DE2516363A1 - LIQUID DETERGENT - Google Patents

Abstract

1458798 Liquid detergent compositions PROCTER & GAMBLE CO 18 April 1975 [19 April 1974] 16112/75 Heading C5D Clear, homogeneous, aqueous, liquid, detergent compositions, suitable for hand washing of tableware, comprise (A) 2 to 12% by weight of a water-soluble sulphonate of formula R 1 SO 3 M, wherein R 1 is a C 8 -C 20 alkyl group and M is alkali metal, ammonium or substituted ammonium; (B) 5 to 30% by weight of a water-soluble ether sulphate of formula wherein R 2 is a C 8 to C 22 aliphatic hydrocarbon radical, n is 1À5 to 12 and M is as defined above; and (c) 2 to 8% by weight of an amine oxide of formula R 3 R 4 R 6 #O wherein R 3 is a C 8 -C 20 aliphatic hydrocarbon group, and R 4 and R 5 are methyl, ethyl, hydroxymethyl or hydroxyethyl; the weight ratio (A) : (B) being 1À15 to 2 : 3; and of (C) : (A)+(B) being 1 : 21 to 1 : 3. The compositions may also comprise up to 15% by weight of a C 8 -C 22 fatty alcohol sulphate and up to 3% by weight of the reaction product of 4 to 15 moles of ethylene oxide with one mole of a C 8 -C 20 fatty alcohol, hydrotropes, solvents, urea, organic acids and salts thereof, sulphuric or phosphoric acid, perfume, dye, fluorescers, tarnish inhibitors, triethanolamine and coconut monoethanolamide.

Description

April 14, 1975

REACHTSANWAtTE

DR. JUR. DIrL-CHEM. WALTER AT

ALFRED HO-Γ ν Μι :? ο C 1 COCQ

DR. JUR. , ■. . ' . H.-J. WOLFP 2 5 ID ό 0 y

DR. JUR. ■ '· ^; -. κ.

6tl FRANKFüäl AM MAlN-HOCHST

Our no. 19 805

Procter & Gamble European Technical Genter Temselaan 100

B - 1820 Strombeek-Bever

Liquid detergent

The present invention relates to a liquid concentrated homogeneous aqueous cleaning agent, which is particularly intended for washing dishes and. the special due proportions ausgev / ählter anionic and nonionic surfactants optimum iteinigungswirkung has, in terms absence of Ji ¹ conversion and banding behaves excellent and shows an appropriate foaming behavior.

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Liquid detergents have become popular over the past few years Washing of dishes, glasses and cutlery and the like by hand largely enforced because they can be easily and quickly dispersed in the cleaning fluid and beq.uem in the Handling are. They mainly contain organic anionic detergent surfactants and also foam boosters and / or builders, the latter in particular to increase the cleaning power of the organic anionic surface active Detergent. It would therefore be logical to improve the effectiveness of a dishwashing detergent by using the amount of detergent surfactants and / or builders or other additives that perform the same function. Scaffolding is often f_Jfree means with large, narrow Surfactants seldom achieve the cleaning effect of those containing builders Gowns, and they can produce negative results such as foaming over, even with only slight movement. Very concentrated remedies are occasionally harsh to the skin, and the excess foam quickly falls in the presence of greasy ones Dirt together.

The liquid cleaning agents should preferably be clear, homogeneous, be resistant and concentrated against freezing and thawing. However, it turned out to be difficult, clear, homogeneous, persistent and to formulate concentrated liquid agents. The aim of achieving clearer, more homogeneous, more concentrated and more stable Means optimal proportions of surface-active Detergents and other customary additives do not always come in the optimal proportions with regard to cleaning behavior together. Such a loss of effectiveness is either accepted or through additional components with abandonment compensated for advantageous properties

The factors that are important when cleaning dishes and the subsequent

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Portions of the hand rinsing agents commercially available today have been studied to find that the effectiveness some detergents based on anionic and nonionic surfactants surprisingly improved can be achieved by carefully balancing certain non-ionic and anionic surface-active agents Detergents, so that one sustained foam capacity

ity in the temperature range between about 50 and about 15 ° G,

further

regardless of the composition of the food residues, optimal Cleaning performance per amount of surfactant detergent, and with no films, stains or streaks on the rinsed objects and no other properties how homogeneity, constancy and concentration have to be sacrificed.

