DK171848B1 - Detergent composition, laundry additive composition and blame additive softening composition - Google Patents

Description

in DK 171848 B1

The present invention relates to detergent compositions. More specifically, it relates to detergent compositions containing a fabric softening amount of the smectite type clay. The compositions further contain a polymeric clay flocculant.

5 In the specification of 6B Patent No. 1,400,898, detergent compositions are described which contain, as a fabric softening component, clay of the smectite type. Any smectite-type clay with a cation exchange capacity of at least 50 meq / 100 g is stated to be suitable.

Gelwhite GP and Volclay BC, both of which are sodium montmorillonite clays, are described therein as preferable in color and cation exchange ability.

It is now recognized in the detergent field that clays of the type disclosed in the specification to GB Patent No. 1,400,898 provide significant fabric softening benefits when used in a detergent. However, it is equally recognized that the deposition of these clays on textiles during the washing process is far from complete; in fact, under typical European washing conditions, less than half of the available clay is deposited on the fabrics, while the remainder is flushed away with the washing liquid during subsequent rinsing steps. Furthermore, the softening effect resulting from the clay deposition is affected by factors that are not fully understood.

25

Accordingly, it is an object of the present invention to provide detergent compositions comprising a fabric softening clay and from which the clay particles are more effectively deposited on fabrics during the washing process. It is a further object of the present invention to provide detergent compositions from which the clay particles are effectively deposited, regardless of the builder system used.

The present invention relates to detergent compositions which contain from 5% to 40% organic surfactant and as fabric softening ingredient from 1% to 30% clay of the smectite type, which compositions are characterized in that they further contain an emollient-promoting amount of polymer clay flocculant, typically from 0.005 to 20% by weight of the smectite-type clay.

DK 171848 B1 2

Preferred clay flocculants are polymers such as poly (ethylene oxide), poly (acrylamide) and poly (acrylate) having a weight average molecular weight of from 100,000 to 10,000,000, most preferably from 150,000 to 5,000,000.

5

Detergent compositions of the invention include conventional detergent surfactants, conventional builders, and optionally other conventional detergent ingredients. The compositions further comprise a fabric softening amount of from 1 to 30% by weight of the detergent composition, the fabric softening clay.

The percentages given herein are percentages by weight of the detergent compositions, unless otherwise stated.

The compositions further contain a polymeric clay flocculant.

It is known that polymeric clay flocculants promote the deposition of cloth softening clays on textiles. The amount of clay flocculant to be used in the present detergent compositions must be such that the deposition of the softening clay on the fabrics is promoted, but remains substantially uniform. For a given polymeric clay flocculant, the amount required in the detergent composition can be readily determined by a simple level test using the clay deposition test described below.

Clay Clay Testing 30 For samples of a detergent composition containing 5% of a fabric softening clay, different levels of the polymeric clay flocculant to be tested are set. Tissue samples are washed in 1% solutions of the respective detergent samples. The samples are rinsed and hung to dry on a string. The clay on the 35 specimens is stained with methylene blue. The color is compared to the color of a sample to which no polymer clay flocculant has been added.

Any level of the polymeric clay flocculant, which results in a color that is visibly darker than that obtained when no clay flocculant has been added, provides the desired softness-enhancing effect. Such a level will hereinafter be referred to as "a softening amount" of the clay flocculant.

Relatively high levels of a clay flocculant result in stain deposition or even diminished deposition of the clay. The colored specimens exhibit blue spots, rather than a substantially uniform color. Such relatively high levels of clay flocculant do not result in the desired improvement in softness and are therefore not considered as softness enhancing amounts.

Typically, the amount of clay flocculant, expressed in percent by weight of the smectite type clay, is from 0.005 to 20% by weight of the clay, preferably from 0.05 to 20% by weight of the clay for clay flocculants having a weight average molecular weight of from 150,000 to 800,000 and from 0.005 to 2% by weight of the clay for MV of 800,000 to 5,000,000.

20

Clay flocculants are not commonly used in detergent compositions. On the contrary, there is a tendency to use clay dispersants which help to remove clay stains from textiles. However, such agents are particularly well known in other industrial fields such as oil drilling and for flotation in the metallurgy field. Most of these substances are fairly long chain polymers and copolymers derived from monomers such as ethylene oxide, acrylamide, acrylic acid, dimethylaminoethyl methacrylate, vinyl alcohol, vinylpyrrolidone, ethyleneimine. Rubber, such as guar gum, is also suitable.

