DE2516391A1 - LIQUID DETERGENT - Google Patents

Abstract

1458783 Liquid detergent compositions PROCTER & GAMBLE CO 18 April 1975 [19 April 1974] 16093/75 Heading C5D Liquid detergent compositions, suitable for hand washing of tableware, comprise (A) 8 to 35% by weight of a water-soluble sulphonate of formula R 1 SO 3 M, wherein R 1 is C 8 -C 20 alkyl and M is alkali metal, or an ammonium or substituted ammonium radical; (B) 2 to 20% by weight of a water-soluble sulphate of formula R 2 SO 4 M, wherein R 2 is a C 8 -C 22 aliphatic hydrocarbon group and M is as defined above; (c) 0À5 to 4% by weight of a water-soluble ether sulphate of formula R 3 O(C 2 H 4 O) n SO 3 M wherein R 3 is a C 8 -C 22 aliphatic hydrocarbon group and M is as defined above; and (D) 3 to 8% by weight of an amine oxide of formula wherein R 4 is a C 8 -C 20 aliphatic hydrocarbon group, R 5 and R 6 each are methyl, ethyl, hydroxymethyl or hydroxyethyl; the weight ratio (A) : (B) being 1 : 2 to 10 : 1, of (A): (C) being 25 : 1 to 12 : 1 and of (D) : (A)+(B)+ (C) being 1 : 40 to 1 : 5. The compositions may also comprise up to 15% by weight of the reaction product of 4 to 15 moles of ethylene oxide and one mole of an aliphatic C 8 -C 20 alcohol, hydrotropes, solvents, urea, organic acids, sulphuric or phosphoric acid, triethanolamine, sodium acetate, ammonium sulphate, coconut monoethanolamide, sodium lactate or sodium citrate.

Description

LAWYERS »* ■ DR. JUR. DIFL-CHEM. WALTER AT

ALFRED HOEPPENER

DR. JUR. DÜL-Cüc.M. H.-J. WOLFP

DR. JUR. HAixS Ci-.3. BtIL

FRANKFURFAM MAIN-HOCHS? ο r A βO Q 1

Our no. 19 804

Procter & Gamble European Technical Genter Temselaan 100

B - 1820 Strombeek-Bever

Liquid detergent

The present invention relates to a liquid cleaning agent with improved cleaning behavior, in particular a Liquid, concentrated, homogeneous aqueous detergent that is specially designed for washing dishes by hand and that due to special proportions of selected anionic and non-ionic surface-active agents an excellent one Has the ability to suspend fat and shows adequate foaming behavior.

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Liquid detergents have been used extensively in the past few years for washing dishes, glasses, cutlery and the like by hand prevailed because they can be easily and quickly dispersed in the cleaning liquid and conveniently in the Handling are. However, it has proven difficult to formulate aqueous liquid cleaning agents that are homogeneous, light can be removed, are resistant to freezing and thawing and are concentrated. Especially alkylbenzenesulfonates, paraffin sulfonates, sulfated fatty alcohol / ethylene oxide adducts must be mixed in certain proportions so that stable, receives clear and homogeneous preparations. Unfortunately, they fall in order to achieve consistent, clear and homogeneous means optimal proportions do not always go hand in hand with the optimal proportions in terms of cleaning behavior, and the latter can still change if additional surface-active agents are added to improve the properties.

The present invention thus relates to a liquid, clear, homogeneous, easily removed, aqueous, stable and concentrated cleaning agent which, in addition to a superior cleaning effect, has a particularly good fat suspension effect and shows an adequate and sustained foam behavior, as it is particularly suitable for hand washing dishes.

