EP0734433B1 - Compositions assouplissantes concentrees liquides, de viscosite stable - Google Patents

Compositions assouplissantes concentrees liquides, de viscosite stable Download PDF

Info

Publication number
EP0734433B1
EP0734433B1 EP95904876A EP95904876A EP0734433B1 EP 0734433 B1 EP0734433 B1 EP 0734433B1 EP 95904876 A EP95904876 A EP 95904876A EP 95904876 A EP95904876 A EP 95904876A EP 0734433 B1 EP0734433 B1 EP 0734433B1
Authority
EP
European Patent Office
Prior art keywords
group
fabric softening
alkyl
acid
formula
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP95904876A
Other languages
German (de)
English (en)
Other versions
EP0734433B2 (fr
EP0734433A1 (fr
Inventor
John Cort Severns
Alice Marie Vogel
Errol Hoffman Wahl
Robert Mermelstein
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=22601878&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0734433(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Publication of EP0734433A1 publication Critical patent/EP0734433A1/fr
Publication of EP0734433B1 publication Critical patent/EP0734433B1/fr
Application granted granted Critical
Publication of EP0734433B2 publication Critical patent/EP0734433B2/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • 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

Definitions

  • the present invention relates to concentrated aqueous textile treatment compositions.
  • it relates to textile treatment compositions for use in the rinse cycle of a textile laundering operation to provide fabric softening/static control benefits, the compositions being characterized by excellent storage stability and excellent viscosity stability after freeze/thaw cycling.
  • Aqueous textile treatment compositions suitable for providing fabric softening and static control benefits during laundering are well-known in the art and have found wide-scale commercial application.
  • aqueous, rinse-added, fabric softening compositions contain, as the active softening component, substantially water-insoluble cationic materials having two long alkyl chains. Typical of such materials are di-hydrogenated tallow di-methyl ammonium chloride and imidazolinium compounds substituted with two stearyl groups. These materials are normally prepared in the form of a dispersion in water.
  • Cationic softener materials are normally supplied by the manufacturer containing about 70%-90% of active material in an organic liquid such as isopropanol or ethanol, sometimes containing a minor amount of water (up to 10%).
  • Retail fabric softening compositions are then prepared by dispersion of the softener in warm or hot water under carefully controlled conditions.
  • the physical form and dispersibility constraints of these industrial concentrates are such as to preclude their direct use by the domestic consumer; indeed, they can pose severe processing problems even for the industrial supplier of retail fabric softening compositions.
  • the present invention contains diester quaternary ammonium material (hereinafter referred to as "DEQA") as an essential component. Two primary types of DEQA are preferred.
  • the first type of DEQA preferably comprises, as the primary active, compounds of the formula: [(R) 4-m -N (+) -[(CH 2 ) n -Y-R 2 ] m ] X (-) wherein each R substituent is a short chain C 1 -C 6 , preferably C 1 -C 3 alkyl or hydroxyalkyl group, e.g., methyl (most preferred), ethyl, propyl, hydroxyethyl, and the like, benzyl or mixtures thereof each m is 2 or 3; each n is from 1 to about 4; each Y is -O-(O)C-, or -C(O)-O-, but not -OC(O)O-; each R 2 is a long chain C 12 -C 22 hydrocarbyl, or substituted hydrocarbyl substituent, preferably C 15 -C 19 alkyl or alkylene, most preferably C 15 -C 17 straight chain alkyl or alkylene
  • substituents R and R 2 can optionally be substituted with various groups such as alkoxyl or hydroxyl groups, and can be straight, or branched so long as the R 2 groups maintain their basically hydrophobic character.
  • the preferred compounds can be considered to be diester variations of ditallow dimethyl ammonium chloride (hereinafter referred to as "DTDMAC”), which is a widely used fabric softener. At least 80% of the DEQA is in the diester form, and from 0% to 20% can be DEQA monoester (e.g., only one of the ester groups is hydrolyzed to yield either-Y-H, or an -OH group).
  • the diester when specified, it can include the monoester that is present.
  • the percentage of monoester should be as low as possible, preferably no more than about 2.5%.
  • the overall ratios of diester to monoester are from 100:1 to 2:1, preferably from 50:1 to 5:1, more preferably from 13:1 to 8:1.
  • the di/monoester ratio is preferably about 11:1.
  • the level of monoester present can be controlled in manufacturing the DEQA.
  • the above compounds used as the biodegradable quaternized ester-amine softening material in the practice of this invention, can be prepared using standard reaction chemistry.
  • an amine of the formula RN(CH 2 CH 2 OH) 2 is esterified at both hydroxyl groups with an acid chloride of the formula R 2 C(O)Cl, then quaternized with an alkyl halide, RX, to yield the desired reaction product (wherein R and R 2 are as defined hereinbefore).
  • RX alkyl halide
  • this reaction sequence allows a broad selection of agents to be prepared.
  • the following are non-limiting examples (wherein all long-chain alkyl substituents are straight-chain): where -C(O)R 2 is derived from hardened tallow fatty acid.
  • stable liquid compositions herein are formulated at a neat pH in the range of from 2.5 to 4. The pH can be adjusted by the addition of a Bronsted acid. pH ranges for making stable softener compositions containing diester quaternary ammonium fabric softening compounds are disclosed in U.S. Pat. No. 4,767,547, Straathof, issued Aug. 30, 1988.
  • Suitable Bronsted acids include the inorganic mineral acids, carboxylic acids, in particular the low molecular weight (C 1 -C 5 ) carboxylic acids, and alkylsulfonic acids.
  • Suitable inorganic acids include HCl, H 2 SO 4 , HNO 3 and H 3 PO 4 .
  • Suitable organic acids include formic, acetic, citric, methylsulfonic and ethylsulfonic acids.
  • Preferred acids are hydrochloric, phosphoric, and citric acids.
  • the primary active has the general formula: wherein each Y, R, R 2 , and X (-) have the same meanings as before.
  • Such compounds include those having the formula: [CH 3 ] 3 N (+) [CH 2 CH(CH 2 OC[O]R 2 )OC(O)R 2 ] C1 (-) where C(O)R 2 is derived from hardened tallow fatty acid.
  • each R is a methyl or ethyl group and preferably each R 2 is in the range of C 15 to C 19 Degrees of branching and substitution can be present in the alkyl chains.
