechst under the name Surfonic~~
Other suitable nonionic surfactants for use herein include polyhydroxy fatty
acid amide surfactants, or mixtures thereof, according to the formula
R2-CIO)-N(R1)-Z,
wherein R 1 is H, or C 1 _C4 alkyl, C 1 _Cq. hydrocarbyl, 2-hydroxy ethyl, 2-
hydroxy propyl or a mixture thereof, R2 is C5_C31 hydrocarbyl, and Z is a
2o polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3
hydroxyls directly connected to the chain, or an alkoxylated derivative
thereof.
Preferably, R 1 is C 1 _C4 alkyl, more preferably C 1 or C2 alkyl and most
preferably methyl, R2 is a straight chain C7_C1 g alkyl or alkenyl, preferably
a
straight chain Cg_C 1 g alkyl or alkenyl, more preferably a straight chain C
11-
C 1 g alkyl or alkenyl, and most preferably a straight chain C 1 1-C 14 alkyl
or
alkenyl, or mixtures thereof. Z preferably will be derived from a reducing
sugar in a reductive amination reaction; more preferably Z is a glycityl.
3o Suitable reducing sugars include glucose, fructose, maltose, lactose,
galactose, mannose and xylose. As raw materials, high dextrose corn syrup,
high fructose corn syrup, and high maltose corn syrup can be utilised as well
as the individual sugars listed above. These corn syrups may yield a mix of
sugar components for Z. It should be understood that it is by no means
intended to exclude other suitable raw materials. Z preferably will be
selected from the group consisting of -CH2-(CHOH)n-CH20H, -CH(CH20H)-
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(CHOH)n_1-CH20H, -CH2-(CHOH)2-(CHOR')(CHOH)-CH20H, where n is an
integer from 3 to 5, inclusive, and R' is H or a cyclic or aliphatic
monosaccharide, and alkoxylated derivatives thereof. Most preferred are
glycityls wherein n is 4, particularly CH2-(CHOH)4-CH20H.
5
In formula R2 - C(O) - N(R 1 ) - Z, R 1 can be, for example, N-methyl, N-
ethyl,
N-propyl, N-isopropyl, N-butyl, N-2-hydroxy ethyl, or N-2-hydroxy propyl. R2
C(O) - N < can be, for example, cocamide, stearamide, oleamide,
lauramide, myristamide, capricamide, palmitamide, tallowamide and the like.
1 o Z can be 1-deoxyglucityl, 2-deoxyfructityl, 1-deoxymaltityl, 1-
deoxylactityi,
1-deoxygalactityl, 1-deoxymannityl, 1-deoxymaltotriotityl and the like.
Suitable polyhydroxy fatty acid amide surfactants to be used herein may be
commercially available under the trade name HOE~ from Hoechst.
Methods for making polyhydroxy fatty acid amide surfactants are known in
the art. In general, they can be made by reacting an alkyl amine with a
reducing sugar in a reductive amination reaction to form a corresponding N-
alkyl polyhydroxyamine, and then reacting the N-alkyl polyhydroxyamine with
2o a fatty aliphatic ester or triglyceride in a condensation/amidation step to
form
the N-alkyl, N-polyhydroxy fatty acid amide product. Processes for making
compositions containing polyhydroxy fatty acid amides are disclosed for
example in GB patent specification 809,060, published February 18, 1959,
by Thomas Hedley & Co., Ltd., US patent 2,965,576, issued December 20,
1960 to E.R. Wilson, US patent 2,703,798, Anthony M. Schwartz, issued
March 8, 1955, US patent 1,985,424, issued December 25, 1934 to Piggott
and W092/06070, each of which is incorporated herein by reference.
Other nonionic surfactants to be used herein are amine oxide surfactants. The
compositions of the present invention may comprise amine oxide in
3o accordance with the general formula I:
1
R (EO)x(PO)y(BO)zN(0)(CH2R')2.qH20 (I)
Inlgeneral, it can be seen that the structure (I) provides one long-chain
moiety
R (EO)x(PO) (B0lz and two short chain moieties, CH2R'. R' is preferably
selected from hydrogen, methyl and -CH20H. In general R1 is a primary or
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16
branched hydrocarbyl moiety which can be saturated or unsatirated,
preferably, R is a primary alkyl moiety. When x + y + z - 0, R is a
hydrocarbyl moiety having chain I ~ gth of from about 8 to about 18. When
x + y + z is different from 0, R may be somewhat longer, having a
chainlength in the range C 12-C24. The general formula also encompasses
amine oxides wherein x + y + z = 0, R 1 - Cg-C 1 g, R' - H and q = 0-2,
preferably 2. These amine oxides are illustrated by C12-14 alkyldimethyl
amine oxide, hexadecyl dimethylamine oxide, octadecylamine oxide and their
hydrates, especially the dehydrates as disclosed in U.S. Patents 5,075,501
and 5,071 (594, incorporated herein by reference.
The invention also encompasses amine oxides wherein x + y ~z is different
from zero, specifically x + y + z is from about 1 to about 10, R is a primary
alkyl group containing 8 to about 24 carbons, preferably from about 12 to
about 16 carbon atoms; in these embodiments y + z is preferably 0 and x is
preferably from about 1 to about 6, more preferably from about 2 to about 4;
EO represents ethyleneoxy; PO represents propyleneoxy; and BO represents
butyleneoxy. Such amine oxides can be prepared by conventional synthetic
methods, e.g., by the reaction of alkylethoxysuifates with dimethylamine
followed by oxidation of the ethoxylated amine with hydrogen peroxide.
