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Publication numberUS3024197 A
Publication typeGrant
Publication dateMar 6, 1962
Filing dateDec 10, 1957
Priority dateDec 11, 1956
Also published asDE1038694B
Publication numberUS 3024197 A, US 3024197A, US-A-3024197, US3024197 A, US3024197A
InventorsDohr Manfred, Wulff Carl, Werdelmann Bruno
Original AssigneeHenkel & Cie Gmbh
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Detergent compositions
US 3024197 A
Abstract  available in
Images(6)
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Claims  available in
Description  (OCR text may contain errors)

3,024,197 Patented Mar. 6, 1952 3,024,197 DETERGENT COMPOSITIONS Manfred Dohr, Dusseldorf-Werster, Carl Wullf, Dusseldorf-Benrath, and Bruno Werdelmann, Ratingen, near Dusseldorf, Germany, assignors to Henlrel 81 Cie. G.m.b.H., Dusseidorf-Holthausen, Germany, a corporation of Germany No Drawing. Filed Dec. 10, 1957, Ser. No. 701,702 Claims priority, application Germany Dec. 11, 1956 13 Claims. (Cl. 252117) This invention relates to improved detergents.

It is known that the properties of certain surface-active agents which are used as detergents or detergent components can be improved by the addition of fatty acid amides and in particular fatty acid alkylol amides. The fatty acid amides and particularly the 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.

These and still further objects will become apparent from the following description.

In accordance with the invention it has been found that the properties of conventional detergents may be improved in many respects, as for example with respect to mechanical strength, water-resistance, compatibility to the skin and the like by the addition of boric acid esters of fatty acid alkylol amides.

.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. 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 In accordance with the invention there can also be employed mixed anhydrides to which a uniform chemical composition cannot be ascribed. There is preferably employed 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. There may be concerned in this connection 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. There are preferably employed 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.

In the preparation of the substances which are to be used in accordance with the invention, 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. Accordingly, 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. However, 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.

In accordance with the invention, however, there may also be employed fatty acid alkylol amide boric acid esters which contain radicals of other alcohols bound in ester form. In this connection, there may be concerned radicals of lower aliphatic, cycloaliphatic or aromatic alcohols, i.e. radicals of alcohols having 1 to 8 carbon atoms in the molecule. Of particular interest, however, are 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. When using the fatty acid alkylol amide/fatty alcohol mixed esters, 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.

These 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. For the preparation of solid products, such as shaped cleaning agents, bar soaps or else powered, flaked and similar washing agents, it is advisable to use boric acid esters having melting points of at least 40 C. and preferably 50 C. and higher. For the preparation of liquid or paste preparations, such as liquid or paste preparations serving for shampooing or shaving, boric acid esters of lower melting points can however also be employed.

The quantity of boric acid esters to be added depends on the nature of the surface-active substances and the effect desired. In general there need not be employed a larger addition of boric acid ester than the quantity of surface-active substance present, the quantity of surfaceactive substance referring to the active substance free from fillers or diluents, One preferably operates, however, with smaller quantities, for instance quantities less than about 50% by weight. Frequently even much smaller quantities, for instance quantities of 2 to 15% by weight, are sufficient to obtain a satisfactory result, and in a few cases a good elfect can still be noted with quantities of the order of 1% by weight. These quantities refer to the quantities of surface-active substance=l% by weight.

In accordance with the invention 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. Among the 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). As further anionic, surface-active substances, mention may be made of the 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.

The preparations in accordance with the invention are, however, used with particular advantage, together with the syndets. Depending on the water-solubilizing radical present, 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. Within the group of sulfonates, there may be mentioned by Way of example the 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. As further representative of 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.

Among the group of anion-active substances of the sulfate type, 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. Finally 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. In addition to these sulfates, however, there should also be mentioned the sulfates of fatty acid partial esters or fatty acid partial ethers of multivalent alcohols. They 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. Finally, in this connection there should also be mentioned the sulfation products of fatty acid amides or fatty acid esters of alkylol amides, and particularly of ethanol amides.

Insofar as mention has been made of 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.

The 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. The addition in accordance with the invention of 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, however, 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 Furthermore, oxygen-liberating substances can be present, particularly perboratese or similar substances. Finally addition sub stances which are customarily employed such as cellulose glycolates or other water soluble cellulose derivatives, optical brighteners, dyes, etc., can be present in the powdered or paste detegrents of the invention. In the case of loose detergents, the boric acid esters to be used in accordance with the invention have proven to be excellent perfume-carriers.

