FI63058B - FLYTANDE BUFFRAD DETERGENTKOMPOSITION SAMT FOERFARANDE FOER DES FRAMSTAELLNING - Google Patents

Abstract

A liquid detergent composition, particularly suitable for use in the underbuilt region of dosages, comprises at least 10 % by weight of a sodium soap, at least 1 % by weight of an organic synthetic detergent, the wieght ratio of soap to synthetic detergent being 10:1 to 1:1, and at least 0.1 % by weight of a buffering agent.

Description

-, D, .... KU RELEASE r 7 No. utlAggninosskript 6 3058 • äig ^ J i nvi n '.: tΠ M 1933 ^ (51 j K ».ik.3 / ii * t.ci.3“' C '' ¥ i 'Da ^ / 02 ENGLISH I —Fl N LAN D (21) PtMnttlhelwmu · - PKwttiwekiiing 781389 (2J) Htkemltpilvl —Ametalnpd · * 0U.05 * 78 (Fl) (23) Alkuplivi —CtMfhMsdif OU.05.78 ( 41) Tullut JulklMkil - Ulvk offantlig 07.11.78

Patent and Registration Offices !! · (44) NlhtivUulputon and other months * »excl. - TL 12 82

Patent and registration authorities Anattkan uttigd och utUkrtften publictrad (32) (33) (31) Requested «uoiksus -» «Girt pdorttet 06.05 * 77 15.07.77 English-England (GB) 19119/77, 29729/77 (71) Unilever NV , Burgemeester s'Jacobplein 1, Rotterdam,

Holland-Holland (NL) (72) Peter John Russell, Wirral, Merseyside, England-England (GB),

Govert Johannes Pieter Augustijn, Zeist, Jacob Adriaan van de Griend,

Maassluis, Holland-Ho Hand (NL) (7U) Leitzinger Oy (5U) Liquid buffered detergent composition and method for its preparation - Flytande buffrad detergentkomposition samt förfarande för dess framställning

The present invention relates to an aqueous liquid detergent composition comprising at least 10% by weight of sodium soap, at least 5% by weight of a synthetic anionic or nonionic detergent and optionally a base salt, wherein the weight ratio of soap to synthetic detergent is greater than 1.

Aqueous liquid detergents are well known in the art. Typically, such compositions will contain one or more synthetic organic detergents, solvents, and, in the case of bulk liquid detergent compositions, inorganic and / or organic backing salts. Such compositions often also contain hydrotropes which allow the addition of sufficiently large amounts of detergents and base salts to provide the desired physical properties as well as good detergency.

In the formulation of such aqueous liquid detergent compositions, physical properties such as shelf life, brightness, viscosity, pourability, etc. play an important role as well as washability and foamability when the mixture is used in a certain volume. Thus, for example, although a mixture may have good washability and foamability at a given dosage, performance is often found to be significantly reduced when lower dosages are used. This is especially the case in situations where the dosage is not sufficient to inactivate the ions that cause the water hardness, i. In so-called "under-built" situations. From an ecological point of view, a reduction in the amount of phosphate backbone salts may be desirable, but such a reduction reduces the washing capacity, especially in an "under-built" situation.

It has already been proposed in the art to formulate so-called base salt-free liquid detergent compositions, which are compositions which do not contain body salts. Thus, English Patent 1,370,402 discloses non-ionic surfactant compositions comprising a nonionic surfactant, an anionic surfactant which is a C8-C4 alkylbenzenesulfonic acid or a C24-C24 fatty acid alkanolamine salt, and a free Canol alkanolamine salt.

British Patent 1,365,464 describes base-salt-free liquid detergents containing a nonionic surfactant, a mixture of a C8-C18 alkylbenzenesulfonic acid and an alkanolamine salt of C8-C24 fatty acids and free ethanolamine.

However, these attempts have not been entirely satisfactory because the achievement of one or more desired traits is often associated with a significant deterioration in other desirable traits. The disadvantages of the above formulations can thus be too low foaming ability or poor washing ability at higher dosages.

