CA1297440C - Fabric softening liquid detergent - Google Patents
Fabric softening liquid detergentInfo
- Publication number
- CA1297440C CA1297440C CA000514035A CA514035A CA1297440C CA 1297440 C CA1297440 C CA 1297440C CA 000514035 A CA000514035 A CA 000514035A CA 514035 A CA514035 A CA 514035A CA 1297440 C CA1297440 C CA 1297440C
- Authority
- CA
- Canada
- Prior art keywords
- alkali metal
- enzyme
- sodium
- detergent composition
- liquid detergent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/10—Salts
- C11D7/16—Phosphates including polyphosphates
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/386—Preparations containing enzymes, e.g. protease or amylase
- C11D3/38663—Stabilised liquid enzyme compositions
Abstract
I.R. 4259- 1 ABSTRACT OF THE DISCLOSURE
A stabilized enzyme-containing built liquid detergent is provided comprising (a) from about 5 to 20%, by weight, of one or more surface active detergent compounds selected from the group consisting of anionic, nonionic and amphoteric detergent compounds;
(b) from about 5 to 30%, by weight, of one or more builder salts selected from the group consisting of alkali metal tripolyphosphates, alkali metal carbonates, alkali metal nitrilotriacetates and polyacetal carboxylates;
(c) from about 5 to 20%, by weight, of a swelling bentonite clay;
(d) an effective amount of an enzyme or an enzyme mixture selected from the group consisting of alkaline protease enzymes and alpha-amylase enzymes;
(e) an enzyme-stabilizing system containing, based on the weight of the detergent composition, (i) from about 1% to 10% glycerine; (ii) from about 1 to 8%
of a boron compound selected from the group con sisting of boric acid, boric oxide and alkali metal borates; and (iii) from about 0.5 to 8% of a carbo-xylic acid compound selected from the group consisting of mono, di and/or polycarboxylic acids having 1 to 8 carbon atoms and water-soluble salts thereof;and (f) the balance comprising water
A stabilized enzyme-containing built liquid detergent is provided comprising (a) from about 5 to 20%, by weight, of one or more surface active detergent compounds selected from the group consisting of anionic, nonionic and amphoteric detergent compounds;
(b) from about 5 to 30%, by weight, of one or more builder salts selected from the group consisting of alkali metal tripolyphosphates, alkali metal carbonates, alkali metal nitrilotriacetates and polyacetal carboxylates;
(c) from about 5 to 20%, by weight, of a swelling bentonite clay;
(d) an effective amount of an enzyme or an enzyme mixture selected from the group consisting of alkaline protease enzymes and alpha-amylase enzymes;
(e) an enzyme-stabilizing system containing, based on the weight of the detergent composition, (i) from about 1% to 10% glycerine; (ii) from about 1 to 8%
of a boron compound selected from the group con sisting of boric acid, boric oxide and alkali metal borates; and (iii) from about 0.5 to 8% of a carbo-xylic acid compound selected from the group consisting of mono, di and/or polycarboxylic acids having 1 to 8 carbon atoms and water-soluble salts thereof;and (f) the balance comprising water
Description
4~
BACKGROUND OF THE INVENTION
This invention relates to stable, built, enzyme-containing liquid detergent compositions suitable for laundry or pre-soak formulations. More particularly, the invention relates to aqueous enzyme-containing liquid detergent CoMposi-tions which contain one or more detergent builders and which are characterized by being physically stable, homogeneous liquid compositions.
The formulation of stabilized enzyme-containing liquid detergent compositions has been the focus of much atten-tion in the prior art. The desirability oE incorporating enzymes into detergent composi-tions is primarily due to the effectiveness of proteolytic and amylolytic enzymes in decompo-sing proteinaceous and starchy materials found on soiled fab-rics, thereby facilitating the removal of s-tains, such as, gravy stains, blood stains, chocolate stains and the like dur-ing laundering. However, enzymatic ma-terials sui-table for laundry compositions, particularly proteolytic enzymes, are relatively expensive. Indeed, they generally are among the most expensive ingredients in a typical commercial liquid de-tergent composition, even though they are present in relatively minor amounts. Moreover, enzymes are known to be unstable in aqueous compositiorls. It is for this reason that an excess of enzymes is generally required in liquid detergent formulations to compensate for the expected loss of enzyme activity during prolonged periods of storage. Accordingly, the prior art is replete with suggestions for stabilizing enzyme-containing liquid detergent compositions, and in particular unbuilt liquid compositions by the use of various materials which are incorpo-rated into the composition to function as enzyme stabilizers.
BACKGROUND OF THE INVENTION
This invention relates to stable, built, enzyme-containing liquid detergent compositions suitable for laundry or pre-soak formulations. More particularly, the invention relates to aqueous enzyme-containing liquid detergent CoMposi-tions which contain one or more detergent builders and which are characterized by being physically stable, homogeneous liquid compositions.
The formulation of stabilized enzyme-containing liquid detergent compositions has been the focus of much atten-tion in the prior art. The desirability oE incorporating enzymes into detergent composi-tions is primarily due to the effectiveness of proteolytic and amylolytic enzymes in decompo-sing proteinaceous and starchy materials found on soiled fab-rics, thereby facilitating the removal of s-tains, such as, gravy stains, blood stains, chocolate stains and the like dur-ing laundering. However, enzymatic ma-terials sui-table for laundry compositions, particularly proteolytic enzymes, are relatively expensive. Indeed, they generally are among the most expensive ingredients in a typical commercial liquid de-tergent composition, even though they are present in relatively minor amounts. Moreover, enzymes are known to be unstable in aqueous compositiorls. It is for this reason that an excess of enzymes is generally required in liquid detergent formulations to compensate for the expected loss of enzyme activity during prolonged periods of storage. Accordingly, the prior art is replete with suggestions for stabilizing enzyme-containing liquid detergent compositions, and in particular unbuilt liquid compositions by the use of various materials which are incorpo-rated into the composition to function as enzyme stabilizers.
~;29~4 ~
62301~1384 In the case of liquid detergent compositions contain-ing a builder, the problem of enzyme instability is particular-ly acute. Primarily this is because detergent builders have a destabilizing effect on enzymes, even in compositions contain-ing enzyme stabilizers which are otherwise effective in unbuilt formulations. Moreover, the incorporation of a builder into a liquid detergent composition poses an additional problem, name-ly, the ability to form a stable single-phase composition' the solubility of sodium tripolyphosphate, for example, being rela-tively limited in aqueous compositions, and especially in thepresence oE anionic and nonionic detergents.
ln V.K. Patent Application G.B. 2,079,305, publ;shed January 20, 19~2, there is disclosed an aqueous built enzyme-containing liquid detergent composition which is stabilized by a mixture of a polyol and boric acid. As noted in the examples of the U.K. application, relatively large amounts of glycerol are required to stabiliæe -the enzymes in the composition. Yet, as demonstrated hereinafter in the present specification, -the enzyme stabilizing effect provided by a mixture of glycerine and borax in a built aqueous liquid detergent composition is relatively modest.
,~ 3 -g2~7~
SUMMARY OF THE INVENTION
The present invention provides a stabilized fabric softening built, enzyme-containing liquid detergent composition comprlslng:
(a) from about 5 to 20%, by weight, of one or more sur-face active detergent compounds selected from the : group consisting o~ anionic, nonionic and amphoteric detergent compounds;
(b) from about 5 to 30~, by weight, of one or more build-er salts selected from the group consisting of alkali metal tripolyphosphates, alkali metal carbonates, alkali metal nitri].otr:iacetates, ~nd polyacetal c~r--boxylates;
(c) from about 5 to 20%, by weight, of a swelling benton-ite clay;
(d) an effective amount of an enzyme or an enzyme mixture selected from the group consisting of alkaline pro-tease enzymes and alpha-amylase enzymes;
(e) an enzyme-stabilizing system containing, based on the weigh-t oE the detergent composition, (i) from about 1 to 10% glycerine; (ii) from about 1 to 8% of a boron compound selected from the group consisting of boric acid, boric oxide and alkali metal borates and; (iii) from about 0.5 to 8% of a carboxylic acid compound selected from the group consisting of mono, di and/or polycarboxylic acids having 1 to 8 carbon atoms and water-soluble salts thereof, and (f) the balance comprising water and optionally perfume and other adjuvants.
~2~7~L.~CI
In a preferred embodiment of the invention, the liquid detergent composition comprises (a) from about 5 to 15% of an alkali metal alkyl-benzene sulfonate wherein the alkyl group contains 12 to 15 carbon atoms' (b) from about O.S to 5% of an alkali metal alkyl poly-ethoxy sulfate wherein the alkyl group contains 10 to 18 carbon atoms and the polyethoxy is of 3 to 11 ethylene oxide groups, the weight ratio of (a) to (b) being from about 2:1 to about 6:1;
(c) from about 5 to 20% of sodium tripolypllosphate;
(d) from about 1 to 10~ oE sodium carbonate, sodium bi-carbonate or mixtures thereof, the weight ratio of (c) to (d) being from about 2:1 to about 6:1;
(e) from about 10 to 15~ of a sodium bentonite, (f) an effective amount of the aforesaid enzyme or enzyme mixture;
(g) an enzyme stabilizing system containing, based on the weight of the detergent composition, (i) from about 1 to 5% glycerine (ii) from about 1 to 5% of an alkali metal borate and (iii) from about 0.5 to 4% of said carboxylic acid compound; and (h) the balance comprising water and optionally perfume and other adjuvants.