The incorporation of the 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,

for instance in powder 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. It is advisable to use for this purpose 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.

The great advantage of the 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.

If synthetic anionic surface-active substances or soaps prepared from synthetic fatty acids are worked into cake soap, considerabl difi lculties occur on the machines customarily employed for this purpose, such as the sticking and smearing of the mass on the milling rolls and the uncut bars formed have a rough nature and non-homogeneous structure and tear apart upon pressing. The cakes obtained, have a dull surface and great sensitivity to water, which makes itself noticeable in the manner that the parts of a piece of soap which come into contact with water swell and are easily rubbed off during the washing, so that a large amount is used and wasted. By the addition of the boric acid esters in accordance with the invention, there are obtained, however, cakes of excellent mechanical strength, particularly when the boric acid esters to be employed have a melting point above 50 C. and preferably a melting point above 65 C.

The 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.

Upon the preparation of detergents, such as cakeshaped detergents the predominant component of which consists of active substance, at large number of fillers and superfatting agents were previously employed. These fillers and super-fatting 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. However, 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. There can furthermore be incorporated additions which serve for the obtaining of special cosmetic or pharmaceutical effects, such as skin protection agents, deodorants, disinfectants, and other medicamental additions.

6 The following examples are given by way of illustration and not limitation.

Example 1 In a mixer customary in the soap industry (crutcher) the following components are mixed together at about 50 C.:

60 kg. of a pasty fatty alcohol sulfate (sodium salt of the sulfuric semi-ester of saturated fatty alcohols having 12 to 18 carbon atoms), which contains 10% by weight water and at most 6% by weight inorganic salts (essentially Na SO and/ or NaCl),

12 kg. of the ester of from 3 mols of coconut fatty acid monoethanolamide and 1 mol of boric acid (clear melting point=98 C.),

6 kg. of a mixture of approximately equal parts of palmityl alcohol and stearyl alcohol,

15 kg. paraffin of a melting point of 50 to 52 C.,

12 kg. carboxylmethylcellulose,

1 kg. perfume Though the mixing of the components can be effected in any desired sequence, it is advisable to first mix the fatty alcohol sulfate paste together with the Other components except the boric acid ester, at a slightly elevated temperature, for instance at about 50 C., and to add the molten boric acid ester to the mixture at this temperature. Afterthorough working of the mass, it is milled three times in the customary manner. The shaving obtained are formed into an endless bar while still warm in a vacuum double-bar press, this bar then being converted into cakes in the known manner.

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:

10 kg. 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. polyethylene glycol (molecular weight=6000) The mixture which is still liquid at about C. is introduced into a plate-cooling machine. After standing for 24 hours, the curd-soap-like blocks are removed from the plate-cooling machine, cut and stamped in the known manner. There are obtained cakes of good foaming property and high cleaning power. Despite the alkyl benzene sulfonate content, no damage or irritation to the skin is produced upon use.

Example 3 Cake cleaning agents of the following composition were prepared by the method described in Example 1:

40% by weight coconut fatty acid monoglyceride sulfate (sodium salt) I 15% by weight alkylhenzenesulfonate (sodium salt,alky1 I 1.0% by ht of an ester 3 mol stearylmonoethanol- 15 i rannerfor the preparation of fine soaps, .t'he're are added, I I 1 I 1 r I j :ferrcd to, the entire soap batch,- a molten mixture of I imonoethanoiaml-d I I by :weight, perfume and 4% by weight of. an ester tures indicatedin the-table. Thereupon' foam waspm- I i duced at these temperatures inan apparatus constructed according to J'. Ross and G. D, Miles; Oil and Soap, I I

vol. 18, pages 99 tov 102 (1941), and the height of the foam read after standing for 0,, 1 3,5 and minutes. Thereupon the heights of the foams wereread after the said periods of time with a given bath liquor and these; I

ch'ain' about C )I I I I I I I I 14% by weight stcaric'acid I I I I I I i I I 4% by weight polyethylene glycol (molecular :we1ght= I 5 5% by weight of apolyether having the, overall general 1 I a I formula I Y I I, f i values were placed 'as foam' values in the'table; The j I HOP--(C2H4O)a+(C3H6O)b-F(C2H4O)j I v I action ofthe additions is more favorable the higher the I I t an r g molecularwfiight 3 a 1 10, indicated foam values. In order to compensate for ex- I I I I ing rang of about'5t) to.55 C., themo r t i perimentali errors by, different amounts of dirtin the i I Of the P the, molecule: indicated by th l h l q ors, the values contained in the table Werecal 3 pa s being i n' t range of 1500 TO 1800? culalted as average values of a series of measurements 7 (Commercial. product Pluronic F 68.) I I I amide and 1 mole boric-acid Foam Values 1% by weight perfume I I O DeItergmt 1 y i h: titanium dioxide I W tltlti WWW: was

