DE2605054A1 - CLEANING AGENT SCREEN AND DETERGENT PREPARATION - Google Patents

Description

2 6 O 5 over 4

D *. in the. DIrL-CiTEM ₁ YfAt ₁ TI *

Ditsa ^ '-.. "In H..J mm 09 Feb. 1976

DR. JUR. ϊ.; ~ .ϊ <Ϊ Out *. BElI. 623 FRANKPURi AM

Our registration number 20

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

Detergent builder and Detergent preparation

The invention relates to a detergent builder, which consists mainly of pyrophosphate and detergent preparations, which contain this builder.

For many years, detergents have been used to reduce water hardness mostly about 50 percent by weight sodium tripolyphosphate, based on the finished cleaning agent preparation, added. Because soluble phosphates like sodium tripolyphosphate

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accelerate overfeeding or aging of water bodies, Attempts have been made for several years to use detergent preparations to reduce the amount of liatriuatripolyphosphate contained as possible. The overfeeding of water bodies can be recognized by the rapid multiplication of algae.

Sodium tripolyphosphate contains 5 sodium atoms in its molecule, 3 phosphorus atoms and 10 oxygen atoms. When using sodium tripolyphosphate as a builder for cleaning agents each binds 1 mole of the tripolyphosphate anion as a soluble compound, one mole of calcium or magnesium cations in complex form. Sodium tripolyphosphate therefore binds Calcium and magnesium ions complex on a 1: 1 mole basis. That Calcium or magnesium tripolyphosphate is relatively stable in the washing solution, thus preventing the 'water hardness with anionic Detergents reacts and thus results in a better cleaning effect. The calcium or magnesium tripolyphosphate exists in the wash solution as a single trivalent negative anion. This trivalent calcium or magnesium tripolyphosphate anion does not fail during the washing process.

It was generally believed that sodium pyrophosphate was compared is an equivalent builder to sodium tripolyphosphate. However, it is also believed that sodium pyrophosphate causes overfeeding of water in a manner equivalent to sodium tripolyphosphate.

Sodium pyrophosphate contains one less phosphorus atom than sodium tripolyphosphate. This results from the empirical formula of sodium pyrophosphate, according to which there are 2 atoms of sodium and 2 atoms of phosphorus and contains 7 atoms of oxygen. Ss is known that sodium pyrophosphate forms a 1: 1 complex with calcium or magnesium ions on a mole basis. In the complex binding of calcium or Magnesium is produced by the tetravalent negative pyrophosphate anion the divalent negative calcium or magnesium pyrophosphate complex. This calcium or magnesium phyrophosphate complex is so stable in the washing solution that it removes the water hardness cations

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prevents interfering with the washing process.

Besides the molecular weight advantage that it "for a given weight Low phosphate allows for more pyrophosphate salt when tripolyphosphate is present in a preparation, it could be assumed that between the use of pyrophosphate and tripolyphosphate in detergent preparations there are only minor differences. However, this is not the case because the pyrophosphate anion in contrast to the tripolyphosphate anion under normal washing conditions as a dicalcium pyrophosphate salt fails. Attempts have hitherto been made to avoid the precipitation of pyrophosphates in washing solutions as much as possible, since the formed Salt tends to get on the fabrics and on the metal parts of the washing machine that come into contact with the washing solution to deposit. Furthermore, the precipitation of calcium; pyrophosphate under normal washing conditions in which Factors such as total hardness, pH and the ratio of calcium to Magnesium ions change from filling to filling, cannot be accurately predicted.

From the U ^ S. Patent Z 381 960 it is known that you can reduce the water hardness if you add the pyrophosphates to a solution containing hardness, which previously a supplementary alkaline material such as sodium orthophosphate, alkali hydroxides and carbonates, soap and sodium silicate with a SiO ^: Ha ₂ O ratio of more than 1.5 was added. It is known from US Pat. No. 2,326,950 that water hardness can be reduced with pyrophosphates if the pyrophosphates are added to the hardness-containing solution before supplementary alkaline material such as sodium borate, sodium metasilicate and disodium dihydrogen phosphate is added. According to both patents, the second component (pyrophosphate or additional alkaline material) is added to the solution before a macroscopic precipitate forms.

