JPH0881693A - Insect-repellent detergent composition - Google Patents

Abstract

A stable oil-in-water microemulsion cleaning composition is provided which is essentially effective for the removal of oily and greasy soil from a hard surface and for repelling insects therefrom. The aqueous phase of said microemulsion comprises by weight of the total composition: (A) from about 0.1 to about 25% of a surfactant mixture of (i) an anionic surfactant; (ii) an ethoxylated glycerol type compound; the weight ratio of (i) and (ii) being from about 1:1 to about 5:1; and (iii) a salt of a multivalent metal cation in an amount sufficient to provide from 0.5 to 1.5 equivalents of cation per equivalent of (i); the anionic surfactant, the nonionic surfactant and amount of multivalent metal cation being selected so as to provide a cloud point of at least about 45 DEG C in the finished microemulsion composition; (B) from about 0.1% to about 30% of a water-soluble cosurfactant having substantially no ability to dissolve oily or greasy soil; and (C) the balance water. The oil phase of said microemulsion is comprised essentially of an effective amount of an insect repellent compound, and optionally a perfume or water insoluble hydrocarbon, said microemulsion composition being effective for removing oily and greasy soils from a hard surface and repelling insects therefrom by solubilizing such soils in the microemulsion while concomitantly depositing the insect repellent compound upon the hard surface to be cleaned to provide insect repelling properties thereto.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention is particularly suitable for cleaning hard surfaces,
It relates to an improved universal liquid cleaner as a microemulsion designed to impart anthelmintic properties to such hard surfaces. More specifically, the present invention relates to a liquid universal detergent composition as a microemulsion containing an anthelmintic substance, a method for cleaning surfaces and products coated with such a microemulsion detergent composition, and controlling insects therefrom. Regarding

[0002]

BACKGROUND OF THE INVENTION Recently, universal liquid detergent compositions have been widely used for cleaning hard surfaces such as painted woodwork and panels, tile walls, washbasins, bathtubs, linoleum or tile floors, washable wallpaper and the like. Is accepted. Such all-purpose liquids include clear or opaque aqueous mixtures of water-soluble synthetic organic detergents and water-soluble detergent builder salts. In order to obtain a cleaning effect comparable to that of a granular or powder universal detergent composition, it was advantageous to use a water-soluble inorganic phosphate builder in the prior art universal fluid. For example, such early phosphate-containing compositions have been described in US Pat. No. 2,560,
No. 839, No. 3,234, 138, No. 3,350, 3
19 and British Patent No. 1,223,739. In light of environmentalists' efforts to reduce phosphate levels in groundwater, improved universal liquids with low concentrations of inorganic or non-phosphate builder salts have emerged. . A particularly useful self-opacified liquid of the latter type is US Pat. No. 4,24.
No. 4,840.

However, these prior art all-purpose liquid detergents, including detergent builder salts or other equivalents, have a fil on the washed but not rinsed side, especially on the shiny side.
m), tends to leave spots or streaks. Therefore, such liquids require a thorough rinse of the cleaned surface,
This is a time-consuming and objectionable task for the user.

To overcome the above drawbacks of the prior art all-purpose liquids, US Pat. No. 4,017,409 teaches that a mixture of paraffin sulfonate and a low concentration of inorganic phosphate builder salt should be used. ing. On the other hand, another alternative means for obtaining a phosphate-free all-purpose liquid is to use a major proportion of anionic detergent / nonionic detergent mixture in small amounts, as shown in US Pat. No. 3,935,130. It was to be used with glycol ether solvent and organic amine. This approach is also not entirely satisfactory and it is generally found that the high levels of organic detergents required to achieve cleaning result in foaming, which is generally unfavorable to current consumers. Creates a need for rinsing.

Another approach for producing hard surface or universal liquid detergent compositions in which product homogeneity and clarity are important considerations is one or more surface active detergent compounds and a water immiscible solvent ( It typically involves the formation of oil-in-water (O / W) microemulsions containing a (hydrocarbon solvent), water, and a "cosurfactant" compound that imparts stability to the product. By definition, an O / W microemulsion is a naturally occurring colloidal dispersion of "oil" phase particles having a particle size in the range of about 25 to about 800Å in a continuous aqueous phase. Considering the extremely fine particle size of the dispersed oil phase particles, microemulsions are transparent to light, transparent and usually very stable to phase separation.

Fat (g in O / W microemulsions)
Rease) Patent disclosures relating to the use of removal solvents include, for example:
European Patent Application No. 013 by Herbots et al.
7615 and 0137616; Johns
ton) et al., European Patent Application No. 0160762; and Harbots et al., U.S. Pat. No. 4,561,991. Each of these patent disclosures also teach the use of at least 5% by weight of a fat removal solvent.

From British Patent Application No. 2144763A to Harbots et al., Issued Mar. 13, 1985,
It is also known that magnesium salts enhance the fat removal performance of fat removal organic solvents, such as terpenes, in O / W microemulsion liquid detergent compositions. The composition of the invention, as described by Harbots et al., Comprises at least 5% of a fat-removing solvent / magnesium salt mixture, at least 5% of solvent (a mixture of a water-immiscible non-polar solvent and a poorly soluble weakly polar solvent), and Requires 0.1% magnesium salt.

However, the amount of mixture of water-immiscible and sparingly soluble components which can be present in an O / W microemulsion with a low total active ingredient without compromising the stability of the microemulsion is rather limited. The presence of such a large amount of fat-removing solvent, such as up to about 18% by weight of the aqueous phase, can be absorbed by and in the microemulsion without causing phase separation. Or it tends to reduce the total amount of oily soil. The following representative prior art patents relate to liquid detergent cleaning compositions as O / W emulsions: Rosario U.S. Pat. No. 4,472,291; Gaute.
er) et al., No. 4,540,448; Sheflin
No. 3,723,330.