In accordance with the process of the invention, laundering of stairled and/or soiled materials is affected by contacting such materials with an aqueous solution of the above-defined liquid detergent compositions.
The described liquid detergent is a commercially acceptable heavy duty laundry detergent, capable of satisfact-orily cleaning laundry items containing both oily and particu-late soils. Addi-tionally, the described compositions may be employed for the pre-treatment of badly soiled areas, such as collars and cuffs, of items to be laundered.
The present invention is predicated upon the discov-ery of a three component enzyme stabilizing system as herein defined which provides an enzyme stabilizing effect to the liquid detergent compositions of the invention far in excess of that which can be achievecl with conventional enzyme stabili-zers. The enzyme stabilizing effect thus achieved reElects a synergy among the three components. In accordance with the invention, the enzyme stability provided by a mixture of glycerine and borax or a mixture of borax and a dicarboxylic acid as disclosed in the prior art can be synergistically improved by the use of the three component stabilizing system herein defined in the present liquid compositions so as to raise the level of enzyme stability significantly above that provided by either the mixture of glycerine and borax or the mixture of borax and dicarboxylic acid when used independently of each other as enzyme stabilizers. For commercial purposes, a desirable enzyme stability generally corresponds -to about a half-life of one week at a temperature of 110F.
~29~0 6230~-1384 DETAILED D~SCRIPTION OF THE I~VENTIO~
The enzyme stabilizing system of the invention is a mixture of glycerine, a boron compound selected from among boric acid, boric oxide and an alkali metal borate and a car-boxylic acid compound as herein defined. The weight of the stabilizing system in the present built liquid detergent compo-sitions is generally from about 3 to 25%, preferably about 6 to 15~, by weight. The weight ratio of glycerine to borax in the stabilizing mixtures is generally from about 0.5 to 3. The preferred amount of glycerine in the composition is ~rom about 1 to 5~, the preferred amount of boron compound is from about 1 to 5%, and the preferred amount of carboxylic compound is Erom about 0.5 to 4~ based on the weight of the composition.
The carboxylic acid compounds which are useful in the enzyme stabilizing system of the invention encompass saturated as well as unsaturated mono, di and polycarboxylic acids having 1 to 8 carbon atoms among which are included oxalic acid (HOOCCOOH), malonic acid (HOOCCH2COOH), maleic acid (HOOCCH:CHCOOH) and succinic acid (HOOCCH2CH2COOH). The carboxylic acids may contain hydroxy or amino substituents as exemplified by malic acid (HOOCCHOHCH2COOH), tartaric acid (dihydroxysuccinic acid) aspartic acid (amino succinic acid) and citric acid. Preferred carboxylic acids of the invention are aspartic acid, tartaric acid, malonic acid and malic acid.
From a commercial standpoint, a particularly preferred carboxy-lic acid compound is citric acid and/or its salts because of their relatively low cost.
The alkaline proteolytic enzymes suitable for the present compositions include the various commercial liquid . . .
12~7~ 1~
62301-138~
enzyme preparations which have been adapted for use in deter-yent compositions. Enzyme preparations in powdered form are also useful although, as a general rule, less convenient Eor incorporation into the built liquid detergent compositions.
Thus, suitable liquid enzyme preparations include "Alcalase"
and "Esperase" sold by ~ovo Industries, Copenhagen, Denmark, and "~axatase" and "AZ-Protease" sold by Gist-Brocades, Delft, The Netherlands.
AMong the suitable~ -amylase liquid enzyme prepara~
tions are -those sold by Novo Industries and Gist-Brocades under the tradenames "Termamyl" and "Maxamyl", respectively.
"Esperase" is particularly preferred for the present compositions because of its optimized activity at the higher pH
values corresponding to the built detergent compositions.
The preferred detergents for use in the present liquid compositions are the synthetic anionic detergent com-pounds, and particularly a mixture of higher alkylben~.ene sulfonate and alkyl polyethoxy sulfate. While other water soluble higher alkylbenzene sulfonates may also be presen-t in the instant formulas, such as potassium salts and in some instances the ammonium or alkanolammonium salts, where appropriate, it has been found that the sodium salt is highly preferred, which is also the case with respect to khe alkyl polyethoxy sulfate detergent component. The alkylbenzene sulfonate is one wherein the higher alkyl is of 12 to 15 carbon atoms, preferably 13 carbon atoms. The alkyl polyethoxy sulfate, which also may be referred to as a sulfated polyethoxylated higher linear alcohol or the sulfated condensation product of a higher fatty alcohol and ethylene oxide or polyethoxylene glycol, is one wherein the 3L2~74~
62301-13~4 alkyl is of 10 to 18 carbon atoms, preferably 12 to 15 carbon atoms, e.g., abou-t 13 carbon atoms, and which includes 3 to 11 ethylene oxide groups, preferably 3 to 7, more preferably 3 to 5 and most preferably 3 or about 3 ethylene oxide groups. The ratio of alkylbenzene sulfonate to polyethoxy sulfate in the detergent mixture is preferably from about 2:1 to 6:1 and most preferably from about 2:1 to ~:1, by weight. A~ ratios about 5:1, the physical stability of the product may ~e adversely affected.
In suitable circumstances other anionic detergents, such as fatty alcohol sulfates, paraefin sulfonates, ol.efin sulfonate~, monoglyceride .sulfates, sarcosinates and similarly functioning detergents, preferably as the alkali metal, e.g., sodium salts, can be present, sometimes in partial replacement of the previously mentioned synthetic organic detergents but usually, if present, in addition to such detergents. Normally, the supplementing detergents will be sulfated or sulfonated products (usually as the sodium salts) and will contain long chain (8 to 20 carbon atoms) linear or fatty alkyl groups. In addition to any supplementing anionic synthetic organic deter-gents, there also may be present nonionic and amphoteric mater-ials, like the Neodols,~ sold by Shell Chemical Company, which are condensation products of ethylene oxide and higher fatty alcohols, e.g., Neodol~ 23-6.5, which is a condensation product of a higher fatty alcohol of about 12 to 13 carbon atoms with about 6.5 moles of ethylene oxide. Illustrations of the various detergents and classes of detergents mentioned may be found in the text Surface Active Agents, Vol. II, by Schwartz, Perry and Berch (Interscience Publishers, 195~), the descriptions of which are incorporated herein by reference.
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The builder salt combination of this invention, which has been found to satisfactorily improve the detergency of the mixture of synthetic anionic organic detergents and produe the desired pH in the liquid detergent and in the wash water, is a mixture of sodium tripolyphosphate and sodium carbonate. The builder salts are employed in the present compositions in amounts generally oE from about 5 to 25%, by weight. For the preferred builder salt combination, sodium tripolyphosphate is present in amounts of from about 5 to 20~, preferably 10 to 16%, and sodium carbonate is present from about 1 to 10~, by weight, preferably 3 to 7%, the weight ratio of tripolyphos-phate to carbonate in the preferred bui1ders mixtures being from about 2:1 to 6:1, and most preferably from about 2:1 to 4:1. As used herein, the term alkali metal "carbonates" or "carbonate" is meant to include the carbonates, bicarbonates and sesquicarbonates of such alkali metal.
For best processing, easier mixing and good end-use properties it i5 preferred that the sodium tripolyphosphate be low in con-tent of Phase I type tripolyphosphate. Thus, normal-ly the content of Phase I type tripolyphosphate will be lessthan 30% of the tripolyphosphate employed. Although in some instances incompletely neutralized tripolyphosphate may be used, normally the phosphate employed may be considered as being pentasodium tripolyphosphate, NasP301o. Of course, in some instances, as when potassium salts of other materials are present, ion interchange in an aqueous medium may result in other salts than the sodium tripolyphosphate being present but for the purpose of this specification it will be considered that sodium tripolyphosphate, as the pentasodium salt, the material which is normally charged to the mixer to make the ., ~ 2~
present liquid detergent, is the tripolyphosphate employed.
Other pre~erred builder salts which may be used in place of sodium tripolyphosphate and sodium carbonate or in addition thereto include a polyacetal carboxylate as herein described and sodium nitrilotriacetate (NTA). of course, vari-ous mixtures of the mentioned water soluble builder salts can be utilized. Yet, the tripolyphosphate-carbonate mixture des-cribed has been found to be most preferred, although the other builders and mixtures thereof are also operative. Other build-ers which may be employed as supplements, in addition to theproportions of the above mentioned builders, include other phosphates, such as ~etrasodium pyrophosphate or tetrapotassium pyrophosphate, sodium bicarbonate, sodium citrate, sodium glu-conate, sodium silicate, and sodium sesquicarbonate. Among the water insoluble builders that may be used are the zeolites, such as Zeolite A, usually in the form of its crystalline hy-drate, although amorphous zeolites may also be useful.
Polyacetal carboxylates are generally described in U.S. Patents 4,144,226 and 4,315,092. U.S. Patent 4,146,495 describes detergent compositions containing polyacetal carboxy-lates as builders.
The polyacetal carboxylates which are useful herein as builders may be considered to be those described in U~S.
Patent 4,144,226 and may be made by the method mentioned there-in. A typical such product will be of the formula Rl - (cHo)n - R2 COOM
wherein M is selected ~rom the group consistiny of alkali metal, ammonium, alkyl groups of 1 to 4 carbon atoms, tetra-alkylammonium groups and alkanolamine groups, both of 1 to 4 ~97~
earbon atoms in the alkyls thereof, n avexages at least 4, and Rl and R2 are any chemic~lly stable groups which stabilize t~e polymer against rapi~ depolymerization in alkali~e solution. Preferably the polyacetal carboxylate will be one wherein M is alkali metal, e.g., sodium, n is from 50 to 200, ~1 is C~3cH2O MOOC
~CO- or H3C-CO-or a mixture thereof, R2 is -CH
and n averages from 20 to 100, more pre~erably 30 to 80.
