JP2002539322A - Perfume composition and method for masking malodor of amine - Google Patents

Abstract

  (57) [Summary] By incorporating a combination of an anionic surfactant, a solvent and a few selected fragrance compositions, detergent compositions free of malodors due to nitrogen-containing components such as amines, especially hand dishwashing detergents A composition is disclosed. Also disclosed is a perfume composition itself comprising 30% to 100% of an odor neutralizer capable of forming a Schiff base by reacting with an amine. The perfume composition has a pH of 8.5 to 12.

Description

DETAILED DESCRIPTION OF THE INVENTION

TECHNICAL FIELD [0001] The present invention relates to detergents and cleaning compositions, especially liquid- or gel-dishwashing compositions, which can be used appropriately for washing dishes by hand. These detergent compositions include anionic surfactants, solvents and perfume compositions specifically selected to mask the malodors generated by nitrogen compounds such as amines. These components, in the combinations disclosed herein, result in dishwashing detergent compositions having favorable food soil cleaning, handling, and lathering properties, generally without the odors generated by amines. The present invention also relates to the perfume composition itself for masking offensive odors and the method thereof.

BACKGROUND OF THE INVENTION Light (LDL) or gel detergent compositions useful for washing dishes by hand are known to those skilled in the art. Such products are formulated to provide a number of broad performance and aesthetic properties and characteristics. First of all, the liquid or gel-dishwashing products show a satisfactory solubility, different types and different amounts of surfactants and different amounts of surfactants for removing food soils, in particular greasy soils, from the dishes to be washed. It must be formulated with other cleaning aids. Thus, formulators of liquid dishwashing compositions are constantly striving to provide users with improved cleaning benefits by incorporating additional components into LDL detergents.

Diamines are a class of nitrogen compounds that can improve the cleaning performance of liquid dishwashing detergent compositions, especially the cleaning of greasy hydrophobic soils on dishes or other kitchen products. However, diamines can also produce extremely strong malodors, such as the unpleasant odor associated with permanent kits used to curl hair.

[0004] Although nitrogen-containing surfactants and polymers provide convenient detergency and foaming, they often contain amine impurities as by-products in commercial materials. When the composition exceeds the pKa of these aminic impurities, the free amine produced can be offensive. Therefore, it is difficult to formulate a light liquid with a malodor at pH higher than 8.5.

[0005] The malodors generally associated with liquid dishwashing detergents are "hidden" by including a perfume component in the liquid dishwashing detergent which, when used in sufficient quantities, masks the malodors arising from the liquid detergent. Is done. These fragrances also have the added advantage that a desired aroma, such as a lemon scent, can be imparted to the liquid detergent product.

However, some malodors cannot be masked by simply adding perfume to the detergent. For example,
When certain special odors are very volatile (and thus diffuse quickly into the air) and / or when the specific odor is very strong, add enough perfume if the liquid dishwashing detergent does not impart a strong aroma Difficult, in view of the above, there remains a need to formulate a liquid dishwashing detergent that provides a good cleaning effect but does not have the odor associated therewith. Thus, an advantage of the present invention is that a liquid dishwashing detergent incorporating a nitrogen-containing compound (eg, a diamine) is provided that provides excellent detergency but generally does not have the odor associated with the use of these compounds. The present invention also relates to a fragrance composition that can be suitably used in a liquid dishwashing detergent.

The benefits of the present invention are available and included for a wider range of products than current LDL. Such products include nitrogen-containing compounds such as amines, liquid hand soaps, shampoos, aftershaves, colons and personal deodorants where it is desired to mask any malodors they generate,
There are other personal care compositions, hard surface cleaners and various other household and personal care products.

SUMMARY OF THE INVENTION A liquid dishwashing detergent containing a nitrogen compound such as an amine, which has excellent cleaning performance, particularly for oils and hydrophobic soils, and has an odor generated by the nitrogen compound. It has now become evident that liquid dishwashing detergents can be produced which contain certain odoriferous substances and / or odor neutralizers, which mask particularly effectively.

[0009] The detergent composition according to the first aspect of the present invention comprises: (a) an anionic surfactant; (b) a solvent; (c) an amine having a pKa greater than 8.0; A fragrance composition comprising about 30% to about 100% of an odor neutralizer that can react with an amine to form a Schiff base. The pH (measured as a 10% aqueous solution) of the detergent composition is about 8.
5 to about 12, and in a preferred embodiment, the molar ratio of the anionic surfactant to the amphoteric surfactant present to the diamine present is about 100:
40: 1 to about 9: 0.5: 1.

According to a second aspect of the present invention, detergent compositions which can be suitably used for hand washing dishes include: (a) from about 0.1 to about 5% by weight of a diamine having a molecular weight of less than 400 g / mol. (B) about 5 to about 50% by weight of an anionic surfactant; (c) about 0.5 to about 10% by weight of an amphoteric surfactant; (d) about 0.1 to about 10.0 of a buffer.
(E) about 0.1 to about 1.5% by weight of the alkali metal inorganic salt; (f) about 0.75 to about 25.0% by weight of the solvent. The detergent composition also includes: (g) about 30% to about 100% of an odor neutralizer that can react with the diamine to form a Schiff base.
Perfume compositions comprising, from about 0.01 to about 0.5% by weight. The pH (measured as a 10% aqueous solution) is from about 10.0 to about 12.0, and the molar ratio of the anionic surfactant to the amphoteric surfactant to the diamine is from about 27: 8: 1 to about 11: 3:
Up to 1.

The present invention also separately relates to a fragrance composition that properly masks diamine odor. The perfume composition comprises an organic substance selected from the group consisting of aromatic substances having a boiling point of 180 ° C. or lower, or neutralizing agents capable of reacting with amines and mixtures thereof to form Schiff bases.

All parts, percentages and ratios used herein are expressed as weight percent unless otherwise specified. All references mentioned herein are incorporated by reference in the relevant part of this specification.

DETAILED DESCRIPTION OF THE INVENTION Definitions- The detergent compositions of the present invention include an "effective amount" or an "oil removal improving amount" of the individual components as defined herein. "Effective amounts" of the diamines and auxiliary components herein
By means an amount sufficient to improve the performance of the cleaning composition of the present invention against at least some target soils, directionally or significantly, with a 90% confidence limit. For example, in compositions intended for certain oily soils, the formulator will use sufficient diamine to at least directionally improve the cleaning performance on such soils.

“Light liquid (LDL) detergent composition” means a detergent composition used for dishwashing by hand (ie, hand washing dishes). "Kitchen utensils" means cooking utensils, flat household utensils, dishes and dishes, silverware and other products commonly found in the kitchen and used for cooking, eating and drinking food, and meals or other foods. Means the product used to wash at the end of cooking. "Nitrogen compound" means a compound that contains nitrogen and relates to ammonia or ammonium. Such compounds are amines, polyamines, amine oxide surfactants, amides, and hydrophilic polar groups neutralized by ammonium cations, alkanolamine solvents (eg, monoethanolamine, diethanolamine, and triethanolamine). Surfactants, and other similar compounds commonly used in detergents or cleaning compositions. "Odor" means a detectable odor due to amines or other nitrogen compounds related to ammonia or ammonium. "Amine" means an ammonia or ammonium derivative in which one or more of the hydrogen atoms has been replaced by an alkyl, cyclic hydrocarbon, fatty alkyl, or aromatic group. By "scent" is meant a detectable odor associated with or derived from a fragrance. "Volatile" means the tendency of a liquid material to transition to a vapor phase at a given temperature. "Ethylene oxide group" means the following structure:

[0015]

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“Propylene oxide group” means the following structure

[0017]

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The present invention has been chosen to mask the odors generated by a wide range of nitrogen compounds,
It is directed to detergent and cleansing compositions, including formulated perfume compositions, especially liquid dishwashing detergent compositions. These nitrogen compounds may be added deliberately to provide some performance benefits to the detergent or detersive composition, or may be included in surfactant additives (especially amine oxides, betaines and polyhydroxy fatty acid amide surfactants). Medium) and as an impurity in amine-containing polymers.

