DE1617181A1 - Detergent mix - Google Patents

Description

Detergent use.

The invention relates to detergent compositions which contain certain detergent builders, the latter are very corrosive to aluminum, nickel silver and zamak. In particular, the invention relates to detergent mixtures, those against corrosion of zamak and possibly aluminum and / or nickel silver due to the presence of ge certain Corrosion inhibitors including special organic phosphonate corrosion inhibitors are inhibited.

Detergent builder mixtures (ohelate-forming materials), show a tendency to corrosion of aluminum, nickel silver and zamak as soon as the detergent builder is added these materials in washing machines, jugs, kitchen equipment, Come into contact with drains and the like. (Zamak is a common zinc-containing alloy that

IVMIt documents <fet7 fittia no. Ι

108I0Ö / 1Ö4Ö

used in particular for washing machine pumps. Zamak # 3f, the most common type of zamak, is on page 1169 des Metals Handbook, 8th ed., Vol. I by the American Society for Metals). With respect to aluminum and nickel silver, this corrosion problem has become usually by incorporating alkali silicates, like sodium silicate with a ratio of SiOp ί Na „0 of about 1.6 and a nickel silver corrosion inhibitor such as benzotriazole in detergent builders loops solved. The alkali silicates are extremely effective in preventing aluminum from corrosion and the benzotriazole inhibits the corrosion of nickel silver very considerably. Furthermore, these additives are in use effective amounts relatively cheap. However, the sodium silicate and the benzotriazole do not prevent these Zamak attack mixtures and, if certain very effective detergent builders and chelating agents, such as Sodium nitrilotriacetate, are present in detergent mixtures, these mixtures are due to corrosion in zamak completely useless. It is therefore necessary to incorporate a corrosion inhibitor into such mixtures the corrosion of zamak is particularly prevented when the mixtures contain the more effective detergent builders, such as Sodium nitrilotriacetate, contain *

Accordingly, it is an object of the present invention to provide a detergent composition that is certain to be specific Contains detergent builders, this mixture being effective against the corrosion of zamak and possibly aluminum and / or silver, the presence of certain corrosion inhibitor compounds is inhibited.

This as well as other goals can be achieved by creating a detergent mixture which

109801/1940

(1) about 1 Ms 98 # of the detergent builder mixture from the water-soluble aminopolyearboxylate, tripolyphosphate and polyphosphonate builders as well Group comprising their mixtures, and

(2) more than about 0.05 # and less than about $ 25 of the entire detergent mixture an anti-corrosion Connection with the general Foimel

Il

RP (OQ) ₀ -

contains, wherein R has one of the following meanings:

(A) a straight chain alkyl chain attached to the phosphorus atom bound by secondary carbon atoms of the chain where the straight chain alkyl radical is from about 12 to about Contains 24 carbon atoms; (B) straight chain alkylbenzyl groups wherein the alkyl group has from about 9 to about 18 carbon atoms Contains, wherein Q is a water-solubilizing cation; this detergent mixture is in terms of Zamak corrosion inhibited. The term "alkyl" as used in the context of the present invention includes saturated and unsaturated alkyl groups.

The detergent mixtures according to the invention preferably consist essentially

(l) from about 1 to about 90 # of the detergent builder mixture from the water-soluble aminopoly carboxylates, tripolyphosphates, polyphosphonates and their Mixtures Comprehensive Group;

109808/1940

(2) from 0 to about 15 wt .- # of the mixture of an alkali metal silicate with a ratio of SiO _{2 to} M ₂ O of about 1.0 to about 3-6, preferably 1.6 to 3.2 above ratio potassium or sodium);

"(3) from more than about 0.05 and less than about 25 weight-per-9 & the total detergent mixture one anti-corrosive acting compound with the formula

Il

R - P (OQ) ₂

wherein R has one of the following meanings: (A) a straight-chain alkyl radical, which with the phosphorus atom through secondary carbon atoms of the chain is linked, being the straight chain alkyl radical from about 12 to about 24 carbon atoms and (B) straight chain alkylbenzyl groups wherein the alkyl group has from about 9 to about 18 carbon atoms contains, where Q denotes a water-solubilizing cation, e.g. a cation from the hydrogen, alkali, Group comprising ammonium and substituted ammonium cations;

(4) from 0 to about 1 #, preferably 0.02 %, of a corrosion-inhibiting compound for the protection of nickel silver;

(5) from 0 to about 40% of an organic detergent from the nonionic, anionic, amphoteric and «weather -

109808/1940

group comprising ionic detergents and mixtures thereof;

(6) from about 0 .Ms about $ 90> other detergent builders from the group comprising alkali pyrophosphates, orthophosphates, perborates, tetraborates, hexaphosphates, sesquicarbonates and bicarbonates and their mixtures, and

(7) from O to about 90 <$> water.

Typical aminopolycarboxylate detergent builders include alkali (sodium, potassium, etc.) »ammonium and substituted ammonium (the term" substituted ammonium "* as used in the invention includes mono-, di- and triethanolammonium cations) salts the following acid ethylenediaminetetraacetic acid, N- (2-hydroxyethyl) ethylenediamine triacetic acid _f N- (2-hydroxyethyl) nitrilodiacetic acid, diethylenetriaminepentaacetic acid, 1,2-diaminocyclohexanetetraacetic acid and nitrilotriacetic acid. The trisodium salts of the above compounds are commonly used. The water-soluble salts of nitrilotriacetic acid are hereinafter referred to as HTA and the water-soluble salts of ethylenediaminetetraacetic acid with EDSA.

Polyphosphonates are also valuable building materials within the scope of the invention and in particular include sodium and potassium salts of methylenediphosphonic acid, sodium and potassium salts of ethylene diphosphonic acid, sodium and potassium salts of ithan-1-hydroxy-1,1-diphosphonic acid and sodium and potassium salts of A ' than-l _f l, 2-triphoephoneic acid ·.

At the"

include suitable detergent builders

trium and potassium tripolyphoephate.

These detergent builder compounds usually do about 1 to about 90%, preferably about 10 to about 60% of the mixture. The detergent builder compounds are preferably in a ratio of detergent builder compounds to any surface active Detergents are present in the mixtures from about 1: 2 to about 10: 1. These detergent builder compounds attack aluminum, nickel silver and zamak when they are applied to these metals in the form of aqueous solutions will.

The silicate corrosion inhibitor defined above is the typical representative of corrosion inhibitors known per se. It can be present in the detergent mixtures according to the invention in an amount from about 1 to about 15%, preferably from about 2 to about 10%. A typical silicate corrosion inhibitor is sodium silicate having a SiO ₂ t NAGO ratio of about 1.6. This silicate corrosion inhibitor prevents the corrosion of aluminum, but in preventing or substantially reducing corrosion of zinc alloys such as zamak by, for example, NTA, it is essentially ineffective regardless of the amount in which the silicate corrosion inhibitor is used. The silicate corrosion inhibitor is an essential ingredient in the manufacture of a general purpose detergent mixture at the lowest cost because the phosphonate corrosion inhibitor is ineffective in preventing corrosion of aluminum and nickel silver at levels below about 2%, as noted below. The phosphonate is more expensive than silicate.

