GB2230021A - Detergent composition comprising as surfactant an ethoxylated succinimide derivative - Google Patents

Abstract

Detergent compositions comprise as surfactant a compound having the formula: <IMAGE> wherein R1 is an alkyl or alkenyl group having 8-22 carbon atoms, R2 is H, an alkyl group having 1-4 carbon atoms, acetyl or phenyl, x is an integer of from 1-20, y is an integer of from 0-5 and z is an integer of from 0-20, optionally admixed with usual components for detergents. These detergent compositions are in particular useful in cleaning textiles or hard surfaces.

Description

DETERGENT COMPOSITION COMPRISING AS SURFACTANT AN ETHOXYLATED SUCCINIMIDE DERIVATIVE This invention relates to detergent compositions comprising as surfactant an ethoxylated succinimide derivative.

Ethoxylated succinimide derivatives, in particular ethoxylated alkenylsuccinimides, are known from U.S. patent specification No. 3,642,713 as additives in polyaznide compositions because of their antistatic properties.

Said patent discloses that in many instances, shaped articles made of synthetic, semisynthetic and natural material undergo electrostatic charging during processing and subsequent application. Said ethoxylated succinimides derivatives showed an antistatic effect.

It is an object of this invention to provide a detergent composition comprising a succinimide derivative as surfactant.

This object is accomplished by a detergent composition comprising as surfactant a compound having the formula:

wherein R1 is an alkyl or alkenyl group having 8-22 carbon atoms, R2 is H, an alkyl group having 1-4 carbon atoms, acetyl or phenyl, x is an integer of from 1-20, y is an integer of from 0-5 and z is an integer of from 0-20, optionally admixed with usual components for detergents.

Preferably said detergent composition comprises as surfactant a compound of the above formula, wherein R1 is an alky or alkenyl group having 8-14 carbon atoms, R2 represents H, x is an integer of from 2-8, y is 0 and z is 0.

It is another object of this invention to provide a detergent composition comprising another surfactant(s) besides said succinimide derivative.

This second object is accomplished by a detergent composition comprising besides the succinimide derivative of the formula at least one other suitable surfactant consisting of the usual anionic, nonionic, amphoteric and cationic surfactants.

The succinimide derivatives used in accordance with the invention are known in the art and can be obtained, for example, by reacting compounds containing double bonds capable of addition, with maleic acid anhydride to form an alkenyl succinic acid anhydride which is converted by reaction with an alkylolamine, for example ethanolamine, into the corresponding imide and subsequently oxalkylated with alkylene oxides, for example ethylene oxide and propylene oxide, optionally after hydrogenation of the double bond.

As anionic surfactant besides the above succinimide derivatives at least one compound may be used selected from the group of alkylbenzene sulphonates, alkylsulphonates, olefin-sulphonates, estersulphonates, alkylsulphates and alkylpolyethersulphates and alkali metal soaps.

Useful anionic surfactants include alkyl sulphonates and sulphates containing from 8 to 18 carbon atoms; alkylbenzene sulphonates with 8-18 carbon atoms in the alkyl chain, olefin sulphonates prepared by the sulphonation of C12-C24 alpha or internal olefins and sulphonated methyl ester sulphonates derived from C12-C18 fatty acid methyl esters, and alkali metal soaps, containing from 12-24 carbon atoms. Particularly useful in liquid dishwashing and foaming agents are alkylether sulphates with 10 to 18 carbon atoms in the alkylresidue and 1-12 ethyleneglycol ether groups.

The anionic surfactants mentioned before are applied in the form of their sodium salt, but also potassium, ammonium, mono-, di-, triethanol amine salts can be used, the latter preferably in liquid formulations.

As nonionic surfactant one may use alcohol ethoxylates, alkylphenolethoxylates, polyethyleneglycol esters of carboxylic acids, alkylpolysaccharides e.g. alkyl polyglucosides and alkanolamides.

