WO1998002513A1

WO1998002513A1 - Substantially odor-free polyhydroxyl solvents

Info

Publication number: WO1998002513A1
Application number: PCT/US1997/008393
Authority: WO
Inventors: Dean Larry Duval; Shintaro Hiki; Shuji Maeno; Mitsuyo Okamoto; Jun-Ichi Toyota
Original assignee: The Procter & Gamble Company
Priority date: 1996-07-11
Filing date: 1997-05-12
Publication date: 1998-01-22
Also published as: AU3207097A; EP0918842A1; JPH11514007A; CA2260101A1; CN1229433A; BR9710356A; CZ4999A3

Abstract

The present invention relates to a substantially odor-free polyhydroxyl solvent, and method of making such odor-free solvent. More specifically, it relates to liquid detergent compositions comprising substantially odor-free polyhydroxyl solvents.

Description

SUBSTANTIALLY ODOR-FREE POLYHYDROXYL SOLVENTS

FIELD The present invention relates to a substantially odor-free polyhydroxyl solvent, and method of making such odor-free solvent. More specifically, it relates to liquid detergent compositions comprising substantially odor-free polyhydroxyl solvents.

BACKGROUND

Polyhydroxyl solvents are known in the art, including its use in liquid detergent compositions. There is a problem with polyhydroxyl solvents because they 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 compositions. Consumers usually expect detergent compositions to 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 malodor may contain larger quantities of perfume in order to mask the malodor. This leads to a higher formulation cost and ultimately, 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 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 consumer noticeable malodorous components: 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 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 specification 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 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. Polvhvdroxyl 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: 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 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- methyl-2-(1-methylpropyl)-; 1 ,3-propanediol, 2-methyl-2-(2-methylpropyl)-; 1 ,3-propanediol, 2-tertiary-butyl-2-methyl-; 1 ,3-butaπediol, 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-trimethyl-; 1 ,3-pentanediol, 2,2,4-trimethyl-; 1 ,3- pentanedio 2,3,4-trimethyl- 1 ,3-pentanediol, 2,4,4-trimethyl- 1 ,3- pentanedio 3,4,4-trimethyl- 1 ,4-pentanediol, 2,2,3-trimethyl- 1 ,4- pentanedio 2,2,4-trimethyl- 1 ,4-pentanediol, 2,3,3-trimethyl- 1 ,4- pentanedio 2,3,4-trimethyl- 1 ,4-pentanediol, 3,3,4-trimethyl- 1 ,5- pentanedio 2,2,3-trimethyl- 1 ,5-pentanediol, 2,2,4-trimethyl- 1 ,5- pentanedio 2,3,3-trimethyl- 1 ,5-pentanediol, 2,3,4-trimethyl- 2,4- pentanedio 2,3,3-trimethyl- 2,4-pentanediol, 2,3,4-trimethyl- 1 ,3- pentanedio 2-ethyl-2-methyl- 1 , 3-pentaned iol , 2-ethyl-3-methyl- 1 ,3- pentanedio 2-ethyl-4-methyl- 1 ,3-pentanediol, 3-ethyl-2-methyl- 1 ,4- pentanedio 2-ethyl-2-methyl- 1 ,4-pentanediol, 2-ethyl-3-methyl- 1 ,4- pentanedio 2-ethyl-4-methyl- 1 ,4-pentanediol, 3-ethyl-2-methyl- 1 ,4- pentanedio 3-ethyl-3-methyl- 1 ,5-pentanediol, 2-ethyl-2-methyl- 1 ,5- pentanedio 2-ethyl-3-methyl- 1 ,5-pentanediol, 2-ethyl-4-methyl- 1 ,5- pentanedio 3-ethyl-3-methyl- 2,4-pentanediol, 3-ethyl-2-methyl- 1 ,3- pentanedio 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, 4,4-dιmethyl-, 1 ,4-hexanedιol, 4,5-dιmethyl-, 1 4-hexanedιol, 5,5-dιmethyl- , 1 ,5-hexanedιol, 2,2-dιmethyl-, 1 ,5-hexanedιol, 2,3-dimethyl-, 1 ,5- hexanediol, 2,4-dιmethyl-, 1,5-hexanedιol, 2,5-dimethyl-, 1,5-hexanedιol, 3,3-dιmethyl-, 1 ,5-hexanedιol, 3,4-dimethyl-, 1 ,5-hexanedιol, 3,5-dιmethyl- , 1 ,5-hexanedιol, 4,5-dιmethyl-, 1 ,6-hexanedtol, 2,2-dιmethyl-, 1 ,6- hexanediol, 2,3-dimethyl-, 1 ,6-hexanedιol, 2,4-dιmethyl-, 1,6-hexanedιol, 2,5-dimethyl-, 1 ,6-hexanedιol, 3,3-dιmethyl-, 1 6-hexanedιol, 3,4-dιmethyl- , 2,4-hexanedιol, 2,3-dimethyl-, 2,4-hexanedιol, 2,4-dιmethyl-, 2,4- hexanediol, 2,5-dimethyl-, 2,4-hexanedιol, 3,3-dιmethyl-, 2,4-hexanedιol, 3 4-dιmethyl-, 2,4-hexanedιol, 3,5-dimethyl-, 2 4-hexanedιol, 4,5-dιmethyl-

, 2,4-hexanedιol, 5,5-dιmethyl-, 2,5-hexanedιol, 2,3-dimethyl-, 2,5- hexanediol, 2,4-dιmethyl-, 2,5-hexanedιol, 2,5-dimethyl-, 2,5-hexanedιol, 3,3-dιmethyl-, 2,5-hexanedιol, 3,4-dimethyl-, 2,6-hexanedιol, 3,3-dιmethyl- , 1 ,3-hexanedιol, 2-ethyl-, 1 ,3-hexanedιol, 4-ethyl-, 1 ,4-hexanedιol, 2- ethyl-, 1 ,4-hexanedιol, 4-ethyl-, 1 ,5-hexanedιol, 2-ethyl-, 2,4-hexanedιol,

3-ethyl-, 2,4-hexanedιol, 4-ethyl-, 2,5-hexanedιol, 3-ethyl-, 1 ,3- heptanediol, 2-methyl-, 1 ,3-heptanedιol, 3-methyl-, 1 ,3-heptanedιol, 4- methyl-, 1 ,3-heptanedιol, 5-methyl- 1 ,3-heptanedιol, 6-methyl-, 1 ,4- heptanediol, 2-methyl-, 1 ,4-heptanedιol, 3-methyl-, 1,4-heptanedιol, 4- methyl-, 1 ,4-heptanedιol, 5-methyl-, 1 ,4-heptanedιol, 6-methyl-, 1 ,5- heptanediol, 2-methyl-, 1 ,5-heptanedιol, 3-methyl-, 1 ,5-heptanedιol, 4- methyl-, 1 ,5-heptanedιol, 5-methyl-, 1 ,5-heptanedιol, 6-methyl-, 1 ,6- heptanediol, 2-methyl-, 1 ,6-heptanedιol, 3-methyl-, 1 ,6-heptanedιol, 4- methyl-, 1 ,6-heptanedιol, 5-methyl-, 1 6-heptanedιol, 6-methyl-, 2,4- heptanediol, 2-methyl-, 2,4-heptanedιol, 3-methyl-, 2,4-heptanedιol, 4- methyl-, 2,4-heptanedιol, 5-methyl-, 2,4-heptanedιol, 6-methyl-, 2,5- heptanediol, 2-methyl-, 2,5-heptanedιol, 3-methyl-, 2,5-heptanedιol, 4- methyl-, 2,5-heptanedιol, 5-methyl-, 2,5-heptanedιol, 6-methyl-, 2,6- heptanediol, 2-methyl-, 2,6-heptanedιol, 3-methyl-, 2,6-heptanedιol, 4- methyl-, 3,4-heptanedιol, 3-methyl- 3,5-heptanedιol, 2-methyl-, 3,5- heptanediol, 3-methyl-, 3,5-heptanedιol 4-methyl-, 2,4-octanedιol, 2,5- octanediol, 2,6-octanedιol, 2,7-octanedιol, 3,5-octanedιol, and/or 3,6- octanediol, nonane diol isomers including 2,4-pentanedιol, 2,3,3,4-tetramethyl-, 2,4- pentanediol, 3-tertιarybutyl-, 2 4-hexanedιol, 2,5,5-trιmethyl-, 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-;

