CH633824A5 - Liquid detergent or cleaning agent - Google Patents

Abstract

Clear stable, liquid detergent or cleaning agent, which has an improved cleaning efficacy. This detergent or cleaning agent has a decreased content of hydrotropic compounds and contains paraffin-sulphonates, ethoxylated alcohols, alkyl ether sulphates and a system for the regulation of the viscosity and clarity consisting of ethanol and urea, and if desired additionally protein. The protein can be admixed to obtain further advantages. The ethanol content is between 0.15 and 4% by weight of the composition and thus significantly below the amounts of known compositions.

Description

The invention relates to a liquid detergent or cleaning agent according to claim 1. Advantageous embodiments are mentioned in claims 2 to 10.

The washing and cleaning agent according to the invention contains the following components in accordance with the definition in claim 1:

(a) a water-soluble salt of a paraffin sulfonate,

(b) an ethoxylated alcohol and

(c) a water-soluble salt of higher alkyl ether sulfonates in a ratio of (a): (b + c) from 10: 1 to 1: 1; Farther

B, C, D a viscosity and clarity regulating system with improved properties compared to products according to US Pat. No. 3,755,206, consisting of urea, ethanol and water, and optionally a protein which has a nourishing effect, prevents skin cracks and enhances the rinsing effect.

In particular, the amount of ether sulfate is kept smaller in the liquid cleaning agent according to the invention without the cleaning power being reduced, specifically by the addition of an ethoxylated C8-C12 alcohol. The addition of the ethoxylated alcohol or ether alcohol reduces the amount of lower alkanols required to adjust the viscosity and clarity.

Clear, stable, liquid washing and cleaning agents are preferably obtained if component A is present in an amount of 30 to 60% by weight.

Liquid detergents containing alkyl aryl sulfonates and alkyl ether sulfates are known. In order to formulate liquid detergents with these two components in sufficient concentration, it has hitherto been necessary to provide relatively high proportions of a solubility-promoting agent or of a hydrotrope, such as lower aliphatic alcohols, e.g. Ethyl alcohol, urea, low molecular weight alkyl benzene sulfonates, for example sodium xylene sulfonate and the like.

The liquid cleaning agents according to the invention have considerable advantages over the previously known products based on alkylarylsulfonates and alkyl ether sulfates and are also superior in terms of their behavior to products which contain paraffin sulfonate and ether sulfate, especially in soft water. This superiority arises in the so-called "miniplate" tests in comparative tests of the composition according to the invention over known products which contain even larger amounts of ether sulfate and also over compositions in which even an ethoxylated alcohol is present. This superiority presumably differs from the ethoxylated alcohols claimed here and is due to the particular alkyl chain length and the extent of the ethoxylation of the ethoxylated alcohol or ether alcohol and the novel mixture of the components.

It has also surprisingly been found that a lower proportion of ethyl alcohol is made possible as a solubilizing agent, depending directly on the amount of ether sulfate which is replaced by a corresponding amount of ethoxylated alcohol or ether alcohol for a given paraffin sulfonate portion. This achieves a second advantage with regard to the product, which shows better behavior and can be produced more economically, since less ether sulfate and in particular less ethyl alcohol is required. The reduction in the alcohol content is achieved without modifying physical properties such as viscosity and cloud point of the product and without adversely affecting the behavior of the product, reducing the production costs of the product and the flash point of the product. This reduction is probably due to the exact installation of the shares

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Ethanol and urea with the selected ethoxylated alcohol as a nonionic detergent.

Although U.S. Patent No. 3,755,206 has a broad general disclosure regarding the alkyl chain length and the extent of ethoxylation of an ethoxylated alcohol required, as an optional ingredient, it has now been found that there is an optimal behavioral outcome, which lies below and within the Revelation lies. In contrast to this disclosure, the alcohols of this reference are not all equivalent and, in fact, optimal results are obtained if one works outside the preferred range of this disclosure.

Compared to the previously known liquid cleaning agents, the product according to the invention has the following advantages:

1. Liquid cleaning agents with comparable effectiveness and properties with a lower percentage of active ingredients and comparable clarity can be produced according to the invention with a considerably lower proportion of solubilizing agents than previously.

