US3024197A - Detergent compositions - Google Patents

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Publication number
US3024197A
US3024197A US701702A US70170257A US3024197A US 3024197 A US3024197 A US 3024197A US 701702 A US701702 A US 701702A US 70170257 A US70170257 A US 70170257A US 3024197 A US3024197 A US 3024197A
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Prior art keywords
fatty acid
boric acid
fatty
ester
esters
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Expired - Lifetime
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US701702A
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English (en)
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Dohr Manfred
Wulff Carl
Werdelmann Bruno
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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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
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/58—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing atoms other than carbon, hydrogen, halogen, oxygen, nitrogen, sulfur or phosphorus
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A61Q19/10—Washing or bathing preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/02—Preparations for cleaning the hair
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q9/00—Preparations for removing hair or for aiding hair removal
    • A61Q9/02—Shaving preparations
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S516/00—Colloid systems and wetting agents; subcombinations thereof; processes of
    • Y10S516/01—Wetting, emulsifying, dispersing, or stabilizing agents
    • Y10S516/07—Organic amine, amide, or n-base containing

Definitions

  • fatty acid amides and in particular fatty acid alkylol amides have, however, the disadvantageous property of swelling in water, so that detergents prepared from the same have a certain sensitivity to water which is disagreeable, particularly when the surface-active agents themselves already exhibit certain hygroscopic properties and do not have suflicient mechanical strength, particularly when wet or moist.
  • One object of this invention is to overcome the above mentioned disadvantages.
  • a further object of this invention is a detergent of superior mechanical strength and properties in shaped form, as for example in the form of bars or pieces.
  • a still further object of this invention is a synthetic detergent which may be utilized in bar or piece form as a personal soap with excellent mechanical properties and compatibility for the skin.
  • a further object of this invention is a detergent with excellent mechanical strength.
  • the borates of fatty acid alkylol amides to be employed in accordance with the invention are obtained in a simple manner by heating acids of boron or their anhydrides with the fatty acid alkylol amides and possibly removing the water produced thereby in known manner, as can be done for example by the passage therethrough of inert gases or with the use of boiling inert solvents.
  • boric acid By anhydrides of boric acid, there are understood here all compounds which contain less bound water of constitution than boric acid of the formula H BO so that as anhydn'de of boric acid there can be used for instance metaboric acid having the formula HBO tetra-boric acid having the formula H B O or boric anhydride having the formula B
  • mixed anhydrides to which a uniform chemical composition cannot be ascribed.
  • boric acid of the formula H 30 which is melted together with the alcoholic esterification component at temperatures of 80 to 160 C. At this temperature, the Water of reaction produced escapes and the substantially anhydrous esters are obtained.
  • the boric acid esters which are to be used in accordance with the invention can however also be prepared by transesterification interchange of ester radicals) of esters of boric acids with corresponding fatty acid alkylol amides.
  • the fatty acid alkylol amides from which the boric acid esters to be employed in accordance with the invention are derived can contain 8 to 30 and preferably 10 to 20 carbon atoms in the fatty acid radical.
  • saturated or unsaturated fatty acids of natural or synthetic origin preference however being given to alkylol amides of straight-chain fatty acids.
  • the one valence of the nitrogen atoms of the fatty acid alkylol amides is replaced by an alkylol radical which may contain up to 5 carbon atoms.
  • the other valence can be bound by a hydrogen atom, an alkyl radical or an alkylol radical, in which connection the alkyl or alkylol radical can also contain up to 5 carbon atoms.
  • a hydrogen atom an alkyl radical or an alkylol radical, in which connection the alkyl or alkylol radical can also contain up to 5 carbon atoms.
  • boric acid esters of fatty acid alkylol amides which are derived from mono- 01' diethanol amines or from monoor dipropanol amines and particularly from the corresponding iso-propanol amines.
  • boric acids or boric acid esters and fatty acid alkylol amides are to be used in such quantity ratios that l to 3 and preferably 2 to 3 molecules of fatty acid alkylol amide are present for each atom or boron.
  • the esters to be employed can be incompletely esterfied, i.e., free hydroxy] groups can be contained in an ester molecule as well as a boric acid radical, or, if fatty acid alkylol amides having more than one hydroxy group in the amide radical are used, also in the amide radical.