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

(A) about 8 to about 35% by weight of the water-soluble aliphatic Hydrocarbon sulfonate of the general formula

where R is a straight or branched chain chain Hydrogen radical with 3 to 20 carbon atoms and

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M is an alkali metal, ammonium, dimethyl, diethyl, trimethyl, Triethyl, dimethanol, diethanol, trimethanol or represent triethanolammonium,

(B) about 2 to about 20 Gevr.? » a water-soluble aliphatic Hydrocarbon sulfate of the general formula

R ² SO ₄ M (II)

wherein R is a straight-chain or branched, saturated or unsaturated hydrocarbon radical having 8 to 22 carbon atoms represents and M has the meaning given above,

(C) about 0.5 to about 4 Gew.Ji of a water-soluble polyethylene glycol ether sulfate the general formula

R ⁵ O (S ₂ H ₄ O) _n SO ₅ M (III)

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

(D) about 3 to about 8% by weight of a tertiary amine oxide of the general formula

R ⁴ R ⁵ R ⁶ N- *) (IV)

wherein R is a straight-chain or branched, saturated one or unsaturated hydrocarbon radical having 8 to 20 and preferably 12 to 16 carbon atoms and R and R a methyl, ethyl, hydroxymethyl or hydroxyethyl radical represent,

the weight ratio of (A) to (B) being between 1: 2 and 10: 1, the weight ratio of (A) to (ü) between 25i1 and 12: 1 and the weight ratio of (D) to (A) + (B) + (G) is between 1:40 and 1: 5.

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

(A) about 15 to about 30 weight 7b of an aliphatic hydrocarbon sulfonate,

(B) about 4 to about 15 weight percent of an aliphatic hydrocarbon Sulfate,

(C) about 1 to about 3 percent by weight of a polyethylene glycol ether sulfate,

(D) about 3 to about 6 wt. I »of a tertiary amine oxide and

(E) up to 15% by weight and preferably 2 to 7% by weight of a reaction product from about 4 to about 15 moles of ethylene oxide and 1 mole of an organic hydrocarbon with a reactive one Hydrogen atom and 8 to 24 carbon atoms,

where the weight ratio of (A) to (B) between 2: 1 and 10; 1 the weight ratio of (A) to (C) between 15 * 1 and 12: 1 and the weight ratio of (D) / (a) + ( B) v * "is between 1:20 and 1: 5, and the maximum ^lü close to (B) + (E) is about 20% by weight and the weight ratio of (B) to (E) is greater than 1: 1 and preferably above 5: 1.

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 the cleaning effect fulfill. However, fatty food residues such as roast beef, meat fat, French fries, salad oil and the like can cause the Foam collapse as soon as these fats liquefy at the beginning of the washing process when the washing liquid is still warm This fat is deposited again on the pieces that were rinsed last and on the hands, if this is greasy Dirt cannot be kept in suspension.

retroactively
changed

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The important factors and disadvantages when cleaning dishes of the handwashing agents commercially available today were investigated, and it was found that the effectiveness of some detergents based on anionic and nonionic surface-active gowns surprisingly improves can be achieved by carefully balancing certain non-ionic and anionic surface-active agents Detergents, so there is a lasting foam capacity in the temperature range between about 50 and about 15 ° C, regardless of the composition of the food residues, and as an iJOlge, it has an overall improved cleaning behavior.

The liquid dishwashing detergents on the market today mainly contain organic anionic surface-active detergents and also foam boosters and / or builders, the latter being intended in particular to increase the cleaning power of the organic anionic surface-active detergent. It would therefore be logical to improve the performance of a dishwashing agent by increasing the level of detergent surfactants and / or builders or other additives that perform the same function. Builder-free agents with large amounts of surfactants seldom achieve the cleaning effect of builder-containing agents, and they can produce negative results such as over-foaming, even with only slight agitation. Very concentrated remedies are occasionally ^{harsh for the i: t} aut, and the excessive foam collapses quickly in the presence of greasy dirt.

It is therefore extremely surprising that by carefully balanced Characteristic ratio of special non-ionic and anionic surface-active detergents a highly effective dishwashing detergent can be formulated that is fluid, clear, homogeneous, stable and concentrated.

