US3892680A - Built detergent composition containing calcium-insensitive detergent and a carbonate-silicate builder - Google Patents

Built detergent composition containing calcium-insensitive detergent and a carbonate-silicate builder Download PDF

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Publication number
US3892680A
US3892680A US341182A US34118273A US3892680A US 3892680 A US3892680 A US 3892680A US 341182 A US341182 A US 341182A US 34118273 A US34118273 A US 34118273A US 3892680 A US3892680 A US 3892680A
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Prior art keywords
detergent
sodium
carbonate
silicate
weight ratio
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Expired - Lifetime
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US341182A
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English (en)
Inventor
Lawrence Benjamin
Jay Harold Saylor
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Procter and Gamble Co
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Procter and Gamble Co
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Publication date
Priority to CH1816171A priority Critical patent/CH570455A5/xx
Priority to AT1069071A priority patent/AT328596B/de
Priority to CA129,967A priority patent/CA947610A/en
Priority to FR7144709A priority patent/FR2118559A5/fr
Priority to DE2161699A priority patent/DE2161699C3/de
Priority to GB5800871A priority patent/GB1348389A/en
Priority to AU36858/71A priority patent/AU460417B2/en
Priority to NL7117148A priority patent/NL7117148A/xx
Priority to US341182A priority patent/US3892680A/en
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Application granted granted Critical
Publication of US3892680A publication Critical patent/US3892680A/en
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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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/10—Carbonates ; Bicarbonates
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • 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
    • C11D3/04—Water-soluble compounds
    • C11D3/08—Silicates