Highly preferred amine oxides herein are solids at ambient temperature, more
preferably they have melting-points in the range 30~C to 90~C. Amine oxides
suitable for use herein are made commercially by a number of suppliers,
including Akzo Chemie) Ethyl Corp., and Procter & Gamble. See
McCutcheon's compilation and Kirk-Othmer review article for alternate amine
oxide manufacturers. Preferred commercially available amine oxides are the
solid, dehydrate ADMOX 1 fi~ and ADMOX 18~, ADMOX 12~ and especially
ADMOX 14~ from Ethyl Corp.
Preferred amine oxides to be used herein include hexadecyldimethylamine
oxide dehydrate, dodecyldimethylamine oxide dehydrate,
octadecyldimethylamine oxide dehydrate, hexadecyltris(ethyleneoxy)dimethyl-
amine oxide, and tetradecyldimethylamine oxide dehydrate.
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Whereas in certain of the preferred embodiments R' - H, there is some
latitude with respect to having R' slightly larger than H. Specifically, the
invention further encompasses embodiments wherein R' - CH20H, such as
hexadecylbis(2- hydroxyethyl)amine oxide, tallowbis(2-hydroxyethyl)amine
oxide, stearylbis(2-hydroxyethyl)amine oxide and oleylbis(2-
hydroxyethyl)amine oxide, dodecyldimethylamine oxide dehydrate.
The liquid compositions according to the present invention may comprise
other surfactants like an anionic surfactant, or mixtures thereof. Anionic
surfactants are suitable herein as they act as wetting agent, i.e., in a
laundry
application they wet the stains on the fabrics, especially on hydrophilic
fabrics. Furthermore, anionic surfactants allow to obtain clear compositions
even when said compositions comprise hydrophobic ingredients such as
hydrophobic surfactants.
Particularly suitable for use herein are suifonate and sulfate surfactants.
The
like anionic surfactants are well-known in the art and have found wide
application in commercial detergents. These anionic surfactants include the
C8-C22 alkyl benzene suifonates (LAS), the C8-C22 alkyl sulfates (AS),
2o unsaturated sulfates such as oley! sulfate, the C 10-C 18 alkyl alkoxy
sulfates
(AES) and the C 10-C 18 alkyl alkoxy carboxylates. The neutralising 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. Preferred herein are the alkyl
sulphate, especially coconut alkyl sulphate having from 6 to 18 carbon atoms
in the alkyl chain, preferably from 8 to 15, or mixtures thereof.
Other anionic surfactants useful for detersive purposes can also be used
herein. These can include salts (including, for example, sodium, potassium,
3o ammonium, and substituted ammonium salts such as mono-, di- and
triethanolamine salts) of soap, Cg-C22 primary or secondary
alkane~ulfonates, Cg-C24 olefinsulfonates, sulfonated polvcarboxylic acids
prepared by suifonation of the pyrolyzed product of alkaline earth metal
citrates, e.g., as described in British patent specification No. 1,082,179, Cg-
C24 alkylpolyglycolethersulfates (containing up to 10 moles of ethylene
oxide); alkyl ester sulfonates such as C 14_ 1 g methyl ester sulfonates; acyl
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glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl phenol ethylene
oxide
ether sulfates, paraffin sulfonates, alkyl phosphates, isethionates such as
the
acyl isethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates,
monoesters of sulfosuccinate (especially saturated and unsaturated C 12-C 18
monoesters) diesters of sulfosuccinate (especially saturated and unsaturated
C6-C 14 diesters), sulfates of alkylpolysaccharides such as the sulfates of
alkylpolyglucoside (the nonionic nonsulfated compounds being described
below). Resin acids and hydrogenated resin acids are also suitable, such as
rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids
present in or derived from tall oil. Further examples are given in "Surface
Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch).
A variety of such surfactants are also generally disclosed in U.S. Patent
3,929,678, issued December 30, 1975 to Laughlin, et al. at Column 23, tine
58 through Column 29, line 23 (herein incorporated by reference).
Other suitable anionic surfactants to be used herein also include acyl
sarcosinate or mixtures thereof, in its acid and/or salt form, preferably long
chain acyl sarcosinates having the following formula:
O
OM
R
2o CH3 O
wherein M is hydrogen or a cationic moiety and wherein R is an alkyl group
of from 11 to 15 carbon atoms, preferably of from 1 1 to 13 carbon atoms.
Preferred M are hydrogen and alkali metal salts, especially sodium and
potassium. Said acyl sarcosinate surfactants are derived from natural fatty
acids and the amino-acid sarcosine (N-methyl glycine). They are suitable to
be used as aqueous solution of their salt or in their acidic form as powder.
Being derivatives of natural fatty acids, said acyl sarcosinates are rapidly
and
completely biodegradable and have good skin compatibility.
Accordingly, particularly preferred long chain acyl sarcosinates to be used
herein include C12 acyl sarcosinate (i.e. an acyl sarcosinate according to the
above formula wherein M is hydrogen and R is an alkyl group of 11 carbon
atoms) and C14 acyl sarcosinate (i.e. an acyl 'sarcosinate according to the
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above formula wherein M is hydrogen and R is an alkyl group of 13 carbon
atoms). C12 acyl sarcosinate is commercially available, for example, as
Hamposyl L-30~ supplied by Hampshire. C14 acyl sarcosinate is
commercially available, for example, as Hamposyl M-30~ supplied by
Hampshire.
Cationic surfactants particularly suitable for use in the liquid compositions
of
the present invention are those having one long-chain hydrocarbyl group.