In addition, these formulations apply to compositions in which the soap component is an alkanolamine salt that is more soluble than more readily available sodium soaps. However, the present invention relates to soap-based liquid detergent compositions in which the soap component is or contains sodium soap.

In fact, liquid detergent compositions which may contain sodium soap have already been proposed in the art. For example, U.S. Patent No. 2,875,153 describes a liquid detergent composition in gel form containing a water-soluble soap and a nonionic detergent. The water-soluble soap may be sodium soap. However, this product is a gel, which makes it unsuitable as a liquid, detergent mixture due to its viscosity and pourability properties.

U.S. Patent No. 2,543,744 discloses a low-foam dishwashing composition comprising an alkali metal soap and a nonionic surfactant. When these formulations are in the form of an aqueous liquid containing sodium soap, they contain the latter up to 7.5%.

Numerous other proposals have been made for liquid detergents containing a soap component. Thus, U.S. Pat. No. 3,723,328 relates to compositions which may contain up to 16.2% sodium soap; U.S. Patent No. 3,707,503 discloses bulking compositions which may contain up to 4.5% sodium soap.

British Patent 1,415,719 discloses liquid compositions comprising a liquid nonionic substance and fatty acids which may be partially neutralized to sodium soaps, and British Patent 1,081,556 discloses liquid detergent compositions comprising a portion of a soap component.

Dutch patent application 7413265 and German patent application 2,411,528 relate to liquid mixtures containing a mixture of sodium soaps of C8-C4 saturated and unsaturated fatty acids together with other synthetic detergents and possibly base salts.

Dutch patent application 7406004 discloses a liquid mixture containing up to 8% of alkali metal soap and up to 60% of a mixture of nonionic surfactants. U.S. Patent No. 2,560,839 discloses a liquid composition containing up to 10% alkali metal soap, up to 30% nonionic surfactant and up to 30% pyrophosphate base salt. Although all of these companies provide products that are suitable for certain washing applications, they are not so well suited for other cleanings, especially at different dosages and / or in "underbuilt" situations.

It has been found that good liquid 4,63058 detergent compositions can be prepared which are isotropic, contain ecologically acceptable components, are particularly suitable for the "underbuilt" dosing range and also have, in higher dosages, similar superior washing properties to conventional salt-containing products. liquid mixtures.

The discovery of such versatile blends has been made possible by the use of rich fatty acid sodium soaps and, with them, suitable amounts of synthetic detergent and some buffers which increase the detergency of these liquid soap blends.

The composition of the present invention is characterized in that the mixture contains (a) 10 to 40% by weight of the total mixture of one or more sodium soap of a straight or branched chain, saturated or unsaturated fatty acid, (b) 5 to 25% by weight of the total mixture of anion or a nonionic synthetic detergent, wherein the weight ratio of sodium soap to organic synthetic detergent is from 10: 1 to 1: 1, and (c) 2-10% by weight of the total mixture of alkanolamine as a buffer buffering the pH of the washing solution to 7-11.

Such aqueous liquid detergent compositions are effective at lower dosages in "underbuilf situations" and are superior to other conventional liquid salt-free liquid compositions at higher dosages, allowing them to even behave at higher dosage levels compared to conventional liquid salts. The compositions of the invention have superior .

The essential ingredients of the composition according to the invention are discussed in detail below.

a. Soap component.

The soap component is or contains sodium soap of straight or branched chain fatty acids having 8 to 24 carbon atoms in the alkyl residue. Such fatty acids include saturated and unsaturated natural fatty acids as well as synthetic fatty acids. In the latter, there may be some branching in the alkyl residue, for example up to 20% of methyl groups in the α-position of the alkyl residue. Typical examples of suitable fatty acids are caprylic, capric, lauric, myristic, palmitic, stearic, oleic, linoleic, behenic acid and mixtures of such fatty acids. Also suitable are fatty acids derived from natural fats and oils, such as coconut oil fatty acids, palm and palm kernel oil fatty acids, soybean oil, safflower oil, pine oil, tallow, fish oil, fatty oil, castor oil, peanut oil. Examples of synthetic fatty acids are fatty acids obtained by oxidizing petroleum or hydrogenating carbon monoxide by the Fischer-Tropsch method.