The present invention thus relates to a liquid cleaning agent, that is clear, homogeneous, easy to remove, watery, persistent and is focused and has optimal refusal properties, exhibits adequate and sustained foam behavior and does not leave behind any films, spots or streaks.

The liquid cleaning agent according to the invention contains, calculated on the total weight of the agent

(A) about 2 to about 12 percent by weight of a water-soluble aliphatic Hydrocarbon sulfonates of the general formula

R ¹ SO ₃ M (I)

wherein R is a straight-chain or branched saturated hydrocarbon radical having 8 to 20 carbon atoms and M is an alkali metal, ammonium, dimethyl, diethyl, tri = methyl, triethyl, dimethanol, diethanol, trimethanol or represent triethanolammonium,

(B) about 5 to about 30 wt. ^ Of a water-soluble polyethylene =

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Glycol ether sulfate of the general formula ² H ₄ O) _n SU ₃ M (II)

2
wherein R is a straight-chain or branched, saturated one

or unsaturated hydrocarbon radical having 8 to 20 carbon atoms and η represent a number from 1.5 to 12 and M has the meaning given above, and (G) about 2 to about 8 wt. ^ Of a tertiary amine oxide of the general formula

R ³ R ⁴ R ⁵ N- ^ O (III)

• 5
wherein R is a straight-chain or branched, saturated or unsaturated hydrocarbon radical with 8 to 20 and

4-5 preferably 12 to 16 carbon atoms and R and R represent a methyl, ethyl, hydroxymethyl or hydroxyethyl radical,

wherein the weight ratio of (A) to (B) between 1: 1.5 and 2: 3 and the weight ratio of (C) to (A) plus (B) between 1:20 and 1: 3.

A preferred liquid cleaning agent according to the present invention contains, calculated on the total weight of the agent,

(A) about 2 to about 5 wt% of an aliphatic hydrocarbon sulfonates,

(B) about 10 to about 27 wt. ^ Of a polyethylene glycol ether sulf = fats,

(C) about 2 to about 5 wt. ^I ; 4 of a tertiary amine oxide,

(D) up to 15% by weight and preferably 2 to 6% by weight of a water-soluble aliphatic hydrocarbon sulfate of the general formula

R ⁶ SO ₄ M (IV)

wherein R is a straight-chain or branched, saturated one

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or unsaturated aliphatic hydrocarbon radical with Represents 8 to 22 carbon atoms, preferably a straight-chain alkyl radical having 12 to 14 carbon atoms and M is as defined above, and (E) up to 3% by weight of a reaction product of from about 4 to about 15 moles of ethylene oxide and 1 mole of an organic hydrocarbon with a reactive hydrogen atom and 8 to 24 carbon atoms,

where the weight ratio of (A) to (B) is between 1:13 »5 and 1: 4, the weight ratio of (G) to (A) plus (B) is between 1:15 and 1: 4 and the maximum amount of (D) plus (e) from about 9 Gew.yo and preferably is 5 wt. $.

The properties of a dish detergent are appreciated by most consumers rated based on foaming. The liquid dishwashing detergents available on the market today are therefore largely geared towards meeting this expectation with regard to the foam behavior, which stands for cleaning meet, with special agents that control the foam behavior such as Pettsäurediethanolamides are added. The consumer, who has adjusted to the cleaning effect of a washing solution through the amount of foam generated and the If the foam remains to be assessed, this is easily mislead, since various protein-containing food residues Re-create and maintain foam produced by the detergent surfactant, even towards the end of the Rinsing process, although the cleaning power is almost used up here is. In the case of the detergents according to the invention, the foam is produced exclusively by the surface-active detergents generated. This foam is created by greasy foods such as roasts, meat fat, french fries, salad oil and the like not eliminated, due to the special proportions of the detergents. Because of this special - "» Narrow ratios of the surface-active detergents

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also a maximum cleaning effect per kenge available Achieved more surface active compared to agents with the same total amount of the same detergents, but in different proportions.

