JPH0631420B2 - Liquid detergent with solvent - Google Patents

Description

FIELD OF THE INVENTION The present invention relates to fabric laundry compositions and methods that utilize large amounts of solvent to enhance grease-like stain and stain removal. The liquid compositions of the present invention not only provide excellent pretreatment cleaning performance, but also show clear, or substantially clear, uniform transparency when used in aqueous laundry liquors that exhibit improved detergency and fabric whiteness retention. It is provided in the form of a stable emulsion. In addition to providing improved removal of greasy stains such as motor oils, cosmetics, the composition is also excellent at removing particulate soil from fabrics. The composition is formulated and stabilized at a pH in the near neutral to alkaline range.

Background Various organic solvents, such as terpenes and terpene-like compounds, are rather well known for use in hard surface cleaners because of their grease removal performance. Such cleaners often contain solvents such as 10% or more of d-limonene, together with surfactants, which are also well known for their degreasing performance, especially nonionic surfactants. Such compositions have also been suggested to clean carpets. British Patent No. 1,60
No. 3,047. EPO Application No. 81200540.
No. 3 discloses a hard surface cleaner consisting of a mixture of benzyl alcohol, terpenes, surfactants and other detergent ingredients.

Citrus juice, which contains a relatively small amount of terpenes,
It has been suggested for use in hand soap and dishwashing liquids. U.S. Pat. No. 3,650,968, Mmoire descriptif 873,051 (Breve
t Anglais 53472/77).

Terpineol, for example from pine oil, has been disclosed for use in wet polishing fabrics. Especially, 19
In 37, U.S. Pat. No. 2,073,464,
Disclosed is a clear composition that can be prepared from pine oil terpineols such as α-terpineol and fatty acid soaps or free acids that are neutralized in situ to alkaline pH.

More recently, Soap Perfumery Cosmetics, 1
April 983, 174, 175, suggests that only small amounts of terpenes (3%) can be incorporated into heavy duty liquid detergents.

European Patent Application No. 0072488 describes a terpene,
For example, it is suggested that d-limonene can be incorporated into the fabric pretreatment composition as a heterogeneous emulsion. Such emulsions are obviously designed to be placed in relatively small volume containers. The container can be shaken just prior to use to restore slight homogeneity and then dispensed directly onto the fabric by spraying.

A transparent emulsion consisting of water, a surfactant and various other solvents is disclosed by David Zorn at the 3rd International Conference on Surface Activeness, Cologne (1960).

The use of relatively high concentrations of solvent in heavy duty liquid laundry detergents offers many advantages. The liquid form of such products allows them to be used as pretreatment agents. Through-the-
Solvents, such as terpenes, when used in wash) have now been found to provide additional cleaning benefits that are higher than those provided by detergent surfactants. Disadvantageously, most heavy duty liquid detergents are packaged in relatively large containers that are difficult for the user to completely shake, so EPO No. 007
The non-uniformity of compositions such as those disclosed in 2488 makes them inconvenient to use as a general purpose laundry detergent.

Furthermore, small amounts (about 3%) of terpenes alone in detergent compositions used in the through-the-wash method have little to do with additional cleaning benefits, as dilution with cleaning fluids eliminates their effect. Do not give.

The present invention is an essentially water-insoluble solvent in the form of a liquid containing a homogeneous fatty acid that is quite suitable for use in both fabric pretreatment and through-the-wash processes.
Provided is a fully formulated heavy duty liquid laundry detergent containing greater than or equal to weight percent.

Importantly, a means of formulating such compositions as stable microemulsions at a pH of about 6.5 or higher is disclosed.

SUMMARY OF THE INVENTION The present composition provides conventional detergent ingredients such as detergent builders,
In heavy duty liquid detergents containing enzymes, detergent surfactants, enzyme stabilizers, etc., formulated as an oil-in-water emulsion (the solvent is the "oil" phase) in an aqueous medium, and the composition is a solvent (eg, , Orange terpene, or d-
Limonene, isoparaffin oil or octylbenzene)
The solvent contains at least 5% by weight (preferably 5 to 50%, more preferably 5 to 20%), and the solvent comprises a fatty acid or soap (preferably C _{12 to} C ₁₈ fatty acid or fatty acid soap) and a detergent surfactant. Microemulsified into a composition by combination, said composition being stabilized by ionic strength and / or suitable selection of surfactant HLB, or (preferably) a nitrogen-functional compound, whereby a pH of 6.5 or higher is obtained. It may be briefly described as a heavy duty liquid detergent characterized in that it provides a transparent, or substantially transparent, stable, uniform liquid.

