EP0075976B1 - Alkalische Wassrig-flüssige Detergenzzusammensetzung mit normalerweise instabilen Esterparfums - Google Patents
Alkalische Wassrig-flüssige Detergenzzusammensetzung mit normalerweise instabilen Esterparfums Download PDFInfo
- Publication number
- EP0075976B1 EP0075976B1 EP19820201075 EP82201075A EP0075976B1 EP 0075976 B1 EP0075976 B1 EP 0075976B1 EP 19820201075 EP19820201075 EP 19820201075 EP 82201075 A EP82201075 A EP 82201075A EP 0075976 B1 EP0075976 B1 EP 0075976B1
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- EP
- European Patent Office
- Prior art keywords
- composition
- water
- group
- carbon atoms
- aqueous liquid
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- 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.)
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Classifications
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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
- C11D9/00—Compositions of detergents based essentially on soap
- C11D9/04—Compositions of detergents based essentially on soap containing compounding ingredients other than soaps
- C11D9/44—Perfumes; Colouring materials; Brightening agents ; Bleaching agents
-
- 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
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
- C11D3/1246—Silicates, e.g. diatomaceous earth
- C11D3/128—Aluminium silicates, e.g. zeolites
Definitions
- This invention relates to alkaline aqueous liquid detergent compositions utilizing ester-containing perfumes.
- the large class of perfumes known as ester perfumes which contain the structure are generally unstable in alkaline aqueous liquid detergent compositions.
- the alkalinity promotes decomposition by hydrolysis. As a consequence, the composition so affected can have an undesirable odor. Therefore, such perfumes generally are not used in alkaline aqueous liquid detergent compositions.
- an object of this invention is to permit the addition of ester perfumes to alkaline aqueous liquid detergent compositions without a stability problem.
- a further object of the invention is to provide alkaline aqueous liquid detergent compositions which contain ester perfumes without a stability problem.
- U.S.-A-4,265,777 discloses liquid detergent compositions consisting of a synthetic detergent surfactant, unsaturated fatty acid soap and an aluminosilicate detergency builder.
- U.S.-A-4,217,250 discloses that polycarboxylates may be added to perfumes to sequester metal ions which act as a catalyst for oxidation.
- the present invention relates to alkaline aqueous liquid detergent compositions comprising:
- the present invention relates to the fact that ester perfumes that are normally unstable in alkaline aqueous liquid detergent compositions are stable in such compositions provided such compositions comprise zeolite A, an unsaturated fatty acid soap, a nonionic surfactant and a polycarboxylate detergency builder and are substantially free of synthetic anionic surfactants.
- the pH of such compositions ranges from about 9.5 to about 11.5 and preferably from about 10 to about 11.
- Such stability is totally unexpected because most ester perfumes in such highly alkaline aqueous liquid detergent compositions decompose by hydrolysis during storage.
- the essential components of the detergent compositions of this invention are (1) zeolite A, (2) an unsaturated fatty acid soap, (3) a nonionic surfactant (4) a polycarboxylate builder, and (5) a normally unstable ester perfume.
- the detergent compositions within the invention are substantially free of synthetic anionic surfactants. The addition of a synthetic anionic surfactant to the detergent compositions within the invention renders the ester perfume unstable.
- Detergency builders are generally characterized by an ability to sequester or precipitate water hardness ions, calcium and magnesium in particular. Detergency builders may also be used to maintain or assist in maintaining an alkaline pH in a washing solution.
- the aluminosilicate detergency builder for use herein is commonly known as hydrated zeolite A. It should contain at least about 10% water of hydration, preferably at least about 18% water of hydration and should have a particle size of from about 0.01 um to about 25 ⁇ m, preferably from about 0.1 ⁇ m to about 10 pm, more preferably from about 0.5 ⁇ m to about 5.
- This aluminosilicate material is more fully described in U.S.-A-4,096,081. Phenicie et al, issued June 20, 1978 and U.S.-A-4,180,485, Llenado, issued December 25, 1979. Both patents are incorporated herein by reference.
- Zeolite A should preferably be free of any substantial amount of particles having a diameter above about 10 pm. Also, it should have a calcium ion exchange capacity of at least about 100 milligram equivalents of calcium carbonate per gram, preferably at least 200 milligram equivalents of calcium carbonate per gram and most preferably at least 250 milligram equivalents of calcium carbonate per gram on an anhydrous basis.