2. The mixtures according to the invention surprisingly produce an equally good or better foam than the known mixtures, both in terms of the amount of foam and the foam resistance.

3. At the same concentration of use as known products, the mixtures according to the invention show considerably better behavior, in particular as dishwashing detergent.

4. Wash liquors with the product according to the invention result in a considerably lower surface tension than known products in the same concentration.

Further advantages according to the invention are the improved and controlled behavior such as foaming, suitability as a dishwashing detergent, viscosity and clarity, which are essential for the consumer.

The paraffin sulfonates of component (a) used are usually mixed secondary alkyl sulfonates having 10 to 20 carbon atoms per molecule, preferably at least about 80 and usually at least about 90% of the products having 13 to 17 carbon atoms per molecule. If the main proportion has 14 to 15 carbon atoms per molecule, optimal foaming behavior is achieved at different concentrations and water hardness. These sulfonates are preferably produced by sulfoxying a paraffin cut corresponding to the chain length given above with sulfur dioxide and oxygen in a known manner. The reaction product is a secondary sulfonic acid, which is then neutralized with a suitable base with the cations below to give the water-soluble secondary alkyl sulfonate. Secondary alkyl sulfonates which are prepared by other processes, such as by sulfochlorination, in which chlorine and sulfur dioxide are reacted with the paraffin in the presence of actinic radiation and the sulfonyl chlorides obtained are hydrolyzed and neutralized to the secondary alkyl sulfonates are similarly suitable. Such sulfonates are generally present in amounts of 15 to 60 and preferably 20 to 35% by weight.

The higher alkyl ether sulfonates used according to the invention have the following general formula:

R0 (C2H40) "S03X

in which R is a primary or secondary alkyl radical, which can be straight-chain or branched and 10 to 18, preferably 3 633824

has 12 to 15 carbon atoms. X is a suitable water soluble cation and n is a number from 1 to 10 and preferably 3 to 6. These detergents are e.g. obtained by sulfating the corresponding ether alcohols and then 5 neutralizing the sulfuric acid half-ester obtained.

The cation of the paraffin sulfonate and alkyl ether sulfate is sodium or potassium, ammonium and / or mono-, di- or triethanolammonium.

One of the essential active constituents of the composition according to the invention is a C8-C12 alcohol, which can be straight-chain or branched-chain and is ethoxylated with 5 to 8 moles of ethylene oxide. Surprisingly, it was found that the incorporation of this compound instead of a part of the ether sulfate enables a corresponding weight reduction of the amount of the latter compound without affecting the behavior of the end product. In addition, the amount of ethyl alcohol required to adjust the Vis-20 viscosity and clarity can be reduced accordingly.

In some cases it is preferred that the liquid detergent contain a higher fatty acid alkylolamide in sufficient amount to act as a foaming agent. The presence of this compound leads to a product 25 which, when used, produces a strong foaming power and in particular an extremely stable foam during washing dishes or laundry. The acyl residue of the alkylolamide is derived from fatty acid having 8 to 18 carbon atoms and each alkylol group usually has up to 3 30 carbon atoms. Monoethanolamides of lauric and myristic acids, but also diethanolamides and isopropanolamides and ultimately also monoethanolamides of fatty acids with 10 to 14 carbon atoms in the acyl radical are preferably used. Examples are monoethanolamides, diethanol-35 amides and / or isopropanolamides which have been prepared using capric acid, lauric acid, myristic acid and a medium cut of coconut fatty acids (Ci2-Cj4). It is also possible to use alkylolamides which are substituted by additional etheneoxy radicals, such as, for example, the above amides which are condensed with 1 to 4 moles of ethylene oxide.

