JPH0633425B2 - Stabilized oil-in-water cleaning micro emulsion - Google Patents

Abstract

Solvent-containing liquid detergent compositions containing degreasing solvents such as n-octyl benzene, terpenes or olefins are prepared with high levels of fatty acid/soap at a pH of ca. 6.5. The compositions are pH-adjusted to neutrality or the alkaline pH range using various amines, amine oxides or quaternary ammonium salts.

Description

TECHNICAL FIELD The present invention adjusts the pH of carboxylic acid-containing oil-in-water microemulsions to the alkaline range using various nitrogen functional components such as amines, quaternary ammonium salts and amine oxides. Regarding the method. Thereby, liquid laundry detergent compositions, liquid hard surface cleaners and the like are provided.

Background Various organic solvents, such as terpenes and terpene-like compounds, are rather well known for use in hard surface cleaners because of their degreasing ability. 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. 1,603,047
Issue specification. EPO Application No. 81200540.3 discloses a hard surface cleaner consisting of a mixture of benzyl alcohol, terpenes, surfactants and other detergent ingredients.

European Patent Application No. 0072488 suggests that terpenes such as d-limonene may 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 a 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 Zone in the 3rd International Conference on Surface Activeness, Cologne (1960).

Terpineol, for example from pine oil, has been disclosed for use in wet polishing fabrics. Especially 1937
In the year U.S. Pat. No. 2,073,464 disclosed clear compositions that could be prepared from pine oil terpineols, such as α-terpineol and fatty acid soaps or free acids neutralized in situ to alkaline pH.

More recently in Soap Perfumery Cosmetics, 19
April 1983, p. 174, p. 175, suggest that only a small amount of terpene (3%) can be incorporated into a heavy duty liquid detergent.

The citrus diuse, which contains a relatively small amount of terpenes,
It has been suggested for use in handsets and dishwashing liquids. U.S. Pat.No. 3,650,968, M
e′moire descriptif No. 873,051 (Brevet Anglais No. 53
472/77 related).

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, some alkylaromatic hydrocarbons, and some olefin hydrocarbon solvents, when used in wash), add more than the cleaning benefit provided by the detergent surfactant. It has now been found to provide cleaning benefits. Disadvantageously, most heavy duty liquid detergents are packaged in relatively large containers that are difficult for the user to completely shake, thus making it difficult to use compositions such as those disclosed in EPO 0072488. The uniformity makes it inconvenient to use as a general purpose laundry detergent.

The present invention is in the form of a homogeneous fatty acid builder-containing liquid, which is quite suitable for use both in fabric pretreatment methods and through the wash washing methods as hard surface cleaners and the like, in amounts as high as 20% by weight and A fully formulated heavy duty liquid detergent composition containing a greater amount of an essentially water-insoluble solvent is provided.

Importantly, a means of formulating such formulations as stable microemulsions at a pH above the "as is" formulation pH of about 6.5 is disclosed.

SUMMARY OF THE INVENTION The present invention typically employs water (10% to 70%), degreasing solvents or solvent mixtures (5% to 20%), fatty acids or fatty acid / sequene mixtures (5% to 35%) and detergent interfaces. The pH of oil-in-water microemulsions consisting of a mixture of activators (1-40%) is adjusted by mixing them with nitrogen functional substances such as amines, quaternary ammonium salts, or amine oxides. , Thereby adjusting the "as is" pH of the microemulsion to a neutral or alkaline pH from the original pH of about 6.5, thereby improving the cleaning performance of the microemulsion, especially the enzyme cleaning action. Including means to be improved.

The invention also includes the compositions prepared by the above methods, and methods of using the compositions to clean fabrics and hard surfaces.

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
Unless otherwise stated, weights are indicated.

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 may be used in commercial laundry. For household use, if malodor is not acceptable, the formulator will likely choose a solvent with 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.

Accordance connexion, one preferred type of solvent used in the present invention, flow paraffins, in particular "iso" C ₁₀ paraffins and monocyclic monoterpene and bicyclic monoterpenes, i.e., those hydrocarbon type, for example terpinene, Limonene and pinene, and mixtures thereof. A highly preferred material 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.

Another preferred class of solvents are C ₆ -C ₉ alkyl aromatic hydrocarbons, in particular C ₆ -C ₉ alkyl benzenes, especially octyl benzene. Short chain alkylbenzenes (eg, toluene) are not preferred in the present invention due to toxicity and odor issues, and longer chain alkylbenzenes cause undesirable soil redeposition problems, especially when used to wash fabrics. Have.