Examples of such cationic surfactants include the ammonium surfactants
1 o such as alkyldimethylammonium halogenides, and those surfactants having
the formula
fR2(OR3)y][R4(OR3)y]2R5N + X-
~ 5 wherein R2 is an alkyl or alkyl benzyl group having from about 8 to about
18
carbon atoms in the alkyl chain, each R3 is selected from the group
consisting of -CH2CH2-, -CH2CH(CH3)-, -CHZCH(CH20H)-, -CH2CH2CH2-,
and mixtures thereof; each R4 is selected from the group consisting of C 1-C4
alkyl, C q -C4 hydroxyalkyl, benzyl ring structures formed by joining the two
2o R4 groups, -CH2CHOH-CHOHCOR6CHOHCH20H wherein R6 is any hexose
or hexose polymer having a molecular weight less than about 1000, and
hydrogen when y is not 0; R5 is the same as R4 or is an alkyl chain wherein
the total number of carbon atoms of R2 plus R5 is not more than about 18;
each y is from 0 to about 10 and the sum of the y values is from 0 to about
25 15; and X is any compatible anion.
Preferred cationic surfactants are the water-soluble quaternary ammonium
compounds useful in the present composition having the formula
30 R 1 R2R3R4N + X- (i)
wherein R1 is Cg-C1 g alkyl, each of R2, R3 and Rq, is independently C1-Cq.
alkyl, C1-C4 hydroxy alkyl, benzyl, and -(C2H40)xH where x has a value
from 1 to 5, and X is an anion. Not more than one of R2, R3 or R4 should be
35 benzyl.
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The preferred alkyl chain length for R 1 is C 12-C 15 Particularly where the
alkyl group is a mixture of chain lengths derived from coconut or palm kernel
fat or is derived synthetically by olefin build up or OXO alcohols synthesis.
Preferred groups for R2R3 and R4 are methyl and hydroxyethyl groups and
5 the anion X may be selected from halide, methosulphate, acetate and
phosphate ions.
Examples of suitable quaternary ammonium compounds of formulae (i) for
use herein are
coconut trimethyl ammonium chloride or bromide;
coconut methyl dihydroxyethyl ammonium chloride or bromide;
decyl methyl ammonium chloride;
decyl dimethyl hydroxyethyl ammonium chloride or bromide;
C12-15 dimethyl hydroxyethyl ammonium chloride or bromide;
15 coconut dimethyl hydroxyethyl ammonium chloride or bromide;
myristyl trimethyl ammonium methyl sulphate;
lauryl dimethyl benzyl ammonium chloride or bromide;
lauryl dimethyl (ethenoxy)4 ammonium chloride or bromide;-
choline esters (compounds of formula (i) wherein R 1 is -CH2-O-C(O)-C 12-14
2o alkyl and R2R3R4 are methyll.
Other cationic surfactants useful herein are also described in U.S. Patent
4,228,044, Cambre, issued October 14, 1980.
The compositions to be used according to the present invention must be
liquids. As used herein, "liquid" includes "pasty" compositions, and liquid
compositions herein preferably have a viscosity of from 1 cps to 10000 cps
when measured with a Brookfield viscometer at 50 rpm shear rate with a
spindle n~2 at 20~C or with a Carri-med rheometer at 50 dyne/cm2 at 20~C,
3o preferably from 100 cps to 1000 cps, more preferably from 150 cps to 600
cps and most preferably 200 cps to 500 cps.
Preferably, the compositions to be used herein are aqueous. Said aqueous
compositions have a pH as is of from 5 to 12, preferably from 6 to 10, and
more preferably from 7 to 9. The pH of the compositions can be adjusted for
instance by using organic or inorganic acids, or alkalinizing agents.
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The liquid compositions according to the present invention are physically
stable. By "physically stable" it is meant herein that the compositions of the
present invention do not split in two or more phases when exposed in
stressed conditions, e.g., at a temperature of 50 ~C during 2 weeks.
The compositions according to the present invention may further comprise
other optional ingredients like builders, stabilizers, chelating agents, dye
transfer agents, radical scavengers, solvents, brighteners, foam suppresors,
1 o perfumes, soil suspending polyamine polymers, polymeric soil release
agents,
catalysts, bleach, bleach activators and dyes.
Processes for cleaning a fabric
The present invention also encompasses processes of cleaning fabrics,
starting from a liquid composition, as described herein.
The processes of cleaning fabrics of the present invention include the steps
of contacting fabrics with a liquid composition, as described herein before,
neat or diluted, and subsequently rinsing said fabrics. In the preferred
embodiment, when the fabrics are "pretreated", the liquid composition is
applied neat on the fabrics, and the fabrics are subsequently rinsed, or
washed and then rinsed in a normal wash cycle. We have observed that the
stain removal performance improvement is particularly noticeable with the
liquid compositions herein when contacted directly with the soiled portion of
fabrics, before they are washed/rinsed.
In the cleaning processes of the present invention, the Liquid composition
3o comprising an enzyme, a surfactant and said solvent system needs to be
contacted with the fabrics to be cleaned. This can be done either in a so-
called "pretreatment mode", where the liquid composition is applied neat
onto said fabrics before the fabrics are rinsed, or washed then rinsed, or in
a
"soaking mode" where the liquid composition is first diluted in an aqueous
bath and the fabrics are immersed and soaked in the bath, before they are
rinsed, or in a "through the wash mode", where the liquid composition is
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added on top of a wash liquor formed by dissolution or dispersion of a typical
laundry detergent. As discussed earlier, the composition to perform the
processes herein is in the form of a liquid as opposed to a solid or a gas.