DETAILED DESCRIPTION OF THE INVENTION The essential solvent / fatty acid (or soap) / water emulsification system used in the practice of the present invention, detergent surfactant ingredients, means for stabilizing formulations at pH greater than 6.5 and Various other optional ingredients are described in further detail below. All percentages and ratios mentioned herein are by weight unless otherwise noted.

Solvent The solvent used in the present invention can be any of the well known "degreasing" solvents commonly known for use in, for example, the commercial laundry and dry cleaning industry, the hard surface cleaner industry and the metalworking industry. Typically, such solvents consist of alkyl or cycloalkyl type hydrocarbon or halogenated hydrocarbon moieties and have a boiling point well above room temperature.

The formulator of the composition of the present invention will select the solvent partly due to the need to provide good degreasing properties and partly due to aesthetic considerations. For example, kerosene hydrocarbons perform quite well in the composition but may have a foul odor. Kerosene can be used in commercial laundry. For domestic use, if malodor is not acceptable, the formulator will likely choose a solvent that has a relatively pleasant odor that can be reasonably modified by perfume use.
Such solvents are, for example, terpene and terpenoid solvents obtained from citrus fruits, especially orange terpenes and d-limonene. Benzyl alcohol is another solvent with a relatively pleasant odor for use in the present invention. Mixtures of orange terpenes and benzyl alcohol are particularly suitable for removing certain stains such as marker inks, shoe inks, and dirty motor oils.

Excellent solvents for use in the present invention are paraffins and monocyclic monoterpenes and bicyclic monoterpenes, ie those of the hydrocarbon type such as terpinene, limonene and pinene, and mixtures thereof. A highly preferred substance of this latter type is a mixture of d-limonene and terpene hydrocarbons obtained from the essence of oranges (eg cold pressed orange terpene and orange terpene oil phases from fruit juice). Also useful are, for example, terpenes squeezed from lemon and grapefruit, such as mixtures of dipentene, α-pinene, β-pinene and terpene hydrocarbons.

Various other solvents that can be used in the composition, especially preferred mixtures of non-polar and polar solvents are described below.

Fatty acids and soaps Fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid and oleic acid, and polyunsaturated fatty acids, and their water-soluble salts (ie soaps)
Is used in the composition to provide a clear, uniform formulation containing solvent and water. Mixtures of C ₁₂ -C ₁₈ carbon chain fatty acids (soaps), such as palm oil acids,
Palm oil acids and the like can be used. Generally, the concentration of fatty acid (or soap) is 5% to 50%, preferably 5% to
35%, most preferably 5% to 30%, and the weight ratio of fatty acid (or) soap to solvent is 4: 1 to 1:
It is in the range of 4, preferably 3: 1 to 1: 2. When using a fatty soap, the potassium and sodium salt forms are preferred, but any convenient water soluble salt is
Can be used.

Apart from functioning as microemulsion stabilizers, these fatty acid / soap materials provide important detergency builder functions in the composition. However, about 6.
It has now been discovered that the presence of fatty acids / soap can actually destabilize the system when formulating oil-in-water microemulsion compositions with pH greater than 5. Means for overcoming this destabilization while maintaining a pH above 6.5 in a microemulsion containing a builder amount of fatty acid / soap are disclosed in detail below.

Water The present composition may be suitably characterized as "water-based," as opposed to organic solvent-based cleaners known in the art.

Surprisingly, water can interfere with the ability of solvents such as terpenes to remove grease-like stains from fabrics. For example, fabrics soiled with motor oil and wet with water prior to treatment with raw terpenes, if any, are not defatted very well by terpenes. In contrast, non-polar solvents,
For example, the present composition in which a terpene is microemulsified in water is an excellent grease-like stain remover when used directly on a dry or wet fabric.

Aside from the obvious environmental and safety benefits of water versus organic solvents and low cost, water-based heavy-duty liquid detergents typically contain components that are water-soluble, such as most cleaning products. It provides the advantage of facilitating formulation with respect to force builders, disinfectants, chelating agents, soil suspending agents, pH control agents and the like.

Thus, the composition presents the flexibility advantages of water-based formulations along with the excellent degreasing properties of solvent-based compositions.

As described in more detail below, the composition generally contains 10% to 70% water, preferably 20% to 50%. The weight ratio of water to solvent is generally 10: 1 to 1: 1, preferably 5: 1 to 2: 1.

pH Stabilizer As is well known in the washing technology, it is preferable that the detergent composition is within a range from near neutral pH to alkaline pH, that is, pH 6.5 or higher. This is for various reasons.
For example, many soils are partially peptized or emulsified by the alkalinity itself. And, many commercially available detergent enzymes (eg, "alkaline proteases") work optimally in alkaline laundry liquors.