The phosphonate corrosion inhibitors that contain several carbon atosi · contain, prevent the corrosion of aluminum and nickel silver besides preventing corrosion

101108/1140

of zamak, if they are used in higher concentrations, e.g. more than about 2 $> . In some cases, however, it would be prohibitively expensive to provide enough phosphonate corrosion inhibitor for this purpose. Certain silicate corrosion inhibitors are therefore always preferred for general cleaning purposes to prevent corrosion in aluminum, although with larger amounts of high molecular weight phosphonate corrosion inhibitors, silicate may be a component that may be used if the corrosion of aluminum is dominated. ,

The phosphonate corrosion inhibitors that are effective in inhibiting "corrosion of aluminum and zamak" at higher levels are those alkyl phosphonates and phosphonic acid in which the alkyl group contains at least about 18 carbon atoms, and the alkyl benzyl phosphonates and phosphonic acids in which the alkyl benzyl groups contain at least about 20 carbon atoms. these larger effective Phosphonatkorrosionsinhibitoren inhibit at Ver application at concentrations above about 2 # and preferably from about 2 i to about 6 »corrosion of aluminum and nickel silver by the effective detergent builders such as those described above. If less than about 18 carbon atoms in the hydrophobic If the hydrophobic group contains more than about 24 carbon atoms, the solubility of the Mo leküls is reduced and undesired precipitation occurs due to free calcium and magnesium ions at lower and less suitable concentrations.

109808/1940

It is believed that the choice of detergent builds off what the phosphonate corrosion inhibitors will do with according to the invention at higher concentrations the Prevent corrosion of aluminum in an excellent way, depends on two factors. The first pactor relates to the effectiveness of the detergent builder in the complex binding of alkaline earth metal ions, e.g. calcium ions, which are present in hard water. If the free (not complexed) calcium ion concentration in the builder solution is sufficiently high to achieve the To make corrosion-inhibiting compounds insoluble with the formation of the calcium salt, so do the corrosion-inhibiting compounds Properties of connections lost. Building materials, such as sodium orthophosphate, do not appear to give complex binding of calcium ions sufficient to to make the corrosion inhibiting compounds insoluble. Apparently the anti-corrosive compounds need to be used Achieving their effectiveness be soluble. The second factor relates to the size of the detergent building block molecule8. Apparently hatches if the builder molecule is too small (e.g. the alkali metal pyrophosphate builder salts), the same through the PiIm of the corrosion inhibitor, as will be described in more detail below. the Tripolyphosphate, polyphosphonate and aminopolyearboxylate builders, as used in the mixtures according to the invention, have sufficient complex-forming properties, to maintain proper solubility of the inhibitor and sufficient molecular space to ensure favorable inhibition.

It is also believed that the effectiveness of the corrosion inhibitors according to the present invention in terms of the corrosion inhibition in zamak, aluminum and

109808/1940

German silver is based on the fact that the hydrophobic group (R-)

Il

is bound to the hydrophilic group (-1 (0Q) ₂ ) »space filling". This "space filling" is achieved in different ways »For example, a straight-chain, hydrophobic alfcyl part (R-) of the corrosion-inhibiting compound can be attached to the hydrophilic group via a secondary carbon Similarly, space filling is achieved by introducing an aryl group, such as a Benayl group, into the hydrophobic group. The alkyl chains may contain some degree of unsaturation and / or branching. Similarly, the presence of certain 1-isomers is acceptable and indeed an arbitrary phosphonate is preferred. "Arbitrary" refers to a substantially equal distribution of isomers, in some cases it will be essential that no 1-isomer be present and in other cases a slightly larger proportion of 1-isomer may be present than a completely arbitrary distribution as a result of the Ver used in the preparation of the phosphonates driving available.

The most important result of this space-filling bond is apparently the increase in the solubility of the compounds in water, especially in the form of their alkaline earth (eg calcium and magnesium) salts. The more bulky bond, for example the closer bond of the hydrophilic group to the center of the straight alkyl chains, is therefore preferred Metal pleases. Corrosion inhibitors, in which the Phoephonat- or Phoephatgrupp · mn ·

106101/1940

- ίο -

relatively unbranched (straight-chain) hydrophobic group terminally is bound, precipitate in the presence of free calcium and magnesium and can therefore not be sufficient tough film to prevent complexing Building materials, e.g. STP, reach the surface.

The phosphonate corrosion inhibitors according to the invention can be prepared in various ways. For example phosphorus trichloride, oxygen and a paraffin containing about 18 carbon atoms can be mixed with one another are reacted and the reaction product is then hydrolyzed to form the phosphonic acid.

Other methods of making these phosphonates are described in U.S. Patent No. 2,724,718. (See also the references given there).

Specific examples of the above compounds include:

Random phosphonated octadecane, like the product, which is formed by the reaction of diisopropyl phosphite with an arbitrary olefin, which on average is 18 carbon atoms, working in the presence of a free radical initiator, whereupon the phosphonate ester is pyrrolysed to form the phosphonic acid.

Other examples of phosphonate corrosion inhibitors include!

The following compounds as well as the sodium, potassium, Ammonium, monoethanolammonium, diethanoiammonium and Triethanolammonium salts of the same:

101108/1940

10-nonadecylphosphonic acid; Pentadecylbenzylphosphonic acid;

Alkylbenzylphosphonic acid mixtures in which the alkyl groups of (1) a chemical of propylene polymers, (2) olefins derived from cracked petroleum waxes, or (3) Olefins that occur in the synthesis reactions of ethylene the Ziegler process, the alkyl groups being a Have a size of 12 to 21 carbon atoms and an average of about 14 to 18 carbon atoms;

Hexadecylbenzylphosphonic acid wherein the hexadecyl group is derived from polymerized isobutylene;

Alkylbenzylphosphonic acid, wherein the alkyl group of a chlorinated kerosene fraction with an average of about 15 to is derived from about 18 carbon atoms;

the mixture of ö-eicosenyl-4-phosphonic acid and 5-vinyloctadecyl-4-phosphonic acid, which arises as follows: Reduction of the reaction between butyric anhydride and the allyl carbanion of 1-hexadecene formed ketones, to alcohol, conversion of the alcohol to the tosyl ester, alkylation of the bibutylphosphonate anion with the ester and hydrolysis of the resulting product;

the hydrolyzed reaction products of phosphorus trichloride, Oxygen and a mixture of olefins which contain from about 18 to about 25 carbon atoms and which are derived can be (l) from cracked petroleum waxes or (2) Ziegler-type synthesis reactions of ethylene (this hydrolyzes The reaction products are a mixture of saturated and unsaturated phosphonic acids and saturated alkyl

