DE2857294A1 - DETERGENT MIXTURE WITH LOW PHOSPHATE CONTENT FOR WASHING TEXTILES - Google Patents

Description

Our no. 22 567 D / wl

The Procter & Gamble

Company,

Cincinnati, Ohio, V.St.A.

Low phosphate detergent mix for Washing of textiles

The present invention relates to detergent compositions, in particular detergent mixtures containing builder, for washing of textiles.

Mixtures containing a detergent and a builder compound are generally referred to as "builder-containing" Called detergent mixtures. If a large amount of detergent builder, based on the detergent, is used, so one calls the mixtures as "heavy detergent" mixtures, which are primarily used for washing heavily soiled Textiles are intended. Detergent mixtures with a lower level of builder are called "light detergent" mixtures and for lightly soiled textiles, "Delicates" and VvO 11, s were used.

The use of detergent builders as additives too organic, water-soluble, synthetic detergents and the property of these substances in terms of improvement the overall washing performance of such detergents are known. A variety of such materials, in particular

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Sodium polyphosphates are known for this use as detergent builders. However, there was some concern Expressed that certain algae in water bodies for nutritional purposes from phosphorus-containing materials Make use. Phosphorus-free builder components would be free from such criticism. There was therefore a need for detergent builders that are biodegradable, however, in terms of their builder effectiveness Sodium tripolyphosphates are comparable.

_The mechanism by which detergent builders work become to improve the detergency of water-soluble organic detergent compounds, is not exactly known; However, there appears to be some combination of factors such as softening of the water, and dirt suspension to be responsible for its redeposition-directed effects as well as pH adjustment. Today's theory however, does not allow any prediction of which compounds might be effective as detergent builders. It has therefore been empirically determined that a large number of substances, including the aforementioned tr! Polyphosphates, also phosphonates, nitrilotriacetates, sodium sulfate and various silicates and aluminosilicates all as detergent builders take effect, at least to some extent.

Recently a number of polycarboxylates have been reported which are effective as detergent builders, water softeners and soap dispersants in detergent mixtures should. For example, the ÜS-PS 2 264 103 concerns the use various polycarboxylic acids as detergent builders and water softeners. This patent teaches

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that polycarboxylates with 3 or more carboxyl groups per Molecule are useful as detergent builders and water softeners. NL-PA 6 501 871 concerns the use of various polymers, for example itaconic acid and aconitic acid, in detergents. GB-PS 1 261 829 describes the use of oxydisuccinic acid as a Dtergent builder, while GB-PS 1,379,241 the Use of carboxymethyloxysuccinic acid as a builder for debrides disclosed. It can thus be seen that a large number of polycarboxylates have already been in use has been proposed as detergent builders. These However, materials exhibit numerous disadvantages and have not been found generally acceptable for this use. For example, many of these substances are difficult and expensive to manufacture, or they have to be in substantial amounts can be used to produce effective builder properties. On the other hand, the The content of polycarboxylate builder is reduced to an economically justifiable value, so the resulting turn out Mixtures often in some areas of builder behavior such as calcium sequestration or pH buffering as poor; in other words, them behave like typical mixtures with too little builder.

Another consideration when using polycarboxylates as builders is that they determine the most common and cheapest materials have their greatest buffering effect at relatively low pH values, where conventional bleaching agents like perborates and percarbonates are the least effective. Hence these are polycarboxylates and bleach to some extent mutually incompatible and the resulting mixtures were found

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hence, defective in the field of bleachable stain removal.

Another aspect related to bleach / polycarboxylate incompatibility is the one that hydroxycarboxylate Like citric acid, it is known to decompose at higher washing temperatures and are therefore only effective in washing processes can be used at a relatively low temperature. Perborate and percarbonate, on the other hand, are lower Temperatures ineffective in the absence of bleach activators. Again, therefore, there must be a builder effect or a bleaching effect a compromise can be found to some extent when employing hydroxycarboxylates as builders.

The present invention provides mixtures of detergents which contain little or no phosphate and essentially equivalent cleaning effect as a conventional, Have tripolyphosphate as a builder-containing mixture. The invention also relates to mixtures with sufficient Detergency and builder properties, based on less than conventional levels of certain polycarboxylate builders. The invention also relates to mixtures of iterants with polycarboxylate builders, the improved cleaning effect in the area of bleachable stain removal to have.

The invention relates to a detergent mixture with a phosphorus content of not more than 6 %, preferably not more than 5 %, and a pH value in 1 ^ aqueous solution of less than 10, which is characterized by

a) 2 to 75 % of an organic detergent from the group of anionic, non-ionic, amphoteric

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and zwitterionic detergents and their mixtures,

b) 4 to 50 % of a carboxylate or polycarboxylate with a logarithmic acidity constant for the first carboxyl group (pK-,) of less than 9> and

c) 0.01 to 4 fo of a polyphosphonic acid or a polyphosphonic acid salt.

The detergent mixtures according to the invention preferably have a pH value of less than about 9.5% in 1% aqueous solution and more preferably a pH value in the range from about 6 to about 9..0, in particular from about 7 to about 8.5 · According to preferred embodiments, the carboxylate or polycarboxylate builder has a logarithmic acidity constant in the range from about 2 to about 8.5. » especially from about 4 to about 7.5 * and a logarithmic calcium stability constant (pK "" ++) in the range of about 2 to about J. Preferred mixtures contain from about 8 to about J50 wt.% of the carboxylate or polycarboxylate builder s, in particular about 12 to about 25% by weight , and about 0.2 to about 3.5% by weight of the polyphosphonate, in particular about 0.5 to 2.2% by weight .

The various compulsory and optional components of the mixtures according to the invention are now described.

Organic detergent

The detergent active component of the present blends can be anionic, nonionic, ampholytic or zwitterionic in nature or a mixture of such detergents.

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The detergent mixtures according to the invention contain the active system in an amount of about 2 to about 75% by weight . In solid, granular mixtures, the active system is generally present in the range from about 4 to about 50 % , more preferably from about 6% to about 15 % of the mixture. In liquid mixtures, higher active levels, for example about 20 % to about 70 %, are usually used. A typical listing of anionic, nonionic, zwitterionic, and amphoteric surfactants useful herein is contained in U.S. Patent J5,925,678. The following list of detergent compounds which can be used in the compositions of the invention is representative of such materials.