Preferred nonionics are the condensation products with 1-12 mol ethylene oxide with detergent range alcohols, such as fatty, oxo and secondary alcohols from the C8-C18 range, and with mono- or dialkylphenols containing 6-12 carbon atoms in the alkyl chain.

Examples of commercially available nonionics of this type include DOBANOL 25-7 (the condensation product of a C12-C15 synthetic linear alcohol with 7 moles of ethylene oxide), DOBANOL 45-4 and DOBANOL 45-7 (the condensation products of a C14-C15 synthetic linear alcohol with 4 moles and 7 moles of ethylene oxide respectively). In laundry powder formulations and in built laundry liquids the use of ethoxylates with 3-8 mol ethylene oxide (EO) per mol alcohol is preferred, in non-built laundry liquids and in dishwashing liquids the preference is given to 5-12 moles EO.

Other useful nonionic surfactants are polyethylene glycol esters based on C12 C18 fatty acids with 2-10 ethylene oxide groups; the condensation products of detergent range alcohols with a mixture of ethylene- and propylene oxide (PO) in which the number of EO groups ranges from 3-12 and the ratio EO/PO is from 10/1 to 3/1; alcohol ethoxylates in which the terminal hydrogen is replaced by a short hydrophobe such as methyl, isopropyl, isobutyl or acetyl.

Suitable amphoteric surfactants are detergent range molecular weight betaines, amidobetaines and sulphobetaines. They are preferably applied as foam stabilizing agents in liquid dishwashing agents.

Finally suitable cationic surfactants can also be included in detergent compositions of the present invention. Cationaic surfactants comprise a wide variety of compounds generally containing at least one quaternary nitrogen and generally associated with an anionic radical. Pentavalent nitrogen ring compounds are also considered quaternary nitrogen compounds. Suitable anions are halides, methyl sulphate and hydroxide.

Tertiary amines can have characteristics similar to cationic surfactants when present in laundry compositions at pH values less than about 8.5.

A more complete disclosure of cationic surfactants useful herein can be found in U.S. patent specification No. 4,228,044, incorporated herein by reference.

The detergent compositions of the invention may contain the usual components for detergents which are selected from builders, bleaches, additives and formulation adjuvants.

Besides the surfactants, the washing and cleaning agents may also contain known builder salts in amounts of 0-50%, preferably from 5-35%, to intensify the cleaning action. Examples of inorganic builders are phosphates, polyphosphates, alkali metal carbonates, silicates and sulphates. Examples of organic builders are polycarboxylates such as polymers and copolymers of acrylic and maleic acid, aminocarboxylates such as ethylenediaminotetraacetates, nitrilotriacetates, hydroxycarboxylates, citrates, succinates and substituted and unsubstituted alkanedi- and poly carboxylic acids. Another type of builder, useful in granular laundry and built liquid laundry agents, includes various substantially water-insoluble materials which are capable of reducing the water hardness e.g. by ion exchange processes. In particular the complex sodium aluminosilicates, known as zeolite A, are useful for this purpose.

The detergent compositions of the invention, designed for textile washing, may also contain per-compounds with a bleaching action such as perborates, percarbonates, persulphates and organic peroxyacids. These per-compounds may contain stabilizing agents, such as magnesium silicate, sodium ethylenediamine-tetra-acetate (EDTA) or sodium salts of phosphonic acids. In addition, bleach activators can be used to increase the efficiency of the inorganic persalts at lower washing temperatures. From the vast number of compounds mentioned in literature are in particular substituted carboxylic acid amides, e.g. tetraacetylethylenediamine (TAED); substituted carboxylic esters e.g. isononyloxybenzenesulphonate and sodiumcyanamide attractive.

In addition to the surfactants, builders and bleaches as described hereinbefore, laundry detergent compositions may contain other ingredients which are usually applied in minor quantities such as antigreying agents and anti-incrustation agents, foam control agents, enzymes, optical brighteners and perfumes.