109808 / 19AO

phosphates. Contain some of the saturated phosphonic acids combined chlorine);

the mixture of octadecylphosphonic acids, which was prepared by alkylating dibutylphosphonate anion with the mixture of 2- to g-octadecylsulfuric acids, which was obtained by reacting 1-octadecene with excess sulfuric acid at 0 0 to 10 ⁰ C for about 2 to 3 hours and hydrolyzing the alkylated Dibutylphosphonate anion (this product is an arbitrary octadecylphosphonic acid containing a mixture of 2 to 9 isomers);

the mixture of phosphonic acids obtained by isomerizing the double bond of 1-octadecene with aluminum chloride, Adding sodium hypophosphinate to the resulting Olefins and oxidation of the resulting phosphinates to phosphonates with nitric acid is obtained (this product is an arbitrary octadecylphosphonic acid containing a mixture of 2 to 9 isomers);

the hydrolyzed reaction product of 1-octadecene, phosphorus trichloride and oxygen (these hydrolyzed Reaction products are a mixture of saturated and unsaturated phosphonic acids and saturated alkyl phosphates. Some of the saturated phosphonic acids contain combined chlorine);

the hydrolyzed reaction product of 1-octadecene, phosphorus trichloride, acetic anhydride and oxygen (this hydrolyzed reaction product is a mixture of saturated and unsaturated octadecylphosphonic acids and saturated Octadecyl phosphates. Some of the saturated phosphonic acids contain bound. Chlorine) and

109808/1940

the hydrolyzed reaction product of ootadecane, Phosphorus trichloride and oxygen (this hydrolyzed The reaction product is an arbitrary octadecylphosphonic acid, which contains a mixture of 1 to 9 isomers).

(He last mentioned 6 corrosion-inhibiting compounds, those listed above as reaction products are complex mixtures consisting primarily, i. to at least 80 #, are phosphonates, wherein the phosphonate groups to the hydrophobic chain through secondary carbon atoms are bound).

The phosphonate corrosion inhibitors according to the invention are useful in preventing the corrosion of zamak in extremely small quantities (more than 0.05 # and less than 2 #, preferably about 0.1 #) effective, whereas the corresponding phosphates, and particularly phosphonate esters, are relatively ineffective when they are in the same Quantities are used. There are also phosphates and phosphonate esters much less effective in preventing the corrosion of aluminum when in amounts greater than about 2 # can be used. The mixture of silicate corrosion inhibitors and phosphonate corrosion inhibitor is more effective in protecting zamak than the phosphonate corrosion inhibitor alone. A mixture of silicate corrosion inhibitor and phosphonate corrosion inhibitor is analogous to the Protecting aluminum is more effective than any of the components alone. This is especially true for those processed by die casting Aluminum too.

Benzotriaaol has been given as an example of inhibitors which inhibit the corrosion of German silver. Zahlreiche.weitere examples of effective compounds are US-Patentflchriften ITr. 2 618 603, No. 2 618 605 *

No. 2,618,606 and No. 2,618,608. Palls essential Amounts of, for example, alkali perborate salts in contained in the mixture is the nickel silver corrosion inhibitor not mandatory.

The corrosion inhibitors of the invention are effective in the presence of a wide variety of detergent surfactants, optionally used with the detergent builders. These detergent surfactants are present in an amount from 0 to about 40 %, and preferably from about 10 to about 20 % of the surfactant mixture. Examples of detergent surfactants that can be used include:

(1) Ordinary alkali soaps, such as the sodium and potassium salts of the higher fatty acids of naturally occurring ones vegetable or animal esters (e.g. palm oil, coconut oil, Babassu oil, soybean oil, castor oil, tallow, whale and table oils, fats and lard and mixtures thereof) or of synthetically produced fatty acids (e.g. rosin and such resin acids in tall oil) and / or naphthenic acids. Sodium and potassium soaps can be made by direct saponification of fats and oils or by neutralizing the free fatty acids, which are produced in a separate manufacturing process be won.

(2) Synthetic, organic detergents, due to their high water solubility, their resistance to precipitation Constituents of hard water and their surface-active and effective detergent properties characterized are including!

(a) Anionic synthetic detergents · (eohter except soaps)} The "β class of synthetic detergent -

Gentien can generally be called water-soluble salts, especially alkali salts (sodium, potassium, etc. salts) of organic Sulfuric acid reaction products are addressed, which in the molecular structure is an alkyl radical with about Contains 8 to about 22 carbon atoms, as well as a radical from sulfonic acid and sulfuric acid ester radicals comprehensive group. Important examples of the synthetic detergents which are part of the preferred blends according to Make up the present invention are sodium or potassium alkyl sulfates, especially those produced by sulfation the higher alcohols obtained by reducing the glycerides of tallow or coconut oil; Sodium or potassium alkylbenzenesulfonates in which the straight or branched chain alkyl group is from about 9 to about Contains 15 carbon atoms, especially those of the types those described in U.S. Patents No. 2,220,099 and No. 2,477,383; Sodium alkyl glyceryl saturating sulfonates, especially those ethers of higher alcohols derived from tallow and coconut oil; Sodium salts sulfonated α-olefins containing 8 to 22 carbon atoms, E.g. those mentioned in the Austrian patent no.

(Application A 67/66 of January 4th, 1966); Sodium coconut oil fatty acid monoglyceride sulfates and sulfonates; Sodium or potassium salts of sulfuric acid esters of Reaction product of 1 mole of a higher fatty alcohol (e.g. tallow or coconut oil alcohols) and about 3 moles of ethylene oxide; Sodium or potassium salts of alkylphenol ethylene oxide ether sulfate with about 4 units of ethylene oxide per molecule, wherein the alkyl radicals contain about 9 carbon atoms; the reaction product of fatty acids which are esterified with isethionic acid and neutralized with sodium hydroxide, whereby for example the fatty acids are derived from coconut oil; Sodium or potassium salts of the fatty acid amide of one

109808/1940

Methyl taurine, in which the fatty acids are derived, for example, from coconut oil, as well as others known per se Products, a number of which are described in U.S. Patents No. 2,486,921, No. 2,486,922, and No. 2,396,278 is.

(b) Nonionic Synthetic Detergents: This class of synthetic detergents can be broadly referred to as compounds are defined by the condensation of alkylene oxide groups (hydrophilic nature) arise with an organic hydrophobic compound that is aliphatic or alkylaromatic can be. The length of the hydrophilic or polyoxyalkylene radical associated with any particular hydrophobic group is condensed, can be conveniently adjusted to form a water-soluble compound, which has the desired ratio between hydrophilic and hydrophobic elements.

- A known class of nonionic synthetic detergents is for example under the trade name "Pluronic" available on the market. These connections are made by condensation of ethylene oxide with a hydrophobic Obtain base, which is formed by the condensation of propylene oxide with propylene glycol. The hydrophobic part of the molecule, which is of course insoluble in water, has a molecular weight of about 1500 to 1800. The addition of polyoxyethylene radicals 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 until the polyoxyethylene content is about $ 50 of the total weight of the condensation product.

