EP0842250B1 - Konzentrierte, stabile textilweichmacherzusammensetzung - Google Patents
Konzentrierte, stabile textilweichmacherzusammensetzung Download PDFInfo
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- EP0842250B1 EP0842250B1 EP96924436A EP96924436A EP0842250B1 EP 0842250 B1 EP0842250 B1 EP 0842250B1 EP 96924436 A EP96924436 A EP 96924436A EP 96924436 A EP96924436 A EP 96924436A EP 0842250 B1 EP0842250 B1 EP 0842250B1
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- EP
- European Patent Office
- Prior art keywords
- composition
- group
- cyclohexanediol
- fabric softener
- principal solvent
- Prior art date
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Classifications
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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 preferably translucent, or, more preferably, clear, aqueous, liquid softening compositions useful for softening cloth. It especially relates to textile softening compositions for use in the rinse cycle of a textile laundering operation to provide excellent fabric-softening/static-control benefits, the compositions being 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.
- EP-A-0 296 995 discloses softening compositions comprising a softening compound (A), a cationic compound (B) having a better water-solubility than (A), and a solvent (C).
- WO-A-96/33800 published on 31 st October 1996, discloses a homogeneous liquid composition comprising one or more cationic, anionic, amphoteric or nonionic agent with a diol and/or diol alkoxylate like 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-ethylhexyl-1,3-diol.
- the present invention provides aqueous liquid textile treatment compositions with low organic solvent level (i.e. below about 40%, by weight of the composition), 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 subnormal temperatures under prolonged storage conditions.
- Said compositions also provide reduced staining of fabrics, good cold water dipersibility, together with excellent softening, anti-static and fabric rewettability characteristics, as well as reduced dispenser residue buildup and excellent freeze-thaw recovery.
- the object of the present invention is to provide aqueous, translucent, or, preferably, clear, rinse-added liquid fabric softening compositions which provide one, or more benefits such as reduced staining on fabrics, ready dispersibility in rinse water, phase stability at low temperatures, and/or, preferably acceptable viscosity and viscosity stability at low temperatures, and/or recovery from freezing.
- compositions herein comprise:
- 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 83:15, 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 befrom 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.
- 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 of the 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, preferably clear, fabric softener compositions herein with the requisite stability is surprisingly 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.
- 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 purposes.
- 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 preferred 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 preferred 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 unilamellar appearance than conventional fabric softener compositions. The closer to uni-lamellar the appearance, the better the compositions seem to perform. These compositions provide surprisingly 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.
- the reference numbers are the Chemical Abstracts Service Registry numbers (CAS No.) for those compounds that have such a number.
- 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.
- compositions containing both saturated and unsaturated diester quaternary ammonium compounds can be prepared that are stable without the addition of concentration aids.
- the compositions of the present invention may require organic and/or inorganic concentration aids to go to even higher concentrations and/or to meet higher stability standards depending on the other ingredients.
- concentration aids which typically can be viscosity modifiers may be needed, or preferred, for ensuring stability under extreme conditions when particular softener active levels are used.
- the surfactant concentration aids are typically selected from the group consisting of (1) single long chain alkyl cationic surfactants; (2) nonionic surfactants; (3) amine oxides; (4) fatty acids; and (5) mixtures thereof.
- the total level is from about 2% to about 25%, preferably from about 3% to about 17%, more preferably from about 4% to about 15%, and even more preferably from 5% to about 13% by weight of the composition.
- These materials can either be added as part of the active softener raw material, (I), e.g., the mono-long chain alkyl cationic surfactant and/or the fatty acid which are reactants used to form the biodegradable fabric softener active as discussed hereinbefore, or added as a separate component.
- the total level of dispersibility aid includes any amount that may be present as part of component (I).
- the mono-alkyl cationic quaternary ammonium compound When the mono-alkyl cationic quaternary ammonium compound is present, it is typically present at a level of from about 2% to about 25%, preferably from about 3% to about 17%, more preferably from about 4% to about 15%, and even more preferably from 5% to about 13% by weight of the composition, the total mono-alkyl cationic quaternary ammonium compound being at least at an effective level.
- Such mono-alkyl cationic quaternary ammonium compounds useful in the present invention are, preferably, quaternary ammonium salts of the general formula: [R 4 N + (R 5 ) 3 ] X - wherein R 4 is C 8 -C 22 alkyl or alkenyl group, preferably C 10 -C 18 alkyl or alkenyl group; more preferably C 10 -C 14 or C 16 -C 18 alkyl or alkenyl group; each R 5 is a C 1 -C 6 alkyl or substituted alkyl group (e.g., hydroxy alkyl), preferably C 1 -C 3 alkyl group, e.g., methyl (most preferred), ethyl, propyl; and the like, a benzyl group, hydrogen, a polyethoxylated chain with from about 2 to about 20 oxyethylene units, preferably from about 2.5 to about 13 oxyethylene units, more preferably from about 3 to about 10 oxyethylene units,
- Especially preferred dispersibility aids are monolauryl trimethyl ammonium chloride and monotallow trimethyl ammonium chloride available from Witco under the trade name Varisoft® 471 and monooleyl trnnethyl ammonium chloride available from Witco under the tradename Varisoft® 417.
- the R 4 group can also be attached to the cationic nitrogen atom through a group containing one, or more, ester, amide, ether, amine, etc., linking groups which can be desirable for increased concentratability of component (1), etc.
- Such linking groups are preferably within from about one to about three carbon atoms of the nitrogen atom.
- Mono-alkyl cationic quaternary ammonium compounds also include C 8 -C 22 alkyl choline esters.
- the preferred dispersibility aids of this type have the formula: R 1 C(O)-O-CH 2 CH 2 N + (R) 3 X - wherein R 1 , R and X - are as defined previously.
- Highly preferred dispersibility aids include C 12 -C 14 coco choline ester and C 16 -C 18 tallow choline ester.
- the compositions also contain a small amount, preferably from about 2% to about 5% by weight of the composition, of organic acid.
- organic acids are described in European Patent Application No. 404,471, Machin et al., published on Dec. 27, 1990, supra, which is herein incorporated by reference.