Polymers of ethylene oxide, acrylamide or acrylic acid are preferred.

For appropriate action on the clay particles, the polymers should be relatively long-chain, i.e., have a weight average molecular weight

OC

of at least 100,000. For sufficient water solubility, the weight average molecular weight of the polymers should not exceed 10,000,000. Most preferred are polymers having a weight average molecular weight of from 150,000 to 5,000,000.

DK 171848 B1 4 Cloth soaking

Smectite-type clays have found wide use as a fabric softening component in detergent compositions. The majority of these 5 clay materials have a cation exchange capacity of at least 50 meq / 100 g.

Montmorillonite clay species are commonly used for this purpose.

However, it appears that some hectorite species have better cloth softening effect than the more commonly used montmorillo-10 rivet types. The hectorite materials that exhibit this better fabric softening effect are hectorite materials of natural origin.

The cation exchange ability of clay materials is a well-known parameter and can be determined by well-known analytical methods, see, for example, H. van Olphen, "Clay Colloid Chemistry", Interscience Publishers, 1963 and the relevant references cited therein.

Other detergent components 20

Detergent Surfactants - The compositions of the invention typically contain organic surfactants ("surfactants") to provide the usual cleaning benefits associated with the use of such substances.

25

Detergent surfactants useful in the invention include well-known synthetic anionic, nonionic, amphoteric and zwitterionic surfactants. Typical examples of this are alkylbenzene sulfonates, all alkyl and alkyl ether sulfates, paraffin sulfonates, 50 olefin sulfonates, alkoxylated (especially ethoxylated) alcohols and all alkyl phenols, amine oxides, α-sulfonates of fatty acids and fatty acid esters and the like well known in the laundry . Generally, such detergent surfactants contain an alkyl group in the range of C 6 -C 8; anionic detergent surfactants may be used in the form of their sodium, potassium or tri-ethanol ammonium salts; the non-ionic generally contains from ca. 5 to approx. 17 ethylene oxide groups. The disclosure of U.S. Patent No. 3,995,669 contains detailed disclosures of such typical detergent surfactants. Cj i-C Alg-Alkyl benzene sulfonates, C C-Cjg-paraffin sulfonates and the -alkyl sulfates and the ethoxylated alcohols and allkyl phenol are particularly preferred for the compositions of the present type.

Suitable surfactants of the invention are also the water-soluble soaps, for example, the well-known sodium and potassium coconut or tallow soaps known in the art.

The surfactant component may comprise as little as 1% of the compositions of the invention, but preferably the composition contains from 5% to 40%, preferably from 10% to 30%, surfactant. Mixtures of the ethoxylated nonionic and anionic, such as all cool benzenesulfonates, all cool sulfates and paraffin sulfonates, are preferred for purification throughout the wash cycle of a wide range of textiles and stains. It is known from the past that high levels of 15 non-ionic surfactants (ie, more than 4%) in clay-containing detergent compositions adversely affect the softening effect of the clay. It has now surprisingly been discovered that such a negative effect does not occur if the clay flocculant of the present invention is also present.

20

Detergent Adjuvants - The composition of the present invention may contain other ingredients which promote the washing effect. For example, it is highly preferred that detergent compositions for use throughout the wash cycle contain a detergent builder and / or a metal ion sequestrant. Compounds which can be classified and well known in the art as detergent builders include nitrile triacetates, polycarboxylates, citrates, carbonates, zeolites, water soluble phosphates such as tri-polyphosphate and sodium ortho and pyrophosphates, silicates and mixtures thereof. Metal ion sequestrants include all of the above as well as substances such as ethylene diamine tetraacetate, aminopolyphosphonates (DEQUEST) and a host of other poly-functional organic acids and salts, which are too extensive to be discussed in detail herein. Reference is made to U.S. Patent No. 3,579,454 for typical examples

OC

use of such substances in various purification compositions. Generally, the builder / sequestering agent is from approx. 0.5% to 45% of the composition. 1-10 µπι of the zeolite builder (for example, zeolite A) of DE Patent No. 2,422,655 is particularly preferred for use in low-phosphate compositions.

