FI96776C - Detergent compositions containing organic surfactant and smectite-type clay - Google Patents

Description

96776

Detergent compositions containing an organic surfactant and a smectite-type clay

The present invention relates to detergent compositions containing 5 to 40% of an organic surfactant and 1 to 30% of a smectite-type clay as a fabric softening ingredient, as well as a softening-enhancing amount of a polymeric clay flocculant.

GB Patent 1,400,898 discloses detergent compositions containing smectite-type clay as a fabric softener. Any smectite-type clay with a cation exchange capacity of at least 50 meq / 100 g is considered suitable. Gelwhite GP and Volclay BC, both of the sodium montmorillonite clay type-15, are shown to be advantageous due to the color and cation exchange capacity.

It is currently well understood in the detergent industry that clays of the type disclosed in GB Patent 1,400,898 provide significant fabric softening benefits in laundry detergent. It is equally well understood that the deposition of these clays on the fabrics during the washing process is far from complete; in fact, under typical washing conditions used in Europe, less than half of the available clay precipitates on the fabrics as the remainder is washed away with the washing solution during the subsequent rinsing steps. In addition, the softening effect resulting from clay precipitation is influenced by factors that are not fully understood.

It is therefore an object of the present invention to provide detergent compositions containing fabric softening clay from which clay particles precipitate more effectively on fabrics during the washing process. Another object of the present invention is to provide detergent compositions from which clay particles are effectively precipitated regardless of the structural material system used.

96776 2 The present invention relates to detergent compositions containing 5 to 40% of an organic surfactant and 1 to 30% of a smectite-type clay as a fabric softening ingredient, which compositions are characterized in that they contain a softening amount of 0.005 to 20% by weight. -% by weight of a smectite-type clay, a polymeric clay flocculant having a weight average molecular weight of 100,000 to 10,000,000 and which is a polymer or copolymer derived from ethylene oxide, ac-10-amylamide or ethyleneimine monomers or mixtures thereof.

The detergent compositions of the present invention include conventional detersive surfactants, conventional detergent builders, and optionally other conventional detergent ingredients.

The percentages reported herein are by weight of detergent compositions unless otherwise indicated.

It has been found that polymeric clay flocculants promote the deposition of fabric softening clays on fabrics. The amount of clay flocculant used in the detergent compositions of the present invention should be such that the deposition of emollient clay on the fabrics is improved but remains substantially constant. The amount of the particular polymeric clay flocculant required in the detergent composition can be readily determined in a simple planar study using the clay precipitation test described below.

Clay Precipitation Test Various amounts of the polymeric clay flocculant to be tested are added to samples of a detergent composition containing 5% fabric softening clay. Fro tea towel drops are washed in 1-35% solutions of these detergent samples. The patches are rinsed and dried with a clothesline. The clay in the patches is stained with methylene blue. The hue is compared to that obtained with a detergent sample to which no polymeric clay flocculant has been added.

5 Each amount of polymeric clay flocculant that results in a color tone that is clearly darker than that obtained without the use of a clay flocculant provides the desired softening effect. This amount is referred to herein as the "softening amount" of the clay flocculant.

Relatively large amounts of clay flocculant result in spotted or even reduced clay precipitation. Stained patches show blue spots and not a substantially uniform color-15. These relatively high amounts of clay flocculant do not result in the desired increase in softness and are therefore not considered to be softeners.

The amount of clay flocculant, expressed as 20% by weight of smectite-type clay, is preferably 0.05 to 20% by weight of clay in the compositions according to the invention, in the case of clay flocculants having a weight average molecular weight of between 150,000 and 800,000, and between 0.005 to 2% by weight of clay with molecular weights between 800,000 and 5 million.

Clay flocculants are not commonly used in detergent compositions. In contrast, there is a tendency to use clay dispersants to help remove clay stains from fabrics. However, such materials are well known in other industries, such as oil drilling and ore flotation in metallurgy. Most of these materials are relatively long chain polymers and copolymers derived from monomers such as ethylene oxide, acrylic amide, acrylic acid, dimethylaminoethyl methacrylate, 4,967,776 vinyl alcohol, vinylpyrrolidone and ethyleneimine. Gums such as guar gum are also suitable.