It is also essential in these processes according to the present invention,
that
the fabrics be rinsed after they have been contacted with said liquid
composition, before said composition has completely dried off.
In the pretreatment mode, the process comprises the steps of applying said
liquid composition in its neat form onto said fabrics, or at least soiled
portions
thereof (i.e., directly applying said liquid composition as described herein
onto
said fabrics without undergoing any dilution), and subsequently rinsing, or
washing then rinsing said fabrics. In this mode, the neat compositions can
optionally be left to act onto said fabrics for a period of time ranging from
1
~ 5 min. to 1 hour, preferably from 1 minute to 30 minutes, before the fabrics
are rinsed, or washed then rinsed, provided that the composition is not left
to
dry onto said fabrics. For particularly though stains, it may be appropriate
to
further rub or brush said fabrics by means of a sponge or a brush, or by
rubbing two pieces of fabrics against each other.
In another mode, generally referred to as "soaking", the process comprises
the steps of diluting said liquid composition in its neat form in an aqueous
bath so as to form a diluted composition. The dilution level of said liquid
composition in an aqueous bath is typically up to 1:85, preferably up to 1:50
and more preferably about 1:25 (composition:water). The fabrics are then
contacted with the aqueous bath comprising the liquid composition, and the
fabrics are finally rinsed, or washed then rinsed. Preferably in that
embodiment, the fabrics are immersed in the aqueous bath comprising the
Liquid composition, and also preferably, the fabrics are left to soak therein
for
3o a period of time ranging from 30 minutes to 48 hours, preferably from 1
hour
to 24 hours.
In yet another mode which can be considered as a sub-embodiment of
"soaking", generally referred to as "bleaching through the wash", the liquid
composition is used as a so-called laundry additive. And in that embodiment
the aqueous bath is formed by dissolving or dispersing a conventional laundry
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23
detergent in water. The liquid composition in its neat form is contacted with
the aqueous bath, and the fabrics are then contacted with the aqueous bath
containing the liquid composition. Finally, the fabrics are rinsed.
Oational ingredients
The compositions according to the present invention may comprise a
chelating agent as an optional but highly preferred ingredient. Indeed, such
chelating agents further contribute to the benefit of the liquid compositions
1 o herein, i.e., they further improve the stain removal properties of the
liquid
compositions herein. Also they contribute to the safety profile of the liquid
compositions of the present invention which may be used for pretreating a
soiled colored fabric upon prolonged contact times before washing said
fabric.
Suitable chelating agents to be used herein include chelating agents selected
from the group of phosphonate chelating agents, amino carboxylate chelating
agents, polyfunctionally-substituted aromatic chelating agents, and further
chelating agents like glycine, salicylic acid, aspartic acid, glutamic acid,
malonic acid, or mixtures thereof. Chelating agents when used, are typically
present herein in amounts ranging from 0.001 % to 5 % by weight of the total
composition and preferably from 0.05% to 2% by weight.
Suitable phosphonate chelating agents to be used herein may include
ethydronic acid as well as amino phosphonate compounds, including
aminotri(methylene phosphonic acid) (ATM P), amino alkylene poly (alkylene
phosphonate), alkali metal ethane 1-hydroxy diphosphonates, nitrilo
trimethylene phosphonates, ethylene diamine tetra methylene phosphonates,
and diethylene triamine penta methylene phosphonates. The phosphonate
3o compounds may be present either in their acid form or as salts of different
cations on some or all of their acid functionalities. Preferred phosphonate
chelating agents to be used herein are diethylene triamine yenta methylene
phosphonates and aminotri(methylene phosphonic acid). Phosphonate
chelating agents are commercially available from Monsanto under the trade
name DEQUEST~~
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Polyfunctionally-substituted aromatic chelating agents may also be useful in
the compositions herein. See U.S. patent 3,812,044, issued May 21, 1974,
to Connor et al. Preferred compounds of this type in acid form are
dihydroxydisulfobenzenes such as 1,2-dihydroxy -3,5-disulfobenzene.
A preferred biodegradable chelating agent for use herein is ethylene diamine
N,N'- disuccinic acid, or alkali metal, or alkaline earth, ammonium or
substitutes ammonium salts thereof or mixtures thereof. Ethylenediamine
N, N'- disuccinic acids, especially the (S, S) isomer have been extensively
described in US patent 4, 704, 233, November 3, 1987, to Hartman and
Perkins. Ethylenediamine N, N'- disuccinic acids is, for instance,
commercially
available under the tradename ssEDDS~ from Palmer Research Laboratories.
Suitable amino carboxylates to be used herein include ethylene diamine tetra
acetates, diethylene triamine pentaacetates, diethylene triamine pentaacetate
(DTPA),N- hydroxyethylethylenediamine triacetates, nitriiotri-acetates,
ethylenediamine tetrapropionates, triethylenetetraaminehexa-acetates,
ethanol-diglycines, propylene diamine tetracetic acid (PDTA) and methyl
glycine di-acetic acid (MGDA), both in their acid form, or in their alkali
metal,
2o ammonium, and substituted ammonium salt forms. Particularly suitable
amino carboxylates to be used herein are diethylene triamine penta acetic
acid, propylene diamine tetracetic acid (PDTA) which is, for in.;tance,
commercially available from BASF under the trade name Trilon FS~ and
methyl glycine di-acetic acid (MGDA).