Us can be seen that pyrophosphate versus tripolyphosphate salts can be a more effective builder. The tetra-

B 0 9 B 3 6/0 9 5 3

valent pyropliosphate anion has for the first calcium ion, with which it reacts, a large constant of association. The first association product is the divalent monocalcium pyrophosphate anion. Compared to the second Calcined.on, with which the Monocalciumpyrophosphat the electrically neutral dicalcium pyrophosphate salt it has a very low association constant. In the absence of a material which is the dicalcium pyrοphosphate stabilized, a calcium ion can dissociate and another, more stable association component like looking for the body dirt on the textiles or the anionic cleaning agents. The calcium ions must be independent whether they are in free form or as a weak complex, are mainly therefore reduced or eliminated, so that the latter reaction is prevented and the ions do not get stuck with the detergent or the contaminated Connect textiles. Since the pyrophosphate anion tightly binds only one mole of calcium ions per mole of pyrophosphate anions, it was It is common to do the first association step (complex formation) on a 1: 1 mole basis. If the pyrophosphate anion, however activated so that it associates (precipitates) two moles of calcium ions, the amount of pyrophosphate can be substantial be reduced. Preferably, some free tetravalent pyrophosphate anion is present in washing solutions, since it causes alumina contamination can peptize.

In the German parallel application P 25 42 704.7 it is proposed that that a cleaning agent preparation alkali pyrophosphates can be added in such a way that the pyrophosphates act as builders by first associating with up to two moles of calcium per mole of pyrophosphate and then precipitating them, will. It is known, however, that pyrophosphates are not particularly effective in maintaining whiteness. One good maintenance of the degree of whiteness depends on the ability of the detergent in the washing liquid dispersed dirt, for example washed out of the soiled objects, to prevent it from settling redeposits on the clean or cleaned objects.

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The invention relates to builder preparations, mainly consist of pyrophosphate and detergent preparations in which these builders are contained and a cause improved maintenance of the degree of whiteness.

In particular, the invention relates to a detergent builder that of water-soluble alkali phosphates, pyrophosphates, tripoly or higher phosphates and orthophosphates consists, the tripoly or higher phosphates in an amount of 1 to 15 percent by weight and the orthophosphates in are present in an amount of less than 1 percent by weight, based on the total phosphates. The cleaning agent preparations according to the invention are made up of the following components:

(a) 1 to 50 percent by weight of an organic anionic, non-ionic, ampholytic or zwitterionic cleaning agents or a mixture of these ingredients and

(b) 5 to 60 percent by weight of the cleaning agent builder described above.

The pyrophosphate salts of the preparations according to the invention have Alkaline cations such as sodium or potassium, preferably sodium. According to the invention suitable pyrophosphate salts are either commercially available or can be obtained by neutralizing the corresponding phosphoric acid or its acid salt v / earth.

Generally speaking, these phosphates can be used in detergent preparations can be used in amounts as small as about half of the tripolyphosphates previously used. The least Amounts can be employed using the methods described below. Some specifically for the pre-wash stage in the washing cycle of modern automatic washing machines Up to now, the cleaning agents provided contained up to about 70 percent sodium tripolyphosphate. Other high performance

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Laundry detergents, on the other hand, only contain around 20 percent. The amount of the phosphate mixture preferred according to the invention, on the other hand, is about 12 to about ! +5 percent by weight, based on the preparation.

The amount of tripolyphosphate (preferred) or that of the higher polyphosphates is preferably about 5 to about 12 percent by weight, based on the total phosphate. amounts above 15 weight percent will not improve whiteness retention. As a tripolyphosphate, less cleaning ability for the same weight is effective as a pyrophosphate, larger amounts are undesirable.

It is essential that the orthophosphate content is kept low will. Small amounts such as 1 percent by weight of orthophosphate, based on the total amount of phosphate, can already be disadvantageous begin to work »Preference is therefore given to using less than 0.5 percent by weight.

In general, the detergent preparations are in produced in such a way that the pH in 1 percent aqueous solution is in the range from 9 to 12, preferably 9 | 8 to 11. lies. This means that the phosphates are usually in completely neutralized form, i.e. as tetrasodium pyro- and pentasodium tripolyphosphate, can be used, but the acidic forms can also be used if this is appropriate. The degree of hydration of the components is not important in accordance with the invention.

Furthermore, the preparations according to the invention can also contain the additives usually contained therein.

Suitable anionic organic detergent components are, for example, the compounds described below. According to the invention, a water-soluble one is preferred Salt of: ethoxylated sulfated alcohols with a ■

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average degree of ethoxylation from about 1 to Zf and an alkyl chain length of about 1Zf to 16; Tallow oxysulfate; Tallow alcohol sulfates; Alkylbenzenesulfonates with an average Alkyl chain length of 11 to 13, preferably 11.2 carbon atoms; C, - - C-Q-Alphasulf ο carboxylic acids or their esters, the 1 to 1Zt carbon atoms in the alcohol residue contain; Cq - C «, - paraffin sulfonates; C-q - Cp, -alphaolefin sulfonates or mixtures thereof or other anionic sulfur-containing surfactants, such preferred Cleaning agents are described below.