The calculated weight average molecular weights of the polymers will normally be within the range of 2,000 to 70,000, preferably 3,500 to l0,000 and more preferably S,000 to 9,000, e.g., about 8,000.
A particularly preferred sodium polyacetal carboxylate is supplied by Monsanto Company and is known as Builder U. It has a calculated average molecular weight of about 8,000 and an acti~e polymer content of about 80%.
Although the preferrPd polyacetal carboxylates have been described above, it is to be understood that they may be wholly or partially replaced by other such polyacetal carbo~ylates or related organic builder salts described in the previously cited patents on such compounds, processes for the manufacture thereof and compositions in which they are employed. Also, the chain terminating groups described in the various patents, especially U.S. 4,144,226, may be utilized, providing ~hat they have the 4~
desired stabilizing properties, which allow the mentioned builders to be depolymeri~ed in acidic media, facilitating biodegradation thereof in waste streams, but maintain their stability in alkaline media, such as washing solutions.
The bentonite employed herein is a colloidal clay (aluminium silicate) containing montmorillonite. Swelling bentonites are generally characterized as sodium bentonites, i.e., bentonite wherein the predominant cation is sodium.
Among the sodium bentonite clays, those from Wyoming (generally referred to as Western or Wyoming bentonite) are especially preferred.
The swelling capacity of bentonite is generally associated with its fabric softening properties. In water the s~elling capacity of sodium bentonite is in the range of 3 to 20 milliliters/gram, preferably 7 to 15 ml/gram, and its viscosity, at 6% concentration in water, is usually in the range of 3 to 30 centipoises, preferably 8 to 30 centipoises.
Preferred swelling bentonites are sold under the trademark ~I-JEL by Georgia Kaolin Co. These materials are the same as bentonites which were formerly sold under the trademarks MIN~AL COLLOID and Tl.~IXO-JEL. They are selectively mined and beneficiated bentonites, and those considered to be most useful are available as HI-JEL Nos. 1,2,3 etc., corresponding to THIXO-JELs No's 1,2,3 and 4. Such materials have a maximum free moisture content (before addition to the liquid medium) o~ 4% to 8% and specific gravities of about 2.6. The bentonite is pre~erably one which will pass through a 200 mesh U.S. Sieve Series sieve, and most preferably at least 90% of the particles will pass through a No. 325 sieve, so that the equivalent diameter of the bentonite may be considered to be less than 74 microns, and more preferably less than about 44 microns.
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Typical chemical analyses of some bentonites that are useful for making the present liquid detergents show that they contain from 64.8 to 73.0% of sio2, 14 to 18% of A12O3, 1.6 to 2.7% of MgO, 1.3 to 3.1% of CaO, 2.3 to 3.4% of Fe2O3, 0.8 to 2.8% of Na2O and 0.4 to 7O0% of K2O.
Although the western bentonites are preferred it is also possible to utilize other bentonites, such as those which may be made by treating Italian or similar bentonites contain-ing relatively small proportions of exchangeable monovalent metals (sodium and potassium) with alkaline materials, c~uch as sodium carbonate, to increase the cation exchancJe capclcities o such products. It is considered that the ~a2O content of the bentonite should be at least about 0.5%, preferably at least 1%
and more preferably at least 2% so that the clay will be satis-factorily swelling, with good softening and dispersing proper-ties in aqueous suspension. Preferred swelling bentonites of the types described above are sold under the trade names Laviosa and Winkelmann, e.g., Laviosa AGB and Winkelmann G-13.
Other bentonites which are particularly useful for the present liquid detergent compositions because of their white or very light color include American Colloid Company's Pol.arite KB 325, a Cali~ornia bentonite, and Georgia Kaolin's GK 129, a Mexican ben-tonite.
The viscosity of the present liquid detergent is normally in the range of about 1000 to 10,000 centipoises, preferably 2000~7000 centipoises, but products of other suit-able viscosities may also be useful. At the viscosities men-tioned, the liquid detergent i6 pourable, stable, non-separa ting and uniform. The pH of the liquid detergent suspension , ~2~7~
usually in the range of 7 to 11.5, preferably 8 to 10.5, appears to help to maintain product stability and pourability.
The following examples illustrate but do not limit the invention. Unless otherwise indicated all parts are by weight and temperatures are in C.
EXAMPLE_l Component Percent Pentasodium tripolyphosphate 11.0 10 Bentonite ~Georgia-Kaolin 129) 12~0 Sodium carbonate 2.0 Sodium sesquicarbonate 2.0 Sodium linear tridecylben~ene 8.0 sulfonate AEOS(l) Carboxymethyl cellulose (CMC) 0.2 Optical brightener 0.3 Perfume 0.4 EnPyme (Esperase 8.0L)(2) 1.0 Glycerine 3.0 Borax 2.5 Citric Acid ~.o Water and adjuvants Balance (1) Sodium alkyl polyethoxy sulfate wherein the alkyl is 12 to 15 carbon atoms and the polyethoxy is 3 ethoxy groups.
(2) "Esperase" sold by Novo Industries having an activity of 8.0 KNPU/gram.
, - 15 -., ~ ., 79L~
The composition shown above was prepared by the following procedure: 30.0 parts of deionized water at 40F are added to a suitable mixing apparatus such as a vertical cylindrical tank equipped with a stirrer. With the stirrer adjusted for medium agitation, a mixture consisting of 2.0 parts anhydrous soda ash, 2.0 parts sodium sesquicarbonate, and 0.2 parts sodium carboxymethyl cellulose is incorporated into the water. The stirrer speed is then increased to maximum agitation and a mixture comprised of 11.0 parts pentasodium tripolyphosphate and 12.0 parts bentonite is slowly added to the mixing apparatus over a period of 10-15 Mlnutes to Eorm an off-white suspension.
The agitation speed is then decreased to a slow/medium setting while 8.64 parts of a high AI (about 55%) LTBS slurry is added.
Thereafter the optical brightener/color solution is added con-sisting of 0.3 parts Tinopal L~'IS-X (CIBA-GEIGY), 0.99 parts colorant, and 4.02 parts deionized water. Once a uniform blueish-green colored solution is obtained, 0.4 parts of perfume are added to the ~ixture under agitation. This is followed by the slow addition of 3.0 parts glycerine and 2.5 parts borax as a two com-ponent slurry. Stirring is continued until the mixture is uniorm in appearance and then 2.0 parts of citric acid and ~.0 parts water are slowly added. Agitation of the mixt~re is then reduced while 10.95 parts of a mixed AI detergent base consisting of an LTBS
slurry (about 30% AI) and AEOS (about 27.5~ AI) is added to the mixture. This is followed by the slow addition of l.O part proteolytic enzyme with continous agitation until all materials are completely dispersed or dissolved.
~2g7~
Enzyme-containing built liquid detergent compositions A to G were formulated as set forth below in Table 1. The percentages shown indicate weight percent. The arrows are meant to indicate the extent to which Compositions ~ -to G are identical to Composition A.
Component A B C D E F G
Pentasodium 11.0 Tripolyphosphate Bentonite (Georgia-Kaolin 129) 12.0 Sodium Carbonate 2.0 Sodium sesquicarbonate 2.0 Sodium Linear tridecyl- 8.0 benzene sulfonate AEOS(l) 3.0 Optical brightener 0.3 (Tinopal LMS-X) Perfume 0.4 CMC 0.2 Enzyme(2) 1.0 ~ ~ ~ / \ / \ / \ ~ \ /
Glycerine - 3.0 - 3.0 - - 3.0 Borax -- 2.5 2.5 - 2.5 2.5 Carboxylic acid compound - - - - 2.0 2.0 2.0 Water and adjuvants - Balance (1) Sodium alkyl polyethoxy sulfa-te wherein the alkyl is 12 to 15 carbon atoms and the polyethoxy is 3 ethoxy groups.
(2) "Esperase" sold by Novo Industries having an activity of 8.0 KNPU/gm (Kilo Novo Protease units/gm).
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Tl~e enzyme ~ctivities of Compositions A to F were tested after 7 days storage at 110F. The measured enzyme activity ~or each co~position after this period of storage is indicated in Table 2 as a percent of the initial value. The ~arious carboxylic acids and salts used in the general formulas of Compositions A, B, C, D, E, and G are shown in Table 2 as well as the enzyme activities corresponding to each composition.
ENZY'~E STABILITY
Percent Active Enzyme Co~position After 7 Days_at 110F
A (control) ND
B (with glycerine) ND
C (with borax) ND
D (with glycerine and borax) 50 CompositionE (with carboxylic acid compound) wherein the carboxylic acid ` compound is:
: (1) Succinic acid - ND
(2) Malonic acid "
62301~1384 In the case of liquid detergent compositions contain-ing a builder, the problem of enzyme instability is particular-ly acute. Primarily this is because detergent builders have a destabilizing effect on enzymes, even in compositions contain-ing enzyme stabilizers which are otherwise effective in unbuilt formulations. Moreover, the incorporation of a builder into a liquid detergent composition poses an additional problem, name-ly, the ability to form a stable single-phase composition' the solubility of sodium tripolyphosphate, for example, being rela-tively limited in aqueous compositions, and especially in thepresence oE anionic and nonionic detergents.
ln V.K. Patent Application G.B. 2,079,305, publ;shed January 20, 19~2, there is disclosed an aqueous built enzyme-containing liquid detergent composition which is stabilized by a mixture of a polyol and boric acid. As noted in the examples of the U.K. application, relatively large amounts of glycerol are required to stabiliæe -the enzymes in the composition. Yet, as demonstrated hereinafter in the present specification, -the enzyme stabilizing effect provided by a mixture of glycerine and borax in a built aqueous liquid detergent composition is relatively modest.
