PT78654B

PT78654B - Process for preparing sabilised built single-phase liquid dete rgent composition containing enzymes

Info

Publication number: PT78654B
Application number: PT78654A
Authority: PT
Inventors: Jack Thomas Inamorato; Michael Christopher Crossin
Original assignee: Colgate Palmolive Co
Priority date: 1983-05-31
Filing date: 1984-05-28
Publication date: 1986-08-05
Also published as: ES8706808A1; NZ208157A; ZA843666B; IT1177763B; ES532929A0; NL8401741A; DK269184A; GB2140818A; DK165187B; DE3418295A1; HK18392A; PT78654A; DK269184D0; CH659478A5; LU85391A1; PH20171A; IT8448276A0; SE8402870L; AU2831584A; DK165187C

Abstract

A stabilized built single-phase enzyme-containing liquid detergent composition is provided comprising: (a) 3 to 10%, by weight, of a surface active nonionic detergent compound; (b) 3 to 15% of a surface active amphoteric detergent compound; (c) 5 to 25% of a non-phosphate detergent builder salt; (d) an effective amount of an enzyme or enzyme mixture selected from alkaline protease enzymes and alpha-amylase enzymes; (e) 3 to 15% of an enzyme stabilizing system consisting of (i) glycerine and (ii) a boron compound or mixture consisting of boric acid, boric oxide or an alkali metal borate capable of reacting with the glycerine; and (f) 30-85% water. -

Description

DETAILED DESCRIPTION OF THE INVENTION

The enzyme stabilizing system object of this invention is a mixture of glycerin and a boron compound selected from the group consisting of boric acid, boric oxide and an alkali metal borate capable of reacting with glycerin. The weight of the stabilizing system in the present structured detergent compositions is from about 3 to 15%, preferably from 4 to 10% by weight. Mixtures of glycerin and borax are especially useful for providing stability of the enzymes, the weight ratio of glycerin to borax in such stabilizer mixtures being generally about 1, 2 to 3, with a ratio of about 1, 5 to 2.5. Accordingly, the preferred amount of glycerin in the composition is about 3 to 7%, the preferred amount of borax is about 1 to 4%, based on the weight of the composition. Suitable alkaline proteolytic enzymes for the present compositions include the various liquid commercial preparations with enzymes which have been adapted for use in detergent compositions, and preparations with enzymes in the form of powder are also useful, although, as a rule, they are less convenient for incorporation into detergent compositions liquidity. Thus, suitable liquid enzyme preparations include Alcalase and Etherase sold to Novo Industries, Copenhagen, Denmark and Maxatase and ΆΖ-Protease sold by Gist-Brocades, Delft, The Netherlands.

Suitable liquid preparations of β-amylases are sold to Novo Industries and Gist-Brocades under the trademarks Termamyl and Maxamyl, respectively.

8 =.

PORTUG. '"

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"Esperase" is particularly preferred for the present compositions because of its optimized activity with high pH values corresponding to the structured detergent compositions.

The nonionic and amphoteric synthetic detergents used in the process of the invention may be any of a wide variety of those compounds which are well known and are described throughout the text "Surface Active Agents". Vol. II, by Schwartz, Peny and Berch, published in 1958 by Interscience Publishers, the important disclosures of which are hereby incorporated by reference.

Nonionic detergents are usually poly-lower alkoxy lipophiles characterized in that the desired hydrophilic-lyophilic balance is obtained by the addition of a hydrophilic, poly-lower alkoxy group to a lipophilic moiety. For the present compositions the nonionic detergent used is preferably a poly (lower) alkoxylated lower alkanol, characterized in that the alkanol includes 10 to 18 carbon atoms and in that the number of moles of the lower alkylene oxide (2 to 3 carbon atoms) include from 3 to 12. Of such materials it is preferred to use those characterized in that the higher alkanol is a higher fatty alcohol of 11 or 12 to 15 carbon atoms, consisting of 5 to 8 or 5 to 9 lower per mol. Preferably, the lower alkoxy is ethoxy, but in some cases may be desirably mixed with propoxy, the latter usually being, if present, a minor (lower than 50%) component. As models of such compounds are those characterized in that the alkanol is 12 to 15 carbon atoms and consists of about 7 ethylene oxide groups per mole, for example, Neodol 25-7 Neodol 23-6, 5, which are manufactured by Shell Chemical

