DE2250236A1 - DETERGENTS AND DETERGENTS - Google Patents

Description

IMiCHTCAMWAlTS A _nPn »" -

I'ir, I '. :. \ V ... '.WVh. V / ALT5R 3SIl 2 ^ 50236

Sf!.; :: ■ '■; ■ ' \ "» ' ^il * I2.ow.t972

Our No. 18 I99

The Procter & Gamble Company Cincinnati, Ohio, V.St.A.

Detergents and cleaning agents

The invention relates to detergents containing builders, which contain an organic water-soluble detergent and (ethylenedioxy) diacetic acid as a builder. If in A large part of the builder is used in relation to the detergent, the detergents are referred to as coarse detergents, which are primarily intended for washing heavily soiled fabrics. Detergents that are proportionate Containing smaller amounts of builders, pain detergents are used for lightly soiled tissues and wool are provided.

The use of builders along with organic water-soluble synthetic detergents and the properties which these substances have in terms of improving the overall detergency of such detergents are known

30 9 8 1.6 / 1 1 73 OHONAL INSPECTED

2 2! "» Π 2 36

Apparitions. A Vie 1 · λί \\ L of such substances, in particular the flatriumpolyphoaphate a ind known for use alr> builders. However, it has been some concern expressed <\\ iV> certain algae in waters to phosphorylated strength materials grab as nutrients. Phosphorus-free builders would not be subject to this criticism. There was therefore a need for builders that are biodegradable but are comparable to sodium tripolyphosphates in terms of their effectiveness.

The mechanism by which the builders have their detergency of water-soluble organic detergents is unknown, seems, however, from a combination of water softening effect, To pass dirt suspension, anti-graying effect and pH value adjustment. This theory allows however, it does not predict which compounds are useful as effective builders. It has therefore been determined empirically that a variety of substances, including the tripolyphosphates listed above, as well as phosphonates, nitrilotriacetates, Sodium sulfate or various silicates all serve as builders, at least to some extent.

The (ethylenedioxy) diacetic acid builders described here can be roughly referred to as carboxylate builders and, more precisely, as polycarboxylate builders, as they contain two carboxyl functional groups. A variety of polycarboxylates as builders. Water softeners and lime soap agents are suitable in detergents. E.g. US-PS 2 26 * J 103 relates to the use of various Polycarboxylic acids as builders and water softeners. The patent states that polycarboxylates have three or more carboxyl groups per molecule are suitable as a builder and water softener. NL patent application 6 501 871 relates to

309816/1173 _{BAD 0RIG1NAL}

Use of different polymers such as itaconic and aconitic acid in detergents. ZA-PS 69/36 * 17 describes the use of oxydisuccinic acid as a builder. It can therefore be seen that a large number of polycarboxylates have already been proposed as builders for improving detergency. However, these substances have a number of disadvantages and therefore have not found general use for this purpose. For example, many such fabrics are difficult and expensive to manufacture. Other of these substances cause unpleasant side effects on human skin. Finally, it is desirable _s to have polycarboxylate builders with a minimum molecular weight _s so that the biological oxygen demand is reduced to a minimum during their biodegradation.

It has now been found that _s (ethylenedioxy) -diacetic acid and its water-soluble salts as DetergenK builder are suitable. This is surprising in view of the prior art to date, according to which only the carboxylic acid _{derivatives 9} which have at least three carboxylate groups are suitable for this purpose. It has also been found that (ethylenedioxy) diacetic acid is readily biodegradable and shows no significant percutaneous toxicity ₉ when it comes into contact with human skin. Finally, (ethylenedioxy) diacetic acid and its water-soluble salts have a degree of activity than the detergent builders that is the same or better than many more complex and expensive polycarboxylates in technology.

ff

Task dor F.rfindung was therefore Dr tergenz builders and WaiJisorvjf-iclimncher in the form of (Ätljvl (mdioxy) di (>r>r> ißSäurf2 and (loron v.'uusi-rlönliolm salts for before! (Jp. unr to ask so

30S816 / 1173 BADORIQINAL

-H-

detergents containing builders, which are water-soluble contain organic detergent and (ethylenedioxy) diacetic acid or its water-soluble salts.

The invention relates to detergents which (1) about 1 to about 95% by weight, preferably about 30 to about 70% by weight, (ethylenedioxy) diacetic acid or a water-soluble salt thereof as a builder and (2) about 5 to about 99 wt -.% of a water-soluble organic detergent contained.

The present invention also relates to a method for softening water which is characterized in that so much (ethylenedioxy) diacetic acid or a water-soluble salt thereof is added to the water that the hardness of the water is reduced is decreased to below about 0.958 °.

In the detergents according to the invention and the inventive The builders used in water softening processes are the water-soluble salts of (Xthylenedioxy) diacetic acid Formula:

MOOCCH ₂ OCH ₂ Ch ₂ OCH ₂ COOM

wherein M can be any cation that a water-soluble Salt with the (ethylenedioxy) diacetic acid anion (i.e. water-soluble Cations). Such water-soluble cations are e.g. hydrogen, the alkali metal cations such as lithium, Sodium, potassium, rubidium and cesium ions, as well as ammonium, tetraalkylammonium, e.g. tetramethylammonium, tetrapropylammonium or tetradecylammonium. Other suitable water-soluble cations are, for example, the alkanolammonium cations, e.g.

3OP316 / 1173

Triethanolammonium, diethanoiammonium, dipropanolammonium or methanolammonium. For the present purpose the (Äthylendioxy) -diaeetate are preferred, wherein the water-soluble cations are hydrogen, sodium, potassium and triethanolammonium. The pinodium salt is particularly preferred.

The water-soluble (! Ethylenedioxy) diacetate builders can either as the only builder in the detergent according to the invention or optionally in conjunction with other well-known ones Builders are used. For example, the sodium and potassium tripolyphosphates, the sodium and Potassium nitrilotriaeetate, the mellitate, the benzene pentacarboxylate, Citrates, carbonates, oxydisuecinates or phloroglucinol trisulfonates all together with the (ethylenedioxy) diacetates used to make detergents containing, mixed builders to manufacture.

