KR950013920B1 - Detergent compositions containing cellulase granulates - 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

Detergent composition containing cellulase granules

The present invention relates to granular detergent compositions that are useful for cleaning and softening fabrics and are beneficial for other fabric protection, such as appearance enhancement and reproducibility.

The composition of the present invention contains a cellulase enzyme in the form of granules containing a fabric-softening clay material and calcium carbonate.

It has been an object of the detergent manufacturing industry to provide detergent compositions which provide the excellent cleaning action expected from detergents and which also exhibit fabric protective properties including softening.

Representatives of such detergent compositions are described in British Patents 1,514,275 and 1,400,898 or European Patent Application 0026 528.

As described in British Patent No. 2,095,275, British Patent No. 2,094,826 or Japanese Patent No. 57108-199, cellulase enzymes have already been used for their detergency in detergent compositions.

Cellulase has also been found to impart flexibility to the fabric as in US Pat. No. 4,435,307.

EP 0 120 528 describes an alkaline softening detergent composition containing a synergistic mixture of a water insoluble C ₁₀ -C ₂₆ tertiary amine and cellulase.

EP 0 177 165 describes an alkaline softening detergent composition containing a mixture of smectite clay and cellulase.

EP 0 220 016 describes the effect of fabric color classification which can be induced using cellulase in the detergent content.

When such detergent and / or emollient compositions are in granular form, the cellulase enzyme is usually incorporated into the composition in granular form and is also identified as a marume or prill supplied from the enzyme manufacturer.

US Pat. No. 4,435,307, which relates to curable reducing agents of detergent compositions, describes the use of cellulase granules, for example for specific non-dusting and color purposes, the specifics required for incorporation into the granules in their preparation. Reference is made to the components.

However, certain of these components have been found to be detrimental to the softening / fabric protection properties of the composition when incorporating cellulase granules containing such components into the detergent composition.

While seeking replacements for these undesirable components, it has been found that the water-insoluble calcium salts according to the present invention surprisingly improve the softening / fabric protection of detergent compositions containing enzyme granules.

It is therefore an object of the present invention to provide detergent compositions having good softening / fabric protection properties by cellulase granules containing water insoluble calcium salts.

The present invention relates to granular detergent compositions containing cellulase granules containing 1 to 50% by weight of the granules, preferably 5 to 15% by weight of calcium carbonate and fabric softening clay materials.

Calcium carbonate is preferably coated on the cellulase granules.

The invention also relates to the cellulase granules themselves described above.

The compositions of the present invention not only can clean and soften the fabric, but also provide advantages in terms of improving the appearance and reproducing the fabric.

This can be achieved by the presence of cellulase granules containing surfactant, fabric softening clay material and calcium carbonate in the granular composition of the present invention.

In the following, these essential and optional ingredients are described in detail.

[Cellulase]

Cellulase useful in the present invention may be any bacterial or fungal cellulase having an optimal pH of 5 to 9.5.

Suitable cellulases are described in US Pat. No. 4,435,307, British Patent No. 2,095,275, German Patent Application Publication No. 2,247,832 and European Patent Application No. 0 220 016.

Examples of these cellulases include the cellulase belonging to the strain of Humicola insolens (Humicola grisea var. Cellulase produced by 212-producing bacteria and cellulase extracted from the liver pancreas of the marine mollusk (Dolabella Auriculs Solander).

Determination of activity for the cellulase of the present invention is based on the hydrolysis of carboxymethyl cellulose. The resulting low molecular weight reduced carbohydrates are measured by calorimetry by ferrocyanide reaction [see; W.S. Hoffman, J. Biol. Chem, 120, 51 (1973). Important conditions of the culture are pH of 7.0, temperature of 40 ° C. and incubation time of 20 minutes.

One unit of CMCase is defined as the amount of enzyme that forms an amount of reducing carbohydrates corresponding to ^10-6 moles of glucose per minute under the conditions described above.

A useful range of cellulase activity of the present invention is 5 to 1360, preferably 60 to 140 CMCase activity unit / detergent composition g.

[Cellulase granules]

Cellulase enzymes for use in granular detergent compositions are typically supplied in the form of granules (marum or prill).

