CN1345364A - Diols and polymeric glycols in dishwashing detergent composition - Google Patents

Abstract

Disclosed are detergent compositions for hand dishwashing which, by incorporating certain organic solvents, results in a liquid dishwashing detergent composition that is not only a more effective cleaning agent, but also offers improved physical and enzymatic stability and more convenient rheology and handling characteristics than typical liquid dishwashing compositions.

Description

Glycols and polyglycols in dishwashing detergent compositions

technical field

The present invention relates to liquid or gel dishwashing detergent compositions suitable for hand dishwashing. These compositions contain amphoteric and anionic surfactants, organic diamines, and solvents selected from glycols, polyglycols and mixtures thereof, as well as other detergent ingredients. The components in the compositions disclosed herein are used to impart the preferred food soil cleaning, removal and sudsing properties to such dishwashing detergent products.

Background of the invention

Light duty liquid (LDL) or gel detergent compositions for hand dishwashing are well known in the art. Typically, such products are formulated to provide a wide variety of properties and characteristics, both in terms of performance and aesthetics. Most importantly, liquid or gel dishwashing detergent products must be formulated with various types and amounts of surfactants and other detergent ingredients that will provide suitable solubility and Removes food soils, especially grease stains, from washed tableware when using or washing in an aqueous solution of the product. Accordingly, formulators of liquid dishwashing compositions have been striving to provide consumers with improved cleaning performance by incorporating additional components into the LDL detergent.

Second, the formulated liquid dishwashing product must be physically stable and free from undesired heterogeneity. Here, "physical stability" means that the liquid composition tends to remain as a homogeneous solution, rather than having one or more components precipitate (if the discontinuous phase is a solid) or separate (if the discontinuous phase is a liquid) from the liquid )come out. Thus, useful detergent compositions cannot be heterogeneous and stable under a wide variety of use conditions and storage temperatures - stability at cold temperatures has been found to be particularly difficult by previous formulators. Physical stability not only makes the product look better, and thus makes the product feel better to the consumer, but is also necessary to provide effective wash performance.

Thirdly, the liquid dishwashing product should be formulated to have a certain viscosity so that the product is convenient and practical to use. Thus, the liquid dishwashing composition should not be so thick that it cannot be easily poured from its container, but at the same time should not be so thin that it cannot be concentrated on the surface of the sponge or kitchen utensil. The liquid dishwashing composition should also have a good "dilution profile", which means that the viscosity of the composition decreases as the liquid dishwashing product is further diluted with water. This is in contrast to how many typical liquid dishwashing compositions work, which become more viscous the first time they are diluted with water, which makes them not only more difficult to work with, but also reduces their solubility. "Solubility" is another important attribute of liquid dishwashing products. Solubility refers to how quickly a liquid dishwashing product mixes with water. In general, it is preferred that the detergent product mixes quickly with water so that the consumer can obtain its stain removal benefits immediately, thereby minimizing the time he or she spends on cleaning.

Fourth, special care must be taken when formulating liquid dishwashing products containing enzymes so that the enzymes do not degrade or break down due to their interaction with other detergent ingredients. Enzymes are important components of dishwashing compositions because they provide improved cleaning of protein-based soils and have been shown to provide consumers with better Mildness or skin feel/appearance benefits. However, adding enzymes to liquid dishwashing compositions is difficult because enzymes are unstable in the presence of many standard LDL ingredients, such as citric acid. Also because the enzyme is active in the presence of water, and most liquid dishwashing compositions are aqueous, care must be taken not to activate the enzyme during storage such that the LDL composition is ready to use the enzyme being depleted.

As stated above, there is a continuing need to formulate hand dishwashing liquids which provide superior cleaning results, have a stable composition over a wide temperature range and have a viscosity and consistency which are convenient for hand dishwashing. Accordingly, it is an advantage of the present invention to provide a light duty liquid dishwashing composition which not only has improved cleaning performance but also has a convenient consistency and viscosity and is colorless, odorless and suitable for a wide range of uses Stable at temperature and having improved enzyme stability over existing liquid dishwashing compositions.

Summary of the invention

It has been determined that using solvents selected from certain glycols, certain polyglycols, and mixtures thereof, as described in detail below, combine amphoteric surfactants, anionic surfactants, and organic diamines in a specific ratio to achieve Provides cleaning, oil removal, physical stability, solubility and rheological properties superior to typical liquid dishwashing compositions. In particular, it has been found that the addition of diols improves the physical and enzymatic stability of liquid dishwashing compositions. Diols prepared in accordance with the present invention and described in more detail below have been shown to improve the physical stability of liquid dishwashing compositions, even when some components would normally separate out of solution in the composition to form High pH (above 10.0) and low temperature of the heterogeneous phase. These diols have also been shown to improve enzyme stability even in high water content compositions.

Additionally, like other solvents, these diols stabilize the dishwashing composition, but, unlike other solvents such as ethanol, they do not thin the dishwashing composition in which they are present. This allows formulators to stabilize dishwashing detergent compositions over a wider range of viscosities, since the diol stabilizes the composition without correspondingly lowering the viscosity of the composition.

Additionally, it has been found that the addition of certain polyglycols, especially in combination with sodium chloride or other alkali metal inorganic salts, can improve the dilution profile and low temperature stability of LDL detergent compositions.

其中，n＝0-3，R₇＝H、甲基或乙基；R₈＝H、甲基、乙基、丙基、异丙基、丁基和异丁基；其中，聚二醇选自：A detergent composition according to the first aspect of the present invention comprises: (a) a low molecular weight organic diamine having pK1 and pK2, wherein the pK1 and pK2 of said diamine are both in the range of about 8.0 to about 11.5; (b ) anionic surfactants; (c) amphoteric surfactants; and (d) solvents selected from glycols, polyglycols and mixtures thereof. Wherein, the diol is selected from:

Wherein, n=0-3, R ₇ =H, methyl or ethyl; R ₈ =H, methyl, ethyl, propyl, isopropyl, butyl and isobutyl; wherein, polyglycol is selected from since:

(PO) _x (EO) _y H wherein PO represents a propylene oxide group, EO represents an oxirane group, x+y is about 17-68, and x/(x+y) is about 0.25-1.0; pH Value (measured as a 10% aqueous solution) of about 5.0-12.5, the molar ratio of the anionic surfactant to the amphoteric surfactant to the diamine is about 100:40:1-9:0.5:1 .

According to a second aspect of the present invention, a detergent composition suitable for hand dishwashing contains: (a) about 0.1-5% by weight of a diamine having a molecular weight less than or equal to 400 g/mol; (b) about 5-50% by weight (c) about 0.5-10% by weight of an amphoteric surfactant; (d) about 0.0001-5% by weight of an enzyme; (e) about 0.75-25.0% by weight of a solvent selected from two Alcohols, polyglycols and mixtures thereof; the diols and polyglycols are those described in the first part of the invention. The detergent composition further comprises: (f) about 0.01 to 5% by weight of the following polymeric suds stabilizers selected from:

其中，R各自独立地选自氢、C₁-C₈烷基及其混合物，R¹为氢、C₁-C₆烷基及其混合物，n为2-约6；i) Homopolymers of (N,N-dialkylamino)alkyl acrylates of the formula:

Wherein, each R is independently selected from hydrogen, C ₁ -C ₈ alkyl and mixtures thereof, R ¹ is hydrogen, C ₁ -C ₆ alkyl and mixtures thereof, and n is 2 to about 6;

其中，R¹为氢、C₁-C₆烷基及其混合物；条件是(ii)与(i)的比例为约2∶1-1∶2；并且其中所述的聚合物泡沫稳定剂的分子量为约1000-2000000道尔顿；和ii) a copolymer of (i) and

wherein R ¹ is hydrogen, C ₁ -C ₆ alkyl and mixtures thereof; provided that the ratio of (ii) to (i) is about 2:1 to 1:2; and wherein said polymeric foam stabilizer is having a molecular weight of about 1,000-2,000,000 Daltons; and

iii) mixtures thereof.

pH (as measured in 10% aqueous solution) of about 5.0-12.5, wherein the molar ratio of said anionic surfactant to said amphoteric surfactant to said diamine is about 27:8:1-11:3:1 .