Fragrance compositions designed to mask these nitrogenous malodors include fragrances and odor neutralizers. These are shown in more detail below. The detergent composition of the present invention comprises from about 0.01 to about 0.5% by weight, more preferably from about 0.02 to about 0.5%.
2%, most preferably from about 0.03 to about 0.08% by weight of the perfume composition.

(A) Fragrance The fragrance composition of the present invention comprises a fragrance which can mask the presence of malodors emanating from amines and thus eliminate amine odors from liquid dishwashing detergents. These fragrances mask the amine odor by providing odors that compete with malodors for access to the nasal receptor sites.

Under typical conditions of use, the malodor associated with dishwashing amines and other such nitrogen-containing components is such that the detergent is exposed to air (eg, opening the bottle and then placing the product on the surface of the dish). Released from the dishwashing product as soon as it is applied or further diluted with water). Generally, such malodors accumulate in the headspace of the container at various times between and when the consumer uses the detergent. The odor diffuses into the ambient air as soon as it exits the detergent container and travels to nasal receptor sites, resulting in an unpleasant olfactory signal that is easily associated with the product by consumers.

Without being limited by theory, the ability of the fragrance material contained in the perfume composition of the present invention to mask malodors is related to both of the following: 1) The odor emitted from the fragrance material is in the air. The length of time required to diffuse and thus travel from the container of the detergent composition to the nasal receptor site; and 2) the relative intensity of the odor or odor.

The rate at which a fragrance diffuses into the air and thus escapes from the detergent composition is also related to the hydrophobicity of the fragrance. This is described in more detail below. Thus, the fragrance material constituting the fragrance composition of the present invention is selected based on three criteria: volatility, hydrophobicity and strength.

I) Volatile An essential component of the fragrance composition of the present invention is a highly volatile fragrance. Highly volatile fragrances have a lower boiling point than other substances, so that odors from these substances quickly diffuse into the air, compete with foul odors, bind to nasal receptor sites, and are perceived by the brain It will be the first smell to be recognized. Since the odor from highly volatile fragrances is more volatile and reaches the nasal receptor site before the amine odor, the nasal receptor site is already occupied when the amine odor finally reaches. Thus, the perception of the odor of the amine is effectively masked.

The perfume composition of the present invention comprises from about 0.10% to about 4% of a highly volatile fragrance,
Preferably from about 0.15% to about 2.5%, most preferably from about 0.20% to about 2.0%. Highly volatile fragrances have a boiling point of less than 180 ° C at 1 atmosphere, preferably less than 160 ° C, and most preferably less than about 140 ° C.

[0026] Most low molecular weight aldehydes, ketones and esters have relatively high boiling points and are examples of highly volatile fragrances that can be suitably used in the present invention. Non-limiting examples of suitable highly volatile fragrances, and their respective boiling points at 1 atmosphere, are described below:

Aroma substance boiling point (° C.) Methyl acetoacetate 172 Cyclohexyl alcohol 161 3-Methyl-1-pentanol 151 1,3-Dimethylbutyl acetate 148 Isopropyl 2-methylbutyrate 138 Ethyl-2-methylbutyrate 131

It is also preferred that the fragrance composition of the present invention comprises a volatile fragrance. The volatile fragrances used in the present invention are more volatile than the highly volatile fragrances, from about 180 ° C. to about 260 ° C. at one atmosphere, more preferably from about 185 ° C. to about 240 ° C., and most preferably from about 185 ° C. to about 240 ° C. It has a boiling point from 190 ° C to about 220 ° C. The fragrance composition of the present invention can include from about 30% to about 50%, preferably from about 35% to about 50%, and most preferably from about 40% to about 45%, volatile fragrance.

The fragrance composition of the present invention more effectively masks the malodor of amines and other malodors generated from nitrogen compounds. As summarized above, the fragrance composition of the present invention comprises a highly volatile fragrance material that reaches the nasal receptor site prior to malodor, thereby effectively masking the malodor and thereby enhancing the perfume composition. Effectively masks these odors. However, after sufficient time, and after the malodor has physically approached the nasal receptor site, odors already present at that site may have decomposed or migrated there;
The odor is thus given the opportunity to bind to the site, whereby the odor may be perceived by the consumer. This is especially true when relatively high concentrations of one or more offensive odors are more intense than the odor of highly volatile fragrances.

To avoid this, it is preferred that the perfume composition include a fragrance composition that is not as volatile as a highly volatile fragrance. The odor emanating from these fragrances arrives at the same time as, or shortly after, the odor, and as the odor generated by the highly volatile fragrance decomposes or moves away from the nasal receptor sites, empties the site with the odor.

The following are non-limiting examples of suitable volatile fragrances, and their respective boiling points at 1 atmosphere:

Aroma substance boiling point (° C.) 3,7-dimethyl-1,6-octadien-3-ol 198 3,7-dimethyl-7-hydroxyoctane-1-al 241 n-decyl aldehyde 215 benzaldehyde 179 anisaldehyde 248 Benzyl acetate 215 Allyl hexanoate 185 Methyl-2-aminobenzoate 237 2-cis-3,7-Dimethyl-2,6-octadien-1-ol 227 3,7-Dimethyl-trans-2,6-octadien-1- All 230 3,7-dimethyl-6-octen-1-ol 225 2,6-dimethyl-7-octen-2-ol 208 2-phenylethyl alcohol 220 1-methyl-4-isopropyl-1-cyclohexene-8- All 219 1-1-methyl 4-isopropenyl-6-cyclohexen-2-one 231
Para-tert-amyl cyclohexanone 211 cyclohexanyl 2-tert-butyl acetate 241 benzyl acetate 211

The boiling points of many perfume substances are described, for example, in S. Arctander, “Perfume and Flavor Chemicals (Aroma Chemicals)”.
Chemicals)) ", published 1969. This is incorporated herein by reference. Other boiling points are described in various chemical handbooks and databases, such as the Beilstein Handbook, Lang's Chemical Handbook, and CR.
It can be known from C Chemistry and Physics Handbook. When the boiling points at different pressures, usually below one standard atmosphere, are given, the boiling point at normal or ambient pressure is the boiling point-pressure monograph, such as AJ Gordon & Ford (
RAFord, "Chemist's Companion", John
Approximately predicted by use of those described in Willie & Sons Publishing, 1972, pp. 30-36. If available, boiling points can also be calculated by computer programs based on molecular structure data. For example, Stanton (D.
T. Stanton et al., “Computer Assisted Prediction of Normal Boiling Points of Pyrans and Pyroles.
Rroles) ", J. Chem. Inf. Comput. Sci. 32 (1992), pp. 306-316, Stanton et al.," Computer-Assisted Prediction of Normal Boiling Points of Furans, Tetrahydrofurans, and Thiophenes. "
ng Points of Furans, Tetrahydrofurans, and Thiophenes) ”, J. Chem. Inf. Com.
put. Sci. 31 (1992), pp. 301-310, and references described therein, and "Estimation of Physical Properties from Molecular Structure" by R. Murugan et al., Chemtec, June 1994, 17- 23 pages. All of which are incorporated herein by reference.

Ii) Hydrophobicity Another important parameter of the fragrance used in the present invention is the hydrophobicity. The liquid detergent compositions of the present invention are significantly diluted and can be formulated to contain as much as 80% water. This product therefore tends to concentrate during storage on the interface between the liquid detergent composition and the air in the headspace of the detergent container (e.g., squeeze bottle). Exists). As the consumer uses the product, the more hydrophobic fragrances are located at the liquid detergent-air interface, and thus tend to evaporate into the air, providing a pleasant fragrance signal.

