EP0254653B1 - Viscous, diluable detergent composition and process for its preparation - Google Patents

Abstract

A clear, concentrated, pourable liquid detergent composition capable of being diluted with water to give a viscous dilute composition. This concentrated composition comprises at least one anionic surface agent, a viscosity regulator for the dilute composition, consisting of at least one surface agent chosen from the group made up of nonionic, amphoteric and zwitterionic surface agents, used in combination with at least one acid or its salt in such a quantity that it is dissolved in the concentrated composition, the surface agent and the acid or the salt being chosen so that the viscosity V2 of the dilute composition decreases, or increases and then decreases, when the quantity of acid or of its salt increases, in the case of given surface agents and water. <??>Application to compositions particularly for dishwashing. <IMAGE>

Description

The present invention relates to a liquid, concentrated, stable detergent composition which can be diluted with water and such that the viscosity of the diluted composition is sufficiently high to satisfy consumers, while the viscosity of the concentrated composition is sufficiently low to allow it to be poured into containers.

The object of the invention is to manufacture a detergent composition which can preferably contain up to approximately 90% of surface-active materials and which can be diluted by several times its volume of water to obtain a final composition whose viscosity is satisfactory for the user.

Indeed, a diluted composition having a high viscosity is perceived by consumers as being more effective than a composition with the same concentration of active materials, but of low viscosity. Until now, when it was desired to obtain a dilute composition of satisfactory viscosity, the viscosity of the starting concentrated composition was too high to allow its industrial use.

Another object of the invention is to manufacture a clear detergent composition which, by dilution with water by the user, gives a clear, viscous, stable composition. The problem to be solved is particular, because the dilution is carried out by the user and therefore under conditions which are not controllable. Thus, the dilution is made with a variable amount of water. This water is in particular tap water, and depending on the region, it can be more or less hard and contain different ions. The water temperature is variable and can be between 0 and 20 ° C. The bottle in which the dilution is made is arbitrary and can be a glass or plastic bottle, of various shapes. These dilution conditions are therefore completely different from an industrial dilution where the temperature, the quantity and the quality of the dilution water are rigorously controlled, as well as the agitation, and the shape or the nature of the container in which the composition is found. The compositions according to the invention are preferably used as a multi-purpose liquid, in particular for washing dishes.

• A) des sels hydrosolubles d'alcanolamines inférieures d'acides alkylbenzènesulfoniques ou alkyltoluènesulfoniques, dans lesquels le radical alkyle contient de 8 à 18 atomes de carbone,
     et
• B) des agents de surface non ioniques qui sont des éthers éthoxylés et/ou propoxylés d'alcools aliphatiques contenant au moins 8 atomes de carbone ou d'alkylphénols dans lesquels le radical alkyle contient de 5 à 18 atomes de carbone,
     et
• C) des amides d'acides gras de mono-, di- ou tri-éthanolamine dans lesquels le radical alkyle des acides gras contient de 10 à 15 atomes de carbone,
     et de l'eau, et des polyphosphates, ainsi que de la méthylcellulose et carboxyméthylcellulose de sodium.

French Patent ^No. 1,462,001 discloses detergent compositions containing:

• A) water-soluble salts of lower alkanolamines of alkylbenzenesulfonic or alkyltoluenesulfonic acids, in which the alkyl radical contains from 8 to 18 carbon atoms,
  and
• B) nonionic surfactants which are ethoxylated and / or propoxylated ethers of aliphatic alcohols containing at least 8 carbon atoms or of alkylphenols in which the alkyl radical contains from 5 to 18 carbon atoms,
  and
• C) fatty acid amides of mono-, di- or tri-ethanolamine in which the alkyl radical of the fatty acids contains from 10 to 15 carbon atoms,
  and water, and polyphosphates, as well as sodium methyl and carboxymethyl cellulose.

The alkanolamine salt of alkylbenzene sulfonic and alkyltoluene sulfonic acids is formed by the final addition of alkanolamine to the mixture of surfactants and the fatty acid alkanolamide, in the presence of cellulose derivatives. These salts are therefore formed in situ when the various compounds are mixed.

However, these compositions are not intended to be diluted and therefore there is no concern for the viscosity of the diluted composition relative to the viscosity of the concentrated composition.

French Patent ^No. 1,501,661 describes a process for preparing a concentrated detergent composition liquid, which comprises adding a compound of agent surface B of the type mentioned above, a diethanolamine, to pour the alkylbenzenesulfonic acid or alkyltoluene -sulfonic acid to effect its neutralization, then to add a fatty acid amide of ethanolamine.

According to this patent, the formation of alkylbenzene- or alkyltoluene-sulfonic acid salts is carried out by in situ neutralization, that is to say during the mixing of the various constituents of the detergent composition. In addition, the compositions obtained, when diluted with water to give compositions with 50-65% of active materials, form gels.

The European patent application ^No. 77 674 describes compositions comprising a amidobetaine, an organic or inorganic salt, water and an anionic surfactant present in amounts between 0.25 and 15% by weight. The purpose described in this document is to obtain a thickened aqueous solution by adding 5 to 25% by weight of amidobetaine. The compositions obtained can be clear or opaque and can be gels or pastes. These compositions are not very concentrated and contain 50 to 70% of water.

