DK153685B - LIQUID CLEANER - 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

ί DK 153685 Β

The present invention relates to a clear, stable liquid cleaner as set forth in the preamble of claim 1.

Liquid cleaners with a content of alkylaryl sulfonates 5 and alkyl ether sulfates are known. Also known are products containing paraffin sulfonate and ether sulfate. Particularly known from German Patent Specification No. 2,434,063 liquid detergents containing, with a total content of detergent exceeding 30%, up to 45% by weight of a water-soluble hydrocarbon sulfonate, up to 45% by weight of a water-soluble alkyl ether sulfate and up to 40% of a non-ionic ethylene oxide condensation product as well as urea and up to 15% by weight alcohols in water.

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These known products require, in order to obtain the desired properties such as clarity, sufficient viscosity, favorable foaming conditions, poor surface tension and satisfactory purity, relatively large amounts of solubilizing agents such as lower aliphatic alcohols, e.g. ethyl alcohol, urea, low molecular weight alkyl benzene sulfonates, e.g. sodium xylene sulfonate and the like.

However, the use of large quantities of alcohol in technical plants causes problems. It poses a security risk and is disadvantageous to the 10 manufacturing costs.

It is therefore the object of the present invention to provide a clear, stable liquid detergent wherein the required amount of alcohol is reduced without damaging the physical properties such as viscosity and cloud point.

This is achieved with the detergent according to the invention, which is characterized in that it contains 1 to 5% urea and the weight ratio of ethanol to urea is less than 1.3: 1.

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The liquid detergents of the present invention have significant advantages over the prior art liquid detergents based on alkylarylsulfonates and alkyl ether sulfonates and are even better in efficacy than agents containing paraffin sulfonate and ether sulfate, especially in soft water. This superiority is demonstrated by "mini-plate" tests with the agent compared to previously known agents containing even greater amounts of ether sulfate and in compositions where there is even an ethoxylated alcohol. This superiority is believed to be due to the particular alkyl chain length and the degree of ethoxylation of the ethoxylated alcohol or ether alcohol and the particular mixture of the constituents.

In particular, in the detergent according to the invention, the amount of ether sulfate is kept less without the purifying power decreasing, namely by the addition of an ethoxylated C 9 -C 4 alcohol. Through this addition, the amount of lower alkanols needed to adjust the viscosity and clarity is reduced.

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Ί

Furthermore, it has surprisingly been found that a reduced level of ethyl alcohol as solubilizing agent is obtained in direct proportion to the amount of ether sulfate which is replaced by a corresponding amount of ethoxylated alcohol or ether alcohol at a given amount of paraffin sulfonate. This provides a further advantage of the product which has better efficacy as shown below and can be produced more economically as less ether sulfate and especially less ethyl alcohol are required. The reduction in alcohol is achieved without modifying the physical properties, e.g. viscosity and cloudiness of the product, and without prejudice to the efficacy of the product, thereby reducing the cost of the product and the flash point of the product. This reduction is believed to be due to proper integration of the amounts of ethanol and urea together with the ethoxylated alcohol of choice as nonionic detergent.

U.S. Patent No. 3,755,206 contains a broad general description regarding the alkyl chain length and the degree of ethoxylation required by an ethoxylated alcohol when used as an optional ingredient, but it has now been found that there is an optimum efficacy result which lies below and within this description. The alcohols of said 20 patent are not all equivalent, as disclosed in the specification, and the optimum results are actually obtained when operating outside the preferred range described.

The paraffin sulfonates used according to the invention are usually mixed secondary alkyl sulfonates which have approx. 10 to 20 carbon atoms per molecule, preferably they will have at least approx. 80S, usually at least approx. 90% with approx. 13-17 carbon atoms per molecule. Where the majority has 14-15 carbon atoms per minute. molecule, the optimal foaming properties appear to be obtained at varying concentrations and water hardnesses.

These sulfonates are prepared, for example, by subjecting a paraffin fraction corresponding to the above chain length effects of sulfur dioxide and oxygen according to the well-known sulfoxidation method. The product of this reaction is a secondary sulfonic acid which is then neutralized with a suitable base to give the water-soluble secondary alkyl sulfonate for use in the invention. Similar useful secondary alkyl sulfonates may be obtained in other ways, e.g. by the sulfochlorination method, by which chlorine and sulfur dioxide are reacted with paraffins in the presence of actinic light, the resulting sulfonyl chlorides being hydrolyzed and neutralized to form the secondary alkyl sulfonates. These sulfonates are generally found in

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quantities of approx. 20% to 35%, based on the weight of the agent.