The degree of hydrophobicity of an aroma substance is correlated with its octanol / water partition coefficient (“P”). The octanol / water partition coefficient of a fragrance is the ratio of the equilibrium concentrations of the fragrance in octanol and in water. Aroma substances having a higher partition coefficient P are more hydrophobic. Conversely, fragrances having a smaller distribution coefficient P are more hydrophilic. Preferred fragrances of the present invention have an octanol / water partition coefficient of 1000 or greater. Since the distribution coefficients of aromatic substances usually show high values, it is convenient to express them in the form of logarithm with a base of 10, log P. The fragrance composition of the present invention comprises about 2 aromatic substances having a ClogP value of greater than 2.5.
0% to about 70%, more preferably about 30% to about 60%, and most preferably about 40% to about 55%.

[0036] The log P of a number of perfume ingredients has been reported; for example, Daylight Chemical.
The Pomona 92 database, available from Information Systems, Inc. (Daylog CIS) (Irvine, Calif.), Contains many with articles on the original literature. However, logP values are most conveniently calculated by the "CLOGP" program, also available from Daylight CIS. This program is
Experimental logP values are also listed when in the Pomona 92 database. "Calculated logP" (ClogP) is determined by the Hansh and Leo fragment method (see: A. Leo, Comp.
rehensive Medical Chemistry, 4 volumes, C. Hansh, Samens (PGSa)
mmens), Taylor (JBTaylor) and Ramsden (CARamsden), 295
Page, Pergamon Publishing, 1990. These are incorporated herein by reference. ) The fragmentation method takes into account the number and type of atoms, the connectivity of the atoms, and the chemical bonds based on the chemical structure of each aroma component. The ClogP value, which is the most reliable and widely used estimate of this physicochemical property, is used in place of the experimental logP value to select perfume ingredients useful in the present invention.

[0037] Non-limiting examples of suitable fragrances and their respective ClogP values include:

Aroma substances ClogP benzyl acetate 2.0 ethyl-2-methylbutyrate 2.2 furfuryl valeate 2.7 isobutyl benzylcarbinol 2.9 para-ethyl-alpha, alpha-dimethylhydro-cinnamaldehyde 3.4 isobutyl Caproate 3.8 4-tert-butylcyclohexyl acetate 4.1

Iii) Intensity Intensity refers to the perceived intensity of a fragrance substance versus the amount of fragrance required to achieve that intensity. All fragrances have unique psychophysical properties (they are not all of equal strength), but in general fragrances with a low boiling point are more potent than fragrances with a high boiling point, and the strength of certain substances Is suggested to be related to the rate at which it evaporates and diffuses into the air to produce a perceivable odor.

Preferably, at least one of the aroma substances used in the present invention has a low odor detection threshold. As used in the present invention, a low-odor threshold odorant, when dissolved in an aqueous substrate, has an odor detection threshold of less than 4.0 mg / L, more preferably less than 1.0, more preferably 0.10 mg. / L less than / L. The perfume compositions of the present invention can include less than about 20%, more preferably less than about 8%, and most preferably less than about 0.08% of a fragrance having a low-odor threshold.

The following are non-limiting examples of suitable strong fragrances and the odor-detection thresholds of each of the fragrances when they are dissolved in a water substrate:

Perfume substance odor-detection-threshold ethyl-2-methylbutyrate 1 × 10 ^-4 ethyl acrylate 0.067 dichloroacetic acid 0.232 hexanoic acid 3.000 4-tert-butylcyclohexyl acetate 3.500

[0043] Odor detection thresholds for fragrances are well known and available, for example, "Compilation of Odoe and Taste Threshold Values Dat.
a) ", edited by FAFazzalari, American Society for Testing and Materials (American S
Society for Testing and Materials), 1978.

Measurement of Odor Detection Threshold To measure the odor detection threshold, measure the hydrocarbon reaction using a hydrocarbon standard with a precise amount of substance injected with a syringe, a fine split ratio, and a known concentration and chain length distribution. Gas chromatography was characterized as follows. Accurately measure airflow,
The sample volume is calculated assuming a human inhalation duration of 0.2 minutes. At any point in time, the exact concentration of the detector is known, so the mass per inhaled dose is known, and therefore the substance concentration. The solution is supplied to the sniff-port at a back-calculated concentration to determine if the threshold for a substance is below 4 mg / L. A panelist sniffs the GC effluent and determines the residence time at which the odor is felt.
The detectable threshold is determined from the average of all panelists.

The required amount of fragrance is injected into the column so as to give a concentration of 4 mg / L at the detector. Typical gas chromatographic parameters for measuring the odor detection threshold are listed below.

GC: 5890 Series II 7673 Autosampler with FID Detector Column: J & W Scientific DB-1 30 meters long 0.25 mm inner diameter 1 micron film thickness Method: split injection: 17/1 split ratio auto Sampler: 1.13 microliters per injection Column flow rate: 1.10 mL / min Air flow rate: 345 mL / min Inlet temperature: 245 ° C Detector temperature: 285 ° C Temperature information Initial temperature: 50 ° C Speed: 5 C / min Final temperature: 280 ° C. Final time: 6 minutes Key assumptions: a) Single sniff time is 0.02 minutes b) GC air adds to sample dilution. To determine if the threshold of a substance is less than 1.0 mg / L or less than 0.1 mg / L, a sufficient amount of fragrance is injected into the column and 1.0 mg / L or 0.1 at the detector.
A mg / L concentration is obtained.

B) Odor neutralizer The manner of action of the odor neutralizer is different from the above-mentioned aroma substances. They do not mask the odor by blocking the odor from approaching the nasal receptor site, but mask the odor by reducing the amount of amines that generate the odor. Chemicals that give products that produce little or no noticeable malodor on reaction with amines are suitable as odor neutralizers. Preferred classes of odor neutralizers are aldehydes; the Schiff reaction reacts the aldehyde with an amine to form a Schiff base and water:

[0048]

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In the above reaction, R ^a and R ^b are both aliphatic substituents. In the present invention, the amine may be a diamine contained to be suitable for stubborn hydrophobic and greasy dirt cleaning. See the description for the diamine below. The Schiff base produces little or no malodor, so that the reaction of the aldehyde with the amine reduces the amount of malodorous amines present. Specific aldehydes that can be suitably used in the present invention include: para-tert-butyl-alpha-methyl hydrocinnamaldehyde, 4- (4-methyl-4-hydroxyamyl) -3-cyclohexane-1-. Carboxaldehyde, 4- (4-hydroxy-4-methylpentyl), hydroxycitronellal, alpha-methyl-beta-3,4-methylenedioxy-phenylpropionaldehyde and most aldehydes. Many odor neutralizers, such as some aldehydes, characteristically generate odor and also serve as fragrances in the present invention. About 30% of the fragrance composition of the present invention
To about 100%, preferably about 45% to about 65%, most preferably about 50%.
% To about 80% consists of odor neutralizers that can form Schiff bases when reacted with aldehydes.

Diamines -As noted above, the detergent compositions of the present invention employ a diamine in combination with a detergent surfactant at a level that can at least directionally improve cleaning performance. Within the scope of dishwashing compositions, such "use levels" depend not only on the type and degree of soiling, but also on the temperature of the wash water, the amount of wash water and the length of time the dishes have been in contact with the wash water. .

Because of the considerable differences in the habits and practices of the user of the detergent composition, the composition may be at least about 0.1% by weight of the composition, more preferably at least about 0.2%, and More preferably, it comprises at least about 0.25%, even more preferably at least about 0.5%, of the diamine. Also, the composition may comprise at most about 15% of the composition by weight.
, More preferably at most about 10%, even more preferably at most about 6%, even more preferably at most about 5%, and even more preferably at most about 1.5%.
It is preferable to include a diamine of

In one of some aspects of the present invention, the present invention provides a means to enhance the removal of greasy / oily soils by combining the special diamines of the present invention with a surfactant. Oily / oily “daily” stains include triglycerides, lipids,
It is a mixture of complex polysaccharides, fatty acids, inorganic salts and proteinaceous substances.