Water-soluble salts of other fatty acids, i.e. "soaps", are useful as the anionic detergent component of the mixtures. This class of detergents includes the common alkali metal soaps such as sodium, potassium, Ammonium and alkylolarnmonium salts of other fatty acids with from about 8 to about 24 carbon atoms, and preferably from about 10 to about 20 carbon atoms. Soaps can be made are made by direct saponification of fats and oils or by neutralizing free fatty acids. Particularly The sodium and potassium salts of fatty acid mixtures can be used from coconut oil and tallow, that is the sodium source Potassium sebum and coconut soap.

A highly preferred class of anionic detergents comprises water-soluble salts, especially the alkali metal, Ammonium and alkylolammonium salts of organic sulfuric acid reaction products, which has an alkyl radical with about 8 to about 22, in particular about 10, in its molecular structure up to about 20 carbon atoms and a sulfonic acid or

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Contain sulfuric acid ester group (the term "alkyl" also includes the alkyl radical of acyl groups). Examples of this group of synthetic detergents which are part of the Forming detergent mixtures according to the invention are the sodium and potassium alkyl sulfates, especially those that are obtained by sulphating the higher alcohols (Co-C-, ρ-

yoursexfcs ο Io

Carbon atoms) obtained by reducing the glycerides of tallow or coconut oilj and sodium and potassium alkylbenzenesulfonates, the alkyl radical of which contains from about 9 to about 15 straight chain or branched chain carbon atoms, for example those in US- = PSS 2,220,099 and 2,477 3% J> type described. Particularly valuable are linear, straight-chain alkylbenzenesulfonates in which the alkyl group has on average about 11.8 carbon atoms, which are abbreviated as C-., η LAS.

A preferred alkyl ether sulfate surfactant component according to the present invention is a mixture of alkyl ether sulfates, which has a mean (arithmetic Medium) carbon chain length in the range from about 12 to 16 carbon atoms, preferably from about 14 to 1'5 Carbon atoms, and an average (arithmetic mean) degree of ethoxylation of about 1 to 4 moles of ethylene oxide Has.

Other anionic detergent compounds that may be used include the sodium alkyl glyceryl ether sulfonates, especially those -ither higher alcohols derived from tallow and coconut oil; Sodium Coconut Oil Fatty Acid Monoglyceride Sulphonates and sulfates; and the sodium or potassium salts of alkyl phenol ethylene oxide ether sulfates with about 1 to about 10 units of ethylene oxide per molecule, the alxy groups of which have about 8 to about 12 carbon atoms.

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To other anionic ones that can be used for the present purposes Detergent compounds include the water soluble salts of esters of c6 sulfonated fatty acids having about 6 to 20 carbon atoms in the fatty acid group and about 1 to 10 carbon atoms in the ester group; the water-soluble salts of 2-acyloxy-alkane-1-sulfonic acids with about 2 to 9 carbon atoms in the acyl group and about 9 to about 23 carbon atoms in the alkane radical; Alkyl ether sulfates with about 10 to 20 carbon atoms in the alkyl radical and about 1 to 30 mol Ethylene oxide; water-soluble salts of olefin sulfonates with about 12 to 24 carbon atoms; water soluble salts of Paraffin sulfonates with about 8 to 24, especially 14 to 18 Carbon atoms, and ß-Alkyloxyalkansulfonate with about 1 to 3 carbon atoms in the alkyl radical and about 8 to 20 carbon atoms in the alkane radical.

Mixtures of anionic surfactants can also be used, for example 5: 1 to 1: 5 mixtures of an alkylbenzenesulfonate having 9 to 15 carbon atoms in the alkyl radical or mixtures thereof, the cation being an alkali metal, preferably sodium, and about 2 to about 15 wt.% of a Alkylethoxysulfats having 10 to 20 carbon atoms in the alkyl radical and 1 to 30 ethoxy groups, or mixtures thereof, with an alkali metal cation, preferably sodium.

Water-soluble, non-ionic synthetic detergents can also be used as detergent components according to the invention. These nonionic detergents can be broadly defined as compounds produced by the condensation of alkylene oxide groups (hydrophilic nature) with an organic hydrophobic compound that is aliphatic or alkyl aromatic in nature can arise. The length of the polyoxyalkylene group that ends with

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the respective hydrophobic group is condensed, can can easily be adjusted to obtain a water soluble compound of the desired degree or balance between receives hydrophilic and hydrophobic elements.

Examples of suitable non-ionic detergents include:

oxide-

1. The polyethylene condensates of alkylphenols for example

the condensation products of alky! phenols with a Alkyl radical with 6 to 12 carbon atoms in straight chain or branched chain configuration and ethylene oxide, where the ethylene oxide in amounts of 5 to 25 moles of ethylene oxide per Moles of alkylphenol is present. The alkyl substituents in these compounds can, for example, from polymerized propylene, Diisobutylene, octene and nonene originate. Further examples include dodecyl phenol, with 12 moles of ethylene oxide per mole of phenol condensed; Dinonylphenol condensed with 15 moles of ethylene oxide per mole of phenol; Nonylphenol, with 20 moles of ethylene oxide per Mol nonylphenol condensed, and Diisooctylphenpl ^ with 15 mol Condensed ethylene oxide.

2. The condensation product of primary or secondary aliphatic Alcohols containing 8 to 24 carbon atoms in either a straight chain or a twisted chain configuration

with 1 to about J> 0 moles of alkylene oxide per mole of alcohol. The aliphatic alcohol preferably contains between 9 and 15 carbon atoms and is between 2 and 12, desirably between 5 and 8 moles of ethylene oxide per mole of aliphatic! Alcohol ethoxylated, such nonionic surfactants are preferred from the point of view that they give good to excellent detergent action on greasy and oily dirt and in the presence of hardness-sensitive anionic surfactants such as alkylbenzenesulfonates. The preferred surface

