WO1997003172A1 - Concentrated, stable fabric softening compositions including chelants - Google Patents

Concentrated, stable fabric softening compositions including chelants Download PDF

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Publication number
WO1997003172A1
WO1997003172A1 PCT/US1996/011572 US9611572W WO9703172A1 WO 1997003172 A1 WO1997003172 A1 WO 1997003172A1 US 9611572 W US9611572 W US 9611572W WO 9703172 A1 WO9703172 A1 WO 9703172A1
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WIPO (PCT)
Prior art keywords
methyl
dimethyl
hexanediol
pentanediol
diol
Prior art date
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PCT/US1996/011572
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English (en)
French (fr)
Inventor
Errol Hoffman Wahl
John Cort Severns
Scott William Waite
Frederick Anthony Hartman
Hugo Jean Marie Demeyere
Marc Johan Declercq
Alice Marie Ward
Original Assignee
The Procter & Gamble Company
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Filing date
Publication date
Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to CA002226550A priority Critical patent/CA2226550C/en
Priority to BR9609823A priority patent/BR9609823A/pt
Priority to AU66365/96A priority patent/AU6636596A/en
Priority to JP50599197A priority patent/JP3916666B2/ja
Priority to MX9800381A priority patent/MX9800381A/es
Priority to EP96926070A priority patent/EP0839180A1/en
Publication of WO1997003172A1 publication Critical patent/WO1997003172A1/en
Priority to US11/044,560 priority patent/US20050202998A1/en

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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
    • D06M23/10—Processes in which the treating agent is dissolved or dispersed in organic solvents; Processes for the recovery of organic solvents thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/62—Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/645—Mixtures of compounds all of which are cationic
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/001—Softening compositions
    • C11D3/0015—Softening compositions liquid
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2041—Dihydric alcohols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2041—Dihydric alcohols
    • C11D3/2044—Dihydric alcohols linear
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2041—Dihydric alcohols
    • C11D3/2048—Dihydric alcohols branched
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2093—Esters; Carbonates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids

Definitions

  • the present invention relates to translucent or clear, aqueous, concentrated, liquid softening compositions which include chelants. It especially relates to softening compositions for use in the rinse cycle of a laundering operation to provide excellent fabric-softening/static-control benefits.
  • the compositions are characterized by, e.g., reduced staining of fabric, excellent water dispersibility, rewettability, and/or storage and viscosity stability at sub-normal temperatures, i.e., temperatures below normal room temperature, e.g., 25°C.
  • Fabric softening compositions containing high solvent levels are known in the art. However, softener agglomerates can form and can deposit on clothes which can result in staining and reduced softening performance. Also, compositions may thicken and/or precipitate at lower temperatures, i.e., at about 40°F (about 4°C) to about 65°F (about 18°C). These compositions can also be costly for the consumer due to the high solvent levels associated with making a concentrated, clear product.
  • the present invention provides concentrated aqueous liquid fabric softening compositions with low organic solvent level (i.e., below about 40%, by weight ofthe composition) and a chelating agent, that have improved stability (i.e., remain clear or translucent and do not precipitate, gel, thicken, or solidify) at normal, i.e., room temperatures and sub-normal temperatures under prolonged storage conditions.
  • the compositions also provide reduced staining of fabrics, good cold water dispersibility, together with excellent softening, anti-static and fabric rewettability characteristics, as well as reduced dispenser residue buildup and excellent freeze-thaw recovery.
  • U.S. Patent No. 3,756,950 discloses the addition of chelants to fabric softening compositions to prevent yellowing of fabrics treated with the compositions.
  • U.S. Patent No. 5,399,272 discloses clear liquid fabric softening compositions.
  • U.S. Patent 5,525,245 also discloses clear liquid fabric softening compositions.
  • a clear or translucent fabric softening composition comprising:
  • each R substituent is hydrogen or a short chain Cj-Cg, 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, preferably 2; each Y is -O-(O)C-, -(R)N-(O)C-, -C(O)-N(R)-, or -C(O)-O-, preferably -O-(O)C-; the sum of carbons in each R 1 , plus one when Y is - O-(O)C- or -(R)N-(O)C-, is C6-C22, preferably Ci2-22> more preferably C1 -C20, but no more than one Rl or YR* sum being less than about 12 and then the other Rl or YR
  • B less than about 40%, by weight of the composition of a principal solvent having a ClogP of from about 0J5 to about 0.64; C. from about 0.001% to about 10% by weight of the composition of a chelating material;
  • water soluble solvents selected from the group consisting of: ethanol, isopropanol, propylene glycol, 1,3-propanediol, propylene carbonate, and mixtures thereof, the water soluble solvents being at a level that will not form clear compositions by themselves; and
  • Each R* in the fabric softening active may comprise a long chain C5-C21 branched alkyl or unsaturated alkyl, optionally substituted.
  • the ratio of branched alkyl to unsaturated alkyl being from about 5:95 to about 95:5, and for the unsaturated alkyl group, the average Iodine Value of the parent fatty acid of this R 1 group is from about 20 to about 140.
  • the composition contains from about 15% to about 70% of the softener active, wherein, in the softener active, each R substituent is hydrogen or a short chain C1-C3 alkyl or hydroxyalkyl group; each n is 2; each Y is -O-(O)C-; the sum of carbons in each R 1 plus one is C12-C22 , and Rl is branched alkyl or unsaturated alkyl, the ratio of branched alkyl to unsaturated alkyl being from about 75:25 to about 25:75, and for the unsaturated alkyl group, the average Iodine Value of the parent fatty acid of this R ⁇ group is from about 50 to about 130; and wherein the counterion, X", is selected from the group consisting of: chloride, bromide, methylsulfate, ethylsulfate, sulfate, and nitrate.
  • each R substituent is hydrogen or a short chain C1-C3 alkyl or hydroxyalkyl group; each n is 2; the sum of carbons in each R* plus one is C12-C2O' and the counterion, X ⁇ , is selected from the group consisting of: chloride, bromide, methylsulfate, ethylsulfate, sulfate, and nitrate, still more preferably each R substituent is selected from the group consisting of: methyl, ethyl, propyl, hydroxyethyl, and benzyl; each m is 2; each n is 2; the sum of carbons in each R , plus one is C14-C20, with each R ⁇ being a long chain C13-C19 branched alkyl or unsaturated alkyl, the ratio of branched alkyl to unsaturated alkyl being from about 50:50 to about 30:70; for the unsaturated alkyl group, the Iodine
  • the level of fabric softening active containing polyunsaturated alkylene groups is optionally at least about 3% by weight of the total softener active present and the average Iodine Value of the parent fatty acid of the R* group is from about 60 to about 140.
  • the chelant in said composition may be selected from the group consisting of diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, ethylenediamine- N ⁇ -disuccinnic acid, diethylenetriamine-N,N,N , ,N",N"-pentakis(methane phos ⁇ phonic acid), nitrilotriacetic acid and mixtures thereof with diethylenetriaminepentaacetic acid being the most preferred.
  • the composition includes from about 0.01% to about 5% by weight of the composition of said chelant and/or from about 4% to about 50%, most preferably from about 10% to about 40% ofthe fabric softener active.
  • a clear or translucent fabric softening composition comprises:
  • the balance being water; wherein the composition has a percentage haze in transmision mode of a Hunter Color analysis ofless than about 90.
  • the percentage haze in transmision mode of a Hunter Color analysis is less than about 50% and most preferably less than about 25%.
  • the chelant may be preferably selected from the group consisting of diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, ethylenediamine- N.N'-disuccinnic acid, diethylenetriamine-N,N,N , ,N",N"-pentakis(methane phos ⁇ phonic acid), nitrilotriacetic acid and mixtures thereof with diethylenetriaminepentaacetic acid being the most preferred.
  • the fabric softening active may be defined as above.
  • the compositions herein are aqueous, translucent or clear, most preferably clear, compositions containing from about 3% to about 95%, preferably from about 5% to about 80%, more preferably from about 15% to about 70%, and even more preferably from about 40% to about 60%, water and from about 3% to about 40%, preferably from about 10% to about 35%, more preferably from about 12% to about 25%, and even more preferably from about 14% to about 20%, ofthe above principal alcohol solvent B.
  • These preferred products (compositions) are not translucent or clear without principal solvent B.
  • the amount of principal solvent B. required to make the compositions translucent or clear is preferably more than 50%, more preferably more than about 60%, and even more preferably more than about 75%, ofthe total organic solvent present.
  • the principal solvents are desirably kept to the lowest levels that provide acceptable stability/clarity in the present compositions.
  • the presence of water exerts an important effect on the need for the principal solvents to achieve clarity of these compositions.
  • the softener active-to- principal solvent weight ratio is preferably from about 55:45 to about 85:15, more preferably from about 60:40 to about 80:20.
  • the softener active-to-principal solvent weight ratio is preferably from about 45:55 to about 70:30, more preferably from about 55:45 to about 70:30. But at high water levels of from about 70% to about 80%, the softener active-to-principal solvent weight ratio is preferably from about 30:70 to about 55:45, more preferably from about 35:65 to about 45:55. At higher water levels, the softener to principal solvent ratios should be even higher.
  • the pH of the compositions should preferably be from about 1 to about 7, preferably from about 1.5 to about 5, more preferably from about 2 to about 3.5.
  • the present invention contains as an essential component from about 2% to about 80%, preferably from about 13% to about 75%, more preferably from about 17% to about 70%, and even more preferably from about 19% to about 65% by weight of the composition, of a fabric softener active selected from the compounds identified hereinafter, and mixtures thereof.
  • the first type of DEQA preferably comprises, as the principal active * , compounds of the formula
  • each R substituent is hydrogen or a short chain C ⁇ -C , 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, preferably 2; each Y is -O-(O)C-, -(R)N-(O)C-, -C(O)-N(R)-, or -C(O)-O-, preferably -O-(O)C-; the sum of carbons in each R 1 , plus one when Y is - O-(O)C- or -(R)N-(O)C-, is C 6 -C22, preferably C 12-22.
  • each R 1 being a long chain C5-C21 (or C ⁇ - C22 preferably C9-C19 (or C9-C20), most preferably C11-C17 (or C ⁇ -Cig), straight, branched, unsaturated or polyunsaturated alkyl.
  • Rl may be branched alkyl and unsaturated alkyl (including polyunsaturated alkyl), wherein the ratio of branched alkyl to unsaturated alkyl is from about 5:95 to about 95:5, preferably from about 75:25 to about 25:75, more preferably from about 50:50 to about 30:70, especially 35:65.
  • the softener active may contain 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 ofthe total softener active present.
  • the "percent of softener active" containing a given Rl group is based upon taking a percentage ofthe total active based upon the percentage that the given R* group is, of the total R* groups present.
  • the Iodine Value of the parent fatty acid of the R* group is preferably from about 20 to about 140, more preferably from about 50 to about 130; and most preferably from about 70 to about 115; and wherein the counterion, X", can be any softener-compatible anion, preferably, chloride, bromide, methylsulfate, ethylsulfate, sulfate, and/or nitrate, more preferably chloride.
  • the fabric softening actives prepared according to the present invention may have the formula:
  • each Y, R, R 1 , and ⁇ (" have the same meanings as before.
  • Such compounds include those having the formula: [CH 3 ] 3 N( + )[CH 2 CH(CH 2 O(O)CR 1 )O(O)CR 1 ] c ⁇ ( - )
  • -O(O)CR 1 is derived partly 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 Cj5 to C ⁇ with degrees of branching and substitution being present in the alkyl chains.
