FI92496C - Detergent compositions containing cellulase granules - Google Patents

Abstract

Detergent compositions for the cleaning and softening of fabrics are claimed, in which cellulase granulates containing a water-insoluble calcium salt, preferably calcium carbonate, are incorporated. Softness and fabric-appearance benefits are excellent. The cellulase granulates per-se are also claimed.

Description

92496

Detergent compositions containing cellulase granules

Technical area

The present invention relates to granular detergent compositions useful in cleaning and softening fabrics and having other fabric care benefits, such as appearance enhancements and rejuvenation.

The compositions disclosed herein comprise a clay material softening the fabric 10 and a cellulase enzyme in the form of granules containing calcium carbonate.

Background of the invention

It has been the subject of many detergent manufacturers to formulate laundry detergent compositions which have the expected good cleaning performance and also have fabric care properties, including softness.

Typical such detergent compositions are those disclosed in GB Patents 1,514,275 to 1,400,898 or EP Patent 0,026,528.

Cellulase enzymes have already been used in detergent compositions due to their cleaning capabilities, as disclosed in GB Patent Applications GB-A 2,095,275, GB-2,094,826 or JP Patent 57,108-199.

Cellulases have been found to provide softness benefits to fabrics, such as in U.S. Patent No. 4,435,307.

EP-A 0 120 528 discloses alkaline softener detergent compositions comprising a synergistic mixture of a water-insoluble C10-C26 tertiary amine and cellulase.

EP-A 0 177 165 discloses alkaline softener detergent compositions comprising a mixture of smectite clay and cellulase.

EP-A 0 220 016 discloses the brightening effect of fabric color resulting from the use of cellulase in connection with detergent 35.

i ... T ”2 92496

When such detergent and / or softener compositions are in granular form, the cellulase enzymes are usually included in the composition in the form of granules, also identified as marumenes or granules obtained from the enzyme producer.

U.S. Pat. No. 4,435,307, which relates to a hardener for reducing the hardness of detergent compositions, discloses the use of cellulase granules and mentions certain additives which need to be added to the granules during their preparation, e.g.

10 polyunsaturation and color purposes.

However, it has been found that certain female additives are detrimental to the softness / fabric care properties of the composition when cellulase granules containing these additives are included in the detergent composition.

In the search for substitutes for these undesirable additives, it has now been found that water-insoluble calcium salts surprisingly substantially improve the softness / fabric care properties of detergent compositions containing enzyme migranulates.

Therefore, it is an object of the present invention to provide detergent compositions which exhibit excellent softness / fabric care properties due to the use of cellulase granules containing a water-insoluble calcium salt.

SUMMARY OF THE INVENTION The present invention relates to a finely divided composition for cleaning and softening fabrics comprising 1-50% by weight of a surfactant, 1-20% by weight of a fabric softening clay material and 1-50% by weight of cellulase granules. The composition is characterized in that the granules contain 1 to 50%, preferably 5 to 15%, by weight of calcium carbonate of the granules.

Calcium carbonate is preferably used as a baling agent for cellulase granules.

The invention also relates to the cellulase granules described above per se.

3,92496

Detailed description of the invention

The compositions herein are capable of cleaning and softening treated fabrics as well as providing benefits in terms of improvements and rejuvenation of the fabric's appearance.

This is achieved by the presence of granular compositions containing surfactants, fabric softening clays and cellulase granules containing calcium carbonate.

The following mandatory non-alternative additives are described in detail below:

cellulase

The cellulase useful in the present invention may be any bacterial or fungal cellulase having a pH optimum between 5 and 9.5.

Suitable cellulases are disclosed in U.S. Pat. No. 4,435,307, GB-A-2,095,275, DE-OS-2,247,832 and EP-A 0 220 016.