Definitions

  • ABSTRACT Biodegradable, phosphate-free detergent compositions comprising a calcium insensitive detergent and a precipitating builder consisting essentially of a mixture of an alkali metal carbonate and an alkali metal silicate, the weight ratio of carbonate to silicate being from 3:1 to 1:3 and the weight ratio of the detergent to builder being in the range of 1:10 to 3:1.
  • Water-soluble polyphosphates and in particular, the water-soluble pyrophosphates and tripolyphosphates, are well known builders for heavy duty detergent compositions.
  • Sodium tripolyphosphate has been widely used in granular detergent compositions.
  • an effective phosphate-free detergent composition comprises a calcium insensitive detergent and a precipitating builder consisting essentially of an alkali metal carbonate and an alkali metal silicate.
  • the invention thus involves the preparation of laundry detergent compositions consisting essentially of the following components:
  • a builder consisting essentially of an alkali metal carbonate and an alkali metal silicate, the weight ratio of carbonate to silicate being from 3:1 to 1:3 and the weight ratio of detergent to builder being from 1:10 to 3:1; said composition having a pH of from 6 to 12 in aqueous solution at a concentration of 0.12%.
  • the calcium insensitive organic synthetic detergents useful herein include certain anionic, nonionic, zwitterionic and ampholytic detergents and mixtures thereof.
  • the term calcium insensitive is used to designate those detergents which possess superior detergency and dispersancy and relative resistance to precipitation or insoluble complex. formation under the conditions of pH and water hardness contemplated.
  • detergency and dispersancy where employed herein refer, respectively, to the capacity to remove particulate and lipid soils from a substrate and the capacity to keep such soils in suspension in a washing solution.
  • Detergent and dispersant compounds to be useful herein must, in addition, perform satisfactorily in washing solutions containing hardness mineral ions normally present in tap water.
  • the detergents must be insensitive to such hardness ions, especially calcium and magnesium.
  • a detergent and dispersant material which forms a precipitate or insoluble-complex with hard water ions, the detergent not available to function for its intended purpose.
  • a detergent useful herein is one whose detergency properties are not compromised by hardness mineral ions, i.e. calcium and the like.
  • the synthetic organic detergent compounds utilizable herein and having the hereinbefore described calcium insensitive properties include certain anionic, semi-polar nonionic, ampholytic and zwitterionic materials. These materials include water-soluble salts of certain materials such as sulfonated fatty acid esters of ,B-acyloxyalkane-l-sulfonic acids; B-alkyloxy alkane sulfonates; alkyl polyoxyethylene sulfates, watersoluble olefin sulfonates; and certain ampholytic and zwitterionic detergents.
  • Anionic organic detergents utilizable herein include alkali metal, ammonium and substituted-ammonium salts of esters of an a-sulfonated fatty acid in which the esters contain about 15 to about 25 carbon atoms.
  • These detergent compounds have the following structure:
  • R is alkyl or alkenyl of about 10 to about 20 carbon atoms (forming with the two carbon atoms a fatty acid group); R is alkyl of 1 to about 10 carbon atoms; and M is a salt-forming cation.
  • the salt-forming radical M in the hereinbefore described structural formula is a water-solubilizing cation and can be, for example, an alkali metal cation (e.g., sodium, potassium, lithium), ammonium or substituted-ammonium cation.
  • alkali metal cation e.g., sodium, potassium, lithium
  • substituted ammonium cations include methyl-, dimethyl,- and trimethylammonium cations and quaternary ammonium cations such as tetramethyl-ammonium' and dimethyl myristic, palmitic, stearic, palmitoleic, oleic,-linoleic acids and mixtures thereof.
  • a preferred ester material herein is the sodium salt of the methyl ester of a-sulfonated tallow fatty acid, the term tallow indicating a carbon chain distribution approximately as follows: C 2.5%, C 28%, C 23%, palmitoleic 2%, oleic 41.5%, and linoleic 3% (the first three fatty acids listed are saturated).
  • Suitable salts of a-sulfonated fatty esters include the ammonium and tetramethyI-ammonium salts of the hexyl, octyl, ethyl, and butyl esters of oz-sulfonated tridecanoic acid; the potassium and sodium salts of the ethyl, butyl, hexyl, octyl, and decyl esters of oz-sulfonated pentadecanoic acid; and the sodium and potassium salts of butyl, hexyl, octyl, and decyl esters of a-sulfonated heptadecanoic acid; and the lithium and ammonium salts of butyl, hexyl, octyl, and decyl esters of a-sulfonated nonadecanoic acid. 7 j
  • anionic organic detergents includes salts of 2-acyloxyalkanel -sulfonic acids.
  • These salts have the formula OCR CHCHSOM where R, is alkyl of about 9 to about 23 carbon atoms (forming with the two carbon atoms an alkane group);
  • acetoxy-hexadecane-l-sulfonic acid the dimethylammonium salt of 2-heptanoyloxy-tridecane-l-sulfonic acid; the potassium salt of 2-octanoyl'oxy-tetradecanel-sulfonic acid; the dimethylpiperdiniuin salt of 2- nonanoyloxy-tetradecane-l-sulfonic acid; the sodium salt of 2-acetoxy-heptadecane-l-sulfonic acid; the lithium salt of 2-acetoxy-octadecarle-l-sulfonic acid; the dimethylamine salt of 2-acetoxyoctadecane l-sulfonic acid; the potassium salt of 2-acetoxy-nonadecane-lsulfonic acid; the sodium salt of 2'-acetoxy-uncosanelsulfonic acid; the sodium salt of 2-propionyloxydocosane-l-sulfonic acid; and
  • Preferred ,B-acyloxy-alkane-l-sulfonate salts herein are the alkali metal salts of ,B-acetoxy-alkane-l-sulfonic acids corresponding to the above formula wherein R is an alkyl of about 14 to about 18 carbon atoms, these salts being preferred from the standpoints of their excellent cleaning properties and ready availability.