  • Mixtures of actives of formula (1) and (2) may also be prepared.
  • the counterion, Xw above can be any softener-compatible anion, preferably the anion of a strong acid, for example, chloride, bromide, methylsulfate, ethylsulfate, sulfate, nitrate and the like, more preferably chloride.
  • the anion can also, but less preferably, carry a double charge in which case X represents half a group.
  • the fabric softener active can comprise mixtures of compounds containing, respectively, branched and unsaturated compounds.
  • Preferred biodegradable quaternary ammonium fabric softening compounds useful in preparing such mixtures can contain the group -O-(O)CR 1 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 unsaturated fatty acids are disclosed hereinafter as DEQA ⁇ to DEQA* .
  • DEQA ⁇ is prepared from a soy bean fatty acid
  • DEQA is prepared from a slightly hydrogenated tallow fatty acid
  • DEQA** is prepared from slightly hydrogenated canola fatty acids.
  • the total of active represented by the branched chain groups is typically from about 5% to about 95%, preferably from about 25% to about 75%, more preferably from about 35% to about 50%.
  • Suitable branched chain fatty acids that can be used to prepare branched, or mixed branched alkyl and unsaturated alkyl DEQAs, can be prepared by a variety of methods.
  • the corresponding branched chain fatty alcohols can be prepared by reduction ofthe branched chain fatty acids by standard reactions, e.g., using borane- THF after the method of Brown, J. Amer. Chem. Soc. (1970), 92, 1637, incorporated herein by reference.
  • the following are non-limiting examples of branched chain fatty acids.
  • Branched Chain Fattv Acid 1 2-n-Heptylundecanoic Acid
  • 2-n-Heptylundecanoic acid [22890-21-7] is available from TCI America, catalog number IO281. It can be made by oxidizing the Guerbet alcohol 2- heptylundecanol which is, in turn, the aldol condensation product of nonanal.
  • 2-n-Heptylundecanoic acid [25354-97-6] is available from TCI America, catalog number H0507. It can be made by oxidizing the Guerbet alcohol 2- hexyldecanol which is, in turn, the aldol condensation product of octanal.
  • Branched Chain Fattv Acid 3 2-n-Butyloctanoic Acid
  • 2-n-Butyloctanoic Acid is available from Union Carbide under the trade name ISOCARB® 12 Acid. It can be made by oxidizing the Guerbet alcohol 2- butyloctanol. Branched Chain Fattv Acid 4: 5.7.9-Trimethylnonanoic Acid
  • Alpha substituted acids can be prepared by the C-alkylation of an enamine which is derived from a straight chained aldehyde such as octanal or decanal.
  • the derived enamine will form the carbanion on the carbon alpha to the terminal nitrogen.
  • Reaction of the enamine anion with an alkyl bromide, in the presence of a catalytic amount of Nal, will give the branched chain enamine which upon hydrolysis gives the alpha alkylated aldehyde.
  • the aldehyde can the be oxidized to the corresponding carboxylic acid.
  • Decanal (aldehyde) can be reacted with an excess of a cyclic amine such as pyrrolidine, by heating at reflux in toluene in the presence of a trace amount of p- toluene sulfonic acid.
  • a cyclic amine such as pyrrolidine
  • the amine condenses with the aldehyde, water is formed and can be removed by reflux through a water trap.
  • heptylbromide and sodium iodide can be added an the alkylation completed in the same solvent system.
  • the reaction mixture is poured over ice and made acidic with 20% HCl. This hydrolysis converts the alkylated enamine to the alpha-heptyl decanal.
  • the product can be isolated by separation, washing, then drying, of the solvent layer and subsequent removal ofthe solvent by vacuum distillation.
  • Branched Chain Fattv Acid 6 9 and 10-Alkoxyoctadecanoic Acids. Other Positional Isomers. and the Corresponding Alkoxyoctadecanols.
  • Positional Isomers of Alkoxyoctadecanoic Acids The same procedure is used except that oleic acid is first isomerized to a mixture of unsaturated acids by heating with methanesulfonic acid.
  • the alkoxybromination-reduction sequence in this case leads to mixtures of additional positional isomers of alkoxyoctadecanoic acids.
  • Branched Chain Fatty Acid 7 Phenyloctadecanoic Acid. Alkylphenyloctadecanoic Acid, and the Corresponding Octadecanols.
  • Phenyloctadecanoic Acid The method of Nakano and Foglia described in The Journal of the American Oil Chemists Society, (1984),61(3), 569-73 is used. About 5 g portion of oleic acid and about 6.91 g of benzene are treated dropwise with about 10.2 g of methanesulfonic acid at about 50C° and then allowed to stir for about 6 hours. The reaction mixture is added to water and extracted with diethyl ether. Removal of the solvents by vacuum stripping gives the crude mixture of positional isomers of phenyloctadecanoic acid.
  • Methylphenyloctadecanoic Acid The synthesis is repeated but with toluene instead of benzene to yield the mixed positional isomers of methylphenyloctadecanoic acid.
  • Branched Chain Fattv Acid 8 Phenoxyoctadecanoic Acid.
  • Hvdroxyphenyloctadecanoic Acids The method of Nakano and Foglia described in The Journal of the American Oil Chemists Society, (1984),61(3), 569- 73 is used. About 1:5:6 mole ratio of oleic acid, phenol, and methanesulfonic acid are allowed to react at about 25C° for about 48 hours. The reaction mixture is added to water and extracted with ether. The extract is stripped of solvent and phenol to give the desired crude mixed positional isomers of hydroxyphenyloctadecanoic acid.
  • Phenoxyoctadecanoic Acids The reaction is repeated with about 1:5:2 mole ratio of oleic acid, phenol, and methanesulfonic acid.
  • the isolated crude product is predominantly phenoxyoctadecanoic acid, but also contains hydroxyphenyloctadecanoic acid.
  • a purified mixture of phenoxyoctadecanoic acid positional isomers is obtained by chromatography.
  • Isostearic acids are produced from the monomeric acids obtained in the dimerization of unsaturated Cjg fatty acids, according to U.S. Pat. No. 2,812,342, issued Nov. 5, 1957 to R. M. Peters, inco ⁇ orated herein by reference.
  • Suitable branched fabric softening actives which can be mixed with the above described unsaturated fabric softening actives (DEQAs) to form the fabric softening actives of this invention can be formed using the above branched chain fatty acids, and/or the co ⁇ esponding branched chain fatty alcohols.
  • the branched chain fatty acids and/or alcohols can be used with unsaturated fatty acids and/or alcohols to form suitable mixed chain actives.
  • DEQA's are those that are prepared as a single DEQA from blends of all the different branched and unsaturated 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.
  • At least a substantial percentage of the fatty acyl groups may be unsaturated, e.g., from about 25% to 70%, preferably from about 50% to about 65%.
  • Polyunsaturated fatty acid groups can be used.
  • the total level of active containing polyunsaturated fatty acyl groups (TPU) can be from about 3% to about 30%, preferably from about 5% to about 25%, more preferably from about 10% to about 18%.
  • Both cis and trans isomers can be used, preferably 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.
  • the "percent of softener active" containing a given R* group is the same as the percentage of that same R 1 group is to the total R 1 groups used to form all ofthe softener actives.
  • the mixed branched-chain and unsaturated materials are easier to formulate than conventional saturated branched chain fabric softener actives. They can be used to form concentrated premixes that maintain their low viscosity and are therefore easier to process, e.g., pump, mix, etc. These 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 compositions of the present invention, even at ambient temperatures. This ability to process the actives at low temperatures is especially important for the polyunsaturated groups, since it mimimizes 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 use of branched chain fatty acyl groups improves the resistance to degradation while maintaining fluidity and improving softening.
  • the present invention can also contain some medium-chain biodegradable quaternary ammonium fabric softening compound, DEQA, having the above formula (1) and/or formula (2), below, wherein: each Y is -O-(O)C-, or -C(O)-O-, preferably -O-(O)C-; m is 2 or 3, preferably 2; each n is 1 to 4, preferably 2; each R substituent is a C ⁇ -C$ alkyl, preferably a methyl, ethyl, propyl, benzyl groups and mixtures thereof, more preferably a C1-C3 alkyl group; each Rl, or YR!, is a saturated Cg-Cj4 preferably a C 12- 14 hydrocarbyl, or substituted hydrocarbyl substituent (the IV is preferably about 10 or less, more preferably less than about 5), (The sum ofthe carbons in the acyl group, R ⁇ +1, when Y is -O-(O)C
  • the saturated Cg-Ci4 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.
  • the groups are preferably saturated, e.g., the IV is preferably less than about 10, preferably less than about 5.
  • the branched R and R 1 substituents can contain various groups such as alkoxyl groups which act as branching, and a small percentage can be straight, so long as the R 1 groups maintain their basically hydrophobic character.
  • the prefe ⁇ ed compounds can be considered to be biodegradable diester variations of hardened ditallow dimethyl ammonium chloride (hereinafter referred to as "DTDMAC”), which is a widely used fabric softener. As used herein, when the diester is specified, it can include the monoester that is present.
  • DTDMAC hardened ditallow dimethyl ammonium chloride
  • At least about 80% of the DEQA is in the diester form, and from 0% to about 20% can be DEQA monoester, e.g., one YR 1 group is either -OH , or -C(O)OH, and, for Formula 1., m is 2.
  • the co ⁇ esponding diamide and/or mixed ester-amide can also include the active with one long chain hydrophobic group, e.g., one YR 1 group is either -N(R)H , or -C(O)OH.
  • any disclosure, e.g., levels, for the monoester actives is also applicable to the monoamide actives.
  • 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 prefe ⁇ ed.
  • 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.
  • each R is a methyl or ethyl group and preferably each R 1 is in the range of C15 to C19. Degrees of substitution can be present in the alkyl or unsaturated alkyl chains.
  • the anion Xw i n 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 prefe ⁇ ed DEQA of formula (2) is the "propyl" ester quaternary ammonium fabric softener active having the formula l,2-di(acyloxy)-3-trimethylammoniopropane chloride, wherein the acyl group is the same as that of DEQA 5 .
  • each R 1 may be an alkyl, branched alkyl, monounsaturated unsaturated alkyl, or polyunsaturated alkyl group.
  • the actives may contain mixtures of branched alkyl and unsaturated alkyl R 1 groups, especially within the individual molecules, in the ratios disclosed hereinbefore.
  • 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 ofthe softener active.
  • compositions of the present invention comprise less than about 40%, preferably from about 10% to about 35%, more preferably from about 12% to about 25%, and even more preferably from about 14% to about 20%, of the principal solvent, by weight ofthe composition.
  • Said principal solvent is selected to minimize solvent odor impact in the composition and to provide a low viscosity to the final composition.
  • isopropyl alcohol is not very effective and has a strong odor.
  • n-Propyl alcohol is more effective, but also has a distinct odor.
  • Several butyl alcohols also have odors but can be used for effective clarity/stability, especially when used as part of a principal solvent system to minimize their odor.
  • the alcohols are also selected for optimum low temperature stability, that is they are able to form compositions that are liquid with acceptable low viscosities and translucent, preferably clear, down to about 40°F (about 4.4°C) and are able to recover after storage down to about 20°F (about 6.7°C).
  • any principal solvent for the formulation of the liquid, concentrated, preferably clear, fabric softener compositions herein with the requisite stability is su ⁇ risingly selective.
  • Suitable solvents can be selected based upon their octanol/water partition coefficient (P).