E. glyceryl ethers and/or di(hydroxyalkyl)ethers including: 1 ,2-propanediol, 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)-, 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-ethyl-4-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-cyclopentaπediol; 3-ethyl-1 ,2-cyclopentanediol; 4,4- dimethyl-1 ,2-cyclopentanediol; 4-ethyl- 1 ,2-cyclopentanediol; 1 ,1- 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- 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- 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- 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-methyl-; 1 ,2-cyclohexanediol, 1- ethenyl-, 1 ,2-cyclohexanediol, 1-methyl-3-methylene-, 1 ,2- cyclohexanediol, 1-methyl-4-methylene-, 1 ,2-cyclohexanedιol, 3- ethenyl-, 1 ,2-cyclohexanediol, 4-ethenyl-, 3-cyclohexene-1 ,2-dιol, 2,6- dimethyl-; 3-cyclohexene-1 ,2-diol, 6,6-dimethyl-, 4-cyclohexene-1 ,2- diol, 3,6-dιmethyl-; 4-cyclohexene-1 ,2-diol, 4,5-dimethyl-, 3- cyclooctene-1 ,2-dιol; 4-cyclooctene-1 ,2-diol; and/or 5-cyclooctene-1 ,2- diol; Alkoxylated derivatives of C3.8 diols [In the following disclosure, "EO" means polyethoxylates, 1 e , -(CH2CH2θ)_nH, Me-E_n means methyl- capped polyethoxylates -(CH2CH2θ)_nCH3 ; "2(Me-En)" means 2 Me-En groups needed; "PO" means polypropoxylates, -(CH(CH3)CH2θ)nH ,

"BO" means polybutyleneoxy groups, (CH(CH2CH3)CH2θ)_nH , and "n-

BO" means poly(n-butyleneoxy) or poly(tetramethylene)oxy groups -

(CH2CH2CH2CH2θ)_nH. The use of the term "(C_x)" herein refers to the number of carbon atoms in the base material which is alkoxylated ] including:

1 1 ,2-propanedιol (C3) 2(Me-E<|_4), 1 ,2-propanediol (C3) PO4, 1 ,2- propanediol (C3) BO_π , 1 ,2-propanedιol, 2-methyl- (C4) (Me-E^io), 1 ,2-propanedιol, 2-methyl- (C4) 2(Me-E-|); 1 ,2-propanedιol, 2-methyl- (C4) PO3; 1 ,2-propanedιol, 2-methyl- (C4) n-BOι_2; 1 ,3-propanedιol

(C3) 2(Me-Ee-8); 1 ,3-propanedιol (C3) PO5.6; 1 ,3-propanedιol, 2,2- diethyl- (C7) E-1.7; 1 ,3-propanedιol, 2,2-diethyl- (C7) PO^ 1 ,3- propanediol, 2,2-diethyl- (C7) n-BO<|_2; 1 ,3-propanediol, 2,2-dιmethyl- (C5) 2(Me Eι_2), 1 ,3-propanedιol, 2,2-dιmethyl- (C5) PO₃^; 1 ,3- propanediol, 2-(1-methylpropyl)- (C7) E1.7, 1 ,3-propanedιol, 2-(1- methylpropyl)- (C7) PO<| , 1 ,3-propanedιol, 2-(1-methylpropyl)- (C7) n- BO1.2; 1 ,3-propanediol, 2-(2-methylpropyl)- (C7) E1.7, 1 ,3- propanediol, 2-(2-methylpropyl)- (C7) PO-j ; 1 ,3-propanedιol, 2-(2- methylpropyl)- (C7) n-BO_π_2; 1 ,3-propanedιol, 2-ethyl- (C5) (Me Eβ- ₁₀), 1 ,3-propanediol, 2-ethyl- (C5) 2(Me E1); 1 ,3-propanedιol, 2-ethyl-

(C5) PO3; 1 ,3-propanedιol, 2-ethyl- (C5) BO1 ; 1 ,3-propanedιol, 2- ethyl-2-methyl- (C6) (Me E-|_6)- 1 ,3-propanedιol, 2-ethyl-2-methyl- (C6) PO2, 1 ,3-propanedιol, 2-ethyl-2-methyl- (C6) BO-| , 1 ,3-propanedιol, 2- isopropyl- (C6) (Me Eι_6); 1 ,3-propanediol, 2-isopropyl- (C6) PO2, 1 ,3- propanediol, 2-ιsopropyl- (C6) BO1 , 1 ,3-propanediol, 2-methyl- (C4) 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) PO-|; 1,3-propanediol, 2- methyl-2-isopropyl- (C7) n-BOι.3; 1,3-propanediol, 2-methyl-2-propyl- (C7) E-j_7; 1,3-propanediol, 2-methyl-2-propyl- (C7) PO-_|; 1,3- propanediol, 2-methyl-2-propyl- (C7) n-BOι_2; 1,3-propanediol, 2- propyl- (C6) (Me E1.4); 1,3-propanediol, 2-propyl- (C6) PO2; 1,3- propanediol, 2-propyl- (C6) BO-|; 2. 1,2-butanediol (C4) (Me E2-8); 1,2-butanediol (C4) PO2.3, 1,2- butanediol (C4) BO_π; 1,2-butanediol, 2,3-dimethyl- (C6) E-μβ; 1.2- butanediol, 2,3-dimethyl- (C6) n-BO^<|_2; 1,2-butanediol, 2-ethyl- (C6) E-1.3; 1,2-butanediol, 2-ethyl- (C6) BO-j; 1,2-butanediol, 2-methyl- (C5) (Me E^<|_2); 1,2-butanediol, 2-methyl- (C5) PO-j; 1,2-butanediol, 3,3- dimethyl- (C6) Eι_β; 1,2-butanediol, 3,3-dimethyl- (C6) BO^; 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) PO5; 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 E^); 1,3-butanediol, 2- ethyl- (C6) PO2-3; 1,3-butanediol, 2-ethyl- (C6) BO^<j; 1,3-butanediol, 2-ethyl--2-methyl- (C7) (Me E_π); 1,3-butanediol, 2-ethyl-2-methyl- (C7) PO1; 1 ,3-butanediol, 2-ethyl~2-methyl- (C7) n-B02-4; 1,3-butanediol, 2-ethyl-3-methyl- (C7) (Me E_π); 1,3-butanediol, 2-ethyl-3-methyl- (C7)

PO_π; 1,3-butanediol, 2-ethyl-3-methyl- (C7) n-B02-4; 1 ,3-butanediol, 2-isopropyl- (C7) (Me E-j); 1,3-butanediol, 2-isopropyl- (C7) PO<ι; 1,3- butanediol, 2-isopropyl- (C7) n-B02-4; 1,3-butanediol, 2-methyl- (C5) 2(Me E<|_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-BO_π_3; 1,3-butanediol, 3-methyl- (C5) 2(Me E-f.3); 1,3-butanediol, 3-methyl- (C5) PO4; 1 ,4-butanediol (C4) 2(Me E2.4); 1 ,4-butanediol (C4) PO4.5; 1,4-butanediol (C4) BO2; 1,4-butanediol, 2,2,3-trimethyl- (C7) E2-9; 1,4-butanediol, 2,2,3-trimethyl- (C7) PO-j; 1,4-butanediol, 2,2,3-trimethyl- (C7) n-BO-1.3; 1,4-butanediol, 2,2- dimethyl- (C6) (Me Eη.e); 1 ,4-butanediol, 2,2-dimethyl- (C6) PO2; 1 ,4- butanediol, 2,2-dimethyl- (C6) BO_n ; 1 ,4-butanediol, 2,3-dimethyl- (C6) (Me E-ι_6); 1 ,4-butanediol, 2,3-dimethyl- (C6) PO2; 1 ,4-butanediol, 2,3- dimethyl- (C6) BO-i; 1 ,4-butanediol, 2-ethyl- (C6) (Me Eη^.); 1 ,4- butanediol, 2-ethyl- (C6) PO2; 1 ,4-butanediol, 2-ethyl- (C6) BO^ ; 1 ,4- butanediol, 2-ethyl-2-methyl- (C7) E1.7; 1 ,4-butanediol, 2-ethyl-2- methyl- (C7) PO-|; 1 ,4-butanediol, 2-ethyl-2-methyl- (C7) n-BO_π.₂; 1 ,4- butanediol, 2-ethyl-3-methyl- (C7) E1.7; 1 ,4-butanediol, 2-ethyl-3- methyl- (C7) PO_π ; 1 ,4-butanediol, 2-ethyl-3-methyl- (C7) n-BO<|_₂, 1 ,4- butanediol, 2-isopropyl- (C7) E1.7; 1 ,4-butanediol, 2-isopropyl- (C7)