Examples of such cellulases are cellulases produced by the strain Humicola insolens (Humicola 20 grisea var. Thermoidea), in particular Humicola strain DSM 1800, and cellulases produced by the strain Bacillus N, or cellulase 212 produced by the strain belonging to the genus Aeromonas , and cellulases extracted from the liver pancreas of the sea lynx (Dolabella Auricula Solander).

: 25 The determination of cellulase activity here is based on the hydrolysis of carboxymethylcellulose. The low molecular weight reduced carbohydrates formed are determined colorimetrically by the ferrocyanide reaction as described by W.S. Hoffman, "J. Biol. Chem." 30 120, 51 (1973). The key incubation conditions are pH = 7.0, temperature 40 ° C and incubation time 20 minutes.

One CMCase unit is defined as the amount of enzyme which, under the conditions described above, forms a reduced amount of reduced carbohydrate per minute corresponding to 10-4 moles of glucose.

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The range of cellulase activity useful in the present context is 5 to 1360, preferably 60 to 140, CMCase activity units / gram of detergent composition.

5 Cellulase granules

The cellulase enzymes used in the granular detergent compositions are usually supplied in the form of granules, e.g. marumens or granules.

Such granules contain for the most part 10 crude cellulase enzyme together with additional additives such as polyethylene glycol, which is usually 5 to 7%, and cellulose, which is usually about 10%. The molecular weight of the polyethylene glycol used herein may range from 500 to 8000.

The cellulase maSrM in the granules is determined according to the total cellulase activity of the composition, which must be within the limits specified above.

It has been found that certain materials used by the enzyme producers as polynessants and bleaches, which are titanium dioxide and magnesium silicate, negatively affect the softening property of the composition.

The compositions of the invention should therefore be preferred. be free of titanium dioxide and magnesium silicate.

It has now been found that calcium carbonate has an anti-politicizing effect when added to cellulase granules and also provides unexpected softness / fabric care benefits, as will be shown later.

Calcium carbonate should be present in the cellulase granules in an amount of 1 to 10%, preferably 5 to 15%, by weight of the granules.

The particle size of calcium carbonate, ranging from 1 to 10 microns, has been found to be particularly suitable for the purpose of the present invention.

II

5,92496 The calcium carbonate used herein can be used as such or in a baled form, usually baled with stearic acid. In a preferred embodiment of the present invention, the calcium carbonate, either as such or coated with e.g. stearic acid, is baled on top of the cellulase granules.

Cellulase granules can be prepared in a number of different ways, for example by means of a "Marumerizer" as described in GB Patents Nos. 1,362,365 and 1,361,387, or by means of a granulating machine as described in Aufbereitungs-Technik No. 3/1970, pages 147-153 and in No. 5/1970, pages 262-278, or may be granular granules as described in BE Patent No. 760 135. In all cases, the granules must have low polishing properties.

The calcium carbonate herein is either mixed with other additives in the preparation of the granules or mixed with the cellulase prior to granulation, or preferably coated on the surface of the granules 20, which granules have been prepared as described above by conventional coating methods.

The cellulase granules according to the present invention have a lasna content of 1 to 50%, preferably 1.5 to 10%. the weight of the detergent composition present.

Surfactant The surfactant useful in TS may be selected from anionic, nonionic, amphoteric ionic surfactants and is present in an amount of from about 1% to about 50%, preferably from about 10% to about 30%, by weight of the composition.

30 Suitable anionic surfactants are the alkyl benzene sulfonates, alkyl sulfates, alkyl-lipolyetoksieetterisulfaattien, paraffin sulfonates, alpha-olefin sulphonates, alpha-sulphocarboxylates and their esters, alkyl, 35 fatty acid monoglyceride sulphates and sulphonates, alkyl * 6 92 496 kyylifenolipolyetoksieetterisulfaattien, 2-acyloxy-alkyl water-soluble salts of canane 1-sulfonates and beta-alkyloxyalkane sulfonates.