Preferred sodium soaps include sodium oleate, sodium salt of coconut fatty acids, and mixtures thereof. In the latter cases, the weight ratio of the two components is between 9: 1 and 1: 9, preferably between 4: 1 and 1: 4.

The minimum amount of sodium soap in the mixture is about 10% by weight; by means of the present invention it is possible to add large amounts of sodium soap, i.e. sodium soap may be added up to 60% by weight. In general, for most practical purposes, the amount of sodium soap is 15 to 50, in particular 20 to 35% by weight of the mixture.

Other soaps with different cations, such as potassium soaps and alkanolamine soaps, may also be added if the amount of sodium soap is in the ranges given above.

Sodium soaps may be added to the mixtures as such or may be formed in situ by neutralizing the corresponding fatty acids in the mixture with the addition of a suitable sodium salt-forming alkaline substance such as alkali liquor or sodium hydroxide. The same applies to soaps that may be used at the same time and contain another cation.

t \ 6 63058 b. Organic synthetic detergent.

This ingredient may be selected from the group consisting of anionic or nonionic organic synthetic detergents. Anionic synthetic detergents (the term does not include salts of natural fatty acids or synthetic fatty acids) are in principle compounds with a hydrophobic radical and a soluble salt-forming anion such as sulfate, sulfonate and phosphate thianion.

Typical examples are C8-C24 straight or branched chain alkylarylsulfonates, C8-C22 primary or secondary alkane sulfonates, C8-C24C * olefin sulfonates, C8-C22 primary or secondary alkyl ether sulfates containing 1-15 moles of butylene oxide, ethyleneoxide and ethylene oxide. a mixture thereof, sulphonated fatty acids or fatty acid esters, C8-C24 acyl taurides, C8-C24 acyl isethionates, C8-C18 alkyl or alkylaryl phosphates or ether phosphates having 1 to 10 moles of ethylene oxide, propylene oxide or propylene oxide thereof. The term anionic synthetic detergents also includes salts of alkyl polyglycol ether carboxylic acid. Additional examples of anionic synthetic detergents have been given in standard textbooks such as Schwartz, Perry and Berch, "Surface-active Agents and Detergents", Vol. I (1949) and vol. II (1958). These anionic substances are used as their sodium, potassium, ammonium or alkanolamine salt.

Nonionic synthetic detergents roughly cover compounds with a hydrophobic radical and a water-soluble group that does not ionize. Usually, this dissolution in water is accomplished by ethoxylation and / or propoxylation of a hydrophobic molecule having a leaving proton.

7 63058

Typical examples are straight-chain or branched, primary or secondary, natural or synthetic alcohols having from 8 to 24 carbon atoms in the alkyl chain, mono- or dialkylphenones having from 8 to 18 carbon atoms in the alkyl chain, C8-24 fatty acids (as defined above for sodium ), ethoxylation and / or propoxylation products of polyethylene or polypropylene glycols, CQ-C22 fatty amines, fatty amides or fatty alkylolamides, etc. Additional examples are given in the standard textbook referenced above. Nonionic detergents are also understood to mean tertiary amine oxides having one alkyl chain of 8 to 18 carbon atoms and two alkyl chains of 1 to 5 carbon atoms, which may be substituted or ethoxylated, as well as sucrose esters.

Usually, mixtures of these synthetic organic detergents, whether belonging to the same class or to a different class, can be used, for example a mixture of two different anionic or nonionic synthetic detergents or a mixture of anionic and nonionic detergents. The liquid mixture should generally contain at least 1% synthetic organic detergent. The maximum amount may be as high as 50% by weight; for most practical purposes the amount will range from 5 to 40, preferably from 9 to 30 weight percent.

Preferred synthetic detergents are calcium-insensitive synthetic detergents with lime soap dispersing properties such as nonionic compounds and alkyl ether sulfates.

