EP0178029A2

EP0178029A2 - Detergent compositions containing compatible organic emetic agent

Info

Publication number: EP0178029A2
Application number: EP85201633A
Authority: EP
Inventors: Roy Goulding; James Pyott Johnston; George Calvin; John Richard Walker
Original assignee: Procter and Gamble European Technical Center; Procter and Gamble Co
Current assignee: Procter and Gamble European Technical Center; Procter and Gamble Co
Priority date: 1984-10-12
Filing date: 1985-10-09
Publication date: 1986-04-16
Also published as: EP0178029A3; GB8425881D0

Abstract

Detergent compositions, preferably liquid compositions which are substantially free of polyphosphate builders, containing surface-active agents, and low level of a detergent compatible organic emetic agent are disclosed.

Description

This invention relates to detergent compositions in general containing a surface-active agent and, if desirable, further matrix components and conventional additives which compositions provide protection against assimilation following (accidental) ingestion of the composition.
In more detail, the invention herein relates to detergent compositions broadly, which contain usual and conventional components at levels established in the art. and in addition an effective amount of an organic emetic agent that is compatible with detergents.
Detergents were previously formulated around high alkalinity, inorganic builder salt, frequently polyphosphate builders, high electrolyte diluents such as sodium sulphate, and a myriad of other conventional detergent additives which taken cumulatively were known to provide excellent emetic properties to the detergents and thus provide additional protection following ingestion by the users beyond that provided by the inherent safety of the ingredients of the products. The same was applicable to liquid detergent compositions formulated along the same principles, i.e., containing substantial levels of polyphosphate builder salts. While a minor part of commercial liquid detergents were formulated with the aid of a limited number of relatively innocuous components, and thus would not exhibit inherent vomitory properties, those compositions were relatively harmless and the need to provide built-in safeguards against assimilation were not necessary.
Over the last decennium, detergent technology, particularly heavy-duty liquid detergent technology, has advanced dramatically chiefly for the purpose of meeting ever increased consumer demands for better performance. In order to meet these objectives, three formulation aspects have received particular attention:

(1) the active ingredient concentration in some particularly heavy-duty liquid detergents has more than doubled;
(2) a number of new categories of ingredients have been used for providing up to now unattainable performance benefits; and
(3) the complex interaction of the multiple components in the formula.

While the consumers are constantly in search of more efficient detergents with better performance, particularly in the care of laundry detergents, the public interest as seen from an individual and environmental standpoint, emphasizes the need to provide safe and relatively mild products for every day use.
Considerable research and development efforts have been undertaken to cope with the problems described hereinbefore and consequently to provide means, built-in through the use of raw materials generally recognized as being safe, or external or both, such that the consumer would be doubly protected in all potential usage and exposure situations. As an example, a mildly alkaline to neutral light duty liquid detergent has been commercialized containing denatonium benzoate as a bitterness agent to prevent large-scale ingestion of the liquid product. Well-known external safety means can be represented by "child-proof" closures, i.e., the detergent is presented in bottles having a fairly complicated closing mechanism thereby preventing easy access to the product.
The prior art approaches are directed to preventing accidental ingestion but, importantly, do not provide any safeguard against assimilation if ingestion were to occur. The external means investigated earlier are cumbersome in the absence of something induced through the inherent ability of the product to produce such an effect, economically unattractive and equally substandard in that they do not provide any safeguard against assimilation following ingestion.
It is a major object of this invention to provide detergent compositions containing surface-active agents and, if desirable other matrix and additive substances, which compositions do have built-in safeguards against assimilation following accidential ingestion by the user.
It is a further objective of this invention to provide liquid heavy duty detergents containing high levels of actives and other ingredients said compositions having emetic properties to forego assimilation following ingestion by the user.
It is still another object of the invention to formulate concentrated heavy-duty liquid detergents which are substantially free of polyphosphate builder salts and which are formulated at neutral to mildly alkaline pH which compositions provide built-in protection against accidental assimilation by the user.
The above and other advantages can now be achieved from the use of the compositions herein, namely detergent compositions, particularly heavy-duty liquid detergent compositions which are substantially free of polyphosphate builder salt, which detergents contain an effective, but low, level of a detergent compatible emetic agent. The major parameters of the invention are described hereinafter.