- the initial ion exchange rate should be at least 2 grains/gallon/minute/gram/gallon as measured at room temperature in the presence of 7 grains of mixed 2:1 Ca ++ :Mg ++ and a level of detergency builder sufficient to control that level of hardness. This initial rate can be approximated by drawing a line from the initial point to the level of hardness after 1/2 minute as determined by a calcium ion specific electrode.
- the amount of zeolite A in the compositions is from 7% to 30%, preferably from 10% to 20% and most preferably from 10% to 15%.
- Additional crystalline aluminosilicate detergency builder materials such as those commonly known as hydrated zeolites X and P(B) and amorphous hydrated aluminosilicate material of the empirical formula wherein M is sodium, potassium or ammonium, Z is from about 0.5 to about 2; and y is 1, can be present.
- aluminosilicate materials are more fully described in the two patents cited above.
- the amount of such additional aluminosilicates in the compositions can be present at levels of from 0% to 3%, but preferably they are not present at all.
- the unsaturated fatty acid soap of this invention contains from 16 to 22 carbon atoms, preferably in a straight chain configuration. Preferably the number of carbon atoms in the unsaturated fatty acid soap is from 16 to 18.
- This unsaturated soap in common with other anionic materials in the detergent compositions of this invention, has a cation which renders the soap water-soluble and/or dispersible.
- Suitable cations include sodium, potassium, ammonium, monethanolammonium, diethanolammonium, triethanolammonium, tetramethylammonium, etc. cations.
- Sodium ions are preferred although in more concentrated liquid formulations potassium, monoethanolammonium diethanolammonium, and triethanolammonium cations are useful.
- a level of at least 5% of the unsaturated fatty acid soap is desirable to provide a noticeable improvement in performance.
- Preferred levels of unsaturated fatty acid soap are from 5% to 40%, preferably from 5% to 30% and most preferably from 5% to 15%.
- the unsaturated fatty acid soap is preferably present at a level that will provide a level of from 150 ppm to 600 ppm, preferably from 150 ppm to 300 ppm in the wash solution at recommended U.S. usage levels and from 150 ppm to 2400 ppm, preferably from 600 ppm to 1500 ppm for European usage levels.
- the aluminosilicate assists in keeping the unsaturated soap from forming an insoluble curd.
- Mono-, di-, and tri-unsaturated fatty acids are all essentially equivalent so it is preferred to use mostly mono-unsaturated soaps to minimize the risk of rancidity.
- Suitable sources of unsaturated fatty-acids are well known. For example, see Bailey's Industrial Oil and Fat Products, Th'ird Edition, Swern, published by Interscience Publisher (1964), incorporated herein by reference.
- the level of saturated soaps is kept as low as possible, preferably less than 50% of the unsaturated soap.
- low levels of saturated soaps can be added and will provide some performance for clay and dirt removal if they contain at least 16 carbon atoms.
- Tallow and palm oil soaps can be used if cost considerations are important, but will not give as good results as can be obtained with all unsaturated soap.
- Coconut soap does not provide a benefit and should not be added in significant amounts.
- the synthetic surfactant is the synthetic surfactant
- nonionic surfactant In addition to the unsaturated fatty acid soap there is a nonionic surfactant present, especially one which is an efficient soap curd dispersant.
- the preferred nonionic surfactant can be either a water-soluble nonionic or a semi-polar nonionic surfactant or mixtures thereof.
- Especially preferred nonionic surfactants are those which are relatively hardness insensitive.
- Suitable nonionic surfactants can be prepared by a variety of methods well known in the art. In general terms, such nonionic surfactants are typically prepared by condensing ethylene oxide with a compound containing an active hydrogen under conditions of acidic or basic catalysis.
- Nonionic surfactants for use herein comprise those typical nonionic surface active agents well known in the detergency arts. Useful nonionic surfactants include those described in U,S.-A-4,075,118, Gault et al, issued February 21, 1978; U.S.-A-4,079,078, Collins, issued March 14, 1978; and U.S.-A-3,963,649; Spadini et al, issued June 15, 1976, all of the above patents being incorporated herein by reference.