US Pat. Nos. 5,076,954, 5,075,026, 5,082,584 and 5,108,643, all under the name Loth et al. A liquid microemulsion composition effective for removing greasy soil and / or bath soil is described.
The described microemulsions contain a specific combination of anionic surfactants, nonionic surfactants, cosurfactants, perfumes and water.

Detergent compositions for hard surfaces having the ability to clean and repel hard surfaces to which the cleaning composition is applied are described in the art. European Patent Application No. 525892A1 to Steltenkamp et al. Relates to an aqueous liquid detergent composition for cleaning hard surfaces, which composition comprises an N-alkyl neoalkanamide [alkyl having 1 to 4 carbon atoms. Yes, the neoalkanoyl part has 7 to 14 carbon atoms
, Which includes anthelmintic substances such as those contained in However, conventional insect repellents effectively clean hard domestic surfaces, such as kitchen walls, oven tops, bathroom floors, etc., while at the same time applying the composition to remove insects from it. It has never been used in combination with a liquid microemulsion composition capable of applying a coating of anthelmintic material that is sufficiently essential to the surface to be controlled.

[0011]

The present invention is a stable oil-in-water microemulsion that is particularly effective for removing oily and greasy soils from hard surfaces and combating insects from the same. The aqueous phase of said emulsion is based on the weight of the total composition: (A) (i) anionic surfactant; (ii) ethoxylated glycerol type compound, (i) to (ii) weight ratio of about 1 1 to about 1: 5;
And (iii) (i) a salt of a polyvalent metal cation in an amount sufficient to supply 0.5 to 1.5 equivalents of cation per equivalent, the anionic surfactant and the polyvalent metal cation. Of the surfactant mixture, about 0.1% to about 25%; and (B) a fatty acid, about 0-5%; (C) a water-soluble co-surfactant having substantially no ability to dissolve oily or greasy soil, about 0.1% to about 30%; and (D) water, the balance; the oil phase of the emulsion. Consisting essentially of an effective amount of anthelmintic compound and any perfume or water-insoluble hydrocarbon; removing such soils from hard surfaces by solubilizing oily and greasy soils in a microemulsion, Remove insects from the hard surface, Occasionally, the anthelmintic compound is attached to the hard surface to be cleaned to provide the detergent composition which is effective for imparting anthelmintic properties to the hard surface.

[0012]

The dispersed oil phase of the microemulsion is from about 0.5 to about 20% by weight of the total composition, preferably from about 2 to about 15%, most preferably from about 2 to about 10.
Account for weight percent. Microemulsions can be formed using anthelmintic substances as the only component of the oil phase,
It is preferable to include a small amount of perfume to improve the consumer acceptance of the product.

Preferred anthelmintic substances useful in the present invention have the structural formula:

Embedded image [Wherein the alkyl R "'has 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms, and a neoalkanoyl moiety:

Embedded image Has 7 to 14 carbon atoms, preferably neotridecanoyl, most preferably neodecanoyl].

Of the above neoalkane amides, methyl neodecaamide (MNDA) is the most preferred anthelmintic substance. A detailed description of the above neoalkane amides and their methods of manufacture can be found in a number of patents such as, for example, US Pat. No. 5,258,408, the disclosure of which is incorporated herein.

Although less preferred than those mentioned above, other useful anthelmintic agents may also be used to advantage in the compositions of the present invention, most notably by the commercial designation DEET.
Is N, N-diethyl-meta-toluamide.

The anthelmintic material is generally present in the microemulsion detergent composition in an amount of about 0.5 to about 20% by weight, depending on the desired level of anthelmintic activity to impart to the hard surface in contact with said microemulsion composition. %, Preferably about 1 to about 8% by weight, most preferably about 1 to about 5% by weight.

It is preferred that the microemulsion composition of the present invention be pesticide free, relying solely on the anthelmintic material to impart anthelmintic properties to the washed hard surface.

According to the process aspect of the present invention, an effective amount of anthelmintic material is sufficient to repel a hard surface after application of the microemulsion detergent composition, as described above. Provided is a method of cleaning a hard surface, including applying an emulsion cleaning composition to the hard surface, and repelling the hard surface.

The present invention provides the possibility that the anthelmintic substance used in the present invention can be effectively solubilized in the oil phase of the defined microemulsion composition to impart anthelmintic properties to the washed and washed surfaces. It is based on the discovery that liquid detergent compositions can be produced with significant benefits. This microemulsion composition is particularly advantageous in that it eliminates the need for the consumer to rinse the washed surface, thereby allowing the hard surface to be administered a more concentrated amount of anthelmintic.

Current commercial microemulsion detergent compositions are generally too hydrophobic, as evidenced by the fact that the composition obtained after addition of MDNA has a cloud point of less than 45 ° C. It is not possible to mix anthelmintic substances such as MNDA into the inside. This is not commercially acceptable for most consumer liquid cleaning products. The present invention provides fully hydrophilic microemulsions having a cloud point of at least 45 ° C, preferably at least 50 ° C, most preferably about 55 ° C.

Cloud point is conveniently measured by the following method: A 5 ml test sample is equilibrated in a 10 ml stoppered test tube in a water bath at about 30 ° C. Gradually increase the bath temperature and record the temperature at which each sample becomes cloudy as the cloud point.