Other suitable nonionic synthetic detergents

109808/1940

Gentlemen include:

(i) The polyethylene oxide condensates of alkylphenols, e.g. the condensation products of alkylphenols with a Alkyl group containing about 6 to 12 carbon atoms either i.n straight-chain or branched-chain configuration, with ethylene oxide, the ethylene oxide being present in amounts that range from 10 to 25 mols of ethylene oxide per mole of alkylphenol correspond. The alkyl substituent in such compounds can, for example, from polymerized propylene, diiso butylene, Octane or nonane derived.

(ii) Those derived from the condensation of ethylene oxide with the product, that of the reaction of propylene oxide and ethylenediamine - products that in their composition depend on the ratio can be varied as desired between hydrophobic and hydrophilic elements. For example, have Compounds containing about 20 to about 80 weight-96 polyoxyethylene and have a molecular weight of about 5000 to about 11,000 and which originate from the reaction of ethylene oxide groups with a hydrophobic base, which is the reaction product of ethylenediamine and excess propylene oxide, this base having a molecular weight in of the order of 2500 to 3000 is considered satisfactory proven.

(iii) The condensation product of aliphatic alcohols with β to 18 carbon atoms that are either straight-chain or branched-chain configuration, with ethylene oxide, e.g., a coconut alcohol ethylene oxide condensate with 10 to 30 moles of ethylene oxide per mole of coconut alcohol, the lokoanut alcohol fraction being 10 to 14 carbon

has lenetoff atoms.

Λ Λ Jt Λ Λ.

(c) Long chain tertiary amine oxides (nonionic detergents) _{corresponding to the following general formula R 1} RpR ^ N ~~~ ^ 0, wherein R _{1 is} an alkyl, alkenyl or monohydroxyalkyl radical having from about 8 to about 18 carbon atoms, 0 to about Contains 10 ethylene oxide radicals and 0 to 1 grlyceryl radical and Rp and R ~ contain 1 to about 3 carbon atoms and 0 to about 1 hydroxyl group, for example methyl, ethyl, propyl, hydroxyethyl or hydroxypropyl radicals. The arrow in the formula represents a common symbol for a semipolar bond. Examples of amine oxides suitable for use in accordance with the invention include dimethyldodecylamine oxide, 01eyl-di (2-hydroxyethyl) amine oxide, dimethyloctylamine oxide, dimethyldeoylamine oxide, dimethyltetradecylamine oxide, 3 , 6,9-tri oxaheptadecyl diethylamine oxide, di (2-hydroxyethyl) tetradecylamine oxide, 2-dodecoxyethyldimethylamine oxide, 3-dodecoxy-2-hydroxypropyl-di- (3-hydroxypropyl) -amine oxide and dimethylhexadecylamine oxide.

(d) Long-chain tertiary phosphine oxides (non-ionic detergents) which ^{correspond to the following general formula RR 1} R ¹¹ P »O, where R is an alkyl,

Alkenyl or monohydroxyalkyl radical with 8 to 18 carbon atoms in the chain length, contains 0 to about 10 ethylene oxide radicals and 0 to 1 grlyceryl radical and R ¹ and R "are each alkyl or monohydroxyalkyl groups containing 1 to 3 carbon atoms. The arrow in FIG Formula represents a common symbol of a semipolar bond. Examples of suitable phosphine oxides are:

Dodecyldimethylphosphine oxide, Tetradecyldimethylphosphine oxide, Te trade oylmethylethylphosphine oxide, 3 »6,9-Trioxaootadeoyldimethylphoaphinoxyd,

C etyl dimethyl phosphine oxide,
3-dodecoxy-2-hydroxypropyl-di- (2-hydroxyethyl) -

phosphine oxide,

St earyl dime thylpho sphinoxyd, G e ty la thyl ρ r opylpho sp hi noxy d, 01eyldiäthylphosphinoxyd,
Dodecyl diethylphosphine oxide j
letradecyl diethylphosphine oxide, dodecyldipropylphosphine oxide, dodecyl di (hydroxymethyl) phosphine oxide, dodecyl di (2-hydroxyethyl) phosphine oxide, tetradecylmethyl 2-hydroxypropylphosphine oxide, oleyldodecethylphosphine oxide, oleyldodecethylphosphine oxide, 2-hydroxymethylphosphine oxydoxy.

(e) Long-chain dialkyl sulfoxides, which are a short-chain Alkyl or hydroxyalkyl radical with 1 to about 3 carbon atoms - material atoms (usually methyl) and a long, hydrophobic one Contain chain, the latter being alkyl, alkenyl., Hydroxyalkyl or ketoalkyl radicals with about 8 to about Contains carbon atoms, 0 to about 10 ethylene oxide radicals and 0 to glyceryl radical.

Examples include:

Octadecylmethylsulfoxide, 2-ketotridecylmethyl sulfoxide, 3,6,9-trioxaoctadecyl-2-hydroxyethyl sulfoxide, Dodecylmethylsulphoxide, 01eyl-3-hydroxypropylsulphoxide, Tetradecylmethylsulfoxide, 3-methoxytri decylmethyl sulfoxide, 3-Hydroxytri decylmethylsulfoxyd and 3-Hydroxy-4-do decoxybutylmethylsulfoxide.

109808/1940

- (f) Ampholytic synthetic detergents can generally be used as derivatives of aliphatic secondary and tertiary Amines are described in which the aliphatic ^ Radically can be straight or branched chain and wherein one of the aliphatic substituents from about 8 to about 18 carbon dioxide and one an anionic, water-dissolving one Contains group, e.g. carboxyl, sulfonate, sulfate, phosphate or phosphonate groups. Examples of Compounds that fall within the scope of this definition are sodium 3-dodecylaminopropionate, sodium 3-dodecylaminopropanesulfonate, Dodecyl-ß-alanine, N-alkyltaurine, such as those obtained by reacting dodecylamine with sodium isethionate according to US Pat. No. 2,658,072 N-higher alkylaspartic acids such as those prepared in U.S. Patent No. 2,438,091 and the products sold under the trade name "Miranol" and in U.S. Patent No. 2,528,378 are described.

(g) Zwitterionic synthetic detergents can generally be used as derivatives of aliphatic quaternary Ammonium, phosphonium and sulfonium compounds addressed in which the aliphatic radicals can be straight or branched chain and in which one of the aliphatic substituents contains about 8 to 18 carbon atoms and one is an anionic one which solubilizes in water Has group, e.g. carboxyl, sulfonate, sulfate, phosphate or phosphonate G groups. A general Formula for these compounds is the following:

109808/1940

_R ² _ γ (+) ___ CH ₂ - fi ⁴ -

ρ
wherein E. an alkyl, alkenyl or hydroxyalkyl radical with about 8 to about 18 carbon atoms, 0 "to about 10 ethylene oxide radicals and 0 Ms 1 grlyceryl radical; Y a nitrogen, phosphorus or sulfur atom; Ir an alkyl or Monohydroxyalkyl group with 1 Ms mean about 3 carbon atoms, while χ stands for 1 if Y is a sulfur atom, and 2 if Y is a nitrogen or phosphorus atom symbolizes R for an alkylene or hydroxyalkylene with up to about 4 carbon atoms and Z for a radical a carboxylate, sulfonate, sulfate, phosphonate and phosphate group.