The weight ratio of sodium soap to synthetic organic detergent is generally 10: 1 to 1: 1 and most preferably 3: 1 to 1: 1.

c. Buffer.

8 63058

The buffer according to the invention is an alkanolamine, which is used to obtain and maintain a washing solution made of a liquid detergent mixture with a suitable pH, usually between 7 and 11, preferably between 8 and 10. The buffer can be used simultaneously for mixing certain acidic substances. to neutralize. In this case, an excess of buffer should be used so that the liquid mixture contains at least 2% by weight of free buffer. Triethanolamine is recommended as a buffer at low pH and monoisopropanolamine at high pH.

The buffer should be at least 0.1% by weight and the maximum amount is about 20% by weight. Optimum properties usually require 1 to 15% and especially 2 to 10% by weight.

The compositions of the invention may further contain a number of non-essential but often desirable optional ingredients.

The mixtures may thus contain a solvent or hydrotropic system. Such systems help to improve the physical properties of the mixture, such as brightness, viscosity and phase stability. Solvents include lower aliphatic alcohols, glycols and mono- and dialkyl glycol ethers, hydrocarbons, tetrahydrofurfuryl alcohol, etc. Hydrotropes include the sodium, potassium, ammonium or alkylolamine salts of xylene, toluene and cumene sulfonic acid, and the corresponding phosphane salts of urea, mono. Mixtures of solvents and hydrotropes can also be used.

The amount of solvent and hydrotrope is generally 0-10% by weight of the mixture.

9 63058

The composition may further contain antifoaming agents such as fatty acid alkylamides, antifoaming agents such as silicones, preservatives, antioxidants, gelling agents, perfumes, fluorescent agents, dyes, suspending agents, cermicides, bacterial binders, enzymes, enzymes substances, opacifiers, electrolyte salts such as alkali metal chlorides, sulfates, acetates and the like.

All of these other ingredients are usually used in minor amounts, for example in the order of 0.1 to 2% by weight.

As mentioned above, the liquid detergent compositions of the invention may be formulated as a non-core salt formulation, which is also recommended, but it is also possible to include core salts. Any conventional organic and / or inorganic backbone salts can be used, such as phosphate-type backbone salts, such as sodium or potassium ortho-, pyro- or tripolyphosphate, further carboxymethyloxysuccinate salts, calcin carbonate, citrates, nitrilotriacetic acid and other sodium screens, molecular sieves. If base salts are added, their amount may vary from 1 to 35%, preferably from 5 to 35% by weight of the mixture.

In this respect, it has also been found that even small amounts of aggregate in these blends give better washability to cotton at 60 ° C.

The compositions according to the invention are particularly well suited for washing fabrics, in particular polyester / cotton blended fabrics, and have been shown to have very good rinsing properties. They are isotropic liquids with excellent physical stability under freezing / thawing conditions.

The products of the invention may be prepared in any suitable manner, but it has been found advantageous to add the ingredients in such sequential order that sodium soaps are finally formed by in-situ neutralization. The recommended method thus consists of the following steps: J '

'r- F

10 63058

Add in succession: 1. fatty acids to be digested; 2. a fluorescent agent, preferably pre-dispersed in a non-ionic surfactant; 3. preservatives; 4. the remainder of the nonionic surfactant; 5. bumpers; 6. hydrotrope; 7. neutralizing agent in aqueous solution; 8. water and perfume if necessary.

The invention is further illustrated by way of example.

Example I

The following clear isotropic liquid mixture was prepared: wt% sodium oleate 17 sodium salt of coconut fatty acids 13 C 12 -C 15 primary alcohol, condensed with 7 moles of ethylene oxide 22 monoisopropanolamine 3 methylated industrial spiro 10 , 12 water remaining This liquid is an isotropic liquid with a freezing point of 3 - 4 ° C.