03G009 / 0 5 6 6

active are made from primary alcohols that are either linear (such as those from natural fats or made from ethylene by the Ziegler process, for example myristyl, cetyl, stearyl alcohol) or partially branched, such as the dobanols and neodoles, the have about 25 % 2-methyl branching (Dobanol and Neodol are trademarks of Shell) or Synperonics, which have about 50 % 2-methyl branching (Synperonic is a trademark of IJCI.) j or the primary alcohols with more than 50 % branched chain structure sold under the trademark Lial by Liquichimica. Specific examples of non-ionic surfactants falling within the scope of the invention are Dobanol 45-4, Dobanol 45-7, Dobancl 45-11, Dobanol 91-3, Dobanol 91-6, Dobanol 91-8, Synperonic 6, Synperonic 14, the condensation products of coconut alcohol with an average of between 5 and 12 moles of ethylene oxide per mole of alcohol, in which the coconut alkyl radical has 10 to 14 carbon atoms, and the condensation products of tallow alcohol with an average of between 7 and 12 moles of ethylene oxide per mole of alcohol, in which the Ta -Ig fraction has essentially between 16 and 22 carbon atoms. Secondary, linear alkyl ethoxylates are also suitable in the present mixtures, in particular the ethoxylates of the Tergitol series with about 9 to 16 carbon atoms in the alkyl portion and up to about 11, in particular from about 3 to 9 ethoxy radicals per molecule.

3 · The compounds that are formed by condensation of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol is. The molecular weight of the hydrophobic portion generally falls in the range of about 1500 to 1800. Such synthetic, non-ionic detergents are under the

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Trade name "Pluronic" in the market and are used by supplied by W'yandotte Chemicals Corporation.

The semi-polar, nonionic detergents include water-soluble amine oxides with an alkyl moiety with about 10 to 28 carbon atoms and two radicals from the group from alkyl radicals and hydroxyalkyl radicals having 1 to about 3 carbon atoms; water soluble phosphine oxide detergents with an alkyl content of about 10 to 23 carbon atoms and two radicals from the group consisting of alkyl radicals and hydroxyalkyl radicals with about 1 to 3 carbon atoms; and water-soluble sulfoxide detergents having an alkyl portion about 10 to 28 carbon atoms and a radical from the group of the alkyl and hydroxyalkyl radicals having 1 to 3 carbon atoms.

Ampholytic detergents include derivatives of aliphatic or aliphatic derivatives of heterocyclic !? secondary and tertiary amines in which the aliphatic radical can be straight-chain or branched and in which one of the aliphatic Substituents have about 8 to 18 carbon atoms and at least one aliphatic substituent contains an anionic, water-solubilizing group.

Second ionic detergents include derivatives of aliphatic quaternary ammonium, phosphonium and sulfonium compounds, in which the aliphatic portion is straight-chain or branched can be and wherein one of the aliphatic substituents has about 8 to 18 carbon atoms and one is an anionic Contains water-solubilizing group. The further use of zwitterlonic detergents is described in US Pat. No. 3,925,262 and 3,929,678.

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It should be noted that any of the above detergents can be used separately or as a mixture.

A particularly preferred mixture of surface-active agents is an anionic / non-ionic mixture, in particular a mixture of a Cg-Cpp-alkylbenzenesulphonate and a CjQ-CpQ-alkanol ethoxylated with 3 to 30 mol of ethylene oxide per mol of alkanol. Particularly preferred mixtures contain a C, ₂ -alkylbenzenesulfonate and C ₁ ^ -C., _[ --Alcohol- (7) -ethoxylate in proportions of 5: 1 to 1: 3. » and preferably from 3: 1 to 1: 1. In even more preferred mixtures, a fatty acid soap is added to the mixture described above, preferably a C, _{0 -Cp Q} soap in an amount of 1 to 5 %.

Polycarboxylate builder

Another mandatory component of the mixtures according to the invention is a polycarboxylate builder of the type in which the carbosylate anion of the highest basicity has a logarithmic Acidity constant (pK-,) less than about 9, preferably between about 2 and about 8.5 * and particularly preferably between about 4 and about 7.5 *.

The logarithmic acidity constant is thus defined with reference to equilibrium

H ⁺ + AH ⁺ A

wherein A is the fully ionized carboxylate anion of the Framework salt means.

The equilibrium constant is therefore

K ₁ = Γη * Al

and PK ₁ = log _1Q K.

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For the purposes of this description, the acidity constants were determined at 25 ° G and ionic strength 0. V / o possible, literature values were used (see Stability Constants of Metal-Ion Complexes, Special Publication Ko. 25, The Chemical Society, London), where there were doubts, they were determined by potentiometric Titration determined with a glass electrode. In the case of polymeric polycarboxylate builders, the various carboxylate acidity constants using the Katchalsky form of the Henderson-Hesselbach equation (see- A. Katchalsky and 'P. Spitnik, J. Polym. Sci., 1957, 23, 451).

Preferred carboxylates can also be determined with the aid of their stability constant of the calcium ion (pK ~ ++) analogous to pK, defined

oa χ

are according to the equations

where K. ",, = Cca ++ λ!
Ca _T + -

The carboxylate preferably has a pKp in the range from about 2 to about 7, in particular from about J> to about Again, literature values of the stability constants have been used where possible. The stability constant is determined at 25 ° C. and an ionic strength of O by a measuring method with a glass electrode, which is described in " ^H Complexation in Analytical Chemistry" by Anders Rongbom (1963).

The carboxy plat- or polycarboxylate builder can be monomeric, be oligomeric or polymeric, although monomeric carboxylates because of their price and properties in general to be favoured.

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1i

Monomeric and oligomeric builders can be acyclic, alicyclic, heterocyclic and aromatic carboxylates the general formulas

(a) Cc)

or

where R, hydrogen, a C-,. ,,, - alkyl or alkenyl radical, which is optionally substituted by hydroxyl, carboxy, sulfo or phosphono groups or is bonded to a polyethyleneoxy radical with up to 20 ethylene oxide groups, R ₂ Hydrogen or a C, ^ -alkyl or alkenyl or hydroxyalkyl or aralkyl radical, the sulfo or phosphono group, X a single bond, O, S, SO, SOp or NR ,, Y hydrogen, the carboxyl, hydroxy, carboxymethyloxy group or a C _n ., "- alkyl or alkenyl radical, the

x-pu

if substituted by hydroxyl or carboxy groups, Z is hydrogen or the carboxyl group, m is an integer of 1 to 10, η an integer from J5 to 6, p, q integers from 0 to 6, where ρ + q is a number from 1 to 6, where X, Y and Z when repeating in a given Molecular formula can have the same or different meanings.