  • the anion X (-) in the molecule is the same as in DEQA (1) above.
  • the diester when specified, it can include the monoester that is present.
  • the amount of monoester that may be present is the same as in DEQA (1).
  • the present invention may also contain mixtures of the two primary types of DEQA.
  • compositions prepared by the present invention contain as an essential component a co-active fabric softening material, as described hereinafter, which is different from the biodegradable diester quaternary ammonium softening material
  • Di(2-amidoethyl)methyl quaternary ammonium salts are also suitable for use as Component (B) in the compositions of the invention herein, especially those having the formula: wherein each R 7 is selected from the group consisting of C 14 to C 20 alkyl and alkenyl groups, wherein each R 8 is selected from methyl, ethyl, and -(C m H 2m O) n 3H, wherein n 3 is from 1 to about 5, preferably 3, and wherein m, and X (-) have the same meaning as before.
  • This class of agents is disclosed in U.S. Pat. No. 4,134,840, Minegishi et al., issued January 16, 1979.
  • Exemplary materials are di((2-hydrogenatedtallowamidoethyl) ethoxylated (2 ethoxy groups) methyl ammonium methylsulfate, di(2-oleylamidoethyl) propoxylated (3-propoxy groups) methyl ammonium bromide, di(2-palmitoleylamidoethyl) dimethyl ammonium ethylsulfate and di(2-stearylamidoethyl) propoxylated (2 propoxy groups) methyl ammonium methylsulfate.
  • An exemplary commercial material suitable for use as Component (B) herein is di(2-tallowamidoethyl) ethoxylated methyl ammonium methylsulfate (such that the I.V. Component B is about 31) sold under the name Varisoft 222, from Witco Chemical Company.
  • a co-active fabric softening material for use as component (B) in the composition of the invention herein can also have the formula: wherein each R 9 is C 15 - C 17 alkyl group such that the IV of the parent fatty acid of this R 9 group is from 20 to 100, preferably from 30 to 70, most preferably from 35 to 60; and X (-) has the-same meaning as before.
  • a preferred fabric softening material of the present invention is prepared according to the synthesis disclosed in U.S. Pat. No. 3,915,867, Kang et al., issued October 28, 1975.
  • the fabric softening material generally comprises the reaction of purified C 14 -C 18 fatty acid alkylester mixture, triethanolamine, and a quaternizing reagent, preferably dimethyl sulfate.
  • the select fatty acid alkylesters are preferably a mixture of substantial amounts of oleic, palmitic, stearic add alkyl esters and may include minor amounts of other fatty substances.
  • a co-active fabric softening material suitable for use as Component (B) in the composition of the invention can also have the formula: wherein each R 10 is a C 12 - C 22 hydrocarbyl or substituted hydrocarbyl substituent, preferably C 15 - C 19 alkyl or alkylene, most preferably C 15 - C 17 straight chain alkyl or alkylene such that the IV of the parent fatty acid of this R 10 group is from 20 to 100, preferably from 30 to 70, most preferably from 35 to 60; and R and X (-) have the same meaning as before.
  • Tallow is a convenient and inexpensive source of long chain alkyl and alkenyl materials.
  • a specific example of a diester quaternary ammonium compound suitable for use in this invention herein include:
  • Suitable diester quaternary ammoniums of this invention are obtained by, e.g.: replacing "tallowyl” in the above compounds with, for example, cocoyl, palmoyl, lauryl, oleyl, stearyl, palmityl, or the like; replacing "methyl” in the above compounds with ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, or the hydroxy substituted analogs of these radicals; replacing "chloride” in the above compounds with bromide, methylsulfate, formate, sulfate, or nitrate.
  • the anion is merely present as a counterion of the positively charged quaternary ammonium compounds disclosed herein.
  • the scope of this invention is not considered limited to any particular anion.
  • the materials herein can be prepared by standard esterification and quaternization reactions, using readily available starting materials. General methods for preparation are disclosed in U.S. Pat. No. 4,137,180.
  • a co-active fabric softening material suitable for use as Component (B) in the composition of the invention can also have the formula: [(R) 4-m -N (+) -[(CH 2 ) n -Y-R 11 ] m ] X (-) except for those according to (3), wherein each R 11 is a long chain C 12 -C 22 , hydrocarbyl, or substituted hydrocarbyl substituent, preferably C 15 -C 19 alkyl or alkylene, most preferably C 15 -C 17 straight chain alkyl or alkylene such that the IV of the parent fatty acid of this R 11 group is from 20 to 100, preferably from 30 to 70, most preferably from 35 to 60; and each m, n, Y, R and X (-) have the same meaning as before.
  • the DEQA (A) material is (1), the requirement for component (B) is not met by this material and it is not present.
  • the present invention may also contain mixtures of the various co-active fabric softening materials.
  • compositions of the present invention herein comprise from about 15% to about 35%, preferably from about 20% to about 32%, most preferably from about 22% to about 27% of component (A) + component (B).
  • the ratio of component (A) to component (B) is from 0.25:1 to 4:1, preferably from 0.3:1 to 1.5:1.
  • the present invention utilizes an acid of sufficient concentration to keep the pH at the desired level and optionally, to fully protonate component (B) to the extent that it is not already quaternized.
  • the composition of the present invention is prepared using a molten premix of components (A) + (B), (hereinafter referred to as premix).
  • premix molten premix of components (A) + (B), (hereinafter referred to as premix).
  • premix molten premix of components (A) + (B), (hereinafter referred to as premix).
  • premix molten premix of components (A) + (B), (hereinafter referred to as premix).
  • premix molten premix of components (A) + (B), (hereinafter referred to as premix).
  • the premix is injected into an acid/water seat, then high shear milling is conducted and, electrolyte is added in no specific order.
  • the electrolyte is selected from the group consisting of the Group IA and IIA metals of the periodic table of elements, e.g., calcium chloride, sodium chloride, potassium bromide, and lithium chloride, and ammonium salts, e.g., ammonium chloride and lysine HCl.
  • the acid/water seat has an acid concentration up to about 2%.
  • the acid to (B) molar ratio is from about 0:1 to about 1.2:1.