3% by weight 3,3,5,5',6,6'-h,exachlor-2,2'-dioxydiphenyl- :lcitl et lmacid ester methane 2O nolumule 5% by weight water I III I I I I I 6 2% by weight inorganic. salts, essentially N32SO4 1M I I I if It is advisable in the preparation to dissolve the halo- 34 I 41 I 47 genphenol in the molten boric acidester and add the re- I I I p I I naining components to the mixture in this form. There i obmmed Cakes which do 99h a h We I I ,If: the ester of 3 mols coconut 'fattyacid'monoethanol- I I 'hlchhave long'lastmg deodonzmg actwn i v :amide and 1 molboricacid is replaced by the same 5quan- Example 4 i tity by Weight of the ester from 2 mols coconut fa tty I I p n acid monoethanolamide and 1 inol of bIo'r ic' acid or by I To customary Soap batch" Such as used m known I the ame quantity by eight ofZ-mols coconutfatjty acid v a I e, l 11101 coconut alcohol and 3 mols i b ric acid, similar results are obtained I E 3 mols coconut fatty acid monoethanolamide and l 3 Example 6 lol boric acid. The soa batch is then thoroughly 5 I I I orlted, milled in known r anner' and worked into an I i Equal Part? by 8 9 l l ,bqne' q f p I v I i ldless bar on an eXtrusion press, I By c'utting and stamp" I i I nut fatty and 'f i j iw m de (mating, =9. I II I g, vthere areobtained cakes of toilet soapp The b'or'ic i the addltmn Product 9f 9731015 0f e h l n 0x155 ap ifoam a very finely-porous creamy structure.

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:

% by weight sodium alkyl benzene sulfonate (alkyl chain about C textiles which consist of synthetic polyamide fibers (nylon or perlon). For this purpose the spotted places are rubbed vigorously with the bar and then washed thoroughly with Warm Water.

melted together to form. 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,

salt) other 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 For this purpose 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.

1e Wash was introduced into the freshly prepared 5, which was heated so that after 35 minutes the rig point was reached. After an additional 15 minof heating while boiling, samples of the bath liquor taken. These samples were cooled tothe tempera- 75 Example 7 For the preparation of a bath addition 25 kg. pine needle oil (terpene free) 20 kg. isopropyl alcohol 50 kg. of an aqueous fatty alcohol sulfate solution, which contains about 35% by weight of the ammonium salt of a sulfuric acid semi-ester of saturated fatty alcohols having l2 to 18 carbon atoms, and not more'than 5% by weight inorganic salts are mixed while heating to 50 there is slowly introduced kg. of a molten ester of 3 mols coconut fatty acid monoethanolamide and 3 mols boric acid (clear melting point=98 C.)

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,

and the mass is stirred until cool. There are then added 4 kg. liquid egg yolk of technical grade whereupon perfuming and coloring are effected as desired. There is obtained a cream hair-wash of excellent foaming power. By the addition of the boric acid ester, the foam becomes creamier, denser and firmer. The degreasing action of the fatty alcohol sulfate is counteracted by the presence of the boric acid ester. For this reason the skin has a pleasant feeling after washing. The hair is soft, supple and particularly easy to treat.

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.

After the mixture has cooled while stirring, there are added 0.5 kg. perfume and 58.5 kg. water Example 11 The boric acid esters as used in the preceding examples may be replaced by the following esters:

(a) Ester prepared from 1 mol of boric acid and 3 mole of lauric acid monoethanolamide. Melting portion of the ester: 108-109" C.

(b) Ester prepared from 1 mol of boric acid, 1 mol of fatty alcohol (derived from coconut fatty acid) and 2 mols of coconut fatty acid monoethanolamide. Melting point of the ester: 74-75" C.

(c) Ester of a composition similiar to this described under (b) wherein the fatty alcohol is derived from tallow fatty acid. Melting point of the ester: 74-75" C. This ester is especially suited as addition for bars on basis of synthetic detergents.

We claim:

1. 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.