According to a third aspect of the present invention, the detergent composition suitable for hand dishwashing contains: (a) about 0.1-5% by weight of an organic diamine with a molecular weight less than or equal to 400 g/mol; (b) about 5-50% by weight % of anionic surfactants; (c) about 0.5-10% by weight of amphoteric surfactants; (d) about 0.1-10.0% by weight of buffers; (e) about 0.1-1.5% by weight of alkali metal inorganic salts; and (f) about 0.75-25.0% by weight of a solvent selected from the group consisting of diols, polyglycols, and mixtures thereof; the diols and polyglycols are those described above. The pH value (measured by 10% aqueous solution) is about 10-12, and the molar ratio of the anionic surfactant to the amphoteric surfactant to the diamine is about 27:8:1-11:3:1.

All parts, percentages and ratios used herein are expressed as percent by weight unless otherwise indicated. All references cited in relevant part are hereby incorporated by reference.

Detailed description of the invention

Definitions - The detergent compositions contain an "effective amount" or "oil removal improving" of each ingredient as defined herein. Herein, an "effective amount" of the diamine and adjuvant component means an amount sufficient to directly or significantly improve the cleaning performance of the cleaning composition on at least some of the target soils and stains at the 90% confidence level. Thus, when a composition is targeted to include certain greasy soils, the formulator will employ sufficient diamine therein to at least directly improve cleaning performance on these soils.

“环氧丙烷基团”是指如下结构：

"Oxirane group" refers to the following structure:

"Propylene oxide group" refers to the following structure:

"Light duty liquid (LDL) detergent composition" means a detergent composition for hand dishwashing.

其中，n＝0-3，R₇＝H、甲基或乙基；R₈＝H、甲基、乙基、丙基、异丙基、丁基和异丁基。优选的二醇包括丙二醇、1，2-己二醇、2-乙基-1，3-己二醇和2，2，4-三甲基-1，3-戊二醇。含有二醇时，本发明的组合物将包含占该组合物重量的至少约0.5％，更优选至少约1％，甚至更优选至少约3％的二醇。该组合物也优选包含不多于该组合物重量的约20％，更优选不多于约10％，甚至更优选不多于约6％的二醇。The liquid detergent compositions of the present invention contain glycols or contain polyglycols or contain mixtures thereof. Diols suitable for use in the present invention have the following formula:

Wherein, n=0-3, R ₇ =H, methyl or ethyl; R ₈ =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 containing diols, the compositions of the present invention will comprise at least about 0.5%, more preferably at least about 1%, even more preferably at least about 3%, by weight of the composition, of diols. The composition also preferably comprises no more than about 20%, more preferably no more than about 10%, even more preferably no more than about 6%, by weight of the composition, of diol.

The present invention may also comprise polyglycols containing ethylene oxide groups (EO) and propylene oxide groups (PO). These materials are formed by adding blocks of ethylene oxide moieties at the ends of polypropylene diol chains. The polyglycol suitable for the present invention is as follows:

(PO) _x (EO) _y H wherein x+y is about 17-68 and x/(x+y) is about 0.25-1.0. A preferred polyglycol is polypropylene glycol (corresponding to when y≈0) having an average molecular weight of about 1000-5000, more preferably about 2000-4000, most preferably about 2000-3000.

When containing polyglycols, the liquid detergent compositions will contain at least about 0.25%, more preferably at least about 0.5%, even more preferably at least about 0.75%, by weight of the composition, of polyglycols. The composition also preferably comprises no more than about 5%, more preferably no more than about 3%, even more preferably no more than about 2%, by weight of the composition.

To ensure satisfactory physical stability, whenever a polyglycol is incorporated in a liquid dishwashing composition, it must also include the glycol and/or an alkali metal inorganic salt, such as sodium chloride. Suitable amounts of diols that provide physical stability are within the above ranges, while suitable amounts of alkali metal inorganic salts are at least about 0.1%, and less than about 1.5%, preferably less than about 0.8%, by weight of the composition. %.

As noted above, the addition of diols can improve the physical and enzyme stability of liquid dishwashing compositions. Of particular importance to the present invention are the diols which provide an important stabilizing effect to certain polymeric foam stabilizers and enzymes. The addition of polymeric foam stabilizers and enzymes can both provide important benefits.

Without being bound by theory, it is believed that the diol limits the activity of the enzyme in the liquid dishwashing composition during storage, thereby resulting in a stabilizing effect of the enzyme. Enzymes require water for optimum performance, therefore, inactivation is achieved by substituting a portion of the water with the aforementioned diols that are fully miscible with water, thereby reducing the amount of free water that interacts with the enzyme. In use, liquid dishwashing compositions are diluted substantially with water, thereby providing the enzymes with an aqueous environment conducive to optimal activity and performance.

Also without being bound by theory, it is also believed that the physical stabilizing effect of diols and polyglycols arises from their ability to act as hydrotropes. By keeping the phase of the composition stable (even at low temperatures), certain components, especially certain polymers, are prevented from precipitating out of the composition and forming a heterogeneous LDL composition.

Thus, the present invention includes a carrier/solvent system which may consist of one or more of the following components: glycols and polyglycols as described above, water, alkali metal inorganic salts and one or more of the following conventional solvents .

Conventional solvents: In addition to propylene glycol and polypropylene glycol, other various water-miscible liquids, such as lower alkanols, glycols, other polyols, ethers, amines, etc., can be used in the present invention. Particular preference is given to C ₁ -C ₄ alkanols.

When a solvent is used, the composition will preferably contain at least about 0.01%, more preferably at least about 0.5%, even more preferably at least about 1%, by weight of the composition, of solvent. The composition will also preferably contain no more than about 20%, more preferably no more than about 10%, even more preferably no more than about 8%, by weight of the composition, of solvent.

These solvents can be used in combination with an aqueous liquid carrier, such as water, or in the absence of any aqueous liquid carrier. Solvents can be broadly defined as compounds that are liquid at 20-25°C but are not considered surfactants. A distinguishing feature of solvents is that they tend to exist as discrete entities rather than as mixtures of compounds in the generalized sense. Examples of solvents suitable for use in the present invention include ethanol, propanol, isopropanol, 2-methylpyrrolidone, benzyl alcohol and morpholine nitroxide. Ethanol and isopropanol are preferred among these solvents.

Solvents suitable for use herein include ethers and diethers containing 4-14 carbon atoms, preferably 6-12 carbon atoms, more preferably 8-10 carbon atoms. Other solvents which are also suitable are, diols or alkoxylated diols, alkoxylated aromatic alcohols, aromatic alcohols, branched fatty alcohols, alkoxylated branched fatty alcohols, alkoxylated straight chain C ₁ -C ₅ alcohols, straight chain C ₁ -C ₅ alcohols, C ₈ -C ₁₄ alkanes and cycloalkanes and halogenated hydrocarbons, C ₆ -C ₁₆ diethylene glycols and their mixtures.

