DE2350009A1 - LIQUID, Aqueous CLEANING AGENT - Google Patents

Description

-CH! SANWALTE. 2 3 5 O Q O 9

^ K. JUi ?. DUL-CHEM. WALTER BHlL -

ALFRED HOcPPEiJGR'L OKI 1973

DR. JUR. HANS CnR. BEIL '* \'

FRANKRUUTAM

Our no. 18 885 Ec / tk

Procter & Gamble European Technical Center B-I82O Strombeek-Bever / Eelgien

Liquid, aqueous cleaning agent

The present invention relates to a liquid cleaning agent which contains practically no builders, for washing dishes and for cleaning hard surfaces is suitable and has an excellent cleaning effect and improved drainage behavior. In particular, the invention relates to a liquid, concentrated, aqueous cleaning agent, particularly the For cleaning dishes, e.g. made of glass or porcelain, as well as tiles and other glazed objects serves and which is a water-soluble olefin sulfonate, preferably an α-olefin sulfonate, and a sulfate of a higher one Contains fatty alcohol and a small amount of gelatin.

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The cleaning agent according to the invention saves drying the washed items with a cloth or a fabric and at the same time prevents.deposition of hardening components of the water on the cleaned, rinsed and air-dried Objects almost completely.

In recent years, liquid cleaning agents, especially those based on soap-free detergents, for washing glasses, plates, porcelain and the like have found great sales. They are also often used to clean windows and other items made of glass or items with glazed surfaces. They are particularly suitable for cleaning these items by hand. In addition to organic surface-active detergents, such cleaning agents normally contain inorganic and / or organic builders in order to improve the cleaning action of the organic detergents and / or to reduce the negative effects of water hardness. Avoided in the cleaning agents of the present invention, v / ith the materials addition of _t scaffold without the cleaning action to negatively influence. Although there are no builders to bind the hardening constituents of the water, hardly any stains can be found on the washed, rinsed (and air-dried) items ₃ which are due to the hardness of the water.

The quality of a dishwashing detergent is determined by the consumer normally, when washing by hand, based on the amount of foam during the washing process and based on the The gloss of the cleaned and / or dried objects. The liquid detergents for washing dishes

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by hand, which are currently available on the market, are largely designed to produce a large amount of foam because the consumer associates it with a large cleaning effect. However, many food residues reduce the formation of foam and the cleaning effect in washing liquors. The detergent residues on the cleaned items must be removed by rinsing or drying them while damp. If the items are not dried immediately after washing, these residues will dry on the surfaces of the cleaned items and leave stains and streaks. If hard or tap water is used, remain difficult to remove white spots on the surfaces of the objects back _s due to the water hardness. If the objects are rinsed in clear tap water and not dried immediately, stains will also remain on the cleaned and dried objects, which can be attributed to the hardening components of the water.

Drying the cleaned items, e.g. glasses and dishes, with cloths immediately after taking them out of the Washing water has been taken out is uneconomical (a lot of water must be removed with many cloths) and also not always feasible (too frequent interruption of the flushing process). That is why many housewives start only then to dry the rinsed items with a cloth after the last item is rinsed and off the detergent solution has been removed and - in some cases rinsed. Other housewives provide the flushed Simply put items aside to drain and air dry Cleaning effect of the cleaning agent used, which the housewife may have directly after the washing process had found, lost and there are streaks to be removed and unsightly surface spots and streaks

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or stains due to water hardness, if the rinsed items have been rinsed. Since these stains, especially those caused by water hardness, can hardly be removed by further rinsing processes, they lose the glasses and other glazed objects lose their shine and are only reluctantly used ♦

The rinsing agents currently available on the market to prevent staining of glasses, tableware, etc. by detergent surfactants and / or water hardness are mainly for use in Dishwashers thought. You must each in one separate rinse cycle can be used after the actual rinse or cleaning cycle, as they are completely ineffective if they are used together with the cleaning agent (detergent mixture). You also need to separately because they react with the ingredients of dishwashing detergents or detergents, causing the The cleaning effect of the cleaning agent is reduced.