A particularly preferred alkyl ether sulfate cleaning agent component according to the invention is a mixture of alkyl ether sulfates, this mixture being an average (arithmetic) carbon chain length of about 12 to 16 carbon atoms, preferably about 1Zf. up to 15 carbon atoms and an average (arithmetic) degree of ethoxylation of about 1 to 1 mole of ethylene oxide, preferably has about 2 to 3 moles of ethylene oxide.

In particular, such preferred mixtures at about O consist to 10 weight percent of the mixture of C.ρ - C., compounds, about 50 to 100 weight percent of the mixture of C -, - C- c- compounds, to about 0 to Zf5 weight percent of Mixture of Cj, - - C. "compounds and about 0 to 10 percent by weight of the mixture of C- η - C-" compounds. Furthermore, such preferred alkyl ether sulfate mixtures contain about 0 to 30 percent by weight of the mixture of compounds with a degree of ethoxylation of 0, about Zf5 to 95 percent by weight of the mixture compounds with a degree of ethoxylation of 1 to Zf, about 5 to 25 percent by weight of the. Mixture of compounds with a degree of ethoxylation of 5 to 8 and about 0 to 15 percent by weight of the mixture of compounds with a degree of ethoxylation of more than 8.Instead of the preferred alkyl ether sulfates described above, sulfated condensation products of ethoxylated alcohols with 8 to 2Zf alkyl carbon atoms and 1 to 30, preferably 1 to Zf mol of ethylene

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oxide can be used.

Suitable cleaning agent components which can be used according to the invention there are also the water-soluble salts, in particular the alkali, ammonium and alkylolammonium salts of organic salts sulfuric acid reaction products, which in their molecule a Alkyl group having from about 8 to about 22 carbon atoms and one Contain sulfuric acid ester group. Examples of this group of synthetic detergents are the sodium and potassium alkyl sulfates, in particular those which are obtained from sulfates of higher alcohols (Co-C.o-carbon atoms). The alcohols are obtained by reducing the glycerides from tallow or coconut oil.

Water-soluble organic cleaning agent compounds preferred according to the invention are also the alkylbenzenesulfonates (preferably linear although "hard" ABS can be used are) that contain about 9 to 15 carbon atoms in the alkyl group contain. Examples are the sodium and potassium alkylbene sulfonates described in US Patents 2,220,099 and 2,477,383, in which the alkyl groups contain from about 11 to about straight or branched chain carbon atoms. Straight-chain alkylbenzenesulfonates in which an average of 11.2 carbon atoms in the alkyl group are particularly useful are included (abbreviation C.- ρ LAS),

Water-soluble components are also suitable as cleaning agent components Salts or esters of alphasulphonated fatty acids containing about 6 to 20 carbon atoms in the fatty acid group and as Ester about 1 to Uj. Contain carbon atoms in the alcohol residue,

"Olefin sulfonate" cleaning agent mixtures preferred according to the invention are for example olefin sulfonates having about 10 to about 2 ^ carbon atoms. Such materials can by sulfonating alpha olefins with non-complex Sulfur trioxide and subsequent neutralization are produced. It is neutralized under such conditions,

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that all sultones present to the corresponding hydroxyalkanesulfonates be hydrolyzed. The alpha olefin starting materials preferably contain 1Zf Ms 16 carbon atoms. Such Alpha olefin sulfonates are described, for example, in U.S. Patent 3 332 880.

The paraffin sulfonates used according to the invention are essentially linear and contain 8 to 2Zj. Carbon atoms, preferably 12 to 20, especially 1Zj. to 18 carbon atoms in the alkyl radical.

Other suitable anionic detergent compounds are the sodium alkyl glyceryl ether sulfates, especially the ethers higher alcohols obtained from tallow and coconut oil; Sodium coconut oil fatty acid monoglyceride sulfonates and sulfates; and sodium or potassium salts of alkylphenolethylene oxide ether sulfates, about 1 to about 10 units of ethylene oxide each Molecule, and in which the alkyl groups contain from about 8 to about 12 carbon atoms.

Water-soluble salts of higher fatty acids, ie “soaps”, are also suitable as cleaning agent components. This class of detergents includes normal alkali soaps such as the sodium, potassium, ammonium and alkylolammonium salts of higher fatty acids containing from about 8 to about 20 carbon atoms, and preferably from about 10 to about 20 carbon atoms. Soaps can be obtained by direct saponification of fats and oils or by neutralizing free fatty acids. The sodium and potassium salts of the mixtures of fatty acids obtained from coconut oil and tallow, ie sodium or potassium tallow soap and coconut soap, are particularly suitable.

Water-soluble, nonionic synthetic detergents are also suitable as cleaning agent components. Such nonionic detergent materials can generally be used as Compounds are defined by condensation of

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Alkylene oxide groups (hydrophilic properties) with an organic hydrophobic compound that is aliphatic or alkyl aromatic can be built, produced. The polyoxyalkylene group condensed with any hydrophobic group can be precisely regulated in their length so that a water-soluble compound is created, which is the desired Has a balance between hydrophilic and hydrophobic elements.