The water-soluble organic detergents which, according to the invention, together with the water-soluble (ethylenedioxy) acetate builders any anionic (soap or non-soap) well known in the art can be used. be nonionic, zwitterionic or ampholytic detergents. Mixtures of these detergents can also be used be used. The chemical nature of the water-soluble organic detergents is therefore not an essential characteristic of the present invention than the water-soluble (ethylenedioxy) diacetate their builder function in use exercise with all kinds of organic detergents. The alkylbenzenesulfonates are used in the present case and polyethylene oxides of alkylphenols because of their cost and the ß-methoxysulfonates, alkylated- <£ -Sulfocarboxy-

h late and ammonio ^ propanesulfonate because of their relative proportions

309316/1173

low calcium sensitivity preferred.

The ratio of water-soluble organic detergents to (ethylenedioxy) diacetate builder in the inventive Detergents can be between about 1: 100 and 1: 1 (by weight), preferably about 1:10 and 1: 2 (by weight) Based on weight).

Among the examples of water-soluble detergents suitable for use with the (ithflendioxy) diacetate builders according to the invention include the following compounds:

A. Anionic soapy and non-soap synthetic detergents

This class of detergents includes common alkali metal soaps such as the sodium, potassium, ammonium and alkanolammonium salts of higher fatty acids having from about 8 to about 2k carbon atoms, and preferably from about 10 to about 20 carbon atoms. Suitable fatty acids can be obtained from natural sources such as vegetable or animal esters (e.g. palm oil, coconut oil, babassu oil, soybean oil, castor oil, tallow, whale and fish oils, lard and mixtures thereof). The fatty acids can also be produced synthetically (for example by oxidation of petroleum or by hydrogenation of carbon monoxide according to the Fischer-Tropsch process). Resin acids such as rosin and the resin acids in tallow oil are suitable.

mi /

Naphthenic acids are also suitable. Sodium and potassium soaps can be made by direct saponifying the fats and oils or by neutralizing the free fatty acids obtained in a separate manufacturing process will. The sodium and potassium salts are particularly suitable

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the mixtures of fatty acids derived from coconut oil and tallow, i.e. sodium or potassium tallow and coconut soap.

This class of detergents also includes water-soluble salts, in particular the alkali metal salts of organic compounds Sulfuric acid reaction products that have an alkyl radical containing from about 8 to about 22 carbon atoms and in their molecular structure have a sulfonic acid or sulfuric acid ester residue. (The term alkyl includes a higher proportion of alkyl Acyl residues). Examples of this group of synthetic detergents which form part of the preferred according to the invention Forming detergents provided with builder are the sodium or potassium alkyl sulfates, especially those that by sulfating the higher alcohols (Cg-C - ^ - carbon atoms), made by reducing the glycerides of tallow or coconut oil; the sodium or Potassium alkylbenzenesulfonates in which the alkyl group has about 9 to about 15 carbon atoms in straight or branched chain Configuration such as those described in U.S. Patents 2,220,099 and 2,477,383 (particularly The linear straight-chain alkylbenzenesulfonates, in which the alkyl groups average about Have carbon atoms, and these are commonly abbreviated G. ^ LAS will); Sodium alkyl glyceryl ether sulfonates, especially those ethers of higher alcohols derived from tallow and Coconut oil originate; Sodium coconut oil fatty acid monoglyceride sulfonates and sulfates; Sodium or potassium salts of sulfuric acid esters of the reaction product of one mole of a higher fatty alcohol (e.g. tallow or coconut oil alcohols) and about up to 6 moles of ethylene oxide; Sodium or potassium salts of alkyl phenol ethylene oxide ether sulfate with about 1 to 10 units, ethylene oxide per molecule, and in which the alkyl radicals are about 8 to contain about 12 carbon atoms.

309816/1173

Surfactants such as anionic phosphates are also useful in the present invention. These are surfactants with substantial detergency in which the hydrophobic "group-linking anionic solubilizing group is a phosphorusoxyacid. The more common solubilizing groups are, of course, -SOhH, -SO, H and -COpH. Alkyl phosphate esters such as (RO) ₂ PO ₂ H and ROPO-H ₂ , in which R is an alkyl chain of from about 8 to about 20 carbon atoms, are suitable.

These esters can be modified by adding 1 to about 40 alkylene oxide units, for example Ethylene oxide units incorporated. The formulas for these modified anionic phosphate detergents are

£ RO- (CH ₂ CH ₂ O) n: 7 ₂ POM or

0 II CH ₀ ) "'J -POM

_n ~ J -P

0-M

in which R is an alkyl group having about 8 to 20 carbon atoms or an alkylphenyl group in which the alkyl group is about Contains 8 to 20 carbon atoms, M is a water-soluble one Cation, such as hydrogen, sodium, potassium, ammonium or substituted ammonium and η is an integer of 1 to about Ί0 mean.

Another class of anionic organic detergents that is particularly useful in the present invention includes salts of 2-acyloxyalkane-1-sulfonic acids. These salts have the following formula

3 CHUM 6/1 17

OCR ₉

CH - CH ₂ SO ₃ M II

in the R, an alkyl radical having from about 9 to about 23 carbon atoms (which form an alkane group with the two carbon atoms), Rp is an alkyl radical with 1 to about 8 carbon atoms and M represents a water-soluble cation.

The water-soluble cationj M, in the above-described Structural formula can, for example, be an alkali metal cation (e.g. sodium, potassium, lithium), ammonium or substituted Be ammonium cation. Specific examples of substituted ammonium cations include methyl, dimethyl and trimethylammonium cations and quaternary ammonium cations, such as tetramethylammonium and dimethylpiperidinium cations as well as those derived from alkylamines such as ethylamine, diethylamine, triethylamine and mixtures descend from the same. ... .