  • the completely esterified products i.e., those which do not contain free hydroxyl groups either in the boric acid radical or in the amide radical are of particular practical importance.
  • fatty acid alkylol amide boric acid esters which contain radicals of other alcohols bound in ester form.
  • radicals of lower aliphatic, cycloaliphatic or aromatic alcohols i.e. radicals of alcohols having 1 to 8 carbon atoms in the molecule.
  • alkylol amide/alcohol mixed esters which contain radicals of higher alcohols, particularly radicals of fatty alcohols, in the molecule, i.e., radicals of aliphatic alcohols having 8 to 30 and preferably 10 to 20 carbon atoms in the molecule.
  • the molar ratio of fatty acid alkylol amide to fatty alcohol is in general not less than 20:80 and preferably greater than 50:50, for instance 60:40, :30, 80.20, etc.
  • boric acid esters are water-insoluble substances which do not swell in water and have a frequently waxlike consistency. Their melting point frequently rises and falls, particularly as compared with homologous series, with the melting point of the organic component contained therein.
  • Boric acid esters of fatty acid ethanolamides which are derived from straight chain saturated fatty acids having 10 to 20 carbon atom have melting points within the range of to C. These are products of preferred use.
  • Boric acid esters of unsaturated and/or branched-chain fatty acid alkylol amides or mixed esters with fatty alcohols have lower melting points.
  • boric acid esters having melting points of at least 40 C. and preferably 50 C. and higher.
  • boric acid esters of lower melting points can however also be employed.
  • both anionic and nonionic surface-active substances can be combined with the fatty acid alkylol amide/boric acid esters.
  • These materials include both soaps and the large group of anionic synthetic surface-active substances, including those which are only partially affected by hard water and those which are unaffected by hard water and included under the name syndet, which as water-solubilizing group contain preferably sulfonic acid group or sulfuric acid semiester groups, in which connection these group may also be neutralized.
  • the soaps to be combined with the boric acid esters can be derived from fatty acids of natural or synthetic origin, in which connection in the case of the fatty acids of natural origin, there can also be concerned hardened or OtherWiSe processed fatty acids of natural origin, particularly fractions of natural fatty acid mixtures.
  • fatty acids of synthetic origin there may be mentioned by way of example those which are obtained by the oxidation of synthetic alcohols, for instance those obtained from the addition of carbon monoxide and hydrogen to olefines (oxosynthesis), or those obtained from the carbon-monoxide hydrogenation (synolsynthesis).
  • ether carboxylic acids which can be prepared from high-molecular aliphatic or cycloaliphatic alcohols by reaction with the corresponding halogen carboxylic acids, particularly with chloracetic acid, in the presence of acid-binding agents, or the derivatives of amino acids or protein hydrolysates which contain fatty acid radicals bound in amide form and can be prepared by known methods.
  • this group of surface-active substances can be divided into sulfonates, which are salts of true sulfonic acids, and into sulfates, i.e., those substances which are derived from sulphuric acid esters.
  • alkyl or cycloalkyl sulfonates which are obtained from aliphatic or cycloaliphatic hydrocarbons by treating the hydrocarbons by radiation with actinic light or by reaction of catalysts With mixtures of sulfur dioxide and chlorine or of sulfur dioxide and oxygen and converting the products produced in this way into the corresponding sulfonates in the known manner by treatment with caustic alkali, of the various types of alkyl-aryl sulfonates which have gained particular importance, mention should be made in particular of the alkyl or cycloalkyl benzene sulfonates in addition to the alkyl or cycloalkyl naphthalene sulfonates.
  • Alkyl benzene sulfonates which are prepared from the tetrapropylene obtained by the polymerization of propylene have gained particularly wide acceptance.
  • the sulfonate type there may be mentioned the fatty acid esters of oxalkylsulfonic acids or the fatty acid amides of amino alkyl sulfonic acids in which the alkyl groups of the sulfonic acid radicals contain 2 to 4, and preferably 2or 3 carbon atoms.
  • the fatty alcohol sulfates should be particularly mentioned, the fatty alcohols from which the fatty alcohol sulfates come can be of natural origin, i.e., they may have been obtained from natural products which contain fatty alcohols, for instance in the form of esters, as for example from whale oil or beeswax, by saponification of these esters.
  • the fatty alcohols can, however, also have been obtained from fatty acids of naturalior synthetic origin by reduction.
