DK164708B - Detergent compositions which comprise cellulase granulates, and cellulase granulates for use therein - 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

DK 164708 B

The present invention relates to granular detergent compositions which can be used for washing and softening fabrics, as well as to provide other beneficial effects on the clothing such as an improved appearance and that the fabric does not look worn.

The compositions of this specification contain a clay material for fabric softening and a cellulase enzyme in the form of granules containing calcium carbonate.

It has been the goal of many detergent manufacturers to formulate the detergent compositions for laundry which provide the good washability expected of them and which also exhibit beneficial properties on the laundry, including a softening effect.

Typical examples of such detergent compositions are disclosed in British Patent No. 1,514,275 1,400,898 or EPA No. 0.026,528.

Cellulase enzymes have already been used in detergent compositions because of their washability, as described in British Patent Application GB-A 2,095,275, GB 2,094,826 or Japanese Patent Nos. 57-108,199.

Cellulases have also been found to produce softening properties in textiles as disclosed in U.S. Patent No. 4,435,307.

European Patent Application No. 0,120,528 discloses 25 alkaline softening detergent compositions comprising a synergistic mixture of a water-insoluble C10-C2g tertiary amine and cellulase.

European Patent Application No. 0,177,165 discloses alkaline detergent compositions containing a mixture of 30 smectites and cellulase.

European Patent Application No. 0,220,016 discloses the color-clarifying effect on the substance which can be obtained by the use of cellulase in conjunction with detergent.

When such detergent and / or softening compositions are in granular form, the cellulase enzymes are usually incorporated into the composition in the form of granules also identified as "marbles" or "prills" sold by the enzyme manufacturers.

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2 U.S. Patent No. 4,435,307, which relates to a hardness reducing agent for detergent compositions, discloses the use of cellulase granules, and mentions certain ingredients to be incorporated into the granules during their preparation, e.g. to avoid dust or for the sake of color.

However, it has been found that some of these ingredients are detrimental to the effect of the composition on the softness / substance appearance when cellulase granules containing these ingredients are incorporated into the detergent composition.

10 In an attempt to replace these undesirable ingredients, it has now surprisingly been found that water-insoluble salts of calcium significantly improve the good effect on the softness / substance appearance of detergent composition containing enzyme granules.

It is thus an object of the invention to provide detergent compositions which exhibit excellent properties in terms of softness and the appearance of the substance using cellulase granules containing a water-insoluble salt of calcium.

The present invention relates to a particulate composition for washing and softening textiles containing 1 to 50% by weight of surfactant, 1 to 20% by weight of clay softening material and 1 to 50% by weight of cellulase granules, characterized in that said granules contain from 1 to 50% by weight of calcium carbonate of the above granules.

Preferably, calcium carbonate is used to coat cellulase granules.

The invention further relates to the above cellulase granules per se.

The compositions of the invention can wash and soften the treated fabric as well as provide beneficial effects in terms of improved appearance and appearance of the fabric.

This is achieved in the presence of surfactants, textile softeners of clay and cellulase granules containing calcium carbonate in the granular composition of the invention.

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3 In the following, these necessary as well as optional ingredients are described in more detail:

The cellulase

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

Suitable cellulases are disclosed in U.S. Patent No. 4,435,307, British Patent Application No. 2,095,275, West German Patent Publication No. 2,247,832, and European Patent Application No. 0,220,016.

Examples of such cellulases are cellulases made from a strain of Humicola insolens (Humicola qrisea var, thermoidea), especially from the Humicola strain DSM 1800, and cellulases made by a fungus from Bacillus N 15 or a cellulase 212-forming fungus of the species Aero -monas, and cellulase extracted from hepatopancreas from a mollusc (Dolabella Auricula Solander).

Determination of activity of the cellulase herein is based on the hydrolysis of carboxymethyl cellulose. Formed low molecular weight reducing carbohydrates are determined colorimetrically by ferrocyanide reaction, as described by W.S. Hoffman "J.Biol.Chem." 120.51 (1973). The main conditions for incubation are pH = 7.0, a temperature of 40 ° C and an incubation time of 20 minutes.

A CMCase unit is defined as the amount of enzyme per minute produces an amount of reducing carbohydrate corresponding to 10-6 moles of glucose under the above conditions.

A useful range of cellulase activity in this context ranges from 5 to 1360, preferably from 60 to 140 CMCase activity units per cell. g of detergent composition.

Cellulasegranulaterne

Cellulase enzymes for use in granular detergent compositions are typically sold in the form of granules, e.g. "marumer" or "priller".