To the specific examples of ß-acyloxy-alkane-1-sulfonates or optionally 2-acyloxy-alkane-l-sulfonates, which in the pre-: lying case are suitable for achieving superior degrees of cleaning under essentially neutral washing conditions, include the sodium salt of 2-acetoxy-tridecane-l-sulphonic acid; the potassium salt of 2-propionyloxy-tetradecane-1-sulfonic acid; the lithium salt of 2-butanoyloxy-tetradecane-1-sulfonic acid; the sodium salt of 2-pentanoyloxypentadecane-1-sulfonic acid; the sodium salt of 2-acetoxy-hexadecane-1-sulfonic acid; the Potassium salt of 2-octanoyloxy-tetradecane-1-sulfonic acid; the Sodium salt of 2-acetoxy-heptadecane-1-sulfonic acid; the Lithium salt of 2-acetoxy-octadecane-1-sulfonic acid; the potassium salt of 2-acetoxy-nonadecane-1-sulfonic acid; the sodium salt

309816/1173

of 2-propionyloxy-docosane-1-sulfonic acid and its isomers.

According to the invention preferred ß-acyloxy-alkane-1-sulfonates are the alkali metal salts of ß-acetoxy-alkane * l-sulfonic acids of the above formula, in which R _{1 is} an alkyl radical with about 12 to about 16 carbon atoms; these salts are preferred because of their excellent cleaning properties and ready availability.

Typical examples of the β-acetoxyalkanesulfonates described above are described in the literature. BE-PS 650 323 describes the preparation of certain 2-acyloxyalkanesulfonic acids. US-PSS 2,094,451 describes similarly and 2,086,215 certain salts of β-acetoxyalkanesulfonic acids.

Another preferred group of anionics according to the invention Detergents because of their excellent cleaning properties as well as their low sensitivity are preferred over water hardness (Ca ++ and Mg ++ ions), the alkylated / sulfocarboxylates are about 10 up to about 23 carbon atoms and the following formula:

0
Il
R-CH-C-OR '

I.
SO ₃ M

in which R denotes a Cg to Cp _Q alkyl, M denotes one of the water-soluble cations described above, preferably a sodium ion, and R ¹ denotes a short-chain alkyl, for example a methyl, ethyl, propyl or butyl. These compounds are obtained by esterifying commercially available ^ -sulfonated carboxylic acids by conventional methods. Specific examples of the alkylated C- sulfocarboxylates preferred for the present application are:

3 0 9> {16/1173

- li -

Ammonium methyl / sulfopalmitate. Triethanolammonium ethyl A. sulfostearate Sodium methyl / sulfopalmitate Sodium ethyl L- sulfopalmitate Sodium butyl -><* - -sulfostearate Potassium methyl- ^ -sulfolaurate Lithium-methyl-, /, -sulfolaurate

as well as their mixtures.

A preferred group of anionic organic detergents are the β-alkyloxy-alkane sulfonates. Have these connections the following formula:

OR ₀ H

ί '

R ₁ -CC- S0, M

H H

in the R-, a straight-chain alkyl group with 6 to 20 carbon atoms, Rp is a lower alkyl group having 1 (preferably) to 3 carbon atoms and M is one of those described above means water-soluble cations.

Specific examples of .ß-alkyloxy-alkane sulfonates or optionally 2-alkyloxy-alkane-1-sulfonates with low hardness sensitivity (Galciumion), which is used in the present to achieve superior cleaning performance under household washing conditions are suitable, for example:

Potassium β-methoxydexane sulfonate Sodium 2-methoxytridecanesulfonate Potassium 2-ethoxytetradecyl sulfonate

3 0? ''-'. 1 6/1 1 7 3

Sodium 2-isopropoxyhexadecyl sulfonate Lithium 2-t-butoxytetradecyl sulfonate, sodium ß-methoxyoetadecyl sulfonate and Ammonium β-n-propoxydodecyl sulfonate.

Other synthetic anionic detergents suitable according to the invention are alkyl ether sulfates. These substances have the formula RO (C ₅ H ₁₁ O) gCUM, where R is an alkyl or alkenyl radical with about 10 to about 20 carbon atoms,. Is a number from 1 to 30 and M is one of the water-soluble cations described above. The alkyl ether sulfates suitable according to the invention are condensation products of ethylene oxide and monohydric alcohols having from about 10 to about 20 carbon atoms. R preferably has 14 to 18 carbon atoms. The alcohols can be derived from fats such as coconut oil or tallow, or they can be synthetic. Lauryl alcohol and straight chain tallow derived alcohols are preferred herein. Such alcohols are reacted with 1 to 30, in particular 6, molar proportions of ethylene oxide and the resulting mixture of such molecules with, for example, an average of 6 mol of ethylene oxide per mol of alcohol, is sulfated and neutralized.

Specific examples of alkyl ether sulfates according to the invention are sodium coconut alkyl ethylene glycol ether sulfate; Lithium tallow alkyl triethylene glycol ether sulphate and sodium tallow alkyl hexaoxyethylene sulphate

Because of their excellent cleaning properties and their easy availability, the alkali metal coconut and alkali metal tallow alkyl oxyethylene ether sulfate with average 1 to about 10 oxyethylene groups are preferred. The invention Alkyl ether sulfates are known compounds and

3Of 10/1173

2250238

are described in U.S. Patent 3,332,876.

Further examples of anionic, soap-free synthetic detergents within the scope of the present invention " are the reaction products of fatty acids, which are esterified with isethionic acid and neutralized with sodium hydroxide where, for example, the fatty acids are derived from coconut oil; the Sodium or potassium salts of fatty acid amides of methyl tauride, in which the fatty acids are derived, for example, from coconut oil. Other anionic synthetic detergents in this group are described in U.S. Patent Nos. 2,486,921, 2,486,922 and 2,396,2-8.