Suitable ratios of paraffin sulfonate salts to the sum of alkyl ether sulfate salts and ethoxylated alcohol are in the range from 10: 1 to 1: 1, preferably 45 in the range from 5: 1 to 1.5: 1, if an optimal combination of properties can be achieved, in particular in the presence of amide or the like. Suitable ratios are 70:30, 75:25 and 80:20, preferably in the presence of 0.5 to 8, preferably 1 to 6 and usually 50 4 to 6% alkylolamide, such as, for example, a coconut monoethanolamide, a diethanolamide or alkanolamide, which is condensed with about 1 to 4 moles of ethylene oxide. The sulfonates and sulfates are in a suitable water-soluble salt form, namely as the sodium, potassium, ammonium 55 and mono-, di- and triethanolamine salt.

Suitable ethoxylated alcohols which are used according to the invention have the following general formula

R0 (C2H40) nH

60 in which R represents an alkyl radical which may be straight-chain or branched-chain and has 8 to 12 carbon atoms, while n denotes a number from 5 to 8. The above compounds are ether alcohols. With higher ether alcohols, the preferred chain length of the alkyl group is 9 to 65 11 carbon atoms.

The nonionic components can be present in amounts of 2 to 10 and preferably at least about 4% by weight.

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The weight ratio of these nonionic components to the alkyl ether sulfates is preferably in the range from 3: 1 to 1: 3 and in particular approximately 1: 1.

To adjust the viscosity and the clarity, urea, ethanol, water and preferably also a water-soluble hydrotropic compound are used in the cleaning agent according to the invention, which improves the compatibility of the constituents in the liquid product and can replace part of the urea and alcohol.

Suitable hydrotropic substances are organic sulfonated and sulfated alkali salts with a lower alkyl group with up to 6 carbon atoms. Preferred sulfonated hydrotropes are alkylarylsulfonates with up to 3 carbon atoms in the lower alkyl group, such as sodium and potassium xylene, toluene, ethylbenzene and isopropylbenzenesulfonates. Xylene sulfonates can be either or-tho-, meta- or para-xylene sulfonates and ethylbenzene sulfonates. Commercial xylene sulfonates usually contain meta-xylene sulfonate as the main ingredient. A common xylene sulfonate contains about 40 to 50% by weight of meta-xylene sulfonate, 10 to 35% by weight of ortho-xylene sulfonate and 10 to 30% by weight of para-xylene sulfonate and 0 to 20% by weight of ethylbenzene sulfonate. Any suitable isomeric mixture can be used. Sodium cumene sulfonate and sodium xylene sulfonate are preferred lower alkyl aryl sulfonates in the products according to the invention. Suitable lower alkyl sulfates having 5 to 6 carbon atoms in the alkyl radical, such as alkali n-amyl and n-hexyl sulfates, can also be used.

By using the components influencing the viscosity and clarity, a much better clarity of the liquid detergent or cleaning agent is achieved at lower temperatures, and the viscosity of the product can be adjusted within a considerably wider range at any relevant concentration of the active ingredients.

The exact proportions of urea and ethanol and, if appropriate, of the hydrotrope component must generally be coordinated with the other active components and their amounts. The proportion by weight of this system, which influences the viscosity and the clarity, based on the overall mixture, generally varies between 0.5 to 15 and preferably 3 to 10%. The amount of urea is 1 to 5% and that of the ethanol 0.15 to 4%, based on the average. The ratio of ethanol to urea is below 1.3: 1, especially below 1: 1, most preferably in a range from 0.37: 1 to 0.85: 1, if the content of active ingredients is preferably around 35 to 45 %, including alkylolamide and the like. Fluctuating amounts of hydrotropes such as xylene sulfonate and the like can be added or partially used instead of the alcohol or urea, so that a ternary system with special properties is formed so that the viscosity is raised to considerably higher values. The amount should be selected so that a sufficient viscosity and cloud point is obtained while maintaining other desired properties. In general, the hydrotrope can make up up to 15% by weight of the total viscosity and control system.

The preferably additionally used protein is a water-soluble, partially degraded protein and can be a partially enzymatically hydrolyzed protein or a protein product obtained by heating. This material is used to reduce skin irritation caused by the surface-active compound. When partially degraded protein is used with or after contact with the surfactant, the prophylactic effect is good. The partially degraded protein has a gel strength of 0 to 200 bloom-g.