The diamines thus have the advantage, in combination with amphoteric and anionic surfactants in the specific proportions described below, of improving the cleaning effect of fats and oils and stubborn foods, so that the compositions according to the invention In the preferred embodiment of the present invention, divalent ions can be eliminated or the amount thereof can be reduced. The improvement in the washing effect is due to the fact that the diamine has a property as a buffer which enhances the alkalinity of the dishwashing composition. Because of the improved dissolution rate due to the removal of divalent ions, the prescriber can achieve significantly higher viscosities (eg, 1,000 centipoise) than conventional formulations while maintaining excellent dissolution and cleaning performance.
It is possible to prepare dishwashing detergents, especially compact detergents.
This is an important and possible advantage for producing compact products with higher viscosities while maintaining satisfactory dissolution. "Compact" or "Ultra" means a detergent composition that has a lower amount of water as compared to conventional liquid detergents.
In "compact" or "ultra" compositions, the amount of water is less than 50%, preferably less than 30%, by weight of the liquid dishwashing detergent composition. The above-mentioned concentrated product offers the advantage of low consumption for the consumer and the advantage of low transportation costs for the producer. For a non-concentrated composition, a suitable water level is less than about 85%, more preferably less than about 70%, by weight of the liquid dishwashing detergent composition.

The diamines used in the present invention preferably contain substantially no impurities. That is, “substantially free” means that the diamines are 95% or more pure.
That is, preferably 97%, more preferably 99%, even more preferably 99%.
It means 0.5% pure (no impurities present). Examples of impurities that may be present in commercially supplied diamines are 2-methyl-1,3-diaminobutane and alkylhydropyrimidine. Further, it is believed that the diamines must not contain oxidizing reactants to avoid diamine decomposition and ammonia formation.

It is important that the liquid dishwashing detergent composition of the present invention contain as little hydrogen peroxide as possible. This is because the nitrogen compounds generated by the reaction of the diamine and the peroxide are believed to produce a foul odor traditionally associated with diamine-containing products. Therefore, it is preferable to minimize the amount of hydrogen peroxide present as an impurity in the composition of the present invention by using a component substantially free of hydrogen peroxide.

Preferred organic diamines have a pK 1 and pK 2 in the range of about 8.0 to about 11.5, preferably in the range of about 8.4 to about 11, and more preferably in the range of about 8.6 to about 1.
It is in the range of 0.75. A preferred material in consideration of performance and supply is 1,3-bis (methylamine) -cyclohexane (pKa = 10 to 10.5).
), 1,3-propanediamine (pK1 = 10.5; pK2 = 8.8), 1,6
Hexane diamine (pK1 = 11; pK2 = 10), 1,3-pentanediamine (Ditek EP) (pK1 = 10.5; pK2 = 8.9), 2-methyl-1,5-pentanediamine (Ditek A) ( pK1 = 11.2; pK2 = 10.0). Other preferred materials are primary / primary diamines having alkylene spacers ranging from C4 to C8. It is generally believed that primary diamines are preferred over secondary and tertiary diamines.

Definitions of pK1 and pK2—As used herein, “pK1” and “pK2” are quantities of a type known collectively to the skilled artisan as “pKa”. In the present invention, pKa is used as generally known to those skilled in the chemical field. The figures cited herein are obtained from Smith and Martel, Critical Stability Constants: Volume 2, Amines, Plenum Publishing, NY and London, 1975. Additional information on pKa can be obtained from affiliated sources, such as information from DuPont, a diamine supplier.

As used herein, the pKa of a diamine is defined as an aqueous solution at 25 ° C. with an ionic strength of 0.1 to 0.5M. pKa is an equilibrium constant that can vary with temperature and ionic strength; therefore, the values reported in the literature may not be consistent depending on the measurement method and conditions. To eliminate ambiguity, the relevant conditions and / or standards used for pKa's of the present invention are described herein or in "Critical Stable Constant: 2
One of the typical methods is potentiometric titration of acids with sodium hydroxide, and a brief reference for chemists by Shugar and Dean. In the Chemist's Ready Reference Handbook, McGraw-Hill, NY, 1990.

Substituents and structural changes that reduce pK1 and pK2 to less than about 8.0 are undesirable,
It has been shown that performance degradation occurs. These are ethoxylated diamines,
Hydroxyethyl-substituted diamines, diamines having oxygen at the beta (even to a lesser extent, gamma) position relative to the nitrogen of the spacer group (eg, Jaffamine ED
R148). In addition, materials based on ethylenediamine are unsuitable.

The diamines useful in the present invention can be defined by the following structure:

[0061]

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In the above formula, R _2-5 is independently selected from H, methyl, —CH ₃ CH ₂ and ethylene oxide; C _x and _Cy are independently selected from a methylene group or a branched alkyl group. . Where x + y is from about 3 to about 6; A is optionally present and is selected from electron donating or electron withdrawing moieties selected to adjust the pKa's of the diamine to the desired range. If A is present, x and y must both be greater than or equal to one.

Examples of preferred diamines are described in P & G Case No. 7167P, filed Jun. 2, 1998, Application No. 60 / 087,693, “Improved Fats and Oils” by Phillip Kyle Vinson et al. Dishwashing detergent compositions containing organic diamines for washing, bubbling, low temperature stability and dissolution can be found in a co-pending provisional patent application. This is incorporated herein by reference.

Anionic surfactants-Anionic surfactants useful in the present invention are preferably linear alkyl benzene sulfonates, alpha olefin sulfonates, paraffin sulfonates, alkyl ester sulfonates, alkyl sulfates, alkyl alkoxy sulfates, alkyl sulfonates, It is selected from the group consisting of alkylalkoxycarboxylates, alkylalkoxylated sulfates, sarcosinates, taurinates, and mixtures thereof. An effective amount, typically from about 0.5% to about 90%, preferably from about 5% to about 50%, by weight;
More preferably, about 10 to about 30% of an anionic detergent surfactant can be used in the present invention.

A suitable example of an anionic surfactant is Chandrika K.
asturi et al., in co-pending provisional patent application entitled "Liquid Detergent Compositions Containing Polymerizable Foaming Agents" (P & G Case No. 6938P, Application No. 60 / 066,344, filed November 21, 1997). This is incorporated herein by reference. Other examples of suitable anionic surfactants are "surfactants and detergents" (I and I
I, Schwartz, Perry and Berch). A variety of such surfactants are disclosed in U.S. Patent No. 3,929,678, issued December 30, 1975 to Laughlin et al., Column 23, lines 58-29.
It is also generally disclosed in line 23. Suitable anionic surfactants are also available in 1995
It is also found in Ofos-Asante et al., U.S. Pat. No. 5,415,814, issued May 16, 2016. All of which are incorporated herein by reference.

Amphoteric Surfactants-Amphoteric surfactants useful in the present invention are preferably selected from amine oxide surfactants. Amine oxides are semi-polar surfactants,
Water-soluble amine oxides containing one alkyl moiety of about 10 to about 18 carbon atoms and two moieties selected from the group consisting of alkyl and hydroxyalkyl groups containing about 1 to 3 carbon atoms; Water-soluble phosphine oxides comprising from about 1 to about 18 1 alkyl moieties and 2 moieties selected from the group consisting of alkyl and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms; and from about 10 to about 10 carbon atoms. There are water-soluble sulfoxides containing 18 1-alkyl moieties and moieties selected from the group consisting of alkyl and hydroxyalkyl moieties of about 1 to about 3 carbon atoms.