  • Octanol/water partition coefficient of a principal solvent is the ratio between its equilibrium concentration in octanol and in water.
  • the partition coefficients of the principal solvent ingredients of this invention are conveniently given in the form of their logarithm to the base 10, logP.
  • the logP of many ingredients has been reported; for example, the Pomona92 database, available from Daylight Chemical Information Systems, Inc. (Daylight CIS), Irvine, California, contains many, along with citations to the original literature. However, the logP values are most conveniently calculated by the "CLOGP” program, also available from Daylight CIS. This program also lists experimental logP values when they are available in the Pomona92 database.
  • 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.
  • the fragment approach is based on the chemical structure of each ingredient, and takes into account the numbers and types of atoms, the atom connectivity, and chemical bonding.
  • the ClogP values which are the most reliable and widely used estimates for this physicochemical property, are preferably used instead of the experimental logP values in the selection of the principal solvent ingredients which are useful in the present invention.
  • Other methods that can be used to compute ClogP include, e.g., Crippen's fragmentation method as disclosed in J. Chem. Inf. Comput. Sci., 27, 21 (1987); Viswanadhan's fragmentation method as disclose in J. Chem. Inf. Comput. Sci., 29, 163 (1989); and Broto's method as disclosed in Eur. J. Med. Chem. - Chim. Theor., 19, 71 (1984).
  • the principal solvents herein are selected from those having a ClogP of from about 0.15 to about 0.64, preferably from about 0.25 to about 0.62, and more preferably from about 0.40 to about 0.60, said principal solvent preferably being asymmetric, and preferably having a melting, or solidification, point that allows it to be liquid at, or near room temperature. Solvents that have a low molecular weight and are biodegradable are also desirable for some pu ⁇ oses.
  • asymmetric solvents appear to be very desirable, whereas the highly symmetrical solvents, having a center of symmetry, such as 1,7-heptanediol, or 1,4- bis(hydroxymethyl)cyclohexane, appear to be unable to provide the essentially clear compositions when used alone, even though their ClogP values fall in the prefe ⁇ ed range.
  • One can select the most suitable principal solvent by determining whether a composition containing about 27% di(oleyoyloxyethyl)dimethylammonium chloride, about 16-20% of principal solvent, and about 4-6% ethanol remains clear during storage at about 40°F (about 4.4°C) and recovers from being frozen at about 0°F (about -18°C).
  • the most prefe ⁇ ed principal solvents can be identified by the appearance of the freeze-dried dilute treatment compositions used to treat fabrics. These dilute compositions appear to have dispersions of fabric softener that exhibit a more uni ⁇ lamellar appearance than conventional fabric softener compositions. The closer to uni-lamellar the appearance, the better the compositions seem to perform. These compositions provide su ⁇ risingly good fabric softening as compared to similar compositions prepared in the conventional way with the same fabric softener active. The compositions also inherently provide improved perfume deposition as compared to conventional fabric softening compositions, especially when the perfume is added to the compositions at, or near, room temperature.
  • Operable principal solvents are listed below under various listings, e.g., aliphatic and/or alicyclic diols with a given number of carbon atoms; monols; derivatives of glycerine; alkoxylates of diols; and mixtures of all of the above.
  • the prefe ⁇ ed principal solvents are in italics and the most prefe ⁇ ed principal solvents are in bold type.
  • the reference numbers are the Chemical Abstracts Service Registry numbers (CAS No.) for those compounds that have such a number. Novel compounds have a method identified, described hereinafter, that can be used to prepare the compounds.
  • Some inoperable principal solvents are also listed below for comparison purposes.
  • the inoperable principal solvents can be used in mixtures with operable principal solvents.
  • Operable principal solvents can be used to make concentrated fabric softener compositions that meet the stability/clarity requirements set forth herein.
  • diol principal solvents that have the same chemical formula can exist as many stereoisomers and/or optical isomers.
  • Each isomer is normally assigned with a different CAS No.
  • different isomers of 4-methyl-2,3-hexanediol are assigned to at least the following CAS Nos: 146452-51-9; 146452-50-8; 146452-49- 5; 146452-48-4; 123807-34-1; 123807-33-0; 123807-32-9; and 123807-31-8.
  • 1,3-propanediol 2-( 1 , 1 -dimethylpropyl)- Method D 1,3-propanediol, 2-( 1 ,2-dimethylpropyl)- Method D 1,3-propanediol, 2-(l-ethylpropyl)- 25462-28-6 1,3 -propanediol, 2-(2,2-dimethylpropyl)- Method D 1,3 -propanediol, 2-ethyl-2-isopropyl- 24765-55-7 1,3-propanediol, 2-methyl-2-( 1 -methylpropyl)- 813-60-5 1,3 -propanediol, 2-methyl-2-(2-methylpropyl)- 25462-42-4 1,3 -propanediol, 2-tertiary-butyl-2-methyl- 25462-45-7
  • 1,3-butanediol 2-(l-methylpropyl)- Method C 1,3-butanediol, 2-(2-methylpropyl)- Method C 1,3-butanediol, 2-butyl- 83988-22-1 1,3-butanediol, 2-methyl-2-propyl- 99799-79-8 1 ,3 -butanediol, 3-methyl-2-propyl- Method D 1,4-butanediol, 2,2-diethyl- Method H 1 ,4-butanediol, 2-ethyl-2,3-dimethyl- Method F 1 ,4-butanediol, 2-ethyl-3 , 3 -dimethyl- Method F 1 ,4-butanediol, 2-( 1 J -dimethylethyl)- 36976-70-2
  • Isomers 1,3-pentanediol, 2-ethyl-2-methyl- Method C 1,3-pentanediol, 2-ethyl-3-methyl- Method D 1,3-pentanediol, 2-ethyl-4-methyl- 148904-97-6 1,3-pentanediol, 3-ethyl-2-methyl- 55661-05-7
  • ol 4-ethyl- 1,6-hexaned ol, 2-ethyl- 1,4-hexaned ⁇ ol, 3-ethyl- 1,5-hexaned ol, 3-ethyl- 1,6-hexanedi ol, 3-ethyl- 1,2-hexanedi ol, 2-ethyl- 1,2-hexanedl ol, 3-ethyl- 1,2-hexaned; ol, 4-ethyl 2,3-hexaned ol, 3-ethyl- 2,3-hexaned ol, 4-ethyl- 3,4-hexanedi ol, 3-ethyl- 1,3-hexaned ol, 3-ethyl-
  • 1,3-heptanediol 2-methyl- 109417-38-1 1,3-heptanediol, 3-methyl- 165326-88-5 1,3-heptanediol, 4-methyl- Method C 1,3-heptanediol, 5-methyl- Method D 1,3-heptanediol, 6-methyl- Method C 1,4-heptanediol, 2-methyl- 15966-03-7 1,4-heptanediol, 3-methyl- 7748-38-1 1,4-heptanediol, 4-methyl- 72473-94-0 1,4-heptanediol, 5-methyl- 63003-04-3 1,4-heptanediol, 6-methyl- 99799-25-4 1,5-heptanediol, 2-methyl- 141605-00-7 1,5-heptanediol, 3-methyl- Method A 1,5-heptanedioi 4 methyl- Method A 1,5-heptanedio
  • 1,7-heptaned ol 2-methyl- 1,7-heptanedi ol, 3-methyl- 1,7-heptanedi ol, 4-methyl- 2,3-heptaned ol, 2-methyl- 2,3-heptanedi ol, 3-methyl- 2,3-heptanedi ol, 4-methyl- 2,3-heptanedl ol, 5-methyl- 2,3-heptanedi ol, 6-methyl- 3,4-heptanedi ol, 2-methyl- 3,4-heptanedi ol, 4-methyl- 3,4-heptaned; ol, 5-methyl- 3,4-heptaned ⁇ ol, 6-methyl- 1,2-heptanedl ol, 2-methyl- 1,2-heptanedi ol, 3-methyl- 1,2-heptaned ol, 4-methyl- 1,2-heptaned: ol, 5-methyl- 1,2-heptane
  • the unsaturated alicyclic diols include the following known unsaturated alicyclic diols:
  • EO means polyethoxylates, i.e., -(CH2CH2 ⁇ ) n H; Me-En means methyl-capped polyethoxylates -(CH2CH2 ⁇ ) n CH3 ; "2(Me-En) H means 2 Me-En groups needed; "PO” means polypropoxylates,
  • M BO means polybutyleneoxy groups
  • n-BO means poly(n-butyleneoxy) or poly- (tetramethylene)oxy groups -(CH2CH2CH2CH2 ⁇ ) n H.
  • the indicated alkoxylated derivatives are all operable and those that are preferred are in bold type and listed on the second line. Non-limiting, typical synthesis methods to prepare the alkoxylated derivatives are given hereinafter.
  • the numbers in this column are average numbers of (CH2CH2CH2CH2O) groups in the polytetramethyleneoxylated derivative.
  • the numbers in this column are average numbers of (CH(CH2CH3)CH2O) groups in the polybutoxylated derivative.
  • C ⁇ _2 mono-ols that provide a clear concentrated fabric softener compositions in the context of this invention.
  • C3 mono-ol, n- propanol that provides acceptable performance in terms of forming a clear product and either keeping it clear to a temperature of about 20°C, or allowing it to recover upon rewarming to room temperature.
  • C4 mono-ols only 2-butanol and 2- methyl-2-propanol provide very good performance, but 2-methyl-2-propanol has a boiling point that is undesirably low.
  • C5.6 mono-ols that provide clear products except for unsaturated mono-ols as described above and hereinafter.
  • principal solvents which have two hydroxyl groups in their chemical formulas are suitable for use in the formulation of the liquid concentrated, clear fabric softener compositions of this invention. It is discovered that the suitability of each principal solvent is su ⁇ risingly very selective, dependent on the number of carbon atoms, the isomeric configuration of the molecules having the same number of carbon atoms, the degree of unsaturation, etc. Principal solvents with similar solubility characteristics to the principal solvents above and possessing at least some asymmetry will provide the same benefit. It is discovered that the suitable principal solvents have a ClogP of from about 0J5 to about 0.64, preferably from about 0.25 to about 0.62, and more preferably from about 0.40 to about 0.60.
  • the 1,2-hexanediol is a good principal solvent, while many other isomers such as 1,3- hexanediol, 1,4-hexanediol, 1,5-hexanediol, 1,6-hexanediol, 2,4-hexanediol, and 2,5- hexanediol, having ClogP values outside the effective 0J5 - 0.64 range, are not.
  • Examples and Comparative Examples I-A and I-B vide infra).