For example, under the trade name "Pluronic ^tf Wyandotte Chemicals a well known group of non-ionic detergent available. These products are obtained by condensing ethylene oxide with a hydrophobic substance produced by condensing propylene oxide with propylene glycol. Other suitable nonionic synthetic detergents are the polyethylene oxide condensates of alkylphenols, for example the condensation products of alkylphenols which contain an alkyl group with about 6 to 12 carbon atoms in a straight or branched chain, with ethylene oxide, the ethylene oxide being present in amounts of 5 to 25 moles per mole of alkylphenol.

Also suitable as nonionic cleaning agents are the water-soluble condensation products of aliphatic alcohols with 8 to ZZ carbon atoms in a straight or branched chain and ethylene oxide, for example a coconut alcohol-ethylene oxide condensate with 5 to 30 moles of ethylene oxide per mole of coconut alcohol, with the coconut alcohol fraction being 10 to 1 f contains carbon atoms.

Semi-polar nonionic detergents include: water soluble Amine oxides, which have an alkyl group with about 10 to 28 carbon atoms and two groups consisting of alkyl and / or contain hydroxyalkyl groups of 1 to about 3 carbon atoms; water soluble phosphine oxide detergents that an alkyl group with about 10 to 28 carbon atoms and two groups consisting of alkyl and / or hydroxyalkyl groups. with

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contain about 1 to 3 carbon atoms; and water soluble Oxide detergents that have an alkyl group of about 10 to 28 carbon atoms and a group which can be an alkyl or hydroxyalkyl group with 1 Ms 3 carbon atoms, contain.

Ampholytic detergents include derivatives of aliphatic secondary and tertiary amines or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic unit can be straight or branched, and wherein one of the aliphatic substituents etv / a 8 to 18 carbon atoms contains and at least one aliphatic substituent carries an anionic water-solubilizing group.

Zwitterionic detergents include derivatives of aliphatic ones quaternary ammonium, phosphonium and sulfonium compounds in which the aliphatic groups are straight or branched can be one of the aliphatic groups about 8 to 18 carbon atoms and one of these groups carries an anionic water-solubilizing group.

Other suitable cleaning agents are the water-soluble salts of 2-acyloxyalkane-1-sulfonic acids containing from about 2 to 9 carbon atoms in the acyl group and from about 9 to about 23 carbon atoms in the alkane group; Beta alkyloxy alkane sulfonates containing from about 1 to 3 carbon atoms in the alkyl group and from about 8 to 20 carbon atoms in the alkane group; Alkyl dimethyl amine oxides in which the alkyl group contains from about 11 to IG carbon atoms; Alkyldimethyl-ammonio-propanesulfonates and alkyldimethyl-ammonio-hydroxypropanesulfonates, in which the alkyl group in both types is about 1 / j. contains up to 18 carbon atoms; Soaps discussed in more detail above; the condensation product of tallow fatty alcohol with about 11 hol of ethylene oxide; the condensation product of a C, -, - (average) secondary alcohol with 9 moles of ethylene oxide; and alkyl glycerol ether sulfates having 10 to 18 carbon atoms in the alkyl radical.

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2 6 O b J ο

US Pat. No. 3,852,2-1 contains a compilation of cleaning agents which can advantageously be used in the context of the present invention. The cleaning agents mentioned so far only serve to illustrate the invention. Of course, other cleaning agents can also be used.

Contains a particularly suitable cleaning agent according to the invention for example:

(i) about 2 to about 15 weight percent of an alkyl sulfate, wherein the alkyl radical has io; to 20 carbon atoms, and mixtures of these compounds in which the cation is an alkali metal, preferably sodium; (ü) about 2 to about 15 percent by weight of an alkylbenzenesulfonate, wherein the alkyl radical has 9 to 15 carbon atoms, and mixtures of these compounds in which the cation is an alkali metal, preferably sodium.

In addition, further components can be added to (i) and (ii) Suitable are, for example:

(iii) about 2 to about 15 percent by weight of an alkyl ethoxy sulfate, wherein the alkyl radical has 10 to 20 carbon atoms and the compound contains 1 to 30 ethoxy groups and mixtures of these compounds in which the cation is an alkali metal, preferably sodium

The detergent is contained in the detergent preparations in an amount of about 1 Ms 50 percent by weight, preferably from about 5 to about Ιφ percent by weight, in particular from about 10 to about 30 percent by weight.