The semipolar detergent surfactant includes an amine oxide surfactant represented by the following formula:

[0068]

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Wherein R ³ is an alkyl, hydroxyalkyl, or alkylphenyl group containing from about 8 to about 22 carbon atoms, or a mixture thereof; R ⁴ contains from about 2 to about 3 carbon atoms X is 0 to about 3; each R ⁵ is an alkyl or hydroxyalkyl group containing from about 1 to about 3 carbon atoms, or an ethylene oxide group of from about 1 to about 3; Is a poly (ethylene oxide) group. The radicals R ⁵ may be for example binding to each other by an oxygen or nitrogen atom, to form a ring structure. These amine oxide surfactants in particular there is a C ₁₀ -C ₁₈ alkyl dimethyl amine oxides and C ₈ -C ₁₂ alkoxy ethyl dihydroxy ethyl amine oxides.

Other amphoteric surfactants are available from Joanna M. Clarle,
Co-pending Provisional Patent Application entitled "Diols and Polymerized Glycols for Improved Dishwashing Detergent Compositions" (P & G Case No. 7408P, Application No. 60 / 119,04).
4). This is incorporated herein by reference. In order to be particularly suitable for use in the present invention because of its low foaming properties, it is desirable to use long chain amine oxide surfactants. This is disclosed in U.S. Pat.
No. 316,824 (Pancelli), Nos. 5,075,501 and 5,071,591
No. 4 is described in more detail.

Preferably, the amphoteric surfactant is present in the composition in an effective amount, more preferably from about 0.1% to about 20%, more preferably from about 0.1% to about 15%, even more preferably from about 0.1% to about 15%. It is present from 0.5% to about 10%.

Second Detergent-The second detersive surfactant is selected from the group consisting of nonionic surfactants, cationic surfactants, amphoteric electrolytes, zwitterionic surfactants, and mixtures thereof. it can. Formulating the detersive composition of the present invention by selecting the type and amount of detersive surfactant with other auxiliary components disclosed herein,
It can be used for cleaning laundry or for other different cleaning applications, especially dishwashing. As such, the particular surfactant used can vary widely depending on the particular end use envisioned. Suitable second surfactants are described in the above-mentioned copending interim patent application entitled "Liquid Detergent Compositions Containing Polymerizable Foaming Agents" (P & G Case No. 6938P, Application No. 60/066, cited above). 344
).

Ratio of Anionic Surfactant to Amphoteric Surfactant to Diamine In the compositions of the present invention, the ratio of anionic surfactant: amphoteric surfactant: diamine may be from about 100: 40: 1 to about 100 moles. 9: 0.5: 1 and the molar ratio of anionic surfactant: amphoteric surfactant: diamine is from about 27: 8: 1 to about 11
: 3: 1 is preferred. Detergent compositions comprising anionic surfactants, amphoteric surfactants and diamines at this particular ratio provide improved low temperature stability,
It has been found that less than H12.5 gives better grease removal performance and a strong food cleaning effect, and improves hard water cleaning.

In another aspect of the present invention, when the molar ratio of anionic surfactant to diamine is greater than 9: 1, more preferably greater than 20: 1, low temperature stability is improved and better grease removal. And a strong food cleaning effect was obtained, and it was found that hard water cleaning was improved.

Solvents- Various water-miscible liquids such as lower alkanols, diols, polyols, ethers, amines, and polymerized glycols containing ethylene oxide (EO) and propylene oxide (PO) groups are included in the present invention. Can be used. Particularly preferred are C1 -C4 alkanols, diols and the above-mentioned polymerized glycols.

When present, the composition preferably comprises at least about 0.01%, more preferably at least about 0.5%, and even more preferably at least about 1%, by weight of the composition, of a solvent. Also, the composition comprises at most about 20%, more preferably at most about 10%, and even more preferably at most about 8% of the solvent by weight of the composition.

These solvents can be used in combination with an aqueous liquid carrier such as water, or can be used without an aqueous liquid carrier. Solvents are broadly defined as compounds that are liquid at temperatures between 20 ° C and 25 ° C and are not considered surfactants. One distinguishing feature is that solvents tend to exist as separate entities, rather than as a broad mixture of compounds. Examples of suitable solvents in the present invention include ethanol, propanol, propylene glycol, polypropylene glycol and isopropanol, 2-methylpyrrolidinone, benzyl alcohol and morpholine n-oxide. Preferred solvents among these are ethanol and isopropanol.

The diols which can be suitably used here are represented by the following formula:

[0079]

Embedded image

Wherein n = 0-3, R ₇ ＨH, methyl or ethyl; and R ₈ is H, methyl, ethyl, propyl, isopropyl, butyl and isobutyl. Preferred diols include propylene glycol, 1,2-hexanediol, 2-ethyl-1,3-hexanediol, and 2,2,4-trimethyl-1,3-pentanediol. When a diol is present, the compositions of the present invention comprise at least about 0.5%, more preferably at least about 1%, and even more preferably at least about 3%, by weight of the above composition of a diol. Also, the composition preferably comprises at most about 20%, more preferably at most about 10%, and even more preferably at most about 6% of the diol by weight of the composition.

Polymerized glycols can also be suitably used in the present invention. Preferred polymerized glycols have an average molecular weight of about 1000 to about 5000, more preferably about 2000 to about 400.
Polypropylene glycol having 0, most preferably from about 2000 to about 3000. Other examples of suitable polymerized glycols, as well as their acceptable concentrations for use in LDL compositions, can be found in Joanna M. Clarle's "
Co-pending Provisional Patent Application entitled "Diols and Polymerized Glycols for Improved Dishwashing Detergent Compositions" (P & G Case No. 7408P, Application No. 60 / 119,04).
4). This is incorporated herein by reference as it is.

Solvents that can be suitably used in the present invention also include ethers and diethers having 4 to 14, preferably 6 to 12, and more preferably about 8 to 10 carbon atoms. Other suitable solvents are glycols or alkoxylated glycols, alkoxylated aromatic alcohols, aromatic alcohols,
Aliphatic branched-chain alcohols, alkoxylated aliphatic branched-chain alcohols, alkoxylated linear C1-C5 alcohols, linear C1-C5 alcohols, C8-C14 alkyl and cycloalkyl hydrocarbons and halohydrocarbons, C6-C16 glycol Ethers and mixtures thereof.

In addition to propylene glycol, polypropylene glycol and the above diols, they are represented by the formula HO—CR 1 R 2 —OH, wherein R 1 and R 2 are independently H or C 2 -C 10 saturated or unsaturated aliphatic hydrocarbon chains. Other and / or cyclic glycols are also suitable and can be used in the present invention. One such suitable glycol is dodecane glycol.

Suitable alkoxylated glycols that can be used in the present invention are represented by the following formula: R- (A) _n -R ¹ -OH wherein R is H, OH, 1 to 20 carbon atoms, preferably Is a straight, saturated or unsaturated alkyl having 2 to 15, more preferably 2 to 10, wherein R ¹ is H or 1 to 20, preferably 2 to 15, more preferably 2 to 10 straight-chain saturated or unsaturated alkyl, A is an alkoxy group, preferably ethoxy, methoxy and / or propoxy;
n is 1 to 5, preferably 1 or 2. Suitable alkoxylated glycols for use in the present invention are methoxyoctadecanol and / or ethoxyethoxyethanol.

Suitable aromatic alcohols which can be used here are represented by the formula R—OH, where R is an alkyl of 1 to 20, preferably 1 to 15, more preferably 1 to 10 carbon atoms. It is a substituted or unalkyl-substituted aryl group.
For example, a suitable aromatic alcohol used herein is benzyl alcohol.

The present invention can also include alkanolamine solvents (eg, monoethanolamine, diethanolamine, and triethanolamine); this is also included in the present invention as an antioxidant.