  • C6 diols that are possible isomers, only the ones listed above are suitable for making clear products and only: 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 1,2-hexanediol are prefe ⁇ ed, of which the most prefe ⁇ ed are: 1,2-butanediol, 2-ethyl-; 1,2-pentaned
  • C7 diol isomers there are more possible C7 diol isomers, but only the listed ones provide clear products and the prefe ⁇ ed ones are: 1,3-butanediol, 2-butyl-; 1,4-butanediol, 2- propyl-; 1,5-pentanediol, 2-ethyl-; 2,3-pentanediol, 2,3-dimethyl-; 2,3-pentanediol, 2,4-dimethyl-; 2,3-pentanediol, 4,4-dimethyl-; 3,4-pentanediol, 2,3-dimethyl-; 1,6- hexanediol, 2-methyl-; 1,6-hexanediol, 3-methyl-; 1,3-heptanediol; 1,4-heptanediol; 1,5-fa ⁇ ptanediol; 1,6-heptanediol
  • Prefe ⁇ ed mixtures of eight-carbon-atom- 1,3 diols can be formed by the condensation of mixtures of butyraldehyde, isobutyraldehyde and/or methyl ethyl ketone (2-butanone), so long as there are at least two of these reactants in the reaction mixture, in the presence of highly alkaline catalyst followed by conversion by hydrogenation to form a mixture of eight-carbon- 1,3 -diols, i.e., a mixture of 8-carbon- 1,3-diols primarily consisting of: 2,2,4-trimethyl- 1,3-pentanediol; 2-ethyl-l,3- hexanediol; 2,2-dimethyl- 1,3-hexanediol; 2-ethyl-4-methyl-l,3-pentanediol; 2-ethyl-3- methyl- 1,3 -pentanediol; 3,5-oct
  • EO means polyethoxylates
  • En means - (CH2CH2 ⁇ ) n H
  • Me-E ⁇ means methyl-capped polyethoxylates -(CH2CH2 ⁇ ) n CH3
  • 2(Me-En) M means 2 Me-En groups needed
  • M PO means polypropoxylates, - (CH(CH3)CH2O)nH
  • BO means polybutyleneoxy groups, (CH(CH2CH3)CH2O) n H
  • n-BO means poly(n-butyleneoxy) groups - (CH 2 CH2CH2CH2 ⁇ ) n H
  • EO means polyethoxylates
  • En means - (CH2CH2 ⁇ ) n H
  • Me-E ⁇ means methyl-capped polyethoxylates -(CH2CH2 ⁇ ) n CH3
  • M means 2 Me-En groups needed
  • M PO means polypropoxylates, - (CH(CH3)CH2O)nH
  • BO means polybutyleneoxy
  • some specific diol ethers are also found to be suitable principal solvents for the formulation of liquid concentrated, clear fabric softener compositions of the present invention. Similar to the aliphatic diol principal solvents, it is discovered that the suitability of each principal solvent is very selective, depending, e.g., on the number of carbon atoms in the specific diol ether molecules.
  • the cyclohexyl derivative but not the cyclopentyl derivative
  • selectivity is exhibited in the selection of aryl glyceryl ethers. Of the many possible aromatic groups, only a few phenol derivatives are suitable.
  • the same na ⁇ ow selectivity is also found for the di(hydroxyalkyl) ethers.
  • bis(2-hydroxybutyl) ether, but not bis(2-hydroxypentyl) ether is suitable.
  • the bis(2-hydroxycyclopentyl) ether is suitable, but not the bis(2-hydroxycyclohexyl) ether.
  • Non-limiting examples of synthesis methods for the preparation of some prefe ⁇ ed di(hydroxyalkyl) ethers are given hereinafter.
  • the butyl monoglycerol ether (also named 3-butyloxy-l,2-propanediol) is not well suited to form liquid concentrated, clear fabric softeners of the present invention.
  • its polyethoxylated derivatives preferably from about triethoxylated to about nonaethoxylated, more preferably from pentaethoxylated to octaethoxylated, are suitable principal solvents, as given in Table VI.
  • Prefe ⁇ ed aromatic glyceryl ethers include: 1,2-propanediol, 3-phenyloxy-; 1,2-propanedioI, 3-benzyloxy-; 1,2- propanediol, 3-(2-phenylethyloxy)-; 1,2-propanediol, 1,3-propanediol, 2-(m- cresyloxy)-; 1,3 -propanediol, 2-(p-cresyloxy)-; 1,3 -propanediol, 2-benzyloxy-; 1,3- propanediol, 2-(2-phenylethyloxy)-; and mixtures thereof.
  • the more prefe ⁇ ed aromatic glyceryl ethers include: 1,2-propanediol, 3-phenyloxy-; 1,2-propanediol, 3- benzyloxy-; 1,2-propanediol, 3-(2-phenylethyloxy)-; 1,2-propanediol, 1,3- propanediol, 2- ⁇ m-cresyloxy)-; 1,3-propanediol, 2-(p-cresyloxy)-; 1,3 -propanediol, 2- (2-phenylethyloxy)-; and mb tures thereof.
  • the most prefe ⁇ ed di(hydroxyalkyl)ethers include: bis(2-hydroxybutyl)ether; and bis(2- hydroxycyclopentyl)ether;
  • the alicyclic diols and their derivatives that are prefe ⁇ ed include: (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-d
  • the most prefe ⁇ ed saturated alicyclic diols and their derivatives are: 1 -isopropyl- 1,2-cyclobutanediol; 3-ethyl-4-methyl-l,2- cyclobutanediol; 3-propyl-l,2-cyclobutanediol; 3-isopropyl-l,2-cyclobutanediol; 1- ethyl- 1 ,2-cyclopentanedioI; 1 ,2-dimethyl- 1 ,2-cyclopentanediol; 1 ,4-dimethyl- 1,2- cyclopentanediol; 3,3-dimethyl-l,2-cyclopentanediol; 3 ,4-dimethyl- 1,2- cyclopentanediol; 3,5-dimethyl-l,2-cyclopentanediol; 3-ethyl- 1,2-cyclopentanediol; 4,4-di
  • Prefe ⁇ ed aromatic diols include: 1 -phenyl- 1,2-ethanediol; l-phenyl-1,2- propanediol; 2-phenyl-l,2-propanediol; 3 -phenyl- 1,2-propanediol; l-(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-l,3-butanediol; and/or 1- phenyl-l,4-butanediol, of which, 1 -phenyl- 1,2-propanediol; 2-phenyl-l,2- propanediol; 3-phenyl-l,2-propaned
  • the specific prefe ⁇ ed unsaturated diol principal solvents are: 1,3-butanediol, 2,2-diaIlyl-; 1,3-butanediol, 2-(l -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-(l-methyl-2-propenyl)-; 1,4- butanediol,
  • Said principal alcohol solvent can also preferably be selected from the group consisting of: 2,5-dimethyl-2,5-hexanediol; 2-ethyl- 1,3 -hexanediol; 2-methyl-2- propyl- 1,3 -propanediol; 1,2-hexanediol; and mixtures thereof. More preferably said principal alcohol solvent is selected from the group consisting of 2-ethyl-l,3- hexanediol; 2-methyl-2-propyl-l,3-propanediol; 1,2-hexanediol; and mixtures thereof. Even more preferably, said principal alcohol solvent is selected from the groups consisting of 2-ethyl- 1,3-hexanediol; 1,2-hexanediol; and mixtures thereof.
  • 2,2-Dimethyl-6-heptene-l,3-diol (CAS No. 140192-39-8) is a prefe ⁇ ed C9- diol principal solvent and can be considered to be derived by appropriately adding a CH2 group and a double bond to either of the following prefe ⁇ ed C8-diol principal solvents: 2-methyl-l,3-heptanediol or 2,2-dimethyl- 1,3 -hexanediol.
  • 2,4-Dimethyl-5-heptene-l,3-diol (CAS No. 123363-69-9) is a prefe ⁇ ed C9- diol principal solvent and can be considered to be derived by appropriately adding a CH2 group and a double bond to either of the following prefe ⁇ ed C8-diol principal solvents: 2-methyl- 1,3 -heptanediol or 2,4-dimethyl- 1,3 -hexanediol.
  • 2-(l -Ethyl- 1 -propenyl)- 1,3 -butanediol (CAS No. 116103-35-6) is a prefe ⁇ ed C9-diol principal solvent and can be considered to be derived by appropriately adding a CH2 group and a double bond to either ofthe following prefe ⁇ ed C8-diol principal solvents: 2-(l-ethylpropyl)- 1,3 -propanediol or 2-(l -methylpropyl)- 1,3 -butanediol.
  • 2-Ethenyl-3-ethyl-l,3-pentanediol (CAS No. 104683-37-6) is a prefe ⁇ ed C9- diol principal solvent and can be considered to be derived by appropriately adding a CH2 group and a double bond to either of the following prefe ⁇ ed C8-diol principal solvents: 3 -ethyl-2-methyl- 1,3 -pentanediol or 2-ethyl-3 -methyl- 1,3 -pentanediol.
  • 3,6-Dimethyl-5-heptene-l,4-diol (e.g., CAS No. 106777-99-5) is a prefe ⁇ ed C9-diol principal solvent and can be considered to be derived by appropriately adding a CH2 group and a double bond to any of the following prefe ⁇ ed C8-diol principal solvents: 3-methyl- 1,4-heptanediol; 6-methyl- 1,4-heptanediol; or 3, 5 -dimethyl- 1,4- hexanediol.
  • 5,6-Dimethyl-6-heptene-l,4-diol is a prefe ⁇ ed C9-diol principal solvent and can be considered to be derived by appropriately adding a CH2 group and a double bond to any of the following prefe ⁇ ed C8-diol principal solvents: 5-methyl- 1,4-heptanediol; 6-methyl- 1,4-heptanediol; or 4,5-dimethyl-l,3- hexanediol.
  • 4-Methyl-6-octene-3,5-diol (CAS No. 156414-25-4) is a prefe ⁇ ed C9-diol principal solvent and can be considered to be derived by appropriately adding a CH2 group and a double bond to any ofthe following preferred C8-diol principal solvents: 3,5-octanediol, 3-methyl-2,4-heptanediol or 4-methyl-3,5-heptanediol.
  • Rosiridol (CAS No. 101391-01-9) and isorosiridol (CAS No. 149252-15-3) are two isomers of 3,7-dimethyl-2,6-octadiene-l,4-diol, and are prefe ⁇ ed ClO-diol principal solvents.
  • 8-Hydroxylinalool (CAS No. 103619-06-3, 2,6-dimethyl-2,7-octadiene-l,6- diol) is a prefe ⁇ ed ClO-diol principal solvent and can be considered to be derived by appropriately adding two CH2 groups and two double bonds to any of the following prefe ⁇ ed C8-diol principal solvents: 2-methyl- 1,5-heptanediol; 5-methyl-l, 5- heptanediol; 2-methyl- 1,6-heptanediol; 6-methyl- 1,6-heptanediol; or 2,4-dimethyl- 1,4-hexanediol.
  • 2,7-Dimethyl-3,7-octadiene-2,5-diol (CAS No. 171436-39-8) is a prefe ⁇ ed ClO-diol principal solvent and can be considered to be derived by appropriately adding two CH2 group and two double bond to any of the following prefe ⁇ ed C8- diol principal solvents.
  • 2,5-octanediol 6-methyl- 1,4-heptanediol; 2-methyl-2,4- heptanediol; 6-methyl-2,4-heptanediol; 2-methyl-2,5-heptanediol; 6-methyl-2,5- heptanediol; and 2,5-dimethyl-2,4-hexanediol.
  • 4-Butyl-2-butene-l,4-diol (CAS No. 153943-66-9) is a preferred C8-diol principal solvent and can be considered to be derived by appropriately adding a CH2 group and a double bond to any ofthe following prefe ⁇ ed C7-diol principal solvents: 2-propyl-l,4-butanediol or 2-butyl- 1,3-propanediol.
  • 3,5-dimethyl-5-hexene-2,4-diol is a poor unsaturated C8 solvent, and can be considered to be derived from the following poor saturated C7 solvents: 3-methyl-2,4-hexanediol; 5-methyl- 2,4-hexanediol; or 2,4-dimethyl- 1,3-pentanediol; and 2,6-dimethyl-5-heptene-l,2-diol (e.g., CAS No.
