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US3202714A - Oxy containing tertiary amine oxides - Google Patents

Oxy containing tertiary amine oxides Download PDF

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Publication number
US3202714A
US3202714A US156995A US15699561A US3202714A US 3202714 A US3202714 A US 3202714A US 156995 A US156995 A US 156995A US 15699561 A US15699561 A US 15699561A US 3202714 A US3202714 A US 3202714A
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United States
Prior art keywords
oxide
hydroxyethyl
bis
sodium
tertiary amine
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Expired - Lifetime
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US156995A
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English (en)
Inventor
Roger E Zimmerer
Howard F Drew
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Procter and Gamble Co
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Procter and Gamble Co
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Filing date
Publication date
Priority to NL286242D priority Critical patent/NL286242A/xx
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to US156995A priority patent/US3202714A/en
Priority to FI2146/62A priority patent/FI41054B/fi
Priority to DK516462AA priority patent/DK109875C/da
Priority to FR917239A priority patent/FR1450374A/fr
Priority to DE19621518086 priority patent/DE1518086C3/de
Priority to GB45799/62A priority patent/GB1018774A/en
Priority to BE651634A priority patent/BE651634A/xx
Priority to US398032A priority patent/US3281368A/en
Priority to SE11967/64A priority patent/SE332868B/xx
Application granted granted Critical
Publication of US3202714A publication Critical patent/US3202714A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/75—Amino oxides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C291/00—Compounds containing carbon and nitrogen and having functional groups not covered by groups C07C201/00 - C07C281/00
    • C07C291/02—Compounds containing carbon and nitrogen and having functional groups not covered by groups C07C201/00 - C07C281/00 containing nitrogen-oxide bonds
    • C07C291/04—Compounds containing carbon and nitrogen and having functional groups not covered by groups C07C201/00 - C07C281/00 containing nitrogen-oxide bonds containing amino-oxide bonds
    • 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
    • C11D3/06—Phosphates, including polyphosphates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids

Definitions

  • Thermal stability is a hi hly desirable property which is lacking in many detergents. Such stability is particularly desirable when detergents are subjected to heat during use or processing, as for example, in spray drying granular detergent compositions.
  • Another advantageous property for an organic detergent is a low degree of hygroscopicity which results in improved crystallinity.
  • detergent surface active agents which are hygroscopic are used in bar or granular cool water to retain their crease resistant properties.
  • the amine oxides of this invention are:
  • R is an alkyl, 2-hydroxyalkyl, 3-hydroxyalky1 or 3-alkoxy-2-hydroxypropyl radical in which the alkyl and alkoxy, respectively, range from 10 to 18 carbon atoms in chain length, R and R are each methyl, ethyl, propyl, isopropyl, 2-hydroxyethyl, 2-hydroxypropyl or 3-hydroxypropyl groups and at least one of the R and R radicals contains a hydroxy group.
  • R1R2R3N O The class of compounds described above will hereinafter be referred to more simply as R1R2R3N O.
  • Examples of the compounds of this invention are bis(2-hydroxyethyl)dodecylamine oxide, bis(2-hydroxyethyl)-2-hydroxy tetradecylarnine oxide, (2-hydroxyeth-.
  • yl)methyltetradecylamine oxide bis(3-hydroxypropyl)- 3-hydroxyhexadecylamine oxide, (2 -hydroxyp1'opyl)-2- hydroxyoctadecylpropylamine oxide, bis(2-hydroxyethyl)- 3-hydroxyhexadecylamine oxide, bis(2-hydroxypropyl)do decylamine oxide, bis(Z-hydroxyethyl)-3-hydroxydo'decy-lamine oxide, bis(2-hydroxyethyl)-2-hydroxydodecylamine oxide, N,N-bis(2 hydroxyethyl) 3-dodecoxy-2-hydroxypropylamine oxide and N-methyl-N-(2-hydroxyethyl)-3 tetradecoxy-2-hydroxypropylamine oxide.
  • Tertiary amine oxides as a broad class of compounds are known. It was surprising to find, however, that the particular trialkylamine oxides containing particularlyplaced hydroxy groups as described above (i.e., a hydroxy group in R and/ or R have such highly desirable properties for use as organic detergents, i.e., improved hygroscopicity, thermal stability and cool water detergency characteristics.
  • R R and R must be as described above. If the alkyl or allroxy in R is longer in chain length than 18 carbon atoms or shorter in chain length than 10 carbon atoms, desired detergency is not obtained. Likewise, if R and R contain more than 3 carbon atoms, such characteristics are not obtained. Either R or R must contain a hydroxy group in the 2 or 3 position, Whether or not R contains a hydroxy group, in order to achieve improved thermal stability, hygroscopicity and, especially, cool-water detergency characteristics. These properties are particularly outstanding when both R and R contain a hydroxy group. containing hydroxymethyl groups are not stable.)
  • those tertiary amine oxides wherein R is a C C alkyl, C -C Z-hydroxyalkyl, C C 3- hydroxyalkyl or C -C 3-alkoxy-2-hydroxypropyl radical and both R and R are 2-hydroxyethyl radicals have cool water detergency properties markedly superior to conventional organic detergent active ingredients such as sodium' dodecylbenzenesulfonate (the dodecyl group being derived fromtetrapropylene).
  • organic detergent active ingredients such as sodium' dodecylbenzenesulfonate (the dodecyl group being derived fromtetrapropylene).
  • bis(2- hydroxyethyl)dodecylamine oxide this compound also has excellent sudsing properties.
  • hydroxy groups in the 2 or 3 position in R provide improved skin-mildness, thermal stability and hygroscopicity characteristics (compared to an unsubstituted 'R alkyl group).
  • the improved mildness, thermal stability and hygroscopicity characteristics of amine oxide compounds containing hydroxy groups in R but not in R or R is set forth in copending application of Howard F. Drew, Serial No. 156,993, tiled concurrently herewith.
  • the improved thermal stability and hygroscopicity characteristics provided by hydroxy groups in R are in addition to these characteristics which are provided by hydroxy groups in R and/ or R
  • the mildness, hygroscopicity and thermal stability characteristics of the tertiary amine oxides which have a hydroxy group in all three alkyl radicals e.g., bis(2- hydroxyethyl)-2-hydroxydodecylamine oxide and N,N- bis(2-hydroxyethyl)-3-dodecoxy-2 hydroxypropylamine oxide