Other examples include? 4- / ~ "N, N-di- (2-hydroxyethyl) -N-octadecylamino ^ -butane-1-carboxylate; 5- / ~ S-3-hydroxypropyl-S-hexadecylsulfonio_7-3-hydroxypentane-i-sulfate ; 3- / P, P-diethyl-P-3,6,9-trioxatetracosanphosphonio J- 2-hydroxypropane-1-phosphate; 3- / ~ Ii »N-dipropyl-N-5-dodecoxy-2-hydroxypropylammonio _7 ~ propane-1-phosphonate; 3- (N, H-bimethyl-N-hexadecylammonio) -propane-1-sulfonate; 3- (N, N-dimethyl-N-hexadecylammonio) -2-hydroxypropane-1-aulfonate; AC N "N-di- (2-hydroxyä thyl) -N- (2-hy droxydo decyl) -ammoni ο J- butan-1-carboxylate; 3- / ~ S-A'thyl-S- (3-dodecoxy-2 -hydroxy propyl) -sulfonio ^ -propane-1-phosphate; 3- / ~ P _f P-DiiBethyl-P-dodeeylphosphonio ^ -propane-1 -phosphonate and S- ^ ~ N, N-di- (3-hydroxypropyl) -N-hexadeeylammonio_7-2-hydroxypentane-1-sulfate.

Examples of compounds that fall under this definition are 3- (N, N-dimethyl-N-hexadecylammonio) propane-1-8ulphonate and 3 ^ (N, N-dimethyl-N-haxadeeylammonio) -2-hydrpxy-

10ÖÖÖÖ / 1Ö4Ö

propane-1-sulfonate, in particular because of its excellent Cold water detergent characteristics are preferred.

The alkyl groups contained in these surface-active detergents can be straight-chain or branched-chain and are preferably straight-chain and saturated or unsaturated as desired. The above list of Detergent surfactants are by way of illustration and not limiting. Mixtures the above detergent surfactants can be used.

The detergent mixtures according to the invention can be used in in any suitable physical form, such as granules (e.g. spray-dried or mechanically mixed), tablets, pastes or liquids.

The mixtures can contain particulate inorganic salts contain, which behave inert in the approach and serve as fillers. Examples of such salts include sodium sulfate and sodium chloride.

Other smaller additives can also be included in the mixtures according to the invention. Dirt suspending agent, such as sodium carboxymethyl cellulose, optical brighteners, dyes, germicidal agents, anti-foaming agents and Foam boosters can be added to the mixture in amounts up to about 10 Grew .- ^ each.

The products according to the invention can be used in aqueous solutions in amounts of about 0.05 to about 1.0 ml; if objects made of zamak are brought into contact with these solutions, there is much less corrosion than in the case of the use of similar mixtures containing the special phosphonate

109808 /

corrosion inhibitor according to the invention not included.

All information regarding parts. Percentages and ratios are based on weight information, unless otherwise stated.

The following examples illustrate the worth seeing and excellent performance according to the invention en corrosion inhibitors.

Example 1;

A spray-dried granulated detergent is prepared which has the following composition; the production takes place by mixing the individual components in the usual way using a quantity of water, sufficient to form a detergent slurry and spray drying the sludge to remove excess moisture and form detergent granules.

Sodium alkylbenzenesulfonate with ge _--- "' chain alkyl radicals, which have an average chain length of about

15 carbon atoms has 13.3%

Sodium tripolyphosphate 41.4%

Sodium Nitrilotriacetate $ 9.6

Sodium silicate with a

SiO ₂ : Ha ₂ O ratio of 1.6 10.0 #

Sea oil fatty acids 0.5 %

Tallow fatty acids 1 * $ 5

Sodium carboxymethyl cellulose 0.33%

Sodium sulfate 11.26%

109808/1940

Water 11.00

Various ingredients including perfume, optical brighteners and pigments 1.12

A similar detergent mixture was also made which contained as an etch ingredient 0.3 $ arbitrary octadecylphosphonic acid, which was prepared by adding phosphorous acid to a random mixture of octadecenes using gamma radiation as all free radical generators. Arbitrary olefins were obtained by isomerizing 1-acetates with 10% of msenpentacarbonyl at about 150 G for about 1 hour

th. The sugesetÄte Octadeeylphosphonsäure ersei ^ ij proportional Percentages of ingredients in the first detergent mix.

The corrosive effects of the above two products were tested in an experiment using Zamak No. 3 test panels which were about 2.5 by 10 cm (1 by 4 inches) and about 3.2 inches thick mm (1/8 inch). Piping PrUfplatten were exposed at a temperature of 60 ⁰ C (140 ⁰ F) solutions of the detergent mixture in distilled or "hard ¹¹ iieitungswasser for 6 hours under stretchers. The corrosion products were removed by scraping with a PlastikborBten having brush and the dried test plates were weighed, to determine the weight loss caused by corrosion The results of these tests are given in the table below.

ORIGINAL INSPECTED

10.9 808/1940

Concentration of the product:

G weight loss in mg:

Type of Water: inhibited: not inhibi- - biert

0.2 *
0.50

tap water

distilled water

5.0
30.7

45.7 88.5

Further examples are listed below in tabular form:

Examples (% by weight of the compound)

Constituent

Sodium tripolyphosphate

Potassium ethane-1-hydroxy-l, 1,2-triphosphonate

Sodium nitrilotriacetate

30th

!

Sodium ethane 1-hydroxy-l, j 1-diphoaphonate

4 *

latriumaalz of arbitrary ootadeoylphoaphonaic acid ^ 0.2

Salium 9-octadecylphosphonate

arbitrary Octadecyl phosphonic acid

20th

20th

20th

0.5

30th

20th

I '

50

ί 20

| OfJ

90

9Θ

1.0

10.3

10

60

39

11

j 0.2

! 0.1

1.0 i

12th

15th

14th

6 6

, 3 '

ON

O OO

Component! 2 3 ■ 10 ! 4th 4th 5 6th 7th • 8th • i. .. 10 11 f
12 j 13 I. ⁸ · I ' 14th Sodium alkyl 1 i bensäolsulfo- of course with just J the alkyl chain 'j (on average J I. ; VJl ■■■! 10 9 Sodium tallow alkyl sulfate j 6th 6th 3- (S, S-DiBe- - j thyl-Jtf-sebum- alkylammo- 5 Ϊ ; ■■. ■ » j nio) -2-hydr- oxypropane-1- '"'. * sulfonate 5 5 The reaction • ■ ■■ '> product of j SO, and C, _o «-
5 Io t "■ '; Olefin that with sodium; 1 hydroxyd new - is centralized 20th 10 y Tallow alcohol ethylene oxide (5 moles) -re- action pro * · _; 1 i duct 5 ⁴ I.

