DE2619668A1 - DETERGENT COMPOSITION - Google Patents

Description

PAT E M TAN WÄ LT LI

DR. A. VAN DERWERTH DR. FRANZ LEDERER REINER F..MEYER

PIPL-ING. (1334-197-4) D1PL.-CHEM. DIPL.-ING.

8000 MUNICH 80

LUCILE-GRAHN-STRASSE 22

TELEPHONE: (089) 472947 TELEX: 524624 LEATHER D TELEGR .: LEATHER PATENT

May 3, 1976 C 534 (R)

UNILEVER N.V.

Burgemeester s'Jacobplein 1, Rotterdam, Netherlands

Detergent composition

The invention relates to a detergent composition.

One of the requirements for a satisfactory dishwashing detergent composition is that this should show good foaming behavior, d. H. the composition "or the means should form a uniform, stable foam. This applies in particular to dishwashing detergents for use in Washing dishes by hand where a uniform, stable foam is a measure of the effectiveness of the detergent compositions is.

Numerous dish detergent compositions provide an acceptable one Pour rank behavior in either hard or soft Water; an alignment or a composition for use in hard water is often unsuitable for use in soft water, and the reverse is also often true.

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2 B ! 9 B ΰ 8

The object of the invention are dishwashing detergent compositions, those for use in both hard and soft Water are suitable.

The dishwashing detergent compositions according to the invention show a peeling behavior in hard as well as in soft water, which is much better than that of known products, so that a formulation is given, its foaming behavior is relatively independent of the water with which the rinse water or wash water is produced.

Essentially this is achieved by incorporating into a dishwashing detergent composition an organic sequestering agent, which will be defined below, and a magnesium salt, which will also be defined below, is entered, the dishwashing detergent composition furthermore preferably particular types of detergent active materials or detergent materials as set forth below are still described in detail contains.

The organic sequestering agents used according to the invention have a difference in the pK value for calcium and magnesium of at least 0.5 and preferably of Λ or more. In addition, they have a pK value for calcium of at least 3

Suitable examples of organic sequestering agents which are used according to the invention are:

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6.5 26th 5.5 19668 xiitr ilo tri acetic acid 4.6 2.4 1.0 Dipicolinic acid (DPA) 10.6 8.7 2.2 Ethylenediaminetetraacetic acid (ÄDTA) 8.0 5.2 1.9 Hydroxyethyl-ethylenediamine triessig-
acid (Hydroxy-ÄDTA) 12.5 10.3 2.8 1,2-diamine cyclohexane-N, N'-tetra-
acetic acid (ECH ¹ IA) 4.57 2.68 2.2 2-sulfoanilinediacetic acid (SADA) 5.06 3.91 1.89 2-aminobenzoic acid-N, N-diacetic
acid (ABDA) 3.96 2.47 1.15 N-aceto-amidoimino-diacetic acid
(AADA) 4.53 3.31 1.49 N-methoxyethylimino-diacetic acid
(MÄDA) 4.63 3.44 1.22 N-hydroxyethylimino-diacetic acid
(HÄDA) 7.12 6.02 1.19 Trimethylenediaminetetraacetic acid
(TMETA) 5.05 3.44 1.10 Tetramethylene diamine tetraacetic
acid (TeMETA) 11.0 5.2 1.61 1,2-bis-C (2-dicarboxymethyl) -amino-
ethoxyethane] (DCMA) 8.4 6.9 5.80 N-hydroxyethyl-Ν, Ν ¹ , N ", N" -diäthy-
lentriaminetetraacetic acid (HÄDÄTA) 1.50

Although the acids are mentioned in the list above are, it is to be understood that the alkali metal salts, e.g. B. the sodium salts, but just as well the ammonium and substituted ammonium salts of these acids can also be used in the invention.

The selection of an organic sequestering agent according to the invention within the scope of the definition given above is further determined by the pH of the dishwashing detergent composition determined in solution: it goes without saying that with

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pH values below the pK values of the organic sequestering agents the complexing capacity is considerably reduced, so that you get an organic sequestering agent with a pK- ¥ ert below the at. Use would or should select the pH obtained.

For dishwashing purposes, the organic sequestering agent, if the pH of the system is 9 or less, a pK for calcium of about 8 or less and preferably below 7-5. For detergents for general Purposes, e.g. B. Hard surface cleaners, floor cleaners and the like that have a higher pH have, the pK value for Cylcium can be higher.

For dishwashing detergent compositions, the preferred organic sequestering agents are NTA, dipicolinic acid and hydroxyethyliminodiacetic acid, and for general purpose detergents, Hydroxy-ÄDTA, DCHTA, ÄDTA be used.

The amount of the organic sequestering agent or mixture of sequestering agents is also relatively critical; in general should be at least 3 wt .-%, based on the total composition, are present. Smaller amounts, e.g. On the order of 1% or less, do not provide what is desired Foaming behavior. The maximum amount of the organic sequestering agent is 60% by weight of the total composition. Preferably the amount is from 8 to 40%. The magnesium salts, which are used according to the invention are soluble or dispersible in water, inorganic and / or organic Magnesium salts. The solubility of the magnesium salts is a dominating factor; the solubility product of the magnesium salt should be larger than about 5x10. In addition, should

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the magnesium salts for dishwashing purposes not "with one pH values above 9 have a buffering effect.