As antigreying agent, watersoluble colloids of an organic nature are preferably used. Examples are water soluble cellulose derivatives such as carboxymethyl cellulose methyl- and hydroxyethylcellulose.

Examples of foam control are high molecular weight fatty acid soaps, paraffinic hydrocarbons, and silicon containing defoamers.

In particular hydrophobic made silica particles are efficient foam control agents in these laundry detergent formulations.

Examples of known enzymes which are effective in laundry detergent agents are protease, amylase and lipase. Preference is given to the enzymes which have their optimum performance at the design conditions of the washing and cleaning agent.

As fluorescent whiteners, a vast number of components is described in literature. For laundry washing agents the derivatives of diaminostilbene disulphonates and substituted distyrylbiphenyl are particularly suitable.

Although the surfactants from the present invention have proper solubility and viscosity characteristics when applied in liquid formulations, it may be desired to add hydrotropes and/or solubilizer alcohols to control the stability and viscosity of the liquid formulations.

Examples of suitable hydrotropic substances are alkali metal salts of benzene, toluene and xylene sulphonic acids; alkali metal salts of formic acid, citric and succinic acid, alkali metal chlorides, urea, mono-, di-, and tri-ethanolamine. Examples of solubilizer alcohols are ethanol, isopropanol, mono- or polyethylene glycols, monopropylene glycol and etheralcohols.

The detergent composition of the invention may be formulated as powdered or liquid detergent composition.

A powdered or liquid detergent composition of the invention has advantageously the following formulation: a. 1-80% of a compound according to the invention, b. 0-50% of a co-surfactant, selected from the class of anionic, nonionic, amphoteric and cationic surfactants, c. 0-50% of detergent builders, selected from the class of phosphates, polyphosphates, sodium aluminosilicates, aminopolycarboxylic acids, and alkali metal carbonates, silicates, sulphates and polycarboxylates, d. 0-25% of peroxy bleaching agents, selected from the class of perborates, e. 0-10% of peroxyacid generating bleach activators, f. 0-10% of foam suppressing or boosting agents, g. 0-10% of other detergent components selected from enzymes, soil suspending agents, optical brighteners, anti-spotting agents, dyes, perfumes, h. 0-50% of solubilizer alcohols and/or hydrotropes.

The invention will be further illustrated by means of the following examples without limiting it.

The preparation of a suitable alkenylsuccinimide ethoxylate having a C10 alkyl chain and an average of 6 ethylene oxide groups per molecule.

To 0.5 mol of decenylsuccinic anhydride, dissolved in 500 ml toluene, 0.53 mol of monoethanolamine was added. The reactants were condensed by refluxing the mixture for about 18 hours under azeotropic removal of the water formed. After removal of the toluene by atmospheric distillation, the decenylsuccinimide compound was distilled off at 160-170 "C at a reduced pressure of 5.10 mbar. Subsequently the product was reacted with ethylene oxide in a stirred autoclave.

The ethoxylation procedure was as follows: 0.4 mol of the decenylsuccinimide compound were mixed with 1 g of a 50% potassium hydroxide solution, the autoclave was sealed and air atmosphere was replaced with high quality nitrogen. The reactor was evacuated to about 15 mbar and heated to about 1 hour at 120 "C, under stripping with nitrogen to remove water. The system was then pressurized with nitrogen to about 2 bar and 2 mol of ethylene oxide of a high purity was fed in slowly in about 2 hours while maintaining a pressure of 4-5 bar and a temperature of 125-135 "C. After the calculated amount of EO had been added, the reaction mixture was stirred for another 1-2 hours till the pressure had reached a steady value.

After completion of the reaction, the excess ethylene oxide was removed by purging the autoclave with nitrogen. The product was cooled down and transferred into a sample bottle containing 0.5 g of acetic acid to neutralize the potassium hydroxide.

Other succinimide ethoxylates were prepared according to an analogous procedure.