- nonionic surfactants useful are those having the formula wherein R is an alkyl, hydroxy alkyl, alkylene, hydroxy alkylene, acyl, or hydroxy acyl group containing from 8 to 22 carbon atoms or an alkylphenyl group wherein the alkyl group contains from 6 to 15 carbon atoms or mixtures thereof;
- X is a number from 0 to 30; and
- R 1 is selected from the group consisting of H, alkyl groups containing from 1 to 4 carbon atoms, acyl groups containing from 2 to 4 carbon atoms and mixtures thereof.
- the HLB of these nonionic surfactants is preferably from 5 to 20, most preferably from 8 to 14.
- Suitable semi-polar nonionic surfactants include tertiary amine oxides containing a straight or branched chain saturated or unsaturated aliphatic hydrocarbon, hydroxy hydrocarbon or halohydrocarbon radical in which the alkyl portion contains from 8 to 24 carbon atoms and two short chain methyl, ethyl, hydroxymethyl or hydroxyethyl radicals.
- Other suitable semi-polar nonionic detergent surfactants include the corresponding tertiary phosphine oxides and the sulfoxides.
- R and X are as stated hereinbefore and each R 2 is selected from the group consisting of C 1 - 4 alkyl and hydroxy alkyl groups and polyethoxylate groups containing from 0 to 10 ether linkages.
- the level of nonionic surfactant present is from 1% to 30%, preferably from 3% to 20% and most preferably from 5% to 15%.
- the polycarboxylate detergency builders of the present invention are essential to stabilizing the ester perfume.
- the water-soluble polycarboxylates of the present invention fall into several classes of organic compounds having carboxylate structures including amino polycarboxylates, cycloalkane polycarboxylates, ether polycarboxylates, alkyl polycarboxylates, epoxy polycarboxylates, tetrahydrofuran polycarboxylates, and benzene polycarboxylates.
- suitable materials for use herein are sodium and potassium ethylenediamine- tetraacetates, the water-soluble salts of phytic acid, e.g., sodium and potassium phytates, disclosed in U.S.-A-No. 2,739,942, Eckey, issued March 27, 1956, incorporated herein by reference; the polycarboxylate materials described in U.S.-A-3,364,103; and water-soluble salts of polycarboxylate polymers and copolymers as described in U.S.-A-No. 3,308,067, Diehl, issued March 7, 1967, incorporated herein by reference. Water-soluble salts of nitrilotriacetic acid can be used herein.
- a useful polycarboxylate which may be employed in the present invention comprises a water-soluble salt of a polymeric aliphatic polycarboxylic acid having the following structural relationships as to the position of the carboxylate groups and possessing the following prescribed physical characteristics: (a) a minimum molecular weight of about 350 calculated as to the acid form; (b) an equivalent weight of about 50 to about 80 calculated as to acid form; (c) at least 45 mole percent of the monomeric species having at least two carboxyl radicals separated from each other by not more than two carbon atoms; (d) the site of attachment of the polymer chain of any carboxyl-containing radical being separated by not more than three carbon atoms along the polymer chain from the site of attachment of the next carboxyl-containing radical.
- polycarboxylates include polymers of itaconic acid, aconitic acid, maleic acid, mesaconic acid, fumaric acid, methylene malonic acid, and citraconic acid and copolymers with themselves.
- polycarboxylates which can be used satisfactorily include water-soluble salts, especially the sodium and potassium salts of mellitic acid, citric acid, pyromellitic acid, benzene pentacarboxylic acid, oxydiacetic acid, carboxymethyloxysuccinic acid, carboxymethyloxymalonic acid, cis-cyclohexanehexacarboxylic acid, cis-cyclopentanetetracarboxylic acid, and oxydisuccinic acid.
- water-soluble salts especially the sodium and potassium salts of mellitic acid, citric acid, pyromellitic acid, benzene pentacarboxylic acid, oxydiacetic acid, carboxymethyloxysuccinic acid, carboxymethyloxymalonic acid, cis-cyclohexanehexacarboxylic acid, cis-cyclopentanetetracarboxylic acid, and oxydisuccinic acid.
- alkali metal and particularly the sodium and potassium salts of the foregoing inorganic and organic detergency builder salts are preferred for use herein from economic and solubility standpoints
- alkanolammonium e.g., triethanolammonium, diethanolammonium, and the like
- water-soluble salts of any of the foregoing builder anions are also useful herein.