PO1 ; 1 ,4-butanediol, 2-isopropyl- (C7) n-BO_n.2; 1 ,4-butanediol, 2- methyl- (C5) (Me E6-10). 1 ,4-butanediol, 2-methyl- (C5) 2(Me E-| ); 1 ,4- butanediol, 2-methyl- (C5) PO3; 1 ,4-butanediol, 2-methyl- (C5) BO-|; 1 ,4-butanediol, 2-propyl- (C7) E-1.5; 1 ,4-butanediol, 2-propyl- (C7) n- BO1-2; 1 ,4-butanediol, 3-ethyl- 1 -methyl- (C7) E2-9; 1 ,4-butanediol, 3- ethyl-1 -methyl- (C7) PO-|; 1 ,4-butanediol, 3-ethy 1-1 -methyl- (C7) n- BO-1.3; 2,3-butanediol (C4) (Me E-\.Q); 2,3-butanediol (C4) 2(Me E1); 2,3-butanediol (C4) Pθ3^; 2,3-butanediol (C4) BO-| ; 2,3-butanediol, 2,3-dimethyl- (C6) E3.9; 2,3-butanediol, 2,3-dimethyl- (C6) PO-| ; 2,3- butanediol, 2,3-dimethyl- (C6) BO1.3; 2,3-butanediol, 2-methyl- (C5)

(Me E_π_5); 2,3-butanediol, 2-methyl- (C5) 2PO2; 2,3-butanediol, 2- methyl- (C5) n-BOi; 2,3-butanediol, 2-methyl- (C5) BO1;

3. 1 ,2-pentanediol (C5) E3.10; 1 ,2-pentanediol, (C5) PO-) ; 1 ,2- pentanediol, (C5) n-B02-3; 1 ,2-pentanediol, 2-methyl (C6) E1.3; 1,2- pentanediol, 2-methyl (C6) n-BO-j; 1 ,2-pentanediol, 2-methyl (C6)

BO-| ; 1 ,2-pentanediol, 3-methyl (C6) E1.3; 1 ,2-pentanediol, 3-methyl (C6) n-BO_π ; 1,2-pentanediol, 3-methyl (C6) BO1 ; 1 ,2-pentanediol, 4- methyl (C6) E-1.3; 1 ,2-pentanediol, 4-methyl (C6) n-BOi ; 1 ,2- pentanediol, 4-methyl (C6) BO-| ; 1 ,3-pentanediol (C5) 2(Me-Eι_2); 1,3- pentanediol (C5) PO3.4; 1 ,3-pentanediol, 2,2-dimethyl- (C7) (Me-Ei );

1 ,3-pentanediol, 2,2-dimethyl- (C7) PO^ ; 1 ,3-pentanediol, 2,2- dimethyl- (C7) n-Bθ2-4; 1 ,3-pentanediol, 2,3-dimethyl- (C7) (Me-E<|); 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-E-j); 1 ,3-pentanediol, 2,4-dimethyl- (C7) PO1 ; 1 ,3-pentanediol, 2,4- dimethyl- (C7) n-BO2-4; 1,3-pentanediol, 2-ethyl- (C7) E2-9; 1,3- pentanediol, 2-ethyl- (C7) PO_π; 1,3-pentanediol, 2-ethyl- (C7) n-BO-_j. 3; 1,3-pentanediol, 2-methyl- (C6) 2(Me-E-j_6); 1,3-pentanediol, 2- methyl- (C6) PO2-3; 1,3-pentanediol, 2-methyl- (C6) n-BO-_|, 1,3- pentanediol, 2-methyl- (C6) BO-j; 1,3-pentanediol, 3,4-dimethyl- (C7)

(Me-E_π); 1,3-pentanediol, 3,4-dimethyl- (C7) PO_π; 1,3-pentanediol, 3,4-dimethyl- (C7) n-BO2_4; 1,3-pentanediol, 3-methyl- (C6) 2(Me-E-_j. 6); 1,3-pentanediol, 3-methyl- (C6) PO2-3; 1,3-pentanediol, 3-methyl- (C6) n-BO-i; 1,3-pentanediol, 3-methyl- (C6) BO1; 1,3-pentanediol, 4,4-dimethyl- (C7) (Me-E_η); 1,3-pentanediol, 4,4-dimethyl- (C7) PO1;

1,3-pentanediol, 4,4-dimethyl- (C7) n-B02-4; 1,3-pentanediol, 4- methyl- (C6) 2(Me-E^<|_6); 1,3-pentanediol, 4-methyl- (C6) PO2.3; 1,3- pentanediol, 4-methyl- (C6) BO_π; 1,4-pentanediol, (C5) 2(Me-E_π_2); 1 ,4-pentanediol (C5) PO3.4; 1 ,4-pentanediol, 2,2-dimethyl- (C7) (Me- E_π); 1 ,4-pentanediol, 2,2-dimethyl- (C7) PO_π; 1,4-pentanediol, 2,2- dimethyl- (C7) n-BO2^; 1,4-pentanediol, 2,3-dimethyl- (C7) (Me-E_η); 1,4-pentanediol, 2,3-dimethyl- (C7) PO-|; 1,4-pentanediol, 2,3- dimethyl- (C7) n-BO2-4; 1 ,4-pentanediol, 2,4-dimethyl- (C7) (Me-E-_j); 1 ,4-pentanediol, 2,4-dimethyl- (C7) PO-|; 1,4-pentanediol, 2,4- dimethyl- (C7) n-BO2-4; 1 ,4-pentanediol, 2-methyl- (C6) (Me-E<|_₆);

1 ,4-pentanediol, 2-methyl- (C6) PO2-3; 1 ,4-ρentanediol, 2-methyl- (C6) n-BOi; 1,4-pentanediol, 2-methyl- (C6) BO_π; 1,4-pentanediol, 3,3- dimethyl- (C7) (Me-E^; 1,4-pentanediol, 3,3-dimethyl- (C7) PO^ 1,4- pentanediol, 3,3-dimethyl- (C7) n-Bθ2-4; 1,4-pentanediol, 3,4- dimethyl- (C7) (Me-Ei); 1 ,4-pentanediol, 3,4-dimethyl- (C7) PO^ 1,4- pentanediol, 3,4-dimethyl- (C7) n-B02-4; 1 ,4-pentanediol, 3-methyl- (C6) 2(Me-E-i_6); 1 ,4-pentanediol, 3-methyl- (C6) PO2-3; 1,4- peπtanediol, 3-methyl- (C6) BO<|; 1,4-pentanediol, 4-methyl- (C6) 2(Me-Eη_6); 1,4-pentanediol, 4-methyl- (C6) PO2-3; 1 ,4-pentanediol, 4-methyl- (C6) BO-j ; 1 ,5-pentanediol, (C5) (Me-E4_ι Q); 1 ,5-pentanediol

(C5) 2(Me-E-|); 1,5-pentanediol (C5) PO3; 1,5-pentanediol, 2,2- dimethyl- (C7) E1.7; 1,5-pentanediol, 2,2-dimethyl- (C7) PO_η; 1,5- pentanediol, 2,2-dimethyl- (C7) n-BOι_2; 1,5-pentanediol, 2,3- dimethyl- (C7) E1.7; 1,5-pentanediol, 2,3-dimethyl- (C7) PO-|; 1,5- pentanediol, 2,3-dimethyl- (C7) n-BO-j.2; 1,5-pentanediol, 2,4- dimethyl- (C7) E1.7; 1 ,5-pentanediol, 2,4-dimethyl- (C7) PO-_| ; 1 ,5- pentanediol, 2,4-dimethyl- (C7) n-BO<|_2; 1 ,5-pentanediol, 2-ethyl- (C7) E-|_5; 1 ,5-pentanediol, 2-ethyl- (C7) n-BO<|_2; 1 ,5-pentanediol, 2- methyl- (C6) (Me-E-j_4); 1 ,5-peπtanediol, 2-methyl- (C6) PO2; 1 ,5- pentanediol, 3,3-dimethyl- (C7) E1.7; 1 ,5-pentanediol, 3,3-dimethyl-

(C7) PO1 ; 1 ,5-pentanediol, 3,3-dimethyl- (C7) n-BO<|_2; 1 ,5- pentanediol, 3-methyl- (C6) (Me-E-|^); 1 ,5-pentanediol, 3-methyl- (C6) PO2; 2,3-pentanediol, (C5) (Me-E_n_3); 2,3-pentanediol, (C5) PO2; 2,3- pentanediol, 2-methyl- (C6) E1.7; 2,3-pentanediol, 2-methyl- (C6) PO<ι ; 2,3-pentanediol, 2-methyl- (C6) n-BO-j.2; 2,3-pentanediol, 3-methyl-