European Patent application ^No. 88612 discloses detergent dilutable liquid compositions containing more than 90% by weight of detergent materials containing more than 50 wt% coconut ethanolamide derivative and polyether, namely more than 50% of agents non-ionic surface. However, these compositions have a moderate detergent action, since the detergent activity of nonionic surfactants is weaker than that of anionic surfactants.
In addition, these compositions are ternary mixtures which do not contain salt for thickening, since the latter tends to precipitate.

British Patent ^No. 1164854 discloses detergent compositions containing ammonium or amine salts of alkylbenzenesulfonates, ethoxylated alcohols and metal salts of di- or trivalent, eg magnesium sulfate. But the viscosity of the compositions at 30% of active ingredients is not adjustable depending on the salt level and the compositions diluted to 15% of active ingredients are cloudy.

The present invention further aims to provide liquid, concentrated, clear, dilutable compositions containing more than 50% by weight of anionic surfactants relative to the total amount of active materials.

French Patent ^No. 2,156,825 discloses aqueous concentrates of sulfates of alkoxylated alcohols with a viscosity lowered by compounds such as lactic acid, glyceric acid, tartaric acid or citric acid, which makes it possible to dilute without gel formation.

French Patent ^No. 2,304,665 relates to compositions containing an olefin sulfonate which is added an acid salt to lower the viscosity of the concentrated compositions. This patent further relates to dilute compositions of these olefin sulfonate and acid salt mixtures. An alkanolamide may optionally be added to the diluted compositions in order to increase the viscosity of this composition.

Thus, this patent describes a concentrated composition which contains an anionic surfactant and a salt, or a diluted composition to which a nonionic surfactant is added.

French Patent ^No. 2,343,804 discloses a composition containing a nonionic polyethoxylated surfactant, and an acid whose function is to increase the detergency of the composition.

U.S. Patent ^No. 4,092,273 discloses a detergent composition which contains an anti-gelling agent at low temperature. This agent is a diacid salt.

French Patent ^No. 2106927 describes a descaling composition containing a detergent, an acid and a thickener based on cellulose ether.

However, surprisingly, and contrary to what was foreseeable in the literature, the Applicant has been able to produce detergent compositions concentrated, limpid, dilutable with water, the dilution of which gave diluted compositions having a viscosity which is not appreciably lowered but on the contrary could even be adjusted with respect to the viscosity of the concentrated composition as desired by adding acids or their soluble salts in the concentrated composition, composition containing anionic surfactants in an amount greater than the amount of nonionic surfactants. In addition, the diluted compositions are clear.

• a) 10 à 70% en poids d'au moins un agent de surface anionique, et
• b) une combinaison de:
  • b₁) 2 à 20% en poids d'au moins un agent de surface choisi dans le groupe formé par les agents de surface non ioniques, amphotères, zwitterioniques et
  • b₂) 0,5 à 20% en poids d'au moins un acide ou son sel de formule générale
    
    $\text{(I) A-C}$
    
    
    
    dans laquelle A est un anion choisi dans le groupe formé par les anions d'acides aliphatiques saturés ou insaturés contenant 1 à 8 atomes de carbone, et renfermant éventuellement des groupes hydroxy, tels que les groupes dérivés des acides lactique, propionique, succinique, malique, glycolique, glycérique, tartrique, citrique, gluconique, saccharique, formique, acétique, butyrique, oxalique, maléique, itaconique; et les groupes sulfate, iodure, bromure, chlorure, thiosulfate, bichromate, orthophosphate; et
    C est H ou un cation choisi dans le groupe formé par les ions sodium, potassium, calcium; ammonium, alcanol-ammonium, magnésium, fer et cuivre, et
  • c) de l'eau,

tandis que la quantité totale d'agents de surface (a+b₁) est de 15 à 90% en poids et le rapport de la quantité totale d'agents de surface anioniques à la quantité totale d'agents de surface non ioniques est supérieur à 1.The present invention therefore relates to a concentrated liquid detergent composition, clear, pourable, dilutable with water to give a dilute viscous composition, characterized in that it comprises, for obtaining a viscous composition after its dilution with. water by use, a mixture of

• a) 10 to 70% by weight of at least one anionic surfactant, and
• b) a combination of:
  • b₁) 2 to 20% by weight of at least one surfactant chosen from the group formed by nonionic, amphoteric, zwitterionic surfactants and
  • b₂) 0.5 to 20% by weight of at least one acid or its salt of general formula
    
    $\text{(I) AC}$
    
    
    
    in which A is an anion chosen from the group formed by anions of saturated or unsaturated aliphatic acids containing 1 to 8 carbon atoms, and optionally containing hydroxy groups, such as groups derived from lactic, propionic, succinic or malic acids , glycolic, glyceric, tartaric, citric, gluconic, saccharic, formic, acetic, butyric, oxalic, maleic, itaconic; and the sulfate, iodide, bromide, chloride, thiosulfate, dichromate, orthophosphate groups; and
    C is H or a cation chosen from the group formed by sodium, potassium, calcium ions; ammonium, alkanol-ammonium, magnesium, iron and copper, and
  • c) water,

while the total amount of surfactants (a + b₁) is 15 to 90% by weight and the ratio of the total amount of anionic surfactants to the total amount of nonionic surfactants is greater than 1.

• d) au moins un solvant non aqueux,
• e) un agent de surface non ionique fluidifiant,
• f) au moins un hydrotrope, et/ou
• g) un acide, régulateur du pH.