In addition to propylene glycol, polypropylene glycol and diol shown above, other diols have the following formula: HO-CR1R2-OH, wherein, R1 and R2 are independently H or C ₂ -C ₁₀ saturated or unsaturated aliphatic hydrocarbon chains and / or circular is applicable and can be used here. One such suitable diol is dodecanediol.

Suitable alkoxylated glycols useful herein are of the formula:

R-(A) _n -R ¹ -OH wherein, R is H, OH, a linear saturated or unsaturated alkyl group containing 1-20, preferably 2-15, more preferably 2-10 carbon atoms; where , ^R is H or contains 1-20, preferably 2-15, more preferably 2-10 straight-chain saturated or unsaturated alkyls of carbon atoms; A is an alkoxy group, preferably ethoxy, methoxy And/or propoxy; n is 1-5, preferably 1-2. Suitable alkoxylated glycols for use herein are methoxystearyl alcohol and/or ethoxyethoxyethanol.

Suitable aromatic alcohols used herein are of the formula R-OH, wherein R is an alkyl-substituted or non-alkyl-substituted aromatic group containing 1-20, preferably 1-15, more preferably 1-10 carbon atoms . For example, benzyl alcohol is a suitable aromatic alcohol for use herein.

Suitable branched chain fatty alcohols for use herein have the formula R-OH, wherein R is a branched chain saturated or unsaturated alkyl group containing 1-20, preferably 2-15, more preferably 5-12 carbon atoms. Particularly suitable branched chain fatty alcohols for use herein include 2-ethylbutanol and/or 2-methylbutanol.

Suitable alkoxylated aliphatic branched alcohols for use herein are of the formula R(A) _n -OH, wherein R is a branched saturated or unsaturated alkyl group containing 1-20, preferably 2-15 , more preferably 5-12 carbon atoms; wherein, A is alkoxy, preferably butoxy, propoxy and/or ethoxy; n is an integer of 1-5, preferably 1-2. Suitable alkoxylated fatty branched alcohols include 1-methylpropoxyethanol and/or 2-methylbutoxyethanol.

Suitable straight-chain C ₁ -C ₅ alcohols for use herein have the formula R-OH, wherein R is a straight-chain saturated or unsaturated alkyl group containing 1-5, preferably 2-4 carbon atoms. Suitable straight-chain C ₁ -C ₅ alcohols are methanol, ethanol, propanol or mixtures thereof.

Other suitable solvents include, but are not limited to, the following classes: butyl diglycol ether (BDGE), butyl triglycol ether, tertiary amilic alcohols, and the like. Particularly preferred solvents for use herein are butoxypropoxypropanol, butyl diglycol ether, benzyl alcohol, butoxypropanol, ethanol, methanol, isopropanol and mixtures thereof.

Other suitable solvents for use herein include, propylene glycol derivatives such as n-butoxypropanol or n-butoxypropoxypropanol, water-soluble Carbitol R solvent or water-soluble Cellosolve R solvent; water-soluble Carbitol R solvent is a compound of 2-(2-alkoxyethoxy) ethanol, wherein the alkoxy group is derived from ethyl, propyl or butyl; preferred water-soluble carbitol is 2 - (2-butoxyethoxy)ethanol, also known as butyl carbitol. The water-soluble cellosolve R solvent is a compound of 2-alkoxyethoxyethanol, preferably 2-butoxyethoxyethanol. Other suitable solvents include benzyl alcohol and diols such as 2-ethyl-1,3-hexanediol and 2,2,4-trimethyl-1,3-pentanediol and mixtures thereof. Some preferred solvents for use herein are n-butoxypropoxypropanol, butyl carbitol (BUTYL CARBITOL®) and mixtures thereof.

The solvent may also be selected from ether derivatives of mono-, di- and tri-ethylene glycol, butanediol ethers, and mixtures thereof. The molecular weight of these solvents is preferably less than 350, more preferably 100-300, even more preferably 115-250. Examples of preferred solvents include, for example, mono-ethylene glycol n-hexyl ether, mono-propylene glycol n-butyl ether and tri-propylene glycol methyl ether. Ethylene glycol and propylene glycol ethers are commercially available from the Dow Chemical Company under the tradename "Dowanol" and from the Arco Chemical Company under the tradename "Arcosolv". Other preferred solvents include mono- and diethylene glycol n-hexyl ether, commercially available from Union Carbide Corporation.

Diamines: As noted above, the diamines employed in the detergent compositions herein are used in combination with detersive surfactants in amounts effective to obtain at least a direct improvement in cleaning performance. In the case of hand dishwashing compositions, such "use level" variations depend not only on the type and severity of soils and stains, but also on the wash water temperature, wash water volume and length of time the dishes are in contact with the wash water.

Because the habits and practices of users of detergent compositions vary widely, the composition preferably contains at least about 0.1%, more preferably at least about 0.2%, even more preferably at least about 0.25%, and even more preferably at least about 0.1% by weight of the composition. At least about 0.5% diamine is preferred. The composition also preferably contains no more than about 15%, more preferably no more than about 10%, even more preferably no more than about 6%, even more preferably no more than about 5%, and even more preferably no more than about 5% by weight of the composition. 1.5% diamine.

In one of several aspects of the present invention, there is provided a method of enhancing the removal of greasy/oily soils by using the specific diamines of this invention in combination with surfactants. Greasy/oily "everyday" soils are mixtures of triglycerides, lipids, polysaccharide complexes, fatty acids, inorganic salts and proteinaceous substances.

Therefore, the use of diamines as described below in combination with amphoteric and anionic surfactants in specific ratios improves the cleaning of greasy and viscous foods, which allows, in preferred embodiments of this formulation, the removal or reduction of divalent ions quantity. Diamines tend to act as buffers for increasing the alkalinity of dishwashing compositions, resulting in improved cleaning performance. Removal of divalent ions yields superior dissolution rates, which even allow formulators to formulate hand dishwashing detergents with significantly higher viscosities (e.g., 1000 centipoise or higher) than conventional formulations while maintaining excellent dissolution and cleaning properties, especially It is a concentrated formula. This has important potential advantages for making concentrated products of higher viscosity while maintaining acceptable solubility. "Concentrated" or "ultra" refers to detergent formulations with reduced water content compared to conventional liquid detergents. For "concentrated" or "ultra" formulations, the water content is less than 50%, preferably less than 30%, by weight of the liquid dishwashing detergent composition. The advantage of the concentrated product to the consumer is that the consumer only uses a smaller amount of product; the advantage to the producer is that the transportation cost is reduced. For compositions that are not concentrated, water levels of less than about 85%, more preferably less than about 70%, by weight of the liquid dishwashing detergent composition are useful.

Preferably, the diamines used in the present invention are substantially free of impurities. Here, "substantially free" means that the purity of the diamine is higher than 95%, that is, preferably 97%, more preferably 99%, more preferably 99.5%, free of impurities. Examples of impurities that may be present in commercially available diamines include 2-methyl-1,3-diaminobutane and alkylhydropyrimidines. Furthermore, the diamine should be free of oxidizing agents to avoid degradation of the diamine and formation of ammonia.