Polymers of ethylene oxide and acrylamide are preferred. In order to interact with the clay particles, the polymers must be relatively long-chain, i. they must have a weight-average molecular weight of at least 100,000. Due to their sufficient water solubility, the weight-average molecular weight of the polymers must not exceed 10 million. Most preferred are polymers having a weight-10 average molecular weight of between 150,000 and 5 million.

Clay that softens the fabric

Smectite-type clays are widely used as fabric softeners in detergent compositions. 15 Most of these clays have a cation exchange capacity of at least 50 meq / 100 g.

Montmorillonite clays are commonly used for this purpose. However, it appears that certain hectorite clays provide a better fabric softening effect than the more commonly used montmorillonites. Hectorites with this better fabric softening effect are hectorites of natural origin.

The cation exchange capacity of the compound is a well-known parameter and can be determined by well-established analytical methods. See, e.g., H. van Olphen, "Clay Colloid Chemistry", Interscience Publishers, 1963, and related references therein.

Other detergent components

Detergent Surfactants - The compositions of this invention contain organic surfactants to provide the usual detergent benefits associated with the use of such materials.

Cleansing surfactants useful herein include well known synthetic anionic, non-ionizable, amphoteric and dipolar surfactants. Typical of these are alkyl benzene sulfonates, alkyl and alkyl ether sulphates, paraffin sulphonates, olefin sulphonates, alkoxylated (especially ethoxylated) alcohols and alkylphenols, amine oxides, fatty acid and fatty acid esters of these, alpha-fatty acid esters Such detersive surfactants generally contain an alkyl group of the order of 10 C99. anionic detersive surfactants can be used in the form of their sodium, potassium or triethanolammonium salts. Nonionizable materials generally contain from about 5 to about 17 ethylene oxide groups. U.S. Patent 3,995,669 contains detailed lists of such typical detersive surfactants. C 1-6 alkyl benzene sulfonates, C 12, 8 paraffin sulfonates and alkyl sulfates, as well as ethoxylated alcohols and alkyl phenols are particularly preferred in compositions of the present type.

Water-soluble soaps are also useful as surfactants, e.g., sodium and potassium coconut or tallow soaps well known in the art.

The surfactant component may be as little as 1% of the compositions in question, but the compositions preferably contain from 5 to 40%, more preferably from 10 to 30% of surfactant. Mixtures of ethoxylated, non-ionizable agents with anionic agents such as alkylbenzenesulfonates, alkyl sulfates, and paraffin sulfonates are preferred for cleaning broad-spectrum dirt and stains by washing fabrics. It has previously been reported that large amounts of non-ionizable surfactants (i.e., greater than 4%) in clay-containing detergent compositions negatively affect the softening ability of the clay. It has now surprisingly been found that such 6 96776 negative interactions do not occur if the clay flocculant of the present invention is also present.

Detergent Auxiliaries - This composition may contain other ingredients that aid in cleaning performance. Thus, for example, it is highly preferred that the detergent compositions used in the wash contain a detergent builder and / or a metal ion sequestrant. Compounds that can be classified as detergent builders and are well known in the art include nitrilotriacetates, polycarboxylates, citrates, carbonates, zeolites, water-soluble phosphates such as tripolyphosphate and sodium ortho- and pyrophosphates, silicates thereof, and silicates thereof. Metal ion sequestrants include all of the above, as well as substances such as ethylenediaminetetraacetate, aminopolyphosphonates (DEQUEST), and a wide variety of other polyfunctional organic acids and salts, which are too numerous to describe in detail herein. U.S. Patent 20 3,579,454 provides typical examples of the use of such agents in various detergent compositions. The builder / sequestrant is generally present in about 0.5 to 45% of the composition. The zeolite (e.g. zeolite A) building blocks with a particle size of 1 to 10 microns disclosed in German Patent Patent 2,422,655 are particularly preferred for use in low phosphate compositions.

Particularly suitable phosphate-free building materials are ether carboxylate mixtures containing from 30 a) 1 to 99% of a tartrate monosuccinate component having the structure HOCH - CH - O - CH - CH »

Il II

35 COOX COOX COOX COOX

ti 7 9 6776 wherein X is H or a salt-forming cation; and b) 1-99% by weight +% of a tartrate disuccinate component having the structure: CH_-CH-O-CH-CH-O-CH-CH,

I l II II

COOX COOX COOX COOX COOX COOX

wherein X is H or a salt-forming cation.

