RU2114907C1 - Aqueous detergent composition for solid surfaces and method for improving quality of solution - Google Patents

Abstract

FIELD: detergents. SUBSTANCE: composition contains 3 to 35 wt % of a surfactant system. The latter includes at least 20% (based on total surfactant weight) of C₁₀-C₁₆-alkylethoxy sulfate with average number of ethylene oxide 1-10 per 1 molecule and other anionic surfactants, C₅-C₂₀- alkyldiethanolamide, and C₈-C₁₆-alkylamine oxide. Composition also contains 0.01-0.5% of calcium ions and functional additives (to 100%). Content of alkylethoxy sulfate in composition is at least 3 wt %. According to invention, calcium ions are added in the form of water-soluble calcium salt. EFFECT: improved touch quality of composition solution, got over deterioration of solution on storage, and improved its detergent ability. 11 cl, 1 tbl

Description

 The invention relates to aqueous detergent compositions for hard surfaces, which (compositions) contain calcium ions, giving a solution improved by touch, but do not impair the storage stability of the composition. This composition is especially useful for dishwashing liquids, especially for washing dishes with soft water.

 Anionic surfactants, such as short ethylene oxide short chain ethylene sulfates, alkyl sulfates, alkyl benzene sulfones, alpha olefin sulfonates and alkyl ethoxy carboxylates, are known to be very effective in cleaning hard surfaces, but are also known as more or less unfavorable “slippery” to the touch means in their practical use. This undesirable quality is a problem for hard surface cleaning compositions, especially compositions intended for washing dishes.

 Therefore, an extremely important requirement for detergent compositions intended for hard surfaces is a high washing ability and high storage stability, and at the same time, good quality of the solution to the touch when cleaning and washing, especially when washing dishes. As defined in this description, the high quality of the solution is considered as the lack of a feeling of “slippery” or “mucous” or “slippage” that is felt when using the composition. "Good touch quality" is a very important indicator for commercial liquid detergent products. Those washing solutions that are of good quality to the touch, for hands and objects can easily be used to wash items and give good washing performance. Such qualities are especially needed when using compositions for washing dishes.

 Many attempts have been made to improve the quality of the solution by touch using various techniques. These attempts are usually directed to the use of non-ionic surfactants and other components such as soap improvers and solvents.

 Typically, the improved touch quality of these compositions is achieved by reducing the washing ability.

 Kokoki Patent 46-43550 (Kao Corporations) describes a liquid detergent composition that softens the skin and has a high washing ability, which includes the alkaline earth metal salts of certain alkyl alkylene oxysulfates and some alkyl alkylenedoxycarboxylates.

 Coca Patent 51-125405 (The Procter and Gamble Company) describes compositions containing calcium and magnesium salts of anionic surfactants, including alkyl ether sulfates and amino oxides, alkanols containing 1-5 C atoms and water, where the mass ratio of amino oxide to anionic surfactant is from 1: 100 to 1: 2. Up to about 25% of surfactants can be monovalent salts.

 US Pat. No. 2,766,212 (General Aniline and Film Corporation) describes compositions comprising alkyl ester alkoxysulfate salts and water-soluble multivalent salts of magnesium, calcium, iron or aluminum with a content of 5-50 wt.% Surfactants. The examples show compositions containing at least 70% anionic surfactants in which magnesium and calcium ions increase the washing ability.

 US Pat. No. 4,681,704 (The Procter and Gamble Company) describes a detergent composition that provides effective fat removal, including 10-50% alkaline earth metal salt, preferably magnesium salt, anionic surfactants, 0.5-10% amine oxides and 0 5-15% betaines.

 However, in the above patents, alkaline earth metals are used mainly because of their cleaning abilities and are not described, and the improvement of the touch solution due to calcium ions is not proposed. In addition, the composition according to the above descriptions have a high concentration of divalent ions, and therefore they are unstable during storage, unlike the compositions of this invention, they can form unwanted precipitates of calcium. Preferred compositions and their examples described in the above patents have high surfactant concentrations, and thus the amount of calcium needed to reduce or eliminate the “slipping sensation” of the composition will shift the composition to a phase where calcium is readily precipitated.