The examples in tables I-III illustrate the washing and cleaning performance of the alkenylsuccinimide ethoxylates in comparison to the detergent alcohol ethoxylates DOBANOL 25-7 and DOBANOL 45-7 and to a Cll-C13 linear alkylbenzenesulphonate (C11 -C13 LAS).

The washing experiments were carried out in a Terg-O-Tometer at 40 "C and a water hardness of 3 mmol/l calcium using soiled permanent press polyester/cotton. The applied soils were radio labeled synthetic sebum (consisting of a mixture of hydrocarbons, fatty acids and higher alcohols), radiolabeled cetane/squalane and radiolabeled clay. The amount of removed soil was determined after 20 minutes by measurement of the radioactivity of the washwater and/or the washed fabric. In the washing experiments three different builder systems were used. System I contained 2 g/l sodium sulphate, system II contained 0.24 g/l silicate and 0.60 g/l sodium sulphate, system III contained 1.25 g/l Zeolite A, 0.25 g/l sodium carbonate, 0.24 g/l sodium silicate and 0.60 g/l sodium sulphate.

Using builder systems I and II, the alkenylsuccinimide ethoxylates appear to be superior over the 7-EO alcohol ethoxylates and the C11-C13 LAS in their removal of sebum soil. Using builder system III, the succinimide ethoxylates have an advantage over the alcohol ethoxylates in the removal of clay soil.

TABLE I: Builder system I : 2 g/l Sodium sulphate Terg-O-Tometer speed: 50 cycles/min.

Alkyl chain Number of % Sebum % Cetane/squalane length EO groups removal removal C10= 6.1 47.6 28.2 C12 4.4 36.2 22.2 C12= 5.5 44.4 26.3 C12= 6.3 45.5 27.5 C14= 4.5 19.6 23.3 C14= 6.9 33.9 21.5 014= 9.1 41.7 25.0 DOBANOL 25-7 32.5 26.5 DOBANOL 45-7 31.3 25.8 C11*-C13 LAS 16.4 28.4 LSD at 95% confidence level 3.4 1.3 LSD = least significant difference TABLE II: Soil removal by alkenylsuccinimide ethoxylates Builder system II : 0.24 g/l Sodium silicate 0.60 g/l Sodium sulphate Terg-O-Tometer speed : 50 cycles/min.

Alkyl chain Number of % Sebum soil % Clay soil length EO groups removal removal C12 3.3 37 35 C12= 5.5 76 36 DOBANOL 25-7 77 33 DOBANOL 45-7 74 30 Cll-C13 LAS 80 31 LSD, at 95% confidence level 4 3 TABLE III: Builder system III : 1.25 g/l zeolite A, 0.25 g/l sodium carbonate, 0.24 g/l sodium silicate, 0.60 g/l sodium sulphate Terg-O-Tometer speed : 100 cycles/min.

Alkyl chain Number of % Sebum soil % Clay soil length EO groups removal removal C12= 3.3 81 41 C12= 5.5 79 42 DOBANOL 25-7 80 37 DOBANOL 45-7 79 33 Cll-Cl3 LAS 80 47 LSD, at 95% confidence level 4 3 The examples in Tables IV and V illustrate compositions of the washing and cleaning agents containing the surfactant of the invention. Table IV summarizes examples of the application in granular laundry detergents, Table V those in liquid laundry detergents.

TABLE IV: Application in granular laundry detergents.

Component Formulation (Composition in %w) 1 2 3 4 5 A C12 succinimide - 4 EO - 6 3 3 C12 succinimide - 6 EO 10 - - - 5 DOBANOL 45-4 - - 3 - DOBANOL 45-7 - - - 3 B C11-C13 LAS - 6 6 6 15 12 22 Soap - 2 2 2 C Sodium tripolyphosphate 25 - - 30 20 Zeolite A - 30 30 - Sodium carbonate - 10 5 - Sodium silicate 5 5 5 5 Sodium sulphate 25 10 10 20 40

Organic builders < ------- 0-10 -------- > D Sodium perborate 20 15 20 15 E TAED 2 3 2 3

F Foam inhibiting agents < -------- 0- 1 G Other detergent components < 2-10 Water < -------------- Balance TABLE V: Application in liquid laundry detergents.