- the organic acid is selected from the group consisting of glycolic acid, acetic acid, acid, and mixtures thereof.
- Ethoxylated quaternary ammonium compounds which can serve as the dispersibility aid include ethylbis(polyethoxy ethanol)alkylammonium ethyl-sulfate with 17 moles of ethylene oxide, available under the trade name Variquat® 66 from Sherex Chemical Company, polyethylene glycol (15) oleammonium chloride, available under the trade name Ethoquad® 0/25 from Akzo; and polyethylene glycol (15) cocomonium chloride, available under the trade name Ethoquad® C/25 from Akzo.
- the dispersibility aid is to increase the dispersibility of the ester softener
- the dispersibility aids of the present invention also have some softening properties to boost softening performance of the composition. Therefore, preferably the compositions of the present invention are essentially free of non-nitrogenous ethoxylated nonionic dispersibility-aids which will decrease the overall softening performance of the compositions.
- quaternary compounds having only a single long alkyl chain can protect the cationic softener from interacting with anionic surfactants and/or detergent builders that are carried over into the rinse from the wash solution.
- Suitable amine oxides include those with one alkyl or hydroxyalkyl moiety of about 8 to about 22 carbon atoms, preferably from about 10 to about 18 carbon atoms, more preferably from about 8 to about 14 carbon atoms, and two alkyl moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups with about 1 to about 3 carbon atoms.
- Examples include dimethyloctylamine oxide, diethyldecylamine oxide, bis-(2-hydroxyethyl)dodecyl-amine oxide, dimethyldodecylamine oxide, dipropyltetradecylamine oxide, methylethylhexadecylamine oxide, dimethyl-2-hydroxyoctadecylamine oxide, and coconut fatty alkyl dimethylamine oxide.
- Stabilizers can be present in the compositions of the present invention.
- the term "stabilizer,” as used herein, includes antioxidants and reductive agents. These agents are present at a level of from 0% to about 2%, preferably, from about 0.01% to about 0.2%, more preferably from about 0.035% to about 0.1% for antioxidants, and more preferably from about 0.01% to about 0.2% for reductive agents. These assure good odor stability under long term storage conditions. Antioxidants and reductive agent stabilizers are especially critical for unscented or low scent products (no or low perfume).
- antioxidants examples include a mixture of ascorbic acid, ascorbic palmitate, propyl gallate, available from Eastman Chemical Products, Inc., under the trade names Tenor® PG and Tenox® S-1; a mixture of BHT (butylated hydroxytoluene), BHA (butylated hydroxyanisole), propyl gallate, and citric acid, available from Eastman Chemical Products, Inc., under the trade name Tenox®-6; butylated hydroxytoluene, available from UOP Process.
- an optional soil release agent can be added.
- the addition of the soil release agent can occur in combination with the premix, in combination with the acid/water seat, before or after electrolyte addition, or after the final composition is made.
- the softening composition prepared by the process of the present invention herein can contain from 0% to about 10%, preferably from 0.2% to about 5%, of a soil release agent.
- a soil release agent is a polymer.
- Polymeric soil release agents useful in the present invention include copolymeric blocks of terephthalate and polyethylene oxide or polypropylene oxide, and the like.
- a preferred soil release agent is a copolymer having blocks of terephthalate and polyethylene oxide. More specifically, these polymers are comprised of repeating units of ethylene terephthalate and polyethylene oxide terephthalate at a molar ratio of ethylene terephthalate units to polyethylene oxide terephthalate units of from 25:75 to about 35:65, said polyethylene oxide terephthalate containing polyethylene oxide blocks having molecular weights of from about 300 to about 2000. The molecular weight of this polymeric soil release agent is in the range of from about 5,000 to about 55,000.
- Another preferred polymeric soil release agent is a crystallizable polyester with repeat units of ethylene terephthalate units containing from about 10% to about 15% by weight of ethylene terephthalate units together with from about 10% to about 50% by weight of polyoxyethylene terephthalate units, derived from a polyoxyethylene glycol of average molecular weight of from about 300 to about 6,000, and the molar ratio of ethylene terephthalate units to polyoxyethylene terephthalate units in the crystallizable polymeric compound is between 2:1 and 6:1.
- this polymer include the commercially available materials Zelcon 4780® (from Dupont) and Milease T® (from Id).
- Highly preferred soil release agents are polymers of the generic formula: in which each X can be a suitable capping group, with each X typically being selected from the group consisting of H, ana alkyl or acyl groups containing from about 1 to about 4 carbon atoms.
- p is selected for water solubility and generally is from about 6 to about 113, preferably from about 20 to about 50.
- u is critical to formulation in a liquid composition having a relatively high ionic strength. There should be very little material in which u is greater than 10. Furthermore, there should be at least 20%, preferably at least 40%, of material in which u ranges from about 3 to about 5.
- the R 14 moieties are essentially 1,4-phenylene moieties.
- the term "the R 14 moieties are essentially 1,4-phenylene moieties” refers to compounds where the R 14 moieties consist entirely of 1,4-phenylene moieties, or are partially substituted with other arylene or alkarylene moieties, alkenyl moieties, alkenylene moieties, or mixtures thereof.
- Arylene and alkarylene moieties which can be partially substituted for 1,4-phenylene include 1,3-phenylene, 1,2-phenylene, 1,8-naphthylene, 1,4-naphthylene, 2,2-biphenylene, 4,4-biphenylene, and mixtures thereof.
- Alkylene and alkenylene moieties which can be partially substituted include 1,2-propylene, 1,4-butylene, 1,5-pentylene, 1,6-hexamethylene, 1,7-heptamethylene, 1,8-octamethylene, 1,4-cyclohexylene, and mixtures thereof.
- the degree of partial substitution with moieties other than 1,4-phenylene should be such that the soil release progenies of the compound are not adversely affected to any great extent.
- the degree of partial substitution which will depend upon the backbone length of the compound, i.e., longer backbones can have-greater partial substitution for 1,4-phenylene moieties.
- compounds where the R 14 comprise from about 50% to about 100% 1,4-phenylene moieties (from 0% to about 50% moieties other than 1,4-phenylene) have adequate soil release activity.
