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SUBSTANTIALLY ODOR-FREE POLYHYDROXYL SOLVENTS
s
FIELD
The present invention relates to a subslantially odor-free polyhydroxyl
10 solvent, and method of making such odor-free solvent. More specifically, it
relates to liquid detergent compositions comprising sl Ihshntially odor-free
polyhydroxyl solvents.
BACKGROUND
Polyhydroxyl solvents are known in the art, including its use in liquid
15 detergent compositions. There is a problem with polyhydroxyl solvents becausethey have malodor. In addition, liquid detergent compositions comprising such
polyhydroxyl solvents also have malodor. When the solvents are used in liquid
detergent compositions, the malodor is noticeable to consumers who use the
detergent cG",positions. Consumers usually expect detergent compositions to
20 have a pleasant smell. In addition, the consumers may believe that the fabric or
hard surface being cleaned by the detergent composition containing such
solvents will also have malodor. Thus, such polyhydroxyl solvents having
malodor are very undesirable by consumers.
In addition, liquid compositions comprising polyhydroxyl solvents having
25 malodor may contain larger quar,lilies of perfume in order to mask the malodor.
This leads to a higher formulation cost and ulli,nately, a higher priced product for
consumers. The more expensive formulation is also undesirable to consumers.
For the foregoing reasons, there is a need for substantially odor-free
polyhydroxyl solvents, especially when such solvents are used in liquid detergent
30 compositions. None of the existing art provides all of the advantages and
benefits of the present invention.
SUMMARY
The present invention is directed to a substantially odor-free polyhydroxyl
solvent wherein the polyhydroxyl solvent is substantially free of the following
35 consumer noticeable malodorous components:
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a. highly volatile malodorous components having a boiling point lower
than the polyhydroxyl solvent; and
b. nonvolatile malodorous components having
(1 ) a boiling point higher than the polyhydroxyl solvent; and
(2) having a lower polarity than the polyhydroxyl solvent.
The present invention is also directed to a process for making a
substantially odor-free polyhydroxyl solvent, wherein the solvent is substantially
free of consumer noticeable malodorous components, comprising the following
steps:
a. removing highly volatile malodorous components from the polyhydroxyl
solvent by separation techniques based upon different boiling points;
b. mixing the polyhydroxyl solvent of step (a) with water; and
c. treating the mixture of step (b) with activated carbon, whereby the
nonvolatile malodorous components are removed.
l 5 These and other features, aspects, and advantages of the present
invention will become evident to those skilled in the art from a reading of the
present disclosure.
DETAILED DESCRIPTION
While the speciricalion concludes with claims particularly pointing and
distinctly claiming the invention, it is believed that the present invention will be
better understood from the following description.
All percentages are by weight of total composition unless specifically
stated otherwise.
All ratios are weight ratios unless specifically stated otherwise.
As used herein, "comprising" means that other steps and other ingredients
which do not affect the end result can be added. This term encompasses the
terms "consisting of" and "consisting essentially of".
The "calculated logP" (CLogP) is determined by the fragment approach of
Hansch and Leo (cf., A. Leo, in Comprehensive Medicinal Chemistry, Vol. 4, C.
Hansch, P.G. Sammens, J.B. Taylor and C.A. Ramsden, Eds., p. 295, Pergamon
Press, 1990). The fragment approach is based on the chemical structure of a
compound and takes into account the numbers and type of atoms, the atom
connectivity, and chemical bonding. The CLogP values are reliable and a widely
used estimate for physicochemical properties.
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All cited references are incorporated herein by reference in their entireties.
Citation of any reference is not an admission regarding any determination as to
its availability as prior art to the claimed invention.
I. Polyhydroxyl Solvent
The present invention is directed to a substantially odor-free polyhydroxyl
solvent being substantially free of consumer noticeable malodorous components.
The polyhydroxyl solvent in which the malodorous components are removed
from are described in detail below.
The polyhydroxyl solvent is selected from the group consisting of:
lO A. hexane diol isomers including: 2,3-butanediol, 2,3-dimethyl-; 1,2-
butanediol, 2,3-dimethyl-; 1,2-butanediol, 3,3-dimethyl-; 2,3-pentanediol,
2-methyl-; 2,3-pentanediol, 3-methyl-; 2,3-pentanediol, 4-methyl-; 2,3-
hexanediol; 3,4-hexanediol; 1,2-butanediol, 2-ethyl-; 1,2-pentanediol, 2-
methyl-; 1,2-pentanediol, 3-methyl-; 1,2-pentanediol, 4-methyl-; and/or
l 5 1 ,2-hexanediol;
B. heptane diol isomers including: 1,3-propanediol, 2-butyl-; 1,3-propanediol,
2,2-diethyl-; 1,3-propanediol, 2-(1-methylpropyl)-; 1,3-propanediol, 2-(2-
methylpropyl)-; 1,3-propanediol, 2-methyl-2-propyl-; 1,2-butanediol, 2,3,3-
trimethyl-; 1,4-butanediol, 2-ethyl-2-methyl-; 1,4-butanediol, 2-ethyl-3-
methyl-; 1,4-butanediol, 2-propyl-; 1,4-butanediol, 2-isopropyl-; 1,5-
pentanediol, 2,2-dimethyl-; 1,5-pentanediol, 2,3-dimethyl-; 1,5-
pentanediol, 2,4-dimethyl-; 1,5-pentanediol, 3,3-dimethyl-; 2,3-
pentanediol, 2,3-dimethyl-; 2,3-pentanediol, 2,4-dimethyl-; 2,3-
pentanediol, 3,4-dimethyl-; 2,3-pentanediol, 4,4-dimethyl-; 3,4-
pentanediol, 2,3-dimethyl-; 1,5-pentanediol, 2-ethyl-; 1,6-hexanediol, 2-
methyl-; 1,6-hexanediol, 3-methyl-; 2,3-hexanediol, 2-methyl-; 2,3-
hexanediol, 3-methyl-; 2,3-hexanediol, 4-methyl-; 2,3-hexanediol, 5-
methyl-; 3,4-hexanediol, 2-methyl-; 3,4-hexanediol, 3-methyl-; 1,3-
heptanediol; 1,4-heptanediol; 1,5-heptanediol; and/or 1,6-heptanediol;
C. octane diol isomers including: 1,3-propanediol, 2-(2-methylbutyl)-; 1,3-
propanediol, 2-(1,1-dimethylpropyl)- 1,3-propanediol, 2-(1,2-
dimethylpropyl)-; 1,3-propanediol, 2-(1-ethylpropyl)-; 1,3-propanediol, 2-(1-
methylbutyl)-; 1,3-propanediol, 2-(2,2-dimethylpropyl)-; 1,3-propanediol, 2-
(3-methylbutyl)-; 1,3-propanediol, 2-butyl-2-methyl-; 1,3-propanediol, 2-
ethyl-2-isopropyl-; 1,3-propanediol, 2-ethyl-2-propyl-; 1,3-propanediol, 2-
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methyl-2-(1-methylpropyl)-; 1,3-propanediol, 2-methyl-2-(2-methylpropyl)-;
1,3-propanediol, 2-tertiary-butyl-2-methyl-; 1,3-butanediol, 2,2-diethyl-;
1,3-butanediol, 2-(1-methylpropyl)-; 1,3-butanediol, 2-butyl-; 1,3-
butanediol, 2-ethyl-2,3-dimethyl-; 1,3-butanediol, 2-(1,1-dimethylethyl)-;
1,3-butanediol, 2-(2-methylpropyl)-; 1,3-butanediol, 2-methyl-2-isopropyl-;
1,3-butanediol, 2-methyl-2-propyl-; 1,3-butanediol, 3-methyl-2-isopropyl-;
1,3-butanediol, 3-methyl-2-propyl-; 1,4-butanediol, 2,2-diethyl-; 1,4-
butanediol, 2-methyl-2-propyl-; 1,4-butanediol, 2-(1-methylpropyl)-; 1,4-
butanediol, 2-ethyl-2,3-dimethyl-; 1,4-butanediol, 2-ethyl-3,3-dimethyl-;
1,4-butanediol, 2-(1,1-dimethylethyl)-; 1,4-butanediol, 2-(2-methylpropyl)-;
1,4-butanediol, 2-methyl-3-propyl-; 1,4-butanediol, 3-methyl-2-isopropyl-;
1,3-pentanediol, 2,2,3-l,i",ell,yl-; 1,3-pentanediol, 2,2,4-trimethyl-; 1,3-
pentanediol,2,3,4-trimethyl-; 1,3-pentanediol,2,4,4-l~imelhyl-; 1,3-
pentanediol,3,4,4-trimethyl-; 1,4-pentanediol,2,2,3-trimethyl-; 1,4-
pentanediol,2,2,4-trimethyl-; 1,4-pentanediol,2,3,3-trimethyl-; 1,4-
pentanediol,2,3,4-trimethyl-; 1,4-pentanediol,3,3,4-trimethyl-; 1,5-
pentanediol,2,2,3-trimethyl-; 1,5-pentanediol,2,2,4-trimethyl-; 1,5-
pentanediol,2,3,3-trimethyl-; 1,5-pentanediol,2,3,4-trimethyl-; 2,4-
pentanediol,2,3,3-trimethyl-; 2,4-pentanediol,2,3,4-l,i",ell,yl-; 1,3-
pentanediol,2-ethyl-2-methyl-; 1,3-pentanediol,2-ethyl-3-methyl-; 1,3-
pentanediol,2-ethyl-4-methyl-; 1,3-pentanediol,3-ethyl-2-methyl-; 1,4-
pentanediol,2-ethyl-2-methyl-; 1,4-pentanediol,2-ethyl-3-methyl-; 1,4-
pentanediol,2-ethyl-4-methyl-; 1,4-pentanediol,3-ethyl-2-methyl-; 1,4-
pentanediol,3-ethyl-3-methyl-; 1,5-pentanediol,2-ethyl-2-methyl-; 1,5-
pentanediol,2-ethyl-3-methyl-; 1,5-pentanediol,2-ethyl-4-methyl-; 1,5-
pentanediol,3-ethyl-3-methyl-; 2,4-pentanediol,3-ethyl-2-methyl-; 1,3-
pentanediol, 2-isopropyl-; 1,3-pentanediol, 2-propyl-; 1,4-pentanediol, 2-
isopropyl-; 1,4-pentanediol, 2-propyl-; 1,4-pentanediol, 3-isopropyl-; 1,5-
pentanediol, 2-isopropyl-; 2,4-pentanediol. 3-propyl-; 1,3-hexanediol, 2,2-
dimethyl-; 1,3-hexanediol, 2,3-dimethyl-; 1,3-hexanediol, 2,4-dimethyl-;
1,3-hexanediol, 2,5-dimethyl-; 1,3-hexanediol, 3,4-dimethyl-; 1,3-
hexanediol, 3,5-dimethyl-; 1,3-hexanediol, 4,5-dimethyl-; 1,4-hexanediol,
2,2-dimethyl-; 1,4-hexanediol, 2,3-dimethyl-; 1,4-hexanediol, 2,4-dimethyl-
; 1,4-hexanediol, 2,5-dimethyl-; 1,4-hexanediol, 3,3-dimethyl-; 1,4-
hexanediol, 3,4-dimethyl-; 1,4-hexanediol, 3,5-dimethyl-; 1,3-hexanediol,
... , , . ~
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4,4-dimethyl-; 1,4-hexanediol, 4,5-dimethyl-; 1,4-hexanediol, 5,5-dimethyl-
; 1,5-hexanediol, 2,2-dimethyl-; 1,5-hexanediol, 2,3-dimethyl-; 1,5-
hexanediol, 2,4-dimethyl-; 1,5-hexanediol, 2,5-dimethyl-; 1,5-hexanediol,
3,3-dimethyl-; 1,5-hexanediol, 3,4-dimethyl-; 1,5-hexanediol, 3,5-dimethyl-
S ; 1,5-hexanediol, 4,5-dimethyl-; 1,6-hexanediol, 2,2-dimethyl-; 1,6-
hexanediol, 2,3-dimethyl-; 1,6-hexanediol, 2,4-dimethyl-; 1,6-hexanediol,
2,5-dimethyl-; 1,6-hexanediol, 3,3-dimethyl-; 1.6-hexanediol, 3,4-dimethyl-
; 2,4-hexanediol, 2,3-dimethyl-; 2,4-hexanediol, 2,4-dimethyl-; 2,4-
hexanediol, 2,5-dimethyl-; 2,4-hexanediol, 3,3-dimethyl-; 2,4-hexanediol,
3,4-dimethyl-; 2,4-hexanediol, 3,5-dimethyl-; 2,4-hexanediol, 4,5-dimethyl-
; 2,4-hexanediol, 5,5-dimethyl-; 2,5-hexanediol, 2,3-dimethyl-; 2,5-
hexanediol, 2,4-dimethyl-; 2,5-hexanediol, 2,5-dimethyl-; 2,5-hexanediol,
3,3-dimethyl-; 2,5-hexanediol, 3,4-dimethyl-; 2,6-hexanediol, 3,3-dimethyl-
; 1,3-hexanediol, 2-ethyl-; 1,3-hexanediol, 4-ethyl-; 1,4-hexanediol, 2-
ethyl-; 1,4-hexanediol, 4-ethyl-; 1,5-hexanediol, 2-ethyl-; 2,4-hexanediol,
3-ethyl-; 2,4-hexanediol, 4-ethyl-; 2,5-hexanediol, 3-ethyl-; 1,3-
heptanediol, 2-methyl-; 1,3-heptanediol, 3-methyl-; 1,3-heptanediol, 4-
methyl-; 1,3-heptanediol, 5-methyl-; 1,3-heptanediol, 6-methyl-; 1,4-
heptanediol, 2-methyl-; 1,4-heptanediol, 3-methyl-; 1,4-heptanediol, 4-
methyl-; 1,4-heptanediol, 5-methyl-; 1,4-heptanediol, 6-methyl-; 1,5-
heptanediol, 2-methyl-; 1,5-heptanediol, 3-methyl-; 1,5-heptanediol, 4-
methyl-; 1,5-heptanediol, 5-methyl-; 1,5-heptanediol, 6-methyl-; 1,6-
heptanediol, 2-methyl-; 1,6-heptanediol, 3-methyl-; 1,6-heptanediol, 4-
methyl-; 1,6-heptanediol, 5-methyl-; 1,6-heptanediol, 6-methyl-; 2,4-
heptanediol, 2-methyl-; 2,4-heptanediol, 3-methyl-; 2,4-heptanediol, 4-
methyl-; 2,4-heptanediol, 5-methyl-; 2,4-heptanediol, 6-methyl-; 2,5-
heptanediol, 2-methyl-; 2,5-heptanediol, 3-methyl-; 2,5-heptanediol, 4-
methyl-; 2,5-heptanediol, 5-methyl-; 2,5-heptanediol, 6-methyl-; 2,6-
heptanediol, 2-methyl-; 2,6-heptanediol, 3-methyl-; 2,6-heptanediol, 4-
methyl-; 3,4-heptanediol, 3-methyl-; 3,5-heptanediol, 2-methyl-; 3,5-
heptanediol, 3-methyl-; 3,5-heptanediol, 4-methyl-; 2,4-octanediol; 2,5-
octanediol; 2,6-octanediol; 2,7-octanediol; 3,5-octanediol; and/or 3,6-
octanediol;
D. nonane diol isomers including: 2,4-pentanediol, 2,3,3,4-tetramethyl-; 2,4-
pentanediol, 3-tertiarybutyl-; 2,4-hexanediol, 2,5,5-trimethyl-; 2,4-
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hexanediol, 3,3,4-trimethyl-; 2,4-hexanediol, 3,3,5-trimethyl-; 2,4-
hexanediol, 3,5,5-trimethyl-; 2,4-hexanediol, 4,5,5-trimethyl-; 2,5-
hexanediol, 3,3,4-trimethyl-; and/or 2,5-hexanediol, 3,3,5-trimethyl-;
E. glyceryl ethers and/or di(hydroxyalkyl)ethers including: 1,2-propanediol,
S 3-(n-pentyloxy)-; 1,2-propanediol, 3-(2-pentyloxy)-; 1,2-propanediol, 3-(3-
pentyloxy)-; 1,2-propanediol, 3-(2-methyl-1-butyloxy)-; 1,2-propanediol, 3-
(iso-amyloxy)-; 1,2-propanediol, 3-(3-methyl-2-butyloxy)-; 1,2-propanediol,
3-(cyclohexyloxy)-; 1,2-propanediol, 3-(1-cyclohex-1-enyloxy)-; 1,3-
propanediol, 2-(pentyloxy)-; 1,3-propanediol, 2-(2-pentyloxy)-; 1,3-
propanediol, 2-(3-pentyloxy)-; 1,3-propanediol, 2-(2-methyl-1-butyloxy)-;
1,3-propanediol, 2-(iso-amyloxy)-; 1,3-propanediol, 2-(3-methyl-2-
butyloxy)-; 1,3-propanediol, 2-(cyclohexyloxy)-; 1,3-propanediol, 2-(1-
cyclohex-1-enyloxy)-; 1,2-propanediol, 3-(butyloxy)-, triethoxylated; 1,2-
propanediol, 3-(butyloxy)-, tetraethoxylated; 1,2-propanediol, 3-(butyloxy)-,
l S pentaethoxylated; 1 ,2-propanediol, 3-(butyloxy)-, hexaethoxylated; 1,2-
propanediol, 3-(butyloxy)-, heptaethoxylated; 1,2-propanediol, 3-
(butyloxy)-, octaethoxylated; 1,2-propanediol, 3-(butyloxy)-,
nonaethoxylated; 1,2-propanediol, 3-(butyloxy)-, monopropoxylated; 1,2-
propanediol, 3-(butyloxy)-, dibutyleneoxylated; 1,2-propanediol, 3-
(butyloxy)-, tributyleneoxylated; 1,2-propanediol, 3-phenyloxy-; 1,2-
propanediol, 3-benzyloxy-; 1,2-propanediol, 3-(2-phenylethyloxy)-; 1,2-
propanediol, 3-(1-phenyl-2-propanyloxy)-; 1,3-propanediol, 2-phenyloxy-;
1,3-propanediol, 2-(m-cresyloxy)-; 1,3-propanediol, 2-(p-cresyloxy)-; 1,3-
propanediol, -benzyloxy-; 1,3-propanediol, 2-(2-phenylethyloxy)-; 1,3-
propanediol, 2-(1-phenylethyloxy)-; bis(2-hydroxybutyl)ether; and/or bis(2-
hydroxycyclopentyl)ether;
F saturated and unsaturated alicyclic diols and their derivatives including:
1. the saturated diols and their derivatives, including:
1-isopropyl-1,2-cyclobutanediol; 3-ethyl4-methyl-1,2-cyclobutanediol;
3-propyl-1,2-cyclobutanediol; 3-isopropyl-1,2-cyclobutanediol; 1-ethyl-
1,2-cyclopentanediol; 1,2-dimethyl-1,2-cyclopentanediol; 1,4-dimethyl-
1,2-cyclopentanediol; 2,4,5-trimethyl-1,3-cyclopentanediol; 3,3-
dimethyl-1,2-cyclopentanediol; 3,4-dimethyl-1,2-cyclopentanediol; 3,5-
dimethyl-1,2-cyclopentanediol; 3-ethyl-1,2-cyclopentanediol; 4,4-
dimethyl-1,2-cyclopentanediol; 4-ethyl-1,2-cyclopentanediol; 1,1-
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bis(hydroxymethyl)cyclohexane; 1,2-bis(hydroxymethyl)cyclohexane;
1,2-dimethyl-1,3-cyclohexanediol; 1,3-bis(hydroxymethyl)cyclohexane;
1,3-dimethyl-1,3-cyclohexanediol; 1,6-dimethyl-1,3-cyclohexanediol; 1-
hydroxy-cyclohexaneethanol; 1-hydroxy-cyclohexanemethanol; 1-
S ethyl-1,3-cyclohexanediol; 1-methyl-1,2-cyclohexanediol; 2,2-dimethyl-
1,3-cyclohexanediol; 2,3-dimethyl-1,4-cyclohexanediol; 2,4-dimethyl-
1,3-cyclohexanediol; 2,5-dimethyl-1,3-cyclohexanediol; 2,6-dimethyl-
1,4-cyclohexanediol; 2-ethyl-1,3-cyclohexanediol; 2-
hydroxycyclohexaneethanol; 2-hydroxyethyl-1-cyclohexanol; 2-
l O hydroxymethylcyclohexanol; 3-hydroxyethyl-1 -cyclohexanol; 3-
hydroxycyclohexaneethanol; 3-hydroxymethylcyclohexanol; 3-methyl-
1,2-cyclohexanediol; 4,4-dimethyl-1,3-cyclohexanediol; 4,5-dimethyl-
1,3-cyclohexanediol; 4,6-dimethyl-1,3-cyclohexanediol; 4-ethyl-1,3-
cyclohexanediol; 4-hydroxyethyl-1-cyclohexanol; 4-
I S hydroxymethylcyclohexanol; 4-methyl-1 ,2-cyclohexanediol; 5,5-
dimethyl-1,3-cyclohexanediol; 5-ethyl-1,3-cyclohexanediol; 1,2-
cycloheptanediol; 2-methyl-1,3-cycloheptanediol; 2-methyl-1,4-
cycloheptanediol; 4-methyl-1,3-cycloheptanediol; 5-methyl-1,3-
cycloheptanediol; 5-methyl-1,4-cycloheptanediol; 6-methyl-1,4-
cycloheptanediol; ; 1 ,3-cyclooctanediol; 1 ,4-cyclooctanediol; 1 ,5-
cyclooctanediol; 1,2-cyclohexanediol, diethoxylate; 1,2-
cyclohexanediol, triethoxylate; 1,2-cyclohexanediol, tetraethoxylate;
1,2-cyclohexanediol, pentaethoxylate; 1,2-cyclohexanediol,
hexaethoxylate; 1,2-cyclohexanediol, heptaethoxylate; 1,2-
cyclohexanediol, octaethoxylate; 1 ,2-cyclohexanediol, nonaethoxylate;
1,2-cyclohexanediol, monopropoxylate; 1,2-cyclohexanediol,
monobutylenoxylate; 1,2-cyclohexanediol, dibutylenoxylate; and/or 1,2-
cyclohexanediol, tributylenoxylate; and
2. the unsaturated alicyclic diols including:
1,2-cyclobutanediol, 1-ethenyl-2-ethyl-; 3-cyclobutene-1,2-diol, 1,2,3,4-
tetramethyl-; 3-cyclobutene-1,2-diol, 3,4-diethyl-; 3-cyclobutene-1,2-
diol, 3-(1,1-dimethylethyl)-; 3-cyclobutene-1,2-diol, 3-butyl-; 1,2-
cyclopentanediol, 1,2-dimethyl-4-methylene-; 1,2-cyclopentanediol, 1-
ethyl-3-methylene-; 1,2-cyclopentanediol, 4-(1-propenyl); 3-
cyclopentene-1,2-diol, 1-ethyl-3-methyi-; 1,2-cyclohexanediol, 1-
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ethenyl-; 1,2-cyclohexanediol, 1-methyl-3-methylene-; 1,2-
cyclohexanediol, 1-methyl4-methylene-; 1,2-cyclohexanediol, 3-
ethenyl-; 1,2-cyclohexanediol, 4-ethenyl-; 3-cyclohexene-1,2-diol, 2,6-
dimethyl-; 3-cyclohexene-1,2-diol, 6,6-dimethyl-; 4-cyclohexene-1,2-
S diol, 3,6-dimethyl-; 4-cyclohexene-1,2-diol, 4,5-dimethyl-; 3-
cyclooctene-1,2-diol; 4-cyclooctene-1,2-diol; and/or 5-cyclooctene-1,2-
diol;
G. Alkoxylated derivatives of C3 8 diols [In the following disclosure, "EO" means polyethoxylates, i.e., -(CH2CH2O)nH; Me-En means methyl-
capped polyethoxylates -(CH2CH2O)nCH3; "2tMe-En)" means 2 Me-En
groups needed; "PO" means polypropoxylates, -(CH(CH3)CH2O)nH;
"BO" means polybutyleneoxy groups, (CH(Ctl2CH3)CH2O)nH; and "n-
BO" means poly(n-butyleneoxy) or poly(tetramethylene)oxy groups -
(CH2CH2CH2CH2O)nH. The use of the term ''(Cx)'' herein refers to the
l S number of carbon atoms in the base material which is alkoxylated.]