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

The detergent according to the invention can have no effect 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, or different ones depending on your 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 detergent surfactants in very specific areas carefully and / or by changing surface-active ethoxylates are incorporated into the detergent in relatively small but precisely measured amounts.

The following are the. liquid detergents according to the invention non-ionic and anionic surface-active agents to be used Detergents and the other ingredients described in more detail. Is referred to in this description to a salt of an anionic detergent surfactant or other acidic ingredient, it is the Sodium, potassium, ammonium, trimethyl, triethyl, dimethyl, Diethy1, trimethanol, diethanol, triethanol and dirnethanol = ammonium salts, unless otherwise specified.

Suitable surface-active detergents are:

/ \ on—

(1) Water-soluble aliphatic hydrocarbon sulfates of the J? Ormel R SO-, 11 (I); they are the salts of the after known Sulfonation methods (including lead and hydrolysis) obtain reaction products from hydrocarbons of the methane series including iso-, neo-, meso- and n-paraffins with 8 to 2 ^ and preferably 14 to 18 carbon

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atoms and sulfonants such as SO ,, H ₂ SO., and oleum. Sulfonated paraffins, in particular secondary paraffin sulfonates, are preferred.

(2) Water-soluble aliphatic hydrocarbon sulfates of

Formula R SO-M (II); they are the salts of a reaction product of a saturated or unsaturated petroleum alcohol with 8 to 22 and preferably 12 to 16 carbon atoms and a sulfonating agent such as SO ₅ , HpSO, or oleum, which were obtained by known sulfonation processes.

(3) polyethylene glycol ether sulfates of the formula R ⁵ O (C ₂ H ₄ O) _n SO, M (III); they are the salts / the reaction products obtained by known processes from 1 IJoI of a straight-chain or branched, saturated or unsaturated hydrocarbon with 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, preferably 3 mol of ethylene oxide. Specific examples are the C-12-I4. Alkyl-O- (O ₂ H ₄ O) ₃ -N- (C ₂ H ₄ OH) ₅ , KOkOSnUB-O- (C ₂ H ₄ O) ₄ -SO ₅ Na, C ₁₄ -AlkVl-0- (C. ₂ H ₄ O) ₅ -SO ₅ NH ₄ and C _12-16 Alky1-0- (C ₂ H ₄ O) ₆ -SO ₅ K.

(4) Non-ionic: tertiary amine oxides of the general formula R ⁴ R ⁵ R N - ^ - O (IV), wherein the arrow denotes a semipolar bond; they are generally made by direct oxidation of the corresponding tertiary amine. R denotes a high molecular weight hydrocarbon radical with 8 to 20, preferably 12 to 16 and particularly preferably 12 carbon atoms, or a mixture of dodecyl and decyl and tetradecyl radicals, in which at least 50% of the radicals consist of dodecyl radicals. R and R, which can be the same or different, denote a methyl, ethyl, hydroxymethyl or hydroxyethyl radical. Specific examples of suitable tertiary amine oxides are dimethyldodecyl amine oxide, diethyl tetradecyl anine oxide, bis (2-hydroxyethyl) ~ / ~ of sulfuric acid esters

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dodecylamine oxide, bis (2-hydroxyethyl) -3-dodecoxy-1-hydroxy = propylamine oxide, dimethyl-2-hydroxydodecylamine oxide and Di = ethyleicosylamine oxide.

(5) The other non-ionic ··., Which can be present in the agents according to the invention, is a condensation product which is obtained by condensation, known to me, of 4 to about 15 mol of ethylene oxide with 1 mol of an organic hydrophobic compound which is alkylaromatic or is preferably aliphatic and has S to 20 carbon atoms and at least one reactive hydrogen atom, preferably one reactive hydroxyl group. The condensation products of about 6 to about 12 moles of ethylene oxide per mole of aliphatic alcohol having 12 to 16 carbon atoms, especially condensation products of the middle fraction of coconut alcohol and about 6 moles of ethylene oxide or algae alcohol and about 10 to 11 moles of ethylene oxide, are preferred. More specific examples are a polyethylene glycol having a molecular weight of about 300 to 800 ^c esterified q_i - fatty acid ester.