Another very suitable mixture of detergents (detergents) comprises nonionic and s-sitterionische means beispialswsise sulfobetaines with an aliphatic Cn o ₁ radical and surfactants Polyätho: qralkohole ·

ORIGINAL INSPECTED 609836/0953

Furthermore, the cleaning agent preparations can preferably also contain an alkali silicate of the formula SiO ^ tM ₂ O, in which M is an alkali metal or a mixture of alkali metals such as the sodium and potassium salt, preferably a sodium salt. The weight ratio SiO-: M_O is about 1.6: 1 to about 4: 1, preferably about 2.4: 1 to about 4: 1, in particular about 2.75: 1 to about 4: 1.

The alkali silicate is about 1 to about 25 percent by weight, preferably about 2 to about 20 percent by weight, in the preparation and especially about 4 to about 15 percent by weight.

The preparations also preferably contain one. Diluents in an amount of about 0.1 to about 80 percent by weight, preferably about 1 to about 55 percent by weight and in particular from about 2 to about 30 weight percent.

Diluents suitable according to the invention are in the preparation preferably, but not absolutely necessary, inert. For example, sodium carbonate serves as a preferred diluent, which gives the preparation an alkaline reaction and thus promotes the cleaning ability. In addition, the sodium carbonate neutralizes those in the dried product or acidic pyrophosphates contained in the slurry, thereby improving their strength as builders. Additional Sodium carbonate reduces the hardness of the water in a particular Scope. On the other hand, sodium sulfate also preferred as a diluent mainly gives a desirable one Granulate characteristics.

Suitable diluents according to the invention are, for example, natural and synthetic clays, alkali, in particular Sodium and potassium carbonates, bicarbonates, sesquicarbonates, -borates, -perborates, -sulphates, -chlorides, -bisulphates and -aluminates. Calcium carbonate is also suitable as a diluent.

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- 12f -

The preparations obtained according to the invention can be used by all Kinds of cleaning room coapoiienten are supplemented, being these components are added to the aqueous slurry to be dried or mixed with the dried preparations can·

Other conventional components of detergent preparations as well can be added to the preparations according to the invention. For example, perhydrate bleaches can be used for this such as perborates and percarbonates, stabilizers, activators or catalysts for these agents; Enzymes and stabilizers or protective agents for these substances; Soil suspending agents; Non-stick material; Means by which the Processing and spray drying of nonionic detergents can be facilitated if these are used; antibacterial fabrics; optical brighteners; Foam regulators; Dyes and perfumes. Some of these agents are well known sensitive to heat and are therefore expediently added to the dried product.

The detergent preparations according to the invention can also contain additional amounts of water-soluble detergent builders can be added.

Examples of suitable organic detergent builder salts are: (1) water-soluble aminopolycarboxylates such as sodium and potassium ethylenediamine tetracetate, hitrilotriacetate and N- (2-hydroxyethyl) nitrilodiacetate; (2) water-soluble salts of phytic acid such as sodium and potassium phytates (see U.S. Patent 2,739,942); (3) water-soluble polyphosphonates such as sodium, potassium and lithium salts e of A * than-1-hydroxy-1,1 -diphos phonic acid; ! Tatrium, Potassium and lithium salts of methylenediphosphonic acid, sodium, Potassium and lithium salts of ethylene diphosphonic acid and sodium, potassium and lithium salts of ethane-1,1,2-triphosphonic acid. Also suitable are the alkali salts of ethane ^ -carboxy-ijl-diphosphonic acid, hydroxymethandiphos- "

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26QbQ54

Phonic acid, carbonyldiphosphonic acid, Ätnan-1-hydroxy-1,1,2-triphosphonic acid, Ä "than-2-hydrosy-i, 1,2-triphosphonic acid, Propane-1,1,3,3-tetraphosphonic acid, propane-1,1, 2,3-tetraphosphonic acid and propane-1,2,2,3-tetraphosphonic acid; and (if.) water soluble salts of polycarboxylate polymers and copolymers (See U.S. Patent 3,308,067).

A detergent builder suitable according to the invention consists of a water-soluble salt of a polymeric aliphatic Polycarboxylic acid having the following arrangement of carboxyl groups and the following physical characteristic: (a) a minimum molar weight of about 350 based on the acid form; (b) an equivalent weight of about 50 to about 80 based on the acid form; (c) at least Jj5 mole percent the monomeric component carry at least two carboxyl groups by no more than two carbon atoms are separated from each other; (d) is the point of attachment of the polymer chain of a radical containing carboxyl groups by no more than three carbon atoms along the polymer chain separated from the point of attachment of the next radical containing carboxyl groups. Examples of the above Builders are polymers and copolymers of itaconic acid, aconitic acid, maleic acid, mesaconic acid, fumaric acid, Methylenemalonic acid and citraconic acid.

Other builders are also suitable, such as water-soluble salts of mellitic acid, citric acid, pyromellitic acid, Benzene pentacarboxylic acid, oxydiacetic acid, carboxymethyloxysuccinic acid and oxydisuccinic acid.