- polyesters made according to the present invention with a 40:60 mole ratio of isophthalic (1,3-phenylene) to terephthalic (1,4-phenylene) acid have adequate soil release activity.
- the R 14 moieties consist entirely of (i.e., comprise 100%) 1,4-phenylene moieties, i.e., each R 14 moiety is 1,4-phenylene.
- suitable ethylene or substituted ethylene moieties include ethylene, 1,2-propylene, 1,2-butylene, 1,2-hexylcne, 3-methoxy-1,2-propylene, and mixtures thereof.
- the R 15 moieties are essentially ethylene moieties, 1,2-propylene moieties, or mixtures thereof. Inclusion of a greater percentage of ethylene moieties tends to improve the soil release activity of compounds. Surprisingly, inclusion of a greater, percentage of 1,2-propylene moieties tends to improve the water solubility of compounds.
- 1,2-propylene moieties or a similar branched equivalent is desirable for incorporation of any substantial part of the soil release component in the liquid fabric softener compositions.
- each p is at least about 6, and preferably is at least about 10.
- the value for each n usually ranges from about 12 to about 113. Typically the value for each p is in the range of from about 12 to about 43.
- soil release agents can also act as scum dispersants.
- the premix can be combined with an optional scum dispersant, other than the soil release agent, and heated to a temperature at or above the melting point(s) of the components,
- the preferred scum dispersants herein are formed by highly ethoxylating hydrophobic materials.
- the hydrophobic material can be fatty alcohol, fatty acid, fatty amine, fatty acid amide, amine oxide, quaternary ammonium compound, or the hydrophobic moieties used to form soil release polymers.
- the preferred scum dispersants are highly ethoxylated, e.g., more than about 17, preferably more than about 25, more preferably more than about 40, moles of ethylene oxide per molecule on the average, with the polyethylene oxide portion being from about 76% to about 97%, preferably from about 81% to about 94%, of the total molecular weight
- the level of scum dispersant is sufficient to keep the scum at an acceptable, preferably unnoticeable to the consumer, level under the conditions of use, but not enough to adversely affect softening. For some purposes it is desirable that the scum is nonexistent.
- the amount of anionic or nonionic detergent, etc., used in the wash cycle of a typical laundering process the efficiency of the rinsing steps prior to the introduction of the compositions herein, and the water hardness, the amount of anionic or nonionic detergent surfactant and detergency builder (especially phosphates and zeolites) entrapped in the fabric (laundry) will vary.
- the minimum amount of scum, dispersant should be used to avoid adversely affecting softening properties.
- scum dispersion requires at least about 2%, preferably at least about 4% (at least 6% and preferably at least 10% for maximum scum avoidance) based upon the level of softener active.
- levels of about 10% (relative to the softener material) or more one risks loss of softening efficacy of the product especially when the fabrics contain high proportions of nonionic surfactant which has been absorbed during the washing operation.
- Preferred scum dispersants are: Brij 700®; Varonic U-250®; Genapol T-500®, Genapol T-800®; Plurafac A-79®; and Neodol 25-50®.
- bactericides used in the compositions of this invention include glutaraldehyde, formaldehyde, 2-bromo-2-nitro-propane-1,3-diol sold by Inolex Chemicals, located in Philadelphia, Pennsylvania, under the trade name Bronopol®, and a mixture of 5-chloro-2-methyl-4-isothiazoline-3-one and 2-methyl-4-isothiazoline-3-one sold by Rohm and Haas Company under the trade name Kathon about 1 to about 1,000 ppm by weight of the agent.
- the present invention can contain any "softener compatible perfume. Suitable perfumes are disclosed in U.S. Pat. 5,500,138, Bacon et al., issued March 19, 1996, said patent being incorporated herein by reference.
- perfume includes fragrant substance or mixture of substances including natural (i.e., obtained by extraction of flowers, herbs, leaves, roots, barks, wood, blossoms or plants), artificial (i.e., a mixture of different nature oils or oil constituents) and synthetic (i.e., synthetically produced) odoriferous substances.
- natural i.e., obtained by extraction of flowers, herbs, leaves, roots, barks, wood, blossoms or plants
- artificial i.e., a mixture of different nature oils or oil constituents
- synthetic i.e., synthetically produced
- perfumes are complex mixtures of a plurality of organic compounds.
- perfume ingredients useful in the perfumes of the present invention compositions include, but are not limited to, hexyl cinnamic aldehyde; amyl cinnamic aldehyde; amyl salicylate; hexyl salicylate; terpincol; 3,7-dimethyl- cis -2,6-octadien-1-ol; 2,6-dimethyl-2-octanol; 2.6-dimethyl-7-octen-2-ol; 3,7-dimethyl-3-octanol; 3,7-dimethyl- trans -2,6-octavdien-1-ol; 3,7-dimethyl-6-octen-1-ol; 3,7-dimethyl-1-octanol, 2-methyl-3-(para-tert-butylphenyl)-propionaldehyde; 4-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carboxalde
- fragrance materials include, but are not limited to, orange oil; lemon oil; grapefruit oil; bergamot oil; clove oil; dodecalactone gamma; methyl-2-(2-pentyl-3-oxo-cyclopentyl) acetate; beta-naphthol methylether, methyl-beta-naphthylketone; coumarin; decylaldehyde; benzaldehyde; 4-tert-butylcyclohexyl acetate; alpha, alpha-dimethylphenethyl acetate; methylphenylcarbinyl acetate; Schiffs base of 4-(4-hydroxy-4-methylpentyl)-3-cyclohexene-l-carboxaldehyde and methyl anthranilate; cyclic ethyleneglycol diester of tridecandioic acid; 3,7-dimethyl-2,6-octadiene-1-nitrite; i
- perfume components are geraniol; geranyl acetate; linalool; linalyl acetate; tetrahydrolinalool; citronellol; citronellyl acetate, dihydromyrcenol; dihydromyrcenyl acetate; tetrahydromyrcenol; terpinyl acetate; nopol; nopyl acetate; 2-phenylethanol; 2-phenylethyl acetate; benzyl alcohol; benzyl acetate; benzyl salicylate; benzyl benzoate; styrallyl acetate; dimethylbenzylcarbinol; trichloromethylphenylcarbinyl methylphenylcarbinyl acetate; isononyl acetate; vetiveryl- acetate; vetiverol; 2-methyl-3-(p-tert-butylphenyl)-propanal, 2-methyl
- the perfmes useful in the present invention compositions are substantially free of halogenated materials and nitromusks.