,~ 3 -g2~7~
SUMMARY OF THE INVENTION
The present invention provides a stabilized fabric softening built, enzyme-containing liquid detergent composition comprlslng:
(a) from about 5 to 20%, by weight, of one or more sur-face active detergent compounds selected from the : group consisting o~ anionic, nonionic and amphoteric detergent compounds;
(b) from about 5 to 30~, by weight, of one or more build-er salts selected from the group consisting of alkali metal tripolyphosphates, alkali metal carbonates, alkali metal nitri].otr:iacetates, ~nd polyacetal c~r--boxylates;
(c) from about 5 to 20%, by weight, of a swelling benton-ite clay;
(d) an effective amount of an enzyme or an enzyme mixture selected from the group consisting of alkaline pro-tease enzymes and alpha-amylase enzymes;
(e) an enzyme-stabilizing system containing, based on the weigh-t oE the detergent composition, (i) from about 1 to 10% glycerine; (ii) from about 1 to 8% of a boron compound selected from the group consisting of boric acid, boric oxide and alkali metal borates and; (iii) from about 0.5 to 8% of a carboxylic acid compound selected from the group consisting of mono, di and/or polycarboxylic acids having 1 to 8 carbon atoms and water-soluble salts thereof, and (f) the balance comprising water and optionally perfume and other adjuvants.
~2~7~L.~CI
In a preferred embodiment of the invention, the liquid detergent composition comprises (a) from about 5 to 15% of an alkali metal alkyl-benzene sulfonate wherein the alkyl group contains 12 to 15 carbon atoms' (b) from about O.S to 5% of an alkali metal alkyl poly-ethoxy sulfate wherein the alkyl group contains 10 to 18 carbon atoms and the polyethoxy is of 3 to 11 ethylene oxide groups, the weight ratio of (a) to (b) being from about 2:1 to about 6:1;
(c) from about 5 to 20% of sodium tripolypllosphate;
(d) from about 1 to 10~ oE sodium carbonate, sodium bi-carbonate or mixtures thereof, the weight ratio of (c) to (d) being from about 2:1 to about 6:1;
(e) from about 10 to 15~ of a sodium bentonite, (f) an effective amount of the aforesaid enzyme or enzyme mixture;
(g) an enzyme stabilizing system containing, based on the weight of the detergent composition, (i) from about 1 to 5% glycerine (ii) from about 1 to 5% of an alkali metal borate and (iii) from about 0.5 to 4% of said carboxylic acid compound; and (h) the balance comprising water and optionally perfume and other adjuvants.
In accordance with the process of the invention, laundering of stairled and/or soiled materials is affected by contacting such materials with an aqueous solution of the above-defined liquid detergent compositions.
The described liquid detergent is a commercially acceptable heavy duty laundry detergent, capable of satisfact-orily cleaning laundry items containing both oily and particu-late soils. Addi-tionally, the described compositions may be employed for the pre-treatment of badly soiled areas, such as collars and cuffs, of items to be laundered.
The present invention is predicated upon the discov-ery of a three component enzyme stabilizing system as herein defined which provides an enzyme stabilizing effect to the liquid detergent compositions of the invention far in excess of that which can be achievecl with conventional enzyme stabili-zers. The enzyme stabilizing effect thus achieved reElects a synergy among the three components. In accordance with the invention, the enzyme stability provided by a mixture of glycerine and borax or a mixture of borax and a dicarboxylic acid as disclosed in the prior art can be synergistically improved by the use of the three component stabilizing system herein defined in the present liquid compositions so as to raise the level of enzyme stability significantly above that provided by either the mixture of glycerine and borax or the mixture of borax and dicarboxylic acid when used independently of each other as enzyme stabilizers. For commercial purposes, a desirable enzyme stability generally corresponds -to about a half-life of one week at a temperature of 110F.
~29~0 6230~-1384 DETAILED D~SCRIPTION OF THE I~VENTIO~
The enzyme stabilizing system of the invention is a mixture of glycerine, a boron compound selected from among boric acid, boric oxide and an alkali metal borate and a car-boxylic acid compound as herein defined. The weight of the stabilizing system in the present built liquid detergent compo-sitions is generally from about 3 to 25%, preferably about 6 to 15~, by weight. The weight ratio of glycerine to borax in the stabilizing mixtures is generally from about 0.5 to 3. The preferred amount of glycerine in the composition is ~rom about 1 to 5~, the preferred amount of boron compound is from about 1 to 5%, and the preferred amount of carboxylic compound is Erom about 0.5 to 4~ based on the weight of the composition.
The carboxylic acid compounds which are useful in the enzyme stabilizing system of the invention encompass saturated as well as unsaturated mono, di and polycarboxylic acids having 1 to 8 carbon atoms among which are included oxalic acid (HOOCCOOH), malonic acid (HOOCCH2COOH), maleic acid (HOOCCH:CHCOOH) and succinic acid (HOOCCH2CH2COOH). The carboxylic acids may contain hydroxy or amino substituents as exemplified by malic acid (HOOCCHOHCH2COOH), tartaric acid (dihydroxysuccinic acid) aspartic acid (amino succinic acid) and citric acid. Preferred carboxylic acids of the invention are aspartic acid, tartaric acid, malonic acid and malic acid.
From a commercial standpoint, a particularly preferred carboxy-lic acid compound is citric acid and/or its salts because of their relatively low cost.
The alkaline proteolytic enzymes suitable for the present compositions include the various commercial liquid . . .
12~7~ 1~
62301-138~
enzyme preparations which have been adapted for use in deter-yent compositions. Enzyme preparations in powdered form are also useful although, as a general rule, less convenient Eor incorporation into the built liquid detergent compositions.
Thus, suitable liquid enzyme preparations include "Alcalase"
and "Esperase" sold by ~ovo Industries, Copenhagen, Denmark, and "~axatase" and "AZ-Protease" sold by Gist-Brocades, Delft, The Netherlands.
AMong the suitable~ -amylase liquid enzyme prepara~
tions are -those sold by Novo Industries and Gist-Brocades under the tradenames "Termamyl" and "Maxamyl", respectively.
"Esperase" is particularly preferred for the present compositions because of its optimized activity at the higher pH
values corresponding to the built detergent compositions.
The preferred detergents for use in the present liquid compositions are the synthetic anionic detergent com-pounds, and particularly a mixture of higher alkylben~.ene sulfonate and alkyl polyethoxy sulfate. While other water soluble higher alkylbenzene sulfonates may also be presen-t in the instant formulas, such as potassium salts and in some instances the ammonium or alkanolammonium salts, where appropriate, it has been found that the sodium salt is highly preferred, which is also the case with respect to khe alkyl polyethoxy sulfate detergent component. The alkylbenzene sulfonate is one wherein the higher alkyl is of 12 to 15 carbon atoms, preferably 13 carbon atoms. The alkyl polyethoxy sulfate, which also may be referred to as a sulfated polyethoxylated higher linear alcohol or the sulfated condensation product of a higher fatty alcohol and ethylene oxide or polyethoxylene glycol, is one wherein the 3L2~74~
62301-13~4 alkyl is of 10 to 18 carbon atoms, preferably 12 to 15 carbon atoms, e.g., abou-t 13 carbon atoms, and which includes 3 to 11 ethylene oxide groups, preferably 3 to 7, more preferably 3 to 5 and most preferably 3 or about 3 ethylene oxide groups. The ratio of alkylbenzene sulfonate to polyethoxy sulfate in the detergent mixture is preferably from about 2:1 to 6:1 and most preferably from about 2:1 to ~:1, by weight. A~ ratios about 5:1, the physical stability of the product may ~e adversely affected.
In suitable circumstances other anionic detergents, such as fatty alcohol sulfates, paraefin sulfonates, ol.efin sulfonate~, monoglyceride .sulfates, sarcosinates and similarly functioning detergents, preferably as the alkali metal, e.g., sodium salts, can be present, sometimes in partial replacement of the previously mentioned synthetic organic detergents but usually, if present, in addition to such detergents. Normally, the supplementing detergents will be sulfated or sulfonated products (usually as the sodium salts) and will contain long chain (8 to 20 carbon atoms) linear or fatty alkyl groups. In addition to any supplementing anionic synthetic organic deter-gents, there also may be present nonionic and amphoteric mater-ials, like the Neodols,~ sold by Shell Chemical Company, which are condensation products of ethylene oxide and higher fatty alcohols, e.g., Neodol~ 23-6.5, which is a condensation product of a higher fatty alcohol of about 12 to 13 carbon atoms with about 6.5 moles of ethylene oxide. Illustrations of the various detergents and classes of detergents mentioned may be found in the text Surface Active Agents, Vol. II, by Schwartz, Perry and Berch (Interscience Publishers, 195~), the descriptions of which are incorporated herein by reference.