Particularly Preferred alkylbenzene sulfonates 5 have 9 to 15 carbon atoms, especially 11 to 13 carbon atoms, in a straight or branched alkyl chain. Suitable alkyl sulphates have from 10 to 22 carbon atoms, more particularly from 12 to 18 carbon atoms, in the alkyl chain. Suitable alkyl polyethoxy ether sulfates have 10 to 18 carbon atoms in the alkyl-10 chain and have an average of 1 to 12 -CH 2 CH 2 O groups per molecule, especially 10 to 16 carbon atoms in the alkyl chain and an average of 1 to 6 -CH 2 CH 2 O groups per molecule.

Suitable paraffin sulfonates are substantially straight and contain from 8 to 24 carbon atoms, more particularly from 14 to 18 carbon atoms. Suitable alpha-olefin sulfonates have from 10 to 24 carbon atoms, more particularly from 14 to 16 carbon atoms; alpha-olefin sulfonates can be prepared by reaction with sulfur trioxide followed by neutralization under conditions such that all sulfones present are hydrolyzed to the corresponding hydroxyalkane sulfonates. Suitable alpha-sulfocarboxylates contain from 6 to 20 carbon atoms; it includes not only salts of alpha-sulfonated fatty acids but also their esters which have been prepared. alcohols containing 1 to 14 carbon atoms.

Suitable alkyl glyceryl ether sulphates are ethers of alcohols having from 10 to 18 carbon atoms, in particular those derived from coconut oil and tallow. Suitable alkylphenol polyethoxy ether sulfates have 8 to 12 carbon atoms in the alkyl chain and an average of 1 to 6 -CH 2 CH 2 O groups per molecule. Suitable 2-acyloxyalkane-1-sulfonates have 2 to 9 carbon atoms in the acyl group and 9 to 23 carbon atoms in the alkane moiety. Suitable beta-alkyloxyalkane sulfonates have 1 to 3 carbon atoms in the alkyl group and 8 to 20 carbon atoms in the alkane moiety.

The alkyl chains of the aforementioned anionic surfactants may be derived from natural sources, such as coconut oil to tallow, or may be prepared synthetically, such as using Ziegler or Oxo methods. Water solubility can be obtained using alkali metal, ammonium or alkanol ammonium cations; sodium is recommended. This invention includes mixtures of anionic surfactants; the satisfactory mixture contains an alkyl benzene sulfonate having 11 to 13 carbon atoms in the alkyl group and an alkyl 10 sulfate having 12 to 18 carbon atoms in the alkyl group.

Suitable nonionic surfactants for addition to the compositions herein include water-soluble ethoxylated HLB 11.5-17.0 materials and include, but are not limited to, primary and secondary C 10 -C 20 alcohol ethoxylates and C 6 -C 10 alkylphenols. -sylaatit. Direct primary C14-C18 g alcohols condensed together with 7-30 moles of ethylene oxide per mole of alcohol are preferred, with examples being C14-C.5 (EO) 7, C16-Cl8 (ΕΟ) Μ and especially C16-Cig (EO) n. Cationic additional surfactants that can be used herein include water-soluble quaternary ammonium compounds of the form R4R5R6R7N + X ', wherein R1 is alkyl having 10 to 20, preferably 12 to 18 carbon atoms, and R5, R' and R7 are each C 1 -C 7 alkyl, preferably methyl; X is an anion, e.g. chloride. Examples of such trimethylammonium compounds include C 12 -C 14 alkyltrimethylammonium chloride and coconut alkyl trimethylammonium methosulfate.

The compositions of the invention are substantially free of water-insoluble long chain alkylamine plasticizers and derivatives thereof, as they have been found to react negatively with cellulase under the pH conditions of the present invention. Derivatives of amine plasticizers contain the corresponding amine compounds. Such amine softeners have been reported e.g.

•> »8 92496 in EP AO 026 528 and EP 1 0120 528 and contain in particular amines of the form R, R 2 R 3 N, in which x the R 1 and R 2 are C 6 -C 20 alkyl chains and R 3 is a C 1 -C 10 alkyl chain or hydrogen .