Another preferred chelating agent for use herein is of the formula:
RtR2RsRd
R7 Rg COOH OH
NH
NH
OH COOH RS ~
RiR2R3R4
3o wherein R 1, R3, and are independently selected fromgroup
R2, R4 the
consisting of -H, alkyl, alkoxy,aryl, aryloxy, -CI, -Br, -N02, and
-C(0)R', -
S02R"; wherein R' is selectedfrom the group consisting of alkyl,
-H, -OH,
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alkoxy, aryl, and aryloxy; R" is selected from the group consisting of alkyl,
alkoxy, aryl, and aryloxy; and R5, Rg, R~, and Rg are independently selected
from the group consisting of -H and alkyl.
5 Particularly preferred chelating agents to be used herein are ATMP,
diethylene
triamine methylene phosphonate, ethylene N,N'-disuccinic acid, diethylene
triamine pantaacetate, glycine, salicylic acid, aspartic acid, glutamic acid,
malonic acid or mixtures thereof.
The compositions according to the present invention may comprise a radical
scavenger as an optional ingredient. Suitable radical scavengers for use
herein include the well-known substituted mono and dihydroxy benzenes and
their analogs, alkyl and aryl carboxylates and mixtures thereof. Preferred
such radical scavengers for use herein include di-tert-butyl hydroxy toluene
~ 5 (BHT), hydroquinone, di-tert-butyl hydroquinone, mono-tert-butyl
hydroquinone, tert-butyl-hydroxy anysole, benzoic acid, toluic acid, catechol,
t-butyl catechol, benzylamine, 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)
butane, n-propyl-gallate or mixtures thereof and highly preferred is di-tert-
butyl hydroxy toluene. Radical scavengers when used, are typically present
2o herein in amounts ranging from 0.001 % to 2% by weight of the total
composition and preferably from 0.001 % to 0.5% by weight.
The liquid compositions according to the present invention may further
comprise a soil suspending polyamine polymer or mixtures thereof, as
25 optional but highly preferred ingredient. Any soil suspending polyamine
polymer known to those skilled in the art may also be used herein.
Particularly suitable polyamine polymers for use herein are polyalkoxylated
polyamines. Such materials can conveniently be represented as molecules of
the empirical structures with repeating units
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[N R] n Amine form
falkoxy)y
and
R1
fN+ R] n nX- Quatemized form
1
(alkoxy)y
wherein R is a hydrocarbyl group, usually of 2-6 carbon atoms; R 1 may be a
~ 5 C 1-C20 hydrocarbon; the alkoxy groups are ethoxy, propoxy, and the like,
and y is 2-30, most preferably from 10-20; n is an integer of at least 2,
preferably from 2-20, most preferably 3-5; and X- is an anion such as halide
or methylsuifate, resulting from the quaternization reaction.
2o The most highly preferred polyamines for use herein are the so-called
ethoxylated polyethylene amines, i.e., the polymerized reaction product of
ethylene oxide with ethyleneimine, having the general formula
(Et0) (N CH2 CH2 ] n N (Et0)y
(Eto)y (Eto)y
when y - 2-30. Particularly preferred for use herein is an ethoxylated
polyethylene amine, in particular ethoxylated tetraethylenepentamine, and
3o quaternized ethoxylated hexamethylene diamine.
It has surprisingly been found that said soil suspending polyamine polymers
contribute to the benefits of the present invention, i.e., that when added on
top of said solvent system in a liquid composition comprising an enzyme and
a surfactant, they further improve the stain removal performance of said
composition, especially under laundry pretreatment conditions. Indeed, they
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allow to improve the stain removal performance on a variety of stains
including greasy stains, enzymatic stains, ciay/mud stains as well as on
bleachable stains.
Typically, the compositions comprise up to 10% by weight of the total
composition of such a soil suspending polyamine polymer or mixtures
thereof, preferably from 0.1 % to 5% and more preferably from 0.3% to 2%.
The compositions herein may also comprise other polymeric soil release
agents known to those skilled in the art. Such polymeric soil release agents
are characterised by having both hydrophilic segments, to hydrophilize the
surface of hydrophobic fibres, such as polyester and nylon, and hydrophobic
segments, to deposit upon hydrophobic fibres and remain adhered thereto
through completion of washing and rinsing cycles and, thus, serve as an
~ 5 anchor for the hydrophilic segments. This can enable stains occurring
subsequent to treatment with the soil release agent to be more easily cleaned
in later washing procedures.
The polymeric soil release agents useful herein especially include those soil
20 release agents having: (a) one or more nonionic hydrophile components
consisting essentially of (i) polyoxyethylene segments with a degree of
polymerization of at least 2, or (ii) oxypropylene or polyoxypropylene
segments with a degree of polymerization of from 2 to 10, wherein said
hydrophile segment does not encompass any oxypropylene unit unless it is
25 bonded to adjacent moieties at each end by ether linkages, or (iii) a
mixture
of oxyalkylene units comprising oxyethylene and from 1 to about 30
oxypropylene units wherein said mixture contains a sufficient amount of
oxyethylene units such that the hydrophile component has hydrophilicity
great enough to increase the hydrophilicity of conventional polyester
3o synthetic fiber surfaces upon deposit of the soil release agent on such
surface, said hydrophiie segments preferably comprising at least about 25
oxyethylene units and more preferably; especially for such components
having about 20 to 30 oxypropylene units, at least about 50% oxyethylene
units; or (b) one or more hydrophobe components comprising (i) Cg
35 oxyalkylene terephthalate segments, wherein, if said hydrophobe components
also comprise oxyethylene terephthalate, the ratio of oxyethylene
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terephthalate:C3 oxyalkylene terephthalate units is about 2:1 or lower, (ii)
Cq,-C6 alkylene or oxy C4-Cg alkylene segments, or mixtures therein, (iii)
poly
(vinyl ester) segments, preferably polyvinyl acetatel, having a degree of
polymerization of at least 2, or (iv) C1-C4 alkyl ether or C4 hydroxyalkyl
ether substituents, or mixtures therein, wherein said substituents are present
in the form of C1-C4 alkyl ether or C4 hydroxyalkyl ether cellulose
derivatives, or mixtures therein, and such cellulose derivatives are
amphiphilic, whereby they have a sufficient level of C 1-Cq, alkyl ether
and/or
Cq, hydroxyalkyl ether units to deposit upon conventional polyester synthetic
fiber surfaces and retain a sufficient level of hydroxyls, once adhered to
such
conventional synthetic fiber surface, to increase fiber surface
hydrophilicity,
or a combination of (a) and (b).