 It was found that through the use of calcium ions of low concentration, a composition is obtained that gives an improved amount of the solution to the touch without compromising storage stability.

 The object of the invention is an aqueous washing composition for washing hard surfaces, which has an improved quality of the solution to the touch during use and does not impair its storage stability.

 In addition, an object of the invention is a liquid detergent composition for hard surfaces, which has a high balanced quality in terms of washing ability, touch characteristics and storage stability.

 The next object of the invention is a method for improving the touch quality of a solution of an aqueous detergent composition for hard surfaces or a washing solution of an aqueous detergent composition for hard surfaces by introducing calcium ions into the composition.

The invention relates to an aqueous detergent composition for hard surfaces, which provides improved quality to the touch, which includes the following components, wt.%:
(1) A system of surfactants selected from the group comprising anionic, nonionic, amphoteric surfactants and mixtures thereof, 3-35
including
(a) at least 20% by weight of the system of surfactants of an alkyl ethoxysulfate with an alkyl group containing 10 to 16 carbon atoms and an average of 1 to 10 mol of ethylene oxide per molecule, and the remaining mass of the surfactant system is up to 100%
(b) other anionic surfactants selected from the group consisting of alkyl benzene sulfonates, alpha olefin sulfonates, alkyl ethoxycarboxylates and mixtures thereof;
(c) diethanolamide with an alkyl chain containing 8 to 20 carbon atoms;
(d) an amine oxide with an alkyl chain containing 8 to 16 carbon atoms;
(2) Calcium ions - 0.01-0.5
(3) Functional additives - up to 100,
moreover, the composition contains 3% by weight of the composition of alkyl ethoxysulfate, where at least 20% of the mass of the surfactant system include in total the components a, b, c and d.

 The invention also relates to a method for improving the touch quality of an aqueous solution of an aqueous detergent composition for hard surfaces or a washing solution of an aqueous detergent composition for hard surfaces by introducing calcium ions into the composition.

This composition has a more acceptable slippery feel and is easy to use when cleaning and rinsing. Compositions corresponding to the invention have high storage stability, that is, this composition is stable under normal conditions of use, it does not form a precipitate or gel in the temperature range from -5 to 40 ^o C.

Anionic Surfactants
The compositions of the invention include from 15 to 35 wt.%, Preferably from 20 to 30 wt.%, Of a system of surfactants selected from the group consisting of anionic, nonionic, amphoteric surfactants and mixtures thereof. At least 20%, preferably at least 40%, more preferably at least 60% by weight of the surfactant system is the sum of anionic surfactants, diethanolamide and amine oxide. Of the anionic surfactants, at least 3%, preferably at least 8%, most preferably at least 12% of the composition are alkyl ethoxysulfate with an alkyl group containing from 10 to 16 carbon atoms with an average of 1 to 10 mol, more preferably 2 to 5 mol of ethylene oxide per molecule.

 Anionic surfactants are selected from these alkyl ethoxysulfates, alkyl sulfonates, alkyl benzene sulfates, alpha olefin sulfonates, alkyl ethoxy carboxylates and mixtures thereof.

 Alkyl ethoxysulfate, in particular having an alkyl group containing 10 to 16 C atoms, with an average of 1 to 10 mol, preferably 2 to 5 mol, more preferably 2.5 to 3.5 mol of ethylene oxide per molecule, gives high detergency and has less negative effect on the quality of the solution to the touch. In addition, compositions comprising a significant amount of such alkyl ethoxysulfates are sensitive to the effect of improved quality of the solution to the touch due to calcium ions. The average mole of ethylene oxide per molecule of alkyl ethoxysulfates can alter the nature of the surfactant. In this case, alkyl sulfate acts as an alkyl ethoxysulfate with zero moles of ethylene oxide per molecule. It is well known that ethylene oxide with a longer chain length lessens the quality of the solution to the touch, but has a more detergent ability. When the average number of ethylene oxide chains is less than 1 mol per molecule, they contribute to the deterioration of the quality of the solution to the touch.