Particularly suitable phosphate-free builders are ether carboxylate mixtures comprising: a) from 1% to 99% of a tartrate monosuccinate component of the formula: 5 HOCH-CH-O-CH-CH, II I I 2

COOX COOX COOX COOX

where X represents H or a salt-forming cation, and b) from 1 to 99% by weight of a tartrate disuccinate component of the formula: CH, -CH-O-CH-CH-O-CH-CH, I 2 I II I I 2

15 COOX COOX COOX COOX COOX COOX

where X represents H or a salt-forming cation.

Builder systems of this type are described in more detail in U.S. Patent No. 4,663,071, issued May 5, 1987 to Bush et al.

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

25

The detergent compositions herein also preferably contain enzymes to enhance their cleaning effect during the washing process on various dirt forms and stains. Amylase and protease enzymes suitable for use in detergents are well known in the art and in commercially available liquid and granular detergents. Commercial detergent enzymes (preferably a mixture of amylase and protease) are typically used at levels of 0.001% to 2% and more in the present compositions. Detergent cellulase enzymes provide both cleansing and softening benefits, especially on cotton textiles. These enzymes are highly desirable in the detergent compositions of the invention.

The compositions described herein may contain other ingredients which enhance their cleaning effect. For example, the compositions herein may advantageously contain a bleaching agent, in particular a peroxyacid bleaching agent. For the purposes of the present invention, the term peroxyacid bleach comprises both peroxyacids, as well as systems capable of delivering peroxyacids in situ.

5 Peroxyacids per se comprise the derived alkali and alkaline earth metals. Peroxyacids and diperoxyacids are commonly used, and examples of these are diperoxydodecanoic acid (DPDA) or peroxyphthalic acid.

Systems capable of delivering peracids in situ include a peroxygen bleach and an activator thereof.

Peroxygen bleaches are agents capable of delivering hydrogen peroxide in an 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, percarbonates, perphosphates, persilicates and the like.

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

The released hydrogen peroxide is reacted with a bleaching activator to form the peroxyacid bleach. Bleach activator classes include esters, imides, imidazoles, oximes and carbonates. In these classes, preferred substances include methyl-o-acetoxybenzoates; sodium p-acetoxybenzenesulfonates such as sodium 4-nonanoxyloxybenzenesulfonate, sodium 4-octanoyloxybenzenesulfonate and sodium 4-3 ° decanoyloxybenzenesulfonate; bisphenol A diacetate; tetraacetylethylen-diamine; tetraacetylhexamethylenediamine; tetraacetylmethylenediamine.

Other very preferred peroxygen bleaching activators described in the disclosures of U.S. Patents Nos. 4,483,778 and Nos.

4,539,130 are α-substituted alkyl or alkenyl esters such as sodium 4 (2-chloroctanoyloxy) benzenesulfonate, sodium 4- (3,5,5-trimethylhexanoyloxy) benzenesulfonate. Suitable peroxyacids are also peroxygen bleaching activators, such as those disclosed in published European Patent Application No. 116,571, that is, compounds of the general type RXAOOH and RXAL, wherein R represents a hydrocarbyl group, X represents a heteroatom, A represents a carbonyl bridging group and L represents a cleavage group, in particular oxybenzenesulfonate.

Other highly desirable detergent components for use in the detergent compositions of the present invention are quaternary ammonium compounds of the formula R4RgRgR7N + X "wherein R4 represents alkyl of from 8 to 20, preferably from 12 to 18 carbon atoms,

R 1 represents all alkyl of from 1 to 10 carbon atoms, and R 8 and R 10 each represent C 1 to C 2 alkyl, preferably methyl: X "represents an anion, for example chloride. Examples of such quaternary ammonium compounds include C C 1-4 alkyltrimethylammonium chloride and coconutyltrimethammonium methosulfate The quaternary ammonium compounds can be used at levels of from 0.5% to 5%, preferably from 1% to 3%.

Additional emollients.

The detergent compositions of the present invention may further contain, in addition to the clay material, other softening ingredients. Suitable examples include amines of the formula R 1 R 2 N, wherein R 2 represents C 9 -C 20 hydrocarbyl, R 2 represents C 1 -C 20 hydrocarbyl, and R 3 represents C 1 -C 2Q hydrocarbyl or hydrogen. A preferred amine of this type is ditalgmethylamine.