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Suitable carboxylates with a carboxyl group include lactic acid, glycolic acid and their ether derivatives, which are described in BE-PSS 821 368, 821 369 and 821 370. Polycarboxylates containing two carboxyl groups include the water-soluble salts of succinic acid, malonic acid, ethylenedioxy-diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as those described in DOSS 2,446,686 and 2,446,687 and in US Pat. No. 3,935,257 ^v thercarboxylates and the sulfinyl carboxylates described in BE-PS 84O 623. Polycarboxylates containing three carboxyl groups include, in particular, water-soluble citrates, aconites and Eitracon- GB-PS 1,389,732 described lacfoxysuccinates and the aminosuccinates and oxypolycarboxylate compounds described in NL-PA 7,205,873, such as the 2-oxa-1,3-propane-tricarboxylates described in GB-PS 1,387,447.

Polycarboxylates containing four carboxyl groups include the oxydisuccinates described in GB-PS 1 26l 829, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1,1,2,3-propane tetracarboxylates. Sulfo substituents Containing polycarboxylates include those described in GB-PSS 1,391,421 and 1,398,422 and in US Pat. No. 3,936,448 Sulfosuccinate derivatives and the sulfonated derivatives described in GB-PS 1,082,179 Citrates, while polycarboxylates containing phosphono substituents are described in GB-PS 1,439,000.

Alicyclic and heterocyclic polycarboxylates include the cyclopentane-ciSjCiSiCis-tetracarboxylate, Cyclopentailienidpentacarboxylat, 2,3 * 4,5-tetrahydrofuran ~ cis, cis-cis-tetracarboxylate, 2,5-tetrahydrofuran-cis-dicarboxylate, 2,2,5 * 5-

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Tetrahydrofuran tetracarboxylate, 1,2,3,4,5,6-hexane hexacarboxylate and carboxymethyl derivatives of polyhydric alcohols such as sorbitol, manitol and xylitol. Aromatic polycarboxylates include mellitic acid, pyromellitic acid and the phthalic acid derivatives described in GB-PS 1 425 34 ^ are.

Of these, the preferred are polycarboxylates the hydroxycarboxylates with up to 3 carboxyl groups per Molecule. Polymeric polycarboxylates suitable for use in the present blends are preferably those homo- or copolymeric polycarbonate oxylates, which have a molecular weight of at least 500 and carboxylic acid units or their salts of the general formulas

(A)

X C

C -

COOH

wherein X, Y and Z are each selected from the group consisting of hydrogen, methyl, aryl, alkaryl, carboxyl, hydroxyl and carboxymethyl, at least one of the radicals X, Y and Z is selected from the group of carboxyl and carboxymethyl, with the proviso that X and Y only then Can be carboxymethyl when Z is carboxyl or carboxymethyl, and where only one of the radicals X, Y or Z Can be methyl, aryl, hydroxyl or alkaryl, or

ι ¹

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wherein R, and Rp each represent a hydrogen atom or a Alkyl radical with 1 to J carbon atoms and FL H, OH or CH-, contain.

Type A polycarboxylates include those from the monomeric poly acids "maleic acid, citraconic acid, aconitic acid, Fumaric acid and mesaconic acid, pheny! Maleic acid, Benzy! Maleic acid, itaconic acid and methylenemalonic acid or their anhydrides are formed.

Type B polycarboxylates include those which, at least

/ carbon— in structural relation, from the monomeric monoacids Acrylic acid, Cxi-hydroxacrylic acid or methacrylic acid were formed are.

Preferably the above carboxyl monomer provides at least 45 moles of the types of monomers in the polymer. The polymer can be made from homopolymers of the above carboxylic monomers or copolymers of two or more of the above carboxyl monomers or copolymers of one or several of the above carboxylic monomers with one unsaturated one be polymerizable monomer, which differs from the specified Car boxy! 'monomers.

A preferred copolymer of the latter type comprises Units of the general formula,

1- HO CH ₂ -I

wherein.R-, a C, _C, p-alkyl radical or a C -, _-, p-acyl radical means and optionally hydroxy- or carboxy-substituted can be.

030009/056 6

Examples of polycarboxylates of the above classes are Sodium polymaleate (molecular weight 2500), maleic acid / acrylic acid copolymer, 70 OO-acrylic acid / hydroxymaleate copolymer, Methyl vinyl ether / maleic acid copolymer, ethyl vinyl ether / maleic acid copolymer, Sodium polymaleic acid sulfonate, 1: 3 copolymer of acrylic acid and itaconic acid, a 1: 4 copolymer of 3-butenoic acid and methylenemalonic acid, a 1: 9 copolymer of isocrotonic acid and citraconic acid, a 1: 1.9 copolymer of methacrylic acid and aconitic acid and 1.2: 1 copolymer of 4-pentenoic acid and itaconic acid.

The polymeric polycarboxylates have average molecular weights (generally measured as the viscosity average in 1m NaOH according to the specification of NL-PS 78/04276) in the range from about 500 to about 2,000,000, and calorie stability constants in the range from 2 to about J.

The polyphosphonate

The preferred polyphosphonates have a calcium stability constant pK " ^{in the} range from about 5 to

Ca ++

about 10.5 *, as desired, from about 6 to about 10, and in particular from about J, Q to about 9 * 5. The definition and method for measuring the stability constants are described in greater detail above.

Preferred polyphosphonates are those of the general formula =

030009/0568

where η at least 2, M is an alkali metal, ammonium or substituted ammonium cation and Z is a connecting organic radical with the effective valence η mean. Z preferably denotes a hydrocarbyl or a hydrocarbyl-substituted amino radical. Various specific classes of polyphosphonates useful in the present invention are set out below described.

The polyphosphonates can be derived from acids of the formulas

R, H
ρ - η 1 PO ₃ H ₂

and-

(D

—A

^PO 3 ^H 2

(2)

where R, and Rp hydrogen or CHpOH, η an integer from 3 to 1Oj R ^ hydrogen, an alkyl radical with 1 to about 20 carbon atoms, alkenyl radical with 2 to about 20 carbon atoms, aryl radical (for example phenyl and naphthyl), phenylethenyl or benzyl radical, halogen (for example chlorine, bromine and fluorine), the amino group, a substituted amino group (for example dimethylamino, diethylamino, N-hydroxy-N-ethylamino, acetylamino), -CH ₂ COOH, -CH ₂ PO ₃ H ₃ , -CH (PO H ₂ ) (OH) or -CH ₂ CH (PO Hg) ₂ and RV / water, lower alkyl (for example chlorine, bromine and fluorine _; the hydroxyl group, -CH ₂ COOH, -CH ₂ PO _{5 is} H ₂ or -CH ₂ CH ₂ PO ₅ H ₂ .