  • the acid to (A) molar ratio is from about 0:1 to about 0.2:1.
  • the neat pH of the final composition is preferably from about 2.5 to about 4.
  • Suitable acids include the Bronsted acids, especially inorganic mineral acids and organic acids such as carboxylic acids.
  • Carboxylic acids include, in particular, the low molecular weight (C 1 -C 5 ) carboxylic acids of the formula R 12 -COOH (R 12 being a C 1 -C 5 or H alkyl group).
  • Suitable organic acids are selected from the group having the formula R 13 CH 2 SO 3 H, wherein R 13 is hydrogen or C 1 to C 4 alkyl.
  • Suitable specific organic acids include formic, methylsulfonic, ethylsulfonic, citric, gluconic, and aromatic carboxylic acids like benzoic acid.
  • Suitable inorganic acids include HCl, HBr, H 2 SO 4 , H 2 SO 3 , HNO 3 , and H 3 PO 4 .
  • Preferred acids are phosphoric, formic, acetic, hydrochloric, citric, and methylsulfonic acids. Mixtures of the above organic and inorganic acids are also suitable. Typically, acids such as citric, hydrochloric, phosphoric, and sulfuric are used because of their low cost and availability.
  • compositions of the present invention herein comprise from about 60% to about 90%, preferably from about 65% to about 85% of an aqueous liquid carrier.
  • the preferred aqueous carrier is water which can contain minor ingredients.
  • Fully-formulated fabric softening compositions made by the process of the present invention can optionally contain one or more of the following ingredients.
  • the fabric softening compositions herein optionally contain an aqueous emulsion of a predominantly linear polydialkyl or alkyl aryl siloxane in which the alkyl groups can have from one to five carbon atoms and can be wholly, or partially, fluoridated.
  • Suitable silicones are polydimethyl siloxanes having a viscosity, at 25°C, of from about 100 to about 100,000 centistokes, preferably from about 1,000 to about 12,000 centistokes. In some applications as low as 1 centistoke materials are preferred.
  • the fabric softening compositions herein can contain from about 0.1% to about 10%, of the silicone component.
  • the fabric softening compositions herein contain from 0% to about 3%, preferably from about 0.01% to about 2%, of a thickening agent.
  • suitable thickening agents include: cellulose derivatives, synthetic high molecular weight polymers (e.g., carboxyvinyl polymer and polyvinyl alcohol), and cationic guar gums.
  • the cellulosic derivatives that are functional as thickening agents herein can be characterized as certain hydroxyethers of cellulose, such as Methocel, marketed by Dow Chemicals, Inc.; also, certain cationic cellulose ether derivatives, such as Polymer JR-125, JR-400, and JR-30M, marketed by Union Carbide.
  • cationic guar gums such as Jaguar Plus, marketed by Stein Hail, and Gendrive 458, marketed by General Mills.
  • Preferred thickening agents herein are selected from the group consisting of methyl cellulose, hydroxypropyl methylcellulose, hydroxybutyl methylcellulose, or mixtures thereof, said cellulosic polymer having a viscosity in 2% aqueous solution at 20C of from about 15 to about 75,000 centipoises.
  • an optional soil release agent may be added.
  • the addition of the soil release agent may 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 ICI).
  • 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, and alkyl or acyl groups containing from about 1 to about 4 carbon atoms.
  • p is selected for water solubility and generally is from about 6 to about 113, preferably from about 20 to about 50.
  • u is critical to formulation in a liquid composition having a relatively high ionic strength. There should be very little material in which u is greater than 10. Furthermore, there should be at least 20%, preferably at least 40%, of material in which u ranges from about 3 to about 5.
  • the 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, alkylene moieties, alkenylene moieties, or mixtures thereof.
  • Arylene and alkarylene moieties which can be partially substituted for 1,4-phenylene include 1,3-phenylene, 1,2-phenylene, 1,8-naphthylene, 1,4-naphthylene, 2,2-biphenylene, 4,4-biphenylene, and mixtures thereof.
  • Alkylene and alkenylene moieties which can be partially substituted include 1,2-propylene, 1,4-butylene, 1,5-pentylene, 1,6-hexamethylene, 1,7-heptamethylene, 1,8-octamethylene, 1,4-cyclohexylene, and mixtures thereof.
  • the degree of partial substitution with moieties other than 1,4-phenylene should be such that the soil release properties of the compound are not adversely affected to any great extent.
  • the degree of partial substitution which can be tolerated will depend upon the backbone length of the compound, i.e., longer backbones can have greater partial substitution for 1,4-phylene 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-hexylene, 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 solubiity 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 a fatty alcohol, fatty acid, fatty amine, fatty acid amide, amine oxide, quaternary ammonium compound, or the hydrophobic moieties used to form soil release polymers.
  • the preferred scum dispersants are highly ethoxylated, e.g., more than about 17, preferably more than about 25, more preferably more than about 40, moles of ethylene oxide per molecule on the average, with the polyethylene oxide portion being from about 76% to about 97%, preferably from about 81% to about 94%, of the total molecular weight.
  • the level of scum dispersant is sufficient to keep the scum at an acceptable, preferably unnoticeable to the consumer, level under the conditions of use, but not enough to adversely affect softening. For some purposes it is desirable that the scum is nonexistent.
  • 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 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 CG/ICP.
  • Typical levels of bactericides used in the present compositions are from about 1 to about 1,000 ppm by weight of the agent.
  • the present invention can include optional components conventionally used in textile treatment compositions, for example, short chain alcohols such as ethanol, or propylene glycol, colorants, perfumes, preservatives, optical brighteners, opacifiers, surfactants, stabilizers such as guar gum and polyethylene glycol, anti-shrinkage agents, fabric crisping agents, spotting agents, germicides, fungicides, anti-oxidants such as butylated hydroxy toluene, anti-corrosion agents, and the like.
  • short chain alcohols such as ethanol, or propylene glycol
  • colorants such as ethanol, or propylene glycol