The first is a condensation product of a mixture of higher fatty alcohols having on average about 12 to 15 carbon atoms with about 7 moles of ethylene oxide and the second is a corresponding mixture, characterized in that the carbon atom content of the higher fatty alcohol is from 12 to 13 and the number of ethylene oxide groups per mole is on average about 6.5 ·

The higher alcohols are primary alkanols. Other examples of such detergents include Tergitol® 15-S-7 θ Tergitol 15-S-9, which are both linear secondary alcohol ethoxylates, manufactured by Union Carbide Corporation. The first is a mixed ethoxylation product of a linear secondary alkanol of 11 to 15 carbon atoms with seven moles of ethylene oxide, and the second is a similar product but in which nine moles of ethylene oxide are reacted.

Also useful in the present compositions are the higher molecular weight nonionics such as Neodol 45-11, which are similar condensation products of ethylene oxide of higher fatty alcohols, the respective higher fatty alcohol having 14 to 15 carbon atoms and having the number of ethylene oxide groups per mole of about 11. Such products are also manufactured by the Shell Chemical Company. Other useful nonionics are shown under the designation Plurafac B-26 (BASF Chemical Company), a reaction product of a higher linear alcohol and a mixture of ethylene and propylene oxides.

In the case of preferred poly-lower alkoxy (lower) alkanes, the best balance of hydrophilic and lipophilic fractions is obtained when the number of lower alkoxys is from about 40% to 100% of the number of carbon atoms in the higher alcohol, preferably 40 to 60% of those numbers. The nonionic detergent preferably consists of at least 5% of the preferred ethoxylated alkanols.

The higher molecular weight alkanols and various other normally solid nonionic detergent compounds and surface active agents may contribute to the liquid detergent composition becoming gel and therefore are normally omitted or limited in quantity in the present compositions, although smaller proportions can be used due to their cleaning properties, etc. With respect to both the preferred and the least preferred nonionic detergents, the alkyl groups present therein are preferably linear, although a minor degree of slight branching, such as a carbon or two carbon atoms near the terminal carbon of the straight chain away from the ethoxy chain, with the proviso that one such branched alkyl contains no more than three carbons in length. Usually the proportion of carbon atoms in such a branched configuration will be less, rarely exceeding 20% of the total alkyl carbon content. Similarly, although linear alkyls, which are terminally bonded to the ethylene oxide chains, are highly preferred and are considered to be capable of resulting in an optimal combination of detergency, bio-degradability and non-gel formation characteristics, they may in the chain chain medium or secondary to ethylene oxide. In this case, such

usually only occurs in a minor proportion of those alkyls, generally less than 20%, but in the case of the above mentioned Tergitols the ratio may be higher. Likewise, when the propylene oxide is present in the lower alkylene oxide chain, it will usually represent less than 20% thereof, and preferably less than 10%.

Amphoteric detergents include sulfates or sulfonates, phosphates and higher fatty carboxylates. which contain a cationic substituent, such as an amino group, which may be quaternized, for example, with a lower alkyl group, or by extending the chain on the amino group by condensation with a lower alkylene oxide, for example ethylene oxide.

Examples of suitable amphoteric detergents include: alkyl-beta-amino dipropionates,

RN alkyl beta-amino propionates, RN (H)

CHH COCOOM; and long chain imidazole derivatives, having the generic formula.

N CH ₂

R-C-F-CH-CH _or -OCH

OH CH ₂ COOM

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(I.e.

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where in each of the above formulas R is an acyclic hydrophlobic group consisting of about 8 to 18 carbon atoms and M is a cation to neutralize the charge of the anion.

In the present detergent compositions, an anionic detergent may also optionally be used in minor amounts as a complement to the amphoteric and nonionic detergent compounds

In general, the amount of anionic detergent will be less than about 5% by weight and preferably less than about 3% by weight of the total composition due to the limited solubility of such detergents in structured liquid detergent compositions . The alkyl benzene sulfonate salts, characterized in that the alkyl group consists of 10 to 18 carbon atoms, exhibit a particularly limited solubility in the present compositions and, therefore, it is preferred that the present compositions are substantially free of such compounds, so to avoid the possibility of product separation.