The higher alkyl ether sulfates used have the general formula

RO (C0H .0) SO_M

2 4 n 3 wherein R is a primary or secondary alkyl group which may be straight or branched chain and has approx. 10-18 carbon atoms, preferably approx. 12-15, M is a suitable water-soluble cation and n is a number of approx. 1 to 10, 10 preferably approx. 3 to 6. These detergents are prepared by sulfating the corresponding ether alcohols and then neutralizing the resulting sulfuric acid ester thereof.

The cation in the paraffin sulfonate and alkyl ether sulfate may be an alkali metal, e.g. sodium or potassium, ammonium or a lower amine, e.g. alkylolamines. It is preferred to use the sodium salt of the paraffin sulfonic acid and an ammonium salt of the alkyl ether sulfuric acid ester.

One of the major active constituents of the present agents is a 20 C8-12 alcohol which is straight or branched chain and ethoxylated with about

5-8 moles of ethylene oxide.

These ethoxylated alcohols and ether alcohols have the formula

R0 (C2H40) nH

wherein R is an alkyl group which may be straight or branched and has 8-12 carbon atoms, while n is a number of 5 to 8. For higher ether alcohols, the appropriate chain length of the alkyl group of 30 is 9 to 11 carbon atoms.

These non-ionic components are found in amounts of 2 to 8% by weight and especially at least 4% by weight. The weight ratio of these non-ionic components to the alkyl ether sulphates ranges from 3: 1 to 1: 3, especially of approx. 1: 1.

DK 153685 B

In some cases, it is preferred that the liquid detergent contains a higher fatty acid alkylolamide in sufficient quantity to act as a foam builder. Its presence results in a product which exhibits high foaming performance during use, especially when stabilizing the foam, which is developed during washing or laundry. The acyl radical in the alkylol amide is derived from fatty acids having 8 to 18 carbon atoms, and each alkylol group usually has up to about 3 carbon atoms. It is preferred to use the monoethanolamides of lauric acid and myristic acid, but the diethanolamides and isopropanolamides, as well as the monoethanolamides 10 of fatty acids, with approx. 10-14 carbon atoms in the acyl radical are satisfactory. Examples are the monoethanolamides, diethanolamides and isopropanolamides and mixtures thereof of capric acid, lauric acid and myristic acid and the heart fraction of coconut oil (C 2 amides condensed with about 1-4 moles of ethylene oxide.

The ratio of paraffin sulfonates to the sum of alkyl ether sulfates to ethoxylated alcohol or ether alcohol ranges from -0.5: 1 to about 1.5: 1 to obtain an optimal combination of properties, especially in the presence of amide or the like. Suitable ratios are 70:30, 75:25 and 80:20 by weight, preferably in the presence of 5-8% alkylol amide, preferably 1-6% and usually 4-6% such as monoethanolamide, diethanolamide or alkanolamide of the heart fraction. of coconut oil -5 condensed with approx. 1-4 moles of ethylene oxide. The sulfonates and sulfates are in a suitable water-soluble form such as the sodium, potassium, ammonium and mono, di and triethanolamine salts thereof or mixtures thereof.

For controlling viscosity and clarity, the liquid detergent of the invention uses urea, a lower aliphatic alcohol and mixtures thereof, and preferably also a water-soluble hydrotropic compound which is effective in promoting the compatibility of the constituents of the liquid product and can replace a part of the urea 5 and the alcohol. In general, the system for controlling viscosity and clarity in concentrated liquid detergents containing at least approx. 30% by weight of active ingredients, namely the sum of paraffin sulphonate, alkyl ether sulphate, nonionic substance and optionally alkylolamide.

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Suitable hydrotropic substances are alkali metal salts of organic sulfonated (including sulfated) compounds having a lower alkyl group of up to approx. 6 carbon atoms, especially alkylaryl sulfonates having up to 3 carbon atoms in the lower alkyl group, e.g. sodium and potassium xylene sulfonate, toluene sulfonate, ethylbenzenesulfonate and isopropylbenzenesulfonate. Sulfonates made from xylene include orthoxylene sulfonate, methaxylene sulfonate, paraxylene sulfonate and ethylbenzene sulfonate. Industrial xylene sulphonate usually contains methaxylene sulphonate as its main constituent. Analysis of typical 10 industrial xylene sulfonate products shows approx. 40-50% methaxylene sulfonate, 10-35% orthoxylene sulfonate and 15-30% paraxylene sulfonate together with 0-20% ethylbenzenesulfonate. However, any suitable isomeric mixture may be used. Sodium cumene sulfonate and sodium xylene sulfonate are preferred lower alkylarylsulfonates for use in the compositions of the invention. It is also possible to use suitable lower alkyl sulfate salts of about

5-6 carbon atoms in the alkyl group such as alkali metal n-amyl and n-hexyl sulfate.