  • the alkyl or alkoxy in the R group can be derived from naturally occurring fats and oils or from synthetic sources. Mixtures of amine oxides are very suitable wherein the alkyl or alkoxy inR varies in chain length in the C to C (Tertiary amine oxidesrange, as for example, the alkyl or alkoxy groups derived from coconut fatty alcohol (or distilled coconut fatty alcohol). Those amine oxides in which the alkyl or alkoxy in R ranges from 12 to 14 carbon atoms are preferred.
  • the 3-alkoxy-2-hydroxypropyl R radical has the following general formula:
  • R 011233110 Hr wherein R ranges from 10 to 18 carbon atoms in chain length.
  • the tertiary amine oxides of this invention can be prepared, in general, by oxidizing the corresponding tertiary amine. See, for example, British Patent 437,566.
  • the corresponding tertiary amine in general, can be prepared by alkylating, with an appropriate long chain alkyl compound, the appropriate secondary amine. The examples explain in detail such reactions.
  • the preparation of alkyl glycidyl ethers (a source of the 3-alkoxy-2-hydroxypropyl R is described in Canadian Patent 582,404 and U.S. Patent 2,989,547.
  • Compounds of this invention are useful per se as detergents and surface active agents. Desirably they are used with other materials to form detergent compositions, particularly solid form compositions as for example, bar, flake, granular or tableted granular compositions.
  • the tertiary amine oxide of this invention can also be used to make liquid detergent compositions.
  • Such detergent compositions can contain from about 5% to about 80% of the tertiary amine oxides of this invention and from about 95% to about 20% of anionic organic detergents, nonionic organic detergents, water soluble inorganic alkaline builder salts, water soluble organic alkaline sequestrant builder salts or mixtures thereof.
  • Granular or flake detergents preferably contain about 5% to about 50% of the amine oxides of this invention and from about 95% to about 50% normally solid, water soluble inorganic alkaline builder salts, or water soluble organic alkaline sequestrant builder agents.
  • Bar formulations contain about 5% to about 50% of the amine oxides of this invention when used with anionic detergents, such as a soap base, and, if desired, alkaline inorganic or organic builders or inert fillers.
  • Bar formulations can contain about 40% to about 80% of the amine oxides of this invention as the only detergent component, if desired, and the balance inert fillers or builders.
  • Anionic organic detergents used alone or in admixture include both the soap and non-soap detergents.
  • suitable soaps are the sodium, potassium, ammonium and alkylolammonium salts of higher fatty acids (C C Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium or potassium tallow and coconut soap.
  • anionic organic non-soap detergents are: alkyl glyceryl ether sulfonates; alkyl sulfates; alkyl monoglyceride sulfates or sulfonates; alkyl polyethenoxy ether sulfates; acyl sarcosinates; acyl esters of isethionates; acyl N-methyl taurides; alkylbenzenesulfonates; alkyl phenol polyethenoxy sulfonates.
  • the alkyl and acyl groups respectively, contain 10 to 20 carbon atoms.
  • nonionic organic detergents are: polyethylene oxide condensates of alkyl phenols wherein the alkyl group contains from 6 to 12 carbon atoms (e.g., 5- octylphenol) and the ethylene oxide'is present in a molar ratio of ethylene oxide to alkyl phenol in the range of 10:1 to :1; condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylene diamine wherein the molecular weight of the condensation products range from water.
  • polyethylene oxide condensates of alkyl phenols wherein the alkyl group contains from 6 to 12 carbon atoms e.g., 5- octylphenol
  • the ethylene oxide' is present in a molar ratio of ethylene oxide to alkyl phenol in the range of 10:1 to :1
  • condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylene diamine wherein the molecular weight of the condensation products range from water.
  • condensation product of from about 5 to 30 moles of ethylene oxide with one mole of a straight or branched chain aliphatic alcohol containing from 8 to 18 carbon atoms (e.g., lauryl alcohol).
  • Water soluble inorganic alkaline builder salts used alone or in admixture are alkali metal carbonates, borates, phosphates, polyphosphates, bicarbonates and silicates. (Ammonium or substituted ammonium salts can also be used.) Specific examples of such salts are sodium tripolyphosphate, sodium carbonate, sodium tetraborate, sodium pyrophosphate, sodium bicarbonate, potassium tripolyphosphate, potassium pyrophosphate, sodium hexametaphosphate, sodium sesquicarbonate, sodium monoand di-ortho phosphate and potassium bicarbonate. Such inorganic builder salts enhance the detergency of the subject amine oxides.