Yet another preferred type of solvent has a boiling point of at least about 100.
It is an olefin having a temperature of ° C. Alpha-olefin has now been found to have excellent cleaning properties and a low rather pleasant odor. The compounds 1-decene and 1-dodecene are particularly preferred olefin solvents for laundry detergent applications.

In a highly preferred method, said relatively non-polar solvent, such as paraffin, olephine, terpene or alkylbenzene solvent, is treated with a more polar solvent, such as benzyl alcohol, n-hexanol, phthalates such as dimethyl phthalate, phthalate. Diethyl acid (preferred), dipropyl phthalate or dibutyl phthalate,
Or used in combination with a "Carbitol" solvent, such as Butyl Carbitol (trademark of 2- (2-butoxyethoxy) ethanol), for a wide spectrum of various polar and non-polar stains. Give cleaning. Such mixtures have a ratio of non-polar solvent to polar solvent of 10: 1 to 1:10, preferably 5: 1 to 1: 5, most preferably the non-polar solvent is polar, especially in the case of fabric washing. It has a slightly higher ratio than the solvent, generally a ratio of 5: 1 to 5: 4.

The examples below describe various other solvents that can be used in the composition.

As will be appreciated from the disclosure below, various conventional detergent ingredients are used in the present invention in conventional amounts and concentrations.

Importantly, in liquid detergent formulations, the solvents of the present invention provide relatively high amounts (15-25% and higher, depending on the solvent) of fatty acid / sequent that provide important detergency builder function. Can be used in combination with.

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 surfactants, nonionic surfactants, amphoteric surfactants 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, olein sulphonates, alkoxylated (especially ethoxylated) alcohols and alkyl phenols, 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. Nos. 4,111,855 and 3,995,669 enclose a detailed listing of such typical detergent surfactants. C _{11 to} C ₁₆ alkylbenzene sulfonate, C ₁₂
-C ₁₈ paraffin sulfonates and alkyl sulphates, and ethoxylated alcohols and ethoxylated alkyl phenols are particularly 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 (eg, alkylbenzene sulfonates, alkyl sulphates and paraffin sulphonates) have been used for through-the-wash cleaning of broad spectrum stains and stains from fabrics. preferable. Such surfactants and mixtures typically have an HLB of 20 or higher.

Polyamines Polyamine substances work together with solvents in many greases.
Solid substances present in ecchymosis (eg motor oil stains
Carbon black inside, clay and coloring in cosmetic stains
The composition may optionally be distributed by 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, namely those of the general formula (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 can contain other ingredients that aid in their cleaning performance. For example, the through-the-wash detergent composition is highly preferred to contain a detergent builder and / or a sequestrant. 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 the like. It is a mixture. Sequestrants include, for example, all of the above, and materials such as ethylenediamine tetraacetate, aminopolyphosphonates and phosphates (DEQUEST) and various other polyfunctional organic acids and salts (too many to be mentioned herein. It is not detailed). See U.S. Pat. No. 3,579,454 for typical examples of the use of such materials in various cleaning compositions. Generally, builders /
The 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 water 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 to aid in grease removal. 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 enzymes (preferably a mixture of amylase and protease) typically work best at pH's above about 7, and 0.001% in this composition.
It is typically used in amounts of ~ 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 contains, in addition to the ingredients already mentioned, various other ingredients typically used in commercial products, where appropriate, to provide aesthetic or additional product performance benefits. be able to. Typical ingredients are, for example, pH adjusting agents, perfumes, dyes, optical brighteners, soil suspending agents, hydrotrope and gel control agents, freeze / thaw stabilizers, bactericides, preservatives, control agents and the like. Such ingredients typically represent 0.1% of the formulation.
Make up ~ 10%.

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

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 Katsuko 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 quaternized substances, the resulting X ⁻
Anions are not important to cleaning performance and are 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 spots, with particular notable benefits in cosmetic and dirty motor oil stains.

It should be understood that the following formulations are in the form of oil-in-water emulsions (where the solvent is believed to be the "oil" phase) and are substantially clear, uniform and stable microemulsions. is there. Surprisingly, the oil-in-water microemulsion of the present invention, when used in a pretreatment process, compares in degreasing performance to water-in-oil emulsions with fairly high concentrations of solvent. The composition also exhibits excellent whiteness retention on cotton cloth, as the solvent obviously reduces the build up of fatty acid soaps on the fabric surface, and the pH of the composition indicates enzyme cleaning performance. These performance advantages are especially significant after multiple cycle washes.