The microemulsions of the present invention designed to contain the anthelmintic materials described herein can be prepared according to the following methods: (1) With respect to the anionic surfactant, the polyvalent cation in the composition (typically (2) by selecting a more hydrophilic anionic surfactant, and (3) using a high ratio of anionic surfactant to esterified polyethoxyether nonionic surfactant. The composition is adjusted by one or more to make it more hydrophilic to provide the desired cloud point.

Alternatively, though less convenient than the above, a highly hydrophilic cosurfactant can be used. However, if the particular nonionic surfactant selected is sufficiently hydrophilic to provide the desired cloud point in the finished composition, a hydrophobic cosurfactant will be effective in the microemulsion composition of the present invention. Can be used for.

The microemulsion composition of the present invention is an improved, clear liquid having improved interfacial tension suitable for cleaning hard surfaces such as plastics, glassy and metallic surfaces having a glossy finish. A cleaning composition is provided. More particularly, this improved detergent composition has good greasy soil removability when used in its undiluted (neat) form and, due to its improved interfacial tension, provides additional rinse or wipe. Leaves a shiny, washed surface without the need for (wiping) or with minimal additional rinsing or wiping. This latter feature is manifested by the presence of little or no visible residue on the non-rinsed washed surface, thus overcoming one of the drawbacks of the prior art products. Surprisingly, these desirable results are obtained in the absence of polyphosphates or other inorganic or organic detergent builder salts and in the complete or substantially complete absence of fat-removing solvents.

The microemulsion composition may be formed as a substantially dilute oil-in-water microemulsion having a composition such that the aqueous phase and the oil phase are as described above. Alternatively, according to the second embodiment of the present invention, oil-in-water (O /
W) Provide highly concentrated microemulsion compositions either as microemulsions or as water-in-oil (W / O) microemulsions that form dilute O / W microemulsion compositions when diluted with additional water prior to use To do. Dilute or concentrated microemulsion compositions generally contain about 0.1-20% by weight of anionic surfactant, about 0.1%.
~ 20% esterified polyethoxyether nonionic surfactant, about 0-5% fatty acid, about 0.4-10% perfume, about 0.5-20% anthelmintic, about 0.1 30%
Co-surfactant, and about 20 to the balance of the composition
Contains 97% water. The mixture of anionic and nonionic surfactants is generally about 0.1-25% and the anion to nonionic weight ratio is about 1: 1 to 5: 1.

The present invention relates to a stable or concentrated microemulsion composition having the above composition.

According to the invention, the role of the hydrocarbons forming the oil phase is fulfilled by the anthelmintic substance as well as by the perfume. Since the perfume is generally a mixture of aromatic essential oils and aromatic hydrocarbons that are not generally water soluble, aqueous compositions include, for example, alkali metal lower alkylaryl sulfonate hydrotropes, triethanolamine, urea and the like. The presence of such solubilizers is typically required for perfume dissolution, especially at perfume levels above about 1%. Therefore, the inclusion of perfume with anthelmintic substances in an aqueous detergent composition as the oil (hydrocarbon) phase of the final O / W microemulsion composition provides several various important advantages. .

First, the cosmetic properties of the final detergent composition are improved; the composition is transparent (as a result of microemulsion formation) and highly aromatic (as a result of perfume level). Is.

Second, the need for the use of solubilizers that do not contribute to cleaning performance is eliminated.

Third, the improved fat-removal capacity in a dilute aspect of the neat (undiluted) use method or after dilution of the concentrate is achieved without detergent builders or buffers or conventional fat-removing solvents. Obtained at neutral or acidic pH and at low levels of active ingredient, improved cleaning performance can also be obtained in dilute use.

As used herein and in the claims, the term "perfume" has its ordinary meaning in its natural meaning (ie, flower, herb, blossom).
Or water-insoluble fragrances or such, including fragrances and artificial (ie natural oils or mixtures of oil components and synthetically derived substances) fragrances. Used to represent or include a mixture of different substances. Typically, the perfume is with a blend of various organic compounds, such as alcohols, aldehydes, ethers, aromatics, for example from about 0 to about 80% by weight, usually from about 10 to about 70% by weight, A complex mixture with various amounts of essential oils (eg terpenes), the essential oils themselves being volatile aromatic compounds, which serve to dissolve the other components of the perfume.

In the present invention, the exact composition of the perfume is not critical to cleaning performance as long as the perfume meets the criteria of water immiscibility and has a pleasant fragrance. Especially for cleaning compositions intended for domestic use,
Naturally, the fragrance as well as all other ingredients are for cosmetic use (c
osmetically) should be acceptable, ie non-toxic, hypoallergenic, etc.

Hydrocarbons such as perfumes are dilute O /
It is present in the W microemulsion in an amount of about 0.4 to about 10% by weight, preferably about 0.4 to about 3.0% by weight, particularly preferably about 0.5 to about 2.0% by weight. Whether derived from anthelmintic substances or fragrances, it becomes difficult to form O / W microemulsions when the amount of hydrocarbons is less than about 0.4% by weight.

Furthermore, even if the excellent fat removal performance of the fragrance composition containing no terpene solvent is obtained, it is about 20%.
A perfume manufacturer can provide a sufficiently inexpensive perfume composition for this type of product containing less than about 30% of such terpene solvent (ie, a consumer product that is very cost sensitive). Clearly difficult to manufacture.

Thus, merely as a matter of fact, based on economic considerations, the dilute O / W microemulsion detergent detergent compositions of the present invention are often terpene solvent incorporated into the composition via a perfume ingredient. About 0.2 to about 7% by weight based on the total composition. However, the amount of terpene solvent in the cleaning composition is less than 1.5% by weight,
Sufficient fat and oil removal capacity is provided by the dilute O / W microemulsions of the present invention, eg, up to about 0.6% by weight or even 0.4% by weight or less.