Such granules contain a large amount of coarse cellulase enzyme as well as additional ingredients such as polyethylene

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4 langlycol in typical amounts from 5% to 7%, and cellulose. in typical amounts of approx. 10%. The polyethylene glycol used herein may have a molecular weight in the range of 500 to 8000.

The amount of cellulase in the granules is determined by the total cellulase activity of the composition to be within the range indicated above.

It has been found that certain materials used in the enzyme preparation to prevent dust formation 10 and as bleaches, namely titanium dioxide and magnesium silicate, adversely affect the softening effect of the compositions of this specification.

Therefore, the compositions of the invention should preferably be free of titanium dioxide and magnesium silicate.

It has now been found that calcium carbonate prevents dust formation when added to the cellulase granules, and further produces an unexpectedly beneficial effect on the softness / appearance of the fabric as shown below.

The calcium carbonate is present in the cellulase granules in amounts of from 1 to 50%, preferably 5 to 15% by weight of the granules.

Calcium carbonates in a particle size range from 1 to 10 µm have been found to be particularly suitable for the purposes of this invention.

The calcium carbonate used in the specification may be used as is or in coated form; typically it is coated with stearic acid. In a preferred embodiment of the invention, the cellulase granules are coated with calcium carbonate either as it is or already coated, e.g. with stearic acid.

Cellulase granules can be prepared in a variety of ways, e.g. by a "Marumerizer®" as disclosed in British Patent Nos. 1,362,365 and 1,361,387 or by a granulator as described in Aufbe-reitungs-Technik No. 3/1970, pp. 147-153 and No. 5 / 1970, pp. 262-278, or they may be prilled granules as described in Belgian Patent Application No. 760,135. In all cases, the granules should have a low dust level.

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5

The calcium carbonate herein is either blended with other ingredients during the preparation of the granules or mixed with cellulase prior to the granulation, or preferably 'used to coat the granules prepared according to the above, by conventional coating methods.

The cellulase granules of the invention occur in amounts of from 1 to 50% by weight of the detergent composition herein, preferably 1.5 to 10% by weight.

10 Surfactant

The surfactant used herein can be selected from anionic, non-ionic, zwitterionic surfactants and is present in amounts of from 1 to 50% by weight of the composition, preferably from 10 to 30%.

15 Suitable anionic surfactants are water-soluble salts of alkylbenzene sulfonates, alkyl sulfates, alkyl polyethoxy ether sulfates, paraffin sulfonates, alpha-olefin sulphonates, alpha-sulphocarboxylates, and their esters, alkylglyceryl ether sulphonates, fatty acids, fatty acids. beta-alkyloxyalkansulphonater.

Particularly preferred alkylbenzene sulfonates have 9 to 15 carbon atoms in a linear or branched alkyl chain, especially from 11 to 13 carbon atoms. Suitable alkyl sulfates have from 10 25 to 22 carbon atoms in the alkyl chain, especially from 12 to 18 carbon atoms. Suitable alkyl polyethoxyether sulfates have from 10 to 18 carbon atoms in the alkyl chain and have an average of from 1 to 12 - CH 2 CH 2 groups per molecule, especially from 10 to 16 carbon atoms in the alkyl chain and an average of from 1 to 6 to 30 CH 2 CH 2 groups per molecule.

Suitable paraffin sulfonates are substantially linear and contain from 8 to 24 carbon atoms, especially from 14 to 18 carbon atoms. Suitable alpha-olefin sulfonates have from 10 to 24 carbon atoms, especially from 14 to 16 carbon atoms; 35 alpha-olefin sulfonates can be prepared by reaction with sulfur trioxide, followed by neutralization under conditions so that all the sultones present are hydrolyzed to the

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6 corresponding hydroxyalkanesulphonates. Suitable alpha-sulphocarboxylates contain from 6 to 20 carbon atoms; included are not only the salts of alpha-sulfonated fatty acids, but also their esters, prepared from alcohols containing 5 1 to 14 carbon atoms.

Suitable alkylglyceryl ether sulphates are ethers of alcohols having from 10 to 18 carbon atoms, especially those derived from coconut oil and sebum. Suitable alkylphenol polyethoxy ether sulfates have from 8 to 12 carbon atoms in the alkyl-10 chain and an average of from 1 to 6 -CH2CH2O groups per molecule. Suitable 2-acyloxyalkane-1-sulfonates contain from 2 to 9 carbon atoms in the acyl group and from 9 to 23 carbon atoms in the alkane moiety. Suitable beta-alkyloxyalkanesulfonates contain from 1 to 3 carbon atoms in the alkyl group and from 8 15 to 20 carbon atoms in the alkane moiety.