As discussed in more detail below, it is important that the composition be free of hydrogen peroxide when the composition contains enzymes. Even small amounts of hydrogen peroxide can cause problems for formulas containing enzymes. However, the diamine reacts with any peroxide present and acts as an enzyme stabilizer, preventing hydrogen peroxide from reacting with the enzyme. The only disadvantage of diamine-stabilized enzymes is the malodorous nitrogen compounds produced, which can be present in diamine-containing compositions. The use of a diamine as an enzyme stabilizer also prevents the diamine from imparting benefits to the composition for its original purpose of action, namely grease cleaning, foaming, dissolution and low temperature stability. Therefore, it is preferred to accomplish this by using essentially no components as enzyme stabilizers (because hydrogen peroxide may be generated), and/or by using non-diamine antioxidants (although diamines may be malodorous compounds) and reducing the The amount of the primary diamine is used to minimize the amount of hydrogen peroxide present as an impurity in the compositions of the present invention.

Preferred organic diamines have a pK1 and pK2 of about 8.0-11.5, preferably about 8.4-11, even more preferably about 8.6-10.75. For performance and availability considerations, preferred starting materials are 1,3-bis(methylamine)-cyclohexane (pKa=10-10.5), 1,3-propanediamine (pK1=10.5; pK2=8.8) , 1,6-hexanediamine (pK1=11; pK2=10), 1,3-pentanediamine (Dytek EP) (pK1=10.5; pK2=8.9), 2-methyl-1,5- Pentanediamine (Dytek A) (pK1 = 11.2; pK2 = 10.0). Other preferred starting materials are primary/primary diamines with alkylene spacing of C4-C8. It is generally believed that primary diamines are preferred over secondary and tertiary diamines.

Definitions of pK1 and pK2 - "pKal" and "pKa2" as used herein are the quantitative symbols "pKa" well known to those skilled in the art, and pKa as used herein is known to those skilled in the chemical arts in the same manner. Reference values here can be obtained from literature, for example, "Critical Stability Constants: Volume2, Amines" by Smith and Martel, Plenum Press, NY and London, 1975. Additional information on pKa can be obtained from relevant company literature, such as that provided by diamine supplier Dupont.

As defined herein, the pKa of a diamine refers to the specified value in full aqueous solution at 25°C and an ionic strength of 0.1-0.5M. pKa is an equilibrium constant that can vary with temperature and ionic strength; therefore, values reported in the literature are sometimes inconsistent due to different measurement methods and conditions. To eliminate ambiguity, relevant conditions and/or references for pKa values used in the present invention are as defined herein or as defined in "Critical Stability Constants: Volume 2, Amines". A typical method of measurement is potentiometric titration of an acid using sodium hydroxide, and by an appropriate method, such as that described in "The Chemist's Ready Reference Handbook" by Shugar and Dean, McGraw Hill, NY, 1990, and The method of reference was used for the determination of pKa.

It has been determined that substituents and structural changes that lower pK1 and pK2 below about 8.0 are undesirable and result in a loss of performance. This can include substituents that would result in ethoxylated diamines, hydroxyethyl substituted diamines, diamines with oxygen atoms beta (and to a lesser extent gamma) to the spacer nitrogen atom (e.g., Jeffamine EDR 148). In addition, raw materials based on ethylenediamine are not suitable.

Diamines useful here can be defined by the following structures: Wherein, R _2-5 are each independently selected from H, methyl, -CH ₂ CH ₃ and oxirane; C _x and C _y are each independently selected from methylene or branched chain alkyl, wherein x+y is about 3-6; A is optional, and is selected from electron-donating or electron-withdrawing groups used to adjust the pKa value of the diamine to a desired range. If A is present, then both x and y must be 1 or greater.

Examples of preferred diamines can be found in co-pending provisional patent application by Phillip Kyle Vinson et al., entitled "Dishwashing Detergent Compositions Containing Organic Diamines for Improved Grease Cleaning, Sudsing, Low Temperature Stability and Dissolution", with P&G Case No. 7167P, application serial number 60/087,693, filed June 2, 1998, incorporated herein by reference.

Anionic Surfactants - Anionic surfactants for use in the present invention are preferably selected from the group consisting of linear alkylbenzene sulfonates, alpha olefin sulfonates, paraffin sulfonates, alkyl ester sulfonates, alkyl sulfates, alkyl Alkoxy sulfates, alkyl sulfonates, alkyl alkoxy carboxylates, alkyl alkoxylated sulfates, sarcosinates, taurates, and mixtures thereof. An effective amount of anionic detersive surfactants for use herein is typically from about 0.5% to 90%, preferably from about 5% to 50%, more preferably from about 10% to 30% by weight.

Examples of suitable anionic surfactants can be found in Chandrika Kasturi et al.'s co-pending provisional patent application entitled "Liquid Detergent Compositions Comprising Polymeric Suds Enhancers" having P&G Case No. 6938P, Serial No. 60/ 066,344, filed November 21, 1997, incorporated herein by reference. More examples of suitable anionic surfactants are given in "Surface Active Agents and Detergents" (Vol. I and II, by Schwartz, Perry and Berch). A variety of such surfactants are also disclosed at column 23, line 58 to column 29, line 23 of US Patent 3,929,678, issued December 30, 1975 to Laughlin et al. Further suitable anionic surfactants can be found in US Patent 5,415,814, Ofosu-Asante et al., issued May 16, 1995, which is incorporated herein by reference in its entirety.

Amphoteric Surfactants: Amphoteric surfactants suitable for use in the present invention are preferably autoxidized amine surfactants. Amine oxides are semi-polar nonionic surfactants, including water-soluble amine oxides containing an alkyl group having a carbon number of about 10-18 and two selected from the group consisting of Alkyl and hydroxyalkyl groups of 1 to 3; water-soluble phosphine oxides containing an alkyl group having from about 10 to 18 carbon atoms and two alkyl groups selected from the group consisting of about 1 to 3 carbon atoms and hydroxyalkyl groups; and water-soluble sulfoxides containing an alkyl group having about 10 to 18 carbon atoms and a group selected from alkyl and hydroxyalkyl having about 1 to 3 carbon atoms base group.

其中，R³为含有约8-22个碳原子的烷基、羟烷基或烷苯基或其混合物；R⁴为含有约2-3个碳原子的亚烷基或羟基亚烷基，或其混合物；x为0-约3；每一个R5都为含有约1-3个碳原子的烷基或羟烷基，或含有约1-3个环氧乙烷基团的聚环氧乙烷基。R⁵基团可以相互连接，例如，通过一个氧原子或氮原子连接形成环状结构。Semi-polar nonionic detergent surfactants include amine oxide surfactants of the formula:

Wherein, ^R3 is an alkyl group, hydroxyalkyl group or alkylphenyl group or a mixture thereof containing about 8-22 carbon atoms; ^R4 is an alkylene group or hydroxyalkylene group containing about 2-3 carbon atoms, or Mixtures thereof; x is 0 to about 3; each R5 is an alkyl or hydroxyalkyl group containing about 1 to 3 carbon atoms, or polyethylene oxide containing about 1 to 3 oxirane groups base. The R ⁵ groups may be linked to each other, for example, via an oxygen or nitrogen atom to form a ring structure.

These amine oxide surfactants include in particular C ₁₀ -C ₁₈ alkyl dimethyl amine oxides and C ₈ -C ₁₂ alkoxyethyl dihydroxyethyl amine oxides.