Typically, the polyoxyethylene segments of (a)(i) will have a degree of
polymerization of from about 1 to about 200, although higher levels can be
used, preferably from 3 to about 150, more preferably from 6 to about 100.
Suitable oxy C4-Cg alkylene hydrophobe segments include, but are not
limited to, end-caps of polymeric soil release agents such as
M03S(CH2)nOCH2CH20-, where M is sodium and n is an integer from 4-6,
2o as disclosed in U.S. Patent 4,721,580, issued January 26, 1988 to
Gosselink.
Polymeric soil release agents useful in the present invention also include
cellulosic derivatives such as hydroxyether cellulosic polymers, co-polymeric
blocks of ethylene terephthalate or propylene terephthalate with polyethylene
oxide or polypropylene oxide terephthalate, and the like. Such agents are
commercially available and include hydroxyethers of cellulose such as
METHOCEL (Dow). Cellulosic soil release agents for use herein also include
those selected from the group consisting of C 1-C4 alkyl and C4 hydroxyalkyl
3o cellulose; see U.S. Patent 4,000,093, issued December 28, 1976 to Nicol, et
al.
Soil release agents characterised by polyvinyl ester) hydrophobe segments
include graft co-polymers of polyvinyl ester), e.g., C 1-Cg vinyl esters,
preferably polyvinyl acetate) grafted onto polyalkylene oxide backbones,
such as polyethylene oxide backbones. See European Patent Application 0
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29
219 048, published April 22, 1987 by Kud, et af. Commercially available soil
release agents of this kind include the SOKALAN type of material, e.g.,
SOKALAN HP-22, available from BASF (West Germany).
One type of preferred soil release agent is a co-polymer having random blocks
of ethylene terephthalate and polyethylene oxide (PEO) terephthalate. The
molecular weight of this polymeric soil release agent is in the range of from
about 25,000 to about 55,000. See U.S. Patent 3,959,230 to Hays, issued
May 25, 1976 and U.S. Patent 3,893,929 to Basadur issued July 8, 1975.
Another preferred polymeric soil release agent is a polyester with repeat
units
of ethylene terephthalate units which contains 10-15% by weight of ethylene
terephthalate units together with 90-80% by weight of polyoxyethylene
terephthalate units, derived from a polyoxyethylene glycol of average
molecular weight 300-5,000. Examples of this polymer include the
commerciaify available material ZELCON 5126 (from Dupont) and MILEASE T
(from ICI). See also U.S. Patent 4,702,857, issued October 27, 1987 to
Gosselink.
Another preferred polymeric soil release agent is a sulfonated product of a
substantially linear ester oligomer comprised of an oligomeric ester backbone
of terephthaloyl and oxyalkyleneoxy repeat units and terminal moieties
covaiently attached to the backbone. These soil release agents are fully
described in U.S. Patent 4,968,451, issued November 6, 1990 to J.J.
Scheibel and E.P. Gosselink. Other suitable polymeric soil release agents
include the terephthalate polyesters of U.S. Patent 4,711,730, issued
December 8, 1987 to Gosselink et al, the anionic end-capped oligomeric
esters of U.S. Patent 4,721 (580, issued January 26, 1988 to Gosselink, and
the block polyester oligomeric compounds of U.S. Patent 4,702,857, issued
3o October 27, 1987 to Gosselink.
Preferred polymeric soil release agents also include the soil release agents
of
U.S. Patent 4,877,896, issued October 31, 1989 to Maldonado et ai, which
discloses anionic, especially sulfoaroyl, end-capped terephthalate esters.
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Still another preferred soil release agent is an o(igomer with repeat units of
terephthaloyl units, sulfoisoterephthaloyl units, oxyethy(eneoxy and oxy-1,2-
propylene units. The repeat units form the backbone of the oligomer and are
preferably terminated with modified isethionate end-caps. A particularly
5 preferred soil release agent of this type comprises about one
sulfoisophthaloyl unit) 5 terephthaloyl units, oxyethyleneoxy and oxy-1,2-
propyleneoxy units in a ratio of from about 1.7 to about 1.8, and two end-
cap units of sodium 2-f2-hydroxyethoxy)-ethanesu(fonate. Said soil release
agent also comprises from about 0.5% to about 20%, by weight of the
oligomer, of a crystalline-reducing stabilizer, preferably selected from the
group consisting of xylene sulfonate, cumene sulfonate, toluene sulfonate,
and mixtures thereof. See U.S. Pat. No. 5,415,807, issued May 16, 1995,
to Gosselink et al.