  • the inoperable unsaturated 2,4-dimethyl-5-hexene-2,4-diol (CAS No. 87604-24-8) having no adjacent hydroxyl groups can be considered to be derived from the prefe ⁇ ed 2,3-dimethyl-2,3- pentanediol which has adjacent hydroxyl groups.
  • an inoperable unsaturated solvent having no adjacent hydroxyl groups can be considered to be derived from an inoperable solvent which has adjacent hydroxyl groups, such as the pair 4,5-dimethyl-6-hexene-l,3-diol and 3,4-dimethyl- 1,2-pentanediol. Therefore, in order to deduce the formulatability of an unsaturated solvent having no adjacent hydroxyl groups, one should start from a low molecular weight saturated homolog also not having adjacent hydroxyl groups. I.e., in general, the relationship is more reliable when the distance/relationship ofthe two hydroxy groups is maintained. I.e., it is reliable to start from a saturated solvent with adjacent hydroxyl groups to deduce the formulatability ofthe higher molecular weight unsaturated homologs also having adjacent hydroxyl groups.
  • the principal solvents are desirably kept to the lowest levels that are feasible in the present compositions for obtaining translucency or clarity.
  • the presence of water exerts an important effect on the need for the principal solvents to achieve clarity of these compositions.
  • the softener active-to-principal solvent weight ratio is preferably from about 55:45 to about 85: 15, more preferably from about 60:40 to about 80:20.
  • the softener active-to-principal solvent weight ratio is preferably from about 45:55 to about 70:30, more preferably from about 55:45 to about 70:30. But at high water levels of from about 70% to about 80%, the softener active-to-principal solvent weight ratio is preferably from about 30:70 to about 55:45, more preferably from about 35:65 to about 45:55. At even higher water levels, the softener to principal solvent ratios should also be even higher.
  • Mixtures of the above principal solvents are particularly prefe ⁇ ed, since one of the problems associated with large amounts of solvents is safety. Mixtures decrease the amount of any one material that is present. Odor and flammability can also be mimimized by use of mixtures, especially when one ofthe principal solvents is volatile and/or has an odor, which is more likely for low molecular weight materials.
  • Suitable solvents that can be used at levels that would not be sufficient to produce a clear product are 2,2,4-trimethyl- 1,3-pentane diol; the ethoxylate, diethoxylate, or triethoxylate derivatives of 2,2,4-trimethyl- 1,3-pentane diol; and/or 2-ethyl-l,3- hexanediol.
  • these solvents should only be used at levels that will not provide a stable, or clear product.
  • Prefe ⁇ ed mixtures are those where the majority of the solvent is one, or more, that have been identified hereinbefore as most prefe ⁇ ed.
  • mixtures of solvents is also prefe ⁇ ed, especially when one, or more, of the prefe ⁇ ed principal solvents are solid at room temperature.
  • the mixtures are fluid, or have lower melting points, thus improving processability ofthe softener compositions.
  • An effective amount of the principal solvent(s) of this invention is at least greater than about 5%, preferably more than about 7%, more preferably more than about 10% ofthe composition, when at least about 15% ofthe softener active is also present.
  • the substitute solvent(s) can be used at any level, but preferably about equal to, or less than, the amount of operable principal solvent, as defined hereinbefore, that is present in the fabric softener composition.
  • HPHP hydroxy pivalyl hydroxy pivalate
  • HO-CH2-C(CH3)2-CH2-O-CO-C(CH3)2-CH2-OH are inoperable solvents according to this invention, mixtures of these solvents with the principal solvent, e.g., with the prefe ⁇ ed 1,2-hexanediol principal solvent, wherein the 1,2-hexanediol principal solvent is present at effective levels, also provide liquid concentrated, clear fabric softener compositions.
  • the principal solvent can be used to either make a composition translucent or clear, or can be used to reduce the temperature at which the composition is translucent or clear.
  • the invention also comprises the method of adding the principal solvent, at the previously indicated levels, to a composition that is not translucent, or clear, or which has a temperature where instability occurs that is too high, to make the composition translucent or clear, or, when the composition is clear, e.g., at ambient temperature, or down to a specific temperature, to reduce the temperature at which instability occurs, preferably by at least about 5°C, more preferably by at least about 10°C.
  • the principal advantage ofthe principal solvent is that it provides the maximum advantage for a given weight of solvent. It is understood that "solvent”, as used herein, refers to the effect ofthe principal solvent and not to its physical form at a given temperature, since some of the principal solvents are solids at ambient temperature. Alkyl Lactates
  • alkyl lactate esters e.g., ethyl lactate and isopropyl lactate have ClogP values within the effective range of from about 0J5 to about 0.64, and can form liquid concentrated, clear fabric softener compositions with the fabric softener actives of this invention, but need to be used at a slightly higher level than the more effective diol solvents like 1,2-hexanediol. They can also be used to substitute for part of other principal solvents of this invention to form liquid concentrated, clear fabric softener compositions. This is illustrated in Example I-C.
  • compositions of the present invention all include one or more chelating agents such as copper and/or nickel chelating agents ("chelators").
  • chelating agents of the present invention are added to aid in the reduction of color forming bodies thereby aiding the clarity ofthe clear or translucent composition and to reduce malodor. While not wishing to be bound by theory, it is believed that the addition of a chelating agent reduces or minimizes the presence of color forming bodies which may be present in the fabric softening active. In addition, the presence of a chelating agent minimizes or reduces any malodor which may be associated with the fabric softening active.
  • compositions of the present invention include the presence of a chelating agent as an essential component of the composition.
  • the chelating agent may be present in the composition in the range of from about 0.001% to about 10% by weight of the composition. More preferably the chelant is present in the range of from about 0.01% to about 5% and most preferably in the range of from about 0.01% to about 3% by weight ofthe composition.
  • 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 and all preferably in their acidic form.
  • Amino carboxylates useful as chelating agents herein include ethylenediaminetetraacetates acid (EDTA), N-hydroxyethylethylenediamine- triacetates acid, nitrilotriacetates (NTA), ethylenediamine tetraproprionates, ethylenediamine-N,N'-diglutamates, 2-hyroxypropylenediamine-N,N'-disuccinates, triethylenetetraaminehexacetates, diethylenetriaminepentaacetates (DETPA) such as diethylenetriaminepentacetic acid (DTPA), and ethanoldiglycines, including their water-soluble salts such as the alkali metal, ammonium, and substituted ammonium salts thereof and mixtures thereof.
  • EDTA ethylenediaminetetraacetates acid
  • NDA nitrilotriacetates
  • DTPA diethylenetriaminepentacetic acid
  • ethanoldiglycines including their water
  • Amino phosphonates are also suitable for use as chelating agents in the compositions of the invention 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 phos ⁇ phonate) (DETMP) and 1 -hydroxyethane- IJ -diphosphonate (HEDP).
  • these amino phosphonates to not contain alkyl or alkenyl groups with more than about 6 carbon atoms.
  • the chelating agents are typically used in the present rinse process at levels from about 2 ppm to about 25 ppm, for periods from 1 minute up to several hours' soaking.
  • the EDDS chelator which may be 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):
  • EDDS can be prepared using maleic anhydride and ethylenediamine.
  • the biodegradable [S,S] isomer of EDDS can be prepared by reacting L-aspartic acid with 1,2-dibromoethane.
  • 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.
  • the EDDS chelator is also typically used in the present rinse process at levels from about 2 ppm to about 25 ppm for periods from 1 minute up to several hours' soaking. At certain pHs the EDDS may be used in combination with zinc cations.
  • chelators may be used herein. Indeed, simple polycarboxylates such as citrate, oxydisuccinate, and the like, may 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 (ofthe 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. Prefe ⁇ ed chelators include DETMP, DETPA, DTPA, NT A, EDDS and mixtures thereof with DTPA being the most preferred.
  • compositions of the present invention comprise liquid rinse added fabric softening compositions which are clear or translucent.
  • clear compositions it is intended that the compositions of the present invention are preferably substantially free of significant color such that the compositions generally appear as clear as water.
  • a small amount of color may be present in the compositions of the present invention.
  • the compositions of the present invention will appear clear when packaged in a suitable container of an offset color shade so that the color of the composition is offset and the composition appears clear when viewed through the container.
  • the color or clarity of the present invention may be measured via a Hunter Color analysis.
  • a Hunter Color analysis is well known to one of ordinary skill in the art. The analysis is performed on a Hunter Lab ColorQuest Instrument available from Hunter Labs of Reston, Va. The Hunter Lab ColorQuest Instrument can perform two separate measurements for the pu ⁇ oses of measuring the color or clarity of the compositions of the present invention, a CEELAB color measurement and a measurement ofthe percentage (%) of Haze in the solution in the transmission mode ofthe instrument. Both measurements are run on the Hunter Lab ColorQuest Instrument using the total transmission mode. The settings for the instrument are 0.25" area view, 0.25" port size, UV filter out, no UV lamp, deionized water as the standard and a 30 mm cell.
  • CIELAB is a scale used to measure the color of solutions.
  • One of ordinary skill in the art is familiar with the CIELAB scale.
  • a Color difference measurement involves measuring the composition at the point of intial mixing and then measuring the color of the composition after a set period of time under specified conditions. The difference between the initial point in time and final point in time is then the CIELAB color difference.
  • the clear compositions have a CIELAB color difference of about 5 or less from initial to 10 days storage at 120°F, more preferably of about 1 or less and most preferably of about 0J or less.
  • Percentage haze in the transmission mode measures the amount of haze, i.e the clarity ofthe compositions.
  • the compositions ofthe present invention have a percent haze in the transmission mode of a Hunter Color analysis of about 90% or less, more preferably of about 50% or less and most preferably of about 25% or less.
  • 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 a 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).
  • These water soluble solvents have a greater affinity for water in the presence of hydrophobic materials like the softener active than the principal solvents.
  • compositions ofthe present invention include, but are not limited to, dye transfer inhibiting agents, polymeric dispersing agents, soil release agents, scum dispersants, suds suppressors, optical brighteners or other brightening or whitening agents, dye fixing agents, light fading protection agents, oxygen bleach protection agents, fabric softening clay, anti-static agents, carriers, hydrotropes, processing aids, dyes or pigments, bactericides, colorants, perfumes, preservatives, opacifiers, anti-shrinkage agents, anti-wrinkle agents, fabric crisping agents, spotting agents, germicides, fungicides, anti-co ⁇ osion agents, and the like.
  • Particularly prefe ⁇ ed optional ingredients include water soluble calcium and/or magnesium compounds, which provide additional stability.
  • the chloride salts are prefe ⁇ ed, 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%.
  • the present invention 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., inco ⁇ orated herein by reference.
  • This synthesis method is a general preparation of ⁇ , ⁇ -type diols derived from substituted cyclic alkenes.
  • cyclic alkenes are the alkylated isomers of cyclopentene, cyclohexene, and cycloheptene.
  • the general formula of useful alkylated cyclic alkenes is
  • each R is H, or C ⁇ -C4-alkyl, and where x is 3, 4, or 5.
  • Cyclic alkenes may be converted to the terminal diols by a three step reaction sequence.
  • Step 1 is the reaction ofthe cyclic alkene with ozone (O3) in a solvent such as anhydrous ethyl acetate to form the intermediate ozonide.
  • Step 2 the ozonide is reduced by, e.g., palladium catalyst /H2 to the dialdehyde which is then converted in Step 3 to the target diol by borohydride reduction.
  • the 1,2- diols are generally prepared by direct hydroxylation of the appropriate substituted olefins.