  • perfumes preservatives, optical brighteners, opacifiers, surfactants, stabilizers such as guar gum and polyethylene glycol
  • anti-shrinkage agents such as guar gum and polyethylene glycol
  • fabric crisping agents such as spotting agents
  • germicides such as fungicides
  • anti-oxidants such as buty
  • compositions of the present invention are preferably used in the rinse cycle of the conventional automatic laundry operations.
  • rinse water has a temperature of from about 15°C to about 60°C.
  • Fabrics or fibers are contacted with an effective amount, generally from about 20 ml to about 300 ml (per 3.5 kg of fiber or fabric being treated), of the compositions herein in an aqueous bath.
  • an effective amount generally from about 20 ml to about 300 ml (per 3.5 kg of fiber or fabric being treated), of the compositions herein in an aqueous bath.
  • the amount used is based upon the judgment of the user, depending on concentration of the softening materials, (A) + (B), fiber or fabric type, degree of softness desired, and the like.
  • from about 20 ml to about 300 ml of 9% to 40% dispersion of the softening materials (A) + (B) are used in a 25 gallon laundry rinse bath to soften and provide antistatic benefits to a 3.5 kg load of mixed fabrics.
  • the rinse bath contains from about 20 ppm to about 250 ppm of the fabric softening materials (A) + (B) herein. More preferably for United States conditions, the rinse bath contains from about 50 ppm to about 150 ppm of the fabric softening materials (A) + (B). More preferably for European conditions, the rinse bath contains from about 250 ppm to about 450 ppm of the fabric softening materials (A) + (B). More preferably for Japanese conditions, the rinse bath contains from about 30 ppm to about 80 ppm of the fabric softening materials (A) + (B). These concentration levels achieve superior fabric softening and static control.
  • the first three ingredients in each Formula are co-melted in a pyrex beaker, covered with a concave watchglass, for three hours at about 80-85°C to form the premix.
  • the water, HCl, and silicone antifoam are separately weighed into a sealed container and heated to about 83°C to form the water seat.
  • the premix is then injected into the water seat over three to four minutes at about 72°C while stirring at from about 1500 to about 3000 r.p.m.
  • a 15% aqueous solution of Lysine/HCl is added to the water seat/premix dispersion over seven minutes at about 71°C while stirring at from about 500 to about 1000 r.p.m..
  • the perfume, and the silicone DC-200 are added to the dispersion over thirty seconds.
  • the dispersion is milled for two minutes at about 70°C at from about 4000 to about 8000 r.p.m. of the mill.
  • a 40% aqueous solution of soil release polymer is added to the dispersion over two minutes at about 66°C while stirring at from about 500 to about 1000 r.p.m..
  • the dispersion is then chilled in an ice bath at about 25°C for 8 minutes while stirring at from about 200 to about 500 r.p.m..
  • compositions containing mixtures of the two softener active materials, Component (A) and Component (B), (Formulas 2-4), have more stable viscosities at temperatures down to 10°C, than compositions containing only the individual softener active Component (A) or Component (B), (Formulas 1 and 5).
  • Ditallow Imidazoline Amide in the amount of 375g is melted by heating to about 93°C.
  • This molten softener is then dispersed into 376g of deionized water at about 82°C containing 90g of a 28.25% HCl solution and 4.8g of the DC-2210 silicone antifoam over five minutes while stirring with an IKA model RW20 DZM stirrer at 400-600 r.p.m..
  • the resulting dispersion is stirred for an additional four minutes.
  • a second aliquot of about 82°C deionized water in the amount of 580g is stirred into the thick dispersion over two and one half minutes.
  • a blend of 20.25g of perfume and 2.85g of DC-200 silicone fluid is then added to the dispersion over thirty seconds, followed by two and one half minutes of mixing with an IKA Ultra-Turrax T50 high shear mill at 8000 r.p.m..
  • the dispersion is then cooled to room temperature over three minutes by passing it through a small plate and frame heat exchanger.
  • the preservative in the amount of 0.3g is added at room temperature following the cool down.
  • N,N-di(hydrogenated tallowyl-oxy-ethyl)-N,N-dimethyl ammonium chloride in the amount of 431g and 24g of ethanol are melted at about 91°C.
  • This molten softener is dispersed into 954g of deionized water at about 82°C containing 8.25g of a 0.968 N HCl solution, 4.8g of DC-2210 silicone antifoam and 18.75g of a 40% solution of soil release polymer over five and one half minutes while stirring at 800-1100 r.p.m.. Subsequently, 35g of an aqueous 15% CaCl2 solution is stirred into the dispersion over four and one half minutes.
  • a blend of 20.25g of perfume and 2.85g of DC-200 silicone fluid is then added to the dispersion over thirty seconds, followed by two and one half minutes of mixing with a high shear mill at 8000 r.p.m..
  • the preservative in the amount of 0.3g is added just prior to cool-out.
  • the dispersion is then cooled to room temperature over two and one half minutes by passing through a small plate and frame heat exchanger.
  • Ditallow Imidazoline Amide in the amount of 214g, 115.5g N,N-di(tallowyl-oxy-ethyl)-N,N-dimethyl ammonium chloride and 19g of ethanol are co-melted at about 91°C.
  • This molten softener mixture is dispersed into 1,102g of deionized water at about 82°C containing 14.55g of HCl and 4.8g of DC-2210 silicone antifoam over five and one half minutes while stirring at 800-1100 r.p.m..
  • 37.5g of an aqueous 15% CaCl2 solution is stirred into the dispersion over four and one half minutes.
  • a blend of 20.25g of perfume and 2.85g of DC-200 silicone fluid is then added to the dispersion over thirty seconds, followed by two and one half minutes of mixing with high shear mill at 8000 r.p.m..
  • the dispersion is then cooled to room temperature over two and one half minutes by passing it through a small plate and frame heat exchanger.
  • the preservative in the amount of 0.3g is added at room temperature following cool-out.
  • Example II Materials prepared in the same manner as Example III except that the amounts of imidazoline, N,N-di(hydrogenated tallowyl-oxy-ethyl)-N,N-dimethyl ammonium chloride, ethanol, and HCl vary according to the formulas shown above.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Biological Depolymerization Polymers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Detergent Compositions (AREA)