Such granules mainly contain coarse cellulase enzymes and additional components (e.g. typically 5-7% polyethylene glycol and typically about 10% cellulose, wherein the polyethylene glycol used may have a molecular weight ranging from 500 to 8000). It contains.

The amount of cellulase in the granules is determined by the total cellulase activity of the composition falling within the range described above.

Certain substances, such as dust inhibitors and bleaches such as titanium dioxide and magnesium silicate, which have been used by enzyme manufacturers, have been found to adversely affect the softening properties of the compositions of the present invention.

Therefore, the composition of the present invention should preferably contain no titanium dioxide and magnesium silicate.

It has been found by the present invention that calcium carbonate acts as a dust protection when added to the cellulase granules and also provides the unexpected softening / fabric protection advantages as shown below.

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

Calcium carbonate having a particle size range of 1 to 10 mu was found to be particularly suitable for the purposes of the present invention.

The calcium carbonate used in the present invention may be used as it is or in a coated form, typically in a form coated with stearic acid. In a preferred practice of the invention, calcium carbonate, which is previously coated by itself or with, for example, stearic acid, is coated on the cellulase granules.

Cellulase granules are described, for example, in the "Marumerizer" or in Aufbereitungs-Technik No., described, for example, in British Patents 1,362,365 and 1,361,387. 3 / 1970.pp. 147-153 and No. 5/1970, pp. 262-278] can be prepared in a number of different ways, such as using the granulator described, and can be prilled granules as described in Belgian patent specification No. 760,135. In all cases, the granules should have low dusting properties.

In the present invention, calcium carbonate is mixed with other ingredients during granule preparation, with cellulase prior to granulation, or preferably coated onto granules prepared as described above by conventional coating methods.

The cellulase granules according to the invention are present in an amount of 1 to 50% by weight, preferably 1.5 to 10% by weight of the detergent composition of the invention.

[Surfactants]

Surfactants useful in the present invention may be selected from anionic, nonionic, zwitterionic surfactants and are present in amounts of 1 to 50% by weight, preferably 10 to 30% by weight of the composition.

Suitable anionic surfactants include alkyl benzene sulfonates, alkyl sulfates, alkyl polyethoxy ether sulfates, paraffin sulfonates, α-olefin sulfonates, α-sulfocarboxylates and their esters, alkyl glyceryl ether sulfonates, fatty acids Water soluble salts of mono glyceride sulfates and sulfonates, alkyl phenol polyethoxy ether sulfates, 2-acyl oct-alkanes-1-sulfonates and β-alkyloxy alkanes sulfonates.

Particularly preferred alkyl benzene sulfoates are those having from 9 to 15, in particular from 11 to 13, carbon atoms in the straight or branched alkyl chains. Suitable alkyl sulfates are those having 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 chain and have an average of 1 to 12 -CH ₂ CH ₂ O- groups per molecule, in particular 10 to 16 carbon atoms and molecules in the alkyl chain. It has an average of 1 to 6 -CH ₂ CH ₂ O- groups per sugar.

Suitable paraffin sulfonates are essentially straight chain and contain 8 to 24 carbon atoms, more particularly 14 to 18 carbon atoms. Suitable α-olefin sulfonates have 10 to 24 carbon atoms, moreover 14 to 16 carbon atoms, and the α-olefin sulfonate is reacted with sulfur trioxide, and then the particular sultone present is the corresponding hydroxy alkane sulfonate. It is prepared by neutralization under the reaction conditions to be hydrolyzed by. Suitable α-sulfocarboxylates contain 6 to 20 carbon atoms and include salts of α-sulfonated fatty acids prepared from alcohols having 1 to 14 carbon atoms as well as esters thereof.

Suitable alkyl glyceryl ether sulfates are ethers of alcohols having 10 to 18 carbon atoms, more particularly those derived from coconut oil and resins. Suitable alkyl phenol polyethoxy ether sulfates have 8 to 12 carbon atoms in the alkyl chain and have an average of 1 to 6 —CH ₂ CH ₂ O— groups per molecule. Suitable 2-acyloxyalkanes-1-sulfonates have 2 to 9 carbon atoms in the acyl group and 9 to 23 carbon atoms in the alkane residue. Suitable β-alkyloxy alkane sulfonates have 1 to 3 carbon atoms in the alkyl group and 8 to 20 carbon atoms in the alkali residue.