-4

Component:

Coconut alkyldimethylphosphine oxide

5-dodecoxy-2-hydroxypropyl methyl sulfoxide

Coconut alkyl di- (2-hydroxyethyl) · Amine oxide

Sodium silicate (SiO ₂ «Na ₉ O -1.6)

Benzotriazole

Potassium pyrophosphate

Sodium perborate

Sodium sulfate

j 0.02 0.02

10 '

'17

IH

I 12

10

0.02

10

ίο! ίο

10

10

14th

Component: 2 3 I. 4th ί 5 6th 7 5
i 8th I.
j
i 9 I. / 10 11 I 12 I 15 1.4 14th ,
I. 4th 2 Fluid
opportunities I. Coconut-
ammonia amide j 2.6 2 1.4 VO Coconut-
diethanol
amide 8th 4th Sodium carb
oxymethyl
_i cellulose 1.6 1.6 1.6 1.6 j 1.6 1.6 1.4 ίο potassium
*> toluene
sulfonate 4th ~ * Water s t => Shape nulate ■ R e

The above mixtures are valuable detergents Used in amounts of about 0.1 # in water detergents and show inhibited corrosiveness towards zamak.

Example 15:

It is allowed to aluminum plates in an aqueous solution are, the 0.35 "fc contains a detergent mixture which jo from 20 ° Batriumtetrapropylenbenzolsulfonat, 50 sodium tripolyphosphate, 25 # sodium sulfate and 5 $> the aforementioned inhibitor is made. All! Above percentages are Weight * - #. The aluminum plates are exposed to the aqueous detergent solutions for 3 hours at 60 ° G (14Q ⁰ J?) And a pH value of 9.5, the water is not stirred. After 3 hours, the aluminum plates are rinsed with water, the corrosion products with concentrated ENT, removed, whereupon rinsed with water and alcohol and, after drying, a determination of the weight loss in mg / cm. The results were determined for soft water as well as for water Potassium carbonate) of Q, 45 g each had 3.78 l (7 grains per gallon).

- ■ 0 Weight loss mg / cm: in 0.45 g hardness / Inhibitor: None . g hardness / 5.78 1 i Oylphosphonic acid 78 1: 0.59 Oleyl phosphate 0.79 0.54 1. 10-nonadecylphosphonic 0.00 0.52 2. acid 0.03 3. 0.01 4th 0.01

109800/1 ^ 0

Weight loss inhibitor; in mg / cm t

α g hardness / 0.45 g hardness / 5.78 1: 3.78 1 i

5. hydrolyzed reaction product of 1-octadene, PCI * *, acetic anhydride

and oxygen (this hydrolyzed reaction product is a mixture of saturated and unsaturated octadecyl phosphonic acids and saturated oetadecyl phosphates. Some of the saturated phosphonic acids contain combined chlorine.) ⁺ Q ₁ 06 0.02

6 »It hydrolyzes reaction product of 1-Octadeeen, fCl » and oxygen (this hydrolyzed reaction product is a mixture of saturated and unsaturated octadecylphosphonic acids and saturated octadecylphosphates. Some of the saturated phosphonic acids contain combined chlorine). + 0.02 0.06

7. Hydrolyzed reaction product of octadecane, PCI- * and oxygen (this hydrolyzed reaction product is an arbitrary octadecylphosphonic acid which

contains a mixture of isomers). 0.01 0.10

8. Dodecylbenzylphosphonic acid 0.36 0.33

9. P entadecylbenzylphosphonic acid 0.02 0.03

⁺ = The content of saturated alkylphosphonic acid was greater than 80 % of the reaction product.

As seen by reviewing the above results

109808/1940

sind.kann.kann are the corrosion inhibitors according to the invention (4, 5 »6, 7 and 9) much more effective, especially in hard water, than similar mixtures that are outside are within the scope of the present invention (Figures 2, 3 and 8). Furthermore, the corrosion inhibitors are relative for comparison (1) extremely beneficial. These mixtures are all inhibited from corrosive attack by Zamak No. 3 ..

If the following detergent builders are used either in whole or in part in the above detergent mixes, so that, for example, a 1: 1 ratio is obtained instead of sodium tripolyphosphate and / or sodium nitrilotriacetate are used, essentially equivalent results are obtained in that the detergent mixtures containing These detergent builders contain, are inhibited against corrosive attack by Zamak No. 3: sodium, potassium, ammonium, Monoethanolammonium, diethanoi ammonium and triethanolaTmr.onium saIζe of the following acids: ethylenediamine tetrae.acetic acid; N- (2-hydroxyethyl) ethylenediamine triacetic acid; N- (2-hydroxyethyl) nitrilodiacetic acid; Diethylenetriaminepentaacetic acid; Nitrilotriacetic acid; Ethylene diphosphonic acid; Ethane-1-hydroxy-1,1-diphosphonic acid; Ethane-1-hydroxy-l , 1-diphosphonic acid; Ethane-1,1,2-triphosphonic acid; Ethane-2-carboxy-l, l-diphosphonic acid; Hydroxymethanediphosphonic acid; Carbonyl diphosphonic acid; Ethane-1-hydroxy-1,1,2-triphosphonic acid; Ethane-2-hydroxy-l, 1,2-triphos phonic acid; Propane-l, l, 3 »3-tetraphosphonic acid; Propane-1,1,2,3-tetraphosphonic acid and propane-l ^^ jS-tetraphosphonic acid and potassium tripolyphosphate.

In the above detergent mixes, the following Phosphonic acid corrosion inhibitors in place of all or part, e.g. in a ratio of 1: 1 of the arbitrary Octadecylphosphonic acids are used, so are im

109808 / 1UO

■ obtained substantially equivalent results since the detergent blends against corrosive attack by Zamak Mr. 3 are inhibited: The corresponding tetracosane, letradecane, Pentadecane, heptadecane, nonadeean, eicosane and docosane homologues - the arbitrary octadecanephosphonic acids; the sodium, potassium, ammonium, monoethanolammonium, Diet hanoiammonium and triethanolammonium oil salts of the above said phosphonic acids; fertilize the following compounds and the sodium, potassium, ammonium, monoethanol ammonium, diethanol ammonium and triethanol ammonium salts the same: 10-nonadecylphosphonic acid; Pentadecylbenzylphosphonic acid; Alkylbenzylphosphonic acid mixtures, in which the alkyl groups of (1) a mixture of propylene polymers, (2) olefins from cracked petroleum waxes or (3) olefins, which arise in the course of the Ziegler-type synthesis reactions of ethylene, can be derived, the alkyl groups Have sizes in the range of 12 to 21 carbon atoms and average 14, 15, 16 or 18 carbon atoms;