  • the fatty alcohols from which the corresponding sulfates are prepared may be obtained completely synthetically, for instance by carbon monoxide hydrogenation or by the addition of carbon monoxide and hydrogen to olefines followed by the reduction of the aldehydes which are thus formed.
  • the sulfates of fatty acid partial esters or fatty acid partial ethers of multivalent alcohols include for instance the sulfated glycol or polyglycol esters of fatty acids, the sulfated fatty acid monoglycerides, sulfated fatty alcohol polyglycol others or fatty alcohol polyglycerin ethers, etc.
  • the sulfation products of fatty acid amides or fatty acid esters of alkylol amides and particularly of ethanol amides.
  • fatty acid or fatty alcohol derivatives in the above enumeration of alkyl or cycloalkyl radicals and corresponding hydrocarbons, there are meant thereby those which contain 8 to 24 and preferably 10 to 18 aliphatic or cycloaliphatic carbon atoms.
  • Washing and cleaning agents in accordance with the invention can consist, aside from the boric acid esters added, substantially only of surface active substances, but they may also contain in addition ordinary detergent additions.
  • the invention makes it possible to prepare detergents which consist essentially of the surface active substance in the same way as was generally possible heretofore, only in the case of soaps. Such detergents can therefore be brought into the form of pieces, shavings, chips, strings, flakes, etc., by the use of the machines customary in the soap industry, such as soap mills, extrusion presses, bar cutters and striking presses.
  • boric esters of fatty acid alkylol amides and boric acid mixed esters of fatty alkylol amides and fatty alcohols therefore imparts to the preparations prepared therewith processing properties such as in general are found only in the case of pure soap products.
  • the preparations in accordance with the invention possess high mechanical strength in use which is revealed in particular in high resistance to rubbing off and to resistance against water. If bar-shaped detergents having this composition and prepared on basis of synthetic surface-active substances become moist, they will of course take up water, but they will give it ofl again upon drying without the formation of swollen parts which are easily rubbed off and no longer give off the water being formed on the surface.
  • the invention cain also be employed in the case of the known loose detergents, particularly the powdered or granulated detergents and the paste detergents, which may then also contain the addition substances customarily employed.
  • these addition substances include for instance dior tri-alkali orthophosphates, mono-or dialkali carbonates and other salts of alkaline reaction, sodium sulfate, magnesium sulfate or other neutral slats, meta-, pyroor polyphosphates, particular mention being made in connection with the latter of the compounds Na P O and Na P O
  • oxygen-liberating substances can be present, particularly perboratese or similar substances.
  • boric acid esters to be used in accordance with the invention in the detergents can be effected by the most varied methods. If the anionactive substances or the detergents or detergent com-- ponents" produced therefrom are in solid, loose form,
  • the loose boric acid esters can first of all be mixed with them or the molten boric acid esters or boric acid esters dissolved in organic solvents can be sprayed onto the finely divided detergents, the powdered detergent being preferably moved about, for instance in mixing drums, or by screws, agitating arms, etc., and preferably by transforming the powdered detergent into a fluidized layer. These powdered detergents can then be further processed to form for instance fine soaps or bar soaps, etc. However, it is also possible to start with a highly concentrated paste batch of the anion-active substances and mix it, preferably in warmed state, with the molten boric acid ester.
  • pastes which contain less than 50% Water and preferably less than water.
  • the mixing can be done in known devices, such as agitators, kneaders, screw presses and similar apparatus.
  • the mixtures obtained in this manner can now either be further processed into bar soaps, or they can be atomized and brought into contact with other detergent components.
  • boric acid esters of fatty acid alkylol amides and their mixed esters with fatty alcohols resides in the fact that the boric acid esters do not swell in water. Accordingly, upon their incorporation in detergents, it is not only possible to avoid an increase of any sensitivity to water which might possibly be present, but in addition, water-sensitive, anion-active substances become less sensitive to water.
  • boric acid esters to be used in accordance with the invention impart an excellent compatibility for the skin to the detergents. Accordingly, the boric acid esters are suitable in particular as additions for detergents which are intended for use on the skin or which upon use necessarily come into contact with the skin.
  • fillers and superfatting agents can of course also be incorporated in the detergents of the invention, particularly when these detergents consist predominantly of anion-active substance.