The use of a system for controlling viscosity and clarity provides better clarity at low temperature of the liquid detergent and provides control of the viscosity of the product within a wider range for any given concentration of active ingredient, as will be apparent in the following details. .

The lower aliphatic alcohols preferably have 2 or 3 carbon atoms. Thus, ethyl alcohol, propyl alcohol, isopropyl alcohol or propylene glycol, preferably ethyl alcohol, may be used.

The exact amounts of urea, lower alcohol, and hydrotrope 30 most suitable for a given agent must be compared with the components and amounts of active ingredient used and can be determined by conventional methods. The weight content of this system for controlling viscosity on the basis of the total agent will range from 0.5 to 15% and preferably will be approx. 3-10%. Within this range, the 35 · amount of urea is 1-5% and the amount of alcohol is 0.15-4%. The weight ratio of alcohol to urea is below 1.3: 1, preferably below about 1: 1. 1: 1 and best in the range of approx. 0.37: 1 to approx. 0.85: 1st The content of

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active ingredient is above 30% by weight, preferably about 35 to 45%, including alkylolamide or the like. Varying amounts of hydrotrope such as xylene sulfonate or the like may be added or used in place of a portion of the alcohol or urea to form a ternary system with particular properties such as a pronounced increase in viscosity to a desired level. The amount must be selected by the composition so as to maintain a satisfactory viscosity and a satisfactory haze, and the other desirable properties are maintained. In general, the hydro-0 trop may comprise up to 15% by weight of the total viscosity control system.

The protein used according to the invention is a water-soluble partially degraded protein and may be a partially enzymatically hydrolyzed protein -5 or a heat derived product of protein. This material can be used as a means of overcoming the irritating effect on the skin of the surfactant. When the partially degraded protein is used with or after contact with the surfactants, the prophylactic effect has been found to be present.

The partially degraded protein is characterized as having a gel strength of approx. 0 to 200 Bloom grams.

Partially degraded protein can also give the preparation rinsing and drainage properties. Such hydrolysis products include proteoses,> 5 peptones and polypeptides containing multi-amino acid molecules. These hydrolysis products can be formed by partial enzymatic hydrolysis, such as by the action of trypsin, erepsin or pancreatic enzymes on protein material. The partially degraded protein may also be a heat-derived decomposition product of protein. Proteins partially broken down by heat and having the necessary Bloom strength for use according to the invention can be produced by heating proteinaceous material such as pigs, bones or skins of pigs or beef which have been comminuted to small pieces and immersed in water by autoclaving. 1

A preferred hydrolyzed protein is a partially enzymatically hydrolyzed protein derived from bovine collagen. Typical proteins that can be partially hydrolyzed for use in the invention include casein, gelatin, collagen, albumin, zein, gliadin, keratin, fibroin, globulin, glutenin, and the like. Typical industrial partially enzymatically hydrolyzed proteins include Bacto-Proteose, Proteose, Peptone, Capein-Peptone,

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peptone, the solubilized collagen being obtained by heating pigs or beef legs, feet or skins. The preferred proteins are solubilized beef collagen and solubilized pig collagen which can be prepared as described in the prior art.

A partially hydrolyzed protein may have a relatively wide range of molecular weights in the range of from ca. 500 to 70,000, preferably approx.

500 to 10,000 for gentle action on the hands, and approx.

. 25,000 to 70,000 to provide good drainage properties. The low molecular weight proteins may contain some completely degraded polypeptides such as dipeptides and tripeptides and even some amino acids as a result of the degradation process.

When the protein is used, it is used in amounts ranging from approx. 0.1 to 2.0% by weight, preferably approx. 0.3 to 0.8% by weight.

The liquid detergents of the invention may also contain any of the additives used heretofore in other liquid detergents such as sequestering agents, e.g. salts of ethylenediaminetetra-! acetic acid such as the sodium and potassium salts, and the salts of hydroxyethyl! the ethylene. It is desirable in some cases to color 2q the liquid detergent, and any suitable dye can be used for this purpose. Perfumes can also be added to these agents to give them a pleasant smell.

As the carrier for the liquid cleaner according to the invention, 25 water is available which can be found in varying amounts depending on the composition of the product.