including:
1. 1,2-propanediol (C3) 2(Me-E14); 1,2-propanediol (C3) PO4; 1,2-
propanediol (C3) BO1; 1,2-propanediol, 2-methyl- (C4) (Me-E4 10);
1,2-propanediol, 2-methyl- (C4) 2(Me-E1); 1,2-propanediol, 2-methyl-
(C4) PO3; 1,2-propanediol, 2-methyl- (C4) n-BO1 2; 1,3-propanediol
(C3) 2(Me-E6 8); 1,3-propanediol (C3) POs 6; 1,3-propanediol, 2,2-
diethyl- (C7) E1 7; 1,3-propanediol, 2,2-diethyl- (C7) PO1; 1,3-
propanediol, 2,2-diethyl- (C7) n-BO1 2; 1,3-propanediol, 2,2-dimethyl-
(C5) 2(Me E1 2); 1,3-propanediol, 2,2-dimethyl- (C5) PO3 4; 1,3-
propanediol, 2-(1-methylpropyl)- (C7) E1 7; 1,3-propanediol, 2-(1-
methylpropyl)- (C7) PO1; 1,3-propanediol, 2-(1-methylpropyl)- (C7) n-
BO1 2; 1,3-propanediol, 2-(2-methylpropyl)- (C7) E17; 1,3-
propanediol, 2-(2-methylpropyl)- (C7) PO1; 1,3-propanediol, 2-(2-
methylpropyl)- (C7) n-BO1 2; 1,3-propanediol, 2-ethyl- (C5) (Me E6
10); 1,3-propanediol, 2-ethyl- (C5) 2(Me E1); 1,3-propanediol, 2-ethyl-
(C5) PO3; 1,3-propanediol, 2-ethyl- (C5) BO1; 1,3-propanediol, 2-
ethyl-2-methyl- (C6) (Me E1 6); 1,3-propanediol, 2-ethyl-2-methyl- (C6)
PO2; 1,3-propanediol, 2-ethyl-2-methyl- (C6) BO1; 1,3-propanediol, 2-
isopropyl- (C6) (Me E1 6); 1,3-propanediol, 2-isopropyl- (C6) PO2; 1,3-
propanediol, 2-isopropyl- (C6) BO1; 1,3-propanediol, 2-methyl- (C4)
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g
2(Me E2 5); 1,3-propanediol, 2-methyl- (C4) PO4 5; 1,3-propanediol,
2-methyl- (C4) BO2; 1,3-propanediol, 2-methyl-2-isopropyl- (C7) E2 9;
1,3-propanediol, 2-methyl-2-isopropyl- (C7) PO1; 1,3-propanediol, 2-
methyl-2-isopropyl- (C7) n-BO1 3; 1,3-propanediol, 2-methyl-2-propyl-
(C7) E17; 1 ,3-propanediol, 2-methyl-2-propyl- (C7) PO1 ; 1 ,3-
propanediol, 2-methyl-2-propyl- (C7) n-BO1 2; 1,3-propanediol, 2-
propyl- (C6) (Me E14); 1,3-propanediol, 2-propyl- (C6) PO2; 1,3-
propanediol, 2-propyl- (C6) BO1;
2. 1,2-butanediol (C4) (Me E2 8); 1,2-butanediol (C4) PO2 3; 1,2-
butanediol (C4) BO1; 1,2-butanediol, 2,3-dimethyl- (C6) E1 6; 1,2-
butanediol, 2,3-dimethyl- (C6) n-BO1 2; 1,2-butanediol, 2-ethyl- (C6)
E1 3; 1,2-butanediol, 2-ethyl- (C6) BO1; 1,2-butanediol, 2-methyl- (C5)
(Me E1 2); 1,2-butanediol, 2-methyl- (C5) PO1; 1,2-butanediol, 3,3-
dimethyl- (C6) E1 6; 1,2-butanediol, 3,3-dimethyl- (C6) BO1 2; 1,2-
butanediol, 3-methyl- (C5) (Me E1 2); 1,2-butanediol, 3-methyl- (C5)
PO; 1,3-butanediol (C4) 2(Me E3 6); 1,3-butanediol (C4) POs; 1,3-
butanediol (C4) BO2; 1,3-butanediol, 2,2,3-trimethyl- (C7) (Me E1 3);
1,3-butanediol, 2,2,3-trimethyl- (C7) PO1 2; 1,3-butanediol, 2,2-
dimethyl- (C6) (Me E3 8); 1,3-butanediol, 2.2-dimethyl- (C6) PO3; 1,3-
butanediol, 2,3-dimethyl- (C6) (Me E3 8); 1,3-butanediol, 2,3-dimethyl-
(C6) PO3; 1,3-butanediol, 2-ethyl- (C6) (Me E1 6); 1,3-butanediol, 2-
ethyl- (C6) PO2 3; 1,3-butanediol, 2-ethyl- (C6) BO1; 1,3-butanediol,
2-ethyl--2-methyl- (C7) (Me E1); 1,3-butanediol, 2-ethyl--2-methyl- (C7)
PO1; 1,3-butanediol, 2-ethyl--2-methyl- (C7) n-BO24; 1,3-butanediol,
2-ethyl-3-methyl- (C7) (Me E1); 1,3-butanediol, 2-ethyl-3-methyl- (C7)
PO1; 1,3-butanediol, 2-ethyl-3-methyl- (C7) n-BO24; 1,3-butanediol,
2-isopropyl- (C7) (Me E1); 1,3-butanediol, 2-isopropyl- (C7) PO1; 1,3-
butanediol, 2-isopropyl- (C7) n-BO2 4; 1,3-butanediol, 2-methyl- (C5)
2(Me E1 3); 1,3-butanediol, 2-methyl- (C5) PO4; 1,3-butanediol, 2-
propyl- (C7) E2 9; 1,3-butanediol, 2-propyl- (C7) PO1; 1,3-butanediol,
2-propyl- (C7) n-BO1 3; 1,3-butanediol, 3-methyl- (C5) 2(Me E1 3);
1,3-butanediol, 3-methyl- (C5) PO4; 1,4-butanediol (C4) 2(Me E2 4);
1,4-butanediol (C4) PO4 ~; 1,4-butanediol (C4) BO2; 1,4-butanediol,
2,2,3-trimethyl- (C7) E2 9; 1,4-butanediol, 2,2,3-trimethyl- tC7) PO1;
1,4-butanediol, 2,2,3-trimethyl- (C7) n-BO1 3; 1,4-butanediol, 2,2-
,
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- 10 -
dimethyl- (C6) (Me E1 6); 1,4-butanediol, 2,2-dimethyl- (C6) PO2; 1,4-
butanediol, 2,2-dimethyl- (C6) BO1; 1,4-butanediol, 2,3-dimethyl- (C6)
(Me E1 6); 1,4-butanediol, 2,3-dimethyl- (C6) PO2; 1,4-butanediol, 2,3-
dimethyl- (C6) BO1; 1,4-butanediol, 2-ethyl- (C6) (Me E14); 1,4-
S butanediol, 2-ethyl- (C6) PO2; 1,4-butanediol, 2-ethyl- (C6) BO1; 1,4-butanediol, 2-ethyl-2-methyl- (C7) E1 7; 1,4-butanediol, 2-ethyl-2-
methyl- (C7) PO1; 1,4-butanediol, 2-ethyl-2-methyl- (C7) n-BO1 2; 1,4-
butanediol, 2-ethyl-3-methyl- (C7) E1 7; 1,4-butanediol, 2-ethyl-3-
methyl- (C7) PO1; 1,4-butanediol, 2-ethyl-3-methyl- (C7) n-BO1 2; 1,4-
butanediol, 2-isopropyl- (C7) E17; 1,4-butanediol, 2-isopropyl- (C7)
PO1; 1,4-butanediol, 2-isopropyl- (C7) n-~O1 2; 1,4-butanediol, 2-
methyl- (C5) (Me E6 10); 1,4-butanediol, 2-methyl- (C5) 2(Me E1); 1,4-
butanediol, 2-methyl- (C5) PO3; 1,4-butanediol, 2-methyl- (C5) BO1;
1,4-butanediol, 2-propyl- (C7) E1 5; 1,4-butanediol, 2-propyl- (C7) n-
lS BO1 2; 1,4-butanediol, 3-ethyl-1-methyl- (C7) E2 9; 1,4-butanediol, 3-ethyl-1-methyl- (C7) PO1; 1,4-butanediol, 3-ethyl-1-methyl- (C7) n-
BO13; 2,3-butanediol (C4) (Me E1 6); 2,3-butanediol (C4) 2(Me E1);
2,3-butanediol (C4) PO34; 2,3-butanediol (C4) BO1; 2,3-butanediol,
2,3-dimethyl- (C6) E3 9; 2,3-butanediol, 2,3-dimethyl- (C6) PO1; 2,3-
butanediol, 2,3-dimethyl- (C6) BO13; 2,3-butanediol, 2-methyl- (C5)
(Me E1 5); 2,3-butanediol, 2-methyl- (C5) 2PO2; 2,3-butanediol, 2-
methyl- (C5) n-BO1; 2,3-butanediol, 2-methyl- (C5) BO1;
3. 1,2-pentanediol (C5) E3 10; 1,2-pentanediol, (C5) PO1; 1,2-
pentanediol, (C5) n-BO2 3; 1,2-pentanediol, 2-methyl (C6) E1 3; 1,2-
pentanediol, 2-methyl (C6) n-BO1; 1,2-pentanediol, 2-methyl (C6)
BO1; 1,2-pentanediol, 3-methyl (C6) E13; 1,2-pentanediol, 3-methyl
(C6) n-BO1; 1,2-pentanediol, 3-methyl (C6) BO1; 1,2-pentanediol, 4-
methyl (C6) E1 3; 1,2-pentanediol, 4-methyl (C6) n-BO1; 1,2-
pentanediol, 4-methyl (C6) BO1; 1,3-pentanediol (C5) 2(Me-E1 2); 1,3-
pentanediol (C5) PO3 4; 1,3-pentanediol, 2,2-dimethyl- (C7) (Me-E1);
1,3-pentanediol, 2,2-dimethyl- (C7) PO1; 1,3-pentanediol, 2,2-
dimethyl- (C7) n-BO24; 1,3-pentanediol, 2,3-dimethyl- (C7) (Me-E1);
1,3-pentanediol, 2,3-dimethyl- (C7) PO1; 1,3-pentanediol, 2,3-
dimethyl- (C7) n-BO2 4; 1,3-pentanediol, 2,4-dimethyl- (C7) (Me-E1);
1,3-pentanediol, 2,4-dimethyl- (C7) PO1; 1,3-pentanediol, 2,4-
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1 1
dimethyl- (C7) n-BO2 4; 1,3-pentanediol, 2-ethyl- (C7) E2 9; 1,3-
pentanediol, 2-ethyl- (C7) PO1; 1,3-pentanediol, 2-ethyl- (C7) n-BO1
3; 1,3-pentanediol, 2-methyl- (C6) 2(Me-E1 6); 1,3-pentanediol, 2-
methyl- (C6) PO2 3; 1,3-pentanediol, 2-methyl- (C6) n-BO1; 1,3-
S pentanediol, 2-methyl- (C6) BO1; 1,3-pentanediol, 3,4-dimethyl- (C7)
(Me-E1 ); 1 ,3-pentanediol, 3,4-dimethyl- (C7) PO1; 1 ,3-pentanediol,
3,4-dimethyl- (C7) n-BO2 4; 1,3-pentanediol, 3-methyl- (C6) 2(Me-E1
6); 1,3-pentanediol, 3-methyl- (C6) PO2 3; 1,3-pentanediol, 3-methyl-
(C6) n-BO1; 1,3-pentanediol, 3-methyl- (C6) BO1; 1,3-pentanediol,
4,4-dimethyl- (C7) (Me-E1); 1,3-pentanediol, 4,4-dimethyl- (C7) PO1;
1,3-pentanediol, 4,4-dimethyl- (C7) n-BO2 4; 1,3-pentanediol, 4-
methyl- (C6) 2(Me-E1 6); 1,3-pentanediol, 4-methyl- (C6) PO2 3; 1,3-
pentanediol, 4-methyl- (C6) BO1; 1,4-pentanediol, (C5) 2(Me-E1 2);
1,4-pentanediol (C5) PO34; 1,4-pentanediol, 2,2-dimethyl- (C7) (Me-
E1); 1,4-pentanediol, 2,2-dimethyl- (C7) PO1; 1,4-pentanediol, 2,2-
dimethyl- (C7) n-BO2 4; 1,4-pentanediol, 2,3-dimethyl- (C7) (Me-E1);
1,4-pentanediol, 2,3-dimethyl- (C7) PO1; 1,4-pentanediol, 2,3-
dimethyl- (C7) n-BO24; 1,4-pentanediol, 2,4-dimethyl- (C7) (Me-E1);
1,4-pentanediol, 2,4-dimethyl- (C7) PO1; 1,4-pentanediol, 2,4-
dimethyl- (C7) n-BO2 4; 1,4-pentanediol, 2-methyl- (C6) (Me-E1 6);
1,4-pentanediol, 2-methyl- (C6) PO2 3; 1,4-pentanediol, 2-methyl- (C6)
n-BO1; 1,4-pentanediol, 2-methyl- (C6) BO1; 1,4-pentanediol, 3,3-
dimethyl- (C7) (Me-E1); 1,4-pentanediol, 3,3-dimethyl- (C7) PO1; 1,4-
pentanediol, 3,3-dimethyl- (C7) n-BO24; 1,4-pentanediol, 3,4-
dimethyl- (C7) (Me-E1); 1,4-pentanediol, 3,4-dimethyl- (C7) PO1; 1,4-
pentanediol, 3,4-dimethyl- (C7) n-BO2 4; 1,4-pentanediol, 3-methyl-
(C6) 2(Me-E1 6); 1,4-pentanediol, 3-methyl- (C6) PO2 3; 1,4-
pentanediol, 3-methyl- (C6) BO1; 1,4-pentanediol, 4-methyl- (C6)
2(Me-E1 6); 1,4-pentanediol, 4-methyl- (C6) PO2 3; 1,4-pentanediol,
4-methyl- (C6) BO1; 1,5-pentanediol, (C5) (Me-E4 10); 1,5-pentanediol
(CS) 2(Me-E1 ); 1 ,5-pentanediol (C5) PO3; 1 ,5-pentanediol, 2,2-
dimethyl- (C7) E1 7; 1,5-pentanediol, 2,2-dimethyl- (C7) PO1; 1,5-
pentanediol, 2,2-dimethyl- (C7) n-BO1 2; 1,5-pentanediol, 2,3-
dimethyl- (C7) E1 7; 1,5-pentanediol, 2,3-dimethyl- (C7) PO1; 1,5-
pentanediol, 2,3-dimethyl- (C7) n-BO1 2; 1,5-pentanediol, 2,4-
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dimethyl- (C7) E1 7; 1,5-pentanediol, 2,4-dimethyl- (C7) PO1; 1,5-
pentanediol, 2,4-dimethyl- (C7) n-BO1 2; 1,5-pentanediol, 2-ethyl- (C7)
E1 5; 1,5-pentanediol, 2-ethyl- (C7) n-BO1 2; 1,5-pentanediol, 2-
methyl- (C6) (Me-E1 4); 1,5-pentanediol, 2-methyl- (C6) PO2; 1,5-
S pentanediol, 3,3-dimethyl- (C7) E17; 1,5-pentanediol, 3,3-dimethyl-(C7) PO1; 1,5-pentanediol, 3,3-dimethyl- (C7) n-BO1 2; 1,5-
pentanediol, 3-methyl- (C6) (Me-E1 4); 1,5-pentanediol, 3-methyl- (C6)
PO2; 2,3-pentanediol, (C5) (Me-E1 3); 2,3-pentanediol, (C5) PO2; 2,3-
pentanediol, 2-methyl- (C6) E1 7; 2,3-pentanediol, 2-methyl- (C6) PO1;
2,3-pentanediol, 2-methyl- (C6) n-BO1 2; 2,3-pentanediol, 3-methyl-
(C6) E17; 2,3-pentanediol, 3-methyl- (C6) PO1; 2,3-pentanediol, 3-
methyl- (C6) n-BO1 2; 2,3-pentanediol, 4-methyl- (C6) E17; 2,3-
pentanediol, 4-methyl- (C6) PO1; 2,3-pentanediol, 4-methyl- (C6) n-
BO1 2; 2,4-pentanediol, (C5) 2(Me-E14); 2,4-pentanediol (C5) PO4;
as 2,4-pentanediol, 2,3-dimethyl- (C7) (Me-E1 4); 2,4-pentanediol, 2,3-
dimethyl- (C7) PO2; 2,4-pentanediol, 2,4-dimethyl- (C7) (Me-E1 4);
2,4-pentanediol, 2,4-dimethyl- (C7) PO2; 2,4-pentanediol, 2-methyl-
(C7) (Me-Es 1o); 2,4-pentanediol, 2-methyl- (C7) PO3; 2,4-
pentanediol, 3,3-dimethyl- (C7) (Me-E1 4); 2,4-pentanediol, 3,3-
dimethyl- (C7) PO2; 2,4-pentanediol, 3-methyl- (C6) (Me-Es 10) ; 2,4-
pentanediol, 3-methyl- (C6) PO3;
4. 1,3-hexanediol (C6) (Me-E1 5); 1,3-hexanediol (C6) PO2; 1,3-
hexanediol (C6) BO1; 1,3-hexanediol, 2-methyl- (C7) E2 9; 1,3-
hexanediol, 2-methyl- (C7) PO1; 1,3-hexanediol, 2-methyl- (C7) n-
BO1 3; 1,3-hexanediol, 2-methyl- (C7) BO1; 1,3-hexanediol, 3-methyl-
(C7) E2 9; 1,3-hexanediol, 3-methyl- (C7) PO1; 1,3-hexanediol, 3-
methyl- (C7) n-BO1 3; 1,3-hexanediol, 4-methyl- (C7) E2 9; 1,3-
hexanediol, 4-methyl- (C7) PO1; 1,3-hexanediol, 4-methyl- (C7) n-
BO1 3; 1,3-hexanediol, 5-methyl- (C7) E2 9; 1,3-hexanediol, 5-methyl-
(C7) PO1; 1,3-hexanediol, 5-methyl- (C7) n-BO1 3; 1,4-hexanediol
(C6) (Me-E1 5); 1,4-hexanediol (C6) PO2; 1,4-hexanediol (C6) BO1;
1,4-hexanediol, 2-methyl- (C7) E2 9; 1,4-hexanediol, 2-methyl- (C7)
PO1; 1,4-hexanediol, 2-methyl- (C7) n-BO1 3; 1,4-hexanediol, 3-
methyl- (C7) E2 9; 1,4-hexanediol, 3-methyl- (C7) PO1; 1,4-
hexanediol, 3-methyl- (C7) n-BO1 3; 1,4-hexanediol, 4-methyl- (C7)
. ,.. , . ~. .. .