Prepare suitable ingredients or additives for the purpose of improvement the cleaning behavior of the agents according to the invention can be added are:

(6) Hydrotropes or solvents consisting of C 1, alcohols, sodium, potassium and ammonium salts of C 1, -alkylphenyl and Cj_ ₂ -dialkylphenylsulfonic 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. Amounts of less than 2% by weight of the solubilizing agent can be used if surface-active detergents with hydrophobic radicals with a specific number of carbon atoms, preferably between 14 and 13, are used. the

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Incidentally, the upper limit should not exceed 10 $ b because it is too much Solubilizing gown adversely affects the viscosity of the detergent. Specific examples for Solubilizing substances are methyl, ethyl, n-propyl, Isopropyl, tert-butyl, η-butyl, 19obutyl, isoamylal = alcohol; Potassium and sodium toluene, -sylene- and -cumene sulfonates.

(7) Low molecular 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, be replaced by sulfuric acid and phosphoric acid or their partially neutralized salts. The organic acids, and preferably the partially neutralized organic acids may be 14 wt · in amounts up;> are added *, while the less soluble inorganic salts tight up to 3 wt ° ß} y calculated only in ^ to the total weight of the composition.. , should be admitted. Acetic acid or citric acid are preferably added to certain cleaning agents for washing glasses. The preferred narrow range is from 5 to 9fo.

(8) Fragrances, dyes, fluorescent substances, substances that inhibit the formation of deposits such as üenzotriazole or ethylene = thiourea and bactericides.

As mentioned earlier, the excellent marketing features 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 surface-active detergents to one another is of such importance that agents in which the weight ratio of paraffin sulfonates to polyethylene glycol ether sulfates is outside the range 25: 1 to 12: 1, part of their lose fat-suspending effect and foam resistance, whether

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equal to the other prescribed weight ratios of Paraffin sulfonates to alkyl sulfates and from tertiary amine oxides to the sum of the paraffin sulfonates and alkyl sulfates complied with are.

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

Zv / ei rows A and B of 5 dishwashing _{liquids each (A ..... A 1} -J Bp.Br) are produced. Each rinsing liquid of the A series contains 0.2% by weight per liter of a detergent according to Example I. Each rinsing liquid of the B series contains 0.2% by weight per liter of a detergent currently on the market, the composition of which is given below.

Tap water is used to produce the flushing liquids a water hardness of about 3.4 millimoles OaCO per liter is used. Each rinsing bath contains approx. 9 liters, the temperature is at the beginning of each flushing process approx. 45 C

In each rinse liquid of the two borrowers (5 rinsing liquids per row), 10 plates about 25 cm in diameter, which are soiled with roast beverages and fat from French fries and obtained from a school restaurant, are immersed. The plates to be rinsed in the rinsing liquids A *, Ap, B .. and Bp are immersed for 15 minutes. 26 ° C falls. The plates to be rinsed in the other rinsing liquids are immersed for 2 minutes (temperature drop, about 10 ⁰ G). Then all plates are lightly rubbed under water for about 15 seconds with a standard dishcloth and then left to drain and dry in the air (room temperature about 23 ° C).

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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 the 10 plates washed in the second washing liquid of row B. compared etc.