[0087] Suitable aliphatic branched alcohols for use in the present invention are represented by the formula R-OH, wherein R is 1-20, preferably 2-15, more preferably 5-12 carbon atoms. Is a branched saturated or unsaturated alkyl group. Particularly suitable aliphatic branched alcohols for use in the present invention include 2-ethylbutanol and / or 2-methylbutanol.

The alkoxylated aliphatic branched alcohol which can be suitably used in the present invention has the formula R (A
) Represented by _n- OH. Where R is 1 to 20 carbon atoms, preferably 2
To 15, more preferably 5 to 12 branched-chain saturated or unsaturated alkyl groups, wherein A is an alkoxy group, preferably butoxy, propoxy and / or
Or ethoxy, and n is an integer from 1 to 5, preferably 1 or 2. Suitable alkoxylated aliphatic branched alcohols include 1-methylpropoxyethanol and / or 2-methylbutoxyethanol.

Suitable straight chain C 1 -C 5 alcohols which can be used in the present invention are those represented by the formula R—OH, wherein R is a straight chain saturated group having 1 to 5, preferably 2 to 4 carbon atoms. Or an unsaturated alkyl group. Suitable C ₁ -C ₅ alcohols are methanol, ethanol, propanol or mixtures thereof.

Other suitable solvents for use herein are co-pending provisional patent applications (P & G) entitled “Liquid Detergent Compositions Containing Polymerizable Foam Enhancers” by Chandrica Kasturi et al.
Case No. 6938P, No. 60 / 066,344, filed Nov. 21, 1997). This is incorporated herein by reference.

Buffer- The dishwashing composition of the present invention, when used, ie, applied to diluted soiled utensils, is exposed to the acidic stresses caused by food soil.
Preferably, the compositions of the present invention have a pH of at least about 8.5, preferably at least about 10, more preferably at least about 10.5;
Preferably, it has a pH of up to about 11.5, more preferably up to about 10.9. Since the detergent compositions of the present invention are broadly alkaline, the detergent compositions include a buffer that can bring the composition and its dilute solution to a generally more alkaline pH.
For example, the dishwashing compositions of the present invention comprise from about 0.5% to about 15%, preferably from about 1% to 12%, most preferably from about 2% to about 10% by weight of a buffer. The pKa value of this buffer should be about 0.5 to 1.0 units lower than the desired pH value of the composition (as measured above). Preferably, the pKa of the buffer is from about 7 to about 12. Under these conditions, the buffer is
It should control pH most effectively.

Preferred inorganic buffers / alkali sources include alkali metal carbonates, alkali metal hydroxides, and alkali metal sulfates, such as sodium carbonate, sodium hydroxide, sodium polyphosphate, and the like.

The buffering agent may itself be an active detergent, or it may be a low molecular weight organic or inorganic material used in the composition only to maintain an alkaline pH. Preferred buffers for the compositions of the present invention are nitrogen-containing substances. Other examples of suitable buffers are found in 7408P.

Optional Detergent Components Polymerizable Foam Stabilizer- The compositions of the present invention can optionally include a polymerizable foam stabilizer. These polymerizable suds stabilizers provide a wide range of suds and lather duration without sacrificing the grease removal properties of the liquid detergent composition. These polymerizable foam stabilizers are selected from: i) homopolymers of (N, N-dialkylamino) alkyl acrylate esters having the formula:

[0095]

Embedded image

In the above formula, each R is independently hydrogen, C ₁ -C ₈ alkyl, and a mixture thereof, R ¹ is hydrogen, C ₁ -C ₆ alkyl, and a mixture thereof, and n is Ii) copolymers of (i) with those represented by the formula:

[0097]

Embedded image

In the above formula, R ¹ is hydrogen, C 1 -C 6 alkyl, and mixtures thereof, provided that the ratio of (ii) to (i) is from about 2 to 1 to about 1 to 2. The molecular weight of the polymerizable foaming agent measured by general gel filtration chromatography is about 1
2,000 to about 2,000,000, preferably about 5,000 to about 1,000,000
000, more preferably from about 10,000 to about 750,000, more preferably from about 20,000 to about 500,000, even more preferably from about 35,000 to about 200,000. The polymerizable foam stabilizer can optionally be present in the form of a salt, an inorganic or organic salt, such as a citrate, sulfate or nitrate of an (N, N-dimethylamino) alkyl acrylate ester.

One of the preferred polymerizable foam stabilizers is (N, N-dimethylamino) alkyl acrylate esters, ie

[0100]

Embedded image

Is as follows.

[0102] When present in the composition, the polymerizable foam enhancer is present in the composition at about 0.5% by weight.
It is present from 01% to about 15%, preferably from about 0.05% to about 10%, more preferably from about 0.1% to about 5%.

Builders -The compositions according to the invention can further comprise a builder system. Builders, such as citric acid and citrate, inhibit enzyme stability in LDL compositions, so builder salts commonly used in LDL compositions incorporating propylene glycol as a builder are reduced or eliminated altogether. Is preferred. When the detergent composition comprises a propylene glycol solvent as part or all of the detergent carrier, the enzymes are relatively stable and require less or no builder salt.

If the use of a builder is desired, any common builder system can be suitably used here: aluminosilicate materials, silicates, polycarboxylates and fatty acids, substances such as ethylenediaminetetraacetic acid, aminopolyphosphonates Sequestering agents such as ethylenediaminetetramethylenephosphonic acid and diethylenetriaminepentamethylenephosphonic acid. Although less preferred for obvious environmental reasons, phosphate builders can also be used here.

Polycarboxylate builders that can be suitably used in the present invention include citric acid (
Form of water soluble salts is preferred), there is a succinic acid derivative having the formula _{R-CH (COOH) CH 2} (COOH). In the above formula, R is C _10-20 alkyl or alkenyl,
It is preferably _C12-16 , and R may be substituted with a hydroxyl, sulfosulfoxyl or sulfone substituent. Special examples are lauryl succinate,
There are myristyl succinate, palmityl succinate 2-dodecenyl succinate and 2-tetradecenyl succinate. The succinate builders are preferably used in the form of water-soluble salts such as sodium, potassium, ammonium and alkanol ammonium salts.

Other suitable polycarboxylates are oxodisuccinates and mixtures of monosuccinate and disuccinate tartrate. These are U.S. Pat.
No. 663,071.

In particular, in the liquid product according to the invention, suitable fatty acid builders used here are saturated or unsaturated C _10-18 fatty acids and the corresponding soaps. Preferred saturated species have 12 to 16 carbon atoms in the alkyl chain. A preferred unsaturated fatty acid is oleic acid. Other preferred builder systems for liquid compositions are based on dodecenyl succinic and citric acid.

If detergency builder salts are included, they may be present in an amount of from 0.5 to 50% by weight of the composition.
, More preferably 5 to 30% by weight, most usually 5 to 25% by weight.

Enzymes- The detergent compositions of the present invention can further comprise one or more enzymes that provide a cleaning benefit. The enzymes include cellulase, hemicellulase, peroxidase, protease, gluco-amylase, amylase, lipase, cutinase, pectinase, xylanase, reductase, oxidase, phenol oxidase, lipoxygenase, ligninase, pullulanase, tannase, pentosanase, malanase, β-glucanase. , Arabinosidase or mixtures thereof. A preferred combination is a detergent composition comprising a cocktail of commonly used enzymes such as proteases, amylase, lipase, cutinase and / or cellulase. When present in the composition, the amount of enzymes is from about 0.0001% to about 5% active enzyme by weight of the detergent composition. Preferred proteolytic enzymes are selected from the group consisting of Alcalase (trade name) (Novo Industry A / S), BPN ', protease A and protease B (Genencor), and mixtures thereof. Protease B is most preferred. Preferred amylase enzymes include TERMAMYL
) (Trade name), DURAMYL (trade name), and amylase enzymes described in Genencol International WO9418341 and Novo WO9402597.