Further examples of anionic, soap-free, synthetic detergents falling within the scope of the present invention are compounds that contain two anionic functional groups. They are called dianionic detergents designated. Suitable dianionic detergents are.die disulfonates, disulfates or mixtures thereof, which by the the following formulas can be represented;

R (SO ₃ )

in which R is an acyclic aliphatic hydrocarbyl group having 15 to 20 carbon atoms and M is a water-solubilizing cation, for example ,, the C - to GPQ "" disodium l, 2-alkyldisulfate, C, -. '' to C ₂₀ -Dikalium -l, 2-alkyl disulfonates or disulfates, disodium-l, 9-hexadecyl disulfate, C, _r - to C _2Q disodium-1,2-alkyl disulfonate, disodium-1, 9-stearyl disulfate and 6,10-octadecyl disulfate.

3 0 9 8 16/1173

- l'l -

The aliphatic portion of the disulfates or disulfates is generally linear so that it is the desired one for the detergent confers biodegradability.

The water-solubilizing cations include the conventional cations known in detergent technology, i.e. the alkali metals and the ammonium cations as well as other metals of groups HA, HB, IHA, IVA and IVB of the periodic table with the exception of boron. The preferred water-solubilizing cations are sodium or potassium. These dianionic detergents are described in more detail in GB-PS 1,151,392.

Examples of other anionic synthetic detergents include the succinamates. This group includes surface-active Agents such as disodium N-octadecyl sulfosuccinamate, Tetrasodium N- (1,2-dicarboxyethyl) -N-octadecyl-sulfo-succinamate , Diamyl ester of sodium sulfosuccinic acid, dihexyl ester of sodium sulfosuccinic acid and dioctyl ester of sodium sulfosuccinic acid.

Other suitable anionic detergents are olefin sulfonates having from about 12 to about Ik carbon atoms. The term "olefin sulfonates" is intended to relate to compounds obtained by sulfonating each -olefins by means of non-complex sulfur trioxide and subsequent neutralization of the acidic reaction mixture under conditions in which any sultones formed during the reaction with formation of the corresponding hydroxy-alkane sulfonates are hydrolyzed. The sulfur trioxide can be liquid or gaseous and is usually, but not necessarily, diluted by inert diluents such as liquid SO2 or chlorinated hydrocarbons when it is liquid

3 0 9 fi 1 6 / M 7 3

Form is used, or by air, nitrogen or gaseous S0 _? when used in gaseous form.

The olefins from which the olefin sulfonates originate are mono-olefins having 12 to 2k carbon atoms, preferably 1 * 1 to 16 carbon atoms. They are preferably straight chain olefins. Examples of suitable 1-olefins are 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and 1-tetracosene.

In addition to the true alkene sulfonates and a proportion of hydroxyalkane sulfonates, the olefin sulfonates can contain smaller amounts Contain quantities of other substances, such as alkene disulfonates, depending on the reaction conditions, the proportion the reactants, the nature of the starting olefins, the impurities in the olefin feed and the side reactions during the sulfonation process.

A specific anionic detergent which is also excellent for the use according to the invention is more fully described in U.S. Patent 3,332,880.

B. Nonionic Synthetic Agents

Nonionic synthetic detergents can be broadly described as compounds formed by condensation of

: * () '■ 1 Ρ / 1 1 7 3

Alkylene oxide groups (hydrophilic type) can be obtained with an organic hydrophobic pre-bond which is aliphatic or alkyl can be aromatic. The length of the hydrophilic or Polyoxyalkylcnrrest, which with any single one hydrophobic group is condensed can easily be adjusted to obtain a water-soluble compound which has the desired degree of balance between hydrophilic and hydrophobic E i 1111 e i t e η 11 a t.

For example, there is a well known class of nonionic synthetic detergents on the market which are obtained by condensing ethylene oxide with a hydrophobic base obtained by condensing propylene oxide with propylene glycol. The hydrophobic part of the molecule, which is naturally insoluble in water, has a molecular weight of about 1 ^r ) OO to 180. pie addition of polyoxyethylene residues to this hydrophobic part causes an increase in the water solubility of the molecule as a whole and the liquid character of the product is maintained at the point where the polyoxyethylene content is about 50% of the total weight of the condensation product.

Further suitable nonionic synthetic detergents are for example:

(1) the Polyäthylenuxidkondensate von Alkylphenolen, beirj'i oil contains the condensation products of alkyl phenols o an alkyl group with. about 6 to 12 carbon atoms in either straight or branched chain configuration, with ethylene oxide, the ethylene oxide in an amount from | j to 25 mol Ethylene oxide is present per mole of alkylphenol. The alkyl substituent in such compounds, for example, from polymerized parts! Pj'opylen, diisobutylen, octene or! Ions originate.

3 0 9 8 16/117 3

BATH ORIGINAL

(2) Compounds resulting from the condensation of ethylene oxide with the reaction product of propylene oxide and ethylene diamine. For example, compounds containing from about ¹ IO to about 80 weight - containing% polyoxyethylene and a molecular weight of about 5000 have to about 11,000 and are obtained by reaction of ethylene oxide groups with a hydrophobic base comprising the reaction product of ethylenediamine and. Excess propylene oxide and has a molecular weight on the order of 2,500 to 3,000,

(3) The condensation product of aliphatic alcohols having 8 to 22 carbon atoms in straight or branched chain configuration with ethylene oxide, for example a coconut alcohol ethylene oxide condensate with 5 to "50 moles of ethylene oxide per mole of coconut alcohol, the coconut alcohol fraction having 10 to 14 carbon atoms.

Non-ionic detergents include nonylphenol, which condenses with from about 10 to about 30 moles of ethylene oxide per mole of phenol became; the condensation products of coconut alcohol with an average of either "about 5.5 or about 15 moles of ethylene oxide per mole of alcohol and the condensate product of about 15 moles of ethylene oxide with one mole of tridecanol.