- Suitable solvents, diluents or carriers for perfumes ingredients mentioned above are for examples, ethanol, isopropanol, diethylene glycol, monoethyl ether, dipropylene glycol, diethyl phthalate, triethyl citrate, etc.
- the amount of such solvents, diluents or carriers incorporated in the perfumes is preferably kept to the minimum needed to provide a homogeneous perfume solution.
- Perfume can be present at a level of from 0% to about 10%; preferably from about 0.1% to about 5%, and more preferably from about 0.2% to about 3%, by weight of the finished composition.
- Fabric softener compositions of the present invention provide improved fabric perfume deposition.
- compositions and processes herein can optionally employ one or more copper and/or nickel chelating agents ("chelators").
- chelators can be selected from the group consisting of amino carboxylates, amino phosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures thereof, all as hereinafter defined.
- the whiteness and/or brightness of fabrics are substantially improved or restored by such chelating agents and the stability of the materials in the compositions are improved.
- Amino carboxylates useful as chelating agents herein include ethylenediaminetetraacetates (EDTA), N-hydroxyethylethylenediaminetriacetates, nitrilotriacetates (NTA), ethylenediamine tetraproprionates, ethylenediamine-N,N'-diglutamates, 2-hyroxypropylenediamine-N,N'-disuccinates, triethylenetetraaminehexacetates, diethylenetriaminepentaacetates (DETPA), and ethanoldiglydnes, including their water-soluble salts such as the alkali metal, ammonium, and substituted ammonium salts thereof and mixtures thereof.
- EDTA ethylenediaminetetraacetates
- NDA nitrilotriacetates
- ethylenediamine tetraproprionates ethylenediamine-N,N'-diglutamates
- 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 ethylenediaminetetratis (methylenephosphonates), diethylenetriaroine-N,N,N',N",N"-pentakis(methane phosphonate) (DETMP) and 1-hydroxyethane-1,1-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 preferred EDDS chelator used herein (also known as ethylenediamine-N,N'-disuccinate) is the material described in U.S. Patent 4,704,233, cited hereinabove, and has the formula (shown in free acid form):
- EDDS can be prepared using maleic anhydride and ethylenediamine.
- the preferred biodegradable [S,S] isomer of EDDS can be prepared by reacting L-aspartic acid with 1,2-dibromoethane.
- the EDDS has advantages over other chelators in that it is effective for chelating both copper and nickel cations, is available in a biodegradable form, and does not contain phosphorus.
- the EDDS employed herein as a chelator is typically in its salt form, i.e., wherein one or more of the four acidic hydrogens are replaced by a water-soluble cation M such as sodium, potassium, ammonium, triethanolammonium, and the like.
- 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 pH's the EDDS is preferably used in combination with zinc cations.
- chelators can be used herein. Indeed, simple polycarboxylates such as citrate, oxydisuccinate, and the like, can also be used, although such are not as effective as the amino carboxylates and phosphonates, on a weight basis. Accordingly, usage levels may be adjusted to take into account differing degrees of chelating effectiveness.
- the chelators herein will preferably have a stability constant (of the fully ionized chelator) for copper ions of at least about 5, preferably at least about 7. Typically, the chelators will comprise from about 0.5% to about 10%, more preferably from about 0.75% to about 5%, by weight of the compositions herein, in addition to those that are stabilizers.
- Preferred chelators include DETMP, DETPA, NTA, EDDS and mixtures thereof.
- the present invention can include optional components conventionally used in textile treatment compositions, for example: colorants; preservatives; surfactants; anti-shrinkage agents; fabric crisping agents; spotting agents; germicides; fungicides; anti-oxidants such as butylated hydroxy toluene, anti-corrosion agents, and the like.
- Particularly preferred ingredients include water soluble calcium and/or magnesium compounds, which provide additional stability.
- the chloride salts are preferred, but acetate, nitrate, etc. salts can be used.
- the level of said calcium and/or magnesium salts is from 0% to about 2%, preferably from about 0.05% to about 0.5%, more preferably from about 0.1% to about 0.25%.
- the present invention can also include other compatible ingredients, including those as disclosed in copending applications Serial Nos.: 08/372,068 (priority document of WO 96/21714), filed January 12, 1995, Rusche, et al.; 08/372,490, filed January 12, 1995, (Priority document of WO 96/21714)Shaw, et al.; and 08/277,558, (Priority document of WO 96/02625) filed July 19, 1994, Hartman, et al., incorporated herein by reference.
- Cis-1,2-bis(hydroxylethyl)cyclohexane has a ClogP of 0.47, which is within the preferred range of 0.40 to 0.60.
- 1,4-Bis(hydroxymethyl)cyclohexane also has a ClogP of 0.47, which is within the preferred range of 0.40 to 6.60, but has a center of symmetry, and does not form an acceptable composition (Composition IIA-5A).
- 1,2-cyclohexanediol and 4,5-dimethyl-1,2-cyclohexanediol have ClogP values which are outside the effective range of 0.15-0.64.
- Example IIA-5 Only the composition of Example IIA-5 is a clear composition with acceptable viscosities both at room temperature and at about 40°F (about 4°C); compositions of Comparative Examples IIA-5A to IIA- 5c are not clear and/or do not have acceptable viscosities.
- 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 of the 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 of the 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 active 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/of loss of materials such as the biodegradable fabric softener active, perfumes, etc., and reduces the need for heating, thus saving on the expenses for processing.
- Additional protection for the softener active can be provided by adding, e.g., chelant such as ethylenedianunepentaacetic acid, during preparation of the active. 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 active 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.
- the temperatures at which the premix is clear and/or liquid for various levels of principal solvent are as follows:
- 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.