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The polyphosphonates of the above formula (I) which can be used include propane-1,2, J5-triphosphonic acid, butane-1,2,3,4-tetraphosphonic acid, hexane-1,2,3,4-5, 6-hexaphosphonic acid, hexane hydroxy-2,; 5,4,5,6-pentaphosphonic acid, hexane-1,6-dihydroxy-2,3j 4,5-tetraphosphonic acid, pentane-1,2, J5,4,5-pentaphosphonic acid, heptane-1, 2,3, 4,5,6,7-heptaphosphonic acid, octane-1,2, j5,4-5,6,7,8-octaphosphonic acid, nonane-1, 2,3 ₃ ^ ₃ 5, 6, J ₃ 8, 9-nonaphosphonic acid, decane-1,2, j5> 4 ·, 5j6,7j 8j9i 10-decaphosphonic acid and the salts of these acids, for example the sodium, potassium, calcium, magnesium, ammonium, triethanolammonium , Diethanol ammonium and monoethanol ammonium salts.

The polyphosphonates of the above formula (2) that can be used include ethane-1-hydroxy- ^ l-diphosphonic acid, methanediphosphonic acid, Methane hydroxydiphosphonic acid, ethane-1,1,2-triphosphonic acid, Propane-lilj ^ j ^ -tetraphosphonic acid, ethane-2-phenyl-1,1-diphosphonic acid, Ethane-2-naphthyl-l, 1-diphosphonic acid, methanophenyldiphosphonic acid, ethane-l-amino-ljl-di-

di—
phosphonic acid, methane chlorodiphosphonic acid, "ionane-5,5-diphosphonic acid, n-pentane-1,1-diphosphonic acid, methanedifluorodiphosphonic acid, methanedibromodiphosphonic acid, propane-2,2-diphosphonic acid, ethane • -2-carboxy-l, l-diphosphonic acid , Propane-1-hydroxy-1,1,3-triphosphonic acid, ethane-2-hydroxy-1 / 1,2-triphosphonic acid, ethane-1-hydroxy-1,1,2-triphosphonic acid, propane-1,3-diphenyl -2,2-diphosphonic acid, nonane-1,1-diphosphonic acid, hexadecane-1,1-diphosphonic acid, pent-4-en-1-hydroxy-1, 1-diphosphonic acid, octadec-9-en-1-hydroxy-1, l-diphosphonic acid , 5-phenyl-l, l-diphosphonoprop-2-en, octane-1, 1- diphosphonic acid, dodecane-1,1-diphosphonic acid, phenylaminomethanediphosphonic acid, naphthylamino-methane-diphosphonic acid, Ν, Ν-dimethylaminomethyldiphosphonic acid, N- (2- Hydroxyethyl) aminomethanediphosphonic acid, N-acetylaminomethanediphosphonic acid, aminomethanediphosphonic acid and the salts of these acids, for example the sodium, potassium, calcium, magnesium, ammonium, triethanolammonium, diethanolammonium and monoetha nolammonium salts.

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Mixtures of any of the above phosphonic acids and / or salts can be used in the mixtures of the invention. Processes for the production of these classes of substances are described in US Pat. No. J> 488,419.

For the purposes of the present invention it is preferred that the polyphosphonates are free of hydroxyl groups.

Another useful and preferred class of polyphosphonates are the aminotrialkylidene phosphonates; these include acids of the general formula

R 'O

I ⁵ Il

N-I-C P OH

L OH

in which R, - and IL- are hydrogen or C, -0, -alkyl radicals. 5 ο 14

Examples of compounds from this general class are aminotri (ethylidene phosphonic acid), aminotri (ethylidenephosphonic acid) and aminomono- (methylenephosphonic acid) di (isopropylidene phosphonic acid).

Polyphosphonates which are particularly preferred here have the general formula

- - iCH ₂ - CH ₂ - N) _n - R

where η is a number from 1 to 14 and each R is individually hydrogen or CHoPO-zHp or a water-soluble salt thereof, with the proviso that at least half of the radicals R CH _? PO H ₂ residues or water-soluble salts thereof. The polyphosphonate is particularly preferred

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general formula

\ K - (CH ₂ - CH ₂ - NJ ₂ - R ¹

R ¹

wherein each R radical is a CEUP (XHp radical or a water-soluble Salt of it means.

Other suitable polyphosphonates are those derived from triethylenetetramine, tetraethylene pentamine, pentaethylene hexamine and polyethyleneimines such as Montrex 600 (Trademark of DOW Chemical Co. for a molecular weight polyethyleneimine about 600).

The polyphosphonate is preferably added to the mixtures according to the invention in an amount of at least 0.1 %, and generally in an amount of from about 0.2 to about 3 * 5% by weight, more preferably from about 0.5 to about 2.2% by weight . % of the mixture added.

Optional components

The mixtures according to the invention can of course be supplemented by all types of detergent components, either by adding these components to the aqueous slurry intended for spray drying or by adding these components to the mixtures according to the invention after the drying stage. Soil suspending agents in amounts of about 0.1 to 10 wt.%, Such as water-soluble salts of carboxymethylcellulose, Carboxyhydroxymethylcellulose and polyethylene glycols having a molecular weight of about 400 to 10,000 are common components according to the invention.

03 0 009/0566

Mixtures containing monomeric polycarboxylates as the builder component can also be supplemented with about 0.1 to about k% of the polymeric polycarboxylates defined above as soil suspending agents, for example

, optical by "Gantrez ANII9. Dyes, pigments, / brighteners and fragrances can be used in varying amounts as desired be admitted. Bleaching agents suitable for present purposes include percarbonates, perborates, and Activators for this.

In addition, other materials such as fluorescent substances, antiseptics, germicides, lesser Amounts of enzymes and anti-caking agents such as sodium sulfosuccinate, sodium benzoate are added. Enzymes suitable for use herein include those disclosed in U.S. Patents 3,519,570 and 3,553,139 (McCarty and McCarty, issued on 4-7.1970 and 5.I.197I, respectively) are described.