With respect to the anionic detergent present in the O / W microemulsion, any of the commonly used water-soluble anionic detergents or mixtures of said anionic and nonionic detergents can be used in the present invention. As used herein, the term "anionic surfactant" is intended to mean a class of anionic detergents and mixed anionic-nonionic detergents that provide a cleaning action.

The water-soluble organic detergent material used to form the final O / W microemulsion composition of the present invention is selected from the group consisting of water-soluble non-soap anionic detergent mixed with fatty acids and non-ionic detergents.

Suitable water-soluble non-soap anionic detergents are:
An organic hydrophobic group generally containing 8 to 26 carbon atoms, preferably 10 to 18 carbon atoms in its molecular structure, and at least one selected from the group consisting of sulfonates, sulfates and carboxylates for forming water-soluble detergents. Water-solubilizing groups, such as surface-active compounds or detergent compounds. Usually, the hydrophobic group is or means including C ₈ -C ₂₂ alkyl, alkenyl or acyl group. Such detergents are used as the water-soluble salts, salts formed cation is usually sodium, potassium, ammonium, magnesium and mono-, - di - or tree C ₂ -C ₃ selected from the group consisting of alkanol ammonium, sodium, magnesium And ammonium cations are also preferred in this case.

Examples of suitable sulphonated anionic detergents are the well known higher alkyl mononuclear aromatic sulphonates, eg higher alkylbenzene sulphonates containing 10 to 16 carbon atoms in a straight or branched higher alkyl group, C ₈ -C. ₁₅ alkyl toluene sulfonates and C ₈ -C ₁₅ alkyl phenol sulfonates.

Preferred sulfonates have a high content of 3 (or greater than 3) -phenyl isomer and a corresponding low content of 2 (well less than 50%) 2 (or less than 2).
A linear alkyl benzene sulphonate with a phenyl isomer, i.e. in this case the benzene ring is preferably attached predominantly at most 3 or more (eg 4, 5, 6 or 7) positions of the alkyl group Has a correspondingly low content of isomers attached at the 2 or 1 position.
Particularly preferred materials are described in US Pat. No. 3,320,174.

Other suitable anionic detergents are olefin sulfonates, including long chain alkene sulfonates, long chain hydroxyalkane sulfonates or mixtures of alkene sulfonates and hydroxyalkane sulfonates. These olefin sulfonate detergents include sulfur trioxide (SO ₃ ) and the formula: RCH = CHR ₁ [wherein, R is a higher alkyl group having 6 to 23 carbon atoms, and R ₁ is 1 to ₁ carbon atoms.
17 alkyl group or hydrogen] to form a mixture of a sultone and an alkene sulfonic acid by reaction with a long chain olefin having 8 to 25 carbon atoms, preferably 12 to 21 carbon atoms. Can be prepared by known methods by subsequent treatment to convert the sultone to a sulfonate. Preferred olefin sulfonates contain 14 to 16 carbon atoms in the R alkyl group, and are α-
Obtained by sulfonation of olefins.

Other examples of suitable anionic sulfonate detergents are paraffin sulfonates having about 10 to 20 carbon atoms, preferably about 13 to 17 carbon atoms. The major paraffin sulfonates are made by reacting long chain alpha-olefins with bisulfite, and paraffin sulfonates having sulfonate groups distributed along the paraffin chain are described in US Pat. Nos. 2,503,280, 2, 507,088
No. 3,260,744, 3,372,188 and German Patent 735,096.

Examples of satisfactory anionic sulphate detergents are C ₈ -C ₁₈ alkyl sulphate salts and the formula: R (OC ₂ H
₄ ) _n OSO ₃ M [wherein n is 1 to 12, preferably 1 to
5, M is sodium, potassium, ammonium,
Solubility (sol) selected from the group consisting of magnesium and mono-, di- or triethanol ammonium ions
Ubilizing) is a C ₈ -C ₁₈ alkyl ether polyethenoxy based Thistle phosphate salt represented by a cation.
The alkyl sulfate can be obtained by sulfating the alcohol obtained by reducing glyceride of coconut oil or tallow or a mixture thereof and neutralizing the obtained product. Alkyl ether polyethenoxy based Thistle sulfates may be obtained by sulfating the condensation product of ethylene oxide with C ₈ -C ₁₈ alkanols, neutralizing the resulting product. The alkyl ether polyethenoxysulfates differ from each other in the number of moles of ethylene oxide reacted with 1 mole of alkanol. Preferred alkyl sulphates and preferred alkyl ether polyethenoxy sulphates have 1 carbon atom in the alkyl group.
Including 0 to 16.

[0044] C ₈ -C ₁₂ alkylphenyl ether polyethenoxy based Thistle sulfates containing from 2 to 6 moles of ethylene oxide groups in the molecule are also suitable for use in the compositions of the present invention. These detergents can be prepared by reacting an alkylphenol with 2 to 6 moles of ethylene oxide and sulfating and neutralizing the resulting ethoxylated alkylphenol.

Among the above non-soapic anionic detergents, the preferred detergents are C ₉ -C ₁₅ linear alkylbenzene sulfonates and C ₁₃ -C ₁₇ paraffins or alkane sulfonates. Particularly, preferred compounds are C ₁₀ -C ₁₃ sodium alkyl benzene sulfonate and C ₁₃ -C ₁₇ sodium alkane sulfonate.

Generally, the proportion of non-soap anionic detergent is from 0.1 to 2 of the dilute O / W microemulsion composition.
It is in the range of 0.0% by weight, preferably 1 to 7% by weight.