(C6) E1.7; 2,3-pentanediol, 3-methyl- (C6) P0<| ; 2,3-pentanediol, 3- methyl- (C6) n-BO_π_2; 2,3-pentanediol, 4-methyl- (C6) E-1.7; 2,3- pentanediol, 4-methyl- (C6) PO-| ; 2,3-pentanediol, 4-methyl- (C6) n- BO1.2; 2,4-pentanediol, (C5) 2(Me-Eι_4); 2,4-pentanediol (C5) PO4; 2,4-pentanediol, 2,3-dimethyl- (C7) (Me-E_π^); 2,4-pentanediol, 2,3- dimethyl- (C7) PO2; 2,4-pentanediol, 2,4-dimethyl- (C7) (Me-E-j.4); 2,4-pentanediol, 2,4-dimethyl- (C7) PO2; 2,4-pentanediol, 2-methyl- (C7) (Me-E5_ιo); 2,4-pentanediol, 2-methyl- (C7) PO3; 2,4- pentanediol, 3,3-dimethyl- (C7) (Me-E-|^); 2,4-pentanediol, 3,3- dimethyl- (C7) PO2; 2,4-pentanediol, 3-methyl- (C6) (Me-E5_₁₀); 2,4- pentanediol, 3-methyl- (C6) PO3;

4. 1 ,3-hexanediol (C6) (Me-Eι.5); 1 ,3-hexanediol (C6) PO2; 1 ,3- hexanediol (C6) BO-j ; 1 ,3-hexanediol, 2-methyl- (C7) E2-9; 1 ,3- hexanediol, 2-methyl- (C7) PO_π ; 1 ,3-hexanediol, 2-methyl- (C7) n- BO1.3; 1 ,3-hexanediol, 2-methyl- (C7) BO_η ; 1 ,3-hexanediol, 3-methyl-

(C7) E2-9; 1 ,3-hexanediol, 3-methyl- (C7) PO-| ; 1 ,3-hexanediol, 3- methyl- (C7) n-BOι.3; 1 ,3-hexanediol, 4-methyl- (C7) E2-9; 1 ,3- hexanediol, 4-methyl- (C7) PO-| ; 1 ,3-hexanediol, 4-methyl- (C7) n- BO1.3; 1 ,3-hexanediol, 5-methyl- (C7) E2-9; 1 ,3-hexanediol, 5-methyl- (C7) PO-|; 1 ,3-hexanediol, 5-methyl- (C7) n-BOι.3; 1 ,4-hexanediol

(C6) (Me-E-1.5); 1 ,4-hexanediol (C6) PO2; 1 ,4-hexanediol (C6) BO_π ; 1 ,4-hexanediol, 2-methyl- (C7) E2-9; 1 ,4-hexanediol, 2-methyl- (C7) PO1 ; 1 ,4-hexanediol, 2-methyl- (C7) n-BOι.3; 1 ,4-hexanediol, 3- methyl- (C7) E2-9; 1 ,4-hexanediol, 3-methyl- (C7) PO_π ; 1 ,4- hexanediol, 3-methyl- (C7) n-BO-1.3; 1 ,4-hexanediol, 4-methyl- (C7) E2-9, 1 ,4-hexanedιol, 4-methyl- (07) PO-|, 1,4-hexanedιol, 4-methyl- (07) n-BO-1.3; ,4-hexanedιol, 5-methyl- (07) E2.9; 1,4-hexanediol, 5- methyl- (07) PO_π; 1,4-hexanedιol, 5-methyl- (07) n-BO-_|_₃; 1,5- hexanediol (06) (Me-E_η_5); 1,5-hexanedιol (06) PO2; 1,5-hexanediol (C6) BO-i; 1,5-hexanediol, 2-methyl- (C7) E2.9; 1,5-hexanediol, 2- methyl- (07) PO<|; 1,5-hexanedιol, 2-methyl- (07) n-BOι.3; 1,5- hexanediol, 3-methyl- (07) E2-9, 1,5-hexanedιol, 3-methyl- (07) PO_η; 1,5-hexanediol, 3-methyl- (07) n-BO-1.3, 1,5-hexanedιol, 4-methyl- (07) E2-9; 1,5-hexanediol, 4-methyl- (07) PO-j; 1,5-hexanediol, 4- methyl- (07) n-BOι.3; 1,5-hexanedιol, 5-methyl- (07) E2.9; 1,5- hexanediol, 5-methyl- (07) PO-|, 1,5-hexanedιol, 5-methyl- (07) n- BO-1.3; 1 ,6-hexanediol (06) (Me-Eι.2), 1,6-hexanedιol (06) PO_π_2; 1,6-hexanediol (06) n-Bθ4; 1,6-hexanedιol, 2-methyl- (07) E1.5; 1,6- hexanediol, 2-methyl- (07) n-BOι_2, 1,6-hexanediol, 3-methyl- (07) E1.5, 1,6-hexanediol, 3-methyl- (07) n-BOι_2, 2,3-hexanediol (06) E-μ

5; 2,3-hexanediol (06) n-BO-|; 2,3-hexanedιol (06) B0-|, 2,4- hexanediol (06) (Me-E3_s); 2,4-hexanedιol (06) PO3; 2,4-hexanediol, 2-methyl- (07) (Me-E_η_2); 2,4-hexanedιol 2-methyl- (07) PO1.2, 2,4- hexanediol, 3-methyl- (07) (Me-E-j.2), 2,4-hexanediol 3-methyl- (07) P0-|_2; 2,4-hexanediol, 4-methyl- (07) (Me-E^<|_2); 2,4-hexanedιol 4- methyl- (07) PO-|_2; 2,4-hexanedιol, 5-methyl- (07) (Me-E_π_2), 2,4- hexanediol 5-methyl- (07) PO-^, 2,5-hexanedιol (06) (Me-E3_8), 2,5- hexanediol (06) PO3; 2,5-hexanedιol, 2-methyl- (C7) (Me-E-|_2), 2,5- hexanediol 2-methyl- (07) POι_2- 2,5-hexanedιol, 3-methyl- (07) (Me- E1.2), 2,5-hexanediol 3-methyl- (07) PO-|_2.3,4-hexanedιol (06) EO-|.

5; 3,4-hexanediol (06) n-BO_π; 3,4-hexanedιol (06) BO1;

5. 1,3-heptanediol (07) E-1.7; 1,3-heptanedιol (07) P0-|; 1,3-heptanediol

(07) n-BOι_2; 1,4-heptanedιol (07) E1.7, 1 ,4-heptanedιol (07) PO1,

1,4-heptanediol (07) n-BO_π.2. 1.5-heptanedιol (07) E1.7, 1,5- heptanediol (07) PO-]; 1,5-heptanedιol (07) n-BOι_2; 1,6-heptanediol

(07) E-|_7, 1,6-heptanedιol (07) PO_η, 1,6-heptanediol (07) n-BO<|_2, 1,7-heptanedιol (07) E-|_2, 1,7-heptanedιol (07) n-BOi; 2,4- heptanediol (07) E3..-10- 2,4-heptanedιol (07) (Me-E-j); 2,4-heptanediol (07) PO-i; 2,4-heptanediol (07) n-B03, 2,5-heptanedιol (07) E3.10, 2,5-heptanediol (07) (Me-Ei), 2,5-heptanedιol (07) PO_1p 2,5- heptanediol (07) n-B03; 2,6-heptanediol (07) E3.10; 2,6-heptanediol

(07) (Me-E-i); 2,6-heptanediol (07) PO1 ; 2,6-heptanediol (07) n-BO₃; 3,5-heptanediol (07) E3.10; 3,5-heptanediol (07) (Me-E-j ); 3,5- heptanediol (07) PO_π ; 3,5-heptanediol (07) n-BO3; 1 ,3-butanediol, 3-methyl-2-isopropyl- (08) PO; 2,4-pentanediol, 2,3,3- trimethyl- (08) PO; 1 ,3-butanediol, 2,2-diethyl- (08) E2-5; 2,4- hexanediol, 2,3-dimethyl- (08) E2-5; 2,4-hexanediol, 2,4-dimethyl- (08) E2-5; 2,4-hexanediol, 2,5-dimethyl- (08) E2.5; 2,4-hexanediol, 3,3- dimethyl- (08) E2-5; 2,4-hexanediol, 3,4-dimethyl- (08) E2-5; 2,4- hexanediol, 3,5-dimethyl- (08) E2-5; 2,4-hexanediol, 4,5-dimethyl- (08)