Preferred anionic detergents for use in this process are sulphated ethoxylated higher fatty alcohols according to the formula RO (CH2) n SO2 SO4 M, where R is a fatty alkyl of 10 to 18 or 20 carbon atoms, m is from 2 to 6 or 8 (preferably having a value of about 1/5 to 1/2 of the number of carbon atoms in R) and M is a cation for solubilizing salt formation, such as an alkali metal, ammonium, lower alkyl or lower alkanolamino, or a higher alkyl benzene sulphonate, wherein the higher alkyl is 10 to 15 carbon atoms.

Ethylene oxide is the preferred lower alkylene oxide of the anionic alkoxylated detergent, and its proportion in the polyethoxylated higher alkanol sulphate is preferably 2 to 5 mol of ethylene oxide groups present per mole of anionic detergent, more preferred with three moles, especially when the higher alkanol is 11 or 12 to 15 carbon atoms. To maintain the desired hydrophilic-lipophilic balance, when the carbon chain content of the alkyl chain is in the lower part of the range of 10 to 18 carbon atoms, the ethylene oxide content of the detergent can be reduced to about two mol per mole, whereas when the higher alkanol is from 16 to 18 carbon atoms in the upper range, the number of ethylene oxide groups may be increased to 4 or 5 and in some cases to as high as 8 or 9. Similarly, the cation for salt formation can be altered to obtain the best solubility. It may be any suitably solubilizing metal or radical, but it will most preferably be an alkali metal, for example sodium or ammonium. If lower alkylamino or alkanolamine groups are used, the alkyls and alkanols will usually consist of 1 to 4 carbon atoms and the amines and alkanolamines may be tri-substituted mono-, di, as in monoethanolamine, diisopropanolamine and trimethylamine.

A preferred polyethoxylated alcohol sulfate detergent is marketed by the Shell Chemical Company and sold under the designation Neodol 25-3S.

The non-phosphated builder salts for detergents are used in the present compositions in amounts generally ranging from about 5 to 25%, and preferably from about 10 to 20% by weight. Specific examples of inorganic builders,

non-phosphorous and water soluble salts include inorganic water soluble inorganic silicate, bicarbonate and carbonate salts. The alkali metal carbonates, bicarbonates and silicates, for example sodium and potassium, are particularly useful in this process.

The water-soluble organic builder agents are also useful and include the alkali metal, ammonium and substituted ammonium polyhydroxyl sulfonates, polycarboxylates, carboxylates and polyacetates. Specific examples of polyacetate and polycarboxylate structuring agents include sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediaminetetraacetic acid, nitrilotriacetic acid, benzene polycarboxylic acids (i.e. penta and tetra-), carboxymethoxysuccinic acid and Citric acid.

The percentage of water, the main solvent in the present compositions, will usually be from about 3θ to 85%, preferably 45 to 75% θ, more preferably from about 60 to 70% by weight of the liquid composition.

Fluorescent or brightening optical brighteners used in the liquid detergent compositions are important components of the modern detergent compositions, which give the laundry and washed materials a shiny appearance, so that the laundry is not only clean but also looks clean. Although it is possible to use a single fanner for the specific purpose intended in the present liquid detergent compositions, it is generally desirable to use fanner blends, which will have good revival effects on cotton, nylons, polyesters. teres and mixtures of these materials, which are also stable in their bleaching action. A good de-

of these types of optical brighteners in the article "The Requirements of Present Day Detergent Fluorescent Whitening Agent" by AE Sjqgrist, J.Am. This article and U.S. Patent 3,812,041, issued May 21, 1974, both incorporated herein by reference, include detailed descriptions of a wide variety of suitable optical brighteners .

Among the enhancers useful in the present liquid detergent compositions are: Calcofluor 5BM (American Cyanamid); Tinopal LTV (Ciba); SOF A-2001 (Ciba); CDW (Hilton-Davis); Phorwite RKH, Phorwite BBH and Phorwite BHC (Verona); CSL, powder and acid (American Cyanamid); FB 766 (Verona); BlMncophor PD (GAF); UNPA (Geigy); Tinopal RBS 200 (Geigy).