The differences in appearance are expressed as follows: the same (O), better (+) and much better (++). the The results are summarized in the following table:

TABEL

line AWAY AWAY AWAY AWAY AWAY Washing liquid 1 1 2 2 3 3 4 4 5 5 Examiner 1
Examiner 2
Examiner 3 ++
+
++ ++
++
++ +
+
++ +
0
+ +
+
+

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

The liquid dishwashing soap series B, which is used as a representative of a market product, consists of 10 wt. $ Of the sodium salt of ^ λο-Λ6 P ^ara ffi ^NSU lf ° ^na ''^'s"10 wt. $ Of the sodium salt of sulfated ü .pg-alcohol-ethylene oxide condensate '(on average 4 ethylene oxide units), 7 wt. ^ potassium coconut alcohol sulfate, 5 i

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amine oxide, 3 wt. 50 xylene sulfonate sodium salt, 5 wt. ethanol and the rest of the water. The total weight amount of surfactants in that used in the A series rinse fluids Detergent was about 29.5 wt.

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

example 1

1 »5? O C ₁₂ _ ₁₄ alcohol-ethylene oxide, sulfate (3) sodium salt, 6, O> 4 C _12-16 -AIkOhOlSuIfat, NH ₄ -SaIz, 19 * 0 ^ C ₁₂ _ ₁₈ -sec -Paraffin sulfonate, sodium salt, dimethylilodecylamine oxide,
Ethanol,
Rest water,

Example 2

2.0 $ G _12-1. -Alcohol-ethylene oxide (3) -sulphate, sodium salt,

25, O ^ C ₁ .__. | G-paraffinsulfonate-triethanolammonium salt,

3.0 ^ 'o C. p ^ ig-alcohol sulfate-triethanolammoniuinsälz,

4, ü '; o diethyldodecylamine oxide,

4,5 / ^ isopropanol,

3.0 ^ toluene sulfonate, sodium salt,

Rest water.

Example 3

1 M C ^ -alcohol-ethylene oxide (4) -sulfate, _{NH 4 -SaIz,}

4.0 ^ C ₁₄ _ ₁₆ alcohol sulfate, _{NH 4 salt,}

15.05'b C ₁₅ _ ₁₃ paraffin sulfonate, NH ₄ salt,

1.0> C _14-1 g-alkyl glyceryl ether sulfonate, _{ITH 4 salt,}

3.5 / "» dihydroxyethyltetradecylamine oxide,

2, Qfo condensation product of coconut alcohol and 6 moles of ethylene oxide per mole of alcohol,

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2.536 Acetic acid, Example 4 $ 2.0; Triethanolamine, 6.096 Ethanol, rest Water.

Coconut alcohol ethylene oxide (3) sulfate, ₄ coconut alcohol sulfate, NH salt,

18.0? «Baraffin sulfonate, NEL salt (average mole weight of the hydrocarbon residue A ^ b)

4.0 ^ 0 dimethyldodecylaiainoxid,

3 »0 ^ ό sodium acetate,

1.0 '/ ammonium sulfate,

2, OJo monoethanol coconut eggid,

6.05 ε ethanol,

Rest water.

Are you replacing 3 / ί of the 8>? Coconut alcohol sulfate ammonium salt through the condensation product of about 6 moles of ethylene oxide and 1 mole of coconut fatty alcohol, a detergent with the same is obtained Cleaning effect, same fat suspension effect and lasting Foam.

Especially for rinsing high-melting fats that contain protein Leftovers such as eggs and flour-containing food leftovers soiled stainless steel plates and dishes Steel suitable detergents are:

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-H-

V VI VII VIII IX _Χ__

Coconut alcohol-lthy- $ 2.0 - $ 0.8 1.5? S $ 2.0 lenoxide (3) sulfate acunonium salt

Coconut Alcohol Ethyl - $ 2.0 '-. - $ 1.5

lenoxide (3) sulfate

Sodium salt

C ₁₅ _ ₁₈ - Paraffin sulfo-24.0 ^ 23.0 $ 17.0 $ 32.0 $ 25.0 $ 20.0 $ nat sodium salt

G ₁₂ _ _i4 - Alcohol Sulphate- $ 16.0 $ 10.0 $ 5.0 $ 10.0 $ 14.0 $ 12.0 Ammonium Salt