Claims (7)

  1. Composition d'adoucissement de tissus liquide aqueuse concentrée stable comprenant:
    (A) un matériau adoucissant de tissus d'ammonium quaternaire biodégradable de type diester choisi dans le groupe constitué des substances de formule suivante: [ (R)4-m-N(+)-[(CH2)n-Y-R2]m ] X(-) dans laquelle chaque groupe R est choisi dans le groupe constitué de groupes alkyle ou hydroxyalkyle en C1-C6; chaque indice m est égal à 2; chaque indice n a une valeur de 1 à 4; chaque groupe R2 est choisi dans le groupe constitué d'un groupe hydrocarbyle ou hydrocarbyle substitué en C12-C22 tel que l'indice d'iode (IV) de l'acide gras apparenté de ce groupe R2 soit inférieur à 10; chaque groupe Y est un groupe -O-(O)C ou -C(O)-O, mais pas OC(O)O; et dans laquelle X(-) est un anion compatible; ou de formule:
    Figure 00450001
    dans laquelle chaque groupe Y, R, R2 et X(-) a la même signification que ci-dessus; ou de leurs mélanges, et
    (B) un matériau adoucissant de tissus co-actif choisi dans le groupe constitué des substances de formule :
    Figure 00450002
    dans laquelle chaque groupe R7 est choisi dans le groupe constitué des groupes alkyle et alcényle en C14-C20; chaque groupe R8 est choisi parmi les groupes méthyle, éthyle et -(CmH2mO)n3H; dans laquelle n3 a une valeur de 1 à 5; et dans laquelle chaque indice m et le groupe X(-) ont la même signification que ci-dessus; ou de formule :
    Figure 00460001
    dans laquelle chaque groupe R9 est un groupe alkyle gras en C15-C17 tel que l'indice d'iode (IV) de l'acide gras apparenté de ce groupe R9 soit de 20 à 100; et X(-) a la même signification que ci-dessus; ou de formule :
    Figure 00460002
    dans laquelle chaque groupe R10 est un substituant hydrocarbyle ou hydrocarbyle substitué en C12-C22 tel que l'indice d'iode (IV) de l'acide gras apparenté de ce groupe R10 soit de 20 à 100; et R et X(-) ont la même signification que ci-dessus; ou de formule : [ (R)4-m-N(+)-[(CH2)n-Y-R11]m ] X(-) excepté pour les substances selon (3), dans laquelle chaque groupe R11 est un substituant hydrocarbyle ou hydrocarbyle substitué à longue chaíne en C12-C22 ou tel que l'indice d'iode (IV) de l'acide gras apparenté de ce groupe R11 soit de 20 à 100, et chacun de m, n, Y, R et X(-) a la même signification que ci-dessus; ou leurs mélanges; dans laquelle la quantité totale de composants (A)+(B) est de 15% à 35%, de préférence de 20% à 32%, mieux encore de 22% à 27%, le rapport de (A) à (B) étant de 0,25:1 à 4:1, et bien mieux encore de 0,3:1 à 1,5:1; dans laquelle, lorsque (A) est (1), (B) n'est pas (5); dans laquelle, lorsque (A) est (2), (B) n'est pas (4); dans laquelle, lorsque (A) est (1), un groupe R étant un groupe méthyle et l'autre étant un groupe C2H4OH, (B) n'est pas (3); dans laquelle, lorsque B(3) est [CH2CH2OH][CH3]+N[(CH2CH2OC)(O)R2]X- où X(-) étant tel que défini ci-dessus, A n'est pas (1); et de préférence dans laquelle l'agent adoucissant de tissus aqueux concentré final a un pH à l'état non dilué de 2,5 à 4.
  2. Composition d'adoucissement de tissus liquide aqueuse concentrée stable selon la revendication 1, comprenant :
    (A) un matériau adoucissant de tissus d'ammonium quaternaire biodégradable de type diester ayant pour formule : [ (R)4-m-N(+)-[(CH2)n-Y-R2]m ] X(-) dans laquelle chaque groupe R est choisi dans le groupe constitué de groupes alkyle ou hydroxyalkyle en C1-C6; chaque indice m est égal à 2; chaque indice n a une valeur de 1 à 4; chaque groupe R2 est choisi dans le groupe constitué d'un groupe hydrocarbyle ou hydrocarbyle substitué en C12-C22 tel que le (IV) de l'acide gras apparenté de ce groupe R2 soit inférieur à 10; chaque groupe Y est un groupe -O-(O)C ou -C(O)-O, mais pas OC(O)O; et dans laquelle X(-) est un anion compatible; et
    (B) un matériau adoucissant de tissus co-actif ayant pour formule :
    Figure 00470001
    dans laquelle chaque groupe R7 est choisi dans le groupe constitué des groupes alkyle et alcényle en C14-C20; chaque groupe R8 est choisi parmi les groupes méthyle, éthyle et -(CmH2mO)n3H; dans laquelle n3 a une valeur de 1 à 5; et dans laquelle chaque indice m et le groupe X(-) ont la même signification que ci-dessus.
  3. Composition d'adoucissement de tissus liquide aqueuse concentrée stable selon la revendication 1, comprenant :
    (A) un matériau adoucissant de tissus d'ammonium quaternaire biodégradable de type diester ayant pour formule :
    Figure 00480001