25

Preferably, the plasticizing amine is present in the form of a fatty acid complex of the formula RCOOH wherein R represents a C 9 -C 20 alkyl or alkenyl. It is desirable that the amine / fatty acid complex be present in the form of microfine particles having a particle size of from, for example, 0.1 to 20 µm. These amine / fatty acid complexes are described in more detail in the specification of EP patent application no.

0133804. Preferred are compositions containing from 1% to 10% of the amine.

35

Also suitable are complexes of the above-described amine and phosphate esters of the formula: DK 171848 B1 9 0?

Rft0-P-OH and HO-P-OH

5 8 I I

ORg ORg

Where Rg and Rg represent C1-C8 alkyl or ethoxylated alkyl groups of the general formula alkyl (OCHgCHgJy * wherein the alkyl substituent is Cj-Cgg »preferably Cg-Cjg and y is an integer of from 1 to 15, 10 preferably 2 -10, most preferably 2-5.

Amine / phosphate ester complexes of this type are described in more detail in the specification of European Patent Application No. 168,889.

Further examples of any softening ingredients include the softening amides of the formula RioR11NCOR12 'wherein Rjq and Rjj are independently selected from C1-C22'alkyl, -alkenyl, hydroxyalkyl, aryl and allkyl-aryl groups; R 2 represents hydrogen or a C 1 -C 8 alkyl or alkenyl, an aryl or alkyl-aryl group or is -R 13 where R 1 represents a C 1 -C 8 alkyl or alkenyl, an aryl or alkyl-aryl group. Preferred examples of such amides are ditalga-cetamide and ditalgbenzamide. Good results are obtained when the amides are present in the composition in the form of a composite with a fatty acid or with a phosphate ester as described above for the softening 2 ^ amines.

The amides are present in the composition with 1-10% by weight.

Suitable plasticizers are also the amines disclosed in the specification of GB Patent Application No. 2,173,827, in particular the substituted cyclic amines described therein. Suitable are imidazolines of the general formula 1- (higher alkyl) amido (lower alkyl) -2- (higher alkyl) imidazoline, wherein higher alkyl represents all carbon with from 12 to 22 carbon atoms and lower alkyl represents all alkyl with 35 from 1 to 4 carbon atoms.

A preferred cyclic amine is 1-talgamidoethyl-2-talgimidazoline. Preferred compositions contain from 1% to 10% of the substituted cyclic amine.

DK 171848 B1 10

The amine and amide softening component can be added to a granular detergent in the form of a dry powder, or it can be sprayed onto the granular detergent or carrier, either in molten or dissolved form. An example of a suitable carrier is perborate monohydrate.

5

The compositions herein may, in addition to the ingredients already mentioned, may also contain various other optional ingredients typically used in commercial products to provide aesthetic or other product effect benefits. Typical constituents include pH regulators, perfumes, dyes, bleaches, optical whites, soil suspending agents, hydrotropes and gel regulators, freeze-thaw stabilizers, bactericides, preservatives, foam regulators, bleach activators and the like.

15

For use during a whole wash process, the compositions are typically used at a concentration of at least 400 ppm, preferably from 0.05% to 1.5% in an aqueous wash bath of pH 7-11 for washing fabrics. The washing can be carried out at from 5 ° C to the boiling point with excellent results.

Industrial application

Detergent compositions of the present invention may be formulated as granular or liquid detergents. It has been discovered that high swelling clay materials can be easily incorporated into a liquid detergent composition while maintaining phase stability.

30

In the preparation of liquid detergent compositions, the polymer clay flocculant can be mixed with the other detergent components with stirring.

In preparing a granular detergent composition, the polymeric clay flocculant can be added in a variety of ways.

It may be added to the crutcher mixture prior to spray drying, or it may be sprayed on a granular detergent as a solution in water or an organic solvent, or it may be dry mixed in the form of particles with a granular detergent. The release of the DK 171848 B1 11 flocculant can be controlled by incorporation into a pill or by microencapsulating it in a suitable microencapsulant.

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

The chemical stability of the clay flocculant is improved by adding in small amounts (typically from 0.05 to 1% by weight of the detergent composition) of a chelating agent. A preferred chelating agent is ethyl diamine tetramethylene phosphonic acid.