2. A detergent composition according to claim 1, in which said water-insoluble boric acid ester of the fatty acid alkylol amide has a melting point of at least 50 C.

3. A detergent composition according to claim 1, in which a molar ratio of fatty acid alkylol amide to alcohol in said ester is between 1:2 and 2: 1.

4. A detergent composition according to claim 1, wherein 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.

5. A detergent composition according to claim 1, wherein 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.

6. A detergent composition according to claim 1, in bar form.

7. A detergent composition according to claim 1, in

which said boric acid ester of said fatty acid alkylol amide is a boric acid ester of a coconut'fatty acid monoethanol-amide.

' 8. A detergent composition according to claim 1 in which said boric acid ester of said fatty acid alkylol amide is a boric acid ester of coconut fatty acid monoethanolamide containing 3 molecules of coconut fatty acid monoethanolamide for each atom of boron present.

9. A detergent composition according to claim 1 in which said boric acid ester of said fatty acid alkylol amide is a boric acid ester of lauric acid monoethanolamide containing 3 molecules of lauric acid monoethanolamide for each atom of boron present.

10. A detergent composition according to claim 1 in which said boric acid ester of said fatty acid alkylol amide is a boric acid ester of stearic acid monoethanolamide containing 3 molecules of stearic acid monoethanolamide for each atom of boron present.

11. A detergent composition according to claim 1 wherein said boric acid ester of said fatty acid alkylol amide is a boric acid ester containing 1 molecule of a fatty alcohol derived from tallow fatty acid and 2 molecules of :oconut fatty acid monoethanolamide for each atom of Boron present.

12. A detergent composition according to claim 1 vherein said boric acid ester of said fatty alkylol amide s a boric acid ester containing 1 molecule of a fatty alco- 101 derived fronrcoconut fatty acid and 2 molecules of coconut fatty acid monoethanolamide for each atom of boron present.

13. 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. 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.

References Cited in the file of this patent UNITED STATES PATENTS 25 2,173,448 Katzmann Sept; 19, 1939 2,216,618 Katz Oct. 1, 1940 2,441,063 Gilmann May 4, 1948

Patent Citations
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US2173448 *May 17, 1937Sep 19, 1939Emulsol CorpPreparation of alkylolamine derivatives
US2216618 *Aug 10, 1939Oct 1, 1940Jacob KatzSurface active anionic boric acid ester compounds of amino alcohols
US2441063 *Jun 4, 1943May 4, 1948Quaker Chemical Products CorpSalts of alkylolamine boric esters
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3330856 *Jan 21, 1963Jul 11, 1967Monsanto CoVicinal sulfocarbamate esters
US4258063 *Jun 23, 1978Mar 24, 1981Henkel CorporationSelf-emulsifying cosmetic base
US4533481 *Apr 20, 1983Aug 6, 1985The Lubrizol CorporationPolycarboxylic acid/boric acid/amine salts and aqueous systems containing same
US4675125 *May 19, 1986Jun 23, 1987Cincinnati-Vulcan CompanyMulti-purpose metal cleaning composition containing a boramide
US5089174 *Aug 2, 1990Feb 18, 1992The Procter & Gamble CompanyLaundry detergent bars free of C12 -C18 fatty acids and containing an alkylbenzene sulfonate, an alkyl sulfonate and a fatty alcohol
CN100529037CMar 9, 2007Aug 19, 2009南开大学Efficient automobile washing liquid
CN102585581A *Dec 29, 2011Jul 18, 2012广东省南方彩色制版有限公司Ultrasonic water-based cleaning agent for printing plate roller and preparation method for cleaning agent
CN102585581BDec 29, 2011Sep 11, 2013广东省南方彩色制版有限公司Ultrasonic water-based cleaning agent for printing plate roller and preparation method for cleaning agent
DE1236704B *Jul 20, 1962Mar 16, 1967Johannes Roedger Dr MedGeruchsschwache desinfizierende Wasch- und Reinigungsmittel
Classifications
U.S. Classification510/150, 510/465, 510/317, 516/14, 510/133, 510/505, 510/159, 510/122, 510/495, 516/DIG.700, 510/350, 510/294
International ClassificationA61Q5/02, C11D1/00, A61Q19/10, A61Q9/02, A61K8/58
Cooperative ClassificationA61Q19/10, C11D1/00, Y10S516/07, A61K8/58, A61Q5/02, A61Q9/02
European ClassificationA61K8/58, A61Q5/02, A61Q19/10, C11D1/00, A61Q9/02