Other non-limiting examples of suitable and preferred enzymes are co-pending applications: “Dishwashing Detergent Compositions Containing Organic Diamines for Grease Cleaning, Foaming, Low Temperature Stability and Improved Solubility” (P & G Case) No. 7167P, Application No. 60 / 087,693). This is incorporated herein by reference.

Since compositions such as hydrogen peroxide and builders, such as citric acid and citrate, inhibit the stability of the enzymes in LDL compositions, reducing or eliminating the concentration of these compounds in compositions containing enzymes is difficult. preferable. Hydrogen peroxide is often found as an impurity in surfactants and surfactant pastes. For example, the desired level of hydrogen peroxide in an amine oxide or in an amine oxide surfactant paste is 0-40 ppm,
More preferably, it is 0-15 ppm. The amine impurities in the amine oxides and betaines (if present) should be minimized to the levels mentioned above for hydrogen peroxide, and should preferably be less than 1 ppm.

Magnesium Ions While it is preferred to remove divalent ions from the LDL compositions made according to the present invention, alternative embodiments of the present invention can include magnesium ions.

[0113] It is desirable to exclude all divalent ions from the LDL compositions of the present invention because such ions lead to slow dissolution as well as low rinsing efficiency and poor low temperature stability. Moreover, it is difficult to formulate such a divalent ion-containing composition in an alkaline pH substrate because divalent ions, especially magnesium, are incompatible with hydroxide ions.

Nevertheless, the presence of magnesium ions offers several advantages. It should be noted that the addition of such divalent ions improves the cleaning of greasy soils in various LDL compositions, especially those containing alkyl ethoxy carboxylate and / or polyhydroxy fatty acid amide. This is especially so when the composition is used in soft water that contains few divalent ions.

However, in the present invention, these benefits can be obtained without adding divalent ions. In particular, the use of organic diamines and amphoteric and anionic surfactants in combination with the above-mentioned specific ratios improves the oil / fat washing without the insertion of divalent ions, while the enzyme is used in the LDL composition of the present invention. It has been shown to improve the mildness of the object on the skin.

If magnesium ion is to be included in another embodiment of the LDL composition of the present invention, the magnesium ion is present in an active amount of about 0.01 to 1% by weight,
Preferably it is present from about 0.015 to 0.5% by weight, more preferably from about 0.025 to 0.1% by weight. The amount of magnesium ions present in the composition of the present invention also depends on the amount of total surfactant, including the amount of alkyl ethoxy carboxylate and the amount of polyhydroxy fatty acid amide, present in the composition.

It is preferred to add magnesium ions to the compositions of the present invention as hydroxides, chlorides, acetates, sulfates, formates, oxides or nitrates. During storage, it is necessary to add certain chelating agents because the presence of compositions containing moderate concentrations of hydroxide ions reduces the stability of these compositions due to the formation of hydroxide precipitates. Suitable chelators are described in detail below and in US Pat. No. 5,739,092, issued Apr. 14, 1998. This is incorporated herein by reference.

Chelating Agents- The detergent compositions of the present invention can also optionally include one or more iron and / or manganese chelating agents. Such chelators can be selected from the group consisting of aminocarboxylates, aminophosphonates, polyfunctionally substituted aromatic chelators and mixtures thereof. All of these are defined below. Without being bound by theory, the benefits of these materials are due, in part, to their excellent ability to remove iron and manganese from washing liquors by the production of soluble chelates.

Aminocarboxylates useful as optional chelating agents include ethylenediaminetetraacetate, N-hydroxyethylenediaminetriacetate, nitrilo-tri-acetate, ethylenediaminetetraproprionate, triethylenetetraminehexaacetate, diethylenetriaminepentaacetate,
And ethanol diglycine, their alkali metal-, ammonium-, and substituted ammonium salts, and mixtures thereof.

Aminophosphonates can also be suitably used as chelating agents in the compositions of the present invention when at least a small amount of total phosphorus is tolerated in the detergent composition, and ethylenediaminetetrakis (methylene phosphonate) can be used in DEQUEST. ). These aminophosphonates preferably do not contain alkyl or alkenyl groups having about 6 or more carbon atoms.

[0121] Polyfunctionally substituted aromatic chelators are also useful in the compositions of the present invention. 1974
See U.S. Pat. No. 3,812,044, issued to Connor et al. Preferred compounds of this type in the acid form are 1,2-dihydroxy-3
And dihydroxydisulfobenzenes such as 5,5-disulfobenzene.

Preferred biodegradable chelators for use in the present invention are ethylenediaminedisuccinate ("EDDS"), particularly Hartman and Perkins, US Pat. No. 4,704,233, Nov. 3, 1987. No. [
[S, S] isomer.

The composition of the present invention may be a water-soluble methyl glycine diacetate (MGDA) salt (or acid form).
Can also be included as chelating agents or auxiliary builders. Similarly, so-called "weak" builders, such as citrate, can be used as chelating agents.

When used, these chelating agents generally comprise from about 0.1 to 15% by weight of the composition of the present invention. More preferably, if used, the chelating agent will comprise from about 0.1% to about 3.0% of such a composition.

Other Perfumes In addition to the above perfumes and fragrances, the detergent compositions of the present invention may also contain various other natural extracts and essences which are complex mixtures of the following ingredients: orange Oil, lemon oil, rose extract, lavender, musk, patchouli, balsam essence, sandalwood oil, pine oil, cedar, etc. The resulting perfume may contain a very complex mixture of such components. Other examples of perfume ingredients useful in the present invention are the co-pending provisional patent applications described above:
Dishwashing detergent compositions containing organic diamines to improve low temperature stability and dissolution "
(P & G case number 7167P, application no. 60 / 087,693). It should be noted that additional components that fall under these "other components" headings are included in addition to the perfume composition formulations described above.

Other Ingredients -The detergent composition preferably further comprises one or more detergent auxiliary substances selected from: soil removal polymers, polymerizable dispersants, polysaccharides, abrasives, germicides and others. Antibacterial agents, discoloration inhibitors, builders, enzymes, pigments,
Buffers, antifungals or mildew inhibitors, insecticides, fragrances, hydrotropes, thickeners, processing aids, foam enhancers, anti-fogging agents, anticorrosives, stabilizers, antioxidants and chelating agents . A variety of other ingredients useful in the above detergent compositions, such as other active ingredients, carriers, hydrotropes, antioxidants, processing aids, pigments or pigments, solvents for liquid compositions, for rod compositions Solid fillers and the like can also be included in the composition. If high sudsing is desired, generally in foam boosters compositions such as C ₁₀ -C ₁₆ alkanolamides can be added at 1% -10% levels. C ₁₀ -C ₁₄ monoethanol and diethanol amides are typical class of such suds boosters. It is also advantageous to use such foam enhancers with high foaming co-surfactants such as the amine oxides, betaines and sultaines described above.

[0127] Antioxidants can optionally be added to the detergent compositions of the present invention. They are common antioxidants used in detergent compositions, such as 2,6-di-tert-butyl-4-.
Methyl phenol (BHT), carbamate, ascorbate, thiosulfate, monoethanolamine (MEA), diethanolamine, triethanolamine and the like may be used. The antioxidant, if present, is preferably present in the composition from about 0.001 to about 5% by weight.

The various detersive components used in the composition may optionally be further stabilized by absorbing the components into a porous hydrophobic substrate and then coating the substrate with a hydrophobic coating. Can be. It is preferred that the detersive component is mixed with a surfactant before being absorbed by the porous substrate. In use, the detersive component is released from the substrate into the aqueous cleaning solution, where it performs its intended cleaning function.