SUMMARY OF THE INVENTION

It has now been discovered that detergent compositions, particularly heavy-duty liquid detergent compositions, which are substantially free of polyphosphate builders, can be formulated having additional protection against assimilation following ingestion by the user. The detergent compositions herein contain in addition to the surface-active agents and additional additives, a detergent compatible organic emetic agent in an effective level, usually in the range from 2 ppm to 1000 ppm.
The major parameters of the invention and preferred embodiments are described hereinafter.
Unless indicated to the contrary, the "percent" indications stand for "percent by weight".

DETAILED DESCRIPTION OF THE INVENTION.

The compositions herein contain a surface-active agent, if desired, conventional detergent components and additives, and a detergent compatible organic emetic agent in an effective amount, frequently of from 2-2000 ppm.
The surface-active agents can be incorporated in levels ranging from 1% to 60%. The surface-active agent levels of a given preferred embodiment can vary depending upon the contemplated utilization of a given composition and the choice of co-components. For example, solid, particularly granular, detergent compositions usually comprise from _3% to 25% of surface-active agents, whereas liquid detergent compositions, especially heavy-duty liquid detergent compositions which are substantially free of polyphosphate builders, frequently comprise the surface-active agents in levels ranging from 10% to 60%.
The surface-active agents which can be used in the compositions of this invention are represented by known organic synthetic and natural surface-active agents which are of the anionic. nonionic, zwitterionic, ampholytic and semi-polar types. Mixtures of these surface-active agents are frequently used in commercial detergent executions and are also contemplated in this invention.
Specific species of suitable surface-active agents for use herein include alkyl benzene sulfonates, alkyl- and alkylether sulfates. paraffin sulfonates. olefin sulfonates, alkoxylated (especially ethoxylated) alcohols and alkyl phenols, amine oxides, alpha-sulfonates of fatty acids and of fatty acid esters, and the like. which are well-known from the detergency art. In general, such detersive surfactants contain an alkyl group in the C₉-C₁₈ range: the anionic detersive surfactants can be used in the form of their sodium, potassium or alkanolamine salts, particularly triethanolamine monoethanolamine or monomethylethanolamine. Cyclohexylamine is another preferred counterion but it is to be understood that the presence of magnesium cations in the compositions usually means that at least some portion of the anionic surfactant will be in the mangesium salt form: the nonionics generally contain from about 5 to about 17 ethylene oxide groups. U.S. Patents 4.111.855 and 3.995.669 contain detailed listings of such typical detersive surfactants. C₁₁-C₁₆ alkyl benzene sulfonates. C12-C18 paraffin-sulfonates and alkyl sulfates, and the ethoxylated alcohols and alkyl phenols are especially preferred in the compositions of the present type.
Mixtures of ethoxylated nonionics and anionics such as alkyl benzene sulfonates. alkyl sulfates and paraffin sulfonates are frequently preferred for use in concentrated heavy-duty liquid detergents which are substantially free of polyphosphate builders. The like liquid compositions can also contain preferably as a co-surfactant a semi-polar surface-active agent, preferably C₈-C₁₈ di-methyl amine oxide.
Surface-active agents of natural origin are frequently represented by soaps and fatty acids of natural or synthetic origin such as lauric. myristic, palmitic. stearic and oleic acids and poly-unsaturated fatty acids. Mixtures of fatty acids and the corresponding alkali-metal soaps derived from palm oil, coconut oil and the like having a C₁₂-C₁₈ carbon chain length are frequently used.
The detergent compatible organic emetic agent can be represented by organic emetic agents well-known in the domain of technology. The emetic agent shall be detergent-compatible i.e. shall remain effective and not be modified, inactivated or more in general altered in the presence of the additional detergent components. The compatibility of a given emetic agent can easily be verified; the result can vary depending upon the composition of the emetic agent as well as its chemical structure.
The emetic agent is utilized in an effective level usually in the range from 2 to 1000 ppm, calculated as active ingredient. It is well-known that the activity of emetic agents can vary considerably and the indicated usage range is believed to represent an effective detergent range.
Examples of suitable emetic agents include mustard (black and white), ipecac, apomorphine and s-triazolo(1,5-a) pyrimidine derivatives having the formula:
acylderivatives or salts thereof wherein R₁ is an amino-. alkylamino-. phenylalkylamino-, dialkylamino-, urea-. carboxyl-, hydroxyalkyl- or carbamoyl-group. R₂ is an alkyl-, cycloalkyl- or alkenyl-group and R₃ is hydrogen. halogen or an alkyl- or hydroxylalkyl-group, one of X or Y is an oxygen- or a sulphur-atom and the other hydrogen or an alkyl-group, wherein the nucleus has a double bond between carbon atoms 6 and 7 if X is sulphur or oxygen and a double bond between carbon atoms 5 and 6 if Y is oxygen or sulphur.
A preferred species has the formula:
wherein R₁ is hydrogen, an alkyl-group with 1 to 4 carbon atoms or a carbethoxy-group. R₂ is an alkyl-group with 1 to 4 carbon atoms or an alkyl group, and R₃ is an alkyl-group with 1 to 4 carbon atoms or addition-salt thereof. (As is well-known a s-triazolo-/1,5-a/pyrimidine-ring is numbered in such a way that the nitrogen atoms have the positions 1. 3. 4 and 7a.) Particularly useful derivatives of the 5-oxo-4.5-dihydro-s-triazolo/1.5-a/pyrimidine are the 6-methyl-4-n-propyl-2-n-propylamino-. 2-amino-6-methyl-4-allyl-, 2-amino-4.6-di-n-propyl- and 2-ethoxycarbonylamino-6-methyl-4-n-propyl-derivatives.