Suitable examples of inorganic magnesium salts are Magnesium sulfate, chloride, bromide, godide, nitrate, and suitable Examples of organic magnesium salts are magnesium citrate, tartrate and ADTA.

The amount of magnesium salts to be used according to the invention varies from 0.5 "to 30% by weight and is preferably in Range from 2 to 15 wt%.

The organic: sequestering agents used in accordance with the invention are particularly useful in compositions containing calcium sensitive detergent active materials. The latter are more or less easily obtained from solutions containing calcium ions, which are present as salts that cause the hardness of the water, e.g. B. in natural types of water, precipitated, whereby a loss of performance in terms of cleaning, wetting and foam stability is given. Examples of such calcium-sensitive, detergent-active materials are C _{/ 1} 2- ^c . <18 ~ ^A - ^I- kylt> ^en zolsulfonate, sec-CL ^ alkanesulfonates, sec-GQ-CpQ-alkyl sulfates, primary ^c ^ q -alkyl sulfates, sulfosuccinates and their mono- and di-Cg-Cp-alkyl esters, C ^ pC ^ g-fatty acid soaps and mixtures thereof. These active materials mentioned above include their alkali metal, ammonium and substituted ammonium salts. The calcium-sensitive, cleaning agent-active materials should have a calcium

—11 solubility product of less than about 6 χ 10 and preferably

-11

wise less than about 3 χ 10. These calcium sensitive active materials can be used in conjunction with other less calcium sensitive active materials, e.g. B. C ₁₀ -C _x , g-alkyl sulfates, which contain 1 to 10 moles of ethylene oxide, non-ionic, detergent-active or detergent-active materials such as condensation products of

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Ethylenoxia nit primary or secondary C.q-C. "- alcohols, C ^ q-C.g-fatty acids and -ITettamides, Cg-C ^ g-alkylphenols etc., as well as zwitterionic, detergent-active substances such as sulfobetaines, alkylaminocarboxylic acids, tertiary amine oxides etc. In general, the calcium-sensitive, detergent-active Materials in connection with less calcium-sensitive, detergent-active materials at least 50% by weight of the mixture. The total amount of detergent-active Materials ranges from 1 to 55 percent by weight. for general For cleaning purposes this amount is preferably from 2 to 25% by weight and for dishwashing purposes this amount is preferred 15 to 45% by weight.

The composition according to the invention can be formed into particulate, solid, paste or liquid detergent formulations can be formulated according to methods well known in the art. The rest of the composition, if any can use the usual auxiliaries or additives make up for detergents, e.g. B. inorganic salts such as alkali metal sulfates, carbonates, orthophosphates, silicates, furthermore foam boosters such as fatty acid mono- and dialkylolamides, Hydrotropes such as urea, ethanol, sodium xylene and -toluenesulfonates, enzymes, germicides, perfumes, coloring Materials, opacifying materials, corrosion inhibitors, agents for preventing a deposit on metals, inhibitors against damage to porcelain samples, etc.

The invention is explained in more detail below with the aid of examples.

In these examples, the foam stability was measured by diluting the product in water with the specified hardness to the specified product concentration and then generating the foam by shaking. Then subsets of dirt to this solution at 4-5 ⁰ G, with further shaking

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Entered "until the foam collapsed. The results are expressed as the number of dirt particles required to destroy the foam. The percentages are in weight unless otherwise specified. Examples to 3 do not fall under the invention, but are "comparative examples, the advantages achieved according to the invention according to Examples 4 to 6 show.

Example 1 (comparative example) A composition containing 27% sodium C --- Chalky lbenzenesulfonat and 3 % sodium sulfate was dosed in water of different hardness up to a product concentration of 0.15%. The following foam stability results were obtained:

Water hardness ( ⁰ I ¹ H, calcium) Number of dirt particles to be destroyed; of the foam

0. 10

1 30

2 44 4 28

10 10

These results show that the performance increases with Water hardness decreases significantly.

Example 2 (comparative example) A composition which contained 27 % sodium C,. ,,. ^ - benzene sulphonate, 15% sodium tripolyphosphate and 58 % sodium sulphate was diluted with water of various hardness up to a product concentration of 0.15%. The results of the foam stability test were as follows:

Water hardness ( ⁰ FH) Number of partial quantities of dirt for

..,. Destruction; of the foam

20 42

10. 30th

. '' 4 ■ 8

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These results show that the lower the performance Water hardness decreases significantly, with a conventional 3uilder salt or builder salt such as sodium tripolyphosphate was used.

Example 3 (comparison example)

Using the same formulation as in Example 2, but replacing 4 % of the sodium sulfate with 4% magnesium sulfate, the following results were obtained:

Water hardness ( ⁰ FH) Number of partial quantities of dirt for

Destruction of the foam

20 40

10 42

4 32

1 "8

These results show that performance is improved in soft water, but that in very soft water Performance drops significantly.