  • R ⁇ ⁇ R wherein each R is H, alkyl, etc.
  • the alkene is reacted with hydrogen peroxide (30%) and a catalytic amount of osmium tetroxide in t-butyl alcohol or other suitable solvent.
  • the reaction is cooled to about 0°C and allowed to run overnight. Unreacted compounds and solvent are removed by distillation and the desired 1,2- diol isolated by distillation or crystallization.
  • Method 2 An alternate method is the conversion of the olefin to the epoxide by the reaction of m-chloroperbenzoic acid, or peracetic acid, in a solvent such as methylene chloride at temperatures below about 25°C.
  • the epoxide generated by this chemistry is then opened to the diol by, e.g., hydrolysis with dilute sulfuric acid.
  • Step 3 to the target diol by borohydride reduction.
  • This preparation is for the general type of 1,3-diols and accommodates a variety of structural features.
  • Enamines are formed from both ketones and aldehydes which react with acid chlorides to form the acylated product.
  • the acylated amine derivative is hydrolyzed back to its acylated carbonyl compound which is the 1,3- dicarbonyl precursor to the desired 1,3-diol.
  • the diol is generated by borohydride reduction ofthe 1,3-dicarbonyl compound.
  • acetaldehyde may be reacted with a secondary amine, preferably cyclic amines such as pyrrolidine or mo ⁇ holine, by heating at reflux in a solvent such as toluene and with a catalytic amount of p-toluene sulfonic acid.
  • a secondary amine preferably cyclic amines such as pyrrolidine or mo ⁇ holine
  • water is produced and is removed, e.g., by reflux through a water trap.
  • the reaction mixture is stripped, e.g., under vacuum, to remove the solvent, if desired (the acylation can be done in the same solvent systems in most cases).
  • the typical reactions involve one or more aldehydes, one or more ketones, and mixtures thereof, which have at least one alpha-hydrogen atom on the carbon atom next to the carbonyl group.
  • Typical examples of some reactants and some potential final products are as follows
  • the aldehyde, ketone, or mixture thereof which is to be condensed is placed in an autoclave under an inert atmosphere with a solvent such as butanol or with a phase transfer medium such as polyethylene glycol.
  • a mixed condensation such as with a ketone and an aldehyde is the target, typically the two reactants are used in about 1 : 1 mole ratio.
  • a catalytic amount of strongly alkaline catalyst such as sodium methoxide is added, typically about 0.5-10 mole% of the reactants.
  • the autoclave is sealed, and the mixture is heated at about 35-100°C until most of the original reactants have been converted, usually about 5 minutes to about 3 hours.
  • the crude mixture is neutralized and the carbonyl functions present are reduced by hydrogenation over Raney Ni at about 100°C and about 50 atm for about 1 hour. Volatile components are removed by distillation and the desired diol principal solvents are obtained by vacuum distillation.
  • n-butanol about 148 g, about 2 mole, Aldrich
  • sodium metal about 2.3 g, about OJ mole, Aldrich
  • a mixture of butyraldehyde (about 72 g, about 1 mole, Aldrich) and isobutyraldehyde (about 72 g, about 1 mole, Aldrich) is added and the system is held at about 40°C until most ofthe original aldehydes have undergone reaction.
  • the base catalyst is neutralized by careful addition of sulfuric acid, any salts are removed by filtration, and the solution is hydrogenated over Raney Ni at about 100°C at about 50 atm of pressure for about 1 hour to yield a mixture of 8-carbonJ,3-diols.
  • the butanol solvent and any isobutanol formed during the hydrogenation are removed by distillation to yield the eight-carbon- 1,3 -diol mixture of: 2,2,4-trimethyl- 1,3- pentanediol; 2-ethyl-l,3-hexanediol; 2,2-dimethyl- 1,3-hexanediol; and 2-ethyl-4- methyl-l,3-pentanediol.
  • this mixture is further purified by vacuum distillation, or by decolorization with activated charcoal.
  • the recovered solvent is used for further batches of diol production.
  • the base catalyst is neutralized by careful addition of sulfuric acid and any salts are removed by filtration. Optionally, unreacted starting materials are removed by distillation along with the reaction solvent.
  • the mixture containing the condensation products is hydrogenated over Raney Ni at about 100°C and about 50 atm.
  • Condition C The above condensation is repeated except that about one mole of 2- butanone is placed in the reaction vessel with the solvent and catalyst and about one mole of butyraldehyde is gradually added. Conditions are adjusted such that the self- condensation rate of 2 -butanone is slow and the more reactive carbonyl of the aldehyde reacts promptly upon addition. This results in a reaction product with a higher proportion of the diols resulting from the condensation of 2-butanone with butyraldehyde and from self-condensation of 2-butanone and a smaller proportion of thediol resulting from self-condensation of butyraldehyde.
  • Condition D The above condensation C. is repeated under low temperature conditions. About 1.0 mole portion of 2-butanone is dissolved in about 5 volumes of dry tetrahydrofuran. The solution is cooled to about -78°C, and about 0.95 mole of potassium hydride is added in portions. After the hydrogen evolution has ceased, the solution is held for about one hour to allow for equilibration to the more stable enolate and then one mole of n-butyraldehyde is added slowly with good stirring while maintaining the temperature at about -78°C. After addition is complete, the solution is allowed to gradually warm to room temperature and is neutralized by careful addition of sulfuric acid. Salts are removed by filtration.
  • unreacted starting materials are removed by distillation along with the reaction solvent.
  • the mixture containing the condensation products is hydrogenated over Raney Ni at about 100°C and about 50 atm. for about 1 hour to yield predominantly the diol resulting from the condensation of the enolate of 2-butanone with butyraldehyde, 3,5-octanediol.
  • Purification is optionally accomplished by distillation.
  • the mixtures prepared by the condensation of butyraldehyde, isobutyraldehyde, and/or methyl ethyl ketone preferably have no more than about 90%, preferably no more than about 80%, more preferably no more than about 70%, even more preferably no more than about 60%, and most preferably no more than about 50%, by weight of any one specific compound.
  • the reaction mixtures should not contain more than about 95%, preferably no more than about 90%, more preferably no more than about 85%, and most preferably no more than about 80%, by weight, of butyraldehyde or isobutyraldehyde.
  • the resulting acetylenic diol is then reduced to the alkene or completely reduced to the saturated diol.
  • the reaction can also be done by using an about 18% slurry of mono-sodium acetylide with the carbonyl compound to form the acetylenic alcohol which can be converted to the sodium salt and reacted with another mole of carbonyl compound to give the unsaturated 1,4- diol.
  • mono-sodium acetylide with the carbonyl compound to form the acetylenic alcohol which can be converted to the sodium salt and reacted with another mole of carbonyl compound to give the unsaturated 1,4- diol.
  • a sodium acetylide (about 18% in xylene) slurry is reacted with isobutryaldehyde to form the acetylenic alcohol
  • the acetylenic (ethynyl) alcohol is converted with base to the sodium acetylide R-CHOH-C ⁇ CNa which is then reacted with a mole of acetaldehyde to give the ethynyl diol R-CHOH-C ⁇ C-CHOH-R'.
  • This method of preparation is for the synthesis of diols, especially several 1,4- diols, which are derived from dicarboxylic acid anhydrides, diesters and lactones, but not limited to the 1,4-diols or four-carbon diacids.
  • diols are generally synthesized by the reduction of the parent anhydride, lactone or diester with sodium bis(2-methoxyethoxy)aluminum hydride (Red-Al) as the reducing agent.
  • This reducing agent is commercially available as a 3J molar solution in toluene and delivers one mole of hydrogen per mole of reagent.
  • Diesters and cyclic anhydrides require about 3 moles of Red-Al per mole of substrate.
  • the typical reduction is carried out as follows.
  • the anhydride is first dissolved in anhydrous toluene and placed in a reaction vessel equipped with dropping funnel, mechanical sti ⁇ er, thermometer and a reflux condenser connected to calcium chloride and soda lime tubes to exclude moisture and carbon dioxide.
  • the reducing agent, in toluene is placed in the dropping funnel and is added slowly to the stirred anhydride solution.
  • the reaction is exothermic and the temperature is allowed to reach about 80°C. It is maintained at about 80°C during the remaining addition time and for about two hours following addition.
  • reaction mixture is then allowed to cool back to room temperature.
  • the mixture is added to a stirred aqueous HCl solution (about 20% concentration) which is cooled in an ice bath, and the temperature is maintained at about 20 to 30°C.
  • acidification the mixture is separated in a separatory funnel and the organic layer washed with a dilute salt solution until neutral to pH paper.
  • the neutral diol solution is dried over anhydrous magnesium sulfate, filtered, then stripped under vacuum to yield the desired 1,4-diol.
  • This method is a general preparation of some 1,3-, 1,4- and 1,5-diols which utilizes the chemistry outlined in Method A-1 and Method A-2.
  • the variation here is the use of a cyclic alkadienes in place of the cycloalkenes described in Methods A.
  • the general formula for the starting materials is
  • each R is H, or Cj-C4-alkyl and wherein x is 1, 2 or 3.
  • the reactions are those of Methods A with the variation of having one mole of ethylene glycol generated for each mole of the desired diol principal solvent formed, e.g., the following preparation of 2,2-dimethyl- 1,4-haxanedioI from 1-ethyl- 5,5-dimethyl-l,3-cyclohexanediol (CAS No. 79419-18-4):
  • the polyethoxylated derivatives of diol principal solvents are typically prepared in a high-pressure reactor under a nitrogen atmosphere.
  • a suitable amount of ethylene oxide is added to a mixture of a diol solvent and potassium hydroxide at high temperature (from about 80°C to about 170°C).
  • the amount of ethylene oxide is calculated relative to the amount of the diol solvent in order to add the right number of ethylene oxide groups per molecule of diol.
  • Methyl-capped polyethoxylated derivatives of diols are typically prepared either by reacting a methoxypoly(ethoxy)ethyl chloride (i.e., CH3 ⁇ -(CH2CH2 ⁇ ) n - CH2CH2-CI) of the desired chain length with the selected diol, or by reacting a methyl-capped polyethylene glycol (i.e., CH 3 O-(CH 2 CH2 ⁇ ) n -CH2CH2-OH) of the desired chain length with the epoxy precursor of the diol, or a combination of these methods.
  • a methoxypoly(ethoxy)ethyl chloride i.e., CH3 ⁇ -(CH2CH2 ⁇ ) n - CH2CH2-CI
  • a methyl-capped polyethylene glycol i.e., CH 3 O-(CH 2 CH2 ⁇ ) n -CH2CH2-OH
  • a ⁇ C-NMR (dmso-de) shows that the reaction is complete by the disappearance of the epoxide peaks.
  • the reaction mixture is cooled, poured into an equal volume of water, neutralized with 6 N HCl, saturated with sodium chloride, and extracted twice with dichloromethane.
  • the combined dichloromethane layers are dried over sodium sulfate and solvent is stripped to yield the desired polyether alcohol in crude form.
  • purification is accomplished by fractional vacuum distillation.
  • Saturated sodium chloride solution is slowly added to the material until the thionyl chloride is destroyed.
  • the material is taken up in about 300 ml of saturated sodium chloride solution and extracted with about 500 ml of methylene chloride.
  • the organic layer is dried and solvent is stripped on a rotary evaporator to yield crude methoxyethoxyethyl chloride.
  • purification is accomplished by fractional vacuum distillation.