Contrary to the general assumption that rinsing and cleaning agents for dishes are packaged and separately must be used, according to the invention a stable, Aqueous, practically builder-free cleaning agent for dishes and similar objects with an excellent Cleaning effect provided due to its improved drainage behavior after rinsing leaves no streaks or stains due to water hardness on the items, regardless of the Water hardness of the cleaning water and the rinsing water.

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The invention is therefore based on the object of providing a liquid, stable, aqueous cleaning agent, especially for use by hand, with excellent cleaning properties and improved drainage behavior after rinsing, which means that it is independent of the hardness of the cleaning and rinsing water staining on the cleaned ,. .- Rinsed and air-dried glasses, dishes and. other glass-like and glazed objects is avoided and drying with cloths is no longer necessary.

The attraction, ease of manufacture and economy of the dishwashing and cleaning agents of the present invention can, and this is a further advantage of the present invention, be easily improved and adapted to the particular end use sought, for example by adding high-foaming surfactants without that as a result the final gloss of the cleaned glasses ₉ plates etc. is lost. The amount of customary additives, such as colorants, opacifiers and fragrances, can be increased since no builders are present. In addition to this, there will be solid residues left after the cleaning process

t can remain on the cleaned objects and - could only be partially removed by rinsing with clear tap water, which washes away with the drainage water.

The liquid detergent of the present invention that can be used in hard water contains calculated on the total weight of the product:

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. A. about 3 to about k5 wt -% of a water-soluble hydrocarbon sulphate having the general formula:

R ₁ OSO ₃ M "(I)

wherein R _{1 is} a saturated or unsaturated aliphatic hydrocarbon radical with 8 to 2k carbon atoms and M is an alkali metal or ammonium ion or a dimethyl, ₃ diethyl, _a trimethyl, triethyl, dimethanol, ₉ diethano, ₃ trimethanol or triethanolammonium radical;

., About 3 to about Ηξ wt -% of a water-soluble Kohlenx ^ asserstoffsulfonates the general formula:

R ₂ -SO ₃ M (H)

wherein R_ \ ieigtkettigen _a represents unsaturated aliphatic hydrocarbon radical having 8 to 2h carbon atoms, and M is as defined above wherein _s has the formula II is preferably an a-olefin sulfonate is a linear or galvanized;

C. about OjI to about 5 wt. a water-soluble gelatin having a molecular weight of at least 12,500 to 100,000, preferably about 15,000 to about 60,000; an isoelectric point of pH 4.5 to pH 9 ₃ 2 and a gel strength of 25 to 300 bloom grams; and

D. the remainder is water

v / whether ei the amount A + B at most 47.5% by weight, preferably up to 36 wt. is and the weight ratio of A: B is 5: 1 to 1: 5.

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A preferred liquid cleaning agent consists essentially of:

ά. about 6 to about 25 weight -% of a sulfate of the general formula (I) in which R ₉ is an alkyl group having 12 to 18 carbon atoms, preferably a radical derived from coconut oil higher fatty alcohol and M is an ammonium or alkali metal ion.

B. about 6 to about 25 wt. % Of a sulfonate of the general formula (II), in which R _? a hydrocarbon radical with 12 to 16 carbon atoms, preferably an α-olefin radical, and M is an ammonium or alkali metal ion

C. about O _S 2 to about 2.0 wt "-S? a water-soluble gelatin with a molecular weight of 15,000 to about 60,000a, preferably 25,000 to 50,00O _3, an isoelectric point above pH 6, preferably at pH 7 to pH 9 and a gel strength above 50 Bloom-Srammj, preferably from 80 to 200 Bloom-grams and

D. the remainder is water;

wherein the total amount of surfactant detergents is 18 to 36 % by weight and the weight ratio of AiB is 2.5: 1 to 1: 3.

The liquid cleaning agents according to the invention usable anionic surfactant detergents, the gelatin and the other ingredients which may be added in minor amounts are described below. If in the following description of the surface-active detergents and additional ingredients

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share on a salt of an anionic surfactant Detergent or other acidic ingredients are referred to, it is a sodium, potassium, Ammonium, trimethyl, triethyl, dimethyl, diethyl, trimethanol, Triethanol, dimethanol or diethanolammonium salts, unless otherwise noted.