Component Formulation (Composition in %w) 1 2 3 4 5 A C10 succinimide - 4 EO - - - 3 C10 succinimide - 6 EO 14 7 20 2 2 DOBANOL 45-4 - - - - 3 DOBANOL 45-7 - 7 - - B C11-C13 LAS 14 12 - 5 5 C12 C22 Soap 10 14 - 2 2

Triethanol amine < 0-10 C Sodium tripolyphosphate - - - 20 Zeolite A - - - - 25 Sodium carbonate - - - - 5 Sodium silicate - - - 2 2 Sodium sulphate - - - 1 1

Organic builders < --------- 0- 5 ------ > F Foam inhibiting agents < ---------- 0- 1 G Other detergent components < 2-10 H Solubilizers < 0-10 Water < Balance

Claims (11)

1. CLAIMS 1. A detergent composition, comprising as surfactant a compound having the formula:

   wherein R1 is an alkyl or alkenyl group having 8-22 carbon atoms, R2 is H, an alkyl group having 1-4 carbon atoms, acetyl or phenyl, x is an integer of from 1-20, y is an integer of from 0-5 and z is an integer of from 0-20, optionally admixed with usual components for detergents.
2. 2. A detergent composition according to claim 1, wherein in the formula:

   R1 is an alkyl or alkenyl group having 8-14 carbon atoms, R2 represents H, x is an integer of from 2-8, y is 0 and z is 0.
3. 3. A detergent composition according to claim 1 or 2, comprising at least one other suitable surfactant consisting of the usual anionic, nonionic, amphoteric and cationic surfactants.
4. 4. A detergent composition according to claim 3, comprising at least one anionic surfactant selected from the group of alkylbenzene sulphonates, alkylsulphonates, olefin-sulphonates, estersulphonates, alkylsulphates, alkylpolyethersulphates, and alkali metal soaps.
5. 5. A detergent composition according to claim 3, comprising at least one nonionic surfactant selected from the group of alcohol ethoxylates, alkylphenolethoxylates, polyethyleneglycol esters of carboxylic acids, alkylpolysaccharides and alkanolamides.
6. 6. A detergent composition according to claim 3, comprising at least one amphoteric surfactant selected from betaines, amidobetaines and sulfobetaines.
7. 7. A detergent composition according to claim 3, comprising at least one cationic surfactant selected from the quaternary ammonium surfactants.
8. 8. A detergent composition according to one or more of the claims 1-7, comprising the usual components for said detergent which are selected from builders, bleaches, additives and formulation adjuvants.
9. 9. A detergent composition according to one or more of claims 1-8, for use in cleaning textiles or hard surfaces.
10. 10. A powdered or liquid detergent composition according to one or more of claims 1-9, consisting essentially of: a. 1-80% of a compound according to claim 1, b. 0-50% of a co-surfactant, selected from the class of anionic nonionic, amphoteric and cationic surfactants, c. 0-50% of detergent builders, selected from the class of phosphates, polyphosphates, sodium aluminosilicates, polycarboxylic acids, aminopolycarboxylic acids, d. 0-25% of peroxy bleaching agents, selected from the class of perborates, e. 0-10% of peroxyacid generating bleach activators, f. 0-10% of foam suppressing or boosting agents, g. 0-10% of other detergent components selected from enzymes, soil suspending agents, optical brighteners, anti-spotting agents, dyes and perfumes, h. 0-50% of solubilizer alcohols and/or hydrotropes.
11. 11. A detergent composition substantially as hereinbefore described with reference to the examples.