Systems of this type are described in U.S. Patent 4,663,071 to Bush et al., Issued May 5, 1987.

Typical detergent compositions contain 5-35% of this builder system.

The detergent compositions of the invention preferably also contain enzymes to improve their ability to clean various soils and stains during washing. Amylase and protease enzymes suitable for use in detergents are well known in the art and are commercially available in liquid and granular detergents. Commercially available cleaning enzymes (preferably a mixture of amylase and protease) are typically used in 0.001 to 2% or more of the compositions of the invention. Cleansing cellulase enzymes provide both cleansing and softening benefits, especially for cotton! fabrics. Such enzymes are highly desirable in the detergent compositions of this invention.

The compositions in question may contain other ingredients which aid in their cleaning performance. Thus, for example, the compositions in question may preferably contain a bleaching agent, in particular a peroxyacid bleaching agent. In the context of the present invention, the term peroxyacid bleaching includes both peroxyacids per se and systems capable of producing peroxyacids in situ.

8 96776

Peroxyacids per se are intended to include their alkali and alkaline earth metal salts. Generally, peroxyacids and diperoxyacids are used; examples are diperoxydodecanoic acid (DPDA) or peroxyphthalic acid.

5 Systems capable of producing peracids in situ consist of peroxygen bleach and its Akti catalyst.

Peroxygen bleaches are those capable of producing hydrogen peroxide in aqueous solution: these compounds are well known in the art and include hydrogen peroxide, alkali metal peroxides, organic peroxide bleaches such as urea peroxide, inorganic persalt bleaches such as alkali metal perborates, caliperates, percarbons, percarbons, percarbons .

Preferred are commercially available sodium perborate in the form of mono- and tetrahydrates, sodium carbonate peroxyhydrate, sodium pyrophosphate peroxyhydrate and urea peroxyhydrate.

The hydrogen peroxide released reacts with the bleach activator to form a peroxyacid bleach. Classes of bleach activators include esters, imides, imidazoles, oximes, and carbonates. Preferred agents in these classes include methyl-o-acetoxybenzoates; sodium p-acetoxybenzenesulfonates such as sodium 4-nonanoyloxybenzenesulfonate, sodium 4-octanoyloxybenzenesulfonate and sodium 4-decanoyloxybenzenesulfonate; biofenoli-A diacetate; tetra acetyl ethylene diamine; tetraacetylhexamethylenediamine-30 amine and tetraacetylmethylenediamine.

Other particularly preferred peroxygen bleach activators disclosed in U.S. Patents 4,483,778 and 4,539,130 include alpha-substituted alkyl or alkenyl esters such as sodium 4- (2-chloroctanoyl-35-yloxy) benzenesulfonate and sodium 4- (3) , 5,5-trimethyls 96776 9 hexaneoyloxy) benzenesulfonate. Also suitable peroxyacids are the activators of peroxygen bleaches described in EP patent application 0 116 571, i. compounds of the general type 5 RXAOOH and RXAL, wherein R is a hydrocarbyl group, X is a heteroatom, A is a carbonyl bridging group and L is a leaving group, especially oxybenzenesulfonate.

Other highly desirable detergent ingredients for use in the detergent compositions of the present invention include quaternary ammonium compounds of the formula R 4 R 11 R 6 R 7 N + X, wherein R 1 is alkyl of 8 to 20, preferably 12 to 18 carbon atoms, R 5 is alkyl of 1 - 10 carbon atoms, and R 6 and R 7 are each C 1-4 alkyl, preferably methyl; X 'is an anion, e.g. chloride. Examples of such quaternary ammonium compounds are C 12-12 alkyltrimethylammonium chloride and coconut alkyltrimethylammonium methosulfate. Quaternary ammonium compounds can be used in amounts of between 0.5 and 5%, preferably between 1 and 3%.

20 Other emollient ingredients

The detergent compositions of the present invention may further contain other emollient ingredients in addition to the clay material. Suitable examples are amines of the formula R 1, R 2 R 3 N, wherein R 1 is C 1 -C 10 hydrocarbyl, R 2 is C 20-20 hydrocarbyl and R 3 is C 1-10 hydrocarbyl or hydrogen. One preferred amine of this type is ditalimethylamine.