 Salts of the anionic surfactant may be amine or ammonium salts, alkali metal or alkaline earth metal salts, preferably sodium or ammonium salts. The alkaline earth metal salts of these surfactants, as is already known, provide good detergency and good soap content. Some or all of the calcium ions of this composition may be administered as calcium salts of an anionic surfactant.

Other surfactants
Compositions of the invention include, for balance of the surfactant system, other anionic surfactants, nonionic surfactants, and amphoteric surfactants. These surfactants are prepared in the form of compositions according to the invention to enhance the washing ability and to increase and stabilize the soap. The types and quantities of other anionic, non-ionic and amphoteric surfactants are selected in such a way as to obtain the optimal balance of washing ability, quality of the solution to the touch and stability during storage.

 The compositions of the invention may comprise nonionic surfactants such as diethanolamides and amino oxides. The composition contains from 0 to 9%, preferably from 4 to 7 wt.% Diethyleneolamide, and from 0 to 10%, preferably from 2 to 5 wt.% Of amido oxide. These two surfactants are known to provide good detergency and high storage stability, but can adversely affect the quality of the solution to the touch. The use of calcium ions to improve the quality of the solution by touch is particularly useful in compositions containing diethylanolamide and / or amino oxide.

,
в которой
R¹ выбран из числа алкильных цепей с содержанием 8 - 20 атомов C, предпочтительно 12 - 14 атомов C.The diethanolamide used according to the invention has the formula

,
wherein
R ^{1 is} selected from among alkyl chains containing 8 to 20 C atoms, preferably 12 to 14 C.

,
в которой
R² выбран из числа алкильных цепей с содержанием 8 - 20 атомов C, предпочтительно 12 - 14 атомов C.The amine oxide used according to the invention has the formula

,
wherein
R ^{2 is} selected from among alkyl chains containing 8 to 20 C atoms, preferably 12 to 14 C.

Calcium
It was found that by introducing calcium ions in low concentrations, the quality of the solution to the touch improves and storage stability increases. The effect of introducing low concentrations of calcium ions in the dishwashing composition is especially positive in conditions of low water hardness, when the amount of calcium introduced with tap water is low.

Calcium ions are introduced into the composition in concentrations from 0.01 to 0.5%, preferably from 0.1 to 0.5%, most preferably in the range from 0.1 to 0.3%. At lower calcium concentrations, there is no effect on the quality of the solution to the touch. At higher calcium concentrations, storage stability is low. In other words, it is known that calcium ions are relatively easy to precipitate at high temperatures and, thus, are able to reduce storage stability when introduced at high concentrations. In addition, as is known, calcium ions affect the washing ability, in particular, affect the removal of fats. Choosing the concentration of calcium in the above limit, get the composition with all three of the above advantages: good quality solution to the touch, a high degree of removal of fats and high stability during storage,
Compositions of the invention should include a total of less than 35% surfactants to eliminate calcium deposition, which is present in doses sufficient to improve the quality of the solution by touch. If the content of the surfactant is excessively high, then the maximum amount of calcium that can be introduced without the formation of a calcium precipitate will be insufficient to improve the quality of the touch of the solution of the composition.

 Calcium ions can be introduced into the composition in any conventional way, since salts containing calcium ions are soluble in water and do not precipitate under normal conditions of use. A suitable way to introduce calcium ions is to enter them in the form of salts selected from the group consisting of chloride, hydroxide, oxide, acetate, nitrate, format, and mixtures thereof. Most preferred is chloride.

 As another possible option, calcium ions can be introduced in the same way as counterions of anionic surfactants, for example, by neutralizing the acid form of anionic surfactants with calcium oxide or calcium hydroxide without reducing their beneficial effect.