E2-5; 2,4-hexanediol, 5,5-dimethyl- (08) E2.5; 2,5-hexanediol, 2,3- dimethyl- (08) E2-5; 2,5-hexanediol, 2,4-dimethyl- (08) E2.5; 2,5- hexanediol, 2,5-dimethyl- (08) E2.5; 2,5-hexanediol, 3,3-dimethyl- (08) E2-5; 2,5-hexanediol, 3,4-dimethyl- (08) E2.5; 3,5-heptanediol, 3- methyl- (08) E2-5; 1 ,3-butanediol, 2,2-diethyl- (C8) n-BO-^; 2,4- hexanediol, 2,3-dimethyl- (08) n-BO-|_2; 2,4-hexanediol, 2,4-dimethyl-

(08) n-BO<|_2; 2,4-hexanediol, 2,5-dimethyl- (08) n-BO-|_2; 2,4- hexanediol, 3,3-dimethyl- (08) n-BOι_2; 2,4-hexanediol, 3,4-dimethyl- (08) n-BO_π_2; 2,4-hexanediol, 3,5-dimethyl- (08) n-BO<|_2; 2,4- hexanediol, 4,5-dimethyl- (08) n-BOι_2; 2,4-hexanediol, 5,5-dimethyl-, n-BOι_2; 2,5-hexanediol, 2,3-dimethyl- (08) n-BO<|_2; 2,5-hexanediol, 2,4-dimethyl- (08) n-BO-1.2; 2,5-hexanediol, 2,5-dimethyl- (08) n-BO-j. 2; 2,5-hexanediol, 3,3-dimethyl- (08) n-BO_π_2; 2,5-hexanediol, 3,4- dimethyl- (08) n-BO-1.2; 3,5-heptanediol, 3-methyl- (08) n-BO_π_2; 1 ,3- propanediol, 2-(1 ,2-dimethylpropyl)- (08) n-BO; 1 ,3-butanediol, 2-ethyl-

2,3-dimethyl- (08) n-BO; 1 ,3-butanediol, 2-methyl-2-isopropyl- (08) n- BO; 1 ,4-butanediol, 3-methyl-2-isopropyl- (08) n-BO; 1 ,3-pentanediol, 2,2,3-trimethyl- (08) n-BO; 1,3-pentanediol, 2,2,4-trimethyl- (08) n-BO; 1 ,3-pentanediol, 2,4,4-trimethyl- (08) n-BO; 1 ,3-pentanediol, 3,4,4- trimethyl- (08) n-BO; 1 ,4-pentanediol, 2,2,3-trimethyl- (08) n-BO; 1 ,4- pentanediol, 2,2,4-trimethyl- (08) n-BO; 1 ,4-pentanediol, 2,3,3- trimethyl- (08) n-BO; 1 ,4-pentanediol, 3,3,4-trimethyl- (08) n-BO; 2,4- pentanediol, 2,3,4-trimethyl- (08) n-BO; 2,4-hexanediol, 4-ethyl- (08) n-BO; 2,4-heptanediol, 2-methyl- (08) n-BO; 2,4-heptanediol, 3- methyl- (08) n-BO; 2,4-heptanediol, 4-methyl- (08) n-BO; 2,4- heptanediol, 5-methyl- (08) n-BO; 2,4-heptanediol, 6-methyl- (08) n- BO; 2,5-heptanediol, 2-methyl- (08) n-BO; 2,5-heptanediol, 3-methyl- (08) n-BO; 2,5-heptanediol, 4-methyl- (08) n-BO; 2,5-heptanediol, 5- methyl- (08) n-BO; 2,5-heptanediol, 6-methyl- (08) n-BO; 2,6- heptanediol, 2-methyl- (C8) n-BO; 2,6-heptanediol, 3-methyl- (C8) n-

BO; 2,6-heptanediol, 4-methyl- (08) n-BO; 3,5-heptanediol, 2-methyl- (08) n-BO; 1,3-propanediol, 2-(1 ,2-dimethylpropyl)- (08) E1.3, 1 ,3- butanediol, 2-ethyl-2,3-dimethyl- (08) E_π_3; 1 ,3-butanediol, 2-methyl-2- isopropyl- (08) E1.3; 1 ,4-butanediol, 3-methyl-2-isopropyl- (08) E1.3; 1 ,3-pentanediol, 2,2,3-trimethyl- (08) E1.3; 1 ,3-pentanediol, 2,2,4- trimethyl- (08) E1.3; 1 ,3-pentanediol, 2,4,4-trimethyl- (08) E1.3; 1 ,3- pentanediol, 3,4,4-trimethyl- (08) E-1.3; 1 ,4-pentanediol, 2,2,3- trimethyl- (08) E1.3; 1 ,4-pentanediol, 2,2,4-trimethyl- (08) E1.3; 1 ,4- pentanediol, 2,3,3-trimethyl- (08) E1.3; 1 ,4-pentanediol, 3,3,4- trimethyl- (08) E1.3; 2,4-pentanediol, 2,3,4-trimethyl- (08) E_π_3; 2,4- hexanediol, 4-ethyl- (08) E1.3; 2,4-heptanediol, 2-methyl- (08) E1.3; 2,4-heptanediol, 3-methyl- (08) E1.3; 2,4-heptanediol, 4-methyl- (08) E-|_3; 2,4-heptanediol, 5-methyl- (08) E1.3; 2,4-heptanediol, 6-methyl- (08) E-j_3; 2,5-heptanediol, 2-methyl- (08) E1.3; 2,5-heptanediol, 3- methyl- (08) E1.3; 2,5-heptanediol, 4-methyl- (08) E-|.₃; 2,5- heptanediol, 5-methyl- (08) E1.3; 2,5-heptanediol, 6-methyl- (08) E- 3; 2,6-heptanediol, 2-methyl- (08) E1.3; 2,6-heptanediol, 3-methyl- (08) E<|_3; 2,6-heptanediol, 4-methyl- (08) E1.3; and/or 3,5- heptanediol, 2-methyl- (08) E-1.3; and 7. mixtures thereof;

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 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- (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- dimethylpropyl)-; 2-Butene-1 ,4-diol, 2-(1-methylpropyl)-; 2-Butene-1 ,4-diol, 2-butyl-; 1 ,3-Pentanediol, 2-etheπyl-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-dioi, 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, 5,6-dιmethyl-; 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-Heρtene-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-ρropenyl)-; 6-Heptene-2,4- diol, 5,5-dimethyl-; 6-Heptene-2,5-diol, 4,6-dιmethyl-; 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-dιmethyl-; 1 ,7-Octadiene-3,6- diol, 2,6-dimethyl-; 1 ,7-Octadiene-3,6-diol, 2.7-dimethyi-; 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-Octadιene-1 ,7-diol, 3,7-dimethyl-; 2,6- Octadiene-1 ,4-diol, 3,7-dimethyl- (Rosiπdol), 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-dιol; 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-dιol, 2,7-dimethyl-; 5,7-Octadiene-1 ,4-diol, 7-methyl-; 5-Octene-1 ,3-diol; 6-Octene-1 ,3-dιol, 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-dιol, 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-dιol; 7-Octene-1 ,6-diol, 5-methyl-; 7- Octene-2,4-diol, 2-methyl-6-methylene-, 7-Octene-2,5-diol, 7-methyl-; 7- 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-Decadiene-4,6-diol; and J. mixtures thereof.

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., -

(CH₂CH₂0)_nH] : 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- 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- 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- 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-tri methyl- 1 ,3-pentanediol, 2,4,4-tr methyl-; 1 ,3- pentanediol, 3,4,4-trι methyl- 1 ,4-pentanediol, 2,2,3-tri methyl-; 1 ,4- pentanediol, 2,2,4-tri methyl- 1 ,4-pentanediol, 2,3,3-tπ methyl-; 1 ,4- pentanediol, 2,3,4-tri methyl- 1 ,4-pentanediol, 3,3,4-tri methyl-; 1,5- pentanediol, 2,2,3-tri methyl- 1 ,5-pentanediol, 2,2,4-trι methyl-; 1,5- pentanediol, 2,3,3-trι methyl- 1 ,5-pentanediol, 2,3,4-tri methyl-; 2,4- pentanediol, 2,3,3-trι methyl- 2,4-pentanediol, 2,3,4-tπ methyl-; 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, 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- 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-octaπediol; 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.

II. 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 103°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 (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- free solvent. The discussion below describes methods to remove the consumer noticeable malodorous components, but the discussion is not limiting as to other methods 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 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. III. 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 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 1

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 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.