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Claims (16)
- Transluzente oder klare, wässrige, stabile Textllwelchmacherzusammensetzung, umfassend:A. 2% bis 80% Textilweichmacherwirkstoff, gewählt aus der Gruppe, bestehend aus:1. Textilweichmacherverbindung der Formel: worin jeder R-Substituent H oder eine kurzkettige C1-C6-Alkyl- oder Hydroxyalkylgruppe, Benzyl oder Mischungen hiervon ist; jedes m 2 oder 3 ist; jedes n 1 bis 4 ist; jedes Y -0-(O)C -(R)N-(O)C-, -C(O)-N(R)- oder -C(O)-O-, jedoch nicht -OC(O)O- ist; the Summe an Kohlenstoffen in jedem R1 oder YR1, wenn Y -O-(O)C- oder -(R)N-(O)C- ist, C6-C22 beträgt, wenn jedoch die Summe an Kohlenstoffen in einem R1 oder YR1 weniger als 12 beträgt, dann ist die andere R1- oder YR1-Summe mindestens 16, wobei jedes R1 eine langkettige Hydrocarbyl- oder substituierte Hydrocarbysubstituentengruppe ist, und für R1 oder YR1, C16-C20-Hydrocarbyl- oder substituierte Hydrocarbylsubstituentengruppen, die Iodzahl einer YR1-Fettsäure, welche diese R1-Gruppe enthält, 20 bis 140 beträgt, und für R1 oder YR1, C8-C14-Hydrocarbyl oder substituierte Hydrocarbylsubstituentengruppen. die Iodzahl einer Fettsäure, welche diese R1-Gruppe enthält, 10 oder weniger beträgt;2. Textilweichmacherverbindung der Formel: worin jedes Y, R, R1 und X(-) die gleichen Bedeutungen wie oben besitzen; und3. Mischungen hiervon; undB. 10 bis 40 Gew.-% der Zusammensetzung Hauptlösungsmittel
dadurch gekennzeichnet, dass das Hauptlösungsmittel eine ClogP von 0,15 bis 0,64 (wie durch die Fragment-Annäherung von Hansch und Leo, wie hierin definiert, berechnet) und mindestens einen gewissen Grad an Asymmetrie besitzt, wobei das Hauptlösungsmittel aus der Gruppe gewählt ist, bestehend aus:1-Isopropyl-1,2-cyclobutandiol; 3-Ethyl-4-methyl- 1,2-cyclobutandlol; 3-Propyl-1,2-cyclobutandiol; 3-Isoopropyl- 1,2-cyclobutandiol; 1-Ethyl-1,2-cyclopentandiol; 1,2-Dimethyl-1,2-cyclopentandiol; 1,4-Dimethyl-1,2-cyclopentandiol; 3,3-Dimethyl-1,2-cyclopentandiol; 3,4-Dimethyl-1,2-cyclopentandiol; 3,5 -Dimethyl-1,2,-cyclopentandiol; 3-Ethyl-1,2-cyclopentandiol; 4,4-Dimethyl-1,2-cyclopentandiol; 4-Ethyl-1,2-cyclopentandiol; 1,1 Bis(hydroxymethyl)cyclohexan; 1,2-Bis(hydroxymethyl)cyclohexan; 1,2-Dimethyl-1,3-cyclohexandiol; 1,3-Bis(hydroxymethyl)cyclohexan; 1-Hydroxy-cyclohexanmethanol; 1-Methyl-1,2-cyclohexandiol; 3-Hydroxymethylcyclohexanol; 3-Methyl-1,2-cyclohexandiol; 4,4-Dimethyl-1,3-cyclohexandiol; 4,5-Dimethyl-1,3-cyclohexandiol; 4,6-Dimethyl- 1 ,3-cyclohexandiol; 4-Ethyl-1,3-cyclohexandiol; 4-Hydroxyethyl-1-cyclohexanol; 4-Hydroxymethylcyclohexanol; 4-Methyl-1,2-cyclohexandiol; 1,2-Cycloheptandiol; 1,2-Cyclohexandiol-pentaethoxylat; 1,2-Cyclohexandiol-hexaethoxylat; 1,2-Cyclohexandiol-heptaethoxylat; 1,2-Cyclohexandiol-octaethoxylat; 1,2-Cyclohexandiol-nonaethoxylat: 1,2-Cyclohexandiol-monopropoxylat; 1,2-Cyclohexandiol-dibutylenoxylat; und Mischungen hiervon; - Wässrige, stabile Textilweichmacherzusammensetzung nach Anspruch 1, umfassend weiterhin:C. eine wirksame Menge, ausreichend um die Klarheit zu verbessern, niedermolekulargewichtige, wasserlösliche Lösungsmittel, gewählt aus der Gruppe, bestehend aus Ethanol, Isopropanol, Propylenglykol, 1,3-Propandiol, Propylencarbonat und Mischungen hiervon, wobei diese wasserlöslichen Lösungsmittel in einem Anteil vorliegen, welcher keine klaren Zusammensetzungen durch diese selbst bildet.
- Wässrige, stabile Textilweichmacherzusammensetzung nach Anspruch 1 oder 2, umfassend weiterhin:D. eine wirksame Menge, um die Klarheit zu verbessern, eines wasserlöslichen Calcium- und/oder Magnesiumsalzes.