The preferred composition corresponding to the invention includes the following components, wt.%:
(1) A system of a surfactant selected from the group including anionic, nonionic, amphoteric surfactants and mixtures thereof - 20-30,
including
a) at least 35% of the surfactant system of alkylate sulfate with an alkyl group containing 10 to 16 C atoms and an average of 2.5 to 3.5 ethylene oxide per molecule;
b) 4 to 7% (mass) of the composition of the diethanolamide with an alkyl chain containing 8 to 20 C atoms;
c) 2 to 5 wt.% of the composition of the composition of the amine oxide with an alkyl chain containing 8 to 16 C atoms;
(2) Calcium ions - 0.1 - 0.3
(3) Magnesium ions - 0.1 - 1
Optional components
Compositions of the invention may optionally contain other components in addition to the components already described above.

 Optional surfactants in the composition of the invention are monoethanolamides, fatty acid polyhydroxyamides, alkyl polyglucosides and alkyl ethoxylates.

,
в которой
R³ выбран из алкильных цепей с содержанием 8 - 20 атомов углерода, предпочтительно 12 - 14 атомов углерода.Monoethanolamide is a possible surfactant according to the invention having the formula

,
wherein
R ³ selected from alkyl chains containing 8 to 20 carbon atoms, preferably 12 to 14 carbon atoms.

,
в которой
R⁴ представляет собой H; содержащие 1 - 4 атома C гидрокарбил, 2-гидроксиэтил, 2-гидроксипропил или их смесь, предпочтительно алкил с содержанием 1 - 4 атома C, еще более предпочтительно метил; R⁵ представляет собой гидрокарбил с содержанием 5 - 31 атомов C, предпочтительно алкил с прямой цепью с содержанием 10 - 16 атомов C; и Z представляет собой полигидроксигидрокарбил, имеющий линейную гидрокарбильную цепь с содержанием не менее 3 гидроксилов, непосредственно связанных с цепью, или его алкоксилированное производное (предпочтительно этоксилированное или пропоксилированное), Z образован предпочтительно от восстанавливаемого сахара в реакции восстановительного аминирования, наиболее предпочтительно Z - это глицитил. Подходящими восстанавливаемыми сахарами являются глюкоза, фруктоза, мальтоза, лактоза, галактоза, манноза и ксилоза.Fatty acid polyhydroxyamide is an optional surfactant of the invention having the formula

,
wherein
R ⁴ represents H; containing 1 to 4 C atoms, hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof, preferably alkyl containing 1 to 4 C atoms, even more preferably methyl; R ⁵ is hydrocarbyl containing 5 to 31 C atoms, preferably straight chain alkyl containing 10 to 16 C atoms; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain containing at least 3 hydroxyls directly linked to the chain, or an alkoxylated derivative thereof (preferably ethoxylated or propoxylated), Z is preferably formed from reducible sugar in a reductive amination reaction, most preferably Z is glycityl . Suitable reducible sugars are glucose, fructose, maltose, lactose, galactose, mannose and xylose.

Alkylpolyglucoside is a possible surfactant according to the invention having the formula
R ⁶ O (C _m H _2m O) _p (glucosyl) _q .

in which R ^{6 is} selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl and mixtures thereof, where the alkyl groups are groups containing 10 to 18, preferably 12 to 14 C atoms; m is 2 or 3, preferably 2; p is from 0 to about 10, preferably 0; q is from 1.3 to 10, preferably 1.3 to 3, most preferably from 1.3 to 2.7. To obtain these compounds, alcohol or an alkylpolyethoxy alcohol is first prepared, and then it reacts with glucose or with a glucose source to form glucose (connection at position 1). Then additional glucose units can be connected between their 1-position and the preceding 2-, 3-, 4- and / or 6-position of the glycosyl units, preferably the 2-position.

 Alkyl ethoxylate is a possible surfactant according to the invention. Such alkyl ethoxylates are aliphatic alcohols with 1 to 25 mol of ethylene oxide. The alkyl chain of an aliphatic alcohol can be either straight or branched, primary or secondary, and usually it contains 8 to 22 carbon atoms. Especially preferred are the condensation products of alcohols having an alkyl group containing 8 to 20 carbon atoms with 2 to 10 moles of ethylene oxide per mole of alcohol. Most preferred are the condensation products of alcohols having an alkyl group containing 8 to 14 carbon atoms with 6 to 10 moles of ethylene oxide per mole of alcohol.