其中，R₁为烷基、2-羟烷基、3-羟烷基或3-烷氧基-2-羟丙基，其中，烷基和烷氧基分别含有约8-18个碳原子；R₂和R₃分别是甲基、乙基、丙基、异丙基、2-羟乙基、2-羟丙基或3-羟丙基；n为0-约10。Also suitable are amine oxides such as propylamine oxide, represented by the formula:

Wherein, R _is alkyl, 2-hydroxyalkyl, 3-hydroxyalkyl or 3-alkoxy-2-hydroxypropyl, wherein the alkyl and alkoxy contain about 8-18 carbon atoms respectively; R ₂ and R ₃ are methyl, ethyl, propyl, isopropyl, 2-hydroxyethyl, 2-hydroxypropyl or 3-hydroxypropyl, respectively; n is 0 to about 10.

其中，R₁为烷基、2-羟烷基、3-羟烷基或3-烷氧基-2-羟丙基，其中，烷基和烷氧基分别含有约8-18个碳原子；R₂和R₃分别是甲基、乙基、丙基、异丙基、2-羟乙基、2-羟丙基或3-羟丙基；n为0-约10。特别优选具有下式的氧化胺：

其中，R₁为C_10-14烷基，R₂和R₃是甲基或乙基。因为它们都是低发泡的，所以使用长链氧化胺表面活性剂也是可取的，这在U.S.Pat.Nos.4,316,824(Pancheri)，5,075,501和5,071,594中有更充分地描述，在此引入作为参考。Another class of suitable amine oxide semi-polar surfactants includes compounds of the formula:

Wherein, _R is alkyl, 2-hydroxyalkyl, 3-hydroxyalkyl or 3-alkoxy-2-hydroxypropyl, wherein the alkyl and alkoxy contain about 8-18 carbon atoms respectively; R ₂ and R ₃ are methyl, ethyl, propyl, isopropyl, 2-hydroxyethyl, 2-hydroxypropyl or 3-hydroxypropyl, respectively; n is 0 to about 10. Particular preference is given to amine oxides of the formula:

Wherein, R ₁ is C _10-14 alkyl, R ₂ and R ₃ are methyl or ethyl. Because they are all low foaming, it is also desirable to use long chain amine oxide surfactants, which are more fully described in US Pat. Nos. 4,316,824 (Pancheri), 5,075,501 and 5,071,594, incorporated herein by reference.

Non-limiting examples of other amphoteric detergent surfactants suitable for use herein include amidopropyl betaines and derivatives of aliphatic or heterocyclic secondary and tertiary amines, wherein the aliphatic moiety can be straight Chain or branched, wherein one of the aliphatic substituents contains about 8 to 24 carbon atoms, and at least one of the aliphatic substituents contains an anionic water-soluble group.

Further examples of suitable amphoteric surfactants are given in "Surface Active Agents and Detergents" (Vol. I and II, by Schwartz, Perry and Berch), incorporated herein by reference.

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

Co-surfactant - The co-detersive surfactant can be selected from nonionic surfactants, cationic surfactants, amphoteric surfactants, zwitterionic surfactants, and mixtures thereof. By selection of the type and amount of detersive surfactant, and other additional components disclosed herein, the detergent compositions of the present invention can be formulated for use in washing machine cleaning or for other various cleaning, especially including dishwashing . Therefore, a wide variety of specific surfactants are used, depending on the end use of the product. Suitable co-surfactants are described in detail in Chandrika Kasturi et al. co-pending provisional patent application, entitled "Liquid Detergent Compositions Comprising Polymeric Suds Enhancers," having P&G Docket No. 6938P, Application No. 60/066,344, Introduced as above.

The ratio of anionic surfactant to amphoteric surfactant to diamine: in the composition of the present invention, the molar ratio of anionic surfactant: amphoteric surfactant: diamine is about 100:40:1-9:0.5: 1. Preferably, the molar ratio of anionic surfactant: amphoteric surfactant: diamine is about 27:8:1-11:3:1. It has been found that detergent compositions containing this specific ratio range of anionic surfactant, amphoteric surfactant and diamine provide improved low temperature stability, better oil removal and The cleaning effect of sticky food is also improved for hard water cleaning.

In another aspect of the present invention, it has been found that a molar ratio of anionic surfactant to diamine greater than 9:1, preferably greater than 20:1, improves low temperature stability, resulting in better oil removal and stickiness The food cleaning effect is also improved for hard water cleaning. Optional detergent components:

Polymeric Foam Stabilizer - The compositions of the present invention optionally contain a polymeric foam stabilizer. These polymeric suds stabilizers expand the volume of the suds and provide suds durability without sacrificing the degreasing power of liquid detergent compositions. These polymeric foam stabilizers are selected from:

i) a homopolymer of (N,N-dialkylamino)alkyl acrylates of the formula: Wherein, each R is independently hydrogen, C ₁ -C ₈ alkyl and mixtures thereof, R ¹ is hydrogen, C ₁ -C ₆ alkyl and mixtures thereof, and n is 2 to about 6;

其中，R¹是氢、C₁-C₆烷基及其混合物，条件是(ii)与(i)的比例为约2∶1-1∶2；通过常规凝胶渗透色谱法测定，聚合物泡沫促进剂的分子量为约1000-2000000，优选约5000-1000000，更优选约10000-750000，更优选为约20000-500000，甚至更优选为约35000-200000。该聚合物泡沫稳定剂任选以盐的形式存在，或者无机盐或者有机盐例如(N，N-二甲基氨基)烷基丙烯酸酯的柠檬酸盐、硫酸盐、或硝酸盐。ii) Copolymers of (i) and substances of the formula:

wherein R ¹ is hydrogen, C ₁ -C ₆ alkyl and mixtures thereof, provided that the ratio of (ii) to (i) is about 2:1 to 1:2; as determined by conventional gel permeation chromatography, the polymer The foam booster has a molecular weight of about 1,000-2,000,000, preferably about 5,000-1,000,000, more preferably about 10,000-750,000, more preferably about 20,000-500,000, even more preferably about 35,000-200,000. The polymeric foam stabilizer is optionally present in the form of a salt, either an inorganic or organic salt such as citrate, sulfate, or nitrate of (N,N-dimethylamino)alkylacrylate.

A preferred polymeric foam stabilizer is (N,N-dimethylamino)alkyl acrylate, i.e.

When present in the composition, the polymeric suds booster is present in the composition at a level of about 0.01-15%, preferably about 0.05-10%, more preferably about 0.1-5% by weight of the composition.

Builders - The compositions of the present invention may further contain a builder system. Because builders such as citric acid and citrates can destabilize enzymes in LDL compositions, it is desirable to reduce or completely eliminate builder salts, which are often used in combination with propylene glycol as a builder for LDL compositions . When the detergent composition contains propylene glycol solvent as part or all of the detergent carrier, the enzyme is more stable and requires less or no builder salts.

If builders are desired, any conventional builder system is suitable here including aluminosilicate materials, silicates, polycarboxylates and fatty acids, materials such as ethylenediaminetetraacetic acid, metal ion chelates Such as amino polyphosphonates, especially ethylenediaminetetramethylenephosphonic acid and diethylenetriaminepentamethylenephosphonic acid. Phosphate, although less preferred for obvious environmental reasons, can also be used here.

Suitable polycarboxylate builders for use herein include citric acid, preferably in the form of a water-soluble salt, derivatives of succinic acid of the formula R—CH(COOH)CH ₂ (COOH), wherein R is C _{10 - 20} Alkyl or alkenyl, preferably C _12-16 , or where R may be substituted by hydroxy, sulfosulfoxylate or sulfone substituents. Specific examples include lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenyl succinate, 2-tetradecenyl succinate. Succinate builders are preferably used in the form of their water-soluble salts, including sodium, potassium, ammonium and alkanolamine salts.