  • alkyl ether sulfates Typical examples of the above described B-acetoxy
  • Other synthetic anionic detergents useful herein are alkyl ether sulfates. These materials have the formula RO(C H O),SO M wherein R is alkyl or alke'nyl of about 10 to about 20 carbon atoms, x is l to 30, and M is a salt-forming cation defined hereinbefore.
  • the alkyl ether sulfates of the present invention are condensation products of ethylene oxide and monohydric alcohols having about 10 to about 20 carbon atoms.
  • R has 14 to 18 carbon atoms.
  • the alcohols can be derived from fats, e.g., coconut oil or tallow, or can be synthetic. Lauryl alcohol and straight chain alcohols derived from tallow are preferred herein. Such alcohols are reacted with l to 30, and especially 3 to 6, molar proportions of ethylene oxide and the resulting mixture of molecular species, having, for example, an average of 3 to 6 moles of ethylene oxide per mole of alcohols, is sulfated and neutralized.
  • alkyl ether sulfates of the present invention are sodium coconut alkyl ethylene glycol ether sulfate; sodium tallow alkyl triethylene glycol ether sulfate; lithium tallow alkyl triethylene glycol ether sulfate; sodium tallow alkyl hexaoxyethylene sulfate; and ammonium tetradecyl octaoxyethylene sulfate.
  • a preferred class of anionic organic detergents are the B-alkyloxy alkane sulfonates. These compounds have the following formula:
  • olefin sulfonates having about 12 to about 24 carbon atoms.
  • the term olefin sulfonates is used herein to mean compounds which are produced by the sulfonation of oz-olefin by means of uncomplexed sulfur trioxide, followed by neutralization of the acid reaction mixture in conditions such that sultones formed in the reaction are hydrolyzed to give corresponding hydroxyalkanesulfonates.
  • the sulfur trioxide may be liquid or gaseous, and is usually, but not necessarily, diluted by inert diluents, for example by liquid S0 chlorinated hydrogen, etc., when used in the liquid form, or by air, nitrogen, gaseous S0 etc., when used in the gaseous form.
  • inert diluents for example by liquid S0 chlorinated hydrogen, etc., when used in the liquid form, or by air, nitrogen, gaseous S0 etc., when used in the gaseous form.
  • the a-olefins from which the olefin sulfonates are derived are mono-olefins having 12 to 24 carbon atoms, preferably 14 to 16 carbon atoms. Preferably, they are straight chain olefins. Examples of suitable l-olefins inelude l-dodecene; l-tetradecene; l-hexadecene; loctadecene; l-eicosene and l-tetracosene.
  • the olefin sulfonates can contain minor amounts of other materials, such as alkene disulfonates depending upon the reaction conditions, proportions of reactants, the nature of the starting olefins and impurities in the olefin stock and side reactions during the sulfonation process.
  • Ampholytic synthetic detergents useful herein are broadly described as derivatives of aliphatic secondary and tertiary amines in which the aliphatic radical is straight chain or branched and wherein one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and one contains an anionic water solubilizing group, e.g., carboxy, sulfonate, or sulfate.
  • These detergents have the formula -NCH ZM such as the ones prepared by reacting dodecylamine with sodium isethionate according to the teaching of US. Pat. No. 3,658,072; sodium salts of N'higher alkyl aspartic acids such as those produced according to the teaching of U.S.'Pat. No. 2,438,091; and the products sold under the trade name Miranol and described in US. Pat. No.”2,528,378.
  • Useful Zwitterionic synthetic detergents are broadly described as derivatives of aliphatic quaternary ammo nium, and sulfonium compounds, in which the aliphatic radicals are straight chain or branched, and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and-one contains an anionic water solubilizing group, e.g., carboxy, sulfonate or sulfate.
  • a general formula for these compounds is:
  • R contains an alkyl, alkenyl, or hydroxyalkyl radical of from about 8 to about 18 carbon atoms having from 0 to about 10 ethylene oxide moieties and from O to l glyceryl moiety;
  • Y is selected from the group consisting of nitrogen and sulfur atoms;
  • R: is an alkyl or monohydroxy alkyl group containing 1 to about 3 carbon atoms; .r is 1 when Y is a sulfur atom and 2 when Y is a nitrogen atom, R is an alkylene or hydroxy alkylene of from I to about 4 carbon atoms and Z is a radical selected from the group consisting of carboxylate, sulfonate, sulfate, phosphonate and phosphate groups,
  • Examples include: 4-[N,N-di(2-hydroxyethyl)-N- octadecylamm'onio]-butane-l-carboxylate; 5-[S-3- hydroxypropyl-S-hexadecylsulfonio]-3-hydroxypentane-l-sulfate; 3-[P,P-diethyl-P-3,6,9- trioxatetracosanephosphonio]-2-hydroxypropanel phosphate; 3-[N,N-dipropyl-N-3-dodecoxy-2- hydroxypropylammonio]-propanel -phosphonate; 3- (N,N-dimethylN-hexadecylammonio)propane-lsulfonate, 3-(N,N-dimethyl-N-hexadecylammonio)-2- hydroxypropanel-sulfonate, 4-[N,N-di( 2- hydroxyethy
  • Examples of compounds falling within this definition are 3-(N,N-dimethylN-N- hexadecylammonio)propane-l-sulfonate and 3-(N,N- dimethyl-N-tridecylammonio)-2hydroxypropanel sulfonate which are especially preferred for their excellent cool water detergency characteristics.
  • the alkyl groups contained in said detergent surfactants can be straight or branched, preferably straight, and saturated or unsaturated as desired.
  • the calcium insensitive detergent compounds of the present invention can be employed in varying amounts in the compositions of the present invention. As there will be considerable variation in the strengths of washing solutions employed by different users, i.e., some users may tend to use more or less than others, the requisite amount of detergent compound in the detergent formulation is an amount sufficient to provide effective cleaning and whitening levels under diverse conditions of soiling and usage.