The compositions herein are formulated over a pH range of 6.5 to 9.5, measured as a 1% solution of the composition in distilled water. In this pH range, the cellulases used herein have optimum performance.

Fabric Softening Clay Material 10 The compositions herein should contain a softening clay material.

Such emollients are well known in the detergent patent literature and are in widespread commercial use in both Europe and the United States. Such emollient clays include various heat-treated kaolins and various multilayer smectites. Preferred emollient clays are the smectite emollient clays described in German Patent 2,334,899 and GB Patent 1,400,898, 20 of which may be incorporated in detail.

The most preferred fabric softening clay materials include materials of bentonite origin, with bento-rivets being mainly montmorillonite-type clays in combination with various impurities, the amount and nature of which depends on the clay material. Emollient clays are used in the preferred compositions in an amount of at least 1%, usually 1 to 20%, preferably 2 to 10%.

Alternative Additives 30 The compositions herein may contain, in addition to the necessary additives, certain alternative additives.

For example, it is recommended that the laundry detergent compositions contain a detergent active ingredient and / or a metal ion separator. Compounds classified as detergent active ingredients and well known in the art include nitrilotriacetates, polycarboxylates, citrates, water-soluble phosphates such as tripolyphosphate and sodium ortho- and pyrophosphates, and mixtures thereof. Metal-5 ion scavengers include all of the above plus materials such as ethylenediaminetetraacetate, aminopolyphosphonates, and a wide variety of other polyfunctional organic acids and salts that are too much to list in detail herein. U.S. Patent 3,579,454, which provides typical examples of the use of such materials in various cleaning compositions. Preferred organic acid species for use herein are citric acid, ethylenediaminetetramethylenephosphonic acid and diethylenetriamine pentamethylenephosphonic acid.

A further useful group of detergent active materials in the present invention are insoluble sodium aluminosilicates. The 1-10 micron zeolite power agents (e.g., zeolite A) disclosed in German Patent 2,422,655 are particularly preferred for use in low phosphate or phosphate-free compositions. Generally, the active ingredient / release agent comprises 0.5 to 45% of the composition.

The compositions herein include myds fatty acids, saturated or unsaturated, and the like. Suitable fatty acids, saturated or unsaturated, have from 10 to 18 carbon atoms in the alkyl chain. Preferred are unsaturated species having 14 to 18 carbon atoms in the alkyl chain, most preferably oleic acid. Similar soaps can also be used. Alternative fatty acids / soaps are used in amounts up to 20%.

The compositions herein may also contain compounds of the general formula R-CH (COOH) CH2 (COOH) 35, namely succinic acid derivatives wherein R 92496 in the formula R is C10-C20 alkyl or alkenyl, preferably C12-Cl6, or wherein R may be substituted by a hydroxyl, sulfo, sulfoxy or sulfone substituent.

The active succinic acid active ingredients are preferably used in the form of their water-soluble salts, including sodium, potassium, ammonium and alkanol ammonium salts.

Specific examples of succinic acid active ingredients include: lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenyl succinate (preferred), 2-pentadecenyl succinate and the like.

Also suitable active ingredients in the present context are the compounds described in U.S. Patent 4,663,071, namely mixtures of tartrate monomeric acid and tartrate dimeric acid in weight ratios of monomeric succinic acid and dimeric succinic acid of 97: 3 to 20:80, preferably 95: 5 to 40:60.

Another alternative additive is bleach. Preferred are peroxy bleaches such as sodium perborate in commercially available mono- and tetrahydrate forms, sodium carbonate peroxyhydrate, sodium pyrophosphate peroxyhydrate and urea peroxyhydrate.