Other examples are dodecylphenol which has been condensed with 12 moles of ethylene oxide per mole of phenol; Dinonylphenol, which with 15 moles of ethylene oxide per mole of phenol was condensed; Dodecyl mercaptan, which condenses with .10 moles of ethylene oxide per mole of mercaptan became; bis (N-2-hydroxyethyl) lauramide; Nonylphenol, that was condensed with 20 moles of ethylene oxide per mole of nonylphenol; Myristyl alcohol containing 10 moles of ethylene oxide per mole of myristyl alcohol was condensed; Lauramide, which was condensed with 15 moles of ethylene oxide per mole of lauramide, and di-isooctylphenol, which was condensed with 15 moles of ethylene oxide.

(5) A detergent of the formula R ¹ R ² R ^ M ^ O (amine oxide detergent

309816/1173

BATH ORIGINAL

genz), where R is an alkyl group with about IC) to about 28 carbon atoms, O to about 2 hydroxyl groups and O bia about ¹ j ether bonds, with at least; a portion of R is an alkyl group with about 10 to about 18 carbon

p t

atoms and 0 is ether bonds and R and R are each alkyl radicals or hydroxyalkyl radicals having 1 to about .5 carbon atoms.

Specific examples of amine oxide detectors include: Diine thyldodecylaininoxid, Dime thy Ltetradecy Lain Lnoxid, Ethy Lmethyl Itetradecylamine Oxide, CetyIdimethylaminoxid, Dirne thy 1stuaryLaminoχid, CetylathyIpropy 1 aminoχid, Diethyidodecylaminoxid, Diethyltetradecylamine oxide, dipropyldodecylamine oxide, bis- (2-hydroxyethyl) -dodecylamine oxide, bis- (2-hydroxyethyl) -3-dodecoxy-1-hydroxypropylamine oxide, (2-hydroxypropyl) methyl tetradecylamine oxide, Dimethyloleyamine oxide, dimethyl (2-hydroxydodecyl) amine oxide and the corresponding Decyl, hexadecyl and octadecyl homologues of the above Links.

(6) A detergent of the formula R R R ^ P- * O (phosphine oxide detergent), in which R is an alkyl group having about 10 to about 28 carbon atoms, 0 to about 2 hydroxy groups and 0 to about 5 ether bonds, with at least a portion of R is an alkyl group having from about 10 to about 18 carbon atoms

2 3 and O is ether bonds and R and R are alkyl radicals or Are hydroxyalkyl create of 1 to about 3 carbon atoms.

Specific examples of the phosphine oxide detergents are: Dimethyldodecylphosphine oxide, dimethyltetradecylphosphine oxide, Ethylmethyltetradecylphosphine oxide, cetyldimethylphosphine oxide, Dimethylstearylphosphine oxide, cetylethylpropylphosphine oxide,

16/117 :) BAD ORIGINAL

Diethyldodecylphosphine oxide, diethyltetradecylphosphine oxide, dipropyldodecylphosphine oxide, bis- (hydroxymethyr) -dodecylphosphine oxide, bis- (2-hydroxyethyl) -dodecylphosphine oxide ₃ (2-hydroxypropyl) -methyltetradecyl-dimethylphosphine oxide, 2-hydroxytetradecyl oxide, dimethylphosphine oxide, and the corresponding dimethyltetradecyl-dimethylphosphine oxide Diacyl, hexadecyl and octadecyl homologues of the above compounds.

(7) A detergent of the following formula:

1 * 2
O ~ Xt

(Sulfoxide-Detorgenz) j in which R means an Al radical with about 10 to about 28 carbon atoms _s 0 to about 5 ether bonds and 0 to about 2 hydroxyl _{substituents s} where at least one part of R is an alkyl with O ether bonds and about 10 to is about 18 carbon atoms., and R is an alkyl radical with 1 to 3 carbon atoms and 1 to hydroxyl groups, such as octadecylmethyl sulfoxide, dodecylmethyl sulfoxide, tetradecylmethyl sulfoxide, 3-hydroxytridecylmethyl sulfoxide, 3-methoxytridecylmethyl sulfoxide, 3-methoxytridecylmethyl sulfoxide, 2-hydroxo-methylsulfoxide, 2-hydroxylmethylsulfoxide, S-hydroxyadoxyethyl sulfoxide, octadecylmethylsulfoxide, octadecylsulfoxide, 2-octadecylsulfoxide and dodecyl ethyl sulfoxide.

C. Ampholytes see synthetic detergents

Ampholytic synthetic detergents can be widely used as derivatives of aliphatic compounds or as aliphatic «? Derivatives of heterocyclic secondary and tertiary amines are described in which the aliphatic radical is straight or can / be verzv eigtkettig _s and wherein one of the aliphatic Subä.ituenten about 8 to 18 carbon atoms and at least one aliphatic Substituente an anionic water ·

311 · H / 1113 BADORK3INAL

solubilizing group, for example! contains a carboxy, sulfonate, or sulfate group. Examples of compounds which fall under this definition are sodium 3- (dodecylamino) propionate, sodium 3 - (iodecylamino) propane-1-sulfonate, sodium 2- (dodecylamino) -al hy! Sulfate, sodium -2- (dimethylamino) octadecanoate, disodium 3- (N-carboxymethyldodecylamine) propane-1-sulfonate, disodium octadecyliminodiacetate, sodium l-carboxymethyl-2-undecyliinidazole and sodium N ₃ N-bis- (2- Hydroxy "thyl) -2-sulfato-3-dodecoxypropylamine.