It has now been discovered that stable oil-in-water microemulsion detergent compositions containing builder amounts of fatty acids / soaps are destabilized when their pH is adjusted to above about 6.5 (instability). Can vary slightly depending on the actual degreasing solvent used in the microemulsion, its amount, and the chain length and unsaturation of the fatty acids). This problem is especially acute in the case of substantially non-polar hydrocarbon degreasing solvents such as orange terpenes and paraffin oil.

Stability issues are very narrow pH range, typically 6.5-
It appears to be caused by fatty acids of about 2 HLB that are almost completely converted to a soap of about 20 HLB over 6.9.
Thus, as fatty acids are present in substantial amounts (above about 5%), major HLB translocation disrupts and destabilizes the HLB of the emulsifying system.

It should be understood that the stability of the formulation can theoretically be achieved by proper selection of surfactants with low HLB (discussed below). For example, nonionic surfactants,
For example C ₁₄ ~ with low ethoxylate numbers (1-3)
₁₅ alcohol was available. However, such low HLB surfactants do not perform well as detergent surfactants, and the purpose of the present invention is not only to provide stable microemulsions, but also good pretreatment and through-the-wash. It is to give detergency.

The microemulsion is stabilized by increasing the ionic strength of the aqueous phase, or by adding a solvent-soluble component of low HLB which increases the solvent polarity to the solvent phase, or by using both means simultaneously. Things are now being found.

In particular, the addition of water-soluble high ionic strength components, such as formates, sulphates, citrates, etc., increases stability. In contrast, the addition of water-soluble low ionic strength substances such as ethanol has no stabilizing effect.

Also, adding a slightly polar component of low HLB that is soluble in a non-polar solvent, such as n-hexanol, benzyl alcohol, mixed fatty alcohols, etc., increases stability.

The combined use of the ionic strength component and the solvent-soluble component further enhances the stability. Of course, the formulator can select the ingredients not only to increase the stability of the microemulsion, but also to provide optimal cleaning benefits. For example, formulators can find citrate as an ionic strength imparting agent that also has detergency builder properties, formate as an ionic strength imparting agent that also stabilizes detergent enzymes, and low HLB components that also serve a useful degreasing function. N-hexanol or benzyl alcohol can be selected.

The amount of ionic strength component or low (eg 2 to 5) HLB solvent soluble component used in the composition, or both, is desired pH, concentration of fatty acids, amount of degreasing solvent, composition of detergent surfactant system, etc. Will be somewhat dependent on. The stability of microemulsions can be monitored rather easily, since a true microemulsion is transparent, but becomes cloudy and inhomogeneous and finally phase separates in terms of instability.

For adjusting the pH of the composition, any of the well known base materials, such as triethanolamine, alkali metal hydroxides, etc., can be used to adjust the pH to about 6.5 to 6.6. Potassium hydroxide is preferred over sodium hydroxide because the ease of formulating a stable system is substantially increased by the potassium cation.

Magnesium hydroxide is another useful neutralizing base. When used, the magnesium cations are believed to associate with the anionic surfactants present in the composition to enhance their degreasing performance.

Adjusting the pH from above 6.5 to 6.6, preferably using various amines, amine oxides and quaternary ammonium salts (ie "nitrogen functional" compounds),
And further stabilizing the microemulsion is described in more detail below.

Detergent Surfactants The compositions of the present invention will typically contain organic surfactants (“surfactants”) to provide the usual cleaning benefits associated with the use of such materials. Let's do it.

Detergent surfactants useful in the present invention are, for example, the well known synthetic anionic, nonionic, amphoteric and zwitterionic surfactants. Typical of these are alkylbenzene sulfonates, which are well known from the washing art,
Alkyl sulphates and alkyl ether sulphates, paraffin sulphonates, olefin sulphonates, alkoxylated (especially ethoxylated) alcohols and alkylphenols, amine oxides, α-sulphonates of fatty acids and α-sulphonates of fatty acid esters and the like. In general, such detergent surfactants, C ₉ ~
It contains alkyl groups within the C ₁₈ range. Anionic detergent surfactants can be used in the form of their sodium, potassium or triethanolammonium salts,
It should be understood that the presence of the magnesium cation in the composition usually means that at least some of the anionic surfactant will be in the form of the magnesium salt. Nonionic surfactants generally contain from about 5 to about 17 ethylene oxide groups. U.S. Pat. No. 4,11
1,855 and 3,995,669 encompass a detailed listing of such typical detergent surfactants. C _{11 to} C ₁₆ alkylbenzene sulfonate, C ₁₂ to
C ₁₈ paraffin sulfonates and alkyl sulphates, and ethoxylated alcohols and ethoxylated alkylphenols are especially preferred in the compositions of the present invention.