    dans laquelle chaque groupe Y est -O(O)C ou -C(O)O-, mais pas -OC(O)O; et dans laquelle chaque groupe R est choisi dans le groupe constitué de groupes alkyle ou hydroxyalkyle en C1-C6; chaque groupe R2 est choisi dans le groupe constitué d'un groupe hydrocarbyle ou hydrocarbyle substitué en C12-C22 tel que le (IV) de l'acide gras apparenté de ce groupe R2 soit inférieur à 10; et dans lequel X(-) est un anion compatible; et
    (B) un matériau adoucissant de tissus co-actif ayant pour formule :
    Figure 00480002
    dans laquelle chaque groupe R7 est choisi dans le groupe constitué des groupes alkyle et alcényle en C14-C20; chaque groupe R8 est choisi parmi les groupes méthyle, éthyle et -(CmH2mO)n3H; dans laquelle n3 a une valeur de 1 à 5; et dans laquelle chaque indice m et le groupe X(-) ont la même signification que ci-dessus.
  4. Composition d'adoucissement de tissus liquide aqueuse concentrée stable selon la revendication 1, comprenant:
    (A) un matériau adoucissant de tissus d'ammonium quaternaire biodégradable de type diester ayant pour formule :
    Figure 00490001
    dans laquelle chaque groupe Y est -O(O)C ou -C(O)O, mais pas -OC(O)O, et dans laquelle chaque groupe R est choisi dans le groupe constitué de groupes alkyle ou hydroxyalkyle en C1-C6; chaque groupe R2 est choisi dans le groupe constitué d'un groupe hydrocarbyle ou hydrocarbyle substitué en C12-C22 tel que le (IV) de l'acide gras apparenté de ce groupe R2 soit inférieur à 10; et dans laquelle X(-) est un anion compatible; et
    (B) un matériau adoucissant de tissus co-actif ayant pour formule :
    Figure 00490002
    dans laquelle chaque groupe R9 est un groupe alkyle gras en C15-C17 tel que le (IV) de l'acide gras apparenté de ce groupe R9 soit de 20 à 100 et dans laquelle le groupe X(-) a la même signification que ci-dessus.
  5. Composition d'adoucissement de tissus liquide aqueuse concentrée stable selon la revendication 1, comprenant :
    (A) un matériau adoucissant de tissus d'ammonium quaternaire biodégradable de type diester ayant pour formule :
    Figure 00490003
    dans laquelle chaque Y est -O(O)C ou -C(O)O-, mais pas -OC(O)O et dans laquelle chaque groupe R est choisi dans le groupe constitué de groupes alkyle ou hydroxyalkyle en C1-C6; chaque groupe R2 est choisi dans le groupe constitué d'un groupe hydrocarbyle ou hydrocarbyle substitué en C12-C22 tel que le (IV) de l'acide gras apparenté de ce groupe R2 soit inférieur à 10; et dans laquelle X(-) est un anion compatible; et
    (B) un matériau adoucissant de tissus co-actif ayant pour formule : [ (R)4-m-N(+)-[(CH2)n-Y-R11]m ] X(-) dans laquelle chaque groupe R11 est un substituant hydrocarbyle ou hydrocarbyle substitué à longue chaíne en C12-C22 tel que le (IV) de l'acide gras apparenté de ce groupe R11 soit de 20 à 100; et chacun de m, n, Y, R et X(-) a la même signification que ci-dessus, ou leurs mélanges.
  6. Procédé de préparation d'une composition selon l'une quelconque des revendications 1 à 5, qui comprend les étapes consistant, en utilisant un pré-mélange fondu :
    A. à pré-mélanger (A) un agent adoucissant de tissus d'ammonium quaternaire biodégradable de type diester et (B) un agent adoucissant de tissus secondaire ; et
    B. à injecter le pré-mélange dans un bain d'acide et d'eau comprenant de préférence un acide choisi dans le groupe constitué des acides inorganiques minéraux et des acides organiques ayant pour formule R12COOH, dans laquelle R12 est H ou un groupe alkyle en C1-C5, ou pour formule R13CH2SO3H, dans laquelle R13 est de l'hydrogène ou un groupe alkyle en C1-C4, et leurs mélanges; mieux encore dans lequel l'acide est l'acide phosphorique, l'acide chlorhydrique, l'acide citrique ou leurs mélanges ; de préférence dans lequel la concentration du bain d'acide et d'eau est jusqu'à 2 % ; et de préférence dans lequel le rapport molaire de l'acide à (B) est de 0:1 à 1,2:1 ; et
    C. à effectuer un broyage à haut taux de cisaillement et à ajouter un électrolyte de préférence choisi dans le groupe constitué de sels de métaux des groupes IA et IIA du tableau périodique des éléments, de préférence le chlorure de calcium ou des sels d'ammonium.
  7. Composition selon la revendication 8, dans laquelle ledit pré-mélange est combiné à un dispersant d'écume.
EP95904876A 1993-12-13 1994-12-12 Compositions assouplissantes concentrees liquides, de viscosite stable Expired - Lifetime EP0734433B2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US16611393A 1993-12-13 1993-12-13
US166113 1993-12-13
PCT/US1994/014255 WO1995016766A1 (fr) 1993-12-13 1994-12-12 Compositions assouplissantes concentrees liquides, de viscosite stable