Other suitable polycarboxylates are oxysuccinates and mixtures of tartrate monosuccinate and tartrate disuccinate, as described in US 4,663,071.

Particularly for liquid applications herein, suitable fatty acid builders for use herein are saturated or unsaturated C _10-18 fatty acids, and corresponding soaps. Preferred saturated types contain alkyl chains of 12-16 carbon atoms. A preferred unsaturated fatty acid is oleic acid. Other preferred builder systems for liquid compositions are based on dodecenylsuccinic acid and citric acid.

Detergency builder salts, if included, are present at levels of 0.5-50%, preferably 5-30%, most often 5-25%, by weight of the composition.

Enzymes: The detergent compositions of the present invention further comprise one or more enzymes capable of imparting cleaning performance. Described enzyme comprises cellulase, hemicellulase, peroxidase, protease, glucose-amylase, amylase, lipase, cutinase, pectinase, xylanase, reductase, Enzymes such as oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, beta-glucanases, arabinases, or mixtures thereof. Preferred combinations are detergent compositions containing mixtures of conventionally used enzymes such as proteases, amylases, lipases, cutinases and/or cellulases. When present in the composition, enzymes comprise from about 0.001% to about 5% active enzyme by weight of the detergent composition. Preferred proteolytic enzymes are selected from Alcalase® (Novo Industri A/S), BPN', Protease A and Protease B (Genencor) and mixtures thereof. Protease B is most preferred. Preferred amylases include TERMAMYL, DURAMYL and those described in WO 9418314 to Genencor International and WO 9402597 to Novo.

Other non-limiting examples of suitable and preferred enzymes are disclosed in co-pending application: "Dishwashing Detergent Compositions Containing Organic Diamines for Improved Grease Cleaning, Sudsing, Low temperature stability and Dissolution", which has P&G docket number 7167P, its application serial number 60/087,693, incorporated herein by reference.

Since hydrogen peroxide and builders such as citric acid and citrates impair the stability of enzymes in LDL compositions, it is desirable to reduce or eliminate these compounds from compositions containing enzymes. Hydrogen peroxide is often found as an impurity in surfactants and surfactant pastes. As such, the amount of hydrogen peroxide in the amine oxide or amine oxide surfactant paste is preferably 0-40 ppm, more preferably 0-15 ppm. Contaminant amines, if present in amine oxides and betaines, should be reduced to a minimum of the above hydrogen peroxide levels.

Magnesium ions

While it is preferred to remove divalent ions from LDL compositions prepared according to the present invention, magnesium ions may be included in alternative embodiments of the present invention.

It is desirable to remove all divalent ions from the LDL compositions of the present invention because these ions reduce the rate of dissolution while deteriorating cleaning effectiveness and reducing low temperature stability. Additionally, it can be difficult to formulate such divalent ion-containing compositions in alkaline pH matrices due to the incompatibility of divalent ions, particularly magnesium and hydroxide ions.

However, the presence of magnesium ions has several benefits. Notably, for various LDL compositions, especially those containing alkyl ethoxy carboxylates and/or polyhydroxy fatty acid amides, the inclusion of such divalent ions improves the cleaning of greasy stains. This is especially true when the composition is used in soft water which contains low amounts of divalent ions.

In the present invention, however, these benefits can also be obtained without including divalent ions. In particular, when the composition contains organic diamines combined with amphoteric surfactants and anionic surfactants in the above-mentioned specific ratios, improved degreasing properties can also be obtained without divalent ions; it has also been shown that enzymes improve Improve the mildness of the LDL composition of the present invention to the skin.

In another embodiment, magnesium ions, if included in the LDL composition, are present in an active level of about 0.01-1 wt%, preferably about 0.015-0.5 wt%, more preferably 0.025-0.1 wt%. The amount of magnesium ions present in the compositions of the present invention will also depend on the total amount of surfactants present therein, including the amount of alkyl ethoxy carboxylates and polyhydroxy fatty acid amides.

Magnesium ions are preferably added to the compositions of the invention in the form of hydroxides, chlorides, acetates, sulfates, fumarates, oxides or nitrates. The addition of certain chelating agents is necessary because, upon storage, the presence of hydroxide precipitates in compositions containing moderate concentrations of hydroxide ions degrades the stability of these compositions due to the formation of hydroxide precipitates. Suitable chelating agents are discussed further below and are described in US Patent No. 5,739,092, issued April 14, 1998 to Ofosu-asante, incorporated herein by reference.

Perfumes: Perfumes and perfume-like components used in the compositions and methods of the present invention include a wide variety of natural and synthetic chemical ingredients including, but not limited to, the following classes: aldehydes, ketones, esters, and the like. Also includes various natural extracts and fragrances, this can include ingredients such as orange oil, lemon oil, rose extract, lavender, musk, patchouli, balsamic essence, sandalwood oil, pine oil, cedarwood A complex mixture of such. Finished fragrances can also include extremely complex mixtures of these ingredients. Finished perfumes typically comprise from about 0.01 to 2% by weight of the detergent compositions, and individual perfume components can comprise from about 0.0001 to 90% of the finished perfume composition.

Non-limiting examples of fragrance components useful herein can be found in co-pending provisional patent application: "Dishwashing Detergent Compositions Containing Organic Diamines for Improved Grease Cleaning, Sudsing, Low temperature stability and Dissolution," having P&G Docket No. 7167P, which Application Serial No. 60/087,693, cited above.

Chelating Agents - The detergent compositions herein may also optionally contain one or more iron and/or magnesium chelating agents. These chelating agents may be selected from amino carboxylates, amino phosphonates, polyfunctionally substituted aromatic chelating agents and mixtures thereof, all of which are defined below. Without being bound by theory, it is believed that the benefits of these materials are due in part to their exceptional ability to remove iron and manganese ions from wash solutions by forming soluble chelates.

Aminocarboxylates useful as optional chelating agents include ethylenediaminetetraacetate, N-hydroxyethylenediaminetriacetate, nitrilo-tri-acetate, ethylenediaminetetrapropionate, Triethylenetetraminehexaacetate, diethylenetriaminepentaacetate, and ethanol diglycine, alkali metal, ammonium, and substituted ammonium salts of said ammonium salts, and mixtures thereof.

Amino phosphonates are also suitable as chelating agents in the compositions of the present invention when at least low levels of total phosphorus are permitted in detergent compositions, including ethylenediaminetetrakis(methylenephosphonate) as a DEQUEST . Preferably, such amino phosphonates do not contain alkyl or alkenyl groups having more than about 6 carbon atoms.

Multifunctionally substituted aromatic chelating agents may also be used in the composition. See US Patent 3,812,044, issued May 21, 1974 to Connor et al. Preferred compounds of this type in acidic form are dihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene.

A preferred biodegradable chelating agent for use herein is ethylenediamine disuccinate ("EDDS"), particularly its [S,S] isomer, as described in November 3, 1987 to Hartman and Perkins described in US Patent 4,704,233.

The compositions described herein may also contain water-soluble methylglycine diacetoacetate (MGDA) salt (or acid form) as a chelating agent or cobuilder. Similarly, so-called "weak" builders, such as citrates, can also be used as chelating agents.