Suitable surfactant detergents used for manufacture The liquid detergents of the present invention that can be used are:

1. Water-soluble hydrocarbon sulfates, shown by the general formula

R ₁ OSO-M (I)

wherein R- represents a saturated or unsaturated aliphatic hydrocarbon radical having 8 to 24 carbon atoms and M is a cation. Examples of preferred carbon vias s first off sulfates, which can be used according to the invention, are the salts of organic sulfuric acid reaction products, which are formed by reaction of a saturated or unsaturated fatty alcohol with 8 to 18 carbon atoms, preferably tallow or coconut alcohol, with SO or H ₂ SO. can be obtained in a manner known per se and optionally subsequent bleaching and / or hydrolysis. Specific examples are: C 1-4 alkyl-O-SO N (C ₂ H ₂₁ OH); Coconut-0-SO Na;

C ₁₂ _ _l6 -alkyl-O-SO K; and TaIk-O-SO N (H)

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2. Water-soluble salts of organic sulfuric acid reaction products of the general formula:

R ₂ -SO ₃ -M -, '(II);

wherein R_ is a straight-chain or branched-chain, unsaturated, aliphatic hydrocarbon radical having 8 to 24 carbon atoms, preferably 12 to 16 carbon atoms, and M is a cation. Examples of preferred synthetic. Detergents that can be used according to the invention are the salts of organic sulfuric acid reaction products of a hydrocarbon of the ethylene series having 8 to 20, preferably 12 to 16 carbon atoms, and 1 to 1 h double bonds, with a sulfonating agent, such as "eg SO · ,, H" SO ^, oleum, obtained by known sulfonation methods, including bleaching and hydrolysis are obtained. Preferably, sulfonated C ₁₂ _ ^ ga-olefins.

3. water-soluble gelatin with a molecular weight of at least 12,500 to 100,000, preferably about 15,000 up to about 60,000.

e Gelatin is a typical protein, and the gelatin molecules like the molecules of other proteins are very large and complex with an average molecular weight of

5,000 to .200,000 and higher »Gelatin molecules in alkaline or acidic solutions are amphoteric and have a specific isoelectric point, which depends on the treatment conditions during production. Gelatin that obtained by acid treatment has an isoelectric. Point above pH 7, generally between pH 7 and 9, whereas gelatine, which is formed by an alkaline

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treatment has an isoelectric point between pH 4.5 and 5. Preferred gelatin for the detergents of the present invention is the acid-treated gelatin having an isoelectric point from pH 7 to 9, preferably around pH 8 and an average molecular weight of 15,000 to 60,000.

The water-soluble gelatin can be contained in the liquid detergent of the present invention in an amount of 0.1 to about 5 % by weight, preferably 0.2 to about 2% by weight, based on the total weight of the detergent. While the very small amount of 0.1 wt -.% Is nötwendig to achieve still an appreciable flow effect, the upper limit of about 5 parts by weight JS based on the formulation requirements, ie, the fact that a liquid composition is to be present, which still pourable and therefore easy to handle, dissolve * and use.

About the comprehensive cleaning effect, i.e. the removal of dirt by simply rinsing and removing residues of dirt, surfactant detergent and hardening components of the water due to the run-off effect after additional rinsing, but without To achieve wiping or towel drying, the molecular weight must be that in the invention liquid cleaning agent to be used gelatin above 12,500, preferably above 15,000 and in particular from 25,000 to 60,000, while the isoelectric point of gelatin is between pH 4.5 and pH 9.2, preferably above pH 6 and especially at pH 7 to pH 9 and the gel strength of the gelatin to be used, above 25 Bloom grams, preferably above 50 Bloom /

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and in particular should be 80 to 200 bloom grams »(The gel strength in bloom grams or bloom strength is the force in g that must be applied to a cylinder with a diameter of 12.7 mm so that it penetrates the surface of a gel made of 6.6? % gelatin with 15 % moisture ^{penetrates 1} l mm deep, see British Standard Method for Sampling and Testing Gelatins.)

Suitable further components or additional compounds contained in the cleaning agents of the present invention can be, are

ty. low molecular weight organic acids such as acetic acid, citric acid, maleic acid and inorganic acids such as boric acid and the corresponding alkali metal salts, which should only be added in very small amounts. Potassium tetraborate is preferred. Obscnon the boric acid or salts in amounts up to 5 parts by weight JS, based on the total weight of the cleaning agent can be added, at least areas between 2 and 3 weight are -.% Being preferred.