  • the enzyme-containing detergent compositions of the present invention can contain from to 85% by weight of the synthetic organic detergent depending upon the detergent employed. A preferred amount of detergent (sole detergent or mixtures) is from to 50%.
  • the builder is a mixture of two inorganic salts selected from alkali metal silicates and carbonates.
  • the preferred salts are the potassium and sodium salts such as sodium carbonate and sodium silicate, and potassium carbonate and potassium silicate.
  • the SiO /M O weight ratio of the silicate, where M is an alkili metal is critical.
  • the effective range of this weight ratio as SiO /M O is from 1:1 to 35:1; the preferred range is from 1.6:] to 3.2:].
  • the heavy duty compositions of this invention can be made into any of the several commercially desirable composition forms, for example, granular, flake, liquid and tablet forms.
  • the essential ingredients are (a) the calcium insensitive detergent and (b) the builder mixture, as described herein.
  • the specific action of the built detergent compositions of this invention will vary to some extent depending upon the ratio of active detergent to building mixture in any given detergent composition. There is considerable variation in the strengths of the washing solutions employed by different housewives, i.e., some housewives tend to use less or more of the detergent compositions than others. Moreover, there are variations in temperature and soil loads as between washing operations. Further, the degree of hardness of the water used to make up the washing solutions can also cause differences in the cleaning and whiteness maintenance results. Different fabrics respond in different ways to different detergent compositions. The most useful detergent composition for household use is a composition which provides effective cleaning and whiteness maintenance under diverse cleaning conditions. The built detergent compositions of this invention are especially valuable in this respect.
  • compositions of this invention can contain various ingredients for special purposes.
  • they can contain such ordinary additives as suds builders, suds depressants, anti-corrosion agents, antiredeposition agents, germicidal agents, anti-bacterial agents, dyes, fluorescers, perfumes, enzymes and the like.
  • liquid detergents liquid vehicles, for example water and alcohol, together with solubilizing agents and the like can be used.
  • EXAMPLE lV An effective granular detergent product has the following composition; the percentages are given by weight:
  • EXAMPLE V An effective granular detergent product has the following composition; the precentages are given by weight:
  • a granular detergent product of this invention has the following composition; the percentages are given by weight:
  • EXAMPLE V11 A granular detergent product of this invention has the following composition; the percentages are given by weight:
  • a facial swatch test was conducted comparing representative compositions of this invention with two other household laundry compositions.
  • One of the household laundry compositions had a linear alkyl benzene sulfonate-tallow alkyl sulfate active and a nitrilotriaceticphosphate builder, while the other composition has a tallow undecyl ethoxylate surface active agent and the carbonate-silicate builder system common to the examples representative of the invention.
  • the facial switch test requires fourteen panelists and is completely replicated, using a second set of fourteen panelists with the two results being averaged to obtain one complete test.
  • the 4X4 inch cotton swatches used in this test are fastened to the concave cup of an electrical massaging device. The cup is then rubbed over designated areas of a panelists face for a period of 30 seconds while the machine is vibrating. The swatches thus become soiled. The soiled swatches are washed in a Tergotometer for 10 minutes in 1 liter of the product solution. The solution, containing 7 grains calcium ion hardness, is kept at 110F. The detergent product is used at a 0.12% level by weight. The swatches are then rinsed for 1 minute at a temperature of F. using water containing 7 grains of calcium ion hardness. They are then dried and graded.
  • compositions of the products used in this test are found in Table 1. Each component was added separately to the wash solution while minor ingredients normally found in household laundry products such as carboxymethylcellulose, optical brightening agents and enzymes were omitted in all cases.
  • the washed and dried facial swatches were graded visually to assess the relative cleaning differences of the products used.
  • Composition I A control product for the test was provided by Composition I, Table 1.
  • Composition 1 was used at two concentration levels, 0.15% product and 0.0671 product. Each of the product grades and usage levels are-presented in Table 11.
  • a laundry composition consisting essentially of l. a synthetic organic detergent having a formula wherein R is alkyl or alkenyl of about 10 to about 18 carbon atoms, is l to 30 and M is a salt-forming radical selected from the group consisting of alkali metals, ammonium and mono-, di-, and tri lower alkyl substituted ammonium, and
  • a mixture of an alkali metal carbonate and an alkali metal silicate wherein the weight ratio of carbonate to silicate is from 3:1 to 1:3 and the SiO /M O weight ratio of the silicate when M is an alkali metal is from 1.0 to 3.5: l; and the weight ratio of the detergent to builder is from 1:10 to 3:1.
  • composition of claim 1 wherein the organic detergent is a compound of the formula RO(C H O),SO M
  • R is tallow alkyl
  • M is alkali metal and .r is
  • composition of claim 2 in which the synthetic organic detergent is sodium triethoxy sulfate.