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E2 9; 1,4-hexanediol, 4-methyl- (C7) PO1; 1,4-hexanediol, 4-methyl-
(C7) n-BO1 3; 1,4-hexanediol, 5-methyl- (C7) E2 9; 1,4-hexanediol, 5-
methyl- (C7) P01; 1,4-hexanediol, 5-methyl- (C7) n-BO1 3; 1,5-
hexanediol (C6) (Me-E1 5); 1,5-hexanediol (C6) PO2; 1,5-hexanediol
S (C6) BO1; 1,5-hexanediol, 2-methyl- (C7) E2 9; 1,5-hexanediol, 2-
methyl- (C7) P01; 1,5-hexanediol, 2-methyl- (C7) n-BO1 3; 1,5-
hexanediol, 3-methyl- (C7) E2 9; 1,5-hexanediol, 3-methyl- (C7)P01;
1,5-hexanediol, 3-methyl- (C7) n-Bo1-3; 1,5-hexanediol, 4-methyl-
(C7) E29; 1,5-hexanediol, 4-methyl- (C7) PO1; 1,5-hexanediol, 4-
methyl- (C7) n-Bo1-3; 1,5-hexanediol, 5-methyl- (C7) E2 9; 1,5-
hexanediol, 5-methyl- (C7) PO1; 1,5-hexanediol, 5-methyl- (C7) n-
BO1 3; 1,6-hexanediol (C6) (Me-E1 2); 1,6-hexanediol (C6) PO1 2;
1,6-hexanediol (C6) n-BO4; 1,6-hexanediol, 2-methyl- (C7) E1 5; 1,6-
hexanediol, 2-methyl- (C7) n-BO 1-2; 1 ,6-hexanediol, 3-methyl- (C7)
lS E1 5; 1,6-hexanediol, 3-methyl- (C7)n-B012; 2,3-hexanediol (C6) E1
5; 2,3-hexanediol (C6) n-BO1; 2,3-hexanediol (C6) BO1; 2,4-
hexanediol (C6) (Me-E3 8); 2,4-hexanediol (C6) PO3; 2,4-hexanediol,
2-methyl- (C7) (Me-E1 2); 2,4-hexanediol 2-methyl- (C7) PO1 2; 2,4-
hexanediol, 3-methyl- (C7) (Me-E1 2); 2,4-hexanediol 3-methyl- (C7)
PO1 2; 2,4-hexanediol, 4-methyl- (C7)(Me-E12); 2,4-hexanediol 4-
methyl- (C7) PO1 2; 2,4-hexanediol, 5-methyl- (C7) (Me-E1 2); 2,4-
hexanediol 5-methyl- (C7) PO1 2; 2,5-hexanediol (C6) (Me-E3 8); 2,5-
hexanediol (C6) PO3; 2,5-hexanediol, 2-methyl- (C7) (Me-E1 2); 2,5-
hexanediol 2-methyl- (C7) PO1 2; 2,5-hexanediol, 3-methyl- (C7) (Me-
E1 2); 2,5-hexanediol 3-methyl- (C7) PO1 2; 3,4-hexanediol (C6) EO
5; 3,4-hexanediol (C6) n-BO1; 3,4-hexanediol (C6) BO1;
5. 1,3-heptanediol (C7) E1 7; 1,3-heptanediol (C7) PO1; 1,3-heptanediol
(C7) n-BO1 2; 1,4-heptanediol (C7) E1 7; 1,4-heptanediol (C7) PO1;
1,4-heptanediol (C7) n-BO1 2; 1,5-heptanediol (C7) E17; 1,5-
heptanediol (C7) PO1; 1,5-heptanediol (C7) n-BO1 2; 1,6-heptanediol
(C7) E1 7; 1,6-heptanediol (C7) PO1; 1,6-heptanediol (C7) n-BO1 2;
1,7-heptanediol (C7) E1 2; 1,7-heptanediol (C7) n-BO1; 2,4-
heptanediol (C7) E3 10; 2,4-heptanediol (C7) (Me-E1); 2,4-heptanediol
(C7) PO1; 2,4-heptanediol (C7) n-BO3; 2,5-heptanediol (C7) E3 10;
2,5-heptanediol (C7) (Me-E1 ); 2,5-heptanediol (C7) PO1; 2,5-
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-14-
heptanediol (C7) n-BO3; 2,6-heptanediol (C7) E3 10; 2,6-heptanediol
(C7) (Me-E1); 2,6-heptanediol (C7) PO1; 2,6-heptanediol (C7) n-BO3;
3,5-heptanediol (C7) E3 10; 3,5-heptanediol (C7) (Me-E1); 3,5-
heptanediol (C7) PO1; 3,5-heptanediol (C7) n-BO3;
6. 1,3-butanediol, 3-methyl-2-isopropyl- (C8) PO; 2,4-pentanediol, 2,3,3-
trimethyl- (C8) PO; 1,3-butanediol, 2,2-diethyl- (C8) E2 5; 2,4-
hexanediol, 2,3-dimethyl- (C8) E2 5; 2,4-hexanediol, 2,4-dimethyl- (C8)
E2 5; 2,4-hexanediol, 2,5-dimethyl- (C8) E2 5; 2,4-hexanediol, 3,3-
dimethyl- (C8) E2 5; 2,4-hexanediol, 3,4-dimethyl- (C8) E2 5; 2,4-
hexanediol, 3,5-dimethyl- (C8) E2 5; 2,4-hexanediol, 4,5-dimethyl- (C8)
E2 5; 2,4-hexanediol, 5,5-dimethyl- (C8) E2 5; 2,5-hexanediol, 2,3-
dimethyl- (C8) E2 5; 2,5-hexanediol, 2,4-dimethyl- (C8) E2 5; 2,5-
hexanediol, 2,5-dimethyl- (C8) E2 5; 2,5-hexanediol, 3,3-dimethyl- (C8)
E2 5; 2,5-hexanediol, 3,4-dimethyl- (C8) E2 5; 3,5-heptanediol, 3-
methyl- (C8) E2 5; 1,3-butanediol, 2,2-diethyl- (C8) n-BO1-2; 2,4-
hexanediol, 2,3-dimethyl- (C8) n-BO1 2; 2,4-hexanediol, 2,4-dimethyl-
(C8) n-BO1 2; 2,4-hexanediol, 2,5-dimethyl- (C8) n-BO1 2; 2,4-
hexanediol, 3,3-dimethyl- (C8) n-BO1 2; 2,4-hexanediol, 3,4-dimethyl-
(C8) n-BO1 2; 2,4-hexanediol, 3,5-dimethyl- (C8) n-BO1 2; 2,4-
hexanediol, 4,5-dimethyl- (C8) n-BO1 2; 2,4-hexanediol, 5,5-dimethyl-,
n-BO1 2; 2,5-hexanediol, 2,3-dimethyl- (C8) n-BO1 2; 2,5-hexanediol,
2,4-dimethyl- (C8) n-BO1 2; 2,5-hexanediol, 2,5-dimethyl- (C8) n-BO1
2; 2,5-hexanediol, 3,3-dimethyl- (C8) n-BO1 2; 2,5-hexanediol, 3,4-
dimethyl- (C8) n-BO1 2; 3,5-heptanediol, 3-methyl- (C8) n-BO1 2; 1,3-
propanediol, 2-(1,2-dimethylpropyl)- (C8) n-BO; 1,3-butanediol, 2-ethyl-
2,3-dimethyl- (C8) n-BO; 1,3-butanediol, 2-methyl-2-isopropyl- (C8) n-
BO; 1,4-butanediol, 3-methyl-2-isopropyl- (C8) n-BO; 1,3-pentanediol,
2,2,3-trimethyl- (C8) n-BO; 1,3-pentanediol, 2,2,4-trimethyl- (C8) n-BO;
1,3-pentanediol, 2,4,4-trimethyl- (C8) n-BO; 1,3-pentanediol, 3,4,4-
trimethyl- (C8) n-BO; 1,4-pentanediol, 2,2,3-trimethyl- (C8) n-BO; 1,4-
pentanediol, 2,2,4-trimethyl- (C8) n-BO; 1,4-pentanediol, 2,3,3-
trimethyl- (C8) n-BO; 1,4-pentanediol, 3,3,4-trimethyl- (C8) n-BO; 2,4-
pentanediol, 2,3,4-trimethyl- (C8) n-BO; 2,4-hexanediol, 4-ethyl- (C8)
n-BO; 2,4-heptanediol, 2-methyl- (C8) n-BO; 2,4-heptanediol, 3-
methyl- (C8) n-BO; 2,4-heptanediol, 4-methyl- (C8) n-BO; 2,4-
, . ~ ~
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heptanediol, 5-methyl- (C8) n-BO; 2,4-heptanediol, 6-methyl- (C8) n-
BO; 2,5-heptanediol, 2-methyl- (C8) n-BO; 2,5-heptanediol, 3-methyl-
(C8) n-BO; 2,5-heptanediol, 4-methyl- (C8) n-BO; 2,5-heptanediol, 5-
methyl- (C8) n-BO; 2,5-heptanediol, 6-methyl- (C8) n-BO; 2,6-
heptanediol, 2-methyl- (C8) n-BO; 2,6-heptanediol, 3-methyl- (C8) n-
BO; 2,6-heptanediol, 4-methyl- (C8) n-BO; 3,5-heptanediol, 2-methyl-
(C8) n-BO; 1,3-propanediol, 2-(1,2-dimethylpropyl)- (C8) E1 3; 1,3-
butanediol, 2-ethyl-2,3-dimethyl- (C8) E1 3; 1,3-butanediol, 2-methyl-2-
isopropyl- (C8) E1 3; 1,4-butanediol, 3-methyl-2-isopropyl- (C8) E1 3;
1,3-pentanediol, 2,2,3-trimethyl- (C8) E1 3; 1,3-pentanediol, 2,2,4-
trimethyl- (C8) E1 3; 1,3-pentanediol, 2,4,4-trimethyl- (C8) E1 3; 1,3-
pentanediol, 3,4,4-trimethyl- (C8) E1 3; 1,4-pentanediol, 2,2,3-
trimethyl- (C8) E1 3; 1,4-pentanediol, 2,2,4-trimethyl- (C8) E1 3; 1,4-
pentanediol, 2,3,3-trimethyl- (C8) E1 3; 1,4-pentanediol, 3,3,4-
IS trimethyl- (C8) E1 3; 2,4-pentanediol, 2,3,4-trimethyl- (C8) E1 3; 2,4-
hexanediol, 4-ethyl- (C8) E1 3; 2,4-heptanediol, 2-methyl- (C8) E1 3;
2,4-heptanediol, 3-methyl- (C8) E1 3; 2,4-heptanediol, 4-methyl- (C8)
E1 3; 2,4-heptanediol, 5-methyl- (C8) E1 3; 2,4-heptanediol, 6-methyl-
(C8) E1 3; 2,5-heptanediol, 2-methyl- (C8) E1 3; 2,5-heptanediol, 3-
methyl- (C8) E1 3; 2,5-heptanediol, 4-methyl- (C8) E1 3; 2,5-
heptanediol, 5-methyl- (C8) E1 3; 2,5-heptanediol, 6-methyl- (C8)E1
3; 2,6-heptanediol, 2-methyl- (C8) E1 3; 2,6-heptanediol, 3-methyl-
(C8) E1 3; 2,6-heptanediol, 4-methyl- (C8) E1 3; and/or 3,5-
heptanediol, 2-methyl- (C8) E1 3; and
7. mixturesthereof;
H. aromatic diols including: 1-phenyl-1,2-ethanediol; 1-phenyl-1,2-
propanediol; 2-phenyl-1,2-propanediol; 3-phenyl-1,2-propanediol; 1-(3-
methylphenyl)-1,3-propanediol; 1-(4-methylphenyl)-1,3-propanediol; 2-
methyl-1-phenyl-1,3-propanediol; 1-phenyl-1,3-butanediol; 3-phenyl-1,3-
butanediol; 1-phenyl-1,4-butanediol; 2-phenyl-1,4-butanediol; and/or 1-
phenyl-2,3-butanediol;
I. principal solvents which are homologs, or analogs, of the above structures
where one, or more, CH2 groups are added while, for each CH2 group
added, two hydrogen atoms are removed from adjacent carbon atoms in
the molecule to form one carbon-carbon double bond, thus holding the
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number of hydrogen atoms in the molecule constant, including the
following:
1,3-Propanediol, 2,2-di-2-propenyl-; 1,3-Propanediol, 2-(1-pentenyl)-; 1,3-
Propanediol, 2-(2-methyl-2-propenyl)-2-(2-propenyl)-; 1,3-Propanediol, 2-
S (3-methyl-1-butenyl)-; 1,3-Propanediol, 2-(4-pentenyl)-; 1,3-Propanediol,
2-ethyl-2-(2-methyl-2-propenyl)-; 1,3-Propanediol, 2-ethyl-2-(2-propenyl)-;
1,3-Propanediol, 2-methyl-2-(3-methyl-3-butenyl)-; 1,3-Butanediol, 2,2-
diallyl-; 1,3-Butanediol, 2-(1-ethyl-1-propenyl)-; 1,3-Butanediol, 2-(2-
butenyl)-2-methyl-; 1,3-Butanediol, 2-(3-methyl-2-butenyl)-; 1,3-
Butanediol, 2-ethyl-2-(2-propenyl)-; 1,3-Butanediol, 2-methyl-2-(1-methyl-
2-propenyl)-; 1,4-Butanediol, 2,3-bis(1-methylethylidene)-; 1,4-Butanediol,
2-(3-methyl-2-butenyl)-3-methylene-; 2-Butene-1,4-diol, 2-(1,1-
dimethyipropyl)-; 2-Butene-1,4-diol, 2-(1-methylpropyl)-; 2-Butene-1,4-diot,
2-butyl-; 1,3-Pentanediol, 2-ethenyl-3-ethyl-; 1,3-Pentanediol, 2-ethenyl-
4,4-dimethyl-; 1,4-Pentanediol, 3-methyl-2-(2-propenyl)-; 1,5-Pentanediol,
2-(1-propenyl)-; 1,5-Pentanediol, 2-(2-propenyl)-; 1,5-Pentanediol, 2-
ethylidene-3-methyl-; 1,5-Pentanediol, 2-propylidene-; 2,4-Pentanediol, 3-
ethylidene-2,4-dimethyl-; 4-Pentene-1,3-diol, 2-(1,1-dimethylethyl)-; 4-
Pentene-1,3-diol, 2-ethyl-2,3-dimethyl-; 1,4-Hexanediol, 4-ethyl-2-
methylene-; 1,5-Hexadiene-3,4-diol, 2,3,5-trimethyl-; 1,5-Hexadiene-3,4-
diol, 5-ethyl-3-methyl-; 1,5-Hexanediol, 2-(1-methylethenyl)-; 1,6-
Hexanediol, 2-ethenyl-; 1-Hexene-3,4-diol, 5,5-dimethyl-; 1-Hexene-3,4-
diol, 5,5-dimethyl-; 2-Hexene-1,5-diol, 4-ethenyl-2,5-dimethyl-; 3-Hexene-
1,6-diol, 2-ethenyl-2,5-dimethyl-; 3-Hexene-1,6-diol, 2-ethyl-; 3-Hexene-
1,6-diol, 3,4-dimethyl-; 4-Hexene-2,3-diol, 2,5-dimethyl-; 4-Hexene-2,3-
diol, 3,4-dimethyl-; 5-Hexene-1,3-diol, 3-(2-propenyl)-; 5-Hexene-2,3-diol,
2,3-dimethyl-; 5-Hexene-2,3-diol, 3,4-dimethyl-; 5-Hexene-2,3-diol, 3,5-
dimethyl-; 5-Hexene-2,4-diol, 3-ethenyl-2,5-dimethyl-; 1,4-Heptanediol, 6-
methyl-5-methylene-; 1,5-Heptadiene-3,4-diol, 2,3-dimethyl-; 1,5-
Heptadiene-3,4-diol, 2,5-dimethyl-; 1,5-Heptadiene-3,4-diol. 3,5-dimethyl-;
1,7-Heptanediol, 2,6-bis(methylene)-; 1,7-Heptanediol, 4-methylene-; 1-
Heptene-3,5-diol, 2,4-dimethyl-; 1-Heptene-3,5-diol, 2,6-dimethyl-; 1-
Heptene-3,5-diol, 3-ethenyl-5-methyl; 1-Heptene-3,5-diol, 6,6-dimethyl-;
2,4-Heptadiene-2,6-diol, 4,6-dimethyl-; 2,5-Heptadiene-1,7-diol, 4,4-
dimethyl-; 2,6-Heptadiene-1,4-diol, 2,5,5-trimethyl-; 2-Heptene-1,4-diol,
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5,6-dimethyl-; 2-Heptene-1,5-diol, 5-ethyl-; 2-Heptene-1,7-diol, 2-methyl-;
3-Heptene-1,5-diol, 4,6-dimethyl-; 3-Heptene-1,7-diol, 3-methyl-6-
methylene-; 3-Heptene-2,5-diol, 2,4-dimethyl-; 3-Heptene-2,5-diol, 2,5-
dimethyl-; 3-Heptene-2,6-diol,2,6-dimethyl-; 3-Heptene-2,6-diol, 4,6-
dimethyl-; 5-Heptene-1,3-diol,2,4-dimethyl-; 5-Heptene-1,3-diol, 3,6-
dimethyl-; 5-Heptene-1,4-diol,2,6-dimethyl-; 5-Heptene-1,4-diol, 3,6-
dimethyl-; 5-Heptene-2,4-diol,2,3-dimethyl-; 6-Heptene-1,3-diol, 2,2-
dimethyl-; 6-Heptene-1,4-diol,4-(2-propenyl)-; 6-Heptene-1,4-diol, 5,6-
dimethyl-; 6-Heptene-1,5-diol, 2,4-dimethyl-; 6-Heptene-1,5-diol, 2-
ethylidene-6-methyl-; 6-Heptene-2,4-diol, 4-(2-propenyl)-; 6-Heptene-2,4-
diol, 5,5-dimethyl-; 6-Heptene-2,5-diol, 4,6-dimethyl-; 6-Heptene-2,5-diol,
5-ethenyl-4-methyl-; 1,3-Octanediol, 2-methylene-; 1,6-Octadiene-3,5-diol,
2,6-dimethyl-; 1,6-Octadiene-3,5-diol, 3,7-dimethyl-; 1,7-Octadiene-3,6-
diol, 2,6-dimethyl-; 1,7-Octadiene-3,6-diol, 2.7-dimethyl-; 1,7-Octadiene-
3,6-diol, 3,6-dimethyl-; 1-Octene-3,6-diol, 3-ethenyl-; 2,4,6-Octatriene-1,8-
diol, 2,7-dimethyl-; 2,4-Octadiene-1,7-diol, 3,7-dimethyl-; 2,5-Octadiene-
1,7-diol, 2,6-dimethyl-; 2,5-Octadiene-1,7-diol, 3,7-dimethyl-; 2,6-
Octadiene-1,4-diol, 3,7-dimethyl- (Rosiridol); 2,6-Octadiene-1,8-diol, 2-
methyl-; 2,7-Octadiene-1,4-diol, 3,7-dimethyl-; 2,7-Octadiene-1,5-diol, 2,6-
dimethyl-; 2,7-Octadiene-1,6-diol, 2.6-dimethyl- (8-Hydroxylinalool); 2,7-
Octadiene-1,6-diol, 2,7-dimethyl-; 2-Octene-1,4-diol; 2-Octene-1,7-diol; 2-
Octene-1,7-diol, 2-methyl-6-methylene-; 3,5-Octadiene-1,7-diol, 3,7-
dimethyl-; 3,5-Octadiene-2,7-diol, 2,7-dimethyl-; 3,5-Octanediol, 4-
methylene-; 3,7-Octadiene-1,6-diol, 2,6-dimethyl-; 3,7-Octadiene-2,5-diol,
2,7-dimethyl-; 3,7-Octadiene-2,6-diol, 2,6-dimethyl-; 3-Octene-1,5-diol, 4-
methyl-; 3-Octene-1,5-diol, 5-methyl-; 4,6-Octadiene-1,3-diol, 2,2-
dimethyl-; 4,7-Octadiene-2,3-diol, 2,6-dimethyl-; 4,7-Octadiene-2,6-diol,
2,6-dimethyl-; 4-Octene-1,6-diol, 7-methyl-; 2,7-bis(methylene)-; 2-
methylene-; 5,7-Octadiene-1,4-diol, 2,7-dimethyl-; 5,7-Octadiene-1,4-diol,
7-methyl-; 5-Octene-1,3-diol; 6-Octene-1,3-diol, 7-methyl-; 6-Octene-1,4-
diol, 7-methyl-; 6-Octene-1,5-diol; 6-Octene-1.5-diol, 7-methyl-; 6-Octene-
3,5-diol, 2-methyl-; 6-Octene-3,5-diol, 4-methyl-; 7-Octene-1,3-diol, 2-
methyl-; 7-Octene-1,3-diol, 4-methyl-; 7-Octene-1,3-diol, 7-methyl-; 7-
Octene-1,5-diol; 7-Octene-1,6-diol; 7-Octene-1,6-diol, 5-methyl-; 7-
Octene-2,4-diol, 2-methyl-6-methylene-; 7-Octene-2,5-diol, 7-methyl-; 7-
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Octene-3,5-diol, 2-methyl-; 1-Nonene-3,5-diol; 1-Nonene-3,7-diol; 3-
Nonene-2,5-diol; 4,6-Nonadiene-1,3-diol, 8-methyl-; 4-Nonene-2,8-diol;
6,8-Nonadiene-1,5-diol; 7-Nonene-2,4-diol; 8-Nonene-2,4-diol; 8-Nonene-
2,5-diol; 1,9-Decadiene-3,8-diol; and/or 1,9-Decadiene4,6-diol; and
S J. mixturesthereof.
The polyhydroxyl solvent in the present invention is preferably selected
from the group consisting of:
[In the following disclosure, "EO" means mono- or polyethoxylates, i.e., -
(CH2CH2O)nHl
1. hexane diol isomers including: 2,3-butanediol, 2,3-dimethyl-; 1,2-
butanediol, 2,3-dimethyl-; 1,2-butanediol, 3,3-dimethyl-; 2,3-
pentanediol, 2-methyl-; 2,3-pentanediol, 3-methyl-; 2,3-pentanediol, 4-
methyl-; 2,3-hexanediol; 3,4-hexanediol; 1,2-butanediol, 2-ethyl-; 1,2-
pentanediol, 2-methyl-; 1,2-pentanediol, 3-methyl-; 1,2-pentanediol, 4-
lS methyl-; and/or 1,2-hexanediol;
2. heptane diol isomers including: 1,3-propanediol, 2-butyl-; 1,3-
propanediol, 2,2-diethyl-; 1,3-propanediol, 2-(1-methylpropyl)-; 1,3-
propanediol, 2-(2-methylpropyl)-; 1,3-propanediol, 2-methyl-2-propyl-;
1,2-butanediol, 2,3,3-trimethyl-; 1,4-butanediol, 2-ethyl-2-methyl-; 1,4-
butanediol, 2-ethyl-3-methyl-; 1,4-butanediol, 2-propyl-; 1,4-butanediol,
2-isopropyl-; 1,5-pentanediol, 2,2-dimethyl-; 1,5-pentanediol, 2,3-
dimethyl-; 1,5-pentanediol, 2,4-dimethyl-; 1,5-pentanediol, 3,3-
dimethyl-; 2,3-pentanediol, 2,3-dimethyl-; 2,3-pentanediol, 2,4-
dimethyl-; 2,3-pentanediol, 3,4-dimethyl-; 2,3-pentanediol, 4,4-
dimethyl-; 3,4-pentanediol, 2,3-dimethyl-; 1,5-pentanediol, 2-ethyl-;
1,6-hexanediol, 2-methyl-; 1,6-hexanediol, 3-methyl-; 2,3-hexanediol,
2-methyl-; 2,3-hexanediol, 3-methyl-; 2,3-hexanediol, 4-methyl-; 2,3-
hexanediol, 5-methyl-; 3,4-hexanediol, 2-methyl-; 3,4-hexanediol, 3-
methyl-; 1,3-heptanediol; 1,4-heptanediol; 1,5-heptanediol; and/or 1,6-
heptanediol;
3. octane diol isomers including: 1,3-propanediol, 2-(2-methylbutyl)-; 1,3-
propanediol, 2-(1,1-dimethylpropyl)- 1,3-propanediol, 2-(1,2-
dimethylpropyl)-; 1,3-propanediol, 2-(1-ethylpropyl)-; 1,3-propanediol,
2-(1-methylbutyl)-; 1,3-propanediol, 2-(2,2-dimethylpropyl)-; 1,3-
propanediol, 2-(3-methylbutyl)-; 1,3-propanediol, 2-butyl-2-methyl-; 1,3-
.. . . , . ~ ...