Publications (3)

Publication Number Publication Date
EP0734433A1 EP0734433A1 (fr) 1996-10-02
EP0734433B1 true EP0734433B1 (fr) 2000-03-22
EP0734433B2 EP0734433B2 (fr) 2004-03-24

Family

ID=22601878

Family Applications (1)

Application Number Title Priority Date Filing Date
EP95904876A Expired - Lifetime EP0734433B2 (fr) 1993-12-13 1994-12-12 Compositions assouplissantes concentrees liquides, de viscosite stable

Country Status (9)

Country Link
EP (1) EP0734433B2 (fr)
JP (1) JP3746294B2 (fr)
CN (1) CN1161450C (fr)
BR (1) BR9408310A (fr)
CA (1) CA2179007C (fr)
DE (1) DE69423650T3 (fr)
ES (1) ES2144603T5 (fr)
MA (1) MA23394A1 (fr)
WO (1) WO1995016766A1 (fr)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6559117B1 (en) * 1993-12-13 2003-05-06 The Procter & Gamble Company Viscosity stable concentrated liquid fabric softener compositions
GB9816659D0 (en) * 1998-07-30 1998-09-30 Dow Europ Sa Composition useful for softening, cleaning, and personal care applications and processes for the preparation thereof
GB0021766D0 (en) 2000-09-05 2000-10-18 Unilever Plc Fabric conditioning compositions
GB0021765D0 (en) 2000-09-05 2000-10-18 Unilever Plc A method of preparing fabric conditioning compositions
MXPA04012377A (es) * 2002-06-13 2005-02-25 Procter & Gamble Composiciones que comprenden un sistema activo suavizante de telas que comprende por lo menos dos activos cationicos suavizantes de telas.
US6927202B2 (en) 2002-09-19 2005-08-09 Unilever Home & Personal Care, Usa Division Of Conopco, Inc. Fabric conditioning compositions
CN102230278B (zh) * 2011-06-07 2013-02-13 廊坊乐万家联合家化有限公司 一种浓缩衣物柔顺剂及其制备方法
US20180371366A1 (en) * 2015-12-15 2018-12-27 Rhodia Operations Method for enhancing stability of composition by using quat and polysaccharides
WO2017107819A1 (fr) * 2015-12-22 2017-06-29 Rhodia Operations Compositions comprenant un composé d'ammonium quaternaire et des polysaccharides

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0052517A1 (fr) * 1980-11-18 1982-05-26 THE PROCTER & GAMBLE COMPANY Compositions concentrées d'adoucissants textiles
EP0079643A2 (fr) * 1981-11-17 1983-05-25 THE PROCTER & GAMBLE COMPANY Compositions adoucissantes concentrées pour matières textiles
US4399045A (en) * 1980-11-18 1983-08-16 The Procter & Gamble Company Concentrated fabric softening compositions
EP0239910A2 (fr) * 1986-04-02 1987-10-07 The Procter & Gamble Company Adoucissants biodégradables pour tissus
EP0295386A2 (fr) * 1987-06-19 1988-12-21 Hüls Aktiengesellschaft Compositions adoucissantes concentrées
US5066414A (en) * 1989-03-06 1991-11-19 The Procter & Gamble Co. Stable biodegradable fabric softening compositions containing linear alkoxylated alcohols
WO1993001265A1 (fr) * 1991-07-05 1993-01-21 Unilever Plc Composition adoucissante pour tissus
EP0550361A1 (fr) * 1991-12-31 1993-07-07 Stepan Europe Tensioactifs à base de composés d'ammonium quaternaire, procédés de préparation, bases et compositions assouplissantes dérivées
WO1993016157A1 (fr) * 1992-02-07 1993-08-19 Henkel Kommanditgeselschaft Auf Aktien Procede de fabrication de concentres aqueux, de faible viscosite, d'esters quaternises
EP0643128A1 (fr) * 1993-09-10 1995-03-15 Kao Corporation Compositions adoucinants aqueuses, nouveau sel d'ammonium quaternaire et procédé pour la préparation de ce sel
WO1995020597A1 (fr) * 1994-01-26 1995-08-03 Ciba-Geigy Ag Oligonucleotides modifies

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4789491A (en) * 1987-08-07 1988-12-06 The Procter & Gamble Company Method for preparing biodegradable fabric softening compositions
DE3876196T2 (de) * 1987-09-23 1993-04-15 Procter & Gamble Lineare alkoxylierte alkohole enthaltende stabile, biologisch abbaubare waescheweichspuelerzusammensetzungen.
EP0345842A3 (fr) * 1988-05-27 1990-04-11 The Procter & Gamble Company Compositions adoucissantes pour le linge contenant des mélanges des esters d'imidazoline substitués et des sels quaternaires d'ammonium ester
NZ235490A (en) * 1989-10-16 1993-08-26 Colgate Palmolive Co Fabric-softening compositions
JP2956274B2 (ja) * 1991-05-10 1999-10-04 ライオン株式会社 液体柔軟剤組成物
JP2970132B2 (ja) * 1991-10-04 1999-11-02 ライオン株式会社 液体柔軟剤組成物
RU94046015A (ru) * 1992-05-12 1996-10-10 Дзе Проктер Энд Гэмбл Компани (US) Концентрированная композиция замасливателя тканей, способ получения твердой порошковой композиции замасливателя, способ получения жидкой композиции замасливателя и способ замасливания тканей

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0052517A1 (fr) * 1980-11-18 1982-05-26 THE PROCTER & GAMBLE COMPANY Compositions concentrées d'adoucissants textiles
US4399045A (en) * 1980-11-18 1983-08-16 The Procter & Gamble Company Concentrated fabric softening compositions
EP0079643A2 (fr) * 1981-11-17 1983-05-25 THE PROCTER & GAMBLE COMPANY Compositions adoucissantes concentrées pour matières textiles
EP0239910A2 (fr) * 1986-04-02 1987-10-07 The Procter & Gamble Company Adoucissants biodégradables pour tissus
EP0295386A2 (fr) * 1987-06-19 1988-12-21 Hüls Aktiengesellschaft Compositions adoucissantes concentrées
US5066414A (en) * 1989-03-06 1991-11-19 The Procter & Gamble Co. Stable biodegradable fabric softening compositions containing linear alkoxylated alcohols
WO1993001265A1 (fr) * 1991-07-05 1993-01-21 Unilever Plc Composition adoucissante pour tissus
EP0550361A1 (fr) * 1991-12-31 1993-07-07 Stepan Europe Tensioactifs à base de composés d'ammonium quaternaire, procédés de préparation, bases et compositions assouplissantes dérivées
WO1993016157A1 (fr) * 1992-02-07 1993-08-19 Henkel Kommanditgeselschaft Auf Aktien Procede de fabrication de concentres aqueux, de faible viscosite, d'esters quaternises
EP0643128A1 (fr) * 1993-09-10 1995-03-15 Kao Corporation Compositions adoucinants aqueuses, nouveau sel d'ammonium quaternaire et procédé pour la préparation de ce sel
WO1995020597A1 (fr) * 1994-01-26 1995-08-03 Ciba-Geigy Ag Oligonucleotides modifies