D. Zwitterionic Synthetic Detergents

Zwitterionic synthetic detergents can broadly be used as derivatives of aliphatic! Quaternary ammonium and phosphonium or tertiary sulfonium compounds are described in which the cationic atom can be part of a heterocyclic ring, the aliphatic radical can be straight or branched, one of the aliphatic substituents contains about 3 to 18 carbon atoms and at least one aliphatic substituent is an anionic water-solubilizing agent Group contains, for example a carboxy, sulfonate, sulfate, phosphate or phosphono group. Examples of compounds of this definition are 3- (N, N-dimethyl-N-hexadecyl-ammonio) -2-hydroxypropane-1-sulfonate, 3 "(N, N -dimethyl-N-hexadecylammonio) propane-1-sulfonate, 2- (N, N-Üimethyl-IJ-dodecylaminonio) -acetate, 3- (N, N-dimethy] -N-dodecylaminonio) -propionate, 2- (NjN-dimethyl-N-octadecylammonioJ-ethyl sulfate, 2- (Trimethylammonio) ethyldodecylphosphonate, ethyl 3- (H, N-dimethyl-N-dodecylammonio) propylphosphonate, 3 "■ (P, F-dimethyl] -P-dodecylphosphonate) -propane-1-sulfonate, 2- (S. -NoIhyl-St ert hexadecyl-sulfonio) -ethane-1-sulfonate, 3- (S-methyl-S-dodecyl-

BAD ORIGINAL 3 0 < 1 F / 11? 3

-21- 2250238

sulfonio) propionate, sodium 2- (M, Η-dimethy1-N-dodecylammonio) ethyl phosphonate, ^ - (S-methyl-S-tetradeeylsulfonioJ-butyrate, 1- (2-hydroxyethyl) ~ 2-undecylimidazolium-1. ~ acetate, 2- (trimethylammonio) octadecanoate and 3-N, N-bi3- (2-hydroxyethyl) -il-ocbadecyLammonio) -2-hydroxy-propane-i-sulfonate. Some of these detergents are described in the following US-PSS; 2,129,264; 2,178,353; 2 77 ¹ »7Ö6; 2,813,898; and 2,828,332. The ammoniopropane sulfonates containing from about 8 to about 21 carbon atoms are one because of their relative proportions. low calcium (hardness) sensitivity preferred class of detergents.

From what has been sown above it can be seen that all kinds of water-soluble organic detergents can be used together with the water-soluble (ethylenedioxy) diacetates to deliver built-in laundry detergents.

The detergents according to the invention can be used in any * for such In the usual physical form, such as powder, globules, flakes, pieces, tablets, Liquids or pastes. The funds are made and used in a conventional manner. Your washing solutions should have a pH of from about 7 to about 12, preferably from about 9 to about 11. The pH of the washing solutions Detergent according to the invention can by adding a base, for example sodium hydroxide, can be added to the detergents.

The detergents described herein can contain other substances that are commonly used in such agents, contained in smaller quantities. For example, various types of dirt carrier substances, corrosion inhibitors, Colorants, proteins, fillers, optical brighteners, foam improvers, foam retardants, germicides, anti-graying agents

309Ü16 / 1173 BAD ORIGINAL

medium, cationic «detergents, (Jewebewächiiiaeher and enzymes, their use in detergents is well known. What can also be used in detergents» a.

The following guidelines apply to the detergents according to the invention. In these examples, the (Äthylendioxy) -dLi! .Iüi.f; ü'iure is produced according to the general in the ^{process described in GIi-FS 63 (} J'Π. In addition, the (rithy Lendioxy) -dieas i ^ üHure available in stores and värd on: h <iLü iithy Len-biis- ([^ ycoUjfiui'e).

WasaerlösLiehe iJal'.ü dei (iithyLendioxy) -dieusigsäure, which in existing PaIL geeL ^ advised to be produced dadui'cfi; LLt, that the stairunic acid with a base, which is a wasserlüalichea Cation of the type described above contains, neutralized. The detergents described below can can be made by simply mixing the different ingredients. Usual spray dry and similar processes can be used to prepare such compositions.

example 1 Component wt .-> t

Alkylbenzenesulfonate, sodium salt (average alkyl chain = CL ₅ ) 15 (ethylenedioxy) diacetic acid, disodium

salt 6O

Sodium Sulphate (filler) 10 Water rest

30 9816/1173 BAD ORIGINAL

-23- 225G236

When used in a conventional washing machine in which water with a hardness of 6.7 and a temperature of about ¹ JO C is used, the above detergent in an amount of 1 cup per 61 1 V / ater of soiled work clothes cleaned .

In the above agent, the disodium salt of (Ethylenedioxy) ~ diacetic acid by an equivalent amount Di kali ums al z, di ammonium salt, I) i- (triethanolammonium) salt or trimethyltetradecylammonium salt replaced, and was obtained equivalent detergent.

Example 2

Part of Gew.-Ji

(Ethylenedioxy) diacetic acid 10

Sodium salt of tallow fatty acids 70

Perfume · 0.5

Water rest

The above composition was made into finely puffed bar soap and showed when used for Washing delicates by hand has a satisfactory cleaning power in water with a hardness of 6.7

The above connection n; u t.zunp; was modified by adding 2% by weight of nitrilotriacelate as the disodium salt, which results in a »further tooling off and water softening effect achieved by ·! · ¹ .

1173

BATH ORIGINAL Example 3

Ingredient wt .- $ £

(Ethylenedioxy) -diesεigsäure, monosodium salt 90

Sodium 2- (dodecylamino) ethyl sulfate 10

The above composition has been made into a spray dried powder which is suitable for use in extremely hard Water was suitable for washing heavily soiled cotton, polyester and polyamide fibers.

Example 4

Component wt. -%

(Ethylenedioxy) diacetic acid,

Dipotassium salt 15

Sodium alkyl sulfates (Cq - C ^ Q alkyl) 10

Carboxymethyl cellulose, sodium salt 10

Sorbitol mono-oleate polyoxyethylene 3

Water rest

The above composition was made into a liquid dishwashing detergent and laundry detergent.

The above composition was modified by adding 0.5% by weight of sodium hydroxide. Resulting to you Composition that had cirn * n pH of about 11.5, was used to wash haumwolj-umi ttr ^ eWeben {, «. 'is suitable.