  • the boric acid esters to be used in accordance with the invention are directly compatible with such fillers and supe'r-fatting agents.
  • Such substances include for instance waxes, fatty acids, fatty alcohols, fatty acid esters, particularly fatty acid glyceridesincluding fatty acid partial glycerideslanolin, lecithin, cellulose derivatives etc., and can therefore be incorporated directly together with such substances in the detergents.
  • the fillers or other substances customarily present in detergents particularly when they are produced as cakes, such as perfume, titanium dioxide, bentonite, kaolin, colloidal silica, boric acid, urea and other compounds can also be used.
  • additions which serve for the obtaining of special cosmetic or pharmaceutical effects, such as skin protection agents, deodorants, disinfectants, and other medicamental additions.
  • Example 1 In a mixer customary in the soap industry (crutcher) the following components are mixed together at about 50 C.:
  • the cakes obtained are equal in appearance to the best toilet soap. in use they give a fine bubble foam.
  • the tendency which is always present in the case of the known cake cleaning agents having a base of synthetic Washactive substances to take up water during use and thereby soften has become as low as in the case of conventional cake soaps by the addition of fatty acid ethanolamide boric acid esters. The water which has been absorbed is given up again immediately without the cake thereby being softened permanently.
  • Example 2 The following substances are melted together in a steam-heated boiler:
  • alkylbenzenesulfonate Na-salt, alkyl chain substantially C 40 kg. sodium l-alkylsulfonate (obtained by reacting coconut fatty alcohol sulfate with Na SO
  • the alkylbenzenesulfonate and the alkylsulfonate each contain about 5% by weight H 0 and about 7% by Weight inorganic salts (substantially Na SO Into the liquid mixture, there is now added while stirring vigorously 10 kg. of an ester of 3 mols coconut fatty acid monoethanolamide and 1 mol boric acid 25 kg. stearine 10 kg. of a mixture of approximately equal parts of palmityl alcohol and stearyl alcohol 5 kg.
  • Example 3 Cake cleaning agents of the following composition were prepared by the method described in Example 1:
  • Example 5 By the hot-spraying of a paste detergent batch and addgeneous mixture. This mixture, which melts approximately in the region of to C. is cast in molds into bars of a diameter of about 2 cm. The shaped articles produced in this manner are excellently suitable for perborate in known manner, there was prepared a 45 the removal of spots, particularly grease spots, from tshing agent of the following composition:
  • alkyl benzene sulfonate alkyl chain about C textiles which consist of synthetic polyamide fibers (nylon or perlon).
  • alkyl chain about C textiles which consist of synthetic polyamide fibers (nylon or perlon).
  • a bomol I ::id,ester in thcse'cakes acts as aniexjcellent fixing'agent 1 I to m of ya'yfalty C hOI pr p red by eduction of coco- I I I Ir the perfume and furthermore .upon use impart the 40 nut fatty fields a y Weight coconut fatty alcohol Sulfate (Sodium 5 Instead of the fatty alcohol polyglycol ether described,
  • non-ionic surface-active substances can be employed '7 by weight Na- O.3.3SiO in the same manner, particularly if they are present in by weight NaBO .H O .3H O the form of oily or pasty substances at the customary 1 y Weight Mgsios storage temperatures of 10 to 40 C. Such substances Y y Weigh!
  • carboxylmethylceuulose 5 include alkylphenolpolyglycol ethers, fatty acid polyglycol y Weight 2 4 esters and polyglycol ethers which are derived from parby weight Water tial ethers of fatty alcohols with polyvalent and particu- 70 by weight Na P O- or NaslsOm larly 3-6-valent alcohols or from partial esters of fatty 7 k sample of this detergent was treated with 25% by acids with the said polyvalent alcohols.
  • the non-ionic ght coconut f tt acid monoethanolamide While compounds which can be employed in accordance with if sample was treated with by weight of an the invention accordingly contain in the molecule as hyfrom 3 mols coconut fatty acid monoethanolamide drophobrc component aliphatic hydrocarbon radicals havone mol of boric acid
  • the mg 8 to 24 and preferably 10 to 18 carbon atoms and as l cats to be added were dissolved in about 10 times hydrophilic Component 4 t0 4, n preferably 6 to 16 r quantity of ethyl alcohol and sprayed onto the powglycol ether Tadlcals- 1d detergent which was kept in motion. Dirty launwas washed with these samples and a further unted sample of detergent in agitator-blade machines, a bath ratio of 1:15 in water of 18 German lness.