The surfactant component can be as much as 1% of the composition, but preferably the composition comprises from 1% to 40% surfactant.
%, Preferably 10% to 40%. Mixtures of ethoxylated nonionic and anionic surfactants such as alkylbenzene sulfonates, alkyl sulphates and paraffin sulphonates have been found to allow wide spectrum stains and stains to pass through the fabric.
Preferred for wash cleaning. Such surfactants and mixtures typically have an HLB of 20 or higher.

Polyamines Polyamine substances work together with solvents in many greases.
Fixing substances present in blemishes (eg motor oil stains
Carbon black in, clay in cosmetic stains and coloring
The composition may optionally be distributed due to its ability to remove
It is a combined ingredient. As used herein, "polyamid"
The term "n" generally refers to those amine forms and
Means both alkoxylated polyamines in quaternized form
It should be understood that Such substances are
Experimentally structured molecules with repeating units (In the formula, R is usually a hydrocarbyl group having 2 to 6 carbon atoms.
R; R'is C₁~ C₂₀Can be a hydrocarbon;
Coxy group is polyethoxy, polypropoxy, etc.
Liethoxy has a degree of polymerization of 2 to 30, most preferably 10 to 20.
X; at least 2, preferably 2 to 20, most preferred
Is an integer from 3 to 5, and X Is the quaternization reaction
Derived anions such as halides or methylsulf
Can be conveniently represented as). Anion X Is
It is not critical to the performance of the polyamine in the present invention, and
It is described only for the completion of the above formula.

The most highly preferred polyamines for use in the present invention are the so-called ethoxylated polyethyleneimines, i.e. (Wherein x is an integer of 3 to 5 and y is an integer of 10 to 20), which is a polymerization reaction product of ethylene oxide and ethyleneimine.

The polyamine will typically make up at least about 0.2% of the preferred compositions of the invention, generally 0.5% to 5%.

Other Ingredients Optionally Incorporated The compositions may contain other ingredients that aid in their cleaning performance. For example, through-the-wash detergent compositions are highly preferred to contain detergent builders and / or sequestrants. Compounds that can be classified as detergent builders and are well known in the art include, for example, nitrilotriacetate, polycarboxylates, citrates, water soluble phosphates such as tripolyphosphate and sodium orthophosphate and sodium pyrophosphate, silicates, and mixtures thereof. Is. Sequestrants include, for example, all of the above, and substances such as ethylenediaminetetrathiacetate, aminopolyphosphonates and phosphates (DEQUES).
T) and various other polyfunctional organic acids and salts (too many to be detailed here). See U.S. Pat. No. 3,579,454 for typical examples of the use of such materials in various cleaning compositions.
Generally, the builder / sequestrant will make up about 0.5% to 15% of the composition. Citrate is one of the most preferred builders because it is readily soluble in the aqueous phase of heavy duty liquid detergent compositions. Such ingredients are also useful in hard surface cleaners.

A source of magnesium ions can be used in the composition for the reasons mentioned above. Besides magnesium hydroxide, water-soluble salts such as magnesium chloride, magnesium acetate, magnesium sulphate, etc. can be used.

The laundry composition of the present invention preferably also contains an enzyme to enhance through-the-wash cleaning performance against various stains and stains. Suitable amylase and protease enzymes for use in detergents are well known in the art and commercially available liquid and granular detergents. Commercial detergent enzyme (preferably a mixture of amylase and protease) is present in the composition at 0.0
It is typically used in amounts of 01% to 2% and higher. Ingredients such as propanediol and / or formate and calcium can be added by well known methods to stabilize the enzyme as desired by the formulator.

In addition, the composition may contain, in addition to the ingredients described above, various other ingredients typically used in commercial products to provide aesthetic or additional product performance benefits. it can. Typical ingredients are, for example, perfumes, dyes, optical brighteners, soil suspension agents, hydrotropes and gel control agents, freeze / thaw stabilizers, bactericides, preservatives, control agents, etc. (0.1% to 15%).
% Amount).

Water or water / alcohol (e.g. ethanol, isopropalle, etc.) mixtures are used as carrier vehicles and alkylated polysaccharides can be used to enhance the stability and performance properties of the composition.

The composition is in liquid form, which may be prepared by simply blending the essential and optional ingredients in an aqueous carrier. The stability of microemulsions can be assessed visually by watching for phase separation, or can be monitored more quantitatively by standard turbidity measurement techniques.