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 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. A. Fabric Softening 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 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 Softening Active Compound

(DEQA) (1) The first type of DEQA preferably comprises, as the principal active, compounds of the formula

(R N^-KCr^n-Y- R¹] I,m χ(-)

(1)

wherein: each R substituent is a short chain C^-CQ, 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 -0-(O)C-, or -0(O)-O-, but 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 R being a long chain C8-C22 (^or C7-C2i)hydrocarbyl, or substituted hydrocarbyl substituent, preferably C10- 20 (^or C9-C19) alkyl or alkylene, most preferably C12- 18 (or C11-C17) alkyl or alkylene, and where, when said sum of carbons is CIQ-C-]Q and R1 is a straight chain alkyl or alkylene group, the Iodine Value (hereinafter referred to as IV) of the parent fatty acid of this R group is preferably 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 Iodine Value of a "parent" fatty acid, or "corresponding" fatty acid, is used to define 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 R group.)

The counterion, χ(^") 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 χ(^") represents half a group.

Preferred biodegradable quaternary ammonium fabric softening compounds can contain the group C(0)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: Fatty Acyl

Group DEQA¹ DEQA2 DEQA³ DEQA⁴ DEQA⁵ C12 trace 66 0 0 0 C14 3 22 0 0 0 C16 4 12 5 5 5 C18 0 5 6 6 014:1 3 0 0 0 016:1 11 0 0 3 018:1 74 71 68 67 018:2 4 8 11 11 018:3 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 (018:1) 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 Acyl Group DEQA6 DEQAZ

C14 0 1

C16 11 25

C18 4 20

014:1 0 0

016:1 1 0

018:1 27 45

018:2 50 6

C18:3 7 0

Unknowns 0 3

Total 100 100

IV 125-138 56 cis/trans (018:1) Not Available 7

TPU 57 6 DEQA⁶ is prepared from a soy bean fatty acid, and DEQA⁷ is prepared from a slightly hydrogenated tallow fatty acid.

Also optionally, but preferably, R 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%.

Fattv Acvl Group DEQAβ DEQA9 DEQA.10

Isomyristic acid — 1-2 —

Myristic acid 7-11 0.5-1 —

Isopalmitic acid 6-7 6-7 1-3

Palmitic acid 4-5 6-7 --

Isostearic acid 70-76 80-82 60-66

Stearic acid -- 2-3 8-10

Isoleic acid — -- 13-17

Oleic acid — — 6-12

IV 3 2 7-12

DEQAS - 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 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 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(0)-0-, preferably -O-(O)0-; m is 2 or 3, preferably 2; each n is 1 to 4, preferably 2; each R substituent is a C-i-Cβ 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- ) C8-C14 preferably a C-|2-14 hydrocarbyl, or substituted hydrocarbyl substituent and the counterion, X-, is the same as above. Preferably X^" does not include phosphate salts.

The saturated C8-C-14 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 C-|2- i4 (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. It will be understood that substituents R and R 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 DEQA^, and N,N- di(lauroyl-oxyethyl)-N,N-dimethyl ammonium chloride.

As used herein, when the diester is specified, 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 or -C(O)OH. For softening, under no/low detergent carry-over laundry 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 diester variation of DTDMAC, an amine of the formula RN(CH2CH2θH)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 C-|_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 r(-)

R -Y^

(2)

wherein each Y, R, R¹ , and χ(^") have the same meanings as before. Such compounds include those having the formula: [CH₃]₃ N(⁺)[CH₂CH(CH2θC[0]R¹)OC(0)R¹] Cl(^") where each R is a methyl or ethyl group and preferably each R is in the range of C15 to C-jg. Degrees of branching and substitution can be present in the alkyl(ene) chains. The anion χ(^") in the molecule 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, 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 R 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. 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 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 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-C18 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- 16 are preferred for lower wash temperatures (e.g., below about 50°C) and C-16- 18 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 C-12- 20 ^alky' ^or hydroxyalkyl, more preferably C12- 18 ^a'M 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 -12C-18 alkyl polyethoxylate (1.0) sulfate, C12-C18 alkyl polyethoxylate (2.25) sulfate, C12-C18 alkyl polyethoxylate (3.0) sulfate, and C12-C-18 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-C18 ^alky' 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 Cg to C12 alkyl phenols, alkylene oxide condensates of C8-C22 alkanols and ethylene oxide/propylene oxide block polymers (Pluronic™-BASF Corp.), as well as semi polar nonionics (e g-, amine oxides and phosphine oxides) can be used in the present 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:

wherein R⁷ is C5-C31 alkyl, preferably straight chain C7-C19 alkyl or alkenyl, more preferably straight chain C9-C17 alkyl or alkenyl, most preferably straight chain C11-C15 alkyl or alkenyl, or mixtures thereof; R⁸ is selected from the group consisting of hydrogen, C1-C4 alkyl, C-|- C4 hydroxyalkyl, preferably methyl or ethyl, more preferably methyl. Q is a polyhydroxyalkyl moiety having a linear 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(CH₂OH)(CHOH)n-i CH₂OH, -CH₂(CHOH)₂-

(CHOR')(CHOH)CH2θH, 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-N< can be, for example, cocamide, stearamide, oleamide, lauramide, myristamide, capricamide, palmitamide, tallowamide, etc. 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- 8 N-(3-methoxypropyl) glucamide. The N-propyl through N-hexyl C12- 18 glucamides can be used for low sudsing. C10- 20 conventional soaps may also be used. If high sudsing is desired, the branched-chain C^<|rj- i6 soaps may be used. 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:

wherein R-| 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, Ri 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 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, R-j is anilino, R2 is N-2-hydroxyethyl- 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, Ri 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. Dispersibilitv 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 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 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:

[R N⁺(R⁵)₃] X- wherein

R⁴ is C8-C22 alkyl or alkenyl group, preferably C10-C18 alkyl or alkenyl group; more preferably C-10- 14 or C16- 18 alkyl or alkenyl group; each R⁵ is a C-|-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 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, 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 8-C22 alkyl choline esters. The preferred dispersibility aids of this type have the formula:

R¹C(O)-0-CH₂CH2N⁺(R)3 X^" wherein R¹, R and X" are as defined previously.

Highly preferred dispersibility aids include C-12-C14 coco choline ester and C<j6-Ci8 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 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® 0/25 from Akzo; and polyethylene glycol (15) cocomonium chloride, available under the trade name Ethoquad® C/25 from Akzo. 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 dimethyloctyla ine 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).

Examples of antioxidants that can be added to the compositions of this invention include a mixture of ascorbic acid, ascorbic palmitate, propyl gallate, available from Eastman Chemical Products, Inc., under the trade names Tenox® PG and Tenox® S-1 ; a mixture of BHT (butylated hydroxytoluene), BHA (butylated hydroxyanisole), propyl gallate, and citric acid, available from Eastman Chemical Products, 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® 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 (C8-C22) of gallic acid, e.g., dodecyl gallate; Irganox® 1010; Irganox® 1035; Irganox® B 1171 ; Irganox® 1425; Irganox® 3114; Irganox® 3125; and mixtures thereof; preferably Irganox® 3125, Irganox® 1425, Irganox® 3114, and mixtures thereof; more preferably Irganox® 3125 alone or mixed with citric acid and/or other chelators such as isopropyl citrate,

Dequest® 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 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® (from ICI).

Highly preferred soil release agents are polymers of the generic formula:

;— (OCH2CH2)_p(O— C ff-R ₁₄ - C Ii ~ OR ₁ ^, ₅ ^q)_u(O-C I-Rl -OC ?-θχCH2CH2θ-)_rι-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 R 1⁴ moieties consist entirely of 1 ,4-phenylene moieties, or are partially substituted with other arylene or alkarylene moieties, alkylene moieties, alkenylene moieties, or mixtures thereof. Arylene and alkarylene moieties which can be partially substituted for 1 ,4-phenylene include 1 ,3-phenylene, 1 ,2- phenylene, 1 ,8-naphthylene, 1 ,4-naphthylene, 2,2-biphenylene, 4,4- biphenylene, and mixtures thereof. Alkylene and alkenylene moieties which can be partially substituted include 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 R '⁴ 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 R ⁴ moieties consist entirely of (i.e., comprise 100%) 1 ,4-phenylene moieties, i.e., each R¹⁴ moiety is 1 ,4-phenylene. For the R 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 R ⁵ 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. Preferably, from about 75% to about 100%, are 1 ,2-propylene moieties.

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. 5. 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 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®; Varonic U-250®; Genapol T-500®, Genapol T-800®; Plurafac A-79®. 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-methyl-4-isothiazoline-3-one and 2-methyl-4-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 - 45 -

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 about 0.2% to about 3%, by weight of the finished composition.