The ethoxylated glycerol type compound is a mixture of a fully esterified ethoxylated polyhydric alcohol, a partially esterified ethoxylated polyhydric alcohol and a non-esterified ethoxylated polyhydric alcohol, the preferred polyhydric alcohol being glycerol. Yes; this compound has the formula:

[Chemical 3] In the formula, w is 1 to 4, and most preferably 1. B
Is hydrogen or the formula:

[Chemical 4] Wherein R is an alkyl group having about 6 to 22 carbon atoms, more preferably about 11 to about 15 carbon atoms and an alkenyl group having about 6 to 22 carbon atoms, more preferably about 11 to 15 carbon atoms. A hydrogenated tallow alkyl chain or coconut oil alkyl chain is most preferred].
At least one of the B groups has the formula:

[Chemical 5] R'is selected from the group consisting of hydrogen and a methyl group; x, y and z are 0 to 60, more preferably 0.
Has a value of ˜40, where (x + y + z) is about 2 to about 1
00, preferably 4 to about 24, most preferably about 4-1
9; in formula (I) the monoester / diester / triester ratio is from 45 to 90/5 to 40/1 to 20.
And more preferably 50 to 90/9 to 32/1 to 1
2; the ratio of formula (I) to formula (II) is from about 3 to about 0.0.
2, preferably 3 to about 0.1, most preferably about 1.5.
Most preferably, there is more compound of formula (II) than formula (I) in the mixture forming the compound.

The ethoxylated glycerol type compound used in the composition of the present invention is Kao Corporation.
manufactured by
nol), for example, Rebenol F-200 [6 average EO
And having a molar ratio of coconut oil fatty acid to glycerol of 0.55] or Levenol V501 / 2 [having an average EO of 17 and a tallow fatty acid to glycerol molar ratio of 1.0]. The molar ratio of fatty acid to glycerol is preferably less than about 1.7, more preferably less than about 1.5, and most preferably less than about 1.0. The ethoxylated glycerol type compound has a molecular weight of about 400 to about 1600 and a pH of about 5 to 7 (50 g / liter of water). Rebenol compounds are not substantially a source of irritation to human skin and exceed 90% primary biodegradability (primary biodegradation) as measured by the Wickbold method Bias-7d.
degradability).

Two examples of rebenol compounds are rebenol V5.
01/2 [has 17 ethoxylated groups, is derived from tallow fatty acids, has a fatty acid / glycerol ratio of 1.0 and has a molecular weight of about 1465], and Rebenol F-2
00 [having 6 ethoxylated groups, derived from coconut oil fatty acid and having a fatty acid / glycerol ratio of 0.55]. Rebenol F-200 and Reberol V5
Both 01/2 consist of a mixture of formula (I) and formula (II). Rebenol compounds are> 100 mg / liter for the algal growth inhibition ecoxicity value (ecoxicity valu
e);> 100 mg / l acute toxicity to Daphniae; and> 100 mg / l acute fish toxicity. Revenol compounds are readily biodegradable and therefore have an easy biodegradability that exceeds the minimum requirement of 60% by OECD 301B.

Polyesterified nonionic compounds which are useful in the compositions of the present invention are commercially available from Croda GMB of The Netherlands.
H-) Crovol PK-40 and Crovol PK-70. Krovol PK-40
Is a polyoxyethylene (12) palm kernel oil glyceride having 12 EO groups.
Preferred Clovol PK-70 is a polyoxyethylene (45) palm kernel oil glyceride having 45 EO groups.

In a preferred dilute O / W microemulsion composition, the proportion of ethoxylated glycerol type compound based on the weight of the final dilute O / W microemulsion composition is 0.1-10.0 wt%, more preferably 0. .5-
It is 5% by weight. Furthermore, in a more preferred composition, the weight ratio of non-soapic anionic detergent to ethoxylated glycerol type compound is in the range of 1: 1 to 5: 1 and is 1: 1.
Particularly good results are obtained at weight ratios of up to 2: 1.

Cosurfactants play an important role in the preparation of dilute O / W and concentrated microemulsion compositions. Very simply, in the absence of cosurfactants, water, detergents and hydrocarbons (eg,
Fragrances or anthelmintic substances) are mixed in suitable proportions to give a micellar solution (low concentration) or an oil-in-water emulsion according to the first aspect of the invention. Addition of a cosurfactant to this system reduces the interfacial tension at the emulsion droplet-water phase interface to very low values. This reduction in interfacial tension results in the destruction of emulsion droplets, resulting in smaller agglomerates and eventually in the form of clear colloidal sized emulsions, eg microemulsions. In the state of microemulsions, thermodynamic factors are balanced with varying degrees of stability with respect to the total free energy of the microemulsion. Some of the thermodynamic factors involved in determining the total free energy of a system are (1) particles-
Particle potential; (2) interfacial tension or free energy (stretching or bending); (3) droplet dispersion entropy; and (4) chemical potential change during formation. Thermodynamically stable systems are obtained when (2) interfacial tension or free energy is minimized and (3) droplet dispersion entropy is maximized. Therefore, the role of co-surfactants in the formation of stable O / W microemulsions is (a)
It is to reduce the interfacial tension (2), (b) modify the microemulsion structure and increase the number of possible configurations (3). In addition, the co-surfactant reduces (c) rigidity.