Partially decomposed protein also affects the drainage and rinsing properties of the detergent. Such hydrolysis products contain proteoses, peptones and polypeptides and numerous amino acid components. The hydrolysis products can be obtained by partial enzymatic hydrolysis, for example by trypsin, erepsin or pancreatic enzymes. Partially decomposed proteins can also be produced by the action of heat on protein, for example by heating a protein-containing material, such as bones, feet or skin of pigs and cattle, which have been comminuted and treated in water, for example by means of an autoclave.

The preferred hydrolyzed protein is an enzymatically hydrolyzed protein from bovine collagen. Other proteins that can be partially hydrolyzed are casein, gelatin, collagen, albumin, zein, gliadin, keratin, fibroin, globulin, glutenin and the like. Enzymatically hydrolyzed proteins include bacto-protease, proteose-peptones, casein-peptones, gelatin-peptones, bacto-peptones, vegetable peptones, such as soybean peptones, while the solubilized collagens are produced by heating bones, feet or skin of pigs or Derive cattle. Preferred proteins are solubilized bovine and porcine collagen.

The partially hydrolyzed proteins have significantly fluctuating molecular weights in the range from 500 to 70,000, preferably 500 to 10,000 for hand care effects and about 25,000 to 70,000 to achieve good drainage properties. The lower molecular proteins can contain completely decomposed polypeptides such as dipeptides and tripeptides or even amino acids due to the decomposition.

The protein can be used in amounts of 0.1 to 2.0 and preferably 0.3 to 0.8% by weight.

The liquid detergents according to the invention may also contain conventional additives such as sequestering agents, e.g. Salts of ethylenediaminetetraacetic acid, such as the sodium and potassium salts, and salts of hydroxyethyl-ethylenediamine triacetate. In some cases it is advisable to dye the detergent or add odorants.

Water, which represents the rest of the agent at 100%, serves as the carrier for the liquid detergent or cleaning agent.

In order to illustrate the advantages of the detergents according to the invention, mixtures with 32% of a sodium - C13-C17-alkyl sulfonate (SAS), 8% ammonium-C12-Ci5-alkyl-triethenoxy ether sulfate (ALES), 4.5% ethanol, 3% urea and the rest of the water (known) compared with mixtures according to the invention which contained 32% SAS, 4% ALES, 4% ethoxylated alcohol (NI), 2.25% ethanol, 3% urea and the rest water. The last group was then further examined by building appropriate mixtures containing different ethoxylated alcohols to show the unexpected properties that the mixtures inherent when taking a selected group of ethoxylated alcohols out of those that were previously thought to be equivalent had been viewed. The results are shown in Table 1 below.

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633824

TABLE 1

TABLE 2

Miniplate wash test

= 1.25 g / 1 number of plates

Water hardness 32SAS / 8ALES

50 ppm 41

300 ppm 50

M 91

Viscosity cps 25 ° C

160

C9-11

5

EO

47

49.5

96.5

170

C9-11

6

EO

45

53

98

160

C9-11

8th

EO

AI

52

99

180

Cl3 "C15

5

EO

46

48

94

220

7

EO

44

50

94

210

8th

EO

45

49

94

220

ClO-12

5

EO

47

50.5

97.5

150

C12-14

5

EO

45

47.5

92.5

210

Influence of

Alkyl chain

c8

5

EO

47

50

97.0

150

C9-11

5

EO

47

49.5

96.5

170

Cl0 ~ Ci2

5

EO

47

50.5

97.5

150

Cl3 "C15

5

EO

46

48

94

220

^ 9-Cj!

8th

EO

47

52

99

180

C-13-15

8th

EO

45

49

94

220

Preferred areas:

% By weight

Paraffin sulfonate alcohol ether sulfate

Influence of the extent of ethoxylation 32SAS / 4ALES / 4NI

C8_12 alcohol, 5-8 EO

10th

Alkylolamide or alkylolamide EtO condensate

Urea jj ethanol water

20-35 2-8 2-8

0-8

1-5 0.15-4.0 Q.S.

at least 30

In the following, the invention will be described in more detail with the aid of Examples 20, all parts relating to the weight.

example 1

25th

35

Table 1 compares the results of two different behavioral experiments with washing solutions. One test is a dishwashing test, which was carried out at two different water hardness levels, namely a water hardness of 50 or 300 ppm hardness. The other test is a viscosity test.