  • the alcohol C 2 H 5 CH(OH)CH(CH 3 )CH2OH (about 116 grams, about 1.0 mole), is placed in a 1 -liter, three-neck round bottom flask equipped with a magnetic stirring bar, condenser, and temperature controller (Thermowatch®, I 2 R) along with about 100 ml of tetrahydrofuran as solvent.
  • sodium hydride about 32 grams, about 1.24 moles
  • Methoxytriethoxyethyl chloride about 242 grams, about 1.2 moles, prepared as above is added and the system is held at reflux for about 48 hours.
  • the reaction mixture is cooled to room temperature and water is cautiously added dropwise with stirring to decompose excess hydride.
  • the tetrahydrofuran is stripped off on a rotary evaporator.
  • the crude product is dissolved in about 400 ml of water and enough sodium chloride is dissolved in the water to bring it nearly to the saturation level.
  • the mixture is then extracted twice with about 300 ml portions of dichloromethane.
  • the combined dichloromethane layers are dried over sodium sulfate and the solvent is then stripped on a rotary evaporator to yield the crude product.
  • purification is accomplished by further stripping of unreacted starting materials and low MW by-products by utilizing a kugelrohr apparatus at about 150°C under vacuum.
  • further purification is accomplished by vacuum distillation to yield the title polyether.
  • the rea ⁇ ion mixture is then heated to about 80-130°C and propylene oxide (Aldrich) is added dropwise from the dropping funnel at a rate to maintain a small amount of reflux from the solid CO2-cooled condenser. Addition of propylene oxide is continued until the desired amount has been added for the target degree of propoxylation. Heating is continued until all reflux of propylene oxide ceases and the temperature is maintained for about an additional hour to ensure complete reaction.
  • the reaction mixture is then cooled to room temperature and is neutralized by careful addition of a convenient acid such as methanesulfonic acid. Any salts are removed by filtration to give the desired propoxylated product.
  • the average degree of propoxylation is typically confirmed by integration ofthe 1 H-NMR spectrum.
  • a three neck, round bottom flask is equipped with a magnetic stir bar, a solid CO2-cooled condenser, an addition funnel, a thermometer, and a temperature control device (Therm-O-Watch, I2R).
  • the system is swept free of air by a stream of nitrogen and then is equipped for blanketing the reaction mixture with a nitrogen atmosphere.
  • To the reaction flask is added the dry alcohol or diol to be butoxylated. About 0J-5 mole % of sodium metal is added cautiously to the reaction vessel in portions with heating if necessary to get all the sodium to react.
  • reaction mixture is then heated to about 80-130°C and ⁇ -butylene oxide (Aldrich) is added dropwise from the dropping funnel at a rate to maintain a small amount of reflux from the solid CO2-cooled condenser. Addition of butylene oxide is continued until the desired amount has been added for the target degree of butoxylation. Heating is continued until all reflux of butylene oxide ceases and the temperature is maintained for about an additional one to two hours to ensure complete reaction.
  • the reaction mixture is then cooled to room temperature and is neutralized by careful addition of a convenient acid such as methanesulfonic acid. Any salts are removed by filtration to give the desired butoxylated product. The average degree of butoxylation is typically confirmed by integration ofthe H-NMR spectrum.
  • sodium hydride (about 5 mole % excess relative to the chloro compound) is added in small portions with good stirring while maintaining a temperature of about 30-120°C After all the hydride has reacted, the temperature is maintained until all of the alcohol groups have been alkylated, usually about 4-24 hours. After the reaction is complete, it is cooled and the excess hydride is decomposed by careful addition of methanol in small portions. Then about an equal volume of water is added and the pH is adjusted to about 2 with sulfuric acid. After warming to about 40°C and holding it there for about 15 minutes to hydrolyze the tetrahydropyranyl protecting group, the reaction mixture is neutralized with sodium hydroxide and the solvents are stripped on a rotary evaporator.
  • the residue is taken up in ether or methylene chloride and salts are removed by filtration. Stripping yields the crude tetramethyleneoxylated alcohol or diol. Further purification may be accomplished by vacuum distillation. If a final average degree of tetramethyleneoxylation of less than one is desired, a co ⁇ espondingly lesser amount of chloro compound and hydride are used. For average degrees of tetramethyleneoxylation greater than one, the entire process is repeated in cycles until the buildup reaches the target level.
  • alkyl and/or aryl monoglycerol ethers consists of first preparing the co ⁇ esponding alkyl glycidyl ether precursor. This is then converted to a ketal, which is then hydrolyzed to the monoglyceryl ether (diol). Following is the illustrative example of the preparation of the preferred n-pentyl monoglycerol ether, (i.e., 3-(pentyloxy)-l,2-propanediol) n-C5Hn-O-CHOH- CH 2 OH. Preparation of 3-(pentyloxy)- 1 ,2-propanediol
  • a 3-neck, 2-liter round bottomed reaction flask (equipped with overhead stirrer, cold water condenser, mercury thermometer and addition funnel) are charged with about 546 g of aqueous NaOH (about 50% concentration) and about 38.5 g of tetrabutylammonium hydrogen sulfate (PTC, phase transfer catalyst). The content of the flask is stirred to achieve dissolution and then about 200 g of 1-pentanol is added along with about 400 ml hexanes (a mixture of isomers, with about 85% n-hexane).
  • PTC tetrabutylammonium hydrogen sulfate
  • 1-pentanol 1-pentanol is added along with about 400 ml hexanes (a mixture of isomers, with about 85% n-hexane).
  • epichlorohydrin which is slowly added (dropwise) to the stirring reaction mix. The temperature gradually rises to about 68°C due to the reaction ex
  • the crude reaction mix is diluted with about 500 ml of warm water, stirred gently and then the aqueous layer is settled and removed.
  • the hexane layer is mixed diluted again with about 1 liter of warm water and the pH of the mix is adjusted to about 6.5 by the addition of dilute aqueous sulfuric acid.
  • the water layer is again separated and discarded and the hexane layer is then washed 3 times with fresh water.
  • the hexane layer is then separated and evaporated to dryness via a rotary evaporator to obtain the crude n-pentyl glycidyl ether.
  • a 3 -neck, 2 liter round bottomed flask (equipped with an overhead sti ⁇ er, cold water condenser, mercury thermometer and addition funnel) is charged with about 1 liter of acetone.
  • To the acetone is added about 1 ml of SnCl4 with stirring.
  • Into an addition funnel positioned over the rea ⁇ ion flask is added about 200 g ofthe just prepared n-pentyl glycidyl ether.
  • the glycidyl ether is added very slowly to the stirring acetone solution (the rate is adjusted to control the exotherm).
  • the rea ⁇ ion is allowed to proceed for about 1 hr after complete addition of the glycidyl ether (maximum temperature about 52°C).
  • the apparatus is converted for distillation and a heating mantle and temperature controller are added.
  • the crude rea ⁇ ion mix is concentrated via distillation of about 600 ml of acetone.
  • To the cooled concentrated solution are added about 1 liter of aqueous sulfuric acid (about 20% concentration) and about 500 ml of hexanes.
  • the content of the flask is then heated to about 50°C with stirring (the apparatus is adjusted to colle ⁇ and separate the liberated acetone).
  • the hydrolysis rea ⁇ ion is continued until TLC (Thin Layer Chromatography) analysis confirms the completion of rea ⁇ ion.
  • the crude rea ⁇ ion mix is cooled and the aqueous layer is separated and discarded.
  • the organic layer is then diluted with about 1 liter of warm water and the pH is adjusted to about 7 by the addition of dilute aqueous NaOH (IN).
  • the aqueous layer is again separated and the organic phase is washed 3 times with fresh water.
  • the organic phase is then separated and evaporated via a rotary evaporator.
  • the residue is then diluted with fresh hexanes and the desired produ ⁇ is extra ⁇ ed into m ⁇ hanol/water solution (about 70/30 weight ratio).
  • the methanol water solution is again evaporated to dryness via a rotary evaporator (with additional methanol added to facilitate the water evaporation).
  • reaction mixture is neutralized with sulfuric acid, the salts are removed by filtration, and the liquid is fra ⁇ ionally distilled under vacuum to recover the excess butanediol.
  • the desired ⁇ her is obtained as a residue.
  • it is purified by further vacuum distillation.
  • 1,2-cyclopentanediol about 306 g, about 3 moles, Aldrich
  • boron trifluoride diethyl etherate about 0.14 g, about 0.01 moles, cis-trans isomer mixture,
  • the rea ⁇ ion mixture is neutralized with sodium hydroxide, and the liquid is fra ⁇ ionally distilled under vacuum to recover the excess cyclopentanediol.
  • the desired ether is obtained as a residue.
  • it is purified by further vacuum distillation.
  • compositions in the Examples below are made by first preparing an oil seat of DEQA softener a ⁇ ive at ambient temperature.
  • the softener a ⁇ ive can be heated to melting at, e.g., about 130-150°F (about 55-66°C), if the softener active is not fluid at room temperature.
  • the softener a ⁇ ive is mixed using an IKA RW 25® mixer for about 2 to about 5 minutes at about 150 ⁇ m.
  • an acid/water seat is prepared by mixing the HCl with deionized (DI) water at ambient temperature. Chelant is then added to the water seat.
  • DI deionized
  • the acid/water seat should also be heated to a suitable temperature, e.g., about 100°F (about 38°C) and maintaining said temperature with a water bath.
  • the principal solvent(s) melted at suitable temperatures if their melting points are above room temperature
  • the acid water seat is then added to the softener premix and mixed for about 20 to about 30 minutes or until the composition is clear and homogeneous.
  • the composition is allowed to air cool to ambient temperature.
  • TPU Total polyunsaturated fatty acyl groups, by weight.
  • ClogP values of 2-ethyl- 1,3 -hexanediol and 1,2-hexanediol are 0.60 and 0.53, respe ⁇ ively, and are within the prefe ⁇ ed ClogP range.
  • Example IA All 1,2-alkanediols in Example IA, except 1,2-hexanediol, have ClogP values outside the effe ⁇ ive 0.15 to 0.64 range. Only the composition of Example 1-8, containing 1,2-hexanediol, is a clear composition with acceptable viscosities both at room temperature and at about 40°F (about 4°C); compositions of Comparative
  • Examples I-8A to I-8F are not clear and/or do not have acceptable viscosities.
  • Example IB All hexanediol isomers in Example IB, except 1,2-hexanediol, have ClogP values outside the effe ⁇ ive 0.15 to 0.64 range. Only the composition of Example I- 8, containing 1,2-hexanediol, is a clear composition with acceptable viscosities both at room temperature and at about 40°F (about 4°C); compositions of Comparative Examples I-8G to I-8L are not clear and/or do not have acceptable viscosities. EXAMPLE I-C
  • compositions of Example 1-8, I-8M, and I-8N which contain effe ⁇ ive levels of the prefe ⁇ ed 1,2-hexanediol principal solvent are clear compositions with acceptable viscosities both at room temperature and at about 40°F (about 4°C).
  • the compositions of Example I-8O and I-8P which contain effe ⁇ ive levels of the prefe ⁇ ed 1,2-hexanediol principal solvent are clear compositions with acceptable viscosities at room temperature, and are clear at about 40°F (about 4°C) with a small layer which is separated on top, but recover and become clear when brought back to room temperature.
  • the compositions of Comparative Examples I-8Q which does not contain an effe ⁇ ive amount of the prefe ⁇ ed 1,2-hexanediol is not clear and/or does not have acceptable viscosities.
