GB2172910A

GB2172910A - Detergent or sheet containing a fabric conditioner

Info

Publication number: GB2172910A
Application number: GB08508128A
Authority: GB
Inventors: Andre Baeck; Alfred Busch
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 1985-03-28
Filing date: 1985-03-28
Publication date: 1986-10-01
Also published as: FI861338L; IE860832L; EP0203626A3; GB8508128D0; FI861338A7; GR860813B; DE3681344D1; GB2172910B; MX164050B; IE58609B1; FI861338A0; JPS61275393A; EP0203626A2; EP0203626B1

Abstract

Intimate mixtures of certain amines and a dispersing aid, e.g. a Bronstedt acid are useful for mixing with conventional detergent ingredients to provide through-the-wash fabric softening. Specified mixtures are lauryl-N,N-dimethylamine and lauric acid, coco-N,N-dimethylamine and coco fatty acid and myristyl-N,N-dimethylamine and citric acid. Alternatively, such mixtures are associated with a sheet suitable for addition to a wash liquor. The mixtures may also contain a clay softener.

Description

1 GB 2 172 910 A 1

SPECIFICATION

Detergent containing a fabric conditioner Technical field

The present invention relates to detergent compositions having fabric softening properties. Certain amines (in intimate mixture with a dispersing aid) in the compositions provide through-the-wash softness and anti-static benefits. Detergent compositions in spray-dried form containing said amines are disclosed. Preferred compositions also contain a smectite clay for additional softening benefits.

Background

The use of softeners to treat fabrics subsequent to a washing operation is a well known laundering practice. Fabric softeners are, in the main, cationic materials which are incompatible with anionic detersive surfactants used in most fabric washing compositions. For that reason, the softening operation is generally carried out in the laundry rinse bath after the surfactant has been removed from the washing machine. This 15 entails additional work for the user.

Formulators of fabric laundering compositions have long sought means whereby the fabric washing and softening could be done concurrently. Methods employing clay softeners, mixtures of clay and various amine materials, and the like, are described in the following patents: German 29/64114.3,28/57163.3, 24/39541.3, 23/34899.4 and EPO 80200570.2, 80200877.1 and 80201015.7.

The use of mixtures of amines and soaps (salts of fatty acids) as throughthe-wash softeners is disclosed in U.K. patent 1514 276. The amines of this reference are selected on the basis of their having an isoelectric point of from 8.3 to 9.8, i.e. such that they have no positive charge during the wash cycle, and become positively charged during the rinse cycle.

The present invention employs a certain class of amines, intimately mixed with a dispersing aid, in an 25 otherwise conventional detergent composition matrix, and optionally clay, to provide cleaning and, concurrently, softening.

Summary of the Invention

The compositions herein may be described succinctly as detergent compositions (preferably, granular) 30 which may contain conventional detergent ingredients such as detersive surfactants (including anionics), detergency buildings, optical brighteners, detersive enzymes, fabric bleaches, and the like, all at conventional levels, as well as clay fabric softeners (preferably, smectite clays), said compositions being characterized in that they contain at least 0.1 % (preferably 1.0% to 20%) of an amine having an isoelectric point of at least 9.5, preferably those of the formula R,R2R3N, wherein R, is C9 to C20 hydrocarbyl and R2 and 35 R3 are each Cl to C4 hydrocarbyl, C2 to C10 alkoxylated hydrocarbyl or hydrogen, the amine being in intimate mixture with a dispersing aid.

Detailed Description of the Invention 40 As noted hereinafter, the compositions of this invention comprise, in major part, conventional ingredients 40 that are quite familiar to formulators of granular detergent compositions. Surprisingly, the amines used herein are entirely compatible with such conventional detergent ingredients, even anionic surfactants.

Amine The amines suitable forthe compositions herein are selected so that they have an isoelectric point in excess of 9.5, preferably in excess of 10.0.

Examples are amines having general formula R1R2R3N, wherein R, is C8 to C20 hydrocarby], preferably C13 to C20 alky], more preferably C10 to C14 alkyl, and most preferably C12 alkyl or a mixture Of C12 and C14 alky].