~ 5 If utilised, soil release agents will generally comprise from about 0.01 %
to
about 10.0%, by weight, of the detergent compositions herein, typically from
about 0.1 % to about 5%, preferably from about 0.2% to about 3.0%.
The compositions of the present invention may also include one or more
20 materials effective for inhibiting the transfer of dyes from one dyed
surface to
another during the cleaning process. Generally, -such dye transfer inhibiting
agents include polyvinyl pyrrolidone polymers, polyamine N-oxide polymers,
co-polymers of N-vinylpyrrolidone and N-vinylimidazole, manganese
phthalocyanine, peroxidases, and mixtures thereof. If used, these agents
25 typically comprise from about 0.01 % to about 10% by weight of the
composition, preferably from about 0.01 % to about 5 %, and more preferably
from about 0.05% to about 2%.
More specifically, the polyamine N-oxide polymers preferred for use herein
3o contain units having the following structural formula: R-Ax-P; wherein P is
a
polymerizable unit to which an N-O group can be attached or the N-O group
can form part of the polymerizable unit or the N-O group can be attached to
both units; A is one of the following structures: -NC10)-, -C(O)O-, -S-, -O-, -
N =; x is 0 or 1; and R is aliphatic, ethoxylated aliphatics, aromatics,
heterocyclic or alicyclic groups or any combination thereof to which the
nitrogen of the N-O group can be attached or the N-O group is part of these
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groups. Preferred polyamine N-oxides are those wherein R is a heterocyclic
group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and
derivatives thereof.
The N-O group can be represented by the following general structures:
O O
(Rt)x- i -(R2)y~ =Nw'(Rt)x
(R3)z
wherein R 1, R2, R3 are aliphatic, aromatic, heterocyclic or alicyclic groups
or
combinations thereof; x, y and z are 0 or 1; and the nitrogen of the N-O
group can be attached or form part of any of the aforementioned groups.
The amine oxide unit of the polyamine N-oxides has a pKa < 10, preferably
pKa < 7, more preferred pKa < 6.
Any polymer backbone can be used as long as the amine oxide polymer
~ 5 formed is water-soluble and has dye transfer inhibiting properties.
Examples
of suitable polymeric backbones are polyvinyis, polyaikylenes, polyesters,
polyethers, polyamide, polyimides, polyacrylates and mixtures thereof. These
polymers include random or block co-polymers where one monomer type is
an amine N-oxide and the other monomer type is an N-oxide. The amine N-
20 oxide polymers typically have a ratio of amine to the amine N-oxide of 10:1
to 1:1,000,000. However, the number of amine oxide groups present in the
polyamine oxide polymer can be varied by appropriate co-polymerization or by
an appropriate degree of N-oxidation. The polyamine oxides can be obtained
in almost any degree of polymerization. Typically, the average molecular
25 weight is within the range of 500 to 1,000,000; more preferred 1,000 to
500,000; most preferred 5,000 to 100,000. This preferred class of
materials can be referred to as "PVNO". The most preferred polyamine N
oxide useful in the detergent compositions herein is poly(4-vinylpyridine-N
oxide) which has an average molecular weight of about 50,000 and an amine
3o to amine N-oxide ratio of about 1:4.
Co-polymers of N-vinylpyrrolidone and N-vinylimidazole polymers (referred to
as a class as "PVPVI"? are also preferred for use herein. Preferably the
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PVPVI has an average molecular weight range from 5,000 to 1,000,000,
more preferably from 5,000 to 200,000, and most preferably from 10,000 to
20,000. (The average molecular weight range is determined by light
scattering as described in Barth, et al., Chemical Analysis, Vol 1 13. "Modern
Methods of Polymer Characterization", the disclosures of which are
incorporated herein by reference.) The PVPVI co-polymers typically have a
molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1:1 to 0.2:1, more
preferably from 0.8:1 to 0.3:1, most preferably from 0.6:1 to 0.4:1. These
co-polymers can be either linear or branched.
The present invention compositions may also employ a polyvinylpyrrolidone
("PVP") having an average molecular weight of from about 5,000 to about
400,000, preferably from about 5,000 to about 200,000, and more
preferably from about 5,000 to about 50,000. PVP's are known to persons
~ 5 skilled in the detergent field; see, for example, EP-A-262,897 and EP-A-
256,696, incorporated herein by reference. Compositions containing PVP
can also contain polyethylene glycol ("PEG") having an average molecular
weight from about 500 to about 100,000, preferably from about 1,000 to
about 10,000. Preferably, the ratio of PEG to PVP on a ppm basis delivered
20 in wash solutions is from about 2:1 to about 50:1 ( and more preferably
from
about 3:1 to about 10:1.
If high sudsing is desired, suds boosters such as C 10-C 16 alkanolamides can
be incorporated into the compositions, typically at 1 %-10% levels. The C10'
25 C 14 monoethanol and diethanol amides illustrate a typical class of such
suds
boosters. Use of such suds boosters with high sudsing adjunct surfactants
such as the amine oxides, betaines and sultaines noted above is also
advantageous. If desired, soluble magnesium salts such as MgCl2, MgS04,
and the like, can be added at levels of, for example, 0.1 %-2%, to provide
3o additional suds and to enhance grease removal performance.