Bleach activators can be used in combination with the above peroxygen bleaches. Groups of bleach activators include esters, imides, imidazoles, oximes and carbonates. Preferred materials in those groups include methyl o-acetoxybenzoates; sodium p-acetoxybenzenesulfonates such as sodium 4-octanoyloxybenzenesulfonate, sodium 4-octanoyloxybenzenesulfonate and sodium 4-decanoyloxybenzenesulfonate; biofenolidiasetaatti; tetraacetylethylenediamine; tetra acetyl; tet ra-acetyl methylene diamine.

Other highly preferred peroxy bleach activators disclosed in U.S. Patents 4,483,778 and 35,439,130 are alpha-substituted alkyl or alkenyl.

II

92496 esters such as sodium 4- (2-chloroctanoyloxy) benzenesulfonate, sodium 4- (3,5,5-trimethylhexanoyloxy) benzenesulfonate. Also suitable peroxyacids are the peroxy bleach activators described in published EP patent application 0 166 571, namely compounds of the general formula RXAOOH and RXAL, in which R is a hydroxycarbyl group, X is a heteroatom, A is a carbonyl bond group, L is a leaving group and L is a leaving group .

Enzymes other than cellulases, such as proteolytic, amylolytic or lipolytic enzymes, may be used in addition to the cellulase therein.

The compositions herein may contain soil release / dirt suspending agents, usually in an amount of 0.1 to 10% by weight. In particular, alkoxylated polyamines suitable as anti-loosening / reprecipitation inhibitors can be used. These components, as well as their preparation, are disclosed in EP-PA 0 112 593, the disclosures of which are incorporated herein by reference.

It is to be understood that the term "polyamines" as used herein generally refers to alkoxylated polyamines both in their amine form and in their quaternary form. Such materials are easy to present as molecular .. empirical structures of repeating units: --NR - s— Amine form (Alkoxy) y 30 and R1 Γ 1 Ί --N + -R — jx 'Quaternary form 35 L _. (Alkoxy) v * 7 12 92496 wherein R is a hydrocarbyl group, usually 2 to 6 carbon atoms; R 1 may be a C 1 -C 20 hydrocarbon; alkoxy groups are ethoxy, propoxy and the like, and y is 2 to 30, most preferably 10 to 20; n is an integer of at least 2, preferably 2 to 20, most preferably 3 to 5; and X 'is an anion derived from the quaternization reaction, such as a halide or methyl sulfate.

The most preferred polyamines for use herein are the so-called ethoxylated polyethyleneimines, the products of the polymerization reaction of ethylene oxide and ethyleneimine with the general formula: (EtO) - N - CH2 - CH2--5-N- (EtO) y (EtO) y (EtO) y where n is an integer from 3 to 5 and y is an integer from 10 to 20.

Dirt suspending agents can also be selected from poly-20 ethylene glycols having molecular weights ranging from 400 to 1000, polyacrylates or copolymers of acrylic acid and maleic anhydride / maleic acid.

The detergent compositions herein are preferably free of carboxymethylcellulose.

In addition, the compositions herein may contain, in addition to the additives already mentioned, various alternative additives commonly used in commercial products for additional aesthetic or product performance benefits. Common additives include pH adjusters, perfumes, dyes, optical brighteners, hydrotropes and gel regulators, freeze-thaw stabilizers, bactericides, preservatives, foam regulators, bleaching agents.

»11 :: 13 92496

Experimental part

A granular detergent composition was prepared according to the following table:

Additives Weight% 5 Linear sodium C12 alkyl benzene sulfonate 11.0

Sodium tallow alkyl sulphate 5.0

Tallow alcohol ethoxylate (E011) 0.3

Sodium tripolyphosphate 24.0 10 Bentonite clay 8.5

Dirt suspending agent * 2.0

Proteolytic enzyme 0.9

Sodium sulphate, water, waxy substances equilibration 15 * copolymer of acrylic and maleic acid, molecular weight 60000 (sodium salt).

Two compositions were prepared from the above base composition: Composition A for use as a control, in which cellulase granules containing crude cellulase enzymes and cellulose (1.79% by weight of the total composition) were dry blended with the final composition.