R2 and R3 are each, independently, Cl to C10, hydrocarby], or hydrogen. Examples of sutable hydrocarbyl 50 radicals are Cl to C4 alkyl or hydroxyalky], and C2 to C10 alkoxylated alkyl, in particular ethoxylated alkyl radicals. Amines wherein R2 and R3 are identical Cl to C4 alkyl, especially methyl, are preferred.

Prior to incorporation into the detergent matrix, the amines are intimately mixed with a dispersing aid. The dispersing aid can be any of a number of such materials. Specific examples include nonionic surfactants, and emulsifiers, like those used in the food industry. Examples of the latter include glycerol esters, e.g. lecithin. 55 It has been found that a specific class of compounds, most of which are not generally considered to be dispersing aids, are particularly suitable to be used as dispersing aids in combination with the amines defined herein. This class of compounds consists of the Bronstedt acids havi-ng a pKa value of not greater than 6, preferably not greater than 5.

Examples of such acids include inorganic acids, like HF, HCl, HBr, H2S04, HN03, HNaS04, H2S03, HNaS03, 60 phosphoric acid esters, like W(CH2CH20),PO(Offi2 and (WO(CH2CH2OW2POOH, wherein R' is a C3-C20 hydrocarbyl, and m has a value in the range of from 1 to 6; organic acids, like carboxylic acids, polycarboxylic acids, hydroxycarboxy acids, hydroxypolycarboxy acids, aminocarboxy acids, phosphoric acids, polymeric carboxy acids, alkyl-ether carboxy acids, and alkylsulforic acids. Particularly suitable for use as dispersing aids herin are carboxylic acids of the formula RCOOH, wherein R is hydrogen or Cl to C15 alkyl. 65 2 GB 2172910 A 2 Preferred acids are formic acid (R is hydrogen) and lauric acid (R is C11H23 n-alkyl).

Although not intended to be limited by theory, a possible mechanism by which Bronstedt acids act as dispersing aids could be as follows. The acids protonate a portion of the amine. The protonated amine, in turn, acts as a dispersing aid forthe remaining unprotonated amine. This mechanism suggests that protonated aminesperse could be used as dispersing aids, instead, or in combination with the Bronstedt acids.

The criticality of the high isoelectric point of the amines (at least 9.5, preferably 10.0 or higher) suggest thit it is important that, if protonation indeed takes place, the amines remain protonated during the wash cycle of a laundry program. On the other hand, it is critical that the dispersing aid be intimately mixed with the amine.

Simply allowing the amines to be contacted by the dispersing aid in the wash liquor apparently is not 10 sufficient to obtain the superior softening performance.

In general terms, the amineldispersing aid mixtures which are key to this invention are prepared separately from the balance of the composition and then added to the conventional detergent ingredients. If the dispersing aid is a Bronstedt acid, this can most conveniently be done by preparing a melt (preferably 1: 1 mole ratio) of the acid and the amine and maintaining under continuous mixing the melt stage for about ten 15 minutes whereby the complex forms.

If the detergent matrix is in granular form, the amineldispersing aid melt can be sprayed onto the granules. Alternately, the melt can be allowed to solidify, then, rduced to the desired particle size in, e.g. a colloid mill. and dry-mixed with the detergent granules.

If the detergent matrix is a liquid, the amineldispersing aid melt can be dispersed into the liquid detergent 20 mixture, or be allowed to solidify, milled to the desired particle size (typically smaller than used in conjunction with granules) and then dispersed into the liquid.

The amineldispersing aid can also be deposited on a sheet, e.g. by coating a sheet with the melt. The sheets may be added to the wash liquor during the wash cycle of a laundering process. The sheets may further contain conventional detergent ingredients. Sheets of the type as has been disclosed for use as a 25 delivery system for detergent ingredients are generally suitable for use herein.

If the dispersing aid is an acid, the molar ratio amine: acid preferably is about 1A, but good fabric softening results can also be obtained by mixing the amine with a sub- stoichiometric amount of acid. For good results, the acid: amine ratio should be at least 1: 10, preferably at least 1:5.