Further, the clay flocculant can be incorporated into a detergent additive, for example in the form of a sheet or bag to be added to the washing liquid in addition to a traditional detergent composition. The detergent additive preferably also contains a fabric softening clay and / or other of the fabric softening ingredients described above and thus can be used in connection with detergent compositions which do not themselves contain such clay or 70 such other softening ingredients. In a very specific embodiment, the polymer clay flocculant is designed as a water-soluble film. The film is formed as a bag which is filled with a single portion of a clay-containing detergent-PC composition. Upon use, the bag will dissolve and release the detergent composition. The dissolved polymer will affect the softening clay, thus increasing its deposition on textiles. Ethylene oxide polymers are particularly suitable for use in this embodiment of the invention.

30

Furthermore, a fabric softening clay and a softness-enhancing amount of polymeric clay flocculant can be incorporated into a rinsing additive softening composition. Other plasticizers, such as quaternary ammonium compounds, may also be present.

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Claims (12)

A detergent composition comprising 5 1) from 5% to 40% of an organic surfactant, and 2. from 1% to 30% clay of the smectite type as a fabric softening component, characterized in that it further comprises 3. a polymer clay flocculant of 0.005 to 20% by weight of the smectite-type clay. Detergent composition according to claim 1, characterized in that the clay flocculant is a polymer derived from monomers selected from ethylene oxide, acrylamide, acrylic acid, dimethylaminoethylmethacrylate, vinyl alcohol, vinylpyrrolidone, ethyleneimine, and a mixture thereof, having a polymer thereof, -20 molecular weight of from 100,000 to 10,000,000. Detergent composition according to claim 2, characterized in that the polymer is derived from monomers selected from ethylene oxide, acrylamide and acrylic acid. 25 Detergent composition according to any one of claims 1-3, characterized in that the polymeric clay flocculant has a weight average molecular weight of from 150,000 to 5,000,000. Detergent composition according to claim 4, characterized in that the clay flocculant has a molecular weight of from 150,000 to 800,000 and is present in an amount of 0.05 to 20% by weight of the smectite-type clay. OC Detergent composition according to claim 4, characterized in that the clay flocculant has a molecular weight of from 800,000 to 5,000,000 and is present in an amount of 0.005 to 2% by weight of the smectite-type clay. DK 171848 B1 Detergent composition according to claim 5 or 6, characterized in that it further comprises from 0.5% to 5% of a quaternary ammonium compound of the formula R 1 RgRgRyhTX, wherein R 2 represents all cooling with from 8 to 20 carbon atoms, R all are 5 to 1 carbon atoms, Rg and Ry each represent C1-C4 alkyl and X represents an anion. Detergent composition according to claim 5 or 6, characterized in that it further comprises from 1% to 10% of a 10 amide of the formula RjgRjjNCORjg, wherein Rjq and Rjj are independently selected from C1-C4 alkyl, -alkenyl, -hydroxyalkyl, aryl and alkyl aryl groups; R 2 represents hydrogen or a C 1 -C 2 alkyl group or alkenyl, aryl or alkyl-aryl group, or represents O-R 1 j, where R 13 is a C 1 -C 22 alkyl or alkenyl, an aryl group. or 13alkyl aryl group. Detergent composition according to claims 5-6, characterized in that it further contains from 1% to 10% imidazoline of the formula 1- (higher alkyl) amido (lower alkyl) -2- (higher alkyl), wherein higher each carbon has from 12 to 20 carbon atoms and lower all carbon has from 1 to 4 carbon atoms. Detergent composition according to any one of claims 5 to 9, characterized in that it further contains from 5% to 35% of a builder system, which builder system comprises: a) from 1% to 99% of a tartrate monosuccinate component of the formula :, n IIII 2 30 coox coox coox coox where X represents H or a salt-forming cation, and b) from 1 to 99% by weight of a tartrate disuccinate component of the formula: I 2 I II II 2 C00X COOX COOX C00X COOX COOX where X represents H or a salt-forming cation. DK 171848 B1 Wash additive composition, characterized in that it comprises smectite-type clay and a softness-enhancing amount of a polymeric clay flocculant. Rinse-added softening composition comprising from 1% to 30% of the smectite type clay, characterized in that it comprises a softening amount of a polymeric clay flocculant ranging from 0.005 to 20% by weight of the smectite type clay. 10 15 20 25 30 35