The preparation of stable heavy duty liquid detergents in their preferred oil-in-water microemulsion form pays attention to the use of water carrier liquids, fatty acids / sockets as detergency builders / emulsion stabilizers, and suitable Care is taken to adjust the pH.

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, soap).
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 (sequens), such as palm oil acids,
Palm oil acids and the like can be used. Generally, the concentration of fatty acid (or soken) is 5% to 50%, preferably 5% to
35%, most preferably 10% to 30%, and the weight ratio of fatty acid (or) soap to solvent is generally in the range 4: 1 to 1: 4, preferably 3: 1 to 1: 2. . When using fatty soaps, the potassium and sodium salt forms are preferred, but any convenient water-soluble salt can be used.

Apart from functioning as microemulsion stabilizers, these fatty acid / sequent materials provide important detergency builder functions in the composition. However, about 6.
It has now been discovered that the presence of fatty acids / sequens 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 of 6.5 or above in a microemulsion containing builder amounts of fatty acids / sequens are disclosed in detail below.

Water The liquid compositions of the present invention may be suitably characterized as "water-based" as opposed to organic solvent-based cleaners known in the art.

Surprisingly, water can interfere with the solvent's ability to remove grease-like stains from the fabric. For example, a fabric that has been soiled with motor oil and wet with water prior to treatment with a terpene solvent will not be sufficiently degreased, even if hot.
In contrast, the present composition, in which the solvent is microemulsified in water, is an excellent grease-like stain remover when used directly on dry or wet fabrics.

Aside from the obvious environmental and safety benefits of water versus organic solvents and low cost, water-based heavy duty liquid detergents typically contain ingredients that are water-soluble, such as predominantly water-soluble ingredients. Detergency of builder, disinfectant, chelating agent, soil suspending agent, pH control agent, etc. are given to facilitate formulation.

Thus, the present compositions exhibit 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 art, it is preferred that the detergent composition be used in the range from near neutral to alkaline pH, ie 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 / sockets are destabilized when their "as is" pH is adjusted to above about 6.5. (Instability is recognized
The pH can vary slightly depending on the actual degreasing solvent used in the microemulsion, its amount, and the chain length and degree of unsaturation of the fatty acids. ) This problem is especially acute in the case of substantially non-polar hydrocarbon degreasing solvents such as alkylbenzenes and alpha-olefins, and fluid paraffin solvents.

The problem of stability is a very narrow pH range, roughly 6.5-6.
It appears to be caused by fatty acids of about 2 HLB which are almost completely converted to soaps of about 20 HLB over 9 hours. In this way, since fatty acids are present in a substantial amount (about 5% or more), HL
The major transition of B disrupts the emulsified HLB and results in destabilization.

It should be understood that the stability of the formulation can theoretically be achieved by proper selection of surfactants with low HLB (see 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 object of the present invention is not only to give stable microemulsions, but also a good pretreatment and through-the- It is to give wash washing power.

The microemulsion is stabilized by increasing the ionic strength of the aqueous phase, or by adding a solvent-soluble component of low HLB that increases the solvent polarity to the solvent phase, or by using both means simultaneously. 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, the addition of a slightly polar but solvent-soluble low HLB component, such as n-hexanol, benzyl alcohol, diethyl phthalate, 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 optimum cleaning benefit. For example, formulators have found that 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 a low HLB component that also serves a useful cosolvent cleaning function. N-Hexanol or benzyl alcohol or diethyl phthalate can be selected.

The amount of ionic strength component or low (eg, 2-5) HLB solvent soluble component, or both, used in the composition depends on the desired p
It will depend to some extent on the concentration of H, fatty acids, the amount of degreasing solvent, the composition of the detergent surfactant system, etc. The stability of the microemulsion can be monitored rather easily, since the true microemulsion is transparent, but becomes cloudy and non-uniform and finally phase separates in terms of instability. Moreover, true oil-in-water microemulsions are cloudy when diluted with water, while water-in-oil emulsions tend to gel, and the micellar oil + water system remains clear.

Regarding the pH adjustment of the composition having a pH of about 6.5 to 6.6,
Any of the well known base materials may be used, for example triethanolamine, alkali metal hydroxides and the like.
Potassium hydroxide is preferred over sodium hydroxide because the ease of formulating a stable system is substantially increased by the potassium cation.