It is therefore extremely surprising that only by carefully balanced proportions of special non-ionic and Anionic detergent surfactants can be formulated into a highly effective dishwashing detergent that is long lasting Creates foam and is liquid, clear, homogeneous, stable and concentrated at the same time.

As already mentioned, this improved behavior could only be achieved by paying special attention to when washing dishes Hand important factors.

The cleaning agents according to the invention can be used be set so that the detergent works optimally under special circumstances, for example when rinsing very greasy dishes or dishes that are mainly soiled with protein residues Dishes, or according to 3 different eating habits Countries incurred dishes, in which a further particular advantage of the invention is seen. The optimization is done by changing the ratio of tertiary amine oxides and anionic surface-active detergents in the specified ranges carefully changed and / or by surface-active ethoxylates are incorporated into the detergent in relatively small but precisely measured amounts.

The following are the liquid in the invention Nonionic and anionic surfactant detergents to be used as dishwashing detergents, as well as the other ingredients described in more detail. Is referred to in this description

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to an anionic detergent surfactant salt or other acidic constituents, it is the sodium, potassium, ammonium, trimethyl, iriethyl, dimethyl, Diethyl, trimethanol, diethanol, triethanol and dimethanol ammonium salts, unless otherwise stated.

Suitable surface-active detergents are:

(1) Water-soluble aliphatic hydrocarbon sulfates of the formula H SOJü (I); they are the salts of the reaction products obtained by known sulfonation methods (including bleaching and hydrolysis) from hydrocarbons of the methane series including the iso-, neo-, meso- and η-paraffins with 8 to 20 and preferably 14 to 18 carbon atoms and sulfonating agents such as SO ,, H ₂ SO. and oleum. Preference is given to sulfonated ^c <ia ^ q ~ paraffins, in particular the secondary paraffin sulfonates.

(2) polyethylene glycol ether sulfates of the formula E ² O (C ₂ H ₄ O) _n SO ₃ M (II); They are the salts / the reaction products obtained by known processes from 1 mol of a straight-chain or branched, saturated or unsaturated hydrocarbon having 8 to 20 carbon atoms and a reactive hydroxyl group, preferably a higher fatty alcohol such as tallow or coconut alcohol, and 1.5 to 12 and preferably 2 to 6, particularly preferably 3 mol of ethylene oxide. Specific examples are the C ₁ O- λα. lcyi_O- (C ₂ H ₄ O) ₃ -SO ₃ ~ N- (C ₂ H ₄ OH) ₃ , coconut-0- (C ₂ H ₄ O) ₄ ~ SO ₃ Na, C ₁₄ A ^ yI-O- (C ₂ H ₄ O) ₃ -SO ₃ NH ₄ and C ₁₂ _ ₁₆ alkyl-O- (G ₂ H ₄ O) ₆ -SO ₃ K.

ionic ¹ ^ a ^

(3) Non-tertiary amine oxides of the general formula R ^ ITl

) ₃ where the arrow indicates a semi-polar bond; they are generally made by direct oxidation of the corresponding tertiary amirre. R ^ denotes a higher_molecular hydrocarbon radical with 8 to

/ ~ of sulfuric acid esters

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and preferably 12 to 16, particularly preferably 12 carbon atoms, or a mixture of dodecyl and decyl and

Tetradecyl radicals, in which at least 50 $ of the radicals from Dode =

A 5
Cyl residues exist. R and R, which can be the same or different, denote a methyl, ethyl or hydroxy =
methyl and hydroxyethyl radical. Specific examples of suitable tertiary amine oxides are dimethyldodecylamine oxide, Di =
ethyl tetradecylamine oxide, bis (2-hydroxyethyl) dodecylamine oxide bis (2-hydroxyethyl) -3-dodec> -1-hydroxypropylamine oxide,
Dimethyl-2-hydroxy-dodecylamine oxide and diethyl eicosylamine oxide.

Optional constituents, which are preferably also present in cleaning agents according to the invention to reinforce a special property, for example the property, none
Films and strips to form are

(4) water-soluble aliphatic hydrocarbon sulfates of
Formula R SO-H (IV); they are the salts of a reaction product of a saturated or unsaturated Fettaiko hol with 8 to 22 and preferably 12 to 16 carbon atoms and a sulfonating agent such as for example

SO. ,, HpSO. or oleum, which according to known sulphonation processes drive were received.