Hexadecylbenzylphosphonic acid, wherein the hexadecyl group is derived from polymerized isobutylene;

Alkylbenzylphosphonic acids, in which the alkyl group is derived from a chlorinated kerosene fraction with an average of 15, 16, 17 or is derived from 18 carbon atoms;

the mixture of 6-excosenyl-4-phosphonic acid and 5-vinyloctadecyl-4-phosphonic acid, by reducing the des in the implementation of butyric anhydride and the allylcarbanion 1 — hexadecene formed ketone to alcohol, conversion of the Alcohol into the tosyl ester, alkylation of the dibutylphosphonate anion is obtained with the ester and hydrolysis of the resulting product;

1098 08/1340

the hydrolyzed reaction products of phosphorus trichloride, Oxygen and a mixture of olefins containing 18, 19 »20 or 22 carbon atoms and those of (1) cracked petroleum waxes or (2) Ziegler-type build-up reactions of ethylene can be derived;

the mixture of Octadecylphosphonsäuren, which is prepared by alkylation of Dibutylphosphonatanion with the mixture of 2- to 9-Octadecylschwefelsäuren obtained by reaction of 1-octadecene with excess sulfuric acid at 0 to 10 ⁰ C for about 2 to 3 hours, and hydrolysis of the alkylated Dlbutylphosphonatanions arises;

the mixture of phosphonic acids obtained by isomerizing the double bond of 1-oetadecene with aluminum chloride, Adding sodium hypophosphite to the resulting Olefins and oxidation of the resulting phosphinates to phosphonates is obtained with nitric acid;

the hydrolyzed reaction product of 1-octadecene, phosphorus trichloride and oxygen;

the hydrolyzed reaction product of 1-octadecene, Phosphorus trichloride, acetic anhydride and oxygen and

the hydrolyzed reaction product of octadecane, phosphorus trichloride and oxygen, e.g. in the ratio of 1: 1 or 2: 1.

If the following organic detergents are used in the above mixtures instead of all or one Part (e.g. in a ratio of 1: 1) of the sodium alkylbenzenesulfonate with an average chain length of about 13 carbon atoms are used »so essentially equivalents

109808/1940

The best results obtained because the detergent mixture is resistant to corrosion of Zamak No. 3

(1) DLe following anionic synthetic detergents, in which the cations are sodium, potassium, ammonium, monoethanolammonium, diethanolammonium, triethanolammonium cations. Salts of the higher fatty acids derived from palm oil, coconut oil, babassu oil, soybean oil, castor oil, tallow, whale oil, fish oils, fat, lard, resin acids from tall oil and / or naphthenic acids; Alkyl sulfates wherein the alkyl group is derived from tallow or coconut oil; Alkylbenzenesulfonates in which the alkyl groups S _t contain 11, 12, 13 or 15 carbon atoms; Alkyl glycidyl ether sulfonates derived from tallow or coconut oil; Coconut fatty acid monoglyceride sulfates and sulfonates; Salts of the sulfuric acid esters of the reaction product of 1 mole of tallow or coconut oil fatty alcohols and 3 or 4 moles of ethylene oxide; Alkylphenolethylene oxide ether sulfates which contain 4 or 9 ethylene oxide radicals per molecule and in which the alkyl radical contains 9, 12, 13 or 15 carbon atoms; the neutralized reaction product of coconut fatty acids with isethionic acid; Coconut fatty acid amide of methyl taurine salts;

(2) the condensation product of ethylene oxide with the condensation product of propylene oxide with propylene glycol, the ethylene oxide content of the compound making up 50% of the total weight of the compound and the total molecular weight of the compound being about 1700; the condensation product of alkylphenols which contain 9 or 12 carbon atoms in the alkyl group with 10, 15 or 20 moles of ethylene oxide per mole of alkylphenol; the condensation product of ethylene oxide with the condensation product of propylene oxide and ethylenediamine, in which the product is about 65 wt .- ^ poly-

1O98O8 / 1! UÜ

Contains ethylene oxide and the total molecular weight of the Compound is about 6000; the condensation product of coconut oil alcohol and about 15 moles of ethylene oxide each Moles of coconut alcohol;

Dirnethyldodecylamine oxide, 01eyl-di- (2-hydroxyethyl) amine oxide, dimethyloctylamine oxide, Dimethyldeeylamine oxide, dimethyltetradecylamine oxide, 3,6,9-Trioxaheptadecyidiäthylaminoxyd, Di- (2-hydroxyethyl) -t et radecylamine oxide, 2-Dodecoxyäthyldimethylaminoxyd, J-Dodecoxy - ^ - hydroxypropyl-di- (3-hydroxypropyl) -aminoxyd,

Diine thylhexadecylamine oxide, dodecyldimethylphosphine oxide, 'ietradecyldimethylphosphine oxide, tetradecylmethylethylphosphine oxide, 3 »6, g-Trihexaoctadecyldimethylphosphine oxide, C etyldimethylphosphine oxide, 3-DodeGOxy-2-hydroxypropyl-di- (2-hydroxyethyl) -phosphine oxide,

Getyläthylpropylphosphinoxyd, Oleyldiäthylphosphinoxyd, Dodecyldiäthylphosphinoxyd, Tetradecyldiäthylphosphinoxyd, Dodecyldipropylphosphinoxyd, dodecyldi (hydroxymethyl) -phosphinoxyd _f Do decyl-di- (2-hydroxyethyl) -phosphinoxyd, tetradecylmethyl-2-hydroxypropylphosphinoxyd, 01eyldimethylphosphinoxyd, 2-Hydroxydodecyldimethylphosphinoxyd, Oetadecylmethylsulfoxyd,

1 !

- 57 -

3, 6,9-Irioxaoc tadecyl-2-hydroxyethylsulfoxide, Itodeeylmethylsulfoxyd, 01 eyl-3-hydroxypropylsulphoxide, tetradecylmethylsulphoxide, 3-Methoxytride.cylmethylsulfoxyd, 3-Hydroxytri de cylmethylsulfoxyd, 3-hydroxy-4-dodecoxybutylmethylsulfoxide, Sodium 3-dodecylaminopropionate, liatrium-3-dodecylaminopropan.-l-sulfonate, Dodecyl-ß-alanine,

W-alkyltaurines;

(3) N-higher alkyl aspartic acids wherein the alkyl group contains about 12 carbon atoms; 4- / ~ N, li-di- (2-hydroxyethyl J-li-octadecylamineinonio ^ -butane-1-carboxylate; 5- / "S- (3-hydroxypropyl) -S-hexadeoylsulphonio_7-3-hydroxypentane-1-sulphate ; 3- £ P, P-diethyl-P- (3,6,9-trioxatetracosanphosphonio) _ / - 2-hydroxypropane-1-phosphate; 3 - / "^ jN-dipropyl-N- (3-dodecoxy-2- hydroxypropylammonio) _7 ~ propane-1-phosphonate; 3- (IT, N-dimethyl-K-hexadecylammonio) -propane-1-sulfonate, 3- (N, M "-dimethyl -N-hexadecylammonio) -2-hydroxypropane-1 sulfonate, 4 - / "N, N-di- (2-hydroxyethyl) -N-2-hydroxydodecylammonio_7-l3utane-1-carlooxylate, 3- / ~ S-ethyl-S- (3-dodecoxy-2-hydroxypropylsulfonio) _7 ~ propane-1-phosphate, 3-J ~ P, P-dimethyl-P-dodecylphosphonio_7-propane-1-phosphonate and 5- / ~ N, N-di- (3-hydroxypropyl) -N-hexadeoylammonio J-2 - hydroxypentane-1-sulfate and

(4) Mixtures thereof, e.g. in a ratio of ItI.