The composition also optionally comprises:

• d) at least one non-aqueous solvent,
• e) a fluidizing nonionic surfactant,
• f) at least one hydrotrope, and / or
• g) an acid, regulator of pH.

est au plus égale à 90% en poids de la composition et le rapport de la quantité totale d' agents de surface anioniques à la quantité totale d'agents de surface non ioniques étant supérieur à 1.Said composition can also optionally comprise a perfume, a dye, a perfume solubilizing agent and / or a preservative. Preferably, the total amount of surfactants $\text{(a + b₁ + e)}$

is at most equal to 90% by weight of the composition and the ratio of the total amount of anionic surfactants to the total amount of nonionic surfactants being greater than 1.

According to the invention, the acid or its salt representing the component (b₂) thus corresponds to the following general formula: AC
in which A is an anion chosen from the group formed by saturated or unsaturated aliphatic groups containing 1 to 8 carbon atoms, and optionally containing hydroxy groups, more preferably groups derived from lactic, propionic, succinic, malic, glycolic acids, glyceric, tartaric, citric, gluconic, saccharic, formic, acetic, butyric, oxalic, maleic or itaconic; and by the sulfate, iodide, bromide, chloride, thiosulfate, dichromate, orthophosphate groups; and
C is H or a cation chosen from the group formed by sodium, potassium, calcium, ammonium, alkanolammonium, magnesium, iron and copper ions.

When it is desired to obtain high concentrations for the composition before dilution, acids or salts such as lactic acid, ammonium lactate or ammonium propionate are preferred.

The amounts of co-regulatory salts (b₂) introduced are preferably from about 0.5% to about 20% by weight.

dans laquelle
R₁, R₂ sont semblables ou différents et sont H, ou un groupe alkyle en C₁-C₄ substitué par un ou plusieurs groupes OH;
les amides d'acide à chaine alkyle saturée ou alcényle insaturée mono ou polyfonctionnels, éventuellement oxyéthylénés ou oxypropylénés;
les alkylbétaïnes de formule

dans laquelle R₃ est un radical alkyle ou alcényle comportant 8 à 20 atomes de carbone,

R₄

est -(CH₂)_z- ou -CH₂-CH(OH)-(CH₂) _z

x

et y sont semblables ou différents et égaux à 0 ou à un entier de 1 à 5

z

est égal à un entier de 1 à 5;

les alkylsulfobétaïnes de formule

dans laquelle R₃, R₄, x, y, et z ont les mêmes significations que ci-dessus;
les alkylaminobétaines de formule

dans laquelle R₃, R₄, x, y, z ont les mêmes significations que ci-dessus et n est un entier entre 1 et 6;
les alkylaminosulfonétaines de formule

dans laquelle R₃, R₄, x, y, z et n ont les mêmes significations que ci-dessus;
les alkylamidosulfobétaïnes de formule

dans laquelle R₃, R₄, x, y, z, n ont les mêmes significations que ci-dessus;
les esters d'acide gras et d'alkylène polyol polyéthoxylé et/ou -propoxylé,contenant de 1 à 200 radicaux oxyde d'éthylène et/ou oxyde de propyléne, les acides gras contenant de 8 à 20 atomes de carbone et les polyols étant choisis parmi l'éthanediol -1,2 , le propanediol-1,2 , le butanediol-1,2 , le glycérol, le sorbitanne, le glucose.According to the invention, the surfactant (b₁) of the viscosity regulator is chosen from the group formed by: the amides of C₈-C₂₀ fatty acid and amine of formula

in which
R₁, R₂ are the same or different and are H, or a C₁-C₄ alkyl group substituted by one or more OH groups;
the amides of mono or polyfunctional saturated alkyl or unsaturated alkenyl or alkenyl chain acid, optionally oxyethylenated or oxypropylenated;
the alkylbetaines of formula

in which R₃ is an alkyl or alkenyl radical containing 8 to 20 carbon atoms,

R₄

is - (CH₂) _z - or -CH₂-CH (OH) - (CH₂) _z

x

and are similar or different and equal to 0 or an integer from 1 to 5

z

is an integer from 1 to 5;

alkylsulfobetaines of formula

wherein R₃, R₄, x, y, and z have the same meanings as above;
the alkylaminobetaines of formula

in which R₃, R₄, x, y, z have the same meanings as above and n is an integer between 1 and 6;
the alkylaminosulfonetaines of formula

in which R₃, R₄, x, y, z and n have the same meanings as above;
the alkylamidosulfobetaines of formula

in which R₃, R₄, x, y, z, n have the same meanings as above;
esters of fatty acid and of polyethoxylated and / or -propoxylated alkylene polyol, containing from 1 to 200 ethylene oxide and / or propylene oxide radicals, the fatty acids containing from 8 to 20 carbon atoms and the polyols being chosen from ethanediol -1,2, propanediol-1,2, butanediol-1,2, glycerol, sorbitan, glucose.

More preferably, the surfactant of the thickener is coconut diethanolamide or ethoxylated propylene glycol dioleate containing 55 EO on average in the molecule.

The amounts of surfactant of the viscosity regulator are from about 2% to about 20% by weight.

The compositions according to the invention contain from about 10% to about 70% by weight of one or more anionic surfactants.