(5) non-ionic condensation products - to improve the Fettsuspendierung -, the known condensation of 4 to about 15 moles of ethylene oxide with 1 mole of an organic hydrophobic compound that is alkylaromatic or is preferably aliphatic and 3 to 20 carbon atoms and at least 1 reactive hydrogen atom, preferably has a reactive hydroxyl group. The condensation products are preferred about 6 to about 12 moles of ethylene oxide per mole of an aliphatic alcohol having 12 to 16 carbon atoms, in particular

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Condensation products from the middle fraction of coconut alcohol and about 6 moles of ethylene oxide and ialg alcohol and about 10 to 11 moles of ethylene oxide. Further specific examples are with a polyethylene glycol - ^ esterified Üq * ..- fatty acid ester / with a molecular weight of about 30QbIs8ÖoV.

Other suitable ingredients or additives for the purpose of improvement the stability or homogeneity of the agents according to the invention can be added

(6) Hydrotropes or solvents consisting of C 1-4 alcohols, sodium, potassium and ammonium salts of C 1-4 alkylphenyl and C, p-dialkylphenyl sulfonic acids and urea. Only small amounts of these solubilizing substances are required in order to prevent phase separation and to promote the mutual solubility of special anionic and nonionic surface-active detergents. Already amounts of less than 2 wt. Fi of the solubilizing agent can be used when surface-active detergents with hydrophobic Hesten atoms with specific number of carbon, preferably between 14 and 18 used. Incidentally, the upper limit should not exceed 10jo, since too much solubilizing agent adversely affects the viscosity of the cleaning agent. Specific examples of solubilizing substances are methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, isoamyl alcohol, potassium and sodium toluene, xylene and cumene sulfonate.

(7) low molecular weight organic acids such as acetic acid, citric acid, Malic acid, gluconic acid, maleic acid, and lactic acid and their alkali metal salts. These acids or salts can, but only to a limited extent, by sulfuric acid and phosphoric acid or partially neutralized Salts are replaced. The organic acids and preferably the partially neutralized organic acids

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nen in amounts up to 14 wt. ^ are added, while the less soluble inorganic salts are only added in amounts of up to 3% by weight, calculated on the total weight of the agent should be. Preferably, cleaning agents intended for washing glasses are acetic acid or citric acid added. The preferred amounts are 5 to 9 yS.

(8) Fragrances, dyes, fluorescent substances, deposit formation inhibiting substances such as benzotriazole or ethylene = thiourea and bactericides.

As mentioned earlier, the excellent properties go with the cleaning agent according to the invention on the carefully balanced Ratio between the selected non-ionic and anionic surfactant detergents. The relationship of these surfactant detergents to one another is of such importance that means in which the weight ratio from paraffin sulfonates to polyethylene glycol ether sulfates outside the range 1:15 to 2: 3, largely lose their lasting foam resistance and with regard to the Cleaning behavior fall off, despite the other prescribed Weight ratios of paraffin sulfonates plus alkyl = ether sulfates to tertiary amine oxide are complied with.

The superior behavior of the agents according to the invention with regard to Fat suspension and foam stability is illustrated by the following test:

Two rows A and B of 5 dishwashing liquids each (A., ... Ac »B ..., .Bc) are produced. Any rinsing liquid row A contains 0.2 Gew.yo per liter of a detergent according to following Example I. Each B-series flushing fluid contains 0.2% by weight per liter of one on the market today Washing-up liquid, the composition of which is given below.

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Tap water with a water hardness of about 3.4 millimoles CaCO ^ per liter is used to produce the rinsing liquids. Each rinsing bath contains approx. 9 liters. The temperature is around 47 ° G at the start of each rinse cycle.