To illustrate some of the beneficial effects of the agent of the invention, agents containing 32% sodium alkyl sulfonate (SAS), 8% ammonium cy2 "Cl5 alkyl triethene oxyether sulfate (ALES), 4.5% ethanol, 3% urea, and the remainder are compared. with agents containing 32% SAS, 4% ALES, 4% ethoxylated alcohol (NI), 2.25% ethanol, 3% urea and the residual water The latter group is then further evaluated by composing similar agents having different ethoxylated 35 alcohols therein , to show the unexpected properties attributed to the agent using a selected group of ethoxylated alcohols among those previously described as being equivalent. The evaluation results are listed in Table 1.

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Table I

Mini plate dish sample = 1.25 g / 1 Viscosity _ Number of plates_ cps 25 ° <

Water hardness 50 ppm 300 ppm T

32SAS / 8ALES_41 _50_91_160

Influence of Ethoxylation Grade 5 '32 SAS / 4ALES / 4NI

C χ 5 EO 47 49.5 96.5 170 C9_H 6 EO 45 53 98 160

Cn ,, 8 EO 47 52 99 180 y — n 10 C13 ~ C15 5 EO 46 48 94 220 7 EO 44 50 94 210 8 EO 45 49 94 220 15

Cin Λ0 47 50.5 97.5 150

1 5 EO

C12-14 5 E0 45 47.5 92.5 210 20 Influence of alkyl chain CQ 5 EO 47 50 97.0 150

ISLAND

C9-II 5 E0 47 49.5 96.5 170 C10-C12 5 E0 47 50.5 97'5 150 25 Cn0-Clc 5 EO 46 48 94 220

iJ ID

C9-C1; L 8 EO 47 52 99 180 C, o Ί c 8 EO 45 49 94 220 U-lo 1 35

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Table I compares the results of two different tests of the effects on wash solutions. One of the tests is a dishwashing test that was performed with two different degrees of water hardness, namely with 50 and 300 parts hardness per unit. million. The second sample is a viscosity-in sample.

They performed dishwashing tests known as the "miniature dishwashing test" described by R.M. Anstett and E. J. Schuck in J.A.O.C.S., Volume 43, page 576, October 1966.

«0

The foregoing results clearly show that with a Cg₂ alkyl chain ethoxylated with at least 5, but not more than 8 moles of ethylene oxide, there is a noticeable improvement in the composition as compared to a non-ethoxylated alcohol and a noticeable improvement over the preparations. containing the ethoxylated alcohol but with higher carbon chain length.

Table II lists the general ranges of the main components within which the preferred agents of the invention are composed.

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Table II

The preferred ranges are the following%

Paraffin Sulfonates 20-35 Alcohol Ether Sulfates 2-8

Cg_i2 alcohol 5-8 EO 2-8

Alkylolamide or alkylolamide EtO condensate 0-8

Urea 1-5

Ethanol 0.15-4.0 Water Q.S.

The following examples further describe the invention and all amounts are by weight.

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Example 1 ο.

Ό

Sodium C ^-C ^ Paraffin Sulfonate 32 (2)

Ammonium C2-2 C15 alkyl triethenoxyethersulfate 4

Cg-C ^ alcohol ethoxamer (6E0) 4 5 Coconut monoethanolamide 2

Urea 3

Ethanol 2.5

Sodium ethylenediamine tetraacetate 0.045

Water (with small amounts of color, preservative and perfume) Residue 10

Total 100 (1) Introduced as an aqueous mixture containing 60% by weight of sulf θ 'night (2) Introduced as an aqueous alcoholic solution containing 60% by weight of sulphates and 10% by weight ethanol. 1 2 3 4 5 6 2

The above product exhibits satisfactory foaming and dishwashing 3 properties combined with preferred physical properties such as a cloudy 4

high point of approx. 5 ° C and a viscosity of approx. 170 centipoise at 25 ° C

5 using a Brookfield viscometer model LVF spindle 1 at 30 rpm. minute. The paraffin sulfonate used has the following approximate composition: 3% C₂, 25% C C, 30% C ^, 25% C ^g, 15% C ^, and 2% C ^g with an average molecular weight of approx. 328. Various impurities can be found in industrial products such as small amounts of free paraffin or disulfonates.

Example 2

A liquid detergent having similar properties to that of Example 1 is prepared by using, instead of the monoethanolamide in the example, an equivalent amount of coconut monoethanolamide condensed with ca. 2 moles of ethylene oxide.