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19 _
propanediol, 2-ethyl-2-isopropyl-; 1,3-propanediol, 2-ethyl-2-propyl-;
1,3-propanediol, 2-methyl-2-(1-methylpropyl)-; 1,3-propanediol, 2-
methyl-2-(2-methylpropyl)-; 1,3-propanediol, 2-tertiary-butyl-2-methyl-;
1,3-butanediol, 2,2-diethyl-; 1,3-butanediol, 2-(1-methylpropyl)-; 1,3-
S butanediol, 2-butyl-; 1,3-butanediol, 2-ethyl-2,3-dimethyl-; 1,3-
butanediol, 2-(1,1-dimethylethyl)-; 1,3-butanediol, 2-(2-methylpropyl)-;
1,3-butanediol, 2-methyl-2-isopropyl-; 1,3-butanediol, 2-methyl-2-
propyl-; 1,3-butanediol, 3-methyl-2-isopropyl-; 1,3-butanediol, 3-
methyl-2-propyl-; 1,4-butanediol, 2,2-diethyl-; 1,4-butanediol, 2-methyl-
2-propyl-; 1,4-butanediol, 2-(1-methylpropyl)-; 1,4-butanediol, 2-ethyl-
2,3-dimethyl-; 1,4-butanediol, 2-ethyl-3,3-dimethyl-; 1,4-butanediol, 2-
(1,1-dimethylethyl)-; 1,4-butanediol, 2-(2-methylpropyl)-; 1,4-
butanediol, 2-methyl-3-propyl-; 1,4-butanediol, 3-methyl-2-isopropyl-;
1,3-pentanediol, 2,2,3-trimethyl-; 1,3-pentanediol, 2,2,4-trimethyl-; 1,3-
pentanediol, 2,3,4-trimethyl-; 1,3-pentanediol, 2,4,4-trimethyl-; 1,3-
pentanediol, 3,4,4-~,i",etl,yl-; 1,4-pentanediol, 2,2,3-trimethyl-; 1,4-
pentanediol, 2,2,4-trimethyl-; 1,4-pentanediol, 2,3,3-trimethyl-; 1,4-
pentanediol, 2,3,4-trimethyl-; 1,4-pentanediol, 3,3,4-trimethyl-; 1,5-
pentanediol, 2,2,3-trimethyl-; 1,5-pentanediol, 2,2,4-trimethyl-; 1,5-
pentanediol, 2,3,3-trimethyl-; 1,5-pentanediol, 2,3,4-trimethyl-; 2,4-
pentanediol, 2,3,3-trimethyl-; 2,4-pentanediol, 2,3,4-trimethyl-; 1,3-
pentanediol, 2-ethyl-2-methyl-; 1,3-pentanediol, 2-ethyl-3-methyl-; 1,3-
pentanediol, 2-ethyl4-methyl-; 1,3-pentanediol, 3-ethyl-2-methyl-; 1,4-
pentanediol, 2-ethyl-2-methyl-; 1,4-pentanediol, 2-ethyl-3-methyl-; 1,4-
pentanediol, 2-ethyl4-methyl-; 1,4-pentanediol, 3-ethyl-2-methyl-; 1,4-
pentanediol, 3-ethyl-3-methyl-; 1,5-pentanediol, 2-ethyl-2-methyl-; 1,5-
pentanediol, 2-ethyl-3-methyl-; 1,5-pentanediol, 2-ethyl4-methyl-; 1,5-
pentanediol, 3-ethyl-3-methyl-; 2,4-pentanediol, 3-ethyl-2-methyl-; 1,3-
pentanediol, 2-isopropyl-; 1,3-pentanediol, 2-propyl-; 1,4-pentanediol,
2-isopropyl-; 1,4-pentanediol, 2-propyl-; 1,4-pentanediol, 3-isopropyl-;
1,5-pentanediol, 2-isopropyl-; 2,4-pentanediol, 3-propyl-; 1,3-
hexanediol, 2,2-dimethyl-; 1,3-hexanediol, 2,3-dimethyl-; 1,3-
hexanediol, 2,4-dimethyl-; 1,3-hexanediol, 2,5-dimethyl-; 1,3-
hexanediol, 3,4-dimethyl-; 1,3-hexanediol, 3,5-dimethyl-; 1,3-
hexanediol, 4,5-dimethyl-; 1,4-hexanediol, 2,2-dimethyl-; 1,4-
. .
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hexanediol, 2,3-dimethyl-; 1,4-hexanediol, 2,4-dimethyl-; 1,4-
hexanediol, 2,5-dimethyl-; 1,4-hexanediol, 3,3-dimethyl-; 1,4-
hexanediol, 3,4-dimethyl-; 1,4-hexanediol, 3,5-dimethyl-; 1,3-
hexanediol, 4,4-dimethyl-; 1,4-hexanediol, 4,5-dimethyl-; 1,4-
S hexanediol, 5,5-dimethyl-; 1,5-hexanediol, 2,2-dimethyl-; 1,5-
hexanediol, 2,3-dimethyl-; 1,5-hexanediol, 2,4-dimethyl-; 1,5-
hexanediol, 2,5-dimethyl-; 1,5-hexanediol, 3,3-dimethyl-; 1,5-
hexanediol, 3,4-dimethyl-; 1,5-hexanediol, 3,5-dimethyl-; 1,5-
hexanediol, 4,5-dimethyl-; 1,6-hexanediol, 2,2-dimethyl-; 1,6-
hexanediol, 2,3-dimethyl-; 1,6-hexanediol, 2,4-dimethyl-; 1,6-
hexanediol, 2,5-dimethyl-; 1,6-hexanediol, 3,3-dimethyl-; 1,6-
hexanediol, 3,4-dimethyl-; 2,4-hexanediol, 2,3-dimethyl-; 2,4-
hexanediol, 2,4-dimethyl-; 2,4-hexanediol, 2,5-dimethyl-; 2,4-
hexanediol, 3,3-dimethyl-; 2,4-hexanediol, 3,4-dimethyl-; 2,4-
hexanediol, 3,5-dimethyl-; 2,4-hexanediol, 4,5-dimethyl-; 2,4-
hexanediol, 5,5-dimethyl-; 2,5-hexanediol, 2,3-dimethyl-; 2,5-
hexanediol, 2,4-dimethyl-; 2,5-hexanediol, 2,5-dimethyl-; 2,5-
hexanediol, 3,3-dimethyl-; 2,5-hexanediol, 3,4-dimethyl-; 2,6-
hexanediol, 3,3-dimethyl-; 1,3-hexanediol, 2-ethyl-; 1,3-hexanediol, 4-
ethyl-; 1,4-hexanediol, 2-ethyl-; 1,4-hexanediol, 4-ethyl-; 1,5-
hexanediol, 2-ethyl-; 2,4-hexanediol, 3-ethyl-; 2,4-hexanediol, 4-ethyl-;
2,5-hexanediol, 3-ethyl-; 1,3-heptanediol, 2-methyl-; 1,3-heptanediol,
3-methyl-; 1,3-heptanediol, 4-methyl-; 1,3-heptanediol, 5-methyl-; 1,3-
heptanediol, 6-methyl-; 1,4-heptanediol, 2-methyl-; 1,4-heptanediol, 3-
methyl-; 1,4-heptanediol, 4-methyl-; 1,4-heptanediol, 5-methyl-; 1,4-
heptanediol, 6-methyl-; 1,5-heptanediol, 2-methyl-; 1,5-heptanediol, 3-
methyl-; 1,5-heptanediol, 4-methyl-; 1,5-heptanediol, 5-methyl-; 1,5-
heptanediol, 6-methyl-; 1,6-heptanediol, 2-methyl-; 1,6-heptanediol, 3-
methyl-; 1,6-heptanediol, 4-methyl-; 1,6-heptanediol, 5-methyl-; 1,6-
heptanediol, 6-methyl-; 2,4-heptanediol, 2-methyl-; 2,4-heptanediol, 3-
methyl-; 2,4-heptanediol, 4-methyl-; 2,4-heptanediol, 5-methyl-; 2,4-
heptanediol, 6-methyl-; 2,5-heptanediol, 2-methyl-; 2,5-heptanediol, 3-
methyl-; 2,5-heptanediol, 4-methyl-; 2,5-heptanediol, 5-methyl-; 2,5-
heptanediol, 6-methyl-; 2,6-heptanediol, 2-methyl-; 2,6-heptanediol, 3-
methyl-; 2,6-heptanediol, 4-methyl-; 3,4-heptanediol, 3-methyl-; 3,5-
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heptanediol, 2-methyl-; 3,5-heptanediol, 3-methyl-; 3,5-heptanediol, 4-
methyl-; 2,4-octanediol; 2,5-octanediol; 2,6-octanediol; 2,7-octanediol;
3,5-octanediol; and/or 3,6-octanediol;
4. nonane diol isomers including: 2,4-pentanediol, 2,3,3,4-tetramethyl-;
2,4-pentanediol, 3-tertiarybutyl-; 2,4-hexanediol, 2,5,5-trimethyl-; 2,4-
hexanediol, 3,3,4-trimethyl-; 2,4-hexanediol, 3,3,5-trimethyl-; 2,4-
hexanediol, 3,5,5-trimethyl-; 2,4-hexanediol, 4,5,5-trimethyl-; 2,5-
hexanediol, 3,3,4-trimethyl-; and/or 2,5-hexanediol, 3,3,5-trimethyl-;
and
5. mixtures thereof.
Il. Malodorous ComPonents
The polyhydroxyl solvent or mixtures of polyhydroxyl solvents of the
present invention are substantially free of malodorous components. If a
polyhydroxyl solvent contains both highly volatile and nonvolatile malodorous
components, it is essential that the solvent be substantially free of both types of
malodorous components in order to have a substantially odor-free solvent.
A. Highly volatile malodorous components are malodorous components
having a boiling point lower than a polyhydroxyl solvent. Since the boiling
point for a polyhydroxyl solvent varies depending on the type of
polyhydroxyl solvent, the types of highly volatile malodorous components
also vary. For example, if the polyhydroxyl solvent is 1,2-hexanediol, the
highly volatile malodorous components are those having a boiling point
lower than the boiling point of 1,2-hexanediol (about 220~C). Non-limiting
examples of such highly volatile malodorous components for 1,2-
hexanediol are butyloxirane (boiling point of about 118~C to 120~C) and
pentanal (boiling point of about 1 03~C).
B. Nonvolatile malodorous components are malodorous components having
a boiling point higher than a polyhydroxyl solvent and having a lower
polarity than a polyhydroxyl solvent. As stated above, since the boiling
point as well as the polarity for polyhydroxyl solvents vary depending on
the type of polyhydroxyl solvent, the types and boiling points of nonvolatile
malodorous components also vary. For example, if the polyhydroxyl
solvent is 1,2-hexanediol, the nonvolatile malodorous components are
those having a boiling point higher than the boiling point of 1 ,2-hexanediol
(about 220~C) and a polarity lower than the polarity of 1,2-hexanediol
.. , . .. ~ , .. ..
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(ClogP value of the nonvolatile malodorous components are greater than
0.60.).
The consumer noticeable malodorous components may be removed from
the polyhydroxyl solvent by many means in order to provide a substantially odor-S free solvent. The discussion below describes methods to remove the consumer
noticeable malodorous components, but the discussion is not limiting as to othermethods in which the malodorous components may be removed.
A. Highly volatile malodorous components may be removed by separation
techniques based upon different boiling points. Non-limiting examples
include removal by sparging with a gas such as steam or Nitrogen. In
addition, highly volatile malodorous components may be removed by
fractional distillation.
B. Nonvolatile malodorous components may be removed by treating with
activated carbon, a polyhydroxyl solvent pre-mixed with water. The
method is described in detail below.
1. A polyhydroxyl solvent is first pre-mixed with water, preferably
deionised water, in order to form a pre-mixture of solvent and water.
The ratio of solvent to water is greater than a 1:1 ratio, preferably
between from about a 1:3 ratio to about a 1:10 ratio. Although not
wanting to be limited by theory, it is believed that the mixing of the
solvent with water makes the mixture more polar and decreases the
solubility of the nonvolatile malodorous components.
2. Next, the pre-mixture of solvent and water in an effective ratio is
treated with activated carbon. Conventional activated carbon that is
commercially available may be used. Preferably, the activated carbon
has a particle size of about 20 microns and an iodine adsorption
capacity of about 200 mg/g. An example of a preferred type of
activated carbon is "Charcoal Activated, Powder" available through
Kanto Chemical Co., Inc. in Japan. There are several methods to treat
the pre-mixture with activated carbon, although the list below is not
limiting:
a. One method is to treat batch mixtures with activated carbon by
mixing a pre-mixture of polyhydroxyl solvent and water in an
effective ratio, with an effective amount of activated carbon. The
ratio of pre-mixture to activated carbon is from about 1:1 to about
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100:1, by weight. The preferred ratio of pre-mixture to activated
carbon is about 5:1, by weight. A filtration step may be preferably
necessary to filter out the activated carbon after treatment.
b. Another method is to pass the pre-mixture of polyhydroxyl solvent
and water in an effective ratio through a flow-through activated
carbon bed. In this method, a filtration step is not necessary. Non-
limiting examples of such flow-through activated carbon beds are
"packed column" chromatography and "fixed bed" chromatography.
Ill. Measurement of "Substantially Odor-free"
The polyhydroxyl solvents of the present invention are substantially odor-
free and substantially free of consumer noticeable malodorous components.
Although there are many methods to determine whether a substance is
substantially odor-free, one non-limiting method is described below. A panel of 3
skilled odor graders smell a sample of polyhydroxyl solvent of the present
15 invention which is substantially free of consumer noticeable malodorous
components. Using an odor grade as described below, grades are assigned to
the sample:
Grade
No odor 0
Very slight odor
Slight odor 2
Some odor 3
Strong odor 4
Very strong odor 5
For example if there are three professional perfumers in one panel, the
20 final odor grade assigned to the sample is the average of the odor grades given
by each perfumer. According to our present invention, the substantially odor-free
polyhydroxyl solvent has a final odor grade of about 2 or less, preferably, a grade
of about 1 or less.
25 IV. Formulation with Liquid Detergent ComPositions
While the substantially odor-free polyhydroxyl solvent (and mixtures of
such solvents) of the present invention can be used alone, it can also be mixed
with one or more detersive ingredients in order to formulate a liquid detergent
. . .
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composition which includes, but is not limited to the following components
discussed below. Although the following description is not limiting as to the
possible types of liquid detergent compositions, several preferred compositions
are described.
5 A. FabricSoftening Compositions
1. A fabric softening composition may contain a polyhydroxyl solvent (or
mixtures thereof), as described above, as a principal solvent. In order
to provide excellent water dispersibility, the molar ratio of the principal
solvent to the fabric softening active (discussed below), should be not
l O less than about 3, preferably from about 3 to about 100, more
preferably from about 3.6 to about 50, and most preferably from about
4 to about 25.
Said principal solvent is less than about 40%, preferably less than
about 35%, more preferably less than about 25%, and even more
preferably from about 14% to about 20%, by weight of the fabric
softening composition
2. A fabric softening composition may also contain a fabric softening
active, typically from about 15% to about 70%, preferably from about
17% to about 65%, more preferably from about 19% to about 60%, by
weight of the fabric softening composition, of a fabric softener active
selected from the compounds identified hereinafter, and mixtures
thereof.
(A) Diester Quaternary Ammonium Fabric Softeninq Active Compound
tDEQA)
(1) The first type of DEQA preferably comprises, as the principal active,
compounds of the formula
(R)4m- N(+)- [(C~)n-Y~ R~m X(-)
(1)
wherein: each R substituent is a short chain C1-C6, preferably C1-C3
alkyl or hydroxyalkyl group, e.g., methyl (most preferred), ethyl, propyl,
hydroxyethyl, and the like, benzyl or mixtures thereof; each m is 2 or
3; each n is from 1 to about 4; each Y is -O-(O)C-, or -C(O)-O-, but
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not -OC(O)O-; the sum of carbons in each R1, plus one when Y is -O-
(O)C-, is C6-C22, preferably C14-C20, but no more than one YR1 sum
being less than about 12 and then the other YR1 sum is at least about
16, with each R1 being a long chain Cg-C22 (or C7-C21)hydrocarbyl,
S or substituted hydrocarbyl substituent, preferably C10-C20 (or Cg-C1g)alkyl or alkylene, most preferably C12-c18 (or C1 1-C17) alkyl or
alkylene, and where, when said sum of carbons is C16-C1g and R1 is
a straight chain alkyl or alkylene group, the lodine Value (hereinafter
referred to as IV) of the parent fatty acid of this R1 group is preferably
I0 from about 40 to about 140, more preferably from about 50 to about
130; and most preferably from about 70 to about 115. (As used
herein, the lodine Value of a "parent" fatty acid, or "corresponding"
fatty acid, is used to dehne a level of unsaturation for an R1 group that
is the same as the level of unsaturation that would be present in a fatty
acid containing the same R1 group.)
The counterion, X(~) above, can be any softener-compatible anion,
preferably the anion of a strong acid, for example, chloride, bromide,
methylsulfate, sulfate, nitrate and the like, more preferably chloride.
The anion can also, but less preferably, carry a double charge in which
case X(~) represents half a group.
Preferred biodegradable quaternary ammonium fabric softening
compounds can contain the group C(O)R1 which is derived from
unsaturated, and polyunsaturated, fatty acids, e.g., oleic acid, and/or
partially hydrogenated fatty acids, derived from vegetable oils and/or
partially hydrogenated vegetable oils, such as, canola oil, safflower oil,
peanut oil, sunflower oil, corn oil, soybean oil, tall oil, rice bran oil, etc.
Non-limiting examples of DEQAs prepared from preferred fatty acids
have the following approximate distributions:
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Fatty Acyl
Group DEQA1 DEQA2 DEQA3 DEQA4 DEQA5
C 12 trace 66 0 0 0
C14 3 22 0 0 0
C16 4 12 5 5 5
C18 0 - 5 6 6
C14:1 3 - 0 0 0
C16:1 11 - 0 0 3
C18:1 74 - 71 68 67
C18:2 4 - 8 11 11
l O C18:3 0 - 1 2 2
C20: 1 0 - 2 2 2
C20 and up 0 - 2 0 0
Unknowns 0 - 6 6 7
Total 99 100 100 100 103
IV 86-90 Unknown 99 100 95
cis/trans (C 18: 1) 20-30 - 4 5 5
TPU~ 4 - 10 13 13
~ Total Polyunsaturates
Mixtures of fatty acids, and mixtures of DEQAs that are derived
from different fatty acids can be used, and are preferred. Non limiting
examples of DEQA's that can be blended, to form DEQA's are as
follows:
Fattv ACYI Group DEQA6 DEQA7
C14 0
C16 11 25
C18 4 20
C14:1 0 0
C16:1 1 0
C18:1 27 45
C18:2 50 6
C18:3 7 0
Unknowns 0 3
Total 100 100
IV 125-138 56
cis/trans (C 18: 1) Not Available 7
TPU 57 6
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DEQA6 is prepared from a soy bean fatty acid, and DEQA7 is
prepared from a slightly hydrogenated tallow fatty acid.
Also optionally, but preferably, R1 groups can comprise branched
chains, e.g., from isostearic acid, for at least part of the R1 groups.
The total of active represented by the branched chain groups, when
they are present, is typically from about 1% to about 90%, preferably
from about 10% to about 70%, more preferably from about 20% to
about 50%.
Fatty Acyl Group DEQA8 DEQA9 DEQA1Q
I0 Isomyristic acid -- 1-2 --
Myristic acid 7-11 0.5-1 --
lsopalmitic acid 6-7 6-7 1-3
Palmitic acid 4-5 6-7 --
lsostearic acid 70-76 80-82 60-66
lS Stearic acid -- 2-3 8-10
Isoleic acid -- -- 13-17
Oleic acid -- -- 6-12
IV 3 2 7-12
DEQA8 DEQA10 are prepared from different commercially
available isostearic acids.
The more preferred DEQA's are those that are prepared as a single
DEQA from blends of all the different fatty acids that are represented
(total fatty acid blend), rather than from blends of mixtures of separate
finished DEQA's that are prepared from different portions of the total
fatty acid blend.
It is preferred that at least a majority of the fatty acyl groups are
unsaturated, e.g., from about 50% to 100%, preferably from about 55%
to about 95%, more preferably from about 60% to about 90%, and that
the total level of active containing polyunsaturated fatty acyl groups
(TPU) be from about 3% to about 30%, preferably from about 5% to
about 25%, more preferably from about 10% to about 18%. The
cis/trans ratio for the unsaturated fatty acyl groups is important, with a
cis/trans ratio of from 1: 1 to about 50: 1, the minimum being 1: 1,
preferably at least 3:1, and more preferably from about 4:1 to about
20:1. (As used herein, the "percent of softener active" containing a
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given R1 group is the same as the percentage of that same R1 group
is to the total R1 groups used to form all of the softener actives.)
The unsaturated, including the preferred polyunsaturated, fatty acyl
groups, discussed hereinbefore and hereinafter, surprisingly provide
S effective softening, but also provide better rewetting characteristics,
good antistatic characteristics, and especially, superior recovery after
freezing and thawing.
The highly unsaturated materials are also easier to formulate into
concentrated premixes that maintain their low viscosity and are
therefore easier to process, e.g., pump, mixing, etc. These highly
unsaturated materials with only the low amount of solvent that normally
is associated with such materials, i.e., from about 5% to about 20%,
preferably from about 8% to about 25%, more preferably from about
10% to about 20%, weight of the total softener/solvent mixture, are
also easier to formulate into concentrated, stable fabric softening
compositions, even at ambient temperatures. This ability to process
the actives at low temperatures is especially important for the
polyunsaturated groups, since it minimizes degradation. Additional
protection against degradation can be provided when the compounds
and softener compositions contain effective antioxidants and/or
reducing agents, as disclosed hereinafter.
The fabric softening compositions can contain medium-chain
biodegradable quaternary ammonium fabric softening compound,
DEQA, as a preferred component, having the above formula (1) and/or
formula (2), below, wherein:
each Y is -O-(O)C-, or -C(O)-O-, preferably -O-(O)C-;
m is 2 or 3, preferably 2;
each n is 1 to 4, preferably 2;
each R substituent is a C1-C6 alkyl, preferably a methyl, ethyl, propyl,
benzyl groups and mixtures thereof, more preferably a C1-C3 alkyl
group;
each R1 is a saturated, (the IV is preferably about 10 or less, more
preferably less than about 5), (The sum of the carbons in R+1 is
increased by one when Y is -O-(O)C-.) Cg-C14 preferably a C12 14
hydrocarbyl, or substituted hydrocarbyl substituent and the counterion,
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X-, is the same as above. Preferably X- does not include phosphate
salts.
The saturated Cg-C14 fatty acyl groups can be pure derivatives or
can be mixed chain lengths.
Suitable fatty acid sources for said fatty acyl groups are coco,
lauric, caprylic, and capric acids.
For C12-C14 (or C11-C13) hydrocarbyl groups, the groups are
preferably saturated, e.g., the IV is preferably less than about 10,
preferably less than about 5.
I0 It will be understood that substituents R and R1 can optionally be
substituted with various groups such as alkoxyl or hydroxyl groups,
and can be straight, or branched so long as the R1 groups maintain
their basically hydrophobic character. The preferred compounds can
be considered to be biodegradable diester variations of ditallow
dimethyl ammonium chloride (hereinafter referred to as "DTDMAC"),
which is a widely used fabric softener.
A preferred long chain DEQA is the DEQA prepared from sources
containing high levels of polyunsaturation, i.e., N,N-di(acyl-oxyethyl)-
N,N-dimethyl ammonium chloride, where the acyl is derived from fatty
acids containing sufficient polyunsaturation, e.g., mixtures of tallow
fatty acids and soybean fatty acids. Another preferred long chain
DEQA is the dioleyl (nominally) DEQA, i.e., DEQA in which N,N-
di(oleoyl-oxyethyl)-N,N-dimethyl ammonium chloride is the major
ingredient. Preferred sources of fatty acids for such DEQAs are
vegetable oils, and/or partially hydrogenated vegetable oils, such as
canola oil, with high contents of unsaturated, e.g., oleoyl groups.