5. Fragrances, dyes, fluorescent substances, agents, that prevent dulling, such as benzotriazole or ethylene thxourea, and bactericides.

6. Hydrotropes and other solubilizers, such as e.g. Ma-cumene sulfonate, Na- or K'-toluenesulfonate, Na- or K-xylene sulfonate, ethanol, butanol or isopropanol.

As already indicated, the cleaning agents are of the present invention Invention intended for use in hard water. Is the water hardness in millimoles CaCO, per liter

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expressed so can both for the cleaning solution as for the rinsing solution water with a water hardness between 0.7 mmol and 3.7 mmol CaCO, per liter and higher be used.

The excellent cleaning effect and especially the superior drainage effect of the liquid dishwashing detergents of the present invention are demonstrated by the experiment below.

Three series A, B _r and C, each consisting of two dishwashing detergent solutions, which are described below, and three series A ', B ¹ and C ¹ , each consisting of two post-rinse solutions, were prepared. Each dishwashing detergent solution of each series contained per liter 0.2 wt -.% Of a below dishwashing detergent marked. The rinsing solutions consisted of clear tap water. The water of the rinsing solution and the post-rinsing solution had a hardness of approximately 3.4 mmol CaCO-r per liter. Each rinse or rinse bath contained approximately 10 liters of water. The temperature of all rinse solutions or baths was about 42 ⁰ C at the start and dropped to 35 ° to 27 ° C at the end of the flushing process from. The temperature of the rinsing baths ranged between 40 and 42 ⁰ C.

In each of the 3 series of 2 dishwashing detergent solutions each, 5 soiled glasses (content: approx 25 el) obtained from a cafeteria, rinsed for 30 seconds, taken out and during Placed on a rack for 30 seconds, then dipped 5 individually in the corresponding rinsing liquid texts and in a vertical position, bottom up, on a rack to drain and air dry (Room temperature: approx. 23 ° C).

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A. B. C. 16 10 10 m 12th 12th 0.7 0.5 0 rest

■ - 13 -

The liquid dishwashing detergents of the individual series had the following composition:

Components in% by weight. Series

Coconut alcohol sulfate ammonium salt

Olefin sulfonate ammonium salt
(mainly from C ₁ I, _{1 (} -
alpha-olefin) ¹⁴ " ^lb

gelatin
water

Gelatin; average molecular weight 30,000; isoelectric point. pH 8.2; Gel strength about 80 bloqm-grams,

If you observe the film of water that followed the last The rinsing process runs off the glasses, so. this film runs off in a few seconds from the glasses that are in the Series A and B solutions had been flushed, and the Glasses were dry long before the glasses were in the Series C solutions had been flushed.

After all the glasses were dry, the outward appearance became rated. The glasses that had been rinsed in Series A and B rinse fluids were the Glasses rinsed in the C series washing fluids had been superior; they showed less or none Spots or streaks and hardly due to water hardness Stains, whereas the glasses of the C series have different stripes and different ones based on water hardness Had stains.

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The following examples illustrate the invention. All percentages relate to weight.

example 1

20.0% C ₂ _. ₁₁ alcohol sulfate, sodium salt 15.0% C ₁₂ _ ₁ g 01efinsulfonat-sodium salt 0.5% gelatin, average molecular weight 25,000, isoelectric point about pH 7,8j gel strength approximately

70 bloom grams

Remainder: water

Example 2

16.0 % CP- ₁ K-AlkOhOlSuIfat-natriumsalζ 15.0 % Ct? __ iß-Olefinsulfonat-triethanolammoniumalz 1.0 % gelatine, average molecular weight 45,000, isoelectric point approx. PH 8.2; Gel strength, for example

100 bloom grams

Remainder: water

Example 3

10.0 % Cp alcohol sulfate ammonium salt 13.0% C ₁ p_ ₁ g-oil sulfonate ammonium salt 0.8 % gelatin, average molecular weight 35,000; isoelectric point about pH 8; Gel strength about 80 bloom grams

Remainder: water

example k

18.0 % coconut alcohol sulfate ammonium salt 10.0% _{CLp -} -I j, -01efinsulfonat sodium salt

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1.0 % ammonium sulfonate

1.5% gelatin, average molecular weight 25,000; isoelectric point about pH 7.8; Gel strength, for example 70 bloom grams

Remainder: water

Examples 5-10 .