A particularly useful triazolo_-pyrimidine derivative for this invention is 2-amino-6-methyl-5-oxo-4-n-propyl-4,5-dihydro-s-triazolo/1.5-a/-pyrimidine.
Mustard --black or white-- is present in the dried ripe seeds of brassica nigra, brassica juncea. brassica alba and varieties of these species (cruciferae) and is a mixture of sinigrin (potassium myronate). myrosin. sinapine sulfocyanate, fixed oil:erucic, behenic and sinapolic acids. It is well-known as the source of volatile oil of commercial mustard.
Ipecac is also of natural origin and is a mixture of emetine, cephaeline, emetamine, ipecacuanhic acid. psychotrine, methylpsychotaine. resin. The level of total alkaloids in ipecac is normally above 2% of which about 60-70% is emetine, about 25% cephaeline and about 2% methylpsychotrine and emetamine. The emetic properties of ipecac are believed to originate from emetine and cephaeline.
In addition to the essential components defined hereinbefore, the compositions of this invention can contain conventional detergent composition additives inclusive of builder salts, detergent enzymes, solvents. diluents, detergent bleaches, polymeric detergent ingredients, chelants and other known detergent additives. These optional ingredients are used in the art established levels. Of course, the proper selection of the like optional ingredients will vary depending upon the physical state of the composition, its choice of major components. the known incompatibilities of certain ingredients and the contemplated utilization. These variables are eminently well-known in this domain of the art and the formula optimization will require routine measures and knowledge.
The granular detergent embodiments of this invention contain usually as a major optional ingredient a detergent builder. Suitable builder species include nitrilotriacetates, polycarboxylates, citrates, water-soluble polyphosphates, mixtures of ortho- and pyrophosphates, synthetic zeolites especially hydrated zeolite A having a particle size diameter in the range of from 1 to 10 microns and mixtures thereof. The builder ingredients are frequently used in levels from 5% to 80%. preferably from 8% to 30%. Detergent builder copolymers inclusive of copolymers from maleic anhydride and acrylic acids having a molecular weight in the range from 10.000 to 60.000 and polyacetate builders.
Detergent bleaches can also be incorporated in the compositions herein. Some compositions, particularly hard surface cleaners, can contain hypochlorite bleaches whereas fabric cleaning compositions very frequently contain peroxybleach ingredients. The oxybleach is frequently represented by sodium perborate, sodium percarbonate. sodium perphosphate or other known persalts if desirable in combination with oxygen-bleach activators such as tetraacetylethylene diamine and isononanoxyloxy- benzylsulfonate. Peroxyacids such as diperazelaic acid or peracetic acid, can also be used possibly in combination with sodium perborate. The oxygen percompounds are frequently used in levels from 5% to 30% whereas the activators, if present, are usually employed in levels from 0.5 to 6% whereby the molar ratio of oxybleach to activator is in the range from 6:1 to 1:1.
The compositions herein can also include film-forming polymers inclusive of homopolymers and copolymers of unsaturated aliphatic acid mono- or polycarboxylic acids. Preferred carboxylic acids are acrylic acid. hydroxyacrylic acid. methacrylic acid, maleic acid. fumaric acid. itaconic acid, aconitic acid, crotonic acid, and citraconic acid. The polycarboxylic acids (e.g., maleic acid) can be polymerized in the form of their anhydrides and subsequently hydrolyzed. The copolymers can be formed of mixtures of the unsaturated carboxylic acids with or without other copolymerizable monomers, or they can be formed from single unsaturated carboxylic acids with other copolymerizable monomers. In either case. the percentage by weight of the polymer units derived from non-carboxylic acids is preferably less than about 50%. Suitable copolymerizable monomers include, for example, vinyl chloride, vinyl alcohol, furan. acrylonitrile. vinyl acetate, methyl acrylate, methyl methacrylate. styrene. vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether. acrylamide, ethylene, propylene and 3-butenoic acid.
Preferred polymers of the above group are the homopolymers and copolymers of acrylic acid, hydroxyacrylic acid, or methacrylic acid, which in the case of the copolymers contain at least about 50%, and preferably at least about 80% by weight of units derived from the acid. Particularly preferred polymers are sodium polyacrylate and sodium polyacrylate and sodium polyhydroxyacrylate. especially the polyacrylates having molecular weight of from about 10,000 to about 200,000. Other specific preferred polymers are the homopolymers and copolymers of maleic anhydride, especially the copolymers with ethylene. styrene and vinyl methyl ether. These polymers are commercially available under the trade names Versicol and Gantrez.
The claimed technology is particularly useful for use in heavy-duty liquid detergent compositions, especially those formulations which are substantially free of polyphosphate builders. These compositions are eminently well-known in the art and have found over the recent years wide-spread commercial acceptance e.g. VIZIR.
A further example concerning the beneficial polyphosphate-free HDL utilization of the claimed technology relates to HDL's containing solvent such as those which are disclosed and claimed in pending European Patent Application 84305317.4, filed August 6, 1984. Inventors Herbots I.. Johnston J.P. and Walker J.R., these disclosures being incorporated herein by reference.
The following example illustrates the technology and facilitates its understanding; it is not intended to limit the invention.
A liquid heavy liquid is prepared by mixing the stated ingredients in the respective proportions.