Will the following nickel silver corrosion inhibitors in whole or in part (possibly in a ratio of 1: 1) instead of the benzotriazole in the above detergent mixes

109806 / lSUn

are used, essentially equivalent results are obtained, since the mixtures of nickel silver in a too * do not discolour objectionable extent: 2-aminobenzothiazole, 3-amino-l, 2,4-triazole, ethyl entiourine tof f, 3, 5-bimethylpyrazole, Adenine and their mixtures (e.g. Mi loop in a ratio of 1: 1).

108 * 01/1 * 40

Claims (10)

Patent applications: 1. A detergent mixture comprising (l) 1 to about 98 io of the mixture of a detergent builder from the group comprising water-soluble aminopolycarboxylate, tripolyphosphate and polyphosphonate detergent builders and mixtures thereof; (2) greater than 0.05 and less than about 25% by weight of the total detergent mixture of a corrosion inhibiting compound of the formula I » R - P (OQ) ₂ * where R = (A) a straight chain alkyl chain in which the phosphorus atom is attached to a secondary carbon atom of the chain is bonded and wherein the straight-chain alkyl radical contains from about 12 to about 24 carbon atoms, or (B) straight-chain Alkylbenzyl groups wherein the alkyl group is from about 9 to about Contains 18 carbon atoms, and wherein Q = one The water-solubilizing cation symbolizes which mixture is inhibited in terms of corrosive attack against zamak is. 2. detergent mixture according to claim 1, characterized in that it consists essentially of (l) from about 1 to about 90 # of the detergent builder mix of aer water soluble aminopolycarboxylate, tripolyphosphate and polyphosphonate detergent builders and mixtures thereof comprehensive group; (2) from 0 to about 15 weight percent of the mixture of an alkali silicate with a ratio of Documents (Art? § I Paragraph Ζ No. I Sate 3 of the amendment ^ s. · /. 4. 9. ·. 109808/1940 SiO ₂ : “MpO from about 1.0 to about 3.6; (3) from greater than 0.05 and less than about 25% by weight of the total detergent mixture of a corrosion inhibiting compound having the formula »I. R - P (OQ) ₂ where R = (A) a straight-chain alkyl radical attached to the Phosphorus atom is bonded via a secondary carbon atom of the chain, the straight-chain alkyl radical about 12 to contains about 24 carbon atoms, or (B) a straight chain alkylbenzyl group »wherein the alkyl group contains from about 9 to about Contains 18 carbon atoms, and where Q = a water-solubilizing agent Cation from the hydrogen, alkali, ammonium and substituted ammonium cations comprising Mean group; (4) from 0 to about 1 $ of an anti-corrosive compound to protect nickel silver; (5) off up to about 40 # of an organic detergent selected from the nonionic, anionic, amphoteric and zwitterionic detergents and mixtures thereof; (6) from 0 to about 90 $ other detergent builders from the alkali pyrophosphate, Orthophosphates, tetraborates, perborates, hexaphosphates, sesquicarbonates and bicarbonates and mixtures thereof comprising group and (7) consists of 0 to about 90% water. 3. detergent mixture according to claim 2, characterized in that that the detergent builder is selected from the group comprising the following compounds: alkali, Ammonium and substituted ammonium salts of the following acids: ethylenediaminetetraacetic acid, N- (2-hydroxyethyl) - 109808/1940 ethylenediamine triacetic acid, N- (2-hydroxyethyl) nitrilodiacetic acid, Diethylenetriaminepentaacetic acid, 1,2-diaminocyclohexanetetraacetic acid, Nitrilotriacetic acid, diphosphonic acid, ethane-l-hydrqxy-ljl-diphosphonic acid, ethane-1,1,2-triphosphonic acid, Ethane-2-carboxy-1,1-diphosphionic acid, Hydroxymethanediphosphonic acid, carbonyl diphosphonic acid, ethane-l-hydroxy-1,1,2-triphosphonic acid, ethane 2-hydroxy-l, l, 2-triphosphonic acid, Propane-l, l, 3,3-tetra-phosphonic acid, propane-l, l, 2,5-tetraphosphonic acid and propane-1,2,2,3-tetraphosphonic acid and potassium tripolyphosphate and sodium and potassium tripolyphosphates. 4. Detergent mixture after. Claim 1, characterized in that that the corrosion-inhibiting compound one is arbitrary octadecyl phosphonate. 5. Detergent mixture according to claim 2, characterized in that it contains about 10 to about 20 fi of a synthetic anionic organic detergent as the organic detergent. 6. Detergent mixture according to claim 2, characterized in that it contains 0.05 to about 2 µl of the corrosion-inhibiting compound and about 2 to about 10 µl of the alkali silicate. 7. Mixture according to claim 1 »characterized in that it is at least about 2 wt .- ^, based on the total Detergent mixture, with an anti-corrosive compound contains, the corrosion-inhibiting compound chosen is that the straight alkyl chain (A) contains at least about 18 carbon atoms and the straight-chain alkylbenzyl (B) groups at least about 20 carbon atoms included, the mixture against corrosive attack is inhibited by aluminum and nickel silver. 8. Mixture according to claim 2, characterized in that that they are at least about 2% by weight of the total detergent mixture of corrosion-inhibiting compound, the corrosion-inhibiting compound being selected so that the straight alkyl chain (A) is at least about 18 carbon contains atoms and the straight chain alkylbenzyl (B) groups contain at least about 20 carbon atoms, wherein the mixture is inhibited against corrosive attack by aluminum and nickel silver. 9. detergent mixture according to claim 6, characterized in that that the detergent builds off a mixture of water-soluble tripolyphosphate and water-soluble nitrilotriacetate in a molar ratio of from about 4: 1 to about 1: 4 is 10. detergent mixture according to claim 9, characterized in that the detergent build-up is a mixture of Sodium tripolyphosphate and sodium nitrilotriacetate in one Molar ratio is from about 3: 1 to about 1: 3. For: The Procter 4 Gamble Company Lawyer BAD OHsGiNAL 109808/1940