Any optical brighteners, fluorescent whitening agents or other brightening or
whitening agents known in the art can be incorporated in the instant
compositions when they are designed for fabric treatment or laundering, at
35 levels typically from about 0.05% to about 1.2%, by weight, of the
detergent compositions herein. Commercial optical brighteners which may be
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useful in the present invention can be classified into subgroups, which
include, but are not necessarily limited to, derivatives of stilbene,
pyrazoline,
coumarin, carboxylic acids, methinecyanines, dibenzothiophene-5, 5-dioxide,
azoles, 5- and 6-membered-ring heterocyclic brighteners, this list being
illustrative and non-limiting. Examples of such brighteners are disclosed in
"The Production and Application of Fluorescent Brightening Agents", M.
Zahradnik, Published by John Wiiey & Sons, New York ( 1982).
Specific examples of optical brighteners which are useful in the present
compositions are those identified in U.S. Patent 4,790,856, issued to Wixon
on December 13, 1988. These brighteners include the PHORWHITE series of
brighteners from Verona. Other brighteners disclosed in this reference
include: Tinopal UNPA, Tinopal CBS and Tinopal SBM; available from Ciba-
Geigy; Artic White CC and Artic White CWD, available from Hilton-Davis,
~ 5 located in Italy; the 2-(4-styryi-phenyl)-2H-naphthol[1 (2-d]triazoles;
4,4'-bis-
( 1,2,3-triazol-2-yl)-stil- benes; 4,4'-bis(styryl)bisphenyls; and the
aminocoumarins. Specific examples of these brighteners include 4-methyl-7-
diethyl- amino coumarin; 1,2-bis(-benzimidazol-2-yl)ethylene; 2,5-
bis(benzoxazol-2-yl)thiophene; 2-styryl-napth-[1,2-d)oxazole; and 2-Istilbene-
20 4-yl)-2H-naphtho- [1,2-d]triazole. See also U.S. Patent 3,646,015, issued
February 29, 1972) to Hamilton. Anionic brighteners are typically preferred
herein.
Depending on the end-use envisioned, the liquid compositions herein can be
25 packaged in a variety of containers including conventional bottles, bottles
equipped with roll-on, sponge, brusher or sprayers, or sprayers.
Although the preferred application of the liquid compositions described herein
3o is laundry application, as a laundry detergent or as a laundry additive and
especially as a pretreater such compositions may also be used to clean hard-
surfaces.
The invention is further illustrated by the following examples.
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Examples
Liquid compositions were prepared which comprise the indicated ingredients
in the indicated proportions (weight%):
Ingredients - . _2
(%w/w) (%w/w) (%w/w)
Neodol~ 45.7 12 - 5
Neodol~ 23.3 - 5 5
Benzyl alcohol (HI =16) 1.0 - -
1-methoxy propanol (HI=37) - 2.0 -
Ethanol (HI=37) - - 3.0
Limonene (H I = 0) 0.2 - -
Pinene (HI=0) - 0.5
Octane (HI=Ol - - 0.4
Lipolase D96/L(100KNU/g) 0.12 0.10 0.05
Protease (34g/1) 0.9 0.9 0.3
Amylase (300KNU/g) 0.1 0.2 0.3
Ethoxylated 15-18 tetraethylenepentamine1.0 2.0 0.5
DTPA" 0.4 - -
DTPMP'"'" - 0.3 -
ATMP*"* *' - - 0.16
Water and minors up to up to up to
100 100 100
NaOH to pH 7.5
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fn~redients 4 5 6
(%w/w) (%w/w) (~~uw/w)
Surfonic~ 24.4 12 8 4
Neodol~ 23.65 - - q.
Na alkyl sulphate 12 15 10
Benzyl alcohol (HI =16) - 1.5 -
1-methoxy propanol (HI=37) - - 3.0
Ethoxy ethoxy ethanol (HI =37) 0.5 - -
Limonene (HI=0) - 0.4 -
Pinene (HI =0) - - O,g
Octane (HI =0) 0.2 - -
Lipolase D96/L(100KNU/g) 0.10 0.12 0.8
Protease (34g/1) 0.7 0.7 0.9
Amylase (300KNU/g) 0.15 0.12 0.07
Ethoxylated 15-18 tetraethylenepentamine- 0.8 2.0
DTPA * 0. 5 - -
DTPMP*~'* - 0.5 -
I~ Water and minors up to up to up to
100 100 100
I NaOH to pH 7.5
DTPA*~ is diethylene triamine pentaacetate.
DTPMP*' ~" is diethylene triamine yenta methylene phosphoric acid.
5 ATMP'* *''* is aminotri(methylene phosphoric acid).
Compositions 1 to 3 can be used in a pretreatment mode. In this mode, such
a composition is applied neat on the stained portion of a fabric and left to
act
thereon for 5 minutes. Then the fabric is washed with a conventional
detergent and rinsed. Excellent stain removal is obtained therewith on various
stains including greasy stains, enzymatic stains, clay stains and bleachable
stains.
Compositions 4 to 5 can be used in a through-the-wash mode. In this mode
15 such a composition is contacted with an aqueous bath formed by dissolution
of a conventional detergent in water. Fabrics are then contacted with the
aqueous bath comprising the liquid detergent, and the fabrics are rinsed.
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Excellent stain removal is obtained on various stains including greasy stains,
enzymatic stains, clay stains and bleachable stains.
Composition 6 can be used in a soaking mode. In this mode 100 ml of such a
liquid composition is diluted in 10 liters of water. The fabrics are then
contacted with this aqueous bath containing the composition, and left to
soak therein for a period of time of 24 hours. The fabrics are eventually
rinsed. Excellent stain removal is obtained therewith on various stains
including greasy stains, enzymatic stains, clay stains and bleachable stains.