Highly preferred medium chain DEQAs are dicocoyl DEQA (derived
from coconut fatty acids), i.e., N,N-di(coco-oyl-oxyethyl)-N,N-dimethyl
ammonium chloride, exemplified hereinafter as DEQA6, and N, N-
di(lauroyl-oxyethyl)-N,N-dimethyl ammonium chloride.
As used herein, when the diester is specihed, it can include the
monoester that is present. Preferably, at least about 80% of the DEQA
is in the diester form, and from 0% to about 20% can be DEQA
monoester, e.g., in formula (1), m is 2 and one yR1 group is either H
3~ or-C(O)OH. For softening, under no/low detergent carry-over laundry
.
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conditions the percentage of monoester should be as low as possible,
preferably no more than about 5%. However, under high, anionic
detergent surfactant or detergent builder carry-over conditions, some
monoester can be preferred. The overall ratios of diester to monoester
are from about 100:1 to about 2:1, preferably from about 50:1 to about
5:1, more preferably from about 13:1 to about 8:1. Under high
detergent carry-over conditions, the di/monoester ratio is preferably
about 11:1. The level of monoester present can be controlled in
manufacturing the DEQA.
The above compounds, used as the biodegradable quaternized
ester-amine softening material in the practice of this invention, can be
prepared using standard reaction chemistry. In one synthesis of a di-
ester variation of DTDMAC, an amine of the formula RN(CH2CH2OH)2
is esterified at both hydroxyl groups with an acid chloride of the
formula R1C(O)CI, then quaternized with an alkyl halide, RX, to yield
the desired reaction product (wherein R and R1 are as defined
hereinbefore). However, it will be appreciated by those skilled in the
chemical arts that this reaction sequence allows a broad selection of
agents to be prepared.
Yet another DEQA softener active that is suitable for the
formulation of a concentrated, clear liquid fabric softener composition
has the above formula (1) wherein one R group is a C1 4 hydroxy alkyl
group, preferably one wherein one R group is a hydroxyethyl group.
An example of such a hydroxyethyl ester active is di(acyloxyethyl)(2-
hydroxyethyl)methyl ammonium methyl sulfate, wherein the acyl group
is the same as that of DEQA1, exemplified hereinafter as DEQA8.
(2) The second type of DEQA active has the general formula:
R1-Y-CH2~
CHcH2N(+)R3 X(-)
R -Y~
- (2)~0
wherein each Y, R, R1, and X(~) have the same meanings as before.
Such compounds include those having the formula:
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[CH3]3 N(+)[CH2CH(CH20C[O]R1 )OC(O)R1 ] Cl(-)
where each R is a methyl or ethyl group and preferably each R1 is in
the range of C1s to C1g. Degrees of branching and substitution can
be present in the alkyl(ene) chains. The anion X(~) in the moiecule is
the same as in DEQA (1) above. As used herein, when the diester is
specified, it can include the monoester that is present. The amount of
monoester that can be present is the same as in DEQA (1). An
example of a preferred DEQA of formula (2) is the "propyl" ester
quaternary ammonium fabric softener active having the formula 1,2-
di(acyloxy)-3-trimethylammoniopropane chloride, wherein the acyl
group is the same as that of DEQA5.
These types of agents and general methods of making them are
disclosed in U.S. Pat. No. 4,137,180, Naik et al., issued Jan. 30, 1979,
l5 which is incorporated herein by reference
In preferred softener actives (1) and (2), each R1 is a hydrocarbyl,
or substituted hydrocarbyl, group, preferably, alkyl, monounsaturated
alkylene, and polyunsaturated alkylene groups, with the softener active
containing polyunsaturated alkylene groups being at least about 3%,
preferably at least about 5%, more preferably at least about 10%, and
even more preferably at least about 15%, by weight of the total
softener active present; the actives preferably containing mixtures of
R1 groups, especially within the individual molecules, and also,
optionally, but preferably, the saturated R1 groups comprising
branched chains, e.g., from isostearic acid, for at least part of the
saturated R1 groups, the total of active represented by the branched
chain groups preferably being from about 1% to about 90%, preferably
from about 10% to about 70%, more preferably from about 20% to
about 50%.
The DEQAs herein can contain a low level of fatty acid, which can
be from unreacted starting material used to form the DEQA and/or as a
by-product of any partial degradation (hydrolysis) of the softener active
in the finished composition. It is preferred that the level of free fatty
acid be low, preferably below about 10%, and more preferably below
about 5%, by weight of the fabric softener active.
. .
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3. Other fabric softening ingredients
Low molecular weight water soluble solvents can also be used at
levels of from 0% to about 12%, preferably from about 1% to about
10%, more preferably from about 2% to about 8%. The water soluble
S solvents cannot provide a clear product at the same low levels of the
principal solvents described hereinbefore but can provide clear product
when the principal solvent is not sufficient to provide completely clear
product. The presence of these water soluble solvents is therefore
highly desirable. Such solvents include: ethanol; isopropanol; 1,2-
propanediol; 1,3-propanediol; propylene carbonate; etc. but do not
include any of the principal solvents.
B. Liquid Laundry Detergent Compositions
A liquid laundry detergent composition, including heavy duty liquid
detergent compositions, typically contains certain anionic surfactants (preferably
in combination with nonionic surfactants). The preferred liquid laundry detergent
compositions contain the following ingredients.
1. Anionic Detersive Surfactants
The compositions of the present invention comprise at least about
0.01%, preferably at least 0.1%, more preferably from about 1% to about
95%, most preferably from about 1% to about 80% by weight, of an
anionic detersive surfactant selected from the group consisting of alkyl
sulfates, alkyl alkoxylated sulfates, and mixtures thereof. Alkyl sulfate
surfactants, either primary or secondary, are a type of anionic surfactant
of importance for use herein. Alkyl sulfates have the general formula
2S ROSO3M wherein R preferably is a C10-C24 hydrocarbyl, preferably an
alkyl straight or branched chain or hydroxyalkyl having a C10-C20 alkyl
component, more preferably a C12-C1g alkyl or hydroxyalkyl, and M is
hydrogen or a water soluble cation, e.g., an alkali metal cation (e.g.,
sodium potassium, lithium), substituted or unsubstituted ammonium
cations such as methyl-, dimethyl-, and trimethyl ammonium and
quaternary ammonium cations, e.g., tetramethyl-ammonium and
dimethyl piperdinium, and cations derived from alkanolamines such as
ethanolamine, diethanolamine, triethanolamine, and mixtures thereof,
and the like. Typically, alkyl chains of C12-C16 are preferred for lower
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wash temperatures (e.g., below about 50~C) and C16-C1g alkyl chains
are preferred for higher wash temperatures (e.g., about 50~C).
Alkyl alkoxylated sulfate surfactants are another category of
preferred anionic surfactant. These surfactants are water soluble salts
or acids typically of the formula RO(A)mSO3M wherein R is an
unsubstituted C10-C24 alkyl or hydroxyalkyl group having a C10-C24
alkyl component, preferably a C12-C20 alkyl or hydroxyalkyl, more
preferably C12-C1g alkyl or hydroxyalkyl, A is an ethoxy or propoxy
unit, m is greater than zero, typically between about 0.5 and about 6,
more preferably between about 0.5 and about 3, and M is hydrogen or
a water soluble cation which can be, for example, a metal cation (e.g.,
sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or
substituted-ammonium cation. Alkyl ethoxylated sulfates as well as
alkyl propoxylated sulfates are contemplated herein. Specific
examples of substituted ammonium cations include methyl-, dimethyl-,
trimethyl-ammonium and quaternary ammonium cations, such as
tetramethyl-ammonium, dimethyl piperdinium and cations derived from
alkanolamines, e.g., monoethanolamine. diethanolamine, and
triethanolamine, and mixtures thereof. Exemplary surfactants are
C12C1g alkyl polyethoxylate (1.0) sulfate, C12-C1g alkyl
polyethoxylate (2.25) sulfate, C1 2-C1 8 alkyl polyethoxylate (3.0)
sulfate, and C12-C1g alkyl polyethoxylate (4.0) sulfate wherein M is
conveniently selected from sodium and potassium.
2. Nonionic Detersive Surfactants
The compositions of the present invention preferably also comprise
at least about 0.01%, preferably at least 0.1%, more preferably from
about 1% to about 95%, most preferably from about 1% to about 80% by
weight, of an nonionic detersive surfactant. Preferred nonionic
surfactants such as C12-C1g alkyl ethoxylates ("AE") including the so-
called narrow peaked alkyl ethoxylates and C6-C12 alkyl phenol
alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), block
alkylene oxide condensate of C6 to C12 alkyl phenols, alkylene oxide
condensates of Cg-C22 alkanols and ethylene oxide/propylene oxide
block polymers (PluronicTM-BASF Corp.), as well as semi polar nonionics
(e.g., amine oxides and phosphine oxides) can be used in the present
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compositions. An extensive disclosure of these types of surfactants is
found in U.S. Pat. 3,929,678, Laughlin et al., issued December 30, 1975,
incorporated herein by reference.
Alkylpolysaccharides such as disclosed in U.S. Pat. 4,565,647
Llenado (incorporated herein by reference) are also preferred nonionic
surfactants in the compositions of the invention.
Further preferred nonionic surfactants are the polyhydroxy fatty acid
amides having the formula:
I I 1 8
R7--C--N--Q
wherein R7 is Cs-C31 alkyl, preferably straight chain C7-C1g alkyl or
alkenyl, more preferably straight chain Cg-C17 alkyl or alkenyl, most
preferably straight chain C11-C1s alkyl or alkenyl, or mixtures thereof;
R8 is selected from the group consisting of hydrogen, C1-C4 alkyl, C1-
C4 hydroxyalkyl, preferably methyl or ethyl, more preferably methyl. Q is
a polyhydroxyalkyl moiety having a Jinear alkyl chain with at least 3
hydroxyls directly connected to the chain, or an alkoxylated derivative
thereof; preferred alkoxy is ethoxy or propoxy, and mixtures thereof.
Preferred Q is derived from a reducing sugar in a reductive amination
reaction. More preferably Q is a glycityl moiety. 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 utilized as well as the
individual sugars listed above. These corn syrups may yield a mix of
sugar components for Q. It should be understood that it is by no means
intended to exclude other suitable raw materials. Q is more preferably
selected from the group consisting of -CH2(CHOH)nCH2OH,-
CH(CH20H)(CHOH)n-1CH2~H, -CH2(cHOH)2-
(CHOR')(CHOH)CH2OH, and alkoxylated derivatives thereof, wherein n
is an integer from 3 to 5, inclusive, and R' is hydrogen or a cyclic or
aliphatic monosaccharide. Most preferred substituents for the Q moiety
are glycityls wherein n is 4, particularly -CH2(CHOH)4CH2OH.
R7Co-Nc can be, for example, cocamide, stearamide, oleamide,
lauramide, myristamide, capricamide, palmitamide, tallowamide, etc.
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R8 can be, for example, methyl, ethyl, propyl, isopropyl, butyl, 2-
hydroxy ethyl, or 2-hydroxy propyl.
Q can be 1-deoxyglucityl, 2-deoxyfructityl, 1-deoxymaltityl, 1-
deoxylactityl, 1-deoxygalactityl, 1-deoxymannityl, 1-deoxymaltotriotityl,
etc.
A particularly desirable surfactant of this type for use in the
compositions herein is alkyl-N-methyl glucomide, a compound of the
above formula wherein R7 is alkyl (preferably C11-C13), R8, is methyl
and Q is 1-deoxyglucityl.
Other sugar-derived surfactants include the N-alkoxy polyhydroxy
fatty acid amides, such as C10-c18 N-(3-methoxypropyl) glucamide.
The N-propyl through N-hexyl C12-C1g glucamides can be used for
low sudsing. C10-C20 conventional soaps may also be used. If high
sudsing is desired, the branched-chain C10-c16 soaps may be used.
l S Other conventional useful surfactants are listed in standard texts.
For the purposes of the present invention other detersive
surfactants, described herein below, may be used in the liquid laundry
detergent compositions.
C. Other optional ingredients
The description below provides other optional ingredients (in addition
to the list of components described above), which are non-limiting and
useful in liquid detergent compositions, including fabric softening
compositions, liquid laundry detergent compositions such as heavy duty
liquid detergent compositions, and hard surface cleaning applications,
such as dish washing liquid detergent compositions.
1. Brighteners
The liquid detergent compositions herein can also optionally
contain from about 0.005% to 5% by weight of certain types of
hydrophilic optical brighteners which also provide a dye transfer
inhibition action. If used, the compositions herein will preferably
comprise from about 0.001% to 1% by weight of such optical
brighteners.
The hydrophilic optical brighteners useful in the present
invention are those having the structural formula:
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R1~ P~
~0
H H N~
~)BM ~\A 'R1
wherein R1 is selected from anilino, N-2-bis-hydroxyethyl and NH-2-
hydroxyethyl; R2 is selected from N-2-bis-hydroxyethyl, N-2-
hydroxyethyl-N-methylamino, morphilino, chloro and amino; and M is a
salt-forming cation such as sodium or potassium.
When in the above formula, R1 is anilino, R2 is N-2-bis-
hydroxyethyl and M is a cation such as sodium, the brightener is 4,4',-
bis[(4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazine-2-yl)amino]-2,2'-
stilbenedisulfonic acid and disodium salt. This particular brightener
l O species is commercially marketed under the tradename Tinopal-
UNPA-GX~) by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the
preferred hydrophilic optical brightener useful in the rinse added
compositions herein.
When in the above formula, R1 is anilino, R2 is N-2-hydroxyethyl-
lS N-2-methylamino and M is a cation such as sodium, the brightener is
4,4'-bis[(4-anilino-6-(N-2-hydroxyethyl-N-methylamino~-s-triazine-2-
yl)amino]2,2'-stilbenedisulfonic acid disodium salt. This particular
brightener species is commercially marketed under the tradename
Tinopal 5BM-GX(~) by Ciba-Geigy Corporation.
When in the above formula, R1 is anilino, R2 is morphilino and M is
a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6-
morphilino-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid, sodium
salt. This particular brightener species is commercially marketed
under the tradename Tinopal AMS-GX~) by Ciba Geigy Corporation
2. Dispersibility Aids
Liquid detergent compositions can optionally contain dispersibility
aids, e.g., those selected from the group consisting of mono-long chain
alkyl cationic quaternary ammonium compounds, mono-long chain
alkyl amine oxides, and mixture thereof. When said dispersibility aid is
present, it is typically present at a total level of from about 2% to about
25%, preferably from about 3 % to about 17%, more preferably from
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4% to about 15%, and even more preferably from about 5% to about
13%, by weight of the composition. These aids are described in P&G
Copending Application Serial No. 08/461,207, filed June 5, 1995, Wahl
et al., specifically on page 14, line 12 to page 20, line 12, which is
herein incorporated by reference.
These materials can either be added as part of the active softener
raw material, (formula (1)), e.g., the mono-long chain alkyl cationic
surfactant or added as a separate component. The total level of
dispersibility aid includes any amount that may be present as part of
l O component ( 1).
(1) Mono-Alkyl Cationic Quaternary Ammonium Compound
When the mono-alkyl cationic quaternary ammonium compound is
present, it is typically present at a level of from about 2% to about
25%, preferably from about 3% to about 17%, more preferably from
about 4% to about 15%, and even more preferably from 5% to about
13% by weight of the composition, the total mono-alkyl cationic
quaternary ammonium compound being at least at an effective level.
Such mono-alkyl cationic quaternary ammonium compounds useful
in the present invention are, preferably, quaternary ammonium salts of
the general formula:
[R4N+(R5)3] X~
wherein
R4 is Cg-C22 alkyl or alkenyl group, preferably C10-c18 alkyl or
alkenyl group; more preferably C10-C14 or C16-C1g alkyl or alkenyl
group;
each R5 is a C1-C6 alkyl or substituted alkyl group (e.g., hydroxy
alkyl), preferably C1-C3 alkyl group, e.g., methyl (most preferred),
ethyl, propyl, and the like, a benzyl group, hydrogen, a polyethoxylated
chain with from about 2 to about 20 oxyethylene units, preferably from
about 2.5 to about 13 oxyethylene units, more preferably from about 3
to about 10 oxyethylene units, and mixtures thereof; and
X~ is as defined hereinbefore for (Formula (I)).
Especially preferred dispersibility aids are monolauryl trimethyl
ammonium chloride and monotallow trimethyl ammonium chloride
available from Witco under the trade name Varisoft(~) 471 and
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monooleyl trimethyl ammonium chloride available from Witco under the
tradename Varisoft~) 417.
The R4 group can also be attached to the cationic nitrogen atom
through a group containing one, or more, ester, amide, ether, amine,
S etc., linking groups which can be desirable for increased
concentratability of component (I), etc. Such linking groups are
preferably within from about one to about three carbon atoms of the
nitrogen atom.
Mono-alkyl cationic quaternary ammonium compounds also include
Cg-C22 alkyl choline esters. The preferred dispersibility aids of this
type have the formula:
R1c(o)-o-cH2cH2N+(R)3 X-
wherein R1, R and X- are as defined previously.
Highly preferred dispersibility aids include C12-C14 coco choline
ester and C16-C1g tallow choline ester.
Suitable biodegradable single-long-chain alkyl dispersibility aids
containing an ester linkage in the long chains are described in U.S.
Pat. No. 4,840,738, Hardy and Walley, issued June 20, 1989, said
patent being incorporated herein by reference.
When the dispersibility aid comprises alkyl choline esters,
preferably the compositions also contain a small amount, preferably
from about 2% to about 5% by weight of the composition, of organic
acid. Organic acids are described in European Patent Application No.
404,471, Machin et al., published on Dec. 27, 1990, supra, which is
'5 herein incorporated by reference. Preferably the organic acid is
selected from the group consisting of glycolic acid, acetic acid, citric
acid, and mixtures thereof.
Ethoxylated quaternary ammonium compounds which can serve as
the dispersibility aid include ethylbis(polyethoxy
ethanol)alkylammonium ethyl-sulfate with 17 moles of ethylene oxide,
available under the trade name Variquat(~) 66 from Sherex Chemical
Company; polyethylene glycol (15) oleammonium chloride, available
under the trade name Ethoquad(É~) 0/25 from Akzo; and polyethylene
glycol (15) cocomonium chloride, available under the trade name
Ethoquad'~) C/25 from Akzo.
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Although the main function of the dispersibility aid is to increase the
dispersibility of the ester softener, preferably the dispersibility aids also
have some softening properties to boost softening performance of the
composition. Therefore, preferably the liquid detergent compositions
are essentially free of non-nitrogenous ethoxylated nonionic
dispersibility aids which will decrease the overall softening
performance of the compositions.
Also, quaternary compounds having only a single long alkyl chain,
can protect the cationic softener from interacting with anionic
surfactants and/or detergent builders that are carried over into the
rinse from the wash solution.
(2) Amine Oxides
Suitable amine oxides include those with one alkyl or hydroxyalkyl
moiety of about 8 to about 22 carbon atoms, preferably from about 10
to about 18 carbon atoms, more preferably from about 8 to about 14
carbon atoms, and two alkyl moieties selected from the group
consisting of alkyl groups and hydroxyalkyl groups with about 1 to
about 3 carbon atoms.
Examples include dimethyloctylamine oxide, diethyldecylamine
oxide, bis-(2-hydroxyethyl)dodecyl-amine oxide, dimethyldodecylamine
oxide, dipropyl- tetradecylamine oxide, methylethylhexadecylamine
oxide, dimethyl-2-hydroxyoctadecylamine oxide, and coconut fatty
alkyl dimethylamine oxide.
3. Stabilizers
Stabilizers can be present in liquid detergent compositions. The
term "stabilizer," as used herein, includes antioxidants and reductive
agents. These agents are present at a level of from 0% to about 2%,
preferably from about 0.01% to about 0.2%, more preferably from
about 0.035% to about 0.1% for antioxidants, and more preferably
from about 0.01% to about 0.2% for reductive agents. These assure
good odor stability under long term storage conditions. Antioxidants
and reductive agent stabilizers are especially critical for unscented or
low scent products (no or low perfume).
~xamples of antioxidants that can be added to the compositions of
this invention include a mixture of ascorbic acid, ascorbic palmitate,
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propyl gallate, available from Eastman Chemical Products, Inc., under
the trade names Tenox(E~) PG and Tenox(~) S-1; a mixture of BHT
(butylated hydroxytoluene), BHA (butylated hydroxyanisole), propyl
gallate, and citric acid, available from Eastman Chemical Products,
S Inc., under the trade name Tenox~6; butylated hydroxytoluene,
available from UOP Process Division under the trade name Sustane~
BHT; tertiary butylhydroquinone, Eastman Chemical Products, Inc., as
Tenox~9 TBHQ; natural tocopherols, Eastman Chemical Products, Inc.,
as Tenox~) GT-1/GT-2; and butylated hydroxyanisole, Eastman
Chemical Products, Inc., as BHA; long chain esters (Cg-C22) of gallic
acid, e.g., dodecyl gallate; Irganox@~) 1010; Irganox~) 1035; Irganox~) B
1171; Irganox(E~ 1425; Irganox~) 3114; Irganox~g) 3125; and mixtures
thereof; preferably Irganox~ 3125, Irganox~g) 1425, Irganox~ 3114,
and mixtures thereof; more preferably Irganox@) 3125 alone or mixed
l 5 with citric acid and/or other chelators such as isopropyl citrate,
Dequest(g) 2010, available from Monsanto with a chemical name of 1-
hydroxyethylidene-1, 1-diphosphonic acid (etidronic acid), and Tiron@~,
available from Kodak with a chemical name of 4,5-dihydroxy-m-
benzene-sulfonic acid/sodium salt, and DTPA~), available from Aldrich
with a chemical name of diethylenetriaminepentaacetic acid.
4. Soil Release Agent
In liquid detergent compositions, an optional soil release agent can
be added. The addition of the soil release agent can occur in
combination with the premix, in combination with the acid/water seat,
before or after electrolyte addition, or after the final composition is
made. The composition can contain from 0% to about 10%, preferably
from 0.2% to about 5%, of a soil release agent. Preferably, such a soil
release agent is a polymer. Polymeric soil release agents useful in the
present invention include copolymeric blocks of terephthalate and
polyethylene oxide or polypropylene oxide, and the like.
A preferred soil release agent is a copolymer having blocks of
terephthalate and polyethylene oxide. More specifically, these
polymers are comprised of repeating units of ethylene terephthalate
and polyethylene oxide terephthalate at a molar ratio of ethylene
terephthalate units to polyethylene oxide terephthalate units of from
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25:75 to about 35:65, said polyethylene oxide terephthalate containing
polyethylene oxide blocks having molecular weights of from about 300
to about 2000. The molecular weight of this polymeric soil release
agent is in the range of from about 5,000 to about 55,000.