The cleaning agent preparations according to the invention preferably contain a water-soluble cleaning agent in an amount of about. 10: 1 to about 1:10, preferably about 3 · 1 to about 1: 3 »based on the total weight of the builders present. In the cleaning agent preparations according to the invention, the amount of additional builders is about 5 to about 50 percent by weight, preferably about 10 to

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about 25 percent by weight. These additional builders can be dried together with the aqueous slurry or mixed with the dried product of the slurry. If desired, the additional builder can be the diluent and then added to the slurry to be dried.

When certain zeolites or aluminum silicates are dried with the components of the slurry, they improve the effect of the silicates contained therein and increase the builder capacity, since the aluminum silicates complex the calcium hardness. When the aluminosilicates are mixed with the dried slurries, they act as co-builders of the pyrophosphates. An aluminum silicate which can advantageously be used according to the invention is an amorphous, water-insoluble hydrated product of the formula Fa _{x CxAlO 2} ⁴ YSiO ₂ ), where χ is an integer from 1 to 1.2. and y means 1. The amorphous material also has a Mg exchange capacity of about JO mg eq. CaCO ^ / g to about 150 mg eq. CaCO ^ / g. This ion exchange builder is described in more detail in patent application 1505/74 published in Ireland (Angern. July 16, 1974).

Another synthetic water-insoluble aluminum silicate ion exchange material which is suitable according to the invention has the formula Na_T (AlQ-,) · (SiO ₀ ) J xH-0, where ζ and y are integers of at least 6; the molar ratio of ζ to y is in the range from 1.0 to about 0.5 \ x is an integer from about 15 to about 264J the aluminum silicate ion exchange material has a particle diameter of about 0.1 microns to about 100 microns, preferably about 15 microns , a calcium ion exchange capacity of at least about 200 mg eq / g and a calcium icnenai exchange rate of at least about 0.034 g / l / min / g. Bite synthetic aluminum silicates? / Are described in more detail in the Belgian patent specification 814 874.

The aluminum silicates described above are used in an amount of about 1 to about 40 percent by weight, preferably about 5 percent by weight up to about 15 percent by weight.

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The builder preparations according to the invention can be used in any Wise prepared, for example, by mixing appropriate amounts of phosphates.

The detergent preparations can be solid, liquid or paste-like; solid granules are preferred. They can be made by any suitable method. However, drying in the heat, for example spray drying, can be disadvantageous because too much pyro- and / or tripolyphosphates are converted into orthophosphates. The phosphates in particulate form, for example crystalline or ground, are therefore preferably mixed with the rest of the preparation. Of course, enough pure products must be used with regard to the orthophosphate content. To produce granulated products, according to a preferred procedure, some or all of the non-heat-sensitive components of the preparation are spray-dried. The products obtained in this way can be mixed with the phosphates and, if desired, the perhydrates. The spray-dried part of the preparations can be produced by any known method. However, in order to achieve the best possible effect of a limited amount of the phosphate builder, the cleaning agent preparations are preferably produced as aqueous slurries which contain the alkali metal silicates, cleaning agents and diluents. The resulting slurry is then either! in a single stage or in multiple stages to a moisture content of no more than about

5 percent by weight dried. Preferably the moisture content is of the product immediately after drying at about 0.1 to about 3 percent by weight, especially at about 0.4 to about 2 percent by weight. The note that the Moisture content to be determined immediately after the final drying is necessary as the product is subsequently can rehydrate to a higher moisture content without significantly affecting its performance.

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Therefore, if the product has a moisture content of 2 percent by weight, based on the total solids present, has been dried, the product may absorb water or hydrate, it being possible for the abovementioned limits to be substantially exceeded. Apparently it is Process according to which the moisture is added or in the dried Product maintained is more important than the total moisture content during storage.

Presumably, the previously dried product does not change back to its original form when it is rehydrated later and therefore retains its effect.

The lower moisture limit of the dried product is based on economic considerations. For example the more the granules are dried, the more complex the manufacturing process. Also can organic components are adversely affected by oxidation if the drying temperature is too high.

The slurry can be dried to a solid product having the requisite moisture content by any of the conventional methods will. The drying is preferably carried out in a single stage, but can also be carried out in several stages will. Including such drying processes of agglomeration are described, for example, in US Pat. No. 2,895,916. Other methods of drying of the preparations according to the invention are, for example, freeze drying, drum drying and oven drying. Preferably However, the products are dried in one stage in drying spray towers, for example in the U.S. Patents 3,629,951 and 3,629,955 are described.