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
"Römpps Chemie-Lexikon", Franckh'sche Verlagshandlung, Stuttgart, 8th edition, p.1918 *
ACKMANN R.G. et al: 'Anomalous high iodine value of squalene and the impact on iodine values of shark liver oils', J.AM.OIL.CHEM.SOC., 1998, vol.75, no.9, pages 1223 to 1225 *
BARLOW S.M. et al: 'Collaborative test of determination of iodine value in fish oils.1.Reaction time and carbon tetrachloride or cyclohexane as solvents', J.AM.OIL.CHEM.SOC., 1997, vol.74, no.9, pages 1077 to 1083 *
Handbook of Chemistry and Physics, ed.by David R.Lide, 73rd edition 1992-1993, page 7-29 *

Also Published As

Publication number Publication date
ES2144603T3 (es) 2000-06-16
WO1995016766A1 (fr) 1995-06-22
JP3746294B2 (ja) 2006-02-15
DE69423650T3 (de) 2004-11-18
MA23394A1 (fr) 1995-07-01
CA2179007A1 (fr) 1995-06-22
BR9408310A (pt) 1997-08-26
CN1161450C (zh) 2004-08-11
JPH09506684A (ja) 1997-06-30
CN1142847A (zh) 1997-02-12
EP0734433B2 (fr) 2004-03-24
DE69423650T2 (de) 2000-11-02
DE69423650D1 (de) 2000-04-27
EP0734433A1 (fr) 1996-10-02
CA2179007C (fr) 2002-04-02
ES2144603T5 (es) 2004-11-16

Similar Documents

Publication Publication Date Title
US5066414A (en) Stable biodegradable fabric softening compositions containing linear alkoxylated alcohols
US4789491A (en) Method for preparing biodegradable fabric softening compositions
CA1340425C (fr) Compositions assouplissantes stables biodegradables pour tissus, a base d'alcools alcoxyles lineaires
CA1316641C (fr) Compositions stables d'assouplissant pour tissus, biodegradable, contenant des sels quaternaires de monoester de 2-hydroxypropyle
US5368756A (en) Fabric softening compositions containing mixtures of softener material and highly ethoxylated curd dispersant
US6797688B2 (en) Concentrated, preferably biodegradable, quaternary ammonium fabric softener compositions containing cationic polymers and process for preparation
US4767547A (en) Biodegradable fabric softeners
US20110219730A1 (en) Concentrated fabric softener active compositions
US5670476A (en) Fabric softening compositions containing mixtures of substituted imidazoline fabric softener materials and highly ethoxylated curd dispersant
US5116520A (en) Fabric softening and anti-static compositions containing a quaternized di-substituted imidazoline ester fabric softening compound with a nonionic fabric softening compound
EP0773982B1 (fr) Adoucisseur s'ajoutant au rincage et contenant des antioxydants protegeant le linge de la decoloration sous l'effet du soleil
WO1995031524A2 (fr) Compositions d'assouplissant concentrees biodegradables
CA2192802C (fr) Compositions d'assouplissement a ajouter au rincage contenant des filtres solaires pour proteger les tissus de la decoloration due au soleil
EP0345842A2 (fr) Compositions adoucissantes pour le linge contenant des mélanges des esters d'imidazoline substitués et des sels quaternaires d'ammonium ester
EP0734433B1 (fr) Compositions assouplissantes concentrees liquides, de viscosite stable
EP0295739A2 (fr) Méthode pour préparer des compositions biodégradables pour le traitement du linge
US6559117B1 (en) Viscosity stable concentrated liquid fabric softener compositions
EP0644925B1 (fr) Compositions adoucissantes, biodegradables et stables, pour tissus
US5376286A (en) Process for preparing concentrated imidazoline fabric softener compositions

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19960528

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): DE ES FR GB

17Q First examination report despatched

Effective date: 19961213

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

RBV Designated contracting states (corrected)

Designated state(s): DE ES FR GB

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE ES FR GB

REF Corresponds to:

Ref document number: 69423650

Country of ref document: DE

Date of ref document: 20000427

ET Fr: translation filed
REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2144603

Country of ref document: ES

Kind code of ref document: T3

PLBQ Unpublished change to opponent data

Free format text: ORIGINAL CODE: EPIDOS OPPO

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

26 Opposition filed

Opponent name: HENKEL KGAA

Effective date: 20001222

Opponent name: UNILEVER PLC

Effective date: 20001221

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

PLAW Interlocutory decision in opposition

Free format text: ORIGINAL CODE: EPIDOS IDOP

PUAH Patent maintained in amended form

Free format text: ORIGINAL CODE: 0009272

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: PATENT MAINTAINED AS AMENDED

27A Patent maintained in amended form

Effective date: 20040324

AK Designated contracting states

Kind code of ref document: B2

Designated state(s): DE ES FR GB

REG Reference to a national code

Ref country code: ES

Ref legal event code: DC2A

Date of ref document: 20040617

Kind code of ref document: T5

ET3 Fr: translation filed ** decision concerning opposition
PLAB Opposition data, opponent's data or that of the opponent's representative modified

Free format text: ORIGINAL CODE: 0009299OPPO

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20131126

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20131126

Year of fee payment: 20

Ref country code: ES

Payment date: 20131218

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20131230

Year of fee payment: 20

REG Reference to a national code

Ref country code: DE

Ref legal event code: R071

Ref document number: 69423650

Country of ref document: DE

REG Reference to a national code

Ref country code: GB

Ref legal event code: PE20

Expiry date: 20141211

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20141211

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20150226

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20141213