3 0 ° 1 6/1 1 7 3 BAD ORIGINAL

Example 5

Component wt. -%

(Ethylenedioxy) diacetic acid »

Disodium salt 40

Sodium metasilicate 15

Alkylbenzenesulfonate, "potassium salt

(average 1st alkyl chain = C ₁₃ ) 5

Sodium carbonate 10

Polydimethylsiloxane

(Average molecular weight 450) 0.1

Water rest

The above composition became a spray-dried Powder processed with a pH value of about 12 - 12.5. The low foaming power of this agent make it the Suitable for use in automatic dishwashers.

Example 6 Part of weight Ϊ

(Ethylenedioxy) diacetic acid, Triethanolammonium salt 80

Sodium 3 ~ (N _J N-dimethyl-N-hexadecylammonio) -propane-1-sulfonate 5

Dimethyldodecylphosphine oxide 5 Sodium hydroxide 2 Water . rest

The above composition was made into a spray dried powder with a pH of about 12. The agent was suitable for washing heavily soiled cotton and polyester and polyamide fabrics in hard and brackish water.

In the above composition, the 3- (N _s N-dimethyl- N-hexadeeylammonio) -nropane-1-sulfonate was replaced by an equivalent

.K ^ j Din-2thyldodc ^ / lanine <> xid, Pndeeylnethylsulfoxid, U) If. · 1 ] '■■ 3

BATH ORIGINAL

225021H

5-Hydroxytr iducyimebhylsulfoxid or Matriumitiethyl- ot-3Ulfopalmltat and equivalent funds were obtained.

Example 7

Part by weight?

Ethyl 3- (N, N-dimethyl-N-dodecylammonio) propylphosphonate 20th

Nonylphenol polyoxyethylene (through-

average 25 moles of ethylene oxide per

Moles of phenol) HO

(Ethylenedioxy) diacetic acid,

Diammonium salt 5

Sodium carbonate 10

Water rest

The above composition was made into a paste suitable for the "stain" treatment of heavily soiled collars and cuffs on cotton and polyamide fiber shirts. The paste was applied directly to the fabric with rubbing, which was then added to the wash broth with the paste.

The above composition was modified by that 5% by weight of nitrilotriacetate (disodium alkali) were added; as a result, additional dirt-bearing capacity and a structural effect were achieved.

30 ^: 16/1173

Example 8

Ingredient weight-5

Potassium ß-methoxydecanesulfonate 10 (Ethylenedioxy) diacetic acid,
dipotassium salt 5 (Ethylenedioxy) diacetic acid,
Monolithium salt '5. (Ethylenedioxy) diacetic acid UO. Perfume 0.5 NaH ₂ PO ₁₁ -Na ₂ HPO ₁₁ (pH value 7 - Buffer) 5 Carboxymethyl cellulose, potassium salt 3 water rest

The above composition was made into a syrupy liquid having a pH of 7. The composition was suitable for use in soap dispensers for liquid soap from which a measured amount of detergent was used flows into the wash broth. .

In the above composition the potassium ßmethoxy-decanesulfonate was replaced by an equivalent amount of sodium methyl-OC-sulfolaurat, 3- (N _i N-dimethyl-N-dodecylammonio) ~ propan-1-sulfonate, sodium .beta.-methoxytridecansulfonat or KaliuTn -β-methoxyhexanedecanesulfonate replaced and equivalent results were obtained. .

From the vornt ehPn lon k.'inn ernehrn worieri, diF. pure variety von War.i'h- and Rt ini ^ ungsmitti-lti, dit rur Vti ^ cnlunf in different ways ■ μοη - / ■ nwendunFSt-t'rf I * π f.foinnct are, under inventive use irr () -. t hylfndii-> y) ~ di (-n: acidic tannins were produced ». This! .Ittel

ORIGINAL BATHROOM IG / 117 3

- 23 -

can be adjusted to different pH values, for example by means of well-known buffer salt combinations (such as the phosphate buffers), by adding sodium carbonate, sodium bicarbonate or hydrochloric acid. Suitable wash liquors may preferably have up to about 100 ⁰ C, from about 38 to about 82 ° C habenj wherein the (ethylenedioxy) diacetates their builder effect within this range, temperatures from about 18th ■

The (ethylenedioxy) diacetic acid and its water-soluble Salts, which have been described above, are also simply suitable for use as water softeners in that than they have multivalent cations such as magnesium ions, calcium ions, peroions or ferric ions bind from the water complex. For example, by dissolving (ethylenedioxy) diacetic acid in water a concentration of about 20 ppm, the concentration of calcium and magnesium ions below about 17.1 mg / 1 (water hardness see 0.958 °). Likewise, by dissolving the disodium salt of (ethylenedioxy) diacetic acid in water at a concentration of about 15 ppm or more, the concentration of iron, calcium, and magnesium cations below about 3 ^ mg / 1 (water hardness = 1.9). These water-softening effect of the water-soluble diacetates used in the present invention occurs own pH of about 3 to about 12, preferably about 7 to about 10.

The (ethylenedioxy) diacetates according to the invention have the additional advantage as a builder and water softener that they are biodegradable. For example, about 21% of (ethylenedioxy) diacetic acid is degraded in wastewater after five days. After 20 days, the (ethylenedioxy) diacetic acid is 60 % biodegraded.

309816/1173

The following test is used to compare the detergent builder activity of (ethylenedioxy) diacetic acid with oxydiacetic acid as a builder. The test consists essentially of measuring the ability of the builders used in various concentrations to suspend particulate matter in water at pH 10 in the presence of 10% calcium ions. Έ & is.the percentage of light transmission through the dispersion measured; the greater the percent permeability, the greater the dispersion and the greater the builder activity of the material to be tested. Typical data are shown in Table I.

Table I.