  • water soluble organic alkaline sequestrant builder salts used alone or in admixture are alkali metal, ammonium or substituted ammonium amino polycarboxylates, e.g., sodium and potassium ethylenediaminetetraacetate, sodium and potassium N-(Z-hydroxyethyl)-ethylenediaminctriacetates, sodium and potassium nitrilotriacetates and sodium potassium, and triethanolammonium N-(2-hydroxyethyl)nitrilodiacetates.
  • alkali metal, ammonium or substituted ammonium amino polycarboxylates e.g., sodium and potassium ethylenediaminetetraacetate, sodium and potassium N-(Z-hydroxyethyl)-ethylenediaminctriacetates, sodium and potassium nitrilotriacetates and sodium potassium, and triethanolammonium N-(2-hydroxyethyl)nitrilodiacetates.
  • organic alkaline sequestrant builder salts which can be used are: hydroxyethylethylenediaminetriacetates; 2-hydroxyethyliminodiacetates; diethylenetriaminepentaacetates; 1,Z-diaminocyclohexanetetraacetates. Mixed salts of these polycarboxylates are also suitable.
  • the alkali metal salts of phytic acid, e.g., sodium phytate are also suitable as organic alkaline sequestrant builder salts (see U.S. Patent 2,739,942).
  • Preferred detergent compositions contain about 10% to about 30% of the tertiary amine oxides of the invention and at least an equal amount of sodium tripolyphosphate.
  • the bis(2-hydroxyethyl)alkylamine oxides wherein the alkyl radical ranges from 12 to 14 carbon atoms in chain length are used in such preferred compositions.
  • the detergent compositions of this invention can contain any of the usual adjuvants, diluents and additives, for example, ampholytic or zwitterionic detergents, cationic deposition agents, bacteriostatic agents, dyes, fiuorescers, oxygen or chlorine bleaches, suds builders, suds depres sors and the like.
  • the yield of the bis(2-hydroxyethyl)dodecylamine was 98%.
  • the material had an amine number of 208 while 205 is calculated.
  • the bis(2-hydroxyethyl)dodecylamine oxide was substantially superior to sodium dodecylbenzenesultonate .(a widely used detergent. active for laundering compositions).
  • This test involved Washing naturally soiled cloth (desized print cloth) in a 0.1% aqueous solution of a composition comprising 20% organic detergent compound (amine oxide being tested or the alkyl benzenesulfonate standard), 50% sodium tripolyphosphate and 30% sodium sulfate.
  • the composition had a pH of 10.0 and the washing was done at 130 F. for 10 minutes using wash water of 7' grains per gallon hardness.
  • the detergency effectiveness was determined by measuring the percentage of lipid soil remaining on a standard size swatch (on a dry basis) after the washing operations. The percentage of lipid soil remaining after washing with the amine oxide test composition was compared with the percentage after washing with the alkylbenzenesulfonate standard composition. 0n the basis of the percent residual lipid soil, the lower the percent, the better the detergency performance. A Tergotometer was used for the washing operation; (Tergotometer testing is described in Detergency Evaluation and Testing, by J. C. Harris, Interscience Publishers, Inc. (1954) page 60.)
  • the hygroscopicity of bis(2-hydroxyethyl)dodecyl amine oxide was determined by exposing dry recrystallized material in a constant 50% relativehumidity chamher at 70 F.; it had weight increases of 3% after 1 day and 6% after 7 days in this hygroscopicity test. Dimethyldodecylamine oxide had weight increases of 32% after 1 day and 30% after 7 days. It is apparent that the former compound is much less hygroscopic than the latter; thus the former compound is preferred for solid form detergent compositions.
  • Bis(2-hydroxypropyl)tetradecylamine oxide, bis (2-hydroxyethyl)hexadecylamineoxide and bis(2-hydroxyethyl)-stearylamine oxide can be made by processes simi lar to that described in Example I. These compounds Will havesubstantially equivalentthermal stability and hygroscopicity characteristics and the detergency efficacy will be slightly less than that of the dodecyl compounds.
  • the bis(2-hydroxyethyl)stearylamine oxide is especially suitable. for asolid form detergent composition-such as atoiletbar.