The dishwashing test or "miniplate" test is described by R. M. Anstett and E. J. Schuck in J.A.O.C.S., volume 43, page 576, October 1966.

The results clearly show that a significant improvement is achieved in the composition according to the invention with a C8-C] 2-alkyl chain which contains at least 5 but not more than 8 moles of ethylene oxide, compared to formulations without ethoxylated alcohol, and that a significant improvement compared to formulations containing ethoxylated alcohol, but with a longer carbon chain.

Table 2 below shows the general quantitative range of the main constituents within which the preferred mixtures according to the invention lie.

% By weight

Sodium C14-Cn-paraffinsulfonate O

32

Ammonium-C12-C15-alkyltriethenoxyether-

sulfate (2)

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Cg-Cu alcohol ethoxamer (6 EO)

4th

Coconut monoethanolamide

O

l *

urea

3rd

Ethanol

2.5

N atrium ethyl 1 endiamine tetraacetate

0.045

Water (with small amounts of dye,

Preservative and fragrance)

rest

O Added as an aqueous mixture containing 60% by weight sulfonate.

45 (2) Added as an aqueous alcoholic solution containing 60% by weight of the sulfate and 10% by weight of ethanol.

The above product shows excellent foaming power and dish washing properties. Along with preferred physical properties, namely a cloud point of about 5 ° C and a viscosity of about 170 cps at 25 ° C using a Bookfield viscometer model LVF, spindle # 1 at 30 rpm. The 55 paraffin sulfonate used had approximately the following composition: 3% C13, 25% C14, 30% C15, 25% C16, 15% C17 and 2% C18 and an average molecular weight of about 328. Various impurities may be present in the commercial products, such as small amounts of free paraffin or disulfonate.

Example 2

A liquid cleaning agent was prepared analogously to Example 1 65, but now an equivalent amount of coconut monoethanolamide which was condensed with 2 moles of ethylene oxide was used instead of the monoethanolamide.

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Example 3

A cleaning agent was prepared analogously to Example 1, but in the following amounts: 22% paraffin sulfonate, 6% alkyl ether sulfate, 6% C9-Cu alkanol 8 EO, 5% lauric acid myristic acid monoethanolamide, 5% urea and 3% ethanol, while the rest was essentially water.

Example 4

A liquid cleaning agent with the same properties as in Example 3 was produced, but the ethoxylated alkanol was now increased by 3% and the amount of ether sulfate was reduced by 3%.

Example 5

A liquid detergent with properties similar to that of Example 3 was prepared by reducing the amount of ethoxylated alcohol to 2% and increasing the ethanol to 3.3%.

Example 6

A liquid cleaning agent with properties similar to that of Example 1 was produced, which had the following composition: 32% sodium C14-C17 paraffin sulfonate, 2% ammonium C12-C15 alkyltriethenoxy ether sulfate, 6% Cg-Cn- Alkanolethoxamer (6EO), 1.1% ethanol, 3% urea and the rest water.

Example 7

A liquid cleaning agent was prepared analogously to Example 1, but containing 2.3% ethanol, 0.6% sodium xylene sulfonate and 1.8% urea.

One of the advantages of the urea / ethanol control system is that the physical properties of the mixture can be changed by changing the ratio of ethanol to urea by changing the ethanol in a range of 0.15 to 4% and the urea in a range of 1 to 5%. In the composition according to Example 1, the ethanol / urea ratio was 2.55: 3 (= 0.85: 1), the clear point being below 7 ° C. and the viscosity being 170 centipoise. The ethanol / urea ratio in the product of Example 2 is likewise 0.85: 1, in Examples 3 to 5 it is 0.6: 1 and in Example 6 it is 0.37: 1.