- Wässrige, stabile Textilweichmacherzusammensetzung nach mindestens einem der Ansprüche 1 bis 3, umfassend:A. 13% bis 75% des Textilweichmacherwirkstoffs, gewählt aus der Gruppe, bestehend aus:1. Textilweichmacherverbindung der Formel: worin jeder R-Substituent H oder eine kurzkettige C1-C3-Alkyl- oder Hydroxyalkylgruppe, Benzyl oder Mischungen hiervon ist; jedes m 2 ist; jedes n 2 bis 3 ist; jedes Y -O-(O ist, jedes R1 ein langkettiges C9-C19-Hydrocarbyl ist, und für R1 C15-C19-Hydrocarbyl- oder substituierte Hydrocarbylsubstituentengruppen, die Iodzahl der korrespondierenden Fettsäure dieser R1-Gruppe 50 bis 130 beträgt; und für R1 C7-C13 oder substituierte Hydrocarbylsubstituentengruppen, die Iodzahl der korrespondierenden Fettsäure der R1-Gruppe 10 oder weniger beträgt;2. Textilweichmacherverbindung der Formel: worin jedes Y, R, R1 und X(-) die gleichen Bedeutungen wie oben besitzen; und3. Mischungen hiervon;B. 10 bis 35 Gew.-% der Zusammensetzung des Hauptlösungsmittels, wobei das Hauptlösungsmittel einen ClogP von 0,25 bis 0,62 besitzt;C. wahlweise 1% bis 10%, und ausreichend um die Klarheit zu verbessern, niedermolekulargewichtige, wasserlösliche Lösungsmittel, gewählt aus der Gruppe, bestehend aus Ethanol, Isopropanol, Propylenglykol, 1,3-Propandiol, Propylencarbonat, wobei die wasserlöslichen Lösungsmittel in einem Anteil vorliegen, welcher keine klaren Zusammensetzungen durch diese selbst bildet;D. wahlweise 0% bis 2%, und ausreichend um die Klarheit zu verbessern, die erwünschte Viskosität zu erzielen oder die Klarheit zu verbessern und die erwünschte Viskosität zu erzielen, wasserlösliches Calcium- und/oder Magnesiumsalz; undE. 10% bis 80% Wasser.
- Wässrige, stabile Textilweichmacherzusammensetzung nach Anspruch 4, umfassend:A. 17% bis 70% des Textilweichmacherwirkstoffs, gewählt aus der Gruppe, bestehend aus:1. Textilweichmacherverbindung der Formel: worin jeder R-Substituent H oder eine kurzkettige C1-C3-Alkyl-oder Hydroxyalkylgruppe, Benzyl oder Mischungen hiervon ist; jedes m 2 ist; jedes n 2 bis 3 ist; jedes Y -O-(O)C- ist, jedes R1 ein langkettiger C9-C19-Hydrocarbyl- oder substituierter Hydrocarbyl-substituent ist, und für R1 C15-C7-Hydrocarbyl- oder substituierte Hydrocarbylsubstituentengruppen, die Iodzahl der korrespondierenden Fettsäure dieser R1-Gruppe 70 bis 115 beträgt; und für R1 C7-C13 oder substituierte Hydrocarbylsubstituentengruppen, die Iodzahl der korrespondierenden Fettsäure der R1-Gruppe 5 oder weniger beträgt;2. Textilweichmacherverbindung der Formel: worin jedes Y, R, R1 und X(-) die gleichen Bedeutungen wie oben besitzen; und3. Mischungen hiervon;B. 12 bis 35 Gew.-% der Zusammensetzung des Hauptlösungsmittels, wobei das Hauptlösungsmittel einen ClogP von 0,40 bis 0,60 aufweist;C. wahlweise 2% bis 8% und ausreichend, um die Klarheit zu verbessern, niedermolekulargewichtiger, wasserlöslicher Lösungsmittel, gewählt aus der Gruppe, bestehend aus Ethanol, Isopropanol, Propylenglykol, 1,3-Propandiol, Propylencarbonat;D. wahlweise 0,05% bis 0,5% und ausreichend, um die Klarheit zu verbessern, die erwünschte Viskosität zu erzielen, oder die Klarheit zu verbessern und die erwünschte Viskosität zu erzielen, wasserlösliches Calcium- und/oder Magnesiumsalz; undE. 20% bis 80% Wasser.
- Wässrige, stabile Textilweichmacherzusammensetzung nach Anspruch 5, wobei die Zusammensetzung klar ist und umfasst:A. 19 bis 65 Gew.-% der Zusammensetzung des Textilweichmachers:1. Textilweichmacherverbindung der Formel: worin jeder R-Substituent Methyl, Ethyl, Propyl, Hydroxyethyl, Benzyl oder Mischungen hiervon ist; jedes n 2 ist; jedes R1 ein langkettiges C13-C17-geradkettiges Alkyl oder Alkylen ist, und für R1 C15-C17-Hydrocarbyl- oder substituierte Hydrocarbylsubsituentengruppen, die Iodzahl der korrespondierenden Fettsäure dieser R1-Gruppe 70 bis 115 beträgt;B. 14 bis 35 Gew.-% der Zusammensetzung des Hauptlösungsmittels, wobei das Hauptlösungsmittel einen ClogP von 0,40 bis 0,60 aufweist;C. wahlweise 2% bis 8%, und ausreichend, um die Klarheit zu verbessern, niedermolekulargewichtige, wasserlösliche Lösungsmittel, gewählt aus der Gruppe, bestehend aus Ethanol, Isopropanol, Propylenglykol, 1,3-Propandiol und Propylencarbonat;D. wahlweise 0,1% bis 0,25%, und ausreichend um die Klarheit zu verbessern, die erwünschte Viskosität zu erzielen, oder die Klarheit zu verbessern und die erwünschte Viskosität zu erzielen, wasserlösliches Calcium- oder Magnesiumchlorid, -acetat oder -nitrat; undE. 30% bis 70% Wasser.
- Zusammensetzung nach Anspruch 1, wobei der ClogP 0,25 bis 0,62 beträgt.
- Zusammensetzung nach mindestens einem der Ansprüche 1 bis 7, wobei der Weichmacherwirkstoff bis zu 20% Monoesterverbindung umfasst, worin m 2 ist und ein YR1 -OH, -N(R)H oder -C(O)OH ist.
- Zusammensetzung nach mindestens einem der Ansprüche 1 bis 7, wobei bei geringen Wasseranteilen von 5% bis 15% das Gewichtsverhältnis von Weichmacherwirkstoff zu Hauptlösungsmittel 55:45 bis 85:15 beträgt; bei Wasseranteilen von 15% bis 70% das Gewichtsverhältnis von Weichmacherwirkstoff zu Hauptlösungsmittel 45:55 bis 70:30 beträgt, und bei hohen Wasseranteilen von 70% bis 80%, das Gewichtsverhältnis von Weichmacherwirkstoff zu Hauptlösungsmittel 30:70 bis 55:45 beträgt.