Another preferred polymeric soil release agent is a crystallizable
polyester with repeat units of ethylene terephthalate units containing
from about 10% to about 15% by weight of ethylene terephthalate
units together with from about 10% to about 50% by weight of
polyoxyethylene terephthalate units, derived from a polyoxyethylene
glycol of average molecular weight of from about 300 to about 6,000,
and the molar ratio of ethylene terephthalate units to polyoxyethylene
terephthalate units in the crystallizable polymeric compound is
between 2:1 and 6:1. Examples of this polymer include the
commercially available materials Zelcon 4780~ (from Dupont) and
Milease T(g) (from ICI).
Highly preferred soil release agents are polymers of the generic
formula:
X--(OCH2CH2)p(~C--R - C--OR ~U(~I~-R 1 40~-oxct 12CH2~)r~-X
in which each X can be a suitable capping group, with each X typically
being selected from the group consisting of H, and alkyl or acyl groups
containing from about 1 to about 4 carbon atoms. p is selected for
water solubility and generally is from about 6 to about 113, preferably
from about 20 to about 50. u is critical to formulation in a liquid
composition having a relatively high ionic strength. There should be
very little material in which u is greater than 10. Furthermore, there
should be at least 20%, preferably at least 40%, of material in which u
ranges from about 3 to about 5.
The R14 moieties are essentially 1,4-phenylene moieties. As used
herein, the term "the R14 moieties are essentially 1,4-phenylene
moieties" refers to compounds where the R14 moieties consist entirely
of 1,4-phenylene moieties, or are partially substituted with other
arylene or alkarylene moieties, alkylene moieties, alkenylene moieties,
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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 1,2-propylene, 1,4-butylene,
1,5-pentylene, 1,6-hexamethylene, 1,7-heptamethylene, 1,8-
octamethylene, 1,4-cyclohexylene, and mixtures thereof.
For the R14 moieties, the degree of partial substitution with
moieties other than 1 ,4-phenylene should be such that the soil release
properties of the compound are not adversely affected to any great
extent. Generally the degree of partial substitution which can be
tolerated will depend upon the backbone length of the compound, i.e.,
longer backbones can have greater partial substitution for 1,4-
phenylene moieties. Usually, compounds where the R14 comprise
from about 50% to about 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 with a 40:60 mole ratio
of isophthalic (1,3-phenylene) to terephthalic (1,4-phenylene) 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 1,4-phenylene for best soil release activity.
Preferably, the R14 moieties consist entirely of (i.e., comprise 100%)
1,4-phenylene moieties, i.e., each R14 moiety is 1,4-phenylene.
For the R15 moieties, suitable ethylene or substituted ethylene
moieties include ethylene, 1,2-propylene, 1,2-butylene, 1,2-hexylene,
3-methoxy-1,2-propylene, and mixtures thereof. Preferably, the R15
moieties are essentially ethylene moieties, 1,2-propylene moieties, or
mixtures thereof. Inclusion of a greater percentage of ethylene
moieties tends to improve the soil release activity of compounds.
Surprisingly, inclusion of a greater percentage of 1,2-propylene
moieties tends to improve the water solubility of compounds.
Therefore, the use of 1,2-propylene moieties or a similar branched
equivalent is desirable for incorporation of any substantial part of the
soil release component in the liquid fabric softener compositions.
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Preferably, from about 75% to about 100%, are 1,2-propylene
molebes.
The value for each p is at least about 6, and preferably is at least
about 10. The value for each n usually ranges from about 12 to about
113. Typically the value for each p is in the range of from about 12 to
about 43.
A more complete disclosure of soil release agents is contained in
U.S. Pat. Nos.: 4,661,267, Decker, Konig, Straathof, and Gosselink,
issued Apr. 28, 1987; 4,711,730, Gosselink and Diehl, issued Dec. 8,
1987; 4,749,596, Evans, Huntington, Stewart, Wolf, and Zimmerer,
issued June 7, 1988; 4,818,569, Trinh, Gosselink, and Rattinger,
issued April 4, 1989; 4,877,896, Maldonado, Trinh, and Gosselink,
issued Oct. 31, 1989; 4,956,447, Gosselink et al., issues Sept. 11,
1990; and 4,976,879, Maldonado, Trinh, and Gosselink, issued Dec.
11, 1990, all of said patents being incorporated herein by reference.
These soil release agents can also act as scum dispersants.
. Scum Dispersant
Liquid detergent compositions optionally contain scum dispersant,
other than the soil release agent. The preferred scum dispersants
herein are formed by highly ethoxylating hydrophobic materials. The
hydrophobic material can be a fatty alcohol, fatty acid, fatty amine,
fatty acid amide, amine oxide, quaternary ammonium compound, or
the hydrophobic moieties used to form soil release polymers. The
preferred scum dispersants are highly ethoxylated, e.g., more than
about 17, preferably more than about 25, more preferably more than
about 40, moles of ethylene oxide per molecule on the average, with
the polyethylene oxide portion being from about 76% to about 97%,
preferably from about 81 % to about 94%, of the total molecular weight.
The level of scum dispersant is sufficient to keep the scum at an
acceptable, preferably unnoticeable to the consumer, level under the
conditions of use, but not enough to adversely affect softening. For
some purposes it is desirable that the scum is nonexistent. Depending
on the amount of anionic or nonionic detergent, etc., used in the wash
cycle of a typical laundering process, the efficiency of the rinsing steps
prior to the introduction of the compositions herein, and the water
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hardness, the amount of anionic or nonionic detergent surfactant and
detergency builder (especially phosphates and zeolites) entrapped in
the fabric (laundry) will vary. Normally, the minimum amount of scum
dispersant should be used to avoid adversely affecting softening
properties. Typically scum dispersion requires at least about 2%,
preferably at least about 4% (at least 6% and preferably at least 10%
for maximum scum avoidance) based upon the level of softener active.
However, at levels of about 10% (relative to the softener material) or
more, one risks loss of softening efficacy of the product especially
when the fabrics contain high proportions of nonionic surfactant which
has been absorbed during the washing operation.
Preferred scum dispersants are: Brij 700~g); Varonic U-250~);
Genapol T-500(~, Genapol T-800(~); Plurafac A-79~g); and Neodol 25-
50~).
6. Bactericides
Examples of bactericides optionally used in the compositions of this
invention include glutaraldehyde, formaldehyde, 2-bromo-2-nitro-
propane-1,3-diol sold by Inolex Chemicals, located in Philadelphia,
Pennsylvania, under the trade name Bronopol~), and a mixture of 5-
chloro-2-methyl4-isothiazoline-3-one and 2-methyl4-isothiazoline-3-
one sold by Rohm and Haas Company under the trade name Kathon~
about 1 to about 1,000 ppm by weight of the agent.
7. Perfume
Liquid detergent compositions can optionally contain
compatible perfume. Suitable perfumes are disclosed in U.S.
Pat. 5,500,138, Bacon et al., issued March 19, 1996, said patent
being incorporated herein by reference.
As used herein, perfume includes fragrant substance or
mixture of substances including natural (i.e., obtained by
extraction of flowers, herbs, leaves, roots, barks, wood, blossoms
or plants), artificial (i.e., a mixture of different nature oils or oil
constituents) and synthetic (i.e., synthetically produced)
odoriferous substances. Such materials are often accompanied
by auxiliary materials, such as fixatives, extenders, stabilizers and
solvents. These auxiliaries are also included within the meaning
.
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of "perfume", as used herein. Typically, perfumes are complex
mixtures of a plurality of organic compounds.
Perfume can be present at a level of from 0% to about 10%,
preferably from about 0.1% to about 5%, and more preferably from
S about 0.2% to about 3%, by weight of the finished composition.
8. Chelatinq A~ents
The liquid detergent compositions can optionally employ one or
more copper and/or nickel chelating agents ("chelators"). Such water-
soluble chelating agents can be selected from the group consisting of
amino carboxylates, amino phosphonates, polyfunctionally-substituted
aromatic chelating agents and mixtures thereof, all as hereinafter
defined. The whiteness and/or brightness of fabrics are substantially
improved or restored by such chelating agents and the stability of the
materials in the compositions are improved.
I 5 Amino carboxylates useful as chelating agents herein include
ethylenediaminetetraacetates (EDTA), N-
hydroxyethylethylenediaminetriacetates, nitrilotriacetates (NTA),
ethylenediamine tetraproprionates, ethylenediamine-N,N'-
diglutamates, 2-hyroxypropylenediamine-N,N'-disuccinates,
triethylenetetraaminehexacetates, diethylenetriaminepentaacetates
(DETPA), and ethanoldiglycines, including their water-soluble salts
such as the alkali metal, ammonium, and substituted ammonium salts
thereof and mixtures thereof.
Amino phosphonates are also optionally suitable for use as
chelating agents in the compositions when at least low levels of total
phosphorus are permitted in detergent compositions, and include
ethylenediaminetetrakis (methylenephosphonates), diethylenetriamine-
N,N,N',N",N"-pentakis(methane phosphonate) (DETMP) and 1-
hydroxyethane-1,1-diphosphonate (HEDP). Preferably, these amino
phosphonates to not contain alkyl or alkenyl groups with more than
about 6 carbon atoms.
The preferred EDDS chelator used herein (also known as
ethylenediamine-N,N'-disuccinate) is the material described in U.S.
Patent 4,704,233, cited hereinabove, and has the formula (shown in
free acid form):
.
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~ N a~Clt~N--H
Çl k ~1 ~1 Ç~
As disclosed in the patent, EDDS can be prepared using maleic
anhydride and ethylenediamine. The preferred biodegradable [S,S]
isomer of EDDS can be prepared by reacting L-aspartic acid with 1,2-
dibromoethane. The EDDS has advantages over other chelators in
that it is effective for chelating both copper and nickel cations, is
available in a biodegradable form, and does not contain phosphorus.
The EDDS employed herein as a chelator is typically in its salt form,
i.e., wherein one or more of the four acidic hydrogens are replaced by
a water-soluble cation M, such as sodium, potassium, ammonium,
triethanolammonium, and the like.
As can be seen from the foregoing, a wide variety of chelators can
be used herein. Indeed, simple polycarboxylates such as citrate,
oxydisuccinate, and the like, can also be used, although such
chelators are not as effective as the amino carboxylates and
phosphonates, on a weight basis. Accordingly, usage levels may be
adjusted to take into account differing degrees of chelating
effectiveness. The chelators herein will preferably have a stability
constant (of the fully ionized chelator) for copper ions of at least about
5, preferably at least about 7. Typically, the chelators will comprise
from about 0.5% to about 10%, more preferably from about 0.75% to
about 5%, by weight of the compositions herein. Preferred chelators
include DETMP, DETPA, NTA, EDDS and mixtures thereof.
9. Other detersive surfactants
In addition to the anionic and nonionic detersive surfactants
described herein above, other detersive surfactants that are suitable
for use in the present invention are cationic, anionic, nonionic,
ampholytic, zwitterionic, and mixtures thereof, further described herein
below.
Nonlimiting examples of other sur~actants useful herein typically at
levels from about 1% to about 55%, by weight, include the
conventional C11-C1g alkyl benzene sulfonates ("LAS"), the C10-C1g
secondary (2,3) alkyl sulfates of the formula CH3(CH2)X(CHOSO3-M+)
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CH3 and CH3 (C1~2)y(CHOS03~M+) CH2CH3 where x and (y + 1) are
integers of at least about 7, preferably at least about 9, and M is a
water-solubilizing cation, especially sodium, unsaturated sulfates such
as oleyl sulfate, C10-C1g alkyl alkoxy carboxylates (especially the EO
1-5 ethoxycarboxylates), the C10-18 glycerol ethers, the C10-c18 alkyl
polyglycosides and their corresponding sulfated polyglycosides, and
C12-C1g alpha-sulfonated fatty acid esters. If desired, the
conventional nonionic and amphoteric surfactants such as the
C12-C1g alkyl ethoxylates ("AE") including the so-called narrow
I 0 peaked alkyl ethoxylates and C6-C 12 alkyl phenol alkoxylates
(especially ethoxylates and mixed ethoxy/propoxy), C12-C1g betaines
and sulfobetaines ("sultaines"), C10-C1g amine oxides, and the like,
can also be included in the overall compositions. The C10-C1g N-alkyl
polyhydroxy fatty acid amides can also be used. Typical examples
IS include the C12-C1g N-methylglucamides. See WO 9,206,154. Other
sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid
amides, such as C10-c18 N-(3-methoxypropyl) glucamide. C10-C20
conventional soaps may also be used. If high sudsing is desired, the
branched-chain C10-C16 soaps may be used. Mixtures of anionic and
nonionic surfactants are especially useful. Other conventional useful
surfactants are listed in standard texts.
Other anionic surfactants useful for detersive purposes can also be
included in the compositions hereof. These can include salts
(including, for example, sodium potassium, ammonium, and
substituted ammonium salts such a mono-, di- and triethanolamine
salts) of soap, Cg-C20 linear alkylbenzenesulphonates, Cg-C22
primary or secondary alkanesulphonates, Cg-C24 olefinsulphonates,
sulphonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl
glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl phenol ethylene
oxide ether sulfates, paraffin sulfonates, alkyl phosphates, isothionates
such as the acyl isothionates, N-acyl taurates, fatty acid amides of
methyl tauride, alkyl succinamates and sulfosuccinates, monoesters of
sulfosuccinate (especially saturated and unsaturated C12-C1 8
monoesters) diesters of sulfosuccinate (especially saturated and
unsaturated C6-C14 diesters), N-acyl sarcosinates, sulfates of
. . .
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alkyipolysaccharides such as the sulfates of alkylpolyglucoside,
branched primary alkyl sulfates, alkyl polyethoxy carboxylates such as
those of the formula RO(CH2CH2O)kCH2COO-M+ wherein R is a Cg-
C22 alkyl, k is an integer from 0 to 10, and M is a soluble salt-forming
cation, and fatty acids esterified with isethionic acid and neutralized
with sodium hydroxide. Further examples are given in Surface Active
Aqents and Detergents (Vol. I and ll by Schwartz, Perry and Berch).
10. Non-cotton and cotton soil release polymers
The non-cotton soil release polymers which can be used include
the following.
A) at least about 0.01% by weight, of a non-cotton soil release agent
selected from the group consisting of a terephthalate co-polymer
comprising:
i) a backbone comprising:
a) at least one moiety having the formula:
~ ;
b) at least one moiety having the formula:
Rl~ Rl~
~--P-9--(~--I 9)i--~--
Rl~ Rl~
wherein R9 is C2-C6 linear alkylene, C3-C6 branched
alkylene, Cs-C7 cyclic alkylene, and mixtures
thereof; R10 is independently selected from hydrogen
or -L-SO3-M+; wherein L is a side chain moiety
selected from the group consisting of alkylene,
oxyalkylene, alkyleneoxyalkylene, arylene,
oxyarylene, alkyleneoxyarylene, poly(oxyalkylene),
oxy-alkyleneoxyarylene, poly(oxyalkylene)oxyarlyene,
alkylene-poly(oxyalkylene), and mixtures thereof; M is
hydrogen or a salt forming cation; i has the value of 0
or 1 ;
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c) at least one trifunctional, ester-forming, branching
moiety;
d) at least one 1,2-oxyalkyleneoxy moiety; and
ii) one or more capping units comprising:
S a) ethoxylated or propoxylated hydroxyethanesulfonate
or ethoxylated or propoxylated
hydroxypropanesulfonate units of the formula
(MO3S)(CH2)m(R1 1O)n-, where M is a salt forming
cation, R11 is ethylene, propylene, and mixtures
thereof, m is 0 or 1, and n is from 1 to 20;
b) sulfoaroyl units of the formula -(O)C(C6H4)(SO3-M+),
wherein M is a salt forming cation;
c) modified poly(oxyethylene)oxy monoalkyl ether units
of the formula R120(CH2CH20)k-, wherein R12
contains from 1 to 4 carbon atoms and k is from about
3 to about 100; and
d) ethoxylated or propoxylated phenolsulfonate end-
capping units of the formula M03S(C6H4)(0R13)no-,
wherein n is from 1 to 20; M is a salt-forming cation;
and R13 is ethylene, propylene, and mixtures thereof;
a sulfonated oligomeric ester composition comprising the
sulfonated product of a pre-formed, substantially linear ester
oligomer, said linear ester oligomer comprising, per mole,
i) 2 moles of terminal units wherein from about 1 mole to about
2 moles of said terminal units are derived from an olefinically
unsaturated component selected from the group consisting
of allyl alcohol and methallyl alcohol, and any remaining of
said terminal units are other units of said linear ester
oligomer;
ii) from about 1 mole to about 4 moles of nonionic hydrophile
units, said hydrophile units being derived from
alkyleneoxides, said alkylene oxides comprising from about
50% to 100% ethylene oxide;
iii) from about 1.1 moles to about 20 moles of repeat units
derived from an aryldicarbonyl component wherein said
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aryldicarbonyl component is comprised of from about 50% to
100% dimethylterephthalate, whereby the repeat units
derived from said dimethylterephthalate are terephthaloyl;
and
iv) from about 0.1 moles to about 19 moles of repeat units
derived from a diol component selected from the group
consisting of C2-C4 glycols;
wherein the extent of sulfonation of said sulfonated oligomeric ester
composition is such that said terminal units are chemically modified
by
v) from about 1 mole to about 4 moles of terminal unit
substituent groups of formula -SOXM wherein x is 2 or 3,
said terminal unit substituent groups being derived from a
bisulfite component selected from the group consisting of
HS03M wherein M is a conventional water-soluble cation;
a capped terephalate co-polymer having the formula
X[(OCH~CH2)n(0R5)n,1[(A-Rl--A-R2)U(A-R3-A-R2)V]--
A-R4-A~(R50)~(cH2cH20)"lx
wherein each of the A moieties is selected from the group
consisting of
--OC-- , --CO--
and combinations thereof, each of the R1 moieties is selected from
the group consisting of 1,4-phenylene and combinations thereof
with 1,3-phenylene, 1,2 phenylene, 1,8-naphthylene, 1,4-
naphthylene, 2,2'-biphenylene, 4,4'-biphenylene, C1-Cg alkylene,
C1-Cg alkenylene and mixtures thereof the R2 moieties are each
selected from the group consisting of ethylene moieties, substituted
ethylene moieties having C1-C4 alkyl, alkoxy substitiuents, and
mixtures thereof; the R3 moieties are substituted C2-C1 8
hydrocarbylene moieties having at least one -CO2M, -
O[(R5o)m(cH2cH2o)n]x or -A[(R2-A-R4-
A)]W[(R50)m(CH2CH20)n]X substituent; the R4 moieties are R1 or
R3 moieties, or mixtures thereof; each R5 is C1-C4 alkylene, or the
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moiety -R2-A-R6- wherein R6 is a C1-C12 alkylene, alkenylene,
arylene, or alkarylene moiety; each M is hydrogen or a water-
solubie cation; each X is C1-C4 alkyl; the indices m and n have the
values such that the moiety -(CH2CH2O)- comprises at least about
50% by weight of the moiety [(R~O)m(CH2CH2O)n], provided that
when R5 is the moiety -R2-A-R6-, m is 1; each n is at least about
10; the indices u and v have the value such that the sum of u + v is
from about 3 to about 25; the index w is 0 or at least 1; and when
w is at least 1 u, v and w have the value such that the sum of u + v
+ w is from about 3 to about 25; and mixtures thereof;
B) at least about 0.01% by weight, of a water-soluble or dispersible,
modified polyamine cotton soil release agent comprising a
polyamine backbone corresponding to the formula:
H, I
[H2N~R]n+l--IN-R]m--[N-R]n-NH2
having a modified polyamine formula V(n+1)wmynz or a
polyamine backbone corresponding to the formula:
,H I IR
[H~N-R3n-k+ ~[N ~R]m--[N ~R]n~N -R3k-NH2
having a modihed polyamine formula V(n-k+1)wmyny kZ, wherein
k is less than or equal to n, said polyamine backbone prior to
modification has a molecular weight greater than about 200
daltons, wherein
i) V units are terminal units having the formula:
E X~ O
E--I--R-- or E--I--R-- or E--I--R--
E E E
ii) W units are backbone units having the formula:
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I X
--I--R or--I--R- or--I--R
E E E
iii) Y units are branching units having the formula:
I X
--I--R or --I--R-- or --I--R
; and
iv) Z units are terminal units having the formula:
I X
--I--E or --I--E or --I--E
E E E
wherein backbone linking R units are selected from the group
consisting of C2-C12 alkylene, C4-C12 alkenylene, C3-C12
hydroxyalkylene, C4-C12 dihydroxy-alkylene, Cg-C12
dialkylarylene, (R1 o)XR1 , (R1 o)xR5(oR1 )x-,
(CH2CH(OR2)CH20)z-(R1o)yR1(0CH2CH(OR2)CH2)W-,
C(O)(R4)rC(o)-~ -CH2CH(OR2)CH2-, and mixtures
thereof; wherein R1 is C2-C3 alkylene and mixtures thereof; R2 is
hydrogen, -(R1O)XB, and mixtures thereof; R3 is C1-C1g alkyl, C7-
C12 arylalkyl, C7-C12 alkyl substituted aryl, C6-C12 aryl, and
mixtures thereof; P~4 is C1-C12 alkylene, C4-C12 alkenylene, Cg-
C12 arylalkylene, C6-C10 arylene, and mixtures thereof; R5 is C1-
C 1 2 alkylene, C3-C 1 2 hydroxy-alkylene, C4-C 1 2
dihydroxyalkylene, Cg-C12 dialkylarylene, -C(O)-,
C(O)NHR6NHC(O)-, -R1 (OR1 )-, -C(o)(R4)rC(o)-,
CH2CH(OH)CH2- -CH2CH(OH)CH20(R10)yR1~
OCH2CH(OH)CH2-, and mixtures thereof; R6 is C2-C12 alkylene
or C6-C12 arylene; E units are selected from the group consisting
of hydrogen, C1-C22 alkyl, C3-C22 alkenyl, C7-C22 arylalkyl, C2-
C22 hydroxyalkyl,-(CH2)pco2M~ -(CH2)qS03M, -CH(CH2C02M)-
CO2M, -(CH2)pPO3M, -(R1O)XB, -C(o)R3, and mixtures thereof;
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provided that when any E unit of a nitrogen is a hydrogen, said
nitrogen is not also an N-oxide; B is hydrogen, C1-C6 alkyl, -
(CH2)q~s03M~ -(CH2)pC02M, -(CH2)q(CHS03M)CH2S03M,
(CH2)q-(CHSO2M)CH2SO3M, -(CH2)pPO3M, -PO3M, and
mixtures thereof; M is hydrogen or a water soluble cation in
sufficient amount to satisfy charge balance; X is a water soluble
anion; m has the value from 4 to about 400; n has the value from 0
to about 200; p has the value from 1 to 6, q has the value from 0 to
6; r has the value of 0 or 1; w has the value 0 or 1; x has the value
from 1 to 100; y has the value from 0 to 100; z has the value 0 or 1.