в которой R⁷ представляет собой алкильную группу с содержанием 7 - 21 атомов C или алкиларильную группу (7 - 21 атомов C в алкиле), предпочтительно 9 - 17 атомов C; R⁸ представляет собой водород или алькильную группу с содержанием 1 - 6 атомов C, предпочтительно 1 - 3 атома C; R⁹ представляет собой алкиленовую группу с содержанием 1 - 10 атомов C, предпочтительно 2 - 6 атомов C, наиболее предпочтительно 3 атома C; каждая из групп R¹⁰ представляет собой алкил с содержанием 1 - 6 атомов C или гидроксиалкильную группу (1 - 6 атомов C), предпочтительно 1 - 3 атома C, наиболее предпочтительно метил или этоксилированный гидроксиалкил, содержащий примерно от 1 до примерно 10 этиленоксидных звеньев; R¹¹ представляет собой алкиленовую группу с содержанием 1 - 6 атомов C, предпочтительно метил.Amphoteric surfactants that are optionally used according to this invention are betaines having the formula

in which R ⁷ represents an alkyl group containing 7 to 21 C atoms or an alkylaryl group (7 to 21 C atoms in the alkyl), preferably 9 to 17 C atoms; R ⁸ represents hydrogen or an alkyl group containing 1 to 6 C atoms, preferably 1 to 3 C atoms; R ⁹ represents an alkylene group containing 1 to 10 C atoms, preferably 2 to 6 C atoms, most preferably 3 C atoms; each of R ¹⁰ groups is alkyl with 1 to 6 C atoms or a hydroxyalkyl group (1 to 6 C atoms), preferably 1 to 3 C atoms, most preferably methyl or ethoxylated hydroxyalkyl containing from about 1 to about 10 ethylene oxide units; R ¹¹ represents an alkylene group containing 1 to 6 C atoms, preferably methyl.

 Magnesium ions with a concentration of 0.1 to 1% are preferably included in the composition corresponding to the invention, to improve the washing ability, without reducing the improved quality of the solution to the touch and stability during storage of the composition.

 The compositions of the invention may also comprise 4-8% by weight of a hydrotropic component selected from the group consisting of sodium and ammonium salts of cumene sulfonates, toluenesulfonates, xylene sulfonates, sulfosuccinates and mixtures thereof. Such components are used to achieve the desired solubility and viscosity. Other desired ingredients include solvents, preservatives, colorants and flavoring agents.

 The solvents used according to the invention include water and low molecular weight alcohols, such as ethanol. Ethanol is also known to reduce the viscosity of the product, if necessary for the composition. Solvents other than water are also present, usually in an amount of 2-10% by weight.

 Preservatives, colorants and flavoring agents are present in the composition of the invention to produce products desired by the consumer. These components are usually present in concentrations of not more than 1%, respectively.

 It is desirable not to include components in the composition that form a precipitate upon binding to calcium ions. Examples are those that include sulfate, carboxylate and fatty acid anions.

 The following examples illustrate the compositions of the invention, but are not a limitation thereof.

Preparation of the drug
The liquid detergent compositions described herein can be prepared in the usual manner, as is known to those skilled in the art. Surfactants, hydrotropic compounds, calcium salts and optional magnesium salts are added to suitable amounts of water and mixed. According to this invention, the order of input of the components is not significant. If necessary, the pH of the mixture is adjusted by means of HCl to a value that is safe for home products, and the viscosity is regulated by alcohol. Flavoring agents, colorants and preservatives are added if desired, and the composition is balanced with water. Thus, a standard product and the product of Examples 1 to 9 are prepared.

Experiment
1. The quality of the solution to the touch.

 500 g of each of the 6% solutions of the standard product and compositions of the invention are prepared in a 1 liter beaker and the porcelain crucible is immersed in this solution.