  • a clear fabric softener having the following composition was prepared and measured for clarity.
  • the clarity was measured on a Hunter Lab ColorQuest Instrument in the total transmission mode with a 0.25" area view, a 0.25" port size, the UV filter out, no UV lamp, deionized water as the standard and a 30mm cell.
  • the composition had a CIELAB difference from initial to 10 days storage at 120°F of 0.04 with DTPA and 20.37 without DTPA.
  • the percetage haze of the composition in the transmission mode when DTPA is included is 1.51%.
  • the principal solvents B. and some mixtures of principal solvents B. and secondary solvents, as disclosed hereinbefore, allow the preparation of premixes comprising the softener active A. (from about 55% to about 85%, preferably from about 60% to about 80%, more preferably from about 65% to about 75%, by weight of the premix); the principal solvent B. (from about 10% to about 30%, preferably from about 13% to about 25%, more preferably from about 15% to about 20%, by weight ofthe premix); and optionally, the water soluble solvent C (from about 5% to about 20%, preferably from about 5% to about 17%, more preferably from about 5% to about 15%, by weight ofthe premix).
  • premixes can optionally be replaced by a mixture of an effective amount of principal solvents B. and some inoperable solvents, as disclosed hereinbefore.
  • These premixes contain the desired amount of fabric softening a ⁇ ive A. and sufficient principal solvent B., and, optionally, solvent C, to give the premix the desired viscosity for the desired temperature range.
  • Typical viscosities suitable for processing are less than about 1000 cps, preferably less than about 500 cps, more preferably less than about 300 cps.
  • Use of low temperatures improves safety, by minimizing solvent vaporization, minimizes the degradation and/or loss of materials such as the biodegradable fabric softener a ⁇ ive, perfumes, etc., and reduces the need for heating, thus saving on the expenses for processing. The result is improved environmental impact and safety from the manufacturing operation.
  • premixes and processes using them include premixes which typically contain from about 55% to about 85%, preferably from about 60% to about 80%, more preferably from about 65% to about 75%, of fabric softener a ⁇ ive A., as exemplified with DEQA 1 and DEQA 8 in the Examples hereinafter, mixed with from about 10% to about 30%, preferably from about 13% to about 25%, more preferably from about 15% to about 20%, of principal solvent such as 1,2-hexanediol, and from about 5% to about 20%, preferably from about 5% to about 15%, of water soluble solvent C. like ethanol and/or isopropanol.
  • principal solvent such as 1,2-hexanediol
  • water soluble solvent C like ethanol and/or isopropanol.
  • premixes can be used to formulate finished compositions in processes comprising the steps of:
  • the fabric softening actives (DEQAs); the principal solvents B.; and, optionally, the water soluble solvents, can be formulated as premixes which can be used to prepare the following compositions.
  • the above compositions are introduced into containers, specifically bottles, and more specifically clear bottles (although translucent bottles can be used), made from polypropylene (although glass, oriented polyethylene, etc., can be substituted).
  • the bottle may have a light blue tint to compensate for any yellow color that is present, or that may develop during storage.
  • clear containers with no tint, or other tints can be used.
  • the bottles may also have an ultraviolet light absorber in the bottle to minimize the effe ⁇ s of ultraviolet light on the materials inside, especially the highly unsaturated a ⁇ ives (the absorbers can also be on the surface). The overall effe ⁇ of the clarity and the container being to demonstrate the clarity of the compositions, thus assuring the consumer ofthe quality ofthe produ ⁇ .

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PCT/US1996/011572 1995-07-11 1996-07-11 Concentrated, stable fabric softening compositions including chelants WO1997003172A1 (en)

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CA002226550A CA2226550C (en) 1995-07-11 1996-07-11 Concentrated, stable fabric softening compositions including chelants
BR9609823A BR9609823A (pt) 1995-07-11 1996-07-11 Composição de amaciamento de pano estável concentrada incluindo quelantes
AU66365/96A AU6636596A (en) 1995-07-11 1996-07-11 Concentrated, stable fabric softening compositions including chelants
JP50599197A JP3916666B2 (ja) 1995-07-11 1996-07-11 キレート化剤を含む濃縮した安定な布帛柔軟化組成物
MX9800381A MX9800381A (es) 1995-07-11 1996-07-11 Composiciones suavizadoras de telas, concentradas, estables que incluyen quelatadores.
EP96926070A EP0839180A1 (en) 1995-07-11 1996-07-11 Concentrated, stable fabric softening compositions including chelants
US11/044,560 US20050202998A1 (en) 1996-07-11 2005-01-27 Concentrated, stable, translucent or clear, fabric softening compositions including chelants

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US105795P 1995-07-11 1995-07-11
US60/001,057 1995-07-11
US62101996A 1996-03-22 1996-03-22
US08/621,019 1996-03-22

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WO1998008924A3 (en) * 1996-08-30 1998-05-07 Procter & Gamble Concentrated premix with reduced flammability for forming fabric softening composition
WO1998053035A1 (en) * 1997-05-19 1998-11-26 The Procter & Gamble Company Clear or translucent fabric softener compositions using mixture of solvents
WO1999045089A1 (en) * 1998-03-02 1999-09-10 The Procter & Gamble Company Concentrated, stable, translucent or clear, fabric softening compositions
US6432911B1 (en) 1999-07-07 2002-08-13 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Fabric conditioning compositions
US6916781B2 (en) 1999-03-02 2005-07-12 The Procter & Gamble Company Concentrated, stable, translucent or clear, fabric softening compositions
US6995131B1 (en) * 1999-05-10 2006-02-07 The Procter & Gamble Company Clear or translucent aqueous fabric softener compositions containing high electrolyte and optional phase stabilizer
US6998381B2 (en) * 1997-07-29 2006-02-14 The Procter & Gamble Company Concentrated, stable, preferably clear, fabric softening composition containing amine fabric softener
WO2009015954A1 (en) * 2007-07-27 2009-02-05 Unilever Plc Fabric softening composition
US9790454B2 (en) 2016-03-02 2017-10-17 The Procter & Gamble Company Compositions containing alkyl sulfates and/or alkoxylated alkyl sulfates and a solvent comprising a diol
US9840684B2 (en) 2016-03-02 2017-12-12 The Procter & Gamble Company Compositions containing alkyl sulfates and/or alkoxylated alkyl sulfates and a solvent comprising a diol
US9856440B2 (en) 2016-03-02 2018-01-02 The Procter & Gamble Company Compositions containing anionic surfactant and a solvent comprising butanediol
US9896648B2 (en) 2016-03-02 2018-02-20 The Procter & Gamble Company Ethoxylated diols and compositions containing ethoxylated diols

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DE69733579D1 (de) * 1997-08-18 2005-07-21 Procter & Gamble Durchsichtige flüssige gewebeweichmacherzusammensetzungen
US6875735B1 (en) * 1997-11-24 2005-04-05 The Procter & Gamble Company Clear or translucent aqueous fabric softener compositions containing high electrolyte content and optional phase stabilizer
US6486121B2 (en) * 1998-04-15 2002-11-26 The Procter & Gamble Company Softener active derived from acylated triethanolamine
US6995124B1 (en) 1998-10-24 2006-02-07 The Procter & Gamble Company Methods for laundering delicate garments in a washing machine
US6966696B1 (en) 1998-10-24 2005-11-22 The Procter & Gamble Company Methods for laundering delicate garments in a washing machine
US7185380B2 (en) 1998-10-24 2007-03-06 The Procter & Gamble Company Methods for laundering delicate garments in a washing machine comprising a woven acrylic coated polyester garment container
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WO2003010265A1 (en) * 2000-05-24 2003-02-06 The Procter & Gamble Company A fabric softening composition comprising a malodor controlling agent
DE10046434A1 (de) * 2000-09-20 2002-04-04 Cognis Deutschland Gmbh Verfahren zur Herstellung von verzweigten Alkoholen und/oder Kohlenwasserstoffen
US6946501B2 (en) 2001-01-31 2005-09-20 The Procter & Gamble Company Rapidly dissolvable polymer films and articles made therefrom
DE10320433A1 (de) * 2003-05-08 2005-02-17 Henkel Kgaa Frostresistente Konditioniermittel
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WO2006124338A1 (en) * 2005-05-12 2006-11-23 The Procter & Gamble Company Fabric softening compositions stable under freeze-thaw conditions
JP4579055B2 (ja) * 2005-06-01 2010-11-10 花王株式会社 透明又は半透明の液体柔軟剤組成物
CN1940045B (zh) * 2005-09-27 2010-09-22 深圳市城洁宝环保科技有限公司 粘胶清除液
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ES2385433T3 (es) * 2007-12-14 2012-07-24 Unilever N.V. Sistema adyuvante para una composición detergente
US8232239B2 (en) * 2010-03-09 2012-07-31 Ecolab Usa Inc. Liquid concentrated fabric softener composition
US10689600B2 (en) 2016-01-25 2020-06-23 The Procter & Gamble Company Treatment compositions
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CN106242954B (zh) * 2016-08-01 2019-03-15 山东一诺威新材料有限公司 聚醚胺用低分子量聚醚多元醇的制备方法
CN112534031A (zh) * 2018-07-18 2021-03-19 德国德之馨香精香料公司 洗涤剂组合物

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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998008924A3 (en) * 1996-08-30 1998-05-07 Procter & Gamble Concentrated premix with reduced flammability for forming fabric softening composition
WO1998053035A1 (en) * 1997-05-19 1998-11-26 The Procter & Gamble Company Clear or translucent fabric softener compositions using mixture of solvents
US6998381B2 (en) * 1997-07-29 2006-02-14 The Procter & Gamble Company Concentrated, stable, preferably clear, fabric softening composition containing amine fabric softener
JP4781527B2 (ja) * 1997-07-29 2011-09-28 ザ プロクター アンド ギャンブル カンパニー アミン布地柔軟剤を含有する濃縮された安定な、好ましくは透明な布地柔軟組成物
WO1999045089A1 (en) * 1998-03-02 1999-09-10 The Procter & Gamble Company Concentrated, stable, translucent or clear, fabric softening compositions
US6608024B1 (en) * 1998-03-02 2003-08-19 The Procter & Gamble Company Concentrated, stable, translucent or clear, fabric softening compositions
US6916781B2 (en) 1999-03-02 2005-07-12 The Procter & Gamble Company Concentrated, stable, translucent or clear, fabric softening compositions
US6995131B1 (en) * 1999-05-10 2006-02-07 The Procter & Gamble Company Clear or translucent aqueous fabric softener compositions containing high electrolyte and optional phase stabilizer
US6432911B1 (en) 1999-07-07 2002-08-13 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Fabric conditioning compositions
WO2009015954A1 (en) * 2007-07-27 2009-02-05 Unilever Plc Fabric softening composition
US9790454B2 (en) 2016-03-02 2017-10-17 The Procter & Gamble Company Compositions containing alkyl sulfates and/or alkoxylated alkyl sulfates and a solvent comprising a diol
US9840684B2 (en) 2016-03-02 2017-12-12 The Procter & Gamble Company Compositions containing alkyl sulfates and/or alkoxylated alkyl sulfates and a solvent comprising a diol
US9856440B2 (en) 2016-03-02 2018-01-02 The Procter & Gamble Company Compositions containing anionic surfactant and a solvent comprising butanediol
US9896648B2 (en) 2016-03-02 2018-02-20 The Procter & Gamble Company Ethoxylated diols and compositions containing ethoxylated diols

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