  • Bis(2-hydroxyethy1)-2-hydroxydodecylamine oxide was tested by the cloth swatch test described in Example I and found to have a detergency effectiveness substantially superior to that of sodium dodecylbenzenesulfonate and approaching the hot F.-t F.) water detergeney of sodium tallow alcohol sulfate which is one of the best commercially used laundry detergent active ingredients.
  • Bis(2-hydroxyethyl)-2-hydroxydodecylamine oxide had Weight increases -of 1% (1 day and 7 days) in the hygroscopicity test described in Example I and decomposed at a temperature in the range of 135 C. to C.
  • the detergency of the amine oxides of this invention was evaluated by washing naturally soiled white dress shirts. Shirts were worn by male subjects under ordinary conditions for two normal working days. The degree to which a detergent composition containing a detergent compound to be tested cleaned the collars and cuifs of the soiled shirts, relative to the cleaning degree of a similar composition containing a standard detergent compound was considered a measure of the detergency effectiveness of the test compound.
  • the washing solution used in the test contained 0.03% organic surface active agent and 0.06% sodium tripolyphosphate. (No fiuorescers or bleaches or antiredeposition agents were used.)
  • the pH of the washing solution was and water of 7 grains per gallon hardness was used.
  • a conventional, agitator-type washer was used.
  • the detergent compound in the standard detergent composition was sodium dodecylbenzenesulfonate, the most commonly used organic detergent compound in heavy duty laundry detergent compositions.
  • the test detergent composition contained the detergent compound to be tested, i.e., compared with the standard composition.
  • bis(2-hydroxyethyl)dodecylamine oxide showed surprising cool water detergency. Similar results are obtained with his (2 hydroxyethyl) 2 hydroxytetradecylamine oxide, bis(2 hydroxyethyl) 2 hydroxydodecylamine oxide and N,N-bis(2-hydroxyethyl)-3-dodecoxy-2- hydroxypropylamine oxide.
  • the cool water detergency of those tertiary amine oxides of this invention wherein R and/or R (preferably both) contain a hydroxy group is best seen in aqueous washing solutions where the temperature is in the range of about 40 F. to about 95 F., the concentration of the active amine oxide compound is in the range of about 0.005% to about 0.5% and the washing solution also contains a water soluble alkaline inorganic builder salt or organic alkaline sequestrant builder salt (as hereinbefore described) in the range of about 0.01% to about 1.0%. Improved detergency is also seen using the amine oxide compositions of this invention in tepid (lukewarm) water (up to about 115 F.).
  • the tertiary amine oxides of this invention can be used in effective solid form detergent compositions having im proved hygroscopicity, thermal stability and cool water detergent characteristics. They have the following formulas:
  • Granular detergent Percent (Z -hydroxyethyl)-2-hydroxydodecyl-ethylamine oxide 10 Sodium dodecylbenzenesulfonate (the dodecyl group being derived from tetrapropylene) 10 Sodium nitrilo triacetate 50 Sodium sulfate 30
  • Granular detergent Bis (2-hyrd oxypropyl tetradecylamine oxide 10 Condensation product of one mole of n-onyl phenol and nine moles of ethylene oxide 10 Sodium pyrophosphate 50 Sodium carbonate 3 Trisodium phosphate 3 Sodium sulfate 24 Milled toilet bar Percent Bis(2-hydroxyethyl)alkylamine oxide, the alkyl group being derived from coconut fatty alcohol 10 Sodium coconut oil soap 15 Sodium tallow soap 65 Moisture 10 Milled toilet bar N,N bis(2 hydroxyethyl) 3 dodecoxy 2 hydroxypropylamine
  • Liquid form detergent compositions provide convenience in use, particularly for measurement and dis-. pensing operations.
  • Liquid detergent compositions can be in the form of solutions, dispersions or emulsions. Preferably, they can contain from about 2% to about 30% of the tertiary amine oxides of this invention and from about 5% to about 40% of a water soluble inorganic alkaline builder salt or a water soluble organic alkaline sequestrant builder salt, the balance of the composition being a solvent, such as water, and/ or other liquid vehicles.
  • R R R N O Tertiary amine oxide compounds having the formula R R R N O, wherein R is selected from the group consisting of Z-hydroxyalkyl, 3-hydroxyalkyl and 3-alkoxy-2- hydroxypropyl radicals in which the alkyl and alkoxy, respectively, range in chain length from 10 to 18 carbon atoms, R and R are each selected from the group consisting of 2-hydroxyethy1, 2-hydroxypropyl and 3-hydr-oxypropyl radicals.