Also additional inorganic alkaline detergent builder salts can be added, although large amounts of strongly alkaline framework salts and phosphorus-containing salts Framework salts should be avoided. In particular, the solution pH of the mixture should be less than about 10, greater preferably in the range from about 6 to about 9 * 5. The "solution pH" is defined as the pH of a 1 ^ igen solution of the E & ergensmixture in distilled Water.

Inorganic framework salts include, for example, alkali metal carbonates, -tetraborates, -pentaborates, -aluminates, -bicarbonates, -sesquicarbonates and water-insoluble aluminosilicates. Such an aluminosilicate, which is used in the inventive

Means

030009 / 056ß

useful is an amorphous, water-insoluble hydrated one Compound of the formula Na (xAlO .ySiO), wherein χ is a number from 1 to 1.2 and y is 1, the amorphous material being further characterized by a

Mg exchange capacity of about 50 mg-Aq. CaCO - * / g to

about ISO mg -'- q. CaCO, / g. This builder from ion exchangers is in published Irish patent application 1505/74 (B.H. Gedge et al., filed on described in more detail.

A second water-insoluble synthetic aluminosilicate ion exchange material, which is _{presently brittle, has the formula Na (AlO 0} ). (SiO ₅ ) xHLO, where ζ and y are integers of at least 6., the molar ratio ζ to y in the range of 1.0 to about 0.5 and χ is an integer from about 15 to about 264, the aluminosilicate ion exchange material having a particle size diameter of about 0.1 to about 100 microns, a calcium ion exchange capacity of at least ett> 200 mg .4 "q./g and a calcium ion exchange rate of at least eti
8l4 874).

of at least about 1.9 ² / min / g (for description, see BE-PS

Inorganic phosphate builders can also be added to the mixtures according to the invention, although they should only be added in smaller amounts so that the total phosphorus content is less than 6, and preferably less than 5% by weight of the mixture. The polyphosphates can be chain-like polyphosphates as well as tripolyphosphates, tetrapolyphosphate and pentapolyphosphate or metaphosphates such as tetrametaphosphate, pentametaphosphate and hexametaphosphate. Higher polyphosphates with the _{empirical formulas Na-, 5P 1} A ⁰ K ^ and Na, pP-, qO. ,, can also be used. Mixtures of chain-like polyphosphates and metaphosphate can also be used.

030009/0566

Preferred polyphosphates are the chain-like polyphosphates with 3 to 9 *, preferably 4 to 6 phosphorus atoms per molecule. A particularly suitable material is (believed to be a sodium _{pentaphosphate)}} which is brought by Albright and Wilson on the market and in amounts up to 10%, in particular up to 4 wt. F ₀ of the mixed, "627 Phosphate Glass" was added and advantages particularly with regard to the removal of particulate clay.

Organic carboxylates or polycarboxylates with a pK greater than 9 can also be added, for example nitrilotriacetates or olefin-maleic acid copolymers. These additional builders are preferably but only in small amounts present, for example up to about 8 wt.% Of the mixture.

Another optional component of the mixtures according to the invention is a foam suppressor. Soap is an effective foam suppressor, especially the C £> ~ ος> "soaps, for example those obtained by neutralizing" Hyfac "(trademark) fatty acids. These are hardened fish oil fatty acids with predominantly chain lengths

C _n QC ₀ ,,. However, not made of Soap foam Io you

damper preferred. A preferred foam suppressor includes Silicones. In particular, one can use a particulate foam suppressor use the silicone and silica in releasable V / eise in a water-soluble or water-dispersible, essentially non-surface-active, and detergent-impermeable carrier included. Foam suppressors of this type are described in GB-PS 1 ^ 07 997.

Am very suitable granular (in the form of prills) foam damper 7 Jo silicic acid / silicone containing (85% by weight silanized silicic acid, 15 <fo of silicone DOtV _Corning.); 65 % sodium tr! Polyphosphate 25 % tallow alcohol (EO ) ^ _{} ΐ} - (i.e. condensed with 25 mol of ethylene oxide) and 3 % moisture. Also suitable and preferred is a combination of 0.02 to 5% by weight , in particular about 0.3 % of the mixture of an essentially water-insoluble wax or wax mixture which melts at 35 to 125 ° C. and has a saponification number of less than 100, and an antifoam amount, usually about 2 % of the mixture, of a particulate antifoam of the type described above.

Another desirable component of the invention Mixtures is a water-soluble, cationic, surface-active substance described in the European patent application 782ΟΟ Ο5Ο.9 described type. The cationic surface-active Fabric improves when used in combination with anionic and non-ionic surfactants in certain amounts and proportions, the detergent effect of the formulation against oily Stains. Preferred cationic surfactants have the general formula

where R is selected from the groups Co_2 ₀ alkyl, alkenyl, alkaryl, R is selected from C, u alkyl or benzyl, A is an anion and m is the number 1, 2 or J5, provided that when m is the number 2 , R has fewer than 15 carbon atoms and, when m is the number 3, R has fewer than 9 carbon atoms.

C, p- and C-alkyltrimethylammonium salts are special preferred.

G3G0Ü9 / .O5 & S

In the production of granular detergent scales according to the invention, the constituents can be mixed in any order and in palverform or in liquid form, for example in an aqueous dispersion. The mixture can be spray dried, drum dried, freeze dried, or otherwise dried to form a granular product. Usually a moisture content of about 3 to about 10 percent is recommended for achieving non-stick, free flowing grains.

Liquid detergent mixtures according to the invention can be used as optional ingredients, organic carriers or solvents such as lower aliphatic alcohols having 2 to 6 carbon atoms and 1 to 3 hydroxyl groups, zither of Diethylenglyeol and lower aliphatic monoalcohols having from 1 to h carbon atoms, or their mixtures. Liquid products can also contain hydrotropes such as the water-soluble alkylarylsulfonates with up to 3 carbon atoms in the alkyl radical, such as the sodium, potassium, ammonium and ethanolamine salts of xylene, toluene, ethylbenzene and isopropylbenzene sulfonic acids.