The amineldispersing aid mixtures are typically used herein at levels of at least 0.1 %, typically at levels of 30 0.5% to 20%, most preferably from 1 % to 10% of the detergent compositions, especially when softener clay is present.

Softener Clay The protonated amine is preferred, but not limited, for use in combination with a detergent-compatible 35 clay softener. Such clay softeners are well known in the detergency patent literature and are in broad commercial use, both in Europe and in the United States. Included among siuch clay softeners are various heat-treated kaolines and various multi-layer smectites. Preferred clay softeners are smectite softener clays that are described in German patent document 2 334 899 and in U.K. patent 1400 898, which can be referred to for details. Softener clays are used in the preferred compositions at levels of at least 1%, generally 1-20%, 40 preferably 2-7%.

Datersive Surfactants The compositions of this invention will typically contain organic surface- active agents ("surfactants") to provide the usual cleaning benefits associated with the use of such materials.

Detersive surfactants useful herein include well known synthetic anionic, nonionic, amphoteric and zwitterionic surfactants. Typical of these are the alkylbenzene sulfonates, alkyl- and alkylether sulfates, paraffin sulfonates, olefin sulfonates, alkoxylated (especially ethoxylated) alcohols and alkyl phenols, amine oxides, et-sulfonates of fatty acids and of fatty acid esters, and the like, which are well known from the detergency art. In general, such detersive surfactants contain an akyl group in the Cg-C18 range; the anionic 50 detersive surfactants can be used in the form of their sodium, potassium or tri-ethanolammonium salts; the nonionics generally contain from about 5 to about 17 ethylene oxide groups. U.S. Patents 4.111.855 and 3.995.669 contain detailed listings of such typical detersive surfactants. Cl,-C16 alkyl benzene sulfonates, C17Cla paraffin sulfonates and alkyl sulfates, and the ethoxylated alcohols and alkyl phenols are especially preferred in the compositions of the present type.

Also useful herein as the surfactant are the water-soluble soaps, e.g. the common sodium and potassium coconut or tallow soaps well known in the art.

The surfactant component can comprise as little as 1 % of the compositions herein, but preferably the compositions will contain 5% to 40%, preferably 10% to 30%, of surfactant. Mixtures of the ethoxylated nonionics with anionics such as the alkyl benzene sulfonates, alkyl sulfates and paraffin sulfonates are preferred forthrough-the-wash cleansing of a broad spectrum of soils and stains from fabrics.

Detersive Adjuncts - The compositions herein can contain other ingredients which aid in their cleaning performance. For example, it is highly preferred that detergent compositions contain a detergent builder and/or metal ion sequestrant. Compounds classifiable and well known in the art as detergent builders include the nitrilotriacetates, polycarboxylates, citrates, water-soluble phosphates such as tri-polyphosphate 65 3 GB 2 172 910 A 3 and sodium ortho- and pyro-phosphates, silicates, and mixtures thereof. Metal ion sequestrants include all of the above, plus materials like ethyl enedia m i netetraacetate, the amino-polyphosphonates (DEQUEST) and a wide variety of other poly-functional organic acids and salts too numerous to mention in detail here. See U.S. Patent 3.579.454 for typical examples of the use of such materials in various cleaning compositions. In general, the builder/ sequestrant will comprise about 0.5% to 45% of the composition. The 1-10 micron size zeolite (e.g. zeolite A) builders disclosed in German patent 2.422.655 are especially preferred for use in low phosphate compositions which contain the amine fatty acid complex.

The laundry compositions herein also preferably contain enzymes to enhance their through-the-wash cleaning performance on a variety of soils and stains. Arnylase, protease and lipase enzymes suitable for use in detergents are well known in the art and in commercially available liquid and granular detergents. Commercial detersive enzymes (preferably a mixture of arnylase and protease) are typically used at levels of 0. 001% to 2%, and higher, in the present compositions.

Moreover, the compositions herein can contain, in addition to ingredients already mentioned, various other optional ingredients typically used in commercial products to provide aesthetic or additional product performance benefits. Typical ingredients include pH regulants, perfumes, dyes, bleach, optical brighteners, 15 soil suspending agents, hydrotropes and gel-control agents, freeze-thaw stabilizers, bactericides, preservatives, suds control agents, bleach activators and the like.