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  • 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)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
US341182A 1970-12-14 1973-03-14 Built detergent composition containing calcium-insensitive detergent and a carbonate-silicate builder Expired - Lifetime US3892680A (en)

Priority Applications (9)

Application Number Priority Date Filing Date Title
AT1069071A AT328596B (de) 1970-12-14 1971-12-13 Reinigungs- und waschmittelmischung
CA129,967A CA947610A (en) 1970-12-14 1971-12-13 Built detergent composition containing calcium-insensitive detergent and a carbonate-silicate builder
FR7144709A FR2118559A5 (enrdf_load_html_response) 1970-12-14 1971-12-13
DE2161699A DE2161699C3 (de) 1970-12-14 1971-12-13 Wasch- und Reinigungsmittel
CH1816171A CH570455A5 (enrdf_load_html_response) 1970-12-14 1971-12-13
NL7117148A NL7117148A (enrdf_load_html_response) 1970-12-14 1971-12-14
AU36858/71A AU460417B2 (en) 1970-12-14 1971-12-14 Built detergent composition containing calcium-insensitive detergent anda carbonate-silicate builder
GB5800871A GB1348389A (en) 1970-12-14 1971-12-14 Built detergent composition
US341182A US3892680A (en) 1970-12-14 1973-03-14 Built detergent composition containing calcium-insensitive detergent and a carbonate-silicate builder

Applications Claiming Priority (2)

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US9811370A 1970-12-14 1970-12-14
US341182A US3892680A (en) 1970-12-14 1973-03-14 Built detergent composition containing calcium-insensitive detergent and a carbonate-silicate builder

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AT (1) AT328596B (enrdf_load_html_response)
AU (1) AU460417B2 (enrdf_load_html_response)
CA (1) CA947610A (enrdf_load_html_response)
CH (1) CH570455A5 (enrdf_load_html_response)
DE (1) DE2161699C3 (enrdf_load_html_response)
FR (1) FR2118559A5 (enrdf_load_html_response)
GB (1) GB1348389A (enrdf_load_html_response)
NL (1) NL7117148A (enrdf_load_html_response)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4009114A (en) * 1974-09-23 1977-02-22 Colgate-Palmolive Company Non-phosphate detergent composition
US4013577A (en) * 1972-04-14 1977-03-22 Colgate-Palmolive Company Heavy duty dry biodegradable detergent composition
US4028282A (en) * 1975-05-14 1977-06-07 Lion Fat & Oil Co., Ltd. Method of manufacturing granular detergents
US4122044A (en) * 1976-05-18 1978-10-24 The Lion Fat And Oil Co., Ltd. Granular detergent composition
US4140657A (en) * 1976-06-18 1979-02-20 The Lion Fat & Oil Co., Ltd. Granular detergent composition
US4692275A (en) * 1986-04-23 1987-09-08 Lever Brothers Company Detergent compositions containing an alkylbenzene sulfonate and alcohol ethoxysulfate surfactant system
US20080064618A1 (en) * 2006-09-07 2008-03-13 Thorsten Bastigkeit Low suds laundry detergents with enhanced whiteness retention
US20080064619A1 (en) * 2006-09-07 2008-03-13 Thorsten Bastigkeit Detergent compositions with unique builder system for enhanced stain removal
WO2014031790A1 (en) 2012-08-23 2014-02-27 Allylix, Inc. Nootkatone as an insecticide and insect repellent
US9839214B2 (en) 2012-12-18 2017-12-12 Evolva, Inc. Solavetivone and 5-epi-beta-vertivone as pest repellants and pesticides