The production of the detergent preparations according to the invention preferably includes the steps of adding alkali silicates, detergent, diluents and others

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compatible ingredients to an .aqueous slurry and then thorough ruffles. The thoroughly mixed slurry is then made according to that described above Spray drying dehydrated. When agglomerating or freeze drying is used, it may be necessary to the product in additional process steps, for example by oven drying to further dry to the desired moisture content. Preferably, the inventive Product as granules. If the product is produced in large, irregular pieces, it can become the desired Particle size can be granulated. The products according to US Pat. No. 3,178,370 and British Patent specification 1 064 414 can be deformed into detergent bars.

According to the invention, granular products are preferably produced by the spray-drying process. This drying process can be carried out in countercurrent or cocurrent drying towers. In the simplest embodiment, the products of the invention are dewatered by pumping the mixed slurry into drying towers. For this purpose, the slurry is directed to a series of atomizing nozzles which are mounted opposite the outlet opening for the lean drying gases. The temperature of the hot air mixture should be in the range of etv / a 66 to about 822 ⁰ C, preferably from about 93 J to about 542 ° C and especially about 104 etv a lying / 374 ⁰ C.

The temperatures which are reached by the granules are from about 49 to about 149 ⁰ C, preferably at about 60 to about 135 ° C and in particular at about 66 to about 121 ⁰ C.

When one is disclosed in U.S. Patents 3,629,951 and 3,629,955 Spray drying device described is used, spray-dried the product is expediently under the conditions specified there.

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The cleaning agent preparation produced according to the invention is preferably in solid form, preferably as granules used. However, the corresponding products can also be "preferably ground to a colloidal size and in one." suspended in a suitable medium such as water. These suspensions are then packaged as liquid preparations.

It can be advantageous to mix the phosphates with the dried granules in the presence of a binder. as Suitable binders are nonionic surfactants such as glue and the like. Through this treatment, the Phosphates on the surface of the spray-dried granules.

example

From the following components v / earth cleansing preparations manufactured:

Components ABCDE

Sodium Dodecylbenzenesulfonate 8.0 8.0 '8.0 8.0 8.0

non-ionic surfactant 3.0 3.0 3.0 3.0 3.0

Fatty acid 3.5 3.5 3.5 3.5 3.5

Uatriuate tripolyphosphate 26.0 - 1.6 1.6 1.6

Sodium pyrophosphate 5, O ⁺ 16 14, 4 14.3 14.0 sodium orthophosphate 1.0 * 0.06 0.05 0.14 0.4

Sodium silicate (solid

(SiO ₂ : Na ₂ O = 1.6: 1) 7.0 7 ₃ O 7 _} 0 7.0 7.0

Sodium perborate 25.0 25.0 25.0 25.0 25.0

Sodium sulfate 12.0 28.0 28.0 28.0 28.0

other components 3.5 3.5 3.5 3.5 3.5

Moisture 6.0 6.0 6.0 6.0 6.0

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+ These values are approximate and illustrate products with approximately. 20 percent reversion during the spray drying of the 32 % tripolyphosphate originally added.

Preparation A is a spray-dried product in granulate form, which contains dry mixed sodium perborate.

Preparation C is a product according to the invention; the other preparations are for comparison purposes.

Preparations B to E are made by dry mixing the phosphates, (B and C commercially available, D and E contain additional Orthophosphate), made with granular products of the other components.

The products had essentially the same cleaning properties. Your ability to maintain whiteness is measured as follows:

Washing process

The samples of white cotton fabric are washed with a washing machine Washed in 18 ° H water (158 ppm CaCO ,,), the artificial Contains dirt of the following composition:

Air filter dirt 200 ppm Alumina 200 ppm

Lipids 100 ppm

The above-mentioned preparations are used as cleaning agents in the concentrations given below. the Samples and the v / ash solutions are placed in the washing machine at 20 ° C given and 75 minutes during the ash process 95 ° C heated. The samples are taken out in 18 ° H water rinsed and dried. In the case of a single wash, the reflectivity is then determined. At a Wash the samples twice again in fresh dirt

609836/0953

Washed containing water, then rinsed, dried and determined the reflectivity. Among the values for that Whiteness retention becomes reflectivity of the washed samples is understood as a percentage of the original reflectivity before treatment.

attempt

(two washes)

Post-treatment reflectivity values are reported as a percentage of the original reflectivity;

preparation

A B C

Concentration (percent by weight in the washing solution)

0.4
95
83
93

0.6

95 80 90

o, 8

93 8G

Try preparation

(a washing process)

Concentration (percent by weight in the washing solution)

A B C D

E.
The margin of error is about + 1 unit %

0.4 0.6 0.8 97 97 9S 89 90 88 92 93 94 89 S? 87 86 84 85

609836/0953

Claims (18)