Examples 1 to 7

Builder-containing low-foam detergent mixtures are used manufactured according to the following recipe. To make the products, a slurry is created that contains all of the Contains ingredients other than bleach and enzyme, and the slurry is then spray dried to form of a granular intermediate. Bleach and enzyme are dry blended with the granular intermediate with formation of the specified mixtures. All numbers are percentages by weight.

030 0 09/0566

Al - 1.0 7.0 * 3 4th 2857294 5 6th 7th 1.0 - 3.0 1.0 8.1 - - 8.0 Sodium-linear-
dodecylbenzenesulfonate Example no
1 2 - 2.5 7.6 - - 4.0 - Dobanol 45-7 (9) 8.0 proteolytic enzyme (6) - - _ 1.9 10.0 1.0 _ Sodium tallow alcohol
sulfate - Gantrez AN119 (7) 4.2 - 11.5 3.0 - - Sodium Coconut Soap Gantrez AN139 (8) - - - - 6.0 4.2 Sodium silicate
(Si0 ₂ : Na ₂ 0.-3.2: 1) 3.0 Sodium sulfate, water
and various 5.5 4.0 - 2.0 8.0 - Dobanol £ 5-4 (10) 6.1 12.0 - - - 2.0 - Sodium-alkyl (C ₁ J, _ ₁ g) -
triethoxysulfate - l4.0 - - 15.0 - 10.0 Sodium bicarbonate - 5.0 10.0 15.0 16.0 24.0 17.0 Tri-
Sodium citrate - 15.0 2.0 - - 8.0 Sodium tripolyphosphate 20.0 0.8 5.0 15.0 - - - Sodium perborate,
Tetrahydrate - 0.5 0.8 0.8 0.8 0.8 1.4 Sodium arboxymethyl
cellulose 10.0. 2.0 0.5 2.0 - 0.5 2.0 Tallow alcohol (EO) ₁₁ 0.8 o, 3 - 2.0 2.0 2.0 2.0 Silicone prills (1) 0.5 - o, 5 0.3 0.3 o, 3 0.3 2.0 - 1.5 1.0 - - - microcrystalline wax
(2). 0.3 1.0 - 0.5 - 1.0 2.0 Dequest 2060 (3) 1.0 - - 1.0 - " - Dequest 2040 (5) - - - 0.5 - 0.8 Dequest 2010 (4) 2.0 5.0 - 7.0 - - 0.5 - - 1.0 - on 100-

030009/0568

Bottom Notes:

(1) Containing 0.14 parts by weight of an 85:15 (by weight) mixture of silanized silica and silicone, granulated with 1.3 parts of sodium tripolyphosphate, and 0.56 part of tallow alcohol condensed with 25 moles of ethylene oxide.

(2) "Witcodur 272", P. 83 ° C (trade name)

0) Trade name for diethylenetriaminepenta (methylene) phosphonic acid, a commercial product of Monsanto.

(4) trade name for ethane-I-hydroxy-1,1-diphosphonic acid, Monsanto commercial product

(5) Trade name for ethylenediaminetetra (methylenephosphonic acid), Monsanto commercial product

(6) Maxatase: 15 % pure enzyme, commercial product from Gist Brocades

(7) Trade name for maleic anhydride / vinyl methyl ether copolymer, probably average molecular weight about 240,000, hand product of GAF. It was before the Addition pre-hydrolyzed with NaOH.

(8) Trade name for maleic anhydride / vinyl methyl ether copolymer, Presumably average molecular weight about 500,000, GAP commercial product. It was before the Addition pre-hydrolyzed with NaOH.

(9) Trade name: primary C -. *, -C ,, - alcohols, condensed with 7 mol of ethylene oxide, commercial product of Shell.

(10) Trade name: primary C ^, - alcohols, with 4 mol Condensed ethylene oxide, a Shell product

These products provide excellent cleaning and l '/ ice level, especially at low washing temperatures and with bleachable soiling.

030009/0566

Products with improved properties are obtained by replacing the Natrxurnalkylbenzolsulfonat by ^C 10-22 ~ ^{01ei> insulfonafci} C ₁₀ _ ₂₀ -paraffinsulfonate and zwitterionic detergents such as C-. _Q _, ο-Alkyldimethylammoniumpropansulfonat or -hydroxypropanesulfonat.

Improved properties are also obtained by replacing the "Gantrez ANII9" with the sodium salts of a copolymer of methyl methacrylate and maleic acid, in which the molar ratio of the monomers is about 1: 1 and the molecular weight is about 10,000, of a 1: ^ copolymer Acrylic acid and itaconic acid, a 1: 4 copolymer of ^ -butyric acid and methylenemalonic acid, a 1: 9 copolymer of isocrotonic acid and citraconic acid, a 1,2: 1 copolymer of 4-pentenoic acid and itaconic acid and the poly (<j £ -hydr oxy- acrylic acid) with a molecular weight of about 50,000.

Improved properties are also obtained if, in the above examples, trisodium citrate is replaced by equal amounts of water-soluble salts of lactic acid, glycolic acid, succinic acid, malonic acid, ethylenedioxy-diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid, fumaric acid, aconitic acid, citraconic acid, carboxoxysuccinic acid, citraconic acid, carboxoxysuccinic acid , 2-Oxa-l, 1, ^ - propane-tricarboxylic acid, 1,1,2,2-ethanetetracarboxylic acid, 1,1,3 » J5-propane-tetracarboxylic acid, 1,1,2, ^ - propane-tetracarboxylic acid, Citrex S5 (commercial product from Citrique, Beige), cyclopentane-ciSjCiSjCis-tetracarboxylic acid, cyclopentadienide-pentacarboxylic acid, 2, ^, 4-, 5-tetrahydrofuran-cis, ice, ice-tetracarboxylic acid, 2nd, 5-tetrahydrofuran-cis-dicarboxylic acid, 2 , 2,5,5-tetrahydrofuran-tetracarboxylic acid, 1,2, ^, 4,5 * 6-hexane-hexacarboxylic acid, mellitic acid or pyromellitic acid replaced.