If employed, these chelating agents will generally comprise from about 0.1% to about 15% by weight of the detergent compositions. More preferably, these chelating agents, if employed, comprise from about 0.1% to about 3.0% by weight of the composition. pH of the composition

The dishwashing compositions of the present invention are susceptible to acidic stress from food soils when in use, ie diluted and applied to soiled dishes. If the composition will be more effective at a pH greater than 7, it will preferably contain a buffer capable of providing a generally more alkaline pH in the composition and in the dilute solution. The dishwashing compositions of the present invention will thus contain from about 0.1 to 15% by weight, preferably from about 1 to 10% by weight. Most preferred is about 2-8% by weight of buffer. The pKa of the buffer should be about 0.5-1.0 pH units (as determined above) below the desired pH of the composition. Preferably, the buffer should have a pKa value of about 7-12. Under these conditions, this buffer provides the most effective pH control while using the least amount.

Preferred inorganic buffer/base sources include alkali metal carbonates, alkali metal hydroxides and alkali metal phosphates, eg, sodium carbonate, sodium hydroxide, sodium polyphosphate.

The buffering agent may itself be an active detergent, or it may be a low molecular weight organic or inorganic material used alone in the composition to maintain an alkaline pH. Preferred buffers for use in the compositions of the present invention are nitrogen-containing materials. Some examples are amino acids such as lysine, or lower alcohol amines such as mono-, di- and tri-ethanolamine. The diamines described in detail above can also be used as buffers and are preferred buffers. Preferred buffer systems for use in the detergent compositions of the present invention include a combination of 0.5% diamine and 2.5% citrate, a combination of 0.5% diamine, 0.75% potassium carbonate and 1.75% sodium carbonate. Other preferred nitrogen-containing buffers are tris(hydroxymethyl)aminomethane (HOCH ₂ ) ₃ CNH ₃ (TRIS), 2-amino-2-ethyl-1,3-propanediol, 2-amino-2-methyl -propanol, 2-amino-2-methyl-1,3-propanol, disodium glutamate, N-methyldiethanolamide, 1,3-diamino-propanol, N,N'-tetra Methyl-1,3-diamino-2-propanol, N,N-bis(2-hydroxyethyl)glycine (N-diglycine) and N-tris(hydroxymethyl)methylglycine (triglycine) . Mixtures of any of the foregoing are also acceptable. For additional buffers, see McCutcheon, EMULSIFIERS AND DETERGENTS, North American Edition, 1997, McCutcheon Division, MC Publishing Company Kirk Publishing, and WO 95/07971, both incorporated herein by reference.

Other Components: The detergent composition will further preferably comprise, one or more soil release adjuncts selected from soil release polymers, polymer dispersants, polysaccharides, abrasives, bactericides and other antimicrobial agents, tarnish Inhibitors, builders, enzymes, dyes, buffers, fungicides or mildew inhibitors, insect repellants, fragrances, hydrotropes, thickeners, processing aids, foam boosters, brighteners, corrosion inhibitors , stabilizers, antioxidants and chelating agents. The compositions of the present invention may comprise a wide variety of other ingredients useful in detergent compositions, including other active ingredients, carriers, hydrotropes, antioxidants, processing aids, dyes or pigments, solvents for liquid formulations, Solid filler for soap compositions, etc. If high foaming is desired, foam boosters such as _C10 - _C16 alkanolamides can be incorporated into the composition, typically at a level of 1-10%. A typical class of such suds boosters is exemplified by the C ₁₀ -C ₁₄ monoethanolamides and diethanolamides. It is also beneficial to use such suds boosters containing high sudsing co-surfactants such as the amine oxides, betaines and sultaines mentioned above.

In the detergent compositions of the present invention, antioxidants may optionally be added. They can be any common antioxidants used in detergent compositions, such as 2,6-di-tert-butyl-4-methylphenol (BHT), carbamates, ascorbates, thiosulfates, monoethanolamine ( MEA), diethanolamine, triethanolamine, etc. If an antioxidant is present, it is preferably present in the composition in an amount of about 0.001 to 5% by weight.

The various soil release ingredients employed in the compositions of the present invention may optionally be further stabilized by absorbing the ingredients onto a porous hydrophobic substrate and then coating said substrate with a hydrophobic coating. These detersive components are preferably mixed with a surfactant prior to adsorption onto the porous substrate. In use, the soil release components are released from the substrate into the aqueous wash liquor where the soil release components exert the soil release properties imparted thereto.

To illustrate the method in more detail, porous hydrophobic silica (trademark SIPERNAT D10, DeGussa) was mixed with a nonionic surfactant containing 3-5% C _13-15 ethoxylated alcohol (EO7). Proteolytic enzyme solution mixed. Typically, the enzyme/surfactant solution is 2.5 times the weight of silica. The obtained powder is stirred and dispersed in silicone oil (silicone oil with a viscosity of 500-12500 can be used). The resulting silicone oil dispersion is emulsified or added to the final detergent matrix. Components such as the aforementioned enzymes, bleaches, bleach activators, bleach catalysts, photoactivators, dyes, optical brighteners, fiber conditioners and hydrolyzable surfactants can be "protected" in this way. " for use in detergents, including liquid laundry detergent compositions.

Additionally, these hand dishwashing detergent embodiments preferably also include a hydrotrope. Suitable hydrotropes include the sodium, potassium, ammonium or water-soluble substituted ammonium salts of toluenesulfonic acid, naphthalenesulfonic acid, cumenesulfonic acid, xylenesulfonic acid. non-aqueous liquid detergent

The manufacture of liquid detergents containing non-aqueous carrier media can be carried out according to the methods disclosed in U.S 4,753,570; 4,767,558; 4,772,413; 4,889,652; U.S.5,266,233; EP-A-225,654 (6/16/87); EP-A-510,762 (10/28/92); EP-A-540,089 (5/5/93); EP-A-540,090 (5/ 5/93); U.S. 4,615,820; EP-A-565,017 (10/13/93); EP-A-030,096 (6/10/81), incorporated herein by reference. Such compositions may contain various particulate soil release ingredients stably suspended therein. Accordingly, such non-aqueous compositions comprise a liquid phase, and optionally but preferably a solid phase, which are described in more detail hereinafter and in the references cited.

The composition of the present invention can be used to prepare aqueous washing solutions for hand dishwashing. Typically, an effective amount of the composition is added to water to form such an aqueous cleaning or soaking solution, which, after forming the aqueous solution, is brought into contact with tableware and kitchenware.

An effective amount of detergent components added to water herein to form an aqueous cleaning solution is an amount sufficient to form about 500-20,000 ppm of the composition in aqueous solution. It is more preferred herein to provide from about 800 to about 5000 ppm of the detergent composition in the aqueous cleaning solution.