In each rinsing liquid of the two rows (5 rinsing liquids per row), 10 plates about 25 cm in diameter, which are soiled with roasted sauce and fat from French fries and obtained from a restaurant, are immersed. The plates to be rinsed in the rinsing liquids A .., A ", B ₁ and B" are immersed for 15 minutes. 26 ° C falls. The plates to be washed in the other washing liquids are immersed for 2 minutes (temperature drop approx. 12 G). Then, all the plates under water for about 15 seconds to be easily abraded with a conventional dish cloth and then to the draining and drying in air turned off (at room temperature about 21 ⁰ C).

As soon as the plates are dry, three experienced examiners compare the appearance of the plates, comparing the sentence the plates that were washed in the first washing liquid in row A with the set of 10 plates that were in the first Rinsing liquid of row B have been rinsed, then the plates rinsed in the second rinsing liquid of row A are also rinsed compared to the 10 plates washed in the second washing liquid of row B, etc.

The differences in appearance are expressed as follows: equal (0), better (+) and much better (++) · The The results are summarized in the following table:

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Tabel

line A. B. A. B. A. B. A. B. A. B. Wash basin. 1 1 2 2 3 3 4th 4th VJl 5

Examiner 1 + ++ + + + Examiner 2 + ++ + O + Examiner 3 ++ + + O +

The superiority of the rinsing liquids of series A ^ and A ₂ over B ₁ and B ₂ (washing at low temperatures) can be clearly seen from the table.

The foam height and density of the rinsing liquids, -Α, - and Έ ^ -Β ^ are about the same, the foam density and foam height of the rinsing liquids A ₁ and A ₂ are better compared to B. and B _2.

The liquid dishwashing detergent of series B, which is used as a representative of a market product, consists of 10% by weight of the sodium salt of C12-16 ^{: Paraffi} ' ^lsulfona " ^teri " 1% by weight of the sodium salt of sulphated C ^ _2-1 g Alcohol-ethylene oxide condensates (on average 4 ethylene oxide units), 7 wt. ^ Sodium coconut ^{alcohol sulfate, 5 wt. ^ C} ip-1 / "" Alkyl-dimethyl = amine oxide, 3 wt. ? i ethanol and the remainder water. The total amount by weight of the surface-active

Substances was about 28% by weight in the detergent used in the A series rinse fluids .

In the following examples, all percentages relate on percent by weight.

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example 1

C _{12 U} alcohol-ethylene oxide (3) sulfate, Na salt, 6.0 $ C ₁₂ _ ₁₆ alcohol sulphate, NH.-salt,

3.0 $ ^C 12-18 ^sec * JParaffin sulfonate sodium salt,

$ 3.0 dimethyldodecyl amiaoxide, $ 7.0 ethanol, remainder water.

Example 2

C _12-1 . -Alcohol-ethylene oxide (3) -sulphate, Na-Salz, 2.5 ^€ / ό G ^. ^^ g paraffin sulfonate triethanolammonium salt,

2.0 $ C ₁ 2 _- -He ~ alcoholsilfate

4.0 $ diethyldodecylamine oxide,

2.5 $ isopropanol,

3.0 $ toluenesulfonate - sodium salt,

Rest water

Example 3

12.0 $ Cjg-alcohol-ethylene oxide (4) -sulphate, NH.-salt,

2.5 $ ^C 13-18 ^paraffin sulfonate »NH.-salt,

3.5 $ dihydroxyethyl tetradecylamine oxide,

$ 2.0 condensation product of coconut alcohol and 6 moles of ethylene oxide per mole of alcohol,

$ 0.5 acetic acid,

$ 2.0 sriethanolamine,

6.0 $ ethanol,

Rest water.

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Example 4

17.0 $ coconut alcohol-ethylene oxide (3) -sulfate, ΝΗ, -salt, 3.0 $ coconut alcohol sulfate, ΝΗ, salt,

2.5 $ paraffin sulfonate ammonium salt (average mol wt Hydrocarbon residues = 196)

Dimethyldodecylamine oxide,

Ammonium sulfate,
2.0fo monoethanol coconut amide,
6.0 56 ethanol,
Rest water.