~r ~2~'?~
The builder salt combination of this invention, which has been found to satisfactorily improve the detergency of the mixture of synthetic anionic organic detergents and produe the desired pH in the liquid detergent and in the wash water, is a mixture of sodium tripolyphosphate and sodium carbonate. The builder salts are employed in the present compositions in amounts generally oE from about 5 to 25%, by weight. For the preferred builder salt combination, sodium tripolyphosphate is present in amounts of from about 5 to 20~, preferably 10 to 16%, and sodium carbonate is present from about 1 to 10~, by weight, preferably 3 to 7%, the weight ratio of tripolyphos-phate to carbonate in the preferred bui1ders mixtures being from about 2:1 to 6:1, and most preferably from about 2:1 to 4:1. As used herein, the term alkali metal "carbonates" or "carbonate" is meant to include the carbonates, bicarbonates and sesquicarbonates of such alkali metal.
For best processing, easier mixing and good end-use properties it i5 preferred that the sodium tripolyphosphate be low in con-tent of Phase I type tripolyphosphate. Thus, normal-ly the content of Phase I type tripolyphosphate will be lessthan 30% of the tripolyphosphate employed. Although in some instances incompletely neutralized tripolyphosphate may be used, normally the phosphate employed may be considered as being pentasodium tripolyphosphate, NasP301o. Of course, in some instances, as when potassium salts of other materials are present, ion interchange in an aqueous medium may result in other salts than the sodium tripolyphosphate being present but for the purpose of this specification it will be considered that sodium tripolyphosphate, as the pentasodium salt, the material which is normally charged to the mixer to make the ., ~ 2~
present liquid detergent, is the tripolyphosphate employed.
Other pre~erred builder salts which may be used in place of sodium tripolyphosphate and sodium carbonate or in addition thereto include a polyacetal carboxylate as herein described and sodium nitrilotriacetate (NTA). of course, vari-ous mixtures of the mentioned water soluble builder salts can be utilized. Yet, the tripolyphosphate-carbonate mixture des-cribed has been found to be most preferred, although the other builders and mixtures thereof are also operative. Other build-ers which may be employed as supplements, in addition to theproportions of the above mentioned builders, include other phosphates, such as ~etrasodium pyrophosphate or tetrapotassium pyrophosphate, sodium bicarbonate, sodium citrate, sodium glu-conate, sodium silicate, and sodium sesquicarbonate. Among the water insoluble builders that may be used are the zeolites, such as Zeolite A, usually in the form of its crystalline hy-drate, although amorphous zeolites may also be useful.
Polyacetal carboxylates are generally described in U.S. Patents 4,144,226 and 4,315,092. U.S. Patent 4,146,495 describes detergent compositions containing polyacetal carboxy-lates as builders.
The polyacetal carboxylates which are useful herein as builders may be considered to be those described in U~S.
Patent 4,144,226 and may be made by the method mentioned there-in. A typical such product will be of the formula Rl - (cHo)n - R2 COOM
wherein M is selected ~rom the group consistiny of alkali metal, ammonium, alkyl groups of 1 to 4 carbon atoms, tetra-alkylammonium groups and alkanolamine groups, both of 1 to 4 ~97~
earbon atoms in the alkyls thereof, n avexages at least 4, and Rl and R2 are any chemic~lly stable groups which stabilize t~e polymer against rapi~ depolymerization in alkali~e solution. Preferably the polyacetal carboxylate will be one wherein M is alkali metal, e.g., sodium, n is from 50 to 200, ~1 is C~3cH2O MOOC
~CO- or H3C-CO-or a mixture thereof, R2 is -CH
and n averages from 20 to 100, more pre~erably 30 to 80.
The calculated weight average molecular weights of the polymers will normally be within the range of 2,000 to 70,000, preferably 3,500 to l0,000 and more preferably S,000 to 9,000, e.g., about 8,000.
A particularly preferred sodium polyacetal carboxylate is supplied by Monsanto Company and is known as Builder U. It has a calculated average molecular weight of about 8,000 and an acti~e polymer content of about 80%.
Although the preferrPd polyacetal carboxylates have been described above, it is to be understood that they may be wholly or partially replaced by other such polyacetal carbo~ylates or related organic builder salts described in the previously cited patents on such compounds, processes for the manufacture thereof and compositions in which they are employed. Also, the chain terminating groups described in the various patents, especially U.S. 4,144,226, may be utilized, providing ~hat they have the 4~
desired stabilizing properties, which allow the mentioned builders to be depolymeri~ed in acidic media, facilitating biodegradation thereof in waste streams, but maintain their stability in alkaline media, such as washing solutions.
The bentonite employed herein is a colloidal clay (aluminium silicate) containing montmorillonite. Swelling bentonites are generally characterized as sodium bentonites, i.e., bentonite wherein the predominant cation is sodium.
Among the sodium bentonite clays, those from Wyoming (generally referred to as Western or Wyoming bentonite) are especially preferred.
The swelling capacity of bentonite is generally associated with its fabric softening properties. In water the s~elling capacity of sodium bentonite is in the range of 3 to 20 milliliters/gram, preferably 7 to 15 ml/gram, and its viscosity, at 6% concentration in water, is usually in the range of 3 to 30 centipoises, preferably 8 to 30 centipoises.
Preferred swelling bentonites are sold under the trademark ~I-JEL by Georgia Kaolin Co. These materials are the same as bentonites which were formerly sold under the trademarks MIN~AL COLLOID and Tl.~IXO-JEL. They are selectively mined and beneficiated bentonites, and those considered to be most useful are available as HI-JEL Nos. 1,2,3 etc., corresponding to THIXO-JELs No's 1,2,3 and 4. Such materials have a maximum free moisture content (before addition to the liquid medium) o~ 4% to 8% and specific gravities of about 2.6. The bentonite is pre~erably one which will pass through a 200 mesh U.S. Sieve Series sieve, and most preferably at least 90% of the particles will pass through a No. 325 sieve, so that the equivalent diameter of the bentonite may be considered to be less than 74 microns, and more preferably less than about 44 microns.
lZ~7~
Typical chemical analyses of some bentonites that are useful for making the present liquid detergents show that they contain from 64.8 to 73.0% of sio2, 14 to 18% of A12O3, 1.6 to 2.7% of MgO, 1.3 to 3.1% of CaO, 2.3 to 3.4% of Fe2O3, 0.8 to 2.8% of Na2O and 0.4 to 7O0% of K2O.
Although the western bentonites are preferred it is also possible to utilize other bentonites, such as those which may be made by treating Italian or similar bentonites contain-ing relatively small proportions of exchangeable monovalent metals (sodium and potassium) with alkaline materials, c~uch as sodium carbonate, to increase the cation exchancJe capclcities o such products. It is considered that the ~a2O content of the bentonite should be at least about 0.5%, preferably at least 1%
and more preferably at least 2% so that the clay will be satis-factorily swelling, with good softening and dispersing proper-ties in aqueous suspension. Preferred swelling bentonites of the types described above are sold under the trade names Laviosa and Winkelmann, e.g., Laviosa AGB and Winkelmann G-13.
Other bentonites which are particularly useful for the present liquid detergent compositions because of their white or very light color include American Colloid Company's Pol.arite KB 325, a Cali~ornia bentonite, and Georgia Kaolin's GK 129, a Mexican ben-tonite.
The viscosity of the present liquid detergent is normally in the range of about 1000 to 10,000 centipoises, preferably 2000~7000 centipoises, but products of other suit-able viscosities may also be useful. At the viscosities men-tioned, the liquid detergent i6 pourable, stable, non-separa ting and uniform. The pH of the liquid detergent suspension , ~2~7~
usually in the range of 7 to 11.5, preferably 8 to 10.5, appears to help to maintain product stability and pourability.
The following examples illustrate but do not limit the invention. Unless otherwise indicated all parts are by weight and temperatures are in C.
EXAMPLE_l Component Percent Pentasodium tripolyphosphate 11.0 10 Bentonite ~Georgia-Kaolin 129) 12~0 Sodium carbonate 2.0 Sodium sesquicarbonate 2.0 Sodium linear tridecylben~ene 8.0 sulfonate AEOS(l) Carboxymethyl cellulose (CMC) 0.2 Optical brightener 0.3 Perfume 0.4 EnPyme (Esperase 8.0L)(2) 1.0 Glycerine 3.0 Borax 2.5 Citric Acid ~.o Water and adjuvants Balance (1) Sodium alkyl polyethoxy sulfate wherein the alkyl is 12 to 15 carbon atoms and the polyethoxy is 3 ethoxy groups.
(2) "Esperase" sold by Novo Industries having an activity of 8.0 KNPU/gram.
, - 15 -., ~ ., 79L~
The composition shown above was prepared by the following procedure: 30.0 parts of deionized water at 40F are added to a suitable mixing apparatus such as a vertical cylindrical tank equipped with a stirrer. With the stirrer adjusted for medium agitation, a mixture consisting of 2.0 parts anhydrous soda ash, 2.0 parts sodium sesquicarbonate, and 0.2 parts sodium carboxymethyl cellulose is incorporated into the water. The stirrer speed is then increased to maximum agitation and a mixture comprised of 11.0 parts pentasodium tripolyphosphate and 12.0 parts bentonite is slowly added to the mixing apparatus over a period of 10-15 Mlnutes to Eorm an off-white suspension.
The agitation speed is then decreased to a slow/medium setting while 8.64 parts of a high AI (about 55%) LTBS slurry is added.
Thereafter the optical brightener/color solution is added con-sisting of 0.3 parts Tinopal L~'IS-X (CIBA-GEIGY), 0.99 parts colorant, and 4.02 parts deionized water. Once a uniform blueish-green colored solution is obtained, 0.4 parts of perfume are added to the ~ixture under agitation. This is followed by the slow addition of 3.0 parts glycerine and 2.5 parts borax as a two com-ponent slurry. Stirring is continued until the mixture is uniorm in appearance and then 2.0 parts of citric acid and ~.0 parts water are slowly added. Agitation of the mixt~re is then reduced while 10.95 parts of a mixed AI detergent base consisting of an LTBS
slurry (about 30% AI) and AEOS (about 27.5~ AI) is added to the mixture. This is followed by the slow addition of l.O part proteolytic enzyme with continous agitation until all materials are completely dispersed or dissolved.