The anionic detergents (a) preferred according to the invention are sulfates or sulfonates of alkali metals, alkaline earth metals, ammonium or alkylamine or alkanolamine; sulfates or sulfonates having an alkyl chain which contains from about 8 to about 22 carbon atoms. Examples of anionic surfactants used in the compositions according to the invention are sodium, magnesium, ammonium, potassium, alkylamine or alkanolamine alkyl sulphates, obtained by sulphating alcohols containing from 8 to 18 carbon atoms, alkylbenzene or alkyltoluene sodium, magnesium, mono-, di- or triethanolamine sulfonates, or alkylamine, in which the alkyl group contains from about 8 to about 18 carbon atoms, the alkyl radical being a branched or unbranched aliphatic chain; paraffin sulfonates and alkenesulfonates and hydroxyalkanesulfonates, for example sodium or magnesium, in which the alkyl or alkenyl radical contains from about 10 to about 20 carbon atoms, (C₁₀-C₂₀) alkyl, ether sulfates, for example tallow or coconut oil or obtained by synthesis

Examples of anionic surfactants are sodium lauryl ether sulfate, triethanolamine, ammonium, sodium paraffinsulfonates, the alkyl chain of which contains from 13 to 15 carbon atoms. An alkyl ether sulfate is preferred, the alkyl chain of which contains from 12 to 14 carbon atoms, for example 70% of C₁₂ and 30% of C₁₄, containing 2.2 ethylene oxides on average in the molecule.

Preferably the anionic surfactant (a) is an alkylbenzenesulfonic acid whose alkyl chain contains from 10 to 12 carbon atoms, neutralized by an amine containing from 1 to 3 alkylol groups, more preferably monoethanolamine which confers a slightly lower viscosity to the concentrated composition, which makes it possible to reduce the level of non-aqueous solvent, and therefore to introduce a higher level of active materials in the composition.

It has been found that an essential characteristic of the invention is that the anionic surfactant or the mixture of anionic surfactants, in solutions containing more than 40% by weight of active materials must be chosen so as to contain sufficiently few ions capable of forming precipitated salts in the concentrated composition. In fact, it is desired that the concentrated compositions according to the invention have a cloud point and a detouble point substantially less than + 5 ° C and even less than 0 ° C. In general, anionic surfactants are chosen comprising less than approximately 0.5% by weight of sodium chloride and less than approximately 2% by weight of sodium sulfate.

Another characteristic of the invention is that the stable sulfonic acids, for example alkylbenzenesulfonic acid, are neutralized before any preparation of concentrated composition, which makes it possible to use them in compositions at 20%, such as 40% or 60% or 80% of active ingredients. Preferably, neutralization is carried out with monoethanolamine in the presence of ethanol and an ethoxylated alcohol containing an alkyl radical of 10 to 12 carbon atoms and preferably 5 EO. By neutralization with a chosen base, compounds are obtained which are sufficiently soluble to avoid precipitation.

The non-aqueous solvent according to the invention is chosen from alcohols, glycol ethers, ketones and their mixtures, and preferably, for example, isopropanol, ethanol, and their mixtures. Quantities of non-aqueous solvents in the composition according to the invention are from about 0% to about 10% by weight. In the most concentrated compositions, the amount of alcohol is less than about 10% by weight.

The composition according to the invention can optionally comprise a nonionic surfactant which has the function of thinning the concentrated composition. Preferably, ethoxylated fatty alcohols, ethoxylated alkylphenols, alkanolamides of optionally ethoxylated fatty acids and their mixtures are chosen. As an example of ethoxylated fatty alcohol, mention may be made of C al-C₁₈ aliphatic alcohols containing from 1 to 100 EO. Preferably, an aliphatic C al-C₁₂ alcohol containing 5 EO is chosen.

According to the invention, the composition may optionally comprise a surfactant solubilizing perfumes, for example a polyethoxylated sorbitan monooleate at 20 EO on average in the molecule, a perfume, a dye a preservative. The total amount of the nonionic surfactant is preferably less than the total amount of the anionic surfactant, since the solutions according to the invention are detergent and the detergency is imparted mainly by the anionic surfactants. The total amount of nonionic surfactant in the concentrated composition is from about 0% to about 45% by weight.

The hydrotropes which can be optionally added are, for example, the sodium, potassium or ammonium salts of xylenesulfonate, toluenesulfonate, ethylbenzenesulfonate, isopropylbenzenesulfonate, n-amylsulfate and n-hexylsulfonate, urea, and their mixtures. The amount of hydrotrope in the composition is from about 0% to about 5% by weight.

According to the invention, when co-regulatory salts capable of decomposing in basic medium, such as ammonium lactate, are used, a pH regulating acid of the concentrated solution, so that the pH is approximately 5 to 7. For example, the compositions according to the invention contain sulfuric acid.

The invention further relates to a method for adjusting the viscosity V₂ of a diluted composition obtained by diluting with water a concentrated composition of viscosity V₁. The concentrated compositions according to the invention are intended to be introduced into rigid or flexible packaging and must therefore be able to be poured into and out of these packaging. The viscosity V₁ must therefore be adjusted so as to be less than approximately 800 mPa.s (centipoise), preferably less than approximately 500 mPa.s, measured with the Brookfield viscometer at 12 revolutions / minute with a mobile 2.
Furthermore, it is desired that the diluted composition has a viscosity acceptable to the housewife, preferably that the viscosity V₂ is greater than 50 mPa.s, more preferably greater than approximately 150 mPa.s, and even of the order of 300 mPa.s approx.

To this end, the viscosity V₁ of the concentrated composition and the viscosity V₂ of the diluted composition are adjusted by adding to at least one anionic surfactant, possibly mixed with at least one nonionic surfactant, a viscosity regulator consisting of a combination of at least one nonionic, amphoteric or zwitterionic surfactant and an acid or its salt below, to obtain a concentrated composition as defined above.