In a through-the-wash mode, the compositions are typically used at a concentration of at least 500 ppm, preferably 0.10% to 1.5%, in an aqueous laundry bath at pH 7-11, preferably at pH 9-11, to launder fabrics.

The laundering can be carried out over the range from 50C to the boil, with excellent results.

Industrial Application The following examples are typical of the preferred compositions of this invention containing excellent smectite softener clays, but are not intended to limit the scope of the invention.

Example 1

Lauricacidand lauryl N,N-dimethylarnine(lA mole ratio) are admixed, melted inajacketed batch,and maintained under continuous mixing asa melt for about 10 minutes (excess heating may cause yellowing).

A detergent composition is formulated as follows:

Ingredients Percent Cll-12 alkyl benzene sulfonate (Na) 6.2 Tallow alcohol ethoxylate (E01 1) 1.0 Sodium perborate (41-120) 20.0 35 Sodium tri polyp hosphate 24.0 Sodium sulfate 22.0 Sodium silicate 8.0 Smectite clay 2.4 Lau ryi-N, N-d i methyl amine/lauric acid mix 3.8 40 Carboxymethyl cellulose 0.4 Polyacrylate (soil suspender) 1.7 Enzymes 0.5 Optical brightener 0.23 Sulphonated zinc phthalocyanine 25 ppm 45 EDTA 0.2 Perfume/copper saits/minors 0.5 Moisture to 100 so natural smectite; ion exchange capacity above 50 meq/100 g clay U.S. patent 3 927 967 The detergent matrix is prepared as a crutcher mix and spray-dried into granules in standard fashion. The amine/lauric acid mixture is sprayed onto the granules, as well as the perfume. Enzymes are dry-mixed.

The composition of Example 1 is free-flowing and exhibits excellent through-the-wash fabric softening 55 performance when fabrics washed therewith are line-dried.

4 GB 2 172 910 A 4 Example 11

A nil-P spray-dried detergent formulation is as follows:

Ingredient Zeolite A (1-10 micron) Sodium nitrilotriacetate Smectite Clay Amineiacid mixture Cll-12 alkyl benzene sulfonate (Na) Tallow ethoxylate (EO 9-11) Sodium perborate (41-120) Sodium silicate Carboxymethyl cellulose Sodium sulfate Enzymes (1: 1 amylaselprotease) Optical brightener Water, minors Percent 26.0 5.0 3.0 2.5 6.5 1.5 20.0 8.0 1.0 20.0 1.5 0.5 to 100 as gelwhite GP (TM); ion exchange capacity: 70 Meq/100 g.

prepared separately from mixed coconut fatty acids and mixed coconut-N,Ndimethyl amine (1:1 mole ratio), spray-dried granules as a dry powder.

In an optional mode, the composition of Example 11 may be modified by removing the clay and replacing it 25 with an equivalent amount (with regards to softening performance) of aminelacid mixture. In another alternate composition, the clay is replaced with ditallowmethylamine.

Example 111

The following composition is prepared as in Example 1.

Sodium linear dodecyl benzene sulphonate Dodecyl-tri methyl ammonium chloride Tallow alcohol ethoxylate (EO 11) Sodium perborate (41-120) Sodium tripolyphosphate Sodium suffate Sodium silicate Montmorillonite clay (agglomerates) M ethyl-di hydrogenated tallow amine N,N-Dimethylcoco aminelcoco fatty acid 0:1 mixture) Enzyme granules Sodium carboxymethyl cellulose Copolymer acrylic acid- maleic acid (70:30 ratio) 40.000-70.000 MW Optical brightener Sulphonated zinc phthalocyanine EDTIVIPA(1) TAED (2) Silicalsilicone suds suppressor Perfume/copper salts/minors Moisture mixture sprayed on detergent granules dry-mixed (1) Ethylenediaminetetramethylene phosphonic acid (2) Tetraacetyl ethylenediamine 6.0 1.6 1.0 20.0 24.0 13.0 7.5 6.0 3.0 5.0 0.6 0.3 2.00 0.23 25pprn 0.3 2.5 0.2 0.5 to 100 GB 2 172 910 A 5 Example IV