Example II

An isotropic liquid was prepared from the following mixture: V rb * 11 63058 pal no »? % sodium oleate 8 Sodium salt of coconut fatty acids 12 C 1-4 primary alcohol, condensed with 7 moles of ethylene oxide and propylene oxide (weight ratio EO: PO = 92: 8) 15 triethanolamine 10

monoethylene glycol 10

fluorescent + color 0.4 water rest This liquid was clear and remained stable for long storage times at temperatures between -5 and + 50 ° C.

Example III

The following isotropic liquid was prepared: wt% sodium oleate 12.5 sodium salt of coconut fatty acids 12.5 secondary linear C 1 -C 6 alcohol, condensed with 9 moles of ethylene oxide 20 C, fi-C straight chain primary alcohol, 1Rondensed with 3 moles of ethylene oxide sodium salt) 5 monoethylene glycol i 10 triethanolamine, ethanol 5 water remaining

Example IV

The following liquid containing the core salts was prepared: 't, · - Ί, -i.

12 63058% by weight sodium oleate 8 Sodium salt of coconut fatty acids 6 C, ~ -C, c alcohol, condensed with 9 moles of ethylene oxide 5

Sodium linear C 1-4 alkylbenzene sulphonate 9 tetrapotassium pyrophosphate 14 tetrasodium pyrophosphate 1 monoethanolamine 2 water remaining

Example V

The following body salt-free liquid detergents were prepared:% by weight

ABC_D

sodium oleate 22.7 17 17 10 Sodium salt of coconut fatty acids 17.3 13 13 10

Calcium, condensed with 7 moles of ethylene oxide 5-14 14 Sodium alkyl ether sulphate 9 Sodium alkyl benzene sulphonate - - 8 - Sodium C 1-4 alkyl sulphate - 6 Triethanolamine 5 5 - 5 Monoisopropanolamine - 3 3 Methylated industrial spirits 15 10 10 10 Fluorosin 2 0.2 water rest rest rest rest • ·: k> ·, 63058 13 4-> OO md OO m I · O I '· IOIO tM II o

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H H 0441 CM Π 44 44dd'HCl44 4J

oi ia o ia ov h h laiaoociia-Hia w> 4 «dduu u ddεε44Λddd · '*' * - '*} 14

Example VII 63058

The liquid of Example I was compared in Tergotometer washing machines with the product of British Patent 1,365,464 containing 33% non-ionic substance, 12% anionic substance and 10.5% triethanolamine as a basic system. Washes were performed in water with a hardness of 6 ° FH at about 25 ° C using 1 kg of 50% soiled laundry for 8 minutes, followed by rinsing three times. Washability was measured using ERTC 41 A and AS 12 specimens and fluorescence and reprecipitation were measured using non-fluorinated cotton pieces. The products were used at concentrations of 0.7, 1.0, 1.5 and 2.0 g / l.

The washability results (reflectance) were as follows: 0.7% of the product. 1 1 ...... "- ..... .....

Ex. L Vert. Ex. L Vert. Es. Vert. Eslm.l Vert.

view ERTC 41 A 67.5 68 70 70 73.5 71 74.5 71.5 AS 12 52 52 56 35.5 60 56 63 58

The product of Example 1 was superior, especially at higher doses.

. * ·· \ ·:> '

Claims (3)

15 63058 Claim An aqueous liquid detergent mixture comprising at least 10% by weight of sodium soap, at least 5% by weight of a synthetic anionic or nonionic detergent and optionally a base salt, wherein the weight ratio of soap to synthetic detergent is greater than 1, characterized in that the mixture contains (a) 10 to 40 (b) 5 to 25% by weight of the total mixture of anionic or nonionic synthetic detergent, wherein the sodium soap and 1 organic , and (c) 2-10% by weight of the total mixture of alkanolamine as a buffer buffering the pH of the wash solution to 7-11. Mixture according to Claim 1, characterized in that the buffer is triethanolamine or monoisopropanolamine. A method of preparing a liquid detergent composition according to claim 1, wherein the various components of the composition are mixed, characterized in that the soap is finally formed in situ by neutralizing the fatty acid.