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  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US156995A 1961-12-04 1961-12-04 Oxy containing tertiary amine oxides Expired - Lifetime US3202714A (en)

Priority Applications (10)

Application Number Priority Date Filing Date Title
NL286242D NL286242A (uk) 1961-12-04
US156995A US3202714A (en) 1961-12-04 1961-12-04 Oxy containing tertiary amine oxides
FI2146/62A FI41054B (uk) 1961-12-04 1962-11-28
DK516462AA DK109875C (da) 1961-12-04 1962-11-29 Rensemiddelblanding.
FR917239A FR1450374A (fr) 1961-12-04 1962-11-30 Nouveaux détergents à base d'oxyde d'amine tertiaire, procédé de préparation etutilisation
DE19621518086 DE1518086C3 (de) 1961-12-04 1962-12-01 Tertiäre Aminoxide und deren Verwendung
GB45799/62A GB1018774A (en) 1961-12-04 1962-12-04 Amine oxide detergents
BE651634A BE651634A (uk) 1961-12-04 1964-08-10
US398032A US3281368A (en) 1961-12-04 1964-09-21 Built tertiary amine oxide detergents
SE11967/64A SE332868B (uk) 1961-12-04 1964-10-05

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US398032A Expired - Lifetime US3281368A (en) 1961-12-04 1964-09-21 Built tertiary amine oxide detergents

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DK (1) DK109875C (uk)
FI (1) FI41054B (uk)
FR (1) FR1450374A (uk)
GB (1) GB1018774A (uk)
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SE (1) SE332868B (uk)

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US3483178A (en) * 1968-04-18 1969-12-09 Monsanto Co Esters,salts,and acids of organo-phosphono-amine oxides
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US5637559A (en) * 1993-03-30 1997-06-10 Minnesota Mining And Manufacturing Company Floor stripping composition and method
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US6080714A (en) * 1997-11-20 2000-06-27 Akzo Nobel Nv Solid composition comprising an amphoteric surfactant, a process for its preparation, and the use thereof
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JP3268597B2 (ja) * 1991-05-24 2002-03-25 インペリアル・ケミカル・インダストリーズ・ピーエルシー 洗浄剤組成物
MA23390A1 (fr) * 1993-12-07 1995-07-01 Procter & Gamble Composition detergente contenant un tensioactif d'oxyde-amine sous forme d'agglomerats
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US3366632A (en) * 1965-08-12 1968-01-30 Millmaster Onyx Corp N-oxides of 1-hydrocarbonoxy-2-hydroxy-3-morpholinopropanes
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US3449431A (en) * 1965-10-22 1969-06-10 Cargill Inc Tertiary gamma-alkoxypropylamine oxides
US3501335A (en) * 1965-11-26 1970-03-17 Lever Brothers Ltd Fabric conditioner
US3548056A (en) * 1966-06-30 1970-12-15 Colgate Palmolive Co Skin protecting composition containing a water - soluble partially degraded protein
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US5055233A (en) * 1989-04-26 1991-10-08 Ethyl Corporation Detergent bar process using trialkylamine oxide dihydrate
US5082600A (en) * 1989-04-26 1992-01-21 Ethyl Corporation Transparent soap bar process using trialkylamine oxide dihydrate
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US5503778A (en) * 1993-03-30 1996-04-02 Minnesota Mining And Manufacturing Company Cleaning compositions based on N-alkyl pyrrolidones having about 8 to about 12 carbon atoms in the alkyl group and corresponding methods of use
US5573710A (en) * 1993-03-30 1996-11-12 Minnesota Mining And Manufacturing Company Multisurface cleaning composition and method of use
US5637559A (en) * 1993-03-30 1997-06-10 Minnesota Mining And Manufacturing Company Floor stripping composition and method
US5744440A (en) * 1993-03-30 1998-04-28 Minnesota Mining And Manufacturing Company Hard surface cleaning compositions including a very slightly water-soluble organic solvent
US6150320A (en) * 1994-07-21 2000-11-21 3M Innovative Properties Company Concentrated cleaner compositions capable of viscosity increase upon dilution
US5824115A (en) * 1995-04-06 1998-10-20 Kao Corporation Method for improving cellulose fiber
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DK109875C (da) 1968-07-22
US3281368A (en) 1966-10-25
SE332868B (uk) 1971-02-22
FR1450374A (fr) 1966-06-24
GB1018774A (en) 1966-02-02
FI41054B (uk) 1969-04-30
BE651634A (uk) 1965-02-10
DE1518086A1 (de) 1969-11-06
NL286242A (uk)
DE1518086B2 (de) 1976-04-01

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