~2g7~
Enzyme-containing built liquid detergent compositions A to G were formulated as set forth below in Table 1. The percentages shown indicate weight percent. The arrows are meant to indicate the extent to which Compositions ~ -to G are identical to Composition A.
Component A B C D E F G
Pentasodium 11.0 Tripolyphosphate Bentonite (Georgia-Kaolin 129) 12.0 Sodium Carbonate 2.0 Sodium sesquicarbonate 2.0 Sodium Linear tridecyl- 8.0 benzene sulfonate AEOS(l) 3.0 Optical brightener 0.3 (Tinopal LMS-X) Perfume 0.4 CMC 0.2 Enzyme(2) 1.0 ~ ~ ~ / \ / \ / \ ~ \ /
Glycerine - 3.0 - 3.0 - - 3.0 Borax -- 2.5 2.5 - 2.5 2.5 Carboxylic acid compound - - - - 2.0 2.0 2.0 Water and adjuvants - Balance (1) Sodium alkyl polyethoxy sulfa-te wherein the alkyl is 12 to 15 carbon atoms and the polyethoxy is 3 ethoxy groups.
(2) "Esperase" sold by Novo Industries having an activity of 8.0 KNPU/gm (Kilo Novo Protease units/gm).
~2g~
Tl~e enzyme ~ctivities of Compositions A to F were tested after 7 days storage at 110F. The measured enzyme activity ~or each co~position after this period of storage is indicated in Table 2 as a percent of the initial value. The ~arious carboxylic acids and salts used in the general formulas of Compositions A, B, C, D, E, and G are shown in Table 2 as well as the enzyme activities corresponding to each composition.
ENZY'~E STABILITY
Percent Active Enzyme Co~position After 7 Days_at 110F
A (control) ND
B (with glycerine) ND
C (with borax) ND
D (with glycerine and borax) 50 CompositionE (with carboxylic acid compound) wherein the carboxylic acid ` compound is:
: (1) Succinic acid - ND
(2) Malonic acid "
(3) Malic acid "
(4) Tartaric acid 1-(5) Aspartic acid "
(6) Citric acid "
(7) Sodium tartrate "
(8~ Sodium citrate "
* ND = not detectable (below 10~ residual acti~ity) 112~74 ~
Composition G (with glycerine/borax/carboxylic acid compound) wherein thePercent Active Enzyme carboxylic acid compound is:After 7 Days at llO~F
~1) Succinic acid 70 (2) Malonic acid 70 (3~ Malic acid 78 (~) Tartaric acid 73 (5) Aspartic acid 90 (6) Citric acid 74 (7) Sodium tartrate 66 (8) SoAium citrate 52 As evident from Table 2, Composition A, the control composition, as well as Compositions B and C containing indivi-dual stabilizers of glycerine and borax, respectively, mani-fested almost no enzyme activity after the 7 day storage period at 10~F. Since enzyme activities below 10% could not be pre-cisely measured they are designated "ND". Composition D con-taining glycerine/borax in the absence of a carboxylic acid compound provided an improvement in enzyme stability relative to Composition A, but about 50% of the enzyme was deactivated.
The various Compositions E containing a variety of carboxylic acid compounds, as indicated, manifested absolutely no improve-ment in enzyme stability relative to Composition A. However, Compositions G ~ormulated in accordance wi-th the invention demonstrate the unexpected and synergistic improvement in enzyme stability which is achieved with the use of glycerine/-borax in combination with a carboxylic acid compound in the present liquid detergent compositions. It is noted that almost every one of the compositions corresponding to Composition G
demonstrated a signiEicant improvement in enzyme activity relative to Composition D (containing glycerine and bGrax).
~ 19 --, ~ .
A comparison of the enzyme activities achieved with Co~positions D (glycerine/borax) and various Compositions F
(borax/carboxylic acid compound) and G (formulated in accordance ~ith the invention) is set forth below in Table 3.
Percent active Enzyme After Composition 7 Days at 110F
D (Glyc~rine/borax) 50 F (Borax/malonic acid) 45 G (Glycerine/borax/malonic acid) 70 F (Borax/aspartic acId) 72 G (Glycerine/borax/aspartic acid) go F (Borax/citric acid) 42 G (Glycerine/borax/citric acid) 74 As shown in Table 3, the various Compositions G containing a three component stabilizer system in accordance with the invention provided a synergistic improvement in enzyme stability relative to Compositions D and F formulated in accordance with the prior art.
(8~ Sodium citrate "
* ND = not detectable (below 10~ residual acti~ity) 112~74 ~
Composition G (with glycerine/borax/carboxylic acid compound) wherein thePercent Active Enzyme carboxylic acid compound is:After 7 Days at llO~F
~1) Succinic acid 70 (2) Malonic acid 70 (3~ Malic acid 78 (~) Tartaric acid 73 (5) Aspartic acid 90 (6) Citric acid 74 (7) Sodium tartrate 66 (8) SoAium citrate 52 As evident from Table 2, Composition A, the control composition, as well as Compositions B and C containing indivi-dual stabilizers of glycerine and borax, respectively, mani-fested almost no enzyme activity after the 7 day storage period at 10~F. Since enzyme activities below 10% could not be pre-cisely measured they are designated "ND". Composition D con-taining glycerine/borax in the absence of a carboxylic acid compound provided an improvement in enzyme stability relative to Composition A, but about 50% of the enzyme was deactivated.
The various Compositions E containing a variety of carboxylic acid compounds, as indicated, manifested absolutely no improve-ment in enzyme stability relative to Composition A. However, Compositions G ~ormulated in accordance wi-th the invention demonstrate the unexpected and synergistic improvement in enzyme stability which is achieved with the use of glycerine/-borax in combination with a carboxylic acid compound in the present liquid detergent compositions. It is noted that almost every one of the compositions corresponding to Composition G
demonstrated a signiEicant improvement in enzyme activity relative to Composition D (containing glycerine and bGrax).
~ 19 --, ~ .
A comparison of the enzyme activities achieved with Co~positions D (glycerine/borax) and various Compositions F
(borax/carboxylic acid compound) and G (formulated in accordance ~ith the invention) is set forth below in Table 3.
Percent active Enzyme After Composition 7 Days at 110F
D (Glyc~rine/borax) 50 F (Borax/malonic acid) 45 G (Glycerine/borax/malonic acid) 70 F (Borax/aspartic acId) 72 G (Glycerine/borax/aspartic acid) go F (Borax/citric acid) 42 G (Glycerine/borax/citric acid) 74 As shown in Table 3, the various Compositions G containing a three component stabilizer system in accordance with the invention provided a synergistic improvement in enzyme stability relative to Compositions D and F formulated in accordance with the prior art.
Claims (22)
1. A stabilized fabric softening enzyme-containing built liquid detergent composition comprising:
(a) from about 5 to 20%, by weight, of one or more sur-face active detergent compounds selected from the group consisting of anionic, nonionic and amphoteric detergent compounds;
(b) from about 5 to 30%, by weight, of one or more build-er salts selected from the group consisting of alkali metal tripolyphosphates, alkali metal carbonates, alkali metal nitrilotriacetates and polyacetal car-boxylates;
(c) from about 5 to 20%, by weight, of a swelling bento-nite clay;
(d) an effective amount of an enzyme or an enzyme mixture selected from the group consisting of alkaline pro-tease enzymes and alpha-amylase enzymes;
(e) an enzyme-stabilizing system containing, based on the weight of the detergent composition, (i) from about 1% to 10% glycerine: (ii) from about 1 to 8% of a boron compound selected from the group consisting of boric acid, boric oxide and alkali metal borates; and (iii) from about 0.5 to 8% of a carboxylic acid com-pound selected from the group consisting of mono, di and/or polycarboxylic acids having 1 to 8 carbon atoms and water-soluble salts thereof; and (f) the balance comprising water and optionally perfume and other adjuvants.
(a) from about 5 to 20%, by weight, of one or more sur-face active detergent compounds selected from the group consisting of anionic, nonionic and amphoteric detergent compounds;
(b) from about 5 to 30%, by weight, of one or more build-er salts selected from the group consisting of alkali metal tripolyphosphates, alkali metal carbonates, alkali metal nitrilotriacetates and polyacetal car-boxylates;
(c) from about 5 to 20%, by weight, of a swelling bento-nite clay;
(d) an effective amount of an enzyme or an enzyme mixture selected from the group consisting of alkaline pro-tease enzymes and alpha-amylase enzymes;
(e) an enzyme-stabilizing system containing, based on the weight of the detergent composition, (i) from about 1% to 10% glycerine: (ii) from about 1 to 8% of a boron compound selected from the group consisting of boric acid, boric oxide and alkali metal borates; and (iii) from about 0.5 to 8% of a carboxylic acid com-pound selected from the group consisting of mono, di and/or polycarboxylic acids having 1 to 8 carbon atoms and water-soluble salts thereof; and (f) the balance comprising water and optionally perfume and other adjuvants.