 One hand is immersed in the solution of the test sample and the other in the solution of a conventional standard product at the same time, and the quality of the crucible to the touch is evaluated according to the scale below.

 The assessment is carried out by three testers and the average estimated value is taken.

Grading scale
0 = no difference;
± I = I believe that there is a difference;
± 2 = I know that there is a difference;
± 3 = I know that the difference is large;
± 4 = I know that the difference is very large;
(+) the sample has the best quality to the touch (less sliding);
(-) the sample has the worst quality to the touch (more sliding).

 Compositions with higher rates than compositions with the same calcium-free surfactant system are rated as compositions with “improved quality of the solution to the touch”.

2. Storage stability
The sample is placed in a 100-milliliter glass container, where it is kept indoors at a temperature of -5 ^o C and 40 ^o C. respectively ^. After two weeks, the condition of the product is evaluated on the following scale. Transparent and unchanged compared to the sample
Before the test - 0
Sludge or turbidity - X
From consideration of the table it is clear that the samples from examples 1, 3, 4 and 7, which are compositions corresponding to the invention, have both improved quality of the solution to the touch, and improved stability during storage.

Claims (10)

1. An aqueous detergent composition for hard surfaces comprising a surfactant system comprising anionic surfactants selected from the group consisting of alkyl ethoxy sulfonate, alkyl ethoxy carboxylate and mixtures thereof, non-ionic surfactants, amphoteric surfactants and mixtures thereof, calcium ions and functional additives, characterized in that it contains these components in the following ratio, wt.%:
Surfactant System - 3 - 35
including a) at least 20% of the total mass of surfactants of C ₁₀ - C ₁₆ -alkylene ethoxysulfate with an average number of ethylene oxide of 1 to 10 mol per molecule and the rest of the mass of the surfactant system up to 100% are b) other anionic surfactants selected from the group including alkyl benzene sulfonate, α-olefin sulfonate, alkyl ethoxy carboxylate, and mixtures thereof; c) diethanolamide with an alkyl chain containing 8 to 20 carbon atoms; d) an amino oxide with an alkyl chain containing 8 to 16 carbon atoms; calcium ions from 0.01 to 0.5, functional additives up to 100, and the composition contains at least 3% by weight of the composition of alkyl ethoxysulfate.  2. The composition according to claim 1, characterized in that it further comprises not more than 9 wt.% Diethanolamine and not more than 10 wt.% Amino oxide.  3. The composition according to claims 1 and 2, characterized in that it contains 0.1 to 0.5 wt.%, More preferably 0.1 to 0.3 wt.% Of calcium ions.  4. The composition according to claims 1 to 3, characterized in that it contains a system of surfactants, comprising at least 35 wt.% Alkyl ethoxysulfate.  5. The composition according to claim 4, characterized in that it contains 20 to 30% of a surfactant system.  6. The composition according to any one of claims 1 to 5, characterized in that it contains an alkyl ethoxysulfate with 2 to 5 mol, more preferably from 2.5 to 3.5 mol of ethylene oxide.  7. The composition according to claims 1 to 6, characterized in that it contains 4 to 7 wt. % of the above diethanolamide.  8. The composition according to PP. 1 to 7, characterized in that it contains 2 to 5% of the above amine oxide.  9. The composition according to claims 1 to 8, characterized in that it contains 0.1 to 1 wt.% Magnesium ions.  10. A method of improving the quality of a solution by touch of an aqueous detergent composition for a solid surface or a washing solution of an aqueous detergent composition for a solid surface, characterized in that 0.01 to 0.5 wt.% Calcium is added to said solution of the detergent composition according to claims 1 to 9 ions in the form of a water-soluble calcium salt. Priority on points:
02/19/92 and 03/30/92 for PP. 3 to 5, 7 to 10;
03/30/92 - for PP. 1, 2, 6;
02/19/92 - according to claim 6, the sign of "2.5 - 3.3 mol of ethylene oxide per molecule ...".

Images