Example 4 (according to the invention)

A composition containing 27% K "atrium-C _{/ 1} ^ _ ^, - alkylbenzenesulphonate, 20 % trisodium nitrilotriacetate, 10% magnesium sulphate and 43% sodium sulphate was mixed with water of various hardnesses to a product concentration of 0.15 % (pH = 8.1). The investigation of foam stability gave the following results:

Water hardness ( ⁰ FH) Number of partial quantities of dirt for

_________________________ Destruction of the foam

20 40

10 41

4 39

1 30

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Lie the following composition: 27% sodium C ..., - alkylbenzene-

II - I Z>

Sulphonate, 14% ITatriunis salt of dipicolinic acid, 10% magnesium sulphate and 49 % sodium sulphate when used under the same conditions as before gave the following results:

Water hardness ( ⁰ PH). Number of partial amounts of dirt to destroy the foam

5. 50

10 '50

24. 40

These results show that there is significantly improved performance over a wide range of water hardness conditions is achieved, d. H. in both soft and hard water.

Example 5 (according to the invention)

Using a liquid formulation that contained the following ingredients:

27 % sodium C 1 -C 4 alkyl benzene sulfonate

3% sodium C ₂ -C ₁₅ alkyl ether sulfate (containing 3 moles of ethylene oxide) ^

4% sodium salt of dipicolinic acid
4% magnesium sulfate

10% urea

2% ethanol
50% water

When the product concentration was 0.15%, the following were found Get results:

Hardness ⁽⁰ I ¹ H) Number of dirt subsets to the destruction of the foam ^

5 '40

10 39

24 41

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These results show that in both soft and in hard water a better performance is achieved.

Example 6 (according to the invention)

A composition which contained 27% sodium C., .. ^ - alkylbenzenesulphonate, ^ O % dipicolinic acid, 10% magnesium sulphate and 23% sodium sulphate gave the following results at a product concentration of 0.5%:

Water hardness (° ΓΞ) number of partial quantities of dirt to be destroyed; of the foam

4 36

24 36

Example 7 C according to the invention and comparison.) The following compositions were compared with one another, using the same method as in the previous examples. The compositions contained 27% of sodium ^C 11 ^ x ^ ^alk yl ^enzolsu l ^f0113 L ^ 1 3 ° / ° sodium sulfate and

a) 0.2% li (2-hydroxyethyl) ethylenediamine-N, N ', N'-triacetate as trisodium salt (Eydroxy-ÄDTA)

b) 0.2% hydroxy ADTA + 1% magnesium sulfate

c) 15% hydroxy ADTA + 10% magnesium sulfate.

Composition b) contained hydroxy-ADTA and magnesium sulfate in the amounts as described in Dutch patent 7-404.849 and containing composition c) the same ingredients xtfie the composition b), however, in higher amounts, namely according to the invention.

These products were dosed in water of varying hardness up to a product concentration of 0.15% and the investigation subjected to foam stability as in previous examples. The following results were obtained:

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Water hardness ( ⁰ UTL, calcium) composition

a be number of partial quantities of dirt to be destroyed; of the foam

25th 34 46 25th 27 37 20th 21 31 16 16 25th

10 20

Example a) shows no improvement in hard water, example b) only shows an improvement in soft water and Example c) shows improved performance for all values of water hardness.

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Claims (8)

261966B claims 1. Detergent composition for use in soft and hard. Water, thereby k en η ζ ei c hn et that they a. Detergent-active material, from $ to 60% by weight of an organic sequestering agent with a pK-Vert for calcium of at least 3 "and a difference between the p £ - ¥ ert for calcium and for magnesium of at least 0.5, as well as zero , 5 to 30% by weight of an inorganic and / or organic magnesium salt with a solubility product of at least 5 "χ 10 ^. 2. Composition according to claim 1, characterized in that the difference in the pK values for calcium and magnesium is at least 1.0. 3. Composition according to claim 1, characterized in that the pK value for calcium is less than 8. 4. Composition according to one of claims 1 to 3 »thereby characterized in that the organic sequestering agent dipieolic acid or its alkali, ammonium or substituted Is ammonium salt. 5. Composition according to Claim 1, characterized in that the magnesium salt is magnesium sulfate. 6. Composition according to one of · Claims 1 to 5 »thereby characterized in that they contain from 8 to 40% by weight of the organic Sequestering agent and from 2 to 15% by weight of the magnesium salt contains. 603847/10 00 7. Composition according to one of claims 1 to 6, characterized characterized in that the detergent-active material is at least 50% by weight of a calcium-sensitive, anionic, detergent-active material with a solubility —1Ί
product "contains less than 6 χ ΊΟ. 8. Composition according to claim 7? characterized in that the detergent-active material at least 50% by weight a sodium C ^ -C ^ o -alkyrbenzenesulfonate or one Sodium sec. -G.q-C. ^ - contains alkanesulfonates. 609847/1000 ORlGiNAL INSPECTED