2. A liquid detergent composition according to claim 1 comprising:
(a) from about 5 to 15% of an alkali metal alkylbenzene sulfonate wherein the alkyl group contains 12 to 15 carbon atoms;
(b) from about 0.5 to 5% of an alkali metal alkyl poly-ethoxy sulfate wherein the alkyl group contains 10 to 18 carbon atoms and the polyethoxy is of 3 to 11 ethylene oxide groups, the weight ratio of (a) to (b) being from about 2:1 to about 6:1;
(c) from about 5 to 20% of sodium tripolyphosphate;
(d) from about 1 to 10% of sodium carbonate, sodium bi-carbonate or mixtures thereof, the weight ratio of (c) to (d) being from about 2:1 to about 6:1;
(e) from about 10 to 15% of a sodium bentonite;
(f) an effective amount of said enzyme or enzyme mix-ture;
(g) the enzyme stabilizing system containing, based on the weight of the detergent composition, (i) from about 1 to 5% glycerine (ii) from about 1 to 5% of an alkali metal borate and (iii) from about 0.5 to 4% of said carboxylic acid compound; and (h) the balance comprising water and optionally minor adjuvants.
(a) from about 5 to 15% of an alkali metal alkylbenzene sulfonate wherein the alkyl group contains 12 to 15 carbon atoms;
(b) from about 0.5 to 5% of an alkali metal alkyl poly-ethoxy sulfate wherein the alkyl group contains 10 to 18 carbon atoms and the polyethoxy is of 3 to 11 ethylene oxide groups, the weight ratio of (a) to (b) being from about 2:1 to about 6:1;
(c) from about 5 to 20% of sodium tripolyphosphate;
(d) from about 1 to 10% of sodium carbonate, sodium bi-carbonate or mixtures thereof, the weight ratio of (c) to (d) being from about 2:1 to about 6:1;
(e) from about 10 to 15% of a sodium bentonite;
(f) an effective amount of said enzyme or enzyme mix-ture;
(g) the enzyme stabilizing system containing, based on the weight of the detergent composition, (i) from about 1 to 5% glycerine (ii) from about 1 to 5% of an alkali metal borate and (iii) from about 0.5 to 4% of said carboxylic acid compound; and (h) the balance comprising water and optionally minor adjuvants.
3. A liquid detergent composition according to claim 2 wherein said alkali metal alkylbenzene sulfonate is sodium linear tridecylbenzene sulfonate and said alkali metal alkyl polyethoxy sulfate is one wherein the alkali metal is sodium, the alkyl group contains 12 to 15 carbon atoms and the poly-ethoxy is of about 3 ethylene oxide groups.
4. A liquid detergent composition according to claim 3 wherein the ratio of tridecylbenzene sulfonate to polyethoxy sulfate is from about 2:1 to about 4:1.
5. A liquid detergent composition according to claim 2 wherein said boron compound is an alkali metal borate.
6. A liquid detergent composition according to claim 5 wherein said borate is borax.
7. A liquid detergent composition according to claim 2 which contains from about 8 to 16% sodium tripolyphosphate and from about 2 to 6% of sodium carbonate, sodium bicarbonate or mixtures thereof.
8. A liquid detergent composition according to claim 2 wherein said carboxylic acid compound is aspartic acid or a water-soluble salt thereof.
9. A liquid detergent composition according to claim 2 wherein said carboxylic acid compound is tartaric acid or a water-soluble salt thereof.
10. A liquid detergent according to claim 2 wherein said carboxylic acid compound is citric acid or a water-soluble salt thereof.
11. A liquid detergent composition according to claim 2 wherein said carboxylic acid compound is malonic acid or a water-soluble salt thereof.
12. A liquid detergent composition according to claim 2 wherein said carboxylic acid compound is malic acid or a water-soluble salt thereof.
13. A method of laundering comprising contacting the stained and/or soiled fabrics to be laundered with a stabilized enzyme-containing built liquid detergent composition compris-ing:
(a) from about 5 to 20%, by weight, of one or more sur-face active detergent compounds selected from the group consisting of anionic, nonionic and amphoteric detergent compounds;
(b) from about 5 to 30%, by weight, of one or more build-ers salts selected from the group consisting of alka-li metal tripolyphosphates, alkali metal carbonates, alkali metal nitrilotriacetates, and polyacetal car-boxylates;
(c) from about 5 to 20%, by weight, of a swelling bento-nite clay;
(d) an effective amount of an enzyme or an enzyme mixture selected from the group consisting of alkaline pro-tease enzymes and alpha-amylase enzymes;
(e) an enzyme-stabilizing system containing, based on the weight of the detergent composition, (i) from about 1% to 10% glycerine (ii) from about 1 to 8% of a boron compound selected from the group consisting of boric acid, boric oxide and alkali metal borates; and (iii) from about 0.5 to 8% of a carboxylic acid com-pound selected from the group consisting of mono, di and/or polycarboxylic acids having 1 to 8 carbon atoms and water-soluble salts thereof; and (f) the balance comprising water and optionally perfume and other adjuvants.
(a) from about 5 to 20%, by weight, of one or more sur-face active detergent compounds selected from the group consisting of anionic, nonionic and amphoteric detergent compounds;
(b) from about 5 to 30%, by weight, of one or more build-ers salts selected from the group consisting of alka-li metal tripolyphosphates, alkali metal carbonates, alkali metal nitrilotriacetates, and polyacetal car-boxylates;
(c) from about 5 to 20%, by weight, of a swelling bento-nite clay;
(d) an effective amount of an enzyme or an enzyme mixture selected from the group consisting of alkaline pro-tease enzymes and alpha-amylase enzymes;
(e) an enzyme-stabilizing system containing, based on the weight of the detergent composition, (i) from about 1% to 10% glycerine (ii) from about 1 to 8% of a boron compound selected from the group consisting of boric acid, boric oxide and alkali metal borates; and (iii) from about 0.5 to 8% of a carboxylic acid com-pound selected from the group consisting of mono, di and/or polycarboxylic acids having 1 to 8 carbon atoms and water-soluble salts thereof; and (f) the balance comprising water and optionally perfume and other adjuvants.
14. A method according to claim 13 wherein said liquid detergent composition comprises:
(a) from about 5 to 15% of an alkali metal alkylbenzene sulfonate wherein the alkyl group contains 12 to 15 carbon atoms;
(b) from about 0.5 to 5% of an alkali metal alkyl poly-ethoxy sulfate wherein the alkyl group contains 10 to 18 carbon atoms and the polyethoxy is of 3 to 11 ethylene oxide groups, the weight ratio of (a) to (b) being from about 2:1 to about 6:1;
(c) from about 5 to 20% of sodium tripolyphosphate;
(d) from about 1 to 10% of sodium carbonate, sodium bi-carbonate or mixtures thereof, the weight ratio of (c) to (d) being from about 2:1 to about 6:1;
(e) from about 10 to 15% of a sodium bentonite;
(f) an effective amount of said enzyme or enzyme mix-ture;
(g) the enzyme stabilizing system containing, based on the weight of the detergent composition, (i) from about 1 to 5% glycerine (ii) from about 1 to 5% of an alkali metal borate and (iii) from about 0.5 to 4% of said carboxylic acid compound; and (h) the balance comprising water and optionally minor adjuvants.
(a) from about 5 to 15% of an alkali metal alkylbenzene sulfonate wherein the alkyl group contains 12 to 15 carbon atoms;
(b) from about 0.5 to 5% of an alkali metal alkyl poly-ethoxy sulfate wherein the alkyl group contains 10 to 18 carbon atoms and the polyethoxy is of 3 to 11 ethylene oxide groups, the weight ratio of (a) to (b) being from about 2:1 to about 6:1;
(c) from about 5 to 20% of sodium tripolyphosphate;
(d) from about 1 to 10% of sodium carbonate, sodium bi-carbonate or mixtures thereof, the weight ratio of (c) to (d) being from about 2:1 to about 6:1;
(e) from about 10 to 15% of a sodium bentonite;
(f) an effective amount of said enzyme or enzyme mix-ture;
(g) the enzyme stabilizing system containing, based on the weight of the detergent composition, (i) from about 1 to 5% glycerine (ii) from about 1 to 5% of an alkali metal borate and (iii) from about 0.5 to 4% of said carboxylic acid compound; and (h) the balance comprising water and optionally minor adjuvants.
15. A method according to claim 14 wherein said alkali metal alkylbenzene sulfonate is sodium linear tridecylbenzene sulfonate and said alkali metal alkyl polyethoxy sulfate is one wherein the alkali metal is sodium, the alkyl group contains 12 to 15 carbon atoms and the polyethoxy is of about 3 ethylene oxide groups.
16. A method according to claim 15 wherein the ratio of tridecylbenzene sulfonate to polyethoxy sulfate is from about 2:1 to about 4:1.
17. A method according to claim 14 wherein said boron compound is borax.
18. A method according to claim 14 wherein the liquid detergent composition contains from about 8 to 16% sodium tri-polyphosphate and from about 2 to 6% sodium carbonate, sodium bicarbonate or mixtures thereof.
19. A method according to claim 14 wherein the carboxylic acid compound is aspartic acid or a water-soluble salt there-of.