The emollient amine is preferably present in complex with a fatty acid of formula RCOOH, wherein R is C 9-20 alkyl or alkenyl. It is desirable that the amine / fat-30 acid complex be present in very small particles with a particle size of the order of e.g. 0.1 to 20 micrometers. These amine / fatty acid complexes are described in more detail in EP patent application 0 133 804. Compositions containing 1 to 10% of amine are preferred.

96776 10

Also suitable are complexes of the amines described above and phosphate esters of the formula

5 0 O

Il II

Rq0— P - OH and HO- P - OH

8 I I

Wherein R 8 and R 8 are C 1-20 alkyl groups or ethoxylated alkyl groups of the general formula alkyl- (OCH 2 CH 2) y in which the alkyl substituent has 1 to 20 C atoms, preferably 8 to 16 C atoms, and Y is an integer from 1 to 15, preferably from 2 to 10, most preferably from 2 to 5. Amine / phosphate ester complexes of this type are described in more detail in EP patent application 0 168 889.

Further examples of possible emollients include emollient amides of formula R 10 R 11 NCC 12 wherein R 10 and R 11 are independently selected from the group consisting of C 1-22 alkyl, alkenyl, hydroxyalkyl, aryl and alkylaryl groups; R 12 is hydrogen or a C 1-6 alkyl or alkenyl, aryl or alkylaryl group, or a group -O-R 13, wherein R 11 is a C 1-22 alkyl, alkenyl, aryl or alkylaryl group. Preferred examples of these amides are dithiacetamide and ditalibenzamide. Good results are obtained if amides are present in the composition in admixture with a fatty acid or phosphate ester, as described above in connection with emollient amines.

Amides are present in the composition in an amount of 1-10% by weight.

Also suitable emollient ingredients are the amines disclosed in GB Patent Application 2,173,827, in particular the substituted cyclic amines disclosed therein. Suitable are imidazolines of the general formula 1- (higher alkyl) amido-35 (lower alkyl) -2- (higher alkyl) imidazoline, in which the higher alkyl is alkyl of 12 to 22 carbon atoms and the lower alkyl is alkyl of 1 - 4 carbon atoms.

96776 11

A preferred cyclic amine is 1-thallamidoethyl-2-thalimidazoline. Preferred compositions contain 1 to 10% of a substituted cyclic amine.

The amine and amide plasticizers may be added as a dry powder to the detergent granules, or may be sprayed onto the detergent granules or carrier either in molten form or in solution. An example of a suitable carrier is perborate monohydrate.

In addition to the ingredients already mentioned, the compositions according to the invention may contain various other possible substances which are typically used in commercial products in order to achieve aesthetic or in addition to improving the effectiveness of the product. Typical ingredients include pH adjusting agents, perfumes, colorants, bleaching agents, optical brighteners, dirt suspending agents, hydrotropes and gelling agents, freezing and thawing agents, bactericides, preservatives, foaming agents, bleaching agents, bleaching agents, .

In the wash treatment, the compositions are typically used at a concentration of at least 400 parts per million, preferably 0.05 to 1.5% in a wash water solution at pH 7-9 for washing fabrics. Washing can be performed with excellent results at a temperature of 5 ° C to boiling point.

Industrial application

The detergent compositions of the present invention may be formulated as granular or liquid detergents. It has been found that clays with high swelling capacity can be easily incorporated into a liquid detergent composition while maintaining phase stability.

To prepare liquid detergent compositions, the polymeric clay flocculant can be mixed with the other detergent ingredients while stirring.

96776 12

To prepare a granular detergent composition, a polymeric clay flocculant can be added in a variety of ways. It can be added to the mixture in the stirrer before spray drying; or it can be sprayed onto the granular detergent when dissolved in water or an organic solvent; or it can be dry blended in the form of particles with a granular detergent. The release of the flocculant can be controlled by incorporating it into a small piece or by microencapsulating it in a suitable microencapsulation agent.

In a preferred embodiment, agglomerates are formed from the fabric softening clay and the clay flocculant. These agglomerates are dry blended with the granular detergent composition.

The chemical stability of the clay flocculant is improved by the addition of small amounts (typically 0.05 to 1% by weight of the detergent composition) of the chelating agent. A preferred chelating agent is ethylenediamine nitetramethylenephosphonic acid.

The clay flocculant may also be included in the detergent additive, e.g. in the form of a sheet or bag, which is added to the washing solution on top of a conventional detergent composition. The laundry additive preferably also contains fabric softening clay and / or the other fabric softeners described above, so that it can be used in connection with detergent compositions which do not themselves contain such clay or other such softening ingredients.