Adjuvants may be present in the liquid detergent compositions in order to provide additional functional and aesthetic properties. Included among the useful adjuvants are soil suspending agents or antiredeposition agents such as polyvinyl alcohol, sodium carboxymethylcellulose and hydroxypropylmethylcellulose, thickeners, for example, gums, alginates, agar agar; foaming agents, for example lauric-myristic diethanolamide; foam destroyers, for example, silicones; bactericides, for example, tribromosalicillanilide, hexachlorophene; dyes; pigments (dispersible in water); preservatives; ultraviolet absorbers; fabric softeners; opacifying agents, for example, polystyrene suspensions; and perfumes. These materials will of course be selected based on the desired properties of the finished product, their compatibility with the other components and

in its solubility in the liquid composition.

The liquid compositions herein are effective and easy to use. In comparisons with laundry laundry detergent powders, much lower volumes of the liquid present are employed to provide a comparable degree of laundry cleanliness. For example, when using a typical preferred formulation of this invention, only about 132 grams or 1/2 cup of liquid is required for a complete washing container of a top loading automatic washing machine in which the volume of required water is 15 to 18 gallons / 55 to 75 liters); and an even smaller amount is required for loading machines from the front. Thus, the concentration of the liquid detergent composition in the wash water is in the range of about 0.2%. Typically, the proportion of the liquid composition in the lavage solution will be in the range of about 0.05 to 0.3%, preferably 0.15 to 0.25%. The proportions of the various components of the liquid composition may vary accordingly. Equivalent results may be obtained by using larger proportions of a more dilute formulation, but the larger amount required will require additional packaging, which will generally be less convenient for consumer use.

EXAMPLE 1

The structured liquid detergent compositions containing enzymes, AP, were formulated as indicated below, in Table 1. The percentages indicated represent percentages by weight.

TABLE 1

Primary alcohol THE B £ D] 3 F ethoxylated C ^ ₂ "^^ 0 5.5% 5.5% 5.5% 5.5% 5.5% 5.5% (7 mol EO / mol of alcohol) Varion CADG® 21 21 21 21 21 21 Aviv 0.2 0.2 0.2 0.2 0.2 0.2 Nitrilotriacetate 15 15 15 15 15 15 of sodium PBB " 1 1 1 1 1 1 perfume 0.3 o, 3 0.3 0.3 0.3 0.3 Proteolytic Enzyme® 1 1 1 1 1 1 Glycerin - 5 5 5 5 - Borax - 1 2 3 - 3 h ₂ o ----part remaining---- Percentage of enzyme 12 62 73 76 21 28

active after 6 days at 110 ° F (43 ° C)

(1) An aqueous 52% coco-amido betaine solution sold by Sherex Chemical Company.

(2) "Polar Brilliant Blue" a dye solution active at

1%.

(3) "Esperase", sold by Novo Industries, consisting of

5% enzyme, 75% propylene glycol and the remainder in H 2 O, having an activity of 8.0 KNPU / g .. (Kilo Novo Protease units / gr.).

The enzyme activities of the AF compositions were tested after 6 days storage at 110Â ° F (43Â ° C) the percentage activity over the starting value is given in Table 1. A, E and F were the only compositions that did not contain a enzyme stabilizing system according to the invention and which showed almost complete loss of enzyme activity after 6 days. Compositions B, C and D reflect the marked improvement in enzyme stability, caused by the inclusion of glycerin and borax in the detergent composition.

Compositions A to F were all homogenous, single-phase and clear compositions, which maintained their physical stability and clarity after 6 months of storage at both room temperature and 110Â ° F (43Â ° C).

EXAMPLE 2

The structured liquid detergent compositions containing enzymes, G and H, were formulated essentially similar to the AF compositions, except that sodium citrate was used as the structuring salt instead of sodium NTA. The compositions are shown below in Table 2.

TABLE 2

Primary alcohol

ethoxylated ^C 12 ^-C 15 (7 mol EO / mol alcohol)

H

5.5%

Varion CADG

Reviver

Sodium citrate PBB ¹

perfume

Proteolytic Enzyme

Glycerin

Borax

21

0.2

13

1

0.3

1

21

0.2

13

1

0.3

h ₂ o

remaining part ------ Percent active enzyme after 6 days at 110 ° F (43 ° C)

26

95

(1) An aqueous 32% coco-amido betaine solution sold by Sherex Chemical Company.