The present invention is illustrated in more detail with reference to the single figure of the accompanying drawings, in which the variation in viscosity of the diluted and concentrated compositions has been shown. The abscissa axis represents the percentage of soluble salt. The percentages of salt in the concentrated composition and in the diluted composition are shown on the abscissa axis. The y-axis represents the viscosity of the composition. The curves in solid lines represent the variation in viscosity of the concentrated compositions containing as co-regulating salts of viscosity of:
magnesium sulfate represented by X
potassium phosphate represented by +
ammonium sulfate represented by △
ammonium propionate represented by ○
sodium lactate represented by □
ammonium lactate represented by ∇
The curves in broken lines represent the variation in the viscosity of the diluted compositions. As a function of the percentage by weight of salt, of the percentage by weight of viscosity regulator and as a function of the dilution (2 to 6 times), a viscosity V₁ of concentrated composition and a viscosity V₂ of diluted composition are obtained which can be adjusted. .

The following description, with reference to the nonlimiting examples, will make it possible to understand how the invention can be put into practice.

OE

oxyde d'éthylène

OP

oxyde de propylène

ABS

alkylbenzènesulfonate

PS

paraffinesulfonate

AES

alkyléthersulfate

NI

non ionique

DEA

diéthanolamide

TEA

triéthanolamine

Unless otherwise indicated, the percentages are given by weight of the total composition and the concentrated compositions are diluted four times. The following abbreviations are used:

OE

ethylene oxide

OP

propylene oxide

ABS

alkylbenzenesulfonate

PS

paraffinesulfonate

AES

alkyl ether sulfate

OR

non-ionic

DEA

diethanolamide

TEA

triethanolamine

Comparative Example 1: It performs the following mixture (Example 3C of EP ^No. 77674)

15.0% cocoamidobetaine
5.0% sodium sulfate
2.4% sodium alpha-olefinsulfonate
qs 100% water.

The composition has a viscosity of 2600 mPa.s. It is a poorly concentrated composition, with 17% active ingredients.

When the level of active ingredients is increased, that is to say when the% of alpha-olefinsulfonate is increased, the viscosity decreases, a dilute composition of satisfactory viscosity is not obtained.

EXAMPLE 1: Preparation of alkyl (C₁₀-C₁₂) benzenesulfonic acid neutralized by triethanolamine :

Triethanolamine (approximately 528 g) is poured into 1000 g of alkylbenzenesulfonic acid little by little, cooling the mixture to approximately 50 ° C. At the same time, a non-ionic surfactant is alternately poured, a C₁₀-C₁₂ alcohol ethoxylated at 5 EO, and ethanol, ie approximately 195 g of ethoxylated alcohol and approximately 220 g of ethanol. The reaction mixture changes from green-brown to light yellow as the neutralization progresses. The final pH is close to 7.

A 73-77% by weight ABS composition of triethanolamine is obtained.

COMPARATIVE EXAMPLE 2 A 40% composition of anionic active materials is produced.

For this composition, the following mixture is prepared: ABS neutralized with triethanolamine 30% ethoxylated alcohol C₁₀-C₁₂ 5 OE 4.5% PS (93% paraffin sulfonate) sodium 2% Sodium LES (laurylethersulfate) 8% amidobetaine 4% diethanolamide on ethoxylated copra (5 EO) 3.4% NaCl 2.25% EtOH 1.75% water qs. 100%

Salt, sodium chloride is not sufficiently soluble in water and alcohol and it is released after a few hours.

EXAMPLE 2 :

The following composition is prepared according to the invention:
32.3% ABS neutralized with triethanolamine
5.2% ethoxylated alcohol C OE-C₁₂ 5 OE
8.5% AES sodium
12.75% coconut diethanolamide
6% ammonium lactate
5% H₂SO₄ 1M solution
3% EtOH
qs 100% water.

Poured into the neutralized ABS sulfuric acid, with stirring, then the ethanol and the coconut amide, and finally the ammonium lactate, then the sodium AES.

The composition obtained is limpid, clear, ocher yellow. It contains 40% of anionic active ingredients, 18% of nonionic active ingredients. Its viscosity is 130 mPa.s the first day and 160 mPa.s the second day.

This composition is diluted four times with water. The viscosity of the diluted composition is 400 mPa.s the first day and 470 mPa.s the second day. Its color is light yellow.

The cloud point is at 0 ° C and the detouble point at + 2 ° C.

This composition is remarkable because:
ABS is neutralized prior to formulation, which makes it possible to obtain neutralized ABS which can be used for any other formulation since it is not neutralized in situ .

the diluted composition has a viscosity greater than the viscosity of the concentrated composition.

the concentrated composition contains 60% of active ingredients.

the concentrated and diluted compositions are clear.

the amount of alcohol is small, which makes it possible to introduce the concentrated composition into polyvinyl chloride cartons without the latter being damaged by alcohol.