EXAMPLE

Claims

1. A detergent composition containing a surface-active agent and, if desirable, conventional detergent composition additives inclusive of builder salts, detergent enzymes, solvents, diluents, detergent bleaches, polymeric detergent additives, and chelants, characterized in that, it contains a detergent compatible organic emetic agent in an amount from 2 ppm to 1000 ppm which emetic agent provides protection against assimilation following ingestion of the composition.

2. The composition in accordance with Claim 1 wherein the emetic agent is selected from the group of mustard, ipecac, apomorphine and s-triazolo(1,5-a)pyrimidine having the general formula recited in the specification, paragraph bridging pages 6 and 7.

3. A heavy-duty liquid detergent composition containing a surface-active agent, and optionally conventional detergent additives inclusive of grease-removal solvents, chelants, pH regulating agents, enzymes, perfumes, dyes, brighteners, said composition being substantially free of polyphosphate builders, characterized in that it contains a detergent compatible organic emetic agent in an amount from 2 ppm to 1000 ppm which emetic agent provides protection against assimilation following ingestion of the composition.

4. The composition in accordance with Claim 3 wherein the emetic agent is selected from the group of mustard, ipecac, apomorphine and s-triazolo(1.5-a)pyrimidine having the general formula recited in the specification, paragraph bridging pages 6 and 7.