_Mmethyl-C12 _ _l6 ~ 5.0 $ 3.0 $ 5.0 $ 6.0 $ 4.0 $ $ 6.0

alkyl amine oxide

Coconut alcohol
Ethylene oxide (6) -
condensate - - 3, Of » 4, Of ₀ - - Lactic acid - - 2, $ 0 - - - Sodium lactate - - 1, $ 5 - $ 3.0 Sodium citrate $ 4.5 $ 2.0 - $ 2.0 - Potassium Toluene =
sulfonate $ 7.5 $ 5.0 3, $ 5 $ 2.0 $ 6.0 Ethanol
water 3, $ 0
rest 4, $ 5

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Claims (4)

Claims liquid, concentrated, easy to remove, watery Cleaning agents containing water-soluble surface-active detergents and customary smaller additives, thereby characterized in that it is calculated on the total weight of the agent (A) about 8 to about 35 wt. ^ Of a water soluble aliphatic Hydrocarbon sulfonates of the formula - R ¹ SO ₅ M (I) wherein R is a straight-chain or branched, saturated hydrocarbon radical having S to 20 carbon atoms and M is an alkali metal, ammonium, dimethyl, diethyl, urimethyl, triethyl, dimethanol, diethanol. Represent trimethanol or triethanol ammonium, (B) about 2 to about 20 weight percent of a water soluble aliphatic Hydrocarbon sulfate of the general formula R ² SO ₄ M (II) wherein R is a straight-chain or branched, saturated one or unsaturated hydrocarbon radical having 8 to 22 carbon atoms and M represents the above has given meaning, (C) about 0.5 to about 4 wt. ^ Of a water-soluble polyethylene glycol ether sulfate the general formula R ⁵ O (C ₂ HO) _n SO M (III) wherein R is a straight-chain or branched, saturated one or unsaturated hydrocarbon radical with 8 509845/1037 to 22 carbon atoms and η a number of 1.5 12 represent and M has the meaning given above, and (D) about 3 to about 8% by weight of a tertiary amine oxide general formula R ⁴ R ⁵ R ⁶ N- * 0 (IV) 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. Contains water in which the weight ratio of (A) to (B) is from 1: 2 to 10: 1, the weight ratio of (A) to (C) is from 25s1 to 12: 1 and the weight ratio of (D) to (A) + (B) + (G) are from 1:40 to 1: 5. 2. Cleaning agent according to claim. 1, characterized in that the water-soluble aliphatic hydrocarbon sulfonate a secondary paraffin sulfonate having 14 to 17 carbon atoms is. 3. Cleaning agent according to claim 1, characterized in that that the water-soluble polyethylene glycol ether sulfate differs from an alcohol with 10 to 16 carbon atoms derives. 4. Cleaning agent according to claim 3, characterized by calculated on the total weight of the product (A) about 15 to about 30 wt. ⁰ Jo a secondary paraffin sulfonate having 14 to 17 carbon atoms, (B) from about 4 to about 15 percent by weight of a petalcohol sulfate 12 to 16 carbon atoms, (G) about 1 to about 3% by weight of a polyethylene glycol ether sulfate of the formula III, _{where R} 3 is _a metal alcohol residue 509845/1037 with 12 to 16 carbon atoms and η a number of about 3 to about 6 represent (D) about 3 to about 6 wt. Yä a tertiäreil amine oxide, (E) about 2 to about half of a reaction product of 4 to 15 moles of ethylene oxide and 1 col. Fatty alcohol with 12 to 12 carbon atoms, and the remainder water., wherein the weight ratio of (A) to (B) from 2: 1 to 10: 1, the weight ratio of (A) au (O) from 15J1 to 12: 1 and the weight ratio of (D) to (A) + (B ) + (C) from 1:20 to 1: 5 and the maximum ^ close to (B) + (E) wt. ^ And the weight ratio of (B) to (E) from 1: 1 to 5: 1 amounts to. For: Procter & Gamble European Technical Center Dr.H.Chr.Beil Lawyer 509845/1037