In one process aspect, the composition is a small amount of composition (m
It can be used to pretreat soiled fabrics by rubbing l) directly onto or into the soiled area and then laundered by standard methods. In the Through The Wash process, the composition is used to wash fabrics in an aqueous laundry bath having a pH of 6.5 or above, typically at a concentration of at least 500 ppm, preferably 0.1% to 1.5%. To be done. Washing can be carried out over a range from 5 ° C to boiling with excellent results.

For use on hard surfaces as a rug cleaner and as a general purpose cleaner, the composition is diluted with water or at full strength, all using standard methods.

INDUSTRIAL APPLICABILITY The following examples describe various formulations that can be prepared by the method of the present invention. The examples are given by way of illustration and do not limit the scope of the invention. In the polyamine-containing formulations below, the symbols "x" and "y" are written in parentheses to indicate the degree of polymerization and alkoxylation of the polyamine. In the case of some polyamines,
The designation R'is also included, thereby indicating a quaternized polyamine. In the case of such a quaternized material, the resulting X
^- anion is not critical to the cleaning performance, and not displayed.

Heavy Duty Liquid Detergents Special attention is directed to highly preferred formulations that are particularly useful as heavy duty liquid detergents suitable for laundering all fabrics in typical home laundry operations. The heavy-duty liquid detergents described below are formulated using various detergent ingredients to provide excellent cleaning of various stains and stains, with particular notable benefits relating to cosmetic and dirty motor oil stains.

It should be understood that the following formulations are in the form of oil-in-water emulsions (detergents are believed to be the "oil" phase) and are substantially clear, homogeneous and stable microemulsions. . Surprisingly, when used in the pretreatment method, the oil-in-water microemulsions of the present invention are comparable in degreasing performance to water-in-oil emulsions with significantly higher concentrations of solvent. The composition also exhibits excellent whiteness retention on cotton fabrics, as the solvent apparently reduces the accumulation of fatty acid soaps on the fabric surface. These performance advantages are especially significant after multiple cycle washes.

The composition is prepared by blending the components to give a clear stable microemulsion. Especially in a laundry test using a pretreatment step, the composition
Gives excellent performance against various stains, especially cosmetics and dirty motor oils.

Example II The composition of Example I is modified slightly by using 0.6 parts by weight magnesium hydroxide instead of 2 parts 50% KOH and adjusting the pH to 7.5. The product obtained is a clear, stable and homogeneous microemulsion.

Example III The compositions of Examples I and II are each modified by the addition of 1.5 parts by weight of tetraethylenepentamine ethoxylated with an average of 15 moles of ethylene oxide per nitrogen atom.
The resulting composition is a clear, stable and uniform microemulsion with a pH higher than 6.9.

As another example, any of, orange terpenes deodorized paraffin oil instead of a solvent of the composition; (2.5% of the total composition) (iso C ₁₀ -C ₁₂ 7.5% of the total composition) and orange terpenes Can be modified by using a mixture of This change in solvent composition never compromises the performance characteristics of the composition, allowing perfume formulators greater freedom to introduce non-citrus perfume elements. If desired, anionic optical brighteners (0.01-0.5%) can be added.

Solvent Selection As mentioned above, the final choice of solvent system used in the composition will depend on the type and loading of the soil, aesthetic properties (odor), etc. However, a number of criteria can be used to guide this selection. For example, the solvent should be substantially water immiscible and, of course, should be able to solubilize a wide range of problematic greasy soils. In this latter point, the thermodynamic solubility coefficient (Hansen coefficient) is useful in making solvent selections.

Any solvent can be described by the Hansen coefficients δd, δp, δh. δd is the dispersive component; δp is the polar component; and δh is the hydrogen bonding component. Similarly,
Greasey stains of key problems can also be described by the "pseudo" Hansen coefficient. To do this, the solubility of each greasy soil in a wide range of solvents with different Hansen coefficients is first evaluated. This means that grease-like stains on a wide range of different fabric types (cotton, polyester cotton, acrylic) can be applied to each solvent for a fixed time (eg 5
Min) can be performed by dipping. Upon removal, excess solvent is drained off and the soiled fabric is
Wash for 5 minutes in cold water containing 1% strength of typical liquid detergent. After final rinsing in cold water and drying, stain removal can be evaluated visually or by any other suitable technique. By proceeding with this method, the solvent that gives the best removal of each problematic greasy stain can be identified, and thereby the range of Hansen coefficients required for optimal removal of a particular stain can be evaluated. Thus, for each stain, a map of the Hansen coefficient is obtained, and the solvent / solvent combination can be selected on this basis to give the target performance profile.