The alkyl chains of the anionic surfactants can be derived from natural sources such as coconut oil or resins, or can be prepared synthetically using, for example, the Ziegler or Oxo Process. Solubility in water can be achieved using alkali metal, ammonium, or alkanol-ammonium cations, with sodium being preferred. Mixtures of anionic surfactants are contemplated by the present invention, and satisfactory mixtures contain alkyl benzene sulfonates having 11 to 13 carbon atoms in the alkyl group and alkyl sulfates having 12 to 18 carbon atoms in the alkyl group.

Suitable nonionic surfactants to be incorporated into the compositions of the present invention are water soluble ethoxylated materials of HLB 11.5 to 17.0 and include C ₁₀ to C ₂₀ primary and secondary alcohol ethoxylates and C ₆ to C ₁₀ alkylphenol ethoxylates. (But not limited to). Preferred are C ₁₄ to C ₁₈ straight chain primary alcohols condensed from 7 to 30 moles of ethylene oxide per mole of alcohol, for example C ₁₄ -C ₁₅ (EO) ₇ , C ₁₆ -C ₁₈ (EO) ₂₅ , and especially C ₁₆ -C ₁₈ (EO) ₁₁ can be mentioned.

Cationic cosurfactant which may be used in the present invention is represented by the general formula _{R 4 R 5 R 6 R 7} N + X - , and [wherein, R ^÷ is alkyl having a carbon number of 10 to 20, preferably 12 to 18, R _5, R ₆ and R ₇ are each C ₁ to C ₇ alkyl, preferably methyl and X ⁻ is an anion (eg chloride). Examples of such trimethyl ammonium compounds include C ₁₂ to C ₁₄ alkyl trimethyl ammonium chloride and cocoalkyl trimethylammonium methosulfate.

The compositions of the present invention should not necessarily contain water-insoluble long-chain alkyl amine emollients and derivatives thereof since they interact adversely with cellulase at the pH conditions of the present invention. Derivatives of amine softeners include the corresponding amine compounds. Such amine softeners are described, for example, in EP 0,026,528 and EP 10,120,528, in particular the amines of the general formula R ₁ R ₂ R ₃ N wherein R ₁ and R ₂ are C ₆ to C ₂₀ alkyl chain, R ₃ is C ₁ to C ₁₀ alkyl chain or hydrogen).

The composition of the invention, measured as a 1% solution of the composition in distilled water, is formulated at a pH of 6.5 to 9.5. In this pH range, cellulase for the use of the present invention has its optimum performance.

[Textile Softening Clay Material]

The composition of the present invention should contain a clay softener.

Such clay softeners are well known in the detergent patent literature and are widely used commercially in Europe and the United States. Such clay softeners include various heat treated kaolins and various multilayer smectites. Preferred clay softeners are described in the literature; Smectite softener clays described in Federal Republic of Germany Patent No. 23 34 899 and British Patent No. 1,400,898.

Most preferred clay fabric softener materials include bentonite-based materials, which are mainly montmorillonite type clays with various impurities, the content and properties of which depend on the source of the clay material. Emollient clays are used in preferred compositions in amounts of at least 1%, generally 1-20%, preferably 2-10%.

[Optional component]

The compositions of the present invention may contain certain optional ingredients in addition to the essential ingredients.

For example, a through-the-wash detergent composition contains detergent enhancers and / or metal ion sequestrants. Compounds that can be classified as detergent enhancers in the art and are well known include nitrilotriacetate, polycarboxylates, citrate, water soluble phosphates such as tri-polyphosphate and sodium ortho- and pyro-phosphate and mixtures thereof. do. Metal ion sequestrants include all such materials ethylenediaminetetraacetate, and the amino-polyphosphonates and a wide variety of other multifunctional organic acids and salts are so numerous that they cannot be described in detail herein. For a typical example of the use of such materials in various detergent compositions, see US Pat. No. 3,579,454. Preferred multifunctional organic acids for use in the present invention are citric acid, ethylene diamine tetramethylenephosphonic acid and diethylenetriaminepentamethylene phosphonic acid.

A further class of detergent enhancer materials useful in the present invention is insoluble sodium aluminosilicate. Particularly preferred for use in low phosphate or non phosphate compositions are 1-10 μ size zeolite (eg zeolite A) enhancers described in Federal Republic of Patent No. 24 22 655. Generally, the enhancer / metal ion sequestrant will contain from 0.5 to 45% of the composition.