The alkyl chains of the aforementioned anionic surfactants can be obtained from natural sources such as coconut oil and sebum, or they can be synthetically prepared, e.g. using the Ziegler or Oxo methods.

Water solubility can be achieved by the use of alkali metal, ammonium or alkanolammonium cations: sodium is preferred. Mixtures of anionic surfactants are contemplated by this invention; a satisfactory mixture contains alkylbenzene sulfonates having 11 to 13 carbon atoms in the alkyl group and alkyl sulfate having 12 to 18 carbon atoms in the alkyl group.

Suitable nonionic surfactants to be incorporated into the compositions listed below are water-soluble ethoxylated materials of HLB 11.5 - 17.0, and include (but are not limited to) C10-C20 primary and secondary alcohol ethoxylates and c6 “ClO alkylphenol ethoxylates. c14 "c18 linear Primary alcohols condensed with from 7 to 30 moles of ethylene oxide per mole of alcohol are preferred, examples of which are C14-C15 (E0) 7, C16-C18 (EO) 25 and especially C16-35 C18 (EO) - j ^ ·

Cationic co-surfactants which can be used herein include water-soluble quaternary ammonium compounds of the formula R4R5R667N + X, wherein R4 is alkyl with

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7 from 10 to 20, preferably from 12 to 18, carbon atoms, and R 1, R 9 and R 7 are each C 1 to Cy alkyl, preferably methyl; X is an anion, e.g. chloride. Examples of such trimethylammonium compounds include C1-2 Cl4 alkyltrimethylammonium chloride and cocoalkyltrimethylammonium methosulfate.

The compositions of the invention are preferably substantially free of water-insoluble long-chain alkylamine plasticizers and derivatives thereof, since they have been found to act negatively with cellulase at the pH conditions of the present invention. Derivatives of the amine plasticizers include the corresponding amine compounds. Such amine plasticizers are described in e.g. European patent applications Nos. 0.026.528 and 0.120.528, and in particular comprise amines of the formula R 1 R 2 R 3 N 'wherein R 1 and R 2 are C 9 to C 20 alkyl chains and R 3 is C 3 to C 10 alkyl chain or hydrogen.

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

The clay material for soft-tube textiles

The compositions of this specification should contain a clay softener.

Such clay softeners are well known in the patent literature on detergents and their detergents and are widely used commercially both in Europe and in the United States. Such clay softeners include various heat-treated kaolins and different types of layered smectite. Preferred clay softeners are 30 softening smectite clays described in West German Patent Specification No. 23 34899 and in British Patent No. 1,400,898, to which reference may be made for detailed information.

The most preferred clay materials for fabric softening include materials of bentonitic origin, with 35 bentonites being primarily montmorillonite type clays together with various impurities where the amount and nature of these

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8 depends on the source of the clay material. Clay softeners are used in amounts of 1 - 20%, preferably 2 - 10%.

Optional ingredients

The compositions of this specification may contain, in addition to the 5 basic ingredients, certain optional ingredients. Eg. it is preferred that full detergents contain a detergent builder and / or metal ion sequestrant. Compounds described in the technical literature which can be classified and known as detergent builders include 10 nitrilotriacetates, polycarboxylates, citrates, water-soluble phosphates such as tripolyphosphate and sodium ortho and pyrophosphates and mixtures thereof. Metal ion sequestrants include the above as well as materials such as ethylene diamine tetraacetate, the aminopolyphosphonates, and a large number of 15 other polyfunctional organic acids and salts, which will be too extensive to mention in detail herein. See US Patent No. 3,579,454, which contains typical examples of the use of such materials in various washing compositions. Preferred polyfunctional organic acid species for use in this specification are citric acid, ethylenediaminetetramethylene phosphonic acid, and diethylenetriamine pentamethylene phosphonic acid.

A further builder material for washing which can be used in the present invention are insoluble sodium aluminosilicates. Builders consisting of zeolite in the size of 1-10 25 μιη (eg zeolite A) described in West German Patent No. 24,22,655 are particularly preferred for use in low or no phosphate compositions. Generally, from 0.5% to 45% of the composition will be builder / sequestering agent.