It has been found that four main compounds provide highly suitable cosurfactants over a temperature range ranging from 5 ° C. to 43 ° C .; these are, for example: 1) water-soluble C ₃ -C ₄ alkanols,
_{Formula: HO (CH 3 CHCH 2 O} ) n H [ wherein, n 2-1
Is a number of 8]
Structural formula: R (X) _n OH and R ₁ (X) _n OH [wherein R
Is C ₁ -C ₉ alkyl, R ₁ is C ₁ -C ₄ acyl group, X is (OCH ₂ CH ₂₎ or (OCH ₃ CHCH ₂₎
And n is a number from 1 to 4], monoalkyl ethers and esters of ethylene glycol and propylene glycol; (2) Aliphatic mono- and di-carboxylic acids containing 3 to 6 carbon atoms in the molecule. An acid; (3) said alkyl ether polyethenoxycarboxylic acid as described above, provided that the anionic carboxylate form of this compound is not present; and (4) triethyl phosphate. Furthermore, mixtures of two or more of the four cosurfactant compounds can be used if a particular pH is desired.

Typical elements of polypropylene glycol include dipropylene glycol and a molecular weight of 200 to 10.
There are polypropylene glycols with 00, for example polypropylene glycol 400. Other satisfactory glycol ethers are ethylene glycol monobutyl ether (butyl cellosolve), diethylene glycol monobutyl ether (butyl carbitol), triethylene glycol monobutyl ether, mono-, di-, tripropylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, propylene. Glycol tertiary butyl ether, ethylene glycol monoacetate and dipropylene glycol propionate.

Yet another type of cosurfactant compound that forms stable microemulsion compositions at low and elevated temperatures is the above alkyl ether polyethenoxycarboxylic acid and a mono-phosphoric acid such as triethyl phosphate. Di- and triethyl ester.

The amount of cosurfactant required to stabilize the microemulsion composition is dependent on the surface tension of the cosurfactant, the type and amount of the first surfactant and the perfume, and the composition. Thus, it will of course depend on such factors as the type and amount of any other ingredients that can affect the thermodynamic factors. Generally 0-30% by weight, preferably about 0.5-1
A co-surfactant amount in the range of 5% by weight, particularly preferably about 1-7% by weight, is stable with respect to the above levels of the first surfactant and perfume and any other additional ingredients described below. Produces a diluted O / W microemulsion.

As will be appreciated by the practitioner, the pH of the final microemulsion will depend on the identity of the cosurfactant compound, and the choice of cosurfactant will depend on cost and cosmetic properties (especially odor). Be seen. For example, a microemulsion composition having a pH in the range of 1 to 10 can use the class (1) or class (4) cosurfactant as the sole cosurfactant, but the polyvalent metal salt is If present, this pH range is reduced to 1-8.5. The class (2) cosurfactant can be used as the sole cosurfactant only if the product pH is below 3.2. Similarly, co-surfactants of type (3) can be used as the sole co-surfactant only if the product pH is below 5. However, if the acidic cosurfactant is used as a mixture with a glycol ether cosurfactant, the composition can be prepared at a substantially neutral pH.

The final essential ingredient of the microemulsion composition of the present invention, which has improved interfacial tension properties, is water. The proportion of water in the microemulsion composition is generally between 20 and 9 of a conventional dilute O / W microemulsion composition.
It is 7% by weight, preferably 70 to 97% by weight.

As described above, the dilute O / W microemulsion liquid universal detergent composition of the present invention is particularly effective when used as it is, that is, without further dilution with water, for the reason O. This is because the properties of the composition as a / W microemulsion are best expressed in a neat (undiluted) form. At the same time, however, it should be understood that depending on the level of surfactants, cosurfactants, perfumes and other ingredients, some dilution is possible without destroying the microemulsion itself. For example, at a preferred low level of active surfactant compound (ie, primary anionic and nonionic detergent), about 50
Dilutions up to% are generally well tolerated without causing phase separation, ie the microemulsion state is maintained.

However, even when diluted on a large scale, for example a 2-fold to 10-fold or higher dilution, the resulting composition is still effective in cleaning greasy, oily and other types of soil. Further, as detailed below, the presence of magnesium ions or other multivalent ions (eg, aluminum) helps to enhance the cleaning performance of the first detergent in dilute use methods.

On the other hand, it is also within the scope of the present invention to prepare concentrated microemulsions which are replenished and diluted with water before use.

The invention also comprises, in approximate weight percent: (a) anionic surfactant, 0.1-20%; (b) ethoxylated glycerol type compound, 0.1-2.
0%; anionic / nonionic surfactant mixtures are generally about 0.1 to 25%; (c) fatty acids, 0 to 5%; (d) cosurfactants, 0.1 to 30%; (e ) Anthelmintic substances (eg MNDA), 0.5-20
%; (F) Water-insoluble hydrocarbon or fragrance, 0.4 to 10%; (g) At least one mono- or dicarboxylic acid, 0 to
18%; (h) Magnesium sulfate heptahydrate, 0 to 15%; and (i) Water, balance. Such concentrated microemulsions are diluted by mixing with up to about 20 times their weight or more, preferably about 4 to about 10 times their weight to give an O / W microemulsion similar to the dilute microemulsion composition above. An emulsion can be formed. It is possible to form an O / W microemulsion composition after dilution with proper selection of the degree of dilution, but be aware that both microemulsions and non-microemulsions may occur consecutively during the course of dilution. Should be.

In addition to the above essential ingredients required to form a microemulsion composition, the compositions of the present invention often and preferably include one or more additional ingredients that serve to improve the overall product performance. You can

One such component is a polyvalent metal cation, especially an inorganic or organic salt or oxide of Mg ⁺⁺ . Metal salts or oxides provide several benefits, including improved cleaning performance especially in dilute use methods in the soft water region and reduction of the amount of perfume required to obtain a microemulsion state. Anhydrate or hydrate (eg heptahydrate)
Is particularly preferred as the magnesium salt. However, good results have also been obtained due to magnesium oxide, magnesium chloride, magnesium acetate, magnesium propionate and magnesium hydroxide. These magnesium salts can be used in the composition at these pHs because magnesium hydroxide does not precipitate at neutral or acidic pH levels.