5 6 7 8 9

Coconut alcohol sulfate

ammoniums al ζ 16% - 1B% 18% - 1Z%

Tallow alcohol sulfate

sodium salt - 22%. -

_12lj
sulfonate ammonium alz 1055 8% lh% 10% 10% 8% gelatin. 0.5? ^1} 1.5X ¹ ^ 3? ² \ O, 32 ³⁾ O, 8? ^{2) O} ' ⁵ water remainder

1) average molecular weight 25,000; isoelectric point about pH 8.5; Gel strength 75 bloom grams

2) average. Molecular weight ¹ JO,000; isoelectric point about pH 8; Gel strength 100 bloom grams

3) average molecular weight 15,000; isoelectric point about pH 7.6; Gel strength 60 bloom grams

4) average molecular weight 32,000; isoelectrical Point about pH 8.2; Gel strength 85 bloom grams.

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Claims (3)

- ie - claims 1. Liquid, aqueous cleaning agent, especially for dishes, which contains practically no builders and usable in hard water, containing a surfactant and a protein derivative, characterized in that it consists essentially of the following components: A. about 3 to about 45 weight percent of a water soluble Hydrocarbon sulfates of the general formula: R ₁ OSO ₃ M (I) wherein R is a saturated or unsaturated aliphatic Represents hydrocarbon radical with 8 to 24 carbon atoms and M represents an alkali metal or ammonium ion or a dimethyl, · diet hy 1-, trimethyl, triethyl, dimethanol, Means diethanol, trimethanol or triethanolammonium radical; B. about 3 to about 45 Qe \ * .-% of a water-soluble hydrocarbon sulfonate of the general formula: R ₂ -SOM, (II) where R _? represents a straight-chain or branched-chain unsaturated aliphatic hydrocarbon radical having 8 to 24 carbon atoms and preferably an α-olefin sulfonate radical and M is as defined above; C. about 0.1 to about 5 weight percent of a water soluble Gelatin with a molecular weight of at least 12,500 up to 100,000, preferably from about 15,000 to about 60,000, an isoelectric point of pH 4.5 to pH 9.2 409816/1080 and a gel strength of 25 to 300 bloom grams; D. balance: water; . wherein the amount of A + B is at most 7.5 wt ^ -%, and preferably 12 to 36 wt -% by weight and the ratio of A: B from 5: 1 to 1: 5.. 2. Cleaning agent according to claim 1, characterized in that it consists essentially of the following components -consists: A. from about 6 to about 25 weight -% of a sulfate of the general formula (I) wherein R ₁ represents an alkyl radical with "12 to 18 carbon atoms, preferably a radical derived from Kokösnußöl higher fatty alcohol moiety and M represents an ammonium or Alkalimetaliion. B. from about 6 to about 25 weight -% of a sulphonate of the general formula (II) wherein R_ is a hydrocarbon radical having 12 to 16 carbon atoms and preferably an a-01efinsulfonat and M represents an ammonium or alkali metal ion. C. about 0.2 to about 2.0 weight percent of a water soluble Gelatin having a molecular weight of 15,000 to about 60,000, preferably 25,000 to 50,000, a isoelectric point above pH 6, preferably at pH 7 to pH 9 and one. Gel strength above 50 bloom grams, preferably from 80 to 200 bloom grams; D. balance: water; wherein the total amount of surface-active detergents is 18 to 36 % and the weight ratio A: B is 2.5: 1 to 1: 3. 3. Cleaning agent according to one of claims 1 or 2, characterized in that it additionally contains 2 to 5% by weight NatriumcumoIsulfonat, Na or K-toluenesulfonate or 409816/1080 7350009 Contains Na or K xylene sulfonate as a hydrotropic agent. k. Cleaning agent according to one of Claims 1 to 3, characterized in that it additionally contains 2 to 10% by weight of an organic alcohol with 2 to 5 carbon atoms. For: Procter & Gamble European Technical / ßenter Dr. H * J. Wo Iff! Lawyer 409816/1080