030009/0566

Examples 8-13

Granular detergent mixes were made according to the following recipe
manufactured:

Examples:

8 9 10 11 12 13

Linear C, p-alkylbenzene

sulfonate " ¹ 7.0-8.0 5.0 3.0 10.0

Myristyl trimethyl

ammonium chloride - - - 5.0 -

8.0 2.4 1.5 3.0 -

Tallow alcohol sulfate 3.0 - 0 Dobanol 45-Ξ-7 - 8th, Tallow alcohol (EO), 3.0 - 0 Dobanol 45-Ξ-4 - 4, 0 C ₁₂ soap - 2, C ₂₂ soap 2.0 -

2.0 -

3.0 4.0 - 2.0

Sodium tripolyphosphate 1.0 2.5 4.5 - 8.0 1.5

Sodium pentametaphos

phat - - -. 1.5

Zeolite A

(Particle size 5 jam) 25.0 30.0 45.0 - 15.0 28, Ό

Gantrez AN 119 0.8 8.0 - 2.0 1.5 - Gantrez AN I36 - - 1.5® - - - Dequest 2θ4θ 1.0 - 0.5 - 0.1 - De quest 2θ6θ - 2.0 0.5 0.2 - 1.5 Sodium silicate
(Si0 ₂ : Na ₂ 0 = 1.6) 3.0 4.0 5.0 4.0 7.0 Sodium citrate 15.0 10.0 20.0 16.0 6.0 10.0 Protease enzyme 0.5 0.5 - 0.5 - 0.5 Sodium perborate - - - 5.0 - 10.0 Sodium percarbonate 8.0 - 12.0 - - 10.0 Sodium sulfate,
Humidity and ver
divorced -to 100

030009/0566

The mixtures of all of the above examples result in good washing behavior, especially in the case of bleachable soils and stains and at low wash temperatures compared to blends that do not contain polyphosphonates.

Similar results are obtained when using the tripolyphosphate replaced by a P.p-vitreous phosphate. The anionic / non-ionic active ingredient system of Examples 10 up to 13 can be replaced by purely non-ionic ones Systems, for example with Dobanol 45-E-7 alone or with 8: 1 mixtures of for example Dobanol 45-E-7 and Dobanol 45-E-4. The zeolite A in Examples 8 to 10, 12 and 13, can be entirely or partially replaced by an amorphous Sodium aluminosilicate can be replaced. Improved properties are also achieved when the lauryltrimethylammonium chloride is replaced by myristyl trimethylammonium bromide, Decyl-trimethylammonium chloride, dioctyl-dimethylammonium bromide, Lauryl dichlorobenzyldimethylammonium chloride and cetyl trimethylammonium ethosulfate. Improved properties can also be achieved if the sodium citrate is replaced by disodium succinate, trisodium carboxymethyloxysuccinate, Trisodium-2-oxa-l, l, 3-propane-tricarboxylate and Citrex S-5

030009/0566

Claims (10)

Patent claims: 1. Detergent mixture with a phosphorus content of not more than 6 % and a pH value in 1 ^ iger aqueous solution of less than 10, can be indicated by a) 2 to 75 % of an organic detergent selected from anionic, non-ionic, amphoteric and zwitterionic detergents and their mixtures, b) 4 to 50 % of a carboxylate or polyearboxylate builder having an logarithmic acidity constant (pK-,) of the first carboxyl group of less than 9, and c) 0.01 to 4 % of a polyphosphonic acid or a salt thereof. 2. Mixture according to claim 1, characterized in that the carboxylate builder einai ρΚ -, - value in the range from 2 to 8.5. 3 · Mixture according to claim 1 or 2, characterized by a pH value in 1 ^ iger aqueous solution in the range from 6 to 9.0. 4. Mixture according to one of the preceding claims, characterized in that the carboxylate builder has a logarithmic calcium stability constant in the range from 2 to J. 5. Mixture according to one of the preceding claims, characterized in that the carboxylate builder is a organic, monomeric or oligomeric, acyclic, ORIGINAL JNSPECTED 030009/0566 alicyclic, heteroeyclic or aromatic carboxylate of the general formula ζ J or
(c) * y is, wherein R, hydrogen, a C, -, Q-alkyl or Alkenyl radical which is optionally substituted by hydroxyl, carboxyl, sulfo or phosphono groups or to a polyethyleneoxy radical with up to 20 ethyleneoxy groups can be bonded, Rp hydrogen, a C,. -alkyl or alkenyl radical or hydroxyalkyl or alkaryl radical, the sulfo or Phosphono group, X is a single bond, O, S; SO, SO ₂ or NR j Y hydrogen, carboxyl, hydroxyl, carboxymethyloxy or a C-, ^ "- alkyl or alkenyl radical which is optionally substituted by hydroxyl or carboxyl groups, Z is hydrogen or the carboxyl group, m is an integer from 1 to 10, η is an integer from 3 to 6, p, q integers from 0 to 6, where ρ + q gives 1 to, mean, v / o for X, Y and Z when repeated in a given molecular formula can have the same or different meanings . 030009/0566 6. Mixture according to one of the preceding claims, characterized characterized in that the carboxylate builder consists of a water-soluble salt of citric acid, succinic acid, Malonic acid, maleic acid, fumaric acid, glycolic acid, tartaric acid or lactic acid or a derivative one of these acids or a mixture of these acid salts. 7 · Mixture according to one of the preceding claims, characterized characterized in that the carboxylate builder is a homo- or copolymeric polycarboxylate having a molecular weight of at least 500, the carboxylic acid units or their salts of the general formula C C contains, in which X, Y and Z are each selected from the group consisting of hydrogen, methyl, aryl, alkaryl, carboxyl, hydroxyl and carboxymethyl, -wherein at least one of the radicals X, Y and Z is carboxyl or carboxymethyl, under the condition, that X and Y can only be carboxymethyl if Z is carboxyl or carboxymethyl, and only one of the radicals X, Y and Z can be methyl, Άχψ.1, hydroxyl or alkaryl. 8. Mixture according to one of the preceding claims, characterized by; 5 to 30% of the carboxylate builder, 9. Mixture according to one of the preceding claims, characterized in that the polyphosphonate is the general formula 030009 / 0SS6 -.R has, where η is an integer from 1 to 14 and R individually hydrogen or CHpPO ^ Hp. or water soluble Salts thereof mean, with the proviso that at least half of the radicals R CH ^ PO ^ Hp. or represent water-soluble salts thereof. 10. Mixture according to one of the preceding claims, characterized by 0.2 to 3.5 % of the polyphosphonic acid or a salt thereof. 030009/0566