Without intending to limit the invention, the technique
A solvent / solvent composition having a Hansen coefficient within the range of d (7-9), δh (0-7), δp (0-4) is the key to formulating a microemulsion having excellent grease-like stain removal performance. Indicates that. Solvent combinations have specific grease-like stains, for example, the optimal Hansen coefficient range is δ
Motor oil with p (7-9), δh (0-4), δp (0-3), optimum range is δd (7-9), δh (2-1)
1), can be targeted to marker inks that are δp (2-7), or can be more broadly targeted to mixed stains by choosing an intermediate point within the Hansen coefficient range.

Solvents and solvent mixtures which are preferred according to the invention, in particular orange terpenes (d-limonene), paraffins (in particular iso-C).
₁₀ -C _12), cyclohexane, kerosene, orange terpene / benzyl alcohol (60/40), n-paraffins (C
_12-15) / hexanol (50/50) fall within the Hansen coefficients as described above.

Any of the above examples may be modified by substituting the above for the indicated solvent, in particular a mixture of terpene or paraffin oil with benzyl alcohol, n-hexanol or 1-butanol. The preferred pH for heavy duty detergents is 6.5-8.
0, and more preferably 6.6 to 7.3. The pH of the product "as is" is normal temperature (23 ° C) using a commercial pH meter.
Measured at. The electrodes are dipped into the product and the pH meter is stabilized before reading.

The following examples relate to compositions within the scope of the invention having a solvent that is particularly suitable in industrial heavy duty laundry / cleaning plants and the like. It is recognized by the formulator that some of the solvents used in such compositions may be unsuitable for general household use due to malodor, skin irritation potential, low flash point, etc. Will. However, such a composition is quite suitable for use under properly controlled conditions by a professional operator who takes such matters into consideration. In Examples IV-IX, the pH is adjusted with magnesium hydroxide as indicated in all compositions. All other ingredients are listed in parts by weight.

As is apparent from the above, the present invention includes various formulations in the form of stable solvent-containing emulsions. Excellent heavy duty liquid detergent compositions include diethyl phthalate (preferred) or dibutyl phthalate and terpenes (preferably orange terpenes) or dipentene,
Alternatively, it may be prepared using a solvent system consisting of paraffin oil or mixtures thereof (most preferred). The following are representative examples of such compositions.

In Example X, an equivalent amount of diethyl phthalate can be used instead of dibutyl phthalate.

It will be appreciated that many of the above compositions containing terpene hydrocarbons will necessarily have a strong citrus odor that is not entirely unacceptable to all formulators of such compositions. C ₆ -C ₉ alkyl aromatic solvents, especially C ₆ -C ₉ alkyl benzenes, preferably octyl benzene, showed excellent grease removal properties and have a low pleasant odor has now been discovered. Similarly, olefin solvents having a boiling point of at least about 100 ° C., especially α-olefins, preferably 1-decene or dodecene, are excellent degreasing solvents. Further, isoparaffin (especially C ₁₀ -C ₁₂ chain length) is noteworthy their low odor, and with high grease removal properties.

Combinations of said alkylaromatic or paraffinic or olefinic solvents with polar liquids such as benzyl alcohol, n-hexanol, butyl carbitol (trademark, 2- (2-butoxyethoxy) ethanol) or phthalates are suitable for the practice of the invention. Constitutes an additional example of a preferred non-polar / polar solvent for use in.

The following additional examples further illustrate oil-in-water emulsion microemulsions. In Example XIV, a quaternary ammonium compound was used to reduce the pH of the formulation to a pH slightly below neutral.
Adjusting to H importantly contributes to product performance while maintaining long term microemulsion stability.

Example XI Component Weight% C _11.8 Alkylbenzene sulfonic acid 10.0 C _14/15 Alkyl ethoxylate (EO7) 10.9 Coconut fatty acid (broad cut) 18.2 Oleic acid 2.3 Monomethylethanolamine 5.8 1-Decene 9 .1 Ethanol (95%) 2.7 Duquest (50%) ¹⁾ 1.09 Formic acid 0.18 Potassium citrate H ₂ O (63.5% in H ₂ O) 4.4 CaCl ₂ .2H ₂ O 0.05 Maxatase enzyme (protease) 0.73 Tamamyl enzyme (amylase) 0.10 Ethoxylated polyamine ²⁾ 1.73 Fragrance / optical brightener / dye 0.5 Water balance Product pH 6.6 1) Diethylenetriamine pentamethylene Phosphonic acid 2) Tetraethylenepentamine 105 EO units / molecule The composition of Example XI is used as a laundry detergent. It is suitable stabilizing oil in water microemulsion.

Example XII The composition of Example XI is modified by substituting the same amount (9.1% of total formulation) of n-octylbenzene instead of 1-decene. The "as is" product pH is 6.6.