Molar concentration (ethylenedioxy) - oxydiacetic acid

diacetic acid permeability (permeability, %)%

IX 10 " ⁴ ~ 38 ~ 40

5 X 10 " ⁴ ~ 38 ~ 40

1 X 10 ^-5 ~ 38 <*, 40

5 X 10 " ³ ", 60 ■ '~ 60

8 X 10 " ⁵ « 80 ^ 75

1 X 10 ² (extrapolated) ~ 90 (extrapolated) ~ 80 (extrapolated)

From the above it can be seen that the builder activity of (ethylenedioxy) diacetic acid is shown in the Volclay dispersion test was measured, a representative polycarboxylate builder is equivalent at low concentrations and superior at higher concentrations. To the optimum use as builder fluids are those according to the invention (Ethylenedioxy) diacetate in a molar concentration

3 0 9 8 16/1173

tration in water of more than about 5 x 10 ~ ^ and preferably

-2
wisely used about 1 χ 10 and higher. The detergents discussed herein provide these optimal concentrations when dissolved in water at normal detergent use concentrations (about 1 cup per 61 liters of water).

The water-soluble (ethylenedioxy) diacetates according to the invention are suitable for use together with enzymes and water-soluble organic detergents for the production of pre-soaking detergents. If they are used in such agents, the (ethylenedioxy) diacetates work as water softeners and thus stabilize the enzymes against the harmful effects of polyvalent metal ions. Such laundry soaking agents generally contain about 20 to about 90 wt. water-soluble (ethylenedioxy) diacetate, about 0.005 to about 5 parts by weight ί an enzyme such as bacterial proteases, amylases, lipases and mixtures thereof, and about 5 to about ¹ IO wt. -JF a water-soluble organic detergent of the type described above. Any enzyme known in the art to be suitable for use in such presoak agents having a pH of from 6 to 11 is suitable with the (ethylenedioxy) diacetate. Other additives commonly used in such presoak agents may optionally be present in such preparations, for example additional builder salts of the type discussed herein, perfumes, or optical bleaching agents. The following example explains a typical laundry presoak which contains a larger proportion of a water-soluble (ethylenedioxy) diacetate.

3098 16/1173

Example 9

A laundry presetting agent was prepared as follows. The detergent granules used as the basis were prepared by agglomerating 2.16 parts of pulverized (ethylenedioxy) diacetic acid as disodium salt with 0.24 parts of the condensation product of 1 mole of tallow alcohol with 30 moles of ethylene oxide (TAE ₃₀ ) in an agglomerating pan. Before was TAE .dem (ethylenedioxy) -diacetic acid disodium salt is added, it is liquefied by heating it to 6O ⁰ C. The average bulk density of these granules was about 0.5 g / cc "were still warm While the granules and the TAE, _{Q was in} a sticky state, 1.2 parts of Alcalase (commercially available enzyme preparation) were glutinated together with the granules to form the finished granules. The final granules were cooled to about 27 ° C, and then were about 0.12 parts liquid TAE, ₀ sprayed uniformly over the surface of the finished granules, to effect encapsulation of the alkali enzyme preparation.

About 3.72 parts of the finished granules produced according to the above description were mixed with 96.38 parts of granules which 70.0 wt -.% (Ethylenedioxy) -diacetic acid, 10 parts by weight 5i sodium tripolyphosphate, 15 parts by weight of sodium carbonate and 55 5.0 wt. 55 ^TAE 3q, the finished laundry preselection agent being obtained.

28.35 g of the above presoak was 7.57 liters given lukewarm water and a cotton-polyester blend, which was stained with blood stains, sauce stains, grease stains and skin lipoid was left in it for an hour soaked. The stains were essentially removed by this treatment.

3 0 fi V. 1 6/1 1 7 3

Claims (8)

Claims (L) detergents and cleaning agents, characterized in that dajf \ (1) about 1 to about 95 wt. Si (ethylenedioxy) diacetic acid or their water-soluble salts as builders and (2) from about 5 to about 99% by weight of one Contains water-soluble organic detergent. 2. Means according to claim 1, characterized in that that the builder is the sodium, potassium or triethanolammonium salt of (ethylenedioxy) diacetic acid. 3. Composition according to claim 1, characterized in that the ratio of water-soluble organic Detergent to builder is about 1:10 to 1: 2 wt. 4. Means according to claim 1, characterized in that that the water-soluble organic detergent is an alkali metal soap, an alkali metal salt of organic sulfuric acid reaction products, which has an alkylbenzene radical in its molecular structure, in which the alkyl group is about 9 to has about 15 carbon atoms, and a sulfonic acid or Have sulfuric acid ester residue, an olefin sulfonate with about 12 to about 24 carbon atoms, a polyethylene oxide of alkylphenols, a ß-methoxysulfonate with about 12 to about 16 carbon atoms, an alkyl oC-sulfocarboxylate having from about 10 to about 22 carbon atoms, an ammoniopropanesulfonate having from about 8 to about 21 carbon atoms 309816/1173 or a mixture thereof. 5. Composition according to claim 1, characterized in that there is (1) about 1 to about 95 wt .- ^ (ethylenedioxy) diacetic acid or its water-soluble salts as a builder and (2) about 5 to about 99 wt. % Of the sodium salt an alkylbenzenesulfonate having an average alkyl chain of about C ₁ . 6. "Process for softening water, characterized in that there is about 15 ppm or more in the water (Ethylenedioxy) diacetic acid or its water-soluble salts dissolve. 7. The method according to claim 6, characterized in that the disodium salt is used as the water-soluble salt of (ethylenedioxy) diacetic acid. 8. laundry softener, characterized in that it (1) about 20 to about 90 wt. % (Ethylenedioxy) diacetic acid or its water-soluble salts; (2) about 0.005 to about 5 wt -.% Of an enzyme such as amylases, proteases and lipases, and (3) about 5 to about 40 wt -.% Of a water-soluble organic detergent. For The Procter ^, Gamble Company Cincinnati, Ohio, V.St.A. Dr. Η! 'J. WoIH (Lawyer) 3098 16/117 3