EXAMPLE 3 :

The following composition is prepared (the percentages are given by weight relative to the weight of the composition):
45.6% of alkylbenzenesulfonic acid, the alkyl chain of which contains from 10 to 12 carbon atoms, neutralized by monoethanolamine, in the presence of ethanol and "LAUROPAL 02-05" which is a C₁₀-C₁₂ alcohol with 5 EO manufactured by the company WITCO.
27% of "LAUROPAL 02-05" including that supplied with neutralized alkylbenzenesulfonic acid.
7% of sodium LES which is a fatty alcohol (C₁₂-C₁₄) ethoxylated to 2.2 EO on average and sulfated.
8% of "ANTIL 141" liquid manufactured by GOLDSCHMIDT, which is a compound of
40% of polyethoxylated propylene glycol dioleate at 55 EO on average,
20% water and
40% propylene glycol.
3.8% ammonium lactate.
5.7% ethanol, including that supplied with neutralized alkylbenzenesulfonic acid.
water qs 100%.

Ammonium lactate is obtained by neutralizing lactic acid with gaseous ammonia or in solution.

The concentrated composition thus obtained according to the invention has a viscosity of 250 mPa.s. When 250 ml of this composition is diluted with 750 ml of water, for example tap water, a diluted composition with a viscosity of 300 mPa.s is obtained. These compositions are clear, without deposit. Their cloud points are below 5 ° C and down to -9 ° C.

EXAMPLE 4

Composition with 24% of active ingredients. Triethanolamine abs 11.2% sodium lauryl sulfate (LS) 2.8% coconut diethanolamide 10% H₂SO₄ 1M 4% sodium cumene sulfonate 0.5% isopropanol 1% salt X Y% water qs. 100%

The percentage of salt and the nature of the salt are varied. salt X concentration Y% Appearance at room temperature of the concentrated composition Ammonium acetate 4% trouble release 3% Claire Sodium chloride 4% trouble release 3% Claire Magnesium sulfate 10% trouble release 9% Claire Ammonium lactate 16% trouble release 15% Claire
This example shows the influence of the amount of salt added, depending on the solubility, on the cloud point of the concentrated composition.

EXAMPLE 5

The following compositions are prepared: see Table I
This example shows the influence of the propylene glycol dioleate polyethoxylated at 55 EO which makes it possible to lower the cloud point of the concentrated compositions to 40% and 60% of active materials in combination with the coconut diethanolamide. The cloud point lowering surfactant represents between 0 and 50% by weight of the viscosity regulating surfactant.

EXAMPLE 6

A composition is prepared with 60% of active materials (total of surfactants) including around 40% of anionic surfactants. Product By weight on 200 g Percentage 76% TEA ABS (Witbarco) 88.6 ABS 33.7% Lauropal 5.2% LES Na (Neopon Witco) 70% 24.3 8.5 DEA of copra (Witcamide LDT / S Witco) 28 11.9 H₂SO₄ 1M 10 5 Antil 141 L (40% propylene glycol dioleate at 55 EO) 6 1.2 Ethanol 4 2 Salt X X / 2 H₂O qs for 200 qs for 100% Percentage of anionics = 42.1
Percentage of nonionics = 18.3
The nature of the salt and its quantity are varied in the compositions.
With the different salts, the following results are obtained: Sodium lactate % salt in the concentrate Viscosity (mPa.s) with sodium lactate Composition concentrated diluted 2 185 312 5.5 166 607 6 170 639 7 177 558 10 457 380 Solubility: slight deposit from 5.5% in the concentrated composition; cloudy and opaque at 10%. Ammonium lactate % salt in the concentrate Viscosity (mPa.s) with ammonium lactate Composition concentrated diluted 2 168 366 3.5 150 656 4.5 146 664 5 141 644 6 140 595 10 166 219 Solubility: greater than 12% in the concentrated composition. Magnesium sulfate % salt in the concentrate Viscosity (mPa.s) with MgSO₄, 7H₂O Composition concentrated diluted 1 212 146 2 196 390 3 185 540 4 171 496 5 173 317 Solubility: In the concentrated composition, cloudy from about 7%. Potassium phosphate % salt in the concentrate Viscosity (mPa.s) with K₂HPO₄ Composition concentrated diluted 2 158 296 4 139 585 5 130 645 6 139 512 8 159 453 Solubility: slight deposit from 4% in the concentrated composition. Significantly deposits only after 6%. Large deposit at 8%. Ammonium sulphate % salt in the concentrate Viscosity (mPa.s) with (NH₄) ₂SO₄ Composition concentrated diluted 1 161 266 2 139 537 3 122 700 4 120 606 5 124 550 Solubility: Phenomenon of salting out from 5% in the concentrate. Ammonium propionate % salt in the concentrate Viscosity (mPa.s) with ammonium propionate Composition concentrated diluted 1 170 268 2 148 472 3.5 129 521 5 117 414 7 117 209 Solubility: solubility limit higher than 10% in the concentrate.

The viscosity curves are given in FIG. 1.

EXAMPLE 7

Compositions are prepared which are concentrated to approximately 80% of active materials. Product By weight on 200 g Percentage 76% monoethanolamine ABS (102 Shell) 119 43.7% LES (Neopon Witco) 70% 20 6.8 Lauropal 0205 (Witco) 40 26 Antil 141 L (20% H₂O, 40% dioleate, 40% propylene glycol) 16 3.2% dioleate 3.2% propylene glycol. Salt X Ethanol 11.2 5.6% Water qs 100%. Percentages of: Total active ingredients = 79.6% Anionics = 50.5% Nonionics = 29.1%

The viscosities of the concentrated and diluted compositions are studied as a function of the level of various salts.

The results are given in the following tables.