(2) "Polar Brilliant Blue" a dye solution active at

1%.

(3) "Waiting" sold by Novo Industries, consisting of

5% of enzyme, 75% of propylene glycol, and the remainder in HgO, having an activity of 8.0 KNPU / g (Kilo Novo Protease units / gr.).

The composition H according to the invention showed an enzyme activity after 6 days of 95% compared to composition G, which did not contain the enzyme stabilizing system, and which suffered a loss of nearly 3/4 of the enzyme activity.

The compositions were clear, single-phase solutions which remained physically stable after 6 months of storage at either room temperature or

110 ° P (43 ° C).

Claims

1. A process for the preparation of a clear, structured, clear, monophasic, aqueous, liquid detergent composition containing enzymes. to be included in said composition;

(a) from about 3 to 10% by weight of a nonionic surfactant detergent compound;

(b) from about 3 to 15% by weight of an amphoteric surfactant detergent compound;

(c) from about 5 to 25% by weight of a non-phosphated, water-soluble detergent builder salt;

(d) an effective amount of an enzyme or mixture of enzymes selected from the group consisting of alkaline protease enzymes and alpha-amylases;

(e) from about 3 to 15% by weight of an enzyme stabilizing system consisting essentially of (i) glycerin and (ii) a boron compound selected from the group consisting of boric acid, boric oxide and alkali metals capable of reacting with said glycerin; and

(f) from about 30-85% by weight of water.

-222δ. 2. A process according to claim 1, wherein said nonionic compound is an alkoxylated alkanol in water.

the claimant

θ2 ~

^ 3 soluble

5a. A process according to claim 1, wherein said structuring salt is sodium citrate.

4 &. 2. A process according to claim 1, wherein said structuring salt is sodium nitrilotriacetate.

5-. - Process according to claim 1, characterized by including in said detergent composition less than about 5%, ^m © weight of a compound anionic detergent.

5. A process according to claim 1, wherein said detergent composition is substantially free of an anionic alkyl benzene sulfonate detergent.

7-. 6. A process according to claim 1, wherein said boron compound is an alkali metal borate.

(i.e.

π

8 ". 7. A process according to claim 7, wherein said detergent composition comprises from about 3 to 7% by weight of said glycerol and from about 1 to 4% by weight of said alkali metal borate.

9 ^ã . 5. A process according to claim 1, wherein said detergent composition is substantially free of a phosphate builder salt for detergents.

10 &. 2. A process according to claim 1, wherein said alkali metal borate is borax.

11. A process according to claim 1, wherein said builder salt is present in said detergent composition in an amount of about 10 to 20% by weight.

12®. A laundry washing method, characterized in that the stained and / or dirty fabrics to be washed are contacted with a clean, monophasic, liquid detergent builder composition containing enzymes, consisting of:

(a) from about 3 to 10% by weight of a nonionic surfactant detergent compound;

(c) from about 5 to 25% by weight of a non-phosphated and water soluble detergent builder salt;

(e) from about 3 to 15% by weight of an enzyme stabilizing system consisting essentially of (i) glycerin and (ii) a boron compound selected from the group consisting of boric acid, boric oxide and borates of alkali metals capable of reacting with said glycerin; and

(f) from about 30-85% by weight of water.

13 ^a . 2. A method according to claim 12, wherein said nonionic detergent compound is a soluble alkoxylated alkanol

in water.

14 ^a . A method according to claim 12, characterized in that said composition comprises less than about 5% by weight of an anionic surfactant detergent compound.

-2515 ^& . 8. A method according to claim 12, wherein said composition is substantially free of an anionic detergent alkyl benzene sulfonate.

16S. A method according to claim 12, wherein said boron compound is an alkali metal borate.

17 ^g . A method according to claim 16, characterized in that said composition comprises from about 3 to 7% by weight of said glycerin and from about 1 to 4% by weight of said alkali metal borate

18 ^â . A method according to claim 12, wherein said alkali metal borate is a borax.

19S. A method according to claim 12, wherein said non-phosphated builder salt is present in the composition in an amount of about 10 to 20% by weight.

J. PEREIRA DA CRUZ ABERTE OHCIAL DE PRSPWíBAD INWSTMAL Rua Vlotor Cordon, 10-A-1. ⁰ USBOA