- Zusammensetzung nach Anspruch 9, wobei bei geringen Wasseranteilen von 5% bis 15% das Gewichtsverhältnis von Weichmacherwirkstoff zu Hauptlösungsmittel 60:40 bis 80:20 beträgt; bei Wasseranteilen von 15% bis 70% das Gewichtsverhältnis von Weichmacherwirkstoff zu Hauptlösungsmittel 55:45 bis 70:30 beträgt; und bei hohen Wasseranteilen von 70% bis 80% das Gewichtsverhältnis von Weichmacherwirkstoff zu Hauptlösungsmittel 35:65 bis 45:55 beträgt.
- Zusammensetzung nach Anspruch 1, welche bei 25°C transluzent oder klar ist, enthaltend Lösungsmittel, welche von dem Hauptlösungsmittel B. verschieden sind, wobei die Menge des Hauptlösungsmittels B. mindestens 5 Gew.-% der Zusammensetzung beträgt, wobei die Zusammensetzung in Abwesenheit des Hauptlösungsmittels B. bei 25°C nicht transluzent oder klar ist.
- Zusammensetzung nach mindestens einem der Ansprüche 1 bis 7, das einen oder mehrere der folgenden wahlweisen Bestandteile enthält:(a) Aufheller in einem Anteil von 0,005% bis 5%;(b) Dispersibilitätshilfe in einem Anteil von 2% bis 25%;(c) Schmutzabweisungsmittel in einem Anteil von 0% bis 10%;(d) Schaumdispergiermittel in einem Anteil von 2% bis 10%:(e) Stabilisator, gewählt aus der Gruppe, bestehend aus Antioxidans, Reduktionsmittel, Komplexbildner und Mischungen hiervon; in einem Anteil von 0% bis 2%;(f) Bakterizid in einem Anteil von 0,005% bis 5%; und(g) Chelatbildungsmittel zusätzlich zu irgendeinem Komplexbildner (e) in einem Anteil von 0,5% bis 10%.
- Premix der Kompenenten nach mindestens einem der Ansprüche 1 bis 7, bestehend im Wesentlichen aus
dem bioabbaubaren Textilweichmacherwirkstoff A.; dem Hauptlösungsmittel B.; und wahlweise dem wasserlöslichen Lösungsmittel C. - Hergestellte Artikel, umfassend die Zusammensetzung nach Anspruch 1 in einer klaren Flasche.
- Artikel nach Anspruch 14, wobei die Flasche einen leichten Blauton besitzt, ausreichend, um irgendeine leichte gelbe Farbe der Zusammensetzung zu kompensieren.
- Artikel nach Anspruch 15, wobei die Flasche in der Flaschenwand einen Ultravioletlicht-Absorber eingearbeitet hat, um die Zusammensetzung zu schützen.
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US62101996A | 1996-03-22 | 1996-03-22 | |
US621019 | 1996-03-22 | ||
PCT/US1996/011556 WO1997003169A1 (en) | 1995-07-11 | 1996-07-11 | Concentrated, stable fabric softening composition |
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EP96924436A Expired - Lifetime EP0842250B1 (de) | 1995-07-11 | 1996-07-11 | Konzentrierte, stabile textilweichmacherzusammensetzung |
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CN (3) | CN1107716C (de) |
AR (1) | AR002814A1 (de) |
AT (1) | ATE233804T1 (de) |
AU (2) | AU6636596A (de) |
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DE (1) | DE69626521T2 (de) |
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JP3419464B2 (ja) * | 1996-07-19 | 2003-06-23 | ザ、プロクター、エンド、ギャンブル、カンパニー | 濃縮布地柔軟化組成物およびそのための高不飽和布地柔軟剤化合物 |
CA2264087A1 (en) * | 1996-08-30 | 1998-03-05 | Hugo Jean-Marie Demeyere | Concentrated premix with reduced flammability for forming fabric softening composition |
AU7578198A (en) * | 1997-05-19 | 1998-12-11 | Procter & Gamble Company, The | Clear or translucent fabric softener compositions using mixture of solvents |
EP1002035A1 (de) * | 1997-07-29 | 2000-05-24 | The Procter & Gamble Company | Konzentrierte, stabile, vorzugsweise durchsichtige textilweichmacherzusammensetzung, die amin-textilweichmacher enthält |
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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 |
ZA991635B (en) * | 1998-03-02 | 1999-09-02 | Procter & Gamble | Concentrated, stable, translucent or clear, fabric softening compositions. |
US6486121B2 (en) * | 1998-04-15 | 2002-11-26 | The Procter & Gamble Company | Softener active derived from acylated triethanolamine |
EP1018541A1 (de) * | 1999-01-07 | 2000-07-12 | Goldschmidt Rewo GmbH & Co. KG | Klare Weichspülmittelformulierungen |
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 |
GB9915964D0 (en) | 1999-07-07 | 1999-09-08 | Unilever Plc | Fabric conditioning composition |
AU2001263062A1 (en) | 2000-05-11 | 2001-11-20 | The Procter And Gamble Company | Highly concentrated fabric softener compositions and articles containing such compositions |
JP2004522010A (ja) * | 2000-05-24 | 2004-07-22 | ザ、プロクター、エンド、ギャンブル、カンパニー | 悪臭制御剤を含んでなる布地柔軟剤組成物 |
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 |
ATE401385T1 (de) * | 2003-10-16 | 2008-08-15 | Procter & Gamble | Wässrige zusammensetzungen mit vesikeln mit gewisser vesikeldurchlässigkeit |
JP4611422B2 (ja) * | 2005-05-12 | 2011-01-12 | ザ プロクター アンド ギャンブル カンパニー | 凍結融解条件下で安定な布地柔軟化組成物 |
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 |
CN101454433B (zh) * | 2006-05-31 | 2011-08-17 | 阿克佐诺贝尔股份有限公司 | 具有改进的软化和抗静电性能的水性衣物洗涤剂组合物 |
GB0714589D0 (en) * | 2007-07-27 | 2007-09-05 | Unilever Plc | Fabric softening composition |
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 |
MX2018009047A (es) | 2016-01-25 | 2018-11-09 | Procter & Gamble | Composiciones de tratamiento. |
US10689600B2 (en) | 2016-01-25 | 2020-06-23 | The Procter & Gamble Company | Treatment compositions |