Especially for washing glasses with high melting points .Fat, protein-containing residues and farinaceous food residues Detergents suitable for dirty plates are:

JL VI VII VIII IX

Coconut Alcohol Ethy = $ 24.0 - - '$ 28.0 $ 14.0

lenoxide (3) sulfate

Ammonium salt

Coconut Alcohol Ethy = - $ 26.0 $ 17.5

lenoxide (3) sulfate

Sodium salt

C _{15- 18} -Paraffinsulfo = 3.0 $ 5.0 $ 2.5 $ 7.0 $ 3.0 $

nat sodium salt

C _{1 2} _ _Λ . - Alcohol Sulphate- - $ 4.0 $ 5.0 $ 3.0 $ 6.0

Ammonium salt

Dimethyl-C ₁₂ _ ₁₆ -alkyl 5.0 $ 3.0 $ 5.0 $ 6.0 $ 4.0 $

amine oxide

Coconut Alcohol Ethy = - - $ 1.0 $ 1.5 -

lenoxide (6) condensate

Lactic Acid - - $ 2.0 - -

Sodium citrate - - - - -

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VI VII VIII IX

Potassium toluene = 4.5 / - 2.0 ^ sulfonate

Ethanol 3, Of ₀ 5, o # 7.55

Water rest

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Claims (4)

Claims Liquid, clear, homogeneous, concentrated, easy to Removable, aqueous cleaning agent containing water-soluble surface-active detergents and customary smaller additives, characterized in that, calculated on the total weight of the agent, (A) about 2 to about 12 wt., J of a water-soluble aliphatic Hydrocarbon sulfonate of the general formula R ¹ SO ₅ M (I) wherein R is a straight-chain or branched saturated hydrocarbon radical having 8 to 20 carbon atoms and M is an alkali metal, ammonium, dimethyl, di = ethyl, trimethyl, triethyl. Dimethanol, diethanoi, Represent trimethanol or triethanol ammonium, (B) about 5 to about 30% by weight of a water-soluble polyether lenglycol ether sulfate of the general formula R ² O (C ₂ H ₄ O) ₁₁ SO ₅ M (II) wherein R is a straight-chain or branched saturated or unsaturated hydrocarbon radical with 8 to 20 carbon atoms and η represent a number from 1.5 to 12 and M has the meaning given above owns, (G) about 2 to about 8 wt. Ψ of a tertiary amine oxide of the general formula R ⁵ R ⁴ R ⁵ IHO (III) wherein R is a straight-chain or branched, saturated or unsaturated hydrocarbon ^{radical having 8 to 20 carbon atoms and R 4} ″ and R ^{5 are} methyl, ethyl, hydroxymethyl or hydroxyethyl radicals, and 509845/0997 . Contains water, and wherein the weight ratio of (A) to (B) is from 1:15 to 2: 3 and the weight ratio of (G) to (A) plus (B) is from 1:20 to 1: 3. 2. Cleaning agent according to claim 1, characterized in that the water-soluble hydrocarbon sulfonate is a secondary Is paraffin sulfonate having 14 to 17 carbon atoms. 3 cleaning agent according to claim 1, characterized in that that the water-soluble polyethylene glycol ether sulfate is different from an alcohol with 12 to 16 carbon atoms derives. 4. Cleaning agent according to claim 1 to 3 »marked calculated on the total weight of the agent (A) about 2 to about 5 weight percent of a secondary paraffin sulfonate with 14 to 17 carbon atoms, (B) about 10 to about 27 wt. ° / o of a Polyäthylenglycoläther = ρ sulfate of the formula II, in which R is a fatty alcohol radical with 12 to 16 carbon atoms and η represent a number from about 3 to about 6,
(G) about 2 to about 5 percent by weight of a tertiary amine oxide, (D) about 2 to about 6 wt. Of a fatty alcohol sulfate with 12 to 16 carbon atoms, (E) up to 3% by weight of a reaction product from 4 to 15 Moles of ethylene oxide and 1 mole of fatty alcohol with 12 to 16 carbon atoms and Rest water, wherein the weight ratio of (A) to (B) is from 1: 13.5 to 1: 4 the weight ratio of (G) to (A) plus (B) from 1:15 to 1: 4 and the maximum amount of (D) plus (E) 9 and preferably Weight '; £ is. For: Procter & Gamble European Technical Center
Strombeek-Bever / Belgium Dr. H. (M ·. Beil Lawyer 509845/0997