In order to explain this method in more detail, a porous hydrophobic silica (trade name SIPERN)
AT D10, Degussa) was mixed with C _13-15 ethoxylated alcohol (EO 7) nonionic surfactant proteolytic enzyme solution containing 3% -5% of. Generally, the enzyme / surfactant solution is 2.5 x silica weight. The resulting powder is dispersed with stirring in silicone oil (various silicone oil viscosities in the range of 500-12500 can be used). The resulting silicone oil dispersion is emulsified or otherwise added to the final detergent matrix. In this way, it protects the enzymes, bleaching agents, bleaching activators, bleaching catalysts, photoactivators, dyes, fluorescers, fabric conditioners and hydrolysable surfactants described above, and is used in detergents including liquid laundry detergent compositions. can do.

Further, these dishwashing detergent embodiments preferably also include a hydrotrope. Suitable hydrotropes include sodium-, potassium-, ammonium- or water-soluble substituted ammonium salts of toluenesulfonic acid, naphthalenesulfonic acid, cumenesulfonic acid, xylenesulfonic acid, and the like.

Non-Aqueous Liquid Detergent Liquid detergent compositions comprising a non-aqueous carrier medium are disclosed in US Pat. No. 4,753,570;
No. 4,767,558; No. 4,772,413; No. 4,889,652; No. 4,89.
No. 2,673; GB-A-2,158,838; GB-A-2,195,125; GB-A-2,195,649; U.S. Pat. No. 4,988,462; No. 5,266,233; EP-A-225,654 (6/16/87); EP-
A-510,762 (10/28/92); EP-A-540,089 (5 /
EP-A-540,090 (5/5/93); U.S. Pat. No. 4,61.
No. 5,820; EP-A-565,017 (10/13/93); EP-A-0
30,096 (6/10/81). These are incorporated herein by reference. Such compositions may include various particulate detersive ingredients stably suspended therein. For this reason, such non-aqueous compositions are prepared in a liquid phase (LIQU
ID PHASE) and optionally but more preferably, a solid phase (SOLID PHASE).

The compositions of the present invention can be used to produce aqueous wash solutions for use in hand washing dishes. Generally, an effective amount of such a composition is added to water and such an aqueous wash-
Or produce a soaking solution. The aqueous solution thus formed is then brought into contact with dishes, dishes and utensils.

An effective amount of the detergent composition of the present invention added to water to produce an aqueous cleaning solution is an amount sufficient to form a concentration of 500 to 20,000 ppm in an aqueous solution. More preferably, the concentration of the detergent composition in the aqueous cleaning solution is between about 800 and 5,000 ppm.

The following examples illustrate the invention but do not limit or limit its scope. All parts, percentages and ratios used herein are expressed as percent by weight, unless otherwise specified.

[0135]

【Example】

 Table I The light liquid dishwashing detergents of the present invention are as follows:

[0136]

[Table 1]

[0137] 1: Average 0.6 ethoxy C12-13 containing alkyl ethoxy sulfonate 2: C ₁₂ -C ₁₄ amine oxide 3: Polymer is (N, N- dimethylamino) ethyl methacrylate homopolymer 4: Nonionic surfactant The activator is either a C10 alkyl ethoxylated surfactant containing eight ethoxy groups or a C10 alkyl ethoxylated surfactant containing eight ethoxy groups. 5: 1,3-bis (methylamine) -cyclohexane 6: Perfume composition is as described in Table IV

Table II The light liquid dishwashing detergents of the present invention are as follows:

[0139]

[Table 2]

1: Sodium C12-13 alkyl ethoxy sulfonate containing on average 1 to 3 ethoxy groups 2: Nonionic surfactant is a C10 alkyl ethoxylated surfactant containing 8 ethoxy groups or 8 ethoxy groups Including C10 alkyl ethoxyl surfactants. 3: Perfume compositions are those listed in Table IV.

Table III The light dishwashing liquid detergents of the present invention are as follows:

[0142]

[Table 3]

[0143] 1: Average 0.6 ethoxy C12-13 containing alkyl ethoxy sulfonate 2: C ₁₂ -C ₁₄ amine oxide 3: Polymer is (N, N- dimethylamino) ethyl methacrylate homopolymer. 4: The nonionic surfactant is either a C11 alkyl ethoxylated surfactant containing 9 ethoxy groups or a C10 alkyl ethoxylated surfactant containing 8 ethoxy groups. 5: 1,3-bis (methylamine) -cyclohexane 6: The perfume composition is as described in Table IV.

Table IV Perfume compositions of the present invention are as follows:

[0145]

[Table 4]

──────────────────────────────────────────────────続 き Continuation of front page (81) Designated country EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE ), OA (BF, BJ, CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, LS, MW, SD, SL, SZ, TZ, UG, ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AE, AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CR, CU, CZ, DE, DK, DM, EE, ES, FI, GB, GD, GE, GH, GM, HR, HU, ID , IL, IN, IS, JP, KE, KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MA, MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, TZ, UA, UG, US, UZ, VN, YU, ZA, ZW (72 Inventor Kayser, Carl Eric, United States Ohio, Mason, Park Lake, Drive 6864 (72) Inventor Goldstain, Alan Scott Ohio, United States of America, Blue, Ash, Berry Hill, Lane 4329 (72) Inventor Kaycher, Mark Leslie 9731 F-term, Mason, Ohio, USA 9731 F-term (reference) 4H003 AB31 AC08 AC15 BA12 BA15 DA17 EA16 EA19 EA21 EB04 EB13 EB22 EB28 EB34 ED02 FA18 FA26 FA2 7 FA28 FA30

Claims (10)

[Claims] 1. A liquid dishwashing detergent composition suitable for use in hand washing dishes, comprising: a) an anionic surfactant; b) a solvent; c) an amine having a pKa greater than 8.0; and d). 30% to 1 of an odor neutralizer capable of forming a Schiff base when reacted with an amine
A perfume composition characterized by 00%; and wherein the composition has a pH of 8.5 to 12. 2. The method according to claim 1, wherein the fragrance composition has a boiling point of less than 180 ° C.
The liquid dishwashing detergent composition according to claim 1, further characterized by comprising 1% to 4%. 3. The liquid dishwashing detergent according to claim 1, wherein the perfume composition further comprises 30% to 50% of an aroma substance having a boiling point between 180 ° C. and 260 ° C. Composition. 4. A liquid dishwashing detergent according to claim 1, wherein the perfume composition further comprises 20% to 70% of a fragrance having a ClogP value of greater than 2.5. Composition. 5. The method according to claim 1, wherein the perfume composition comprises less than 20% of an aroma substance having an odor detection threshold of less than 4.0 mg / L in a solution of the aroma substance and water. The detergent composition for washing liquid dishes according to claim 1 or 2. 6. The composition of claim 1, wherein the composition comprises less than 0.5% of hydrogen peroxide.
The detergent composition for washing a liquid dish according to any one of the above. 7. A method for preventing a user from perceiving an amine odor emanating from a composition, comprising: a) 0.1% to 4% of a fragrance having a boiling point of less than 180 ° C .; and b) reacting with the amine. A perfume composition containing 30% to 100% of an odor neutralizer capable of forming a Schiff base when prepared is prepared, a second composition containing an amine generating malodor is prepared, A method characterized in that it is added as one component to the second composition. 8. The method according to claim 7, wherein the perfume composition is characterized by 30% to 50% of a fragrance having a boiling point of 180 ° C. to 260 ° C. 9. The method according to claim 7, wherein the perfume composition is further characterized by 20% to 70% of a fragrance having a ClogP of greater than 2.5. 10. When the fragrance composition is tested in a solution of a fragrance substance and water,
10. The method according to any one of claims 7 to 9, further characterized by less than 20% of a fragrance having an odor detection threshold of less than 0.0 mg / L.