CONCENTRATE AND DILUTE VISCOSITES AS A FUNCTION OF MISCELLANEOUS SALTS

Viscosity of the salt-free concentrate = 262 mPa.s
Viscosity of diluted salt-free = 664 mPa.s % salt in the concentrate Viscosity (mPa.s) with ammonium citrate Composition concentrated diluted 0.5 259 558 1 254 520 2 238 471 Solubility: At 2% of ammonium citrate in the concentrate, appearance of a cloudiness. % salt in the concentrate Viscosity (mPa.s) with MgSO₄, 7H₂O Composition concentrated diluted 0.5 258 587 0.75 258 587 1 259 439 2 261 324 Solubility: At 2% MgSO₄, there is a cloudy concentrate. % salt in the concentrate Viscosity (mPa.s) with ammonium propionate Composition concentrated diluted 0.5 262 575 1 236 460 2 244 327 4 232 161 6 221 95 Solubility: at 6% salt in the concentrate, appearance of a cloud on the diluted. % salt in the concentrate Viscosity (mPa.s) with ammonium lactate Composition concentrated diluted 0.5 254 574 1 260 518 2 246 392 4 254 221 6 265 132 8 265 98 Solubility: at 8% salt in the concentrate: appearance of a cloud on the diluted.

EXAMPLE 8 DILUTIONS OF THE COMPOSITIONS CONCENTRATED WITH 80% OF ACTIVE MATERIALS

When diluting by the housewife, errors can be easily made: quantity of concentrated product used, capacity of the dilution bottle ... It is therefore important that we accept a fairly high margin of error for dilution without the physical characteristics of the diluted are significantly modified. Type of product Composition of the formula % Anionic ABS W / MEA (Wibarco monoethanolamine ABS) 44 Anionic LES Na (Neopon Witco) 6.75 Nonionic fluidifying concentrate Lauropal 0205 (Witco) (alcohol C₁₀-C₁₂ 5 OE) 26 Non-ionic viscosity regulator Antil 141 L (Goldschmidt) propylene glycol dioleate at 55 EO) 7.7 Viscosity regulating salt Ammonium lactate 3.7 Non-aqueous solvent Ethanol 5.6 H₂O qsq 100 Physical characteristics Brookfield, mobile 2 V₁₂ Concentrate viscosity (mPa.s) 367 Concentrate cloud point (° C) <-8
NB: Antil 141 L is expressed as gross product.

DILUTION

Dilution report Appearance of diluted Viscosity (mPa.s) (Brookfield V₁₂ mobile 2 at 20 ° C) 1/2 diluted cloudy, quickly out of phase low 1/3 diluted clear 149 1/4 diluted clear 268 1/5 diluted clear 470 1/6 diluted clear 385 1/8 diluted clear -
NB: The dilutions are made with cold tap water and by manual stirring.

It is seen that with these compositions, large margins of dilution error can be accepted.

EXAMPLE 9

Preparations are prepared with 24% of active materials, containing cumenesulfonate as hydrotrope. The results are given in Table II below.

EXAMPLE 10

Compositions containing 36% of active materials are prepared. The viscosities of the dilute are given in Table III below.

Claims (19)

1. A process for making a concentrated, pourable, clear liquid detergent composition water-dilutable to give a viscous diluted composition, characterized in that it comprises, in order to obtain a viscous composition after its dilution in water by the user, a mixture of:

   a) 10 to 70% by weight of at least one anionic surfactant, and

   b) a combination of:

   b₁) 2 to 20% by weight of at least one surfactant selected from the group formed by non-ionic, amphoteric and zwitterionic surfactants, and

   b₂) 0.5 to 20% by weight of at least one acid or its salt having the general formula
   
   $\text{I) A-C}$

   

   
   
   wherein A is an anion selected from the group formed by the anions of saturated or unsaturated aliphatic acids optionally containing 1 to 8 carbon atoms, and containing hydroxy groups, such as the groups derived from lactic, propionic, succinic, malic, glycolic, glyceric, tartaric, citric, gluconic, saccharic, formic, acetic, butyric, oxalic, maleic or itaconic acids; and the sulphate, iodide, bromide, chloride, thiosulphate, bichromate or orthophosphate groups; and C is H or a cation selected from the group formed by sodium, potassium, calcium, ammonium, alkanol-ammonium, magnesium, iron and copper ions, and

   c) water,
   while the total quantity of surfactants (a+b₁) is from 15 to 90% by weight and the ratio of the total quantity of anionic surfactants to the total quantity of non-ionic surfactants is greater than 1.
2. A process according to Claim 1, characterized in that it also comprises:

   d) at least one non-aqueous solvent,

   e) a non-ionic fluidity-imparting surfactant,

   f) at least one hydrotrope, and/or

   g) a pH-regulating acid.
3. A process according to Claim 2, characterized in that the total quantity of surfactants (a+b₁+e) is at most 90% by weight, and the ratio of the total quantity of anionic surfactants to the total quantity of non-ionic surfactants is greater than 1.
4. A process according to one of Claims 1 or 2, characterized in that the viscosity-regulating surfactant (b₁) comprises a surfactant selected from the group formed by the amides of C₈-C₂₀ fatty acids and amines having the formula

   

   wherein
   R₁ and R₂ are identical or different and are H, or a C₁-C₄ alkyl group substituted by one or more OH groups;
   the amides of monofunctional or polyfunctional acids having a saturated alkyl or an alkenyl chain, said amides optionally being oxyethylenated or oxypropenylated;
   alkylbetaines having the formula