Composition B. The composition of the present invention, wherein the cellulase granules (1.79% by weight of the total composition) contained crude cellulase enzyme, cellulose and polyethylene glycol (5% by weight of the granules, molecular weight 1500) and calcium carbonate coating (10% by weight) of granules.

In both compositions A and B, the cellulase was of the type described in U.S. Patent 4,435,307, and its amounts were such that it gave an activity of 68 CMCase activity units / g of the composition.

Compositions A and B were compared for softness and fabric performance of the fabric.

• · 14 524 96

The design of the experiment was such as to compare the softness of the textile pieces, which were washed 4, 8 and 12 times (multicyclic) each time with the composition of the invention and the reference composition.

5 The experimental conditions were as follows: - use of the product: 92 grams = 0.75% conc.

- washing lamp temperature: 40 ° C.

- water hardness 18 grains / gallon (0.31 g / l) (3: l Ca / Mg ratio).

10 The washed and cord-dried patches were compared by two groups of expert judges who worked independently, using an even comparison method using a 9-point Scheffe scale. Differences were expressed in group point units (psu), with posi-15 seals having better performance. (*) shows significant results with a minimum significant difference (LSD) calculated with 95% confidence.

The test results were as follows: a) Soft cycles maarå ver. B against

20 (bath towels) ver. A

4 +0.38 psu 8 + 1.00 * psu 12 + 0.75 * psu b) Fabric appearance (improved color performance and * 25 anti-quilting performance) (average for main cotton products) number of cycles ver. B against

ver. A

4 + 0.69 * psu 30 8 + 0.75 * psu 12 + 0.75 * psu

The effect of polyethylene glycol coating alone was also measured, and the results showed a negative performance effect, indicating that the positive effect on both softness and fabric appearance was due to the presence of calcium carbonate.

Claims (15)

1S 92496 Patented Applications A finely divided composition for cleaning and softening fabrics, which composition contains 1 to 50% by weight of a surfactant, 1 to 20% by weight of a fabric softening clay material and 1 to 50% by weight of cellulase granules, characterized in that that the granules contain 1 to 50% by weight of said granules of calcium carbonate. Composition according to Claim 1, characterized in that the calcium carbonate is 5 to 15% by weight of the cellulase granules. Composition according to Claim 1, characterized in that the calcium carbonate is applied to the surface of the cellulase granules. Composition according to Claim 1, characterized in that the cellulase is a bacterial or fungal cellulase having a pH optimum of between 5 and 11.5. Composition according to Claim 1, characterized in that the cellulase is an alkaline cellulase having a pH optimum of 6.5 to 9.5. Composition according to Claim 1, characterized in that the composition has a cellulase activity of between 5 and 1360 units of CMCase activity per gram of composition. Composition according to Claim 1, characterized in that the cellulase granules are present in an amount of 1.5 to 10% by weight and the clay material softening the fabric is present in an amount of 2 to 10% by weight. Composition according to Claim 1, characterized in that the clay material which softens the fabric is bentonite clay. Composition according to Claim 1, characterized in that the cellulase granules do not contain titanium dioxide or magnesium silicate. . · 92496 Cellulase granules for use in the composition according to claim 1, characterized in that they contain 1 to 50% by weight of calcium carbonate. Cellulase granules according to Claim 10, characterized in that the calcium carbonate is 5-15% by weight. Cellulase granules according to Claim 10, characterized in that they are coated with calcium carbonate. Cellulase granulates according to Claim 10, characterized in that the cellulase is a bacterial or fungal cellulase having a pH optimum between 5 and 11.5. Cellulase granulates according to Claim 10, characterized in that the cellulase is an alkaline cellulase having a pH optimum of 6.5 to 9.5. Cellulase granules according to Claim 10, characterized in that they do not contain titanium oxide or magnesium silicate. <17 92496