By changing the ethanol / urea ratio by increasing the ethanol content, it is possible to lower the viscosity and raise the clear point, while lowering the clear point and increasing the viscosity when reducing the ethanol content. Hydrotropes such as sodium xylene sulfonate have a similar effect to that of ethanol, i.e. an increased content increases the clear point but reduces the viscosity. Example 7 relates to a product which contains sodium xylene sulfonate, ethanol and urea. As already mentioned, it is essential to balance these components of the control system within the specified ranges in order to achieve the desired results. With an optimal balance of clear point and viscosity, the total content of the control system also fluctuates with the content of active ingredients such as paraffin sulfonate, alcohol ether sulfate and nonionic surfactants in the overall mixture.

2o The clarification point is further influenced by the amount of the ester in the amide and the sodium sulfate in the paraffin sulfonate and alkyl ether sulfate, which are used as the base material in the preparation of the mixture; for cleaning agents with a low clear point, starting products with a low content of these impurities should be used. The properties which are given for the special product according to Example 1 are best obtained when the amide contains no more than 2% ester and the paraffin sulfonate does not contain more than 4% sodium sulfate 30.

Example 8

Example 1 was repeated, but now 0.5% of a protein solution containing 55% solids and having a gel strength of 100 bloom-g was added.

Example 9

Example 1 was repeated, but now the alkanolamide was omitted and the ethanol concentration was reduced to 40 2.25%, the ethanol / urea ratio being 2.25: 3 (= 0.75: 1).

v

Claims (10)

633 824 1. Liquid detergent or cleaning agent, characterized by (A) at least 30% by weight of a mixture (a) a water-soluble salt of a C10-C20 paraffin sulfonate, (b) a C8-C12 alcohol ethoxylated with 5 to 8 moles of ethylene oxide and (c) a water-soluble salt of an alkyl ether sulfate of the general formula R0 (C2H40) nS03X, in which R is an alkyl radical having 10 to 18 carbon atoms, n is a number from 1 to 10 and X is a cation, wherein the weight ratio of (a) to (b + c) is in a range from 10: 1 to 1: 1 and the cation of the sulfonate and the sulfate sodium, potassium, ammonium and / or mono-, di- or Are triethanolammonium, (B) 1 to 5% by weight of urea, (C) 0.15 to 4 wt .-% ethanol, based on the washing or. Detergent, the weight ratio of ethanol to urea is less than 1.3: 1 and (D) water, the stated relative amounts of the components being based on the total weight of the composition. 2. Detergent or cleaning agent according to claim 1, characterized in that the paraffin sulfonate is a mixture of compounds with 13 to 17 carbon atoms per molecule. 2nd PATENT CLAIMS 3. Detergent or cleaning agent according to claim 1, characterized in that in the general formula of the water-soluble salt of alkyl ether sulfate the alkyl radical has 12 to 15 carbon atoms per molecule and n has a value of 3 to 6. 4. washing or cleaning agent according to claim 3, characterized in that it contains a nonionic foaming agent from the group of mono- and diethanolamides and isopropanolamides of C10-Ci4 fatty acids in an amount of 8 wt .-%, based on the total weight of the agent. 5. Detergent or cleaning agent according to claim 4, characterized in that the nonionic foaming agent is a lauric acid-myristic acid monoethanolamide. 6. Washing or cleaning agent according to claim 4, characterized in that it contains 20 to 35% by weight of a sodium C14-C15 paraffin sulfonate, 2 to 8% by weight of an ammonium C12-C15- alkyltriethenoxy ether sulfate and 2 to 8 wt .-% of a C8-C12 alkanol with 5 to 8 moles of ethylene oxide, and that the sum of components (a), (b) and (c) plus the alkanolamide foaming agent is 35 to 45% by weight of the total mixture. 7. Detergent or cleaning agent according to claim 6, characterized in that the weight ratio of ethanol to urea is in the range from 0.37: 1 to 0.85: 1. 8. Washing or cleaning agent according to claim 7, characterized in that the weight ratio of components (b): (c) is approximately 1: 1. 9. washing or cleaning agent according to claim 1, characterized in that it also contains a lower alkylbenzene sulfonate as hydrotrope. 10. Detergent or cleaning agent according to claim 1, characterized in that it still contains 0.1 to 2.0 wt .-% of a water-soluble protein.