1 1. Enzymes
Enzymes can be included in the present detergent compositions for
a variety of purposes, including removal of protein-based,
carbohydrate-based, or triglyceride-based stains from surfaces such as
lS textiles, for the prevention of refugee dye transfer, for example in
laundering, and for fabric restoration. Suitable enzymes include
proteases, amylases, lipases, cellulases, peroxidases, and mixtures
thereof of any suitable origin, such as vegetable, animal, bacterial,
fungal and yeast origin. Preferred selections are influenced by factors
such as pH-activity and/or stability optima, thermostability, and stability
to active detergents, builders and the like. In this respect bacterial or
fungal enzymes are preferred, such as bacterial amylases and
proteases, and fungal cellulases.
"Detersive enzyme", as used herein, means any enzyme having a
cleaning, stain removing or otherwise beneficial effect in a laundry,
hard surface cleaning or personal care detergent composition.
Preferred detersive enzymes are hydrolases such as proteases,
amylases and lipases. Preferred enzymes for laundry purposes
inciude, but are not limited to, proteases, cellulases, lipases and
peroxidases.
Enzymes are normally incorporated into detergent or detergent
additive compositions at levels sufficient to provide a "cleaning-
effective amount". The term "cleaning effective amount" refers to any
amount capable of producing a cleaning, stain removal, soil removal,
whitening, deodorizing, or freshness improving effect on substrates
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such as fabrics. In practical terms for current commercial preparations,
typical amounts are up to about 5 mg by weight, more typically 0.01
mg to 3 mg, of active enzyme per gram of the detergent composition.
Stated otherwise, the compositions herein will typically comprise from
0.001 % to 5%, preferably 0.01 %-1 % by weight of a commercial
enzyme preparation. Protease enzymes are usually present in such
commercial preparations at levels sufficient to provide from 0.005 to
0.~ Anson units (AU) of activity per gram of composition. For certain
detergents, it may be desirable to increase the active enzyme content
of the commercial preparation in order to minimize the total amount of
non-catalytically active materials and thereby improve spottinglfilming
or other end-results. Higher active levels may also be desirable in
highly concentrated detergent formulations.
Suitable examples of proteases are the subtilisins which are
obtained from particular strains of B. subtilis and B. Iicheniforrnis. One
suitable protease is obtained from a strain of Bacillus, having
maximum activity throughout the pt I range of 8-12, developed and sold
as ESPERASE~) by Novo Industries A/S of Denmark, hereinafter
"Novo". The preparation of this enzyme and analogous enzymes is
described in GB 1,243,784 to Novo. Other suitable proteases include
ALCALASE~ and SAVINASE(~) from Novo and MAXATASE(~) from
International Bio-Synthetics, Inc., The Netherlands; as well as
Protease A as disclosed in EP 130,756 A, January 9, 1985 and
Protease B as disclosed in EP 303,761 A, April 28, 1987 and EP
130,756 A, January 9, 1985. See also a high pH protease from
Bacillus sp. NCIMB 40338 described in WO 9318140 A to Novo.
Enzymatic detergents comprising protease, one or more other
enzymes, and a reversible protease inhibitor are described in WO
9203529 A to Novo. Other preferred proteases include those of WO
9510591 A to Procter & Gamble . When desired, a protease having
decreased adsorption and increased hydrolysis is available as
described in WO 9507791 to Procter & Gamble. A recombinant
trypsin-like protease for detergents suitable herein is described in WO
9425583 to Novo.
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The preferred liquid laundry detergent compositions according to
the present invention further comprise at least 0.001% by weight, of a
protease enzyme. However, an effective amount of protease enzyme
is sufficient for use in the liquid laundry detergent compositions
described herein. The term "an effective amount" refers to any amount
capable of producing a cleaning, stain removal, soil removal,
whitening, deodorizing, or freshness improving effect on substrates
such as fabrics. In practical terms for current commercial preparations,
typical amounts are up to about 5 mg by weight, more typically 0.01
mg to 3 mg, of active enzyme per gram of the detergent composition.
Stated otherwise, the compositions herein will typically comprise from
0.001% to 5%, preferably 0.01%-1% by weight of a commercial
enzyme preparation. The protease enzymes of the present invention
are usually present in such commercial preparations at levels sufficient
to provide from 0.005 to 0.1 Anson units (AU) of activity per gram of
composition.
Preferred liquid laundry detergent compositions of the present
invention comprise a protease enzyme, referred to as "Protease D",
which 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 a plurality of amino
acid residues 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 WO
95/10615 published April 20, 1995 by Genencor International.
Useful proteases are also described in PCT publications: WO
95/30010 published November 9, 1995 by The Procter & Gamble
Company; WO 95/30011 published November 9, 1995 by The Procter
& Gamble Company; WO 95/2g979 published November 9, 1995 by
The Procter & Gamble Company.
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Preferred proteolytic enzymes are also modified bacterial serine
proteases, such as those described in European Patent Application
Serial Number 87 303,761.8, filed April 28, 1987 (particularly pages
17, 24 and 98), and which is called herein "Protease B", and in
European Patent Application 199,404, Venegas, published October
29, 1986, which refers to a modified bacterial serine proteolytic
enzyme which is called "Protease A" herein, Protease A as disclosed
in EP 130,756 A, January 9, 1985 and Protease B as disclosed in EP
303,761 A, April 28, 1987 and EP 130,756 A, ~lanuary 9, 1985.
l 0 Amylases suitable herein, include, for example, a-amylases
described in GB 1,296,839 to Novo; RAPIDASE~, International Bio-
Synthetics, Inc. and TERMAMYL(g), Novo. FUNGAMYL(~ from Novo is
especially useful. Engineering of enzymes for improved stability, e.g.,
oxidative stability, is known. See, for example J. Biological Chem., Vol.
Z60, No. 11, June 1985, pp 6518-6521. Certain preferred
embodiments of the present compositions can make use of amylases
having improved stability in detergents, especially improved oxidative
stability as measured against a reference-point of TERMAMYL(~) in
commercial use in 1993. These preferred amylases herein share the
characteristic of being "stability-enhanced" amylases, characterized, at
a minimum, by a measurable improvement in one or more of: oxidative
stability, e.g., to hydrogen peroxide / tetraacetylethylene-diamine in
buffered solution at pH 9-10; thermal stability, e.g., at common wash
temperatures such as about 60~C; or alkaline stability, e.g., at a pH
from about 8 to about 11, measured versus the above-identified
reference-point amylase. Stability can be measured using any of the
art-disclosed technical tests. See, for example, references disclosed in
WO 9402597. Stability-enhanced amylases can be obtained from
Novo or from Genencor International. One class of highly preferred
amylases herein have the commonality of being derived using site-
directed mutagenesis from one or more of the Baccillus amylases,
especially the Bacillus a-amylases, regardless of whether one, two or
multiple amylase strains are the immediate precursors. Oxidative
stability-enhanced amylases vs. the above-identified reference
amylase are preferred for use, especially in bleaching, more preferably
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oxygen bleaching, as distinct from chlorine bleaching, detergent
compositions herein. Such preferred amylases include (a) an amylase
according to the hereinbefore incorporated WO 9402597, Novo, Feb.
3, 1994, as further illustrated by a mutant in which substitution is
S made, using alanine or threonine, preferably threonine, of the
methionine residue located in position 197 of the B.licheniformis alpha-
amylase, known as TERMAMYL(~), or the homologous position
variation of a similar parent amylase, such as B. amyloliquefaciens,
B.svbtilis, or B.stearothermophilus; (b) stability-enhanced amylases as
described by Genencor International in a paper entitled "Oxidatively
Resistant alpha-Amylases" presented at the 207th American Chemical
Society National Meeting, March 13-17 1994, by C. Mitchinson.
Therein it was noted that bleaches in automatic dishwashing
detergents inactivate alpha-amylases but that improved oxidative
stability amylases have been made by Genencor from B.licheniforrnis
NCIB8061. Methionine (Met) was identified as the most likely residue
to be modified. Met was substituted, one at a time, in positions 8, 15,
197, 256, 304, 366 and 438 leading to specific mutants, particularly
important being M197L and M197T with the M197T variant being the
most stable expressed variant. Stability was measured in CASCADE~)
and SUNLIGHT(~'; (c) particularly preferred amylases herein include
amylase variants having additional modification in the immediate
parent as described in WO 9510603 A and are available from the
assignee, Novo, as DURAMYL(~. Other particularly preferred oxidative
stability enhanced amylase include those described in WO 9418314 to
Genencor International and WO 9402597 to Novo. Any other oxidative
stability-enhanced amylase can be used, for example as derived by
site-directed mutagenesis from known chimeric, hybrid or simple
mutant parent forms of available amylases. Other preferred enzyme
modifications are accessible. See WO 9509909 A to Novo.
Cellulases usable herein include both bacterial and fungal types,
preferably having a pH optimum between 5 and 9.5. U.S. 4,435,307,
Barbesgoard et al, March 6, 1984, discloses suitable fungal cellulases
from Humicola inso/ens or Humicola strain DSM1800 or a cellulase
212-producing fungus belonging to the genus Aeromonas, and
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cellulase extracted from the hepatopancreas of a marine mollusk,
Dolabella Auricu/a Solander. Suitable cellulases are also disclosed in
GB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832.
CAREZYME(~) (Novo) is especially useful. See also WO 9117243 to
Novo.
Suitable lipase enzymes for detergent usage include those
produced by microorganisms of the Pseudomonas group, such as
Pseudomonas stutzeri ATCC 19.154, as disclosed in GB 1,372,034.
See also lipases in Japanese Patent Application 53,20487, laid open
Feb. 24, 1978. This lipase is available from Amano Pharmaceutical
Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano," or
"Amano-P." Other suitable commercial lipases include Amano-CES,
lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var.
Iipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan;
Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A.
and Disoynth Co., The Netherlands, and lipases ex Pseudomonas
gladioli. LIPOLASE~ enzyme derived from Humicola lanuginosa and
commercially available from Novo, see also EP 341,947, is a preferred
lipase for use herein. Lipase and amylase variants stabilized against
peroxidase enzymes are described in WO 9414951 A to Novo. See
also WO 9205249 and RD 94359044.
Cutinase enzymes suitable for use herein are described in WO
8809367 A to Genencor.
Peroxidase enzymes may be used in combination with oxygen
sources, e.g., percarbonate, perborate, hydrogen peroxide, etc., for
"solution bleaching" or prevention of transfer of dyes or pigments
removed from substrates during the wash to other substrates present
in the wash solution. Known peroxidases include horseradish
peroxidase, ligninase, and haloperoxidases such as chloro- or bromo-
peroxidase. Peroxidase-containing detergent compositions are
disclosed in WO 89099813 A, October 19, 1989 to Novo and WO
8909813 A to Novo.
A range of enzyme materials and means for their incorporation into
synthetic detergent compositions is also disclosed in WO 9307263 A
and WO 9307260 A to Genencor International, WO 8908694 A to
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Novo, and U.S. 3,553,139, January 5, 1971 to McCarty et al
Enzymes are further disciosed in U.S. 4,101,457, Place et al, July 18,
1978, and in U.S. 4,507,219, Hughes, March 26, 1985. Enzyme
materials useful for liquid detergent formulations, and their
incorporation into such formulations, are disclosed in U.S. 4,261,868,
Hora et al, April 14, 1981. Enzymes for use in detergents can be
stabilized by various techniques. Enzyme stabilization techniques are
disclosed and exemplified in U.S. 3,600,319, August 17, 1971, Gedge
et al, EP 199,405 and EP 200,586, October 29, 1986, Venegas
Enzyme stabilization systems are also described, for example, in U.S
3,519,570. A useful Bacillus, sp. AC13 giving proteases, xylanases
and cellulases, is described in WO 9401532 A to Novo.
12. Enzyme stabilizing system
Enzyme-containing,. including but not limited to, liquid compositions,
herein may comprise from about 0.001% to about 10%, preferably
from about 0.005% to about 8%, most preferably from about 0.01% to
about 6%, by weight of an enzyme stabilizing system. The enzyme
stabilizing system can be any stabilizing system which is compatible
with the detersive enzyme. Such a system may be inherently provided
by other formulation actives, or be added separately, e.g., by the
formulator or by a manufacturer of detergent-ready enzymes. Such
stabilizing systems can, for example, comprise calcium ion, boric acid,
propylene glycol, short chain carboxylic acids, boronic acids, and
mixtures thereof, and are designed to address different stabilization
problems depending on the type and physical form of the detergent
composition.
One stabilizing approach is the use of water-soluble sources of
calcium and/or magnesium ions in the finished compositions which
provide such ions to the enzymes. Calcium ions are generally more
effective than magnesium ions and are preferred herein if only one
type of cation is being used. Typical detergent compositions,
especially liquids, will comprise from about 1 to about 30, preferably
from about 2 to about 20, more preferably from about 8 to about 12
millimoles of calcium ion per liter of finished detergent composition,
though variation is possible depending on factors including the
. . ...
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multiplicity, type and levels of enzymes incorporated. Preferably
water-soluble calcium or magnesium salts are employed, including for
example calcium chloride, calcium hydroxide, calcium formate, calcium
malate, calcium maleate, calcium hydroxide and calcium acetate; more
generally, calcium sulfate or magnesium salts corresponding to the
exemplified calcium salts may be used. Further increased levels of
Calcium and/or Magnesium may of course be useful, for example for
promoting the grease-cutting action of certain types of surfactant.
Another stabilizing approach is by use of borate species. See
Severson, U.S. 4,537,706. Borate stabilizers, when used, may be at
levels of up to 10% or more of the composition though more typically,
levels of up to about 3% by weight of boric acid or other borate
compounds such as borax or orthoborate are suitable for liquid
detergent use. Substituted boric acids such as phenylboronic acid,
butaneboronic acid, p-bromophenylboronic acid or the like can be used
in place of boric acid and reduced levels of total boron in detergent
compositions may be possible though the use of such substituted
boron derivatives.
Stabilizing systems of certain cleaning compositions may further
comprise from 0 to about 10%, preferably from about 0.01% to about
6% by weight, of chlorine bleach scavengers, added to prevent
chlorine bleach species present in many water supplies from attacking
and inactivating the enzymes, especially under alkaline conditions.
While chlorine levels in water may be small, typically in the range from
about 0.5 ppm to about 1.75 ppm, the available chlorine in the total
volume of water that comes in contact with the enzyme, for example
during fabric-washing, can be relatively large; accordingly, enzyme
stability to chlorine in-use is sometimes problematic. Since perborate
or percarbonate, which have the ability to react with chlorine bleach,
may present in certain of the instant compositions in amounts
accounted for separately from the stabilizing system, the use of
additional stabilizers against chlorine, may, most generally, not be
essential, though improved results may be obtainable from their use.
Suitable chlorine scavenger anions are widely known and readily
available, and, if used, can be salts containing ammonium cations with
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sulfite, bisulfite, thiosulfite, thiosulfate, iodide, etc. Antioxidants such
as carbamate, ascorbate, etc., organic amines such as
ethylenediaminetetracetic acid (EDTA) or alkali metal salt thereof,
monoethanolamine (MEA), and mixtures thereof can likewise be used.
Likewise, special enzyme inhibition systems can be incorporated such
that different enzymes have maximum compatibility. Other
conventional scavengers such as bisulfate, nitrate, chloride, sources of
hydrogen peroxide such as sodium perborate tetrahydrate, sodium
perborate monohydrate and sodium percarbonate, as well as
phosphate, condensed phosphate, acetate, benzoate, citrate, formate,
lactate, malate, tartrate, salicylate, etc., and mixtures thereof can be
used if desired. In general, since the chlorine scavenger function can
be performed by ingredients separately listed under better recognized
functions, (e.g., hydrogen peroxide sources), there is no absolute
lS requirement to add a separate chlorine scavenger unless a compound
performing that function to the desired extent is absent from an
enzyme-containing embodiment of the invention; even then, the
scavenger is added only for optimum results. Moreover, the formulator
will exercise a chemist's normal skill in avoiding the use of any enzyme
scavenger or stabilizer which is majorly incompatible, as formulated,
with other reactive ingredients, if used. In relation to the use of
ammonium salts, such salts can be simply admixed with the detergent
composition but are prone to adsorb water and/or liberate ammonia
during storage. Accordingly, such materials, if present, are desirably
protected in a particle such as that described in US 4,652,392,
Baginski et al.
1 3. Builders
Detergent builders can optionally be included in the compositions
herein to assist in controlling mineral hardness. Inorganic as well as
organic builders can be used. Builders are typically used in fabric
laundering compositions to assist in the removal of particulate soils.
The level of builder can vary widely depending upon the end use of
the composition and its desired physical form. When present, the
compositions will typically comprise at least about 1% builder. Liquid
formulations typically comprise from about 5% to about 50%, more
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typically about 5% to about 30%, by weight, of detergent builder.
Granular formulations typically comprise from about 10% to about
80%, more typically from about 15% to about 50% by weight, of the
detergent builder. Lower or higher levels of builder, however, are not
meant to be excluded.
Inorganic or P-containing detergent builders include, but are not
limited to, the alkali metal, ammonium and alkanolammonium salts of
polyphosphates (exemplified by the tripolyphosphates,
pyrophosphates, and glassy polymeric meta-phosphates),
l 0 phosphonates, phytic acid, silicates, carbonates (including
bicarbonates and sesquicarbonates), sulphates, and aluminosilicates.
However, non-phosphate builders are required in some locales.
Importantly, the compositions herein function surprisingly well even in
the presence of the so-called "weak" builders (as compared with
phosphates) such as citrate, or in the so-called "underbuilt" situation
that may occur with zeolite or layered silicate builders.
Examples of silicate builders are the alkali metal silicates,
particularly those having a SiO2:Na2O ratio in the range 1.6:1 to 3.2:1
and layered silicates, such as the layered sodium silicates described in
U.S. Patent 4,664,839, issued May 12, 1987 to H. P. Rieck. NaSKS-6
is the trademark for a crystalline layered silicate marketed by Hoechst
(con""only abbreviated herein as "SKS-6"). Unlike zeolite builders,
the Na SKS-6 silicate builder does not contain aluminum. NaSKS-6
has the delta-Na2SiOs morphology form of layered silicate. It can be
prepared by methods such as those described in German DE-A-
3,417,649 and DE-A-3,742,043. SKS-6 is a highly preferred layered
silicate for use herein, but other such layered silicates, such as those
having the general formula NaMSixO2x+1 yH2O wherein M is sodium
or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a
number from 0 to 20, preferably 0 can be used herein. Various other
layered silicates from Hoechst include NaSKS-5, NaSKS-7 and
NaSKS-11, as the alpha, beta and gamma forms. As noted above, the
delta-Na2SiOs (NaSKS-6 form) is most preferred for use herein. Other
silicates may also be useful such as for example magnesium silicate,
which can serve as a crispening agent in granular formulations, as a
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stabilizing agent for oxygen bleaches, and as a component of suds
control systems.
Examples of carbonate builders are the alkaline earth and alkali
metai carbonates as disclosed in German Patent Application No.
2,321,001 published on November 15,1973.
Aluminosilicate builders are useful in the present invention.
Aluminosilicate builders are of great importance in most currently
marketed heavy duty granular detergent compositions, and can also
be a significant builder ingredient in liquid detergent formulations.
Aluminosilicate builders include those having the empirical formula:
Mz(zAl02)y] XH20
wherein z and y are integers of at least 6, the molar ratio of z to y is in
the range from 1.0 to about 0.5, and x is an integer from about 15 to
about 264.
Useful aluminosilicate ion exchange materials are commercially
available. These aluminos I .,~tes can be crystalline or amorphous in
structure and can be naturally-occurring aluminosilicates or
synthetically derived. A method for producing aluminosilicate ion
exchange materials is disclosed in U.S. Patent 3,985,669, Krummel, et
al, issued October 12, 1976. Preferred synthetic crystalline
aluminosilicate ion exchange materials useful herein are available
under the designations Zeolite A, Zeolite P (B), Zeolite MAP and
Zeolite X. In an especially preferred embodiment, the crystalline
aluminosilicate ion exchange material has the formula:
Na1 2[(AI~2)1 2(Si~2)1 2] XH2O
wherein x is from about 20 to about 30, especially about 27. This
material is known as Zeolite A. Dehydrated zeolites (x = 0 - 10) may
also be used herein. Preferably, the aluminosilicate has a particle size
of about 0.1-10 microns in diameter.
Organic detergent builders suitable for the purposes of the present
invention include, but are not restricted to, a wide variety of
polycarboxylate compounds. As used herein, "polycarboxylate" refers
to compounds having a plurality of carboxylate groups, preferably at
least 3 carboxylates. Polycarboxylate builder can generally be added
to the composition in acid form, but can also be added in the form of a
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neutralized salt. When utilized in salt forrn, alkali metals, such as
sodium, potassium, and lithium, or alkanolammonium salts are
preferred.
Included among the polycarboxylate builders are a variety of
categories of useful materials. One important category of
polycarboxylate builders encompasses the ether polycarboxylates,
including oxydisuccinate, as disclosed in Berg, U.S. Patent 3,128,287,
issued April 7, 1964, and Lamberti et al, U.S. Patent 3,635,830, issued
January 18, 1972. See also "TMS/TDS" builders of U.S. Patent
4,663,071, issued to Bush et al, on May 5, 1987. Suitable ether
polycarboxylates also include cyclic compounds, particularly alicyclic
compounds, such as those described in U.S. Patents 3,923,679;
3,835,163; 4,158,635; 4,120,874 and 4,102,903.
Other useful detergency builders include the ether
hydroxypolycarboxylates, copolymers of maleic anhydride with
ethylene or vinyl methyl ether, 1, 3, 5-trihydroxy benzene-2, 4, 6-
trisulphonic acid, and carboxymethyloxysuccinic acid, the various alkali
metal, ammonium and substituted ammonium salts of polyacetic acids
such as ethylenediamine tetraacetic acid and nill:!clliacetic acid, as
well as polycarboxylates such as mellitic acid, succinic acid, oxy-
disuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid,
carboxymethyloxysuccinic acid, and soluble salts thereof.
Citrate builders, e.g., citric acid and soluble salts thereof
(particularly sodium salt), are polycarboxylate builders of particular
importance for heavy duty liquid detergent formulations due to their
aYailability from renewable resources and their biodegradability.
Citrates can also be used in granular compositions, especially in
combination with zeolite andlor layered silicate builders.
Oxydisuccinates are also especially useful in such compositions and
combinations.
Also suitable in the detergent compositions of the present invention
are the 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the related
compounds disclosed in U.S. Patent 4,566,984, Bush, issued January
28, 1986. Useful succinic acid builders include the Cs-C20 alkyl and
alkenyl succinic acids and salts thereof. A particularly preferred
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compound of this type is dodecenylsuccinic acid. Specific examples of
succinate builders include: laurylsuccinate, myristylsuccinate,
palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2-
pentadecenylsuccinate, and the like. Laurylsuccinates are the
preferred builders of this group, and are described in European Patent
Application 86200690.5/0,200,263, published November 5,1986.