Example XIII The composition of Example XI was prepared by replacing one of the following solvent mixtures in place of 1-decene with the following solvent mixtures (% relative to the total formulation is specified in parentheses): 1-decene (6.1
%) / Diethyl phthalate (3.0%), 1-dodecene (7.3%) / benzyl alcohol (1.8%), n-
Modified by using octylbenzene (6.2%) / diethyl phthalate (2.9%), n-octylbenzene (6.0%) / butyl carbitol (3.1%). The raw product pH is 6.6.

Example XIV The compositions of Examples XI, XII and XIII are modified by adding sufficient dioctyldimethylammonium chloride to adjust the "as is" pH of the composition from 6.6 to 6.94. The resulting composition exhibits very good fabric cleaning and whiteness maintenance.

It should be understood that the preferred compositions of Examples VI-XIV are in the form of true oil-in-water microemulsions. Upon dilution with water, the composition appears cloudy. In contrast, water-in-oil emulsions tend to gel upon dilution, while micellar oil-in-water compositions remain clear upon dilution.

Example XIV uses a nitrogen functional component (quaternary) to produce a product pH
To adjust. Other such pH adjusters include, for example, the following (product pH is shown in parentheses): coconut alkyldiethanolamine (6.65), coconut dimethylamine (6.7).
5), trioctylamine (7.0), cyclohexylamine (7.5), coconut alkyl trimethyl ammonium chloride (6.66), coconut alkyl dimethyl amine oxide (6.70), dicoconut alkyl dimethyl ammonium chloride (6) .84), coconut alkylbenzyldimethylammonium chloride (6.84), dihexyldimethylammonium chloride (6.89), and dioctylmethylamine oxide (approximate> 7). Such a nitrogen functional material is p
H is adjusted and, importantly, is used in an amount of 0.5-5% in the composition to contribute to cleaning and whiteness maintenance of the washed fabric. Cyclohexylamine (1-5%) is preferred for this application.

Another olefin solvent preferred in the present invention due to its relatively low odor is the so-called "P" available in the detergent industry from many petrochemical companies as a raw material for branched alkylbenzenes.
-4 "polymer. P-4 is an isomer mix of the condensation product of 4 moles of propylene, i.e., C ₁₂ branched olefins. P-4 is non-polar and is preferably used in combination with polar solvents such as benzyl alcohol, diethyl phthalate, butyl carbitol and the like.

"Carbitol" 2- (2-alkoxyethoxy) besides other polar solvents useful in the present invention ethanol, for example, "Cellosolve", for example, 2-alkoxyl alkanols such as 2-butoxyethanol; C ₄ -C ₁₂ alkyl Alcohols such as dodecanol, phenethyl alcohol, and diglycol ether acetate.

Example XV A preferred composition due to its low odor properties and low compatibility with polyethylene containers is 6% diethyl phthalate / isoparaffin liquid (C ₁₀ -C ₁₂ ) as a percentage of the total composition instead of 1-decene of Example I. Prepared by using a solvent mixture consisting of 2% / 2% orange terpene.

Importantly, all microemulsion compositions of the present invention do not affect high density polyethylene and therefore can be packaged in high density polyethylene bottles. In contrast, many solvent-containing cleaners that are not in the form of true microemulsions must be placed in more expensive metal cans or polyvinyl chloride bottles.

Example XVI The following is yet another example of a degreasing solvent mixture of polar and non-polar solvents used in the present invention.

In a preferred use aspect, the composition is used in an aqueous laundry liquor (laundry liquor pH 6.5-8.0, preferably measured as 1% composition in water) for laundering fabrics. Excellent cleaning is due to this p
Achieved by stirring in H range laundry liquor.

Example XVII A highly preferred liquid laundry detergent due to its low odor properties of its degreasing solvent system, its stability in microemulsion form, and its enzymatic cleaning activity (depending on its pH) is as follows:

Ingredient Parts by Weight alkyl (C _11.8) benzenesulfonic acid 11.0 alkyl (C _14/15) ethoxylate (EO 7) 12.0 topping total cut coconut fatty acid (1) 20.5 C ₁₀ ~ ₁₁ isoparaffins 4.0 phthalate Diethyl 6.0 Cyclohexylamine 2.0 Monomethylethanolamine (2) 4.3 Potassium citrate monohydrate (63.5% in water) 2.4 Deuquest 2060S 1.7 Ethoxylated polyamine (x = 5, y = 15) 1.5 Ethanol 3.0 Potassium hydroxide (50% in water) (2) 3.0 Formic acid 0.2 CaCl ₂ 2H ₂ O 0.05 Optical brightener (anion) 0.18 Maxatase enzyme (3 ) 0.71 Tamamyl 300L Enzyme (4) 0.10 Dye 20ppm Fragrance 0.5 Water up to 110 parts Product pH 6.9 (1) Chain length mixture: C ₁₀ (5%), C ₁₂ (55%), C ₁₄ (2
2%), C ₁₈ (2%), oleic acid (10%) (2) Adjust pH to 6.6 (3) From KNGS (4) From NOVO The composition of Example XVII was prepared at a concentration of 100 ml / 10. Used in an aqueous laundry bath and gives a pH of about 7.2 in use (varies with water hardness).