- the preferred polycarboxylates for use in the present invention are nitrilotriacetates and citrates and mixtures thereof, especially sodium and potassium nitrilotriacetate, sodium and potassium citrate, and mixtures thereof.
- the nitrilotriacetates are the most preferred.
- the amount of polycarboxylate detergency builder contained in the detergent compositions is from 5% to 15% and most preferably from 6% to 12%.
- esters that can be used in the practice of the invention are ester perfumes.
- esters that can be used are acetates, anthranilates, benzoates, butyrates, cinnamates, formates, isobutyrates, phenylacetates and propionates.
- ester perfumes that can now be contained in alkaline aqueous liquid detergent compositions, but could not be before are: anisyl acetate, benzyl benzoate, cedryl formate, cinnamyl isobutyrate, citronellyl acetate, citronellyl formate, dihydrocarvyl acetate, diheptyl acetate, ethyl phenyl acetate, furfuryl phenyl acetate, geranyl benzoate, geranyl butyrate, hexyl caproate, isobutyl phenol acetate, isononyl acetate, isononyl propionate, linalyl acetate, linalyl formate, phenoxy ethyl isobutyrate, benzyl acetate, tricyclodecenyl acetate, tricyclodecenyl propionate, geranyl acetate, phenyl e
- the ester perfume may contain other perfume ingredients that are stable in alkaline aqueous liquid detergent compositions. Examples are acetals, alcohols, aldehydes, cyclic nitrogen compounds, ethers, hydrocarbons, ketones, lactones, musks and phenols. Thus it can easily be seen that numerous perfumes may be used within the scope of the invention.
- An example of such a perfume is:
- the amount of perfume material contained in the detergent compositions is from 0.01% to 4%, preferably from 0.1 % to 1% and most preferably from 0.2% to 0.8% with normally unstable ester perfumes constituting from 4% to 90%, preferably from 10% to 60% and most preferably from 25% to 50% of the total weight of the perfume material.
- compositions of this invention can contain all of the usual components of detergent compositions including the ingredients set forth, except for the perfume, in U.S.-A-3,936,537, Baskerville et al, incorporated herein by reference.
- Such components include color speckles, bleaching agents, bleach activators, suds boosters, suds suppressors, antitarnish and/or anticorrosion agent, soil-suspending agents, soil-release agents, dyes, fillers, optical brighteners, germicides, pH adjusting agents, alkalinity sources, hydrotropes, antioxidants, enzymes, enzyme stabilizing agents, etc.
- Preferred optional ingredients include suds modifiers particularly those of suds suppressing types, exemplified by silicones, and silica-silicone mixtures.
- the silicone material can be represented by alkylated polysiloxane materials such as silica-aerogels and xerogels and hydrophobic silicas of various types.
- the silicone material can be described as siloxane having the formula: wherein x is from 20 to 2,000 and R 3 and R 4 are each alkyl or aryl groups, especially methyl, ethyl, propyl, butyl and phenyl.
- the polydimethylsiloxanes (R 3 and R 4 are methyl having a molecular weight within the range of from 200 to 2,000,000, and higher, are all useful as suds controlling agents.
- Additional suitable silicone materials wherein the side chain groups R 3 and R 4 are alkyl, aryl, or mixed alkyl or aryl hydrocarbyl groups exhibit useful suds controlling properties. Examples of the like ingredients include diethyl-, dipropyl-, dibutyl-, methyl-, ethyl-, phenylmethylpolysiloxanes and the like.
- Additional useful silicone suds controlling agents can be represented by a mixture of an alkylated siloxane, as referred to hereinbefore, and solid silica.
- a preferred silicone suds controlling agent is represented by a hydrophobic silanated (most preferably trimethylsilanated) silica having a particle size in the range from 0.01 pm to 0.02 pm and a specific surface area above 50 m 2 /g. intimately admixed with dimethyl silicone fluid having a molecular weight in the range from 500 to 200,000 at a weight ratio of silicone to silanated silica of from 1:1 to 1:2.
- the silicone suds suppressing agent is advantageously releasably incorporated in a water-soluble or water-dispersible, substantially non-surface-active detergent-impermeable carrier.