Nitrogen Functional Stabilizers / pH Adjusters Various alkylamines and cycloalkylamines, quaternary ammonium compounds and amine oxides are a highly preferred class of pH adjusters and stabilizers in the oil-in-water microemulsion detergent compositions of the present invention. Has now been found to constitute. Obviously, such a substance
Complex that stabilizes the microemulsified oil (solvent) by slightly associating with fatty acid or anionic surfactant (cm)
plex) is generated. Nitrogen-functional compounds do not raise the pH too much towards the alkaline range (only about 4/5 pH units measured "as is" formulated products), but the resulting improvement in cleaning performance is substantially Target.

Dioctyldimethylammonium chloride is a highly preferred quaternary compound for use in the present invention as a pH adjuster, but in order of preference of use, the following quaternary compounds: coconut trimethylammonium chloride. (6.66), di-coconut dimethylammonium chloride (6.84), coconut benzyldimethylammonium chloride (6.84), and dihexyldimethylammonium chloride (6.89) can also be mentioned. The numbers in Katsuko indicate the pH achievable by adding the respective quaternary compound to a liquid oil-in-water microemulsion containing fatty acids and formulated at pH 6.5 "as is". In the case of the preferred dioctyldimethylammonium chloride, the pH figure is 6.94.

Suitable alkylamines and cycloalkylamines (incidental pH) useful in the present invention include, for example, coconut alkyldiethanolamine (6.65), coconut alkyldimethylamine (6.75), trioctylamide (7.0). And cyclohexylamine (7.5).

Suitable amine oxides in the present invention are, for example, coconut alkyldimethylamine oxide (6.7) and dioctylmethylamine oxide (approximate> 7).

It should be understood that the nitrogen compound is added to the composition until the desired pH is obtained. To achieve the indicated pH, 0.5% to 5% of the compound is typically used in the composition. Cyclohexylamine (1-5
%) Is most preferred for use in the present invention.

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

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

For use on hard surfaces as rug cleaners and as general purpose cleaners, such compositions are usually diluted with water.

The following examples illustrate the practice of this invention, but are not intended to be limiting.

Example I The composition of Example I is a stable oil-in-water microemulsion suitable for use as a laundry detergent.

Example II The composition of Example I is modified by using the same amount (9.1% of total formulation) of 1-decene instead of n-octylbenzene. The “as is” product pH is 6.6. The pH is adjusted to 6.94 with dioctyldimethylammonium chloride.

Example III The composition of Example I was prepared by using one of the following solvent mixtures in place of n-octylbenzene (% as specified in Katsuko): 1-decene (6.1%) /
Diethyl phthalate (3.0%), 1-dodecene (7.3
%) / Benzyl alcohol (1.8%), n-octylbenzene (6.2%) / diethyl phthalate (2.9)
%), Octylbenzene (6.0%) / butyl carbitol (3.1%).
The raw product pH is 6.6. Product in each case
pH is 6. Dioctyl dimethyl ammonium chloride.
Adjusted to 9.

Example IV The composition of Example III containing the solvent mixture is adjusted to pH 7.0 with trioctylamine and pH 7.1 with dioctylmethylamine oxide, respectively, and a stable microemulsion is obtained.

As can be seen from the above, the present invention is mono - and di -C ₆ -C ₁₈ tri- and dimethyl ammonium salts; or C ₄ -C ₈ alkyl amine or cycloalkyl amine; or a mono - and di -C ₆ ~ Microemulsions containing large amounts of fatty acids / sequenes using C ₁₈ alkyl dimethylamine oxide and monomethylamine oxide provide an effective means by which the preferred pH range of 6.65 to 7.3 can be adjusted.

Still other examples of the composition are as follows.

Example V The composition of Example I comprises the following alkoxylated polyamine A having the general formula above in place of the ethoxylated polyamine:
Modified by using either B or C.

Polyamine A: x = 2, y = 2, R = ethylene, alkoxy = ethoxy Polyamine B: x = 20, y = 30, R = propylene, alkoxy = propoxy Polyamine C: x = 3, y = 15, R = ethylene , Alkoxy = ethoxy, R ′ = butyl The alkoxylated polyamine contributes to the clay soil removal performance of the present invention.

Example VI The pH of the composition of Example V is adjusted to 7.3 by adding 5 parts of cyclohexylamine (based on the weight of the composition).

Example VII The composition of Example II uses 6% diethyl phthalate / 2% liquid isoparaffin / orange terpene 2 instead of 1-decene.
Corrected by using a mixture of. The product is dioctyl dimethyl ammonium chloride about 2.
It is stable at pH 6.94 when present in an amount of 5%.