8. Chelating Agents

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. Amino carboxylates useful as chelating agents herein include ethylenediaminetetraacetates (EDTA), N- hydroxyethylethylenediaminetriacetat.es, 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):

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 surfactants useful herein typically at levels from about 1% to about 55%, by weight, include the conventional C-| i-C-jβ ^a,ky' benzene sulfonates ("LAS"), the C10- 18 secondary (2,3) alkyl sulfates of the formula CH3(CH2)_x(CHOSθ3^"M⁺) CH₃ and CH₃ (CH₂)_y(CHOSθ3 -^~.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- 18 alkyl alkoxy carboxylates (especially the EO 1-5 ethoxycarboxylates), the C10-I8 giycerol ethers, the C 0-C18 alkyl polyglycosides and their corresponding sulfated polyglycosides, and Cl2^_Cl8 ^aIP^na-^su.f°^natecl fatty acid esters. If desired, the conventional nonionic and amphoteric surfactants such as the C12-C18 alkyl ethoxylates ("AE") including the so-called narrow peaked alkyl ethoxylates and Cg-C 2 alkyl phenol alkoxylates

(especially ethoxylates and mixed ethoxy/propoxy), C 2-C18 betaines and sulfobetaines ("sultaines"), C 0-C 8 amine oxides, and the like, can also be included in the overall compositions. The C 0-C18 N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples include the C 2-C18 N-methylglucamides. See WO 9,206,154. Other sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as C10- 18 N-(3-methoxypropyl) glucamide. C 0-C20 conventional soaps may also be used. If high sudsing is desired, the branched-chain Cirj-C g 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, C9-C20 linear alkylbenzenesulphonates, C8-C22 primary or secondary alkanesulphonates, C8-C24 olefmsulphonates, sulphonated polycarboxylic acids, alkyl giycerol sulfonates, fatty acyl giycerol sulfonates, fatty oleyl giycerol 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 C 2-C 8 monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C -Ci4 diesters), N-acyl sarcosinates, sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside, branched primary alkyl sulfates, alkyl polyethoxy carboxylates such as those of the formula RO(CH2CH2θ)kCH2COO-M⁺ wherein R is a Cs- 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 Agents and Detergents (Vol. I and II 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:

wherein R⁹ is C2-C6 linear alkylene, C3-C6 branched alkylene, C5-C7 cyclic alkylene, and mixtures thereof; R 0 is independently selected from hydrogen or -L-Sθ3'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 ; 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: a) ethoxylated or propoxylated hydroxyethanesulfonate or ethoxylated or propoxylated hydroxypropanesulfonate units of the formula (Mθ3S)(CH2) (^{Rl 1} °)n". where M is a salt forming cation, RU is ethylene, propylene, and mixtures thereof, m is 0 or 1 , and n is from 1 to 20; b) sulfoaroyl units of the formula -(0)C(CgH4)(S03-M⁺), wherein M is a salt forming cation; c) modified poly(oxyethylene)oxy monoalkyl ether units of the formula R1²0(CH2CH20)|<-, wherein R ² 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 Mθ3S(C6H4)(OR ³)_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 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 -SO_xM wherein x is 2 or 3, said terminal unit substituent groups being derived from a bisulfite component selected from the group consisting of HSO3M wherein M is a conventional water-soluble cation; a capped terephalate co-polymer having the formula

X[(OCH₂CH₂)n(OR₅)_mI[(A-Rl-A-R2)_u(A-R3-Λ-R2)_vl— A-R⁴-A[(R5θ)_m(CH₂CH₂θ)_n]X wherein each of the A moieties is selected from the group consisting of

O I I O I I

— 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, Cι-Cs alkylene,

C1-C8 alkenylene and mixtures thereof the R 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-C18 hydrocarbylene moieties having at least one -CO2M, -

0[(R⁵0)_m(CH₂CH₂0)_n]X or -A[(R2-A-R⁴-

A)]_w[(R⁵0)_m(CH2CH2θ)_n]X substituent; the R⁴ moieties are R¹ or R³ moieties, or mixtures thereof; each R⁵ is C -C4 alkylene, or the moiety -R2-A-R⁶- wherein R⁸ is a C -C12 alkylene, alkenylene, arylene, or alkarylene moiety; each M is hydrogen or a water- soluble 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 [(R⁵0)_m(CH2CH2θ)_n], provided that when R⁵ is the moiety -R2-A-R⁸-, 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; 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:

[H₂N-R]n+ι -[N-R]_m-[N-R]_n-NH₂ having a modified polyamine formula V(_n+ )W_mY_nZ or a polyamine backbone corresponding to the formula:

H | R

[H₂N-R]_n- +t— [N-R]_m-[N-R]_n-fN-R]k-NH₂ having a modified polyamine formula

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:

O

E X

E— N-R — _or E— N-R — _or E— N t-R — I °^r I ^or I

E E E ii) W units are backbone units having the formula:

iii) Y units are branching units having the formula:

iv) Z units are terminal units having the formula:

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, C8-C12 dialkylarylene, -(Rlθ)_xR¹-, -(R θ)_xR⁵(OR )_x-,

(CH₂CH(OR2)CH2θ)_z-(Rlθ)yR¹(OCH2CH(OR2)CH2)_w-, C(0)(R⁴)_rC(0)-, -CH2CH(0R2)CH₂-, and mixtures thereof; wherein R1 is C2-C3 alkylene and mixtures thereof; R2 is hydrogen, -(Rlθ)_xB, and mixtures thereof; R³ is C1-C 8 alkyl, C7-

C 2 arylalkyl, C7-C12 alkyl substituted aryl, C5-C 2 aryl, and mixtures thereof; R⁴ is C1-C 2 alkylene, C4-C12 alkenylene, Cs- C 2 arylalkylene, C5-C10 arylene, and mixtures thereof; R5 is Cι- C 2 alkylene, 3-C12 hydroxy-alkylene, C4-C12 dihydroxyalkylene, C8-C12 dialkylarylene, -C(O)-,

C(0)NHR6NHC(0)-, -R1(0R1)-, -C(0)(R⁴)_rC(0)-, CH₂CH(OH)CH2-, -CH₂CH(OH)CH2θ(R¹0)yRl-

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)_pC0₂M, -(CH₂)_qS03M, -CH(CH2C0₂M)- C0₂M, -(CH₂)pP0₃M, -(R θ)_xB, -C(0)R³, and mixtures thereof; provided that when any E unit of a nitrogen is a hydrogen, said nitrogen is not also an N-oxide; B is hydrogen, C -Cg alkyl, -

(CH₂)q-S0₃M, -(CH₂)_pC02M, -(CH₂)q(CHSθ3M)CH₂Sθ3M, -

(CH₂)q-(CHSθ2M)CH2Sθ3M, -(CH₂)_pPθ3M, -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 Enzymes

Enzymes can be included in the present detergent compositions for a variety of purposes, including removal of protein-based, carbohydrate-based, or tnglycende-based stains from surfaces such as 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 include, 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 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 0.1 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 spotting/filming 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. licheniformis. One suitable protease is obtained from a strain of Bacillus, having maximum activity throughout the pH 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. 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 95/29979 published November 9, 1995 by The Procter & Gamble Company. 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, January 9, 1985. Amylases suitable herein, include, for example, α-amylases described in GB 1 ,296,839 to Novo; RAPIDASE®, International Bio- Synthetics, Inc. and TERMAMYL®, 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. 260, 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 α-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 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 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 8. amyloliquefaciens, B.subtilis, 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.licheniformis

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 insolens or Humicola strain DSM1800 or a cellulase 212-producing fungus belonging to the genus Aeromonas, and cellulase extracted from the hepatopancreas of a marine mollusk, Dolabella Auricula 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. lipolyticum 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 Novo, and U.S. 3,553,139, January 5, 1971 to McCarty et al. Enzymes are further disclosed 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 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 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 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. 13. 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 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), 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 Siθ2'Na2θ 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 (commonly abbreviated herein as "SKS-6"). Unlike zeolite builders, the Na SKS-6 silicate builder does not contain aluminum. NaSKS-6 has the delta-Na2Siθ5 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 NaMSi_xθ2_X+ yH2θ 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-Na2Siθ5 (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 stabilizing agent for oxygen bleaches, and as a component of suds control systems.

Examples of carbonate builders are the alkaline earth and alkali metal 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:

M_z(zAI0₂)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 aluminosilicates 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: Naι₂[(Alθ2)i2(Siθ2)i2] H₂0 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 neutralized salt. When utilized in salt form, 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 nitrilotriacetic 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 availability from renewable resources and their biodegradability. Citrates can also be used in granular compositions, especially in combination with zeolite and/or 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 C5-C20 a'kyl and alkenyl succinic acids and salts thereof. A particularly preferred 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 3,723,322.