Claims Ύ «Detergent builder based on water-soluble Alkali phosphates, characterized in that they contain pyrophosphates, tripoly- or higher phosphates and orthophosphates contains, with tripoly- or higher phosphates in an amount of 1 "to 15 percent by weight and the orthophosphates are present in an amount of less than 1 percent by weight based on the total phosphates. 2. finishing agent builder according to claim 1, characterized in that that the tripoly or higher phosphates in an amount of 5 to 12 percent by weight and the orthophosphates are present in an amount of not more than 0.5 percent by weight, based on the total phosphates. 3. Detergent preparation containing: (a) 1 to 50 percent by weight of an organic anionic, nonionic, ampholytic or zwitterionic Cleaning agent or a mixture of two or more of these components; (b) 5 to 60 percent by weight of a phosphate builder according to claim 1 or 2. 4 cleaning agent preparation according to claim 3, containing: (a) 5 to IfO weight percent organic cleaning agent and (b) 12 to Zj-5 weight percent phosphate builder. 5. detergent preparation according to claim 3 or if, characterized characterized in that they are used as cleaning agents alkali and ammonium alkyl ether sulfates, alkyl sulfates, alkyl benzene sulfates, Contains salts of alpha sulfocarboxylic acids or mixtures of these components. BO9H36 / 0953 2 6 G j 3 5 6. cleaning agent preparation according to claims 3 to 5, additionally containing: (c) 1 to 25 percent by weight of an alkali silicate of the formula SlO-UlJ), in which the SiO_: M, O weight ratio is about 1.6: 1 to about 4: 1 "and M is an alkali metal or a mixture of alkali metals is. 7. cleaning agent preparation according to claim 6, characterized in that that the weight ratio of SiO-: M_0 is 2.4: 1 to 4: 1. 8. Detergent preparation according to claim 6 and 7 »thereby characterized in that it contains 2 to 20 percent by weight of the silicate. 9. Cleaning agent preparation according to claims 3 to 8, additionally containing: (d) 0.1 to 80 percent by weight of a diluent. 10. Cleaning agent preparation according to claim 9, characterized in that that it contains 1 to 55 percent by weight of diluent and one or more diluents the following components are used: alkali carbonates, bicarbonates, sesquicarbonates, chlorides, borates, perborates, Sulfates, bisulfates and aluminates, calcium carbonate and Clay. 11. Cleaning agent preparation according to claims 3 to 10, additionally containing: (e) 1 to 40 percent by weight of a synthetic water-insoluble hydrated aluminum silicate of the formula Na _z [(A10 ₂ ) _z · (SiO ₂ ) JxH ₂ O, wherein ζ and y are integers of at least 6; the molar ratio of ζ to y is in the range from 1.0 to about 0.5 and χ is an integer from about 15 to about 264, this aluminum 60 ⁽ J 836/0953 _Λβ1ΛΙ ORIGINAL INSPECTED 28U5ÜÖ4 silicate exchange material has a particle diameter from about 0.1 to about 100 microns, a calcium ion exchange capacity of at least about 200 mg eq / g and a calcium ion exchange rate of at least about 0.03 ^ g / l / minute / g. 12. Detergent preparation according to claims 3 to 10 » additionally containing: (f) 1 to if 0 percent by weight of an amorphous aluminum silicate of the formula Ha (xAlOp'ySiOp), where χ is an integer of 1 to 1.2 means and the aluminum silicate ion exchange material a magnesium ion exchange capacity of about 50 mg eq. CaCO, / g to about 150 mg e * qu. Has CaCO, / g * 13. detergent preparation according to claims 3 to 12, characterized in that the pH is 9 to 12 in a 1 percent by weight aqueous solution. 14. Cleaning agent preparation according to claim 13, characterized in that that the pH in a 1 percent strength by weight aqueous solution is 9.8 to 11. 15 «Detergent preparation according to claims 3 to 14» characterized in that the crystalline or ground crystalline phosphate builder without hot drying in the Preparation is incorporated. 16. Detergent preparation according to claims 1 to 5 » containing dried granules which contain component (a) and one or more of components c, d, e and f dry-mixed with component (b). 17. Cleaning agent preparation according to claim 16, characterized in that that the dried granules contain the following components? 1 to 50 percent by weight of component (a) according to Claims 3 and 5 » ORIGINAL INSPECTED :; ■ η yi 38/0953 , _Ν 260ο054 1 to 25 weight percent; the component (c) according to the Claims 6 and 7 and 0.1 to 80 percent by weight of component (d) according to the Claims 9 and 10, and that the granules have a moisture content of not more than 5 percent by weight have been dried. 18. Cleaning agent preparation according to claim 17, characterized in that that the moisture content is not more than 3 percent by weight. 19 cleaning agent preparation according to claims 16 to 18, characterized in that the phosphates are mixed with the spray-dried granules in the presence of a binder will. For: The Procter & Gamble Company Cincinnati, ΟίιίοΛ V.St.A. Dr.H.J.VoIff Lawyer 609836/09 53 OiWINAL »« PKTED