The compositions herein may further contain saturated or unsaturated fatty acids and the corresponding soaps. Suitable saturated or unsaturated fatty acids have from 10 to 18 carbon atoms in the alkyl chain. Unsaturated acids having from 14 to 18 carbon atoms in the alkyl chain are preferred, most preferably 35 oleic acid. The corresponding soaps can also be used. Optional. fatty acids / soaps are used in amounts up to 20%,

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9

The compositions of this specification may also contain compounds of the general formula R-CH (COOH) CH 2 (COOH), i.e. derivatives of succinic acid wherein R is C 10 -C 2 C 1-6 alkyl. or alkenyl, preferably c1-2-c6 'or wherein R can be substituted with hydroxyl, sulfo, sulfoxy or sulfone substituents.

The succinate builders are preferably used in the form of their water-soluble salts, including the sodium, potassium, ammonium and alkanol ammonium salts.

Specific examples of succinate builders include: 10 lauryl succinate, myristyl succinate, palmitylsuccinate, 2-dodecenyl succinate (preferred) and 2-pentadecenyl succinate.

Further, the compounds disclosed in U.S. Patent No. 4,663,071, i.e. mixtures of tartrate monoracic acid and tartrate diravic acid in a weight ratio monoracic acid: diravic acid of 15 from 97: 3 to 20:80, preferably 95: 5 to 40:60, useful in this context.

Another optional ingredient is a bleach. Preferred bleaches are peroxygen agents such as sodium perborate which are commercially available in the form of mono- and tetrahydrates, sodium carbonate peroxyhydrate, sodium pyrophosphate-peroxyhydrate, and ureaperoxyhydrate.

Bleach activators can be used with the above peroxygen bleaches. The nature of bleach activators includes esters, imides, imidazoles, oximes and carbonates. Of these 25, preferred materials include methyl o-acetoxybenzoates? sodium p-acetoxybenzenesulfonates such as sodium 4-octanoyl oxybenzenesulfonate; sodium 4-octanoyloxybenzenesulfonate, and sodium 4-decanoyloxybenzenesulfonate: biophenol diacetate; tetraacetylethylenediamine; tetraacetylhexamethylendiamin; Tetraacetylmethylenediamine.

Other particularly preferred peroxygen bleach activators described in U.S. Patents Nos. 4,483,778 and 4,539,130 are alpho-substituted alkyl or alkenyl esters such as sodium 4 (2-chlorooctanoyloxy) benzenesulfonate, sodium 4- (3, 5, 5-trimethylhexanoyloxy) benzene. Suitable peroxyacids are also peroxygen bleach activators, as described in published European Patent Application No. 0,166,571, namely compounds of the general type RXAOOH and RXAL, where R is a

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X is a heteroatom, A is a carbonyl "bridging group" and L is a leaving group, especially oxybenzene sulfonate.

Enzymes other than cellulases such as proteolytic, amylolytic or lipolytic enzymes can be used with the cellulase herein.

Dirt removal agents / dirt suspending agents may be present in the composition of this specification in amounts typically ranging from 0.1% to 10% by weight. In particular, alkoxylated polyamines suitable as dirt removal with clay / antifouling agents may be used. These components and their preparation are described in European Patent Application No. 0,112,593.

It is to be understood that the term "polyamines" used in this specification represents in generic form alkoxylated polyamines, both as amine and in quaternized form. Such materials can most easily be described as molecules of empirical structure with repeating units: 20 - N - R - Aminform L -I n (Alkoxy) y and 25 R1 - N + - R - X Quaternized J n form 30 (Alkoxy) y where R is a hydrocarbyl group, usually having from 2 to 6 carbon atoms; R1 may be a C1-C20 carbohydrate; the alkoxy groups are ethoxy, propoxy and the like, and γ is 2-30, most preferably 10-20; n is an integer of at least 2, preferably 2-20, most preferably 3-5; and X 'is an anion such as halide or methyl sulfate from the quaternizing reaction.

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11

The most preferred polyamines for use in this specification are the so-called ethoxylated polyethyleneimines, i.e. the polymerized reaction product of ethylene oxide with ethyleneimine of the general formula: 5 (EtO) - N - CH2 - CH2 - N - (Eto) y * - - * n (EtO) y (EtO) y 10 where n is an integer of 3 to 5 and y is a unit of 10 to 20.

Furthermore, dirt suspending agents can be selected from polyethylene glycols of molecular weight 400 to 1000, polyacrylates or copolymers of acrylic acid and maleic acid / anhydrate.

The detergent compositions of this specification are preferably free of carboxymethyl cellulose.

In addition to the ingredients already mentioned, the compositions of this specification may further contain various other optional ingredients typically used in commercial products to provide products with aesthetic or other beneficial effects. Typical ingredients include pH regulators, perfumes, dyes, optical whites, hydrotropes and gel controllers, freeze / thaw stabilizers, bactericides, preservatives, antifoam, bleach stabilizers.