Fatty acids, e.g., C 2-C18 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 alkali 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- 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 Application 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 Dispersing 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 antiredeposition. 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. 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. 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 C 8- 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 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, alicydic, 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 exemplary silicone based suds suppressor for use herein is a suds suppressing amount of a suds controlling agent consisting essentially of: (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)3SiOι/2 units of Siθ2 units in a ratio of from (CH3)3 SiOι/2 units and to Siθ2 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 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. 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 Cg- Ci6 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 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-A_x-P; wherein P is a polymerizable unit to which an N-0 group can be attached or the N-0 group can form part of the polymerizable unit or the N-0 group can be attached to both units; A is one of the following structures: -NC(O)-, -C(0)0-, -S-, -0-, -N=; x is 0 or 1 ; and R is aliphatic, ethoxylated aliphatics, aromatics, heterocyclic or alicydic groups or any combination thereof to which the nitrogen of the N-0 group can be attached or the N-0 group is part of these groups Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridme, pyrrole, imidazole, pyrrolidine, pipendine and derivatives thereof

The N-0 group can be represented by the following general structures

O O

I I

(R, )χ-N -(R₂)y, =N — (R,

(R₃)z wherein R , R2, R3 are aliphatic, aromatic, heterocyclic or alicydic groups or combinations thereof, x, y and z are 0 or 1, and the nitrogen of the N-0 group can be attached or form part of any of the aforementioned groups The amine oxide unit of the polyamine N- oxides has a pKa <10, preferably pKa <7, more preferred pKa <6

Any polymer backbone can be used as long as the amine oxide polymer formed is water-soluble and has dye transfer inhibiting properties Examples of suitable polymeric backbones are polyvmyls, 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 copolymeπzation 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 1 ,000 to 500,000, most preferred 5,000 to 100,000 This preferred class of materials can be referred to as "PVNO" The most preferred polyamine N-oxide useful in the detergent compositions herein is poly(4-vιnylpyrιdιne-N-oxιde) which as an average molecular weight of about 50,000 and an amine to amine N- oxide ratio of about 1 4 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 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 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. 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 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 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 2 j|η_e substantially odor-free polyhydroxyl solvent made by the description in Example 1.

Example 4

This example illustrates a heavy duty liquid detergent composition containing a substantially odor-free-polyhydroxyl solvent. The heavy duty liquid detergent composition is substantially free of consumer noticeable malodorous components.

Component wt. %

Polyhyd roxy Coco-Fatty Acid Amide 4.15

C14-C15 Alcohol Ethoxylate E2.25 Sulfate 21.90

C 10 Amidopropyl Amine 1.20 Polyhydroxyl Solvent 1 10.00

Citric Acid 3.50

Fatty Acid (C12-C 4) 4.50

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 Water and Minors³ Balance

1 The substantially odor-free polyhydroxyl solvent made by the description in Example 1.

² Eg Ethoxylated Alcohols as sold by the Shell Oil Co. 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, including CaCθ3, talc, silicates, etc. Example 5

This example illustrates 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. %

C-12-15 Alcohol Ethoxylate E2.5 Sulfate 6.00

Alkyl N-Methyl Glucose Amide 1.00

C 2-13 ^6.5 Nonionic 10.0

Polyhydroxyl Solventl 5.00 Fatty Acid (C12-C 14) 0.70

Citric Acid 0.40

NaOH 0.85

Monoethanolamine 1.00

Propanediol 2.00 Xylene Sulfonic Acid 2.00

Water and Minors2 Balance

1 The substantially odor-free polyhydroxyl solvent made by the description in Example 1. 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, including CaC03, talc, silicates, etc.

Example 6 This example illustrates 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. %

Sodium Ci2- 4 Alcohol Ethoxylate E2.2 Sulfate 22.0

C 2- 4 Alkyl Dimethyl Amine Oxide 2.30

C 12-14 Alkyl Dimethyl Betaine 2.30

C9_ι E8 Alkyl Ethoxylate 6.70

C12-14 Glucose Amide 0.40

Polyhydroxyl Solvent 5.00

Sodium Cumene Sulphonate 4.50

Ethanol 7.00

Water and Minors² Balance

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, including CaC03, talc, silicates, etc.

Claims

WHAT IS CLAIMED IS:

1. A substantially odor-free polyhydroxyl solvent, wherein the solvent is substantially free of the following consumer noticeable malodorous components: a. highly volatile malodorous components having a boiling point lower than the polyhydroxyl solvent; and b. nonvolatile malodorous components having a boiling point higher than the polyhydroxyl solvent and having a lower polarity than the polyhydroxyl solvent.

2. A liquid detergent composition comprising the solvent of claim 1.

3. A fabric softening composition comprising the solvent of claim 1.

4. A heavy duty liquid detergent composition comprising the solvent of claim 1.

5. 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.

6. A substantially odor free polyhydroxyl solvent, wherein the solvent is substantially free of consumer noticeable malodorous components, made by the process of Claim 2.

7. A liquid detergent composition comprising the solvent of claim 6.

8. A fabric softening composition comprising the solvent of claim 6.

9. A heavy duty liquid detergent composition comprising the solvent of claim 6.

10. A substantially odor-free polyhydroxyl solvent, wherein the solvent is 1,2- hexanediol and is substantially free of the following consumer noticeable malodorous components: a. highly volatile malodorous components having a boiling point lower than about 220°C; and b. nonvolatile malodorous components having a boiling point higher than about 220°C and having a ClogP greater than about 0.60.

11. A substantially odor-free polyhydroxyl solvent of Claim 10, wherein the highly volatile malodorous components are selected from the group consisting of butyloxirane, pentanal, and mixtures thereof.

12. A fabric softening composition comprising the solvent of Claim 11.

13. A fabric softening composition comprising: a. 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 composition, of a fabric softener active selected from the group consisting of:

(1 ) softener having the formula:

(R)4-_m- N(⁺)- KCH2)n- Y-

wherein each R substituent is a short chain C^-CQ, 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-; the sum of carbons in each R^, plus one when Y is -0-(0)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 C5-C22 (or C7-C2i)hydrocarbyl, or substituted hydrocarbyl substituent, preferably C 0-C20 (or C9-C19) alkyl or alkylene, most preferably C 2-C 8 (or C11-C17) alkyl or alkylene, and where, when said sum of carbons is C 6-C 8 and R1 is a straight chain alkyl or alkylene group, the Iodine Value (hereinafter referred to as IV) of the parent fatty acid of this R¹ group is preferably 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 Iodine Value of a "parent" fatty acid, or "corresponding" fatty acid, is used to define a level of unsaturation for an R1 groups that is the same as the level of unsaturation that would be present in a fatty acid containing the same R group.); and wherein the counterion, X", can be any softener-compatible anion, preferably, chloride, bromide, methylsulfate, sulfate, and nitrate, more preferably chloride; (2) softener having the formula:

R¹-Y-CH2

CHCH2N(⁺)R3 Γ(-)

R -Y^

( ) wherein each Y, R, R1 , and χ(") have the same meanings as before (Such compounds include those having the formula:

[CH₃]₃ N(⁺)[CH₂CH(CH₂OC[0]R¹)OC(0)R¹] CI(-)

where C(0)R^'' is derived from unsaturated, e.g., oleic, fatty acid and, preferably, each R is a methyl or ethyl group and preferably each R is in the range of C 5 to C19 with degrees of branching and substitution optionally being present in the alkyl chains); and (3) mixtures thereof; b. 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 composition of the solvent of Claim 11 ; and c. the balance being water, wherein molar ratio of said solvent to said fabric softener active is not less than 3.

14. A process for making a substantially odor-free polyhydroxyl solvent, wherein the solvent is 1 ,2-hexanediol and substantially free of consumer noticeable malodorous components, comprising the following steps: a. removing highly volatile malodorous components selected from the group consisting of butyloxirane, pentanal, and mixtures thereof from the polyhydroxyl solvent by separation techniques based upon different boiling points; b. mixing the polyhydroxyl solvent of step (a) with water, wherein the ratio of solvent to water is from about a 1 :3 to 1 :10 ratio; and c. treating the mixture of step (b) with activated carbon, whereby the nonvolatile malodorous components are removed.

15. A substantially odor free polyhydroxyl solvent, wherein the solvent is substantially free of consumer noticeable malodorous components, made by the process of Claim 14.