The composition of the present invention may also comprise saturated or unsaturated fatty acids and the corresponding soaps. Suitably, saturated or unsaturated fatty acids have 10 to 18 carbon atoms in the alkyl chain. Unsaturated species having 14 to 18 carbon atoms in the alkyl chain are preferred, and ureic acid is most preferred. Corresponding soaps can also be used. Any fatty acid / soap is used in amounts up to 20%.

The composition of the invention is also a general formula R-CH (COOH) CH ₂ (COOH) which is a derivative of succinic acid, wherein R is C ₁₀ to C ₂₀ , preferably C ₁₂ to C ₁₆ alkyl or alkenyl, R may be substituted by hydroxyl, sulfo, sulfoxy or sulfone substituents.

Succinate enhancers are preferably used in the form of their water-soluble salts, including sodium, potassium, ammonium and alkanolammonium salts.

Specific examples of succinate enhancers include lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenyl succinate (preferably), 2-pentadecenyl succinate, and the like.

Also useful as enhancers in the present invention are those compounds described in US Pat. No. 4,663,071, i.e. tartrate monosuccinic acid and tartrate disuccinic acid (monosuccinic acid to disuccinic acid have a weight ratio of 97: 3 to 20:80, preferably 95: 5 to 40: 60).

Another optional ingredient is bleach. Peroxygen bleaches such as sodium perborate (commercially available in the form of mono- and tetra-hydrates), sodium carbonate peroxyhydrate, sodium pyrophosphate peroxyhydrate and urea peroxyhydrate are preferred.

Bleach activators can be used in combination with the peroxygen bleach. Classes of bleach activators include esters, imides, imidazoles, oximes and carbonates. Methyl o-acetoxy benzoate in this class; Sodium-p-acetoxy benzene sulfonate (eg sodium 4-octanoyloxybenzene sulfonate); Sodium-4-octanoyl oxybenzene sulfonate and sodium-4-decanoyloxy benzenesulfonate; Biphenol diacetate; Tetraacetyl ethylene diamine; Tetraacetyl hexamethylene diamine; And tetra acetyl methylene diamine are preferred materials.

Other highly preferred peroxygen bleach activators described in US Pat. Nos. 4,483,778 and 4,539,130 are α-substituted alkyl or alkenyl esters [eg; Sodium-4 (2-chlorooctanoyloxy) benzene sulfonate and sodium 4- (3,5,5-trimethylhexanoyloxy) benzene sulfonate]. Suitable peroxy acids are also the general formulas RXAOOH and RXAL as described in EP 0 166 571, wherein R is a hydroxylcarbyl group, X is a heteroatom, and A is a carbonyl bridge group. and L is a leaving group] peroxygen bleach activator, in particular oxybenzene sulfonate.

In addition to the cellulase of the present invention, enzymes other than cellulase (e.g., proteolytic, nutrient starch, or lipolytic enzymes) can be used.

Contaminant removers / contaminant suspending agents may also be present in the compositions, typically in amounts of 0.1 to 10% by weight. In particular, it is possible to use alkoxylated polyamines suitable as clay decontamination agents / antideposition agents. These components and also their preparations are described in European Patent Application No. 0 112 593.

The term "polyamine" as used herein generally refers to an alkoxylated polyamine in both amine form and quaternized form. Such materials can be conveniently represented as molecules of an empirical formula having the following repeating units:

Wherein R is usually a hydrocarbyl group having 2 to 6 carbon atoms; R ¹ may be C ₁ to C ₂₀ hydrocarbon; (Alkoxy) groups are ethoxy, propoxy and the like; y is 2 to 30, most preferably 10 to 20; n is an integer of 2 or more, preferably 2 to 20, most preferably 3 to 5; X ⁻ is an anion such as halide or methyl sulfate resulting from the quaternization reaction.

Most preferred polyamines for use in the present invention are ethoxylated polyethylene imines of the general formula: a polymerization product of ethylene oxide and ethylene-amine:

Wherein n is an integer from 3 to 5 and y is an integer from 10 to 20.