  • Example 8 For the preparation of a cream hair-wash 90 kg. of a paste fatty alcohol sulfate (sodium salt of the sulfuric acid semi-ester of saturated fatty alcohols having 12 to 18 carbon atoms) which contains by weight water and at most 6% by weight inorganic salts (essentially Na So and/ or 'NaCl) are mixed with heating to 50 C. There are then slowly added while stirring 6 kg. of the molten ester of boric acid and fatty acid ethanolamide described in Example 7 C. Into this mixture,
  • Example 9 For the preparation of hair wash whereupon the mixture is stirred until cool and perfumed as desired. There is obtained a hair-wash in which the addition of the boric acid ester acts in the same manner as in the case of the preparation described in the preceding example.
  • Example 10 For the preparation of a shaving soap 13.5 kg. stearic acid 4.5 kg. sorbitan-monostearate-polyglycol ether and 2.5 kg. petrolatum oil are stirred with each other at 90 C. At this temperature, there are introduced 4.5 kg. sorbitol 1.0 kg. borax 2.0 kg. t-riethanolamine It is allowed to cool to 40 C. while stirring, whereupon there are slowly added id 4 kg. of the molten boric acid-coconut fatty acid ethanolamide ester described in Examples 7 to 9.
  • a detergent composition consisting essentially of a surface-active agent which is a member selected from the group consisting of synthetic organic anionic and nonionic surface-active agents and from l-l00% by weight, referred to said surface-active agent, of a water-insoluble boric acid ester of a fatty acid alkylol amide having a melting point of at least 40 C., the fatty acid radical of said fatty acid alkylol amide containing between 8 and 30 carbon atoms, the alcohol radical of said fatty acid alkylol amide containing up to 5 carbon atoms, said boric acid ester of said fatty acid alkylol amide containing from 1 to 3 fatty acid alkylol amide molecules for each atom of boron present, any free hydroxyl groups of said boric acid ester of said fatty acid alkylol amide having been esterified with an alcohol having between 1 and 30 carbon atoms.
  • the surface-active agent is a synthetic organic anionic surface-active agent selected from the group consisting of fatty acid soaps, sulfated surface-active agents, sulfonated surface-active agents, fatty acid derivatives of amino acids, fatty acid derivatives of protein hydrolysates and mixtures thereof.
  • the surface active agent is a synthetic organic anionic surface-active agent selected from the group consisting of sulphate esters of natural fatty alcohols, sulphate esters of alcohols which are prepared by hydrogenation of natural and synthetic acids, sulphate esters of polyvalent alcohols, sulphated fatty acid monoglycerides, sulphated fatty acid polyglycol ethers and sulphated fatty alcohol polyglycerine ethers.
  • boric acid ester of said fatty acid alkylol amide is a boric acid ester of a coconut'fatty acid monoethanol-amide.
  • The. method of preparing a detergent composition consisting essentially of a surface-active agentwhich is a member selected from the group consisting of synthetic organic anionic and non-ionic surface-active agents and from 1-100% by Weight, referred to said surface-active agent, of a water-insoluble boric acid ester of a fatty acid alkylol amide having a melting point of at least 40 C., the fatty acid radical of said fatty acid alkylol amide containing between 8 and carbon atoms, the alcohol radical of said fatty acid alkylol amide containing up to 5 carbon atoms, said boric acid ester of said fatty acid alkylol amide containing from 1 to 3 fatty acid alkylol amide molecules for each atom of boron present, any free hydroxyl groups in said boric acid.
  • a surface-active agent which is a member selected from the group consisting of synthetic organic anionic and non-ionic surface-active agents and from 1-100% by Weight, referred to said
  • ester of said fatty alkylol amide having been. esterified with an alcohol having between 30 and carbon atoms, which comprises admixing the synthetic organic surface-active agent with said water-insoluble boric acid ester of a fatty acid alkylol amide, while thoroughly agitating said mixture.