Other suitable polycarboxylates are disclosed in U.S. Patent
4,144,226, Crutchfield et al, issued March 13, 1979 and in U.S. Patent
3,308,067, Diehl, issued March 7, 1967. See also Diehl U.S. Patent
l 0 3,723,322.
Fatty acids, e.g., C 12-C 18 monocarboxylic acids, can also be
incorporated into the compositions alone, or in combination with the
aforesaid builders, especially citrate and/or the succinate builders, to
provide additional builder activity. Such use of fatty acids will generally
result in a diminution of sudsing, which should be taken into account
by the formulator.
In situations where phosphorus-based builders can be used, and
especially in the formulation of bars used for hand-laundering
operations, the various all<ali metal phosphates such as the well-
known sodium tripolyphosphates, sodium pyrophosphate and sodium
orthophosphate can be used. Phosphonate builders such as ethane-
1-hydroxy-1,1-diphosphonate and other known phosphonates (see, for
example, U.S. Patents 3,159,581; 3,213,030; 3,422,021; 3,400,148
and 3,422,137) can also be used.
14. Clay soil removal/anti-redoposition agents
The compositions of the present invention can also optionally
contain water-soluble ethoxylated amines having clay soil removal and
antiredeposition properties. Granular detergent compositions which
contain these compounds typically contain from about 0.01% to about
10.0% by weight of the water-soluble ethoxylates amines; liquid
detergent compositions typically contain about 0.01% to about 5%.
The most preferred soil release and anti-redeposition agent is
ethoxylated tetraethylenepentamine. Exemplary ethoxylated amines
are further described in U.S. Patent 4,597,898, VanderMeer, issued
July 1, 1986. Another group of preferred clay soil removal-
... .. . . . .
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antiredeposition agents are the cationic compounds disclosed in
European Patent Application 111,965, Oh and Gosselink, published
June 27, 1984. Other clay soil removal/antiredeposition agents which
can be used include the ethoxylated amine polymers disclosed in
European Patent Application 111,984, Gosselink, published June 27,
1984; the zwitterionic polymers disclosed in European Patent Appli-
cation 112,592, Gosselink, published July 4, 1984; and the amine
oxides disclosed in U.S. Patent 4,548,744, Connor, issued October 22,
1985. Other clay soil removal and/or anti redeposition agents known
in the art can also be utilized in the compositions herein. Another type
of preferred antiredeposition agent includes the carboxy methyl
cellulose (CMC) materials. These materials are well known in the art.
15. Polymeric DisPersin~g Agents
Polymeric dispersing agents can advantageously be utilized at
levels from about 0.1% to about 7%, by weight, in the compositions
herein, especially in the presence of zeolite and/or layered silicate
builders. Suitable polymeric dispersing agents include polymeric
polycarboxylates and polyethylene glycols, although others known in
the art can also be used. It is believed, though it is not intended to be
limited by theory, that polymeric dispersing agents enhance overall
detergent builder performance, when used in combination with other
builders (including lower molecular weight polycarboxylates) by crystal
growth inhibition, particulate soil release peptization, and anti-
redeposition.
Polymeric polycarboxylate materials can be prepared by
polymerizing or copolymerizing suitable unsaturated monomers,
preferably in their acid form. Unsaturated monomeric acids that can
be polymerized to form suitable polymeric polycarboxylates include
acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic
acid, aconitic acid, mesaconic acid, citraconic acid and
methylenemalonic acid. The presence in the polymeric
polycarboxylates herein or monomeric segments, containing no
carboxylate radicals such as vinylmethyl ether, styrene, ethylene, etc.
is suitable provided that such segments do not constitute more than
about 40% by weight.
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Particularly suitable polymeric polycarboxylates can be derived
from acrylic acid. Such acrylic acid-based polymers which are useful
herein are the water-soluble salts of polymerized acrylic acid. The
average molecular weight of such polymers in the acid form preferably
ranges from about 2,000 to 10,000, more preferably from about 4,000
to 7,000 and most preferably from about 4,000 to 5,000. Water-
soluble salts of such acrylic acid polymers can include, for example,
the alkali metal, ammonium and substituted ammonium salts. Soluble
polymers of this type are known materials. Use of polyacrylates of this
type in detergent compositions has been disclosed, for example, in
Diehl, U.S. Patent 3,308,067, issued march 7,1967.
Acrylic/maleic-based copolymers may also be used as a preferred
component of the dispersing/anti-redeposition agent. Such materials
include the water-soluble salts of copolymers of acrylic acid and maleic
acid. The average molecular weight of such copolymers in the acid
form preferably ranges from about 2,000 to 100,000, more preferably
from about 5,000 to 75,000, most preferably from about 7,000 to
65,000. The ratio of acrylate to maleate segments in such copolymers
will generally range from about 30:1 to about 1:1, more preferably from
about 10:1 to 2:1. Water-soluble salts of such acrylic acid/maleic acid
copolymers can include, for example, the alkali metal, ammonium and
substituted ammonium salts. Soluble acrylate/maleate copolymers of
this type are known materials which are described in European Patent
Application No. 66915, published December 15, 1982, as well as in EP
193,360, published September 3, 1986, which also describes such
polymers comprising hydroxypropylacrylate. Still other useful
dispersing agents include the maleic/acrylic/vinyl alcohol terpolymers.
Such materials are also disclosed in EP 193,360, including, for
example, the 45/45/10 terpolymer of acrylic/maleic/vinyl alcohol.
Another polymeric material which can be included is polyethylene
glycol (PEG). PEG can exhibit dispersing agent performance as well
as act as a clay soil removal-antiredeposition agent. Typical molecular
weight ranges for these purposes range from about 500 to about
100,000, preferably from about 1,000 to about 50,000, more preferably
from about 1,500 to about 10,000.
..... . . . ..
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Polyaspartate and polyglutamate dispersing agents may also be
used, especially in conjunction with zeolite builders. Dispersing agents
such as polyaspartate preferably have a molecular weight (avg.) of
about 10,000.
16.Suds Suppressors
Compounds for reducing or suppressing the formation of suds can
be incorporated into the compositions of the present invention. Suds
suppression can be of particular importance in the so-called "high
concentration cleaning process" as described in U.S. 4,489,455 and
4,489,574 and in front-loading European-style washing machines.
A wide variety of materials may be used as suds suppressors, and
suds suppressors are well known to those skilled in the art. See, for
example, Kirk Othmer Encyclopedia of Chemical Technology, Third
Edition, Volume 7, pages 430-447 (John Wiley & Sons, Inc., 1979).
One category of suds suppressor of particular interest encompasses
monocarboxylic fatty acid and soluble salts therein. See U.S. Patent
2,954,347, issued September 27, 1960 to Wayne St. John. The
monocarboxylic fatty acids and salts thereof used as suds suppressor
typically have hydrocarbyl chains of 10 to about 24 carbon atoms,
preferably 12 to 18 carbon atoms. Suitable salts include the alkali
metal salts such as sodium, potassium, and lithium salts, and
ammonium and alkanolammonium salts.
The detergent compositions herein may also contain non-surfactant
suds suppressors. These include, for example: high molecular weight
hydrocarbons such as paraffin, fatty acid esters (e.g., fatty acid
triglycerides), fatty acid esters of monovalent alcohols, aliphatic C1g-
C40 ketones (e.g., stearone), etc. Other suds inhibitors include N-
alkylated amino triazines such as tri- to hexa-alkylmelamines or di- to
tetra-alkyldiamine chlortriazines formed as products of cyanuric
chloride with two or three moles of a primary or secondary amine
containing 1 to 24 carbon atoms, propylene oxide, and monostearyl
phosphates such as monostearyl alcohol phosphate ester and
monostearyl di-alkali metal (e.g., K, Na, and Li) phosphates and
phosphate esters. The hydrocarbons such as paraffin and haloparaffin
can be utilized in liquid form. The liquid hydrocarbons will be liquid at
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room temperature and atmospheric pressure, and will have a pour
point in the range of about-40~C and about 50~C, and a minimum
boiling point not less than about 110~C (atmospheric pressure). It is
also known to utilize waxy hydrocarbons, preferably having a melting
point below about 100~C. The hydrocarbons constitute a preferred
category of suds suppressor for detergent compositions. Hydrocarbon
suds suppressors are described, for example, in U.S. Patent
4,265,779, issued May 5, 1981 to Gandolfo et al. The hydrocarbons,
thus, include aliphatic, alicyclic, aromatic, and heterocyclic saturated or
unsaturated hydrocarbons having from about 12 to about 70 carbon
atoms. The term "paraffin," as used in this suds suppressor
discussion, is intended to include mixtures of true paraffins and cyclic
hydrocarbons.
Another preferred category of non-surfactant suds suppressors
comprises silicone suds suppressors. This category includes the use
of polyorganosiloxane oils, such as polydimethylsiloxane, dispersions
or emulsions of polyorganosiloxane oils or resins, and combinations of
polyorganosiloxane with silica particles wherein the
polyorganosiloxane is chemisorbed or fused onto the silica. Silicone
suds suppressors are well known in the art and are, for example,
disclosed in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et
al and European Patent Application No. 89307851.9, published
February 7, 1990, by Starch, M. S.
Other silicone suds suppressors are disclosed in U.S. Patent
3,455,839 which relates to compositions and processes for defoaming
aqueous solutions by incorporating therein small amounts of
polydimethylsiloxane fluids.
Mixtures of silicone and silanated silica are described, for instance,
in German Patent Application DOS 2,124,526. Silicone defoamers
and suds controlling agents in granular detergent compositions are
disclosed in U.S. Patent 3,933,672, Bartolotta et al, and in U.S. Patent
4,652,392, Baginski et al, issued March 24, 1987.
An exempiary silicone based suds suppressor for use herein is a
suds suppressing amount of a suds controlling agent consisting
essentially of:
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(i) polydimethylsiloxane fluid having a viscosity of from about 20
cs. to about 1,500 cs. at 25~C;
(ii) from about 5 to about 50 parts per 100 parts by weight of (i) of
siloxane resin composed of (CH3)3SiO1/2 units of SiO2 units in
a ratio of from (CH3)3 SiO1/2 units and to SiO2 units of from
about 0.6:1 to about 1.2:1; and
(iii) from about 1 to about 20 parts per 100 parts by weight of (i) of a
solid silica gel.
In the preferred silicone suds suppressor used herein, the solvent
for a continuous phase is made up of certain polyethylene glycols or
polyethylene-polypropylene glycol copolymers or mixtures thereof
(preferred), or polypropylene glycol. The primary silicone suds
suppressor is branched/crosslinked and preferably not linear.
To illustrate this point further, typical liquid laundry detergent
compositions with controlled suds will optionally comprise from about
0.001 to about 1, preferably from about 0.01 to about 0.7, most
preferably from about 0.05 to about 0.5, weight % of said silicone suds
suppressor, which comprises (1) a nonaqueous emulsion of a primary
antifoam agent which is a mixture of (a) a polyorganosiloxane, (b) a
resinous siloxane or a silicone resin-producing silicone compound, (c)
a finely divided filler material, and (d) a catalyst to promote the reaction
of mixture components (a), (b) and (c), to form silanolates; (2) at least
one nonionic silicone surfactant; and (3) polyethylene glycol or a
copolymer of polyethylene-polypropylene glycol having a solubility in
water at room temperature of more than about 2 weight %; and without
polypropylene glycol. Similar amounts can be used in granular
compositions, gels, etc. See also U.S. Patents 4,978,471, Starch,
issued December 18, 1990, and 4,983,316, Starch, issued January 8,
1991, 5,288,431, Huber et al., issued February 22, 1994, and U.S.
Patents 4,639,489 and 4,749,740, Aizawa et al at column 1, line 46
through column 4, line 35.
The silicone suds suppressor herein preferably comprises
polyethylene glycol and a copolymer of polyethylene
glycol/polypropylene glycol, all having an average molecular weight of
less than about 1,000, preferably between about 100 and 800. The
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polyethylene glycol and polyethylene/polypropylene copolymers herein
have a solubility in water at room temperature of more than about 2
weight %, preferably more than about 5 weight %.
The preferred solvent herein is polyethylene glycol having an
average molecular weight of less than about 1,000, more preferably
between about 100 and 800, most preferably between 200 and 400,
and a copolymer of polyethylene glycol/polypropylene glycol,
preferably PPG 200/PEG 300. Preferred is a weight ratio of between
about 1:1 and 1:10, most preferably between 1:3 and 1:6, of
polyethylene glycol:copolymer of polyethylene-polypropylene glycol.
The preferred silicone suds suppressors used herein do not contain
polypropylene glycol, particularly of 4,000 molecular weight. They also
preferably do not contain block copolymers of ethylene oxide and
propylene oxide, like PLURONIC L101.
l S Other suds suppressors useful herein comprise the secondary
alcohols (e.g., 2-alkyl alkanols) and mixtures of such alcohols with
silicone oils, such as the silicones disclosed in U.S. 4,798,679,
4,075,118 and EP 150,872. The secondary alcohols include the C6-
C16 alkyl alcohols having a C1-C16 chain. A preferred alcohol is 2-
butyl octanol, which is available from Condea under the trademark
ISOFOL 12. Mixtures of secondary alcohols are available under the
trademark ISALCHEM 123 from Enichem. Mixed suds suppressors
typically comprise mixtures of alcohol + silicone at a weight ratio of 1 :5
to 5: 1.
For any detergent compositions to be used in automatic laundry
washing machines, suds should not form to the extent that they
overflow the washing machine. Suds suppressors, when utilized, are
preferably present in a "suds suppressing amount. By "suds
suppressing amount" is meant that the formulator of the composition
can select an amount of this suds controlling agent that will sufficiently
control the suds to result in a low-sudsing laundry detergent for use in
automatic laundry washing machines.
The compositions herein will generally comprise from 0% to about
5% of suds suppressor. When utilized as suds suppressors,
monocarboxylic fatty acids, and salts therein, will be present typically in
..... . . .
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amounts up to about 5%, by weight, of the detergent composition.
Preferably, from about 0.5% to about 3% of fatty monocarboxylate
suds suppressor is utilized. Silicone suds suppressors are typically
utilized in amounts up to about 2.0%, by weight, of the detergent
composition, although higher amounts may be used. This upper limit
is practical in nature, due primarily to concern with keeping costs
minimized and effectiveness of lower amounts for effectively controlling
sudsing. Preferably from about 0.01% to about 1% of silicone suds
suppressor is used, more preferably from about 0.25% to about 0.5%.
As used herein, these weight percentage values include any silica that
may be utilized in combination with polyorganosiloxane, as well as any
adjunct materials that may be utilized. Monostearyl phosphate suds
suppressors are generally utilized in amounts ranging from about 0.1%
to about 2%, by weight, of the composition. Hydrocarbon suds
suppressors are typically utilized in amounts ranging from about 0.01%
to about 5.0%, although higher levels can be used. The alcohol suds
suppressors are typically used at 0.2%-3% by weight of the finished
compositions.
17. DYe transfer inhibitors
The compositions of the present invention may also include one or
more materials effective for inhibiting the transfer of dyes from one
fabric to another during the cleaning process. Generally, such dye
transfer inhibiting agents include polyvinyl pyrrolidone polymers,
polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-
vinylimidazole, manganese phthalocyanine, peroxidases, and mixtures
thereof. If used, these agents 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 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: -NC(O)-, -C(O)O-, -S-, -O-, -N=; x is 0 or 1; and R is
aliphatic, ethoxylated aliphatics, aromatics, heterocyclic or alicyclic
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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 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
(R~ N--(R2)y; =N--(R~ h~
(R3)z
wherein R1, 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 c10, preferably pKa <7, more preferred pKa <6.
Any polymer backbone can be used as long as the amine oxide
I S polymer formed is water-soluble and has dye transfer inhibiting
properties. Examples of suitable polymeric backbones are polyvinyls,
polyalkylenes, polyesters, polyethers, polyamide, polyimides,
polyacrylates and mixtures thereof. These polymers include random or
block copolymers where one monomer type is an amine N-oxide and
the other monomer type is an N-oxide. The amine N-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
copolymerization or by an appropriate degree of N-oxidation. The
polyamine oxides can be obtained in almost any degree of
polymerization. Typically, the average molecular weight is within the
range of 500 to 1,000,000; more preferred l,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 as an
average molecular weight of about 50,000 and an amine to amine N-
oxide ratio of about 1:4.
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Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers
(referred to as a class as "PVPVI") are also preferred for use herein.
Preferably the 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 113. "Modern Methods of Polymer
Characterization", the disclosures of which are incorporated herein by
reference.) The PVPVI copolymers 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
copolymers can be either linear or branched.
The present invention compositions also may 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 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
in wash solutions is from about 2:1 to about 50:1, and more preferably
from about 3:1 to about 10:1.
19. Minors
Liquid detergent compositions can also include optional
components conventionally used in textile treatment compositions, for
example: colorants; preservatives; anti-shrinkage agents; fabric
crisping agents; spotting agents; germicides; fungicides; anti-oxidants
such as butylated hydroxy toluene, anti-corrosion agents, and the like.
Particularly preferred ingredients, when used, include water
soluble calcium and/or magnesium compounds, which provide
additional stability. The chloride salts are preferred, but acetate,
nitrate, etc. salts can be used. The level of said calcium and/or
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magnesium salts is from 0% to about 2%, preferably from about 0.05%
to about 0.5%, more preferably from about 0.1% to about 0.25%.
Liquid detergent compositions can also include other compatible
ingredients, including those as disclosed in copending applications
Serial Nos.: 08/372,068, filed January 12, 1995, Rusche, et al.;
08/372,490, filed January 12, 1995, Shaw, et al.; and 08/277,558, filed
July 19,1994, Hartman, et al., incorporated herein by reference.
The substantially odor-free solvents of the present invention can
also be optionally pre-purified further purified by recrystallization and/or
l O hydrogenation.
EXAMPLES
The following examples further describe and demonstrate the preferred
embodiments within the scope of the present invention. The examples are given
solely for the purpose of illustration, and are not to be construed as limitations of
the present invention since many variations thereof are possible without
departing from its spirit and scope.
Example 1
This example shows how to make a substantially odor-free polyhydroxyl
solvent. Highly volatile malodorous components such as butyloxirane and
pentanal are removed by nitrogen gas sparging of 1,2-hexanediol solvent. 25
grams of the 1,2-hexanediol solvent is then mixed with 75 grams of deionised
water in a container at room temperature and agitated with a magnetic stirrer,
thereby forming a pre-mixture of solvent to water of 1:4. Next, 20 grams of
activated carbon (charcoal activated, powder, supplied by Kanto Chemical Co.,
Ltd.) and the pre-mixture is mixed in a container using an agitator. The
composition is left overnight. Then the activated carbon is filtered out. The
remaining solvent is substantially free of consumer noticeable malodorous
components.
. .
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Example 2
This example shows how to make a substantially odor-free polyhydroxyl
solvent. Highly volatile malodorous components such as butyloxirane and
pentanal are removed by fractional distillation of 1,2-hexanediol solvent. 25
S grams of the 1,2-hexanediol solvent is then mixed with 75 grams of deionised
water in a container at room temperature and agitated with a magnetic stirrer,
thereby forming a pre-mixture of solvent to water of 1:4. Next, the pre-mixture is
passed through a flow-through activated carbon bed. The remaining solvent is
substantially free of consumer noticeable malodorous components.
Examples 3-6 are example liquid compositions comprising substantially
odor-free polyhydroxyl solvents of the present invention:
ExamPle 3
This example illustrates a fabric softener composition containing a
15 substantially odor-free polyhydroxyl solvent. The fabric softener composition is
substantially free of consumer noticeable malodorous components.
Component wt.%
DEQA1 26.0
Polyhydroxyl Solvent2 19.0
HCL (pH2-3.5) 0.25
Ethanol 2.00
Deionised water Balance
DEQA: N, N-di(oleoyl - oxyethyl)-N, N-dimethyl ammonium chloride
25 2 The substantially odor-free polyhydroxyl solvent made by the description in Example 1.
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Example 4
This example illustrates a heavy duty liquid detergent composition
containing a substantially odor-free-polyhydroxyl solvent. The heavy duty liquiddetergent composition is substantially free of consumer noticeable malodorous
S components.
Component wt. %
Polyhydroxy Coco-Fatty Acid Amide 4.15
C14-C1s Alcohol Ethoxylate E2 25 Sulfate 21.90
C10 Amidopropyl Amine 1.20
Polyhydroxyl Solvent1 10.00
Citric Acid 3.50
Fatty Acid (C1 2-C14)
NEODOL 23 92 2.75
Ethanol 5 . 50
Monoethanolamine 1.50
Propanediol 8.00
Boric Acid 3.50
Sodium Toluene Sulfonate 2.50
NaOH 0 49
Waterand Minors3 Balance
The substan~ially odor-free polyhydroxyl solvent made by the description in
Example 1.
2 Eg Ethoxylated Alcohols as sold by the Shell Oil Co.
2S 3 Balance to 100% can, for example, include minors like optical brightener,
perfume, suds suppresser, soil dispersant, protease, lipase, cellulase, chelating
agents, dye transfer inhibiting agents, additional water, and fillers, includingCaCO3, talc, silicates, etc.
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Example 5
This example illusll ates a liquid detergent composition containing a
substantially odor-free-polyhydroxyl solvent. The liquid detergent composition is
substantially free of consumer noticeable malodorous components.
Component wt. %
C12 15 Alcohol Ethoxylate E2 5 Sulfate 6.00
Alkyl N-Methyl Glucose Amide 1.00
C12-13 E6 5 Nonionic 10.0
Polyhydroxyl Solvent1 5.00
Fatty Acid (C12-C14)
Citric Acid 0.40
NaOH 0.85
Monoethanolamine 1.00
Propanediol 2.00
Xylene SulfonicAcid 2.00
Water and Minors2 Balance
The substantially odor-free polyhydroxyl solvent made by the description in
Example 1.
20 2 Balance to 100% can, for example, include minors like optical brightener,
perfume, suds suppresser, soil dispersant, protease, lipase, cellulase, chelating
agents, dye transfer inhibiting agents, additional water, and fillers, includingCaCO3, talc, silicates, etc.
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Example 6
This example illusl,ates a liquid detergent composition containing a
substantially odor-free-polyhydroxyl solvent. The liquid detergent composition is
sul.sl~nlially free of consumer noticeable malodorous components.
Component wt. %
Sodium C12 14 Alcohol Ethoxylate E2 2 Sulfate 22.0
C12 14 Alkyl Dimethyl Amine Oxide 2.30
C12 14 Alkyl Dimethyl Betaine 2.30
C9-11 E8 Alkyl Ethoxylate 6.70
C12 14GlucoseAmide 040
Polyhydroxyl Solvent1 5.00
Sodium Cumene Sulphonate 4.50
Ethanol 7.00
Water and Minors2 Balance
The substar,lially odor-free polyhydroxyl solvent made by the description in
Exa""~le 1.
2 Balance to 100% can, for example, include minors like optical brightener,
perfume, suds suppresser, soil dispersant, protease, lipase, cellulase, chelating
20 agents, dye transfer inhibiting agents, additional water, and fillers, including
CaCO3, talc, si~ic~tes, etc.