The contaminant suspending agent may also be selected from polyethylene glycols, polyacrylates having a molecular weight of 400 to 1000, or copolymers of acrylic acid and maleic anhydride / maleic acid.

The detergent composition of the present invention is preferably free of carboxymethyl cellulose.

In addition, the compositions of the present invention may contain not only the aforementioned components, but also various other optional components that are commonly used to provide an advantage in appearance or additional product performance. Typical ingredients include pH adjusters, fragrances, dyes, optical brighteners, hydrotrope and gel adjusters, cold-thaw adjusters, fungicides, preservatives, foam control agents and bleach stabilizers.

[Experimental part]

Granular detergent compositions are prepared according to the following table:

Component weight%

Straight Sodium C ₁₂ Alkyl Benzene Sulfonate 11.0

Sodium Tallow Alkyl Sulfate 5.0

Tallow Alcohol Ethoxylate (EO11) 0.3

Sodium tripolyphosphate 24.0

Bentonite Clay 8.5

Contaminant Suspension ^* 2.0

Protease 0.9

Sodium sulfate, water, and other equilibrium amounts

* Copolymer of maleic acid maleic acid having a molecular weight of 60,000 (sodium salt) From the basic composition described above, two compositions are prepared:

Composition A: Obtained by anhydrous mixing of cellulase granules (1.79% by weight of the total composition) with crude cellulase enzyme and cellulose, for reference.

Composition B: Cellulase granules (1.79% by weight of the total composition) containing a coating of coarse cellulase enzyme, cellulose and polyethylene glycol (5% by weight MW 1500 in granules) and calcium carbonate (10% by weight in granules) Obtained accordingly.

In both compositions A and B described above, the cellulase is in the form described in US Pat. No. 4,435,307, the amount of which provides an activity of 68 CMCase active units per gram of composition.

The softness and fabric protection performance of Compositions A and B are compared.

The test is planned to compare the softness of the fabric pieces washed four, eight and twelve (multicycle) with the compositions of the present invention and the control composition, respectively.

Test conditions are as follows:

Handling product: 92 g = 0.75% concentration

-Washing temperature: 40 ℃

18 grain / gallon (0.31 g / l) water hardness

(3: 1 Ca / Mg ratio)

Washed and line dried springs are compared by two experts, each performing independently using a comparison technique using a 9-point Scheffe scale. The difference is reported in panel score units (psu) indicating positive values when excellent. (*) Indicates a valid result with a calculated minimum significant difference (LSD) of 95% confidence interval.

a) flexibility recovery component B: component A

(Bath towel) 4 + 0.38psu

8 +1.00 ^* psu

12 75 ^* psu

b) fabric appearance [enhanced color and anti-pilling performance] (usually average value in cotton)

Recovery Composition B: Composition A

4 +0.69 ^* psu

8 +0.75 ^* psu

12 +0.75 ^* psu

The effect of the polyethyleneglycol coating alone is easily measured and the measurement results show a negative performance effect, so the positive effect on both flexibility and fabric appearance seems to be due to the presence of calcium carbonate.

Claims (9)

1) 1 to 50% by weight of a surfactant selected from anionic, nonionic and zwitterionic surfactants, 2) 1 to 20% by weight of fabric softening clay material, and 3) 1 to 50% by weight of cellulase granules. A granular composition for cleaning and softening, wherein the cellulase granules contain from 1 to 50% by weight of water insoluble calcium salt and at least 50% by weight of cellulase enzyme. The composition of claim 1, wherein the water insoluble calcium salt is present in an amount of from 5 to 15% by weight of the cellulase granules. The composition of claim 1 wherein the water insoluble calcium salt is coated on the cellulase granules. The composition of claim 1 wherein the water-insoluble calcium salt is calcium carbonate. The composition of claim 1 wherein the cellulase is a bacterial or fungal cellulase having an optimal pH of 5 to 11.5. The composition of claim 1 wherein the cellulase is an alkaline cellulase having an optimal pH of 6.5 to 9.5. The composition of claim 1 wherein the cellulase activity is between 5 and 1360 CMCase active units per gram of composition. The composition of claim 1, wherein the cellulase granules are present in an amount of 1.5 to 10% by weight and the fabric softening clay material is present in an amount of 2 to 10% by weight. The composition of claim 1 wherein the fabric softening clay material is bentonite clay.