In a very specific embodiment, the polymeric clay flocculant is formed into a water-soluble film. The film is formed into a bag filled with a simple dose of a clay-containing detergent composition. In use, the bag dissolves and releases the detergent composition. The dissolved polymer interacts with the emollient clay to improve its deposition on fabrics. Ethylene oxide polymers are particularly suitable for use in this embodiment of the invention.

The fabric softening clay and the softening amount of polymeric clay flocculant may also be included in the fabric softener composition to be added to the rinse. Other emollients, such as quaternary ammonium compounds, may also be present.

Examples I to VIII

The following granular detergent compositions are prepared: 14 96776

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Claims (13)

96776 Patented suction A detergent composition comprising 5 to 40% organic surfactant and 1 to 30% smectite-type clay as a fabric softening component, characterized in that it contains a softening amount of 0.005 to 20% by weight. by weight of a smectite-type clay, a polymeric clay flocculant having a weight average molecular weight of 100,000 to 10,000,000 and a polymer or copolymer derived from ethylene oxide, acrylamide or ethyleneimine monomers or mixtures thereof. Detergent composition according to Claim 1, characterized in that the polymer is derived from ethylene oxide, acrylamide or ethyleneimine monomers. Detergent composition according to Claim 1 or 2, characterized in that the polymeric clay flocculant has a weight-average molecular weight of 20,150,000 to 5,000,000. Detergent composition according to one of Claims 1 to 3, characterized in that the clay flocculant has a molecular weight of 150,000 to 800,000 and is present in an amount of 0.05 to 20% by weight, based on the amount of smectite-type clay. Detergent composition according to one of Claims 1 to 3, characterized in that the clay flocculant has a molecular weight of between 800,000 and 5,000,000 and is present in an amount of 0.005 to 2% by weight of the amount of smectite-type clay. Washing composition according to one of Claims 1 to 5, characterized in that it further contains 0.5 to 5% of a quaternary ammonium compound of the formula R 4 R 5 R 6 R 7 N + X ', in which R 1 is alkyl of 10 to 35 carbon atoms, R 5 , R 1 and R 7 are each C 1-4 alkyl and X 'is an anion. Il 17 96776 Washing composition according to one of Claims 1 to 6, characterized in that it further contains 1 to 10% of an amide of the formula R 10 R 11, NCOR 2, in which R 10 and R 11 are, independently of one another, alkenyl, hydroxyalkyl, aryl or alkylaryl groups, R 12 is hydrogen or a C 1-22 alkyl or alkenyl, aryl or alkylaryl group or is O-R 3, wherein R 13 is C 1-4 alkyl; an alkyl or alkenyl, aryl or alkylaryl group. Detergent composition according to one of Claims 1 to 7, characterized in that it further contains 1 to 10% of an imidazoline of the formula 1- (higher alkyl) amido (lower alkyl) -2- (higher alkyl) imidazoline , wherein the higher alkyl has 12 to 22 carbon atoms and the lower alkyl has 1 to 4 carbon atoms. Detergent composition according to any one of claims 1 to 8, characterized in that it further contains 5 to 35% of a building material system comprising a) 1 to 99% of a tartrate monosuccinate component having the structure 20 HOCH - CH - O - CH - CH 2 2 COOX COOX COOX COOX. Wherein X is H or a salt-forming cation; and b) 1-99% by weight of a tartrate disuccinate component having the structure 30 CH_-CH-O -CH-CH- O - CH - CH_ I 2 I II I I 2 COOX COOX COOX COOX COOX COOX wherein X is H or a salt-forming cation. Laundry additive, characterized in that it contains a softening amount of a polymeric clay flocculant as defined in claim 1, wherein the additive is in the form of a sheet or bag 96776 or as a film forming a bag filled with a single dose of clay-containing detergent composition. Laundry additive according to Claim 10, characterized in that it further contains fabric softening clay and / or other fabric softening ingredients. Softener for rinsing laundry, characterized in that it contains 1 to 30% of a smectite-type clay and a softening-enhancing amount of a polymeric clay flocculant as defined in claim 1. A fabric softener for laundry rinsing according to claim 12, characterized in that it further contains a fabric softener and / or other fabric softening ingredients. tl 96776