Another olefin solvent preferred in the present invention because of its relatively low odor is the so-called "P" available from the numerous petrochemical companies as a raw material for branched alkylbenzenes in the detergent industry.
-4 "polymer. P-4 is an isomer mixture of a condensate of 4 moles of propylene, namely C ₁₂ branched olefin. 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.

Other polar solvents useful in the present invention, for example, "Serosorupu", for example, alkoxylated alkanols, such as 2-butoxyethanol; (including benzyl alcohol) C ₆ -C ₁₂ alkanols such as dodecanol, full energy chill alcohol, and diglycol Ether acetate and the like.

Example VIII Other solvent mixtures useful in the present invention are as follows.

In a preferred use aspect, the composition is used for laundering fabrics, preferably in an aqueous laundry liquor at a liquid pH of 6.5-8.0 (measured as 1% composition in water). Excellent cleaning is achieved by stirring the fabric in a wash liquor, particularly in this preferred in-use pH range.

Example IX 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:

The composition of Example IX is used in an aqueous laundry bath at a concentration of 100 ml / 10 and gives a pH in use of about 7.2 (varies with water hardness).

As can be seen from the above, primary amines are the preferred pH adjusters in the present invention. Generally, C ₄ -C ₁₈ alkyl amines are used because low molecular weight amines tend to be overly malodorous. Other examples of amines useful in the present invention are dibutylamine and diisobutylamine.
For typical use in detergent compositions intended for household use, amines with boiling points above 100 ° C. are preferred.

The pH of the product as it is can be measured using a commercial pH meter at room temperature (23
℃). The electrodes are immersed in the product, and
The pH meter is stabilized before reading.

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Claims (12)

[Claims] 1. A detergent composition in the form of a liquid oil-in-water microemulsion, said oil comprising one or more non-polar or polar degreasing solvents, said composition comprising 10 parts of water.
% -70%, degreasing solvent or solvent mixture 5%-
20%, fatty acid or fatty acid / soap mixture 5% to 3
5%, containing 1% to 40% of detergent surfactant, 6.65
An amine having an alkyl group having at least 4 carbon atoms in an amount sufficient to provide the pH of the above composition (undiluted);
And a component selected from a quaternary ammonium salt having at least 6 carbon atoms or an amine oxide. 2. The amine is selected from alkylamines or cycloalkylamines and has a pH of 6.65.
Composition according to claim 1, which is within the range of 7.5. 3. A composition according to claim 2 wherein the amine is selected from coconut diethanolamine, coconut alkyldimethylamine, trioctylamine, dibutylamine, diisobutylamine and cyclohexylamine. 4. The composition according to claim 1, wherein the quaternary ammonium salt is selected from mono- and di-C ₈ -C ₁₈ tri- and di-methyl ammonium salts. 5. The composition according to claim 4, wherein the quaternary ammonium salt is selected from coconut alkyltrimethylammonium chloride, dicoconut alkyldimethylammonium chloride, dihexyldimethylammonium chloride and dioctyldimethylammonium chloride. object. 6. The amine oxide comprises mono- and di-C ₆
A composition according to claim 1 selected from ~ C ₁₈ alkyldimethyl and monomethylamine oxide. 7. A composition according to claim 6 wherein the amine oxide is selected from coconut alkyl dimethyl amine oxide and dioctyl methyl amine oxide. 8. A detergent surfactant selected from alkylbenzene sulfonates, paraffin sulfonates, alkyl sulphates, ethoxylated alcohols or ethoxylated alkylphenols, or mixtures thereof. The composition according to any one of 1. 9. The solvent is selected from C _{6 to} C ₉ alkylbenzenes, liquid olefins having a boiling point of at least 100 ° C., terpene hydrocarbons, C _{6 to} C ₁₂ alcohols, paraffins, and mixtures thereof. The composition according to any one of items 1 to 8. 10. The solvent is (a) n-octylbenzene, 1-decene, -dodecene, liquid C ₁₀ isoparaffin or terpene, and (b) benzyl alcohol, diethyl phthalate, dibutyl phthalate, or 2- (2 -Butoxyethoxy) ethanol mixture (weight ratio of (a) to (b) 10: 1 to 1: 1)
The composition according to any one of claims 1 to 9, which is selected from 0). 11. The composition according to claim 10, which contains 0.5% to 5% of cyclohexylamine. 12. The composition according to any one of claims 1 to 11, which further comprises a detergent enzyme.