20. A method according to claim 14 wherein the carboxylic acid compound is citric acid or a water-soluble salt thereof.
21. A method according to claim 14 wherein the carboxylic acid compound is malic acid or a water-soluble salt thereof.
22. A method according to claim 14 wherein the carboxylic acid compound is malonic acid or a water-soluble salt thereof.
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US75952385A | 1985-07-26 | 1985-07-26 | |
US759523 | 1985-07-26 | ||
US79271085A | 1985-10-30 | 1985-10-30 | |
US792710 | 1985-10-30 |
Publications (1)
Publication Number | Publication Date |
---|---|
CA1297440C true CA1297440C (en) | 1992-03-17 |
Family
ID=27116693
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA000514035A Expired - Lifetime CA1297440C (en) | 1985-07-26 | 1986-07-17 | Fabric softening liquid detergent |
Country Status (31)
Country | Link |
---|---|
KR (1) | KR940010118B1 (en) |
AT (1) | AT397810B (en) |
AU (1) | AU590589B2 (en) |
BE (1) | BE905167A (en) |
BR (1) | BR8603479A (en) |
CA (1) | CA1297440C (en) |
CH (1) | CH669958A5 (en) |
DE (1) | DE3623943A1 (en) |
DK (1) | DK165331C (en) |
EG (1) | EG17901A (en) |
ES (1) | ES2001483A6 (en) |
FR (1) | FR2585361B1 (en) |
GB (1) | GB2178055B (en) |
GR (1) | GR861947B (en) |
HK (1) | HK1993A (en) |
IE (1) | IE59691B1 (en) |
IL (1) | IL79450A0 (en) |
IN (1) | IN170204B (en) |
IT (1) | IT1195869B (en) |
LU (1) | LU86526A1 (en) |
MA (1) | MA20741A1 (en) |
MX (1) | MX167431B (en) |
MY (1) | MY101616A (en) |
NL (1) | NL8601927A (en) |
NO (1) | NO165928C (en) |
NZ (1) | NZ216792A (en) |
PH (1) | PH22908A (en) |
PT (1) | PT83023B (en) |
SE (1) | SE468518B (en) |
SG (1) | SG108692G (en) |
ZW (1) | ZW13386A1 (en) |
Families Citing this family (17)
Publication number | Priority date | Publication date | Assignee | Title |
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SE467827B (en) * | 1985-07-26 | 1992-09-21 | Colgate Palmolive Co | STABILIZED ENZYMINE-CONTAINING EFFECTIVE LIQUID DETERGENT COMPOSITION AND ITS USE IN WASHING TEXTILES |
GB8519047D0 (en) * | 1985-07-29 | 1985-09-04 | Unilever Plc | Detergent composition |
GB2200132B (en) * | 1986-12-15 | 1991-09-18 | Colgate Palmolive Co | Stabilised enzyme systems and compositions containing them |
DE3704465C2 (en) * | 1987-02-13 | 1995-11-02 | Roehm Gmbh | Liquid formulations of enzymes |
US6287841B1 (en) | 1988-02-11 | 2001-09-11 | Genencor International, Inc. | High alkaline serine protease |
PT89702B (en) | 1988-02-11 | 1994-04-29 | Gist Brocades Nv | PROCESS FOR PREPARING NEW PROTEOLITIC ENZYMES AND DETERGENTS THAT CONTAINS THEM |
AU3667189A (en) * | 1988-06-23 | 1990-01-04 | Unilever Plc | Enzyme-containing liquid detergents |
GB8822374D0 (en) * | 1988-09-23 | 1988-10-26 | Abster Co Ltd | Detergent composition |
US5500151A (en) * | 1988-10-07 | 1996-03-19 | Colgate-Palmolive Co. | Heavy duty fabric softening laundry detergent composition |
DE3911099A1 (en) * | 1989-04-06 | 1990-10-11 | Henkel Kgaa | METHOD FOR CLEANING ENZYME SOLUTIONS |
DE3915277A1 (en) * | 1989-05-10 | 1990-11-15 | Henkel Kgaa | METHOD FOR PURIFYING ENZYME LIQUID CONCENTRATES |
DE68928569D1 (en) * | 1989-11-06 | 1998-03-05 | Colgate Palmolive Co | Softening heavy-duty detergent composition for laundry |
NZ237570A (en) * | 1990-04-13 | 1993-09-27 | Colgate Palmolive Co | Enzyme stabilising composition and stabilised enzyme-containing built detergent compositions |
JPH05507441A (en) * | 1991-02-12 | 1993-10-28 | バックマン・ラボラトリーズ・インターナショナル・インコーポレーテッド | Compositions and methods for removing biofilm from or preventing biofilm deposition on surfaces in industrial water systems |
AU669900B2 (en) * | 1992-07-20 | 1996-06-27 | Colgate-Palmolive Company, The | Stabilized built aqueous liquid softergent compositions |
ZA943640B (en) * | 1993-06-07 | 1995-01-26 | Buckman Labor Inc | Synergistically stabilized liquid enzymatic compositions |
GB9822797D0 (en) * | 1998-10-19 | 1998-12-16 | United States Borax Inc | Pourable aqueous boron-containing compositions and their preparation |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FI61715C (en) * | 1976-11-01 | 1982-09-10 | Unilever Nv | ENZYMER INNEHAOLLANDE STABILIZERAD FLYTANDE DETERGENTKOMPOSITION |
IT1129814B (en) * | 1980-07-02 | 1986-06-11 | Unilever Nv | LIQUID ENZYMATIC DETERGENT COMPOSITION |
EP0080748B1 (en) * | 1981-11-13 | 1985-07-10 | Unilever N.V. | Enzymatic liquid cleaning composition |
AU547579B2 (en) * | 1981-11-13 | 1985-10-24 | Unilever Plc | Low foaming liquid detergent composition |
US4462922A (en) * | 1981-11-19 | 1984-07-31 | Lever Brothers Company | Enzymatic liquid detergent composition |
US4529525A (en) * | 1982-08-30 | 1985-07-16 | Colgate-Palmolive Co. | Stabilized enzyme-containing detergent compositions |
US4469605A (en) * | 1982-12-13 | 1984-09-04 | Colgate-Palmolive Company | Fabric softening heavy duty liquid detergent and process for manufacture thereof |
GB8305790D0 (en) * | 1983-03-02 | 1983-04-07 | Unilever Plc | Liquid detergent composition |
GB8311314D0 (en) * | 1983-04-26 | 1983-06-02 | Unilever Plc | Aqueous enzyme-containing compositions |
NZ208157A (en) * | 1983-05-31 | 1986-11-12 | Colgate Palmolive Co | Built single-phase liquid detergent compositions containing stabilised enzymes |
NZ208156A (en) * | 1983-05-31 | 1986-11-12 | Colgate Palmolive Co | Built single-phase liquid detergent compositions containing stabilised enzymes |
US4507219A (en) * | 1983-08-12 | 1985-03-26 | The Proctor & Gamble Company | Stable liquid detergent compositions |
DE3574729D1 (en) * | 1984-05-14 | 1990-01-18 | Procter & Gamble | LIQUID CLEANING AGENTS CONTAINING BORIC ACID FOR STABILIZING ENZYMS. |
SE467827B (en) * | 1985-07-26 | 1992-09-21 | Colgate Palmolive Co | STABILIZED ENZYMINE-CONTAINING EFFECTIVE LIQUID DETERGENT COMPOSITION AND ITS USE IN WASHING TEXTILES |
-
1986
- 1986-07-08 NZ NZ216792A patent/NZ216792A/en unknown
- 1986-07-08 SE SE8603036A patent/SE468518B/en not_active IP Right Cessation
- 1986-07-10 IN IN606/DEL/86A patent/IN170204B/en unknown
- 1986-07-14 AU AU60132/86A patent/AU590589B2/en not_active Ceased
- 1986-07-16 DE DE3623943A patent/DE3623943A1/en not_active Ceased
- 1986-07-16 ZW ZW133/86A patent/ZW13386A1/en unknown
- 1986-07-17 CA CA000514035A patent/CA1297440C/en not_active Expired - Lifetime
- 1986-07-17 IL IL79450A patent/IL79450A0/en not_active IP Right Cessation
- 1986-07-21 FR FR868610550A patent/FR2585361B1/en not_active Expired - Lifetime
- 1986-07-21 PT PT83023A patent/PT83023B/en unknown
- 1986-07-21 MA MA20969A patent/MA20741A1/en unknown
- 1986-07-22 CH CH2942/86A patent/CH669958A5/de not_active IP Right Cessation
- 1986-07-22 IT IT48289/86A patent/IT1195869B/en active
- 1986-07-22 PH PH34051A patent/PH22908A/en unknown
- 1986-07-23 AT AT0199086A patent/AT397810B/en not_active IP Right Cessation
- 1986-07-23 BR BR8603479A patent/BR8603479A/en not_active IP Right Cessation
- 1986-07-24 ES ES8600598A patent/ES2001483A6/en not_active Expired
- 1986-07-24 GB GB8618043A patent/GB2178055B/en not_active Expired
- 1986-07-24 GR GR861947A patent/GR861947B/en unknown
- 1986-07-24 EG EG464/86A patent/EG17901A/en active
- 1986-07-25 KR KR1019860006065A patent/KR940010118B1/en active IP Right Grant
- 1986-07-25 NL NL8601927A patent/NL8601927A/en not_active Application Discontinuation
- 1986-07-25 IE IE197486A patent/IE59691B1/en not_active IP Right Cessation
- 1986-07-25 LU LU86526A patent/LU86526A1/en unknown
- 1986-07-25 MX MX003265A patent/MX167431B/en unknown
- 1986-07-25 BE BE0/216971A patent/BE905167A/en not_active IP Right Cessation
- 1986-07-25 NO NO862996A patent/NO165928C/en unknown
- 1986-07-25 DK DK355186A patent/DK165331C/en not_active IP Right Cessation
-
1987
- 1987-09-28 MY MYPI87002055A patent/MY101616A/en unknown
-
1992
- 1992-10-14 SG SG1086/92A patent/SG108692G/en unknown
-
1993
- 1993-01-14 HK HK19/93A patent/HK1993A/en unknown
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