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  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Dermatology (AREA)
  • Chemical & Material Sciences (AREA)
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  • Birds (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
US701702A 1956-12-11 1957-12-10 Detergent compositions Expired - Lifetime US3024197A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEH28793A DE1038694B (de) 1956-12-11 1956-12-11 Waschmittel

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US701702A Expired - Lifetime US3024197A (en) 1956-12-11 1957-12-10 Detergent compositions

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US (1) US3024197A (enrdf_load_stackoverflow)
BE (1) BE560646A (enrdf_load_stackoverflow)
CH (1) CH364064A (enrdf_load_stackoverflow)
DE (1) DE1038694B (enrdf_load_stackoverflow)
FR (1) FR1186790A (enrdf_load_stackoverflow)
GB (1) GB836939A (enrdf_load_stackoverflow)
NL (1) NL223085A (enrdf_load_stackoverflow)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1236704B (de) * 1962-07-20 1967-03-16 Johannes Roedger Dr Med Geruchsschwache desinfizierende Wasch- und Reinigungsmittel
US3330856A (en) * 1963-01-21 1967-07-11 Monsanto Co Vicinal sulfocarbamate esters
US4258063A (en) * 1978-06-23 1981-03-24 Henkel Corporation Self-emulsifying cosmetic base
US4533481A (en) * 1983-04-20 1985-08-06 The Lubrizol Corporation Polycarboxylic acid/boric acid/amine salts and aqueous systems containing same
US4675125A (en) * 1984-07-02 1987-06-23 Cincinnati-Vulcan Company Multi-purpose metal cleaning composition containing a boramide
US5089174A (en) * 1989-01-19 1992-02-18 The Procter & Gamble Company Laundry detergent bars free of C12 -C18 fatty acids and containing an alkylbenzene sulfonate, an alkyl sulfonate and a fatty alcohol
CN100529037C (zh) * 2007-03-09 2009-08-19 南开大学 汽车清洗液
CN102585581A (zh) * 2011-12-29 2012-07-18 广东省南方彩色制版有限公司 一种印刷版辊超声波水基清洗剂及其制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2173448A (en) * 1937-05-17 1939-09-19 Emulsol Corp Preparation of alkylolamine derivatives
US2216618A (en) * 1939-08-10 1940-10-01 Katz Jacob Surface active anionic boric acid ester compounds of amino alcohols
US2441063A (en) * 1943-06-04 1948-05-04 Quaker Chemical Products Corp Salts of alkylolamine boric esters

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2173448A (en) * 1937-05-17 1939-09-19 Emulsol Corp Preparation of alkylolamine derivatives
US2216618A (en) * 1939-08-10 1940-10-01 Katz Jacob Surface active anionic boric acid ester compounds of amino alcohols
US2441063A (en) * 1943-06-04 1948-05-04 Quaker Chemical Products Corp Salts of alkylolamine boric esters

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1236704B (de) * 1962-07-20 1967-03-16 Johannes Roedger Dr Med Geruchsschwache desinfizierende Wasch- und Reinigungsmittel
US3330856A (en) * 1963-01-21 1967-07-11 Monsanto Co Vicinal sulfocarbamate esters
US4258063A (en) * 1978-06-23 1981-03-24 Henkel Corporation Self-emulsifying cosmetic base
US4533481A (en) * 1983-04-20 1985-08-06 The Lubrizol Corporation Polycarboxylic acid/boric acid/amine salts and aqueous systems containing same
US4675125A (en) * 1984-07-02 1987-06-23 Cincinnati-Vulcan Company Multi-purpose metal cleaning composition containing a boramide
US5089174A (en) * 1989-01-19 1992-02-18 The Procter & Gamble Company Laundry detergent bars free of C12 -C18 fatty acids and containing an alkylbenzene sulfonate, an alkyl sulfonate and a fatty alcohol
CN100529037C (zh) * 2007-03-09 2009-08-19 南开大学 汽车清洗液
CN102585581A (zh) * 2011-12-29 2012-07-18 广东省南方彩色制版有限公司 一种印刷版辊超声波水基清洗剂及其制备方法
CN102585581B (zh) * 2011-12-29 2013-09-11 广东省南方彩色制版有限公司 一种印刷版辊超声波水基清洗剂及其制备方法

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NL223085A (enrdf_load_stackoverflow)
GB836939A (en) 1960-06-09
CH364064A (de) 1962-08-31
BE560646A (enrdf_load_stackoverflow)
DE1038694B (de) 1958-09-11
FR1186790A (fr) 1959-09-01

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