EXAMPLE

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

Ingredients Weight% 12

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Sodium linear C12 alkyl benzene sulfonate 11.0

Sodium talgalkyl sulfate 5.0

Tallow alcohol ethoxylate (E011) 0.3 Sodium tripolyphosphate 24.0

Bentonitles 8.5

Dirt suspension agent * 2.0

Proteolytic enzyme 0.9 sodium sulfate, water, miscellaneous up to 100 10 * Copolymer of acrylic and maleic acid, molecular weight 60,000 (sodium salt)

Of the above-mentioned basic composition, two compositions were prepared:

Composition A, for comparison, in which cellulase granules (1.79% by weight of the total composition) containing coarse cellulase enzymes and cellulose were dry mixed with the rest of the composition.

Composition B. a composition according to the invention wherein cellulase granules (1.79% by weight of the total composition) containing coarse cellulase enzymes, cellulose and a coating of polyethylene glycol (in an amount of 5% by weight of granules, molecular weight 1500) and calcium carbonate (in an amount of 10% by weight of granules).

In both Composition A and B, the cell lulase was of the type described in U.S. Patent No. 4,435,307 and in such amounts that an activity of 68 CMCase activity units / g of composition was obtained.

Softening effect and effect on the appearance of the substance in compositions A and B were compared.

30 The test was performed in such a way as to compare the softening effect of textile pieces that were

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13 washed 4, 8 and 12 times (multi-cycle) each time with the composition of the invention and the comparative composition. The test conditions were as follows: - Product consumption: 92 g = 0.75% concentration 5 - Wash temperature: 40 ° c - 18 grains / gallon (0.31 g / 1) water hardness (Ca / Mg 3: 1 ratio).

After washing and drying on a drying line, the patches were compared by a panel consisting of two, independently working expert judges by a pairwise comparison technique using a 9-point Scheffe scale. Differences in rating were listed in panel scoring units (psu), with a positive result indicating better performance. (*) indicates significant results with the least significant difference (LSD) 15 calculated as 95% confidence.

The test results were as follows:

a) Softness number of cycles Comp. B: Comp. A

(bath towels) 4 +0.38 psu 8 + 1.00 * psu 20 12 + 0.75 * psu b) Appearance of the fabric (improved color and lint properties) (cotton average) Number of cycles Comp. B: Comp. A 25 4 + o, 69 * psu 8 + 0.75 * psu 12 + 0.75 * psu

The effect of coating with polyethylene glycol alone was also measured and the results showed a negative effect, of which it is seen that the positive result on the softening effect and appearance of the substance is due to the presence of calcium carbonate.

Claims (15)

A particulate composition for washing and softening textiles containing 1 to 50 wt% surfactant, 1 to 20 wt% clay material for fabric softening 5 and 1 to 50 wt% cellulase granules, characterized in that said granules contain from 1 to 50% by weight of calcium carbonate of the above granules. A composition according to claim 1, wherein calcium carbonate is present in amounts of from 5 to 15% by weight of the cellulase granules. A composition according to claim 1, wherein the cellulase granules are coated with the calcium carbonate. A composition according to claim 1, wherein the cellulase is bacterial or fungal cellulase having a pH optimum between 5 and 11.5. A composition according to claim 1, wherein the cellulase is an alkaline cellulase having a pH optimum of 6.5 to 9.5. A composition according to claim 1, wherein the composition has a cellulase activity of from 5 to 1360 CMCase activity units / g composition. A composition according to claim 1, wherein the cellulase granules are present in an amount of from 1.5 to 10% by weight and the clay material for fabric softening is present in an amount of from 2 to 10% by weight. A composition according to claim 1, wherein the clay material for fabric softening is of the bentonite type. DK 164708 B A composition according to claim 1, wherein the cellulase granules do not contain titanium dioxide and magnesium silicate. The cellulase granules for use in the composition of claim 1, wherein they contain from 1 to 50% by weight of calcium carbonate. The cellulase granules of claim 10, wherein calcium carbonate is present in amounts of from 5 to 15% by weight. Cellulase granules according to claim 10 coated with the calcium carbonate. The cellulase granules of claim 10, wherein the cellulase is bacterial or fungal cellulase having a pH optimum between 5 and 11.5. The cellulase granules of claim 14, wherein the cellulase is an alkaline cellulase having a pH optimum between 6.5 and 9.5. Cellulase granules according to claim 10 which do not contain titanium oxide and magnesium silicate.