   

   wherein R₃ is an alkyl or alkenyl radical having 8 to 20 carbon atoms,
      R₄ is -(CH₂)_z or -CH₂CH(OH)-(CH₂)_z
      x and y are identical or different integers of value 0 to 5,
      z is an integer from 1 to 5;
   alkylsulphobetaines having the formula

   

   wherein R₃, R₄, x, y and z have the same meanings as above;
   alkylaminobetaines having the formula

   

   wherein R₃, R₄, x, y and z have the same meanings as above and n is an integer of 1 to 6;
   alkylaminosulphobetaines having the formula

   

   wherein R₃, R₄, x, y and z and n have the same meanings as above;
   alkylamidosulphobetaines having the formula

   

   wherein R₃, R₄, x, y and z and n have the same meanings as above;
   esters of fatty acids and alkylene polyols which are polyethoxylated and/or polypropoxylated, containing from 1 to 100 ethylene oxide and/or propylene oxide groups, the fatty acid groups containing from 8 to 20 carbon atoms and the polyols being selected from 1,2-ethanediol, 1,2-propanediol, 1,2-butanediol, glycerol, sorbitan and glucose.
5. A process according to one of Claims 1 or 2, characterized in that one prepares a composition comprising at least 40% by weight of surfactants and comprising at least one anionic surfactant (a) containing practically no ions capable of forming precipitatable salts, to lower the cloud temperature of the concentrated composition.
6. A process according to Claim 1, characterized in that the viscosity-regulating surfactant (b₁) is selected from copra diethanolamide, an amidosulphobetaine wherein the R₃ radical is a saturated alkyl radical containing from 10 to 16 carbon atoms and R₄ is -CH₂-CHOH-CH₂- and ethoxylated propylene glycol dioleate containing an average of 55 OE in the molecule.
7. A process according to any of Claims 1 to 6, characterized in that the anionic surfactant (a) is previously neutralized.
8. A process according to Claim 5, characterized in that the cloud-temperature-lowering surfactant represents between 0 and 50% by weight of the viscosity-regulating surfactant.
9. A process according to any of Claims 1 to 8, characterized in that it contains a mixture of viscosity-regulating non-ionic surfactants which is formed by propylene glycol dioleate polyoxyethylated to 55 OE and copra diethanolamide.
10. A process according to any of Claims 1 to 9, characterized in that the surfactant (a) is an alkylarylsulphonic acid, the alkyl chain of which contains from 8 to 18 carbon atoms and which is neutralized by an amine containing from 1 to 3 hydroxyalkyl groups.
11. A process according to Claim 10, characterized in that the surfactant (a) is a (C₈-C₁₄ alkyl) benzenesulphonic acid neutralized by monoethanolamine in the presence of ethanol and an ethoxylated alcohol containing a C₁₀-C₁₂ alkyl radical and 5 OE.
12. A process according to Claim 11, characterized in that the surfactant (a) contains at least approximately 0.5% by weight of sodium chloride.
13. A process according to Claim 12, characterized in that the surfactant (a) contains less than approximately 2% by weight of sodium sulphate.
14. A process according to any of Claims 1 to 13, characterized in that the solvent is an alcohol selected from ethanol, isopropanol and mixtures thereof.
15. A process according to any of Claims 1 to 14, characterized in that one prepares a composition comprising:
       from 15 to 90% by weight of a mixture of at least one anionic surfactant and at least one viscosity-regulating surfactant,
       from 0.5 to 20% of a dissolved salt,
       from 0 to 10% of an alcoholic solvent,
       optionally an acid,
       the balance being water.
16. A process according to Claim 15, characterized in that it contains:
       from 10 to 70% by weight of at least one anionic surfactant,
       from 2 to 20% by weight of at least one viscosity-regulating surfactant,
       from 0.5 to 20% of a dissolved salt,
       from 0 to 45% by weight of a non-ionic fluidity-imparting surfactant,
       from 0 to 10% of an alcoholic solvent,
       the balance being water.
17. A process according to one of Claims 15 or 16, characterized in that one prepares a composition comprising:
       45% of monoethanolamine (C₁₀-C₁₂) alkyl benzenesulphonate,
       7% sodium lauryl ether sulphate,
       3% 55 OE propylene glycol dioleate,
       3% propylene glycol,
       27% (C₁₀-C₁₂) alcohol ethoxylated to 5 OE,
       4% ammonium lactate,
       6% ethanol,
       the balance being water.
18. A process according to one of Claims 15 or 16, characterized in that one prepares a composition comprising:
       34% of monoethanolamine (C₁₀-C₁₂) benzenesulphonate,
       5% of C₁₀-C₁₂ alcohol ethoxylated to 5 OE,
       8.5% of a 2.2 OE sodium (C₁₂-C₁₄) alkyl,
       11.9% copra diethanolamide
       1.2% of a propylene glycol dioleate ethoxylated to 55 OE,
       1.2% propylene glycol,
       3.5% ammonium lactate,
       5% 1M sulphuric acid solution,
       2% ethanol,
       the balance being water.
19. A process for regulating the viscosity V₁ of a concentrated liquid detergent composition and the viscosity V₂ of the diluted composition obtained by addition of water, characterized in that it comprises the addition, to at least one anionic surfactant optionally mixed with at least one non-ionic surfactant, of a viscosity regulator formed by a combination of at least one non-ionic, amphoteric or zwitterionic surfactant and an acid or its dissolved salt, to obtain a concentrated composition prepared according to Claims 1 or 2.

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