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT1080880B (it) * 1976-06-30 1985-05-16 Church & Dwight Co Inc Composizione detergente miscelata a secco e metodo di suo impiego

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3265624A (en) * 1963-10-01 1966-08-09 Colgate Palmolive Co Detergent composition
US3600318A (en) * 1969-06-02 1971-08-17 Procter & Gamble Enzyme-containing detergent compositions for neutral washing
US3658727A (en) * 1969-05-02 1972-04-25 Procter & Gamble Enzyme-containing detergent compositions for neutral washing
US3801511A (en) * 1972-04-17 1974-04-02 Procter & Gamble Spray-dried detergent composition

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3265624A (en) * 1963-10-01 1966-08-09 Colgate Palmolive Co Detergent composition
US3658727A (en) * 1969-05-02 1972-04-25 Procter & Gamble Enzyme-containing detergent compositions for neutral washing
US3600318A (en) * 1969-06-02 1971-08-17 Procter & Gamble Enzyme-containing detergent compositions for neutral washing
US3801511A (en) * 1972-04-17 1974-04-02 Procter & Gamble Spray-dried detergent composition

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4013577A (en) * 1972-04-14 1977-03-22 Colgate-Palmolive Company Heavy duty dry biodegradable detergent composition
US4009114A (en) * 1974-09-23 1977-02-22 Colgate-Palmolive Company Non-phosphate detergent composition
US4028282A (en) * 1975-05-14 1977-06-07 Lion Fat & Oil Co., Ltd. Method of manufacturing granular detergents
US4122044A (en) * 1976-05-18 1978-10-24 The Lion Fat And Oil Co., Ltd. Granular detergent composition
US4140657A (en) * 1976-06-18 1979-02-20 The Lion Fat & Oil Co., Ltd. Granular detergent composition
US4692275A (en) * 1986-04-23 1987-09-08 Lever Brothers Company Detergent compositions containing an alkylbenzene sulfonate and alcohol ethoxysulfate surfactant system
US20080064618A1 (en) * 2006-09-07 2008-03-13 Thorsten Bastigkeit Low suds laundry detergents with enhanced whiteness retention
US20080064619A1 (en) * 2006-09-07 2008-03-13 Thorsten Bastigkeit Detergent compositions with unique builder system for enhanced stain removal
US7354892B2 (en) 2006-09-07 2008-04-08 The Dial Corporation Low suds laundry detergents with enhanced whiteness retention
US7417017B2 (en) 2006-09-07 2008-08-26 The Dial Corporation Detergent compositions with unique builder system for enhanced stain removal
WO2014031790A1 (en) 2012-08-23 2014-02-27 Allylix, Inc. Nootkatone as an insecticide and insect repellent
US9839214B2 (en) 2012-12-18 2017-12-12 Evolva, Inc. Solavetivone and 5-epi-beta-vertivone as pest repellants and pesticides
US10206393B2 (en) 2012-12-18 2019-02-19 Evolva, Inc. Solavetivone and 5-epi-β-vetivone as pest repellants and pesticides

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DE2161699C3 (de) 1980-06-19
NL7117148A (enrdf_load_html_response) 1972-06-16
DE2161699B2 (de) 1979-10-11
AU460417B2 (en) 1975-04-24
FR2118559A5 (enrdf_load_html_response) 1972-07-28
CA947610A (en) 1974-05-21
DE2161699A1 (de) 1972-06-29
CH570455A5 (enrdf_load_html_response) 1975-12-15
AU3685871A (en) 1973-06-21
GB1348389A (en) 1974-03-13
AT328596B (de) 1976-03-25

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