- Particularly useful suds suppressors are the self-emulsifying silicone suds suppressors, described in U.S.-A-4,073,118, Gault et al, issued February 21,1978, incorporated herein by reference.
- An example of such a compound is DB-544, commercially available from Dow Corning, which is a siloxane/glycol copolymer.
- Suds modifiers as described above can be used at levels of up to approximately 2%, preferably from 0.1 to 1-1/2% by weight of the surfactant.
- Nonlimiting examples of suitable water-soluble inorganic alkaline detergent builder salts include the alkali metal carbonates, borates, bicarbonates, and silicates. Specific examples of such salts include the sodium and potassium tetraborates, bicarbonates and carbonates.
- Preferred soil suspending and antiredeposition agents include methyl cellulose derivatives and the copolymers of maleic anhydride and either methyl vinyl ether or ethylene, e.g., Gantrez AN119 or Gantrez 595 (trade names of GAF).
- the oder of the detergent compositions was determined by a sensory evaluation. Sensory evaluations are generally used in making such determinations. Analytical determinations are generally not possible.
- a perfume containing esters that are generally unstable in alkaline aqueous liquid media, was prepared by admixing the following components:
- compositions A, G, H, K and L which contain components within the practice of the invention, have relatively more acceptable product odors. It should be noted that composition J, which contains 3% of a synthetic anionic surfactant, had an unacceptable product odor whereas a similar composition, composition K, which contains only 1% of the same synthetic anionic surfactant, had an acceptable product odor.
- the detergent compositions of the invention stabilize the normally unstable ester perfume compounds: anisyl acetate, benzyl benzoate, cedryl formate, cinnamyl isobutyrate, citronellyl acetate, citronellyl formate, dihydrocarvyl acetate, diheptyl acetate, ethyl phenyl acetate, fufuryl phenyl acetate, geranyl benzoate, geranyl butyrate, hexyl caproate, isobutyl phenol acetate, isononyl acetate, isononyl propionate, linalyl acetate, linalyl formate, phenoxy ethyl isobutyrate, benzyl acetate, tricycl
- the following detergent compositions can contain ester perfumes without a stability problem:
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Claims (12)
worin das Mittel im wesentlichen frei von synthetischen anionischen Tensiden ist.
worin R und X vorstehende Bedeutung haben und R2 ausgewählt ist aus der Gruppe bestehend aus C'-4-Alkyl- und Hydroxyalkylgruppen und Polyethoxylatgruppen enthaltend 0 bis 10 Etherbindungen und
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US30167381A | 1981-09-14 | 1981-09-14 | |
US301673 | 1981-09-14 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0075976A1 EP0075976A1 (de) | 1983-04-06 |
EP0075976B1 true EP0075976B1 (de) | 1985-06-19 |
Family
ID=23164364
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19820201075 Expired EP0075976B1 (de) | 1981-09-14 | 1982-09-02 | Alkalische Wassrig-flüssige Detergenzzusammensetzung mit normalerweise instabilen Esterparfums |
Country Status (2)
Country | Link |
---|---|
EP (1) | EP0075976B1 (de) |
DE (1) | DE3264287D1 (de) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3929591A1 (de) * | 1989-09-06 | 1991-03-07 | Henkel Kgaa | Zeolithhaltiges fluessigwaschmittel |
MX9700498A (es) * | 1994-07-19 | 1997-04-30 | Procter & Gamble | Perfumes para composiciones de lavanderia y limpieza. |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE837914C (de) * | 1950-01-12 | 1952-05-02 | Max Loehner | Verfahren zur Fixierung von Riechstoffen zur Verwendung in der Seifen- und kosmetischen Industrie |
FI780439A (fi) * | 1978-01-12 | 1979-07-13 | Unilever Nv | Tvaettmedel |
US4265777A (en) * | 1980-04-17 | 1981-05-05 | The Procter & Gamble Company | Detergent compositions containing an aluminosilicate detergency builder and an unsaturated fatty acid soap |
-
1982
- 1982-09-02 DE DE8282201075T patent/DE3264287D1/de not_active Expired
- 1982-09-02 EP EP19820201075 patent/EP0075976B1/de not_active Expired
Also Published As
Publication number | Publication date |
---|---|
DE3264287D1 (en) | 1985-07-25 |
EP0075976A1 (de) | 1983-04-06 |
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