Magnesium is the preferred polyvalent metal from which the salts (including oxides or hydroxides) are formed, but other polyvalent metal ions also have nontoxic salts thereof.
It can be used as long as it is soluble in the aqueous phase of the system at the preferred pH level. Thus, depending on factors such as the pH of the system, the nature of the first and co-surfactants, etc. and availability and cost factors, other suitable polyvalent metal ions include aluminum, There are copper, nickel, iron, calcium, etc. It should be noted, for example, that the preferred paraffin sulfonate anionic detergent should not be used as it will precipitate calcium salts. The aluminum salt has a low level, for example, about 1 at a pH of less than 5, or for compositions designed to have a neutral pH.
It has also been found to work best when adding wt% citric acid. Alternatively, the aluminum salt can be added directly as the citrate salt in such cases. Anions of the same general type described above for magnesium salts are salts such as halides (eg bromide, chloride), sulphates, nitrates, hydroxides,
Oxides, acetates, propionates and the like can be used.

Preferably, in a dilute composition, the metal compound is in the composition and at least a stoichiometric equivalence relationship between the anionic surfactant and the polyvalent metal cation.
c equivalence) is added in sufficient quantity to form. For example, for each gram ion of Mg ⁺⁺ , there are 2 gram moles of paraffin sulfonate, alkylbenzene sulfonate, etc., and for each gram ion of Al ³⁺ , 3
There are gram moles of anionic surfactant. Therefore, the proportion of polyvalent salt is generally such that 1 equivalent of the compound is 0.5 to 1.5 equivalents of the acid form of the anionic detergent, preferably 0.9 to.
It is selected to neutralize 1.1 equivalents. At high concentrations of anionic detergent, the amount of polyvalent salt ranges from 0.5 to 1.5 equivalents per equivalent of anionic detergent, preferably 0.8 to 1.2 polyvalent salts per equivalent of anionic detergent. It is in the equivalent range.

The O / W microemulsion composition contains 0 to 5% by weight of the composition of C ₈ -C ₂₂ fatty acid or fatty acid soap as a foam suppressant, preferably 0.1.
~ 2.0 wt%. Addition of fatty acids or fatty acid soaps, whether in neat or diluted form, improves the rinseability of the composition. However, in general, when fatty acids or soaps are present, it is necessary to increase the amount of co-surfactant to maintain product stability.

Examples of fatty acids which can be used on their own or as soaps include distilled coconut oil fatty acids, "mixed vegetable" type fatty acids (eg high percentages of saturated mono- and / or polyunsaturated C ₁₈ chains). ); Oleic acid, stearic acid, palmitic acid, eicosanoic acid, etc. can be mentioned, and generally, a fatty acid having 8 to 22 carbon atoms is accepted.

The universal liquid detergent composition of the present invention may also contain other ingredients, if desired, to provide an additional effect or to make a product more appealing to the consumer. The following components may be mentioned by way of example: colorants or dyes in amounts of up to 0.5% by weight; fungicides in amounts of up to 1% by weight;
Preservatives or antioxidants such as formalin, 5-bromo-5-nitro-dioxane-1, up to 2% by weight.
3; 5-chloro-2-methyl-4-isothaliazoline-
3-one; 2,6-di-tert-butyl-p-cresol and the like; and optionally a pH adjuster such as sulfuric acid or sodium hydroxide. In addition, up to 4% by weight of opacifying agent can be added if an opaque composition is desired.

This all-purpose liquid is a clear oil-in-water microemulsion in its final form and is stable at low and high temperatures. More particularly, such compositions have from 5 to 50
It is transparent and stable at 0 ° C, particularly in the range of 10 to 43 ° C. Such compositions have a pH in the acidic or neutral range, depending on the intended end use. These liquids are easily pourable and can be used by the Brookfield®
It has a viscosity in the range of 6-60 millipascal-seconds (mPas) measured at 25 ° C. with a # 1 spindle rotating at 20 RPM on a VT viscometer. It is preferred to maintain the viscosity within the range of 10-40 mPas.

The composition can be used directly or can be optionally diluted, but in each case no or only a slight rinse is required, no residue or streaks are formed. Virtually nothing is left behind. Moreover, since the composition is free of detergent builders such as alkali metal polyphosphates, it is environmentally acceptable and gives good "gloss" on the washed hard surface.

When the use in a neat form is planned, the liquid composition is so-called spray-and-wipe.
type) It can be packaged under pressure in an aerosol container or pump type or trigger sprayer for use.

Since the as-prepared composition is an aqueous liquid composition and does not require special mixing for O / W microemulsion formation, simply mix all ingredients in a suitable container or container. This composition can be easily manufactured. The order of mixing the components is not particularly important and generally the various components can be added sequentially or all at once, or separately prepared as an aqueous solution of each of the first detergent and the cosurfactant or all of them. Can be combined with each other, and with perfumes. The magnesium salt or other polyvalent metal compound, if present, can be added as an aqueous solution of these or can be added directly. It is not always necessary to use high temperatures in the manufacturing process, room temperature is sufficient.

The following examples illustrate the microemulsion liquid detergent compositions of the invention described above. Unless otherwise specified
All percentages are by weight. The illustrated compositions are merely exemplary and are not intended to limit the scope of the invention.

[0075]

Example 1 The following anthelmintic microemulsion composition was prepared.