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 |
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 |
US9896648B2 (en) | 2016-03-02 | 2018-02-20 | The Procter & Gamble Company | Ethoxylated diols and compositions containing ethoxylated diols |
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 |
US20210261887A1 (en) * | 2018-07-18 | 2021-08-26 | Symrise Ag | A detergent composition |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1993023510A1 (en) * | 1992-05-12 | 1993-11-25 | The Procter & Gamble Company | Concentrated fabric softener compositions containing biodegradable fabric softeners |
WO1996011248A1 (en) * | 1994-10-07 | 1996-04-18 | The Procter & Gamble Company | Fabric softening composition containing chlorine scavengers |
WO1996019552A1 (en) * | 1994-12-21 | 1996-06-27 | Colgate-Palmolive Company | Clear, concentrated liquid fabric softener compositions |
WO1996033800A1 (en) * | 1995-04-27 | 1996-10-31 | Witco Corporation | Compositions containing diol and/or diol alkoxylate |
EP0763592A1 (de) * | 1995-09-18 | 1997-03-19 | The Procter & Gamble Company | Stabilisierte Textilweichmacherzusammensetzungen |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA913309A (en) * | 1968-08-01 | 1972-10-31 | A. Gluck Bruno | Fabric softening compositions |
CH1824769D (de) * | 1968-12-09 | |||
US3756950A (en) * | 1971-03-08 | 1973-09-04 | Lever Brothers Ltd | Fabric softening compositions |
US3920564A (en) * | 1972-09-20 | 1975-11-18 | Colgate Palmolive Co | Softener-detergent composition |
US4298480A (en) * | 1978-12-11 | 1981-11-03 | Colgate Palmolive Co. | Detergent softener compositions |
GB8312619D0 (en) * | 1983-05-07 | 1983-06-08 | Procter & Gamble | Surfactant compositions |
JPH01501492A (ja) * | 1987-06-16 | 1989-05-25 | コートル・ソシエテ・アノニム | 濃厚な柔軟剤組成物 |
GB8914054D0 (en) * | 1989-06-19 | 1989-08-09 | Unilever Plc | Fabric softening composition |
ES2080241T3 (es) * | 1991-09-27 | 1996-02-01 | Procter & Gamble | Composiciones suavizantes de tejidos concentradas. |
DE4307186A1 (de) * | 1993-03-08 | 1994-09-15 | Henkel Kgaa | Wäßrige Textilweichmacher-Zusammensetzung |
US5490944A (en) * | 1994-08-11 | 1996-02-13 | Colgate-Palmolive Company | Liquid fabric softener compositions |
-
1996
- 1996-07-11 BR BR9609800A patent/BR9609800A/pt not_active Application Discontinuation
- 1996-07-11 JP JP9505982A patent/JPH11506810A/ja active Pending
- 1996-07-11 KR KR1019980700197A patent/KR100274684B1/ko not_active IP Right Cessation
- 1996-07-11 AU AU66365/96A patent/AU6636596A/en not_active Abandoned
- 1996-07-11 HU HU9802404A patent/HUP9802404A3/hu unknown
- 1996-07-11 MX MX9800382A patent/MX9800382A/es unknown
- 1996-07-11 BR BR9609823A patent/BR9609823A/pt not_active Application Discontinuation
- 1996-07-11 HU HU9802207A patent/HUP9802207A3/hu unknown
- 1996-07-11 MX MX9800381A patent/MX9800381A/es unknown
- 1996-07-11 CN CN96196853A patent/CN1107716C/zh not_active Expired - Fee Related
- 1996-07-11 CA CA002226550A patent/CA2226550C/en not_active Expired - Fee Related
- 1996-07-11 KR KR1019980700196A patent/KR100263870B1/ko not_active IP Right Cessation
- 1996-07-11 KR KR1019997011199A patent/KR100263216B1/ko not_active IP Right Cessation
- 1996-07-11 TR TR1998/00029T patent/TR199800029T1/xx unknown
- 1996-07-11 EP EP96926070A patent/EP0839180A1/de not_active Ceased
- 1996-07-11 AT AT96924436T patent/ATE233804T1/de not_active IP Right Cessation
- 1996-07-11 WO PCT/US1996/011572 patent/WO1997003172A1/en not_active Application Discontinuation
- 1996-07-11 EP EP96924436A patent/EP0842250B1/de not_active Expired - Lifetime
- 1996-07-11 CZ CZ9838A patent/CZ3898A3/cs unknown
- 1996-07-11 CA CA002226564A patent/CA2226564C/en not_active Expired - Fee Related
- 1996-07-11 CZ CZ9862A patent/CZ6298A3/cs unknown
- 1996-07-11 DE DE69626521T patent/DE69626521T2/de not_active Expired - Lifetime
- 1996-07-11 AU AU64889/96A patent/AU6488996A/en not_active Abandoned
- 1996-07-11 JP JP50599197A patent/JP3916666B2/ja not_active Expired - Fee Related
- 1996-07-11 CN CN96196787A patent/CN1195369A/zh active Pending
- 1996-07-11 WO PCT/US1996/011556 patent/WO1997003169A1/en not_active Application Discontinuation
- 1996-07-12 AR ARP960103546A patent/AR002814A1/es not_active Application Discontinuation
-
2002
- 2002-09-17 CN CNB021432295A patent/CN1232692C/zh not_active Expired - Fee Related
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1993023510A1 (en) * | 1992-05-12 | 1993-11-25 | The Procter & Gamble Company | Concentrated fabric softener compositions containing biodegradable fabric softeners |
WO1996011248A1 (en) * | 1994-10-07 | 1996-04-18 | The Procter & Gamble Company | Fabric softening composition containing chlorine scavengers |
WO1996019552A1 (en) * | 1994-12-21 | 1996-06-27 | Colgate-Palmolive Company | Clear, concentrated liquid fabric softener compositions |
WO1996033800A1 (en) * | 1995-04-27 | 1996-10-31 | Witco Corporation | Compositions containing diol and/or diol alkoxylate |
EP0763592A1 (de) * | 1995-09-18 | 1997-03-19 | The Procter & Gamble Company | Stabilisierte Textilweichmacherzusammensetzungen |
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