Example 3

A satisfactory liquid cleaner is prepared by use

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of the same materials as in Example 1 in the following amounts: 22% paraffin sulfonate, 6% alkyl ether sulfate, 6% alkanol 8 EO, 5% laurine myristin monoethanolamide, 5% urea and 3% ethanol, the remainder being essentially water.

Example 4

A liquid cleaner having similar properties to that of Example 3 is prepared by reducing the amount of ethoxylated alkanol therein to 2% and by increasing the ethanol therein to 3.3%.

Example 5

A liquid detergent having properties similar to that of Example 1 is prepared with the following composition: 32% sodium C ^-C. Paraffin sulfonate, 2% ammonium Cx₂-C15 alkyl triethene oxyether sulfate, 6% Cg-C₂ alkanol ethoxamer (6E0), 1.1 % ethanol, 3% urea and the rest water.

Example 6

A satisfactory liquid cleaner is prepared with the same composition as in Example 1 except that it contains 2.3% ethanol, 0.6% sodium xylene sulfonate and 1.8% urea.

One of the advantages of the urea and lower alcohol control system is that a change in the physical properties of the agent is possible by varying the ratio of alcohol to urea using amounts selected from the range of 0.15% to 4% ethanol and 1% to 5% urea. In the particular composition of Example 1, the ratio of ethanol to urea is 2.55: 3 (0.85: 1), resulting in a clarity point below 7 ° C and a viscosity of 170 centipoise. The ratio of ethanol to urea is also 0.85: 1 in Example 2, 0.6: 1 in Example 3, 0.66: 1 in Example 4, 0.37: 1 in Example 5, and 1.28: 1 in Example 6.

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By changing the ratio of alcohol to urea by increasing the alcohol content it is possible to decrease the viscosity and raise the point of clarity, whereas by decreasing the alcohol content one can decrease the point of clarity and increase the viscosity. Hydrotropes such as sodium similar effect to the alcohol, ie increases which will raise the point of clarity but decrease the viscosity. Example 6 discloses a composition containing sodium xylene sulfonate, ethanol and urea. As mentioned above, it is important to balance these components of the control system before the IQ for the intervals mentioned to achieve the desired results. In order to provide optimum balance between clarity and viscosity, the total content of the regulatory system must also vary with the content of the active ingredients in the finished agent such as paraffin sulfonate, alcohol ether sulfate and nonionic detergents.

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The point of clarity is also influenced by the amount of esters in the amide and sodium sulfate in the paraffin sulfonate and alkyl ether sulfate used as starting materials for the preparation of the agents, and for agents having a low clarity point, raw materials having a low content of 20 must be used. 'these impurities. The properties listed above for the final composition of Example 1 can best be achieved if the amide does not contain more than 2% esters and the paraffin sulfonate does not contain more than 4% sodium sulfate.

Example 7

Example 1 is repeated with the addition of 0.5% of a solution with 55% solids of protein having a gel strength of 100 Bloom grams. 1

Example 1 is repeated except that the alkanolamide is omitted and the concentration of ethanol is reduced to 2.25% to give a ratio of ethanol to urea of 2.25: 3 (0.75: 1).

Example §

Claims (4)

A clear, stable liquid detergent containing, based on the total weight of the detergent, 20 to 35% of a water-soluble * salt of secondary C ^-C₂q paraffin sulfonates, 2 to 8% alkyl ether sulfates of the formula R (C2H40) nSO3M where R is a C10 -C18 alkyl group, n = 1 to 10, and M is a cation and the cation of the sulfonate and sulfate is sodium, potassium, ammonium and / or mono-, di- or triethanolammonium, and 2 to 8% of a Cg-C ^ alcohol or ether alcohol ethoxylated with 5 to 8 10 moles of ethylene oxide, the total amount of these detergents being at least 30% by weight, and the weight ratio of sulfonate to total amount of sulfate and non-ionic detergent is in the range of 5: 1 to 1.5: 1, and the weight ratio of non-ionic detergent to sulfate detergent is in the range of 3: 1 to 1: 3, and furthermore, urea, 0.15 to 4% ethanol, and water, characterized in that it contains 1 to 5% urea and the weight ratio of ethanol to urea is less than 1.3: 1. A detergent according to claim 1, characterized in that it further contains fatty acid alkanolamides, the total amount of detergents including the fatty acid alkanolamides being 35 to 45% by weight. Cleaner according to claim 1, characterized in that the weight ratio of ethanol to urea is in the range of 0.37: 1 to 0.85: 1. Purifier according to claim 1, characterized in that it additionally contains a lower alkylbenzene sulfonate as a hydrotrope.