Weight% Material A B C D Deionized Water 89.65 89.9 89.3 89.3 Paraffin Sulfonate 2.0 2.0 2.0 2.0 2.0 Lebenol F200 2.0 2.0 2.0 2.0 _{2.0 MgSO 4 · 7H 2 O 0.75} 0.5 0.5 0.5 DEGMBE (1) 2.8 2.8 2.8 2.8 MNDA (2) 2.0 2.0 2.0 0.0 DEET (2) 0.0 0.0 0.0 2.0 Perfume 0.8 0.8 0.8 0.8 Coconut oil fatty acid 0.0 0.0 0.5 0.5 0.5 Colorant 0 0.0 0.0 0.12 0.12 pH 6.5 6.5 6.5 6.5 6.5 Cloud point ° C 65>70>70> 70 (1) Diethylene glycol monobutyl ether (2) The above anthelmintic substance The above composition All produced acceptable cloud points. Cleaning tests were carried out by comparing the fat-cleaning effect of composition C according to the invention with a commercial microemulsion detergent composition having the following general composition: wt% substance E C ₁₄ -C ₁₇ paraffin sulfonate 4.0 Ethoxylated alcohol 2.5 Magnesium sulfate heptahydrate 1-2 Diethylene glycol monobutyl ether 2.8 pH 6.5 Water balance Composition C according to the invention is good both when used in perfect concentration and when diluted. Caused a fat cleaning. This was comparable in performance to commercial composition E when used at the same dilution.

Example 2 Composition E of Example 1 (commercial microemulsion composition not according to the invention) was used as a base composition, to which was added 2% by weight of MNDA anthelmintic agent. The resulting composition had a cloud point of about 38 ° C. and at temperatures above 38 ° C. resulted in a distinct phase separation of the composition. In comparison, the compositions of the present invention are characterized by a cloud point above about 45 ° C.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical indication C11D 3/32 3/36 3/37 (72) Inventor Thomas Francis Connors Piscataway, NJ, USA , Windmill Road 66 (72) Inventor Miriam Mondan Belgium 4100 Llans / Em, Rue de la Valerie 185/11

Claims (15)

[Claims] 1. A stable oil-in-water microemulsion detergent composition which is particularly effective for removing oily and greasy soils from hard surfaces and combating insects from the same, said emulsion comprising: The aqueous phase is based on the weight of the total composition: (A) (i) anionic surfactant; (ii) ethoxylated glycerol type compound, (i) to (ii) weight ratio of about 1: 1 to about. Up to 5: 1;
And (iii) a salt of a polyvalent metal cation in an amount sufficient to supply 0.5 to 1.5 equivalents of cation per equivalent of (i), the anionic surfactant and the polyvalent metal. The amount of cations and the amount of cation selected to provide a cloud point of at least about 45 ° C. to the finished microemulsion composition, about 0.1% to about 25%; (B) fatty acids, about 0-5%. (C) a water-soluble co-surfactant having substantially no ability to dissolve oily or greasy soil, about 0.1% to about 30%; and (D) water, the balance; The oil phase consists essentially of an effective amount of anthelmintic compounds and any perfume or water-insoluble hydrocarbons; removing such dirt from hard surfaces by solubilizing oily and greasy dirt in a microemulsion. Drive insects from the hard surface Excluding
At the same time, the cleaning composition, which is effective for attaching the anthelmintic compound to the hard surface to be cleaned to give the hard surface anthelmintic properties. 2. The cosurfactant is (a) water-soluble C ₃ -C ₄
Alkanols, propylene glycol and C ₁ -C ₉ alkyl ethers and C ₁ -C ₄ alkyl esters of ethylene glycol or propylene glycol; (b) aliphatic mono- and di-carboxylic acids containing 3 to 6 carbon atoms in the molecule; (C) Formula: R (OC ₂ H ₄ ) _n OXCOOH [in the formula,
R is C ₉ -C ₁₅ alkyl, n is a number from 4 to 12, X is selected from the group consisting of CH ₂ , C (O) R ₁ and C (O), R ₁ is C _1-. C ₉ -C ₁₅ alkyl ether polyethenoxycarboxylic acid represented by C ₃ alkylene group]; and (d) a mono-, di- and triethyl phosphate detergent composition. Stuff. 3. The cleaning composition according to claim 1, wherein the polyvalent metal cation is magnesium or aluminum. 4. The cleaning composition according to claim 3, wherein the polyvalent salt supplying the magnesium cation is magnesium oxide, magnesium chloride or magnesium sulfate. 5. The detergent composition of claim 4, wherein the magnesium salt is present in an amount to provide about 0.8 to 1.2 equivalents of cation per equivalent of anionic surfactant. 6. The cleaning composition according to claim 1, wherein the anionic surfactant is paraffin sulfonate. 7. The detergent composition according to claim 1, wherein the anthelmintic agent is an N-alkyl neoalkanamide, wherein the alkyl has 1 to 2 carbon atoms and the neoalkanoyl moiety has 7 to 14 carbon atoms. Stuff. 8. The cleaning composition according to claim 7, wherein the anthelmintic substance is methyl neodecane amide. 9. The cleaning composition according to claim 1, wherein the anthelmintic agent is N, N-diethyltoluamide (DEET). 10. The cleaning composition according to claim 1, which is essentially free of an insecticide. 11. A method of cleaning a hard surface and combating insects from the hard surface, the method comprising applying the microemulsion cleaning composition of claim 1 to the hard surface. 12. The method according to claim 11, wherein the anthelmintic substance is methyl neodecane amide. 13. The method according to claim 11, wherein the polyvalent metal cation is magnesium or aluminum. 14. The method of claim 11, wherein the microemulsion detergent composition is essentially free of insecticide. 15. A magnesium or aluminum salt in the amount of about 0.8 to about cation per equivalent of anionic surfactant.
14. The method of claim 13, which is present in an amount that provides 1.2 equivalents.