The following examples illustrate the invention but are by no means meant to limit its scope. All parts, percentages and ratios used herein are by weight unless otherwise specified. Example Table I

Light service type liquid dishwashing detergent of the present invention is as follows:

Example 1

AE0.6S ¹ 26.1

Amine oxide ² 6.5

Citric acid 2.6

Foam Boost 0.2

Polymer ³

Isopropyl 3.50

Sodium benzenesulfonate

Propylene glycol 9.8

Non-ionic ⁴ 3.0

Diamine ⁵ 50.50

water balance

Total activity 36%

Viscosity (cps@ 780

20℃)

pH@10% 9.0

1: C _12-13 alkyl ethoxy sulfonate with an average of 0.6 ethoxy groups

2: C _12-14 amine oxide

3: The polymer is (N, N-dimethylamino) ethyl methacrylate homopolymer

4: Non-ionic can be a C ₁₁ alkyl ethoxylated surfactant containing 9 ethoxy groups, or a C ₁₀ alkyl ethoxylated surfactant containing 8 ethoxy groups

5: 1,3 bis(methylamine)-cyclohexane Table II

Light service type liquid dishwashing detergent of the present invention is as follows:

Example 2 Example 3 Example 4 Example 5 Example 6

AE0.6S ¹ 26.1 26.1 26.1 13.05 26.1

Amine oxide ² 6.5 6.5 6.5 3.25 5.5

Nonionic ³ 3 3 3 1.5 3

Foam Boost 0.2 0.2 0.2 0.1 0.2

Polymer ⁴

Diamine ⁵ 0.5 0.5 0.5 0.25 0.5

Sodium cumene sulfonate 3.5 3.5 3.5 1.75 2.0

Sodium chloride -- 0.5 0.5 0.25 0.6

Propylene Glycol 9.8 -- 10.0 5.0 --

Polypropylene glycol -- 1.0 1.0 0.5 1.0

Citrate 2.6 -- -- -- -- -- --

Mg ²⁺ -- -- -- -- 0.04

Protease ⁶ -- -- 0.015 0.0075 --

Ethanol -- 7.0 0.0 0.0 7.0

Anion: amine oxide: 23:8:1 23:8:1 23:8:1 23:8:1 23:8:1

The molar ratio of diamine

pH@10% 9 9 9 9 9

1: C _12-13 alkyl ethoxy sulfonate with an average of 0.6 ethoxy groups

2: C _12-14 amine oxide

3: Non-ionic can be a C ₁₁ alkyl ethoxylated surfactant containing 9 ethoxy groups, or a C ₁₀ alkyl ethoxylated surfactant containing 8 ethoxy groups

4: The polymer is (N, N-dimethylamino) ethyl methacrylate homopolymer

5: 1,3 bis(methylamine)-cyclohexane

6: Protease selected from: Savinase®; Maxatase®; Maxacal®; Maxapem 15®; Subtilisin BPN and BPN'; Protease B; Protease A; Protease D; Primase®; . Table III

Light-duty liquid dishwashing detergent of the present invention is as follows:

Example 7 Example 8 Example 9 Example 10

AE0.6S ¹ 26.09 26.09 26.09 28.80

Amine oxide ² 6.50 6.5 8.0 8.0

Foam Boost 0.20 0.20 0.20 0.22

Polymer ³

Isopropyl 3.50 3.50 3.50 3.90

Sodium benzenesulfonate

Non-ionic ⁴ 3.00 3.00 3.00 3.30

Diamine ⁵ 0.50 0.50 0.50 0.55

Sodium chloride 1.5 1.5 1.5 1.5

NaOH 0.35 0.35 0.35 0.35

Na ₂ CO ₃ 1.75 1.75 1.75 1.75

K ₂ CO ₃ 0.75 0.75 0.75 0.75

Propylene Glycol 4.0 4.0 4.0 4.0

Polypropylene Glycol 1.0 1.0 1.0 1.0

Ethanol 3.0 0.7 0.7 --

Water and Misc. Balance Balance Balance Balance

Viscosity (cps@ 353 640 635 848

70F)

pH@10% 10.8 10.8 10.80 10.8

1: C _12-13 alkyl ethoxy sulfonate with an average of 0.6 ethoxy groups

2: C _12-14 amine oxide

3: The polymer is (N, N-dimethylamino) ethyl methacrylate homopolymer

4: Non-ionic can be a C ₁₀ alkyl ethoxylated surfactant containing 8 ethoxy groups, or a C ₁₀ alkyl ethoxylated surfactant containing 8 ethoxy groups

5: 1,3 bis(methylamine)-cyclohexane

Claims (10)

1. liquid dishwashing detergent compositions that is applicable to manual dishwashing, described composition is characterised in that:

A) have the lower molecular weight organic diamine of pK1 and pK2, the pK1 of wherein said diamines and pK2 are all in the scope of about 8.0-11.5;

B) anion surfactant;

C) amphoterics; With

D) be selected from the solvent of glycol, polyglycol and composition thereof; Wherein, described glycol is selected from: Wherein, n=0-3, R ₇=H, methyl or ethyl; R ₈=H, methyl, ethyl, propyl group, sec.-propyl, butyl and isobutyl-; Wherein, polyglycol is selected from:

(PO) _x(EO) _yH wherein PO represents propylene oxide group, and EO represents ethylene oxide group, and x+y is 17-68, and x/ (x+y) is 0.25-1.0; Wherein pH value (determination of aqueous solution with 10%) is 5.0-12.5, and the mol ratio of wherein said anion surfactant and described amphoterics and described diamines is 100: 40: about 9: 0.5: 1 of 1-.

2. the liquid dishwashing cleaning composition of claim 1, its feature also is to contain buffer reagent, and the pH of said composition is 10-11.5.

3. each liquid dishwashing cleaning composition of claim 1-2, wherein said glycol is selected from propylene glycol, 1,2-hexylene glycol, 2-ethyl-1,3-hexylene glycol and 2,2,4-trimethylammonium-1, the 3-pentanediol, and composition thereof.

4. each liquid dishwashing cleaning composition of claim 1-3, wherein said polyglycol is that molecular weight is the polypropylene glycol of 1000-5000.

5. each liquid dishwashing cleaning composition of claim 1-4, wherein said diamines is selected from:

Wherein, R _2-5Be selected from H, methyl, ethyl and oxyethane independently of one another; C _xAnd C _yBe selected from methylene radical or branched-chain alkyl independently of one another, wherein x+y is 3-6; A is optional the existence, is selected from order to the pKa value of this diamines is adjusted to power supply or the electron-withdrawing group of the scope of wanting, if wherein A exists, x and y are necessary for 2 or bigger so.

6. each liquid dishwashing cleaning composition of claim 1-5, wherein said polyglycol is that molecular weight is the polypropylene glycol of 2000-4000, and its amount is the 0.25-5.0% of composition weight.

7. each liquid dishwashing cleaning composition of claim 1-6, its feature is that also the foam of polymers stablizer is selected from:

I) homopolymer of (N, N-dialkyl amido) alkyl acrylate, suc as formula:

Wherein, R is selected from hydrogen, C independently of one another ₁-C ₈Alkyl and composition thereof, R ¹Be hydrogen, C ₁-C ₆Alkyl, and composition thereof, n is 2-6; With

The ii) multipolymer of (i) and following formula

Wherein, R ¹Be hydrogen, C ₁-C ₆Alkyl and composition thereof; Condition is to be 2 with the ratio of (i) (ii): 1-1: 2; Wherein, described foam of polymers stablizer molecular weight is 1000-2000000 dalton.

8. each liquid dishwashing cleaning composition of claim 1-7, its feature also is to contain α-Dian Fenmei, and this amylase that records by the activity analysis of Phadebas  α-Dian Fenmei is the specific activity at least high 25% of 25-55 ℃ and the pH value specific activity when being 8-10 than Termamyl  in temperature.

9. method of cleaning substrate when manual dishwashing is operated is characterized in that may further comprise the steps:

(a) described substrate is contacted with the liquid dishwashing cleaning composition for preparing according to claim 1; With

(b) described cleaning composition and described substrate are still kept in touch for some time, provide effective cleaning performance for substrate so that be enough to.

10. when each method of claim 1-9, wherein said liquid dishwashing cleaning composition were used for described substrate, dilute with water was no more than 90%.