Sodium linear dodecyl benzene sulphonate 5.3 Sodium tallow alkyl sulphate 2.3 Dodecyl-di methyl ammonium-N-oxide 0.4 5 Tallow alcohol ethoxylate (EO 11) 1.0 Sodium perborate (41120) 15.0 Sodium tripoly phosphate 8.0 Zeolite Type A (11-10 micron) 15.0 Sodium sulfate 12.0 10 Sodium silicate 3.0 Sodium carbonate 10.0 Smectite clay 5.0 N,N-Dimethyl-myristyl aminelcitric acid 7.0 (11:1 mixture) 15 Enzyme granules (Alcalase) 0.6 Sodium carboxymethyl cellulose 0.3 Copolymer acrylic acid-maleic acid 1.5 (70:30) MW 5.000-20.000 Polyacrylic acid (1.000-15.000) 1.5 20 EDTMPA1) 0.3 TAED 2) 0.5 lso-nonanoyi-oxy-benzene-sulphonate 2.5 Sulphonated Zinc phthalocyanine 40 ppm Paraffin oil/was 0.4 25 Perfumelcopper salts/minors 0.5 Moisture to 100 1) Ethylenediamine -N,N,N',N'-tetramethylene phosphonic acid 30 2) Tetraacetyl ethylenediamine Dry-mixed Preparation of the dimethyl myristyl aminelcitric acid mixture Ciric acid is dissolved in methanol (+/- 30'C). After the addition of the amine, the.mixture is stirred for about 15 minutes. Then the methanol is evaporated (e.g. by heating) and the solid residue (mixture of citric 35 acid/dimethyl myristyl amine) is subsequently dried and ground to the desired particle size.

This method for preparing the mixture of amine/dispersing aid is suitable when the melting point of the dispersing aid is too high.

Claims

1. A detergent composition comprising detersive surfactant, builders, and conventional detersive ingredients, characterized in that it contains at least 0.1 %of an intimate mixture of an amine having an iso-electric point of at least 8.5, and a dispersing aid.

2. A composition according to claim 1 wherein the amine has an isoelectric point of at least 10.0. 45

3. A composition according to claim 1 or 2 wherein the amine has the formula R1R2R3N wherein R, is C8 to C20 hydrocarby], and R2 and R3 are each Cl to C4 hydrocarbyl, C2 to Clo alkoxylated hydrocarby], or hydrogen.

4. A composition according to any of claims 1 to 3, wherein the dispersing aid is a Bronstedt acid having a pKa value not greater than 6, preferably not greater than 5.

5. A composition according to any of the preceding claims wherein the dispersing acid is a carboxylic acid of the formula R COOH, wherein R is hydrogen or a Cl to C15 hydrocarbyl, preferably formic acid or lauric acid.

6. A composition according to any of the preceding claims wherein the amine and the dispersing aid are present in an (amine): (dispersing aid) molar ratio in the range as from 10: 1 to 1:5.

7. A composition according to any of the preceding claims which contains from 0.5% to 20% of the amine/dispersing aid mixture.

8. A composition according to any of the preceding claims wherein the amine/dispersing aid is prepared by admixing same at a temperature above the melting point of both the amine and the dispersing aid.

9. A composition according to any of the preceding claims which additionally contains a clay softener, 60 preferably a smectite clay.

10. A composition according to any of the foregoing claims which comprises:

a) from 1%to 10% of an intimate mixture of lauryl-N,N-dimethyl amine and lauricbcid in a molar ratio as from 1:0.9to 1:1.11; b) from 2%to 7% of a smectite clay softener; 6 GB 2172910 A 6 c) the balance comprising conventional detergent ingredients at conventional levels; said composition being in the form of spray-dried granules.

11. A sheet suitable for addition to awash liquor, having dispersibly associated therewith a fabric softening amount of the amineldispersing aid mixturez of any of the preceding claims.

Printed in the UK for HMSO, D8818935, 8186, 7102. Pubjished by The Patent Office, 25 Southampton Buildings, London, WC2A IlAY, from which copies may be obtained.