Paraffins, especially iso C ₁₀ ~ ₁₂ (most preferably iso C
₁₀ ) The most highly preferred solvent mixture of paraffin hydrocarbons and diethyl phthalate (or less preferred dibutyl phthalate than those mentioned above) cleans the fabric in both pretreatment and through-the-wash processes. It works extremely well. These particular solvents, formulated in the ratio 5: 1 to 1: 5, are particularly advantageous because of their extremely low odor. Mixtures of these solvents with cyclohexylamine (ratio of solvent mixture to cyclohexylamine 10: 1 to 1:10, preferably 5: 1).
To 2: 1) give a homogeneous liquid composition in the form of an oil-in-water microemulsion, which is preferred for all methods of cleaning operation when grease stain removal is considered.

Besides their excellent cleaning performance, the microemulsion compositions of the present invention are notable for their mildness to the skin. This unexpected benefit in solvent-containing compositions allows the compositions to be used in hand-washing of fine fabrics, pottery, glassware and the like.

Continuation of front page (56) Reference JP-A-60-212498 (JP, A) JP-A-60-212499 (JP, A)

Claims (9)

[Claims] 1. An aqueous carrier, 10 to 40% by weight of a non-soap detergent detergent, and terpenes or terpenes, paraffins, halogenated hydrocarbons, C ₆ -C ₉ alkylaromatic compounds, liquid olefins and mixtures thereof. a liquid detergent composition containing 5 to 20 wt% grease removal solvent selected from, contain C ₁₂ -C ₁₈ fatty acids or their soaps 5-30 wt% and microemulsion stabilizer, the stabilizer , A water-soluble high ionic strength component selected from formate, sulphate or citrate,
A non-polar solvent-soluble component having an HLB of 2-5, a nitrogen-functional compound or a mixture thereof, wherein the composition is in the form of a stable oil-in-water microemulsion at pH 6.5-8.0. A liquid detergent composition. 2. A non-soap detergent surfactant is C ₉ to C.
₁₈ alkylbenzene sulfonates, paraffin sulfonates, fatty acid α-sulfonates, alkyl sulphates, ethoxylated alcohols and ethoxylated alkylphenols having 5 to 17 ethylene oxide groups,
A composition according to claim 1, which is selected from: and mixtures thereof. 3. The solvent is terpene, paraffin oil, C _6- .
C ₉ alkyl aromatics, liquid olefins or mixtures thereof, or terpenes, paraffin oil,, C ₆ ~
C ₉ alkylaromatic compound or olefin and benzyl alcohol, C ₄ -C ₁₂ alcohols, phthalic acid esters, 2- consisting (2-alkoxyethoxy) mixture of ethanol or 2-alkoxyalkanol, the first term claims or The composition according to item 2. 4. The solvent is (a) a terpene, iso C ₁₀ -C ₁₂ paraffin oil, C
A mixture of a non-polar solvent selected from _6- C ₉ alkylbenzenes or liquid olefins and (b) a polar solvent selected from benzyl alcohol, diethyl phthalate, dibutyl phthalate or 2- (2-butoxyethoxy) ethanol (provided that The weight ratio of (a) to (b) is 10: 1.
To 1:10), the composition according to claim 3. 5. The fatty acid or soap is a mixture of lauric acid / myristic acid or soaps, a coconut alkyl fatty acid or a mixture of fat soaps, or palm /
It is a mixture of coconut fatty acids or soaps,
The composition according to any one of claims 1 to 4. 6. Formulated at pH 6.6-7.3,
The composition according to any one of claims 1 to 5. 7. A high density polyethylene container packaged in any one of claims 1 to 6.
The composition according to the item. 8. A paraffin-to-phthalate mixture of iso-C ₁₀ -C ₁₂ paraffins with diethyl phthalate or dibutyl phthalate in a weight ratio of 5: 1 to 1: 5, according to claim 4. Composition. 9. A composition according to claim 8 wherein the nitrogen functional compound is cyclohexylamine.